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The action of carbon monoxide and dicobalt octacarbonyl on some aromatic oximes O'Donnell, Joseph Patrick 1959

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THE ACTION OP CARBON MONOXIDE AND DICOBALT OCTACARBONTL ON SOME AROMATIC OXIMES  by  Joseph P a t r i c k  O'Donnell  & THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF  MASTER OF SCIENCE  i n t h e Department of Chemistry  We a c c e p t t h i s t h e s i s a s c o n f o r m i n g t o t h e r e q u i r e d standard  THE UNIVERSITY OF BRITISH COLUMBIA  July, 1959  (ii)  Abstract  When syn-benzaldoxime was r e a c t e d w i t h carbon monoxide c o n t a i n i n g about 0.04 volume p e r c e n t o f hydrogen and d i c o b a l t o c t a c a r b o n y l i n benzene s o l u t i o n a t e l e v a t e d temperatures f o l l o w i n g compounds were produced; sym-dibenzylurea b e n z y l u r e a (10$) and benzaldehyde (10$).  and p r e s s u r e s t h e  (35/0,  mono-  A l s o i s o l a t e d were 15$  y i e l d s o f two u n i d e n t i f i e d components r e f e r r e d t o as compounds A and B.  When benzophenone oxime was s u b j e c t e d t o t h e same r e a c t i o n c o n d i t i o n s t h e major p r o d u c t was 3 - p h e n y l p h t h a l i m i d i n e  (75$).  Also  i s o l a t e d was a 5% y i e l d o f an u n i d e n t i f i e d component c a l l e d compound B.  I t was demonstrated t h a t under t h e r e a c t i o n c o n d i t i o n s u s e d  con-  s i d e r a b l e amounts o f d i c o b a l t o c t a c a r b o n y l a r e needed f o r s u c c e s s f u l reaction.  When t h e o c t a c a r b o n y l was p r e s e n t i n o n l y c a t a l y t i c amounts  the c o u r s e o f t h e observed  r e a c t i o n was g r e a t l y a f f e c t e d and t h e major  i s o l a t e d p r o d u c t was benzophenone (70$). 3-phenylphthalimidine  S m a l l amounts o f  and o f t h e o r i g i n a l oxime were a l s o i s o l a t e d .  When t h e 0-methyl e t h e r o f benzophenone oxime was r e a c t e d the o n l y p r o d u c t i s o l a t e d was 3 - p h e n y l p h t h a l i m i d i n e i n 75$ y i e l d .  R e a c t i o n p r e s s u r e s c o r r e c t e d t o c o n s t a n t temperature a r e p l o t t e d a g a i n s t r e a c t i o n time f o r each s u b s t r a t e and t h e r e s u l t s discussed.  (iii)  A new  method o f s y n t h e s i z i n g the O-methyl e t h e r o f benzo-  phenone oxime ( u s i n g O-methyl h y d r o x y l a m i n e ) , a c i d o x i d a t i o n o f sym-dibenzylurea are d e s c r i b e d .  and a d i c h r o m a t e - a c e t i c  g i v i n g a high y i e l d of dibenzoylurea  A platinum oxide i n a c e t i c a c i d reduction o f  3-phenylphthalimidine  which reduced  b o t h benzene r i n g s but l e f t  the  l a c t a m group i n t a c t i s a l s o d e s c r i b e d .  I n f r a r e d s p e c t r a are i n c l u d e d f o r a l l compounds o b t a i n e d .  In the  presenting  requirements  of B r i t i s h it  this thesis  f o r an  Columbia,  freely available  agree that for  copying  gain  shall  Department  or  his  for reference  and  study.  I  for  extensive be  copying  granted  representatives.  not  be  of  Chemistry  of  by It  this thesis  a l l o w e d w i t h o u t my  Columbia,  of  the  of  University shall  publication  J u l y 20, 1959  the  Library  The U n i v e r s i t y o f B r i t i s h V a n c o u v e r 6*, C a n a d a . Date  degree at the  p u r p o s e s may  D e p a r t m e n t o r by that  advanced  fulfilment  I agree that  permission  scholarly  in partial  make  further this  Head o f  thesis my  i s understood for financial  written  permission.  Acknowledgement  The writer wishes to express h i s 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 o f t h i s research project.  The writer also wishes to thank Dr. J  e  Halpern f o r h e l p f u l discussion o f reaction pressure plots.  Table o f Contents  Page T i t l e Page  (i)  Abstract  (ii)  Acknowledgement  (iv)  T a b l e o f Contents  (v)  L i s t of Figures  (viii)  I. . H i s t o r i c a l I n t r o d u c t i o n  1  A.  R e a c t i o n s o f oximes  1  B.  Isomerism o f oximes  1  C.  R e a c t i o n s o f carbon monoxide  2  D.  D i c o b a l t o c t a c a r b o n y l and r e l a t e d compounds  6  E.  H y d r o f o r m y l a t i o n - t h e oxo r e a c t i o n  11  F.  Carbonylation  14-  G.  Reactions r e l a t e d to hydroformylation  16  H.  R e a c t i o n s i n v o l v i n g carbon monoxide. w i t h n i t r o g e n compounds  I.  R e a c t i o n s o f carbon monoxide i n v o l v i n g r i n g formation  II.  17  Discussion  20  25  R e a c t i o n s o f carbon monoxide and d i c o b a l t octacarbonyl with A.  Syn-benzaldoxime  25  B.  Benzophenone oxime  30  (vi)  Page  III.  C,  0-methyl e t h e r o f benzophenone oxime  D.  D i s c u s s i o n of pressure p l o t s  3  4 35  39  Experimental A. G e n e r a l  3  9  B. R e a c t i o n o f syn-benzaldoxime w i t h carbon monoxide i n t h e presence o f d i c o b a l t o c t a c a r b o n y l a.  Preparation of reactants  4  b.  R e a c t i o n procedure  c.  S e p a r a t i o n and i d e n t i f i c a t i o n  d.  Repeat o f r e a c t i o n between carbon monoxide  AO 0 40  o f products  43  and syn-benzaldoxime i n t h e presence o f d i c o b a l t octacarbonyl  54  C. A c t i o n o f carbon monoxide on benzophenone oxime i n t h e presence o f d i c o b a l t o c t a c a r b o n y l  59  a.  P r e p a r a t i o n o f benzophenone oxime  59  b.  R e a c t i o n procedure  59  c.  S e p a r a t i o n and i d e n t i f i c a t i o n  d.  Repeat o f r e a c t i o n o f benzophenone oxime  e.  R e a c t i o n o f benzophenone oxime i n t h e  o f products  60 65  presence o f a s m a l l amount o f d i c o b a l t octacarbonyl  69  D. R e a c t i o n o f 0 - m e t h y l e t h e r o f benzophenone oxime i n t h e presence o f d i c o b a l t o c t a c a r b o n y l a.  71  P r e p a r a t i o n o f 0 - m e t h y l e t h e r o f benzophenone oxime  71  (vii)  IV.  b.  R e a c t i o n procedure  71  c.  S e p a r a t i o n and i d e n t i f i c a t i o n o f p r o d u c t s  72  Bibliography  76  (viii)  L i s t of Figures Page  1.  P l o t o f p r e s s u r e a g a i n s t time f o r t h e r e a c t i o n o f syn-benzaldoxime  v i t h carbon monoxide i n the presence  42  of dicobalt octacarbonyl  Chromatography o f syn-benzaldoxime  3.  I n f r a r e d spectrum o f compound A  46  4.  I n f r a r e d spectrum o f compound B  47  5.  I n f r a r e d spectrum o f s y m - d i b e n z y l u r e a compared w i t h t h a t of  r e a c t i o n products  44  2.  sym-dibenzoylurea  6.  I n f r a r e d spectrum o f mono-benzylurea  7.  I n f r a r e d spectrum o f 3 - p h e n y l p h t h a l i m i d i n e compared w i t h  49 55  t h a t o f i t s reduced p r o d u c t  64 8.  P l o t o f p r e s s u r e a g a i n s t time f o r t h e r e a c t i o n o f benzophenone oxime w i t h carbon monoxide i n the presence of d i c o b a l t octacarbonyl  66 9.  P l o t o f p r e s s u r e a g a i n s t time f o r the r e a c t i o n o f the O-methyl e t h e r o f benzophenone oxime w i t h carbon monoxide i n the presence o f d i c o b a l t o c t a c a r b o n y l  73  1  HISTORICAL INTRODUCTION  A.  Reactions of Oximes.  The Beckmann rearrangement workers. (47),  has been investigated by many  I t s generality and mechanism are now well established (23),  Catalysts f o r t h i s reaction include concentrated sulphuric acid,  phosphorous pentachloride, polyphosphoric acid (35)» chloride, boron t r i f l u o r i d e and benzenesulphonyl  (27), hydrogen  chloride.  Hydrolysis of an oxime w i l l regenerate the parent carbonyl compound.  Oximes are generally amphoteric and form well characterised  s a l t s of both types*  They are reduced by many agents to amines*  Aldoximes may be dehydrated to produce n i t r i l e s ; oximes w i l l form esters with common e s t e r i f y i n g agents.  This i s believed to be the  necessary f i r s t step i n the Beckmann rearrangement  B.  (47).  Isomerism of Oximes  Three d i s t i n c t types of isomerism are possible f o r oximes* F i r s t i s the geometrical syn and anti type where the hydroxyl can be c i s or trans to an i d e n t i f i a b l e r a d i c a l attached to carbon.  These  isomers have been i s o l a t e d i n the aromatic series but s i m i l a r i s o l a t i o n of pure compounds has not yet been achieved with a l i p h a t i c analogs (26), Second i s the oxime-nitroso tautomeric equilibrium.  T i l l recently i t  2 has been believed that this equilibrium was almost 100$ i n favor of the oxime form, for primary and secondary oximes (56).  However recent work  has shown that large scale preparation of many primary and secondary nitroso compounds i s possible (12), (7).  The opinion has been expressed  (16) that hydroxylic solvents and low concentrations favor formation of the oxime. Third i s the oxime-nitrone equilibrium.  Recent information  (9) indicates that oximes may normally exist i n equilibrium with a small percentage of the nitrone form.  Semper and Liehenstadt (45) isolated  four different methyl ethers when they treated benzaldoxime with methyl sulphate.  C.  0- and N- ethers were formed i n approximately equal amounts,  Reactions of Carbon Monoxide  The reactions of carbon monoxide have been reviewed recently by Orchin and Wender (33).  These authors show carbon monoxide can  react as a Lewis base, a Lewis acid, or as a free radical. As a base i t can react with carbonium ions according to the following scheme +  +  3 This carbonium ion can now react with nucleophilic reagents present i n the system to form esters, acids or anhydrides.  Anhydride  formation i s shown here  OHO II  RCKjCO  +  R COOH  it  i  R-CHg-^O-G-R  0 Hi  0 HI  RCEJC-O-C-R"  +  H  +  These reactions allow the formation of esters, acids, or anhydrides from olefins, alcohols, ethers and to a limited extent from ketones or aldehydes provided the conditions for formation of the appropriate carbonium ion are present i n the system. Carbon monoxide also acts as an electron acceptor though examples of this are less extensive.  The synthesis of sodium formate  i s an established example  6'::bV  +  OH"  H0:C:0r  Acid formation from alcohols i s known i n the presence of alkoxide ion  C H 0H 2  5  +  CO  HC00C H 2  5  4 Carbon monoxide reacts v i t h Grignard reagents; f o r example the reaction with t e r t - b u t y l magnesium chloride i s shown  0 ni  2(CH ) -G-MgCl 3  3  +  2C0  ^  (C^^fc-CHOB-CCCHj)  There are i s o l a t e d examples i n vhich carbon monoxide reacts by a r a d i c a l mechanism e s p e c i a l l y when photosensitized*  I t s reaction  with ammonia to produce formamide i s believed to proceed by such a mechanism,  MH  3  +  CO  >  HCONRj  However r a d i c a l s with a carbonyl group more commonly decompose according to the following scheme  RCH^CO  ^  RCH-  A r a d i c a l i n i t i a t e d copolymer!zation ethylene has recently been reported.  +  CO  of carbon monoxide and  Foster e t a l (14) report formation  of such a polymer i n c l u d i n g such chain t r a n s f e r agents as e t h y l mercaptan, carbon tetrachloride, and alcohols.  An unusual reaction discovered by Buckley and Ray (6) t r a t e s the reducing action of carbon monoxide.  illus-  When a n i l i n e containing  a small amount of a n i l i n e hydrochloride reacted at 250° C under 3000  5 atmospheres pressure carbon dioxide and a brown amorphous s o l i d were obtained.  This was shown to be a cross l i n k e d polymer of I.  I I t was believed t h i s intermediate was obtained by reduction of I I  ^  CH^  ^> NH  2  OH II which i n turn had been formed by condensation and rearrangement of two moles of formanilide.  The same authors found manyjorganic compounds  were reduced by carbon monoxide a t high temperatures and pressures with the formation o f carbon dioxide.  Without c a t a l y s t n l t r o , nitroso and  azoxybenzenes were reduced to azobenzene and phenylhydroxeylamine was reduced to a n i l i n e .  In the presence of Raney cobalt benzyl alcohol,  phenylmethylcarbinol and benzhydrol were reduced to the corresponding hydrocarbons.  Buckley and Ray also discovered a remarkable stepwise reduction to produce I I I  6  N n  -  N tii  HC.  /CH N  NE,  III  from carbon monoxide and h y d r a z i n e u n d e r extreme c o n d i t i o n s .  D.  may  Dicobalt octacarbonyl  I.  F o r m a t i o n and  The  formation  and  r e l a t e d compounds.  p r o p e r t i e s ( r e f 53,  of d i c o b a l t octacarbonyl  pp 89 t o  106)  from a c o b a l t  salt  be w r i t t e n i n the f o l l o w i n g manner  Hg  2H  +  +  2e 2Co  +  00(0^)2 +  This r e a c t i o n i s c a r r i e d out  as has  5*  +  Co  +  2e  +  2H0A  Q  SCO  ^  a t 160°  C using a s l u r r y of a cobalt  w i t h benzene under 3200 p . s . i . hydrogen.  2H  5?  o f a 111  Co (C0)g 2  m i x t u r e o f carbon monoxide  salt and  T h i s r e a c t i o n a c t u a l l y forms c o b a l t h y d r o c a r b o n y l (H Co(CO)^)  been proven by c o o l i n g the r e a c t i o n v e s s e l t o -51°  r e l e a s i n g the gas p r e s s u r e .  Dicobalt octacarbonyl  C  before  i s formed o n l y  on  7 r e l e a s i n g the p r e s s u r e a t room  temperatures.  Under a s l i g h t p r e s s u r e o f carbon monoxide the o c t a c a r b o n y l i s s t a b l e i n d e f i n i t e l y a t room temperatures. monoxide d e c o m p o s i t i o n  2 Co (C0) 2  I n the absence o f  carbon  t a k e s p l a c e a c c o r d i n g t o the f o l l o w i n g e q u a t i o n  >  8  C  %  (  C  0  )  12  +  4  0  0  The o c t a c a r b o n y l i s r e a d i l y s o l u b l e i n hydrocarbon s o l v e n t s but r e a c t s more o r l e s s r e a d i l y w i t h p o l a r s o l v e n t s such as a l c o h o l s , ketones,  amides and  The  amines.  tetramer,  (Co^GO)^)*  i  s  pyrophoric but  indefinitely  s t a b l e i n an i n e r t s o l v e n t .  Cobalt hydrocarbonyl  (HCo(CO) ), forms p a l e y e l l o w 4  s t a b l e below t h e i r m e l t i n g p o i n t (-26°  C).  crystals  Above t h i s temperature i t  decomposes r a p i d l y .  2 HCo(CO)^  +  Co (C0)g 2  I t i s a s t a b l e s t r o n g a c i d i n oxygen f r e e aqueous s o l u t i o n a t 25° may  be t i t r a t e d u s i n g p h e n o l p h t h a l e i n as an i n d i c a t o r .  The  G  accepted  e l e c t r o n i c s t r u c t u r e s f o r these compounds are shown below: ( I I I , IV)  and  8  0 It;  c  c  v  \/\/  0=C —Co C  /  c  Co-  \  /  C  C H-Co  C~-0 \  C  I V  c  Cx  G  IV  III  II..  Reactions  The r e a c t i o n s o f d i c o b a l t o c t a c a r b o n y l may  be c l a s s i f i e d  as  follows  (a)  Homomolecular d i s p r o p o r t i o n a t i o n  \ 3Cb (C0)g  +  2  B may formamide.  f o r m a t i o n may  00(00)^  CbBx  group B must be a L e w i s base and f u l f i l l Where B i s a p r i m a r y  geometric  o r secondary a l i p h a t i c amine  salt  take place according to the f o l l o w i n g equation  N B  +  be ammonia, water, methanol, e t h a n o l , p i p e r i d i n e o r  The  requirements.  xB  +  Co (C0)g 2  BCo(CO),  N,  00(00)^  SCO  H i e b e r and Wiesboeck  (21) examined  t h e p r o d u c t s when many n i t r o g e n bases  reacted with d i c o b a l t octacarbonyl.  They u s e d p i c o l i n e ,  quinoline,  p y r i d i n e , a n i l i n e and o t h e r s , and a r r i v e d a t t h i s g e n e r a l e q u a t i o n where B r e p r e s e n t s a m o n o f u n c t i o n a l n i t r o g e n base.  /Co(C0V  CoB,  12B  00(00)^  +  SCO  Formamide a l s o formed a compound o f analogous c o m p o s i t i o n .  Oxygen bases formed compounds o f d i f f e r e n t c o m p o s i t i o n . Acetophenone  f o r example r e a c t e d as f o l l o w s  0 n 3 (Co(CO) j A  +  ph-C-CH  0  it  y-f-  Co(ph-C-CHo)i-  3  Co(CO)^  These compounds were g e n e r a l l y formed n e a r 5  +  8C0  C and some c o u l d be des-  t r o y e d by r e f l u x i n g s l i g h t l y above room temperature i n l i g h t p e t r o l e u m ether.  (b) E x t e r n a l e l e c t r o n  transfer  D i c o b a l t o c t a c a r b o n y l w i l l r e a c t w i t h m e t a l l i c sodium o r hydroxyl i o n according to the f o l l o w i n g equations.  10  2 Na  +  2 Co(C0)  (c)  Co (C0) 2  8  +  8  40H"  Replacement  ^  ^  2 NaCo(C0)  4  Co(CO),  A  +  2^0  +  0  2  o f t h e c a r b o n y l group  I s o n i t r i l e s , the RS group o f mercaptans, been shown t o r e p l a c e one o r more c a r b o n y l groups.  and a c e t y l e n e have Acetylene f o r  example r e p l a c e s t h e two b r i d g e c a r b o n y l groups a c c o r d i n g t o  Co (C0)g 2  +  HG 5.GH  5 ^  Co^CO^E,  +  2C0  S l y (A6) r e p o r t s a d e t a i l e d X^-ray c r y s t a l l o g r a p h i c study o f d i p h e n y l a c e t y l e n e d i c o b a l t h e x a c a r b o n y l and r e p o r t s i t s s t r u c t u r e as shown.  He found t h a t each carbon was bonded t o each c o b a l t and t h a t t h e p l a n e o f t h e carbon-carbon bond was r o u g h l y a t 90° t o t h e p l a n e o f t h e  11  Cobalt-cobalt  bond.  S l y stated that t h i s structure represents  the f i r s t m o l e c u l e s t o be s t u d i e d which e x h i b i t s a m u l t i p o i n t o f a s i n g l e o r g a n i c m o l e c u l e t o more t h a n one m e t a l atom. t h i s i s p o s s i b l y analogous t o the p o s t u l a t e d substrate  E.  Hydroformylation  -  The  Oxo  Reaction  scope o f the  reaction  I.  Nature and  The  l i t e r a t u r e concerning  reviewed by Vender e t a l (53).  The  t h i s r e a c t i o n has  of  attachment  He f e e l s  attachment o f an  to a m e t a l s u r f a c e d u r i n g heterogeneous c a t a l y t i c  one  organic  reactions.  been e x t e n s i v e l y  o v e r a l l r e a c t i o n i s most e a s i l y  v i s u a l i z e d as i n v o l v i n g the a d d i t i o n o f a hydrogen atom and group a c r o s s the double bond o f an o l e f i n . are a p p r o x i m a t e l y 75 t o 2 0 0 ° C u n d e r 100  Conditions  t o 300  a  f o r the  formyl reaction  atmospheres o f a m i x t u r e  o f carbon monoxide and hydrogen i n the presence o f a c o b a l t c a t a l y s t . I t appears t h a t a t l e a s t t h r e e c a r b o n y l s  o f c o b a l t are i n v o l v e d i n the  a d d i t i o n o f c a r b o n monoxide and hydrogen to an o l e f i n . d i c o b a l t octacarbonyl, tetramer.  c o b a l t h y d r o c a r b o n y l , and  These  are  the c o b a l t t r i c a r b o n y l  I t i s o f i n t e r e s t t o n o t e t h a t the h y d r o f o r m y l a t i o n  of  an  o l e f i n o c c u r s p r a c t i c a l l y t o the complete e x c l u s i o n o f i t s h y d r o g e n a t i o n even though the f r e e energy change f o r the h y d r o g e n a t i o n i s much than t h a t f o r the h y d r o f o r m y l a t i o n competitive  reaction.  H y d r o g e n a t i o n becomes a  r e a c t i o n when the o l e f i n i c l i n k a g e i s c o n j u g a t e d .  simple o l e f i n submitted t o h y d r o f o r m y l a t i o n t o undergo t h i s r e a c t i o n ^  greater  c o n d i t i o n s has  Every  been shown  12  Double bond i s o m e r i z a t i o n o c c u r s r e a d i l y under hydroformyl a t i o n conditions.  F o r example the p r o d u c t s o b t a i n e d  when 1-pentene  and 2-pentene are submitted t o the r e a c t i o n are the same.  This i s  f o u n d i n s p i t e o f the o b s e r v e d f a c t t h a t i s o m e r i z a t i o n i s a slow p r o c e s s compared t o h y d r o f o r m y l a t i o n has no  (55).  The  amount o f hydrogen  p a r t i c u l a r e f f e c t on the r a t e o f i s o m e r i z a t i o n .  present  Isomerization  o c c u r s i n the absence o f hydrogen and i s n o t f a s t even when l a r g e amounts o f hydrogen are added (10,  11).  These f a c t s l e a d t o the  sumption t h a t the s t r u c t u r e o f the o l e f i n c a r b o n y l f o r b o t h 1 and 2-pentene.  complex i s the same  Some mechanism must e x i s t f o r the  movement o f hydrogen i n t h e s e complexes.  as-  I n g e n e r a l the  facile  straight  c h a i n aldehyde i s the f a v o u r e d p r o d u c t .  II.  Mechanism  Wender and S t e r n b e r g (55)  p o i n t o u t t h a t the  Fischer-Tropsch  synthesis i s probably a heterogeneously c a t a l y z e d r e a c t i o n since i t takes place at comparatively tendency toward f o r m a t i o n  low  below the p o i n t where the  of metal carbonyls  mation o f m e t a l complexes d e s t r o y hydroformylation  pressures  the s u r f a c e i n t e r m e d i a t e .  i s homogeneously c a t a l y z e d .  c a t a l y z e d by the c a r b o n y l s  becomes l a r g e .  i n v o l v e formation  The In  for* contrast  Homogeneous r e a c t i o n s o f s o l u b l e m e t a l complexes.  They a l s o observe t h a t i t i s l i k e l y t h a t a l l t h r e e r e a c t a n t s , t h a t i s , o l e f i n , carbon monoxide and hydrogen are u n i t e d i n one stage o f the r e a c t i o n .  The  complex a t some  f o l l o w i n g mechanism i s p r e s e n t e d i n the  13 l i g h t o f t h i s i d e a and appears t o agree w i t h a l l a v a i l a b l e d a t a . Cyclohexene i s u s e d i n t h i s  C H 6  V may  1 £ )  +  Co (C0) 2  example.  Co (CO) C H  8  2  7  6  +  1 G  CO  have the s t r u c t u r e shown, by analogy w i t h the proven  o f a c e t y l e n e complexes  structure  (4-6). 0  II  (CO),  R  Co  Co  C  C H  (co).  H  The ease o f f o r m a t i o n o f V i s s t r o n g l y i n f l u e n c e d by the r e q u i r e m e n t s o f the o l e f i n  Co (C0) C H 2  7  6  1 0  +  ( r e f 53,  H  p.  2  T h i s e q u a t i o n i s most p r o b a b l y r e a l i z e d  steric  79).  Co (C0) 2  6  i n two s t e p s .  +  C H CH0 6  n  The complex  V  p r o b a b l y s p l i t s a hydrogen m o l e c u l e , as shown, t o o b t a i n t h e complex  VI.  14 0 n  (CO),  Co—  H  —Co  H  —  (CO),  C  A  H  R  H  VI  I n the n e x t s t e p VI p r o d u c t aldehyde.  s p l i t s t o form d i c o b a l t h e x a c a r b o n y l and  the  Then d i c o b a l t h e x a c a r b o n y l r e a c t s w i t h c a r b o n  monoxide t o r e f o r m d i c o b a l t  octacarbonyl.  I n c o n t r a s t w i t h the above mechanism A l d r i d g e e t a l ( l ) suggest t h a t the h y d r o f o r m y l a t i o n catalyzed.  r e a c t i o n may  be  heterogeneously  They r e p o r t d a t a f r o m which i t can be deduced t h a t the  of hydroformylation  o f an o l e f i n i s n o t d i r e c t l y dependent upon the  amounts o f s o l u b l e c o b a l t p r e s e n t u n d e r r e a c t i o n c o n d i t i o n s . i n s o l u b l e c o b a l t may  provide  h y d r o c a r b o n y l s may  F.  by c a r b o n y l  formation  which and  These authors conclude t h a t i t appears l i k e l y t h a t any  r o l e i n hydroformylation  cobalt  The  a f r e s h h i g h l y a c t i v e metal surface  i s c o n s t a n t l y b e i n g consumed and d e p o s i t e d breakdown.  rate  c a t a l y s i s that cobalt carbonyls  or  p l a y must be c a r r i e d o u t i n c o n j u n c t i o n  direct  cobalt with a solid,  surface.  Carbonylation  Relatively l i t t l e  appears i n the l i t e r a t u r e about a system  which c o n t a i n s no hydrogen, c o n s i s t i n g o f the s u b s t r a t e , c a r b o n monoxide  15 and  the m e t a l c a r b o n y l  catalyst.  by T i r p a k e t a l (50) f o r the  A r e a c t i o n mechanism has  been proposed  system where a d i s u b s t i t u t e d a c e t y l e n e  a l l o w e d t o r e a c t w i t h carbon monoxide and d i c o b a l t o c t a c a r b o n y l absence o f hydrogen. by r e p l a c i n g the r e f . 46).  Disubstituted  bridge  acetylenes  in  the  f o r m s t a b l e compounds  carbonyls of d i c o b a l t octacarbonyl  (see page  10,  These have the c o m p o s i t i o n R C 2 R ' C O 2 ( C 0 ) ^ .  T r i p a k quotes S t e r n b e r g e t a l (48) who a d i c o b a l t n o n a c a r b o n y l can  have e s t a b l i s h e d  carbonyl  that  be produced under c e r t a i n c o n d i t i o n s .  i n v o l v e s the h o m o l y t i c f i s s i o n o f the c o b a l t - c o b a l t bridge  is  t o produce the s t r u c t u r e  bond t o add  a  This third  VII.  0 n  0 —  0  Co  C  •  Co  C =  0  n 0  VII  By V I I I i n the  analogy w i t h t h i s compound he acetylenic  reaction.  s u g g e s t s the presence o f  16 0  tt;  (CO),  Go  C—Co  \  (CO)-  o / c= c /  \  R  R VIII  T h i s would be formed i n the f i r s t  s t e p o f the r e a c t i o n  lowed by decomposition t o o b t a i n the more s t a b l e s t r u c t u r e to  that of S l y  G.  fol-  analogous  (46).  Reactions Related to Hydroformylation  Lonsbury  and Meschke (25)  r e a c t e d cyclohexene  300° C w i t h carbon monoxide and hydrogen.  a t 800 atm  and  They o b t a i n e d b e s i d e s t h e  expected h y d r o f o r m y l a t i o n p r o d u c t s a p e r h y d r o f l u o r e n o n e  0  They showed t h i s compound c o u l d be produced or  any c a t a l y s t .  An analogous  i n the absence o f hydrogen  p r o d u c t c o u l d be o b t a i n e d from c y c l o p e n -  tene but no r e a c t i o n o c c u r r e d w i t h a v a r i e t y o f a l i p h a t i c o l e f i n s .  The  a u t h o r s o f f e r no s u g g e s t i o n s o f a p o s s i b l e mechanism f o r the r e a c t i o n .  17  A 91$ c o n v e r s i o n o f o l e f i n s t o aldehydes has been r e p o r t e d (43) u s i n g a c o b a l t , t h o r i a , magnesia, c a t a l y s t under h y d r o f o r m y l a t i o n conditions.  The p r o d u c t appeared i n a g r e e n i s h b l a c k s o l u t i o n  con-  t a i n i n g cobalt carbonyls.  Nakamura (31) r e p o r t s r e d u c t i o n o f S c h i f f bases under hydroformylation conditions. a t 1 3 5 ° C produced  R e a c t i o n o f b e n z a l c y c l o h e x y l i m i n e f o r 4 hours  79$ o f b e n z y l c y c l o h e x y l a m i n e .  The a u t h o r s n o t e d  those S c h i f f bases which a r e most c o n j u g a t e d a r e most e a s i l y and form the l o w e s t amounts o f r e s i n o u s byproducts.  reduced  They a l s o n o t e d  amines, e s p e c i a l l y a l i p h a t i c s , l o w e r t h e y i e l d c o n s i d e r a b l y .  This i s  p o s s i b l y connected w i t h t h e type o f r e a c t i o n mentioned by H i e b e r (page 9, r e f . 2 1 ) . K i r c h and O r c h i n ( 2 4 ) showed t h a t complex f o r m a t i o n does take p l a c e i n a t o l u e n e s o l u t i o n o f c o b a l t h y d r o c a r b o n y l and 1-hexene. A t 0 ° C t h e s o l u t i o n absorbed 2 moles o f carbon monoxide. the complex decomposed t o form aldehydes.  A t 25° C  The a u t h o r s s t a t e t h e complex  has the c o m p o s i t i o n 2HCo(C0)^RC0 where R r e p r e s e n t s o l e f i n .  R o s e n t h a l and Read (41) r e p o r t e d t h a t when 3, 46, t r i O - a c e t y l - D - g a l a c t a l was a l l o w e d t o r e a c t under h y d r o f o r m y l a t i o n cond i t i o n s a hydroxymethyl  group was added a c r o s s the double bond.  Nuss-  baum e t a l (32) r e c e n t l y r e p o r t e d a s i m i l a r a d d i t i o n o f a hydroxy methyl group t o a double bond o f a s t e r o i d n u c l e u s .  H.  R e a c t i o n s o f carbon monoxide i n v o l v i n g n i t r o g e n compounds.  The work o f Buckley and Ray (6) and t h a t o f H i e b e r and Wies-  18  boeck (21)  has  a l r e a d y been r e f e r r e d t o .  formation  of dimethylglycine  according  t o the  equation  HGHO  +  f r o m formaldehyde and  (CH ) NH 3  Tyson and  Hall well  2  Shaw (51)  j^  >  1  was  d i m e t h y l amine  produced the 3 carboxaldehyde d e r i v a t i v e catalyst.  The  authors concluded t h a t N-formyl i n d o l e  r e a d i l y to the 3 d e r i v a t i v e under r e a c t i o n c o n d i t i o n s . no  u s e d (52).  conclusive  These a u t h o r s  r e s u l t s when 2 o r 3 s u b s t i t u t e d i n d o l e s were  Winteler  e t a l (57) r e a c t e d  amines w i t h c a r b o n monoxide a t 150 The  When  isomerized  S t e r i c e f f e c t s were b e l i e v e d r e s p o n s i b l e f o r t h e  o f the r e a c t i o n .  h o l ate.  the  r e a c t e d under s i m i l a r c o n d i t i o n s the N - f o r m y l compound  isolated.  obtained  reported  (CE^HCHgCOGH  f r o m potassium i n d o l e u s i n g a d i c o b a l t o c t a c a r b o n y l i n d o l i n e was  (19)  overall reaction  atm  p r i m a r y and  failure  secondary  i n the p r e s e n c e o f sodium a l c o -  was  0 n  R'R"NH  RVN-CH  >  They n o t e d the r a t e o f r e a c t i o n i n c r e a s e d They p o s t u l a t e d  t h a t the f i r s t  c a r b o n monoxide t o the  RO  +  r a p i d l y w i t h temperature.  s t e p i n the r e a c t i o n was  alcoholate  CO  ^>  R-C  =  0  — ^  R-C  the a d d i t i o n  of  19  T h i s t h e n r e a c t e d w i t h the amine  R-COOH  R2NH  +  ^  F^NCH  +  ROH  T e t e r and O l s o n (49) produced n i t r i l e s from o l e f i n s  and  ammonia u s i n g a m i x t u r e o f CoSO^ and NiSO^ as c a t a l y s t a t 340° C and 100 atmospheres;  CH -CH 3  the o v e r a l l r e a c t i o n  =  CHg  +  NH  was  CH -CH -C=N  3  3  2  U s i n g extreme c o n d i t i o n s B e n g e l s d o r f (3) produced IX from  aromatic  nitriles  Ar t C  3 Ar - C =  =5*  N  N I  '/ \  N ||  IX T h i s s - t r i a z i n e t r i m e r was formed  a t 50,000 atm and 500° G.  Benzamide under these c o n d i t i o n s was dehydrated i n s i t u produced  an analogous p r o d u c t .  o f benzamide, when s u b j e c t e d t o produce  Syn-benzaldoxime,  and  a s t r u c t u r a l isomer  t o these c o n d i t i o n s decomposed e x p l o s i v e l y  ammonia and a carbonaceous m a t e r i a l r e s e m b l i n g amorphous carbon.  20  When O - t o l u n i t r i l e was  s u b j e c t e d t o r e a c t i o n c o n d i t i o n s the  analogous p r o d u c t was o b t a i n e d i n poor y i e l d showing s t e r i c i s n o t overcome even a t these extreme p r e s s u r e s .  hindrance  Phosphoric a c i d  however a l l o w e d a q u a n t i t a t i v e y i e l d from O - t o l u n i t r i l e .  {$5%)  Phthalonitrile  y i e l d e d phthalocyanine.  Saner e t a l ( 4 4 ) r e a c t e d 3 , d i e t h y l a m i n o - p r o p y n e - 1 a t 1 2 5 ° C and 5 0 0 atmospheres o f carbon monoxide t o produce 2 , 3 d i h y d r o , 3 d i e t h y l formamido), 5 d i e t h y l amino f u r a n , i n 4 4 $ y i e l d .  R  Et I  \  N  - CH-, - C=E  CH  Et  /  0  n  N - C  H  (NN  They r e p o r t e d  H  T T  —  N  o  t h a t c a t a l y t i c amounts o f d i c o b a l t o c t a c a r b o n y l were r e q u i r e d f o r t h i s reaction.  I,  R e a c t i o n s o f Carbon Monoxide I n v o l v i n g Ring F o r m a t i o n .  Pritchard  (36) c y c l i z e d the aromatic amide  a n i l i n e w i t h carbon monoxide a t 3 2 5  0  C using a n i c k e l carbonyl catalyst.  0  tt  0  it  n  ph - C - N — C -  t  ph  N,N-dibenzoyl~  ph  - ph  <x ^  /  ^ V ^ C n  0  +•  21  The p r o d u c t s were N-phenylphthalimide  and benzene.  Benzoic  anhydride  r e a c t e d s i m i l a r l y t o produce p h t h a l i c anhydride and benzene. and b e n z o i c a c i d a p p a r e n t l y r e a c t e d above 250° C t o g i v e which subsequently c y c l i z e d to give phthalimide. no carbon monoxide i s used. reactions f a i l  without  Benzonitrile  dibenzamide,  I t i s n o t e d here  that  I t s f u n c t i o n i s n o t known a l t h o u g h the  it.  P r i t c h a r d (37) s u b s e q u e n t l y p r e p a r e d N - s u b s t i t u t e d p h t h a l i midine s f r o m N - s u b s t i t u t e d i m i n e s as shown.  CH = N -  ph  N -  0  He c a r r i e d out the r e a c t i o n w i t h d i f f e r e n t s u b s t i t u e n t s b o t h a t the 3 p o s i t i o n and on the r i n g on which the r i n g c l o s u r e o c c u r r e d .  P r i t c h a r d a l s o submitted p h e n y l bromide t o the r e a c t i o n c o n d i t i o n s adding a l k a l i c a r b o n a t e s .  The p r o d u c t s were p h t h a l i c  an-  h y d r i d e and benzene which a p p a r e n t l y were o b t a i n e d through p r e l i m i n a r y f o r m a t i o n o f benzoic a n h y d r i d e .  P r i t c h a r d (38) f u r t h e r r e a c t e d azobenzene w i t h c a t a l y t i c amounts o f n i c k e l c o r b o n y l a t 250° C. two moles o f carbon monoxide. from the m i x t u r e .  The r e a c t i o n absorbed a t l e a s t  They i s o l a t e d 2 p h e n y l i n d a z o l o n e  (X)  ph  22  H N N -  ph  C  X  Murahashi and H o r i i e (30) shoved t h a t a t 190° reported  also reported  G the c h i e f p r o d u c t was  on azobenzene.  the i n d a z o l o n e  X but  t h a t a t 230° C a second mole o f carbon monoxide was  They they  absorbed  t o produce XI  H N  /° N -  ph  XI  Substituents  i n the A p o s i t i o n ( c h l o r o o r d i m e t h y l a m i n o ) d i d  n o t a f f e c t the r e a c t i o n e x c e p t t h a t r i n g c l o s u r e o c c u r r e d c a r r y i n g the s u b s t i t u e n t . as a byproduct.  D i p h e n y l u r e a was  obtained  on the r i n g  i n s m a l l amounts  23  Murahashi (29) r e p o r t e d  t h a t the r e a c t i o n w i t h benzaldehyde  a n i l f a i l e d w i t h n i c k e l c a t a l y s t s but r i n g c l o s u r e o c c u r r e d y i e l d with d i c o b a l t octacarbonyl  in  80%  present.  C H  N-ph  200  2  atm N-ph  230° C 6 hours C II  1-Naphaldehyde a n i l produced an analogous compound. worthy o f note t h a t r i n g c l o s u r e o c c u r r e d  It i s  t o produce the l i n e a r isomer,  whereas 2 s u b s t i t u t e d n a p t h a l e n e s u s u a l l y s u b s t i t u t e f u r t h e r i n the position. using  R o s e n t h a l e t a l (40) have r e p o r t e d  oxime.  examples o f r i n g c l o s u r e  aromatic oximes t o produce s u b s t i t u t e d phthalimidines.,  r e a c t i o n has  been s u c c e s s f u l f o r benzophenone oxime and  This  acetophenone  B e n z y l p h e n y l ketoxime gave b o t h p o s s i b l e p r o d u c t s .  Cyclization  took p l a c e t o each a v a i l a b l e r i n g t o produce 3 b e n z y l p h t h a l i m i d i n e 3-phenyl,  3-4-dihydroisocarbostyril.  1  and  2A  ph  /  C H  / V  CH.  2  S -  H/ OH  00(150 Co (C0) 2  atm) 8  230° C  I t i s n o t a b l e t h a t t h e expected compound.  \  t  V  \  7  it  p r o d u c t would be t h e N-hydroxy  A p p a r e n t l y the known r e d u c i n g a c t i o n o f carbon  c o n v e r t s t h i s t o the NH compound e i t h e r b e f o r e o r a f t e r t a k e s place..  C  NH  /  monoxide  cyclization  25  DISCUSSION  A.  Syn- ben z aldoxime  The  p r i n c i p a l e f f o r t o f the p r e s e n t work was  d i r e c t e d towards  e s t a b l i s h i n g the f u r t h e r g e n e r a l i t y o f the r e a c t i o n r e p o r t e d e t a l (4-0).  These a u t h o r s showed t h a t c e r t a i n aromatic oximes  i n the presence o f d i c o b a l t o c t a c a r b o n y l 4100  by R o s e n t h a l  p . s . i . and  a t 200  and  reacted  c a r b o n monoxide a t about  - 2 5 0 ° C t o y i e l d l a c t a m s as shown i n e q u a t i o n  I.  R ^N -  OH  A  CO  /  8 I!  0  I  T h i s r e a c t i o n was  s u c c e s s f u l where R was  p h e n y l , methyl o r  b e n z y l (See i n t r o d u c t i o n page 2 3 ) .  I n the p r e s e n t work syn-benzaldoxime, benzophenone oxime  and  the O-methyl e t h e r o f benzophenone oxime were a l l o w e d t o r e a c t u n d e r the f o l l o w i n g c o n d i t i o n s .  The  temperature range was  170°  to 230° C  26  and i n i t i a l p r e s s u r e s  were n e a r 2200 p . s . i .  under r e a c t i o n c o n d i t i o n s was  Maximum p r e s s u r e  n e a r 4500 p . s . i .  The  reached  r e a c t i o n s were  c a r r i e d out i n p u r i f i e d benzene s o l u t i o n s i n the p r e s e n c e o f preformed dicobalt  octacarbonyl.  I n the case o f syn-benzaldoxime the f o l l o w i n g p r o d u c t s were i s o l a t e d from the r e a c t i o n m i x t u r e ; s y m - d i b e n z y l u r e a (35$), monobenzylurea  (1056), benzaldehyde (10#), compound A  (15/0,  compound B  By a n a l o g y w i t h the above d e s c r i b e d e s t a b l i s h e d r e a c t i o n phthalimidine  c o u l d be expected as a p r o d u c t o f t h i s r e a c t i o n .  It  (15/0. (40) was  n o t f o u n d p o s s i b l e t o i s o l a t e any o f t h i s compound.  T o t a l recovery considerable  shown above i s &5%*  amounts o f o r g a n i c m a t e r i a l s were complexed w i t h  p r o d u c t s o f the c a t a l y s t . experimental  An example o f t h i s i s m a t e r i a l I  s e c t i o n ) which c o n t a i n e d  w e l l as c o b a l t .  degradation (see page  carbon, hydrogen and n i t r o g e n  Other examples o f i g n i t a b l e , c o b a l t c o n t a i n i n g ,  appear i n the e x p e r i m e n t a l  No  I t i s believed that  as  materials  section.  c h a r a c t e r i z a t i o n work was  t h e i r i n f r a r e d s p e c t r a showed no  done on compounds A and  B since  a b s o r p t i o n i n the c a r b o n y l r e g i o n  the p r i n c i p a l i n t e r e s t l a y i n the c a r b o n y l a t e d pounds f a i l e d a l s o t o show a b s o r p t i o n i n the OH  compounds. o r NH  and  These com-  s t r e t c h i n g regions  o f the i n f r a r e d .  The  56  presence o f benzaldehyde i n the r e a c t i o n m i x t u r e seems t o  i n d i c a t e t h a t h y d r o l y s i s o f the oxime has o c c u r r e d .  Care was  taken to  27  use d r y s o l v e n t and s u b s t r a t e b u t a s m a l l amount o f water may have been p r e s e n t i n the carbon monoxide used. large y i e l d  However t h e c o m p a r a t i v e l y  (10%) o f benzaldehyde i n d i c a t e s some o t h e r method o f pro-  d u c i n g t h i s compound i s p r o b a b l e .  T h i s c o u l d have o c c u r r e d i n some  manner such as rearrangement o f t h e oxime w h i l e complexed w i t h t h e carbonyl  catalyst.  Cit!  Co  (OC^-  /  \  c I  ph  Co  (CO),  N 'OH  H  Formula I r e p r e s e n t s a h y p o t h e t i c a l i n t e r m e d i a t e analogous t o those e s t a b l i s h e d f o r alkynes page 10).  and alkenes  (4-6, 50, 2 4 ) (See i n t r o d u c t i o n  I t was p o i n t e d o u t e a r l i e r ( i n t r o d u c t i o n page 12) t h a t some  mechanism must e x i s t f o r t h e f a c i l e movement o f hydrogen i n t h e comp l e x e s suggested  for olefin reactions.  Some analogous rearrangement  i n v o l v i n g t h e h y d r o x y l group c o u l d produce benzaldehyde.  The behaviour  o f t h e f i r s t m a t e r i a l e l u t e d from t h e chroma-  tographic separation o f the r e a c t i o n products  (see page 44 ) i s s i m i l a r  t o t h a t r e p o r t e d f o r a complex w i t h d i c o b a l t o c t a c a r b o n y l by G r e e n f i e l d  28  e t a l (17).  These a u t h o r s l i s t e d the f o l l o w i n g p r o p e r t i e s f o r a c e t y l e n i c  d i c o b a l t h e x a c a r b o n y l s ; deep r e d c o l o r , weak i n t e r m o l e c u l a r f o r c e s , h i g h v o l a t i l i t y , high s o l u b i l i t y i n organic a c t i v a t e d alumina.  s o l v e n t s and e a s y removal f r o m  These p r o p e r t i e s are c o n s i s t e n t w i t h the  behaviour  o f the e l u t e d m a t e r i a l mentioned above, s i n c e the m a t e r i a l from column f i r s t formed a homogeneous r e d a l c o h o l s o l u t i o n . isolate  An  the  attempt t o  the d i s s o l v e d m a t e r i a l produced a brown s o l i d i n s o l u b l e i n  a l c o h o l p l u s an o r g a n i c  component which has been r e f e r r e d t o as Compound  A.  shown t o c o n t a i n c o b a l t .  The  brown s o l i d was  reported  t h a t b e n z i l was  diphenylacetylene o b s e r v a t i o n may  Greenfield et a l also  a major component i n the d e c o m p o s i t i o n o f  d i c o b a l t h e x a c a r b o n y l a t room temperature.  This  p a r a l l e l the i s o l a t i o n o f benzaldehyde as a r e a c t i o n  product.  Mono-benzylurea and melting point using authentic  s y m - d i b e n z y l u r e a were i d e n t i f i e d by mixed samples ( 8 ) .  These compounds a l s o  possessed i n f r a r e d s p e c t r a i d e n t i c a l w i t h those o f the a u t h e n t i c (pages A9  and  55  )•  Sym-dibenzylurea was  o x i d i z e d t o produce  samples  sym-  dibenzoylurea.  T h i s w r i t e r i s u n a b l e to p o s t u l a t e a r e a s o n a b l e f o r the f o r m a t i o n  o f the observed s u b s t i t u t e d u r e a s .  f i c i e n t t o e x p l a i n the p r o d u c t i o n  mechanism  I t would be  o f mono-benzylurea s i n c e  sym-  d i b e n z y l u r e a can be o b t a i n e d from mono-benzylurea by h e a t i n g and be expected under the r e a c t i o n c o n d i t i o n s i f mono-benzylurea were present  (8).  suf-  would  29 I t may  be mentioned t h a t the h y d r o l y s i s i n f o r m a t i o n  i s c o n s i s t e n t w i t h the b e h a v i o u r o f u r e a s . (page 50)  The  t h a t each o r g a n i c was  alkaline conditions  should h y d r o l y z e most amides (13) but h i g h e r  and/or l o n g e r t i m e s are needed f o r u r e a s (42). compound r e c o v e r e d  these compounds i t was  felt  temperatures  I t i s worthy o f n o t e  from the chromatographic  accompanied by a y e l l o w o i l y m a t e r i a l .  reported  A t f i r s t on  t h a t an o x i d a t i o n was  separation  recrystallizlng  taking place.  Sub-  sequent i s o l a t i o n o f the y e l l o w m a t e r i a l , however, always showed the presence o f c o b a l t .  It is felt  t h a t the amides p r e s e n t may  manner be complexed w i t h a c o b a l t compound and fairly  slowly.  octacarbonyl  H i e b e r (21)  may  i n some  the complex decomposes  i n d i c a t e d amide complexes w i t h d i c o b a l t  be broken down i n r e f l u x i n g p e t r o l e u m e t h e r .  I n the f i r s t run o f the syn-benzaldoxime r e a c t i o n the a b s o r p t i o n o f carbon monoxide was r e r u n showed an a b s o r p t i o n second r u n was  2.1  o f 1.25  moles per mole o f s u b s t r a t e .  moles per mole o f s u b s t r a t e .  c a r r i e d out i n a new  The  The  s t a i n l e s s s t e e l bomb w i t h o u t a g l a s s  l i n e r whereas the f i r s t r u n u s e d a g l a s s l i n e r . f e r e n c e i n c a r b o n monoxide a b s o r p t i o n be i s o l a t e d f r o m both r e a c t i o n s .  overall  In s p i t e of t h i s  the same o r g a n i c  I t was  impossible  dif-  components c o u l d  t o compare r e l a t i v e  y i e l d s because o f an a c c i d e n t i n v o l v i n g s h a t t e r i n g o f a d i s t i l l i n g c o n t a i n i n g the r e a c t i o n p r o d u c t f r o m run two. of d i c o b a l t octacarbonyl  The volume p e r c e n t  I n each case the  a f t e r c o m p l e t i o n o f the r e a c t i o n was  flask  presence  shown.  carbon monoxide u s e d f o r the r e a c t i o n s c o n t a i n e d o f hydrogen a c c o r d i n g t o an a n a l y s i s s u p p l i e d by  0.04 the  30  manufacturer  (Matheson, New  Jersey),  Vapor phase chromatography c a r r i e d  o u t i n t h i s department o b t a i n e d a r e s u l t o f 1.5$  by volume.  Vapor  phase chromatography o f the p r o d u c t gases showed the absence o f hydrogen. The c o n d i t i o n s under which the sampling was  done do n o t p r e c l u d e the  p o s s i b i l i t y t h a t any hydrogen p r e s e n t had u n i t e d w i t h c a t a l y s t  molecules  r a t h e r than w i t h the s u b s t r a t e .  temperature  and h i g h p r e s s u r e (2000 p . s . i . ) .  The  sampling was  done a t room  Under t h e s e c o n d i t i o n s c o b a l t  hydro-  c a r b o n y l i s s t a b l e and does n o t decompose u n t i l t h e p r e s s u r e i s r e l e a s e d (33).  I t was mentioned above t h a t no p h t h a l i m i d i n e c o u l d be d e t e c t e d i n the p r o d u c t m i x t u r e .  I t i s p o s s i b l e t h a t any p h t h a l m i d i n e formed  condensed t o more c o m p l i c a t e d p r o d u c t s under the s e v e r e r e a c t i o n c o n d i t i o n s s i n c e two u n c h a r a c t e r i z e d p r o d u c t s were p r e s e n t . suggested h e r e t h a t s u b j e c t i o n o f the O-methyl e t h e r o f t o the r e a c t i o n c o n d i t i o n s may group may  made c o n s i d e r i n g the analogous  reactions.  methyl  T h i s statement i s  c a s e o f the O-methyl e t h e r o f benzo-  phenone oxime where the o n l y o r g a n i c p r o d u c t was  3-phenylphthalimidine  and the s i d e p r o d u c t found w i t h benzophenone oxime was  B.  benzaldoxime  l e a d t o r i n g c l o s u r e s i n c e the  p r o v i d e hindrance t o competing  It i s  not present.  Benzophenone Oxime.  I n the r e a c t i o n w i t h benzophenone oxime t h e major p r o d u c t (70$) was  3-phenylphthalimidine.  A minor p r o d u c t ( a p p r o x i m a t e l y  5%)  31  was  the u n i d e n t i f i e d compound B.  3-Phenylphthalimidine  by d i r e c t comparison w i t h an a u t h e n t i c sample (39).  was  identified  A mixed m e l t i n g  p o i n t showed no d e p r e s s i o n and t h e i r i n f r a r e d s p e c t r a were i d e n t i c a l . An a c e t a t e d e r i v a t i v e was  also  prepared.  The r e a c t i o n w i t h benzophenone oxime was amounts o f c a t a l y s t .  I n one t r i a l  moles o f c a t a l y s t were used. and 0.02  moles o f s u b s t r a t e and  I n t h e second  moles o f c a t a l y s t were used.  c o r r e s p o n d i n g t o 1.75 Case two  0.07  run with v a r y i n g 0.02  case 0.1 moles o f s u b s t r a t e  Case one  showed an a b s o r p t i o n  moles o f carbon monoxide p e r mole o f s u b s t r a t e .  showed an a b s o r p t i o n o f 1.80  moles per mole o f s u b s t r a t e .  c o m p o s i t i o n o f the r e c o v e r e d o r g a n i c p r o d u c t d i d n o t seem t o be by the d i f f e r e n c e i n s u b s t r a t e t o c a t a l y s t r a t i o . t r i a l the amount o f c a t a l y s t was  reduced  affected  However i n a t h i r d  t o a p p r o x i m a t e l y 0.002 moles  and a major d i f f e r e n c e i n the c o u r s e o f r e a c t i o n was A l s o p r e s e n t i n t h i s r e a c t i o n was  The  noted  cobaltous carbonate.  (see page 3A).  The r e s u l t s o f  the r e a c t i o n i n d i c a t e t h a t a p p r e c i a b l e amounts o f d i c o b a l t o c t a c a r b o n y l were n o t formed from the c o b a l t o u s carbonate under the r e a c t i o n c o n d i t i o n s .  In m a t e r i a l was B.  b o t h o f the f i r s t  two  c a s e s the r e c o v e r y o f o r g a n i c  n e a r 75% o f which r o u g h l y 5% was  An e x a c t y i e l d f o r compound B i s n o t a v a i l a b l e because no  s e p a r a t i o n was  c a r r i e d out.  I t was  n o t e d t h a t compound B was  s o l u b l e i n e t h e r than 3 - p h e n y l p h t h a l i m i d i n e . of  the u n i d e n t i f i e d component complete more  Therefore ether e x t r a c t i o n s  the t o t a l o r g a n i c amount were c a r r i e d out t o o b t a i n a s o l u t i o n  t a i n i n g a l a r g e r p r o p o r t i o n o f compound B.  T h i s s o l u t i o n was  then  con-  32  chromatographed t o s e p a r a t e B f r o m r e m a i n i n g 3 - p h e n y l p h t h a l i m i d i n e . I t was n o t p o s s i b l e t o s t a t e how q u a n t i t a t i v e the e t h e r s e p a r a t i o n was.  I t was s i m p l e t o o b t a i n pure 3 - p h e n y l p h t h a l i m i d i n e s i n c e  r e c r y s t a l l i z a t i o n o f t h e o r i g i n a l m i x t u r e from e t h a n o l , methanol, o r benzene would produce  pure compound.  l i c a t i o n s o l v e n t s f a i l e d t o produce  Extensive t r i a l s of r e c r y s t a l pure compound B.  The b e h a v i o u r  o f a mixture o f B and 3 - p h e n y l p h t h a l i m i d i n e was u n u s u a l when r e c r y s t a l l i z a t i o n from e t h e r was attempted.  The f i r s t c r o p o f c r y s t a l s was  l a r g e l y 3 - p h e n y l p h t h a l i m i d i n e t h e second was 60$ compound B and 40% 3-phenylphthalimidine.  The t h i r d was l a r g e l y  >phenylphthalimidine.  These r e s u l t s were o b t a i n e d through alumina chromatography (page 64  ).  A r e d u c t i o n o f compound B was c a r r i e d o u t u s i n g hydrogen o v e r platinum oxide i n a c e t i c acid s o l u t i o n .  The p r o d u c t s o f t h i s r e d u c t i o n  were compared t o t h e p r o d u c t s o f a p a r a l l e l r e d u c t i o n o f 3 - p h e n y l p h t h a l i midine.  The major p r o d u c t f o r t h e r e d u c t i o n o f 3 - p h e n y l p h t h a l i m i d i n e  was 3 - c y c l o h e x y l h e x a h y d r o - p h t h a l i m i d i n e ( H I ) as i s shown on page 6 3  C  n  0 XII  33 A s m a l l sample (5% y i e l d ) o f an i d e n t i c a l compound  (mixed  m e l t i n g p o i n t and i n f r a r e d s p e c t r a ) was secured from t h e r e d u c t i o n o f compound B.  T h i s same compound was a l s o o b t a i n e d by a p a r a l l e l  r e d u c t i o n o f an a u t h e n t i c sample o f 3 - p h e n y l p h t h a l i m i d i n e p r e p a r e d by t h e method o f Rose (39).  These experiments  provided e x t r a proof o f  the i d e n t i t y o f t h e 3 - p h e n y l p h t h a l i m i d i n e produced.  However t h e r e s u l t s  a r e n o t b e l i e v e d t o g i v e an i n d i c a t i o n o f the s t r u c t u r e o f compound B s i n c e the m a t e r i a l used f o r the r e d u c t i o n i s n o t now c o n s i d e r e d pure. The compound B used was o b t a i n e d by a r e c r y s t a l l i z a t i o n procedure and s h a r p l y a t 197 -  melted  199°  G.  The a n a l y s i s o b t a i n e d showed an  e m p i r i c a l f o r m u l a c o r r e s p o n d i n g t o a dimer o f 3 - p h e n y l p h t h a l i m i d i n e ^ 2 8 2 2 2 ^ 2 )• H  N  )  However subsequent  chromatographic  purification  failed  t o change t h e m e l t i n g p o i n t though i t d i d change t h e a n a l y s i s so t h a t t h e b e s t f i t e m p i r i c a l f o r m u l a became  Cg^H^^^s*  ^ p o s s i b l e explan-  a t i o n o f t h e observed phenomena i s t h a t t h e compound B used f o r t h e r e d u c t i o n was contaminated  with 3-phenylphthalimidine but t h a t suf-  f i c i e n t s i m i l a r i t y i n c r y s t a l s t r u c t u r e p r e v e n t e d l o w e r i n g o f the melting point.  A summary o f t h e p r o p e r t i e s o f compound B f o l l o w s : s o l u b l e i n e t h e r , benzene and a l c o h o l s .  I t was  I t was i n s o l u b l e i n b o i l i n g  water, b o i l i n g 20$ sodium h y d r o x i d e , o r b o i l i n g c o n c e n t r a t e d h y d r o c h l o r i c acid.  C o n d i t i o n s s u i t a b l e f o r h y d r o l y s i s o f a l l b u t t h e most h i n d e r e d  aromatic amides f a i l e d t o a f f e c t compound B.  Even though i t s i n f r a r e d  34  spectrum i n d i c a t e d a c t i v e hydrogen f a i l e d t o a f f e c t t h e compound.  stringent acetylation conditions  (Fused sodium a c e t a t e r e f l u x e d i n a c e t i c  anhydride f o r 6 h o u r s ) .  When t h e amount o f c a t a l y s t was reduced t o 0.002 moles  (trial  I I I ) t h e major p r o d u c t o f t h e r e a c t i o n was benzophenone which was r e c o v e r e d i n 70$ y i e l d .  L e s s t h a n a 1$ y i e l d o f 3 - p h e n y l p h t h a l i m i d i n e  was r e c o v e r e d and no t r a c e o f compound B was found. f r o m t h e r e a c t i o n was 5$ o f t h e o r i g i n a l oxime.  Also recovered  This indicates that  con-  v e r s i o n o f t h e oxime t o benzophenone i s a slow p r o c e s s s i n c e some o r i g i n a l oxime was r e c o v e r e d a f t e r 4 hours h e a t i n g .  C.  0-Methyl E t h e r o f Benzophenone  Oxime.  The O-methyl e t h e r o f benzophenone oxime was s u b j e c t e d t o t h e r e a c t i o n c o n d i t i o n s i n an attempt t o produce  an N - s u b s t i t u t e d c y c l i c  compound i n accordance w i t h e q u a t i o n I  co  C = N-OCH,  Co (C0)g 2  N-OCH,  However t h e r e s u l t i n g p r o d u c t was a 70$ y i e l d o f 3 - p h e n y l p h t h a l i m i d i n e , Only a t r a c e o f another o r g a n i c component c o u l d be found.  35  I t i s o f i n t e r e s t t h a t on washing an alumina acetone  a f t e r e l u t i o n o f the r e a c t i o n p r o d u c t s a l i g h t brown o i l was  o b t a i n e d which was the r e a c t i o n . potassium  o b v i o u s l y ( j u d g i n g from q u a n t i t y ) n o t a p r o d u c t  of  This material reacted instantaneously with i c e cold  2%  permanganate and w i t h bromine i n carbon  b o i l i n g p o i n t o f the m a t e r i a l was  tetrachloride.  163 - 166° C ( c o r r e c t e d ) .  a t u r e v a l u e f o r d i a c e t o n e a l c o h o l i s 164. - 166°  D.  column w i t h  The  The  liter-  C.  Discussion of Pressure P l o t s  D e t a i l e d r e c o r d s were k e p t o f the v a r i a t i o n o f p r e s s u r e w i t h time and temperature f o r a l l r e a c t i o n s . a r e shown on pp 42, 66,  P l o t s f o r each s u b s t r a t e u s e d  73.  The p l o t s show v a r i a t i o n o f p r e s s u r e w i t h r e a c t i o n time c o n s t a n t temperature.  A l l p r e s s u r e s a r e c o r r e c t e d t o 0° C.  at  A l l pressures  are c o r r e c t e d f o r the v a p o r p r e s s u r e o f the benzene s o l v e n t .  The  assumption I s made t h a t the v a r i a t i o n s i n p r e s s u r e r e m a i n i n g  after  c o r r e c t i o n s a r e due  t o a b s o r p t i o n o r r e l e a s e o f carbon monoxide.  these It i s  r e a l i z e d t h a t the s o l u b i l i t y o f carbon monoxide I n the l i q u i d phase change w i t h temperature i n t h e c l o s e d system. for  However t h i s cannot  the sudden changes i n p r e s s u r e n o t e d a t f a i r l y c o n s t a n t  may account  temperature.  Another p o s s i b i l i t y i s t h a t some o t h e r gas b e s i d e s carbon monoxide i s r e l e a s e d i n the system. at  T h i s c o u l d b e s t be checked by sampling  the peak o f the p r e s s u r e c u r v e .  T h i s procedure  dangerous w i t h the p r e s e n t equipment due  i s difficult  t o the h i g h t o x i c i t y o f  the gases and carbon  36  monoxide and c o b a l t c a r b o n y l s and the h i g h r e a c t i o n p r e s s u r e s temperatures. purpose. if  and  However a r e d u c i n g v a l v e c o u l d be i n s t a l l e d f o r t h i s  P l o t s o f the n a t u r e  submitted would be o f more d e f i n i t e  the benzene s o l u t i o n c o n t a i n i n g c a t a l y s t c o u l d be heated  value  to reaction  temperature w i t h carbon monoxide under p r e s s u r e b e f o r e i n j e c t i o n o f t h e substrate.  I f t h e r e a c t i o n were then c a r r i e d o u t a t c o n s t a n t temperature  any p r e s s u r e v a r i a t i o n s c o u l d d e f i n i t e l y be a s c r i b e d t o be r e s u l t s o f the r e a c t i o n .  I t s h o u l d be mentioned t h a t carbon monoxide may as an I d e a l gas throughout T h i s was  be t r e a t e d  the p r e s s u r e temperature range i n v o l v e d .  e s t a b l i s h e d by use o f the reduced  p r e s s u r e reduced  temperature  approximation.  Comparison o f the p l o t s f o r benzophenone oxime (page 66) i t s 0-methyl e t h e r (page 73)  and  shows both m a t e r i a l s cause a r e l e a s e o f  carbon monoxide a t low temperatures  (20 t o 55° C ) , n e a r l y 2i moles p e r  mole o f s u b s t r a t e i n the case o f the e t h e r , b u t o n l y 0.6 moles f o r the oxime i t s e l f .  Both o f these f i g u r e s are minimums f o r two  the carbon monoxide r e l e a s i n g r e a c t i o n may the carbon monoxide was  reasons.  First  have taken p l a c e p a r t l y w h i l e  b e i n g added.  The i n i t i a l p r e s s u r e c o u l d n o t  measured u n t i l a l l the added gas was  p r e s e n t and some time had t o be  allowed f o r s o l u b i l i t y e q u i l i b r i u m t o be reached.  Secondly  there i s  l i t t l e d e t a i l on the p l o t s i n t h i s a r e a so t h e a c t u a l maximum may have been r e c o r d e d .  not  In the case o f syn-benzaldoxime no p o i n t s were  r e c o r d e d i n the c o r r e s p o n d i n g  area.  S i n c e s t e r i c hindrance p l a y s an  be  37  important  p a r t i n the r a t e o f f o r m a t i o n  o f complexes (see page 13) i t  i s f e l t t h a t the O-methyl e t h e r s h o u l d f o r m a complex l e a s t and  readily  t h e r e f o r e p a r t o f the i n i t i a l p r e s s u r e r e c o r d e d i n the c a s e s  benzophenone oxime and  syn-benzaldoxime may  r e a c t i o n o f the s u b s t r a t e and c a t a l y s t .  a c t u a l l y have come f r o m  This conjecture could  checked by e q u i l i b r a t i n g the r e a c t i o n m i x t u r e a t c o n s t a n t b e f o r e i n j e c t i o n o f the  AU sorbed.  The  be  substrate.  the p l o t s show t h a t any gas r e l e a s e d i s q u i c k l y reabO-methyl e t h e r p l o t remains c o m p a r a t i v e l y  turned o f f .  n e a r the  original  heating  A f t e r t h i s p o i n t i t shows an a b s o r p t i o n o f 1  mole o f c a r b o n monoxide per mole o f s u b s t r a t e . correspond  the  temperature  p r e s s u r e v a l u e once the temperature reaches 165° G' u n t i l the element was  of  t o some r e a c t i o n a b s o r b i n g  T h i s phenomenon c o u l d  carbon monoxide o r t o the conden-  s a t i o n o f some unknown gaseous component.  The  benzaldoxime shows s i m i l a r  b e h a v i o u r i f the assumption i s made t h a t o r i g i n a l complex f o r m a t i o n v e r y r a p i d and  t h a t the o r i g i n a l p r e s s u r e r e c o r d e d  was  a l r e a d y i n c l u d e s the  carbon monoxide r e l e a s e d by the complexing a c t i o n .  The benzophenone p l o t shows remarkable p r e s s u r e t h e p o i n t where the temperature r e a c h e s 160° C.  changes f r o m  There i s a sudden  e v o l u t i o n o f 1 mole o f carbon monoxide f o l l o w e d by a sudden a b s o r p t i o n o f 2 moles.  A l l t h i s t a k e s p l a c e i n 5 minutes.  o f f e r e d f o r t h i s i n t e r e s t i n g phenomenon. peak a t the 37 minute mark i s e v i d e n c e d  No  e x p l a n a t i o n can  I t i s r e a l i z e d the by o n l y one  p o i n t but  be  pressure the  38  b e h a v i o u r was o b t a i n e d  on a second t r i a l  and t h e phenomenon a l s o  appears i n t h e work o f Hubscher ( 2 2 ) .  A t l e a s t two examples appear i n t h i s work o f c o b a l t c o n t a i n i n g compounds which were s o l u b l e i n benzene and l o s t t h e i r s o l u b i l i t y i n t h i s solvent a f t e r r e f l u x i n g i n l i g h t petroleum ether.  T h i s behaviour  c o u l d be s i m i l a r t o t h a t r e p o r t e d by H i e b e r (21) and mentioned on page  39  EXPERIMENTAL  A.  General  A l l infrared  s p e c t r a r e p o r t e d were o b t a i n e d u s i n g a Perkinr:  Elmer Model 2 1 s p e c t r o m e t e r i n t h i s department  e x c e p t f o r the  o f the reduced p r o d u c t o f 3 - p h e n y l p h t h a l i m i d i n e which was  spectrum  o b t a i n e d on  a Baird-Atomic s p e c t r o m e t e r i n the F o r e s t P r o d u c t s L a b o r a t o r y . v a p o r phase chromatography was i n t h i s department.  c a r r i e d o u t on equipment c o n s t r u c t e d  A l l alumina used f o r chromatography was  Drug Houses chromatographic  grade c a l c i n e d alumina.  were c a r r i e d o u t by Dr. A. B e r n h a r d t o f the Max Mulheim, Ruhr, Germany.  The  British  Elemental analyses  Planck I n s t i t u t e ,  M e l t i n g p o i n t s were determined u s i n g a  p o l a r i z i n g microscope on an e l e c t r i c a l l y heated h o t s t a g e .  Corrected  m e l t i n g p o i n t s were r e a d d i r e c t l y .  Acknowledgement i s hereby e x p r e s s e d t o Mr. H a r o l d Maclean the F o r e s t P r o d u c t s L a b o r a t o r y and Mrs.  M l  o f t h i s department  i n f r a r e d d e t e r m i n a t i o n s and t o Dr. S. Ryce and Mr. department  f o r vapor phase chromatography.  of  for  S. R u z i c k a o f t h i s  AO  B.  R e a c t i o n o f Syn-benzaldoxime  w i t h Carbon Monoxide  i n the Presence o f D i c o b a l t O c t a c a r b o n y l ,  a.  Preparation of reactants  Syn-benzaldoxime  was  p r e p a r e d a c c o r d i n g t o the method o f  Beckmann (2);.  The y i e l d o b t a i n e d was  31% o f pure p r o d u c t based on  benzaldehyde.  An i n f r a r e d spectrum i n c h l o r o f o r m s o l u t i o n was o b t a i n e d  as a check on the p u r i t y o f the aldoxLme (34-) and f o r comparison w i t h r e a c t i o n products,  D i c o b a l t o c t a c a r b o n y l was  method o f Wender e t a l (54-),  p r e p a r e d a c c o r d i n g t o the  The c a t a l y s t was n o t i s o l a t e d but was  d i r e c t l y i n the benzene s o l u t i o n i n which i t was o b t a i n e d . p r e p a r e d i n t h i s manner c o n t a i n s 0.25  The  used  catalyst  gm o r 7.3 x 10"^ moles p e r ml.  S p e c i a l l y d r i e d and p u r i f i e d t h i o p h e n e - f r e e benzene was u s e d b o t h t o p r e p a r e the c a t a l y s t and t o c a r r y out the r e a c t i o n s . used c o n t a i n e d 1.5$ chromatography.  by volume o f hydrogen as determined by vapor  by volume.  phase  Ah a n a l y s i s s u p p l i e d by the Matheson Company from whom  the c a r b o n monoxide was 0.0A%  The carbon monoxide  purchased i n d i c a t e d a hydrogen p e r c e n t a g e o f  The a n a l y s i s here was  c a r r i e d o u t by comparing  the  o b s e r v e d peak h e i g h t o f 100$ hydrogen w i t h the hydrogen peak from the carbon monoxide,  A b e t t e r procedure would have been t o use a known  m i x t u r e c l o s e r i n c o m p o s i t i o n t o t h e unknown.  T h i s may  have g i v e n  r e s u l t s c l o s e r t o the Matheson f i g u r e .  b.  R e a c t i o n procedure.  The r e a c t i o n was  c a r r i e d o u t i n a g l a s s l i n e d Aminco super-  41  p r e s s u r e r e a c t i o n v e s s e l which was Temperature  c o n t r o l was  equipped w i t h a r o c k e r mechanism.  a c h i e v e d t h r o u g h a Brown pyrometer u s i n g  a  thermocouple which had been c a l i b r a t e d a g a i n s t a s t a n d a r d thermometer.  An amount o f 6.5  gm o f syn-benzaldoxime  (0.054 mole) was  p l a c e d i n the g l a s s l i n e r w i t h 25 ml o f c a t a l y s t s o l u t i o n (0.02 m o l e ) . A homogeneous s o l u t i o n r e s u l t e d .  P u r i f i e d benzene was  added t o make the  t o t a l volume 60 ml and the l i n e r p l a c e d i n the r e a c t i o n v e s s e l t i v e v o i d 180 m l ) .  The s e a l e d v e s s e l was f l u s h e d t w i c e w i t h c a r b o n  monoxide t o remove a i r .  Carbon monoxide was r u n i n t o a t o t a l p r e s s u r e  o f 2300 p . s . i . a t 12° C (2200 p . s . i . a t 0° C ) . commenced.  (effec-  The Thermostat was  t o t h i s p o i n t i n 39 minutes.  H e a t i n g was  then  s e t a t 170° C and the temperature r o s e A f t e r 6 minutes a t t h i s temperature the  l a c k o f v a r i a t i o n i n the observed p r e s s u r e i n d i c a t e d no r e a c t i o n , the temperature was r a i s e d i n s t e p s o f t e n d e g r e e s t o 2 2 0 ° G. :temperature was  so  The  h e l d a t each t e n degree l e v e l f o r 6 t o 8 minutes.  F i n a l l y the temperature was m a i n t a i n e d a t 220° C f o r 17 minutes b e f o r e t u r n i n g o f f the h e a t i n g element. end o f h e a t i n g was 100 minutes.  The t o t a l e l a p s e d time from s t a r t t o The r e a c t i o n v e s s e l was  t o c o o l t o room temperature o v e r n i g h t . was 2070 p . s . i . a t 11° C (1990 a t 0° C ) . 210 p . s . i .  then a l l o w e d  The f i n a l p r e s s u r e o b s e r v e d T h i s i s an o v e r a l l d r o p o f  a t 0° G and c o r r e s p o n d s t o 0.115  mole o f carbon monoxide  which i s 2.1 moles per mole o f s u b s t r a t e o r 5.8 moles p e r mole o f catalyst.  A d e t a i l e d r e c o r d o f p r e s s u r e time and temperature was  and the r e s u l t s p l o t t e d on page 42,  kept  H^-^cT  TOTAXL •to  0°C  P R E S S U R E  F O R  0.054O . O Z  S x t ^  -  C o « « t c T t ?  6 E N Z A V . O O / \ M E  N\oi_es M O L E S  2300--  N o t e . : V^Vou«  VoR V^E.'S'_\--{._.  1 0  k 0 0 V0 2000  \900 80  \55 \70  205  _J  L-  0  V85  20  40  I  60  80 T\w\e  \M  L_  \CO W\\NUTSS  oo  43  The r e a c t i o n p r o d u c t was a brown homogeneous s o l u t i o n .  This  s o l u t i o n was evaporated a t 25 - 35° C u s i n g a water a s p i r a t o r t o remove any unchanged c a t a l y s t and the benzene s o l v e n t .  c.  Separation  and i d e n t i f i c a t i o n o f p r o d u c t s  The r e a c t i o n p r o d u c t a f t e r removal o f t h e benzene was a g r e e n tarry material.  I t d i s s o l v e d completely  o f 51 ml t o t a l volume.  i n warm benzene t o a s o l u t i o n  A 3 ml a l i q u o t o f t h i s s o l u t i o n was p l a c e d on  an alumina column (12-& cm x 3 cm d i a m e t e r ) f o r chromatography.  The  r e s u l t s f o r t h i s a l i q u o t (one s e v e n t e e n t h o f the t o t a l r e a c t i o n p r o d u c t ) are d e t a i l e d on page 44.  ( i ) F i r s t f r a c t i o n from chromatogram (compound  On commencing  e l u t i o n w i t h benzene a p u r p l e band moved q u i c k l y  down the column and r e s u l t e d i n a r e d benzene s o l u t i o n . the c o l o r o f t h i s s o l u t i o n g r a d u a l l y changed t o brown. the s o l v e n t l e f t ethanol  a m i x t u r e o f white and brown s o l i d s .  produced a r e d c o l o r e d e t h a n o l  t a l l i n e residue.  On  standing  Evaporation  of  Addition of  s o l u t i o n and l e f t  a white c r y s -  T h i s white m a t e r i a l was e a s i l y s o l u b l e i n benzene  l e a v i n g the brown r e s i d u e . and l e f t  A)  T h i s brown r e s i d u e f a i l e d t o m e l t a t 350° C  a c o b a l t - c o n t a i n i n g r e s i d u e on i g n i t i o n .  The white m a t e r i a l  was r e c r y s t a l l i z e d f r o m petroleum e t h e r and m e l t e d a t 239 - 2 4 2 ° G -with some change i n c r y s t a l s t r u c t u r e n e a r 220 -  225°  C.  The i n f r a r e d  spectrum o f t h i s m a t e r i a l (compound A) showed no a b s o r p t i o n i n the  44  Chromatography o f R e a c t i o n P r o d u c t o f Syn-benzaldoxime ( A l i q u o t c o n t a i n i n g one-seventeenth o f r e a c t i o n p r o d u c t )  Amt. used i n ml  Eluent  Weight i n mgm  Product  Description  Compound A  purplish o i l y c r y s t a l s odor o f benzaldehyde  40  white c r y s t a l s  40  yellow o i l y material plus white c r y s t a l s  120  Benzene  0-125  Benzene  125-175  Nothing  Benzene  175-325  Compound B  Benzene  325-775  Nothing  Benzene e t h a n o l 99 r l  775-875  Nothing  Benzene e t h a n o l 99 r l  875-1075  Compound C  Benzene e t h a n o l 98*2  1075-1225  Nothing  Benzene e t h a n o l 98:2  1075-1225  Nothing  Benzene e t h a n o l 9812  1225-1275  Compound D  Benzene e t h a n o l 98 tZ  1275-1325  Nothing  yellow o i l  27  F u r t h e r washings w i t h 200 ml benzene e t h a n o l 50:50, 200 ml o f a b s o l u t e e t h a n o l , and 200 ml o f acetone produced n o t h i n g . Apparent o r g a n i c y i e l d from a l i q u o t  227 mgm  T o t a l apparent  3.86 gm  yield  45  c a r b o n y l r e g i o n so no f u r t h e r work was done on i t .  The i n f r a r e d  spectrum (potassium bromide d i s c ) showed t h e f o l l o w i n g major absorpt i o n peaks:  3050W> 1598sh, 1589W, 1523S, 1369S, 1301W, 1175W, 1069W,  1029W, 843M, 746S, 686S, 648M.  The i n f r a r e d spectrum i s r e p r o d u c e d  on page 46.  (ii)  Second f r a c t i o n f r o m chromatogram (Compound B)  T h i s f r a c t i o n appeared w h i t e b u t p i c k e d up a y e l l o w during evaporation  color  o f t h e s o l v e n t (water a s p i r a t o r l e s s t h a n 3 5 ° C ) .  M e l t i n g range o f t h e crude m a t e r i a l was 100 - 2 3 0 ° C.  L i g h t petroleum  e t h e r d i s s o l v e d t h e y e l l o w m a t e r i a l l e a v i n g a white r e s i d u e which m e l t e d a t 280 - 2 8 2 ° G a f t e r two r e c r y s t a l l i z a t i o n s from 30 - 6 0 ° C petroleum ether.  The i n f r a r e d spectrum o f compound B f a i l e d t o show  a b s o r p t i o n i n t h e c a r b o n y l r e g i o n so no f u r t h e r work was done on i t . The  i n f r a r e d (potassium bromide d i s c ) showed t h e f o l l o w i n g major ab-  sorptions:  3055W, 1601W, 1579W, 1507W, 1492M, 1465M, 1447W, 1414W,  1400W, 1325W, 1204W, 1153W, 1072W, 973W, 917W, 767M, 736M, 714M, 698S.  (iii)  T h i r d f r a c t i o n from chromatogram ( s y m - d i b e n z y l u r e a )  T h i s f r a c t i o n a l s o c o n s i s t e d o f a w h i t e m a t e r i a l w i t h some yellow.  The y e l l o w c o l o r was s l i g h t l y s o l u b l e i n l i g h t p e t r o l e u m  and v e r y s o l u b l e i n e t h e r . either solvent.  ether  White c r y s t a l s were s l i g h t l y s o l u b l e i n  Crude m a t e r i a l was e x t r a c t e d w i t h e t h e r and 30 - 6 0 ° C  p e t r o l e u m e t h e r t o l e a v e a white m a t e r i a l m e l t i n g  a t 160 - 1 6 7 ° C  Infrared spectrum (potassium bromide disc) Compound A  4oe»o  — I 3ooo  2 0 O O  \9  \a  \1  \€»  \5  \A-  \3  va.  w  \ooo  3  -t1  48  (Compound C ) .  Compound C d i s s o l v e d f a i r l y r e a d i l y i n benzene and l e f t a s m a l l amount o f green r e s i d u e . and f a i l e d t o m e l t a t 3 1 0 ° C  T h i s green m a t e r i a l c o n t a i n e d I t dissolved readily i n  h y d r o c h l o r i c a c i d t o a green s o l u t i o n .  cobalt  concentrated  On d i l u t i o n and t r e a t m e n t w i t h  sodium h y d r o x i d e t h e presence o f c o b a l t was proven.  Compound C was now r e c r y s t a l l i z e d from benzene petroleum e t h e r and m e l t e d a t 168 - 169^"° C.  The i n f r a r e d spectrum ( p o t a s s i u m  bromide d i s c ) showed t h e f o l l o w i n g major a b s o r p t i o n s :  3337S, 3043W,  2922W, 1625S, 1591S, 1575S, 1497W, 1475W, 1458M, 1435W, 1369W, (1275 t o 1225 broad a b s o r p t i o n ) , 1080S, 1027W, 757W, 733W, 698S.  The  i n f r a r e d spectrum I s reproduced on page 49.  Compound C was s o l u b l e i n benzene, a l c o h o l , e t h e r , l i t t l e i n l i g h t petroleum e t h e r .  The compound was i n s o l u b l e i n c o l d  water but d i s s o l v e d s l o w l y i n h o t c o n c e n t r a t e d was  i n s o l u b l e i n c o l d concentrated  sodium h y d r o x i d e .  h y d r o c h l o r i c a c i d but slowly  s o l v e d on h e a t i n g t o a l i g h t y e l l o w c o l o r e d s o l u t i o n . c o u l d be o b t a i n e d  but v e r y  It dis-  No p r e c i p i t a t e  f r o m e i t h e r t h e b a s i c o r a c i d i c s o l u t i o n s by n e u t r a l -  i z i n g w i t h h y d r o c h l o r i c a c i d o r sodium h y d r o x i d e r e s p e c t i v e l y .  Compound C was s o l u b l e i n c o n c e n t r a t e d p r e c i p i t a t e was o b t a i n e d  The  s u l p h u r i c a c i d and no  on d i l u t i o n w i t h water.  a c i d s o l u t i o n s above were e x t r a c t e d w i t h benzene.  m a t e r i a l recovered  The  proved i d e n t i c a l w i t h o r i g i n a l by mixed m e l t i n g  point.  Infrared spectrum (potassium bromide disc) sym-dibenzylurea ( _____) sym-dibenzoylurea (— - =) —I 30OO  1  2000  j I/ \i 1  1  1  1  1  IS  \8  \7  \€>  1 \50O  1  1  \4  V3  1 U  1 U  1  1  1  1  \000  <3  e>  7  1  6oo  S  50 Compound C was now heated a t r e f l u x temperature h o u r s i n 20$ sodium h y d r o x i d e i n e t h a n o l water.  f o r forty  On n e u t r a l i z a t i o n  with  h y d r o c h l o r i c a c i d c r y s t a l s were o b t a i n e d i d e n t i c a l t o o r i g i n a l by mixed m e l t i n g p o i n t .  Ah attempt  t o prepare an a c e t a t e d e r i v a t i v e under t h e f o l -  l o w i n g c o n d i t i o n s produced  an o i l .  An amount o f 5 mgm  o f compound C  was r e f l u x e d f o r f o u r hours w i t h f u s e d sodium a c e t a t e (50 mgm) o f a c e t i c anhydride.  On p o u r i n g t h e a c e t y l a t i n g m i x t u r e  and 5 ml  onto i c e a  s m a l l amount o f o i l which was i n s o l u b l e i n h o t water was o b t a i n e d . T h i s o i l was n o t c r y s t a l l i z a b l e from t h e common s o l v e n t s .  An amount o f 50 mgm  o f compound C was heated on a steam b a t h  i n concentrated hydrochloric acid r e s u l t i n g i n a l i g h t l y yellow colored solution.  Aqueous d i l u t i o n o f t h i s a c i d s o l u t i o n produced  appearance w i t h some curdy white m a t e r i a l . the m i l k y appearance.  E t h e r e x t r a c t i o n removed  E v a p o r a t i o n o f the e t h e r l a y e r r e s u l t e d i n  recovery o f the o r i g i n a l m a t e r i a l . hydrolysis.  a milky  Ah amount o f 10,8 mgm  Y e l l o w c o l o r a t i o n shows s l i g h t o f compound C was now r e f l u x e d f o r  6 hours w i t h c o n c e n t r a t e d h y d r o c h l o r i c a c i d . t o 6 normal and allowed t o s t a n d o v e r n i g h t .  The s o l u t i o n was d i l u t e d No c r y s t a l s appeared.  ether e x t r a c t o f t h i s s o l u t i o n contained nothing. was now n e u t r a l i z e d w i t h sodium h y d r o x i d e .  The aqueous l a y e r  There was no immediate  p r e c i p i t a t e b u t on s t a n d i n g o v e r n i g h t a f l o c c u l e n t p r e c i p i t a t e T h i s m a t e r i a l was e x t r a c t e d w i t h c h l o r o f o r m . i s o l a t e d was t h e o r i g i n a l .  An  appeared.  Again t h e m a t e r i a l  51  The aqueous l a y e r r e m a i n i n g a f t e r the c h l o r o f o r m e x t r a c t i o n was  extracted with ether.  The e t h e r c o n t a i n e d n o t h i n g .  O x i d a t i o n of p h t h a l i m i d i n e was s u i t a b l e o x i d a t i o n procedure  now  f o r compound C.  attempted  to develop  The p h t h a l i m i d i n e  prepared from p h t h a l i m i d e by the method o f Graebe ( 1 8 ) . spectrum  o f p h t h a l i m i d i n e was  products.  One  s l o w l y w h i l e the s o l u t i o n was was  infrared  o f p h t h a l i m i d i n e was gm  d i s s o l v e d i n 50  o f s o l i d sodium dichromate  heated  was  s t r o n g l y on a steam bath.  c a r r i e d o u t f o r 4 hours a f t e r c o m p l e t i o n o f the dichromate  The r e a c t i o n m i x t u r e was homogeneous s o l u t i o n .  was  o b t a i n e d f o r comparison w i t h r e a c t i o n  An amount o f 239 mgm  ml o f g l a c i a l a c e t i c a c i d .  An  a  poured  added  Reflux addition.  i n t o 50 ml o f water r e s u l t i n g i n a  T h i s aqueous s o l u t i o n was  extracted with chloro-  form t o y i e l d a r e s i d u e o f an a c e t i c a c i d s o l u t i o n .  A d d i t i o n o f water  t o the a c e t i c a c i d produced  crystals.  form and the c h l o r o f o r m was  washed w i t h water t o g e t r i d o f most o f the  a c e t i c a c i d and a g a i n evaporated. p i t a t i o n o f c r y s t a l s which were now  These were r e d i s s o l v e d i n c h l o r o -  Water added now  a g a i n caused  preci-  r e c r y s t a l l i z e d d i r e c t l y from water.  The m a t e r i a l d i s s o l v e d s l o w l y i n b o i l i n g water and r e c r y s t a l l i z e d on c o o l i n g (m.p.  236 - 2 3 8 ° C w i t h s o f t e n i n g a t 2 3 0 ° G-).  i s exact f o r phthalimide. Y i e l d was  product.  o f compound C were now  o x i d i z e d u n d e r the same  c o n d i t i o n s u s i n g 25 ml o f g l a c i a l a c e t i c a c i d and 0.3 dichromate.  behaviour  A mixed m e l t i n g p o i n t showed no d e p r e s s i o n .  79$ o f r e c r y s t a l l i z e d  S i x t y - t h r e e mgm  This  rapidly  The o x i d i z i n g m i x t u r e was  gm o f sodium  extracted d i r e c t l y with chloroform.  52  Treatment as above y i e l d e d 42 mgm o f a p r o d u c t m e l t i n g a t 202 - 2 0 3 ° C a f t e r two r e c r y s t a l l i z a t i o n s f r o m e t h a n o l water.  The i n f r a r e d  spectrum  (potassium bromide d i s c ) o f t h i s o x i d i z e d product i s shown on page 4-9 compared t o compound C.  The major a b s o r p t i o n peaks were measured as  f o l l o w s : 3240W, 1753S, 1670S, 1603W, 1577W, 1534M, 1506M, 1480M, 1288M, 1266S, 1200M, 1192W, 1067W, 771M, 696S.  This product d i d n o t r e a c t w i t h  sodium b i c a r b o n a t e and was n o t an a c i d .  The p r o d u c t d i s s o l v e d v e r y  r e a d i l y i n acetone  b u t r e q u i r e d warming t o d i s s o l v e i n e t h a n o l .  d i s s o l v e d by b o i l i n g water.  I t was  The p r o d u c t was s m a l l w e l l formed n e e d l e s .  The aqueous l a y e r from t h e o x i d a t i o n r e a c t i o n r e m a i n i n g  after  c h l o r o f o r m e x t r a c t i o n was now a c i d i f i e d w i t h s u l p h u r i c a c i d s i n c e an a c i d s t r o n g e r than a c e t i c a c i d i f formed i n t h e r e a c t i o n would n o t otherwise  be e x t r a c t e d by o r g a n i c s o l v e n t s .  added t o d e s t r o y excess o x i d a n t .  Now sodium b i s u l f i t e was  Ether e x t r a c t i o n o f the r e s u l t i n g  green  a c i d s o l u t i o n r e c o v e r e d 5 mgm o f an o r g a n i c a c i d which was e a s i l y s o l u b l e i n e t h e r , e t h a n o l o r benzene, b u t s o l u b l e l e s s r e a d i l y i n l i g h t ether.  The a c i d f a i l e d t o c r y s t a l l i z e f r o m l i g h t petroleum  r e c r y s t a l l i z e d from water a t 0 ° C. 120 - 1 2 2 ° C.  petroleum  ether but  A f t e r 2 r e c r y s t a l l i z a t i o n s m.p. was  Mixed m e l t i n g p o i n t w i t h an a u t h e n t i c sample o f b e n z o i c  a c i d was 120 - 1 2 2 ° Q.  T h i o n y l c h l o r i d e was added t o 3 mgm o f d r y m a t e r i a l f r o m above and r e f l u x e d on steam b a t h f o r o n e - h a l f hour. i n t o 1 ml o f c o l d c o n c e n t r a t e d ammonium h y d r o x i d e . s e p a r a t e d and was washed w i t h water.  M i x t u r e was poured A precipitate  The p r e c i p i t a t e was d i s s o l v e d i n  e t h a n o l and p r e c i p i t a t e d o u t w i t h water.  M e l t i n g p o i n t was 126 - 1 2 7 ° C.  53  L i t e r a t u r e f o r benzamide i s 1 2 7 ° G;  Analysis calculated for C  1 5  H  l 6  N p  C,  75.00;  H,  6.67j  N,  11.67;  M o l . wt. 240  i  2  Found  C,  74.87;  H,  6.79;  N,  11.91;  Mol. wt. (Rast) 263 The h i g h amount o f hydrogen suggests  a l i n e a r s t r u c t u r e and  the i n f r a r e d o f t h e o x i d a t i o n product demands 2 d i f f e r e n t  carbonyls.  Sym-dibenzylurea f i t s m.p., a n a l y s i s , i n f r a r e d , s o l u b i l i t y , and hydrol y s i s information.  So an a u t h e n t i c sample was prepared  the procedure o f D a v i s and B l a n c h a r d  (8).  T h i s a u t h e n t i c sample proved  t o have an i d e n t i c a l i n f r a r e d spectrum w i t h compound C. was  o b t a i n e d i n a mixed m e l t i n g p o i n t  according to  No d e p r e s s i o n  determination.  The o x i d i z e d product must now be sym-dibenzoylurea whose m.p. i s 2 0 3 ° C as r e p o r t e d by B i l t z  (5).  No e x p l a n a t i o n i s o f f e r e d here f o r  t h e m e l t i n g p o i n t o f 2 0 8 ° C r e p o r t e d by B i l l e t e r ( 4 ) .  (iv)  F o u r t h f r a c t i o n from chromatogram (mono-benzylurea)  Compound D was a l s o accompanied by a y e l l o w o i l y m a t e r i a l . Repeated r e c r y s t a l l i z a t i o n from benzene - petroleum  e t h e r was r e q u i r e d  t o produce a pure sample which m e l t e d a t 147 - 1 4 9 ° C. spectrum i n a potassium absorptions;  The i n f r a r e d  bromide d i s c showed t h e f o l l o w i n g major  3440S, 3323S, 3035W, 2922W, 2876W, 1651S, 1601S, 1564S,  1499W, 1471M, 1458M, 1389M, 1338W, 1329W, 1312W, 12C9W, 1144M, 1109M,  54  1079W, 1027W, 758M, 752M, 697S. 55.  S i n c e t h e expected  product  T h i s spectrum i s reproduced  o f the r e a c t i o n was p h t h a l i m i d i n e  ( m e l t i n g p o i n t 1 5 0 ° G), by analogy al  t o p r e v i o u s work o f R o s e n t h a l e t  (40) immediate comparison was made w i t h an a u t h e n t i c sample o f  p h t h a l i m i d i n e (18).  The i n f r a r e d s p e c t r a were c o n s i d e r a b l y d i f f e r e n t  and a mixed m e l t i n g p o i n t showed 2 5 ° C d e p r e s s i o n was  on page  not phthalimidine.  so t h a t compound D  The i n f r a r e d spectrum o f D s t r o n g l y  the presence o f a primary  suggested  amine o r amide s i n c e i t showed s t r o n g ab-  s o r p t i o n a t 3440, 3328, 1601, and 1564.  S o l u b i l i t y considerations  r u l e d o u t t h e amino group and presence o f an apparent c a r b o n y l f u n c t i o n a t 1651 cm""'' supported  the primary  amide.  The c a r b o n y l f u n c t i o n f a i l e d  to r e a c t w i t h 2, 4, d i n i t r o - p h e n y l h y d r a z i n e thus c o n f i r m i n g t h e amide hypothesis.  S i n c e sym-dibenzylurea  may be o b t a i n e d from mono-benzylurea  by simple h e a t i n g , a sample o f mono-benzylurea was prepared  (8),  Mixed  m e l t i n g p o i n t and comparison o f i n f r a r e d s p e c t r a showed compound D t o be i d e n t i c a l w i t h mono-benzylurea,  d.  Repeat o f r e a c t i o n between carbon monoxide and syn-benzaldoxime i n t h e presence o f d i c o b a l t o c t a c a r b o n y l ,  Syn-benzaldoxime and d i c o b a l t o c t a c a r b o n y l were prepared and r e a c t e d as on page 40,  A sample o f t h e product gases was a n a l y z e d b y  vapor phase chromatography.  The o n l y gas d e t e c t e d was carbon monoxide  showing any hydrogen o r i g i n a l l y p r e s e n t had r e a c t e d . observed  corresponded  The p r e s s u r e d r o p  t o t h e a b s o r p t i o n o f 0.075 moles o f c a r b o n monoxide.  WAVE.  NVIM\^^-^S  NT*  CV\"'  56  S i n c e 0.06  moles o f s u b s t r a t e were used t h i s i s 1 . 2 5  moles per mole o f  substrate.  The solution.  r e a c t i o n p r o d u c t was  T h i s s o l u t i o n was  a homogeneous d a r k brown benzene  evaporated under vacuum (water a s p i r a t o r )  at l e s s than 35° C t o remove or decompose any u n r e a c t e d c a t a l y s t and benzene s o l v e n t .  The  distillate  c o n t a i n i n g excess c a t a l y s t .  The  r e s i d u e was  The  was  a l i g h t y e l l o w benzene s o l u t i o n  s o l i d r e s i d u e appeared b l a c k i n c o l o r .  e x t r a c t e d twice with b o i l i n g  T h i s l e f t a d a r k green ( c o b a l t c o n t a i n i n g ) r e s i d u e solution.  T h i s r e s i d u e was  appeared p a r t l y s o l u b l e .  now  and  chloroform. a brownish green  e x t r a c t e d w i t h b o i l i n g acetone  F i l t r a t i o n o f the acetone a f t e r c r y s t a l -  l i z a t i o n produced a l i g h t green s o l i d  ( m a t e r i a l I ) (0.4 gm)  n i t e d i n a f l a m e and l e f t a c o b a l t c o n t a i n i n g r e s i d u e . s t a b l e a t 350° C on the m e l t i n g  point slide.  which i g -  This s o l i d  The  i n f r a r e d spectrum o f m a t e r i a l I was  and f a i l e d t o show a b s o r p t i o n  a t t r i b u t a b l e t o the c a r b o n y l s  but  of a cobalt  A n a l y s i s o f m a t e r i a l I f a i l e d t o show any  r e l a t i o n s h i p between the  constituents.  Co,  31.26;  C,  12.28;,  N,  2.99;  H,  was  determined  c a r b o n y l compound (33).  Founds  was  I t d i s s o l v e d i n hydro-  c h l o r i c a c i d t o a b r i g h t green s o l u t i o n w i t h o u t e f f e r v e s c e n c e i n s o l u b l e i n water.  and  simple  2.75.  F u r t h e r e x t r a c t i o n o f the r e s i d u e w i t h r e f l u x i n g acetone dissolved nothing (2.3 gm)  which was  and l e f t  a green i n s o l u b l e m a t e r i a l ( m a t e r i a l I I )  s i m i l a r i n appearance t o m a t e r i a l I and  also i g n i t e d  57  i n t h e flame t e s t l e a v i n g a b l a c k c o b a l t r e s i d u e .  The was e v a p o r a t e d  above c h l o r o f o r m  s o l u t i o n containing organic  products  t o l e a v e a green r e s i d u e which was r e p e a t e d l y e x t r a c t e d  w i t h r e f l u x i n g petroleum  e t h e r (30 - 6 0 ° C ) .  The petroleum  c o l o r e d wine straw and on c o o l i n g became o p a l e s c e n t .  e t h e r was  The green r e s i d u e  remained unchanged i n appearance.  Evaporation  o f t h e petroleum  e t h e r s o l u t i o n y i e l d e d 0.8 gm  o f a brown v i s c o u s l i q u i d whose s m e l l resembled benzaldehyde.  S a t u r a t e d aqueous sodium b i s u l p h i t e was added and some i n soluble c r y s t a l s extracted with ether.  On a d d i t i o n o f t h e e t h e r a v e r y  s m a l l amount o f c o b a l t c o n t a i n i n g v i o l e t m a t e r i a l s e p a r a t e d . f i l t e r e d o f f and d i s c a r d e d . 5 mgm  The e t h e r l a y e r on e v a p o r a t i o n  T h i s was produced  o f a m a t e r i a l which m e l t e d a t 229 - 2 3 0 ° C w i t h a change i n c r y s t a l  s t r u c t u r e a t 210 - 2 1 5 ° C a f t e r r e c r y s t a l l i z a t i o n from a l c o h o l .  This  was shown i d e n t i c a l by mixed m e l t i n g p o i n t w i t h Compound A (page 4 3 ) .  The  aqueous l a y e r was a c i d i f i e d w i t h h y d r o c h l o r i c a c i d and  warmed t o d e s t r o y t h e b i s u l p h i t e .  2, 4 - D i n i t r o p h e n y l h y d r a z i n e  reagent  was added and an immediate y e l l o w p r e c i p i t a t e was formed (0.54 gm) m.p. 235 - 2 3 7 ° C.  Mixed m.p. w i t h an a u t h e n t i c sample o f benzaldehyde  2, 4-dinitrophenylh.ydrazone  The  was 235 - 2 3 7 ° C.  green r e s i d u e from t h e petroleum  e t h e r e x t r a c t i o n was now  e x t r a c t e d w i t h benzene and a v i o l e t s o l i d was f o u n d (1.6 gm).  t o be i n s o l u b l e  The major p a r t o f t h e o r g a n i c p r o d u c t was now c o n t a i n e d i n  58  the benzene s o l u t i o n .  On s t a n d i n g 0.4 gm o f white c r y s t a l s p r e c i p i t a t e d .  Chromatography o f a s m a l l sample o f these c r y s t a l s showed them t o be a mixture  o f compound C and compound D (pages 41 and 53).  The green benzene s o l u t i o n on e v a p o r a t i o n y i e l d e d 2.26 gm o f a brown o i l which d i s s o l v e d chromatography.  c o m p l e t e l y i n 15 ml o f c o l d benzene f o r  Chromatography o f the above benzene s o l u t i o n on  ( 7 i x 10 cm) gave t h e f o l l o w i n g  Eluent  results.  Amount  Benzene  0-400  Benzene  400 -  Benzene e t h e r 50:50  800  0 - 4 0 0  compound A m.p. 2 4 4 - 2 4 5 ° C  Benzene e t h e r 50*50  800 - 1000  Benzene e t h e r 50:50  1000 - 1200  yellow o i l  Benzene e t h e r 50:50  1200 - 1400  nothing  0 -  500  Ethanol  500 -  Ethanol  700 - 1000  700  mgm  100  mgm  0.2  gm  0.4  gm  1.1  gm  nothing  400 -  800  130  nothing  Benzene e t h e r 50:50  Ethanol  alumina  compound B m.p. 2 8 7 i - 2 8 9 ° C nothing  compound C m.p. 165 - 172  C  nothing brown o i l  The f i n a l f r a c t i o n from t h i s chromatographic shown by r e c r y s t a l l i z a t i o n t o c o n t a i n c o b a l t  s e p a r a t i o n was  and 0.2 gm o f compound D.  59  Y i e l d from chromatogram was 1.93 gm from 2.3 added. y i e l d o f o r g a n i c m a t e r i a l from t h e r e a c t i o n was 5.2  C.  Total overall gm.  A c t i o n o f Carbon Monoxide on Benzophenone Oxime i n the Presence o f D i c o b a l t  a.  Octacarbonyl.  P r e p a r a t i o n o f benzophenone oxime  A m i x t u r e o f 20 gm o f benzophenone, 20 gm o f hydroxylamine h y d r o c h l o r i d e , 20 ml o f p y r i d i n e and 200 ml o f e t h a n o l was r e f l u x e d on a steam b a t h f o r f o u r h o u r s .  The a l c o h o l was then removed by  d i s t i l l a t i o n to leave a syrupy mixture.  T h i s m i x t u r e was c o o l e d i n  an i c e b a t h and 150 ml o f water added s l o w l y w i t h s t i r r i n g .  The  r e s u l t i n g c r y s t a l s were r e c r y s t a l l i z e d twice from e t h a n o l water.  Yield  a f t e r two r e c r y s t a l l i z a t i o n s was 13.5 gm (62$ o f t h e o r e t i c a l ) (m.p. U3  - 1A5° C ) .  b.  L i t e r a t u r e 144° C.  Reaction  procedure  The c a t a l y s t was prepared  as on page 40 and r e a c t i o n was  c a r r i e d o u t i n e s s e n t i a l l y t h e same manner.  T h i r t e e n gm (0.07 mole)  o f benzophenone oxime and 25 ml o f c a t a l y s t s o l u t i o n were used (0.02 moles).  O r i g i n a l p r e s s u r e ima 2210 p . s . i . c o r r e c t e d t o 0° C,  p r e s s u r e was 1990 p . s . i . c o r r e c t e d t o 0 ° C.  final  T h i s i s an a b s o r p t i o n o f  0.12 mole o f carbon monoxide o r 1.75 moles p e r mole o f s u b s t r a t e .  60  T o t a l h e a t i n g time was seventy-two m i n u t e s .  c.  S e p a r a t i o n and i d e n t i f i c a t i o n o f the p r o d u c t s  The g l a s s l i n e r c o n t a i n e d c r y s t a l l i n e m a t e r i a l and a brown benzene s o l u t i o n . brown c r y s t a l s .  The benzene was evaporated  a t 25 - 3 5 ° C t o l e a v e  Some u n r e a c t e d d i c o b a l t o c t a c a r b o n y l d i s t i l l e d  with  t h e benzene t o produce an orange c o l o r e d s o l u t i o n .  S o l u t i o n o f t h e brown c r y s t a l s i n h o t c h l o r o f o r m produced a deep blue s o l u t i o n .  N o r i t e was added and t h e s o l u t i o n f i l t e r e d , h o t  a f t e r a few minutes r e f l u x .  The s o l u t i o n r e t a i n e d t h e b l u e  Some p i n k m a t e r i a l remained w i t h the n o r i t e . was  c o o l e d and white  color.  The chloroform s o l u t i o n  c r y s t a l s s e p a r a t e d which melted 197 - 2 1 0 ° C  (material I ) .  R e c r y s t a l l i z a t i o n from c h l o r o f o r m f a i l e d t o change t h i s  m e l t i n g range.  A l l common s o l v e n t s were used i n an attempt t o f i n d a  suitable r e c r y s t a l l i z a t i o n solvent.  Repeated r e c r y s t a l l i z a t i o n o f t h e  m a t e r i a l from benzene o r from e t h a n o l gave c r y s t a l s m e l t i n g a t 225 2 2 7 ° G.  M a t e r i a l I was e x t r a c t e d i n a S o x h l e t apparatus  using ether.  An e t h e r i n s o l u b l e r e s i d u e (20 mgm) m e l t e d  f o r 4 hours a t 280 -  2 8 4 ° C (compound A ) .  E v a p o r a t i o n o f t h e e t h e r s o l u t i o n gave c r y s t a l s m e l t i n g a t 198 - 2 3 0 ° C ( M a t e r i a l I I ) .  M a t e r i a l I I was white f l u f f y n e e d l e s which gave a r e d c o l o r with concentrated  sulphuric acid d i s s o l v i n g t o a l i g h t yellow  solution.  61  D i l u t i o n destroyed  the c o l o r and  r e p r e c i p i t a t e d white m a t e r i a l .  Con-  c e n t r a t e d h y d r o c h l o r i c a c i d showed a green c o l o r a t i o n and f o r m i c produced a r e d c o l o r .  I t was  n o t e d t h a t these same c o l o r s can  produced by a c t i o n of the above r e a g e n t s on c o b a l t o u s  Ah e t h e r and  s o l u t i o n of m a t e r i a l I I was  the r e s u l t i n g c r y s t a l s s e p a r a t e d .  three  times s t i l l  m a t e r i a l was  197  a c e t i c anhydride and  be  salts.  p a r t i a l l y evaporated  These r e c r y s t a l l i z e d from methanol  gave above c o l o r s w i t h a c i d s . - 199°  acid  C (compound B).  Reaction  M e l t i n g p o i n t of  this  o f the m a t e r i a l  with  sodium a c e t a t e under anhydrous c o n d i t i o n s  l i g h t y e l l o w c r y s t a l s which melted a t 197  - 199°  C.  produced  Analytical results  on compound B were:  C,  80.21;  H,  5.35;  N,  Calculated f o r 2 7 2 2 2 ° 2 C  C,  79.80;  H,  H  N  5.40; C  C,  80.38;  H,  H  5.26;  N  0  N,  Mol.  wt.  380  6.89;  Mol.  wt.  406  6.70;  Mol.  wt.  418  !  N,  Calculated f o r 2 8 2 2 2 2  6.53;  :  Repeated r e c r y s t a l l i z a t i o n from methanol o f t h a t p a r t  of  m a t e r i a l I I which seemed l e a s t s o l u b l e i n e t h e r gave c r y s t a l s m e l t i n g a t 225  - 227° C (compound C ) ,  Compound C was  compared w i t h an  authentic  sample o f 3 - p h e n y l p h t h a l i m i d i n e (39) and found t o be i d e n t i c a l t h r o u g h i n f r a r e d spectrum and mixed m e l t i n g m e l t e d a t 153  - 154°  point.  C; l i t e r a t u r e m.p.  154°  The C  acetate d e r i v a t i v e (39).  62  A n a l y s i s o f compound C:  Calculated f o r G  H 11 H  C, 80.38;  N 0  M  Found:  o  1  H,  5.27;  ,  2  C, 80.35; H, Mol. wt.  0  N,  6.70;  9  5.56; N, ( R a s t ) 226  6.65;  Compound B was reduced u s i n g the f o l l o w i n g e x p e r i m e n t a l conditions;  compound B (63 mgm)  (.0015 m o l e s ) , 17 mgm  i n 25 ml o f g l a c i a l a c e t i c a c i d .  Hydrogen was  temperature and p r e s s u r e (64..4 ml) (.003 in  5^ h o u r s ) .  a steady r a t e .  The hydrogen was  added a t atmospheric  moles o f hydrogen were absorbed  absorbed r a p i d l y i n i t i a l l y  and then a t  No s i g n i f i c a n t change i n the r a t e o f hydrogen  c o u l d be d e t e c t e d a t any time. of  of platinum oxide  The m a t e r i a l l e f t a f t e r e v a p o r a t i o n  s o l v e n t s m e l t e d a t 100 t o 210° C.  benzene f o r chromatography  absorption  T h i s m a t e r i a l was d i s s o l v e d i n  u s i n g an alumina column ( 1 ^ " x 4"').  f i r s t 120 ml o f benzene e l u e n t produced n o t h i n g .  The "  The n e x t 40 ml  produced a y e l l o w o i l from which h o t l i g r o i n e x t r a c t e d white c r y s t a l s ( m a t e r i a l B 1, m.p.  l e s s than 110° C ) .  F u r t h e r benzene (100 ml)  benzene c o n t a i n i n g 2% e t h a n o l (100 ml) produced n o t h i n g .  and  Benzene  (100 ml) c o n t a i n i n g 10% e t h a n o l y i e l d e d s m a l l n e e d l e s which grew t o l a r g e n e e d l e s a t 175° C and m e l t e d a t 223 - 224° C ( M a t e r i a l B-2). One hundred p e r c e n t e t h a n o l (100 ml) produced c r y s t a l s m e l t i n g a t 175 - 185° C ( m a t e r i a l B-3).  Compound C ( 3 - p h e n y l p h t h a l m i d i n e ) was experimental conditions.  reduced u s i n g the same  Chromatography o f the r e a c t i o n p r o d u c t gave  63 three f r a c t i o n s of melting point; 125 - 150° C ( C - l ) , 169 - 170° C (C-2) and 223 - 224° C (C-3),.  These materials were also obtained from  a p a r a l l e l reduction of 3-phenylphthalimidine prepared by the method of Rose (39).  Material B-2 and C-3 were shown to be i d e n t i c a l by com-  parison o f i n f r a r e d spectrum and mixed melting point.  The i n f r a r e d  spectrum of compound C-3 i n potassium bromide d i s c showed the following major absorptions; 3210S, 2920S, 2830S, 1673S, 1440M (broad), 1383W, 1347W, 1325W, 1275M, 1255M, 1195W, 1172W, 1142W, 982W, 888W, 862W, 752M, 717W.  The spectrum o f 3-phenylphthalimidine compared to i t s reduced product i s shown on page 64.  Detailed comparison of the spectra  of C-3 was made with that of 3-phenylphthalimidine.  Bands present i n  3-phenylphthalimidine at 1458 cm" , 1472 cm" , 1497 cm" , 1599 cm" and 1  1  1  1608 cm * were not present i n the reduced product.  1  The 3-phenylphthalmi-  dine band at 3020 cm" associated with aromatic C-H i s not present i n 1  the reduced product.  The bands i n the 700 cm* region associated with 1  r i n g substitution also are not found i n C-3.  The 2830 cm" v i b r a t i o n 1  associated with t e r t i a r y CH i s stronger i n the reduced product than i n 3-phenylphthalimidine.  The lactam carbonyl (1677 cm" ) of 1  3-phenylphthalimidine appears i n the reduced product with a s l i g h t change i n frequency (1673 cm" ). 1  A l l of these observations are con-  s i s t e n t with the reduction of both benzene rings to produce 3-cyclohexyl hexahydro-phthalimidine.  W/we  NUMBERS  AV*  CV\~  X  T h i s c o n c l u s i o n i s supported by a n a l y s i s o f C-3.  Calculated f o r C H N0i  C,  76.02;  H,  10. 41;  N,  6.33;  m.w.  221  Found:  C,  76.17;  H,  10.37;  H,  6.15;  m.w.  216  u  2 3  d.  Repeat o f r e a c t i o n o f benzophenone oxime  Benzophenone oxime was r e a c t e d w i t h carbon monoxide u n d e r the same g e n e r a l c o n d i t i o n s as on page 40. monoxide was 2250 p . s . i .  I n i t i a l p r e s s u r e o f carbon  a t 1 8 ° C (2105 p . s . i . a t 0 ° C ) .  Benzophenone  oxime (19.5 gm) (0.1 mole) was d i s s o l v e d i n 30 ml o f c a t a l y s t  solution  (0.02 mole) and t h e t o t a l volume brought t o 60 ml w i t h benzene. D e t a i l s o f p r e s s u r e r e a d i n g s were p l o t t e d , and are graphed on page 66.  The o v e r a l l p r e s s u r e d r o p was 1.77 moles p e r mole o f s u b s t r a t e ,  c a l c u l a t e d as carbon monoxide.  The m a t e r i a l from t h e bomb was heated f o r 30 m i n u t e s a t t h e temperature o f r e f l u x i n g benzene. brown c r y s t a l l i n e m a t e r i a l .  Benzene was e v a p o r a t e d t o l e a v e  T h i s m a t e r i a l was e x t r a c t e d w i t h h o t  c h l o r o f o r m and an i n s o l u b l e r e s i d u e f i l t e r e d o f f ( m a t e r i a l I ) .  Evapo-  r a t i o n o f the c h l o r o f o r m y i e l d e d a d a r k brown m a t e r i a l which formed a d a r k brown s o l u t i o n i n methanol and l e f t a d a r k r e d r e s i d u e ( m a t e r i a l  II).  20  AO  60  TIMS.  80  \00  \20  140  -2. ON  67 M a t e r i a l I I t u r n e d green on d r y i n g and f a i l e d t o m e l t a t 350° C. I t l e f t a b l a c k r e s i d u e on i g n i t i o n which t e s t e d f o r c o b a l t .  White c r y s t a l s  ( 7 gm) c r y s t a l l i z e d from t h e methanol (m.p.  180 - 2 1 0 ° C) ( m a t e r i a l I I I ) .  Extensive t r i a l s of r e c r y s t a l l i z a t i o n  from o r g a n i c s o l v e n t s f a i l e d t o produce a pure compound c o r r e s p o n d i n g t o compound B o f s e c t i o n I . repeated r e c r y s t a l l i z a t i o n s mother l i q u o r ,  Pure compound C c o u l d be o b t a i n e d by f r o m benzene o r methanol.  containing catalyst  decomposition  From t h e methanol  p r o d u c t s , i t was  p o s s i b l e t o i s o l a t e 6 gm o f o r g a n i c m a t e r i a l making t h e t o t a l y i e l d 13 gm.  Ah e t h e r e x t r a c t was made o f m a t e r i a l I I I . crystals  (1 gm) melted  a t 194 - 2 0 0 ° C.  These were r e c r y s t a l l i z e d  e t h e r and 3 s e p a r a t e c r o p s were o b t a i n e d . 220 - 2 3 0 ° C; t h e second 220 - 2 3 0 ° C.  The r e s u l t i n g  The f i r s t  from  (100 mgm) m e l t e d  (200 mgm) 170 - 1 9 5 ° C; and t h e t h i r d  (100  mgm)  The m i d d l e c r o p (200 mgms) was d i s s o l v e d i n 3 ml o f  benzene p l a c e d on an alumina column ( 3 ^ cm x 8 cm) and e l u t e d w i t h benzene w i t h t h e f o l l o w i n g r e s u l t s ;  t h e f i r s t 250 ml o f benzene p r o -  duced n o t h i n g ; t h e n e x t 200 ml produced, a f t e r r e c r y s t a l l i z a t i o n , 120 mgm o f compound B (m.p. 197 - 1 9 9 ° C ) .  The i n f r a r e d  spectrum  o f t h i s m a t e r i a l showed t h e f o l l o w i n g  major a b s o r p t i o n s (potassium bromide d i s c ) ; 3420(broad)S, 2885W, 1704M, 1690W, 1627M, 1535M, H99W, 1A75W, 1463W, 1366W, 1346W, 1329W, 11A0M, 1086M, 774W, 765W, 753W, 741W, 731W, 700M. on page 47.  The spectrum  i s reproduced  68  A f u r t h e r 100 ml o f benzene produced 50:50 (100 ml) produced  Benzene e t h a n o l  3-phenylphthalimidine.  The f i r s t and t h i r d c r o p s were now  chromatographed and  y i e l d e d o n l y t r a c e s q u a n t i t i e s o f compound B. wholly of  nothing.  both  They c o n s i s t e d almost  3-phenylphthalimidine.  Compound B f a i l e d t o r e a c t w i t h c o l d aqueous o r a l c o h o l i c potassium  permanganate.  carbon t e t r a c h l o r i d e . formic acids.  I t f a i l e d t o r e a c t w i t h bromine i n water o r No r e a c t i o n was  v i s i b l e with hydrochloric or  A r e d c o l o r c o u l d be d e t e c t e d by p o u r i n g c o n c e n t r a t e d  s u l p h u r i c a c i d onto d r y c r y s t a l s which would s u b s e q u e n t l y t o a p a l e green  solution.  A h y d r o l y s i s was Twenty mgm  attempted  o f compound B and 8 gm  u s i n g the f o l l o w i n g c o n d i t i o n s .  o f potassium h y d r o x i d e were d i s -  s o l v e d i n 30 ml o f e t h a n o l and 20 ml o f water. i n the c o l d m i x t u r e was  dissolve  Compound B was  but d i s s o l v e d a t r e f l u x temperature.  c a r r i e d out f o r 30 hours.  The  s o l v e n t was  p r e s s u r e , and a l l o w e d t o c r y s t a l l i z e a t 0° C.  insoluble  Reflux  e v a p o r a t e d under reduced C r y s t a l s r e c o v e r e d were  shown i d e n t i c a l w i t h compound B by mixed m e l t i n g p o i n t .  Twenty mgm  o f compound B were heated on the steam b a t h f o r  o n e - h a l f hour w i t h c o n c e n t r a t e d s u l p h u r i c a c i d . was  poured  compound B.  The r e a c t i o n  mixture  i n t o c o l d water and c r y s t a l s r e c o v e r e d proved i d e n t i c a l  to  69  3-Phenyloxindole  was  prepared  by the method o f Meisenheimer  (28) f o r comparison w i t h compound B, because o f s i m i l a r i t y i n a n a l y s i s , solubilities  and c h e m i c a l  properties,,  Mixed m e l t i n g p o i n t produced  a  marked d e p r e s s i o n .  A r e - a n a l y s i s o f compound B produced the f o l l o w i n g r e s u l t s :  Calculated f o r G  27 22 2°2 H  N  H,  5.42;  N,  6.90;  Mol. wt.  406  C, 79.44;  H,  5.28;  N,  6.86;  Mol.  379  J  Found:  e.  G, 79.80;  wt.  R e a c t i o n o f benzophenone oxime i n the presence of  s m a l l amount o f d i c o b a l t o c t a c a r b o n y l  R e a c t i o n between benzophenone oxime and c a r b o n monoxide  was  c a r r i e d out i n the presence o f a s m a l l amount o f d i c o b a l t o c t a c a r b o n y l i n the f o l l o w i n g manner. c a t a l y s t s o l u t i o n was c o b a l t o u s carbonate solution.  poured o f f l e a v i n g the u n r e a c t e d  with approximately  A s o l u t i o n o f 16 gm  benzene was  2 ml  residue of  (0.002 mole) o f c a t a l y s t  (0.088 mole) o f benzophenone oxime i n  added t o t h i s r e s i d u e and t h e t o t a l volume made e x a c t l y  50 ml w i t h benzene. r e a c t i o n was v e s s e l was  A f t e r p r e p a r a t i o n o f the c a t a l y s t most o f t h e  On r e a c h i n g 2 0 0 ° C i t was  not proceeding  as d e s c r i b e d i n s e c t i o n I I I .  allowed t o c o o l and r e h e a t e d  r e a c t i o n might be p r o c e e d i n g  The  benzene was  apparent t h a t the  slowly.  evaporated  The r e a c t i o n  t w i c e on the assumption  T o t a l h e a t i n g time was  o f f and  the product was  i n c h l o r o f o r m t o o b t a i n a brown f i l t r a t e and a p i n k r e s i d u e .  the  four  hours.  digested This  70) r e s i d u e c o n t a i n e d no o r g a n i c m a t e r i a l , but d i d c o n t a i n c o b a l t and appeared i d e n t i c a l i n appearance w i t h c o b a l t o u s carbonate. r a t i o n o f t h e brown c h l o r o f o r m s o l u t i o n a brown o i l was product  (10.5  a t 0° C.  gm).  The  brown o i l was  evapo-  obtained  d i s s o l v e d i n e t h e r and  as  cooled  C r y s t a l s were o b t a i n e d and r e c r y s t a l l i z e d from methanol,  t o y i e l d 90 mgm  o f 3-phenylphthalimidine.  i n a l c o h o l s , acetone, chloride.  I t was  The  soluble tetra-  s t a b l e t o the a c t i o n o f hot c o n c e n t r a t e d h y d r o c h l o r i c  h y d r o c h l o r i c a c i d o r sodium h y d r o x i d e . produced a green  brown o i l was  e t h e r , benzene, c h l o r o f o r m , o r carbon  a c i d o r h o t c o n c e n t r a t e d sodium h y d r o x i d e .  was  On  solution.  I t was  i n s o l u b l e i n water,  Concentrated  sulphuric acid  On d i l u t i o n a c o l o r l e s s c o l l o i d a l  suspension  o b t a i n e d which would n o t d i s s o l v e on b a s i f y i n g w i t h sodium  hydroxide.  The o i l b o i l e d a t 2 9 0 ° C ( u n c o r r e c t e d ) 305 - 307° C ( c o r rected).  I t d i s t i l l e d without decomposition  a t atmospheric  pressure.  R e a c t i o n w i t h hydroxylamine h y d r o c h l o r i d e i n aqueous e t h a n o l y i e l d e d white c r y s t a l s (m.p.  144- - 145° C ) .  Reaction with 2-4-dinitrophenyl-  h y d r a z i n e y i e l d e d y e l l o w c r y s t a l s (m.p.  245  - 247° C).  v a l u e s f o r benzophenone oxime and benzophenone, o are 144  The  literature  2-4-dinitrophenylhydrazone  o C and 247  i s 306° C.  C.  The l i t e r a t u r e b o i l i n g p o i n t f o r benzophenone  These o b s e r v a t i o n s i d e n t i f y the major r e a c t i o n component  as benzophenone. The r e s i d u e from t h e d i s t i l l a t i o n o f the brown o i l was c r y s t a l l i z e d from a water-ethanol  mixture  (m.p.  144 - 145° C ) .  reMixed  71  m e l t i n g p o i n t w i t h an a u t h e n t i c sample o f benzophenone oxime was 144 145° C.  The r e s i d u e r e a c t e d w i t h bromine i n c a r b o n t e t r a c h l o r i d e  w i t h o u t e v o l u t i o n o f hydrogen bromide.  C r y s t a l s produced m e l t e d a t  223 - 224° C.  D.  R e a c t i o n o f 0-methyl E t h e r o f Benzophenone  Oxime  i n t h e Presence o f D i c o b a l t O c t a c a r b o n y l  a.  P r e p a r a t i o n o f t h e 0-methyl e t h e r o f benzophenone  Benzophenone h y d r o c h l o r i d e (14 gm)  oxime  (20 gm)  (0.11 mole) and 0-methyl hydroxylamine  (0.195 mole) were r e f l u x e d f o r 4 h o u r s w i t h 20  ml o f p y r i d i n e and 200 ml o f e t h a n o l . u n d e r reduced p r e s s u r e . crystals.  The e t h a n o l was then removed  Slow a d d i t i o n o f water w i t h s t i r r i n g produced  These were r e c r y s t a l l i z e d t w i c e i n the f o l l o w i n g manner.  The c r y s t a l s were d i s s o l v e d i n minimum q u a n t i t y o f acetone and an e q u a l q u a n t i t y o f methanol was added. p o i n t was reached.  Water was added t i l l  the cloud  C r y s t a l l i z a t i o n was a l l o w e d t o proceed a t 0° C.  The y i e l d was 20.0 gm  (0.095 mole) (87$ o f t h e o r e t i c a l ) .  This recrys-  t a l l i z a t i o n p r o c e d u r e was t a k e n f r o m Hauser and H o f f e n b e r g ( 2 0 ) .  b.  Reaction procedure  The c a r b o n y l a t i o n r e a c t i o n was c a r r i e d o u t e s s e n t i a l l y as i n previous sections.  An amount o f 10.5 gm (0.05 mole) o f 0-methyl e t h e r  72  o f benzophenone oxime and 35 ml used.  The  s t a t was  (0.026 mole) o f c a t a l y s t l i q u o r were  t o t a l volume o f r e a c t i o n s o l u t i o n was  o r i g i n a l l y s e t a t 180° C.  temperature so t h e temperature was  50 ml.  No r e a c t i o n was  The  thermo-  apparent  at t h i s  r a i s e d i n 10 degree s t e p s t o 2 2 0 ° C  m a i n t a i n i n g the temperature f o r 6 o r 7 m i n u t e s a t each l e v e l . was  c o n t i n u e d a t 220° C f o r 71 minutes; a f t e r c o o l i n g the  p r e s s u r e d r o p was  120 p . s . i . measured a t 0° C.  mole o f carbon monoxide o r 1.3  Heating  overall  T h i s r e p r e s e n t s 0.065  moles p e r mole o f s u b s t r a t e .  A detailed  p l o t o f p r e s s u r e v e r s u s time a t c o n s t a n t temperature I s shown on page 73.  was  c.  S e p a r a t i o n and i d e n t i f i c a t i o n o f  The  p r o d u c t was  removed u n d e r reduced  products  a homogeneous benzene s o l u t i o n .  m a t e r i a l was  benzene  p r e s s u r e t o produce a y e l l o w d i s t i l l a t e  which a v e r y few orange c r y s t a l s s e p a r a t e d which had dicobalt octacarbonyl.  The  The r e s i d u e was  from  the appearance o f  a dark t a r r y m a t e r i a l .  This  sludged w i t h c o l d c h l o r o f o r m t o produce 50 ml o f a brown  c h l o r o f o r m s o l u t i o n and a r e s i d u e which c o n t a i n e d o r g a n i c m a t e r i a l and cobalt.  Seven ml o f t h i s s o l u t i o n were e v a p o r a t e d  and d i s s o l v e d i n  benzene then p l a c e d on a column ( 5 0 $ alumina and 50$ c e l i t e ) (3 diameter x 6 cm)  f o r chromatography.  The f i r s t 100 ml o f benzene e l u e n t  produced a brown o i l which on warming i n l i g h t p e t r o l e u m i n s o l u b l e i n petroleum  e t h e r o r benzene.  and gave a p o s i t i v e t e s t f o r c o b a l t . duced n o t h i n g .  cm  e t h e r became  This m a t e r i a l f a i l e d to melt  F u r t h e r e l u t i o n w i t h benzene p r o -  E l u t i o n w i t h e t h a n o l produced a s i m i l a r o i l which a l s o  TOT/\U To  ^CACTVOVA  0 ° C  0.0%  Vb«.  P R E S 5 U « t  0-W\^TV\><\_  \V\0W«  C o ^ l C T E O ^L"\ V\<c^«.  OIF  CKTrW-^ST  ui  a  u K lit iii V v  IP 0-  •i  <*»  \t%  w 2\oo  in v>  V ti  is.  aZOOO _  TEMPERATURE.  20  40  6O  8O TIME  \M  \N  + \0O WWUTES  00 V*)  n contained cobalt. s o l u t i o n o f m.p.  M a t e r i a l (20 mgm)  220 - 222° C.  c r y s t a l l i z e d from t h e e t h a n o l  The r e s i d u e from t h e c h l o r o f o r m ex-  t r a c t i o n was t r e a t e d w i t h c o l d benzene. and  a v i o l e t residue.  A" blue s o l u t i o n was o b t a i n e d  On e v a p o r a t i o n o f t h e s o l u t i o n white c r y s t a l s  covered w i t h a deep b l u e o i l y m a t e r i a l r e s u l t e d .  C o l d acetone d i s s o l v e d  the b l u e c o l o r c o m p l e t e l y l e a v i n g some white c r y s t a l s . evaporated  The acetone  was  t o l e a v e a b l u e o i l y m a t e r i e l which burned b r i g h t l y on an  i g n i t i o n test l e a v i n g a black residue.  The r e s i d u e c o n t a i n e d c o b a l t .  The i n f r a r e d spectrum o f t h i s m a t e r i a l f a i l e d t o show a h i g h a b s o r p t i o n which c o u l d be a s s o c i a t e d w i t h the c a r b o n y l f r e q u e n c y o f a c o b a l t c a r b o n y l compound..  frequency  stretching  T h i s o i l was s o l u b l e i n o r g a n i c  s o l v e n t s (acetone, benzene, c h l o r o f o r m , a l c o h o l s ) and s o l u b l e w i t h o u t effervescence i n concentrated h y d r o c h l o r i c acid. o f t h e o i l was a l l o w e d t o c r y s t a l l i z e a t 0° C., produced melted  a t 217 - 222° C.  3-phenylphthalimidine  after  An acetone  solution  The c r y s t a l s which were  These were shown i d e n t i c a l t o  recrystallization.  The r e s i d u e f r o m t h e c o l d benzene e x t r a c t was now t r e a t e d w i t h hot c h l o r o f o r m t o g i v e a green  s o l u t i o n and a v i o l e t r e s i d u e .  The  r e s i d u e seemed t o c o n t a i n no o r g a n i c m a t e r i a l b u t d i d c o n t a i n c o b a l t . The above c h l o r o f o r m and benzene s o l u t i o n s were e v a p o r a t e d 7 gm o f l i g h t brown o r g a n i c m a t e r i a l m.p.  200 - 2 1 7 ° C.  e x t r a c t i o n d i s s o l v e d 2.7 gm l e a v i n g a r e s i d u e o f 4.3 gm.  to y i e l d  A warm benzene A 10$ a l i q u o t  o f t h e benzene s o l u t i o n was chromatographed on an alumina column ( 9 cm x 3 cm).  The column r e t a i n e d a narrow brown band a t t h e t o p and pro-  d u c t appeared v e r y s l o w l y on benzene e l u t i o n .  Each f r a c t i o n  collected  75  m e l t e d i n the range 210 - 217° C.  These f r a c t i o n s were combined  r e c r y s t a l l i z e d from methanol and benzene. after recrystallization. (m.p.  153  Mixed m.p.  T h e i r m.p.  gm was  produced 150 mgm  then washed w i t h 500 ml o f acetone.  (7 gm)  o b t a i n e d which was  reaction. potassium  Ethanol  elution The  A l i g h t brown f l u i d  o b v i o u s l y not a product of the  original  T h i s f l u i d r e a c t e d i n s t a n t a n e o u s l y w i t h i c e c o l d 2% aqueous permanganate and w i t h bromine i n carbon t e t r a c h l o r i d e .  b o i l i n g p o i n t o f t h i s m a t e r i a l was for  224° C,  210 - 250° G ( m a t e r i a l V ) .  column was was  -  3-phenylphthalimidine.  r e c o v e r e d from the column.  o f a component m.p.  222  and p r e p a r a t i o n o f a c e t a t e d e r i v a t i v e  - 154° C) proved t h i s compound t o be  A t o t a l o f 0.25  was  and  di-acetone  163 - 166° C ( c o r r e c t e d ) . L i t e r a t u r e  a l c o h o l i s 164 - 166° C.  u s e d were evaporated  The  A l l s o l v e n t s which had  down t o t r y t o reproduce t h i s l i q u i d  been  without  success.  M a t e r i a l V (150 mgm) rechromatographed. 222° C.  ( t h e h i g h m e l t i n g f r a c t i o n ) was  Benzene e l u t i o n produced 140 mgm  A l c o h o l e l u t i o n produced 1 mgm  T h i s l a s t 1 mgm p r e s e n t which i s n o t  now  m e l t i n g 219  o f m a t e r i a l m e l t i n g 218  - 300° C.  i s a p p a r e n t l y the o n l y o r g a n i c compound  3-phenylphthalimidine.  76  IV.  BIBLIOGRAPHY  A l d r i d g e , C. L., Posce, E. V. and Jonassen, H. B.; J . Phys. Chem. &>, 869 (1958). Beckmann, E. j Ber. 23., 1685 (1890). B e n g e l s d o r f , I . S . j J . Am. Chem. Soc. 80, 1442 (1958). B i l l e t e r , 0. G.; Ber. 36, 3219 (1903). B i l t z , H. j Ber. _)» 2635 (1907). Buckley, G. D. and Ray, N. H.j J . Chem. Soc. 1151 (1949). Coe, C. S. and Doumani, T. F. j J . Am. Chem. Soc. JO, 1516 (1948). D a v i s , T. L. and B l a n c h a r d , K. C . j J . Am. Chem. Soc. 45. 1819, (1923). Donahue, J . j J . Am. Chem. Soc. 7_, 4172 (1956). E i d u s , Y. T. and I z m a i l o v , R. I . ; Chem. 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