University Microfilms International300 N

8009261

CHANG, SOU-JEN UNY

PART I: THERMAL AND PHOTOLYTIC BEHAVIOR OE DIAZOACENAPI1THENONE SYSTEMS; CHEMISTRY OF ACHNAPHTHENEQUINONE BIS (PARA-TOSYLHYDRAZONE), PART II: 5-BROMO-4-QUINOLYLDIAZOMETHANE AND 4-QUINOLYLDIAZOMETHANE: SYNTHESIS, THERMOLYSIS AND PHOTOCHEMISTRY

Hie Ohio State University PH.D. 1979

University Microfilms International300 N. Zccb Road, Ann Arbor, M I 48106 18 Bedford Row, London 3VC1R 4FJ, England PART Is THERMAL AND PHOTOLYTIC BEHAVIOR OF DIAZO-

ACENAPHTHENONE SYSTEMS; CHEMISTRY OF ACENAPH-

THENEQUINONE BIS(o-TOSYLHYDRAZONE)

PART II: 5-BROMO-^-QUINOLYLDIAZOMETHANE AND ^-QUINOLYL-

DIAZOMETHANE: SYNTHESIS, THERMOLYSIS AND

PHOTOCHEMISTRY.

DISSERTATION

Presented in Partial Fulfillment of the Requirements for

the Degree Doctor of Philosophy in the Graduate

School of The Ohio State University

Sou-Jen Chang, B. Sc.

The Ohio State University

1979

Reading Committee: Approved By Professor Mathew A. Plats

Professor Harold Shechter

Professor John S. Swenton

Advisor Department of Chemistry DEDICATION

for Mr. and Mrs. Y.-T. Chang,

my parents, without whom

this would not have been possible ACKNOWLEDGMENTS

I wish to express my sincere gratitude to Professor

Harold Shechter for his intellectual quidance arid inspiration

during the course of this research. His patience,

encouragement and understanding should not be forgotten.

I would also like to extend my appreciation to the

Ohio State University, the National Science Foundation and

the National Institutes of Health for their financial

support. VITA

November 10, 1950...... Born-Taiwan, Republic of China.

1973...... B. Sc. National Taiwan Normal University.

1973-1975...... Teaching Assistant, Department of Chemistry, National Taiwan Normal University; Research Chemist, Department of Chemistry, Academia Sinica, Taipei, Taiwan.

1975-1977...... Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio.

1977-1979...... Research Associate, Department of Chemistry, The Ohio State University, Columbus, Ohio. TABLE OF CONTENTS

Page

DEDICATION...... ii

ACKNOWLEDGMENTS...... iii

VITA...... iv

LIST OF TABLES AND FIGURES...... vii

PART Is THERMAL AND PHOTOLYTIC BEHAVIOR OF DIAZO-

ACENAPHTHENONE SYSTEMS j CHEMISTRY OF

ACENAPHTHENEQUINONE BIS(jd-TOSYLHYDRAZONE) . . 1

STATEMENT OF PROBLEM...... 2

HISTORICAL...... 6

RESULTS AND DISCUSSION...... 38

SUMMARY...... 96

EXPERIMENTAL...... 98

PART II: 5-BR0M0-4-QUIN0LYLDIAZ0METHANE AND

'+-QUINOLYLDIAZOMETHANE s SYNTHESIS,

THERMOLYSIS AND PHOTOCHEMISTRY...... 1^3

STATEMENT OF PROBLEM...... 1^1

HISTORICAL...... 14?

RESULTS AND DISCUSSION...... 157

SUMMARY...... 176

v CONTENTS (CONT’D)

Page

EXPERIMENTAL...... 1?8

REFERENCES

PART 1...... 198

PART II...... 203

vi LIST OF TABLES

Table Page

1 Bond Angles(°) and Bond Distances(A0) of ^2

and ...... 153

LIST OF FIGURES

Figure

1 Diagram of 1-Bromo-lH-cyclobutafde]naphthalene

(2)...... 1^5

vii PART I

THERMAL AND PHOTOLYTIC BEHAVIOR OF

DIAZOACENAPHTHENONE SYSTEMS; CHEMISTRY OF

ACENAPHTHENEQUINONE BIS(£-TOSYLHYDRAZONE)

1 STATEMENT OF PROBLEM

Recently lH-cyclobuta [de]naphthalene (1), 1-methylene-

lH-cyclobuta [de] naphthalene (2 ) and its derivatives, and

lH-cyclobuta [dejnaphthalen-l-one (^) have been prepared in

this laboratory'1'. These unusual molecules have been found

(1) (a) R. J. Bailey, Ph. D. Dissertation, The Ohio State University, 197^; (b) P. Card, Ph.D. Dissertation, The Ohio State University, 1976; (c) F. Friedli, Ph.D. Dissertation, The Ohio State University, 1978* to be surprisingly stable1" and their chemistry1" is of great interest at present. As yet however the preparative methods for 1-^, their derivatives, and their analogs are lengthy, inversatile, and unadaptable for large-scale synthesis. A study has been presently made of the chemistry of various

2 3 diazoacenaphthenone derivatives ((+). The principal objectives of this effort are (1 ) to determine the electronic and steric effects of substituents in inducing possible Wolff rearrangements of k to their corresponding ketenes, 1H- cyclobutafde]naphthalen-l-ylidenemethanone derivatives (6 ), as in equation 1 , (2 ) to study the various insertion and

Z Z 7 Z

capture reactions of the intermediate alpha-ketocarbenes £ derivable from thermolysis, photolysis, and metal ion- catalyzed decompositions of 4, and (3 ) to elaborate various

1 ,3-dipolar addition reactions of 4 with appropriate acceptor substrates. The specific diazo ketones selected for this research are: diazoacenaphthenone (£), 2-diazo-5-nitroacenaphthenone (8 ), 2-diazo-5 ,6-dinitroacenaphthenone (§),

2 -diazo-3 »S-dimethoxyacenaphthenone (10) and 2-diazoaceanthrenone (11). OCH

10 11

A further aspect of this research is investigation of base-catalyzed decomposition of acenaphthenequinone bis(jc- tosylhydrazone) (12). One of the objectives is to study possible generation of 1 ,2-bisdiazoacenaphthene (1^) and its subsequent decomposition to acenaphthylyne (1^-) as in equation 2. Acenaphthylyne (1^) is of our interest because

TosHNN NNHTos

2B -2N, -> -> (2) -2B ,-Toj

12 of its structural similarity to benzyne and it is expected to have significant reactivity in cycloaddition and with various electrophiles and nucleophiles. In this work, some interesting results have been observed and will be presented. HISTORICAL

1-Bromo-lH-cyclobuta [de]naphthalene (12)» the first naphthalene bridged in its 1,8 positions by a single carbon 2 atom moiety, has been synthesized by photolysis of either

8-bromo-l-naphthaldehyde p-tosylhydrazonate (1£) or 8-bromo-

1-naphthyldiazomethane (16) in ether (Eq 3)» Bromide 12

®Na H=NNTos ©

15 (3)

B CHN, 11

16 is surprisingly stable and is storable for long periods in air at room temperature. X-Ray^ analysis reveals that 12 is planar and that much of the strain in its cyclobutane section is relieved by accommodation within its naphthalene moiety. 7

(2) R. J. Bailey and H. Shechter, J. Amer. Chem. Soc., 96, 8116 (197*0 - .

(3) M. A. Gessner, Master's Thesis, The Ohio State University, 1977.

Bromide 1£ undergoes a series of nucleophilic

displacements to give stable bridged compounds. For

example, treatment of 1£ with sodium azide yields 1 -azido-

lH-cyclobuta [de] naphthalene (18, 9^ » Eq *0 • Similar

NaN^ (*0

HMPA

18 displacements have been effected with lithium aluminum hydride, sodium thiophenoxide, potassium cyanide, etc. The Grignard reagent (lg) of 1£ is easily prepared and is usuable as a typical organometallic synthon. Thus, acidification of lg yields lH-cyclobuta [de] naphthalene (20,

Eq 5)i displacement of methyl iodide gives 1-methyl-lH- cyclobuta Qi§3 naphthalene (21), and carboxylation and hydrolysis results in lH-cyclobuta OieJ naphthalene-1- carboxylic acid (22, Eq 5). 8

H MgBr CH

11 + Mg (5)

12 21

1) co^ 2) H^O®

The varied chemistry of 1£ and lg is summarized further in the Ph.D. dissertations of Baileyla, Cardlb, and Friedlilc,

lH-cyclobuta[d§] naphthalene (20) is also a stable, readily handled, planar hydrocarbon. Its structure is very 3 similar to that of VJ< Electrophilic substitution of 20 by various reagents occurs efficiently at the C-^ and C-5 9

positions and without destruction of the four-membered ring.

Thus, nitration of 20 with nitric acid in sulfuric acid or

acetic acid produces 4-nitro-lH-cyclobuta [de] naphthalene (2^)

and 4,5-dinitro-lH-cyclobuta[le]naphthalene (24, Eq 6 ).

HNO (6)

NO NO 2 2 20 24-

Similar substitutions have been effected with acetyl chloride/

aluminum chloride and bromine and iron. The cyclobutyl

ring of 20 is cleaved by hydrogenation however to give

1-methylnaphthalene (2£, Eq 7).

H. H

H, (7) 10% Pd-C

20 25

Of significance to the purposes of the present proposal for synthesis of ketenes such as 6 is that bromide 1£ reacts with triphenylphosphine to form phosphonium bromide 26 which is converted efficiently by sodium dimsylate to phosphorane 10

22 (Eq 8). The strained Wittig reagent 2£ reacts rapidly

H ®PPh3 Br0 PPh © © CHoS0CH0 Na

11 CH-SOCH

-NaBr 26 11

(8 ) 28, R^R^CH- -Ph^PO j ^ „1 „ „2 22, R = Ph, R = H. with a wide variety of aldehydes and ketones to give the highly strained products, 1-alkylidene-lH-cyclobuta[de] - naphthalenes in high yields (Eq 8 ). Thus acetone and benzaldehyde condense with 2£ to form 1-isopropylidene- lH-cyclobuta[de] naphthalene (28) and 1-benzylidene-lH- cyclobuta[de] naphthalene (2g), respectively. Olefins such as 28 and 22 are quite stable and undergo a wide variety of electropholic and free-radical addition reactions'^’ with retention of the cyclobutanoid moiety. Reduction of

28 with hydrogen over palladium on carbon does result in cleavage of the four-membered ring to give 11

1-isobutylnaphthalene (^2 * ^q 9 )•

CH CH

Pd/C

28 30 ^ m Ni rv

At elevated temperature, 1-methylene-lH-cyclobuta-

[de]naphthalene (2 ) undergoes cleavage of its cyclobutyl

ring and subsequent hydrogen migration to give 1-naphthyl- acetylene (^1* 73$>» Eq 10). The temperatures necessary

550 (10) 0.1 mm

2 21 for this isomerization is indicative of the thermal stability of 2 .

Of further relevance to the objectives of the present investigation is that ozonolysis of 28 and work-up with 12 dimethyl sulfide yields lH-cyclobuta [&e] naphthalen-l-one

Eq 11), a stable low melting (mp 40-^4°) compound.

CH CH

0. (11)

28 2

The strain in ketone 2 is revealed by its rapid ring

cleavage with a variety of nucleophiles. For instance,

2 reacts with anhydrous methanol at room temperature to

produce methyl 1-naphthoate (22) presumably via hemiketal

(22, Eq 12). Other nucleophiles that result in ring

HO ✓0CH3 c o 2c h 3

CH. OH 3 -■-> (12)

22 opening of 2 are potassium hydroxide, aniline, 2 ,^-dinitro- phenylhydrazine, Wittig reagents, etc.lb

It has thus been clearly demonstrated that compounds such as 1 , 2 , and 2 and many of their derivatives are 13

stable, usable molecules. Thus ketene such as 6 should be

preparable and of advantage for varied synthetic purposes. o(-Diazo ketones such as k are readily available and their

Wolff rearrangements to ketenes 6 (Eq 1) would appear

feasible. A study of the varied chemistry of ^ has thus

been made as subsequently described.

<*-Diazo aldehydes and ketones are readily

prepared from 1,2-dicarbonyl compounds. Such o(-diazo

carbonyl derivatives are represented structurally as 2^a-c

and are usable preparatively for a variety of applications. 4 Wolff rearrangements of these compounds, induced thermally, photochemically or catalytically^, afford ketenes (2%) with loss of nitrogen (Eq 13)*

1 0 N, R i |i ii^ R — C - C 2-R-R'2 , cat. 0 = 0 = 0 (13) R‘2 '

25 1U

(^) L. Wolff, Justus Liebigs Ann. Chem., 32£» 129 (1902); -ibid.. 222 * 1 ibid., ,39^, 23 (191277 for recent review see H. Meier and K.-P. Zeller, Anp;ew. Chem. Intemat. Edit., 1^, 32 (1975).

(5) W. Kirmse and K. H. Pook, Chem. Ber.. §8 , ^022 (1965); H. Erlenmeyer and M . Aeberli, Helv. Chim. Acta.. (19^-3); P. Yates and R. J. Crawford, J. Amer. ChemT Soc., 8 8 , 1562 (1966).

Wolff rearrangements have been observed in various acyclic, cyclic, aromatic and heterocyclic systems. Thermal energy can induce an o(-diazo aldehyde or ketone to lose nitrogen and undergo Wolff rearrangement at temperatures ranging from 25° to 750° in the gas phase.^ The thermal

(6 ) M. P. Cava and R. J. Spangler, J. Amer. Chem. Soc., 8Q, 4550 (1967). stabilities of substituent effects on the rates of thermolysis of para-substituted phenyl benzoyldiazomethanes (^6 and ^2 ) n _ have been studied. At temperatures ranging from 60 to

95°, the reaction is kinetically first-order for the

compounds ^6 lg k1= + 0. 75 /h -2 . 39 (1*0

compounds 2Z Ig kx= -1.49/l+-2.89 (15) step c^-ketocarbene (2§)-ketene mechanism with rate- determining loss of nitrogen has been proposed (Eq 16).

1 R k R1- c! -C -R 2 C = C = 0

(16)

(7) W. Jugelt and D. Schmidt, Tetrahedron, 2 5 , 969 (i960); A. Melzer and E. F. Jenny, Tetrahedron Lett.7 4503 (1968). 16

Thermal decomposition of substituted o(-diazoacetophenones O (2 2 ) reveal that the ortho-substituted derivatives decompose at much faster rates than the meta- and para- isomers. The magnitude of the ralative rates correlate in

general with the sizes of the ortho-substituents. Steric acceleration is rationalized on the basis that the ortho- substituents restrict resonance of the aryl ring with the

-COCHH^ group. As a result, ortho-substituted compared to meta- and para-isomers, are less resonance stabilized in the ground state and their carbon-nitrogen bonds have less double bond character. Further aspect of

(8 ) D. M. Jordan, Ph.D. Dissertation, The Ohio State University, 1965*

steric effects^ on decomposition is illustrated by diazoketon kO in which the -CO-CN,- group is twisted because of ring strain and which decomposes at room temperature (Eq 17). 17

= o + s + (17) S'J,

(9) A. de Groot, J. A. Boerma, J. de Valk, and H. Wynberg, J. Org. Chem., 22* ^025 (1968).

10 Photochemical Wolff rearrangement is frequently 11 superior to other methods. As seen for diazocamphor (^0)^ thermal or catalytic decomposition results in C-H insertion to give 42, whereas ketene 42 is obtained by photolysis

(Eq 18). In cyclic systems photolytic ring contraction

0 » cat

(18) 2

41 h^ 18

(10) L. Horner and E. Spietschka, Chem. Eer.. 8£, 225 (1952).

(11) J. Bredt and W. Holz, J. prakt. Chem.. 05 , 133 (191?); L. H o m e r and E. Spietschka. Chem. Ber., 88. 9*4 (1955); T. Gibson and W. F. Erman, J. Org. Chem..~3l. 3028 (1966).

frequently occurs and the method is useful for synthesis of 12 strained small-ring compounds such as 44 (Eq 19).

Fh Ph Ph

PhH

Ph Ph Ph

44 (19)

ring size imposes few restrictions on the Wolff rearrangement.

Photochemical Wolff rearrangement often yields compounds

(12) K. Ueda and F. Toda, Chem. Lett.. 779 (1975). which are very difficult or impossible to be prepared by

other methods. Thus photolysis of 3-diazo-2,6-dimethyl-

4-pyridone (4£) at low temperatures in water yields

2,5-dimethylpyrrole-3-carboxylic acid (46, Eq 20) (13) 0. Siis and K. Moller, Justus Liebigs Ann. Chem.. £9 91 (1955); 0. Siis, M. Glos, K. Moller and H. D. Eberharat, ibid., 583, 150 (1953); 0. Siis and K. Moller, ibid., 599. 23TT193ST.

Quinoline derivative decomposes in a similar manner on

irradiation to give, after decarboxylation, indene (^8 ,

Eq 21). 20

The limit of the photochemical method is reached when the

desired reaction product is photolabile under the irradiation

conditions, e.g. with 2-diazo-l,3-indandione Eq 22).

A, hP

, cHjOn it2 /CKjOH

H ^\^CH-C00CH3 -COO CH.

1+5-50'.

CH^OH

CH2-C00CH3 (22) COOCH'

30 %

Photosensitized decomposition differs from direct photolysis of an o^-diaso ketone in that the Wolff rearrange ment is greatly reduced or suppressed and products derived 21 from radical-like abstraction and insertion are obtained. 14 Thus photosensitization of diazoacetophenone (£0) in

2-propanol results in a decrease in yield of the Wolff rearrangement product (£1) and an increase in reduced product (£2) as compared to direct photolysis (Eq 23).

0 Ph-C-CHN2 + Me2CH0H PhCH2C02CHMe2 + PhCOMe (23)

52 51 52

51/52 Direct Yw 2.5

Sensitized h^ 0.003

(14) A. Padwa and R. Layton, Tetrahedron Lett.. 216? (1965)*

Diazocyclohexanone (52) undergoes Wolff rearrangement to intermediate ketene (55) on unsensitized irradiation (Eq

24) and the intermediate carbene (5^) is not trapped by

MeOH

55 5it 55 (24)

MeOH 55 22 olefins^ Photosensitized decomposition however results in an intermediate that does not give Wolff rearrangement directly but is trapped by olefins. It is presumed that

(15) M. Jones, Jr., and W. Ando, J. Amer. Chem. Soc. . 90 2200 (1968). the singlet carbene (£4) involved in unsensitized decomposition reacts with a pair of electrons in the adjacent carbon-carbon single bond, and undergoes rearrangement at

a faster rate than reaction with the more remote 711 - electrons of external olefins. If triplet carbene (£6) were to follow the same reaction path it would have to rearrange to a triplet ketene, many kilocalories/mole in energy above the ground-state singlet. The difficulty of this reaction allows intermediate £6 to add to the external

7C system of the solvent. The loss of stereochemical integrity of cyclopropanes is consistent with what has been *L & observed for postulated triplet carbenes in solution.

(16) M. Jones, Jr., W. Ando, and A. Kulczycki, Jr., Tetrahedron Lett.. 1391 (1967); M. Jones, Jr., and K. R. Rettig, J. Amer. Chem. Soc., 8£, 4013, 4015 (I965K and references therein.

It is, therefore, believed that the singlet carbene is responsible for the Wolff rearrangement. 23

Catalysts are sometimes used during photolysis of o/-diazo carbonyl compounds.17 The decomposition temperatures of

Pt, Pd, Rh, etc. Copper catalysts with the exception of cuprous iodide (Cul) accelerate nitrogen elimination and 18 stabilize the resulting carbene by complex formation.

The same applies to rhodium 19 7 and palladium 20 catalysts.

(17) U. R. Ghatak, P. C. Chakraborti, B. C. Ranu and B. Sanyal, J. C . S . Chem. Comm., 5**8 (1973)*

(18) W. Kirmse "Carbene Chemistry" 2nd Edit., Academic Press, New York 1971; L. L. Rodina and I. K. Korobitsyna, Russ. Chem. Rev., ^6, 260 (1967); A. Mustafa, Advan. Photochem. . 2, 113 (196*0.

(19) R. Paulissen, H. Reimlinger, E. Hayez, A. J. Hubert and Ph. Teyssie, Tetrahedron Lett., 2233 (1973)*

(20) N. Yoshimura, S.-J. Murahashi, and J. Moritani, J. Organometal. Chem., £2C, 58 (1973).

As a consequence, Wolff rearrangement no longer occurs or becomes very difficult.

The mechanism of the Wolff rearrangement has been controversal for a long time. Studies with optically active diazo ketones have domonstrated predominant or complete 21 retention of stereochemistry of the migrating group.

However, certain experiments with optically active diazo 2k

(21) N. A. Preobrashenski, A. K. Poljakowa, and W. A. Preobrashenski, Ber. Deut. Chem. Ges., 68, 850 (1935); J. F. Lane, J. Willenz, A. Weissberger,~and E. S. V/allis, J. Ore. Chem,, £, 276 (1940).

22 ketone , l-diazo-3-methyl-3-phenyl-2-pentanone,

(CH^)(C2H^)(C^H^)G*-C0-GHN2 , indicate that racemization

accompanies rearrangement. This observation is in sharp

contrast to Curtius, Hofmann, and Lossen rearrangements,

(22) J. F. Lane and E. S. Wallis, J. Amer. Chem. Soc.. 62f I6?k (1941).

22 in which no appreciable racemization occurs. Wallis has pointed out the difference in the behavior of the migrating asymmetric group in the two types of rearrangement.

(23) E. S. V/allis and P. I. Bowman, J. Org. Chem., 1. 333 (1936).

In Curtius rearrangement the asymmetric carbon atom retains at all times its complete octet of electrons; whereas, in

Wolff rearrangement at some point the migrating group is left with only a sextet of electrons. In general, such a sextet of electrons is incapable of preserving the asymmetry of a carbon atom in such an intramolecular 25 process and extensive or complete racemization occurs.

Many studies have attempted to determine whether loss of nitrogen precedes migration to give the intermediate ketocarbene (2§) and/or the isomeric oxirene (££)•

0 1 II R — C - C R

R R

£2

The oxirenes antiaromatic 4 71 electron systems possibly formed by valence isomerization of the primary fragments, should possess similar energies to o(-oxocarbenes

28?^ Photolysis of C^-labelled azibenzil (£8) has demonstrated the absence of an oxirene, or any other symmetrical intermediate, in the rearrangement^ (Eq 25).

Ph-^CO-C-PhJ

lL Ph2CH-Cl402H Ph-C 0-CN2-Ph

Ju Fh / Ph ^ (25) Clk \ / 0

25 However, more recently, it has been found in photolysis 13 of C -labelled azibenzil (5§) in cyclopentane that the 26

(2*0 M. J. S. Dewar and C. A. Ramsden, Chem. Commun., 688 (1973); A. C. Hopkinson, J. C. S. Perkin II. 79k (1973): J. G. Csizmadia, H. E. Gunning, R. K. Gosavi and 0. P. Strausz, J. Amer. Chem. Soc.. !33 (1973)•

(25) V. Franzen, Justus Liebigs Ann. Chem.. 6l^, 31 (1958).

isotopic composition of the carbon monoxide (CO) formed indicates scrambling of oxygen to an extent corresponding to 5^% oxirene participation in the reaction (Scheme 1).

SCHEME 1

0 N~ 0 II II2 hif II •• Ph -*C - C -Ph * Ph — *C -C — Ph -> Ph2C ~ C = 0

52 5^% hu N v

0 0 Ph2C: + *C0 II •• Ph — *C — C — Ph R-H ^ \ Ph Ph Ph2CH-R

hv1 * Ph2*C =C = 0 Ph2C: +C0

R-H v Ph2C*H-R

Further proof for oxirene formation without Wolff rearrangement is obtained with unsymmetrical °<-diazo 27

? 7 dialkyl ketones'"' such as 3-diazo-^-heptanone (60) and aryl P R substituted c(-diazo ketones (Eq 26).

1,2-shift

(26) G. Prater and 0. P. Strausz, J. Amer. Chem. Soc., g2, 665^ (1970).

(27) M. Regitz and J. Ruter, Chem. Ber., 102, 3877 (1989)*

(28) K. G. Nogai, Dissertation, Technische Universitat, Hannover, 1972. 28

Only recently has conformational control in decomposition

of c^-diazoketones and Wolff rearrangement been studied.

Dynamic nuclear magnetic resonance (dnmr) techniques have

shown that o(-diazoketones can exist in solution as 32 equilibrium mixtures of s-Z (6,2) and s-E (62,) conformers .

(32) F. Kaplan and G. K. Meloy, J. Amer. Chem. Soc.. 88, 950 (1966); R. Curi, F. DiFuria and V. Lucchini, Spec.~I.ett. , 7, 211 (1974); H. Kessler and D. Rosenthal, Tetrahedron Lett., 393 (1973).

33 Kaplan and Mitchell-'-' have investigated the difference in behavior between 4-diazo-2,2 ,5,5-tetramethyl-3-hexanone (64), a s-E dominated o^-diazoketone, and 2-diazo-3,3,6,6-tetramethyl- cyclohexanone (££), a s-Z locked analog of 64. Fhotolysis and thermolysis^' ^ of s-E locked £4 give o(,p-unsaturated ketone £5 as the major product. Very little di-t-butyl- ketene (66) is formed at best (Eq 28). In sharp Contrast to s-E dominated 64, photolysis and thermolysis of s-Z 29

The trapping reaction - yielding epoxide strongly suggests that oxirenes are true intermediates and not transition states (Eq 2 7 ) in Wolff Systems. Other

0 OMe Me OH (2 7 ) N - V

(29) H. Meier, IVth IUPAC Symposium, 1972, 162 experiments which show no scrambling of oxygen include photolysis of S-diazo-l-^C-naphthalen-lC 2H) -one^° and dimethyl diazomalonate^i.

(30) K. P. Zeller, Chem. Commun., 31? (1975).

(31) K. P. Zeller, Chem. Ztg.. 2Z» 37 (1973). 30

+ + N,

6k hv 78/o (28) A 120 81%

0 + c=c=o X 66

h » 17% 3% A , 120( 16% none locked c^-diazoketone 67 yield primarily the ring contracted ketene 6 8 ; o(,[3-unsaturated ketone 62 or £0 are minor products (Eq 29). Due to severe steric crowding of

or or +

(29)

62 68 22 96%

A , 70°(or 110°) 85% 150/ 31

(3 3 ) F * Kaplan, M. L. Mitchell, Tetrahedron Lett.. 759 (1979)- (3 4 ) M. S. Newman and A. Arkell, J. Org. Chem., 24, 383 (1959). eclipsed t-butyl groups, £4 exists predominately in a s-E conformation; £7 cannot occupy a s-E conformation however because of cyclic ring strain. The striking difference in products obtained from this conformational pair 64 and 67 under controlled conditions clearly demonstrates a conformational requirement for ketene formation in both thermal and photochemical Y/olff rearrangements. These reactions are in accord with a concerted process for Wolff reactions. In concerted rearrangement, only the s-Z conformer will allow facile backside attack by the migrating group on the diazo-carbon. It is noted that the conformational control described here is consistent with ketocarbene formation only if carbenes 77 and 72 retain the conformational identity of their precursors respectively.

21 22 Photochemical isomerization of c^-diazocarbonyl compounds to diazirines has been reported for certain linear^ and cyclie36 c^-diazoamides. Only recently, has this type of

(35) R. A. Franich, G. Lowe and J. Parker, J. C. S. Perkin I., 2034 (1972); G. Lowe and J. Parker, Chem. Comm.. 1135 (1971).

(36) E. Voigt and H. Meier, Angew. Chem. Internat. Edn.. alb,* 103 (1975). isomerization been observed for o(-diazoketones-^. When

8-diazotricyclo [5 »3»0,o] deca-3 »5-dien-9-one (2 2) a9ueous dioxane is irradiated (>290 nm), endo-carboxylic acid 22 and the diazirine 2b are isolated along with recovered 22

(Eq 30). The structure of 2*2 -*-s unequivocally 33

(37) T. Miyashi, T. Nakajo and T. Mukai, J.C.S. Chem. Comm., kk2 (1978).

determined by its spectral properties. This is the first example of isolating a stable o(-ketodiazirine. Diazirine is much more stable than is 1-oxospiro [cyclohexane-2,3”- diazirine]^ which decomposes at room temperature. The behavior of 2^ is similar to that of 22' irradiation of

(33) E. Schmitz, A. Stark and Ch. Horig, Chem. Ber., 93, 2509 (1965).

gives 22 22' yields of 2it from 22 are less than

15-17:.i and those of 22 from £(£ are less than 12-13^. These observations indicate that the diazo ketone-aiazirine interconversion is photo-reversible and the Vr'olff rearrangement takes place from both 22 Zit a_t: slightly different rates.

When saturated diazo ketone £6 is photolyzed in v;ater, diazirine 22 is obtained along with carboxylic acid £3 (

Eq 31).

N = N

(31) 22 22 22 3k

These experiments illustrate that both unsaturated

and saturated c(-diazoketones (22 and £6) undergo valence

isomerization to af-keto diazirines. The thermal and

photochemical lability of

hypothetical stabilization by 7L-bonds (structure 22) is

thus responsible for the valence isomerization of o(-diazo

carbonyl compounds.

Diazoacenaphthenone (?) is one of the very few

diazo ketones which has not been found to undergo V.’olff

rearrangement under normal conditions-^ (pq 32).

hi> ~/fr (3-1) R.T. or -73°

Attempts to prepare lH-cyclobuta [de]naphthalen-l-ylidenemethanone (80) via thermal ring contraction of 2 are not 35

successful.

(39) W. Ried and H. Lowasser, Justus Liebigs Ann. Chem., ^-39 0955)? D. C. DeJongh and R. Y. Van Fossen, tetrahedron. 28, 3603 (1972).

Thermolysis of 2 "boiling xylene gives biacenedione

(or diacenaphthylidenedione) (81) as the main oroduct, »•»* r** along with trace amounts of acenaphthenequinone ketazine

(82, Eq 33).

A 1 (33) 160

81 82

40 Further, Photolysis of diazoacenaphthenone (£) in benzene yields spironorcaradiene §3 (84£) which isomerizes to 2-phenylacenaphthenone (84) via acid or silver ion catalysis (Eq 34). Thermolysis^1 of 2 in olefinic

* Recent development on the synthesis of 80 will be discussed in "Results and Discussion". 36

(34) o or Ag 33 y-

(40) C. G. F. Bannerman, J. I. G. Cadogan, I. Gosney and N. H. Wilson, Chem. Commun.. 613 (1975)*

solvents results in addition of c<-oxocarbene (8£) to the olefenic double bonds. For example, refluxing £ in various olefins (36), gives the respective two isomeric spirocyclopropanes 3£ and 83 in good yields (L'q 35)-

c h 2 ='x 2 R 7 -N 86

+ (35)

38 37

(^1) 0. Tsuee, I. Shinkai and M. Koga, J. Org. Chem., 36, 7^5 (1971). RESULTS ANiJ DISCUSoIO:

■Synthesis of Starting Diazo Ketones. tf-Diazo ketones are generally prepared by base-catalyzed decomposi- L\,2 tion of 1,2-diketone mono-p-tosylhydrazones, or by oxidation of 1,2-diketone monohydrazones with mercuric oxide or A 3 manganese dioxide. y In this study, the former method has been applied for the synthesis of diazo ketones 7 to 11. A* ^

(42) M. P. Cava, R. L. Litle and D. R. Napier, J. Amer. Chem. Soc.. 80, 2257 (1958).

(43) Org. Syn. Coll. Vol. II, 496; ibid.. Ill, 351.

Acenaphthenequinone mono-u-tosylhydrazone (gO) was prepared from acenaphthenequinone (Sg) and p-tosylhydrazine 42 by the method of Cava et al. Decomposion of gO with sodium hydroxide at room temperature readily yielded diazoacenaphthenone (g, 8?c/o) as stable orange crystals (Eq 36).

JiNHTos

c?h?so2nhnh2 aq NaOH

38 39

Nitration^ of acenaphthenequinone (8g) with one. equivalent of nitric acid at 0° afforded 5-nitroacenaphthenequinone (gl, 53%)* Reaction of gl with one equivalent of

£-tosylhydrazine gave 5-nitroacenaphthenequinone 2-jo- tosylhydrazone (g£) decomposition of which with aqueous sodium hydroxide formed 2-diazo~5-nitroacenaphthenone (8,

100^., Scheme 2), a stable, high melting yellow solid. The

SCHEME 2

NNHTos

HNO C?H ?SOpNHNHP

NO2

aq NaOH CH2d 2

(44) S. Ruhemann, Chem. Ber., £2B, 287 (1920); F. M. Rowe and J. H. S. Davis, J. Chem. SocT, 1344 (1920). ko

structure of 8 , a new diazoacenaphthenone, is assigned as

shown on the basis of its elemental analysis and its spectral

properties. The diazo group is believed to be at the 2-

position in 8 because the NMR of the proton at C-3 is shifted to higher field (£=7 .37) as compared to that in £1 (5 =8 .18).

The up-field shift for hydrogen at C-3 in 3 is probably due to the accumulation of negative charge on the carbon atom bearing the diazo group. This assignment of 8 in turn establishes the regiochemistry of 22* The selectivity in reactivity of the carbonyl groups in 2i toward p-tosylhydrazine may be rationalized on the basis that the carbonyl group at the 2-position is the more electron deficient due to the electron-v/ithdrawing effect of the nitro group at

C-5. The ketone group at C-2 is thus more susceptible to nuoleophilic condensation.

5 ,6-Dinitroacenaphthenequinone (22) w&s obtained by reaction of §2 with two equivalents of nitric acid in I4.I1 sulfuric acid. Condensation of 22 p-tosylhydrazine followed by decomposition of 5 ,6 -dinitroacenaphthenequinone

2-n-tosylhydrazone (2^) with aqueous sodium hydroxide yielded 2-diazo-5,6-dinitroacenaphthenone (9 , 73/*, Scheme 3), a new compound. The structure of 2 is established from

its elemental analysis and spectral properties. 4i

SCHEKE 3

-NNHTos

2 HNO CoHnS0~NHNH 1 § 2 ------> h 2s o „. NO

aa NaOH — > c h 2ci2

2-Diazo-3,8-dimethoxyacenaphthenone (10) was prepared as follows: 2,7-Dimethoxynaphthalene (g6) was obtained by deprotonation of 2,7-dihydroxynaphthalene (g£) with sodium I4.K hydroxide and subsequent methylation with dimethyl sulfate.

Friedel-Crafts acylation of g6 with oxalyl chloride and aluminum chloride resulted in 3»8-dimethoxyacenaphthenequinone (gg) in l°v; yield^ (14$). Condensation of £-

(45) F. Ullmann, Justus Liebigs Ann. Chem. . 2£Z» H ? (1903) •

(46) H. Staudinger, H. Goldstein and E. Schlenker, Helv. Chim. Acta., 4. 342 (1921). tosylhydrazine with 22 yielded 3»8-dimethoxyacenaphthene-

quinone 2-£-tosylhydrazone (g8). Decomposition of 2^ to

10 was accomplished by sodium methoxide in dry methylene

chloride (Scheme k ). Complete conversion of 2^ to-10 was

SCHEME k

1) NaOH - => 2) (CHOoSO

00 II II Cr,H„S0oNHMi- C1CCC1 3 CH > A1C1 3

22 NNHTos

NaOCH 0CK 3. - > c h 2c i 2

10 not successful even with excess base. Sodium hydroxide hydrolyzes tosylhydrazone 2§ in Part back to quinone 27' k3

Separation of 10 from %3 was achieved by column chromatography on silica gel.

Synthesis of 2-diazoaceanthrenone (11) , a new diazo ketone, is summarized in Scheme 5* Thus, anthracene (22^ was converted by oxalyl chloride and aluminum chloride to U-7 aceanthrenequinone (100). ' Treatment of 100 with p- tosylhydrazine gave aceanthrenequinone 2-p-tosylhydrazone

(101) which, upon reaction with sodium hydroxide, yielded I V M 2-diazoaceanthrenone (11, Scheme 5).

SCHEME 5

C1C0C0C1

A1C1. 22 100

NHTos

CoHoS0oNHNH NaOH

101 11

(4?) C. Liebermann and M. Zsuffa, Chem. Ber., k k , 202 (1911). ~~ kb

Elemental analysis and spectral data establish the

structure of 11. The hydrogen at C-3 in 100 comes at £=8.3k, whereas, that in 11 appears at higher field 7-bO). This up-field shift is apparently due to the introduction of the diazo group at C-2. Assignment as 11 is consistent with the fact that the carbonyl group at C-2 of 100 is nore exposed than at C-l and thus, more accessible to attack by p- tosylhydrazine.

Decomposition of Diazo Ketones 2"ii* Diazo ketones

2-11 are very stable at room temperature and under normal light, and are purified by recrystallization and/or chromatography (silica gel) before their decompositions are effected.

One of the purposes of this research was to prepare one carbon peri-bridged naphthalenes upon Y/olff rearrangement of diazoacenaphthenone (£) to lH-cyclobuta[de] naphthalene-

1-ylidenemethanone (80, Eq 32). Photolysis of 2 in methanol

0 II

1 80 45 at 25° f 0° or -70° resulted in intractable products and recovery of starting material. No evidence for formation of ketene 80 was found. Failure to obtain any identifiable product from solution photolysis of 2 may result from the poor solubility of 2 in methanol.

2-Propanol, a better solvent than methanol for 2» was then chosen for study. Photolysis of 2 in 2-propanol at

25° resulted in formation of acenaphthenone (102, 24.3%),

1,8-naphthalic anhydride (lO^, 14.4$), biacenedione (81,

1.7%) and acetone (42.7%, Eq 37) determined by GC on carbowax 20iv; at 80°. Products as derived from ketene 80

7 4 (C H ^ C H O H - > 2 + 81

102 m

+ CH^COCH^ (37)

or by incorporation with the 2-propanol in any direct manner were not found. Formation of 102 may be visualized that carbene 8£, as a triplet, effects hydrogen abstraction from the secondary carbon of the alcohol to give keto radical 104 which further abstracts hydrogen from the 46

SCHEME 6

1 T " 0 "1 H (CHp)?ioH ^ i x H-0C(CH?)p

104

-+ CH^COCH^

102

2-hydroxy-2-propyl radical yielding acenaphthenone (102,

Scheme 6) and acetone. A similar mechanism involving a triplet ketocarbene is also proposed for photosensitized 48 photolysis of dibenzoyldiazomethane (10£) in 2-propanol which leads to formation of dibenzoylmethane (106, Eq 33) presumably form the lowest triplet state of 10£.

0 0 * T

Sens Ph

106 (38) 47

(48) N. Baumann, Helv. Chim. Acta.. 274 (1972).

Production of 1,8-naphthalic anhydride (10^) is rationalized by reaction of carbene 8£ with oxygen in the system to give dioxirane 102 which rearranges as in Scheme

?. This is, to the author's knowledge, the first example

SCHEME 7

v — > I 2

m of reaction of an tf-ketocarbene with oxygen to give a

carboxylic anhydride. Whether there is oxygen scrambling

and formation of intermediate oxirene 108 is not clear,

though this equilibrating process is known for some other

108 related systems (see Scheme 1 and reference 2 5 ). 48

Biacenedione (81) may arise By reaction of 8£ with 2

with loss of nitrogen and/or "by more complex processes.

Since 2-propanol resulted in reduction of £, diazo-

acenaphthenone (£) was then photolyzed in t-butanol.

2-t-Butoxyacenaphthenone (10g, 1?.4?J) and biacenedione (81,

were obtained along with intractables (Eq 39)* Ketene 80

or compounds derived from it were not identifiable in these

h^ -0 -t -Bu 2 + t-3uOH - N. + 81 (39)

109

experiments. 2-t-Butoxyacenaphthenone (10g) possibly

results from direct insertion of carbene 3£ into the 0-H

bond of t-butanol or by some competitive cationic process.

While the present study was in progress, 0. Chapman

reported^9 that photolysis of / in argon matrix at 3°K gave lH-eyclobuta [de]naphthalen-l-ylidenemethanone (80,

Eq 40). The ketene vibration in 80 was detected by IR and

(40) Ar, 8°K

2 80 1+9

this absorption peak disappeared on prolonged irradiation.

This low temperature technique cannot be used on preparative

scale and is not synthetically useful. The report by

Chapman gave further incentive to the present research

effort. Photolyses of £ in methanol, 2-propanol and

(1+9) 0. Chapman, Chemical & Engineering News, American Chemical Society, September l(3, 1978, p. .17*

t-butanol however do not give any evidence for Wolff rearrangement to ketene 80 and its subsequent products.

Study was then focused on further exploration of the chemistry of diazoacenaphthenone (£) and in particular decompositions of £ in various environments. Diazo acenaphthenone (£) does decompose photochemically and thermally (150°) in cyclooctane, from which oxygen was not completely removed, to give 2-cyclooctylacenaphthenone

(110, 52°/o, 62°/o respectively) and 1,8-naphthalic anhydride

(lO^, 21^, 36/S respectively) (Eq ij-1). Formation of 110

110 50

is readily explained by direct C-H insertion into

cyclooctane by carbene 8£ possibly in its singlet state.

All efforts to trap carbene as generated photoly-

tically with cyclohexene or ethyl vinyl ether were unsuccessful; only intractables were obtained. Elimination

of nitrogen from diazo compounds and addition of carbenes to olefins intermolecularly'^ or intramolecularly'^ are usually accelerated by copper salts as shown in equations k2 and kj. However, in refluxing cyclohexene containing

(42) GuGl

Cu (43) :HN or CuCl

(50) J. Haywood-Farmer, R. E. Pincock and J. I. Wells, Tetrahedron, 22, 2007 (1966).

(51) M. Fawzi and C. D. Gutsche, J. Org. Chem., 1390 (1966); J. Trotter, C. S. Gibbons, N. Nakatsuka and S. Masamune, J. Amer. Chem. Soc., 8g, 2792 (1967). a catalytic amount of cuprous bromide, diazoacenaphthenone 51

(2) yielded biacenedione (81, ?6%, Eq 44). This latter

0 S'2

4 > (44) CuBr

result is in agreement with the known fact that formation 41 of 81 from £ Is greatly enhanced by copper salt catalysts

So far, photochemical and thermal cyclopropanations

of olefins with £ have not been successful. However, reactions of £ with certain <*,p-unsaturated olefins do produce fair yields of spirocyclopropanes as already

demonstrated in Equation 35*

o^-Diazo ketones and ketocarbenes which do not undergo

Wolff rearrangements are known to be excellent 1,3-dipolar

reagents. Studies were then focused on thermally and

photochemically induced 1,3-dipolar cycloadditions of

diazoacenaphthenone (£) and/or carbene 8£ to nitriles and

acetylenes. In fact, irradiation of diazoacenaphthenone

(7) in acetonitrile did result in 8-methylacenaphth [l,2-d]-

oxazole (111, 62%, Eq 45). Attempts to carry out the 52 analogous 1 ,3-dipolar cycloaddition by refluxing £ in acetonitrile resulted in quantitative recovery of £.

Palladium acetate is known to catalyze the decomposition of 52 diazo compounds. However, diazoacenaphthenone (£) is

(52) U. Mende, B. Raduchel, W. Skuballa and H. Vorbruggen, Tetrahedron Lett., 629 (1975)*

stable in boiling acetonitrile even in the presence of palladium acetate only traces of biacenedione (31) are obtained in this experiment (Eq 45). The structure of 111

— /

111 £ -I- CH^CN (45)

is assigned based on spectral properties and elemental

analysis. Further support for 111 is its degradative

hydrogenation-^ to l-(N-acetylamino)acenaphthene (112,

Eq 46). 53

NHCOCH-

H, ill (46) Pto,

112

(53) 0. Tsuge and K. Koga, Heterocycles, 6 , 411 (1977).

Formation of 111 is explainable in that diazoacenaph

thenone (£) undergoes photochemical loss of nitrogen to

form singlet ketocarbene which is also representable as 1,3-dipole 11,2* Concerted addition of 113 to the C-N triple bond of acetonitrile can then give 111 (Scheme 8).

An alternative mechanism may be that carbene 8£ undergoes stepwise electrophilic attack on the C-N triple bond

forming twitterion rv-rwrv 114 which then closes up r to 111. Such

SCHEME 8

N2 J a 1,3-dipolar cycloaddition is well known^ for diazo

compounds such as ethyl diazoacetate (11^) which reacts with

nitriles to yield oxazoles of structure 116 (Eq ft-7).

0 N0 II n 2 A C?H5OC-CH + RCN (ft7) - N,

116

(5ft) R» Huisgen, H. J. Sturm and G. Binsch, Chem. Ber., 97, 286ft (1964); R. Huisgen, G. Binsch and L. Ghosez, ibid., 97, 2628 (.196ft).

Benzonitrile reacts with 7 both thermally and

photochemically to afford 8-phenylacenaphth (i,2-d}oxazole

(11£, Eq ft8) apparently by a carbene mechanism. However,

in refluxing benzonitrile containing a catalytic amount of

?6h 5

h^ or A 2 + c 6h 5cn - N, (ft3)

112

cupric sulfate, no 11? was obtained; the only isolable product was biacenedione (81, 78#). It is thus apparent 55

that cupric sulfate does not lead to generation and

cycloaddition of presumably in its singlet state.

Photolysis of £ in acrylonitrile resulted only in trace

amounts of spirocyclopropanes 118 and llg* Thermolysis of

2 in acrylonitrile in the presence of palladium acetate

resulted however in two isomeric 2 "-cyanospiro Qacenaphthenone-

2,1'-cyclopropanes] (118 and llg, 37$ and 38$, Eq 49).

2 + ch2=chcn > Pd(OAc)2 +

118 (49)

The assignments of stereochemistry of 118 and 119 are based on the NMR spectra of their cyclopropyl protons.

Both 118 and llg exhibit clear ABX patterns for cyclopropyl

protons. In 118, £Hx=2.54, SH =1 .98, SHb=2.l6 with

JAX=^ JBX=^ Hz*and j aB=Z| Hz* In SHx =2.46, $Ha=2.06, SHb=2.2? with JM =9-6 Hz, Jfixs6.9 Hz and ^ = 3 - 6 I

It is well known-^ that cis cyclopropyl protons exhibit larger coupling constants (8-10 Hz) than do trans protons

(4-7 Hz). Since a j9-carbonyl group exerts a shielding 56

(55) K. B. VViberg and B. J. Nist, J. Amer. Chem. Soc., 2788 (1963); J* D. Graham and M. T. Rogers, ibid.. 8^, 2249 (1962).

effect on protons facing it, H of 118 is expected to come

at lower field (higher $ value) than that of 112- The

present assignments for 118 and llg are opposite that Zfl tentatively proposed in the literature.

No exazole is obtained from either thermolysis or

photolysis of £ in acrylonitrile.

Diazoacenaphthenone (£) also undergoes regiospecific

1,3-dipolar photolytic cycloaddition to phenylacetylene with loss of nitrogen to give 8-phenylacenaphtho[l,2-b]furan

(120, 21fj, Eq 50). Similar regiochemistry is observed in

hzJ I -+ PhC=CK - N, (50)

120

.56 thermolysis-' of tetrachlorobenzene-1,2-diazooxide (121)

in phenylacetylene which affords 4,5,6,7-tetrachloro-2-

phenylbenzo[b]furan (122, Eq 51). The structure of 120 57

Cl Cl Cl A -+ PhC=CH II (51) Cl 0 N

Cl Cl

121 122

(56) R. Huisgen, G. Binsch and H. Konig, Chem. Ber.. $2* 2884 (1964).

is derived from its elemental analysis and in particular its

spectral properties. The N O spectrum of 120 exhibits a

singlet at 5=6.99 which is assigned to the (5-proton of its

furan ring. The chemical shift for this hydrogen as

compared to that in furan (5^6.37 for the ^-proton) is attributed to the deshielding effects of the phenyl group and the acenaphthene moiety. The NNR of the tf-proton of furan comes at 5=7*42 and should be shifted to an even lower field by an adjacent phenyl substituent. Thus on the basis of the singlet at 5=6.99, 120 is the correct structure.

The regiochemistry of addition leading to 120 is opposite that predicted from nucleophilic cycloaddition of

1,3-dipole 113 to phenylacetylene. Formation of 120 may 58

be rationalized in that singlet ketocarbene undergoes

electrophilic addition to phenylacetylene to give zwitterion

122 which closes to 120 (Scheme 9, route a). Alternatives are that (1) carbene adds to the C-C triple bond of

phenylacetylene to give cyclopropene 12^+ (route b) which

isomerizes via 12^ or 12£ to 120, and/or (2) triplet

SCHEME Q

122 120

m 122

-> 120

126 59

carbene 8£ adds to the C-C triple bond to form a triplet diradical 126 which then undergoes spin inversion and ring closure to give the final product (route c).

2-Diazo-5-nitroacenaphthenone (8) was then chosen for study of possible Wolff rearrangement with the expectation that the nitro group at C-5 would make the carbene center

(C-2) in 127 highly electron deficient. Therefore,

3 (52) U

NO2 NO2

m127 ^ ^ 128

migration of bond a to the carbene center of 122 would

become more favorable and thus Wolff rearrangement to

ketene 128 (Eq 52) might be induced.

Photolysis of 8 was attempted in methanol at 25°, 0°

and -70°. In all cases, a majority of the starting material (8) was recovered and only trace amounts of

intractable products were isolable. The minor photochemical

response of 8 is apparently due to its poor solubility in methanol. However, when methylene chloride solutions of 8

were subjected to photolysis, only tars were obtained.

Direct pyrolysis of 8 at 200° led to black amorphous

materials which were insoluble in organic solvents. The

IR spectra of the products of decomposition of 8 by the

various methods gave no evidence for Wolff contraction to

128.

A study of the varied photochemical and thermal

chemistry of 2-diazo-5-nitroacenaphthenone (8) was then made.

Diazo ketone 8 is very stable thermally and is recovered unchanged when refluxed in acetonitrile (bp 82°).

Photochemical cycloaddition of 8 to acetonitrile does occur however with loss of nitrogen to form 8-methyl-3-nitro-

acenaphth[l,2-dJoxazole (122, bQfo, Eq 53) as established from its elemental analysis and spectral properties. 61

Hydrogenation of 12g over platinum dioxide led to only

tarry products. Prolonged irradiation of 12g left 12g

unchanged. Some simple alkyl and aryl substituted isoxazoles

are known to undergo thermal^ and photochemical^®

isomerization to oxazoles. These oxazoles are stable

(57) A. Padwa and E. Chen, J. Org. Chem.. 22» 1976 (197*0*

(58) E. F. Ullmann, B. Singh, J. Amer. Chem. Soc., 88, 1 8 ^ (1966).

toward heat and light. Conversion of oxazoles to isoxazoles by thermal or photochemical means has not been observed.

Product 12g is assumed to be an oxazole rather than an

isoxazole based on the similarity of reactions of 8 to those of £ with all the dipolarophiles and benzene. Its thermal and photochemical stabilities further confirm the oxazole structure.

Investigation of possible thermal, photochemical, and metal-ion catalyzed reactions of 8 with benzonitrile was then initiated. Benzonitrile is of advantage over acetonitrile for thermal reactions in that it is higher boiling (bp 191°). Indeed thermolysis (190°) and photolysis of 8 in benzonitrile afforded 3-nitro-8-phenylacenaphth [l,2-cf)oxazole (122» 50# respectively, Eq 5*+)* 62

+ PhCONH 8 + C^H.CN 2

NO 2 (5*0

Small quantities of cupric sulfate greatly accelerate reaction of 8 with benzonitrile to give oxazole l^O* The yield was comparable (39$) "to that obtained thermally but the system was complicated by copper salt-catalyzed hydrolysis of the benzonitrile to benzamide during chromatography. The structure of 1^0 is proved by spectral data and elemental analysis.

2-Diazo-5-nitroacenaphthenone (8) undergoes photo chemical cycloaddition to phenylacetylene with loss of nitrogen giving 3-nitro-8-phenylacenaphtho[l,2-b]furan

(131, 60£, Eq 55)’ Elemental analysis and spectral

Ph 63

properties establish the structure of 12i* The regio-

chemistry of addition to give 12g is unequivocally assigned

from its furan proton singlet at £=7«10 upon comparison with

that of 2 ,5-diphenylfuran which exhibits resonance at $-

6.71. Since the absorption of °<-H of phenyl-substituted

furans comes at lower field than ^ 7 .42, the regioisomer of

171 with its phenyl group at the 9 -position is excluded.

The thermal and photolytic behaviors of 8 in phenyl acetylene differ greatly however. Thus, thermolysis of 8

in phenylacetylene occured without loss of nitrogen and with

formation of 3-nitro-10-phenvl-7H-benzo[dej pyrazolo[5.1-a]-

isoquinolin-7-one (132* 67%. Eq 56) presumable via 1,5- rearrangement of 5"-phenylspiro[5-nitroacenaphthenone-

2,J'(3*H)pyrazole] (132) as derived from initial 1,3-dipolar

Ph H

(56) 8 + FhC=CH shift

cycloaddition. Structure 133 is established by elemental analysis and by comparison of its UV spectrum (^^(CHCl^)

248 and 385) to that of 135 (9 ^ (EtOH) 252, 332 and 370) DiclX 6k prepared similarly from diazoacenaphthenone (£) and phenylacetylene in this laboratory^ (Eq 57)* Product 1 ^ is also recovered quantitatively after having been refluxed in chlorobenzene (bp 132°) for long periods or irradiated in benzene for 3 h. Since 3H-pyrazoles such as 1^2 are known to undergo thermo- and photodecompositions to cyclopropene derivatives^, the observed photochemical and

(59) T. Yamazaki and H. Shechter, Tetrahedron Lett., ^533 (1972).

(60) G. L. Closs and W. A. Boll, J. Amer. Chem. Soc., 85f 3904 (1963); G. L. Closs and V/. A. Boll, Angew. Chem. Intern. Ed. Eng.. 2, 399 (1963); G. L. Closs, W. A. Boll, H. Heyn and V. Dev7 J. Amer. Chem. Soc.. go, 173 (1968); G. Ege, Tetrahedron Lett., 1667 (19^3); R.~Anet and F. A. L. Anet, J. Amer. Chem. Soc., 86, 525 (1964-); A. C. Day and E. C. Whiting, Chem. CommunTT 292 (1965); A. C. Day and E. C. Whiting, J . Chem. Soc.. C, 1719 (1967); L. Closs, L.R. Kaplan and V. I. Bendall, J. Amer. Chem. Soc., 8 9 . 3376 (1967). thermal stabilities of product 1^2 eliminate 1^2 as a likely structure.

■Ph

£ + PhC=CH (57) shift

i2i 65

It is relevant to discuss the rearrangement of 1£^ to

1££* Indeed 1£4 was first proposed to be the product of reaction of £ ^ 8 phenylacetylene. Later work in this co laboratory^7 has proved 1££ to be the correct structure.

Thus 1£5 is readily hydrolyzed by potassium hydroxide; reacidification gives back 1££. Most importantly, 1££ is proved by unambiguous synthesis upon condensation of 1,8- naphthalic anhydride (10£) and acetophenone with sodium hydride, followed by reaction with hydrazine (Eq 58).

HO C0-CH~C0Ph

Nall > + CH^CPh

(58)

Further, the C^-NMR of a similarly prepared product

dimethyl 7-oxo-7H-benzo [de^pyrazolo [5»1-§G isoquinoline-

10,11-dicarboxylate (1£6) exhibits carbonyl absorption at

£=163»^2 typical of an amide (Eq 59)*

A 7 4 CH302C-C=C-C02CH3 (59)

126 66

Spontaneous isomerization as in spiropyrazole 1^4 to N-

acylpyrazole 1 ^ is also observed in reactions of other <*-

diazo ketones^1 with acetylenes. For example, 2-diazo-

indanone (1^2) reacts with dimethyl acetylenedicarboxylate to give 12§ as the only product-^ (Eq 6o). Failure to

CH<,0oC-CeC-C0oCH 3

2 3 (60)

133

(61) T. Yamazaki and H. Shechter, Tetrahedron Lett., 1417 (1973); M. Martin and M. Regitz, Justus Liebigs Ann. Chem., 1702 (1974); A. Katner, J. Org. Chem.. 38. 52 6 (1972) ; M. Frank-Neumann and C. Buchecker, AngewT Chem.. 8£, 259 (1973); B. L. Rodina, V. V. Bulusheva, T. G. Ekimova and I. K. Korobitsyna, Zh. Org. Khim., 10, 55 (1974); L. L. Rodina V. V. Bulusheva and I. K. Korobitsyna, ibid ., 10, 1937 (197^)*

isolate spiropyrazoles such as 1^2 and 1^4 must be due to the facile thermally-allowed 1,5-sigmatropic shift of an acyl group to nitrogen.

The behavior of 8 with dimethyl acetylenedicarboxylate is similar to that with phenylacetylene. Thus, thermolysis 67

of 8 in dimethyl acetylenedicarboxylate afforded diemthyl

3-nitro-?-oxo-?H-benzo[de]pyrazolo[5,1-a]isoquinoline-

10 ,11-dicarboxylate (140, 83%, Eq 61) presumably via

sigmatropic isomerization of 4',5'-dimethoxycarbonylspiro-

[5-nitroacenaphthenone-2,3'(3'H)pyrazole'l (122^* Isoquinoline

C02CH3

A- C02CH3

ch?o2 c-cec-co2 gh3 8

NO NO2

i22 140 (61)

derivative 140 is thermally and photochemically stable.

The UV of 140 20? and 374) is also comparableto

that of 122 anc* "t*16 structure is believed to be as shown.

Elemental analysis and spectral properties further confirm

structure 140.

Photolysis of 2-diazo-5-nitroacenaphthenone (8) in

benzene yielded 5-nitro-2-phenylacenaphthenone (144, 55%,

Scheme 10) as the only isolable product. The structure of

144 is derived from its elemental analysis, spectral m w properties and its NMR spectrum which shows only aromatic

protons and a singlet at S=5»10 for a single benzylic

proton. Formation of 144 may be visualized as involving 68

SCHEME 10

Ph NO o >

NO NO 2 NO 2

i£2

NO2

1^3K* attack of ketocarbene 122, presumably as a singlet, on benzene to form spironorcaradiene 141 which undergoes heterolytic or/and homolytic ring opening to 342 or/and 34g followed by hydrogen shift(s) to 1^4 as in Scheme 10.

Since one nitro group does not lead to Y.’olff rearrange ment in decomposition of 2-diazo-5-nitroacenaphthenone (8),

2-diazo-5,6-dinitroacenaphthenone (g) was then designed for determination of its carbenic properties. The idea was that the nitro groups at the 5- and 6-positions in 14£ 6 9

should make the carbene center (C-2) even more electron-

deficient than that of 122* Therefore, migration of bond a

to C-2 would be accelerated due to the increased demand of

an electron pair from bond a. Furthermore, the two nitro

groups in the 5- and 6-positions in carbene 1^£ should

sterically repel each other, therefore, pushing the carbonyl

group and bond a closer to the carbene center and enhancing

shrinkage of 14£ (Eq 62).

0 II 01 8

3 r; ------> r l (6?)

02n n o 2

1U-6

Photolytic Wolff rearrangement of 2» first attempted in methylene chloride, gave only black intractables after

chromatography. When methanol was used to trap ketene 146 as possibly formed, only strating material (§, 36%) was

isolated. No evidence for ketene ]>6 nor compounds derived therefrom was found. The poor photochemical efficiency and the messy products may result from complication by the nitro groups upon irradiation of diazo ketone §.

The chemistry of 2-diazo-5»6-dinitroacenaphthenone (9) was then studied further. Photolyses of 2 in acetonitrile 70

and in benzonitrile resulted in 8-methyl-3,4-dinitroacenaphth-

[l ,2-d]oxazole (14£, 67^) and 3 ,4-dinitro-8-phenylacenaphth-

[l •2-d]oxazole (148, 26%, Eq 63) respectively. Both 142

CH.

0 X N

CH?CN 2 >

V NO2

V i l 1 fl r N \ (63) o2n NO, c6h 5 O' ^ o/C

148 and 148 are assignable from their elemental analyses, their spectra and mechanistic principles.

Photochemical reaction of g with phenylacetylene

occured with loss of nitrogen and afforded 3 ,4-dinitro-8-

phenylacenaphtho[1,2-b]furan (14§» 43^-, Eq 64). Spectral

properties and elemental analysis establish the structure of 71

\ —

hi) 2 + PhCECH (64)

NO2

iit2 14§. The NTCR spectrum of 14§ shows a singlet at S-?.l6 assigned to the J3-H of the furan moiety. The down field shift as compared to furan in which J3-H comes at S=6.34 is attributed to deshielding by the phenyl, acenaphthene and nitro groups.

Thermolysis of § in dimethyl acetylenedicarboxylate afforded dimethyl 3 ,4-dinitro-7-oxo-7H-benzo[dejpyrazolo-

[5,1-a]isoquinoline-10,11-dicarboxylate (1£1, 83?°, Eq 65) presumably via 1 ,5-sigmatropic rearrangement of spiropyrazole l^O. Structure 1£1 is identified by elemental analysis,

c o 2c h 2

O^CH 2wn3 C02CH3

c o 2c h ^ CH?02C-C5C-C02CH3 a------^ A

OoN N02

U l (65) 72 spectral data and its thermal and photochemical stabilities.

The overall behavior of g with dimethyl acetylenedicarboxylate is thus similar to that of 8 and 2*

When benzene solutions of g were irradiated, 2-hydroxy-

5,6-dinitro-2-phenylacenaphthenone (lg2, Eq 66) was

hu , 0, + - No (66)

obtained. Production of a hydroxy ketone (1£2) in these reactions is striking. The structure of 1£2 is proved by its IR which shows a strong 0-H band at 3 ^ 0 c m - '*' and its

NMR, mass spectral and elemental analyses. Formation of 132 may involve addition of ketocarbene 1V> to benzene giving spironorcaradiene l£g which ring opens and rearranges as in Scheme 11 to 5»6-dinitro-2-phenylacenaphthenone (l£f+).

SCHEME 11

[0] -> 152

NO NO 0 NO 2 153 73

Since nitrogen was bubbled through the reaction mixture before

and during photolysis, oxidation of 1£{* appears to occur

during work-up. 5.6-Dinitro-2-phenylacenaphthenone (1£4)

was not isolated in two attempted photolyses. Oxidation of

1^4 may involve formation of peroxide 1 ^ which decomposes

to alkoxyl radical 1^6 (Scheme 12) which picks up hydrogen

from 1 ^ to give 1£2.

SCHEME 12

0-0H

* +

o 2n n o 2 °2N N02

So far, studies of 2-diazo-5~nitroacenaphthenone (8) and 2-diazo-5.6-dinitroacenaphthenone (g) reveal that the electronic effects originally designed to induce Wolff reactions of carbenes 12g and are not successful.

Photolyses of 8 and g in matrix or in totally inert solvents should be investigated in the near future.

Possible strain relief leading to Wolff rearrangement

in decomposition of 2-diazoacenaphthenone derivatives was then studied. The idea was to put bulky groups at the

3- and/or 8-positions of diazoacenaphthenone as in 157 with 7^

6 5

i.52 the expectation that steric crowding will push the carbonyl

group and carbon center bearing the diazo group away from

the substituents at the 3- and 8-positions of 1£2* Thereby,

the carbene center derived from 1%% would be relatively

strained and moved toward the carbonyl group making it

easier for Wolff reaction to occur. For these reasons,

2-diazoaceanthrenone (11), a new o(-diazo ketone, was prepared and its chemistry investigated.

2-Diazoaceanthrenone (11) was first irradiated in methanol. Work-up led only to intractables even after

chromatography and there was no evidence for ketene 1£8 and/ or its derivatives (Eq 6 7 ). Attempts to decarbonylate 0

aceanthrenequinone (100, Eq 68) by photolysis in tetrahydro-. furan result in intractables and recovery of part of the strating material. No bridged ketone 15^ was obtained. 75

(63) THF

100

Efforts to effect C-H insertion of 11 into cumene and into toluene were also without success.

Research was then focused on cycloadditions of 2-diazo aceanthrenone (11) to nitriles and acetylenes. The chemistry found for 11 is virtually identical to that of diazoacenaphthenone (£). Thus, photolyses of 11 in acetonitrile and in benzonitrile produced 2-methylaceanthryleno[2,1-dJ - oxazole (160, 36f£) and 2-phenylaceanthryleno [2 ,1-dJ oxazole

CHq

oA j

*******160

11 Ph (69)

PhCN 76

(161, 11%, Eq 69) respectively. Elemental analyses and

spectral data verify the assignments as 160 and 161. Photolysis of 11 in phenylacetylene afforded 10-phenyl-

aceanthro [l ,2-b]furan (162, 10%, Eq 70) as dark purple

crystals. The structure of 162 is supported by its

h»> 11 4- PhC=CH --- -

162 combustion analysis and its spectra. In particular, the NMR absorption of 162 exhibits a singlet at $=7*09 for hydrogen

J3 to the furan oxygen; the resonance is similar to that of the £-proton of furan 120 (Z-6 .99)• The color of 162 seems to be typical of furans highly substituted with aromatic rings; 2,5-diphenylbenzofuran exists as black crystals.

Thermolysis of 2-diazoaceanthrenone (11) in acetylenes leads to products different from photolysis. For example, heating 11 in phenylacetylene yielded 2-phenyl-12H-dibenzo-

[dje ,hj pyrazolo [l, 5-bJ isoquinolin-12-one (164, 98%, Eq 71) probably via 5*-phenylspiro[aceanthrenone-2,3,’(3*H)pyrazoleJ

(162). Quantitative analysis, spectral data and chemical properties establish structure 164. The C^-NMR of 164 77 exhibits carbonyl carbon resonance at 162.08 ppm which is assigned to its amide carbonyl group (such absorptions have

N Ph

11 + PhC=CH

P h m

(71)

164 been found to occur in 140-160 ppm region). Ketones related to 16^ usually show carbonyl resonances at 180-210 ppm region. Adduct 164 is thermally and photochemically stable.

Analogously, 11 and dimethyl acetylenedicarboxylate reacted on heating to yield dimethyl 12-oxo-12H-debenzo-

[de,h]pyrazolo [l,5-b]isoquinoline-2,3-dicarboxylate (166,

100$, Eq 72) possibly via 4',5"-dimethoxycarbonylspiro-

[aceanthrenone-2,3”” ( 3^H)pyrazole] (16£). Adduct 166 is stable thermally (refluxing toluene for 24 h) and photolytically (irradiation for 3 h) and its structure is confirmed from its analysis, spectra and, in particular its 13 C -NMR for carbonyl carbon at 5=162.88 ppm (compared to 78

11 + CH^OgC-CHC-COgCH^ shift

(72)

166 that of 136 at £=163*^2). Based on C^-NMR and literature precedent^®*60 ang go) for rapid isomerization of intermediates similar to 16^* structure I65 is excluded.

2-Diazoaceanthrenone (11) on irradiation in benzene yielded 2-phenylaceanthrenone (120, 68fo) possibly as in

Scheme 1 3 . The product is identified as 120 rather than 16 icx>

h it 11 N-,

167 168 -Ph 79

or its cycloheptatriene valence isomer by its singlet NMR

resonance for a benzylic proton at 5=4.90.

2-Diazoaceanthrenone (11) reacts with electronegatively-

substituted olefins with loss of nitrogen to give spiro-

cyclopropanes in good yields. For example, 11 in refluxing

acrylonitrile resulted in the isomeric 2'-cyanospiro [ace-

anthrenone-2,l'-cyclopropanes] l^l and 1£2 (Eq 73) in 42?£

H_ hb CN 0 1 0 ^ H A \ H CHP=CHCN X A HX H — ------> I T " ^ 1 A - N J 2

1 2 1 1 2 2 (7 3 ) and 54# yields respectively. Both 1£1 and 122 are established from their spectral properties and their elemental analyses. Clear ABX NMR patterns are observed for the cyclopropyl protons in 121 and 122. In 121. $HX=2.56, 5Ha =

2.14, 5Hb=1.98 with JAX=9 Hz, JBX=7 Hz and J^g-5 Hz; in 122,

5H =2.51, SHa-2.37, SHb=2.13 with JAX=6.8 Hz, JfiX=8.2 Hz and Ja b =3*7 H z . Since Hx in 172 is syn to the carbonyl group, its £Hv comes at a higher field than that for 171.

The J values of 171 and 172 are also consistent with previous facts'^ in that cis cyclopropyl protons exhibit larger coupling constants than trans ones. 80

A number of mechanism can be considered for reaction of

11 with acrylonitrile. 2-Diazoaceanthrenone (11) might undergo thermal loss of nitrogen to give ketocarbene 162 ( either singlet or triplet) which reacts with acrylonitrile to yield two cyclopropanes 121 and 122 (path a). On the other hand, 11 might cycloadd to acrylonitrile resulting in

SCHEME 14

b 171

1?4 81

syn and anti-pyrazolines 17^ which then lose nitrogen to give the final products (path t>) either concertedly or non-

concertedly. A third possibility is that 11 adds to acrylonitrile to afford zwitterion 1 which closes to cyclopropanes upon loss of nitrogen (path c, Schems 14-). Since

2-diazoaceanthrenone (11), in the absence of acrylonitrile, does not decompose in solution at the temperature in which addition occurs, path a can not be followed. Fath b and c are much more reasonable but cannot be differentiated yet.

Similarly, 11 reacts with methyl acrylate when warmed to give the two isomeric 2 '-methoxycarbonylspiro[aceanthrenone-2,1'-cyclopropanes] l^^ and 1 £6 (Eq 7^-) in 51% and 39% yields respectively. The isomers are distinguishable by

H A A C02CH3 11 + CH2=CHC02CH3 82

NMR methods. In 175. =2.86, £H =2.2^, £H,=2.07 with X cl D JAX=^ H?f JBX=^ Kz JAB = Z| Hz; in iZ§» SV2.90, SHa=2.60,

^Hb=2.08 with JAX=JBX=8 Hz and Jab = /+ Hz*

2-Diazo-3.8-dimethoxyacenaphthenone (10) was then chosen for study in the hope that steric crowding by the methoxy groups at the 3- and 8-positions would lead to Wolff rearrangement to ketene 127 (Eq 75). All efforts to effect

^OCH^ OCH ///-> CH3° 3 l2 (75)

10 m ring contraction to 122 failed. Further, dihydrofuran 123, a possible intramolecular insertion product, was not found in any of these attempts (Eq 76). Failure to form 122 and

10 (76)

128 implies that the carbene from 10 is insufficiently

strained and its methyl groups are preferentially oriented

av/ay from the diazo and the carbenic centers as in 122 rather than in 180. 83

CH CH 3

0 0 ■CH. CH.

122 180 Photolysis of 10 in methanol does give 2,3»8-trimethoxy-

acenaphthenone (131, ?8^, Eq 77) in good yield. The

OCH.

CHoO OCH.

10 + Me OH (77)

131

structural assignment is drawn from analytical data and in

particular from its IR and NKR spectra. Ester 132, as

derived from V/olff rearrangement and addition of methanol to the ketene, is excluded on the basis that the carbonyl absorption of the product (1720 cm""'*') is too low for that of

an ester. Furthermore, the chemical shift of the benzylic proton in 181 (S=5*0 5) is much lower than that of an lb analogous proton in I83 (£=5 *9*0 synthesized independently.

CF 3

182 84

When 10 was photolyzed in tetrahydrofuran, spiro[3*8-

dimethoxyacenaphthenone-2,2'’-tetrahydropyran3 (184, 53%* Eq

?3) was obtained. The structure of 184 is confirmed by its

10 +

184 elemental analysis and spectral properties. The IR of 184 shows a strong C=0 absorption at 1700 cm-1. The NMR exhibits two sets of multiplet at 2.6 and 1.7 ppm integrating for two and six protons respectively. The chemical shift of 2.6 ppm is comparatively lower than unsubstituted pyran where the protons alpha to the oxygen come at 3*56 ppm.

The high field shift of the two protons alpha to the oxygen in pyran 184 may be attributed to the shielding effects from the methoxy and carbonyl groups. This up-field shift is also observed in some alkyl substituted anisols. Any simple C-H insertion product can be ruled out based on the absence of benzylic proton resonance as a doublet in the region of 3-0-5-0 ppm. A similar overall C-0 insertion reaction of a carbene into an ether was also observed in the reaction ' of ethyl diazoacetate (11^) with the formal of catechol (1 ,2-dihydroxybenzene) to yield rearrangement 85

product 18£ as in equation 79

0 C02Et \ A / + N2CHC02Lt ^ 7 ^ -0 1 (79)

(62) A. W. Johnson, A. Langemann and J. Murray, J. Chem. Soc., 2136 (1953).

Formation of 18^ may be rationalized in that ketocarbene

122 as a singlet attacks the oxygen atom in tetrahydrofuran

to give ylide intermediate 186. Rearrangement and ring

opening as shown afford 18^ (Scheme 15)* Study of the

SCHEME 15

JOCH 3 m l§!t

186 behavior of 2-diazo-3,8-dimethoxyacenaphthenone (10) was thus concluded.

The direction of this research was then focused on the

synthesis and the chemistry of 2 -benzylidene-l-diazoacenaphthene (188) as possibly derived from the 86 tosylhydrazone (182) of benzylideneacenaphthenone (Eq 80).

Ph TosHNN CHPh CHPh

Base

188

One of the reasons for preparing 183 is to attempt its conversion to strained cyclopropene lSg by various methods.

The outcome of this effort led to some unusual chemistry and is the center of the following discussion.

Benzylideneacenaphthenone (Igl) is obtained J from reaction of acenaphthenequinone (8g) with benzyltriphenyl- phosphorane as prepared in situ from benzyltriphenylphosphonium bromide (IgO) and sodium methoxide (Eq 81).

HPh

@ © 1) NaOCH Ph^PCHgPh Br (81) 122 121

(63) 0. Tsuge, M. Tashiro and I. Shinkai, Bull. Chem. Soc. Jap.. 42, 181 (1969).

Attempts to isolate benzylideneacenaphthenone p-tosylhydrazone (182) from reaction of lgl with p-tosylhydrazine 87

failed; instead,, acenaphthenequinone bis(p-tosylhydrazone)

(12, Eq 82) is obtained in 58% yield. The structure of 12

TosH NHTos

■> + FhCH lgl + C7H?S02NHNH2 3

(82) 12 is established from spectral data and combustion analysis.

Formation of 12 is further proved by independent syntheses from (1) acenaphthenequinone (8g) and two equivalents of p-tosylhydrazine (Eq 83) and (2) £-nitrobenzylideneacenaphthenone (1§2) and p-tosylhydrazine (Eq 83).

C„ HnS0 oNHNH^ 2 CoH„S0oNHNH C„HnS0oNHNH^

i22 (83)

A mechanism of this surprising conversion of lgl (and

1§2) to 12 may involve condensation of the carbonyl group of lgl with £-tosylhydrazine and then eventual displacement of toluene from 1§2 "by £-tosylhydrazine (Scheme 16). Trace amounts of toluene were indeed detected by GC. Even with one equivalent of p-tosylhydrazine to lgl, no 18£ is isolable. 88

SCHEME 16

TosHNN CHFh TosHNK

CoHoS00NHNH CoHoS0oNHNH

m - PhCH 1

Reactions of the type for lgl and p-tosylhydrazine to give

12 are unprecedented.

Many 1,2-diketone bis(£-tosylhydrazones) undergo basic decompositions to give acetylenes.^ For example, benzil bis(p-tosylhydrazone) (1§^) affords diphenylacetylene (lg^t

73!^. Eq 84) on treatment with base and pyrolysis.^

Ph-C=NNHTos Na I PhC =CPh (84) Ph-C=NNHTos ethylene glycol i2ft m

(64) G. Vi ittig and A. Krebs, Chem. Ber.. §4, 3260 (1961).

(65) Vi. R. Bamford and T. S. Stevens, J. Chem. Soc., 4735 (1952).

Therefore, decompositions of acenaphthenequinone bis(p- tosylhydrazone) (12), a new 1,2-bis(p-tosylhydrazone), was then explored in attempts to effect formation of 1,2-bisdiazoacenaphthene (1^) and its decomposition to 89

acenaphthylyne (14, Eq 2). All attempts to trap 14 with

NHTos

2 Base -2 N, (2)

14 12 12

2,5-diphenylbenzofuran, tetraphenylcyclopentadienone or

cyclopentadiene on pyrolysis of the disodium salt (lg6) of

12 fail to indicate generation of 14. Photolysis of

126 ^-n 2-methyl-1,3-t>utadiene similarly gives no evidence for 14 or its adducts.

Decompositions of 12 were then investigated under different conditions. Thus, thermolyses of the mono- (1§^) and disodium (12§) salts of 12 in chlorobenzene resulted in

2-2-tosylacenaphthenone £-tosylhydrazone (12§, Eq 85. 58'/° and 35^ respectively) on work-up. The overall conversion

TosHNN*. JUNTOS KHTos @N a

-> s °2c ?h7 TosHNN.

1)C7H?S020 0 (85) TosNN NNTos TosNN © N a © N a H^O 90

from 1Q£ may involve generation of tosylhydrazonocarbene 122

which reacts with £-toluenesulfinate anion to give 1§8 after

protonation (Eq 85)* A similar mechanism may he involved

for lg6.

The dilithium salt (122) 22 leads to chemistry which

is different from lg^ and 22§* Thus, heating 122 in diglyme at 160° resulted in 1,8-dicyanonaphthalene (201, 11$, Eq 86)

presumably via 1,2-bisdiazoacenaphthene (l^)i its isomeri

zation to 1,2,3,4-tetrazine 200 and subsequent loss of

nitrogen. This is the first known transformation of a 1,2- _.© © Li Li TosNN. NTos

A -5»

(8 6 ) A N — N

ry13 Iv 200 bis(p-tosylhydrazone) to a dicyano compound. Other 1,2,3,^- tetrazines have been proposed, but later study has shown that the structures are wrong.^ Formation of intermediate

tetrazine 200 and its subsequent decomposition of 201 is

new and the first example of this type. Attempts to improve

the yield of 201 by pyrolyzing dry 122 a_t 250° led only to

intractables. The conversion to 201 has not been maximized

as yet.

The structure of 201, a new dinitrile, is proved from

its elemental analysis and spectral properties. The IR of

201 shows two absorptions for cyano groups at 2220 and 22^-0

cm-1. 1,8-Dicyanonaphthalene (201) is also identical with

the sample synthesized independently from 1,8-dibromo-

naphthalene (202) and cuprous cyanide (44$, Eq 87).

Br Br CN CN

CuCN

Acenaphthenequinone bis(p-tosylhydrazone) (12) was then

decomposed with potassium hydroxide in refluxing ethylene

glycol giving 128 (8 .5$) and 1,8-naphthalimide (203, 28^,

Eq 83)* 1,8-Naphthalimide (20^) is believed to derived from H 92 hydrolysis of initially formed 1 ,8-dicyanonaphthalene (201).

In fact, hydrolysis of 201 was carried out under the same conditions as in equation 89, and 1,8-naphthalimide (20^) was obtained. 1,8-Dicyanonaphthalene (201) is the only parallel dinitrile known. Such dinitriles should be quite interesting and their chemistry should be explored.

In seeking an improved method for preparing lH-cyclobuta [de]naphthalen-l-one (2)lb, 1-aminobenz [cdjindol-2(1H)- one (204) was investigated. The major purpose was to determine if 204 can be converted to 20£ which then decomposes to 2 (E9 89)•

o-Cl-PhCH0

(66) Neunhoeffer and Hans: "Chemistry of 1,2,3-Triazines and 1,2,4-Triazines, Tetrazines and Pentazines" Wiley, New York, 1978, p. 1287-1295. 93

l-Aminobenz£qd]indol-2(lH)-one (204) was prepared by

literature procedures^ from 1 ,8-naphthalic anhydride as

follows. Mercuration of sodium 1 ,8-dinaphthalate and

decarboxylation gives anhydro-B-hydroxymercuri-l-naohthoic

acid which is brominated by tribromide ion to 8-bromo-l-

naphthoic acid. Treatment of 8-bromo-l-naphthoic acid with

thionyl chloride and hydrazine yields 3-bromo-l-naphthoyl

hydrazine, dehydrobromination of which to 204 (82%) is

accomplished by copper and magnesium oxide. l-Aminobenz [c^j-

indol-2(1H)-one (204) has had little study and its structure

(6?) N. S. Dokuniknin and G. I. Bystritskii, J. of Gen. Chem.. USSR.. 32, 1303 (1962).

has been presently confirmed upon its condensation with

o-chlorobenzaldehyde resulting in l-(o-chlorobenzylidene-

amino)benz[cdjindol-2(1H)-one (206, Q6%, Eq 9 0 ).

l-Aminobenz[cdJindol-2(1H)-one (204) is photolytically

stable. Irradiation of 204 in benzene results in quantitative recovery of starting molecule. Oxidation of

204 with lead tetraacetate at -?3° in tetrahydrofuran

containing tetramethylguanidine resulted in naphthostyril

(20^, 5#) in low yield. The overall process can be

rationalized as in Scheme 17 but other routes can be

envisaged. When sodium bicarbonate was used instead of 94

schem; 17

N — NH ■N

Pb(OAc)

-N - N = N - N —

Pb(OAc)

N -H

2Q2 tetramethylguanidine, an unidentified yellow crystalline solid (~12fo) was obtained which analyzed for C22^12N2°4 and exhibited IR absorption at 1740 cm-1. The mass spectrum of the product however indicates a molecular ion of

("'22^12N402 an(^ Attempts to brominate 204 with sodium hypobromite and with N-bromosuccinimide and effect base-catalyzed decomposition of N-bromo compound 208 to 20£ (Eq 91) were unsuccessful. Efforts to trap 20£ by carrying out these 95

H -N-NBr N-N:

NBS Base -> SOB (91) 204 -----> - HBr

208

reactions in cyclopentadiene or 2-methyl-1 ,3-butadiene and

other reagents were in vain.

1-Tosylaminobenz[cdjindol-2(1H)-one (202), PreP&red

from 204 and £-tosyl chloride, was investigated for its

possible (^-elimination with base to form 20^ (Eq 92).

N-NTos / ^ ?H?S02 C^SO-Cl 204 -J— L— £----^ © (92) 0 Na v— N-NTos 202 NaH l)hu OTA ^20 2 2) H20

;io

However, thermolysis (in diglyme) or photolysis (in benzene) of the sodium salt (210) of 202 resulted only in recovery of strating material (Eq 52).

All attempts to oxidize 204 with various oxidizing agents and to effect basic decomposition of 209r** m A* to 205 ** failed. SUMMARY

Wolff rearrangements do not occur in either photolysis or thermolysis of diazoacenaphthenone (£), 2-diazo-5-nitroacenaphthenone (8), 2-diazo-5,6-dinitroacenaphthenone (2)»

2-diazo-3»8-dimethoxyacenaphthenone (10) and 2-diazoaceanthrenone (11). However, carbenes generated from £-11 photolytically or/and thermally are excellent 1,3-dipoles and undergo cycloadditions to nitriles forming oxazoles.

Similarly, photochemical reactions of £-11 with acetylenes yield furans with loss of nitrogen. These carbenes also insert into a C-H bond of cyclooctane thermally and photochemically. Photolysis of 2 results in insertion into 0-H bond of t-butanol and reduction by 2-propanol to acenaphthenone. The carbene derived from 10 also coordinates with the oxygen of tetrahydrofuran followed by ring expansion to afford a spiropyran derivative. Though diazo ketones such as 7 do not effect photochemical cyclopropanation of olefins, they do react with electronegatively substituted olefins such as acrylonitrile and methyl acrylate to form isomeric spirocyclopropanes in good yields.

Thermolyses of 7-11 in acetylenes, however, result in initial 1,3-dipolar additions to the C-C triple bonds to

96 97 give spiropyrazoles, which rearrange via 1,5-sigmatropic

shifts of their carbonyl groups to nitrogen to yield

isoquinoline derivatives. These isoquinolines are thermally and photochemically stable.

Attempts to prepare benzylideneacenaphthenone p-tosylhydrazone (182) from benzylideneacenaphthenone (lgl) and p-tosylhydrazine are not successful; instead, acenaphthenequinone bis(p-tosylhydrazone) (12) is obtained. Efforts to trap acenaphthylyne (1^), as possibly generated by base- catalyzed decomposition of 12, with cyclopentadiene, 2,5- diphenylbenzofuran, tetraphenylcyclopentadienone or 2-methyl-

1,3-butadiene are without success. Decomposition of the lithium salt (lgg) of 12 at 160° leads to 1,8-dicyanonaphthalene (201) presumably via 1,2-bisdiazoacenaphthene

(13) and 1,2,3.^-tetrazine 200. The transformation of 12 to 201 is the first example of this type. Decomposition of

12 using potassium hydroxide, however, yields 1,8-naphthalimide (20^) and 2-p-tosylacenaphthenone p-tosylhydrazone

(i28)- Efforts to synthesize lH-cyclobuta [de] naphthalen-l-one

(^) oxidation of 1-aminobenz [cd]indol-2(1H)-one (20^) with lead tetraacetate, sodium hypobromite and N-bromosuccinimide or by basic decomposition of 1-tosylaminobenz-

[cdj indol-2(1H)-one (202) are vain * EXPERIMENTAL

Melting Points Melting points were determined using a

Thomas Hoover capillary melting point apparatus and a

Fisher melting point block, and were uncorrected.

Elemental Analyses Elemental analyses were performed by

Microanalysis, Inc., Wilmington, Delaware.

Infrared Spectra Infrared spectra were obtained using a Perkin Elmer, Model 457 recording spectrophotometer. All spectra were calibrated against a polystyrene absorption peak at 1601 cm-'*'.

Proton Nuclear Magnetic Resonance Spectra Proton nuclear magnetic resonance spectra were obtained using Varian

Associates (Model A-60A and EM-36OL) and Bruker (HX-90) spectrometers. Chemical shifts were measured in ppm downfield from tetramethylsilane.

Mass Spectra Mass spectra were determined by Mr. C. R.

Weisenberger on an MS-9 mass spectrometer.

98 99

Column Chromatography EK silica gel (70-325 mesh) or

MN-Kieselgel 60 (70-270 mesh) was used for column

chromatography.

Acenaphthenequinone Mono-p-tosylhydrazone(go). ^

suspension of acenaphthenequinone (1.5g» 8.2 mmole) and

jq-tosylhydrazine (1.53g» 8.2 mmole) in acetonitrile (10ml)

was refluxed for 1 h. The yellow crystals which separated

after cooling were filtered and recrystallized from methanol

to give acenaphthenequinone mono-o-tosylhydrazone(20)

(2.82g, 98^, mp 181-133°; lit!2 mp 179°(dec.)).

Diazoacenaohthenone(7)♦ Aqueous sodium hydroxide

(80ml, 0.1N, 8mmole) was added to a stirred solution of

acenaphthenequinone mono-2 -tosylhydrazone(2.8g, Smmole)

in methylene chloride (150ml). Stirring was continued for

3 h and the methylene chloride layer was separated, washed with water and dried over calcium chloride. Evaporation

of solvent gave diazoacenaphthenone(2 • 1.35g» 87/j,

mp 94-96°(cyclohexane); lit^“~ mp 94°).

5-NitroacenaT)hthenequinone( q i ) . A mixture of nitric

acid (2ml, 70^, D=1.42, 27*4 mmole) and conc. sulfuric

acid (4ml) was added drop by drop to a solution of

acenaphthenequinone (5*0g, 27.4 mmole) in conc. sulfuric

acid (25ml) keeping the temperature at 0-5°. After the 100

addition, the mixture was wanned at 30° for 2 h and poured

into ice water (1 liter). The yellow precipitate was

filtered and washed well with water until the filtrate was no longer acidic. The precipitate was then

chromatographed (silica gel, benzene) and recrystallized from glacial acetic acid to give 5-nitroacenaphthenequinone

(2i» 3 .32g, 53*3/-, mp 208-209°; l i t ^ mp 218°) as yellow needles; IR (KBr, cm"1) 1?40 (C=0, s, doublet), 1535, 1350

(N02> s ).

Anal. Calcd. for C-^H^NO^ : ^ 6 .16^.

Found : N , 6. 06c/o.

5-Nitroacenaphthenequinone 2-jo-tosylhydrazone(22).

A mixture of 5-nitroacenaphthenequinone (l.Og, 4.4 mmole) and j?-tosylhydrazine (0.84g, 4.4 mmole) in tetrahydrofuran

(30ml) containing 5 drops of concentrated hydrochloric acid was stirred for 4 h. The yellow crystals which separated were filtered and recrystallized from toluene/acetonitrile

(1:1) to give 5-nitroacenaphthenequinone 2-o-tosylhydrazone

(g£, l.22g, 70^, mp 208°(dec.)) as yellow prisms; IR

(KBr, cm"1) 3130 (NH, w), 1690 (C=0, s), 1510,1360 (N02 , s),

1330,1150 (S02 , s); NI-1R (CDC13,^) 12.68 (s, 1H, NH), 9 .11

(doublet of doublet, 1H), 8.67 (d, 1H), 8.20-7.31 (m, 7H),

2.42 (s, 3H, CH3 ).

Anal. Calcd. for C ^ H ^ N ^ ^ S : C, 57*97; H, 3*29; N,10,63.

Found: C, 57.85; H, 3-24; N,10.37. 101

2-Diazo-5-nitroacenaDhthenone(8). Cava, Litle and

Napier's method for diazoacenaphthenone was used to prepare 2-diazo-5-nitroacenaphthenone.

A mixture of aqueous sodium hydroxide (0.1N, 13ml,

1.26 mmole) and a methylene chloride (30ml) solution of

5-nitroacenaphthenequinone 2-n-tosylhydrazone (0.5g, 1.26 mmole) was stirred overnight. The methylene chloride layer was separated, washed with water and dried over calcium chloride. Evaporation of solvent and recrystallization gave yellow crystals of 2-diazo-5-nitroacenaphthenone

( 0.35g, 100^, mp 190°( dec.)(toluene)) ; IR (KBr, cm-'*')

2100 (=N2 , s), 1670 (C=0, s), 1430, 1320 (NOp, s); NKR

(CDCl^,*) 9.05 (doublet of doublet, 1H), 3.62 (d, 1H),

8.16-7.87 (m, 2H), 7-37 (u, 1H).

Anal. Calcd. for C^pH^N^O^: K, 17-57-

Found: N, 17.26.

5,6-Dinitroacenanhtheneouinone(73). Acenaphthenequinone

(2.Og, 11 mmole) was dissolved in concentrated sulfuric acid (30ml) and cooled to 0°. A solution of concentrated nitric acid (1.5ml, 70/3, D=.1.42, 24 mmole) in concentrated sulfuric acid (4ml) was added dropwise to the mixture keeping the temperature at 0-5°. After the addition, the mixture was warmed at 65° for 3 h and then poured into ice water. The precipitate was filtered, washed with water 102

and dried to give yellow-orange crystals of 5 »6-dinitro-

acenaphthenequinone(22* 2 *^3g» 8l.3/» mp 300°(toluene/

acetonitrile); lit^ mp 300°); IR (KBr, cm-1) 1765, 1750

(C = 0, s), 15^4-5 , 1370 (N°2' ’ exac_t mass calcd. m/e for

c12h^N2°6=272 -00693, obs. m/e=272.00756, diff.-2.2 ppm.

5 ,6 -Dinitroacenaphthenequinone 2-p-tosylhydrazone(24).

A suspension of 5»6-dinitroacenaphthenequinone (l.Og, 3-67 mmole) and 2 -tosylhydrazine( 0. 753g» ^.03 mmole) in tetrahydrofuran (15ml) was refluxed for ^ h. The yellow

crystals which separated on cooling were filtered and recrystallized from toluene/acetonitrile to give 5»6-

dinitroacenanhthenequinone 2-p-tosylhydrazone(2^, 1.36g,

84/, mp 213°(dec.)) ; IR (KBr, cm"1) 3200 (Nil, w), 1700

(C=0, s), 1535, 1370 (N02 , s), 1350, 1170 (S02, s).

Anal. Calcd. for cq2H12N^°7S: S ’ ?*23* Found: S, 7-17•

2-Diazo-5.6-dinitroacenaPhthenone(9). A methylene chloride (200ml) solution of 5»6-dinitroacenaphthenequinone

2-£-tosylhydrazone (4.0g, 9.1 mmole) and aqueous sodium hydroxide (100ml, 0.1N, 10 mmole) was vigorously stirred for 9 h. The methylene chloride layer was separated, washed with water and dried over calcium chloride to give

2-diazo-5*6-dinitroacenaphthenone(2» 2 -0g, 78/, mp 103

234-236°(dec.)(toluene/acetonitrile)) as orange needles;

IR (KBr, cm"1) 2100 (=N2 , s), 1?00 (C=0, s), 15^0, 1370

(N02, s ); NI.1R (CDCl3+DMS0-d6 , S' ) 8.39 (d, 1H) , 8.37 (d, 1H),

8.17 (d, 1H), 7.43 (d, 1H); exact mass calcd. m/e for

284.01316, obs. m/e=284.01897* diff. = 2.8 ppm.

Anal. Calcd. for C ^ H ^ N ^ : C, 50.70; H, 1.41; N, 19-72.

Found: C, 51-1^; H, 1.78; N, 20.00.

Aceanthrenequinone(lOO)• In a 500ml three-necked flask

fitted with a mechanical stirrer and a thermometer were

placed anthracene (lO.Og, 43.1 mmole), oxalyl chloride

(25ml) and carbon disulfide (75^1). The mixture was kept

at 0-5° and anhydrous aluminum chloride (5-0g) was added.

The thick dark-red solution was stirred at this temperature for 1 h and additional aluminum chloride (lO.Og) and

carbon disulfide (75^1) were added slowly. The mixture was stirred overnight, then poured into ice water containing concentrated hydrochloric acid and heated on a steam bath to remove carbon disulfide. The orange gummy product which separated after cooling was dissolved in methylene chloride and washed with saturated aqueous sodium carbonate.

Evaporation of solvent and recrystallization from toluene/ acetonitrile gave aceanthrenequinone (100, 3-7g* 28.4^, mp 268-270°; lit^7 mp 270°) in form of red crystals; io4

IR (KBr, cm"1) 1740, 1710 (C=0, s) 5 NI.'R (CDCl^,/) 9.16

(doublet of doublet, 1H), 8.38 (s, 1H), 8.34 (doublet of doublet, 1H), 8 .26-7.69 (m, 5H).

Aceanthrenequinone 2-p-tosylhydrazone (101).

A tetrahydrofuran (70ml) solution of aceanthrenequinone

(7«4g, 32 mmole) and p-tosylhydrazine (6 .53g» 35 mmole) was refluxed for 5 h. The mixture was cooled and the yellow precipitate of aceanthrenequinone 2-j)- tosylhydrazone (101, 12.04g, 94.4/^, mp 220-224°(dec.)

(toluene/acetonitrile)) was filtered; IR (KBr, cm"1) 3160

(Nil, w), 1670 (C = 0, s), 1360, 1180 (S07, s).

Anal. Calcd. for C23^i6N2°3S: C ’ ^9.00; 4.00; Found: C, 68.63; H, 3-92;

Calcd: N, 7 .00; S, 8.00.

Found: N, 7 .24; S, 7-97-

2-Diazoaceanthrenone(11). Aqueous sodium hydroxide

(50ml, 0.1N, 5 mmole) was added to a methylene chloride

(175ml) solution of aceanthrenequinone 2-p-tosylhydrazone

(l*57g» 3*9 mmole) and stirred overnight. The methylene chloride layer was separated, washed with water and dried over sodium sulfate. Removal of solvent and chromatography

(silica gel, benzene) gave yellow crystals of 105

2-diazoaceanthrenone(11, 0.6lg, 63*47', mp 130-131°

(cyclohexane)); IR (KBr, cm"'1') 2120 (=N2 , s), 1660 (C=0, s);

NMR (CDCl^ ,f ) 9.07 (doublet of doublet, 1H), 8 .50 (s, 1H),

8.07 (doublet of doublet, 1H), 7*80-7.15 (m, 5H, aromatic).

Anal • Calcd. for C^HgNgO: C, 78.6 9 ; H, 3*28; N, 11.48.

Found: C, 73.70; H, 3*48; N, 11.46.

Further elution allowed recovery of unreacted aceanthrenequinone mono-o-tosylhydrazone (101, 0.47g, 307'.).

2.7-Dimethoxyna~Phthalene(96). Dimethyl sulfate (20ml) was added slowly to a vigorously stirred cold solution of

2.7-dihydroxynaphthalene (16.Og, 0.1 mole) in 10^ aqueous sodium hydroxide (90ml). The thick yellow-green mixture was stirred for 2 h. Water (200ml) was added to the mixture and the gray precipitate was filtered, washed with water until the filtrate was colorless, and dried to give

2.7-dimethoxynanhthalene (g6, I8.l4g, 96.5^, mp 134-136°

(hexane/toluene); lit^ mp 135°)•

3,S-Dimethoxyacenanhthenequinone(97). In a 250 ml three-necked flask fitted with a mechanical stirrer and a thermometer were placed 2,7-dimethoxynaphthalene (lO.Og,

53.2 mmole), anhydrous aluminum chloride (lO.Og) and carbon disulfide (100ml). The mixture was cooled to 0° and oxalyl chloride (30ml) was added through a dropping 106

funnel keeping the temperature at 0-5°. The mixture was

then stirred at 25° overnight, poured into ice water,

and then heated on a steam bath to remove carbon disulfide.

The orange gummy product which separated on cooling was

dissolved in methylene chloride and washed with water.

Evaporation of the solvent and recrystallization from toluene/acetonitrile gave 3 >8-dimethoxyacenaphthenequinone

(22, 1.82g, 14/., mp 2?8°; lit^6 mp 279°) ; IR (KBr, cm"1)

1730, 1715 (C = 0, s) ; exact mass calcd. m/e for -

242.05790, obs. m/e=242.05860, diff.-3 PPm.

3,8-Dimethoxyacenaphthenequinone Kono-n-tosylhydrazone(g8 ).

A mixture of 3»8-dimethoxyacenaphthenequinone (6.l4g, 25.4 mmole) and n-tosylhydrazine (5 .21g, 23 mmole) in tetrahydrofuran (60ml) containing concentrated hydrochloric acid (1ml) was refluxed for 4 h until a clear solution was obtained. The mixture was cooled and the yellow crystals were filtered to yield 3 >3-dimethoxyacenaphthenequinone mono-p-tosylhydrazone (2§, 8.30 g, 80/, mp 173-175°(dec.)

(tetrahydrofuran)); IR (KBr, cm-1) 3150 (NH, w), 1630

(C=0, s), 1360, 1170 (S02 , s).

Anal. Calcd. for C21H18N2°5S: C ’ 61.46; H, 4.39;

Founds C, 61.65; H, 4.49;

Calcd: H, 6.83; S, 7.80.

Found: N , 6.32; S, 7 .83. 107

2-Diazo-3.8-dimethoxvacenaphthenone(10). Sodium methoxide (0.6 g, 11.1 mmole) was added to a dry methylene

chloride (100 ml) solution of 3*8-dimethoxyacenaphthene quinone mono-n-tosylhydrazone (3-0 g, 7-3 mmole) and stirred

overnight. Water was added and the methylene chloride

layer was separated and dried over calcium chloride. The residue after solvent removal and chromatography (silica gel, benzene/chloroform 1:1) gave orange crystals of

2-diazo-3»8-dimethoxyacenaphthenone (10, 0.924 g, 64*;', mp 145-146°(toluene)); IR (KBr, cm-1) 2100 (=h’2, s), 1670

(C = 0, s); Nl'R (CDC13 , % ) 7-37 (d, IK), 7-56 (d, 1H), 7.07

(d, 2H), 4.14 (s, 3H, 0CH3), 3.95 (s, 3H, OCH.^.

Anal. Calcd. for C^H-^NgCy C, 66.14; H, 3.93; N, 11.02.

Found: C, 66.13; H, 4.06; N, 11.30.

Decomnositions of Diazo Compounds

Fhotolysis All photolyses were conducted by by irradiating the diazo compounds in 220 ml of the solvent specified using a Hanovia 450 V.: medium pressure mercury lamp dipped in a pyrex well. All solvents for photolyses were dried and distilled before using. Nitrogen was bubbled through the solution before and/or during photolysis.

Photolyses were generally effected at room temperature unless otherwise mentioned. 108

Thermolysis All thermolyses were carried out by refluxing solutions of the diazo compounds in the indicated solvents under nitrogen.

Photolysis of Diazoacenanhthenone in Cyclooctane. A solution of diazoacenanhthenone (O.k g, 2 mmole) in cyclooctane was photolyzed for 3 h. The residue after removing cyclooctane under reduced pressure was chromatographed on silica gel (hexane:benzene 2:1). The yellow oil obtained, on purification by chromatography and sublimation, gave 2-cyclooctylacenaphthenone (110,

0.295 g, 51*5/5) as light yellow oil; IR (CH9C19, cm-1)

2930-2360 (cyclooctyl C-H, s), 1720 (0=0, s); NMR (CDCl^,^)

8.12-7.33 (m, 6H, aromatic), 3*65 (d, 1H, benzylic),

1.9-1*0 (broad singlet, 15H, cyclooctyl); mass spectrum

273 (M+). The 2 ,4-dinitrophenylhydrazone of 2-cyclo-

Anal. Calcd. for ^20^Z2G: C ’ S6 .33; H, 7-91.

Found: C, 86.^7; H, 7 .72. octylacenaphthenone was recrystallized from toluene/ acetonitrile as red crystals, mp 23^-236°(dec.).

Further elution with benzene and recrystallization from toluene/acetonitrile gave 1 ,8-naphthalic anhydride

85 mg, 20.8/; mn 266-269°; lit^ mp 267-269°), identified by compariig its IR, NMR and Mass spectra with 109

those of an authentic samnle.

(68) Ng. Ph. Bun-Hoi and Denije J.avit, Rec. trav. Chim.t 77, 724 (1953); G. P. Fetrenko and K. I\'. Dashevskii, Znur. Priklad. Khim., ^2, 1126 (1959)*

Thermolysis of Diazoacenaphthenone in Cyclooctane. A

solution of diazoacenaphthenone (0.4 g, 2 mmole) in

cyclooctane (100 ml) was refluxed under nitrogen for 19 h.

The solvent was removed under reduced pressure and the

residue was purified "by chromatography, as described in

the previous photolysis, to give 2-cyclooctylacenaphthenone

(110, 0.35? g, 62. J;'j) .

Further elution with benzene yielded 1,8-naphthalic

anhydride( 10(3, 0.146 g, 35*3/).

Fhotolysis of Diazoacenaphthenone in t-Butanol. A

t-butanol solution of diazoacenaphthenone (0.5 g, 2.57 mmole) was photolyzed for 5 h. Upon removal of the solvent

and chromatography of the residue on silica gel (benzene), two compounds were obtained:

(i) Biacenedione (or diacenaphthylidenedione) (§1, n ^1 5 mg, 1.8yo, mp 292-295 (petroleum ether/toluene); lit. mp 2940); exact mass calcd. m/e for C2^K^202=332.03372,

obs. m/e=332.03442, diff.=2.l ppm. 110

(ii) 2-Butoxyacenaphthenone(10g, 71 mg, 17*4/, mp

212-214°( toluene)) as yellow crystals; IR (KBr, cm”"1)

1725 (0 = 0, s); NKR (CDCl^, %) 8.1-7.23 (m, 6H, aromatic),

5.05 (s, 1H, benzylic) , O.7O (broad singlet, 9H, 3CH^) ; exact mass calcd. m/e for C ^ H . ^ 02^240.11502, obs. m/e=

240.11576, diff.=3 ppm.

Anal. Calcd. for 80.00; H, 6 .67.

Found: C, 80.42; H, 6.12.

Photolysis of Diazoacenaphthenone in 2-Propanol. A solution of diazoacenaphthenone (0.4 g, 2 mmole) in

2-propanol was irradiated 3 h. The residue after removing solvent and chromatography on silica gel (benzene) yielded the following compounds:

(i) Biacenedione (81, 6 mg, 1.7#) as previously characterized; (ii) Acenaphthenone (102, 84 mg, 24.3/, mp 113-ll6°(petroleum ether/benzene); l i t ^ mp 120-121°);

IR (KBr, cm-1) 1710 (C=0, s); NKR (CDCl^, d) 8.15-7.26

(m, 6H, aromatic), 3*77 (s, 2H, benzylic); exact mass calcd. m/e=168.05751» obs. m/e=163.05790» diff.=2 .4 ppm.

(iii) 1 ,8-Naphthalic anhydride (10^, 59 mg, 14.4/) as previously characterized.

(6 9 ) A. Bosch and R. K. Brov/n, Canadian J. of Chem. . 46, 715 (1963); L. F. Fieser and J. Carson, J. Amer. Chem.~3oc.. 6 2 , 432 (1940). Ill

Thermolysis of Diazoacenaphthenone in Cyclohexene in the

Presence of Cuprous Bromide. A mixture of diazoacenaph thenone (0.2 g, 1.03 mmole) and catalytic amount of cuprous bromide in cyclohexene (40 ml) was refluxed under nitrogen for 2.5 h. Cuprous bromide was filtered off and the residue crystal was chromatographed (silica gel, chloroform) to give biacenedione (81, 0.131 g, 76*53).

Thermolysis of Diazoacenaphthenone in Acrylonitrile in the

Presence of Palladium Acetate. A mixture of diazo acenaphthenone (0.2 g, 1 mmole) and a trace amount of palladium acetate in acrylonitrile (25 ml) was refluxed 8 h.

The catalyst was filtered and the filtrate, after removing the solvent and chromatograohy on silica gel, yielded two compounds:

(i) Elution with benzene gave 2'-cyanospiro[acenaphthenone-2,1'-cyclopropane] (118, 84 mg, 37*2:3, mo 115-116°

(petroleum ether/toluene); lit.^ mp 113-119°); IR (KBr, cm-1) 2250 (CsK, w), 1715 (C=0, s); N O (CDCl^.S )

3.23-7*25 (m, 6H, aromatic), 2.63-1*66 (m, 3H, cyclopropyl

C-H)l Jg e O H Z ' Jcis'9 Hz' Jtrans'7 Hz)i exact mass calcd. m/e for C^^H^N0=219.06341, obs. m/e=219.O6905, diff.2.7 ppm. 112

(ii) Further elution with chloroform yielded 2'-cyanospiro [acenaphthenone-2 , 1'-cyclopropane]] (llg, 87 mg, 38^, mp 163-164-°; lit.^1 mp 163-164-°) isomeric with 118; IH

(KBr, cm-1) 2260 (C=N, w) , 1?15 (C=0, s); exact mass calcd.'* m/e for C^^H^N0=219.0684-1, obs. m/e=219.06905. diff.=2.7 ppm.

The assignments of structures of spirocyclopropanes

118 and llg are based on their NMR spectra and are opposite that previously given^ as explained in the Results and

Discussion.

Photolysis of Diazoacenaphthenone in Acetonitrile. An acetonitrile solution of diazoacenaphthenone (1.0 g, 5*15 mmole) was irradiated for 2.5 h. Acetonitrile was removed under vacuum and the crystalline residue was chromatographed on silica gel (benzene). 8 -Methylacenaphth [l, 2-cfj oxazole

(111, 0.657 g» 6 1 . 7 mp 108-110°; lit.53 mp 115-116°); was obtained as yellow crystals; NMR (acetone-d^,£ ) 7.6-7*17

(m, 6H, aromatic), 2.27 (s, 3H, CH^); exact mass calcd. m/e for C1^H^N0=207•0684-1, obs. m/e=207.06876, diff.=1.7 ppm.

Anal. Calcd. for C^H^NO: C, 81.16; H, 4-.35; N, 6 .76.

Founds C, 81.41; H, 4.28; N, 6 .83.

Thermolysis of Diazoacenaphthenone in Acetonitrile in the

Presence of Palladium Acetate. A solution of 113 diazoacenaphthenone (0.2 g, .1 mmole) and a trace amount of palladium acetate in acetonitrile (50 ml) was refluxed for

7 h and then filtered. After removing the solvent, the residue was chromatographed on silica gel and eluted with benzene and chloroform. Biacenedione (81, 20 mg, 11.7^) and recovered diazoacenaphthenone (0.121 g, 60.5:'') respectively were obtained.

Photolysis of Diazoacenaphthenone in Benzonitrile. A benzonitrile solution of diazoacenaphthenone (0.5 g. 2.57 mmole) was photolyzed 9 h* Upon removal of the benzonitrile and chromatography (silica gel, benzene), there was isolated yellow crystals of 8-phenylacenaphth[l,2-dJ oxazole (ll£,

0.165 6» 24;', mp 217-218°; lit.-^ mp 217-213°); exact mass calcd. m/e for C^gK1^NO = 269• 03405, obs. m/e =269. 03469, diff.=2.2 ppm.

Anal. Calcd. for C^H-^NO: C, 84.76; H, 4.09; N. 5-20.

Found: C, 34.51; H, 4.41; N, 5 .28.

Thermolysis of Diazoacenaphthenone in Benzonitrile. A solution of diazoacenaphthenone (0.5 g» 2.57 mmole) in benzonitrile was refluxed at 160° for 65 h. The solution gradually turned to a deep red color. Benzonitrile was removed under vacuum and the residue was chromatographed 114

(silica gel, benzene) to yield 8-phenylacenaphth[l,2-dJ oxazole

(112, 0.245 g» 3^-35) as characterized in the orevious experiment.

Thermolysis of Diazoacenauhthenone in Benzonitrile in the

Presence of Cupric Sulfate. A mixture of diazoacenanhthenone (0.4 g, 2 mmole) and anhydrous cupric sulfate (0.2g) in benzonitrile (50 ml) was refluxed (160°) for 24 h. The cuoric sulfate was filtered off, work up as previously gave biacenedione (81, 0.27 g, 785) as the only product.

Photolysis of Diazoacenaphthenone in Phenylacetylene.

A phenylacetylene solution of diazoacenaphthenone (0.5 g,

2.57 mmole) was irradiated for 3 h. The phenylacetylene was removed under vacuum and the residue was chromatographed on silica gel (hexane). 3-?henylacenaphtho[l,2-b] furan

(120, 0.147 g, 21.35, mp 130-131°(petroleum ether)) was isolated as orange crystals; (CDC1^,S ) 7.35-7.15 (m,

11H, aromatic), 6.99 (s, 1H); exact mass calcd. m/e for

C20Hl?O=268,OB331’ ol3S* m/e=263.08946, diff.=2.2 ppm.

Anal. Calcd. for C20H120: G’ ^*^3. Found: C, 89.64; H, 4.45. 115

Thermolysis of Diazoacenaphthenone in Dimethyl Acetylene-

dicarboxylate. A mixture of diazoacenaphthenone (0.3 g»

1.5 mmole) and dimethyl acetylenedicarboxylate (1 ml) in benzene (10 ml) was reflused for 22 h. After cooling the mixture, the yellow precipitate obtained was filtered and

recrystallized from toluene/acetonitrile to give dimethyl 7-

oxo-?H-benzo[delpyrazolo [5»1-a]isoquinoline-10,11-dicarboxylate (136, 0.46 g, 88.54, mp 204-205°) as orange crystals;

IR (KBr, cm"1) 1750-1700 (0=0, broad, s) ; NP.R (CDCl^, £)

8.37-7.23 (m, 6H, aromatic), 4.02 (broad singlet, 6H, 20CH^); exact mass calcd. m/e for C3gH^2N20^=336.07461, obs. m/e =

336.07533, diff.=2 ppm.

.Anal. Calcd. for O ^ g H - ^ I ^ O ^4.29; h , 3*57; N, 3.33*

Found: C, 64.14; H, 3.44; N, 8.64.

Jhotolysis of 2-Diazo-5-nitroacenanhthenone in Acetonitrile.

A solution of 2-diazo-5-nitroacenaphthenone (0.5 g, 2.1 mmole) in acetonitrile was irradiated for 1.5 h and then concentrated. Chromatography of the residue on silica gel

(benzene) yielded red crystals of 8-methyl-3-nitroacenaphth-

[l, 2-dJ oxazole (122, 0.225 g, 48.4.5, mp 2l4-2l6°( petroleum ether/benzene)); IR (KBr, cm"1) 1510, 1320 (N02, s); RT.'.R

(CDCl^, 5 ) 3.62-8.50 (doublet of doublet, 1H), 8.45 (d, 1H),

7-79 (d, 1H), 7.7-7-5 (m, 2H), 2.66 (s, 3H, CH3); exact 116 mass calcd. m/e for C ^ H g l ^ O ^ 252. 053^-3 t obs. m/e =252.05393 # diff.=1.9 ppm.

Anal. Calcd. for C ^Kgl'^O^: C, 66.66; H, 3*17; N, 11.11.

Found: C, 66.64; H, 2.93; N, 10.9 6 .

Photolysis of 2-Diazo-6-nit.rn acenanhthenone in Benzonitrile.

A benzonitrile solution of 2-diazo-5-nitroacenaphthenone

(0.5 g, 2.1 mmole) was photolyzed for 12 h. Removal of the benzonitrile under reduced pressure and chromatography of the residue on silica gel (benzene) gave 3-nitro--

(8-phenylacenaphth)[1,2-d]oxazole (130, 0.226 g, 3i+«5""» mp275 -2?7°(dec.)( petroleum ether/chloroform)) as red- brown crystals; IR (KBr, cm~^) 1435, 1330 (NO-,, s);

NKR (CBC1^,3 ) 3.9^-7.25 (m, 10H, aromatic); exact mass calcd. for C ^ H ^ I ^ G ^ l ^ - 06914, obs. m/e=3l4.06968, diff.=1.6 ppm.

Anal. Calcd. for C^^H^QPo0g: C, 72.61; H, 3-13; N, 3.92.

Found: C, 72.71; K, 2.94; K, 3 .90.

Thermolysis of 2-Diazo-5-nitroacenarhthenone in Benzonitrile.

2-Diazo-5-nitroacenaphthenone (0.4 g, I.67 mmole) was dissolved in benzonitrile (150 ml) and refluxed for 24 h.

Removal of solvent and chromatography as in the photolysis experiment gave 3-nitro-8-phenylacenaphth[l,2-d]oxazole 117

(120, 0.267 g, 50.3/6, mp 275-277°( dec. )).

Thermolysis of 2 -Diazo -5-nitroacenaphthenone in Benzonitrile

in the Presence of Cupric Sulfate. A mixture of

2 -diazo-5-nitroacenaphthenone (0.173 6. 0.724 mmole),

anhydrous cupric sulfate (0.1 g) and benzonitrile (150 ml)

was refluxed for 24 h. Filtration of the cupric sulfate

and work up as previously described afforded 3-nitro-

(8-phenylacenaphth)[l,2-d]oxazole (IgO, 0.3 g, 39.35).

Flution with methanol yielded benzamide (0.124 g, 1.03

mmole, mp 123-124°(toluene); lit?0 mp 128-129°); exact

mass calcd. m/e for 0^11^1^0=121.05276, obs. m/e=121.053°7 ,

diff.=2.6 ppm.

(70) 2. Zil'bemian, A. I. Kulkova and N. A. Sazanova, Khim. Kaukai. Prom., 4, 135 (1959); Pfleger and I-".. v. Strandfmannl chem. Ber.. go, 1455 (1957).

Photolysis of 2~Diazo-5"hitroacenanhthenone in Phenylacetylene.

A phenylacetylene solution of 2-diazo-5-nitroacenaphthenone

(0.5 g, 2.1 mmole) was photolyzed 3 h and the phenylacetylene was then removed under vacuum. Chromatography of the residue on silica gel (benzene) yielded dark brown crystals of 3-nitro-8-phenylacenaphtho [l,2-b]furan (131. 118

0-393 g» 60/, mp 186-183°(petroleum ether/toluene));

IR (KBr, cm-1) 1515, 1330 (K0o, s); IWR ( CDCly Dl.'.SO-dg, S )

8.30 (doublet of doublet, 1H), 7«90-?.30 (m, 9H, aromatic),

7.10 (s, 1H) ; exact mass calcd. m/e for C2q H ^ N 0^ =

313-07339, obs. m/e=313 - 07999, diff.=1.6 ppm.

Anal. Calcd. for C20H11N°3: c * 76.6 8 ; H, 3-51; K, 9.97.

Found: C, 76.91; H, 3-57; U, 9.65-

Thermolysis of 2-Diazo-5-nitroacenaohthenone in

Phenylacetylene. A mixture of 2-diazo-5-nitro acenaphthenone (0.3 g, 1.25 mmole) and phenylacetylene (2 ml) in chlorobenzene (20 ml) was refluxed under nitrogen for 19 h and concentrated. Chromatography (silica gel, chloroform) of the residue resulted in isolation of 3-nitro-10-phenyl-

7H-benzo [dejpyrazolo [5,1-jf) isoquinolin- 7-one (123* 0.29 g,

6 7 .0;', mp 298°(chloroform)) as yellow crystals; IR (KBr, cm"1) 1710 (c=o, s), 1520, 1350 (no2 , s ) ; nl:r (CDC1?,S )

9.06-7.9-3(m, 11H, aromatic); exact mass calcd. m/e for

C2ohh i'tC3= 3^1 • 08003, obs. m/e =39-1.03057, diff. = 1.5 ppm.

Anal. Calcd. for C^H-j^I^Oy C, 70.33; H, 3-23; N, 12.32.

Found: C, 70.93; H, 3-30; N, 12.39-

Thermolysis of 2-piazo-3-nitrnacenaohthenone in Dimethyl

Acetylenedicarboxylate. A mixture of 2-diazo-5- nitroacenaphthenone (0.2 g, 0.83 mmole) and dimethyl 119 acetylenedicarboxylate (0,5 ml) in chlorobenzene (20 ml) was refluxed under nitrogen for 21 h. Removal of solvents and chromatography (silica gel, chloroform) yielded yellow crystals of dimethyl 3-nitro-7-oxo-7H-benzo Qdejpyrazolo-[

5,1-a]isoquinoline-10,11-dicarboxylate (140, 0.265 g, 83$, mp 235-238°(toluene/acetonitrile)); IR (KBr, cm”1) 1730

(C=0, broad, s), 1530, 1350 (N02 , s); M R (CDCl^,^) 9-14-

8.96 (m, 3H), 8.41 (d, 1H), 8.17-8.05 (m, 1H), 4.06 (s, 3H,

OCH^), 4.03 (s, 3H, OCH^); exact mass calcd. m/e for

C18H11N3°7=381,05969’ obs* n>/e=381.06036, diff.=1.8 ppm. Anal. Calcd. for C ^ H ^ N ^ s C, 56.69; H, 2.89; N, 11.02.

Found: C, 56.17; H, 2.85; N, 11.04.

Photolysis of 2-Diazo-5-nitroacenaphthenone in Benzene.

A benzene solution of 2-diazo-5-nitroacenaphthenone (0.4 g,

I.67 mmole) was irradiated for 3 h. Removal of benzene and chromatography on silica gel (benzene) resulted in

5-nitro-2-phenylacenaphthenone (144, 0.263 g. 54.5>1, mp 153-1540 (dec.) (petroleum ether/toluene)) as yellow crystals; IR (KBr, cm"1) 1730 (C=0, s), 1520, 1330 (N02 , s);

NMR (CDCl^,3 ) 9 .O6 (doublet of doublet, 1H), 8.6 (d, 1H),

8.04 (d, 1H), 7 .52-7 .O (m, 7H, aromatic), 5.0 (s, 1H, benzylic); exact mass calcd. m/e for cigHllN °3 -

289.07389* obs. m/e=289.07459. diff.=2.4 ppm. 120

Anal. Calcd. for C ^ H ^ O y C, 74.74; K, 3*81; N, 4.84.

Found: C, 74.74; H, 4.00; N, 4.99.

Photolysis of 2-Diazo-5.6-dinitroacenaT>hthenone in

Acetonitrile. 2-Diazo-5.6-dinitroacenaphthenone (0.4 g,

1.4 mmole) was photolyzed in acetonitrile for 6 h.

Acetonitrile was removed and chromatography of the residue on silica gel (tetrahydrofuran) yielded brown crystals of

8-methyl-(3 »4 -dinitroacenaphth) [l, 2-gf] oxazole (1471

0.232 g f 67.4,'a, mp 275°(dec.) (toluene/acetonitrile)) ;

IF (KBr, cm-1) 1530, 1360 (K02 , s) ; KKR (CDCl^DMSO-d^, S )

3.13 (d, 2H), 7-32 (d, 2H), 3-04 (s, 3H, CH3); exact mass calcd. m/e for C^H^N^O^ s297 • 03856, obs. m/e=297.03907. diff.=1.7 ppm.

Anal. Calcd. for C^H^K^O^: C, 56.5 8; H, 2 .36; N, 14.14.

Found: C, 56.73; H, 2 .56 ; N f 13-88.

Photolysis of 2-Diazo-5t6 -dinitroacena'ohthenone in

Benzonitrile. A solution of 2-diazo-5*6-dinitroacenaphthenone (0.427 g. 1.49 mmole) in benzonitrile was photolyzed for 5 h. Upon removing the benzonitrile under vacuum, the residue was chromatographed (silica gel, benzene). 3,4-dinitro-8-phenylacenaphth[l,2 -d] oxazole

(1^+8, 0.142 g, 26.2/, mp 233-286° ( dec.) (toluene/ acetonitrile)), brown crystals, was the only isolable 121 product; IR (KBr, cm”'*') 1530, 1360 (N0?, s); exact mass calcd. m/e for C - ^ H ^ O ^ =359-05^21 , obs. m/e =359«05492, diff.=2 ppm.

Anal. Calcd. for C-^H^O^: C, 63 .51; H, 2.51; N, 11.70.

Found: C, 63.71; H, 2.65; N, 11-92.

Photolysis of 2-Diazo-5.6-dlnitroacenanhthenone in

Phenylacetylene. A solution of 2-diazo-5,6-dinitroacenaphthenone (0.5 g* 1-75 mmole) in phenylacetylene was irradiated for 2 h and then concentrated under vacuum.

Chromatography (silica gel, chloroform) of the residue yielded 3 ,4-dinitro-8-phenylacenaphtho [l,2-bJfuran

(l^g, 0.3 g, 47.6;3, mp 267-270°(ethyl acetate)) as black crystals; IR (KBr, cm”'*') 1530, 1350 (KOg* s); exact mass calcd. m/e for C2qH-, ^20 ^ = 353.05896, obs. m/e = 353. 05969» diff.=1.9 ppm.

Anal. Calcd. for C20H10N2°5: C| 67.04; H, 2.79; N, 7-32.

Found: C, 67-3^; H, 2 .9 8 ; K, 7-76.

Thermolysis of 2-Diazo-5,6-dinitroacenar)hthenone in Dimethyl

Acetylenedicarboxylate. A mixture of 2-diazo-5»6-dinitroacenaphthenone (0.163 g, 0.57 mmole) and dimethyl acetylenedicarboxylate ( 1 ml) in chlorobenzene (20 ml) was refluxed for 20 h. Upon removal of the solvents under vacuum, the residue was chromatographed (silica gel, 122

chloroform). Dimethyl 3,4-dinitro-7-oxo-7H-benzo [delpyrazolo-

[5 fl-ajisoquinoline-1 0 ,11-dicarhoxylate (1£1 * 0 .2g, 83*3^»

mp 290-293°(toluene/acetonitrile)), yellow crystals, was

the only isolable product; IR (KBr, cm"1 ) 1740 (C=0, s) ,

1550, 1350 (N02, s ); exact mass calcd. m/e for =

426.04477, obs. m/e =426.0^-537, diff.=1.4 ppm.

Anal. Calcd. for : C, 50.?0; H, 2.35; K, 13-1^.

Found: C, 51-23; H, 2.29; N, 12.70.

Photolysis of 2-Diazo-5.6-dinitroacenarhthenone in .Benzene.

A benzene solution of 2-diazo-5»6-dinitroacenaphthenone

(0.4 g, 1.4 mmole) was photolyzed for 5 h. Removal of benzene and chromatography (silica gel, chloroform) led to isolation of 2-hydroxy-5 ,6-dinitro-2-phenyiacenaphthenone

0.232 g, 45.21, mp 227-229°(dec.)(toluene/ acetonitrile)) as yellow crystals; IR (KBr, cm"1) 3440

(broad, OH), 1730 (C=0, s), 1530, 1350 (N02 , s); N O

(CDC13 , J) 8.6-3.46 (m, 2H), 8.20 (d, 1H), 7-76 (d, 1H),

7.32 (s, 5H, phenyl C-K), 5*26 (s, 1H, OH); exact mass calcd. m/e for cx3HioN206 = -^0 ‘05333, obs. m/e=350.05455, diff.=1.9 ppm.

Anal. Calcd. for ci9HxoN2°6: C* ^1.71; H * 2 *S6 ; N, 8.00.

Found: C, 61.72; H, 3*1^; N, 7*95.

C, 61.66; H, 3-15; N, 8.00. 123

Photolysis of 2-Diazoaceanthrenone in Acetonitrile.

2-Diazoaceanthrenone (0.4 g, 1.6 mmole) was irradiated in acetonitrile for 4 h. Solvent removal and chromatography

(silica gel, benzene) resulted in 2-methylaceanthryleno(^2,1-dQ - oxazole (1§0, 0.153 g, 36.3/^, mp 132-135°(petroleum ether/ toluene)) in form of red crystals; NFR (CDClg ,% ) 8.14-7.16

(n, 6H, aromatic), 2.6 (s, 3H, CH^); exact mass calcd. m/e for CigH11NO=257.03406, obs. m/e=257•03452, diff.=1.9 ppm.

Anal. Calcd. for Cl8Hn N0: C, 34.05; H, 4.23; N, 5.45.

Found: C, 83-85; H, 4.47; N , 5 .54.

Photolysis of 2-Diazoaceanthrenone in Benzonitrile.

2-Diazoaceanthrenone (0.4 g, 1.6 mmole) in benzonitrile was photolyzed for 4 h. Removal of the benzonitrile under vacuum and chromatography (silica gel, hexane/benzene 1:1) of the residue allowed isolation of red-brown crystals of

2-phenylaceanthryleno[2,1-dJoxazole (161, 58 mg, 11.1%, mp

160-165°( petroleum ether/toluene)) ; NI.'.R (CDClg , $ )

3.33-7*1? (m, 13H); exact mass calcd. m/e for CpgH^gH0 =

319.09971, obs. m/e=319.10043, diff.=2.5 ppm.

Anal. Calcd. for C2gHigN0: C, 36.52; H, 4.07; N, 4.39.

Found: C, 86.69; H , 4.01; II, 4.21.

Photolysis 0f 2-Diazoaceanthrenone in Phenylacetylene.

A phenylacetylene solution of 2-diazoaceanthrenone (0.5 g, 124

2 mmole) was irradiated for 5 h. Removal of phenyl

acetylene under vacuum and chromatography (silica gel,

hexane) gave dark purple crystals of 10-phenylaceanthro[

l,2-b]furan (162, 65 mg, 10/, mp 176-173°(petroleum ether));

NliR (CDC13, S ) 8.4-7 (doublet of doublet, 1H) , 8.30 (s, 1H),

3.07-7.24 (m, 11H, aromatic), 7-09 (s, 1H); exact mass

aclcd. m/e for C2^H^^0=313.10446, obs. m/e=318.10525,

diff.=2.5 ppm.

Anal. Calcd. for C^H-^O: C, 90.57; H, 4.40.

Found: C, 90.25; H, 4.33.

Thermolysis of 2-Diazoaceanthrenone in Phenylacetylene.

A mixture of 2-diazoaceanthrenone (0.3 g, 1.2 mmole) and

phenylacetylene (2 ml) in toluene (20 ml) was refluxed

under nitrogen for 20 h. The residue, after removing

solvents, was chromatographed (neutral alumina) to give

two compounds:

(i) Elution with benzene yielded 2-diazoaceanthrenone

(11 mg, 3-7/).

(ii) Elution with benzene:chloroform 1:1 gave

2-phenyl-12H-dibenzo [de ,h] pyrazolo [l, 5-bJ isoquinolin-12-one

0.418 g, 98*2/, mp 222-222,5° (toluene/chloroform)) as red needles; IR (KBr, cm“^) 1685 (C=0, s); NKR (CDCl^.S" )

8.64-7*10 (m, 14h , aromatic and pyrazole C-H); exact mass 125

calcd. m/e for ^24^14^2° 3^6.11060, obs. m/e 3^6.11111,

diff. 1.4 ppm.

Anal. Calcd. for C24Hl4N2°! C, 83.2k; H, 4.05; N, 8 .09.

Found: C, 83.32; H, 4.25; N, 8 .29.

Thermolysis of 2-Diazoaceanthrenone in Dimethyl

Acetylenedicarboxylate. A mixture of 2-diazoaceanthrenone

(0.26 g, 1 .Ok mmole) and dimethyl acetylenedicarboxylate

(1 ml) in toluene (20 ml) was refluxed under nitrogen for

22 h and concentrated. Chromatography of the residue on neutral alumina (chloroform) yielded orange needles of dimethyl 12-oxo-12H-dibenzo[de,h]pyrazolo [l,5-b]isoquinoline-.

2,3-dicarboxylate (166, O.kl g, 100$, mp 268-269°(toluene/ acetonitrile)); IR (KBr, cm”1) 1750, 1720, 1710 (C 0, s);

NMR (CDCl^, ) 8.92 (doublet of doublet, 1H), 8.67 (s, 1H),

8.13-7.15 (m» 6H, aromatic), 4.00 (s, 6H, 20CH^); exact mass calcd. m/e for C22^l4N2°5 336.09026, obs. m/e 386.09090, diff. 1.5 ppm.

Anal. Calcd. for C ^ H ^ N g O ^ : C, 68.39; H, 3-63; N, 1.25.

Found: C, 68.81; H, 3-74; N, 7 .18.

Photolysis of 2-Diazoaceanthrenone in Benzene. A benzene solution of 2-diazoaceanthrenone (0.5 g, 2 mmole) was irradiated for 4 h. The concentrate was chromatographed on silica gel (hexane:benzene 1:1) and led to yellow-orange 126

crystals of 2 -phenylaceanthrenone (l^O, 0.41 g, 68/, mp

210-212°(dec.)(toluene/acetonitrile)); IR (KBr, cm"1)

1690 (C=0, s); N O (CDCl^, 5) 9 .06 (doublet of doublet, 1H),

8.6 (s, 1H), 8 .2-7.2 (m, 11H), 4.90 (s, 1H); exact mass

calcd. m/e for ^22^14° = 294. 10446 , obs. m/e = 294. 10512 ,

diff.=2 ppm.

Anal. Calcd. for C2pH3ii|0: C, 89.79 ; H, 4.76.

Found: C, 8 9 .9 8 ; H, 4 .9 3 .

Thermolysis of 2-Diazoaceanthrenone in Acrylonitrile.

A mixture of 2-diazoaceanthrenone (0.4 g, 1.6 mmole) and

acrylonitrile (5 nil) in toluene (20 ml) was refluxed for

20 h. After evaporating the solvents the residue was

chromatographed on silica gel to give two isomeric compounds:

(i) Elution with benzene gave 2'-cyanospiro [ace-

anthrenone-2 ,1 '-cyclopropane] (l£i» 0.135 g, 41.9:5, mp

199-200°(toluene)), fluorescent yellow crystals; IR

(KBr, cm"1) 2250 (C=N, w), 1700 (C=C, s); NKR (CDCl^.S )

9.20 (doublet of doublet, IK), 8.73 (s, IK), 8.23-7.17

(m, 6H, aromatic), 2.67-1.86 (m, 3H, cyclopronyl C-H) with

Shx=2.56, / H a=2.l4, $ H^=l.98, JAX = 9 K z , J3x=7 H z , J ^ 5 H z ; exact mass calcd. m/e for C-^H^NO =269.08406, obs. m/e =

269.08469, diff.=2.2 ppm.

Anal. Calcd. for C ^ H ^ N O : C, 84.76; H, 4.09; N, 5.20.

Found: C, 84.74; H, 4.23; N , 5 .56. 12 7

(ii) Further elution with chloroform yielded

2 *-cyanospiro[aceanthrenone-2 fl'-cyclopropaneJ (1£2 ,

O .236 g, 53.5rS, mp 195*5-19?°(toluene/acetonitrile)); IR

(KBr, cm”1) 2260 (C=N, w), 1695 (C=0 , s); NKR (CDCly S ’ )

8.95 (doublet of doublet, 1H), 8.60 (s, 1H), 8.14-7.20

(m, 6H, aromatic), 2.60-2.00 (m, 3H, cyclopropyl C-H) with

£hx=2 .5 1 , 5 Ha= 2.37, i H b=2.13, JAX = 6.8 Hz, Jbx=B.2 Hz,

Jab“3• 7 Hz; exact mass calcd. m/e for C^H^-iRO 269*08406, obs. m/e 269*08469» diff. 2.2 ppm.

Anal. Calcd. for C^H-j^NO: C, 84.76 ; H, 4.09; N, 5-20.

Found: C, 84.40; H, 4.05; N, 5-39*

Thermolysis of 2-Diazoaceanthrenone in Nethyl Acrylate.

A solution of 2-diazoaceanthrenone (0.2 g, 0.32 mmole) and methyl acrylate (3 ml) in toluene (10 ml) was refluxed for 22 h, concentrated and chromatographed on silica gel.

Elution with benzene and recrystallization from petroleum ether (65-110°)/toluene (1 :1 ) yielded

2 *-me thoxy carbonyl spiro [aceanthrenone-2 , l' -cyclopropane^)

0.127 g, 51-3/0, mp 158-159°) as fluorescent yellow needles; IR (KBr, cm-1) 1725, I69O (C=0, s); NKR (CDCl^.S )

9 .O5 (doublet of doublet, 1H), 8.43 (s, 1H), 8 .1-7.2

(m, 2H); mass spectrum calcd. m/e for ^20^114-®3 ~

302.09423, obs. m/e =302.09495, diff. = 2ppip. 128

Anal. Calcd. for C20^l4°3! C ’ 79*^7; H, 4.64. Found: C, 79.10; H, 4.53.

Further elution with chloroform led to isolation of

2 '-methoxycarbonylspiro [aceanthrenone-2 ,1 '-cyclopropane]

97 mg, 39*2/, mp 173-174°(petroleum ether/toluene)

12 (KBr, cm-1) 1730, I69O (C = 0, s) ; Nil2 (CDCl^.S )

9.04 (doublet of doublet, 1H), 3.47 (s, 1H), 8.1-6.84

(m, 6K), 3-73 (s, 3H, OCH^), 2 .9-2.36 (m, 2H, cyclopropyl),

1.97-1*77 (two doublet, 1H); mass spectrum calcd. m/e for

C20Hi4^ = 302.09^28, obs. m/e=302.09495, diff.=2ppm.

Anal. Calcd. for C20Hl4°3: c * 79*^7; H, 4.64. Found: C, 79*42; H, 4.65.

"hotolysis of 2-Diazo-3.8-dimethoxvacenarhthenone in

Pethanol. 2-Diazo-3 ,8-dimethoxyacenaphthenone (0.4 g,

1.57 mmole) was irradiated in methanol for 3 h. The

residue obtained after removing the methanol was

chromatographed on silica gel (chloroform) to give

2 , 3, 3-trimethoxyacenaphthenone (181, 0.313 g, 73.3::^» mp 130-132°(toluene)); IR (KBr, cm~“) 1720 (C=0, s),

1620, 1600 (C=C, s) 1370, 1350, 1330 (CH3, m), 1170, 1100,

1050 (C-0, s); KliR (CDC1,,S) 7*96 (d, IK), 7*76 (d, 1H), j 7.17 (d, 1H), 7*12 (d, 1H), 5*05 (s, 1H), 4.10 (s, 3H, 0CH3), 129

4.06 (s, 3H, OCHg), 3*53 (s , 3H, OCH^); exact mass calcd.

m/e for C-^H^O^-258.O8920, obs. m/e=258.08966, diff. = 1.8

ppm.

Anal. Calcd. for C ^ H ^ O ^ : C, 6 9 .76; H, 5-^3-

Found: C, 69.9 8 ; H, 5-22.

Fhotolysis of 2-Diazo-3 .B-dimethoxvacenaohthenone in

T e t rahyd r0 furan. 2-Diazo-3,8-dimethoxyacenaphthenone

(0.4 g, 1.57 mmole) was dissolved in tetrahydrofuran and

photolyzed for 2.5 h. Removal of solvent and chromatography on silica gel (benzene/chloroform 1 :1) yielded spiro [3 ,3-dimethoxyacenaphthenone-2,2 '-tetrahydropyran)

0.25 g, 53*3;3, mp 135-133°( ether) ) as pale yellow crystals; IR (K3r, cm-1) 1700 (C=C, s), 1350, 1370 (CHg, w) ,

1170, 1050 (c-o, s); ni.;r (cdci3,S ) 7-95 (d, ih), 7.75

(c, 1H), 7.20 (d, 1H), 7.14 (d, 1H), 4.09 (s, 3H, 0CH3 ),

4.01 (s, 3H, 0CH3), 2.6-1.7 (m, 8K, tetrahydronyran C-H); exact mass calcd. m/e for Cpg^gO^ 298.12049, obs. m/e

293.12116, diff. 2 ppm.

Anal. Calcd. for O^H^gO^: C, 72.43; H, 6.04.

Found: C, 72.26; H, 6.15.

Benzylideneacenarhthenone (191). Triphenylphosphine

(10.0 g, 38 mmole) and benzylbromide (6.53 g, 35 mmole) 130 v/ere stirred in dry benzene (50 ml) under nitrogen for

5 h. The white crystals of benzyltriphenylphosphonium bromide (i2 2» 16-53 g» 100^) v/ere filtered and v/ashed with dry benzene.

Tsuge, Tashiro and Shinkai’s method63 was adapted for the present synthesis.

Sodium methoxide (0.6 g, 11.1 mmole) was added to a stirred solution of benzyltriphenylphosphonium bromide

(4.76 g, 10.8 mmole) in absolute ethanol (50 ml) under nitrogen. The clear yellow mixture was stirred for 10 min and acenaphthenequinone (2.0 g, 10.9 mmole) was added. The mixture was stirred 30 min and then heated in a water bath for another 30 min. Water (100 ml) was then added to the mixture and heating was continued for another 3° min.

Upon cooling and filtration, there was isolated yellow crystals of benzyliaeneacenaphthenone (1§1 » 2.71 g, 96 .36, mp 107-110°(methanol) ; lit6.3 mp 120°).

n-l\Titrobenzylideneacenaphthenone(122) . o-Nitro- benzylideneacenaphthenone was prepared according to the precedure of Tsuge.

Sodium methoxide (0.6 g, 11.1 mmole) was added to a stirred solution of p-nitrobenzyltriphenylphosphonium bromide (5-25 g* 10.9 mmole) in absolute ethanol (50 ml) 131 under nitrogen. After 10 min the solution became pink and acenaphthenequinone (2.0 g, 10.9 mmole) was added. The mixture was refluxed under nitrogen for 2 h and quenched with water (50 ml). The yellow solid which precipitated after cooling was filtered and dried. Recrystallization from toluene afforded p-nitrobenzylideneacenaphthenone

(1§2, as yellow crystal (2.2 g, 67/-". mp 237-2390 ; lit.^ mp 239°); exact mass calcd. m/e for C^qH^N0^=301 .07333, obs. m/e=301.07464, diff. = 2.3 ppm.

Reaction of Benzylideneacenaphthenone v/ith n-Tosylhydrazine.

Benzylideneacenaphthenone (1.0 g, 3*9 mmole) and 0- tosylhydrazine (O.727 g» 3*9 mmole) were stirred 24 h in methanol (30 ml) containing concentrated hydrochloric acid

(3 drops). The yellow precipitate was filtered and recrystallized from toluene/acetonitrile to yield acenaphthenequinone bis(£-tosylhydrazone) (12, 0.59.g»

53.4/, mp 200°( dec.)); IR (KBr, cm"1) 3200 (I , w),

1300, 1170 (S02 , s); NKR (CDC1 y 'b ) 12.10 (s, 2H, KH),

5.22-7.36 (m, 14H), 2.47 (s, 3H, CH.,), 2.39 (s, 3H, CH3).

Anal. Calcd. for C26^22^4°4S2 : C ’ ^0.23; H, 4-.25;

Found: C, 60.31; H, 4.15;

Calcd. N, 10.31; S, 12.36.

Found: K , 10.72; S, 12.60. 132

Reaction of o-Nitrobenzylideneacenaohthenone with p-Tosylhydrazine. A mixture of p-nitrobenzylideneacenaphthenone (1.0 g, 3*3 mmole) and p-tosylhydrazine

(0.93 g» 5 mmole) in tetrahydrofuran (20 ml) was refluxed for 3-5 h. The mixture became a clear solution after heating for 3° min. Tetrahydrofuran was removed and benzene

(30 ml) was added to the residue to give pale yellow' crystals after stirring. Filtration and recrystallization from toluene/acetonitrile yielded acenaphthenequinone bis(o- tosylhydrazone (12, 1.23 g, 99/’» mp 200-201°( dec.)) as previously characterized.

Acenaphthenequinone Bis(o-tosylhydrazone) (12).

Acenaphthenequinone (2.0 g, 10.8 mmole) and n-tosylhydrazine

(4.5 g, 24.1 mmole) was refluxed in tetrahydrofuran (25 ml) with concentrated hydrochloric acid (5 drops) for 3 h.

The light yellow crystals which formed after cooling were filtered. The filtrate was dried and triturated with benzene to yield a second crop of product. Recrystallization from toluene/acetonitrile gave acenaphthenequinone bis(p-tosylhydrazone) (12, 5.63 g, 99/, mp 200°(dec.)) identical with that obtained from benzylideneacenaphthenone with 2 -tosylhydrazine. 133

Thermolysis of I.lono Sodium Salt of Acenaphthenequinone

£-Tosylhydrazone. Sodium hydride (60 mg, 50/, 1*2 mmole)

was washed with hexane, dried under nitrogen and added to a

stirred solution of acenaphthenequinone bis(p-tosylhydrazone)

(0.5 g, O.96 mmole) in tetrahydrofuran. After 20 min,

tetrahydrofuran was removed and the dry sodium salt was

suspended in chlorobenzene (30 ml) and refluxed for 1 h.

The mixture was poured into ice water and extracted with

chloroform. Evaporation of chloroform and trituration

with hexane yielded 2-(p-toluenesulfonyl)acenaphthenone

p-tosylhydrazone (128, 0.271 g, 57*3/> mp 199°(dec.)

(toluene/acetonitrile)); IR (Or, cm"'*') 3160 (NH, w) , 1350,

1300, 11?0, 1130 (S02 , s); NIIR (CDCl3+D;,"S0-d6, i ) 10.51

(s, 1H, I'lH), 8.1-7.36 (m, 6H, aromatic), ?.26 (s, 3H,

aromatic), 5*31 (s, 1H, benzylic), 2.10 (s, 6H , 2CH^);

exact mass calcd. m/e for £ 26^22^'2G^ 2 = ^9° * 10209 , obs. m/e = Eco.10302, diff.=1.3 ppm.

Anal. Calcd. for C26K22I:2°4S?: C * ^3 • 6 7 ; H, 4.49; N, 5 .71.

Found: C, 63.86; H, 4.22; K , 5-77.

Thermolysis of Dilithium Acenaphthenequinone Bis(n-tosyl- hydrazide) in Diglyme. n-Butyl lithium (2.14 ml, 2.16

!>i, 4.6 mmole) was added to a tetrahydrofuran (50 ml) solution of acenaphthenequinone bis(p-tosylhydrazone) (1.0 g, 1.9 mmole) 13^ and stirred for 20 min under nitrogen. Tetrahydrofuran was then removed under vacuum and the dry lithium salt was thermolyzed in diglyme by reflusing the mixture for 30 min.

The solid was filtered and the diglyme was removed under reduced pressure. Chromatography of the residue on silica gel (chloroform) led to isolation of 1,8-dicyanonaphthalene

(£2i» 3? mg, 10.?f, mp 223-230°(toluene/acetonitrile)), identical with the authentic sample prepared independently from 1,3-dibromonaphthalene.

1,3-Dicyanonarhthalene(201).-* — '« ■ n- , ■ , i , » ■ i i ■ ■ — "ii ii A * ^ Friedman and Shechter's 71 method for 1-cyanonaphthalene was adapted for the present synthesis of 1,3-dicyanonarhthalene.

A stirred mixture of 1,3-dibromonaphthalene^^ (3*0 c,

0.01 mole), cuorous cyanide (2.25 E» 0.025 mole) and dimethylformamide (25 ml) was refluxed for ^ h. The dark brown mixture was poured into ice water (600 ml) containing sodium cyanide (10 g). The mixture was well stirred until all of the gummy solid dissolved (more sodium cyanide v/as added until all of the solid dissolved) and then extracted with chloroform. The chloroform solution was washed several times with water, dried over sodium sulfate and evaporated. Chromatography (silica gel, chloroform) of the residue gave 1,8-dicyanonaphthalene (201, 0.82 g, 135 mp 232-233°(toluene/acetonitrile)) as white crystals; IR

(KBr, cm"1) 2240, 2220 (CSN, medium); NI.'R (CDCl^,^)

8.45-7-^0 (m, aromatic); exact mass calcd. m/e for Cq2^6^2 =

178.05309, obs. m/e=178.05355, diff.=2.3 ppm.

Anal. Calcd. for C12H6I\T2: C, 80.90; H, 3*37; N, 15-73-

Pounds C, 80.47; K, 3-^0; N,16.18.

(71) L. Friedman and H. Shechter, J . Org. Chem.. 26, 2522 (1961).

(72) L. F. Fieser and A. 1'. Seligman, J. Amer. Chem. Soc.. 61, 136 (1939).

Decomposition of Acenaphthenequinone Bis(p-tosylhydrazone) with Potassium Hydroxide in Ethylene Glycol.

Acenaphthenequinone bis(p-tosylhydrazone) (2.0 g, 3*86 mmole) and potassium hydroxide (1.0 g, 17.86 mmole) was refluxed in ethylene glycol (15 ml) for 1.5 h. The dark red solution was poured into ice water and extracted with chloroform. Ivaporation of chloroform and chromatography

(silica gel, chloroform) gave naphthalimide (20^, 0.21 g,

27.65, mp 293-295°(toluene/acetonitrile); lit.^ mp 300°); exact mass calcd. m/e for cq2H7N02 197*°^?67* obs. m/e 197-04806, diff. 2 ppm.

The aqueous layer on neutralization with hydrochloric acid and extraction with chloroform yielded 136

2 -(2 -toluenesulfonyl)acenaphthenone r-tosylhydrazone

(128, 0.16 g, 8.5,1, mp 199°(dec.)).

(73) G. Caronna, Gazz. Chim. ital., £2» (19^9)•

Basic Hydrolysis of 1,8-DicyanonaPhthalene. A mixture of

1 ,8-dicyanonaphthalene (0.3 g, 1.7 mmole) and potassium hydroxide (0.5 g, 3-9 mmole) in ethylene glycol (10 ml) was refluxed for 2 h. The clear yellow solution was poured into ice water and acidified with hydrochloric acid. Filtration and recrystallization from toluene/acetonitrile yielded

1 .3-naphthalimide (20^, 0.23 g, 34.3/, mp 297-293°; lit.^ mp 300°); IR (KBr, cm"1) 3130 (HH, v;), 1700, 1680 (0=0, s)j exact mass calcd. m/e for Cn 2Hr7N09= 197• 04767, obs. m/e =

197-04323, diff.=3 ppm.

Anhyjro-3-hydroxymercuri-l-na'ohthoic Acid.

Anhydro-S-hydroxymercuri-l-naphthoic acid was prepared 74 according to Leuk, Perkins and V.'hitmore' s method from

1 .3-naphthalic anhydride in 97/ yield.

(7*) G. J. Leuck, R. ?. --erkins and F. 0. V.’hitmore, J. Amer. Chem. Soc., 51, 1331 (I929). 137

8-3romo-l-nat>hthoic Acid. Rule, Purse 11 and Brown's

method?-^ was used for this preparation.

Anhydro-3-hydroxymercuri-l-naphthoic acid (93 g, 0.25 mole) was suspended in a solution of glacial acetic acid

(330 ml) and water (60 ml) in a 2 1 3-necked round bottom

flask, fitted with a condenser, an addition funnel and a mechanical stirrer. The mixture was vigorously stirred and cooled to 0°. A solution of sodium bromide (170.0 g,

1.66 mole) in water (310 ml) and bromine (41.7 g, 14.3 ml,

0.26 mole) was placed in the addition funnel and added slowly to the contents of the flask keeping the temperature at 0-5°. The resulting slurry was then slowly heated to

100° and poured into ice water. The tan crystals were purified by dissolution in sodium hydroxide and reprecipitation with hydrochloric acid. Recrystallization from toluene gave 3-bromo-l-naphthoic acid (53.1 g, 355) white crystals, mp 163-170°; lit.^ mp 177-173°; exact mass calcd. m/e for C ^ K ^ O ^ B r ^ = 249.96799, obs. m/e =

249.96332, diff.=1.2 ppm.

(75) H. G. Rule, V/. rursell and R. R. H. Brown, J. Chem. Soc., 163 (1934). ' 138

8-Bromo-l-na'ohthoyl Chloride. Kang's procedure?^ was adapted for the synthesis of 8-bromo-l-naphthoyl chloride.

3-Bromo-l-nanhthoic acid (h-7.0 g, 0.137 mole) was added to freshly distilled thionyl chloride (115 ml) with stirring. The mixture was refluxed until a clear solution was obtained(3 h). Lxcess thionyl chloride was removed by distillation and the residue was recrystallized from hexane after the insoluble impurities had been filtered. 3-Uromo-

1-naphthoyl chloride (^3*1 £. 35.//) v.'as obtained as white crystals, mp 66-63°; lit.^ mp 67-63°; exact mass calcd. m/e for C ^ H ^ G U l ^ B r 7'^ 267.92910, obs. m/e=267.9297/, diff.=2.2 n'xn.

(?6 ) u. 0. Kang, Ph. D. Dissertation, hichigan State University (1972).

3-Bromo-l-nanhthoic Hydrazide. 3-Promo-1- narhthoic hydraside was prepared according to the method of Dokunikhin and Bustritskii.

3-bromo-l-naphthoyl chloride (5.0 g, 13.6 mmloe) in toluene (30 ml) was dropped into a stirred mixture of hydrazine hydrate (5.0 g, 99-100./, 0.1 mole) and methanol

(10 ml) at 0-5°. The mixture was stirred for 30 min and methanol was distilled off. The crystals which separated 139

after cooling were filtered, washed with toluene and dried.

Treatment with water, filtration, drying and recrystalliza tion from ethanol resulted in 8-bromo-l-naphthoic hydrazide

( ^-5 g» 93/3) as white crystal, mp 172-173°; lit.^ mp 173-175°; exact mass calcd. m/e for C-^H^NpOBr^=

263*9893?» obs. m/e=263-99053» diff.=2.3 ppm.

1-Aminobenz lcdHndol-2( 1H) -one ( 203). Dokunikhin and 7 Bystritskii's procedure ' was used for the preparation of

204.

8-3romo-l-naphthoyl hydrazide (16.12 g, 61 mmole) and magnesium oxide (2.3 g, 60 mmole) were refluxed 2 h in 953 ethanol (160 ml) in the presence of a small amount of copper powder and cupric acetate. The mixture was filtered hot; the crystals which separated on cooling were then filtered. Recrystallization from toluene gave 1-aminobenz- fcd]indol-2(1H)-one £03, 9.2 g, 82/), yellow needles, mp I69-1700 ; lit£^ mp 173-173.5°; exact mass calcd. m/e for Cj-^Hg^O = 184.06366, obs. m/e=l83.063l3, diff.- 2 .5 ppm.

Reaction of 1-Aminobenz [cd]indol-2(1H)-one with o-Chloro- benzaldehyde. A mixture of 1-aminobenz [cdjindol-2(1H)-

one (0.3 g> 1.63 mmole) and o-chlorobenzaldehyde (1 ml) was refluxed in ethanol (10 ml) containing 2 drops of 140

concentrated hydrochloric acid until the solution became clear. The solid which separated after cooling was filtered and recrystallized from petroleum ether/toluene (1:1) to yield l-(o-chlorobenzylideneamino)benz(cdjindol-2( 1H)-one 0.43 g, 36%), yellow crystals, mp 155-157°; IR

(KBr, cm-1) 1715 (C-0, s); exact mass calcd. m/e for

Cl8HllN2OCl3^ 3°6.°5598, obs. m/e-306.05661, diff.=2 ppm.

Anal. Calcd. for C^H-j^N^Od: Cl, 11.53; N, 9.14.

Found: Cl, 11.75; N, 9.12.

Reaction of 1-Aminobenz fed] indol-2 (1H) -one with jd-

Toluenesulfonyl Chloride. p-Toluenesulfonyl chloride

(1.14 g, 5*98 mmole) in tetrahydrofuran (10 ml) was added dropwise to 1-aminobenz [cd]indol-2(1H)-one (1.0 g, 5.43 mmole) in tetrahydrofuran (35 ml) and pyridine (5 ml) at

0-5°. The mixture was stirred at 0-5° for 1 h, concentrated to 20 ml and poured into ice water. The yellow precipitate was filtered and recrystallized from toluene to afford

N-(p-toluenesulfonyl)-1-aminobenz [cd] indol-2(1H)-one ( 202,

1.02 g, 55*5%) as fuzzy yellow needles, mp 213-214°; IR

(KBr, cm"1) 3210 (NH, m), 1725 (C=0, s), 1350, 1170 (S0£ , s); exact mass calcd. m/e for C^gH-^N^OgS=338.07251, obs. m/e =

338.07323, diff.-2.1 ppm. 141

Anal. Calcd. for C^gH^^O^S: C, 63.9 0 ; H, 4.14;-

Found: C, 63.25; H, 4.13;

Calcd: N, 8.28; S, 9-47.

Found: N, 8.05; S, 8 .99 .

Photolysis of 1-Aminobenzfed]indol-2(1H)-one . A benzene solution of 1-aminobenz [cd]indol-2(1H)-one (0.5 g»

2.71 mmole) was photolyzed using a Hanovia 450 W medium pressure mercury lamp for 3 h. Upon removal of solvent,

1-aminobenz[cd]indol-2(1H)-one was recovered quantitatively.

Oxidation of 1-Aminobenzfed] indol-2( lH)-one with Lead

Tetraacetate Buffered with Tetramethylguanidine. Lead tetraacetate (3*0 g, 6.76 mmole) was added to a stirred solution of 1-aminobenz [cd]indol-2(1H)-one (1.0 g, 5*43 mmole) in tetramethylguanidine (10 ml) and methylene chloride

(50 ml) at -78° under nitrogen. The mixture was stirred at -78° for 1 h, slowly raised to room temperature and then stirred for 3 h. The mixture was washed with water, and the methylene chloride layer was dried over calcium chloride and evaporated. Chromatography on silica gel

(chloroform) gave yellow crystals. Recrystallization from toluene yielded naphthostyril (207, 45 mg, 5%» mp

176-178°; lit.^? mp 179-180°) as yellow prism; exact mass 14-2 calcd. m/e for Cn H?N0 = l6 9 .05276, obs. m/e=169.05320, diff.=2 .4 ppm.

Oxidation of 1-Aminobenz fcdlindol?2nH)-one with Lead .

Tetraacetate Buffered with Sodium Bicarbonate. Lead tetraacetate (2.4-1 g, 5*43 mmole) was added to a stirred mixture of 1-aminobenz [cd] indol-2(1H)-one (1.0 g, 5*43 mmole) and sodium bicarbonate (1 g, 11.9 mmole) in tetrahydrofuran (75 ml) at -78° and stirred for 2 h under nitrogen. The mixture was slowly raised to room temperature and stirred for 2 h. After filtering the solid, and vacuum removal of the tetrahydrofuran, the residue was dissolved in chloroform and washed with water.

Evaporation of chloroform and chromatography on silica gel (chloroform) gave yellow crystal (0.11 g, 12$).

Recrystallization from toluene/acetonitrile afforded a compound with formula ^22^12^2^4-’ 262-263°; IR (KBr, cm-^) 1740 (C 0, s); NMR (CDC1y $ ) 8.43 (doublet of doublet,

1H), 8.29-8.13 (triplet, 2H), 7.89-7-68 (m, 3H); mass spectrum 364-, 336.

Anal. Calcd. for ^22^12^2^4-! 71-74; H, 3-26; N, 7-61.

Found: C, 71.45; H, 3-23; N, 7 .65.

71.24 3-31 7.34. PART II

5-BROMO-4-QUINOLYLDIAZOMETHANE AND

4-QUIN0LYLDIAZ0METHANE:

SYNTHESIS, THERMOLYSIS AND PHOTOCHEMISTRY

143 STATEMENT OF PROBLEM

Recently, 1-bromo-lH-cyclobuta [de] naphthalene' (^) has

been synthesized1 by photolysis of sodium 8-bromo-l-

naphthaldehyde p-tosylhydrazonate (1) or 8-bromo-l-naphthyl-

diazomethane (2) in ether at 25° (Eq 1). Bromide ^ can

Br CH NNTos

1 2 S be handled without difficulty and undergoes typical nucleo- la 2 philic substitutions '“ with a variety of nucleophiles a without cleavage of its cyclobutyl ring. X-Ray study shows

(1) (a) R. J. Bailey, Ph.D. Dissertation, The Ohio State University, 197^5 (b) R. J. Bailey and H. Shechter, J. Amer. Chem. Soc., §6, 8116 (197*0*

(2) P. Card, Ph.D. Dissertation, The Ohio State University, 1976.

(3) M* A. Gessner, Master's thesis, The Ohio State University, 1977*

that bromide 3 is planar. The bond distances (A0) and 145 angles (°) of 2 are presented in Figure 1. The success in

1.952

83?

89' 89

119.' 114.' .368

.382 124' 112 * 120' [}0? 121?

Figure 1. Diagram of 1-Bromo-lH-cyclobuta[del -

naphthalene (^)* achieving the synthesis of such a manageable, though strained molecule leads to the present study. The present research is thus concerned with the possible synthesis of a quinoline (6) bridged in its 4,5-positions by a 1*4-6

bromomethylene group by photolysis of 5-bromo-*4--quinolyl

diazomethane (k) and/or sodium 5-bromo-*4-quinolinecarbox

aldehyde p-tosylhydrazonate (£, Ea 2). The principal

objectives of this effort are: (1) to prepare 5-bromo-4- quinolyldiazomethane (4) and *4—quinolyldiazomethane (g); (2) to explore the thermal and photochemical reactions of k and

2 and their carbenes 8 and g; (3) to study the possibility

Br CHH, Br : CH

of generating carbene g via ^-elimination; and (*4-) to

effect photochemical synthesis of 6 from 4 or % and to

compare its chemical behavior with that of naphthalene

analog g. HISTORICAL

The intramolecular participation of divalent carbon

with heteroatoms containing non-bonded electrons has been

a major interest to organic chemists. A major recent

effort of this laboratory concerned with such effects has

involved study of the thermal and photochemical decomposi- la tions of 8-substituted 1-naphthyldiazomethanes (10)

The initial design of this research was based on the possible

participation of substituents in the 8-(peri-) position

with 1-naphthyl carbenic centers as in equation 3« In

(3)

10 11 12 theory a carbene such as 11 could stabilize itself by formation of an ylide of type 12. Ylides 12 if sufficiently stable and delocalized would be novel heterocyclo systems.

Experimentally, thermolysis and photolysis of 8- substituted 1-naphthyldiazomethane systems have turned out quite surprisingly. For example, thermolysis of sodium

14? 148

8-bromo-l-naphthaldehyde ;p-tosylhydrazonate (1) in refluxing

chlorobenzene gives 9-bromo-3H-benz [ejindazole (1^, Eq 4) ®Na Br CH=NNTos Br

(4)

I 22

and 5 »8-dichloro-l-naphthyldiazomethane (14) yields 6,9-

dichloro-3H-benz [ejindazole (1£, Eq 5) along with trans-bis-

(5.8-dichloro-l-naphthyl)ethylene. Similarly, 9-iodo-3H-

HN Cl NH A (5)

Cl Cl

14 22

benz[e]indazole (17) is formed from 8-iodo-l-naphthyldiazo-

methane (16) as generated in situ by heating the sodium salt

of S-iodo-l-naphthaldehyde p-tosylhydrazone (Eq 6). Thermal -N \ H A (6)

i§ i2 formation of the 8-halo-3H-benz [e]indazoles (20) is rationalized on the basis of sterically assisted electrophilic attack at C-2 by the terminal nitrogen of the diazo group in 18 to give intermidiate IQ followed by tautomerization (Eq 7). The steric effects of halogens in the 8-

H (7)

18 20 position leading to cyclization of 8-halo-1• 'phthyldiazo- methanes (18) are quite profound, since 1-na yldiazo- methane (21) does not undergo a similar conversion (Eq 8).

The behaviors of 21 and 1-naphthvlcarbene are typical in that thermolysis of 21 in benzene gives 7-(l-naphthyl)cycloheptatriene (22), trans-bis-l-naphthylethylene (2^3) and

1-naphthalazine (24, Eq 8). It is thus presumed that a peri 150

halo substituent in lg forces the diazo group out of co

planarity with the naphthalene system and facilitates

electrophilic attack from above or below the aromatic ring

at C-2 by the terminal nitrogen of the diazo group.

The photochemical behavior of 8-bromo-l-naphthyldiazomethane (2) and sodium 8-bromo-l-naphthaldehyde p-tosylhydrazonate (1) is completely different however from their thermal chemistry. Carbene precursors 1 and 2 undergo photolytic loss of nitrogen to yield l-bromo-lH-c,yclobuta[de] - naphthalene Q ) as a major product along with trans-bis-(8- bromo-l-naphthyl)ethylene (2^, Eq ®N a CH=NNTos e

Br Br

(1) A 1 4- Dr CHN

Formation of 2 c&n be rationalized on the basis of photochemically-induced loss of nitrogen from 2 to form 8-bromo-

1-naphthylmethylene (26) which may react in two ways: (1) interaction with the peri bromine atom to give bromonium 151

ylide 2£ which collapses to 2 and (2) electrophilic attack

S 7

The remarkable utility of bromide 2 Is demonstrated by its reactions with a variety of nucleophiles without rupture 2 of the cyclobutane ring. For example, 2 reacts with lithium aluminum hydride or sodium bis(2-methoxyethoxy)- aluminum hydride in ether to afford lH-cyclobutafde]naph- '“V thalene (2g, Eq 10), a new hydrocarbon. The physical

H H

LiAlHi d o )

22 properties and chemical behavior of bridged hydrocarbon 2g 152

2 are discussed in detail in the Ph.D. dissertations of Card . 4 and Fnedli.

(4) F. Friedli, Ph.D. Dissertation, The Ohio State University, 19?8.

Since a purpose of this research is to synthesize bridged quinoline 6 (Eq 2) by a method similar to that for preparation of 2 it is important to examine and compare the structures of naphthalene and quinoline. The X-ray dimensions of naphthalene (22) anc^ quinoline^ (21) reveal that the bond

5 b 6

21 angles C(5)-C(10)-C(4) and C(8)-C(9)-C(1) and the bond distances C(5)-C(10), C(4)-C(10), G(8)-C(9) and C(9)-C(l) of naphthalene and quinoline are very similar(Table 1). Thus participation of bromine with the carbenic center in 26 might occur in 5-bromo-^-quinolylmethylene (8) and lead to

(5) P. S. Shetty and Q. Fernando, J. Amer. Chem. Soc., 92, 396^ (1970). 153

TABLE 1

BOND ANGLES(0) AND BOND DISTANCES(A°) OF £0 AND ^l.

# naphthalene quinoline

C( 1)-C(2) 1.361 1.33

C(2)-C(3) 1.^32 1.44

C(3)-C(4) 1.361 1.38

C( M-) -C( 10) 1.425 1-39

c (10)-C(9 ) 1.410 1.43

C(9)-C(l) 1.^35 1.38

c(5)-c(10) 1.425 1.45

C(9)-C(8) 1.435 1.39

C( 5) “C( 10) -C( A) 121.5 123.2

C(8)-C(9)-C(l) 121.5 119.8

* Dimensions of quinoline in Ni[SpFEtg] C^H^N complex.^

6 as in equation 1.1. Further, due to the electron-withdraw ing effect of the nitrogen the carbene center of 8 would be H Br

(11)

N N

§ 6 highly electron demanding. Thus formation of ylide ^2 and 154

its subsequent collapse to 6 might be favored. Therefore, photolysis of 4 to produce 6 would be more promising and is a goal of the present study. An alternative mechanism via an intermediate similar to 28 may also be involved in formation of 6.

Since quinolyldiazomethanes were unknown until this research was carried out, the chemistry of pyridyldiazomethanes is reviewed. 2-Pyridyldiazomethane (^2) decomposes with rearrangement upon photolysis at 8°K to give 1-aza-

1,2,4,6-cycloheptatriene (^4, The presence of

22 2it

(6) 0. Chaoman and J. P. LeRoux, J. Amer. Chem. Soc., 100, 282 (1978).'

strained ketenimine 2^ is confirmed by the intense absorption at I895 c m ”'*' and also by generating the intermediate in an argon matrix (80/20, Ar/O^) which gives an isocyanate,

HC0-CH=CH-CH=CH-N=C=0, (^NC0 22?0 cm"1) on further irradiation. Ketenimine ^4 is also obtained upon photo lysis of phenyl azide (35 , Eq 14) ; in the presence of secondary amines lH-azepines (22) anc* then 2H-azepines form

(28, Eq 13). 155

2Z 23

Carbene-nitrene rearrangements have also been n observed/ in the pyrolyses of 3- and 4-pyridyldiazomethanes

(22S, b) at 90°. Carbenes 40a and 40b as generated from

29a and 22£ convert to 2-pyridylmethylene (41) which rearranges to phenylnitrene and eventually results in 1-cyanocyclopentadiene (42, Scheme 1).

SCHEIE 1

32b 40b 156

(7) W. D. Crow, M. N Paddon~Row and D. S. Sutherland, Tetrahedron Lett., 2239 (1972); W. D. Crow, A. R. Lea and M. N. Raddon-Row, ibid., 2235 (1972). RESULTS AND DISCUSSION

The molecules needed for this research are 5-t>romo-

4-quinolyldiazomethane (4) and 4-quinolyldiazomethane (£)•

Since 4 and 2 are Ughf sensitive and gradually change color at room temperature, they were usually prepared in situ from their sodium quinolinecarboxaldehyde p-tosylhydrazonate precursors. Synthesis of 5-bromo-4-quinolinecarboxaldehyde

(4g) and 4-quinolinecarboxaldehyde (£2) are described as follows:

Syntheses of 4g and £2. Direct bromination of

4-methylquinoline (^1) gives a mixture of all possible monobrominated isomers along with the products of di- and 3 tn-brommation. An alternative route was therefore chosen for synthesis of 5-bromo-4-methylquinoline (48) as a precursor to 4g.

(8) S. E. Krahler and A. Burger, J. Amer. Chem. Soc., 63, 2367 (1941).

2-Hydroxy-4-methylquinoline (4^) was first converted to 2-chloro-4-methylquinoline (44) with phosphorous oxychloride in almost quantitative yield. Nitration of 44

157 158 with fuming nitric acid at 0° resulted in a mixture of 2- chloro-4-methyl-5-nitroquinoline 53%) and 2-chloro-4- methyl-6-nitroquinoline Eq 1*0. Separation of 4^

P0C1

N -^OH

(i^) from *l5a was readily accomplished by fractional recrystal lization of a saturated hot ethanol solution of the mixture at 55°• 2-Chloro-*i--methyl-6-nitroquinoline (^5g crystallizes out at 55°; cooling the filtrate at 0° then gives

Reduction of the nitro group and removal of chlorine from was carried out either simultaneously or stepwise as in Scheme 2. In a two-step operation (path a), was hydrogenated over Raney nickel to 5-amino-2-chloro-*i-methylquinoline (^6). For large scale synthesis, k6 was easily obtained by reducing with iron powder in concentrated hydrochloric acid. Removal of chlorine from k6 was then achieved by hydrogenation with Raney nickel and one equivalent of potassium hydroxide to form 5-amino-*J-methyl - quinoline (^?). The second route involved simultaneous reductions of the nitro group and chlorine in k5 by rv hydrazine hydrate catalyzed by 10% calladium on carbon to 159

SCHEME 2 (b) NH2NH2*H20"

10# Pd/( n!/

(a) H? , Ra-Ni ■Ni 1) HNO _6 5- or Pe/HCl KOH 2) CuBr

Br CH^ Br CHO Br CH=NNHTos

SeO, C^HySOoNHNlL

48 42

produce 4£. Hydrogen evolution occurred when the hydrazine

hydrate was added to a suspension of 4£ and 10;' palladium

on carbon in ethanol. The excess hydrazine hydrate served

to neutralize the hydrochloric acid liberated during the

reaction. This latter process is excellent and especially

convenient for large scale preparations of 4£ from 4£.

The yields are generally greater than 80>J. Sandmeyer bromination of 4? led to 5-bromo-4-methylquinoline (48) which was oxidized with selenium dioxide to 5-bromo-4- quinolinecarboxaldehyde (4g) of proper analysis and spectra.

Condensation of 4g with p-tosylhydrasine in the dark resulted in 5-bromo-4-quinolinecarboxaldehyde p>-tosylhydrazone (£0, s°heme 2). Tosylhydrazone £0 is unstable 160

and sensitive to light. Thus it was prepared only prior to

the decomposition reactions and used directly without

further purification.

4-Quinolinecarboxaldehyde (%2, Eq 15) was prepared^ by oxidation of 4-methylquinoline (£1) with selenium dioxide.

The yields of £2 depend highly on the purity and freshness

^ Cr,HoS0oNHNH

Si1 32 £2 of the selenium dioxide used. 4-Quinolinecarboxaldehyde p-tosylhydrazone (5(3) was obtained by reaction of £2 with p-tosylhydrazine (Eq 15)• Tosylhydrazone 52 as rather unstable and was identified by IR techniques.

(9) K. Kaplan, J. Amer. Chem. Soc., 6 5 , 2654 (1941).

Syntheses and Decompositions of 5-Bromo-4-quinolyI- diazomethane (4) and 4-Quinolyldiazomethane (£).

5-Bromo-4-quinolyldiazomethane (4) was preparable as an unstable orange crystalline solid by decomposition of 5 in refluxing benzene for appropriate periods (Eq 16). A yield 161

Na CH-N,

(16) PhH

of (t of 60% was obtained but was very difficult to reproduce.

Quinolyldiazomethane k melts at 146° but is quite light

sensitive, even at room temperature on exposure to laboratory

luminescence. Identification of k is based on its strong

diazo (=^2 ) absorption at 2080 c m -'*', proper mass analysis

and H1-NIv'R.

Photolysis of k in benzene led to complex intractable

products along with trace amounts of 5-bromo-^-quinoline-

carboxaldehyde azine (^, Eq 17). The NMR of the crude

CH=N-N=CH

hv - > (17) PhH

& product shov:s no evidence for hydrogen on bridged carbon as expected for 6 or its bridged derivatives. Treatment of the crude product with silver nitrate revealed the absence of bromide ion, thus indicating that bromine had not transferred from its naphthalene position to form 162

bromide £5 and/or its derivatives. Further, thermolysis of

k in refluxing benzene for long periods gave only intractables,

Ylide 12, if formed in these experiments, is not stable

enough to be isolated and characterized. Other reasonable

reaction products such as pyrazole and pyrazine derivatives

£6 and ££ are not found.

N H Br-N "

Br H

Since it was difficult to study the direct decomposition of k in detail because of the difficulties in reproducibility of the synthesis of the diazo compound, investigation was then shifted to photolysis and thermolysis of sodium

5-bromo-^-quinolinecarboxaldehyde £-tosylhydrazonate (£) in various environments. As summarized previously, synthesis of 2 occurs essentially as efficiently upon photolysis of

1 as of 2. In suspension in benzene, £ was found to photolyze at room temperature (3 h) to 5-bromo-^-quinolinecarboxaldehyde azine (£4, 16$), a mixture (19$) of 163

5-bromo-4-cyanoquinoline (£8) and 5-bromo-4-quinolinecarboxaldehyde (42^* anc^ intractables (Eq 18). Azine £4-

Br CN Br CHO

i2 is proved by its elemental analysis and spectral properties.

A reasonable mechanism for £4 is condensation of 4 with itself to form ^2 which further loses nitrogen to give £4 as in Scheme 3- Identification of £8 and 4g is based on

SCHEME 3

52 the IR, NTilR and mass spectra of the mixture. Nitrile £8 may be possibly derived from decomposition of azine £4 under the photolysis conditions. Aldehyde 4g might arise from oxygenation of 4 or/and related intermediates.

The thermal behavior of 5 was then investigated. In chlorobenzene at 130°, £ decomposed to azine £4 (9%), a 164 mixture (13/») of 5-6romo-4-methylquinoline ((+8) and 5-t>romo-

4-cyanoquinoline (£3), and complex unidentifiables (Eq 19).

Br CH.

A (19) & + 59 + CgH^Cl

Thermolysis and photolysis of £ are grossly similar and there is no evidence for carbenic bridging to 6 and for intramolecular dipolar cyclization to £6.

Since there was yet no real demonstration of generation of carbene 8 upon heating or irradiation of £ and 4, study was initiated of possible metal-ion catalyzed decomposition of £ under various conditions. Thermolysis of £ in benzene

(30°) in the presence of cuprous bromide resulted in effective formation of l,2-bis(5-bromo-4-quinolyl)ethylene

(61, 60['/o) possibly via 60 as in equation 20. Efforts to

.0 Cu \ 2 Br CH -— CH Br r (j-H = yH

, CuBr -N PhH -Cu1

60 generate and trap carbene 3 by refluxing £ with cuprous 165

bromide in cyclohexene failed; instead, only azine was

obtained.The difference in the behavior of 5 in benzene

(10) C.-T. Ho, R. T. Conlin and P. P. Gaspar, J. Amer. Chem. Soc., 2§* 3109 (197^)* Tetraphenylethylene is reported to catalyze decomposition of diphenyldiazomethane and enhance the yield of benzophenone azine.

and in cyclohexene is not clear as yet. Further, 5 decomDosed

in benzene at 80° in the presence of silver nitrate (0.5 equivalent) with formation of 5-bromo-5--quinolinecarboxaldehyde (^+2» 21>o) and 5-bromo-^-quinolinecarboxaldehyde azine (£*+, Z0%, Eq 21). Formation of ^2 may come from

A , AgHO (21) FhH reaction of nitrate anion with the silver ion-complexed diazo compound 62 followed bv loss of silver nitrite from * I V « V * 6^ as in equation 22 or by related oxidation processes.

Br CH-N AgNO. 0N0 - AgNOAgNOp > ^

Since 5-brcmo-4-quinolyldiazomethane (£) is poorly behaved as a source of carbene 8 and its metal-ion chemistry 166

is so diverse, it was deemed essential to investigate the

ability of ^ to undergo typical 1,3-dipolar addition

reactions with activated double and triple-bonded systems.

Indeed k as derived in situ at 83° from £ containing silver-

nitrate did cycloadd to acrylonitrile to produce 5~(5'~

bromo-4'-quinolyl)-3-cyano-2-pyrazoline (66, kl%) presumably

via tautomerization of the initially formed 1-pyrazoline

6k (Eq 23). The structure of 6j5 is assigned on the basis

H CN

c h 2= chcn (23) A , AgNO 3

6k of its elemental analysis and spectral properties and the assumption that the hydrogen alpha to the cyano group in 6k

is the most acidic and is involved in the rearrangement.

The later argument is similarly supported by the reaction of phenyldiazomethane (66) with dimethyl maleate giving 6£

(Eq 2k)11 rather than the alternate conjugated product 68.

(11) W. K. Jones, J. Amer. Chem. Soc., 81, 37?6, 5153 (1959)- 167

co2ch3 H C09CHq H - J ^ C02CH3 2 3 I— ^ C02CH3 Ph-CHN2 t Ph \\ Ph-4N/ H (24) ch3o2c h 5H' : H

It is of further note that decomposition of £ in acrylonitrile

in the presence of cuprous bromide did not give any cyclo-

addition product(s).

The behavior of £ with triple bonds is typical in that

£ reacted with phenylacetylene at 80° to yield 3~(5 *-bromo-

4'-quinolyl)-5~phenyl(lH)pyrazole (6g f 20#, Eq 25) upon

hydrogen migration. Elemental analysis and spectral

22 properties establish 6g. The regiochemistry of 6g is presumably as shown on the basis of the NftiR singlet proton at 6.94 ppm. An unusual coproduct of reaction of £ with phenylacetylene is 5-bromo-4-quinolinemethanol (£0 , 23#).

Assignment of £0 based on its spectral data, combustion 168 analysis and independent synthesis from 5-bromo-^-quinolinecarboxaldehyde by reduction with lithium aluminum hydride.

Formation of 72 may rationalized in that diazo compound

U reacts with jo-tosylsulfinate anion with nitrogen extrusion to give £1 which is protonated and subsequently hydrolyzed to £0 during work-up (Eq 26). © Na 0 Br ©CH-OSC^H^ © © © c?h ?s o 2 Na H > 22 (26) - N 2 h 2°

The present study has thus revealed that 5-bromo-4- quinolyldiazomethane (4), although functioning as a typical

1,3-dipolar reagent with acrylonitrile and with phenylacetylene, resists conversion to its carbene 8 and bridging to bromide 6. The principal photolytic and thermal reactions of k lead to formation of azine and products thereof.

The reasons for the resistance of k to give typical carbenic reaction are unclear. However from the overall general behavior of 4 (or £) it is apparent that the 5-bromo-4- quinolyl moiety in £ and presumably in 4 is functioning as a highly electron attracting unit.

In an attempt to define the "behavior of a ^--quinolyldiazo compound and its subsequent carbene more definitively, 169 an investigation of the generation of 4-quinolyldiazomethane (£) was initiated. Indeed thermal decomposition of the sodium salt (22) of ^f-quinolinecarboxaldehyde £- tosylhydrazone in toluene at 110° did yield 9--quinolyldiazomethane (£» 36$); an accompany product is also 4-quinolinecarboxaldehyde azine (£2* Eq 27) as possibly derived from dimerization of 2 and loss of nitrogen. Diazo compound 8 does behave as a 1,3-dipole since thermolysis of

']?- in phenylacetylene resulted in 5-phenyl-3-(^-quinolyl)-

(lH)pyrazole (2^» 3^$. Eq 28). Pyrazole 2^; is assigned

A (2 8 ) 22 + PhC =CH

from its elemental analysis, its spectral data and in particular, its NMR spectrum which exhibits a singlet at

7.01 ppm for a single proton. The down field shift for the l?o

^-proton of pyrazole 2*£ is attributed to the deshielding

of the phenyl and quinoline moieties.

In order to study possible generation of 4-qainolyl- methylene (o) and its insertion into aromatic system, 22 was heated in toluene for long periods. No product derived from insertion of 2 into the aromatic hydrocarbon was IP obtained. ~ Further, thermolysis of £2 in the presence of

la (12) Thermolysis of 1-naphthyldiazomethane (21) in benzene results in insertion of 1-naphthylmethylene into solvent to give ring expansion product 22 as in equation S.

silver nitrate at 110 in toluene and in diglyme yielded azine 22 (19 ?° and 23‘/0 respectively) and amorphous materials

There were no products of simple insertion of carbene o into toluene or diglyme detectable. Photolysis of 22 benzene and in acetonitrile resulted in 9--cyanoquinoline (££, 16% and 9-0 and intractables (Eq 2 9 ). Similarly, decomposition

hu 11 (29) PhH

of 22 benzonitrile containing cupric sulfate

yielded 22 (8*0 in low yield. Formation of nitrile 22

presumably arises from thermolysis and photolysis of azine 171

££. The important point again is that these decomposition

reactions did not lead to formation and insertion of carbene

2 into the solvent environments.

Since generation and trapping of 5-bromo-4-auinolyl-

methylene (8) and 4-quinolylmethylene (g) from their

corresponding diazomethanes (4 and £) or their ]>-tosyl-

hydrazonate precursors (£ and £2) were not satisfactorily

controllable, and alternative route to 4-quinolylmethylene

by a base-catalyzed ^-elimination method became of interest.

Indeed the strong hindered base, lithium 2,2,6,6-tetramethyl-

piperidide (LiTMP), has been used successfully for generat- 18 ing phenylcarbenes trimethylsilylcarbenes and tnmethyl-

stannlycarbenes 14 from benzyl chlorides, trimethylsilyl- methyl chloride, and trimethylstannylmethyl chloride, respectively. A study was thus initiated of possible

(13) R. A. Olofson and C. M. Dougherty, J. Amer. Chem. Soc., 25, 531, 532 (1973).

(14) R. A. Olofson, D. H. Hoskin and k. D. Lotts, Tetrahedron Lett., 1677 (1973).

generation of carbene 2 by ^-elimination of 4-chloromethyl- auincline (£6) as in equation 3 0 .

©CH-C1 : CH

ci° --- HTfoF

2 172

Synthesis-^ of 26. a stable solid if kept cold (5°). was effected from thionyl chloride and 4-quinolinemethanol

(28)^ as prepared by reduction of 4-quinolinecarboxaldehyde

(£2) with lithium aluminum hydride (Eq 31)* Addition of lithium 2 ,2 ,6 ,6 -tetramethylpiperidide to £6 in toluene at

(15) K. Carelli, IV'. Cardellini and F. Liberatore, Ann. Chim. , 50, 6 9 S (i9 6 0 ) (Rome); C. E. Kaslow and J. M. Schlatter, JT Amer. Chem. Soc., 22* 1054 (1955)*

(16) C. E. Kaslow and W. R. Clark, J. Org. Chem., 18, 55 (1053); B. R. Brown, D. L. Hammick and E. H. Thewlis7 J. Chem. Soc,, 1145 (1951).

CHO CHo0H H2C1 LiAlH; ^ ] S0C1, (31) so > 'N

2§

25° resulted in rapid formation of 1 ,2 -bis(4-quinolyl)ethylene

(2 2 * 845'.) and 2 ,2 ,6 ,6 -tetramethylpiperidine hydrochloride

(80, 10$, Eq 32). Inverse addition of JG to lithium 2,2,6,6-

LiTKI + (32) 26 > ''N H *HC1 22 80 173 tetramethylpiperidide or similar addition of lithium 2.,2,6,6- tetramethvlpiperidide to 76 at temperatures ranging from

-78° to 25° in various solvents gave ££ and complex uniden tified mixtures. There was no evidence for carbenic insertion of g into the solvents. Further attempts to trap carbene

0 or a carbenoid species derived from 22 and lithium 2,2,6,6- tetramethylpiperidide with ethyl vinyl ether, cyclopentene or cyclooctene at various temperatures (25°-1^5°) and different conditions led only to mixtures of £2 and intractables. The behavior of A--chloromethylquinoline (£6) with lithium 2,2,6,6-tetramethylpiperidide is not that expected for carbene 2* Quenching of a mixture of £6 and lithium

2,2,6,6-tetramethylpiperidide after a short reaction period

(5 min) at -70° by addition of deuterium oxide yielded o(- deutero-4-chloromethylquinoline (81, lk%) along with recovery of £6 (Eq 33) and thus established generation of

D H-Cl

£6 (33) 2) D20

81 carbanion 77. It therefore appears likely that formation of ethylene 72 from 76 and lithium 2,2,6,6-tetramethyl piperidide involves a sequence such as in Scheme 4. 1?4

SCHEME 4

LiTMP ---- 22 +§£ LiTMP 11

Resistance of 77 to loss of chloride ion to give carbene §

presumably is related to the marked electron-withdrawing

capacity of the 4-quinolyl moiety. The behavior of £6 toward lithium 2,2,6,6-tetramethylpiperidide is similar to that of p-cyanobenzyl chloride (82) and hydroxide ion from which p,p'-dicyanostilbene (8£) is obtained. Kinetic study1”'’ has demonstrated that is formed via E-2 elimination of 84 as presumably derived from Sn2 displacement on 82 by anion 8£

c h 2ci CH CH 0 OK (34)

I CN CN CN

13 as in equation Analogously, reactions of p-nitro-

benzylsulfonium salts (86) with hydroxide ion to give

p,p*-dinitrostilbene (8£) have failed to indicate involve

ment of p-nitrophenylcarbene (88) since attempts to trap 175

OH + r 2s (35)

NO, NO NO2

86 88

88 have been unsuccessful (Eq 35)

(1?) S. B. Hanna, Y. Iskander and Y. Riad, J . Chem. Soc., 21? (1961).

(18) I. Bothberg and E. R. Thornton, J. Amer. Chem. Soc.. 86, 3296, 3302 (196*0 . SUMMARY

5-Bromo-i4--quinolyldiazomethane (^+) and ^-quinolyldiazo

methane (£) are preparable by controlled thermal decomposi

tions of their corresponding sodium p-tosylhydrazonates (£

and £2). Diazo compounds k and 2 behave as typical 1,3-

dipolar reagents with phenylacetylene and acrylonitrile

though the yields of the products are generally low and the

systems are sometimes complicated by formation of unusual biproducts. Decompositions of ^ and 2 or 2 and 22 ei'ther thermally or photochemically yield 5-bromo-^-quinoline-

carboxaldehyde azine (£(+) and 4-quinolinecarboxaldehyde azine (22^ respectively as common products. 5-Bromo-4-

cyanoquinoline (£8) is obtained from £ both thermally and photochemically and ^-cyanoquinoline (22) similarly isolated upon photolysis of 22 in benzene. Nitriles £8 and 22 are apparently derived from decompositions of azines

and 22• Efforts to trap 5-bromo-4-quinolylmethylene (8) and ^--quinolylmethylene (g) with olefins or effect their insertion into various types of C-H bonds are in vain.

No evidence for formation of bridged quinoline 6 or its derivatives has been found.

176 17?

Attempted ^-elimination of 4--chloromethylquinoline (£6 ) with lithium 2 ,2 ,6 ,6-tetramethylpiperidide results in 1 ,2- bis(^-quinolyl)ethylene (22) £°od yield. Formation of the anion (£?) of 2§ is proved by deuterium labelling experiment. Ethylene 22 Is presumably obtained by reaction of 76 with 22 followed by dehydrochlorination. Efforts to trap carbene 2 » as possibly formed by base-catalyzed <=(- elimination of 2 2 , with cyclopentene, cyclooctene and ethyl vinyl ether at temperatures ranging from 25° to 1^5° have not been successful. EXPERIMENTAL

Melting Points Melting points were determined using a

Thomas Hoover capillary melting point apparatus and a

Fisher melting point "block, and were uncorrected.

Elemental Analyses Elemental analyses were performed by

Microanalysis Inc., Wilmington, Delaware.

Infrared Spectra Infrared spectra were obtained using a

Perkin Elmer, Model 457 recording spectrophotometer. All spectra were calibrated against a polystyrene absorption peak at 1601 cm"*"*-.

Proton Nuclear Magnetic Resonance Spectra Proton nuclear magnetic resonance spectra were obtained using Varian

Associates nuclear magnetic resonance spectrometers, Model

EM-360L, and Bruker HX-9°* Chemical shifts were measured in ppm downfield from tetramethylsilane.

Mass Spectra Mass spectra were determined by Mr. C. R.

Weisenberger on an MS-9 mass spectrometer.

1?8 179

Column Chromatography EK silica gel (70-325 mesh) or

MN-Kieselgel 60 silica gel (70-270 mesh) and alumina

"Woelm", neutral, activity Gr. I were used for column

chromatography.

2-Chloro-4-methylquinoline (4 4 ) . ^ 2-Hydroxy-4-methylquinoline (50 g, 0.314 mole) was added to stirred phosphorous oxychloride (40 ml) at 70-80°. The mixture was stirred until the solid dissolved completely. This clear solution was then poured into ice water (3 1) and neutralized with sodium carbonate. The white crystals were filtered and dried under vacuum to yield 2-chloro-4-methylquinoline (44,

55*4 g, 9 9 .2^, mp 54-56°(dilute ethanol); lit.® m? 55°) •

(19) Reference 8 is followed for the preparation of the compound.

2-Chloro-4-methyl-5-nitroquinoline (4£) and 2-chloro-4- methyl-6 -nitroquinoline (^a).1^ 2-Chloro-4-methylquinoline (55*4 g, 0.311 mole) was added slowly to a stirred mixture of fuming nitric acid (180 ml) and concentrated sulfuric acid (180 ml) at 0-5°. After the addition, the mixture was heated on a steam bath for 15 min and poured into ice water (3 1)» The white precipitate was filtered, washed with water until the filtrate was no more acidic and 180

dried. The solid was dissolved in a minimum amount of hot

95% ethanol and allowed to cool to 55°• Filtration then gave 2-chloro-4-methyl-6-nitroquinoline (4£a, 7.5 g» 12%, mp 213-2l4°(ethanol); lit.8 mp 213.5-214°). The filtrate was cooled in a refrigerator and filtered to form 2 -chloro-

4-methyl-5-nitroquinoline (4£, 36.6 g, 52.7%, mp 13^-136°

(ethanol); lit.® mp 133-134°).

5-Amino-2-chloro-4-methylquinoline (^6 ).1^ A mixture of

2-chloro-4-methyl-5-nitroquinoline (0.5 g, 2.2 mmole), iron powder (0.5 g, 8.9 mmole) and concentrated hydrochloric acid

(2 ml) in tetrahydrofuran (20 ml) was refluxed for 2 h.

After filtering the iron the filtrate was poured into ice water, made alkaline with aqueous sodium hydroxide and extracted with methylene chloride. Evaporation of methylene chloride yielded 5-amino-2-chloro-4-methylquinoline (46,

0.35 g» 81%, mp 93-100°(50% ethanol); lit.8 mp 102.5-103°); exact mass calcd. m/e for C^qH^^CI8^: 192 . 04542, obs. m/e =

192.04582, diff.=2 ppm.

5-Amino-4-methylquinoline (^2^* 5-Amino-4-methy1- quinoline can either be prepared from 5-amino-2-chloro-4- methylquinoline (Method A) or directly from 2-chloro-4- methyl-5-nitroquinoline (4£, Method B).

Method A : A misture of 5-amino-2-chloro-4-methylquinoline 181

(1,0 g, 5*2 mmole), potassium hydroxide (0.3 g, 5*3 mmole) and a catalytic amount of Raney nickel in ethanol (40 ml) was hydrogenated at 44 psi for 2.5 h. The Raney nickel was filtered off and the filtrate concentrated, poured into ice water and extracted with chloroform. Evaporation of the chloroform and sublimation at 1 mm Hg and 90° led to 5- o 8 amino-4-methylquinoline (4£, 0.65 g» 79*2/, mp 74-77 ; lit. mp 82.5-83.5°); exact mass calcd. m/e for C]_o^l0^2=

153.03439, obs. m/e=158.08469, diff.=1.9 ppm.

Method B ?° Hydrazine hydrate (5 ml, 99-100/) was added drop by drop to a stirred suspension of 2-chloro-4-methyl-

5-nitroquinoline (0.5 g» 2.2 mmole) and 10/ palladium on carbon (50 mg) in ethanol (50 ml). After the evolution of hydrogen had subsided, the mixture was refluxed for 2 h.

Nitrogen was then bubbled through the solution, the catalyst was filtered and the ethanol removed. The crystalline residue was dissolved in methylene chloride, washed with water and dried over calcium chloride. Removal of methylene chloride gave 5-amino-4-methylquinoline (4£, 0.32 g, 78/).

For larger scale experiments, lesser amounts of hydrazine hydrate and palladium on carbon may be used.

(20) Method B is followed from modification of M. J. S. Dewar and T. Mole, J. Chem. Soc., 2556 (1956). 182

5-Bromo-4-methylquinoline (48). 5-Amino-4-methylquinoline

(1.0 g, 6.3 mmole) was dissolved in hydrobromic acid (20 ml,

k8fo) and water (5 ml) and diazotized with sodium nitrite (

0.52 g, 6.3 mmole) in water (5 ml) at 0-5°. The clear red

solution was then poured into a mixture of cuprous bromide

(3-0 g, 20.9 mmole) in hydrobromic acid (20 ml, 48%) at 60°.

After the evolution of nitrogen had subsided the mixture was

heated to boiling and poured into ice water. The mixture

on basification with ammonium hydroxide liberated the

quinoline. The white precipitate was filtered, washed with

water and dried. Chromatography (silica gel, chloroform)

afforded 5-bromo-4-methylquinoline (^8 , 0 .8? g, 6Z‘/b, mp

110-111°(petroleum ether/toluene); lit.^ mp 102.5-103.5°);

Nr:.R (CDCl^, S) 8.53 (d, 1H), 7 .73-7.40 (m, 2H), 7-10-6.84

(m, 2K), 2.30 (s, 3H, CH^); mass spectrum 221, 223 (K+)*

5-Bromo-4-quinolinecarboxaldehyde (4g). 5-Bromo-4-methyl-

quinoline (2.0 g, 9 mmole) in dioxane (25 ml) was heated to

60° and selenium dioxide (1.1 g, 9-9 mmole) in water (1 ml)

and dioxane (5 ml) was added with stirring. After the mixture had been refluxed 5 h, the black selenium was filtered

through Celite using a sintered glass funnel. The dioxane P 1 solution was further treated with deactivated Raney nickel to remove the remaining selenium. Evaporation of dioxane and chromatography (silica gel, benzene) gave 183

(21) M. Heller, S. M. Stalar and S. Bernstein, J. Org. Chem., 26, 5044 (1961).

5-bromo-4~quinolinecarboxaldehyde (4g, 1.53 gt 72%, mp l60-l6l°(petroleum ether/toluene)); IR (KBr, cm-'1') 2850, 2740

(aldehyde proton, w) , 1700 (C 0, s); NMR (CDCl^, $) 10.6

(s, 1H, CHO), (d, 1H), 9*05 (doublet of doublet, 1H),

8.24 (doublet of doublet, 1H), 7 .94 (d, 1H), 7-78-7.32 (m,

1H) ; exact mass calcd. m/e for C^QH^NOBr^ 234.96332, obs. m/e=234.9628I , diff.=2.1 ppm.

Anal. Calcd. for C^H^NOBr: N, 5*93; Br, 33*90*

Found: N, 5*53; Br, 34.49*

4-Quinolinecarboxaldehyde (£2). A solution of selenium dioxide (19*2 g, 0.173 mole) in dioxane (150 ml) and water

(10 ml) was added to 4-methylquinoline (21.4 g, 0.15 mole) in dioxane (20 ml). The mixture was refluxed for 1 h and the selenium was removed as described previously. The residue after evaporating the dioxane was chromatographed

(silica gel, benzene) to give 4-quinolinecarboxaldehyde (£2,

11.15 g. 47.4%, mp 49-50°(petroleum ether/toluene); lit.^ mp 50-52°).

4-Quinolinecarboxaldehyde £-Tosylhydrazone (£3). p-Tosylhydrazine (1.3 g, 7.0 mmloe) was added to 184

4-quinolinecarboxaldehyde (1.0 g, 6.4 mmole) in benzene

(10 ml). The mixture was stirred for 1 h and protected from light. Filtration and drying under vacuum yielded 4-quino linecarboxaldehyde p-tosylhydrazone 2.03 g> 98%)* Since this tosylhydrazone is unstable to heat and light, it was used for the subsequent thermal or photochemical decompositions without further purification. Longer reaction times for preparing the tosylhydrazone led to gummy orange products.

5-Bromo-4-quinolinecarboxaldehyde p-Tosylhydrazone (£0).

A mixture of 5-bromo-4-quinolinecarboxaldehyde (1.0 g, 4.23 mmole) and p-tosylhydrazine (C.9 g, 4.8 mmole) in benzene

(15 ml) was stirred for 2 h in the dark. The light yellow precipitate was filtered and vacuum-dried yielding 5-bromo-

4-quinolinecarboxaldehyde p-tosylhydrazone (£0, 1.67 g,

97.5%); IR (KBr, cm"1) 3200 (NH, m), 1340, 1165 (S02 , s).

Preparation of Sodium Quinolinecarboxaldehyde p-Tosyl- hydrazonate. Sodium quinolinecarboxaldehyde p-tosylhydrazonate was generally prepared from the corresponding tosylhydrazone in tetrahydrofuran by adding a slight excess of sodium hydride (washed with hexane and dried under nitrogen). After the mixture had been stirred under nitrogen for 20 min, tetrahydrofuran was removed under vacuum and the dry sodium salt was suspended in a solvent in which thermolysis or photolysis was to be effected. 185

Thermolysis of Sodium 5-Bromo-^-quinolinecarboxaldeh.yde p-Tosylhydrazonate in benzene. The sodium salt of 5- bromo-^-quinolinecarboxaldehyde ^-tosylhydrazone (1.18 g,

2.92 mmole) was suspended in benzene (75 ml) and refluxed under nitrogen for 2 h. After filtering the precipitate and removing the benzene 5-bromo-^-quinolyidiazomethane (^,

0.^36 g, 60$) was isolated as unstable orange needles, mp

1^6°(dec.); IR (KBr, cm"1) 2080 (=N9, s); NMR (CDCl^, $ )

8.83 (d, 1H), 8.1-7.26 (m, 3H), 6.90 (d, 1H), 5-6 (s, 1H,

CHN2); mass spectrum calcd. m/e for C^0H^K^Br^^= 2^4-6.97^56, obs. m/e=246.97527. diff.=2.8 ppm.

Thermolysis of Sodium 5-Bromo-4-ouinolinecarboxaldehyde

P-Tosylhydrazonate in Benzene in the Presence of Cuprous

Bromide. Sodium hydride (0.13 g, 505, 2.7 mmole) was added to 5-bromo-^-quinolinecarboxalaehyde p-tosylhydrazone

(1.0 g, 3*5 mmole) in tetrahydrofuran and stirred for 20 min. The tetrahydrofuran was removed under reduced pressure and the dry salt refluxed for 2 h in benzene (75 ml) containing a trace amount of cuprous bromide. Upon filter ing solid and concentrating the filtrate, the residue was chromatographed (silica gel, chloroform). l,2-Bis(5-bromo-

^-quinolyl)ethylene (6 1 , 0.326 g, 605, mp 278-28l°(toluene)) was separated as yellow crystals; NMR (CDCl^, $) 8.69 (d,

2H), 8.22-7.99 (m, 4H), 8.13 (s, 2H), 7.65-7.21 (m, 2H), 186

6.89 (d, 2H); mass spectrum 438, 440, 442 (1:2:1) (M + ).

Anal. Calcd. for C2Q^-jL2'^2^’r2 t 5^*55; H, 2.73; N» 6.36. Found: C, 55.02; H, 2.92; N, 6.72.

Thermolysis of Sodium 5-Bromo-4-quinolinecarboxaIdehyde p-Tosylhydrazonate in Benzene in the Presence of Silver Nitrate.

Sodium 5-bromo-4-quinolinecarboxaldehyde 2 -tosylhydrazonate was obtained from 5-bromo-4-quinolinecarboxaldehyde tosylhydrazone (O.98 g, 2.4 mmole) and sodium hydride (0.13 g,

50/5, 2.7 mmole). The dry sodium salt was refluxed in benzene for 2 h in the presence of a catalytic amount of silver nitrate. Filtration, solvent removal, and chromato graphy (silica gel, chloroform) gave:

(i) 5-Bromo-4-quinolinecarboxaldehyde (4g> 0.118 g, 20.6,;5) as comoared with the authentic sample.

(ii) 5-Bromo-4-quinolinecarboxaldehyde azine (£4, 0.115 g,

20.3/5, mp 295°(glacial acetic acid/chloroform)); NKR (CDC1^+

Dr.'.S0-d6, S) 8.95 (s, 2H, CH=N-), 8-75 (d, 2H), 8.51-8.43 ( m, 2H), 7.80-7.71 (m, 4H), 7.64 (d, 2H).

Anal. Calcd. for C^H-^N^Br^ C, 51.28; H, 2 .56; N , 11.97-

Found: C, 51.46; H, 2.65; K . 12.00.

Thermolysis of Sodium 5-Bromo-4-quinolinecarboxaldehyde p-Tosylhydrazonate in Chlorobenzene. A suspension of the sodium salt of 5-bromo-4-quinolinecarboxaldehyde 187

2 -tosylhydrazone (1.55 g* 3*8 mmole) was refluxed in chlorobenzene (50 ml) for 2 h. The solid was filtered off and the residue, after removing the chlorobenzene, was suspended in benzene (20 ml). Filtration yielded 5-bromo-4-quinolinecarboxaldehyde azine (£4, 78 mg, 8.7$) as previously characterized.

The filtrate was chromatographed on neutral alumina to give a mixture of 5-bromo-4-methylquinoline (48) and

5-bromo-4-cyanoquinoline (£8, 0.121 g, 13/S) which could not be separated; IR (KBr, cm~^) 2240 (C=N, w ) ; mass spectrum

221, 223 and 232, 234 (K+).

Thermolysis of Soldium 5-Bromo-4-quinolinecarboxaldehvde p-Tosylhydrazonate in Cyclohexene in the Presence of Cuprous

Bromide. Sodium hydride (0.15 g» 50"°, 3*1 mmole) was added to 5-8romo-4-quinolinecarboxaldehyde p-tosylhydrazone

(1.15 g, 2.8 mmole) in tetrahydrofuran (50 ml) and stirred for 30 min. Upon removing the solvent the dry sodium salt was refluxed in a mixture of cyclohexene (75 ml) and catalytic quantity of cuprous bromide for 2 h. The mixture was filtered and the solvent was evaporated from the filtrate. Chromatography of the residue (silica gel, chloroform) yielded 5-bromo-4~quinolinecarboxaldehyde azine

(£4, 0.338 g, 50.4/) as previously characterised. 188

Thermolysis of Sodium 5-Eromo-4-quinolinecarboxaldehyde

P-Tosylhydrazonate in Acrylonitrile in the Presence of

Silver Nitrate. The sodium salt of 5-bromo-4-quinoline-

carboxaldehyde ^-tosylhydrazone was synthesized from

5-bromo~4-quinolinecarboxaldehyde ^-tosylhydrazone (1.03 g,

2.55 mmole) and sodium hydride (0.13 g, 505, 2.71 mmole).

The dry sodium salt was then refluxed in acrylonitrile ( 75

ml) in the presence of silver nitrate (0.3 g) for 1 h. The

solid was filtered hot from the mixture and extracted with

chloroform. The chloroform extracts were combined with

the filtrate and evaporated. Chromatography (silica gel,

chloroform) and trituration with hexane yielded 5-(5'-

bromo-4'-quinolyl)-3-cyano-2-pyrazoline (6£, 0.312 g, 40.3/,

mp 134-185°(dec.)); IR (KBr, cm"1) 3320 (NH, m), 2240 (CsN,

m); NKR (CDCl^, S) 9-06 (d, 1H), 8.13 (doublet of doublet,

1H), 7*31 (doublet of doublet, 1H), 7-57-7-39 (m, 2H),

5.77 (broad triolet, 1H), 3-64 (two doublet, 1H), 2.86

(two doublet, 1H, pyrazoline C-H); exact mass calcd. m/e

for C ^ H ^ B r ? 9: 300.00110, obs. m/e= 300.00180, diff. = 2.3 ppm.

Anal. Calcd. for C^HqN^Br: C, 51-83; H, 2.99; K, 18.60.

Found: C. 52.37; H, 3-00; N , 13.70.

Thermolysis of Sodium ^-Bromo-4-quinolinecarboxaldehyde p-Tosylhydrazonate in Phenylacetylene. A solution of 189

5-bromo-4-quinolinecarboxaldehyde p-tos.ylhydrazone (1.0 g,

2.14-7 mmole) and sodium hydride (0.13 g» 505, 2.7 mmole) in

tetrahydrofuran was stirred for 20 min. Upon removing the

solvent, the dry salt was refluxed in a mixture of benzene

(50 ml) and phenylacetylene (3 ml) for 3 h. Filtration of

the solid and chromatography (silica gel) after removal of

the solvents led to two compounds:

(i) Elution with chloroform gave 3-(5 *-bromo-4''-quinolyl)-

5-phenyl(lH)pyrazole (6°, 0.1? g, 19.6/, mp 193~195°(

toluene)); IR (KBr, cm-1) 3140 (NH, w); NMR (CDCl^, $)

9.05 (d, 1H), 8.55 (doublet of doublet, 1H), 8 .O9 (doublet

of doublet, 1H), 7*34-7*31 (m, 7H, aromatic), 6.94 (s, 1H); 70 exact mass calcd. m/e for C^gH^NgBr - 349 .02150, obs . m/e =

349.02209, diff.=l.? ppm.

Anal. Calcd. for C^gH-^NgBr: C, 61.71; H, 3*42; N , 12.00.

Found: C, 62.01; H, 3.47; N, 12.04.

(ii) Further elution with methanol led to 5-bromo-4-

quinolinemethanol (£0, 0.134 g, 22.7/5, mp l66-l67°(toluene/

acetonitrile)); exact mass calcd. m/e for C^QHgN0Br^=

236.97397, obs. m/e=236.97966, diff.=2.9 ppm; identical with an authentic sample prepared from lithium aluminum hydride reduction of 5-bromo-4-quinolinecarboxaldehyde.

5-Bromo-4-quinolinemethanol (£0). A solution of 5-bromo-

4-quinolinecarboxaldehyde (1.0 g, 4.2 mmole) in 190 tetrahydrofuran (30 ml) was added to a stirred suspension of lithium aluminum hydride (0.10 g, 2.6 mmole) in tetra hydrofuran (25 ml) at -55°• The mixture was stirred at

-55° for 30 min and warmed to -^0°; then tetrahydrofuran

(10 ml) in water (10 ml) was added slowly. tVhen the mixture warmed to 0°, sodium hydroxide (0.3 g) in water (10 ml) was added. The clear solution was decanted from the gummy white precipitate and concentrated. The oily residue was dissolved in chloroform, washed with water and dried over sodium sulfate. Evaporation of the chloroform allowed isolation of 5-bromo-h--quinolinemethanol (£0 , 0.837 E, mp 160-162°(toluene/acetonitrile)); IR (KBr, cm-'*') 3^-00

(OH, m); NMR (CDCl^, $) 9.0 (d, 1H), 8.17-7.20 (m, hH),

5.23 (s, 2H), 2,32 (s, 1H, OH); exact mass calcd. m/e for

C10H8N0Br79=236.97397, ohs. m/e=236.97966, diff.=2.9 ppm.

Anal. Calcd. for C^HgNOBr: C, 50.^2; H, 3-36; N, 5* 38.

Found: C, 50.82; H, 3-36; U, 6 .2 5 .

Photolysis of Sodium 5-Bromo-^-quinolinecarboxaIdehyde p-Tosylhydrazonate in Ethyl Ether. The sodium salt of

5-bromo-^-quinolinecarboxaldehyde ^-tosylhydrazone (1.92 g,

4.75 mmole) was photolyzed in ethyl ether for 3 h.

Filtration of the solid, evaporation of the solvent and chromatography (neutral alumina, benzene) yielded 191

5-bromo-4-methylquinoline (48, 0.27 g, 25.6'u, mo 108-109,5°)

as previously identified.

Photolysis of Sodium 5-Bromo-4-quinolinecarboxaldehyde

p-Tosylhydrazonate in Benzene. Sodium 5-bromo~4-

quinolinecarboxaldehyde p-tosylhydrazonate was prepared

from 5-bromo-4-quinolinecarboxaldehyde ^-tosylhydrazone

(1.16 g, 2.87 mmole) and sodium hydride (0.16 g, 50$$, 3-33

mmole). The dry sodium salt was suspended in benzene and

irradiated for 3 h. Chromatography on silica gel after

filtration and solvent removal resulted as follows:

(i) Elution with benzene yielded a mixture of 5-bromo-4-

quinolinecarboxaldehyde (4§) and 5-bromo-4-cyanoquinoline

(£3, 0.127 g, 13.7^).

(ii) Elution with chloroform allowed isolation of 5-bromo-

4-quinolinecarboxaldehyde azine (£4, 0.108 g, 16$$).

Thermolysis of Sodium ^-Quinolinecarboxaldehyde p-Tosyl- hydrazonate in Toluene. The dry sodium salt prepared

from 4-quinolinecarboxaldehyde ^-tosylhydrazone (2.0 g,

6.15 mmole) and sodium hydride (0.53 6. 50;$, 11.0 mmole), was decomposed in refluxing toluene (75 ml) under nitrogen

for 1 h. After filtering the precipitate and removing the toluene the residue was chromatographed on neutral alumina as follows: 192

(i) Elution with benzene afforded 4-quinolyldiazomethane

(£, O .388 g, 36/S) as unstable orange crystals, mp 85°(dec.);

TR (KBr, cm"1) 2080 (=N2 , s); KMR (CDCl^, $) 8.71 (d, 1H),

8.2-7.3 (m, 4H), 6.86 (d, 1H), 5*6 (s, 1H, CHN2); mass

spectrum calcd. m/e for C^qH^N2=169-06399» obs. m/e =

169.06435, diff.=2.4 ppm.

(ii) Elution with chloroform gave yellow crystals which were recrystallized from toluene/chloroform to give

4-quinolinecarboxaldehyde azine (22* 0.133 g, 14/) as fuzzy yellow needles, mp 220-221°; NMR (CDCl^, S) 9-33 (s, 2H,

CH=N-), 9-0? (d, 2H), 8.82-8,71 (m, 2H), 8.28-3.17 (m, 2H),

7.94 (d, 2H), 7*9-7*6 (m, 4h); mass spectrum calcd. m/e

for C20H1/fN^=282.11569, obs. m/e=282.11641, diff.=2.5 pom.

Anal. Calcd. for C20H14N4 : C, 77-42; H, 4.52; N, 18.06.

Found; C, 77-05; H, 4.30; N, 17-63-

Thermolysis of Sodium 4-Qiuinolinecarboxaldehvde p-l'osyl- hvdrazonate in Toluene in the Presence of Silver Nitrate.

Sodium 4-quinolinecarboxaldehyde p-tosylhydrazonate was obtained from 4-quinolinecarboxaldehyde p-tosylhydrazone

(1.20 g, 3-7 mmole) and sodium hydride (0.23 g» 50/, 4.8 mmole). The dry sodium salt was refluxed in toluene (50 ml) with silver nitrate (0.3 g) for 0.5 h. After filtering the solid, removing the toluene and chromatography of the 193

residue on silica gel (ethyl acetate) 4-quinolinecarbox-

aldehyde azine (22* 0*108 g, 13.9%) was obtained as

previously characterized.

Thermolysis of Sodium 4-Quinolinecarboxaldehyde p-Tosyl- hydrazonate in Diglyrae. The sodium salt of 4-quinoline-

carboxaldehyde p-tosylhydrazone (4.0 g, 12.3 mmole) was refluxed in diglyme (50 ml) under nitrogen for 2 h.

Filtration of the precipitate, removal of the solvent under vacuum and chromatography on neutral alumina (chloroform) yielded 4-quinolinecarboxaldehyde azine (22• 0.45 g» 22.8%) as previously characterized.

Photolysis of Sodium 4-Quinolinecarboxaldehyde p-Tosyl- hydrazonate in Benzene. The sodium salt, prepared from 4-quinolinecarboxaldehyde p-tosylhyarazone (1.9 g, 5*8 mmole) and sodium hydride (O.365 g, 50 ?.6 mmole), was dried, suspended in benzene and photolyzed for 3 h. The residue, after filtration and concentration, was chromato graphed on neutral alumina (benzene); white crystals of

4-cyanoquinoline (22* 0.154 g, 15*7%i mp 96-97°(petroleum ether); lit.22 mp 98-101°) were obtained; IR (KBr, cm-^)

2240 (CN, w); exact mass calcd. m/e for C^qH^N2 =154.05309, obs. m/e=154.05341, diff.=2 ppm. 194

(22) U. Haug and H. Fiirst, Chen. Ber. . 593 (i960); F. M. Hamer, J. Chem. Soc., 1008 (1939)*

Thermolysis of Sodium 4-Quinolinecarboxaldehyae p-Tosyl-

hydrazonate in Phenylacetylene. A suspension of the

sodium salt of 4-quinolinecarboxaldehyde r-tosylhydrazone

(1.2 g, 3*7 mmole) in a mixture of benzene (50 ml) and

phenylacetylene (3 ml) was refluxed for 3 h under nitrogen.

Upon filtration, removal of the solvents and chromatography

(silica gel, ethyl acetate), 5-pbenyl-3-(4‘’-quinolyl)(1H)-

pyrazole (£4, 0.34 g, 345, nip 205-207°) was obtained as white crystals; IR (KBr, cm-^) 3140 (NH, w) ; NFR (CDCly

CD^OD, £) 8.38 (d, 1H), 8.16-7.41 (m, 10H, aromatic), 7-0

(s, 1H); exact mass calcd. m/e for 271.110p4,

obs. m/e=271•11153, fiff.=2.2 ppm.

Anal. Calcd. for C ^ H ^ N y C, 79-70; H, 4.80; H , 15.50.

Found: C, 79-^8; H, 4.70; N, 15-03.

4-quinolinemethanol (2§)- I10 a stirred suspension of

lithium aluminum hydride (0.40 g, 10.4 mmole) in tetrahydrofuran (75 ml) at -50° was added 4-quinolinecarbox aldehyde (5-0 g, 31-3 mmole) in tetrahydrofuran (75 ml).

The mixture was stirred at -50° for another 30 min, slowly 195

raised to -25° and tetrahydrofuran (10 ml) in water (5 nil)

was added. After the mixture had warmed to 0° sodium

hydroxide (1.5 g) in water (10 ml) was added. The clear

solution was decanted from the gummy v/hite precipitate and

concentrated. The oily residue was dissolved in chloroform

and washed with water. Removal of chloroform and recrystal

lization from toluene/acetonitrile afforded 4-quinoline-

methanol (£8 , 4.75 g, 93-8/, mp 97-99°; lit.16 mp 97-98°);

exact mass calcd. m/e for C^qHqN0=259.06841, obs. m/e-

159-06571, diff.=1.9 ppm.

4-Chloromethylquinoline (2£)» 4-Quinolinemethanol (2.5 g

15-6 mmole) was dissolved in hot benzene (75 ml) and

saturated with hydrogen chloride. Thionyl chloride (7-5 ml)

in benzene (10 ml) was then added at room temperature.

After the initial reaction subsided, the mixture was refluxed for 1 h, cooled to room temperature and additional benzene

(70 ml) was added. The yellow-brown precipitate was filtered washed with benzene until free of thionyl chloride, dried in vacuum, then dissolved in water and filtered. The filtrate was cooled to 0° and neutralized carefully with ammonium hydroxide. The white crystals deposited were filtered and dried. Recrystallization from hexane gave

4-chloromethylquinoline (£6 , 1.76 g, 63*2/ mp 56-56.5°; 196

lit.^ mp 55“57‘5°); exact mass calcd. m/e for C^qHqNCI^^z

177.03/152, obs. m/e=177-03505, diff.=2.8 ppm. 4-Chloro-

methylquinoline decomposes slowly at room temperature but

can be kept for a longer period of time in a refrigerator.

Reaction of 4-Chloromethylquinoline with Lithium 2.2,6,6-

Tetramethyloineridide. To 4-chloromethylquinoline (

0.7 g, 3.9 mmole) in toluene (50 ml) at 0° was added lithium

2 ,2 ,6 ,6 -tetramethylpiperidide prepared in situ by adding n-butyllithium (2.32 ml, 1.7 M, 3.9 mmole) to 2 ,2 ,6 ,6- tetramethylpiperidine (0.61 g, 3.9 mmole) in toluene (10 ml) under nitrogen. The brown mixture was then stirred at

room temperature under nitrogen for 36 h. Upon addition

of chloroform (100 ml), the mixture was washed with water

to remove the inorganic salt. The chloroform layer was

separated, dried over calcium chloride and evaporated.

Chromatography (neutral alumina, chloroform) allowed

isolation of l,2-bis(4-quinolyl)ethylene (2g, 0.467 g*

84/, mp 203-203° (toluene); lit.^ mp 207°); IR (KBr, cm”“)

1535 (C=C, s); NMR (CDC13, $) 9-01 (d, 2H), 8.4-3.1 (m,

4h ), 8.0 (s, 2H), 7-85-7*l6 (m, 6H); exact mass calcd. m/e for C20H1/+N2=282.11569, obs. m/e=282.11641, diff.=2.5 ppm.

Further elution with methanol yielded 2,2,6,6-tetramethylpiperidine hydrochloride (80, 79 mg, 10.4/, mp 275° 197

(toluene/chloroform)); IR (KBr, cm-1) 3020-24-60 (complex, strong, aliphtic C-H), 1335, 1390 (s, CH^b NMR (CDCl^, $)■

1.6? (s, 6H, -(CH0)0-), 1.52 (s, 12H, 4- CH~); mass snectrum j j 14-1 (n + -HCl).

Anal. Calcd. for C^H^CIN: C, 60.85; H, 11.27; N, 7.83.

Found: C, 60.90; H, 11.35; N, 8 .2 5 .

The spectral date of 30 were identical with those of authentic sample synthesized from 2 ,2 ,6 ,6-tetramethyl- pineridine and hydrochloric acid. REFER.;: RCJ.S

PART I

1. (a) R. J. Bailey, Ph.D. Dissertation, The Ohio State University, 197**-• (b) P. Card, Fh.D. Dissertation, The Ohio State Uni versity, 1976. (c) F. Friedli, Ph.D. Dissertation, The Ohio State University, 1973.

2. R. J. Bailey and H. Shechter, J . Amer. Chem. Soc., §6, 8116 (197*0 . 3. M. A. Gessner, Master's Thesis, The Ohio State University, 19 77. 4. L. Wolff, Justus Liebigs Ann. Chem., 32 5, 129 (1902); ibid.. 333. 1 (1904); ibid., 39*+. 23 U912); for recent review see H. Meier and K.-P. Zeller, Angew. Chem. Intemat. Edit., 1^, 32 (1975)*

5 . W. Kirmse and K. H. Pook, Chem. Ber.. ^3, k022 (1965); H. Erlenmeyer and M. Aeberli, Helv. Chim. Acta.. 28 (19*13); P. Yates and R. J. Crawford, J. Amer. Chem? Soc., 88, 1562 (1966).

6. M. P. Cava and R. J. Spangler, J. Amer. Chem. Soc., 83, h550 (1967).

?. W. Jugelt and D. Schmidt, Tetrahedron. 2 5, 969 (1969); A. Melzer and E. F. Jenny, Tetrahedron Lett., h503 (I968).

8. D. M. Jordan, Fh.D. Dissertation, The Ohio State Uni versity, 1965 •

9 . A.de Groot, J. A. Boerma, J. de Valk, and H. Wynberg, J. Org. Chem., 22* **025 (1968).

10. L. Horner and E. Spietschka, Chem. Ber.. 85, 225 (1952).

11. J. Bredt and W. Holz, J. Prakt. Chem., 22* 133 (1917); L. Horner and E. Spietschka, Chem. Ber. . 88, 93*+ (1955); T. Gibson and W. F. Erman, J. Org. Chem..~^l. 3028 (1966).

12. K. Ueda and F. Toda, Chem. Lett., 779 (1975)*

13* 0. Siis and K. Moller, Justus Liebigs Ann. Chem.. 592* 91 (1955); 0. Sus, M. Glos, K. Moller and H. D. Eberhardt,

198 199

ibid.. 533, 150 (1953); 0. Sus and K. Moller, ibid., 233 (1955). 14. A. Padwa and R. Layton, Tetrahedron Lett.. 2167 (1965).

15* to* Jones, Jr., and Y.;. Ando, J. Amer. Chem. Soc.. 90, 2200 (I968).

16. M. Jones, Jr., W. Ando, and A. Kulczycki, Jr., Tetrahedron Lett., 1391 (1967); M. Jones, Jr., and K. R. Rettig, J. Amer. Chem. Soc., 82, 4013, 4015 (1965)» and references therein.

17- U. R. Ghatak, P. C. Chakraborti, B. C. Ranu and B. Sanyal, J. C. S. Chem. Comm.. 548 (1973).

18. W. Kirmse "Carbene Chemistry" 2nd Edit., Academic Press, New York 1971; L. L. Rodina and I. K. Korobitsyna, Russ. Chem. Rev., 36, 260 (1967); A. Mustafa, Advan. Photochem.. 2, 113 (1964).

19* R- Paulissen, H. Reimlinger, E. Hayez, A. J. Hubert and Ph. Teyssie, Tetrahedron Lett., 2233 (1973).

20. N. Yoshimura, S.-J. Murahashi, and J. Moritani, J. Organo- metal. Chem.. ^2C, 58 (1973).

21. N. A. Preobrashenski, A. M. Poljakowa, and W . A. Preo- brashenski, Ber. Deut. Chem. Ges.. 68, 850 (1935); J* F» Lane, J. Willenz, A. Weissberger, an3 E. S. Wallis, J. Org. Chem., 276 (1940).

22. J. F. Lane and E. S. Wallis, J. Amer. Chem. Soc., 63, 1674 (1941).

2 3 . E. S. Wallis and P. I. Bowman, J. Org. Chem., 1, 383 (1936).

24. M. J. S. Dewar and C. A. Ramsden, Chem. Commun.. 683 (1973); A. C. Hopkinson, J. C. S. Perkin II. 794 (1973); J. G. Csizmadia, H. E. Gunning, R. K. Gosavi and 0. P. Strausz, J. Amer. Chem. Soc.. 133 (1973).

25. V. Franzen, Justus Liebigs Ann. Chem., 6l4, 31 (1958).

26. G. Frater and 0. P. Strausz, J. Amer. Chem. Soc., 92, 6654 (1970).

2 7 . M. Regitz and J. Ruter, Chem. Ber.. 102, 3877 (1969). 200

28. K. G. Nogai, Dissertation, Technische Universitat, Hannover, 1972.

2 9 . H. Meier, IVth IUPAC Symposium, 1972, p. 163•

30. K. P. Zeller, Chem. Commun., 317 (1975)*

31. K. P. Zeller, Chem. Ztg.. g2» 37 (1973)-

32. F. Kaplan and G. K. Meloy, J. Amer. Chem. Soc. . 88, 950 (I966); R. Curi, F. DiFuria and V. Lucchini, SpecT Lett., 7, 211 (197^); H. Kessler and D. Rosenthal, Tetrahedron Lett.. 393 (1973).

33* F. Kaplan, M. L. Mitchell, Tetrahedron Lett., 759 (1979).

34. M. S. Newman and A. Arkell, J. Org. Chem., 24, 385(1959)*

35* R* A. Franich, G. Lowe and J. Parker, J.C. S. Perkin I., 2034 (I972); G. Lowe and J. Parker, Chem. Commun., 1135 (197D.

3 6. E. Voigt and H. Meier, Angew. Chem. Intemat. Edit., 14, 103 (1975).

37. T. Miyashi, T. Nakajo and T. Mukai, Chem. Commun., 442 (I978).

38. E. Schmitz, A. Stark and Ch. Horig, Chem. Ber.. 9 8 , 2509 (1965). 39* W. Ried and H. Lowasser, Justus Liebigs Ann. Chem., 68^, 118 (1965); D. C. DeJongh and R. Y. Van Fossen, Tetrahedron, 28, 3603 (1972).

40. C. G. F. Bannerman, J. I. G. Cadogan, I. Gosney and N. H. Wilson, Chem. Commun., 618 (1975)*

41. 0. Tsuge, I. Shinkai and M. Koga, J . Org. Chem. , ^6, 7^5 (1971). 42. M. P. Cava, R. L. Litle and D. R. Napier, J. Amer. Chem. Soc.. 80, 2257 (1958).

^3. Org. Svn. Coll. Vol. II, 4961 ibid., III, 351.

44. S. Ruhemann, Chem. Ber., 52B, 287 (1920)} F. M. Rowe and J. H. S. Davis, J. Chem. Soc.. 1344 (1920). 201

45* F. Ullmann, Justus Liebigs Ann. Chem.. 727, 117 (19°3)•

46. H. Staudinger, H. Goldstein and E. Schlenker, Helv. Chim. Acta., 4, 3^2 (1921).

4 7 . C. Liebermann and M. Zsuffa, Chem. Ber.. 44, 202 (1911).

48. N. Baumann, Helv. Chim. Acta.. 274 (1972).

4 9 . 0. Chapman, Chemical & Engineering News, American Chemical Society, September 18, 197S, p. 17*

50. J. Haywood-Farmer, R. E. Pincock and J. I. Wells, Tetrahedron,1 1,1 22, 2007 (1966). 51. M. M. Fawzi and C. D. Gutsche, J. Org. Chem., ^1* 139° (1966); J. Trotter, C. S. Gibbons, N. Nakatsuka~and S. Masamune, J. Amer. Chem. Soc., 8g, 2792 (1967).

52.. U. Mende, B. Raduchel, W. Skuballa and H. Vorbruggen, Tetrahedron Lett., 629 (1975)*

53* 0. Tsuge and M. Koga, Heterocycles, 6, 411 (1977).

54. R. Huisgen, H. J. Sturm and G. Binsch, Chem. Ber.. 9 7 , 2864 (1964); R. Huisgen, G. Binsch and L. Ghosez, ibid., 2£, 2628 (1964).

55* K. B. Wiberg and B. J. Nist, J. Amer. Chem. Soc., 85, 2788 (1963); J. D. Graham and K. T. Rogers, ibid.,~84, 2249 (1962).

56. R. Huisgen, G. Binsch and H. Konig, Chem. Ber., 97, 2884 (1964).

57* A. Padwa and E. Chen, J. Org. Chem.. 72* 1976 (1974).

58. E. F. Ullmann, B. Singh, J. Amer. Chem. Soc.. 88, 1844 (1966).

59* T. Yamazaki and H. Shechter, Tetrahedron Lett., 4533 (1972).

60. G. L. Closs and W. A. Boll, J. Amer..Chem. Soc., 8£, 390^ (1963)! G. L. Closs and W. A. Bb'll, Angew, cKem. Intern. Ed. Eng., 2 , 399 (1963); G. L. Closs, W. A. Boll, H. Heyn and V. Dev7 J. Amer. Chem. Soc., 22* 173 (1968); G. Ege, Tetrahedron Lett.. 1667 (I963T; R.~Anet and 202

F. A. L. Anet, J. Amer. Chem. Soc., 86, 525 (1964); A. C. Day and M. C. Whiting, Chem. Commun.7 292 (1965); A. C. Day and M. C. Whiting, J. Chem. Soc.. C, 1719 (196?); G. L. Closs, L. R. Kaplan and V. I. Bendall, J. Amer. Chem. Soc., 3g, 33?6 (1967)-

61. T. Yamazaki and H. Shechter, Tetrahedron Lett., 1417 (1973); M» Martin and M. Regitz, Justus Liebigs Ann. Chem., 1702 (1974)5 A. Katner, J. Org. Chem., $8, 825 (1972); M. Frank-Neumann and C. Buchecker, Angew. Chem., 85, 259 (1973); L. L. Rodina, V. V. Bulusheva, T. G. Skimova and I. K. Korobitsyna, Zh. Org. Khim., 10, 55 (.1974); L. L. Rodina, V. V. Bulusheva and I. K.~Roro- bitsyna, ibid.. 10, 1937 (1974).

62. A. W. Johnson, A. Langemann and J. Murray, J. Chem. Soc., 2136 (1953).

63. 0. Tsuge, M. Tashiro and I. Shinkai, Bull. Chem. Soc. Jap., 42, 181 (1969)•

64. G. Wittig and A. Krebs, Chem. Ber.. §4, 3260 (1961).

6 5 . W. R. Bamford and T. S. Stevens, J . Chem. Soc., 4735 (1952).

66. Neunhoeffer and Hans: "Chemistry of 1,2,3-Triazines and 1,2,4-Triazines, Tetrazines and Fentazines" Wiley, New York, 1978, p. 1237-1295.

67. N. S. Dikuniknin and G. I. Bystritskii, J. of Gen. Chem., USSR., 32, 1303 (1962).

68. Kg. Ph. Bun-Hoi* and Denije Lavit, Rec. Trav. Chim., 77, 724 (1958); G. P. Petrenko and M. K. Dashevskii, Zhur. Priklad. Khim.. 32, 1126 (1959).

6 9 . A. Bosch and R. K. Brown, Canadian J. cl Chem.. 46, 715 (1968); L. F. Fieser and J. Carson, J. Amer. Chem? Soc., 62, 432 (1940).

70. Z. Zil'berman, A. I. Kulkova and N. A. Sazanova, Khim. Naukai. Prom., 4, 135 (1959); R. Pfleger and K. V. Strandfmann, Chem. Ber., gO, 1455 (1957).

71. L. Friedman and H. Shechter, J. Org. Chem.. 26. 2522 (1961). ~~

72. L. F. Fieser and A. I-i. Seligman, J. Amer. Chem. Soc., 61, 136 (1939). 203

73* G. Caronna, Gazz. Chim. Ital., £2* ^03 (19^9). 7^. G. J. Leuck, R. P. Perkins and F. C. V.hitmore, J. Amer. Chem. Soc., £1, 1831 (1929).

75- H. G. Rule, v V . Fursell and R. R. H. Brown, J. Chem. Soc. , 163 (193*0• 7 6 . U. G. Kang, Ph.D. Dissertation, Michigan Satte University (1972).

PART II

1. (a) R. J. Bailey, Ph.D. Dissertation, The Ohio State University, 197^+; (b) R. J* Bailey and H. Shechter, J. Amer. Chem. Soc., £6, 3116 (197*0•

2. P. Card, Ph.D. Dissertation, The Ohio State University, 1976.

3 . F.. A. Gessner, Paster's Thesis, The Ohio State University, 1977.

4. F. Friedli, Ph.D. Dissertation, The Ohio State University, 1973.

5 . P. S. Shetty and Q. Fernando, J. Amer. Chem. Soc., 92, 396'+ (1970).

6. 0. Chapman and J. P. LeRoux, J. Amer. Chem. Soc., 100, 282 (1973).

7. v;. D. Crow, P. N. Padaon-Row and D. S. Sutherland, Tetrahedron Lett., 2239 (1972); W. D. Crow, A. R. Lea and K. U. Raddon-Row, ibid. , 2235 (1972).

8. S. S. Krahler and A. Burger, J . Amer. Chem. Soc. , 63. 2367 (19^1).

9 . K. Kaplan, J. Amer. Chem. Soc., 6^, 265*+ (19^1)*

10. C.-T. Ho, R. T. Conlin and P. P. Gaspar, J. Amer. Chem. Soc., §6, 8IO9 (197*0* Tetraphenylethylene is reported to catalyze decomposition of diphenyldiazomethane and enhance the yield of benzophenone azine. zok

11. W. K. Jones. J. Amer. Chem. Soc., 81. 3776. 3137 (1939). la 12. Thermolysis of 1-naphthyldiazomethane (21) in benzene results in insertion of 1-naphthylmethylene into solvent to give ring expansion product 22 as in equation 8 .

13. R. A. Olofson and C. M. Dougherty, J. Amer. Chem. Soc., 25, 581, 582 (1973).

14. R. A. Olofson, D. H. Hoskin and K. D. Lotto, Tetrahedron Lett., 1677 (1978).

15. K. Carelli, M. Cardellini and F. Liberatore, Ann. Chim., 50, 698 (i960) (Rome); C. E. Kaslow and J. M. Schlatter, JT Amer. Chem. Soc.. ££, 1054 (1955).

16. C. E. Kaslow and W. R. Clark, J . Org. Chem., 18, 55 (1953); B. R. Brown, D. L. Hammick and E. H. (FKewlis, J . Chem. Soc. , 1145 (1951).

17* S. B. Hanna, Y. Iskander and Y. Riad, J. Chem. Soc., 217 (1961).

18. I. Bothberg and E. R. Thornton, J. Amer. Chem. Soc., 86, 3296, 3302 (1964).

19. Reference 3 is followed for the preparation of the compound.

20. Method B is followed from modification of M. J. S. Dewar and T. Mole, J. Chem. Soc.. 2556 (1956).

21. M. Heller, S. M. Stalar and S. Bernstein, J. Org. Chem., 26, 5044 (1961).

22. U. Haug and H. Furst, Chem. Ber., 593 (i960); F. M. Hamer, J. Chem. Soc.. 1008 (1939).