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A kind of method for preparing 2-hydroxyl-4-methyltetrahydropyran

A methyltetrahydropyran, hydroxyl technology, applied in the direction of carbon monoxide reaction preparation, chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problem that rhodium catalysts are difficult to recycle, rhodium catalysts and phosphine Difficult to recycle ligands, catalyst loss and other problems, to achieve the effect of inhibiting acetal side reactions, simple and reliable process route, and improving reaction selectivity

Active Publication Date: 2020-04-10
WANHUA CHEM GRP CO LTD
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  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In this method, by introducing the general formula P(OR) 3 The tertiary phosphine ligand, the reaction selectivity is effectively improved; but because the rhodium catalyst is easy to form rhodium clusters in the process of distillation and separation of products and deactivate, and then cause the loss of the catalyst, there are still disadvantages that the rhodium catalyst and the phosphine ligand are difficult to recycle
[0006] In view of the deficiencies of the existing technology, it is necessary to develop a rhodium-phosphine catalyst system capable of efficiently synthesizing 2-hydroxy-4-methyltetrahydropyran (MHP), and at the same time effectively solve the problems that the rhodium catalyst is difficult to recycle.

Method used

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  • A kind of method for preparing 2-hydroxyl-4-methyltetrahydropyran
  • A kind of method for preparing 2-hydroxyl-4-methyltetrahydropyran
  • A kind of method for preparing 2-hydroxyl-4-methyltetrahydropyran

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Embodiment 1

[0061] Ligand L1 is 4,8-di(1,1-tert-butyl)-N,N,1,2,10,11-hexamethyl-dibenzo[d,f][1,3,2] Synthesis of Dioxaphosphorin-6-amine

[0062] a) Synthesis of 3,4-dimethyl-6-tert-butylphenol

[0063] Preheat 122.0g of 3,4-dimethylphenol to 65°C, add 2.5ml of concentrated sulfuric acid, feed isobutene at a flow rate of 0.2L / min, keep the reaction at 70°C for 2h, add 20wt% sodium hydroxide aqueous solution to neutralize the reaction solution , separated and retained the organic phase, and distilled under reduced pressure to obtain 114.1 g of 3,4-dimethyl-6-tert-butylphenol.

[0064] b) Synthesis of 3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-2,2'-dihydroxybiphenyl

[0065] Dissolve 82g of 3,4-dimethyl-6-tert-butylphenol and 5g of potassium chromate in 300ml of acetic acid, heat to 90°C, and inject oxygen for 5h. Oxygen was released after the reaction, acetic acid was removed by atmospheric distillation, then 200ml of deionized water was added, and 46.9g of solid was obtained by filtratio...

Embodiment 2

[0069] Ligand L2 is 4,8-bis(1,1-tert-butyl)-1,2,10,11-tetramethyl-N,N-bis(1-methylethyl)-dibenzo[d ,f][1,3,2]Synthesis of dioxaphosphorin-6-amine

[0070] Dissolve 3.4g of phosphorus chloride in 40ml of ether, add 2.5g of diisopropylamine dropwise, stir at room temperature for 0.5h, raise the temperature to 100°C for 3h, release hydrogen chloride gas, and obtain dichlorodiisopropylaminophosphine ether solution. Dissolve 8.2g of 3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-2,2'-dihydroxybiphenyl and 2g of pyridine in 50ml of ether, stir and heat to reflux, slowly Dichlorodiisopropylaminophosphine ethyl ether solution was added dropwise, and the addition was completed in 1h. Cool down to room temperature, filter, diethyl ether is removed from the filtrate by vacuum distillation, 100ml of deionized water is added to the residue, solids are precipitated, the filter cake is washed with deionized water after filtration, and 6.5g of solids are obtained after drying, namely 4,8- Bis(1,1...

Embodiment 3

[0072] Ligand L3 is 4,8-di(1,1-tert-butyl)-1,2,10,11-tetramethyl-N,N-diphenyl-dibenzo[d,f][1, 3,2] Synthesis of dioxaphosphorin-6-amine

[0073]Dissolve 3.4g of phosphorus chloride in 40ml of diethyl ether, add 4.2g of diphenylamine dropwise, stir at room temperature for 0.5h, raise the temperature to 100°C for 3h, and obtain dichlorodiphenylaminophosphine ether solution. Dissolve 8.2g of 3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-2,2'-dihydroxybiphenyl and 2g of pyridine in 50ml of ether, stir and heat to reflux, slowly Dichlorodiphenylaminophosphine ethyl ether solution was added dropwise, and the addition was completed in 1h. Lowered to room temperature, filtered, the filtrate was distilled under reduced pressure to remove ether, 100ml of deionized water was added to the residue, and solids were precipitated. After filtration, the filter cake was washed with deionized water and dried to obtain 6.9g of solids, namely 4,8- Bis(1,1-tert-butyl)-1,2,10,11-tetramethyl-N,N-dipheny...

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Abstract

The invention relates to a method of preparing 2-hydroxy-4-methyltetrahydropyran from 3-methyl-3-butene-1-alcohol (IPEA) under the catalysis of a rhodium metal compound and a tertiary phosphine ligand (MHP) method, after the reaction is finished, the product and catalyst are separated by water extraction, the rhodium catalyst and the tertiary phosphine ligand remain in the organic phase, the product remains in the water phase, the IPEA conversion rate can be as high as 99.7%, and the product MHP selectivity reaches 85.9%. , the method overcomes the difficult problem that the expensive rhodium catalyst is difficult to recover in the hydroformylation reaction process, and is more conducive to industrial application.

Description

technical field [0001] The invention relates to a method for preparing 2-hydroxyl-4-methyltetrahydropyran (MHP) from 3-methyl-3-buten-1-ol (IPEA) through hydroformylation reaction and hemiacetal reaction The method belongs to the technical field of chemical industry. [0002] technical background [0003] 2-Hydroxy-4-methyltetrahydropyran (MHP) is an important intermediate compound for the preparation of 3-methyl-1,5-pentanediol (MPD for short). The MPD molecule contains two primary hydroxyl branched chains Fatty alcohol, the unique molecular structure of MPD makes it have special advantages in many application fields, especially in the field of polyurethane resin production. [0004] U.S. published patent US04663468 discloses a kind of preparation method of 2-hydroxyl-4-methyltetrahydropyran (MHP): in rhodium catalyst and synthesis gas (CO and H 2 In the presence of a volume ratio of 1:1), 3-methyl-3-buten-1-ol (IPEA) is hydroformylated to generate 2-hydroxyl-4-methyltetra...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D309/10B01J31/22C07C45/50C07C47/19
CPCB01J31/185B01J2231/321B01J2531/822C07C45/50C07D309/10C07C47/19
Inventor 许晓涛吕英东张红涛张永振黎源
Owner WANHUA CHEM GRP CO LTD
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