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A proposed study of the cyclopentadienyl anion using carbon-14 as a tracer Tkachuk, Russell 1956

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PROPOSED  STUDY  USING  OF....:. THE  CAKBON-14  GYGLOPEHTADIEEYL ANION  AS  A  TRACER,  by RUSSELL  TKACHUK  A THESIS SUBMITTED I N PARTIAL FIILFLLMEM 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 as c o n f o r m i n g t o the standards r e q u i r e d from candidates f o r t h e degree o f MASTER OF SCIENCE  Members o f t h e department o f Chemistry  THE  UNIVERSITY  OF  BRITISH COLUMBIA  A p r i l , 1956  ABSTRACT I t i s thought t h a t some i n f o r m a t i o n about t h e bond s t r u c t u r e i n t h e c y c l o p e n t a d i e n y l a n i o n can be p r o v i d e d b y s y n t h e s i z i n g c y c l o p e n t a d i e n e - 5 - C ^ , making t h e c y c l o p e n t a d i e n y l a n i o n ( a s t h e p o t a s s i u m s a l t ) , and d e g r a d i n g t h e c y c l o p e n t a d i e n e r e g e n e r a t e d from t h i s a n i o n f o r t h e d e t e r m i n a t i o n o f t h e d i s t r i b u t i o n o f carbon-14:  DEGRADATION  A method f o r t h e s y n t h e s i s o f c y c l o p e n t a d i e n e , s t a r t i n g f r o m formaldehyde,  h a s been shown.  p e n t a d i e n y l s a l t was t h e n made.  The p o t a s s i u m  cyclo-  The c y c l o p e n t a d i e n e  r e g e n e r a t e d from t h i s s a l t was c o m p l e t e l y degraded. i t i o n o f t h i s work, u s i n g f o r m a l d e h y d e - C ^  Repet-  would g i v e t h e  desired cyclopentadiene-5-C^, e t c . U s i n g carbon-14,  the precursor t o cyclopentadiene-5-G^  was made, b u t t h e s y n t h e s i s o f c y c l o p e n t a d i e n e - 5 - C ^ not be c a r r i e d  out i n t h e a v a i l a b l e t i m e .  could  ACKN0TO5DGMEHT The a u t h o r w i s h e s t o express h i s a p p r e c i a t i o n o f t h e encouragement, a d v i c e , and a s s i s t a n c e g i v e n b y D r . C. G. Lee d u r i n g t h e c o u r s e o f t h i s  research.  TABLE OF CONTENTS  General I n t r o d u c t i o n - - - - - - - - - - -  1  Historical Introduction A.  General  . 2  B.  The C y c l o p e n t a d i e n y l A n i o n  7  Discussion A.  Synthesis of Cyclopentadiene  - - - -  B.  S y n t h e t i c and D e g r a d a t i v e P r o c e d u r e s  10 14  Experimental A.  S o l v e n t s and Reagents  B.  S y n t h e t i c and D e g r a d a t i v e P r o c e d u r e s  Bibliography  - - - - - - -  - - - - - - - - - - - - - - -  19 21 38  GENERAL INTRODUCTION The o b j e c t o f t h i s work i s a proposed  study o f t h e  bond-structure of the cyclopentadienyl anion.  The p r e s e n t  theory of "aromatic c h a r a c t e r " a s c r i b e s the s t a b i l i t y of arom a t i c compounds, o f w h i c h t h e c y c l o p e n t a d i e n y l a n i o n i s a member, t o t h o s e u n s a t u r a t e d c o n j u g a t e d c y c l i c systems h a v i n g six resonating TT-electrons.  I n the cyclopentadienyl anion,  t h e s e . c o n d i t i o n s a r e f u l f i l l e d by u t i l i z i n g t h e two e l e c t r o n s w h i c h f o r m e r l y h e l d a carbon-hydrogen bond t o g e t h e r i n t h e methylene group o f c y c l o p e n t a d i e n e :  He—CH  II  II  HC  H __ H  HC-—CM +K°.  //  C  w  OH 8  C  /• — 1} H  H  However, e x p e r i m e n t a l v e r i f i c a t i o n o f t h e s e p r e d i c a t i o n s i s incomplete.  I t i s thought  that t h i s v e r i f i c a t i o n ,  or other-  w i s e , c a n be o b t a i n e d i n t h e case o f t h e c y c l o p e n t a d i e n y l a n i o n , by t h e use o f carbon-14- as a t r a c e r . s y n t h e s i z i n g cyclopentadiene-5-C^- , 4  T h i s c a n be done by making t h e p o t a s s i u m  and t h e n r e g e n e r a t i n g c y c l o p e n t a d i e n e from t h i s l a t t e r  anion,  salt*  DEGRADATION  2. I f the anion i s aromatic according t o our present d e f i n i t i o n of  a r o m a t i c i t y , t h e n t h e carbon-14 i n t h e r e g e n e r a t e d  cyclo-  pentadiene w i l l be d i s t r i b u t e d e q u a l l y on e v e r y carbon atom. I f t h e n e g a t i v e charge remains on t h e former methylene group, the o r i g i n a l c y c l o p e n t a d i e n e - 5 - c l "  w i l l be r e g e n e r a t e d , e t c .  4  The aim i n t h e p r e s e n t work was t o f i n d a s u i t a b l e h y p o t h e t i c a l synthesis f o r cyclopentadiene-5-C ", 14  for  and a method  t h e r e g e n e r a t i o n o f c y c l o p e n t a d i e n e from i t s p o t a s s i u m  salt.  T h i s was done.  To f a m i l i a r i z e o n e s e l f w i t h t h e r e a c t i o n  procedures and t o l e a r n t h e o v e r - a l l y i e l d , a  complete  s y n t h e s i s , f o r m a t i o n o f t h e p o t a s s i u m s a l t , r e g e n e r a t i o n , and a complete d e g r a d a t i o n o f c y c l o p e n t a d i e n e were e f f e c t e d .  Time  p e r m i t t i n g , t h e above work was t o be r e p e a t e d as f a r as p o s s i b l e , u s i n g carbon-14.  C y c l o p e n t a n e - l , 2 - d i o l - 5 - C - ( c i s - t r a n s ) was 14  s y n t h e s i z e d , but the d e h y d r a t i o n o f i t t o cyclopentadiene c o u l d not be r e p e a t e d .  HISTORICAL INTRODUCTION (A)  GENERAL  A r o m a t i c compounds were so c l a s s i f i e d because o f t h e i r odor.  originally  Today a r o m a t i c i t y o r a r o m a t i c c h a r a c t e r  i n f e r s a much d i f f e r e n t meaning.  A l t h o u g h t h e r e i s much d i s -  agreement on t h e d e f i n i t i o n o f a r o m a t i c i t y , v e r y b r i e f l y i t may be a s s o c i a t e d w i t h c y c l i c compounds p o s s e s s i n g t h e f o l l o w i n g properties: (1) A v e r y s t a b l e n u c l e u s o f carbon atoms  (2)  A p a r t i c u l a r l y r e s i s t a n t t y p e o f u n s a t u r a t i o n towards the f o r m a t i o n o f a d d i t i o n a l p r o d u c t s  (3)  A tendency t o undergo s u b s t i t u t i o n r e a c t i o n s  (4)  A c i d i c e n o l i c d e r i v a t i v e s w i t h l i t t l e tendency t o form the " k e t o form"  (5)  A tendency t o form quinone and d i a z o n i u m s a l t s  (6) H a l i d e d e r i v a t i v e s w h i c h a r e v e r y i n e r t (7)  A pronounced tendency towards t h e i r f o r m a t i o n .  Benzene and i t s d e r i v a t i v e s o f c o u r s e p r o v i d e t h e c l a s s i c a l example o f i l l u s t r a t i n g t h e s e p r o p e r t i e s . Chemists e l u c i d a t i n g t h e p r o p e r t i e s and s t r u c t u r e s o f t h e s e a r o m a t i c compounds have come up w i t h many t h e o r i e s . One s c h o o l o f t h o u g h t , due t o Armstrong, v o n Baeyer and Bamberger, suggested t h a t a r o m a t i c c h a r a c t e r was due t o t h e s y m m e t r i c a l arrangement o f c o n j u g a t e d l i n k a g e s i n t h e s e c y c l i c compounds. I n d e p e n d e n t l y , Armstrong (3) i n 1888  i n 1887  and von Baeyer  (4)  p r o v i d e d f o r benzene a symbol based on t h e 2 4 - a f f i n i t i e s  o f t h e s i x c a r b o n atoms.  Of t h e s e 2 4 - a f f i n i t i e s , 12 a r e engaged  i n t h e f o r m a t i o n of t h e s i x - c a r b o n r i n g and s i x r e t a i n i n g t h e s i x hydrogen atoms, w h i l e t h e r e m a i n i n g s i x r e a c t upon each o t h e r — " a c t i n g towards a c e n t r e as i t w e r e " — s o  that the  " A f f i n i t y " m a y be s a i d t o be u n i f o r m l y and s y m m e t r i c a l l y distributed  (3):  H  C / \  M  C / \  4 Bamberger ( 6 ) ,  in  1891-1893, suggested t h a t t h e s i x  v a l e n c e s unnecessary f o r t h e f o r m a t i o n o f benzene " s a t u r a t e d each o t h e r " .  R i n g s n o t h a v i n g s i x such v a l e n c e s c o u l d n o t  a t t a i n the same s t a b i l i t y .  Bamberger extended h i s h e x a c e n t r i c  argument t o u n s a t u r a t e d h e t e r o c y c l i c s by u t i l i z i n g the s a l t f o r m i n g v a l e n c e s o f the hetero-atoms:  0 5 P 5  Pyridine  Pyrrole  T h i e l e (53)  Thiophene i n 1899,  Pyrazole(Imidazole)  Q  Furan  c o n s i d e r e d t h a t each c a r b o n atom  o f a double-bond t o possess a p a r t i a l v a l e n c e , and t h a t i n a d i e n e t h e s e p a r t i a l v a l e n c e s n e u t r a l i z e each o t h e r w i t h t h e r e s u l t i n g a c c u m u l a t i o n o f r e s i d u a l energy a t the ends o f t h e c o n j u g a t e d system (t© e x p l a i n 1 , 4 - a d d i t i o n s ) :  I •  A p p l y i n g t h i s argument t o 4ke  —  "  I I  Kekules cyclohexatriene formula  f o r benzene w i t h i t s c l o s e d c o n j u g a t e d system, t h r e e i n a c t i v e double bonds a l t e r n a t i n g w i t h t h e o r i g i n a l / , d e a c t i v a t e d d o u b l e bonds a r e formed, r e s u l t i n g i n s i x n e a r l y e q u i v a l e n t i n e r t linkages:  5  I n the n i n e t e e n t h c e n t u r y , t h e v a l e n c e bond  was  r e p r e s e n t e d by a l i n e drawn between t h e symbols of two elements,  the n a t u r e o f the bond b e i n g unknown.  chemical  F o l l o w i n g the  d i s c o v e r y o f t h e e l e c t r o n i n 1897• e l e c t r o n s i n s t e a d o f t h e former l i n e s soon appeared as the l i n k between atoms i n c h e m i c a l compounds.  not u n t i l 1 9 1 6 ,  However, i t was  when G. N. L e w i s  (40)  f o r m u l a t e d t h e b a s i s o f the modern e l e c t r o n i c t h e o r y o f v a l e n c e . And  so e l e c t r o n i c f o r m u l a e f o r benzene soon appeared i n t h e H  literature:  H--c  *  'C-.H  H  , „  .-. -H  > c  C  C • M  The f i r s t a l t e r n a t i v e f o r m u l a t i o n f o r benzene, where a l l the n u c l e a r c a r b o n atoms a r e connected was  suggested  by t h r e e e l e c t r o n s ,  by Kauffmann(37)» and drawn by Kermac and  R o b i n s o n (39)«  H  ri-c ...  . c . ' c*u ••• %  *C ' H L a t e r , A r m i t and R o b i n s o n ( 2 )  suggested  t h a t the "aromatic s e x t e t "  i n t h e b e n z o i d group i n f e r s marked s t a b i l i t y and p o s t u l a t e d t h a t groups o f two o r f o u r e l e c t r o n s a l s o o c c u r , f o r example, i n a c i d s and c y c l o p e n t a d i e n e .  Gross and I n g o l d (28)  extended Bamberger's  t h e o r y by a s s i g n i n g e l e c t r o n i c s t r u c t u r e s t o t h e h e t e r o - c y c l i c compounds:  aromatic  ««  H Pyrrole - ( b )  P y r r o l e - (a) The second f o r m u l a  ( b ) , again gives r i s e t o the aromatic  The a r o m a t i c s i n c e Huckel(39) i n  sextet.  s e x t e t t h e o r y has r e c e i v e d much a t t e n t i o n  1931 i n v e n t e d  t h e quantum m e c h a n i c a l f o u n -  d a t i o n i n w h i c h he a s c r i b e s t h a t a r o m a t i c  character with i t s  r e l a t i v e s t a b i l i t y , o r i g i n a t e s f r o m those c o n j u g a t e d  unsaturated  cycles containing s i x i r - electrons. The f i r s t a t t e m p t s t o t e s t t h i s a r o m a t i c  sextet  weweby W i l l s t a t t e r on t h e n o n - e x i s t e n t c y c l o b u t a d i e n e  theory  (63) and  cyclo—octatetraene(62,69)? w h i c h t h e o r e t i c a l l y a r e n o n - a r o m a t i c molecules.  Cyclobutadiene  s t i l l has n o t been s y n t h e s i z e d and  w o u l d , i n any c a s e , have a l a r g e o b s c u r i n g a n g u l a r  strain.  C y c l o - o c t a t e t r a e n e , a l t h o u g h s y n t h e s i z e d , has a n o n - p l a n e r s t r u c t u r e and so i s " I m p e r t i n e n t t o t h e theory(38). predictions.^ concerning definite  t h e f i v e and s even-member ed r i n g s a r e  (26,34,59)•(CH)5  s h o u l d be more s t a b l e t h a n (CH)y, and  (CH)£ s h o u l d be more s t a b l e t h a n ( C H ) ^ i has n e v e r been p r e p a r e d ;  Theoretical  The p o s i t i v e i o n (CH)"£  but from the f a i l u r e o f c y c l o p e n t a -  dienone t o e x i s t as c o n t r a s t e d w i t h t h e s t a b i l i t y and b a s i c i t y o f c y c l o h e p t a t r i e n o n e , i t c a n be i n f e r r e d t h a t t h e (CH) + i o n i s much more s t a b l e t h a n t h e (CH)£ i o n  (15.20).  In  1954-,  D o e r i n g and Kn©x s y n e t h e s i z e d t h e c y c l o -  heptatrienylium (tropylium) i o n (21).  From i t s p r o p e r t i e s i t appears t h a t resonance  stabilization  i n t h e c y c l i c i o n i s l a r g e enough t o overcome t h e normal tendency ©f t h e carbon-bromine bond t© be c o v a l e n t .  Thus we  have a n o t h e r new a r o m a t i c system i n w h i c h l a r g e resonance energy o r i g i n a t e s f r o m t h e c y c l i c n a t u r e ©f t h e system. I n summary t h e p r e s e n t " a r o m a t i c s e x t e t " t h e o r y p r e d i c t s t h a t t h e c y c l e p e n t a d i e n y l i o n , benzene and t h e cycloheptatrienylium i o n  c o n s t i t u t e a t r i a d p o s s e s s i n g a r o m a t i c resonance energy and hence r e m a r k a b l e s t a b i l i t y .  (B)  THE CYCLOPENTADIENYL ANION  The resonance energy ©f c y c l o p e n t a d i e n e , c a l c u l a t e d f r o m t h e h e a t ©f h y d r o g e n a t i o n , i s o n l y about 3 k c a l / m o l e  (5).  But c y c l o p e n t a d i e n e p o s s e s s e s an a c t i v e methylene group, and has an e x c e p t i o n a l l y h i g h a c i d i t y f o r a h y d r o c a r b o n , as  8. potassium t-butoxide (pK^ 19) converts cyclopentadiene quantitatively into i t s potassium s a l t ( 4 9 ) .  This shows that  the negatively charged i o n  Is very stable, although very reactive chemically.  The  reason given by Goss and Ingold (28) i n 1928, was that t h i s ion had s i x *7T -electrons d i s t r i b u t e d over f i v e equivalent CH groups, thus constituting a stable aromatic system s i m i l a r to benzene.  The resonance energy of the Ion has been calculated  to be about 42 kcal./mole, and apparently i s i n harmony with the observed s t a b i l i t y (48).  The tendency of the cyclo-  pentadiene system to accept an electron and thus achieve aromatic s t a b i l i t y i s also shown by the fulvenes.  Dimethylfulven (R-RlnMe) has a dipole moment of 1.44D, the r i n g being negative and the carbon atom-6 positive(60).  This  indicates the electron a t t r a c t i n g nature of the ring which tends to acquire a stable sextet of electrons.  The recently  prepared diazocyclopentadiene (19)  i s a very stable molecule.  I t i s suggested that the molecule  i s a resonance hybrid of the two following structures:  9.  0  fu-  ll  N +  \\\  N  N -  The  f©rm i n w h i c h t h e r i n g accommodates t h e n e g a t i v e  charge  pr©bably c o n t r i b u t e s most t© t h e h y b r i d . The  aromatic  character of the  cyclopentadienium  r i n g i s b e s t i l l u s t r a t e d by dicycl©pentadienyl ir©n ( 5 ) *  T h i s compound i s i n s o l u b l e i n , and does n o t r e a c t w i t h w a t e r , sodium h y d r o x i d e ,  ©r cone, h y d r o c h l o r i c a c i d .  composed a t 470®. known.  I t i s n e t de-  The e x a c t n a t u r e o f t h e Fe-C bonds i s n o t  Regarding the c y c l o p e n t a d i e n y l r i n g s , i n f r a r e d  spectrum i n d i c a t e s o n l y one t y p e ©f C-H bond, and X - r a y e v i d e n c e i n d i c a t e s t h a t t h e five-membered r i n g s a r e p l a n a r , and s y m m e t r i c a l ,  t h e C-C d i s t a n c e s b e i n g about 1*4 A.  D i c y c l o p e n t a d i e n y l i r o n does n o t r e a c t w i t h m a l e i c  anhydride,  cannot be c a t a l y t i c a l l y h y d r o g e n a t e d , and undergoes t h e Friedel-Crafts reaction.  Because o f t h e s e t y p i c a l l y  aromatic  c h a r a c t e r i s t i c s , t h e compound has been named f e r r o c e n e .  10. The  only experimental  work on t h e s t r u c t u r e o f  c y c l o p e n t a d i e n y l a n i o n seems t o be t h a t by A l d e r and r i c h t e r ( 1 ) , who  t r e a t e d the potassium s a l t of  the  Holz-  cyclopentadiene  w i t h b e n z y l c h l o r i d e and o b t a i n e d b o t h b e n z y l - and d i b e n z y l cyclopentadienes the 1-and  and t h e i r d i m e r s .  2-benzyl cyclopentadienes  From t h e s e p r o d u c t s were f o u n d .  S t r a n g e l y , t h e !ir b e n z y l d e r i v a t i v e was  not formed.  T h i s work  i s l i m i t e d i n t h a t one does not know whether o r not t h e p o l y m e r i z a t i o n ©f d i c y c l o p e n t a d i e n e tautomeric  changes.  Besides  de-  derivatives involves  the f a c t t h a t the 5-benzyl  v a t i v e d i d not f o r m , t h e a u t h o r s  only  c o u l d not add any  t o the s t r u c t u r e of the c y c l o p e n t a d i e n y l  deri-  information  anion.  DISCUSSION (A) The  SYNTHESIS OF CYCLOPENTADIENE immediate p r e c u r s o r t o c y c l o p e n t a d i e n e ,  labelled  i n t h e methylene group w i t h carbon-14  was  chosen t o be ( c i s - t r a n s ) c y c l o p e n t a n e - l - d i o l - 4 - C ^ s i n c e  i t was  shown i n the p r e s e n t work t h a t c y c l o p e n t a d i e n e  could  11.  be p r e p a r e d from t r a n s - c y c l o p e n t a n e - l , 2 - d i o l i n a y i e l d o f 2 0 $ :  CC -«-a Whether t h e d e h y d r a t i o n does proceed as shown above c a n o n l y be determined  by an a c t u a l d e h y d r a t i o n . a t t e m p t  * cyclopentane-l,2-^iol-4-C  1 4  of (cis-trans)  f o l l o w e d by d e g r a d a t i o n o f t h e  cyclopentadiene obtained to a s c e r t a i n the l o c a t i o n of C  1 4  in  the r i n g . I f t h e d e h y d r a t i o n , as shown i n t h e p r e c e d i n g paragraph, was n o t s u c c e s s f u l , we s t i l l have two o t h e r p o s s i b i l i t i e s o f o b t a i n i n g c y c l o p e n t a d i e n e from ( c i s - t r a n s ) c y c l o p e n t a n e - l , 2 - d i o l - 4 - C - , o r from i t s p r e c u r s o r , 1 4  dione-4-C - . 3  4-  One p o s s i b i l i t y would be a  1,2-cyclopenta-  dehydrohalogenation  of l ^ - d i b r o m o c y c l o p e n t a n e ^ - c l " according to the f o l l o w i n g 4  scheme:  <z - cc - cc  o  The d i a c e t a t e o f c y c l o p e n t a n e - l , 2 d i o l has been p r e p a r e d ( 4 1 ) , and t h e two r e m a i n i n g s t e p s a r e s i m i l a r t o t h e s u c c e s s f u l preparation of 1,3-cyclohexadiene  (65).  Furthermore,  a  s i m i l a r p r e p a r a t i o n has been s u c c e s s f u l i n t h e p r e p a r a t i o n o f c y c l o h e p t a t r i e n e by W i l l s t a t t e r ( 6 l ) . The second p o s s i b i l i t y would be t h e p r e p a r a t i o n o f the d i o x i m e and t h e n t h e diamine from  l,2-cyclopentadione-4  w h i c h has been r e a l i z e d by Jaeger and Blumendal ( 3 5 ) :  12.  =N-OH =N-OH  From t h e d i a m i n e , a Hoffmann d e g r a d a t i o n c o u l d be a t t e m p t e d  as i n t h e attempted  s y n t h e s i s o f c y c l o b u t a d i e n e by Buchman and  h i s c o l l a b o r a t o r s (10) o r t h e famous s y n t h e s i s o f c y e l o o c t a t e t r a e n e by W i l l s t a t t e r and co-workers ( 6 2 , 6 4 ) , and more r e c e n t l y by Cope and O v e r b e r g e r ( 1 2 ) . Besides the cleavage of d i c y c l o p e n t a d i e n e , there seem t o be o n l y t h r e e r e p o r t e d r e a c t i o n s w h i c h l e a d t o cyclopentadiene.  O n l y one o f t h e s e methods would be u s e f u l i n  t h i s p r e s e n t w o r k , namely, t h e h y d r o l y s i s o f t h e d i - p - t o l u e n e sulphonate o f cyclopentane-l,2-di©l  a c c o r d i n g t o Owen and  Smith(44).  The y i e l d o f c y c l o p e n t a d i e n e was n o t r e c o r d e d by Owen and S m i t h . However, i n two a t t e m p t s t o r e p e a t t h e work o f t h e s e no c y c l o p e n t a d i e n e c o u l d be d e t e c t e d .  authors,  13. T h l e l e i n 1901 o b t a i n e d c y c l o p e n t a d i e n e by t h e r e d u c t i o n o f 2,4-dibromo c y c l o p e n t e n e w i t h z i n c d u s t i n glacial acetic acid  (55).  T h i e l e d i d not m e n t i o n t h e y i e l d , but f r o m h i s d e s c r i p t i o n o f t h e r e a c t i o n , t h e y i e l d o f c y c l o p e n t a d i e n e seemed considerable.  However 2,4-dibromo-cyclopentene i s made f r o m  c y c l o p e n t a d i e n e , and t o s y n t h e s i z e pentene-3  2,4-dibromo-l-cyclo-  seems a v e r y f o r m i d a b l e , i f not i m p o s s i b l e ,  task. F i n a l l y , B r a u n and Kuhn have r e p o r t e d t h a t , d u r i n g the p r e p a r a t i o n o f o - c y c l o p e n t e n y l p h e n o l , by condensing  sodium  p h e n o l a t e and 2 - c y c l o p e n t e n y l , ( 8 ) ,  an a l k a l i - i n s o l u b l e p o r t i o n o f the product was  obtained.  l a t t e r o i l , w i t h a b o i l i n g p o i n t o f 110-200° a t 12 mm., a d i s t i n c t odor o f c y c l o p e n t a d i e n e .  This evolved  I t w o u l d seem t h a t t h i s  r e a c t i o n i s not v e r y s u i t a b l e f o r the p r e p a r a t i o n o f c y c l o p e n t a d i e n e l a b e l l e d i n t h e 5-  position.  14 (B)  SYNTHETIC AND DEGRADATIVE PROCEDURES The  p r e l i m i n a r y s y n t h e t i c p r o c e d u r e s l i s t e d below  were donewithAview t £ p e r f e c t i n g a r o u t e f o r t h e f o r m a t i o n o f 14 cyclopentadiene-5-C C r t l =  °  tooar  c«<coo£t),  coot*  The  :  C  0  C  H  C00£+  synthesis of cyclopentadiene  s t a r t e d from formaldehyde,  as e v e n t u a l l y t h e carbon-14 c o u l d t h e n be i n t r o d u c e d i n t h e f o r m o f formaldehydeThus t e t r a e t h y l p r o p a n e - 1 , 1 , 3 , 3 * t e t r a c a r b o x y l a t e ( I ) was  p r e p a r e d from t h e c o n d e n s a t i o n  malonate and h y d r o l y z e d  o f formaldehyde and d i e t h y l  t o g l u t a r i c a c i d ( I I ) . This  a c i d was t h e n e s t e r i f i e d t o d i e t h y l g l u t a r g t e ( I I I ) . Dieckmann c o n d e n s a t i o n  glutaric A  o f t h e l a t t e r w i t h d i e t h y l o x a l a t e gave  3,5-dicarboethoxycyclopentadione-l,2(IV), afforded cyclopentadione-l,2(V).  w h i c h on h y d r o l y s i s  H y d r o g e n a t i o n o f (V) o v e r  p l a t i n u m oxide, gave a p p a r e n t l y a n i s o m e r i c m i x t u r e o f ( c i s - t r a n s ) cyclopentane-l,2-diolsCVT).  As t h i s l a t t e r p r o d u c t c o u l d n o t  be c h a r a c t e r i z e d by o r d i n a r y means, a u t h e n t i c t r a n s - c y c l o pentane-l,2-diol(XXIII)  was s y n t h e s i z e d , s t a r t i n g from a d i p i c  a c i d as i n t h e f o l l o w i n g sequence:  ci ci a cr oH  H  xtx  *x  xxi  xxn  xxti!  15. Cyclopentanone(XX),  p r e p a r e d by h e a t i n g a d i p i c a c i d ( X I X ) w i t h  barium h y d r o x i d e , was c o n v e r t e d t o c y c l o p e n t a n o l ( X X I ) w i t h l i t h i u m aluminum h y d r i d e . w i t h 85$  Dehydration of the l a t t e r a l c o h o l  o r t h o - p h o s p h o r i c a c i d gave c y c l o p e n t e n e ( X X I I ) , w h i c h  i n t u r n was t r a n s - e s t e r i f i e d w i t h p e r f o r m i c a c i d and h y d r o l y z e d to give trans-cyclopentane-l,2-diol(XXIII).  The o v e r - a l l  yield  •from a d i p i c a c i d was 1 9 . 5 $ . A f t e r t h e t r a n s - c y c l o p e n t a n e - l , 2 - d i o l was c h a r a c t e r i z e d , an i n f r a r e d spectrum was t a k e n o f i t , and a l s o o f t h e c y c l o p e n t a n e - l , 2 - d i o l o b t a i n e d by h y d r o g e n a t i o n 2(V).  of  cyclopentadione-1,  The i n f r a r e d a b s o r p t i o n c u r v e s o b t a i n e d f o r t h e s e two  a l c o h o l s , as 3% s o l u t i o n s i n c h l o r o f o r m , were  superimposable  except f o r one e x t r a s l i g h t peak i n t h e " f i n g e r - p r i n t " r e g i o n f o r t h e d i o l ( V I ) from t h e h y d r o g e n a t i o n o f V. ( F i g . 1, p. 37) C y c l o p e n t a d i e n e ( V T I ) , i n a y i e l d o f 20$, was  prepared  by p a s s i n g t r a n s - c y c l o p e n t a n e - l , 2 - d i o l over a l u m i n a p e l l e t s a t 400°i  The c y c l o p e n t a d i e n e produced, b e s i d e s i t s v e r y  characteristic  odor, was c h a r a c t e r i z e d as t h e m a l e i c a n h y d r i d e adduct.  The  p r e p a r a t i o n o f c y c l o p e n t a d i e n e by t h i s method i s n o t l i s t e d i n the l i t e r a t u r e . Potassium  c y c l o p e n t a d i e n i d e ( I Q I I ) was made by r e a c t i n g  c y c l o p e n t a d i e n e w i t h m e t a l l i c p o t a s s i u m i n benzene and e t h e r .  16 By u s i n g t h i s m i x t u r e o f s o l v e n t s i n s t e a d o f benzene a l o n e , a p r o d u c t i s o b t a i n e d w h i c h i s more f i n e l y d i v i d e d and n o t apt t o c o n t a i n v e r y s m a l l p i e c e s o f u n r e a c t e d p o t a s s i u m . t h i s potassium-cyclopentadiene  as If  s a l t does c o n t a i n m e t a l l i c  p o t a s s i u m , t h e n the next r e a c t i o n on t h i s s a l t would be v e r y v i g o r o u s , and u s u a l l y would end i n a f i r e . Regeneration of cyclopentadiene(IX), i n a y i e l d 43$,  was  of  a f f o r d e d by a d d i t i o n o f c o l d cone, h y d r o c h l o r i c a c i d :  I n f u t u r e work, p r o b a b l y h i g h e r y i e l d s o f c y c l o p e n t a d i e n e c o u l d be o b t a i n e d by d i s s o l v i n g t h e p o t a s s i u m  s a l t i n tetrahydro.-->•  fiMfy and t h e n adding t h e t h e o r e t i c a l amount of hydrogen c h l o r i d e gas.  T h i e l e (5^) mentioned t h a t c y c l o p e n t a d i e n e i s  regenerated from potassium  s a l t by t h e a d d i t i o n o f w a t e r .  R e p e t i t i o n o f T h i e l e ' s work r e s u l t e d i n a r e s i n f o r m a t i o n t o g e t h e r w i t h a poor y i e l d o f c y c l o p e n t a d i e n e .  In this reaction  j H ) V <w—* (Tj  +K0H  the r e a c t i n g m i x t u r e becomes b a s i c as the r e a c t i o n p r o c e e d s . Thus, p r o b a b l y , the c y c l o p e n t a d i e n e formed i s r a p i d l y p o l y m e r i z e d , as a c i d s and bases c a t a l y z e such p o l y m e r i z a t i o n .  17.  By a d a p t i n g former d e g r a d a t i o n s o f c i s - c y c l o p e n t a n e - 1 , 2 - d i a m i n e ( 4 5 ) and s u c c i n i c a c i d ( 7 ) > the scheme f o r t h e  location  o f t h e c a r b o n - C l 4 i n t h e c y c l o p e n t a d i e n e samples i s a s f o l l o w s :  !£. . COOH **• CM7 ^ COOH  Z  *3_  xl  xm  coorle  COHHNHZ  cO/V*  I*. -> cH coort^  i«t ctfi ^ CO/Vff-Jtff/i  CM, ' cHi co/v\t  ^  t  XV  XVI  The d i - e t h y l e s t e r o f  xv^l  xTy  CHa-**coo* ' cH,-NHcoo6t  ^  XVIII  ^  -  S  C  o  CH,. H N  1  XIX  XX  2,3-diazabicycle(2.2.1)-!?-heptehe-2,  3 - d i e a r b o x y l i c a c i d ( X ) was o b t a i n e d by a D i e l s - A l d e r r e a c t i o n between c y c l o p e n t a d i e n e and e t h y l a z o d i c a r b o x y l a t e . Hydrogenation  o f the D i e l s - A l d e r adduct gave t h e d i e t h y l e s t e r  of 2 , 3 - d i a z a b i c y c l e ( 2 . 2 . 1 ) h e p t a n e - 2 , 3 - d i c a r b o x y l i c  acid(XI),  w h i c h , o n h y d r o l y s i s w i t h m e t h a n o l i c p o t a s s i u m h y d r o x i d e , gave 2,3-diazabicycle(2.2.1) c h l o r i d e complex.  heptane ( X I I ) , i s o l a t e d as t h e cuprous  R e d u c t i o n o f X I I w i t h t i n and h y d r o c h l o r i c  a c i d gave c i s - c y c l o p e n t a n e - 1 , 3 - d i a m i n e ( X I I I ) , w h i c h was o x i d i z e d w i t h n e u t r a l potassium  permanganate t o s u c c i n i c a c i d ( X I V ) .  U s i n g t h e C u r t i u s d e g r a d a t i o n method('3,l^), t h e s u c c i n i c was  acid(XIV)  d e g r a d e d . I a l o n g the sequence o f the d i m e t h y l e s t e r ( X V )  dihydrazide(XVI) —  diazide(XXVII) ~  f i n a l l y t o ethylenediamine(XIX)  —  d i u r e t h a n ( X V I I I ) , and  and c a r b o n d i o x i d e ( X X ) . The  o v e r - a l l y i e l d o f ethylenediamine  f r o m c y c l o p e n t a d i e n e was 0,4$  18.  The l o c a t i o n o f t h e carbon-14 i n t h e w o u l d , h y p o t h e t i c a l l y , be determined  cyclopentadiene  i n t h e f o l l o w i n g manner:  The d i f f e r e n c e between the m a l e i c a n h y d r i d e adduct o f c y c l o p e n t a d i e n e ( I X ) and the s u c c i n i c a c i d ( X I V ) w o u l d r e p r e s e n t t h e a c t i v i t y o f the methylene group i n I X .  The  carbon d i o x i d e  produced i n the o x i d a t i o n o f X I I I cannot be used f o r t h e measurement o f the a c t i v i t y o f the methylene group i n t h e c y c l o p e n t a d i e n e ( I X ) because p o t a s s i u m permanganate o x i d a t i o n o f c i s - c y c l o p e n t a n e - l , 3 - d i a m i n e ( X I I I ) would be expected cleave other p a r t s of the r i n g .  As the 1,4-and  to  2,3-positions  a r e e q u i v a l e n t i n c y c l o p e n t a d i e n e , t h e n the d i f f e r e n c e i n radioactivity  o f XIV and XIX would r e p r e s e n t t h e a c t i v i t i e s o f  the 1- and 4 - p o s i t i o n s o f I X .  The a c t i v i t y o f XX, i s o l a t e d  as  barium c a r b o n a t e , c o u l d be used as a check f o r t h e a c t i v i t y  of  the l $ 4 * p d s i t l g i i s . v *  XIX  F i n a l l y , measurement o f the a c t i v i t y ©f  would g i v e the a c t i v i t y of the 2 , 3 - p o s i t i o n s .  A check f©r  a c t i v i t y o f the methylene g r o u p , would be o b t a i n e d by  the  adding  the a c t i v i t i e s o f XIX and XX, and s u b t r a c t i n g t h i s v a l u e f r o m the value obtained f o r IX. The above was  complete s y n t h e t i c and d e g r a d a t i o n r o u t e l i s t e d  done u s i n g " n o n - l a b e l l e d " compounds.  r e a c t i o n s were done a t l e a s t t w i c e . work was  repeated to the  Most o f  th©  U s i n g carbon-14, the above  (cis-trans)cyclopentane-l,2-diol(VI).  A number o f a t t e m p t s were made i n t r y i n g t o s y n t h e s i z e c y c l o p e n t a d i e n e - C " ; however t h e y a l l f a i l e d , and l a c k o f time 14  p r e v e n t e d any f u r t h e r r e s e a r c h .  19. I n f u t u r e r e s e a r c h , more e x p e r i m e n t a l d e t a i l s on the d e h y d r a t i o n o f ( c i s - t r a n s ) c y c l o p e n t a n e - l , 2 - d i o l  have t o  be o b t a i n e d f i r s t , b e f o r e t h e Cl4-phase o f t h e work c a n be completed t o shed some l i g h t on t h e s t r u c t u r e o f t h e c y c l o pentadienyl anion.  EXPERIMENTAL (#) A.  REAGENTS AND SOLVENTS  Chloroform  F o r i n f r a r e d measurements, r e a g e n t  grade  c h l o r o f o r m was shaken w i t h cone, s u l f u r i c a c i d , washed w i t h sodium b i c a r b o n a t e s o l u t i o n and t h e n w i t h w a t e r .  3$  The r e s u l t i n g  c h l o r o f o r m was d r i e d f i r s t w i t h c a l c i u m c h l o r i d e , t h e n w i t h c a l c i u m s u l f a t e , and f i n a l l y d i s t i l l e d .  The f r a c t i o n c o l l e c t e d  b o i l e d a t 6l° ( 2 4 ) . Ethanol  F o r r e a c t i o n s i n v o l v i n g m e t a l l i c sodium,  t h i s r e a g e n t was made " a b s o l u t e " by t h e Lund and B j e r r u m method ( 2 2 ) . Ether  F o r r e a c t i o n s i n v o l v i n g m e t a l l i c sodium o r  p o t a s s i u m , commercial " a b s o l u t e " e t h e r was d r i e d over sodium w i r e and t h e n d i s t i l l e d f r o m phosphorous p e n t o x i d e , b.p. 35°. E t h y l Oxalate  Reagent grade as s u p p l i e d by Eastman  Kodak, was shaken w i t h 3% sodium b i c a r b o n a t e , washed w i t h w a t e r , d r i e d w i t h c a l c i u m s u l f a t e and vacuum d i s t i l l e d a t 42-44° a t 0.6 mm. (#) A l l m e l t i n g p o i n t s r e p o r t e d i n t h e p r e s e n t work, were o b t a i n e d b y h e a t i n g a copper b l o c k c o n t a i n i n g t h e sample and thermometer, and a r e u n c o r r e c t e d .  20.  Methanol  When " a b s o l u t e " methanol was needed,  commercial r e a g e n t grade methanol was d r i e d and p u r i f i e d by t h e Lund and B j e r r u m method ( 2 3 ) . P l a t i n u m Oxide  C a t a l y s t f o r h y d r o g e n a t i o n s , was  used as s u p p l i e d by B r i c k m a n and Company. Alumina  Catalyst f o r dehydrations, i n p e l l e t s of  a p p r o x i m a t e l y 3 mm. i n d i a m e t e r , as s u p p l i e d by The Harshaw C h e m i c a l Company. Sodium E t h o x i d e  P r e p a r e d by a d d i n g f r e s h l y c u t  sodium t o an a p p r o x i m a t e l y t e n - f o l d e x c e s s o f " a b s o l u t e " e t h a n o l i n a n i t r o g e n "dry-box".  A r e f l u x condenser was t h e n a t t a c h e d  t o t h e r e a c t i o n v e s s e l and under a slow stream o f d r y n i t r o g e n , t h e r e a c t i o n was a l l o w e d t o proceed a t room t e m p e r a t u r e . A f t e r t h e r e a c t i o n was complete (approx. 24 h r s . ) t h e e x c e s s e t h a n o l was removed a t t h e w a t e r pump.  To remove t h e a l c o h o l  c o m p l e t e l y , t h e sodium e t h o x i d e was d r i e d a t 1 0 0 ° f o r approximately four hours.  a t 0 . 1 mm.  C a r e f u l work w i l l r e s u l t i n a  p r o d u c t w h i c h i s easy t o powder, and w h i t e i n c o l o r . p-Toluenesulfonvl Chloride  C. P. g r a d e , as s u p p l i e d  by Eastman Kodak, was p u r i f i e d by s h a k i n g a benzene s o l u t i o n with %  sodium h y d r o x i d e , washing w i t h w a t e r and vacuum d i s -  tilling  (25).  had  a m.p.  The p r o d u c t w h i c h c r y s t a l l i z e d i n t h e r e c e i v e r ,  of 6 8 . 5 ° .  L i t . , 69°  (25).-  E t h y l h y d r a z o d i c a r b o x y l a t e P r e p a r e d f r o m 8$% h y d r a z i n e h y d r a t e and e t h y l e h l o r o f o r m a t e ( 4 5 ) i n 8 3 $ y i e l d w i t h a m.p. o f 1 2 7 . 5 - 1 3 0 ° .  L i t . 131° ( 4 5 )  21. E t h y l A z o d i c a r b o x y l a t e P r e p a r e d by o x i d i z i n g e t h y l h y d r a z o d i c a r b o x y l a t e w i t h c h l o r i n e gas(45 i n 57*2$ y i e l d . The p r o d u c t , a b e a u t i f u l orange-red l i q u i d , b o i l e d a t 104° a t 11.0 mm.  L i t . 1 1 1 ° a t 15 mm.(45). Nitrosomethylurea  P r e p a r e d by a d d i n g a 50$ sodium  n i t r i t e solution to a hot, p r e f i l t e r e d s o l u t i o n of  methylamine  h y d r o c h l o r i d e and p o t a s s i u m c y a n a t e , f o l l o w e d by t h e a d d i t i o n o f c o l d 15$ s u l f u r i c a c i d t o t h i s s o l u t i o n a t -5 t o 0 ° (58). The s l i g h t l y cream c o l o r e d c r y s t a l l i n e p r o d u c t was f i l t e r e d o f f , t h o r o u g h l y washed w i t h water and d r i e d over phosphorous p e n t o x i d e a t 0.5 mm. p r e s s u r e . mately -15°»  The p r o d u c t s t o r e d a t a p p r o x i -  and p r o t e c t e d f r o m l i g h t , was s t i l l s t a b l e and  u s a b l e s i x months l a t e r .  B.  SYNTHETIC AND DEGRADATIVE PROCEDURES  Tetraethyl Propane—1.1.3.3-tetracarboxylate  ( I ) (11)  To a m i x t u r e o f 320 gm. o f f r e s h l y r e d i s t i l l e d d i e t h y l malonate  and 84 m l . o f 35$ f o r m a l d e h y d e , c o o l e d t o 2 ° i n a n  i c e - b a t h , was added 6.0 gm. o f p o t a s s i u m c h l o r i d e and t h e n 5.0 gm. o f f r e s h l y d i s t i l l e d d i e t h y l a m i n e .  The components were  w e l l shaken and t h e n a l l o w e d t o come t o room temperature and thus kept f o r 16 hours w i t h o c c a s i o n a l s h a k i n g .  The r e a c t i o n  m i x t u r e was t h e n h e a t e d on a steam b a t h f o r s i x h o u r s , c o o l e d t o room t e m p e r a t u r e , t h e w a t e r s e p a r a t e d o f f and t h e r e m a i n i n g l i q u i d vacuum d i s t i l l e d .  The f r a c t i o n c o l l e c t e d b o i l e d a t  143-1460 a t 0.5 mm. and weighed 266.4 gm. (82.7$).  22. Glutaric Acid (II) (11) Into a three-necked f l a s k , f i t t e d with a r e f l u x condenser, s t i r r e r and thermometer, was placed tetraethyl propane-1,1,3,3-tetracarboxy.late hydrochloric acid.  386.4 gm. of  and 78O ml. of  50$  With s t i r r i n g , the reaction mixture was  slowly refluxed u n t i l the mixture became homogenous (approx. six hours).  The reaction mixture was then d i s t i l l e d under  reduced pressure u n t i l the water and hydrochloric acid were removed.  As ©n cooling the material i n the d i s t i l l a t i o n f l a s k  did not s o l i d i f y , i t was further refluxed f o r two hours with 200 ml. of 50$  hydrochloric acid, and then the water and hydro-  c h l o r i c acid removed under reduced pressure. gm.  On cooling,  (104.5$) of crude g l u t a r i c acid was obtained.  147.0  A small  portion r e c r y s t a l l i z e d twice from benzene, had a melting point of 95-96°, L i t . 97°  (30).  A mixed m.p. with authentical, once  r e c r y s t a l l i z e d g l u t a r i c acid showed no depression. E t h y l Glutarate (III) (42) Into a one-liter d i s t i l l a t i o n f l a s k were placed  146.5  (1.11 moles) of crude g l u t a r i c acid, 400 ml. of absolute ethanol, 200 ml. of toluene and O.83  ml. of cone, s u l f u r i c a c i d .  The  f l a s k was connected to an ordinary d i s t i l l i n g apparatus and heated u n t i l the azeotropic mixture of ethanol, toluene and water began to d i s t i l at 75°. the  D i s t i l l a t i o n was continued u n t i l  b.p. of the d i s t i l l a t e reached 78°.  The d i s t i l l a t e was  dried with 170 gm. of anhydrous potassium carbonate, f i l t e r e d and returned to the d i s t i l l a t i o n f l a s k which was again heated u n t i l the b.p. of the d i s t i l l a t e reached 80°.  At t h i s point  vacuum d i s t i l l a t i o n was at  112-119°,  10-11  at  commenced.  The  product c o l l e c t e d b o i l e d  and weighed 124.0  mm.,  gm.  (59.6$).  I n o t h e r r u n e , when the g l u t a r i c a c i d used was c r y s t a l l i z e d from benzene, a y i e l d of was o b t a i n e d , b o i l i n g a t I 3 6 - I 3 7 20  N  D  0  88.6$  of e t h y l  a t 32 mm.,  1.4241; hp. 103-104° a t 7 mm. gm.  (1.29  (30). (17)  moles) of e t h a n o l - f r e e ,  sodium e t h o x i d e , c o v e r e d w i t h 500  glutarate  1.4234. L i t . ,  ^-?-Dicarboeth©xycyclopentadione-1.2 (IV) To 88.0  re-  white  m l . of anhydrous e t h e r ,  con-  t a i n e d i n a o n e - l i t r e round-bottomed f l a s k f i t t e d w i t h a r e f l u x condenser, o x a l a t e was  95.8  added.  orange c o l o r . was  (O.656  gm.  Now  moles) o f f r e s h l y r e d i s t i l l e d  On m i x i n g t h i s t u r n e d i n t o a p a l e  123.4  (O.656  gm.  moles) of e t h y l  added d r o p w i s e over a p e r i o d o f 30 m i n u t e s , the  m i x t u r e deepening i n c o l o r d u r i n g t h i s a d d i t i o n . was  yellowish-  glutarate reaction  The  mixture  r e f l u x e d f o r one h o u r , the e t h e r d i s t i l l e d o f f , and  r e s i d u e heated to  125-130°  of 10$  T h i s r e s i d u e was  ground i n t o a  s l o w l y added t o a w e l l s t i r r e d i c e - c o l d s o l u t i o n  s u l f u r i c a c i d , whereupon the e s t e r p r e c i p i t a t e d out  a cream-colored s o l i d .  The  p r e c i p i t a t e was  r e c r y s t a l l i z e d from a p p r o x i m a t e l y 500 d r i e d c r y s t a l l i n e p r o d u c t w e i g h t was of  115.5-116.5°• of "near 118°,  gm.  and  ethanol.  (69*2$)  and had  The a  A s m a l l p o r t i o n o f the e s t e r , r e c r y s t a l -  l i z e d once more, had a m.p. a m.p.  m l . o f 95$ 110  as  washed w i t h i c e -  c o l d w a t e r , f i l t e r e d , sucked d r y on the Buchner f u n n e l  m.p.  the  f o r f o u r h o u r s , when i t changed t o  a y e l l o w i s h - b r o w n , d r y cake. f i n e powder and  ethyl  of 116-117°.  and a y i e l d o f 50$.  The  l i t e r a t u r e reports  (17)  24. Cvclopentadione-1.2  (V) (31)  I n a o n e - l i t r e round-bottomed f l a s k equipped  with  a r e f l u x condenser were p l a c e d 108.6 gm. (0.499 moles) o f 3,5-dicarboethoxycyclopentadione-l,2, a c i d and 20 m l . o f e t h a n o l .  sulfuric  The m i x t u r e was r e f l u x e d f o r  110 mins., w i t h a b a t h temperature s o l u t i o n t u r n e d reddish-brown  400 m l . o f 17$  o f 117°. The r e s u l t i n g  i n color.  A f t e r c o o l i n g (under  n i t r o g e n ) , t h e s o l u t i o n was c o n t i n u o u s l y e x t r a c t e d w i t h e t h e r f o r eleven hours.  M a i n t a i n e d under a n atmosphere o f n i t r o g e n  t h e e t h e r was removed on a w a t e r b a t h and t h e product vacuum distilled.  Cyclopentadione, which c r y s t a l l i z e d i n the  r e c e i v i n g f l a s k , b o i l e d a t 70-80° a t 1.7-1.9 mm., and weighed 24.2 gm. (55.0$).  I t melted a t 54-55°.  L i t . 56°  A i r v e r y r a p i d l y decomposes t h i s d i k e t o n e i  (31). However,  when s e a l e d o f f under n i t r o g e n and kept a t a p p r o x i m a t e l y 0° i t i s s t a b l e f o r a t l e a s t s i x months.  On c o n t a c t w i t h s k i n ,  prominent b l a c k s p o t s form a f t e r some t i m e , and r e m a i n f o r a long period. Cvclopentane-1.2-diol (VI) I n t o a g l a s s - l i n e r was p l a c e d a s o l u t i o n o f 12.5 § « m  (0.128 moles) o f c y c l o p e n t a n e d i o n e - 1 , 2  i n 50 m l . o f a b s o l u t e  e t h a n o l and 0.104 gm. o f p l a t i n u m o x i d e .  The l i n e r was p l a c e d  i n a bomb whose t o t a l v o i d was 278 c c .  The a i r was t h o r o u g h l y  f l u s h e d o u t o f t h e bomb w i t h hydrogen.  The bomb was t h e n  charged t o 500 p . s . i . w i t h hydrogen, and s h a k i n g commenced a t room t e m p e r a t u r e .  I n o n e - h a l f an hour t h e p r e s s u r e dropped  280 p . s . i . , whereupon t h e bomb was r e c h a r g e d t o 400 p . s . i .  25.  w i t h hydrogen and s h a k i n g recommenced. drop o f 450 p . s . i . o c c u r r e d . drop o f 400 p . s . i .  A f t e r 42 h o u r s a t o t a l  Complete h y d r o g e n a t i o n  required a  The c a t a l y s t was f i l t e r e d o f f , and t h e  e t h a n o l removed under r e d u c e d p r e s s u r e a t t h e w a t e r pump. c l e a r , c o l o r l e s s , v i s c o u s l i q u i d was o b t a i n e d . approximately t o 20°  A  On c o o l i n g t o  -10° some c r y s t a l l i z a t i o n o c c u r r e d , b u t on warming  complete s o l u t i o n r e s u l t e d . The  d i - p - n i t r o b e n z o a t e . p r e p a r e d i n t h e r u s u a l manner,  •was r e c r y s t a l l i z e d f r o m e t h a n o l , m.p. 90-104°. R e c r y s t a l l i z e d once more, m.p. 9 3 - 1 2 5 ° .  L i t . , c i s - 117°; t r a n s - 145° (44)  F o r i n f r a r e d a n a l y s i s some of t h i s h y d r o g e n a t e d p r o d u c t was vacuum d i s t i l l e d t w i c e , and made I n t o a 3.0% s o l u t i o n i n pure c h l o r o f o r m . ( F i g . 1, p. 37) Cyclopentadiene The  dehydrating  (VII)  column c o n s i s t e d o f a P y r e x  tube,  30 cm. l o n g and 22 mm. i J d . , wound e x t e r n a l l y i n a s p i r a l w i t h approximately  900 cm. o f No. 27 Chromel-"A" w i r e . , A thermo-  c o u p l e w e l l was c o n s t r u c t e d so t h a t i t would r e s t i n t h e c e n t r e o f t h e c a t a l y s t mass. provided  To one end o f t h e t u b e , a n i n l e t was  so t h a t t h e s u b s t a n c e t o be d e h y d r a t e d and n i t r o g e n gas  c o u l d be i n t r o d u c e d s i m u l t a n e o u s l y .  To t h e " e x i t - e n d " o f t h e  t u b e , a n a r r o w e r p i e c e o f g l a s s t u b i n g was a f f i x e d , w h i c h i n t u r n c o u l d be connected t o two c o n s e c u t i v e  "Dry-ice"-acetone  cooled t r a p s . T h i s tube was f i l l e d w i t h p e l l e t s o f commercial 8-mesh alumina. was  W i t h a slow stream o f n i t r o g e n f l u s h i n g t h r o u g h , i t  h e a t e d a t 4000 f o r a p p r o x i m a t e l y  48 h o u r s t o d r y and  26. a c t i v a t e the c a t a l y s t .  W i t h the temperature a t 400 i 3°, t h e  e x i t end connected t o t h e two D r y - i c e " - a c e t o n e t r a p s , and a u  slow stream o f n i t r o g e n f l u s h i n g t h r o u g h t h e t u b e , 2.47 t r a n s - c y e l o p e n t a n e - l , 2 - d i o l was column over a p e r i o d o f 10-15  gm.  of  slowly introduced i n t o the  minutes.  The p r o d u c t , w h i c h  possessed t h e v e r y c h a r a c t e r i s t i c odor o f c y c l o p e n t a d i e n e , c o n s i s t e d o f 0.4  m l . (21$)  of a s l i g h t l y g r e e n i s h o i l f l o a t i n g  on a p p r o x i m a t e l y one m l . o f w a t e r . The m a l e i c a n h y d r i d e adduct o f t h i s p r o d u c t , t w i c e r e c r y s t a l l i z e d from e t h e r had a m.p.  of  161.5-162.5°. L i t . 165°  (32). Potassium Cyclopentadienide ( V I I I ) C y c l o p e n t a d i e n e was generated' by s l o w l y r e f l u x i n g d i c y c l o p e n t a d i e n e and c o l l e c t i n g t h e d i s t i l l a t e a t 44-46° ( 4 3 ) . T h i s m a t e r i a l was s t o r e d a t " D r y - i c e " temperature t o keep p o l y m e r i z a t i o n a t a minimum.  J u s t b e f o r e use t h e c y c l o p e n t a d i e n e  was r e d i s t i l l e d - b.p. 41-42°. The p o t a s s i u m used i n t h i s r e a c t i o n was h a n d l e d i n t h e f o l l o w i n g manner:  I n s i d e a box f r o m w h i c h a l l a i r was  displaced  w i t h d r y n i t r o g e n gas, the p o t a s s i u m was p l a c e d i n t o a deep mortar c o n t a i n i n g pure anhydrous benzene.  The o u t e r o x i d e -  .coating was c u t o f f , and t h e f r e s h l y cut m e t a l t r a n s f e r r e d i n t o a t a r e d , beaker c o n t a i n i n g anhydrous benzene. p o t a s s i u m (10.7  gm.)  was t h e n i n t r o d u c e d i n t o a 500  bottomed f l a s k c o n t a i n i n g a p p r o x i m a t e l y 100 anhydrous benzene.  The  required ml. round-  ml. of pure,  The f l a s k was t h e n s t o p p e r e d .  The  potassium  s c r a p s r e m a i n i n g i n the mortar were i m m e d i a t e l y decomposed by  27.  the c a u t i o u s a d d i t i o n of d r y t e r t - b u t y l a l c o h o l .  Small  specks  o f p o t a s s i u m r e m a i n i n g on t h e k n i f e and tweezers were a l s o decomposed w i t h t e r t - b u t y l a l c o h o l . The f l a s k c o n t a i n i n g 11.0 gms. (0.282 moles) o f p o t a s s i u m was u n s t o p p e r e d ,  and heated u n t i l t h e m e t a l  liquified.  Once a g a i n t h e f l a s k was s t o p p e r e d , wrapped i n a t o w e l and s h a r p l y shaken t h r e e t i m e s .  An e f f i c i e n t r e f l u x - c o n d e n s e r  was t h e n a t t a c h e d t o t h e f l a s k i n p l a c e o f t h e s t o p p e r , and w i t h d r y n i t r o g e n s l o w l y sweeping i n t o t h e f l a s k , t h e c o n t e n t s were a l l o w e d t o come t o room t e m p e r a t u r e .  Then, w i t h o u t  intro-  d u c i n g a i r , a s o l u t i o n o f 23.0 gm. (0.348 moles) o f c y c l o p e n t a d i e n e i n 100 m l . o f p u r e , anhydrous e t h e r was s l o w l y added t o t h i s f i n e g r a n u l a r p o t a s s i u m i n benzene.  A f t e r the i n i t i a l  r e a c t i o n had s u b s i d e d , t h e m i x t u r e was r e f l u x e d f o r f o u r h o u r s . The e t h e r and benzene were removed under reduced p r e s s u r e and the s l i g h t l y p i n k i s h s a l t f i n a l l y d r i e d a t 0.1 mm. a t 60° f o r three hours. T h i s d r y s a l t , kept i n a w e l l - s t o p p e r e d f l a s k , was i  s t a b l e f o r a t l e a s t t h r e e months. Cyclopentadiene  ( I X ) from P o t a s s i u m  Cyclopentadienide  I n t o a 100 m l . round-bottomed f l a s k was p l a c e d 4.37 gm. o f p o t a s s i u m c y c l o p e n t a d i e n i d e , and t h e n c o o l e d t o -80°.  To  t h i s c o l d s a l t , a p p r o x i m a t e l y 30 m l . o f c o l d (-80°) 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 was added, t h e c o n t e n t s i n t h e r e a c t i o n f l a s k being w e l l s t i r r e d .  Twenty m l . o f i c e - c o l d w a t e r was. n e x t  i n t r o d u c e d , and t h e m i x t u r e d i s t i l l e d a t a b a t h temperature o f 60°.  The r e c e i v e r c o l l e c t i n g t h e product was c o o l e d i n " D r y - i c e "  acetone m i x t u r e . (43.3$).  Approx. 1.2 gm o f c y c l o p e n t a d i e n e was o b t a i n e d .  28. A slow a d d i t i o n o f 20 m l . o f r e d i s t i l l e d b u t a n o l a t j u s t above i t s f r e e z i n g p o i n t t o 24 gm.  of potassium  cyclo-  p e n t a d i e n i d e , f o l l o w e d by a d i s t i l l a t i o n , u s i n g a r e f l u x condenser w i t h a j a c k e t temperature 3*9  gm.  (26$)  of  o f 50° as a column y i e l d e d  cyclopentadiene.  D i e t h y l e s t e r o f 2 . 3 - d i h y d r a z o b i c y c l o (2.2.1.)-5-heotene-2. 3 - d i c a r b o x y l i c a c i d (X) (18) N.N-Dicarbethoxv-endomethylenetetra  hydropvridazine  I n a 250-ml. round-bottomed f l a s k equipped w i t h an e f f i c i e n t r e f l u x condenser were p l a c e d 3-9 pentadiene  gm.  of the c y c l o -  o b t a i n e d i n the l a s t r e a c t i o n and 11.0  gm.  cyclopentadiene obtained from d i c y c l o p e n t a d i e n e . r e f l u x condenser 33.27 gm.  s l o w l y added.  m i x t u r e warmed up on t h i s a d d i t i o n .  After refluxing for  p r e s s u r e , and t h e  v e r y v i s c o u s , s l i g h t l y y e l l o w i s h l i q u i d was y i e l d i n g 43.9 0.2-0.25 mm.: a t 0.5 mm.;  gm.  (96$)  colorless,  of e t h y l a z o d i c a r b o x y l a t e .  removed under reduced  ml.  The r e a c t i o n  12 h o u r s , the r e s u l t i n g m i x t u r e was  i n d i c a t i n g the d i s a p p e a r a n c e e t h e r was  Through the  o f e t h y l a z o d i c a r b o x y l a t e i n 80  o f pure anhydrous e t h e r was  approximately  of  The  remaining  vacuum d i s t i l l e d ,  of p r o d u c t b o i l i n g a t 109-112° a t  Dibromo d e r i v . , m.p. dibromo d e r v . , m.p..  66.0-66*5° L i t . b.p.  67°  (18)  ( D i - e t h y l e s t e r of 2 . V D i a z a b i c y c l o ( 2 . 2 . 1 ) a i c a r b o x y l i c a c i d ) (XIO  120°  heptane-2.^-  (18)  I n t o a g l a s s - l i n e r were p l a c e d 11.55 o f d i e t h y l e s t e r o f 2,3-dihydrazobicyclo(22.2.1)  gm.  (0.0481 moles)  5-heptane-2,  3 - d i c a r b o x y l i c a c i d i n 38 m l . o f a b s o l u t e methanol and  O.O87  gm.  29. of platinum oxide.  The l i n e r was a t t a c h e d t o t h e h y d r o g e n a t o r  w i t h a t o t a l v o i d of 4260 c c , and t h e a i r c o m p l e t e l y f l u s h e d out w i t h hydrogen. t o 239  The l i n e r was t h e n charged w i t h  p . s . i . , and s h a k i n g commenced.  hydrogen  The r e q u i r e d t h e o r e t i c a l  drop of 4.1 p . s . i . o c c u r r e d i n two h o u r s , whereupon hydrogena t i o n was s t o p p e d , t h e l i n e r removed f r o m t h e h y d r o g e n a t o r and t h e c a t a l y s t removed by f i l t r a t i o n .  The p r o d u c t I n t h i s  methanol s o l u t i o n was used" d i r e c t l y i n the n e x t r e a c t i o n . I n a p r e l i m i n a r y r u n , 9-29 2,3-dihydrazo(2.2.1)  gm.  of diethyl e s t e r of  5-neptene-2,3-dicarboxylic a c i d  hydrogenated a t 22.00 p . s . i .  A f t e r one hour 97$ o f t h e  t h e o r e t i c a l amount o f hydrogen was a b s o r b e d j h y d r o g e n a t i o n was complete.  was  i n two hours  F u r t h e r h y d r o g e n a t i o n f o r an hour  r e s u l t e d i n no f u r t h e r d r o p I n p r e s s u r e .  The p r o d u c t  was  i s o l a t e d by f i l t e r i n g o f f t h e c a t a l y s t , removing the methanol a t t h e w a t e r - a s p i r a t o r , and vacuum d i s t i l l i n g t h e r e s i d u e . The f r a c t i o n b o i l i n g a t 115-117° a t 0.9-1.0 mm. and weighed 7.80  gm.  was  collected  (84.3$)  2 3 - D i a z a b l c y c l o ( 2 . 2 . 1 ) heptane T  (Cuprous C h l o r i d e Complex)  ( X I I ) (18) To t h e m e t h a n o l i c s o l u t i o n o f the d i e t h y l e s t e r o f 2,3-diazabicyclo(2.2.1)heptane-2,3-dicarboxylic acid obtained i n t h e l a s t r e a c t i o n , 16.0 added.  gm.  o f p o t a s s i u m h y d r o x i d e was  The r e s u l t i n g s l i g h t l y y e l l o w i s h s o l u t i o n was  r e f l u x e d on a w a t e r - b a t h f o r two h o u r s .  gently  The p o t a s s i u m c a r -  bonate, w h i c h formed I n the r e a c t i o n , was f i l t e r e d o f f , and  30. washed twice w i t h 10 ml. o f a b s o l u t e methanol.  The potassium  carbonate, a f t e r d r y i n g , weighed 13.24 gm. (99.8$).  The com-  bined methanolic f i l t r a t e and washings was c a r e f u l l y  evaporated  o f f under reduced pressure and the r e s i d u e was steam d i s t i l l e d . Steam d i s t i l l a t i o n was continued u n t i l no r e d c o l o r was produced when c u p r i c c h l o r i d e was added t o a few drops o f the distillate.  To the steam d i s t i l l a t e , 8.2 gm. (0.0481 moles)  of c u p r i c c h l o r i d e d i h y d r a t e was slowly added w i t h The r e d cuprous  c h l o r i d e complexrimmediately  c i p i t a t e as long g l i s t e n i n g prisms. p r e c i p i t a t e was f i l t e r e d  stirring.  started to pre-  The next day t h i s r e d  o f f , washed w i t h 30 ml. o f water, and  d r i e d a t 0.1 mm. f o r two hours oyer phosphorous pentoxide. T h i s d r i e d product weighed 3*42 gm. crop was c o l l e c t e d .  (35$).  The t o t a l weight  (44.6$) (From d i e t h y l e s t e r o f  I n a week, a second  o f product was 4.37 gm.  2,3-dihydrazobicyclo$2.2.1)-5-  heptene-2,3-dicarboxylic acid) Anal.  C a l c d . f o r CjHS^.CuCl.^B^O  " Found:  "  C5H8N.CUCI.  8  C l , 17.37  :  C l , 18.17  C l , 18.01, 18.10  Cis-cyclopentane-1.^-diamine  (Stannous  C h l o r i d e Complex) ( X I I I ) ( 1 8 )  A mixture o f 2.707 gm. o f the cuprous c h l o r i d e comp l e x of 2 , 3 - d i a z a b i c y c l o ( 2 . 2 . 1 ) heptane, 24.5 gm. of mossy t i n and 40 ml. o f concentrated h y d r o c h l o r i c a c i d was heated i n a b o i l i n g water bath f o r 6.5 hours.  Then t o the s t i l l hot r e a c t i o n  mixture, 10 ml. o f 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 was added.  31.  A f t e r c o o l i n g t o 6 0 ° , the r e s u l t i n g mixture was f i l t e r e d through a $i,:nt.er-e.d:-«jlass Ct f u n n e l .  A f t e r standing a t 5°  over  n i g h t , the long s i l k y needles were f i l t e r e d o f f . Drying over phosphorous pentoxide and sodium hydroxide p e l l e t s a t 1.0 mm. f o r s i x hours i n a vacuum d e s i c c a t o r gave 5*563 gm. (74-.3$) of a product melting a t 1 5 5 - 1 6 3 ° , L i t . 145-146° ( 4 6 ) ; 172° (18). Anal.  Calcd. »  Found:  f o r C^HgCNR^.(SnCl )2.2HCl.H 0 2  "  2  C5H8(NH )2(SnCl )2.2HCl 2  2  : N,  : H, 4.91$ 5.07$  N (Duma) 4.90, 4.97$  S u c c i n i c A c i d (XIV) (46) To 5.06 gm. of the stannous c h l o r i d e complex of cis-cyclopentane-l,3-diamine d i h y d r o c h l o r i d e , a s o l u t i o n o f 12.24 gm. of potassium permanganate i n 122.5 ml. of water was added.  The mixture was r e f l u x e d i n a b o i l i n g water bath f o r  15 minutes and immediately cooled.  The manganese d i o x i d e was  f i l t e r e d o f f and washed w i t h water.  The combined f i l t r a t e s ,  i f colored, were d e c o l o r i z e d w i t h s u l f u r d i o x i d e and continuously extracted w i t h pure ether f o r 60 hours.  The ether from t h i s  e x t r a c t was evaporated, l e a v i n g a mixture of white and. s l i g h t l y yellowish crystals.  R e c r y s t a l l i z a t i o n from water (charcoal)  y i e l d e d 0.109 gm. (9.7$) of product w i t h a m.p. Of 176-J#d°. A s m a l l p o r t i o n , r e c r y s t a l l i z e d twice more, had a m.p. of 179-1800.  The reported m.p. of s u c c i n i c a c i d i s 188° but the  above o n c e - r e c r y s t a l l i z e d product d i d not depress the mixed m.p. w i t h a u t h e n t i c s u c c i n i c a c i d .  32.  M.p.  of once r e c r y s t a l l i z e d commercial s u c c i n i c a c i d : 1 8 4 - 1 8 5 . 5 ° : 184.5-186°  mixed m.p. Di-p-biomophenacyl e s t e r , m.p. L i t . m.p.  211°  208.5 -  210°  (36)  D i m e t h y l S u c c i n a t e ( X V ) ( 7 ) ( C h a r a c t e r i z e d as the H y d r a z i d e ) To a s o l u t i o n o f 1 5 mgm. i m a t e l y 4 . 5 m l . of methanol a t 0 ° ,  of s u c c i n i c a c i d i n approxa s l i g h t excess of d i a z o -  methane i n c o l d e t h e r was s l o w l y added w i t h s w i r l i n g .  After  a p p r o x i m a t e l y 15 minutes t h e r e s u l t i n g s o l u t i o n was a l l o w e d t o come t o room temperature and t h e e t h e r , diazomethane,  and  methanol removed i n a stream o f n i t r o g e n . To t h e e s t e r o b t a i n e d i n t h e same t e s t - t u b e , used i n t h e above p r e p a r a t i o n  0.14 m l . o f 85$ h y d r a z i n e h y d r a t e  was added t o g e t h e r w i t h 5 d r o p s o f m e t h a n o l .  The c o n t e n t s o f  t h e tube were c o o l e d i n a " D r y - i c e " Q a c e t o n e m i x t u r e , t h e tube e v a c u a t e d , s e a l e d and t h e n h e a t e d a t 1 2 0 ° f o r one h o u r . A f t e r c o o l i n g , the tube was opened and t h e c r y s t a l l i n e p r o d u c t s c r a p e d out and p r e s s e d on f i l t e r paper t o d r y .  Recrystalli-  z a t i o n f r o m e t h a n o l gave w h i t e c r y s t a l s w h i c h m e l t e d a t 164165°.  L i t . 167°  (14).  The above c r y s t a l s , when mixed w i t h  s u c c i n y l h y d r a z i d e o b t a i n e d from a u t h e n t i c a l d i e t h y l gave a m.p.  succinate,  of 1 6 3 . 5 - 1 6 4 . 5 . 0  S u c c l n v l H y d r a z i d e (XVI) (9.14) I n t o a 20 m l . C^iius tube c o n t a i n i n g 1 . 0 0  gm.  (0.00|69  moles) of e t h y l s u c c i n a t e a t 0 ° , 0 . 5 9 m l . ( 0 . 0 1 0 3 moles) o f h y d r a z i n e h y d r a t e a t Oo was added.  The c o n t e n t s o f t h e t u b e  33. were f r o z e n out i n a Dry-ice"-acetone mixture, the !,  s e a l e d , and then heated at 1 2 0 °  evacuated,  tube  f o r one hour.  The c r y s t a l l i n e product r e c r y s t a l l i z e d from e t h a n o l weighed 0.77 gm. (91.6$), had a m.p.  of 1 6 4 . 5 - 1 6 5 . 5 ° .  L i t . l67°(l£).  E t h y l e n e D i u r e t h a n (XVII) ( H ) To 0.592 gm.  o f s u c c i n y l hydrazide i n a 100 ml.  beaker, 6.0 ml. of l N K t i ^ d r o c h l o r i c a c i d and 4 ml. of water were added. was  A f t e r the h y d r a z i d e d i s s o l v e d , 10 ml. o f ether  added and the mixture c o o l e d t o - 5 ° i n an i c e - s a l t  To t h i s c o l d mixture, 0.689 gm. o f sodium n i t r i t e was added w i t h s t i r r i n g . was  The temperature  not allowed t o r i s e above 2 ° .  hath. slowly  of the r e a c t i o n mixture  A f t e r the a d d i t i o n was  completed, the mixture was w e l l s t i r r e d and the e t h e r l a y e r separated.  The aqueous l a y e r was  e x t r a c t e d once w i t h 10 ml.  of f r e s h ether and the combined ether e x t r a c t s were shaken once w i t h sodium b i c a r b o n a t e , s o l u t i o n , f i l t e r e d , and washed once w i t h 15 ml. of water.  then  The e t h e r l a y e r was  separated,  d r i e d w i t h c a l c i u m c h l o r i d e f o r f i v e minutes and f i n a l l y w i t h anhydrous c a l c i u m s u l f a t e .  To t h i s d r i e d e t h e r s o l u t i o n o f  s u c c i n y l a z i d e p l a c e d i n an Erl§nmeyer a b s o l u t e e t h a n o l was a hot p l a t e .  f l a s k , 20 ml. o f  added, and the s o l u t i o n b o i l e d g e n t l y on  When the t o t a l volume was  reduced t o a p p r o x i -  mately 1 ml. the Erlgnmeyer was  t r a n s f e r r e d t o a steam bath  where e v a p o r a t i o n was  t o dryness.  proceeded  c r y s t a l l i n e product weighed 0.145  of 1 0 6 . 5 - 1 0 8 ° .  L i t . 110°  (13)  gm.  T h i s white  (17.5$) and had a m.p.  34-.  H y d r o l y s i s of E t h y l e n e d i u r e t h a n ( X V I I I ) (7) I n a 30 m l . two-necked d i u r e t h a n e i n 6.0  f l a s k , 130 mg.  of e t h y l e n e -  m l . o f 4 8 $ hydrobromic a c i d was  refluxed  for  two h o u r s w i t h a s l o w stream of C 0 2 - f r e e n i t r o g e n  the  system.  sweeping  T h i s n i t r o g e n swept the c a r b o n d i o x i d e g e n e r a t e d  i n the r e a c t i o n out t h r o u g h t h e condenser i n t o a gas d i s p e r s i o n tube immersed i n l N - c a r b o n a t e f r e e sodium h y d r o x i d e s o l u t i o n . A d d i t i o n o f 100 m l . of IN ammonium c h l o r i d e s o l u t i o n and gm.  o f barium c h l o r i d e i n 2 0 m l . o f w a t e r t o t h e  h y d r o x i d e p r e c i p i t a t e d t h e BaCO^.  0.28  sodium  This carbonate, a f t e r being  f i l t e r e d t h r o u g h a g l a s s - s i n t e r e d c r u c i b l e ( M - p o r o s i t y ) , washed w i t h b o i l i n g wateraand a b s o l u t e a l c o h o l and t h e n d r i e d f o r one hour a t 1 2 0 ° weighed  239 mgm.  (94.8$).  The c o n t e n t s o f t h e r e a c t i o n f l a s k were e v a p o r a t e d j u s t t o d r y n e s s a t room t e m p e r a t u r e under r e d u c e d p r e s s u r e . E x c e s s m e t h a n o l i c KOH was added, and the s o l u t i o n a g a i n d i s t i l l e d to dryness, the d i s t i l l a t e  collected i n a receiver  cooled i n a "Dry-ice"-acetone mixture.  Hydrogen c h l o r i d e  bubbled i n t o the d i s t i l l a t e , and t h e r e s u l t i n g  precipitate  was f i l t e r e d o f f . R e c r y s t a l l i z e d f r o m w a t e r - m e t h a n o l ,  the  e t h y l e n e diamine d i h y d r o c h l o r i d e , a f t e r d r y i n g o v e r P2O5 KOH  p e l l e t s , weighed 70.9  mgm.  (85$).  P i c r a t e , r e c r y s t a l l i z e d from a b s o l u t e e t h a n o l , melted w i t h  dec.  a t 229.5-232°.  was  L i t . 230 - 235°  (33)  a n  d  35.  Cyclopentanone Two hundred gm.  (57)  o f powdered a d i p i c a c i d and 10.0  gm.  of powdered Ba(0H)2 were t h o r o u g h l y mixed and t h e n h e a t e d a t 300° i n a s a l t - h a t h .  The crude c y c l o p e n t a n o n e and w a t e r  d i s t i l l e d o v e r a t 101-102°.  The d i s t i l l a t e was  saturated  w i t h anhydrous  K2CO3.  w i t h anhydrous  C a C l 2 , and d i s t i l l e d t h r o u g h a s h o r t column t o  y i e l d 886 gm. at atmospheric  The c y c l o p e n t a n o n e was  separated, d r i e d  (77.1$) o f a c y c l o p e n t a n o n e b o i l i n g a t 128-129° pressure. Cyclopentanol  Cyclopentanone  (SXI) (47)  (88 gm.,  105 moles) was  s l o w l y added,  o v e r a p e r i o d of 105 m i n u t e s , t o a w e l l s t i r r e d s u s p e n s i o n o f 12.3 gm.  (0.324 moles) o f l i t h i u m aluminum h y d r i d e I n approx.  300 m l . o f p u r e , anhydrous  ether.  The r e a c t i o n m i x t u r e was  t h e n r e f l u x e d f o r one and a h a l f h o u r s . was  C a u t i o u s l y , wet  ether  t h e n i n t r o d u c e d , f o l l o w e d by c o l d 10$ H 2 S O 4 , u n t i l most  o f the i n o r g a n i c s o l i d s d i s s o l v e d and two d i s t i n c t formed.  T h i s m i x t u r e was  phases  then continuously extracted w i t h  e t h e r f o r 20 h o u r s , and the r e s u l t i n g e t h e r e x t r a c t d i s t i l l e d . The f r a c t i o n b o i l i n g a t 124-128© was  collected.  t i l l a t e d r i e d w i t h CaS04 and r e d i s t i l l e d  This  y i e l d e d 38.8  (43.5$) o f c y c l o p e n t a n o l b o i l i n g a t 138-139.5°.  disgm.  C y c l o p e n t e n e ( X X I I ) (16) I n a 250 m l . two-necked f l a s k , equipped w i t h a s e p a r a t o r y f u n n e l and a 20 cm. l o n g , f o u r - n e c k e d f i l l e d w i t h p i e c e s o f g l a s s t u b i n g ( 5 mm.  Wurtz column  l o n g and 6 mm. i n  d i a m e t e r ) , was p l a c e d 1 5 . 0 gm. o f 85$ p h o s p h o r i c  acid.  The  column was a t t a c h e d t o a condenser, and t h e r e c e i v i n g f l a s k was heated t o 1 7 3 ° , u s i n g a s a l t - b a t h o f p o t a s s i u m and p o t a s s i u m  nitrate.  From t h e d r o p p i n g  nitrite  f u n n e l , over a  p e r i o d o f two h o u r s , 4 3 . 0 gm. o f c y c l o p e n t a n o l was s l o w l y added. to  A f t e r t h i s a d d i t i o n , t h e b a t h t e m p e r a t u r e was r a i s e d  200° and m a i n t a i n e d a t 200° f o r 40 m i n u t e s .  The  temperature o f t h e d i s t i l l a t e d i d n o t r i s e above 8 5 ° d u r i n g the whole o p e r a t i o n .  The d i s t i l l a t e was d r i e d w i t h anhydrous  c a l c i u m c h l o r i d e , t h e n w i t h anhydrous c a l c i u m s u l f a t e .  The .  d r i e d d i s t i l l a t e was d i s t i l l e d t h r o u g h a 25 em. l o n g - 1 cm. i.d.  eolumn, packed w i t h 4 mm. g l a s s h e l i c e s , y i e l d i n g  3 2 . 0 gm.  (95:*9$)  of product  boiling  at 42-44°.  Trans-cyclopentane-1.2-diol  L i t . 46©.  ( X X I I I ) (44)  I n a 3-necked, 1 - l i t r e f l a s k , equipped w i t h a condenser, d r o p p i n g f u n n e l and s t i r r e r , was p l a c e d 3 1 * 5 gm. ( 0 . 4 6 4 moles) o f c y c l o p e n t e n e .  of the r e a c t i o n mixture  C o n t r o l l i n g the temperature  so t h a t o n l y s l i g h t r e f l u x i n g was  o b t a i n e d , a m i x t u r e o f 207 gm. o f 30$ hydrogen p e r o x i d e (0..?41/}moles) and 558 gm. o f 90$ f o r m i c a c i d (PQ:°w moles) was s l o w l y added w i t h s t i r r i n g  through the dropping  funnel.  3 7 .  A f t e r t h i s a d d i t i o n was complete, t h e r e a c t i o n m i x t u r e was kept a t 40° f o r f o u r h o u r s .  The n e x t day, t h e f o r m i c a c i d  and water were removed under reduced p r e s s u r e (water a s p i r a t o r ) . The r e m a i n i n g o i l was d i s s o l v e d i n a p p r o x i m a t e l y 1 0 0 m l . o f 1 2 $ sodium h y d r o x i d e , and t h e n r e f l u x e d f o r 40 m i n u t e s .  To  t h e c o n t e n t s o f t h e r e a c t i o n f l a s k , d i l u t e s u l f u r i c a c i d was added u n t i l t h e m i x t u r e was j u s t s l i g h t l y b a s i c ( p H . 8 ) .  The  water was d i s t i l l e d o f f under reduced p r e s s u r e and t h e r e m a i n i n g o i l was vacuum d i s t i l l e d . a b.p. o f  1 1 0 - 1 1 3 °  at  mm.,  2 - 3  The p r o d u c t , w h i c h had  weighed 2 6 . 4 gm.  ( 5 5 - 9 $ ) .  D i - p - n i t r o b e n z o a t e , c r y s t a l l i z e d from e t h a n o l , 141.5-142.5°.  m.p.  L i t . 143°  (44).  y , f  #  "i.0  "  5.0  1.C  u  ?.o  19.0  TO  lit  l*i  /  \  I  \  w  '  \h  !  U'  \F il  J—[°* TR  fi«s <  (xxvi)  y\Jj \  /  1  HYDRttENATED  s 1 6  ° (l) v  i  \j  .*«  ieoo  c  m  - i  looo  Pig.  2DOC  IIH  '  tut  *«o  -  itno  im  an  1 . — I n f r a r e d spectrum o f ( c i s - t r a n s ) c y c l o p e n t a n e -  1 , 2 - d i o l , ( V I I ) , and t r a n s - c y c l o p e n t a n e - l , 2 - d i o l ( X X V l ) , as Z% s o l u t i o n s i n c h l o r o f o r m . Pol,  The a n a l y s i s was done b y E. H.  o f t h e B r i t i s h Golumbia R e s e a r c h  Council.  38  BIBLIOGRAPHY 1. A l d e r , K. and H o l z r i c h t e r , H.  Ann. 524: 145. 1936  2. A r m i t , J . W. and R o b i n s o n , B.  J . Chem. Soc. 1604.  3. A r m s t r o n g , H. E .  P r o c . Chem. Soc. (London). 2 5 8 .  Ann. 245: 1 0 3 .  4. B a e y e r , E .  1888; 2 5 1 « 2 8 5 .  5. B a k e r , W. and McOmie, J . F. W.  1887  I889  P r o g r e s s i n O r g a n i c Chem.  1955  3s 44.  6 . Bamberger, E .  B e r . 24: 1758.  273s 373.  1891} 2 6 : 1946.  1893; Ann.  1893  7. Benson, A. A. and Bassham, J . A. 3939.  1925  J . Am. Chem. Soc. 70:  1948  8. Braun, J . and Kuhn, M.  B e r . 60: 2 5 5 1 .  1927  9. Buchmann, E . R., S c h l a t t e r , M. J . and Reim, A. 0.  J . Am.  Chem. Soc. 64: 2701. 1942. 10. Bulow, C. and W e i d l i c h , R.  B e r . 39: 3 3 7 2 .  11. Cason, J . and R a p o p o r t , H.  Laboratory text i n organic  chemistry.  1433.  1 9 5 0 . p. 290  P r e n t i c e - H a l l , New Y o r k .  12. Cope, A. C. and O v e r b e r g e r , C. G.  J . Am. Chem. Soc. 70:  1948  13. C u r t i u s , T.  J . p r a k t . Chem. 5 2 : 210.  1895  14. C u r t i u s , T., S c h o f e r , G. and Schwan, N. 5 1 : 180.  15.  1906  J . p r a k t . Chem.  1895  Dauben, H. J . and R i n g o l d , H. J . J . Am. Chem. Soc. 73: 876.  1951  1 6 . Dehn, W. M. and J a c k s o n , K. E . 4284.  1933  J . Am. Chem. Soc. 5 5 :  39. 17. Dieckmann, W.  B e r . 27: 965.  1894; 30: 1470. 1897;  32:  1930. 1899 18. D i e l s , 0.,  Blom, J . H. and K o l l , W.  1925  Ann. 443: 242.  19. D o e r i n g , W. E . and DePuy, C. H. J . Am. Chem. Soc. 75:  5955. 1953 20. D o e r i n g , W. E. and D e t e r t , F. L. J . Am. Chem. S o c . 73:  876. 1951 21.  D o e r i n g , W. E. and Knox, L. H. J . Am. Chem. Soc. 76:  3203.  1954 22. F i e s e r , L. F. E x p e r i m e n t s i n o r g a n i c c h e m i s t r y , 2nd E d . D. C. Heath Co., B o s t o n . 23.  1941. p. 358  i b i d , p. 359  24. i b i d , p. 365 25. i b i d , p. 380 26. F r a n k l a n d , J.,L. and F i e l d , F. H. J . Am. Chem. Soc. 75:  2819. 1953 27. G i l m a n , H. O r g a n i c C h e m i s t r y , An advanced John W i l e y & Sons, I n c . , New Y o r k . 28.  1938.  treatise. p. 65  Goss, F. R. and I n g o l d , C. K. J . Chem. Soc. 1268.  29. H e i l b r o n , I . D i c t i o n a r y o f o r g a n i c compounds. S p o t t i s w o o d e , London. 30.  1928  E y r e and  1946. V o l . I I . p. 30  i b i d , p. 120  31. Hesse, G. and B u c k i n g , E v a , Ann. 563: 32. Hopkins and W i l l i a m s , S t a f f o f  31.  1949  Organic reagents f o r  o r g a n i c a n a l y s i s . 2nd E d . H o p k i n and W i l l i a m s L t d . Essex, England. 33.  i b i d , p. 172  1950.  p. 82  40. 34. Huckel, E.  Z. Physik. 70: 204. 1931  3 5 . Jaeger, F. M. and Blumendal, H. B. 175:  161.  1928  (C. A. 2 3 : 5 7 3 . 1929)  3 6 . Judefind, W. L. and Reid, E. E. 3 7 . Kauffman  Z. Anorg. allgem. Chem.  J . Chem. Soc. 1043. 1920  (Foot-note i n reference 2 7 , p. 6 5 )  3 8 . Karle, I. L.  J . Chem. Phys. 20: 6 5 . 1 9 5 2  3 9 . Kermac, W. 0. and Robinson, R.  J . Am. Chem. Soc. 3 8 : 762. 1916  40. Lewis, G. N. 41. Meiser, W.  J . Chem. Soc. 121: 427. 1922  Ber. 3 2 : 2049. 1 8 9 9  42. Micovic, V. M.  Org. Syn. 2nd Ed. C o l . V o l . I I : 264. 1943  43. Moffett, R. B.  Org. Syn. 3 2 : 41. 1 9 5 2  44. Owen, L. N. and Smith, P. N. 45. Rabjohn, N.  J . Chem. Soc. 4026. 1 9 5 2  Org. Syn. 28: 5 8 . 1948  46. Roberts, J . D., Lee, C. C. and Saunders, W. H. J r . Chem. Soc. 7 6 : 4 5 0 1 .  1954  47. Roberts, J . D. and Sauer, C. W. 3925.  J . Am.  J . Am. Chem. Soc. 71:  1949  48. Roberts, J . D., Streitweisser, A. and Regan, C. M.  J . Am.  Chem. Soc. 74: 4579. 1952 49. Rouse, R. S.  Yale Univ. Unpublished r e s u l t s . Foot-note  i n reference 21. 5 0 . S c a g l i a r i n i , G. and Lucchi, E.  B o l l . s c i . f a c o l t a chim.  ind., Bologna. 1-2: 5 8 . 1940. (C. A. 34: 2287. 1940) 5 1 . Shriner, R. L. and Fuson, R. C. cation of organic compounds. 1948.  The systematic  identifi-  John Wiley & Sons, Inc.  p. 261.  5 2 . Steyermark, A.  Quantitative organic microanalysis.  Blakiston Co., Philadelphia.  1951. p. 181.  The  41.  53.  Thiele, J.  Ann. 306:  87.  54. T h i e l e , J .  B e r . 33s 666.  55.  Ann. 314-1 296.  Thiele, J.  56. T h i e l e , J . 57.  B e r . 34-: 68.  1900 1901 1901 Org. Syn. 2nd  Thorpe, J . F. and Kon, G. A. R. V o l . I1 192.  58.  1899  V o g e l , A. I .  Ed. C o l .  1941  A text-book of p r a c t i c a l organic chemistry  Longmans, Green and Co. London. J . Chem. P h y s . 2:  59. Wheland, G. W.  1948. p. 843 474.  60.  Wheland, G. W. and Mann, D. E.  61.  W i l l s t a t t e r , R.  62.  W i l l s t a t t e r , R. and H e i d e l b e r g e r , M.  63.  W i l l s t a t t e r , R. and Schmaedel, W.  Ann. 308:  1899 B e r . 46: 517-  B e r . 44:  3423.  B e r . 44 : 34-23.  65.  W i n s t e i n , S.  66.  Z i e g l e r , IC., S p a t h , A., S h a a f , E., Schumann, W.  J . Am. Chem. Soc. 64: 2792.  Winkelmann, E.  Ann. 551:  1949  J . Chem. Phys. 17:264  339.  64. W i ' l l s t a t t e r , R. and Waser, E.  1934  80.  1942  1911  1942 and  1913 1911  

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