CN107652242B - Synthesis of pyrimidine salicylic acid oxime ester and application of pyrimidine salicylic acid oxime ester as herbicide - Google Patents

Synthesis of pyrimidine salicylic acid oxime ester and application of pyrimidine salicylic acid oxime ester as herbicide Download PDF

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CN107652242B
CN107652242B CN201710929598.6A CN201710929598A CN107652242B CN 107652242 B CN107652242 B CN 107652242B CN 201710929598 A CN201710929598 A CN 201710929598A CN 107652242 B CN107652242 B CN 107652242B
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salicylic acid
pyrimidine salicylic
compound
formula
pyrimidine
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CN107652242A (en
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覃兆海
张磊
车传亮
杨冬燕
刘雪莲
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China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings

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  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

The invention discloses a pyrimidine salicylic acid compound, which is shown as a general formula (I),

Description

Synthesis of pyrimidine salicylic acid oxime ester and application of pyrimidine salicylic acid oxime ester as herbicide
Technical Field
The invention belongs to the technical field of herbicides, relates to application of a herbicide in selectively preventing and controlling gramineous weeds and broadleaf weeds in crops, and particularly relates to synthesis of pyrimidine oxime salicylate and application of the pyrimidine oxime salicylate as the herbicide.
Background
For example, pyrimidinyloxyl compounds (EP0658549) have an action mechanism similar to sulfonylurea and imidazolinone herbicides, are acetolactate synthase (a L S) inhibitors, have selective ultra-high-efficiency postemergence herbicidal activity against rice, wheat and the like, have no preemergence herbicidal activity, are useful for controlling various gramineae, cyperaceae and broadleaf weeds such as barnyard grass, alopecurus macrocarpesii, polygonum hydropiper and the like, are highly effective and safe for rice and wheat.
Disclosure of Invention
The object of the present invention is to provide a herbicidally active compound which has improved properties over the compounds already disclosed in the art and which is particularly suitable for use as a herbicide.
The invention provides a pyrimidine salicylic acid compound shown in a general formula (I),
Figure BDA0001428387960000011
wherein
R1Is methyl or (substituted) phenyl, the 'substitution' can be 1-5, and in the case of polysubstitution, the substituents can be the same or different. The substituent here is (C)1～C5) Alkyl radicals, (C)1～C5) Alkoxy, trifluoromethyl, trifluoromethoxy, nitro, halogen (fluorine, chlorine, bromine, iodine), (C)1～C5) Alkylthio, mesyl, trifluoromethanesulfonyl, phenyl, phenoxy, which may be linear or branched when there are alkyl groups with more than two carbon atoms, and the same applies to alkoxy;
q is selected from one of the following heterocycles:
Figure BDA0001428387960000021
wherein
N on the pyridine ring may be 2-, 3-or 4-position, R2Represents 1 to 4 substituents on the ring, which may be the same or different, and which include (C)1～C2) Alkyl radicals, (C)1～C2) Alkoxy, halogen (Cl, Br), trifluoromethyl, (substituted) phenoxy, and the like;
R3、R4is one of H, methyl and methoxy, which can be the same or different;
R5is one of H, methyl and trifluoromethyl.
Cis and trans isomers may be present in the compounds of formula (I), and the present invention also relates to cis and trans isomers encompassed by formula (I) but not specifically defined.
Preferred compounds of the formula (I), in which
R1Is methyl, 4-tolyl, 3, 4-xylyl, 4-tert-butylphenyl or 3-nitro-4-tolyl;
q is pyridin-4-yl, 2-chloropyridin-4-yl, 4, 6-dimethoxypyrimidin-2-yl or 1-methyl-3-trifluoromethylpyrazol-5-yl;
in all the following formulae, the substituents and symbols have the same definitions as those described in formula (I) unless otherwise indicated.
The preparation method of the pyrimidine salicylic acid compound comprises the following steps:
1) heterocyclic carboxylic acid, substituted benzene and thionyl chloride are used as raw materials to prepare an arone compound shown in a structural formula II;
2) respectively reacting the compounds with the structural formula II and the structural formula IV with hydroxylamine hydrochloride to prepare corresponding intermediates IIIa and IIIb;
3) and carrying out esterification reaction on the intermediates IIIa and IIIb and [2, 6-bis- (4, 6-dimethoxypyrimidine-2-yl) ] benzoic acid to obtain the compound shown in the formula (I).
Figure BDA0001428387960000031
The compounds of the general formula (I) of the present invention, collectively referred to as "the compounds of the present invention", have excellent herbicidal activity against harmful plants. The invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in crops.
The compound of the present invention can be applied in a conventional formulation in the form of wettable powder, emulsifiable concentrate, granules or suspension concentrate, and therefore, the present invention also provides a herbicidal composition containing the compound of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
1. Chemical examples
Preparation of O- (2, 6-bis ((4, 6-dimethoxypyrimidin-2-yl) oxy) benzoyl) -phenyl (pyridin-4-yl) methanone oxime (code I-70)
Step 1: synthesis of 4-methylphenyl (pyridin-4-yl) methanone
Adding 12.30g of isonicotinic acid and 100m L of thionyl chloride into a 100ml round-bottom flask, then dropwise adding 2 drops of DMF as a catalyst, heating and refluxing for 4h until the solution reacts to be light yellow and transparent, stopping heating, and after the reaction flask is cooled to room temperature, carrying out reduced pressure rotary evaporation to remove excessive thionyl chloride to obtain light yellow isonicotinoyl chloride solid for later use.
Adding 80m L dichloromethane as solvent into isonicotinoyl chloride in the round bottom flask, stirring in a prepared ice bath kettle for 10min, and slowly adding AlCl while stirring after the temperature is reduced326.67 g. toluene 11.07g was weighed into the dropping funnel and diluted with 50m L m dichloromethane, slowly added dropwise to the ice-bath round bottom flask reaction system for about 1 hour, monitored by T L C, after the reaction of the raw materials (about 16-24 hours), the ice-bath was removed and slowly poured into a 500m L beaker filled with crushed ice with stirring3Washing with saturated solution, washing with clear water, spin-drying, and purifying by column chromatography to obtain white solid 4-methylphenyl (pyridin-4-yl) methanone 12.80g with yield of 65%.
Step 2: synthesis of 4-methylphenyl (pyridin-4-yl) ketoxime
Adding 1.70g of 4-methylphenyl (pyridin-4-yl) methanone, 5.53g of potassium carbonate and 30m L of ethanol into a 100ml round-bottom flask, fully stirring, slowly adding 2.64g of hydroxylamine hydrochloride into the flask, heating to 43 ℃, monitoring the reaction to be complete in real time by using T L C, stopping heating after the reaction is finished after about 4 hours, cooling the reaction liquid to room temperature, slowly dropwise adding the mixture into 400ml of ice water while stirring, separating out a white solid, performing suction filtration by using a Buchner funnel, drying the product in the air, and recrystallizing ethyl acetate and methanol to obtain 1.77g of white solid 4-methylphenyl (pyridin-4-yl) methylketoxime with the yield of 97%.
And step 3: preparation of O- (2, 6-bis ((4, 6-dimethoxypyrimidin-2-yl) oxy) benzoyl) -4-methylphenyl (pyridin-4-yl) methanone oxime
2.64g of bispyribac-sodium (acid), 1.06g of 4-methylphenyl (pyridine-4-yl) ketoxime, 0.61g of 4-dimethylaminopyridine, 1.55g of dicyclohexylcarbodiimide and 25m of dichloromethane are added into a 100m L round-bottom flask, the mixture is heated and stirred to reflux, the reaction process is detected, the heating is stopped after 16h, 30m L saturated saline solution is added into the reaction solution after the reaction solution is cooled to room temperature, the mixture is fully stirred, filtered to remove filter residue, separated, washed by dichloromethane for three times, 5m L each time, organic phases are combined, anhydrous sodium sulfate is dried, and separation and purification are carried out by reduced pressure rotary evaporation chromatographic column, thus obtaining 2.68g of O- (2, 6-bis ((4, 6-dimethoxypyrimidine-2-yl) oxygen) benzoyl) -4-methylphenyl (pyridine-4-yl) ketoxime white solid, the yield is 86%, and the melting point is 48-50 ℃.
1H NMR(300MHz,CDCl3)8.67(d,2H),7.56–7.45(m,1H),7.33(d,2H),7.12(dd,4H),5.74(s,2H),3.74(s,12H),2.36(s,3H).13C NMR(75MHz,CDCl3)172.44,163.37,161.70,160.29,151.32,149.42,141.47,139.84,131.39,129.98,128.89,128.23,122.79,119.84,118.93,84.71,53.77,21.04.HRMS(M+H+)，[C32H29N6O8]+Calculated 625.2041, measured 625.2047.
The examples listed in table I below were prepared by similar methods as described above. These compounds are particularly preferred.
Table 1.
Figure BDA0001428387960000051
Figure BDA0001428387960000061
Figure BDA0001428387960000071
Figure BDA0001428387960000081
Figure BDA0001428387960000091
Figure BDA0001428387960000101
Figure BDA0001428387960000111
Figure BDA0001428387960000121
Figure BDA0001428387960000131
Figure BDA0001428387960000141
Figure BDA0001428387960000151
Figure BDA0001428387960000161
Figure BDA0001428387960000171
Figure BDA0001428387960000181
Figure BDA0001428387960000191
Figure BDA0001428387960000201
Figure BDA0001428387960000211
Figure BDA0001428387960000221
Figure BDA0001428387960000231
Figure BDA0001428387960000241
Figure BDA0001428387960000251
Figure BDA0001428387960000261
Figure BDA0001428387960000271
Figure BDA0001428387960000281
Figure BDA0001428387960000291
Figure BDA0001428387960000301
Figure BDA0001428387960000311
Figure BDA0001428387960000321
Figure BDA0001428387960000331
Figure BDA0001428387960000341
Figure BDA0001428387960000351
Figure BDA0001428387960000361
2. Formulation examples
(1) The powder is prepared by mixing 10 wt% of compound (I) with 90 wt% of talcum powder, and pulverizing the mixture in a hammer mill.
(2) The wettable powder is obtained by mixing 25% by weight of compound (I), 64% by weight of kaolin, 10% by weight of sodium lignosulfonate and 1% by weight of oleoyl methyltaurine and grinding the mixture in a grinder.
(3) Aqueous dispersion concentrates 20% by weight of compound (I), 6% by weight of alkylphenol polyglycol ether (Triton X207), 3% by weight of isotridecanol polyglycol ether (8E0) and 71% by weight of mineral oil were mixed and the mixture was ground in a ball mill to a particle size of less than 5 μm.
(4) Water dispersible granules A mixture of 75% by weight of Compound (I), 10% by weight of calcium lignosulphonate, 5% by weight of sodium lauryl sulphate, 3% by weight of polyvinyl alcohol and 7% by weight of kaolin is ground in a mill and the powder is granulated in a fluidised bed by spraying with water.
(5) Emulsifiable concentrate 72% by weight of xylene and 12% by weight of emulsifier 2201 were added to a reaction vessel, stirred for 15 minutes, then 5% by weight of compound (I) and 1% by weight of antioxidant BHT were added, and stirred for 1 hour until all were dissolved.
3. Biological control example
The compounds of the invention and of the closest known prior art are used in the comparative examples:
table 2.
Figure BDA0001428387960000371
Figure BDA0001428387960000381
Postemergence herbicidal activity (amount 20g AI/ha):
seeds of gramineous weeds and broadleaf weeds are placed in a pot containing sandy loam and covered with soil to grow under good growth conditions. After sowing for 2-3 weeks, the test plants growing to the two-leaf period are treated. The compound (I) of the present invention or the herbicidal composition containing (I) is formulated into an Emulsion Concentrate (EC), diluted with water and applied to the green parts of plants. The test plants were placed in a greenhouse and growth conditions were maintained. Herbicidal activity was assessed visually after 3 weeks by control: 100% activity is dead, 0% activity is similar to control, and/is not tested. The results show that the compounds of the present invention have higher herbicidal activity than the control compounds.
Table 3.
Figure BDA0001428387960000391
And (3) crop compatibility test:
the same method for measuring the post-emergence herbicidal activity is adopted to test rice, wheat and tobacco, and the phytotoxicity condition is observed by visual observation: 0, the plant grows completely normally; 1, leaves are slightly yellow; 2, the yellowing of leaves is serious; 3, the individual leaves turn yellow and wither again strictly; 4-plant growth was severely inhibited; the 5 ═ plant died completely. The results are shown in Table 4.
Table 4.
Figure BDA0001428387960000392
Figure BDA0001428387960000401

Claims (5)

1. A preparation method of a pyrimidine salicylic acid compound is characterized in that the pyrimidine salicylic acid compound is shown as a general formula (I),
Figure FDA0002521954210000011
wherein
R1Represents methyl or substituted phenyl, the substituted phenyl is 4-tolyl, 3, 4-xylyl, 2, 3-dichlorophenyl, 3-nitro-4-tolyl,
q is pyridin-4-yl or 2-chloropyridin-4-yl;
the preparation method comprises the following steps:
1) heterocyclic carboxylic acid, substituted benzene and thionyl chloride are used as raw materials to prepare an arone compound shown in a structural formula II;
2) respectively reacting the compounds with the structural formula II and the structural formula IV with hydroxylamine hydrochloride to prepare corresponding intermediates IIIa and IIIb;
3) carrying out esterification reaction on the intermediates IIIa and IIIb and [2, 6-bis- (4, 6-dimethoxypyrimidine-2-yl) ] benzoic acid to obtain a compound shown in a formula (I);
Figure FDA0002521954210000012
r is R1Substituted phenyl groups as shown.
2. The method of claim 1, wherein the compound of formula (I) comprises cis and trans isomers.
3. Use of a pyrimidine salicylic acid compound prepared by the method according to claim 1 or 2 in the preparation of herbicides, wherein the pyrimidine salicylic acid compound is applied in conventional dosage forms.
4. The use according to claim 3, wherein the conventional formulation comprises dusts, wettable powders, water dispersible concentrates, water dispersible granules, emulsifiable concentrates, and suspension concentrates.
5. The use as claimed in claim 3, wherein the herbicide is used for the weeding of rice, wheat and tobacco.
CN201710929598.6A 2017-10-09 2017-10-09 Synthesis of pyrimidine salicylic acid oxime ester and application of pyrimidine salicylic acid oxime ester as herbicide Expired - Fee Related CN107652242B (en)

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CN109553574B (en) * 2018-12-27 2020-07-24 北京颖泰嘉和生物科技股份有限公司 Pyridine acid compound, preparation method thereof, herbicide composition and application thereof
CN111269223B (en) * 2020-04-07 2023-08-11 西安近代化学研究所 Isoxazole oxime ester derivative and application thereof
CN115124477B (en) * 2022-08-08 2024-05-10 中国农业大学 Novel pyrimidine salicylic acid phenolic ester, synthetic method thereof and application of pyrimidine salicylic acid phenolic ester as herbicide

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CN103319421A (en) * 2013-06-07 2013-09-25 常州大学 Preparation method of pyribenzoxim belonging to pyrimidinylthiobenzoate herbicide
CN104302629A (en) * 2013-12-03 2015-01-21 南京慧博生物科技有限公司 Novel herbicidal active pyridine salicylic acid compound, prepare method thereof, and purpose of being herbicidal

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CN103319421A (en) * 2013-06-07 2013-09-25 常州大学 Preparation method of pyribenzoxim belonging to pyrimidinylthiobenzoate herbicide
CN104302629A (en) * 2013-12-03 2015-01-21 南京慧博生物科技有限公司 Novel herbicidal active pyridine salicylic acid compound, prepare method thereof, and purpose of being herbicidal

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