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A kind of method for preparing pinoxaden and its intermediate

A pinoxaden and intermediate technology, applied in the field of organic synthesis, can solve the problems of high cost, three wastes pollution, halogen corrosion, etc., and achieve the effect of low cost, less three wastes, and favorable industrial production

Active Publication Date: 2019-12-03
ZHEJIANG ZHUJI UNITED CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, the diazo-halogenation reaction process not only produces a large amount of three waste pollution, but also has potential safety hazards and halogen corrosion problems
Not only that, the metal-catalyzed coupling reaction of halides and malonic acid derivatives requires the use of expensive organometallic catalysts, which are difficult to recycle and costly

Method used

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  • A kind of method for preparing pinoxaden and its intermediate
  • A kind of method for preparing pinoxaden and its intermediate
  • A kind of method for preparing pinoxaden and its intermediate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Example 1: Preparation of 2-(2,6-diethyl-4-methyl-2-ene-1-cyclohexylene) malononitrile

[0033] 32.4g (0.20mol) of 2-(4-heptidene)malononitrile, 14.0g (0.20mol) of 2-methacrolein and 2.2g (0.02mol) of triethylenediamine were successively added to toluene, at 130 reaction at ℃. After the reaction is complete, the temperature is lowered, washed with 1N dilute hydrochloric acid, extracted with ethyl acetate, dried, concentrated and distilled to obtain the product 2-(2,6-diethyl-4-methyl-2-ene-1-cyclohexylene) propanedi Nitrile 39.4g, yield 92%. 1 H NMR (CDCl 3 ,500MHz,TMS):δ6.14-6.14(m,1H),3.08-3.04(m,1H),2.82-2.75(m,1H),2.57-2.46(m,2H),2.04-2.01(m, 1H), 1.56-1.51 (m, 2H), 1.48-1.41 (m, 1H), 1.12-1.01 (m, 6H), 1.00-0.98 (m, 3H). 13 C NMR (CDCl 3 , 125MHz): δ175.12, 148.74, 134.78, 113.99, 113.74, 43.75, 34.75, 28.13, 16.55, 15.52, 20.91, 13.59, 11.98.

Embodiment 2

[0034] Example 2: Preparation of methyl 2-cyano-2-(2,6-diethyl-4-methyl-1-cyclohexenylene) acetate

[0035] 58.6g (0.300mol) of methyl 2-cyano-3-propyl-2-enehexanoate, 27.3g (0.390mol) of 2-methacrolein and 30.3g (0.300mol) of triethylamine were added to toluene in turn During the reaction, the temperature was raised and refluxed until the reaction was complete. The warm, 1N dilute hydrochloric acid was washed, dried, and concentrated to obtain 62.8 g of methyl 2-cyano-2-(2,6-diethyl-4-methyl-1-cyclohexenylidene)acetate in a yield of 62.8 g. 84%. 1 H NMR (CDCl 3 ,500MHz,TMS):δ6.02-5.90(m,1H),3.83-3.82(m,3H),3.63-3.07(m,1H),2.91-2.44(m,2H),2.22-1.95(m, 2H), 1.58-1.42 (m, 3H), 1.08-1.04 (m, 4H), 1.00-0.90 (m, 5H).

Embodiment 3

[0036] Example 3: Preparation of 2-(2,6-diethyl-4-methylphenyl)malononitrile

[0037] 2-(2,6-diethyl-4-methyl-2-ene-1-cyclohexylene) malononitrile 10g (0.05mol) and Pd / C 0.5g were heated to 220℃ in nitrogen atmosphere to react , after the reaction is complete, the temperature is lowered, the catalyst is removed by filtration, and washed with a small amount of solvent. The organic phase was extracted with 1N aqueous sodium hydroxide solution, the aqueous phase was washed with methyl tert-butyl ether, and the pH was adjusted to 3-5 with concentrated hydrochloric acid. The aqueous phase was then extracted twice with ethyl acetate. The organic phase was dried and concentrated to obtain 8.4 g of 2-(2,6-diethyl-4-methylphenyl)malononitrile with a yield of 85%. 1 H NMR (CDCl 3,500MHz,TMS):δ7.00(s,2H),5.29(s,1H),2.81(q,J=7.5Hz,4H),2.34(s,3H),1.32(t,J=7.5Hz, 6H). 13 C NMR (CDCl 3 , 125MHz): δ142.66, 140.73, 128.74, 120.00, 112.24, 26.48, 21.21, 21.13, 15.03.

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Abstract

The invention provides a preparation method and an intermediate of pinoxaden. The preparation method includes: using 2-methylacrolein as a raw material; subjecting the raw material to cyclization andaromatization to obtain herbicide-pinoxaden. Compared with the prior art, the preparation method has the distinguishing features and the advantages that a completely different preparation strategy isadopted; a completely different nonaromatic compound is used as the raw material which is safe and easy to obtain; the preparation method is few in three wastes, low in cost and conducive to industrial production.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of a herbicide pinoxaden and an intermediate thereof. Background technique [0002] Pinoxaden is an important new high-efficiency herbicide (WO000 / 78881, WO 00 / 78712). It is widely used in weed control of crops such as wheat, and has a good market prospect. At present, the method for synthesizing pinoxaden is through 2-(2,6-diethyl-4-methylphenyl)malonic acid diester or 2-(2,6-diethyl-4-methyl) Phenyl)malonamide and [1,4,5]-oxodiazepine After cyclization reaction, 8-(2,6-diethyl-4-methylphenyl)tetrahydropyrazolo[1,2-d][1,4,5]oxadiazepine was obtained -7,9-dione, which in turn reacts with pivaloyl chloride to give pinoxaden. [0003] 2-(2,6-Diethyl-4-methylphenyl)malonic acid diester is obtained by using 2-(2,6-dibromo-4-methylphenyl)malonic acid diester as raw material, It is prepared by metal catalyzed coupling reaction with tributyl vinyl...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D498/04C07C255/33C07C255/31C07C253/30C07C255/41
CPCC07C253/30C07C255/31C07C255/33C07C255/41C07D498/04
Inventor 孙殷卫张盼赖腾陈邦池
Owner ZHEJIANG ZHUJI UNITED CHEM
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