2-cyclohexene-1-ketone preparation method

A technology of cyclohexene and alkyl vinyl ether, applied in the preparation of organic compounds, chemical instruments and methods, preparation of carbon-based compounds, etc., can solve problems such as large equipment investment, achieve low environmental pollution and strong industrial application value , the effect of high yield

Active Publication Date: 2016-02-24
HUAZHONG UNIV OF SCI & TECH
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  • Abstract
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  • Claims
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Problems solved by technology

Although the raw material cost of this method is low, the equipment investment is large, and there is no report for industrial production of cyclohexenone

Method used

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  • 2-cyclohexene-1-ketone preparation method
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  • 2-cyclohexene-1-ketone preparation method

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preparation example Construction

[0024] The preparation method of 2-cyclohexen-1-one among the present invention is mainly realized through the following steps:

[0025] Step (1): Put 1,3-dicarbonyl compound, alkyl vinyl ether and formaldehyde into a reactor equipped with magnetic stirring, wherein the molar ratio of 1,3-dicarbonyl compound to alkyl vinyl ether is 3 : 1 to 1: 3, the molar ratio of 1,3-dicarbonyl compound to formaldehyde is 1: 1 to 1: 3, the above materials are mixed and reacted at 50 to 110 ° C for 1 to 8 hours, and after the reaction is completed, they are distilled under reduced pressure to obtain 2-Alkoxy-3,4-dihydropyran derivatives.

[0026] Step (2): Put the 2-alkoxy-3,4-dihydropyran derivative obtained in step (1), acid and solvent into a reactor equipped with magnetic stirring to obtain a mixed solution; wherein, the acid and 2 - The molar ratio of alkoxy-3,4-dihydropyran derivatives is 1:1 to 8:1, and the ratio of solvent volume to 2-alkoxy-3,4-dihydropyran derivatives is 0.5 to 5 ...

Embodiment 1

[0029] Embodiment 1: Ethyl vinyl ether, formaldehyde and methyl acetoacetate prepare cyclohexenone

[0030]

[0031] Take 144.2 g (2.0 mol) of ethyl vinyl ether, 30.0 g (1.0 mol) of paraformaldehyde, and 116.1 g (1.0 mol) of methyl acetoacetate, mix them in methanol (500 ml), and stir at 50° C. for 5 hours. After the reaction was completed, the solvent and unreacted raw material ethyl vinyl ether were distilled off, and then distilled under reduced pressure to obtain 6-methyl-2-ethoxyl-5-carboxymethyl-3,4-dihydropyran 160.1g ( 0.8mol). 1 HNMR (400MHz, CDCl 3 ,TMS,25℃)δ=5.10–4.97(m,1H),3.92–3.79(m,1H),3.69(s,3H),3.66–3.54(m,1H),2.42–2.28(m,2H) ,2.24(s,3H),1.90–1.82(m,1H),1.82–1.70(m,1H),1.22ppm(td,J=7.1,0.8Hz,3H). 13 CNMR (100MHz, CDCl 3 ,25℃)δ=168.9,162.0,102.0,98.0,64.3,51.1,26.3,20.0,18.0,15.2ppm.IR(KBr):v=2976,2947,1711,1630,1436,1379,1276,1185, 1120,1079,1013,971,861,769cm -1 .HRMS(TOF,ESI):m / zcalcdforC 10 h 17 o 4 ,[M+H] + 201.1127, found 201.1122. 160.1 g (...

Embodiment 2

[0032] Embodiment 2: Butyl vinyl ether, formaldehyde and ethyl acetoacetate prepare cyclohexenone

[0033]

[0034] Take 300.2 g (3.0 mol) of butyl vinyl ether, 162.1 g (2.0 mol) of formaldehyde aqueous solution, and 130.1 g (1.0 mol) of ethyl acetoacetate, mix and react at 110° C. for 6 hours. After the reaction was completed, the unreacted raw material butyl vinyl ether was distilled off, and then distilled under reduced pressure to obtain 171.9 g (0.71 mol ). 1 HNMR (600MHz, CDCl 3 ,TMS,25℃)δ=5.02(d,J=1.0Hz,1H),4.21–4.10(m,2H),3.80(dt,J=8.5,6.7Hz,1H),3.59–3.48(m,1H ),2.42–2.27(m,2H),2.24(s,3H),1.88–1.83(m,1H),1.81–1.71(m,1H),1.64–1.51(m,2H),1.40–1.33(m ,2H),1.28(t,J=7.1Hz,3H),0.91ppm(t,J=7.4Hz,3H). 13 CNMR (150MHz, CDCl 3 , 25°C) δ=168.32, 161.51, 102.04, 97.92, 68.40, 59.57, 31.64, 26.11, 19.89, 19.18, 17.81, 14.35, 13.7ppm. 171.9 g (0.71 mol) of the obtained dihydropyran derivative, 547 g (4.5 mol) of hydrochloric acid aqueous solution (30 wt %) were mixed in butan...

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Abstract

The invention discloses a 2-cyclohexene-1-ketone preparation method which comprises the following steps: (1) performing a 1-8 hours' reaction on a raw material which comprises alkyl vinyl ether, a 1,3-dicarbonyl compound and formaldehyde at 50-110 DEG C, and performing separation to obtain a 2-alkoxyl-3,4-dihydropyran derivative, wherein the molar ratio of the 1,3-dicarbonyl compound to the alkyl vinyl ether is (3-1):(1-3), and the molar ratio of the 1,3-dicarbonyl compound to formaldehyde is 1:(1-3); (2) putting the 2-alkoxyl-3,4-dihydropyran derivative obtained in the step (1) in an acid alcohol medium for a 1-8 hours' reaction at 0-100 DEG C, so as to obtain 2-cyclohexene-1-ketone. Compared with the conventional cyclohexene oxidation and cyclohexanone bromination methods, the 2-cyclohexene-1-ketone preparation method provided by the invention has the advantages of being high in reaction selectivity, easy for product separation, low in environmental pollution, very high in industrial application value, and the like.

Description

technical field [0001] The invention belongs to the technical field of fine chemicals preparation, and more specifically relates to a method for preparing cyclohexenone by using 1,3-dicarbonyl compound, alkyl vinyl ether and formaldehyde as raw materials. Background technique [0002] Cyclohexenone, also known as 2-cyclohexen-1-one, is an important class of fine organic chemical intermediates, widely used in medicine, pesticides, spices, surfactants, polymer materials and other fields. Cyclohexenone can be used to synthesize cyclohexenone herbicides and steroids, and substituted cyclohexenone is an intermediate for synthesizing phenol derivatives. [0003] Currently, the methods for synthesizing cyclohexenone mainly include cyclohexene oxidation, cyclohexanone bromination and phenol hydrogenation. Using glacial acetic acid as a solvent, chromic anhydride as a chemical oxidant to oxidize cyclohexene can obtain cyclohexenone; cyclohexene is in Cu(acac) 2 、Pd(acac) 2 In the ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/603C07C45/00
CPCC07C45/00C07D211/78C07C49/603
Inventor 顾彦龙刘昌会周炳华潘晓娟王维
Owner HUAZHONG UNIV OF SCI & TECH
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