Alkylation of p-Cresol with Isohexyl Alcohol

Alkylation of p-Cresol with Isohexyl Alcohol Russian Journal of Applied Chemistry, Vol. 74, No. 2, 2001, p. 350. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 2, 2001, pp. 342 3343. Original Russian Text Copyright C 2001 by Osadchenko, Tomilov. BRIEF ˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝ ˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝ COMMUNICATIONS I. M. Osadchenko and A. P. Tomilov State Research Institute of Organic Chemistry and Technology, Moscow, Russia Received June 23, 2000 Abstract-The feasibility of p-cresol alkylation with isohexyl alcohol, using phosphotungstic heteropoly acid as catalyst, was examined. Alkyl derivatives of p-cresol find application as The experiment with phosphomolybdic acid H PMo O failed, because the catalyst appeared antioxidants, surfactants, and perfumes. In particular, 7 12 42 to be reactive toward the starting compounds. products of p-cresol alkylation with isohexyl alcohol are used in synthesis of vetinone perfume (see scheme). Below is given a typical procedure for condensa- tion of p-cresol with isohexyl alcohol. OH A reactor equipped with a reflux condenser with +(CH ) CH 3C(CH ) 6 a Dean3Stark trap, a stirrer, a thermometer, and a drop- 3 2 3 2 ping funnel was charged with 102 g (0.982 mol) of OH p-cresol and 2.0 g of H PW O . The mixture was CH 3 7 12 42 heated on an oil bath to 85395oC, and 51 g (0.50 mol) OH OH O of isohexyl alcohol was added dropwise at this tem- g g g g R R R perature over a period of 40 min. The temperature was j j j j H O 2 2 76 76 gradually raised to 1053120oC, and the mixture was re- 3H O 2 88 fluxed for 4 h 40 min. In the process, water was sepa- g g g rated in the Dean3Stark trap. After the reaction was CH CH CH 3 3 3 complete, the content of the target product was de- termined by GLC to be 50.5%. To isolate the product, where R = (CH ) C 3CH(CH ) . 3 2 3 2 the mixture was neutralized with 3 g of sodium carbon- Kheifits et al. [1, 2] studied the alkylation of ate. The neutralized mixture was vacuum-distilled. p-cresol in the presence of various catalysts including The target fraction (bp 125 3140oC/8310 mm Hg) con- Fe (SO ) , ZnCl ,BF , and H SO . Sulfuric acid ap- 2 4 3 2 3 2 4 tained, according to GLC, 97% 4-methyl-2-isohexyl- peared to be the most suitable. At a 2 : 1 molar ratio phenol. The product yield was 53 g (55.2% in terms of of p-cresol to alcohol and a temperature of 110 3 loaded isohexyl alcohol), and the amount of bottoms, 120oC, the target product was obtained in about 50% 7.2 wt % relative to the target fraction (with sulfuric yield. A major drawback of the process is the ap- acid as catalyst, the amount of bottoms was 15 wt %). preciable tarring of the reaction mixture containing The alkylation of p-cresol with 2-methyl-2-pentan- about 15 wt % tar. ol was performed similarly. The yield of the condensa- tion product, 4-methyl-2-(2-methyl-2-pentyl)phenol, The tarring, and also the high corrosive activity was 50%. of sulfuric acid stimulated us to look for new cata- lysts for this process. We decided to test heteropoly REFERENCES acids which have recently found use as catalysts in many processes [3]. Among the tested heteropoly 1. Kheifits, L.A. and Podberezina, A.S., in Problemy or- ganicheskogo sinteza (Problems of Organic Synthesis), acids, the best results were obtained with reagent- Moscow: Nauka, 1965, pp. 124 3132. grade phosphotungstic acid H PW O [TU (Techni- 7 12 42 2. Kheifits, L.A., Podberezina, A.S., Klimakhina, S.T., cal Specifications) 6-09-4376 378]. With this catalyst, and Grigor’eva, L.T., Maslozhir. Prom 3st., 1976, no. 7, the formation of tars under the conditions recom- pp. 32334. mended for the process with sulfuric acid decreased 3. Kozhevnikov, I.V., Usp. Khim., 1987, vol. 56, no. 9, by more than a factor of 2. pp. 141731442. 1070-4272/01/7402-0350 $25.00 C 2001 MAIK [Nauka/Interperiodica] http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Russian Journal of Applied Chemistry Springer Journals

Alkylation of p-Cresol with Isohexyl Alcohol

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Publisher
Kluwer Academic Publishers-Plenum Publishers
Copyright
Copyright © 2001 by MAIK “Nauka/Interperiodica”
Subject
Chemistry; Chemistry/Food Science, general
ISSN
1070-4272
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1608-3296
D.O.I.
10.1023/A:1012771528282
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Abstract

Russian Journal of Applied Chemistry, Vol. 74, No. 2, 2001, p. 350. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 2, 2001, pp. 342 3343. Original Russian Text Copyright C 2001 by Osadchenko, Tomilov. BRIEF ˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝ ˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝ COMMUNICATIONS I. M. Osadchenko and A. P. Tomilov State Research Institute of Organic Chemistry and Technology, Moscow, Russia Received June 23, 2000 Abstract-The feasibility of p-cresol alkylation with isohexyl alcohol, using phosphotungstic heteropoly acid as catalyst, was examined. Alkyl derivatives of p-cresol find application as The experiment with phosphomolybdic acid H PMo O failed, because the catalyst appeared antioxidants, surfactants, and perfumes. In particular, 7 12 42 to be reactive toward the starting compounds. products of p-cresol alkylation with isohexyl alcohol are used in synthesis of vetinone perfume (see scheme). Below is given a typical procedure for condensa- tion of p-cresol with isohexyl alcohol. OH A reactor equipped with a reflux condenser with +(CH ) CH 3C(CH ) 6 a Dean3Stark trap, a stirrer, a thermometer, and a drop- 3 2 3 2 ping funnel was charged with 102 g (0.982 mol) of OH p-cresol and 2.0 g of H PW O . The mixture was CH 3 7 12 42 heated on an oil bath to 85395oC, and 51 g (0.50 mol) OH OH O of isohexyl alcohol was added dropwise at this tem- g g g g R R R perature over a period of 40 min. The temperature was j j j j H O 2 2 76 76 gradually raised to 1053120oC, and the mixture was re- 3H O 2 88 fluxed for 4 h 40 min. In the process, water was sepa- g g g rated in the Dean3Stark trap. After the reaction was CH CH CH 3 3 3 complete, the content of the target product was de- termined by GLC to be 50.5%. To isolate the product, where R = (CH ) C 3CH(CH ) . 3 2 3 2 the mixture was neutralized with 3 g of sodium carbon- Kheifits et al. [1, 2] studied the alkylation of ate. The neutralized mixture was vacuum-distilled. p-cresol in the presence of various catalysts including The target fraction (bp 125 3140oC/8310 mm Hg) con- Fe (SO ) , ZnCl ,BF , and H SO . Sulfuric acid ap- 2 4 3 2 3 2 4 tained, according to GLC, 97% 4-methyl-2-isohexyl- peared to be the most suitable. At a 2 : 1 molar ratio phenol. The product yield was 53 g (55.2% in terms of of p-cresol to alcohol and a temperature of 110 3 loaded isohexyl alcohol), and the amount of bottoms, 120oC, the target product was obtained in about 50% 7.2 wt % relative to the target fraction (with sulfuric yield. A major drawback of the process is the ap- acid as catalyst, the amount of bottoms was 15 wt %). preciable tarring of the reaction mixture containing The alkylation of p-cresol with 2-methyl-2-pentan- about 15 wt % tar. ol was performed similarly. The yield of the condensa- tion product, 4-methyl-2-(2-methyl-2-pentyl)phenol, The tarring, and also the high corrosive activity was 50%. of sulfuric acid stimulated us to look for new cata- lysts for this process. We decided to test heteropoly REFERENCES acids which have recently found use as catalysts in many processes [3]. Among the tested heteropoly 1. Kheifits, L.A. and Podberezina, A.S., in Problemy or- ganicheskogo sinteza (Problems of Organic Synthesis), acids, the best results were obtained with reagent- Moscow: Nauka, 1965, pp. 124 3132. grade phosphotungstic acid H PW O [TU (Techni- 7 12 42 2. Kheifits, L.A., Podberezina, A.S., Klimakhina, S.T., cal Specifications) 6-09-4376 378]. With this catalyst, and Grigor’eva, L.T., Maslozhir. Prom 3st., 1976, no. 7, the formation of tars under the conditions recom- pp. 32334. mended for the process with sulfuric acid decreased 3. Kozhevnikov, I.V., Usp. Khim., 1987, vol. 56, no. 9, by more than a factor of 2. pp. 141731442. 1070-4272/01/7402-0350 $25.00 C 2001 MAIK [Nauka/Interperiodica]

Journal

Russian Journal of Applied ChemistrySpringer Journals

Published: Oct 13, 2004

References

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