CN103923012A - 一种4-氯吡唑衍生物的制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
本发明公开了一种4-氯吡唑衍生物(通式II)的制备方法。其以吡唑衍生物(通式I)在催化剂的存在下与氯化亚砜反应得到通式II化合物。该方法与已有方法相比，操作简单，区域选择性和官能团相容性好，成本低，应用范围广。
Description
技术领域
本发明属于有机合成领域。具体涉及一种4-氯吡唑衍生物的制备方法。
技术背景
自日本三菱油化成功开发杀螨剂吡螨胺以来，4-氯吡唑衍生物因高效、低毒、选择性好及环境友好，在绿色新农药的研发中扮演着越来越重要的角色，其研究已涉足杀菌、杀虫/杀螨、除草等多个领域(WO2009012998，DE2131298和EP371947)。此外，该类化合物还是重要的有机合成中间体，其吡唑环4-位的氯可参与偶联等反应(J Am Chem Soc，2010，132，14073)。然而，目前国内外报道的该类物质的合成方法较少，已有的几种方法，如氯代丁二酰亚胺或硫酰氯直接氯代法(Synth Commun，2007，37，137)、次氯酸钠间接氯代法(J Org Chem，2008，73，3523)、氯气间接氯代法(WO2008129280)、肼和丙烯酸类(J Heterocycl Chem，1999，36，767)或1，3-二羰基类物质(Tinctoria，2002，99，26)缩合制备法等，又存在如底物范围较局限、反应选择性差、易发生多氯代、成本较高等不足。因此探索并建立合成该类物质的通用方法对有机合成和医药研究具有重要意义。
发明内容
本发明的目的在于提供一种4-氯吡唑衍生物的制备方法。
本发明的技术方案如下：
本发明中，4-氯吡唑衍生物(通式II)的制备方法如下：将1倍量的吡唑衍生物(通式I)，物质的量为单位，溶于有机溶剂中，然后加入1～3倍量的氯化亚砜，物质的量为单位，和0.05～0.5倍量的催化剂，物质的量为单位，回流反应1h～24h，最后经分离提纯得到通式II的化合物。其过程为：
其中，通式I和通式II的取代基R1、R2和R3选自氢、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基氨基，其中所述的卤代基中的卤素选自氟、氯、溴或碘中的一种或几种。
反应选用的有机溶剂为二氯甲烷、三氯甲烷、四氯化碳、四氢呋喃、二氧六环、丙酮或乙腈；反应选用的催化剂为N，N-二甲基甲酰胺、吡啶或三乙胺。
具体实施方式
以下具体实施例用来进一步说明本发明。
合成实施例
实施例1：4-氯-1-(4-三氟甲基苯基)-1H-3-羟基吡唑(化合物II-1)的合成
往100mL单口烧瓶中加入化合物(I-1)2.28g(10mmol)和30mL无水三氯甲烷，然后加入氯化亚砜3.57g(30mmol)和N，N-二甲基甲酰胺0.37g(DMF，5mmol)，回流反应12h。冷却至室温，减压蒸去溶剂得粘稠物，经柱层析分离提纯(硅胶填充，石油醚/乙酸乙酯)，得化合物II-1，产率75％，熔点为110-111℃，核磁数据(1HNMR，400MHz，内标TMS，溶剂CDCl3)如下：6ppm7.74(s，1H，CH)，7.64(t，J＝7.6Hz，2H，Ar-H)，7.55(t，J＝7.6Hz，1H，Ar-H)，7.47(d，J＝7.6Hz，1H，Ar-H)。
实施例2：4-氯-1-苯基-3，5-二甲基-1H-吡唑(化合物II-2)的合成
往100mL单口烧瓶中加入化合物(I-2)1.72g(10mmol)和30mL无水三氯甲烷，然后加入氯化亚砜3.57g(30mmol)和N，N-二甲基甲酰胺0.18g(DMF，2.5mmol)，回流反应12h。冷却至室温，减压蒸去溶剂得粘稠物，经柱层析分离提纯(硅胶填充，石油醚/乙酸乙酯)，得化合物II-2，产率75％，核磁数据(1HNMR，400MHz，内标TMS，溶剂CDCl3)如下：6ppm7.48～7.32(m，5H，Ph-H)，2.35(s，3H，CH3)，2.26(s，3H，CH3)。
实施例3：4-氯-1-苯基-5-(4-甲基苯基)-1H-3-氧乙酰噻唑硫酮吡唑(化合物II-3)的合成
往100mL单口烧瓶中加入化合物(I-3)4.10g(10mmol)和30mL无水四氯甲烷，然后加入氯化亚砜3.57g(30mmol)和吡啶0.20g(2.5mmol)，回流反应16h。冷却至室温，减压蒸去溶剂得粘稠物，经柱层析分离提纯(硅胶填充，石油醚/乙酸乙酯)，得化合物II-3，产率60％，熔点为195-196℃，核磁数据(1HNMR，400MHz，内标TMS，溶剂CDCl3)如下：6ppm7.27～7.14(m，9H，Ar-H)，5.78(s，2H，CH2)，4.61(t，J＝7.6Hz，2H，CH2)，3.38(t，J＝7.6Hz，2H，CH2)，2.36(s，3H，CH3)。
实施例4：4-氯-3，5-二甲基-1H-吡唑(化合物II-4)的合成
往100mL单口烧瓶中加入化合物(I-4)0.96g(10mmol)和30mL无水二氯甲烷，然后加入氯化亚砜2.38g(20mmol)和N，N-二甲基甲酰胺0.18g(DMF，2.5mm0l)，回流反应8h。冷却至室温，减压蒸去溶剂得粘稠物，经柱层析分离提纯(硅胶填充，石油醚/乙酸乙酯)，得化合物II-4，产率50％，核磁数据(1HNMR，400MHz，内标TMS，溶剂CDCl3)如下：6ppm11.83(s，1H，NH)，2.26(s，6H，CH3)。
实施例5：4-氯-1，3，5-三甲基-1H-吡唑(化合物II-5)的合成
往100mL单口烧瓶中加入化合物(I-5)1.1g(10mmol)和30mL无水二氯甲烷，然后加入氯化亚砜2.38g(20mmol)和N，N-二甲基甲酰胺0.18g(DMF，2.5mmol)，回流反应8h。冷却至室温，减压蒸去溶剂得粘稠物，经柱层析分离提纯(硅胶填充，石油醚/乙酸乙酯)，得化合物II-5，产率55％，核磁数据(1HNMR，400MHz，内标TMS，溶剂CDCl3)如下：6ppm3.67(s，3H，CH3)，2.20(s，3H，CH3)，2.19(s，3H，CH3)。
实施例6：4-氯-1，3，5-三甲基-1H-吡唑(化合物II-6)的合成
往100mL单口烧瓶中加入化合物(I-6)1.88g(10mmol)和30mL无水三氯甲烷，然后加入氯化亚砜3.57g(30mmol)和三乙胺0.15g(Et3N，1.5mmol)，回流反应6h。冷却至室温，减压蒸去溶剂得粘稠物，经柱层析分离提纯(硅胶填充，石油醚/乙酸乙酯)，得化合物II-6，产率60％，核磁数据(1HNMR，400MHz，内标TMS，溶剂DMSO-d6)如下：6ppm12.66(s，1H，NH)，7.70-7.43(m，5H，Ph-H)，4.24(q，J＝7.0Hz，2H，CH2)，1.34(t，J＝7.0Hz，3H，CH3)。
虽然已经用优选实施例详述了本发明，然而其并非用于限定本发明。任何本领域的技术人员，在不脱离本发明的精神和范围的情况下，应当可以作出各种修改与变更。因此本发明的保护范围应当视为所附的权力要求书所限定的范围。
Claims (4)
1.一种4-氯吡唑衍生物(通式II)的制备方法，其特征在于：将1倍量的吡唑衍生物(通式I)，物质的量为单位，溶于有机溶剂中，然后加入1～3倍量的氯化亚砜，物质的量为单位，和0.05～0.5倍量的催化剂，物质的量为单位，回流反应1h～24h，最后经分离提纯得到通式II的化合物，其过程为：
2.一种如权利要求1所述的通式I和通式II，其特征在于：取代基R1、R2和R3选自氢、卤素、氰基、硝基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6烷基羰基、C1-C6烷氧基羰基、C1-C6烷基氨基，其中所述的卤代基中的卤素选自氟、氯、溴或碘中的一种或几种。
3.一种如权利要求1所述的合成方法，其特征在于：选用的有机溶剂为二氯甲烷、三氯甲烷、四氯化碳、四氢呋喃、二氧六环、丙酮或乙腈。
4.一种如权利要求1所述的合成方法，其特征在于：选用的催化剂为N，N-二甲基甲酰胺、吡啶或三乙胺。
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