CN103766393A - Pyrimidine-containing organophosphorus fungicide and application - Google Patents
Pyrimidine-containing organophosphorus fungicide and application Download PDFInfo
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- CN103766393A CN103766393A CN201410046039.7A CN201410046039A CN103766393A CN 103766393 A CN103766393 A CN 103766393A CN 201410046039 A CN201410046039 A CN 201410046039A CN 103766393 A CN103766393 A CN 103766393A
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Abstract
The invention belongs to the technical field of fungicide compounds, and particularly relates to a pyrimidine-containing organophosphorus fungicide and application. The pyrimidine-containing organophosphorus fungicide can be used for controlling and preventing damage of fungi to plants in the farmland, the garden and the park, and is shown in a formula I described in the specification. According to a novel fungicide compound, by fully utilizing the characteristic of an existing compound, the structure is effectively modified, so that a brand-new compound structure is obtained, and thus a method is a known and feasible method of a novel pesticide product disclosed by the invention.
Description
Technical field:
The invention belongs to the technical field of fungicide compound, be specially a kind of organophosphorus fungicide that contains pyrimidine and application, can be used in farmland, orchard, gardens control and the injury of prevention fungi to plant.
Technical background:
Organophosphorus fungicide is for controlling and a series bactericidal agent that prevents fungi to plant injury in agriculture field, wherein in commercial product, there are edifenphos (edifenphos), iprobenfos (iprobenfos), pyrazophos (pyrazophos), tolelofos-methyl (tolclofos-methyl). all kinds of fungal diseases such as the bactericide of these organic phosphors has been used for the success of agriculture field has prevented and treated white powder, it is withered to stand, rice blast, soybean rust, obtain good control efficiency.But the problem facing is that due to extensively using for many years of this series products, the fungi in plant corpus has produced resistance to this compounds, and the effect of control is declined.
The compound of miazines all has application very widely in agricultural chemicals and medicine, and Bai Suzhen etc. have pointed out pyrimidine ring specifically application in agricultural chemicals and medicine in having delivered " the application study progress of pyrimidine compound " in " Shanxi chemical industry " the 29th volume first phase.5-flurocytosine (CAS NO.2022-85-7) is used for the anti-fungal infection of human body as a kind of medicine of extensive use in medicine, Ye You company study its in agriculture field the purposes as bactericide, and declare a class patent, as: Dow AgroSciences, at the CN103319826 of China's application, has pointed out the concertedness agrohorticultural bactericide of 5-flurocytosine and other fungicide.
Dow AgroSciences has also applied for the derivative of 5-flurocytosine (CAS NO.2022-85-7), as CN 101977900, CN 102497781, CN 102574831, CN 102548979, CN 102548980, CN 102548981, CN 102762210, the a series of patents such as CN 102946730, but in its patented invention, do not mention in Dow AgroSciences the compound that this patent relates to, even change its structure by " biological wait for row theory " rule, can not obtain the compound that this patent relates to, the compound of this patent invention can effectively solve the resistance problem of current bactericide.
Summary of the invention:
The object of the invention is to the problem for above-mentioned existence, and a kind of better resistance, the organophosphorus fungicide that contains pyrimidine and application that cost is low are provided.
Technical scheme of the present invention is:
Containing an organophosphorus fungicide for pyrimidine, this fungicide compound is suc as formula shown in I:
Wherein,
R
1for oxygen (O) or sulphur (S);
R
2for C
1-C
6alkyl, C
2-C
6thiazolinyl or C
2-C
6alkynyl;
R
3, R
4, be respectively following substituted radical in one:
H；
Optionally by 1 to 3 R
5the C replacing
1-C
6alkyl;
Optionally by 1 to 3 R
5the C replacing
2-C
6thiazolinyl;
5-or 6-unit heteroaromatic rings group, it is selected from: furyl, pyridine radicals, N-pyridine oxide base, pyrimidine radicals, pyridazinyl, pyrazinyl, thiazolyl, triazinyl, thiadiazolyl group, oxazolyl, isoxazolyl and triazolyl, wherein each heteroaromatic rings group is optionally by 1 to 3 R
6replace;
Imidazoles: Ben, oxazole, isoxazole, furans, thiazole, pyrimidine, pyridine, pyrroles, pyrazine and thiophene that aromatic ring group or heteroaromatic rings group condense, wherein each aromatics or heteroaromatic rings are optionally by 1 to 3 R
6replace;
Benzo [1,3] dioxa cyclopentenyl;
3H-isobenzofuran-1-ketone group;
Cyano group;
Optionally by 1 to 3 R
5the C replacing
3-C
6alkynyl;
-C(＝O)R
7；
-C(＝O)OCH
2C(＝O)R
8；
-C(＝S)R
7；
-C(＝S)NHR
8；
-C(＝O)N(R
8)R
9；
-OR
7；
-P(O)(OR
10)
2；
-S(O)
2R
8；
-SR
8；
-Si(R
8)
3；
-N(R
11)R
9；
-N＝C(R
12)R
13；
-(CHR
14)
mr
15, the integer that wherein m is 1-3;
-(CHR
16) OR
17; Or
-C(＝NR
13)SR
13；
R
5for halogen, C
1-C
6alkyl, C
1-C
4haloalkyl, C
1-C
4alkoxyl, C
1-C
4halogenated alkoxy, C
1-C
4alkyl sulfenyl, C
1-C
4haloalkyl sulfenyl, amino, C
1-C
3alkyl amino, C
2-C
6alkoxy carbonyl, C
2-C
6alkyl-carbonyl, C
2-C
6alkyl amino-carbonyl ,-OH, N methyl piperazine or C
3-C
6one in trialkylsilkl;
R
6for being selected from the one in following radicals: halogen, cyano group, nitro, C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6hydroxy alkyl, C
2-C
6alkoxyalkyl, C
2-C
6halogenated alkoxy alkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group, C
3-C
6alkynyl, C
3-C
6halo alkynyl, hydroxyl, C
1-C
6alkoxyl, C
1-C
6halogenated alkoxy, C
2-C
6thiazolinyl oxygen base, C
2-C
6haloalkenyl group oxygen base, C
3-C
6alkynyloxy base, C
3-C
6halo alkynyloxy base, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6thiazolinyl sulfenyl, C
2-C
6haloalkenyl group sulfenyl, C
2-C
6haloalkenyl group sulfonyl, C
3-C
6alkynyl sulfenyl, C
3-C
6alkynyl sulfonyl, C
3-C
6halo alkynyl sulfonyl, C
1-C
6alkyl amino, C
2-C
8dialkyl amido, C
3-C
8dialkyl amino carbonyl, C
3-C
6trialkylsilkl, thiazolyl, phenyl, pyrimidine radicals or pyridine radicals, wherein said thiazolyl, phenyl, pyridine radicals or pyrimidine radicals are optionally by 1 to 3 R
18replace;
R
7for being selected from the one in following radicals: H; C
1-C
6alkyl; C
2-C
6thiazolinyl; C
1-C
5haloalkyl; Benzyl, it is optionally by 1-5 R
18replace; CHR
19c (O) OR
20or contain the saturated or unsaturated ring of 1 to 3 heteroatomic 5-or 6-unit, wherein each ring is optionally by 1 to 3 R
21replace;
R
8for being selected from the one in following radicals: C
1-C
6alkyl, C
1-C
6haloalkyl, amino, C
1-C
6alkyl amino, C
2-C
6dialkyl amido, optionally by 1 to 3 R
30the phenyl replacing or contain 1 to 3 heteroatomic 5-or the saturated or unsaturated ring of 6-unit, wherein each ring is optionally by 1 to 3 R
21replace;
R
9for H, C
1-C
6alkyl, C
1-C
6haloalkyl or optionally by 1 to 3 R
18the phenyl replacing;
R
10for H or C
1-C
6alkyl;
R
11for H, C
1-C
6alkyl, C
1-C
6haloalkyl ,-C (=O) R
17or optionally by 1 to 3 R
18the phenyl replacing;
R
12for H or C
1-C
6alkyl;
R
13for H, C
1-C
6alkyl or optionally by 1 to 3 R
18the phenyl replacing;
R
14for being selected from the one in following radicals:
H；
Halogen;
Cyano group;
Nitro;
C
1-C
6alkyl;
C
1-C
6haloalkyl;
Optionally by 1 to 3 R
20replace phenyl or optionally by 1 to 3 R
18the benzyl replacing;
C
1-C
6hydroxy alkyl;
C
2-C
6alkoxyalkyl;
C
3-C
6halo alkynyl;
C
2-C
6thiazolinyl;
C
2-C
6haloalkenyl group;
C
3-C
6alkynyl;
C
1-C
6alkoxyl;
C
1-C
6halogenated alkoxy;
C
1-C
6alkyl sulfenyl;
C
1-C
6alkyl amino;
C
2-C
8dialkyl amido;
C
3-C
6cycloalkyl amino;
C
4-C
6(alkyl) cycloalkyl amino;
C
2-C
6alkyl-carbonyl;
C
2-C
6alkoxy carbonyl;
C
2-C
6alkyl amino-carbonyl;
C
3-C
8dialkyl amino carbonyl;
C
3-C
6trialkylsilkl;
The heteroaromatic rings group that condenses of ring, it is selected from: benzothienyl, quinolyl, isoquinolyl, thieno [2,3-b] pyridine radicals, 1-methyl isophthalic acid H-thieno [2,3-c] pyrazolyl and benzimidazolyl, wherein each described ring is optionally by 1 to 3 R
18further replace; Or 5-or 6-unit heteroaromatic rings group, it is selected from: furyl, pyridine radicals, N-pyridine oxide base, pyrimidine radicals, pyridazinyl, pyrazinyl, thiazolyl, triazinyl, thiadiazolyl group, oxazolyl, isoxazolyl, triazolyl or thienyl;
R
15for being selected from the one in following radicals: H, halogen or optionally by 1-5 R
18the phenyl replacing;
R
16for H, C
1-C
6alkyl, C
1-C
6alkoxyl, benzyl or phenyl, wherein benzyl or phenyl are separately optionally by 1 to 3 R
18replace;
R
17for being selected from the one in following radicals:
H；
C
1-C
6alkyl;
C
1-C
6haloalkyl;
C
1-C
6alkoxyalkyl;
C
2-C
6alkyl-carbonyl;
Benzyl or phenyl, wherein benzyl or phenyl are separately optionally by 1 to 3 R
18replace; Or contain the saturated or unsaturated ring of 1 to 3 heteroatomic 5-or 6-unit, wherein each ring is optionally by 1 to 3 R
21replace;
R
18for being selected from the one in following radicals: halogen, cyano group, nitro, amino, C
1-C
6alkoxyl alkoxyl, C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6hydroxy alkyl, C
2-C
6alkoxyalkyl, C
2-C
6halogenated alkoxy alkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group, C
3-C
6alkynyl, C
3-C
6halo alkynyl, hydroxyl, C
1-C
6alkoxyl, C
1-C
6halogenated alkoxy, C
2-C
6thiazolinyl oxygen base, C
2-C
6haloalkenyl group oxygen base, C
3-C
6alkynyloxy base, C
3-C
6halo alkynyloxy base, C
1-C
6alkyl sulfenyl, C
1-C
6haloalkyl sulfenyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6thiazolinyl sulfenyl, C
2-C
6haloalkenyl group sulfenyl, C
2-C
6haloalkenyl group sulfonyl, C
3-C
6alkynyl sulfenyl, C
3-C
6alkynyl sulfonyl, C
3-C6 halo alkynyl sulfonyl, C
1-C
6alkyl amino, C
2-C
8dialkyl amido, C
3-C
8dialkyl amino carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6alkyl-carbonyl, C
3-C
6trialkylsilkl, 2-[(E)-methoxyimino]-N-methyl-acetylamino, phenyl, benzyl, benzyloxy, phenoxy group or 5-or 6-unit heteroaromatic rings group, wherein phenyl, benzyl, benzyloxy, phenoxy group or 5-or 6-unit heteroaromatic rings group are optionally independently selected from R by 1 to 3 separately
22substituting group replace;
R
19for H, C
1-C
6alkyl or C
1-C
6haloalkyl;
R
20for H, C
1-C
6alkyl, C
1-C
6haloalkyl or benzyl;
R
21for being selected from the one in following radicals: halogen, C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl, C
1-C
6halogenated alkoxy, C
1-C
6alkyl sulfenyl, C
1-C
6haloalkyl sulfenyl, amino, C
1-C
6alkyl amino, C
2-C
6dialkyl amido, C
2-C
6alkoxy carbonyl or C
2-C
6alkyl-carbonyl;
R
22for being selected from the one in following radicals: halogen, cyano group, nitro, C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6hydroxy alkyl, C
2-C
6alkoxyalkyl, C
2-C
6halogenated alkoxy alkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group, C
3-C
6alkynyl, C
3-C
6halo alkynyl, hydroxyl, C
1-C
6alkoxyl, C
1-C
6halogenated alkoxy, C
2-C
6thiazolinyl oxygen base, C
2-C
6haloalkenyl group oxygen base, C
3-C
6alkynyloxy base, C
3-C
6halo alkynyloxy base, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6thiazolinyl sulfenyl, C
2-C
6haloalkenyl group sulfenyl, C
2-C
6haloalkenyl group sulfonyl, C
3-C
6alkynyl sulfenyl, C
3-C
6alkynyl sulfonyl, C
3-C
6halo alkynyl sulfonyl, C
1-C
6alkyl amino, C
2-C
8dialkyl amido, C
3-C
8dialkyl amino carbonyl or C
3-C
6trialkylsilkl.
As preferably, fungicide compound of the present invention, wherein,
R
1for oxygen (O) or sulphur (S);
R
2for C
1-C
6alkyl;
R
3, R
4, be respectively following substituted radical in one:
H；
C
1-C
6alkyl.
As further preferred, fungicide compound of the present invention, wherein,
R
1for oxygen (O) or sulphur (S);
R
2for methyl or ethyl;
R
3for methyl or H;
R
4for methyl or H.
As further preferred, fungicide compound of the present invention, wherein,
R
1for sulphur (S);
R
2for ethyl;
R
3for methyl;
R
4for methyl or H.
As further preferred, fungicide compound of the present invention, wherein,
R
1for oxygen (O);
R
2for methyl or ethyl;
R
3for methyl or H;
R
4for methyl or H.
As further preferred, fungicide compound of the present invention, wherein,
R
1for oxygen (O);
R
2for methyl;
R
3for methyl or H;
R
4for methyl or H.
As further preferred, fungicide compound of the present invention, wherein,
R
1for oxygen (O);
R
2for ethyl;
R
3for methyl or H;
R
4for methyl or H.
As further preferred, fungicide compound of the present invention, wherein,
R
1for oxygen (O);
R
2for ethyl or methyl;
R
3for methyl;
R
4for methyl or H.
Fungicide compound of the present invention, for preventing and treating the fungal disease on cereal crops, economic crops, flowers, forest, fruit; As preferably, for preventing and treating damping off, powdery mildew, rust, rice blast, gall rust, yellow rust, late blight, downy mildew, gray mold, stalk break, balck shank, head blight, damping off, root rot.
Fungicide compound of the present invention can be prepared into solution, granule, wettable pulvis, the preparation such as concentrate or missible oil, aqua can flow, as in some solvents as toluene or methyl alcohol, add fungicide compound of the present invention to be prepared into missible oil, or add other auxiliary agents such as kaolin to be prepared into pulvis etc.Fungicide compound of the present invention is prepared into operable formulation products, is that the industry is the technology of widely knowing.Above-mentioned just illustrates that it is the technology that the industry is widely known that compound of the present invention is prepared into preparation for example, is not that this compound of explanation can only be prepared into preparation in the content relating to for example.
In addition, the preparation method of the fungicide compound the present invention relates to, can be by containing substituent pyrimidines and reacting and obtain target compound containing substituent sulfo-(or oxo) phosphoryl chloride phosphorus oxychloride compound.
Beneficial effect of the present invention is: the invention provides a kind of novel fungicide compound, make full use of the characteristic of existing compound, carry out effective structure of modification, obtain brand-new compound structure, this is also generally acknowledged, an effective method of invention novel agrochemical product.In fact, also just by the research of this class, it is lower that people have obtained cost, the better types of applications of control efficiency is in the compound in agriculture field, in a word, the organophosphorus fungicide that contains pyrimidine and the application that the invention provides a kind of better resistance, cost is low, consumption is low, control efficiency are good, its control efficiency (in the situation that amount ratio commercially available prod is few) can be up to more than 90%, there is outstanding substantive distinguishing features and significant progressive, possess creativeness.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in detail, but is not limitation of the present invention.
Embodiment 1:
O-(4-amino-5-fluorine pyrimidine-2-base) O, the preparation of O-dimethyl disulfide substituted phosphate
With stir and the four-hole boiling flask of 1000 milliliters, thermometer in, add 500 milliliters of anhydrous N, dinethylformamide, add the 5-flurocytosine of 0.1 mole, the at room temperature sodium metal that adds 0.1 mole slowly, finish, stir 2 hours, add O, O-dimethyl thiophosphoryl chloride, under room temperature, stir 48 hours, under 1mmHg, distill out N, dinethylformamide is clean to solvent distillation, vapo(u)rizing temperature is not more than 80 degree, the product obtaining filters to remove salt by 500 milliliters of rear mistakes of dissolving of methyl alcohol, methyl alcohol is removed in distillation, obtain O-(4-amino-5-fluorine pyrimidine-2-base) O, O-dimethyl disulfide substituted phosphate crude product, with liquid-phase chromatographic analysis content be 78%, yield is 80%.As chromatographic solution, obtain sterling with ethyl acetate-n-hexane (4:1).Elementary analysis calculated data is: C, 28.46; H, 3.58; N, 16.60; The actual result recording is: C, 28.51; H, 3.56; N, 16.58.
Can synthesize and obtain following compounds by method above:
O-(4-amino-5-fluorine pyrimidine-2-base) O, O-systox
Elementary analysis calculated data: C, 34.16; H, 4.66; N, 14.94; The actual result recording is: C, 34.19; H, 4.68; N, 14.91.
O-(4-amino-5-fluorine pyrimidine-2-base) O, O-diethyl substituted phosphate
Elementary analysis calculated data C, 36.23; H, 4.94; N, 15.85; The actual result recording is: C, 36.22; H, 4.95; N, 15.88.
Embodiment 2:
O-(4-acetamido-5-FU-2-yl) OO-systox
With stir and the four-hole boiling flask of 1000 milliliters, thermometer in, add 500 milliliters of anhydrous N, dinethylformamide, add the 5-acetyl fluoride cytimidine of 0.1 mole, the at room temperature sodium metal that adds 0.1 mole slowly, finish, stir 2 hours, add O, O-dimethyl thiophosphoryl chloride, under room temperature, stir 48 hours, under 1mmHg, distill out N, dinethylformamide is clean to solvent distillation, vapo(u)rizing temperature is not more than 80 degree, the product obtaining filters to remove salt by 500 milliliters of rear mistakes of dissolving of methyl alcohol, methyl alcohol is removed in distillation, obtain O-(4-acetamido-5-FU-2-yl) O, O-systox crude product, with liquid-phase chromatographic analysis content be 42%, yield is 39%.Purify as chromatographic solution column chromatography with ethyl acetate-n-hexane (6:4), obtain sterling, elementary analysis calculated data is: C, 32.55; H, 3.76; N, 14.23; The actual result recording is: C, 32.53; H, 3.78; N, 14.22.
Embodiment 3:
O-(the fluoro-4-(methylamino of 5-) pyrimidine-2-base) O, O-dimethyl disulfide substituted phosphate
With stir and the four-hole boiling flask of 100 milliliters, thermometer in, add 50 milliliters of anhydrous butanone, add the 5-fluorine 4-methylamino-pyrimid-2-one of 0.01 mole, the at room temperature sodium hydroxide that adds 0.011 mole slowly, finish, stir 2 hours, add O, O-dimethyl thiophosphoryl chloride, under room temperature, stir 96 hours, under 10mmHg, distill out butanone clean to solvent distillation, vapo(u)rizing temperature is not more than 40 degree, 500 milliliters of rear mistakes of dissolving of residual ight toluene filter to remove salt, toluene is removed in distillation, obtain O-(the fluoro-4-(methylamino of 5-) pyrimidine-2-base) O, O-dimethyl disulfide substituted phosphate crude product, with liquid-phase chromatographic analysis content be 56%, yield is 49%.Purify as chromatographic solution column chromatography with ethyl acetate-n-hexane (6:4), obtain sterling, elementary analysis calculated data is: C, 31.46; H, 4.15; N, 15.73; The actual result recording is: C, 31.48; H, 4.17; N, 15.71.
Preferred compound of the present invention is in table 1.
Compound list 1
The field experiment of the compounds of this invention is as follows:
Compound in upper table is processed into wetting powder, missible oil, aqua, soluble concentrate, aqueous emulsion, suspending agent etc., be watered spraying control gardens, the fungal disease of ornamental plants, the fruit diseases such as grape and soybean rust, rice seedling blight, rice blast, powdery mildew of cucumber etc., contrast with the agricultural chemicals of the conventional corresponding disease of control, control efficiency has notable difference, also compare with the conventional pesticide that uses the long period simultaneously, even if strengthening dosage, conventional pesticide can not effectively prevent and treat corresponding disease, produced resistance, and noval chemical compound can effectively solve these resistance problems, test data is as follows:
(1) control pine tree gall rust (ultra low volume spray):
The preventive effect of compound 1 in the time that active ingredient dosage is 200 grams/acre, is that the preventive effect of 300 grams/acre has significant difference with contrasting 10% nitrile bacterium azoles missible oil dosage, can not effectively prevent and treat disease even if 20% pyrazophos missible oil strengthens dosage.
(2) chrysanthemum powdery mildew (conventional spraying) is viewed and admired in control:
The preventive effect of compound 2 in the time that dosage is 100 mg/kg, with contrast 50% and cough up preventive effect that the clear wetting powder dosage of bacterium is 150 mg/kg without significant difference, but preventive effect when dosage is 125 mg/kg is with contrasting preventive effect, there were significant differences, can not effectively prevent and treat disease even if 50% pyrazophos wetting powder strengthens dosage.
(3) control rice blast (conventional spraying):
Compound 103 is in the preventive effect of high and low two dosages, and all there were significant differences compared with the control, higher than contrast, can not effectively prevent and treat disease even if 50% edifenphos breast strengthens dosage.
(4) control soybean rust (conventional spraying):
Compound 104 is in the preventive effect of high and low two dosages, and all there were significant differences compared with the control, higher than contrast, can not effectively prevent and treat disease even if 25% Zineb wettable powder strengthens dosage.
(5) control grape powdery mildew (conventional spraying):
Compound 126 is in the preventive effect of high and low two dosages, and all there were significant differences compared with the control, higher than contrast, can not effectively prevent and treat disease even if 25% pyrazophos missible oil strengthens dosage.
(6) control rice blast (conventional spraying):
Compound 127 is in the preventive effect of high and low two dosages, and all there were significant differences compared with the control, higher than contrast, can not effectively prevent and treat disease even if 3% Iprobenfos aqueous emulsion strengthens dosage.
(7) control rice seedling blight (spraying in seedling stage):
Compound 172 is in the preventive effect of high and low two dosages, and all there were significant differences compared with the control, higher than contrast, can not effectively prevent and treat disease even if 15% tolelofos-methyl wetting powder strengthens dosage.
(8) prevent and treat powdery mildew of cucumber (conventional spraying):
Compound 173 is in the preventive effect of high and low two dosages, and all there were significant differences compared with the control, higher than contrast, can not effectively prevent and treat disease even if 10% pyrazophos missible oil strengthens dosage.
Claims (10)
1. containing an organophosphorus fungicide for pyrimidine, this fungicide compound is suc as formula shown in I:
Wherein,
R
1for oxygen (O) or sulphur (S);
R
2for C
1-C
6alkyl, C
2-C
6thiazolinyl or C
2-C
6alkynyl;
R
3, R
4, be respectively following substituted radical in one:
H；
Optionally by 1 to 3 R
5the C replacing
1-C
6alkyl;
Optionally by 1 to 3 R
5the C replacing
2-C
6thiazolinyl;
5-or 6-unit heteroaromatic rings group, it is selected from: furyl, pyridine radicals, N-pyridine oxide base, pyrimidine radicals, pyridazinyl, pyrazinyl, thiazolyl, triazinyl, thiadiazolyl group, oxazolyl, isoxazolyl and triazolyl, wherein each heteroaromatic rings group is optionally by 1 to 3 R
6replace;
Imidazoles: Ben, oxazole, isoxazole, furans, thiazole, pyrimidine, pyridine, pyrroles, pyrazine and thiophene that aromatic ring group or heteroaromatic rings group condense, wherein each aromatics or heteroaromatic rings are optionally by 1 to 3 R
6replace;
Benzo [1,3] dioxa cyclopentenyl;
3H-isobenzofuran-1-ketone group;
Cyano group;
Optionally by 1 to 3 R
5the C replacing
3-C
6alkynyl;
-C(＝O)R
7；
-C(＝O)OCH
2C(＝O)R
8；
-C(＝S)R
7；
-C(＝S)NHR
8；
-C(＝O)N(R
8)R
9；
-OR
7；
-P(O)(OR
10)
2；
-S(O)
2R
8；
-SR
8；
-Si(R
8)
3；
-N(R
11)R
9；
-N＝C(R
12)R
13；
-(CHR
14)
mr
15, the integer that wherein m is 1-3;
-(CHR
16) OR
17; Or
-C(＝NR
13)SR
13；
R
5for halogen, C
1-C
6alkyl, C
1-C
4haloalkyl, C
1-C
4alkoxyl, C
1-C
4halogenated alkoxy, C
1-C
4alkyl sulfenyl, C
1-C
4haloalkyl sulfenyl, amino, C
1-C
3alkyl amino, C
2-C
6alkoxy carbonyl, C
2-C
6alkyl-carbonyl, C
2-C
6alkyl amino-carbonyl ,-OH, N methyl piperazine or C
3-C
6one in trialkylsilkl; R
6for being selected from the one in following radicals: halogen, cyano group, nitro, C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6hydroxy alkyl, C
2-C
6alkoxyalkyl, C
2-C
6halogenated alkoxy alkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group, C
3-C
6alkynyl, C
3-C
6halo alkynyl, hydroxyl, C
1-C
6alkoxyl, C
1-C
6halogenated alkoxy, C
2-C
6thiazolinyl oxygen base, C
2-C
6haloalkenyl group oxygen base, C
3-C
6alkynyloxy base, C
3-C
6halo alkynyloxy base, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6thiazolinyl sulfenyl, C
2-C
6haloalkenyl group sulfenyl, C
2-C
6haloalkenyl group sulfonyl, C
3-C
6alkynyl sulfenyl, C
3-C
6alkynyl sulfonyl, C
3-C
6halo alkynyl sulfonyl, C
1-C
6alkyl amino, C
2-C
8dialkyl amido, C
3-C
8dialkyl amino carbonyl, C
3-C
6trialkylsilkl, thiazolyl, phenyl, pyrimidine radicals or pyridine radicals, wherein said thiazolyl, phenyl, pyridine radicals or pyrimidine radicals are optionally by 1 to 3 R
18replace;
R
7for being selected from the one in following radicals: H; C
1-C
6alkyl; C
2-C
6thiazolinyl; C
1-C
5haloalkyl; Benzyl, it is optionally by 1-5 R
18replace; CHR
19c (O) OR
20or contain the saturated or unsaturated ring of 1 to 3 heteroatomic 5-or 6-unit, wherein each ring is optionally by 1 to 3 R
21replace;
R
8for being selected from the one in following radicals: C
1-C
6alkyl, C
1-C
6haloalkyl, amino, C
1-C
6alkyl amino, C
2-C
6dialkyl amido, optionally by 1 to 3 R
30the phenyl replacing or contain 1 to 3 heteroatomic 5-or the saturated or unsaturated ring of 6-unit, wherein each ring is optionally by 1 to 3 R
21replace;
R
9for H, C
1-C
6alkyl, C
1-C
6haloalkyl or optionally by 1 to 3 R
18the phenyl replacing;
R
10for H or C
1-C
6alkyl;
R
11for H, C
1-C
6alkyl, C
1-C
6haloalkyl ,-C (=O) R
17or optionally by 1 to 3 R
18the phenyl replacing;
R
12for H or C
1-C
6alkyl;
R
13for H, C
1-C
6alkyl or optionally by 1 to 3 R
18the phenyl replacing;
R
14for being selected from the one in following radicals:
H；
Halogen;
Cyano group;
Nitro;
C
1-C
6alkyl;
C
1-C
6haloalkyl;
Optionally by 1 to 3 R
20replace phenyl or optionally by 1 to 3 R
18the benzyl replacing;
C
1-C
6hydroxy alkyl;
C
2-C
6alkoxyalkyl;
C
3-C
6halo alkynyl;
C
2-C
6thiazolinyl;
C
2-C
6haloalkenyl group;
C
3-C
6alkynyl;
C
1-C
6alkoxyl;
C
1-C
6halogenated alkoxy;
C
1-C
6alkyl sulfenyl;
C
1-C
6alkyl amino;
C
2-C
8dialkyl amido;
C
3-C
6cycloalkyl amino;
C
4-C
6(alkyl) cycloalkyl amino;
C
2-C
6alkyl-carbonyl;
C
2-C
6alkoxy carbonyl;
C
2-C
6alkyl amino-carbonyl;
C
3-C
8dialkyl amino carbonyl;
C
3-C
6trialkylsilkl;
The heteroaromatic rings group that condenses of ring, it is selected from: benzothienyl, quinolyl, isoquinolyl, thieno [2,3-b] pyridine radicals, 1-methyl isophthalic acid H-thieno [2,3-c] pyrazolyl and benzimidazolyl, wherein each described ring is optionally by 1 to 3 R
18further replace; Or 5-or 6-unit heteroaromatic rings group, it is selected from: furyl, pyridine radicals, N-pyridine oxide base, pyrimidine radicals, pyridazinyl, pyrazinyl, thiazolyl, triazinyl, thiadiazolyl group, oxazolyl, isoxazolyl, triazolyl or thienyl;
R
15for being selected from the one in following radicals: H, halogen or optionally by 1-5 R
18the phenyl replacing;
R
16for H, C
1-C
6alkyl, C
1-C
6alkoxyl, benzyl or phenyl, wherein benzyl or phenyl are separately optionally by 1 to 3 R
18replace;
R
17for being selected from the one in following radicals:
H；
C
1-C
6alkyl;
C
1-C
6haloalkyl;
C
1-C
6alkoxyalkyl;
C
2-C
6alkyl-carbonyl;
Benzyl or phenyl, wherein benzyl or phenyl are separately optionally by 1 to 3 R
18replace; Or contain the saturated or unsaturated ring of 1 to 3 heteroatomic 5-or 6-unit, wherein each ring is optionally by 1 to 3 R
21replace; R
18for being selected from the one in following radicals: halogen, cyano group, nitro, amino, C
1-C
6alkoxyl alkoxyl, C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6hydroxy alkyl, C
2-C
6alkoxyalkyl, C
2-C
6halogenated alkoxy alkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group, C
3-C
6alkynyl, C
3-C
6halo alkynyl, hydroxyl, C
1-C
6alkoxyl, C
1-C
6halogenated alkoxy, C
2-C
6thiazolinyl oxygen base, C
2-C
6haloalkenyl group oxygen base, C
3-C
6alkynyloxy base, C
3-C
6halo alkynyloxy base, C
1-C
6alkyl sulfenyl, C
1-C
6haloalkyl sulfenyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6thiazolinyl sulfenyl, C
2-C
6haloalkenyl group sulfenyl, C
2-C
6haloalkenyl group sulfonyl, C
3-C
6alkynyl sulfenyl, C
3-C
6alkynyl sulfonyl, C
3-C6 halo alkynyl sulfonyl, C
1-C
6alkyl amino, C
2-C
8dialkyl amido, C
3-C
8dialkyl amino carbonyl, C
2-C
6alkoxy carbonyl, C
2-C
6alkyl-carbonyl, C
3-C
6trialkylsilkl, 2-[(E)-methoxyimino]-N-methyl-acetylamino, phenyl, benzyl, benzyloxy, phenoxy group or 5-or 6-unit heteroaromatic rings group, wherein phenyl, benzyl, benzyloxy, phenoxy group or 5-or 6-unit heteroaromatic rings group are optionally independently selected from R by 1 to 3 separately
22substituting group replace;
R
19for H, C
1-C
6alkyl or C
1-C
6haloalkyl;
R
20for H, C
1-C
6alkyl, C
1-C
6haloalkyl or benzyl;
R
21for being selected from the one in following radicals: halogen, C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl, C
1-C
6halogenated alkoxy, C
1-C
6alkyl sulfenyl, C
1-C
6haloalkyl sulfenyl, amino, C
1-C
6alkyl amino, C
2-C
6dialkyl amido, C
2-C
6alkoxy carbonyl or C
2-C
6alkyl-carbonyl;
R
22for being selected from the one in following radicals: halogen, cyano group, nitro, C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6hydroxy alkyl, C
2-C
6alkoxyalkyl, C
2-C
6halogenated alkoxy alkyl, C
2-C
6thiazolinyl, C
2-C
6haloalkenyl group, C
3-C
6alkynyl, C
3-C
6halo alkynyl, hydroxyl, C
1-C
6alkoxyl, C
1-C
6halogenated alkoxy, C
2-C
6thiazolinyl oxygen base, C
2-C
6haloalkenyl group oxygen base, C
3-C
6alkynyloxy base, C
3-C
6halo alkynyloxy base, C
1-C
6alkyl sulfenyl, C
1-C
6alkyl sulphonyl, C
1-C
6halogenated alkyl sulfonyl, C
2-C
6thiazolinyl sulfenyl, C
2-C
6haloalkenyl group sulfenyl, C
2-C
6haloalkenyl group sulfonyl, C
3-C
6alkynyl sulfenyl, C
3-C
6alkynyl sulfonyl, C
3-C
6halo alkynyl sulfonyl, C
1-C
6alkyl amino, C
2-C
8dialkyl amido, C
3-C
8dialkyl amino carbonyl or C
3-C
6trialkylsilkl.
2. the organophosphorus fungicide containing pyrimidine according to claim 1, is characterized in that,
Wherein,
R
1for oxygen (O) or sulphur (S);
R
2for C
1-C
6alkyl;
R
3, R
4, be respectively following substituted radical in one:
H；
C
1-C
6alkyl.
3. the organophosphorus fungicide containing pyrimidine according to claim 2, is characterized in that,
R
1for oxygen (O) or sulphur (S);
R
2for methyl or ethyl;
R
3for methyl or H;
R
4for methyl or H.
4. the organophosphorus fungicide containing pyrimidine according to claim 3, is characterized in that,
R
1for sulphur (S);
R
2for ethyl;
R
3for methyl;
R
4for methyl or H.
5. the organophosphorus fungicide containing pyrimidine according to claim 3, is characterized in that,
R
1for oxygen (O);
R
2for methyl or ethyl;
R
3for methyl or H;
R
4for methyl or H.
6. the organophosphorus fungicide containing pyrimidine according to claim 5, is characterized in that,
R
1for oxygen (O);
R
2for methyl;
R
3for methyl or H;
R
4for methyl or H.
7. the organophosphorus fungicide containing pyrimidine according to claim 5, is characterized in that,
R
1for oxygen (O);
R
2for ethyl;
R
3for methyl or H;
R
4for methyl or H.
8. the organophosphorus fungicide containing pyrimidine according to claim 5, is characterized in that,
R
1for oxygen (O);
R
2for ethyl or methyl;
R
3for methyl;
R
4for methyl or H.
9. according to the organophosphorus fungicide containing pyrimidine described in the arbitrary claim of claim 1-8, for preventing and treating the fungal disease on cereal crops, economic crops, flowers, forest, fruit.
10. the organophosphorus fungicide containing pyrimidine according to claim 10, for preventing and treating damping off, powdery mildew, rust, rice blast, gall rust, yellow rust, late blight, downy mildew, gray mold, stalk break, balck shank, head blight, damping off, root rot.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410046039.7A CN103766393A (en) | 2014-02-08 | 2014-02-08 | Pyrimidine-containing organophosphorus fungicide and application |
| CN201410260832.7A CN104004019B (en) | 2014-02-08 | 2014-06-12 | A kind of organic phosphorus compound containing pyrimidine and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410046039.7A CN103766393A (en) | 2014-02-08 | 2014-02-08 | Pyrimidine-containing organophosphorus fungicide and application |
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| Publication Number | Publication Date |
|---|---|
| CN103766393A true CN103766393A (en) | 2014-05-07 |
Family
ID=50559523
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410046039.7A Pending CN103766393A (en) | 2014-02-08 | 2014-02-08 | Pyrimidine-containing organophosphorus fungicide and application |
| CN201410260832.7A Active CN104004019B (en) | 2014-02-08 | 2014-06-12 | A kind of organic phosphorus compound containing pyrimidine and application |
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Cited By (1)
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|---|---|---|---|---|
| WO2021177160A1 (en) * | 2020-03-04 | 2021-09-10 | 日本曹達株式会社 | Azinyl azole compound and pest control agent |
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|---|---|---|---|---|
| EP2562162B1 (en) * | 2008-01-22 | 2015-08-19 | Dow AgroSciences LLC | N-cyano-4-amino-5-fluoro-pyrimidine derivatives as fungicides |
| CN101690496A (en) * | 2009-03-20 | 2010-04-07 | 孙德群 | O,O-methyl ethyl-O-(2-isopropyl-6-methyl-4-pyrimidyl) thiophosphate pesticide |
-
2014
- 2014-02-08 CN CN201410046039.7A patent/CN103766393A/en active Pending
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| CN104004019A (en) | 2014-08-27 |
| CN104004019B (en) | 2016-08-31 |
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