声化学法制备格利雅试剂及其合成二甲基苄基甲醇的研究
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摘要
二甲基苄基甲醇是一种重要的香料，它除了可用于制备花香型香精，如百合，水仙，铃兰等高级花香型香精外，它的乙酸酯有清新的香韵，因而使其价值倍增，常用在风信子，百合，茉莉花等花香型香精中。
格利雅试剂在香料、医药的合成中应用很广泛，但传统的制备工艺要求苛刻。本研究采用的在超声波条件下制备格利雅试剂，工艺简单，反应时间大大缩短，对设备的要求低，条件温和，反应可以用普通试剂级的乙醚或THF而无需干燥，且不需要对周围环境的条件提出严格要求，反应的诱导期大大缩短，可直接得到高产率的格利雅试剂，而且相当一部分较难合成的格利雅试剂在超声波条件下合成时不需要引发剂。这些对格利雅试剂的工业化生产具有重要的意义。
本文探讨了超声波合成格利雅试剂的机理，研究了声化学法制备格利雅试剂氯化苄基镁的最佳工艺条件为：在超声波的功率为500W，频率为25KHZ，有12个换能器的条件下，水浴温度为20℃，以THF为溶剂，不搅拌。
本论文首次利用声化学法制备格利雅试剂-氯化苄基镁，并研究了利用氯化苄基镁合成二甲基苄基甲醇的原理及最佳工艺条件，其工艺条件为：丙酮的浓度为12.5％，丙酮与格利雅试剂的摩尔比为1：1.1，温度为10℃。
主要研究内容如下：
1．探讨了超声波合成格利雅试剂的机理
2．研究超声波法制备格利雅试剂氯化苄基镁的工艺条件。探索合成格利雅试剂的新工艺。
3．研究二甲基苄基甲醇制备方法，寻找制备二甲基苄基甲醇的最佳工艺条件和工艺路线。
Dimethylbenzyl carbinol is a kind of important spices, it not only can be used for preparing the fragrant essence of flower, for instance lily, the advanced fragrant essence of flower, the narcissus , the lily of the valley ,etc., but also Dimethylbenzyl carbinol acetate have fresh fragrant and it make it's value double. Dimethylbenzyl carbinol acetate usually used in the fragrant essence of flower of hyacinth, lily, jasmine etc..
Grignard reagents are used very extensive in being synthetic in spices, medicine. The traditional preparation craft requests were rigor. Under ultrasonic, the craft of preparation Grignard reagents is simple, reactive time being shorten greatly, only needing simple equipments, mild condition and the reactive impregnant can used ordinary ether or THF that can not need to be dry. Reactive induction period shorten greatly, Grignard reagents of high yield rate can get directly and quite a few Grignard reagents that more difficult to preparation did not need initiator while synthesized under the ultrasonic condition. It has important meanings in industrialization of Grignard reagents.
This paper has probed into the synthetic mechanics of Grignard reagents under ultrasonic condition. This paper has studied preparation of Grignard reagents under phonochemistry and optimum technologic conditions is: the power of ultrasonic is 500W and frequency is 250KHZ, having twelve energy conversion devices, water bath temperature being 20C, solvent being THF,unstirred.
This paper first prepared Grignard reagent benzylmagnesium chloride under phonochemistry and we have researched the principle and optimum technologic conditions while used benzylmagnesium chloride preparation Dimethylbenzyl carbinol .The optimum technologic conditions is: the concentration of acetone being 12.5 percent, mol ratio being 1.1:1 between acetone and Grignard reagent, temperature being 10C.
The main research contents are as follows:
1. Discuss mechanism of preparing Grignard reagents under ultrasonic condition.
2. Study the technologic conditions of preparing Grignard reagent benzylmagnesium chloride under ultrasonic condition. Explore the new craft of preparing Grignard reagents.
3. Study prepared method of dimethylbenzyl carbinol and seek the best technologic conditions and craft route of dimethylbenzyl carbinol.
格利雅试剂在香料、医药的合成中应用很广泛，但传统的制备工艺要求苛刻。本研究采用的在超声波条件下制备格利雅试剂，工艺简单，反应时间大大缩短，对设备的要求低，条件温和，反应可以用普通试剂级的乙醚或THF而无需干燥，且不需要对周围环境的条件提出严格要求，反应的诱导期大大缩短，可直接得到高产率的格利雅试剂，而且相当一部分较难合成的格利雅试剂在超声波条件下合成时不需要引发剂。这些对格利雅试剂的工业化生产具有重要的意义。
本文探讨了超声波合成格利雅试剂的机理，研究了声化学法制备格利雅试剂氯化苄基镁的最佳工艺条件为：在超声波的功率为500W，频率为25KHZ，有12个换能器的条件下，水浴温度为20℃，以THF为溶剂，不搅拌。
本论文首次利用声化学法制备格利雅试剂-氯化苄基镁，并研究了利用氯化苄基镁合成二甲基苄基甲醇的原理及最佳工艺条件，其工艺条件为：丙酮的浓度为12.5％，丙酮与格利雅试剂的摩尔比为1：1.1，温度为10℃。
主要研究内容如下：
1．探讨了超声波合成格利雅试剂的机理
2．研究超声波法制备格利雅试剂氯化苄基镁的工艺条件。探索合成格利雅试剂的新工艺。
3．研究二甲基苄基甲醇制备方法，寻找制备二甲基苄基甲醇的最佳工艺条件和工艺路线。
Dimethylbenzyl carbinol is a kind of important spices, it not only can be used for preparing the fragrant essence of flower, for instance lily, the advanced fragrant essence of flower, the narcissus , the lily of the valley ,etc., but also Dimethylbenzyl carbinol acetate have fresh fragrant and it make it's value double. Dimethylbenzyl carbinol acetate usually used in the fragrant essence of flower of hyacinth, lily, jasmine etc..
Grignard reagents are used very extensive in being synthetic in spices, medicine. The traditional preparation craft requests were rigor. Under ultrasonic, the craft of preparation Grignard reagents is simple, reactive time being shorten greatly, only needing simple equipments, mild condition and the reactive impregnant can used ordinary ether or THF that can not need to be dry. Reactive induction period shorten greatly, Grignard reagents of high yield rate can get directly and quite a few Grignard reagents that more difficult to preparation did not need initiator while synthesized under the ultrasonic condition. It has important meanings in industrialization of Grignard reagents.
This paper has probed into the synthetic mechanics of Grignard reagents under ultrasonic condition. This paper has studied preparation of Grignard reagents under phonochemistry and optimum technologic conditions is: the power of ultrasonic is 500W and frequency is 250KHZ, having twelve energy conversion devices, water bath temperature being 20C, solvent being THF,unstirred.
This paper first prepared Grignard reagent benzylmagnesium chloride under phonochemistry and we have researched the principle and optimum technologic conditions while used benzylmagnesium chloride preparation Dimethylbenzyl carbinol .The optimum technologic conditions is: the concentration of acetone being 12.5 percent, mol ratio being 1.1:1 between acetone and Grignard reagent, temperature being 10C.
The main research contents are as follows:
1. Discuss mechanism of preparing Grignard reagents under ultrasonic condition.
2. Study the technologic conditions of preparing Grignard reagent benzylmagnesium chloride under ultrasonic condition. Explore the new craft of preparing Grignard reagents.
3. Study prepared method of dimethylbenzyl carbinol and seek the best technologic conditions and craft route of dimethylbenzyl carbinol.
引文
[1]何坚，季儒英．香料概论．中国石化出版社．1993，1-2
[2]舒宏福．近十五年来香料的进展(上)[J]．香料香精化妆品，2001，3：29-31
[3]舒宏福．近十五年来香料的进展(下)[J]．香料香精化妆品，2001，4：29-33
[4]刘树文．合成香料技术手册编著．中国轻工业出版社，2000：前言
[5]近年来国外主要合成香料发展情况．国内外香料香精化妆品信息．2002，(3)：3-5
[6]曾育才．格利雅试剂制备性质及其在合成中应用．宁德师专学报(自然科学版)，1999，11(3)：170-176
[7]顾小焱。格氏试剂氯乙烯镁的制备。试剂与精细化学品，1999(9)：33-38
[8]Metals and Thermit Corporation. Vinylic Magnesium Chloride Complexes and method of making same[P].US, 1957,777158
[9]Emil Kaiser, Lorraine Spora. PREPARATION OF GRIGNARD REAGENTS[P].US, 1959,2881225.
[10]Hugh E. Ramsden, Scotch Plains, Allen E.Balind, Woodbridge and Clarence K.Bank, Westfied,N.J.ARYL HLORIDE-CYCLIC ETHER GRIGNARD REAGENTS[P] .US, 1960,2959596.
[11]John Stanley Hill. Method of manufacturing organometallic compounds[P]. US, 1951,2552676.
[12]Hugh E.Ramsden, Scotch Plains,N.J. Chemical process and product[P].US, 1958,2838508.
[13]Coates,G.E., Wade,K., MLH Green. Organometallic Compounds, 3rd ed.,vol, 1,p. 77,Methuen and Co.,Ltd.,London, 1967.
[14]Johu F.Nobis,Robert E.Robinson. Preparation of di-grignard organometallic derivatives[P]. US, 1957,2759624.
[15]John F.Nobis, Robert E. Robinson. Process for organo-metallic derivatives[P]. US, 1957,2759626.
[16]Coates,G.H. Principles of Organometallic Chemistry, Chapman & Hall,London, 1977.
[17]Houghton,R.P, Metal Complexes in Organic Chemistry, Cambridge Univ. Press, 1979.
[18]Pauling,L．，“The Nature of the Chemical Bond”，卢嘉锡译，《化学键的本质》。上海：上海科学技术出版社，1966，84
[19]Xiulin Ye. Confor-mational Effects in Organic Reactions.
Org.Chem. 1985,(1):60～70
[20] Xiulin Ye. Principle of Least Conformational Change. Chemistry. 1986(4): 1～11
[21] Ingold,C.K., Structure and Mechanism in Organic Chemistry, 2nd ed.,pp. 1027～1029,G.Bell & Sons Ltd.,London,1969.
[22] Gould,E.S.,Mechanism and Structure in Organic Chemistry, pp.403～404,Henry Holt & Co.,New York,1959.
[23] 醛、酮与格利雅试剂的反应。王协璜，安徽师大学报(自然科学版)，1994，17(1)：75—79
[24] 邢其毅．基础有机化学(上)，北京：高等教育出版社，1980，319
[25] 龚跃法。有机化学。北京：高等教育出版社，1988，(6)：481
[26] Metals and Thermit Corporation. ORGANOMANESIUM CHLORIDE COMPLEXES[P].US, 1959,823958.
[27] Metals and Yhermit Corporation. PREPARATION OF ORGANOMAGNESIUM CHLORIDES [P]. US, 1960,829243.
[28] Robert van helden. PROCESS FOR THE PREPARATION OF 2-PHENYLETHANOL OR DERIVATIVES THEREOF[P].US, 1979,1542112.
[29] 邝生鲁，贡长生。声化学及其应用。化学通报，1990(6)：23-27
[30] 熊大民。声化学的研究与应用现状。昆明理工大学学报，2001，26(6)：84-88
[31] 冯若，赵逸云，陈兆华等。声化学主动力．声空化及其检测技术。声学技术，1994，13(2)56-61
[32] 黄昆，嵇学林，刘华。有机声化学最新进展．化学通报，1993，5：7-11
[33] 荣建辉。超声波在有机合成方面的新进展．化学通报，1991，2：8-14
[34] 赵逸云，鲍慈光，冯若，王双维，朱昌平．声化学应用研究的新进展．化学通报，1994，8：26-29
[35] Mason T J. Sonochemistry:The use of Ultrasound in chemistry,Royal Society of Chemistry, 1990.
[36] 赵之平，陈澄华．超声传质过程机理．化工设计，1997，6：30-33
[37] 李广学．超声波在化工过程中的应用．化学反应工程与工艺，1991，7(4)：416-421
[38] Geankoplis C J. transport processes and unit operations.2nd ed. Massachusetts:Allyn and Bacon Inc. 1983:371-464.
[39] 李晖．超声波强化液-固传质的机理研究．沈阳化工学院学报，1994，8(3)：175-181
[40] 陈健，肖凯军，李琳等．超声波强化超滤过程．应用声学，2002，21(3)：45-48
[41] 陈健，李琳，肖凯军等．超声波强化超滤的研究进展．水处理技术，2003，29(4)：191-193
[42] 于凤文，计建炳，刘化章．超声波在催化过程中的应用．应用声学，2002，21(2)：40-45
[43] 陈先庆．超声波防垢技术在油田中的应用研究．钻采工艺，2000，23(3)：58-61
[44] 刘岩，蔡伟民。超声波空化效应和声化学研究进展。大自然探索，1994，13(27)：81-88
[45] 刘岩。声致发光中原子光谱强度的一个定量模型。应用声学，1991，10(6)：16-19
[46] Lauterborn W.ed. Cavitation and Inhomogeneitcs in Underwater Acoustics. Springer-Verlag.Berlin, 1980.
[47] Teaching and research action of organic chemistry, chemistry department, Lanzhou university, Teaching and research action of organic chemistry, chemistry department, Fudan university, Edrs. organic chemistry experiment[M].Beijing:High Education Press, 1988:214
[2]舒宏福．近十五年来香料的进展(上)[J]．香料香精化妆品，2001，3：29-31
[3]舒宏福．近十五年来香料的进展(下)[J]．香料香精化妆品，2001，4：29-33
[4]刘树文．合成香料技术手册编著．中国轻工业出版社，2000：前言
[5]近年来国外主要合成香料发展情况．国内外香料香精化妆品信息．2002，(3)：3-5
[6]曾育才．格利雅试剂制备性质及其在合成中应用．宁德师专学报(自然科学版)，1999，11(3)：170-176
[7]顾小焱。格氏试剂氯乙烯镁的制备。试剂与精细化学品，1999(9)：33-38
[8]Metals and Thermit Corporation. Vinylic Magnesium Chloride Complexes and method of making same[P].US, 1957,777158
[9]Emil Kaiser, Lorraine Spora. PREPARATION OF GRIGNARD REAGENTS[P].US, 1959,2881225.
[10]Hugh E. Ramsden, Scotch Plains, Allen E.Balind, Woodbridge and Clarence K.Bank, Westfied,N.J.ARYL HLORIDE-CYCLIC ETHER GRIGNARD REAGENTS[P] .US, 1960,2959596.
[11]John Stanley Hill. Method of manufacturing organometallic compounds[P]. US, 1951,2552676.
[12]Hugh E.Ramsden, Scotch Plains,N.J. Chemical process and product[P].US, 1958,2838508.
[13]Coates,G.E., Wade,K., MLH Green. Organometallic Compounds, 3rd ed.,vol, 1,p. 77,Methuen and Co.,Ltd.,London, 1967.
[14]Johu F.Nobis,Robert E.Robinson. Preparation of di-grignard organometallic derivatives[P]. US, 1957,2759624.
[15]John F.Nobis, Robert E. Robinson. Process for organo-metallic derivatives[P]. US, 1957,2759626.
[16]Coates,G.H. Principles of Organometallic Chemistry, Chapman & Hall,London, 1977.
[17]Houghton,R.P, Metal Complexes in Organic Chemistry, Cambridge Univ. Press, 1979.
[18]Pauling,L．，“The Nature of the Chemical Bond”，卢嘉锡译，《化学键的本质》。上海：上海科学技术出版社，1966，84
[19]Xiulin Ye. Confor-mational Effects in Organic Reactions.
Org.Chem. 1985,(1):60～70
[20] Xiulin Ye. Principle of Least Conformational Change. Chemistry. 1986(4): 1～11
[21] Ingold,C.K., Structure and Mechanism in Organic Chemistry, 2nd ed.,pp. 1027～1029,G.Bell & Sons Ltd.,London,1969.
[22] Gould,E.S.,Mechanism and Structure in Organic Chemistry, pp.403～404,Henry Holt & Co.,New York,1959.
[23] 醛、酮与格利雅试剂的反应。王协璜，安徽师大学报(自然科学版)，1994，17(1)：75—79
[24] 邢其毅．基础有机化学(上)，北京：高等教育出版社，1980，319
[25] 龚跃法。有机化学。北京：高等教育出版社，1988，(6)：481
[26] Metals and Thermit Corporation. ORGANOMANESIUM CHLORIDE COMPLEXES[P].US, 1959,823958.
[27] Metals and Yhermit Corporation. PREPARATION OF ORGANOMAGNESIUM CHLORIDES [P]. US, 1960,829243.
[28] Robert van helden. PROCESS FOR THE PREPARATION OF 2-PHENYLETHANOL OR DERIVATIVES THEREOF[P].US, 1979,1542112.
[29] 邝生鲁，贡长生。声化学及其应用。化学通报，1990(6)：23-27
[30] 熊大民。声化学的研究与应用现状。昆明理工大学学报，2001，26(6)：84-88
[31] 冯若，赵逸云，陈兆华等。声化学主动力．声空化及其检测技术。声学技术，1994，13(2)56-61
[32] 黄昆，嵇学林，刘华。有机声化学最新进展．化学通报，1993，5：7-11
[33] 荣建辉。超声波在有机合成方面的新进展．化学通报，1991，2：8-14
[34] 赵逸云，鲍慈光，冯若，王双维，朱昌平．声化学应用研究的新进展．化学通报，1994，8：26-29
[35] Mason T J. Sonochemistry:The use of Ultrasound in chemistry,Royal Society of Chemistry, 1990.
[36] 赵之平，陈澄华．超声传质过程机理．化工设计，1997，6：30-33
[37] 李广学．超声波在化工过程中的应用．化学反应工程与工艺，1991，7(4)：416-421
[38] Geankoplis C J. transport processes and unit operations.2nd ed. Massachusetts:Allyn and Bacon Inc. 1983:371-464.
[39] 李晖．超声波强化液-固传质的机理研究．沈阳化工学院学报，1994，8(3)：175-181
[40] 陈健，肖凯军，李琳等．超声波强化超滤过程．应用声学，2002，21(3)：45-48
[41] 陈健，李琳，肖凯军等．超声波强化超滤的研究进展．水处理技术，2003，29(4)：191-193
[42] 于凤文，计建炳，刘化章．超声波在催化过程中的应用．应用声学，2002，21(2)：40-45
[43] 陈先庆．超声波防垢技术在油田中的应用研究．钻采工艺，2000，23(3)：58-61
[44] 刘岩，蔡伟民。超声波空化效应和声化学研究进展。大自然探索，1994，13(27)：81-88
[45] 刘岩。声致发光中原子光谱强度的一个定量模型。应用声学，1991，10(6)：16-19
[46] Lauterborn W.ed. Cavitation and Inhomogeneitcs in Underwater Acoustics. Springer-Verlag.Berlin, 1980.
[47] Teaching and research action of organic chemistry, chemistry department, Lanzhou university, Teaching and research action of organic chemistry, chemistry department, Fudan university, Edrs. organic chemistry experiment[M].Beijing:High Education Press, 1988:214