any "3‘ 1 w 3 {“1 R? r.” ’u s n‘ T ‘n’ L UES 5:335?H SNYBER 1 2A.}- ‘R h TEE PRESENCE OF a._:._:::_.:_:::_E.,;_____‘:_E: mm A iguajJfiaflkuawpirtdxa \ . 4 14 F _ CONDENSATION OF THE BUTYL EETHYL ETHYL CAREINOLS WITH PHZNOL IN THE PRESEKCE OF ALUEINUJ CHLORIDE A The-1e Submitted to the Faculty of Michigan State College of Agriculture and Applied Science in Partial fulfillment of the re- quirements for the Master of Science Degree. BY LOUIS JOSEPH SNYDER 1989 w ! Ni) \0 u ‘ ACKNOWLEDGEE EN T To Dr. R. C. Huston. who-e friendly advice and guidance made thie work possible. grateful QCKROWIOGEOQOnteeeeoee eee eeeeeeeee 0 831667 .. h; .. fog-$13.1 1 (If. I. II. III. IV. V. VI. VII. TABLE OF CONTENT Page Introduction 1 Hietoricel 1 Diecueeion 6 ExPerimentcl 11 Tables of Result. 1. Phyeical constants of tort. octanoil 19 2. Condeneatione of tort. octenolo with phonoi 21 3. Phyeicai constants of p-tirt. ootyl phenol! 22 4. Bonzoyl enters 25 5. Alpha naphthyi urethanee 25 6. Phenyl urethnnoc 25 7. Pure tort. octyl benzenoe 30 8. Phy. constante of p-tert. octyl benzene. 31 9. Parachute and surface tension. 31 10. P-nitro-tert. octyl benzeneo 32 11. P-emino-tort. octyl benzenel 32 Summary 53 Bibliography 35 INTRODUCTon In the past. tertiary butyl. tertiary amyl. the tertiary hexyl. the tertiary heptyl. and some of the tertiary octyl phen- ols were prepared in this laboratory. 1’2’3 To further complete this investigation the following four butyl. methyl. ethyl carbinols; 3-methyl. heptanol-S; 3,4 dimethyl. hexanol~43 2.4 dimethyl hexanol-dz 3.2.3 trimethyl pentanol-S were prepared and condensed with phenol in the presence of A1013. Yields ranged from 21.1% to 81.5% of the para-tort. octyl phenol. The bensoyl esters. alpha napthyl urethanes and phenylurethanes were pre- pared and analysed. Three p-tert. octyl benzenes were prepared. The physical constants were obtained and the molecular volumes and parachors were experimentally determined. In the year 1897 Net (4) mentioned the condpnsation of bensyl alcohol and benzene in the presence of aluminum chloride. to form diphenylmethane. In 1916 Huston and Friedeman (5) con- densed benzyl alcohol and benzene in the presence of aluminum chloride. with a 30i'yield of diphenylmethane. They further reported that aromatic secondary alcohols such as benzhydrol. phenyl methyl and phenyl ethyl carbinols also reacted with bensene in the presence of aluminum chloride to give the cor- responding hydrocarbons with good yields. Triphenylcarbinol reacts with benzene in the presence of aluminum chloride to give triphenylmethane and not tetraphenylmethane (6). In 1924 Huston (7) showed that anisole and phenetole acted like benzene in that they condense with benzyl alcohol to give the para sub- stitute! benzyl anieole and phenetole. Huston and Sager (8) condensed allyl alcohol with benzene in the presence of aluminum chloride. The principal product was ellyl bensens. can: on - cases -- 0635 ALOL3 one s CH‘CHB’CGHQ Huston and Wilsey (9) round l.l diphenyl-l-propene was the principal product from the reaction of 1.1 diphenyl ethyl carbincl with benzene, which was a dehydration reaction instead of a condensation. Huston and Gootsmott (10) showed that in condensation rs~ actions with benzene in the presence of aluminum chloride the cycloalkyl carbincls show a progressive increase in activity as the number of carbon attcms of the ring is reduced from six to 1' four. or as the strain on the carbonyl carbon is increased. Likewise. Huston and Hradel (ll) and Huston and Maccaber (13) found that neither diaryl-alkyl carbinols nor dielkyl- aryl carbinols condensed with aluminum chloride. Instead. de- hydration occurred. DimethyloN-butyl carbinol. dimethyl isonbutyl carbinol. and dimethyl sec-butyl carbinol were successfully condensed with benzene to obtain the corresponding alkyl benzenes, but no yield was obtained by condensing dimethyl tort. butyl carbinol with bensene (13). Huston and Hsieh (14) condensed aliphatic alcohols with phenol. The primary alcohols were found not to react at all; the secondary alcohols reacted with difficulty; and the tort. alcohols reacted very readily to form the corresponding alkyl benzenes. Huston and Sculati (15) condensed dimethyl. amyl carbinols with benzene in the presence of aluminum chloride to the corres- ponding tort. octyl benzenes. Huston and Fox (16) condensed tert. butyl and tort. anyl alcohols with benzene in the presence of aluminum chloride. Summagz l. Unsaturated aliphatic primary alcohols. with the double bond adjacent to the hydroxyl carbon. condense with benzene. 8. Primary and secondary aromatic alcohols condense with benzene in the presence of aluminum chloride to form the corres:’ ponding benzene derivatives. 3. Dehydration of carbinole occurs to form the correspond- ing unsaturated hydrocarbon when aliphaticcaromatic alcohols react with benzene. 4. The primary aliphatic alcohols do not condense with benzene, The secondany aliphatic alcohols condense with dif- ficulty. The tert. aliphatic alcohols react very readily to form corresponding alkyl benzenes. CONDEHSATION OF ALCOHOLS WITH PHENOL In 1920 Huston.(l7) discovered that Benzyl Alcohol rs- acted with Phenol in the presence of Aluminum Chloride to give a good yield of p-Benzyl Phenol. Later Huston. Lewis and Gro— tsmut (18) condensed methyl phenyl carbinol with phenol. (yield 33.0%) ethyl phenyl carbinol with Phenol. (yield 27.0%) and benzhydrol with Phenol. (yield 40.0%). Huston. Swarthout and Wardell (19) benzylated o-eresol by condensing benzyl alcohol with o-cresol in the presence of Alum- inum Chloride. The main product was 2-methyl 4-benzyl-phenol. Huston and Lewis (20) condensed p-cresol and benzyl alcohol with Aluminum Chloride. A 35.0£'yield of 2-benzyl. 4-methy1 phenol and a 36.0% yield of 4- methyl 8.6. dibenzyl phenol were obtained. Huston and Stricklsr (21) condensed phenyl prepyl carbinel and a-chlcro-butyl benzene with phenol to yield 4 (sophenyl~ butyl) Phenol. Huston and Newmann (22) reported the condensation of allyl alcohol with Phenol. Huston and Hsieh (23) found that ethyl alcohol. primary propyl and butyl alcohols did not condense with phenol in the presence of aluminum chlofide. Isa-propyl alcohol reacted with Phenol. but the product was not identified. Sec. butyl alcohol did not react with phenol. The tort. aliphatic alcohols were found to condense readily with Phenol to give the para tort. alkyl phenols. Huston and Jackson 8.1. (24) condensed tert. butyl and tert. amyl alcohols with p-oresols in the presence of aluminum chloru ids. Huston and Hedrick (25) condensed some tort. heptyl alco- hols with Phenol. using a mixture of Zinc and Aluminum Chloride as a condensing agent. A small amount of o—tert. butyl phen01 was found, and the principal product being the p-isomer. DISCUSSION 0f the four tertiary octanols prepared, the secondary butyl methyl ethyl carbinol was not recorded in literature, but was prepared by H. F. Hunter (27). Physical constants of the n-butyl. methyl ethyl carbincl, iso-butyl methyl ethyl car- binol, and tort. butyl methyl ethyl carbincl checked with those recorded in literature. Physical constants for sec. butyl methyl ethyl carbinol did not check well with H. F. Hunter's therefore the tertiany octanol was prepared in another manner. The first method was by adding methyl ethyl kctone to sec. butyl magnesium bromide. and hydrolyzing. The second method was by adding sec. butyl methyl ketone to ethyl magnesium bromide. and hydrolyzing. The constants of each tert. carbinol were determined with good checks, and the analysis for carbon and hydrogen also agreed, ' indicating the presence of the actancl. The four tertiary octanols gave good yields when condensed with Phenol in the presence of aluminum chloride. (21.02-81.329 yields. The 3 methyl. 3-p-hydroxyphenylheptane, and 2.2.3 tri- methyl 3-p-hydroxypheny1pentane were prepared by J.E. Anderson (28) 1936. These two p-tert. alkyl phenols were repeated. and 2.4 di- methyl 4-p-hydroxyphenylhexane. and 3.4.dimethyl-4—p-hydrox- phenylhexane were also prepared. 0! these four the 2.2.3 trie methyl~3-p-hydroxyphenylpentane crystalized and was placed on a porus plate. and the melting point taken. H.P.8 61° which corresponded with the melting point given by J. B. Anderson, M.P. 3 57-589. This product was further recrystallized eight times from pet. other and the H.P. became constant on the electric plate at 112°. Later a portion of the phenol pre- pared in 1936 was recrystallized from pet ether. at first dif- ficult to recrystalise and finally when more of the oil disap- peared, the phenol recrystallized fairly well and the H.P. was increased to 108°-110° on an electric plate. The phenylureth- ans was prepared and recrystallized and a constant melting point obtained. The alpha naphthyl urethane could not be pre- pared as there was no alpha naphthyl iso cyanate on hand. In the fractionation of the phenol-tertiary octanol con- densaticne a little tart. octanol was received, then the tem- perature rose rapidly to the condensation product. and the last portion could not be identified. It was a hard polmer- iced product. In the case of the n-butyl methyl ethyl oar~ binol and phenol there was little polymerized product. The iso. and sec. butyl methyl ethyl carbinol with phoned gave between 8-6 gms. of the polymerized product. The tort. butyl methyl ethyl carbincl with phenol did not give any. but a high boiling fraction and more of the tort. octanol was rec- eived than the other three condensations. The alpha naphthal urethanes, phenyl urethanes. and the benzoyl esters were pre- pared for 2-methyl 3-p-hydroxphenylheptane; 2.4 dimethyl~4-p~ hydroxyphenylhexane. 3.4. dimethyl-a-p-hydroxyphenylhexane. The phenyl urethane was prepared from 2,2,3 trimethyl 3-p- hydrcxyphenylpentane. The p~tert. octyl phenols and benzoyl esters were analyzed for carbon and hydrogen. The phenyl urethane and alpha naphthyl urethanes were analyzed for nitrogen. The 2,8,3 trimethyl 3-p-hydrcxphenylpentane was not prepared untill late and sufficient time was not avail- able to analyze this compound for carbon and hydrogen. The para positions of the four tert. octyl groups were determined through syntheses. The tert. butyl methyl ethyl p-hydroxypenylmethane, and the n-butyl methyl ethyl p-hydroxy phenylmethane had been prepared (28). and their structure proven. In this work the four tort. octyl phenols were pre- pared. and the structure of n-butyl methyl ethyl-p-hydroxyph- enylmethane, iso-hutyl methyl ethyl-p-hydroxyphenyl methane. ' and sec. butyl methyl ethyl para-hydroxyphenyl methane were proven by synthesis. First the three p-tert. octyl benzenes 'were prepared and then nitrated according to Malherbs's method (29) to get the p-nitro tort. octylbenzenes. The pore posit- ion of the nitro group was determined by oxidation of the tert. octyl group with dilute nitric acid (1.80), in a sealed tube heated to 130° for several hours in a carius combustion furnace. to p-nitro bensoic acid. h.P. 8 250°. The pnnitro tort. cotyl- benzenes were reduced to the p-amino compounds by means of tin and hydrochloric acid. The three p-tert. octyl phenols thus synthesized were proven to be identical with the phenylurethanes of the phenols from the direct condensations. A small portion of the three para tort. octyl benzenee Iere taken. and the physical constants were determined. Density. re- fractive indices. surface tension, parachar, and molecular vol- ume. The parachors and molecular volumes of these three para tort. octyl benzenes checked well with the calculated parachar and molecular volumes. Analysis of the fractions from the benzeneeoctanol con- densation showed in all cases first a low but not constant ”rection. which when heated with KOH then acidified. and treat- ed with Agnes, showed a large percipitate of silver halide. the probable compound would be the chloride of the original oc- ‘ tanol, This fraction was found just below the boiling point org/f the corresponding tort. octanol. and in each case from 5-10 CC of the original octanol was recovered. In one condensation of benzene and sec. butyl methyl ethyl carbinol. the temperature was held at 15°C and the rocovered tort. octanol was over 3&3. When the benzene condensations eere carried out at the higher temperatures 25° - 53°. a better yield of condensation product was obtained and the percentmre of unreacted octanol use den creased but more high boiling material came over which was not identified. The high building fraction was not a constant boiling liquid. When the temperature was kept low there was little high boiling material and more of the original octanol recovered and more of this unidentified halide. This probably was the chloride of the corresponding octanol. due to the loser boiling point. and halogen content. The four tort. butyl methyl ethyl carbinols condensed with phenol to give the para-tort. octyl phenols. The n-butyl methyl ethyl p-hydroxy-phonylmethane was the highest yield. (81.5%) The ice-butyl methyl ethyl~p-hydroxyphenyl methane was the next 10 highest yield (63.0%). The sec. butyl methyl ethyl-p-hydroxy- phenyl methane was the third highest yield (40.Q€ and the tort. butyl nethvl ethylcp~hydroxylphenyl methane was the lowest. (21.11 yield). The yields of the four petert. octyl phenols corresponded with the amount of branching in the side channe. The n-hutyl methyl ethyl carbinol reacted very well with phenol. The ice- butyl methyl ethyl carbinol gave a somewhat lower yield of the potert. octyl phenol. The sec. butyl ethyl methyl carbinol gave a lower yield than the lee-butyl ethyl methyl cerhinol with phenol. The tert. butyl methyl ethyl carbinol with the most branching gave the lowest yield when condensed with phenol. m ERIMENTAL 11 Nornal bufiyl bromide. ieo butyl bromide, and sec. butyl bromide were prepared by treating the corresponding alodhole with HBr (48%) and concentrated eulfuric acid. Methyl ethyl ketone was a C.P. grade. and dried complete- 1y before ueing. Magnesium (turninge) prepared for Grignerd reactione wee ueed. The phenol was dietilled before ueing. The benzene wee C.P. thicphene-free. The aluminum chloride one of excellent commercial grade. Acetone was distilled and dried before using. The rquent need for eetere. alpha naphbhyl ieocyanete, phenyl ieooyanote, and benzoyl chloride were of the Eaetman Kodak variety. 18 BEEPARATION OF THE FOUR TERTIARY OCTANQEQ 0f the four poeeible butyl. methyl. ethyl. carbinole three are recorded in literature with their physical con- etente. The eecondary butyl. methyl. ethyl carbinol ie not recorded, but hae been prepared by n. F. Hunter (27) ”Senior Theeie'. Phyeical conetante given by Hunter did not check well with the once prepared in thie theaie. co the sec. butyl. methyl. ethyl carbinol wae prepared by two different methode. and the reeult of these two preparatione check well. The two methods are ae followe: methyl, ethyl eeo. butyl carbinol wae prepared by Whit- more'e modification of the grignard reaction. (30) In a five liter. three necked. round—bottom flaek. fitted with an offbe- ient etirrer. reflex condeneer and drOpping funnel. and placed firet a few emall crystale of Iodine and then 98 arena (4 moleQ of fresh. dry Hagneeium turningeg The bottom of the flask ie heated with a email flame until the Iodine commencee to vapor- ize; and ie then allowed to cool while the eec. butyl bromide ie being weighted out; 30 c.c. of a 50% mixture of the wee; butyl bromide and di-ethyl ether ie added to the dry magneeium turninge. If the reaction doee not etart, the bottom of the flaek ie heated with warm water. and the reaction then etarte rapidly; After the reaction had progreeeed for a minute. 200 c.c; of dry di-ethyl ether (dried over sodium) ie added direct- ly to the reaction mixture. The remaining portion of the 4 melee of halide, and 500 c.c. of other ie placed into a drap- ping funnel. and added with etirring. one drop per eecond. The mixture is then allowed to reflux during the halide-ether add- 13 ition. with no external heating being applied. and occeeion- ally cooled with cold water. The stirring ie continued for four hours after the addition of theether-halide solution, and let etand over night. To the eec. butyl magnesium bromide is added a solution of four melee of pure. dry methyl ethyl ketone in an equal volume of anhydrous ether. The remaining procedure is eimilar to that etated above for the preparation of the grignard reagent. The magnesium complex ie decomposed in a four liter erlen- meyer flask with.ice and hydrochloric acid. by the addition of small portions of the magnesium complex to the ice in the erlen- meyer flask. and finally neutralized with hydrochloric acid. The hydrolyzed product is extracted three times with ether. The ether extract is then further neutralized with a sodium carbonate solution and then dried over anhydroue sodium sulfate. The alcohol ie obtained by fractional distillation at reduced pressure after the other has been boiled off on the eteam bath. The yield was (400%) and the constants are B.P. - 1539/741.0sa; GO-Bl/ldmm. D25 . .8348: NB‘D i 1.4338: 40-dL/3mm. Hunter (1) gave the following phyeical constants for eec. butyl methyl ethyl carbinol: 93‘ - .8431 Ne‘ - 1.3880 s.p. 42-44 / 5 mm. DZ‘ ~ .8421 N3‘ - 1.5800 24 D - .8439 N34 - 1.3880 1d The second method of preparing the sec. butyl methyl ethyl carbinol ie: a two liter, three neck flask was fitted with an efficient stirrer. dropping funnell. and reflux con- denser. One mole of magnesium turnings were placed into the flask. and three crystals of Iodine vaporized and let cool. The sec. butyl bromide was mixed with an equal quantity of anhydrous di-ethyl ether. about 25 c.c.. of the halide ether solution was let dr0p into the magnesium burnings and the re- action started as in the other preparation. When the halide- ether solution was all added drop by dr0p the grignard re- agent wae let stand over night. The next day acetyl chloride was not added to the grlgnard as in the usual procedure but the sec. butyl magnesium grignard see added to the (1 mole) of acetyl chloride. After the sec. butyl magnesium bromide was added dr0p by dr0p the reaction was again let stand. hydrolyzed, acidified, and washed thoroughly with sodium carbonate solution. Dried with anhydrous sodium sulfate. the sec. butyl methyl ketone was distilled at 118 C. In the meantine ethyl magnesium bromide was prepared as was the sec. butyl magnesium bromide. the sec. butyl methyl ketone was added to the ethyl magnesium bromide and let stand and the product hydrolyzed as before. The tertiary octanol was distilled under a reduced pressure. and the yield from th. ketona "a“ 61ft Th9 PhYBical constants for this sec. butyl l 4 ”GtHYI ethyl oarbinol are: 5-90 r 158‘/ 740 mm. 59/14mm.40/2.5mm.‘ 1535- .8545 Calculated: c - 73.3495; H - 13.84% ANALYSIS:- ‘JNB 1.4332 Found: C - 73.72%: H - 13.67% 15 The physical constants for the sec. butyl methyl ethyl csrbinel checked well with the physical constants obtained when the sec. butyl methyl ethyl carbinel was prepared from the ethyl methyl ketcne and sec. butyl magnesium bromide, but disagreed with Hunter's to some extent. The normal butyl methyl ethyl carbinol. iseebutyl methyl ethyl carbinol. and sec. butyl methyl ethyl carbinol were all made by the same procedure (30). The tertiary butyl ethyl Lglsx methyl carbinol was prepared by first making Pinacol Hydrate (31), rearrangement of Pinacel Hydrate of Pinacelone. and the addition of an ethyl magnesium bromide grignard to the Pina~ celene. the procedure is discribed below. In a 5 liter round bottom flask fitted with a stepper held- ing a separatory funnel and a reflux condenser with a wide bore (.51n) closed at the top with a calcium chloride tube. are placed 80 gme. of magnesium turninge and 800 c.c. of dry benzene. Through the dropping funnel is added a solution of 90 gms. of mercuric chloride in 400 gms of acetone (dry) carefully at first, then faster as the reaction starts. Sometimes the reaction does not start until after a quantity of acetone has been added. in this case it proceeds very rapidly and the flask must be cooled. When all the 50% solution of acetone and benzene are added the reaction slows down and the flask is heated on a water bath till no further reaction is evident. During this time the magnesium pinacelate swells until it fills the flask about three-quarters full. The flask is removed from the condenser and shakmn until the reaction mass is well broken up. Through the separatory funnel is then added 230 c.c. of water and the reaction mixture is heated another hour. with occasional shak- ing of the flask. The reaction mixture is cooled to about 50° and filtered. The solid is returned to the flask and heat- ed with a fresh 500 c.c. portion of benzene to dissolve any re- maining pinaool. The original filtrate, and the second portion of benzene, after it is filtered from the magnesium hydroxide. are mixed and distilled to one—half the original volume in order to remove the acetone, the remaining benzene solution is treated with 300 c.c. of water and cooled to 10-15°. The pin- acol hydrate separates and after about 30 minutes it is collect- ed en a suction filter and washed with benzene. the pinacel hydrate is air~dried at room temperature (47% yield) M.P. - 46 - 47°. Rearrangement: Pinacel hydrate to pinaoolone in a two liter round bottom flask. fitted with a stepper carrying a drepping funnel and a connection to a condenser set for distillation are placed 750 gms. of G N sulfuric acid and 250 gms pinacol hydrate. The mixture is then distilled until the upper layer of distillate ceases to increase in volume ( 15-20 minutes). The pinaoolone layer in the distillate is separated from the water and the water is returned to the reaction flask. First 60 c.c. of concentrated H2804 is added to the water and then a second 253 gms portion of pinacel hydrate is used. The combined pinaoolone fraction is dried over calcium chloride. filtered and fractionally distilled. The pinaoolone comes over at 1032107°. 17 The pinaoolone is then added with an equal portion of dry di-ethyl ether to ethyl magnesium bromide in a 3 liter 3 neck flask fitted with a stirrer. reflux condenser and dropping funnel. This is added a drop per sec. and let stand over night, hydrolyzed, neutralized and fractionated under a reg/ I ,7 duced P’T‘essure. am. - so / 1.3 mm. yield - 5334'. t/ 18 ngunrxous: I. o 0 (Q? 1' OHS-CHS-C'H-BR + 1‘13 -9 0143- utlg- C'IIC-ngr CH CH 3 3 CH CH , 3,, 3 OHS-CHZ-CrmgBr 3 CHS-C32.c=o-cn3-9ens-CH8-CH-C-Caa-Cu3 CH3 OEgBr ngr ' OH . . , I CH -CH -CH-C-CH -C3 + HOH -» " HBr + on ~03 ~CH-C-CH ~08 . 3 2 , . 2 3 “3° 3 2 . , 2 3 CH CH CH CH 3 3 3 3 CH II. I 3 CH ~CH ~CH-Br + Hg -¢ CH «CH ~CH¢HgBr 3 2 , 3 2 CH 3 CH3 I CL\Q§gBr CH ~CH oCH-mgBr + CH ~COCL -9 CH -C-CH-CH -CH CH 3 CL omgBr \/ CH -c-CH-CH -011 + HOB -» CH -Co-CH.CH -CH + 1. .. BrCL 3 , 2 3 3 , 2 3 g CH CH 3 3 CH ~00-CH-CH «CH + CH -CH -mgBr + HOH --9 3 I 8 3 3 2 CH . 3 on I CH3.CH3.$H.?-CH8-CH3 CHacH5 19 «.583? 83233 on $.33 ooa§owm muwuwoaw non-«nan. mononaaa ub rpoonmozuo ”we". cos-u. mavsnwp sonzuw H-oudcpwu aoauew moo. «snap aoozww eon». Gavan Banyan 093%» candpbow anyww omn6»30u oaruw onnupsow oanw» unqupnow mow. Hom0\.~.m “a. Han-Hao\duo Ba. H‘WO - Humahmo 530 u um .. 0.23 can .. . oaoo Hm #0 EU 2 DI Hohmaau 2 U I Hohflmo N NhOwO OUQOR wrap—op» nosuopbau anon P? 5%}36 as. 50.53.... S. So...~a~a\§o.oaa. uamoafiookam.» as. P? 8o Scuba as. 8o..mmobm as. . waffle}. as. umosuoobm as. u an. .. .mmuo Q own- .mmou Una .. .35 < . 3 mo 2 a «2.: gram 3.3 «Pox mobm ”fl“. H 20 communes: or weary“ ocmeewm 91-132!ij : The N-butyl methyl ethyl carbinol. leoubutyl methyl ethyl carblnol. eec. butyl methyl ethyl carbinol, and tart. butyl methyl ethyl carbinol were prepared and condensed with phenol in the presence of Aluminum Chloride. A typical run in diecribed here.‘ Thirty-two and one-half grams (.25h) of sec. butyl methyl ethyl carbinol and 23.5 grams. (.Bsh) of phenol were treated with 80 6.0. of petroleum ether in a 500 0.8. three necked tleek. fitted with a stirrer and reflux condeneor which car- ried a thermometer reaching to the alcohol phenol mixture, and a bent tube for the outlet of the HCl gee evolved; Then 17 gas. (.lZSM) of A1013 one added to the mixture at such a rate so that the temperature was kept at about 30° centigrade.’ The flask was cooled with ice water when neceeearys After the addition of A1013. the ice water was removed and the stirring continued for tour (4) hours. After the flask was allowed to stand overnight ite contents aeeumed a dark reddish color and was treated with ice and hydrochloric acid; The hydrolyzed product was then extracted four (4) times with ether and dried. The other was removed by distillation; and the residue fraction- ated.' The first fraction collected was phenol. B.P.I3 720/7 me. Then the temperature roee rapidly to 1430-lddo/3 mm; which was the p-tert. octyl phenol. (27.4 gme or 4§£0% yield).4n.ffiflx The reeulte of the remaining condensatione-arenlietodoen”3 table 2 with the percentage yielde. The physical constante‘ Li" and analysis are tabulated on table 3. 81 oozum2m>aHozm ow ammmMemw one>zorm seam emmzpw. ”.03 Q on». O Zodcouw aeonww 33;. 02.32; Zuuopww ecanww canww omndwnoH Hecaccpww song; 03.6w condunow Haoncanwu aevfiww casww anaconda moo. «snap 905.3. 3.33 needpoow moo. unwavn Boonew cnrwu oonu»50~ 605$ e UCGVH 82.3% 3.33. omnupnow owne- am.u am.m aw.u um.m um.m am.u mm.» muenow .QeOWe #Qoom no.0m #QOOW hdoom “400m we». mo. mo. m0. mo. m0. m0. mo. ovuenvbwowu 00. HQ. W on. H4. m on. we. m no. we. m 00. HQ. N on. we. m on. we. m Mum. w encode» «13033... «cussed Hana... wuehawreuaene anaconwwc uuvozwnnoxwa vnenwwneveooe m.a.a»e.«;e~. a-e-p«a auoxwvnenwwnexene NUD&PB.GE H. . batmv-~uw' oncuwvuohwwnoxebo m.nou»eoasww. anvarwu anonkveepwwneuene aeoaoneeanww. aoonnwn ancxamnepwwnexobo ”Om. udvqflsafiwflww. ununnwanoxvaepwut venoeoe mana- awou «0.0 ”0.0 «v.0 No.0 ”0.4 Q.uo «no: m~.mm am.oN m3.a& mm.o& amen“ po.u& Nu.HN mmdea>r nozme>zem ow muflmwan OQHME wmmzormn 0 euno. onenaou manna» om. unaaauwu. mowswwnwoxwo o. muou vuwawwuovnaao - e. .3 m.paa»aoarww. Acv::%n o.mmmm afloxwvuopwpwapro by xi, MN ... ww 0 an, . a.hunpsonsaw. Anvswwo o.m4Hp nudwaWoSKHUmmeo mw, a N m .aaefipaoevew msvu sundoxwv3¢pwwwanawbo w.mwao ~ .V. w . Tax kw . .\ Hommuo 41.9.3 \ \l littu. u ‘ .. . W9“. a m.mu Annmo-paom\u as. ”.mfi\fl BB. p&wm p\.gmu Hamwnwpbn\4 as. wmm \u 85. V‘ 3 x nfl\ 2‘ \; Hamogpbmo\m as. K.‘ a 3”“ ‘x\§ ‘9 F 5g... ...1\ . m.m. - ppmo >anpwnno appan." manna 0 canon.“ #0930 O O onwoc.u wanna onwoc." mocha 0Ho00&m “Hammfiu my." \cm mH.¢Q&» m~.umwu QF 0.“. a" mHomufiu SH: 331 33$ Ho.mmfi no.4mfl uo.mma uo.qum wo.mmfi HO.G4N H0.mmfi 83 PREPARATION OF DEREVATIVES u w Eetere: The Benaoyl eetere were prepared by the Pyridine method (32). A typical run ie described here. One and one half cc. of benzoyl chloride ie edded to a mixture of 1.6 gme. of eec. butyl methyl ethyl-p-hydroxyphen- ylmethane dieeolved in 8 cc. pyridine in a 225 cc. fleck oer- rying a reflux condeneor. The flask was heated with a free flame until the mixture boiled. After heating for two houre in the hood. the flock nae cooled and then filled with water. The eater wee eeparated from the acqueoue layer. and extracted with ether twice. The ether extract wee washed eucceecively w with dilute sulfuric acid. water. dilute eodium bicarbonate. and agdn with water. The other wee then boiled off on the eteam bath. The remaining eater wae then placed into a 25 co. distilling flack. Dietilled under reduced preeeure. When the low boiling materials were distilled ctr. and the temperature roee above 1600/6 mm; the dietillation wee etopped; end the remaining actor that wee in the flask upon cooling immediately oryetellized. and wee recrystallized from Petroleum ether or ethyl alcohol. The results are given in Fig. 01). §§ETHANES The Alpha naphthyl and phenyl urethanee were prepared (33). About 1 gm. of Alpha naphthyl ieooyanate was added to 1 gm. of the p-tert. octyl phenol in a 50 cc. erlenmeyer flack. Then four or five cryetale ct anhydrcue potaeeium carbonate were added to the mixture end a calcium chloride tube wae 24 immediately ineerted. The flack wae heated on the eteam bath with choking for ten minutee. After cooling. the eolid impure urethane eae dieeolved in boiling ligroin. In caee the di-naphthyl urea wee formed. it would be ineoluble in ligroin. The hot ligroin was filtered through a warm auction filter and oryetallized. The crystale then were recryetal- lized from alcohol until the melting point did not increaee. The alpha-naphthyl urethanee of the three fi-tertiery ootyl phenole were eaeily cryetallized, and the resulte are given in Fig. (4). The phenyl urethanee were prepared from the four potert. octyl phenole in the same manner, ueing phenyl ieocyanatee in place of alpha naphthyl ieocyanate. CAUTION: The phenyl ieocyanate is very goieonoue and ehould he handled carefully. The phenyl urethanee crystallized well. and the reeulte are found in fig. (4). AEALYSIS: The Benzoyl eetere were analyeed for Carbon and Hydrogen by Fieher'e hodificetion of the Liebig C ombuetion method (34). The results are tabulated in Fig. (4). The Alpha naphthylurethanee. and the phenyl urethanee were analyzed for Nitrogen content. Allen's hicro KJeldahl apparatue and modification of the Pregyl method were ueed. (35) and (36). The resulte are lieted in Fig. (4). EENZOYL agrees or PfiTERT. OCTYL gnnnogg Octyl ghenol 3 methyl. 3-p-hydroxy- phenylheptane gg‘d lmathyl . "’p"hy- dorxyphenylhexane 3 .“'d incthyl . 4“p-hy- droxyphenylhexane Analzgigi u.P.-122° Calo.; c-ei.29g; H-8.39% Found.; 0-81.139Z; H-8e23% e.P.-123° Calc.; c-e1.eeg} H-6.39% Found.; 0-81.18%}‘H~8.31£ u.P.-125° Calc.: C-Bl.29%; H-8.39% Found.: 0-81.23%; H-8.29¢" ALPHA NAPHTHYL UHETHANES Symethyl. 3-p-hydroxy- phenylheptane 2,4-dimethy1. d-p-hy- droxyphenylhexane 3'4‘d1methy1 . “'p"hy- droxyphenylhexane h.P. - 94° Calculated: Found : u.r. - 90° Calculated: Found : h.P. - 129° Calculated: Found : EHENYL URETHANES Hope "' 104° Calculated: S-m ethyl . 3-p-hyd roxy- phenylheptane 2 .4od imethyl , dup-hy- dorxyphenylhexane 8,4-dimethyl, 4-p-hy- droxyphenylhexane 2.2.3-trimethyl, 3-p- hYdrOXthenylpentane mop. "' Found: 94° Calculated: Found: m.p. ~ 119° Calculated: Found: u.P. - 134° Calculated: Found: N - 4.82% N " 4e289: N - 4.32% N " 4e21,: “' 4.18? d.32% be... j 22 z I 25 26 VROOF OF STRUCTURE The etructure of methyl ethyl N-butyl p-hydroxyphenyl- methane wee proven by preparing the p-tertiary octyl benzene. then nitrating the tort. octyl benzene. The poetion of the Octyl group wee proven by the Cariue oxidation of the nitro tert. octylbenzene to p-nitrobenzoic acid. The p-nitro tert. octyl benzene wee then reduced to the p-amino tert. octyl benzene. and the p-amino tort. Octyl benzene wee diazatized and hydrolyzed to the p-tert. Octyl phenol. This p-tert.0ctyl phenol wee then treated with Phenyl leocyanate and the result- ing urethanee whowed a eimilar melting point. Analyeie and ' mixed melting point ehowed it to be the wame urethane-aw deri~ red directly from the methyl ethyl N-butyl Cerbinol and phenol in the presence of Aluminum Chloride. ; PREPARATION OF THE TERT. OCTYL BENZENES The tort. octyl benzene were prepared by the Huston A1~ uminum Chloride Condeneation hethod (37). A typical run ie described here. A 500 ml. three-necked flask wee fitted with an efficient stirrer. a dropping funnel and a condenser. A thermometer wee introduced into the flash from the condeneer and woe euepended from the letter with a copper wire. A drying tube wee placed at the tap of the condenser. The benzene was introduced into the flask. and the etirrer started. The (.25 mole) of A1613 was added to the benzene. The carbinol wee then added drOp by drop 30 ac to keep the temperature below 30°. The etirring wee 27 continued for tour (4) hours after the addition of the Carbinol. The mixture was then allowed to stand from forty-eight to ninety six hours; then decomposed eith ice and hydrochloric acid. The benzene layer was separated and the acqueoue portion extracted several times with ether. A little HCl was added in extracting with other. to break up the eateroether emulsiun that formed. The combined ether and benzene extracts were washed with dilute sodium carbonate solution to remove any remaining H61. The mixture was dried and the ether distilled off. and the remain- der was fractionally distilled. mannon or THE PGTERT OCTYL BENZENES The nitration of the Octyl benzene was carried out by an adeptation of halherbe's procedure (29). An equal weight of the hydrocarbon was added slowly to fuming nitric acid (Sp.Gr~ -l.51) in a 850 cc. flash. After the first violent reaction is completed the mixture was shaken vigorously and allowed to remain in a water bath at 90° for one hour. being shaken from time to time; Water was poured into the flask, the product was separated, washed with sodium carbonate solution. dried with anhydrous calcium chloride and distilled under reduced pressure; The product foamed during distillation and in the case of the Sec; butyl methyl ethyl phenylmethane the nitro compound decomposed very easily upon heating; In the case of the Isa-butyl methyl ethyl p-nitro phenyl methane was not so easily decomposed as the Sec. butyl methyl ethyl p-nitro phenylmethane. The N-butyl methyl ethyl p-nitro phenylmethane did not show decompostion upon distillation. The results and analysis are tabulated on Fit. (7). EEQQCIION 0E E-NITRO TERT: OCTYL BENZENE Reduction was carried out by means of tin and concentrated H01. A typical run is as follows. (38) Thirty grams of tin are put into a 500 cc. round bottom flask fitted with an air condenser. and a mechanical stirrer. 100 cc. of concentrated HCl is added and then 20 grams of . p-nitro tart. octyl benzene. The mixture is earned under the hood. After two hours it is allowed to cool. treated with a large amount of water and made alkaline with Neon. Then steam distilled from a 2 liter flask. The amino compounds coming over with the steam is salted out, separated, dried with crus- ed. solid K03 and distilled under pressure. gxgnnrgon pr P-Npg‘zo TERT. OCTYL Bmzsng The oxidation was adapted from halherbe's method (89). One gram of the Octyl nitrc compound and 20 cc. of dilute nitric acid ( 1.80 or 6 N.) were sealed in a carius tube. and heated at 1300 in the carriue combustion furnace. After 3 days yellow-white crystals appeared in the tube. The tube was cold when opened. The contents were poured into a 400 cc. beaker of H20“ The crystals were suction filtered and freed from some unchanged nitro compound by washing with a little cooled ether. Then were further recrystallized M.P. 235° to 838°. Mixed h.?. with p-nitro bsnscic acid shame no depression in the melting point. 88 29 W PROS: PaAlgLNO TERT. OCTYL Bmzzzzm A typical diasation is as follows (39). la grams of p-amino tert. octyl benzene are treated with 10 cc. of concentrated 3230‘ in 60 cc. of water. The solid salt formed is suspended in 303 cc. of water. After cooling in an ice bath at 0°, 7.6 grams of sodium nitrite in 32 cc. of eater is added drOp by drOp to the stirred sus- pension from a dropping funnel with a capillary tube attach- ed to the stem. Starch Iodine paper is used to determine -shen enough sodium nitrite has been added. The diazotization mixture is acid throughout the reaction. The diazotised solution is warmed on the steam bath and then steam distilled. The patert. octyl phenol was a liquid ’ae the original one. The Alpha napthylurethane was prepared, as this was the most convenient to prepare. A mixed melting point of this urethane showed no depression with the original phenol from the tort. octanol with phenol in the presence of A1013. The compound was colorless. h.P. 3 94°. QQEDEESATION 0F TEHT. OCTANOLS WITH BENZENE Tort: Octane; N-butyl methyl ethyl carbinol N-butyl methyl ethyl c arbinol N-butyl methyl ethyl carbinol Ideobutyl methyl ethyl carbinol Inc-butyl methyl ethyl carbinol loo-butyl methyl ethyl carbinol Isa-butyl methyl ethyl carbinol Sec. butyl methyl ethyl carbinol Sec. butyl methyl ethyl carbinol Sec. butyl methyl ethyl carbinol seCe bfltyl methyl ethyl carbinol §ensene AlCla Eroduct 97.0 97.0 97.0 97.0 97.0 97.0 97.0 97.0 97.0 97.0 97.0 Es Be 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 Fig. 5 3“m3thy1. 3- phenylheptane 3-methyl. 3“ phenylheptane 3“m°thy1. 5’ phenylheptane 2.4-dimethyl dophenylhex- ane 2,4-dimethyl 4-pheny1hexane 2.4'd1methy1 4-phenylhex ane 2.4-dimethyl 4-phenylhex ans 4~phenylhex ane 3.4cdimethyl 4-phenylheXa ans 4~phenylhexane 3.4-dimethyl 4-phenylhexane Gmsg Yield 29.0 26.0 88.2 14.5 12.0 11.2 12.6 6.5 7.5 8.4 8.0 61.4% $7.65!. 60.3% 28.4% 25.7? 29.2% 5.4% 17.2% 18.9% 18.3% 30 31 PHYSICAL CONSTANTS or PARA TERT. ocrrg:ezmzzsss Para Tert. Octyl Benzene B. E. 3-methyl. e- 120°~121°/17 mm. phenylheptane 8.4-dimethyl 114°-116°/1o mm. 4-phenylhex ans 3,4-dimethyl 1110-1140/10 mm. _4-phenylhex- ane PARACHORSJ SURFACEMIENSION‘dHD i *0'7"":Ap :3 . -vfide-l—L 20° N 1.4932 1..%$. 1.49%9 a Surface D20 Teneion 0.8738 31.95 3 . 0.8755 31.27 .eéfiif 0.8757 31.05 Para tert. Surface Octzl Benzene Tension 3-methyl. 3- 31.95 phenylheptane 2.4-dimethyl 31.27 4-phenylhexane .. ' 3,4—dimethyl 51.o5 4-phenylhexane Molecular Volume gale. Eound. 220.76 218.58 220.76 218.23 920.76 218.12 Figs 6 ._VOLUhE Parachore Edlsi. £2298. 516.43 516.04 515.43 513.42 513.¢3 515.31 EAHA NITRO TERT. OCTZEVBENZENES 3-methyl. 3-p-nitro B.P.-1452-147:/3mm. Calcu: N = 5.89% phenylheptane 171 -173 /11mm. Found: N a 5.72% 2.4-dimethyl. 4-p-nitro B.P.-16?°~163°/9mm. Calou: N 3 5.89% phenylhexane Found::N 3 5.81% 3,4—dimethyl. 4-p—nitro B.F.-159°—60°/9mm. Calcu: N = 5.39% phenylhexane Found: H 3 EAEALAfllNO TERT.VOCTY§_BEEZENES 3-methyl. 3-p-amino B.P.-123°-133°/3mm. Calcu: N a 6.82% phenylheptane Found: N 3 6.74% 2.4 dimethyl.3-p-amino B.P.-l$0°~l$l°/3mm. Galen: N 8 6.82% phenylhexane Found: h s 6.67% 3,4 dimethYI. 3-p-amlno B.f’.-1340*136°/3mm. Calou: I" 3 6.82?! phenylhexane Found: N l 0'33 f‘ I! gUKMARY (1) Sec. butyl methyl ethyl carbinol was not reported in literature and was prepared by two methods. the physical con- stants determined and analysis for carbon and hydrogen deter- mined. (2) The four butyl methyl ethyl carbinols were condensed with phenol in the presence of aluminum chloride to give good yields of 3-methyl. Sépchydroxyphenylheptane, 2.4 dimethyl. 4-p-hydroxypheqylhexane. 3.4odimethyl. 4-p-hydroxyphenylhexane. and 2.2.3-trimethyl. bop-hydroxyphenylpentane. The structures of 3-methyl. 3-p-hydroxypheny1heptene3 2.4 dimethyl, dop-hydroxyphenylhexane and 3.4 dimethyl. 4-p-hydrony- phenylhexane were proven by syntheses. (3) The bensoyl esters. alpha naphthyl urethanes and phenyl urethanes were prepared from 3-mothy1 Sop-hydronyphenylheptane3 2,4 dimethyl, 4-p-hydroxyphenyl hexane, and 3.4 dimethyl. 4-p- hydroxyphenylhexane. and 3,4 dimethyl. 4-p-hydroxyphenylhexane and all derivatites eere solids. (4) The bensoyl esters were analysed for carbon and hydro- gen. The alpha naphthyl urethanes and phenyl urethanes were analysed for nitrogen. (5) N-butyl methyl ethyl carbinol. inc-butyl methyl ethyl carbincls and sec. butyl methyl ethyl carbinols were condensed with Benzene in the presence or Aluminum Chloride to give the corresponding tert. ootyl benzenes. (6) Only the phenyl urethane wee prepared from the 2. 3’.3 trimethyl- ~2-p-hydroxyphenylpentane. (7) The physical constants of theihree p-tert. octyl benzenee were determined. The calculated parachcrs and calculated molecular volume c- hacked with that determined eXperimentally. (a) The p-nitro tert. octyl benzenes, and p-amino tort. octyl benzenee were analyzed-fermearbonwand hydrogen.Antfz / -¢ EIQLIOGRAPHY R.C. Huatan and Te.Y. “Slab. JeAme Chem. §Oc.. L. ‘39 (1936 .B.C. Huston and G.W. Hedrich. ibid. g2, 2001. (1837) ReCe Huston and R.L. Gu110. J.Am. Chem. 800.. 513 69 '71939) Not, Ann. see. 255 (1897) Huston and Griedemann. lafim: Chem Soc.. 38 2527 (1916): ibid. 40. 785 (1918) Davis. Thesis. 1933. Mich. State College. Huston. J.Am. Chem. 800., gg, 8775 (1924) Huston and Sager. M” 33,1955. (1926) Wileey 8.V..Aggeterb Thesis, Mich. State ooiiogo.(1933) Huston and Goetemoot,‘ggég,. §§, 2432. (1934) Hrendel J.R.. heaters Thesis. hich. State College.(1934) Kacowber R.A., masters Thesis. hich. State College.(1935) Binder E.N.. heaters Thesis, Mich. State College.(1935) Heeih T.Y.. Doctort Thesis, hich. State Co1lege.(1935) Sculati J.J.. Eastern Thesis, Rich. State College.(1936) Huston and Fox. Master! Thesis, Mich.$tate College.(1934) , Huston. Janna Chem, Soc.. fig, 2775 (1924) hi Huston. Lewis and Grotemut. g.Am. Chem, 200.. 9.1365 (1924) Huston. Searthcut and harden. lbidu £54484 (1930) Huston and Leela. £333.. £13 2379. (1931) Hueton and Stricklerf J.Am. Chem, Sog..‘§§J 4317.(1953) Newmann P.F. Master! Thesis. Mich. State College (1933( Huston and Heieh T.Y.. Doctors Thesis. Mich. State coiéggg Huston and Jackson H. Master! Thesis. hich. State College) 1937 (30) (31) (32( (ea) (34) (3e) (36) (57) (38) (40) Huston and Hedrick, ggctorh Thesi2.. Eich. State College Agett A. Eastern Thesis Eich. State College (1937) Iunter E.F. Senior Thesis, Eich. State College. (1936) Anderson J.E. Eastern Thesis. Eich. Ctate College (1936) Eelherhe, Ber..1§§, 319. £919) Whitmere and Badertecher, J.Am. Chem. 800.. 55. 1559 (1933) Org. 33-31. F. ~. V01. Einhorn and Holland. Ann.. 501. 95. (1898) Bickel and French. gum. Chem. 803;, 5g, 74?, (1926) Fisher H.L.. Lab. Ean. of Org. Chem., Willey and Sons. New York 243. 293. (1934) Allen, w., Eastern Iheeis. Eich. State College.(1929). Fregyl F.. Quantitative Organic Eiorcanalyeie. 942102,) 1924 IIustun and Friedmann, J .fi.m. Chem . $00., 39, 2587, (1916) Anderson and Eeckman, Lab.Ean. of Org. Chem. 33 (1933) ibid., 45 (1937) 36 .fil 41 Ilmmulmlm um: nnumamlywlymuuln 3 1293 03