CN102190629B - Method for preparing azoxystrobin from hydrocyanic acid in acrylonitrile waste gas - Google Patents

Abstract

The invention relates to a method for preparing azoxystrobin from hydrocyanic acid in acrylonitrile waste gas. A ratio of (3H)-benzofuran-2-one to a catalyst to hydrocyanic acid to dimethyl sulfate is 1.0:(1.0-1.5):(1.0-1.5):(0.9-2.5), and the method comprises the following steps of: reacting the (3H)-benzofuran-2-one with the hydrocyanic acid to obtain an intermediate of 3-formoxylbenzofuran-2(3H)-one; performing methoxylation by using the dimethyl sulfate to obtain 3-(alpha-methoxy)-methylenebenzofuran-2(3H)-one; and reacting with 4,6-dichloropyrimidine and 2-cyanophenol to obtain the azoxystrobin. The method has the advantages of simple operation of reaction process, low cost of raw materials, a small quantity of three wastes, light environmental pollution and high yield.

Description

Utilize vinyl cyanide waste gas-hydrogen cyanic acid to prepare the method for ICIA 5504

Technical field

The invention belongs to the organic synthesis field, particularly a kind of compound method of ICIA 5504.

Background technology

ICIA 5504 is methoxy acrylate (β-methoxyacrylates) sterilant or a strobilurins analogue; Have characteristics such as efficient, wide spectrum, systemic activity are strong; Nearly all Eumycetes germ evil all there is good active; Can be used for cereal, paddy rice, grape, yam, vegetables, fruit tree and other stem of plant foliar spray mists, seed treatment, also can carry out soil treating.ICIA 5504 uses to crop safety, no poisoning, to underground water and environmental safety under recommended dose.

The synthetic route of ICIA 5504 all is by 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone, and with 4,6-dichloro pyrimidine and the reaction of 2-cyanophenol generate.Document WO 2008043977, US20080214587 and Dong Jie etc. are at document " synthesizing of ICIA 5504 " reports such as (fine-chemical intermediate Vol.27 No.2, in April, 2007), and the synthetic of ICIA 5504 mainly is:

Wherein, 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone is to be reacted in the presence of diacetyl oxide by cumarone-2 (3H)-ketone and trimethyl orthoformate, and diacetyl oxide is promptly done catalyst for reaction; While generates methyl acetate with the methyl alcohol of by-product again, and reaction is proceeded, otherwise; Reaction times is very long; Reaction yield is very low, and cost is high, and a large amount of methyl acetate of by-product.

Summary of the invention

Technical problem to be solved by this invention is to overcome the deficiency that exists in the prior art, and a kind of new method for preparing ICIA 5504 is provided, and technology is fairly simple, yield is high, and cost is lower.

The present invention is a kind of method for preparing ICIA 5504, it is characterized in that at first by cumarone-2 (3H)-ketone in the presence of catalyzer, reacting with prussic acid; Generate 3-formyl benzofuran-2 (3H)-ketone, the latter re-uses the methyl-sulfate methoxylation, obtains 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone; Again with 4; 6-dichloro pyrimidine and the reaction of 2-cyanophenol generate ICIA 5504, wherein:

The reaction mass mol ratio is: cumarone-2 (3H)-ketone: catalyzer: prussic acid: methyl-sulfate=1.0:1.0～1.5:1.0～1.5:0.9～2.5;

Formylation reaction temperature-10～25 ℃, 2～4 hours reaction times;

0～60 ℃ of methoxy temperature of reaction, 1～4 hour reaction times;

Said catalyzer is hydrogen halide such as hydrogenchloride or hydrogen bromide

Concrete reaction formula is (catalyzer is example with hydrogenchloride):

Advantage of the present invention:

The cost of material that reaction is used is low, and yield is high, and product cost is low.

Embodiment

Below in conjunction with embodiment the present invention is described, but does not limit the present invention.

Embodiment 1:

In the 500ml reaction flask, add dry toluene 200ml, prussic acid 5.5g, cumarone-2 (3H)-ketone 27g; Stirring cools to below-10 ℃, feeds 7.5g exsiccant hydrogen chloride gas, and mixture reacted 2 hours for 0 ℃, adds then in the 200g trash ice to be hydrolyzed; Toluene layer is told in room temperature hydrolysis 30 minutes, and water re-uses the 100ml extracted in toluene; The combining methylbenzene layer through anhydrous magnesium sulfate drying, reclaims toluene and obtains pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-ketone.

Above-mentioned oily matter is dissolved among the 150mlDMF, adds salt of wormwood 42g powder simultaneously, drips the 32g methyl-sulfate under the room temperature, after dropping finishes; Continued insulation reaction 2 hours, and added in the 200ml water, the 300ml ether divides the extraction hydrolyzed solution three times, suitable quantity of water washing ether extracted liquid; Reclaim ether, add 30ml methyl alcohol, the cooling crystallization filters; Obtain the faint yellow crystallization 3-of 24.5g (α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone, 100～101 ℃ of fusing points, yield 70%.

Embodiment 2:

In the 500ml reaction flask, add dry toluene 200ml, prussic acid 6.75g, cumarone-2 (3H)-ketone 27g; Stirring cools to below 0 ℃, feeds 9.2g exsiccant hydrogen chloride gas, and mixture reacted 2 hours for 0 ℃, adds then in the 200g trash ice to be hydrolyzed; Toluene layer is told in room temperature hydrolysis 30 minutes, and water re-uses the 100ml extracted in toluene; The combining methylbenzene layer through anhydrous magnesium sulfate drying, reclaims toluene and obtains pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-ketone.

Above-mentioned oily matter is dissolved among the 150mlDMF, adds salt of wormwood 42g powder simultaneously, drips the 32g methyl-sulfate under the room temperature, after dropping finishes; Continued insulation reaction 2 hours, and added in the 200ml water, the 300ml ether divides the extraction hydrolyzed solution three times, suitable quantity of water washing ether extracted liquid; Reclaim ether, add 30ml methyl alcohol, the cooling crystallization filters; Obtain the faint yellow crystallization 3-of 28g (α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone, 100～101 ℃ of fusing points, yield 79.5%.

Embodiment 3:

In the 500ml reaction flask, add dry toluene 200ml, prussic acid 6.0g, cumarone-2 (3H)-ketone 27g; Stirring cools to below-10 ℃, feeds 8.2g exsiccant hydrogen chloride gas, and mixture reacted 2 hours for 0 ℃, adds then in the 200g trash ice to be hydrolyzed; Toluene layer is told in room temperature hydrolysis 30 minutes, and water re-uses the 100ml extracted in toluene; The combining methylbenzene layer through anhydrous magnesium sulfate drying, reclaims toluene and obtains pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-ketone.

Above-mentioned oily matter is dissolved among the 150mlDMF, adds salt of wormwood 35g powder simultaneously, drips the 26g methyl-sulfate under the room temperature, after dropping finishes; Continued insulation reaction 2 hours, and added in the 200ml water, the 300ml ether divides the extraction hydrolyzed solution three times, suitable quantity of water washing ether extracted liquid; Reclaim ether, add 30ml methyl alcohol, the cooling crystallization filters; Obtain the faint yellow crystallization 3-of 26.5g (α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone, 100～101 ℃ of fusing points, yield 75%.

Embodiment 4:

Control 20～25 ℃, 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone 17.6g and 4,6-dichloro pyrimidine 16.5g is dissolved among the methyl-formiate 60ml under stirring; In 8 hours, drip 28% sodium methylate 24.5g, add all sodium methoxide solutions after, mixture was stirred 2 hours; An amount of acetate is transferred reaction solution pH6～7, and low-boiling-point substance is removed in distillation from reaction mixture then, obtains residue; Add toluene 100ml and water 100ml, under 50 ℃, stirred the mixture 30 minutes, separate organic phase and water; Organic phase reclaim under reduced pressure toluene adds the 0.25g sal enixum at 140 ℃ of reaction 2h, obtains oily matter 25g; The content 75% of (E)-2-[2-(6-chloropyrimide-4-oxygen base) phenyl]-3-methoxy-methyl acrylate wherein, yield 65% refiningly directly is used for step reaction down.

Control 85～95 ℃; The mixed solution that drips 2-cyanophenol 11.5g, salt of wormwood 8.7g and water 25ml is in the 25.0g mixture that contains (E)-2-[2-(6-chloropyrimide-4-oxygen base) phenyl]-3-methoxy-methyl acrylate; Add the back and heat up, constantly steam water, 130 ℃ are incubated 3 hours.Then this mixture is cooled to 70 ℃, adds methyl alcohol 50m1, dissolve 30 minutes after-filtration, filtrating is cooled to and keeps crystallization in 2 hours about 0 ℃.Filter and promptly obtain (E)-2-[2-(6-cyano-benzene oxygen pyrimidine-4-oxygen base) phenyl]-3-methoxy-methyl acrylate, be ICIA 5504, content 95%, productive rate 82.0%.

Claims (1)

1. method of utilizing vinyl cyanide waste gas-hydrogen cyanic acid to prepare ICIA 5504; It is characterized in that at first being reacted in the presence of catalyzer by cumarone-2 (3H)-ketone and prussic acid, generate 3-formyl benzofuran-2 (3H)-ketone, the latter and methyl-sulfate reaction generate 3-(α-methoxyl group)-methylene radical benzo furans-2 (3H)-ketone; Again with 4; 6-dichloro pyrimidine and the reaction of 2-cyanophenol generate ICIA 5504, wherein:

The reaction mass mol ratio is: cumarone-2 (3H)-ketone: catalyzer: prussic acid: methyl-sulfate=1.0:1.0～1.5:1.0～1.5:0.9～2.5;

Formylation reaction temperature-10～25 ℃, 2～4 hours reaction times;

0～60 ℃ of methoxy temperature of reaction, 1～4 hour reaction times;

Said catalyzer is a hydrogenchloride.