Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
  • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/32—One oxygen, sulfur or nitrogen atom
  • C07D239/34—One oxygen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/52—Two oxygen atoms

Definitions

• the invention relates to a novel preparation method of an agricultural fungicide, azoxystrobin and the like. Background technique
• Azoxystrobin is the first commercially available --methoxyacrylates fungicide developed by Jielikon.
• the chemical name of azoxystrobin is (E)-2-(2-(6- (2-Cyanophenoxy)pyrimidine _4-oxy)phenyl)-3-decyloxy decyl acrylate, the mechanism of action is to act as a mitochondrial respiratory inhibitor, ie by blocking electron transfer between cytochrome b and d To inhibit the mitochondrial respiration, and play a bacteriostatic effect.
• the fungicide can control almost all fungi, oomycetes, algae, sclerotium and deuteromycetes, and through stem and leaf treatment, seed treatment in grains, rice, grapes, potatoes, Vegetables, fruit trees, legumes, and other crops are used, and many patent documents have reported their synthetic methods, such as patents EP-A-0382375, WO92/08703A1, GB229174, and the like.
• Method (B) is one of the earliest introductions. It is also the first synthetic method introduced in the patent literature. Although this route can realize the synthesis of products, the protection of raw materials and the deprotection of intermediates and series conversion increase the reaction steps. Summary of the invention
• the group is hydrogen, a Crdo hydrocarbon group, a 6-(2-cyanophenoxypyrimidin)-4-yl group or a 6-position pyrimidin-4-yl group substituted by a halogen.
• the terminology in this specification includes fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.
• the intermediate product obtained in the step (1) is subjected to a thiolation reaction with a thiolation reagent in the presence of a base at - 20 ° C to 100 ° C to obtain a compound of the formula (I).
• the Lewis acid used in the present invention broadly refers to any Lewis acid, without any limitation or exclusion, and may be any Lewis acid known to those skilled in the art, for example, titanium tetrachloride, aluminum trichloride, aluminum chlorochloride, Tin chloride, iron chloride, chlorinated, boron trifluoride etherate or the like is preferably titanium tetrachloride.
• the Lewis acid is used in an amount such that the oxime acylation reaction proceeds smoothly.
• the Lewis acid may be used in an amount of from 0.1 to 6.0 molar equivalents, preferably from 1.0 to 3.0 molar equivalents, based on the amount of the compound of the formula (II) being 1.00 molar equivalent.
• the oxime acylating agent used in the present invention includes all oxime acylating agents, and may be any oxime acylating agent known to those skilled in the art, for example, decyl decanoate, ethyl decanoate, tridecyl decanoate, Triethyl orthoformate or the like is preferably tridecyl orthoformate.
• the amount of the oxime acylating agent is such that the oxime acylation reaction proceeds smoothly.
• the guanidration reagent may be used in an amount of from 1.0 to 10.0 molar equivalents, preferably 1.0. - 3.0 molar equivalents.
• the organic base in the present invention includes all kinds of organic bases, such as amines, alcohol metals, etc., preferably tertiary amines in amines such as tridecylamine, triethylamine, tributylamine, diisopropylethylamine and pyridine. Wait. The amount of the organic base to be used is such that the reaction proceeds smoothly.
• the amount of the compound of the formula (II) is 1.00 molar equivalent
• the amount of the organic base may be 0.2 to 10.0 molar equivalents, preferably 2.0 to 6.0 molar equivalents.
• the base in the present invention includes all inorganic bases and organic bases, and may be any base known to those skilled in the art, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, cesium.
• Sodium alkoxide, sodium ethoxide, sodium t-butoxide and the like are preferably sodium hydroxide or potassium hydroxide.
• the amount of the base is such that the thiolation reaction proceeds smoothly.
• the amount of the thiolation reagent should be such that the thiolation reaction proceeds smoothly, for example, based on the amount of the formula (II) of 1.00 molar equivalent, the thiolization test
• the agent may be used in an amount of from 0.8 to 6.0 molar equivalents, preferably from 1.0 to 3.0 molar equivalents.
• the oxime acylation reaction is suitably carried out in an aprotic solvent which is a solvent which does not give protons or accept protons, such as [3 ⁇ 4 generation hydrocarbons, benzene, saturated hydrocarbons, dimercaptosulfoxides, etc., preferably [3 ⁇ 4 generation hydrocarbons)
• an aprotic solvent which is a solvent which does not give protons or accept protons
• the compound of the formula (II) is in an aprotic solvent at -20 ° C to 200 ° C, preferably -20 ° C to 100 ° C, more preferably -10 ° C to 50 ° C, More preferably, it is reacted with a hydrazylation reagent in the presence of a temperature of -5 ° C to 5 ° C in the presence of a Lewis acid, and after stirring for a while, an organic base is further added, and stirring is further continued to further promote the reaction.
• the obtained reaction mixture was washed with 40 mL of 10% hydrochloric acid, dried over anhydrous magnesium sulfate
• the brown viscous material was dissolved in 100 mL of hot benzene, cooled to room temperature, and 0.9 g of benzyltriethylammonium chloride, 15 g of 20% aqueous sodium hydroxide, and 12.6 g of dinonyl sulfate were added. After the addition was completed, the mixture was stirred at room temperature for 5 hours, and further heated to 50 ° C, and then reacted for 1 hour while stirring. The resulting mixture was washed with water (50 mL), evaporated and evaporated.
• the brown viscous material was dissolved in 100 mL of hot benzene, cooled to room temperature, and 0.9 g of benzyltriethylammonium chloride, 15 g of 20% aqueous sodium hydroxide, and 12.6 g of dinonyl sulfate were added. After the addition was completed, the mixture was stirred at room temperature for 5 hours, and further heated to 50 ° C, and then reacted for 1 hour while stirring. The resulting mixture was washed with EtOAc (EtOAc) (EtOAc). Melting point: 125- 126.5 ° C. NMR (500 NMR, CDC1 3 ): ⁇ 3.70 (s, 3H), 3.83 (s, 3H), 6.68 (d, Is), 6.82-7.02 (m, 2H), 7.12-7.32 (m, 2H).
• Azoxystrobin was prepared according to the method of Example 2 at the following different reaction temperatures, and the results are shown in Table 1. Among them, in Example 7 and Example 8, dimercaptosulfoxide was used in place of dichlorodecane.
• azoxystrobin was prepared in accordance with the method of Example 2 under the following various reaction reagents, and the results are shown in Table 2. Table 2 Preparation of azoxystrobin under different reaction reagents
• the brown viscous material was dissolved in 100 mL of hot benzene, cooled to room temperature, and 0.7 g of benzyltriethylammonium chloride, llg of 20% aqueous sodium hydroxide, and 9.5 g of dinonyl sulfate were added. After the addition was completed, the mixture was stirred at room temperature for 5 hours, and further heated to 50 ° C, and then reacted for 1 hour while stirring. The obtained mixture was washed with 50 mL of water, and then evaporated and evaporated.

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• 2007
  • 2007-10-24 CN CNB2007101633868A patent/CN100564362C/zh active Active
• 2008
  • 2008-09-19 WO PCT/CN2008/072429 patent/WO2009052719A1/zh not_active Ceased
  • 2008-09-19 BR BRPI0812999-1A2A patent/BRPI0812999A2/pt not_active IP Right Cessation
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  • 2008-09-19 US US12/668,219 patent/US8278445B2/en active Active

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