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Preparation method and intermediate of pinoxaden

A technology of pinoxaden and intermediates, applied in the field of organic synthesis, can solve the problems of high cost, three-waste pollution, halogen corrosion, etc., and achieves the effects of low cost, less three-waste and favorable industrial production

Active Publication Date: 2018-07-10
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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  • Preparation method and intermediate of pinoxaden
  • Preparation method and intermediate of pinoxaden
  • Preparation method and intermediate of pinoxaden

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] Add 32.4g (0.20mol) of 2-(4-heptyl)malononitrile, 14.0g (0.20mol) of 2-methacrolein and 2.2g (0.02mol) of triethylenediamine to toluene in sequence, and at 130 Reaction at ℃. After the reaction is complete, lower the temperature, wash with 1N dilute hydrochloric acid, extract with ethyl acetate, dry, concentrate and distill to obtain the product 2-(2,6-diethyl-4-methyl-2-en-1-cyclohexylene) propane 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] Add 58.6g (0.300mol) of 2-cyano-3-propyl-2-enhexanoic acid methyl ester, 27.3g (0.390mol) of 2-methacrolein and 30.3g (0.300mol) of triethylamine to toluene in sequence In, the temperature was raised to reflux until the reaction was complete. Wash with warm, 1N dilute hydrochloric acid, dry, and concentrate to obtain 62.8 g of methyl 2-cyano-2-(2,6-diethyl-4-methyl-1-cyclohexenylidene) acetate. The yield is 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] Embodiment three: the preparation of 2-(2,6-diethyl-4-methylphenyl) malononitrile

[0037] Heat 10g (0.05mol) of 2-(2,6-diethyl-4-methyl-2-en-1-cyclohexylene)malononitrile and 0.5g of Pd / C to 220°C in a 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 the product 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 the 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 the control of weeds in crops such as wheat, and has a good market prospect. At present, the method of synthesizing pinoxaden is through 2-(2,6-diethyl-4-methylphenyl) malonate diester or 2-(2,6-diethyl-4-methyl Phenyl)malonamide and [1,4,5]-oxodiazepine 8-(2,6-diethyl-4-methylphenyl)tetrahydropyrazolo[1,2-d][1,4,5]oxadiazepine was obtained through cyclization reaction -7,9-dione, which is then reacted with pivaloyl chloride to obtain pinoxaden. [0003] 2-(2,6-diethyl-4-methylphenyl)malonate diester is made from 2-(2,6-dibromo-4-methylphenyl)malonate diester, It is prepared sequentially through metal-catalyzed coupling reaction with tributylvinylstanna...

Claims

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Application Information

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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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