W I *t W" W i | } MI I ‘ \ KIM ‘ W K 0).; 0—; .4 I (1)0003 ACTION OF TER‘TEARY DEALKY; ARM. CARBENCLS "E-‘ZTH BENZENE LN THE PRESENCE c r A L. L: M 1 A; L) M C LOR 1 1: E ‘ o ‘I‘I l HIG TA mfinju S mmnmmnm W 21!? mm 015914157 m 1 ,‘,: ‘u ', [‘l> o; I "' I v I 3 ..- .' -L. ‘1 .‘ ' .1 E l I w | }‘ ‘ 1 l : z i . I ‘ 4 ‘ ‘ :4 W513: Hum ”0' ”MRS IANQI~°."c" CJ’L: .21.:- fififihw‘k ‘ .. \.-J|..4.-.-'4 l C? TffiTIflRY DI$L7YL AK} CL“ WI n“ C? J...J ":17, '5} 7'». I "' fir”? - ‘- «'- 1.1.“. '-I .‘0 ;.lo I ..-.‘ B THE P? T“.‘T“Yf~p fry-fl? IAS‘AI".T:I Pix-JV. 4.;HJAL VALLAJL“ - I... ACTION CF TCRTIARY DIfiLKYL ARYL CARBIHCLS WITH BTfi7EME IN TNT PR"V7YCE ¢F ALUVINUW CHLCFIDE Thesis Submitted to the Faculty of Hichigan State College In Partial Fulfillment of the Requirements for the Degree of Pastor of Science Department of Chemistry Richard Allen Hacomber August, 1955 AcKWOTlmflfienent The writer w shes to express his sincere anpreciation to Dr. R. C. Huston, whose guidance made possible this work. 33.16512 CCIITEZ‘ITS Organic Synthesis by Condensation Historical Dehydrating Agents Summary Other Methods for Preparing Diaryl Hydrocarbons ExPerimental Materials Condensations A. Dimethylphsuyl Carbinol B. Mothylsthylphenyl Carbinol C. Disthylphenyl Carbinol Analysis Summary Biblicaraphy pugs 10 ll 3351f” airfinesls “Y corner ATICH Condensation when applied to organic chem- istry has been defined as "the union of two or more molecules or parts of the same molecule with or oi hout the elimination of a molecule of water or inorganic acid in which the new molecule is effect- ed between carton atoms". The union referred to may be accowpanied by unsaturetion with these un- saturated groups tending to saturate themselves. According to this condensation may be divided into two parts: those effected by the separation of th elements and those effected by addition. In the scope of this present work both processes may take place, but the former heing the main reaction involved. Condensation by tLe separation of the elements may be divided still further into cata- lytic and dehydrativs reactions. Houover, these may he united again when the reagent used may serve both pur‘oses in the same reaction. The work in- volved here deals mainly with the elimination of watsr, thus, the review of previous work will he liritefl to condensations by dehydration. C :31. .- Meir YET (1?” fi 0*” i? STCTTI CAL Dehydrating Asents l-Culfuric acid 1”ecker (Eer. 15, 2090) condensed m-nitro- benzyl alcohol and benzene to give m-nitrodipheryl- methane. Noelting (Per. 24, 5126) formed tetra- methyltriaminodibhenyltolylmethane from tetramethyl- diaminobenzhydrol and p-toluidine. Gathermann and Kegpert (Ear. 26, 2810) prepared dinitrohenzyltel- name using sulfuric acid. Bistrzycki. Flateau, and Simonis (her. 28, 989; 31, 2712) prepared hydroxydiphenyl acetic lactone andcx- hydroxydi- phenyl acetolactone. Other workers using sulfuric acid are ”eyer and Turster (Ter. 6, 984) and Fritsch (Per. 29, 2500). 2-Zinc chloride Fischer and Roser (Ber. 13, 674) condensed benzhyfirol and aniline hydrochloride to yield awino- triphenylmethane. Liebermann (Ber. 14, 1342) pre- pared butglphenol, angl;henol, and henzylghenol using butql alcohol, aa;l alcohol, and ten2jl al~ cohol with phenol reshectiveiy. Yerz and fierth (Per. 14, 137) prepared diphenylether from phenol. Auer (Ber. 17, 660) condensed ethyl alcohol and -3- phenol to give ethyl phenol. Kippenherg (Ber. 30, 1140) also worked with zinc chloride condensa- tion. 3-?hosphorous pentoxide Hemilian (Ber. 16, 2360) prepared diphenyl p- xylymethene from benzhydrol end p-xylene. Hicheal and Jeenpretre (Ber. 25, 1615) condensed phenyl- hydroxy acetonitrile and benzene to yield diphenyl- ecetonitrile. 4-Acetic acid Khotineki end Petzewitch (Ber. 24. 3104) found that triphenyl cerbinols condensed with pyr- role. Szeki (Acts. R. B, 5) condensed benzhydrol with di and trimethoxyhenzenos in glacial acetic acid solution by passing hydrogen chloride through the solution. 5-2ulfuric and Acetic acid mixture Eeyer end Wureter (Ber. 6, 963) condensed tenzyl alcohol and tenzene to give diphenylmethane. Paterno and Fileti (Gezz. Chim. ital. 5, 381) con- densed benzyl alcohol and phenol. Pistrzycki end fiyr (Per. 57, 65:) condensed diphenyl p-tolylcaro binol with phenol. flohlau and Klopfer (Ber. 52. 2147) condensed benzhydrol and p-quinone in sul- -4- furic acetic acid or in absolute alcohol. 6-?egnesium chloride Yazzare (Gees. Chim. ital. 12. 505) pre- pared propyl m-cresol from propyl alcohol and m- cresol. 7-Stannic chloride hicheal and Jeanpretre (Ber. 25, 1615) condensed phenylhydroxy acetonitrile and mesitylene to give phenyltrinethylphenylecetonitrile. Pistrzychi (Ber. 57, 65?) prepared diphenyl p- tolylnothane from .enshydrol and toluene. -Nydrogen chloride 'Noelting (Ber. 24, 553) prepared p-nitro- dimethy draminodiphonyltolylmethane using hydrogen chloride as a dehydrating agent. Euais (Bull. 1, 517) also used hydrogen chloride as a condensing agent. 9-Aluminum chloride Aluminum chloride came into use as a catalw yet in condensation reactions wit the work of Fridel and Craft (Comp. fiend. 84, 1592). Their work was entirely in.the aliphatic series; they went so for as to say it would not hold for the aromatic series, this, however, was disproven by -5- by later work. Nerz and Weith (Ber. 14, 18?) con- densed phenol with itself using aluminum chloride to form diphenyl ether. Wass (Ber. 15, 1123) ob- tained triphenyl ethane by condensing dichlor- ethyloxide. It is shown here that aluminum chloride acts not only as a catalyst but also as a dehydrat- ing agent. Graebe (Ber. 34, 1778) obtained aniline in small yields by condensing benzene and hydroxyl- amine with the elimination of water. It was reported by Frankforter (J. am. Chem. Soc. 36, 1511: 57, 535) that he and his co- workers had obtained condensation products from chloral, chloral hydrate,and trioxymethylene with the elimination of water by using aluminum chloride. but could not obtain all of the same final products by the Eaeyer or sulfuric acid reaction. Thus he maintained that aluminum chloride acts primarily as a catalyst and only secondary as a dehydrating agent. It was not until Prins in 1927 (Chem. Weekblad 24, 615) that some light was thrown on the mechanism of aluminum chloride condensation. He stated that benzene under the influence of al- uminum chloride acted as if it had a mobile hydrogen and was Comparable at this time to an alcohol. With aluminum chloride a carbon to hydrogen link- age corresponds to an oxygen to hydrogen linkage. The former linkage apparently has undergone ioniza- tion under the influence of aluminum chloride's strong positive ion. Dougherty (J. Am. Chem. Soc. 51, 570) agreed mainly with Prins but more gener- ally believed in an addition compound between ben- Izene and aluminum chloride with the hydrogen only lightly held. Wohl and fierlsporoch (Ber. 64. 1357) were of the same opinion. The dthdrative power of aluminum chloride should not be lost sight of whatever its catalytic action is tonerd aromatic compounds. I Huston and Friedmann (J. Am. Chem. Soc. 33, 2527) were the first to apply aluminum chloride condensation to the aromatic alcohols. They ob- tained diphenylmothane as the principle product ween treating benzyl alcohol with benzene in the presence of aluminum-chloride. The amounts of reagents and temperature of the re- action controlled the yielde of the final product villi“: Q7. and bg-proeLete. 'hon eL"i~cle Lwl r quantities are used, .ho yiolfl of fiijhonylmothone ens much eneller than when a lo rge exeeoe of eon one Lse uoso, while the re on :r; Lrofiuote eo.e corree on: in~l" co eoreceed. The; oxtooded the work 'Jo ‘e. Chem. Soc. 40. 7T5) to the eeconlnry elooIc-ln, methyl phenyl. etILL'l phenjl certinole. an: tcnztyirol obtaining on ccnu e:Lt Lion wit! tenzeLo in them; econco of uLLn l-n c loriIo digh.ualaou no 51 131 lyre efie, and tri- ghanylmethare recrccti"cly. The reaction on too lowing c‘urtion: p...) ‘Q {nzbaflu’u'a «,1 3., Q‘.‘ f k3 rc“ 1 -.— “.3 ‘J'Lo LJ 0-1-3 ".3 . fi*f‘~.~v ”a 9? f - r-I 9f pare-no 71- up . . ~,- 2.x: - '2 .12. m . . + I \ G? 5 a + L ‘4 U U 1.: G 5 2323.; :1 3'. Lao beet yiolfio ' ore o‘LtuiL 101 when tIL 16 n wee a F'fi ‘Tc 1 Jo'ep. ”hen tIo R "Le net‘Vl the roeulte "i e.oecfi I: otter ryiel e than ehsn it Le-e eth"l. It tee 23111.9, cone 1‘ ed “III I. .e 93.12 '1;""~‘.:“’> 11.1.3 a greater raterfiin; effect than the netflgl group. Thie eerie was on once“ by Huston (J. Am. item. 300. 46, H77L) to £319 O“fiw?fio tIon of Len3;l alcohol and phenol to give F~Eont’l“ro :01. CG .5 ”2’33““:3 31:: ring ! 367:5 "L'zce*'4c::(p) +3220 ('3‘? 1.“-..- .. , ‘3‘. . ‘H_ - 3-," ur' ._ 5. ...L'. g .. Lu: mt: U:.J’l {TIL-3d Oil-~dvl ct.s‘3rs Elvra ACE-yaks. 5-334/33 6.118019 and the onetole tore need. Llue the phenolic hyIroxsl sroup presented no m1 ..Iersnce with the introduction of a benzgl groLp into the benzene ring when using aluminum chloride as a dehydrating agent. Attention was then turned to the aliphatic alcohols by Huston and Sager (J. Am. Chem. Soc. 48. 355), who reported at that time that methyl, ethyl, propy , loo-propVI, butyl, iso-butyl, and iso-amyl alcoh 13 would not confienee with benzene in the pre3once of aluminum chloride. Since that time, the field has been again cpo‘.Lod by Heieh (Doctor's Thesis 193 5) who moIifieI the former procedure and condensed iso-proPyl. lee-butyl. and iso-amyl a1- cohole(but not the normal alcohols) with benzene. CTIs I C"3 C330?! 4» CGIIG 19.1313 ’ C t! CH 1- P190 C115 6 W5C 33 H It will be well to note at this time the change in procedure. Reretofore the en‘: ydrous aluminum chlo- ride was aILIed to the mieture of ben7ene and a1- cohol in email amounts, while the mixture was stirred vigorously. The modified procefiure is to ofid the alcohol drOpeiee to the stirred euepension of al- uminum chloride in bennone.' Fox (flootor's Thesis 1331) obte ined corrofinon in; hydrocarbons with ter- tiery Lutyl, tertiary amyl alcohol, dimethyl n- prOpyl, and Cineth yl 130-; :ropyl ce rLirols with :en— zone in the presence of aluminum chloride using this eodified procedure. Binder (”eeter'a Thesis 193 5) prepared several heptyl benzenes with this method. The unsaturated alcohol, ellyl alcohol did give in small "ield the allyl Lenzene when it was condensed with benzene. CE; 2-Cnu 051'.- 36:16 ..".1-:l':" ’ C 2=CZICITBCGH5* H20 It was therefore advanced that the presence of un~ saturation when adjacent to the carbinol carbon in— creased the activity of the alcoholic hydroxyl group. Huston and Bartlet (fiester's Thesis 1926) Condensed phen31 hutyl carbinol and phenol to give p-hyiroxy 1,1 diph-en; lpentene. The large yield of p-hyflroxytripL ee"lwntnune confirms the h} potheeia that unsaturetion of carbon atoms adjacent to the alcoholic group increases the reectivity of the hydroxyl group. 05.735”??? + CQHs .-‘.1Cl‘.r; % CGUc-CHCGHS + H20 4:19 C4119 Huston, Lewis, and drotemut (J0 Am. Chem. Soc. 49, 1365) obtained p-hydroxy 1, l diphenylprOpane. and p-hy droxytriphohrlm tho.ne by conx3n neation. p-Hydroxy ~10- l, 1 digshe n'lhute e was later added to this list by Suston end Stickler (J. Am. Chem. Soc. 55, 4317). The large yield of p-hydroxytrighenylmc have con- firr.s the hypothesis that unseturs tion of cars atoms adjacent to the alcoholic group increases the reactivity of the hydroxyl group. Hradel ("astor's Thesis 1954) reported to have hcd no condens ation of diphen3wl th} 1 or di- phenylprcpyl carhihol with benzene in the presence of aluminum chloride. Instead there was noted marked pulling out of a molecule of Water from the carbincl itself to form an unsaturated hydr c rhon. 5'5 2635,, C61: Jen + 6T76 uni-v13 ? 06::5'02 V 11513 + 112C 2‘! This uns: ureted product is believed to polymerize to a cycle tutsne derivative. Fox (Bachelor's Thesis 1935) reported no conde_3s::ticn of diethyl- yhenyl carbinol. he inability of these latter cartinols to condense is explained by the fact that the OH group is drawn closely to the carbon atom, thereby inhibiting it from being Split off. Sumusry of Alcoholic Condensations Using Aluminum Ch oride l-Cf the aromatic alcohols (primary and ~11» secondary only) only those having the hydroxyl group on the carbon adjacent to the bensene ring will condense with benzene in the presence of aluminum chloride. 2-Cf the mixed tertiary alcohols no con- deneation has been reported instead dehydration took place. B-In the saturated aliphatic series the tertiary carbinols show the greatest condensation with benzene in the presence of aluminum chloride; secondary carbinols next, but the normal carbinols do not condense at all. 4-In the unsaturated aliphatic series Only th se with the unsatureticn adjacent to the carbon having the hydroxyl group show aluminum chloride condensation with benzene. ther Yethods for Preparing Diphenyl Fropane, Butane, and Pentane. ‘gfi-Diphenylpropane has been prepared by Sabatier and Furat (Com. Rand. 155, 328). It was obtained by the condensation of;®d~dichlor0propane and benzene in the presence of aluninum chloride. -12- The Prciuct had the fellomir" n“"