CN1060615C - Guanidine derivatives, their production and insecticides - Google Patents
Guanidine derivatives, their production and insecticides Download PDFInfo
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Abstract
An insecticidal composition containing a guanidine derivative of the formula: (I) wherein R1 is an optionally substituted homocyclic or heterocyclic group, n is 0 or 1, R2 is a hydrogen atom or an optionally substituted hydrocarbon group, R3 is a primary, secondary or tertiary amino group, X is an electron attractive group such as nitro or trifluoroacetyl group, provided that when n is 0, R1 is an optionally substituted heterocyclic group or a salt thereof.
Description
The present invention relates to guanidine derivatives or its salt as insecticide, their production method and contain guanidine derivatives or the Pesticidal combination of its salt.
Various synthetic compounds with pest control effectiveness are used as insecticide, and the great majority of these compounds are organophosphorus esters, carbamate, chlorine-containing organic compounds or pyrethroid compound.People know, and often use these several limited compounds can have a negative impact as increasing the pesticide resistance of insect, and this has caused disclosed discussion in various places.Some compound in the above-mentioned insecticide has the effective insecticidal activity, but performance can not gratifying effect in actual applications, for example to the mankind, the high toxicity of animal and fish is to contingent toxicity of pest natural enemy and the high residue in soil etc.
On the other hand, about guanidine derivatives or its salt, for example 3-nitro-1-(3-picolyl) guanidine is described in Chemical﹠pharmaceutical Bulletin 23,2744 (1975); Guanidine compound such as cimetidine (cimetidine) with antiulcer activity are reported in various documents or patent, but about guanidine derivatives or its salt report that yet there are no as insecticide.
In this case, the object of the present invention is to provide the Pesticidal combination that contains guanidine derivatives or its salt.It is to the mankind, and the natural enemy toxicity of animal and fish and insect is low, and safety, has effectively preventing insect ability, can be used for agricultural, in gardening and/or the family garden.
Therefore, the invention provides (1) a kind of guanidine derivatives of formula (I) or Pesticidal combination of its salt of containing,
R wherein
1Be carbocyclic ring or the heterocycle that replaces arbitrarily, n is 0 or 1, R
2Be hydrogen atom or any alkyl that replaces, R
3Be primary, the second month in a season, the amino and X of uncle is an electron-withdrawing group.If when X is cyano group, R
1Be halogenated pyridyl then, when n is 0, R
1It then is the heterocyclic radical that replaces arbitrarily; (2) formula (I
a) guanidine derivatives or its salt,
R wherein
1aBe the heterocyclic radical that replaces arbitrarily, R
2aBe hydrogen atom or any alkyl that replaces, R
3aBe primary, secondary, uncle is amino, and if work as R
2aWhen being hydrogen atom, R
3aThen be the second month in a season or uncle's amino, X
aBe nitro or trifluoroacetyl group; (3) preparation guanidine derivatives (I
a) or the method for its salt, it comprises the compound or its salt that makes formula (II),
(R wherein
1a, R
2aAnd X
aIdentical with above-mentioned definition, Y is a leaving group) and ammonia or the primary, or secondary amine or its salt react; (4) preparation formula (I
a) guanidine derivatives or the method for its salt, it comprises the compound or its salt with formula (III),
The compound or its salt reaction of (wherein each symbol is identical with above-mentioned definition) and formula (IV),
(wherein each symbol is identical with above-mentioned definition); (5) preparation formula (I
a) guanidine derivatives or the method for its salt, it comprises formula (V) compound or its salt,
The reaction of (wherein each symbol is identical with above-mentioned definition) and formula (VI) compound or its salt,
R
1a-CH
2-Y (VI) (wherein each symbol is identical with above-mentioned definition); (6) preparation formula (I
a) method of guanidine derivatives or its salt, it comprises the compound or its salt with formula (VII),
(R wherein
1aAnd X
aIdentical with above-mentioned definition, R
2bBe hydrogen atom or any alkyl that replaces, R
3bBe the primary, if the second month in a season or uncle's amino are and R
3bWhen being uncle's amino, R
2bThen be hydrogen atom), and the reaction of the compound of formula (VIII),
Y-R (VIII) (wherein Y is identical with above-mentioned definition, and R is the alkyl that replaces arbitrarily); (7) preparation guanidine derivatives (I
a) or the method for its salt, it comprises the compound or its salt with formula (IX),
The compound of (wherein the definition of each symbol is with above-mentioned identical) and formula (X) or nitrating agent reaction,
Y-X
a(X) (wherein the definition of each symbol is with above-mentioned identical)
In the said structure formula, R
1The carbocyclic ring or the heterocyclic radical that refer to replacement arbitrarily.With R
1The carbocyclic ring of expression or heterocyclic radical be respectively only contain atom of the same race or contain two or more not homoatomic cyclic groups.R
1aRefer to the heterocyclic radical of replacement arbitrarily, R
1Definition be applicable to this heterocyclic radical.
R
1The cyclic hydrocarbon radical of expression comprises C
3-8Cycloalkyl, cyclopropyl for example, cyclobutyl, cyclopenta or cyclohexyl; C
3-C
8Cycloalkenyl group, acrylic for example, 1-cyclopentenyl, 1-cyclohexenyl group, 2-cyclohexenyl group, 1,4-cyclohexadiene base; And C
6-14Aryl, phenyl for example, 1-or 2-naphthyl, 1-, 2-, or 9-anthryl, 1-, 2-, 3-, 4-or 9-phenanthryl, perhaps 1-, 2-, 4-, 5-, or 6-Azulene base.Cyclic hydrocarbon radical is an aryl preferably, for example C
6-14Aryl such as phenyl etc.
R
1Or R
1aThe heterocyclic radical of expression comprises and contains 1-5 oxygen, and the 5-8 unit of sulphur or nitrogen heteroatom encircles or their condensed ring.The example of heterocyclic radical is 2-or 3-thienyl, 2-or 3-furyl, 2-or 3-pyrrole radicals, 2-, 3-or 4-pyridine radicals, 2-, 4-, or 5-oxazolyl, 2-, 4-or 5-thiazolyl, 3-, 4-or 5-pyrazolyl, 2-, 4-or 5-imidazole radicals, 3-, 4-or 5-isoxazolyl, 3-, 4-or 5-isothiazolyl, 3-or 5-(1,2,4-oxadiazole base), 1,3,4-oxadiazole base, 3-or 5-(1,2, the 4-thiadiazolyl group), 1,3,4-thiadiazolyl group, 4-, or 5-(1,2, the 3-thiadiazolyl group), 1,2, the 5-thiadiazolyl group, the 1,2,3-triazoles base, 1,2,4-triazolyl, 1H-or 2H-tetrazole radical, N-oxygen-2-, 3-or 4-pyridine radicals, 2-, 4-or 5-pyrimidine radicals, N-oxygen-2-, 4-or 5-pyrimidine radicals, 3-or 4-pyridazinyl, pyrazinyl, N-oxygen-3-or 4-pyridazinyl, benzofuranyl, benzothiazolyl, benzoxazolyl, triazinyl, oxygen triazinyl, tetrazolo [1,5-b] pyridazinyl, triazol [4,5-b] pyridazinyl, oxygen imidazole radicals, dioxy triazinyl, pyrrolidinyl, piperidyl, pyranose, thiapyran base, 1,4-Evil pyridine base (oxadinyl), morpholinyl, 1, the 4-thiazinyl, 1, the 3-thiazinyl, piperadinyl, benzimidazolyl, quinolyl, isoquinolyl, cinnolines base, 2, the 3-phthalazinyl, quinazolyl, quinoxalinyl, the indolizine base, quinolizine base, 1, the 8-phthalazinyl, purine radicals, pteridyl, dibenzofuran group, carbazyl, acridinyl, phenanthridinyl, phenazinyl, fen thialdine base (phenolthiadinyl) Huo phenoxazine group.Heterocyclic radical is 5 or 6 yuan of nitrogenous heterocyclic radicals preferably, 2-for example, 3-or 4-pyridine radicals or 2-, 4-or 5-thiazolyl, R
1Carbocyclic ring or the heterocyclic radical and the R of representative
1aThe heterocyclic radical of representative can have 1-5 (preferably one) substituting group, and these substituting groups can be identical or different.Substituent example is C
1-15Alkyl is methyl for example, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl or pentadecyl; C
3-10Cycloalkyl cyclopropane base for example, cyclobutane base, pentamethylene base or cyclohexyl; C
2-10Alkenyl is vinyl for example, pi-allyl, 2-methacrylic, 2-cyclobutenyl, 3-cyclobutenyl or 3-octenyl; C
2-10Alkynyl group, acetenyl for example, 2-propynyl or 3-hexin base; C
3-10Cycloalkenyl group, cyclopropanyl for example, cyclopentenyl or cyclohexenyl group; C
6-10Aryl phenyl or naphthyl for example; C
7-10Aralkyl, for example benzyl or phenethyl; Nitro; Hydroxyl; Sulfydryl; Oxo; Sulfo-; Cyano group; Carbamoyl; Carboxyl; C
1-4Alkoxy carbonyl group, for example methoxycarbonyl group or carbethoxyl group; Sulfo group; Halogen atom is fluorine for example, chlorine, bromine or iodine; C
1-4Alkoxyl, methoxyl group for example, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy or tert-butoxy; C
6-10Aryloxy group is phenoxy group for example; C
1-4Alkylthio group, methyl mercapto for example, ethylmercapto group, positive rosickyite base, different rosickyite base, positive butylthio or uncle's butylthio; C
6-10Arylthio, thiophenyl for example; C
1-4Alkyl sulphinyl, for example methylsulfinyl or ethyl sulfinyl; C
6-10Aryl sulfonyl kia, phenyl sulfinyl for example; C
1-4Alkyl sulphonyl such as mesyl or ethylsulfonyl; C
6-10Aryl sulfonyl such as benzenesulfonyl; Amino; C
2-6Acylamino-, for example acetylamino or propionamido; Single-or two-C
1-4Alkyl amino, methylamino for example, ethylamino, n-propylamine base, isopropylamino, n-butyl amine base, dimethylamino or lignocaine; C
3-6Naphthene amino, for example hexamethylene amino; C
6-10Virtue is amino, for example phenylamino; C
2-4Acyl group, for example acetyl group; C
6-10Aryl carbonyl such as benzoyl; And contain and be selected from oxygen, sulphur, the 1-4 of nitrogen heteroatomic 5-6 unit heterocyclic radical, for example 2-or 3-thienyl, 2-or 3-furyl, 3-, 4-or 5-pyrazolyl, 2-, 4-or 5-thiazolyl, 3-, 4-or 5-isothiazolyl, 2-, 4-or 5-oxazolyl, 3-, 4-or 5-isoxazolyl, 2-, 4-or 5-imidazole radicals, 1,2,3 or 1,2,4-triazolyl, 1H-or 2H-tetrazole radical, 2-, 3-or 4-pyridine radicals, 2-, 4-or 5-pyrimidine radicals, 3-or 4-pyridazinyl, quinolyl, isoquinolyl or indyl.1-5 the substituting group that is selected from the substituting group that exemplifies above can be connected on above-mentioned carbocyclic ring or the heterocyclic radical.When substituting group for example is C
6-10Aryl, C
7-10Aralkyl, C
3-10Cycloalkyl, C
3-10Cycloalkenyl group, C
6-10Aryloxy group, C
6-10Arylthio, C
6-10Aryl sulfonyl kia, C
6-10Aryl sulfonyl, C
6-10When virtue amino or heterocyclic radical, it can be further by 1-5 above-mentioned halogen atom; Hydroxyl; C
1-4Alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group; C
2-4Alkenyl such as vinyl, pi-allyl, 2-methacrylic; C
2-4Alkynyl group such as acetenyl or 2-propynyl; C
6-10Aryl; C
1-4Alkoxyl; Phenoxy group; C
1-4Alkylthio group or thiophenyl replace.When substituting group is C
1-15Alkyl, C
2-10Alkenyl, C
2-10Alkynyl group, C
1-4Alkoxyl, C
1-4Alkylthio group, C
1-4Alkyl sulphinyl, C
1-4Alkyl sulphonyl, amino, single-or two-C
1-4Alkylamino, C
3-6Naphthene amino or C
6-10When virtue was amino, it can also be further by 1-5 above-mentioned halogen atom, hydroxyl, C
1-4Alkoxyl or C
1-4Alkylthio group replaces.
R
1Example preferably be nitrogenous 5-or 6-unit heterocyclic radical, for example be pyridine radicals or thiazolyl, they can be replaced by 1 or 2 halogen.
" n " refers to 0 or 1, preferably 1.
At R
2, R
2a, R
2bAnd the alkyl in " alkyl that the replaces arbitrarily " speech among the R comprises C
1-15Alkyl, C
3-10Cycloalkyl, C
2-10Alkenyl, C
2-10Alkynyl group, C
3-10Cycloalkenyl group, C
6-10Aryl and C
7-10Aralkyl, they are addressing R
1The time referred.At R
1Those substituting groups of being mentioned on the carbocyclic ring of representative or the heterocyclic radical also are applicable to the substituting group in " alkyl that replaces arbitrarily " speech.
R
2, R
2aAnd R
2bExample preferably be hydrogen atom and C
1-4Alkyl, as methyl, ethyl or propyl group, the better example of R is above-mentioned C
1-4Alkyl.
R
3, R
3a, and R
3bRefer to the primary, the second month in a season, uncle's amino can be represented by the formula:
R wherein
4And R
5Can be identical or different, be the alkyl or the R of hydrogen atom or replacement arbitrarily
4And R
5Both and contiguous nitrogen-atoms are amino (in addition, as the R of following formula in conjunction with forming a ring
4And R
5When being hydrogen atom, this primary amino radical is unsubstituted amino, works as R
4And R
5In any one when being hydrogen atom, this secondary amino group is mono-substituted amino, works as R
4And R
5When both all were not hydrogen atom, this uncle's amino was disubstituted amido.) at R
2, R
2a, R
2bAnd the alkyl of any replacement of being mentioned among the R is applicable to R
4And R
5
By R
4And R
5Forming the amino example of ring together with contiguous nitrogen-atoms is '-aziridino, azelidinyl, pyrrolidinyl, morpholinyl and sulfo-sign indicating number quinoline base.R
3, R
3a, R
3bBetter example be unsubstituted amino, single C
1-4Alkylamino such as methylamino, the ethylamino or third amino; Two C
1-4Alkylamino such as dimethylamino, Methylethyl amino and C
1-4Acylamino-such as formamido group, N-methyl formamido group or acetylamino.
The example of the electron withdraw group that X represents is a cyano group, nitro, alkoxy carbonyl group (C for example
1-4Alkoxy carbonyl group such as methoxycarbonyl group or carbethoxyl group), hydroxycarbonyl group, C
6-10Aryloxy carbonyl (for example carbobenzoxy), heterocycle oxygen carbonyl (above-mentioned heterocyclic radical is applicable to this group, therefore particularly pyridine oxygen carbonyl or thiophene oxygen carbonyl), C
1-4Alkyl sulphonyl, it can be by halogen such as chlorine, and bromine or fluorine replace (for example methyl sulphonyl, trifluoromethyl sulfonyl, ethylsulfonyl), and sulfamoyl is two-C
1-4Alcoxyl phosphoryl (for example diethoxy phosphoryl), C
1-4Alkanoyl, it can be by halogen such as chlorine, and bromine or fluorine replace (for example acetyl group, tribromo-acetyl base or trifluoroacetyl group), C
6-10Aryl carbonyl (for example benzoyl), carbamoyl or C
1-4Alkyl sulphonyl thiocarbamoyl (for example methyl sulphonyl thiocarbamoyl).The better example of electron withdraw group is a nitro.X
aRefer to nitro or trifluoroacetyl group.
The example of leaving group Y is halogen atom such as chlorine, bromine, iodine or fluorine; C
1-4Alkylsulfonyloxy, it can be replaced by 1-3 halogen atom (as Cl, Br, or F), sulfonyloxy methyl oxygen base for example, ethyl sulfonyloxy, butyl sulfonyloxy or trifluoromethyl sulfonyloxy; C
6-10Aryl-sulfonyl oxygen, it can be replaced by 1-4 halogen atom (as Cl, Br or F), and for example phenylsulfonyloxy is right-tosyloxy, and is right-bromobenzene sulfonyloxy or 1,3,5-trimethylbenzene sulfonyloxy; C
1-6Acyloxy, it can be replaced by 1-3 halogen atom (as Cl, Br or F), acetoxyl group for example, propionyloxy or trifluoroacetyl oxygen base; C
6-10Aryl-carbonyl oxygen such as benzoyloxy; Hydroxyl; C
1-4Alkoxyl such as methoxy or ethoxy; C
1-4Alkylthio group is as methyl mercapto or ethylmercapto group; C
1-4Alkyl sulphinyl such as methylsulfinyl, C
1-4Alkyl sulphonyl is as mesyl; C
6-10Aryloxy group, it can be replaced by 1-3 halogen (as Cl, Br or F) or nitro, and phenoxy group for example is to chlorophenoxy or p-nitrophenyl oxygen base; Heterocyclic oxy group such as 2-pyridine oxygen base or 2-benzoxazole oxygen base; C
6-10Arylthio, it can replace by 1 or 2 nitro etc. thiophenyl for example, p-nitrophenyl sulfenyl; C
7-12Aromatic alkylthio, it can replace by 1 or 2 nitro etc., for example benzylthio is right-the nitrobenzyl sulfenyl; Heterocycle sulfenyl such as 2-pyridine sulfenyl or 2-[4-morpholinodithio sulfenyl; Amino, single-or two-C
1-4Alkyl amino such as methylamino, the nitrogen heterocycle of ethylamino or dimethylamino and 5 yuan of rings, as 1-imidazole radicals or 1,2, the 4-triazol-1-yl.
The better example of Y in compound (II) and (III) is C
1-4Alkylthio group such as methyl mercapto or ethylmercapto group, C
7-12Aromatic alkylthio such as benzylthio; C
1-4Alkoxyl such as methoxy or ethoxy, amino and single-or two-C
1-4Alkyl amino such as methylamino, ethylamino or dimethylamino.In compound (VI), the Y in (VIII) and (X) is halogen atom such as chlorine or bromine, C
1-4Alkylsulfonyloxy, it can be replaced by 1-3 halogen atom, as mesyloxy or trifluoromethyl sulfonyloxy, C
6-10Aryl-sulfonyl oxygen such as phenylsulfonyloxy or right-tosyloxy, hydroxyl and C
1-4Acyloxy, it can be replaced by 1-3 halogen atom, as acetoxyl group or trifluoroacetyl oxygen base.
The better example of guanidine derivatives (I) or its salt is a formula (I
b) representative compound or its salt:
R wherein
1bBe pyridine radicals, halogenated pyridyl or halo thiazolyl, R
2a, R
4a, and R
5aCan be identical or different, they are hydrogen atoms, or methyl, ethyl, formoxyl, acetyl group.Particularly, formula (I
b) in R
1bBe the 3-pyridine radicals, halogenated pyridyl such as 6-chloro-3-pyridine radicals, 6-bromo-3-pyridine radicals or 5-bromo-3-pyridine radicals or halo thiazolyl such as 2-chloro-5-thiazolyl or 2-bromo-5-thiazolyl.
Guanidine derivatives or its salt of formula (I) can form cis-trans isomer, and this is because the position difference of X causes.Work as R in theory
2Be hydrogen or R
3Can also form dynamic isomer when being uncle or secondary amino group.The isomer of these guanidine derivatives or its salt (I) belongs to model of the present invention
Each symbol in the top reaction equation is identical with above-mentioned definition.
Formula (I), (I
a), and (I
b) salt that the example of salt is and inorganic acid forms of guanidine derivatives, these inorganic acids for example are hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid or perchloric acid; Or and the salt that forms of organic acid, these organic acids for example are formic acid, acetate, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, benzoic acid, picric acid or right-toluenesulfonic acid.
Guanidine derivatives (I) or its salt can be used as insecticide with any type of service that is suitable for for general agricultural chemicals.That is to say, according to its application target, it is dissolved or dispersed in the suitable liquid-carrier or with it is adsorbed in the suitable solid carrier, a kind of, two or more compound (I) or its salt can be used with dosage form, these preparations are as missible oil, finish, but warm nature pulvis, pulvis, granule, tablet, aerosol or ointment.If necessary, these preparations can contain emulsifier, suspending agent, and dispersant, bleeding agent, moistening temperature agent, thickener or stabilizing agent also can prepare with any known usual way.
The contained compound (I) or the ratio of its salt are generally 10-90% weight in missible oil or wetting powder form insecticide, when being finish or dry powder doses, be generally 0.1-10% weight, when being granule, be generally 1-20% weight, but according to application target, but above-mentioned concentration appropriate change.Missible oil, wetting powder etc. can use on-the-spot water etc. towards rare (for example 100 to 100000 times) and then spray.
The example of the liquid-carrier (solvent) that is suitable for is a water, and alcohols (as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol or ethylene glycol), ketone is (as acetone, MEK), ethers (such as diox, oxolane, glycol monoethyl ether, tirethylene glycol monomethyl ether or propylene glycol monomethyl ether), aliphatic hydrocarbon (as kerosene, fuel oil or machine oil), aromatic hydrocarbon is (as benzene, toluene, dimethylbenzene, solvent naphtha or methyl naphthalene), halogenated hydrocarbon is (as carrene, chloroform or carbon tetrachloride), amide-type (as dimethyl formamide or dimethylacetylamide), ester class (as ethyl acetate, butyl acetate or fatty glyceride) or nitrile (as acetonitrile or propionitrile).These solvents can use separately, also can mix its two or more and use.
The example of suitable solid carrier (thinner or pulvis carrier) comprises that the plant powder is (as soybean meal, tobacco powder, flour or wood chip), the mineral powder is (as clay as kaolin, bentonite or acid clay, talcum is as talcum powder or pyrophyllite in powder etc.), silica is (as diatomite or mica powder, alumina, sofril or active carbon).They can use separately or its two or more suitable mixing used.
The example that is fit to do at the bottom of the ointment base comprises polyethylene glycol, pectin, higher aliphatic acid polyol ester (as glyceryl monostearate), cellulose derivatives (as methylcellulose), mosanom, bentonite, higher alcohol, polyalcohol (as glycerine), vaseline, albolene, atoleine, lard, each vegetable oil, lanolin, anhydrous lanolin, fixed oil or resin.They can use separately, also can suitably mix its two or more or and the following surfactant use that is mixed.
As for as emulsifier, spreading agent, the surfactant that bleeding agent or dispersant adopted if necessary can adopt nonionic or anion surfactant, for example soap; Polyoxyethylene alkylaryl ether (Nonal_ that Noigen_ that for example Japanese Dai-ichi Kogyo Seiyaku K.K. produces and EA142_ and Japanese Toho Chemical produce); Alkyl sulfate (for example Emal_10 and Emal_40, Japanese Kao K.K. produces), alkylsulfonate (for example Neogen_ and Neogen T_, Dai-ichi KogyoSeiyaku K.K. and Neopellex
_, Kao K.K.); Polyglycol ether (Nonipol85 for example
_, Nonipol 100
_, Nonipol 160
_, Japanese Sanyo Kasei K.K. produces); Polyol ester (Tween20 for example
_, and Tween80
_, Kao K.K.).
When needs, guanidine derivatives (I) or its salt can cooperate or with the insecticide of form of mixtures and other (pyrethroid insectide for example, organophosphorus insecticide, carbamate pesticide or natural insecticide), miticide, nematocide, weed killer herbicide, plant hormone, plant growth regulator, bactericide (for example copper fungicide, organochlorine biocide agent, organosulfureous fungicide or phenol bactericide), synergist, attractant, repellent, colorant and/or fertilizer use together.
Guanidine derivatives (I) or their salt are effectively preventing and treating aspect health or gardening pest insect and the vegeto-animal parasite, and when directly contacting them with insect, can bring into play the effective insecticidal activity when for example they being applied to animals and plants alive.And the characteristic of having found this compound is, when the root by plant, after leaf or stem absorbed this compound in the plant corpus, plant was sucked by insect or when biting or contacting with insect, can show the effective insecticidal activity.This character is favourable for control suctorial type or maxilla type insect; And compound (I) and their salt are safe, have favorable properties as the preparation of preventing and treating pest, for example to the essentially no harm of plant and little to toxicity in fish.
Specifically, the preparation that contains guanidine derivatives (I) or its salt is effective especially for the following insect of control.They are Semiptera insects, and as the dish Chinese toon, rice is deceived Chinese toon, excellent honeybee coried, pear flower net Chinese toon, the rice small brown rice planthopper, brown plant-hopper, rice leafhopper, arrowhead scales, soybean aphid, sieve is foretold aphid, broccoli aphid, cotten aphid, lepidoptera pest, as prodenia litura, diamond-back moth, imported cabbageworm, striped rice borer, the Y Autographa spp, Helicoverpa assulta, oriental armyworm, cabbage army worm, the tea steinernema, Notarcha derogate, the vertical volume of rice snout moth's larva, potato tuberworm; Coleopteran pest such as mexican bean ladybird, aulacophora femoralis, phyllotreta striolata; Rice leaf beetles, rice plant weevil; Diptera pest such as housefly, Five continents Culex pipiens pallens, fly, delia platura are planted in Tabanas trigous green onion ground; Orthosptera order insect such as migratory locusts, African mole cricket; Dictyoptera insect such as Groton bug, smoke Perilpaneta americana; Section pest mite such as two-spotted spider mite, tangerine Panonychus citri, Tetranychus, Kanzawai, Zhu Sha tetranychid, golden melon mite, Aculops pelelassi, and nematode order insect such as aphelenchoides.
The Pesticidal combination that contains guanidine derivatives of the present invention (I) or its salt is the fabulous agricultural product of low toxicity and safety.It can be to be used with the similar method of common Pesticidal combination and relatively to have fabulous effect with common composition.For example, Pesticidal combination of the present invention can be used for the insect that will kill by handling in the case of seedbed, be applied to stem and the leaf of crop, and insect is sprayed, and is applied to the water in rice field or handles the soil in rice field.According to using season, place and method etc., amount of application can in very large range change.But generally speaking, active component (guanidine derivatives (I) or its salt) consumption is per hectare 0.3g-3000g, and 50g-1000g is better.When but Pesticidal combination of the present invention was the warm nature pulvis, the ultimate density of dilution back active component was 0.1-1000ppm, preferably 10-500ppm.
Guanidine derivatives (I
a) or its salt can be with the method for following (A)-(F) preparation.When compound (I
a) be when obtaining with free form or salt, available suitable method is translated into corresponding salt (the salt type of having addressed) or free type.Simultaneously, when being used as preparation compound (I
a) the raw material of other compound the time, compound (I
a) in any compound all can be free type or the salt type.Salt type compound (I
a) in addition other raw material also can use with any free type or salt type.Therefore, the product that obtains in the raw materials used and following method has comprised their salt separately.[salt of for example in compound (I), mentioning that forms with acid].
(A): in the present invention, guanidine derivatives (I) or its salt can pass through compound (II) or its salt and ammonia, and uncle or secondary amine or its salt react and prepares.
Used ammonia, primary amine or secondary amine or its salt are the represented amine of following formula or its salt:
R
3a-H (XI) is R wherein
3aDefinition is with above-mentioned identical.In reaction, preferably use Y to be C
1-4Alkylthio group (as methyl mercapto) or amino formula (II) compound.For compound (II) or its salt, the preferably about 0.8-2.0 equivalent of the quantity of compound used therefor (XI) or its salt, but, also can adopt about 2-20 equivalent as long as do not hinder reaction to carry out.
Though also can be without solvent, reaction generally is to carry out in appropriate solvent.The example of solvent is a water; Alcohols such as methyl alcohol, ethanol, normal propyl alcohol or isopropyl alcohol; Aromatic hydrocarbon such as benzene, toluene or dimethylbenzene; Halogenated hydrocarbons such as carrene or chloroform; Saturated hydrocarbon such as hexane, heptane or cyclohexane; Ethers such as ether, oxolane (is abbreviated as THF) Huo diox thereafter; Ketone such as acetone; Nitrile such as acetonitrile; Sulfoxide such as methyl-sulfoxide (being abbreviated as DMSO thereafter); Amide-type such as dimethyl formamide (hereinafter being abbreviated as DMF), ester class such as ethyl acetate or carboxylic acids such as acetate or propionic acid.These solvents can use separately, also can proper proportion as 1: 1-1: 10 use with two or more form of mixtures.When reactant mixture when being heterogeneous, reaction can be carried out under phase transfer catalyst such as quaternary ammonium salt (for example triethyl benzyl ammonia chloride, three-n-octyl ammonio methacrylate, trimethyl decyl ammonium chloride, 4 bromide) or crown ether exist.
But add alkali or slaine accelerated reaction, its quantity is the 0.01-10 equivalent, and the 0.1-3 equivalent is better.The example of alkali is inorganic base such as sodium bicarbonate, saleratus, sodium carbonate, potash, sodium hydroxide, potassium hydroxide, slaked lime, phenyl lithium, butyl lithium, sodium hydride, hydrofining, sodium methoxide, caustic alcohol, sodium metal or metallic potassium, also available organic base such as triethylamine, tri-n-butylamine, N, accelerine, pyridine, lutidines, but power pyridine, 4-(dimethylamino) pyridine or DBU (1,8-diazabicyclo [5,4,0] hendecene-7).Above-mentioned organic base itself also can be used as solvent and uses.The example of slaine is a mantoquita, as copper chloride, and copper bromide, Schweinfurt green or copper sulphate; Or mercury salt such as mercury chloride, mercuric nitrate or mercuric acetate.
Usually reaction temperature be-20-150 ℃, and 0-100 ℃ better, and the reaction time is 10 minutes to 50 hours, and 1-20 hour better.
(B) compound (I
a) or its salt useful raw materials (III) or its salt and compound (IV) or its salt react and prepare.
Preferably described in the same method of the example of Y and reaction condition (A).
(C) compound (I
a) or the also available compound of its salt (V) or its salt and compound (VI) react and prepare.
The leaving group of representing with Y in the compound (VI) is preferably halogen such as chlorine or bromine; C
1-4Alkylsulfonyloxy such as sulfonyloxy methyl oxygen base; C
6-10Aryl-sulfonyl oxygen such as right-tosyloxy or C
1-4Acyloxy, it can be replaced by 1-3 halogen, as acetoxyl group or trifluoroacetyl oxygen base.
Though as long as do not hinder reaction can use a large amount of excessive compounds (VI), it is better that its consumption is about the 0.8-1.5 equivalent with respect to compound (V).For accelerated reaction, can in the presence of alkali, react, the alkali described in the method (A) is suitable for.With respect to compound (V), the consumption of alkali is about 0.5 equivalent to excessive in a large number, and the 0.8-1.5 equivalent is better.When using organic base, it also can be as solvent.
As described in method A, reaction is preferably in the solvent to be carried out, if reaction is a heterogeneous system, carries out in the presence of the phase transfer catalyst that can mention in as method (A).Reaction temperature is generally-20-150 ℃, and 0-80 ℃ is better.Reaction time was generally 10 minutes to 50 hours, and 2-20 hour better.
(D) compound (I
a) or its salt can prepare by compound (VII) or its salt and compound (VIII) reaction.
In this reaction, preferably described in the same method of the example of Y and reaction condition (C).
(E) compound (I
a) and salt can prepare by compound (IX) or its salt and compound (X) reaction.
In this reaction, the example of Y is halogen such as bromine or chlorine preferably; Or C
1-4Acyloxy, it can be replaced by 1-3 halogen, for example acetoxyl group or trifluoroacetyl oxygen base.Reaction can be carried out under the similarity condition described in the method (C).
X wherein
aIt is the compound (I of nitro
a), i.e. the compound or its salt of representing with following formula
R wherein
1a, R
2aAnd R
3aDefinition as above can not only prepare with any method of above-mentioned (A)-(E), and available following method preparation.
(F) compound (I
a) or its salt can prepare by compound (IX) or the nitrated of its salt.
The nitric acid of 60-100% is often used as nitrating agent.Other nitrating agent such as alkali nitrates (for example sodium nitrate or potassium nitrate), alkyl nitrate (for example ethyl nitrate or amyl nitrate), nitronium tetrafluoroborate (NO
2BF
4) or trifluoromethane sulfonic acid nitre (NO
2CF
3SO
3) can be used.
For compound (IX) or its salt, when making nitrating agent, can use the nitrating agent of 1.0-20 equivalent with nitric acid, the 2.0-10 equivalent is better.
Reaction can be carried out under no any solvent condition, but normally at sulfuric acid, acetate, and acetic anhydride carries out in the such solvent of trifluoroacetic anhydride or trifluoromethane sulfonic acid.According to circumstances, but the solvent of mentioning in the using method (A) or its mixture.Reaction temperature is-50-100 ℃, and-20-60 ℃ is better.Reaction time is 10 minutes to 10 hours, and 30 minutes to 2 hours better.
Compound (the I that obtains thus
a) or the separated and purification of its salt energy.For example use usual way as concentrating, concentrating under reduced pressure distills, fractionation, and solvent extraction, basicity changes, reallocation, chromatogram, crystallization is recrystallized etc.
Be used as compound (II) and (III) or their salt of raw material in the method for the invention, part is known and can be according to for example J.Med.Chem.20,901 (1977), Chem.pharm.Bull.23,2744 (1975) and GB-A-2,201,596 described methods or similar method prepare.
Primary amine or secondary amine (XI) [using in said method (A)], compound (IV) or its salt can prepare with method described in for example " SHIN JIKENKAGAKU KOZA (New Experimental ChemistryHandbook) " (Japanese Maruzen Publishing Co.Ltd. publishes Vol.14 IIIpp.1332-1339) or similar approach.
Compound (V) and (IX) or its salt can be with the Chemistry ofCarbon Compounds Vol 1 that for example Rodd showed, Patc pp341-353 or Chemical Reviews, the method described in 51,301 (1952) or similarly method prepare.Compound (VII) or its salt can be with methods (A) for example, (B), (C), (E) and any one method (F) prepare (I is a) or in its salt because they are included in compound.
Compound (VI), (VII), and (X) can prepare with method described in " SHIN JIKENKAGAKU KOZA (NewExperimental Chemistry Handbook) " (Japanese Maruzen PublishingCo.Ltd. publishes, Vol14-Ipp307-450 and Vol.14-II pp 1104-1133) or similar approach.
Active
Can find out that from following test guanidine derivatives (I) and salt thereof have excellent insecticidal activity
Test example 1. (anti-brown plant-hopper effect)
Each test compound (compound that obtains among the following embodiment, No represents with sequence number) 5mg is dissolved in contains Tween20
_0.5ml acetone in, the Dyne (Ltd. produces for a kind of spreading agent, Japanese Takeda Chemical Industries) that adds 3000 times of dilute with waters then is diluted to predetermined concentration (500ppm).This solution is sprayed on the leaf of the rice seedling that is planted in the two leaf stage in the case with 10ml/ basin quantity and on the stem, treated water rice seedling is put in the moisture test tube in bottom, toward the brown plant-hopper larva of wherein putting 10 3 ages.After sealing with the aluminium plug, test tube is placed in the incubator that is adjusted to 25 ℃, calculates death toll after 7 days.Calculate lethality according to following formula and be listed in table 1.
The table 1 compound N o death rate (%) 1 100 2 100 3 100 4 100 5 100 6 100 7 100 8 100 9 10,010 10,011 10,012 10,013 10,014 10,015 10,016 10,017 10,018 10,019 10,020 10,021 10,022 10,023 10,024 10,025 10,026 10,027 10,028 10,029 10,030 10,031 10,032 10,033 10,034 100
Table 1 illustrates that clearly guanidine derivatives (I) or its salt pair brown plant-hopper have excellent pesticidal effect.
Test example 2 (anti-twill laphyqma effect)
Each test compound of 1mg (compound that following embodiment mentions, No represents with sequence number) is dissolved in contains Tween20
_0.5ml acetone in, and the Dyne that adds 3000 times of dilute with waters is diluted to predetermined concentration (500ppm).This solution is sprayed onto on the bean seedlings of single leaf expansion phase with every basin 20ml quantity.Behind the solution airing, cut two single leaves of seedling and put in the ice cream cup, toward the Spodoptera litura larvae of wherein putting 10 3 length of times, after putting into, cup is stored in the incubator that is adjusted to 25 ℃, count death toll down two days later, lethality is calculated by the formula described in the test example 1 and is listed in table 2.Table 2 compound N o lethality (%) 5 100 7 10,016 10,018 10,019 10,023 10,025 10,026 10,027 10,031 100
Table 2 shows that guanidine derivatives (I) or its salt pair prodenia litura have the excellent insecticidal effect.
Embodiment
By further sets forth in detail, they only as an example but do not limit the present invention with reference example and embodiment in the present invention.Improvement within the scope of the invention allows.
When with TLC (thin layer chromatography) monitoring, need carry out wash-out to the column chromatography among reference example and the embodiment.In the TLC monitoring, used TLC plate is the Kieselgel that Merck company makes
_60 F
254(70-230 order), solvent during with the column chromatography wash-out used solvent identical, with the calibrating of UV comparator.The silica gel that column chromatography is used is (the Kieselgel 60 (70-230 order) that West Germany makes of Merck company.The NMR spectrum is
1H-NHR, mark is measured in doing with tetramethylsilane, instrument is Varian EM90 (90MHz), all δ values all represent with ppm, when making solvent for mixed solvent in () represented numerical value be the volumetric mixture ratio of composition solvent.Abbreviation connotation used in embodiment and table 3 is as follows: Me: methyl Et: ethyl ph: phenyl S: unimodal br: wide
D: doublet
T: triplet
Q: quartet
M: multiplet
Dd: doublet of doublet
J: coupling constant
Hz: hertz
CDCl
3: deuterochloroform DMSO-d
6: deuterated dimethyl sulfoxide
%: percentage by weight
M.p.: fusing point.
Also have, room temperature refers to 15-20 ℃, and all fusing points and temperature all are degree centigrade.Reference example 1.
With 70.3g 2-chloro-5-(methylol) pyridine and 50ml 1, the mixture of 2-dichloroethane was added drop-wise to 87.4g thionyl chloride and the 100ml 1 in 5-20 ℃ water-bath in 30 minutes, in the 2-dichloroethane mixture.In room temperature mixture was stirred 1.5 hours, refluxed again 4.5 hours.After concentrating, add 200ml chloroform and 60ml water in residue, gradation under agitation adds the 20g sodium bicarbonate then.Telling organic layer, also concentrate with charcoal treatment and obtain 75.9g2-chloro-5-(chloromethyl) pyridine, is the yellowish-brown solid.
1H?NMR(CDCl
3)：4．57(2H，s)7．34(1H，d，J=8．5Hz)
7．72(1H，dd，J=8．5，2．5Hz)
8．40(1H，d，J=2．5Hz)
Use same quadrat method, can obtain 5-(chloromethyl) thiazole, 5-chloromethyl-2-methylthiazol and 5-chloromethyl-2-phenyl thiazole.Reference example 2
In oil bath in 80 ℃ with 14.99g 2-chloro-5-(chloromethyl) pyridine, the ammoniacal liquor of 63.01g25%, stirred two hours in the stainless steel autoclave with the mixture of 60ml acetonitrile, after adding 12.3g 30% sodium hydrate aqueous solution reactant mixture is concentrated, in residue, add 200ml ethanol, use anhydrous magnesium sulfate drying again, the elimination insoluble matter, filtrate concentrated and with column chromatography purify [solvent: methylene chloride-methanol (4: 1)], obtain 7.66g 5-(aminomethyl)-2-chloropyridine, yellow solid.
1HNMR(CDCl
3)：1．60(2H，s)3．90(2H，s)
7．28(1H，d，J=8．5Hz)
7．67(1H，dd，J=8．5，2．5Hz)
8．33(1H，d，J=2．5Hz)
Use same quadrat method, can make 5-(aminomethyl)-2-bromopyridine, 5-(aminomethyl)-2-diuril azoles, 3-cyano group-benzylamine, 5-(aminomethyl) thiazole, 5-(aminomethyl)-2-methyl-thiazole, 5-(aminomethyl)-2-phenyl thiazole and 5-(aminomethyl-2-(trifluoromethyl) thiazole.Reference example 3
In 1 hour, the mixture of 15.05g 2-chloro-5-(chloromethyl) pyridine and 50ml acetonitrile is added drop-wise in the mixture of 36g 40% methylamine water solution and 200ml acetonitrile and stirred 1.5 hours in room temperature.Reactant mixture is concentrated, in the gained residue, add 100ml water, neutralize with sodium bicarbonate then, saturated and extract (200ml * 2) with sodium chloride again with carrene, with the organic layer anhydrous magnesium sulfate drying, concentrating and purify by [solvent: methylene chloride-methanol (4: 1)] with column chromatography, obtain 8.77g 2-chloro-5-(methylamino methyl) pyridine, is yellowish-brown liquid.
1HNMR (CDCl
3): 1.30 (1H, br.s), 2.44 (3H, s), 3.75 (2H, s), 7.30 (1H, d, J=8.4Hz) 7.68 (1H, dd, J=8.4,2.4Hz) 8.35 (J=2.4Hz) reference example 4 for 1H, d
In 20 ℃ of water-baths, in 30 minutes, the 6.30g trifluoroacetic anhydride is added drop-wise to 3.15gS, in the solution of S '-Methyl disulfide for imido-carbonic acid ester hydrochloride and 30ml pyridine, stirred subsequently 5 hours.Reactant mixture is concentrated, in residue, add 20ml water, extract (30ml), organic layer is also concentrated with anhydrous magnesium sulfate drying with carrene.Residue is with the column chromatography (solvent: carrene) obtain 2.33gS, S '-dimethyl N-TFA base two sulfo-imido-carbonic esters, yellow liquid of purifying.
1HNMR (CDCl
3) 2.66 (s) reference example 5
In 30 minutes the 0.89g 5-aminomethyl-drips of solution of 2-chloropyridine in the 5ml isopropyl alcohol is added to 1.0gS down in refluxing, S ＇-dimethyl N-cyano group two sulfo-iminocarbonic esters are in the mixture of 15ml isopropyl alcohol.Mixture was refluxed 1.5 hours again, use ice-cooled then.Filter to collect the white solid that obtains, obtain 1.35g 1-(6-chloro-3-picolyl)-3-cyano group-2-methyl-isourea.
1HNMR(CDCl
3)：2．63(3H，s)，4．51(2H，d，J=6Hz)
7．51(1H，d，J=8Hz)
7．83(1H，dd，J=8．3Hz)
8．38(1H，d，J=3Hz)，8．95(1H，br．s)
Use same quadrat method; can obtain 1-(6-chloro-3-picolyl)-2-methyl-3-trifluoroacetyl group isothiourea; 1-(6-chloro-3-picolyl)-1,2-dimethyl-3-trifluoroacetyl group isothiourea and 1-(2-chloro-5-thiazolyl methyl)-3-cyano group-2-methyl isothiourea.Reference example 6
60% sodium hydride (in mineral oil) (0.80g) is suspended in the 20ml dimethyl formamide (DMF) after washing with benzinum.In 10 minutes, in this suspension, drip 2.58g 3-cyano group-1, the 10ml DMF solution of 2-dimethyl-isothiourea in room temperature.Stir after 1 hour, in 5 minutes, 3.24g 2-chloro-5-(5-chloromethyl) pyridine is added in this reactant mixture, subsequently in stirring at room 15 hours.Decompression steams DMF, in residue, add the 100ml carrene, wash with water again, the organic layer anhydrous magnesium sulfate drying, concentrate and with column chromatography purify [solvent: chloroform-ethanol (20: 1)] obtain 3.50g 1-(6-chloro-3-pyridylmethyl)-3-cyano group-1,2-dimethyl isothiourea is a yellow liquid.
1HNMR(CDCl
3)：2．84(3H，s)，3．20(3H，s)，4．82(2H，s)
7．35(1H，d，J=8Hz)
7．63(1H，dd，J=8．2Hz)
8．31(1H，d，J=2Hz)
Use same quadrat method, can obtain 1-(6-chloro-3-pyridylmethyl)-3-cyano group-1-ethyl-2-methyl isothiourea, 1-(6-chloro-3-pyridylmethyl)-1,2-dimethyl-3-nitro isothiourea, 1-(6-chloro-3-pyridylmethyl)-1-ethyl-2-methyl-3-nitro isothiourea, 1-(2-chloro-5-thiazolyl methyl)-1-ethyl-2-methyl-3-nitro isothiourea and 1-(2-chloro-5-thiazolyl methyl)-1,2-dimethyl-3-nitro isothiourea.Reference example 7
With 4.07g 2-chloro-5-aminopyridine, the mixture of 2.55g methyl-isorhodanate and 30ml acetonitrile refluxed 13.5 hours, toward wherein adding the 0.70g methyl-isorhodanate again, mixture was refluxed 13.5 hours again.Reactant mixture is concentrated, residue is obtained 4.51g 1-(6-chloro-3-pyridine radicals)-3-methylthiourea with column chromatography purification [solvent: carrene-acetate acetate (1: 1)].
Mp.164-164.5 ℃ (from acetonitrile, being recrystallized)
1HNMR(CDCl
3)：3．12(3H，d，J=4．8Hz)，
6．86(1H，br．q，J=4．8Hz)
7．33(1H，d，J=8．5Hz)
7．86(1H，dd，J=8．5，2．8Hz)
8.31 (1H, d, J=2.8Hz), 8.63 (1H.br.s) reference example 8
With 4.45g 2-bromo-5-methylthiazol, the 4.89g N-bromosuccinimide, the mixture of 0.2g benzoyl peroxide and 50ml carbon tetrachloride refluxed 50 minutes, was chilled to room temperature then.Remove by filter insoluble matter, concentrated filtrate.Obtaining 4.53g 2-bromo-5-(bromomethyl) thiazole with the column chromatography residue [solvent: hexane-carrene (2: 3)] of purifying, is yellow solid.
1HNMR(CDCl
3)：4．64(2H，s)，7．54(1H，s)
In kind, can make 5-(bromomethyl)-3-(difluoromethyl) thiazole-2-ketone.Reference example 9
In following 20 minutes of room temperature, in the mixture of 1.85g potassium phthalimide and the dry DMF of 20ml, add 2.57g 2-bromo-5-(bromomethyl) thiazole in batches, stirred subsequently 1 hour.Remove by filter insoluble matter, concentrated filtrate.In residue, add 30ml ethanol, in 20 ℃ of oil baths in 2 minutes toward wherein dripping the 0.60g hydrazine hydrate.With reaction mixture refluxed 1 hour and concentrated.After adding 20ml water and 10ml concentrated hydrobromic acid mixture is continued to reflux 30 minutes.After cold, with 20% sodium hydrate aqueous solution neutralization reaction mixture and concentrated.In residue, add the 50ml acetonitrile, remove by filter insoluble matter, concentrated filtrate.Residue is purified by [solvent: methylene chloride-methanol (5: 1)] with column chromatography, obtains 0.76g5-(aminomethyl)-2-bromo thiazole, is brown oil.
1HNMR(CDCl
3-DMSO-d
6)：2．65(2H，br．s)，4．01(2H，s)，
7.40 (1H, s) reference example 10
In the mixture of 1.35g S-methyl-N-nitro isothiourea and 5ml acetonitrile, add the 0.88g diethylamine, in 60 ℃ of oil baths, stirred 6 hours subsequently.Concentrated reaction mixture, residue is purified by [solvent: methylene chloride-methanol (20: 1)] with column chromatography, obtains 0.85gN, and N-diethyl-N ＇-nitroguanidine is white solid.
mp．96-97℃
1HNMR(CDCl
3)：1．23(6H，t，J=7．2Hz)，
3.47 (J=7.2Hz), 7.93 (2H, br.s) reference example 11 for 4H, q
In 2 minutes, in the mixture of 1.0g S-methyl-N-nitro isothiourea and 15ml acetonitrile, drip the 0.61g pyrrolidines, stirred subsequently 30 minutes.Reactant mixture being concentrated, with ether washing gained precipitation, obtain 1.09g 1-(N-nitro-guanyl) pyrrolidines, is white crystals.
mp．188-191℃
1HNMR(DMSO-d
6)：1．7-2．1(4H，m)，3．2-3．5(4H，m)，
8.19 (2H, br.s) reference example 12
In following 10 minutes of room temperature, in the mixture of 5.0g S-methyl-N-nitro isothiourea and 25ml pyridine, drip the 11.3g acetic anhydride, under same temperature, continue to stir 5 hours.Concentrated reaction mixture is also inclined to residue in the 50ml 2N hydrochloric acid.Filter and collect the gained solid, drying obtains 5.1g N-acetyl group-5-methyl-N-nitro isothiourea.m．p．109-110℃
1H?NMR(CDCl
3)：2．30(3H，s)，2．42(3H，s)，
11.20-12.00 (1H, br) reference example 13
In 80 ℃ of oil bath last 1 hours,, blast dichlorodifluoromethane gas in the mixture of 100ml diox and 100g 40% sodium hydrate aqueous solution to 11.5g 2-hydroxy-5-methyl base thiazole (5-methyl-thiazole-2-ketone).Reactant mixture is poured in the 500ml water and with twice of extracted by ether.Combined ether layer is with anhydrous magnesium sulfate drying and concentrated.Residue separates [solvent: carrene-hexane (1: 1)] through column chromatography, obtain 2.0g2-(difluoro-methoxy)-5-methylthiazol [
1HNMR (CDCl
3): 2.35 (3H, d, J=1.5Hz), 6.88 (1H, br.q, J=1.5Hz), 7.18 (1H, t, J=72.OHz)] and 4.0g 3-(difluoromethyl)-5-methylthiazol-2-ketone [
1HNMR (CDCl
3): 2.16 (J=1.5Hz), 6.51 (J=1.5Hz), 7.07 (1H, t J=60.OHz), are light yellow liquid for 1H, br.q for 3H, d.Reference example 14
Stir 11.22g 2,2 under 70 ℃ of oil baths, the mixture of 2-trifluoro thioacetamide and 10.14g2-chloro-2-formoxyl ethyl acetate 30 minutes then, stirred 1.5 hours down in 100 ℃ of oil baths, to wherein adding the 100ml carrene.Filter after the insoluble matter, concentrate.Residue is purified by [solvent: hexane-ethyl acetate (10: 1)] through column chromatography, obtains 3.74g 2-(trifluoromethyl) thiazole-5-carboxylic acid ethyl ester, is yellow liquid.
1HNMR(CDCl
3)：1．41(3H，t，J=7．2Hz)，
4．43(2H，q，J=7．2Hz)，8．50(1H，s)
In following 45 minutes of room temperature, the drips of solution of above-mentioned product of 2.51g and 10ml dry THF is added in the solution of 0.50g lithium aluminium hydride and 80ml dry THF, then stirred 30 minutes.Behind freezing this reactant mixture, add 0.5ml water successively, 0.5ml 10% sodium hydrate aqueous solution and 1.5ml water.Then, under ice bath, stirred this mixture 10 minutes, at room temperature stirred 30 minutes.Fall insoluble matter through diatomite filtration.Concentrated filtrate adds the 100ml chloroform in residue, anhydrous magnesium sulfate drying concentrates, and obtains 1.24g 5-(methylol)-2-(trifluoromethyl) thiazole, is brown liquid.
1HNMR(CDCl
3)：3．45(1H，br．s)，4．93(2H，s)，7．7(1H，s)。
In 40 ℃ in following 10 minutes with above-mentioned product of 0.80g and 20ml 1, the drips of solution of 2-dichloroethane is added to 0.4ml thionyl chloride and 1ml 1, in the mixture of 2-dichloroethane, then, stirs 1 hour under same temperature.In reactant mixture, add 2ml carrene and 2ml water, under agitation add sodium bicarbonate and be adjusted to pH7 (in water layer).Tell organic layer and extract water layer with carrene.Merge organic layer and filter insoluble matter.With saturated common salt washing gained organic layer, anhydrous magnesium sulfate drying concentrates, and obtains 0.74g 5-(chloromethyl)-2-(trifluoromethyl) thiazole, is rufous liquid.
1HNMR(CDCl
3)：4．84(2H，s)，7．90(1H，s)。
Use same quadrat method, can obtain N-ethyl-N-methyl-N '-nitro-guanidine, mp124-125 ℃
Embodiment 1
Divide 6 times (3.0g), restrained the methylamine water solution that adds 0.5g 40% in the mixture of 1-(6-chloro-3-pyridylmethyl)-3-cyano group-1-ethyl-2-methyl isothiourea and 5ml acetonitrile toward 0.42, reflux simultaneously and stir every 1 hour.Reactant mixture stirred 6 hours altogether, then mixture was concentrated, and obtained 0.32g 1-(6-chloro-3-pyridylmethyl)-2-cyano group-1-ethyl-3-methylguanidine (compound the 3rd).
mp?122-123℃
1HNMR(DMSO-d
6)：1．07(3H，t，J=7Hz)
3．00(3H，d，J=5Hz)
3．35(2H，q，J=7Hz)，4．62(2H，s)，
7．23(1H，br．s)，7．50(1H，d，J=8Hz)，
8．33(1H，d，J=3Hz)
Embodiment 2
In in 20 minutes, in the suspension of 10ml DMF, adding 1.32g N, N-dimethyl-N '-nitroguanidine under the room temperature toward 0.44g 60% sodium hydride (in mineral oil).Stir after 10 minutes, added 1.62g 2-chloro-5-(chloromethyl) pyridine in this mixture in 5 minutes, and stirred 2 hours under room temperature, heating is 4 hours in 60 ℃ of oil baths.Behind the elimination insoluble matter, concentrated filtrate.With column chromatography purification gained residue [solvent: carrene-ethyl acetate (5: 1-3: 1)], 0.82g 1-(6-chloro-3-picolyl)-3,3-dimethyl-2-nitroguanidine (compound the 6th)
mp?160．5-162．5℃
Elementary analysis (C
9H
12N
5O
2Cl)
Calculated value: C:41.95, H:4.69, N:27.18
Measured value: C:41.73, H:4.59, N:26.94
1HNMR (CDCl
3): 3.10 (6H, s), 4.49 (2H, br.s)
7．27(1H，d，J=8．5Hz)，
7．70(1H，dd，J=8．5，2．5Hz)，
8．2-8．5(2H，m)
Embodiment 3
With 0.45g 1,2-dimethyl-3-nitro isothiourea, the mixture of 0.43g 5-(aminomethyl)-2-chloropyridine and 25ml ethanol refluxed 6 hours and concentrated.Residue is purified by [solvent: chloroform-ethanol (5: 1)] with column chromatography, obtains 0.25g 1-(6-chloro-3-pyridylmethyl)-3-methyl-2-nitroguanidine (compound the 5th).
mp?150-152℃
Elementary analysis (C
8H
10N
5O
2Cl)
Calculated value: C:39.44, H:4.14, N:28.74
Measured value: C:39.92, H:4.12, N:28.91
1HNMR(CDCl
3-DMSO-d
6)：
2．94(3H，d，J=5Hz)，4．51(2H，d，J=5Hz)，
7．32(1H，d，J=8Hz)，7．75(1H，dd，J=8．2Hz)，
7．82(1H，br．s)，8．37(1H，d，J=2Hz)，
8．90(1H，br．s)
Embodiment 4
With 0.676g S-methyl-N-nitro isothiourea, the mixture of 0.783g 2-chloro-5-(methylamino methyl) pyridine and 6ml acetonitrile refluxed 7 hours and concentrated.The residue ethyl alcohol recrystallization obtains 0.38g 1-(6-chloro-3-pyridylmethyl)-1-methyl-2-nitroguanidine (compound the 7th)
mp?167-170℃
Elementary analysis (C
8H
10N
5O
2Cl)
Calculated value: C:39.44, H:4.14, N:28.74
Measured value: C:39.89, H:4.07, N:28.85
1HNMR(DMSO-d
6)：
3．01(3H，s)，4．70(2H，s)，
7．48(1H，d，J=8．4Hz)，
7．78(1H，dd，J=8．4，2．2Hz)，
8．37(1H，d，J=2．2Hz)，8．56(2H，br．s)
Embodiment 5
With 0.82g 1-(6-chloro-3-pyridylmethyl)-1,2-dimethyl-3-nitro isothiourea, the mixture of 0.464g 40% methylamine water solution and 10ml acetonitrile stirred 2 hours and concentrated under 70 ℃.Residue is purified by [solvent: methylene chloride-methanol (10: 1)] with column chromatography, obtain 0.56g 1-(6-chloro-3-pyridylmethyl)-1,3-dimethyl-2-nitroguanidine (compound N o8).
mp?136-137℃
Elementary analysis (C
9H
12N
5O
2Cl)
Calculated value: C:41.95, H:4.69, N:27.18
Measured value: C:41.89, H:4.75, N:27.15
1HNMR(CDCl
3)：29．6(3H，d，J=4．8Hz)，3．05(3H，s)，
4．67(2H，s)，7．33(1H，d，J=8．3Hz)，
7．68(1H，dd，J=8．3，2．4Hz)，
7．96(1H，br．q，J=4．8Hz)，
8．30(1H，d，J=2．4Hz)
Embodiment 6
With the 0.53g nitroguanidine, the mixture of 0.61g 3-(aminomethyl) pyridine and 10ml water stirred 1.5 hours under 70-80 ℃, and under room temperature standing over night.Filter the sediment of collecting with washing with alcohol, obtain 0.48g N-nitro-N '-(3-pyridylmethyl) guanidine, (compound the 12nd).
mp?185-190℃
1HNMR(DMSO-d
6)：4．47(2H，d，J=5Hz)
7．40(1H，dd，J=6．4Hz)，
7．67-7．85(1H，m)，
7．85-8．30(2H，br．s)，
8．47-8．67(2H，m)
Embodiment 7
In under the room temperature 0.045g 60% sodium hydride (in mineral oil) being added to 0.24g 1-(6-chloro-3-pyridylmethyl)-3, in the mixture of 3-dimethyl-2-nitroguanidine (compound the 7th) and 6ml dry tetrahydrofuran (THF), stirred subsequently 30 minutes.Join the solution of 0.16g iodomethane in 1ml THF in this reactant mixture and reacted 3 days.After adding 0.1ml acetate, filtering mixt is removed insoluble matter, concentrated filtrate.Residue is purified by [solvent: methylene chloride-methanol (20: 1)] with column chromatography, obtains 0.17g 1-(6-chloro-3-pyridylmethyl)-1,3, and 3-trimethyl-2-nitroguanidine (compound the 14th) is a white solid.
mp99-101℃
1HNMR(CDCl
3)：2．90(3H，s)，3．02(6H，s)，
4．03(2H，s)，7．38(1H，d，J=8．5Hz)，
7．79(1H，dd，J=8．5，2．7Hz)，
8．37(1H，d，J=2．7Hz)
Embodiment 8
In 20 ℃ of water-baths,, add 0.08g60% sodium hydride (in mineral oil) in the mixture of 3-dimethyl-2-nitroguanidine (compound the 6th) and 3ml dry THF, stirred subsequently 30 minutes toward 0.26g 1-(6-chloro-3-picolyl)-3.In 1 minute, the solution of 0.26g acetic formic anhydride in 0.5ml THF is added in this reactant mixture; the back is removed in water-bath stirred 12 hours; after adding 0.5ml acetate reactant mixture is concentrated; residue is with column chromatography purify [solvent: methylene chloride-methanol (30: 1)]; obtain 0.10g 1-(6-chloro-3-picolyl)-1-formoxyl-3,3-dimethyl-2-nitroguanidine (compound the 22nd).It is slurry.
1HNMR(CDCl
3)：3．03(6H，s)，4．70(2H，s)，
7．36(1H，d，J=8．7Hz)，
7．74(1H，dd，J=8．7，2．7Hz)，
8．40(1H，d，J=2．7Hz)，8．44(1H，s)
Embodiment 9
In 60 ℃ with 0.20g 1-(6-chloro-3-picolyl)-3,3-dimethyl-2-nitroguanidine (compound N o6), the mixture of 0.095g acetic anhydride and 1ml dry pyridine stirred 2 hours, stirred 5 hours in 100 ℃ again, concentrated then.Residue is purified by [solvent: methylene chloride-methanol (40: 1)] with column chromatography, obtains 0.12g 1-acetyl group-1-(6-chloro-3-pyridylmethyl)-3,3-dimethyl-2-nitroguanidine (compound the 23rd).Be slurry (genial anti--mixture of isomers).
1HNMR(CDCl
3)：2．10+2．16(3H，S+S)，2．6-3．3(6H，m)，
4．1-5．2(2H，m)，7．23-7．45(1H，m)，
7．67-7．90(1H，m)，8．30-8．50(1H，m)
Embodiment 10
With 1.03g 1-(6-chloro-3-pyridine radicals)-3-methylthiourea, 0.32g cyanamide, 1.58g dicyclohexyl carbodiimide, the mixture of 3 ethyl diisopropyl amines and 10ml acetonitrile stirred 34 hours and filtered collects insoluble matter in room temperature.Insoluble matter with the acetonitrile recrystallization, obtains 0.31g 1-(6-chloro-3-pyridine radicals)-2-cyano group-3-methylguanidine (compound the 24th) again with the mixed solvent recrystallization of acetonitrile and methyl alcohol
mp?227-228℃
Elementary analysis (C
8H
8N
5Cl)
Calculated value: C45.84, H3.85, N33.41
C46．12，H3．68，N33．37
1HNMR(DMSO-d
6)：2．85(3H，d，4．8Hz)，7．2-7．65(2H，m)，
7．83(1H，dd，J=8．5，3．0Hz)，
8．36(1H，d，J=3．0Hz)，9．06(1H，br．s)
Embodiment 11
With 0.39g 5-(aminomethyl)-2-bromo thiazole, 0.38g 1 in 60 ℃ of oil baths, 2-dimethyl-3-nitro isothiourea, and the 0.58g cuprous bromide, the mixture of the dry acetonitrile of 0.55g Anhydrous potassium carbonate and 4ml stirred 45 minutes.Reactant mixture is purified by [solvent: methylene chloride-methanol (10: 1)] with column chromatography, obtain 1-(2-bromo-5-thiazolyl methyl)-3-methyl-2-nitroguanidine (compound the 39th), be white solid.
mp?170℃
1HNMR(DMSO-d
6)：2．81(3H，d，J=5．0Hz)，
4．51(2H，s)，7．60(1H，s)，
8.08 (1H, br.s), 8.93 (1H, br.s) embodiment 12
Under the ice bath cooling, in the mixture of 0.5g N-acetyl group-S-methyl-N '-nitro isothiourea and 5ml acetonitrile, drip the solution of 0.44g 5-(amino methyl)-2-chloropyridine and 3ml acetonitrile, then, under the ice bath cooling, stirred 30 minutes.Concentrated reaction mixture, residue is recrystallized from ethanol, obtains that 0.59g N-acetyl group-N '-" nitroguanidine (compound the 42nd) is white crystals to (6-chloro-3-pyridylmethyl)-N.
mp?125-126℃
1HNMR(CDCl
3)：2．33(3H，s)，4．60(2H，d，J=6．0Hz)，
7．33(1H，d，J=7．8Hz)，7．50-7．87(1H，m)，
8．37(1H，d，J=2．5Hz)，9．70(1H，br．s)，
11．85(1H，br．s)。
Listed compound is pressed the foregoing description 1-12 and preparation method of the present invention preparation in the table 3.In addition, the compound of the foregoing description is also included within the table 3.
Table 3
A)
1HNMR (CDCl
3): 2.87 (6H, s), 4.59 (4H, s), 7.37 (2H, d, J=8Hz), 7.72 (2H, dd, J=8,2Hz), 8.37 (2H, d, J=2Hz) .b)
1HNMR (CDCl
3): 3.00 (3H, d, J=4Hz), 4,53 (2H, d, J=6Hz), 6.76 (1H, br.s), 7.46 (1H, dd, J=8Hz), 7.67 (1H, dd, J=8,3Hz), 8.20 (1H, d, J=3Hz), 8.83 (1H, br.s) .c)
1HNMR (CDCl
3): d)
1HNMR (CDCl
3):
Embodiment 8
Embodiment 9e)
1HNMR (CDCl
3): 1.26 (3H, t, J=7Hz), 2.98 (3H, d, J=2Hz), 3.47 (2H, q, J=7Hz), 4.70 (2H, s), 7.50 (1H, s), 7.96 (1H, br.s) .f)
1HNMR (CDCl
3): 3.00 (3H, d, J=4Hz), 3.09 (3H, s), 4.69 (2H, s), 7.50 (1H, s), 8.00 (1H, br.s) .g)
1HNMR (CDCl
3): 1.23 (6H, t, J=7Hz), 3.46 (4H, q, J=7.2Hz), 4.60 (2H, br.s), 7.44 (1H, s), 8.30 (1H, br.s) .h)
1HNMR (CDCl
3): 3.11 (6H, s), 4.42 (2H, d, J=6.0Hz), 6.86 (1H, s), 7.07 (1H, t, J=60.0Hz), 7.78 (1H, br.t, J=6.0Hz). embodiment 13
A kind of missible oil is by fully mixing 20wt% compound the 1st, and (Nonipol 85 for 75wt% dimethylbenzene and 5wt% polyoxyethylene glycol ether
_) prepare.
Embodiment 14
Wetting powder passes through fully to mix 30wt% compound the 6th, the 5wt% sodium lignosulfonate, and (Noniol 85 for 5wt% polyoxyethylene glycol ether
_, 30wt% hard charcoal and 30wt% clay prepare.
Embodiment 15
Pulvis is by fully mixing 3wt% compound the 7th, and 3wt% hard charcoal and 94wt% clay prepare.
Embodiment 16
Granule is by fully pulverizing and mix 10wt% compound the 8th, and 5wt% sodium lignosulfonate and 85wt% clay, and water mediates this mixture are made into particle again and drying prepares.
Claims (8)
1. Pesticidal combination, said composition contain the guanidine derivatives of formula (I) of 0.1-90% (weight) and carrier or the thinner of 10-99.9 (weight),
R in the formula
1Be that (1) can be selected from the phenyl that the substituting group of halogen and cyano group replaces, the pyridine radicals that (2) can be replaced by halogen, (3) can be selected from (ⅰ) halogen, (ⅱ) C that can be replaced by halogen
1-4Alkyl, (ⅲ) phenyl and (ⅳ) thiazolyl or (4) pyrazinyl of the substituting group replacement of oxo;
R
2Be hydrogen, methyl, ethyl, formoxyl or acetyl group;
R
3Be amino, single-or two-C
1-4Alkyl amino, C
1-4Acylamino-or pyrrolidinyl; With
X is a nitro, trifluoroacetyl group or cyano group,
Condition is when X is cyano group, R
1Be halogenated pyridyl or halo thiazolyl.
2. the Pesticidal combination of claim 1, the R in its formula of (I)
1Be pyridine radicals, halogenated pyridyl or halo thiazolyl.
3. the Pesticidal combination of claim 1, the R3 in its formula of (I) are single-or two-methylaminos.
4. the Pesticidal combination of claim 1, the X in its formula of (I) is a nitro.
5. the Pesticidal combination of claim 1, wherein guanidine derivatives is 1-(6-chloro-3-pyridylmethyl)-3-methyl-2-nitroguanidine.
6. the Pesticidal combination of claim 1, wherein guanidine derivatives is 1-(3-pyridylmethyl)-3-methyl-2-nitroguanidine.
7. the Pesticidal combination of claim 1, wherein guanidine derivatives is 1-(2-chloro-5-thiazolyl methyl)-3-methyl-2-nitroguanidine,
8. the Pesticidal combination of claim 1, wherein guanidine derivatives is 1-(2-chloro-5-thiazolyl methyl)-3,3-dimethyl-2-nitroguanidine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93101375A CN1060615C (en) | 1988-12-27 | 1993-02-10 | Guanidine derivatives, their production and insecticides |
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP332192/1988 | 1988-12-27 | ||
| JP33219288 | 1988-12-27 | ||
| JP332192/88 | 1988-12-27 | ||
| JP2358989 | 1989-01-31 | ||
| JP23589/89 | 1989-01-31 | ||
| JP23589/1989 | 1989-01-31 | ||
| JP18778989 | 1989-07-19 | ||
| JP187789/1989 | 1989-07-19 | ||
| JP187789/89 | 1989-07-19 | ||
| CN89109577A CN1026981C (en) | 1988-12-27 | 1989-12-26 | Guanidine derivative, their production and insecticides |
| CN93101375A CN1060615C (en) | 1988-12-27 | 1993-02-10 | Guanidine derivatives, their production and insecticides |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89109577A Division CN1026981C (en) | 1988-12-27 | 1989-12-26 | Guanidine derivative, their production and insecticides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1077843A CN1077843A (en) | 1993-11-03 |
| CN1060615C true CN1060615C (en) | 2001-01-17 |
Family
ID=27509643
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93101375A Expired - Lifetime CN1060615C (en) | 1988-12-27 | 1993-02-10 | Guanidine derivatives, their production and insecticides |
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|---|---|
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| CN103621552B (en) * | 2012-08-29 | 2016-01-20 | 南京华洲药业有限公司 | Compound pesticide compositions of a kind of clothianidin-containing and Profenofos and uses thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0306696A1 (en) * | 1987-08-04 | 1989-03-15 | Ciba-Geigy Ag | Substituted guanidines |
| EP0364844A1 (en) * | 1988-10-21 | 1990-04-25 | Nihon Bayer Agrochem K.K. | Insecticidally active cyano compounds |
| EP0375907A1 (en) * | 1988-11-29 | 1990-07-04 | Nihon Bayer Agrochem K.K. | Insecticidally active nitro compounds |
-
1993
- 1993-02-10 CN CN93101375A patent/CN1060615C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0306696A1 (en) * | 1987-08-04 | 1989-03-15 | Ciba-Geigy Ag | Substituted guanidines |
| EP0364844A1 (en) * | 1988-10-21 | 1990-04-25 | Nihon Bayer Agrochem K.K. | Insecticidally active cyano compounds |
| EP0375907A1 (en) * | 1988-11-29 | 1990-07-04 | Nihon Bayer Agrochem K.K. | Insecticidally active nitro compounds |
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|---|---|
| CN1077843A (en) | 1993-11-03 |
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