CN108863845B - Preparation method of trifloxystrobin and intermediate thereof - Google Patents
Preparation method of trifloxystrobin and intermediate thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of trifloxystrobin; the preparation reaction of trifloxystrobin is as follows:
r is selected from: c2～C5Straight chain alkyl or C3～C5A branched alkyl group; in the bromination reaction, NBS or 1, 3-dibromo-5, 5-dimethylhydantoin is selected as a brominating agent.
Description
Technical Field
The invention relates to a preparation method of a compound, in particular to a preparation method of trifloxystrobin and an intermediate 2-methyl-alpha-methoxyimino phenylacetamide thereof.
Background
Trifloxystrobin (trifloxystrobin, trade name Flint) chemical name: (2Z) -2-methoxyimino-2- [2- [ [1- [3- (trifluoromethyl) phenyl ] ethylamino ] oxymethyl ] phenyl ] acetic acid methyl ester:
the trifloxystrobin is a high-efficiency, safe and environment-friendly strobilurin fungicide, is used as a novel mitochondrial respiration inhibitor, has the characteristics of high efficiency, broad spectrum, low toxicity, environmental friendliness, unique action mechanism and the like, and is a hotspot of fungicide research at present. The compound bactericide is mainly used for stem and leaf treatment, has special effects on powdery mildew and leaf spot, and also has good activity on rust disease, downy mildew, damping off and apple scab.
Chinese patent No. [ CN 1049426C,2000] takes o-bromomethyl phenylacetate as a starting material, firstly generates etherification reaction with phenylglyoxylic acid, then generates o-methoxyaminophenylacetic acid methyl ester by reaction with methanol under an acidic condition, then performs oximation reaction with m-trifluoromethyl acetophenone, and prepares trifloxystrobin by oximation of tert-butyl nitrite and methylation of dimethyl sulfate, wherein the total yield is 40.5%:
the route has five steps, the reaction steps are reasonable, but the expensive o-bromomethyl phenylacetate is used in the reaction.
The world patent [ WO 9520569,1995] researches trifloxystrobin, namely, firstly carrying out etherification reaction on o-bromomethylphenyl boric acid and m-trifluoromethyl acetophenone oxime, and then carrying out condensation reaction on the o-bromomethylphenyl boric acid and 2-chloro-2-methoxy imine methyl acetate under the catalysis of palladium to generate the trifloxystrobin:
the synthetic route is short, but the price of the raw material o-bromomethylbenzeneboronic acid is high; the yield is low due to the harsh conditions for the synthesis of methyl 2-chloro-2-methoxyiminoacetate and the presence of isomerization.
U.S. Pat. No. [ US 5194662,1993] uses methyl o-methylphenylacetate as an initial raw material, and obtains methyl o-bromomethylphenylacetate through bromination reaction, then the methyl o-bromomethylphenylacetate is condensed with m-trifluoromethyl acetophenone oxime, and then the trifloxystrobin is obtained through oxidation and oximation reactions:
the third oxidation step of the route is difficult.
Nibepo et al CN 101941921,2011 and ginger billow et al organic chemistry 2014,34(4),774-782 take toluene or substituted toluene as raw material, under the catalysis of anhydrous aluminum trichloride, take Friedel-crafts acylation reaction with oxalyl chloride monomethyl ester, then oximation and chlorination are carried out, and finally condensation with m-trifluoromethyl acetophenone oxime is carried out to obtain trifloxystrobin, wherein the total yield is 50.2%:
the friedel-crafts acylation reaction in the route has lower selectivity, which leads to lower yield; the price of the oxalyl chloride monomethyl ester is higher.
Plum flame and the like [ university of china, 2005,39(1),54-56] take o-bromotoluene as a raw material, and react with oxalyl chloride monomethyl ester under the action of an organic copper lithium reagent to generate a coupling reaction to obtain o-methyl benzoyl methyl formate, and then the o-methyl benzoyl methyl formate reacts with methoxylamine hydrochloride to generate an intermediate oxime ester, and the intermediate oxime ester is obtained through bromination and oximation reactions to obtain trifloxystrobin, wherein the total yield is 25%:
the coupling reaction in the first step of the route is complex, the conditions are harsh, the number of byproducts is large, and the process has high requirements on equipment.
Chinese patents [ CN 1560027,2005; CN 1793115,2006] o-methylacetophenone is used as a raw material, oxidized by potassium permanganate under the alkalescent condition, esterified, oximated and brominated, and finally condensed with m-trifluoromethyl acetophenone oxime to obtain trifloxystrobin, wherein the total yield is 39%:
chenwei et al [ chemical research, 2014,25(1),16-19] use o-tolylacetic acid as raw material, firstly oxidize by potassium permanganate under alkaline condition, then carry out esterification, oximation and bromination reactions, finally generate trifloxystrobin by condensation reaction, and the total yield is 17%:
in the potassium permanganate oxidation method, the reaction process is difficult to control by using potassium permanganate as an oxidant, and methyl can be oxidized.
World patents [ WO 2013144924, US 5221762,1993], Chen-Can and so on [ fine chemical intermediates, 2004,34(5),25-26] and Ron and so on [ fine chemical intermediates, 2016,46(2),19-21] use o-methylbenzoic acid as raw material, and reflux with thionyl chloride to obtain o-methylbenzoyl chloride; then carrying out cyanation, esterification, oximation and bromination on the obtained intermediate, and etherifying the intermediate with m-trifluoromethyl acetophenone oxime to obtain trifloxystrobin, wherein the total yield is 16.2%:
the raw materials of the route are cheap and the operation is simple, but the second step reaction uses sodium cyanide with high toxicity.
Deluxe et al [ pesticide 2011,50(3),187-191] and chinese patent [ CN 101139308,2008] use o-hydroxymethyl benzoic acid lactone as a raw material, generate o-chloromethyl benzoyl chloride through ring opening, react with sodium cyanide as a cyanogen source to prepare o-chloromethyl benzoyl cyanide, and finally etherify the intermediate obtained through esterification and oximation with m-trifluoromethyl acetophenone oxime to obtain trifloxystrobin with a total yield of 22%:
according to the method, phthalide is used for ring opening to generate acyl chloride and chloromethyl, and the reaction conditions in each step are mild; but the second reaction step uses sodium cyanide, which is highly toxic.
Chinese patent [ CN 103524378,2015] takes o-tolylacetic acid as a raw material, and synthesizes trifloxystrobin through cyclization, oxidation, hydrolysis, oximation, chlorination and etherification, wherein the yield is 50.6%:
the raw materials of the route are cheap and easy to obtain, and the yield is high. But the oxidation process uses the expensive oxidant CAT 9901.
According to Chinese patent [ CN 105294490,2016] and world patent [ WO 2010089267], an o-hydroxymethylphenylacetic acid lactone method is used as a raw material, trifloxystrobin is obtained through 4 steps of reaction, and the total yield is 25%:
the price of o-hydroxymethylphenylacetic acid lactone used as a raw material in the route is high, and the first-step oximation reaction needs anhydrous and anaerobic operation.
Firewood and the like [ pesticide 2013,52(4), 258-:
the diazotization reaction condition adopted by the route is harsher, and more byproducts are generated.
Plum red [ the master thesis of the university of Hebei science and technology, 2015] takes o-methyl phenylacetonitrile as a raw material, and is subjected to oximation, methylation, hydrolysis, bromination and etherification to synthesize trifloxystrobin, wherein the yield is 30.8%:
the raw materials of the route are cheap and easy to obtain, and the reaction conditions are relatively mild. However, concentrated sulfuric acid is used in the esterification process, so that the equipment is highly corrosive.
The method is characterized in that the method takes o-methylbenzyl chloride as a starting material, and obtains a key intermediate 2-bromomethyl-alpha-methoxyimino phenylacetic acid methyl ester of trifloxystrobin through cyanation, oximation, methylation, esterification and bromination, wherein the yield is 41.6%.
The route is relatively mild, but uses highly toxic sodium cyanide.
U.S. Pat. No. 3, 5145980,1992 discloses a process for preparing 2-bromomethyl-alpha-methoxyimino methyl phenylacetate by reacting o-methylbenzaldehyde as a raw material with methoxyamine hydrochloride after cyanation and oxidation and then brominating, with a total yield of 16%:
the route is long, the total yield is low, and the first step reaction uses potassium cyanide with high toxicity.
Weixinghui et al [ Zhejiang chemical engineering, 2013,44(2),7-9] use o-methylphenylacetic acid as raw material, and synthesize 2-bromomethyl-alpha-methoxyimino phenylacetic acid methyl ester through esterification, oximation, methylation and bromination, with a total yield of 32%:
the reaction condition of the route is mild, and the method is a better method for preparing 2-bromomethyl-alpha-methoxyimino phenylacetic acid methyl ester.
Chinese patent [ CN 101711232,2010] uses o-chlorobenzyl chloride as raw material, uses morpholine to protect methylene, and then obtains 2-chloromethyl-alpha-methoxyimino phenylacetic acid methyl ester through 4 steps of Grignard reaction, esterification and oximation, the total yield is 22%:
the second step of the process is difficult to control, and the yield is 30.3%.
The world patent [ WO 9714688,1997] takes o-tolylacetonitrile as a raw material, and 2-chloromethyl-alpha-methoxyimino phenylacetic acid methyl ester is obtained through 5 steps of reaction, wherein the total yield is 23%:
the third reaction step of the route requires anhydrous and oxygen-free operation.
U.S. Pat. No. 4, 5756811,1998 discloses a method for preparing trifloxystrobin intermediate 2-chloromethyl- α -methoxyimino phenylacetic acid methyl ester by 3-step reaction using N, N-dimethylbenzylamine and dimethyl oxalate as raw materials, wherein the total yield is 55%:
the method has the advantages of relatively simple route and high yield, but n-butyllithium is required for the first step of reaction, and the reaction conditions are harsh.
In conclusion, the existing technology for preparing trifloxystrobin has the defects of difficult raw material source, high price, long synthesis route, harsh reaction conditions, difficult process control, high requirement on production equipment, high safety and environmental protection pressure, low yield and the like.
Disclosure of Invention
The invention aims to provide a preparation method of 2-methyl-alpha-methoxyimino phenylacetamide shown in a chemical structural formula I; the method is characterized by comprising the following preparation reactions:
r is selected from: c2～C5Straight chain alkyl or C3～C5A branched alkyl group.
The invention aims to provide a preparation method of 2-methyl-alpha-methoxyimino phenylacetamide, which comprises the following steps: the preparation method is characterized by comprising the following preparation operation processes:
stirring and dissolving 12mmol of sodium hydroxide and 10mL of methanol at 40 ℃, adding 5mmol of o-tolylacetonitrile, adding 7.5mmol of tert-butyl nitrite, heating to 60 ℃, and reacting for 1 h. The 2-methyl-alpha-hydroxyimino phenylacetonitrile is obtained by post-treatment with the yield of 100 percent.
Stirring 4mmol of 2-methyl-alpha-hydroxyiminophenylacetonitrile, 15mL of acetonitrile and 8mmol of KOH or NaOH at the temperature of 35-40 ℃ for 0.5h, cooling, slowly dropwise adding 4.8mmol of dimethyl sulfate at the temperature of below 10 ℃, stirring at the temperature of 35 ℃ for 3h, and performing aftertreatment to obtain 0.626g of light yellow oily liquid with the yield of 90%.
Adding 5mmol of 20% potassium hydroxide solution into 5mmol of 2-methyl-alpha-methoxyimino phenylacetonitrile and 5mL of ethanol, reacting for 3h at 60 ℃, and performing post-treatment to obtain 0.900g of (E) -2-methyl-alpha-methoxyimino phenylacetamide with single configuration, wherein the yield is 92.5% and the melting point is 123-125 ℃.
The invention also provides a method for preparing trifloxystrobin from 2-methyl-alpha-methoxyimino phenylacetamide shown in a chemical structural formula I; the method is characterized by comprising the following preparation reactions:
r is selected from: c2～C5Straight chain alkyl or C3～C5A branched alkyl group; in the bromination reaction, NBS or 1, 3-dibromo-5, 5-dimethylhydantoin is selected as a brominating agent.
Compared with the prior art, the method has the advantages of mild reaction conditions, cheap and easily-obtained raw materials, simple and convenient post-treatment and high total yield (43.5%). The invention adopts the key intermediate of 2-methyl-alpha-methoxyimino phenylacetamide to prepare the trifloxystrobin for the first time.
Detailed Description
The following examples are intended to illustrate the invention without further limiting it.
Example 1
Preparation of 2-methyl-alpha-hydroxyiminophenylacetonitrile
0.480g (12mmol) of sodium hydroxide and 10mL of methanol are dissolved by stirring at 40 ℃, 0.655g (5mmol) of o-tolylacetonitrile is added, and 0.773g (7.5mmol) of nitroso is addedAnd (4) tert-butyl ester, heating to 60 ℃, monitoring by TLC, and reacting for 1 h. And (3) carrying out desolventizing under reduced pressure to recover methanol, adding 20mL of water, adjusting the pH value to be neutral by hydrochloric acid, extracting by ethyl acetate, drying by anhydrous sodium sulfate, carrying out desolventizing to recover the ethyl acetate, wherein the yield is 100%, and directly using the ethyl acetate in the next step. (E) -2-methyl- α -hydroxyiminophenylacetonitrile:1H NMR(400MHz，CDCl3)：13.78(s，1H，OH)，7.53～7.32(m，4H，C6H4)，2.44(s，3H，CH3) (Z) -2-methyl- α -hydroxyiminophenylacetonitrile:1H NMR(400MHz，CDCl3)：13.78(s，1H，OH)，7.46～7.33(m，4H，C6H4)，2.25(s，3H，CH3)。
example 2
Preparation of 2-methyl-alpha-methoxyimino phenylacetonitrile
0.640g (4mmol) of 2-methyl-alpha-hydroxyiminophenylacetonitrile, 15mL of acetonitrile, 0.448g (8mmol) of powdered KOH, stirring at 35-40 ℃ for 0.5h, cooling, slowly adding dropwise 0.605g (4.8mmol) of dimethyl sulfate below 10 ℃, stirring at 35 ℃ for 3h, and monitoring by TLC. Standing, performing suction filtration, and performing rotary evaporation to recover acetonitrile. The residue was dissolved in ethyl acetate, neutralized with dilute hydrochloric acid, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, desolventized, and separated by column chromatography (PE: EA ═ 8:1) to give 0.626g of 2-methyl- α -methoxyiminophenylacetonitrile in a yield of 90%. (E) -2-methyl- α -methoxyiminophenylacetonitrile:1H NMR(400MHz，CDCl3)：7.56～7.25(m，4H，C6H4)，4.20(s，3H，NOCH3)，2.51(s，3H，CH3) (ii) a (Z) -2-methyl- α -methoxyiminophenylacetonitrile:1H NMR(400MHz，CDCl3)：7.38～7.25(m，4H，C6H4)，4.06(s，3H，NOCH3)，2.31(s，3H，CH3)。
example 3
Preparation of 2-methyl-alpha-methoxyimino phenylacetamide
0.870g (5mmol) of 2-methyl-. alpha. -methoxyiminophenylacetonitrile and 5mL of ethanol were added with 1.400g (5mmol) of 20% potassium hydroxide or NaOH solution, and reacted at 60 ℃ for 3 hours, followed by TLC. The solvent was recovered by rotary evaporation, the residue was poured into 20mL of ice water, and the solid precipitated, filtered off with suction and washed with water. Drying the filter cake, extracting the filtrate with ethyl acetate, drying with anhydrous sodium sulfate, desolventizing and drying to obtain 0.900g of 2-methyl-alpha-methoxyimino phenylacetamide, wherein the yield is 92.5 percent and the melting point is 123-125 ℃.1H NMR(400MHz，DMSO-d6)：7.97(s，1H，NH2)，7.73(s，1H，NH2)，7.40～7.22(m，4H，C6H4)，3.89(s，3H，NOCH3)，2.42(s，3H，CH3)。
Example 4
Preparation of 2-methyl-alpha-methoxyimino methyl phenylacetate
0.960g (5mmol) of 2-methyl-alpha-methoxyimino phenylacetamide and methanol, introducing hydrogen chloride gas, stirring for 12h at 60 ℃, monitoring by TLC, desolventizing under reduced pressure, adding 20mL of water, extracting with ethyl acetate, washing with saturated sodium bicarbonate, washing with water, drying with anhydrous sodium sulfate, desolventizing under reduced pressure, and drying to obtain 2-methyl-alpha-methoxyimino phenylacetic acid methyl ester, wherein the yield is 90.5%, and the melting point is 69-71 ℃.1H NMR(400MHz，DMSO-d6)：7.34～7.09(m，4H，C6H4)，3.94(s，3H，NOCH3)，3.76(s，3H，OCH3)，2.09(s，3H，CH3)。
Example 5
(E) Preparation of (E) -2-bromomethyl-alpha-methoxyiminophenylacetic acid methyl ester
0.414g (2.00mmol) of methyl (E) -2-methyl-. alpha. -methoxyimino-phenylacetate, 5mL of dichloroethane, 0.300g (1.05mmol) of 1, 3-dibromo-5, 5-dimethylhydantoin (abbreviated as dibromohydantoin), 0.100g (0.61mmol) of AIBN, reaction at 82 ℃ for 5.0h, monitoring by TLC and desolventizing. Adding 5mL of water, extracting with ethyl acetate, washing with sodium hydroxide solution, drying with anhydrous sodium sulfate, desolventizing, and separating by column chromatography (PE: EA is 20:1) to obtain 0.472g of (E) -2-bromomethyl-alpha-methoxyimino phenylacetic acid methyl ester with the yield of 82.5%.1H NMR(400MHz，CDCl3)：7.52～7.35，7.17～7.12(m，4H，C6H4)，4.34(s，2H，CH2)，4.07(s，3H，NOCH3)，3.88(s，3H，OCH3)。
Example 6
Preparation of m-trifluoromethyl acetophenone oxime
1.000g (5.0mmol) of m-trifluoromethyl acetophenone, 0.5g (7.0mmol) of hydroxylamine hydrochloride and 10mL of ethanol are added, 0.350g (8.8mmol) of sodium hydroxide is added to adjust the pH value to 8.0, the mixture is refluxed for 1.0h, poured into ice water, adjusted to the pH value of 2.0 by hydrochloric acid, a large amount of white solid is separated out, and the white solid is filtered, washed and dried to obtain 0.965g of white solid m-trifluoromethyl acetophenone oxime with the yield of 95.5 percent.1H NMR(400MHz，CDCl3)：7.92～7.48(m，4H，C6H4)，2.32(s，3H，CH3)。
Example 7
Preparation of trifloxystrobin
0.25g (1.22mmol) of m-trifluoromethylacetophenone, 4ml of DMF, 0.133g (2.46mmol) of sodium methoxide are stirred at room temperature for 15min, cooled to 5 ℃, added with 0.422g (1.47mmol) of (E) -2-bromomethyl-alpha-methoxyimino phenylacetic acid methyl ester, reacted at room temperature for 5h, poured into ice water, extracted by ethyl acetate, washed by dilute hydrochloric acid, washed by water and separated by column chromatography (PE: EA is 20:1) to obtain 0.375g of m-trifluoromethylacetophenoneTrifloxystrobin, yield 70%.1H NMR(400MHz，CDCl3)：7.90～7.15(m，8H，2×C6H4)，5.15(s，2H，CH2)，4.03(s，3H，NOCH3)，3.82(s，3H，OCH3)，2.22(s，3H，CH3)；13C NMR(100 MHz，CDCl3)：163.34，153.66，149.58，137.23，135.99，129.84，129.42，129.28，128.83，128.80，128.56，127.79，125.65，125.61，122.91，122.87，74.94，63.81，52.90，12.54。
Claims (1)
1. A preparation method of trifloxystrobin; the method is characterized by comprising the following preparation reactions:
wherein R is selected from: a tertiary butyl group; in the bromination reaction, a brominating agent selects 1, 3-dibromo-5, 5-dimethylhydantoin;
the specific operation process is as follows:
(1) stirring and dissolving 12mmol of sodium hydroxide and 10mL of methanol at 40 ℃, and reacting 5mmol of o-tolylacetonitrile and 7.5mmol of tert-butyl nitrite at 60 ℃ for 1 h; 2-methyl-alpha-hydroxyimino phenylacetonitrile is obtained through post treatment, and the yield is 100 percent;
(2) stirring 4mmol of 2-methyl-alpha-hydroxyimino phenylacetonitrile, 15mL of acetonitrile and 8mmol of KOH at the temperature of 35-40 ℃ for 0.5h, cooling to the temperature lower than 10 ℃, dropwise adding 4.8mmol of dimethyl sulfate, stirring at the temperature of 35 ℃ for 3h, and performing post-treatment to obtain 0.626g of 2-methyl-alpha-methoxyimino phenylacetonitrile with the yield of 90%;
(3) adding 5mmol of 20% potassium hydroxide solution into 5mmol of 2-methyl-alpha-methoxyimino phenylacetonitrile and 5mL of ethanol, reacting for 3h at 60 ℃, and performing post-treatment to obtain 0.900g of (E) -2-methyl-alpha-methoxyimino phenylacetamide with single configuration, wherein the yield is 92.5%, and the melting point is 123-125 ℃;
(4)0.960g of 2-methyl-alpha-methoxyimino phenylacetamide and methanol, introducing hydrogen chloride gas, stirring for 12h at 60 ℃, monitoring by TLC, carrying out desolventizing under reduced pressure, adding 20mL of water, extracting with ethyl acetate, washing with saturated sodium bicarbonate, washing with water, drying with anhydrous sodium sulfate, carrying out desolventizing under reduced pressure, and drying to obtain 2-methyl-alpha-methoxyimino phenylacetic acid methyl ester, wherein the yield is 90.5%, and the melting point is 69-71 ℃;
(5)0.414g of (E) -2-methyl-alpha-methoxyimino-phenylacetic acid methyl ester, 5mL of dichloroethane, 0.300g of 1, 3-dibromo-5, 5-dimethylhydantoin, 0.100g of AIBN, reaction at 82 ℃ for 5.0h, TLC monitoring and desolventization; adding 5mL of water, extracting with ethyl acetate, washing with a sodium hydroxide solution, drying with anhydrous sodium sulfate, desolventizing, and separating by column chromatography (PE: EA is 20:1) to obtain 0.472g of (E) -2-bromomethyl-alpha-methoxyimino phenylacetic acid methyl ester with the yield of 82.5%;
(6)0.25g of m-trifluoromethylacetophenone, 4ml of DMMF and 0.133g of sodium methoxide are stirred at room temperature for 15min, cooled to 5 ℃, added with 0.422g of (E) -2-bromomethyl-alpha-methoxyimino phenylacetic acid methyl ester, reacted at room temperature for 5h, poured into ice water, extracted by ethyl acetate, washed by dilute hydrochloric acid, washed by water and separated by column chromatography (PE: EA is 20:1) to obtain 0.375g of trifloxystrobin with the yield of 70 percent.
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