CN105399715A - Substituted phenoxyacetate compound as well as preparation method and applications thereof - Google Patents

Substituted phenoxyacetate compound as well as preparation method and applications thereof Download PDF

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CN105399715A
CN105399715A CN201510744978.3A CN201510744978A CN105399715A CN 105399715 A CN105399715 A CN 105399715A CN 201510744978 A CN201510744978 A CN 201510744978A CN 105399715 A CN105399715 A CN 105399715A
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substituted
unsubstituted
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phenoxyacetic acid
acid compound
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CN105399715B (en
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曹永松
丁光龙
郭明程
张文兵
耿倩倩
王佰涛
郭栋
张兆鹏
李健强
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China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A01N39/04—Aryloxy-acetic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides a substituted phenoxyacetate compound as well as a preparation method and applications thereof. The substituted phenoxyacetate compound disclosed by the invention is prepared by taking substituted phenoxyacetate (2,4-D, agroxone) as a raw material through the steps of acylation and nucleophilic substitution, and the structural formula of the substituted phenoxyacetate compound is shown in a formula I. The prepared compound is novel in structure, and has the advantages of high activity, quick acting, strong selectivity, and the like. The compound is simple in preparation process, environmentally friendly, and short in reaction process. The compound has good biological activity to broadleaf weeds (e.g., kochia scoparia, quinoa), and the biological activity of part of the compound is obviously higher than that of the parent compound.

Description

Substituted phenoxyacetic acid compound and preparation method and application thereof
Technical Field
The invention belongs to the field of pesticide chemistry, and particularly relates to a substituted phenoxyacetic acid compound as well as a preparation method and application thereof.
Background
The phenoxyacetic acid compound has good biological activity and can be widely applied to the fields of pesticides, medicines and the like. In agriculture, phenoxyacetic acid compounds are mainly used as plant growth regulators and herbicides, wherein the representative herbicides are 2,4-D (2, 4-dichlorophenoxyacetic acid) and methoxone (2-methyl-4-chlorophenoxyacetic acid). The 2,4-D and methoxone herbicide has the advantages of good selectivity, wide application period, good effect and the like, but the defects of large dosage, easy drift, strong water solubility, easy water environment pollution and the like of the 2,4-D and methoxone herbicide greatly limit the use of the 2,4-D and methoxone herbicide, and the emergence of resistant weeds (such as wild capsella bursa-pastoris and the like) causes the herbicide to face a more severe situation. Therefore, the finding of the phenoxyacetic acid herbicidal compound with novel structure, high activity and high safety has better application prospect. Currently, an important approach to chemical pesticide development is to perform functional structural engineering on the active parent compound. The patent (CN1250435A) takes phenoxyacetic acid compounds as a parent body, and prepares a series of phenoxyacetic acid derivatives for weeding through structural modification. The invention takes 2,4-D and methoxone as parent compounds, prepares a series of substituted phenoxyacetic acid derivatives through acylation and nucleophilic substitution reaction, and is used for field weeding.
Disclosure of Invention
In order to overcome the defects of large dosage, easy drift, strong water solubility, easy water environment pollution and the like of the conventional phenoxyacetic acid herbicide in the using process, the invention provides a phenoxyacetic acid compound with novel structure, high action speed and low dosage and a preparation method thereof.
The structural formula of the substituted phenoxyacetic acid compound provided by the invention is shown as the formula I:
in the formula I, X is methyl or chlorine, Y is oxygen or sulfur,
r is the following group:
wherein,showing the connection end; r1And R2Each independently selected from any one of: h; substituted or unsubstituted C1-C18 alkyl, such as methyl, ethyl; substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C2-C18 alkenyl, substituted or unsubstituted C3-C18 cycloalkenyl, substituted or unsubstituted C2-C18 alkynyl, substituted or unsubstituted nitrogen, oxygen, sulfur C1-C18 alkyl, substituted or unsubstituted nitrogen, oxygen, sulfur C3-C18 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle.
Specifically, R is:
the substituted phenoxyacetic acid compound can be any one of the compounds in the following table 1:
table 1 partial compound structure
The substituted phenoxyacetic acid compound is prepared by the following steps:
1) carrying out acylation reaction on substituted phenoxyacetic acid shown as a formula II and thionyl chloride under the catalysis of N, N-dimethylformamide to obtain substituted phenoxyacetyl chloride;
in the formula II, X is chlorine or methyl;
2) adding a nucleophilic reagent and alkali into a solvent, and adding the substituted phenoxyacetyl chloride under the ice bath condition to enable the nucleophilic reagent and the substituted phenoxyacetyl chloride to carry out nucleophilic substitution reaction, thereby obtaining a system containing the substituted phenoxyacetic acid compound.
In the step 1) of the method, the thionyl chloride is excessive relative to the substituted phenoxyacetic acid shown in the formula II.
The N, N-dimethylformamide is a catalytic amount.
The reaction is carried out in an organic solvent selected from at least one of: tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, trichloromethane, methanol, ethanol, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine.
The acylation reaction is carried out under the reflux condition, and the time of the acylation reaction is 3-6 hours.
In step 2) of the method, the nucleophilic reagent is any one of the following reagents:
wherein Y is oxygen or sulfur;
R1and R2Each independently selected from any one of: h; substituted or unsubstituted C1-C18 alkyl, such as methyl, ethyl; substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C2-C18 alkenyl, substituted or unsubstituted C3-C18 cycloalkenyl, substituted or unsubstituted C2-C18 alkynyl, substituted or unsubstituted nitrogen, oxygen, sulfur C1-C18 alkyl, substituted or unsubstituted nitrogen, oxygen, sulfur C3-C18 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle.
The alkali is at least one of the following: sodium (potassium) hydroxide, sodium (potassium) carbonate, sodium (potassium) bicarbonate, sodium (potassium) acetate, triethylamine, tri-N-propylamine, N-diisopropylethylamine, and pyridine.
The molar ratio of the nucleophilic reagent to the alkali to the substituted phenoxyacetyl chloride is 1.0: (2.0-8.0): (0.8-3.0).
The solvent is selected from at least one of the following: tetrahydrofuran, acetonitrile, acetone, butanone, cyclohexane, dimethylformamide, dichloromethane, trichloromethane, methanol, ethanol, dioxane, methylnaphthalene, dimethyl sulfoxide, N-methylpyrrolidone, N-formylmorpholine and N-acetylmorpholine.
The nucleophilic substitution reaction is carried out at room temperature, and the time of the nucleophilic substitution reaction is 3-12 hours.
The method also comprises an operation of separating the substituted phenoxyacetic acid compound from the system containing the substituted phenoxyacetic acid compound, wherein the operation comprises the following steps: and (3) carrying out decompression desolventizing, extracting, washing an oil layer with alkali water, washing the oil layer to be neutral, desolventizing and recrystallizing on the system containing the substituted phenoxyacetic acid compound.
The application of the substituted phenoxyacetic acid compound in weed control also belongs to the protection scope of the invention.
The weeds may be orchard weeds and/or weeds in cereal crops.
In the above application, the weeds are broadleaf weeds such as Kochia scoparia, Chenopodium quinoa, and Aralia elata.
The substituted phenoxyacetic acid compound provided by the invention has a novel structure and has the advantages of high activity, quick action, strong selectivity and the like. The compound has the advantages of simple preparation process, environmental friendliness and short reaction process.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The preparation method of the substituted phenoxyacetic acid compound shown in the formula I is illustrated by taking compounds C1-C8 as examples.
Example 1 preparation of Compound C1
(1) Preparation of 2, 4-dichlorophenoxyacetyl chloride: adding 2, 4-dichlorophenoxyacetic acid of 0.1mol, THF of 20ml, thionyl chloride of 40ml and N, N-dimethylformamide of 10 drops into a 250ml four-mouth bottle provided with a magnetic stirring device, a thermometer, a drying tube and a tail gas absorbing and refluxing device, stirring and dissolving, heating to reflux, reacting for 5 hours, decompressing and distilling out the solvent and the residual thionyl chloride to obtain 2, 4-dichlorophenoxyacetyl chloride in a light yellow liquid state, and using the product for the next reaction.
(2) Preparation of compound C1: adding 0.01mol of maltol and 0.03mol of sodium carbonate into 50ml of acetonitrile, slowly dropwise adding 20ml of 0.02mol of the prepared THF solution of 2, 4-dichlorophenoxyacetyl chloride under the ice bath condition, stirring at room temperature for reaction after dropwise adding is finished, monitoring by liquid chromatography until the reaction end point, using for 7h, performing desolventization under reduced pressure, dissolving the rest substance by dichloromethane, washing and extracting by saturated sodium bicarbonate aqueous solution, taking an oil layer, washing by water to be neutral, performing desolventization, recrystallizing by methanol, and obtaining the yield of 79%.
Nuclear magnetic data:1HNMR(300.13MHz；CDCl3；Me4Si)ppm＝2.47(s,3H,CH3),4.67(s,2H,CH2),6.44(d,J＝5.22Hz,1H,CH),6.74(d,J＝8.27Hz,1H,CH),7.11(dd,J1,2＝2.55Hz,J1,3＝8.34Hz,1H,CH),7.33(d,J＝2.51Hz,1H,CH),7.71(d,J＝5.47Hz,1H,CH).
example 2 preparation of Compound C2
(1) Preparation of 2, 4-dichlorophenoxyacetyl chloride: adding 2, 4-dichlorophenoxyacetic acid of 0.1mol, dioxane of 20ml, thionyl chloride of 40ml and N, N-dimethylformamide of 10 drops into a 250ml four-mouth bottle provided with a magnetic stirring device, a thermometer, a drying tube and a tail gas absorbing and refluxing device, stirring, dissolving, heating to reflux, reacting for 6 hours, decompressing and distilling out the solvent and the residual thionyl chloride to obtain yellow liquid 2, 4-dichlorophenoxyacetyl chloride, and using the product for the next reaction.
(2) Preparation of compound C2: adding 0.01mol of ethyl maltol and 0.05mol of pyridine into 50ml of N-methylpyrrolidone, slowly dropwise adding 20ml of 0.015mol of acetonitrile solution of the prepared 2, 4-dichlorophenoxyacetyl chloride under the ice bath condition, stirring at room temperature for reaction after dropwise adding is finished, monitoring by liquid chromatography until the reaction end point, taking 9 hours, performing desolventization under reduced pressure, dissolving the rest substance by cyclohexane, washing and extracting by 0.5mol/L potassium hydroxide aqueous solution, taking an oil layer, washing by water until the oil layer is neutral, performing desolventization, and recrystallizing by methanol to obtain the yield of 77%.
Nuclear magnetic data:1HNMR(300.13MHz；CDCl3；Me4Si)ppm＝1.19(t,J＝7.58Hz,3H,CH3),2.71(q,J＝7.58Hz,2H,CH2),4.67(s,2H,CH2),6.45(d,J＝5.48Hz,1H,CH),6.75(d,J＝8.80Hz,1H,CH),7.11(dd,J1,2＝2.57Hz,J1,3＝8.36Hz,1H,CH),7.33(d,J＝2.51Hz,1H,CH),7.71(d,J＝5.47Hz,1H,CH).
example 3 preparation of Compound C3
(1) Preparation of 2, 4-dichlorophenoxyacetyl chloride: adding 2, 4-dichlorophenoxyacetic acid of 0.1mol, methylnaphthalene of 20ml, thionyl chloride of 40ml and N, N-dimethylformamide of 10 drops into a 250ml four-mouth bottle equipped with a magnetic stirring device, a thermometer, a drying tube and a tail gas absorbing and refluxing device, stirring and dissolving, heating to reflux, reacting for 3 hours, decompressing and distilling off the solvent and the residual thionyl chloride to obtain yellow liquid 2, 4-dichlorophenoxyacetyl chloride, and using the product for the next reaction.
(2) Preparation of compound C3: adding 0.01mol of R- (+) -2- (4-hydroxyphenoxy) propionic acid and 0.08mol of tri-n-propylamine into 50ml of acetone, slowly dropwise adding 20ml of 0.03mol of dichloromethane solution of the prepared 2, 4-dichlorophenoxyacetyl chloride under the ice bath condition, stirring at room temperature for reaction after dropwise adding is finished, monitoring to the end point of the reaction by liquid chromatography, using the time for 4 hours, carrying out desolvation under reduced pressure, dissolving residues by chloroform, washing and extracting by saturated sodium bicarbonate aqueous solution, taking an oil layer, washing by water to be neutral, carrying out desolvation, recrystallizing by chloroform, and obtaining the yield of 73%.
Nuclear magnetic data:1HNMR(300.13MHz；CDCl3；Me4Si)ppm＝1.54(d,J＝6.52,3H,CH3),4.63(q,J＝6.52,1H,CH),4.83(s,2H,CH2),6.76-6.84(m,3H,CH),6.91-6.97(m,2H,CH),7.13(dd,J1,2＝2.52Hz,J1,3＝8.66Hz,1H,CH),7.34(d,J＝2.32,1H,CH),12.53-13.11(s,1H,COOH).
example 4 preparation of Compound C4
(1) Preparation of 2, 4-dichlorophenoxyacetyl chloride: adding 2, 4-dichlorophenoxyacetic acid of 0.1mol, acetonitrile of 20ml, thionyl chloride of 40ml and N, N-dimethylformamide of 10 drops into a 250ml four-mouth bottle provided with a magnetic stirring device, a thermometer, a drying tube and a tail gas absorbing and refluxing device, stirring for dissolving, heating to reflux, reacting for 4 hours, decompressing and distilling out the solvent and the residual thionyl chloride to obtain 2, 4-dichlorophenoxyacetyl chloride in a light yellow liquid state, and using the product for the next reaction.
(2) Preparation of compound C4: adding 0.01mol of R- (+) -2- (4-hydroxyphenoxy) ethyl propionate and 0.04mol of triethylamine into 50ml of butanone, slowly dropwise adding 20ml of 0.013mol of acetonitrile solution of the prepared 2, 4-dichlorophenoxyacetyl chloride under the ice bath condition, stirring at room temperature for reaction after dropwise adding, monitoring by liquid chromatography until the reaction end point, using for 3 hours, carrying out desolvation under reduced pressure, dissolving residues by using chloroform, washing and extracting by using saturated potassium bicarbonate aqueous solution, taking an oil layer, washing by using water until the oil layer is neutral, carrying out desolvation, recrystallizing by using ethanol, and obtaining the yield of 82%.
Nuclear magnetic data:1HNMR(300.13MHz；CDCl3；Me4Si)ppm＝1.18(t,J＝7.12,3H,CH3),1.54(d,J＝6.78,3H,CH3),4.14(q,J＝7.12,2H,CH2),4.63(q,J＝6.78,1H,CH),4.83(s,2H,CH2),6.77-6.84(m,3H,CH),6.92-6.97(m,2H,CH),7.13(dd,J1,2＝2.55Hz,J1,3＝8.79Hz,1H,CH),7.34(d,J＝2.52,1H,CH).
example 5 preparation of Compound C5
(1) Preparation of 2-methyl-4-chlorophenoxyacetyl chloride: adding 2-methyl-4-chlorophenoxyacetic acid, 20ml dichloromethane, 40ml thionyl chloride and 10 drops of N, N-dimethylformamide into a 250ml four-mouth bottle equipped with a magnetic stirring device, a thermometer, a drying tube and a tail gas absorption and reflux device, stirring, dissolving, heating to reflux, reacting for 6h, decompressing and evaporating the solvent and the residual thionyl chloride to obtain light yellow liquid 2-methyl-4-chlorophenoxyacetyl chloride, and using the product in the next reaction.
(2) Preparation of compound C5: adding 0.01mol of maltol and 0.06mol of sodium acetate into 50ml of N-formyl morpholine, slowly dropwise adding 20ml of 0.025mol of the prepared THF solution of 2-methyl-4-chlorophenoxyacetyl chloride under the ice bath condition, stirring at room temperature for reaction after the dropwise adding is finished, monitoring by liquid chromatography until the reaction end point, performing desolventization under reduced pressure after 6 hours, dissolving the residual substance by dichloromethane, washing and extracting by 0.5mol/L of sodium hydroxide aqueous solution, taking an oil layer, washing by water until the oil layer is neutral, performing desolventization, and recrystallizing by methanol to obtain the yield of 81%.
Nuclear magnetic data:1HNMR(300.13MHz；CDCl3；Me4Si)ppm＝2.19(s,3H,CH3),2.47(s,3H,CH3),4.67(s,2H,CH2),6.44(d,J＝5.22Hz,1H,CH),6.74(d,J＝8.27Hz,1H,CH),7.07-7.29(m,2H,CH),7.71(d,J＝5.47Hz,1H,CH).
example 6 preparation of Compound C6
(1) Preparation of 2-methyl-4-chlorophenoxyacetyl chloride: adding 2-methyl-4-chlorophenoxyacetic acid, 20ml THF, 40ml thionyl chloride and 10 drops of N, N-dimethylformamide into a 250ml four-mouth bottle equipped with a magnetic stirring device, a thermometer, a drying tube and a tail gas absorption and reflux device, stirring, dissolving, heating to reflux, reacting for 5h, decompressing, evaporating the solvent and the residual thionyl chloride to obtain light yellow liquid 2-methyl-4-chlorophenoxyacetyl chloride, and using the product for the next reaction.
(2) Preparation of compound C6: adding 0.01mol of ethyl maltol and 0.03mol of N, N-diisopropylethylamine into 50ml of N-acetyl morpholine, slowly dropwise adding 20ml of 0.01mol of the prepared chloroform solution of 2-methyl-4-chlorophenoxyacetyl chloride under the ice bath condition, stirring at room temperature for reaction after dropwise adding is finished, monitoring the reaction end point by liquid chromatography, using the reaction time for 12 hours, carrying out desolventization under reduced pressure, dissolving the rest substance by cyclohexane, washing and extracting by 1mol/L potassium carbonate aqueous solution, taking an oil layer, washing by water to be neutral, carrying out desolventization, recrystallizing by ethanol, and obtaining the yield of 79%.
Nuclear magnetic data:1HNMR(300.13MHz；CDCl3；Me4Si)ppm＝1.19(t,J＝7.45Hz,3H,CH3),2.18(s,3H,CH3),2.71(q,J＝7.34Hz,2H,CH2),4.67(s,2H,CH2),6.45(d,J＝5.48Hz,1H,CH),6.75(d,J＝8.77Hz,1H,CH),7.07-7.29(m,2H,CH),7.71(d,J＝5.33Hz,1H,CH).
example 7 preparation of Compound C7
(1) Preparation of 2-methyl-4-chlorophenoxyacetyl chloride: adding 2-methyl-4-chlorophenoxyacetic acid, 20ml acetonitrile, 40ml thionyl chloride and 10 drops of N, N-dimethylformamide into a 250ml four-mouth bottle equipped with a magnetic stirring device, a thermometer, a drying tube and a tail gas absorption and reflux device, stirring for dissolving, heating to reflux, reacting for 4h, decompressing and evaporating the solvent and the residual thionyl chloride to obtain light yellow liquid 2-methyl-4-chlorophenoxyacetyl chloride, and using the product in the next reaction.
(2) Preparation of compound C7: adding 0.01mol of R- (+) -2- (4-hydroxyphenoxy) propionic acid and 0.07mol of potassium acetate into 50ml of dimethyl sulfoxide, slowly dropwise adding 20ml of 0.027mol of acetonitrile solution of 2-methyl-4-chlorophenoxy acetyl chloride prepared above under the ice bath condition, stirring at room temperature for reaction after dropwise adding is finished, monitoring to the end point of the reaction by liquid chromatography, using for 6 hours, carrying out desolventization under reduced pressure, dissolving residues by chloroform, washing and extracting by saturated sodium bicarbonate aqueous solution, taking an oil layer, washing by water to be neutral, carrying out desolventization, and recrystallizing by ethanol, wherein the yield is 71%.
Nuclear magnetic data:1HNMR(300.13MHz；CDCl3；Me4Si)ppm＝1.54(d,J＝6.27,3H,CH3),2.18(s,3H,CH3),4.63(q,J＝6.11,1H,CH),4.83(s,2H,CH2),6.76-6.84(m,3H,CH),6.91-6.97(m,2H,CH),7.13(dd,J1,2＝2.75Hz,J1,3＝8.34Hz,1H,CH),7.34(d,J＝2.36,1H,CH),12.49-13.52(s,1H,COOH).
example 8 preparation of Compound C8
(1) Preparation of 2-methyl-4-chlorophenoxyacetyl chloride: adding 2-methyl-4-chlorophenoxyacetic acid, 20ml chloroform, 40ml thionyl chloride and 10 drops of N, N-dimethylformamide into a 250ml four-mouth bottle provided with a magnetic stirring device, a thermometer, a drying tube and a tail gas absorption and reflux device, stirring, dissolving, heating to reflux, reacting for 6 hours, decompressing and evaporating the solvent and the residual thionyl chloride to obtain light yellow liquid 2-methyl-4-chlorophenoxyacetyl chloride, and using the product for the next reaction.
(2) Preparation of compound C8: adding 0.01mol of R- (+) -2- (4-hydroxyphenoxy) ethyl propionate and 0.02mol of triethylamine into 50ml of dimethylformamide, slowly dropwise adding 20ml of 0.008mol of the prepared THF solution of 2-methyl-4-chlorophenoxyacetyl chloride under the ice bath condition, stirring at room temperature for reaction after dropwise adding is finished, monitoring by liquid chromatography until the reaction end point, using for 11h, carrying out desolventization under reduced pressure, dissolving the rest substance by dichloromethane, washing and extracting by a saturated potassium bicarbonate aqueous solution, taking an oil layer, washing by water to be neutral, carrying out desolventization, recrystallizing by methanol, and obtaining the yield of 81%.
Nuclear magnetic data:1HNMR(300.13MHz；CDCl3；Me4Si)ppm＝1.18(t,J＝7.32,3H,CH3),1.54(d,J＝6.31,3H,CH3),2.18(s,3H,CH3),4.14(q,J＝7.23,2H,CH2),4.63(q,J＝6.21,1H,CH),4.83(s,2H,CH2),6.76-6.84(m,3H,CH),6.91-6.97(m,2H,CH),7.14(dd,J1,2＝2.54Hz,J1,3＝8.80Hz,1H,CH),7.34(d,J＝2.42,1H,CH).
example 9 Activity study of C1-C8
And selecting an orchard grassland to perform a pharmacodynamic test, and evaluating the pharmacodynamic effect of the substituted phenoxyacetic acid compound. The application concentration of each medicament is 500, 1000mg/L, each concentration is provided with 3 treatments, and each treatment area is 10m2. Investigating the drug effect on weeds 30 days after applicationThe results are shown in Table 2.
TABLE 2 efficacy of the compounds on weeds
As can be seen from the table above, the synthesized substituted phenoxyacetic acid compounds have better herbicidal activity and the control effect on Chenopodium quinoa is obviously better than that of Kochia scoparia; at the same concentration, the control effect of the synthesized substituted phenoxyacetic acid compounds on broadleaf weeds (Kochia scoparia and Chenopodium quinoa) is obviously better than or almost equal to that of the parent compounds, and particularly, the activity of the compounds C4 and C8 is obviously higher than that of the parent compounds.

Claims (10)

1. A substituted phenoxyacetic acid compound has a structural formula shown as a formula I:
in the formula I, X is methyl or chlorine, Y is oxygen or sulfur
R is the following group:
wherein,showing the connection end; r1And R2Each independently selected from any one of: H. substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C2-C18 alkenyl, substituted or unsubstituted C3-C18 cycloalkenyl, substituted or unsubstituted C2-C18 alkynyl, substituted or unsubstituted nitrogen, oxygen, sulfur C1-C18 alkyl, substituted or unsubstituted nitrogen, oxygen, sulfur C3-C18 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle.
2. A process for preparing a substituted phenoxyacetic acid compound of claim 1, comprising the steps of:
1) carrying out acylation reaction on substituted phenoxyacetic acid shown as a formula II and thionyl chloride under the catalysis of N, N-dimethylformamide to obtain substituted phenoxyacetyl chloride;
in the formula II, X is chlorine or methyl;
2) adding a nucleophilic reagent and alkali into a solvent, and adding the substituted phenoxyacetyl chloride under the ice bath condition to enable the nucleophilic reagent and the substituted phenoxyacetyl chloride to carry out nucleophilic substitution reaction, thereby obtaining a system containing the substituted phenoxyacetic acid compound.
3. The method of claim 2, wherein: in the step 1) of the method, the acylation reaction is carried out under reflux conditions, and the time of the acylation reaction is 3-6 hours.
4. A method according to claim 2 or 3, characterized in that: in step 2), the nucleophilic reagent is any one of the following:
wherein Y is oxygen or sulfur;
R1and R2Each independently selected from any one of: H. substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C2-C18 alkenyl, substituted or unsubstituted C3-C18 cycloalkenyl, substituted or unsubstituted C2-C18 alkynyl, substituted or unsubstituted nitrogen, oxygen, sulfur C1-C18 alkyl, substituted or unsubstituted nitrogen, oxygen, sulfur C3-C18 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle.
5. The method according to any one of claims 2-4, wherein: the nucleophilic substitution reaction is carried out at room temperature, and the time of the nucleophilic substitution reaction is 3-12 hours.
6. The method according to any one of claims 2-5, wherein: the molar ratio of the nucleophilic reagent to the alkali to the substituted phenoxyacetyl chloride is 1.0: (2.0-8.0): (0.8-3.0).
7. The method according to any one of claims 2-6, wherein: the method also comprises the operation of separating the substituted phenoxyacetic acid compound from the system containing the substituted phenoxyacetic acid compound,
the operation is as follows: and (3) carrying out decompression desolventizing, extracting, washing an oil layer with alkali water, washing the oil layer to be neutral, desolventizing and recrystallizing on the system containing the substituted phenoxyacetic acid compound.
8. The substituted phenoxyacetic acid compound of claim 1, for use in weed control.
9. The use of claim 8, wherein: the weeds are broadleaf weeds.
10. The use of claim 9, wherein: the broadleaf weeds are at least one of the following weeds: kochia scoparia, Chenopodium quinoa and Potentilla anserina.
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CN1250435A (en) * 1997-02-06 2000-04-12 罗纳-普朗克农业公司 Phenoxyacetic acid derivatives and their use as herbicides
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Publication number Priority date Publication date Assignee Title
US4383850A (en) * 1981-04-15 1983-05-17 Hoechst Aktiengesellschaft Benzthiazole or benzoxazole ethers, herbicidal compositions and use
CN1250435A (en) * 1997-02-06 2000-04-12 罗纳-普朗克农业公司 Phenoxyacetic acid derivatives and their use as herbicides
US6337305B1 (en) * 1997-03-20 2002-01-08 Basf Aktiengesellschaft Substituted 2-benz(o)ylpyridines, their preparation and their use as herbicides

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