;:.,:,, ,:,g,:,g,_: _ . .1 ‘. 1'. ... _. a magi LIBRAR Y Michigan‘ Stags University (.. / Al, I V4. . M CONDENSATION OF PHENYL BUTYL CARBINOL WITH PHENOL IN THE PRESENCE OF ALUMINUM CHLORIDE THESIS Submitted to the Faculty of Michigan State College in Partial Fulfillment of the Requirements for the Degree of Master of Science. By Jeffrey Hobart Bartlett 1986 I"! ‘J;_. Acknowledgements I wish at this time to express my appreciation of the help and kindly assist- ance given by Professor R. C. Huston during the progress of this work. 83.1606 TABLE OF CONTENTS I. Review of Previous Work 1. Condensation as Used in Organic Syntheses ...............................1 2. Dehydrating Agents Used on Alcohols and Aromatic Compounds ......................3 3. Aluminum Chloride as a Dehydrating Agent ooaooooooooooo.o00.00000000000000005 II, Experimental 1 1. Preparation of Phenylbutyloarbinol';.....7 2. Preparation of Parahydroxydiphenyl- butylmethane 9 3. Investigation of Eeterification of Parahydroxydiphenylbutylmethane ........13 III. Summary OOOOOOOOOOOOOIOCOOOOO9.0.0.00000000015 Iv. Bibliography OOOOOOOOOOOOOOOOOOOOOOOOI0.0.0.16 -1— QQW .13 13.3551 1:1 REM MS he . Condensation as applied to organic chemistry is defined by Cohen as “the union of two or more organic molecules or parts of the same molecule (with or without elimination of component elements) in which the new com- bination is effected between carbon atoms". As further eXplanation, it may be said that the union referred to is usud ly accompanied by unsaturation and consequently there would be a tendency for the unsaturated groups to saturate themselves. Such processes may therefore be divided into two groups: those which takeplace by sep- aration of elements and those which take place by addit- ion. In the present work we shall only be concerned with the first group. The process of condensation by separation ofthe elements may be further divided into catalytic and de- hydrative reactions. This is only a rough division, how- ever for the reagent used may serve both purposes in the same reaction. Since this work has to do only with the elimination of water taking place in the main reaction, this discussion shall be confined to a review of condensation by dehydration. I In the condensation of aromatic alcohols with aromatic bases, Fischer (Ann. 206, 85, 1880) maintains that the reaction takes place with the elimination of water, the _ product formed being a combination of one mol of the alcohol with one mol of the base; and that the relative position of the amino or basic group to the combining carbon is always the same, viz., l : 4. -3.— When the condensation is effected with phenol and aromatic alcohols, it is reasonable to assume that the relative position of the OH group is likewise in the l = 4 position with respect to the entering radical, from the fact that the 0H grain: directs to the same position as the NH, group. Substantiat ion of the above assumMion is offer- ed by Holleman (Chem. Rev. 1, 202, 1934) in which he main- tains that the substituents already present in the benzene ring which direct entering substituents to the para or ortho position do so with varying velocities which are as follows: 03> NH.) I > 13:) 01> CH, thus showing that the 0H has the strongest directing in- fluence to the para or ortho position. .211” w 9.1 Estimating Agents Head 2n We and m o 9.2mm. Dehydrating agents used before 1914 to bring about condensation of the alcohols with aromatic coupounds were chiefly the following: zinc chloride, sulfuric acid, acetic acid, absolute alcohol, magnesium chloride, hydrof chloric acid and phosphoric anhydride. A resume of the literature in which each of the above are used is as follows: Zflng_Chloridg. l. Benzhydrol + Anilinehydrochloride —-> Aminotri- phenylmethane (Fischer and Roser, Ber. 13,674, 1879). 8. (a) Butyl alcohol 4- Phenol -——>- Butyl phenol (b) Amyl alcohol + Phenol -—-—>v Amyl phenol (c) Benzyl alcohol + Phenol ~9— Benzyl phenol (Liebmann, Ber. 14, 1842, 1881. He also found the higher homolOgues of phenol failed to give the ferric chloride test). 3. Phenol -—-> Diphenylether (“an and Weith, Ber. 187, 1881). 4. Absolute alcohol + Phenol -—-* Ethyl phenol (Auer. Ber. 17, 669, 1884). Sulfur io Acid 1. Metanitrob enzylalcohol + benzene H ‘ . Metanitrodiphenylmethane (Becker, Ber. 15, 2090, 1882). 2. Tetramethyldiaminobenzhydrol + Paratoluidine _—> Tetramethyltriaminodiphenyltolylmethane (Noelting, Ber. 24, 3186, 1891). ' 3. Paranitrobenzylic alcohol + Paranitrotoluene -——> Dinitrobenzyltoluene (Gattermann and KOppert, Ber. 28, 2810, 1893). 4. Phenol + Mandelic acid -—-> Hydroxydiphenylaoetic lactone (Bistrzycki and hates, Ber. 28, 989, 1895). 5. Phenol + Mandelonitrile —-> Alphahydroxydiphenyl- acetolactone (Bistrzycki and Simonis, Ber. 31, 3813,1898). mm 1914 and 8.9.9.118 8.9.19. missed) 1. Benzyl alcohol 4- Benzene ___>- Diphenylmethane (Meyer and Wurster, Ber. 6, 963, 1873). 3. Benzyl alcohol + Phenol ->- Benzylphenol (Paterno and Fileti, Gazz. Chin. ital. 5, 381, 1875). -4— 3. Diphenylparatolylcarbinol + Phenol -———>- Para- hydroxytriphenylparatolylmethane (Bistrzycki and Gyr, Ber. 37, 655, 1904). 4. Mohlau and Klopfer (Ber. :52, 2147, 1899) were also successful in condensing benzhydrols with a para— quinone or derivative of the same with the mixture of sul- furic and acetic acids or in absolute alcohol. We M119. 1. Benzhydrol + Paraxylene ———>~ Diphenylparaxyly— methane (Hemilian, Ber. 16, 2360, 1886). 3. Phenylhydroxyacetonitrile + Benzene ~—>— Diphenyl- aoetonitrile (Michael and Jeanpretre, Ber. 25, 1615, 1898) Magnesium 911192.199. 1. PrOpyl alcohol + Metacresol —-5;r Propylmetracresol. (Mazzara, Gazz. 12, 505, 1882) annals 911123.95. l. Phenylhydrcxyacetcnitrile + Mesitylene —> Phenyl- trimethylphenylacetonitrile (Michael and Jeanpretre, Ber. 85, 1615, 1892). B. Benzhydrcl + Toluene Mes—- Diphenylparatclyl- methane (Bistrzycki, Ber. 37, 659, 1904). £119.11 6 £9.19. 1. Khotinski and Patzewitch (Ber. 84, 3104, 1909) found that the triphenylcarbinols of the type triphenylcar- binol condense with pyrrole. But this same reaction does not hold true for prunary or secondary alcohols. 2. Szeki (Acta. R. 2, 5, 1925) found that benzhydrol and various other aromatic carbincls condense readily with die and trimethoxybenzenes in glacial acetic acid solution under the influence of hydrOgen chloride. Hydrochloric Acid. 1. Paranitrodimethyldiaminobenzhydrol + Metatoluidine _—_> ParanitrodMethyldiaminodiphenyltolylmethane (Hoelt- ing, Ber. 24, 553, 1891). 2. Suais also did a meager amount of work in which hydrochloric acid was used as a condensing agent. (Bull. 1, 517, 1897). W W as a W m Aiminum/‘ilel‘falét any best known in the Friedel- crafts reaction, although even there its mechanism is not thoroughly understood. It is also used as a dehydrating agent in reactions in which there is a subsequent splitting out of water. Merz and Weith (Ber. 14, 187, 1881) used aluminum chloride on phenol and obtained a mixture of compounds of which benzene, diphenylether andmethylenediphenyloxide were the chief constituents. Waas (Ber. 15, 1138, 1883) condensed dichlorethyl oxide with benzene using the same agent obtained triphenylethane. He maintains that such a reaction is due tothe action of the aluminum chloride con- verting the dichlorethyloxide into monochloraldehyde, which reacting with benzene, forms first monochlorodiphenylethsne. -6— If such is the case the aluminum chloride undoubtedly serves not only as a catalyst, but also as a dehydrating agent. Graebe (Ber. 34, 1778, 1901) was able to obtain aniline by using hydroxylamine and benzene in the presence of aluminum chloride, but the percentage yield was small. Jaubert (Compt. Rend. 132, 41, 1901) carried out similar experiments using the hydrochloride of hydroxylamine, but he likewise obtained a rather poor yield. In 1914' Frankforter and co-workers reported in a series of articles ( J. Am. Chem. Soc. 36, 1511, 1529; 37, 385) the results of their investigations in which they used aluminum chloride as a condensing agent. They were success- ful in condensing chloral, chloral hydrate, bromal and tri- oxymethylene on various organic compounds in which there was an elimination of water. Many of the compounds Irepared could not be obtained by the Baeyer or sulfuric acid react- ion. Consequently he maintains that the aluminum chloride acts as a catalyst, at the same time, however, playing the part of a simple dehydrating agent. Aromatic alcohols had not been condensed with aromatic compounds in the pesence of aluminum chloride until Huston and Friedeman began their investigations in 1916 (J. Am. Chem. Soc. 38, 2527). They prepared diphenylmethane with anthracene as a by—product from benzene and benzyl alcohol in the presence of aluminum chloride. It was found that the amounts of reagents used and the temperature at which the reaction took place influenced the final yield. Later (J. Am. Chem. Soc. 40, 785) they‘extended their -7- experiments to secondary alcohols with benzene and aluminum chloride, using methyl phenyl carbinol, ethyl phenyl car- binol and benzhydrol, obtaining diphenyl methane, diphenyl propane and triphenyl methane respectively. The reaction with the methyl phenyl carbinol took place much more smooth- ly and gave a higher percentage yield ofthe condensation product than did the ethyl phenyl carbinol. Consequently they concluded that the ethyl group probably had a greater retarding effect than the methyl group. In 1934 Huston con- densed benzyl alcohol with phenol in the presence of aluminum chloride, obtaining parabenzyl phenol. The methyl and ethyl others were prepared in good yield by condensing benzyl alcohol with anisole and phenetol. It was noticeable that the phenolic hydroxyl group did not interfere with the sub- stitution of the benzyl group in the benzene ring. generation 21; maujzlflarbinsl By the reaction of benzaldehyde on an alkyl mag- nesium halide secondary alcohols can conveniently be pre- mred if heat is not applied. In the preparation of phenyl butyl carbinol the following reagents were used: Normal butyl bromide . . . . . . . . . ..... . . . 3 mOIB Magnesium............. ........... ....3.8 " Benzaldehyde 3.7 ' There was obtained 1.9 mole of the oarbinoi, making a 70% yield of the theoretical. The technique employed in the Grignard reaction was briefly as follows: the magnesium ribbon with a crystal of iodine was placed in a five liter balloon flask and dur- _ 8 _ ing the course of three or four hours the butyl bromide dissolved.in ether was added. Care was taken to have all reagents thoroughly dry. The butyl magnesium bromide was refluxed on a water bath for an hour to insure com- plete reaction. It was then cooled in an ice mixture and the benzaldehyde dissolved in ether was added during a period of one and one-half’hours. The flask was removed from the ice mixture and.allowed to stand at room temperat- ure (33°) for three quarters of an hour, after which the complex compound was decomposed with ice and hydrochloric acid, extracted with ether and the extract distilled tn vacuum. The yield on second distillation gave 380 grams coming over 94°—96° under 6 mm., most of it boiling at 94°—95°. The distillate from 90°-100° at 6 mma made a total of 305 grams. The'boiling point of the carbincl corresponds very closely to that obtained by Fourneau and co-workers (.Anales Soc. espan. fie. quin. 18, 323, 1920) of 120°- 1350 under 13 mm. and also that of Vernimmen (Bull. soc. chim. Belg. 33, 96, 1924) of 123° under 12 mm. It may be well to mention at this time that Hess and.Rheinboldt (Ber. 54, 2043, 1931) found that when an alkyl magnesium.halide was refluxed with benzaldehyde in ether or benzene, gave a.mixture of compounds due to the reducing action of the Grignard reagent. Benzyl alcohol was in every case one of the products formed. To avoid the side reducing action when alkyl magnesium halides (methyl excluded) are used heat should.nct be applied to the reaction mixture. -9... An analysis was made on the rroduct obtained from butyl magnesium bromide and benzaldehyde on refluxing with the following results: Substance, 0.1808 : 00., 0.5303; 820, 0.1444. Calculated for 0113160 : C, 80.43; H, 9.88. Found: C,80.03; 3. 8.94. An analysis was also made on the product without being refluxed, but alload to stand at room temperature for three quarters of an hour. substance, 0.1317 : 00., 0.3582; 3.0, 0.1089. Calculated for 0115160" 0, 80.43; H, 9.82. Found: C, 80.30; H. 9.83. With such results we can be reasonably certain that there is a reaction of some kind when heat is applied to the complex compound of benzaldehyde with butyl magnesium. bromide. This was further made evident from the fact that some benzylphenol was isolated in the condensation product. Condensation 91 Phony; butyl cgbinol 11th Phenol m the. Presence sf Aluminum 911.19.111.91. 1. Method In the two condensations that were made the follow- ing proportions were used: ‘ Phenyl butyl carbinol .............. 1 mol Phenol ..................... ..... ... 1.3 ' Aluminum chloride .................. .5 ' PetI‘OliO ether e....o......e...o.eoo1500000 ...10- The quantities that were actually used, how- ever, were: Phenyl butyl carbinol . . . . . . . . . . . . 50 grams Phenol ........... ..... ........... 34.4 ' Aluminum chloride 80.35 " Petrolic ether ................... 450 cc. During the course of the first condensation the oarbinol and phenol were suspended in petrolic ether and stirred constantly with a.mechanical stirrer. Aluminum chloride was added in small portions over a period of two hours at such a rate. that one third was added the first hour and the remainder the second hour. At the end of an hour and a half the temperature had risen to 30°. There was also a noticeable change in color, the milky appearance of the first few'minutes giving way to a violet color, which deepened to a red on first noticeable evolution of hydrogenchloridc. Approximately two thirds of the aluminum chloride had.been added at this point. on further addit- ion, the temperature gradually fell and by the time all of the chloride had been added the temperature had fallen to 34°. The stirring of the mixture was continued for one and one half hours after the final addition of the chloride, much hydrogen chloride being driven off in the meantime. When the stirring was discontinued the intermediate compound of a thick gummy consistency settled to the bottom. After standing overnight (31 hours) the mixture was decomposed with ice and a small quantity of hydrochloric acid,and ex- tracted with ether. The ether extract was then fractionally _ 11 _ distilled. A second condensation was carried out using the same quantities and same technique as before, with the ex- ception that the mixture was stirred for two and one half hours after the final addition of the aluminum chloride. 1. The distillation fractions were as follows: Up to 125° (petrolic ether and water) Up to 135° at 6 mm., ................ 1250 - 1850 at 8 mm., 1850 - 2300 at 8 mm., ....OOOOOOOOOOO 0.000000000000000 Up to 125° 00.000... Up to 185° at 6 mm., ssseeeseeeeosess 135° - 185° at 6 mms’ essseseesoeesss 185° - 2300 at 8 mm., discarded 14 grams 36 " 36 " discarded 14 grams 38 " 34 " The corresponding fractions from the above distillations were combined and redistilled.yielding: UptolKW..n.n.n.u.u.u.n.n. 170° - 195° (recovered phenol) ...... UP to 1600 at 6 mm., ................ 160° - 1800 at 6 mm., 1800 - 3300 at 6 mm., ............... The fraction 180° - 3300 at 6 mm., ated three more times yielding: Up to 1800 at 6 mm., .. soasesssoossoo 180° - 3450 at 6 mm., Regime ......OOOOOOOOOOCO ......... O. 3 grams 33 P 10 P 66 s 50 m was fract ion- 16 grams 36 * B ' .. 12 .. The combined fractions 160° - 13800 at 6 mm., making a total of 83 grams were subjected to two more distillations, yielding: Up to 1690 at 5mm., 34 grams 169° - 1730 at 5 mm., .............. 33 " 1730 - 180° at 5 mm., .............. 16 " An analysis was made on the fraction 169° - 1730 at 5 mm., with the following results: Substance, 0.1463 : C0,, 0.4583; H,0, 0.1806. Calculated for 0173300 : C, 84.95; H, 8.39. Found: C, 85.46; H, 8.31. A five gram portion of the fraction 1730 - 180° at 5 mm., was purified as follows: It was dissolved in Claissen's solution, (Arm. 443, 210, 1923.) and shaken out twice with petrolic ether to remove any others that may has been formed in the condensation. The solution was then acidified and extracted with ethyl ether. After evaporat- ion of the solvents,nc residue remained from the petrolic ether, and that from the ethyl ether was carried thru two distillat ions; the second time practically the whole quantity ( 5 grams ) came over 170° - 171° at 5 mm. Cu cooling the product, it solidified to a mass of paraffin-like consistency. Small portions of the solid obtained above were used to seed the other fractions of the compound, but only two responded, 169° - 172° and 172° — 180° at 5 mm. Several attempts were made at recrystallization, but no solvait that was used seemed to be suit able. Furthermore, the product responds very slowly to being dried between filter papers, and when brought to room temperature began to melt. There may be a possibility that it has no definite crystalline form, due to the comparatively long paraffin chain that is attached. If we use that portion of the product which solidified as the compound sought for; we would then have a theoretical yield cf 33%, which is somewhat in keeping with yields Obtained by other condensations of a similar nature in which aluminum dlloride was used as a condensing agent. Attemptstfiatanifiastion 1. Schotten-Baumann Reaction. As a.means of recOgnizing compounds containing an OH group, the benzoyl derivative is often prepared.- In.the attempt at its preparation,one gram of the product was used with the calculated amount of potassium hydroxide and.benzoyl chloride. Other attempts were made by varying the quantities of the benzoyl chloride and the potassium hydroxide, but none of the trials were successful. The chief cause of the difficulty was likely the fact that the product would not dissolve in either potassium or sodium hydroxide. 3. Carbonyl or Urethan Derivative. An attempt was also made to recOgnize the OH group by preparing the urethan according to the technique employed by Fourneau and co—workers (Anales. soc. eepan. fie. quim. 18, 333, 1930) but no reaction took place and the pro- duct was recovered. 3. Qualitative tests. The product failed to give the ferric chloride ..u— test for phenols, which might be expected from higher phenols of that type. It did, however, respond readily to the test for phenols described by Moir ( J. S. African Chem. Inst. 5, 8, 1933). -1 5... Summary 1. Phenol reacts with phenyl butyl carbinol in the presence of aluminum chloride to produce parahydroxy— diphenylbutylmethane according to the following reaction: OH . + A1011, + H30 H 0.11 008 8.890 OH H 9H 3. Attempt to prepare the benzoyl derivative and the urethan were unsuccessful. BIBLIOGRAPHY I. Condensation in Organic Syntheses. 1. Cohen, Organic Chemistry, Vol. I. 2. Fischer, Ann. 306, 85 (1880). 3. Holleman, Chem. Rev. L 202 (1924). II. Dehydrating Agents. 1. Zinc Chloride as a Dehydrating Agent. 1. Fischer and Roser, Ber. 13. 874 (1879). 2. Liebmann, Ber. 14, 1842 (1881). 3. More and Weith, Ber. 14.. 187 (1881). 4. Auer, Ber. 11, 889 (1884). 3. Sulfuric Acid. 1. Becker, Ber. 15, 2090 (1882). 2. Noelting, Ber. 34,, 3128 (1891). 3. Cattermann and Koppert, Ber. 88, 2810 (1893). 4. Bistrzycki and Flatau, Ber. 28, 989 (1895). 5. Bistrzyoki and Simonis, Ber. 31, 2812 (1898). 3. Sulfuric Acid and Acetic Acid (Mixed). 1. Meyer and Wureter, Ber. .5. 983 (1873). 3. Paterno and Fileti, Gazz. Chim. ital. EL 381 (1875). 3. Bistrzycki and Gyr, Ber. 31, 855 (1904). 4. Mohlau and Kloppert, Ber. 33, 3147 (1899). 4. Phosphoric Anhydride. 1. Hemilian, Ber. 16.. 2380 (1888). 3. Michael and Jeanpretre, Ber. 35, 1615 (1893). 5. Hagnesium.Chloride. 1. Mazzara, Gazz. 1_3_, 505 (1883). ...-17... 6. Stannic Chloride. 1. Michael and Jeanpretre, Ber. 35,1615 (1893). 2. Bistrzycki, Ber. 31, 859 (1905). 7. Acetic Acid. 1. Khotinski and.Patzewitch, Ber. 85,3104 (1909). 2. Szeki, Acta. R. g, 5 (1925). 3. Noelting, Ber. 31. 553 (1891). 4. Suais,'Bu11. 1, 517 (1897). 8. Aluminum Chloride. 1. More and Weith, Ber. 14, 187 (1881). 2. Waas, Ber. 15, 1128 (1882). 3. Gaebe, Ber. 34, 1778 (1901). . 4. Jaubert, Compt. rend. 133, 41 (1901). 5. Frankforter and Kritchevsky, J. Am. Chem. Soc. 38, 1511 (1914). 6. Frankforter and Kokatnur, J. Am. Chem. Soc. 31. 385 (1915). 7. Huston and.Friedemann,J. Am. Chem. Soc. 38, 2527 (1918). 8. Huston and Friedemann, J. Am. Chem. Soc. 40, 785 (1918). 9. Huston, J. Am. Chem. Soc. 48, 2775 (1924). III Experimental 1. Cilman and McCracken, J. Am. Chem. Soc. 45, 2482 (1923). 3. Fourneau, Anales. soc. espan. fis. Quim. 18, 323 (1920). . Vernimmen, Bull. soc. chim. Belg. 3;, 96 (1934). 3 4. Hess and Rheinboldt, Ber. 54, 2043 (1921). 5. Gattermann, Practical Methods of Organic Chemistry. 6 . Moir, J. S. African Chem. Inst. .5, 8 (1933). .13.ww¢1sfiw.a:~..7mwf $35884 . ...... 1...... ......s... s......--.......- ...... . v.8.» .... . 3.5... I.) ..m‘w-nw. as-.. .....umpuwn'mwtd 4... 11...». . .mhm..n..u..ued-r.t..m-.n.. 41.1w...- ar. .. u... the... “..--905...... . . . ...—.4... 1.4.9. no. -u- ...-......q.....ln. . ..4317 -:.n..b...b’)“0.~h g. ..reltx. 1 I . . . -.. ...... .. . _ .... ..2............,.Io4.a.4..n.. . . .. fl .. v ._ l. .. . . 4-. . I. .. .... .....z. .-. .. .. . iii-...-..- v .. 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