CN105399715B - Substituted phenoxy acetic acid class compound and preparation method and application - Google Patents

Substituted phenoxy acetic acid class compound and preparation method and application Download PDF

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CN105399715B
CN105399715B CN201510744978.3A CN201510744978A CN105399715B CN 105399715 B CN105399715 B CN 105399715B CN 201510744978 A CN201510744978 A CN 201510744978A CN 105399715 B CN105399715 B CN 105399715B
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acetic acid
phenoxy acetic
substituted phenoxy
class compound
acid class
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CN105399715A (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)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides substituted phenoxy acetic acid class compound and preparation method and application.The present invention for raw material, obtains substituted phenoxy acetic acid class compound, structural formula is as shown in formula I with substituted phenoxy acetic acid (2,4 D, MCPA,MCP,methoxone) by acylation, nucleophilic substitution.Prepared compound structure is novel, many advantages, such as active high, effect is rapid, selectivity is strong etc..Such compound preparation technology is simple, and environment-friendly, the reaction mechanism mechanism of reaction is shorter.The compound has good bioactivity to broad leaved weed (such as summer cypress, lamb's-quarters), and the bioactivity of part of compounds is apparently higher than parent compound.

Description

Substituted phenoxy acetic acid class compound and preparation method and application
Technical field
The invention belongs to field of pesticide chemistry, and in particular to substituted phenoxy acetic acid class compound and preparation method thereof is with answering With.
Background technology
Phenoxy carboxylic acid derivatives herbicide has good biological activity, is widely used in agricultural chemicals, medicine and other fields.Agriculturally, Phenoxy carboxylic acid derivatives herbicide is mainly used as plant growth regulator and herbicide, wherein representational herbicide is 2,4-D (2,4- Dichlorphenoxyacetic acid) and MCPA,MCP,methoxone (2-methyl-4-chlorophenoxyacetic acid).2,4-D, MCPA,MCP,methoxone are prevented and kill off in cereal crop Weeds have the advantages that selectivity is good, be applicable that period is wide, effect is good, but 2,4-D and MCPA,MCP,methoxone use in use The shortcomings of big, the easy drift of amount, water-soluble strong easily pollution water environment, significantly limit it and use, resistant weed (such as bitter cress) Appearance so that this kind of herbicide faces more acute situation.Therefore, structure novelty, high activity, safe benzene are found Fluoroacetic acid class herbicides compounds will have preferable application prospect.At present, an important channel of chemical pesticide exploitation is in work Property parent compound on carry out functionalization structure of modification.Patent (CN1250435A) is led to using phenoxy carboxylic acid derivatives herbicide as parent Structure of modification is crossed, a series of phenoxy acetic acid analog derivatives are prepared for and for weeding.The present invention is using 2,4-D and MCPA,MCP,methoxone as mother Body compound, is prepared for a series of substituted phenoxy acetic acid analog derivatives by acylated and nucleophilic substitution and is removed for field Grass.
The content of the invention
In order to overcome the big consumption of existing phenoxy acetic acid class herbicide in use, easy drift, water-soluble strong easily dirt The shortcomings of contaminating water environment, the invention provides the low phenoxy carboxylic acid derivatives herbicide of a kind of structure novelty, work fast, consumption and Its preparation method.
Substituted phenoxy acetic acid class compound provided by the present invention, its structural formula is as shown in formula I：
In formula I, X be methyl or chlorine, Y be oxygen or sulphur,
R is following radicals：
Wherein,Represent connection end；R1And R2Separately selected from it is following any one：H；It is substituted or unsubstituted C1-C18 alkyl, such as methyl, ethyl；Substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C2-C18 alkenyls, take Generation or unsubstituted C3-C18 cycloalkenyl groups, substituted or unsubstituted C2-C18 alkynyls, substituted or unsubstituted nitrogenous, oxygen, sulphur C1- C18 alkyl, substituted or unsubstituted nitrogenous, oxygen, sulphur C3-C18 cycloalkyl, substituted or unsubstituted aryl, substitution or unsubstituted Heterocycle.
Specifically, R is：
Any one of the substituted phenoxy acetic acid class compound concretely in table 1：
The part of compounds structure of table 1
Above-mentioned substituted phenoxy acetic acid class compound is prepared by the method comprising the following steps：
1) under DMF catalysis, the substituted phenoxy acetic acid shown in Formula II and thionyl chloride are acylated Reaction, obtains substituted benzene oxygen chloroacetic chloride；
In Formula II, X is chlorine or methyl；
2) nucleopilic reagent, alkali are added in solvent, the substituted benzene oxygen chloroacetic chloride are added under condition of ice bath so that institute State nucleopilic reagent and carry out nucleophilic substitution with the substituted benzene oxygen chloroacetic chloride, obtain containing substituted phenoxy acetic acid class compound System.
Above method step 1) in, thionyl chloride is excessive relative to the substituted phenoxy acetic acid shown in Formula II.
N,N-dimethylformamide is catalytic amount.
The reaction is carried out in organic solvent, and the organic solvent is selected from following at least one：Tetrahydrofuran, acetonitrile, Acetone, butanone, hexamethylene, dimethylformamide, dichloromethane, chloroform, methanol, ethanol, dioxane, methyl naphthalene, two Methyl sulfoxide, 1-METHYLPYRROLIDONE, N- formyl-morpholines and N- acetylmorpholines.
The acylation reaction is carried out under reflux conditions, and the time of the acylation reaction is 3-6 hours.
Above method step 2) in, the nucleopilic reagent for it is following any one：
Wherein, Y is oxygen or sulphur；
R1And R2Separately selected from it is following any one：H；Substituted or unsubstituted C1-C18 alkyl, such as methyl, second Base；Substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C2-C18 alkenyls, substituted or unsubstituted C3-C18 rings Alkenyl, substituted or unsubstituted C2-C18 alkynyls, substituted or unsubstituted nitrogenous, oxygen, sulphur C1-C18 alkyl, substitution or unsubstituted Nitrogenous, oxygen, sulphur C3-C18 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle.
The alkali is following at least one：Sodium hydroxide (potassium), sodium carbonate (potassium), sodium acid carbonate (potassium), sodium acetate (potassium), Triethylamine, Tri-n-Propylamine, N, N- diisopropylethylamine and pyridine.
The mol ratio of the nucleopilic reagent and alkali, substituted benzene oxygen chloroacetic chloride is 1.0：(2.0-8.0)：(0.8-3.0).
The solvent is selected from following at least one：Tetrahydrofuran, acetonitrile, acetone, butanone, hexamethylene, dimethylformamide, Dichloromethane, chloroform, methanol, ethanol, dioxane, methyl naphthalene, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, N- formyls Base morpholine and N- acetylmorpholines.
The nucleophilic substitution is carried out at room temperature, and the time of the nucleophilic substitution is 3-12 hours.
The above method also includes the isolated substituted benzene oxygen from the system containing substituted phenoxy acetic acid class compound The operation of phenylacetic acid compound, the operation is：The system containing substituted phenoxy acetic acid class compound is depressurized into precipitation, extraction Take, alkali water washed reservoir, water washed reservoir to neutrality, precipitation, recrystallize, you can.
Application of the above-mentioned substituted phenoxy acetic acid class compound in management of weeds falls within protection scope of the present invention.
The weeds can be the weeds in orchard weed and/or cereal crop.
In above-mentioned application, the weeds are broad leaved weed, such as summer cypress, lamb's-quarters, field thistle.
The substituted phenoxy acetic acid class compound that the present invention is provided, its structure is novel, and active high, effect is rapid, selection Property by force wait many advantages, such as.Such compound preparation technology is simple, and environment-friendly, the reaction mechanism mechanism of reaction is shorter.
Embodiment
Below by specific embodiment, the present invention will be described, but the invention is not limited in this.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments Reagent, material etc., unless otherwise specified, are commercially obtained.
Below by taking compound C1-C8 as an example, substituted phenoxy acetic acid class compound shown in formula I provided by the present invention is illustrated Preparation method.
The preparation of embodiment 1, compound C1
(1) preparation of 2,4 dichloro benzene oxygen chloroacetic chloride：To equipped with magnetic agitation, thermometer, drying tube, tail gas absorption and return Flow addition 0.1mol 2 in the 250ml four-hole bottles of device, 4- dichlorphenoxyacetic acids, 20ml THF, 40ml thionyl chlorides and 10 drops Decompression after backflow, reaction 5h is warming up to after DMF, stirring and dissolving and steams solvent and remaining thionyl chloride, is obtained Weak yellow liquid shape 2,4- Dichlorophenoxy chloroacetic chlorides, product is used for the next step.
(2) compound C1 preparation：0.01mol maltols, 0.03mol sodium carbonate are added in 50ml acetonitriles, in ice The THF solution of 2, the 4- Dichlorophenoxy chloroacetic chlorides of the above-mentioned preparations of 20ml 0.02mol is slowly added dropwise under the conditions of bath, after completion of dropwise addition, Reaction is stirred at room temperature, liquid chromatogram is monitored to reaction end, used time 7h, is depressurized precipitation, surplus materials dichloromethane dissolves, is satisfied Wash and extract with sodium bicarbonate aqueous solution, take oil reservoir, be washed to neutrality, precipitation, recrystallizing methanol, yield 79%.
Nuclear magnetic data：1H NMR(300.13MHz；CDCl3；Me4Si) δ 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)
The preparation of embodiment 2, compound C2
The preparation of (1) 2,4- Dichlorophenoxy chloroacetic chloride：To equipped with magnetic agitation, thermometer, drying tube, tail gas absorption and return Flow device 250ml four-hole bottles in add 0.1mol 2,4- dichlorphenoxyacetic acids, 20ml dioxane, 40ml thionyl chlorides and Decompression after backflow, reaction 6h is warming up to after 10 drop DMFs, stirring and dissolving and steams solvent and remaining dichloro Asia Sulfone, obtains yellow liquid 2, and 4- Dichlorophenoxy chloroacetic chlorides, product is used for the next step.
(2) compound C2 preparation：0.01mol ethylmaltols, 0.05mol pyridines are added to 50ml N- methyl pyrroles In pyrrolidone, the acetonitrile of 2, the 4- Dichlorophenoxy chloroacetic chlorides of the above-mentioned preparations of 20ml 0.015mol is slowly added dropwise under condition of ice bath Solution, after completion of dropwise addition, is stirred at room temperature reaction, liquid chromatogram is monitored to reaction end, used time 9h, depressurizes precipitation, surplus materials Dissolved with hexamethylene, 0.5mol/L potassium hydroxide aqueous solutions are washed and extracted, and take oil reservoir, be washed to neutrality, precipitation, methanol is tied again Crystalline substance, yield 77%.
Nuclear magnetic data：1H NMR(300.13MHz；CDCl3；Me4Si) δ 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)
The preparation of embodiment 3, compound C3
(1) preparation of 2,4 dichloro benzene oxygen chloroacetic chloride：To equipped with magnetic agitation, thermometer, drying tube, tail gas absorption and return Flow and 0.1mol 2,4- dichlorphenoxyacetic acids, 20ml methyl naphthalenes, 40ml thionyl chlorides and 10 are added in the 250ml four-hole bottles of device Drip and backflow be warming up to after DMF, stirring and dissolving, decompression steams solvent and remaining thionyl chloride after reaction 3h, Yellow liquid 2 is obtained, 4- Dichlorophenoxy chloroacetic chlorides, product is used for the next step.
(2) compound C3 preparation：By 0.01mol R- (+) -2- (4- hydroxyphenoxies) propionic acid, 0.08mol tri- positive third Amine is added in 50ml acetone, and 2, the 4- Dichlorophenoxy acetyl of the above-mentioned preparations of 20ml 0.03mol is slowly added dropwise under condition of ice bath The dichloromethane solution of chlorine, after completion of dropwise addition, is stirred at room temperature reaction, liquid chromatogram is monitored to reaction end, used time 4h, and decompression is de- Molten, surplus materials chloroform is dissolved, and saturated sodium bicarbonate aqueous solution is washed and extracted, and takes oil reservoir, is washed to neutrality, precipitation, chlorine Imitative recrystallization, yield 73%.
Nuclear magnetic data：1H NMR(300.13MHz；CDCl3；Me4Si) δ 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).
The preparation of embodiment 4, compound C4
(1) preparation of 2,4 dichloro benzene oxygen chloroacetic chloride：To equipped with magnetic agitation, thermometer, drying tube, tail gas absorption and return Flow addition 0.1mol 2 in the 250ml four-hole bottles of device, 4- dichlorphenoxyacetic acids, 20ml acetonitriles, 40ml thionyl chlorides and 10 drops Decompression after backflow, reaction 4h is warming up to after DMF, stirring and dissolving and steams solvent and remaining thionyl chloride, is obtained Weak yellow liquid shape 2,4- Dichlorophenoxy chloroacetic chlorides, product is used for the next step.
(2) compound C4 preparation：By 0.01mol R- (+) -2- (4- hydroxyphenoxies) ethyl propionate, 0.04mol tri- Ethamine is added in 50ml butanone, and 2, the 4- Dichlorophenoxies of the above-mentioned preparations of 20ml 0.013mol are slowly added dropwise under condition of ice bath The acetonitrile solution of chloroacetic chloride, after completion of dropwise addition, is stirred at room temperature reaction, liquid chromatogram is monitored to reaction end, used time 3h, and decompression is de- Molten, surplus materials chloroform is dissolved, and the saturated potassium hydrogen carbonate aqueous solution is washed and extracted, and takes oil reservoir, is washed to neutrality, precipitation, second Alcohol is recrystallized, yield 82%.
Nuclear magnetic data：1H NMR(300.13MHz；CDCl3；Me4Si) δ 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)
The preparation of embodiment 5, compound C5
(1) preparation of 2- methyl -4- chlorine phenoxyacetyl chlorides：To equipped with magnetic agitation, thermometer, drying tube, tail gas absorption And 0.1mol 2-methyl-4-chlorophenoxyacetic acids, 20ml dichloromethane, 40ml dichloros are added in the 250ml four-hole bottles of reflux Decompression after backflow, reaction 6h is warming up to after sulfoxide and 10 drop DMFs, stirring and dissolving and steams solvent and remaining Thionyl chloride, obtains weak yellow liquid shape 2- methyl -4- chlorine phenoxyacetyl chlorides, and product is used for the next step.
(2) compound C5 preparation：0.01mol maltols, 0.06mol sodium acetates are added to 50ml N- formoxyls In quinoline, the THF that the 2- methyl -4- chlorine phenoxyacetyl chlorides of the above-mentioned preparations of 20ml 0.025mol are slowly added dropwise under condition of ice bath is molten Liquid, after completion of dropwise addition, is stirred at room temperature reaction, liquid chromatogram is monitored to reaction end, used time 6h, depressurizes precipitation, and surplus materials is used Dichloromethane is dissolved, and 0.5mol/L sodium hydrate aqueous solutions are washed and extracted, take oil reservoir, be washed to neutrality, precipitation, methanol is tied again Crystalline substance, yield 81%.
Nuclear magnetic data：1H NMR(300.13MHz；CDCl3；Me4Si) δ 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)
The preparation of embodiment 6, compound C6
(1) preparation of 2- methyl -4- chlorine phenoxyacetyl chlorides：To equipped with magnetic agitation, thermometer, drying tube, tail gas absorption And 0.1mol 2-methyl-4-chlorophenoxyacetic acids, 20ml THF, 40ml thionyl chlorides are added in the 250ml four-hole bottles of reflux And 10 drop DMFs, it is warming up to after stirring and dissolving to depressurize after backflow, reaction 5h and steams solvent and remaining dichloro Sulfoxide, obtains weak yellow liquid shape 2- methyl -4- chlorine phenoxyacetyl chlorides, and product is used for the next step.
(2) compound C6 preparation：0.01mol ethylmaltols, 0.03mol N, N- diisopropylethylamine are added to In 50ml N- acetylmorpholines, the 2- methyl -4- chlorobenzene oxygen of the above-mentioned preparations of 20ml 0.01mol is slowly added dropwise under condition of ice bath The chloroformic solution of chloroacetic chloride, after completion of dropwise addition, is stirred at room temperature reaction, liquid chromatogram is monitored to reaction end, used time 12h, decompression Precipitation, surplus materials hexamethylene is dissolved, and 1mol/L wet chemicals are washed and extracted, and take oil reservoir, are washed to neutrality, is taken off It is molten, ethyl alcohol recrystallization, yield 79%.
Nuclear magnetic data：1H NMR(300.13MHz；CDCl3；Me4Si) δ 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 (d, J=5.33Hz, 1H, the CH) of 6.75 (d, J=8.77Hz, 1H, CH), 7.07-7.29 (m, 2H, CH), 7.71
The preparation of embodiment 7, compound C7
(1) preparation of 2- methyl -4- chlorine phenoxyacetyl chlorides：To equipped with magnetic agitation, thermometer, drying tube, tail gas absorption And 0.1mol 2-methyl-4-chlorophenoxyacetic acids, 20ml acetonitriles, 40ml thionyl chlorides are added in the 250ml four-hole bottles of reflux And 10 drop DMFs, it is warming up to after stirring and dissolving to depressurize after backflow, reaction 4h and steams solvent and remaining dichloro Sulfoxide, obtains weak yellow liquid shape 2- methyl -4- chlorine phenoxyacetyl chlorides, and product is used for the next step.
(2) compound C7 preparation：By 0.01mol R- (+) -2- (4- hydroxyphenoxies) propionic acid, 0.07mol potassium acetates It is added in 50ml dimethyl sulfoxide (DMSO)s, the 2- methyl -4- chlorine of the above-mentioned preparations of 20ml 0.027mol is slowly added dropwise under condition of ice bath The acetonitrile solution of phenoxyacetyl chloride, after completion of dropwise addition, is stirred at room temperature reaction, liquid chromatogram is monitored to reaction end, used time 6h, subtracted Pressure-off is molten, and surplus materials chloroform dissolves, and saturated sodium bicarbonate aqueous solution is washed and extracted, and takes oil reservoir, is washed to neutrality, takes off It is molten, ethyl alcohol recrystallization, yield 71%.
Nuclear magnetic data：1H NMR(300.13MHz；CDCl3；Me4Si) δ 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).
The preparation of embodiment 8, compound C8
(1) preparation of 2- methyl -4- chlorine phenoxyacetyl chlorides：To equipped with magnetic agitation, thermometer, drying tube, tail gas absorption And 0.1mol 2-methyl-4-chlorophenoxyacetic acids, 20ml chloroforms, 40ml thionyl chlorides are added in the 250ml four-hole bottles of reflux And 10 drop DMFs, it is warming up to after stirring and dissolving to depressurize after backflow, reaction 6h and steams solvent and remaining dichloro Sulfoxide, obtains weak yellow liquid shape 2- methyl -4- chlorine phenoxyacetyl chlorides, and product is used for the next step.
(2) compound C8 preparation：By 0.01mol R- (+) -2- (4- hydroxyphenoxies) ethyl propionate, 0.02mol tri- Ethamine is added in 50ml dimethylformamides, and the 2- first of the above-mentioned preparations of 20ml 0.008mol is slowly added dropwise under condition of ice bath The THF solution of base -4- chlorine phenoxyacetyl chlorides, after completion of dropwise addition, is stirred at room temperature reaction, liquid chromatogram is monitored to reaction end, used When 11h, depressurize precipitation, surplus materials dichloromethane dissolves, the saturated potassium hydrogen carbonate aqueous solution is washed and extracted, and takes oil reservoir, water It is washed till neutrality, precipitation, recrystallizing methanol, yield 81%.
Nuclear magnetic data：1H NMR(300.13MHz；CDCl3；Me4Si) δ 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)
The activity research of embodiment 9, C1-C8
Choose orchard meadow and carry out the test of pesticide effectiveness, evaluate the drug effect of substituted phenoxy acetic acid class compound.Every kind of medicament application Concentration is 500,1000mg/L, and each concentration sets 3 processing, and each processing area is 10m2.It is investigated to miscellaneous within 30 days after dispenser The drug effect of grass, statistical result such as table 2.
Drug effect of the compound of table 2 to weeds
As seen from the above table, synthesized substituted phenoxy acetic acid class compound has preferable activity of weeding, and lamb's-quarters is prevented Effect is significantly better than summer cypress；Under same concentration, the substituted phenoxy acetic acid class compound of synthesis is to broad leaved weed (summer cypress and lamb's-quarters) Preventive effect is significantly better than or active apparently higher than parent compound no better than parent compound, particularly compound C4, C8.

Claims (10)

1. a kind of substituted phenoxy acetic acid class compound, its structural formula is as shown in formula I：
In formula I, X is methyl or chlorine, and Y is oxygen；
R is following radicals：
Wherein,Represent connection end；R1For H or CH3；R2For H or CH2CH3。
2. preparing the method for the substituted phenoxy acetic acid class compound described in claim 1, comprise the steps：
1) under DMF catalysis, the substituted phenoxy acetic acid shown in Formula II and thionyl chloride be acylated instead Should, obtain substituted benzene oxygen chloroacetic chloride；
In Formula II, X is chlorine or methyl；
2) nucleopilic reagent, alkali are added in solvent, the substituted benzene oxygen chloroacetic chloride are added under condition of ice bath so that the parent Core reagent carries out nucleophilic substitution with the substituted benzene oxygen chloroacetic chloride, obtains the body containing substituted phenoxy acetic acid class compound System.
3. method according to claim 2, it is characterised in that：Methods described step 1) in, the acylation reaction is in backflow Under the conditions of carry out, time of the acylation reaction is 3-6 hours.
4. method according to claim 2, it is characterised in that：Methods described step 2) in, the nucleopilic reagent is following Any one：
Wherein, Y is oxygen；
R1For H or CH3；R2For H or CH2CH3。
5. method according to claim 2, it is characterised in that：The nucleophilic substitution is carried out at room temperature, the parent The time of core substitution reaction is 3-12 hours.
6. method according to claim 2, it is characterised in that：The nucleopilic reagent and alkali, substituted benzene oxygen chloroacetic chloride rub You are than being 1.0：(2.0-8.0)：(0.8-3.0).
7. method according to claim 2, it is characterised in that：Methods described also includes containing substituted phenoxy acetic acid from described The operation of isolated substituted phenoxy acetic acid class compound in the system of class compound,
The operation is：The system containing substituted phenoxy acetic acid class compound is depressurized into precipitation, extracted, alkali water washed reservoir, Water washed reservoir to neutrality, precipitation is recrystallized, you can.
8. application of the substituted phenoxy acetic acid class compound in management of weeds described in claim 1.
9. application according to claim 8, it is characterised in that：The weeds are broad leaved weed.
10. application according to claim 9, it is characterised in that：The broad leaved weed is following at least one：Summer cypress, lamb's-quarters And field thistle.
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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
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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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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A facile synthesis of novel optically active R,R-2-(4-(2-(4-(5-chloro-3-halo-pyridin-2-yloxy)-phenoxy)-propionyloxy)-phenoxy)-propionic acid esters using cyanuric chloride as potential herbicide;Hassan Tajik et al.;《 Chinese Chemical Letters》;20110302;第22卷;535-538 *

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