WO2002066158A1 - Tetraoxyde d'osmium supporte par un polymere comportant un groupe d'echange ionique - Google Patents

Tetraoxyde d'osmium supporte par un polymere comportant un groupe d'echange ionique Download PDF

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WO2002066158A1
WO2002066158A1 PCT/JP2002/001416 JP0201416W WO02066158A1 WO 2002066158 A1 WO2002066158 A1 WO 2002066158A1 JP 0201416 W JP0201416 W JP 0201416W WO 02066158 A1 WO02066158 A1 WO 02066158A1
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group
osmium tetroxide
atom
represented
bond
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PCT/JP2002/001416
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English (en)
Japanese (ja)
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Mutsumi Sato
Kuniaki Okamoto
Keiji Oono
Atsunori Sano
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Wako Pure Chemical Industries, Ltd.
Kobayashi, Shu
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Priority to JP2002565709A priority Critical patent/JP4133334B2/ja
Publication of WO2002066158A1 publication Critical patent/WO2002066158A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
    • 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
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • 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
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • 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
    • 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
    • B01J31/30—Halides

Definitions

  • the present invention relates to a polymer-supported osmium tetroxide having an ion exchange group, the catalytic activity of which does not decrease even when used repeatedly.
  • Osmium tetroxide is an excellent catalyst for the diolification (dihydroxylation) reaction of olefins, but is highly toxic, sublimable, and expensive, and is hardly used industrially.
  • polyvinyl pyridine derivatives poly (N-vinyl carbazole) or 'are linked to Si (OR) 3 -units via n-propylene residues, primary, secondary and Z or tertiary
  • a catalyst obtained by supporting osmium tetroxide on a derivative of a polymer having a secondary amino group or the like has also been reported (Japanese Patent Application Laid-Open No. 4-505884), but the catalyst supported on the two derivatives is as described above. It is not practical for the same reasons as the supporting method and the reason, and in the case of a catalyst using a polymer having a Si (OR) 3 -unit as a support, the amount of osmium tetroxide supported is small. On the other hand, when used, osmium tetroxide itself easily leaks into the reaction system in large quantities from the carrier, so the recovery rate is low and it cannot be used repeatedly. Therefore, the catalyst has not been put to practical use.
  • a catalyst that is easy to handle and that can be used repeatedly to some extent has been conceived by microencapsulating osmium tetroxide using a commercially available olefin polymer compound such as polystyrene.
  • microencapsulated osmium tetroxide requires a complicated mic mouth encapsulation operation, and has a problem that it is difficult to increase the holding efficiency of osmium tetroxide on the polymer.
  • the present invention has been made in view of the circumstances as described above, and can be manufactured more industrially, is easy to handle, has excellent solvent resistance, and its catalytic activity is not reduced by repeated use.
  • An object is to provide an osmium oxide supporting compound.
  • the present inventors have conducted intensive studies to achieve the above object. As a result, they have contained a primary amino group or a group represented by one NHR (R represents an alkyl group, an aryl group or an aralkyl group).
  • NHR represents an alkyl group, an aryl group or an aralkyl group.
  • Osmium tetroxide which is supported on a polymer such as a polyolefin to which a group is bonded by an easy operation in an organic solvent, is easy to handle and has excellent solvent resistance. It was found that the amount of osmium tetroxide supported was larger than that of osmium, and that its catalytic activity was not easily reduced even by repeated use.
  • NRR ⁇ one NRR'R "+ (where R, R 'and R" are each independently an alkyl group, aryl group or Represents an aralkyl group) or a group containing a sulfonic acid group.
  • Oxmium tetraoxide is bound to a polymer such as a bound polyolefin in various solvents.
  • a polymer such as a bound polyolefin in various solvents.
  • the primary amino group or a group containing a group represented by 1N HR is bound, polyolefin, etc.
  • the present inventors have found that a catalyst having the same catalytic activity as osmium tetroxide supported on a polymer can be obtained, and have completed the present invention.
  • the present invention relates to a primary amino group, one NHR, one NRR ', one NR R'R "+ (where R, R' and R" are each independently an alkyl group) which are ion exchange groups. , An aryl group or an aralkyl group.) Or a polyolefin-supported osmium tetroxide, a primary amino group, —NHR, _NRR ′, —NR R′R to which a group containing a sulfonic acid group is bonded.
  • the present invention provides a method for producing osmium tetroxide supported on a carrier, comprising contacting the carrier with osmium tetroxide, and supporting osmium tetroxide on the carrier. It is an invention of a method for preserving osmium tetroxide.
  • the present invention is an invention of a method for producing a diol compound, wherein an oxidation catalyst composed of osmium tetroxide supported on the above-mentioned carrier is allowed to act on olefins.
  • polyolefin having a group containing an ion exchange group which constitutes the support for supporting osmium tetroxide of the present invention
  • examples of the polyolefin having a group containing an ion exchange group, which constitutes the support for supporting osmium tetroxide of the present invention include those containing an aromatic olefinic repeating unit and / or an aliphatic olefinic repeating unit. These include, for example, an ether bond, an ester bond or an amide in the molecule.
  • the crosslinked polyolefin may be crosslinked with a hydrocarbon group which may contain a bond or a bond.
  • the crosslinked polyolefin is more preferable as an osmium tetroxide carrier than an uncrosslinked type. '
  • Examples of the ion-exchange group include a primary amino group, —NH R, one NR R ′, one NR R′R ′′ + (where R, R ′ and R ′′ each independently represent an alkyl group, an aryl group or an aralkyl group). And a sulfonic acid group.
  • Primary amino groups are those designated by 1 NH 2 .
  • the groups represented by —NH R, —NR R ′ and —NR R′R ′′ + are respectively a secondary amino group according to the present invention, and a tertiary tertiary group according to the present invention. It may be abbreviated as an amino group and a quaternary ammonium group according to the present invention.
  • the sulfonic acid group is represented by 1 SO 3 H, which may form a salt with an alkali metal such as lithium, sodium, and potassium.
  • the alkyl group represented by R, R 'and R may be any of linear, branched and cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec- Pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, cyclopropyl group, cyclopentyl group, These alkyl groups usually have 1 to 3 substituents such as a hydroxyl group, a carboxyl group or an alkali metal salt thereof (eg,
  • the aryl groups represented by R, R 'and R "usually have 6 to 14 carbon atoms, Preferred are those having 6 to 10 carbon atoms, more preferably 6 carbon atoms, and specific examples include phenyl, tolyl, xylyl, mesityl, naphthyl, anthryl, and phenanthryl groups.
  • R, R 'and R usually have 6 to 14 carbon atoms, Preferred are those having 6 to 10 carbon atoms, more preferably 6 carbon atoms, and specific examples include phenyl, tolyl, xylyl, mesityl, naphthyl, anthryl, and phenanthryl groups.
  • the aralkyl groups represented by R, R 'and R generally include those having 1 to 10 carbon atoms, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl and the like.
  • Examples of the group containing an ion exchange group include a primary amino group, one N'HR, -NR R ', -NRR'" + (R, R 'and R" are the same as above) or A hydrocarbon group which usually has 1 to 5, preferably 1 to 3, and more preferably 1 sulfonic acid group and which may contain a hetero atom in the molecule is exemplified.
  • the hydrocarbon group of the hydrocarbon group which may contain a hetero atom in the molecule is usually divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent, and usually has 1 to 1 carbon atoms. These hydrocarbon groups have a low molecular weight to a high molecular weight.
  • the hydrocarbon group usually has 1 to 10, preferably 1 to 3 hydrophilic groups as substituents. May be. ,
  • Examples of the low-molecular-weight hydrocarbon group include those having usually 1 to 100 carbon atoms. Specific examples include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, and a 1-methyl group.
  • Trimethylene group 2-methyltrimethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,3-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 2-e Tiltrimethylene, hexamethylene, 1,4-dimethyltetramethylene, 2,3-dimethyltetramethylene, 1,2,3-trimethyltrimethylene, 1,2-getylethylene, heptamethylene , 1,5-one group, 1,6-dimethylhexamethylene group, nonamethylene group, decamethylene group, cyclopropylene group, dipentylene group, cyclohexylene group, Cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cyclopropane-12-dimethylene group, cyclopentane-1,3-dimethylene group, cyclohexane-1,4-dimethylene group, cyclohexene
  • an arylene group having 614 carbon atoms preferably 6 carbon atoms, such as a phenylene group, a naphthylene group, an anthracenediyl group, and a phenanthracenediyl group, or a combination of the above alkylene group and an arylene group.
  • C 6 H 4 -CH 2 --C 6 H 4 -C 2 H 4 --C 6 H 4 -C 3 H 6 --Q HA -C 4 lg -C 6 ⁇ 4 J3 (then HL ) C 6 H C_H CH xl 3 no, i 2 - ⁇ 6 H 4 -CH 2 - 2 H 4 - ⁇ 6 H -CH - ⁇ - ⁇ e H 4 -G 2 -C 6 - ⁇ G 6 H 4 - C 2 HC 6 H 4 - 2 divalent hydrocarbon group, for example one is substituted in the bond group include methanetriyl group hydrogen atom of said alkylene group such as, 1,1, 2-eth Ntoriiru group, 1,2 , 3-propanetriyl group, 1,2,4-butanetriyl group, 2-methyl-1,2,3-propanetriyl group, 1,3,5-pententriyl group,
  • Alkantriyl groups such as
  • Arylalkanetriyl groups such as c3 ⁇ 4, c3 ⁇ 4
  • Alkylarenetriyl groups such as
  • Trivalent hydrocarbon groups such as groups in which three hydrogen atoms of arylalkane are substituted by a bond, etc.
  • Tetravalent hydrocarbon groups such as
  • Pentavalent hydrocarbon groups such as
  • the high molecular weight hydrocarbon group may be linear, branched, or cyclic, and usually have a molecular weight of 100 to 200, and specifically,
  • the above-mentioned low molecular weight hydrocarbon groups are suitable: i: those obtained by combining them, and the like.
  • alkyl group, aryl group and aralkyl group represented by R ′′ ′ examples include R, R ′ and R ′ of the secondary amino group, tertiary amino group and quaternary ammonium group according to the present invention.
  • the number of hetero atoms in the case where a hetero atom is contained in the molecule of the hydrocarbon group is usually 1 to 5, preferably 1 to 3 in the low molecular weight hydrogenated group, and in the high molecular weight hydrocarbon group. Is usually 1 to 500, preferably 1 to 300, more preferably 1 to 20.
  • hydrocarbon group containing a hetero atom in the molecule include those represented by the following general formulas [3], [4], [5] or [6].
  • R 7 , R 9 , R 11 , R 12 and R 14 each independently represent an alkylene group, an arylene group or an aralkylene group, and R s and R 13 each independently represent Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group;
  • R 1 Q , R 15 and R 16 each independently represent a bond, an alkylene group, an arylene group or an aralkylene group;
  • E represents an oxygen atom or a sulfur atom,
  • m and t each independently represent a natural number, and
  • n and k each independently represent 0 or a natural number. ⁇ ⁇ Except when n and k are both 0. )
  • the alkylene group represented by R 7 R 9 R 10 R 11 R 12 R 14 R 15 and R 16 May be linear, branched or cyclic, and usually include those having 110, preferably 16, carbon atoms.
  • methylene group ethylene group, methylmethylene group, trimethylene Group, propylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, Hexamethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1-ethyltetramethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, cyclopropylene
  • the Examples include a lopentylene group, a hexylene group, a hexylene group, a cyclooctylene group, a cyclononylene group, and a cyclodecylene group.
  • R '. R ⁇ The R ⁇ ⁇ R 1 1 ⁇ 1 2 ⁇ 1 4 ⁇ 1 5 and Ariren group represented by R 1 6, typically include those having a carbon number of 6 1 4, specifically, For example, a phenylene group, a naphthylene group, an anthracenyl 'group, a phenanthylene diyl group and the like can be mentioned.
  • the 1 4 ⁇ 1 5 and Ararukiren group represented by R 1 6, as also the one generally having 7 1 0 may be branched linear and the like, specifically, for example, - C 6 H 4 -CH 2 - - C 6 H 4 2 H 4 - 6 H 4 - C 3 1 6 - H 4 -C 4 H 8 - -C 6 H 4 - HH 3) _ - C 6 H 4 -CH 2 CH (CH 3) - , and the like.
  • ' - C 6 H 4 -CH 2 - - C 6 H 4 2 H 4 - 6 H 4 - C 3 1 6 - H 4 -C 4 H 8 - -C 6 H 4 - HH 3) _ - C 6 H 4 -CH 2 CH (CH 3) - , and the like.
  • the alkyl group represented by R 8 and R 13 may be linear or branched. Alternatively, they may be cyclic, and usually include those having 1 to 10 carbon atoms, preferably 1 to 6, more preferably 1 to 4, and specifically, for example, methyl group, ethyl group, n-propyl Group, isopropyl group, n-butyl group, isobutyl group sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, Isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, n-octyl group, sec-octyl group, tert- Oct
  • the 1 3 Ariru group represented include ordinary ones with carbon number 6-1 4, specifically, for example phenyl group, naphthyl group, anthryl group, etc. Fuenantoriru group.
  • the Ararukiru group represented by R 8 and R 1 3, usually include those of carbon number 7-1 0, 'specifically, for example, base Njiru group, Fueniruechiru group, phenylpropyl group, phenylbutyl group, etc. Is mentioned. .
  • E represents an oxygen atom or a sulfur atom, preferably an oxygen atom.
  • the natural number represented by m is usually 1 to 500, preferably 1 to 300, and more preferably 1 to 20.
  • n, k and t are usually 1 to 100, preferably 1 to 50, and more preferably 1 to 20.
  • 'Specific examples of the group represented by the general formula [3] include, for example, -CH 2 -0-CH 2 -,-(CH 2 -0) 2 -CH 2 -,-(CH 2 -0) 3- CH 2 -,-(CH 2 -0) 4 -CH 2 -,-(CH 2 -0) 5 -CH 2 -,-(CH 2 -0) 6 -CH 2 -,-(CH 2 -0) 7 -CH 2 -,-(CH 2 -0) 8 -CH 2 -,-(CH 2 -0) 9 -CH 2 -,-(CH 2 -0)!
  • R 7 in the general formula [3] is an ethylene group are preferred.
  • Specific examples of the group represented by the general formula [4] include, for example, -NH-CH-,- (NH-CH 2 ) 2 -,-(NH-CH 2 ) 3 -,-(NH-CH 2 ) 4 -,-(NH-CH 2 ) 5 -,-(NH-CH 2 ) 6-,- (NH-CH 2 ) 7 -,-(NH-CH 2 ) 8 -,-(Marauder-CH 2 ) 9 -,-(NH-CH ⁇ .-, -N (CH 3 ) -CH 2 CH 2- ,-[N (CH 3 ) -CH 2 CH 2 ] 2 -,-[N (CH 3 ) -CH 2 CH 2 ] 3 -,-[N (CH 3 ) -CH 2 CH 2 ] 4 -,- [N (CH 3 ) -CH 2 CH 2 ] 5 -,-[N (CH 3 ) -CH 2 CH 2 ] 6-,-[N (CH 3 )
  • R 9 , R 1 Q and R 11 in the general formula [4] are an ethylene group are preferred.
  • R 13 in the general formula [5] is a hydrogen atom and R 14 is an ethylene group are preferred.
  • R 15 in the general formula [6] is a bond or a phenyl group.
  • divalent hydrocarbon groups which crosslink polyolefin, which may contain an ether bond, an ester bond or an amide bond in the molecule include, for example, an alkylene group and an arylene group. And a divalent hydrocarbon group obtained by combining an alkylene group and an arylene group.
  • the alkylene group may be linear, branched or cyclic, and generally has 1 to 10 carbon atoms, preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4.
  • Specific examples include, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a pentamethylene group, a 1-methyltetramethylene group, 2-methyltetramethylene group, 1,3-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 2-ethyltrimethylene group, hexamethylene group, 1,4-dimethyltetramethylene group, 2,3-dimethyl Tetramethylene group, 1,2,3-trimethyltrimethylene group, 1,2-diethylethylene group, heptamethylene group, 1,5-dimethylpentamethylene group, 3-ethylpentmethylene group Group, Okutam
  • the arylene group usually has 6 to 14 carbon atoms, preferably 6 carbon atoms, and specifically includes, for example, a phenylene group, a tolyl group, a xylyl group, a mesityl group, a naphthylene group, Anthracenyl group, phenanthracenzyl group and the like.
  • the number of carbon atoms is usually 7500, preferably 720, more preferably? Include those having 1 to 4, specifically, for example, - C 6 H 4 -CH 2 - - 6H 4 - 2 H 4 - 6 ⁇ 4 - 3 ⁇ 6 - 6 H 4 _ 4 U 8 _ 6 ⁇ 4 - H ⁇ 3) _ - 1 ⁇ 2 ⁇ ( " and H 3 l 2 - fj - and ri 2 - -C 2 ⁇ 4 - 6 H 4 - teeth 2 H 4 - - C 6 H 4 -CH 2 - C 6 H 4 - -C 6 H 4 -C 2 H 4 -C 6 H 4 - and the like, as particularly preferable examples - C 2 H 4 -C 6 H 4 -C 2 H 4 - mentioned Can be
  • the number of ether bonds, ester bonds or amide bonds that may be contained in the molecule is usually 18, preferably 14, and more preferably 2, the divalent hydrocarbon group. .
  • Preferred examples of the divalent hydrocarbon group which may have an ester bond, an amide bond or an ether bond in the molecule as described above include an alkylene group having 18 carbon atoms, a phenylene group and the following general formulas. Examples include groups represented by the formulas [7], [8] and [9].
  • R 17 to R 20 each independently represent an alkylene group, an arylene group or a divalent hydrocarbon group obtained by combining an alkylene group and an arylene group; G is a bond, alkylene Group, an arylene group or a divalent hydrocarbon group in which an alkylene group and an arylene group are appropriately combined, and T represents an ester bond, an amide bond or an ether bond.
  • the alkylene group represented by R 17 to R 20 may be linear, branched or cyclic, and usually has 1 to 10 carbon atoms. And preferably 1 to 6, more preferably 2 to 4, and specific examples include R 7 in the above general formulas [3], [4], [5] and [6].
  • R 9 to 11 , R 12 and R 14 to 16 The same as the alkylene group represented by R 9 to 11 , R 12 and R 14 to 16 can be mentioned.
  • Examples of the arylene group represented by R 17 to R 2 ° include those having 6 to 14 carbon atoms. Specific examples thereof include the general formulas [3], [4], [5], and [5]. And the arylene groups represented by R 7 , R 9 to R 11 , R 12 and R 14 to R 6 in the above [6].
  • Examples of the divalent hydrocarbon group obtained by combining the alkylene group represented by R 17 to R 20 with an arylene group ′ include those having 7 to 20 carbon atoms, preferably 7 to 14 carbon atoms. As a specific example, R 17 to R 2 described above. And a divalent hydrocarbon group in which the specific examples of the alkylene group represented by and the specific examples of the arylene group are appropriately combined.
  • the alkylene group represented by G may be linear, branched or cyclic, and usually has 1 to 10 carbon atoms, preferably:! To 6 carbon atoms.
  • Examples of the arylene group represented by G include those having carbon atoms and a number of 6 to 14, and specific examples thereof include the general formulas [3], [43, [5], and '[6 7 'in! ⁇ 9 ⁇ ! ⁇ 1 1 ! ⁇ 1 2 and ⁇ Li represented by R 1 4 to Ri 6 - include the same alkylene groups.
  • the divalent hydrocarbon group formed by combining the alkylene group represented by G and the arylene group usually has 7 to 20 carbon atoms, preferably?
  • a specific example is a divalent hydrocarbon group obtained by appropriately combining the specific examples of the alkylene group represented by G and the specific examples of the arylene group.
  • groups represented by the general formulas [7], [8] and [9] groups represented by the following general formulas [10], [11] and [12] are mentioned as preferred examples.
  • T- J (wherein, R 2 1 ⁇ R 2 4 are independently an alkylene group having 2 to 4 carbon atoms, T is an ester bond, amino de bond or an ether bond, J is binding Represents a joint or an alkylene group having 1 to 4 carbon atoms.)
  • groups represented by the general formula [1 0] for example, -COO-CH 2 CH 2 -OCO-, -COO- (CH 2) 4 -OCO-, -CbO- (CH 2) 6 -OCO-,-COOCH (CH 3 ) -CH 2 CH 2 -OCO-, -C00-CH 2 CH 2 -O-CH 2 CH 2 -0- CH 2 CH 2 -0C0-, -C0NH-CH 2- NHCO- and the like.
  • a group containing a primary amino group, one NHR, one NRR ', one NRR'R "+, (where R, R' and R" are the same as described above) or a sulfonic acid group is formed.
  • the polyolefin that is combined for example, the following general formula [1]
  • ⁇ 6 each independently represent a hydrogen atom or an alkyl group, and M and M 'each independently represent a primary amino group, one NHR, one NRR', -NRR '" + ⁇
  • R, R 'and R represent the same as above, or a sulfonic acid group.
  • X may have a hydrophilic group as a substituent, and may be an oxygen atom which is a hetero atom in the molecule; Represents a divalent to hexavalent hydrocarbon group having 1 to 2000 carbon atoms which may contain a sulfur atom and / or a nitrogen atom, q generally represents an integer of 1 to 5, and A represents a bond or a molecule.
  • An alkylene group which may have an ester bond, an amide bond or an ether bond, an arylene group or Represents a divalent hydrocarbon group formed by combining an alkylene group and an arylene group, and represents [A], [B], [C] and [D] in the general formula [1], or a general formula
  • the structural units represented by [2], [' ⁇ ], [C], [D], and [E] in [2] mean that they are connected in any number and in any order. However, it must include [A] and Z or [C].
  • 'Q is usually an integer of 1 to 5, preferably 1 to 3, and more preferably 1.
  • X having 1 to 2 carbon atoms which may have a hydrophilic group represented by X as a substituent and may contain a hetero atom such as an oxygen atom, a sulfur atom and / or a nitrogen atom.
  • examples of the substituent exhibiting hydrophilicity which the hydrocarbon group may have include, for example, a hydroxyl group, a carboxyl group and an amino group. They may be usually substituted with 1 to 10, preferably 1 to 3 hydrocarbon groups.
  • the number of carbon atoms of the hydrocarbon group represented by X as described above includes a low molecular weight to a high molecular weight of usually 1 to 2000, and among them, a low molecular weight one preferably has 1 to 10 carbon atoms. More preferably, those having a molecular weight of from 1 to 3 are preferable, and those having a high molecular weight are preferably from 100 to 2000.
  • the number of hetero atoms in the case where a hetero atom is contained in the hydrocarbon molecule is usually 15 in the case of a low molecular weight compound, and preferably 13 in the case of a high molecular weight compound. And preferably 130 '.
  • hydrocarbon group represented by X include the same as those of the hydrocarbon group which may contain a hetero atom in the molecule exemplified above. ⁇
  • the divalent hydrocarbon group formed by combining the above is a divalent hydrocarbon group which may have an ether bond, an ester bond or an amide bond in the molecule cross-linking the polyolefin, as described above. And the same.
  • Preferred examples of the polyolefin according to the present invention represented by the general formula [1] or [2] include, for example, R 1 and R 3 are hydrogen atoms, and R 2 and R 4 are each independently a hydrogen atom or An alkyl group having 14 carbon atoms, wherein X is — (CH 2 2 ) m-CH 2 — (where m is 1 to L; a natural number of L00), a phenylene group or
  • R 7 , R 9 , R 11 , R 12 and R 14 each independently represent an alkylene group, an arylene group or an aralkylene group.
  • R 8 and R 13 represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group
  • R 1 , R 15 and R 16 represent a bond, an alkylene group, an arylene group or an aralkylene group
  • E represents an oxygen atom or a sulfur atom
  • m and t represent natural numbers
  • n and k each independently represent 0 or a natural number, except that both n and k are 0.)
  • q 1, and M and M 'are dialkylamino
  • R 1 and R 3 are a hydrogen atom
  • R 2 and R 4 are each independently a hydrogen atom or
  • X is a phenylene group
  • d l
  • 'Particularly preferred examples of the polyolefin according to the present invention represented by the general formula [2] include, for example, R 1 , R 3 and R 5 are hydrogen atoms, and R 2 , R 4 and R 6 are each Is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X is — (CH 2 —0) m-CH 2 1 (where m is a natural number from :! to 100); Diene group or
  • R 2 1 ⁇ R 2 4 represents an alkylene group having 2 to 4 carbon atoms
  • T is E ester bond
  • J is a bond or alkylene of 1 to 4 carbon atoms Which represents a group).
  • the ratio of the number of repeating units represented by [A] and [C] to the total number of repeating units is usually from 0.099 to 100 mol%, preferably from 0. 0 3 2 3 to 100 mol% (that is, the number of structural units represented by [B] and [D] with respect to the number of structural units represented by [A] and [C]] Is usually 0 to 100-fold mole, preferably 0 to 30-fold mole. ).
  • the ratio of the number of repeating units represented by [A] and [C] to the total number of repeating units is usually 1 to 99.9 mol%, preferably 3 to 30 mol%. .
  • the ratio of the repeating unit represented by [E] to the total number of repeating units is usually 0.1 to 40 mol%, preferably 0.1 to 20 mol, more preferably 0.3 to 10 mol. %, More preferably 0.1 to 5 mol%, particularly preferably 0.3 to 3 mol%.
  • the carrier for supporting osmium tetroxide according to the present invention includes a primary amino group, —NHR, —NRR ′, —NRR′R ′′ + (where R, R ′ and R ′′ are the same as described above) or a sulfonic acid group.
  • a polyolefin to which the containing group is bonded for example, a polymerizable double bond and a primary amino group
  • a monomer having a sulfonate group is polymerized, or the monomer has a polymerizable double bond in a molecule and is reactive with an amino group. What is necessary is just to polymerize with the monomer which does not contain a group.
  • polystyrene resin in order to obtain a crosslinked type, a polymerizable double bond and a primary amino group, one NHR, _NRR ', one NR R'R " + (R, R ′ and R ′′ are the same as described above) or a monomer having a sulfonic acid group and a group having two or more polymerizable double bonds in the molecule and having reactivity with an amino group (for example, a hydroxyl group, And a monomer that does not contain a carboxylic acid group.
  • Preferred specific examples of the monomer represented by the general formula [ ⁇ '] include, for example, butadiene, isoprene, vinyl acrylate, vinyl methacrylate, aryl acrylate, aryl methacrylate, ethylene diacrylate, ethylene dimethacrylate, and ethylene dimethacrylate. 1,4-butanediol acrylate, 1,6-hexanediol acrylate, ethylene dalicol dimethacrylate, 1,3-butanediol dimethacrylate, triethylene dalicol dimethacrylate, ⁇ , ⁇ '-methylene-bis (acrylamide), divinylbenzene and the like.
  • the crosslinked polyolefin of the present invention represented by the general formula [2] is obtained by combining the uncrosslinked polyolefin of the present invention represented by the general formula [1] with a dicarboxylic acid such as an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid.
  • a dicarboxylic acid such as an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid.
  • the primary amino group of the uncrosslinked polyolefin, —NHR, one NRR ′ or —NRR′R ′′ + (where R, R ′ and IR ”are the same as described above) remains to some extent. As described above, it can also be obtained by performing a dehydration condensation reaction.
  • the dehydration condensation reaction may be performed according to a method known per se.
  • the present invention relates to the present invention.
  • the polyolefin to which a tertiary amino group or a quaternary ammonium group or a sulfonic acid group-containing group according to the present invention is bonded has a structure similar to that generally used as an ion exchange resin. Since they also include those, commercially available ion exchange resins can be used as carriers as they are.
  • Osmium tetroxide can be supported on the carrier for supporting osmium tetroxide of the present invention (hereinafter abbreviated as the carrier of the present invention), for example, as follows.
  • the carrier of the present invention may be reacted with osmium tetroxide. That is, after dissolving osmium tetroxide in a suitable organic solvent, the carrier of the present invention is added thereto, and the mixture is stirred and reacted. After the reaction is completed, the precipitate is collected by filtration and dried under vacuum to obtain osmium tetroxide. Thus, a compound supported on the primary amino group or the NHR portion of the carrier of the present invention is obtained.
  • the polyolefin to which the tertiary amino group, quaternary ammonium group or sulfonic acid group-containing group according to the present invention is bonded carries osmium tetroxide.
  • the carrier of the present invention is added thereto, and the mixture is stirred and reacted. After the reaction is completed, the precipitate is collected by filtration and dried under vacuum to obtain osmium tetroxide.
  • a compound supported on —NR R ′, —NR R′R ′′ + (where R, R ′ and R ′ ′′ are the same as described above) or the sulfonic acid group moiety of the carrier of the present invention is obtained.
  • Examples of the organic solvent used for supporting osmium tetroxide on the carrier include alcohols such as methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, tert-butanol, sec-butanol, and the like.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, isobutanol, n-butanol, tert-butanol, sec-butanol, and the like.
  • ketones such as acetone and methyl ethyl ketone, etc.
  • ethers such as diethyl ether, dioxane, tetrahydrofuran, etc.
  • halogenated hydrocarbons such as dichloromethane, chloroform, etc., for example, acetonitrile, ptyronitrile, etc.
  • Nitriles for example, hydrocarbon
  • the amount of the organic solvent used is usually 1 to 100, preferably 2 to 20 times the weight of the carrier of the present invention.
  • the aqueous solvent may be water alone, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, sec-butanol, and tert-butanol; ketones such as acetone and methylethylketone; and acetonitrile, for example.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, sec-butanol, and tert-butanol
  • ketones such as acetone and methylethylketone
  • acetonitrile for example.
  • Nitriles such as ptyronitrile
  • water-soluble organic solvents such as tetrahydrofuran in water are usually 0 to 50%, preferably 0 to 3%.
  • the amount of the carrier of the present invention is determined by the amount of the primary amino group, one NRR ', -N
  • the sulfonic acid group is usually 0.5 to 10 moles, preferably 1 to 2 moles, per osmium tetroxide. Is set as appropriate.
  • the reaction temperature is usually 0 to 100 ° C, preferably 10 to 30 ° C.
  • the reaction time is generally 1 minute to 24 hours, preferably 3 to 6'0 minutes, and more preferably 10 to 30 minutes.
  • osmium tetroxide easily supported on the carrier of the present invention (hereinafter sometimes abbreviated as the polymer-supported osmium tetroxide of the present invention) is obtained.
  • the polymer-supported osmium tetroxide of the present invention is not only useful as various reaction catalysts, but also the osmium tetroxide itself acts stably for a long period of time, and has excellent durability and solvent resistance. Many because of their nature Even if used repeatedly, its activity does not decrease.
  • the polymer-supported osmium tetroxide of the present invention is particularly toxic because the osmium tetroxide is supported on the carrier of the present invention.
  • Easy to handle without consideration That is, by supporting osmium tetroxide, which is highly toxic and sublimable, on the carrier of the present invention, it is possible to safely store and use osmium tetroxide itself for a long period of time while maintaining the activity of osmium tetroxide itself. Become.
  • the carrier comprising a polyolefin having a primary amino group or a secondary amino group according to the present invention may be an aromatic heterocyclic or aliphatic heterocyclic polymer conventionally used for microencapsulation of osmium tetroxide.
  • the amount of osmium tetroxide supported thereon is much larger than that of osmium tetroxide, and the catalytic activity of the osmium tetroxide of the present invention supported on such a carrier is extremely superior to that of the conventional one. ' 1
  • the amount of an aqueous solvent is larger than that of an organic solvent.
  • Some of these can support osmium tetroxide.
  • Such a catalyst is particularly preferable as a catalyst used in an aqueous solvent.
  • organic solvents Today, the use of organic solvents is considered to be one of the causes of air and groundwater pollution, and particularly highly volatile organic solvents are easily flammable, and their use involves the risk of fire. .
  • organic solvents are carcinogenic substances, and the amount of ultraviolet rays reaching the ground increases as a result of destruction of the ozone layer by organic solvents released into the atmosphere. There are also concerns about the effects of use on the human body.
  • osmium tetroxide is added to the carrier in an aqueous solvent. It is important to obtain an oxidation catalyst by supporting a catalyst on the working environment, to protect the natural environment, etc., and to use inexpensive water as the main solvent. It is extremely useful.
  • the polymer-supported osmium tetroxide of the present invention can be industrially advantageously used as a catalyst for various chemical reactions. Among them, it can be particularly effectively used as an oxidation catalyst when a compound having a reactive double bond is converted into a diol.
  • the action of the polymer-supported osmium tetroxide of the present invention (hereinafter sometimes abbreviated as the oxidation catalyst of the present invention) cleaves the double bond having a reactive activity, and introduces two hydroxyl groups. This forms a dial compound.
  • Any compound having a reactive double bond may be used as long as it has a reactive double bond.
  • the compound include an olefin, a gen compound, and an unsaturated cyclic hydrocarbon compound.
  • the compound may be a polymer compound or a compound having any functional group or / and aromatic ring as a substituent.
  • R 2 5, R 2 6 , R 2 7 and R 2 8 are independently a hydrogen atom, an alkyl group, a Ariru group and Ararukiru group.
  • Orefi down compounds suitable ⁇ medium represented by And the polymer-supported oxide of the present invention is added thereto.
  • the reaction is performed by adding a smear and, if necessary, a co-oxidizing agent, to obtain the following general formula [15] '
  • aryl group examples include those having 6 to 14 carbon atoms, and specific examples include a phenylene group, a naphthylene group, an anthracenedyl group, and a phenanthracenedil group.
  • the aralkyl group usually has 7 to 10 carbon atoms, and specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group. ,
  • reaction solvent examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol; ketones such as acetone and methyl ethyl ketone; and acetonitrile and ptyronitrile, for example.
  • Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol
  • ketones such as acetone and methyl ethyl ketone
  • acetonitrile and ptyronitrile for example.
  • Water, a water-soluble organic solvent such as tetrahydrofuran, water, and the like.These may be used alone or in combination of two or more. Among them, a combination of water and one or more water-
  • the amount of the reaction solvent to be used is generally 1 to 50 times, preferably 1 to 20 times, more preferably 3 to 5 times, the weight of the starting material.
  • the oxidizing agent used if necessary is, for example, 4-methylmorpholine-N-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, pyridine-N-oxide, ⁇ -picoline-N-oxide.
  • N-oxides such as i-picoline- ⁇ -oxide and a-picoline-N-oxide; for example, hydrogen peroxide, tert-butyl hydroperoxide, acetylhydroxide peroxide, tert-butyl peroxide, benzoyl alcohol Oxide, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl peroxy isopropyl Peroxides such as rucaponate, potassium persulfate, sodium persulfate, ammonium persulfate, and metabenzo-peroxybenzoic acid; for example, hypochlorous acid such as sodium hypochlorite, potassium hypochlorite, and ammonium hypochlorite Chlorate, potassium ferricyanide, oxygen and the like.
  • hypochlorous acid such as sodium hypochlorite, potassium hypochlorite, and ammonium hypochlorite Chlorate, potassium ferricyan
  • the amount of the co-oxidizing agent to be used is generally 1 to 10 equivalents, preferably 1 to 5 equivalents, more preferably 1 to 3.5 equivalents, still more preferably 1 to 3 equivalents, still more preferably 1 to 10 equivalents to the starting material. To 1.5 equivalents, particularly preferably 1 to 1.1 equivalents.
  • the reaction time is generally 1 minute to 48 hours, preferably 1 minute to 36 hours, more preferably 10 minutes to 24 hours, and further preferably 10 minutes to 16 hours.
  • the reaction temperature is usually from 10 to: L0O :, preferably from 0 to 60 ° C, more preferably from 10 to 60 ° C.
  • asymmetric especially Orefin represented by the general formula [14] is centered reactive double bond moiety in R 2 5 and R 2 7, and R 2 7 and R 2 9 Togaotto people different from one another
  • an asymmetric oxidation reaction occurs if the above reaction is carried out for coexistence of an asymmetric ligand, and the corresponding diol compound is produced with high stereoselectivity.
  • Examples of asymmetric ligands include 1,4-bis (9-0-dihydroquinidine) phthalazine, 1,4-bis (9-0-dihydroquinidine) anthraquinone, and 6,4-bis (9-0- Dihydroquinidine) 2,5-diphenylpyrimidine, dihydroquinidine, dihydrocinchonidine, 1,4-bis (9-0-dihydroquinine) phthalazine, 1,4-bis (9-0-dihydroquinine) anthraquinone, 6,4 -Bis (9-0-dihydroquinine) 2,5-diphenylpyrimidine, dihydroquinine, and dihydrocinchonine.
  • the amount of the asymmetric ligand to be used is usually 0.01 to 0.3 times mol, preferably 0.01 to 0.05 times mol, of olefin. That is, for example, Olefin is mixed with a solvent of about 15 times the weight of acetonitrile monohydrate (5/1) with respect to Olefin, and the polymer-supported osmium tetroxide of the present invention is contained therein. Osmium oxide was added to 5 mol 1% of the olefin, and 1.1 equivalents of N-methylmorpholine oxide were added to the olefin, followed by stirring and reaction at room temperature for about 16 hours. After filtering to remove the polymer-supported osmium tetroxide, the reaction solution is concentrated and, if necessary, purified to obtain the corresponding diol compound.
  • the substrate dropwise later from the viewpoint of asymmetric yield. That is, for example, in a solvent of about 15 times the weight of acetonitrile-monohydric water (5Z1) with respect to olefin, the osmium tetroxide and the asymmetric ligand present therein are each 5 mol%.
  • the polymer-supported osmium tetroxide of the present invention and an asymmetric ligand are added to the mixture, and N-methylmorpholine oxide is added in an amount equivalent to 1.1 equivalents of the olefin. Thereafter, the olefin is reacted at room temperature for about 24 hours. After completion of the reaction, the mixture was filtered to remove the polymer-supported osmium tetroxide, and then the reaction solution was concentrated and, if necessary, purified.
  • the volimer-supported osmium tetroxide of the present invention is filtered from the residue of the reaction solution, dried and isolated. Then, it can be used repeatedly as a reaction catalyst without decreasing its activity.
  • Example 1 Polymer-supported osmium tetroxide of the present invention
  • osmium tetroxide l.Og (3.9 mmol) in lOmL of methanol was added 5 g of the polymer obtained in Example 2 while stirring at room temperature, and the mixture was stirred and reacted at the same temperature for 15 minutes. After the completion of the reaction, the polymer was washed with methanol and dried under vacuum at room temperature for 12 hours to obtain 6.0 g of polymer-supported osmium tetroxide as a black powder. The content of osmium tetroxide was 16.7%.
  • Tris- (2-aminoethyl) -amine polystyrene resin [1%: DVB cross-linked, containing 4.4 mmol / g as amino group: nova while stirring at room temperature in a solution of osmium tetroxide l.Og (3.9 mmol) in methanol lOmL 5 g of -biochem brand name (containing ⁇ 2bis (2-aminoethyl) aminoethyl ⁇ aminomethyl group) was added, and the mixture was stirred and reacted at the same temperature for 15 minutes. After completion of the reaction, the polymer was washed with methanol and vacuum-dried at room temperature for 12 hours. 6.0 g of supported osmium tetroxide was obtained. The content of osmium tetroxide was '16 .7%.
  • Example 7 Polymer supported osmium tetroxide of the present invention
  • Anion exchange resin [trade name: IRA910CT Cl, -N + (CH 3 ) 2 (CH 2 CH 2 OH) Cl— group—with stirring at room temperature in a solution of 0.5 g (2mniol) of osmium tetroxide in 50 mL of water It was added organo Co.] 5 g, 1 2 h c after the reaction was allowed to stir the reaction at the same temperature, the Borima one was washed with methanol, and 1 2 hour vacuum drying at room temperature, polymer supported tetroxide black powder 5.3 g of osmium were obtained. The content of sodium tetroxide was 5.7%.
  • Example 8 Osmium tetroxide supported on a polymer of the present invention
  • a solution of 0.5 g (2 mmol) of osmium tetroxide in 50 mL of water was stirred at room temperature.
  • 5 g of a cation exchange resin [trade name: IR120B Na, 8% DVB cross-linked, -SO 3 Na group-containing: manufactured by Organo Corporation] was added, and the mixture was stirred and reacted at the same temperature for 12 hours.
  • the polymer was washed with methanol and dried under vacuum at room temperature for 12 hours to obtain 5.32 g of a polymer-supported osmium tetroxide as a black powder.
  • the content of osmium tetroxide was 6.4%.
  • Example 1 Diolation reaction 0.91 g (7.7 mmol) of -methylstyrene, 10 mL of acetonitrile and 2 mL of water are mixed, and 1.14 g (8.5 mmol) of 4-methylmorpholine-N-oxide and the polymer-supported tetroxide obtained in Example 1 are mixed.
  • Example 15 Asymmetric diolation reaction, "Acetonitrile lOmL and 2 mL of water were mixed, and 0.30 g of 1,4-bis (9-0-dihydroquinidine) phthalazine and 1.14 g of N-methylmorpholine oxide were added thereto. And 0:59 g of the polymer-supported osmium tetroxide obtained in Example 1 (corresponding to 0.39 mmol of OsO 4 ), and 0.91 g of trans- / 3-methylstyrene was added for 24 hours while stirring at room temperature.
  • the present invention provides a catalytically active substance which can be produced more industrially, has excellent solvent resistance and heat resistance, its activity is hardly reduced by repeated use, and is easy to handle.
  • the polymer-supported osmium tetroxide of the present invention can be safely stored for a long period of time because osmium tetroxide is supported on a carrier, and can be handled without special consideration for its toxicity.
  • the action of osmium tetroxide itself is stable over a long period of time, and it has excellent durability and solvent resistance. It is very useful as a catalyst. Because of these excellent characteristics, the polymer-supported osmium tetroxide of the present invention can be used as an industrially useful oxidation catalyst in various chemical reactions such as diolation of a compound having a reactive double bond. I can do it.

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Abstract

L'invention concerne : (1) un tétraoxyde d'osmium supporté par un polymère auquel est lié un groupe d'échange ionique, tel qu'un groupe amino primaire, -NHR, -NRR', -NR'R''+ (dans lequel R, R' et R'' représentent chacun indépendamment alkyle, aryle ou aralkyle) ou un groupe sulfonate ; des supports permettant de supporter le tétraoxyde d'osmium qui contiennent une polyoléfine à laquelle ledit groupe d'échange ionique est lié ; des catalyseurs d'oxydation comprenant du tétraoxyde d'osmium supporté sur ces supports ; (2) un procédé permettant de produire un tétraoxyde d'osmium en utilisant ces supports contenant du tétraoxyde d'osmium ; (3) une méthode permettant de stocker le tétraoxyde d'osmium en plaçant du tétraoxyde d'osmium sur ces supports ; et (4) un procédé permettant de produire un composé diol en traitant une oléfine avec un catalyseur d'oxydation comprenant le tétraoxyde d'osmium tel que décrit ci-dessus. La méthode décrite ci-dessus permet de produire, à l'échelle industrielle, un composé contenant de l'osmium, qui peut être facilement manipulé, qui présente une excellente résistance aux solvants et qui ne subit aucune diminution de l'activité catalytique, y compris après une utilisation répétée.
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US6646168B2 (en) 2001-10-23 2003-11-11 Council Of Scientific And Industrial Research Supported osmates, process for preparation thereof, and a process for the preparation of chiral vicinal diols using supported osmate catalyst
WO2005085307A1 (fr) * 2004-03-08 2005-09-15 Japan Science And Technology Agency Compositions d’agglomérats de métal supportés sur polymère
KR100540377B1 (ko) * 2003-05-22 2006-01-11 동우 화인켐 주식회사 이중으로 작용기가 도입된 공중합체를 이용한 촉매 고정화
JP2011201862A (ja) * 2010-03-04 2011-10-13 National Institute Of Advanced Industrial Science & Technology 磁性ナノ粒子固定型オスミウム（ｖｉ）酸塩
JP2013185150A (ja) * 2012-03-08 2013-09-19 Tokyo Kasei Kogyo Kk ポリスチレン担持ピリジンビスオキサゾリン誘導体−カルシウム触媒

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6646168B2 (en) 2001-10-23 2003-11-11 Council Of Scientific And Industrial Research Supported osmates, process for preparation thereof, and a process for the preparation of chiral vicinal diols using supported osmate catalyst
US6815566B2 (en) 2001-10-23 2004-11-09 Council Of Scientific And Industrial Research Supported osmates, process for preparation thereof, and a process for the preparation of chiral vicinal diols using supported osmate catalyst
WO2003080242A1 (fr) * 2002-03-21 2003-10-02 Council Of Scientific And Industrial Research Osmates sur support, leur procede de preparation, et procede de preparation de diols vicinaux chiraux
KR100540377B1 (ko) * 2003-05-22 2006-01-11 동우 화인켐 주식회사 이중으로 작용기가 도입된 공중합체를 이용한 촉매 고정화
WO2005085307A1 (fr) * 2004-03-08 2005-09-15 Japan Science And Technology Agency Compositions d’agglomérats de métal supportés sur polymère
EP1739104A1 (fr) * 2004-03-08 2007-01-03 Japan Science and Technology Agency Compositions d' agglomerats de metal supportes sur polymere
JPWO2005085307A1 (ja) * 2004-03-08 2007-12-13 独立行政法人科学技術振興機構 高分子担持金属クラスター組成物
EP1739104A4 (fr) * 2004-03-08 2009-01-07 Japan Science & Tech Agency Compositions d' agglomerats de metal supportes sur polymere
US8110519B2 (en) 2004-03-08 2012-02-07 Japan Science & Technology Agency Polymer-supported metal cluster composition
JP5055525B2 (ja) * 2004-03-08 2012-10-24 独立行政法人科学技術振興機構 高分子担持金属クラスター組成物
JP2011201862A (ja) * 2010-03-04 2011-10-13 National Institute Of Advanced Industrial Science & Technology 磁性ナノ粒子固定型オスミウム（ｖｉ）酸塩
JP2013185150A (ja) * 2012-03-08 2013-09-19 Tokyo Kasei Kogyo Kk ポリスチレン担持ピリジンビスオキサゾリン誘導体−カルシウム触媒

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