CN1260786A - 链烯烃的环氧化方法 - Google Patents
链烯烃的环氧化方法 Download PDFInfo
- Publication number
- CN1260786A CN1260786A CN98806295A CN98806295A CN1260786A CN 1260786 A CN1260786 A CN 1260786A CN 98806295 A CN98806295 A CN 98806295A CN 98806295 A CN98806295 A CN 98806295A CN 1260786 A CN1260786 A CN 1260786A
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- China
- Prior art keywords
- alkene
- reaction
- transition metal
- molecular oxygen
- epoxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 30
- 150000003624 transition metals Chemical group 0.000 claims abstract description 30
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- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 29
- -1 cyclic olefin Chemical class 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 6
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- 230000000881 depressing effect Effects 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims 1
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- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000013460 polyoxometalate Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 31
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- 150000004032 porphyrins Chemical class 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 150000004965 peroxy acids Chemical class 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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Abstract
本发明提供链烯烃的催化环氧化方法,包括让过渡金属取代多金属氧酸盐和分子氧与链烯烃接触。
Description
本发明涉及用于利用过渡金属取代多金属氧酸盐作为催化剂的链烯烃环氧化反应的分子氧的催化活化。
链烯烃的环氧化是重要的化学转变，据此氧原子被加成到碳-碳双键上形成环氧化物。环氧化物常常用作中间体化合物，然后被转化成最终的产品。其实例包括但不特定地限于从环氧乙烷得到的乙二醇和聚乙二醇，从环氧丙烷得到的丙二醇，从氧化苯乙烯得到的苯乙醛和从2R-(2，3-环氧-1-丙醇)得到的萘心安。
链烯烃的环氧化能够使用许多技术来进行。最古老和最常用的方法是让链烯烃与有机过酸根据反应式(1)进行反应。
在本领域使用的典型过酸包括过苯甲酸，过乙酸，过甲酸，过邻苯二甲酸和取代的过苯甲酸如3-氯过苯甲酸。此类酸的盐类也是高效氧化剂，与单过氧邻苯二甲酸镁一样。该酸可以作为纯化合物使用或通过在乙酸酐上加成过氧化氢形成过乙酸而在反应混合物中就地制得。虽然基于反应式(1)中所述反应的方法是已知的，但仍有一些与该反应相关的缺点。其中可列举(a)由环氧化物与水和/或酸在反应介质中的反应形成副产物如二醇类和二醇酯类的倾向，(b)回收和/或回用酸联产品的必要性和(c)由于在有机过酸(酰化过氧氢)使用中存在安全隐患而导致严格的反应控制的必要性。
为了最大程度地减少使用过氧化物作为氧化剂的危害性，使用烷基和烷基芳基过氧化氢代替酰化过氧氢的方法已被建议和采用。这些氧化剂在正常情况下不与链烯烃反应而是需要添加催化剂，如反应式(2)中所述的反应所示。
通常用于这些反应的过氧化氢是叔丁基过氧氢，枯烯过氧氢和乙基苯过氧氢。所使用的催化剂最常见地基于含有Ti(IV)、V(V)、Mo(VI)或W(VI)的化合物，不过许多基于其它金属的化合物也被视作高效催化剂。这些反应是比较安全的，因为烷基和烷基芳基过氧化氢比有机过酸具备更低的反应活性，然而，与酰化过氧氢的使用相关的其它缺点也保留下来。因此，该反应未必更具选择性，因为催化剂的存在常常导致附加的副反应，例如在链烯烃的烯丙位碳上发生取代和氧化而不是氧在双键上的加成。与使用酰化过氧化氢遇到的问题类似，醇联产物必须加以回收，回用和/或另外利用。
使链烯烃环氧化的另一方法是使用含水的过氧化氢作为氧化剂，如反应式(3)所述的反应中所示。
该反应代表了与有机过氧化氢的使用相比而言在概念上的改进：联产物是水，因而对环境友好且不需要回收或回用。与烷基和烷基芳基过氧化氢的使用一样，催化剂的存在是必要的，该催化剂也是常用的含有Ti(IV)、V(V)、Mo(VI)或W(VI)的化合物。仅在特定情况下，对于链烯烃的环氧化报道了高选择性。一些高效和选择性催化剂包括钛硅质岩-1和其它钛取代的沸石，以及多金属氧酸盐如[WZnMn2(ZnW9O19)2]12-和{PO4[WO(O2)2]4}3-。在许多情况下，过氧化氢的使用代表了理想的氧化剂，条件是反应是选择性的。例外的情况是环氧化物的低价格使得过氧化氢的使用过于昂贵。
从链烯烃合成环氧化物的另一重要方法是借助于表卤醇(优选表氯醇)的形成，在第一步中使用次氯酸，随后在第二步中使用碱例如氢氧化钠用于闭环，如反应式(4)中所述反应所示。
这是非常简单的操作程序，然而，具有两个问题。首先，分子氯在次氯酸中的存在常常导致作为不希望有的副产物且必须废弃的二氯化有机物形成。其次，该方法也会形成大量同样必须进行处理或回用的盐类联产物。
从生态和经济两方面考虑，用于链烯烃环氧化的理想氧化剂是空气中的分子氧(二氧)。二氧在链烯烃上的加成在动力学上是不利的，因此需要使用催化方法。对于双键上没有烯丙位碳的情况，可通过使用银催化剂在升高的温度下将氧加成到双键上。以这种方式，从乙烯制备了环氧乙烷。对于使用其它链烯烃如1-丁烯、丙烯等的类似操作方法，该反应无法提供数量显著的环氧化物。在二氧用于链烯烃的环氧化反应时的基本问题在于分子形式的氧分子的自由基性质。在均相反应中，这一自由基性质总是导致在烯丙位碳原子上通过氢取代发生的优先自由基反应。所以，在液相催化反应中常见的利用二氧的模式无法得到作为主要产物的环氧化物。气相反应中的情形类似，其中链烯烃的活化导致烯丙基类型碳阳离子、碳阴离子或碳自由基再次阻止环氧化物作为主要产物来形成。
从概念上讲，为了将二氧用于链烯烃的环氧化反应，二氧的活化应该借助于在氧-氧键断裂之后高价态金属氧合化合物的形成来实现。这些高价态金属氧合中间体是高效环氧化试剂。最常见的作法是本质上利用单氧醇型酶如细胞色素P-450或甲烷单氧酶来进行。这类酶可通过使用锰和铁卟啉作为催化剂来模仿。然而，单氧酶机理需要还原剂的两个电子，以断裂氧-氧键进而形成了在链烯烃环氧化反应中表现活性的高价态金属氧合中间体。从工艺观点考虑，还原剂变成了代替二氧的有限试剂并否定该工艺的诱人之处。
作为可供选择替代的方式，二氧按二氧酶类型机理活化。在该反应中，二氧通过使用两个金属中心而被断裂，导致形成两种高价态金属氧合物质。这一类型反应仅通过使用钌取代四卟啉(RuTMP)得以实现。形成环氧化物的转变速率非常低并且催化剂具有有限的稳定性。
卟啉配体的有限稳定性意味着过渡金属取代多金属氧酸盐是金属卟啉的重要替代催化剂，其公开和讨论于Hill的US专利4,864,041。这些催化剂将保留它们的金属卟啉配对物的高活性，然而却具有明显地更高的热和氧化稳定性，因此可使它们用作长效催化剂。这一现有技术描述了过渡金属取代的多金属氧酸盐在利用氧给体如亚碘酰苯使链烯烃发生环氧化反应方面的应用。其它报道的学术研究在这一报道基础上进一步发展并描述了使用其它氧给体如叔丁基过氧化氢、过氧化氢和对-氰基-N，N-二甲基苯胺-N-氧化物进行链烯烃环氧化反应。但从未描述过渡金属取代的多金属氧酸盐作为催化剂用于由分子氧将链烯烃环氧化的用途。
因此，本发明的目的是提供一种新型的使用分子氧作为氧化剂将链烯烃环氧化的方法。本发明的另一个目的是提供一种用过渡金属催化剂由分子氧进行链烯烃的环氧化的方法。此外，本发明的另一目的是使用过渡金属取代的多金属氧酸盐作为催化剂进行该环氧化反应。
根据本发明，现已发现使用过渡金属取代多金属氧酸盐作为催化剂用于由分子氧将链烯烃加以环氧化的方法。
更具体地说，本发明提供将链烯烃催化环氧化的方法，其中包括让过渡金属取代的多金属氧酸盐和分子氧与链烯烃接触。
本发明描述的方法涉及使用过渡金属取代多金属氧酸盐(TMSP)根据以下反应式(5)催化链烯烃与分子氧的环氧化反应。
多金属氧酸盐是以钨、钼、铌或钒或其混合物的附加物为基础的确定结构的低聚氧化物。更具体地说，过渡金属取代多金属氧酸盐是具有通式Xx(TM)yMmOz q-的化合物，其中杂原子X，若存在(x_0)，可以是主族或过渡族金属，附加原子M是钼，钨，铌或钒或其混合物，以及TM是一种或多种不同的过渡金属。在由本发明描述的方法中使用的特定类型的过渡金属取代多金属氧酸盐[WZnTM2(XW9O19)2]q-被表征为具有W、Zn的“带”的一截keggin结构的二聚体和其结构如附图1所示的“夹心”在两个B-XW9O19三空位keggin片段之间的其它过渡金属(TM)阳离子。过渡金属阳离子被假设位于端部并与至少一个不稳定的配体如水形成六配位。TM原子可以是第一行、第二行或第三行的任何过渡金属。更优选地，TM原子是选自钌、铑、钯、锇、铱和铂的贵金属。最优选地，TM原子是钌。三空位keggin片段的杂原子X能够是现有技术中众所周知的、已知为keggin化合物的任何杂原子。例如，X能够是非金属，如磷、硅、锗、硼或砷。此外X还能够是诸如锌、钴、铁等的金属。该方法的优选过渡金属取代多金属氧酸盐是[WZnRu2(ZnW9O19)2]11-。过渡金属取代多金属氧酸盐或具有以上所述和所示通式结构的物质在此之前从未被用作利用分子氧环氧化链烯烃的催化剂。以上过渡金属取代多金属氧酸盐的阳抗衡离子可以是例如包括碱金属、碱土金属、过渡金属阳离子或有机阳离子如季铵盐在内的任何阳离子。
在反应式(5)中描述的催化反应是通过催化剂与分子氧和链烯烃接触来进行的。在一个方法中催化剂与分子氧接触，随后与链烯烃接触。在另一个方法中，催化剂同时与分子氧和链烯烃接触。在催化剂和反应物(链烯烃和分子氧)之间的反应或接触可在溶剂中进行，据此反应物被加入到已溶解在液相中的催化剂中。一些典型的溶剂是脂族，芳族或卤代烃类。这类溶剂的实例为1，2-二氯乙烷，庚烷，甲苯，二甲苯，氯苯或其混合物。此外，催化剂能够被置于载体上或作为简单的固体使用，随后添加反应物。催化剂所用的载体可以是在非均相催化中使用的任何载体，其中包括其它硅石，氧化铝和其它氧化物。
在该方法中用作反应物的链烯烃可以是任何类型已知链烯烃。这包括简单的端部和线性链烯烃如乙烯，丙烯，1-丁烯，1-辛烯等。该链烯烃也可以是内部支化或线性链烯烃如2-丁烯，2-辛烯，2-甲基-2-庚烯，2，3-二甲基-2-丁烯等。链烯烃也可以是环状的，例如环己烯，环辛烯，降冰片烯等。分子氧可以纯净形式，以空气形式，以富含氧气的空气形式或以消耗氧的空气形式使用。可添加惰性气体。建议的反应温度范围是在0-350℃之间。更优选在25℃和250℃之间和最优选在60℃和180℃之间。该反应可在常压、低于常压或超常压的压力下操作。最优选地，该反应是在超常压下进行。
现在结合下面实施例中的某些优选实施方案和参考附图描述本发明以使本发明的各个方面能够更充分地被理解和了解，但是不应该将本发明限定于这些具体的实施方案。相反，它应该覆盖所有包括在权利要求定义的本发明范围内的替换方案，改进形式和等同方案。因此，包括优选实施方案的下面实施例用于说明本发明的实施，应该理解的是，给出的具体方案是通过举例来说明和仅仅为了示例性讨论本发明的优选实施方案，而且给出的原因是为了提供据信为本发明的配方操作程序及其原理和概念方面最有用和容易理解的叙述。
图1-说明在分子氧加成到链烯烃上形成环氧化物的催化作用中表现活性的一种示例性的过渡金属取代多金属氧酸盐[WZnRu2(ZnW9O19)2]11-的分子结构。
实施例1
含有100μmol Q11WZnRu2(ZnW9O19)2(其中Q是三辛基甲基铵)的5ml脱气1，2-二氯乙烷溶液在密闭的容器中在1atm的分子氧中在90℃下保持9小时。氧溶液被冷却至室温和添加11.2mg的环辛烯。2小时后溶液由GLC进行分析。分析显示67.5％转化成环辛烯氧化物。
实施例2：
含有100μmol Q11WZnRu2(ZnW9O19)2(其中Q是三辛基甲基铵)的5ml脱气1，2-二氯乙烷溶液在密闭容器中在1atm分子氧中在120℃下保持6小时。氧溶液被冷却至室温和添加11.2mg环辛烯。2小时后溶液由GLC进行分析。分析显示72.1％转化成环辛烯氧化物。
实施例3：
含有100μmol Q11WZnRu2(ZnW9O19)2(其中Q是三辛基甲基铵)的5ml脱气1，2-二氯乙烷溶液在密闭容器中在1atm分子氧中在90℃下保持9小时。氧溶液被冷却至室温和添加9.4mg降冰片烯。2小时后溶液由GLC进行分析。分析显示82.1％转化成降冰片烯氧化物。
实施例4：
含有100μmol Q11WZnRu2(ZnW9O19)2(其中Q是三辛基甲基铵)的5ml脱气甲苯溶液在密闭容器中在1atm分子氧中在90℃下保持9小时。氧溶液被冷却至室温和添加11.2mg环辛烯。2小时后溶液由GLC进行分析。分析显示63.7％转化成环辛烯氧化物。
实施例5：
含有100μmol Q11WZnRu2(ZnW9O19)2(其中Q是三辛基甲基铵)的5ml脱气1，2-二氯乙烷溶液在密闭容器中在1atm分子氧中在90℃下保持9小时。氧溶液被冷却至室温和添加8.4mg2，3-二甲基-2-丁烯。2小时后溶液由GLC进行分析。分析显示78.4％转化成2，3-二甲基-2-丁烯氧化物。
实施例6：
含有100μmol Q11WZnRu2(ZnW9O19)2(其中Q是三辛基甲基铵)的5ml脱气1，2-二氯乙烷溶液在密闭容器中在1atm分子氧中在90℃下保持9小时。氧溶液被冷却至室温，然后溶液被吹扫和重新用1atm丙烯加压。在80℃下2小时后溶液由GLC进行分析。分析显示只产生96％环氧丙烷和4％丙烯醛。
实施例7：
含有100μmol Q11WZnRu2(ZnW9O19)2(其中Q是三辛基甲基铵)的5ml脱气1，2-二氯乙烷溶液在密闭容器中在1atm分子氧中在120℃下保持6小时。氧溶液被冷却至室温，然后溶液被吹扫和重新用1atm丙烯加压。在室温下2小时后溶液由GLC进行分析。分析显示只产生98％环氧丙烷和2％丙烯醛。
实施例8：
含有100μmol Q11WZnRu2(ZnW9O19)2(其中Q是三辛基甲基铵)的5ml脱气1，2-二氯乙烷溶液在密闭容器中在1atm分子氧中在90℃下保持18小时。氧溶液被冷却至室温和添加11.2mg1-辛烯。在60℃下18小时后溶液由GLC进行分析。分析显示76％转化成1-环氧辛烷。
实施例9：
含有2.5μmol Q11WZnRu2(ZnW9O19)2(其中Q是三辛基甲基铵)的5ml脱气甲苯溶液和280mg在密闭容器中在5atm分子氧中在90℃下保持24小时。冷却后，GLC分析显示了15％环辛烯转化成环辛烯氧化物。
对于本技术领域技术人员很显然的是，本发明不限于前面示例性实施例中的细节而且本发明能够在不脱离其宗旨的前提下以其它特定形式实施，所以希望这些给出的实施方案和实施例在所有方面被认为是说明性质而并不是限制性的，在参照权利要求而不是上述内容的条件下，在权利要求的等同意义和范围内的所有变化都属于本发明保护范围。
Claims (9)
1、链烯烃的催化环氧化方法，包括让过渡金属取代多金属氧酸盐和分子氧与链烯烃接触。
2、根据权利要求1的方法，其中过渡金属取代多金属氧酸盐首先与分子氧接触，然后与链烯烃接触。
3、根据权利要求1的方法，其中过渡金属取代多金属氧酸盐同时与分子氧和链烯烃接触。
4、根据权利要求1的方法，其中链烯烃选自支化、线性和环状烯烃。
5、根据权利要求1的方法，其中环氧化反应在25-250℃之间的温度下进行。
6、根据权利要求1的方法，其中环氧化反应在超常压下进行。
7、根据权利要求1的方法，其中过渡金属是贵金属。
8、根据权利要求1的方法，其中分子氧用至少惰性气体稀释。
9、根据权利要求1的方法，其中过渡金属是钌。
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| IL120942 | 1997-05-29 | ||
| IL12094297A IL120942A0 (en) | 1997-05-29 | 1997-05-29 | A process for the epoxidation of alkenes |
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|---|---|
| US (1) | US6229028B1 (zh) |
| EP (1) | EP0984950A1 (zh) |
| JP (1) | JP2002502390A (zh) |
| KR (1) | KR20010012833A (zh) |
| CN (1) | CN1260786A (zh) |
| AU (1) | AU729005B2 (zh) |
| BR (1) | BR9809485A (zh) |
| CA (1) | CA2290994A1 (zh) |
| IL (1) | IL120942A0 (zh) |
| WO (1) | WO1998054165A1 (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7425519B2 (en) | 2002-07-18 | 2008-09-16 | Nippon Shokubai Co., Ltd. | Liquid phase oxygenation reaction using tungsten species |
| CN106582815A (zh) * | 2016-12-20 | 2017-04-26 | 聊城大学 | 钒系氧簇化合物催化剂、制备方法及应用 |
| CN107148315A (zh) * | 2014-03-02 | 2017-09-08 | 耶达研究及发展有限公司 | 使用多金属氧酸盐催化剂和氧化氮由烯烃制备醛和酮 |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6326502B1 (en) * | 1997-07-11 | 2001-12-04 | Aventis Research & Technologies Gmbh & Co. Kg | Method for producing epoxides through olefin oxidation with air or oxygen |
| IL128206A0 (en) * | 1999-01-24 | 1999-11-30 | Yissum Res Dev Co | A process for the epoxidation of alkenes and polyoxofluorometalates for use therein |
| US6692916B2 (en) * | 1999-06-28 | 2004-02-17 | Source Precision Medicine, Inc. | Systems and methods for characterizing a biological condition or agent using precision gene expression profiles |
| JP3920020B2 (ja) | 1999-12-24 | 2007-05-30 | 株式会社日本触媒 | 含酸素有機化合物製造用触媒および含酸素有機化合物の製造方法 |
| DE10055173A1 (de) * | 2000-11-08 | 2002-05-29 | Degussa | Verfahren zur Epoxidation von cis-ständigen Doppelbindungen |
| US7417008B2 (en) | 2006-05-31 | 2008-08-26 | Exxonmobil Chemical Patents Inc. | Supported polyoxometalates and process for their preparation |
| US7514577B2 (en) * | 2006-05-31 | 2009-04-07 | Exxonmobil Chemical Patents Inc. | Pd- and Pt-substituted polyoxometalates and process for their preparation |
| WO2011039744A2 (en) * | 2009-10-01 | 2011-04-07 | Yeda Research And Development Co. Ltd. | Aerobic oxidation of primary aliphatic alcohols |
| AU2017286055B2 (en) | 2016-06-15 | 2021-07-01 | BASF Agro B.V. | Process for the epoxidation of a tetrasubstituted alkene |
| AU2017284971B2 (en) * | 2016-06-15 | 2021-01-21 | BASF Agro B.V. | Process for the epoxidation of a tetrasubstituted alkene |
| CN107903164A (zh) * | 2017-10-24 | 2018-04-13 | 山东联创互联网传媒股份有限公司 | 同时制备有机酸和环氧丁烷的方法 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4447231A1 (de) * | 1994-12-30 | 1996-07-04 | Hoechst Ag | Verfahren zur Herstellung von Epoxiden durch Oxidation von Olefinen mit Luft oder Sauerstoff |
| EP0043192A1 (en) * | 1980-06-26 | 1982-01-06 | Imperial Chemical Industries Plc | Process for the oxidation of olefinic compounds to olefine oxides or derivatives thereof |
| US4864041A (en) | 1987-02-04 | 1989-09-05 | Emory University | Transition metal-substituted polyoxometalates as catalysts for homogenous liquid-phase organic oxidation processes |
| US5223631A (en) | 1992-06-30 | 1993-06-29 | National Science Council | Bimetallic complexes as catalysts in an oxidation process |
| DE19519008A1 (de) * | 1995-05-24 | 1996-11-28 | Hoechst Ag | Neue ruthenium- und selen- oder schwefelhaltige Metalloxidkatalysatoren sowie ein Verfahren zu ihrer Herstellung und ihre Verwendung |
| DE19530787A1 (de) * | 1995-08-22 | 1997-02-27 | Hoechst Ag | Mangan enthaltende Polyoxometallate, Synthese und Verwendung |
-
1997
- 1997-05-29 IL IL12094297A patent/IL120942A0/xx unknown
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1998
- 1998-05-27 US US09/424,787 patent/US6229028B1/en not_active Expired - Fee Related
- 1998-05-27 JP JP50043799A patent/JP2002502390A/ja active Pending
- 1998-05-27 AU AU75458/98A patent/AU729005B2/en not_active Ceased
- 1998-05-27 EP EP98923032A patent/EP0984950A1/en not_active Withdrawn
- 1998-05-27 CN CN98806295A patent/CN1260786A/zh active Pending
- 1998-05-27 CA CA002290994A patent/CA2290994A1/en not_active Abandoned
- 1998-05-27 KR KR19997010798A patent/KR20010012833A/ko not_active Application Discontinuation
- 1998-05-27 WO PCT/IL1998/000245 patent/WO1998054165A1/en not_active Application Discontinuation
- 1998-05-27 BR BR9809485-8A patent/BR9809485A/pt not_active IP Right Cessation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7425519B2 (en) | 2002-07-18 | 2008-09-16 | Nippon Shokubai Co., Ltd. | Liquid phase oxygenation reaction using tungsten species |
| CN100439349C (zh) * | 2002-07-18 | 2008-12-03 | 株式会社日本触媒 | 使用含钨化合物的液相氧化反应 |
| CN107148315A (zh) * | 2014-03-02 | 2017-09-08 | 耶达研究及发展有限公司 | 使用多金属氧酸盐催化剂和氧化氮由烯烃制备醛和酮 |
| CN106582815A (zh) * | 2016-12-20 | 2017-04-26 | 聊城大学 | 钒系氧簇化合物催化剂、制备方法及应用 |
| CN106582815B (zh) * | 2016-12-20 | 2019-04-19 | 聊城大学 | 钒系氧簇化合物催化剂、制备方法及应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002502390A (ja) | 2002-01-22 |
| EP0984950A1 (en) | 2000-03-15 |
| WO1998054165A1 (en) | 1998-12-03 |
| BR9809485A (pt) | 2000-06-20 |
| AU729005B2 (en) | 2001-01-25 |
| IL120942A0 (en) | 1997-09-30 |
| US6229028B1 (en) | 2001-05-08 |
| CA2290994A1 (en) | 1998-12-03 |
| KR20010012833A (ko) | 2001-02-26 |
| AU7545898A (en) | 1998-12-30 |
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