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The synthesis of some new derivatives of cinnamic acid and o-oxyphenyl Moore, Ralph G. D. 1934

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I CAT no. LEt&i- HM.R*.,..ML i> a ACC. NO. gy-v-s-^ | THE SYNTHESIS OP SOIvIE HEW DERIVATIVES OF COTAMIG AGID A O O-QXYDIPHEKYL by Ralph G. D» Moore A Thesis submitted f o r the Degree of Iv'IASTER OF ARTS i n the Department of CHEMISTRY Table of Contents Page I n t r o d u c t i o n I A. Prepa r a t i o n of 'benzyl m-io&o cinnamate . 1 B, Pr e p a r a t i o n of m-io&o benzyl cinnamate . , 7 G. Reaction of sodium on (1) m-io&o benzaldehyde and e t h y l acetate (2) benzaldehyde and.benzyl acetate 13 D. Prepa r a t i o n of d e r i v a t i v e s of 2-oxydiphenyl . 17 Synopsis of r e s u l t s . . . . . 26 r THE SYNTHESIS OF SOME NEW DERIVATIVES 0I\ GEfflAMIC ACID AND O-OXYDIPHSNYL. In t r o d u c t i o n . The purpose of t h i s research was to b u i l d up d e r i v a t i v e s of cinnamic a c i d ( e s p e c i a l l y of i t s benzyl ester) and of o-oxydiphenyl f o r f u r t h e r use i n b a c t e r i o l o g i c a l and b i o l o -g i c a l work i n connection w i t h the prevention or cure of t u b e r c u l o s i s . Much work has been done on chemiGO-thera-p e u t i c treatment of t u b e r c u l o s i s , and many simple compounds have been used w i t h v a r y i n g degrees of success ( o u t l i n e d below). I t was held by c e r t a i n p h y s i c i a n s of Vancouver that i f these v a r i o u s simple substances could be u n i t e d and yet r e t a i n t h e i r i n d i v i d u a l e f f e c t on the disease, a more e f f i -c i e n t method of treatment could be devised. We have worked s o l e l y with t h i s end i n view, since the synthesis of a new compound f o r no other reason than that i t i s new i s now g e n e r a l l y considered a. waste of time and money, rather than an o r i g i n a l c o n t r i b u t i o n to progress. A d e t a i l e d l i s t of the simpler compounds already t r i e d , together w i t h the source of i n f o r m a t i o n , f o l l o w s . The " B r i t i s h Medical Journal," Dec. S6, 1908, p. 1893, and the "Lancet," v o l . 1, 1909, p. 413 describe the use of sodium cinnamate. Galmette, i n h i s t e x t "Tuberculous I n f e c t i o n and Tuberculosis i n Man and Animals," p. 665, states that benzyl a l c o h o l has a solvent a c t i o n on the tough I I l i n i n g s of the " b a c i l l i . Benzyl cinnamate i s "being used today "by i n j e c t i n g i t s s o l u t i o n i n o l i v e o i l (H. Gainsborough, Lancet, May 5, 1928, "Benzyl Oinnamic Ester in. Tuberculosis."), Dr. G r i l e ( P r a c t i t i o n e r , 1913, "Treatment of T. B„ by Nascent I o d i n e " ) , D r . S o l i s Cohen (Pharmaoo-Therapeutics, 1928, p. 550), and Galmette ( i b i d . , p. 56) f i n d nascent io d i n e of value. Sodium o-phenyl phenate (U. S. Dept. of A g r i c u l t u r e , G l i p Sheet 778; Jour. F r a n k l i n I n s t i t u t e , J u l y 1933) has been used ?/ith suocess to destroy the b a c i l l u s outside of the body. Some a s t o n i s h i n g r e s u l t s have been obtained by the a d m i n i s t r a t i o n of urea, both o r a l l y and i n t r a v e n o u s l y (Dr. H. Harper, Lancet, Mar, 9, 1901, and June 15, 1901, "Pure urea i n the treatment of T. B."). 1. A. P r e p a r a t i o n of benzyl m-io&o cinnamate. Owing to l a c k of success w i t h the method f i r s t t r i e d (the a c t i o n of "benzyl c h l o r i d e on the sodium s a l t of the a c i d , as o u t l i n e d i n the e a r l i e r paper), I t r i e d the a c t i o n of the a c i d c h l o r i d e on "benzyl a l c o h o l . To conserve the c o s t l y iodo a c i d I used f i r s t cinnamyl c h l o r i d e and "benzyl alcohol.. ' 6.1 p a r t s of a warm melt of cinnamyl c h l o r i d e were added slowly to 4 p a r t s (a s l i g h t excess) of benzyl a l c o h o l . Vigorous e b u l l i t i o n and intense fuming of HC1 were n o t i c e d during the a d d i t i o n . The r e a c t i o n mixture was warmed to expel HG1 and ensure completion of the r e a c t i o n , and sub-jected to vacuum d i s t i l l a t i o n . A l i t t l e c l e a r o i l came over up to £00°, but the l a r g e r part b o i l e d at 237*(30 mm. pressure), i n f a i r l y close agreement with the b o i l i n g point of 225°- 2.35° at u n s p e c i f i e d pressure, given by Grimaux (O.r. 67, 1049). The d i s t i l l a t e was an o i l that s o l i d i f i e d on long standing at low temperatures. On c r y s t a l l i z i n g once from a l c o h o l c r y s t a l s were, obtained which melted at 36.5°. (Melting p o i n t of benzyl cinnamate i s 39° according to Grimaux). m-iodo cinnamyl c h l o r i d e . To u t i l i z e the above method i n the p r e p a r a t i o n of benzyl m-io&o cinnamate, i t was necessary f i r s t to prepare m-io&o cinnamyl c h l o r i d e . Two methods were employed to do t h i s ; f l ) by the a c t i o n of P Q l g (2) by the a c t i o n of SOClg. The second was the one f i n a l l y adopted f o r reasons of economy and expediency. 1. The dry a c i d , not c r y s t a l l i z e d , but merely p r e c i -p i t a t e d from i t s sodium s a l t , was t r e a t e d w i t h a s l i g h t -t h e o r e t i c a l excess of PGlg. On gentle warming a v i o l e n t r e a c t i o n ensued. A f t e r the POGl^ had been d i s t i l l e d o f f on o the steam bath, the main product came over at 195°- 205° (20 mm.) or 190°- 195°(16 mm.). A s l i g h t decomposition was n o t i c e d , the d i s t i l l a t e being colored w i t h i o d i n e . On standing i n the i c e chest, c r y s t a l s formed i n needles r a d i -a t i n g from v a r i o u s centres. The y i e l d was between 85 - 90$ of the theory. 2. Y/ith t h i o n y l c h l o r i d e i t was found necessary to employ a l a r g e excess p a r t l y because of the voluminous nature of the iodo a c i d , p a r t l y because of the s l u g g i s h nature of the r e a c t i o n . At l e a s t an equal weight of SOOl^ was r e f l u x e d w i t h the a c i d f o r several hours, u n t i l a l l the a c i d had disappeared to form a reddish brown s o l u t i o n and no more HOI fumes came o f f . I f the s o l u t i o n was not per-f e c t l y c l e a r , with no i n s o l u b l e residue, i t was found to ensure b e t t e r r e s u l t s to f i l t e r i t through asbestos. The excess S001 p was d i s t i l l e d o f f on the steam bath,and the residue subjected to vacuum d i s t i l l a t i o n . B o i l i n g p o i n t , 184°- 187* at 6 mm., 213°- 218° at 40 mm. This l a s t i s however accompanied by much, decomposition, which, besides i n v o l v i n g a l o s s , contaminates the d i s t i l l a t e w i t h i o d i n e , which i s extremely d i f f i c u l t to remove, even on repeated f r a c t i o n a t i o n s . C r y s t a l s formed i n a r e d i s t i l l e d sample at 35.3 V The product i s soluble i n ether, benzene, chloroform, carbon d i s u l p h i d e . With the above method a y i e l d of 93$ was obtained, which makes i t a b e t t e r procedure than the f i r s t , since the iodo a c i d i s comparatively expensive. To confirm the i d e n t i t y of t h i s substance I proceeded as f o l l o w s : an a c c u r a t e l y weighed sample, p u r i f i e d by care-f u l f r a c t i o n a t i o n s , was placed i n a beaker, covered w i t h water,-and decomposed by the a d d i t i o n of KOH. I t was neces-sary to heat f o r quite a time to ensure s o l u t i o n . When no p a r t i c l e s remained, the s o l u t i o n was a c i d i f i e d w i t h HNOg and cooled* The white f l o c o u l e n t p r e c i p i t a t e thus obtained was f i l t e r e d o f f through asbestos, and AgKOg s o l u t i o n i n excess was added to the f i l t r a t e , along w i t h the washings. The AgCl so formed was then determined i n the us u a l way, i t being-found necessary, however, to run blanks to determine the c o r r e c t i o n to be applied f o r the c h l o r i n e content of the KOH and HNOg used. 4, R e s u l t s : Wt. sample Corrected wt. AgCl fo CI .3543 g. .1741 g. IS.16 fa .3455 g. .1709 g. 12.24 fa The c a l c u l a t e d value f o r C H I (GH)„C0C1 i s 12.13%. 6 4 2 This r e s u l t was su b s t a n t i a t e d "by an examination of the f l o c c i i l e n t p r e c i p i t a t e obtained on a c i d i f i c a t i o n i n the above a n a l y s i s . R e c r y s t a l l i s e d s e v e r a l times from d i l u t e a.lcohol i t gave a corrected melting p o i n t of 191.5 . This seemed h i g h , as G a b r i e l and Herzberg (B. 16, 2037) give o 182-3 w i t h decomposition f o r m-iodo cinnamic a c i d , so I r e -examined some iodo a c i d .prepared from m-iodo benzaldehyde. A f t e r s e v e r a l c r y s t a l l i z a t i o n s t h i s y i e l d e d an a c i d w i t h e x a c t l y the same melting point (191.5°) w i t h very l i t t l e de-composition, G a b r i e l ' s and Herzberg's r e s u l t s are then about 10 degrees too low, the apparent checks obtained i n my f i r s t paper probably being due p a r t l y to i m p u r i t i e s , p a r t l y to neglect of thermometer stem c o r r e c t i o n . A c o n s i d e r a t i o n of the table below w i l l i n d i c a t e that the higher value i s the more l o g i c a l one. •Compound M.P. Compound M.P. cinnamic a c i d 133°G benzoic a c i d 121-2°C m-nitro " TT 196-7° m-nitro w " 140° m-amino " " 180-1° m-amino n 174° m-chlor " " 176° m-chlor " . » 153(158)' m-broin » . ». 176-179 ° m-brom » « 155" m-iodo " " 181°(?)or m-iodo " " 188° 191.5° Pre p a r a t i o n of the benzyl e s t e r . 40 g. of the iodo c h l o r i d e prepared as above were warmed w i t h 15 g. CgHgCHgOH. A vigorous e v o l u t i o n of HC1, accompanied by a r i s e i n temperature was n o t i c e d . On standing, f i n e c r y s t a l s were deposited. The r e a c t i o n mix-ture was d i s t i l l e d under a vacuum, the benzyl a l c o h o l f i r s t coming over c a r r y i n g w i t h i t the iodi n e which had contami-nated the a c i d c h l o r i d e . At 17 mm. 45 g. (90fo y i e l d ) came over between 260°- 280°. O n . r e d i s t i l l a t i o n , the major a o . p o r t i o n b o i l e d at 265 - 275 (16 mm.). At 12 mm. a sample of t h i s d i s t i l l a t e b o i l e d at 255°- 260°, and f o r a n a l y s i s the middle p o r t i o n (273° at 15-16 mnu) was taken. The product i s a pale yellow o i l when d i s t i l l e d . On c o o l i n g , i t becomes t h i c k l i k e honey, g r a d u a l l y becoming t u r b i d . On long standing, or on c o o l i n g w i t h i c e , c r y s t a l s form about s e v e r a l centres, l i k e spokes i n a wheel. To obtain a, pure sample f o r a n a l y s i s and melt i n g p o i n t , i t was 6. c r y s t a l l i z e d from 95% a l c o h o l as follows-: some of the o i l was warmed w i t h a l a r g e amount of a l c o h o l t o about 50° and s t i r r e d u n t i l no more d i s s o l v e d . The c l e a r s o l u t i o n was decanted from the excess o i l , and the operation repeated u n t i l a l l the o i l d i s s o l v e d . On standing some time i n a c o o l p l a c e , f i n e white needles separated, of m e l t i n g p o i n t 50.0 . An a n a l y s i s (method of Oarius) gave the f o l l o w i n g r e s u l t s : Sample Ag l fa I .1968 g. .1268 g. 34 883 .2691 g. .1739 g. 34.93 The t h e o r e t i c a l value f o r C K I(GK) COOCEL CH_ i s 34.87% 6 4 2 2 6 5 i o d i n e . The compound i s very soluble i n benzene, chloroform, e t h y l acetate, carbon d i s u l p h i d e , and ether. I t i s only s l i g h t l y s o l u b l e i n c o l d a l c o h o l , and i n s o l u b l e i n water. I t i s very s l i g h t l y soluble i n g l a c i a l a c e t i c a c i d at 0 G, r a t h e r soluble at room temperature, and very soluble i n the hot a c i d . For q u a n t i t y production of t h i s ester I used the f o l l o w -i n g m o d i f i c a t i o n : 40 g. of the a c i d were r e f l u x e d with SOG1 and the excess d i s t i l l e d o f f , the l a s t traces being removed by warming i n a vacuum. Without f u r t h e r p u r i f i c a t i o n I . added to the warm mass 15-20 g. of benzyl a l c o h o l , and proceeded as above. Y i e l d was almost q u a n t i t a t i v e - 50 g. of o i l , not r e c r y s t a l l i z e d . B». P r e p a r a t i o n of m-iodo "benzyl cinnamate. This was done by a method analogous to that used i n pre p a r i n g benzyl m-iodo cinnamate' — m-iodo benzyl a l c o h o l was allowed to react w i t h cinnamyl c h l o r i d e . 1. P r e p a r a t i o n of m-iodo benzyl a l c o h o l . As I had on hand some m-iodo benzaldehyde, a d i r e c t conversion of t h i s to m-iodo benzyl a l c o h o l and m-iodo benzoic a c i d seemed the most convenient way of o b t a i n i n g the former.. For"notes on the procedures given i n the l i t e r a t u r e to t h i s end see l a t e r . I proceeded, then, as f o l l o w s : 20 g. m-iodo benzaldehyde were t r e a t e d w i t h a s o l u t i o n of 10 g. potassium hydroxide i n 95$ a l c o h o l . The mixture became warm and s o l u t i o n ensued. A f t e r heating to b o i l i n g the s o l u t i o n was allowed to c o o l , and i n some hours the dark l i q u i d had become a t h i c k paste of c r y s t a l s (potassium benzoate, p r o b a b l y ) . Water was added t o d i s s o l v e t h i s by-product (or p a r t of the a l c o h o l was f i r s t d i s t i l l e d o f f ) , and the r e s u l t a n t c l e a r dark brown l i q u i d evaporated on the steam bath u n t i l most of the a l c o h o l had been d r i v e n off.. This removal was complete enough when the e v o l u t i o n of vapor had become very slow and the dark brown o i l which c o l l e c t e d at the bottom of the f l a s k no longer increased. A f t e r c o o l i n g , the water s o l u t i o n was decanted and extracted w i t h ether to recover the, small amount soluble i n the water ( s m a l l , that i s , i f most of the a l c o h o l had "been d r i v e n o f f ) . The dark o i l was e i t h e r taken up i n the ether or d i s t i l l e d d i r e c t l y , depending on the amount. Treatment of the crude product w i t h e i t h e r sulphurous a c i d or sodium a c i d s u l p h i t e was found unnecessary, there being no f r e e i o d i n e or uncon-v e r t e d iodo benzaldehyde present as impurity. The e t h e r e a l e x t r a c t (or the o i l ) , was d r i e d with, calcium c h l o r i d e and d i s t i l l e d . At IE mm. the major p o r t i o n came over at 160°- 165°; according to Langguth f B. 38, 2063), m-iodo benzyl a l c o h o l at 5 mm. b o i l s at 154". The y i e l d proved to be almost q u a n t i t a t i v e , being i n t h i s case j u s t under 10 g., and i n l a t e r r e p e t i t i o n s v a r y i n g from 90 - 100% of the t h e o r e t i c a l y i e l d . To recover the by-product, m-iodo benzoic a c i d , the aqueous s o l u t i o n obtained as above, a f t e r being extracted w i t h ether, was a c i d i f i e d w i t h d i l u t e s u l p h u r i c a c i d , and the r e s u l t a n t n e a r l y white p r e c i p i t a t e f i l t e r e d o f f . C r y s t a l l i z e d . o o from acetone, the substance melted at 188 - 189 , i n close agreement w i t h the melting poi n t of 188° given i n the l i t e r -ature f o r m-iodo benzoic a c i d . As the above procedure y i e l d e d such good r e s u l t s , most of the iodo benzyl a l c o h o l needed was prepared so. Some, however, was made from m-nitro benzaldehyde as f o l l o w s : m-nitro benzaldehyde to m-nitro benzyl a l c o h o l (Becker, B. 15, 2090). With c o o l i n g , 2 p a r t s of m-nitro benzaldehyde were added to a s o l u t i o n of 1 p a r t potassium hydroxide and 6 p a r t s of water, and the mixture l e t stand overnight, (Somewhat b e t t e r y i e l d s were obtained u s i n g 1.2 p a r t s of KOH i n s t e a d of 1 ) . The product obtained by e x t r a c t i o n w i t h ether was used d i r e c t l y , without f u r t h e r p u r i f i c a t i o n , i n the f o l l o w i n g r e d u c t i o n : m-a.mino benzyl a l c o h o l from the n i t r o compound (fa t t t e r , B. 30, 1005). With constant c o o l i n g , 125-150 g. of mossy z i n c were added g r a d u a l l y to a s o l u t i o n of 50 g. m-nitro benzyl a l c o h o l i n 200 cc. of a l c o h o l and 325 cc. of HG1 (sp. g.1.19). The mixture was l e f t overnight, and the excess zi n c then f i l t e r e d o f f . Hot d e s i r i n g the pure amino compound, I attempted to vary the orthodox method as f o l l o w s : m-diazo benzyl a l c o h o l c h l o r i d e . As the a c i d i n the above f i l t r a t e had been p r a c t i c a l l y exhausted by the excess z i n c , 60-70 cc. of HG1 (1.19) were e f i r s t added to the s i r u p y f i l t r a t e ; a f t e r c o o l i n g to 0 0, the amino hydrochloride s o l u t i o n was d i a z o t i z e d w i t h 10% sodium n i t r i t e s o l u t i o n , about 200 cc. being r e q u i r e d . Conversion, of the above diazo c h l o r i d e to m-iodo benzyl a l c o h o l . I f i r s t f o l lowed Langguth's procedure (B.38, 2063). Ho the above diazo s o l u t i o n a s o l u t i o n of 65 g. EI i n 200cc. water was added; then, w i t h warming, copper poy/der was added. (The powder paste was prepared according to Gattermann, B. 23, 1219). Vigorous e b u l l i t i o n ensued. At the end of the e v o l u t i o n of n i t r o g e n the mixture was cooleu and extracted w i t h ether. I t was found d i f f i c u l t to remove the f i n e copper powder, which may account f o r the poor r e s u l t s obtained. When vacuum d i s t i l l a t i o n was attempted ( a f t e r the evaporation of the e t h e r ) , the r e s u l t was, i n seve r a l experiments, that a few grams of a c l e a r l i q u i d passed over at the b o i l i n g p o i n t of m-iodo benzyl a l c o h o l , and then the residue i n the f l a s k ( c o n t a i n i n g the greater part of the r e a c t i o n product) foamed up, changing i n t o a black, t a r r y , voluminous mass of i r r i t a t i n g odor, w i t h separation of i o d i n e , which contaminated what product had already d i s t i l l e d over. This miscarriage seemed due to a condensation between two molecules catalysed by, perhaps, t r a c e s of copper powder. Time d i d not permit a close i n v e s t i g a t i o n , but more work i s i n d i c a t e d (probably the s u b s t i t u t i o n of another c a t a l y s t , e.g., cuprous c h l o r i d e , would be s u f f i c i e n t , or again i t might be found necessary to p u r i f y the m-amino benzyl a l c o h o l before d i a z o t i z i n g ) . 11. S l i g h t l y "better r e s u l t s were obtained by the omission of copper powder from the above procedure. The r e a c t i o n was not so smooth, however, and even i n t h i s case some' decom-p o s i t i o n took place on d i s t i l l a t i o n , f¥ote: i f the e t h e r e a l e x t r a c t was a very dark red, de-composition n e a r l y always ensued on d i s t i l l a t i o n ; so p o s s i b l y a by-product of the r e a c t i o n c a t a l y s e s the imdesired conden-s a t i o n on d i s t i l l a t i o n ) . I t may r e a d i l y be seen t h a t the f i r s t method given above fthe a c t i o n of a l c o h o l i c potash on m-iodo benzalde-hyde) i s the most convenient and economical. 2. m-iodo benzyl cinnamate from the above. About 13 p a r t s f a s l i g h t ' excess) of a warm melt of cinnamyl c h l o r i d e were poured'into 16 p a r t s of m-iodo ben-z y l a l c o h o l . A f t e r a moment HG1 s t a r t e d coming o f f , accom-panied by a r i s e i n temperature, u n t i l the mixture was e f f e r v e s c i n g v i o l e n t l y . When the v i g o r of the r e a c t i o n had somewhat abated, the f l a s k was warmed said shaken, to obtain a more complete r e a c t i o n by removal of HOI.. Viftien no more HOI was evolved, the mixture was subjected to vacuum d i s -t i l l a t i o n . F i r s t a yellow o i l , probably the excess cinnamyl c h l o r i d e , came o f f below 150 , then the temperature rose r a p i d l y to 260°. The greater f r a c t i o n came over f a i r l y c o n s t a n t l y at 262-264* at 7 mm. or 269-270° at 11-12 mm. The y i e l d was about 75% of t h e o r e t i c a l . As received the d i s t i l l a t e was a yellow o i l , v i s c o u s at-room temperatures 0 and "becoming almost b r i t t l e at - £0 0, without, however, c r y s t a l l i z i n g . On standing some ,days i n the i c e chest w i t h a few seed c r y s t a l s i t s l o w l y c r y s t a l l i z e d from s e v e r a l centres i n r a d i a t i n g needles, To o b t a i n c r y s t a l s f o r a n a l y s i s , the o i l was warmed to about 40" w i t h 95$ a l c o h o l ; a f t e r s t i r r i n g f o r some time the s o l u t i o n was decanted through a f i l t e r and allowed to c o o l . C r y s t a l formation i s very s l u g g i s h , seeding w i t h p r e v i o u s l y obtained c r y s t a l s and c o o l i n g w i t h i c e and s a l t being-necessary f o r best r e s u l t s . On r a p i d c o o l i n g , small r e c t a n -gula r prisms, of a very pale yellow, were obtained, and on slow c o o l i n g l a r g e , r ectangular , almost c o l o r l e s s p l a t e s , A specimen me l t i n g at 35° was analysed f o r iodine (method of C a r i u s ) . Sample A g l $1 .2374 g. .1524 g, . 34.70$ .2740 g. .1755 g. 34.62$ The t h e o r e t i c a l value f o r m-iodo benzyl cinnamate i s 34,87$I. A combustion a n a l y s i s gave carbon 52.5$, hydrogen 3,7$, The c a l c u l a t e d values f o r m-iodo benzyl cinnamate are carbon 52.75$, hydrogen 3.6$. Prom the, above r e s u l t s i t f o l l o w s that there can be very l i t t l e doubt as to the i d e n t i t y of the substance. 13. The a c t i o n of solvents on t h i s product i s very s i m i l a r t o t h e i r a c t i o n on "benzyl m-iodo cinnamate, as was expected. I t i s very soluble i n ether, e t h y l acetate, "benzene, acetone, carbon d i s u l p h i d e , and chloroform. I t i s r a t h e r i n s o l u b l e i n 957<J a l c o h o l or g l a c i a l a c e t i c a c i d at 0 G, but very soluble i n the l a t t e r at elevated temperatures, while more soluble i n the former at 40°0 than benzyl m-iodo cinnamate. G. Reaction of sodium on .(1) m-iodo benzaldehyde and e t h y l acetate (2) benzaldehyde and benzyl acetate. While i n v e s t i g a t i n g v a r i o u s p o s s i b l e methods of synthe-s i z i n g benzyl m-iodo cinnamate, the work of Glaisen (B, S3, 976) on condensation of benzaldehyde w i t h e t h y l acetate to e t h y l cinnamate by means of sodium came to my n o t i c e . By s u b s t i t u t i n g m-iodo benzaldehyde and benzyl acetate f o r the above a p o s s i b l e means of preparing benzyl m-iodo cinnamate seemed o f f e r e d , although, as the work of Bacon (Am. 33, 94) showed, the s u b s t i t u t i o n of the benzyl f o r the e t h y l group a f f e c t s the r e a c t i o n s of an ester towards sodium so markedly that there seemed l i t t l e chance of working out a procedure to y i e l d b e t t e r r e s u l t s than that given above. However, a very convenient method f o r the pre p a r a t i o n of e t h y l m-iodo cinnamate seemed i n d i c a t e d : 06H4ICHtS; CHgG-^Q^Et 0 H^IGJH = C H C ^ ^ E t '.Fa-'' 14. I proceeded as f o l l o w s : A s o l u t i o n of EO g, m-iodo benzaldehyde i n about 50 cc. pure e t h y l acetate was added slow l y to a f l a s k c o n t a i n i n g 2 g. of sodium wire i n 50 cc. of e t h y l acetate, the whole being cooled down to 0°C. A f t e r a l l the s o l u t i o n had been added, I l e t the r e a c t i n g mixture stand u n t i l a l l the sodium had vanished, then added aboxxt 6 g. g l a c i a l a c e t i c a c i d , mix-ed w e l l and added water u n t i l a l l the s o l i d sodium acetate had d i s s o l v e d . The l a y e r of e s t e r s was separated, washed w i t h IfaoGGg s o l u t i o n , d r i e d w i t h GaOl , and the excess e t h y l acetate d i s t i l l e d o f f . The residue was d i s t i l l e d i n a va-cuum. B o i l i n g p o i n t , 180-190° at 16 mm. melting point 3 7 — the same c h a r a c t e r i s t i c s as the e s t e r obtained e a r l i e r by an e n t i r e l y d i f f e r e n t method (Paper f o r the degree of Bachelor of A r t s , IT.B.C. 1932) 1. To make s t i l l more c e r t a i n I s a p o n i f i e d some of the product w i t h KOH, p r e c i p i t a t e d w i t h HpSO^, and r e c r y s t a l l i z e d twice from d i l u t e a l c o h o l . The m e l t i n g p o i n t of the c r y s t a l s so obtained was 191 , as found above f o r m-iodo cinnamic a c i d . In the above procedure, the y i e l d , as determined by s e v e r a l experiments, was 73-74$ of the t h e o r e t i c a l . This, coupled w i t h the comparative ease and economy of the method, In t h i s paper the pressure was given as 10 mm. Since then the manometer then used has been r e c a l i b r a t e d . Corrected pressure: 30 mm. B. P. 210 - 2 1 5 " , • ' . 15. makes i t f a r superior to that employed i n my f i r s t paper, which i n v o l v e d two operations, (1) making of the iodo a c i d from m-iodo "benzaldehyde (E) conversion to the e s t e r "by absolute a l -cohol . However, when I came.to attempt the synthesis of benzyl cinnamate by an analogous method, I d i d not meet wi t h the same success. Benzyl acetate, as shown by Conrad, and Hodgkinson (A. 193,300) and more f u l l y by Bacon (Am. 33,94), does not rea c t towards sodium i n the same way that the lower a l i p h a t i c acetates do, the c h i e f product of the r e a c t i o n being benzyl a l c o h o l . In the i n i t i a l experiments i t was found impossible to add sodium wire t o an e t h e r e a l s o l u t i o n of benzyl acetate, as a vigorous r e a c t i o n ensued even at 0°. A t y p i c a l e x p e r i -ment was as f o l l o w s : • To 100 cc. of anhydrous ether, c o n t a i n i n g 2.3 g. sodium wire was added s l o w l y a mixture of 20 g. benzyl acetate and 10 g. benzaldehyde, the temperature of the whole being kept o l e s s than 5 . There was no n o t i c e a b l e r e a c t i o n u n t i l about one t h i r d of the mixture had been added, when a white f l o c -culent p r e c i p i t a t e became evident, accompanied by e v o l u t i o n of bubbles from the sodium. In s p i t e of good c o o l i n g , a a gradual r i s e i n temperature set i n , u n t i l 10 had been reached, when momentarily the r e a c t i o n went out of c o n t r o l , the temper-ature p a s s i n g 20°. The p r e c i p i t a t e had become a r e d d i s h brown. A f t e r the a d d i t i o n of a l l the mixture, the product was 16. t r e a t e d i n the -usual way - n e u t r a l i z e d w i t h g l a c i a l a c e t i c a c i d , washed w i t h water, separated, and washed w i t h soda s o l u t i o n . The soda wash was a c i d i f i e d , on which a p r e c i p i t a t e , h a l f o i l , h a l f s o l i d , came down, which s o l i d i f i e d on c o o l i n g . ' A f t e r washing the e t h e r e a l e x t r a c t w i t h soda s o l u t i o n and d r y i n g w i t h Ga01 o, the ether was d i s t i l l e d o f f , and the residue subjected to vacuum d i s t i l l a t i o n . At 10 mm. the great-9 er p o r t i o n d i s t i l l e d at 96 0; then the temperature rose inde-f i n i t e l y to over 800°, w i t h comparatively l i t t l e o i l passing over. Obviously, then, there could have been very l i t t l e benzyl-cinnamate present. The low b o i l i n g p o r t i o n was f r a c -t i o n a t e d at atmospheric pressure, w i t h most passing over at 204 ( c o r r e c t e d ) , and possessing the c h a r a c t e r i s t i c sweet smell and o i l y f e e l of benzyl a l c o h o l . From the above i t i s seen t h a t , under the c o n d i t i o n s of the experiment, the benzyl acetate, f a r from condensing to a more complex molecule, had been s a p o n i f i e d at 3ome stage to the a l c o h o l . As time was l a c k i n g f o r side i n v e s t i g a t i o n s , t h i s r e a c t i o n was not gone i n t o as f u l l y as i t should have been. By v a r y i n g the c o n d i t i o n s (e.g. a more rig o r o u s c o n t r o l of temperature, use of sodium lumps instead of w i r e , and s e l e c t i o n of a d i f f e r e n t solvent) the desired condensation may p o s s i b l y be a t t a i n e d . A point of i n t e r e s t f o r f u t u r e work would be the inves-t i g a t i o n of side products obtained by the above procedure, 17, such, as the acid, or acid s obtained above from the soda wash, and the higher f r a c t i o n s of the n e u t r a l p o r t i o n . These l a t -t e r are undoubtedly i n part e s t e r s , as treatment w i t h XOH y i e l d e d a c i d i c and n e u t r a l c o n s t i t u e n t s ; these i n t e r e s t i n g p o i n t s 'could n ot, however, be followed up i n the time at my d i s p o s a l . D, . Pr e p a r a t i o n of d e r i v a t i v e s of E-oxydiphenyl. Our a t t e n t i o n was drawn to o-oxydiphenyl by a d e s c r i p -t i o n (U. 3. Dept. of A g r i c u l t u r e , C l i p Sheet No. 778) of i t s use as a d i s i n f e c t i n g agent f o r des t r o y i n g t u b e r c l e b a c i l l i on premises where t u b e r c u l o s i s i s being e r a d i c a t e d . I t i s described as being most e f f e c t i v e without being severely t o x i c t o the animals. (Jour. F r a n k l i n I n s t , , J u l y 1933). 1. Unsuccessful attempt to prepare an iodo d e r i v a t i v e of o-oxydiphenyl from p - i o d o a n i l i n e and phenol. H i r s c h (B. E3, 3705 ff.) obtained a mixture of ortho and para isomers of oxydiphenyl, besides a considerable amount of the isomeric diphenyl ether, from the i n t e r a c t i o n of benzene diazo c h l o r i d e and phenol. Y i e l d s were not stated, nor the method of separating the isomeric oxydiphenj/ls. Hoping to obtain iodo d e r i v a t i v e s by t h i s method, I proceeded as o u t l i n e d below, 50 g. p - i o d o a n i l i n e were d i s s o l v e d i n 100 cc. of con-centrated HOI (36$) and EOO-300 cc. H 20 by heating. The 18. r a p i d l y cooled mixture was then d i a z o t i z e d w i t h 18 g. IfaMOp to "blueing of starch-KI paper. The r e s u l t i n g s o l u t i o n was extra c t e d w i t h successive 100 g. p o r t i o n s of 95% phenol. F i v e p o r t i o n s were used, "but the l a s t two showed only the constant gain i n weight due to the water taken up. This r a p i d l y darkening phenol s o l u t i o n was p a r t l y d r i e d w i t h a l i t t l e s o l i d HaCI, then heated on the water bath i n small p o r t i o n s frun i n w i t h a dropping funnel) under a r e f l u x . The gas e v o l u t i o n was very s l u g g i s h as compared w i t h that observed i n the i n t e r a c t i o n of benzene diazo c h l o r i d e and phenol. When the r e a c t i o n was at an end, the product was washed w i t h saturated KaCl s o l u t i o n and d i s t i l l e d . When most of the phenol had come over (some i o d i n e fumes were n o t i c e -able) the d i s t i l l a t i o n was continued i n a vacuum. The only product other than phenol which d i s t i l l e d was a s l u g g i s h black o i l which s o l i d i f i e d i n the condenser and r e c e i v e r . At 10 mm. pressure most of t h i s came over (with some decom-p o s i t i o n , as iodi n e vapors were s t i l l evident) up to S35°0. The product was worked up f o r a c i d i c and n e u t r a l con-s t i t u e n t s . (a) The s o l u t i o n i n hot toluene was extracted w i t h hot d i l u t e KaOH s o l u t i o n u n t i l nothing p r e c i p i t a t e d on a c i d i f i c a t i o n . (b) This UaOH e x t r a c t , green i n c o l o r when d i l u t e , was ex-t r a c t e d w i t h hot toluene a f t e r a c i d i f i c a t i o n . On d i s t i l l a t i o n , the toluene s o l u t i o n (b) afforded a bla c k t a r , which, when subjected to vacuum d i s t i l l a t i o n , y i e l d e d only phenol, there "being p r a c t i c a l l y no high "boiling c o n s t i t u e n t s . ( a ) , however, when subjected to the same procedure, gave a pale yellow d i s t i l l a t e to 200"G (10 mm.) which s o l i d i f i e d i n the r e c e i v e r . On c r y s t a l l i z a t i o n from a l c o h o l , i t formed s i l v e r y white p l a t e s melting at 128°G. The a n a l y s i s f o r iodine proved very u n s a t i s f a c t o r y : Wt. sample A g l . % iodine .2425 g, .3459 g. 77.11 % .1921 .2742 77.16 The t h e o r e t i c a l amount of i o d i n e i n CgH^I - 0 - GgHg i s 42.88%, i n GgH^I - 0 - CgH^I, 60.16%. The above compound may have been formed during d i s t i l l a t i o n by the free i o d i n e vapors observed, which p o s s i b l y introduced more iodine i n t o the nucleus. However, as the compound was c e r t a i n l y not what we d e s i r e d (being i n s o l u b l e i n HaOH s o l u t i o n ) , and as time was short, f u r t h e r i n v e s t i g a t i o n was dropped f o r the time being. 2. P r e p a r a t i o n of 5-iodo-2-oxydiphenyl. The above compound was obtained from 5-amino-2-oxydi-phenyl by the u s u a l r e a c t i o n s . The amino compound v/as prepared from 5-benzeneazo-2-oxydiphenyl obtained according to Borsche and Scholten, B. 50 (1917), 601. 17 g, of o-oxydiphenyl were d i s s o l v e d i n a s o l u t i o n of 15 g. KaOH i n 350 cc. HgO. To t h i s cooled s o l u t i o n was 20. added g r a d u a l l y , w i t h vigorous s t i r r i n g , a cold diazo benzene c h l o r i d e s o l u t i o n from 10 g. a n i l i n e . A f t e r f i l t e r i n g from the s l i g h t p r e c i p i t a t e , the s o l u t i o n was decomposed w i t h carbon d i o x i d e . The crude may be c r y s t a l l i z e d from g l a c i a l a c e t i c a c i d . (a) P r e p a r a t i o n of the amine from the above. Borsche 1s method of reduction i n aqueous, hot a l k a l i n e s o l u t i o n with, sodium hyposulphite (RagSgQ^.) was discarded as being both too l a b o r i o u s , i n v o l v i n g the preparation of EaoSgO^, and too slow, quite l o n g heating being necessary f o r complete d e c o l o r i z a t i o n . In i t s place the usual reduction method f o r s i m i l a r azo compounds was used, z i n c dust and g l a c i a l a c e t i c a c i d on the hot a l c o h o l i c s o l u t i o n of the azo compound. This afforded a quick, e f f i c i e n t method of prepa-r a t i o n of the amine hydrochloride,: 40 g. of the crude benzeneazooxy-diphenyl were d i s s o l v e d by h e a t i n g i n about 800 cc. Of 95$ a l c o h o l , and about 20 g, of z i n c dust added to the f i l t e r e d s o l u t i o n . While the mix-ture was being r e f l u x e d , 25 cc. of g l a c i a l a c e t i c a c i d were added slowly through the condenser. A f t e r a short time, a heavy white p r e c i p i t a t e appeared, whioh r a p i d l y increased u n t i l the m a t e r i a l w i t h i n the f l a s k was almost a s o l i d , some-what l i k e a s t i f f J e l l y . I f , a f t e r extended heating, the mixture d i d not become.'pure white, a small amount more of z i n c and a c e t i c a c i d was added and the whole r e f l u x e d again 21. • to d e c o l o r i z a t i o n . 'When t h i s r e s u l t was obtained, the whole r e a c t i o n mixture was t r a n s f e r r e d to a beaker, cooled r a p i d l y ft p prevent o x i d a t i o n and r e s i n i f i c a t i o n ) , f i l t e r e d , and washed w i t h c o l d a l c o h o l , This removed the a n i l i n e by-product. The residue was l a r g e l y z i n c acetate and the amino oxy-d i p h e n y l , and because of t h e i r s i m i l a r s o l u b i l i t y curves i n a l c o h o l could not be p u r i f i e d from that medium. E x t r a c t i o n w i t h benzene y i e l d e d a f a i r l y pure product but was extremely t e d i o u s , due to the low s o l u b i l i t y of the product i n benzene. The method found to give best r e s u l t s was to d i s s o l v e the p a r t l y d r i e d product i n excess h y d r o c h l o r i c a c i d and c r y s t a l -l i z e out the h y d r o c h l o r i d e , the ZnCl remaining i n s o l u t i o n . By u s i n g a small amount of solvent the y i e l d approaches the t h e o r e t i c a l but i s quite impure. By u s i n g a t o t a l volume of about 200 cc. ( f o r the above run) and a d j u s t i n g the HC1 concentration to give a good y i e l d of c r y s t a l s i n a cooled t e s t p o r t i o n , a y i e l d of 2.9 g, of w e l l c r y s t a l l i z e d , only s l i g h t l y colored needles of m e l t i n g p o i n t 214°- 216° G was obtained. The t h e o r e t i c a l y i e l d on the b a s i s of the benzene-azooxy-diphenyl used i s about 53 g. I f the pure amino com-pound was d e s i r e d , the aqueous s o l u t i o n of the hydrochloride so obtained was decomposed wi t h HagGOg s o l u t i o n , the r e s u l -t ant white p r e c i p i t a t e , a f t e r being c r y s t a l l i z e d from a l c o h o l , g i v i n g a m e l t i n g point of 20rc.(corr.) (Borsche gives 201° as the m e l t i n g p o i n t of pure 5-amino.-2-oxy-diphenyl). (b) D i a z o t i z a t i o n and. conversion to the iodo d e r i v a t i v e . In the work done on the preparation of t h i s compound the notes of Neumann (A. 241, 70 - 74) on the preparation of iodo phenols were found of the utmost value. In the i n i t i a l attempts d i a z o t i z a t i o n of a s o l u t i o n of the amino compound i n an excess of 'HOI was attempted. This g e n e r a l l y r e s u l t e d i n much t a r formation. When the s o l u t i o n of KI was added, a yellow p r e c i p i t a t e was noted, which on warming to l e s s than 50°0 r a p i d l y darkened w i t h some gas e v o l u t i o n . A black spongy t a r was formed which continued to evolve gas w i t h i n i t s e l f f o r some days. A f t e r ending t h i s r e a c t i o n by more heat (to about 80" G), the t a r was taken up i n NaOH s o l u t i o n , r e p r e c i p i t a t e d w i t h HG1, and taken up i n ether. On vacuum d i s t i l l a t i o n , some c l e a r o i l passed over at 190° -200° 0„ Another run was d i s t i l l e d with super-heated steam i n s t e a d of i n a vacuum, and y i e l d e d an o i l which, on conver-s i o n t o the a c e t y l d e r i v a t i v e , gave a melting point of 82 P0 (see l a t e r ) . The second attempts were patterned more c l o s e l y a f t e r Neumann's procedure (A. 241, 70). F i r s t 3.1 g. NaNOg i n 50 cc. of H 20(T <- 5° G) , then 7.5 KI i n 50 cc. % 0 were added slowly to a s o l u t i o n of 10 g. amino oxydiphenyl hydrochloride i n 150 cc. of H 20(T < 5° G). A yellow f l o c c u l e n t p r e c i p i t a t e of the diazo compound formed. The r e a c t i o n mixture was then decomposed by the gradual a d d i t i o n of 8.75 g. of the usual concentrated HG1 (about 36 - 37$). No t a r was formed. A very slow gas e v o l u t i o n was observed. On standing over night at room temperature, the yellow p r e c i p i t a t e turned green and darkened s l o w l y w i t h gradual gas e v o l u t i o n , hastened by mild warming. From 35° to 50° the s o l i d g r a d u a l l y changed to a black, tumescent t a r , which continued to evolve gas w i t h i n i t s e l f f o r some time. A f t e r d i s s o l v i n g the t a r i n d i l u t e BaOH s o l u t i o n c o n t a i n i n g some s u l p h i t e , i t was p r e c i p i t a t e d w i t h d i l u t e HC1 and extracted w i t h CHClg. By vacuum d i s t i l -l a t i o n , 5 g. of a product b o i l i n g at £00°- 205 (10 mm.) were obtained, somewhat d i s c o l o r e d w i t h i o d i n e . By u n i t i n g the y i e l d s from seve r a l runs and r e d i s t i l l i n g , a f a i r l y l i g h t colored o i l was obtained 'which did not s o l i d i f y on long standing at low temperatures.. Because of t h i s supercooling c h a r a c t e r i s t i c of the product, i t was converted to the a c e t y l d e r i v a t i v e as f o l l o w s : 7 g, of the o i l were r e f l u x e d 2 hours wi t h 20 g. a c e t i c anhydride and 2 g. sodium acetate. A f t e r c o o l i n g , the product was taken up i n ether and washed a l t e r n a t e l y w i t h cold HgO and 5'p EaOH s o l u t i o n u n t i l the wash water showed an a l k a l i n e r e a c t i o n . A f t e r washing once more w i t h water the s o l u t i o n was evaporated on the water bath. The r e s u l t a n t o i l , on standing i n the i c e chest, c r y s t a l l i z e d from several centres, G r y s t a l -l i z a t i o n may be hastened by the use of seed c r y s t a l s . The y i e l d was 7 g. By c r y s t a l l i z i n g twice from l i g r o i n (B.P. 90°-105° ), white c r y s t a l s of M.P. 82° G (corr.) were obtained, which gave the f o l l o w i n g r e s u l t s when analyzed f o r iodine by the 24. method of Garius: Wt, sample Wt. A g l Percent iodine .1552 g. .1068 g. 37.68$ .2558 .1646 57.73 The value c a l c u l a t e d f o r 0 6H 5G 6H 3IO0OGH 3 i s 37.57$ i o d i n e . As a f i n a l t e s t of the i d e n t i t y of the substance w i t h that obtained by Mr. l i v e n by an e n t i r e l y d i f f e r e n t procedure, the m e l t i n g p o i n t of a mixture of the two was taken. I t proved u n a l t e r e d , i . e . , 82° 0. In an e f f o r t to improve the y i e l d , the dry diazo c h l o r i d e was i s o l a t e d as below; I am indebted to Neumann ( i b i d . ) f o r a d e s c r i p t i o n of the method as ap p l i e d to iodophenols. 20 g. of crude amino hydrochloride were d i s s o l v e d i n a l i t t l e absolute a l c o h o l , cooled w i t h i c e water, and 10 g. of e t h y l n i t r i t e were allowed to evaporate i n t o the s o l u t i o n . A heavy p r e c i p i t a t e formed when the r e a c t i o n was w e l l under way. When a l l the n i t r i t e had passed over, much anhydrous ether was added. The f i l t e r e d product, washed w i t h ether, formed a pale grey-green powder of melt i n g point about 107 G. w i t h decomposition. A y i e l d of 20 g. was obtained, the theo-r e t i c a l being 21 g. The above obtained 20 g. of diazo c h l o r i d e were added to about 150 cc. of c o l d water. L i t t l e s o l u t i o n ensued, From 11 a burette 33 cc. of h y d r i o d i c a c i d ( c o n t a i n i n g 4 0 0 0 — equi-v a l e n t s per cc.) were added. No r e a c t i o n was n o t i c e d u n t i l the mixture was warmed, when the r e a c t i o n ran e x a c t l y the same course as when the diazo c h l o r i d e was not f i r s t i s o l a t e d . A b e t t e r y i e l d was obtained, however, there being 18 g. of t a r e x t r a c t e d , 3, P r e p a r a t i o n of sodium orthophenylphenate. In p r e paring t h i s s a l t i n the dry s t a t e , the procedure given i n B e i l s t e i n ' s Handbuch f o r the p r e p a r a t i o n of sodium phenolate was f o l l o w e d . One mol of sodium was d i s s o l v e d i n absolute a l c o h o l and added to a s o l u t i o n of one mol o-oxydiphenyl i n absolute a l c o h o l . The r e a c t i o n mixture was evaporated i n a stream of hydrogen, and the crude product c r y s t a l l i s e d from acetone. The c r y s t a l s so formed could not be d r i e d by warming, as they charred i n a very short time, even at 50B G. i n an evacuated d e s i c c a t o r . Dried at room temperature i n a vacuum, the product was analyzed by t i t r a t i o n of the aqueous s o l u t i o n w i t h standard HC1, u s i n g phenolphthalein as i n d i c a t o r . Values obtained f o l l o w : Wt. sample V o l . HGlf.1123 n.) Peroent l a .5995 g. 21.4 cc. 9.22 % .5992 21.3 9.18 The c a l c u l a t e d value f o r GsHgGgH^OHa i s 11.98% f o r GgHgGgH^OHa*(CH3)2C0, 9.20%. Hence the product i s obviously the sodium s a l t c r y s t a l l i z e d w i t h one molecule of acetone. £6. Synopsis of R e s u l t s . 1. P r e p a r a t i o n of benzyl cinnamate from benzyl a l c o h o l and cinnamoyl c h l o r i d e (method not given i n l i t e r a t u r e ) . E. P r e p a r a t i o n of the new compound m-iodo-cinnamoyl c h l o r i d e - p r o p e r t i e s , a n a l y s i s. 5. A c o r r e c t e d melting p o i n t f o r m-iodo cinnamic a c i d (191,5" G. i n s t e a d of 181° G, w i t h decomposition as given by G a b r i e l , Herzberg, B, 16, £037). 4. P r e p a r a t i o n of the new compound benzyl m-iodo cinnamate-properties^ a n a l y s i s . 5. P r e p a r a t i o n of m-iodo benzyl a l c o h o l from m-iodo benzaldehyde (method not a p p l i e d b e f o r e ) , 6. P r e p a r a t i o n of the new compound m-iodo benzyl cinnamate-properties, a n a l y s i s . 7. P r e p a r a t i o n of e t h y l m-iodo cinnamate (see previous paper f o r b a c h e l o r 1 s degree, 193S) by condensation of m-iodo benzaldehyde w i t h e t h y l acetate by means of sodium; subse-quent s a p o n i f i c a t i o n of the e s t e r to the a c i d . 8. P r e p a r a t i o n of 5-amino-2-oxydiphenyl by reduction of the benzeneazo compound wi t h z i n c and a c e t i c a c i d (method not given i n l i t e r a t u r e ) . 9. P r e p a r a t i o n of the new compound 5-iodo-E-oxydiphenyl -p r o p e r t i e s . 10. P r e p a r a t i o n from the above of the new compound 5-iodo-E-acetoxydiphenyl - p r o p e r t i e s , a n a l y s i s , i d e n t i f i c a t i o n w i t h 27. the product obtained by Mr. Eive n ( t h e s i s f o r bachelor's degree, 1934). 11. P r e p a r a t i o n of the new compound CgH gG„H 4OF a.(CE3)2GO. A n a l y s i s . Some negative r e s u l t s were obtained, such as the r e a c t i o n between benzyl acetate and benzaldehyde induced by sodium, and the r e a c t i o n between phenol and p-iodo benzene diazo c h l o r i d e . These r e a c t i o n s , while not g i v i n g the des i r e d compounds, y i e l d e d products which i t was not p o s s i b l e to i n v e s t i g a t e f u r t h e r , on account of l a c k of time. /VoU: All jo Vizte.c( etS i -h H>e//spin's H$(r\<s( budj S-5 c / e 7 1 GcstJ/s elicit,1 

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