vF‘ "' H... ...-.- \..l.\.AA\, p . . ' HIHHHHHH |, ,v‘lim >u.:.u - ..‘ ,,..u._.,.. .,.:. CUNDENSATIDN DE ALLYE ALCOHOL WITH BENZE‘EE IN THE PRESENCE OF ALUMINIUM CHLORIDE f THESIS FOR DEGREE OF M. 8. DEWITT DUNN SAGEP. ‘ :;=1.-;'}‘E-~- 9 2 5 a-.\ ..:.¢. . .‘\ ,. .. .._'. ‘I -.-..rn'o--.| 'Aa.--'.!Iv0 .,-,.-... ‘r‘ . v - .‘....".‘.u~.->-I‘ I _. ...~“ .I" - n.4,, ‘ ~ \ |. - u, ,. . ‘ ' ‘ E I ' - All‘d-lvl‘pit‘l‘ - - ‘ V - . . W 4 “W?! 9!? fi‘!’ 1 7 --..\..\.~ . , ... ... .. . . ”7‘"...qu mam“ ............................... "WNW!“I”!UHWIUHIUWI.WWI'MIMNII w 300627 9644 ' L1 [I L I B R A R Y i "viichégan State J3:22:25:if???1:12: E University ', 7-=-;:i:e:-.:;'a;;‘;;#:; 1.43;; - r»; a — CO'TiFf‘T'RfiT-TON OF PLLYL AL’TOHOL WITH FENZE‘NE IN TEE? P‘PEESEY'WE 0F ALEFST‘I EUM CHLOQEDE "C'JTVBATIOW CF fiLLYL fiLCOHOL WITH BVHYIEE ALUIIYIUH CHLORIDE lxj IN THE PFFSFNCE C TH“3IS Submitted to the iculty of hichitan State College in Partial Fulfillment of the requirements for the degree of flaster of Science. BY Defiitt Dunn Sager 1925 Acknowlekbexeuts Why writer 3 Sreatly indebted EC s‘L‘.) Profussor V. R. Huntcn fcr hell? . J _ , " _ .- ‘ ._ , ‘ . ' in “h {a erluenunx Jerk and 1n {cf-u * of Lh.s L per. 331.661 ul gtlidz-z.z.(:e, 1h: vr1115¢i 1. Review of Previous 1. NJ 0 3. 4. EABLE CF CO’TEYTS Page ork.----------------------- l. Aluminium chloride as a dehydrating agent in Urbanic Chemistry ----«--------------¢---l. Condensation of Alipbatic alcohols natn benzene by other dcugdratiné atenta -------- 4. Allylat.on of benzene --------~----~-~--~--- 5. Preparation of'u chlorc chpyl benzene ~----12. II. Allylation of benzene and formation of u-" chlorogroyyl benzene ln the preaches of H O (0 0 III. Iv. Summary and Conclusion ---------------------;$ Experixental. Eye tEIOd CDC-G-------‘-"""‘“"“-"------—-----14. PICLfiTfiLiOL of propenyl benzene and 9’; > dibromprcpyl benzene -----------*--~-------20- Preparatxcu of{¢-w—dioroxcproyyl DCMLCLC --41. Preparation Off~'thrO belzoic acid, and Lao Lethjl esLer of ~“nitro benzolc acid, also preparation of benzoic acid -----~-~-------b2. Attempt to identafy high bo‘ling fraction-~z3. kn attenpt to condense n-propyl alcohol wLLh benzene in presence of aluninium Cllloride ---‘----‘--n’c‘--‘----—--u-——----;‘C . ' O r)! - N . ~ . -1- I. Review of Previous Work. 1. Aluminium chloride as a dehydrating agent in organic chemistry. Aluminium chloride has been used as a dehydrating agent in organic chemistry by a considerable number of investigators: waas (1882) (1) prepared di and tri phenyl- ethane by the action of aluminium chloride on dichlorethyl oxxde and benzfne. The course of the roastion was exgeri- mentally shown to be as follows: the aluminium chloride first converts the dichlorethyl oxide into mono chloralde- hyde, which, reacting with benzine, forms first mono chlorodiphingdethane and finally triphenylethane. hers and Weith (1881) (2) prepared diphenylether by the action of aluminium chloride on phenol. Graebe (1901) (3) prepared aniline in small quantities by the action of hydrox§damine on benztne in the presence of aluminium or ferric chloride, but not in the presence of zinc chloride. By the same method Toluene gave a m.xture of p-toluidine with a little 0-- toluidine,.o-xylene Lave a relatively good yield of a-anino-- 1:2 xylene; m—xylene gave Q—amino—l:5-xylene, and p-xylene gave: a small amount of 2-amino-lz4xylene. Mesitylene was partial- ly converted into mesidine. Haphthalene gave a small yield of a- and/Q naphthylamine. Jaubert (1901) (4) similarly prepared the hydrochloride of the amine by using hydro- glamine hydrochloride. The yield however was low. Scholl & Seer (1912) (5) succeeded in uniting aromatic neuclei, esbecially in case of aromatic ketones eg. 1 part (1) naphthylphenylketon-2-carboyyéacid with 5 parts of aluminium chloride and heated for 2 hours at 130 gave 1-2 f. -d- benzanthra chinon according to equation: // / n" gl 1 , . . 9 2/ v /\ I ”"---./ /) 05.1"? 1:: /\/ ‘V' .' if L /( N ‘‘‘‘‘‘‘‘‘ t 'l L 3‘ l .14 (‘l' ‘ .- a ~.,, -.- ' ,' .1 a o"! y 0. B. Frankforter & W. Kritchevsky (1914) (6).state f " ) 24 I’- A that the applicability of aluminium chloride as dlhydrdr ting agent appears to be aloost as universal as that of sulphuric acid. and they have employed it in preparing condensation products of the aliphatic, benzihe. naphtho- lens and anthracene series, rot only with chloral, but also with chloral hydrate and bromal. Benztne, toluene and xylene yroduced with chloral the same condensation products as are obtained by means of other condensation agents, formed according to the equation: 2RH+CCLL.CH0=CHRL.CCL;+H19. Pentane and chloral react very violently: the product is a mixture of substances which is being investigated, but is evidently produced by dthydroiimT‘Bfinyzfil dcohol, chloral, and aluminium chloride at ordinary temperatures produces benzaldehyde and a mixture of two or more chlorinated unidentified substances. Resorcinal and chloral in cold carbon disulfide were converted by aluminium chloride into dichloro as duesoreylethylene. scrim ((1 Hammjt Phonetole, chloral, & aluminium chloride gave trichloro- diphenethl ethane, .m’mmcg Hyoozpay)?‘ Phenetole, bronal, and aluminium chloride give the similiar tribromo compound. Frankforter & Kokatnur (1914) (7) prepared diphenyl-- methane and anthracene by the action of aluminium chloride the above reaction by the followxng equation: 4CQH,*(CH o) .-. on.(c H )—+’C H was on! . 7.. .7) I_ :1 .' [I'd l’, ;_ 2... v - a , The reaction between tOIUGL: and trioxymethylene in presence of aluminium chloride was similiar, producing benzrne in small amounts and also ditalylrethane and dimethylanthracene according to the equation: 4st H5085 ((0319);: Catt? uses? ) C,“ --;3I{2~04I{L. O-xylene under s.miliar ccndit ons yielded a m.xture of substances from which was isolated; benzfne, possibly ' some toluene. dixylylmethane (975,.) and tetsamethylanth- racene. hesitylene treated in the same way Lave; tetia- methylanthraoene, benzfne, toluene, x-ylene, dimesitylme- thane and durene. Frankforter & Kritcnevsky (1315) (8) extended their researches to the more complex aromatic derivatives and found that they condensed with chloral and bromal as well as the less complex conpounds. A mixture of naphthalene and chloral when treated with aluninium chloride gave ac—dinaphthyldichloroethylene (c H ) (2 cm; ) and fidimm- thyldichloroethylene. t worked equally well with bronal giving dibromo compound instead of the dichlcro. Anthra- cene treated in a siniliar manner have dianthraoete diohloro- ethylene, when the mixture was suspended in petrolic ether, ‘fihen suspended in benzene or carbon disulphide it gave 9, 10-anthracenediohloroethylene. Phenanthrene cave similier compounds. Ihenanthrene, benzaldehyde in carbon disulfide gave diphenanthrene phenylmethane (1%‘H?)t:CH.Q$H{and dibenzalmesotriphenanthrene (Q HIGH ) -- (Cm,Hg) (Qt H?)v: Huston and Friedeman (1916) (9) were first to use aluminium chloride as a condensing agent for aromatic illll'lulllllll -4- alcohols w.th aromatic coniounds. They prepared diphenylm- ethane and anthracene from benzene and benzyl alcohol in presence of aluminium chloride. They found that the amounts of reagents used and :he termerature at which the reaction totk place Lreatly influenced the yield. The same authors (1818) (10) extended their experiments to secondary alcohols with benzene and aluminium chloride. They used methylphenyl carbinoletnyl phenyl curbinol, and benzhydrol and obtained diphenylmethane, dighenyl prepone and triphenylmethane reapecttvely. In (1%24) R. C. Huston (11) condensed benzyl alcohol with phenol by neans of aluminium chloride to form benzyl phenol. He also con- densed benzyl alcohol with anisol and phenetol and obtained the methyl and ethyl esters respectively of benzyl phenol. 2. Condensation of aliphatic alcohols with benzene. very lit 1e has been accomplished alont the line of condensing aliphatic alcohols with benzene by any dehy- dieting aLent. Coldschnidt (lcc2) (1) prepared h(aolotues of benzene by the action of zinc chloride on mixtures of aliphatic alcohols and benzene at high temperatures. Thus benzene and istbutyl alcohol pave iscbutyl tenzene and the dibutyl benzene. Toluene and butyl alcohol nge methyl butyl benzene. Penzene and ethyl alcohol Lave ethyl benzene. In the latter case the yield was small owing to the difficulti ies of manipulation. A. Brochfit and P. C. Boulenger (lt93) (2) found that ethyl benzene and hexethyl benzene were forned when 1 part benzene was heated with 2 pa H ts of ethyl alcohol and 4 1 0 parts sulphuric acid in a sealed tube at 175(-200 for 3-4 -5- hours. Similiar results were obtained With n—prolgf’ alcohol and also butyl alcohol. The mechanism of the react.on sprears to be exhibited in the case of hexyl alcohol. Benzene 3U1§h0016 8Cid was formed and recognized by conversion into its calcium salt and phenol. The hydrogen hexylic sulphate first formed appears to react with benzene according to the equation: OH. SOL. CCQ H: 5" 2C9 H‘rti Ii) SOLE-4 Co 113 C" H 3 J 32.0 The two references abover are the only two I have been able to find of aliphatic alcohols, saturated or unsaturated, being candensed with benzene. 3. Allylation of benzene by other hethods. In reviewing the literature there seems to be consider- able differences cf opinion as to the trcterties of allyl benzene. This is probably due to the fact that the allyl benzene was preyared only in 63811 quantities and not sufficiently purified. Also there has not been a clear distin- ction made between allyl benzene (QQHECHLfCHvCHl) and pro- tenyl benzene (qkthHeCH-Chg). Wagner and Tolleus (1573) (l) attergted to rake allyl benzene by heating at FOB a rixture of 4e tarts of allyl / bromide, 55 parts of brom benzene, 102 parts of benzene and 73 parts of sodium. ihey found that this yielded principally benzene and diallyl. Another experiment yielded diphinyl and a dark oil. From this data they considered it probable that al yl benzene was formed and its polyaerization products were contained in the dark oil. C. Chojhncki (1873) (2) / heated equal parts of benzene and allyl iodide or bromide o with L/s part of powdered zinc at 100 under pressure. The -5- quantity of ihenyl allyl was very small. It boiled at 153 . An lysis: Calculated ~ Found. C. 91.5 91.0 & 91.2 H. 5.5 7.8 & &.3 He said that he wanted to extend his researches in order to assure himself of the constitution and proterties of this hydrocarbon. Ruchein or (1874) (5) prepared what he called allyl benzene (CbHE-CH3CHCH1) by reducing cynamil alcohol with sodium amalgam. The allyl benzene as he prepared it boiled 1,/ at 155 f The dibromderivative (q H eCHBrCHBrCHi), made by direct union with bromine melted at 66.5 . Fittig (1874) (4) tried without success to prepare CAH5CHL-CHZCHQ_from brom— benzene and allyl iodide, also from brom benzene and allyl- / bromide. He tried to prepare the same compound by heating brombenzene. allyl bromide, sodium and a little ether in a sealed cube but without success. He replaced the sodium in the-preceding experiment with pulverized~silver but obtained no-results. B. Radziszewski”(lb74) (b) heated yhenyl grotane (CLH£CHICH:C%k) to loodiléo“ and found that it absorbed 1 molecule of bromine. He found that HBr was given off when the product was distilled and that the entire fraction came over between 165€il706 at 728 m.m. This fraction after three fractionations boiled at 162,-165‘at.728 m.r. This on analysis proved to be C HECQH §Hhe found that it combined easily with bromine in a chloroform solution. The bromide separated upon standing. The bromide crystals melted {I g» at 65 -66 . This upon analysis gave the formula C Hf? H_Pr. q a- J!- R. Fittig (1874) (6) reviewed his unsuccessful attempts to -7- to prepare allyl benzene, Q3H5CH3fCHaCHL. He spreared to doubt the correctness of Chojnacki's assertion that this hydrOcerbon is formed when a :zxture of brorbenzene and allyl iodide was treated by Zihcke's method. In (1875) M. Ecsivitz and B. Aranheim (7) atteryted to prepare allyl benzeLe. fihey diluted, with ether, a mixture of vinyl bromide and benzyl chloride and treated the mixture with sodium. Crotonylene and dibenzyl were forsed. They found that allyl cyanide and benzyl chloride do not react at a terperature of EOOé: Binder (1877) (8) showed that hydrobrcmo or hydricdo cinnamic acid, then treated with bases. not only lost hydro broric or hydicdia acids, but also carbonic anhydide, cheaiCally pure cinnamene being 21/ produced in considerable quantities. W. H. Perkin (187?) (9) aLLIied the aoove irincital to the hydro bromo derivat ves of phenylcrotonic, phenyl angelic acids and others. he 1/ cbta.hed allyl benzene (?) (Q 34CH*CHCH£) from the 1henyl chtOLlC cid according to the equatiors: CVH fgcnfiml-fliCOOH + Fat... CKI’HLCHQE‘JHBsCh £003 Cb HSCHv 314‘s". 81115100?! A 7:63 123:?“3. CHE" (301+ H730- II (a '"13 lbs allgl UCLLGHS (?) bo.1ed at 174 -173 and had 3 3p. gr. 0 .918. Its dioronidc melted at 67 . Analysis Cave the folioeinb results: Theorit-c 1 Found. C. 9 05‘? cello-'12:; H. 8.47 8.43 Triaan (18/8) (1.) prepared phenyl p ogylcns along with _ c$~vu4u+ I «Lari. ,Je’s is ¢+¢dI toluene by heating 10 vols71o fuminqfll in a sealed tube h// ‘J 1.3 A) at 180 ~2CC for 4-5 hours. The phenyl propylene boils at -5- 0 165 . It was idGDtifiéd by its boiling point sline. In (1884) Tabner (ll) obtaLned allyl benzene (7) (C H CEI CHCH ) by treat”D ethyl ghenyl ca LiflOl with 2// Hcl. This al;yl benzene (7) boiled at 174I-1756 and yielded a dibroride Which melted at 6‘.5’. G. Frera (18.5) (12) preiared the urzsaturated hydro carbon" o Hf H by treating the monochloro prolyl benzene with hot saturated /> . alcoholic non. mic boiled at 178 am and (,2 vs a V dibromide sh.ch melted at 65 : N. H. Perkin, Jr. and J. Stenhouse (1891) (13) pre- pared 31131 benzene (?) c H i on os-oa by heating methyl, ihenyl hydroxyyrcrionio acid. "hey gave the boilir.g point as 174 ~l7b . They treated the hydro carbon with a calculated amount~of bromine in a chloroform solution and 2// allowed it to stand at ordinary temperatures. This gave them dibrompropyl benzene, which melted at 66.5 . a. F. Genvresse (1993) (14) prepared sllyl benzene (?) by heating 36 grams of prcpyl benzene up to 150?)and adding 50 grams of bromine drop by drop. after all the bromine was _Z/// added the heating was continued until no more HBr was given off. The usultiz;L mixture was then distilled. The fraction boiling between 165;;186’ was redistilled several times until finally it came over between 172 e175A. This consisted mostly of allyl benzene (?) of which the dibroride melted at 65 2 He gave the following equation for this re- action: cbs J,cshcn 1on; 2Br 3. CLH’JCHQ’CHBrCHJHBr ch HSCHAICE-{BrCHa' " o H so Ef— c w: H, 51" HPr. Senrter and Tafel (1:94) (15) prepared jrtgenyl- 1' -9- benzene Q,pr :Ch-Cfllirom phenyl prcpyl trimethyl ammonium iodide. They warned the itdide on a water bath with an excess of silver oxide and strong alkali. The resulting syrup was distilled on an oil bath until the residue was a dark zitchy rese. The distillate Was treated with strong H130i4 until an oil segernted out which was extracted with ether. *he ether solution was washed several times with dilute H.303 and then neutral zed with K3601. A fraction boiling between 174(;l76!)wee obtained from the ether solut.on after several fractionationa. It was analyzed for thl. Calculated. Found. C. 91.52 91.31 H. 8.47 8.51 Alfons Luib (1894) (16) prepared phenyl tropylehe I .J C H CH_§H"CHA_by refluxing phenyl brocbutyrix acid with 100 parts of water and then distilling with steam. The // bromine derivative of th.s melted at 900-1000(?). August KIFCBB (1902) (1?) prepared groythyl benzene. is reduced chyionyl benzene with sodium and H100;01, according to the method workeu out by KEOEes and Alledorff. He then took the resulting onrbinel and formed the chloride which treated with pyridin under a reflux condenser. The hydro 22’ Carbon was dissolved with ether. The ether was washed with water and dried with sodium sulfate. The gropenyl beizene was distilled over sodium and under reduced pressure. It (r) L .) boiled at 74 at 13 m.m., and had a sp. gr. .9083 15J/4O -10- Calculated. found. Analysis C. 21.35 91.52 H. 8.47 8.42 C. Hell and H. Bauer (1903) (is) Lrepared l-phenyl prcyene by treating ethyl Lhenyl carbinol with htl, and :hen Lciling with water free Lyridin. xhe lnphenyl trogene boiled at 2L 174-175 and formed a dibromide in chloroform solution with bromine. The dibromtde melted at 66 . August Klates (1303) (19) continuing his researches prepared allyl benzene (?) or propenyl benzene from phenyl ethyl carbinol. The carbinol was converted into the chloride. The chloride was treated With two mol. of Lyridin under 2/“ pressure at 125 . This caused the addition product of pyridine and the chloride to be contlexely decomposed. The jrcgenyl benzene bailed at 72 :74.~&1 15 m.m. and had a 8;. er. of 9338, 1424 . At ordinary tergerature it boiled at 1740-1750. He found that the troyenyl benzene was not easily reduced to n-trcghyl benzene. F. Kunekell and W. Dettnnr (1903) (20) cede the aseu:_ticn that ;rc;enyl benzene .3 easily gclynerinc ow ng to the d.fferencee in boiling telnt and also differences in 59. Cr. heretofore recorded. They added to 10 are. of chlor/gnbrcmtrc;yl benzene. dissolved in 100 c.c. of ether, 10 grams of sodium. They heated this for 4 1/2 hours on a water bath under a reflux condenser. The ether solution was ZL/ filtered off and washed with water and finally dried over calcium chloride. They obtained 4 grams of propenyl benzene that coded at esfj-e'zfi at 10 m.m. men they distilled this at ordinary pressure they obtained one drop at 165._16n.; most of remainder came over at 167 -170 . flfter three dastill- -11- ations they obtained three grams at 167u-l7C , which had a specific gravity of .908 at 15 . The fraction at 167 - N 170 they called pure tropyl benzene. Calculated Found. Analysis C 91.5% 91.4% H 8-5% 8.9% A. Klaces (190$) (21) in replying to Kunckell (20) asserted that allyl benzene prepared by the two methods described by him in other papers possessed the following phycial properties: Sp. gr. .9141 at 21;4fl, N 1.5497 at / 12 , 3. Pt. l76l-178 at 754 m.m. He clwined this data ZL/ agrees with Perkins (8) but not with Kunckell. Kloges also claimed this was due to the presence of small amounts of prprogyl benzene in Knnckell's prepar+tion as to the presence of an isomeric hydro carbon. F. Kunckell (1903) (22) in reply to Kloges (21) said that the n-propyl benzene was easily removed from his preparation by fractional distillation. He claimed also that his allyl benzene (?) gave a normal yield of the dibrom.de. n. Tiffeneau (1904) (23) obtained aiiy;_benzehe CuHSCH; H CHqflby the action of allyl bromide on Q Hggpcr. It possessed the follow-n¢ physical data: BPt. 156Ile7'; D -o.9012, N 1.5145. The allyl benzene was characterized // by its trans formation when boiled with alcoholic KOH. to propenyl benzene, CijiCilr—CHCHZThe dibrom derivertive of the latter melted at 70 i E. Chabloy (1907) (24) reduced :i/, cinuamyl alcohol by Naflhyat-80{; This reduction gave a small quantity of phenyl propylene (allyl benzene) which. b0iled at 165 -170 . The dibrom derivative melted at cv‘fi -12- H. Emdi (1911) (25) in reviewing the preparation of propenyl benzene by the reduction of quarteruary clmnnz-hyl arm-'onium salts with sodium amolyam considered the possibility of the \ material so prepared containing allyl benzene or propyl benzene. Tie preparation was divided into four equal parts and each of these decomposed by ozone. In no case was phenyl acetaldehyde or phenyl acetic acid obtained. All four parts gave benzaldehyde or benzoio acid. Hence allyl benzene was not present. 4. Preparation of chloroprcpyl benzene. G. Errors (1) in order to determine the constitution of the chlorcpropyl benzene obtained by the action of chlorine on the boiling hydro carbon, prepared the three alcohols derivably from propyl benzene and converted them into their corresponding chloro derivations. Phenyl progyl alcohol C H CHwCprHGG, when heated in a sealed tube with concentrated hel acid yielded the cheoro derivative Cbfiggflépfitghlgl. He described this compound as a pale yellow liquid which boiled at 219(. hethyl benzyl carbinol CCHgCELCQoEHishen heated with hel acid in a sealed tube 0 yielded QOHECHflChchHlia yellowish linuid which botled at 204 LOVtJWith partial decomposition into allyl benzene. Ethyl phenyl carbinol CHH Chfih‘HLCHawwas converted by gaseous hsl, even at ordinary temperatures into 9,1{3‘03513319313 yellow liquid which boiled at 200 “205.. but with considerable de- composition into "allyl benzene". The qghyC§clchzeEhiwas dis- tinguished from the other two by the readiness with which it reacted with silver aoetdIe yielding the acetyl derivative 0 boiling at 227. -15- P. Genvresse (1895) (2) subjected the vapours of boilinL propyl benzene to the action of a slow current of chlorine in a reflux ap-aratus, until a txernometer placed in the vapour indicated' 0t. The Iroduct w s a chloro- propyl benzene which boiled st 208 :210 with a sliLht decomposition. It did not attack the eyes and had n sp. Lr. of 1.0667. snen he ted with a concentrated solution of K C01 P in a sealed tube at 160 -£CO for 2 days, allyl benzene and a-chloro pro,yl benzene boiling at 205 -20d was obtained. The latter resisted the action of choibut was converted into allyl benzene by KOH and yielded benzcic acid when boiled with alkaline KanLe B. sarck (1912) (5) prepared QLHSCHhCHkCchl, a color- less oil with a penetrating odor. B.Pt. 21922209 or 110 “at 21 m.m. in a 98% yield by diazotizing jrcloro propyl aniline and then reducing with staunous chloride in alkaline solution. J. Prsun and F. Aust (1916) (4) prepared trchloro propyl benzene. B.Pt. 110 at 20 m.m., but the action of phosphorus chloride on the platinum salt of methyl animo—propyl benzene. -14- II. Allylation of Penzene and Format.cn oft/chloro;ropyl in the Presenceof Aluminium Chloride. In reviewing the literature one finds that there has been no attempt to allylate benzene by the condensation of benzene and allyl alcohol. When a mixture of allyl alcohol and benzene was nech— anically stirred during the adniticn of aluminium chloride it was found that ;he temperature rose and that hydro- chloric acid fumes were co,iously evolved. After the evolution of hel Lee had ceased the Fixture was decomposed in finely cracked ice. The benzene yortion was separated from the water portion and the latter extracted with ether. The ether, benzei and allyl alcohol were removed by distillation. The residue when fractionated yielded a distinct fraction from 157”- 152} at ordinars pressure, one at 90.5192.5cat 18 m.n., and one at l48&;1533 at 18 m.m. The first of these fractions is allyl benzene and the second ist/chloro prctyl benzene, while the third ;s Lrobably a m.xture of the chloride and hiLher hydro o rbtns. This will be yrcven in the experi- mental part of this thesis. Exterinental. 1. 2.36 thod . In all the condensat.one that were run: 1 mol (87 Lrs) allyl alcohol, five nols (585 grs.) benzene, and one half mol (99) aluminium chloride were used. The allyl alcohol was mixed with the benzene and cooled to the required testerature by placing an ice solution around it. “he mixture was stirred mechanically. The aluminium chloride was added slowly so that the temperature would not rise. The add tion of the 41 ‘§ -15- aluminium chloride to. N. 1‘10 :31. lo. 16. A. A. 1L. C. 1'. ‘19 “‘1. E". -_ 7'! ““0. 1,. i If ".4". 5“. I ~‘to E. 4. Prepnrnt1cn : netncds. 1. G. 2. P. 3. E. 4. J. 5. Teinann ( ‘-";E(£110r (11:4:- 9 ) E61? 0 Er181¥1 (lfiii Senfter and Tdfel (1 a.) Sex I. -a&- l~'r;-'5 0 5.11531 La '8. Lbrl-‘J o Bender (1L7?) Ber. 19, ole. H. Eerkine (1e77) Jr. Soc. $118.53). lb'c’t‘.) 881'. ll. (710 17, 517. 1:0. .1111. Bar. H. Pelklna’; e1; J. Ste:.r'1c-use (lcfal) Sec. 1., 191;. P. Ceuvreene (iced) Full. (5) 9e; 0 fir]. LuLb (lceq) finn. ~eu, ”Le. (lnLee (lrbu) Ber. b:). ”9:10 3:311 cm”: H. 73 ~ I 1 o ‘ . ‘ I flights (1 e.) Ber. UL. 011. -. .,.1-. 1‘,- -11.. - ; 1 ~.. f11;4c1i\kl.L.L t!!- "'6 . Lt 31:.I Llr (l: bu) {ICJ KJ.1"C8 (JEL\/) P31. \Jr. 0-4;.1'? O Knnehelg (1;Lu) Per. U1, .Ln . TiffBijau (lL‘t) ”$31,. Find. 1 u L . iflrfbo t.;l£.. O uer (lELé) Ber. be, LLC. F. Fittig (1e74) Ann. Chem. fherm. CLIXII Aranuean (1073) Per. VIII, lice. ”hnblnj (1:07) Jr. Chem. Soc. 1, £3. Fmde (1:14) Eer. 44, azeq-e. ** enicro yrclyl Ir") Frrera. Gazzetta 16, 310-325. , Cenvreeee (1893) p1111'. (3) 9 \ ('1 o". . 01419-117. Xerck (1912) Jr. Am. Chem. ?ec. 214$. Praun & E. General refereuces used. rust (1916) rer. 4e, 501-510. -29- Organic Synthesis by H. T. Clark. PIEQCsCxl Hethcds cf CrganLc Chemistry by Getternxnn. Lehebuxk ?er Organieehen-Cnemie_ty V. MULGI wnj P. J1ccbscn. Be ilsfm'gignzbucn. Richters Lex1ccn. Handbcpk of Chen airy & Phyeics. [11... 2 .... L: . r til: up... a.” . p HICHIGQN STQTE UNIV H (an) n I) )1fo 31293006279644 ‘1 H 1..- ,arnuuuv .§.IlI-0 |.4 .l4s.ut .o..‘..-.- ....,.> ---.~.:. ,...,,..; -.w . .‘ul' ',1...,'.ar.. .... n' -;‘.u"--. ..-..“.. 1 col , . n" o _,..-.....r..."' t 1 ' H (a.