\ ‘_ ‘ ‘ v t I"t I ‘ lLfll Wm H H H H. H 'I N H 7,.- I“ 1 ,i l .40.; 320000 _(DCD\I THE REAC'HON OF ALPHA-HALOGEN ACID HALIDES WITH GRIGNARD REAGENTS L THE REACTIONS OF ALPHA- BROMOACETYL BROMIDE. AND ALPHA-CHLOROACETYL CHLORIDE WITH METHYL AND ET'HY L‘ MAGNESIUM BROMIDES AND lODlDES Thesis for the Degrec of M. S. MICHiGAN STATE COLLEGE George B. Spero 1940 .L.tt‘..!.....‘9 . 1.“... w... JOLHMOP.W.NKV§Q..N.J. a A§.IA THE REACTION OF ALPHA-HALOGEN ACID HLLIIIES 'ITH GRIGNZARD REAGENTS I. THE REACTIONS OF HEEL-BROMOAGETYL BROMIDE AND HEEL-CEOROACETYL CHLORIDE IITH METHYL 1ND ETHYL-MLGNESIUM BROMIDES AND IODIDES by George 3. Spore A THESIS Submitted to the Graduate School of Michigan State College of Agriculture and Applied Science in partial fulfilment of the requirements for the degree of MASTER OF SCIENCE Department of Chemistry 19% T‘ 54 \' 814% [ACKNOILEDGEMENT The writer wishes to acknowledge his sincere appreciation to Dr. R. c. Huston, whose guidance and helpful suggestions made this work possible. fl: 1" a ‘UV Q 4 a... 3 y. {I ”I I. II. III. IV. TABLE OF CONTENTS Introduction Historical Experimental 1. 3. C. Materials Preparation of reactants l. Ghloroacetic chloride 2. Bromoacetyl bromide 3. Bromoacetone h. Grignard reagents Reactions proper l. GEéIOOI‘+ 3.5 Bug: 2. Bromoacetyl bromide + l methylmagnesium bromide 3. Bromoacetone +~2 methyl magnesium iodide Proof of Structure Table of results Summary Bibliography THE REACTION OF ALPHA.HALOGEN IALIDES WITH GRIGNARD REAGENTS. I. THE REACTIONS OF ALPHA-BROMOACETYL BROMIDE AND ALPHA-CHLOR- OACETYL CiflaORIDB IITH METHYL AND ETHYL- MAGNESIUM BROMIDES AND IODIDCS. Elimination In conjunction with the work being done in this laboratory on the preparation and condensation of alcohols with phenol, benzene and their derivatives, the reaction of alpha-halogen acid halides with Grignard reagents was investigated as a possible means of preparing some of the branched, tertiary alcohols. If the reaction were to proceed in the expected manner, it would yield, upon hydrolysis, a tertiary alcohol, the halogen in the alpha position of the acid halide being replaced by the alkyl radical of the Grignard reagent. This was not found to be the case. Instead of a tertiary, a secondary alcohol was obtained. This thesis will give a description of the different reactions car- ried out. It will also attempt to explain the deviation of the reaction from the expected course by preposing a reaction mechanism. HISTORICAL 2. W To the author's knowledge, this paper represents the original work done on the reaction of Grignard reagents with alphaphalogen acid halides. The search in the literature revealed that no such reaction has been carried out previously. The historical portion of this thesis will, therefore, give a brief discussion of the work carried out in related fields; namely, the hydrocarbon synthesis, the reaction of Grignard re— agents with acid halides, the reaction of Grignard reagents with alphan halogen compounds, and the reaction.of Grignard reagents with dialkyl zinc. The hydrocarbon synthesis by use of a Grignard reagent and an alkyl halide has long been.known and has been widely employed. In 1913, Spdth (1) published a comprehensive paper dealing with the reactions of a large number of alkyl halides with Grignard reagents. He found that the yields of the desired hydrocarbons were usually low, and.that other hydrocarbons were produced. This led him to the conclusion that alkyl radicals were first produced by the reaction, and.that the subsequent combination of those radicals gays rise to the variety of hydrocarbons. Previous to Spdth, in 1903, Ebuben (2) found that unless Rug! and.nix were heated together, the hydrocarbon.npn' would not be formed. In 1906, Gomberg and Gone (3) prepared PhBG-cfiéPh.in.good yields from bensylmagnesium chloride and triphenylchloromethane. Trotman (h) in 1925, tried to prepare quaternary compounds of the type (cssscs)2osisa by the reaction.of Grignard reagent with tertiary haIOgen derivatives. His success was somewhat limited. Carothers and Purchet (5) were able to prepare phenyi-h-butadiene 1,2 from chloro-h- butadiene 1,2 and phenylmagmesium bromide. litchovits (6) in 1935, in order to show the stability of the five-membered ring, reacted 3. o-chlorocyclopentanone with methyl, ethyl, propyl and phenyl Grignards. In all cases the chlorine was replaced by the alkyl of the Grignard. ‘ The reaction between acid halides and Grignard reagents has been used to prepare tertiary alcohols. Gilman and l'othergill (7) were able to prepm tertiary alcohols in as high yields as 93$. Gilman and say- hue (8) reported the effect of varying the amounts of the Grignard re- agent. i‘hey reacted bensoyl chloride with phenylmagnesium iodide and found that if the reactants were used mole for mole, the product was bensophenone. If an excess of the Grignard reagent was used, the prod- not was mainly triphenylcarbinol. 'ihey further reported that the yield of ketone was affected by the halogen present in the Grignard reagent in the order I >01>Br. Some work has been done recently on the reaction of Grignards with alpha-halogen compounds. In 1930 Fisher (9) found that the alpha halogen in some alpha-halo-ketones was repaced by the hydrogen under the influence of a Grignard reagent. He found that if bensoyldiphenylmthyl bromide were reacted with PhllgBr, the product ma hydrolysis was bensoyldiphenyl methane. He explained the reaction through the formation of unsaturated intermediate compounds, which upon hydrolysis gave the compound with hydrogen in place of the halogen. Kohler and Tishler (10) found that if an alpha-bromoketone were re- acted with one mole of Grignard reagent, the product was an unsaturated compound and an allql halide formed by combination of the alkyl from the Grignard reagent and the alpha-halogen. i'hey expressed the reaction as £0110!" ? [/0 NOW B-gc-R + mugs:- _____) sags-s + R'Br Aston (11) working with alpha-halo nitroso compounds and Grignard reagents h. found.that an unsaturated compound was produced. Home of these workers 'used an excess of Grignard reagent. The only work done which is closely related to that of this thesis was done by linogradow'Ilz) in 1878. as reacted one mole of alphapbromo- acetyl bromide with three moles of sinc dimethyl. The product he obtained was methylisoprOpyl carbinol. lhen sine diethyl was used, N—ethyl hexanol- 3 was obtained. He explains the mechanism of the reaction by assuming a rearrangement to have occurred. 5. e re 6. Dis s In all of these reactions, the ratio of alpha-halogen acid halide to the Grignard reagent was 1 2 3.5. Three moles of Grignard reagent were used as the calculated amount and a half mole was used as an excess. If the reaction were to proceed in the dunner expected, the product would be a tertiary alcohol. 95gb? GRZBrGOBr M9 seem-3:31; _,' _____> saga-W3 3 01133:, ' 8:83? pm; CRZZBrCII—CH3 m 9 932'. 033 mg 9 ‘ 033 CH} 033 on 633632-| H cl‘3 The first mole of the Grigiard reagent would react with the acid halide group and slit off HgBra (13) to give h-omoacetone. The second mole of Grignard would react normally with the carbonyl group, and the third mole would react with the alpha-halogen, splitting off 11th and putting in a 633 grow. The final product won hydrolysis would be tertiary awl a1~ cohol. This alcohol was not found to be the product. A secondary alco- hol was obtained, methyl isopropyl carbinol. That the course of the re- action did not proceed as expected was further shown by the fact that a secondary octyl alcohol, lI--ethy1--hexanol--3, was obtained when ethylmag- nesium bromide was used. In order to explain the deviation of the reaction from the expected course, two possible courses of reaction are given. 93 m 03231'0031‘ ___sn2L__> Garza-Br _z:n3mz__, H OMgBr I | ' Egg-9:115 + on), .293ng g . 9-033 3 use: 330 MgBr - H __2mL__, (639203-33: In this reaction, the bromoacetyl bromide is asstmed to enolise under the influence of the Grignard reagent (11!). Two moles of Grignard re-' agent then react, one with the active enol hydrogen (15) and one with the double bond. The next two moles react respectively with the carbonyl group formed and with the alpha-hydrogen. The final product upon hydrol- ysis will be methylisopropyl carbinol. It is also possible that the‘unstable enolisation product nigit split off EB:- -to give a brominated lestene. If the ketene were to react with three males of Origin-d reagent, the product would be nethylisopmpyl carbincl. 31‘th 0337c:— ___Hg§__, (origami? 033 The first mole of Grignard reagent reacts with the carbonyl group, the second sole with the double bond, and the third mole with the alpha ha10gen. lo EBr was observed to be given off during the course of the reaction. Also, it will be observed that four moles of Grignard reagent were necessary to carry the reaction to completion. This is possible due to the fact that excess Grignard reagent was used. A gag-B; 7e (3) cnzsrconr __QH_3mm-__, mam-$133.} ; H3 0 moon 1: maggot! EBr $1103 H23 3 -—-991—> 3 m 33 3‘53} /03 on W 3" EX} __.§.Q§__y (633)203ch3 Br In this reaction, bromoacetone produced by the reaction of one mole of GHngBr is assumed to undergo enolisation (16), (17). The second.mole reacts with the double bond, and the third mole replaced the alpha hal- ogen. If the second mole were to react with the active enolic hydrogen, four moles would be needed to complete the reaction, and the product would still be methylisopropyl carbinol. Due to the fact that the yields were low and that excess Grignard reagent was used, it is pos- sible that the reaction.proceeded in the ratio of one mole of bromo~ acetyl bromide to four moles of methylmagnesium bromide. In an effort to establish the mechanism of the reaction, attempts were made to isolate one of the intermediate products. Such attempts were unsuccessful, the difficulty being the tendency of the intermediate products to polymerise. If reaction (1) represented the correct mechanp ism, the reaction product of two moles of methylmagnesium bromide and bromoacetyl bromide upon.hydrolysis should be alphanbromopropionald0hyd0. This in itself polymerises. If it lost HBr, acrylic aldehyde, which polymerises very readily, would be formed. neither the lromoaddehyde nor acrylic aldehyde were isolated. If reaction (3) represented the true mechanism, then the product of bromoacetyl bromide and one mole of methylmagnesium bromide would be bromoacetone. A.small fraction was isolated in the range of bromoacetone, 8. but it failed to yield a derivative. This fraction had the irritating effect on the eyes common to bromoacetone. The fraction polymerized readily (18). Since bromoacetone could not be isolated as an intermediate, it was decided to prepare it by a known method and react it with methylmagnesium bromide. This was carried out (as described in experimental) and the product obtained was methyl isopropyl carbinol. The fact that methylisopropyl carbinol was obtained from bromoacet- one and methylmagnesium bromide indicates that the probable mechanism of the reaction is that shown in (B). EXPERIMENTAL 12. 13. 1h. 15. 16. 17. 18. 19. 9. MATERIALS USED Chloroacetic acid, m.p. 62-611, Central Scientific Phosphorus trichloride, Pract. Sodium bromide “ethyl abcholl Pract. Merck Sulfuric acid, conc.. G.P. Methyl iodide, m. ’41-’50, Eastman mm bromide, 3.2. 3s-ho", Dow Chem. Anhydrous Ether (kept over sodium) Acetic acid, glacial, G.P. Acetone, C.P., Herc}: Bromine Red Phosphorous Diethyl carbinol, 3.19. 1114.110. lastman n—Propyl alcohol, B.P. 96-98°, Eastman Potassium dichromate Hydrochloric acid, G.P. Magnesium turnings lthyl ester of chloroacetic acid, prepared in this laboratory, P.P. ind-115°. Methylisopropyl carbinol, B.P. 110.113°, Iastmen 10. We We (19) In a 5-liter, three-neck, round bottom flask, fitted with.a glycerine sealed stirrer, reflux condenser and dropping funnel, was placed 756 gms. (8 moles) of chloroacetic acid. The flask was warmed until the chloro- acetic acid melted. The stirrer was started and ’415 gm. (3 moles) of phosphorous trichloride was added drop by drop. The addition required about one hour, after which time the reaction mixture was allowed to stand in the flask for two hours. The liquid portion was decanted from the phosphorous acid and the white solid formed on the sides of the flask, and was fractionated. The fraction boiling at 103-106° was taken. Yield, 370 5mg. W (19). (20) This compound was prepared in two steps. First, the acetyl bromide was prepared and then the alpha position was broninated. In a 5-liter, three-neck, round bottom flask fitted with a glycerine sealed stirrer, a reflux condenser, and dropping funnel was placed 600 gms. (10 moles) of glacial acetic acid. The stirrer was started, and 750 gms. (3.75 moles) of PM} was added dropwise. The reaction. mixture was allowed to stand for two hours. The acetyl bromide was decanted from the phosphorous acid and fractionated. The fraction boiling 7o.so° was collected. The acetyl bromide prepared above was placed in a 3-liter, three-neck round bottom flask, fitted with a glycerine sealed stirrer, a reflm con- denser, and a dropping funnel. To this was added 5 gms. of red phosphor- us. The stirrer was started, and 1300 gram. of bromine was added throxgh the dropping funnel. The addition required three hours. The reaction 11. mixture was allowed to stand overnight. The flask was then gently heated until all excess bromine had been given off. The mixture was fractionated and 1150 gms. of bromoacetyl bromide was collected, boiling at 116-1190. W Bromoacetone was prepared by brominating acetone with bromine in the presence of acetic acid (21). The bromoacetone must be used as soon as possible, or refrigerated. It was found that if bromoacetone were allow- ed to stand at room temperature, it blackened. Upon refractionation, the product could not be obtained, in its original state of purity, and on reaction with methyl magnesium bromide, it did not give the desired prod- uct. re 0 e Methylmagnesium iodide and ethylmagnesium bromide were prepared in the usual manner, e.g., the calculated amount of alkyl halide in anhydrous ethyl ether was added to magnesium turnings in a three-neck, round bottom flask, fitted with a glycerine sealed stirrer, reflux condenser and drop- ping funnel. The rate of addition was such that the reaction mixture refluxed gently. Methylmagnesium bromide was prepared by passing methyl bromide gas into a mixture of magnesium in anhydrous ether. Methyl bromide was pre- pared by heating a mixture of sodium bromide, methyl alcohol and concen- trated sulfuric acid (22). The gas was passed through a battery of wash bottles containing 30% sodium hydroxide and concentrated sulfuric acid. The base was used to neutralize any EBr that might have formed, and the acid was used to dry the methyl bromide gas. 12. 1‘ In a 3-liter, three-neck, round bottom flask fitted with a glycerine sealed stirrer, a reflux condenser, and a methyl bromide delivery tube was placed 97 gms. (ll moles) of magnesium turnings. The flask was warmed, and 2 cc. of methyl iodide was added. To this was added about 20 cc. of anhydrous ether. As soon as the initial reaction had subsided, the stir- rer was started, and 2 liters of anhydrous ether was added. Kethyl brom- ide was allowed to pass in at such a rate that the reaction mixture re- fluxed gently. The reaction mixture darkened in the course of two to three hours. The reaction was complete when all of the magnesium had re- acted. This required from 10 to 15 hours. The reaction was found to be about 90% efficient (by titration), so that for every four moles of mag- nesium used, there was formed 3.5 moles of Grignard reagent. 13. Bessiisns.2:snez o of The following reactions of this type were carried out. The results are shown in the Table of Results. 1. Ghloroacetyl chloride + methylmagnesium bromide 2. chloroacetyl chloride + methylmagnesium iodide 3. Chloroacetyl chloride + ethylmagnesium bromide It. Bromoacetyl bromide + methylmagnesium bromide 5. Bromoacetyl bromide + methylmagnesium iodide 6. Bromoacetyl bromide + ethylmagnesium bromide Also the ethyl ester of chloroacetic acid was reacted with methylmagnesium bromide. Since the same procedure was used in carrying out all of the above reactions, only one run will be described. In a 3-liter, three-neck, round bottom flask, fitted with a rflux condenser, stirrer, and dropping funnel, 3.5 moles of methylmagnesium iodide were prepared as described above. To this was added, dropwise. 113 gms. (1 mole) of chloroacetyl chloride in 500 cc. of anhydrous ethyl ether. The reaction was very violent, and addition was slow. The reaction mixture turned to a yellowish color and finally darkened. After all of the chloroacetyl chloride had been added, the reaction mixture was allowed to stand in the flask for about one hour. The flask was then removed and plhced on the steam bath. A condenser was fitted to the flask so that a downward distillation would be accomplished. The steam bath was gradually turned on until all of the ether in the reaction flask had distilled over. The steam bath was then turned on completely and the contents of the reaction flask were alllewed to bake for an to 1h. to 36 hours. .At the end of this time, the contents of the flask were a yellowish, brittle solid. The solid was removed and hydrolised with ice and concentrated hydrochldric acid. Enough acid was used to disperse the precipitate of magnesium hydroxide. The hydrolised mixture divided into two layers. The top layer was separated out, and.the lower layer was extracted three times with ether. The ether extracts were mixed with the top lay» er and dried over a mixture of anhydrous sodium sulfate and sodium car- bonate. The ether was then removed and the product was fractionated. The portion coming over at lO9--112o was taken as the main fraction. This was later identified.as methylisopropyl carbinoh. In all cases where methyl Grignard.was used, a small, lowbboiling fraction was obtained, but no high fractions. In the case of ethyl Grignards, both low and high.fractions were present. The main fraction came over at N3—h50 at h mm. of pressure. This was found to be h—ethyl- hexanol-3. : em;_ a I} en’s». + '{E 9" 11.4500: nu I 0}}! e'. ;!d o3 enema '_ _0 en L.- W. In an attexpt to isolate any intermediate compounds, bromoacetyl bromide was reacted with one and two moles of methylmagnesium bromide. In these reactions the bromoacetyl bromide was kept in excess by adding the Grignard reagent to it. In a Z-liter, three-neck, round bottom flask, fitted with a stirrer, a reflux condenser and a dropping funnel was placed 101 gms. (5 moles) of bromoacetyl bromide in 250 cc. of anhydrous ether. The stirrer was started, and..5 mole of methylmagnesium bromide was added drOp by drop. The reaction mixture separated into layers in the final stages of addit- ion. The contents of the flask were hydrolysed with ice and hydrochloric 15. acid, extracted with ether, and dried over anhydrous sodium sulfate. Upon fractionation under reduced.pressure (13 mm.) no constant boiling fraction could be obtained. In the course of distillation, the contents of the distilling flask became black and.viscous, until no fur- ther distillate would.come over. If this viscous material were allowed to stand at room temperature, it finally solidified into a black, brittle substance. The distillate which came over clear, darkened upon standing. Some of the distillate came over in the range of bromoacetone (ass-115° at 13 mm.), which was expected to be the intermediate. .Attempts to pre- pare the semi-carbosone were unsuccessful (23). Further attempts to identify any fraction of the distillate were unsuccessful. In the reaction of bromoacetyl bromide with two moles of methyl- magnesium bromide, the results were the same as those above. so inter- mediate compound was isolated. e‘g eA: o ems; ; eg: s l_|e ;-. e_ ‘: Q I to o 5 «:5 (n ; D - . A '. We. The procedure for both of these reactions is the same as that des— cribed for chloroacetyl chloride and methylmagnesium iodide. Bromoacetone in anhydrous ether was added to the Grignard reagent. The reaction mixt- ure was set on the steam bath for 25 hours and was then hydrolysed. The product obtained from both of these reactions was methylisopropyl carbdnol. 16. 2222£_2£_§122£IE£: Methylisopropyl carbinol was identified by means of derivatives. 3,5 Dinitrobensoates and alphapnapthyl urathans were prepared from the product of the reaction of chloroacetyl chloride + 3.5 moles of methyl- magnesium iodide, and from known methylisopropyl alcohol. The melting points of the derivatives were the same, and mixed melting points were found to melt the same (Constant given in Tabde of Results). The derive atives were papared by the general method of preparing alcohol derivatives (21$). No difficulty was encountered in their preparation. The proof of structure of h—ethyl-hexanol-3, which was the product of the reaction of chloroacetyl chlorida.with 3.5 moles of athylmagnesium bromide, was established by synthesis. It may be shown as follows: 3:: s; e s-g-on+ssr___,n-sr+ug 35%”! HZ Ha E tn3 033 c s * 0E3GE2°HO H-ingacgzcfi tag 3 ts} The bromide was made by refluxing for two hours diethyl carbinol with an excess (3 : 1) of heat hat. The bromide boiled at 1114417". This was re- acted with magnesium (as in the general method.preparing Grignard reagb cuts) for the Grignard reagent. To the Grignard reagent was then added propionaldehyde in.anhydrous ether. The aldehyde was prepared by oxide ising propyl alcohol (25). The reaction mixture was hydrolysed with ice and.hydrochloric acid, dried over sodium sulfate and fractionated.under reduced pressure. The alcohol distilled ath2-h5olh, 162-650/7h5. 17. Other constants were found to be as follows: 8p. Gr. 32/32 = .8365: 28 2 2 ' up 3 1.11287; 1? 25.20 dynes/cm. Efforts to prepare derivatives of this alcohol and of the alcohol obtained by the reaction of chloroacetyl chloride with ethylmagnesium bromide were unsuccessful. Therefore, physical constdnts were used to show that (both alcohols were Lethyl—hexanol-3. The boiling point of the tertiary alcohol, diethyl-nppropyl carbinol (which would be the product 1: the reaction went as expected) is 155-159°. This is about 5° lower than the alcohol obtained. age" no “menu. «Sam .3 .& m5??? «new w a» «motommomma {owls :3" 34833453 aoe eased .oeeeeeeo mm weight :72. a2 «2&2 aaaoaeoofiafio: doses me .e a 838883 H8383 edge.“ agnoswss mama. “ma mfiumoa Haaoaaoenafle: Asses do .e N 338858 Hodges 0.3303. 33 0333330 .1. mm. «242 138%. 33:: s3. 335.33: do we»: Hanan 330.3 330.5 mm {99.qu maaoaoacdhmaot: gagging Aha oososoam Houdphdo ovum—0.3. 0630.3. 1 :72. wow Seneca decodes Sacco: ssaeoemeaaafle: one eoeoaeam defined 333 «35.5 m: £11. a3 9279: Haeeaeoeflafiox fiaeodefiafioa aaooeeoeeam mm; 9:}.de .333 823% mam £919 mnaoeewoeuaafieu: asaeeemeeaafln £889.36 . Houses 832... .382». .31. «an 9319: aRoaeoezafioa as: osmosis»... Haeeeeoaods 239.8 383 oeaaode 937a: :72. am: 93.78” $3382.33: Steamefiafioa Haaoeeoaode can: 11 Humans: evacuate seeds 952:. man 4%: .. 33 a]; an e communal magma ho was 18. l. The reaction of alpha-halogen acid halides with Grignard reagents was studied. 2. A reaction mechanism was preposed. 3. Bromoacstone was established as one of the intermediate compounds. 1!. The product of the reaction of chloroacetyl chloride and bromoacetyl bromide with msthylmagnesium bromide and iodide was found to be methylisopropyl carbinol. 5. The product of the reaction of chloroacetyl chloride and bromoacetyl bromide with ethylmgnesium bromide was found to be ll-ethyl-hexanol-3. 6. Constants of 1lOethgrlnhexanol-fi were determined as follows: 3. P09 “445”". 153-65°/7h5: 8p. Gr. 32/32 .8372: 111238 1.1291: {"3 25.32 dines/cm.2 . 19. BIBLIOGRAPHY (1) spam, Monatsh, 33. 1965, 1913, British Chem. Abst. 190, 1. 19111. (2) Houben, Ben. 16,, 3033, 1903. (3) Gomberg and Gone, Ben. 39,, 11161. 2975, 1906. (h) Trotman, J.8.G., 1.21, 88, 1925. (5) carothers and Berchet, J.A.C.8., 55, 2313. 1933. (6) Mitchovits. Gompt. rend. ggg, 1601. 1935. (7) Gilman and Fothergill, sec. traw. chim., fig. “(’48, 1929. (8) 611mm and nayhue, Rec. trav. chim.. 5;, In. 1932. (9) Fisher, J.A.c.s.. 5_2,, 5038, 1930 (10) Xohler and Tishler, J.A.G.8.. 55. 1591:, 1932 (11) Aston, J.L.G.8.. 51. 1920, 1935 (12) Iinogradow, l.. Ann. 111,. 125. 1878. (13) Gilman and Fothergill, J.1.c.s.. 51. 3501. 1929. (1h) Bhagwat and Sudborough, 0.1., g, 1671;, 1920 (15) Gilman and Beck, J.A.c.s.. 52, 119119. 1930 (16) Hughes, latson and rates, J.G.S.. 3318, 1931 (17) Grignard and Blanchon, 0.1.. 21;. 13112, 1930 (18) Giovanni and Racciu. 0.1.,‘21, 5719 (19) Anderson and Backmann, Lab. Man. of Org. chem. p. 11, 1933 (20) lard, J.c.s.. _1_2_1,. 1161. 1922. p . (21) 01mm, Org. mu... 101. 10. p. 12 (22)Clarke, Org. Synth" Vol. 10, p. 32 (23) Eoogeveen and Jansen, Rec. Trev. Chin" 5;, 260, 1932 (2k) Shriner and Fuson, Ident. of Org. Gomp.. Iiley 5 Sons, R. 1., p. 138 (25) lhitemors, Org. Synth. Vol. 12, p. 65 ‘Irtn... . l.-. . . . n I Q I. DI . o I ..'1| .13.! I17)!!’}1..".M’|1 I ) T ’tluil THU- - . . y \I' “((7 .. . (Ln- (I . I v ! (a! , (131?.- , . . . yy . . . . . ..V. .0. H.. w «I .1. u 4 . a . s ‘ ah.» i... l... 1.. .1. by ... t , 1.14 -.. 1.4; l 8749 132645 1.4 CI P (.1 Spero 31293 024466