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CN1283602C - 催化氧化烯烃成烯醇、烯酮和环氧化合物的方法 - Google Patents

催化氧化烯烃成烯醇、烯酮和环氧化合物的方法 Download PDF

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CN1283602C
CN1283602C CNB2003101105337A CN200310110533A CN1283602C CN 1283602 C CN1283602 C CN 1283602C CN B2003101105337 A CNB2003101105337 A CN B2003101105337A CN 200310110533 A CN200310110533 A CN 200310110533A CN 1283602 C CN1283602 C CN 1283602C
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CN1544404A (zh
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郭灿城
刘�文
马金勇
毛彦利
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    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
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    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
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Abstract

本发明公开了在氧化剂为空气或氧气或氧气与惰性气体的混合气体或其它化学氧化剂的存在下，控制反应压力为1-10atm，温度为20-150℃，选用单金属卟啉或μ-氧双金属卟啉或它们的固载物单独作催化剂或它们与过滤金属盐或氧化物构成的复合催化剂，催化剂浓度为1-50PPM，反应0.5-5小时，催化氧化烯烃或环烯烃生成α，β-烯醇、α，β-烯酮和环氧化合物。该工艺反应条件温和，所用催化剂用量小、催化效率高，反应选择性好，该催化反应可以均相催化，也可以固载后进行异相催化。

Description

催化氧化烯烃成烯醇、烯酮和环氧化合物的方法
                           技术领域
本发明涉及金属卟啉催化下烯烃或环烯烃被空气或化学氧化剂选择氧化制备α，β-烯醇、α，β-烯酮和环氧化合物的方法。
                           背景技术
烯烃的空气氧化一般需要在金、银等贵金属催化和高温条件下进行。由于反应对碳碳双键和烯丙基氢的反应选择性差，导致副反应多，产物难分离，反应收率不高。烯烃的化学氧化由于较多深度氧化产物生成而无法控制和利用。减少烯烃空气氧化副反应和利用烯烃化学氧化的途径是使用合适的催化剂提高反应的选择性。现已有某些选用单金属卟啉作催化剂的报道，是利用单金属卟啉作为均相催化剂，催化NaClO等氧化剂对烯烃的氧化。这种方法可提高烯烃氧化反应的选择性，但NaClO同时氧化单金属卟啉而使其失去催化效果，尚未投入工业生产。
                           发明内容
本发明的目的是提供一种选择性好、转化率和回收率高、可避免深度氧化产物的生成、产品纯度高、容易分离的烯烃或环烯烃氧化制备α，β-烯醇、α，β-烯酮和环氧化合物的方法。
本发明的技术方案是：在氧化剂为空气或氧气或氧气与惰性气体的混合气体或其它化学氧化剂的存在下，控制反应压力为1-10atm，温度为20-150℃，选用由通式(I)或(II)的单金属卟啉或μ-氧双金属卟啉或它们的固载物单独作催化剂或它们与过滤金属盐或氧化物构成的复合催化剂，催化剂浓度为1-50PPM，反应0.5-5小时，催化氧化烯烃或环烯烃生成α，β-烯醇、α，β-烯酮和环氧化合物。
所述化学氧化剂可以为NaClO，H2O2，过氧乙酸等，当用化学氧化剂时，反应温度为20-80℃，压力为常压，并在水，乙酸，乙酸乙酯，苯，甲苯等溶剂中进行。
所述烯烃可以是C3-C10链烯烃、C5-C8单环烯烃、多环烯烃，芳香烯烃，以及它们的衍生物。
所述复合催化剂是由通式(I)或(II)金属卟啉或它们的固载物作为主催化剂，主催化剂浓度为1-50PPM，以过渡金属盐或氧化物或无机盐作为添加剂，主催化剂与添加剂的摩尔比为1∶1-20。
Figure C20031011053300051
通式(I)中的金属原子M可以是Fe，Mn，Co，Cr，Cu，Ni，Pt，Pd，Tb，等过渡金属原子或镧系金属原子；苯环上取代基R1，R2，R3可以是氢，烃基，烷氧基，羟基，硝基，卤素，胺基，氨基，糖基，取代糖基和环糊精。配位基X可以是乙酸，乙酰丙酮，卤素及其他酸根负离子。
通式(II)中的金属原子M1，M2可以是Fe，Mn，Cr等过渡金属原子。苯环上取代基R1，R2，R3可以是氢，烃基，烷氧基，羟基，硝基，卤素，胺基，氨基，糖基和环糊精。
本发明优选的压力范围是4-8atm，优选的温度范围是50-110℃，优选的催化剂浓度为2-8PPM。
复合催化剂中的添加物可以为Cu，Zn，Fe，Co，Mn，Cr，Ni等金属的盐或氧化物，也可以是磷酸盐、膦酸盐、胺或铵盐，还可以是氢和CO等还原性气体。这些添加物能明显改善金属卟啉对空气氧化烯烃和环烯烃的催化性能。
与上述金属卟啉构成固载金属卟啉催化剂的载体有：硅胶，分子筛，氧化铝，沸石，硅藻土，活性碳，海泡石，多孔陶瓷，聚氯乙烯，聚过氯乙烯，聚苯乙烯，纤维素，壳聚糖，甲壳素及它们的改性物。
                          具体实施方式
实施例1：
将5mg具有结构式(I)的金属卟啉，R1＝R2＝R3＝CH3，M＝Mn，和20mg Cu2Cl2加入300ml环己烯中，通入4atm空气。在55℃下搅拌反应物3小时，环己烯转化率为4.2％，反应产物中α，β-环己烯醇、α，β-环己烯酮和环氧环己烷收率90％。
实施例2：
将3mg具有结构式(II)的金属卟啉，R1＝R2＝OH，R3＝Cl，M1＝M2＝Fe，和20mg磷酸钠加入400ml苯乙烯中，通入5atm空气，在80℃下搅拌反应物4小时，苯乙烯转化率为10.8％，反应产物中环氧苯乙烷收率60％。
实施例3：
将7mg具有结构式(I)的金属卟啉，R1＝OCH3，R2＝R3＝H，M1＝Co，和24mg三乙胺加入400ml 2-丁烯中，通入8atm空气，在80℃下搅拌反应物2小时，丁烯转化率为30.8％，反应产物中环氧丁烷和丁烯醛收率80％。
实施例4：
将分子筛固载6mg结构式(II)的金属卟啉，R1＝NO2，R2＝R3＝H，M1＝M2＝Mn，加入100mlα-派烯和300ml乙酸的混合体系中。在70℃搅拌下慢慢加入50克NaClO，压力为常压，反应1小时，α-派烯转化率为50.3％，反应产物中环氧化合物、烯醇和烯酮收率90％。
实施例5：
将聚氯乙烯固载4mg结构式(I)的金属卟啉，R1＝R2＝N(CH3)2，R3＝C2H5，M＝Cr，加入400ml丙烯中。通入10atm氧气。在50℃下搅拌反应物4小时，丙烯转化率为26％，反应产物中环氧丙烷、丙烯醛和丙烯酸收率88％。
实施例6：
将5mg具有结构式(I)的金属卟啉，R1＝C4H9，R2＝R3＝H，M＝Fe，和30mg醋酸钴加入300ml环戊烯与100ml苯的混合体系中，通入6atm含氧6％，含氢2％的混合空气。在100℃下搅拌反应物1小时，苯戊烯转化率为18.5％，反应产物中环氧化物，烯醇和烯酮收率92％。
实施例7：
将8mg具有通式(I)结构的金属卟啉，R1＝R2＝R3＝Cl，M＝Fe，用3克纤微素固载后，加入500ml环己烯中，通入6atm含2％CO的混合空气。在110℃下搅拌反应物0.5小时，环己烯转化率为20.5％，反应产物中环氧化物，烯醇和烯酮收率83％。
实施例8：
将3mg具有通式(II)结构的金属卟啉，R1＝R2＝H，R3＝2，3，4，6-四乙酰葡萄糖基，M1＝M2＝Fe，加入100ml苯并环戊烯中，通入6atm空气。在120℃下反应1小时，苯并环戊烯转化率为35％，反应产物中环氧化物，烯醇和烯酮收率94％。
实施例9：
将8mg具有通式(II)的金属卟啉，R1＝OC2H5，R2＝R3＝H，M1＝M2＝Cr，和50mgNiO加入500ml苯丙烯中，通入8atm空气。在130℃下搅拌反应物0.5小时，苯丙烯转化率为12.4％，反应产物中环氧化物，烯醇和烯酮收率86％。
实施例10：
将6mg具有通式(I)的金属卟啉，R1＝R2＝R3＝CH3，M＝Cu，和10mg三苯膦加入500ml环庚烯中，通入5atm空气。在75℃下搅拌反应物3小时，环庚烯转化率为10.5％，反应产物中环氧化物，烯醇和烯酮收率90％。

Claims (7)

1.一种催化氧化烯烃和环烯烃成烯醇、烯酮和环氧化合物的方法，其特征在于，在氧化剂为空气或氧气或氧气与惰性气体的混合气体或化学氧化剂NaClO，H2O2，过氧乙酸的存在下，控制反应压力为1-10atm，温度为20-150℃，选用由通式(I)或(II)的单金属卟啉或μ-氧双金属卟啉或它们的固载物单独作催化剂或它们与过滤金属盐或氧化物构成的复合催化剂，金属卟啉催化剂浓度为1-50PPM，反应0.5-5小时；
通式(I)中的金属原子M是过渡金属原子或镧系金属原子Fe、Mn、Co、Cr、Cu、Ni、Pt、Pd或Tb；苯环上取代基R1、R2、R3是氢、烃基、烷氧基、羟基、硝基、卤素、氨基或环糊精基；配位基X是乙酸基、乙酰丙酮基或卤素基；
通式(II)中的金属原子M1，M2是过渡金属原子Fe、Mn或Cr；苯环上取代基R1、R2、R3是氢、烃基、烷氧基、羟基、硝基、卤素基、氨基或环糊精基。
2、、根据权利要求1所述方法，其特征在于所述复合催化剂是由通式(I)或(II)的金属卟啉或它们的固载物作为主催化剂，金属卟啉催化剂浓度为1-50PPM，以过渡金属盐或氧化物作为添加剂，金属卟啉催化剂与添加剂的摩尔比为1∶1-20。
3.根据权利要求1或2所述方法，其特征在于当用化学氧化剂时，反应温度为20-80℃，压力为常压，并在水、乙酸、乙酸乙酯、苯或甲苯溶剂中进行。
4.根据权利要求1或2所述方法，其特征在于所述烯烃为C3-C10链烯烃、C5-C8单环烯烃、多环烯烃或芳香烯烃。
5.根据权利要求1或2所述方法，其特征在于压力范围是4-8atm，温度范围是50-110℃，催化剂浓度为2-8PPM。
6.根据权利要求1或2所述方法，其特征在于复合催化剂中的添加剂为Cu、Zn、Fe、Co、Mn、Cr、Ni盐或氧化物。
7.根据权利要求1或2所述方法，其特征在于所述固载金属卟啉的载体有：硅胶、分子筛、氧化铝、沸石、硅藻土、活性炭、海泡石、多孔陶瓷、聚氯乙烯、聚过氯乙烯、聚苯乙烯、纤维素、壳聚糖或甲壳素。
CNB2003101105337A 2003-11-18 2003-11-18 催化氧化烯烃成烯醇、烯酮和环氧化合物的方法 Expired - Fee Related CN1283602C (zh)

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FR0452664A FR2862302A1 (fr) 2003-11-18 2004-11-17 Procede pour l'oxydation catalytique d'olefines en enols, olefine-cetones et epoxydes
NL1027537A NL1027537C2 (nl) 2003-11-18 2004-11-17 Een werkwijze voor katalytische oxidatie van olefinen naar enolen, olefineketonen en epoxiden.

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US8080677B2 (en) 2005-10-25 2011-12-20 University Of Kansas Process for selective oxidation of olefins to epoxides
EP1943237B1 (en) * 2005-10-25 2015-06-17 University Of Kansas Process for selective oxidation of olefins to epoxides
CN101899022B (zh) * 2010-07-27 2012-01-18 中山大学 一种仿生催化丙烯环氧化制备环氧丙烷的方法
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CN112341407A (zh) * 2020-10-23 2021-02-09 如皋市丹凤纺织有限公司 一种纱线浸渍助剂合成方法
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