CN103880764B - A kind of cyano group fluoro s-triazine compound and its preparation method with weeding activity - Google Patents

A kind of cyano group fluoro s-triazine compound and its preparation method with weeding activity Download PDF

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CN103880764B
CN103880764B CN201210555028.2A CN201210555028A CN103880764B CN 103880764 B CN103880764 B CN 103880764B CN 201210555028 A CN201210555028 A CN 201210555028A CN 103880764 B CN103880764 B CN 103880764B
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triazine
fluoro
methyl
preparation
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CN103880764A (en
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王瑛
李学敏
尉宏伟
苗雨
林长福
刘君丽
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Shenyang Research Institute of Chemical Industry Co Ltd
Sinochem Corp
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Sinochem Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/48—Two nitrogen atoms
    • C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
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Abstract

A kind of cyano group fluoro s-triazine compound and its preparation method with weeding activity. The invention belongs to field of agricultural herbicide, specifically disclose the cyano group fluoro s-triazine or its ammonium salt with weeding activity, and the preparation and application of this compound. The compound structure of the present invention is as shown in formula I:

Description

A kind of cyano group fluoro s-triazine compound and its preparation method with weeding activity
Technical field
The invention belongs to field of agricultural herbicide, specifically relate to a kind of cyano group fluoro s-triazine compound and its preparation method with weeding activity.
Background technology
Due to chlorine for s-triazine weedicide or its composition in use for some time, it can be produced resistance by weeds, and chlorine is not easily degraded in soil for s-triazine weedicide, and second stubble crop is existed poisoning. Consequently, it is desirable to constantly invent herbicidal compounds that is novel or that improved and composition. Moreover, it is contemplated that the factor of the aspect such as economy and environment, invent the weedicide different from existing herbicide action mechanism and also it is very important. GB1327060 disclose as weedicide containing cyano group chlorine for s-triazine compound, its general formula is as follows:
In formula: R1For cyclopropyl, ethyl cyclopropyl; R2For hydrogen, methyl, ethyl; R3For methyl, ethyl. Cyanuric chloride is prepared mono-substituted chlorine for s-triazine compound with organic primary amine reaction by the preparation method of this patent disclosure at-15 ~-5 DEG C, then continuing to send out with amido nitrile at 30 ~ 50 DEG C to generate target compound, prepared cyano group chlorine has the weeding activity of wide spectrum for s-triazine. But, disclosed in prior art there is the shortcoming of poor selectivity in s-triazine weedicide: soil and stem leaf process all have herbicidal performance, therefore medicament pedo relict phase length, be difficult to degraded. So far, cyano group fluoro s-triazine compound as representative of the present invention and be used as foliar herbicide and have no report.
Summary of the invention
The cyano group fluoro s-triazine compound it is an object of the invention to provide a kind of novel structure, having stalk leaf weedicide characteristic, to alleviate the residual harm of weedicide in soil.
The technical scheme of the present invention is as follows:
A kind of equal substituted triazine compound of cyano group fluorine or ammonium salt, structure is as shown in formula I:
In formula:
R1It is selected from hydrogen, C1-C6Alkyl, halogen, C2-C4Alkenyl, C2-C5Alkynes base, C3-C6Cycloalkyl, C2-C5Alkoxyl group, C2-C5Alkylthio, cyano group C2-C5Alkyl, carboxyl, phenyl, substituted-phenyl, heteroaryl; Described heteroaryl is selected from furans, morpholine, thiophene, pyrroles, different azoles, thiazole, pyridine, pyrimidine, pyrazine, cumarone, thionaphthene, benzo pyrazoles, benzoglyoxaline, benzotriazole, quinoline or isoquinoline 99.9; Its substituting group of described substituted-phenyl is selected from 1-3 following group: halogen, nitro, cyano group, C1-C3Alkyl, C1-C3Alkoxyl group or halogen are for C1-C3Alkyl;
R2It is selected from hydrogen, C1-C6Alkyl, C2-C4Alkenyl, C2-C5Alkynes base, C3-C6Cycloalkyl, C2-C5Alkylthio, cyano group C2-C5Alkyl, carboxyl, phenyl, substituted-phenyl, heteroaryl; Described heteroaryl is selected from furans, morpholine, thiophene, pyrroles, different azoles, thiazole, pyridine, pyrimidine, pyrazine, cumarone, thionaphthene, benzo pyrazoles, benzoglyoxaline, benzotriazole, quinoline or isoquinoline 99.9; Described substituted-phenyl is selected from 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-nitrophenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-trifluoromethyl, 4-bromophenyl, 3-fluorophenyl, 3-chloro-phenyl-, 4-Trifluoromethoxyphen-l, 4-cyano-phenyl, 2-fluorophenyl, 2-chloro-phenyl-, 2-Trifluoromethoxyphen-l, 3,5-difluorophenyl, 3,5-dichlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2, chloro-4 fluorophenyls of 5-difluorophenyl, 3-, 3, the chloro-5-trifluoromethyl of 4-difluorophenyl, 3-or 3,4,5-trifluoro-benzene base;
R3It is selected from hydrogen, halogen, C1-C6Alkyl, C2-C4Alkenyl, C2-C5Alkynes base, C3-C5Cycloalkyl, C2-C5Alkoxyl group, C2-C5Alkylthio, carboxyl, phenyl, substituted-phenyl, heteroaryl; Described heteroaryl is selected from furans, morpholine, thiophene, pyrroles, different azoles, thiazole, pyridine, pyrimidine, pyrazine, cumarone, thionaphthene, benzo pyrazoles, benzoglyoxaline, benzotriazole, quinoline or isoquinoline 99.9; Its substituting group of described substituted-phenyl is selected from 1-3 following group: halogen, nitro, cyano group, C1-C3Alkyl, C1-C3Alkoxyl group or halogen are for C1-C3Alkyl;
R4Select hydrogen, C1-C6Alkyl, C2-C4Alkenyl, C2-C5Alkynes base, C3-C6Cycloalkyl, C2-C5Alkoxyl group, C2-C5Alkylthio, carboxyl, phenyl, substituted-phenyl, heteroaryl; Described heteroaryl is selected from furans, morpholine, thiophene, pyrroles, different azoles, thiazole, pyridine, pyrimidine, pyrazine, cumarone, thionaphthene, benzo pyrazoles, benzoglyoxaline, benzotriazole, quinoline or isoquinoline 99.9; Its substituting group of described substituted-phenyl is selected from 1-3 following group: halogen, nitro, cyano group, C1-C3Alkyl, C1-C3Alkoxyl group or halogen are for C1-C3Alkyl.
In the present invention, comparatively preferred compound is, in formula I:
R1It is selected from hydrogen, C1-C6Alkyl, C2-C4Alkenyl, C2-C5Alkynes base, C3-C6Cycloalkyl, C2-C5Alkoxyl group or C2-C5Alkylthio;
R2It is selected from hydrogen, C1-C6Alkyl, C2-C4Alkenyl, C2-C5Alkynes base, C3-C5Cycloalkyl, C2-C5Alkylthio, cyano group C2-C5Alkyl, carboxyl, phenyl, substituted-phenyl, heteroaryl; Described substituted-phenyl is selected from 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-nitrophenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-trifluoromethyl, 4-bromophenyl, 3-fluorophenyl, 3-chloro-phenyl-, 4-Trifluoromethoxyphen-l, 4-cyano-phenyl, 2-fluorophenyl, 2-chloro-phenyl-, 2-Trifluoromethoxyphen-l, 3,5-difluorophenyl, 3,5-dichlorophenyl, 2,4-difluorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2, chloro-4 fluorophenyls of 5-difluorophenyl, 3-, 3, the chloro-5-trifluoromethyl of 4-difluorophenyl, 3-or 3,4,5-trifluoro-benzene base;
R3It is selected from hydrogen, C1-C6Alkyl or halogen;
R4Hydrogen, C can be selected1-C6Alkyl, C2-C4Alkenyl or C2-C5Alkynes base, C3-C6Cycloalkyl, C2-C5Alkoxyl group, C2-C5Alkylthio or carboxyl.
The present invention further preferred compound be, in formula I:
R1It is selected from H;
R2It is selected from C1-C6Alkyl, C2-C4Alkenyl, C2-C5Alkynes base, C3-C6Cycloalkyl, C2-C5Alkylthio or cyano group C2-C5Alkyl;
R3It is selected from C1-C6Alkyl;
R4It is selected from C1-C6Alkyl, C2-C4Alkenyl or C2-C5Alkynes base.
The present invention further preferred compound be:
2-(4-fluoro-6-(ethylamino-)-1,3,5-triazine-2-base amine)-2-methyl-prop cyanogen 2-(4-(isopropylamine base)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl fourth cyanogen
2-(4-(cyclopropyl amino)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl fourth cyanogen.
The acid forming ammonium salt with generalformula?compound can be selected from mineral acid or organic acid. Described mineral acid is selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Hydrogen bromide, hydroiodic acid HI or hydrofluoric acid; Described organic acid is selected from oxalic acid, acetic acid, propionic acid, oxyacetic acid, methylsulphonic acid, Phenylsulfonic acid, tosic acid, C2-C20Alkyl benzene sulphonate (ABS) or trifluoroacetic acid.
Preferred mineral acid is selected from hydrochloric acid, Hydrogen bromide, sulfuric acid or phosphoric acid further; Organic acid is selected from oxalic acid, acetic acid, propionic acid, methylsulphonic acid or tosic acid.
Preferred mineral acid is selected from hydrochloric acid or sulfuric acid; Organic acid is selected from oxalic acid or acetic acid.
In the definition of the compound of Formula I provided above, collect term used and generally it be defined as follows:
So-called alkyl refers to straight or branched form, such as the group such as methyl, ethyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, tertiary butyl, n-pentyl, isopentyl, just own base. Naphthenic hydrocarbon refers to and comprises closed chain form, such as groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. ��-cyanoalkyl refers to the group being connected with cyanogen atom on alkyl.
So-called alkene base refers to that straight or branched form has the group of 1 to 2 carbon-carbon double bonds, such as vinyl, propenyl, allyl group etc.
So-called alkynes base refers to straight or branched form, has the group of 1 to 2 carbon carbon triple bonds, such as ethynyl, proyl, propargyl etc.
So-called alkoxyl group refers to straight or branched form, and end is connected with the group of Sauerstoffatom, such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, special butoxy etc.
So-called alkylthio refers to straight chain or linear form, and end is connected with the group of sulphur atom, such as methylthio group, ethylmercapto group etc.
So-called carboxyl refers to direct-connected or branched form, and end is connected with the group of carboxylic acid, such as second carboxyl, the third carboxyl, isopropyl carboxyl etc.
So-called nitrile (base) alkyl refers to straight or branched form, and end is connected with the group of itrile group, such as second cyanogen itrile group, propionitrile base, isopropyl itrile group etc.
The substituting group that so-called substituted-phenyl refers on phenyl ring is selected from 1-3 following group: halogen, nitro, cyano group, C1-C3Alkyl, C1-C3Alkoxyl group or halogen are for C1-C3Alkyl;
So-called heteroaryl refers to containing heteroatomic aromatics substituting group, such as thienyl, thiazolyl, furyl etc.
So-called halogen refers to fluorine, chlorine, bromine, iodine.
Having now found that, the cyano group fluoro s-triazine compound shown in general formula I of the present invention or its ammonium salt have good weeding activity. 2-cyano substituent-4-substituted amido-6-fluorine s-triazine compound as shown in general formula I provided by the invention, introduces cyano group because of fluoro s-triazine 2-position and shows unexpected selection weeding activity well. The compound of Formula I of the present invention not only can effectively be prevented and kill off unifacial leaf and broadleaf weed, especially broadleaf weed be had good anti-effect, more desirably, the process of stem leaf is only had special efficacy by this medicament, soil can be degraded rapidly, noresidue, even if crop also can not be produced poisoning by heavy dose of soil treatment, do not affect rear stubble crop rotation, thus environmental protection more simultaneously. Therefore another technical scheme of the present invention is the purposes of compound of Formula I as foliar herbicide.
Present invention also offers a kind of herbicidal composition, said composition is taking the I of the general formula of the present invention as active ingredient, and simultaneously containing agriculturally acceptable carrier, wherein the weight content of active ingredient is 0.1 ~ 99% simultaneously. Therefore, present invention includes a kind of method controlling weeds: the above-mentioned composition of herbicidally effective amount is applied to as broad-spectrum herbicide weeds or weed growth medium, thus achieves the object of the present invention.
The technical scheme of the present invention also comprises the preparation method of the cyano group fluoro s-triazine compound shown in formula I.
General formula compound I can be prepared by the following method:
Acid binding agent exist under, compound ii and compound III reacting generating compound IV, and then with compound V reacting generating compound I, reaction formula is as follows:
In formula, each group definition is the same.
Reaction carries out usually in inert organic solvents, and solvent load is 100-150 milliliter/mole cyanuric fluoride.
Suitable solvent is: aromatic hydrocarbon, such as benzene, toluene, dimethylbenzene, oil of mirbane; Halohydrocarbon, such as methylene dichloride, chloroform, chlorobenzene; Ether, such as diethyl ether, t-butyl methyl ether, tetrahydrofuran (THF); Ketone, such as acetone, methyl ethyl ketone; And dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE. Preferred solvent is: tetrahydrofuran (THF), methylene dichloride, acetone or toluene. Also can use the mixture of above-mentioned solvent.
Suitable feed molar ratio is: II and III mol ratio 1:1 ~ 2, and the mol ratio of IV and V is 1:1 ~ 10; Preferred ratio is the mol ratio 1:1.2 of II and III further, and the mol ratio of IV and V is 1:1.1.
Suitable temperature of reaction is-20 DEG C of boiling points to solvent. Preferable reaction temperature is-10 ~ 50 DEG C. Reaction times was advisable with 0.5 ~ 20 hour.
Suitable acid binding agent is selected from: the oxyhydroxide of basic metal or alkaline-earth metal, such as lithium hydroxide, sodium hydroxide, potassium hydroxide; The hydride of basic metal or alkaline-earth metal, such as lithium hydride, sodium hydride, potassium hydride KH or hydrolith; The carbonate of basic metal or alkaline-earth metal, such as Quilonum Retard, sodium carbonate, salt of wormwood or calcium carbonate; The supercarbonate of basic metal, such as sodium bicarbonate, saleratus; The alkoxide of basic metal or alkaline-earth metal, such as sodium methylate, sodium ethylate, potassium ethylate, potassium tert.-butoxide, dimethoxy magnesium; Organic bases, such as Trimethylamine 99, triethylamine, triisopropyl ethamine, N-methyl piperidine, pyridine or substituted pyridines. Preferred acid binding agent is triethylamine, sodium hydroxide, potassium hydroxide or salt of wormwood.
Acid binding agent is usually with the equimolar amount of raw material or excessive use, and the selection of acid binding agent and consumption are appreciated by those skilled in the art, and some suitable acid binding agent above-mentioned can also use as solvent.
Compound ii can adopt known preparation method (see US3641020, US284542, GB873251, US1532389, GB1532388, US4332939, US5171856, US4329458).
Compound III can be commercially.
Compound V can be prepared in accordance with known methods: such as can react obtained in autoclave by nitrile alcohol that is that buy on market or known formula legal system and ammonia, or by suitable aldehydes or ketones and sodium cyanide (potassium cyanide), ammoniacal liquor reaction obtained (see US3803208, JournlofAmericaChemicalSociety.1960.82.696��698).
The technician of this area can prepare the ammonium salt of compound of Formula I of the present invention according to known technology.
The present invention has following useful effect:
1, when the compound of Formula I of the present invention is used as weedicide, there is better weeding activity. Biological activity test result shows, owing to the compound of Formula I structure of the present invention is simultaneously with cyano group and fluoro s-triazine structure, the weeding activity of the compound shown in general formula I had both been better than chlorine for s-triazine compound.
2, by making after introducing cyano group on fluoro s-triazine structure, compound shows excellent weeding selectivity in the present invention: only the process of stem leaf is had special efficacy. User can see the rear dispenser of grass, overcomes the shortcoming of soil processing herbicide blindness dispenser, is not only beneficial to peasant and reduces unnecessary medication expenditure, and dispenser is by the restriction of soil humidity, without pedo relict, does not affect rear stubble crop rotation, environmental protection more.
3, preparation method's selectivity provided by the present invention is good, receipts rate height; Overcome when traditional method prepares this compounds due to active high, the poor shortcoming that by product is many, product yield is low caused of reaction preference of cyanuric fluoride.
Should it is clear that, in the claim limited range of the present invention, multiple conversion and change can be carried out.
Embodiment
Being below the representational specific embodiment of the present invention, in order to the present invention to be described further, but they should not be construed as limitation of the scope of the invention.
Preparation embodiment
Embodiment 12-(4-fluoro-6-(ethylamino-)-1,3,5-triazine-2-base amine)-2-methyl-prop cyanogen (compound 1)
By 2.70g(0.02mol) cyanuric fluoride and 0.8g (0.02mol) sodium hydroxide joins in the tetrahydrofuran (THF) reaction vessel filling 30ml, the bath of ice salt makes mixing solutions be cooled to-10 DEG C, drip and add containing 1.68g(0.02mol) the tetrahydrofuran solution 3ml of 2-amino-2-methyl third cyanogen, dripping the temperature adding solution in process all the time in less than-5 DEG C, within 0.5 hour, dropwise, continuing insulated and stirred and react 2 hours, TCL detection reaction is complete. Filtering out insoluble salt, decompression is de-molten obtains white crystal 2-(4,6-bis-fluoro-1,3,5-triazine-2-base ammonia)-2-methyl-prop cyanogen 3.62g, receipts rate 90.5%, mp:102 ~ 105 DEG C.
By above-mentioned containing white crystal 3.62g(0.009mol) 2-(4,6-bis-fluoro-1,3,5-triazine-2-base ammonia)-2-methyl propionitrile loads in the reaction vessel filling 20ml acetone, is under agitation warmed up to 30 DEG C. Dripping and add containing 3.67g(0.018mol) the acetone soln 5ml of ethamine is in reactor, within 1 hour, dropwise, then drip in reactor and add containing 1.12g(0.02mol) aqueous solution 5ml of potassium hydroxide, within 15 minutes, dropwise, continuing to stir 3 hours by mixture, TCL detection reaction is complete. Being poured into by mixture in 100ml cold water, adularescent crystal precipitates out immediately, filters out white crystal. Obtain 2-(4-fluoro-6-(ethylamino-)-1,3,5-triazine-2-base ammonia)-2-methyl-prop cyanogen 3.59g, receipts rate 80.1%, mp:212��214 DEG C
Embodiment 22-(4-(cyclopropyl amino)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl fourth cyanogen (compound 3)
By 2.70g(0.02mol) cyanuric fluoride and 0.8 gram of (0.02mol) sodium hydroxide joins in the dichloromethane solution filling 30ml, the bath of ice salt makes mixing solutions be cooled to-10 DEG C, drip and add containing 1.18(0.02mol) the dichloromethane solution 5ml of cyclopropylamine, dripping the temperature adding solution in process all the time in less than-5 DEG C, within 1 hour, dropwise. Insulated and stirred reacts 2 hours. Filtering out insoluble salt, decompression is de-molten obtains the fluoro-1,3,5-triazine-2-amine 3.19g of white crystal N-cyclopropyl-4,6-two, receipts rate 92.7%, mp:118 ~ 120 DEG C.
By above-mentioned white crystal 3.19g(0.018mol) the fluoro-1,3,5-triazine-2-amine of N-cyclopropyl-4,6-two joins in 100ml round-bottomed flask, adds 30ml acetone and make solvent, be under agitation warmed up to 30 DEG C. Dripping and add containing 2.11g(0.0216mol) the acetone soln 5ml of 2-amino-2-methyl fourth cyanogen is in reactor, within 1 hour, dropwise, then drip in reactor and add containing 1.38g(0.024mol) aqueous solution 5ml of potassium hydroxide, within 15 minutes, dropwise, continue to stir 3 hours by mixture. Being poured into by mixture in 100ml cold water, adularescent crystal precipitates out immediately, filters out white crystal. Obtain 2-(4-(cyclopropylamine)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl fourth cyanogen 3.35g, receive 71%.mp:206��208 DEG C
According to the method described above, suitably changing IV and II, can obtain other compound in formula I, the physical property of part of compounds is in table 1.
Part of compounds in table 1 general formula I
Compound number Compound title Fusing point (DEG C)
1 2-(4-fluoro-6-(ethylamino-)-1,3,5-triazine-2-base amine)-2-methyl-prop cyanogen 212~214
2 2-(4-(isopropylamine base)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl fourth cyanogen 202~204
3 2-(4-(cyclopropyl amino)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl fourth cyanogen 206~208
4 2-(4-(cyclohexylamino)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl-prop cyanogen 214~216
5 2-(4-(Tri N-Propyl Amine base)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl-prop cyanogen 157~159
6 2-(4-(1-methyl cyclopropyl amino)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl-prop cyanogen 235~237
Part of compounds in general formula I1HNMR (300MHz, DMSO-d6) nuclear magnetic data is as follows:
Compound 1:8.38 ~ 8.40ppm (m, 1H), 8.05 ~ 8.15ppm (br, 1H), 3.26 ~ 3.38ppm (q, 2H), 1.74ppms, (s, 6H), 1.16ppm (t, 3H)
Compound 2:8.25 ~ 8.36ppm (m, 1H), 8.01 ~ 8.12ppm (br, 1H), 4.11 ~ 4.20ppm (m, 1H), 2.10ppm (q, 2H), 1.73ppm (q, 6H), 1.07ppm (d, 6H)
Compound 3:7.25 ~ 7.32ppm (br, 1H), 7.01 ~ 7.18ppm (br, 1H), 1.70ppm (s, 6H), 0.80ppm (d, 4H), 0.59ppm (d, 4H)
Compound 4:5.88 ~ 5.92ppm (m, 1H), 6.15 ~ 6.23ppm (m, 1H), 3.80 ~ 3.87ppm (m, 1H), 1.75 ~ 2.18ppm (m, 2H), 1.70ppm (s, 6H) 1.46 ~ 1.49m (m, 3H), 1.07 ~ 1.21ppm (m, 8H)
Compound 5:8.32 ~ 8.35ppm (m, 1H), 7.01 ~ 7.20ppm (m, 1H), 3.2ppm (t, 2H), 1.70ppm (s, 6H), 1.57ppm (m, 2H), 0.90ppm (t, 3H)
Compound 6:7.05 ~ 7.18ppm (m, 1H), 6.75 ~ 6.80ppm (m, 1H), 1.72ppm (t, 2H), 1.30ppm (s, 3H), 0.82ppm (d, 4H), 0.61ppm (d, 4H).
Biological activity determination embodiment
Embodiment 3
Test before seedling: carrying out after sowing, test compound is sprayed in soil surface, process is placed on room temperature, then waters;
Testing after seedling, seed germination also grows 10 ~ 21 days, it may also be useful to have the examination material of a series of growing stage before process, then selects the examination material that size, growing stage are consistent, processes, and process is placed on greenhouse and waters. Comparison medicament is former medicine G-30027, does not make blank with the examination material of compound treatment, and examination material is broadleaf weed youth-and-old-age, piemarker; Monocotyledon weed is barnyard grass and lady's-grass.
Testing method: dissolve former medicine with a small amount of acetone (being no more than the 10% of liquor strength, in weight), by design flow, joins in the standing tap water containing 2 �� tween 80s, obtained certain density preparation. Spray with mobile band atomizer. Examination material is put in the scrolling bands in spraying cupboard, and medicament, through examination material top, is sprayed onto on examination material by mobile shower nozzle with covering of the fan Sprayable, and nozzle is usually identical with on field spray device. Rolling band moves out outside cupboard by examination material, is placed in loft drier dry.
Examination material after spraying dry is placed in greenhouse. Test is from top water spray before seedling, tests and pour water from bottom and keep 48 hours so that water does not touch blade face after seedling.
Process and investigate for 2 ~ 3 weeks. Invalid with 0%() control completely to 100%() carry out active classification. Inhibiting rate is various infringement such as total effect of chlorosis, withered, retarded growth or the calcination of leaf angle, with compare after obtain effect. Part test result is such as following table.
Test the weeding activity of control compound according to same condition simultaneously, the results are shown in Table 2. Wherein control compound A be chlorine for triazine commercialization agricultural chemicals ring third cyanogen Tianjin (compound prepared by example 2 in GB-1327060), control compound B is the compound 5 in CN102464625A. Control compound A and B structure formula are as follows:
The weeding activity of table 2 generalformula?compound
Test result shows:
1, unifacial leaf and broadleaf weed are had inhibit activities by the compound of Formula I of the present invention, and lady's-grass, piemarker, youth-and-old-age stem leaf are especially had outstanding anti-effect when processing by compound 1,2,3, and its herbicidal effect is obviously better than control compound A.
2, the compound of Formula I of the present invention show good stem leaf select weeding activity, its outstanding advantage is noresidue in soil compared with compound B, even if at high doses soil treatment to target also without poisoning, do not affect rear stubble crop rotation.

Claims (7)

1. a cyano group fluoro s-triazine compound or ammonium salt, it is characterised in that following particular compound:
2-(4-fluoro-6-(ethylamino-)-1,3,5-triazine-2-base amine)-2-methyl-prop cyanogen 2-(4-(isopropylamine base)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl fourth cyanogen
2-(4-(cyclopropyl amino)-6-fluoro-1,3,5-triazine-2-base amine)-2-methyl fourth cyanogen.
2. a preparation method for general formula compound I as claimed in claim 1, comprising:
Acid binding agent exist under, compound ii and compound III reacting generating compound IV, and then with compound V reacting generating compound I, reaction formula is as follows:
In formula:
R1It is selected from hydrogen;
R2It is selected from ethyl, sec.-propyl or cyclopropyl;
R3It is selected from methyl;
R4Select methyl or ethyl.
3. according to preparation method according to claim 2, it is characterised in that: II and III reinforced mol ratio 1:1��2, IV and V reinforced mol ratio is 1:1��10; Temperature of reaction is-20 DEG C of boiling points to solvent, and the reaction times is 0.5-20 hour; Reaction carries out in inert organic solvents, and solvent load is 100-150 milliliter/mole II.
4. according to preparation method according to claim 3, it is characterised in that: II and III reinforced mol ratio 1:1.2, IV and V reinforced mol ratio is 1:1.1, and temperature of reaction is-10��50 DEG C; Described inert organic solvents is selected from tetrahydrofuran (THF), methylene dichloride, acetone or toluene.
5. one kind is used as the purposes of stem leaf process weedicide according to generalformula?compound according to claim 1.
6. a herbicidal composition, it is characterised in that: containing according to generalformula?compound according to claim 1 and agriculturally acceptable carrier, in composition, the weight content of active ingredient is 0.1��99% in composition.
7. one kind controls the method for weeds, it is characterised in that: use herbicidal composition as claimed in claim 6 to weeds or weed growth medium.
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US3787199A (en) * 1966-07-16 1974-01-22 Degussa Herbicide based on cyanoalkylaminotriazines
FR2093871A5 (en) * 1970-05-29 1972-01-28 Agripat Sa
CH550546A (en) * 1971-08-05 1974-06-28 Ciba Geigy Ag HERBICIDAL AGENT.
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