CN1088913A - Nitroethylene two amines of using as sterilant - Google Patents

Nitroethylene two amines of using as sterilant Download PDF

Info

Publication number
CN1088913A
CN1088913A CN 93120592 CN93120592A CN1088913A CN 1088913 A CN1088913 A CN 1088913A CN 93120592 CN93120592 CN 93120592 CN 93120592 A CN93120592 A CN 93120592A CN 1088913 A CN1088913 A CN 1088913A
Authority
CN
China
Prior art keywords
compound
alkyl
group
heterocycle
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 93120592
Other languages
Chinese (zh)
Inventor
S·F·麦肯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of CN1088913A publication Critical patent/CN1088913A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Have the active compound of Arthropodicidal, composition and their using method, this compounds has above general formula.
Wherein Q, Y and R 2-R 4Definition as described in the specification sheets.

Description

Nitroethylene two amines of using as sterilant
The present invention includes nitroethylene two amines of using as sterilant.The characteristics of The compounds of this invention are that the methylene radical of its nitroethylene part replaces, and this compound is different with the compound of following patent of invention: EP437,784, U.S.4,845,106, GB1,483,633 and WO91/17659.
The present invention relates to formula I compound, comprise all how much with the spatial isomer, with and agricultural go up the salt that is suitable for, contain their agricultural composition, and the purposes of their pest controls in agronomy and non-agronomy environment.This compounds is:
Figure 931205921_IMG4
Wherein
Q represents one of following groups
Figure 931205921_IMG5
Y is selected from halogen and R 1X;
X is selected from S(O) a, O and NR 5;
R 1Be selected from C 1-C 20Alkyl, C 3-C 10Cycloalkyl, C 4-C 7Cycloalkylalkyl, C 2-C 6Alkenyl, C 2-C 6Alkynyl, above-mentioned each group can at random be replaced by 1 or 2 group that is independently selected from following groups: CN, NO 2, OH, C 1-C 4Alkoxyl group, OC(O) R 6, OCO 2R 6, OS(O) 2R 6, SH, C 1-C 4Alkylthio, C(O) R 6, C(O) OR 6, CO 2H, SO 3H, N(R 7) R 8, C(O) N(R 7) R 8, OS(O) 2N(R 7) R 8, C(S) N(R 7) R 8, C 1-C 4Alkylamino, C 2-C 6Dialkyl amido, S(O) 2N(R 7) R 8, Si(R 9) (R 10) R 11, C 1-C 4Alkyl sulfinyl, C 1-C 4Alkyl sulphonyl, by R 12Any phenyl that replaces, and one five yuan or hexavalent saturated, part is unsaturated or complete undersaturated heterocycle, this heterocycle contains 1-4 heteroatoms independently separately, these heteroatomss are independently selected from 0-1 O, 0-1 S and 0-4 N, each heterocycle all can be by R 12Replace arbitrarily; H; C 1-C 6Haloalkyl; C 3-C 7Halogenated cycloalkyl; C 4-C 7The halogenated cycloalkyl alkyl; C(O) N(R 7) R 8; SO 2R 6; SO 2N(R 7) R 8; C(S) N(R 7) R 8; C(O) R 6; CO 2R 6; C(S) R 6; C(S) OR 6; C(S) SR 6; C(O) SR 6; By R 12Any phenyl that replaces; Five yuan or hexavalent saturated, part is unsaturated or complete undersaturated heterocycle, this heterocycle contains 1-4 heteroatoms, these heteroatomss are independently selected from 0-1 O, a 0-1 S and 0-4 N, each heterocycle all can be by R 12Replace arbitrarily; Condition is: (ⅰ) when X be NR 5The time, R 1And R 5Can merge into arbitrarily-CH 2CH 2CH 2CH 2-,-CH 2CH 2OCH 2CH 2-, perhaps-CH 2CH 2CH 2CH 2CH 2-; (ⅱ) when X be S(O) nAnd when n=1 or n=2, R then 1Not H, C(S) N(R 7) R 8, C(O) R 6, CO 2R 6, C(S) R 6, C(S) OR 6, C(S) SR 6, C(O) SR 6, C(O) N(R 7) R 8, SO 2N(R 7) R 8Or S(O) 2R 6
R 2Be selected from H and C 1-C 3Alkyl;
R 3Be selected from H and CH 3; Perhaps
R 2And R 3Be merged together to form and be selected from CH 2CH 2, CH(CH 3) CH 2, CH 2CH 2CH 2And CH(CH 3) CH 2CH 2Group, when Q is Q-2, Q-3, when Q-4 or Q-5, this group then is CH(CH 3) CH 2Or CH(CH 3) CH 2CH 2;
R 4Be selected from H, CH 2CN, C 1-C 4Alkyl, C 1-C 4Haloalkyl, formyl radical, C 2-C 4Alkyl carbonyl, C 2-C 4Carbalkoxy, C 2-C 4Alkoxyalkyl, C 3-C 6The dialkoxy alkyl, C 1-C 3Alkoxyl group, C 1-C 3Alkyl sulphonyl, C 2-C 4Alkenyl, C 2-C 4Alkynyl, C 1-C 4Alkylamino, C 2-C 4Dialkyl amido and by R 12Any benzyl that replaces;
R 5Be selected from H, C 1-C 6Alkyl, CHO, C 2-C 4Alkyl-carbonyl, C 2-C 4Carbalkoxy and C 1-C 4Alkyl sulphonyl, condition is: work as R 5During for H, R 2, R 3And R 4Not not H just;
R 6Be selected from C 1-C 15Alkyl, C 2-C 6Alkenyl and C 1-C 6Haloalkyl, these groups of representative all can be replaced arbitrarily by phenyl, and phenyl can be by R 12Replace arbitrarily; By R 12Any phenyl that replaces; Five yuan or hexavalent saturated, part is undersaturated or undersaturatedly fully contain 1-4 heteroatomic heterocycle, these heteroatomss are selected from 0-1 O independently of one another, 0-1 S and 0-4 N, each heterocycle all can be by R 12Replace arbitrarily;
R 7And R 8Be selected from H independently of one another, C 1-C 6Alkyl and C 3-C 6Cycloalkyl;
R 9, R 10And R 11Be selected from C independently of one another 1-C 4Alkyl, C 1-C 4Alkoxyl group and phenyl;
R 12Be selected from 1-5 halogen, C 1-C 2Alkyl, C 1-C 2Haloalkyl, C 1-C 2Alkoxyl group, C 1-C 2Alkylthio, C 1-C 2Halogenated alkylthio, C 1-C 2Halogenated alkoxy, NO 2And CN;
N represents 0,1 or 2.
Preferred compd A is a formula I compound, wherein:
Y is R 1X;
X is S;
R 1Be selected from C 1-C 6Alkyl, C 3-C 7Cycloalkyl, C 4-C 7Cycloalkylalkyl, C 2-C 3Alkenyl and C 2-C 3Alkynyl, above-mentioned each group can be selected from CN, C 1-C 4Alkylthio and C(O) OR 6Group replace arbitrarily;
R 4Be selected from H and CH 3
Preferred compd B is a formula I compound, wherein:
Y is R 1X;
X is S;
R 1Be five yuan or hexa-atomic saturated, part is undersaturated or undersaturatedly fully contain 1-4 heteroatomic heterocycle, these heteroatomss can be independently selected from 0-1 O, 0-1 S, 0-4 N, each heterocycle all can be by R 12Replace arbitrarily;
R 12Be selected from 1-5 halogen, C 1-C 2Alkylthio.
Preferred Compound C is that wherein Q is the compd A of Q-1.Preferred Compound D is that wherein Q is the compd B of Q-1.Preferred compd E is a compd A, and wherein Q is selected from group Q-2, Q-3, Q-4 and Q-5, R 2And R 3Merge one of formation and be selected from CH(CH 3) CH 2And CH(CH 3)-CH 2CH 2Group, wherein terminal CH 2Carbon atom with have a R 4Nitrogen-atoms connect.Preferred compound F 17-hydroxy-corticosterone is a compd B, and wherein Q is selected from group Q-2, Q-3, Q-4 and Q-5, R 2And R 3Merge one of formation and be selected from CH(CH 3) CH 2And CH(CH 3) CH 2CH 2Group, wherein terminal CH 2Carbon atom with have a R 4Nitrogen-atoms connect.
Compound of the present invention can one or more steric isomers form exist.Various isomer comprise enantiomer, diastereomer and geometrical isomer.Those skilled in the art is clear, and a kind of isomer may have more activity than other isomer, and knows and how to remove to separate said steric isomer.Correspondingly, present invention includes the racemic mixture of formula I compound, the optically-active mixture of single steric isomer and this compound, and agricultural goes up their salt that is suitable for.
In the above-mentioned definition, term " alkyl " is no matter separately use or constitute compound word as " alkylthio " or " haloalkyl ", all represent alkyl straight chain or side chain, as methyl, ethyl, n-propyl, sec.-propyl and the various isomer that contain 4-20 carbon atom.Alkoxyl group is represented methoxyl group, oxyethyl group, positive propoxy and the various isomer that contain 4 carbon atoms.Alkenyl is represented the alkylene of straight or branched, as vinyl, and 1-propenyl, 2-propenyl and various butenyl, pentenyl and hexenyl isomer.Alkynyl is represented the alkynes base of straight or branched, as ethynyl, and 1-proyl, 2-propynyl and various butynyl, pentynyl and hexin base isomer.Alkylthio is represented methylthio group, ethylmercapto group, positive rosickyite base, iprotiazem base and various butylthio isomer.
" halogen " speech, and though single with or constitute compound word as " haloalkyl ", all represent fluorine, chlorine, bromine or iodine.In addition, in the time of in being used in compound word as in " haloalkyl ", said alkyl can partly or wholly be replaced by halogen atom, and these halogen atoms can be identical, also can be different.The example of haloalkyl comprises CH 2CHF 2, CF 2CF 3And CH 2CHFCl.
Term " heterocycle " is defined as five yuan or six-ring, this ring can be undersaturated fully, part is undersaturated or complete saturated ring, and can contain 1-4 heteroatoms that is selected from 0-4 N, 0-2 O and 0-2 S.A carbon atom on the ring can be replaced the formation carbonyl arbitrarily by Sauerstoffatom.The heterocyclic example comprises pyrrolidyl, imidazolinyl, imidazolidyl, pyrazolinyl, pyrazolidyl, piperidyl, piperazinyl ， oxazolinyl oxazolidinyl, dioxolanyl ， Yi oxazinyl, furyl, the furazan base, thienyl, pyrryl, pyrazolyl ， oxazolyl ， oxadiazole base, imidazolyl ， isoxazolyl, thiazolyl, thiadiazolyl group, isothiazolyl, tetrazyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl and triazinyl, described heterocycle can connect by any one attachable carbon or nitrogen-atoms, for example, when ring was furyl, this ring can be 2-furyl or 3-furyl, if pyrryl, this heterocycle can be the 1-pyrryl, and if 2-pyrryl or 3-pyrryl are pyridyl, heterocycle can be the 2-pyridyl, 3-pyridyl or 4-pyridyl, and other heterocycle is also similar.
The sum of carbon atom represents that with " Ci-Cj " wherein i and j represent the numeral of 1-20 in the substituting group.For example: C 1-C 3Alkyl represents that methyl is to propyl group; C 2Alkoxyl group is represented OCH 2CH 3And C 3Alkoxyl group is represented OCH 2CH 2CH 3And OCH(CH 3) 2
As described in scheme 1, (wherein Y is R to formula I compound 1X, X are S and R 1Be not H) formula II compound and formula III compound are reacted under the condition that can in suitable solvent, have formaldehyde to exist to prepare.Except as otherwise noted, the substituting group described in following each scheme, its meaning is as hereinbefore.
Scheme 1 described reaction conditions generally comprises formula II, formula III compound and the formaldehyde that uses equivalent, though preferably using excessive slightly formaldehyde on the stoichiometry under the situation about having.Scheme 1 described reaction is generally carried out in the temperature range that makes solvent refluxing at 0 ℃, preferred 0-25 ℃.Suitable solvent comprises alcohols such as methyl alcohol and ethanol, water, polar aprotonic solvent such as tetrahydrofuran (THF) and dimethyl formamide.No matter be that the solid Paraformaldehyde 96 or the formaldehyde solution of liquid can be used.In some cases, preferably use a kind of a spot of non-oxide strong acid (example hydrochloric acid) to make catalyzer.This area professional can know that formula III compound comprises thio-alcohol, thiocarboxylic acid class, dithionic acid class and dithiocarbamic acid class.
As described in scheme 2, wherein Y is R 1X and X is SO 2Formula I compound the-sulfinic acid of formula II compound and formula IV or-sulfinate and polyformaldehyde reaction are prepared.
Wherein M=H, Li, Na or K
Suitable solvent comprises dimethyl formamide and N,N-dimethylacetamide, and range of reaction temperature is generally from room temperature to the temperature that makes solvent refluxing.General formula II, formula IV compound and the Paraformaldehyde 96 that uses equimolar amount.When the formula IV is-sulfinate (M=Li, Na or K), with the organic acid such as the acetate of 1 to 10 mole of a great deal of.Can be at Chem.Ber., (1965) find the example of the scheme of being similar to 2 described methods in 98,638..
As described in scheme 3, wherein Y is R 1X and X is NR 5Formula I compound can prepare with formula II compound and formula V compound and formaldehyde reaction.The reaction conditions of scheme 3 is similar to the reaction conditions of scheme 1.Those skilled in the art can know, scheme 3 described reactions be the Mannich reaction variant [Org.React., 1,303(1942), Synthesis, 703(1973); Angew.Chem, 69,463(1957) .]
As described in scheme 4, wherein Y is R 1X and X are that the formula I compound of O can react with formula II compound and formaldehyde and formula VI compound and prepares.One skilled in the art will recognize that formula VI compound comprises water, alcohols and carboxylic-acid.
Figure 931205921_IMG9
Formula VI compound generally is used as reaction solvent, and with the formaldehyde of 1 to 20 mole of a great deal of (or as the aqueous solution, or as the solid Paraformaldehyde 96).Scheme 4 described reactions are generally carried out for from room temperature to 200 ℃ the time in temperature range.When formula VI compound was alcohol, reaction was generally carried out the alkali of available 0 to 5 a great deal of such as salt of wormwood at 100 ° to 200 ℃.When formula VI compound was water or carboxylic acid, the described reaction of scheme 4 was carried out in the temperature range of room temperature to 100 ℃ usually.The alkali of available 0 to 10 a great deal of is as K 2CO 3, triethylamine or 1,4-diazabicyclo-[2,2,2] octanes (DABCO).Reaction method similarly: J.Am.Chem.Soc. is arranged, (1959), 81,2521 in the following document; Synthesis, (1986), 857; Synth.Commun., (1987), 17,291; And Ind.J.Chem., (1988), 278,537.
As described in scheme 5, wherein Y is that the formula I compound of halogen atom can react with the haloid acid of formula II compound and formaldehyde and formula VII and prepares.
Figure 931205921_IMG10
Wherein: Y is a halogen
Scheme 5 described reactions generally need lump together the formolation of formula VII compound excessive on the stoichiometry and formula II compound and 1 to 5 a great deal of.Available polar solvent such as water or acetate.Sometimes also add a kind of Lewis acid, as ZnCl 2Or ZnBr 2The reaction of scheme 5 is generally carried out in 0 to 30 ℃ temperature range.Similar reaction method: J.Org.Chem. is arranged, (1946), 68,2002 and J.Am.Chem.Soc., (1942), 64,477. in the following document
In addition, wherein Y is R 1X and X are S(O) nAnd the n described three-step approaches preparation that is 1 or 2 formula I compound available solutions 6.
Figure 931205921_IMG11
Wherein: R 3And R 4≠ H, R 1Be the alkyl or phenyl that replaces arbitrarily, Y 1Be leavings group such as halogen, Q as defined above
In the 1st step of scheme 6, the described reaction conditions of the used condition of production IX compound and scheme 1 is similar.In the 2nd step of scheme 6, in solvent such as water, alcohols (as methyl alcohol, ethanol or Virahol), ethyl acetate, methylene dichloride, chloroform, acetone or mixed solvent, with formula IX sulfide with a kind of oxygenant such as hydrogen peroxide, metachloroperbenzoic acid, NaIO 4Or permonosulphuric acid potassium is handled.Temperature of reaction is generally 0 ℃ of reflux temperature to solvent, and the reaction times is 1 to 72 hour.
In the described reaction of scheme 6 the 2nd step, when oxygenant uses with 1 mole of a great deal of, obtain n wherein and be 1 formula X compound, when using more than 2 or 2 mole a great deal of oxygenant, obtained n wherein and be 2 formula X compound.The reaction needed that generates n wherein and be 2 formula X compound is 1 the required higher temperature (30 ℃ of temperature to solvent refluxing) of temperature of reaction of formula X compound than generating n wherein.
In the 3rd step of scheme 6, in the presence of a kind of alkali, in suitable solvent, be 20 to 150 ℃, when general preferred temperature range is 50-100 ℃, handle compounds X with formula XX IV alkylating agent in temperature range.Typical alkali comprises K 2CO 3Or NaH, suitable solvent comprises the polar aprotonic solvent, as DMF, and THF or CH 3CN.With removing the typical method that carries out silica gel column chromatography then that desolvates product is separated, the column chromatography eluting solvent that is suitable for comprises chloroform, methylene dichloride, methyl alcohol, ethanol, ethyl acetate, triethylamine, saturated ammonium hydroxide aqueous solution or the mixture of these solvents.
The synthetic method of formula II or formula V III compound was described (seeing WO91/17659) in the past.
In addition, as described in scheme 7, R wherein 2And R 3Merge and form CH 2CH 2, CH(CH 3) CH 2, CH 2CH 2CH 2Or CH(CH 3) CH 2CH 2But the diamine of the formula II compound through type XI of group and formula XII compound react and prepare.
Figure 931205921_IMG12
(R 2And R 3The common alkylidene group that replaces, the R of forming 4=H)
Wherein: X 1Be leavings group, as SCH 3, OC 6H 5Or halogen, X 2Be H or methyl, q is 1 or 2.
The reaction of scheme 7 generally comprise in a kind of polar solvent (as methyl alcohol, ethanol, acetonitrile, tetrahydrofuran (THF), water or their mixture), be up under the temperature condition of solvent refluxing, the XI and the XII compound (being generally 1, two (the methylthio group)-2-nitroethylenes of 1-) of equimolar amount are mixed.Available NaOH, Na 2CO 3Or proton acceptor such as triethylamine.
Can prepare the wherein diamine of the formula XI of q=1 with the two-step approach shown in the scheme 8.
Figure 931205921_IMG13
X wherein 2=H or methyl
Scheme 8 the 1st is in the step, under the condition that the acid of 1 to 3 a great deal of exists, handles the primary amine of formula X III with the aldehyde (formaldehyde or acetaldehyde) of potassium cyanide and formula X VI in a kind of solvent, generates amino-nitrile X IV.In this method available other salt, HCN and the hydrohalogen of prussiate and other hydrochlorate shown in the X III.Suitable solvent comprises methyl alcohol, ethanol, Virahol and water, and the mixture of solvent.Following document has other method (Synth.Commum., (1985), 15,157 of the amino nitrile of preparation (amino-nitrile shown in the X IV); Synthesis, (1979), 127).
Scheme 8 is in the 2nd step, and amino-nitrile X IV is reduced into diamine XI (q=1).Usually in solvent such as ether or tetrahydrofuran (THF), in the temperature range of the reflux temperature of solvent, this reduction reaction is realized with the lithium aluminum hydride of 0.75 to 3 mole of a great deal of at-20 ℃.Perhaps, also can finish the reaction that the X IV is reduced to XI with diborane or with catalyzer (as palladium carbon or Raney nickel) hydrogenation.Sometimes ammonification is useful to the diamine XI of obtaining maximum production in hydrogenation.
Scheme 9 has provided the another kind of method of preparation diamine XI (q=1).
Figure 931205921_IMG14
Scheme 9 the 1st is in the step, at the alkali that 1 to 3 mole of a great deal of is arranged (as NaHCO 3, NaOH, KOH, K 2CO 3, pyridine or triethylamine) under the condition that exists, with the chloride of acid X IX processing acid amides XX of 1 to 2 mole of a great deal of.The solvent that is suitable for comprises tetrahydrofuran (THF), methylene dichloride, water or pyridine.Product X XI can be through extracting and separating, and way is to remove solvent more easily, and the raw product of product X XI is adapted at scheme 9 usually and uses in the 2nd step.The acid amides XX can be as described here used with neutral form, and perhaps to use (generally be hydrochloride or CF to form that also can salt 3CO 2H salt, other salt also can).When making initiator, in the 1st step of scheme 9, need add the alkali of 1 a great deal of in addition with the acid amides XX of salt form.
Scheme 9 is transformed into diamine XI (q=1) with acid amides X XI in the 2nd step, and treatment process is to use a kind of reductive agent, as LiAlH 4, BH 3THF or BH 3SMe 2, solvent is with THF or Et 2O, temperature range from 0 ℃ to the temperature that makes solvent refluxing.Similarly method can be consulted relevant document (seeing Synthesis, (1981), 441).
In addition, formula X XI compound also can prepare by the ester of the described two step method of scheme 10 with formula X XII.
Figure 931205921_IMG15
R wherein 13=C 1-C 5Alkyl or benzyl
Scheme 10 the 1st is in the step, and alkali (triethylamine for example, pyridine or NaHCO are being arranged 3, but be not limited to these) make the normal ester XX of 1 to 10 stoichiometry II (or with free alkali form, or with the halogen acid salt form) and chloride of acid X IX chemical combination under the condition that exists.
The 2nd step of scheme 10 is included in and makes ester XX III and excessive (2 to 100 a great deal of) anhydrous ammonia reaction generation acid amides X XI in the anhydrous methanol.The temperature range of this reaction is generally 15 to 65 ℃.
In the reaction of scheme 9 and scheme 10, use D-or L-type alanimamides XX or alanine ester X XII or their salt, the diamine XI (q=1, the X that provide a kind of acquisition to be rich in enantiomeric forms 2=methyl) make things convenient for method.When coming preparation formula II compound (q=1) by scheme 7 described reactions with the formula XI compound (q=1) that is rich in enantiomer formation, products therefrom formula II compound (q=1) is for being rich in the form of enantiomer.When the formula II compound that is rich in enantiomeric forms by scheme 1 to 5 described usefulness came preparation, products therefrom formula I compound was the form that is rich in enantiomer.
In addition, the acid (as tartrate) with enantiomorph can make the diamine XI become the form that is rich in enantiomorph by splitting.Those skilled in the art know this method for splitting (seeing for example Synthesis, (1991), 789 corresponding example).
Two step method with scheme 11 can prepare the wherein diamine XI of q=2.
Figure 931205921_IMG16
Scheme 11 made amine X III directly mix with nitrile X V (vinyl cyanide or crotononitrile) under 0-150 ℃ of temperature range or (comprise water, methyl alcohol, ethanol, the mixture of THF or these solvents) in suitable solvent and mix in the 1st step, generated amino-nitrile XX V.The amount of used formula X III compound is 1 to 10 mole of a great deal of.
Shown in the step of the 2nd in the scheme 11, can make amino-nitrile XX V be reduced to diamine XI (q=2) with similar condition of the 2nd step in the aforementioned schemes 8.
In addition, as described in scheme 12, (wherein Y is R to make formula I compound 1X, X are O, S or NR 5, R 1Be H) can prepare such formula I compound with the reaction of formula X VII compound, wherein Y is R 1X, X=O, S or NR 5, R 1Be not H.
Wherein: X 3Be a leavings group, as halogen
The reaction of general scheme 12 comprises use greater than the normal formula X of 1 stoichiometry VII compound with greater than the normal proton acceptor of 1 stoichiometry, suitable solvent, the reflux temperature of temperature range from 0 ℃ to solvent.Typical proton acceptor comprises amine, as pyridine, and triethylamine, DBU and DABCO, and mineral alkali such as NaHCO 3, K 2CO 3, NaOH and KOH.The solvent that is suitable for comprises acetonitrile, CH 2Cl 2, THF and EtOAc.Proton acceptor can be used as solvent (pyridine for example, Et under some situation 3N or other liquid amine).Those skilled in the art can know that formula X VII compound comprises alkylogen, allyl halide, propargylic halide, acyl halide, haloformate, acid anhydride class, alkylsulfonyl halogen, formamyl halogen, halo thiocarboxylic and halo dithio formate.
In addition, prepare such formula I compound with scheme 13 described methods, wherein Y is R 1X, X are O, S or NR 5, R 1Be C(O) NHR 8Or C(S) NHR 8
Figure 931205921_IMG18
In the described reaction of scheme 13, a kind of compound of formula I (R wherein 1Be H, X is O, S or NR 5) with isocyanic ester or the lsothiocyanates chemical combination shown in the formula X VIII of 1 a great deal of, suitable solvent comprises THF, EtOAc or DMF.Temperature of reaction is generally 0 to 50 ℃.
As described in scheme 14, through type I compound (R wherein 1Be an acyl group (R for example 6(C) O), X is S) but the hydrolysis preparation (wherein Y is R 1X, R 1Be H, X is S).These reactions generally are that (as THF, MeOH, EtOH and water) carries out with alkali (as NaOH, KOH, NaOMe and NaOEt) in a kind of polar solvent.
Figure 931205921_IMG19
Provided the synthetic method of the initiator (I) of scheme 14 in the scheme 1.
Embodiment 1
The 1st step: the 2-(Nitromethylene)-imidazolidine
With 4.0ml(0.06mol) quadrol, 10g(0.06mol) 2, two (methylthio group) nitroethylenes of 2-and 60ml alcoholic acid vlil 12 hours, after concentrating the 7.6g beige solid.
1H NMR（200MHz，（CH 3） 2SO-d 6）δ6.33（s，1H），3.58（s，4H）.
The 2nd step: the ethyl 1-[2-(methylthio group)]-2-(nitro ethylidene) imidazolidine
Under the room temperature with 2.0g(0.016mol) the 1st the step product be added to 60% sodium hydride (0.7g, 0.017mol) and 31ml dimethyl formamide (DMF) suspension liquid in.The gained mixture was stirred 10 minutes, adds 1.5ml(0.016mol then) 2-chloroethyl methyl thioether.The mixture that forms was heated 12 hours at 100 ℃, then cool to room temperature.Add 20ml ethanol, reactant is concentrated in the time of 70 ℃.Enriched material is dissolved among the 50mlEtOH; Add 5g silica gel, again mixture is concentrated.With 100g silica gel the enriched material chromatography is separated, use CH 2Cl 2-EtOH-48%NH 4OH(20: 1: 0.1) wash-out gets the 1.0g brown oil, becomes solid after the placement.Develop this solid with MeOH and generate faint yellow solid; Fusing point=102-104 ℃.
1H NMR
（400MHz，CDCl 3）δ8.65（br s，1H），6.55（s，1H），3.78（m，4H），3.38（t，2H），2.70（t，2H），2.16（s，3H）.
The 3rd step: [the 2-[1-[2-(methylthio group) ethyl]-2-imidazolidine subunit]-the 2-nitro-ethyl] sulfenyl] acetate methyl ester (compound 1)
With 0.5g(0.0025mol) product, the 0.2ml(0.0025mol in the 2nd step) sulfo-glycolic acid methyl esters, 0.2ml(0.003mol) 37% formalin and 15ml alcoholic acid vlil 4 hours, cool to room temperature and concentrating then.The product crude product (0.8g) that generates is dissolved in the methylene dichloride, uses the 3g silica gel treatment, concentrate then.With gained residue purifying, use silica gel 50g with the flash chromatography method, elutriant is 20: 1: 0.1 CH 2Cl 2-EtOH-48%NH 4OH gets 0.5g viscosity oily product, and this oil is with after fixing; Fusing point=44-47 ℃.
1H NMR（400MHz，CDCl 3）δ9.64（brs，1H），4.05（s，2H），3.85-3.78（m，6H），3.75（s，3H），3.45（s，2H），2.81（t，2H），2.19（s，3H）.
Embodiment 2
The 1st step: the ethylamino 2-[2-(methylthio group)] propionitrile
In 15 minutes, 294ml 1M HCl is added drop-wise to by 24.4g(0.27mol) the 2-(methylthio group) in the solution that constitutes of ethamine and 100ml methyl alcohol, and maintain 5-10 ℃ with the ice bath cooling and handle.Use by 17.4g(0.27mol in 5-10 ℃ of solution gained) solution-treated that potassium cyanide and 150ml water constitute, add 13g(0.29mol in 5-10 ℃ again) acetaldehyde handles.After the solution that generates at room temperature stirred 6 hours, pour saturated sodium bicarbonate aqueous solution and 300ml CH then into by 1L 2Cl 2In the mixture that constitutes.With water layer additional C H 2Cl 2Extracting twice (each 200ml) is with the organic layer saturated NaHCO of 500ml that merges 3Solution washing is with anhydrous MgSO 4Drying is filtered, and concentrates, and generates 37.6g(97%) lark oily matter.
1H NMR（200MHz，CDCl 3）δ3.78-3.60（m，1H），3.17-2.97（m，1H），2.94-2.74（m，1H），2.71-2.62（m，2H），2.12（s，3H），1.67（br s，1H），1.52（d，J＝7 Hz，3H）.
The 2nd step: N 2-[the 2-(methylthio group) ethyl]-1, the 2-propylene diamine
With the lithium aluminium hydride (1M(CH of 84ml 3CH 2) 2O solution is 0.084mol) with (CH 3CH 2) 2O(163ml) solution stirs with mechanical stirrer is powerful, and 0 ℃ drips 6.04g(0.042mol down) product in the 1st step is at 82ml(CH 3CH 2) 2Solution among the O is handled.The white heterogeneous mixture that generated was stirred 1 hour at 0 ℃,, be cooled to 0 ℃ then, under 0 ℃, sequentially add the solution of the 10ml tetrahydrofuran (THF) of 3.1ml water carefully, 3.1ml15%NaOH and 9.3mlH stirring at room 1 hour 2O makes the stopping of reaction.Use 155ml(CH 3CH 2) 2O is with resulting mixture diluted, stirred overnight at room temperature.The mixture of gained is filtered, and filtrate concentrating obtains 6.4g deep yellow oily thing.
1H NMR（200MHz，CDCl 3）δ2.97-2.45（m，7H），2.11（s，3H），1.75（br s，3H），1.05（d，J＝6Hz，3H）.
The 3rd step: the 5-methyl isophthalic acid-[the 2-(methylthio group) ethyl]-the 2-(Nitromethylene)-imidazolidine
Will be by 2.6g(0.018mol) product, the 2.9g(0.018mol in the 2nd step) 2,2-is two-vlil that (methylthio group)-1-nitroethylene and 18ml dehydrated alcohol constitute 5 hours, cool to room temperature concentrates, and obtains the 4.8g brown oil.This oily matter is carried out the flash chromatography method separate on silica gel, with 40: 1: 0.1 CH 2Cl 2: CH 3CH 2OH: 48%NH 4The OH wash-out obtains the 1.8g yellow oil, places after fixing, fusing point 60-62 ℃.Grind this solid with 1-chlorobutane and obtain a kind of subalbous solid, fusing point is 66-68 ℃.
1H NMR（200MHz，CDCl 3）δ8.63（br s，1H），6.53（s，1H），4.21-4.03（m，1H），3.90（t，1H），3.40-3.28（m，3H），2.78-2.58（m，2H），2.16（s，3H），1.36（d，3H）.
The 4th step: [[the 2-[5-methyl isophthalic acid-[and the 2-(methylthio group) ethyl]-2-imidazolidine subunit]-the 2-nitro-ethyl] sulfenyl] acetate methyl ester (compound 2)
Will be by 0.5g(2.3mmol) product, the 0.2ml(2.3mmol in the 3rd step) sulfo-glycolic acid methyl esters, 0.2ml(2.8mmol) vlil that constitutes of 37% formalin and 14ml ethanol 4 hours.The solution cool to room temperature that generates concentrates, and gets 0.8g dark-brown oily matter.
1H NMR（200MHz，d 6-DMSO）δ9.18（br s，1H），4.12-4.00（m，1H），3.85（s，2H），3.80-3.70（m，2H），3.64（s，3H），ca.3.6-3.2（m，3H），3.41（s，2H），2.70（q，2H），2.09（s，3H），1.22（d，3H）.
Embodiment 3
The 1st step: carbonyl N-[(6-chloro-3-pyridyl)]-the L-Ala methyl ester
Will be by 50.5g(0.29mol) 6-chloronicotinoyl chloride and 290ml CH 2Cl 2The solution that constitutes is added to by 60g(0.43mol) in the hydrochloride of DL-alanine methyl ester and the solution that the saturated sodium bicarbonate aqueous solution of 290ml constitutes.Add 5ml aliquat 336(Aldrich then), the biphase mixture that is generated was stirred 24 hours down fast at 25 ℃.The mixture that generates is distributed in CH 2Cl 2With saturated NaHCO 3In, use CH 2Cl 2With water layer extraction three times.Organic layer is merged back with saturated NaHCO 3Washed twice is used MgSO 4Drying concentrates, and gets the 56.1g title compound, is the heavy-gravity yellow oil.
1H NMR(300MHz, CDCl 3) δ 8.82(d, J=2.4Hz, 1H), 8.10(dd, 1H), 7.41(d, 1H), 7.10(brd, 1H), the 4.78(quintet, 1H), 3.80(s, 3H), 1.53(d, 3H).
The 2nd step: 6-chloro-N-[1-(aminocarboxyl)-ethyl]-the 3-pyridine carboxamide
Will be by 50.5g(0.21mol) product in the 1st step and the solution that the anhydrous MeOH of 150ml constitutes joins in the absolute methanol solution of 575ml 15% anhydrous ammonia.The solution that generates was stirring at room 48 hours.The solids removed by filtration product is used washing with alcohol, and vacuum-drying obtains the 43.5g title compound, is white solid, fusing point＞220 ℃.
1H NMR(400MHz, (CH 3) 2SO-d 6) the obvious s of δ 8.87(, 1H), 8.79(d, 1H), 8.29(d, 1H), 7.65(d, 1H), 7.45(br s, 1H), 7.03(br s, 1H), the 4.41(quintet, 1H), 1.33(d, 3H).
The 3rd step: N 2-[(6-chloro-3-pyridyl)-methyl]-1, the 2-propylene diamine
In the time of 50-60 ℃ to 8.5g(0.04mol) drip 18.7ml(0.19mol in the product in the 2nd step and the mixture that the mechanical stirring of 112ml THF) borane-methyl thioether mixture.The orange-yellow suspension liquid that generates was refluxed 2 hours, and cool to room temperature drips 62ml 6NHCl(thermopositive reaction carefully, the violent hydrogen of putting! ) make the stopping of reaction.The light yellow mixture that generates stirring at room 24 hours, is washed with three parts of ether then.Add down with 25ml 50% NaOH(cooling) make the water layer alkalization, use 2: 1 methylene dichloride then: chloroformic solution extraction (3 * 150ml).To use K after the organic layer merging 2CO 3Drying concentrates, and obtains the title compound of 3.5g yellow oily.
1H NMR(400MHz, CDCl 3) the obvious s of δ 8.33(, 1H), 7.69(d, 1H), 7.30(d, 1H), 3.78(ABq, 2H), 2.75(d, 1H), 2.63(dd, 1H), 2.53(dd, 1H), ca.1.50(br s, 3H), 1.07(d, 3H).
The 4th step: 2-chloro-5-[[5-methyl-2-(Nitromethylene)-the 1-imidazolidyl] methyl] pyridine
Will be by 2.5g(0.013mol) product, the 1.6g(0.009mol in the 3rd step) 1, the suspension liquid reflux that two (methylthio group)-2-nitroethylenes of 1-and the anhydrous EtOH of 63ml constitute 3 hours was placed 72 hours at 24 ℃ then.The mixture that generates is concentrated, separate in the enterprising circumstances in which people get things ready for a trip spectrum of silica gel, with 15: 1: 0.1 CH 2Cl 2: EtOH: 30% NH 4The OH wash-out obtains the title compound of 0.70g yellow solid shape, fusing point=127-131 ℃.
1H NMR（400MHz，CDCl 3）δ8.70（br s，1H），8.27（s，1H），7.56（d，1H），7.35（d，1H），6.56（s，1H），4.33（ABq，2H），3.95-3.85（m，2H），3.45-3.35（m，1H），1.33（d，3H）.
The 5th step: ethylidene 2-chloro-5-[[5-methyl-2-[1-nitro-2-(propyl group sulfenyl)]-the 1-imidazolidyl] methyl] pyridine (compound 7)
Will be by 0.5g(0.002mol) product in the 4th step and the solution that 12mlEtOH constitutes uses 0.17ml(0.002mol successively) 1-propylmercaptan and 0.16ml(0.002mol) 37% formalin handles.The mixture that generates was stirred 18 hours and concentrated in 25 ℃.Silica gel flash chromatography method was separated, with 15: 1: 0.1 CH 2Cl 2: EtOH: 30%NH 4The OH wash-out obtains the 0.17g title compound, is yellow solid.Fusing point=127-129 ℃.
1H NMR（300MHz，CDCl 3）δ9.87（br s，1H），8.37（s，1H），7.63（d，1H），7.39（d，1H），4.92（ABq，2H），4.00-3.82（m，3H），3.46（d，1H），3.36（t，1H），2.50（t，2H），1.55-1.43（m，2H），1.32（d，3H），0.90（t，3H）.
Can prepare the compound of table 1 with method as one of described herein or through obvious improved method to table 15 and concordance list A-C.To table 15 and concordance list A-C, the meaning of used character is as follows at table 1:
Figure 931205921_IMG20
Figure 931205921_IMG21
Figure 931205921_IMG22
The table 1-15 by list with above-mentioned tabulation in the corresponding Y value of structure specifically name compound.The compound of table among the 1-15 can number be represented by the ranks at its place.For example four compounds of the 1st row can be expressed as 1-1 in the table 1,1-2,1-3 and 1-4(promptly with row number and be listed as number represent).Included all available this mode of other particular compound of table 1-15 is represented.
Figure 931205921_IMG25
Figure 931205921_IMG26
Figure 931205921_IMG27
Figure 931205921_IMG28
Figure 931205921_IMG29
Figure 931205921_IMG31
Figure 931205921_IMG32
Figure 931205921_IMG33
Figure 931205921_IMG34
Figure 931205921_IMG35
Figure 931205921_IMG36
Figure 931205921_IMG38
Preparation/application
The present invention also comprises the Pestcidal compositions that contains one or more as former defined formula I compound.The carrier (comprising the liquid or solid thinner) that compound of the present invention is suitable on general and a kind of agricultural in preparation is used.Useful preparation comprises pulvis, granule, poison bait, pill, solution, clouding agent, emulsion, wettable powder, missible oil, dry powder flowing agent (dry flowables) or the like, consistent with physical properties, method of application and the environmental factors (such as soil type, humidity and temperature) of activeconstituents.Available suitable medium is made into to spray uses preparation, and per hectare spray consumption is raised to hundreds of liters from about 1.The composition of high density can mainly be used as the intermediate of further preparation.Generally contain effective amount of actives in the preparation, thinner and tensio-active agent, approximate range following (total amount is 100%):
Weight percent
Activeconstituents thinner tensio-active agent
Wettable powder 5-90 0-74 1-10
The oil clouding agent, emulsion 5-50 40-95 0-15
(comprising missible oil)
Pulvis 1-25 70-99 0-5
Granule, poison bait and pill 0.01-99 5-99.99 0-15
High concentration composition 90-99 0-10 0-2
The typical solid thinner is seen people such as Watkins, Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, typical liquid diluent of New Jersey. and solvent are seen Marsden, Solvents Guide, 2nd Ed., Interscience, New York, (1950) .McCutcheon ' sDetergents and Emulsifiers Annual, Allured Publ.Corp., Ridgewood, New Jersey, and Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ.Co., Inc., New York, (1964)
Listed the usage of tensio-active agent and recommendation.All can contain minor amounts of additives in all preparations to reduce foam, caking, the generation of burn into microorganism or the like.
Simply various compositions are mixed and promptly make solution.Preparing fine solids composition can use polishing usually with smashing method to pieces, just as in mill or water mill.The water-dispersible granular material agent can prepare by the fine powder composition that condenses, referring to people such as Cross, and Pesticide Formulations, Washington, D.C., (1988), pp251-259.Clouding agent prepares by wet milling process, referring to U.S.3, and 060,084.Granule and pill can prepare by activeconstituents is sprayed on the ready made granular carrier or by coagulation method.See Browning, " Agglomeration ", Chemical Engineering, December4,1967, pp147-148, Perry ' s Chemical Engineer ' s Handbook, 4th Ed., McGraw-Hill, New York, (1963), pp8-57 and following, and WO91/13546.
The further situation of relevant preparation, referring to U.S.3, the 235,361, the 6th be listed as the 16th walk to the 7th be listed as the 19th the row and embodiment 10-41; U.S.3, the 309,192, the 5th is listed as the 43rd walks to the 7th and is listed as the 62nd row and embodiment 8,12,15,39,41,52,53,58,132,138-140,162-164,166,167 and 169-182; U.S.2, the 891,855, the 3rd be listed as the 66th walk to the 5th be listed as the 17th the row and embodiment 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, (1961), pp81-96; And people such as Hance, Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, (1989).
All per-cents in the following example all are weight percentage, and all preparations are all prepared by method in common.Compound number refers to the compound among the concordance list A.
Embodiment A
Wettable powder
Compound 1 65.0%
4-dodecylphenol polyglycol ether 2.0%
Sodium lignosulfonate 4.0%
Sodium silicoaluminate 6.0%
Polynite (calcining) 23.0%
Embodiment B
Granule
Compound 1 10.0%
The attapulgite particle (low volatility materials,
0.71/0.30mm; The U.S.S.No.25-50 order) 90.0%
Embodiment C
The pill that squeezes out
Compound 1 25.0%
Anhydrous sodium sulphate 10.0%
Rough calcium lignosulfonate 5.0%
Sodium alkyl naphthalene sulfonate 1.0%
Calcium magnesium wilkinite 59.0%
Embodiment D
Missible oil
Compound 1 20.0%
Oil-soluble sulfonic acid salt and polyethenoxy ether class
Mixture 10.0%
Isophorone 70.0%
Compound of the present invention to food leaf, food fruit, food rhizome, food seed, (arthropods comprises insect to the aquatic and native arthropods that dwells, mite class and nematode) have the insecticidal activity of wide spectrum, these arthropodss are insects growth and agricultural-food, Forest products, greenhouse effect, ornamental plant, nursery crop, grain storage and fibre product, domestic animal, family members and public health and animal health storage.Those skilled in the art know, being not all compound all has identical insecticidal action to each etap of all insects.Yet compound of the present invention all has insecticidal activity to comprising following various insects: lepidopterous ovum, larva and adult; The larva and the adult of ovum of Coleoptera and food leaf, food fruit, food root, food seed; The ovum of Hemiptera and Homoptera, children's phase and adult; The ovum of acarina, larva, nymph and adult; The ovum of Thysanoptera, Orthoptera and Dermaptera, children's phase and adult; Ovum, the young and the adult of dipterous ovum, children's phase and adult and nematode.Compound of the present invention also can kill Hymenoptera, Isoptera, Siphonaptera,
Figure 931205921_IMG39
Lian order, Thysanura and psocopteran insect; Kill the insect that belongs to Arachnida and Platyhelminthes.Especially, compound of the present invention has insecticidal activity to following insect: cucumber 11 asterophyllite first food root subspecies, and two leafhoppers, Mexico's cotton boll resembles, two-spotted spider mite, fall army worm, aphis fabae, Heliothis virescens, rice root weevil, Oulema oryzae, white backed planthopper, rice green leafhopper, brown paddy plant hopper, small brown rice planthopper, striped rice borer, cnaphalocrocis medinalls guenee, scotinophora lurida, America Leptocorisa spp, brown Leptocorisa spp, rice spiny coreid, Leptocorisa spp.Compound of the present invention has effect to the mite class, shows that the mite to following each section all has the ovum of killing, kills larva and pest control with insecticide activity, and above-mentioned mite comprises: the two-spotted spider mite of Tetranychidae, tetranychus telarius, step tetranychid, Pacific Ocean tetranychid, strawberry tetranychid, Byrobia rubrioculus, the elm Panonychus citri, the tangerine Panonychus citri
Figure 931205921_IMG40
Beginning tetranychid north subspecies, the Xi Shi tetranychid that begin, Eotetranychus sexmaculatus, Yuma beginning tetranychid, Ban Shi begin tetranychid and meadow unguiculus mite; The grape brevipalpus of Tenuipalpidae, purplish red short hairs mite, California short hairs mite and priet mite; The tangerine of the Eriophyidae rust mite that rues, tangerine bud goitre mite, peach thorn rust mite, pears dust goitre mite and Man goitre mite.More detailed insect famous-brand clock is referring to WO 90/10623 and WO92/00673.
Compound of the present invention also can with the compound of one or more other insecticide, mycocide, nematocides, sterilant, miticide, growth regulator, chemosterilant, half chemicals, repellent, attractive substance, pheromone, stimulation feed agent or other biologically active; form multi-component sterilant, thereby have agricultural protection spectrum widely.Can have with other agricultural protection agent that compound of the present invention is mixed: sterilant, as avermectin B, monocrotophos, furans pellet, tetrachlorvinphos, Malathion, methyl 1, Insecticide 1179, the desinsection amidino groups, diazinon, Deltamethrin, careless oxime prestige, nitrile chlorobenzene phenothrin, esfenvalerate, Permanone, profenofos, sulprofos, triflumuron, deflubenzuron, it is plain that methoxy is protected the children, brprofezin, thiodicarb, acephate, R-1582, chlorine pyrrole phosphorus, Rogor, fipronil, careless fluorine peace, N-2790, isofenphos, first thiophene sulphur phosphorus, acephatemet, R-1504, phosphamidon, Phosalone, go out and decide prestige, phorate, special fourth phorate, Trichlorphon, methoxy DDT, bifenthrin, biphenate, cyfluthrin, tefluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, imidacloprid, Halizan and tubatoxin; Mycocide, as derosal, thiuram, dodine, maneb, chloroneb, F-1991, cymoxanil, fenpropidine, fenpropimorph, triadimefon, Vancide 89, thiophanate methyl, thiabendazole, phosethyl-Al, m-tetrachlorophthalodinitrile, dicloran, metalaxyl, Difolatan, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difenoconazole, diniconazole, fluguinconazole, ipconazole, metconazole, penconazole, propiconazole, uniconazole, flutriafol, prochloraz, pyrifenox, the phonetic alcohol of two chlorobenzenes, triadimenol, diclobutrazol, Cupravit, furalaxyl, Phaltan, flusilazol, miewensu, diclomezine, Hinosan, isoprothiolane, iprobenfos, mepronil, monomethylarsinic acid iron ammonium, pencycuron, thiophene bacterium alkene, pyroquilon, triazole benzene thiophene, validamycin, and flutolanil; Nematocides such as aldoxycarb, Nemacur, and fosthietan; Sterilant such as terramycin, Streptomycin sulphate and Basic Chrome Sulphate; Miticide such as Niagara 9044, quinomethionate, G-23922, kelthane, Hooker HRS 16, cyhexatin, hexythiazox, amine three nitrogen mites, propargite, tebufenpyrad and mite are finished tin; And biotechnological formulation, as entomopathogenicity bacterium, virus and fungi.
In some cases, with have identical insecticidal spectrum but different other Arthropodicidal medicament of the mode of action is used in the resistance management meaningful especially.
In comprising the environment that the insect life is arranged agricultural and/or non-agricultural; and the area that is needing protection; or directly facing to the controlling object insect; use one or more compounds of the present invention by significant quantity; can prevent and treat arthropod, reach the purpose of protection farm crop, garden crop and special crop and human and livestock health.Therefore; the present invention also comprises a kind of method; this method is in agricultural that insect life is arranged and/or environment such as non-agricultural; and the area that is needing protection; or directly facing to controlling object insect itself; use one or more formula I compounds or contain the composition of at least a this compounds by significant quantity, prevent and treat the food leaf and perch arthropod and nematode pests in soil, thereby protection is agricultural and/or non-agricultural crop.Preferred application process is to spray.In addition, can be on the leaf of plant or use the granule of this compounds in the soil.Other application process comprises direct sprinkling, residual spray, and air-atomizing, seed soaking, microcapsule, interior suction, poison bait, ear tag, bolus, smoke substance, fumigant, aerosol, pulvis and other are all.Compound of the present invention can be mixed with arthropodan bait or be used for bait that lures by device or the like.
Compound of the present invention can former medicine form use, but the more frequent preparation that is to use, wherein contain one or more and plant this compounds and suitable carriers, thinner and tensio-active agent, and probably according to the use that combines of deliberate end-use and a kind of food.Preferred application process relates to the water dispersant that sprays this compounds or meticulous finish.With insecticide oil, concentrate insecticide oil, sprawl tackiness agent, auxiliary and synergistic agent, and other solvent such as piperonyl butoxide are used in combination the effect that regular meeting increases The compounds of this invention.
The consumption that reaches effective dispensary need depends on some factors like this, as the pest species of being prevented and treated, and the life history of insect, worm phase, physical size is perched the place, season, host crop or animal species, feeding habit, mating habit, the humidity of surrounding environment, temperature or the like.Under the normal circumstances, the consumption of about 0.01 to 2kg activeconstituents/hectare is enough to prevent and treat the insect in the agroecosystem, but only needs the 0.001kg/ hectare sometimes, and the consumption that but needs 8kg/ hectare nearly sometimes.For the application on non-agricultural, effective level is about 1.0 to 50mg/m 2, but 0.1mg/m only perhaps sometimes 2Just enough, but need nearly 150mg/m sometimes 2Consumption.
Following test has illustrated that compound of the present invention prevents and treats the effect of specific insect.But the insect that this compounds can be prevented and treated is not limited in these kinds.Allied compound is described referring to concordance list A and B.
Concordance list A
Compound Y fusing point ℃
1 MeO 2CCH 2S 44-47
Concordance list B
Compound R 1X fusing point ℃
2 MeO 2CCH 2S oily matter
3 cyclohexyl S oily matter
4 n-PrS oily matter
5 (EtO) 3Si (CH 2) 2S oily matter
6 NaO 2CCH 2The S viscous solid
Concordance list C
Figure 931205921_IMG43
Compound R 1X fusing point ℃
7 n-PrS 127-129
Cmpd No. 1H NMR data (a)
3 (b) 9.22 (s, 1H), 2.82-2.65 (m, 3H), 2.11 (s, 3H), 1.98-1.89 (m, 2H), 1.32-1.19 (eclipsed m and d, 7H total amount), 1.06 (apparent t, 4H).
4(b) 9.22(s,1H),2.82-2.75(m,1H),2.74-2.64(m,1H),2.51(t,2H),
2.11 (s, 3H), 1.55 (sextet, 2H), 1.23 (d, 3H), 0.92 (t, 3H).
5(b) 9.22(s,1H),2.10(s,3H),1.23(d,3H),1.15(t,9H),1.06(t,2H).
6(b) (in D 2O,HDO=δ4.66)1.98(s,3H),1.05(d,3H).
A, except as otherwise noted, the nuclear-magnetism spectrum all is at CDCl 3In when 400MHz, obtain.S=singlet, d=doublet, t=triplet, m=multiplet, coupling constant (J) unit are hertz.
B, partial data.
Test A
Cucumber 11 asterophyllite first food root subspecies
Every group of test is one 8 ounces of (230ml) plastic cups, 1 square inch of soybean of interior Sheng-Fructus Hordei Germinatus bait.Spray the solution (solvent is acetone/distilled water of 75/25) of each testing compound in each glass respectively.Cup is placed on the travelling belt, makes rim of a cup, with the pressure of 30 pounds/square inch (207kPa) amount compound is sprayed in the cup by 0.5 pound of effective constituent/acre (about 0.55kg/ hectare) by nozzle directly under a flat fan hydraulic pressure nozzle.After waiting to be sprayed on medicine in the cup and doing, the II instar larvae of 5 cucumber 11 asterophyllite first foods of inoculation root subspecies in each cup.Then cup is built, under 27 ℃ and 50% relative humidity environment, kept somewhere after 48 hours and check, calculate mortality ratio.Again cup is built, after placing 6 days again under 27 ℃ and the 50% relative humidity environment, checked, calculate mortality ratio.In the compound of being tested, cause that with the concentration of 1000ppm the compound more than or equal to 80% mortality ratio is after 48 hours: 1,2,5,6.
In the compound of being tested, causing that the compound of examination worm death more than 80% or 80% is after 8 days altogether with the concentration of 1000ppm: 1,2,4,5,6.
Test B
Two leafhoppers
With the cup of several 12 ounces (350ml), one deck 1 inch (2.54cm) thick sterilization soil and 1/2 inch (1.27cm) thick one deck sand in shop in each cup, oat seedling on the kind.Spray method is as described in the test A, and solution that respectively will following each compound is sprayed onto in the cup and (sprays a kind of compound in each cup).After treating that oat seedling spray medicine is done, bowl cover is good, open a mouth on the lid, suck 10-15 two leafhoppers adult in each cup.Cup is placed in 27 ℃ and the 50% relative temperature environment kept 48 hours, check, calculate mortality ratio then.Survey in the compound, cause that with the concentration of 1000ppm the compound more than or equal to 80% mortality ratio is: 1,3,4,5,6.
Test C
Mexico's cotton boll resembles
With the cup of several 9 ounces (260ml), put into 5 Mexico's cotton bolls in each cup and resemble adult.Spray method is sprayed onto the solution of following compounds respectively (a kind of compound of spray in each cup) in the cup as described in the test A.Cup is built with the lid that has an opening, placed 27 ℃ and 50% relative temperature environment to keep 48 hours, check, calculate mortality ratio then.Survey in the compound, cause that with the concentration of 1000ppm the compound more than or equal to 80% mortality ratio is: 2.
Test D
Aphis fabae
With the leaf of the nasturtium of monolithic, inoculation 10 to 15 aphids (each budding aphis fabae) on the every leaf, with the leaf back side up, by the described spray medicine of test A.Leaf is put in the bottle of 3/8 inch (0.94cm) diameter then, fills the 4ml sugar aqueous solution in the bottle, build in case the aphid that falls down from leaf is run away with 1 ounce of (29ml) plastic cup of a cleaning.Bottle is placed in 27 ℃ and the 50% relative humidity environment kept 48 hours, check, calculate mortality ratio then.Survey in the compound and cause that with 1000ppm concentration the compound more than or equal to 80% mortality ratio is: 2,3.
Test E
Contact toxicity to the rice green leafhopper nymph
The about 10cm height of plantation 3 strains, the rice seedlings of 1.5 leaf phases in filling 1/2 ounce of (14ml) plastic cup of Kumiai Brown artificial soil.In cup, add 7ml distilled water then.Testing compound is dissolved in earlier in the acetone, and adding water then, to make final experimental concentration be 75: 25(acetone: water).Put 4 plastic cups on a spray medicine-chest rotating disk, each cup is as a repetition.With the aerosol nozzle with 2.0kg/cm 2Pressure with the 50ml compound solution to 45 seconds of cup spray medicine, this in 45 second inner rotary table changeed 7.5 circles.Behind the spray medicine cup is placed the medicine drying that made spray in the joint sealing of opening in 2 hours.After medicine is done cup is put into the proofing box of taper, the thick quartz sand of soil surface shop one deck 2-3mm.Be drawn onto in the proofing box with the III nymph in age of pest sucking device, proofing box is placed 27 ℃ and 65% relative humidity environment 8 to 10 rice green leafhoppers.24 and 48 hours statistics are survived and dead nymph number after connecing worm.All insects that can not climb promptly are judged to death.Survey in the compound, with what 100ppm caused more than 80% or 80% the death of examination worm at 48 hours be: 1,2,3,4,5,6.
Test F
Contact toxicity to the brown paddy plant hopper nymph
The about 10cm height of plantation 3 strains, the rice seedlings of 1.5 leaf phases in filling 1/2 ounce of (14ml) plastic cup of Kumiai Brown artificial soil.In cup, add 7ml distilled water then.Testing compound is dissolved in earlier in the acetone, and adding water then, to make final experimental concentration be 75: 25(acetone: water).Put 4 plastic cups on a spray medicine-chest rotating disk, each cup is as a repetition.With the aerosol nozzle with 2.0kg/cm 2Pressure with the 50ml compound solution to 45 seconds of cup spray medicine, than 45 second inner rotary table changeed 7.5 circles.Behind the spray medicine cup is placed the medicine drying that made spray in the joint sealing of opening in 2 hours.After medicine is done cup is put into the proofing box of taper, the thick quartz sand of soil surface shop one deck 2-3mm.Be drawn onto in the proofing box with the III nymph in age of pest sucking device, proofing box is placed 27 ℃ and 65% relative humidity environment 8 to 10 brown paddy plant hoppers.24 and 48 hours statistics are survived and dead nymph number after connecing worm.All insects that can not climb promptly are judged to death.Survey in the compound, with what 100ppm caused more than 80% or 80% the death of examination worm at 48 hours be: 2,3,4,5,6.
Test G
Inner sucting killing insect activity to the rice green leafhopper nymph
The compound of test directly is added in the 10ml distilled water and makes it to dissolve fully.This compound solution is poured in the test chamber of a taper.With a sponge disk of having beaten the hole three strain rice seedlings are fixed in this container.The effect of sponge disk is that the root system of rice seedlings is immersed in the compound solution fully, is isolated in more than the liquid level and make plant extend in airborne part.The sponge disk can prevent that also tested nymph from touching tested solution by accident.Leave the space of 7mm-10mm between the bottom of sponge disk and the liquid level and be infected with the sponge disk by accident to prevent compound solution.Container was placed in the raising chamber of 27 ℃ and 65% relative humidity 24 hours, and allowed rice seedlings absorption compound from solution.With pest sucking device 8 to 10 rice green leafhopper III nymphs in age are moved in the test chamber.The container that has connect worm is placed under the temperature and humidity conditions identical with the above.Connect 24 and 48 hours dead, nymph numbers of living of statistics behind the worm.All can not climb then be judged to dead worm.In the compound of being surveyed, cause at 48 hours that with the concentration of 100ppm the compound of examination worm death more than 80% or 80% is: 1,2,3,4,5,6.
Test H
Inner sucting killing insect activity to the brown paddy plant hopper nymph
The compound of test directly is added in the 10ml distilled water and makes it to dissolve fully.This compound solution is poured in the test chamber of a taper.With a sponge disk of having beaten the hole three strain rice seedlings are fixed in this container.The effect of sponge disk is that the root system of rice seedlings is immersed in the compound solution fully, is isolated in more than the liquid level and make plant extend in airborne part.The sponge disk can prevent that also tested nymph from touching tested solution by accident.Leave the space of 7mm-10mm between the bottom of sponge disk and the liquid level and be infected with the sponge disk by accident to prevent compound solution.Container was placed in the raising chamber of 27 ℃ and 65% relative humidity 24 hours, and allowed rice seedlings absorption compound from solution.With pest sucking device 8 to 10 brown paddy plant hopper III nymphs in age are moved in the test chamber.The container that has connect worm is placed under the temperature and humidity conditions identical with the above.Connect 24 and 48 hours dead, nymph numbers of living of statistics behind the worm.All can not climb then be judged to dead worm.In the compound of being surveyed, cause at 48 hours that with the concentration of 100ppm the compound of examination worm death more than 80% or 80% is: 2,3,4,5,6.
Test I
Inner sucting killing insect activity to black peach aphid
Each test unit is by being grown in Oasis
Figure 931205921_IMG44
The radish seedling in 2 weeks in the wedge (available from Smithers-Oasis Kent Ohion) constitutes.All prematurity leaves of radish seedling are pruned away, stay two main leaves.To the plant inoculation black peach aphid in last 30 to 40 each ages.Connecing worm is to fetch the leaf that has connect worm from former plant, be placed on used two leaves of test or two leaves between.Then plant is placed 22 ℃, 50% relative humidity, 16 hours: (illumination: kept 24 hours in controlled raising chamber dark) in 8 hours.Then the leaf that will inoculate worm is taken away.Every strain plant is a repetition, and four strain plants constitute one group of processing.Then plant is taken away from the growth dish, extrude Oasis
Figure 931205921_IMG45
Unnecessary moisture content in the wedge.The preparation of every kind of test compound stoste is that test compound is dissolved in the 10ml distilled water, if compound not immediately the dissolving use ultrasonication it.The way of using distilled water to add stoste prepares diluent.Plant is placed in the bottle of the testing liquid that fills the given concentration of 10ml then.Place controlled environment as mentioned above to keep 48 hours the plant of handling then.Handle and checked the dead worm on blade face and the filter paper and the borer population of living in back 48 hours, calculate mortality ratio.Appendage actively but the aphid that can not climb, or body colour blackening, or the bodily form is distored all is judged to be dead worm.Mortality ratio is recently represented with the percentage that dead worm accounts for test aphid sum.Four multiple percentage control rates of every kind of processing give on average.Survey in the compound, what cause 80% or 80% above mortality ratio after 48 hours with 100ppm concentration is No. 1 compound.

Claims (9)

1, the compound of following formula
Figure 931205921_IMG2
Wherein
Q is selected from the group of following formula representative
Figure 931205921_IMG3
Y is selected from halogen and R 1X;
X is selected from S (O) n, O and NR 5
R 1Be selected from C 1-C 20Alkyl, C 3-C 10Cycloalkyl, C 4-C 7Cycloalkylalkyl, C 2-C 6Alkenyl, C 2-C 6Alkynyl, above-mentioned each group can at random be replaced by 1 or 2 group that is independently selected from following groups: CN, NO 2, OH, C 1-C 4Alkoxyl group, OC (O) R 6, OCO 2R 6, OS (O) 2R 6, SH, C 1-C 4Alkylthio, C (O) R 6, C (O) OR 6, CO 2H, SO 3H, N (R 7) R 8, C (O) N (R 7) R 8, OS (O) 2N (R 7) R 8, C (S) N (R 7) R 8, C 1-C 4Alkylamino, C 2-C 6Dialkyl amido, S (O) 2N (R 7) R 8, Si (R 9) (R 10) R 11, C 1-C 4Alkyl sulfinyl, C 1-C 4Alkyl sulphonyl, by R 12Any phenyl that replaces, and one five yuan or hexavalent saturated, part is unsaturated or complete undersaturated heterocycle, this heterocycle contains 1-4 heteroatoms independently separately, these heteroatomss are independently selected from 0-1 0,0-1 S and 0-4 N, each heterocycle all can be by R 12Replace arbitrarily; H; C 1-C 6Haloalkyl; C 3-C 7Halogenated cycloalkyl; C 4-C 7The halogenated cycloalkyl alkyl; C (O) N (R 7) R 8SO 2R 6SO 2N (R 7) R 8C (S) N (R 7) R 8C (O) R 6CO 2R 6C (S) R 6C (S) OR 6C (S) SR 6C (O) SR 6By R 12Any phenyl that replaces; Five yuan or hexavalent saturated, part is unsaturated or complete undersaturated heterocycle, this heterocycle contains 1-4 heteroatoms, these heteroatomss are independently selected from 0-1 0, a 0-1 S and 0-4 N, each heterocycle all can be by R 12Replace arbitrarily; Condition is: (ⅰ) when X be NR 5The time, R 1And R 5Can merge into arbitrarily-CH 2CH 2CH 2CH 2-,-CH 2CH 2OCH 2CH 2-, perhaps-CH 2CH 2CH 2CH 2CH 2-; (ⅱ) when X be S (O) nAnd when n=1 or n=2, R then 1Not H, C (S) N (R 7) R 8, C (O) R 6, CO 2R 6, C (S) OR 6, C (S) SR 6, C (O) SR 6, C (O) N (R 7) R 8, SO 2N (R 7) R 8Or S (O) 2R 6
R 2Be selected from H and C 1-C 3Alkyl;
R 3Be selected from H and CH 3Perhaps
R 2And R 3Be merged together to form and be selected from CH 2CH 2, CH (CH 3) CH 2, CH 2CH 2CH 2And CH (CH 3) CH 2CH 2Group, when Q is Q-2, Q-3, when Q-4 or Q-5, this group then is CH (CH 3) CH 2Or CH (CH 3) CH 2CH 2
R 4Be selected from H, CH 2CN, C 1-C 4Alkyl, C 1-C 4Haloalkyl, formyl radical, C 2-C 4Alkyl carbonyl, C 2-C 4Carbalkoxy, C 2-C 4Alkoxyalkyl, C 3-C 6The dialkoxy alkyl, C 1-C 3Alkoxyl group, C 1-C 3Alkyl sulphonyl, C 2-C 4Alkenyl, C 2-C 4Alkynyl, C 1-C 4Alkylamino, C 2-C 4Dialkyl amido and by R 12Any benzyl that replaces;
R 5Be selected from H, C 1-C 6Alkyl, CHO, C 2-C 4Alkyl-carbonyl, C 2-C 4Carbalkoxy and C 1-C 4Alkyl sulphonyl, condition is: work as R 5During for H, R 2, R 3And R 4Not not H just;
R 6Be selected from C 1-C 15Alkyl, C 2-C 6Alkenyl and C 1-C 6Haloalkyl, these groups of representative all can be replaced arbitrarily by phenyl, and phenyl can be by R 12Replace arbitrarily; By R 12Any phenyl that replaces; Five yuan or hexavalent saturated, part is undersaturated or undersaturatedly fully contain 1-4 heteroatomic heterocycle, these heteroatomss are selected from 0-1 O independently of one another, 0-1 S and 0-4 N, each heterocycle all can be by R 12Replace arbitrarily;
R 7And R 8Be selected from H independently of one another, C 1-C 6Alkyl and C 3-C 6Cycloalkyl;
R 9, R 10And R 11Be selected from C independently of one another 1-C 4Alkyl, C 1-C 4Alkoxyl group and phenyl;
R 12Be selected from 1-5 halogen, C 1-C 2Alkyl, C 1-C 2Haloalkyl, C 1-C 2Alkoxyl group, C 1-C 2Alkylthio, C 1-C 2Halogenated alkylthio, C 1-C 2Halogenated alkoxy, NO 2And CN;
N represents 0,1 or 2.
2, the compound of claim 1, wherein:
Y is R 1X;
X is S;
R 1Be selected from C 1-C 6Alkyl, C 3-C 7Cycloalkyl, C 4-C 7Cycloalkylalkyl, C 2-C 3Alkenyl and C 2-C 3Alkynyl, above-mentioned each group can be selected from CN, C 1-C 4Alkylthio and C(O) OR 6Group replace arbitrarily;
R 4Be selected from H and CH 3
3, the compound of claim 1, wherein:
Y is R 1X;
X is S;
R 1Be five yuan or hexa-atomic saturated, part is undersaturated or undersaturatedly fully contain 1-4 heteroatomic heterocycle, these heteroatomss can be independently selected from 0-1 0,0-1 S, 0-4 N, each heterocycle all can be by R 12Replace arbitrarily;
R 12Be selected from 1-5 halogen, C 1-C 2Alkyl and C 1-C 2Alkylthio.
4, the compound of claim 2, wherein Q is Q-1.
5, the compound of claim 3, wherein Q is Q-1.
6, the compound of claim 2, wherein Q is selected from Q-2, Q-3, Q-4 and Q-5, R 2And R 3Common formation is selected from CH(CH 3) CH 2And CH(CH 3) CH 2CH 2Group, wherein terminal CH 2Carbon connecting and having R 4Nitrogen-atoms.
7, the compound of claim 3, wherein Q is selected from Q-2, Q-3, Q-4 and Q-5, R 2And R 3Common formation is selected from CH(CH 3) CH 2And CH(CH 3) CH 2CH 2Group, wherein terminal CH 2Carbon connecting and having R 4Nitrogen-atoms.
8, a kind of insect-killing composition, said composition contain any compound and carrier thereof among the claim 1-7 that kills the arthropod significant quantity.
9, the arthropodan method of a kind of control comprises with any compound among the claim 1-7 of insecticidal effective dose and handles arthropods or its living environment.
CN 93120592 1992-11-24 1993-11-24 Nitroethylene two amines of using as sterilant Pending CN1088913A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US98083092A 1992-11-24 1992-11-24
US980,830 1992-11-24

Publications (1)

Publication Number Publication Date
CN1088913A true CN1088913A (en) 1994-07-06

Family

ID=25527878

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 93120592 Pending CN1088913A (en) 1992-11-24 1993-11-24 Nitroethylene two amines of using as sterilant

Country Status (3)

Country Link
CN (1) CN1088913A (en)
AU (1) AU5611094A (en)
WO (1) WO1994012491A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669660A (en) * 2014-11-20 2016-06-15 华东理工大学 Nitrogenous heterocyclic compound and use thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3717837A1 (en) * 1987-05-27 1988-12-08 Bayer Ag HETEROCYCLIC SUBSTITUTED 2- (1'-NITROALKYLIDES) -1,3-HETEROCYCLES
IL94027A (en) * 1989-04-14 1995-03-15 Takeda Chemical Industries Ltd Diaminoethylene compounds, process for their preparation and insecticidal compositions containing them.
MY106503A (en) * 1989-12-28 1995-06-30 Ishihara Sangyo Kaisha Imidazolidine derivatives, process for producing the same and pesticides containing the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669660A (en) * 2014-11-20 2016-06-15 华东理工大学 Nitrogenous heterocyclic compound and use thereof
CN105669660B (en) * 2014-11-20 2019-07-19 华东理工大学 Nitrogen-containing heterocycle compound and application thereof

Also Published As

Publication number Publication date
WO1994012491A1 (en) 1994-06-09
AU5611094A (en) 1994-06-22

Similar Documents

Publication Publication Date Title
CN1059672C (en) 1,2,4-oxadiazole derivatives and their use as parasiticides for animals
CN1192651A (en) Compositions for combatting ectoparasites
JP3597194B2 (en) Arthropodic oxazolines and thiazolines
CN1054854C (en) Insecticidal tetrahydrofuran-compound
CN1173172A (en) Insecticidal and acaricidal oxaxolines and thiazolines
CN87103168A (en) The pyrimidines that replaces
CN1918144A (en) Anthranilamide-based compound, method for producing the same, and pest-controlling agent containing the same
CN1098093A (en) The amides of Arthropodicidal
CN1100768C (en) Substituted diphenyl oxazolines
CN85109754A (en) The preparation method of organo phosphorous compounds
CN1113238A (en) Substituted pyrazoline derivatives
CN1088913A (en) Nitroethylene two amines of using as sterilant
CN1023476C (en) Process of preparing trifluoromethylvinyl derivatives starting with appropriate halogenovinyl derivatives
CN1071322C (en) Process for producing 5,6-dihydro-1,3-oxazines
CN1059671C (en) 3-aryl akenyl-1,2,4-oxadiazole derivatives and their use as parasiticides for animals
CN1143957A (en) Arthropodicidal 2-oxa and thia-zolines
CN1078233A (en) The pyrazole sulfonates class of Arthropodicidal
CN1042630C (en) Substituted AZA(Cyclo)Alkanes
CN1079462A (en) New 7-ethynyl-α-(methoxyl group methylene radical)-1-naphthylacetic acid derivant and preparation method thereof and as sterilant
CN1072410A (en) Arthropodicidal and nematicide sulphonate
CN1079217A (en) Tool saves the aryl sulfonate of sufficient active animal extremely
KR19990064197A (en) Live arthritic oxazoline and thiazoline
CN1140452A (en) Arthropodicidal tetrahydropyrimidines
CN1077451A (en) The nitroethylene class and the nitrofuanidine of Arthropodicidal
JPH08500605A (en) Arthropodicidal tetrahydropyrimidines

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication