二氯代甲氧基苯的合成与动力学研究
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摘要
主要对二氯代甲氧基苯的合成工艺与合成动力学进行了研究。确定了以1,2,4-三氯苯和甲醇钠为原料制备二氯代甲氧基苯的工艺路线,系统地研究了原料配比、反应温度、反应时间、溶剂用量等因素对反应的影响,通过L_9(3~4)安排试验,得到了1,4-二氯-2-甲氧基苯优化工艺条件:n(1,2,4-三氯苯):n(甲醇钠)=1:1.3,反应温度90℃,反应时间120min,溶剂质量百分比含量为140%。在优化的条件下,产物收率达到74%以上。
在相同物料配比、相同的溶剂用量、不同的反应温度条件下,测定不同反应时间时1,4-二氯-2-甲氧基苯(U)、1,2-二氯-4-甲氧基苯(V)、2,4-二氯-1-甲氧基苯(W)的产率和1,2,4-三氯苯的含量,以此确定动力学方程中的待定参数。通过分析反应温度为353.15K、358.15K、368.15K、373.15K、378.15K、383.15K时的产物含量,确定该反应为一级反应。得到的动力学方程为:
得到主反应活化能为70.329kJ·mol~(-1)。实验数据验证表明:动力学方程能较好与实验数据相吻合,实验值和计算值的平均相对误差约为2.08%,该动力学方程比较准确描述在优化工艺条件下的反应过程。
采用气相色谱对1,2,4-三氯苯和甲醇钠的反应产物进行了定量分析,通过红外光谱、质谱和核磁共振波谱对1,4-二氯-2-甲氧基苯的结构进行了表征,对合成1,4-二氯-2-甲氧基苯的反应机理进行了探讨,认为1,2,4-三氯苯和甲醇钠的反应机理属于SN2亲核取代反应。
The synthesis and kinetics of dichloromethoxybenzene were studied in this paper. dichloromethoxybenzene was synthesized with 1, 2, 4-trichlorobenze and sodium methoxide as raw materials. Factors that had effect on the product's yield, such as material's ratio, reaction temperature, time and solvent were systematically studied. By L_9(3~4) arrangements test, the optimal process conditions of 1, 4-dichloro-2- methoxybenzene were obtained, which were at a n(NaOCH_3)/n(1, 2, 4-TCB) ratio of 1.3, a reaction temperature of 90℃, a reaction time of 120min and solvent percentage of quality 140%. At the most optimal conditions, the product yield was over 74%.
The 1, 4-dichloro-2-methoxybenzene's(U), 1, 2-dichloro-4-methoxybenzene's(V), 2,4-dichloro-1-methoxybenzene's(W) yield and the content of 1, 2, 4-trichlorobenze were determined at the same raw materials' ratio and solvent but different reaction temperature conditions so that the kinetics parameters could be determined. The reaction series at different reaction temperatures(353.15K、358.15K、368.15K、373.15K、378.15K、383.15K)are 1, so it can be determined as the first, and the kinetic equations are, and the value of the main activation energy obtained is 70.329kJ·mol~(-1). It's showed by the experiment's verifying that kinetic equations can match well with the experimental data and the average relative error of the experimental and calculated values is about 2.08%, while the optimum conditions of the reaction process can be accurately described by the kinetic equation.
The products of the reaction were analyzed by GC. The structure of 1, 4-dichloro-2-methoxybenzene was identified by IR, MS and 1HNMR. The possible mechanism of the reaction was also discussed, which is classified as S_N2 nucleophilic substitution reactions.
在相同物料配比、相同的溶剂用量、不同的反应温度条件下,测定不同反应时间时1,4-二氯-2-甲氧基苯(U)、1,2-二氯-4-甲氧基苯(V)、2,4-二氯-1-甲氧基苯(W)的产率和1,2,4-三氯苯的含量,以此确定动力学方程中的待定参数。通过分析反应温度为353.15K、358.15K、368.15K、373.15K、378.15K、383.15K时的产物含量,确定该反应为一级反应。得到的动力学方程为:
得到主反应活化能为70.329kJ·mol~(-1)。实验数据验证表明:动力学方程能较好与实验数据相吻合,实验值和计算值的平均相对误差约为2.08%,该动力学方程比较准确描述在优化工艺条件下的反应过程。
采用气相色谱对1,2,4-三氯苯和甲醇钠的反应产物进行了定量分析,通过红外光谱、质谱和核磁共振波谱对1,4-二氯-2-甲氧基苯的结构进行了表征,对合成1,4-二氯-2-甲氧基苯的反应机理进行了探讨,认为1,2,4-三氯苯和甲醇钠的反应机理属于SN2亲核取代反应。
The synthesis and kinetics of dichloromethoxybenzene were studied in this paper. dichloromethoxybenzene was synthesized with 1, 2, 4-trichlorobenze and sodium methoxide as raw materials. Factors that had effect on the product's yield, such as material's ratio, reaction temperature, time and solvent were systematically studied. By L_9(3~4) arrangements test, the optimal process conditions of 1, 4-dichloro-2- methoxybenzene were obtained, which were at a n(NaOCH_3)/n(1, 2, 4-TCB) ratio of 1.3, a reaction temperature of 90℃, a reaction time of 120min and solvent percentage of quality 140%. At the most optimal conditions, the product yield was over 74%.
The 1, 4-dichloro-2-methoxybenzene's(U), 1, 2-dichloro-4-methoxybenzene's(V), 2,4-dichloro-1-methoxybenzene's(W) yield and the content of 1, 2, 4-trichlorobenze were determined at the same raw materials' ratio and solvent but different reaction temperature conditions so that the kinetics parameters could be determined. The reaction series at different reaction temperatures(353.15K、358.15K、368.15K、373.15K、378.15K、383.15K)are 1, so it can be determined as the first, and the kinetic equations are, and the value of the main activation energy obtained is 70.329kJ·mol~(-1). It's showed by the experiment's verifying that kinetic equations can match well with the experimental data and the average relative error of the experimental and calculated values is about 2.08%, while the optimum conditions of the reaction process can be accurately described by the kinetic equation.
The products of the reaction were analyzed by GC. The structure of 1, 4-dichloro-2-methoxybenzene was identified by IR, MS and 1HNMR. The possible mechanism of the reaction was also discussed, which is classified as S_N2 nucleophilic substitution reactions.
引文
[1]王玉玲,李绮云,间溴苯甲醚的合成,沈阳化工,1993,6:5-6
[2]高建荣,何玲辉,何西等,间溴苯甲醚合成工艺的研究,精细石油化工,1999,6:17-19
[3]丁德毅,液状冰染染料,染料工业,1990,27(3):18-21
[4]Shimizu T,Dyeing fibers and leather products with ice color uses a reactive dichlorotriazine dye,JP2002212885,2001-01-10
[5]李洪林,孟明扬,色酚AS系列产品催化合成新工艺,精细与专用化学品,1999,11:15-17
[6]何岩彬,杨新玮,国内冰染染料发展概况—国产冰染色酚在有机颜料上的应用,上海染料,2000,28(1):5-12
[7]A. John Blacker,Matthew J. Stirling, and Michael I. Page,Catalytic racemisation of chiral amines and application in dynamic kinetic resolution,Organic Process Research & Development 2007,11:642-648
[8]黄卫平,高效液相色谱法测定豆芽中4-氯苯氧乙酸钠残留量,中华预防医学杂志,2002,36(1):44-45.
[9]美国环保局,美国环保局农药毒性资料库[EB/OL],[2005-04-1], http://www.epa.gov
[10]Ashikati M,Sakakibara H,Lin S,et a1,Cytokinin oxidaseregulates rice grain producfion, Science,2005, 309:741-745
[11]Multani D S,Btiggs P S,Chamberlin M A,et a1,Lossof an MDR transporter in compact stalks of maize br2 and sorghum dw3 mutants, Science ,2003,302:81-84
[12]Sakamoto T,Morinaka Y,Ohnishi T,Erect leaves caused by brassinosteroid deficiency increase biomass production and grain yield in rice, Nat Bioteclmo1,2006, 24:105-109
[13]Filler R,The asymmetric synthesis ofα-amino acids remains an important challenge for organic chemists,Chemtech,1974,752
[14]Kumadaki I,Synthesis of enantiomerically pure phenylalanine analogues,J Synth Org Chem Jpn,1984,42:786
[15]Yaskioka H,Takayama C, Matsuo N,α-amino acid synthesis,J Synth Org Chem Jpn,1984,42:809
[16]Penglist A AE, Systhesis of 3-(2-furoyl)-L-alanine,Adv Carbohyder Chem Biochem,1981,38:195
[17]Foster A B,Westwood J H,Forstudies on the biosynthesis to isolation and biological activity,Pure and Applied Chem,1973,35:147
[18]Kent P W, Total synthesis of L-β-(5-hydroxy-2-pyridyl)alanine, Chem Ind 1969, 1128
[19]US,Department of Agrlculture,Soil Conservation Service.SCS/ARS/CES Pesteci- ide Properties Datebase:Version2.0(summary) Syracuse,NY:USDA,Soil Conservation Service,1990
[20]Worthing,C.R.The Pesticide Manual:A World Compendium 8th Ed,Croydon,England,British Crop Protection Council,1987: 99-101
[21]章小波等,安息香酸系除草剂麦草畏的合成,农药,2002,11(41):13-14
[22]张咏,陆敏,麦草畏合成工艺的研究,农药,2002,7:15-17
[23]落合道彦,上门敏也,3,6-二氯-2-甲氧基苯甲酸的制备方法,日本公开特许:昭48-5574,1973
[24]Dong-WheeKim,Process for the Production of 2-Methoxy-3,6-Dichlorobenzoic Acid,US4161611,1979
[25]Sidney B Richer,2-Methoxy-3,6-Dichlorobenzoates,US3013054,1961-12-12
[26]Heinz Manfred Becher,Richard Sehring,Process for the Production of 2-Methoxy-3,6-Dichlorohenzoic acid,US3928432,1974
[27]Arthur W.C,Crystal Lake,Process for the preparation of 2,5-dichlorophenol, USP 4094913,1978-06-13
[28]Henrick C A, Scheuerman R A,Preparation of 2,5-dichlorophenol, for preparation of dicamba, comprises selectively oxidizing 1,4-dichlorobenzene using vanadium species in presence of acid e.g. alpha-hydroxy-, di- or tribasic- and/or sulfonic acid, USP 6586624-B1,2003-06-01
[29] Richard H.Sehring, et al ,Preparation of 2,5-dichlorophenol, USP4670610, 1987-01-02
[30]Payne,Kenneth Richard,process for the production of dihalophenols,US P3726929,1971-02-03
[31]Shakirov lenar gazizovich, Isolation of alkali metal 2,4-dichlorophenolate and 2,4-dichlorophenol from a mixture of chlorophenols,GB2175299,1986
[32]Behramkamdin M M,et al Process for the separation of dichlorophenol isomers,GB 2341178,2000
[33]Wilfrit,Lowe,Process for isolation of 2,5-dichlorophenol an isomeric mixture of dichlorophenols,USP 3462498,1965-09-10
[34]黑中一,王红学,寇俊杰,制备高纯度2,4-二氯苯酚的几种方法,农药,2003,10(24):9-11
[35] Anwar M M,Dissociation extraction,Trans.Instn.0Chem.Engrs,1971,49:95-100;1973,151:151-158
[36]肖刚,染料工业技术,北京:化学工业出版社,2004,144-158
[37]Ciba,Higher wash fastness in PES dye-ing,Dyer,2003(9):43-50
[38]黎其万,王继良,6-(3-甲基-4-对甲苯磺酰基-2-丁烯基)-2,3,4,5-四甲氧基甲苯的合成,精细化工,2003,20(11):668-670
[39]Filippo Maiolo,Lorenzo Testaferri,Fragmentation of Aryl Alkyl Sulfides,A Simple,One-Pot Synthesis of Polymercaptobenzenes from Polychlorobenzenes, J.Org.Chem, 1981,46:3070-3073
[40]Lorenzo Testaferri,Marco Tingoli,and Marcello Tiecco,Reactions of Polychlorobenzenes with Alkanethiol Anions in HMPA,A Simple,High-Yield Synthesis of Poly(alky1thio)benzenes,J. Org. Chem,1980,45:4376-4380
[41]Pietro Cogolli,Filippo Maiolo,et al,Nucleophilic Aromatic Substitution Reactions of Unactivated Aryl Halides with Thiolate Ions in Hexamethylphosphoramide,J. Org. Chem, 44(15), 1979
[42]曹玉庆,杜云飞,陈保华,间溴苯甲醚的合成,中国医药工业杂志,2005,36(2):73-74
[43] Manchand PS, Belica PS, Wong HS, Synthesis of 3, 4, 5-trimethoxybenzalde -hyde,Synthetic Communication,1990,20(17):2659
[44]胡益民等,1,3,5-三甲氧基苯合成新方法研究,合成化学,1999,7(2):191-193
[45]Ji YF, Zong ZM,Wei XY,Efficient and convenient synthesis of 3, 4, 5-trimethox- ybenzaldehyde from p-cresol,2002,18(32):2809-2814
[46]朝广甸,范如霜,李述方,有机制备手册(上卷),北京:化学工业出版社,1985: 138
[47]王积涛,胡青眉,张宝申,工永梅,有机化学,南开大学出版社,1993
[48]Jayme N,Alison Butler,Vanadium Bromoperoxidase-Catalyzed Biosynthesis of Halogenated Marine Natural Products . J. Am. Chem. Soc, 2004, 126: 15060-15066
[49]Bert F .Sels,DirkE .De Vos,Mieke Brntinx,et al,Transition metal anion exchanged layered double hydroxides as a bioinspired model of vanadium bomoperoxidase, Jounal of catalysis,2003,216:288-297.
[50]AshutoshV .Joshi,Mubeen Baidossi,Sudip Mukhopadhyay,et al,Oxidative Bromination of Activated Aromatic Compounds Using Aqueous Nitric Acid as an Oxidant,Organic Process Research&Development, 2004, 8: 568-570
[51]Subhas Chandra Roy, Chandrani Guin, Kalyan Kumar Rana, et al. An efficient chemo and regioselective oxidative nuclear bromination of activated aromatic compounds using lithium bromide and ceric ammonium nitrate,Tetrahedron Letters, 2001,42: 6941-6942
[52]王玉玲,李绮云,间溴苯甲醚的合成,沈阳化工,1993(6):5-6
[53]秦付云等,过碳酸钠的热分解反应动力学,华东理工大学学报,2001-04, 27(2):214-216
[54]Gavin Macfie, Benjamin A,et al.The mechanism and kinetics of the fluorination of 2, 4-dinitrochlorobenzene using solid potassium fluoride in dimethylformamide, J. Phys. Chem. B,2001,105:12534-12546
[55]Heidi Markus,Sigmund Fugleberg,et al,Kinetic modelling of a solid-liquid reaction:reduction of ferric iron to ferrous iron with zinc sulphide,Chemical Engineering Science , 2004,59:919-930
[2]高建荣,何玲辉,何西等,间溴苯甲醚合成工艺的研究,精细石油化工,1999,6:17-19
[3]丁德毅,液状冰染染料,染料工业,1990,27(3):18-21
[4]Shimizu T,Dyeing fibers and leather products with ice color uses a reactive dichlorotriazine dye,JP2002212885,2001-01-10
[5]李洪林,孟明扬,色酚AS系列产品催化合成新工艺,精细与专用化学品,1999,11:15-17
[6]何岩彬,杨新玮,国内冰染染料发展概况—国产冰染色酚在有机颜料上的应用,上海染料,2000,28(1):5-12
[7]A. John Blacker,Matthew J. Stirling, and Michael I. Page,Catalytic racemisation of chiral amines and application in dynamic kinetic resolution,Organic Process Research & Development 2007,11:642-648
[8]黄卫平,高效液相色谱法测定豆芽中4-氯苯氧乙酸钠残留量,中华预防医学杂志,2002,36(1):44-45.
[9]美国环保局,美国环保局农药毒性资料库[EB/OL],[2005-04-1], http://www.epa.gov
[10]Ashikati M,Sakakibara H,Lin S,et a1,Cytokinin oxidaseregulates rice grain producfion, Science,2005, 309:741-745
[11]Multani D S,Btiggs P S,Chamberlin M A,et a1,Lossof an MDR transporter in compact stalks of maize br2 and sorghum dw3 mutants, Science ,2003,302:81-84
[12]Sakamoto T,Morinaka Y,Ohnishi T,Erect leaves caused by brassinosteroid deficiency increase biomass production and grain yield in rice, Nat Bioteclmo1,2006, 24:105-109
[13]Filler R,The asymmetric synthesis ofα-amino acids remains an important challenge for organic chemists,Chemtech,1974,752
[14]Kumadaki I,Synthesis of enantiomerically pure phenylalanine analogues,J Synth Org Chem Jpn,1984,42:786
[15]Yaskioka H,Takayama C, Matsuo N,α-amino acid synthesis,J Synth Org Chem Jpn,1984,42:809
[16]Penglist A AE, Systhesis of 3-(2-furoyl)-L-alanine,Adv Carbohyder Chem Biochem,1981,38:195
[17]Foster A B,Westwood J H,Forstudies on the biosynthesis to isolation and biological activity,Pure and Applied Chem,1973,35:147
[18]Kent P W, Total synthesis of L-β-(5-hydroxy-2-pyridyl)alanine, Chem Ind 1969, 1128
[19]US,Department of Agrlculture,Soil Conservation Service.SCS/ARS/CES Pesteci- ide Properties Datebase:Version2.0(summary) Syracuse,NY:USDA,Soil Conservation Service,1990
[20]Worthing,C.R.The Pesticide Manual:A World Compendium 8th Ed,Croydon,England,British Crop Protection Council,1987: 99-101
[21]章小波等,安息香酸系除草剂麦草畏的合成,农药,2002,11(41):13-14
[22]张咏,陆敏,麦草畏合成工艺的研究,农药,2002,7:15-17
[23]落合道彦,上门敏也,3,6-二氯-2-甲氧基苯甲酸的制备方法,日本公开特许:昭48-5574,1973
[24]Dong-WheeKim,Process for the Production of 2-Methoxy-3,6-Dichlorobenzoic Acid,US4161611,1979
[25]Sidney B Richer,2-Methoxy-3,6-Dichlorobenzoates,US3013054,1961-12-12
[26]Heinz Manfred Becher,Richard Sehring,Process for the Production of 2-Methoxy-3,6-Dichlorohenzoic acid,US3928432,1974
[27]Arthur W.C,Crystal Lake,Process for the preparation of 2,5-dichlorophenol, USP 4094913,1978-06-13
[28]Henrick C A, Scheuerman R A,Preparation of 2,5-dichlorophenol, for preparation of dicamba, comprises selectively oxidizing 1,4-dichlorobenzene using vanadium species in presence of acid e.g. alpha-hydroxy-, di- or tribasic- and/or sulfonic acid, USP 6586624-B1,2003-06-01
[29] Richard H.Sehring, et al ,Preparation of 2,5-dichlorophenol, USP4670610, 1987-01-02
[30]Payne,Kenneth Richard,process for the production of dihalophenols,US P3726929,1971-02-03
[31]Shakirov lenar gazizovich, Isolation of alkali metal 2,4-dichlorophenolate and 2,4-dichlorophenol from a mixture of chlorophenols,GB2175299,1986
[32]Behramkamdin M M,et al Process for the separation of dichlorophenol isomers,GB 2341178,2000
[33]Wilfrit,Lowe,Process for isolation of 2,5-dichlorophenol an isomeric mixture of dichlorophenols,USP 3462498,1965-09-10
[34]黑中一,王红学,寇俊杰,制备高纯度2,4-二氯苯酚的几种方法,农药,2003,10(24):9-11
[35] Anwar M M,Dissociation extraction,Trans.Instn.0Chem.Engrs,1971,49:95-100;1973,151:151-158
[36]肖刚,染料工业技术,北京:化学工业出版社,2004,144-158
[37]Ciba,Higher wash fastness in PES dye-ing,Dyer,2003(9):43-50
[38]黎其万,王继良,6-(3-甲基-4-对甲苯磺酰基-2-丁烯基)-2,3,4,5-四甲氧基甲苯的合成,精细化工,2003,20(11):668-670
[39]Filippo Maiolo,Lorenzo Testaferri,Fragmentation of Aryl Alkyl Sulfides,A Simple,One-Pot Synthesis of Polymercaptobenzenes from Polychlorobenzenes, J.Org.Chem, 1981,46:3070-3073
[40]Lorenzo Testaferri,Marco Tingoli,and Marcello Tiecco,Reactions of Polychlorobenzenes with Alkanethiol Anions in HMPA,A Simple,High-Yield Synthesis of Poly(alky1thio)benzenes,J. Org. Chem,1980,45:4376-4380
[41]Pietro Cogolli,Filippo Maiolo,et al,Nucleophilic Aromatic Substitution Reactions of Unactivated Aryl Halides with Thiolate Ions in Hexamethylphosphoramide,J. Org. Chem, 44(15), 1979
[42]曹玉庆,杜云飞,陈保华,间溴苯甲醚的合成,中国医药工业杂志,2005,36(2):73-74
[43] Manchand PS, Belica PS, Wong HS, Synthesis of 3, 4, 5-trimethoxybenzalde -hyde,Synthetic Communication,1990,20(17):2659
[44]胡益民等,1,3,5-三甲氧基苯合成新方法研究,合成化学,1999,7(2):191-193
[45]Ji YF, Zong ZM,Wei XY,Efficient and convenient synthesis of 3, 4, 5-trimethox- ybenzaldehyde from p-cresol,2002,18(32):2809-2814
[46]朝广甸,范如霜,李述方,有机制备手册(上卷),北京:化学工业出版社,1985: 138
[47]王积涛,胡青眉,张宝申,工永梅,有机化学,南开大学出版社,1993
[48]Jayme N,Alison Butler,Vanadium Bromoperoxidase-Catalyzed Biosynthesis of Halogenated Marine Natural Products . J. Am. Chem. Soc, 2004, 126: 15060-15066
[49]Bert F .Sels,DirkE .De Vos,Mieke Brntinx,et al,Transition metal anion exchanged layered double hydroxides as a bioinspired model of vanadium bomoperoxidase, Jounal of catalysis,2003,216:288-297.
[50]AshutoshV .Joshi,Mubeen Baidossi,Sudip Mukhopadhyay,et al,Oxidative Bromination of Activated Aromatic Compounds Using Aqueous Nitric Acid as an Oxidant,Organic Process Research&Development, 2004, 8: 568-570
[51]Subhas Chandra Roy, Chandrani Guin, Kalyan Kumar Rana, et al. An efficient chemo and regioselective oxidative nuclear bromination of activated aromatic compounds using lithium bromide and ceric ammonium nitrate,Tetrahedron Letters, 2001,42: 6941-6942
[52]王玉玲,李绮云,间溴苯甲醚的合成,沈阳化工,1993(6):5-6
[53]秦付云等,过碳酸钠的热分解反应动力学,华东理工大学学报,2001-04, 27(2):214-216
[54]Gavin Macfie, Benjamin A,et al.The mechanism and kinetics of the fluorination of 2, 4-dinitrochlorobenzene using solid potassium fluoride in dimethylformamide, J. Phys. Chem. B,2001,105:12534-12546
[55]Heidi Markus,Sigmund Fugleberg,et al,Kinetic modelling of a solid-liquid reaction:reduction of ferric iron to ferrous iron with zinc sulphide,Chemical Engineering Science , 2004,59:919-930