CN104710400B - 一种合成环状碳酸酯的方法 - Google Patents

一种合成环状碳酸酯的方法 Download PDF

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CN104710400B
CN104710400B CN201310696222.7A CN201310696222A CN104710400B CN 104710400 B CN104710400 B CN 104710400B CN 201310696222 A CN201310696222 A CN 201310696222A CN 104710400 B CN104710400 B CN 104710400B
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epoxides
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高爽
赵公大
李军
戴文
吕迎
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明涉及一种四齿氮有机配体和金属化合物形成的手性络合物催化剂催化CO2和环氧化物环加成制备环状碳酸酯的方法。该方法是以CO2和环氧化物为原料，四齿氮有机配体和金属化合物形成的手性络合物为催化剂，含氮化合物为助催化剂，手性四齿氮有机配体和金属元素的摩尔比为1:1，手性四齿氮有机配体与底物环氧化物的摩尔比为1:3000～1:100，手性四齿氮有机配体与含氮化合物的摩尔比为1:3～1:1，环氧化物和CO2的摩尔比为1:10～1:1，在25～120℃下反应1～12h，得到产物环状碳酸酯。本发明提供的金属手性络合物催化剂制备简单，稳定性好，具有较高的催化活性和选择性，工业应用前景巨大。

Description

一种合成环状碳酸酯的方法
技术领域
本发明涉及CO2和环氧化物加成反应得到环状碳酸酯的方法，还涉及适用于此目的的有机配体本身。
背景技术
环状碳酸酯是一类性能优异的有机溶剂和重要的精细化工中间体，其应用非常广泛,可用作高能密度电池和电容的电解液,还用于合成聚碳酸酯、热硬化性树脂、合成热记录材料等。目前公开报道的环状碳酸酯的制备大多采用的是环氧化物与CO2环加成反应的方法。能够催化环氧化物与CO2环加成反应的催化剂种类繁多，其中金属配合物是一类非常重要的催化剂，尤以二氮络和物使用最为广泛，而很少的文献报道了以四齿氮有机络合物为催化剂催化环氧化物与CO2环加成反应。四齿氮有机络合物催化剂主要包括金属卟啉和酞青络合物催化剂。
文献：Kruper W J,Dellar D V.Catalytic formation of cyclic carbonatesfrom epoxides and CO2with chromium metalloporphyrinates[J].The Journal ofOrganic Chemistry,1995,60:725报道了以Cr卟啉和DMAP一起作为环氧化物和CO2环加成反应催化剂。
文献：Paddock R L,HiyamaY,Mckay J M,et al.Co(Ⅲ)porphyrin/DMAP:anefficient catalyst system for the synthesis of cyclic carbonates from CO2andepoxides[J].Tetrahedron Letters,2004,45:2023报道了利用Co(Ⅲ)四苯基氯化物与DMAP组合作为环氧化物和CO2环加成反应催化剂。
文献：Jin L L,Chang T,Jing H W.Coupling of epoxides with carbondioxide catalyzed by ruthenium porphyrin complex[J].Chinese Journal ofCatalysis,2007,28(4):287以及文献Jin L L,Jing HW,Chang T,et al.Metalporphyrin/phenyltrimethyl-ammonium tribromide:High efficient catalysts forcoupling reaction of CO2and epoxides[J].Journal of Molecular Catalysis A:Chemical,2007,261:262报道了一系列金属卟啉络合物（金属包括Co、Fe、Ru或Mn），并与不同的碱性物质（PTAT、TBAB或DMAP）组合作为环氧化物和CO2环加成反应催化剂。
文献：Kasuga K,Kabata N,KatoT,Sugimori T,Handa M.Fixation of carbondioxide with l,2-epoxypropane catalysed by tetra-t-butyl-phthalocyaninatoaluminium(Ⅲ)acetate,tetra-t-butylphthalo-cyaninatoaluminium(Ⅲ)trimethylsilanolate and tetra-t-butylphthalo-cyaninatoaluminium(Ⅲ)triphenylsilanolate[J].Inorganica Chimica Aeta,1998,278:223报道了利用四叔丁基酞青铝络合物与三乙基（2-羟丙基）碘化铵组成的催化体系在室温下对环氧化物和CO2环加成反应有一定的催化活性。
文献：季东锋，吕小兵，何仁等，碱性配体对氯铝酞著催化CO2与环氧烷烃合成烷撑碳酸酯的促进作用[J].催化学报,1999,20(6):675报道了氯铝酞青在有机碱存在下对环氧化物和CO2环加成反应具有较高的催化活性。此外，该研究组还在文献：张英菊,梁斌,潘玉珍,等.四叔丁基金属酞青催化活化CO2与环氧化物的环加成反应.催化学报,2003,24(10):765中考察了四丁基酞青镁和四丁基酞青铁在有机碱存在下对环氧化物和CO2环加成反应的催化活性。
发明内容
本发明的目的在于提供一种全新的四齿氮有机配体和金属化合物形成的络合物催化剂，并应用于催化环氧化物和CO2环加成反应。
为实现上述目的，本发明采用的技术方案如下：
以CO2和环氧化物为原料，四齿氮有机配体和金属化合物形成的手性络合物为催化剂，含氮化合物为助催化剂，手性四齿氮有机配体和金属元素的摩尔比为1:1，手性四齿氮有机配体与底物环氧化物的摩尔比为1:3000～1:100，手性四齿氮有机配体与含氮化合物的摩尔比为1:3～1:1，环氧化物和CO2的摩尔比为1:10～1:1，在25～120℃下反应1～12h，得到产物环状碳酸酯。
所述的手性四齿氮配体是具有如下结构的化合物，其中R1、R2、R3分别为氢、烷基（分子式为CnH2n+1，n=1～5）、芳基，芳基烷基（分子式为C6H5CnH2n+1,n=1～5）或烷氧基（分子式为OCnH2n+1,n=1～5），R1、R2、R3相同或不同；X为O、S或N。
底物环氧化物为是手性环氧化物或对映体环氧化物，其中R，R’，R”为氢，直链烷基（CnH2n+1,n=1～10）,环状烷基（CnH2n-1，n=5～8）,芳基。
手性金属络合物由下列金属元素的一种组成：铜、镁、铁、铝、镍、钌、钴、铬或锰
助催化剂含氮化合物为三乙胺、吡啶、2,2'-联吡啶、4,4'-联吡啶、4-二甲氨基吡啶、四乙基溴化铵、四乙基碘化铵、四丁基溴化铵、四丁基碘化铵、十二烷基三甲基溴化铵、十二烷基三甲基碘化铵、十六烷基三甲基溴化铵、十六烷基三甲基碘化铵、十八烷基三甲基溴化铵或十八烷基三甲基碘化铵中的至少一种。
本发明环状碳酸酯的收率对应选择性均大于95%。该反应具有反应条件温和，高转化率和对应选择性。具有工业应用前景。
具体实施方式
下面通过一些实施例详细说明本发明的具体实施步骤，不应将这些实施例当作本发明范围限制。
实施例1
一种手性四齿氮配体的合成：
在50mL甲苯溶液中加入22.5mg(0.1mmol)醋酸钯和72mg（0.3mmol）三叔丁基膦，搅拌10min.。依次加入2.36g(10mmol)邻二溴苯，3.63g(24mmol)2-氨基苯甲酸甲酯和10.1g(31mmol)碳酸铯。反应液加热回流24h后，冷却至25℃,加入50mL饱和氯化铵溶液。加入200mL二氯甲烷，分出有机相，水相用二氯甲烷萃取两次，每次用60mL二氯甲烷。合并有机相，干燥，浓缩，经柱层析（乙酸乙酯/石油醚=1:50)得到1.47g化合物1(收率为39%)。1HNMR(400MHz,CDCl3)δ9.21(2H,s),7.89(2H,d,J=7.4),7.42(2H,s),7.25(3H,s),7.11(2H,d,J=2.8),7.04(2H,d,J=8.1),6.70(2H,s),3.80(6H,s)。13CNMR(101MHz,CDCl3)δ169.11(s),148.30(s),135.34(s),134.46(s),132.07(s),125.01(s),124.50(s),117.85(s),115.09(s),113.23(s),77.93(s),77.61(s),77.30(s),52.25(s)。
在40mL甲醇溶液中加入3.46g(9.2mmol)化合物1和40mL浓度为30%的氢氧化钾水溶液，加热搅拌回流10h。反应完成后冷却至室温，加入200mL水进行稀释，用6mol/L盐酸将溶液的pH值调节到4～5，然后用乙酸乙酯萃取（120mL x3）。水洗，盐洗，浓缩，柱分离（乙酸乙酯/石油醚=1:1）得到3.1g（收率96.9%）化合物2。
在50mL干燥的四氢呋喃中加入800mg(2.3mmol)化合物2，2.08g(10.1mmol)N,Nˊ-二环己基碳二亚胺,0.684g(5.1mmol)1-羟基苯并三唑和0.694g(5.1mmol)(S)-2-氨基-2-苯基乙醇，-5℃下搅拌1h。然后再25℃下搅拌12h。反应混合物经浓缩，柱层析（乙酸乙酯）得到1.2g化合物3（88.8%收率）。1HNMR(400MHz,CDCl3)δ8.65(2H,s),7.42(2H,d,J=7.7),7.29(4H,dd,J=8.8,5.0),7.23(6H,d,J=6.9),7.14(2H,t,J=7.7),7.02(6H,dd,J=11.2,5.9),6.67(2H,t,J=7.4),5.71(2H,s),5.17(2H,s),3.82(2H,d,J=9.4),3.76–3.66(2H,m),1.92(4H,s)。13CNMR(101MHz,CDCl3)δ170.43(s),145.70(s),139.43(s),134.98(s),132.79(s),129.39(s),128.56(s),128.34(s),127.30(s),124.37(s),123.30(s),119.60(s),118.73(s),115.93(s),77.93(s),77.62(s),77.30(s),66.47(s),56.41(s)。
在50mL干燥的乙腈中加入1.29g(2.2mmol)化合物3,2.31g(8.8mmol)三苯基膦，0.89g(8.8mmol)三乙胺和1.36g(8.8mmol)四氯化碳，25℃搅拌12h。反应物浓缩后溶于50mL二氯甲烷，水洗，干燥，除去溶剂，混合物经柱层析（乙酸乙酯/石油醚=1:3）得到0.9g(收率74.4%)白色固体化合物4。1HNMR(400MHz,CDCl3)δ10.35(1H,s),7.78(1H,d,J=7.7),7.47(1H,d,J=3.5),7.15(5H,dd,J=19.8,10.8),7.07(3H,s),6.72(1H,t,J=6.9),5.15(1H,t,J=9.1),4.54(1H,t,J=8.8),3.95(1H,t,J=8.0)。13CNMR(101MHz,CDCl3)δ165.19(s),146.88(s),142.87(s),135.76(s),132.64(s),130.53(s),129.00(s),127.70(s),126.91(s),124.54(s),124.17(s),117.30(s),114.13(s),110.92(s),73.39(s),70.32(s)。
其它手性四齿氮配体按照上述方法制备。
实施例2
在N2气保护和15℃条件下，将1.0g含有0.0168mmol/g钴化合物的乙腈溶液加入到1.0g含有0.0168mmol/g四氮配体的乙腈溶液中，搅拌3h。蒸干溶剂得到固体催化剂。
实施例3
将实施例2中的钴化合物改为锰化合物，最后得到固体催化剂
实施例4
在高压反应釜中加入0.0168mmol实施例2中得到的催化剂，0.0336mmol DMAP，2.0g环氧丙烷，密闭高压釜，用CO2置换2～3次后冲压至2.5MPa，升温至50℃，当压力低于3MPa时补充CO2至3MPa，直至反应釜压力不变。反应2h后反应釜用冰浴冷却，慢慢泄压，反应液用气相色谱分析。碳酸丙烯酯的产率为93%。
实施例5
将实施例4中的催化剂改为实施例3中得到的催化剂，反应温度为80℃，反应时间4h，碳酸丙烯酯的产率为88%。
实施例6
在N2气保护和15℃条件下，将1.0g含有0.0168mmol/g钴化合物的环氧丙烷溶液加入到1.0g含有0.0168mmol/g四氮配体的环氧丙烷溶液中，搅拌3h。将反应液加入高压反应釜中，加入0.0336mmol DMAP，密闭高压釜，用CO2置换2～3次后冲压至2.5MPa，升温至50℃，当压力低于3MPa时补充CO2至3MPa，直至反应釜压力不变。反应2h后反应釜用冰浴冷却，慢慢泄压，反应液用气相色谱分析。碳酸丙烯酯的产率为95%，没有发现其它副产物生成。
实施例7
在实施例6的基础上，减压蒸馏出碳酸丙烯酯产品，回收的催化剂循环使用10次，碳酸丙烯酯的产率均大于90%。

Claims (4)

1.一种合成环状碳酸酯的方法，其特征在于：
以CO2和环氧化物为原料，手性四齿氮有机配体和金属化合物形成的手性络合物为催化剂，含氮化合物为助催化剂，手性四齿氮有机配体和金属元素的摩尔比为1:1，手性四齿氮有机配体与底物环氧化物的摩尔比为1:3000～1:100，手性四齿氮有机配体与含氮化合物的摩尔比为1:3～1:1，环氧化物和CO2的摩尔比为1:10～1:1，在25～120℃下反应1～12h，得到产物环状碳酸酯；
所述的手性四齿氮配体是具有如下结构的化合物，
其中R1、R2分别选自氢；烷基，其分子式为CnH2n+1，n＝1～5；芳基；芳基烷基，其分子式为C6H5CnH2n+1,n＝1～5；烷氧基，其分子式为OCnH2n+1,n＝1～5；
R3选自烷基，其分子式为CnH2n+1，n＝1～5；芳基；芳基烷基，其分子式为C6H5CnH2n+1,n＝1～5；烷氧基，其分子式为OCnH2n+1,n＝1～5；
R1、R2、R3相同或不同；X为O、S或N。
2.按照权利要求1所述的方法，其特征在于：手性金属络合物由下列金属元素的一种组成：铜、镁、铁、铝、镍、钌、钴、铬或锰。
3.按照权利要求1所述的方法，其特征在于：助催化剂含氮化合物为三乙胺、吡啶、2,2'-联吡啶、4,4'-联吡啶、4-二甲氨基吡啶、四乙基溴化铵、四乙基碘化铵、四丁基溴化铵、四丁基碘化铵、十二烷基三甲基溴化铵、十二烷基三甲基碘化铵、十六烷基三甲基溴化铵、十六烷基三甲基碘化铵、十八烷基三甲基溴化铵或十八烷基三甲基碘化铵中的至少一种。
4.按照权利要求1所述的方法，其特征在于：
底物环氧化物为是手性环氧化物或对映体环氧化物，其中R，R’，R”为氢；直链烷基，其分子式为CnH2n+1,n＝1～10；环状烷基，其分子式为CnH2n-1，n＝5～8；芳基。
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