Please wait a minute...
Acta Physico-Chimica Sinca  2018, Vol. 34 Issue (6): 598-617    DOI: 10.3866/PKU.WHXB201711231
How to Synthesize Vitamin E
WANG Zhe, MAO Shanjun, LI Haoran, WANG Yong
ZJU-NHU United R & D Center, Institute of Catalysis, Department of Chemistry, Zhejiang University, Hangzhou 310028, P. R. China
Download:   PDF(2573KB) Export: BibTeX | EndNote (RIS)      


Vitamin E compounds are biologically active and are frequently used as antioxidants. The demand for Vitamin E compounds has increased significantly in recent years, and at present, more than 80 percent of the market demand for Vitamin E is fulfilled by its synthetic counterparts. Therefore, it is imperative to increase the production of Vitamin E. Vitamin E compounds contain tocopherol and tocotrienol derivatives, and α-tocopherol, which dominates the sound, is the most biologically active. This review covers the methods of preparation of α-tocopherol, focusing on the synthesis routes, chemical reactions, and corresponding catalysts. The synthesis of Vitamin E, including preparation of 2,3,5-trimethylhydroquinone (TMHQ), preparation of isophytol, and condensation of TMHQ and isophytol are discussed in detail. The disadvantages and issues related to the preparation methods are also included. In general, the preparation of TMHQ comprises three steps:(1) methylation of m-cresol to 2,3,6-trimethylphenol, (2) oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethylbenzoquione (TMBQ), and (3) hydrogenation of TMBQ to TMHQ. Recently, a novel and attractive method using isophorone, which can be produced by self-condensation of acetone, as a source for synthesizing TMHQ has been developed. Among these procedures, it is important to attain high selectivity in the oxidative reactions, including oxidation of 2,3,6-trimethylphenol and isophorone (α-isophorone or β-isophorone), and to replace H2O2, a common oxidant, by oxygen or air. One of the methods of preparation of isophytol using citral as a source has been abandoned because of shortage of oil of litsea cubeba, which is a natural source of citral. Linalool, produced from 6-methyl-5-hepten-2-one, is a key intermediate in the main process of preparation of isophytol. Both BASF SE and Roche have developed effective methods for the preparation of 6-methyl-5-hepten-2-one, respectively. Semi-hydrogenation of alkynols plays a key role in the whole process. The selectivity, especially at high conversion is directly related to the profit; therefore, it is of great importance for industries. The condensation of TMHQ and isophytol is essentially a Friedel-Crafts alkylation reaction catalyzed by acids. Similar reactions include methylation of m-cresol. Bronsted acids are usually effective for these reactions; however, it is difficult to recover these catalysts from the homogeneous systems. Therefore solid acid has a great potential in this area and it is also a promising topic to reduce the loss of acid sites when using acid-immobilized catalysts. The supply of various sources of the reactants and the local policy need to be considered while choosing an appropriate method for the preparation of Vitamin E.

Key wordsVitamin E      Tocopherol      2,3,5-trimethylhydroquinone      Isophytol      Catalyst     
Received: 11 October 2017      Published: 23 November 2017
MSC2000:  O643  

The project was supported by the National Natural Science Foundation of China (21622308, 91534114, 21376208).

Corresponding Authors: WANG Yong     E-mail:
Cite this article:

WANG Zhe, MAO Shanjun, LI Haoran, WANG Yong. How to Synthesize Vitamin E. Acta Physico-Chimica Sinca, 2018, 34(6): 598-617.

URL:     OR

(1) Traber, M. G. Annu. Rev. Nutr. 2007, 27, 347. doi: 10.1146/annurev.nutr.27.061406.093819
(2) Sun, J. M.; Lu, H. F.; Nan, J. L. Tianjin Chem. Ind. 2002, 5, 26.[孙建梅, 陆洪芳, 南家莲. 天津化工, 2002, 5, 26.]doi:10.3969/j.issn.1008-1267.2002.05.012
(3) Eckstein, S.; Hintermeier, P. H.; Olarte, M. V.; Liu, Y.; Baráth, E.; Lercher, J. A. J. Catal. 2017, 352, 329. doi: 10.1016/j.jcat.2017.06.002
(4) Leach B. L. Process for direct methylation of phenol in liquid phase.US 3994982A, 1975.
(5) Leach B. E. Process for the synthesis of 2, 6-xylenol and 2, 3, 6-trimethylphenol. US 4283574A, 1980.
(6) Velu, S.; Sivasanker, S. Res. Chem. Intermediat 1998, 24, 657. doi: 10.1163/156856798x00555
(7) Grabowska, H.; Wrzyszcz, J.; Syper, L. Catal. Lett. 1999, 57, 135. doi: 10.1023/a:1019083112771
(8) Xiao, G. M.; Li, Z. S; Jiang, F.; Niu, L.; Xiong, Z. Catalyst forsynthesizing 2, 3, 6-trimethylphenol and preparation method thereof.CN 102974354A, 2013.
(9) Niu, L.; Li, Z. S.; Jiang, F.; Zhou, M. H.; Wang, Z. H.; Xiao, G. M. React. Kinet. Mech. Cat. 2014, 112, 199. doi: 10.1007/s11144-014-0697-z
(10) Gandhe, A. R.; Fernandes, J. B. Catal. Commun. 2004, 5, 89. doi: 10.1016/j.catcom.2003.11.017
(11) Gandhe, A. R.; Naik, S. P.; Kakodkar, S. B.; Fernandes, J. B. Catal. Commun. 2006, 7, 285. doi:10.1016/j.catcom.2005.09.013
(12) Santacesaria, E.; Grasso, D.; Gelosa, D.; Carrá, S. Appl. Catal. 1990, 64, 83. doi:10.1016/S0166-9834(00)81555-9
(13) Sreekumar, K.; Sugunan, S. Appl. Catal. A 2002, 230, 245. doi: 10.1016/S0926-860X(02)00006-6
(14) Bezouhanova, C.; Al-Zihari, M. A. Appl. Catal. A 1992, 83, 45. doi: 10.1016/0926-860X(92)80024-7
(15) Qian, D.; He, H. Q.; Wang, K. Y. Chem. Reagents (Beijing, China) 2002, 4, 231.[钱东, 何厚群, 王开毅. 化学试剂, 2002, 4, 231.]doi:10.3969/j.issn.0258-3283.2002.04.016.
(16) Bodnar, Z.; Mallat, T.; Baiker, A. J. Mol. Catal. A-Chem. 1996, 110, 55. doi:10.1016/1381-1169(96)00042-8
(17) Li, X.; Wang, X. Y.; Shu, W. G.; Qian, D. Hunan Chem. Ind. 1998, 5, 24.[李雄, 王歆燕, 舒万艮, 钱东. 湖南化工, 1998, 5, 24.]doi:10.19342/j.cnki.issn.1009-9212.1998.05.010
(18) Chu, Z. H.; Zang, H. C. Guangzhou Chem. Ind. 2011, 9, 104.[储振华, 臧恒昌. 广东化工, 2011, 9, 104.]doi:10.3969/j.issn.1001-9677.2011.09.037
(19) Takehira, K.; Shimizu, M.; Watanabe, Y.; Orita, H.; Hayakawa, T. J. Chem. Soc., Chem. Commun. 1989, 1705. doi: 10.1039/C39890001705
(20) Takehira, K.; Shimizu, M.; Watanabe, Y.; Orita, H.; Hayakawa, T. Tetrahedron Lett. 1989, 30, 6691. doi: 10.1016/S0040-4039(00)70652-6
(21) Shimizu, M.; Watanabe, Y.; Orita, H.; Hayakawa, T.; Takehira, K. B. Chem. Soc. Jpn. 1992, 65, 1522. doi:10.1246/bcsj.65.1522
(22) Sun, H. J.; Harms, K.; Sundermeyer, J. J. Am. Chem. Soc. 2004, 126, 9550. doi:10.1021/ja0391964
(23) Wang, X. P.; Yang, R. Y.; Li, W.; Li, X. A.; Yan, J.; Liu, W. T.; Zhang, H. H. Ind. Catal. 2013, 8, 73.[王宪沛, 杨瑞云, 李文, 李小安, 阎俊, 刘卫涛, 张辉辉. 工业催化, 2013, 8, 73.]doi:10.3969/j.issn.1008-1143.2013.08.016
(24) Guan, W. H.; Wang, C. M.; Yun, X.; Hu, X. B.; Wang, Y.; Li, H. R. Catal. Commun. 2008, 9, 1979. doi:10.1016/j.catcom.2008.03.028
(25) Wang, C.; Guan, W.; Xie, P.; Yun, X.; Li, H.; Hu, X.; Wang, Y. Catal. Commun. 2009, 10, 725. doi:10.1016/j.catcom.2008.11.027
(26) Kholdeeva, O. A.; Golovin, A. V.; Kozhevnikov, I. V. React. Kinet. Catal. L. 1992, 46, 107. doi:10.1007/bf02096685
(27) Kholdeeva, O. A.; Golovin, A. V.; Maksimovskaya, R. I.; Kozhevnikov, I. V. J. Mol. Catal. 1992, 75, 235. doi: 10.1016/0304-5102(92)80128-4
(28) Qian, D.; Zhang, M.; Wang, K. Y. Chin. J. Synth. Chem. 1998, 2, 2.[钱东, 张敏, 王开毅. 合成化学, 1998, 2, 2.]doi:10.15952/j.cnki.cjsc.1998.02.001
(29) Palacio, M.; Villabrille, P. I.; Romanelli, G. P.; Vázquez, P. G.; Cáceres, C. V. Appl. Catal. A 2012, 417, 273. doi: 10.1016/j.apcata.2011.12.049
(30) Lin, T. H.; Chen, C. C.; Jang, L. Y.; Lee, J. F.; Cheng, S. Micropor. Mesopor. Mater. 2014, 198, 194. doi: 10.1016/j.micromeso.2014.07.027
(31) Trukhan, N. N.; Romannikov, V. N.; Paukshtis, E. A.; Shmakov, A.N.; Kholdeeva, O. A. J. Catal. 2001, 202, 110. doi: 10.1006/jcat.2001.3264
(32) Zhou, J.; Hua, Z. L.; Cui, X. Z.; Ye, Z. Q.; Cui, F. M.; Shi, J. L. Chem. Commun. 2010, 46, 4994. doi:10.1039/C0CC00499E
(33) Kholdeeva, O. A.; Ivanchikova, I. D.; Guidotti, M.; Ravasio, N.; Sgobba, M.; Barmatova, M. V. Catal. Today 2009, 141, 330. doi: 10.1016/j.cattod.2008.06.005
(34) Wu, M. Z.; Li, Y.; Huang, X. Z.; Liu, W.; Yi, Z. Z. Appl. Chem. Ind. (Xi'an, China) 2014, 3, 456.[吴明珠, 李应, 黄相中, 刘卫, 易中周. 应用化工, 2014, 3, 456.]doi:10.16581/j.cnki.issn1671-3206.2014.03.004
(35) Li, Y.; Liu, W.; Wu, M. Z.; Yi, Z. Z.; Zhang, J. C. Mendeleev. Comm. 2010, 20, 218. doi:10.1016/j.mencom.2010.06.012
(36) Liu, Y. C.; Hsu, J.; Fu, Y. P.; Tsai, K. Int. J. Hydrog. Energy 2016, 41, 15696. doi:10.1016/j.ijhydene.2016.04.127
(37) Zhang, T. Y.; Wang, M. Y.; Li, B.; Liu, Q. Chem. Ind. Eng. Prog. (Beijing, China) 2016, 2, 513.[张天永, 王梦颖, 李彬, 刘茜. 化工进展, 2016, 2, 513.] doi:10.16085/j.issn.1000-6613.2016.02.025
(38) Zhu, Z. Q.; Yuan, Z. F.; Xu, Q. F. Preparation method of 2, 3, 5-trimethylhydroquinone. CN 102241577A, 2011.
(39) Zhang, T. Y.; Yin, G.; Li, B.; Wang, X.; Jiang, S.; Yuan, Z. F. Res. Chem. Intermediat 2015, 41, 663. doi:10.1007/s11164-013-1219-8
(40) Qian, D.; Wang, K. Y.; Yang, L. Y.; Zhang, M. K. J. Cent. South Univ. (Sci. Technol.) 2000, 1, 41.[钱东, 王开毅, 杨礼义, 张茂昆.中南工业大学学报(自然科学版), 2000, 1, 41.]
(41) Qian, D.; Wang, K. Y.; Yang, L. Y.; Zhang, M. K. J. Cent. South Univ. (Sci. Technol.) 1998, 5, 97.[钱东, 王开毅, 杨礼义, 张茂昆.中南工业大学学报(自然科学版), 1998, 5, 97.]
(42) Zhao, X. M.; Jin, Y.; Zhang, F. M.; Zhong, Y. J.; Zhu, W. D. Chem. Eng. J. 2014, 239, 33. doi:10.1016/j.cej.2013.11.003
(43) Zhang, T. Y.; Yin, G.; Li, B.; Deng, Y. F.; Yuan, Z. F. Appl. Chem. Ind. (Xi'an, China) 2013, 8, 1363.[张天永, 尹观, 李彬, 邓永峰, 袁仲飞. 应用化工, 2013, 8, 1363.]doi:10.16581/j.cnki.issn1671-3206.2013.08.034
(44) Mukhopadhyay, S.; Chandnani, K. H.; Chandalia, S. B. Org. Process. Res. Dev. 2000, 4, 254. doi:10.1021/op990074z
(45) Su, D. F.; Wei, Z. Z.; Mao, S. J.; Wang, J.; Li, Y.; Li, H. R.; Chen, Z.R.; Wang, Y. Catal. Sci. Technol. 2016, 6, 4503. doi: 10.1039/C5CY02171E
(46) Qiao, J. C.; Chen, Q.; Cai, D. W. Process for synthesizing 2, 3, 6-trimethylphenol by 4-tert-butylphenol. CN 102976902A, 2013.
(47) Zhao, J. C.; Han, Q. Y.; Liu, J. F.; Liu, L.; Hu, L. L.; Liu, Y. H.Method for extraction of 2, 4, 6-trimethylphenol from 2, 6-dimethylphenol waste. CN 104045522A, 2014.
(48) Teijin LTD Preparation of 2, 4, 6-trimethylphenol. GB 1451091A, 1973.
(49) Bonrath, W.; Schuetz J.; Cavani F. Manufacture of 2, 4, 6-trimethylphenol. WO 2015197586A1, 2015.
(50) Ichikawa, Y.; Yamanaka, Y.; Tsuruta, H. Novel process forpreparation of 4-hydroxy-2, 4, 6-trimethyl-2, 5-cyclohexadiene-1-one.US 3966818A, 1973.
(51) Toyoda, Y.; Ikeda, Y.; Hase, T.; Kitano, N. Preparation of 4-hydroxy-2, 4, 6-trimethyl-2, 5-cyclohexadien-1-one. JPS 5841835A, 1981.
(52) Tomita, T.; Kino, M.; Takada, T. Preparation of 4-hydroxy-2, 4, 6-trimethylcyclohexa-2, 5-dien-1-one. JPS 58116435A, 1981.
(53) Tomita, T.; Kino, M.; Takada, T. Prepn. of hydroxy-tri:methyl-cyclohexa-dienone-by reacting tri:methyl-phenol with hypohalous acid.JPS 59163337A, 1983.
(54) Yoshida, D. Production of high-purity 4-hydroxy-2, 4, 6-trimethyl-2, 5-cyclohexadien-1-one. JPS 62238230A, 1986.
(55) Gogou, T. Preparation of 4-hydroxy-2, 4, 6-trimethyl-2, 5-cyclohexadien-1-one. JPS 5953438A, 1982.
(56) Costantini, M.; Igersheim, F.; Krumenacker, L. Process for thepreparation of 4-hydroxy-2, 4, 6-trimethyl-2, 5-cyclohexadienone. US4565895A, 1984.
(57) Costantini, M.; Igersheim, F.; Krumenacker, L. 4-Hydroxy 2, 4, 6-tri:methyl cyclohexadienone prepn.-by chlorination and hydrolysisof 2, 4, 6-tri:methyl phenol. US 4612401A, 1986.
(58) Teijin LTD Preparation of trimethyl hydroquinone. GB 1439494A, 1973.
(59) Qiao, J. C.; Chen, Q.; Cai, D. W. Process for synthesizing 2, 3, 6-trimethylphenol by phenol. CN 102976903A, 2013.
(60) Arnold, L.; Pasedach, H.; Pommer, H. 2, 3, 6-Trimethylphenolprodn.-by reacting diethyl ketone in presence of base with e.g.crotonaldehyde. DE 1668874B1, 1971.
(61) Tavs, P.; Laas, H.; Schauer, H.; Arnold, L. Increasing the yield of2.5.6-trimethylcyclohex-2-en-1-one. US 4820874A, 1989.
(62) Rittinger, S.; Rieber, N.; Arnold, L.; Hoercher, U. Prodn. of 2, 3, 6-tri:methylphenol-by reacting di:ethyl ketone with 1-amino-vinylmethyl ketone at 50-200 deg.C. DE 4414877A1, 1995.
(63) Nissei IND CO LTD Trimethylbenzoquinone prodn. in aq.soln.-from 3, 6-dinitrotrimethyl benzene sulphonate using ferric saltas oxidising agent. JP 75028426B, 1975.
(64) Bao, J.; Liu, G. F.; Gao, R.; Zhang, Y. Chemical EnterpriseManagement 2016, 4, 187.[包吉, 刘高赋, 高荣, 张雨. 化工管理, 2016, 4, 187.] doi:10.3969/j.issn.1008-4800.2016.04.121
(65) Chen, H.; Wu, Y.; Xu, G. M. Adv. Fine Petrochem. 2002, 4, 25.[陈红, 吴缨, 徐国梅. 精细石油化工进展, 2002, 4, 25.]doi:10.3969/j.issn.1009-8348.2002.04.008
(66) Zhao, F.; Yang, B. Y.; Gu, J. J.; Guan, P. M. Ind. Catal. 2012, 6, 62.[赵峰, 杨蓓玉, 顾剑江, 管盘铭. 工业催化, 2012, 6, 62.]doi:10.3969/j.issn.1008-1143.2012.06.014
(67) Zhang, T. Y.; Liu, X. S.; Li, B.; Wang, M. Y.; Wang, Z. C.; Hai, L. Chem. Bull. (Beijing, China) 2017, 6, 573.[张天永, 刘晓思, 李彬, 王梦颖, 王智超, 海莉. 化学通报, 2017, 6, 573.]doi:10.14159/j.cnki.0441-3776.2017.06.010
(68) Zhang, T. Y.; Duan, Y. J.; Li, B.; Wang, X.; Du, J.; Yin, G.; Yuan, Z.F. Chem. Reagents (Beijing, China) 2013, 1, 3.[张天永, 段永洁, 李彬, 王晓, 杜晶, 尹观, 袁仲飞. 化学试剂, 2013, 1, 3.]doi:10.13822/j.cnki.hxsj.2013.01.016
(69) Dawson, B.; Pugach, J. Method of making ketoisophorone viaoxidation of isophorone with tert-butyl hydroperoxide. WO9615094A1, 1996.
(70) Noesberger, P.; Vieth, A. Process for manufacture of betaisophorone. US 5276197A, 1994.
(71) Krill, S.; Giray, G.; Huthmacher, K.; Huebner, F.; Tanner, H.Method of producing 3, 5, 5-trimethylcyclohexa-3-ene-1-one(beta -isophorone) by the isomerization of 3, 5, 5-trimethylcyclohexa-2-ene-1-(alpha-isophorone). US 6005147A, 1999.
(72) Takahashi, I.; Shibata, H. Oxidation catalyst and oxidation processusing the same. US 6462239B2, 2002.
(73) Ina, T.; Miura, H.; Takahashi, I. Process for the production ofketoisophorone derivatives and equipment therefor. US 6410797B1, 2002.
(74) Murphy, E. F.; Baiker, A. J. Mol. Catal. A-Chem. 2002, 179, 233. doi: 10.1016/S1381-1169(01)00342-9
(75) Bellut, H. Method of producing 2, 6, 6-trimethyl-2-cyclohexane-1, 4-dione. US 4970347A, 1990.
(76) Hu, X. B.; Mao, J. Y.; Sun, Y.; Chen, H.; Li, H. R. Catal. Commun. 2009, 10, 1908. doi:10.1016/j.catcom.2009.06.024
(77) Chen, Z. R.; Fang, T. T.; Yuan, S. F.; Yin, H. Int. J. Chem. Kinet. 2016, 48, 295. doi:10.1002/kin.20987
(78) Beyrhouty, M.; Sorokin, A. B.; Daniele, S.; Hubert-Pfalzgraf, L. G. New J. Chem. 2005, 29, 1245. doi:10.1039/B507211E
(79) Sorokin, A. B.; Quignard, F.; Valentin, R.; Mangematin, S. Appl. Catal. A 2006, 309, 162. doi:10.1016/j.apcata.2006.03.060
(80) Burns, E.; Huang, T.; Weare, W. W.; Bartolotti, L.; Wang, X. Y.; Yao, J.; Li, H. R.; Franzen, S. J. Mol. Catal. A-Chem. 2015, 410, 110. doi:
(81) Thatte, C. S.; Rathnam, M. V.; Pise, A. C. J. Chem. Sci. 2014, 126, 727. doi:10.1007/s12039-014-0601-4
(82) Mao, J. Y.; Li, N.; Li, H. R.; Hu, X. B. J. Mol. Catal. A-Chem. 2006, 258, 178. doi:10.1016/j.molcata.2006.05.051
(83) Zhang, P. F.; Li, H. R.; Wang, Y. Chem. Commun. 2014, 50, 6312. doi: 10.1039/c4cc02676d
(84) Kishore, D.; Rodrigues, A. E. Catal. Commun. 2007, 8, 1156. doi: 10.1016/j.catcom.2006.10.037
(85) Kishore, D.; Rodrigues, A. E. Appl. Catal. A 2008, 345, 104. doi: 10.1016/j.apcata.2008.04.029
(86) Wang, C. M.; Wang, G. L.; Mao, J. Y.; Yao, Z.; Li, H. R. Catal. Commun. 2010, 11, 758. doi:10.1016/j.catcom.2010.02.010
(87) Chen, K. X.; Sun, Y.; Wang, C. M.; Yao, J.; Chen, Z. R.; Li, H. R. Phys. Chem. Chem. Phys. 2012, 14, 12141. doi: 10.1039/C2CP41617D
(88) Zhong, W. Z.; Mao, L. Q.; Xu, Q.; Fu, Z. H.; Zou, G. Q.; Li, Y. Q.; Yin, D. L.; Luo, H.; Kirk, S. R. Appl. Catal. A 2014, 486, 193. doi: 10.1016/j.apcata.2014.08.005
(89) Murphy, E. F.; Mallat, T.; Baiker, A.; Schneider, M. Appl. Catal. A 2000, 197, 295. doi:10.1016/S0926-860X(99)00491-3
(90) Crier, S.; Huthmacher, K. Method for preparation of 2, 3, 5-trimethylhydrochinone di-ester. CN 1265390A, 2000.
(91) Weigel, H.; Krill, S.; Hasselbach, H.; Huthmacher, K.; Wegel, H.; Kelier, S.; Haserbach, H. Process for preparing esterified chromancompounds. US 6329535B1, 2001.
(92) Bonrath, W.; Schneider, M.; Werner, B.; Michael, S. Manufacture oftrimethylhydroquinone diacylates. CN 1604888A, 2005.
(93) Weigel, H.; Krill, S.; Hasselbach, H.; Huthmacher, K.; Wegel, H.; Kelier, S.; Haserbach, H. Preparation process of exterified chromancompound. CN 1308077A, 2001.
(94) Wildermann, A.; Foricher, Y.; Netscher, T.; Bonrath, W. Pure Appl. Chem. 2007, 79, 1839. doi:10.1351/pac200779111839
(95) Zeng, Q. Y.; Song, W. J.; Zhang, Q.; Pan, H.; Gao, J. Y.; Ni, C. Y.Method for synthesizing 2, 3, 5-trimethylhydroquinone diester. CN102180793A, 2011.
(96) Schneider, M.; Zimmermann, K.; Aquino, F.; Bonrath, W. Appl. Catal. A 2001, 220, 51. doi:10.1016/S0926-860X(01)00704-9
(97) Rác, B.; Molnár, Á.; Forgo, P.; Mohai, M.; Bertóti, I. J. Mol. Catal. A-Chem. 2006, 244, 46. doi:10.1016/j.molcata.2005.08.043
(98) Hinze, R.; Laufer, M. C.; Hölderich, W. F.; Bonrath, W.; Netscher, T. Catal. Today 2009, 140, 105. doi:10.1016/j.cattod.2008.07.008
(99) AEC CHIM ORGAN BIOLOG Improvements in and relating toprocess of preparing isophytol. GB 1087837A, 1967.
(100) Ku?trowski, P.; Su?kowska, D.; Chmielarz, L.; Dziembaj, R. Appl. Catal. A 2006, 302, 317. doi:10.1016/j.apcata.2006.02.003
(101) Abelló, S.; Vijaya-Shankar, D.; Pérez-Ramírez, J. Appl. Catal. A 2008, 342, 119. doi:10.1016/j.apcata.2008.03.010
(102) Díez, V. K.; Di Cosimo, J. I.; Apesteguía, C. R. Appl. Catal. A 2008, 345, 143. doi:10.1016/j.apcata.2008.04.035
(103) Abelló, S.; Medina, F.; Tichit, D.; Pérez-Ramírez, J.; Rodríguez, X.; Sueiras, J. E.; Salagre, P.; Cesteros, Y. Appl. Catal. A 2005, 281, 191. doi:10.1016/j.apcata.2004.11.037
(104) Díez, V. K.; Apesteguía, C. R.; Di Cosimo, J. I. J. Catal. 2006, 240, 235. doi:10.1016/j.jcat.2006.04.003
(105) Hoelderich W.; Ritzerfeld, V. Preparing pseudoionone by aldolcondensation of citral and acetone using heterogeneous catalyst, comprises utilizing supported heterogeneous catalysts based on rareearth metals applied on e.g. zirconium dioxide carrier as carriermaterials. DE 102012012785A1, 2013.
(106) Wang, Z.; Lu, G. Z.; Guo, Y.; Guo, Y. L.; Gong, X. Q. ACS Sustain. Chem. Eng. 2016, 4, 1591. doi:10.1021/acssuschemeng.5b01533
(107) Raju, V.; Radhakrishnan, R.; Jaenicke, S.; Chuah, G. K. Catal. Today 2011, 164, 139. doi:10.1016/j.cattod.2010.10.043
(108) Horst, P.; Herbert, M.; Hermann, O. Preparing alkenones 2-methylheptene-1-on-6 from. DE 1268135B, 1968.
(109) Babler, J. H. Process for preparing tertiary alkynols. US 5349071A, 1994.
(110) Vorobyeva, E.; Chen, Z.; Mitchell, S.; Leary, R. K.; Midgley, P.; Thomas, J. M.; Hauert, R.; Fako, E.; Lopez, N.; Perez-Ramirez, J. J. Mater. Chem. A 2017, 5, 16393. doi:10.1039/C7TA04607C
(111) Crespo-Quesada, M.; Yarulin, A.; Jin, M.; Xia, Y.; Kiwi-Minsker, L. J. Am. Chem. Soc. 2011, 133, 12787. doi:10.1021/ja204557m
(112) Yarulin, A.; Yuranov, I.; Cárdenas-Lizana, F.; Abdulkin, P.; KiwiMinsker, L. J. Phys. Chem. C 2013, 117, 13424. doi: 10.1021/jp402258s
(113) Semagina, N.; Renken, A.; Kiwi-Minsker, L. J. Phys. Chem. C 2007, 111, 13933. doi:10.1021/jp073944k
(114) Tripathi, B.; Paniwnyk, L.; Cherkasov, N.; Ibhadon, A. O.; LanaVillarreal, T.; Gómez, R. Ultrason. Sonochem. 2015, 26, 445. doi: 10.1016/j.ultsonch.2015.03.006
(115) Tschan, R.; Schubert, M. M.; Baiker, A.; Bonrath, W.; LansinkRotgerink, H. Catal. Lett. 2001, 75, 31. doi: 10.1023/a:1016727904935
(116) Tschan, R.; Wandeler, R.; Schneider, M. S.; Burgener, M.; Schubert, M. M.; Baiker, A. Appl. Catal. A 2002, 223, 173. doi: 10.1016/S0926-860X(01)00755-4
(117) Studt, F.; Abild-Pedersen, F.; Bligaard, T.; Sørensen, R. Z.; Christensen, C. H.; Nørskov, J. K. Science 2008, 320, 1320. doi: 10.1126/science.1156660
(118) Yarulin, A.; Yuranov, I.; Cárdenas-Lizana, F.; Alexander, D. T. L.; Kiwi-Minsker, L. Appl. Catal. A 2014, 478, 186. doi: 10.1016/j.apcata.2014.04.003
(119) SNAM SPA(SNAM-C) Selective hydrogenation of alkynols toalkenols-in aqs medium using palladium catalyst and soluble zinccpd. NL 136588B, 1972.
(120) Okhlopkova, L. B.; Matus, E. V.; Prosvirin, I. P.; Kerzhentsev, M.A.; Ismagilov, Z. R. J. Nanopart. Res. 2015, 17, 475. doi: 10.1007/s11051-015-3289-6
(121) Deng, D. S.; Yang, Y.; Gong, Y. T.; Li, Y.; Xu, X.; Wang, Y. Green Chem. 2013, 15, 2525. doi:10.1039/c3gc40779a
(122) Shen, L. F.; Mao, S. J.; Li, J. Q.; Li, M. M.; Chen, P.; Li, H. R.; Chen, Z. R.; Wang, Y. J. Catal. 2017, 350, 13. doi: 10.1016/j.jcat.2017.01.021
(123) Bonrath, W.; Mueller, T.; Kiwi-Minsker, L.; Renken, A.; Iouranov, I.; Kiwi, M. Hydrogenation process. CN 102741206A, 2012.
(124) Bonrath, W.; Kiwi-Minsker, L.; Iouranov, I.; Kiwi, M. New catalyticsystem. CN 103906569A, 2014.
(125) Bonrath, W.; Buss, A. Metal powderdous catalyst comprising a Fealloy. CN 104136114A, 2014.
(126) Grjaznov, V.; Keravanov, A.; Belosljudo, N.; Ermolaev, A.; Maganjuk, A.; Saryceva, I. Process for the preparation of ethylenealcohols having 4 to 10 carbon atoms. DE 3114240A1, 1982.
(127) Kido, Y.; Kumagai, N.; Iwasaki, H.; Onishi, T.; Ueyama, F.; Kamiyama, F.; Kajiyashiki, T.; Kito, Y.; Iwagasaki, S. Process forproducing 6-methyl-3-hepten-2-one and 6-methyl-2-heptanoneanalogues, and process for producing phyton or isophytol. US5955636A, 1999.
(128) Wilson, S. R.; Price, M. F. J. Org. Chem. 1984, 49, 722. doi:10.1021/jo00178a036
(129) Constant, S.; Tortoioli, S.; Müller, J.; Lacour, J. Angew. Chem. Int. Ed. 2007, 46, 2082. doi:10.1002/anie.200604573
(130) Linder, D.; Buron, F.; Constant, S.; Lacour, J. Eur. J. Org. Chem. 2008, 5778. doi:10.1002/ejoc.200800854
(131) Linder, D.; Austeri, M.; Lacour, J. Org. Biomol. Chem. 2009, 7, 4057. doi:10.1039/B910475E
(132) Bizet, V.; Lefebvre, V.; Baudoux, J.; Lasne, M.-C.; Boulangé, A.; Leleu, S.; Franck, X.; Rouden, J. Eur. J. Org. Chem. 2011, 4170. doi: 10.1002/ejoc.201100120
(133) De Castro, K. A.; Byun, E. Y.; Rhee, H. B. Kor. Chem. Soc. 2009, 30, 2155. doi:10.5012/bkcs.2009.30.9.2155
(134) Oost, C.; Stroezel, M.; Etzrodt, H.; Weller, D.; Rheude, U.; Kaibel, G.; Krug, T.; Spiske, L.; Jaedicke, H.; Dietmar, W.; et al.Preparation of higher unsaturated ketone. CN 1271716A, 2000.
(135) Oost, C.; Stroezel, M.; Etzrodt, H.; Weller, D.; Bockstiegel B.; Reimer, K.; Kaibel, G.; Jaedicke, H.; Dietmar, W.; Aust, C.; et al.Method for continuous preparation of unsaturated ketone. CN1251832A, 2000.
(136) Takasago Perfumery CO (TAKS-C) soprene trimer prepn.-using acatalyst contg. zero-valent nickel and phosphines. JP 77016084B, 1977.
(137) Akutagawa, S. Geranyl acetone prepn.-by reacting myrcene withacetone imine in presence of alkali metal catalyst, and hydrolysing.JP 53071005A, 1978.
(138) Kido, Y.; Kitayama, M.; Yoneda, K.; Iwasaki, H.; Onishi, T.; Kitayama, K. Process for producing 6-methylheptan-2-one. US5840992A, 1998.
(139) Fujita, Y.; Wada, T.; Onishi, T.; Nishida, T.; Omura, S.; Mori, F.; Hosogai, T.; Aihara, F. 6, 10-Di:methyl-6, 9-undeca:diene-2-oneprodn.-by ethynylating substd. ketone obtd. from prenyl halide andmesityl oxide, partially hydrogenating and thermally rearranging. JP55055131A, 1980.
(140) Kuraray Co LTD(KURS-C) Preparation of phytone and isophytol.JPS 53105409A, 1978.
(141) Onishi, T.; Fujita, Y.; Nishida, T.; Ishiguro, M.; Hosogai, T. Phytoneor isophytol prodn.-by heating propargyl alcohol cpd.hydrogenating the resulting ketone and opt. vinylation of resulting phytone. JP 54014906A, 1979.
(142) De Jong, A. J.; Van, H. R. Process for the preparation of 6, 10, 14-trimethylpentadecan-2-one. CH 623021A5, 1981.
(143) Kuraray Co LTD(KURS-C) 3, 7-dimethyl-1-octanal prepn.-byhydroformylation of 2, 6-dimethyl-2-or -3-heptenes. JP 74020170, 1974.
(144) Goebbel, H.; Kaibel, G.; Miller, C.; Dobler, W.; Dirnsteiner, T.; Hahn, T.; Breuer, K.; Aquila, W.; Gobbel, H.; Gobbel, G.; et al.Production of tetrahydrogeranylacetone, for use in production ofVitamins E and K, involves selective, liquid-phase hydrogenation ofpseudo-ionone using a device which inhibits the transport of catalystparticles. CN 1668564A, 2005.
(145) Clamoe, A.; Siegel, W. Method for preparing higher ketone byunsaturated aldehyde. CN 1330062A, 2002.
(146) Teles, J.; Hoffmann, W. Preparation of hexahydrofarnesylacetoneform 6, 7-dihydrogeraniol, and novel intermadiates therefor. CN1172795A, 1998.
(147) Zhao, Z. D.; Liu, X. Z. Biomass Chem. Eng. 2001, 2, 41.[赵振东, 刘先章. 林产化工通讯, 2001, 2, 41.]doi:10.3969/j.issn.1673-5854.2001.02.011
(148) Luo, J. Y.; Wang, H. Z.; Peng, S. J. Chem. Ind. For. Prod. 2000, 3, 47.[罗金岳, 王汉忠, 彭淑静. 林产化学与工业, 2000, 3, 47.]doi:10.3321/j.issn:0253-2417.2000.03.009
(149) Liu, X. Z.; Hu, X. E.; Jiang, T. F.; Li, D. M.; Hu, G. X. Chem. Ind. For. Prod. 1997, 3, 25.[刘先章, 胡樨萼, 蒋同夫, 李冬梅, 胡贵贤. 林产化学与工业, 1997, 3, 25.]doi:10.3321/j.issn:0253-2417.1997.03.005
(150) Sun, M. H.; Qi, X.; Tang, X. Y.; Zhao, W. T. Chem. Ind. Eng. (Tianjin, China) 2016, 1, 51.[孙美环, 齐欣, 唐向阳, 赵温涛.化学工业与工程, 2016, 1, 51-56.]doi:10.13353/j.issn.1004.9533.20131188
(151) Renninger, N. S.; Newman, J.; Reiling, K. K.; Regentin, R.; Paddon, C. J. Production of isoprenoids. WO 2007140339A2 2007.
(152) Renninger, N. S.; Mcphee, D. J. Fuel compositions comprisingfarnesane and farnesane derivatives and method of making and usingsame. US 2008083158A1, 2008.
(153) Tsuruta, H.; Lenihan, J. R.; Regentin, R. WO 2009042070A2, 2009.
(154) Chua, P. R.; Meadows, A. Methods for stabilizing production ofacetyl-coenzyme a derived compounds. WO 2015020649A1, 2015.
(155) Lowack, R.; Meyer, J.; Eggersdorfer, M.; Grafen, P. Preparation ofalpha-tocopherol and alpha-tocopheryl acetate in liquid orsupercritical carbon dioxide. US 5523420A, 1996.
(156) Baldenius, K.; Kaiser, W.; Bockstiegel, B.; Laas, H.; Schulz, B.; Schmitt, P.; Glietenberg, H. Preparation of alpha-tocopherol oralpha-tocopheryl acetate by reacting trimethylhydroquinone andphytol or isophytol, with recycling of the zinc halide condensationcatalyst. US 6005122A, 1999.
(157) Krill, S.; Kretz, S.; Huthmacher, K. Process for the production ofalpha-tocopherol acetate by condensation of trimethylhydroquinonewith isophytol. EP 1132384A2, 2001.
(158) Duan, H. Y.; Wang, Z. H.; Li, J. T.; Li, S. H.; Li, L. J.; Li, T. S. Synthetic. Commun. 2003, 33, 1867. doi:10.1081/SCC-120020197
(159) Coman, S. M.; Wuttke, S.; Vimont, A.; Daturi, M.; Kemnitz, E. Adv. Synth. Catal. 2008, 350, 2517. doi:10.1002/adsc.200800411
(160) Wuttke, S.; Coman, S. M.; Scholz, G.; Kirmse, H.; Vimont, A.; Daturi, M.; Schroeder, S. L. M.; Kemnitz, E. Chem. -Eur. J. 2008, 14, 11488. doi:10.1002/chem.200801702
(161) Candu, N.; Wuttke, S.; Kemnitz, E.; Coman, S. M.; Parvulescu, V. I. Appl. Catal. A 2011, 391, 169. doi:10.1016/j.apcata.2010.08.004
(162) Baak, M.; Bonrath, W.; Pauling, H. Process for manufacturing d, 1-alpha-tocopherol. CN 1237163A, 1999.
(163) Bonrath, W.; Gockel, S.; Haas, A.; Netscher, T.; Pauling, H.Preparation of (all-rac)-alpha-tocopherol, which is an important member of vitamin E group, involves acid catalysis of trimethylhydroquinone with isophytol or phytol in presence of bis(perfluoroalkylsulfonyl)-methane. WO 2003070718P1, 2003.
(164) Bonrath, W.; Wang, S. N. Preparation of d, 1-alpha-tocopherol. US 6423851B2, 2002.
(165) Bonrath, W.; Dittel, C.; Netscher, T.; Pabst, T.; Giraudi, L. Process for the manufacture of alpha-tocopheryl acetate. WO2004063182A1, 2004.
(166) Bonrath, W.; Haas, A.; Hoppmann, E.; Netscher, T.; Pauling, H.; Schager, F.; Wildermann, A. Adv. Synth. Catal. 2002, 344, 37. doi: 10.1002/1615-4169(200201)344:1<37::aid-adsc37>;2-4
(167) Netscher, T.; Bonrath, W.; Haas, A.; Hoppmann, E.; Pauling, H. Chimia Inter. J. Chem. 2004, 58, 153. doi: 10.2533/000942904777678181
(168) Bonrath, W.; Dittel, C.; Giraudi, L.; Netscher, T.; Pabst, T. Catal. Today 2007, 121, 65. doi:10.1016/j.cattod.2006.11.022
(169) Hasegawa, A.; Ishihara, K.; Yamamoto, H. Angew. Chem. Int. Ed. 2003, 42, 5731. doi:10.1002/anie.200352382
(170) Coman, S. M.; Pop, G.; Stere, C.; Parvulescu, V. I.; El Haskouri, J.; Beltrán, D.; Amorós, P. J. Catal. 2007, 251, 388. doi: 10.1016/j.jcat.2007.08.001
(171) Schager, F.; Bonrath, W. J. Catal. 1999, 182, 282. doi: 10.1006/jcat.1998.2351
(172) Wang, H.; Xu, B. Q. Appl. Catal. A 2004, 275, 247. doi: 10.1016/j.apcata.2004.07.038
(173) Kozhevnikov, I. V.; Kulikov, S. M.; Chukaeva, N. G.; Kirsanov, A. T.; Letunova, A. B.; Blinova, V. I. React. Kinet. Catal. L. 1992, 47, 59. doi:10.1007/bf02063560
(174) Xing, H. B.; Wang, T.; Zhou, Z. H.; Dai, Y. Y. Synthetic. Commun. 2006, 36, 2433. doi:10.1080/00397910600781166
(175) Laha, S. C.; Venkatesan, C.; Sakthivel, A.; Komura, K.; Kim, T. H.; Cho, S. J.; Huang, S. J.; Wu, P. H.; Liu, S. B.; Sasaki, Y.; Kobayashi, M.; Sugi, Y. Micropor. Mesopor. Mater. 2010, 133, 82. doi: 10.1016/j.micromeso.2010.04.018
(176) Hirose, N.; Inoue, H.; Matsunami, T.; Yoshimura, T.; Morita, K.; Horikawa, Y.; Iwata, N.; Hayashi, K.; Seki, C.; Minami, N.; et al.Process for the preparation of alpha-tocopherol. CN 1123278A, 1996.
(177) Kokubo, Y.; Hasegawa, A.; Kuwata, S.; Ishihara, K.; Yamamoto, H.; Ikariya, T. Adv. Synth. Catal. 2005, 347, 220. doi: 10.1002/adsc.200404312
(178) Xing, H. B.; Wang, T.; Dai, Y. Y. J. Supercrit. Fluid. 2009, 49, 52. doi: 10.1016/j.supflu.2008.12.003

[1] Yueqi YIN,Mengxu JIANG,Chunguang LIU. DFT Study of POM-Supported Single Atom Catalyst (M1/POM, M = Ni, Pd, Pt, Cu, Ag, Au, POM = [PW12O40]3-) for Activation of Nitrogen Molecules[J]. Acta Physico-Chimica Sinca, 2018, 34(3): 270-277.
[2] Chi CHEN,Xue ZHANG,Zhi-You ZHOU,Xin-Sheng ZHANG,Shi-Gang SUN. Experimental Boosting of the Oxygen Reduction Activity of an Fe/N/C Catalyst by Sulfur Doping and Density Functional Theory Calculations[J]. Acta Physico-Chimica Sinca, 2017, 33(9): 1875-1883.
[3] Pei-Yi LIAO,Chen ZHANG,Li-Jun ZHANG,Yan-Zhang YANG,Liang-Shu ZHONG,Xiao-Ya GUO,Hui WANG,Yu-Han SUN. Influences of Cu Content on the Cu/Co/Mn/Al Catalysts Derived from Hydrotalcite-Like Precursors for Higher Alcohols Synthesis via Syngas[J]. Acta Physico-Chimica Sinca, 2017, 33(8): 1672-1680.
[4] Ling-Xiao HU,Lian WANG,Fei WANG,Chang-Bin ZHANG,Hong HE. Catalytic Oxidation of o-Xylene over Pd/γ-Al2O3 Catalysts[J]. Acta Physico-Chimica Sinca, 2017, 33(8): 1681-1688.
[5] Yang ZHOU,Qing-Qing CHENG,Qing-Hong HUANG,Zhi-Qing ZOU,Liu-Ming YAN,Hui YANG. Highly Dispersed Cobalt-Nitrogen Co-doped Carbon Nanofiber as Oxygen Reduction Reaction Catalyst[J]. Acta Physico-Chimica Sinca, 2017, 33(7): 1429-1435.
[6] Xiao ZHAI,Yi DING. Nanoporous Metal Electrocatalysts for Oxygen Reduction Reactions[J]. Acta Physico-Chimica Sinca, 2017, 33(7): 1366-1378.
[7] . Effects of CeO2 Addition on Improved NO Oxidation Activities of Pt/SiO2-Al2O3 Diesel Oxidation Catalysts[J]. Acta Physico-Chimica Sinca, 2017, 33(6): 1242-1252.
[8] Shuai-Qi SUN,Yan-Hui YI,Li WANG,Jia-Liang ZHANG,Hong-Chen GUO. Preparation and Performance of Supported Bimetallic Catalysts for Hydrogen Production from Ammonia Decomposition by Plasma Catalysis[J]. Acta Physico-Chimica Sinca, 2017, 33(6): 1123-1129.
[9] Yi-Hao HU,Tong-Yang SONG,Yue-Juan WANG,Geng-Sheng HU,Guan-Qun XIE,Meng-Fei LUO. Gas Phase Dehydrochlorination of 1, 1, 2-Trichloroethane over Zn/SiO2 Catalysts: Acidity and Deactivation[J]. Acta Physico-Chimica Sinca, 2017, 33(5): 1017-1026.
[10] Chong-Yi LING,Jin-Lan WANG. Recent Advances in Electrocatalysts for the Hydrogen Evolution Reaction Based on Graphene-Like Two-Dimensional Materials[J]. Acta Physico-Chimica Sinca, 2017, 33(5): 869-885.
[11] Jun WANG,Zi-Dong WEI. Recent Progress in Non-Precious Metal Catalysts for Oxygen Reduction Reaction[J]. Acta Physico-Chimica Sinca, 2017, 33(5): 886-902.
[12] Xiao-Ping GAO,Zhang-Long GUO,Ya-Nan ZHOU,Fang-Li JING,Wei CHU. Catalytic Performance and Characterization of Anatase TiO2 Supported Pd Catalysts for the Selective Hydrogenation of Acetylene[J]. Acta Physico-Chimica Sinca, 2017, 33(3): 602-610.
[13] Yang Lü,Yu-Jiang SONG,Hui-Yuan LIU,Huan-Qiao LI. Pd-Containing Core/Pt-Based Shell Structured Electrocatalysts[J]. Acta Physico-Chimica Sinca, 2017, 33(2): 283-294.
[14] . Solid-State NMR Characterization of the Structure and Catalytic Reaction Mechanism of Solid Acid Catalysts[J]. Acta Physico-Chimica Sinca, 2017, 33(2): 270-282.
[15] Xiao-Fang BAI,Wei CHEN,Bai-Yin WANG,Guang-Hui FENG,Wei WEI,Zheng JIAO,Yu-Han SUN. Recent Progress on Electrochemical Reduction of Carbon Dioxide[J]. Acta Physico-Chimica Sinca, 2017, 33(12): 2388-2403.