Solid-loaded ionic-liquid catalyst for olefin-dihydroxy reaction, its production and use

A technology of ionic liquid and catalyst, which is applied in the field of immobilized ionic liquid-loaded transition metal catalytic active center catalyst and its preparation, can solve the problems of complicated separation and purification, difficulty in catalyst recycling, high price, etc., and achieve the effect of simple product separation

Inactive Publication Date: 2007-11-21
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Perfluorosulfonic acid resin catalyst Nation NR50 is more effective for olefin dihydroxylation reaction, the yield of unpurified 1,2-cyclohexanediol is 98%, the catalyst can be recycled, but a large amount of H 2 o 2 (2 times the amount of olefin) and longer reaction time (24 hours) all can bring burden for industrialization, and perfluorinated sulfonic acid resin synthesis difficulty, expensive (Y.Usui, K.Sato, M.Tanaka, Angew .Chem.Int.Ed.2003, 42, 5623-5625)
[0005] In summary, the current olefin dihydroxylation process still has one or more of the following disadvantages: the catalyst or oxidant is toxic, the cost is high, and a high concentration of H is required. 2 o 2 , risky operation, increased cost, low reaction yield, complex separation and purification, difficulty in catalyst recycling, etc.
Immobilized monolayer imidazolium ionic liquid supported transition metal catalyst system has also been applied in olefin epoxidation reaction (K.Yamaguchi, J.Am.Chem.Soc., 2005, 127:530-531), but The application of liquid catalytic system in olefin dihydroxylation has not been reported yet

Method used

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  • Solid-loaded ionic-liquid catalyst for olefin-dihydroxy reaction, its production and use
  • Solid-loaded ionic-liquid catalyst for olefin-dihydroxy reaction, its production and use

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Take 8.00g (11.5mmol) peroxytungstate K 2 [{W(=O)(O 2 )(H 2 O)} 2 (μ-O)]·2H 2 O was dissolved in 100mL distilled water, and 15.0g of SiO 2 / tri-RTILs-CH 3 / PF 6 (For the synthesis method, see Chinese patent ZL.200710017755.2, the structure is shown in Formula 2) Suspend in the solution, and react with mechanical stirring at room temperature for 3 days. After the reaction, filter with suction, wash the solid with distilled water, and dry it in vacuum (50°C, -0.07MPa) to obtain powdered catalyst SiO 2 / tri-RTILs-CH 3 / W. Environmental scanning electron microscopy (SEM-EDAX) analysis of the surface of the catalyst revealed: C, 24.93; O, 26.59; Br, 0.53; Si, 38.45; W, 9.51wt%.

[0037] SiO 2 / tri-RTILs-CH 3 / PF 6

[0038] Formula 2

[0039] will be prepended with H 3 PO 4 1.135 g (10 mmol) of 30% H adjusted to pH = 1.5 2 o 2 , 1.64g (20mmol) freshly distilled cyclohexene, immobilized three-layer ionic liquid catalyst SiOx / tri-RTILs-CH 3 / W 1mol% mixed, ...

Embodiment 2-9

[0041] The composite catalysts used successively in the dihydroxylation reaction of embodiment 2-9 are four kinds of immobilized monolayer imidazole ionic liquid SiO 2 / mono-RTIL-R / W and four immobilized bilayer imidazolium ionic liquid SiO 2 / di-RTILs-R / W, their preparation method is the same as the composite catalyst preparation method of embodiment 1, by base catalyst SiO 2 / mono-RTIL-R / PF 6 (Equation 3) and SiO 2 / di-RTILs-R / PF 6 (Formula 4) and peroxytungstate K 2 [{W(=O)(O 2 )(H 2 O)} 2 (μ-O)]·2H 2 Formed by the action of O, the preparation method of the immobilized double-layer imidazole ionic liquid in these two types of basic catalysts can be found in Chinese patent ZL.

[0042] R=a)-C 4 h 9 b)-C 8 h 17 d)-C 6 h 5 CH 2 e)-C 12 h 25 SiO 2 / mono-RTIL-R / PF 6

[0043] Formula 3

[0044] R=a)-C 4 h 9 b)-C 8 h 17 d)-C 6 h 5 CH 2 e)-C 12 h 25 SiO 2 / di-RTILs-R / PF 6

[0045] Formula 4

[0046] implement

[0047...

Embodiment 10

[0049] 2.50g (10mmol) tungstic acid H 2 WO 4 Add to 7 mL 30% H in portions 2 o 2 The solution was stirred and reacted for 2 hours, the reaction mixture was suction filtered with a funnel, and 0.3 mL (1.25 mmol) of 80% H was added to the filtrate at room temperature. 3 PO 4 Solution, 5mL acetone, 1.00g immobilized three-layer ionic liquid SiO 2 / tri-RTILs-CH 3 / PF 6 (See Chinese patent ZL.200710017755.2 for the synthesis method, the structure is shown in Formula 2), and the reaction was stirred for 72 hours. Suction filtration, the solid was washed with distilled water, and dried in vacuum (50°C, -0.07MPa) to obtain powdered catalyst SiO 2 / tri-RTILs-CH 3 / PW (its anion is [PO 4 {W(O)(O 2 ) 2} 4 ] 3- form exists). Environmental scanning electron microscope energy spectrum (SEM-EDAX) analysis catalyst surface, measured: C, 20.17; O, 33.66; Si, 36.78; P, 0.46; W, 8.93wt%.

[0050] The dihydroxylation reaction of cyclohexene is by the method for embodiment 1, and th...

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Abstract

The invention is concerned with immobilization ion liquid activators, production for the dihydroxylation of olefin and the method producing rare H2O2 solution into vicinal diol by those activators and under the acidity condition with organic solution or without organic solution. The said activator is based with immobilization ion liquid and loaded transition metal active center. The activator can be reused and the loaded transition metal tungsten is innocuous and cheap. Compare with traditional method, it takes rare H2O2 solution as oxidant with high utilization ratio and cleaning to avoid pollute for too much of organic acid. The transform ration is 98 percent of H2O2 during the process without organic solution and superfluous olefin and the separate ration of 1,2-cyclohexanediol is 92 percent. The activator can be reused for eight times and still has good active nature and the process is easy and applied for industry exploitation.

Description

technical field [0001] The invention relates to a class of immobilized ionic liquid catalysts for olefin dihydroxylation reactions, as well as their preparation and usage. Specifically, a class of immobilized ionic liquid supported transition metal catalytic active center catalyst and its preparation method are provided, and it is provided as a catalytic system in catalytic H 2 o 2 Solution dihydroxylation of alkenes for use in the preparation of vicinal diols. Background technique [0002] The dihydroxylation of olefins to vicinal diols is an important organic oxidation reaction, and many dihydroxylation products are widely used organic chemical raw materials or intermediates. For example: cyclohexene dihydroxylation product - trans-1,2-cyclohexanediol can be used as a raw material for the synthesis of medicines, pesticides, high-grade coatings, surfactants, rubber additives, liquid crystal materials, plasticizers, etc. In recent years, the preparation of catechol by cat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/06C07C35/14C07C29/04
CPCY02P20/584
Inventor 魏俊发王彦明毕元元石先莹
Owner SHAANXI NORMAL UNIV
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