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Preparation method for 2-(cyclohexenyl) malonic acid derivative and application thereof

A technology of cyclohexenyl and malonic acid, which is applied in the direction of botanical equipment and methods, applications, and preparation of carboxylic acid nitriles, can solve the problems of unsuitability for industrial production, limited application, high cost, etc., and is beneficial to industrial production, The effect of less waste and mild conditions

Active Publication Date: 2018-07-10
ORIENTAL LUZHOU AGROCHEM
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

This reaction can obtain the target product with a moderate yield, but requires the use of a large amount of metal reagents and ultra-low temperature operation, resulting in high cost and heavy pollution of the method, which is not suitable for industrial production
[0005] Due to the lack of effective methods for synthesizing this type of 2-(cyclohexenylene) malonic acid derivatives with multifunctional groups, the application of this type of compound in organic synthesis, especially in drug synthesis, is greatly limited

Method used

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  • Preparation method for 2-(cyclohexenyl) malonic acid derivative and application thereof
  • Preparation method for 2-(cyclohexenyl) malonic acid derivative and application thereof
  • Preparation method for 2-(cyclohexenyl) malonic acid derivative and application thereof

Examples

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preparation example Construction

[0031] Preparation of 2-(4-heptylene)malononitrile

[0032] Add 65.0 g (0.569 mol) of 4-heptanone, 39.4 g (0.569 mol) of malononitrile, 6.6 g (0.086 mol) of ammonium acetate, 10.3 g (0.171 mol) of acetic acid, and toluene into the reaction flask in sequence, and reflux for water separation reaction After the reaction was complete, the temperature was lowered, washed with water, concentrated and purified to obtain 84.9 g of the product 2-(4-heptylene)malononitrile, with a yield of 92%. 1 H NMR (CDCl 3 , 500MHz, TMS): δ2.57-2.53 (m, 4H), 1.64-1.60 (m, 4H), 1.02 (t, J=7.5Hz, 6H). 13 C NMR (CDCl 3 ,125MHz): δ186.08, 111.88, 85.91, 37.47, 21.44, 12.81.

[0033] Preparation of 2-(1-(4-methoxyphenyl)-2-propylene)malononitrile

[0034] 82.1g (0.50mol) of 1-(4-methoxyphenyl)-2-propanone, 33.0g (0.50mol) of malononitrile, 5.8g (0.075mol) of ammonium acetate, 9.0g (0.15mol) of acetic acid, Add toluene into the reaction flask in turn, reflux and divide water for reaction. After the rea...

Embodiment 1

[0035] Example 1: Preparation of 2-(2,6-diethyl-4-methyl-2-ene-1-cyclohexylene)malononitrile

[0036] Add 24.3g (0.15mol) of 2-(4-heptylene)malononitrile, 10.5g (0.15mol) of 2-methacrolein and 15.2g (0.15mol) of triethylamine into toluene in turn, and heat up to reflux for reaction until the reaction is complete. Cool down, wash with 1N dilute hydrochloric acid, dry, concentrate, and purify to obtain 25.7 g of the product 2-(2,6-diethyl-4-methyl-2-en-1-cyclohexylidene) malononitrile with a yield of 80 %. 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

[0037] Example 2: 2-(2,6-diethyl-4-methyl-2-ene-1-cyclohexylene)malononitrile and 2-(2,6-diethyl-4-methyl- Preparation of 3-ene-1-cyclohexylene)malononitrile

[0038] Add 25.0 g (0.154 mol) of 2-(4-heptylethylene) malononitrile, 14.0 g (0.200 mol) of 2-methacrolein and 15.6 g (0.154 mol) of triethylamine into toluene in sequence, and heat up to reflux for reaction until the reaction is complete. Cool down, wash with 1N dilute hydrochloric acid, dry, and concentrate the solvent to obtain 2-(2,6-diethyl-4-methyl-2-en-1-cyclohexylene)malononitrile and 2-(2,6-di 30.4 g of a mixture of ethyl-4-methyl-3-en-1-cyclohexylene)malononitrile. The ratio of the two was 91:9 by GC-MS analysis.

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Abstract

The invention provides a preparation method for a 2-(cyclohexenyl) malonic acid derivative and application thereof. The method takes polylefin and a 2-substituted malonic acid derivative as raw materials, the two materials are subjected to a cyclization reaction in the presence of catalyzer, and the 2-(cyclohexenyl) malonic acid derivative is obtained. Compared with the prior art, the preparationmethod adopts a completely different strategy and has the special functions that (1) a 2-(2, 6-disubstituted cyclohexenyl) malonic acid derivative can be more efficiently synthesized; (2) the reactionyield is high, the reaction conditions are mild, the three wastes are less, and the method is beneficial to industrial production. More importantly, the method expands the application of the 2-(cyclohexenyl) malonic acid derivative in organic synthesis, especially the synthesis of a 2-aryl malonic acid derivative and corresponding pesticides such as a herbicide of pinoxaden.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a new method for preparing 2-(cyclohexenylene)malonic acid derivatives and its application. Background technique [0002] 2-(Cyclohexenylene)malonic acid derivatives are a class of organic compounds with multifunctional groups. There are currently two methods for preparing such compounds (J. Mol. Cata. A. Chem. 2003, 195(1-2), 263; Organometallics 1989, 8(10), 2474). [0003] The first method for preparing 2-(cyclohexenylene) malonic acid derivatives is starting from cyclohexenone derivatives (J.Mol.Cata.A.Chem.2003,195(1-2),263 ). Cyclohexenone derivatives and malonic acid derivatives undergo Knoevenagel condensation reaction to obtain 2-(cyclohexenylene) malonic acid derivatives. This method requires the highly active cyclohexenone. For the cyclohexenone raw material substituted at the 6-position with low activity, the Knoevenagel condensation reaction yield is ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/30C07C253/34C07C255/31C07C255/33C07C67/30C07C69/612C07D498/04
CPCC07C67/30C07C253/30C07C253/34C07C255/31C07D498/04C07C255/33C07C69/612A01N43/90C07C67/317C07C67/343C07C2601/16C07C69/608C07C55/28C07C13/20C07C67/22C07C69/38
Inventor 孙殷卫王忠元张盼陈邦池
Owner ORIENTAL LUZHOU AGROCHEM
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