CN112574119B - Process for preparing hydantoin derivatives - Google Patents

Process for preparing hydantoin derivatives Download PDF

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CN112574119B
CN112574119B CN202010999866.3A CN202010999866A CN112574119B CN 112574119 B CN112574119 B CN 112574119B CN 202010999866 A CN202010999866 A CN 202010999866A CN 112574119 B CN112574119 B CN 112574119B
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enantiomers
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ratios
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CN112574119A (en
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刘永江
曾伟
周磊
左翔
程柯
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Lier Chemical Co Ltd
Guangan Lier Chemical Co Ltd
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Guangan Lier Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
    • C07D233/78—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
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  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a process for the preparation of hydantoin derivatives by reacting a compound of formula (II), or a salt, enantiomer or a mixture of enantiomers in all ratios thereof, with a compound of formula (III) to give a compound of formula (IV), or a salt, enantiomer or a mixture of enantiomers in all ratios thereof; and then subjecting the compound of formula (IV) to intramolecular condensation in the presence of an acid to give the compound of formula (I) or a salt, enantiomer or mixture of enantiomers in all proportions thereof. The hydantoin derivative provided by the invention is used for synthesizing glufosinate-ammonium, so that the problems of high cost, low efficiency and the like in the prior art can be solved, and the hydantoin derivative is a method with a high cost advantage.

Description

Process for preparing hydantoin derivatives
Technical Field
The present invention relates to a process for the preparation of hydantoin derivatives.
Background
Glufosinate is a broad-spectrum organophosphorus contact-type herbicide developed successfully in 80 s by hoechst, is a glutamine synthesis inhibitor, has weak internal absorption effect, is different from the early glyphosate root killing, firstly kills leaves by glufosinate, then can be conducted on plant xylem through plant transpiration, has quick-acting performance between paraquat and glyphosate, and is a non-selective contact-type herbicide. In the prior art, the preparation method of glufosinate-ammonium generally has the problems of complex reaction, low efficiency and high production cost.
Disclosure of Invention
The present invention provides a process for the preparation of a hydantoin derivative of formula (I):
Figure GDA0002736900810000011
or a salt, an enantiomer or a mixture of enantiomers thereof in all proportions, in particular a mixture of enantiomers thereof, in particular a racemic mixture thereof, comprising the steps of:
(a) reacting a compound of formula (II)
Figure GDA0002736900810000012
Or salts, enantiomers or mixtures of enantiomers in all ratios thereof, in particular enantiomers in the L-configuration thereof,
with compounds of the formula (III)
Figure GDA0002736900810000013
Reaction to give the compound of formula (IV)
Figure GDA0002736900810000021
Or salts, enantiomers or mixtures of enantiomers thereof in all proportions, in particular mixtures of enantiomers thereof, especially in particular racemic mixtures thereof;
(b) intramolecular condensation of the compound of formula (IV) in the presence of an acid to give the compound of formula (I) or a salt, enantiomer or mixture of enantiomers in all ratios thereof;
wherein:
x is halogen, -OR 3 or-SR 4 ；
Y is O or S;
R 1 is hydrogen or an amino protecting group;
R 2 is hydrogen or C 1 -C 4 An alkyl group;
R 3 is hydrogen or a hydroxy protecting group;
R 4 is hydrogen or a mercapto protecting group.
Further, X is O, R 1 Is hydrogen.
Further, Y is O, R 2 Is hydrogen.
Further, in the step (a), the temperature of the reaction is 80 to 120 ℃, preferably 90 to 110 ℃. In step (a), the reaction time is between 1 to 30 hours, 3 to 30 hours, 5 to 20 hours, or 5 to 10 hours. By carrying out the step (a) reaction in this temperature range and time range, the compound of formula (IV) can be more easily prepared.
Further, in step (a), the aforementioned reaction is carried out in a solvent selected from water or a polar organic solvent.
Further, in the step (b), the acid is any one of hydrochloric acid, sulfuric acid, acetic acid, or a mixture thereof.
Further, the step (b) is carried out at 60 to 120 ℃.
Preferably, the aforementioned process is a one-pot process, i.e. the compound of formula (IV) prepared by step (a) is directly involved in step (b) without isolation from the reaction medium.
The invention also provides a preparation method of glufosinate-ammonium, the compound of formula (I) is prepared by the method, the compound of formula (I) and diethyl methylphosphite undergo Arbuzov rearrangement reaction, and glufosinate-ammonium is obtained through hydrolysis reaction. The Arbuzov rearrangement reaction, also known as Michaelis-Arbuzov reaction, is carried out in a manner known to the person skilled in the art, for example by adding elemental iodine.
Further, in the rearrangement reaction, the reaction temperature is 60 to 200 ℃.
Furthermore, the rearrangement reaction is carried out under the catalysis of Lewis acid, and the reaction temperature is 20-200 ℃.
Further, the aforementioned hydrolysis reaction is carried out in the presence of an acid or a base.
The invention provides a method for preparing a hydantoin derivative, and the hydantoin derivative is used for synthesizing glufosinate-ammonium, can solve the problems of high cost, low efficiency and the like in the prior art, and has the advantage of high cost.
Unless stated to the contrary, the following terms used in the specification and claims have the following meanings.
The term "alkyl" refers to a saturated aliphatic hydrocarbon group, including straight and branched chain groups of 1 to 18 carbon atoms. Alkyl groups having 1 to 6 carbon atoms are preferred, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, pentyl and the like. The alkyl group may be substituted or unsubstituted, and when substituted, the substituent may be halogen, nitro, sulfonyl, etheroxy, etherthio, ester, thioester, or cyano.
The term "alkenyl" refers to an alkyl group as defined above consisting of at least two carbon atoms and at least one carbon-carbon double bond. Such as ethenyl, 1-propenyl, 2-propenyl, 1-, 2-or 3-butenyl, and the like. The alkenyl group may be substituted or unsubstituted, and when substituted, the substituent may be halogen, nitro, sulfonyl, etheroxy, etherthio, ester, thioester, or cyano.
The term "aryl" refers to a group having at least one aromatic ring structure. The aryl group is preferably a phenyl group or a benzyl group. Phenyl and benzyl groups may be substituted or unsubstituted.
The term "amino protecting group" refers to a group that can be attached to a nitrogen atom on an amino group to protect the amino group from reaction and which can be easily removed in a subsequent reaction. Suitable amino protecting groups include, but are not limited to, the following:
a carbamate group of the formula-C (O) O-R, wherein R is, for example, methyl, ethyl, tert-butyl, benzyl, phenethyl, CH 2 ＝CH-CH 2 -, etc.; amide groups of the formula-c (o) -R ', wherein R' is, for example, methyl, ethyl, phenyl, trifluoromethyl, and the like; formula-SO 2 The N-sulfonyl derivative-group of-R ', wherein R' is, for example, tolyl, phenyl, trifluoromethyl, 2,5,7, 8-pentamethylchroman-6-yl-, 2,3, 6-trimethyl-4-methoxybenzene, and the like.
C 1 -C 4 Alkyl groups are linear or branched, saturated hydrocarbon chains containing from 1 to 4 carbon atoms. It may be a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl group.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
The preparation process of the present invention will be further described with reference to examples.
The ee value of the raw material L-homoserine is more than 95%.
Example 1
Figure GDA0002736900810000041
Adding L-homoserine (140g, 1.18mol), urea (106g, 1.76mol) and water (250mL) into a 500mL three-necked flask, heating to raise the internal temperature to 100 ℃ for reaction for 8 hours, cooling to room temperature, drying the water by spinning, pulping by using methanol (100mL), washing by using methanol for three times (50mL x 3), and drying to obtain white crystals of 4-hydroxy-2-ureidobutyric acid 181.7g, wherein the yield is 95%, the HPLC purity is 96%, and the white crystals are detected to be a racemic mixture.
Product structure analysis data are as follows: MS (ESI) M/z [ M + H] + calcd for C 5 H 11 N 2 O 4 :163.06；found:163.1.
Example 2
Figure GDA0002736900810000042
In a 250mL three-necked flask, 4-hydroxy-2-ureidobutyric acid (28g, 172.7mmol) prepared in example 1 and 18% HCl (57.6mL, 345.4mmol) were added, the mixture was heated and stirred to an inner temperature of 90 ℃ for reaction for 6 hours, cooled to room temperature, and water was spun off to obtain a white solid, and the white solid was washed with ethanol (100mL × 3) and dried to obtain 5- (2-hydroxyethyl) imidazolidine-2, 4-dione as a white solid in a yield of 97%, purity by HPLC of 97%, which was detected as a racemic mixture.
Product structure analysis data are as follows:
MS(ESI):m/z[M+H] + calcd for C 5 H 9 N 2 O 3 :145.06；found:145.3.
1 H NMR(D 2 O,400MHz)δ：4.22(dd,J＝8.0,4.0Hz,1H),3.72–3.50(m,2H),1.97(dtd,J＝14.4,6.0,4.8Hz,1H),1.87(dtd,J＝14.4,7.2,6.0Hz,1H).
13 C NMR(D 2 O,100MHz)δ：179.0,159.3,57.4,56.2,32.7.
example 3
Figure GDA0002736900810000051
Into a 250mL three-necked flask, 4-hydroxy-2-ureido butane prepared in example 1 was addedAcid (28g, 172.7mmol), 18% H 2 SO 4 (57.6mL, 345.4mmol), heating and stirring, raising the temperature to the internal temperature of 100 ℃, reacting for 4h, cooling to room temperature, removing part of water by rotation, cooling to 0 ℃, crystallizing, washing the white solid with ethanol (50mL x 3), and drying to obtain 23.6g of white solid 5- (2-hydroxyethyl) imidazolidine-2, 4-dione, wherein the yield is 95%, the HPLC purity is 99%, and the product is detected to be a racemic mixture.
Example 4
Figure GDA0002736900810000052
Into a 250mL three-necked flask, 4-hydroxy-2-ureidobutyric acid (28g, 172.7mmol) prepared in example 1 and CH were added 3 COOH (50mL), heated and stirred until the internal temperature reaches 80 ℃ for reaction for 8h, cooled to room temperature, and CH is removed 3 COOH gave a white solid which was washed with ethanol (50mL x 3) and dried to give 22.4g of 5- (2-hydroxyethyl) imidazolidine-2, 4-dione as a white solid in 90% yield and 95% HPLC purity as a racemic mixture.
Example 5
Figure GDA0002736900810000053
Adding L-homoserine (140g, 1.18mol), urea (85.5g, 1.42mol) and water (250mL) into a 500mL three-necked flask, heating to an internal temperature of 100 ℃ for reaction for 8h, detecting the disappearance of raw materials by MS, cooling to room temperature, dropwise adding 36% HCl (200mL, 2.36mol), heating and stirring to an internal temperature of 90 ℃ for reaction for 6h, cooling to room temperature, spin-drying water to obtain a white solid, washing the white solid with ethanol (150mL x 3), and drying to obtain 163.2g of 5- (2-hydroxyethyl) imidazolidine-2, 4-dione as the white solid, wherein the yield is 96%, the HPLC purity is 97.5%, and detecting that the white solid is a racemic mixture.
Example 6
Figure GDA0002736900810000061
Adding 5- (2-hydroxyethyl) imidazolidine-2, 4-dione (12g, 83.2mmol) and a 48% hydrobromic acid acetic acid solution (34mL, 50g, 300mmol) into a 250mL sealed tube, sealing and pressing, reacting at 90 ℃ for 10h, naturally cooling to room temperature, spin-drying a solvent in a reaction system, recrystallizing with ethyl acetate, performing suction filtration, and drying to obtain a white solid product, namely 14.6g of 5- (2-bromoethyl) imidazolidine-2, 4-dione, wherein the yield is 85% and the HPLC purity is 96.5%.
Example 7
Figure GDA0002736900810000062
Adding 5- (2-hydroxyethyl) imidazolidine-2, 4-dione (20g, 138.8mmol) and 37% hydrochloric acid into a 250mL sealed tube, sealing and pressing, reacting at 100 ℃ for 10h, naturally cooling to room temperature, spin-drying a solvent in a reaction system, recrystallizing with ethyl acetate, performing suction filtration and drying to obtain a white solid product, namely 20.3g of 5- (2-chloroethyl) imidazolidine-2, 4-dione, wherein the yield is 90% and the HPLC purity is 98%.
Product structure analysis data are as follows:
1 H NMR(DMSO-d6,400MHz)δ：10.69(s,1H),8.05(s,1H),4.19–4.11(m,1H),3.92–3.65(m,2H),2.16(dtd,J＝14.8,7.6,4.8Hz,1H),2.01(ddt,J＝14.4,8.4,6.0Hz,1H).
example 8
Figure GDA0002736900810000063
Diethyl methylphosphonite (20.5g,150.1mmol), 5- (2-bromoethyl) imidazolidine-2, 4-dione (25.7g,125mmol) and 20mL of toluene were added to a 250mL three-necked flask, replaced with argon gas three times, stirred, heated to 100 ℃ to react for 5 hours, and the solvent and unreacted raw materials were removed by desolventization under reduced pressure to obtain 25.2g of a pale yellow viscous liquid with a yield of 86.0% and an HPLC purity of 97%.
Product structure analysis data are as follows:
1 H NMR(DMSO-d6,400MHz)δ：1.20(t,J＝7.0Hz,3H),1.40(d,J＝13.7Hz,3H),1.64(dq,J＝15.2,7.6Hz,4H),3.93–3.89(m,2H),4.07(t,J＝5.6Hz,1H),8.05(s,1H),10.75(s,1H).
example 9
Figure GDA0002736900810000071
The method comprises the following steps: diethyl methylphosphonite (20.5g,150.1mmol), 5- (2-chloroethyl) imidazolidine-2, 4-dione (20.3g,125mmol) and chlorobenzene (20mL) were added to a 250mL three-necked flask, replaced with argon, stirred, heated to 140 ℃ to react for 20h, and the solvent and unreacted raw materials were removed by desolventization under reduced pressure to obtain 23.1g of a pale yellow viscous liquid with a yield of 79% and a purity of HPLC of 96%.
The second method comprises the following steps: diethyl methylphosphonite (20.5g,150.1mmol), 5- (2-chloroethyl) imidazolidine-2, 4-dione 3(20.3g,125mmol), tetrabutylammonium bromide (2.1g, 6.25mmol) and 20mL of chlorobenzene were added to a 250mL three-necked flask, and replaced with argon for three times, followed by stirring, heating to 140 ℃ for reaction for 8 hours, and removing the solvent and unreacted raw materials by desolvation under reduced pressure to obtain 24.0g of a pale yellow viscous liquid, the yield is 82%, and the HPLC purity is 96.5%.
Example 10
Figure GDA0002736900810000072
The product from example 8 (24g,102.5mmol), 36% HCl (40mL) was added to a sealed tube, the reaction was allowed to warm to 130 ℃ for 40h, desolventized under reduced pressure to give a pale yellow viscous liquid, ethanol (20mL) was added and stirred at room temperature for 3h to give a large amount of white solid, which was filtered, washed with ethanol (20mL x 3), and dried to give 17.6g of glufosinate-ammonium in 95% yield and 98.7% HPLC purity.
Example 11
Figure GDA0002736900810000081
A250 mL three-necked flask was charged with the product from example 9 (24g,102.5mmol), water 100mL, Ba (OH) 2 ·8H 2 O (31.6g,100mmol) was heated under reflux for 30 h. Addition of H 2 SO 4 Adjusting the pH value to 5-6, filtering, adjusting the pH value of the filtrate to 12 by using ammonia water, performing rotary evaporation to remove the solvent, and adding methanol for recrystallization. Drying to obtain 17.8g of glufosinate-ammonium with the yield of 96% and the HPLC purity of 98.5%.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.

Claims (13)

1. A process for the preparation of a hydantoin derivative of formula (I) or a salt, enantiomer or a mixture of enantiomers in all ratios thereof:
Figure FDA0003780785850000011
the method is characterized in that: the method comprises the following steps:
(a) reacting a compound of formula (II)
Figure FDA0003780785850000012
Or salts, enantiomers or mixtures of enantiomers in all ratios thereof with a compound of the formula (III)
Figure FDA0003780785850000013
Reaction to give the compound of formula (IV)
Figure FDA0003780785850000014
Or salts, enantiomers or mixtures of enantiomers in all ratios thereof;
(b) intramolecular condensation of the compound of formula (IV) in the presence of an acid to give the compound of formula (I) or a salt, enantiomer or mixture of enantiomers in all ratios thereof;
wherein:
x is-OR 3 ；
Y is O;
R 1 is hydrogen or an amino protecting group;
R 2 is hydrogen or C 1 -C 4 An alkyl group;
R 3 is hydrogen.
2. The method of claim 1, wherein: in said step (a), the compound of formula (II) or a salt, enantiomer or mixture of enantiomers thereof in all proportions is the L-configured enantiomer of the compound of formula (II).
3. The method of claim 1, wherein: the hydantoin derivatives of formula (I) or salts, enantiomers or mixtures of enantiomers in all ratios thereof refer to mixtures of enantiomers of hydantoin derivatives of formula (I);
in said step (a), the compound of formula (IV) or a salt, enantiomer or mixture of enantiomers in all proportions thereof is a mixture of enantiomers of the compound of formula (IV).
4. The method of claim 1, wherein: the hydantoin derivatives of formula (I) or salts, enantiomers or mixtures of enantiomers in all ratios thereof refer to racemic mixtures of hydantoin derivatives of formula (I);
in said step (a), the compound of formula (IV) or a salt, enantiomer or mixture of enantiomers in all ratios thereof is a racemic mixture of the compound of formula (IV).
5. The method of claim 1, wherein: said R is 1 Is hydrogen.
6. According to claimThe method of 1, characterized by: the R is 2 Is hydrogen.
7. The method of claim 1, wherein: in the step (a), the reaction temperature is 80-120 ℃.
8. The method of claim 1, wherein: in step (a), the reaction is carried out in a solvent selected from water or a polar organic solvent.
9. The method of claim 1, wherein: in step (b), the acid is any one of hydrochloric acid, nitric acid, sulfuric acid and acetic acid or a mixture thereof.
10. The method of claim 1, wherein: the step (b) is carried out at 60-120 ℃.
11. The method of claim 1, wherein: said step (b) is carried out in water or an organic solvent.
12. The method of claim 1, wherein: the method is a one-pot method.
13. A process for the preparation of glufosinate, characterized in that a compound of formula (I) is prepared according to any one of claims 1 to 12, and is subjected to an Arbuzov rearrangement reaction with diethyl methylphosphite and hydrolysis reaction to obtain glufosinate.
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JP4304916B2 (en) * 2002-04-26 2009-07-29 昭和電工株式会社 Method for producing hydantoins

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JP4304916B2 (en) * 2002-04-26 2009-07-29 昭和電工株式会社 Method for producing hydantoins

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Title
Cyclization reactions of N-carbamoyl and N-acyl derivatives of DL-homoserine;Knobler, Yehuda，等;《Tetrahedron》;19671231;第23卷(第3期);第1557-1563页 *
海因衍生物法制备草铵膦;李以名，等;《农药》;20120331;第53卷(第3期);第172-174页 *

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