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The action of carbon monoxide and hydrogen on deoxybenzoin oxime and on 2-acetonaphthone oxime Hubscher, Arthur Ronald 1959

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THE ACTION OF CARBON MONOXIDE AND HYDROGEN ON DEOXYBENZOIN OXIME AND ON 2-ACETONAPHTHONE OXIME by Arthur Ronald Hubsoher A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS POR THE DEGREE OP MASTER OF SCIENCE in the Department of Chemistry We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA May, 1959 ABSTRACT When d e o x y b e n z o i n oxime was r e a c t e d w i t h c a r b o n monoxide and h y d r o g e n i n t h e p r e s e n c e o f d i c o b a l t o o t a c a r b o n y l a t e l e v a t e d t e m p e r a t u r e s and p r e s s u r e s 5 - b e n z y l p h t h a l i m i d i n e and 3 - p h e n y l - 3 , 4 -d i h y d r o i s o c a r b o s t y r y l were p r o d u c e d . When 2 - a c e t o n a p h t h o n e oxime was r e a c t e d u n d e r s i m i l a r c o n d i t i o n s 2 - ( ^ - n a p h t h y l ) - 4 - m e t h y l -benzo[h] q u i n o l i n e , 2 - m e t h y l b e n z o f f ] p h t h a l i m i d i n e and 1- ( ^ - n a p h t h y l ) e t h y l u r e a were p r o d u c e d . V e r i f i c a t i o n o f t h e s t r u c t u r e o f 2 - ( ^ - n a p h t h y l ) - 4 - m e t h y l b e n z o [ h ] -q u i n o l i n e was a t t a i n e d i n p a r t t h r o u g h t h e h y d r o -c h l o r i d e s a l t , t h e m e t h i o d i d e s a l t , t h e p i c r a t e d e r i v a t i v e and t h e 2 - ( ^ - n a p h t h y l ) - 4 - f o r m y l b e n z o f h ] -q u i n o l i n e d e r i v a t i v e . 2 - ( ^ - K . a p h t h y l ) - 4 - m e t h y l -b e n z o f h ] q u i n o l i n e was a l s o s y n t h e s i z e d b y r e a c t i n g 2- a c e t o n a p h t h o n e oxime w i t h 2 - a c e t o n a p h t h o n e a t e l e v a t e d t e m p e r a t u r e s . The i n f r a r e d s p e c t r a o f t h e above compounds a r e d e s c r i b e d . In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make i t freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the Head of my Department or by his representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of The University of British Columbia, Vancouver 8, Canada. ACKNOWLEDGEMENT I wish to express my sincere thanks to Dr. A. Rosenthal for his patience, advice and encouragement in the direction of this researoh project. TABLE OF CONTENTS PAGE I. HISTORICAL BACKGROUND (a) High Pressure Reactions of Carbon Monoxide with Nitrogen Containing Compounds 1 (b) ©xlmes 7 (o) Cobalt Complexes of Oximes and other Bases 10 II. DISCUSSION Reactions of carbon monoxide and hydrogen with: (a) Deoxybenzoin oxime 1 3 (b) 2-Aoetonaphthone oxime 14 III. EXPERIMENTAL 2 6 Reactions of carbon monoxide and hydrogen with: 28 (a) Deoxybenzoin oxime (b) 2-Aeetonaphthone oxime 31 ( Q ) Reaction of 2-aoetonaphthone with 2-aoetonaphthone oxime 5 6 IV. BIBLIOGRAPHY 5 8 V. ADDENDUM l - ( £ - N a p h t h y l ) e t h y l u r e a f r o m 2 - a e e t o n a p h t h o n e oxime 6 2 LIST OF FIGURES 1. Ultraviolet speotra of phenanthrene, 2,4-dlmethyl-benzo[bJquinoline and 2- (^-naphthylj-4-methylbenzorh]-quinoline 2 5 a 2. Plot of Pressure against Time for the Reaction of 2-Aoetonaphthone Oxime with Carbon Monoxide and Hydrogen at 195° 25b 2. Separation of the 2-Acetonaphthone Oxime Reaction Produots 2 6 4. Infrared Spectra of 2-(^-Naphthyl)-4-methylbenzoCh]quinoline, 3-Methyl-benzo[fJphthalimidine and 3,4-Dihydro-3- phenyliso carbostyryl 57a I. HISTORICAL (a) High Pressure Reactions of Carbon Monoxide  with Nitrogen Containing Compounds A considerable amount of investigative work has been done on both a purely scientific and a commercial basis on a study of carbon monoxide and hydrogen with olefins. An excellent review of this work has been presented by Wender, Sternberg and Orohin (21). To the best knowledge of the author there i s only one recent paper by other workers (48) on a study of the reactions of carbon monoxide and hydrogen with organic oompounds containing the C=N system yielding reduced products but giving no addition with carbon monoxide. However, several workers have reoently investigated the carbonylation of a few organic com-pounds containing the N=N, the C=N and the C-N groupings. In 1949 Buckley and Ray (12) reported that they reaoted oarbon monoxide with aniline to produce a cross linked polymer containing varying amounts of oxygen in the hydroxyl form and having a l l i t s nitrogen in the primary amino form. They also investigated the a b i l i t y of carbon monoxide to aot as a reducing agent (13). Nitrosobenzene and azoxy--2-benzene were reduced to azobenzene, U-phenyl-hydroxylamine was reduced to aniline, and N-phenyl-benzaldoxime was reduced to benzylideneaniline. Work of a commercial nature has been done in the preparation of amides from carbon monoxide, olefins, and amines (49, 51, 52) and formamide has been success-f u l l y prepared from ammonia and carbon monoxide (41). Tyson and Shaw in 1952 (68) prepared 3-indole-oarboxaldehyde from carbon monoxide and the potassium salt of indole. They did not produce any N-formylated products of indole but in 1956 (63) they produced l -£ormylindoline in good yield from both carbon monoxide and potassium indoline. Prom this they deduced that l i k e l y the U-formyl form of indole i s produced but that this very readily isomerizes to the 3-oarboxal-dehyde form. Priehard in 1956 (53) cyolized the aromatlo amide H,N-dibenzoylaniline with oarbon monoxide at 325°G. using nickel carbonyl as the catalyst. E-phenylphthalimidine and benzene were produced. Similarly an equimolor mixture of benzonitrile and -2-benzoic aoid, which react to form aibenzamide above 250°G. (17), when heated at 325°e. with carbon mon-oxide and nickel carbonyl gave phthalimide. In 1955 Murahashi (46) heated benzaiaehyde anil in benzene with dioobalt octaoarbonyl and 100-200 » • — atmospheres oarbon monoxide at 22O-230°C. for 5-6 hours. 2-Phenylphthalimidine was obtained in 80% yield. In a similar way p-hydroxybenzaldehyde anil yielded 70% 6-hydroxy-2-phenylphthalimidine. 0 cc-Haphthaldehyde anil afforded 2-phenylbenzo [e]-phthalimidine in 90o yield. ^-Naphthaldehyde anil yielded 2-phenylbenzo [f]phthalimidine. The faot that ring closure oocurred in the 2-position of the naph-thalene moiety i s noteworthy since most ring closure reactions of ^-substituted naphthalene derivatives 0 -4-take place in the 1- o r ° c - position. In 1956 Murahashl and Horiie (47) reaoted azobenzene with oarbon monoxide at 150 atmospheres and 190°C. to form indazoline. At 230°C. an additional mole of carbon monoxide was absorbed per mole of indazoline and the product formed was 3-phenyl-2,4-dioxo-l,2,3,4-tetrahydroquinazoline. That this compound proceeded through indazoline was shown 0 by the fact that the indazoline reacted with carbon monoxide at 230°C. to give 3-phenyl-2,4-dioxo-l,2,2, 4-tetrahydroquinazoline in quantitative yield. Sim-i l a r oonversion to the analogues of the above compounds were carried out with 4-ohloroazobenzene and 4-dimethyl-aminoazobenzene. In the case of the substituted azobenzenes ring closure occurred on the ring contain-ing the substituent. -5-In 1958, Priohard (54) prepared N-substituted phthalimidines from N-substituted imines of carbocyelic aromatio ketals. Por example, he prepared 2-phenyl-phthalimidine from N-benzylidine aniline and he also prepared the following derivatives of phthalimldine: 6-MeO, 6-C1, g-Me, S-Ph, 6-Me2N, 2-Me, 2-(1-naphthyl), S-(p-diethylaminophenyl), and N,N -ethylenediphthal-amidine. In 1958 Kakamura and Hagihara (48) hydrogen-ated Sohiff bases in the presence of carbon monoxide, hydrogen and dicobalt octacarbonyl at elevated temperatures and pressures. They reduced benzal-phenylimine (PhCH=NPh), benzalcyclohexylimine (PhCH=WCgHn), cyolohexanophenylimine (C6Hi0=NPh) oyolohexanooyclohexylimine (CgH^o^l^Hj^ ). a n d cyclohexaloyclohexylimine ( C 6 H J L X C H = U G5H I X ) "to second-ary amines. The Sohiff bases which were the most conjugated were the most easily reduced and formed the lowest amounts of resinous by products. Non polar solvents gaye the highest yields with cyclo-hexane giving higher yields than benzene which, in turn, gave higher yields than did dioxane. Sulphur compounds did not retard the reaotion although amines, especially the aliphatics, lowered the yields -6-o o n s i d e r a b l y . A l t h o u g h r e c e n t work was r e p o r t e d i n t h e s t u d y o f i m i n e s and azo compounds i n t h e i r r e a o t i o n w i t h c a r b o n monoxide no work was r e p o r t e d o u t s i d e t h a t o f K o s e n t h a l and A s t b u r y ( 55) f o r t h e r e a c t i o n o f c a r b o n monoxide and h y d r o g e n w i t h o x i m e s . I n 1958 t h e y f o u n d t h a t b enzophenone oxime r e a c t e d w i t h o a r b o n mon-o x i d e and h y d r o g e n t o y i e l d 3 - p h e n y l p h t h a l i m i d i n e i n 80$ y i e l d . G y c l i z a t i o n o f t h e oxime w i t h c a r b o n mon-o x i d e t o o k p l a c e when t h e r a t i o o f c a r b o n monoxide t o h y d r o g e n was l a r g e ( 9 8 : 2 ) . O - B e n z o y l b e n z o i o a c i d 0 oxime a l s o gave S - p h e n y l p h t h a l i m i d l n e i n a l m o s t q u a n t i t a t i v e y i e l d a nd, h e n c e , s h o w i n g t h a t u n d e r t h e c o n d i t i o n s o f t h e r e a o t i o n d e c a r b o x y l a t i o n had t a k e n p l a o e . When a c e t o p h e n o n e oxime r e a o t e d w i t h c a r b o n monoxide i n t h e p r e s e n c e o f h y d r o g e n and d i c o b a l t o c t a o a r b o n y l a s y r u p was o b t a i n e d w h i c h was s e p a r a t e d i n t o t h r e e f r a c t i o n s by a l u m i n a c h r o m a t o g r a p h y . The f i r s t f r a c t i o n (10$) c o n t a i n e d no c a r b o n y l g r o u p and was n o t worked w i t h f u r t h e r . C h e m i c a l a n a l y s i s o f -7-one of the other fractions indicated that two moles of acetophenone oxime had condensed with a mole of hydrogen and a mole of carbon monoxide to yield a dimer which lost a mole of hydroxylamine. This compound failed to give a derivative with 2,4-dinitrophenylhydrazine a l -though i t showed a strong oarbonyl peak at 17G0 cm. ^ in i t s infrared spectra. The third fraction recovered from the reaction mixture was identified as 3-methyl-phthalimidine by comparison with an authentio sample. (b) Oximes An aldehyde or ketone with the structure RTC=0 when treated with hydroxylamine gives a single oxime i f the radical groups R and T are identical. However, i f the two groups R and T are different i t turns out in most cases that two isomeric oximes can be detected (1, 7, 27). An explanation put forward by Hantzsoh and Werner (29, 30) states in effect that the two isomers were stereoisomers of an ethylenic nature as postulated in formulas I and I I . The nitrogen atom R-C-T R-C-T ll I  N-OH HO-U I II like the oarbon atom i s tetrahedral but differs from -8-t h e o a r b o n atom i n h a v i n g a n u n s h a r e d p a i r o f e l e c t r o n s a t one o f t h e a p i c e s o f t h e t e t r a h e d r o n r a t h e r t h a n a n a t o m i c o r m o l e o u l a r g r o u p ( 7 8 ) . T h a t t h i s i s t h e most s a t i s f a c t o r y s t r u c t u r e e x p l a i n i n g t h e i s o m e r i s m o f t h e o x i m e s i s e x p l a i n e d i n c o n s i d e r a b l e d e t a i l i n "Advanced O r g a n i c C h e m i s t r y " b y Wheland ( 7 2 ) . An i m p o r t a n t r e a c t i o n f o r d e t e r m i n i n g t h e c o n -f i g u r a t i o n o f o x i m e s i s t h e so o a l l e d Beokmann r e -ar r a n g e m e n t ( 4 , 5, 6 ) . When a k e t o n e oxime i s t r e a t e d w i t h a r e a g e n t s u o h a s p h o s p h o r u s p e n t a o h l o r i d e , a c e t y l c h l o r i d e o r s u l p h u r i c a o i d a r e a r r a n g e m e n t t a k e s p l a c e t o g i v e a s u b s t i t u t e d amide. The a r r a n g e m e n t i s b e l i e v e d t o t a k e p l a c e i n two s t e p s . F i r s t , t h e h y d r o x y l g r o u p e x c h a n g e s p l a c e s w i t h one o f t h e r a d i c a l s j o i n e d t o t h e oxime o a r b o n and t h e r e s u l t i n g l a o t i m f o r m r e a r r a n g e s t o t h e l a o t a m f o r m ( 7 2 ) . T h e r e i s PCI R 2 C = NOH S> RC(OH) = NS * RCONHR c o n s i d e r a b l e e v i d e n c e t o s u p p o r t a t r a n s r e a r r a n g e m e n t r a t h e r t h a n a c i s one (42, 4 5 ) . The h y d r o x y l g r o u p on t h e n i t r o g e n e x c h a n g e s p l a o e s w i t h t h e r a c l l d a l a n t i t o i t on t h e oxime o a r b o n . Due t o t h e s t e r e o i s o m e r i s m o f t h e o x i m e s i t i s t o be e x p e c t e d t h a t 2 - a o e t o n a p h t h o n e oxime i t s e l f o o u l d f o r m two i s o m e r s when t h e oxime i s p r e p a r e d f r o m the ketone (61). The ratio of the two forms was found by- Baohman and Barton (2) to be 99:1 with the naphthyl group anti to the hydroxyl group being the predominant Isomer. The oxime was prepared from the ketone with the aid of hydroxylamine hydrochloride in pyridine. A Beckmann rearrangement was carried out on the oxime produced and the resulting amide hydro-lysed. Helative proportions of amines and acids present gave the proportion of the oximes originally pre sent. L i t t l e seems to have been done to investigate the isomerism of deoxybenzoin oxime. A Beckmann transformation done by Stephen and Bleloeh (64) using thionyl chloride gave for the rearranged product phenylaoetanilide. No mention was given that any N-phenylphenylaoetamide, which would be the other amide for the other oxime isomer, was found. Hence, the original oxime must have been syn-phenylbenzyl-ketone oxime and the reaction was as follows: 0 -10-(o) Cobalt Complexes of Oximes and other  Organic Bases Glyoximes and alkyl derivatives of glyoxlmes have been known for a long time to reaot with metallic salts including cobalt salts. For example, Tsohagaeff in 1906 (67) prepared the compound (H0N=CMeCMe=K0)2 " CoUHgBr from dimethyl-glyoxime. Many other salts of glyoximes have been prepared and considerable research has gone into these complexes in order to eluoidate their structure and also as agents in the deteotion and separation of metallic salts. An example of the use of glyoximes i s in the detection of niokel salts by the precipitation of the red preoipitate of niokel dimethyl-glyoxime (69). Hot only do the glyoximes form metallic salts but other compounds related to them do also. Oximes which form metallic complexes are the benzil monoxlme (26,44), monomethyl ether of benzil glyoxime (33), o-hydroxybenzaldoxime (9), oxime hydrazone of benzil (66), and £-£urfuraldoxime (11). It w i l l be noticed that in a l l cases the oxime i s adjacent to a functional group of some kind. Examples of where this was not the oase were offered by Hieber and Leutert (33) who successfully prepared both the nickel and the cobalt salts of acetaldehyde oxime, isobutyraldehyde oxime, -11-benzaldehyde oxime and cinnamaldehyde oxime. They found that four moles of oxime oomplexed with one mole of oobalt(IIJhalide. Less sucoess was shown with ketone oximes (34). Cobalt chloride did not react with acetone oxime in aqueous solutions although sus-pensions of cobalt chloride in inert solvents beoame an intense blue when acetone oxime was added. No compound was isolated. When antibenzaldehyde oxime was reacted with cobalt halides the oxime rearranged to the syn form showing that metal salts can have an influence on the geometrical isomerism of the oximes (33, 35). Up to date there i s no published knowledge of any complex which may form between dioobalt oota-carbonyl and oximes. However, reoent work shows that cobalt carbonyls reaot with N-bases leading in general to a definite compound of polar structure as follows (36): SJCofCOjJg + 12B * 2^oB 6][Co(G0) 4] 2 + 8C0 The bases used were oc and £ picoline, quinoline, pyrrolidine, morpholine, ethyleneimine, formamiae, diaoetyl-dianiline (a Sohiff base), diethylenetriamine and aromatic amines. Diacetyl-dianiline oomplexed with the oobalt oatalyst in the ratio of 1:2 rather t h a n 1:4 t o g i v e t h e f o l l o w i n g s t r u c t u r e : Go ye • H = G I H = C C 6 H 5 [Co ( C O L ] 4J 2 D i e t h y l e n e t r i a m i n e , on t h e o t h e r hand, complexed w i t h d i c o b a l t o o t a o a r b o n y l a o c o r d i n g t o t h e g e n e r a l i z e d s t r u c t u r e CoB 2(Co( C 0 ) 4 ] g . The above w o r k e r s a l s o p r e p a r e d c o b a l t c a r b o n y l c o m p l e x e s w i t h o x y g e n c o n t a i n i n g b a s e s ( 3 7 j . F o r example, a c e t o p h e n o n e r e a c t e d w i t h t h e m e t a l o a r b o n y l a c c o r d i n g t o t h e f o l l o w i n g e q u a t i o n : 3 [ C o ( C 0 ) 4 ] 2 - f , C 6 H 5 C 0 C H 3 . 2[Co(C 6 H e e o e H g ) ^ ] [ C o ( C 0 ) 4 ] 2 -f 8GG Benzophenone c o m p l e x e s t o g i v e t h e f o l l o w i n g s t r u c t u r e : 3 [ G O ( C 0 ) 4 ] 2 + £ C 6 H 5 C 0 C 6 H 5 * 2 [ G o ( C 6 H 5 C 0 e 6 H ^ ) J [ C 0 ( C G ) 4 ] 2 + 8GG -13-II. DISCUSSION (a) Beaotion of Carbon Monoxide and Hydrogen  with Deoxybenzoin Oxime When deoxybenzoin oxime was reaoted with carbon monoxide and hydrogen (98.5:1.5) in the presence of preformed dicobalt octaoarbonyl (71) at 3600 p.s.i. and 250°C. two crystalline products were obtained. The minor crystalline product (16$) was isolated by fractional crystallization of the products with ethanol. The crystalline product so obtained was purified by subsequent recrystallization from ethanol to give colorless needle like crystals, m. 202-203°C. On the basis of chemical and infrared analysis the product was concluded to be 3,4-dihydro-3-phenylisooarbqstyryl. The absorption peak at 3250 cm."L i s attributed to a bonded N-H stretch frequency for a N-monosubstituted amide (70) and the peak at 1670 cmT 1 i s attributed to a cyclic secondary amide (19). The major component was obtained by ohromato-graphing the remainder of the product on an alumina column and recrystaliizing the chromatographed product from ether-light petroleum ether. A mixed melting point of this sample with 3-benzylphthalimidine (26) gave no melting point depression and, henoe, the -14-product was concluded to be 3r.benzylphthalimidine. The overall equation for the reaction was as follows: (b) Reaotion of Carbon Monoxide and Hydrogen  with 2-Acetonaphthone Oxime When 2raoetonaphthone oxime was reacted with carbon monoxide and hydrogen in the presence of pre-formed dioobalt octaoarbonyl (71) at 4100 p.s.i. and 235°C. three crystalline products were obtained. The major product was the unexpected compound 2-(B-naphthyl)-4-methylbenzo [h]quinoline (A) present in 41$ yield. The second compound was the expected (46, 55) 3,-me.thylbenzo [f ] ph thai imi dine (B) present in 17$ yield. The third component (19$) appeared to be an unstable one whioh changed in a short time into the stable orystalline compound C the identity of o -15-whioh i s , at present, s t i l l unknown. (See p. 6 2 ) . The overall reaction was as follows: Compound A was a white crystalline compound and could be reprystallized from either ethanol or li g r o i n . It fluoresced with an intense blue light in the presence of ultraviolet radiation. Elemental analysis showed the empirical formula of product A to be Cg^H^N. Infrared spectra indicated the absence of the N-H bonding system and the presenoe of an imine linkage conjugated to an -1 aromatic system (Peak at 1623 cm. ) (28, 40, 70). Ultraviolet spectroscopy indicated that the compound had a phenanthradine type structure. When the ultra-violet spectrum of A was oompared with the ultraviolet spectra of phenanthrene and 2,4-dimethylbenzo[h]-quinoline (39) there was a peak at 3450 angstroms for -16-o. product A corresponding to peaks of 3460 A'' for o. phenanthrene and 3480 A for 2,4-dimethylbenzo[h] -o quinoline, and also a peak at 3220 A ; for product A o ' corresponding to a peak of 3220 A for phenanthrene (See figure 1; p.25a). Pyridine and quinoline derivatives form salts with strongly proton donating solvents (20) and product A formed brightly coloured salts with sul-phuric acid, formic acid and hydrochloric acid. When the hydrochloride salt was dissolved in aqueous ethanol and titrated against base a molecular weight olose to the theoretical value was obtained. Further verification of a benzoquinoline struoture was obtained beoause of the failure of the compound to reduce in the presence of either magnesium methoxide (73) or lithium aluminum hydride (8). An attempt at oxidation with potassium ferrocyaniae (58) failed to affect the molecule. The imine linkage showed great chemioal st a b i l i t y in that attempted degradation of the moleoule with fused sodium hydroxide (16) at 250°C. for six hours gave baok most of the un-changed produots thus confirming further that the imine linkage was part of a heterocyclic system. When the oompound was subjected to oxidation with chromic acid in acetic acid a bright orange -17-proauct was obtained in low yield whioh proved to have no aoidio function and slowly reddened in the presence of sunlight. Treatment with strong base gave rise to immediate blackening. This was the same kind of behaviour as that observed by Johnson and Matthews (39) in their attempt to oxidize 2,4-dimethyl-benzo[g]-quinoline with chromic aoid in acetic acid. They also obtained an orange product which they proved to be a quinone and this quinone reddened in the presence of sunlight and gave intractable decomposition products in the presence of strong base. On the basis of the results of the chromic acid oxidation of product A a quinone had been formed and, henoe, the original oom-pound was a oondensed aromatic or heterocyclic system. That the system was heterocyclic was indicated by the presence of nitrogen in the obtained oxidized produot. Any attempts to oxidize produot A with ehromic acid past the quinone stage met with failure, the failure being consistent with that of Seitz (62) who attempted to oxidize both 2-methylbenzo[g]quinoline and 2-methyl-benzofh] quinoline to pyridine carboxylic acid derivatives using chromic acid without success. An attempt was made to convert product A into the known oompound 2-(B-naphthyl) benzo [h] quinoline (15) by removal of the methyl group by a series of -18-oxidation steps as follows: The product was oxidized at the methyl position with the aid of selenium dioxide (14) to give 2-(^-naphthyl)-4-formylbenzo[h] quinoline ((?). This oxidized product was a bright yellow crystalline solid, m. 159-142.5°G. which by elemental analysis agreed in com-position to the postulated structure. It showed the behaviour of an aromatic aldehyde by rapidly reducing Tollen's reagent but not Jehling's and by showing a -1 strong infrared peak at 1700 om. , a characteristic frequency of aromatic aldehydes (37, 38). The oxime o derivative was prepared melting in the range 170-185 0. without attempt at purification. Oxidation of the obtained aldehyde was then -19-attempted with the use of an ammoniacal solution of silver oxide (14) to prepare the known compound 2-(p-naphthylj-4-carboxybenzo[h] quinoline (H), m. 227-228°C. (15). A oompound was obtained melting over the range 220-262°G. without purification. The 2-(§-naphthyl)-4-earboxybenzo[h] quinoline i s easily decarboxylated to 2-(B-naphthyl)-benzo[h]-quinoline (J), m. 117°0., by heating under vacuum. The compound obtained by oxidizing the aldehyde with selenium dioxide was heated under reflux in ethanol and chromatographed to give back some of the original aldehyde plus small amounts of white crystalline product, m. 35-50°G. It i s f e l t that the wanted heterocyclic oompound may be present but in an impure form. An attempt to oxidize the aldehyde with ni t r i o acid was unsuccessful leading only to intractable de-composition products. On the basis of a l l the above evidence i t was concluded that product A must be 2-(§-naphthyl)-4-methylbenzofh] quinoline and that i t was formed in-dependently of the presence of carbon monoxide as follows: -20-Since i t was postulated that this compound could be produced independently of the presence of carbon monoxide and probably even that of the dicobalt octacarbonyl i t s e l f , the two oompounds, 2-acetonaphthone and 2-acetonaphthone oxime were mixed in equimolar amounts in benzene and placed in an autoclave which was evacuated and the whole heated at 235°C. for 90 minutes. A colourless crystalline compound was isolated identical to product A on the basis that i t gave no melting point depression with product A and that i t gave an identical infrared spectrum. Hence, the oompound must be 2-(^-naphthyl)-4-methylbenzo[h]quinoline. On the basis of the above mechanism i t follows that 2-acetonaphthone must be produced. Attempts to find this ketone were unsuccessful. However, isolation of a ketone after the subjection of an oxime to the experimental conditions of carbonylation i s known. F o r example, J . O ' D o n n e l l h a s s u c c e s s f u l l y p r o v e d t h e p r e s e n c e o f benzophenone i n t h e r e a o t i o n m i x t u r e r e c o v e r e d a f t e r t h e c a r b o n y l a t i o n o f b e n z o -phenone oxime had t a k e n p l a c e ( 5 6 ) . T h a t no 2- a c e t o n a p h t h o n e was f o u n d c o u l d be e x p l a i n e d on t h e b a s i s t h a t u n d e r t h e c o n d i t i o n s o f r e a c t i o n t h e k e t o n e would be h i g h l y r e a c t i v e and would i m m e d i a t e l y c ondense w i t h 2 - a c e t o n a p h t h o n e oxime t o f o r m p r o d u c t A a s s o o n a s i t was f o r m e d . I t was c o n c l u d e d t h a t p r o d u c t B was t h e e x p e c t e d 3- m e t h y l b e n z o £ f J p h t h a l i m i d i n e . I n f r a r e d a n a l y s i s i n d i c a t e d t h e p r e s e n o e o f t h e c y c l i c amide, t h e c h a r a c t e r i s t i c p e a k f o r t h e N-H s t r e t o h i n g f r e q u e n c y f o r an amide a t 3280 cm. 1 ( 1 8 ) and t h e c h a r a c t e r i s t i c -1 p e a k f o r t h e c a r b o n y l o f t h e amide a t 1638 om. ( 1 9 ) b o t h b e i n g p r e s e n t . The a b s e n c e o f an u n s a t u r a t e d t r i c y c l i c s y s t e m was shown by t h e a b s e n c e o f a b s o r p t i o n o t i n t h e u l t r a v i o l e t above 3300 A ( 3 9 ) . E l e m e n t a l a n a l y s i s g i v e s an e m p i r i c a l f o r m u l a c o n s i s t e n t w i t h t h e p r o p o s e d s t r u c t u r e o f oompound B ( s e e p . 1 5 ) . T h a t t h e N-H bond was p r e s e n t was f u r t h e r sub-s t a n t i a t e d by t h e a o e t y l a t i o n o f p r o d u c t B. T h a t a c e t y l a t i o n was s u c c e s s f u l was a p p a r e n t due t o t h e d i s a p p e a r a n c e o f t h e i n f r a r e d p e a k f o r t h e N-H s t r e t c h i n g f r e q u e n c y and t h e s h i f t i n t h e c a r b o n y l f r e q u e n c y t o 1695 cm. 1 The a c e t y l a t e d p r o d u o t was n o t s u c c e s s f u l l y o r y s t a l l i z e d . -22-Work previously done further substantiates the proposed struoture. Sinoe acetophenone oxime formed 3-methylphthalimidine and benzophenone oxime formed 3-phenylphthalimidine in the presence of oarbon mon-oxide, hydrogen and dioobalt octaoarbonyl at elevated temperatures and pressures (55), and since Murahashi (46) prepared the linear isomer N-phenylbenzoff]-phthalimidine rather than the angular Isomer by carbonylating B-naphthaldehyde anil i t was concluded that product B was 3-methylbenzo[fjphthalimidine. A syrup F recovered from the reaction mixture appeared to have polarity properties very similar to B on the basis of similar solubility and chromato-graphic properties but i t was concluded that this produot was not the angular isomer of B due to the wide differences in carbonyl frequencies in the infra--1 red spectra of both B and F being at 1690 em. for F. When the original reaotion mixture was dis-solved in chloroform and the cobalt removed there resulted a dark green solution which upon standing overnight became brown and a white residue was deposited. This residue gave a positive ferrid ohloride test for a hydroxyl group and i t appeared to o slowly decompose even under vacuum, at 10 C., and in the absenoe of sunlight giving off a putrescent type of odour. Purification of the resultant degredative produot by chromatography gave rise to a white crystalline compound G which appeared to be stable. The crystalline product G gave no f e r r i c chloride test and so i t appeared that the hydroxyl funotion disappeared. Elemental analysis of produot C showed that an extra oarbon and an extra nitrogen had been added to the reactant. Infrared showed a strong oarbonyl peak at 1650 om.1 (19) and a strong N-H peak for an -1 N-substituted amide at 3230 cm. (18) showing that the oompound was l i k e l y a eyolic amide. Two strong peaks -1 -1 of equal intensity at 3435 om. and 3350 om. (42) also appeared which may be attributed to a hydroxyl or a N-H function or probably both. However, the application of the Hinsberg test (59) using benzene-sulfonyl chloride indicated the absence of either a primary or a secondary amine group. Furthermore, the oompound behaved indifferently In the presence of strongly proton donating solvents thus confirming the absence of an amino group. That no hydroxylamine group was present was verified on the basis that no result came from the attempt to oxidize C with mercuric oxide tSl). When a hydroxylamine compound i s oxidized with mercuric oxide a bright blue or green -24-solution appears due to the nitroso group and mercury metal i s also deposited. U l t r a v i o l e t analysis indioated that oompound C did not oontain an unsatur-ated t r i c y c l i c system as shown by oompound A. What has apparently happened i s that the re-action of the carbon monoxide on the oxime produced a mixture of compounds, one of which was a nitroso compound (blue-green i n colour) which was unstable and in a few days changed into colourless nitrogen r i o h amide C. No further attempt was made at t h i s stage to elucidate the i d e n t i t y of either the n i t r o s o oompound or the product C. - Iafrared spectra were taken on the remaining two components of the reaotion mixture, D and E, and i t was found that a carbonyl frequency of 1710 cm.1 (10) existed f o r E, but that D possessed no carbonyl frequenoy i n i t s infrared spectrum. The infrared also showed an absence of the N-H function i n both com-ponents. No further work was done on these two components beoause of the small amount of each present. Although oximes undergo a Beokmann rearrange-ment under the influence of an aoid oatalyst no evidenoe was brought forward that a Beckmann rearrange-ment had ocourred i n the reaction of 2-acetonaphthone oxime with oarbon monoxide and hydrogen i n the presence --25-o f d i o o b a l t o c t a c a r b o n y l . I t was n o t a s i m p l e m a t t e r t o i s o l a t e and p u r i f y t h e components o f t h e r e a c t i o n . Much p a i n s t a k i n g work was r e q u i r e d u s i n g b o t h column c h r o m a t o g r a p h y and f r a c t i o n a l c r y s t a l l i z a t i o n t o s e p a r a t e t h e m i x t u r e i n t o i t s components and t o p u r i f y t h e components. The p r e s e n o e o f one component a f f e c t e d b o t h t h e r e c r y s t a l l -i z i n g and c h r o m a t o g r a p h i c p r o p e r t i e s o f a n o t h e r compon-e n t m a k i n g s e p a r a t i o n and p u r i f i c a t i o n a m a j o r p r o b l e m . (See f i g . 3, p . 36 f o r t h e i n i t i a l s e p a r a t i o n o f t h e m i x t u r e i n t o i t s c o m p o n e n t s ) . I n t e r e s t i n g k i n e t i c r e s u l t s w e r e ; o b t a i n e d i n f o l l o w i n g t h e r e a c t i o n o f c a r b o n monoxide and h y d r o g e n w i t h 2 - a c e t o n a p h t h o n e oxime a t 1 9 5 ° C . A t t h i s t e m p e r a t u r e ( s e e f i g . 2, p . 25b ) t h e r e was a sudden r i s e i n p r e s s u r e c o r r e s p o n d i n g t o a mole and a h a l f o f g a s r e l e a s e d p e r mole o f s u b s t r a t e . I m m e d i a t e l y f o l l o w i n g t h i s r i s e t h e r e was a d r o p i n p r e s s u r e t a k i n g p l a c e a t a s l o w e r r a t e e q u a l i n m a g n i t u d e t o t h e r i s e i n p r e s s u r e . A f t e r t h e bomb had c o o l e d i t was n o t i o e d t h a t a d r o p i n p r e s s u r e had t a k e n p l a c e and b y s i m p l e c a l c u l a t i o n i t was f o u n d t h a t t h e d r o p i n p r e s s u r e was e q u a l i n m o l a r m a g n i t u d e t o t h e c h a n g e s i n p r e s s u r e t h a t t o o k p l a c e a t 1 9 5 ° G . "^ ro ro rt) CJ CVJ Wavelength In Angstroms Fig. I- Ultraviolet Absorption Spectra of: (J) 2-(f-Naphthyl)-4-methylben2oIh]quinolin e (2) 2,4-Dimethylbenzo[h] quinoline (39) (3) Phe nahthrene (39) 3 800 T Fig.2 -Plot of Pressure against Time for Reaction of 2-Acetonaphthone Oxime wrth Carbon Monoxide and Hydrogen at 195" -26-III. EXPERIMENTAL Instrumentation The high pressure reactions were carried out in an Aminioo Superpressure rocker reaction vessel having a void of 280 ml. The infrared spectra were obtained using a Perkin - Elmer model 21 Recording Infrared Spectrophotometer. The ultraviolet absorption spectra were obtained using a Cary Recording Quartz Spectro-photometer. The melting points were determined by means of a polarizing 100 Z microscope attached to an eleotrioally heated E. Leitz (Wetzlar) melting point block. Reagents Deoxybenzoin and 2-acetonaphthone of reagent grade purchased from Eastman Kodak Company were used. Hydroxylamine hydrochloride of reagent grade was used. Pure thiophene free benzene was prepared by the method of Pieser (25). The oarbon monoxide, obtained from The Matheson Co., East Rutherford, N. J., contained 1.5% hydrogen. The hydrogen used was obtained from The Canadian Liquid Air Co. Ltd. of Vancouver, B. C. in 99.7% purity. The aluminum oxide used for the chromatography was procured from the Bri t i s h Drug Houses (Canada) l t d . , Toronto 14. Chemloal analysis Microanalyses were done by Dr. A. Bernhardt, Mikroanalytisob.es Lab or at or ium, im Max-Planck-Inst i t at fur Kohlenforschung, Mulheim (Ruhr), Germany.. Both elemental analysis and molecular weight determinations (Rast Method) were done. Preparation of dloobalt ootaoarbonyl Dicobalt ootaoarbonyl was prepared by the method of Wender, Greenfield and Orohin (71). To a glass liner was added 18 g. cobalt(II)carbonate and 60 oo. dry thiophene free benzene. The li n e r was placed in an autoclave (effective void 280 cc.) and carbon monoxide was run in up to 1660-10 p. s . i . followed by hydrogen up to 3230*10 p. s . i . The auto-olave was heated and rocked for 60 minutes at 160°C. where a maximum pressure of 4820*10 p.s. i . was attained. Upon oooling to room temperature the pressure dropped to 2,350*10 p.s. i . or a differenoe in pressure of 880*10 p.s.i. The dark solution was stored at -12°G. in a stoppered container in order to hinder the slow decomposition of the catalyst. -28-(a) The Reaotion of Carbon Monoxide and Hydrogen  with Deoxybenzoin Oxime Preparation of deoxybenzoin oxime Into 50 ml. water was dissolved 15 g. (0.21 m.) hydroxylamine hydrochloride and the aqueous solution neutralized with 67 ml. 10$ aqueous sodium hydroxide. To the solution was added 30 g. (0.135 m. } deoxybenzoin and a homogeneous mixture obtained by the addition of 1050 ml. 95$ ethanol. The reaction vessel was allowed to stand at room temperature for six days after which the solution was diluted with 2000 ml. water to bring down a copious white precipitate. The precipitate was fil t e r e d and repeatedly washed with water. Recrystallization of the oxime from a water ethanol mixture gave 23.9 g. (75$) of the oxime having a melting point of 97-99°C. literature m.p. 98°C. (65). Reaotion of carbon monoxide with deoxybenzoin oxime Deoxybenzoin oxime (15.8 g.; 0.0635 m. ) was mixed with 23 ml.[0.02 m. Co g(C0) 8] catalyst liquor and the whole diluted up to 55 ml. with dry thiophene free benzene in a liner which in turn was placed into the autoclave. Carbon monoxide was run in up to 2000*10 p.s. i . and the whole was heated and rooked for -29-2 hours at 250°C. whereupon a pressure of 3600*10 p.s.i. was reached. After cooling to room temperature the pressure was 1800*10 p.s. i . or a drop of 200 p . s . i . had occurred. The product obtained was heated under reduced pressure at 55°C. in order to decompose the catalyst and to remove the solvent. Dissolving the syrup in chloroform and treating with norite to remove the residual cobalt l e f t after evaporating the chloroform 15.9 g. of syrup. Characterization of the products Recrystallization of the syrup with the use of 600 ml. anhydrous ethanol at 0°C. for 3 hours led to 2.5 g. of white needlelike crystals (16$). After two more crystallizations from ethanol the compound melted at 202-203° and was assumed to be 3,4-dihydro-3-phenylisooarbostyryl. Anal. Calod. for C 1 5H 1 2N0: C, 80.69; H, 5.87; 0, 7.17; N, 6.28. Pound: C, 80.32; H, 6.01; 0, 7.54; N, 6.19. Infrared ;spectrum of 3,4-dihydro-3-phenyliso-carbostyryl in Nujol (cmT1): 3250(W), 2920(S), 1670(3), 1600(1}, 1528(W), 1450(S), 1376(S), 1245(W), 1150(W), 1070(W), 1028(W), 755(M), 720(M), 695(M). After removal of the ethanol from the f i l t r a t e , -30-the syrup was triturated with 500 ml. ether to yield a crystalline solid (0.2 g.) which was removed by f i l t r a t i o n . leerystallization of this product from methanol gave a compound melting sharply at 286°C. Beoause of the low yield of product obtained no further work was done on i t . After removal of the ether by evaporation the syrup was subjected to column chromatography using an alumina oolumn 100 mm. x 38 mm. diameter. A portion of the syrup (0.85 g.) was dissolved in 5 ml. benzene and the solution eluted on the column with benzene. A trace of substance came down and this was disoarded. Further elution using benzene-ethanol 99:1 v:v brought down the bulk of the oompound in a pale yellow form whioh when recrystallized from benzene-petroleum ether caused removal of most of the colouration. A further recrystallization from alcohol-water mixture gave a white crystalline oompound melting at 135-136°C. A mixed melting point determination with 3-benzyl-phthalimidine gave no depression (26). -31-( b) The Reaotion of Carbon Monoxide and Hydrogen  with 2-Aoetonaphthone Oxime Preparation of 2-aoetonaphthone oxime Into 150 ml. water was dissolved 40 g. (0.567 m. ) hydroxylamine hydrochloride and the aqueous solution neutralized with 150 ml. 10$ aqueous sodium hydroxide. To the solution was added 60 g. (0.553 m. ) 2-acetonaphthone and a homogeneous mixture obtained by the addition of 950 ml. 95$ ethanol. The reaction vessel was allowed to stand at room temperature resulting in the formation of a copious white precipitate in less than three hours. After 15 hours the precipitate was f i l t e r e d , washed repeatedly with water and recrystallized twice from a water-ethanol mixture to yield 48 g. (73.5$) oxime after drying over phosphorus pentoxide, m. 149-150°C. Literature m.p. 145°C. (3). Reaction of oarbon monoxide with 2-acetonaphthone oxime 2-Aoetonaphthone oxime (15.0 g.; 0.08 m. ) and 20 ml. catalyst liquor [0.025 moles Co 2(C0 ) e J l n benzene were added to 40 ml. thiophene free benzene in a liner which was placed in an autoclave. Carbon monoxide was run in up to 2140*10 p.s. i . and the system rocked and heated at 21G-235°C. for 50 minutes. After the vessel had cooled the pressure was 1950*10 p.s.i. or a drop of -22-190 p . s . i . (0.09 m o l e s ) had o c c u r r e d . The b e n z e n e s o l u t i o n was h e a t e d a t 7 G - 8 0 ° C . t o decompose t h e c a t a l y s t and t h e s o l v e n t was t h e n removed b y e v a p o r a t i o n . The r e s i d u a l wax was d i s s o l v e d i n c h l o r o f o r m and t r e a t e d w i t h n o r i t e t o remove t h e c o b a l t a f t e r w h i c h a d a r k g r e e n s o l u t i o n was o b t a i n e d . Removal o f t h e c h l o r o -f o r m gave 14.1 g. o f brown wax. The above r e a c t i o n was r e p e a t e d and p r e s s u r e r e a d i n g s were r e o o r d e d and p l o t t e d a g a i n s t t i m e a t c o n s t a n t t e m p e r a t u r e ( s e e f i g . 2, p . 2 5 b ) . The a u t o -c l a v e w i t h c o n t e n t s were h e a t e d up t o 1 9 5 ° C . where a r a p i d p r e s s u r e change t o o k p l a c e . The r e a d i n g s a t 1 9 5 ° C . were a s f o l l o w s : Time T e m p e r a t u r e P r e s s u r e 0 m i n u t e s 1 9 0 ° C . 2470 p . s . i . 1 1 9 5 ° 2720 2 2 0 0 ° 5620 4 1 9 8 ° 3650 5 2 0 0 ° 3550 7 1 9 5 ° 3510 10 1 9 2 ° 3470 11 1 9 0 ° 3460 A f t e r 20 m i n u t e s more h e a t i n g a t 195°e. t h e -33-autoolave was allowed to cool. A pressure drop of 190 p.s. i . (0.09 moles) was obtained and 13.8 g. of product removed. Separation of the Products After removal of the cobalt from the reaotion product obtained at 210-235°C. the product was dissolved in ohloroform to give a dark green solution which when allowed to stand overnight at -15°C. turned brown and a white residue C had formed yield 1.6 g., m. 170-205°Ci, insoluble in benzene, soluble in ethanol. A portion of the orystalline fraction (0.35 g.) dissolved in 1 ml. pyridine was added to the top of an alumina column (90 mm. x 28 mm. diameter) and developed as follows: Effluent fraotions (in m i l l i l i t r e s ) Wt. of Fractions (in grams) 700 ml. benzene 400 ml. 9:1 v:v benzene-ethanol 600 ml. ethanol Trace of brown o i l 0.25 g. white orystalline oompound C Trace of brown wax The orystalline produot C was further purified by recrystallization from 3-pentanone to give white needle like crystals, m. 204.5-205.5°G. -34-After removal of the product C from the ohloro-form solution the ohloroform was removed by evaporation and a portion of the residue (7.8 g.) was dissolved in 15 ml. benzene and added to the top of an alumina column (150 mm. x 70 mm. diameter) and developed as follows: Effluent Fractions (in m i l l i l i t r e s ) Wt. of Efaotions (in grams) 80 ml. Benzene-light pet.ether (1:1 v:vi 1000 ml. Benzene-light pet.ether (1:1 v:vi 1000 ml. Benzene 1700 ml. Benzene - t^BuOH 900 ml. Benzene-ethanol (1:1 v:v) 0.16 g. pale yellow sweet smelling syrup D 3.15 g. white crystalline compound A 0.32 g. dark brown wax E 2.23 g. dark brown wax -mixture ( i i i ) Pig. 3 1.32 g. pale brown amorphous solid G Total recovery was 7.2 g. or 92$. It was easy to follow the zones as they were either highly fluorescent in the presence of ultraviolet light or were coloured a yellowish brown or else had both characteristics. The fourth zone from the oolumn (mixture i i i , see f i g . 3, p.36 ) was fractionally crystallized from benzene to yield the white orystalline oompound B. -35-The remaining f i l t r a t e (mixture iv, f i g . 2) was re-ohromatographed by dissolving 1.64 g. in 7 ml. benzene, added to the top of an alumina column (140 mm. x 52 mm. diameter) and developed as follows: Effluent Fractions (in m i l l i l i t r e s ) Fractions and weight (in grams) 150 ml. benzene-ether (7:2 vv) 0.10 g. sweet smelling o i l 1000 ml. benzene-ether (7:2 W ) -900 ml. benzene-ether (7:3 vv) 0.94 g- brown solid amorphous B 1000 ml. benzene-ether (7:3 vv) 0.08 g- brown solid amorphous F 1000 ml. benzene-ether-ethanol (69:30:1 vvv) 0.40 g- brown solid amorphous F 500 ml. ethanol 0.08 g- brown solid amorphous Again, as above, the zones could be followed by ultraviolet light. Total yield was 1.60 g. or 97$. Characterization of 2-(g-naphthyl)-4-methylbenzorhJ-quinoline (Compound A) 2-((3-naphthyl )-4-methylbenzo[h] quinoline oame down as the second chromatographic zone (41$) on an alumina column and was purified further by recrystall-ization twice from absolute ethanol to give oolourless -36-F i g . 3 - S e p a r a t i o n o f t h e.2 - A c e t o n a p h t h o n e Oxime R e a c t i o n P r o d u c t s M i x t u r e ( i ) and c a t a l y s t i n benzene r M i x t u r e ( i ) i n c h l o r o f o r m P r a o t i o n a l c r y s t a l l i z a t i o n D e c o m p o s i t i o n o f c a t a l y s t and r e m o v a l by a i d o f c h l o r o f o r m \ Co 1 M i x t u r e ( i i ) C h r o m a t o g r a p h y Zone 5 C-r c r y s t a l l i n e C - o r y s t a l l i n e (7%) (11%) Zone 4 Zone 3 E - s y r u p ( 4 $ ) Zone £ Zone 1 D-syrup (2%) A - e r y s t a l l i n e (41%) M i x t u r e ( H i ) F r a c t i o n a l C r y s t a l l i z -a t i o n - benzene M i x t u r e ( i v ) 1 1 R e o h r o m a t o g r a p h y 1 1 . 1 1 B < - c r y s t a l l i n e B- impure (3%) (14%) P - s y r u p (5fo) -37-needle l i k e c r y s t a l s , m. 123-124°C. R e c r y s t a l l -i z a t i o n oould also be done with l i g r o i n giving higher y i e l d s than with ethanol but with a lower degree of purit y . The oompound was soluble i n acetone, benzene and chloroform. Anal, calcd. f o r C 2 4H 1 7U: C, 90.26; H, 5.22; U, 4.39. Mol. wt. 207.4. Pound: C, 89.63; H, 5.36; N, 4.55. Mol. wt. (East) 288. Infrared spectrum of A i n KBr (cm. 1): 2080-3060(W), 2935{W), 2860-2890(W), 1623(W), 1595(S), 15561M), 1548(W), 1520-1505(W), 1503(W), 1460(W), 1445(W), 1410(W), 1388(W), 1279(W), 1246(W), 1197(W), 1150(W), 1138(W), 1125(W), 1097(f), 1035(W), 1025(W), 962(W), 922(W), 904(W), 888(W), 867(S), 829(S), 801(S) f 776(W), 763(S), 756(S), 741(W), 731(W), 683(W), 645(W). U l t r a v i o l e t spectrum of A i n 95% ethanol; angstroms (log molar ex t i n c t i o n c o e f f i c i e n t ): 3620 (4.14); 5450 (4.16); 3220 (4.56); 3150 (4.31); 2870 (4.30); 2780 (4.50); 2430 (4.60); 2120 (4.44). Attempted reduction of 2-(g-naphthvl)-4-methylbenzo[hj-quinoline with l i t h i u m aluminum hydride (8) To a solution of 5 ml. p u r i f i e d and dried d i e t h y l ether (22) and 0.05 g. l i t h i u m aluminum hydride was added dropwise with considerable s t i r r i n g a solution of 0.2 g. produot A i n 5 ml. p u r i f i e d and dried ether. - 2 8 -After 2 0 minutes of refluxing the reaction vessel was cooled in ice water and water was added slowly to destroy any complex and any unreaoted lithium aluminum hydride. Ether was added to compensate for any ether lost in the refluxing and was followed by the addition of 3 ml. concentrated sodium potassium tartrate and 2 ml. lOfo sodium hydroxide to dissolve the white precipitate. The ether layer was separated from the aqueous layer, dried over calcium chloride, and the ether removed by evaporation to leave behind a white residue which when reorystallized from ethanol gave white needle like crystals m.p. 1 2 2 - 1 2 2 ° C . A mixed melting point with A gave no depression. Attempted reduction of 2-(g-naphthyl)-4-methylbenzo-[h]quinoline with magnesium methoxide ( 7 2 ) To 4 0 ml. of almost ( 2 drops water added) anhydrous methanol was added 0 . 1 1 2 g. product A. About 0 . 8 g. freshly polished magnesium metal was added and by heating the metal dissolved. After removal of the solvent by evaporation there was l e f t a greenish yellow residue which was treated with ice water and 20% acetic acid to dissolve most of the solid and leave behind a bright yellow residue. Recrystallization from ethanol gave white crystals m.p. 1 1 9 - 1 1 2 .5°C. which gave a: mixed melting point of 1 1 9 i r - 1 2 2 . 5 C. with product A. Oxidation of 2-(8-Naphthyl)-4-methylbenzo[h]quinoliae (Compound A) by ohromio acid (25) To a solution of 0.1152 g. product A dissolved in 20 ml. acetic acid was added 0.5 ml. chromic acid -acetic acid - water solution (4:2:2 by weight) drop by drop. Precipitation took place and 21 drops con-centrated sulphuric acid at 60^3. were required to dissolve the precipitate. The green solution was filtered leaving behind 0.0117 g. of orange precipitate (10$ yield). The f i l t r a t e was made weakly acid with 10$ aqueous sodium hydroxide and concentrated cupric acetate was added. No preoipitation took place. The orange precipitate produced did not re-orystallize from ethanol and did not dissolve in lig r o i n . It started to melt at 125°C. and crystals persisted beyond 260°C. An aqueous alcoholic solution proved neutral to indicator paper and no effervescence was observed when the product was treated with aqueous sodium bioarbonate. Treatment of a small amount of the recovered substance with concentrated aqueous sodium hydroxide caused blackening and tar formation. A nitrogen determination by the sodium fusion method (50) gave a positive test for nitrogen. The product appeared to slowly polymerize in the presence of air. Attempted Oxidation of 2-(6-naphthyl)-4-methylbenzo-[hl^guinoline with potassium ferrocyanide (57) Into 120 ml. water were added 0.26 g. product A -40-25 g. potassium ferrooyanide and 4.3 g. potassium hydroxide. The mixture was refluxed with Vigorous stirring at 60°C. for 24 hours. At the end of this time 8 g. potassium ferrooyanide and 1.4 g. potassium hydroxide were added and refluxing was continued. At the end of 48 hours 4 g. potassium ferrooyanide and 0.7 g. potassium hydroxide were added and refluxing was continued until a total of 67 hours had passed. The original product was recovered. Oxidation of 2--naphthyl )-4-methylbenzo fbj quinoline  (Compound A) to yield 2-(ff-naphthyl )-4-formylbenzo-[h]quinoline (Compound S) To a semimioro three necked flask equipped with a stirrer was added 0.2553 g. product A. The flask was heated to 180°C. with stirring and at this temperature 0.0904 g. of pulverized selenium dioxide was slowly o added and the mixture heated for 15 minutes at 180-200 C. The reddish brown viscous syrup produced was repeatedly extracted with diethyl ether to form a bright yellow-orange solution. The ethereal solution was dried over calcium chloride and the ether evaporated off to yield 0.2166 g. of bright yellow produot. Purification of the oxidized produot The product was dissolved in 3 ml. benzene and placed on a 150 mm. x 35 mm. diameter alumina column -41-prewashed with benzene-petroleum ether (b.p. 30-60 C.) 1:3 v:v mixture. The separation was as follows: Effluent Fractions (in m i l l i l i t r e s ) Fraotions and Weight (in grams) 1. 300 ml. CcHg- pet. ether (1:3 v:v) 0.0555 S« colourless crystals 2. 1250 ml. C 6 H 6 - pet. ether (1:3 v:v) 0.0102 g» brown crystals 3. 2300 ml. C 6 H 6 - pet. ether (1:3 v:v) 0.0476 g- bright yellow crystals G 4. 850 ml. C 6 H 6 - pet. ether (1:1 v:v) 0.0288 g» orange tarry residue 5. 500 ml. Ethanol 0.0661 brown residue Total recovery was 0.2022 g. or 93.4$. Zone 1 proved to be the original product A by mixed melting point. Zones 2, 4 or 5 were not worked with. Characterization of 2-(j?-naphthyl )-4-f ormvlbenzo[hj -quinoline (Compound G) (Zone 3) The produot was recrystallized from l i g r o i n (b.p. 100-120°C.) to give bright yellow crystals* m.p. 139-142.5°G. Anal, oalcd. for C24I15ITO: C, 86.6; H, 4.51; H, 4.20; 0, 4.80; Mol. wt. 333.4. Found: C, 86.26; H, 4.68; N, 4.18; 0, 4.7. -42-I n f r a r e d s p e c t r u m o f G w i t h K B r (om. ): 2 9 4 0 ( S ) , 2870{M), 1 7 0 0 ( S ) , 1685 ( W ) , 1655(W), 1647(W), 1585(W), 1560(W), 1547(W), 1525(W), 1510(W), 1460(W), 1S65(W), 1S25(W), 1212(W), 1197(W), 1157(W), 1125(W), 1122(W), 1090(W), 1025(W), 928(W), 882(M), 852(M), 827(W), 815(M), 798(W), 7 4 5 ( S ) , 712(W), 707(W). The y e l l o w p r o d u c t gave a b r i g h t y e l l o w s o l u t i o n h a v i n g a v i v i d g r e e n i s h f l u o r e s o e n c e . A d d i t i o n o f c o n o e n t r a t e d a l c o h o l i c p o t a s s i u m h y d r o x i d e o a u s e d t h e c o l o u r t o d i s a p p e a r . A o i d i f i c a t i o n o r n e u t r a l -i z a t i o n o f t h e b a s i c s o l u t i o n w i t h g l a c i a l a c e t i c a c i d l e d t o r e s t o r a t i o n o f t h e y e l l o w c o l o u r a t i o n . The compound gave a f a i r l y r a p i d T o l l e n ' s t e s t and a n e g a t i v e t e s t w i t h P e h l i n g ' s s o l u t i o n . T r e a t m e n t w i t h h y d r o x y l a m i n e h y d r o c h l o r i d e oaused i m m e d i a t e d i s a p p e a r -ance o f t h e y e l l o w c o l o u r a t i o n and t h e f o r m a t i o n o f a o o l o u r l e s s c r y s t a l l i n e oxime m e l t i n g i n t h e r a n g e 1 7 0 - 1 8 5 ° C . w i t h o u t r e c r y s t a l l i z a t i o n . O x i d a t i o n o f 2 - ( ^ - n a p h t h y i J - 4 - f o r m y l b e n z o [ h ] q u i n o l i n e  (compound G) w i t h s i l v e r o x i d e t o y i e l d 2-((3-n a p h t h y l - 4 - o a r b o x y b e n z o [ h 3 q u i n o l i n e (oompound H) ( 1 4 ) To 0.0076 g . o f 2 - ( ^ - n a p h t h y l ) ^ 4 - f o r m y l b e n z o -f h ] q u i n o l i n e d i s s o l v e d i n 10 m l . e t h a n o l was added d r o p b y d r o p a n a m m o n i a c i a l e t h a n o l i o s o l u t i o n o f s i l v e r o x i d e (0.022 g. AggO). R e f l u x i n g was o a r r i e d -43-out for three hours and the solution allowed to stand overnight. After making the solution basic with potassium hydroxide in alcohol the coagulated silver •oxide ' was filtered to give a pale yellow solution. A silver mirror had formed in the flask. The solution was neutralized with glacial acetic acid, evaporated to dryness and the residue extracted with chloroform. Recrystallization of the residue from isoamyl aloohol was unsuccessful but after removal of the solvent a crystalline residue resulted whioh melted in the range 220-862°C. Attempted decarboxylation of 2-(fl-naphthyl)-4-oarboxy-benzoLhJ quinoline The 2-(^-naphthyl)-4-carboxybenzo[h]quinoline was reorystallized from ethanol to give a crystalline product melting in the range 125-140°C. (mainly the unoxidized aldehyde). The produot after being refluxed in ethanol for 6 hours was freed of solvent and the residue dissolved in 1 ml. benzene and chromatographed on a 110 mm. x 10 mm. diameter alumina column pre-washed with 10 ml. benzene-ligroin (b.p. 30-60°C.) 1:3 v:v mixture. The separation was as follows: -44-Effluent Fractions (in m i l l i l l t r e s ) Fraotions collected 1. 60 ml. 2:1 light pet. ether-benzene 2. 390 ml. 2:1 light pet. ether-benzene 220 ml. benzene 2. 120 ml. ethanol pale brown o i l 1 mg. greenish yellow orystals 2 mg. brown wax 1 mg. The contents of zone 2 proved to be unreacted aldehyde. Attempts to crystallize zone 2 from ethanol were unsuccessful. The product of zone 1 was recrystallized from ethanol to give a mass of white flu f f y crystals. This product appeared greasy at room temperature and melted over a range of 25-50°G. The amount of substance isolated was less than a milligram and was not worked with further. Sodium Hydroxide fusion of 2-(g-naphthyl)-4-methyl-benzorh] quinoline (A) (16) To a thiok walled glass test tube was added a mixture of 0.2 g. produot A and 2 g. powdered sodium hydroxide. Another 1 g. powdered sodium hydroxide was added on top. A well containing a few drops of water was suspended above the reaoting mixture in order to absorb any ammonia which might be produced. The test tube and contents were heated for six hours in a sand bath at 250°C, oooled, and the contents -45-dissolved in a minimum amount of water and f i l t e r e d . Neutralization of the solution with 6N sulphuric acid gave a oopious'white gelatinous precipitate which was repeatedly extracted with ethanol. The remaining residue proved to be inorganic by the flame test. The aqueous solution was evaporated down and also extracted with ethanol. The original residue l e f t after dissolving the solid basic mixture in water was reorystallized to give back product A in 60$ yield. The ethanolic extraot gave a small amount of intract-able decomposition product not worked on. Behaviour of strongly proton donating solvents with 2-(^-naphthyl)-4-methylbenzo[h]quinoline (Oompound A) Compound A reacted with concentrated hydro-chloric acid to give a bright yellow insoluble salt. With oonoentrated sulphuric acid a bright yellow oolouration was imparted to the product and i t slowly dissolved. Upon heating the solution the yellow colouration turned to pink. Dilution of the acid with water resulted in the loss of the pink colouration and a greenish-yellow precipitate formed. With formic acid Immediate dissolving took place to give a yellow solution. Dilution of this solution with diethyl ether resulted in the loss of colouration and in the precipitation of a colourless compound. -46-R e a o t i o n o f 2 - ( f f - n a p h t h y l ) - 4 - m e t h y l b e n z o [h] q u i n o l i n e w i t h d r y h y d r o g e n c h l o r i d e t o y i e l d t h e h y d r o -c h l o r i d e s a l t The h y d r o c h l o r i d e s a l t o f p r o d u o t A was made by p a s s i n g d r y h y d r o g e n c h l o r i d e t h r o u g h a d r y e t h e r e a l s o l u t i o n o f p r o d u c t A t o g i v e a n Immediate y e l l o w c o p i o u s p r e c i p i t a t e w h i c h was f i l t e r e d , washed r e p e a t e d l y w i t h d r y e t h e r and d r i e d i n a vacuum d e s i c c a t o r o v e r p h o s p h o r u s p e n t o x i d e and p o t a s s i u m h y d r o x i d e f o r 48 h o u r s whereupon a b r i g h t y e l l o w s a l t was c o l l e c t e d i n h i g h y i e l d h a v i n g a deep g r e e n i s h f l u o r e s c e n c e . H e a t i n g t h e s a l t a t 9 0 - 1 0 0 ° G . r e l e a s e d t h e h y d r o g e n o h l o r i d e and t h e o r i g i n a l p r o d u c t A was r e c o v e r e d . U l t r a v i o l e t s p e c t r u m o f t h e HG1 s a l t o f A i n 95% e t h a n o l ; a n g s t r o m s ( l o g m o l a r e x t i n c t i o n c o -e f f i c i e n t ): 3920 ( 4 . 2 3 ) , 3660 ( 4 . 1 4 ) , 3460 ( 4 . 0 4 ) , 3160 ( 4 . 4 7 ) , 2870 ( 4 . 4 9 ) . Of t h e d r i e d p r o d u c t a known w e i g h t was d i s s o l v e d i n 90% e t h a n o l and a l i q u o t p o r t i o n s were t i t r a t e d a g a i n s t a s t a n d a r d , s o l u t i o n o f p o t a s s i u m h y d r o x i d e i n 90% e t h a n o l u s i n g p h e n o l p h t h a l e i n a s i n d i o a t o r . The m o l e c u l a r w e i g h t o f A was f o u n d t o be 314.3; T h e o r e t i c a l , 307.4. -47-Reaction of 2-(g-naphthvl)-4-methylbenzo[hjquinoline  with methyl iodide to yield the methiodide salt The methiodide salt was prepared (24) by dissolving 0.082 g. produot A in 3 ml. methyl iodide and adding to a thick walled tube which was sealed. It was heated for 170 hours at 100°C., cooled, wrapped in metal f o i l , and kept under refrigeration for several days. Black orystals formed which were removed from the tube and washed with dry diethyl ether (40$ yield), m. 182-184°G. After evaporation of the methyl iodide solvent there remained pale yellow crystals which after recrystallization from ethanol proved by mixed melting point to be the original product A (0.049 g.). Anal, oalod. for G 2 3 H 1 8 N I : G, 65.7; H, 3.92; JSt 3.24; I, 29.5. Pound: G, 57.12; H, 5.98; N, 3.26; I, 31.26. Reaotion of 2-(ff-naphthyl)-4-methylbenzo(h] quinoline with pidrio aoid to yield the picrate derivative (60) To 3 ml. ethanol was added 0.041 g. picric acid and the pic r i c acid solution was in turn added to 0.052 g. compound A dissolved in 3 ml. ethanol. A copious yellow precipitate formed immediately which was dissolved by diluting the mixture up to 250 oo. with 95$ ethanol and refluxing. Refluxing was carried on for five hours after which the ethanolic solution was allowed to stand and cool. The crystallized product -48-was filtered and recrystallized from 95$ ethanol to give G.068 g. (75$) bright yellow crystals, m. 223-236°G. Anal, calcd. for C H N 0 ; G, 66.0; 30 20 4 7 H, 3.67; BT, 10.22; 0, 20.04; Mol. wt. 549.4. Pound: G, 63.63; H, 3,59; N, 9.99. Attempted reaction of 2-(g-naphthyl)-4-methylbenzo[h]-quinoline with maleic anhydride (39) To 2 ml. benzene was added 0.23 g. freshly d i s t i l l e d maleic anhydride and 0.0792 g. product A. The solution was refluxed under anhydrous conditions for eight hours. When the reaction had copied more benzene was added and dry hydrogen chloride passed through. A bright yellow precipitate formed which was separated from the solvent and treated with sodium acetate in boiling acetone to decompose the salt. After f i l t e r i n g off the inorganio salt and evaporating down the solution a yellow o i l formed which solidified on cooling, m. 117-124GC. A recrystallization from ethanol yielded a compound m. 122-125°C. A mixed melting point with product A was at 121-124°G. Characterization of 3-methylbenzo[fjphthalimidlne (oompound B i ) (portion collected from chromatography  of mixture iv) Yield 14$. This fraotion was triturated with -49-s u o c e s s i V e p o r t i o n s o f l i g r o i n , b . p . 6 5 - 7 5 ° C . t o l e a v e b e h i n d a t r a o e o f d a r k brown r e s i n o u s m a t e r i a l w h i c h was d i s o a r d e d . The p a l e brown s y r u p r e c o v e r e d was v e r y s o l u b l e i n m e t h a n o l , 3 - p e n t a n o n e , i s o a m y l a l o o h o l , a c e t i c a c i d , c h l o r o f o r m and b e n z e n e . A t t e m p t s a t r e o r y s t a l l i z a t i o n f r o m p e t r o l e u m e t h e r - b e n z e n e o r p e t r o l e u m e t h e r - c h l o r o f o r m r e s u l t e d o n l y i n o i l i n g o u t . I n f r a r e d s p e c t r a u s i n g a GHClg d e p o s i t e d f i l m on N a C l d i s o (omT1): 3 3 1 0 ( H ) , 3050(W), 3005(W), 2960(W), 2905(W), 1 6 2 8 ( S ) , 1598(W), 1 5 6 0 ( 3 ) , 1608 (H) f 1452(W), 1375(W), 1272(W), 1245 W , 1 2 1 7 ( S ) , 1177(W), 1 1 2 7 ( f ) , 1017(W), 950(W), 890(W), 855(M), 815(M), 7 5 2 ( S ) , 665(W). An a o e t y l a t i p n was c a r r i e d o u t on B a s f o l l o w s : To 0.023 g. B i n 0.70 m l . d r y a c e t i c a n h y d r i d e was a d d e d 0.037 g. f u s e d s o d i u m a c e t a t e and t h e m i x t u r e was a l l o w e d t o r e f l u x f o r s i x h o u r s . A f t e r c o o l i n g t h e c o n t e n t s were p o u r e d i n t o i c e c o l d w a t e r and v i g o r o u s l y a g i t a t e d . The w a t e r was d e c a n t e d and t h e g r e a s y brown r e s i d u e d i s s o l v e d i n d i e t h y l e t h e r and t h e e t h e r e a l s o l u t i o n washed w i t h w a t e r . The e t h e r s o l u t i o n was d r i e d o v e r a n h y d r o u s c a l c i u m c h l o r i d e and t h e e t h e r removed b y e v a p o r a t i o n t o r e c o v e r 0.0125 g. o f p r o d u c t w h i c h r e c r y s t a l l i z e d f r o m m e t h a n o l g i v i n g f a i n t w h i t e c r y s t a l s i n low y i e l d w h i c h p r e s u m a b l y -50-were the acetate derivative as shown by infrared analysis. Infrared spectra of acetylated B using a CH013 deposited film on HaCl disc (cmT1): 3350(W), 3060(W), 3020(W), 2945(M), 2910(M), 2840(W), 1695(S), 1665(M), 1597(W), 1534{W), 1508(W), 1435(W), 1377(M), 1368(M), 1270(M), 1230(S), 1180(W), 1127(W), 950(W), 890(W), 855(M), 818(M), 750(S), 663(W). Characterization of 3-methylbenzoff]phthalimidine  (compound B) (portion collected from fractional  crystallization of mixture i i i . f i g . 4) Yield dfo. This orystalline component was recrystallized from a benzene-ethanol mixture and then from chloroform to give white flake like crystals, m. 218-239°C. Anal, oalod. for C^B^NO: C, 78.8; H, 5.65; N, 7.10. Mol. wt., 197.3. Found: G, 77.90; H, 6.23; U, 6.97. Infrared spectrum in KBr (cmT1): 3280(M), 2940(W), 1638(S), 1598(H), 1585(M), 1577(W), 1550(W), 1525(1), 1460(M), 1388(W), 1345(M), 1300(W), 1285(1), 1193(W), 1145(H), 1100(W), 907(W), 870(M), 835(S), 760(S), 687(W). -51-U l t r a v i o l e t s p e o t r u m o f B i n 95% e t h a n o l ; a n g s t r o m s ( l o g m o l a r e x t i n c t i o n c o e f f i c i e n t ): 35 0 0 ( S h ) ( 2 . 5 9 8 J , 3205 ( 3 . 1 0 0 ) , 3160 ( 3 . 0 6 4 ) , 2 9 2 5 ( S h ) ( 3 . 6 9 5 ) , 2825 ( 3 . 7 9 0 ) , 2 7 2 0 ( S h ) ( 2 . 7 5 0 ) , 2270 ( 4 . 6 0 4 ) , 2280 ( 4 . 5 9 2 ) . C h a r a c t e r i z a t i o n o f C ( p o r t i o n c o l l e c t e d f r o m  c h r o m a t o g r a p h y o f m i x t u r e i i . f i g . 4 ) Y i e l d 12$. The f r a c t i o n r e c o v e r e d was a d a r k brown r e s i n o u s wax. I t was d i s s o l v e d i n b e n z e n e (1.22 g . i n 2 ml.) and added t o an a l u m i n a column > (120 mm. x 52 mm. d i a m e t e r ) and e l u t e d a s f o l l o w s : E f f l u e n t F r a c t i o n s ( i n m i l l i l i t r e s ) F r a c t i o n s and W e i g h t ( i n grams) 1700 m l . C 6 H g : t-BuOH (98:2 v : v ) 200 m l . C AH f i: EtOH b b ( l : l v : v ) 0.22 g . d a r k brown r e s i d u e 0.82 g. p a l e brown r e s i d u e C The f i r s t f r a c t i o n was n o t worked w i t h f u r t h e r . The seoond f r a c t i o n ( 1 1 % o f t h e t o t a l ) was v e r y s o l u b l e i n 2 - p e n t a n o n e , i s o a m y l a l c o h o l and g l a c i a l a c e t i c a c i d . R e c r y s t a l l i z a t i o n w a s a c c o m p l i s h e d f r o m a c h l o r o f o r m - p e t r o l e u m e t h e r s o l v e n t and t h e n f r o m o h l o r o f o r m t o g i v e a w h i t e c r y s t a l l i n e p r o d u o t , m. 2 0 1 - 2 0 7 ° C . -52-Anal. calcd. for ^ i^lZ^Z0*' c» 70.1; H, 6.00; U, 14.00; 0, 8.00. Found: C, 71.35; H, 6.02; 14.12; 0, 8.02. -1 Infrared spectrum in KBr I cm. ): 5300(S), 3210(M), 3040(W), 2950(W), 2910(W), 2850(W), 1660(S), 1607(S), 1575(1), 1565(W), 1475(W), 1395(H), 1317(W), 1290(W), 1195(W), 1160(H), 1143(W), 985(W), 970(W), 925(W), 912(W), 893(W), 875(H), 840(S), 793(W), 767(S), 678(W). Sublimation of C at 175°G. at about 0.05 mm. Hg. gave a white crystalline product, m. 35-60°C. The sublimed product failed to give a derivative with 2,4-dinitrophenylhydrazine. Characterization of 0 (portion collected from fractional crystallization of mixture i . f ig. 3) Yield 7%. After three reprystallizations from 3-pentanone the compound melted at 204-205.5°C. It was soluble in alcohol, insoluble in benzene, diethyl ether or ligroin and oould be recrystallized from chloroform. Anal, oalod. for OigHj^NgO: G, 72.8; H, 6.58; N , 13.1; 0, 7.46; Mol. wt,, 214.3. Found: C, 72.6; H, 6.62; N , 13.1; 0, 7.81; Mol. wt. (last) 301. The molecular weight determination was likely in error as the oompound reacted with camphor to give a red produot. -53-Infrared spectrum of C in KBr (cm. ): 3430(S), 3250(S), 3230(M), 3070(W), 2990(W), 2930(W), 1682(W), 1648(S), 1621(S), 1595(S), 1567(S), 1540(S), 1511(M), 1477(W), 1460{W), 1384(M), 1341(W), 1330(W), 1301(W), 1276(W), 1252(W), 1182(M), 1145(M), 1128(M), 1055(W), 1019(W), 968(W), 954(W), 909(W), 896(W), 878(W), 860(W), 825(S), 775(W), 75G(S), 662(M). Ultraviolet spectrum of C in 95$ ethanol; angstroms (log molar extinction coefficient ): 3170 (2.310), 3120(Sh) (2.389), 3035 (2.540), 2830(Sh) (3.603), 2730 (3.767), 2650 (3.748), 2240 (4.898). Some of the original crystalline product collected from the chloroform crystallization gave a positive ferric chloride test and slowly became brown upon standing giving off a putrescent odour even at -10°C. under vacuum and in the absence of ligh t . The oily component produced was easily separated from the crystalline compound C by chromatography on alumina. The .degraded oompound did not give a f e r r i c chloride test. Prolonged refluxing for six days with mercuric oxide in chloroform (31) gave no apparent change. Oompound C behaved Indifferently to proton donating solvents although blackening took place in concentrated sulphuric aoid. -54-C h a r a o t e r l z a t l o n o f Oompound D. ( Y i e l d Z%; a p a l e y e l l o w sweet s m e l l i n g s y r u p ) . No a t t e m p t was made t o c r y s t a l l i z e t h i s f r a c t i o n . I t was s o l u b l e i n e t h a n o l and b e n z e n e , p o o r l y s o l u b l e i n l i g r o i n . I n f r a r e d s p e c t r u m o f D i n K B r ( c m T 1 ) : 3060(W), 2 9 1 5 ( S ) , 2 8 5 0 ( S ) , 1632(W), 1600(W), 1 4 6 0 ( S ) , 1 3 8 0 ( H ) , 1270(W), 1125(W), 1020(W), 958(W), 947(W), 890(W), 8 5 4 ( H ) , 8 1 7 ( S ) , 7 4 7 ( S ) . An a t t e m p t t o p r e p a r e t h e 2 , 4 - d i n i t r o p h e n y l -h y d r a z o n e d e r i v a t i v e was u n s u c c e s s f u l . C h a r a c t e r i z a t i o n o f Compound E The f r a c t i o n r e c o v e r e d was a d a r k brown r e s i n o u s wax, y i e l d 4 $ . A s m a l l c r y s t a l was s u c c e s s f u l l y i s o l a t e d f r o m a l i g r o i n s o l u t i o n b. 1 0 0 - 1 2 0 ° G . a f t e r s t a n d i n g s e v e r a l d a y s , m. 2 0 6 - 2 3 3 ° C . The f r a c t i o n was v e r y s o l u b l e i n e t h a n o l , i s o a m y l a l c o h o l , 3 - p e n t a n o n e , a c e t i c a o i d , o h l o r o f o r m and b e n z e n e . I t o i l e d o u t o f l i g r o i n s o l u t i o n s . I n f r a r e d s p e c t r u m u s i n g a CHClg d e p o s i t e d f i l m on N a C l d i s o ( c m : 1 ) : 3060(W), 3 0 2 0 ( H ) , 2 9 6 0 ( S ) , 2 9 2 0 ( S ) , 2860(M), 1 7 1 0 ( 8 ) , 1 6 7 5 ( H ) , 1635(W), 1600(W), 1 5 3 3 ( H ) , 1 5 0 8 ( H ) , 1455(M), 1405(W), 1377(W), 1 3 5 3 ( H ) , 1515(W), 1273(W), 1245(W), 1 2 1 7 ( S ) , 1182(W), U 4 2 ( W ) , 1128(W), 1019(W), 953(W), 890(W), 855(W), 8 2 0 ( H ) , 7 6 0 ( S ) , 6 6 8 ( H ) . -55-A small amount of the fraction was dissolved in ethanol and 2,4-dinitrophenylhydrazine in ethanol was added along with two drops concentrated sulphuric acid and the solution refluxed. After standing overnight a minute amount of red precipitate appeared which melted over a wide range being oily at room temperature and containing orystalline solid at temperatures above 2G0°C. Characterization of Compound F Yield 5%. This fraction was triturated with successive portions of li g r o i n , b. 65-75°C. to leave behind a trace of dark brown resinous material which was discarded. The pale brown syrup reoovered was very soluble in methanol, 3-pentanone, isoamyl alcohol, acetic acid, chloroform and benzene. Attempts at re-crystallization from petroleum ether-benzene or petroleum ether-chloroform resulted only in oiling out. Infrared spectra using a CBXJlg deposited film on HaCl diso (oml 1): 2210(W), 2G5G(W), 2005(W), 2960CW), 2905(W), 1708(H), 1690(S), 1598(W), 1550(l), 1525(W), 1505(W), 1455(W), 1278(W), 1245(W), 1272(W), 1216(S), 1127(W), 1016(W), 950(W), 887(W), 855(W), 817(M), 752(S), 663(W). -56-( c ) R e a o t i o n o f 2 - a c e t o n a p h t h q n e w i t h 2 - a c e t o n a p h t h o n e oxime t o y i e l d 2 - ( f f - n a p h t h y l ) - 4 - m e t h y l b e n z o [h]  q u i n o l i n e I n t o a g l a s s l i n e r was p l a c e d 1.85 g . (0.01 m.) 2 - a c e t o n a p h t h o n e oxime, 1.70 g . (0.01 m.) 2 - a c e t o -n a p h t h o n e and 10 m l . d r y b e n z e n e . The l i n e r was p l a c e d i n t o an a u t o c l a v e and t h e s y s t e m e v a c u a t e d t o 1.0 mm. Hg p r e s s u r e . The a u t o c l a v e was h e a t e d and r o c k e d a t 2 3 5 ° C . f o r 90 m i n u t e s whereupon t h e p r e s s u r e r o s e t o 90-10 p . s . i . When c o o l e d t h e c o n t e n t s were r e c o v e r e d i n t h e s o l i d s t a t e , t h e b e n z e n e s o l v e n t h a v i n g removed i t s e l f t o o u t s i d e t h e l i n e r . A p o r t i o n o f t h e r e c o v e r e d s o l i d (0.701 g.} was d i s s o l v e d i n 4 m l . benzene and d e v e l o p e d on an a l u m i n a column (35 mm. d i a m e t e r x 120 mm.). E l u t i o n was c a r r i e d out w i t h b e n z e n e - l i g r o i n ( 1 : 1 , v : v ) t o r e c o v e r 0.1896 g. o f m a t e r i a l w h i c h f l u o r e s c e d u n d e r u l t r a -v i o l e t r a d i a t i o n and w h i c h e x h i b i t e d i d e n t i c a l c h r o m a t o -g r a p h i c b e h a v i o u r t o t h a t shown by 2 - ( ^ - n a p h t h y l - 4 -m e t h y l b e n z o f h ] q u i n o l i n e . The r e m a i n i n g z o n e s were d i s c a r d e d . The r e c o v e r e d compound was d i s s o l v e d i n d r y e t h e r and d r y h y d r o g e n c h l o r i d e was p a s s e d t h r o u g h t h e e t h e r e a l s o l u t i o n t o p r e c i p i t a t e a b r i g h t y e l l o w s a l t . F i l t r a t i o n o f t h e y e l l o w s a l t and r e m o v a l o f t h e e t h e r -57-by evaporation l e f t a pale yellow o i l 0.1168 g. Hence, 0.07E8 g. (11$) of the products were recovered as the hydrochloride salt. The bright yellow salt was de-composed by dissolving in acetone and adding sodium acetate (39) whereupon the yellow colouration dis-appeared rapidly. The acetone was removed by evaporation and the residue dissolved in one ml. benzene which was placed on an alumina column (10 mm. diameter x 90 mm.). The compound was eluted with benzene-petroleum ether (1:1 v:v). The fraotion collected was recrystallized from ethanol to give a white crystalline oompound, m. 120-124°C. A mixed melting point with 2-(£-naphthyl)-4-methylbenzo[h]quinoline gave 119-124°C. The infrared spectra of the oompound was identical to the infrared spectra of 2-(£-naphthyl)-4-methylbenzo-[h] quinoline. Woveoumbers in cm. Fig. 4-Infrared Absorption Spectra of: (1) 2-(B-Naphthyl)-4-methylbenzo[h]quinoline (in KBr) (2) 3-Methylbenzoff]phthalimidine (in KBr) (3) 3,4-Dihydra-3-phenylisocorbostyryl (in Nujol on Intracord Spectrophotometer) -58-IV. BIBLIOGRAPHY 1. Auwers, K. and Meyer, V.; B e r . 22, 7G5 ( 1 8 8 9 ) . 2. Baohman, W. E . and B a r t o n , S i s t e r M. X a v e r i a ; J . O r g . Chem. 3, 300-11 ( 1 9 3 8 ) . 3. B a r b o t ; B u l l . s o c . chi m . 47, 1318 ( 1 9 3 0 ) . 4. Beckmann, E . ; B e r . 19, 988 (1886) 5. Beckmann, E . ; B e r . 20. 1507, 2580 ( 1 8 8 7 ) . 6. : Beckmann, E . ; B e r . 22, 514 (1889) • 7. I b i d . , 1531. 8. B i l l m a n , J . H. and T a i , 535-9 ( 1 9 5 8 ) . K. M. ; J . O r g . Chem. 23, 9. B r a d y , 0. L.; J . Chem. Soo. 1931, 105-7. 10. B r i n e r , E . t S u s y , B. and D a l l w i g k , E . , H e l v . Chim. A c t a . 35, 340, 345, 353 ( 1 9 5 2 ) . 11. B r y s o n , A. and Dwyer, P. P.; J . P r o c . Roy. S c i . U.S. W a l e s 74, 107-9 ( 1 9 4 0 ) . 12. B u c k l e y , G. D. and Ray, N. H.; J . Chem. S o c . 1949. 1151-4. 13. I b i d . ; 1154-6. 14. B u r g e r , A. and M o d l i n , 1. R., J r . ; J . Am. Chem. Soo. 62, 1079 ( 1 9 4 0 ) . 15. B u u H o i and C a g n i e n t , P.; B u l l . s o c . c h i m . 1946. 134-9. 16. C h e r o n i s , R., T e c h n i q u e o f O r g a n i c C h e m i s t r y . v o l . V I , p . 453 ( 1 9 3 0 ) . 17. C o l b y , C.E. and Dodge, P. D.; J . Am. Ghem. Soo. 13, 1 ( 1 8 9 1 ) . 18. D a v i e s , M. and E v a n s , J . C ; J . Chem. P h y s . 20, 342 ( 1 9 5 2 ) . 19. Edwards, 0. E . and S i n g h , T.; Can. J . Chem. 32, 683 ( 1 9 5 4 ) . -59-2G. Ilderfield, R. G., Heterocyclic Compounds, vol. IV, New York, John Wiley & Sons, 1957. 21. Emmett, P. H.; Catalysis, vol. V, New York, Reinhold, 1957, pp. 1-130. 22. Pieser, L. P.; Experiments in Organic Chemistry, 2nd ed., D. C. Heath & Co., 1941, pp. 360-2. 23. Ibid.; p. 363. 24. Peigel, P.; II Spot Tests in Organic Applications. New York, Elsevier, 1954, p.224. 25. Pieser, L. P.; Experiments in Organic Chemistry. 3rd ed., D. C. Heath & Co., 1955, p.209. 26. Gabriel, S.; Ber. 18, 1251, 2433 (1885). 27. Goldschmidt, H.; Ber. 16, 2176 (1883). 28. Goulden, J. D. S.; J. Chem. Soo. 1953. 997. 29. Hantzsoh, A. and Werner, A.; Ber. 23, 11 (1890). 30. Hantzsch, A.; Ber. 24, 13 (1891). 31. Harries, C. and Jablonski, Ludwig; Ber. 31, 1379 (1898). 32. Hartwell, E. J., Richards, R.E. and Thompson, H.W.; J. Chem. Soc. 1948. 1436. 33. Hieber, W. and Leutert, P.; Ber. 60B, 2296-310 (1927). 34. Ibid.; 2310-7. 35. Hieber, W. and leutert, P.; Ber. 62B, 1839 (1929). 36. Hieber, W. and Wiesboeck, R.; Ber. 91, 1146-55 (1958). 37. Ibid.; 1156-61. 38. Hunsberger, I. M.; J. Am. Chem. Soc. 72, 5626 (1950). 39. Johnson, W.S. and Matthews, P. J.; J. Am. Ghem. Soc. 66, 210 (1944). -60-40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. Kirrmann, A. and Laurent, P.; Bull. soo. chim. 6, 1657 (1939). Kbdama, S., Nose, S. and Tdmilisa, N.• Japan 5519 (1956). Chem. Abstr. 52: 11901° (1958). Letaw, H., Jr., and Gropp, A.H.; J. Chem. Phys. 21, 1621 (1953). Meisenheimer, J.; Ber. 54, 3206 (1921). Meisenheimer and Thielacker in Freudenberg's Sterioohemie. Deutloke, Leipzig & Vienna (1933), pp. 1039 f f . Meisenheimer, J., Zimmerman, P. and Krummer, U. V., Ann. 446, 205 (1925). Murahashi, S.; J. Am. Chem. Soo. 77, , 6403-4 (1955). Murahashi, S. and Horiie, S.; J. Am. Chem. Soo. 78, 4816-7 (1956). Nakamura, A. and Hagihara, N.• Mem. Inst. Ind. Research, Osaka Univ. 15, 195-9 (1958) of Chem. Abstr. 53, 1197h (1959). Nienburg, H. J. and Keunecka, E.; Germany 865, 799 (1955) of Chem. Abstr. 48: 1427h (1954). Openshaw, H.T.; A Laboratory Manual of Qualitative Organic Analysis, Cambridge, 1946, p. 4. Piero, P.; I t a l . 471,913 (1952). Chem. Abstr. 48, 7627gTl954). Pino, P. and Magri, R.; Ghimioa e industria (Milan) 34, 511-17 (1952). Chem. Abstr. 47, 10492S (1953). Priohard, W. W.; J. Am. Chem. Soo. 78, 6137 (1956). Chem. Abstr. 52, ZOl97h (1958). Rosenthal, A., Astbury, R and Hubsoher, A.; J. Org. Chem. 23, 1037 (1958). -61-56. Rosenthal., A. and O ' D o n n e l l , J . ; P r i v a t e C ommunioation, 1959. 57. R u z i k a , L., De G r a a f , G. B. R. and H o s k i n g , J . R.; H e l v . Chim. A c t a . 14, 238 ( 1 9 3 1 ) . 58. S a h n i , R. C ; T r a n s F a r a d a y S o c . 49, 1 ( 1 9 5 3 ) . 59. S c h r i n e r , R. 1. and F u s o n , R. C.; The S y s t e m a t i c I d e n t i f i c a t i o n o f O r g a n i c Compoands. 3 r d E d . , New Y o r k , J o h n W i l e y , 1948, p. 91. 60. I b i d . ; p . 180. 61. I b i d . ; p. 202. 62. S e i t z , F.; B e r . 22, 257 ( 1 8 8 9 ) . 63. Shaw, J . T. and T y s o n , F. T.; J . Am. Chem. S o c . 78, 2538 ( 1 9 5 6 ) . 64. S t e p h e n , H. and B l e l o c h , Wm.; J . Chem. Soo. 1931, 886-95. 65. S t o b b e , H.; B e r . 35, 911 ( 1 9 0 2 ) . 66. T a y l o r , T. W. J . , C a l l o w , M r s . N. H. and F r a n c i s , C. R., J . Chem. Soo. 1939, 257-63. 67. T s c h a g a e f f , L.; B e r . 39, 2672 ( 1 9 0 6 ) . 68. T y s o n , F . T. and Shaw, J . T.; J . Am. Chem. S o c . 74, 2293 ( 1 9 5 2 ) . 69. V o g e l , A. I . ; A T e x t b o o k o f Q u a l i t a t i v e C h e m i o a l A n a l y s i s . Longmans, T o r o n t o , 1952, p. 204. 70. W e i s s b e r g e r , A.; T e c h n i q u e o f O r g a n i c Chemistry;.; Y o l . I X. C h e m i c a l A p p l i c a t i o n s o f S p e c t r o s -copy , New Y o r k , I n t e r s c i e n c e , 1956, p . 517-8. 71. Wender, I . , G r e e n f i e l d , G. and O r o h i n . M.; J . Am. Chem. S o c . 73, 2656 ( 1 9 5 1 ) . 72. Wheland, C. W., Advanoed O r g a n l o C h e m i s t r y . 2nd E d . , New Y o r k , J o h n W i l e y & S o n s , 1949, p . 337. 73. Z e o h m e i s t e r , L . and T r u k a , J . ; B e r . 63B, 2883-4 ( 1 9 3 0 ) . -62-V. ADDENDUM 1-((?-Naphth.yl ) e t h . y l u r e a f r o m 2 - a c e t o n a p h t h o n e oxime . Compound C ( s e e exp. p.51 and d i s c . p.22) h a s now b e e n t e n t a t i v e l y e s t a b l i s h e d t o be r a o e m i c l - ( ^ - n a p h t h y l ) e t h y l u r e a on t h e f o l l o w i n g b a s e s : t h e m e l t i n g p o i n t o f oompound C was f o u n d t o be 1 9 6 - 1 9 8 ° C . w h i c h i s i n e x c e l l e n t agreement w i t h t h e l i t e r a t u r e m e l t i n g p o i n t o f 1 9 8 ° C . f o r 1 - ( ^ - n a p h t h y l J e t h y l u r e a ( 7 5 ) , e l e m e n t a l a n a l y s i s ( s e e e x p . p.52) i s i n agreement w i t h t h e p o s t u l a t e d s t r u c t u r e a s shown below: I • C H N H C O N H „ CO C ( d , l fo r m ) -1 i n f r a r e d a n a l y s i s shows p e a k s a t 3430 and 3550 cm. w h i c h a r e a t t r i b u t e d t o t h e N-H s t r e t c h i n g i n a p r i m a r y amide -1 , V ( 7 6 ) . U r e a shows p e a k s a t 3434 and 3376 cm. (74) and -1 b e n z y l u r e a shows p e a k s a t 3440 and 3328 cm. ( 5 6 ) . The -1 p e a k a t 5230 cm. f o r p r o d u c t C c a n be a s s i g n e d t o t h e N-H o f a s e c o n d a r y amide ( 7 6 ) . F u r t h e r m o r e , t h e p e a k s -1 a t 1648 and 1537 cm. a r e a t t r i b u t e d t o t h e amide I and th e amide I I b a n d s ( 7 7 ) . - 6 3 -A s u g g e s t e d mechanism f o r t h e f o r m a t i o n o f l - ( ^ - n a p h t h y l ) e t h y l u r e a f r o m E - a c e t o n a p h t h o n e oxime i s shown below: Work i n o u r l a b o r a t o r y ( 56) h a s c o n c l u s i v e l y shown t h a t t h e o x i m e s u n d e r g o h y d r o l y s i s u n d e r t h e c o n d i t i o n s u s e d t o y i e l d some k e t o n e . F u r t h e r m o r e , o t h e r w o r k e r s (48) have shown t h a t u n s a t u r a t e d compounds u n d e r g o r e d u c t i o n w i t h h y d r o g e n i n t h e presence o f d i o o b a l t o o t a c a r b o n y l . -64-BIBLIOGRAPHY K e l l n e r , L . ; P r o c . Hoy. Soo. L o n d o n 177 447, 456 ( 1 9 4 1 ) . S a m u e l s s o n , E . ; T h e s i s , U n i v . Lund 1922, Chem. A b s t r . 18: 1 8 2 4 1 ( 1 9 2 4 ) . W e i s s b e r g e r , A.; T e c h n i q u e o f O r g a n i c C h e m i s t r y . Y o l . IX, C h e m i c a l A p p l i c a t i o n s o f S p e c t r o s c o p y . New Y o r k , I n t e r s c i e n c e , 1956, p . 511, 514. I b i d . ; p.521-2. 

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