JPS62263172A - Production of epoxy compound - Google Patents
Production of epoxy compoundInfo
- Publication number
- JPS62263172A JPS62263172A JP61104749A JP10474986A JPS62263172A JP S62263172 A JPS62263172 A JP S62263172A JP 61104749 A JP61104749 A JP 61104749A JP 10474986 A JP10474986 A JP 10474986A JP S62263172 A JPS62263172 A JP S62263172A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- molybdenum
- complex
- ligand
- carbon
- 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
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- 239000004593 Epoxy Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 150000002466 imines Chemical class 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 11
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011733 molybdenum Substances 0.000 abstract description 6
- -1 oxoethoxo(5 Chemical compound 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 5
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 abstract description 3
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 8
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000006735 epoxidation reaction Methods 0.000 description 5
- 150000004032 porphyrins Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- LIESJAYIOKBLIL-UHFFFAOYSA-N 2-methyl-3-propyloxirane Chemical compound CCCC1OC1C LIESJAYIOKBLIL-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JYJVVHFRSFVEJM-UHFFFAOYSA-N iodosobenzene Chemical compound O=IC1=CC=CC=C1 JYJVVHFRSFVEJM-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- SBTXZBOBSRZUPE-UHFFFAOYSA-N 5,10,15,20-tetrapyridin-2-yl-21,23-dihydroporphyrin Chemical compound c1cc2nc1c(-c1ccccn1)c1ccc([nH]1)c(-c1ccccn1)c1ccc(n1)c(-c1ccccn1)c1ccc([nH]1)c2-c1ccccn1 SBTXZBOBSRZUPE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DSGVIQLRGSBXEQ-UHFFFAOYSA-N Cc1c(C)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(C)c5C)c(C)c4C)c(C)c3C Chemical compound Cc1c(C)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(C)c5C)c(C)c4C)c(C)c3C DSGVIQLRGSBXEQ-UHFFFAOYSA-N 0.000 description 1
- SZKKRCSOSQAJDE-UHFFFAOYSA-N Schradan Chemical group CN(C)P(=O)(N(C)C)OP(=O)(N(C)C)N(C)C SZKKRCSOSQAJDE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 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
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- FHHZOYXKOICLGH-UHFFFAOYSA-N dichloromethane;ethanol Chemical compound CCO.ClCCl FHHZOYXKOICLGH-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Chemical compound [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 0.000 description 1
- HCIIFBHDBOCSAF-UHFFFAOYSA-N octaethylporphyrin Chemical compound N1C(C=C2C(=C(CC)C(C=C3C(=C(CC)C(=C4)N3)CC)=N2)CC)=C(CC)C(CC)=C1C=C1C(CC)=C(CC)C4=N1 HCIIFBHDBOCSAF-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- GXZZNUGESLEFGV-UHFFFAOYSA-N trioxomolybdenum;hydrate Chemical compound O.O=[Mo](=O)=O GXZZNUGESLEFGV-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はエポキシ化合物の製造法に関するものである。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing an epoxy compound.
さらに詳しくいえば、本発明は、特定の触媒を用いて、
炭素−炭素二重結合を有する不飽和炭化水素から、極め
て高い選択率でかつ工業的に有利にエポキシ化合物を製
造する方法に関するものである。More specifically, the present invention uses a specific catalyst to
The present invention relates to a method for producing an epoxy compound from an unsaturated hydrocarbon having a carbon-carbon double bond with extremely high selectivity and industrially advantageously.
エポキシ基は反応性に優れた官能基であり、他の官能基
、例えば水酸基、カルボキシル基、アミノ基などと極め
て容易に反応するので、このエポキシ基を含有する化合
物は、例えば医薬品、農薬をはじめ種々の有機薬品の合
成原料などとして、工業的に重要な化合物である。Epoxy groups are functional groups with excellent reactivity and react extremely easily with other functional groups, such as hydroxyl groups, carboxyl groups, and amino groups. It is an industrially important compound as a raw material for the synthesis of various organic drugs.
従来、脂肪族オレフィンや環式オレフィンあるいはこれ
らの芳香族置換オレフィンのエチレン性二重結合を酸化
してエポキシ化する方法として種々の方法が知られてい
る。例えば、触媒としてモリブデンやクロムの酸化物を
用い分子状酸素で酸化する方法（特開昭５２−３０３６
）、酸化モリブデン水化物と有機過酸化物で酸化する方
法（特開昭５３−１３１９９２号公報）、触媒としてモ
リブデン、バナジウム、タングステン、チタンなどの化
合物を用い、α−ヒドロパーオキシイソ酪酸第一級アル
コールエステルで酸化する方法（特開閉５２−２１１号
公報）、鉄のポルフィリン錯体とヨードシルベンゼンを
用いて酸化する方法〔「ジャーナル・オブ・アメリカン
・ケミカル・ソサエティ（Ｊ、Ａａ＋、Ｃｈｅａ＋、Ｓ
ｏｃ、） Ｊ第１０５巻、第５７８６ページ（１９８３
年）〕などが知られている。Conventionally, various methods have been known for oxidizing the ethylenic double bonds of aliphatic olefins, cyclic olefins, or aromatic substituted olefins to epoxidize them. For example, a method of oxidizing with molecular oxygen using molybdenum or chromium oxide as a catalyst (Japanese Patent Application Laid-open No. 52-3036
), a method of oxidizing with molybdenum oxide hydrate and an organic peroxide (JP-A-53-131992), using compounds such as molybdenum, vanadium, tungsten, and titanium as catalysts, A method of oxidation using a porphyrin complex of iron and iodosylbenzene (Japanese Patent Publication No. 52-211), a method of oxidation using an iron porphyrin complex and iodosylbenzene [Journal of the American Chemical Society (J, Aa+, Chea+, S
oc,) J Volume 105, Page 5786 (1983
)] are known.
また、触媒としてバナジウムイオン交換ゼオライトを用
い、分子状酸素で酸化する方法が提案されている（米国
特許第４．１８２．７２２号明細書）。 しかしながら
、これらの方法においては、いずれも使用する酸化物が
高価であったり、酸化剤は安価であるものの、エポキシ
化合物の選択率が十分でなく、副生成物が生ずるという
欠点がある。Furthermore, a method of oxidizing with molecular oxygen using vanadium ion exchange zeolite as a catalyst has been proposed (US Pat. No. 4,182,722). However, these methods all have the disadvantage that the oxides used are expensive, and although the oxidizing agent is inexpensive, the selectivity of the epoxy compound is insufficient and by-products are produced.
本発明の目的は、このような従来の方法が有する欠点を
改良し、炭素−炭素二重結合を有する不飽和炭化水素か
ら、高い選択率でエポキシ基を有する化合物を工業的に
有利に製造する方法を提供することにある。The purpose of the present invention is to improve the drawbacks of such conventional methods and to industrially advantageously produce compounds having epoxy groups with high selectivity from unsaturated hydrocarbons having carbon-carbon double bonds. The purpose is to provide a method.
本発明者らは、先に炭素−炭素二重結合を有する不飽和
炭化水素を、大環状イミンを配位子としたニオブ−酸素
錯体を用い、可視光の照射下に分子状酸素で酸化するこ
とにより、極めて高い選択率で効率よくエポキシ化合物
が得られることを見出したく特願昭５９−１７７５９４
号）。The present inventors first oxidized an unsaturated hydrocarbon having a carbon-carbon double bond with molecular oxygen under visible light irradiation using a niobium-oxygen complex with a macrocyclic imine as a ligand. Patent application No. 59-177594 to discover that epoxy compounds can be efficiently obtained with extremely high selectivity by
issue).
本発明者らは、さらに鋭意検討を進めた結果、モリブデ
ン−酸素錯体を用いても炭素−炭素二重結合が酸化され
て高い選択率でエポキシ化合物が得られることを見出し
、本発明を完成するに至った。 すなわち、本発明は、
炭素−炭素二重結合を有する不飽和炭化水素を酸化して
エポキシ基を有する化合物を製造するにあたり、反応系
に大環状イミンを配位子としたモリブデン−酸素錯体を
添加し、かつ、可視光照射下に、該不飽和炭化水素を分
子状酸素により酸化することを特徴とするエポキシ化合
物の製造法を提供するものである。As a result of further intensive studies, the present inventors discovered that even when a molybdenum-oxygen complex is used, carbon-carbon double bonds can be oxidized and epoxy compounds can be obtained with high selectivity, thereby completing the present invention. reached. That is, the present invention
When producing a compound having an epoxy group by oxidizing an unsaturated hydrocarbon having a carbon-carbon double bond, a molybdenum-oxygen complex with a macrocyclic imine as a ligand is added to the reaction system, and visible light is added to the reaction system. The present invention provides a method for producing an epoxy compound, characterized in that the unsaturated hydrocarbon is oxidized with molecular oxygen under irradiation.
本発明方法において用いる大環状イミンを配位子とした
モリブデン−酸素錯体は、中心金属のモリブデンに大環
状イミン配位子と酸素とが配位した、構造式
％式％
（式中の−ＮＮ−は大環状イミン配位子を示し、Ｒは１
級または２級のアルキル基を示す）で表される錯体であ
る。したがって、大環状イミン配位子がポルフィリン環
で、かつＲがエチル基の場合は、この錯体は（ＭｏＯＣ
０Ｃｔ Ｈｓ ）（ＰＯＲ）〕 （ただし、ＦＯＲはポ
ルフィリンを示す）と表すことができる。The molybdenum-oxygen complex with a macrocyclic imine as a ligand used in the method of the present invention has a structural formula (-NN - indicates a macrocyclic imine ligand, R is 1
It is a complex represented by (representing a class or secondary alkyl group). Therefore, when the macrocyclic imine ligand is a porphyrin ring and R is an ethyl group, the complex is (MoOC
0Ct Hs ) (POR)] (where FOR represents porphyrin).
この錯体における大環状イミン配位子としては、例えば
ポルフィリン、テトラフェニルポルフィリン、テトラ−
１）−トリルポルフィリン、３．５−ジ−ｔ−ブチルフ
ェニルポルフィリン、テトラピリジルポルフィリン、テ
トラ−ｐ−スルホフェニルポルフィリン、オクタエチル
ポルフィリン、オクタメチルポルフィリン、フタロシア
ニン、テトラスルホフタロシアニン、オクタエチルフタ
ロシアニン、オクタメチルフタロシアニンなどが挙げら
れる。Examples of macrocyclic imine ligands in this complex include porphyrin, tetraphenylporphyrin, and tetra-
1)-Tolylporphyrin, 3.5-di-t-butylphenylporphyrin, tetrapyridylporphyrin, tetra-p-sulfophenylporphyrin, octaethylporphyrin, octamethylporphyrin, phthalocyanine, tetrasulfophthalocyanine, octaethyl phthalocyanine, octamethyl Examples include phthalocyanine.
このような大環状イミンを配位子としたモリブデン−酸
素錯体は種々の方法により製造することができる。その
好適な製造方法の一例について説明すると、まず、デカ
リンなどの溶媒中において、所望の大環状イミンと化学
量論的な量より若干過剰量のモリブデンヘキサカルボニ
ルなどのモリブデン化合物とを、例えば１５０〜２５０
℃の範囲の温度において５〜３０時間加熱して反応させ
、次いで溶媒の留去、抽出、洗浄、精製、再結晶などの
操作を行うことにより、その操作過程で空気酸化されて
、所望の該大環状イミンを配位子としたモリブデン−酸
素錯体が得られる。A molybdenum-oxygen complex using such a macrocyclic imine as a ligand can be produced by various methods. To explain one example of a suitable manufacturing method, first, a desired macrocyclic imine and a molybdenum compound such as molybdenum hexacarbonyl in a slightly excess amount than the stoichiometric amount are mixed in a solvent such as decalin, for example, from 150 to 250
The reaction is carried out by heating for 5 to 30 hours at a temperature in the range of °C, followed by operations such as distillation of the solvent, extraction, washing, purification, and recrystallization. A molybdenum-oxygen complex with a macrocyclic imine as a ligand is obtained.
この大環状イミンを配位子としたモリブデン−酸素錯体
は、そのまま反応系に添加してもよいし、所望により、
例えばシリカ、アルミナ、シリカ−アルミナなどの担体
に担持して用いてもよい。また、その使用量は原料の不
飽和化合物に対し、通常０．０００１〜１．０モル％、
好ましくは０．００１〜０．１モル％の範囲で選ばれる
。The molybdenum-oxygen complex with this macrocyclic imine as a ligand may be added to the reaction system as it is, or if desired,
For example, it may be supported on a carrier such as silica, alumina, or silica-alumina. In addition, the amount used is usually 0.0001 to 1.0 mol%, based on the unsaturated compound of the raw material.
It is preferably selected within the range of 0.001 to 0.1 mol%.
本発明方法において原料として用いる不飽和炭化水素は
、炭素−炭素二重結合を有するものであって、一般的に
は炭素数４〜２０の無置換またはハロゲン原子、各種官
能基、芳香族残基などで置換された脂肪族または脂環式
の不飽和炭化水素が使用される。このような不飽和炭化
水素としては、例えばエチレン、プロピレン、ｎ−ブテ
ン、イソブチン、１−ペンテン、２−ペンテン、２−ヘ
キセン、３−ヘキセン、２−メチル−２−ブテン、２．
３−ジメチル−２−ブテン、２−ヘプテン、３−ヘプテ
ン、２−１３−または４−オクテン、２−１３−または
４−ノネン、シクロペンテン、シクロヘキセン、スチレ
ン、α−メチルスチレンなどの不飽和結合を１個有する
もの、１．３−ペンタジェン、ｌ、３−へキサジエン、
１，４−へキサジエン、２．４−ヘキサジエン、１．４
−１１．５−．２．４−または２．５−へブタジェンな
どの不飽和結合を２個有するものなどが挙げられる。The unsaturated hydrocarbon used as a raw material in the method of the present invention has a carbon-carbon double bond, and is generally unsubstituted or has a carbon number of 4 to 20, a halogen atom, various functional groups, and an aromatic residue. Aliphatic or cycloaliphatic unsaturated hydrocarbons substituted with, etc. are used. Examples of such unsaturated hydrocarbons include ethylene, propylene, n-butene, isobutyne, 1-pentene, 2-pentene, 2-hexene, 3-hexene, 2-methyl-2-butene, 2.
Unsaturated bonds such as 3-dimethyl-2-butene, 2-heptene, 3-heptene, 2-13- or 4-octene, 2-13- or 4-nonene, cyclopentene, cyclohexene, styrene, α-methylstyrene, etc. Those with one, 1,3-pentadiene, l,3-hexadiene,
1,4-hexadiene, 2.4-hexadiene, 1.4
-11.5-. Examples include those having two unsaturated bonds such as 2.4- or 2.5-hebutadiene.
本発明方法においては、このような炭素−炭素二重結合
を有する鎖状不飽和炭化水素を原料とし、これに前記の
大環状イミンを配位子としたモリブデン−酸素錯体を添
加して可視光の照射下に、分子状酸素で酸化することに
より、二重結合がエポキシ化される。この反応機構につ
いては必ずしも明確ではないが、可視光の照射によりま
ず該錯体が開裂し、さらに酸素によって酸化されて、い
わゆるスーパーオキソ錯体が形成され、このものが前記
不飽和化合物に作用して、エポキシ基が形成されるもの
と推定される。したがって、可視光を照射しないと、こ
のエポキシ化反応は進行しない。In the method of the present invention, a chain unsaturated hydrocarbon having such a carbon-carbon double bond is used as a raw material, a molybdenum-oxygen complex having the macrocyclic imine as a ligand is added thereto, and visible light is emitted. The double bond is epoxidized by oxidation with molecular oxygen under irradiation. Although the mechanism of this reaction is not necessarily clear, the complex is first cleaved by irradiation with visible light, and then oxidized by oxygen to form a so-called superoxo complex, which acts on the unsaturated compound, It is presumed that an epoxy group is formed. Therefore, this epoxidation reaction does not proceed unless visible light is irradiated.
照射する可視光の強さや波長などについては特に制限は
ないが、エポキシ化反応を円滑に進行させるためには、
室内光だけでは不十分であるので、少なくともタングス
テン電灯程度の強さの光、具体的にはｓｏｏｗのタング
ステン電灯を３０ｃｎ＋離して照射する場合の光の強さ
以上の強さを存する可視光を照射することが好ましい、
また、可視光の波長は、使用する該錯体の吸収特性に応
じて適宜選択することが望ましいが、例えばテトラ−ｐ
−トリルポルフィリン（ＴＴＰ）を配位子とするオキソ
エトキシ（５，１０，１５，２０−テトラ−ｐ−トリル
ポルフィナトモリブデン） （Ｍｏ□Ｃ０Ｃ２Ｈ，（
ＴＴＰ） ）は４００〜５００ｎｍに強い吸収帯をもち
、かつ５５０〜６５０ｎｍに中程度の吸収帯を有するの
で、このようなポルフィリン錯体を用いる場合には、可
視光のほぼ全波長領域にわたって吸収帯があるため、い
かなる種類の可視光も使用可能である。There are no particular restrictions on the intensity or wavelength of visible light to be irradiated, but in order for the epoxidation reaction to proceed smoothly,
Since indoor light alone is not enough, we irradiate visible light that is at least as strong as a tungsten electric lamp, specifically, more intense than the light intensity of a SOOW tungsten electric lamp when irradiated from a distance of 30cm+. It is preferable to
The wavelength of visible light is preferably selected appropriately depending on the absorption characteristics of the complex used, but for example, tetra-p
-Oxoethoxy (5,10,15,20-tetra-p-tolylporphynatomolybdenum) with tolylporphyrin (TTP) as a ligand (Mo□C0C2H, (
TTP) has a strong absorption band in the 400-500 nm range and a moderate absorption band in the 550-650 nm range, so when using such a porphyrin complex, the absorption band will be over almost the entire wavelength range of visible light. Therefore, any type of visible light can be used.
本発明方法において酸化剤として用いる分子状酸素とし
ては、酸素、または酸素と窒素やアルゴンなどの不活性
ガスとの混合ガスが挙げられる。The molecular oxygen used as an oxidizing agent in the method of the present invention includes oxygen or a mixed gas of oxygen and an inert gas such as nitrogen or argon.
この混合ガスとしては空気が好ましく用いられる。Air is preferably used as this mixed gas.
エポキシ化反応は、該分子状酸素をバブリングなどによ
って反応系に供給して行ってもよいし、単に分子状酸素
の存在下に、反応系を攪拌することにより行ってもよい
０例えば反応系を開放系にして攪拌すれば、この反応に
必要な酸素は十分に供給され、エポキシ化反応は進行す
る。The epoxidation reaction may be carried out by supplying the molecular oxygen to the reaction system by bubbling or the like, or may be carried out simply by stirring the reaction system in the presence of molecular oxygen. If the system is stirred in an open system, oxygen necessary for this reaction will be sufficiently supplied and the epoxidation reaction will proceed.
反応温度については、通常、室温から１００℃までの範
囲が望ましいが、さらに好ましくは２０〜４０℃で行わ
れる。The reaction temperature is usually preferably in the range from room temperature to 100°C, more preferably from 20 to 40°C.
また、反応圧力については反応系が液相を保つのに十分
な圧であれば、減圧、常圧、加圧いずれでもよいが、通
常、常圧から１０ｋｇ／ｃ＋Ｊ−Ｇまでの範囲内で反応
が行われる。さらに、エポキシ化反応は無溶媒下でも進
行するが、所望により溶媒を使用して行ってもよい、こ
の溶媒としては、例えばベンゼンやトルエンなどの芳香
−族炭化水素、ヘキサンやヘプタンなどの脂肪族炭化水
素などが用いられる０反応時間については、原料不飽和
化合物、錯体、可視光などの種類や、温度、圧力などに
よって左右されるが、通常１〜２０時間程度である。Regarding the reaction pressure, as long as the pressure is sufficient to maintain the liquid phase of the reaction system, it may be reduced pressure, normal pressure, or increased pressure, but usually the reaction pressure is within the range of normal pressure to 10 kg/c + J-G. will be held. Furthermore, although the epoxidation reaction proceeds without a solvent, it may be carried out using a solvent if desired. Examples of such solvents include aromatic hydrocarbons such as benzene and toluene, and aliphatic hydrocarbons such as hexane and heptane. The zero reaction time when a hydrocarbon or the like is used depends on the type of raw material unsaturated compound, complex, visible light, etc., temperature, pressure, etc., but is usually about 1 to 20 hours.
本発明方法によると、例えばシクロヘキセンからシクロ
ヘキセンオキシドが、２−ヘキセンから２．３−エポキ
シヘキサンのみがそれぞれほぼ１００％の選択率で得ら
れる。According to the method of the present invention, for example, only cyclohexene oxide from cyclohexene and only 2,3-epoxyhexane from 2-hexene can be obtained with approximately 100% selectivity.
以下、本発明を実施例に基づいて詳細に説明するが、本
発明はこれに限定されるものではない。Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.
調製例 触媒調製
内容積２０００ｍ１の３つロフラスコに、５，１０．１
５．２０−テトラ−ｐ−１−リルポルフィリンＣＨｔ
ＴＴＰ） ７８０ｍｌ （１，２Ｘ １０弓ｍ。Preparation example Catalyst preparation In a three-bottle flask with an internal volume of 2000 m1,
5.20-tetra-p-1-lylporphyrin CHt
TTP) 780ml (1,2X 10 bows m.
ｌ）とデカリン３５０ｍ１を入れ、窒素を吹き込み溶存
酸素を置換した後、モリブデンヘキサカルボニル５．５
ｇ （２，Ｉ Ｘ １０−”ｎｏ ｌ）を加えた。窒
素気流下、油浴温度１９０℃で５時間加熱攪拌した後、
反応固形物を濾別する。この固形物を少量のクロロホル
ムに溶かし、クロロホルムで湿式充填したアルミナカラ
ム（φ３０ｍｘ １７ Ｑｍ）を用いてクロマトグラフ
法により分離精製した。最初クロロホルムで展開し、最
初の留出液を分取した。展開溶媒をクロロホルム／メタ
ノール＝８／２に変えて留出液を得た。このクロロホル
ム／メタノール留出液を減圧乾固し、塩化メチレン−エ
タノール混合溶媒より再結晶を行ない、オキソエトキソ
（５，１０，１５，２０−テトラ−ｐ−トリルポルフィ
ナト）モリブデン（Ｍ ｏ Ｏ（ＯＣ２Ｈｓ ） （
ＴＴ Ｐ ） ３４１５ｍｇを得た。1) and 350 ml of decalin, and after blowing in nitrogen to replace the dissolved oxygen, 5.5 ml of molybdenum hexacarbonyl
g (2, I X 10-"no l) was added. After heating and stirring at an oil bath temperature of 190°C for 5 hours under a nitrogen stream,
The reaction solids are filtered off. This solid was dissolved in a small amount of chloroform, and separated and purified by chromatography using an alumina column (φ30m x 17 Qm) wet-packed with chloroform. First, it was developed with chloroform, and the first distillate was collected. The developing solvent was changed to chloroform/methanol=8/2 to obtain a distillate. This chloroform/methanol distillate was dried under reduced pressure and recrystallized from a methylene chloride-ethanol mixed solvent to obtain oxoethoxo(5,10,15,20-tetra-p-tolylporphinato)molybdenum (M o O(OC2Hs ) (
3415 mg of TTP) was obtained.
実施例１
内容積２０ｍ１のガラス製容器に調製例で得た（ＭｏＯ
（ＯＣｚ Ｈｓ ）（ＴＴＰ））１．０ｍｇ （１゜２
１Ｘ１０−’ｍｏｌ）、シクロヘキセン２ｍ１（１゜９
７ＸＩＯ−”ｍｏｌ）、ベンゼン２ｍｌを入れた。Example 1 The sample obtained in the preparation example (MoO
(OCz Hs ) (TTP)) 1.0 mg (1゜2
1×10-'mol), cyclohexene 2ml (1°9
7XIO-'' mol) and 2 ml of benzene were added.
室温（２５℃）で反応器に５００Ｗタングステンランプ
にて光を当てながら１２時間攪拌した。反応終了後、生
成液をガスクロマトグラフィー法にて分析し、表−１に
示す結果を得た。なお、生成物はシクロヘキセンオキシ
ドのみであった（選択率１００％）。The reaction vessel was stirred at room temperature (25°C) for 12 hours while being illuminated with a 500W tungsten lamp. After the reaction was completed, the resulting solution was analyzed by gas chromatography, and the results shown in Table 1 were obtained. Note that the product was only cyclohexene oxide (selectivity 100%).
実施例２
実施例１において、シクロヘキセンの代わりに、２−ヘ
キセン２ｍｌ （１，５９Ｘ １０−”ｍｏ １）を用
いた他は、実施例１と同様の操作を行った。結果を表−
１に示す。なお、生成物は、２，３−エポキシヘキサン
のみであった（選択率１００％）。Example 2 The same operation as in Example 1 was carried out, except that 2 ml of 2-hexene (1,59X 10-"mo 1) was used instead of cyclohexene. The results are shown in the table below.
Shown in 1. Note that the product was only 2,3-epoxyhexane (selectivity 100%).
比較例１．２．３
実施例１において、触媒、光および酸素の条件のうち、
１つを除去した以外は、実施例１と同様な操作を行った
。結果を表−１に示す。Comparative Example 1.2.3 In Example 1, among the catalyst, light and oxygen conditions,
The same operation as in Example 1 was performed except that one was removed. The results are shown in Table-1.
以下余白
〔発明の効果〕
本発明方法は、炭素−炭素二重結合を有する不飽和炭化
水素を特殊な酸化剤を用いないで、分子状酸素で酸化し
、エポキシ基を有する化合物を選択率よく高収率で得る
ことができ、その工業的価値は極めて大である。Blank space below [Effects of the Invention] The method of the present invention oxidizes unsaturated hydrocarbons having carbon-carbon double bonds with molecular oxygen without using a special oxidizing agent, and oxidizes compounds having epoxy groups with high selectivity. It can be obtained in high yield and its industrial value is extremely large.
Claims (1)
してエポキシ基を有する化合物を製造するにあたり、反
応系に大環状イミンを配位子としたモリブデン−酸素錯
体を添加し、かつ、可視光照射下に、該不飽和炭化水素
を分子状酸素により酸化することを特徴とするエポキシ
化合物の製造法。1. When producing a compound having an epoxy group by oxidizing an unsaturated hydrocarbon having a carbon-carbon double bond, a molybdenum-oxygen complex having a macrocyclic imine as a ligand is added to the reaction system, and A method for producing an epoxy compound, which comprises oxidizing the unsaturated hydrocarbon with molecular oxygen under irradiation with visible light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61104749A JPS62263172A (en) | 1986-05-09 | 1986-05-09 | Production of epoxy compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61104749A JPS62263172A (en) | 1986-05-09 | 1986-05-09 | Production of epoxy compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62263172A true JPS62263172A (en) | 1987-11-16 |
Family
ID=14389141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61104749A Pending JPS62263172A (en) | 1986-05-09 | 1986-05-09 | Production of epoxy compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62263172A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03112710A (en) * | 1990-03-14 | 1991-05-14 | Toyota Motor Corp | Control device for vehicle roll |
| JP2005306803A (en) * | 2004-04-23 | 2005-11-04 | Hamamatsu Kagaku Gijutsu Kenkyu Shinkokai | Oxidation method for unsaturated compound |
| JP2007269790A (en) * | 2006-03-09 | 2007-10-18 | Kyushu Univ | Molybdenum porphycene complex and oxidative catalyst |
-
1986
- 1986-05-09 JP JP61104749A patent/JPS62263172A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03112710A (en) * | 1990-03-14 | 1991-05-14 | Toyota Motor Corp | Control device for vehicle roll |
| JP2005306803A (en) * | 2004-04-23 | 2005-11-04 | Hamamatsu Kagaku Gijutsu Kenkyu Shinkokai | Oxidation method for unsaturated compound |
| JP2007269790A (en) * | 2006-03-09 | 2007-10-18 | Kyushu Univ | Molybdenum porphycene complex and oxidative catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Simonian et al. | Adsorption effects on the efficiency of cobalt-mediated cyclizations of allylpropargyl ethers into derivatives of 3-oxabicyclo [3.3. 0] oct-5-en-7-one | |
| Higuchi et al. | Highly efficient epoxidation of olefins with pyridine N-oxides catalyzed by ruthenium porphyrins | |
| Taniguchi | Stereoselective synthesis of (E)-alkenyl sulfones from alkenes or alkynes via copper-catalyzed oxidation of sodium sulfinates | |
| Li et al. | Preparation and catalysis of DMY and MCM-41 encapsulated cationic Mn (III)–porphyrin complex | |
| Takeda et al. | Ru-salen catalyzed asymmetric epoxidation: photoactivation of catalytic activity | |
| EP1754693B1 (en) | Process for the production of esters or lactones | |
| Uchida et al. | New Asymmetric Catalysis by (Salen) cobalt (III) Complexes (Salen=[Bis (salicylidene) ethylenediaminato]={{2, 2′‐[ethane‐1, 2‐diyl] bis [(nitrilo‐κN) methylidyne] bis [phenolato‐κO]}(2−)}) of cis‐β‐Structure: Enantioselective Baeyer‐Villiger Oxidation of Prochiral Cyclobutanones | |
| JPS62263172A (en) | Production of epoxy compound | |
| US6762310B2 (en) | Process for the epoxidation of alkenes and polyoxofluorometalates for use therein | |
| Leung et al. | Synthesis and reactivity of dihydroxoruthenium (IV) complex of tetramesitylporphyrin. Aerobic epoxidation of norbornene by ruthenium porphyrins | |
| JP2001240561A (en) | Catalyst for preparing of oxygen-containing organic compound and preparation method of the same compound | |
| US5274139A (en) | Method for effective reaction between oxygen and organic substance utilizing regenerable hydroperioxide oxidant | |
| CN113173862B (en) | Method for synthesizing olefin by selective desaturation of inert carbon-carbon bond | |
| Neves et al. | Performance of chiral tetracarbonylmolybdenum pyrindanyl amine complexes in catalytic olefin epoxidation | |
| JPS62263171A (en) | Production of epoxy compound | |
| JPH08500286A (en) | Epoxidation catalyst | |
| EP1706205B1 (en) | A catalytical asymmetric epoxidation | |
| JPH0361670B2 (en) | ||
| Cristea et al. | Stereoselective trans-dihydroxylation of terpinen-4-ol: synthesis of some stereoisomers of p-menthane-1, 2, 4-triol | |
| Evtushok et al. | Hydrogen peroxide activation and liquid‐phase selective oxidations over Ti, Zr‐based metal–organic framework PCN‐415 | |
| Kato et al. | Marked effect of a catalytic amount of an amine on selective epoxidation of aliphatic and aromatic olefins witht-butyl hydroperoxide and a molybdenum oxide chelate | |
| JP4386675B2 (en) | Liquid phase oxidation reaction using tungsten species | |
| FR2489710A1 (en) | NOVEL OXO-TYPE VANADIUM COMPLEXES, PROCESS FOR THEIR MANUFACTURE, AND THEIR USE AS REAGENTS AND AS OXIDATION CATALYSTS OF UNSATURATED HYDROCARBON SUBSTRATES | |
| EP0159619A2 (en) | Process for the catalytic epoxidation of low molecular weight olefins, and catalyst for performing said process | |
| JP2005002027A (en) | Heteroelement substituted heteropolyoxometalate compound |