CN1006796B - Process for preparation of organic phosphorus compound - Google Patents
Process for preparation of organic phosphorus compoundInfo
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- CN1006796B CN1006796B CN 85103896 CN85103896A CN1006796B CN 1006796 B CN1006796 B CN 1006796B CN 85103896 CN85103896 CN 85103896 CN 85103896 A CN85103896 A CN 85103896A CN 1006796 B CN1006796 B CN 1006796B
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Abstract
The present invention relates to an organic phosphorus compound which is expressed in a general formula I. In the general formula I, X1 and X3 are hydrogen atoms, alkyl groups or alkoxyl groups(which can be substituted by halogen, alkyl chloride, alkyl sulfide, phenoxy groups, halogenated phenoxy groups, benzenesulfenyl or halogenated benzenesulgenyl), carboxyl, carbalkoxy or the phenyl groups(which can be substituted by the halogen); X2 and X4 respectively are the hydrogen atoms or the alkyl groups; methylene can be formed by the X2 and the X3; Y1, Y2 and Z are oxygen atoms or sulfur atoms; R1 and R2 are the alkyl groups.
Description
The present invention relates to have desinsection, kill the new organo phosphorous compounds of mite and eelworm-killing activity.2-thiazolidone (or the 2-thiazolidine thioketones) ring that The present invention be more particularly directed to contain substituent 2-oxazolidone (or 2-oxazole thioketones) ring or replace, the preparation process of this organophosphorus compounds and contain the desinsection of this organic compound as activeconstituents is killed mite and nematicidal compositions.
The organo phosphorous compounds that the 2-oxazolidone (or replace 2-oxazolidine thioketones) that contains replacement among the present invention encircled or contained the 2-thiazolidone of replacement (or the 2-thiazolidine thioketones that replaces) ring is a new compound.The uncensored patent publication No. 144794/1984 of Japan has been revealed and has been contained 1, the organo phosphorous compounds of 3-oxazole (or thiazole) alkane 2-thioketones.But the chemical structure of the compound of being revealed is different with the structure of compound of the present invention, and they are used as the activator of carboxyl, there is no material and points out or advise purposes of the present invention, promptly as desinsection, kills mite, or nematicidal compound.
In other words, the invention provides new organic compound, comprise their steric isomer such as optical isomer with following general formula (I) expression.
X in the formula
1And X
3All are hydrogen atoms, the alkyl or the alkoxyl group that can be replaced by halogen, alkoxyl group, alkylthio, phenoxy group, halogenated phenoxy, thiophenyl or halogeno-benzene sulfenyl, carbonyl, carbalkoxy or the phenyl that can be replaced by halogen, X
2And X
4Be hydrogen atom or alkyl, condition is X
2And X
3Can form alkylidene group, Y together
1, Y
2And Z is Sauerstoffatom or sulphur atom, R
1And R
2Be alkyl.
The invention provides the preparation process of formula I compound, this process is made of following reaction, promptly in the presence of sour accepting agent, and the compound of representing with the general formula II,
X
1, X
2, X
3, X
4, Y
1And Y
2Definition as mentioned, with the compound reaction that is representative with logical formula III,
Hal is a halogen atom in the formula, Z, R
1And R
2Definition as mentioned.
The Insecticiding-miticiding or the nematicide significant quantity of the organo phosphorous compounds of formula I have been the present invention further provides.
Now, the present invention will be described in detail with embodiment preferred.
In above-mentioned formula I, by X
1To X
4The alkyl of expression or the moieties of alkoxyl group, or by R
1And R
2The alkyl of expression comprises methyl, ethyl, propyl group or butyl.By X
1And X
3Halogen part in halogenated alkyl, alkoxyl group, phenoxy group, thiophenyl or the phenyl of expression can be fluorine, chlorine, bromine, iodine.
In above-mentioned formula I, X
1And X
3All preferred hydrogen atom can be by the low alkyl group (C of alkoxyl group or alkylthio replacement
1-6) or lower alkoxy, the phenyl that can be replaced by halogen; Hydrogen atom more preferably, but the low alkyl group that alkoxy or alkylthio replace, or lower alkoxy; Most preferably hydrogen atom or low alkyl group.
X
2And X
4Preferably all be hydrogen atom or low alkyl group (C
1-6).
Y
2And Z preferably all is Sauerstoffatoms.
R
1And R
2Preferably all are low alkyl group (C
1-6).More preferably R
1With R
2Different.R most preferably
1Be n-propyl, isobutyl-, sec-butyl, R
2Be methyl or ethyl.
As mentioned above, formula I compound of the present invention can prepare by the represented process of following equation:
HaI is a halogen atom, X
1, X
2, X
3, X
4, Y
1, Y
2, Z, R
1And R
2Definition as mentioned.
This reaction is carried out in-100 to 50 ℃ temperature range usually, is preferably in-80 ℃ and carries out to room temperature (30 ℃).
This has been reflected under the sour accepting agent existence and has carried out, organolithium compound such as n-Butyl Lithium, and tert-butyl lithium or phenyl lithium can be used as sour accepting agent, mineral alkali such as sodium hydroxide, potassium hydroxide, sodium hydride or potassium hydride KH; Or organic bases such as triethylamine or pyridine also can be used as sour accepting agent.Reaction is preferably carried out in solvent.Aromatic hydrocarbon such as benzene, toluene, dimethylbenzene or chlorobenzene, ring-type or non-annularity aliphatic hydrocarbon such as hexane or hexanaphthene, ethers such as diethyl ether, methyl ethyl ether, dioxane or tetrahydrofuran (THF); Nitrile compound such as acetonitrile, propionitrile, vinyl cyanide, sprotic polar solvent such as dimethyl formamide, methyl-sulphoxide, the tetramethylene sulfone, HMPA (HMPT) can be used as solvent.
In the represented raw material of general formula II, the 2-oxazolidone of replacement (or the 2-oxazole thioketones that replaces) is easily by the beta-alkamine and the urea element that replace, and phosgene or diethyl carbonate (or thiophosgene) get through annulation; The 2-thiazole thione that replaces is easily got through annulation by the sulfuric ester and the dithiocarbonic anhydride of the beta-alkamine that replaces.Further, the 2-thiazolidone of replacement easily makes according to laxative remedy: the beta-amino mercaptan that (1) replaces and the annulation of urea element, (2) replace the oxidizing reaction of 2-thiazole thione, the beta-alkamine sulfuric ester that (3) replace and the annulation of carbon oxysulfide.
Now, the present invention will describe in detail with relevant example.But, should be appreciated that the present invention does not also mean that and is confined to these specific examples.
Example 1:
The preparation of trans O-ethyl S-n-propyl [4-(4-chlorophenyl)-5-methyl-2-oxo 3-thiazolidyl] thiophosphatephosphorothioate (compound 2)
Erythro form-1-amino-1-(4-the chlorophenyl of (1) 9.3 gram) 2-propylthio acid esters is suspended in 60 milliliters the ethanol, and 40 milliliters the 5.4 gram dithiocarbonic anhydride and the aqueous solution of 4.4 gram potassium hydroxide progressively splash in the above-mentioned suspension.Reaction mixture stirs reaction down 3 hours at 40 ℃, after reacting completely, and pressure reducing and steaming ethanol, residue ethyl acetate extraction.Extracting solution washes with water, uses anhydrous sodium sulfate drying then, removes solvent under reduced pressure, promptly obtains the trans-4-(4-chlorophenyl of 5 grams)-5-methyl-2-thiazole thione.
(2) 5 of above-mentioned reaction (1) gained grams anti--4-(-4-hydrogen is for phenyl)-5-methyl 2-thiazole thione is dissolved in 50 ml methanol, add and contain 30 milliliters of 5.35 gram methanol solutions, then, progressively drip 30% aqueous hydrogen peroxide solution of 10.7 grams, temperature is no more than 40 ℃ during dropping, reaction mixture is in room temperature, and stirring state reacted one hour down.After reacting completely, remove methyl alcohol under reduced pressure, the residue ethyl acetate extraction.Extract phase washes with water, uses anhydrous sodium sulfate drying, removes solvent under reduced pressure, promptly gets fusing point and be trans-4-(-4-chlorophenyl of 119～121 ℃)-5-methyl-2-thiazolidone 1.8 grams.
(3) trans-4-(4-chlorophenyl of reaction (2) gained)-5-methyl-2-thiazolidyl ketone 0.8 gram is dissolved in 20 milliliters of tetrahydrofuran (THF)s, this solution is chilled to-78 ℃, progressively splash into the hexane solution (1.65 mol) of 2.3 milliliters n-Butyl Lithium then, reaction mixture stirred 30 minutes, then, progressively drip 5 milliliters of the muriatic tetrahydrofuran solutions of the 0-ethyl S-n-propyl thiophosphatephosphorothioate contain 0.78 gram, reaction mixture stirred 30 minutes, then room temperature reaction 3 hours, after reacting completely, in the reaction product impouring frozen water, use ethyl acetate extraction, extract phase washes with water, use anhydrous sodium sulfate drying, remove solvent under reduced pressure, the residue silica gel chromatography, get the required product of 0.5 gram, the refractive index of product is 1.5426(24.6 ℃).
Example 2:
Trans 0-ethyl S-n-propyl [the 5-(4-chlorophenyl)-preparation (compound 1) of 4-methyl 2-oxo-3-thiazolidyl Thiophosphonate
Trans-5-(4-the chlorophenyl that makes by reaction (1) and (2) same procedure in the example I)-4-methyl-2-thiazolidyl ketone 1.0 grams are dissolved in 20 milliliters of tetrahydrofuran (THF)s, this solution is chilled to-78 ℃, then, progressively drip 3.2 milliliters of the hexane solutions of n-Butyl Lithium, (1.65 molconcentration), reaction mixture stirred 30 minutes, then, progressively dripped 5 milliliters of the muriatic tetrahydrofuran solutions of the 0-ethyl S-n-propyl thiophosphatephosphorothioates that contain 1.0 grams, reaction mixture stirred 30 minutes, and then room temperature reaction 3 hours, after reacting completely, in reactant impouring frozen water, use ethyl acetate extraction, extract phase washes with water, uses anhydrous sodium sulfate drying, then, remove solvent under reduced pressure, residue silica gel column chromatography purifying gets the required product of 1.0 grams, and refractive index is 1.5592(27.6 ℃).
Example 3:
The preparation (compound 5) of S-second month in a season-butyl 0-ethyl (2-oxo-3-thiazolidyl) Thiophosphonate
2-thiazolidone 1.5 by reaction (1) and (2) same procedure preparation in the example 1 restrains in the tetrahydrofuran (THF) that is dissolved in 30 milliliters, solution is chilled to-78 ℃, progressively drip 11 milliliters of the hexane solutions (1.65 molconcentration) of n-Butyl Lithium then, reaction mixture stirred 15 minutes, progressively drip 10 milliliters of muriatic tetrahydrofuran solutions containing 5 gram S-second month in a season-butyl 0-ethyl phosphorothioic acid ester then, reaction mixture stirred 30 minutes, and then room temperature reaction 3 hours.After reacting completely, in the reaction product impouring water, use ethyl acetate extraction.Extract phase washes with water, uses anhydrous sodium sulfate drying.Then, remove solvent under reduced pressure, get required product 2.3 grams, refractive index is 1.5334(19.6 ℃).
Example 4:
The preparation of the S-second month in a season-butyl-0-ethyl (5-methyl-2-oxo-3-oxazolidinyl) Thiophosphonate (compound 9).
The amino 2-propyl alcohol of (1) 10 gram 1-, the mixture of 20 milliliters of diethyl carbonates and 67 milligrams of sodium methylates, reaction is 15 minutes under reflux temperature.After reacting completely, steam about 14 milliliters of ethanol under standard atmosphere pressure, the residue underpressure distillation gets 5-methyl-2-oxazolidone 7.6 grams, boiling range 150～155 ℃/7 mmhg.
The 5-methyl 2-oxazolidone of (2) 2 grams is dissolved in 40 milliliters of tetrahydrofuran (THF)s, and solution is chilled to-78 ℃.Then, the hexane solution of n-Butyl Lithium (1.65 molconcentration) progressively is added dropwise in the above-mentioned solution for 12 milliliters, and reaction mixture stirred 15 minutes.Then, the muriatic tetrahydrofuran solution that contains 4.3 gram S-second month in a season-butyl 0-ethyl phosphorothioic acid ester progressively splashes into for 10 milliliters, and reaction mixture stirred 30 minutes, again room temperature reaction 2 hours.After reacting completely, in the reactant impouring water, use ethyl acetate extraction.Ethyl acetate layer washes with water, uses anhydrous sodium sulfate drying, then, removes solvent under reduced pressure, and residue silica gel column chromatography purifying gets required product 1.6 grams, and refractive index is 1.4923(20.5 ℃).
Example 5:
0-ethyl S-just-preparation of propyl group (4-ethyl-2-oxo 3-oxazolidinyl) thiophosphatephosphorothioate (compound 20 etc.).
Make to such an extent that 4-ethyl-2-oxazolidinyl ketone 2.5 grams are dissolved in 40 milliliters of tetrahydrofuran (THF)s by example 4 reactions (1) with quadrat method, solution is chilled to-78 ℃, then, progressively splash into 14 milliliters of the hexane solutions (1.55 molconcentration) of n-Butyl Lithium, reaction mixture stirred 10 minutes, then, progressively splashed into the 0-ethyl S-n-propyl thiophosphatephosphorothioate muriate of 5.3 grams, mixture is warming up to room temperature, reacts 2.5 hours again.After reacting completely, boil off solvent, in residue impouring water, use ethyl acetate extraction.Extract phase is washed with saturated common salt, uses anhydrous sodium sulfate drying.Then, the pressure reducing and steaming solvent, the residue silica gel chromatography gets the required product of 3.84g (compound 20), its refractive index is 1.4948(22.6 ℃).
Yin Zai oxazolidine ring 4-contains unsymmetrical carbon on the position, and contains asymmetric phosphorus atom, so this compound is the mixture of diastereomer, carries out the folding branch of diastereomer, isolated compound 20 with silica gel column chromatography
a, its refractive index is 1.4956(19.8 ℃) and compound 20
b, its refractive index is 1.4950(20.3 ℃).
Preparation can be undertaken by the same procedure in the above-mentioned example with separating, except (+) 4-ethyl 2-oxazolidone ([α] to make with the amino 1-butanols of (L) 2-
30 D+ 4.29(C 1.86, CHCl
3)) when replacing 4-ethyl-2-oxazolidone used in example 5, can obtain compound 20-I as raw material, have refractive index 1.4982(16.2 ℃) (compound 20
aA composition, [α]
30 D-46.19
(C 4.55, CHCl)) and compound 20
b-I has refractive index 1.4978(16.2) (compound, 20
bA composition, [α]
30 D-2.12(C 20.28, CHCl
3))
Similarly, (-) 4-ethyl 2-oxazolidone ([α] that makes with the amino 1-butanols of usefulness-2-
30 D-2.48(C2.82, CHCl
3)) be raw material, by being prepared with quadrat method and separating, can obtain compound 20
a-II has and analyses optical index 1.4990(14.8 ℃) (another composition of compound 20, [α]
30 D+ 62.33(C9.45, CHCl
3)) and compound 20
b-II has refractive index 1.4966(17.2 ℃) (another composition of compound 20, [α]
30 D+ 4.53(C11.70, CHCl
3)).
Example 6:
The preparation of S-second month in a season-butyl 0-ethyl (4,4 dimethyl-2-oxo-3-oxazolidinyl) Thiophosphonate (compound 39).
By example 4 reaction (1) same methods make 4,4 dimethyl-2-oxazolidone 1.0 grams are dissolved in 10 milliliters of tetrahydrofuran (THF)s, solution is chilled to-78 ℃, then, the hexane solution of the n-Butyl Lithium of Dropwise 5 .3 milliliter (1.65 molconcentration) progressively, mixture stirred 15 minutes, then, progressively be added dropwise to the 1.88 gram S-second month in a season-butyl-0-ethyl phosphorothioic acid ester muriates, reactant stirred 30 minutes.Then, at room temperature react 3 hours.After reaction is finished, in reaction product impouring water, use ethyl acetate extraction, extract phase washes with water, uses anhydrous sodium sulfate drying, and pressure reducing and steaming solvent, residue silica gel column chromatography purifying gets required product 1.1 grams, has refractive index 1.4899(19.2 ℃).
Example 7:
The preparation of S-second month in a season-butyl 0-ethyl (5,5 dimethyl-2-oxo-3-oxazolidinyl) Thiophosphonate (compound 41).
By the same quadrat method of example 4 reaction (1) make 5,5 dimethyl-2-azolactone 1.5 grams are dissolved in 30 milliliters of tetrahydrofuran (THF)s, solution is chilled to-78 ℃, then, progressively splash into the hexane solution (1.65 molconcentration) of 10 milliliters n-Butyl Lithium, reactant stirred 15 minutes, then, progressively drip 10 milliliters of tetrahydrofuran solutions containing the S-second month in a season-butyl-0-ethyl phosphorothioic acid ester muriate 3.1 grams, reactant stirred 30 minutes.At room temperature reacted then 3 hours.After reacting completely, in product impouring water, use ethyl acetate extraction, extract phase washes with water, uses anhydrous sodium sulfate drying, the pressure reducing and steaming solvent, residue silica gel column chromatography purifying gets required product 1.7 grams, has refractive index 1.4877(16.0 ℃).
Example 8:
The preparation of S-second month in a season-butyl 0-ethyl (4-methoxyl group-2-oxo-3-oxazolidinyl) Thiophosphonate (compound 55).
1.2 the 4-methoxyl group 2-oxazolidone of gram is dissolved in 30 milliliters of tetrahydrofuran (THF)s, solution is chilled to-78 ℃, then, progressively drip the hexane solution (1.65 molconcentration) of 7.5 milliliters n-Butyl Lithium, reactant stirred 15 minutes, then, progressively drip and contain 10 milliliters of the 2.4 muriatic tetrahydrofuran solutions of the S-second month in a season-butyl-0-ethyl phosphorothioic acid ester that restrain, reactant stirred 30 minutes, then, at room temperature reacted 3 hours again.After reacting completely, in reaction product impouring frozen water, use ethyl acetate extraction, extract phase washes with water, uses anhydrous sodium sulfate drying, the pressure reducing and steaming solvent, crude product silica gel column chromatography purifying gets required product 0.6 gram, has refractive index 1.4955(14.6 ℃).
Example 9:
The preparation of S-second month in a season-butyl 0-ethyl (4-methoxyl group 5-trichloromethyl-2-oxo-3-oxazolidinyl) Thiophosphonate (compound 54).
2.3 the 4-methoxyl group 5-trichloromethyl 2-oxazolidone of gram is dissolved in 30 milliliters of tetrahydrofuran (THF)s, solution is chilled to-78 ℃, then, 6.5 the hexane solution (1.65 molconcentration) of the n-Butyl Lithium of milliliter progressively splashes into, reaction solution stirred 15 minutes, then, 10 milliliters the S-second month in a season-butyl-muriatic tetrahydrofuran solution of 0-ethyl phosphorothioic acid ester that contains 2.5 grams progressively splashes into, and reactant stirred 30 minutes.At room temperature reacted again 3 hours.After reacting completely, in reaction product impouring frozen water, use ethyl acetate extraction, extract phase washes with water, uses anhydrous sodium sulfate drying, then the pressure reducing and steaming solvent.Crude product gets required product 0.9 gram with the pure system of silica gel column chromatography, has refractive index 1.5052(17.4 ℃).
Example 10:
S-second month in a season-butyl 0-ethyl (5-trifluoromethyl-2-oxo-3-oxazolidinyl) Thiophosphonate (compound 56a, preparation b).
(1) mixture of being made up of the 5-trichloromethyl 2-oxazolidones and 20 milliliters the antimony pentafluoride of 4.0 grams reacted 4.5 hours under stirring state at 150 ℃.After reacting completely, reaction mixture is poured in the water, used dichloromethane extraction.Extract phase is washed with saturated common salt, anhydrous sodium sulfate drying, and steaming vibrating dichloromethane, residue gets the 1.2 5-trifluoromethyl 2-oxazolidones that restrain, fusing point 61-65 ℃ with the pure system of silica gel column chromatography.
(2) 0.5 gram 5-trifluoromethyl 2-oxazolidones are dissolved in 10 milliliters of tetrahydrofuran (THF)s, and solution is chilled to-78 ℃, then, progressively drips the hexane solution (1.55 molconcentration) of 2.10 milliliters n-Butyl Lithium, and reactant stirred 15 minutes.Progressively drip 2 milliliters the S-second month in a season-butyl-muriatic tetrahydrofuran solution of 0-ethyl phosphorothioic acid mercaptan ester that contains 0.77 gram then, reactant is warming up to room temperature then, at room temperature stirs 14 hours.After reacting completely, in reaction product impouring water, use ethyl acetate extraction, extract phase washes with water, uses anhydrous sodium sulfate drying, the pressure reducing and steaming solvent, residue is used the pure system of silica gel column chromatography and is separated, and gets required product 0.24 gram, has refractive index 1.4538(24.4 ℃) (compound 56a) and 0.32 another required product of gram, the latter is the former diastereomer, has refractive index 1.4500(24.2 ℃) (compound 56b)
Example 11:
3-[second month in a season-butanethiol base (oxyethyl group) phosphonate group] preparation of 2-oxazolidone 4-carboxylate methyl ester (compound 58).
1.5 gram 2-oxazolidone 4-carboxylate methyl ester is dissolved in 30 milliliters of tetrahydrofuran (THF)s, solution is chilled to-78 ℃, progressively drips the hexane solution (1.65 molconcentration) of 6.9 milliliters n-Butyl Lithium.Reactant stirred 15 minutes, and temperature keeps-78 ℃ during stirring, progressively splashed into 5 milliliters of muriatic tetrahydrofuran solutions that contain the S-second month in a season-butyl-0-ethyl phosphonic acid mercaptan of 2.7 grams then.After dropwising, temperature is risen to room temperature gradually, reacted again 2 hours.After reacting completely, in 100 milliliters of frozen water of reaction mixture impouring, use ethyl acetate extraction then, the extract phase anhydrous sodium sulfate drying, steaming desolventizes, gained crude product silica gel column chromatography purifying, get the required product of 1.7 grams, refractive index is 1.4950(16.1 ℃).
Example 12:
S-second month in a season-butyl 0-ethyl (4-methyl thiomethyl-2-oxo-3-oxazolidine ketone group) Thiophosphonate (compound 66a, preparation b).
1.5 gram 4-methyl thiomethyl 2-oxazolidone is dissolved in 30 milliliters of tetrahydrofuran (THF)s, solution is chilled to-78 ℃, then, progressively drips the hexane solution (1.55 molconcentration) of 8.0 milliliters n-Butyl Lithium.Stirred 15 minutes at-78 ℃, then progressively the Dropwise 5 milliliter contain 2.4 grams S-in addition-butyl-muriatic tetrahydrofuran solution of 0-ethyl phosphonic acid mercaptan ester.After dropwising, mixed solution progressively rises to room temperature, and this thermotonus 2 hours.After reacting completely, reaction mixture is poured in 100 milliliters of frozen water, use ethyl acetate extraction, the extract phase anhydrous sodium sulfate drying, steaming desolventizes then, and the gained crude product gets the required product of 0.6 gram with pure system of silica gel column chromatography and separation, its refractive index is 1.5068(27.4 ℃) (compound 66a) and 0.58 the gram another required product be its isomer, it analyses optical index is 1.5102(27.4 ℃) (compound 66b).
The present invention is prepared or list in the table 1 with the typical specific compound of usual way preparation in the 1-12 example.
Compound of the present invention is to desinsection, kill mite and nematicide and show good active, as they antagonism garden pest 2 spiders mites (Tetranychus Urticae), carmetta spider mite (Tetra-nyehus Cinnabarinus), or the red mite of citrus (Panonychuscitri); Insect on the agricultural such as diamond back moth (Plutella xylostella), Caulis et Folium Brassicae capitatae mythimna separata (Mamestra brassi-cae), common burglar moth (Spodoptera litura), Ke Luolatuo potato beetle (lasptein-otarsa decemlineata), codlin moth (laspeyresiapomo nella), corn earworm (Heliothis zea), tobacco budworm (Heliothisvirescens), corn earworm weevil (Anthonomus grondis), jeep plug moth (lymantria dispar), budworm, plant locust leaf locust, scale insect, bedbug, white fly, the insect that eats plant of Thripidae, locust, coral fly, scarabaei, black burglar moth (Agrot is ipsilon) or burglar moth (Agrotis se-getum); Sanitary insect pest such as ornithonyssus bacoti (Ornithonyssus bacoti), cockroach, fly (Musca domesticca) or mosquito (Culex pipienspallens); Grain storage insect such as blue bean weevil (Callosohruchus chincnsis) or muddled floor beetle (Tribolium confusum); Family expenses implements insect is as building suit moth (Tineapellionella), black carpet beetle (Anthrenus scrophularidae) or underground white hard ant; Other resembles poultry insect such as flea, flea and fly, they also resist Plant nematode, as root knot nematode, and the packing nematode, root infringement nematode, the white top line worm of paddy rice (Aphelenchoides hesseyi), careless mould dental floss worm (Nothotylenchus acris), or pine wilt nematode (Bursaphelenchus lignicolus), in addition, they can resist has the mite of resistance to reach budworm and the fly that organic phosphorous insecticide is had resistance to Mitigan (dicofol) and organic phosphorous insecticide; Moreover compound of the present invention has good interior absorption energy, uses compound treatment soil of the present invention, not only can control soil pests and nematode, and can control the foliage insect.
When compound of the present invention is used as sterilant, during the composition of the active ingredient of miticide or nematocides, they can be mixed and made into multiple formulation such as dust, particle with the assistant medicament on the agricultural, but wet-milling, emulsifiable concentrates, dispersion agent, aerosol or paste, just as common agrochemistry medicine, these medicaments often by predetermined concentration, dilute with suitable diluent such as water earlier in use.
This medicament is often by active ingredient of 0.5-90 part (by weight) and the agriculture assistant medicament of 10-99.5 part (by weight), and they are carrier, emulsifying agent, suspension agent, dispersion agent, diffusant, permeate agent, adhesion agent or stablizer, these assistant medicaments can add as required.Carrier can divide solid carrier and liquid vehicle.As solid carrier, may on address the powder of animal and plant origin, as starch, gac, bean powder, flour, timber powder, fish meal or milk powder; Or be mineral dust such as talcum powder, kaolin, wilkinite, lime carbonate, barren rock, diatomite, hard charcoal, clay, aluminium powder or sulphur powder.May address water, alcohols such as methyl alcohol or ethylene glycol; Ketone such as acetone or methyl ethyl ketone, ethers such as amylene oxide or tetrahydrofuran (THF); Aliphatic hydrocarbon such as kerosene etc.; Aromatic hydrocarbons such as dimethylbenzene, Three methyl Benzene, tetramethyl-benzene or solvent naphtha; Halogenated hydrocarbon such as chloroform, Benzene Chloride; Acid acid amides such as dimethyl formamide; Ester such as ethyl acetate or glycerin fatty acid ester; Nitrile compound such as acetonitrile; Or the compound of sulfur-bearing such as dimethyl sulfoxide (DMSO).
In addition, compound of the present invention according to circumstances needs, and can be used in combination with the pharmaceutical chemicals of other agriculture usefulness, as pesticide, Acaricide, nematicide, sterilant, antiviral agent, attractant, weedkiller or plant-growth regulator.In some cases, this merging is used and can be promoted effect.
For example, this pesticide, Acaricide or nematicide can be the organo phosphorous compoundss mentioned as 0-ethyl S-propyl dithiocarbamate phosphoric acid ester 0-(4-bromo-2-chlorobenzene), 2,2-Ethylene Dichloride dimethyl phosphoric acid ester, ethyl 3-methyl-4-(methylthio group) benzene sec.-propyl phosphoro-amidate, 0,0-dimethyl 0-(4-nitro-m-tolyl) thiophosphatephosphorothioate, 0-ethyl-10-(4-oil of mirbane) phenyl thiophosphatephosphorothioate, 0,0-diethyl 0-2-sec.-propyl-6-methylpyrimidine-4-base thiophosphatephosphorothioate, 0,0-dimethyl 0-(3,5, the 6-trichloro-2-pyridyl) thiophosphatephosphorothioate, 0-S-dimethyl acetyl thio phosphamide or 0-(2,4-dichlorophenyl) 0-ethyl S-propyl disulfide substituted phosphate; Amino formate compounds is as 1-naphthyl methyl carbamate, 2-o-phenyl-isopropyl methyl carbamate, 2-methyl-2-(methylthio group) propionic aldehyde 0-methylamino carbamoyl oxime, 2,3-dihydro-2,2-dimethyl benzofuran-7-ylmethyl carbamate, two (N-the 1-(methylthio group)-ethylidene ammonia oxygen carbonyl }-N-first ammonia] sulfide S-methyl N-(methylamino methanoyl) thioacetyl polyurethane, N, N-dimethyl-2-methylamino methanoyl imino--2-(methylthio group) ethanamide, 2-(ethyl thiomethyl) phenol methylcarbamate, 2-dimethylamino-5,6-dimethyl pyrimidine-4-base dimethyl carbamate, or S, S '-2-dimethylamino trimethylene two (thiocarbamate); Organochlorine compound as: 2,2,2-three chloro-1, two (4-chloro-phenyl-) ethanol of 1-or 4-chloro-phenyl--2,4,5-trichlorobenzene sulfone; Organometallic compound is as three cyhexatin oxyhydroxide; Pyrethroid compound is as (RS)-α-cyanogen-3-benzyloxy phenoxy base (RS)-2-(4-chloro-phenyl-)-the 3 Methylbutanoic acid ester, 3-benzyloxy phenoxy base (1RS)-suitable, instead-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester, (RS)-and α-cyanogen-3-benzyloxy phenoxy base (1RS)-suitable, anti--3-(2, the 2-Ethylene Dichloride)-2,2-dimethyl cyclopropane carboxylic acid ester, (S)-and α-cyanogen-3-benzyloxy phenoxy base (1R)-suitable-3-(2, the 2-sym-dibromoethane)-2,2-dimethyl cyclopropane carboxylic acid ester, or (RS)-α-cyanogen-3-benzyloxy phenoxy base (1RS)-suitable-3-(2-chloro-3,3, the 3-trifluoro-propenyl)-2,2-dimethyl cyclopropyl alkane carboxylicesters; Benzoyl urea compounds as: the 1-(4-chlorobenzene)-3-(2,6-two fluorobenzoyl) urea, 1-{ 3,5-two chloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-phenyl }-3-(2,6-two fluorobenzoyl) urea or 1-(3,5-two chloro-2,4 difluorobenzene bases)-and 3-(2,6-two fluorobenzoyl) urea; Other compound is as 2-tert-butyl imido-3-sec.-propyl-5-phenyl-3,4,5,6-tetrahydrochysene-2H-1,3,5-thiadiazine-4-ketone, 4-methyl-5-(4-chloro-phenyl-)-3-cyclohexyl carboxyamide base-2-thiazolidone or N-methyl-two (2,4-dimethylbenzene formamino) amine; The neotonin compounds as: sec.-propyl-(2E, 4E)-11-methoxyl group-3,7,11-trimethylammonium-2,4-dodecadienoic acid ester; Also have other compound such as dinitro compound, organosulfur compound, urea compound or triaizine compounds.In addition, (B Thurigiensis) agent of microbial pesticide such as bacillus thuringiensis or nuclear polyhedral virus also can merge application with compound of the present invention.
As fungicide, the organo phosphorous compounds that can mention is such as S-benzyl O, O-di-isopropyl thiophosphatephosphorothioate, O-ethyl S, S-phenylbenzene phosphorodithioate or ethyl phosphonic acid hydrogen aluminium; Organochlorine compound, such as 4,5,6,7-tetrachloro 2-benzo [c] furanone or termil; Two thiocarbamate ester cpds, such as two (two thiocarbamates) manganese of ethene, two (two thiocarbamates) zinc of ethene, the mixture of two (two thiocarbamates) manganese of ethene and zinc salt, two (two thiocarbamate esters) two zinc salts of two (dimethyl dithiocarbamate ester)-ethene or two (two thiocarbamates) zinc of polymeric propylene; The N-fontanel is for sulphur alkyl compound, such as the N-(trichloro-methylthio) hexamethylene-4-alkene-1,2-dicarboxylic acid imines, N-(1,1,2,2-tetrachloro ethylmercapto group) hexamethylene-4-alkene-1,2-dicarboxylic acid imines or N-(trichloro-methylthio) phthalic imidine; The dicarboxylic acid group with imine moiety, such as 3-(3, the 5-dichlorophenyl)-and N-sec.-propyl-2,4-dioxy imidazolidyl-1-carbonyl acid amides, (RS)-3-(3, the 5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-diketone or N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboxylic acid imines; Benzimidazole compound is such as methyl 1-(butyl carbamyl)-2-benzoglyoxaline-carboxylamine or dimethyl 4,4 '-(O-phenylene) two (3-thiourea carbamates); Azole compounds is such as the 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2, the 4-triazol-1-yl) butanone, 1-(hexichol-4-base oxygen)-3,3-dimethyl-1-(1H-1, the 24-triazol-1-yl) fourth-2-alcohol, 1-[N-(4-chloro-2-trifluoromethyl)-2-propoxy--acetylimino] imidazoles, (±)-1-[2-(2, the 4-dichlorophenyl)-4-ethyl-1,3-dioxolane-2-ylmethyl]-1H-1,2, the 4-triazole, (±)-1-[2-(2, the 4-dichlorophenyl)-and 4-propyl group-1,3-dioxolane-2-ylmethyl]-1H-1,2, the 4-triazole or-1-[2-(2, the 4-dichlorophenyl) amyl group]-1H-1,2, the 4-triazole; Carbinol compound, such as (±)-2,4 '-two chloro-α-(pyrimidine-5-yl) benzhydrol, perhaps (±)-2,4 '-two chloro-α-(1H-1,24-triazol-1-yl methyl) benzhydrol; N-benzanilide compound, such as 3 '-isopropoxy-2-toluyl aniline, perhaps 3 '-isopropoxy-α, α, α-three fluoro-O-is to toluyl aniline; 2,6-dimethyl-N-anilid compound is such as methyl N-(2-methoxy ethanoyl)-N-(2,6-xylyl)-the DL-alanine ester; With other compound such as diethylenediamine compound, morpholinium compound, anthraquinone compounds, quinoxaline compounds, Ba Dousuan compound, sulfenic acid compound, urea compounds or germ resistance material.
Sterilant of the present invention, Acaricide and nematicide are to controlling various harmful insect, and mite that has and deleterious nematode are effective.With its active ingredient concentration is 1-20, and 000ppm is preferably from 20 to 2,000ppm, and in time, used.The concentration of active ingredient can change along with the situation of specific prescription, mode, purpose, time or application site and harmful insect.For example, aquatic harmful insect can be applied to the prescription of above-mentioned concentration the place that insect breaks out and be controlled, and like this, what the concentration of active ingredient in water just can be than above-mentioned scope is low.
The amount that active ingredient is used at the per unit surface-area preferably from 10 to 1,000 restrains (per 10 per surface area) from about 0.1 to 5,000 gram usually.Yet under a certain particular case, the amount of application can exceed above-mentioned scope.
The various prescriptions that contain The compounds of this invention and their diluted compositions can adopt the convention method of common use to use; such as spraying (promptly spray, atomize, spray, scatter its powder or particulate or be dispersed in the water); use (as mixing or soaking into) in the soil, surface applications (as be coated with, rub powder or cover) or soak into to obtain deleterious feed.Further, can the forage feed poultry of above-mentioned active ingredient will be contained, to be controlled at prolific insect, especially insect pest in its movement.In addition, active ingredient can also use with a kind of application method that is called ultra-small volume.In this method, composition can be formed with 100% active ingredient.
Test examples 1
Each the prescription in contained active ingredient shown in the table 2 be dispersed in the water, each active ingredient concentration be the dispersion liquid of 800ppm and 200ppm, the French bean seedlings of only depositing a slice primary leaf are transplanted to-diameter be 7 centimetres high be 4 centimetres the cup in.Larva and the adult of about 30 2 spider mites (Tetranychusyrtucae) are infected on French beans blade.Then, French beans soaked for ten seconds in the above-mentioned dispersion liquid of measuring concentration in advance, were placed on behind the air drying in the constant temperature, in 28 ℃ (compound N is O.1 to examples of 38) or 26 ℃ of (other example) illumination.Handled back two days, the mite of checkmating counting calculates mortality ratio by following equation:
Mortality ratio (%)=(dead mite number)/(total mite number) * 100
The result is as shown in table 2.
Table 2
Compound mortality ratio (%) compound mortality ratio (%)
Number active ingredient is that the activeconstituents number of being activeconstituents is that active ingredient is
800ppm 200ppm 800ppm 200ppm
1 100 100 31 100 100
2 100 100 32 100 100
3 100 100 33 100 100
4 100 100 34 100 100
5 100 100 35 100 100
6 100 100 36 100 100
7a 100 100 37 100 100
7b 100 100 38 100 100
8a 100 100 39 100 100
8b 100 100 40 100 100
9 100 100 41 100 100
10 100 100 42 100 100
11 100 100 43 100 100
12 100 100 44 100 100
13 100 100 45 100 100
14 100 100 46 100 100
15 100 100 47 100 100
16 100 100 48 100 100
17 100 100 49 100 100
18 100 100 50 100 100
19 100 - 51 100 100
20 100 100 52 100 100
20a 100 100 53 100 100
20b 100 100 54 100 100
20a-Ⅰ 100 100 55 100 100
20b-Ⅰ 100 100 56a 100 100
20a-Ⅱ 100 100 56b 100 100
20b-Ⅱ 100 100 57 100 100
21 100 100 58 100 100
22a 100 100 59 100 100
22b 100 100 60 100 100
23 100 100 61 100 100
24 100 100 62 100 100
25 100 100 63 100 100
26 100 100 64 100 100
27a 100 100 65 100 100
27b 100 100 66a 100 100
28 100 100 66b 100 100
29 100 100 67 100 100
30 100 100
Table 2(is continuous)
Mortality ratio (%) mortality ratio (%) _
The compound compound
Number activeconstituents is that the activeconstituents number of being active ingredient is that active ingredient is
800ppm 200ppm 800ppm 200ppm
68 100 -
69 ″ -
70 ″ 100
71 ″ ″
72 ″ ″
73 ″ ″
74 ″ ″
Comparative compound
*40 0
Annotate: this compound of * is 0, and 0-diethyl (4,4-dimethyl-2-sulphur-3-oxazolinyl) phosphonic acid ester is disclosed in Japanese unexamined patent publication number 144,794/1984.
Test examples 2
Each prescription contains the activeconstituents shown in the table 3, is dispersed in to obtain containing the dispersion liquid that each activity component concentration is 800ppm and 200ppm in the water, and the Caulis et Folium Brassicae capitatae leaf soaks about 10 seconds in relevant dispersion liquid, then at air drying.Be the filter paper of putting a humidity on 9 centimetres the Petri dish at a diameter, dried cabbage leaf is placed on the filter paper.Put diamond back moth (Plutella xylostella) larva of second phase or three phases on paper, covering Petri dish, to be placed on illumination temperature be in 26 ℃ the thermostat container, to put larva two days later, and the insect counts of checkmating calculates mortality ratio by following equation:
Mortality ratio (%)=(dead insect number)/(insect sum) * 100
The result is as shown in table 3.
Table 3
Mortality ratio (%) mortality ratio (%)
The compound compound
Number activeconstituents is that the activeconstituents number of being active ingredient is that active ingredient is
800ppm 200ppm 800ppm 200ppm
1 100 100 31 100 100
2 100 100 32 100 100
3 100 100 33 100 100
4 100 100 34 100 100
5 100 100 35 100 100
6 100 100 36 100 100
7a 100 100 37 100 100
7b 100 100 38 100 100
8a 100 100 39 100 100
8b 100 100 40 100 100
9 100 100 41 100 100
10 100 100 42 100 100
11 100 100 43 100 100
12 100 100 44 100 100
13 100 100 45 100 100
14 100 90 46 100 100
15 100 100 47 100 90
16 100 100 48 100 100
17 100 90 49 100 100
18 100 100 50 100 100
20 100 100 51 100 100
20a 100 100 52 100 100
20b 100 100 53 100 100
20a-Ⅰ 100 100 54 100 100
20b-Ⅰ 100 100 55 100 100
20a-Ⅱ 100 - 56a 100 100
20b-Ⅱ 100 100 56b 100 100
21 100 100 57 100 100
22a 100 100 58 100 100
22b 100 100 59 100 100
23 100 100 60 100 100
24 100 100 61 100 100
25 100 100 62 100 100
26 100 100 63 100 100
27a 100 100 64 100 100
27b 100 100 65 100 100
28 100 100 66a 100 100
29 100 100 66b 100 100
30 100 100 67 100 100
68 ″ ″
69 ″ ″
71 ″ ″
Relatively
＊ 0 0
Compound
Annotate: this compound of * is identical with the comparative compound of table 2.
Test examples 3
Test is undertaken by method same in the test examples 2, just replaces the diamond back moth of second phase or three phases with common burglar's moth larvae of second phase or three phases, the results are shown in table 4.
Table 4
Mortality ratio (%) mortality ratio (%)
The compound compound
Number activeconstituents is that the activeconstituents number of being active ingredient is that active ingredient is
800ppm 200ppm 800ppm 200ppm
1 100 100 28 100 100
2 100 100 29 100 90
3 100 100 30 100 100
4 100 90 31 100 100
5 100 100 32 100 100
6 100 100 33 100 100
7a 100 100 34 100 100
7b 100 100 35 100 100
8a 100 100 36 100 100
8b 100 100 37 100 100
9 100 100 38 100 100
10 100 100 39 100 100
11 100 100 40 100 90
12 100 100 41 100 100
13 100 100 42 100 -
14 100 95 43 100 -
15 100 100 44 100 100
16 100 95 45 100 100
17 100 100 46 100 100
18 100 100 47 100 100
20 100 100 48 100 90
20a 100 100 49 100 100
20b 100 100 50 100 -
20a-Ⅰ 100 100 51 100 -
20b-Ⅰ 100 100 52 100 100
20a-Ⅱ 100 90 53 100 100
20b-Ⅱ 100 100 54 100 -
21 100 100 55 100 100
22a 100 90 56a 100 100
22b 100 90 56b 100 100
23 100 95 57 100 100
24 100 95 62 100 100
25 100 100 63 100 100
26 100 100 64 100 100
27a 100 100 70 ″ ″
27b 100 100 71 ″ ″
72 ″ ″
73 ″ ″
74 ″ ″
Compare 00
＊
Compound
Annotate: this compound of * is identical with the comparative compound of table 2.
Test examples 4
Only there are the French bean seedlings of a slice primary leaf to be transplanted to (identical) in one glass with test examples 1.2 spider mites (Tetranychus urticae) adult is infected in the French beans leaf, and allowed them lay eggs, then adult is removed.France's beans immersed for 10 seconds in each dispersion liquid that is dispersed in the activeconstituents that contains predetermined concentration that generates in the water of filling a prescription by the listed activeconstituents of table 5.Then, French beans at air drying, and are kept in the thermostat container of 28 ℃ (in examples of No. 1 to 37, compound) or 26 ℃ of (in other example) illumination.After handling five days, check the hatching situation of ovum, calculate dead ovum rate by following equation:
Dead ovum rate (%)=(dead ovum number)/(sum of ovum) * 100
The result is as shown in table 5.In addition, the squab dead larva number ovum number of seeking death is handled.
Table 5
The dead ovum rate of compound (%)
Activeconstituents is that active ingredient is
Number 800ppm 200ppm
1 100 100
3 100 100
4 100 100
5 100 100
12 100 100
16 100 100
17 100 100
20 100 100
20a 100 100
20b 100 100
23 100 100
25 100 100
37 100 100
39 100 100
40 100 100
58 100 -
61 100 -
62 100 -
70 100 100
72 100 100
73 100 100
Compare 00
＊
Compound
Annotate: this compound of * is identical with the comparative compound of table 2.
Test examples 5
The rice plant seedling soaked in the dispersion liquid that contains various activeconstituents 800ppm 10 seconds, surround with absorbent cotton at the air drying back root part and to put into test tube, put into 10 little brown plant locust (Laodelphax striatellus) adults then in the test tube, the test tube mouth covers with gauze.Test tube is placed in the thermostat container of 26 ℃ of illumination, puts into two days later, and the insect counts of checkmating, mortality ratio are pressed test examples 5 used same procedure and calculated.The results are shown in table 6.
Table 6
Mortality ratio (%) mortality ratio (%)
The compound activity composition for the compound activity composition is
Number 800ppm 800ppm
1 100 35 100
2 100 36 100
3 100 37 100
4 100 38 100
5 100 39 100
6 100 40 100
7a 100 41 100
7b 100 42 100
8a 100 43 100
8b 100 44 100
9 100 45 100
11 100 46 100
12 100 47 100
16 100 48 100
17 100 49 100
20a 100 51 100
20a-Ⅰ 100 52 100
21 100 53 100
22a 100 55 100
22b 100 56a 100
25 100 56b 100
27a 100 57 100
28 100 60 100
29 100 61 100
30 100 63 100
31 100 64 100
32 100 65 100
33 100 66a 100
34 100 66b 100
68 100
69 100
72 100
73 100
Comparative compound
*30
Annotate: this compound of * is identical with comparative compound in the table 2.
Test examples 6
Pollution has the earth of southern root nematode (Meloidgyne incognita) to put into 1, the 000a(square measure) jar in, it is 250 gram/a(square measures that the dispersion liquid that impouring contains activeconstituents in jar makes the concentration of activeconstituents).Handle two days later, the earth of handling mixed, with the tomato seedling transplantation of a strain 3-leaf or 4-leaf phase in jar, in the activeconstituents processing after 20 days, inspection root galls index.The result is as shown in table 7, and the root galls index is pressed following standard formulation:
0: no insect gall
The 1:1-25% root has insect gall
The 2:26-50% root has insect gall
The 3:51-75% root has insect gall
The 4:76-100% root has insect gall
Table 7
Compound number root galls index compound number root galls index compound number root galls index
1 0 20b-Ⅰ 0 40 0
2 0 20a-Ⅱ 1 41 0
3 0 20b-Ⅱ 0 42 0
4 0 21 0 43 0
5 0 22a 0 44 0
6 1 22b 0 45 0
7a 0 23 0 46 0
7b 0 24 0 47 0
8a 0 25 0 48 0
8b 0 26 0 49 0
9 0 27a 0 50 1
10 0 27b 0 51 0
11 2 28 0 52 0
12 0 29 0 53 0
13 1 30 0 54 0
14 1 31 0 55 0
15 0 32 0 56a 0
16 1 33 0 56b 0
17 1 34 0 57 0
18 0 35 0 58 0
20 0 36 0 59 0
20a 0 37 0 60 0
20b 0 38 0 61 0
20a-Ⅰ 0 39 0 62 1
63 0
64 0
65 0
66a 0
66b 0
67 0
68 2
69 1
71 1
Test examples 7
The various prescriptions that will contain active ingredient are dispersed in and obtain a dispersion liquid with predetermined concentration in the water.The Caulis et Folium Brassicae capitatae leaf soaked for 10 seconds in dispersion liquid, then at air drying.In diameter is 9 centimetres Petri dish, put the filter paper of a humidity, on paper, put dried, the Caulis et Folium Brassicae capitatae leaf.Ye Shangfang is with the female worm of aptery viviparity of green black peach aphid worm (Myzus persicae), and the thermostat container of 26 ℃ of illumination is added a cover and placed to Petri dish.Put behind the worm two days, the same quadrat method that the insect counts of checkmating, mortality ratio are pressed in the test examples 2 is calculated, and the results are shown in table 8.
Table 8
Mortality ratio (%) mortality ratio (%)
The compound number activeconstituents is that activeconstituents is that active ingredient is for the compound number active ingredient
800ppm 200ppm 800ppm 200ppm
1 100 - 33 100 100
2 100 - 34 100 100
3 100 - 35 100 100
4 100 100 36 100 100
5 100 100 37 100 100
6 100 100 38 100 100
7a 100 100 39 100 100
7b 100 100 40 100 100
8a 100 100 41 100 100
8b 100 100 42 100 100
9 100 100 43 100 100
10 100 100 44 100 100
11 100 100 45 100 100
12 100 100 46 100 100
13 100 100 47 100 90
14 100 100 48 100 100
15 100 100 49 100 100
16 100 100 51 100 -
17 100 100 52 100 100
18 100 100 53 100 100
20a-Ⅰ 100 100 54 100 100
20b-Ⅰ 100 100 55 100 100
20a-Ⅱ 100 100 56a 100 100
20b-Ⅱ 100 100 56b 100 100
21 100 100 57 100 -
22a 100 100 58 100 100
22b 100 100 59 100 100
23 100 100 60 100 100
24 100 100 61 100 100
25 100 100 62 100 100
26 100 100 63 100 100
27a 100 100 64 100 100
27b 100 100 65 100 100
28 100 - 66a 100 -
29 100 100 66b 100 -
30 100 100 68 ″ 100
31 100 100 69 ″ ″
32 100 100 71 ″ ″
72 ″ ″
73 ″ ″
74 ″
Comparative compound
*00
Annotate: the * compound is identical with comparative compound in the table 2,
Test examples 8
The listed various prescriptions that contain active ingredient are scattered in the dispersion liquid that gets a predetermined concentration in the water in table 9.Each strain only has the French bean seedlings of a slice primary leaf to transplant in one glass (identical with test examples 1), makes French beans infect about 30 larva and adults to Mitigan and resistive 2 the spider mites of organic phosphorous insecticide (Tetranychus urticae).Then, French bean seedlings soaked for 10 seconds in the dispersion liquid of above-mentioned predetermined concentration, at air drying and be placed in the thermostat container of 28 ℃ (in examples of compound number 1 to 38) or 26 ℃ of (in other examples) illumination.Handle two days later, the mite of checkmating counting, it is described with quadrat method calculating mortality ratio to press test examples 1.The result is as shown in table 9.
Table 9
Compound mortality ratio (%) compound mortality ratio (%)
Number activeconstituents is that the activeconstituents number of being activeconstituents is that activeconstituents is
100ppm 50ppm 100ppm 50ppm
1 100 100 32 100 100
2 100 100 33 100 100
3 100 100 34 100 95
4 100 100 35 100 60
5 100 86 36 100 100
6 100 90 37 93 63
7a 95 88 38 100 44
7b 100 75 39 100 80
8a 100 96 41 100 100
9 100 100 46 100 72
10 85 50 48 90 74
11 100 80 51 100 84
12 100 100 52 93 86
13 100 90 53 100 75
14 91 93 54 100 100
15 94 92 55 100 100
16 100 100 56b 100 90
17 100 100 57 100 100
18 100 75 58 100 52
20a 100 100 59 100 77
20b 93 94 61 100 31
20a-Ⅰ 100 100 63 100 75
20b-Ⅱ 100 100 64 100 19
21 100 65 65 100 100
22a 100 36 66a 88 77
23 93 87 66b 88 75
24 100 100 67 100 95
25 100 100 70 100 100
26 100 100 71 100 100
27a 100 100 72 100 100
27b 100 93 73 100 100
28 100 71 74 100 100
29 100 95 Mitigans
*85 10
30 100 90 0 0
31 96 67 demeton-methyls
*
0 0
Comparative compound
*
Annotate: the * comparative example
The used comparative compound of this compound of * and table 2 is identical.
Test examples 9
Each prescription contains the listed activeconstituents of table 10, is dispersed in and obtains a dispersion liquid that contains the 100ppm activeconstituents in the water.The French bean seedlings that each strain had two primary leafs are transplanted to (identical with test examples 1) in one glass, with the dispersion liquid of 10 milliliters of above-mentioned concentration earth are soaked into.Handle two days later, with the larvas of about 30 2 spider mites that Mitigan (dicofol) and organic phosphorous insecticide had a drag with become insect infection to blade, cup is placed in the thermostat container of 26 ℃ of illumination, infect two days later, the mite of checkmating counting is pressed test examples 1 used same quadrat method and is calculated mortality ratio.The result is as shown in table 10.
Table 10
Compound number mortality ratio (%) compound number mortality ratio (%)
4 100 26 100
5 100 27a 100
7a 92 27b 100
7b 100 28 100
9 100 29 100
18 100 30 90
20 100 36 100
20a 100 37 100
20b 100 38 80
20a-Ⅰ 100 39 100
20b-Ⅰ 100 41 100
20a-Ⅱ 100 45 100
20b-Ⅱ 100 46 100
22a 100 49 100
22b 100 53 81
23 100 55 100
24 100 60 100
25 100 61 80
65 95
66a 100
66b 100
72 100
73 100
74 100
Test examples 10
40 gram dry soils are placed in the oyster white cup 10 milliliters of dispersion liquids that contain active ingredient 500ppm of impouring.Even with mixing with soil.Put a slice onion after 24 hours in the earth as feed, on earth, put 10 larvas that the onion maggot (Hylemya untigua) in 10 day age is arranged then.Put behind the worm 48 hours, dead insect counts press the identical methods calculating mortality ratio of test examples 2.The results are shown in table 11.
Table 11
Compound number mortality ratio (%) compound number mortality ratio (%)
1 100 17 100
2 100 20b 100
3 100 20a-Ⅰ 100
4 100 20b-Ⅱ 100
5 100 22a 100
6 100 22b 100
7a 100 25 100
7b 100 26 100
8a 100 27a 100
8b 100 27b 100
9 100 29 100
10 100 39 100
11 100 41 100
13 100 52 100
14 100 55 100
15 100 60 100
Experiment embodiment 11
Test is undertaken by test examples 7 identical methods, and just using has the green peach budworm (Myzus persicae) of resistance to replace common green peach budworm to organic phosphorous insecticide.The result is as shown in table 12.
Table 12
Compound mortality ratio (%)
Number activeconstituents is 800ppm
3 100
4 100
5 100
7a 100
7b 100
8b 100
9 100
12 100
20a-Ⅰ 100
20b-Ⅱ 100
21 100
22a 100
23 100
26 100
29 100
32 100
33 100
34 100
36 100
37 100
38 100
39 100
41 100
45 100
46 100
48 100
49 100
52 100
54 100
55 100
56a 100
56b 100
59 100
60 100
63 100
Sumithion
*0
Rogor
*20
The lucky purulence of platform
*30
Comparative compound
*0
Annotate: the * comparative example
The * compound is identical with the comparative compound of table 2.
Test examples 12
Diameter is that 7 centimetres filter paper is placed in the oyster white cup, drips on the filter paper that to contain active ingredient concentration with 1 milliliter be the dispersion liquid of 800ppm in water.Putting into 24 in the cup has the housefly (No 3 Yume-no-shima clusters) of resistance to organic phosphorous insecticide, and the oyster white cup is gone in the thermostat container of 26 ℃ of illumination.Put and released fly one day, calculate dead fly number, press test examples 2 identical methods and calculate mortality ratio.The result is as shown in table 13.
Table 13
Compound number mortality ratio (%)
1 100
4 100
5 100
7a 100
8a 100
8b 100
20 100
20a 100
20b 100
20a-Ⅰ 100
20b-Ⅱ 100
39 100
41 100
Sumithion
*60
The Malathion
*60
Annotate:
*Comparative example
Formulation examples 1
(a) O.1 20 parts by weight for compound N
(b) N, 70 parts of N '-dimethyl formamide are by weight
(c) 8 parts in polyoxyethylene alkylphenyl base ether by weight
It is one emulsifiable concentrate that above-mentioned composition mixes and is dissolved into.
Formulation examples 2
(a) 50 parts of compound N o41 by weight
(b) 38 parts of tetramethyl-benzenes by weight
(c) a kind of emulsifier mixture contains the benzene sulfonamide acid esters, and 12 parts of polyxyethylated alkylphenol and polyoxyethylene phenyl phenolic ethers (trade mark is called Aglysolp-311, by kao soap company limited make) are by weight
Above-mentioned uniform ingredients ground mixes also dissolving, one emulsifiable concentrate.
Formulation examples 3
(a) 85 parts of compound N o8a by weight
(b) emulsifier mixture and formulation examples
In 2 used identical 15 parts by weight
Above-mentioned uniform ingredients ground mixes, and gets the emulsifiable concentrate of a high density.
Formulation examples 4
(a) 5 parts of compound N o63 by weight
(b) 95 parts of talcum powder by weight
Formulation examples 5
(a) 5 parts of compound N o20a by weight
(b) 45 parts of boron-moisten soils by weight
(c) 50 parts of kaolin by weight
Add small amount of water and kneading together in the above-mentioned composition, be squeezed into little granular, dry particle then.
Formulation examples 6
(a) 0.50 part of compound N o5 by weight
(b) 0.15 part of polyoxyethylene octyl phenylate by weight
(c) 0.10 part of polyoxyethylene phosphate by weight
(d) 99.25 parts of calcium carbonate granules by weight
Composition (a) to (c) mixes in advance equably, uses the acetone diluted of sufficient quantity then, and they are sprayed on the composition (d).Remove acetone and promptly obtain particle.
Formulation examples 7
(a) 50 parts of compound N o7a by weight
(b) 15 parts of thin ground silicas by weight
(c) 25 parts in fine clay powder by weight
(d) 2 parts of the condensess of naphthalene sulfonate salt and formalin by weight
(e) 3 parts of dialkyl group esters of sulfosuccinic acids by weight
(f) 5 parts in the polyxyethylated propylene ether of sulfuric acid by weight
Above-mentioned uniform ingredients ground pulverize and mix contain a wettable powder.
Formulation examples 8
(a) 5 parts of compound N o34 by weight
(b) 5 parts of glycerine by weight
(c) 3 parts of milk powder by weight
(d) 87 parts of fish meal by weight
Knead to above-mentioned uniform ingredients a mashed prod.
Formulation examples 9
(a) 10 parts of compound N o39 by weight
(b) 3 parts of polyoxyethylene octyl phenylates by weight
(c) 87 parts of kerosene by weight
Above-mentioned uniform ingredients ground mixes and dissolving obtains an available pressurized air.The aerosol of ejection.
Claims (4)
1, the preparation process of the organo phosphorous compounds represented of formula I:
X in the formula
1And X
3Be hydrogen atom, the alkyl or the alkoxyl group that can be replaced by halogen, alkoxyl group, alkylthio, phenoxy group, halogenated phenoxy, thiophenyl or halogeno-benzene sulfenyl, and carboxyl, carbalkoxy or the phenyl that can be replaced by halogen, X
2And X
4Be hydrogen atom or alkyl, X
2And X
3Can form alkylidene group, Y together
1, Y
2And Z is Sauerstoffatom or sulphur atom, R
1And R
2Be alkyl, this process comprises the reactant of being represented by the general formula II:
X in the formula
1, X
2, X
3, X
4, Y
1And Y
2Be top fixed group, the compound of representing with the general formula III
Hal is a halogen atom in the formula, Z, R
1And R
2Be top fixed group, having in the presence of the sour accepting agent in-100 to 50 ℃ in solvent, to react.
2, process according to claim 1, wherein reaction process is carried out in the scope of room temperature at-80 ℃.
3, process according to claim 1, wherein reaction process is carried out in ether.
4, process according to claim 1, wherein used sour accepting agent is an organolithium compound in the reaction process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103896 CN1006796B (en) | 1985-05-10 | 1985-05-10 | Process for preparation of organic phosphorus compound |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103896 CN1006796B (en) | 1985-05-10 | 1985-05-10 | Process for preparation of organic phosphorus compound |
| JP60138133A JPH068309B2 (en) | 1985-06-25 | 1985-06-25 | Organophosphorus compounds and insecticides, acaricides and nematicides containing them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103896A CN85103896A (en) | 1987-09-16 |
| CN1006796B true CN1006796B (en) | 1990-02-14 |
Family
ID=25741662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85103896 Expired CN1006796B (en) | 1985-05-10 | 1985-05-10 | Process for preparation of organic phosphorus compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006796B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445519B (en) * | 2008-12-19 | 2011-08-24 | 山东华阳科技股份有限公司 | Thiazole organophosphorus compound, and synthesis method and application thereof |
| CN101434621B (en) * | 2008-12-26 | 2012-09-05 | 山东师范大学 | Thiazole organo phosphorous compounds, and synthesis and use thereof |
| CN102246818A (en) * | 2011-08-08 | 2011-11-23 | 陕西美邦农药有限公司 | Insecticidal composition containing organophosphorus compound |
| CN103288876B (en) * | 2012-02-22 | 2015-11-18 | 上海交通大学 | A kind of Chiral phosphamide compound and preparation method thereof |
| CN103214519B (en) * | 2013-04-02 | 2016-01-06 | 武汉工程大学 | O-ethyl-S-n-propyl-(3-ethyl-2-cyano group imines-1-imidazoles) phosphate synthesis technique |
-
1985
- 1985-05-10 CN CN 85103896 patent/CN1006796B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85103896A (en) | 1987-09-16 |
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