JP5972314B2 - 過酸化水素およびマンガン錯体を用いたエピクロロヒドリンの製造方法 - Google Patents
過酸化水素およびマンガン錯体を用いたエピクロロヒドリンの製造方法 Download PDFInfo
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- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 title claims description 61
- 239000011572 manganese Substances 0.000 title claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 23
- 229910052748 manganese Inorganic materials 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000012431 aqueous reaction media Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 239000012074 organic phase Substances 0.000 claims description 19
- 239000007800 oxidant agent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 5
- AWNOGHRWORTNEI-UHFFFAOYSA-N 2-(6,6-dimethyl-4-bicyclo[3.1.1]hept-3-enyl)ethyl acetate Chemical compound CC(=O)OCCC1=CCC2C(C)(C)C1C2 AWNOGHRWORTNEI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 235000018936 Vitellaria paradoxa Nutrition 0.000 claims 2
- 238000009826 distribution Methods 0.000 claims 1
- 150000002924 oxiranes Chemical class 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000006735 epoxidation reaction Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- 150000002696 manganese Chemical class 0.000 description 6
- 239000012429 reaction media Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001260 acyclic compounds Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 150000001923 cyclic compounds Chemical class 0.000 description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 3
- 229940039790 sodium oxalate Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000007306 turnover Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000000466 oxiranyl group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- -1 (substituted) triazacyclononane Chemical class 0.000 description 1
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- BHKKSKOHRFHHIN-MRVPVSSYSA-N 1-[[2-[(1R)-1-aminoethyl]-4-chlorophenyl]methyl]-2-sulfanylidene-5H-pyrrolo[3,2-d]pyrimidin-4-one Chemical compound N[C@H](C)C1=C(CN2C(NC(C3=C2C=CN3)=O)=S)C=CC(=C1)Cl BHKKSKOHRFHHIN-MRVPVSSYSA-N 0.000 description 1
- FOLYKNXDLNPWGC-UHFFFAOYSA-N 1-chloro-3-methoxypropan-2-ol Chemical compound COCC(O)CCl FOLYKNXDLNPWGC-UHFFFAOYSA-N 0.000 description 1
- PSYQXTDKRKLJQC-UHFFFAOYSA-N 1-chloropropane-1,3-diol Chemical compound OCCC(O)Cl PSYQXTDKRKLJQC-UHFFFAOYSA-N 0.000 description 1
- FIDXMAOFOOZFJE-UHFFFAOYSA-N 3-chloro-2-methoxypropan-1-ol Chemical compound COC(CO)CCl FIDXMAOFOOZFJE-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 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
- 238000004945 emulsification Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229940039748 oxalate Drugs 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
-
- 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
- C07D301/12—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D255/00—Heterocyclic compounds containing rings having three nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D249/00 - C07D253/00
- C07D255/02—Heterocyclic compounds containing rings having three nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D249/00 - C07D253/00 not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
したがって、本発明は、
−酸化剤を用いて塩化アリル(「AC」)を接触酸化し、水性反応媒体中で前記接触酸化を実施し、酸化触媒として水溶性マンガン錯体を用い、
−次いでエピクロロヒドリン(「ECH」)を分離することによる、
エピクロロヒドリンの製造方法を提供する。
[LMnX3]Y (I)
および一般式(II)の二核の種:
[LMn(μ−X)3MnL]Y2 (II)
を含む。
好ましい対イオンは、PF6 −である。
AC 約9100kg/h
H2O2(35%) 約6457kg/h
H2O 約2140kg/h
この物質収支の結果によると、ECH/cat比は約8000mol/molである。
一般的なエポキシ化の反応において、水50mL中の触媒9.3μmol、H2O7.5mL中のシュウ酸ナトリウム112.5μmolおよびH2O7.5mL中のシュウ酸112.5μmolを、機械式撹拌器を備えた三つ口丸底フラスコに取り入れた。オレフィン(150mmol)および希H2O2(200mmol)を添加して、4℃で反応を開始した。
マンガン錯体は、溶媒として水を用いて効率的にECHを生成した。溶媒として水を用いたエポキシ化の間、反応初期に、ACは水性触媒溶液の上部に分離層として存在した。エポキシ化が進むにつれ、いくらかのACが分離相に溶解するのに伴い、ECHが分離相に形成された。反応は数回実施した。時折、反応系は上相から下相まで3相:有機相、水相およびもう1つの有機相を形成した。反応の終了時に、上相および下相の両方の有機相は多量のECHおよびACを含んでいた。微量のACおよびECHは、水相にも認められた。一方、反応系は、(ACおよびECHを含む。)有機相ならびに水相を含む2層系ももたらした。
ECHの生成率は触媒の濃度と比例していた。この実施例は、触媒の量の増大によりECHの生成が増大することを示している。
前の実験では、エポキシ化の反応を約3.5から3.6の低いpHで実施した。以下に、本発明者らは、触媒は、シュウ酸のみが存在するpH=2.6の酸性条件、およびシュウ酸ナトリウムのみが存在するpH=8の塩基性条件の両条件において活性であったことを示す。これらの結果は、触媒系はACのエポキシ化において幅広いpH範囲で活性であったことを立証する。
Claims (15)
- エピクロロヒドリンの製造方法であって、
塩化アリルを過酸化水素と、水性反応媒体中で触媒の存在下に反応させること、ここで、前記触媒は水溶性マンガン錯体を含み、且つ塩化アリルと過酸化水素とのモル比は1:0.1から1:1であり、
前記水性反応媒体を攪拌すること、および
エピクロロヒドリン生成物を分離すること、ここで、前記水溶性マンガン錯体が、一般式(I)の一核のマンガン錯体:
[LMnX3]Y (I)
または一般式(II)の二核のマンガン錯体:
[LMn(μ−X)3MnL]Y2 (II)
から選択される、
[式中、Mnはマンガン原子であり;Lまたは各Lは独立にトリアザシクロノナン又は置換トリアザシクロノナン多座配位子であり;各Xは独立に配位種であり、RO−、Cl−、Br−、I−、F−、NCS−、N3 −、I3 −、NH3、NR3、RCOO−、RSO3 −、RSO4 −、OH−、O2−、O2 2−、HOO−、H2O、SH−、CN−、OCN−およびS4 2−ならびにそれらの組合せからなる群から選択され(式中、Rは、C1−C20アルキル、C1−C20シクロアルキル、C1−C20アリール、ベンジルおよびそれらの組合せからなる群から選択される。)、各μ−Xは独立に架橋配位種であり、RO−、Cl−、Br−、I−、F−、NCS−、N3 −、I3 −、NH3、NR3、RCOO−、RSO3 −、RSO4 −、OH−、O2−、O2 2−、HOO−、H2O、SH−、CN−、OCN−およびS4 2−ならびにそれらの組合せからなる群から選択され(式中、Rは、C1−C20アルキル、C1−C20シクロアルキル、C1−C20アリール、ベンジルおよびそれらの組合せからなる群から選択される。);Yは陰対イオンであり、RO−、Cl−、Br−、I−、F−、SO4 2−、RCOO−、PF6 −、アセテート、トシレート、トリフレート(CF3SO3 −)およびそれらの組み合わせからなる群から選択される(式中、Rは、C1−C20アルキル、C1−C20シクロアルキル、C1−C20アリール、ベンジルおよびそれらの組合せからなる群から選択される。)]、
を含み、
前記水性反応媒体が、pHを安定化するための緩衝系をさらに含有し、前記水性反応媒体が、3から6.5の範囲内のpHで構成される、製造方法。 - エピクロロヒドリン生成物またはエピクロロヒドリン生成物の一部が有機相として分離され、前記有機相がエピクロロヒドリン生成物、または塩化アリルおよびエピクロロヒドリンの混合物を含む、請求項1に記載の方法。
- 前記マンガン触媒が、以下の式の二核のマンガン錯体:
[MnIV 2(μ−X)3L2]Y2
を含む、請求項1に記載の方法
[式中、Mnはマンガン原子であり;Lはトリアザシクロノナン又は置換トリアザシクロノナン多座配位子であり;各μ−Xは独立に架橋配位種であり、RO−、Cl−、Br−、I−、F−、NCS−、N3 −、I3 −、NH3、NR3、RCOO−、RSO3 −、RSO4 −、OH−、O2−、O2 2−、HOO−、H2O、SH−、CN−、OCN−およびS4 2−ならびにそれらの組合せ(式中、Rは、アルキル、シクロアルキル、アリール、ベンジルおよびそれらの組合せからなる群から選択されるC1−C20の基である。)からなる群から選択され;YはSO4 2−、PF6 −、アセテートまたはそれらの組み合わせからなる群から選択される。]。 - 前記水性反応媒体の攪拌には、100rpmと650rpmとの間で攪拌器により系を攪拌することが含まれる、請求項1に記載の方法。
- 前記水性反応媒体が、緩衝剤対触媒比10:1から100:1にある緩衝系を更に含む、請求項1に記載の方法。
- 前記緩衝系が、酸−塩の組み合わせを含む、請求項5に記載の方法。
- 前記酸−塩の組み合わせが、シュウ酸−シュウ酸塩または酢酸−酢酸塩を含む、請求項6に記載の方法。
- 前記触媒が、0.001mmol/Lから10mmol/Lの濃度で存在する、請求項1に記載の方法。
- 前記触媒が、前記触媒(Mn)対前記塩化アリルのモル比が1:10から1:10,000,000で用いられる、請求項1に記載の方法。
- 前記水性反応媒体が、3.0から4.2の範囲内のpHで構成される、請求項1に記載の方法。
- 前記塩化アリル対前記過酸化水素のモル比が1:0.2から1:0.8の範囲内で、前記塩化アリルを前記酸化剤と反応させる、請求項1に記載の方法。
- 前記反応がバッチ法、連続法または半連続法で実施される、請求項1に記載の方法。
- 前記水性反応媒体が、いずれもの溶解したエポキシドおよび塩化アリルを除き、100%水性媒体を含む、請求項1に記載の方法。
- 前記マンガン錯体が、式[MnIV 2(μ−O)3L2]Y2(式中、Lはトリアザシクロノナン又は置換トリアザシクロノナンであり、対イオンYはPF6 −又はCH3CO2 −である。)を含む、請求項1に記載の方法。
- 前記錯体が、一般式(II):
[LMn(μ−X)3MnL]Y2 (II)
を含み、
[式中、Mnはマンガンであり;Lまたは各Lは独立にトリアザシクロノナン又は置換トリアザシクロノナン多座配位子であり;各μ−Xは独立に次の架橋配位種:O2−、RCOO−、RSO3 −、RSO4 −であり(式中、Rは、C1−C20アルキル、C1−C20シクロアルキル、C1−C20アリール、ベンジルおよびそれらの組合せからなる群から選択される。);YはSO4 2−、PF6 −、アセテートおよびそれらの組み合わせからなる群から選択される陰イオンである。]
前記水性反応媒体が、3.0から4.2のpH範囲を有する緩衝系をさらに含み、および
前記塩化アリルと過酸化水素とのモル比が1:0.2から1:0.8の範囲である、請求項1に記載の方法。
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US8802873B2 (en) | 2014-08-12 |
RU2011107718A (ru) | 2012-09-10 |
AU2009275559A1 (en) | 2010-02-04 |
AU2009275559B2 (en) | 2012-11-29 |
BRPI0915572A2 (pt) | 2017-06-27 |
EP2334660A1 (en) | 2011-06-22 |
JP5709171B2 (ja) | 2015-04-30 |
US20110137055A1 (en) | 2011-06-09 |
KR20140117701A (ko) | 2014-10-07 |
JP2011529861A (ja) | 2011-12-15 |
MY159525A (en) | 2017-01-13 |
RU2482115C2 (ru) | 2013-05-20 |
KR101475558B1 (ko) | 2014-12-22 |
JP2014237652A (ja) | 2014-12-18 |
KR101501890B1 (ko) | 2015-03-12 |
WO2010012360A1 (en) | 2010-02-04 |
CN104045609A (zh) | 2014-09-17 |
KR20110040959A (ko) | 2011-04-20 |
CN102112457A (zh) | 2011-06-29 |
EP2149570A1 (en) | 2010-02-03 |
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