CN103694255A - Pyridinooxazone-pyridinopyrimidone compounds and preparation method and application thereof - Google Patents
Pyridinooxazone-pyridinopyrimidone compounds and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses pyridinooxazone-pyridinopyrimidone compounds and a preparation method and an application thereof. The pyridinooxazone-pyridinopyrimidone compounds have the following structures shown in formulae 1 and 2: R1 is hydrogen or chlorine; R2 is hydrogen, chlorine or fluorine; R3 is hydrogen, amido, methyl or carboxymethyl; X, Y and Z are nitrogen or hydrocarbon. The synthetic line comprises the following steps: dissolving amino substituted picolinic acid in an organic solvent; in the presence of organic alkali, carrying out reaction with substituted phenoxyacetyl chloride to obtain the pyridinooxazone compounds; and reacting the pyridinooxazone compounds with substituted amine in an organic solvent to obtain the pyridinopyrimidone compounds. The pyridinooxazone-pyridinopyrimidone compounds are used for preventing and treating weed. Part of the pyridinooxazone and pyridinopyrimidone compounds has high herbicidal activity and can effectively inhibit growth of dicotyledon.
Description
Technical field
The present invention relates to pyrrole pyridine oxazinone compounds and Pyridopyrimidine ketone compounds and preparation method thereof, and this two compounds application in controlling weeds.
Background technology
Weeds are one of main harm during farm crop produce, and adopt herbicide weed control to be grown in and in modern agricultural production, occupy critical role.Weed growth consumes the nutrition in earth, covers sunlight, hinders crop growth; Part weeds meeting release inhibiting factor, or hold pathogenic former that farm crop are harmful to, reduce output or the economic worth of periphery farm crop.World Herbicide development experience from high dosage, broad spectrum weeding agent, to current ultra low-volume, selective herbicide.The development of World Herbicide is to improving agricultural productivity, guaranteeing Biosafety safety and preserve the ecological environment significant.
The weedicide using is at present of a great variety, mainly contains glyphosate class, sulfonylurea, sulphonamide triazolinones, imidazolone type, triazolo pyrimidine class, pyrimidine phosphorothioate benzoates etc.But due to the life-time service of part weedicide kind, weeds also highlight the resistance problem of weedicide thereupon, improve usage quantity for this reason and also will cause the problem of biological and ecological security aspect.Therefore, designing and synthesizing the high reactivity weedicide small molecules with different types of structure is modern weedicide developing direction.
Bi Ding Bing oxazinone and pyrido-pyrimidines are the nitrogen heterocyclics that a class has varied organisms activity, in medicine and pesticide research, are used widely.The patent and the periodical literature report that constantly have in recent years the synthetic and related application of this analog derivative.Wherein, patent (EP.Pat.No.1851217) has been reported the class Pyridopyrimidine compound application aspect medical; Patent (CA.Pat.No.1267414) has reported that a class Bi Ding Bing oxazinone compounds is in the application that suppresses not need plant-growth; Patent (HU.Pat.No.196410B) has been reported the application of a class Bi Ding Bing oxazinone compounds as weedicide; Patent (US.Pat.No.3862191) has reported that all kinds of pyrido-pyrimidines are as the application of weedicide aspect; Patent (IL.Pat.No.75572A) has been reported the application of a class pyrido-pyrimidines as weedicide and plant-growth regulator.
Summary of the invention
Primary and foremost purpose of the present invention is to provide a kind of pyrrole pyridine oxazinone compounds and Pyridopyrimidine ketone compounds of novel structure.
Another object of the present invention is to provide the preparation method of above-mentioned pyrrole pyridine oxazinone compounds and Pyridopyrimidine ketone compounds.
A further object of the present invention is to provide the application of above-mentioned pyrrole pyridine oxazinone compounds and Pyridopyrimidine ketone compounds.
Object of the present invention is achieved through the following technical solutions:
A Bi Ding Bing oxazinone compounds, its structure as shown in Equation 1:
Wherein, R
1for hydrogen or chlorine; R
2for hydrogen, chlorine or fluorine; A kind of in X, Y and Z is nitrogen, all the other are hydrocarbon (CH-).
A Pyridopyrimidine ketone compounds, its structure as shown in Equation 2:
Wherein, R
1for hydrogen or chlorine; R
2for hydrogen, chlorine or fluorine; R
3for hydrogen, amino, methyl or carboxymethyl; X and Y are hydrocarbon (CH-) or nitrogen, and Z is hydrocarbon (CH-).
The synthetic route chart of above-mentioned pyrrole pyridine oxazinone compounds or Pyridopyrimidine ketone compounds as shown in Figure 1, by amino substituted pyridines formic acid (formula 3) and substituted benzene oxygen Acetyl Chloride 98Min. (formula 4), under alkali exists, carry out acidylate and ring closure reaction, obtain compound shown in formula 1; Compound shown in formula 1 is reacted with replacement amine (formula 5), obtain the compound shown in formula 2.
In formula 3, the definition of X, Y and Z is identical with formula 1; R in formula 4
1and R
2definition identical with formula 1 or formula 2; R in formula 5
3definition identical with formula 2.
The preparation method of Bi Ding Bing oxazinone compounds, comprise the steps: amino substituted pyridines formic acid (formula 3) to be dissolved in organic solvent, under organic bases exists, react with substituted benzene oxygen Acetyl Chloride 98Min. (formula 4), obtain Bi Ding Bing oxazinone compounds (formula 1).
Described amino substituted pyridines formic acid (formula 3) comprises 2-amino-nicotinic acid (3a), 3-aminoisonicotinic acid (3b) and 3-aminopyridine-2-carboxylic acid (3c).
Described organic solvent can be DMF or pyridine.
Described organic bases is preferably triethylamine.
Described substituted benzene oxygen Acetyl Chloride 98Min. (formula 4), can adopt conventional chloride method synthetic by corresponding phenoxy acetic acid, and the acylating reagent of employing can be phosphorus pentachloride or sulfur oxychloride; Wherein, substituted benzene oxygen acetic acid comprises 2,4-dichlorphenoxyacetic acid, p-chlorophenoxyacetic acid, to fluorobenzene fluoroacetic acid, phenoxy acetic acid, the substituted benzene oxygen Acetyl Chloride 98Min. (formula 4) that chloride obtains is respectively 2,4 dichloro benzene oxygen Acetyl Chloride 98Min. (4a), to chlorine phenoxyacetyl chloride (4b), to fluorine phenoxyacetyl chloride (4c) and phenoxyacetyl chloride (4d).
The temperature of described reaction is preferably-5 ℃～room temperature.
The preparation method of described Pyridopyrimidine ketone compounds, comprises the steps: pyrrole pyridine oxazinone compounds (formula 1) to react in organic solvent with replacement amine (formula 5), obtains Pyridopyrimidine ketone compounds (formula 2).
Described replacement amine (formula 5) comprises ammonium acetate (5a), hydrazine hydrate (5b), methylamine (5c), glycine (5d).
Described organic solvent is preferably ethanol or acetic acid.
The temperature of described reaction is preferably between 70～100 ℃.
Above-mentioned pyrrole pyridine oxazinone compounds and/or the application of Pyridopyrimidine ketone compounds in controlling weeds.Described pyrrole pyridine oxazinone compounds and/or Pyridopyrimidine ketone compounds can be used as weedicide and use separately; Or with the carrier allowing in other plant protection or mixing diluents, be mixed with and comprise that mixture, granule or aqueous emulsion are used; Or with the composite use of other agricultural bactericide, Insecticides (tech) & Herbicides (tech) or plant-growth regulator or while use.
The present invention has the following advantages and effect with respect to prior art tool: pyrrole pyridine of the present invention oxazinone compounds and Pyridopyrimidine ketone compounds compounds novel structure, there is good weeding activity, and can effectively suppress dicotyledons growth.Part of compounds of the present invention, when low concentration 1.0ppm, has shown selective herbicidal activity, and weeding activity with contrast commercialization weedicide 2,4-D is suitable.
Accompanying drawing explanation
Fig. 1 is the synthetic route schematic diagram of pyrrole pyridine of the present invention oxazinone compounds and Pyridopyrimidine ketone compounds; Amino substituted pyridines formic acid (formula 3) and substituted benzene oxygen Acetyl Chloride 98Min. (formula 4) carry out acidylate and ring closure reaction in alkali and organic solvent, obtain 2-Phenoxymethyl-4H-3,1-Bi Ding Bing oxazin-4-one derivatives (formula 1, EQN1～12); Further react with various replacement amine (formula 5) EQN1～8, obtains corresponding 2-Phenoxymethyl Pyridopyrimidine-4 (3H)-one derivatives (formula 2, MDN1～32).
Embodiment
Below in conjunction with embodiment, the present invention is done to further detailed description, but embodiments of the present invention are not limited to this.
Embodiment 1
Synthesizing of various phenoxyacetyl chlorides (formula 4)
Phenoxyacetyl chloride in the present invention (formula 4) is prepared by conventional chloride method by corresponding substituted benzene oxygen acetic acid.Its synthetic logical method is as follows: phosphorus pentachloride is dissolved in methylene dichloride, under ice bath, add substituted benzene oxygen acetic acid, oil bath heating reflux reaction 10h, until emit without gas, methylene dichloride is removed in air distillation, phosphorus oxychloride is removed in underpressure distillation, obtains brown color liquid, is substituted benzene oxygen Acetyl Chloride 98Min. (formula 4).
Embodiment 2
2-(2,4 dichloro benzene oxygen methyl)-4H-pyridine [2,3-d] [preparation of 1,3] oxazine-4-ketone (EQN1)
2-amino-nicotinic acid (3a, 0.3g, 2.2mmol) is dissolved in 10mL DMF solution, under ice bath, drips 2,4 dichloro benzene oxygen Acetyl Chloride 98Min. (4a, 0.35mL, 2.2mmol), add triethylamine (0.32mL, 2.2mmol), continue room temperature reaction 12h.Filter, with saturated aqueous common salt and sodium hydrogen carbonate solution washing, organic layer is silica gel column chromatography after anhydrous sodium sulfate drying successively, obtain faint yellow solid 2-(2,4 dichloro benzene oxygen methyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN1), yield 75%, m.p.198.8-199.6 ℃.
1H?NMR(600MHz,DMSO-d6):δ9.03(d,J=3.0Hz,1H),8.56(d,J=7.2Hz,1H),7.56(q,J=7.2Hz,1H),7.40(s,1H),7.18(d,J=6.6Hz,1H),7.05(d,J=8.4Hz,1H)，5.10(s,2H).EI-MSm/z,(%):321.93(M
+,1.03),286.96(100.00)。
Embodiment 3
The preparation of 2-(4-chlorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN2)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-(4-chlorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN2), faint yellow solid, yield 70%, m.p.184.5-185.5 ℃.
1H?NMR(400MHz,CDCl
3):δ9.03(d,J=2.8Hz,H),8.55(d,J=6.4Hz,H),7.56(
q,J=3.2Hz,H),7.25(d,J=2.0Hz,2H),7.01(d,J=2.4Hz,2H),5.07(s,2H).EI-MS?m/z,(%):287.98(M
+,47.98),146.93(100.00)。
Embodiment 4
The preparation of 2-(4-fluorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN3)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-(4-fluorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN3), deep yellow solid, yield 80%, m.p.156.4-157.3 ℃.
1H?NMR(400MHz,CDCl
3):δ9.03(d,J=2.8Hz,H),8.54(d,J=6.0Hz,H),7.55(q,J=3.0Hz,H),7.25(d,J=2.0Hz,2H),7.01(d,J=2.4Hz,2H),5.06(s,2H).EI-MS?m/z,(%):272.04(M
+,11.67),179.00(100.00)。
Embodiment 5
2-Phenoxymethyl-4H-pyridine [2,3-d] [preparation of 1,3] oxazine-4-ketone (EQN4)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-Phenoxymethyl-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN4), light yellow solid, yield 70%, m.p.119.4-120.2 ℃.
1H?NMR(600MHz,DMSO-d6):δ8.96(d,J=3.0Hz,H),8.52(d,J=8.4Hz,H),7.55(q,J=4.2Hz,H),7.34(d,J=6.0Hz,2H),7.08(t,J=8.4Hz,2H),6.99(t,J=9.0Hz,H),5.08(s,2H).EI-MSm/z,(%):253.98(M
+,56.87),146.94(100.00)。
Embodiment 6
2-(2,4 dichloro benzene oxygen methyl)-4H-pyridine [2,3-d] [preparation of 1,3] oxazine-4-ketone (EQN5)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-(2,4 dichloro benzene oxygen methyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN5), deep yellow solid, yield 85%, m.p.173.3-173.9 ℃.
1H?NMR(400MHz,CDCl
3):δ9.08(s,H),8.86(d,J=4.8Hz,H),8.01(d,J=4.8Hz,H),7.43(s,H),7.20(d,J=8.4Hz,H),7.01(d,J=8.8Hz,H),5.08(s,2H).EI-MS?m/z,(%):322.19(M
+,9.54),287.18(100.00)。
Embodiment 7
The preparation of 2-(4-chlorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN6)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-(4-chlorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN6), yellow solid, yield 80%, m.p.159.5-160.4 ℃.
1H?NMR(400MHz,CDCl3):δ9.08(s,H),8.84(d,J=5.2Hz,H),7.99(d,J=4.8Hz,H),7.28(d,J=8.8Hz,H),6.96(d,J=8.8Hz,H),5.03(s,2H).EI-MS?m/z,(%):288.17(100.00)。
Embodiment 8
The preparation of 2-(4-fluorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN7)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-(4-fluorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN7), yellow solid, yield 78%, m.p.135.6-136.6 ℃.
1H?NMR(400MHz,CDCl
3):δ9.09(s,H),8.84(d,J=4.8Hz,H),7.99(d,J=4.4Hz,H),7.24(d,J=3.6Hz,H),6.99(d,J=3.6Hz,H),5.01(s,2H).EI-MS?m/z,(%):272.20(100.00)。
Embodiment 9
2-Phenoxymethyl-4H-pyridine [2,3-d] [preparation of 1,3] oxazine-4-ketone (EQN8)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-Phenoxymethyl-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN8), light yellow solid, yield 75%, m.p.101.3-102.2 ℃.
1H?NMR(400MHz,CDCl
3):δ9.09(s,H),8.84(d,J=4.8Hz,H),7.99(d,J=4.4Hz,H),7.35(d,J=3.6Hz,H),7.30(t,J=3.6Hz,H),7.04(t,J=8.0Hz,H),5.04(s,2H).EI-MS?m/z,(%):254.19(100.00)。
Embodiment 10
2-(2,4 dichloro benzene oxygen methyl)-4H-pyridine [2,3-d] [preparation of 1,3] oxazine-4-ketone (EQN9)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-(2,4 dichloro benzene oxygen methyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN9), deep yellow solid, yield 90%, m.p.166.3-166.6 ℃.
1H?NMR(600MHz,CDCl
3):δ8.91(d,J=4.2Hz,H),8.00(d,J=8.4Hz,H),7.77(q,J=4.2Hz,H),7.41(s,H),7.19(d,J=4.8Hz,H),7.00(d,J=8.4Hz,H),5.09(s,2H).EI-MS?m/z,(%):321.93(M
+,1.03),286.96(100.00)。
Embodiment 11
The preparation of 2-(4-chlorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN10)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-(4-chlorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN10), light brown solid, yield 85%, m.p.157.3-158.2 ℃.
1H?NMR(600MHz,CDCl
3):δ8.89(d,J=8.4Hz,H),8.00(d,J=8.4Hz,H),7.77(q,J=4.2Hz,H),7.25(d,J=8.4Hz,2H),6.97(d,J=8.4Hz,2H),5.02(s,2H).EI-MS?m/z,(%):287.98(M
+,47.98),146.93(100.00)。
Embodiment 12
The preparation of 2-(4-fluorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN11)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-(4-fluorine Phenoxymethyl)-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN11), yellow solid, yield 89%, m.p.139.8-140.4 ℃.
1H?NMR(600MHz,CDCl
3):δ8.91(d,J=4.2Hz,H),8.03(d,J=8.4Hz,H),7.77(q,J=4.2Hz,H),7.02(d,J=3.0Hz,2H),6.99(d,J=3.0Hz,2H),5.02(s,2H).EI-MS?m/z,(%):272.04(M
+,11.67),179.00(100.00)。
Embodiment 13
2-Phenoxymethyl-4H-pyridine [2,3-d] [preparation of 1,3] oxazine-4-ketone (EQN12)
Adopt the synthetic method similar to embodiment 2 to obtain compound 2-Phenoxymethyl-4H-pyridine [2,3-d] [1,3] oxazine-4-ketone (EQN12), yellow solid, yield 80%, m.p.109.8-110.7 ℃.
1H?NMR(600MHz,DMSO-d6):δ8.89(d,J=3.6Hz,H),8.02(d,J=7.8Hz?H),7.76(q,J=4.2Hz,H),7.33(d,J=7.2Hz,2H),7.03(t,J=4.8Hz,2H),7.02(t,J=4.8Hz,H),5.05(s,2H).EI-MSm/z,(%):253.98(M
+,56.87),146.94(100.00)。
Embodiment 13
The preparation of 2-(2,4 dichloro benzene oxygen methyl)-pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-1)
By EQN1(0.15g, 0.47mmol) be dissolved in 8mL Glacial acetic acid, add ammonium acetate (5a, 0.11g, 1.40mmol), be warming up to gradually 100 ℃ of reaction 5h.Be cooled to room temperature, add ethyl acetate, with sodium hydroxide solution and water washing; Organic phase, with after anhydrous sodium sulfate drying precipitation, obtains light brown solid 2-(2,4 dichloro benzene oxygen methyl)-pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-1), yield 20%, m.p.225.1-225.7 ℃.
1H?NMR(400MHz,DMSO-d6):δ12.82(s,H),8.95(d,J=2.4Hz,H),8.53(d,J=8.0Hz,H),7.58(q,J=4.8Hz,H),7.39(s,H),7.35(d,J=8.8Hz,H),7.27(d,J=8.4Hz,H),5.12(s,2H).EI-MSm/z,(%):320.26(M
+,1.00),286.20(100.00)。
Embodiment 14
The preparation of 2-(4-chlorine Phenoxymethyl)-pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-2)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-chlorine Phenoxymethyl)-pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-2), yellow solid, yield 30%, m.p.212.7-213.5 ℃.
1H?NMR(400MHz,DMSO-d6):δ12.80(s,H),9.03(d,J=2.8Hz,H),8.55(d,J=6.4Hz,H),7.56(q,J=3.2Hz,H),7.25(d,J=2.0Hz,2H),7.01(d,J=2.4Hz,2H),5.09(s,2H).EI-MS?m/z,(%):287.20(M
+,50.05),133.09(100.00)。
Embodiment 15
The preparation of 2-(4-fluorine Phenoxymethyl)-pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-3)
Adopt the synthetic method similar to embodiment 13 to obtain compound 2-(4-fluorine Phenoxymethyl)-pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-3), yellow solid, yield 35%, m.p.210.7-211.6 ℃.
1H?NMR(400MHz,DMSO-d6):δ12.82(s,H),9.03(d,J=2.8Hz,H),8.54(d,J=6.0Hz,H),7.55(q,J=3.2Hz,H),7.25(d,J=2.0Hz,2H),7.01(d,J=2.4Hz,2H),5.08(s,2H).EI-MS?m/z,(%):271.20(M
+,81.39),133.10(100.00)。
Embodiment 16
The preparation of 2-Phenoxymethyl pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-4)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-Phenoxymethyl pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-4), faint yellow solid, yield 32%, m.p.192.6-193.4 ℃.
1H?NMR(400MHz,DMSO-d6):δ12.77(s,H),8.96(d,J=2.0Hz,H),8.52(d,J=7.6Hz,H),7.54(q,J=3.0Hz,H),7.34(d,J=4.8Hz,2H),7.08(t,J=7.2Hz,2H),6.99(t,J=8.8Hz,H),5.12(s,2H).EI-MS?m/z,(%):253.26(M
+,93.57),133.10(100.00)。
Embodiment 17
The preparation of 2-(2,4 dichloro benzene oxygen methyl)-3-aminopyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-5)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(2,4 dichloro benzene oxygen methyl)-3-aminopyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-5), faint yellow solid, yield 75%, m.p.229.1-229.7 ℃.
1H?NMR(600MHz,DMSO-d6):δ8.91(d,J=6.6Hz,H),8.55(d,J=7.2Hz,H),7.63(q,J=4.2Hz,H),7.55(s,H),7.29(d,J=9.0Hz,2H),7.17(d,J=9.0Hz,H),5.70(s,2H),5.48(s,2H,-CH2O-).EI-MS?m/z,(%):336.14(M
+,0.95),301.20(100.00)。
Embodiment 18
The preparation of 2-(4-chlorine Phenoxymethyl)-3-aminopyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-6)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-chlorine Phenoxymethyl)-3-aminopyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-6), faint yellow solid, yield 85%, m.p.215.8-216.7 ℃.
1H?NMR(400MHz,DMSO-d6):δ8.91(d,J=3.6Hz,H),8.55(d,J=8.0Hz,H),7.63(q,J=7.2Hz,H),7.33(d,J=4.2Hz,2H),7.07(d,J=8.8Hz,H),5.43(s,2H),5.70(s,2H).EI-MS?m/z,(%):302.22(M
+,51.32),286.19(100.00)。
Embodiment 19
The preparation of 2-(4-fluorine Phenoxymethyl)-3-aminopyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-7)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-fluorine Phenoxymethyl)-3-aminopyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-7), yellow solid, yield 80%, m.p.214.8-215.2 ℃.
1H?NMR(600MHz,DMSO-d6):δ8.93(d,J=7.2Hz,H),8.55(d,J=8.4Hz,H),7.60(q,J=6.6Hz,H),7.15(d,J=8.4Hz,2H),7.09(d,J=13.2Hz,H),5.75(s,2H),5.40(s,2H).EI-MS?m/z,(%):286.28(M
+,39.97),270.19(100.00)。
Embodiment 20
The preparation of 2-Phenoxymethyl-3-aminopyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-8)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-Phenoxymethyl-3-aminopyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-8), yellow solid, yield 80%, m.p.195.8-196.7 ℃.
1H?NMR(600MHz,DMSO-d6):δ8.93(d,J=7.2Hz,H),8.55(d,J=8.4Hz,H),7.60(q,J=6.6Hz,H),7.15(d,J=8.4Hz,2H),7.09(t,J=13.2Hz,H),6.96(t,J=7.2Hz,H),5.75(s,2H),5.40(s,2H).EI-MS?m/z,(%):268.24(M
+,69.11),252.20(100.00)。
Embodiment 21
The preparation of 2-(2,4 dichloro benzene oxygen methyl)-3-picoline [2,3-d] pyrimidine-4 (3H)-one (MDN-9)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(2,4 dichloro benzene oxygen methyl)-3-picoline [2,3-d] pyrimidine-4 (3H)-one (MDN-9), deep yellow solid, yield 75%, m.p.186.0-186.7 ℃.
1H?NMR(600MHz,CDCl
3):δ9.00(d,J=2.4Hz,H),8.63(d,J=7.8Hz,H),7.49(q,J=4.8Hz,H),7.38(s,H),7.25(d,J=9.0Hz,2H),7.19(d,J=9.0Hz,H),5.36(s,2H),3.84(s,3H).EI-MS?m/z,(%):335.12(M
+,1.56),300.00(100.00)。
Embodiment 22
The preparation of 2-(4-chlorine Phenoxymethyl)-3-picoline [2,3-d] pyrimidine-4 (3H)-one (MDN-10)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-chlorine Phenoxymethyl)-3-picoline [2,3-d] pyrimidine-4 (3H)-one (MDN-10), yellow solid, yield 81%, m.p.181.5-182.5 ℃.
1H?NMR(600MHz,CDCl
3):δ9.00(d,J=4.2Hz,H),8.62(d,J=6.0Hz,H),7.49(q,J=4.8Hz,H),7.25(d,J=8.4Hz,2H),7.05(d,J=9.0Hz,H),5.34(s,2H),3.76(s,3H).EI-MS?m/z,(%):301.00(M
+,27.25),132.99(100.00)。
Embodiment 23
The preparation of 2-(4-fluorine Phenoxymethyl)-3-picoline [2,3-d] pyrimidine-4 (3H)-one (MDN-11)
MDN-11
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-fluorine Phenoxymethyl)-3-picoline [2,3-d] pyrimidine-4 (3H)-one (MDN-11), deep yellow solid, yield 73%, m.p.179.5-180.3 ℃.
1H?NMR(600MHz,CDCl
3):δ9.00(d,J=4.2Hz,H),8.62(d,J=6.0Hz,H),7.48(q,J=4.8Hz,H),7.20(d,J=8.4Hz,2H),6.99(d,J=9.0Hz,H),5.27(s,2H),3.78(s,3H).EI-MS?m/z,(%):285.01(M
+,36.17),132.98(100.00)。
Embodiment 24
The preparation of 2-Phenoxymethyl-3-picoline [2,3-d] pyrimidine-4 (3H)-one (MDN-12)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-Phenoxymethyl-3-picoline [2,3-d] pyrimidine-4 (3H)-one (MDN-12), deep yellow solid, yield 88%, m.p.176.3-177.0 ℃.
1H?NMR(600MHz,CDCl
3):δ9.00(d,J=1.8Hz,H),8.61(d,J=1.8Hz,H),7.47(q,J=4.2Hz,H),7.31(d,J=8.4Hz,2H),7.10(t,J=9.0Hz,H),6.99(t,J=7.2Hz,H),5.29(s,2H),3.78(s,3H).EI-MS?m/z,(%):267.04(M
+,67.04),132.99(100.00)。
Embodiment 25
The preparation of 2-(2,4 dichloro benzene oxygen methyl)-3-carboxymethyl pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-13)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(2,4 dichloro benzene oxygen methyl)-3-carboxymethyl pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-13), deep yellow solid, yield 86%, m.p.247.6-248.5 ℃.
1H?NMR(600M?Hz,DMSO-d6):δ13.32(s,H),8.91(d,J=1.8Hz,H),8.46(d,J=7.8Hz,H),7.53(q,J=4.8Hz,H),7.46(s,H),7.28(d,J=9.0Hz,H),7.21(d,J=9.0Hz,H),5.36(s,2H),4.81(s,2H).EI-MS?m/z,(%):379.01(M
+,1.39),161.99(100.00)。
Embodiment 26
The preparation of 2-(4-chlorine Phenoxymethyl)-3-carboxymethyl pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-14)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-chlorine Phenoxymethyl)-3-carboxymethyl pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-14), brown solid, yield 80%, m.p.230.6-231.4 ℃.
1H?NMR(600MHz,DMSO-d6):δ13.36(s,H),9.01(d,J=4.8Hz,H),8.56(d,J=7.8Hz,H),7.63(q,J=4.8Hz,H),7.16(d,J=9.0Hz,2H),7.08(d,J=7.2Hz,2H),5.32(s,2H),4.89(s,2H).EI-MS?m/z,(%):345.01(M
+,6.33),127.94(100.00)。
Embodiment 27
The preparation of 2-(4-fluorine Phenoxymethyl)-3-carboxymethyl pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-15)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-fluorine Phenoxymethyl)-3-carboxymethyl pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-15), brown solid, yield 78%, m.p.218.5-219.3 ℃.
1H?NMR(600MHz,DMSO-d6):δ13.36(s,H),9.01(d,J=4.8Hz,H),8.56(d,J=7.8Hz,H),7.63(q,J=4.8Hz,H),7.16(d,J=9.0Hz,2H),7.08(d,J=7.2Hz,2H),5.32(s,2H),4.89(s,2H).EI-MS?m/z,(%):328.98(M
+,42.05),111.94(100.00)。
Embodiment 28
The preparation of 2-Phenoxymethyl-3-carboxymethyl pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-16)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-Phenoxymethyl-3-second carboxyl pyridine [2,3-d] pyrimidine-4 (3H)-one (MDN-16), brown solid, yield 82%, m.p.204.5-205.3 ℃.
1H?NMR(600MHz,DMSO-d6):δ13.38(s,H),9.01(d,J=2.4Hz,H),8.56(d,J=1.8Hz,H),7.63(q,J=4.8Hz,H),7.31(d,J=7.8Hz,2H),7.08(t,J=10.8Hz,2H),6.98(t,J=7.2Hz,H),5.33(s,2H),4.88(s,2H).EI-MS?m/z,(%):310.98(M
+,37.89),93.98(100.00)。
Embodiment 29
The preparation of 2-(2,4 dichloro benzene oxygen methyl)-pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-17)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(2,4 dichloro benzene oxygen methyl)-pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-17), brown solid, yield 15%, m.p.247.1-247.7 ℃.
1H?NMR(600MHz,DMSO-d6):δ9.98(s,H),9.15(s,H),8.75(d,J=2.4Hz,H),8.06(d,J=2.4Hz,H),7.45(s,H),7.28(d,J=4.4Hz,H),7.16(d,J=8.4Hz,H),5.11(s,2H).EI-MS?m/z,(%):321.25(M
+,4.81),286.18(100.00)。
Embodiment 30
The preparation of 2-(4-chlorine Phenoxymethyl)-pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-18)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-chlorine Phenoxymethyl)-pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-18), yellow solid, yield 35%, m.p.241.1-241.9 ℃.
1H?NMR(600MHz,CDCl
3):δ9.98(s,H),9.15(s,H),8.75(d,J=2.4Hz,H),8.06(d,J=2.4Hz,H),7.35(d,J=4.8Hz,2H),6.98(d,J=4.8Hz,2H),5.11(s,2H).EI-MS?m/z,(%):287.18(M
+,77.10),133.10(100.00)。
Embodiment 31
The preparation of 2-(4-fluorine Phenoxymethyl)-pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-19)
MDN-19
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-fluorine Phenoxymethyl)-pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-19), yellow solid, yield 30%, m.p.239.0-239.9 ℃.
1H?NMR(600MHz,CDCl
3):δ9.98(s,H),9.15(s,H),8.75(d,J=7.2Hz,H),8.06(d,J=4.8Hz,H),7.08(d,J=4.8Hz,2H),6.98(d,J=4.8Hz,2H),5.10(s,2H).EI-MS?m/z,(%):271.20(M
+,81.39),133.10(100.00)。
Embodiment 32
The preparation of 2-Phenoxymethyl pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-20)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-Phenoxymethyl pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-20), yellow solid, yield 40%, m.p.221.9-222.5 ℃.
1H?NMR(600MHz,DMSO-d6):δ12.95(s,H),9.06(s,H),8.69(d,J=3.6Hz,H),7.97(d,J=3.6Hz,H),7.34(d,J=5.4Hz,2H),7.08(t,J=4.8Hz,2H),6.98(t,J=4.8Hz,H),5.06(s,2H).EI-MS?m/z,(%):253.22(M
+,80.82),133.16(100.00)。
Embodiment 33
The preparation of 2-(2,4 dichloro benzene oxygen methyl)-3-aminopyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-21)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(2,4 dichloro benzene oxygen methyl)-3-aminopyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-21), faint yellow solid, yield 70%, m.p.199.4-200.1 ℃.
1H?NMR(600MHz,CDCl
3):δ9.25(s,H),8.75(d,J=2.4Hz,H),8.06(d,J=4.8Hz,H),7.45(s,H),7.33(d,J=7.2Hz,H),7.16(d,J=8.4Hz,H),5.32(s,2H),5.31(s,2H).EI-MS?m/z,(%):336.41(M
+,7.90),301.29(100.00)。
Embodiment 34
The preparation of 2-(4-chlorine Phenoxymethyl)-3-aminopyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-22)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-chlorine Phenoxymethyl)-3-aminopyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-22), faint yellow solid, yield 79%, m.p.190.1-190.7 ℃.
1H?NMR(600MHz,CDCl
3):δ9.21(s,H),8.74(d,J=5.4Hz,H),8.06(d,J=4.8Hz,H),7.28(d,J=8.4Hz,2H),7.01(d,J=8.4Hz,2H),5.33(s,2H),5.28(s,2H).EI-MS?m/z,(%):302.22(M
+,60.35),146.11(100.00)。
Embodiment 35
The preparation of 2-(4-fluorine Phenoxymethyl)-3-aminopyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-23)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-fluorine Phenoxymethyl)-3-aminopyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-23), faint yellow solid, yield 85%, m.p.178.3-179.2 ℃.
1H?NMR(600MHz,CDCl
3):δ9.20(s,H),8.73(d,J=2.4Hz,H),8.06(d,J=4.8Hz,H),7.03(d,J=6.0Hz,2H),7.01(d,J=6.0Hz,2H),5.33(s,2H),5.31(s,2H).EI-MS?m/z,(%):286.27(M
+,60.35),146.15(100.00)。
Embodiment 36
The preparation of 2-Phenoxymethyl-3-aminopyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-24)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-Phenoxymethyl-3-aminopyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-24), faint yellow solid, yield 89%, m.p.145.3-145.8 ℃.
1H?NMR(600MHz,CDCl
3):δ9.20(s,H),8.72(d,J=3.0Hz,H),8.05(d,J=4.2Hz,H),7.34(d,J=1.8Hz,2H),7.07(t,J=6.6Hz,2H),7.02(t,J=6.0Hz,H),5.35(s,2H),5.30(s,2H).EI-MSm/z,(%):286.22(M
+,93.19),146.11(100.00)。
Embodiment 37
The preparation of 2-(2,4 dichloro benzene oxygen methyl)-3-picoline [3,4-d] pyrimidine-4 (3H)-one (MDN-25)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(2,4 dichloro benzene oxygen methyl)-3-picoline [3,4-d] pyrimidine-4 (3H)-one (MDN-25), light brown solid, yield 35%, m.p.189.5-190.4 ℃.
1H?NMR(600MHz,CDCl
3):δ9.15(s,H),8.73(d,J=4.8Hz,H),8.06(d,J=5.4Hz,H),7.36(s,H),7.23(d,J=8.4Hz,H),7.10(d,J=8.4Hz,H),5.19(s,2H),3.77(s,3H).EI-MS?m/z,(%):335.12(M
+,1.56),300.00(100.00)。
Embodiment 38
The preparation of 2-(4-chlorine Phenoxymethyl)-3-picoline [3,4-d] pyrimidine-4 (3H)-one (MDN-26)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-chlorine Phenoxymethyl)-3-picoline [3,4-d] pyrimidine-4 (3H)-one (MDN-26), yellow solid, yield 55%, m.p.165.5-166.5 ℃.
1H?NMR(600MHz,CDCl
3):δ9.15(s,H),8.73(d,J=5.4Hz,H),8.06(d,J=5.4Hz,H),7.29(d,J=2.4Hz,2H),7.10(d,J=1.8Hz,2H),5.19(s,2H),3.76(s,3H).EI-MS?m/z,(%):301.12(M
+,27.20),132.98(100.00)。
Embodiment 39
The preparation of 2-(4-fluorine Phenoxymethyl)-3-picoline [3,4-d] pyrimidine-4 (3H)-one (MDN-27)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-fluorine Phenoxymethyl)-3-picoline [3,4-d] pyrimidine-4 (3H)-one (MDN-27), light yellow solid, yield 59%, m.p.154.9-155.8 ℃.
1H?NMR(600MHz,CDCl
3):δ9.15(s,H),8.73(d,J=4.8Hz,H),8.06(d,J=5.4Hz,H),7.02(d,J=5.4Hz,2H),7.00(d,J=5.4Hz,2H),5.19(s,2H),3.77(s,3H).EI-MS?m/z,(%):285.03(M
+,36.17),132.99(100.00)。
Embodiment 40
The preparation of 2-Phenoxymethyl-3-picoline [3,4-d] pyrimidine-4 (3H)-one (MDN-28)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-Phenoxymethyl-3-picoline [3,4-d] pyrimidine-4 (3H)-one (MDN-28), faint yellow solid, yield 39%, m.p.114.4-115.3 ℃.
1H?NMR(600MHz,CDCl
3):δ9.15(s,H),8.73(d,J=4.8Hz,H),8.06(d,J=5.4Hz,H),7.34(d,J=4.8Hz,2H),7.20(t,J=5.4Hz,2H),7.08(d,J=5.4Hz,H),5.18(s,2H),3.77(s,3H).EI-MSm/z,(%):267.03(M
+,67.04),132.99(100.00)。
Embodiment 41
The preparation of 2-(2,4 dichloro benzene oxygen methyl)-3-carboxymethyl pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-29)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(2,4 dichloro benzene oxygen methyl)-3-carboxymethyl pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-29), Vandyke brown solid, yield 46%, m.p.243.6-244.5 ℃.
1H?NMR(600MHz,DMSO-d6):δ13.32(s,H)9.17(s,H),8.76(d,J=8.4Hz,H),8.06(d,J=4.8Hz,H),7.46(s,H),7.28(d,J=9.0Hz,H),7.11(d,J=9.0Hz,H)5.36(s,2H),4.81(s,2H).EI-MS?m/z,(%):379.01(M
+,1.39),161.99(100.00)。
Embodiment 42
The preparation of 2-(4-chlorine Phenoxymethyl)-3-carboxymethyl pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-30)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-chlorine Phenoxymethyl)-3-carboxymethyl pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-30), obtain black solid, yield 44%, m.p.231.4-232.1 ℃.
1H?NMR(600MHz,DMSO-d6):δ13.32(s,H),9.10(s,H),8.76(d,J=8.4Hz,H),8.06(d,J=8.4Hz,H),7.28(d,J=7.2Hz,2H),7.11(d,J=7.2Hz,2H),5.33(s,2H),4.79(s,2H).EI-MS?m/z,(%):345.01(M
+,6.33),127.94(100.00)。
Embodiment 43
The preparation of 2-(4-fluorine Phenoxymethyl)-3-carboxymethyl pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-31)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-(4-fluorine Phenoxymethyl)-3-second carboxyl pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-31), brown solid, yield 54%, m.p.220.9-221.7 ℃.
1H?NMR(600MHz,DMSO-d6):δ13.32(s,H),9.10(s,H),8.76(d,J=8.4Hz,H),8.06(d,J=8.4Hz,H),7.10(d,J=6.0Hz,2H),7.08(d,J=6.0Hz,2H),5.33(s,2H),4.79(s,2H).EI-MS?m/z,(%):329.98(M
+,42.05),111.94(100.00)。
Embodiment 44
The preparation of 2-Phenoxymethyl-3-carboxymethyl pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-32)
Adopt the synthetic method similar to embodiment 13, obtain compound 2-Phenoxymethyl-3-carboxymethyl pyridine [3,4-d] pyrimidine-4 (3H)-one (MDN-32), deep yellow solid, yield 32%, m.p.210.8-211.5 ℃.
1H?NMR(600MHz,DMSO-d6):δ13.32(s,H),9.12(s,H),8.73(d,J=7.2Hz,H),8.06(d,J=7.2Hz,H),7.40(d,J=8.4Hz,2H),7.30(t,J=4.8Hz,2H),7.08(t,J=6.0Hz,H),5.36(s,2H),4.80(s,2H).EI-MS?m/z,(%):310.98(M
+,37.89),93.98(100.00)。
Experimental example 45
1. the shaker test of weeding activity
The Bi Ding Bing oxazinone compounds of synthesized and the weeding activity of pyrido-pyrimidines adopt the indoor herbicidal activity test Plating of industry standard agricultural chemicals (NY/T1155.1-2006) to carry out indoor weeding activity primary dcreening operation.Take rape as dicotyledons model plant, take rye grass as monocotyledons model plant, compd E QN1-12 and MDN1-32 are carried out to the test of weeding activity.
Institute's test compounds is dissolved with a little DMF, and tween-80 emulsification, adds distilled water to be made into two sample concentration: 10ppm and 1.0ppm.Culture dish diameter 9cm, built-in two layers of filter paper, the sample solution that adds 10mL to configure, plants 20 seeds to be measured.In incubator in 25 ℃ of constant temperature culture 8 days.The random length of selecting five strain rapes, rye grass to measure stem and root.Contrast medicine is selected 2,4-D.According to blank growth length, calculate inhibition percentage: inhibiting rate=[(root/stem length mean value of root/stem length mean value-experimental group of blank group)/(root/stem length mean value of control group)] * 100%.
2. experimental result
Table 1 is the test result of 44 illnesss after compound dispenser: 100% for suppressing completely; 0% for not suppressing completely.
Table 1. compd E QN1-12 and MDN1-32 Plating weeding activity test-results
From the result of weeding activity test, can draw:
(1) all compounds of the present invention all have certain inhibition activity to the root of unifacial leaf and dicotyledons and stem, substantially active higher than the inhibition to stem to the inhibition activity of root.
(2) during lower concentration, the compounds of this invention declines to monocotyledonous inhibition is active, but part of compounds still has good inhibition active to dicotyledons as EQN1, EQN5, EQN9, MDN5, MDN21, MDN22 etc., with suitable according to medicament to test, mainly cause that dicotyledons basal part of stem expands or explosion, cauline leaf distortion deformity, and then occur that whole strain is dead.
(3) the above data of holistic approach, the compounds of this invention shows the inhibition of dicotyledons selectivity with the reduction of concentration, and monocotyledons is suppressed to activity decreased.This show the restraining effect phenotype of this compounds and the restraining effect phenotype of 2,4-D similar, the root selectivity of dicotyledons is suppressed.
When compound of the present invention is used as weedicide, can be separately or with other plant protection on the carrier or the mixing diluents that allow, be mixed with normally used various formulation, as mixture, granule, aqueous emulsion etc. are used, also can be with other agricultural chemicals as the composite uses such as sterilant, Insecticides (tech) & Herbicides (tech), plant-growth regulator or while use.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. pyrrole pyridine an oxazinone compounds, is characterized in that structure is as shown in Equation 1:
Wherein, R
1for hydrogen or chlorine; R
2for hydrogen, chlorine or fluorine; A kind of in X, Y and Z is nitrogen, all the other are for hydrocarbon.
2. a Pyridopyrimidine ketone compounds, its structure as shown in Equation 2:
Wherein, R
1for hydrogen or chlorine; R
2for hydrogen, chlorine or fluorine; R
3for hydrogen, amino, methyl or carboxymethyl; X and Y are hydrocarbon or nitrogen, and Z is hydrocarbon.
3. the preparation method of Bi Ding Bing oxazinone compounds claimed in claim 1, it is characterized in that comprising the steps: compound shown in formula 3 is dissolved in to organic solvent, under organic bases exists, react with compound shown in formula 4, obtain Bi Ding Bing oxazinone compounds;
Wherein, in formula 3, the definition of X, Y and Z is identical with formula 1; In formula 4, the definition of R1 and R2 is identical with formula 1 or formula 2.
4. the preparation method of Bi Ding Bing oxazinone compounds according to claim 3, is characterized in that: described organic solvent is DMF or pyridine; Described organic bases is triethylamine; The temperature of described reaction is-5 ℃～room temperature.
5. the preparation method of Pyridopyrimidine ketone compounds claimed in claim 2, it is characterized in that comprising the steps: pyrrole pyridine claimed in claim 1 oxazinone compounds are reacted in organic solvent with the replacement amine shown in formula 5, obtain Pyridopyrimidine ketone compounds;
H
2N-R
3
Formula 5
Wherein, R in formula 5
3definition identical with formula 2.
6. the preparation method of Pyridopyrimidine ketone compounds according to claim 2, is characterized in that: described organic solvent is ethanol or acetic acid; The temperature of described reaction is 70～100 ℃.
7. pyrrole pyridine claimed in claim 1 oxazinone compounds and/or the application of Pyridopyrimidine ketone compounds claimed in claim 2 in controlling weeds.
8. application according to claim 7, it is characterized in that: pyrrole pyridine claimed in claim 1 oxazinone compounds and/or Pyridopyrimidine ketone compounds claimed in claim 2 are used separately as weedicide, or with the carrier allowing in other plant protection or mixing diluents, be mixed with and comprise that mixture, granule or aqueous emulsion are used, or also use with the composite use of other agricultural bactericide, Insecticides (tech) & Herbicides (tech) or plant-growth regulator or while.
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