CN102675163B - 一种磺酰胺的制备方法 - Google Patents
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Abstract
本发明公开了一种磺酰胺的制备方法，通过亚磺酸或亚磺酸盐与硝基化合物在惰性气体氛围下，以过渡金属或过渡金属化合物作为催化剂，反应温度为20℃～200℃，加热3～30小时，生成磺酰胺。本发明具有如下的技术效果，改善了反应体系，硝基化合物性质稳定、廉价易得，此方法直接使用硝基化合物作为初始原料，省去了硝基的选择性还原成氨基化合物；而亚磺酸盐也较其它磺化剂稳定易储藏；同时此反应体系简单，易于实现工业化生产。本发明的方法比已有方法更安全、更经济有效，所用的催化剂也更安全；本发明的方法通常以90％，往往是95％以上的转化率将硝基苯原料转化为磺酰胺。
Description
技术领域
本发明涉及一种制备磺酰胺的方法。
背景技术
N-(取代苯基)磺酰胺化合物是功能性材料、药物等的重要构成。合成这些化合物的方法有许多，大致可以归纳为两类：一类是卤代芳烃(或者拟卤代芳烃)和磺酰胺的反应；一类是苯胺和磺化试剂的反应。例如在专利US4,818,275中报道的作为除草剂的磺酰胺类物质就是通过在二氯甲烷中将相应的芳基胺与甲磺酰氯和过量的三乙胺反应，然后用氢氧化钠处理所得磺酰胺衍生物。只是，当此反应进行大规模反应时，过量的三乙胺必须回收、循环利用或者作为工艺的一部分进行处理，这种回收/循环利用或处理导致巨大的生产成本。因此专利WO01/94320又报道了不需要加入酸清除剂的条件下，由芳基胺直接制备N-(取代苯基)磺酰胺，因其简单，同时基本不形成副产物而令人关注。
近些年来有关合成磺酰胺的文献报道也大都基于芳卤或者苯胺与磺化试剂的反应，且都能以较好的收率进行反应。但某些体系中还存在着一些不足：(1)反应中需要加入单膦或者双膦配体来提高产率；(2)一些体系中需要加入大量的吸潮性的碳酸铯作为碱，或者加入其它助剂；(3)一些磺化试剂活性高、对水敏感、不易保存，例如芳基磺酰氯。
发明内容
本发明的目的是提供一种磺酰胺的制备方法。
本发明的技术方案是，一种磺酰胺的制备方法，其特征在于：通过使用相对于硝基化合物为1.5～6∶1摩尔比的亚磺酸或亚磺酸盐与硝基化合物在惰性气体氛围下，以相对于硝基化合物为0.001～0.09∶1摩尔比的过渡金属或过渡金属化合物作为催化剂，反应温度为20-200℃，加热3～30小时，生成磺酰胺。
所述亚磺酸通式为：
所述的亚磺酸盐通式为：
式中n、m、p、q为1～6之间，r为0～6之间的数，反离子M(m+)为金属或者有机化合物，R为有机基团且Y-为阴离子。
取代基R为烷基、烯基、芳基、杂芳基、烷氧基、芳氧基、芳基酰胺基、酰基、芳基氨基、二烷基、二芳基氨基、甲酰基、羟基、羧基、硝基、氰基、亚硝基或卤素取代基。
反离子M(m+)为Li、Na、K、Mg、Ca、B、Al、Ag、Cu、Mn、Fe、Co、Ni、Mo或Ru的金属阳离子。
反离子M(m+)为铵、吡啶鎓、膦鎓的有机阳离子。
Y-为I-、Br-、Cl-、F-、CO3 -、CN-、OH-、氧烷基、HCO3 -、PO4 3-、HPO4 2-或HPO4 -。
所述的硝基化合物通式为：
R1-NO2
式中R1是烷基或C1-C10-芳基酰胺基、酯基、烯基、芳基、杂芳基、烷氧基、芳氧基、酰基、芳基氨基、二烷基、二芳基氨基、甲酰基、羟基、羧基、硝基、氰基、亚硝基、卤素取代基。
反应在溶剂存在下或在本体中进行，溶剂为烃、芳香烃、醚、酯、酰胺、二甲亚砜、环丁砜、乙腈、异丁腈、丙腈、碳酸丙烯酯或卤代脂肪。
本发明具有如下的技术效果，改善了反应体系，硝基化合物性质稳定、廉价易得，此方法直接使用硝基化合物作为初始原料，省去了硝基的选择性还原成氨基化合物；而亚磺酸盐也较其它磺化剂稳定易储藏；同时此反应体系简单，易于实现工业化生产；本发明的方法比已有方法更安全、更经济有效，所用的催化剂也更安全；本发明的方法通常以90％，往往是95％以上的转化率将硝基苯原料转化为磺酰胺。
具体实施方式
本发明是在存在催化剂且不使用任何添加剂的条件下，通过亚磺酸或亚磺酸盐与硝基化合物在惰性气体氛围下，以过渡金属或过渡金属化合物作为催化剂，反应温度为20-200℃，加热3～30小时，生成磺酰胺，基本上不生成过渡酰基化副产物的方法。
本发明的亚磺酸盐与硝基化合物的反应式
本发明的技术方案是以下述方式实现的：优选的催化剂选自Pd、Ni、Fe、Au、Rh、Pt、Ru、Ir、Ag、Cu、Mn、Co。金属可以任选以单质形式、作为络合物或作为盐使用。特别优选使用钯化合物，还特别优选使用铜化合物更特别优选使用氯化亚铜或者溴化亚铜。
反应可任选通过在反应混合中加入以上例举的成分而由适合的金属前体制备的适合的催化剂来进行。
在本发明中可以使用如通式1亚磺酸：
或者如通式2亚磺酸盐：
式中n、m、p、q为1～6、r为0～6，R为有机基团且Y-为阴离子，其中反离子M(m+)为优选选自Li、Na、K、Al、Mg、Ca、B、Ag、Cu、Mn、Fe、Co、Ni、Mo、Ru的金属阳离子或优选选自铵、吡啶鎓、膦鎓的有机阳离子。任选除了亚磺酸盐外还可以配位另一种阴离子，优选选自I-、Br-、Cl-、F-、CO3 -、CN-、OH-、氧烷基、HCO3 -、PO4 3-、HPO4 2-、H2PO4 -。
将所述的亚磺酸或者亚磺酸盐以预制备成的形式加入或者由亚磺酸与适合的碱原位制备。
取代基R为有机基团，优选可选自直链、支链或环状C1-C20-烷基；直链、支链或环状C2-C20-链烯基以及C6-C20-芳基和选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、异噁唑、咪唑、噁唑、噻唑、噻吩、呋喃的杂芳基，并本身可以带有选自直链、支链或环状C1-C20-烷基；直链、支链和环状C2-C20-链烯基以及C6-C20-芳基或杂芳基；直链、支链或环状C1-C10-烷氧基或C1-C10-芳氧基；直链、支链或环状C1-C10-烷基或C1-C10-芳基酰胺基或酯基；直链、支链或环状C1-C10-酰基；直链、支链或环状C1-C10-烷基或C1-C10-芳基氨基；直链、支链或环状C1-C10-二烷基或C1-C10-二芳基氨基、甲酰基、氧、硫、羟基、羧基、硝基、氰基、亚硝基或卤素如F、Cl、Br和I的其他取代基。
特别优选R可选自直链、支链或环状C1-C20-烷基；直链、支链或环状C2-C20-链烯基以及C6-C20-芳基或选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、异噁唑、咪唑、噁唑、噻唑、噻吩、呋喃的杂芳基，并本身可以带有如上所述的其他取代基。
所述硝基化合物的通式为：
R1-NO2
式中R1是有机基团并优选可分别选自直链、支链或环状C1-C20-烷基或C1-C10-芳基酰胺基或酯基；直链、支链或环状C2-C20-链烯基以及C6-C20-芳基或选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、异噁唑、咪唑、噁唑、噻唑、噻吩、呋喃的杂芳基，并本身可以带有选自直链、支链或环状C1-C20-烷基；直链、支链或环状C2-C20-链烯基以及C6-C20-芳基或杂芳基；直链、支链或环状C1-C10-烷氧基或C1-C10-芳氧基；直链、支链或环状C1-C10-烷基或C1-C10-芳基酰胺基或酯基；直链、支链或环状C1-C10-酰基；直链、支链或环状C1-C10-烷基或C1-C10-芳基氨基；直链、支链或环状C1-C10-二烷基或C1-C10-二芳基氨基、甲酰基、氧、硫、羟基、羧基、硝基、氰基、亚硝基、或卤素如F、Cl、Br或I的其他取代基。
特别的优选R1可选自直链、支链或环状C1-C20-烷基；直链、支链和环状C1-C10-烷基或C1-C10-芳基酰胺基或酯基；直链、支链或环状C2-C20-链烯基以及C6-C20-芳基或选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、异噁唑、咪唑、噁唑、噻唑、噻吩、呋喃的杂芳基，并本身可以带有上述的其他取代基。
根据本发明方法，催化剂的用量为以基于硝基化合物为0.01mol％至100mol％的量使用，并特别优选为0.1％至10％的量使用。
根据本发明方法，反应温度为20-200℃，并优选为在60-160℃的温度实施。
本发明的方法可以在溶剂存在下或在本体中实施。例如可以使用投入物料、直链、环状或支链烃(例如己烷、庚烷和辛烷)、芳香烃(例如苯、二甲苯、乙苯、均三甲苯)、醚(例如1，4-二氧六环、四氢呋喃、甲基四氢呋喃、二丁醚、甲基叔丁基醚、二乙二醇二甲醚)、酯(例如乙酸乙酯、乙酸丁酯)、酰胺(例如N，N-二甲基甲酰胺、N，N-二乙基甲酰胺、N-甲基吡咯烷酮、N，N-二甲基乙酰胺)、二甲亚砜、环丁砜、乙腈、异丁腈、丙腈、碳酸丙烯酯、卤代脂肪或芳香烃中的一种作为溶剂。
优选使用N，N-二甲基甲酰胺、N，N-二乙基甲酰胺、N-甲基吡咯烷酮、N，N-二甲基乙酰胺、二甲亚砜、环丁砜、乙腈、碳酸丙烯酯、二乙二醇二甲醚作为溶剂。本发明方法优选这样实施，即通过使反应在惰性氛围保护体系中实施。
下面结合具体实施例对本发明做进一步说明。
实施例1～15(如表一所示)
制备N-对甲苯基-对甲苯磺酰胺反应式为：
使用0.6mmol的对甲苯亚磺酸钠和0.2mmol的对甲基硝基苯在铜化合物(0.01mmol)和惰性氛围的存在下在0.6mL溶剂中于120℃搅拌24小时。使用均三甲苯作为内标物质借助气相色谱-质谱联用测定产率。
表一
表一中实施例15为在空气氛围中实施的。
由实施例1～15看出使用氯化亚铜和N-甲基吡咯烷酮的组合在120℃的特别低的温度下制备磺酰胺产物达到了出色的产率。
实施例16～36(如表2所示)
以硝基化合物为0.2mmol的量，来证明本发明的广泛适用性。滤出无机化合物后，经硅胶色谱分析测定产率并借助NMR、MS清楚地表征。
表二
Claims (1)
1.一种磺酰胺的制备方法，其特征在于：通过使用相对于硝基化合物为1.5～6∶1摩尔比的亚磺酸或亚磺酸盐与硝基化合物在惰性气体氛围下，以相对于硝基化合物为0.001～0.09∶1摩尔比的氯化亚铜作为催化剂，在溶剂存在下进行，反应温度为60-160℃，加热3～30小时，生成磺酰胺；
其中所述溶剂为N-甲基吡咯烷酮；
所述亚磺酸通式为：
所述的亚磺酸盐通式为：
式中n、m、p均为1，反离子M(m+)为Li、Na、K、Rb、Cs的金属阳离子；R为直链、支链或环状C1-C10-烷基；C6-C20-芳基；
所述的硝基化合物通式为：
R1-NO2；
式中R1为直链、支链、或环状C1-C10-烷基；C6-C20-芳基或选自吡啶、嘧啶、哒嗪、吡嗪、三嗪、四嗪、吡咯、异噁唑、咪唑、噁唑、噻唑、噻吩、呋喃的杂芳基。
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