THE SYI'ithesis of 1-Bromobehzd

THE SYI'ITHESIS OF

1-BROMOBEHZd [C ]PH:nmTHRENE

. DISSERTATION

Presented in Partial Rilfillment of the Requirements . for the Degree Doctor of Philosophy in the ° • Graduate School of The Ohio State° U niversity

DONALD KENNEY PHILHPS, B .S .

the Ohio S tate U niversity ° 1958

Approved by

r ^ T k d v w ^ ' Adviser Department of Chemistry

0 0 * 0 0 o o O o o o o

° o O o O o ACKNOnLEDQDiNT » «

I am deeply indebted to Professor Melvin S,°Ne%man, who suggested this problem, for his^advice, encouragement and personal friendship throughout the course of this .work,

I would also like to thank the Department of Chemistry for financial assistance in the form of several assistantships and an assistant instructorship and the Office of Ordnance

Research, U .S. Array, for a research fellowship,

11 CC^TJ^TS

Page

Intrcductiori I ” » , Statenenf o f‘the Problem 12

• o ° Outline of 5enzo[c]phenanthrene Syntheses 13 Discussion of Results • ‘ ‘ 29 '

Experimental . . tl

Generalizations • •■ • • hi-

e-Broniobenzaldehyde ' ' ' hi

Diethyl o-Dromobenzalraalonate <3 o-Brom.obenzalmalonic Acid and l-Bromocinnanic Acid

' Diethyl o-Bromo’oenzhydrj'lmalcnat®,

2-(o-Bromobenzhydryl )-l,3-propanediol Via Diethyl o-Dromobenzhydrylmalonate 56

o-Dromobenzalmalononitrile' ' . . 58

0- Bromobenz hydrylmalononitri l e 59

Ethyl o-3romobenzalcyanoacetate • 61 '

Ethyl o-Bromobenzhydrylcyanoacetate . ’ 62

o-Bromobenzhydrj'lmalonic Acid 6!i . * Dimethyl o-Broraobenzhydrj'lmalonate . 66 2-(o-Bromobenzhydryl )-lj3-propanediol Via Dimethyl o-Br.omobenzhydrylmalonate 67

2-(o-Bromobenzhydryl )-l, 3-propanediol-bis-’ (methanesiilfonate ) 68

3_(o-Bromobenzhydryl )glutaric Acid 70

6a, 12b-Dihydro-l-bromobenzc[ 0]phenanthrene- • 5j8(6H,7H)-dione 72

i i i (contd.)

tape

S,if 6a,7,3,12b-H3xahydro-l-bromobGnzo[c]- phenanvfü'ene-6, o-di 75

1 - or o."'iObenso [ c ] phenan bhr ene 78

ether Attempted methods of Dehydration of VIII 85

1-Cyonobenso[ c jp'nenantkrene 87

Su'in'riP.ry 89

Autobiography 91

IV TABLES

Table Page ® o 1. Variation of Double Bond Absorption Bands of the Unsaturated Esters and Nitriles» 3C

2. Positions of the liaxima and° Corresponding Intensities in the Ultraviolet Absorption Spectra of Benzo[cJphenanthrene, 1-Methyl- and 1-Eromobenzo[c]phenanthrene h3 3. Reaction of Ethyl o-Bromobenzalmalonate (II) with Phenyimagnesium Bromide 57

li, Gyclization of 3-(o-Bromobenzhydryl)glutaric Acid (IV) to 6a, 12b-Dihydro-l-bromobenzo[c]- phenanthrene-5',8(6H,7H)-dione (VII) vrith Polyphosphoric Acid

5. Deh^'dration Using Iodine in Xylene 3i; f j-u' K;;iO

Figure Page

1. Outline of the Djerassi and Srossnickle Synthesis

2. Outline of the Gaind, Mulcherji and Coworkers Syntheses 17

3. Outline of the Thoi and Belloc Synthesis

U. Outline of the Phillips and Ji)hnson Synthesis; Path A /'J

5. Outline of the Phillips and Johnson Synthesis: Path 3

6, Outline of the Mousseron, Christel and Salle Synthesis

7. Outline of the Davies and Porter Synthesis 23

8, Outline of the Klibansky and Ginsburg Synthesis 25

9» Outline of the Phillips and Chatterjee Syntheses 26 10, Outline of the Proposed Synthesis of 1-Bromobenzo[c]phenanthrene 30 11, Outline of Possible Modifications of Proposed Synthesis 33 12, Outline of the Synthesis of l-3romobenzo[c]- phenantiirene 35 13# Ultraviolet Absorption Spectrum of 1-Bromobenz o[ c.] phenanthrene 12

VI EJTRODUCTÏON ^

° 0 0 Uniplanarity is a well-established characteristic of many f^oljmuclear arom atic hydrocarbons. 1 "■ 7 However, there are a number o

(1) H. h. Ehrlich, Acta Cryst., 10, 699 (1957).

(2) "E, C lar, W. Kelly, J.. "U. Robertson and M, G, Rossmcinn, J . Chem. Soc., 3878 (1956). - -

(3) H. 17, Ehrlich and C. A. Beevers, Acta Crvst,, 9, 602 - ' (1956). . .

(li) D. M. Burns, Acta Cry st., £j (1956).

(5) V. C. Sinclair, J. H. Robertson and A. McL. Mathieson, . Acta Cryst., 25l (1950).

(6) J . Ib a ll, Z, K rist., 99, 230 (1938). C.A., 32, 8236^ (1938).

(7) J* il. Robertson, Proc. Roy. Soc. ' (London), Allt2, 67U (1933). polynuclear aromatic hydrocarbons, termed "overcrowded" by Bell and

-r • 8

(8) F. Bell and D. H. Waring, J. Chem. Soc., 2689 (19^9). intramolecular repulsions between non-bonded atoms.

(9) E. Harnik, F. H. Herbstein, G. M. J. Schmidt and F. L. ^Hirshfeld, J. Chem. Soc., 3288 (195U) and references cited “th e re in .

(10) A. 0. McIntosh, J.M. Robertson and V. Vand, J. Chem. Soc., "1661 (195L).

Benzo[cjphenanthrene (I) and its derivatives have been shown to be exanples of the latter type of confound." \ recent X-ray

O o cristallographie investigation^^- has demonstrated, that the rings of

(11) F. H. Herbstein and G, *•?. J. Schraidt, J, Chern, Soc., 3302 (195L). the parent hydrocarbon (I) are folded so that the distance between

1 ! plana of paper 1 = 3

plane bent up lU* from t— 1

nïïTiïi plhne bent up 11* from

plane bent down lU* from 1 1

plane bent down 11® from carbons 1 and 12 is 3.0 & instead cf 2.1 S, the distance expected between the two atoms if the molecule were p l a n a r , ^2 because of this-

(12) It is interesting to note that &enzo[ghi]fluoranthene (II) has been sho;m to be planar, although the new bond (l.ij.9 A) causes considerable stress in the molecule, mainly "in bond * * angle distortions [H. W, Erlich and G, A, Beevers, Acta Cryst,, £, 602 (1936); sge N. Campbell and D*. H. Reid, J. Chem. Soc,, 3281 (1932) and 0. Kruber and G, Grigoleit, Ber., §2, 1893 (193L) for the synthesis and*other properties]. o o o o

non-planarity there is a possibility of separating benzo[c]- phenanthrene into d and 1 isomers, Herbstein and Schmidt comment that

’the crystallographlc evidence indicates resolution of 3j4-benzophenanthrene into (*)- and (-)- crystals, vfe have not yet succeeded

in groifing crystals either of large enough sise or with sufficiently well-developed h]

benzophenanthrene: experiments in this direction are in progress."

The deformation of the rings caused by the sterio interference

of the carbons (and hydrogens) at positions 1 and 12 would be

expected to affect the physical and chemical properties of benzo[c]-

' phenanthrene and there is evidence that it does. The theoretical

resonance energy of ben%o[c]phenanthrene as calculated by the molecular

orbital method for a planar molecule is 13h.9 kcal, per mole,

determined with allowance for overlap between adjacent atomic prbitals

and 133.8 kcal, per mole, with no allowance for'overlap. ^ .The

(13) G. ^erthier, C. A. Goulson, H.H, Greenwood and .A, Pullman, - Conç)t. re n d ., 226, 1906 (19U8). ------s------— ------

0 0 © Q o ©

e:{peri%entally daterMred valus îs 127.7 kcal,’per mole,-’-* The

(Ik) A, Magnus and F, Becker, Erdttl u. Koîile, U, ll5 (l?5l)j G. A., 6038° (1951).

en erg y difference of six or seven kcal, must be related to the

energy of Intramolecular repulsion, neglected in the theoretical

calculations, and. to the deformation of the hypothetically-planar

ring system,^^

Benzo[cJphenanthrene is reported to have a dipole moment of

Q„07 t 0,0? which has been attributed to the dipoles of the G-H

(l5 ) E, D, Bergmann, E, Fischer and 3, Pullman, J . chim, nhys., h8, 356 (1951).

bonds, which do not cancel in the deformed structure as they would

in a regular planar molecule

The X-ray determination shows bond angles of 110® at carbons

3 and 10 and 111® at carbons 5 and 8, Thus the te tra h e d ra l angle of

109-1/2® is approached. This implies that the valency electrons of

these secondary atoms do not occupy pure (sp^)p orbitals, appropriate

to a planar aromatic structure, but more nearly approximate to the

tetrahedral sp^ hybridization and iirplies & greater localization of

the pi electrons at these atoms* This view^^ would explain,- in part,

the preferential attack o f electrophilic agents at the 5-positio'n

during bromination, nitration, of acetylatioft of the nucleus.l^ " ...... ’ ------—-----° -a (l6 ) M, S, Newman and A* Î , Kosak, J , Org. Ghem., ih , 375 (19k9). o 0 o o o

o ®

It can be seen then that the steric interference of the carbon

(and hydrogen) atoms at positions 1 and 12 alters the properties of benzo[c]phenantlirene considerably. The introduction of various groups at the 1- and 12-pasitions should result in even greater steric interference and consequently greater non-planarity of the aromatic system. The effect on the physical and chemical properties

should be much more pronon.'uiced.

Few cormounds containing su b stitu en ts a t the desired p o sitio n s have been studied, however, The main problem has been their

îjinavailability due to difficulties in synthesis. The total number of 1- substituted and 1, 12-disubstltuted bensofcjphenantlirene derivatives that have been synthesized numbers less than ten and most of these have been prepared quite recently* The first reported synthesis o f a 1-substituted benzoFc jphenanthrene was that of 5- isopropyl-?-methylben2o[c]phenaatlirene-l,2-dlcarboxylic acid (III) and its anhydride along with 8-5.sopropyl-i|-methylbenzo[c]phenantIirene

(2,6-benzoretene)(iy) from reten e (V ).^? However, a recen t

(17) D. E. Adelson and II* Ï, Bogert, J* Am* Chem, Soc,, 1776 (1937). investigation^® has indicated that the structure of the compound

(18) L,-V, Thoi and A, Belloc, Gonçit* rend*, 239, ^00 (195U). o

pictivred as III is incorrect and coul-? be VI or VII, but more likely VIII or IX because of steric considerations.

CH CH3 CÙ%H

CH,

30:

WoCs

Cûj« C«3 7

The first unambiguous synthesis of a 1-substituted benzo[c]-

•phenanthrene derivative was that of l-methylbenzo[c]phenanthrene (X),

along with l-raethylbenao[c]phenanthrene-l;-acQtic acid (XI), in

19^8.^^ The synthesis of X by a different route has been reported,20

(19) M. S. Newman and II, B, Wheatley, J, Am, Chem, Soc,, 70, 1913 (I9k8),

(20) M, S,Newman and IÎ, Wolf, J, Am, Chem, Soc,, 7L, 3225 (1952).

Recently, l,l;,5-trlmethylbenzo[cJphenanthrene (XII)21 and

(21) A, W, Johnson, Ph,D, Dissertation, Cornell University, 1957; Dissertation Abstr,, 2W.9 (1957).

l,3,5,8-tetrameth7lbenzo[c]phenantlirene (XIII)22 have been synthesized.

(22) V, S, Gaind, R, P, Gandhi, I , C, Ihkhumna and S, M, liukherji, J, Indian Chem, Soc,, 33, 1 (1955); I, C, Lakhumna, V, S, Gaind and S, N, liukherji, Current Sci* (India), 23, 159 (195U); C. A ,, U9, 9596b (1955).

The preparation of li-methylbenzo[c]phenantlirene-l-ol acetate (XIV),

• ' . ^

the first behzo[cJphenanthrene derivative containing a reactive

function in the 1-position, by way of a dienone-phenol rearrangement

O 0 O o o ° o ° . ° e o ® © ® o has teen r e p o r t e d , 23 HoHever, the stru ctu re of the compound was not

(23) Ca Djerassi and T, T. Crossnichle, J* Am* Ghem. Soc., 76* ITUl (19SL).

rigorously proved.

"SOI - y m

A few 1, 12-disubstituted benzojcjphenanthrens derivatives

have been synthesized. The synthesis of 1, 12-dimethylbenzo[ c] -

phenanthrene (X7) and 1,$,8,12-tetramethylbenzo[cjphenanthrene

(XVI) has been reported,^^ Recently 1, 12-dimethylbenzo[c]-

phenanthrene-5-acetlc acid (XVII) was synthesized.^^ A preliminary

(2li) H. S. Kewraan and R. M. Wise, J , Am, Chem* Soç«« 7 ^ h$0 (1956).

dH3

9 0 irV TT

9 9

O o o

report of X-ray crj-stallographlc studies of l,12-dimethylbenzo[c]-'

phenanthrene (XV) indicates that the nolecule has a considerably

more non-planar structure than benzo[c]phenanthrene, as would be

exnected,^^

(25) F. L. H irshfeld and G, II.J, Schmidt, Acta Cryst,, 9, 233 (1956).

The effects of out-cf-plane deformations on the properties of

1 - substituted and 1 ,12-disubstituted bcr«ic[cjphci.Rntl-irene derivatives

have not been studied extensively. Resolution of l-meth;/lbenso[c]-

phenanthrene-!+-acet3c acid (XI) has resulted in the isolation of an

isomer having a specific rotation of +1,0 to +2,3*,^^ On standing

the rotation gradually disappeared. The resolution of l,12-benzo[c]-

phenanthrene-5-acetic acid (XVII) has been accomplished,^^ The

enantiomorphs, (+) XVII, M ^ ^ 3l7,6 't 3.6" and ( - ) XVII, [o<]25

=362,7" 2 2,5% were optically stable. Racémisation occurred only

at temperatures (ca, 250") at which decomposition began.

Recent eiiperiments have shovm that the greater the departure

from a non-planar structure, the greater the localization of the

.electrons which are usually delocalized in aromatic rings and, as a

result,' for cxangjle, the greater the availability of the electrons

for-reaction with free radicals, Methyl radicals add to aromj+lc

compounds and the relative rate constants are referred to as methyl

affinities. The methyl* affinities have been measured for ,benzo[c]- o » a © ® ® 0 ® © phenanthrene, all the raonomethylbenzo[c]phenanthrenes, and fpr ° C 9

® c 9

O 9 3 a O ® ® o 0 0

. • 10

l , 12-^lmethyIben 2o[c]phenanthrene. 2 G xhe methyl a f fin itie s of 2-,

(26) M, Levy, S. Nei-man and H, Szv;arc^ J* Am, Chem, Soc,, 77, 1225 (1955).

3-, L-, 5-, and D-methylbenzofc jphenanthrene are rougîily the same

(in the range 55-71', the rate of benzene being taken as nnity) and

ai'e about equal to that of benzo[c]phenanthrene (6U), However, the

methyl affinity rises somewhat for l-methylbenzo[c]phenanthrene

(107-108) and considerably for l,12-dlmethylbenzo[cjphenanthrene

(181 -181 ).

The ultraviolet absorption spectrum of l-methylbenzo[cjphenan

threne has been compared to the spectra of benzo[c]phenanthrene and

the other nonomethi'lbenzo[c]phenanthrenes and shows an anomalous 27 bathochronic shift of all peaks and loss of fine structure, which

(27) G, M, Badger and I . S, Walker, J, Chen, Soc,, 3238 (195L).

are probably associated with the distortion of the aromatic ring

system.

The failure of l-nethylbenzo[cjphenanthrene to form a picrate^?

in contrast to the five other monomethylbenzo[c]phenanthrenes has

been attributed to the non-planari.ty of the molecule,

(28) M. Crchin, J, Org.'Chem., 16, ll65 (1951).

Dissociation constant measurements of the"2,q,7-trlnitrofluore«

■hone complexes of the monomethylbenzo[cjphenanthrenes have shown that_^

a the complex l-methylbehz&[c jphenanthrene is the most unstable one o e 0 0 0 © 0 o © u cf Viw se rie s. ??

(29) K, H. Tcdceriura, M, D, Cameron and II, S.Ketnnan, J, Am, Chem, Soc,, 79, 320 0 (1953).

Since only two molecules. III (or VI), and XIV, have been reported containing functional groups in the 1-position and these '

have structures not conclusively proven, little or no work lias been

done with compounds of this type.

From the foregoing discussion it can be seen that steric

interference in benac[cjphenanthrerie derivatives between groups or

atoms at the 1- and 12-positions inparts unusual properties to the

molecules and that the greater the interference the greater the

effect. It would be of interest then to devise a route to

benzo[c]phenanthrene derivatives containing functional groups in

the 1-p o sitio n . These molecules would o ffe r a method of studying

not only the effects of steric interference on the aromatic ring

system but also on the functional groups themselves. STATHviENT OF THE PROBLEIA ’

The purpose of this research vras to synthesize 1-bromobenzo [c ]- phenanthrene which might be useful as an intermediate in the preparation of a number of 1-substituted benzo[c jphenanthrene

derivatives and in the synthesis of hepta-, octa-_, aona- or 1 decahelicene•

(l) See M. S* Newman and D. Lednicer, Jo Am. Chem. Soc.,

7 8 , U765 (1956 ) for the synthesis of hexahelicene.

12 o o o o o 0 o o o

OUTLINE OF BENZO [aJPHENAKTHRENE SYNTHESES

The synthetic routes to the benzo[c Jphenanthrene ring system

have been reviewed by Kosak (through by Wolf (through 19^0)^

(1) A. I. Kosak, Ph. D* Dissertation, The Ohio State University, 1918.

(2) M. Wolf, Ph. D» Dissertation, The Ohio State University, 19^1.

and by Wise (through 19$L) Further syntheses o f th is system

(3) R. M. Wise, Ph. D. Dissertation, The Ohio State University, 1953.

(through Chemical Abstracts, 19^6, and several syntheses reported

later) are outlined below.

The synthetic route used ty Newman and Wolf^ to synthesize

(li) U, S. Newman and If. Wolf, J . Am. Chem. S oc., 7 ^ 322^ (1952).

several benzo [cjphenanthrene derivatives has been modified.^' ^

(5) K. S. Newman and R. If. Wise, J. Am. Chem. Soc., ?8, U50 (1956). “ “

(6) M. S. Newman and D. Lednicer, J . Am. Chem. S oc., 78 U765 (1956). ^

Since this method forms the basis for the present research, it will

be described in another section (see page 29),

® 0 23 ® o © © o ®® © g $

o ® © o o O a 0

Dienone-phefiol rearrangement^ of 5>6-dihydl*o-iia-methylbenzo[c]-

(7) C. Djerassi and T» T, Grossnickle, J, Am. Chem. Soc., 76, I7I1I (195U).

phenanthren-2(LaH)-one (II, Figure l), prepared in 23$ yield from

I, resulted in a mixture of two isomeric acetates, ^,6-ditydrc-li-

methylbenzo[cJphenanthren-2-ol acetate (ill) and 5,6-dihydro-U-

methylbenzo[c]phenanthren-l-ol acetate (IV). Del^drogenation over

palladium on charcoal led to the fully aromatic acetates V and VI#

The structure of V was proven by independent synthesis of the phenol

(VIl) by a knovm route,^

(8) A. L. ¥ilds and C« Djerassi, J. Am, Chem, Soc., 68, 171^ (I9îi6),

(9) A. L. Wilds and R* G. Werth, J, Org, Chem., I7, U$L (19$2), The preparation of Ii,Ua,5,6-tetrahydro-lHnethyTbenzo[c]- phenanthren-2(3H)-one (VIIl), but not its conversion to a fully aromatic compound, is also reported in this article*

VIII

,CHOH No H CHO 2 ; CH3I CH 3 I

I. GH3GOGH3 piperidine, HOAC 2 KOH, G H ,O H OAC

HbS04 CH, Ac«0 GHs 2S I Pd-C 23% from I ^ ACgO oyridine OAC AcO

CHj

TZ %

P d-C üAlHj

CH, CH

Pd-C p -cymene 0 I CH3COCH «GHCH, NoOCH, CfeCH3 2 KOH, H2O

• FIGURE I

A number of $-methylbenzo [c Jphenanthrene derivatives have been

synthesized by a general method (Figure 2) starting from 2-allyl-l-

tetralone (IX) and its derivatives The compounds 5-ffiethylbenzo[c]-

(10) V. S . Gaind and S. M. Mukherji, Current S c i. (India), 22, 23$ (1953); C. A ., 18, 2676b (1951).

(11) Ibid., 23, 159 (1951); C. A., h9, 9596b (1955). (12) S. M. Mukherji, V. S. Gaind and P. N. Eao, J. Org. Chem., 19, 328 (1951).

(13) V. S. Gaind, R. ? . Gandhi, I . C. Lakhumna and S. M. Mukherji, J. Indian Chem. Soc., 1 (1956).

phenanthrene (X), 2,5-dimethylbenzo[cJphenanthrene (Xl), 5*8-dimettgrl-

benzo[cJphenanthrene (XII), 2,5,8-trimethylbenzo[cJphenanthrene (XIIl),

1 ,3 ,5 j8-tetrametlylbenzo [cJphenanthrene (XIV), 2-methoxy-8-methyl-

benzo [cJphenanthrene (XV) and 2 ,5-dimethyl-U-methoxybenzo [c Jphenan

threne (XTl) have been synthesized by this method.

The ^nthesis of 5,6-benzoretene (XVIII), (Figure 3), a possible

active carcinogen,, in s ix steps from dehydroabietic and (XVIl) has

been d escrib ed .^ The compound XVIII d iffers from the compound

(m) I.-Y. Thoi and A. Belloc, Conçt. rend., 239, 500 (195k).

previously ascribed this formula,^^ Tihich is now believed to possess

(1 5 ) D. E. Adelson and M. T. Bogert, J. Am. Chpm. Soc., 1776 (1937) .

. ■ the structure XIX#.

0 . “ I l

I. NoOEt 2 GHg = CHCHgl 3. NaOH 82% CHOrt. IZ

CfiHg, AlCI, 82%

A l (OiPr)j * iPrOH 8 6 %

H2SO4 QO 70%

Pd-C 58 % CH

XL: R| = Rg = = Rg = H) Rg ~ CH3

XjL'* R| " Rg- R3 — Rg ” H •, R4 - CH3

Xiii : R| " R3 " Rs "H ) R g - CH3 XiV : RI “ R3“ R4 =CH3 ; Rg = Rg = H Xl3T‘ R| ^Rg^Rg-R^ "H; Rg - OCH3 3C!ZE‘*^R| - R 3 “ R4"H; Rg'CHgj Rg = OCH3

FIGURE 2 • o

«o CHpCO I > CHgCO AIGU . 60%

I. Clemmensen

FIGURE 3 19

A new method of preparation of benzo[c]phenanthrene was developed from the readily available ^-methallylsaccinic acid (XX). 1 3

( l 6 ) I), D, Phillips and A, ’X, Jo}inson, J. Am, Chem. Soc,, 77, 2977 (1953).

By path X (Figure U) XX was converted to XXI in 21:3 yield. By path

3 (Figure 5), XXI was obtained in about 9% yield, XXI was converted in 3S;3 yield (92;3 based on unreacted XXI) to 2-methylbenzo[c]- phenanthrene (XXII), Variations of the above methods yielded 5,6- dimethylbenzo[c]phenanthrene (XCIII) and i,L , 5-trimethylbenzo[c]- 17 phenantlirene (XXr/).

(17) A. V7. Johnson, Ph.D. Dissertation, Cornell University, 1957; Dissertation Abstr., 17, 2hl9 (1957).

Ben2o[cjphenanthrene has been prepared in good yield (^h%) in a five-step synthesis from 2-h;rdroxymethylsne-l-t 9 tralone (XX7)

(Figure 6 ).^^ The method involved a ring expansion during the acid

(18) II. Ilousseron, 11. Christol and P., Salle, Coiipt. rend., 2U5, 1366 (1957), deliydration of an alcohol.

A convenient synthesis of benzo[cjphenanthrene from 2-vinylnaphthalene (XXVII) in 19^ yield hasbeen described (Figure 7).I?

(19) v7. Davies and Q. II. porter, J. Chem. Soc,, 1+967 (1957).

Path A:

ÇH, CHg* CCHjCHCO SbCIs 0 44% CHjCO CH, zr

1. C ^ , AlCI, 2. H „ Pd -C 56%

I PCts .C H j ,CH. 2 .AlCI, 8 9 %

,1. LiAIH, 2. HgSO* 60%

CH, ,CH, CHj OH,

P d -C , 70%

P d-C 33% . CH, CH, (92% b 08«d on un;«ocM ZZt

FIGURE 4* .

CH, OH, HGi CH: C-CHgCHCO I 78% GHjGO

C«H,, AlCI, 91%

CH, CM CH, C H ,

f. ACgO 2. AlCI, HO, 60%

1. G^HgMgBr 2. Glemmensen 43%

!. PCÎ,

GO,H 2. AlCI, 78%

H,, Pd-C, 65% 2. Pd-C

XDC FIGURE 5 0

0 ® ® 11U

CHeCOCH = GHz 75% HOH xn r

1. KOf-Bu 2.Br (GHg^Br 8 0 %

I. Li AIH4

2. KHSO4 90%

P d -C 100%

FIGURE 6

9 9 * . •* % 2 3

Af (O iPr )3 iPrOH 86 % ,CH, COCHj H OH

distill 6 5 %

3 7 % z m c X E n r

Li AIM* 50% THF

XXIX

FIGURE 7 .. - - ' - ' ' -

Diels-Alder'addition of benzoqninone to 2-vinylnaphthalene (prepared

in yield from XXVI afforded an adduct (1:07111), which on

(20) Ibid., (1957).

reduction with lithium aluminum hydride in tetrahydrofuran yielded

XXIX.

Employing a Michael condensation as one of the key step s (XX:{I

to XXXII), l-'X-naphthylcyclohexene (XXX) has been converted to

benzo[c]phenanthrene (Figure 8 ), The y ie ld from XXX to XX:(II

(21) Y. Klibansky and D, Ginsburg, J. Chem, Soc,, 1293 (1957),

was 22^* The use of the carbonyl groups in several intermediates

and the differences in their reactivities for introduction of

substituents in positions X to these groups was suggested,

Benzo[c]phenanthrene has beer, prepared in small quantities

during an investigation of the Friedel-Crafts condensation of trans-

2-hydroxycyclohexaneacetic acid lactone (XXXIV) with naphthalene

(Figure 9).A small amount of 5-methylbenzo[c]phenanthrena (XXXV)

(22) D. D, Phillips and D. N. Chatterjee, J. Am. Chem. Soc.,

BO, 1360 (1958).

was,obtained when 1-raethylnaphthalene was [email protected]

(23) Ibid., 1911 (1958).'

O O O o oo @ o 0 o 0 . , ° o » o O® o * O o O 0 0 9 0 O O

2. (COgH);, toluene 70%

1. CHglCHg), NOg, H* 2. KOH, EtOH 3. HCHO, HCI dioxane 71%

1. Nort, CHjCCOaCHaCeHal^

2. HBr, HOAc 3. A 33 % 2 Z Z X

HF 9 5 %

1. CgHgCHgSH BFj • EtgO

2. Roney Ni

Pd-C

FIGURE 8

9 O • 9 o* 0 o AlCIi OO'c»o * XXXIV:

1. LiAIH4 2. Pd-C

OHs

AlCIin*

HOgC

I. LiAIH* • 1 2 . Pd-C

FIGURE 9 » o

o o o o

0 o

o 0 0

It is of interest to note that the diene synthesis developed

by Szmuszkovdcz and Modest^^' and employed by Nemnan, Anderson

(2li) J . Szmuszkowicz and E. J . Modest, J . Am* Chem, Soc., 70, 25U2 (1918 ).

(25) Ibid., 72, 566 (1950).

and Takemura^^ to prepare a number o f benzo[c]phenanthrene derivatives

(26) M .S . Neviman, H. V. Anderson and K. H. Takemura, J , Am. Chem, Soc., 7 i, 3^7 (1953).

vas unsuitable for the preparation of lwnethylbenzo[c]phenanthrene,

l-methoxybenzo[c]phenanthrene and l,U-dimethylbenzo[c]phenanthrene.

In these cases maleic anhydride failed to add to 1-(o-tolyl)-3 , h-

dihydronaphthalene (XXXVl),^^ l-(o -a n isy l)- 3 ,ü-dihydronaphthalena

(XXXVll)^^ and l-(o-tolyl)-7-methyl-3,Zi-dihydronaphthalene (XXXVlll),^

respectively, ■even under forcing conditions.

XXX.VI XKX VIII

o e 0

o o 0 28 .

After a consideration of the previous routes to benzo[c]- phenanthrene derivatives, it can be seen that the following ' requirements should be met in order to achieve a successful synthesis of 1-bromobenzo[c]phenanthrenex

1. The steric hindrance in the molecule should be introduced stepwise and not a ll at once. The bromine should be introduced early in the synthesis.

2. All reactions that might involve attack on the bromine on an aromatic bromide, such as very strongly alkaline reactions at h i^ temperatures or reactions involving reactive metals, Should be avoided. The synthesis^”^ which had been used successfully for the preparation of several 1-substituted and 1 , 12-disubstituted benzo [c ]phenanthrene derivatives was chosen as the method tliat would meet these requirements and would most likely be successful for the .. sy n th esis. © o (?>

DISCUSSION OF RESULTS

The original plan for the synthesis of l-broraobenzo[c]-

phenaithrene was to employ the method (Figure 1C) of Nemian and

Wolf^ as modified by Nev/man and .Wise^ and Newman and Lednicer^

(1) M, S, Newman and M, Wolf, J, Am* Chem, Soc,, Jkj 322$ (19$2),

(2) N, S, Newman and R, M. Wise, J , Am, Chem, Soc,, 78, L$0 (1956). - -

(3 ) H, 3, Kewirian and D. Lednicer, J . Am, Chem, Soc,, 7 ^ U?65 (1956).

starting from o-bromobenzaldehyde,

o-Bromobenzaldehyde^ was nrenared in 68 ^ yield from o-bromo-

(i;) o-Broraobenaaldehyde has been prepared [R, Adams and E, H, Vollweiler, J, Am. Chem. Soc., l£0, 1737 (1918)] essentially by ■ the method employed in th is work in 80^ y ield . I t has also been prepared in 6$^ yield bj* treatment of o-bromobenzylbromide with the sodium salt of 2-nitropropane [D, F, DeTar and ■ L, A, Carpino, J, Am. Chem, Soc,, 78, U7$ (19$6)], in 70^ yield by hydrolysis of o-bromobenzalbromide with sodium acetate in 7$^ ethanol followed by refluxing with calcium carbonate and w ater [D, F, DeTar and L, A, Carpino, J, Am, Chen. Soc., 78, U75 ( 1956 )], in 1$$ yield by catalytic hydrogenation of o-brqmobenzonitrile over a nickel catalyst followed by acid hydrolysis [7, H. Rupe and F. Bernstein, Helv, Chim, Acta,, 13 « (1930)], by oxidation of o-bromotoluene with chromic acid in acetic acid to o-bromobenzaldiàcetate, followed by ■ acidic hydrolysis [0, L, Brady, A, N, Cosson, and A, J, Roper, • J, Chem. Soc,, 127, 2ii27 (192$)], and by boiling o-bromo benzylbromide with plumbic nitrate and water in a carbon dioxide artraosphere [C, L, Jackson and J, F, White, Am, Chem, J ,, ^ 30 (1881 )], ' "" ' ' ' ■■''■■■■ ■ ■ II ■ ■ I—■■ W "" ■ ■ i toluene by dibromination to o-bromobenzalbromide followed by mild

alkaline hydrolysis using calcium carbonate and water. The method is » 29 O ® • o • 0 o • • o c » " . .. ". . ;

0.0 „ o . . © ©

3 0

C H ,(C O ,E iy

CHO II C ErOgC*' ^COgEf H

L iA fH *

CHjSOgCl

HOCH, CHgOH Y IZ

1. KCN 2. NaOH, HgO HOCHgCHgOH

Friedel - Crofts cyclizotion HO,C

Li AIM.

1.-2H2O 2 .-2 H . . HO" OH VTTT FIGURE 10

« e ■ 31

quite satisfactory since the starting material is inexpensive and

the method is adaptable to large scale work.

The aldehyde condensed readily with diethyl malonate to form

diethyl o-bromobenzalmalonate (II) in 8 % yield. The diester was

hydrolyzed to o-bromobenzalmalonlc acid, which was decarboxylated

to o-bromocinnamlc acid.

The l,L-addition^^C pj- phenylmagnesium bromide to dieth y l

(5) E, P, Kohler, Am# Chem, J , , 3L, 132 (190S),

( 6 ) M, S, Kharasch and 0, Reinmuth, "Grignard Reactions of Mon- Metallic Substances," Prentice-Kall, Inc,, Mew York, N,Y, (19SL), pp. S63-56U,

o-bromobenzalmalonate (II) to yield diethyl o-brcmobenzhydrylmalonate

(III) did not proceed well. Normal and inverse additions using ten

per cent excesses of Grignard reagent afforded 28^ and

respectively, of crude l,L-addition product and large quantities

of recovered starting ester. Reaction in the presence of magnesium

bromide did not increase the yield. Inverse addition followed by

refluxing at 65® and Inverse or normal addition using large excesses

(100^ excess) of Grignard reagent raised the crude yields to

6$-S9%} however, redistillation lowered these yields considerably.

In each procedure tried, the product on distillation was contaminated

by starting unsaturated ester, even when 10QÈ excesses of Grignard

reagent were'used, and considerable high boiling tarry residues

were obtained. It is possible that reaction* at low temperatures or

0 . " . ' " , ... * e e e « , O n A O a *» ® ® o

. ' ' ' - . . 22

. reaction in the presence of cuprous, chloride'*■ 7 B would •result in an

(7) J. î-îunch-Petersen, J* Org, Chem,, 22, 170 (19^7) and references cited therein,

( 8 ) Dr, J, Munch-Petersen (private communication) states, however, that he has obtained variable results in his work depending on the sample of cuprous chloride and that, apparently, some unl-:nown factor has been responsible for its remarkable effect, lie also reports that, in the reactions of Grignard reagents with sec,-butyl crotonate, the yields of l,h-addition product are increased by using an excess (2-]/2 moles) of Grignard reagent,

improved yield of l,li-addition product.

Lithium aluminum hydride reduction of diethyl o-bromobenzhydrjl-

Toalonate (III) to 2-(o-broraobenzhydryl)-l,3-propanediol (IV) proceeded

in good y ield ( 865?), The dlol was converted to 3-( o-bromobenzhydrjl )-

glutaric acid (VI) by the method of Kewman and coworkers^*^ (see .

later discussion).

Although the desired 3-(o-bromobenzhydryl)glutaric acid could

be obtained by the method outlined above, it was felt that an alternate

. route avoiding the reaction of phenylmagnesium bromide with diethj'’l

o-bromobenzalmalonate (II) was desirable. Two possible routes • .

involving the same general method of synthesis which seemed worthy of

trial are.shown in Figure 11,

Path A seemed reasonable since, in a similar series of reactions,^

.(9 ) M, S, Newman and H, R, Flanagan, J, Org, Chem,, 2 ^ 796 (1958),

, 1-naphthaldehyde had been condensed with ethyl cyanoacetate to afford

ethyl 1-naphthylidene-cyanoacetate (X, Ar » 1-naphthyl) iji 92,8% yield.

O * . o 0 3 5

Path A:

CN ArCHO + CH, — COzEt ArCH = C(GN) COgEt Z

Ar MgX

, CHjO] , ArArCHCHCOOgH), ------. ArArGHCH(CN)COgE* 33E ZI

GHgNg

UAIH4 ArAr'GHCHIGOgGH,)* Af A/CHCH(CHgOH)g JŒL z i r

Path B‘

ArGHO + CHg(CN)g ArCri • C(CN)g

j Ar'MgX

[HgO] 33: ArAr'CHCH(CN)g 333

I LiAlrt4

ArAr'CHGH (GHgNHGOGHg^g ArAr'ÇHGH (GHgNHg), zzm: zsm

* NO ArAr'CHGH (CHgNCOCHa); ArAr'GHCH(CHgOGOCH,)g TTTT

FIGURE Ik © O ©

9 O o oo

' ' ' ' 3%, . .

The cyanoacetate was reacted with 1 -naphthylmagnesium brora.de to

yield ethyl di-l-naphthylmethylcyaiio’acetate (XI, Ar = Ar' = 1-naphthyl)

in 9h% yield, îîydrolysis of the product :d.th % potassium hydroxide

in ethanol afforded the malonic acid (XII, Ar " Ar' = 1-naohthyl)

in 92% yield*

In path 3, conversion of the diamine (r/II, Ar ■ o-BrCgH*,

At’ = C5H5 ) to 2-(o-bromobenzhydryl}-l,3-propanediol (17) or one

of its derivatives might be accomplished by decomposition of a

di-I'-alk;\'-l-N-nitrosoa'TLide^*' or sim ilar conversion*^'

(1 0 ) E, H, "Jhite [J, Am, Chem. Soc,, 77, 6Oil (195S)] converted a number of aliphatic ami.nes to "the corresponding alcohols by this method. The steps involved (XVII to XX) were acylation of the amine, nitrosation of the amide and thermal elimination of nitrogen from the resulting N-alkyl-N-nitrosoamide to form the corresponding ester. Good yields were obtained for primary carbinamines,

(11) C. Paal and L, Lowitsch [Ber,, 30, 869 (1897)] converted benzylamine to benzyl alcohol by preparation of the sulfamic acid. Treatment of its N-nitroso potassium salt with water ■ yielded benzyl alcohol;

CgHsCHaNHg + CsHsMHSOaNKgCHgCsHs

. % + ;

CgHgCHgOH CgHjiSOgK M in . ^

With these possibilities in mind, o-bromobenzhydrylmalononitrila

(XVI, Ar ■ c-BrCçH^, A r' ■ CgHg) and e th y l o-doromobenzhydrylcyano»

acetate (XXII, Figure 12) were prepared, . o-Bromobenzaldehyde was condensed with malononitrile to afford • * o-bromobenz^lmalononitrile (XV, Ar = o-BitlgH^) in® 71^ yield. Reaction . # » e ® ® o

0 o CN h i . ♦ CH,. ^'^^CHO CO,Et CC'X j^ C H = C(CN)CO,EfC X xzx

I C,HaMgBr

Br 2 5 % KOH in EtOH

•CO.H

CHgNg

LIAIH4

CHaP*C ^OjCH, HOCH. CH.OM XD7

CHjSOgCr, C^HjN

I. KCN

2. NoOH, H,0 . MOGHgCH^OH SC

polyphospTiorift Y o d d

xylene HO OH

FIGURE 12 O

"o' o A 0 0

of the dinitrile with phenyl'nagnesiun broînida in ether-benzene

yielded of crude oily 1,^4-addition product, which was

crystallized to yield o-brotnobenzhydryLTialononitrile (XVI,

Ar = o-BrCeH4, Ar‘ - CgHg) in 59% yield. When the reaction was

run in ether alone nuch of the starting nitrile was recovered.

This was apparently due to the insolubility of the Grignard complex

in this solvent,

c-3romobenzaldehyde condensed readily with ethyl cyanoacetate

to yield ethyl n-hromobenzalcyanoacetate (X)ÎI) in 91.2^ yield.

The Grignard reaction of XXI with phenylmagnesium bromide afforded

ethyl o-bromobenzhydrylcyanoacetate (XXIT) in 90,7% y ie ld ,

Apparently, the replacement of a carbethoxj^l group in diethyl

o-bromobenzalmalonate (II) by a c;zano group added enough positive

character to the ^-carbon to allow l,b-addition to occur with

■.ease. It is interesting to note that replacement of the carbethoxyl

groups by cyano groups causes a shift to higher wave-lengths o.f the

•double bond absorption in the infrared spectrum (Table 1), This can

Table 1

CoKTOOund G=G(KBr wafer)

o-BrCgHjCHbCCCOgEtja 6 ,1 0 p

o-BrC 6H4CH=C(CN)G OgEt 6,20 p - • •

. o-BrGgH4CH=C(GN)2 ;^6,30 ]i

0 • % o

G G

G O O 0 O e G . be attributed-ira:’.nly to the greater electron attracting power of the _

nitrile group (from r.odels it appears that steric factors are at a minimum]. Compare the double bond absorption band of ethyl crotonate

( 6,02 u In chloroform) with that of crotononitrile ( 6, 10$ p in chloroform).

(12) D, G, T, Felton and 3, F, L, Orr [J, Chem, Soc,, 2170 (1?$5)] observed a similar trend for the following compounds:

(C"3)aC=C(C023t)a 6,10 n

(CI*3CH2)2C=C(CN)CC2Et 6.lli ^

(C%3C%2 )gC=C(C %)2 6.29$ p

Tlie small difference between the diester and the cyanoester may be due to the greater electron-repelling effect of the ethyl group than that of the methyl group. Compare the double bond absorption band of ethyl crotonate ( 6,02 u in chloroform) with that of ethyl 3-methylbut-2-enoata ( 6, 0$ u In chlorof orïP-),

The l,U-addition product (XXII) is probably a .mixture of

Isomers, It could be crystallised to colorless crystals, m,p,

61-68", However, on recrystallization of 1,00 g, of the crystals,

only O.LS g, of crystals, m,p, 8 $-88 ", could be obtained, the

remainder remaining as an oil. The crj'stals, on further purification

analyzed correctly for XXII,

Ethyl o-bromobenzhydrylcyanoacetate (XXII) was hydrolyzed by

2$% potassium hydroxide in ethanol to o-bromobenzhydrylmalonic acid

(XIII) in Bii.cçê yield. Use of IC^ sodium hydroxide in ethylene '

glycol at high temperatures resulted in decarboxylation.

The bis-hom ologation of the malonate to 3-( o-bromobenzhydjrj'l )- glutaric acid (VI) was accomplished in ih*h% yield by reduction of the malonate to the diol (r/) i n '91 .75? yield, followed by conversion of the diol to the bis-(methanesnlfonate) (V), double replacement by cyanide ion and basic hydrolysis of the dinitrile

to the diacid (V I), This method of bis-homologation of diacids

has been used successfully for the conversions of diethyl ( 2, 2 ’-

dimethylbsnzhydrp/l )malonate to 3-( 2,2 ' -dimethylbenzhydryl )glutaric

acid (91,8^ yield),' and of diethyl di-l-naphthylmethylmalonate'

to 3-[di-(l-naphthyl)-methyl]glutaric acid ( 5l^ ) .^

The double cyclization of the glutaric acid (VI) to 6a,12b-

dih;rdro-l-bromobenzo[c]phenanthrene-5j8(6K,7H)-dione (VII) was

achieved by use of polyphosphoric acid. The maximum yields

(66-72^) were obtained when mixtures of the diacid and polyphosphoric

acid were vigorously stirred at 127-135® for 70-100 minutes. In

, the series of runs, 10-155^ of low and wide-melting (lL 5- l 80 ®)

neutral material that could not be purified easily b'/ reci-ystallization

Was obtained. The :uaterial showed a cai’boryl band identical to that

of the-sharp-melting diketone but the spectrum differed considerably

in the 12 u to l 6 u region. It is probably a mixture of isomeric

diketones or perhaps the diketone containing a difficultly removable

inpurity. ’ . . * 9 In the experimen-^s at lower temperatures and shorter times, for 0 * O example a t 115* 120* for thirty-five*minutes, an-acidic substance, o » o e o 0 0 o o o 0

m,p. 13*1- 153°, wMch was apparently mostly a ketoacid, was obtained..

The infrared- spectrum (potassium bromide wafer) showed a double

carbon^/'l band a t 5. 81 - 3.86 u- (s), a shoulder at 6,o5 p. (m), a

’medium band a t 6.21 p , and bands at 12,2 p (w), 13.2 p (s),

13.5 p (w), lU .l p (w-m), and 13.5 u (m) in the 12 u to l6 p

region. The diacid (VI) could cyclize to two possible ketoacids,

XXV and XXVI (disregarding stereoisomers). The infrared spectrum

XXVI

of acid XXV, which contains two o-disubstituted aromatic rings,

would be, expected to show a strong band in the region, 13.0 p to

. 13,6 p , whereas that of XXVI, containing one monosubstituted and

one 1 , 2, 3-trisubstituted aromatic ring, wo’uld be expected to absorb

strongly in the regions, 12,3 p to 13.% vi , 13.0 u to 13,7 p

and l l i .l u to lli,5 u Since the solid absorbs strongly at

(13) L, J. Bellamy, "The Infra-red Spectra of Complex Molecules," John Wiley and Sons, Inc., New York) N.I. (195U), pp.'65-67.

13,2 p only, in the 12 to 16 P region, it probably consists

mostly of l,2,3,U-tetrahydro-l-(o-bromophenyl)-2-naphthaleneacetic

• o • acid (XXV), indicating that the glutaric acid (VI) cyclized stepwise

in the expected waf (from j.nductive effects).

0 o » ® ®o . e 0 0 o o e o o o ® o ® Uc

Reduction cf the d lie et one (VII] witVi -.lurlnum is opr nr; oxide ■

and iRoproppl a] cohol or with lithiuF: alurainiua hydilde pave a wide

ir.eltinp: solid which is apoai'entl'. a mixture of diastereoisomeric

riicls." Separation, by recrystallization was rot readily achieved

(ll.) It is possible that side reactions, such as partial dehydration, of the diol may have occurred. See A, L, Wilds, "Organic Reactions." Vol. II, John Wiley and Sons, Inc., Ilew York, Y.Y,, Ijlju , p . 167,

and nicroanalysis of the recrystallixed mixture gave no reasonable

results. However, the diol, m.p, l?c-2I5'*> formed a sharp melting;

dicarbethoxy derivative (iX/II), m.p. l5?-loC“, in 7 2 . yield.

OdO^Ef

XXVII hydrolysis of XXVII with methanolic potassium hydroxide afforded

after recrystallization a sharp melting diol, n.p. 222- 223*.

A concentrated solution of the diol in xylene containing a

small quantity of iodine was refluxed for 120 hours to afford

• ,1-bromobenzo[c]phenanthrene (XX) directly in 53.^ yield and not

■ the expected dihydro compound,

(l5) See, for example, R, M, Wise, Ph.D. Dissertation,• The Ohio . State University, 1955^ pp. 55-58.

O O • îhus, 1-bronoben2o[q]phenanthrene has been' synthesized from

o-broraobenaa?Ldehy'de, using eth;;l cyanoacetate (see Figure 12), in

111.3^ overall yield (I to XXI, 91,2%; XJvI to XXII, 90.7%; m i to

' XXIII, 81|.C%; XXIII to XXIV, 88 ,]%;. to IV, 91.7%; VJ to '

VI, 70.3%; VI to V II, 67.8%; VII to V III, 100%; V III to IX,

23.6% . IL.3%).

The fully aromatic character of the bromide was confirmed by

the following data:

1 . ’licroanalytical. data corresponded more closely to Cir,HnBr

thicin to CigHisBr.

2. The bromide formed a tetranitroflnorenone complex, which

analyzed for a 1 :1 coirolex.

3. The ultraviolet absorption spectrum (Figure 13) agreed

closely orith those of hnovm fcenzo[c]phenanthrene derivatives.16,17

(16 ) R. A. Friedel and M. Crchin, "Ultraviolet Spectra of Aromatic Compounds," John Xdley and Sons, Inc., New York, N.Y., 195l, Figures k6L-b70.

(17) G. II. Badger and I. S. Valker, J. Chem. Soc., 3238 (1921).

The spectrum shows a bathochromic s h if t and lo ss of fine structure

when con^ared to the parent hydrocarbon, as does l-methylbenzo[c]-

phenanthrene (see Table 2). Although there are undoubtedly other

facto rs involved,the difference between the spectrum of

.l-bromobenzo[c]phenanthrene and that of the parçnt hydrocarbon is

probably due considerably to the steric strain in the molecule. ” 5.0

4.5

• 40

3.5 o

I “ Bromobenzo [c] phenonthren#

3.0

Solvent: 95% Ettianol 2.5

200 220 2 4 02 6 0 2 8 0 3 0 0 3 2 0 3 4 0 0 3 8 036 4 0 0 Wavelength (mp.)

FIGURE 13

O o : • ' • . • ’ . Table 2

Positions of the Maxlna (:n'^) and Corresponding Intensities (log ( max) in 'th e U ltrav io let Absorption Spectra of Benzo- [cjohenanthrene, 1-Methyl- and l-3romobenzo[c]phenanthrene 95% Ethanol.a ' . .

Maximmn Unsübstituted^ 1-Methyl^ 1-Brorno . mja log (. max mu log 6 max Tog 4 r\

. 1 . 217 ® k.65 . 221° 1.55 225 1.66 2 230= 1*.31 - 3 (2kS) 3.99 2l3° 1.22 -

h 1.16 - - (259)? 1.13 - . 5 (26L) I.L 8 - (269)? 1.39 6 272 1.76 278 1.73 ( 282 ) 1.66

7 232 1*.90 286 . 1.83 239 1.76

8 291* 1.09 (300) 1.08 - 9 302 ■ 1.03 308 3.99 - -

10 311* 1 .0 0 321 3.95 323 3.96

11 326 3.63 (333) . 3.67 (338) 3.62

12 351* . 2.52 362 . 2.19 363 ■ 2.61

13 363 2.29 - (376) 2.31

Ih 372 2.30 m (382) 2.27

a. Numbers in parentheses are points of inflection. • • b. From'G, M. Badger and I . &. Walkdr, J . Chem. Soc ., 3238 (1951)

"c. Prom M. Wolf, Ph.D. Dissertation, The Ohio State University, O O 0 0 » 1 9 5 1 , ‘ 0 0 0 0 0 0 0 0 “o » « 0 0 0 0 » 0 0 0 0 <1 0 0 0 * O 0 o L. The nuclear Tna;;:netic-resonance" spectrj.:7i, determined and 18 interpreted by Dr, George-SIomp," showed no aliphatic, vinylic

(18) The Upjohn Company, Kalamazoo, Mich,

or a lly lic hydrogens, as would be exi^ected fo r a dihydro compound,

5* Treatment of the bromide :fith the chemical dehydrogenation

agents, chloranil and 2, 3-d ich lo ro - 5, 8 -dicyano-l,îi-bénzoquinone, ■

gave negative results, whereas a dihydro compound might be expected

to be dehydrogenated,

A study of the effect of concentration and the length of time

of reaction on the iodine in ;

yields of dehydrated product were obtained when a fairly concentrated

solution of the diol in xylene was re fluxed for a long time (greater

than eighty hours). The percentage of dehydration, but not the

percentage of aromatic broimlde was determiined in these runs. From

one reaction, run only twenty-six hours, was isolated a substance,

which analyzed most nearly fo r CigHigBrO, a monodehydrated alcohol,

which is either XXVIII or XXIX (disregarding stereoisomers).

xxviin XXIX

The most surprising fact concerning the iodine in xylene reactions ' » * ® • “ . * is that dehydrpgenation occured along with dehydration. This phenomenon

0 9 e . . . 15 ha.-î beoa otüeiTed r.t le^^t once before in iodine dehydrations. .In the conversion of 6a ,12b-dihydrobenzo[c]phenanthrene-?, 8 ( 6H,7H)- dione (liXXj to t , 6-di!;Ktt.hylbenzo[c]phenanthrene (X^GCIII), the product obtained from the reaction of méthylmagnésium bromide with

OH CH: OH XXX

C44

X X V 11

XU. was refluxed >ri.th a few crystals of iodine in xylene for one hour.

The solvent was distilled raising the temperature to 235“. From the

crude product was obtained XXXIII in 29% yield (from XXX), Use of

iodine alone (without xylene) in the dehydration also resulted in

the form ation of a considerable quantity of XXXIII, 19 .

(19) Dr, M, Ckawara, The Ohio State University, unpublished - r e s u lts .

“ ' L6

It seems likely that, in these conversions, the diol is first . dehydrated by means of iodine^C and that a disproportionation

(20) M, L. Char, S. D. Hughes, C. K .'Ingold, A. If. M. Mandour, G, A, Haw and L, I , Woolf [J, Chem.. See., 2093 (19U6)] have suggested the following mechanism for iodine, dehydrations;

P.CH + 2I 2 ^ ROIH ♦ In . rast

+ ROHI -* R * HOI slow

R o le fin ♦ V* f a s t

H, Hibbert [J, Am. Chem, Soc., 17^6 (191o)] has speculated on the possible intermediates of the reaction.

yielding the fully aromatic structure and, perhaps, the hexahydro compound followed, A number of disproportionations at relatively

% 4-

low tem peratures to y ie ld aromatic compounds are known, but almost PI 22 all of these are heterogeneously catalyzed. ' For example,

(21) R, P, linstead, E, A. Braude, P, W. B. Mitchell, K, R. H, Woolridge and L, M, Jackman,. Nature, 169, 100 (1952).

(22) E, A. Braude, R. P, Linstead and P, W. Mitchell, J. Chem, Soc., 3578 (195i|). . .

O O o 0 o o o ■ ■ . hi cyclohexene disproportionâtes quite ranidly at room température in the presence of a suitable catalyst, bu.t requires temp^eratures as high as 600“ in the absence of a c a ta ly s t.^3 Only a few cases of

(23) M. Zelinsky, Bar. 185 (1925).

apparently thermal disproportionation of hydroaromatic compounds at relatively low temperatures are known. For example, 6,7,8- trimethoxy- 3-m ethyl- 3,b-dihydronaphthalenc-l, 2-dicarboxylic anhydride (XXXIV) disproportionates to XXXV and XXXVI (isolated as the diacid) on slow sublimation at 19C>-2CO® at I 6 mm,^^ However, ■

(2ii) J, ’V, Cook, T, y, Johnston and J, D. Loudon, J, Chem. Soc,, 527 (1950).

these reactions are regarded as probably being heterogeneously

l9ô-7 ô û *

l i I# mm.

JO&V. yxv \\l 4-

' y xx\T' k8 0 O 0 ° 0 g r' catalysed reactions

(2S) E,‘A, Braude and R. P. Linstead, J, 'Chem. Soc., 8Shh (19SL).

'Since much less than'an equivalent amount of iodine is used, the reaction could not be a direct dehydrogenation, except in pai't, 26 by iodine. The reaction may be a homogeneously catalyzed'

(26) Iodine has the power of removing hydrogen from hydroaromatic rings at high temperature. For exanq:)le, 1,2,3,1-tetrahydronaphthalene and 1 , 1 -dim ethyl- 1, 2, 3, L-tetrahydronaphthalene have been dehydrogenated to naphthalene and l,ii-dimethj'l- naphthalene,r espectively, by use of iodine. See K. Shishido and H. Nozaki, J. Soc. Chem. Ind. Jacan, 17, 819 (1911); G.A., Ig, 635lh (1918).

disproportionation grossly resembling the many homogeneously catalyzed 29 27 28 hydrogen transfers knovm; ' ' however, too little is knovm about

(27) E. A. Braude, L. M. Jackmanand P.. P. Linstead, J , Chem* Soc., 3918, 3961 (1991).

(28) S. A. Braude, A. G. Brook and R. P, Linstead, J , Chem, Soc., 3969, 3971 (1991).

the conversion at this time to state what the reaction path is.

Various other methods of dehydration were tried. Thermal dehydration, thermal dehydration in the presence of an iodine crystal, and thermal dehydration in the presence of potassium bisulfate all led to high melting materials. Apparently idiat

happened was that polymeriza,tion (diraerization, etc.) occurred along

with dehydration. There are a number of examples in the literature

• in which styrene and dihydronaphthaflene type substances formed

% O ; o o o o o

: " ' b? • * c 4 * diners, etc. For example, A -dialin (1,2-dihydronaphtbalene) PQ in formed dimers in-the presence of acids, *" Anethole (XXXVII)

(29) J , V , Srann and G, Kirschbattm, Ser, SLB, ^97 (1921).

(30) II, D. Scott and J, F. ’lalker, Ind. 3ng. Chen,, _32, 312 (19U0),

dimerized readily to isoanethole (XXXVIII),■ In the presence of

(31) G, D, Goodall and R, D. Haworth, J, Chem. Soc,, 2^82 (1930),

C«3 -CHiCWCW^ HCl Br CMC ÛH3 0 H

XXXVII PC xxVm

mineral acid, 7~methox^’'-l,2-diIiydronaphthalene (XXXIX) dimerized to

XL (structure by analogy to the dimerization of anethole).•

( 32) ¥, S, Johnson, J, M, Anderson and W, E, Shelberg, J, Am, . Chem, Soc,, 66, 216 (19LL). 50

Treatment of the diol with phenylisocyanate, thionyl chloride °

in pyridine y and pyrolysis of the dicarbethoxy derivative did not

give proMsing results»

The conversion of l-bromobenzo[c]phenanthrene to l-cyanobenzo[c]-

phenanthrene was accomplished in 7 1 . yield by refluoslng a mixture

of the bromide and cuprous cyanide in H-me t hy 1 - 2 -pyrr ol id one

(b .p . 202®} for an hour.

0 O O O e o o

0 oo o o 0 °

KCPERIMENTAL . .

Generalizations

1» AU melting.points are uncorrected unless otherwise stated..

2. Microanalyses were by Galbraith Microanalytical Laboratories,

Knoxville, Term.

3. The phrase "treated in the usual manner" used throughout this

section means th a t the organic solvent layer was washed successively

with water and saturated sodium chloride solution, filtered through

anhydrous magnesium sulfate, and the solvent distilled under reduced

pressure* The term ether-benzene refers to 1:1 mixture (by volume)

of diethyl ether and benzene* The Skellysolves (petroleum ether)

used for crystallizations were distilled: Skellysolve F, b.p. 35-55°J

Skellysolve B, b.p. 65-69°j Skellysolve C, b.p. 90-97°»

L* Infrared spectra were recorded on a Baird double-beam

spectrophotometer* A letter w, m, or s in parentheses following

the wavelength indicates the intensity of the band as weak, medium

or strong, respectively.

"I o-Bromobenzaldehyde

(l) The method used was essentially the procedure employed by G. K. Coleman and G. E. Honeywell, "Organic Syntheses," Coll. Vol. II, John Wiley and Sons, Inc., New York, N. Y., 19^3» P» 89, in the preparation of p-bromobenzaldehyde*

To 300 g. (1.7^ çoles) of o-bromotoluene (Dow Chemical Company)

in a 1 lite r round-bottomed flask immersed in an oil bath heated to 9 ®

% « 51 ' . O % @ o e* * 0 0 * o o ® * » o o o o o ° ° o o 0 o ° o ° o ° ° :, ° . o o o

and Illum inated’ t y two 200 T att tungsten. îarAps, vas added w ith

-stirrin g 196 m l. (61^ g ., 3 * 89 ‘moles) of bromine sc that .only a

small excess was present at one time. About 120 ml. of bromine

was added in three hours* The temperature of the bath vras raised

to 160-165° and the remainder was added in six hours * The. total

gain in weight of the mixture was 288 g. (theory, 280 g.)*

The crude red-brown oil (a lachrymator) was transferred to a ■

3 liter flask and mixed with 600 g, of calcium carbonate and 900 m l.

of water. The mixture was heated cautiously and refluxed for twenty-

four hours. The cooled mixture was steam distilled. The heavy

yellow oil was separated from the aqueous solution, which was then 2 extracted Tdth ether-benzene. The combined organic solutions

(2) In a later experiment it was found that about h% o f the product vra,s contained in the aqueous solutions.

Were washed with 10^ potassium carbonate solution and treated in

the usual manner. On distillation, 258 g. of a light yellow oil,

b.p. 100-125° at 8-9 mm., was obtained. Redistillation afforded

222 g* of light yellow aldehyde,^ b.p. 101-116° at 8-9 mm., which was

(3) D. F. DeTar and L. A. Carpino [J. Am. Chem. Soc., 78, Ii77 (1956)] reported a b.p. of 81.8-91.2° at 3»^ mm. and a b.p. of 63.5- 77° at 0.13-().28 mm., V. H. Rape and F. Bernstein [Helv. Chim. Acta, 13, Ü6l|. (1930)] reported a b.p. of 118-119° at 12 mm. and R. Adams and E. H. VoÜweiler [J. Am. Chem.. Soc., W) 1737 (1918)] reported à b .p . of 230° .

•sufficiently pure for use in subsequent experiments,

O 0 o o ** o o o o ° oo o ® o ® o ° ® o o °

° ° ° The aldehyde could be purified bv preparation of the busulfite ^ « addition conpiound, washing' with absolute ethanol and eth er, followed

by steam distillation in the presence- of a snail excess of potassium

carbonate and distillation under reduced pressure, I'sinp this method

o-bromol)enzaldehyde, b.p, 10C-1C1{“ at 8 -? nr.,, was obtained in

. y ie ld .

Diethyl o-Bronobenzalmalonate (11)^

(Ii) See C, F, IÎ, Allen and F, ”, Spangler, "Organic Syntheses," Coll. Vol. Ill, John Wiley and Sons, Inc., Mew York, I!,Y,, P. 377.

A mixture of 180 g, (0,973 mole) of o-bromobenzaldehyde, h*OG ml,

of benzene, 160 g, (1,00 mole) of diethyl malonate (Eastman ''Jhite

Label, 6 g, of benzoic acid and 7 ml, of piperidine in a 2 liter

flask e quipped TTith a 60 cm, packed column (glass helices) and

phase-separating head was refluxed until no more ivater separated

(eleven hours). An additional 2 ml, of piperidine was added and the

mixture was refluxed for eight hours to yield 0,5 ml, of aqueous

layer. In all 17,5 ml, of ac^ueous layer (about 97% of theory^) was

obtained. The deep orange so lu tio n was washed w ith w ater, 1 K

hydrochloric acid and treated in the usual manner. Distillation

afforded 280 g, ( 88 . 0%) of light yellow oil, b.p, 178 -181 " a t 1 ram,,

after a forerun of 2 1 ,6 g.

Trituration of the ester with Skellysolve F yielded white

crystals, ra.p. h2-lt3". The infrared spectrum (potassium bromide

0®

o wafer) showed bands a t 5*79 u (s) (CO^R), and 6.10 p (s) (C ■ C) ♦

The analytical sample, recrystallized several times from Skellysolve

F, melted at U2.6-1*3»$° (corr.).

Anal. Calculated fo r C, 51.1*j H, h»6; Br, 2h»h

Founds C, ^l.O j H, U.7j Br, 2Ü.1

o-Bromobenzalmalonic Acid and o-Bromocinnamic Acid

A mixture of 1^.00 g. (0.0li$9 mole) of diethyl o-bromobenzal-

malonate, m.p. 12- 1*3 °» 1$.0 g* of potassium hydroxide, and ISO ml.

of 9$% ethanol was refluxed gently for 1 .5 hours, during which

time a mass of tan crystals precipitated. The deep red mixture was

cooled several hours in the refrigerator and then filtered cold.

The orange-tan crystalline solid was dissolved in 150 ml. of vater.

The solution was washed several times with ether-tenzene and added

droprdse with mechanical stirring to ?5 m l. o f 6 N hydrochloric

acid kept at 0° to yield 6.60 g» (53^) of light tan diacid,^ m.p.

(5) C. M. Stuart [J. Chem. Soc., 11*0 (1888)] reported t^e m .p. as 198 ° with effervescence, the residue melting again at 208 •

196 - 197 ° with effervescence (sealed tube), the residue melting again

at 212-216°. The aqueous filtrate was cooled in the refrigerator

overnight and then filtered, to yield 0 .6 0 g, of colorless crystals,

• m.p. less than I 60 w. dec* The deep red ethariolic filtrate was

concentrated to 50 ml. and dissolved in 1*00 ml. of water. After

the solution was washed several times with ether-benzene and added

O O 0 o o

. ' : : ' o o o $$ ... • . • . - . « dropvâse with stirrin g to 200 ml. of 6 N hydi’ochloric acid kept a t «

• ' ■ 0°, 0.1^ g, of yellow-brov.Ti so lid , m.p, 171- 21$°, was obtained*

The diacid (2,00 g.) was heated at 230-2ii0° for fifteen minutes

until no more carbon dioxide was evolved. From one recrystallization

. of the resulting tan solid from ethanol, 1,$$ g. of tan acid, m.p*

21$-2l6°, was obtained. Sublimation and recrystallization yielded

colorless o-bromociimamic acid," m.p, 216.9- 218,1° (co rr.).

(6) S . Reich and P. Chaskelis [Bull, soc, chim, France, 1^, 287 (1916)] reported the m.p, as 215- 216° ,

Neutralization equivalent! calculated 227 j found 227, 22$,

Diethyl o-Bromobenzhydrylmalonate (ill)

To a well-stirred solution of the Grignard reagent, prepared

from 3U»6 g , (0,222 mole) of bromobenzene (Dow Chemical Company), . .

5«10 g, (0,210 mole) of magnesium turnings and 1$0 ml, of dry ether,

cooled to 5-10° was.added dropwise in h$ minutes a solution of 32,7 g,

(0.100 mole) of diethyl o-bromobenzalmalonate, m.p* Ii2- 1^3° , in $0 ml*

of dry ether* After refluxing for three hours, the mixture was

hydrolyzed .with saturated ammonium chloride solution* The ether

layer was decanted and the residue washed four times with benzene*

The combined organic layers were treated in the Usual manner# Distillation yielded 26,1 g, (,6k%) o f crude yellow-green d iester,

b ,p , 196- 239° at 1/2 mm,, a fter a forerun of 5»1 g , bf a mixture

of biphenyl and an oil, b.p. less than 196° at 1/2 mm, A large

amount of dark-brown tarry residue remained in the d istillin g ' fla sk .

9 o o CD

56°

The crude diester was contaminated by startiiîg unsaturated diester

as evidenced by a band at 6.10 p. (w) (C = C) in the infrared spectrum*

The crude oil was redistilled to yield 1.6 g. of yellow oil, b.p,

90-182° at 1/2 to 1 mm., 3.3 g. of yellow oil, b.p. 182-201° at 1/2

to 1 mm., and 18.0 g, (Ub.W) of yellow diester, b.p. 20^ -213° a t 1/2

to 1 mm. The infrared spectrum (no solvent) showed a band at 3.8 u

(s) and no band near 3*0 ja or 6.10 iu. All attempts to crystallize

the diester were unsuccessful#

The results, of several runs are sunmarized in Table 3# The ,

column labeled yield** represents the crude once-distilled (from

. a modified Claisen flask) product# In each case, except the one

involving magnesium bromide the product lis te d was contaminated by

some starting diester# Considerable .quantities of tarry residue

were obtained during distillation,

2-(o-Bromobenzhydryl)-l,3-propanediol (IV) Via Diethyl o-Bromo**

benzhydrylmalonate (ill)

To a well-stirred mixture of 9.3 g# (0.2U mole) of lithium

aluminum hydride and LOO ml, of dry e th e r was added dropwise a t a

rate sufficient to maintain gentle reflux 39*7 g* (O.O 98 O mole)

of diethyl o-bromobenzhydrylmalonate, b.p# 203- 21U® a t 1 /2 to 1 mm.,

in ISO ml# of diy ether. After the addition was complete (forty

minutes), the mixture was re fluxed for twenty-one hours# The excess

. ' - hydride was decomposed by the careful dropwise addition of water

and the mixture poured onto a mixture of 3OO g# qf ice and '700 m l.

o o o

■Eable 3

Reaction of Ethyl b-Brcmobenzalmalonatè (II) with-

Phenylmagnesium Bromide

Moles of Moles of Method of Reaction Per Cent Ester C^I^MgBr Addition Conditions Yield B.p#

0,100 0.11 Inverse Add at 10-15°} 3l^ 203- 236° (10^ excess) reflux 5 hrs# a t 1 mm#

0.077 0.08 Inverse Add at rm. temp# 6?^ . 182-21:00 (10^ excess) to ester in 1:1 a t 3 mm# ether-benzene soln,; dist. solvent to react# mix. temp, of 65° reflux 1 hr#

0.100 0.12 Inverse Add to MgBrg (10% 35® 208-212 (20^ excess) excess) in ether a t 2 mm. (two layers)} add G. reagent at re flux temp.} rm# temp, 1 hr#

0.300 0.6C Inverse Add at 5-10°; rm# 66 19U-217° (100^ excess) temp, li hrs# at 1/2 mm#

0,069 .. 0.H& Inverse Add at 5-10° 69 203- 230° (100^ excess) reflux over a t 1/2 - night 1 mm#

0.100 0.11 Normal Add (in 1:1 . 28^ 201- 236° . (10^ excess) ether-benzene) at 1/2 - at reflux temp.; 1 mm. . reflux 2-1/2 hrs.

0.10Ô 6.20 Normal Add at 5-10°; . 6U 196- 239° (^.00^ excess) reflux 3 hrs. at 1/2 mm

a. Recovered about 26^ of starting diester» b. Contained a"considerable quantity of starting diester# c. Recovered about 28^ of starting, diester % d. Distilled twice « * « e

9 O O o o o of 10^ sulfuric acid and stirred well* The two layers were separated,

and the aqueous layer extracted with ether-benzene* The combined

organic layers were washed with 10$o potassium carbonate solution

and treated in the usual manner* Distillation afforded 2 7 «0 g*

(86^) of very viscous light yellow diol, b.p* 213- 232° a t 1/2 mm.,

after a forerun of 1,9 g. of light yellow oil, b.p. 155-213° at 1/2

mm. The infrared spectrum (chloroform) showed a band at 2.9-3.0

(s) (oh) and none near 5.8 h* All attempts to crystallize the diol

were unsuccessful*

o-3romobenzalmalononitrile (X7, Ar “ o-BrC^H^^^)

A mixture of 20.0 g. (0,108 mole) of o-bromobenzaldehyde, 7«13 g»

(0,108 mole) of malononitrile (Kay-Fries Chemicals, Inc.), 300 ml*

of benzene, 0.5 ml* of piperidine and 0.15 g* of benzoic acid in a

500 ml* round-bottomed flask equipped fdth 60 cm* packed column (glass

helices) and phase-separating head was refluxed for seven hours* One

and eight-tenths ml. of aqueous layer (about 93!» of theory) was

obtained,* The deep orange-red mixture was washed iTith 1 N hydrochloric

acid, 10^ potassium carbonate solution and treated in the usual

manner to yield an orange-brown oil which solidified* After three •

■ recrystallizations from ethanol-water, 17.9 g. ( 71 .1$) o f tan

crystals,"^ m.p. 89 - 91 ° , and 1 .0 g. of tan crystals, m.p. 8 U-90 °,

(7 ) o-Bromobenzalmalononitrile is a sternutator and skin ° i r r i t a n t . A number of sim ilar compounds have th is property [B. B. Corson aind R. W, Stoughtbn, J. Am. Chem. Soc., 50, 2825 (1928 )]. '

e o 0 ® 0

0 e ' ' ' ' $9 were obtained* îhe infrared spectrum (potassium bromide wafer)

showed.bands at (a (m) (C : N) and 6.30-6.35 u (m-s) (C * C)*

The analytical sample, recrystallized several times from ethanol-

0 water to give long white needles, melted at B9J 4- 9 0 (c o rr.)*

(8) H. G, Sturz and C. E. Holler [J. Am. Chem. Soc., J1» 29k9 ( I 9 U9 )] reported the m.p. as 9 0 .0- 90 .$°*

Anal. Calculated for C^QH^BrNg* C, $1.$; H, 2.2; N, 12.0

Found: C, $l.?j H, 2.3; N, 12.2

In a larger run, 111.0 g. of the aldehyde was reacted with

3 9 . 6 g. of malonitrile for 3 - 1 / 2 hours to yield 69.5 g* (6L.0%)

of light yellow dinitrile, b.p. 1$1-1$$° at 2-1/2 nm* Upon

solidification and one recrystallization, tan crystals, m.p*

88.5-90.0°, were obtained*

o-Bromobenzhydrylmalononitrile (X7I, Ar “ 6-BrC^H^, Ar* ■ C^H^)

To a well-stirred solution of 9.08 g. (0.0390 mole) of 0-

bromobenzalmalononitrile, m.p. 89-91°, and 190 ml. of dry 1:1

ether-benzene cooled in an ice-bath was added dropwise in twenty-

fiv e minutes L9 ml. (0.0$9 mole) of 1.19 N phenylmagnesium bromide

in dry ether A gummy orange-red conçlex separated during the

( 9 ) The concentration was estim ated by the method o f H. Gilman, P . D. M lkinson, W. P. F ish el and C. H. Meyers [J. Am. Chem. Soc, lj£, 1$0 (1923)].

O 0 c '

o O ' - . 60 addition* After 12$ ml. of dry benzene was added the solvent was slowly distilled until the temperature of the mixture reached 65°.

Most o f the conçlex did not go in to so lu tio n . The mixture was refluxed and stirred vigorously for an additional five hours* Ih© mixture was cooled and hydrolyzed by addition of 1 N hydrochloric acid* The organic layer was separated and the aqueous layer extracted with ether-benzene* The combined organic layers were washed with 10^ potassium carbonate solution and treated in the usual manner* Distillation yielded 9.2 g* (?6^) of a light yellow- green oil, b.p. I 9 O-213® a t 1 - I - I /2 ram* and l e f t 2.7 g* of dark brown residue*

Crystallization of the o il from chloroform-Skellysolve C, yielded 7.2 g. ($9%) of white crystals, m.p. 109-111°* The infrared spectrum (potassium bromide wafer) showed a band a t

U.U5 h (wHa) (C : h) and no bands near 3.0 u or p. The analytical sample, recrystallized three times from chloroform-

Skellysolve C, melted at 110*2-111,0° (corr.)*

Anal. Calculated fo r Ci^H^jBrNg: C, 6I .83 H, 3.63 Br, 2^,7

Found; C, 62. 03 H, 3*&; Br, 2$,$

In another run, 92 ml. (O.U mole) of 1.19 N phenylmagnesium bromide in ether was added to 23.2 g. (O.lOO mole), of o-bromobenzalmalononitrile in 100 ml. of dry tetrahydrofuran, An additional 100 ml* of tetrahydrofuran was added and the solvent distilled until the temperatuaje of the deep blue-black mixture reached 60°, at which temperature a ll of the complex was in soltftion#

0-0

os O .61

After refluxing for an additional four hours, the product was worked up to yield 23.2 g. (.1$%) of a viscous light yellow oil, b.p. 175-217° at 1-1/2 ffifli.j 'Which solidified to pale tan crystals, m.p. 106-112°.

Using ether alone as a solvent, a very insoluble cream-colored

Grignard complex was formed and 2»$9 g» (51.8^ of an original 5.00 g.) of starting nitrile was recovered unreacted.

Ethyl o-Bromobenzalcyanoacetate (XXI)

A mixture of 168 g. (0,908 mole) of o-bromobenzaldehyde, b.p. lOli-108® at 10 mm., 105 g. (0.928 mole) of ethyl cyanoacetate, b.p.

110-111^ at 26-27 mm., 600 ml. of benzene, 1 g. of benzoic acid and 5 ml. of piperidine in a 1 liter flask equipped with a 60 cm. packed column (glass helices) and phase-separating head was refluxed seven hours until no more water separated. Seventeen m illiliters of aqueous layer (about9h% of theory) was obtained.

The deep orange solution was washed with water, 1 N hydrochloric acid, 10^ potassium carbonate solution and treated in the usual manner. Distillation afforded 11.2 g. of a light yellow forerun, b.p. less than lli8° at 1/2 mm. 232 g . (91.2%) of yellow ethyl o- bromobenzhydrylcyanoacetate, b.p. 1U8-150° at 1/2 mm., which solidified to pale yellow crystals, m.p. 67- 69° , and 6.9 g. of yellow oil, . b .p . 150- 168 ° a t 1/2 mm., which solidified to yellow crystals, m.p. h2-i|.5°# The infrared spectrum (potassium bromide .wafer) of the’ crystals, m.p. 67- 69° , showed bands a t h.53 p (w) (C ; N), 5.7S p

(s) (CO2R) and 6.20 p (a) (C C)* ^ O •• 0 e * ® • o o

9 9 . • . ê j

The analytical sample, recrystallized sevéral times from 6 kelly< solve C to yield long colorless needles, melted at 68.9-69.3°.

Anal. Calculated for C-j_2H2_QBrN0 2 : C, $ l.b ; H, 3 .6 ; Br, 28.S; N, 5*0

Found: C, 51.2; H, 3.7; Br, 28.2; N, h.9 28.0

Ethyl o-Bromobenzhydrylcyanoacetate (XXIl)^®* ^

(10) See E. P. Kohler and M. Reimer, Am. Chem. J., 33, 333 (1905).

(11) See M. S. NeTOuan and II. R. Flanagan, J. Org. Chem., 23j 796 (1958).

To a veil-stirred solution of 257 g« (0.919 mole) of ethyl

o-tromobenzalcyanoacetate, m.p, 67- 69 ° , in 550 ml. of dry benzene vas added dropvise in 2-l/li hours 980 ml. (1.23 moles) of l.OU N phenylmagnesium bromide in ether^ vith enough cooling to maintain

the temperature at about room temperature. After 100 ml. of dry benzene vas added, the solvent vas slovly distilled until the temperature of the mixture vas 60° (two h o u rs). The now homogeneous

orange-red solution vas refluxed vith stirring an additional two hours and then poured vith stirring into ?50 ml. of ice-cold 2 N hydrochloric acid. The organic layer vas separated and the aqueous layer extracted vith ether-benzene. The combined organic layers were washed vith water, 10$ potassium carbonate solution and treated

in the usual manner. Distillation afforded 197 g. of yellow oil, b .p . 196 - 199 ° at 1/2 mm., and IO 3 g. of yellow oil, b.p. 199-225°

. . . ' . ' 63 . at 1/2 mm.’, after a forerun of 8.1 g. of a mixture, b.p. 100-197° at 1/2 mm., v;hich contained mostly biphenyl. The dark browi residue weighed 18.5 g . R e d istilla tio n of the fra c tio n , b .p . 199-22%° a t

1/2 mm. yielded 102 g. of yellow oil, b.p. 188-189° at ca, 1/h mm«

The infrared spectra (Nujol mull) of the two fractions (showing bands at h«L8 u (vw) (C s N) and 5.73 (s) (CO^R) and no bands near

3.0 u or 6.20 u were identical* Therefore, the yield of ethyl o-bromobenzhydrylcyanoacetate, b.p# 196-199° at ca* 1/U mm., was

298 g. (90.7%).

The oily cyanoester crystallized to colorless crystals, m.p. 61-68°, Recrystallization of 1.00 g. from Skellysolve C yielded 0.1i5 g. of colorless crystals, m.p. 85-88°* The cyanoester remaining in the mother liquor could not be crystallized, indicating that the original oily cyanoester was probably a mixture of iscsaers.

The analytical sample, recrj>^tallized several times from Skellysolve C, melted a t 8 7 *0- 88 . 8 ° (c o rr.)*

Anal. Calculated for C^gH^^BrNOg: C, 60.Uj H, U.5j Br, 22.3

Found: C, 60.3; H, k.5; Br, 22.2

o 0 ' ; . 6 1

o-Dromobenzhydrylmalonic- Acid (XaIII)

A mixtpre of 55.0 g, (0.15U mole) of ethyl o-bromobenzhydryl

cyanoacetate and 25% potçissium hydroxide in ethanol (101 g. of. 12 potassium hydroxide dissolved in 328 ml., of absolute ethanol), -was

(12) M. S. Neman and H. R. Flanagan [J. Org. Chem., 23, 796 (1958)] hydrolyzed ethyl di-l-naphthylmethylcyanoacetate to di-1- naphthylmethylmalonic acid in 92% yield by re fluxing i t m th 50% potassium hydroxide in ethanol for thirty-one hours. I. Vogel [J. Chem. Soc.,' 2010 (1928)] hydrolyzed a number of ethyl dialkyl- methylcyanoacetates to the corresponding malonic acids in high yields by use of 39% potassium hydroxide in 2:1 ■nater-ethanol m ixtures.

refluxed under nitrogen, the aumonia that evolved being trapped in

151.6 ml. of 1.016 N sulfuric acid in a series of test tubes. The

course of the reaction was followed roughly by the change in color

of the indicator^^ in each test tube. After 21-1/2 hours 90.9%

(13) A mixture of 2:1 methyl red-methylene blue. The color changes from violet to gray to green,

(by titration) of the theoretical amount of ammonia had evolved.

The mixture was allowed to cool overnight and the tan dipotassium

salt that precipitated was isolated by filtration and dissolved in

.1 5 0 ml, of water. The solution was treated twice with activated

» . charboal.and added dropwise with mechanical stirring to I 30 ml. of

6 N hydrochloric acid maintained at -5® to 0° with an ic'e-salt

bath. The viscous semisolid that formed, solidified after several

hours in the cold jnrxtmje and was filtered, washed several times

• • . 0 . '

O ° ° ° % o o o 0 o o o o 8 8 o o o o o o 0 0 ° g ® o o o o o o

° ° oO o 1, 3 .- ! ' o o ° o° o o o o' ■with water and dried in a vacutun desiccator to yield k$.2 g,t ^ % 0 (8 ij»0^) of cream-colored diacid, m.p. 167° dec. Neutralization-

o o„ o , equivalent; Calculated 17$; Found 173, 17^. The infrared spectrum, . ° ° ° ° (potassium'bromide wafer) showed bands at 3.2-3.$ p (s) (COgH, etc.), *

3*8 p (m-s) shoulder (COgH), $.7$-$.60 p (s) triple-b (COgH), and

6.09 u (m-s) shoulder.

The analytical sample, recrystallized several times from

acetone-benzene, melted at 168 - 170° w. dec.

Anal. Calculated for C, $S*0; K, 3*8; Br, 22.9,

Found: C, $ $ .l; H, 3*8; Br, 22.6

. In a la rg e r run, 302 g. (O. 8 I4I1 mole) of cyanoester was refluxed

■with a solution of UOO g. ( 7 .lb.moles) of potassium hydroxide) in

1300 ml. of absolute ethanol for $0 hours. During this time a large

quantity of the dipotassium salt precipitated. Upon working up,

there ■was obtained 262 g. of cream-colored acid, m.p. l 6ii° w. dec.,

■which gave neutralization equivalents of 210, 210 and 206, indicating

some decarboxylation* Purification ■was-accomplished by conversion

to the dimethylester (see following experiment) and subsequent

recrystallization*

Other methods of hydrolysis that were tried gave evidence of

decarboxylation or appeared to o ffe r no adyan^tage over the above °

method. Trea-tment of 3 .b g. of cyanoester-w ith 10^ sodium hydroxide

in ethylene glycol at 17$-180<5 for eighteen hours yielded 2 .9 g * of

tan solid, m.p. 132- 138 °. Recrys-^Uizat^on"from ethanol-water

afforded whi^be crystals, m.p. 138 .0- l b l . 5 °, which gave neutralization O ° O equivalents d"f 313 and 319* ® o 0

O ' O ® O O o O o o 0 « o o o oo o o o

o ® 7/hen 2$% potassium hydroxide in methanol was used to hydrolyze o 3.16 g. of cyanoester, only UO^ of the ammonia was evolved in

twenty-nine hçurs. After thirty-seven hours, with more than h,0%

of the ammonia yet to be evolved, the reaction was stopped, since

the method appeared to be too slow to be practical*

Use of 10^ potassium hydroxide in n-propanol to hydrolyze

1.00 g. of cyanoester required twenty-three hours to evolve of

the ammonia. On working up., a tan gum, which did not solidify

overnight in the refrigerator, .was obtained. This vfas not further

p u rifie d .

Dimethyl o-Bromobenzhydrylmalonate (XÂIV) TI N-methyl-N-nitrosourea was prepared from potassium cyanate in

(lU) F. Arndt, Org. Syntheses, it 8 (1935).

93 ^ y ield (132 g. scale).

A solution of about 12.9 g. (O.3O mole) of diazomethane^^

(1^) Prepared by the method of F. Arndt, "Organic Syntheses," Coll. Vol^ II,"John Wiley and Sons, Inc., New York, N. Y., 19W, p. 165. " .

(from 36.0 g. of N-methyl-N-nitrosourea) in ether" was added slowly

to a solution of 3^.9 g. (0.100 mole) of o-bromobenzhydrylmalonic o o acid in 100 ml. of methanol cooled to 0-5°. The m ixture was' gwirled, » allowed to stand for a few minutes and dii^ute acetic acid was added o ® ® o o * o to decompose the excess diazomethane* The yellow solution *jfas o o o o o o o o 0 0 0 A o 67 concentrated and cooled to yield 3^*3 g* of cream-colored crystals, m.p. 8 3 .0- 86 .5° upon filtration. From the filtrate, 0.21 g. of light yellov; crystals, m.p. 83 .5-8 6 .5°, vra,s obtained by extraction vdth ether-benzene and working up the combined organic layers in the usual way. The potassium carbonate v/ashings were acidified to y ie ld 0 .2 9 g. of pale yellow crystals, m.p. 163° dec.

One recrystallization of the diester from methanol-water afforded 33*2 g. ( 8 8 .1^) of colorless needles, m.p. 87 - 90 °# and

1.73 g. of tan oil, ■vdiich could not be crystallized. The infrared spectrum (potassium bromide wafer) of the crystals showed bands at

5.68 u (s) (COgR) and 5*7L u (s) shoulder (COgR). The analytical sample, re crystallized several times from methanol-water, melted at

91 .7- 9 2 .6° ( c o r r .) .

Anal. Calculated for G^gH^^BrO^i C, 57*3# H, U.5j Br, 21.2

Found: C, 57*3# H, b.5# Br, 21.0

2-(o-Bromobenzhydryl)-1 ,3-propanediol (IV) v ia Dimethyl o-Bromo- benzhydrylmalonate (XXI7)

.To a well-stirred mixture of 8.0 g. (0.21 mole) of lithium aluminum hydride in 350 ml. of dry ether was added dropwise at a rate sufficient to maintain a gentle reflux a solution of 3I.O g.

(O.O823 mole) of dimethyl o-bromobenzhydrylmalonate,.m.p. 87-90°, in 7$ ml. of dry ether* After the addition was complete (one hour), the mixture was re fluxed with stirring for twelve hours £ The excess hydride was decomposed by the careful drop7ase avdditiorp of "water » o o o 0 0 o o o o p " 0 „ O « o « 0 « and the mixture was poured onto a mixture .of 2^0 g« of ice and SSO

ml» of 10% sulfuric acid and stirred well* The two layers were

separated and the aqueous layer extracted v/ith ether-benzene* The

combined organic lay ers were washed ?d.th w ater, 10% potassium

carbonate solution and treated in the usual manner* Distillation

yielded 2b.2 g* (91.7%) of a very viscous oil, b.p. 221- 236° a t

1-1/2 mm. The infrared spectrum of the oil was identical to that

of the diol obtained froa reduction of the diethyl ester* All

. attempts to crystallize the diol were unsuccessful.

A direct reduction of the malonic acid to the diol Td.th lithium

., aluminum hydride^^ was tried. The diacid was too insoluble in ether

(16) N. G. Gaylord, "Reductions vdth Complex Metal Hydrides," Interscience Publishers, Inc.,, liev; York; N. Y., 19^6, pp. 322-365*

to use the usual procedure but, by use of a Soxhlet extractor, 5.00 g*

. of the diacid was reacted* After refluxing the mixture for fifty-one

hours and l'ïorking up in the usual way, 3*7 g* of a mixture, b.p,

160-225° at 1 mm., which consisted of a very viscous yellow oil and

a colorless liquid, was obtained. The viscous oil (about 3 g., 7b%)

was the diol, but the colorless liquid (about 0.3 g.) showed neither

carbonyl nor hydroxyl bands in the infrared spectrum.

2-(o-Bromobenzhydryl)-l,3-propanediol-bis(methanesulfonate) (V)^^)

(17) M. "S. Newman and R. M. Wise, J . Am.. Chem* Soc., 78 , b50 (1956). ^ . -

o =’ a o o I O o Ù o - % ' " . . ; • • .* • • . . o ® o e O o ® o o o ^ (18) M. S, îîeTOian and D. Xednlcer, J , Am* Chem* Soc*. ?8, L?6$ (1956).

To a solution of 23.7 g* (O.O 738 mole) of 2-Co-bromobenzhydxyl)-

1,3-propanediol, b.p. 221-236° at 1-1/2 mm., in 160 ml. of dry pyridine

(distilled from barium oxide) cooled to -5® vfas added dropiid.se with

stirring in fifteen minutes 27,5 g» (0.2li0 mole) of methane sulfonyl

chloride (Eastman %hite label)* After the addition was complete,

the stirring was stopped and the mixture was allowed to stand in the

cooling bath fo r four hours. A larg e amount o f assumed pyridine

hydrochloride precipitated during this time. The light orange

mixture was poured into 500 ml. of cold water and stirred well. A

viscous light yellow oil separated but did not solidify* The mixture

was extracted several times with ether-benzene* The combined

organic layers were washed with water, 3 N hydrochloric acid, 10^

potassium carbonate solution and treated in the usual manner to yield

35*1 g. of viscous light yellow oil (expected, 35.2 g.), part of

which was crystallized from chloroform-Skellysolve B by extended

cooling in the refrigerator to give light tan crystals, m.p. 110-llli®«

■ The infrared spectrum (potassium bromide wafer) showed bands at

7.35 p (s) (ROSOgR) and 8.5 p ( s ) •(ROSO^R), b u t no band near 3.0 p .

The analytical sample, recrystallized several times from

chloroform-Skellysolve B, melted at .0° (corr.),

Anal. Calculated for C-j_gH22^BrO£^S2 : C, L5*3; H, h.b

• . ■ Found: C, L5.2; H, U.5 '

O o

• . • ■ 7 0 3~('o-Bromobenzhydryl)glutarlc Acid (71)^?*

To a solution of 19.6 g. (0.301 mole) of potassium cyanide and

0.^ g, of potassium iodide in 12$ ml. of water was added a solution

of 3U.9 S« (0.0731 mole) of crude diester in 200 ml. of dimethyl-

formamide* Upon warming and addition of $0 ml. of dimethylformamide

the mixture became homogeneous. After stirring 83-90° for h-l/2

hours, the orange solution T/as poured onto 1000 g. of ice and water

and stirred well. A yellow-brown gum separated but did not solidity

and the mixture ms extracted several times with ether-benzene. The

combined organic layers were treated in the usual manner to yield

2h»S go of a viscous red-brown oil. The infrared spectrum (chloroform)

showed bands a t 2.9 (w) (NH), h,$ p. (m) (C 5 N), $.9 p (s) (C ■ 0)

and 6.2 p (w-m) indicating that the dinitrile had partially hydrolyzed*

A mixture of 23.9 go of the oil, 20 g. of sodium hydroxide and

225 ml. of ethylene glycol was heated in an oil bath with occasional

swirling to the reflux temperature, during vfliich time the oil and

sodium Iqrdroxide had dissolved. The condenser was removed until the

temperature of the orange-brown solution rose to 180°, After the

solution was re fluxed for about five minutes, the tan di sodium salt

began to precipitate and in a few minutes the bulky precipitate had

fiU ed most of the flask# The mixture was re fluxed for an additional

three hours, cooled and filtered* The tan disodium salt was dissolved

300 ml# ci watejf and the 'Solution was filtered and washed with

ether-benzene* Addition fcf the aqueous solution to ®100 ml. of cold

t It hydrochloric" acid yielded % gum*which soon solidified to afford

® e * - 4» f I Ëreafflaselofed I82-l8it 0

00 0 ® o 0 o

o o ® o® o ^ o® o o

The red-brown" glyool filtrate was poured into $00 ini, of water

and the so lu tio n was f ilte r e d and washed w ith ether-benzene. Addition

of the solution to 200 ml* of cold 6N l^ydrochloric acid yielded

8.L g, of tan-colored solid, n.p, 170.2-177*0°, Recrystallization

from chloroform-Skellysolvo B yielded 6.16 g, of white crystals,

m.p, 182.2-182.0°. A total of 19.0 g. (70.3^ based on the diol, 17)

of diacid, m.p. 182-182°, was obtained. The infrared spectrum

(Nujol m ull) showed a band a t 5*3U pi (s) (COgH),

%e analytical sample, recrystalHzed several times from

chlorofonn-Skellysolve B, melted at 18? .8-188.6° (corr.).

Anal. Calculated for C]l8^17®^U* C, 27*3î H, L.2; Br, 21.2

Found: C, 27*1; H, h.2j Br, 21.3 27.2; li.6; 21.3

In a larger run, 127 g* of crude diol (IV) (obtained from the

lithium aluminum hydride reduction of the dimethyl malonate (XXIV)

and not distilled) was converted in 69.8% yield to recrystallized

diacid, m.p. 183.0-182.2°, In another series of experiments using 110 g. of recrystallized

disulfonate ester,m.p. 110.2-Hii.0°, 72.1 g. (83*2%) of

(19 ) The use of recrystallized disulfonate ester is desirable since i t y ield s a more e a sily p u rified d ia c id . However, the e s te r 'crystallizes only with difficulty and consequently was used unpurified in most of the runs.

recrystallized diacid, m.p. 181|.0-186.2°,'and 9.2 g. çf red-brown oil, . • * » which did not crystallize,.were obtained. , •

. . ,. . ° °. °. . ' ' ' "",, ' ° : °. ' ' ' ° ' -' V ' ' . ' \ \ " - ^ o ° ëa,lgb-I)iAydr6-l-breiaefeeîî2ofc?phenatithyefte-$jS(6g,7H)-»31otte (VII)

'A mixture of 2Ô*0Ô g# mole) of finely ground l-Co-bromo-

benzhydryl)-^utâric acid , m.p* I8!t-186®, and liOO g , o f polyphosphoric 20—22 acid, in a 1 liter round-bottomed flask immersed in an oil bath

(20) A sanç»le of polyphosphoric acid “was generously supplied by the Victor Chemical Co., Chicago, 111*

(21) R» M. Wise, Ph. D. Dissertation, The Ohio State University, pp. Ii9-g0*

(22) ?. D. Popp and S. S. Mc»en, Chem. Revs., $8, 321 (1958).

heated to 130-135*^ was vigorously stirred for ninety minutes. During

this time the color of the mixture changed from colorless to deep

red to broTOi. The hot mixture was poured into 1500 g. of ice and

water and stirred well. The solution containing a tan solid was

allowed to stand in the refrigerator overnight. The solid was

separated by filtration, dried and then dissolved in ether-benzene*

The deep red solution was washed twice with water* Ten per cent

potassium carbonate solution was added and the two layers mixed

well* A tan solid separated and, since it was mainly confined to

the aqueous layer, the lower layer was separated and the organic

layer was washed two additional times with carbonate solution, which

removed all of the solid from the organic layer* .The organic layer

TOs treated in the usual manner* The resulting orange-red oil readily

crystallized from ethanol to yield 12.91 g* of tan needles, m.p* •

O e * * " " . I". o o . . © 0 0 o o o * O® ® ® o o ° " 73 o 0 0 ® . ” • • a a . One recrystallization of the first crop afforded 12.33 g« (67.8^)

o f lig h t tan needles, m.p. .0-178,2°. The infrared spectrum

(Nujol mull) showed bands a t $,90 u (s) (Ph-CO) and 6.28-6.37 u (m)

(doublet) and no band near 2,9b u. The analytical sample, recrystal

lized several times from ethanol to yield colorless needles,

melted at 179.3-179.8° (corr.).

Anal. Calculated fo r C28%^Br02* C, 6 3 H, 3 . 8 ; Br, 23.U

Found* C, 63.3; H, k.l; Br, 23.3

The second crop of crystals, m.p. 150-176°, vas not readily

purified* Several activated charcoal treatments and recrystallizations

afforded 2.56 g. of light yellow crystals, m.p. 11*9 - 170°*

On filtration of the potassium carbonate washings, I .36 g. of

tan solid vas obtained# Addition of an aqueous solution of this

solid to cold 6 N hydrochloric acid yielded a light gray solid, which

on drying in air turned to a black tar*

A cid ific atio n o f th e potassium c£u*bonate washings yielded 0.18 g#

of a tan solid not further studied*

The results of several runs are summarized in Table I*. The

column labeled dione" represents the yield of recrystallized dione-

melting above 176°*

In experiments 3j L, 7 to 10, a cream- to tan-colored crystalline-

precipitate formed upon addition of potassium carbonate solution to * * » the crude reaction product dissolved in ether-benzene* This solid

was formed in only small quantities in experiments ? to 10, but was

produced in considerable quantity In experiment and wa

~~O 0» o o o o o 00 o O " « . Table U~~

Cyclization of 3-(o-Bromobenzhydryl)glutarie Acid (Vl) to 6a^ 12b- lïhydro-l-brciraobenzo [c ]phenanthrene-5j8(6H,7H)-dione (VIl) ■with . Polyphosphoric Acid*

~~Expt* Grams of Grams of Heating No* Acid PPA^ Time (min.) Bath. Temp* $ Dione~~

~~1 1.00 20 25 130° 12~~

~~2 1.00 20 70 lU 0-ll2° . 59~~

~~3 2.50 50 35 115-120* 27~~

~~L 2.50 . 50 35 125- 130* 12~~

~~5 2.50 50 70 130- 132* 70~~

~~6 5.00 100 70 133- 135° 59~~

~~7 20.00 Uoo 70 127- 130° 66~~

~~8 20.00 llOO 75 130- 135® 68~~

~~9 20.00 . loo 90 130- 135° 68~~

~~10 100.00^ 2000 100 130- 135° 72~~

a. PPA ■ polyphosphoric acid*

b. The 100 g, reaction was run by treating four 2$ g. samples of the diacid each vâth ^00 g, of PPA under the conditions stated, combining the crude hydrolysis products and working up 'the to ta l mixture in the manner sta te d before *

~~o .- ' - - ' . 72 product in experiment 3» In experiment 3> 1.19 g# of cream-colored~~

~~solid was isolated in the manner described before# The solid was ■~~

~~dissolved in water and added to cold 6 N hydrochloric acid to yield~~

~~0.99 g. of pale tan solid, m.p. lSl-l>L°, Several recrystallizations~~

~~from chlorofonn-Skellysolve B afforded colorless crystals, m.p#~~

~~1S2.9-1$^.0" (corr.)« Neutralization equivalent: Calcd., 359}~~

~~found, 355 # The infrared spectrum (potassium bromide wafer) showed~~

~~bands at 3.2-3.L p (s), 3.8 w (w), if.O u (vr;), 5.51 p (s) (COgH),~~

~~5.36 u (s) (Ph-CO), 6.05 u (m) (?), 6.21 u (m) (phenyl), 12.2 u (w)~~

~~(1,2,3-trisubst. phenyl), 1 3,2 u (s) (o-subst. phenyl), 13,5 ju (w),~~

~~l i i .l u (yr-m) (monosubst.-and/or 1,2,3-trisubst.-phenyl) and 15.5 ju (m)~~

~~indicating the ketoacid, 1,2,3,U-tetrahydro-l-o-brcxnophenyl-i;-oxo-2-~~

~~naphthaleneacetic acid (XX7) as the major constituent uf the solid.~~

~~5,6,6a,7,8,12b-Hexahydro-l-br6mobenzo[c]phenanthrene-5,8-diol (VIII)~~

~~To a clear solution, of 97,6 g. (O.U?7 mole) of aluminum isopropoxide^^~~

( 23) A. L. Wilds, "Organic Reactions," Vol. II, John Wiley and Sons, Inc., New York, N. Y«, 19hhf p. 198. Viscous colorless aluminum isopropoxide, b.p. 102-112° at about 1/h mm, which solidified overnight was obtained in 90 . 2# y ield by th is method#

~~in 500 ml. of isopropyl alcohol (distilled from calcium oxide) in a~~

~~1 liter flask equipped with a 20 cm# packed distilling column (glass~~

~~h elices) was added 61.1 g . (0.179 mole) o f the diketone, m.p# I 77.2 -~~

~~178.5®* The mixture was re fluxed for 1/2 hour, at the end of which,~~

~~time the reflux temperature remained constant at 73 • The solvent~~

~~Vas slowly distilled after thlrtee# Wrs* «f Solvent~~

~~<0 O O O~~

~~o 0 o ° o 0 0 0^0 °°^o °°o o 8 o o o° ° o ° ° o (, o o o o 0~~

~~. " , " '?&~~

~~had teen distilled, the refliuî temperature had risen to .81°, and the~~

~~distillate gave a negative test %vith 2 ,U-dinitrophenylhydrazin 9~~

~~reagent The mixture ivas re fluxed overnight j 100 ml. of the~~

~~(21) Ibid., p. 200.~~

~~solvent was distilled and the warm solution was poured into 2000 g.~~

~~of ice and water containing 100 ml. of concentrated sulfuric acid.~~

~~The mixture was stirred mechanically for two hours, cooled and~~

~~filtered. The white solid was stirred again with 1 liter of 1 N~~

~~sulfuric acid for 1 /2 hour, cooled and filtered to yield 61.9 g* of~~

~~white solid, m.p. 110-l8ii°* The infrared spectrum (Nujol mull)~~

~~showed a strong band at 2,90-3.0^ p (OH) but no band near $.90 u.~~

~~Crystallization of 6»h6 g. of the diol from chloroform yielded~~

~~3 .$ 6 g. of fluffy white solid, n.p. 178 - 21$°, 1.82 g. of light tan~~

~~solid, m.p. 110- 128 ° , 0 .3$ g. of light tan solid, m.p. 128 - 196 ° , 2$ and 0 .3h g. of tan oil.~~

~~(2$) Lithium aluminum hydride reduction of the diketone resulted in the same kind of mixtures.~~

~~The dicarbethoxy derivative (X X V II) o f the d io l was prepared~~

~~(26) L. F. F ieser, J* 2» Hei-z, .M. Klohs» Jfomer® ■ T . Utne, J . Am-. Chem* S o c.| 7li> 3309 (I9$2j# '~~

: . " " . s * *

~~O ® o “ e @ *00 ® ^ * e % o ® » e o»o ® OcPO o 00 Ç o O ^ 0 O O g o O ^ O ® o o® ® O 00 ' = ^ \ ° o O o ° ° °~~

~~» 80®'' , ^ , . s ® ** ° 0 ° 0 0 « o“ o o °» ?T 0~~

~~in .th e ’fellO'S'/îîig manner; To & sdl'ütlea tï 1,00 g. (2.9 cmôles) cf~~

~~the dici, a.j»« 178-215 , In 20 ml# cf dry pyridine (dried over hariun.~~

~~oxide) cooled in an Ice hath vas added dropvdse vith swirling 3 ml#~~

~~jri ethyl cJiloroformate, b.p. 91-92° at ?Ll mm* (redistilled Eastman~~

~~White label). During the addition the mixture turned froin colorless~~

~~to- pink to deep red and a white solid fomed# The mixture was~~

~~■ allowed to stand at room temperature for five hours and then re fluxed~~

~~• gently for one hour. The cooled mixture was poured onto 100 g# of~~

~~ice and water and stirred well, in oil separated which solidified~~

~~on scratching the side of the flask. After cooling in the refrigerator~~

~~overnight J filtering and drying, the white, solid was recrystallized~~

~~from etlianol to y ie ld l .l i t g. (80.3%) of au all co lo rless p la te s ,~~

~~m.p. 156-I 59 ®, and 0.06 g. of white solid, m.p, Ih2-160®. One~~

~~recrystallization of the first crop from ethanol yielded I .03 g .~~

~~(72 ,5%) of the diester, m.p. 159-160°. The infrared spectrum~~

~~(Kujol mull) showed a sharp band at 5*72 p (s) (C ■ 0 in ROCO^F.)#~~

~~The analytical sample, recrystallized several times Arom etlianol,~~

~~melted at 159.8-161.3® (corr*).~~

~~• Anal. Calculated for 58.9j H, 5*1; Br, 16.3~~

~~Pound; C, 58,6; H, 5*1; Br, 16.1 58*7; 5.2} 16.2~~

~~A mixture of 0.150 g. of the diester, 0.2 g . of potassium~~

~~hydroxide, h m l. o f methanol and 1 ml. of water was re fluxed for ® e ® 1 /2 hour and then poured onto 50 g. of ice and water and s tir re d~~

~~® • * ** f ® ® ® Irell* The cold mixture was filtered and washed with water to~~

~~@ . ÿ le id O#10d g# cf 'whit# s o lid , m.p# 206-222®# Three reery sta lliza tien s 9 . # 9 • . / - " " ■% @ ®~~

~~° a so # 9 ' " « % _ o ®o®o e o~~

o o d o o 0 jof tli* A o l fjrÿ» t ’Sipi 0.06^ g*

(2?) Obtained from Antara Chemicals, & sa le s divisiott o f • General Aniline and Film Corporation*

of short white fib e r s, m.p# 222- 223° and 0,007 g* of white fiber?*

~~Pi.p# 220-221 • An a n a ly tica l sample from .the f ir s t crop was dried~~

~~in a desiccator over phosphorous pentoxlde for several days* ' ' ' .~~

~~/j.al. Calculated for C, 62.6; H, 2*0; Br,’ 23.2~~

~~Fouxidj . C, 62.2; r, 2.0; Br, 23*3~~

~~1-Bromobengo [e]phenanu!irene (IX)~~

~~A solution of 10 g. of the diol, m.p. 1 1 0 - 1 8 in 1200 ml. of~~

~~hot chloroform was filtered and the solvent removed to yield 10.00 g.~~

~~of cream-colored solid, m.p. 120-193°.~~

~~A mixture of 1.99? g* (2*79 mmoles) of the diol, m.p. 120-193°, .~~

~~2 ml* of sylene (redistilled Mallenckrodt Analytical Reagent) and~~

~~8*2 mg. of iodine were heated to the reflux temperature. Within a .~~

~~minute after refluxing started, the iodine color disappeared and~~

~~vhithin fifteen minutes a ll cf the diol had dissolved leaving a~~

~~Ught yellow solution. After the mixture had refluxed for twenty-~~

~~four hours, an additional 3.9 mg. of iodine was added to the yellow~~

~~solution. The iodine color again Àsappeared rapidly. After having~~

~~been refluxed for 120 hours, the deep red-brown solu tion was diluted .~~

~~with ether4)en%ene, washed with sodium b isu lfite xolutlon and '~~

~~. treated In the Usual manner* Ibe yellow-browa o il w&s dissolved ' . . *t. : in 2 ohlorofom and chromatographed m & % 160 m® tolw#~~

~~. 0 * " * J " "~~

~~. ' . , .7? ,ç)f' activated gcrma^hed vlth bêftsent* îhree fraeUoas «er«~~

~~®t>taiftedî.~~

~~1* 259 ml. c f lig h t yellow benze»e solation containing the~~

~~m aterial that fluoresced as a dark graywvlolet hand under~~

the ultraviolet light*

~~; 2* yOO ml, o f very 11 ^ t yellow benzene solution which, wlien~~

~~evaporated, yielded 0*072 g. of red-brown o i l , which showed~~

a wide hand at 5*7-5*9 p (C » 0) in its infrared spectrum*

~~3* 1300 ml* of yellow ethanol solution vMch, when evaporated,~~

~~yielded 0*361 g. of red-brown o i l .~~

~~The f ir s t fraction was rechromatographed on a 35 X JO mm. column o f~~

~~alumina prewashed with Skellysolve B, to yield the following fractions;~~

~~U* 2500 ml* of Skellysolve B solution, containing the dark~~

~~gray-violet band (under u ltra v io let lig h t).~~

~~1000 ml* of Skellysolve fi solution which, when evaporated,~~

~~yielded 0*02li g « of red-brown o i l .~~

~~6* Loo Bil. of ethanol solution idiich,wdien evaporated, yielded~~

~~0*13$ g* o f red-brown oil* iraction h was evaporated and crystallization from chloroform-~~

~~. Skellysolve B afforded I.O78 g* of yellow crystals, m.p. l39*0-lh3*S®~~

and an, o il. Several reczystallizations from chlorofom -Skellysolve - B. afforded 0*95$ g* ($3 «6^) of yellow •crystals, m.p* lWi-lL6®» STorîs • '' * . " «1 • " bp o f the mother liq,uer.an.d the e l l ebtained above yielded 0*082 g# *»*^ 0 ®. o « e f yelled erystals^ m.p# 128*161% 6*D$2 g* « f yeUewlbrewa eiyatal»^ . S e . , " ; e « %.p# 1084ltl% W g»'#f yellôw « i l l % » da#a&e&

~~showed no hydroj^l or carbonyl bands, but possessed significant~~

~~. bands at 11.111 (m), 11.$ ft (s}, 12.0 «I (s), 12.3 ? (s)> 12.5 U (w^),~~

~~13.0 fi (s), 13.2 fi (s), 13.$ » (s) Iha n (a-s), 15.1 u (s) and 15.8 p (vf). A sajiple, purified for analysis by several recrystalli~~

~~zations from chlorofoza«£kelly8olve B, followed by vacuum sublimation,~~

~~formed pale yellow crystals, n.p* lh6.8-ll;7.3® (corr.).~~

~~Anal. Calculated for C^gH^^Br* C, 65,5; H, i».2; Br, 25.9~~

~~for C^gHj^Brî C, 70,h; H, 3.6; Br, 26,0~~

~~Found: G, 70.U; H, 3.7; Br, 26.2 70.2; 3.6; 26,3 28 The tetranitrofluorenone complex was prepared by mixing a hot~~

~~(26) M. S. Newman and W. B. lu tz , J . Am. Chem. S oc., 76, 2li69 (1956 ) . ~~~

~~solution of 100 mg. of the bromide, m.p. IhU.0-115.5°» in g la cia l~~

~~acetic acid T d t h a hot solution of I30 mg. o f 2 ,h,5 ,7-tetran itro-~~

~~9-fluorenone,29 m.p. 253.0-25U.5® (corr.), concentrating the solution~~

~~(29) Prepared and purified by Br. Wilson B. Lutz, The Ohio State University.~~

~~■ to 4 ml. and cooUjig, to yield 0,187 g. of dark wine-red needles^~~

~~. m.p* 191.5-192.5^ and 0.006 g . o f dark wine-red needles-, mvp, .~~

~~l?0*5-19i«5^* The analytical sample, recsy)stallizf d several times~~

~~e Am glacial aeetle acid, melted at 19^#3-493.5^ (corr.)#, %~~

~~°. " ’ • . El~~

~~Anal, C&Jcwlatgj forCa 3,%^:~~

~~C, S5.8; H, 2 . 3 ; 3r,' 3.îj; !*, 12.0~~

~~Found: C, 5^>.l; H, 2.6; 3r, 8 . 6 ; i:, 12,C~~

~~The ultraviolet absorption spectrum of the bromide in~~

~~ethanol (Figure 13, p. Ii2 ) was indicative of a completely aromatic~~

~~benz0[c]pher.anthrene derivative,20,31~~

~~( 30) R. A, F ried el and ÎÎ. Orchin, "U ].traviolet Spectra of Aromatic Compounds,” John Wiley and Sons, I n c ., Few York, N.Y., 1951, Figures 0.~~

~~(31) G. M. Badger and I . S. Walker, J. Cherj, Soc., 3233 (1951;).~~

~~The nuclear magnetic resonance spectrum^^ showed no a lip h a tic .~~

( 32) Determined and interpreted by Dr* George Slomp, The Upjohn CoTipany, Kalamazoo, Mich. The spectrum wag obtained on a concentrated solution of the sarçile in deuterochloroforra using a Varian V-I|3C0-2 spectrophotometer a t LO megacycles per second in a magnetic field of 9U00 gauss. The spectrum was calibrated by the audio frequency sidebond technique [J, T. Arnold and E, Packard, J. Chem. Phys., 19, I 6O8 ( 1 9 5 1 ) ] against water in a precision externa] annular cell [J* R, Zimmerman and iî, R, Foster, J* Phys. Chem,, 61, 262 (195?)].

~~vinylic or allylic hydrogens.~~

~~The evidence presented indicates that the bromide was not the~~

~~expected dihydro-l-bromoben 2 o[c]phenanthrene, but the fully aromatic~~

~~l-bromobenzo[c]phenanthrene (IX).~~

~~Before the. fu lly aromatic character o f the bromide was determined,~~

~~several atteint* ver* mad* to deV^regerato it# For exanple.~~

~~o o 00 o Ù i o % o 0 ® ® o o O O « 0 00 O ^ 9) -» . ® « o o " o 0 ^ 0 ° o 00° 00 00 ° ° ^ 0 0 ° ° 00 o o % * " " 00 " u o " . « ^ _ "o : _~~

~~treatmer.t c f tî;é cr:de bronWe with chlor?ir.i2.^^»'^ In reflvwîîrt*. “~~

~~• (33) R. T, Arnold and C, J» C o llin s, J , Am, Chen, Soc,, 6I, . _ II07 (193?).~~

~~(3h) R, M. Wise, Ph,D, Dissertation, The Ohio State University, 1923, pp. 22- 60.~~

~~xylene for as long as s eventy-foiir hours or vdth 2,3-~~

~~dicyano-1, L-benzoqninone^^*^^ in refluxing xylene for thirty-one~~

~~(32) E, A. Braude, A, G, Brook and ?., P, Linstead, J. Chenu Soc., 3269 (1921).~~

~~( 36) Prepared and purified by Dr. P. M, G, Bavin, The Ohio State University.~~

~~hours or in dineth;;lforrsanide at 100" for sixty-one hours yielded the~~

~~starting material v irtu a lly unchanged. Treatment o f the bromide,~~

~~m.p. 141-1 !4^3", with an equivalent amount of sulfur at 212-232" for~~

~~1-1/2 hours yiel ded cry sta ls, m.p. 128-1hh*. Treatment of the bromide,~~

~~ffl.p. lL2.C-lii6.2", with an emlvalent amount of sulfur at 272-282"~~

~~for one hour yielded an oil that could net be crystallized.~~

~~The effect of concentration and length of time of reaction was~~

~~investigated in the iodine In xylene reaction. The results show that~~

~~a fairly concentrated, solution of the diol. in xylene refluxed for a~~

long period (greater than eighty hours) gave the highest yields of ■ . . ■ ■ ^ dehydration* The results are summarised in Table 2* The procedure • * . • . tsed was the following; .X mixtur# f f diol and'sj^lene wag. heated

~~® o es o~~

~~o o o~~

~~to the reflux temperature, several cr^'stals of iodine rrere added, and-~~

~~the mixture reflu>:ed for a number of hours. At the end of the~~

~~reaction the usually v e r y dark solution vas diluted with ether-~~

~~benzene, isashed with sodium b isu lfite solution, treated in the~~

~~usual manner, and chromatographed on alumina using benzene as~~

~~eluant for non oxygen-containing substances and ethanol for bydroxyl-~~

~~and carbonyl-containing substances.~~

~~In experiment 1 (Table 5) during the 'worlnç after treating~~

~~in the usual manner, concentration of the solvent yielded 0.9k g,~~

~~of tan crystals, m,p, 160-162°, 0.23 g, of tan crystals, m.p. 155-~~

~~l58°, and 0,69 g. of yellow-orange o il. The infrared spectrum of~~

~~the first and second crops showed hydroxyl groups present. Several~~

~~recrystallizations of the first crop from chloroform-Skellysolve 3~~

~~yielded fluffy white needles, m,p. 165,5-166.8° (corr.).~~

~~Anal, Calculated for diol)j C, 62*6; E, 5.0; Br, 23.2~~

~~for O^gH^gBrO* C, 66.1; H, U,6; Br,~~

~~for C, 69.9; H, k.2; Hr, 25.8~~

~~Found* C, 65.2; K, U.6; Br, 2k,3~~

~~O O 0 o 0 0~~

~~O 0 0 o o o o 0~~

~~(§> @ 5~~

~~DahydPAtion Ualag IW ^ e in Xylene~~

~~MiWiT Sixpt* Êrâm? ©f ■ M##'. T?©ltta® ©f Baflux Height of % W eight-of Slo* A lcobel lle sh o l ^lesi© time Hon-oxgeaated flei^ration^ Reqovered Oxygenated~~

» * ' 1 t»tk g« a%% 6 m l. 26 tor. 0*39 g . 20 0 .91* g ., m.p. Ié0«l62® 0*23 g*, m.p. 156-153® 9 0.22 g. oil * 91 0,178 121*139^ 2 6? 0.306 66 0.227 g. oil 0.202 121.193*) ® o 0.23U o n oo 0 ,21*9 2 99-1/2 0.180 81 O.OhO g . o il ,

*jl 1 , 9 1 65-^19® % 8i* 1.332 77 0.321 g. oil • . o 0.02 o n

0*336 o i l 1 120 0.209 62 0.026 g. oil . Î ', 1 , 1 0 1 182. 217® 1 0 7 9 0.290 29 0.650 g.^(0.ii5 g.> m.p.l6U-166® o ' . «• 0.19 g, oil) O 9 o o 0,LS 164-166® 2 120 0.528 61* 0,086 g. oil . 9 » 0 * 1 9 o i l 0 0 @ 9 O .»« Ip.elttdoe a ll non-os^gonated material, b# Recycled.

~~r - o a e o~~

~~OO oo _ ^ O o o O oo O 0 0 o o ° O o O c O o o O O O o c " . . 82.~~

~~lndi.ea.%e8 that the s^ibstanca Is nostl^ a non~~

~~alcohol, either r -I /II I cr Z"I%.~~

~~Other Attempted Methods of Dehydration of vTTT~~

~~The d io l, ra*p, 6o»2l5*, rmen heated elo'fly from 2G0* to 270" 1ft~~

~~•forty-five minutes, yielded, after chromatography, an o il (6L^~~

~~dehydration). Treatment of 0.032 g* of the oil with sulfur at~~

~~205-210* for one hour yielded an oil. Crystallization affordad~~

0*07 g, of so lid , m*p, 1/+7-172*, and 0,02 " , of so lid , n;,p, 102-lîil**

~~In another experiment, 0*31 g. of diol, m,p, 173-222*, when heated~~

~~At 2 05-2 W for fifteen Mm tes, yi.elded, after chroiuatograp,hy,~~

~~0.086 g. of yellow o il, which contained no hydroxyl band but a, very~~

~~vresdc carbonyl h&nd in the infrared spectrum, and an o i l ( ethanol~~

~~elu tio n ). The second, o,il, when heated at 250-265* for fifteen~~

~~iaiwt«s gave m oil with a medium to strong carbonyl band in the infrared st-ectrurü,~~

~~Ketti,ng cf the d io l, m.p, 177-222*, with one crystal of potassium~~

~~bisulfate^^ #,t 220-230" fw thirty sdmtes,, yielded sa oil~~

~~$ (37) U Brunei, Bull. «oc. chlm. JYanee, (3),* 270 (19055. ft «~~

~~9 9 J 9 ® ®~~

~~' ' ' * . ' . . . . •- • • •• • “ • „ O o O ® 0 o O - ®~~

o ® 0 m 0 m O A A ** o o o o 6 5 o " O Q dehydration); T^iich On refluxing vfith 2,3“Hichlor°o-5,6-dicyano-l,U- o ^enzoquionone^^ irt chlorobenzene for fourteen hours afforded yellow o Solid, m.p. 261-297 , which did not fora a complex with tetranitro- 23 fluorenone • ° °

~~“ The d io l, n.p» 1Û8-19Û®, was heated a t 200-205® for ten minutes.~~

~~One érj’^tal of iodine^S was added and the mixture was heated to 230®~~

~~(38) H. Kibbert, J. An. Chem. Soc., 17ii8 (191$).~~

~~in five minutes. Working up yielded an o il (87% dehydration), from~~

~~0.50 g . o f which was crystallized 0.23 g* of so lid , m.p. 203-228®,~~

~~and 0.07 g. of solid, m,p. 1$5-I8l®. When ire oil was refluxed with~~

~~diehlorodieyanoqpinone in xylene for twenty hours, solid material,~~

~~m.p. greater than 160*^ to greater than 280®, was obtained.~~

~~Treatment of the d io l, m.p. 68-215®, with pfaetQrlisocyaaate^^~~

~~(39) W. Oroshnlk, G. ^rmas, and A. D. Mebane, J . Am. Chem. Soc., 7h, 295 (1952).~~

~~yielded an oil (38# dehydration).~~

~~The dicarbethojqr derivative (XWII) was pyrolyzed at 235-2U5®~~

~~fof one hour. The infrared spectrum of tiie product showed a weak~~

~~to medium tand "at it with » wide shoulder at 5 *8-5.9 p. i^rolysls~~

~~at 2&5-27Q® for ten minutej yielded jthe same product» Chromatography~~

~~’ * . 3«ii «alumina gave indications that the product Was a mixture#~~

~~o o ' ° ' ' . 87 ■ Treatment o f 0.^0 g, o f the diol, la.n, 176,21$°, Tdth thionyl~~

~~’■ chloride in p^.nridine^*^* a t room temperature for li-1/2 hours yielded~~

~~(liO) A. Arkell, Ph. D. Dissertation, The Ohio State University, 1928, p. ii9.~~

~~(Ul) B. E llis and V. A. Pet row, J . Chem. Soc., 1081 (1939).~~

~~0.110 g. of tan solid (weak hydroxyl band, sharp band at 6,1 p. (w-m).~~

~~Heating at 90® for 1-1/2 hours yielded 0.128 g. of brown-black solid.~~

~~1-Cyanobenzo [o}phenanthreng~~

~~A mixture of 0.200 g. (1.62 mmoles) of 1-bromobenzo[c]phcnanthrene~~

~~m.p. l!i3.0-llili.2^, 0.223 g. (2.93 mmoles) of dry cuprous cyanide^^*'^~~

~~(112) ÎÎ. S , îlewman, «Organic Syntheses,” C oll. Vol. I l l , John Wiley and Sons, In c., New York, M. I , , 1922, P* 631.~~

~~(113) J . E. Call en, C. A. Domfeld and G. H. Coleman, «Organic Syntheses,” Coll. Vol. I ll, John Wiley and Sons, Inc., New York, N. Y ., 1922, p . 212.~~

~~(liii) C* P. Koelsch and A. G. Whitney, J . Org. Chem., 6, 795 (1 9 ia ).~~

~~and 2.2 ml. of N-oethyl-2-pyrolidone,^7, ^2 b .p . 96 ® at 22 mm., was~~

(U2) T. F. Corbin (Ph. D. Dissertation^ The Ohio State University, 1926} converted several m- and p-substituted bromobensene derivatives to the corresponding benzonitriles by refluxing a mixture o f the bromide and cuprous cyanide in dimethylformamide (b.p. 123®} for several hours. High y ield s (72-82^) were obtained in each case.

~~• •~~

~~O O O 0^ re fluxed (b .p , 202*) for one hour. During th is time the dark red-~~

~~brcwn solution changed to a dark broinn color and a brown precipitate~~

~~formed. The cooled mixture was poured into a warm solution of 20 ml,~~

~~of water containing 1,0 g, of ferric chloride hexahydrate and 1 ml,~~

~~of concentrated hydrochloric acid, A dark solid formed. When~~

~~ether-benzene was added and the mixture was stirred and warmed^ most~~

~~o f the solid dissolved. %e two layers were separated and the aqueous~~

~~layer was extracted with ether-benzene. The combined organic layers~~

~~were treated in the usual manner. The concentrated yellow-bro:m~~

~~solution (5 m l.) was chromatographed on a 3$ 1 130 mm. column of~~

~~activated alumina, prewashed with benzene. The f ir s t 600 ml. of~~

~~benzene contained the substance which had a brilliant violet~~

~~fluorescence in ultraviolet light. Concentration of the solution and~~

~~crystallization from benzene-ethanol yielded 0,310 g, of flat cream-~~

~~colored crystals, m.p* 167-169®, and 0,019 g, of flat yellow crystals,~~

~~m.p. 115-161®, Several recrystallizations from benzene-ethanol .~~

~~afforded 0,292 g, (?1.0^) of flat cream-colored crystals^ n.p,~~

~~169-1?1®* The infrared spectrum (potassium bromide wafer) showed~~

~~bands at h.52 u (w-m) (C a N), 11 .U u (w-m), 11.8 p ( s ) , 12.1 p (w-m),~~

~~12.L n (w), 12,9 p(s), 13,0 n (w) (shoulder), 13.2 p (s), I3.3 p (m) • ,~~

~~(shoulder), 13.5 P (w) (shoulder), lh.9 p (s), 15.5 T» ..W and 15.9 p.(w-m)»~~

~~-The analytical sample, reciystallized several times from benzenen#~~

~~ethanol, melted At 171*2-172«0® (corr#)* * @~~

~~Anal* Calculated fop PO.l; If, $ 4~~

~~' . "goundt K, % SS » «~~

~~o eo o o o o g o o o ° o o o o n ° O O o 0 o 0< o û o 0 Q O O ^ O «0 " O o . . . ° " 0 'CS O Q a rrü m ï : ° o o~~

~~, The synthesis of l-bro3ioben%o[c]rhénantlirene In lîu3!? J'ielâ ° ' In eleven steps from o-hrpmobenzaldehyde (I) is described.~~

Condensation of ethyl cyanoaectate with I afforded athj^l o-hromo*

~~benaalcyanoacetata (II) in 91,?'? yield. Addition of phenyl-~~

~~magnesiura, bromide to II yielded ethyl o-broraobenzhj^drylcyaTio-~~

~~acetate (III) in 9Q,7% yield, ’-(ydr^Iysls of III with potassiuia~~

~~hydroxide in ethanol yielded o-bromobenshydr^/]malonic acid (TV)~~

~~in 8U.QS yield. Estérification of I? with diasomethane yielded the~~

~~dimetiiyl ester (?) in 88*1^ yield. Lithium aluminum hydride~~

~~reduction of V afforded 2-(o-bromobenzhz'dryl)-],3-propanediol (VI)~~

~~in 91.7# yield. The diol (VI) was converted to 3-( o-bromobenzhydr:-.l )~~

~~glutaric acid (VII) in 70,3# yield by conversion of VI to the bis-~~

~~methanesulfonate, followed by replacement of the ester groups with~~

~~cyanide and alkaline hydrolysis of the dinitrile to VII, Double~~

~~• cyclisation of VII with polyphosphoric acid afforded 6a,12b-~~

~~dihydro-l"bromobeiso(c]phenanthrene-?,8(6H,7H)-dione (VIII) in . '~~

~~67,8# yield. Lithium aluminum hydride reduction of VIII afforded ■~~

~~the corresponding diol (IX; quantitatively. The diol (DC), when~~

refluxed with a catalytic amount of iodine in xylene for 120 hours • •' " ^ 9 yielded l-bi'omobenzo^c] pher.anthr ene (XIX) in $3,6# yield*

* ^ ° . .. ' f « Treatment of X with cuprous cyanide in N-mathyi»2-pyrolidon«°

~~o ^ ^afforded l*<:}’'anobenzo(cJphenanthrene (XII).in 71,0# yield/ ® ” * ♦ . ’ o * » SS» o ® « «’ o # » ® S » o o o~~

~~® ® o o ® D o ® 0 o o O 9G %pndengatiom of (tietr;rl naîônats w ith I yielded diethyl~~

~~©«■'bromobenaalmalonate {XIH) in 68*QS y ie ld . Addition of pi'ier^'l- magnesiiim bromide to XIII afforded diethyl o-brotnobenzhydrylmslonate~~

~~{XIV3 in poor y ie ld . Lithium aluminum hydride reduction of XIV yielded VI»~~

~~Condensation of malononitrile with I yielded o-bromo-~~

~~benzalmalononitrile (P/J, Addition of phenylma^nesium bromide to~~

~~XV afforded o-bromobenshydrylmalononitrile (XVI),~~

~~o o 0 o 0 o o 0 0 O 0 o o o o o o 0 ° c 0 o o~~

~~■ AUTOBlOGmPHt~~

~~• I , Donald Kenney P h illip s, vas bora in Nevarfc, Délavaro$ oa~~

~~April 2U, 1931» I received my secondary school education in tha „~~

~~public schools of Newark, Delaware,and my undergraduate training~~

~~at the University of Delaware, which granted me a Bachelor of~~

~~Science degree in 1953* In September, 1953,1 entered the Graduate School of The Ohio State University. VMle completing the~~

~~requirements for the degree Doctor of Philosophy I held the~~

~~following positions: Assistant in the Department of Chemistry,~~

~~1953-1955 end summer quarter, 195^5 Assistant Instructor in the~~

~~Department of Chemistry, 1955-1956» and Research Fellow supported “~~

~~by a grant from the Office of Ordnance Research, U. S . Amy~~

~~1956-1958. ' .~~

~~(* a~~

~~^ - 0 ® fl A O Oo 0 o 9~~

~~o o~~