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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 t h i s thesis as conforming required standard  to the  THE UNIVERSITY OF BRITISH COLUMBIA May, 1959  ABSTRACT  When d e o x y b e n z o i n carbon  monoxide  dicobalt  oxime  and h y d r o g e n  i n the presence  ootacarbonyl at elevated  pressures  were  conditions  benzo[h] q u i n o l i n e ,  the structure  quinoline chloride  derivative quinoline  reacted  Verification  of 2-(^-naphthyl)-4-methylbenzo[h]i n part  through salt,  the hydro-  the picrate  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 ] derivative.  2- a c e t o n a p h t h o n e  2-(^-K.aphthyl )-4-methyl-  was a l s o oxime w i t h  synthesized by  reacting  2-acetonaphthone  at  temperatures. The  are  was  produced.  the methiodide  benzofh] q u i n o l i n e  elevated  oxime  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  was a t t a i n e d salt,  3-phenyl-3,4-  2-(^-naphthyl)-4-methyl-  1- ( ^ - n a p h t h y l ) e t h y l u r e a w e r e of  of  produced.  When 2 - a c e t o n a p h t h o n e similar  with  t e m p e r a t u r e s and  5 - b e n z y l p h t h a l i m i d i n e and  dihydroisocarbostyryl  under  was r e a c t e d  described.  infrared  spectra  o f t h e above  compounds  In presenting  t h i s thesis i n p a r t i a l fulfilment of  the requirements for an advanced degree at the  University  of B r i t i s h Columbia, I agree that the Library s h a l l make i t f r e e l y available for reference  and study.  I further  agree that permission for extensive copying of t h i s thesis for scholarly purposes may  be granted by the Head of my  Department or by his representatives.  It i s understood  that copying or publication of this thesis for f i n a n c i a l gain s h a l l not be allowed without my written permission.  Department of The University of B r i t i s h Columbia, Vancouver 8, Canada.  ACKNOWLEDGEMENT  I wish to express my sincere thanks to Dr. A . Rosenthal f o r h i s patience, advice and encouragement i n the d i r e c t i o n of t h i s researoh project.  TABLE OF CONTENTS  I.  PAGE  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 II.  10  DISCUSSION Reactions of carbon monoxide and hydrogen with: (a) Deoxybenzoin oxime  1  (b) 2-Aoetonaphthone oxime III.  EXPERIMENTAL  3  14 26  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 IV. V.  BIBLIOGRAPHY  5  6  5  8  ADDENDUM l-(£-Naphthyl)ethylurea 2-aeetonaphthone  from  oxime  6  2  LIST OF FIGURES  1.  U l t r a v i o l e t speotra of phenanthrene, 2,4-dlmethyl-benzo[bJquinoline and 2- (^-naphthylj-4-methylbenzorh]quinoline  2.  2 5  a  Plot of Pressure against Time f o r the Reaction of 2-Aoetonaphthone Oxime with Carbon Monoxide and Hydrogen at 195°  2.  25b  Separation of the 2-Acetonaphthone Oxime Reaction Produots  4.  2 6  Infrared Spectra of 2-(^-Naphthyl)-4methylbenzoCh]quinoline,  3-Methyl-  benzo[fJphthalimidine and 3,4-Dihydro3- phenyliso carbostyryl  57a  I. (a)  HISTORICAL  High Pressure Reactions of Carbon Monoxide with Nitrogen Containing Compounds A considerable amount of investigative work has  been done on both a purely s c i e n t i f i c and a commercial basis on a study of carbon monoxide and hydrogen with olefins.  An excellent review of t h i s 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 y i e l d i n g  reduced products but giving no addition with carbon monoxide.  However, several workers have reoently  investigated the carbonylation of a few organic compounds containing the N=N, groupings.  the C=N and the  C-N  In 1949 Buckley and Ray (12) reported  that they reaoted oarbon monoxide with a n i l i n e to produce a cross linked polymer containing varying amounts of oxygen i n the hydroxyl form and having a l l i t s nitrogen i n 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-phenylhydroxylamine was reduced to a n i l i n e , and N-phenylbenzaldoxime was reduced to benzylideneaniline. Work of a commercial nature has been done i n the preparation of amides from carbon monoxide, o l e f i n s , and amines (49, 51, 52) and formamide has been successf u l l y prepared from ammonia and carbon monoxide (41). Tyson and Shaw i n 1952 (68) prepared 3-indoleoarboxaldehyde from carbon monoxide and the potassium salt of indole.  They did not produce any N-formylated  products of indole but i n 1956 (63) they produced £ormylindoline  l-  i n good y i e l d from both carbon monoxide  and potassium indoline.  Prom t h i s they deduced that  l i k e l y the U-formyl form of indole i s produced but that t h i s very r e a d i l y isomerizes to the 3-oarboxaldehyde form. Priehard i n 1956 (53) cyolized the aromatlo amide H,N-dibenzoylaniline with oarbon monoxide at 325°G. using n i c k e l carbonyl as the c a t a l y s t .  E-  phenylphthalimidine and benzene were produced.  S i m i l a r l y 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 monoxide and n i c k e l carbonyl gave phthalimide. In 1955 Murahashi (46) heated benzaiaehyde a n i l i n benzene with dioobalt octaoarbonyl and 100-200 »  • —  atmospheres oarbon monoxide at 22O-230°C. f o r 5-6 hours. 2-Phenylphthalimidine was obtained i n 80% y i e l d .  In  a similar way p-hydroxybenzaldehyde a n i l yielded 70% 6-hydroxy-2-phenylphthalimidine.  0  cc-Haphthaldehyde a n i l afforded 2-phenylbenzo [e]phthalimidine i n 90o y i e l d .  ^-Naphthaldehyde  yielded 2-phenylbenzo [f]phthalimidine.  anil  The faot that  r i n g closure oocurred i n the 2-position of the naphthalene moiety i s noteworthy since most r i n g closure reactions of ^-substituted naphthalene derivatives  0  -4-  take place i n the 1- o r ° c - p o s i t i o n . In 1956 Murahashl and Horiie (47) reaoted azobenzene with oarbon monoxide at 150 and 190°C. to form indazoline.  atmospheres  At 230°C. an  additional mole of carbon monoxide was absorbed per mole of indazoline and the product formed was 3phenyl-2,4-dioxo-l,2,3,4-tetrahydroquinazoline.  That  t h i s 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 i n quantitative y i e l d .  Sim-  i l a r oonversion to the analogues of the above compounds were carried out with 4-ohloroazobenzene aminoazobenzene.  and 4-dimethyl-  In the case of the substituted  azobenzenes ring closure occurred on the r i n g containing the substituent.  -5-  In 1958, Priohard (54) prepared  N-substituted  phthalimidines from N-substituted imines of carbocyelic aromatio k e t a l s .  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-Me N, 2-Me, 2-(1-naphthyl), 2  S-(p-diethylaminophenyl),  and N,N -ethylenediphthal-  amidine. In 1958 Kakamura and Hagihara (48) hydrogenated Sohiff bases i n the presence of carbon monoxide, hydrogen and dicobalt octacarbonyl at elevated temperatures and pressures. phenylimine  They reduced benzal-  (PhCH=NPh), benzalcyclohexylimine  (PhCH=WCgHn), cyolohexanophenylimine (C H =NPh) 6  oyolohexanooyclohexylimine  (CgH^o^l^Hj^ ).  cyclohexaloyclohexylimine ( C ary amines.  6  i0  a  HJLXCH=UG5HIX )  n  d  "to second-  The Sohiff bases which were the most  conjugated were the most e a s i l y reduced and formed the lowest amounts of resinous by products.  Non  polar solvents gaye the highest y i e l d s with cyclohexane giving higher y i e l d s than benzene which, i n turn, gave higher y i e l d s than did dioxane.  Sulphur  compounds did not retard the reaotion although amines, especially the a l i p h a t i c s , lowered the y i e l d s  -6-  oonsiderably. Although of  imines  carbon  and a z o compounds  monoxide  Kosenthal monoxide  r e c e n t w o r k was r e p o r t e d  no work was r e p o r t e d  and A s t b u r y  that  oxide  and hydrogen  benzophenone  yield.  oxide  took  oxime  Gyclization  h y d r o g e n was l a r g e  oximes.  to yield  p l a c e when  reaotion with outside  (55) f o rthe r e a c t i o n  and h y d r o g e n w i t h  found  80$  i n their  i n the study  of  I n 1958  reacted with  of  carbon  they  oarbon  mon-  3-phenylphthalimidine i n  o f t h e oxime  the ratio  (98:2).  that  with  of carbon  carbon  mon-  monoxide t o  O-Benzoylbenzoio  acid  0 oxime  also  gave  quantitative conditions  S-phenylphthalimidlne  yield  and, hence,  i n almost  showing  that  under t h e  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  taken  plaoe. When a c e t o p h e n o n e monoxide  i n the presence  octaoarbonyl into  three  first was  a syrup  fractions  fraction  n o t worked  oxime  reaoted  of hydrogen  was o b t a i n e d by alumina  with  and  which  carbon  dicobalt  was  separated  chromatography.  The  (10$) contained  no c a r b o n y l group and  with  Chemical  further.  analysis of  -7-  one of the other f r a c t i o n s indicated that two moles of acetophenone oxime had condensed with a mole of hydrogen and a mole of carbon monoxide to y i e l d a dimer which l o s t a mole of hydroxylamine.  This compound f a i l e d 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 t h i r d f r a c t i o n recovered  from the reaction mixture was i d e n t i f i e d as 3-methylphthalimidine 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 r a d i c a l groups R and T are i d e n t i c a l .  However,  i f the two groups R and T are d i f f e r e n t 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 i n effect that the two isomers were stereoisomers of an ethylenic nature as postulated i n formulas I and I I . R-C-T ll N-OH I  The nitrogen atom R-C-T II HO-U II  l i k e the oarbon atom i s tetrahedral but d i f f e r s from  -8-  the at  oarbon  atom  i n having  an unshared  of electrons  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  atomic  or moleoular  satisfactory oximes  group  structure  (78).  That  explaining  Chemistry"  reaction  figuration  o f oximes  i s t h e so o a l l e d  ( 4 , 5, 6 ) .  a reagent  chloride give  suoh  a substituted t o take  hydroxyl  group  joined form  place  i n "Advanced  Beokmann r e -  When a k e t o n e  aoid  oxime  a rearrangement  amide.  takes  The arrangement  i n two s t e p s .  oarbon  i s treated  pentaohloride, acetyl  exchanges p l a c e s with  t o t h e oxime  o f the  f o r d e t e r m i n i n g t h e con-  as phosphorus  or sulphuric  believed  i s t h e most  b y Wheland ( 7 2 ) .  important  arrangement  than an  the isomerism  An  with  this  i s explained i n considerable detail  Organic  to  pair  form  i s  F i r s t , the one o f t h e r a d i c a l s  and t h e r e s u l t i n g  rearranges to the laotam  place  (72).  laotim  There i s  PCI R C 2  S>  = NOH  considerable rather  than  evidence  the nitrogen  to  i t on t h e oxime  to  form  *  a trans  RCONHR  rearrangement  The h y d r o x y l  exchanges p l a o e s with  group  the raclldal  that  anti  oarbon.  t o the s t e r e o i s o m e r i s m o f t h e oximes  be expected  oould  t o support  a c i s one ( 4 2 , 4 5 ) .  on  Due  R C ( O H ) = NS  2-aoetonaphthone  two i s o m e r s when  t h e oxime  oxime  i t  i s  itself  i s prepared  from  the ketone (61).  The r a t i o 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 i n pyridine.  A Beckmann rearrangement was carried out  on the oxime produced and the r e s u l t i n g amide hydrolysed.  Helative proportions of amines and acids  present gave the proportion of the oximes o r i g i n a l l y 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 f o r the rearranged product phenylaoetanilide.  No mention was given that any  N-phenylphenylaoetamide, which would be the other amide f o r the other oxime isomer, was found.  Hence,  the o r i g i n a l oxime must have been syn-phenylbenzylketone oxime and the reaction was as follows: 0  -10-  (o)  Cobalt Complexes of Oximes and other Organic Bases Glyoximes and a l k y l derivatives of glyoxlmes  have been known f o r a long time to reaot with m e t a l l i c s a l t s including cobalt s a l t s .  For example, Tsohagaeff  i n 1906 (67) prepared the compound (H0N=CMeCMe=K0)2 " CoUHgBr from dimethyl-glyoxime.  Many other s a l t s of  glyoximes have been prepared and considerable research has gone into these complexes i n order to eluoidate t h e i r structure and also as agents i n the deteotion and separation of metallic s a l t s .  An example of the use  of glyoximes i s i n the detection of niokel s a l t s by the p r e c i p i t a t i o n of the red preoipitate of niokel dimethylglyoxime (69). Hot only do the glyoximes form metallic s a l t s but other compounds related to them do also.  Oximes  which form metallic complexes are the b e n z i l monoxlme (26,44), monomethyl ether of b e n z i l glyoxime (33), o-hydroxybenzaldoxime  (9), oxime hydrazone  (66), and £-£urfuraldoxime (11).  of b e n z i l  I t w i l l be noticed  that i n a l l cases the oxime i s adjacent to a functional group of some kind.  Examples of where t h i s was not  the oase were offered by Hieber and Leutert (33) who successfully prepared both the n i c k e l and the cobalt s a l t s 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 suspensions of cobalt chloride i n inert solvents beoame an intense blue when acetone oxime was added. compound was i s o l a t e d .  No  When antibenzaldehyde oxime  was reacted with cobalt halides the oxime rearranged to the syn form showing that metal s a l t s 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 ootacarbonyl and oximes.  However, reoent work shows that  cobalt carbonyls reaot with N-bases leading in to a d e f i n i t e compound of polar structure as  general  follows  (36): SJCofCOjJg  +  12B  *  2^oB ][Co(G0) ] 6  4  2  + 8C0  The bases used were oc and £ p i c o l i n e , quinoline, p y r r o l i d i n e , morpholine, ethyleneimine, d i a o e t y l - d i a n i l i n e (a Sohiff base), and aromatic amines.  formamiae,  diethylenetriamine  D i a c e t y l - d i a n i l i n e oomplexed  with the oobalt oatalyst i n the r a t i o of 1:2  rather  than  1:4 t o g i v e  the following  structure:  ye •H = G  I  Go H C  6 5 H  Diethylenetriamine, dicobalt  on t h e other  ootaoarbonyl  structure  [Co ( C O L ] 4J 2  = C  aocording  hand,  complexed  with  to the generalized  CoB (Co( C 0 ) ] . 2  The complexes example,  4  above  with  g  workers  oxygen  prepared  containing bases  acetophenone  according  also  reacted with  cobalt (37j.  the metal  carbonyl For  oarbonyl  t o the following equation:  3[Co(C0) ] 4  2  -f  ,C H C0CH 6  5  .  3  2[Co(C H eoeHg)^] 6  Benzophenone  3[GO(C0) ] 4  2  complexes  +  t o give  £C H C0C H 6  5  [Co(C0) ]  e  6  4  the following  5  -f  8GG  structure:  *  5  2[Go(C H C0e H^)J [C0(CG) ] 6  2  6  4  2  + 8GG  -13-  II. (a)  DISCUSSION  Beaotion of Carbon Monoxide and Hydrogen with Deoxybenzoin Oxime When deoxybenzoin oxime was reaoted with  carbon  monoxide and hydrogen (98.5:1.5) i n the presence  of  preformed dicobalt octaoarbonyl (71) at 3600 p . s . i . and 250°C. two c r y s t a l l i n e products were obtained. minor c r y s t a l l i n e product (16$) was  isolated  The  by  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 of the products with ethanol. The c r y s t a l l i n e product so obtained was p u r i f i e d  by  subsequent r e c r y s t a l l i z a t i o n from ethanol to give colorless needle l i k e c r y s t a l s , m. 202-203°C. basis of chemical and infrared  On the  analysis the product  was concluded to be 3,4-dihydro-3-phenylisooarbqstyryl. The absorption peak at 3250 cm."  i s attributed  L  bonded N-H  stretch  to a  frequency f o r a N-monosubstituted  amide (70) and the peak at 1670  cmT  1  i s attributed  to  a c y c l i c secondary amide (19). The major component was obtained by ohromatographing the remainder of the product on an  alumina  column and r e c r y s t a l i i z i n g the chromatographed product from ether-light  petroleum ether.  A mixed melting  point of t h i s sample with 3-benzylphthalimidine gave no melting point depression and, henoe, the  (26)  -14-  product was  concluded to be 3r.benzylphthalimidine.  The overall equation f o r the reaction was  as  follows:  o  (b)  Reaotion of Carbon Monoxide and Hydrogen with 2-Acetonaphthone Oxime When 2raoetonaphthone oxime was reacted with  carbon monoxide and hydrogen i n the presence of preformed dioobalt octaoarbonyl (71) at 4100 p . s . i . and 235°C. three c r y s t a l l i n e products were obtained. major product was  the unexpected compound  naphthyl)-4-methylbenzo 41$ y i e l d .  The  2-(B-  [h]quinoline (A) present i n  The second compound was the expected  (46, 55) 3,-me.thylbenzo [f ] ph thai imi dine (B) present i n 17$ y i e l d .  The t h i r d component (19$) appeared to  be an unstable one whioh changed i n a short time into the stable o r y s t a l l i n e  compound C the i d e n t i t y  of  -15-  whioh i s , at present, s t i l l unknown.  ( S e e p. 6 2 ) .  The overall reaction was as follows:  Compound A was a white c r y s t a l l i n e compound and could be r e p r y s t a l l i z e d ligroin.  from either ethanol or  I t fluoresced with an intense blue l i g h t  i n the presence of u l t r a v i o l e t  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. Ultraviolet  ) (28, 40, 70).  spectroscopy indicated that the compound  had a phenanthradine type structure.  When the u l t r a -  v i o l e t spectrum of A was oompared with the u l t r a v i o l e t spectra of phenanthrene and 2,4-dimethylbenzo[h]quinoline (39) there was a peak at 3450 angstroms f o r  -16-  o. product A corresponding to peaks of 3460 A'' f o r  o. phenanthrene and 3480 A  f o r 2,4-dimethylbenzo[h] o quinoline, and also a peak at 3220 A f o r product A o ' ;  corresponding to a peak of 3220 A (See figure 1;  f o r phenanthrene  p.25a).  Pyridine and quinoline derivatives form s a l t s with strongly proton donating solvents (20) and product A formed b r i g h t l y coloured s a l t s with sulphuric acid, formic acid and hydrochloric acid.  When  the hydrochloride salt was dissolved i n aqueous ethanol and t i t r a t e d against base a molecular weight olose to the t h e o r e t i c a l value was obtained. Further v e r i f i c a t i o n of a benzoquinoline struoture was obtained beoause of the f a i l u r e of the compound to reduce i n the presence of either magnesium methoxide (73) or l i t h i u m aluminum hydride (8).  An  attempt at oxidation with potassium ferrocyaniae (58) f a i l e d to a f f e c t the molecule.  The imine linkage  showed great chemioal s t a b i l i t y i n that attempted degradation of the moleoule with fused sodium hydroxide (16) at 250°C. f o r six hours gave baok most of the unchanged produots thus confirming further that the imine linkage was part of a heterocyclic system. When the oompound was subjected to oxidation with chromic acid i n acetic acid a bright orange  -17-  proauct was obtained i n low y i e l d whioh proved to have no aoidio function and slowly reddened i n the presence of sunlight.  Treatment with strong base gave r i s e to  immediate blackening.  This was the same kind of  behaviour as that observed by Johnson and Matthews (39) i n t h e i r attempt to oxidize 2,4-dimethyl-benzo[g]quinoline with chromic aoid i n acetic acid.  They also  obtained an orange product which they proved to be a quinone and t h i s quinone reddened i n the presence of sunlight and gave intractable decomposition products i n the presence of strong base.  On the basis of the  r e s u l t s of the chromic acid oxidation of product A a quinone had been formed and, henoe, the o r i g i n a l oompound was a oondensed  aromatic or heterocyclic  system.  That the system was heterocyclic was indicated by the presence of nitrogen i n the obtained oxidized produot. Any attempts to oxidize produot A with ehromic acid past the quinone stage met with f a i l u r e , the f a i l u r e being consistent with that of Seitz (62) who attempted to oxidize both 2-methylbenzo[g]quinoline and 2-methylbenzofh] 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 p o s i t i o n with the aid of selenium dioxide (14) to give 2-(^naphthyl)-4-formylbenzo[h] quinoline ((?).  This oxidized  product was a bright yellow c r y s t a l l i n e s o l i d , m.  159-  142.5°G. which by elemental analysis agreed i n comp o s i t i o n 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 i n the range 170-185 0. without attempt at p u r i f i c a t i o n . Oxidation of the obtained aldehyde was  then  -19-  attempted with the use of an ammoniacal solution of s i l v e r oxide (14) to prepare the known compound 2-(p-naphthylj-4-carboxybenzo[h] 228°C. (15).  quinoline (H), m.  227-  A oompound was obtained melting over  the range 220-262°G. without p u r i f i c a t i o n . The 2-(§-naphthyl)-4-earboxybenzo[h] quinoline i s e a s i l y 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 r e f l u x i n ethanol and chromatographed to give back some of the o r i g i n a l aldehyde plus small amounts of white product, m. 35-50°G.  crystalline  It i s f e l t that the wanted  heterocyclic oompound may be present but i n an impure form. An attempt to oxidize the aldehyde with n i t r i o acid was unsuccessful leading only to intractable decomposition products. On the basis of a l l the above evidence i t was concluded that product A must be 2-(§-naphthyl)-4methylbenzofh] quinoline and that i t was formed i n dependently of the presence of carbon monoxide as follows:  -20-  Since i t was postulated that t h i s 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 i n equimolar amounts i n benzene and placed i n an autoclave which  was  evacuated and the whole heated at 235°C. f o r 90 minutes. A colourless c r y s t a l l i n e 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 i d e n t i c a l 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. f i n d t h i s ketone were unsuccessful.  Attempts to  However,  i s o l a t i o n of a ketone after the subjection of an oxime to the experimental  conditions of carbonylation i s  known.  For  proved  the  example,  presence  J . O'Donnell  of benzophenone  mixture  recovered  after  the  phenone  oxime  taken  place  had  found  basis  that  the  conditions of  would  be  with as  reactive  2-acetonaphthone  i t was  That  c o u l d be  and  oxime  to  benzo-  no  e x p l a i n e d on reaction  would  the  product  A  B was  the  the ketone  immediately  form  was  concluded  that  product  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 . indicated  the  presenoe  characteristic an  reaotion  condense as  soon  formed.  It  for  i n the  (56).  was  highly  successfully  carbonylation of  2- a c e t o n a p h t h o n e under  has  amide  peak  at  of  the  f o r the  3280 cm.  Infrared cyclic  N-H  (18)  1  analysis  amide,  stretohing  and  the  expected  the frequency  characteristic -1  peak  f o r the  both  being present.  tricyclic  carbonyl of  system  the  The  was  amide  absence  shown b y  at of  the o  1638 an  om.  (19)  unsaturated  absence  of absorption  t  in  the  ultraviolet  analysis  g i v e s an  proposed  structure  That stantiated  the by  acetylation  disappearance stretching frequency  of  bond  successfully  was  of  the  1695  cm.  was  infrared and 1  B  Elemental  consistent  (see p.  present  aoetylation  successful  (39).  formula  oompound  frequency to  3300 A  empirical  N-H  the  was  above  was  apparent  due  f o r the  shift  The  acetylated  orystallized.  further B.  the  the  15).  of product  peak  with  i n the  sub-  That to  the  N-H carbonyl  produot  was  not  -22-  Work previously done further substantiates the proposed struoture.  Sinoe acetophenone oxime formed  3-methylphthalimidine  and benzophenone oxime formed  3-phenylphthalimidine  i n the presence of oarbon mon-  oxide, hydrogen and dioobalt octaoarbonyl at elevated temperatures  and pressures (55), and since Murahashi  (46) prepared the l i n e a r isomer N-phenylbenzoff]phthalimidine rather than the angular Isomer by carbonylating B-naphthaldehyde a n i l i t was concluded that product B was 3-methylbenzo[fjphthalimidine. A syrup F recovered from the reaction mixture appeared to have p o l a r i t y properties very similar to B on the basis of similar s o l u b i l i t y and chromatographic properties but i t was concluded that t h i s produot was not the angular isomer of B due to the wide differences i n carbonyl frequencies in the i n f r a -1 red spectra of both B and F being at 1690 em.  f o r F.  When the o r i g i n a l reaotion mixture was d i s solved i n 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 f e r r i d  ohloride test f o r a hydroxyl group and i t appeared to o slowly decompose even under vacuum, at 10 C., and i n the absenoe of sunlight giving o f f a putrescent type  of odour.  P u r i f i c a t i o n of the resultant degredative  produot by chromatography gave r i s e to a white c r y s t a l l i n e compound G which appeared  to be stable.  The c r y s t a l l i n e 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. at 1650 om.  1  Infrared showed a strong oarbonyl peak (19) and a strong  N-H peak f o r 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 benzenesulfonyl chloride indicated the absence of either a primary or a secondary amine group.  Furthermore,  the  oompound behaved i n d i f f e r e n t l y In the presence of strongly proton donating solvents thus confirming the absence of an amino group.  That no  hydroxylamine  group was present was v e r i f i e d on the basis that no r e s u l t came from the attempt oxide  tSl).  to oxidize C with mercuric  When a hydroxylamine  compound i s  oxidized with mercuric oxide a bright blue or green  -24-  s o l u t i o n appears due  to the n i t r o s o group and  metal i s a l s o d e p o s i t e d . indioated  Ultraviolet analysis  t h a t oompound C did not  ated t r i c y c l i c  system as  What has a c t i o n of the  mercury  shown by  o o n t a i n an oompound  unsatur-  A.  a p p a r e n t l y happened i s that the  carbon monoxide on the  mixture of compounds, one  oxime produced a  of which was  a nitroso  compound  (blue-green i n c o l o u r ) which was  i n a few  days changed i n t o c o l o u r l e s s n i t r o g e n  amide C.  No  f u r t h e r attempt was  to e l u c i d a t e the  - Iafrared two  nitroso  C.  s p e c t r a were taken on the  remaining E,  found that a carbonyl frequency o f 1710  existed  f o r E, but  that D possessed no  frequenoy i n i t s i n f r a r e d spectrum. showed an absence o f the N-H ponents.  No  and  rioh  components of the r e a o t i o n mixture, D and  i t was (10)  unstable  made at t h i s stage  i d e n t i t y of e i t h e r the  oompound or the product  re-  function  f u r t h e r work was  components beoause of the  The  and cm.  1  carbonyl  infrared  also  i n both com-  done on these  two  small amount of each p r e s e n t .  Although oximes undergo a Beokmann r e a r r a n g e ment under the evidenoe was ment had  influence  of an aoid  oatalyst  no  brought forward that a Beckmann rearrange-  ocourred i n the r e a c t i o n of 2-acetonaphthone  oxime w i t h oarbon monoxide and  hydrogen i n the  presence  --25-  of  dioobalt It  octacarbonyl. was  the  components  was  required  fractional its  izing ent  the  to  its  with  and  for  corresponding  a  rise  slower  After  the  pressure was  found  magnitude 195°G.  rate  was  had  taken  that to  of  equal  bomb had  f i g . 2,  mole  there  the  the  chromatography separate  the  the  mixture  components.  initial  a  into  The  another  of  work  and  properties  recrystall-  major  separation  results  carbon  oxime  in  this  purify  Much p a i n s t a k i n g  purification  r e a c t i o n of  (see  per  and  the  the  temperature  released  isolate  affected both  kinetic  2-acetonaphthone  pressure  to  componproblem.  of  the  components).  Interesting the  to  purify  separation  into  following  column  component  p . 36  matter  reaction.  both  and  one  f i g . 3,  mixture  of  chromatographic  making  (See  simple  crystallization  of  and  a  using  components  presenoe  not  at  a  mole  drop  cooled place drop  changes  i t was and  by  was  and  a  to  a  rise  notioed simple  i n pressure i n pressure  was  hydrogen  sudden  half  taking  the  in  this  Immediately  i n pressure  i n magnitude  and  At  ) there  substrate. a  monoxide  195°C.  p . 25b to  were;obtained  that  of  gas  following place in a  that  in  at  pressure. drop  calculation equal  rise  in  i t  molar  took place  at  ^"  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  2-Acetonaphthone at 195"  against  Oxime  wrth  Time  for  Carbon  Reaction Monoxide  of  and Hydrogen  -26-  III.  EXPERIMENTAL  Instrumentation The high pressure reactions were carried out i n 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 u l t r a v i o l e t absorption spectra  were obtained using a Cary Recording Quartz Spectrophotometer.  The melting points were determined by  means of a p o l a r i z i n g 100 Z microscope attached to an e l e o t r i o a l l y heated E. L e i t z (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 A i r Co. Ltd. of Vancouver, B. C. in 99.7% purity.  The aluminum oxide used f o r the  chromatography was procured from the B r i 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 l i n e r was added 18 g. cobalt(II)carbonate and 60 oo. dry thiophene free benzene.  The l i n e r was  placed i n an autoclave ( e f f e c t i v e void 280 cc.) and carbon monoxide was run i n up to 1660-10 p . s . i . followed by hydrogen up to 3230*10 p . s . i .  The auto-  olave was heated and rocked f o r 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 i n pressure of 880*10 p . s . i .  The dark solution was  stored at -12°G. i n a stoppered container i n 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 f o r s i x days after which the solution was diluted with 2000 ml. water to bring down a copious white p r e c i p i t a t e .  The  p r e c i p i t a t e was f i l t e r e d and repeatedly washed with water.  R e c r y s t a l l i z a t i o n of the oxime from a water  ethanol mixture gave 23.9 g. (75$) of the oxime having a melting point of 97-99°C.  literature  m.p.  98°C. (65). Reaotion of carbon monoxide with deoxybenzoin oxime Deoxybenzoin oxime (15.8 g.;  0.0635 m. ) was  mixed with 23 ml.[0.02 m. Co (C0) ] catalyst l i q u o r g  8  and the whole diluted up to 55 ml. with dry thiophene free benzene i n a l i n e r which i n turn was placed into the autoclave.  Carbon monoxide was run i n up to  2000*10 p . s . i . and the whole was heated and rooked f o r  -29-  2 hours at 250°C. whereupon a pressure of 3600*10 p . s . i . was reached.  After cooling to room temperature the  pressure was 1800*10 p . s . i . or a drop of 200 p . s . i . had occurred. The product obtained was heated under reduced pressure at 55°C. i n order to decompose the catalyst and to remove the solvent.  Dissolving the syrup i n  chloroform and treating with norite to remove the residual cobalt l e f t a f t e r evaporating the chloroform 15.9 g. of syrup. Characterization of the products R e c r y s t a l l i z a t i o n of the syrup with the use of 600 ml. anhydrous ethanol at 0°C. f o r 3 hours l e d to 2.5 g. of white needlelike c r y s t a l s (16$).  After two  more c r y s t a l l i z a t i o n s from ethanol the compound melted at 202-203° and was assumed to be 3,4-dihydro-3phenylisooarbostyryl. Anal. Calod. f o r C H N 0 : 15  0, 7.17;  N, 6.28.  0, 7.54;  N, 6.19.  Pound:  12  C, 80.69;  C, 80.32;  H, 5.87;  H, 6.01;  Infrared spectrum of 3,4-dihydro-3-phenyliso;  carbostyryl i n Nujol (cmT ): 3250(W), 2920(S), 1670(3), 1  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 y i e l d a c r y s t a l l i n e solid (0.2 g.) which was removed by filtration.  l e e r y s t a l l i z a t i o n of t h i s product from  methanol gave a compound melting sharply at 286°C. Beoause of the low y i e l d 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 i n 5 ml. benzene and the solution eluted on the column with benzene. trace of substance came down and t h i s was Further e l u t i o n using benzene-ethanol  A  disoarded.  99:1 v:v brought  down the bulk of the oompound i n a pale yellow form whioh when r e c r y s t a l l i z e d  from benzene-petroleum ether  caused removal of most of the colouration.  A further  r e c r y s t a l l i z a t i o n from alcohol-water mixture gave a white c r y s t a l l i n e oompound melting at 135-136°C. mixed melting point determination with 3-benzylphthalimidine gave no depression (26).  A  -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 r e s u l t i n g i n the formation of a copious white p r e c i p i t a t e i n l e s s than three hours. After 15 hours the p r e c i p i t a t e was f i l t e r e d , washed repeatedly with water and r e c r y s t a l l i z e d twice from a water-ethanol mixture to y i e l d 48 g. (73.5$) oxime a f t e r 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 l i q u o r [0.025 moles C o ( C 0 ) e J l n benzene 2  were added to 40 ml. thiophene free benzene i n a l i n e r which was placed i n an autoclave.  Carbon monoxide  was  run i n up to 2140*10 p . s . i . and the system rocked and heated at 21G-235°C. f o r 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  moles)  had  solution  was  heated  catalyst  and  the  solvent  wax  was  The  residual  with green  norite  t o remove  solution  f o r m gave  14.1 The  was g.  above  r e a d i n g s were constant  at  with  rapid  pressure  195°C. were  7G-80°C. was  dissolved the  removed  by  after  was  and  which  a  of the  repeated  plotted  (see f i g .  2, up  took place.  and  against p.25b).  treated  dark chloro-  pressure  time The  at auto-  t o 195°C. where The  readings  a  at  Pressure  Temperature  190°C.  2470  1  195°  2720  2  200°  5620  4  198°  3650  5  200°  3550  7  195°  3510  10  192°  3470  11  190°  3460  minutes  After  evaporation.  follows:  Time  0  the  wax.  c o n t e n t s were h e a t e d  as  benzene  decompose  Removal  reaction  r e o o r d e d and  The  i n chloroform  cobalt  o f brown  change  to  then  obtained.  temperature  clave  occurred.  20  m i n u t e s more  heating  at  p.s.i.  195°e.  the  -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 2 1 0 - 2 3 5 ° C . the product was  dissolved  i n ohloroform to give a dark green solution which when allowed to stand overnight at - 1 5 ° C . turned brown and a white residue C had formed y i e l d 1.6  g., m. 1 7 0 - 2 0 5 ° C i ,  insoluble in benzene, soluble i n ethanol. A portion of the o r y s t a l l i n e f r a c t i o n (0.35 g.) dissolved i n 1 ml. pyridine was added to the top of an alumina column (90 mm.  x 28 mm.  diameter) and developed  as follows: Effluent f r a o t i o n s (in m i l l i l i t r e s )  Wt. of Fractions ( i n grams)  700 ml. benzene  Trace of brown o i l  400 ml. 9:1 v:v benzeneethanol  0.25 g. white o r y s t a l l i n e oompound C  600 ml. ethanol  Trace of brown wax  The o r y s t a l l i n e produot C was further p u r i f i e d by r e c r y s t a l l i z a t i o n from 3-pentanone to give white needle l i k e c r y s t a l s , m.  204.5-205.5°G.  -34-  After removal of the product C from the ohloroform solution the ohloroform was removed by evaporation and a portion of the residue (7.8 g.) was dissolved i n 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 ( i n grams)  0.16 g. pale yellow sweet 80 ml. Benzene-light smelling syrup D pet.ether (1:1 v:vi 1000 ml. Benzene-light pet.ether (1:1 v:vi  3.15 g. white c r y s t a l l i n e compound A 0.32 g. dark brown wax E  1000 ml. Benzene 1700 ml. Benzene - t^BuOH 900 ml. Benzene-ethanol (1:1 v:v)  2.23 g. dark brown wax mixture ( i i i ) Pig. 3 1.32 g. pale brown amorphous s o l i d G  Total recovery was 7.2 g. or 92$.  It was  easy to follow the zones as they were either highly fluorescent i n the presence of u l t r a v i o l e t l i g h t 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 f r a c t i o n a l l y c r y s t a l l i z e d from  benzene to y i e l d the white o r y s t a l l i n e  oompound B.  -35-  The remaining f i l t r a t e (mixture i v , f i g . 2) was reohromatographed  by dissolving 1.64 g. i n 7 ml. benzene,  added to the top of an alumina column (140 mm. x 52 mm. diameter) and developed as follows:  Fractions and weight ( i n grams)  Effluent Fractions (in m i l l i l i t r e s )  0.10 g. sweet smelling o i l  150 ml. benzene-ether (7:2 vv)  -  1000 ml. benzene-ether (7:2 W ) 900 ml. benzene-ether (7:3 vv)  0.94 g- brown amorphous solid B  1000 ml. benzene-ether (7:3 vv)  0.08 g- brown amorphous solid F  1000 ml. benzene-etherethanol (69:30:1 vvv)  0.40 g- brown amorphous solid F 0.08 g- brown amorphous solid  500 ml. ethanol  Again, as above, the zones could be followed by u l t r a v i o l e t l i g h t .  Total y i e l d was 1.60 g. or 97$.  Characterization of 2-(g-naphthyl)-4-methylbenzorhJquinoline (Compound A) 2-((3-naphthyl )-4-methylbenzo[h] quinoline oame down as the second chromatographic zone (41$) on an alumina column and was p u r i f i e d further by r e c r y s t a l l i z a t i o n twice from absolute ethanol to give oolourless  -36-  Fig.  3 -  S e p a r a t i o n of the.2-Acetonaphthone  Oxime  Reaction Products  Mixture  (i)  and c a t a l y s t  in  benzene  Decomposition of 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 Mixture  r  \  (i) in chloroform Praotional crystallization  Co  1  Mixture  (ii) Chromatography  Zone 5  Zone 4  Zone 3  (2%)  C-orystalline (11%) A-erystalline (41%) Mixture  1  B<-crystalline  (3%)  .  1 B-impure (14%)  Zone 1  D-syrup  E-syrup (4$) C-r c r y s t a l l i n e (7%)  Zone £  (Hi) Fractional Crystalliza t i o n - benzene Mixture 1 1 Reohromatography 1 1 P- syrup  (5fo)  (iv)  -37-  needle l i k e c r y s t a l s , m. 123-124°C.  Recrystall-  i z a t i o n oould a l s o be done w i t h l i g r o i n g i v i n g  higher  y i e l d s than w i t h e t h a n o l but w i t h a lower degree o f purity. and  The oompound was s o l u b l e  i n acetone,  benzene  chloroform. Anal, calcd. f o r C  U:  C, 90.26;  H, 5.22;  Pound:  C, 89.63;  H, 5.36;  2 4  H  1 7  U, 4.39.  Mol. wt. 207.4.  N, 4.55.  Mol. wt. ( E a s t ) 288. Infrared  spectrum  o f A i n KBr ( c m . ) : 20801  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), 1 0 9 7 ( f ) , 1035(W), 1025(W), 962(W), 922(W), 904(W), 888(W), 867(S), 829(S), 756(S),  801(S)  f  776(W),  763(S),  741(W), 731(W), 683(W), 645(W). Ultraviolet  spectrum  o f A i n 95% e t h a n o l ;  angstroms ( l o g molar e x t i n c t i o n c o e f f i c i e n t 5450 (4.16);  3220 (4.56);  3150 (4.31);  2780 (4.50);  2430 (4.60);  2120  Attempted r e d u c t i o n of  ): 3620  (4.14);  2870 (4.30);  (4.44).  2-(g-naphthvl)-4-methylbenzo[hj-  q u i n o l i n e w i t h l i t h i u m aluminum h y d r i d e (8) To a s o l u t i o n of 5 ml. p u r i f i e d and d r i e d  diethyl  e t h e r (22) and 0.05 g. l i t h i u m aluminum h y d r i d e was added dropwise w i t h c o n s i d e r a b l e s t i r r i n g a s o l u t i o n o f 0.2 g. produot A i n 5 ml. p u r i f i e d and d r i e d  ether.  -28-  After 2 0 minutes of refluxing the reaction vessel was cooled i n ice water and water was added slowly to destroy any complex and any unreaoted hydride.  l i t h i u m aluminum  Ether was added to compensate f o r any ether  l o s t i n the r e f l u x i n g and was followed by the addition of 3 ml. concentrated  sodium potassium t a r t r a t e 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 r e o r y s t a l l i z e d from ethanol gave white needle l i k e c r y s t a l s m.p.  122-122°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.  A f t e r 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.  R e c r y s t a l l i z a t i o n from  ethanol gave white c r y s t a l s m.p. a: mixed melting point of  119-112.5°C.  119ir-122.5  which gave  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.  P r e c i p i t a t i o n took place and 21 drops con-  centrated sulphuric acid at 60^3. dissolve the p r e c i p i t a t e .  were required to  The green solution  was  f i l t e r e d leaving behind 0.0117 g. of orange precipitate (10$ y i e l d ) .  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 p r e o i p i t a t i o n took place.  The orange precipitate produced did not reo r y s t a l l i z e from ethanol and did not dissolve i n l i g r o i n . It started to melt at 125°C. and c r y s t a l s 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 t a r formation.  A  nitrogen determination by the sodium fusion method (50) gave a p o s i t i v e test for nitrogen.  The product  appeared to slowly polymerize i n the presence of a i r . 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  s t i r r i n g at 60°C. f o r 24 hours.  At the end of t h i s  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 u n t i l a t o t a l of 67 hours had passed.  The  o r i g i n a l product was recovered. Oxidation of 2 - - n a p h t h y l )-4-methylbenzo fbj quinoline (Compound A) to y i e l d 2-(ff-naphthyl )-4-formylbenzo[h]quinoline  (Compound S)  To a semimioro three necked f l a s k equipped with a s t i r r e r was added 0.2553 g. product A.  The f l a s k was  heated to 180°C. with s t i r r i n g and at t h i s  temperature  0.0904 g. of pulverized selenium dioxide was slowly o added and the mixture heated f o r 15 minutes at 180-200 C. The reddish brown viscous syrup produced was repeatedly extracted with d i e t h y l ether to form a bright yelloworange solution.  The ethereal solution was dried over  calcium chloride and the ether evaporated o f f to y i e l d 0.2166 g. of bright yellow produot. P u r i f i c a t i o n of the oxidized produot The product was dissolved i n 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 ) 1.  300  ml.  CcHg-  2. 1250  ml.  C H -  ether (1:3 6  pet.  0.0555 S« colourless crystals  pet.  0.0102 g» brown c r y s t a l s  v:v)  6  ether (1:3  Fraotions and Weight ( i n grams)  v:v)  3. 2300 ml. C H - pet. ether (1:3 v:v)  0.0476 g- bright yellow crystals G  4.  0.0288 g» orange tarry residue  6  850  ml.  6  C H 6  5.  pet.  6  ether (1:1  v:v)  500 ml. Ethanol  Total recovery was proved  brown residue  0.0661  0.2022  g. or 93.4$.  Zone 1  to be the o r i g i n a l 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 r e c r y s t a l l i z e d from l i g r o i n (b.p. 100-120°C.) to give bright yellow c r y s t a l s *  m.p.  139-142.5°G. Anal, oalcd. f o r C24I15ITO: H, 4 . 2 0 ;  0, 4.80;  Mol. wt. 333.4.  H, 4.68;  N, 4.18;  0,  4.7.  C, 86.6; Found:  H,  4.51;  C, 86.26;  -42-  Infrared  spectrum  of G with  KBr  (om.  ):  2940(S),  2870{M),  1700(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),  827(W),  815(M),  798(W),  The y e l l o w solution of  having  conoentrated  the  a vivid  gave  greenish  alcoholic  of the basic  to restoration  compound  gave a  negative  test  hydroxylamine ance  product  with  170-185°C.  without  of  (compound  hydroxide  solution. oaused  oxime  G) w i t h  g.  of  acetic  acid  The  and  a  Treatment  disappear-  the formation i n the  with  of  a  range  oxide  to yield  2-((3-  (oompound  H)  2-(^-naphthyl)^4-formylbenzo-  drop  an ammoniacial  oxide  neutral-  immediate  melting  silver  dissolved  silver  oaused  2-(^-naphthyiJ-4-formylbenzo[h]quinoline  0.0076  drop  Addition  recrystallization.  fh]quinoline by  or  glacial  naphthyl-4-oarboxybenzo[h3quinoline To  yellow  colouration.  c o l o u r a t i o n and  crystalline  707(W).  Tollen's test  Pehling's  oolourless  Oxidation  rapid  852(M),  fluoresoence.  with  of the yellow  hydrochloride  of the yellow  a bright  Aoidification  solution  fairly  712(W),  potassium  colour to disappear.  ization led  745(S),  882(M),  i n 10  ml. ethanol ethanolio  (0.022 g. AggO).  was  added  solution  R e f l u x i n g was  of oarried  (14)  -43-  out for three hours and the solution allowed to stand overnight.  A f t e r making the solution basic with  potassium hydroxide •oxide '  was  i n alcohol the coagulated  f i l t e r e d to give a pale yellow  A s i l v e r mirror had formed i n the f l a s k .  silver solution.  The  solution was neutralized with g l a c i a l acetic acid, evaporated  to dryness and the residue extracted with  chloroform.  R e c r y s t a l l i z a t i o n of the residue from  isoamyl aloohol was unsuccessful but a f t e r removal of the solvent a c r y s t a l l i n e residue resulted whioh melted i n the range 220-862°C. Attempted decarboxylation of 2-(fl-naphthyl)-4-oarboxybenzoLhJ quinoline The  2-(^-naphthyl)-4-carboxybenzo[h]quinoline  was r e o r y s t a l l i z e d from ethanol to give a c r y s t a l l i n e product melting i n the range 125-140°C. (mainly the unoxidized aldehyde).  The produot a f t e r being refluxed  i n ethanol f o r 6 hours was freed of solvent and the residue dissolved i n 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 l i g h t pet. ether-benzene  pale brown o i l  1 mg.  2.  390 ml. 2:1 l i g h t pet. ether-benzene 220 ml. benzene  greenish yellow orystals  2 mg.  2.  120 ml. ethanol  brown wax  1 mg.  The contents of zone 2 proved to be unreacted aldehyde.  Attempts to c r y s t a l l i z e zone 2 from  ethanol were unsuccessful.  The product of zone 1 was  r e c r y s t a l l i z e d from ethanol to give a mass of white fluffy crystals.  This product appeared greasy at  room temperature and melted over a range of 25-50°G. The amount of substance isolated was l e s s than a milligram and was not worked with further. Sodium Hydroxide fusion of 2-(g-naphthyl)-4-methylbenzorh] 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 i n order to absorb any ammonia which might be produced. The test tube and contents were heated f o r s i x hours in a sand bath at 250°C, oooled, and the contents  -45-  dissolved i n 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 p r e c i p i t a t e which was repeatedly extracted with ethanol.  The remaining  residue proved to be inorganic by the flame t e s t . The aqueous solution was evaporated down and also extracted with ethanol.  The o r i g i n a l residue l e f t  a f t e r dissolving the solid basic mixture i n water was r e o r y s t a l l i z e d to give back product A i n 60$ y i e l d . The ethanolic extraot gave a small amount of i n t r a c t 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 hydroc h l o r i c acid to give a bright yellow insoluble s a l t . 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.  D i l u t i o n of the acid with  water resulted i n the l o s s of the pink colouration and a greenish-yellow precipitate formed.  With formic  acid Immediate dissolving took place to give a yellow solution.  D i l u t i o n of t h i s solution with d i e t h y l  ether resulted i n the l o s s of colouration and i n the p r e c i p i t a t i o n of a colourless compound.  -46-  Reaotion  of  with  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  dry  hydrogen  chloride The by  passing  ethereal yellow  chloride  to y i e l d  hydrochloride salt dry  hydrogen  copious  of  of  chloride  product  precipitate  to  which  give was  dry  desiccator  over  phosphorus pentoxide  collected  A was  the  Heating hydrogen  ethanol;  efficient 3160  having  the  salt  an  dry Immediate  filtered, in a  washed  vacuum  and  potassium  bright  yellow  a  greenish  at  o h l o r i d e and  (4.47),  dissolved titrated  2870  the  i n 90% The  of  deep  salt  90-100°G. the  the  ( l o g molar  (4.23),  original  product  3660  HG1  salt  of A  extinction  (4.14),  in  co-  3460  (4.04),  (4.49).  dried  against  indioator. 314.3;  3920  i n 90%  hydroxide  spectrum  angstroms  ):  Of  be  a  a  made  recovered. Ultraviolet  95%  dried  whereupon  i n high yield  fluorescence. released  hours  and  A was  through  with  f o r 48  ether  A  produot  repeatedly  was  hydro-  salt  solution  hydroxide  the  product  ethanol a  and  a  known w e i g h t  aliquot  p o r t i o n s were  standard,solution of  ethanol  potassium  using phenolphthalein  molecular  Theoretical,  was  weight  307.4.  o f A was  as  found  to  -47-  Reaction of 2-(g-naphthvl)-4-methylbenzo[hjquinoline with methyl iodide to y i e l d the methiodide  salt  The methiodide salt was prepared (24) by dissolving 0.082 g. produot A i n 3 ml. methyl iodide and adding to a thick walled tube which was sealed. It was heated f o r 170 hours at 100°C., cooled, wrapped i n metal f o i l , and kept under r e f r i g e r a t i o n f o r several days.  Black orystals formed which were removed from  the tube and washed with dry diethyl ether (40$ y i e l d ) , m. 182-184°G.  After evaporation of the methyl iodide  solvent there remained pale yellow c r y s t a l s which a f t e r r e c r y s t a l l i z a t i o n from ethanol proved by mixed melting point to be the o r i g i n a l product A (0.049 g.). Anal, oalod. f o r JS 3.24;  I, 29.5.  N, 3.26;  I, 31.26.  t  G  2 3  Pound:  H  1 8  NI:  G,  G, 57.12;  65.7; H, 3.92;  H, 5.98;  Reaotion of 2-(ff-naphthyl)-4-methylbenzo(h] quinoline with pidrio aoid to y i e l d the picrate derivative ( 6 0 ) To 3 ml. ethanol was added 0.041 g. p i c r i c acid and the p i c r i c acid solution was i n turn added to 0.052 g. compound A dissolved i n 3 ml. ethanol.  A  copious yellow p r e c i p i t a t e formed immediately which was dissolved by d i l u t i n g the mixture up to 250 oo. with 95$ ethanol and r e f l u x i n g .  Refluxing was carried on  for f i v e hours after which the ethanolic solution was allowed to stand and cool.  The c r y s t a l l i z e d product  -48-  was f i l t e r e d and r e c r y s t a l l i z e d from 95$ ethanol to give G.068 g. (75$) bright yellow c r y s t a l s , m.  223-  236°G. Anal, calcd. f o r C H, 3.67; Pound:  BT, 10.22; G, 63.63;  H N 0 ; 30 20 4 7  0, 20.04;  H, 3,59;  Attempted reaction of  N,  G,  66.0;  Mol. wt. 549.4. 9.99.  2-(g-naphthyl)-4-methylbenzo[h]-  quinoline with maleic anhydride  (39)  To 2 ml. benzene was added 0.23  g. f r e s h l y  d i s t i l l e d maleic anhydride and 0.0792 g. product A. The solution was refluxed under anhydrous conditions for eight hours.  When the reaction had copied more  benzene was added and dry hydrogen chloride passed through. was  A bright yellow p r e c i p i t a t e formed which  separated from the solvent and treated with sodium  acetate i n b o i l i n g acetone to decompose the s a l t . After f i l t e r i n g o f f the inorganio salt and evaporating down the solution a yellow o i l formed which s o l i d i f i e d on cooling, m. 117-124 C. G  A r e c r y s t a l l i z a t i o n from  ethanol yielded a compound m. 122-125°C.  A mixed  melting point with product A was at 121-124°G. Characterization of 3-methylbenzo[fjphthalimidlne (oompound B i ) (portion collected from chromatography of mixture i v ) Yield 14$.  This f r a o t i o n was t r i t u r a t e d with  -49-  suocessiVe  portions  leave  behind  which  was  was  traoe  very  soluble acetic  acid,  The  pale  1  65-75°C.  resinous  brown  and  from petroleum  syrup  recovered  a  3310(H),  isoamyl  benzene.  Attempts  ether-benzene  resulted only  using  to  material  3-pentanone,  chloroform  spectra  (omT ):  diso  b.p.  d a r k brown  ether-chloroform  Infrared NaCl  of  i n methanol,  reorystallization  petroleum  on  ligroin,  disoarded.  aloohol, at  a  of  GHClg  in oiling  deposited  3050(W),  or out.  film  3005(W),  2960(W),  2905(W),  1628(S),  1598(W),  1560(3),  1608(H)  1452(W),  1375(W),  1272(W),  1245 W ,  1217(S),  1177(W),  1127(f),  1017(W),  950(W),  752(S),  a o e t y l a t i p n was  0.023 g.  added  B  0.037  allowed  to  contents  i n 0.70  g.  fused  reflux  were  agitated. brown  The  residue  water  solution  was  removed  product  which  white  carried dry  acetic  s i x hours.  815(M),  and  the  and  i n low  the  ether  water.  mixture  The  the ether  chloride  recover  which  the  greasy  0.0125  from methanol  yield  was  vigorously  and  calcium to  was  and  decanted  evaporation  follows:  cooling  was  anhydrous  as  After water  in diethyl  B  anhydride  ice cold  recrystallized  crystals  on  into  over by  out  sodium a c e t a t e  washed w i t h  dried  ether  faint  ml.  dissolved  solution  of  for  poured  ethereal  the  855(M),  665(W). An  To  890(W),  f  and g.  giving  presumably  -50-  were the acetate derivative as shown by infrared analysis. Infrared spectra of acetylated B using a CH01 deposited f i l m on HaCl disc (cmT ): 1  3  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 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 of mixture i i i . Yield dfo.  f i g . 4)  This o r y s t a l l i n e component was  r e c r y s t a l l i z e d from a benzene-ethanol mixture and then from chloroform to give white flake l i k e c r y s t a l s , m. 218-239°C. Anal, oalod. f o r C^B^NO: N, 7.10.  Mol. wt., 197.3.  H, 6.23;  U, 6.97.  Found:  C, 78.8;  H, 5.65;  G, 77.90;  Infrared spectrum i n KBr (cmT ): 1  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-  Ultraviolet angstroms  ( l o g molar  3500(Sh)  (2.598J,  (3.695),  2825  2280  speotrum  extinction  3160 (3.064),  2925(Sh)  (3.790),  2720(Sh)  (2.750),  2270  (4.604),  collected  from  of C (portion of mixture  12$.  r e s i n o u s wax.  (1.22  g. i n 2 ml.) and added mm.  x 52 mm.  I t was  diameter)  6  g  ml. C H  and e l u t e d  f i b  The seoond  soluble acetic a  acid.  was n o t worked  (11% o f the t o t a l ) isoamyl  chloroform-petroleum ether  201-207°C.  alcohol  Recrystallizationwas  to give  as  column  >  follows:  0.82 g . p a l e b r o w n residue  fraction  fraction  i n benzene  0.22 g . d a r k b r o w n residue  v:v)  i n 2-pentanone,  ohloroform m.  first  dark  F r a c t i o n s and Weight ( i n grams)  : EtOH ( l : l v:v)  A  b  r e c o v e r e d was a  t o an alumina  t-BuOH  (98:2  f i g . 4)  dissolved  Effluent Fractions (in millilitres) ml. C H :  i i .  The f r a c t i o n  brown  The  ):  (4.592).  Yield  200  coefficient  (3.100),  chromatography  1700  i n 95% e t h a n o l ;  3205  Characterization  (120  of B  a white  solvent  with  was and  further.  very glacial  accomplished and t h e n  crystalline  C  from  from  produot,  -52-  Anal. calcd. for ^i^lZ^Z *' 0  H, 6.00;  U, 14.00;  0, 8.00.  H, 6.02;  14.12;  0, 8.02.  c  » 70.1;  Found:  C, 71.35;  -1 Infrared spectrum i n 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 i g . 3) Yield 7%.  After three reprystallizations  from 3-pentanone the compound melted at 204-205.5°C. It was soluble in alcohol, insoluble i n benzene, diethyl ether or l i g r o i n and oould be recrystallized from chloroform. Anal, oalod. for OigHj^NgO:  G, 72.8;  N , 13.1;  0, 7.46;  Mol. wt,, 214.3. Found:  H, 6.62;  N , 13.1;  0, 7.81;  H, 6.58; C, 72.6;  Mol. wt. (last) 301.  The molecular weight determination was l i k e l y in error as the oompound reacted with camphor to give a red produot.  -53-  Infrared spectrum of C i n KBr (cm. ): 3250(S),  3230(M), 3070(W), 2990(W), 2930(W),  3430(S),  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).  U l t r a v i o l e t spectrum of C i n 95$ ethanol; angstroms (log molar extinction c o e f f i c i e n t  ):  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 o r i g i n a l c r y s t a l l i n e product collected from the chloroform c r y s t a l l i z a t i o n gave a positive f e r r i c chloride test and slowly became brown upon standing giving o f f a putrescent odour even at -10°C. under vacuum and i n the absence of l i g h t .  The  o i l y component produced was e a s i l y separated from the c r y s t a l l i n e compound C by chromatography  on alumina.  The .degraded oompound did not give a f e r r i c chloride test.  Prolonged refluxing f o r s i x days with mercuric  oxide i n chloroform (31) gave no apparent Oompound C behaved  change.  I n d i f f e r e n t l y to proton donating  solvents although blackening took place i n concentrated sulphuric aoid.  -54-  Charaoterlzatlon (Yield No  attempt  was  Z%;  was  soluble  o f Oompound a pale  made  D.  yellow  sweet  to crystallize  i n ethanol  and  smelling  this  benzene,  syrup).  fraction.  poorly  It  soluble  in  ligroin. Infrared  spectrum  of D  2915(S),  2850(S),  1632(W),  1600(W),  1270(W),  1125(W),  1020(W),  958(W),  854(H),  817(S), An  hydrazone  yield  4$.  A  from  standing  several  soluble  acetic  aoid,  ligroin  NaCl  the  947(W),  1380(H),  890(W),  small  a  was  d a r k brown  206-233°C. isoamyl  and  resinous  successfully  s o l u t i o n b. 100-120°G.  i n ethanol, ohloroform  was  crystal  m.  days,  2,4-dinitrophenyl-  E  recovered  a ligroin  The  alcohol,  benzene.  after  fraction  was  3-pentanone,  It oiled  out o f  solutions. Infrared  on  1460(S),  unsuccessful.  o f Compound  fraction  isolated  very  to prepare  d e r i v a t i v e was  Characterization  wax,  3060(W),  1  747(S).  attempt  The  (cmT ):  i n KBr  diso  spectrum  (cm: ): 1  using  3060(W),  a  CHClg  3020(H),  deposited  film  2960(S),  2920(S),  2860(M),  1710(8),  1675(H),  1635(W),  1600(W),  1533(H),  1508(H),  1455(M), 1405(W),  1377(W),  1353(H),  1515(W),  1273(W),  1245(W),  1182(W),  U42(W),  1128(W),  1019(W),  953(W),  668(H).  1217(S), 890(W),  855(W),  820(H),  760(S),  -55-  A small amount of the f r a c t i o n was dissolved i n ethanol and 2,4-dinitrophenylhydrazine i n ethanol was added along with two drops concentrated sulphuric acid and the solution refluxed.  A f t e r standing overnight a  minute amount of red p r e c i p i t a t e appeared which melted over a wide range being o i l y at room temperature and containing o r y s t a l l i n e solid at temperatures  above 2G0°C.  Characterization of Compound F Yield 5%.  This f r a c t i o n was t r i t u r a t e d with  successive portions of l i 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 i n methanol, 3-pentanone, isoamyl alcohol, acetic acid, chloroform and benzene.  Attempts at re-  c r y s t a l l i z a t i o n from petroleum ether-benzene or petroleum ether-chloroform resulted only i n o i l i n g out. Infrared spectra using a CBXJlg deposited f i l m 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)  Reaotion oxime  of to  2-acetonaphthqne yield  with  2-acetonaphthone  2 - ( f f - n a p h t h y l ) - 4 - m e t h y l b e n z o [h]  quinoline Into  a  glass liner  2-acetonaphthone  oxime,  naphthone  ml.  into Hg  an  10  autoclave  pressure.  235°C. 90-10 in  and  for  The  90  When  solid  state,  itself  outside  the  A  portion  of  dissolved column  in 4  (35  carried  out  0.1896 g. violet  mm.  ml.  of  graphic  behaviour  was  the  the  x  and  placed  1.0  mm. at  rose  were  to  recovered  having  120  which that  methylbenzofh]quinoline.  solid  developed mm.).  benzene-ligroin  to  m.)  rocked  pressure  solvent  was  to  and  contents  recovered  benzene  and  liner  heated the  (0.01  removed  liner.  m a t e r i a l which  radiation  2-aceto-  evacuated  benzene  diameter  with  m.)  system  whereupon  the  g.  The  cooled  to  (0.01  1.85  benzene.  the  minutes  placed  g.  autoclave  p.s.i.  the  1.70  dry  and  was  g.}  on  alumina  an  Elution  (1:1,  fluoresced exhibited  shown b y The  (0.701  v:v)  was  was  to  under  recover  ultra-  identical  chromato-  2-(^-naphthyl-4-  remaining  zones  were  discarded. The ether  and  ethereal  recovered  dry  hydrogen  solution  Filtration  of  compound  the  to  was  dissolved  c h l o r i d e was  precipitate  yellow  salt  and  a  passed  in  through  bright yellow removal  dry  of  the  the salt. ether  -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 s a l t .  The bright yellow salt was de-  composed by dissolving i n acetone and adding sodium acetate (39) whereupon the yellow colouration disappeared rapidly.  The acetone was removed by  evaporation and the residue dissolved i n 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  r e c r y s t a l l i z e d from ethanol to give a white c r y s t a l l i n e 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 i d e n t i c a l 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.  A u w e r s , K.  and Meyer, V.;  2.  B a o h m a n , W. E . a n d B a r t o n , S i s t e r M. J . O r g . Chem. 3, 3 0 0 - 1 1 ( 1 9 3 8 ) .  3.  Barbot;  4.  Beckmann,  E.;  B e r . 1 9 , 988  5.  Beckmann,  E.;  B e r . 20. 1507,  6.  : Beckmann,  E.;  B e r . 22, 514  Bull.  s o c . chim.  B e r . 2 2 , 7G5  (1889).  Xaveria;  47, 1318 ( 1 9 3 0 ) . (1886) 2580 ( 1 8 8 7 ) .  (1889) •  7.  Ibid.,  1531.  8.  B i l l m a n , J . H. a n d T a i , K. M. ; 535-9 ( 1 9 5 8 ) .  9.  Brady,  0. L . ;  J . Chem. S o o .  J . Org.  Chem. 2 3 ,  1931, 105-7.  10.  Briner, E. Susy, 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 . a n d D w y e r , P . P.; J . Proc. U.S. W a l e s 74, 1 0 7 - 9 ( 1 9 4 0 ) .  12.  Buckley,  t  G. D.  1949.  a n d R a y , N . H.;  Roy.  S c i .  J . Chem. S o c .  1151-4.  13.  Ibid.;  1154-6.  14.  B u r g e r , A . a n d M o d l i n , 1 . R., J r . ; Chem. S o o . 6 2 , 1 0 7 9 ( 1 9 4 0 ) .  15.  Buu H o i and C a g n i e n t , 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 v o l . V I , p . 453 ( 1 9 3 0 ) .  17.  C o l b y , C . E . a n d D o d g e , P . D.; Soo. 13, 1 (1891).  18.  Davies, 20,  19.  E d w a r d s , 0. E . a n d S i n g h , 32, 683 ( 1 9 5 4 ) .  M. a n d E v a n s , 342 ( 1 9 5 2 ) .  P.;  Bull.  J. C ;  T.;  J . Am.  s o c . chim.  Chemistry.  J . Am.  J . Chem.  Ghem.  Phys.  C a n . J . Chem.  -59-  2G.  I l d e r f i e l d , R. G., Heterocyclic Compounds, v o l . IV, New York, John Wiley & Sons, 1957.  21.  Emmett, P. H.; Catalysis, v o l . V, New York, Reinhold, 1957, pp. 1-130.  22.  Pieser, L. P.;  Experiments i n Organic Chemistry,  2nd ed., D. C. Heath & Co., 1941, pp. 360-2. 23.  Ibid.;  24.  Peigel, P.; I I Spot Tests i n Organic Applications. New York, E l s e v i e r , 1954, p.224. Pieser, L. P.; Experiments i n Organic Chemistry.  25.  p. 363.  3rd ed., D. C. Heath & Co., 1955, p.209. 26.  Gabriel, S.;  27.  Goldschmidt, H.;  28.  Goulden, J . D. S.;  29.  Hantzsoh, A. and Werner, A.;  30.  Hantzsch, A.;  31.  Harries, C. and Jablonski, Ludwig; Ber. 31, 1379 (1898). Hartwell, E. J . , Richards, R.E. and Thompson, H.W.; J. Chem. Soc. 1948. 1436. Hieber, W. and Leutert, P.; Ber. 60B, 2296-310  32. 33.  Ber. 18, 1251, 2433 (1885). Ber. 16, 2176 (1883). J . Chem. Soo. 1953. 997. Ber. 23, 11 (1890).  Ber. 24, 13 (1891).  (1927). 34.  Ibid.;  2310-7.  35.  Hieber, W. and l e u t e r t , P.;  36.  Hieber, W. and Wiesboeck, R.;  Ber. 62B, 1839 (1929). Ber. 91,  1146-55 (1958). 37.  Ibid.;  38.  Hunsberger, I. M.; J . Am. Chem. Soc. 72, 5626 (1950). Johnson, W.S. and Matthews, P. J.; J . Am. Ghem. Soc. 66, 210 (1944).  39.  1156-61.  -60-  40.  Kirrmann, A. and Laurent, P.; chim. 6, 1657 (1939).  41.  Kbdama, S., Nose, S. and Tdmilisa, N.• Japan 5519 (1956). Chem. Abstr. 52: 11901° (1958).  42.  Letaw, H., J r . , and Gropp, A.H.; Phys. 21, 1621 (1953).  43.  Meisenheimer, J.;  44.  Meisenheimer and Thielacker i n Freudenberg's Sterioohemie. Deutloke, L e i p z i g & Vienna (1933), pp. 1039 f f .  45.  Meisenheimer, J., Zimmerman, P. and Krummer, U. V., Ann. 446, 205 (1925).  46.  Murahashi, S.; J . Am. Chem. Soo. 77, , 6403-4 (1955).  47.  Murahashi, S. and H o r i i e , S.; Soo. 78, 4816-7 (1956).  48.  Nakamura, A. and Hagihara, N.• Mem. Inst. Ind. Research, Osaka Univ. 15, 195-9 (1958) of Chem. Abstr. 53, 1197 (1959).  B u l l . soo.  J . Chem.  Ber. 54, 3206 (1921).  J. Am. Chem.  h  49.  Nienburg, H. J . and Keunecka, E.; Germany 865, 799 (1955) of Chem. Abstr. 48: 1427h (1954).  50.  Openshaw, H.T.; A Laboratory Manual of Qualitative Organic Analysis, Cambridge, 1946, p. 4.  51.  Piero, P.;  52.  Pino, P. and Magri, R.; Ghimioa e i n d u s t r i a (Milan) 34, 511-17 (1952). Chem. Abstr. 47, 10492S (1953).  53.  Priohard, W. W.; 6137 (1956).  54. 55.  Ital.  471,913 (1952).  48, 7627gTl954).  Chem. Abstr.  J . Am. Chem. Soo. 78,  Chem. Abstr. 52, ZOl97  h  (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 , Communioation, 1959.  57.  R u z i k a , L . , De G r a a f , G. B . R. a n d 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.  Sahni,  59.  S c h r i n e r , R. 1 . a n d 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 , 1 9 4 8 , p . 9 1 .  60.  Ibid.;  p . 180.  61.  Ibid.;  p. 202.  62.  S e i t z , F.;  63.  Shaw, J . T . a n d T y s o n , F . T . ; S o c . 78, 2538 ( 1 9 5 6 ) .  J . Am.  64.  Stephen,  J . Chem. S o o .  R.  C;  and B l e l o c h ,  Private  Soc. 49, 1  (1953).  (1889).  Wm.;  Chem.  886-95.  65.  Stobbe,  H.;  66.  Taylor,  T . W.  C. R.,  Faraday  B e r . 22, 257  H.  1931,  Trans  J.;  B e r . 3 5 , 911 J . , Callow,  (1902). M r s . N . H. a n d  Francis,  J . Chem. S o o . 1 9 3 9 , 2 5 7 - 6 3 .  67.  Tschagaeff, L.;  68.  T y s o n , F . T . a n d Shaw, J . T . ; J . Am. Chem. S o c . 74, 2293 ( 1 9 5 2 ) . 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 Chemioal A n a l y s i s . Longmans, T o r o n t o , 1952, p . 204.  69.  B e r . 3 9 , 2672  (1906).  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 . IX. Chemical A p p l i c a t i o n s o f Spectrosc o p y , New Y o r k , I n t e r s c i e n c e , 1 9 5 6 , p . 5 1 7 - 8 .  71.  W e n d e r , I . , G r e e n f i e l d , G. a n d O r o h i n . J . Am. Chem. S o c . 7 3 , 2 6 5 6 ( 1 9 5 1 ) .  72.  W h e l a n d , C. W., A d v a n o e d O r g a n l o Chemistry. 2 n d E d . , New Y o r k , J o h n W i l e y & S o n s , 1949, p . 337.  73.  Zeohmeister, L. and Truka, 2883-4 ( 1 9 3 0 ) .  J.;  M.;  B e r . 63B,  -62-  V.  ADDENDUM  1-((?-Naphth.yl ) e t h . y l u r e a Compound now  been  C  ( s e e exp. p.51  tentatively established  l-(^-naphthyl)ethylurea melting which  point  point  elemental the  analysis  postulated  C was  agreement  o f 198°C.  and  t o be  found with  oxime .  d i s c . p.22) has raoemic  on t h e f o l l o w i n g  o f oompound  i s i n excellent  melting  from 2-acetonaphthone  bases:  t o be the  the  196-198°C.  literature  f o r 1-(^-naphthylJethylurea (75),  (see exp. p.52) i s i n agreement  structure  CO C  as  shown  with  below:  I • CHNHCONH„  ( d , l form) -1  infrared  analysis  are  attributed  N-H  of a  shows p e a k s  t o t h e N-H  a t 3430  and 3550  cm.  which  i n a p r i m a r y amide -1 , V (76). U r e a s h o w s p e a k s a t 3 4 3 4 a n d 3 3 7 6 cm. ( 7 4 ) and -1 b e n z y l u r e a s h o w s p e a k s a t 3 4 4 0 a n d 3 3 2 8 cm. (56). The -1 p e a k a t 5 2 3 0 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 s e c o n d a r y amide  stretching  (76).  Furthermore, the peaks  -1 at the  1648  and 1537  amide  cm.  are attributed  I I bands ( 7 7 ) .  t o t h e amide  I and  -63-  A  suggested mechanism f o r the f o r m a t i o n  l-(^-naphthyl)ethylurea shown  Work the to  from E-acetonaphthone  of  oxime  i s  below:  i n our laboratory oximes  yield  undergo  some  have  shown  with  hydrogen  hydrolysis  ketone.  that  (56) has c o n c l u s i v e l y under  shown  that  the conditions  used  Furthermore, other  unsaturated  compounds  workers  undergo  i n the presence o f d i o o b a l t  (48)  reduction  ootacarbonyl.  -64-  BIBLIOGRAPHY  K e l l n e r , L.; P r o c . Hoy. Soo. London 447, 456 ( 1 9 4 1 ) .  177  Samuelsson, E.; T h e s i s , U n i v . Lund 1922, Chem. A b s t r . 1 8 : 1824 (1924). 1  W e i s s b e r g e r , A.; Technique of Organic Chemistry. 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 , Interscience, 1956, p . 5 1 1 , 514.  Ibid.;  p.521-2.  

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