二元双功能催化剂催化合成五元杂环化合物
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摘要
本论文以Salen型配合物为亲电试剂和季铵盐(或有机碱)为亲核试剂组成二元催化体系,研究了二硫化碳和环氧烷烃、二硫化碳和环硫烷烃以及二氧化碳和吖丙啶在该体系催化下的环加成反应。
合成了一系列烷基、卤素取代的Salen型西佛碱,与三乙基铝反应制得催化剂SalenAlEt;与Co(OAc)_2反应生成的SalenCo(Ⅱ)配合物再与酸作用,经氧化后得到SalenCo(Ⅲ)配合物,原位用于催化环加成反应。以环氧丙烷为原料,与硫氰化钾反应制得中间体环硫丙烷;环氧丙烷与氨水或有机胺反应,开环后采用Wenker方法制备1-甲基吖丙啶及1,2-二甲基吖丙啶等中间体用于环加成反应。
制备的催化剂及环加成反应产物的结构分别用~1H NMR及FT IR进行了表征,合成的吖丙啶等中间体用气相色谱检验了纯度并用~1H NMR表征了结构。
亲电—亲核二元催化体系(SalenAlEt/季铵盐)可以在温和条件下催化二硫化碳和环氧丙烷反应。考察了催化剂用量、投料比、反应温度和时间等条件对环加成反应的影响。探索出最佳反应条件:100℃,PO/CS_2/Cat.=1000/200/1,9hrs,在此条件下环加成反应产率可达94%。控制反应条件可以在一定范围内改变主产物及各组份的含量。
在SalenCo(Ⅲ)/季铵盐催化体系下,吖丙啶与二氧化碳的环加成反应得到相应的两种区域异构体。以1,2-二甲基吖丙啶为底物时,与二氧化碳反应首次得到了3,4-二甲基噁唑烷-2-酮。
Salen-type complex and quaternary halide or organic bases were used as the binary catalyst in the cycloadditon of carbon disulfide and epoxide, carbon disulfide and episulfide, carbon dioxide and aziridines, respectively.A series of alkyl, halogen substituted Schiff base ligands were prepared. SalenAlEt, fromed by the reaction of H_2Salen and Et3Al, was employed in the cycloadditon of carbon disulfide and epoxide (or episulfide). SalenCo(II) complexes derived from the reaction of H2Salen ligand and Co(OAc)2, were oxided to afford the SalenCo(III) complexes in the presence of acid under an atmosphere of oxygen. It was used in the cycloaddition of aziridines and carbon dioxide in situ. -Propylene oxide was used as the starting material for the preparation of episulfide. Also, propylene oxide was ring-opened after the reaction of ammonium or amine to afford the p-amino alcohol. Then the p-amino alcohol was transformed into the corresponding aziridine through Wenker method.All the catalysts and the products of the catalytic reaction were characterized by ~1H NMR and FT IR. The purities of the aziridines were tested by Gas Chromatography and their structures were determined by ~1H NMR.This electrophile-nucleophile catalytic system (SalenAlEt/quaternary ammonia salt) was effective for the coupling reaction of carbon disulfide and epoxide under mild conditions. A series of factors such as the amount of catalyst, the ratio of the substrates, temperature, time etc were investigated. The optimized condition was determined: 100℃, PO/CS2/Cat.=1000/200/1, 9hrs, with a yield of 94%. The major product and its ratio could be varied according to different conditions employed.In the coupling reaction of aziridine and carbon dioxide which was catalyzed by SalenCo(III)/quaternary system, two regioselective products were obtained. Compound 3, 4-dimethyloxazolidin-2-one was reported the first time and its structure was determined by ~1H NMR when 1, 2-dimethylaziridine was used as substrate.
合成了一系列烷基、卤素取代的Salen型西佛碱,与三乙基铝反应制得催化剂SalenAlEt;与Co(OAc)_2反应生成的SalenCo(Ⅱ)配合物再与酸作用,经氧化后得到SalenCo(Ⅲ)配合物,原位用于催化环加成反应。以环氧丙烷为原料,与硫氰化钾反应制得中间体环硫丙烷;环氧丙烷与氨水或有机胺反应,开环后采用Wenker方法制备1-甲基吖丙啶及1,2-二甲基吖丙啶等中间体用于环加成反应。
制备的催化剂及环加成反应产物的结构分别用~1H NMR及FT IR进行了表征,合成的吖丙啶等中间体用气相色谱检验了纯度并用~1H NMR表征了结构。
亲电—亲核二元催化体系(SalenAlEt/季铵盐)可以在温和条件下催化二硫化碳和环氧丙烷反应。考察了催化剂用量、投料比、反应温度和时间等条件对环加成反应的影响。探索出最佳反应条件:100℃,PO/CS_2/Cat.=1000/200/1,9hrs,在此条件下环加成反应产率可达94%。控制反应条件可以在一定范围内改变主产物及各组份的含量。
在SalenCo(Ⅲ)/季铵盐催化体系下,吖丙啶与二氧化碳的环加成反应得到相应的两种区域异构体。以1,2-二甲基吖丙啶为底物时,与二氧化碳反应首次得到了3,4-二甲基噁唑烷-2-酮。
Salen-type complex and quaternary halide or organic bases were used as the binary catalyst in the cycloadditon of carbon disulfide and epoxide, carbon disulfide and episulfide, carbon dioxide and aziridines, respectively.A series of alkyl, halogen substituted Schiff base ligands were prepared. SalenAlEt, fromed by the reaction of H_2Salen and Et3Al, was employed in the cycloadditon of carbon disulfide and epoxide (or episulfide). SalenCo(II) complexes derived from the reaction of H2Salen ligand and Co(OAc)2, were oxided to afford the SalenCo(III) complexes in the presence of acid under an atmosphere of oxygen. It was used in the cycloaddition of aziridines and carbon dioxide in situ. -Propylene oxide was used as the starting material for the preparation of episulfide. Also, propylene oxide was ring-opened after the reaction of ammonium or amine to afford the p-amino alcohol. Then the p-amino alcohol was transformed into the corresponding aziridine through Wenker method.All the catalysts and the products of the catalytic reaction were characterized by ~1H NMR and FT IR. The purities of the aziridines were tested by Gas Chromatography and their structures were determined by ~1H NMR.This electrophile-nucleophile catalytic system (SalenAlEt/quaternary ammonia salt) was effective for the coupling reaction of carbon disulfide and epoxide under mild conditions. A series of factors such as the amount of catalyst, the ratio of the substrates, temperature, time etc were investigated. The optimized condition was determined: 100℃, PO/CS2/Cat.=1000/200/1, 9hrs, with a yield of 94%. The major product and its ratio could be varied according to different conditions employed.In the coupling reaction of aziridine and carbon dioxide which was catalyzed by SalenCo(III)/quaternary system, two regioselective products were obtained. Compound 3, 4-dimethyloxazolidin-2-one was reported the first time and its structure was determined by ~1H NMR when 1, 2-dimethylaziridine was used as substrate.
引文
[1] 陈长虹,鲍仙华.全球能源消费与CO_2排放量.上海环境科学,1999,18(2):62-64.
[2] 王绍武,龚道溢.对气候变暖问题争议的分析.地理研究,2001,20(2):153-160.
[3] 李昆俞.CO_2的应用及产品开发.天然气化工(C1化学与化工),199621(3):40-43.
[4] 曲格平.关于我国参加联合国环境与发展大会的情况报告-迈向21世纪.北京:中国环境科学出版社.1992.
[5] 周忠清.二氧化碳催化还原成碳的发展.精细石油化工,1994,(4):92-96.
[6] 李虎阳,李智超,李赫亮.CO_2气体保护焊镀铜焊丝缓蚀处理试验研究.表面技术,2001,30(2):3-5.
[7] 李淑芬,陈宝良,韩金玉.超临界CO_2萃取天然产品的特性研究.化工进展,1997,(2):10-14.
[8] 谈士海,张文正.非混相CO_2驱油在油田增产中的应用.石油钻探技术,2001,29(2):58-59.
[9] 顾蕊英,李颖华.CO_2资源的综合利用.湖北化工,1993,(2):3-35.
[10] Svoronos P D N, Bruno T J. Carbonyl Sulfide: A Review of Its Chemistry and Properties. Ind. Eng. Chem. Res. 2002, 41(22): 5321-5336.
[11] (a) Choi W, Sanda F, Endo T. Dependence of Ring-Opening Reaction of Five-Membered Dithiocarbonates on Cationic Catalyst: Control of Isomerization and Polymerization. Macromolecules. 1998, 31(8): 2454-3460.
(b)Choi W, Sanda F, Endo r. A Novel Construction of Living Polymerization by Neighboring Group Participation: Living Cationic Ring-Opening Polymerization of a Five-Nembered Cyclic Dithiocarbonate. Macromolecules. 1998, 31(25), 9093-9095.
(c) Choi W, Sanda F, Endo T. Novel one-pot syntheses of sulfur-containing polymers from a bifunctional five-membered cyclic ditbiocarbonate. Journal of Polymer Science Part A: Polymer Chemistry. 1998, 36(7): 1189-1195.
[12] Hayashi S, Furukawa M, Nakao T et al. Studies on antitumor substances. Ⅺ. Reactions of Bunte salts with nucleophiles. Chem Pharm Bull. 1971, 19(8): 1557-1561.
[13] Kihara N, Nakawaki Y, Endo T. Preparation of 1, 3-Oxathiolane-2-thiones by the Reaction of Oxirane and Carbon Disulfide. J. Org. Chem. 1995, 60(2): 473-475.
[14] Nobuo A, Yasuji K, Kazuo S. Copolymerization of propylene oxide and carbon disulfide with diethylzinc-electron-donor catalyst. J. Poly. Sci: Poly. Chem. Edi. 1977, 15, 937-944.
[15] Inoue S, Koinuma H, Tsuruta T. Paper presented at the 17th Polymer Symposium, Japan, 1968;Preprin
[16] Taguchi Y, Yasumoto K, Shibuya I et al. The synthesis of 1, 3-dithiolane-2-thione derivatives. Bull. Chem. Soc. Jpn. 1987, 60(2): 727-930.
[17] Taguchi Y, Yanagiya K, Shibuya I et al. The reaction of oxiranes with carbon disulfide under high pressure. Bull. Chem. Soc. Jpn. 1988, 61(3): 921-925 and and references cited therein.
[18] Taguchi Y, Yasumoto M, Shibuya I et al. The synthesis of 1, 3-dithiolan-2-ones on the reaction of oxiranes with carbon disulfide under high pressure. Bull. Chem. Soc.Jpn.1989, 62(2): 474-478.
[19] Durden J A, Stansbury H A, Catlette W H. The Preparation of Alkene Trithiocarbonates. J. Am. Chem. Soc. 1960, 82(12):3082-3084.
[20] Kihara N, Nakawaki Y, Endo T. Preparation of 1, 3-oxathiolane-2-thiones by the reaction of oxirane and carbon disulfide. J.Org. Chem. 1995, 60(2):473-475.
[21] Motokucho S, Takeuchi D, Sanda F et al. Synthesis of cyclic trithiocarbonates from cyclic ethers and carbon disulfide catalyzed by titanium complex. Tetrahedron. 2001,57(33):7149-7152.
[22] Kubota S, Taguchi E, Eto M et al. Agric. Biol. Chem. 1977, 41,1621
[23] (a) Sugawara A, Ishiyama M, Abe Yet al. Sulfur Lett. 1990,12, 55. (b) Sugawara A, Sato T, Sato R. Convenient synthesis of cyclic trithiocarbonates from 1, 2- or 1, 3- dihaloalkanes and sodium trithiocarbonate in the presence of phase-transfer catalyst. Bull. Chem. Soc. Jpn. 1989, 62(1) :339-341.
[24] Takeuchi D, Aida T, Endo T. The first example of the copolymerizalion of cyclic acid anhydrides with oxetane by bulky titanium bisphenolates. Macromol Rapid Commun. 1999, 20(12) :646-649.
[25] Shen Y M, Duan W L, Shi M. Chemical fixation of carbon dioxide Co-catalyzed by a combination of Schiff bases or phenols and organic bases. Eur. J. Org. Chem. 2004, (14):3080-3089.
[26] Shen Y M, Duan W L, Shi M, Phenol and Organic Bases Co-Catalyzed Chemical Fixation of Carbon Dioxide with Terminal Epoxides to Form Cyclic Carbonates. Advanced Synthesis & Catalysis, 2003,345(3): 337-340.
[27] Tascedda P, Dunach E. Electrosynthesis of cyclic carbamates from aziridines and carbon dioxide. Chem Commun, 2000, (6):449-450.
[28] Kawanami H, Ikushima Y. Regioselectivity and selective enhancement of carbon dioxide fixation of 2-substituted aziridines to 2-oxazolidinones under supercritical conditions. Tetrahedron Letters. 2002, 43(21): 3841-3844.
[29] Hancock M T, Pinhas A R. A convenient and inexpensive conversion of an aziridine to an oxazolidinone. Tetrahedron Letters. 2003, 44 (29): 5457-5460.
[30] Sudo A, Morioka Y, Koizumi E et al. Highly efficient chemical fixations of carbon dioxide and carbon' disulfide by cycloaddition to aziridine under atmospheric pressure. Tetrahedron Letters, 2004, 44 (7): 7889-7891.
[31] Sudo A, Morioka Y, Sanda F, Endo T. N-Tosylaziridine, a new substrate for chemical fixation of carbon dioxide via ring expansion reaction under atmospheric pressure. Tetrahedron Letters, 2004, 45 (7): 1363-1365.
[32] Miller A W, Nguyen S T.(Salen) chromium(Ⅲ)/DMAP: An Efficient, Catalyst System for the Selective Synthesis of 5-Substituted Oxazolidinones from Carbon Dioxide and Aziridines. Org. Lett. 2004, 6(14): 2301-2304.
[33] 吕小兵.大连理工大学博士学位论文.2002.
[34] Bermejo M R, Castineiras A, Garcia-Monteagudo J C et al. Electronic and steric effects in manganese schiff-base complexes as models for the wearer oxidation complex in photosystem Ⅱ. The isolation of manganese-(Ⅱ) and -(Ⅲ) complexes of 3- and 3, 5-substituted N, N-bis(salicylidene)ethane-1, 2-diamine(H_2salen) ligands. J. Chem. Soc., Dalton Trans. 1996, (14): 2935-2944.
[35] Kerr J M, Suckling C J. Selective functionalisation. Part Ⅱ. Selective hydrogenation by a novel palladium salicylidene-ethylenediamine complex and the properties of derivatives of some square planar homogeneous hydrogenation catalysts. J. Chem. Soc. Perkin Trans. 1, 1990,(4): 887-895.
[36] Scott E S, Bridget D B, Jay F L et al. Highly selective hydrolytic kinetic resolytion of terminal epoxides catalyzed by chiral (salen)Co~(111) complexes. Practical synthesis of enantioenriched terminal epoxides and 1, 2-Diols. J. Am. Chem. Soc, 2002, 124(7): 1307-1315.
[37] Reeves W A, Drake G L, Hoffpauir C L. Ethylenimine by Flash Distillation 1. J. Am. Chem. Soc, 1951, 73(7): 3522-3522.
[38] 苗华,孙兰英,郭惠元.(S)-(-)-2-氨基丙醇的制备.中国医药工业杂志,1998,29(10),470-470.
[39] Xu J X, Xu S. A general route to the synthesis of N-Protected 1-Substituted and 1, 2-disubstituted Taurines. Synthesis. 2004, 2: 276-282.
[40] Minoura Y, Takebayashi M, Price C C. Preparation and Polymerization of D- and L-Propylenimine and N-Methylpropylenimine. J. Am. Chem. Soc. 1959, 81(17): 4689-4692.
[41] Correa A, Denis J n, Greene A E. A safe simple one-pot preparation of N-Derivatized β-amino alcohols and oxazolidinones from amino acids. Synth. Commun. 1991, 21(1): 1-9.
[2] 王绍武,龚道溢.对气候变暖问题争议的分析.地理研究,2001,20(2):153-160.
[3] 李昆俞.CO_2的应用及产品开发.天然气化工(C1化学与化工),199621(3):40-43.
[4] 曲格平.关于我国参加联合国环境与发展大会的情况报告-迈向21世纪.北京:中国环境科学出版社.1992.
[5] 周忠清.二氧化碳催化还原成碳的发展.精细石油化工,1994,(4):92-96.
[6] 李虎阳,李智超,李赫亮.CO_2气体保护焊镀铜焊丝缓蚀处理试验研究.表面技术,2001,30(2):3-5.
[7] 李淑芬,陈宝良,韩金玉.超临界CO_2萃取天然产品的特性研究.化工进展,1997,(2):10-14.
[8] 谈士海,张文正.非混相CO_2驱油在油田增产中的应用.石油钻探技术,2001,29(2):58-59.
[9] 顾蕊英,李颖华.CO_2资源的综合利用.湖北化工,1993,(2):3-35.
[10] Svoronos P D N, Bruno T J. Carbonyl Sulfide: A Review of Its Chemistry and Properties. Ind. Eng. Chem. Res. 2002, 41(22): 5321-5336.
[11] (a) Choi W, Sanda F, Endo T. Dependence of Ring-Opening Reaction of Five-Membered Dithiocarbonates on Cationic Catalyst: Control of Isomerization and Polymerization. Macromolecules. 1998, 31(8): 2454-3460.
(b)Choi W, Sanda F, Endo r. A Novel Construction of Living Polymerization by Neighboring Group Participation: Living Cationic Ring-Opening Polymerization of a Five-Nembered Cyclic Dithiocarbonate. Macromolecules. 1998, 31(25), 9093-9095.
(c) Choi W, Sanda F, Endo T. Novel one-pot syntheses of sulfur-containing polymers from a bifunctional five-membered cyclic ditbiocarbonate. Journal of Polymer Science Part A: Polymer Chemistry. 1998, 36(7): 1189-1195.
[12] Hayashi S, Furukawa M, Nakao T et al. Studies on antitumor substances. Ⅺ. Reactions of Bunte salts with nucleophiles. Chem Pharm Bull. 1971, 19(8): 1557-1561.
[13] Kihara N, Nakawaki Y, Endo T. Preparation of 1, 3-Oxathiolane-2-thiones by the Reaction of Oxirane and Carbon Disulfide. J. Org. Chem. 1995, 60(2): 473-475.
[14] Nobuo A, Yasuji K, Kazuo S. Copolymerization of propylene oxide and carbon disulfide with diethylzinc-electron-donor catalyst. J. Poly. Sci: Poly. Chem. Edi. 1977, 15, 937-944.
[15] Inoue S, Koinuma H, Tsuruta T. Paper presented at the 17th Polymer Symposium, Japan, 1968;Preprin
[16] Taguchi Y, Yasumoto K, Shibuya I et al. The synthesis of 1, 3-dithiolane-2-thione derivatives. Bull. Chem. Soc. Jpn. 1987, 60(2): 727-930.
[17] Taguchi Y, Yanagiya K, Shibuya I et al. The reaction of oxiranes with carbon disulfide under high pressure. Bull. Chem. Soc. Jpn. 1988, 61(3): 921-925 and and references cited therein.
[18] Taguchi Y, Yasumoto M, Shibuya I et al. The synthesis of 1, 3-dithiolan-2-ones on the reaction of oxiranes with carbon disulfide under high pressure. Bull. Chem. Soc.Jpn.1989, 62(2): 474-478.
[19] Durden J A, Stansbury H A, Catlette W H. The Preparation of Alkene Trithiocarbonates. J. Am. Chem. Soc. 1960, 82(12):3082-3084.
[20] Kihara N, Nakawaki Y, Endo T. Preparation of 1, 3-oxathiolane-2-thiones by the reaction of oxirane and carbon disulfide. J.Org. Chem. 1995, 60(2):473-475.
[21] Motokucho S, Takeuchi D, Sanda F et al. Synthesis of cyclic trithiocarbonates from cyclic ethers and carbon disulfide catalyzed by titanium complex. Tetrahedron. 2001,57(33):7149-7152.
[22] Kubota S, Taguchi E, Eto M et al. Agric. Biol. Chem. 1977, 41,1621
[23] (a) Sugawara A, Ishiyama M, Abe Yet al. Sulfur Lett. 1990,12, 55. (b) Sugawara A, Sato T, Sato R. Convenient synthesis of cyclic trithiocarbonates from 1, 2- or 1, 3- dihaloalkanes and sodium trithiocarbonate in the presence of phase-transfer catalyst. Bull. Chem. Soc. Jpn. 1989, 62(1) :339-341.
[24] Takeuchi D, Aida T, Endo T. The first example of the copolymerizalion of cyclic acid anhydrides with oxetane by bulky titanium bisphenolates. Macromol Rapid Commun. 1999, 20(12) :646-649.
[25] Shen Y M, Duan W L, Shi M. Chemical fixation of carbon dioxide Co-catalyzed by a combination of Schiff bases or phenols and organic bases. Eur. J. Org. Chem. 2004, (14):3080-3089.
[26] Shen Y M, Duan W L, Shi M, Phenol and Organic Bases Co-Catalyzed Chemical Fixation of Carbon Dioxide with Terminal Epoxides to Form Cyclic Carbonates. Advanced Synthesis & Catalysis, 2003,345(3): 337-340.
[27] Tascedda P, Dunach E. Electrosynthesis of cyclic carbamates from aziridines and carbon dioxide. Chem Commun, 2000, (6):449-450.
[28] Kawanami H, Ikushima Y. Regioselectivity and selective enhancement of carbon dioxide fixation of 2-substituted aziridines to 2-oxazolidinones under supercritical conditions. Tetrahedron Letters. 2002, 43(21): 3841-3844.
[29] Hancock M T, Pinhas A R. A convenient and inexpensive conversion of an aziridine to an oxazolidinone. Tetrahedron Letters. 2003, 44 (29): 5457-5460.
[30] Sudo A, Morioka Y, Koizumi E et al. Highly efficient chemical fixations of carbon dioxide and carbon' disulfide by cycloaddition to aziridine under atmospheric pressure. Tetrahedron Letters, 2004, 44 (7): 7889-7891.
[31] Sudo A, Morioka Y, Sanda F, Endo T. N-Tosylaziridine, a new substrate for chemical fixation of carbon dioxide via ring expansion reaction under atmospheric pressure. Tetrahedron Letters, 2004, 45 (7): 1363-1365.
[32] Miller A W, Nguyen S T.(Salen) chromium(Ⅲ)/DMAP: An Efficient, Catalyst System for the Selective Synthesis of 5-Substituted Oxazolidinones from Carbon Dioxide and Aziridines. Org. Lett. 2004, 6(14): 2301-2304.
[33] 吕小兵.大连理工大学博士学位论文.2002.
[34] Bermejo M R, Castineiras A, Garcia-Monteagudo J C et al. Electronic and steric effects in manganese schiff-base complexes as models for the wearer oxidation complex in photosystem Ⅱ. The isolation of manganese-(Ⅱ) and -(Ⅲ) complexes of 3- and 3, 5-substituted N, N-bis(salicylidene)ethane-1, 2-diamine(H_2salen) ligands. J. Chem. Soc., Dalton Trans. 1996, (14): 2935-2944.
[35] Kerr J M, Suckling C J. Selective functionalisation. Part Ⅱ. Selective hydrogenation by a novel palladium salicylidene-ethylenediamine complex and the properties of derivatives of some square planar homogeneous hydrogenation catalysts. J. Chem. Soc. Perkin Trans. 1, 1990,(4): 887-895.
[36] Scott E S, Bridget D B, Jay F L et al. Highly selective hydrolytic kinetic resolytion of terminal epoxides catalyzed by chiral (salen)Co~(111) complexes. Practical synthesis of enantioenriched terminal epoxides and 1, 2-Diols. J. Am. Chem. Soc, 2002, 124(7): 1307-1315.
[37] Reeves W A, Drake G L, Hoffpauir C L. Ethylenimine by Flash Distillation 1. J. Am. Chem. Soc, 1951, 73(7): 3522-3522.
[38] 苗华,孙兰英,郭惠元.(S)-(-)-2-氨基丙醇的制备.中国医药工业杂志,1998,29(10),470-470.
[39] Xu J X, Xu S. A general route to the synthesis of N-Protected 1-Substituted and 1, 2-disubstituted Taurines. Synthesis. 2004, 2: 276-282.
[40] Minoura Y, Takebayashi M, Price C C. Preparation and Polymerization of D- and L-Propylenimine and N-Methylpropylenimine. J. Am. Chem. Soc. 1959, 81(17): 4689-4692.
[41] Correa A, Denis J n, Greene A E. A safe simple one-pot preparation of N-Derivatized β-amino alcohols and oxazolidinones from amino acids. Synth. Commun. 1991, 21(1): 1-9.
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