- Method for preparing 2-arylmalonic acid derivative, intermediate and application thereof
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The invention provides a method for preparing a 2-arylmalonic acid derivative, an intermediate and application thereof. According to the method, a cyclohexadiene compound is used as a raw material, and the 2-arylmalonic acid derivative 3 is obtained through an isomerization reaction, a halogenation reaction in the presence of a halogenation reagent and a dehydrohalogenation aromatization reactionat a certain temperature in sequence. Compared with the prior art, the method has the following remarkable characteristics and advantages: (1) expensive metal catalysts are not needed in the reaction;(2) strong base with potential safety hazards is not needed in the reaction; and (3) the reaction is safe, the conditions are mild, the yield is high, the cost is low, and industrial production is facilitated.
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Paragraph 0054-0055
(2020/07/15)
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- Conjugated triene compound and preparation method and application thereof
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The invention provides a novel conjugated triene compound 1 and a preparation method and application thereof. By taking a 2-(cyclohexenyl) malonic acid derivative compound as a raw material, isomerization reaction, halogenation reaction in the presence of a halogenation reagent and dehydrohalogenation reaction at a certain temperature are sequentially carried out to obtain a conjugated triene compound 1; 2-aryl malonic acid derivative obtained by aromatization reaction of the conjugated triene compound 1 can be applied to synthesis of compounds with biological activity. The invention has the following remarkable characteristics and advantages: (1) the invention provides a novel conjugated triene compound 1 and a synthetic method thereof; and (2) the new compound 1 with the multifunctionalgroup can be used for synthesizing other compounds with important values through further functional group conversion reaction.
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- METHOD FOR PREPARING 2-ARYL MALONAMIDE AND APPLICATIONS THEREOF
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Disclosed are a method for preparing 2-aryl malonamide and an application thereof. This method uses 2-(cyclohexenylidene) malononitrile as a raw material, which undergoes an aromatization-hydrolyzation reaction in the presence of an oxidant and water to produce 2-aryl malonamide by one step. Compared to the prior art, the method for preparing 2-aryl malonamide of this application has the following features and advantages: (1) this method employs a completely different synthetic strategy; (2) raw materials used in this method are easily obtained; (3) this method not only has high yield, but also does not require expensive metal catalysts. This method is lower-cost, suitable for the industrial production.
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Paragraph 0025-0026
(2020/02/13)
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- One-pot method for preparing pinoxaden
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The invention discloses a method for preparing pinoxaden by a one-pot method, which takes 2-(2, 6-diethyl-4-methylphenyl) malonamide, 1-oxo-4, 5-diazacycloheptane and pivaloyl chloride as raw materials to prepare pinoxaden in one step by the one-pot method under the action of a catalyst, and the reaction general formula of the pinoxaden is shown as a formula (1). The method has the advantages of short route, simple operation and high conversion rate, can effectively reduce the amount of three wastes and prolong the online reaction time, and is very suitable for industrial production.
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Paragraph 0020-0043
(2020/12/15)
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- Method for synthesizing pinoxaden through 2,6-diethyl-4-methylphenyl malonate
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The invention relates to the field of organic synthesis, in particular to a method for synthesizing pinoxaden through 2,6-diethyl-4-methylphenyl malonate. The method comprises the following steps that1, the 2,6-diethyl-4-methylphenyl malonate reacts with hydrazine hydrate to form 4-(2,6-diethyl-4-methyl)-1,2,4,5-tetrahydropyrazole-3,5-diketone; 2, the 4-(2,6-diethyl-4-methyl)-1,2,4,5-tetrahydropyrazole-3,5-diketone is subjected to cyclization with diethylene glycol dimethanesulfonate or dibromo-diethylene glycol under the effect of triethylamine to generate 8-(2,6-diethyl-4-methylbenzene)-1,2,4,5-tetrahydropyrazole[1,2-d][1,4,5]oxo-dinitrogen-7,9-diketone; 3, the 8-(2,6-diethyl-4-methylbenzene)-1,2,4,5-tetrahydropyrazole[1,2-d][1,4,5]oxo-dinitrogen-7,9-diketone reacts with pivaloyl chloride under an alkaline condition to generate the pinoxaden. The method has the advantage that the use of expensive noble metal catalysts and hypertoxic cyaniding reagents is avoided, the adopted reagents are environmentally friendly, the cost is lowered, the process is simplified, the yield is high, the defects of the prior art are overcome, and the method is suitable for large-scale industrial production.
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Paragraph 0031; 0034; 0035; 0038; 0039; 0042
(2019/10/15)
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- Preparation method of pinoxaden
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The invention relates to the field of organic synthesis, in particular to a synthesis method of pinoxaden. The synthesis method comprises the following steps that under catalysis of copper chloride orcuprous chloride, 4-methyl-2,6-diethyl aniline reacts with 1,1-dichloroethylene and nitrous acid ester to generate a compound 1; the compound 1 reacts with sodium alcoholate, and a reaction product is subjected to acidic hydrolysis to obtain a compound 2; the compound 2 reacts with diester carbonate and strong base to obtain an intermediate 3; after diethylene glycol dimethanesulfonate reacts with hydrazine hydrate, salifying with hydrochloric acid is conducted to obtain an intermediate 4; the intermediate 3 and the intermediate 4 are subjected to ring forming under the effect of base to obtain a compound 5; and the compound 5 and pivaloyl chloride react under the effect of the base or base/DMAP to obtain the pinoxaden. The synthesis method of the pinoxaden does not use expensive or toxiccatalysts, does not need to adopt a protection/deprotection strategy, and has the characteristics of low cost and high atomic economy.
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Paragraph 0041; 0047; 0048; 0054
(2019/12/25)
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- A zuozuo lin grass ester synthesis method (by machine translation)
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The invention discloses a method for synthesizing zuozuo lin grass ester, which belongs to the field of chemical industry. The specific process is as follows: the 2, 6 - diethyl - 4 - methylaniline by thermal decomposition is diazotized with sodium nitrite to generate 2, 6 - diethyl - 4 - methyl bromo; the malonic acid diethyl ester is added to the [1, 4, 5] - oxa diazepine b hydrobromide and alkali catalyst, synthesis of dihydro - 1 H - pyrazolo [1, 2 - d] [1, 4, 5] oxygen mixed two aza - 7, 9 (2 H, 8 H) - dione, it with 2, 6 - diethyl - 4 - methyl bromophenylacetic after coupling reaction to obtain the 8 - (2, 6 - diethyl - 4 - methyl phenyl) and four hydrogen pyrazole [1, 2 - d] [1, 4, 5] oxygen and nitrogen weed - 7, 9 (2 H, 8 H) - dione; will it with new pivaloyl chloride reaction zuozuo lin grass ester synthesis of the final product. This invention shortens the synthesis step, the operation is simple, and the cost is reduced, high economical efficiency and less pollution to the environment. (by machine translation)
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Paragraph 0021; 0025; 0026; 0028
(2018/12/14)
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- Preparation process and application of dinitrogen oxide heterocyclic compound
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The invention relates to a preparation process and application of a dinitrogen oxide heterocyclic compound. The preparation process is characterized in that a N,N-diacyl dinitrogen oxide heterocycliccompound is used as the raw material, the N,N-diacyl dinitrogen oxide heterocyclic compound is allowed to have reaction with alkali in a nonpolar solvent to obtain the dinitrogen oxide heterocyclic compound, and the dinitrogen oxide heterocyclic compound is subjected to further reaction to be converted into herbicides such as pinoxaden. Compared with the prior art, the preparation process is highin yield, convenient to operate, little in waste gas, wastewater and solid waste and beneficial to industrial production.
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Paragraph 0037; 0038
(2018/07/30)
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- Preparation method and intermediate of pinoxaden
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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.
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Paragraph 0046; 0047
(2018/07/30)
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- Method for preparing 2-aryl malonamide and application thereof
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The invention provides a method for preparing 2-aryl malonamide and application thereof. According to the method, 2-(cyclohexadienylidene)malononitrile is used as a raw material and undergoes an aromatization-hydrolysis reaction under the action of an oxidizing agent and water so as to obtain 2-arylmalonamide in one step. Compared with the prior art, the method for preparing 2-arylmalonamide provided by the invention has the following remarkable features and advantages: (1) completely different synthesis strategies are adopted; (2) the raw material is simple and easily available; and (3) yieldis high, the use of expensive metal catalysts is avoided, cost is low, and the method is suitable for industrial production.
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Paragraph 0029-0030
(2018/11/04)
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- Preparation process and application of oxygen dinitrogen heterocyclic compound
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The invention provides a preparation process and application of an oxygen dinitrogen heterocyclic compound. The preparation process includes: enabling N-carbalkoxy hydrazine and disubstituted ether tobe in cyclization reaction under action of alkali to obtain a N-carbalkoxy oxygen dinitrogen heterocyclic compound; enabling the N-carbalkoxy oxygen dinitrogen heterocyclic compound to be in deprotection reaction with the alkali to obtain the oxygen dinitrogen heterocyclic compound. A new N-protection strategy is used, so that consumption of expensive protection agents is avoided, and reaction yield is increased. In addition, the preparation process has the advantages that three wastes are few, operation is simple and equipment is less prone to corrosion, and is conducive to industrial production.
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Paragraph 0061; 0062
(2018/07/30)
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- Preparation method and application of 2-aryl malonic acid derivative
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The invention provides a preparation method and application of 2-aryl malonic acid derivative. The preparation method includes: using a cyclohexenone derivative as a raw material to be in condensationreaction with a malonic acid derivative at the presence of a catalyst A to obtain a 2-(cyclohexenylene) malonic acid derivative; enabling the 2-(cyclohexenylene) malonic acid derivative to be in aromatization reaction under action of a catalyst B to obtain the 2-aryl malonic acid derivative. Compared with the prior art, the preparation method is totally different from existing methods in synthesis strategy and used raw materials and has the advantages that reaction raw materials are easy to obtain; no solvent is needed during reaction, and yield is high; the catalyst B can be recycled, so that cost is lowered; the preparation method is high in yield, few in three wastes, environment-friendly and conducive to industrial production.
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Paragraph 0058-0059
(2018/07/30)
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- Preparation method of pinoxaden
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The invention relates to a preparation method of pinoxaden. The preparation method comprises the following steps: carrying out sandmeyer reaction on 2,6-diethyl-4-methylaniline to obtain 2,6-diethyl-4-methylbromobenzene; then coupling the 2,6-diethyl-4-methylbromobenzene with malononitrile under the catalysis of copper iodide and the like to obtain 2,6-di-ethyl-4-methylphenyl malononitrile; finally, hydrolyzing in a hydrogen peroxide solution to obtain 2,6-diethyl-4-methylphenyl malonamide; afterwards, reacting the 2,6-diethyl-4-methylphenyl malonamide with [1,4,5]-oxa-diazepine dihydrobromide under the action of triethylamine to obtain 8-(2,6-diethyl-4-methyl benzene)tetrahydropyrazole [1,2d][1,4,5]-oxa-diazepine-7,9-dione, and finally reacting the 8-(2,6-diethyl-4-methyl benzene) tetrahydropyrazole[1,2d][1,4,5]-oxdiazepine-7,9-dione with pivalyl chloride to obtain the pinoxaden. According to the preparation method disclosed by the invention, by adopting a catalyst with low price, the production cost is reduced; besides, hydrogen peroxide-alkali is adopted in a preparation process to serve as a hydrolyzed system, so that environmental pollution is greatly reduced.
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- Aryldiones incorporating a [1,4,5]oxadiazepane ring. Part I: Discovery of the novel cereal herbicide pinoxaden
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Derivatives of the new class of 3-hydroxy-4-phenyl-5-oxo-pyrazolines were optimized towards both herbicidal activity on key annual grass weed species and selectivity in small grain cereal crops. The generic structure can be separated into three parts for the analysis of the structure-activity relationships, namely the aryl, the dione with its prodrug forms and the hydrazine moiety. Each area appears to play distinct and different roles in overall expression of biological performance which is further beneficially influenced by adjuvant response and safener action. Pinoxaden 6, a novel graminicide for use in wheat and barley incorporating a [1,4,5]oxadiazepane ring, eventually emerged as a development candidate from the discovery and optimization process.
- Muehlebach, Michel,Boeger, Manfred,Cederbaum, Fredrik,Cornes, Derek,Friedmann, Adrian A.,Glock, Jutta,Niderman, Thierry,Stoller, Andre,Wagner, Trixie
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experimental part
p. 4241 - 4256
(2009/10/02)
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