a..\. «oh u Cg. . A. C. T. 0. .a..v v. D .r ' -. t. ._ LL .1.— h u.» x .u h L. "if. .V. . FM. | 1" 3 1 g , LIBRARY Michigan State University ;« IV1531_J RETURNING MATERIALS: Place in book drop to LIBRAfiJES remove this checkout from .—:—. your record. FINES Win be charged if book is returned after the date stamped be10w. .‘i’3' Wild}: 2?; a") r d . i; ‘A'I‘u, 7" V: ‘ I 6‘. -: JR?“- Mi I 7 A ‘fl‘UflY C THE Cf“? RTXTIG mm C! AUNIW C‘TMRIDE I"? m CMDMQATIM CF AOMIO {WIN WITH 31mm AV‘D mom. STEWED To THE I'AOMT'! of tho HICHTG W mummm AT. 0 women by IR AWE? ”META Candidate for the has”. of Bachelor of mum. 192 4 lint roiuot Log Aluminum chloride is e. oelgli‘zer has been the eu‘bJeot of a great den of reaearohi the exact nature and mechaniem of its reaction htthie enmity ie not definitely known, although many theoriee are advanced. Iriedel and Crafts (1) are responsible for this general method of condensing organic compoundxr with aluminum chloride as a. eatalyet. The catalytic activitiee in triedel and drafts reaction of the anhydreue aluminum chloride may he etnl ained by the nroduotion of a temporary combination between the chloride and the organic mat erial , Ch. Leas-H + Fun,5 .4, \\c\ + r-‘.\\Q a C 5" the latter would then react with the halide R‘: Q‘o“f¢“\Q‘H- +Hc-O A mixture of methyl-phenyl-carbdncl and five molecules of benzene kept at ten degrees in the presence of 5/10 molecules of alminum chloride gives a 65". yield of diaohenyl ethane together with other products of the continued act ion of the alminmn chloride. Cng- Chumcug i Q. H" -—> gdwcmc “LCQHS‘ -\ who dondensation of Acct ic Anhyiride and Esnsene. tn the oresent experiment the prooort ions used were acetic anhydride one mole, benzene five mole, alumina: chloride one mole] The liquids were stirred by machine, with the gradual addition of the anhydrtda alumimxn chloride. The temperature of the mixture rose rapidly but was kept -- below 60 degrees: twdrcgen chloride was given off. After about half the aluminum chloride had been added, the temperature was more con. stant so that the rest could be added in larger portions] At first the mixture was a golden yellow color, later turning bright green,and finally black. Aft or all the alumina chloride had been added . the orocese took- about two and one~half hours «- the vessel was covered an allowed to stand twenty-four hours. The sub. stance was neared over cracked ice and allowed to decomocse. The acquecus layer was then separated off and extracted with ether. The other was distilled off, the residue added to the oily nortion and distilled. Acetcnhencne sac collected from nfl°hhc12m°. After the acetophenene had been collected, the temnerature rose raoidlv to about 250°. In the first In the first experiment the yield was about 10! but in latter «port-mo about 9, 30¢ yield wee obtained. The acetophenone nae purified by e. rediet illat ion, giving e golden yellow product. In order to prove that thie prodmt was ecetOo phenone it was reduced ee with zinc mm in the following manner: (3) x 1 200 ml of mosey Zinc stood in 400 cc of e of eolut ion of mm, for one hour; the solution was then poured off, 5- gm! of aceto- ohenone nee added and enough F01 (l cert crude to 3 parts H903 so that the zinc wee Just covered. The mixture nee heated under s. reflex counser for 5 hours with the occasional sddit ion of null portione of the diluted R01 to heep the evolution of the hydrogen lively: see cc of diluted ml were added in 311. The cqeaoue portion was extracted with ether, md the ether distilled off; the reeidue was added to the oily portion and distilled at 135° to 133°. The distillate was redietilled and dried. Yield use about 4C! . The production of ccetophenone in thie was hue been not ed by triedel and Crafts in their study of ohthlic and acct ic arydrides (4). condensation of Acetic Anydride and Phenol. Further experiments were made in the condensation of acetic Sll’ydl'ld. with phenol. The pronort ions used were: Acetic snhy iride one mole, Phenol one and one-tenth mole, aluminum chloride one mole. 95,4 gm. of acetic snhydride, 25.9 gm. of phenol suspended in 100 cc of carbon di-sulo- phide, was stirred by machine with a gradual addition of 33.4 gm. of aluminum chloride. A muddy light brown oercipit ate was formed later becoming too thick to stir. After standing in a covered vessel for 24 hours, it was transferred to cracked ice and allowed to decompose/ A white psecinitwe was formed upon decomposition. The acueous was extracted with ether, the ether diet illed off, and the residue distilled «- phenyl acetate distilling over 189° to l"l°. Due to the fact that the carbon di-eulohide portion see not distilled, a yield of only 23 gm. use obtained. The experiment was repeated using .4 mole of alminum chloride, giving a. yield of 31 gm. The experiment we: again repeated with .1 mole aluminum chloride, giving e theoretical yield of 33 gm. When repeated with no elminum chloride 9. yield of 22 331. was obtained. The experiment was repeated with no aluminum chloride not allowing the substance to stand 24 hours, but pouring over cracked ice immediately after stirring. Yield 92 go. The experiment was repeated in the latter manner with .1 mole of aluminum chloride! Yield 20 gm. ~ In all experiments but the first, the carbon di-eulnhide portion. was added and distilled. It is then evident that in order to 9.110?! the slumimzm chloride to have its full catalytic effect, it is necessary to allow the mixture to stand T“. hours. It is also evident that the action between acetic enhydride and phenol will take place to e. considerable degree with- out the aid of e cetalytic agent, but e complete react ion will take place in the presence of .1 of 9. mole of eluninun chloride. In an effort to UNV. that the product attained wee nhenfl acetate and attempt was made to decompose it to ecdiun phenylate and sodium acetate. The enh- et nnoe wee heat ed with e! eodiwn mix-oxide under a. reflex condenser fior eeven been to try to dEolve the oily lifiuid. Hone of it dissolved, showing that this condeneetion product in extremely stable. Corrected for the error due to the length of the thermometer out eide of the flash the boiling point of the substance was found to be 195.40 which is the boiling point of phenyl. acct ate, Conclueiog Acetic anhydride will condense with benzene to give acetophenone in the presence of aluminum chloride. Evidence ie given to ehcw that anhydrous aluminum chloride has It catalytic effect in the condensa- tion of acetic anhydride and phenol. 2132;333:232 Catalysis of Inorganic Chemistry 1{ ”age 54 2. ”age 82 International Congress 0! Applied Chemistry 3, Volume 6, Page 68 Comets: Rendus de !‘ Acadenie dee Sciences 4. 1878 ‘ Volme 86, page 1368 1857 «- Volume 45, l3age 1014 Bullet in de la. Societe Chimique 1879 . Vclmne 32, ”age 61‘ 1881 . Values 35, Page 55 1886 - Velma 46, Page 273 Journal of the Chemical Society of London 1779 - Volme 1880 «- Volume 1882 - VOIMO 1889 «- Volume 1891 «- Volume ”8 3?. as, ea, Page 785 Pages 487 a: 721 lags 115 Page 962 “age 9’71 Sabetier - Reid ‘0 _-—-u__w M M“..- ML: _ 2.13:4... A “4 _ 4. ‘ ‘J?\ Iii- MICHIGAN STATE UNIVERSI H II II"! | hfllmifiliifllTl'es 3 1193 03082 2328