Chemistry of the Diazooxides: 10-Diazoanthrone

Home , Anthraquinone, Diazodinitrophenol

This dissertation has been 65—5635 microfilmed exactly as received

FLEMING, James Charles, 1938- CHEMISTRY OF THE DIAZOOXIDES; 10-DIAZO ANTHRONE.

The Ohio State University, Ph.D., 1964 Chemistry, organic

University Microfilms, Inc., Ann Arbor, Michigan CHEMISTRY OF THE DIAZOOXIDES;

lO-DIAZOANTHRONE

DISSERTATION

Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University

James Charles Fleming, B.S.

The Ohio State University

1964

Approved by

rA\J Adviser Depai/tment of Chemistry ACKNOWLEDGMENTS

I wish to express my sincere gratitude to Professor

Harold Shechter for four most interesting years of tutelage in organic chemistry. His leadership, his intense interest in chemistry, and his profound dedication to his profession will well serve as inspiration in years to come.

I wish to thank the Sinclair Oil Company and the

Lubrizol Corporation for financial assistance afforded me during this work.

I am also grateful to my sisters, Mrs. B. Kilbarger and

Miss K. Fleming, for help in preliminary preparations of this manuscript.

ii VITA

August 25, 1938 Born— Lancaster, Ohio

I960 . . . • • B. S., Ohio University, Athens, Ohio

1960-1961 . . Teaching Assistant, Department of Chemistry The Ohio State University, Columbus, Ohio

1961-1962 • . Research Assistant, Department of Chemistry The Ohio State University, Columbus, Ohio

1962-1963 . . Sinclair Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio

1963-196^ • . Lubrizol Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio CONTENTS Page

INTRODUCTION 1

DISCUSSION OF RESULTS 13

EXPERIMENTAL 40

General Procedures Melting Points Elemental Analyses Infrared Spectra Nuclear Magnetic Resonance Spectra Photolysis Apparatus

Preparation of 10,10-Dibromoanthrone ...... 4l

Preparation of Anthraquinone Monotosylhydrazone . . . 4l

Preparation of Anthraquinone Monohydrazone ...... 4-2

Preparation of 10-Diazoanthrone ...... 44 A. From Anthraquinone Monotosylhydrazone B. From Anthraquinone Monohydrazone C. From Anthraquinone Monooxime

Preparation of Anthraquinone Triphenylphosphazine . . 46

Copper-catalyzed Decomposition of 10-Diazoanthrone in Benzene...... 46

Photolysis of 10-Diazoanthrone in Benzene ...... 48 A. Without Ethanol B. With Ethanol

Photolysis of 10-Diazoanthrone in Toluene ...... 50

Thermolysis of 10-Diazoanthrone in Mesitylene .... 50

Photolysis of 10-Diazoanthrone in Benzene and in Toluene in the Presence of Triphenylphosphine; . Anthronylidenetriphenylphosphorane...... 51

Thermolysis of Anthraquinone Triphenylphosphazine . . 52

iv CONTENTS— (Continued) Page

Reaction of 10-Bromoanthrone with Triphenylphosphine 53 A. In §enzene B. Ixi Chloroform; Anthracene-9-oxytriphenylphosphonium Bromide

Reactio'ns of Anthronylidenetriphenylphosphorane . . 5^ A. With Acetone B. With Benzaldehyde C. With £-Nitrobenzaldehyde D. With m-Nitrobenzaldehyde

Reaction of 10-Diazoanthrone with Acetic Acid . . • 56

Reaction of 10-Diazoanthrone with Boron Trifluoride Etherate...... 56

Reaction of 10-Diazoanthrone with Phenanthrenequinone 57

Reaction of 10-Diazoanthrone with Nitrosobenzene . . 58

Attempted Reaction of 10-Diazoanthrone with N-Sulfinylaniline ...... 58

Reaction of 10-Diazoanthrone with Acrylonitrile . . 59

Reaction of 10-Diazoanthrone with Methyl Vinyl K e t o n e ...... 59

Reaction of 10-Diazoanthrone with Methyl Methacrylate 60

Reaction of 10-Diazoanthrone with trans-l,2-Diben- zoylethylene ...... 6l

Reaction of 10-Diazoanthrone with £-Benzoquinone . . 62 A. At 80° B. At Room Temperature

Reaction of 10-Diazoanthrone with Diethyl Azodicarboxylate * 6k

Reaction of 10-Diazoanthrone with Dimethyl Acetylenedicarboxylate ...... 65

v CONTENTS— (Continued) Page

Photolysis of k ',5,-Dicarbomethoxyspi^o[anthrone- 10,3,-pyrazolei ...... 66

Reaction of 10-Diazoanthrone with Benzyne ...... 66

Preparation of 7-Piazo-8-acenaphthenone ...... 67

Reaction of 7-Diazo-8-acenaphthenone with Dimethyl Acetylenedicarboxylate ...... 68

Reaction of 7-Diazo-8-acenaphthenone with Benzyne . . 68

Attempted Reaction of 7-Diazo-8-acenaphthenone with Acrylonitrile ...... 69

Photolysis of 3-Methylnaphthalene-l,if-diazooxide in the Presence of Triphenylphosphine ...... 70

Reaction of 3-Methylnaphthalene-l,4-diazooxide with trans-1,2-Dibenzoylethylene ...... 70

Reaction of 3i5-Dimethylbenzene-l,4-diazooxide with trans-1,2-Dibenzoylethylene ...... 71

Reaction of 3-Meth.ylnaphthalene-l,4— diazooxide with Benzyne ...... 72

Improved Preparation of Phenanthrene-9,10-diazooxide • 73

Attempted Reaction of Phenanthrene-9,10-diazooxide with Acrylonitrile...... 7^

APPENDIX...... 75

Infrared Spectra...... 76

Nuclear Magnetic Resonance Spectra ...... 85

vi INTRODUCTION

In 1858 Peter Griess treated an ethanolic solution of picramic acid with gaseous "nitrous acid" (NgO^) and obtained a precipitate which he recognized as the first diazo compound.3.

(1) P. Griess, Ann., 106, 123 (1858); ibid., 113, 201 (i860).

He called the material diazodinitrophenol; today it is named 2 3 ,5-dinitrobenzene-l,2 -diazooxide.

(2) Compounds of this class are frequently referred to as quinone diazides.

Structures I and II depict the parent ortho and para diazooxides; la and Ila are important resonance contributors to 3 the actual hybrid structure. ’

(3) B. Glowiak, Bull. Acad. Polon. Sci., 8, 1 (i9 6 0); R. J. W. Le Fevre, J. B. Sousa, and R. L. Werner, J. Chem. Soc., *f686 (195*0, C. Anderson, R. J. W. Le Fevre, and I. R. Wilson, ibid., 2082 (19^9).

(*0 L. C. Anderson and M. J. Roedel, J. Am. Chem. Soc., 67,. 955 (19^5).

The parent benzenediazooxides (I and II) were first 5 synthesized in 1896 though the ortho isomer was not isolated as a solid. In the naphthalene series the 1,2- and 2,1-diazooxides 2

(5) A. Hantzsch and W. B. Davidson, Ber., 29, 1522 (1896).

a la

II H a were reported^ as early as 189^+ whereas the 1,^-isomer was not

(6) E. Bamberger, Ber., 27, 679 (189*0 •

4 described until 19^5 • Phenanthrene-9,10-diazooxide was first 7 prepared in 1957* There are no examples reported of syntheses

(7) (a) M. P. Cava and R. L. Litle, Chem. and Ind., 367 (1957); (b) M. P. Cava, R. L. Litle, and D. R. Napier, J. Am. Chem. Soc., 80, 2257 (1958). of anthracene-9,10-diazooxides; in the present study the parent

10-diazoanthrone has been synthesized and its chemistry studied. In general the diazooxides are soluble in mineral acids, existing in such as phenolic diazonium salts, and are regenerated by base. Simple diazooxides undergo the standard coupling re actions of diazonium compounds to yield azo dyes; occasionally they are explosive; and they decompose with loss of nitrogen when exposed to light.

The above general properties suggest that diazooxides should have commercial value. Indeed, the photographic industry has utilized their photosensitivity in the manufacture of copying machines and printing plates. They have also been used in the dye industry and have found limited use in the manufacture of explosives•

Due to the commercial value of diazooxides a great number of such compounds have been prepared. Only two general methods have been found, however, for their synthesis. The classical method (Equation 1) involves diazotization of the corresponding ortho- or para-aminophenol to give the diazonium salt which is

NaNO

neutralized with base to yield the diazooxide. In the second method (Equation 2) the diazooxide is formed by basic decompo sition of the quinone monotosylhydrazone. The latter method was 8 7 9 first discovered in 1 9 2 6; it has not been until recently, ’ (8) W. Borsche and R. Frank, Ann., ^50, 75 (1926).

(9) W. Ried and R. Dietrich, Ber., 9^;, 387 (1961). however, that this reaction has been exploited and found to be fairly general for syntheses of diazooxides.

0 0 C-H-SO-NENH (2) y* u U r -j

0 N-NHSO-C-H, N

In that diazooxides exist in acid solution primarily as diazonium salts,their chemistry in such media approximates

(10) L. A. Kazitsyna et_al., Zh. Obshch. Khim., 33, 223 (1963); see Chem. Abstr., 5 8, 13299 (1963). that of diazonium compounds; thus they undergo coupling, re duction, etc.

Tetrabromo-lj^f-benzoquinone has been prepared’*''*' by re-

(11) H. H. Hodgson and C. K. Foster, J. Chem. Soc., 581 (19^2). action of 3*5-dibromobenzene-l,^-diazooxide with bromine in hot acetic acid. Replacement of the diazo function by a keto group 12 13 also occurs upon photolysis or thermolysis of para-diazooxides in the presence of nitrobenzene; nitrosobenzene is also formed in this reaction. 5

(12) J. K. Stille, P. Cassidy, and L. Plummer, J. Am. Chem. Soc., 8^, 1518 (1963).

(13) M. J. S. Dewar and A. N. James, J. Chem. Soc., 4265 (1958).

The conversion of quinone tosylhydrazones by bases to the 14 corresponding diazooxides is reversible. Several benzene-1,4-

(14) W. Pied and R. Dietrich, Ann., 649, 57 (1961). diazooxides have been converted to their tosylhydrazones (Equation

3 ) and it has been suggested that the latter probably exist in the tautomeric phenolic form (III) in the benzene series.

OH 0

+ HS02 C?H7 ------► (3)

0 N=N N, so2 c7h7

III

The electropositive character of the terminal nitrogen of para-diazooxides appears responsible for many reactions. The nitrogen of diaryldiazomethanes is displaced by diazooxides to give azines in high yields (Equation 4 ) . ^ Similarly, coupling

(15) R. Huisgen and R. Fleischmann, Ann., 623, 47 (1959). of diazooxides with triphenylphosphine gives quinone phosphazines 6

N2 II -N, 'O' + Ar-C-Ar O' (4) N, N. N II X=C1 or Br Ar-C-Ar

• ^ 1 6 (Equation 5)« The latter reaction has been studied fairly

(l6) W. Ried and H. Appel, Z. Naturforsch. Pt. B, 15, 684 (i9 6 0); idem., Ann., 646, 82 (1961).

I I PPh, (5)

N N-PPh. e © extensively and the reactivities of various diazooxides have been correlated with the infrared wavenumbers of their diazo absorp tions. The wavenumber was taken as a measure of the relative contributions of IV and IVa to the actual hybrid. Thus, as the

N o " N. 2 n 2 © IV IVa wavenumber increased, the contribution of IVa increased, and the tendency to couple increased. 17 One example has been reported of coupling of the oxide function with an electron deficient center. Thus, reaction of 7

(17) T. Kunitake and C. C. Price, J* Am. Chem. Soc., 8 5, 761 (1963).

3,5-dii»ethylbenzene-l,4-diazooxide in dioxane with excess boron trifluoride etherate gives the crystalline complex V.

0*BF

• 2H20

Considerable attention has been directed to photolysis and thermolysis of ^-diazooxides in various reaction media. 3.8 Photolysis of an aqueous solution of naphthalene-1,4-diazooxide

(18) J. de Jonge and R. Dijkstra, Rec. Trav. Chim., 68, 426 (1949). gives a poor yield of naphthalene-1,4-diol. Irradiation of para- 19 diazooxides in primary alcohols gives fair yields of arylalkyl

(19) 0. Stts, K. Moller, and H. Heiss, Ann., 5 9 8, 123 (1956).

ethers (Equation 6); in aromatic solvents 4-arylphenols are ob

tained in yields generally less than 50& (Equation 7)» 8

0 ROH (6) N„

0 0 ArH (7) N,

13 20 21 Dewar and his colleagues ’ ’ studied the thermolysis

(20) M. J. S. Dewar and A. N. James, J. Chem. Soc., 917 (1958).

(21) M. J. S. Dewar and K. Narayanaswami, J. Am. Chem. Soc., 8 6, 2422 (1964). of 3»5-dihalobenzene-l,4-diazooxides (VI a,b) in a variety of solvents, The following results were obtained:

0 -- 0 -- x x y Y XT V N2 ' Ar VI a, X=C1 b, X=Br VII VIII

1. Thermolysis of VI in chlorobenzene, ortho- or meta- dichlorobenzene, or bromobenzene yielded molecular halogen and polymers consisting of the recurring units VII and VIII. 2. Thermolysis in benzene, fiuorobenzene, anisole,

N,N-dimethylaniline, methyl benzoate, or benzonitrile resulted in high yields of biphenyls (IX).

3. Thermolysis of VI in any of the aforementioned sol vents containing 1% methanol or ethanol resulted in high yields of biphenyls (IX) with no polymer formation.

k. When VI was thermolysed in the presence of 1,1- dideuteroethanol no deuterium could be detected in the product nor did the recovered alcohol contain detectable hydrogen in the

1- position. ^-Butanol exhibited the same effect as that of primary alcohols.

5. Competitive experiments in mixed aromatic solvents showed that there is little selectivity of the diazooxide in choosing between the solvents to form biphenyls. The results indicated that the reagent is electrophilic but far less selec tive than the nitronium ion.

6. The selectivity in choosing the position of aromatic substitution is very pronounced, the reagent appears more selec tive than the nitronium ion.

7. A competitive experiment using a mixture of 1,3*5- trideuterobenzene and benzene as aromatic substrates showed the 1 0 deuterated molecule to be substituted randomly and at a rate no different from that of pure benzene.

These results were explained in terms of four possible intermediates (X-XIII). It was explained that carbene X and

1I> © t

X XI XII XIII zwitterion XI are chemically indistinct resonance hybrids and that singlet diradical XII is in rapid equilibrium with X XI. In solvents containing heavy atoms (chloro- and bromobenzenes) the forbidden spin crossover to the triplet diradical XIII is facili tated and polymerization in such solvents proceeds via a radical mechanism involving this species. The effect of added alcohol is to hydrogen bond with the initially formed singlet carbene

(X *-* XI), stabilizing it against conversion to the diradical species (XIII), enhancing its electrophilicity, and thus allowing

for electrophilic substitution.

The mechanism suggested for this electrophilic substi

tution is shown in Equation 8. To explain the lack of selec tivity toward various benzene derivatives, it was postulated that initial spiran (XIV) formation is rate determining, highly exo

thermic, and of low activation energy. This argument allows for retention of high selectivity .in positioning of the aryl group

on the aromatic substrate. Based on the reaction in benzene- 11

XV trideuterobenzene it was argued that k ^ ^ k^, an argument that is unsound unless XIV and XV are assumed to be in equilibrium; the authors did not make this assumption.

When para-diazooxides are thermolyzed in chloro- or bromobenzene,.the product contains the biphenyl XVI derived from displacement of halogen from the solvent. This product is found 21 17 whether alcohol is present or not. It is also notable that

OH CH.

XVI XVII XVIII

^-hydroxy-3*5-dimethylbenzenediazonium chloride (XVII) is obtained in low yield by photolysis or thermolysis of 3i5-

1,^-diazooxide in chlorobenzene, 1,2-dichloroethane, carbon 17 tetrachloride, or dichloromethane. It has been suggested that the diradical XVIII gives rise to this product. 12

A nearly 1:1 copolymer of structure XIX is formed when the respective diazooxide is photolyzed or heated in tetrahydrofuran. An ionic mechanism based on the intermediate 12 17 zwitterion XI has been postulated. *

XIX

Electron spin resonance spectra have been determined for the intermediates produced upon photolysis of some simple para- 22 diazooxides. In all cases studied, the ground states were ob-

(22) E. Wasserman and E. W. Murray, ibid., p. ^203. served to be triplets (XIII) with one electron in the -ir-system and one in the a~-orbital at C-l. DISCUSSION OF RESULTS

9,10-Anthraquinone does not react readily with amine functions because of steric and electrical factors; anthraquinone oxime and dioxime are formed, however, by the action of hydroxyl- 23 amine in pyridine on anthraquinone. This reaction is probably

(23) J. Meisenheimer and E. Mahler, Ann., 3 0 8, 191 (193*0 • base-catalysed, proceeding through a more nucleophilic anion of 2k hydroxylamine. Imine derivatives of anthraquinone such as the

(2k) D. E. Pearson and 0. D. Keaton, J. Org. Chem., 28, 1557 (1963). phenylhydrazone have been prepared by reaction of the respective 25 hydrazine with 10,10-dibromoanthrone (XX).

(25) K. H. Meyer and K. Zahn, Ann., 396, 152 (1913).

It has now been found that the monotosylhydrazone (XXI) and the monohydrazone (XXII) of anthraquinone can be prepared from 10,10-dibromoanthrone and either of these may be readily converted to 10-diazoanthrone (XXIII) (Equation 9). The method of choice for synthesis of XXIII is through the tosylhydrazone; the yield of diazo compound from 10,10-dibromoanthrone is 76$.

13 Late in the preparation of this manuscript, synthesis of 10-diazoanthrone was reported CM. Regitz, Ber., 97, 2742 (1964)] by reaction of anthrone with £-toluenesulfonylazide in the presence of piperidine; the crude yield was 94%. 10-Diazo- anthrone was converted to anthraquinone azine by the action of piperidine/pyridine and to 10-acetoxyanthrone by refluxing acetic acid. Reaction of 10-diazoanthrone with formic acid and with hydrochloric acid gave 10-formyloxy-10,10’-bianthrpne and 10-chloro-10,10'-bianthrone respectively. Anthraquinone tri phenylphosphazine was obtained by reaction of 10-diazoanthrone with triphenylphosphine in acetonitrile and was hydrolyzed to anthraquinone monohydrazone by refluxing in aqueous ethanol under acetic acid catalysis.

Although the hydrazone XXII is quantitatively oxidized to 10- diazoanthrone, it could be prepared in only 40% yield; 10-bromo-

0 NH2NHTo s NaOH

N-NHTos

(9)

Br Br XX XXIII

HgO

N-NH

XXII

10,10'-bianthrone (XXIV), possibly formed via Equation 10, is a

side product and is the major product at 0° in this reaction. 26 Debromination of active halides by hydrazine is well documented

and 10-bromoanthrone is converted to XXIV by a variety of amines. 15 0

NH-NH ,Br (10)

Br Br Br

0 XXIV

(26) C. C. Clark, "Hydrazine,” Mathieson Chemical Corpo ration, Baltimore, Maryland, 1953* P* 103*

(27) E. B. Barnett, J. W. C. Cook, and H. H. Grainger, J. Chem. Soc., 121, 2059 (1922).

28 The Forster reaction of anthraquinone oxime, a rela tively available material, is an attractive route for synthesis

(28) M. 0. Forster, ibid., 107, 260 (1915)• of 10-diazoanthrone (XXIII). Although 10-diazoanthrone is ob tained, anthraquinone monoimine (XXV) is also a major product

(Equation 11). Imines have not been reported previously in re action of oximes with chloramine. Initial carbon amination of anthraquinone monooxime to give the intermediate XXVI, followed by loss of [HNO] explains the formation of anthraquinone mono imine though other mechanisms can be written. 16

XXIII (1 1 )

N-OH N-H

XXV

N=0 XXVI

10-Diazoanthrone decomposes slowly in refluxing benzene*

However, in the presence of copper powder the reaction proceeds smoothly as shown in Equation 12. Anthraquinone azine (XXVII) may be formed by bimolecular reaction of XXIII with displacement 15 of nitrogen or by coupling of 10-anthronylidine, the inter- 29 mediate carbene, with XXIII. Displacement of nitrogen in XXIII

(29) The term "carbene” is used for simplicity to denote the intermediate formed by loss of nitrogen from diazooxides. Structures XII-XV depict plausable intermediates, three of which are notr truly carbenic. The nature of the carbene, 10-anthronylidene, will be considered later in this discussion.

(12) Ph-H

0 0 XXIII XXVII XXVIII by 10-anthronylidene explains the formation of -bianthrone (XXVIII) though the latter may also arise by a carbene 17

coupling mechanism. Anthraquinone azine (XXVII) is not converted

to XXVIII under the reaction conditions.

Photolysis of 10-diazoanthrone in benzene (Equation 13)

produced 10,10'-bianthrone (XXIX) as the major product. The

formation of biphenyl shows that reaction involves formation of

the carbene which abstracts hydrogen from solvent to give the

phenyl radical. The resulting anthrone radical may then dimerize

to XXIX or couple with a phenyl radical to give 10-phenylanthrone

(XXX). -Bianthrone (-XXVIII) does not serve as an inter

mediate in this reaction, for under the photolytic conditions

XXVIII is not converted to XXIX. When 1% ethanol was added to

the reaction mixture, the radical mechanism was not suppressed

for XXIX was isolated in k7% yield. However, anthraquinone azine

was not formed and the yield (8.5%) of biphenyl was markedly

Ph-Ph 36% + XXIII h V + (13) Ph-H

XXVII

XXIX

diminished. It appears that ethanol serves as a ready source of

hydrogen atoms. The gas evolved in this experiment was well in

excess of theoretical nitrogen; it is postulated that the radical

derived from alcohol proceeds to acetaldehyde which is photolyzed 18 to carbon monoxide and methane (Equation 1*0. The gaseous products were not analyzed.

“H * A CH^’CHOH ---- »• CHjCHO - — -»» CH^ + CO (1*0

The abstraction of hydrogen from benzene appears to be a relatively slow process. When 10-diazoanthrone was photolyzed in benzene with one equivalent of triphenylphosphine present

(Equation 15)» anthronylidenetriphenylphosphorane (XXXI) was produced in Bk% yield. Anthraquinonetriphenylphosphazine (XXXII), as derived from reaction of 10-diazoanthrone and triphenylphos phine (Equation 16), is not an intermediate since it is not con verted to the ylide under photolytic conditions.

In solution, phosphazines are in equilibrium with their parent diazo compounds and triphenylphosphine.^ Such would

(30) H. J. Bestmann and L. GSthlich, Ann., 655. 1 (1962).

account for the products observed in the thermolysis of anthraqui none triphenylphosphazine (XXXII) in benzene (Equation 17). Azine

formation is more rapid here than when 10-diazoanthrone is

thermolyzed in benzene alone. Thus, it appears that XXXII is

more readily susceptible to nitrogen displacement by XXIII than

is XXIII itself. Ylides have been proposed as intermediates in

conversions of diazo compounds to azines.^ Such a postulate

(31) W. R. Bamford and T. S. Stevens, J. Chem. Soc., *f675 (1952); E. E. Schweizer, G. J. O'Neill, and J. N. Wemple, J. Org. Chem., 29, 17*0 (196*0. 19

XXIII A 2/ PPh3 , Ph-H (15)

PPh

XXXI

dark XXIII PPh,, PhCH, (16)

N-N XXXII PPh. seems unnecessary in the present system.

PhH> Azine(XXVII) + PPh3 + XXIII (17)

N = PPh.

Thermolysis of 10-diazoanthrone in mesitylene at 120

proceeded readily to give 10,10'-bianthrone (XXIX) in 30% yield

along with small amounts of 10,10-bis(3»5-dimethylbenzyl)

anthrone (XXXIII). Apparently the thermally produced carbene

abstracts a benzylic hydrogen atom from mesitylene and the

anthronyl radicals couple to form 10,10'-bianthrone; the mesityl

radicals may then couple with carbene to form XXXIII. The chemistry of anthronylidenetriphenylphosphorane

(XXXI) has been investigated briefly. Attempts to synthesize the phosphorane by standard procedures were largely unsuccessful.

When 10-bromoanthrone was treated with triphenylphosphine in chloroform, a yellow crystalline compound, which exhibited no carbonyl absorption in the infrared, was produced in 6l% yield.

The product was readily hydrolyzed to anthrone and triphenyl phosphine oxide and is assigned the structure XXXIV, anthracene-

9-oxytriphenylphosphonium bromide. Reaction of 10-bromoanthrone and triphenylphosphine in benzene gave a mixture of solids which exhibited a weak carbonyl absorption and is believed to be a mixture of the 0- and C-phosphonium bromides (XXXIV and XXXV).

e & 0-PPh^ Br 0

XXXIV 21

Upon treating this mixture with potassium t-butoxide in benzene, anthronylidenetriphenylphosphorane (XXXI) was obtained in low yield. Ample precedent exists for formation of O-phosphonium bromides in related systems and in the present case the mechanism probably involves initial attack' of triphenylphosphine on bromine 32 to displace the anthrone anion.

(32) B. Miller, ibid., 2 8 , 3^5 (1963); I. J. Borowitz and R. Virkhaus, J. Am. Chem. Soc., 8£, 2183 (1963) and refer ences cited therein.

Anthronylidenetriphenylphosphorane is unreactive toward acetone and reacts only slowly with benzaldehyde. Both meta- and para-nitrobenzaldehydes, however, react readily to give the respective benzylideneanthrones (XXXVI a,b) in high yields.

Experimental comparisons show that anthronylidenetriphenylphosphorane is more stable than fluorenylidenetriphenylphosphorane

(XXXVII).55

(33) A. W. Johnson, J. Grg. Chem., 24, 282 (1959)•

✓ CN PPh Ar

XXXVI a, Ar = m-nitrophenyl XXXVII b, Ar = £-nitrophenyl 3if It has been reported that XXXVIa exhibits "pronounced thermochromism." It is presently found that neither XXXVIa nor 35 b is thermochromic.

(3*0 V. M. Ingram, J. Chem. Soc., 2318 (1950).

(35) For a review on thermochromism see J. H. Day, Chem. Rev., 6^, 65 (1963).

An attempt to prepare anthronylidenetriphenylphosphorane by trapping the carbene, thermally produced in xylene, with triphenylphosphazine was unsuccessful. The product isolated was

10,10'-bianthrone (XXIX). Similarly, attempted copper catalyzed decomposition of 10-diazoanthrone in benzene in the presence of triphenylphosphine did not give the ylide but, instead, a 60% yield of anthraquinonetriphenylphosphazine (XXXII) was obtained.

In this case it appears that phosphazine formation is fast at benzene reflux and the compound is stable under reaction con ditions. Further, the phosphazine-diazo equilibrium, discussed earlier, apparently favors the phosphazine and, therefore,

generation of carbene is unfavored because of the low concen

tration of 10-diazoanthrone.

When 10-diazoanthrone was warmed in acetic acid, nitrogen was evolved steadily and 10-acetoxyanthrone (XXXVIII) was iso

lated in high yield. Initial protonation of oxygen or carbon

could lead to product via carbonium ion processes (Equation 18). 23 OH

0 H OAc

XXXVIII

Aliphatic diazo compounds generally react with 9,10-

•Z C 'Z ry phenanthrenequinone to yield dioxoles * though diazomethane

(36) N. Latif and I. Fathy, Gan. J. Chem., 37, 863 (1959).

(37) A. Schonberg and G. Schutz, Ber., 9£, 2386 (1962). can react by addition to one of the carbonyl groups to give the 38 ketoepoxide. It has been found in the present study that

(3 8) B. Eistert, G. Fink, and R. Wollheim, Ber., 91* 2710 (1958). phenanthrenequinone reacts slowly with 10-diazoanthrone in refluxing benzene to give a yellow, high-melting crystalline com pound which is assigned the dioxole structure, XXXIX. The pos sibility that the product is the isomeric ketoepoxide (XL) is ruled out on the basis of its infrared spectrum. The ketoepoxide should show two distinct carbonyl absorptions; the anthrone carbonyl should be above 6 and that of phenanthrone below XXXIX XL

6 >f ipkg reaction product exhibits sharp absorption at

6.01 M . The dioxole XXXIX might be expected to display ab sorptions near this wavelength for the anthrone carbonyl and for 37 the vinyl ether function;"^ apparently the absorptions for these groups coincide.

Boron trifluoride does not react with 10-diazoanthrone in di.oxane to give a complex analogous to structure V as derived

from 3»5“di!nethylbenzene-l,if-diazooxide. Loss of nitrogen is effected and anthraquinone is obtained. The reaction was not

further investigated.

Nitrosobenzene reacts with 10-diazoanthrpne at room tem perature in benzene to give N-phenylanthraquinone oxime (XLI) in

72% yield. The product is assigned the nitrone structure rather

than the isomeric oxazirane structure (XLII) because of its

0 0 25 orange color. Analogous nitrones have been obtained previously from reactions of diphenyldiazomethane and 9-diazofluorene with 39 nitrosobenzene. '

(39) A. W. Johnson, J. Org. Chem., 28, 282 (1963)#

Sulfenes have been postulated as intermediates in re actions of sulfur dioxide with diazo compounds to give sulfones ZfO (Equation 19); their intermediacy has been demonstrated in 4l other reactions. The similarity of N-sulfinylaniline to sulfur

(40) H. Staudinger and F. Pfenninger, Ber., 49, 1941 (1916); see also G. Hesse and E. Reichold, Ber., 90, 2101 (1957) and references therein.

(41) J. F. King and T. Durst, J. Am. Chem. Soc., 86, 287 (1964); W. E. Truce, R. W. Campbell and J, R. Norell, ibid., p. 2 8 8.

> so ° Y ° / \ 2 Ph-C-Ph — Ph-C-Ph ---- ► Ph2C----CPh2 (19) dioxide suggested the possibility of it reacting with diazo com pounds. However, after refluxing equivalents of N-sulfinylaniline and 10-diazoanthrone in benzene for four hours the diazo compound was recovered unchanged.

Spiro Canthrone-10,1*-cyclopropane] and two of its 42 derivatives have been reported. They were obtained by reaction

(42) A. Mustafa and M. K. Hilmy, J. Chem. Soc., 1434 (1952). 26 of 10-methyleneanthrone with diazomethane, diazoethane, and diphenyldiazomethane respectively. It is presently found that suitably activated and nonhindered alkenes react with 10- diazoanthrone with displacement of nitrogen to give spiro-

[anthrone-10,1’-cyclopropanes]. Thus, by reactions of 10- diazoanthrone with acrylonitrile, methyl vinyl ketone, methyl

0 0 0 0

CH PhC CiN H C=0 l 0-CH, Ph XLIII XLIV XLV XL VI methacrylate, and trans-l,2-dibenzoylethylene, compounds XLIII-

XLVI were prepared in good yields. Though these were not further investigated, they appear as quite stable, colorless, crystalline materials. The reactions were conducted in refluxing benzene and evolution of nitrogen was complete in 7 to 48 hours.

The n. m. r. spectrum of XLV exhibits two-methyl singlets

(6.95 7* , 0-methyl; 8 .9 8 7* , C-methyl) and a quartet (7*63 7") for the cyclopropyl hydrogens; that of XLVI shows one cyclopropyl singlet (5«6l 7*) in accord with the structure assigned. Based 43,44 on mechanism considerations and the work on similar compounds,

(43) L. I. Smith and K. L. Howard, J. Am. Chem. Soc., J£, 159 (1943).

(44) L. Horner and E. Lingnau, Ann., 391. 21 (1955)* XLVI is assigned the trans structure. Formation of cyclopropanes from diazo compounds and electronegatively substituted alkenes if5 proceeds by an ionic mechanism as depicted in Equation 20.

(^5) W. M. Jones, T. H. Glenn, and D. G. Baarda, J. Org. Chem., 28, 2887 (1963) and references therein. VB ON- N C-' 2 I 0CN- B E E E -N. I© + Nc = or * (20) n 2© z VE N C- II I N-C-Z I

k k 9-Diazofluorene has been found to react with £-benzoquinone, 1,^-naphthoquinone and quinizarin quinone to yield indazoles of the general structure XLVII along with "nitrogen free" products (less than 5% yield). Though the minor products

HO 0

XLVII XLVIII were further described (ketonic, empirical formulas, color, etc.), their structures were not assigned. It was noted that XLVII does not yield the' ''nitrogen free" product upon thermolysis. Since then, compounds of the general structure XLVIII have been syn- 47 thesized by other routes and characterized. It has been

(46) See also A. R. Bader and M. G. Ettlinger, J. Am. Chem. Soc., 7£, 730 (1953).

(47) E. J. Corey and H. J. Burke, ibid., 78, 174 (1956); J. F. Garden and R. H. Thomas, J. Chem. Soc., 2851~Tl957); see also F. M. Dean, P. G. Jones, and P. Sidisunthorn, ibid., 5186 (1962). presently found that 10-diazoanthrone reacts with |>-benzoquinone at room temperature to give the spiroindazole XLIX and the spirocyclopropane L in low yields; a 36% yield of L is obtained at 80°

The n. m. r. spectrum of L shows two singlets (6.77 "T , aliphatic

3*37 7*, vinylic) and an aromatic multiplet. The intermediate LI may account for XLIX by enolization and for L by loss of nitrogen

It is probable that the "nitrogen free" compounds isolated by 44 Horner and Lingnau are cyclopropanes of general structure

XLVIII.

0 o 0

0 XLIX L LI

The reaction of 10-diazoanthrone with diethyl azodicarboxylate proceeds readily in refluxing benzene to give a 72% 29 yield of 1 ’,2,-dicarboethoxyspiroCanthrone-10,3'-diaziridine] 2f8 (LII). An analogous structure (LV) has been proposed for the

(*f8) H. Staudinger and A. Gaule, Ber., ^9, 196l (1916).

N N - N Et02c' 'N-C02Et / \ EtO*C CO_Et O

LII LIII LIV product from reaction of diethyl azodicarboxylate with diazofluorene. However, such structures have been opened to question by the demonstration that analogously prepared compounds, exemplified Zf9 by LIV, apparently exist in the ring-open form shown. The

(^9) R.-Huisgen, R. Fleischmann, and A. Eckell, Tetra hedron Letters, No. 12, 1 (i9 6 0); R. Huisgen and A. Eckell, ibid., p. 5.

assignment of structure LII, as opposed to the ring-open structure

LIII, is based on the n. m. r. spectrum. LII should display

equivalent ethyl functions; a single ethyl pattern consisting of

the methylene quartet at 5*82 T and the methyl triplet at 8 .8 7 7* k & is observed. It is reported that compound LV rearranges to

hydrazone LVI when heated (I5O-I8O0) above its melting point

(138-1390). The possibility of LII actually being N,N-dicarbo- 30 methoxyanthraquinone hydrazone (LVII) is real and cannot at present be discounted.

N-N / I N-C02Et Et02C C02Et CO-Et LV LVI

N-C02Et

LVII i02Et

Reaction of dimethyl acetylenedicarboxyDate and 10- diazoanthrone results in k 1t5 ,-dicarbomethoxyspiro[anthrone-10,3'- pyrazole] (LVIII; yield). Photolysis in ether converts LVIII

N C-CO-CH. II 2 N c -c o 2c h 5

LVIII LIX

to 1 1,2'-dicarbomethoxyspiroCanthrone-lOjJ'-cyclopropene] (LIX) with loss of nitrogen. Photolysis of pyrazoles has been utilized previously to produce cyclopropenes^ and benzocyclopropenes 52 The infrared spectrum of LIX displays the characteristic ring

vibration of cyclopropenes at M . The n. m. r. spectrum 31

(30) G. L. Closs and W. Boll, Angew, Chem*, Intern* Ed. Engl., 2, 399 (1963); G. Ege, Tetrahedron Letters, 166? (1963).

(31) R. Anet and F. A* L. Anet, J. Am. Chem. Soc., 86, 525 (196*0.

(52) G. L. Closs and L. E. Closs, ibid.. 8 3, 1003 (1961). exhibits a singlet methyl peak (6.20 7"*) and an aromatic multiplet in the ratio 6:8. 53 Ethyl diazoacetate adds to benzyne to give the indazole

LX; similarly, benzyne reacts with o<-diazoketones to give

H I

5*f indazoles in high yields. In the present study benzyne has

(53) R* Huisgen and R. Knorr, Naturvissenshaften, *f8, 716 (1961).

(5*0 W. Ried and M. Schon, Angew. Chem., 76, 98 (196*0. been found to react with 10-diazoanthrone to produce spiroEan- throne-10,3'-indazole] (LXI) in 87% yield (Equation 21). The reaction may be regarded simply as a 1,3 dipolar addition of benzyne to the diazo function. Photolysis of LXI afforded quantitative loss of nitrogen but the product mixture could not be characterized. 32

BONO

(21) Cf^ NH,

LXI

One of the objectives of this investigation was to extend the chemistry of 10-diazoanthrone to other diazooxides. Some success has been attained toward this end.

J-Methylnaphthalene-l,*)— diazooxide (LXII) reacts with trans-1,2-dibenzoylethylene (Equation 22) to give the spiro- 0 II CH P h - C ^ H -N CH II C (22) h ' SC-Ph M N 0 C-Ph C=0 H LXII I Ph LXI 11 cyclopropane-naphthalenone LXIII in yield; the reaction oc curred during one week at room temperature. The stereochemistry about the cyclopropane ring in LXIII is unequivocally demon strated to be trans by the n. m. r. spectrum. Either of the two possible cis products have equivalent protons on the 3-membered ring whereas in the trans adduct the hydrogens are nonequivalent; nonequivalence is demonstrated by the quartet signal for the cyclopropyl hydrogens (5*5^ 7*). The balance of the spectrum is wholly in agreement with structure LXIII. LXIII is the first C=0 H LXIV I Ph LXV spirocyclopropane-naphthalenone to be described.

Synthesis of spiro(2,5)octa-l,4-diene-3-one (LXIV), a 55 highly reactive intermediate, has been previously recorded. x

(55) Baird and S. Winstein, J. Am. Chem. Soc., 8 5. 567 (1963).

It is now found that 3i5-dimethylbenzene-l,4-diazooxide reacts with trans-1,2-dibenzoylethylene to give a stable derivative of

LXIV, 2,4-dimethyl-trans-6,7-dibenzoylspiro(2,5)octa-l,4-diene-

3-one (LXV). The product is obtained in 43% yield after stirring the reactants for four weeks in benzene at room temperature. The infrared spectrum of LXV displays carbonyl absorptions at 6.00>*

(benzoyl) and 6.14 H (dieneone). The n. m. r. spectrum shows singlets of proper area for the methyl, cyclopropyl and vinyl hydrogens at 8.07 T » 5*56 T and 3»29 T* respectively. The benzoyl groups are again assumed to be trans about the cyclo propane ring.

Benzyne adds to 3-methylnaphthalene-l,4-diazooxide to give 3'-methylspiro[indazole-3,4'-naphthalene-1’-one] (LXVI) in

47% yield; the reaction is not as clean as that with 10-diazo- 3^

LXV I anthrone. Photolysis of LXVI effected loss of nitrogen but again an unseparated mixture of products was obtained. 56 Copper salts decompose diazo compounds in the presence

(5 6) G. Wittig and M. Schlosser, Tetrahedron, 18, 1023 (1962). of triphenylphosphine to give triphenylphosphoranes in modest yields. Carbenes, as generated by other methods, also react with 57 triphenylphosphine to yield ylides. Though synthesis of

(57) Seyferth, S. 0. Grim, and T. 0. Read, J. Am. Chem. Soc., 82, 1511 (i960). anthronylidenetriphenylphosphorane (XXXI) from 10-diazoanthrone was successful, a similar attempt to prepare phosphorane LXVIII from 3-methylnaphthalene-l,if-diazooxide and triphenylphosphine did not succeed (Equation 23); 2-methyl-1,^-naphthoquinone-^- triphenylphosphazine (LXVII) was obtained. A distinct color change upon mixing the reagents for photolysis suggested that

the phosphazine LXVII was formed quickly; LXVII is apparently

stable to irradiation because the parent diazo compound loses 35 nitrogen rapidly under the reaction conditions without tri phenylphosphine present. 10-Diazoanthrone shows a diazo ab sorption at 2070 cm."’'*' in the infrared while LXII absorbs at

2090 cm.-^ Based on the correlations of Ried and Appel^ (see

CH, + PPh.

N-N=PPh

LXVII LXII (23) CH

PPh

LXVIII page 6) it is then expected that LXVII should form more rapidly than anthraquinone triphenylphosphazine (Equation 16).

Phenanthrenequinone-9,10-diazooxide .(LXIX) does not react with acrylonitrile in refluxing benzene. The reaction product was 2-fluorenylidenephenanthroC9»10]“l*3-dioxole (LXX); 58 the dioxole has be«n obtained by others upon thermolysis of

LXIX.

(58) W. Ried and R. Dietrich, Ann., 639, 32 (1961). 36

LXIX LXX

7-Diazo-8-acenaphthenone (LXXI) reacted readily with benzyne and with dimethyl acetylenedicarboxylate (Equations 2*0 to give high yields of compounds analyzing as adducts of LXXI with the respective reagents.

Adduct

LXXI I (2*0

\CH( O 2 C - C ^ V . LXXI -► Adduct

LXXIII

The adduct LXXII, rec*“oran6e» n°t fected by irradiation in benzene through quartz, and is soluble in aqueous base being regenerated by acid. Its insolubility thwarted attempts to obtain a good n. m. r. spectrum. A strong band at 5.86 is present in the infrared spectrum. Structure

LXXIV is tentatively assigned to adduct LXXII, LXXIV

The adduct LXXIII, (C^gH^2N20^)» Is yellow and melts without decomposition at 201-203°. Its n. m. r. spectrum shows aromatic protons (area 1) and a sharp aliphatic singlet at 5*98 "T*

(area 1). The infrared spectrum exhibits bands at 5.75 and 5»83-*f

Me02CK ^C02Me MeO.C CO-Me C 2 \ / ^ II CSC. c w N N H / ll / II N

LXXV LXXVI LXXVII

Possible structures for LXXIII are depicted by LXXV-LXXVII.

No reaction occurred upon refluxing 7-diazo-8-acenaphthenone (LXXI) with acrylonitrile in methylene chloride for 29 hours•

Certain of the thermal and photochemical experiments with 10-diazoanthrone may be rationalized in terms of the multi plicities of the intermediate 10-anthronylidene. Singlet carbene is depicted by LXXVIII; triplet carbene by LXXIX. Based on the 11- © LXXVIII

LXXIX

e. s. r. studies on related carbenes it cam be assumed tbat 10- 22 59 anthronylidene has the triplet ground state, LXXIX. The high selectivity of the carbene produced by copper catalyzed

(59) Wasserman et_al., J. Am. Chem. Soc., 86, 2304 (1964). decomposition of 10-diazoanthrone in benzene (Equation 12) may be explained by invoking an intermediate carbene-copper complex.^

(60) K. P. Kopecky, G. S. Hammond, and P A. Leermakers, ibid., 83, 2397 (1961). *

Assuming that the thermally or photolytically excited 10- diazoanthrone (singlet) loses nitrogen to produce singlet carbene

LXVIII which sooner or later spin-inverts to the triplet state

LXXIX, the following interpretations may be proposed:

1. Photolysis in benzene (Equation 13) gives singlet carbene which spin-inverts to the diradical triplet LXXIX which 39 then reacts by a radical mechanism to produce biphenyl and

10,10'-bianthrone along with 10-phenylanthrone.

2. Photolysis in benzene in the presence of triphenyl phosphine (Equation 15) gives singlet carbene which is trapped by singlet triphenylphosphine before spin-inversion can occur.

The yield of anthronylidenetriphenylphosphorane is 84% but is reduced to 21% when toluene is employed as solvent. No 10,10'- bianthrone was detected in the toluene experiment and it is believed that a singlet carbene insertion reaction is responsible for the yield decrease; the product of such a process, 10- benzylanthrone, has not been investigated in the reaction mixture.

3. Photolysis in pure toluene gave a 21% yield of

10,10'-bianthrone (triplet product) as opposed to 44% in benzene.

Again a singlet insertion process is postulated to explain the yield decrease. The formation of the triplet product in toluene suggests that spin-inversion is competitive with singlet in sertion. EXPERIMENTAL

Melting Points:

All melting points were taken in open capillaries in a

Hershberg apparatus and are uncorrected.

Elemental Analyses;

Elemental analyses were performed by Galbraith Labora tories, Inc., Knoxville, Tennessee, or by Micro-analysis, Inc.,

Wilmington, Delaware.

Infrared Spectra:

All infrared spectra were determined with a Perkin-Elmer,

Infracord recording spectrophotometer. The spectra of solids were recorded as potassium bromide wafers.

Nuclear Magnetic Resonance Spectra;

All nuclear magnetic resonance spectra were obtained with a Varian Associates nuclear magnetic resonance spectrometer,

Model A—60, at ca. b 0 ° using chloroform-d as solvent unless specified otherwise.

Photolysis Apparatus:

Photolyses were effected externally with a Hanovia ^50 watt mercury arc lamp, Type L (679A-10). The reaction vessel consisted of a quartz tube (^.5 x *f00 cm.) having a standard taper joint (2b/k0) into which was. fitted a condenser. Stirring was accomplished magnetically and the temperature was maintained at

^0 or below that of the room by means of a stream of water passed over the photolysis tube. Evolution of nitrogen was monitored by collection over water.

Preparation of 10,10-Dibromoanthrone. ^ — A solution of

(6l) Modification of the procedure of Fr. Goldmann, Ber., 20, 2kj6 (1887). bromine (Mf ml., 0.86 mole) in carbon disulfide (100 ml.) was added dropwise to anthrone (69 g., 0.35 mole) in carbon disulfide

(1^00 ml.). ’Stirring was continued for several hours after ad dition was complete; throughout the reaction nitrogen was passed over the surface of the mixture to sweep out evolved hydrogen bromide.

The mixture was washed once with saturated aqueous sodium thiosulfate. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was diluted with petroleum ether (30-60°, 1600 ml.) and refrigerated overnight to complete crystallization. The product was filtered and washed with petroleum ether; yield: 8? g. (70%), m.p. 1^8-151° (dec.).

Two recrystallizations from carbon tetrachloride (A.E.) gave off- white rhombic prisms of 10,10-dibromoanthrone (63 g.* 50% yield), m.p. 155-1560 (dec. with prior darkening). The material was best stored under nitrogen in a refrigerator.

Preparation of Anthraquinone Monotosylhydrazone (XXI).— 62 A solution of £-toluenesulfonylhydrazide (95 g«» 0.50 mole) in A2

(62) Prepared according to L. Friedman, R. Litle, and W. Reichle, Org. Syn., AO, 93 (I960). anhydrous ethanol (1500 ml.) at 38° was added to a flask charged with finely-ground 1 0 ,10-dibromoanthrone (5 2 .7 g.» 0 .1 5 mole).

After six hours stirring, the reaction mixture, which had not been allowed to go below 35°* was cooled to 5° to complete pre cipitation of the product.

The yellow solid was collected, washed with cold absolute ethanol, and dried in a vacuum desiccator. The crude tosylhydrazone weighed A3 g. (76% yield) and melted around 150° (dec.).

Due to the instability of the product under purification con ditions, it was used without further treatment.

Preparation of the product using benzene as a solvent gave crystalline anthraquinone monotosylhydrazone (XXI) as yellow square rods in low yield, m.p. IA9-I5I0 (dec.).

Anal. Calcd. for C ^ H ^ N ^ S : C, 6 7.'01; H, A.28; N, 7.AA.

Found: C, 6 7.1 6; H, A.07; N, 7.32.

The infrared spectrum of XXI is shown in Figure 1. The } carbonyl absorption of the tosylhydrazone appears at 6.10 m . A shoulder or distinct band between 6.00 and 6 .0 5 M * in the spectrum of the crude product is due to an impurity believed to be 10-bromo-

10,10’-bianthrone (XXIV) and is lost in the subsequent conversion to 10-diazoanthrone.

Preparation of Anthraquinone Monohydrazone (XXII).— A solution of hydrazine hydrate (35 ml., 0 .7 0 mole) in absolute 43

ethanol (600 ml.) at 45° was added to a flask charged with powder-

fine 10,10-dibromoanthrone (24.6 g., 0.0? mole). During 0.5 hour

the temperature was raised to 60° while all of the 10,10-dibromo

anthrone went into solution and product began to separate. Water

(150 ml.) was added and the system was cooled to 5°. Filtration

and drying gave yellow powder (13.2 g.).

The product was heated to reflux in 95% ethanol (500 ml.)

and filtered; 10-bromo-10,10 '-bianthrone (XXIV, 5*3 g»* 32%

yield) remained, m.p. 186-189° (dec.). Crystalline anthraquinone

monohydrazone (XXII, 6.15 g., kQP/o yield) separated upon cooling

the filtrate to 4°, m.p. 174-175° (dec.). Recrystallizations

from ethanol gave brown-orange needles, m.p. 175-176° (dec.).

Anal. Calcd. for C * 75.66; H, 4.54; N, 12.61.

Found: C, 75.50; H, 4.47; N, 12.64.

The infrared spectrum of XXII, shown in Figure 2, exhibits

a carbonyl absorption at 6.12 4 and amine absorptions at 3*0 5,

3.17, 6.31, and 13.6 M .

After four recrystallizations from xylene the 10-bromo-

• lOjlO’-bianthrone, m.p. 186-189° (dec.) (lit.^ 187°), gave the

(6 3) K. H. Meyer and A. Sander, Ann., 396. 133 (1913).

following poor analysis:

Anal. Calcd. for C ^ H ^ B r C ^ : C, 72.27; H, 3 .6 8;

Br, 17.17.

Found: C, 73.49; H, 3*86;

Br, 13.52. kk

When the above reaction was conducted at 0°, a 92% yield of 10-bromo-10,10'-bianthrone was obtained; 95% hydrazine was used but the type of hydrazine does not seem to be critical.

Preparation of 10-Diazoanthrone (XXIII)

(A) From Anthraquinone Monotosylhydrazone.— A 2-1. separatory funnel was charged with anthraquinone monotosylhydra zone (^3 g»» O.ll^f mole), methyiene chloride (530 ml.), and aqueous sodium hydroxide (1 N, 530 ml.) in that order. The mix ture was shaken for several minutes. The deeply-colored lower organic layer was separated and the aqueous layer washed once with methylene chloride (100 ml.). The combined methylene chloride extracts were dried over anhydrous magnesium sulfate, filtered, and the solvent removed in vacuo. The resultant crystalline 10-diazoanthrone weighed 2^.9 g. (98% yield).

Three recrystallizations from carbon tetrachloride af forded red-brown needles which decomposed before melting.

Anal. Calcd. for .C^HgNgO: C, 76.3^5 H, 3.66; N, 12.77.

Found: C, 76.19; H, 3.57; N, 12.80.

The infrared spectrum (Figure 3) exhibits absorptions at

^ .8 7 M (diazo) and 6.11 M (carbonyl).

(B) From Anthraquinone Monohydrazone.— Anthraquinone monohydrazone (XXII, 2.2 g., 0,01 mole) in tetrahydrofuran (40 ml.) was stirred magnetically at room temperature with yellow mercuric oxide (2.*f g., 0.011 mole) for 28 hours. Suction filtration using a cellulose filtering aid and removal of the solvent in vacuo yielded crystalline 10-diazoanthrone (2.1 g., 96% yield). 45

The same conversion was effected more rapidly and in 97% yield using silver oxide.

(C) From Anthraquinone Monooxime.— A solution of the sodium salt of anthraquinone monooxime was prepared by dissolving the parent oxime^ (2.2 g., 0.01 mole) in aqueous sodium hydroxide

(64) Prepared according to P. L. Julian, W. Cole, and G. Diemer, J. Am. Chem. Soc., 67, 1721 (1945).

(4%, 200 ml.), washing with ether (100 ml.), and separating the clear red aqueous layer.

The mixture was cooled to 0°, concentrated ammonium hydroxide (20 ml., 0 .3 0 mole) added, and then over a one hour period sodium hypochlorite (140 ml., 5.25%, 0.10 mole) was added dropwise to the stirred solution. Gas was evolved. After one hour of additional stirring the precipitate was collected and dried; yield 1.3 g.

The infrared spectrum of the crude product indicated that it was a 50-50 (approximately) mixture of 10-diazoanthrone and anthraquinone monoimine. The imine was separated by subliming it out under vacuum (0.7 g.). It was quantitatively converted by aqueous acetic acid to anthraquinone and its infrared spectrum 65 was identical to that of an authentic sample.

(65) Prepared according to M. L. Stein and H. von Euler, Gazz. Chim. Ital., 84, 290 (1954). Several attempts under various conditions, including the 66 use of hydroxyamine-O-sulfonic acid as diazotizing agent, were

(66) J. Meinwald, P. G. Gassman, and E. G. Miller, J. Am. Chem. Soc., 8l, 4751 (1959). not successful in the development of this synthesis.

Preparation of Anthraquinone Triphenylphosphazine (XXXII).

A solution of 10-diazoanthrone (2.2 g., 0.01 mole) and triphenylphosphine (5.2 g., 0.02 mole) in benzene (250 ml.) was stored in the dark. After three weeks red prisms of anthraquinone tri phenylphosphazine were collected (3.2 g., 67% yield), m.p. 170-

173° (dec.). Recrystallization from-'toluene, avoiding undue heating, afforded an analytical sample melting with decomposition at 169-171°. % * Anal. Calcd. for C ^ H ^ N ^ P : . C, 79.65? H, 4.80; N, 5.81.

Found: C, 79.88; H, 4.99; N, 5.64.

The infrared spectrum of XXXII is shown in Figure 4; the carbonyl absorption appears at 6.15 •

Copper-catalyzed Decomposition of 10-Diazoanthrone in

Benzene.— A stirred solution of 10-diazoanthrone (2,2 g., 0.01 mole) in dry benzene (100 ml.) under nitrogen was refluxed over 67 copper powder (0.5 g.). Nitrogen evolution was monitored by

(67) "44F Venus, natural copper fine,” U. S. Bronze Powder Works, Inc., Flemington, N. J. 47 , collection over water and had ceased after one day. After two days the hot solution was filtered. An orange powder (1.45 g.) was separated which bn the basis of its infrared spectrum ap peared to be a mixture of copper (0.5 g.) and anthraquinone azine (XXVII, 0.95 g., 46%).

The filtrate upon cooling crystallized -bianthrone (XXVIII, 0.60 g.); additional XXXIII (0.15 g.) was isolated by removal of the solvent from the filtrate and washing of the residue with acetone. The total yield of -bianthrone was 39% and its structure was confirmed by comparison 68 of its infrared spectrum with that of an authentic sample.

(68) Prepared according to A. Schonberg and A. F. A. Ismail, J. Chem. Soc., 307 (1944).

Anthraquinone azine was characterized independently. It occurred as a side product in reaction of 10,10-dibromoanthrone with three equivalents of hydrazine in ethanol. Small orange needles melting above 315° were obtained by recrystallization from xylene.

Anal. Calcd. for C2 gHl6N2 02: C, 81.51; H, 3.91; N, 6.79.

Found: C, 81.85; H, 4.29; N, 6.64.

The infrared spectrum of XXVII is shown in Figure 5*

Anthraquinone azine was refluxed in benzene for 30 hours in the presence of copper powder. The material was recovered unchanged. Photolysis of 10-Diazoanthrone in Benzene

(A) Without Ethanol.— A solution of 10-diazoanthrone

(1.80 g., 8.2 mmole) in freshly distilled benzene (150 ml. from calcium hydride) was irradiated under nitrogen at 29° in the quartz photolysis tube. After 4.5 hours, evolution of gas had ceased (137 ml., 0.75 equivalents nitrogen). Filtration of the suspension yielded anthraquinone azine (30 mg., 2% yield).

The orange filtrate was concentrated to ca. 30 ml. and filtered to give crystalline 10,10’-bianthrone (XXIX, O.69O g.,

44% yield). The latter was characterized by spectral comparison 69 with an authentic sample.

(69) Prepared according to 0. Dimroth, Ber., 34, 219 (1901).

The solvent was removed from the filtrate and the sticky solid residue was extracted with hot petroleum ether (30-60°).

The gummy residue was removed by hand and solidified upon drying in vacuum (650 mg.). The petroleum ether extracts were evapo rated in vacuo and the residue (600 mg.) chromatographed on neutral alumina (Woelm I) using benzene as eluant. The forband yielded crystalline biphenyl (220 mg., 36% yield based on every

10-diazoanthrone molecule giving a phenyl radical), the infrared spectrum of which was identical to that of a commercial sample.

Further elution with ether gave a fraction which yielded a few milligrams of a crude solid which gave an infrared spectrum es sentially identical to that of a similarly chromatographed 70 authentic sample of 10-phenylanthrone. k9

(70) Prepared according to E. Barnett and J. W. Cook, J. Chem. Soc., 123, 2636 (1923).

Careful chromatography on neutral alumina (Woelm I) of the residue left from the petroleum ether extraction gave a

530 mg. recovery in twelve fractions. A trace of biphenyl, ca.

150 mg. of anthraquinone and, again, strong spectral evidence for the presence of a small amount of 10-phenylanthrone resulted from this chromatography.

To check the possibility of -bianthrone serving as an intermediate in this reaction, it was irradiated in sus pension (0.85 g. in 300 ml. of benzene) under the above photolysis conditions. After four hours the suspension was filtered free of

0.25 g. of an uncharacterized solid whose infrared spectrum showed the absence of 10,10'-bianthrone. Solvent removal from the filtrate left solid starting material.

(B) With Ethanol.— This experiment was run exactly as above except that absolute ethanol (3*5 ml., 1%) was added to

the 10-diazoanthrone solution. The photolysis was complete in

two hours, at which point 220 ml. (120% of theoretical nitrogen) of gas had evolved. Anthraquinone azine was not detectable.

10,10'-Bianthrone was isolated in k 7 % yield while only an 8.5% yield of biphenyl was obtained.

The residue after petroleum ether extraction again weighed

65O mg. and its infrared spectrum differed only in minor respects

from that of the same residue of the previous experiment. It was

not chromatographed. 50

Photolysis of 10-Diazoanthrone in Toluene.— A solution of

10-diazoanthrone (1.6 g., 7*3 mmole.) in toluene (300 ml., dis

tilled from calcium hydride) in the quartz vessel was purged with

nitrogen for 20 minutes. Irradiation under nitrogen for two

hours effected theoretical nitrogen evolution. The yellow

solution was stripped of solvent in vacuo and the residue treated

with ether. Cooling to k° and filtering allowed collection of

10,10'-bianthrone (0.30 g., 21% yield). Solvent removal from

the filtrate left an orange oil which was not identified.

Thermolysis of 10-Diazoanthrone in Mesitylene.— A

solution of 10-diazoanthrone (2.2 g», 0.01 mole) in mesitylene

(100 ml., freshly distilled) was heated under nitrogen for eight

hours at 120-125°• Concentration of the orange solution to ca.

30 ml. in vacuo and filtration enabled isolation of crystalline

10,10'-bianthrone (0.58 g., 30% yield). Solvent removal from

the filtrate gave a viscous brown residue which was placed on a

column of neutral alumina (Woelm I, 2 x 13 cm.) with benzene.

The leading edge of the dark band was collected in 50 ml. of

eluant and evaporated. The oily crystalline residue was tritu

rated with Skellysolve F (8 ml.), filtered, and dried to yield

10,10-bis(3,5-

yield).

Several recrystallizations from absolute ethanol gave

the analytical sample of XXXIII as colorless needles, m.p. 212-

214°. 51

Anal. Calcd. for C^H^qO: c, 89.26; H, 7.02.

Found: C, 88.71; H, 7.00.

The infrared spectrum of XXXIII is shown in Figure 6.

The n. m. r. spectrum (Fig. 28) exhibits singlets at 8.15 7"*

(methyl, area 12 ) and 6.42 7* (methylene, area 4), unresolved peaks at 4.08 'T (benzyl C-2, area 4) and 5*51 ** (benzyl C-4, area 2) and an aromatic multiplet (1.7-2.9 7" , area 8) assigned to the anthrone protons.

Photolysis of 10-Diazoanthrone in Benzene and in Toluene in the Presence of Triphenylphosphine; Anthronylidenetriphenyl- phosphorane (XXXI).— A freshly prepared solution of 10-diazoanthrone (3.50 g., 0.015 mole) andtriphenylphosphine (4.20g.,

0.016 mole) in anhydrous benzene (300 ml.) was photolyzed at 13° in the quartz vessel. After seven hours the precipitated product had collected on the walls of the photolysis tube inhibiting light passage. Anthronylidenetriphenylphosphorane (XXXI, 3.2 g.) was removed by filtration and the filtrate returned to the cleaned tube for further irradiation. Two additional crops brought the total yield of XXXI to 5*7 g. (84%), m.p. 202° (dec.). Three recrystallizations from absolute ethanol gave the product as orange needles, m.p. 21'l-2l4° (dec.).

Anal. Calcd. for G ^ ^ S . ^ O ’P: C, 84.56; H, 5*10.

Found: C, 84.39; H, 5.07.

The infrared spectrum of XXXI (Fig. 7) exhibits a shifted carbonyl at 6.40 . 52

A suspension of anthraquinone triphenylphosphazine

(XXXII, 2 g., 4.1 mmole) in benzene (300 ml.) was similarly photolyzed. After seven hours about one-half of the starting material was recovered. No anthronylidenetriphenylphosphorane was detected.

A freshly prepared solution of 10-diazoanthrone (2.2 g.,

0.01 mole) and triphenylphosphine (2.75 g»* 0.0105 mole) in toluene (300 mi., distilled from calcium hydride) was similarly irradiated. Theoretical nitrogen was evolved during four hours and filtration enabled the isolation of anthronylidenetriphenylphosphorane (0.95 g»» 21% yield). No further products were iso lated from this reaction.

Thermolysis of Anthraquinone Triphenylphosphazine (XXXII).--

A suspension of anthraquinone triphenylphosphazine (XXXII, 3»1 g«»

6.4 mmole) in dry benzene (100 ml.) was refluxed. The mixture became homogeneous after several hours. Continued reflux for two days, followed by cooling and filtration allowed isolation of anthraquinone azine (XXVII, 0.5 g., 37% yield) as shown by the infrared spectrum.

Removal of the solvent in vacuo from the filtrate and extraction of the residue with petroleum ether (30-60°, 51 ml.) left a dark red solid (1.4 g.) shown by its infrared spectrum to, contain anthraquinone triphenylphosphazine and 10-diazoanthrone.

After the ether extract had been treated with charcoal and the solvent removed in vacuo, crystalline triphenylphosphine (0.8 g.,

48% yield) remained. Reaction of 10-Bromoanthrone with Triphenylphosphine

(A) In Benzene.— A solution of triphenylphosphine (5.24 g., 0.02 mole) in dry benzene (70 ml.) was added dropwise to a 71 magnetically stirred solution of 10-bromoanthrone (5.46 g.,

0.02 mole) in benzene (200 ml.). A precipitate began to form

(71) Prepared according to E. Barnett, J. W. Cook, and M. A. Mathews, ibid., 123. 2006 (1923). immediately. Stirring for one hour after the addition was com plete followed by filtration allowed isolation of a pale yellow solid (5*6 g.). A weak carbonyl band at 6.00 M suggested that the material was a mixture of the C- and 0- phosphonium bro mides (XXXV and XXXIV) with the latter predominating.

The above mixture was stirred with an equivalent of potassium t^-butoxide (0.01 mole) in benzene (200 ml.) for four

hours and then filtered. The orange filtrate yielded a solid

(4.4 g.) upon removal of the solvent in vacuo. Several solvent manipulations led to the isolation of crystalline anthronylide-

netriphenylphosphorane (XXXI, 0.13 g.) from the orange mixture.

(B) In Chloroform; Anthracene-9-oxytriphenylphosphonium

Bromide (XXXIV).— In a system protected from moisture, a solution

of triphenylphosphine (5*24 g., 0.02 mole) in ethanol-free

chloroform (50 ml.) was added dropwise to a stirred solution of

10-bromoanthrone (5.46 g., 0.02 mole) in the same solvent (80 ml.),

The reaction warmed somewhat during the addition but no precipi

tation occurred. Upon continued stirring overnight the vivid yellow solution separated a white solid (ca. 0.5 g.) which was removed by filtration. It quickly decomposed with fuming upon exposure to the atmosphere. Disolvated anthracene-9-oxytriphenylphosphonium bromide (XXXIV, 9*5 g»* 6l% yield) separated from the filtrate as large yellow prisms upon two days refrig eration at V 3. The crystals tarnished in the atmosphere but could be washed clean with alcohol-free chloroform. Since the crude sample could not be recrystallized, it was analyzed directly,m.p. 208-210 °,

Anal. Calcd. for C^ H ^ B r O P ^ C H C l ^ : C, 52.7^; H, 3.39.

Found: C, 5^.96; H, 3.33.

The infrared spectrum of XXXIV (Fig. 8) exhibits a strong broad absorption for -CCl^ at 13.6 •

A sample (k g.) of the above phosphonium bromide was hydrolyzed in aqueous ethanol (kO ml.) at room temperature to anthrone and triphenylphosphine oxide in yields of 95% and 85% respectively.

Reactions of Anthronylidenetriphenylphosphorane

(A) With Acetone.— After refluxing a suspension of anthronylidenetriphenylphosphorane (1.35 g») in acetone (100 ml.)

for 10 days, the ylide was recovered unchanged.

(B) With Benzaldehyde.— A solution of anthronylidenetriphenylphosphorane (l g., 2.18 mmole) and benzaldehyde (0.235 g.»

2.18 mmole) in chloroform (50 ml.) was refluxed for 3*5 days.

Solvent removal in vacuo and washing of the orange residue with large amounts of water to remove benzaldehyde led to a solid 55

(950 mg.) melting at 159-179° (dec.). The infrared spectrum of the mixture showed it to contain a preponderance of starting ylide. However, a weak carbonyl absorption at 6.02 A suggested the presence of a small amount of 10-benzylideneanthrone.

(C) With p-Nitrobenzaldehyde.— A solution of anthronylidenetriphenylphosphorane (1.00 g., 2.18 mmole) and an equiv alent (0.35 g.) of £-nitrobenzaldehyde in chloroform (50 ml.) was refluxed for 78 hours. Solvent removal in vacuo left a dark oil from which,triphenylphosphine oxide was removed by treatment with hot 95% ethanol (10 ml.). The alcohol precipitated yellow

10-(£-nitrobenzylidene)-anthrone (XXXVIb, 0.60 g., 8b%), m.p.

177-182°. Three recrystallizations from absolute alcohol yielded the analytical product as long yellow needles, m.p. 182-18**°.

Anal. Calcd. for C ^ H ^ N O ^ : C, 77.05; H, **.00; N, **.28.

Found: C, 76.82; H, **.10; N, **.27.

The infrared spectrum, shown in Figure 9» displays a carbonyl absorption a t ,6.03 *1 and nitro absorptions at 6.65 and

7.50 A .

The crystals fluoresced yellow under ultraviolet light but showed no thermochromism upon refluxing in xylene, pressing, in potassium bromide (piezochromism), or fusion in a sealed capillary under nitrogen.

(D) With a-Nitrobenzaldehyde.— Using the same procedure as in reaction of £-nitrobenzaldehyde with anthronylidenetriphenylphosphorane, m-nitrobenzaldehyde reacted with the ylide to give 10-(m-nitrobenzylidene)anthrone (XXXVIa, 77% yield), m.p. , . . . •' 56 • r * 172-174°. Recrystallization from acetic acid gave yellow prisms melting at 173-175° (lit.3lf 174.5-175.5°).

The crystals fluoresced green under ultraviolet light, but, like the £-nitro isomer, did not exhibit thermochromism.

Reaction of 10-Diazoanthrone with Acetic Acid.— A stirred solution of 10-diazoanthrone (2.2 g., 0.01 mole) in glacial acetic acid (100 ml.) was heated at £a. 90° for five hours.

During this period the solution progressed from dark red to light orange and the theoretical volume of nitrogen (224 ml.) was evolved. After the cooled solution had been filtered, the filtrate was diluted with a large amount of water. 10-Acetoxy- anthrone (XXXVIII, 2.0 g., 79%) was collected; after one re- o 72 crystallization from ethanol-water it melted at 107-109 (lit.

108°).

(72) K. H. Meyer, Ann., 379, 66 (1911).

Reaction of 10-Diazoanthrone with Boron Trifluoride

Etherate.--Freshly distilled boron trifluoride etherate (6 ml.) was added dropwise to a stirred solution of 10-diazoanthrone

(2.2 g., 0.01 mole) in dioxane (100 ml., purified by chroma

tography on alumina). The system was protected from moisture by a drying tube..

After the addition was complete, the deep-red solution

effervesced slowly and after 43 hours had changed in color to

yellow. Near the end of this period a crystalline precipitate 57 formed. Filtration separated anthraquinone (600 mg.); additional anthraquinone (700 mg.) was isolated after basification of the filtrate with saturated sodium bicarbonate (100 ml.) and further dilution with water (200 ml.). The total yield of anthraquinone was 62%,

Reaction of 10-Diazoanthrone with Phenanthrenequinone.—

A mixture of 10-diazoanthrone (2.20 g., 0.01 mole) and phen anthrenequinone (2.08 g., 0.01 mole) was refluxed for k ,5 days in dry benzene (100 ml.). During the reaction nitrogen (195 ml.,

87%) was evolved. Filtration of the cooled reaction mixture separated anthraquinone azine (XXVII, 150 mg., 7*2% yield) as shown by its infrared spectrum.

The solid residue obtained by removal of solvent from the filtrate was treated with activated charcoal in boiling acetonitrile (550 ml.). The mixture was filtrated while hot; upon cooling, the yellow filtrate separated spiroCanthrone-10,2 '-

(phenanthroC9»10]-l',3'-dioxole)] (XXXIX, l . k g., 35% yield), m.p. 269-273°. After the filtrate had been concentrated to ca.

200 ml., a second crop of crystals was obtained which was con

taminated with appreciable amounts of -bianthrone as shown by its infrared spectrum and its green fluorescence under ultraviolet light.

An analytical sample of the spiro compound was obtained

as yellow needles and plates after chromatography on alumina and.

several recrystallizations from acetonitrile; m.p. 271-273° (dec.

with prior darkening). Anal. Calcd. for C ^ H ^ O ^ s C, 83.98; H, 4.02.

Founds. C, 83.96; H, 3.98.

The infrared spectrum of XXXIX (Fig. 10) exhibits a single sharp carbonyl absorption at 6.00 <*1.

Reaction of 10-Diazoanthrone with Nitrosobenzene.— A solution of 10-diazoanthrone (2.2 g., 0.01 mole) and nitrosobenzene (1.1 g., 0.01 mole) in benzene (100 ml.) was stirred at room temperature for 1.5 days during which time an equivalent of nitrogen was evolved. Removal of the solvent in vacuo left an orange-red oil which solidified upon refrigeration. Trituration

with petroleum ether (30-60°, 50 ml.) followed by filtration left an orange powder which after recrystallization from 95%

ethanol yielded N-phenylanthraquinone oxime (XLI, 2.15 g*» 72%

yield), m.p. 144-146° (dec.).

Several recrystallizations from alcohol yielded an

analytical sample of XLI, burned orange crystals, m.p. 147-149°

(dec.).

Anal. Calcd. for C ^ H ^ N O : C, 80.25; H, > . 38; N, 4.68.

Found: C, 79.57; H, 4.42; N, “4.63.

The infrared spectrum (Fig. 11) shows a carbonyl ab

sorption at 6.03

Attempted Reaction of 10-Diazoanthrone with N-Sul-

finylaniline.— -A solution of 10-diazoanthrone (2.2 g., 0.01 mole) 73 and an equivalent (1.4 g.) of N-sulfinylaniline in benzene

(100 ml.) was refluxed for four hours, cooled, and filtered to

remove a trace of brown solid. 59

(73) For preparation and review see G. Kresze et_al., Angew. Chem., Intern* Ed* Engl. 1, 89 (1962),

Solvent removal in vacuo left a moist crystalline residue which was treated with petroleum ether (30-60°), filtered, and dried. Thus was obtained a 91% recovery of 10-diazoanthrone.

Reaction of 10-Diazoanthrone with Acrylonitrile.— A solution of 10-diazoanthrone (2.2 g,, 0.01 mole) and acryloni trile (2 ml., 0.03 mole) in dry benzene (100 ml.) and under nitrogen was refluxed for 20 hours during which time theoretical nitrogen (224 ml., 0.01 mole) was evolved. After the mixture had been cooled to room temperature, filtered, and concentrated in vacuo, a powder resulted which crystallized from 95% ethanol to yield fine needles of 2'-cyanospiroCanthrone-10,1'-cyclo propane] (XLIII, 1.6 g., 65% yield), m.p. 184-186°.

Further crystallizations from ethanol yielded constant- melting colorless needles, m.p. I85-I860 of analytical purity.

Anal. Calcd. for C ^ H ^ N O : C, 83.24; H, 4.52; N, 5.71.

Found: C, 82.75; H, 4.56; N, 5.58.

The infrared spectrum (Fig. 12) of XLIII shows bands at

6.07 (carbonyl), and 4.53 M (nitrile). The n. m. r. spectrum

(Fig. 20) exhibits an aliphatic multiplet centered at 7.62 7*

(area 3) and aromatic multiplets of area 8.

Reaction of 10-Diazoanthrone with Methyl Vinyl Ketone.—

A solution of 10-diazoanthrone (2.2 g., 0.01 mole) and methyl 60 vinyl ketone (2.1 g., 0.03 mole) in dry benzene (100 ml.) and under nitrogen was refluxed until gas evolution was complete

(8 hours). Upon removing the solvent in vacuo a red oil was ob tained which crystallized upon seeding and storing in a refrig erator overnight. Trituration with petroleum ether (30-60°,

25 ml.) and filtration gave a crude product (2.5 g.) which was recrystallized from cyclohexane (120 ml.) with the aid of acti vated charcoal. The crystals of 2'-acetylspiroCanthrone-10,1'- cyclopropane] (XLIV) weighed 1.6 g. (6l% yield) and melted at

113-115°• An analytical sample (pale yellow needles) melted at

115-116°.

Anal. Calcd. for C* 82*2f2» H » 5*58.

Found: C, 81.97; H, 5.23.

The infrared spectrum (Fig. 13) of XLIV shows a carbonyl band at 5*91 M (acetyl) and another at 6.07 (anthrone). The n. m. r. spectrum (Fig. 30) exhibits a multiplet between 7*0 and

7.9 ~T (area 3» cyclopropyl hydrogens), a singlet at 8.27 T*

(area 3» acetyl hydrogens) and aromatic multiplets of area 8.

Reaction of 10-Diazoanthrone with Methyl Methacrylate.—

A solution of 10-diazoanthrone (2.2 g., 0.01 mole) and methyl methacrylate (3 g.» 0.03 mole) in dry benzene (100 ml.) and under nitrogen was refluxed for two days during which time approximately theoretical nitrogen was evolved. Solvent removal in vacuo left a mixture of an oil and an amorphous solid. This mixture was re

fluxed briefly with absolute alcohol (50 ml.) and then refrig erated overnight. After filtering off the presumedly polymeric 61 residue, the filtrate was concentrated to a red oil by vacuum evaporation. The oil crystallized upon treatment with petroleum ether (25 ml.), cooling and scratching the walls of the vessel with a glass rod. The crude product was collected and re crystallized from cyclohexane (55 ml.) with the aid of activated charcoal to give light yellow crystals of 2 ,-carbomethoxy-2'- methylspiroCanthrone-10,1'-cyclopropane] (XLV, 1.65 g.» 56%), m.p. 107-110°. An analytical sample as colorless needles melted at 110-112°.

Anal. Calcd. for C ^ H ^ O ^ : C, 78.06; H, 5.52.

Found: C, 77.9^; H, 5.67.

The infrared spectrum (Fig. l*f) shows carbonyl bands at

5.80 (ester) and 6.0*f (anthrone). The n. m. r. spectrum in carbon tetrachloride (Fig. 51) exhibits singlets at 8.98 7*

(area 3» C-ijebhyl) and 6.95 7* (area 3» 0-methyl), a quartet at

7.63 7* (area 2, cyclopropyl hydrogens, J =7*5 cps.), and two aromatic multiplets (area 8).

Reaction of 10-Diazoanthrone with trans-1,2-Dibenzoyl- ethylene.— A solution of 10-diazoanthrone (2.2 g., 0.01 mole) and trans-1,2-dibenzoylethylene (2,6l g., 0.011 mole) under nitrogen in dry benzene (100 ml.) was refluxed until evolution of nitrogen had ceased (7 hours).

. The solid residue obtained by vacuum evaporation of the solvent was triturated with 95% ethanol (35 ml.) and the slurry

filtered. The residual off-white powder melted at 211-215°

(dec.) and weighed 3.9 g. (91% yield). Recrystallization from 62 benzene afforded prisms of trans-2 * ,3 t-dibenzoylspiro[anthrone-

10,1*-cyclopropane] (XLVI, 3.1 g.) m.p. 220-222° (dec.). Two further recrystallizations from benzene gave colorless prisms of m.p. 221° (dec.).

Anal. Calcd. for C, 84.09; H, 4.70.

Found: C, 84.31; H, 4.71.

The infrared spectrum of XLVI (Fig. 15) shows a carbonyl doublet absorption centered at 6.0 M • The n. m. r. spectrum

(Fig. 32) shows a singlet at 5*61 7"* (area 2, cyclopropyl hydrogens) and two aromatic multiplets (area 18).

Reaction of 10-Diazoanthrone with p-Benzoquinone

(A) At 80°.— A solution of 10-diazoanthrone (2.2 g.,

0.01 mole) and £-benzoquinone (3.2 g., 0.03 mole) in dry benzene

(100 ml.) was refluxed for 22 hours during which an equivalent of nitrogen was evolved. The dark reaction mixture was cooled, filtered free of tarry material, and concentrated in vacuo. The residue was boiled for a few minutes in absolute alcohol (25 ml.), cooled and filtered to give a very crude product (2.2 g.) which was treated with activated charcoal in boiling absolute ethanol

(150 ml.). After filtering the hot suspension, the yellow fil trate upon cooling deposited yellow plates of 2 1,5’-diketospiro-

[anthrone-10,7,-bicyclo[4.1.0]hept-3,-ene] (L, 1.3 g.). Re- crystallization from alcohol yielded yellow crystals of L (1.2 g,,

3 7 % yield), m.p. 168-170° (dec.). An analytical sample as yellow leaves melted at 168-170° (dec. with prior darkening). 63

Anal. Calcd. for 79*99; H, 4.03.

Found: C, 80.64; H, 4.10. s _ The infrared spectrum (Fig. 16) shows a double ca;rl3ohyl absorption centered at 6.0 -c/ . The n. m. r. spectrum 0*yr&^33) shows singlets at 6.77 1* (area 2, cyclopropyl hydrogens) and

3.37 (area 2, vinylic hydrogens) and aromatic multiplets of area 8.

(B) At Room Temperature.— In a similar experiment 10-. diazoanthrone was allowed to react with £-benzoquinone at room temperature. In three days the benzene solution deposited an orange-yellow solid (0.7 g.). The infrared spectrum of this material exhibited intense absorption in the diazo region

(4.83 )j however, the balance of the spectrum did not suggest the presence of 10-diazoanthrone.

The material was treated with hot acetonitrile (70 ml.), filtered, and the filtrate cooled. Crude 4 ’,7’-dihydroxyspiro-

[anthrohe-10,3'-indazole] (XLIX, 0.2 g., 6%) of indiscrete de composition point was deposited. Three recrystallizations from acetonitrile afforded an analytical sample (small yellow prisms) which slowly decomposed above l40°.

Anal. Calcd. for C ^ ^ ^ O ^ : C, 73.16; H, 3.68; N, 8.53.

Found: C, 73.14; H, 3.73; N, 8.64. j ‘ Workup of the initial filtrate of this reaction led to a low yield of 2 1,5 l-diketospiro[anthrone-10,7,“bicyclo^*'*'*^^- hept-3'-ene] (L). 64

The infrared spectrum (Fig. 17) of the spiroindazole

(XLIX) shows absorptions at 3.1 ** (hydroxy) and 6.11 •*# (carbonyl).

Reaction of 10-Diazoanthrone with Diethyl Azodicarboxy- late.— A solution of 10-diazoanthrone (2.2 g., 0.01 mole) and diethyl azodicarboxylate (3.5 g»» 0.02 mole) in dry benzene

(100 ml.) was stirred magnetically at room temperature for one day during which time ca. 50 ml. of nitrogen was evolved. The solution was then refluxed for 20 hours and the theoretical quantity of nitrogen (0.01 mole) was evolved. Solvent removal in vacuo gave a red oil which eventually solidified at room tem perature. Trituration with 15 ml. of benzene/petroleum ether

(30-60°) and filtration gave 3*5 g. of crude product. Recrystal lization from absolute ethanol yielded yellow leaves of l',2'- dicarboethoxyspiro[anth.rone-10,3'-diaziridine[] (LII, 2.55 g.»

75% yield), m.p. 148-152°. Several additional recrystalli zations from ethanol and one from benzene with the aid of acti vated charcoal afforded an analytical sample as yellow leaves of m.p. 151-152.5°.

Anal. Calcd. for C ^ H ^ N ^ : C, 65.57; H, 4.95; N, 7.64.

Found: C, 65.49; H, 5.10; N, 7.52.

The infrared spectrum of LII (Fig. 18) shows carbonyl absorptions at 5*73 M (urethane) and 5*97 M (anthrone). The n. m. r. spectrum (Fig. 34) exhibits a triplet at 8.87 7* (methyl, areai 6), a quartet at 5*82 'f* (methylene, area 4) and aromatic multiplets of area 8. 65 I Reaction of 10-Diazoanthrone with Dimethyl Acetylene- dicarboxylate.— A solution of 10-diazoanthrone (6.6 g., 0.03 mole) and dimethyl acetylenedicarboxylate (4.26 g., 0.03 mole) in dry benzene (250 ml.) was stirred at room temperature for five days. The solution turned from dark red to light orange but no nitrogen was evolved.

Solvent removal in vacuo left an orange solid melting at 109-115° (dec.) which, upon crystallization from benzene/

Skellysolve C, yielded crystals (7,g., 64%) of 4',5'-dicarbomethoxyspiro[anthrone-10,3*-pyrazole] (LVIII), m.p. 123-125°

(dec.).

An analytical sample, yellow irregular crystals which became orange upon drying in vacuo at 56° for one hour, was ob tained by further recrystallizations from benzene/Skellysolve C and alcohol, m.p. 124.5-125.5° (dec.).

Anal. Calcd. for C ^ H ^ N ^ : C, 66.30; H, ,3.89s N, 7.73.

Found: C, 66.53; H, 4.00; N, 7.86’.

This compound may crystallize in one or both of two forms; square rods or irregular prisms. Both decompose at the same temperature but their infrared spectra in potassium bromide wafers are markedly different. However, their spectra in chloro form are identical. It was concluded that the two forms are isomorphs.

The infrared spectrum of the irregular-prism form is shown in Figure 19 (5.78 M , ester carbonyls; 6.01 *4 , anthrone carbonyl). The n. m. r. spectrum (Fig. 35) shows singlets at 66

5»99 T (area 3) and 6.54 T* (area 3) for the O-methyl groups and three aromatic multiplets (area 8).

Photolysis of 4* t3 >-DicarbomethoxyspiroCanthrone-10t3 1-;

pyrazole] (LVIII).— A solution 4',5'-dicarbomethoxyspiro[an-

throne-10,3'-pyrazole3 (3 .0 g,, 8.3 mmole) in anhydrous ether

(300 ml.) in the quartz photolysis tube was purged with dry

nitrogen for 20 minutes. Irradiation of the solution brought

about the evolution of approximately one equivalent of nitrogen.

Solvent reduction in vacuo to ca. 25 ml. caused the

crystallization of pale yellow 1 ',2 ,-dica^bomethoxyspiro[an-

throne-10,3,-cyclopropene] (LIX) of indiscrete decomposition

point. Yield: 1.3 g., 47%. Several recrystallizations from

carbon tetrachloride afforded an analytical sample which slowly

decomposed over a wide range above 125°.

Anal. Calcd. for C ^ H ^ C y C, 71.85; H, 4.22.

Found: C, 71.67; H, 4.22.

The infrared spectrum (Fig. 20) of LIX shows bands at

5.44 m (cyclopropene ring vibration), 5*83 *4 (ester carbonyls),

and 6.10 Af (anthrone carbonyl). The n. m. r. spectrum (Fig. 36)

exhibits a singlet (area 6) at 6.20 ~T (0-methyls) and two

aromatic multiplets (area 8).

74 Reaction of 10-Diazoanthrone with Benzyne. — A solution

of 10-diazoanthrone (2.2 g., 0.01 mole) and isoamyl nitrite

(74) The generation of benzyne is based on a procedure of L. Friedman and F. M. Logullo, J. Am. Chem. Soc., 85, 1549 (1963)* (1.35 g*» 0.0115 mole) in dichloromethane (50 ml.) was brought to reflux and a solution of anthranilic acid (1.44 g., 0.0105 mole) in acetone (12 ml.) was added dropwise in 1.5 hours.

During the addition the theoretical volume of gas (nitrogen and carbon dioxide, 450 ml., 0.02 mole) required for generation of

0.01 mole of benzyne was evolved.

After the addition was complete, the dark red solution was refluxed for a few minutes, cooled and concentrated in vacuo at room temperature. The oily crystalline residue was washed with 95% ethanol (50 ml.) and filtered to yield fine yellow needles of spiro[anthrone-10,3'-indazole] (LXI, 2.60 g., 87% yield), m.p. 174° (dec.). Several recrystallizations from acetonitrile yielded an analytical sample as near-colorless prisms, m.p. 179-l80° (dec.).

Anal. Calcd. for C ^ H ^ O : C, 81.06; H, 4.08; N, 9.45.

Found: C, 81.05; H, 3.88; N, 9.71.

The infrared spectrum of LXI is shown in Figure 21; the carbonyl absorption appears at 6.02 M •

Preparation of 7-Diazo-8-acenaphthenone.— In a modifi- nv cation of a literature procedure, acenaphthenequinone toSylhydrazone (8.97 g»i 0.026 mole) was shaken for five minutes in dichloromethane (128 ml.) and water (200 ml.) with sodium hydroxide (l N, 30 ml., 0.03 mole). After filtration, the organic layer was separated and dried over anhydrous magnesium sulfate and then filtered. Solvent removal from the filtrate in vacuo left orange 7-diazo-8-acenaphthenone (4.8 g., 97%). 68

The infrared spectrum of the product was identical to that of a purified sample; the crude material was used in subsequent ex periments without further purification.

Reaction of 7-Diazo-8-acenaphthenone with Dimethyl

Acetylenedicarboxylate.— A solution of 7-diazo-8-acenaphthenone

(5.40 g., 0.0281 mole) and dimethyl acetylenedicarboxylate

(4.12 g., 0.029 mole) in dichloromethane (120 ml.) was refluxed

for 44 hours. Solvent removal left a yellow powder melting at

194-197° which, upon recrystallization from acetonitrile, gave

an unidentified yellow compound (6.8 g., 72%), m.p. 200 -203 °

having the empirical formula ^18^12 ^ 2^5 (LXXIII). An analytical

sample as bright yellow prisms melted without decomposition at

201-203°.

Anal. Calcd. for c18Hi2N2°5: C ’ H » 5 *85* N ’ 8*31, Found: C, 64.40; H, 3*65; N, 8.21.

The infrared spectrum of LXXIII is shown in Figure 22. -

Ester absorptions are apparent (carbonyl at 5*83 M ). A band at

5.75 M is also present. In chloroform solution a single band

is observed at 5*80 M . The n. m. r. spectrum (Fig. 37) shows a

sharp singlet at 5*98 7” (area 6, 0-methyl) and an aromatic

multiplet (area 6) between 1.1 and 2.8 T,

74 Reaction of 7-Diazo-8-acenaphthenone with Benzyne. — A

solution of anthranilic acid (3*55 g»* 0.0259 mole) in acetone

(30 ml.) was added dropwise in 70 minutes to a refluxing stirred

solution of 7-diazo-8-acenaphthenone (4.80 g., 0.0247 mole) and isoamyl nitrite (3*35 g.» 0.0304 mole) in dichloromethane (90 ml.)

After a few minutes of additional reflux, the solution was cooled ■' r and the solvent removed in vacuo.

The dark residue was treated with methanol (70 ml.) and filtered. There was thus collected a brick-red powder (4.9 g»)» m.p. 214-215°. Recrystallization from methanol using activated charcoal afforded long, red-orange needles of an unidentified compound (3*8 g., 57% yield) of empirical formula C]_8^10N2^

(LXXII). Three recrystallizations from dichloromethane gave an analytical sample melting at 218-219° (a possible phase change at 205°).

Anal. Calcd«_ for Cl8H1()N20: C, 79.98; H, 3.73; N, 10.37.

Found: C, 79.78; H, 3.98; N,. 10.22.

The solutions of LXXII are quite fluorescent. Photolysis of a benzene solution through quartz for one hour caused no loss of nitrogen and the material was recovered unchanged. The com pound forms a light-yellow solution in hot aqueous sodium hydroxide and is recovered unchanged upon acidification.

The infrared spectrum (Fig. 23) shows absorption at

5.86 M • Due to a lack of solubility the n. m. r. spectrum could not be obtained.

Attempted Reaction of 7-Diazo-8-acenaphthenone with

Acrylonitrile.— A solution of 7-diazo-8-acenaphthenone (1.94 g.,

0.01 mole) and acrylonitrile (O.58 g., 0.011 mole) in methylene chloride (lOO ml.) was refluxed for 29 hours. No nitrogen was evolved and. solvent removal gave only unchanged diazo compound. 70

Photolysis of 3-Methylnaphthalene-l,4-diazooxide in the

Presence of Triphenylphosphine.— Triphenylphosphine (2.62 g.,

0.02 mole) was added to a solution of 3-methylnaphthalene-l,4- 75 diazooxide (1.84 g., 0.01 mole) in dry benzene (300 ml.) in

(75) See Ref. (9) for preparation. the quartz photolysis tube. The dark red solution was purged with dry nitrogen for 20 minutes during which time the solution turned orange. The mixture was photolyzed for nine hours. The solution did not change appearance and only a small amount

(30 ml.) of nitrogen was evolved.

Solvent removal in vacuo left a dark oil which solidified to a dark-orange material showing no diazo absorption in the infrared. Several recrystallizations from absolute ethanol gave an analytical sample of 2-methyl-l,4-naphthoquinone-4-triphenylphosphazine (LXVII) as large orange prisms, m.p. 165-166° (dec.).

Anal. Calcd. for C ^ H ^ l ^ O P : C, 78.01; H, 5.19; N, 6.27.

Found; C, 78.04; H, 5.30; N, 6.50.

The irufrared spectrum of LXVII is shown in Figure 24.

Reaction of 3-Methylnaphthalene-l,4-diazooxide with trans-

1,2-Dibenzoylethylene.— A solution of 3-methylnaphthalene-l,4- 75 diazooxide J (1.84 g., 0.01 mole) and trans-1,2-dibenzoylethylene

(2.37 g., 0.01 mole) in benzene (100 ml.) was stirred magneti cally at room temperature. Approximately one equivalent of nitrogen was evolved in one week. The snow-white powder which 7 1 had formed was collected. Thus was isolated trans-2,3-dibenzoyl-

2 1-methylspiro[cyclopropane-1,k •-(1'-naphthalenone)] (LXIII,

3.3 g.» 8*f% yield), m.p. 215-217°. Three recrystallizations from benzene gave an analytical sample as colorless prisms which crumbled to a chalky white powder upon vacuum drying at 56°, m. p. 216-217°.

Anal. Calcd. for C ^ H ^ q O^: C, 82.63; H, 5.1**-.

Found: C, 82.**9; H, 5.15. ■

The infrared spectrum (Fig. 25) of LXIII shows three maxima in the carbonyl region; 5*98 M , 6.0^ <

The n. m. r. spectrum (Fig. 38) exhibits a doublet at 7.93 7*

(area 3» methyl split by vinylic hydrogen, J = 1 . 0 cps.), a quartet at 5*5^ 7* (area 2, nonequivalent cyclopropyl hydrogens,

J = 7i7 cps.), an unresolved peak at 3.19 7* (area 1, vinylic hydrogen) and an aromatic multiplet (area 14).

Reaction of 3»5-Dimethylbenzene-l,it—diazooxide with trans it 2-Dibenzoylethylene.— A solution of 3*5-dimethylbenzene-l,4- 76 diazooxide (1.0 g., 6.8 mmole) and trans-1,2-dibenzoylethylene

(76) Prepared according to Ref. (9).

(1.66 g., 7.0 mmole) in dry benzene (100 ml.) and protected from light was stirred magnetically for four weeks and then refluxed

for two hours. The residue left by solvent removal in vacuo was recrystallized from absolute ethanol to yield yellow plates

(1.05 g., yield), m.p. 1^9-156°. Further recrystallizations 72 from ethanol and benzene gave an analytical sample of 2,4-di methyl -trans-6,7-diberizoylspiro(2,5)octa-l,*f-diene-3-one (LXV) as colorless plates, m.p. 165-167°.

Anal. Calcd. for C, 80.88; H, 5.66.

Found: C, 80.11; H, 5.67.

The infrared spectrum (Fig. 26) shows carbonyl ab sorptions at 6.00 (benzoyl) and 6.1*f *1 (dienone). The n. m. r. spectrum (Fig. 39) exhibits singlets at 8.07 7* (methyl, area 6), 5*56 7* (cyclopropyl, area 2), an unresolved peak at

3.29 T (vinyl, area 2), and an aromatic multiplet (area 10).

Reaction of 3-Methylnaphthalene-l.^— diazooxide with 74 Benzyne. — A solution of anthranilic acid (3.55 g»» 0.0259 mole) in acetone (3 0 ml.) was added dropwise in one hour to a refluxing nc stirred solution of 3-methylnaphthalene-l,if-diazooxide (^.55 g. »

0.02^7 mole) and isoamyl nitrite (3.35 g«* 0.0 2 8 6 mole) in di chloromethane (90 ml.). After an additional few minutes of reflux, the mixture was cooled to room temperature.

After drying over anhydrous magnesium sulfate and fil tering, the red solution was stripped of solvent in vacuo and the dark semicrystalline residue refrigerated overnight. Tri turation, filtration and washing with methanol (35 ml.) enabled the isolation of a light-brown powder (*f.2 g.).

Recrystallization from methanol, with the aid of activated charcoal yielded large crystals of 2 ,-methylspiro[ind'azole-3,^'-

(1'-naphthalenone)] (LXI, 3.0 g., k-7% yield), m.p. 125-126°

(dec.). This material was somewhat discolored and was best 73 purified by elution with dichloromethane through a short column of basic alumina. An analytical sample as large, pale-yellow prisms was obtained by several recrystallizations from methanol, m.p. 126-127° (dec.).

Anal. Calcd. for C17H12 N2 0: C, 7 8.Vf; H, k.6l\ N, 10.76.

Found: C, 7 8.^8; H, *f.69; N, 10.89.

The infrared spectrum of LXVI is shown in Figure 27.

The n. m. r. spectrum (Fig. *f0) exhibits a doublet at 7*87

(area 3» methyl split by vinylic hydrogen, J = 1 . ^ cps.), an unresolved peak at *t-.l6 7"* (area 1, vinylic hydrogen) and three aromatic multiplets (area 8).

Improved Preparation of Phenanthrene-9.10-diazooxide.f 77

Phenanthrenequinone (16.5 g.» 0.08 mole) was added to a hot

(77) Literature preparations: Ref.' (7) and 0. Sus, H. Steppen, and R. Dietrich, Ann., 617, 20 (1958). solution of £-toluenesulfonylhydrazide (1 5 .6 g., O.O85 mole) in benzene (300 ml.). After refluxing for five minutes, the mixture was cooled to 10° and the precipitated £-toluenesulfinic acid filtered.

The filtrate was washed with saturated sodium bicarbonate

(500 ml.) in three portions and then with water (200 ml.). After drying the benzene layer over anhydrous magnesium, sulfate, the solvent was removed in vacuo and the yellow residue was immedi ately recrystallized from cyclohexane (600 ml.) with the aid of activated charcoal to yield yellow needles (10.5 g.» 60%) of phenanthrene-9»10-diazooxide, m.p. 110-112°.

Attempted Reaction of Phenanthrene-9«10-diazooxide with

Acrylonitrile.— A solution of phenanthrene-9t10-diazooxide

(2.2 g., 0.01 mole) and acrylonitrile (0 .5 8 g., 0.011 mole) in dry benzene (100 ml.) was stirred for one day at reflux. Fil tration isolated fine lavender needles of 2-fluorenylidene- phenanthroC9»10]-l,3-dioxole (LXX, 0.730 g., 7*3% yield), m.p. above 520°. The infrared spectrum of this material was identical to that recorded in the literature.

(7 8) W. Ried and R. Dietrich, Ann., 639, ^3 (1961).

Solvent removal in vacuo from the filtrate left an 82% recovery of crude looking but spectrally pure phenanthrene-9t10- diazooxide. APPENDIX

75 76 to>m rjn i

4000 3000 2000 1500 700 100 00

- 2cd

-■32

Fig. 1 WAVELENGTH (MICRONS)

CM' 4000 3000 2000 1500 iqoo 990 800 700 1001 . 00

-2cd 160 - co o -32

20 -

WAVELENGTH (MICRONS) Fig. 2 1 4000 3000 2000 1500 1000 990 890 700 100 - 1 — 00

Ll I 160 - 2cd

20 :I0

WAVELENGTH (MICRONS) Fig. 3

f 77

CM 4000 3000 2000 1500 700 100 .. rO.O

LlJ ’60 .203 ~~o -33 -,4z 5m 20~~

~~Fig. k WAVELENGTH (MICRONS)~~

~~CM'1 4000 3000 2000 1500 loop 990 890_____ 790 100 .. 0.0~~

80 8 UJ 2ro 2 60 to 2 o ^40 z 4 z < 5m tr. .6 h 20 - 7 :I.O 0 +-—1 1----- 1----- 1------1----- 1----- 1----- 1----- 1----- r “I I I I I I •' I I S 14 15 3 4 5 6 7w a v e l ! n g t h 9(m ic r o n s ) 11 12 13 I Fig. 5

~~CM'1 4000 3000 2000 1500 1000 99O 89O 700 100 — 1 i_^. — - 1- 0.0~~

~~CHj~~

~~o-l 1----- 1----- 1----- r 12 13 7w a v e lI n g t h 9(m ic r o n s ) Fig. 6 78 f«.« n»~~

~~c m - 40003000 2000 1500 700 100 00~~

~~!60 i40~~

~~:I0~~

~~Fig. 7 WAVELl i 4000 3000 2000 1500 700 100..... r 0 0~~

~~•60- - 2cocd o~~

~~,4z -5m~~

~~:I0~~

~~WAVELENGTH (MICRONS)~~

~~4000 3000 2000 1500 iqoo 990 890 700 100 ■ 1 ■ rOO~~

~~■2od •60 r co 4 -4z -5m 20~~

~~WAVELENGTH (MICRONS) Fig. 9 79 i~~

~~4000 3000 2000 1000 900 800 7001500 100. 00~~

~~8 0~~

~~-3g -Az -5m 20 :I0~~

~~Fig. 10 WAVELENGTH (MICRONS)~~

~~CM' 4000 3000 2000 . ' „ 1500 1000 900 89O 700 100 “ri— -00~~

~~8 0~~

~~-203 to I 0~~

~~-Az ,5m 20~~

~~Fig. 11 WAVELENGTH (MICRONS) 1 4000 3000 2000 1500 1000 900 800 700 100.. 00~~

~~8 0~~

~~■60- .203 oto -•33 Az -5m 20 CN =10~~

~~WAVELENGTH (MICRONS) Fig. 12 80~~

~~'o'* 737« CM' 4000 3000 2000 1500 700 100 . 00~~

~~.80~~

~~-.2cd ■60- -•3S Az -,5m~~

~~■c-c h .~~

~~f 8 9 10 , Fig. 13 WAVELENGTH (MICRONS) to*m 7379 I CM' 4000 3000 2000 1500 iqoo 990 890 700 1001. 0.0~~

~~160- -.33~~

~~20 - :I0~~

~~WAVELENGTH (MICRONS)~~

~~1 4000 3000 2000 1500 1000 9Q0 800 700 1001 — 00~~

~~!60~~

~~Az 5m Ph-c 20 'C-Ph~~

~~Fig. 15 WAVELENGTH (MICRONS) 8]r~~

~~CM' lOQL^J4000 3000-- 2000 1500 looo 990 890 700 00~~

~~•60- -.203co o -33 ,4z -.5m 20~~

~~7379 I 4000 3000 2000 15001000 990 700 1001 " ■' rO.O~~

~~'60 -.2ro~~

~~20 OH :I.O~~

~~Fig. 17 1 4000 3000 2000 • 1500 1000 990 800 700 100..... rO.O~~

~~>60~~

~~20 :I.O~~

~~WAVELENGTH (MICRONS) Fig. 18 82~~

~~Him717 * i~~

~~4000 3000 2000 15001000 990 890 700 1001““— 00~~

~~■60- i40-~~

~~Fig. 19 WAVELENGTH (MICRONS) 1 40003000 2000 1500 1000 990 890 700 100 — 00~~

~~- 2dd~~

~~•33 -42 -5m~~

~~CHAC ■CO.CH,~~

~~Fig. 20 1 4000 3000 2000 1500 1000 990 700 1001... 00~~

~~1.2 CD ’60- 33 -42 -,5m 2a :I.O~~

~~Fig. 21 WAVELENGTH (MICRONS) CM'1 4000 3000 2000 1500 700 1001.. 0 0~~

~~>60~~

~~Fig. 22 WAVELENGTH (MICRONS)~~

~~CM 2000 1500loop 990 700 00~~

~~m - !60 2cd~~

~~Fig. 23 WAVELl~~

~~CM 4000 3000 2000 1500 1000 990 700 100 h— r“1—■ rOO~~

~~80-~~

~~2od '60~~

~~20 :I0~~

~~WAVELl 8*f~~

~~r*M>n»~~

~~4000 3000 2000 1500 1000 990 890 700 100..... 0.0~~

~~'60~~

~~i40- t-Ph 2 0 Ph-c :I.O~~

~~Fig. 25 WAVELl 1 40003000 2000 1500 1000 990 700 1001 . rO.O~~

~~- 2cd ■60 co o H.C ,CHJ -33 -Az -5rn e-Ph~~

~~:I.O~~

~~Fig. 26 1 40003000 2000 1500 700 1001... rO.O~~

~~80 iij '60~~

~~.CH-~~

~~Fig. 27 8.I5t~~

~~T.M.S~~

~~4.08t~~

~~oo VJ1 T.M.S~~

~~762t CN~~

~~Fig. 29~~

~~oo o\ 8.27 t~~

~~T.M.S 6 .9 5t 8.98 r~~

~~C O i C H j~~

~~7.63 r~~

~~Fig. 31~~

~~00 00 c-Ph Ph-c 5.61 T T.M.F~~

~~Fig. 32~~

~~oo vO m s . 6.77 T~~

~~VO o 8.87 t~~

~~T.M.S. EtOzC CO.£t A ■ ' 5.82t m s.~~

~~Fig. 35~~

~~VO I\> I~~

~~6.20 r~~

~~CO, CH.~~

~~T.M.S.~~

~~S*0y*yTh*«*y»*«*» V 1 *fi ww"»^rtwrt»/J~~

~~Fig. 36~~

~~VO V* 5.98 r~~

~~C „ H „ N , 0 , T.M.S~~

~~Fig. 37~~

~~VO ■F T. M.S.~~

~~P fi -c 7.93 t~~

~~3.19 r 5.54 r~~

~~\o VJl 0 HaC CH~~

~~Ph-C T.M.S.~~

~~5.56 r O~~

~~3 .2 9 r~~

~~Fig. 39 \£> cr> 4.I6t T.M.S~~

~~Fig. *fO~~

~~VO -v]~~