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The preparation of the four-mono-brom-normal-valeric acids Johnston, Frederick Blaney 1928

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jU.B.C. *CC. HO. THE PREPARATION of the FOUR-MONO-BROM-NORMAL-VALERIC ACIDS.  BY  FREDERICK BLANEY JOHNSTON*  A T h e s i s submitted f o r the Degree of MASTER OF ARTS in the DEPARTMENT OF CHEMISTHY.  THE UNIVERSITY OF BRITISH COLUMBIA. APRIL, 1928.  LIBRARY  TABLE OF IMTPODUCT IO:T. Discussion  '•£ s:> .e of  r» •<r - . ii-io ;-;»Li:ir of •ne thod 2 f i.o.a  . t ^V-l* '.) :>ds •  . 31 i;  Uu? f'-ur ao-io-bro;:-n-valeric a c i d s , a-vl  u ssd . SXP^HXT^TTAL.  A. B.  The i^lcin^; of oC-brom-a-valftric -brom-n-valeric  acid.  C.  T-bro;t>-n-va 1 er-ic a c i d .  D.  5-broa-n-valeric  S.  °oLi.  acid.  An attempt t o make a -brom-proprionic a c i d ,  r-iv? l i v e s 1 1  3ation of the p r o p e r t i e s of the compound obtained.  THE PREPARATION OF THE FOUR MONO-BROM-NORMAL VALERIC ACIDS* INTRODUCTION. In c e r t a i n work undertaken in t h i s l a b o r a t o r y the f o u r mono-brom d e r i v a t i v e s of normal v a l e r i c acid were r e q u i r e d , t h a t i s - theory*?, v ,  and S compounds. Only one of t h e s e ,  the  ex-compound, could be bought. T h e r e f o r e the p r e p a r a t i o n of the other t h r e e was undertaken h e r e . Search in the l i t e r a t u r e y i e l d e d a s u i t a b l e method f o r but one o f these t h r e e , t h e V - a c i d . For the o t h e r two,  the  methods g i v e n were not p r a c t i c a b l e f o r the amount of the a c i d s needed f o r the f u r t h e r work. For the sake of completeness i n t h i s r e s e a r c h ,  some o f  t h e e * - a c i d was a l s o p r e p a r e d . Analagous cases of the d i r e c t 1 ^ bromination of n o r m a l - b u t y r i c acid and i s o - v a l e r i c a c i d " t o g i v « the corresponding <X-acids suggested a s i m i l a r procedure i n the case of the n o r m a l - v a l e r i c a c i d . Ixperiment  confirmed  t h i s . A second method was suggested by the common method of using red phosphorus and bromine^ i n the making of t h i s  class  of compounds. T h i s was a l s o confirmed by experiment, and l a t e r h  much the same method was found in a r e c e n t paper . Theytf-acid presented a d i f f i c u l t problem, and f i n a l l y a combination of former methods had t o be used. The e s t e r of the c(-acid  was made i n t o the unsaturated  ya "pent en''-acidS and on  t r e a t i n g t h i s with hydro-bromlc a c i d the/tf-brom v a l e r i c was  obtained® An attempt t o make the « - b r o m - v a l e r i c e a t e r from the corresponding acid by the s i l v e r s a l t method of making e s t e r s was not v e r y s u c c e s s f u l . The Y - a c i d was made according t o a procedure given in the l i t e r a t u r e ' ' ^ . This was, in b r i e f , theformation of  allyl-acetic  acid and the a d d i t i o n of hydrogen bromide t o t h i s t o y i e l d the Q required v a l e r i c acid . A comparison of two ways of making the a l l y l - a c e t i c acid was made, and some s l i g h t improvements made in the procedures. A small quantity of the v a l e r i c acid was a l s o made from Y - v a l e r o - l a c t o n e The methods g i v e n f o r the making of S - b r o m - n - v a l e r i c acid were t o o c o s t l y t o a l l o w the preparation of any considerable amount of the a c i d . The f i r s t p o s s i b l e method that  suggested  i t s e l f was t o make one bromine only of the symmetrical 1-4 d i brom-butane undergo a G-rlgnard's r e a c t i o n . From t h i s  last-  named compound have been made a d i p l c and sebacic acids by the use of s u f f i c i e n t magnesium t o form the metal complex with both ends of the compound 11 . Since 1-4 dlbrom-butane could not be obtained a s t a r t was made l a s t year in i t s manufacture.  It  was hoped, by F i t t i g ' s r e a c t i o n , adding one mole of sodium t o two molecular weights of ethelyne blbromide, t o obtain the d e s i r e d compound. Repeated experimenting gave no r e s u l t s . Next was attempted the making of the same compound s t a r t i n g with 12 butadiene, which was t o be made from ethelyne and a c e t y l e n e . '13 i4 1-4 dibrom-butadlen had p r e v i o u s l y Seen made from butadien I t seemed quite probable that t h i s compound could be reduced t o the corresponding 1-4 dibrom-butane. The d e s c r i p t i o n  for  the manufacture of butadiene along the proposed l i n e s  being  v e r y meagre, i t was soon found that t o o long a time would be p  required f o r the study of proper c o n d i t i o n s ,  so that attemf,  was dropped. The l a c t o n e being used o f t e n in the making of  brom-acids  by a d d i t i o n of hydrogen bromide, i t was decided t o use S - v a l e r o lactone in the formation of the 5 - a c i d ^ ° The r e q u i r e d l a c t o n e was made by the a c e t o - a c e t i c e s t e r synthesis from 3 - c h l o r - a propyl a l c o h o l . Treatment of t h i s with concentrated hydrogen bromide s o l u t i o n y i e l d e d the S - a c i d . As a matter of i n t e r e s t , a n attempt t o makey^-brom-proprion i c acid from ethylene dlbromide was made, t h i s being analagous with the procedure t r i e d in the case of S - b r o m - v a l e r i c  acid.  EXPERIMENTAL«  A. of-brom-n-valerlc  Acid.  As a l r e a d y s t a t e d i n the i n t r o d u c t i o n , oc-brom-butyric acid has been prepared by the d i r e c t broicination of  n-butyric  acid? One m o l e c u l a r weight of the a c i d was sealed up i n a g l a s s tube w i t h one molecular weight of bromine. The tube was then h e a t e d . The products of the r e a c t i o n were oc-brom-\'aleric  acid  and hydrogen bromide. 10 grams of n - v a l e r l c a c i d were sealed ?/ith 16 grams of bromine In a t u b e . The tube was heated i n a furnace f o r hours at II0°C. The tube, a f t e r c o o l i n g ,  was c a r e f u l l y  several opened,  since a c o n s i d e r a b l e volume of gas v/ould be formed by the reactionC H j C H 2 C H 2 C H 2 C O O H + Br2  CH^CHOCI^CHBrCOOH +• H B R .  The bromine remaining was e x p e l l e d by h e a t i n g and the a c i d s f r a c t i o n a t e d . Some unchanged n - v a l e r i c a c i d was r e c o v e r e d , a small amount of * - b r o n a u a - v a l e r i c a c i d , b o i l i n g - p o i n t  and  -about  135° at 30 mm. p r e s s u r e .  oC-brom-n-butyrlc acid has been prepared by the a c t i o n bromine on the n - a c l d in the presence of red phosphorus, and the subsequent h y d r o l y s i s of the ot-brom-n-buteryl bromide so formed w i t h the exact amount of water r e q u i r e d ? 10 grams o f n - v a l e r i c a c i d were p l a c e d in a f l a s k p r o v i d e d w i t h a r e f l u x condenser. 2 grams of phosphorus were added and then bromine, g r a d u a l l y , u n t i l f i n a l l y the mixture  of  remained reddish in colour on he?.ting, Th.; jhos h-srus xxybromide formed was f i l t e r e d o f f and j u s t enough water P i l e d decompose the c < - b r o m ~ n - v a l e r y l  to  bromide. The mixture was then  b o i l e d f c r a few minutes. A f t e r drying over concentrated sulpnuric acid and s o l i d pots .-slum hydroxide in d e s s l c a t o r s , the o i l was f r a c t i o n a t e d , and as before a small amount of both the o r i g i n a l acid and oC-brom-n-valeric acid was obtained. 4 The method l a t e r found , which corresponds v e r y with t h i s l a s t ,  is, briefly,  closely  as f o l l o w s . The n - v a l e r i c acid Is  bromlnated, as b e f o r e , in the presence of red phosphorus. Tne mixture i s poured i n t o e t h y l a l c o h o l and the e s t e r of the bromacid i s formed. B. ^?-brom-n-valeric  Acid.  No method could be worked out which would be b e t t e r than those already in the l i t e r a t u r e f o r the preparation of the ^ - a c i d . Therefore,  since t h e o c - a c i d was e a s i l y procurable,  was decided t o t r y t o make t h i s i n t o the c o r r e s p o n d i n g *  it acid  with a l c o h o l i c potassium hydroxide, and then, by treatment of t h i s unsaturated acid with hydrogen bromide s o l u t i o n , t o get theytf-brom-valeric a c i d . However, I t was not known whether the potassium s a l t of the ex-brom-acid would r e a d i l y  split  off  hydrogen bromide, so that t h i s method was g i v e n up f o r one r" already t r i e d out elsewhere? In t h i s one, c( - b r o m - n - v a l e r i c e s t e r was r e f l u x e d with q u i n o l i n e , when the e s t e r of the required unsaturated acid was obtained. A c c o r d i n g l y ,  some of  t h i s acid was so prepared by t h i s method and subsequent  s a p o n i f i c a t i o n v'lth potassium hydroxide  gri £  a c i d i f i c a t i o n with  sulphuric a c i d . A f t e r e x t r a c t i o n and p u r i f i c a t i o n , the acid was shaken f o r s e v e r a l days with hydrogen bromide s o l u t i o n at CTC.  saturated  Une l a y e r f i n a l l y r e s u l t e d from which the /?-brom acid  formed was recovered by d i l u t i n g the s o l u t i o n . The acid was e x t r a c t e d with ether and d r i e d as was the o<-compound. An attempt t o make the « - b r o m - v a l e r i c e s t e r required by the s i l v e r s a l t method ?/as not so s u c c e s s f u l as t h i s i s said t o be. To 25 grams of acid was added a water s o l u t i o n of 43 grains of s i l v e r n i t r a t e . The s i l v e r s a l t was f i l t e r e d o f f and d r i e d . I t was then r e f l u x e d with 50 grams of e t h y l i o d i d e , but the y i e l d o f the a - e s t e r was v e r y poor. The method was t h e r e f o r e discarded f o r the one d e s c r i b e d immediately b e f o r e t h i s . ( N o t e : - This acid was made by Mr. Guy Haddington.) C. y-brom-n-valeric  Acid.  A f t e r c o n s i d e r a t i o n of methods which presented themselves and of such as were found in the l i t e r a t u r e ,  i t was decided  to  make the Y - a c i d by a method already w e l l - t r i e d . By the malonic e s t e r synthesis a l l y l bromide was converted t o  allyl-acetic  acid , and t h i s t r e a t e d with hydrogen bromide y i e l d e d the Y - a c i d . 23 grams of sodium metal were d i s s o l v e d in 300 grams of absolute e t h y l a l c o h o l , d i s t i l l e d  over l i m e . Through a r e f l u x  water condenser was added j u s t one mole ( 1 6 0 grams) of malonic e s t e r . A pasty, white mass was produced. ^COOSt XOOEt NaO&t + CHp • NaHC + EtOH. >xGOOEt COQEt  7  S l i g h t l y more than the calculated amount (120 grams) of  ailyl  bromide was then added. The r e a c t i o n wa3 accompanied by the e v o l u t i o n of considerable  heat.  CK2=CH-CH2Br + NaHC(COOEt)2 * CH2»CH-CH2-CH(COOEt)2 J k v H . The r e a c t i o n mixture was then heated a short time on the steam bath, r e f l u x i n g , and i t vms found t o be n e u t r a l . The excess a l l y l bromide and the a l c o h o l were d i s t i l l e d bath. ( I f  o f f on the steam  a l l the a l c o h o l was not removed here, i t  d i f f i c u l t y in the drying of the e s t e r l a t e r . )  caused  S u f f i c i e n t water  was added t o d i s s o l v e the sodium bromide, and the e s t e r was extracted with e t h e r . The e t h e r e a l solution was d r i e d , ether d i s t i l l e d  the  o f f , and the e s t e r f r a c t i o & a t e d , the p o r t i o n  b o i l i n g from 218-225° being r e t a i n e d . ( Y i e l d - 7 0 ^  theoretical).  The e s t e r was t r e a t e d with twice the t h e o r e t i c a l amount of concentrated potassium hydroxide s o l u t i o n ( 1 . 2 gram a l k a l i t o I gram of water). A f t e r two hours heating on the steam-bath, the e s t e r was completely  saponified.  CH 2 «CH-CH 2 -CH(COOEt) 2 +2K0H  CH2=CH-CH2-CH(CoOE ) 2 +2 EtOH  Here a departure was made from the method of the l i t e r a t u r e in that a step was l o f t out. P r e c i p i t a t i o n of barium a l l y l malonate, a3 advised, caused t r o u b l e , as the barium hydroxide also formed caused much t r o u b l e . So the a l k a l i solution was n e u t r a l i z e d with the calculated amount of sulphuric a c i d . C5H5-CH(C00I)2 + H2S04 * C3H5-CH(GOOH)2  K0SO4.  Since a l l y l - m a l o n l c Acid i s soluble in water, the solution was extracted upwards of ten times. Even with t h i s , . t h e amount of acid obtained was only 20$ of the amount calculated from the  o  •J *  e s t e r used. The acid was d r i e d over potassium hydroxide r e o r y s t a i l i z a t i o n from e t h e r . M e l t i n g - p o i n t  after  of c r y s t a l s - 103°C.  The a l l y l - m a l o n l c acid v.-a a then heated on an o i l - b a t h t o 130°, o r , as was found e q u a l l y s a t i s f a c t o r y , with a small flame, thermometer in the l i q u i d , u n t i l no more gas was generated. F i n a l l y the l i q u i d was f r a c t i o n a t e d , the f r a c t i o n between l32° & 134° being c o l l e c t e d  C3H5-CH(COOH)2  separately,  - this  is a l l y l - a c e t i c  acid.  C3H5-CH0COOH + C0 2 .  A s o l u t i o n of hydrogen bromide,  saturated at O^C, was  prepared. Two volumes of t h i s were shaken f o r s e v e r a l days with one volume of a l l y l - a c e t i c  a c i d . Gradually the two merge i n t o  one. CH2rCH-CH2-CH2-COOH + HBr  CH3-CHBr-CH2-CH2-CU0H.  V  The Y - b r o m - v a l e r i c acid was obtained by d i l a t i n g the  solution  and e x t r a c t i n g with e t h e r . The ether being d i s t i l l e d o f f ,  the  acid was washed with water, and dried over concentrated sulphuric a c i d . On standing, the acid became q u i t e black, but t h i s colour can be removed with animal charcoal. Tnen tbe f r a c t i o n a t i o n of the acid was attempted,  i t was found that  this  could not be e f f e c t e d , even at 30 mm. pressure. In spite of  all  precautions, the 11 qui? burvpei. A very f i n e j e t of a i r was introduced beneath the surface of the l i q u i d by means of a c a p i l l a r y tube, and g l a s s Ss were a l s o used, but t o no purpose. Since 110 b o i l i n g - p o i n t  i s given in the l i t e r a t u r e ,  t h i s same  d i f f i c u l t yV has orobablv V been encountrerl b e f o r e . In g e n e r a l , the malonic e s t e r synthesis g i v e s a b e t t e r y i e l d than does the a c e t o - a c e t i c synthesis, but recent work has  given  -us  „.• • f'drl  ^i'.'.-J  r l c X"  v.-ry  - - b. iJ.  yi=?ld r,  J •.-•.•.  . Tit.; e >oli-g,  3 "•  i  •! . \j  .1j i ".2.r  ha:  •-•.«>  . ,-r  n  jn • !  i  • ,. • , _ 0 . : ^ •. •  -,-.  • „ ."! ... ** - ^ . • -i'v £ .» 'J.T'.t 3 1- ->\" ± ,  /COCH-r T.TpO^:-'; + GH0 ^ COO'S'  ^COCHNr-.CH ' +E "^COOEt  OH.  T h r - u g i P. r. f l •:: '..--^r •:•: > •ere  ad ^  ~0  .->? a i ; y l • r x i i d .  sl>oly.  /COCHCHo«CH-CHo3r + MaCH ' v COOEt  x COCH-  CH0«CH~CKg-CH " + -Te.3r. v COOEt  The m i x t u r e -p.s theo r e "luxe 1 Mat51 it. reaction.-The  alcohol  wss added t o d i s s o l v e and the a l l y ! '.he e t h e r e a l  the  extract  off  -ed i o the : -voti-  e s t e r extract':-'  v l •' h - t h e r .  Af t e r  ha 1 besn dri-.d w i t h anhydrous pota.ee-lee.:.  t h e e t h e r wa a - l i s M i l e '  The  -1  on a s t r am-ba.f h,  sodl^e 1 ro  ace t o - a c e t i c  acid carbonate, fractionated.  -j?3 i i s t i l l e - . ;  o *>  ;.orti^n V d i i n ;  c o l l e c t e d , b e i n g a.l -.ost pare The p r o c e d u r e n e x t  h. t.„ ,  -it:v.  fol" 1 >w-  the 200° an.?  Y i > -1 il -  s t er-  213C.  70".  in the l i t . f u t u r e was to  r e f l u x the e s t e r w i t h 3-4 t i r . . ?  the t h e o r e t i c a l poount  potassium hydroxide J.  oat- r . Tn • s v.?.. t r i e d and ht  in a l U M - .  • ielde-"* no aid!1 1 ace t i c  a c i d -/hen tne  -ed,  of  but only a. m i x t u r e  tried  a modification  hydroxide  In I S grama o f  The a l l y l  when the t o o l a y e r  acet^-aCctic  of e s t e r  s f .irtoer  treat  u d e s i r e d products-. l T ext  t u i s method. AO rirams of  ./ere d i s s o l v e d  _ .r-3 r e s u l t i n g . oally,  of  other,  el;. tor.-  of  potassium  alcohol, vster  ws  two  ^dd1'd  and alcohol. i l " v ; l y  rrad-  dissolved  COCHC-Hr-GpT + 2K0H + CrHr-GOOK + CH.-COOK + St OH. gooe^ " Tui-. r e a c t i o n  . •-.£ j"fUxtd int.) 250 o . c . of v/^itr and the  vviioie ei'.t : net': 1 ,;ith eth-.r t0 ro .ore .®ri7 i-l - J ^ i—V I - t » for-. e  acetone  i.'i.n + •-• 1 -L - --v. "'•  en* unchanged est*: r . The aeneous solution ••v3  a c i d i f i e d '-.-it.:; sulphuric ^ - i d a>-d thf-. a l l y l e x t r a c ' : : v,r' t • e.thvr. a e l i was d r i e d and t r e a t s  calculate"  a c t ! then Wit e c t e r used, tic  as in the previous method.  Since i t had teen decided to use one of the methods of the l i t e r a t u r e t o maice the Y-brom-val< r i c a c i d , an attemot was made to obtain i t through the use of the Y - l a c t o n e . A b r i e f TO summary of the combination of various procedures synthesis  in  this  follows:-  100 grams of cane-sugar were heated f o r twenty-four hours with 500c.c. of 1:4 h y d r o c h l o r i c acid on a stean-bath.  Phe  mixture was f i l t e r e d and 35 grams of sodium hydroxide added g r a d u a l l y . The whole v/«s then evaporated " i n vacuo" to IOOc.c. and the sodium c h l o r i d e which s- parated out f i l t e r e d o f f . The l a e v u l i n i c acid vms e ;tr acted with ether and f r a c t i o n a t e d - ' H . P . - I 4 0 ° - I 7 0 ° at 15-30 mm. 34 grams of ?c1.d were d i s s o l v e d in 12 grams of sodium hydroxide in 100 c . e . of 95,% e t h y l a l c o h o l ,  in a f l a s k with a '  r e f l u x condenser attached. During an hour, 13.3 grams of sodium metal in f i n e s l i c e s were introduced into the mixture with continual s t i t r i n g . A f t e r a l l the sodium had been added, 30 c . e .  TT .  :>f the a l c o h o l  12otilled  o f f . Trie r e s i d u e wss t r e a t e d r i ' . h  25c. o. of ivaier t o dec oncost the so-:!' ul.  thy l a t e  r e a c t i o n and the a l c o h o l x-. s u i t i n g removed After cooling, of d i l u t e  : 'y  formed in th<  distillation.  the f i x t u r e r e g a i n i n g ••?.?.3 a c i d i f i - d w'.th 7 . tc:.c  sulphuric a c i d . The y e l l o w o i l  f l o a ' ivi; on two was  removed, the aqueous s o l .it ion n e u t r a l i s e d w i t h sodium carbonate and e x t r a c t e d r e p e a t e d l y w i t h e t h e r . The o i l f r a c t i o n a t e d and the l a c t o n e ,  obtained was  " . P . - .11*3-13^° at 60mm.,  collected.  On h e a t i n g t h i s l a c t o n e w i t h saturated hydrobromic a c i d in a sealed tube at 100°C, the Y - b r o r ; - n - v a l e r i c The y i e l d s a l l  through were v e r y  a c i d v;as o b t a i n e d .  poor.  D. **  8-broa-n-valeric As has a l r e a d y been s t a t e d ,  S-acid  it  Acid. via<3 hoped t o make the  f r o n 1:4 dibrombutane. however, no method could be  e v o l v e d which would v i e l d s u f f i c i e n t of t h i s l a s t  com-oound f o r  the purpose in v i e w . Theoretically, t o be by F l t t i g ' s  the e a s i e s t way of making the butane seesaed  reaction,  Br-gH?-CHc.-^r A number of t r i a l s ,  2TTa  according t o the  3ri-CHo-CK?-Br  equation-  Br-l GH2)4-Br + 2Na3r.  made under v a r y i n g c o n d i t i o n s of  temperature  and d i l u t i o n gave no r e s u l t s . The use of metyl cyanide as a c c a t a l vv s t d i d no /rood, i t mav / v be that the l a c k of results  expected  i s accounted f o r by B i s c h o f f ' s "Dynamic H y p o t h e s i s " .  A second p o s s i b l e way of making i : 4 dibrombutane i s the reduction of dibrombutadien. This l a s t compound had already  been made by what seemed a simple method, so an attempt was TO  made to r e d u p l i c a t e the experiment. Ethylene was prepared by passing e t h y l a l c o h o l vapours over anhydrous aluminium sulphate, contained in a combustiontube heated t o 350°C.IThis procedure g i v e s about 99% y i e l d of e t hV y l e n e . Acetylene was male from calcium c a r b i d e . Any V V arunonia present in i t was removed by bubbling i t through water, i t was then f r e e d from any hydrogen phosphides by passing through a suspension of calcium h y p o c h l o r i t e  in water. At t h i s p o i n t ,  the  ethylene and acetylene were mixed by bubbling them i n t o a f l a s k containing more water, thus a l l o w i n g the admixture of the gases in equal volumes. The mixed gases then passed over granular calcium oxide in a tube i n t o a p o r c e l a i n  combustion-  tube heated t o 500°-600°C which was f u l l of fragments of pumice-stone. The o u t f l o w i n g gases were cooled in a s p i r a l condenser In a f r e e z i n g mixture ( - 2 0 ° C ) . A small y i e l d of butadien, 3 . P . - -5°C, was obtained, but not s u f f i c i e n t t o be of use. For lack of time the attempt was abandoned. The method f i n a l l y used f o r the S - a c l d was the treatment of the 5 - l a c t o n e with assaturated solution of hydrobromic  acid.  The l a c t o n e was made from 3 - c h l o r - n - p r o p y l a l c o h o l by both the malonic e s t e r and aceto-acet-ic e s t e r  syntheses.  The required chlor-propanol was made by a method which proved q u i t e s a t i s f a c t o r y 1 ^ . R e d i s t i l l e d trimethylene  glycol  was saturated in the cold with dry h y d r o c h l o r i c acid gas. The increase in volume amounted t o about one-fourth of the  original  volume of the l i q u i d . At f i r s t the mixture was sealed In -tubes  13.  th--n --.ated '»n a steam-bath, '. ui i a t t r so l i t t l e  I t was ?rw.i t;.»*t  pressure was developed that ordinary r~agc.it botti--s  with, rubber corks wire-J. irt "'ere q u i t e strong enough. The heating was continued f o r X'our hours, the containing v e s s e l cooled and opened. The l i q u i d , ated with hydrogen c h l o r i d e , hours l o n g e r .  now v i s c o u s , was agMn satur-  and heated as N-'.'ore f o r two  I t was then d i s t i l l e d . There was a great  v.Un ;  towards bumping, even with g l a s s beads. This was best r<•;;>:••?.led by g e n t l y tapping the 3ide of the f r a c t l o n a t l n g - f l a s k  until  a l l the hydrogen c h l o r i d e had cone o f f , when the bumping ceased. The f r a c t i o n b o i l i n g from I 6 0 ° - I 6 2 ° was c o l l e c t e d , being the c h l o r - p r o p y l  alcohol.  The procedure from here on was,in both the malonic  ester  and the a c e t o - a c e t l c e s t e r syntheses, e x a c t l y the same as that f o l l o w e d in the making of the Y - a c i d , the chlor-prooanol being substituted f o r the a l l y l bromide. In n e i t h e r case, a f t e r the a d d i t i o n of the h a l i d e t o the mono-sodium e s t e r , p u r i f i c a t i o n of the r e s u l t i n g compound attempted,  was thesince no  information could be obtained about e i t h e r o f th*m. They were used in the f o l l o w i n g r e a c t i o n s as i f pure and were found t o act f a i r l y w e l l . The f i n a l product of each r e a c t i o n w*s 8-hydr o x y - n - v a l e r i c a c i d . On d i s t i l l a t i o n ,  t h i s y i e l d e d , by  B P. 2/40- 22 0' <xt ico  the l o s s of one molecule of water, 8 - n - v a l e r o - l a c t o n oA. This was heated with saturated hydrobromic acid in a sealed tube t o I45°C. The mixture was d i l u t e d and the S - t r o m - n - v a l e r i c acid e x t r a c t e d with e t h e r . IT.P. of the acid  It.  TP  j3-bro:..-propriooic  Acid.  Iii order t o get an idea as t o bov/ the proposed synthesis of S - t i ' i - v a l e r i c acid f r o n the dibrom-butane n3.ght go, an ttempt ".-as made t o obtainy0-brom-propr3onic a c i d 1:y drignard's reaction  fr >.„ ethylene  d'bromide.  To ?•:• -ran'S of ethylene d i V - y . l i e was aide I thr  in ? 0 0 c . c . of i r -  ether  t e - h a l f mole ~ef magn '.si am, in the for-:;. of r i 'oh on,  a re f l a x condenser. Trhen a l l  the ui-. t a l had d i s s o l v e d ,  the f l a s h v;as put in an i c e - b a t h , and a steam of carbon d i o x i d e bubbled through the l i q u i d . At the end of SO minutes the temperature rose suddenly fro-- 2 ° to I5°C, and a s o l i d  settled  out. The carbon d i o x i d e -jas passed in. u n t i l no more s o l i d precipitated.  The two.- r e a c t i o n s v:ere presumably as f o l l o w s : -  Br-CH2 - C Ho - Br + Jig *  Br-OHo-GIb-hgBr  Br-CH2-CH2-i:gBr + COp + 3r-CH 2 -CH 2 -C00Mg3r. Three times the t h e o r e t i c a l amount of  sulphuric  acid,  c o o l e d , v/as added, since j u s t e x a c t l y the t h e o r e t i c a l amount did hot d i s s o l v e  the s o l i d . 'Tien e x t r a c t i o n of the expected  acid *;/as attempted, three d i s t i n c t l a y e r s of l i q u i d  I  resulted.  The top one consisted of ».• ther plus a s'.uall amount of t thyl-ne d i b r o d.de. The middle lay-..r contained sows e t h e r -*nd a Dure ° l i q u i d which bo3led entir- l y at 73°-73 J G at 8-IOcm. This l i q u i d './as p e r f e c t l y ..ilscible with e t h e r , i t s freezing-point  soluble  ./as -AO 0 , aul b o i l i n g - p o i n t  12 3  water, was 1.73.  1  In /.eater, at 760mm.  I t s d e n s i t y , determined by depression of f r e e z i n g - p o i n t  1  of  O  . „  ....  &> . I .  1 'J  1 »• •  othis  •»-  T V  '•'!••  n  ,< r.Mi. ~>n ' v-V  ' 1 1 ••*>  search. To Dr. K o . e j  De : .si-h,e.)t of Che mist x-y at the U n i v e r s i t y a... indebted f  in formation i- • re j ? r d  1:4 dlbrom-butone,  r  -  i  t  VI ;(•>'•  3, Tie ad of I l l i n o i s ,  *£ the els">, 1  to the man a fa c -ure '<f  as '.veil ^s t o Dr. Johnston,  now ;-it o o r n e l l ,  wno - u n f i l e d me with i n f o r m a t i o n in the same 15-v.;. La oh of Lt  u'rvenled th<- use of t h i s in for:-at ion..  UBC Scanned by UBC Library  j^TjJ-ITTT'pVM QT? C ^ NAUHA'TU. T R I E DEL,  T.!ACLUCA.  o I .ivcj i . s-jrv.  L IE.Hi' T'8 A .pier. A •VU'-.l en 120. P . 233 ° Zi Q A anal en 171, ft: i / -•, ..* T !r^r-y P >*I4.  2.  Annalen 267,i,<.l47.  'T0I *~:ARD. I'lriAZL..  A a al e t 3 .i 2, o . 161. 3o r i c h ,e 7-4 , p. 404" .  5. r." fpE, HO"TI3, LOT 2. 7 ITT  , SP5T! CTK.  • i ' t. A a  ;  - _ ,—•at v. A -  >  •?  ;OrTRAO, 3 I S C H O F ? .  a •.-I.V - i.«-!; n -i •w - J'ta'., •- 1t iu"i Awns A  3. F i T T i ' r , Mb*S5h;-HSCH7IDT. Aon&l* ZSIDL£R. Annalea 9. F I T T A n n a 1 e n  2Oh,p.94.  10.taxLOH, WL03E. SKHUBTTS,SAH. LO'JIS H31TRI.  J . A . C . S . 1917,0.427. J . A . C . S . 1926,p.3155. Cot rotes Ren-lues l 0 2 , p . 3 o 3 .  II.OrAUTHIER.  Annales -Is Chiaie  I2.27RTHEL0T. PRU1TI2R.  Annales Annales  17.THIOLS.  Annalen 3"3,pp.374-779.  14 .STRAUS•  B e r i e n t e 42 ,p.277-3.  I^.IRIUSR.  Conotes Reniues 117,p.553.  TX i"'T 'T75; 1 w . e i_v.' V .j .  A ••, r 1 T .:> fUi-J 1,-a. —J * ,  17.7:720.11.  A/rialee de Cniiuiu ( 7 ) , 14 , p . 4 9 1 .  <6),l6,.p»350,  Cni-'.ie 1 4 ) , 9 , p * 4 6 6 . Chi ie U 7 ) , 17,p. 17.  ' T ,"' w« .  

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