., HI I t l «m IH w l H CONDENSATION OF TERT-BL‘TYL ALCOHOL mm RHENOLzN THE PRESENCE OF ANHYDROUS 2ch CHLORIDE "UNDER THIRTY DEGREES TEMPERATURE Thesis for the Degree of M. S. MICHIGAN STATE COLLEGE Albert H. Agett I938 Q CONDENSATION OF TERTGBUTYL ALCOHOL WITH PHENOL IN THE PRESENCE OF ANHYDROUS ZINC CHLORIDE UNDER THIRTY DEGREES TEMPERATURE THESIS Submitted to the Faculty of Michigan State College in partial fulfilment of the requirements for the Qegree Master of Science by Albert H Agett Organic Chemistry 1935 CONDETSATION OF TERT‘BUTYL ALCOHOL WITH PHENOL IN THE PRLSENCE OF AN- HYDROUS ZINC CHLORIDE UNDER THIRTY DEGREES TEMPERATURE tieee+ AC KN O WLE DGMENT The writter takes this Opportunity to express his sincere appreciation for the assistance and guid- ance given by Dr.R.C.Huston. TABLE OF CONTINTS I. Introduction 1. II. Historical 2. III. Discussion 5. IV. Experimental 9. A. Tertiary butyl alcohol with phenol in the presence of zinc chloride and aluminum chloride mixture 9 9. B. Para tertiary butyl phenol with zinc Chloride and aluminum chloride 11. C. Tertiary butyl alcohol with para bromo phenol in the presence of zinc chloride and aluninum chloride. 12. D. Tertiary butyl alcohol and para tertiary phenol in the presence of zinc and aluminum chlorides. 12. . Tertiary butyl alcohol and phenol in presence of zinc chloride 12. F. Tertiary butyl aecohol and phenol in presence of aluminum chloride 13. G. Para Tertiary butyl phenol on the preSence of aluminum chloride. 14. h. Tertiary butyl alcohol with para bromo phenol in the presence of anhydrous aluminum chloride. 14. I. Tertiary butyl alcohol with para tertiary butyl phenol with aluminum chloride 15. J. Para tertiary butyl phenol with tertiary butyl alcohol with zinz chloride. 15. TABLE OF CONTENTS cont. K. Tertiary butyl alcohol with phenol in presence of phosphoric acid. 15. L. Tertiary butyl alcohol with para bromo phenol with phosphoric acid. 16. M. Tertiary butyl bromide and phenol in presence of metallic sodium. 16. N. Bromination of para tert.butyl phenol. l7. 0. Bromination of ortho tert.butyl phenol. 18. v. Tables of Results 20. V1. Summary 23. VII. Bibliography 25. -1- INTRODUCTION In 1916 Huston and Freedman (1) condensed benzyl alcohol and benzene by useing anhydrous aluminum chloride as the condensing agent. In 1920 (2) benzyl alcohol and phenol were condensed by the same method. ln 1929 (3) benzyl alcohol and para-cresol were also condensed by the use of anhydrous aluminum chloride as the condensing agent. in 1934 nuston and Fox (4) condensed tart-butyl and tert-amyl alcohols with benzene.(same method) In 1936 tert-butyl and tert-amyl alcohols were con- densed with phenol.(5). To investigate the use of zinc chloride as a conden- sing agent below thirty degrees temperature the author has attempted to condense tertiary butyl alcohol with phenol. -2- ll HISTORICAL Previous workers have used anhydrous [inc chloride as a condensing agent ans as a catalyst in many instances.In all cases that were investigated an elevated temperature was required to bring about the desired reaction. Liebmann (6) condensed benzyl alcohol with phenol in the presence of anhydrous zinc chloride.The reaction took place rapidly and with a fair yield. Kippernberg (7) brought about the condensation of an alcohol and an amine.nere again an elevated temper- ature was require to bring about the reaction in the presence of anhydrous zinc chloride. Fisher and Roser (8) (9) condensed alcohols with aromatic bases.rhis reaction took place only at elevated temperatures and required a long period of time. Liebermann(10) condensed butyl,benzyl and amyl al- cohols with phenol.Finding also that the higher homolo- gues of phenol failed to give the ferric chloride tests. An elevated temperature was required to initiate the re- action. Merz and Weith (11) also produced diphen,’ ether by the action of anhydrous zinc chloride at 110° on phenol. Auer (12) prepared ethyl phenol by heating absol- ute alcohol (ethyl) and phenol in the presence of an- hydrous zinc chloride. In the crotonization of aldehydes and ketoned Perkins (13) discovered that in a liquid medium acet- aldehyde was converted into crotonaldehyde with zinc chloride at a temperature of 97°. Prieb (l4) condensed benzaldehyde with nitro- methane in the presence of anhydrous zinc chloride to give the nitro derrivatives of phenyl ethylene. Frank and Kohn (15) found that hot para-alde- hyde was converted into mono-molecular aldehydes at 1009. hnownagin (16) acetylated aldehydes in the presen- ce of anhydrous zinc cholride at a very high tempera- ture. Sabateir and Mailhe 917) used zinc chloride as a dehydrating agent,espec1ally in the dehydration of alcohols to give ethers and unsaturated (usuallyo .4- hydrocarbons.lt was also found that it was impossible to use zinc chloride to dehydrate methyl alcohol to give di-methyl ether as gaseous products are produced through a very complicated reaction and a certain am- out of hexamethylbenzene is also formed. The author was unable to find any references in which anhydrous zinc chloride had been used suc- cessflully as a condensing agent at reduced temperatures. - 5- DISCUSSION The condensation of tertiary butyl with phenol was attempted by the author-(l9).No alkylated phenol was isolated by this method.Many different methods were used to bring about this reaction a} the desired temperature but they were all unsuccessfu1.lt was found,however,that by the addition of a small quanity of anhydrous aluminum chloride to the reaction mixture that the zinc chloride was activated and the reaction took place.The percent yield of the para isomer com- pares favorably with that of the aluminum chloride condensations with less gummy material being formed. Upon purifying the para isomer it was noticed that there was a low and a high boiling fraction that could not be any of the original reactants.During the course of the investigation these fractions were proven to be the ortho and the dialkylated phenols which appar- ently exist in equilibrum with the para isomer,but in very small quanities.Attempts were made to produce the ortho and the dialkylated isomers by heating the para isomer in the presence of the aluminum chloride zinc chloride mixture (same amounts as used in condensations) but only the ortho-tertiary butyl phenol was iso- lated.in very small quanities.The dialkylated pro- duct was not obtained in this procedure although it was found in small amounts when tert-butyl alcohol and phenol were condensed in the presence of the zinc chloride aluminum chloride mixture.When the same method was used with aluminum chloride alone (20) both the orflb and the dialkylated phenols were isolated in saall quanities (see tables).When the ortho isomer was treated with aluminum chloride only the para tertiary bytyl phenol could be isolated.The same procedure was also followed useing anhydrous zinc chloride as the equilibrum producing agent,but no ortho or dialkylated phenols were isolated.With phosphoric acid as the equilibrum producing agent no ortho or dialkylated phenols were isolated.how- ever when tertiary butyl alcohol and phenol were condensed in the presence of phosphoric acid (21) a small yield 0! ortho tertiary butyl phenol was found but no dialkylated isomer was isolated . The structure of the alkylated phenols were proven by comparison with those produced by Perkins,Dietzler,and Lundquist(20).In addition -7- Swayzee (22) condensedortho bromo phenol with tert- butyl alcohol useing the aluminum chloride method.The author upon the bromination of the 4-tertiary butyl phenol found that the product formed was identicih in Melting Point and Boiling Point to that of Swayzee's above.A mixed melting point was run with no depression. A bromine determination was made (23) (see tables) on both compounds and close agreement with the theoretical were obtained.One atom of bromine being attached to the ring. A carbon and hydrogen determination (24) was run on the ortho alkylated phenol and the calculated results agree favorably with the theoretical (see tables).The orhto tertiary butyl phenol was then bromine determination made (23).It was also found to have only one atom of Br attached to the ring.Since the melting point and the boiling point of this compound does not agree with that of 2-bromo 4-terthary butyl phenol and since there are no other likely possibilties it can be safely stated that it is 2-tertiary butyl phenol.A1so when the ortho tertiay butyl phenol was treated with aluminum chloride it rearranged almost quantitively to the 4-tertiary butyl phenol. Carbon and hydrogen determinations(24) were made on the 2,4 ditertiary butyl phenol and the calculated re- sults were in agreement with the theoretical (see tables) -8... The author also attempted to alkylate para- bromo phenol with tertiary butyl alchhol in the presence of anhydrous aluminum chdoride,anhydrous zinc chloride and aluminum chloride mixture,and in the presence of phOSphoric acid.I n all three cases no alkylated phenols were recovered.Apparently the ortho position under these conditions is not receptive to alkylation. Tertiary butyl bromide and phenol were condensed in the presence of metallic Sodium (25).The only alkalyated phenol that was isolated was the para isomer and no ortho or dialkalyated were obatained. In order to facilitate the separation of the ortho isomer from the para isomer it was found that it was very conveinient to use a 5% solution of KOH.The para tertiary butyl phenol being soluble and the ortho tertiary butyl phenol insoluble in this solution (see tables). A. EXPERIMENTAL Condensation of Tertiary Butyl Alcohol with Phenol in the Presence of Zinc Chloride and Aluminum Chloride Under Thirty Degrees Temperature. Eighteen and five-tenths grams (.25 mole) or Tertiary butyl alcohol and 23.5 grams (9.25 mole) of phenol were treated with 80 ml. of petroleum ether in a five hundred ml. round bottomed three necked flask equipted with mecury sealed mechanical stirrer,and a condenser which carries both a therometer which reaches into the reaction mixture and a bent tube for the outlet of HCl gas.This apparatus was placed in the hood.Then seventeen grams (.125 mole) of Zinc Chloride was added to the mixture and stirred for one half an hour.Then to this mixture was added three grams of anhydroui aluminum chloride.No rise in temperature was noted.After the addition of the aluminum chloride the stirring was continued for four or five hours.During this time only a very little amount of HCl gas was given off.The contents became a slight pink in color and upon standing overnight became quite dark. at which time it was decomposed with ice water and HCl.The hydrolyzed product was then extracted three times with ether and dried over CaClQ.The ether was removed by distillation and the residue fractionated.The first fraction was collected from 90°-120° @ l4 mm.pressure and was found to be mostly unchanged phenol and ortho tertiary butyl phenol.The second fraction was collected at 1200-135o @ 14 mm. pressure and was found to be almost pure para tert—buyyl phenol.The third fraction was collected at 135°-150° @ 14mm. pressure and was found to be mostly 2,4 ditertiary butyl phenol.These three fractions were purified by fractional distillation.The para tertiary butyl phenol was recrystallized from petroleum ether and was to be a 36% yield .M.P.97.5°;B.P.I20:l22o @ 14 mm. pressure.The ortho tertiary butyl phenol was found to be a slightly yellow colored liquid upon purification.Yield 1.5%;B.P.ll5o-ll7° @ 23 mm pres- sure.The 2,4 ditertiary butyl phenol was purified by fractionation.It crysatllized as a white solid with M.P. 530 and B.P. 1430-1450 @ 23 mm pressure.Less than 1% yield was obtained. ,5 B. -11- Reaction of Para Tertiary Butyl Phenol with Zinc Chloride and Aluminum Chloride. Seventy-five grams (.5 mole) of pure tert butyl phenol (para isomer) were placed in a 500ml. modified Clathen flask fitted with a capillary, thermometer,and a condensing flask.Thirty-four grams of of anhydrous zinc chloride and six grams of anhydrous aluminum chloride was added cautiously to the warmed para tertiary butyl phenol.A small amount of HCl was given off at this time and some iso-butylene.The reaction was carried out under reduced pressure,water pump,and the mixture was heated for three hours at 35 mmwpressure.At the end of the three hour period the heat was gradually in- creased and about twenty grams of phenol was distil- led fractionally from the mixture.A solution made up of five m1. of distilled water and eleven grams of sodium carbonate was then added to the residue and filtered immediately,wnile hot.Upon purification by fractional distillation obtained 54.5 grams (73%) yield of para tertiary butyl phenol M.P. 97°.One and five tenths grams (2%) of 2,4 ditertiary butyl phenol .. 1 O was ohtainea M.P.54 . Condensation of Tertiary Butyl Alcohol with Para Bromo Phenol in the Presence of Anhydrous Zinc Chloride and Aluminum Chloride. The procedure the same as in A above and upon purifiaction obtained 35.5 grams (82%) of para bromo phenol and 5 grams (3%) of an unidentified compound.B.P. 1250_127o @14mmm pressure. Condensation of tertiary Butyl Alcohol and Para Tertiary Butyl Phenol in the Presence Of Zinc Chloride and Aluminum Chloride. The procedure the same as in A above.Upon purification recovered thirty grams (80%0 of para tertiary butyl phenol.No other alkalyated phenol was isolated. Condensation of Tertiary Butyl Alcohol and Phenol in the Presence of Anhydrous Zinc Chloride Under Thirty Degrees Temperature. The procedure the same as in A above with the exception that 17 grams of anhydrous (fused) Zinc Chloride was used as the condensing agent.No alkalyated phenols were isolated.hinety % (21 grams) of para teritary butyl phenol was recovered. Condensation of Tertiary Butyl Alcohol with Phenol in the Presence of Anhydrous Aluminum Chloride. The procedure the same as in A above. Upon purification a 41% yield of para tertiary butyl phenol was obtained.M.P.97.5°; B.P.12OO-l22o @ 14 mm. pressure.The ortho tertiary butyl phenol upon purification was 1.5% yield of a slight yeldow liquid with a b.P.115°~117° e23 mm. pres- sure.The 2,4 ditertiary butyl phenol was purified by fractional distillation and crystallized as a white solid with a M.P. 53.5° and B.P.l43o-1450 @23 mm pressure.A 5 % yield of the pure product was Obtained. -14- Reaction of Para Tertiary Butyl Phenol in the Presence of Anhydrous Aluminum Chloride. The procedure the same as in B above. Thirty-four grams of anhydrous aluminum Chloride was added.A great deal of HCl was evolved at this time.The filtrate was fractionated and obtained 58% (43.5 grams) of para tertiary butyl phenol, five grams (6.6%) of 2,4 ditertiary butyl phenol, two grams (2.6%) of ortho tertiary butyl phenol. Reaction of Tertiary Butyl Alcohol with Para Bromo Phenol in the Presence of Anhydrous Aluminum Chloride. Eighteen and five-tenths grams of(.25mnle) tertiary butyl alcohol and 43.5 grams (.25 mobs) of para bromo phenol was treated with 80 m1. of petroleum ether in a 500 ml. round bottomed three necked flask.The procedure the same as in A above. Upon hydrolysis,extraction,and purification obtain- ed 39 grams of para bromo phenol and no alkalyated product was identified. -15- Condensation of Tertiary Butyl Alcohol and Para Tertiary Butyl Phenol with Anhydrous Aluminum Chloride. The procedure is identical to that in A above.Upon hydrolysis,extraction and purification twenty grams (80%) of para tertiary butyl phenol were recovered.Five grams (1.5%) of 2,4 ditert- iary butyl phenol were obtained M.P.53.5°. Reaction of Para Tertiary Butyl Phenol with Teft. Butyl Alcohol in the presence of Anhydrous Zinc Chloride. The procedure the same as in A above .25 mole of the reactants being used.No dialkalyated phenols were isolated.Twenty-two grams (92%) of para tertiary butyl phenol recovered. Condensation of Tertiary Butyl Alcohol with Phenol in the Presence of Phosphoric Acid. (26) Eighteen and five-tenths grams (.25 mole) of tertiary butyl alcohol and 23.5 grams (.25 mole) of phenol and 200 grams of phosphoric acid were placed injan5OO ml. round bottomed flask fitted with a M. -16).. mecury sealed mechanical stirrer and reflux con- denser.The flask was then placed on the staem bath and heated for eight hours at 1000 with constant ntirring.At the end of this period the phosphoric acid was siphoned off and the residue was fraction- ally distilled.0btained 19 grams (80%0 of para tertiary butyl phenol,M.P. 95°; .5 grams (2%) of 2,4 ditertiary butyl phenol,h.P.53.5°. Condensation of Tertiary Butyl Alcohol with Para Bromo Phenol in the Presence of Phosphoric Acid The procedure the same as in K above. Fourty-three grams of para bromo phenol (.25 mole) was used.Upon purification 95% (41.5 grams) of para bromo phenob was recovered.No alkalyated phenol was obtained. Reaction of Tertiary Butyl Bromide and Phenol in the Presence of Metallic Sodium. Eleven and five-tenths grams of (.5 mole) metallic sodium w as suspended in one hundred mls. of toluene in 500ml. round bottomed three necked flask -17- fitted with a mecury sealed mechanical stirrer and reflux condenser.Fourty-seven grams (.5mole) of phenol were added carefully and the mixture stirrered until the reaction was completed.ihen 68.5 grams (.5 mole) of tertiary butyl bromide added slowly by means of a separatory funne1.The reaction mixture was stirred for six hours and allowed to stand overnight.Upon purification 42.5% (20 grams) of para tertiary butyl phenol were isolated,M.P. 97.5°.No other alkalyated phenob was obtained. Bromination of Para Tertiary Butyl Phenol Twenty-three grams (.25 mole) of para- tertiary butyl phenol was displved in sixty mls of carbon tetra chloride in a two hundred ml. round bottomed three necked f1ask,to which waS‘ fitted a mecury sealed mechanical stirrer,reflux condenser fitted with a therometer reaching below the surface of the liquid,and a separatory funnel.Fourty grams (.25 mole) of Bromine was added by use of the separatory funne1.During the addition of the Bromine the mixture was cooled with an ice and salt mixture and kept around 10°.The mixture was then allowed to come to room temperature with stirring for four he re after the Bromine was -15- added.It was allowed to stand overnight and then it was purified by fractional distillation under reduced pressure.0btained a white crystalline solid,B.P. 121-1230 e lbmm/pressure and M.P. 45° 0. Bromination of Ortho Tertiary Butyl Phenol The procedure indetical to that of N above. Upon purification a wnite colorless solid M.P. 55- 560 and a H.P.145-148° e 14mm. pressure was obtained. 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SOLUBILITY (573mm p-bromo o-tert.butyl phenol insoluble Ortho tert.butyl phenol insoluble 4 o-bromo p-tert.butyl phenol soluble Para tert.butyl phenol soluble l PERCENT CARBON AND HYDROGEN 7% c 9!. c % n 7% H + COMPOUND THEO. CALQ/ THEO. CALC. P-tert.buty1 phenol 80.00 79.85 9.33 10.250 O-tert.buty1 phenol 80.00 78.35 9.33 10.305 4 I 2,4 ditert,tert.butyl phenol 81.55 82.01 10.67 10.790 Pmcmvr 1313.01»an Cale. THEO. COMPOUND % Br )4; Br 3 bromo 4 tert.butyl phenol M.P. 36.38 34.93 2 tert.butyl 4 bromo phenol M.P. 35.85 34.93 l. Tertiary butyl alcohol will not condense in the presence of zinc chloride at or below 30° as with aluminum chloride. 2. Tertiary butyl alcohol and phenol will con- dense in the presence of zinc chloride and alum- inum chloride mixture to give para tertiary butyl phenol,ortho t rtiary butyl phenol,and 2,4 ditert- iary butyl phenol. 3. Ortho and 2,4 ditertiaryhmtyl phenol apparent- ly exist in equilibrum with para tertiary butyl phenol when in the presence of zinc chloride and aluminum chloride mixture.It is possible to isolate them from this reaction mixture. 4. Orhhl tertiary butyl phenol in the presence of aluminum chloride rearranges almost quanitatively to give para tertiary butyl phenol. 5. Para bromo phenol will not condense with tertiary butyl alcohol in the presence of aluminum chloride, zinc chloride,zinc chloride and aluminum chloride mixture,or in the presence of phosphoric acid. .21}— SUMMARX Cont. e. Appare ntly the para position is strongly favored when both the ortho and para pesitions are Open for alkalyation. 7. The ortho alkalyated phenols are insoluble in 5% KOH while the para alkalyated isomers are soluble in this solution. -25- VII BIBLIOGRAPHY (l) Huston and Friednman- J.A.C.S. 38,2527 (1916) (2) Huston and Science_§g__206 (1930) (3) Huston and Lewis— J.A.C.S. 53 2379 (1931) (4) Huston and Fox— Masters Thesis Michigan State College (1934) (5) Huston and Hseih- J.A.C.S..§§'439 (1936? Huston,Lewis and Grotemut-J.A.C.S. 5g 1365 (1927) Huston and Goodemoot-J.A.C.S. 5Q 2434 (1934) Huston and Binder-Master's Thesis Michigan State College (1935) Huston and Anderson- Masters Thesis Michigan State College (1936) Huston and Hedrick-Doctors Thesis Michigan State College (1937) Hustbn and Petty- Master's Thesis Michigan State College (1937) (6) Liebmann- Ber. 15.152 (1888) (7) Kippernborg- Her. 39_ 1140 (1897) (8) Fisher and Hoser- Ann 113_ (1880) (9) Fisher And Hoser— Her 13_674 (1879) (10) Lieberman Ber. 1fl_1842 (1881) (ll) Merz and Weith. Her. 187 (L881) (12) Auer Ber. 11_ 669 (1889) (13) Perkins Her. 15,2804 (1882) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) -26- Prlebs Annalin (1884) .225 325 Frank and Kohn Monatash Chem. 12, 354 (1889) Knoewnagene Annalin 402 111 (1913? Sabatier and Moelhe Bull. Soc. Chem. fill 524 (1907) Dumas and Peligot ann.chem.phys. (2) 58.19 (1835) Author- 8.8. Thesis Michigan State College (1938) Perkins? Dietzler and Lundquest- C.A. g§_ 6532 (1935) U.S. 1,972,599 Tchitchibabine— Comptes Rendues 128 1239 91934) Bull.de la 80c. Chem de France fie ser. 2Pbl Swayzee- Work unfinished- michigan State College (1936) i Gatterman and Weinland,lst ed.p.65-68,l934 Ibid “8 ‘. Huston and Hseih- J.A.C§S. (1936) CHEMISIRY LIB“! 2:598'. '* :11 , (MAIL: 932T. ' A265 118094 Agett A265 118094 Agett Condensation of tert-butyl alcphol with phenol in the preSence of anhydrous zinc .3 chloride under thirty t“ ~ "L. ‘. :.'_"','4-’;/‘ fifi‘dgp‘rz—I’fiflf . . . IIHIHBHIIIHIIIHHHIIIHHIWHMIII'IIHIIIHIIIHHII 31293 02446 7239 _’ “A A‘=_’xfi _._._—i 1.— .—-‘