Thesis for tit. Degree. of 1:5: Mic-41m: SKATE. COL Richard} IQCLKO 7937 '0', U. . CONDENSATION OF TERT-BUTYL AND TERT—AMYL ALCOHOLS WITH PARA-ORESOL IN THE PRESENCE OF ALUMINUM CHLORIDE Thesis Submitted to the Faculty of Michigan State College in partial fulfillment of the re- quirements for the degree of Master of Science by Richard Ives Jackson 1957 - "J .y-; 4;, . 1‘ l"? & Cf Acknowledgment To Dr. R. C. Huston, The author wishes to express his thanks for his invaluable aid and advice in the accomplishment of this WOI‘k 0 331-641. II III IV V (4) (5 )Proof of structure Introduction Historical Theoretical Discussion (1) para-ores (2) (5) butyl alc Experimental Table of Contents 01 and tert-amyl alcohol para-cresol and tert-butyl alcohol 2-bromo, 4 methyl phenol and tert- ohol Preparation of derivatives VI Tables of Results VII Summary VIII Bibliography 18 19 25 28 SO -1- I INTRODUCTION In 1916, Huston and Friedeman (l) condensed benzyl alcohol and benzene with the use of anhydrous aluminum chloride as condensing agent. In 1920, Huston (2) condensed benzyl alcohol and phenol. In 1929, Huston and Lewis (5) condensed benzyl alcohol with para-cresol. In 1954, Huston and Fox (4) condensed tert-butyl and tert-amyl alcohols with benzene. In 1956, Huston and Hsieh (5) condensed tert-butyl and tert-amyl alcohols with phenol. To investigage further the use of anhydrous alum- inum chloride as a condensing agent, the author has condensed éert-butyl and tert-amyl alcohols with para-cresol. -2- II HISTORICAL The first mention of the use of anhydrous alumin- um chloride as an agent for the condensation of alcohols and aromatic compounds was by Nef (6) who, in 1897, men- tioned the formation of diphenyl methane from the con- densation of benzyl alcohol and benzene. This condensation was repeated in 1916 by Huston and Friedeman (1). Since that time, Huston and co-work- era (7), using aluminum.dhloride as a condensing agent, have condensed primary and secondary aromatic alcohols with benzene, anisole, phenetole, phenols, and cresols, and tert. aliphatic alcohols with benzene, phenol, cresols, and halogenated phenols. Similar work on the condensation of tert. aliphatic alcohols with phenol in the presence of aluminum chloride has been reported by Tzukervanik and Nazarova (8). Anhydrous aluminum chloride was used as a catalyst for the rearrangement of phenyl and cresyl ethers by Smith (9)(lO) and by Perkins, Dietzler, and Lundquist (11) to condense tert aliphatic halides with phenol and cresols. Of the other condensing agents which have been used to condense tert. aliphatic alcohols with phenols, the following may be mentioned:l Sulphuric acid (70 to 80%) was used by Meyer and Bernhauer (12), Zinc chloride by Liebmann (15), Sen- kowski (l4), and Baur (15), and use was made of phos- phoric acid by Tchitchibabine (16). -5- Tert-butyl and tert-amyl phenyl ethers were rear- ranged by heat alone by Smith (17) and Natelson (18). The preparation of 2 tert-butyl 4 methyl phenol was mentioned by Eaur (15) from the condensation of isobutyl alcohol and p-cresol with the use of zinc chlor- ide as condensing agent. It was definitely prepared by Tchitchibabine (16) from tert-butyl alcohol, p-cresol, and phosphoric acid. He did not prove its structure. Other substituted p-cresols which have been report- ed are: 2 ethyl 4 methyl phenol (l9), 2 propyl 4 methyl phenol (l9), 2 butyl 4 methyl phenol (20), 2 amyl 4 methyl phenol (20), 2 hexyl 4 methyl phenol (20), 2 iso- propyl a methyl phenol (l9)(2l)(22)(25)(24), 2 iso-but- yl 4 methyl phenol (25), 2 sec-butyl 4 methyl phenol (IO), 2 oyCIOpentyl 4 methyl phenol (26)(27), 2 allyl 4 methyl phenol (28)(29), 2 methylallyl 4 methyl phenol (25), 2 pentenyl 4 methyl phenol (50), 2 phenylallyl 4 methyl phenol (51), 2 benzyl & methyl phenol (50)(5), 2 cinnamyl 4 methyl phenol (29)(50), and 5 methyl 6 hydroxy triphenyl methane. -4- III THEORETICAL Alkylation 2f Para Substitutgg Phenols. The low yields resulting from the condensations of tart-butyl and tert-amyl alcohols with para-cresol in the presence of aluminum chloride are in accord with the results from practically all of the attempts at conden- sation of para substituted phenols with tart-aliphatic alcohols or halides. In this laboratory, with the use of aluminum chlor- ide as condensing agent, several para substituted phenols were condensed with tart-butyl alcohol. In Table I the results are tabulated along with results from the con- densation of the isomeric ortho substituted phenols placed there for the purpose of comparison. Meyer and Bernhauer (12) attempted to alkylate para- cresol without success. The condensing agent used was sul- phuric acid. (70-80%). Agett (55) attempted to condense p-bromo phenol with tert-butyl alcohol using a mixture of zinc and alum- inum chlorides (Zn012-17g., AlCls-O.5 to 5.0g.) as con- densing agent. A very small yield of a substance, unident- ified as yet, resulted. Also, he was unable to condense p-tert-butyl phenol with tert-butyl alcohol by this method. Tchitchibabine (16), using phosphoric acid as con- densing agent, condensed p-cresol and tert-butyl alcohol (yield 75%) and o-cresol and tart-butyl alcohol (yield 78%) 7'70 -l-‘ :3 wwnrr‘vo'“ r3; tit» Irt‘cnl“, I’WO‘T’evn‘P, ‘9 “- ”it“. ‘":""" 11° .,.' L" '» . ~‘ -« .., '.'—~ .~ g , .\ A -- ..I _ - ”i ,\ A ~ TH ‘.*. . "‘5 ~- strrct“vc t TQTiII c tart—Wut*l wuufiwl. 'rofl RVIUPlfie i , , 1 -. ‘ n w_ -. J- _ _._~ ‘ _. ‘ _‘ , ‘ ‘R , A _a 77 ., LW'V I‘ J_ _« ’_\ Unsoriwov 1° 0:, L are is r'w30< tw we loll tn,. b.9 ' J..- J (v .-+_‘... f +11», 1.11.‘ h -~ '1 ' ‘ “‘ ". ‘ "1 “‘fi , ,N L _ f) 2' if.) :‘P‘I‘IT: (IT-1.1411!“ L, -‘ L‘s—g .1. S r- 7 .J . H1 (7.. .JF .3 L,- t- -1- I p l — C 5‘ctt (#3) wrs U“ablc to co ”ease tart—h“t71 also 01 others and substitute“ alkyl 5 enols ”stelso” (if) an 'este . J!" ._ ”Lu. Y! . ‘ - w. , ..2 4. J— . x, 3* e wv’t*oi” '.*il"o:a_‘ 1 i “1‘8 , ”\c 9‘) 91,. "‘1’“, “in r! - ~.‘~ (V J“ ".1 J‘s} J" («‘7‘- T 7~ <1 I 1 (‘V P‘ “,‘arx 4" h '7 a" n ,3 , -—~ 7‘) (W 71' 1h "j m\ ' f‘ ‘- i" " I ll x) V {: I - [1‘ V K 9' I. 7 P ‘4‘ ,H 1.7 (J t V ”7' .L e V. ' =‘ X T LW 2' J'_~ f " A ‘ ‘7‘.) . ‘ " I’ ‘7' . I - ‘\‘ u“0 draw 0. ISO-fiyo' 1 Jxlfl 1 ..I v- , 4-7 ‘ .— . a ' x . ._ . -- - "‘5: — - J- r - ' at oer" - , ru» ?0 :1“ ri 3%)-1 I“ 91? ')'.)~'ft ‘ a ' t*, ‘s:"1 ’1 C! 3‘" '3 ”—1 -. 71 fir; - (\r‘ -11\(“‘. \n mam '11’1 1 D. 7‘ J“ m an ‘ w‘ '1‘ ‘3 ;- b. F (- - f . ' - 1 _. v i ( ~. *. -- - .. l '1 O- (J F (“I - I fi‘r‘a" ’i‘1'fl ". (“IL/‘1 I" \VI’OI’ "“7" (‘7':4‘I7t r.) ‘1 ’1! my '3- ' m .)"\’\ 1". (~ ,- *3 .1 . , f, , ‘L‘. i .' j_)t: - ., O_ 4],. : I ‘1)». fly“! [j _l_ ' I. (31‘-.. I} i ) 1 n L} _l L) L I a 2.1- 3 . .1 , .2-“ " J- 3 ‘J l r . h r' Pa ‘ x (V W (1 r «W b »-u-'~_ L. (,6? his c,'.,tltrte,t 3%» ”at I.) -\ ‘q‘r -. ~’ L“ TNfiI A‘F’f‘ Fl ."’) as" .1 ~~"~./'-‘ .—,,.. 'q ‘ J" -- “1 ,7» w J, ‘- J- .‘j Melting, i,“ on 6.1. , u-"-.-'. Lyman l1} 1,. ]__ (M?- O ‘.,- 1-7“? LP» .x-‘ . .- -" - .'._1 “q .0 7 ‘1 - w - 1| . V . ,—\ a I q _ (‘1 srx \ -’-\ 4 "T - ,——l-. ’. - - - 7“ ’ , ._ - , - _ t:ti In two «rescues 0; an} discs aid.-l ! c 10?} C at -. TOO i1) 1C($”3., teifibdritfl_(r“lorfi’hc ani ‘2 cool, -+» erwtt'ol- -5- ecular amounts, give the following equilibrium mixture: (by weight) 10.5% phenol, 7012% p-tert-butyl phenol, 1.2% o-tert-butyl phenol, and 9.1% 2,4 ditert-butyl phenol. From phenol, tert-amyl chloride, and aluminum chloride at 100°C, they report 0.14% (by weight) o-tert-amyl phenol, 5.0% 2,4 ditert—amyl phenol, the remainder being p-tert- amyl phenol. These last results are strikingly in agree- ment with those of Hatelson (18) from the rearrangement of tert-amyl phenyl ether. That there is also an almost exclusive formation of the para isomer when tert-alkyl phenols are prepared by other methods has been demonstrated in the following cas- es. Using aluminum chloride as condensing agent, Huston and Hsieh (5) and Huston and Hedrick (7) condensed phenol with tert-butyl, tert-amyl, tert-hexyl, and tert-heptyl alcohols. They reported only the p-tert-alkyl phenols. Using a mixture of zinc and aluminum chlorides as condensing agent, Agett (55) found only a minute yield of o-tert-butyl phenol from the condensation of tort-butyl alcohol and phenol, the principal product being the para isomer. The tert-amyl phenol prepared by Liebmann (15) with the use of zinc chloride as condensing agent was proved by Anschutz and Beckerhoff (54) to be p-tert-amyl phenol. -7- Tchitchibabine's Investigations. Considerable work was done by Tchitchibabire (16) on the condensation of alcohols and phenols with the use of phosphoric acid as condensing agent. Included in this investigations were the following condensations: tert-butyl alcohol and m-cresol tart-butyl alcohol and o-cresol tert-butyl alcohol and p-cresol He did not report the condensation of tart-butyl alcohol with phenol. To the tart-butyl m-cresol, he assigned the structure, 5 methyl, 6 tort-butyl phenol, He proved its structure by conversion to the methyl ether and comparison of its dinitro derivative with the dinitro derivative of 5 methyl 6 tort-butyl anisole which had been previously prepared and identified (55). The tert-butyl m-cresol prepared by Tchitchibabine is not appreciable soluble in 20% NaOH solution. To the tert-butyl o-cresol, by analoqy to the tert-butyl m-cresol, he assigned the structure 2 methyl 6 tert-butyl phenol, It is soluble in 20% NaOH solution. Tchitchibabine stated further that, in the condensat— ions of tert-aliphatic alcohols with phenols in the presence of phOSphoric acid (sp. g. 1.7 to 1.87), the principal product, at moderate temperatures, contains the alkyl group in the position ortho to the hyiroxyl; only insignificant quantities of the para isomer are produced. -8- Even at high temperatures the para isomer is never ob- tained in very great quantities. The author wishes to present proof that the above statement by Tchitchibabine is at least in part erroneous. The author wishes to present also very good indications, but not proof, that the structure of the tert-butyl o- cresol prepared by the use of phosphoric acid is 2 methyl 4 tert-butyl phenol, not 2 methyl, 6 tert-butyl phenol. Agett (55) prepared tert-butyl phenol from phenol, tert-butyl alcohol, and phosphoric acid following the methods used by Tchitchibabine. The principal product (yield, 70 to 80% of the theoretical) boiled at 1229-1250 /14mm. and melted at 950. By mixed melting points it was proved to be p-tert-butyl phenol. Less than 5% of the theoretical yield boiled within the range reported for o-tert-butyl phenol by Perkins, Dietzler, and Lundquist (11). He thus demonstrated that where both of the ortho postions and the para position are open, the tert-butyl group exhibits a decided preference for the position para' to the hydroxyl. Concerning the structure of the tart-butyl o-cresol prepared with the use of phosphoric acid, the follwwing evidence is presented. Considering the fact that p-tert-butyl phenol and 2 methyl, 4 tert-amyl phenol are soluble in alkali solution and that o-tert-butyl phenol, 2,4 ditert-butyl phenol, and -9- 2 tert-butyl 4 methyl phenol are not, it would seem that insolubility in alkali solution is characteristic of tert alkyl phenols only when the alkyl group is ortho to the hydroxyl. It is therfore significant that the tert-butyl o-cresol prepared by Tchitchibabine is soluble in 20% NaOH solution. Huston and Petty (7), using aluminum.chloride, con- densed tert-butyl and tert-amyl alcohols with opcresol. The tert-amyl o-cresol was proved to have the structure 2 methyl 4 tert-amyl phenol by comparison of its bromin- ation product with the product from the condensation of tert-amyl alcohol and 2 methyl, 6 bromo phenol. 0H 0H CH : CH O’ 1‘ a CHIC ACaHy C H3-C'Ca H: ’ éH, OH CH CH; Br 0H CH3 3' 3 + CaHrC-OH ——> + HOH CH3 CHyG'CaHJ' CH3 The two bromo tert-amyl o-cresols were proved to identical by the mixed metling point of their diphenyl urethanes. -10- The author prepared tert-amyl o-cresol by the pro- cedure of Tchitchibabine. By the melting point of its aryloxy acetic acid, it was proved to be identical with the 2 methyl 4 tert-ampl phenol prepared by Huston and Petty. I In conclusion, it may be safely stated that, in general, the introduction of a tert. alkyl group into the ring of a para substituted phenol is accomplished with more difficulty than the corresponding alkylation of the isomeric ortho substituted phenol. It may also be stated that, with a few exceptions, in the introduction of a tert. alkyl group into a phenol in which both ortho and para positions are not substituted, the position para to the hydroxyl is strongly favored. -11.. .onaaoano ESCHEHHw Sufi: soapmmCopcoom Homong Anny upowm nun codpsmsoocoo oz Annapupaop Handpuuaopnm .112. \ Honone Hanan . - Anny on m.o wmm nuaop w nzxrfihm Haydn vamp HonoSQ oann o Anny upomm In: cofipmmcoucoo oz ampsnlpAop Homoza oanQuc a Honcho Hanan a .,n -. I Abv cwEoHoo pom upaop ¢ omoaflo m Hzpsp upon Honor: OLOHSO 0 Any cwfioaoo It: soapsmconcoo oz Hmunpnpaop. Honcho oaoanoun Abv mppom won Hocosdeahpsn ampsnnuaop Homoaouo upon a Hesposm Hononq finance m I and aspspupnop m thSpupeop Homoeo-o mOB¢GHBmfi>FH QQWHWV Bonomm domooqfi dozmmm *H mqm¢9 -12- Anna psome w Honond thdpuunopno Hosooaw thdpnuaop Honcho 3---: was a... ..- a , - Rom Hononm ahpdpupaopum Hoflooaw thgpupaop Hocono - Hocosa Hmpdfl (I mmw upnop m Hmmnoa m Honooaw Hmfiwuuaop Homoaono mfiv onnmpeflopHLoe Hocosa Hmnpoe m mmb ampsnupaopw Ho£00Hw ampsnuuaop acmopono pal oneneparooanoe I Hocoso Hashes e . . Ammv upom< nun mCOHumeoocoo o: Hoflooam Handpupaou HonoSQ oannuo Ufiom capoflamozm Spas mcofipwmcopsoo Anny upow< m0 Hocona ampsn (I, ll . H0C®£Q uptouao 4.m Honooao Hapsp-ptop Hepspuptmp-o Amwv ppmu< mm ooagapcooaca UGSOQEOO Honooaw thfipupaop Hocond 0509910 I.nooahosu‘assasawmIuqmIamamInuAalmqdAqmuqudaquIIIIIIIIIIIIIIIIIIlIIIIIII. HH mqmme -15- IV DISCUSSION I Tort-amyl alcohol and para cresol. The condensation of tert-amyl alcohol and p-cresol, which results in the formation of 2 tert-amyl 4 methyl phenol, may be represented by the equation: OH H: OH H, 9 - + CaHs'QgH AL—Ci Oven?” + W“ C 3 CH3 CH3 Two different procedures were used for this condensation. By the first procedure, anhydrous aluminum chloride was suSpended with stirring in petroleum ether and a solution of the alcohol and cresol was added drOpwise. In each case, by this procedure, the yield of 2 tert-amyl 4 methyl phenol was small (not exceeding 7% of the theor- etical ) and a large amount of tarry residue was formed. Where an excess of the alcohol or aluminum chloride or both was used, a larger percentage of the tarry residue and a smaller percentage of the product resulted. No differences in yields were noticed when the reaction was carried out at 5° to 10° or at 50° to 55°. By the second procedure, the cresol and alcohol were placed in a flask and dry aluminum chloride was added over a period of 50 minutes to 2 hours. By this procedure, higher yields of the product were obtained. (maximum yield 12.5%) It was found that by increasing the molecular equivalent of the p-cresol from 1 to 1%, a noticeable increase in yield resulted. A p-cresol resulted i not practically no yield. In the second, the m of In two condene n put -14- further increase in the (0 - 1 r. (WWI 7 ' '\ L (ann‘fislhlib U- ‘light increase in yield. “tions, the reaction mixture, during a pale blue jelly-like mess, the nature investigated. more petrole The yield w 2 tert-amyl 4 y\I l" l/ s - enolic, but .1... KW . Vt audition Ff the aluminum chloride, solidified, forn- Wthfi W58 In the first condensation, there was A AC- -.w h V was broken um ether and aluminum chloride were f; I re considerably reduced. methyl pheno' is a clear viecuous oil A\s'-\f~ .r“ . q‘ 1' ,—»-‘I t~ r. , r' . ,. ,n . 0331ch To Lived"; “181.3"; fit, CLOTH, ‘«".’).‘lCh failed to crystallize when placed in an ice-salt mixture or when left in the refrigerator for more than It boil~ "t lseo to 1300/14nn. and st 2450 to .— :2 month. 473/739.im7 Analysed by combustion, it was found to have the following composition: 0:30.975, H210.813, W . ‘_\ \ ‘AL II ~ . I‘ 3‘ . g) ,' ‘ “lien u‘on the lorfluifl C: .J Tert—butyl alcohol and para creeo . } OH CH3 9“! L 3 7" CHs‘COH jig-e” CH: CH ffi H; CH3 —r“ .1 r-7r- “I "Qro (f—ai) C CC‘CH’ + HOH l L -15- Condensations of tert—butyl alcohol and p-cresol were, with the following exception, run by a procedure analogous to the second procedure used for tert-amyl alcohol and p-cresol. Due to the tendency of the condensation mixtures to solidify, they were cooled in an ice-water bath which al- lowed more rapid addition of the aluminum chloride. This procedure seemed to assist in the prevention of solidif- ication and the lowering of the yield which accompanied it. The molar proportions of the alcohol and cresol which produced the maximum yields were found to be the same as in the condensations with tert-amyl aloohol,11anely: p- cresol 1% to 2, alcohol 1. 2 tert—butyl 4 methyl phenol, upon purification, crystallizes readily. When crystallized from petroleum ether by very slow evaporation of the ether, the crystals closely resemble those of menthol in general appearance. The odor is indistinguishable from that of 2 tert-amyl 4 methyl phenol. 2 tert-butyl 4 methyl phenol melts at 50.0-50.4OC?,, boils at 117° to 1190/15.5mm. and at 2520 to 254°/740.2mm. It was found by combustion to have the following composition: C=80.29%, H-9.87%, 0-9.84% The theoretical, based upon the formula C11H16O, is: 0:80.4ofl, H=9.ol%, 0-9.73%. Separation of the p-cresol and the alkylated cresol was accomplished by fractional distillation. However, -15- advantage may be taken of the insolubility of the two alkylated cresols in 10% NaOH solution in their separation. The reported yield from the condensation of tert- butyl alcohol and p-cresol by Tchitchibabine (16) by the use of phosphoric acid as condensing agent, was 75% and the melting point (of the unrecrystallized product (?) ) was reported to be 44°C. To compare the two products and to investigate the differences in melting points, the condensation was re- peated by use of phosphoric acid (sp. g. 1.7). The yield was 75%, m.p. 50.00-50.400. Tert-amyl alcohol and p-cresol were also condensed by use of phosphoric acid. The yield of 2 tert-amvl 4 methyl phenol was 65%. From the high boiling fractions from the condensat- ions of tert-butyl alcohol and p-cresol, were separated 10.5g. of material boiling at 124° to l52°/14mm., about two thirds of which crystallized at room temperature when seeded with crystals of 2 tert-butyl 4 methyl phenol. An attempt was made to condense 2 tert-butyl 4 methyl phenol with tert-butyl alcohol by use of phOSphoric acid, No condensation resulted. Therefore it was concluded that tert-butyl alcohol and 2 tert-butyl 4 methyl phenol do not condense in the presence of either phosphoric acid or aluminum chloride. III 2 bromo 4 methyl phenol and tert-butyl alcohol. As a further investigation of the directing influence of the hydroxyl group and of the use of aluminum chloride as a condensing agent, attempts were made to condense 2 bromo 4 methyl phenol with tert-butyl alcohol. No conden- sation resulted. Moreover, no condensation resulted from using phosphoric acid as the condensing agent. For purposes of comparison, 2 tert-butyl 4 methyl phenol was brominated, chlororform being used as the 0H CH: ("{st ' Br ~CH O 065:4: ‘F Br; .4 (3 CH3 3 + H Br CH: CH: medium. The theoretical amount of bromine reacted readily, but a fewldrops in excess produced a distinctly red color. 2 tert-butyl 4 methyl 6 bromo phenol is a colorless viscuous liquid boiling at 155° to l54°/14.5mm. At atmos- pheric pressure (74l.8mr:1.), it boils at 255° to 2570mm slight decomposition. Analysis for bromine by the Carius method gave 55.05%. The theoretical is 52.92fl. 918- IV) Preparation of derivatives. The aryloxy acetic acids were prepared from 2 tert- butyl 4 methyl phenol and 2 tert- amyl 4 methyl phenol by the method of Hoelsch (57). This method was modified some- what due to the slight solubility of the two compounds in 55% HaOH solution. Due to the slight solubility of the aryloxy acetic acids in hot water, they were crystallized from 50% ethyl alcohol. 2 tert-butyl 4 methyl phenoxy acetic acid melts at 129.00-129.50C. Neutralization equivalent calculated 222.14. Found 227.6. 2 tert-amyl 4 methyl phenoxy acetic acid melts at 125.50-126.0°. Neutralization equivalent calculated 256.16. Found 258.0. The p-toluene sulphonic esters, 5,5 dinitro benzoyl esters, and diphenyl urethanes were formed in very small yiells, if any, and could not be separated from the orig- inal compounds. Phenyl iso-cyanate gave no evidence of reaction with either of the compounds. 7' .. ‘Jf’ ...? 1..-..77 .1-“ ‘1 iI‘C‘Oi C1,; ScP-lC are. An gflrtempt TKLS red<>tn: groiwsiii“ strrnfinire (j? the ethymnrwls, 2 tert-butyl 4 netle phenol {JuiiB'tert-agvl 4; nettqu if era 1 Cf* tin: PCiKYthfl: H CH3 . 0H CH! R . 6- 6’3 -+'CFhIr Afl£l#>- CH) 4” HI (3:! ~ J‘ J- l‘".‘ J——,.. ,. 1" ‘7 r “. "‘~.- ,'1 I, v oo,. o-tert-oao l j_cacl were ,rcoaer as a ty- - -5. to - ., - : . , :- .i .n-,- a, 4-..- , 1..“ P, .3. predict oi tLC preparatitn oi p-tert-oao l thelcl and v ‘1“ allowed ta react with netnil iodide aha anhrdr n inum chloride. The result Wis an almost quantitative re- arrangement of the o-tert-but; rhenol to p-tert-butfl ‘plier1c]_. Lrevicuslp, several attempts were m&fi0 to prepare }~ n ,J H :3 fl (\ w V3; 2 pa til 1' H. C 1' w (IV‘ U3 1- 1"" ' -- .‘v . ‘ J- -"\ r ""Vv .1\ K ‘\ ‘. C‘bSTt‘Ufltgl 84m O-U03t-Jdrl ynOhClS 13-, ‘,_‘ . "" .f ‘ l... .. _ 7.4-7- ," ()(‘ .V- ._ '_ 2. .47 (l) 14““: tile (J-..— o: -...53 Q: 1 1 Chair LA. (CJL ) , 1.7.1 !.QC;.L71I)81J (iii. 5]. '- V ,_ ‘- “ . " ’9, ‘i‘ 4 ‘ “ -'.- ‘1 .“ ‘.‘ "a -' '7 vv . '4" ‘ l". " “, ~ 1‘ ‘ ' 4‘ “ ‘ p;atic :a ides in, be CC as sea mitt sod um WMGHClao€ to -" - .. ‘ ° . - n ...-e“ - - t: .. :. -,'- ~. lorm t;e ortwo elotituted picnols. some er, it has ictn» that when tert-butfl brcwide vii soliun n enclate in tol- uene are allowed to react, g-tert-butrl wheucl is the principhl groouct. j a ‘ ' "" :"' " ‘\ (V - i F‘ ' ‘\ ’ 7" '1 ' J" :1 " "'7 "' (2) an attehct Mtg we to pre aie ie the o—tert- (v. alx;l phenols by the following scheme 0? reaction: CHr -CH3 H3508 CH3 'CHa N 0.. CH: ' f4.0 9H: CH —cH: HNOa CHI ' 50,0H H: CH3 NH; Cl) [2141071250 AND Hyprotyszo Tcrt-aurl and tert-sutyl benzenes liCthioii of‘ TsitYrvjooliJi', ad}; L 6'1 Y." 3.. t tures )- 2? 5030” CH: CH,- -CH: N01 #5:! + HCL § A, *1 211.1 :3 t o n. ._,_, 'H -- l L 11 C were f \ \J .2 sulgnuric asiu (be fuglflf r K steam (iouo to 1730). ‘V‘IFEI’G 01:1.(1 1.23 '1': (f‘ .- 4- ".1. ore a neltiNf zoic acid. had replaced the sulohonic acid aroun in the position para 1“) 1 r '1 I} ben3(ic t} a) and ElllfiL i‘C)Ii ( lin' and, after the poured into water, r“ steam distilled The resultin“ e vetFC' (, «al 301418 irerwa fut; 4 methyl :ficnul wrs :roved tc an analogous Jenner. The Iracticn isclatei we .. ‘ ,3 4- 1.. . ,J,_ 1.! ,2.1.1. V. , .... e , I." -... \-~/‘ , - Provca to as iujvticsl ti 'Lthrj product r