CN1175248A - 4 -aryl -and 4 -heteroaryl -5 -oxopyrazoline derivatives having pesticidal properties - Google Patents

4 -aryl -and 4 -heteroaryl -5 -oxopyrazoline derivatives having pesticidal properties Download PDF

Info

Publication number
CN1175248A
CN1175248A CN95197652A CN95197652A CN1175248A CN 1175248 A CN1175248 A CN 1175248A CN 95197652 A CN95197652 A CN 95197652A CN 95197652 A CN95197652 A CN 95197652A CN 1175248 A CN1175248 A CN 1175248A
Authority
CN
China
Prior art keywords
base
group
alkyl
wan
compound
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
CN95197652A
Other languages
Chinese (zh)
Inventor
M·伯格
P·马恩费施
F·塞德巴姆
T·皮特纳
P·J·纳德卡尼
V·S·埃库恩迪
S·U·库尔卡尼
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.)
Novartis AG
Original Assignee
Novartis AG
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 Novartis AG filed Critical Novartis AG
Publication of CN1175248A publication Critical patent/CN1175248A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic 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
    • C07D401/02Heterocyclic 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
    • C07D401/12Heterocyclic 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 chain containing hetero atoms as chain links
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/28Two oxygen or sulfur atoms
    • C07D231/30Two oxygen or sulfur atoms attached in positions 3 and 5
    • C07D231/32Oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D487/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04Ortho-condensed systems

Abstract

The present invention relates to novel, pesticidally effective, 4-aryl- and 4-heteroaryl-5-oxo-pyrazoline derivatives of formula (I), in which R1, R2, R3 and G are as defined in claim 1, to compositions comprising these compounds, to their use as insecticides, acaricides or herbicides, especially in crops of useful plants, and to selective-herbicidal compositions comprising compounds of formula (I) and, as safeners, herbicide-antagonistically effective quantities of either a quinoline derivative of formula (X), in which R15 and X2 are as defined in the description, or a 1-phenylazole-3-carboxylic acid derivative of formula (XI), in which E, R16, R17, R18 and R19 are as defined in the description.

Description

Has the 4-aryl of pesticidal properties-and 4-heteroaryl-5-oxopyrazoline derivatives
The present invention relates to the 4-aryl of novel pesticide activity-and 4-heteroaryl-5-oxopyrazoline derivatives, relate to its preparation method, comprise the composition of these compounds as active substance, and relate to it as agricultural chemicals, particularly sterilant, miticide or herbicide applications.
Have desinsection, kill the 4-aryl-5-oxopyrazoline of mite and herbicide effect and 4-aryl-and 4-heteroaryl pyrazolidine-3, the 5-diketone is known, and for example is described among the EP-A-0 508 126 and WO-92/16510.
Have now found that the 4-aryl of the novelty with pesticidal properties-and 4-heteroaryl-5-oxopyrazoline derivatives, they have very outstanding excellent activity.
The compounds of this invention Shi Xia Shi compoundQi Zhong R1The Shi group
Figure A9519765200172
Qu is for basic R4Xiang is basic, the C of Shi halogen, Xiao base, Qing independently mutually1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 10-alcoxyl base, C1-C 4-halogenated alkoxy, C3-C 6-alkenyloxy, C1-C 4-alcoxyl base-C2-C 4-alcoxyl base, C3-C 6-Que Yang base, C1-C 4-Wan base Tang base, C1-C 4-alcoxyl Tang base, C1-C4-Wan sulfenyl, C1-C 4-Wan base sulfinyl, C1-C 4-Wan base sulfonyl, amino, C1-C 4-Wan base amino or two (C1-C 4-Wan yl) amino; R5The Shi group
Figure A9519765200181
N Shi 0,1,2,3 or 4; M Shi 0 or 1, Qie m is Yu n Zhi and Shi 0,1,2,3 or 4; Q Shi 0,1,2 or 3; X1Shi Yang, sulphur ,-CH2-or-N (R7)-; Qu is for basic R6Xiang is Shi C independently mutually1-C 4-Wan base, halogen, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, Xiao base, Qing are basic, C1-C 4-alcoxyl base Tang base, amino, C1- C 4-Wan base amino or two (C1-C 4-Wan yl) amino; R7Shi Qing, C1-C 4-Wan base, formoxyl or C1-C 4-alcoxyl Tang base; R2And R3Xiang is Shi Qing, C independently mutually1-C 8-Wan base, C3-C 8-alkenyl, C3-C 8-alkynyl, C1-C 8-alcoxyl base Wan base, C1-C 8-Wan sulfenyl Wan base, C3-C 8-cycloalkyl or Qu generation or unsubstituted aryl; Or R2And R3That Yi Qi Xing becomes is saturated or unsaturated, Wei Qu generation or Qu generation single, two, the divalent group of San or polycyclic system, Zhe Xie Ti Xi can Ren Xuan Zai not Yu the nitrogen-atoms Xiang neighbour's of Shi Yu Shi I Wei Zhi Shang contain Yi or a plurality of ring hetero atom; G Shi group-CO-A (a) or-SO2-B (b); A Shi C1-C 8-Wan base, Ta You Xiao is basic, Qing is basic, Si (C1-C 4-Wan yl)3, amino, C1-C 4-Wan base is amino, two (C1-C 4-Wan yl) amino, Qu generation or unsubstituted benzyloxy or group
Figure A9519765200182
Qu generation, or A Shi C3-C 8-cycloalkyl, Ru fruit Xu Yao, Ta can contain Za elemental oxygen, sulphur or nitrogen, and this cycloalkyl of Qie can You C1-C 4-Wan base, C1-C 4-alcoxyl base, C1-C 4-Wan sulfenyl, C1-C 4-Wan base sulfinyl, C1-C 4-Wan base sulfonyl or Qu generation or unsubstituted phenyl substituted, or A Shi C3-C 8-cycloalkyl oxy, Ru fruit Xu Yao, Ta can contain Za elemental oxygen, sulphur or nitrogen, and this cycloalkyl of Qie can You C1-C 4-Wan base Qu generation, or A Shi gold steel Wan base, Nai are basic, You halogen, C1-C 4-Wan base, C1-C 4-haloalkyl or C1-C 4The Nai base in-alcoxyl base Qu generation, or A Shi group-(CR8R 9) p-(Y) o-CO- (Z) r -R 10 、-(CR 8R 9) p-R 11Or-N (R10)R 13;R 08、R 09And R010Xiang is Shi Qing or C independently mutually1-C 6-Wan base; R8And R9Xiang is Shi Qing, C independently mutually1-C 6-Wan base or phenyl; R10Shi Qing, C1-C 10The C in-Wan base, You halogen Qu generation1-C 10-Wan base, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, C3-C 12-cycloalkyl, Qing base, aryl or aryloxy group, C3-C 8-cycloalkyl, You halogen or C1-C 4The C in-Wan base Qu generation3-C 8-cycloalkyl, C3-C 10-alkenyl, C3-C 10-alkynyl, C3-C 10-halogenated alkenyl, C3-C 10-halo alkynyl, aryl, You Xia row Qu are for basic Qu aryl halogen, the C in generation1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 6-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, phenoxy group or halogenated phenoxy; O and r Xiang be Shi 0 or 1 independently mutually; Y and Z Xiang be Shi Yang or NR independently mutually12 P Shi 1 is Zhi 10; R11Shi C3-C 8-cycloalkyl, You halogen or C1-C 4The C in-Wan base Qu generation3-C 8-cycloalkyl, aryloxy group, You halogen, C1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, phenoxy group or aryloxy group, benzyloxy, You halogen, the C in halogenated phenoxy Qu generation1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, phenoxy group or benzyloxy, norborny or the golden steel Wan base in halogenated phenoxy Qu generation, the aryloxy group of Qi Zhong except phenoxy group, the aryloxy group that each can what Suo Xu of Shi Ren; R12Shi Qing, C1-C 4-Wan base, C3-C 8-cycloalkyl, C3-C 10-alkenyl or C3-C 10-alkynyl; R13Shi C3-C 8-cycloalkyl, You halogen or C1-C 4The C in-Wan base Qu generation3-C 8-cycloalkyl or Qing base-C1-C 6-Wan base; B Shi C1-C 10-Wan base, Ta You Xia row Qu is for basic Qu generation: C1-C 4-alcoxyl base, C1-C 6-alcoxyl base-C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, C1-C 4-halogenated alkylthio, C1-C 4-Wan base sulfinyl, C1-C 4-Wan base sulfonyl, C1-C 4-Wan base sulfonyloxy, C1-C 4-Wan base Tang base, C1-C 4-alcoxyl base Tang base, C1-C 4-Wan base Tang Yang base, two (C1-C 4-Wan yl) amino, C3-C 8-cycloalkyl, aryl, aryloxy group, arylthio, aryl sulfonyl, aryl sulfonyl kia, aryl-sulfonyl oxygen, aryl carbonyl or Bi Ding base, Ru fruit Xu Yao, aryl or Bi Ding base can You Xia row Qu for basic Qu generation: halogen, C1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, phenoxy group, halogenated phenoxy, thiophenyl or halogeno-benzene sulfenyl, or B Shi C3-C 10-alkenyl, C3-C 10-halogenated alkenyl, C3-C 10-alkynyl, C3-C 10-halo alkynyl, C3-C 8-cycloalkyl, You halogen or C1-C 4The C in-Wan base Qu generation3-C 8-cycloalkyl, Bian base, You halogen, C1-C 4-Wan base, C1-C 4-haloalkyl or C1-C 4The Bian base in-alcoxyl base Qu generation, Nai are basic, You halogen or the Nai base in Xiao base Qu generation, or B Shi group-N (R21)R 22; R 21Shi C1-C 10-Wan base, Ta You Xia row Qu is for basic Qu generation: C1-C 4-alcoxyl base, C1-C 6-alcoxyl base-C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, C1-C 4-halogenated alkylthio, C1-C 4-Wan base sulfinyl, C1-C 4-Wan base sulfonyl, C1-C 4-Wan base sulfonyloxy, C1-C 4-Wan base Tang base, C1-C 4-alcoxyl base Tang base, C1-C 4-Wan base Tang Yang base, two (C1-C 4-Wan yl) amino, C3-C 8-cycloalkyl, aryl, aryloxy group, arylthio, aryl sulfonyl, aryl sulfonyl kia, aryl-sulfonyl oxygen, aryl carbonyl or Bi Ding base; Ru fruit Xu Yao, aryl or Bi Ding base can You Xia row Qu for basic Qu generation: halogen, C1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, phenoxy group, halogenated phenoxy, thiophenyl or halogeno-benzene sulfenyl, or R21Shi C3-C 20-alkenyl, C3-C 20-halogenated alkenyl, C3-C 20-alkynyl, C3-C 20-halo alkynyl, C3-C 8-cycloalkyl, You halogen or C1-C 4The C in-Ji Qu generation3-C 8-cycloalkyl, Bian base or aryl, Ru fruit Xu Yao, but Bian base or aryl You Xia row Qu for basic Qu generation: halogen, C1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, benzoyl, halogeno-benzene formoxyl, phenoxy group or halogenated phenoxy; R22As R21Zhi definition, or Shi C in addition1-C 10-Wan base; Or R21And R22Yu the nitrogen-atoms Yi Qi that Zhi Suo Xiang connects, Xing becomes unsubstituted or single Zhi is trisubstituted, non-aromatic, list or bicyclic heterocycles, and Qi Zhong Qu can Shi C for base1-C 4-Wan base, You halogen, C1-C 4The C of-alcoxyl base, phenyl, benzo dioxo base or trifluoromethyl phenyl substituted1-C 4-Wan base, C1-C 4-alcoxyl base, C1-C 4-alcoxyl base Tang base, C1-C 4-Wan base Tang base, phenyl, You halogen, C1-C 4-Wan base, C1-C 4Phenyl or Bi Ding base, Mi Ding base or the formoxyl in-alcoxyl base, Xiao base or trifluoromethyl Qu generation, and Yan and the diastereoisomer of Shi I compound, Qi Qian Ti Tiao spare Shi, Ru fruit R21And R22Shi Wan base, the Wan base in Ze Zhi Shao Zhe Xie group Zhi Yi Wei Qu generation.
In above-mentioned definition, halogen (halo) is meant iodine, and preferably is meant fluorine, chlorine and bromine.
Unless specialize; alkyl, alkenyl and alkynyl preferably have 1 or be respectively 2 to 8 carbon atoms; and can be straight or branched, this explanation also be suitable for alkyl, alkenyl and the alkynyl part of alkyl tin groups, alkyl silane groups, haloalkyl, alkoxyl group, halogenated alkoxy, alkoxyalkyl, alkoxyl group alkoxyl group, alkenyloxy, alkynyloxy group, alkyl-carbonyl, alkoxy carbonyl, alkylthio, alkenyl thio, alkynes sulfenyl, alkylthio alkyl, alkyl sulphinyl, alkyl sulphonyl, alkylamino and dialkyl amido.
The example that appears at the alkyl in the substituting group definition is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-and the tertiary butyl and isomerized amyl group, hexyl, heptyl and octyl group.Occurred or the alkyl in substituting group preferably has 1-8 carbon atom.
Alkenyl is meant for example allyl group, methacrylic, 1-methyl ethylene or but-2-ene-1-base.Preferred alkenyl is those alkenyls with 2 to 8 carbon atoms of chain length.Alkenyl preferably links to each other with heteroatoms through saturated carbon atom.
The example of alkynyl is propargyl, fourth-2-alkynes-1-base, 2-methyl crotonylene-Ji, fourth-3-alkynes-2-base and penta-4-alkynes-1-base.Preferred alkynyl is those alkynyls with 2 to 8 carbon atoms of chain length.Alkynyl preferably links to each other with heteroatoms through saturated carbon atom.
Haloalkyl preferably has 1 to 8 carbon atom of chain length.Haloalkyl is for example methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoro ethyl, 2-chloroethyl, pentafluoroethyl group, 1,1-two fluoro-2,2,2-three chloroethyls, 2,2,3,3-tetrafluoro ethyl and 2,2, the 2-trifluoroethyl; Preferably trifluoromethyl, difluoro chloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
The halogenated alkenyl that is fit to is by halogen replacement one or alkenyl repeatedly, wherein halogen is bromine, iodine and particularly fluorine and chlorine, the example is 2,2-two fluoro-1-methyl ethylenes, 3-fluorine propenyl, chlorallylene base, 3-bromopropenyl, 2,3,3-trifluoro-propenyl, 2,3,3-tri chloropropene base and 4,4,4-trifluoro but-2-ene-1-base.At the C that replaces 1,2 or 3 time by halogen 3-C 20In the alkenyl, preferably those have the alkenyl of 3 to 5 carbon atoms of chain length.
The halo alkynyl that is fit to is for example by halogen list or polysubstituted alkynyl, and wherein halogen is bromine, iodine and particularly fluorine and chlorine, and embodiment is 3-fluorine proyl, 3-chloroallylene base, 3-propargyl bromide base, 3,3,3-trifluoropropyl alkynyl and 4,4,4-trifluoro fourth-2-alkynes-1-base.In by halogen replacement one or alkynyl repeatedly, preferably those have the alkynyl of 3 to 5 carbon atoms of chain length.
Alkoxyl group preferably has the chain length of 1 to 6 carbon atom.Alkoxyl group is for example methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert.-butoxy and isomerized pentyloxy and hexyloxy; Preferred methoxyl group and oxyethyl group.
Alkyl-carbonyl is ethanoyl and propionyl particularly.
Alkoxy carbonyl is methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, n-butoxy carbonyl, isobutoxy carbonyl, sec-butoxy carbonyl and tert-butoxycarbonyl; Methoxycarbonyl and ethoxy carbonyl are preferred.
Halogenated alkoxy preferably has the chain length of 1 to 8 carbon atom.Halogenated alkoxy is for example fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, 2,2,2-trifluoro ethoxy, 1,1,2,2-tetrafluoro oxyethyl group, 2-fluorine oxyethyl group, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-three chloroethoxies; Difluoro-methoxy, 2-chloroethoxy and trifluoromethoxy are preferred.
Alkylthio preferably has the chain length of 1 to 8 carbon atom.Alkylthio is for example methylthio group, ethylmercapto group, rosickyite base, iprotiazem base, positive butylthio, secondary butylthio or uncle's butylthio; Preferred methylthio group and ethylmercapto group.
Alkyl sulphinyl is methylsulfinyl, ethyl sulfinyl, propyl group sulfinyl, sec.-propyl sulfinyl, normal-butyl sulfinyl, isobutyl-sulfinyl, sec-butyl sulfinyl, tertiary butyl sulfinyl; Preferable methyl sulfinyl and ethyl sulfinyl.
Alkyl sulphonyl is methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, sec.-propyl alkylsulfonyl, normal-butyl alkylsulfonyl, isobutyl-alkylsulfonyl, sec-butyl alkylsulfonyl or tertiary butyl alkylsulfonyl; Preferable methyl alkylsulfonyl and ethylsulfonyl.
The alkoxyl group alkoxyl group preferably has the chain length of 1 to 8 carbon atom.The example of alkoxyl group alkoxyl group is methoxymethoxy, methoxy ethoxy, methoxy propoxy oxyethyl group methoxy base, ethoxy ethoxy, propoxy-methoxyl group and butoxy butoxy.
Alkylamino is for example methylamino-, ethylamino, n-propylamine base, isopropylamino and isomerized fourth amino.
Dialkyl amido is for example dimethylamino, first and second amino, diethylamino, n-propyl-methylamino, dibutylamino and diisopropylaminoethyl.The alkylamino that preferably has 1 to 4 carbon atom chain length.
Alkoxyalkyl preferably has the chain length of 1 to 8 carbon atom.Alkoxyalkyl is for example methoxymethyl, methoxy ethyl, ethoxyl methyl, ethoxyethyl group, n-propoxymethyl, positive propoxy ethyl, isopropoxy methyl and isopropoxy ethyl.
Alkylthio alkyl preferably has the chain length of 1 to 8 carbon atom.Alkylthio alkyl is for example methylthiomethyl, methylmercaptoethyl, ethylmercapto group methyl, ethylmercapto group ethyl, positive rosickyite ylmethyl, positive rosickyite base ethyl, iprotiazem ylmethyl, iprotiazem base ethyl, butylthio methyl, butylthio ethyl or butylthio butyl.
Cycloalkyl preferably has 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.These cycloalkyl can be inserted heteroatoms such as Sauerstoffatom and/or sulphur atom and/or nitrogen-atoms if desired.Similar note is suitable for cycloalkyl oxy.
Phenyl, or itself is as such as substituent parts such as phenoxy group, benzyl, benzyloxy, benzoyl, thiophenyl, benzene alkyl or phenoxyalkyls, can be not replace or replace usually.Under latter event, substituting group can adjacent, and/or contraposition on.The preferred substituted position is to be adjacent and right position for the ring connection site.Preferred substituted is halogen, nitro, cyano group, C 1-C 4-alkoxyl group, C 1-C 4-halogenated alkoxy, C 1-C 4-alkylthio, C 1-C 4-halogenated alkylthio, C 1-C 4-alkyl and C 1-C 4-haloalkyl.
In radicals R 2, R 3And R 10Definition in aryl be α-or betanaphthyl, particularly phenyl, its aromatic ring can carry one or more identical or different substituting group, substituent example is halogen, nitro, cyano group, C 1-C 4-alkoxyl group, C 1-C 4-halogenated alkoxy, C 1-C 4-alkylthio, C 1-C 4-halogenated alkylthio, C 1-C 4-alkyl and C 1-C 4-haloalkyl.Corresponding note is suitable in radicals R 10, R 11, R 21, R 22With aryloxy, arylthio, aryl sulfonyl, aryl sulfonyl kia, aryl-sulfonyl oxygen and the aryl carbonyl among the B.
Unsubstituted or single to trisubstituted, non-aromatics, list or bicyclic heterocycles, they are substituent R 11And R 22With nitrogen-atoms that they connected can form, their example is for example 1-pyrrolidyl, piperidino, 2,6-dimethyl-piperidino, 4-morpholinyl, 4-methylpiperazine-1-base, 4-phenylpiperazine-1-base, 4-benzyl diethylenediamine-1-base, 4-(3, the 4-dichlorophenyl) piperazine-1-base, 4-thio-morpholinyl, 2,6-dimethyl-4-morpholinyl, 2,6-diformazan sulfenyl-4-morpholinyl, 1,2,3,4-tetrahydroquinoline-1-base or indoline-1-base.
Saturated or unsaturated, do not replace or replace single, two, three or polycyclic system, they are substituent R 2And R 3With two nitrogen-atoms of the pyrazoline ring that they connected can form, their example for example is:
These member ring systems can be replaced by following substituting group: halogen, C 1-C 16-alkyl, C 1-C 16-haloalkyl, C 2-C 16-alkenyl, C 1-C 16-alkoxy-C 2-C 6-alkyl, C 1-C 6-many alkoxy-Cs 2-C 6-alkyl or phenyl or benzyl, described phenyl or benzyl are not replace or replaced by following substituting group: halogen, nitro, C 1-C 4-alkyl, C 1-C 3-alkoxyl group or C 1-C 3-haloalkyl; And R 14Be halogen or do not replace or halogenated C 1Or C 2-alkoxyl group.
Corresponding connotation also can be given the substituting group of combination definition aspect, for example halogenated alkoxy, halogenated alkylthio, alkoxyl group alkoxyl group, alkoxy carbonyl, alkyl-carbonyl, alkyl sulphinyl, alkyl sulphonyl, alkenyloxy, alkynyloxy group, alkenyl thio, alkynes sulfenyl and cycloalkyl sulfenyl.
The present invention comprises formula I compound and the sour salt that can form equally.The acid that is suitable for forming acid salt is organic and mineral acid.These sour examples are spirit of salt, Hydrogen bromide, nitric acid, various phosphoric acid, sulfuric acid, acetate, propionic acid, butyric acid, valeric acid, oxalic acid, propanedioic acid, fumaric acid, organic sulfuric acid, lactic acid, tartrate, citric acid and Whitfield's ointment particularly.
The salt that contains the formula I compound of acidic hydrogen is for example in the definition of substituent A as by R wherein 010It is the group of hydrogen
Figure A9519765200252
The C that replaces 1-C 8In-the alkyl, also can be an alkali metal salt, for example sodium salt and sylvite; Alkaline earth salt, for example calcium salt and magnesium salts; Ammonium salt, promptly unsubstituted ammonium salt and list or polysubstituted ammonium salt and the salt that forms with other organic nitrogen(ous) base.
Correspondingly, the salt formation thing that is fit to is alkali metal hydroxide and alkaline earth metal hydroxides, particularly lithium hydroxide, sodium, potassium, magnesium or calcium, particularly importantly its sodium or sylvite.
The example that is suitable for forming the amine of ammonium salt not only comprises ammonia, also comprises primary, the second month in a season and uncle C 1-C 18-alkylamine, C 1-C 4-hydroxyalkyl amine and C 2-C 4-alkoxyalkyl amine, methylamine for example, ethamine, Tri N-Propyl Amine, Isopropylamine, four kinds of isomerized butylamine, n-amylamine, isobutylcarbylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, pentadecyl amine, hexadecylamine, heptadecyl amine, octadecylamine, thyl methyl amine, methyl isopropyl amine, tuaminoheptane, the methyl nonyl amine, methyl pentadecyl amine, the methyl octadecylamine, ethyl butyl amine, the ethyl heptyl amice, the ethyl octylame, the hexyl heptyl amice, the hexyl octylame, dimethyl amine, diethylamide, di-n-propylamine, Diisopropylamine, Di-n-Butyl Amine, two n-amylamines, di-iso-amylamine, dihexylamine, two heptyl amices, Di-Octyl amine, thanomin, n-propyl alcohol amine, Yi Bingchunan, N, the N-diethanolamine, the N-ethylpropanolamine, the N-butylethanolamine, allyl amine, n-butene base-2-amine, positive amylene-2-amine, 2,3-dimethyl butyrate thiazolinyl-2-amine, dibutene base-2-amine, n-hexylene-2-amine, the propenyl diamines, Trimethylamine, triethyamino, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, tri-isobutylamine, three TERTIARY BUTYL AMINE, tri-n-amyl amine, methoxyethyl amine and ethoxy ethyl amine; Heterocyclic amine for example pyridine, quinoline, isoquinoline 99.9, morpholine, N-methylmorpholine, thiomorpholine, piperidines, tetramethyleneimine, indoline, rubane and azepine _; Uncle's arylamines such as aniline, anisidine, phenetidine, o-, m-and p-Tolylamine, phenylenediamine, p-diaminodiphenyl, naphthylamines and o-, m-and p-chlorobenzene are pressed; Particularly triethylamine, Isopropylamine and Diisopropylamine.
In addition, if desired, can form corresponding inner salt, for example under the situation of group A, as by group The C that replaces 1-C 8-alkyl, wherein R 08, R 09, R 010Be hydrogen.
In addition, some substituent R 1, R 4To R 13, and R 2And R 3, this R 2And R 3Can be independent or combination or that linked to each other with them mutually main structure combination, can show chirality.The present invention comprises the various steric isomers of the pure form of optically-active of racemic modification and enrichment.
In the described method of this patent application, unless the formula I compound of asymmetric replacement usually-use chiral precurser-obtain with the form of racemic modification.Steric isomer can be by known method afterwards; split according to physical and chemical performance, for example, after optics soda ash, acid or metal complexes formation salt; fractional crystallization, or by chromatographic process as on the ethanoyl Mierocrystalline cellulose, carrying out high performance liquid chromatography (HPLC).In the present invention, the formula I active substance of indication comprises pure optical isomer and racemic modification and/or diastereoisomer.As independent optical isomer is not had concrete indicating, the structural formula that then provides will be understood that and refers to the racemic mixture that those are produced with specified preparation method.When having aliphatic C=C pair of key, rotamerismization can appear.
Formula I is intended to comprise all possible isomer and composition thereof.
For desinsection and acaricidal action, what should emphasize is following formula I compound: preferred formula I compound is R wherein 1It is group
Figure A9519765200271
Compound.In these compounds, particularly preferably be following compound: R wherein 4Be fluorine, chlorine or C 1-C 4-alkyl; N is 1,2 or 3; And m is 0.
In these compounds, compound very particularly preferably is such compound: R wherein 4Be fluorine, chlorine or methyl; N is 2 or 3.
Equally, preferably also has such compound: R wherein 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-.
Equally, preferably compound is that wherein G is the compound of group-CO-A (a).In these compounds, particularly preferably be such compound: wherein A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10,-(CR 8R 9) p-R 11Or-N (R 10) R 13, replace or unsubstituted naphthyl.
In these compounds, very particularly preferably be such compound: R wherein 8And R 9Be hydrogen or methyl independently of each other; And p is 1 or 2.
In these compounds, very particularly preferably be R wherein 8And R 9It is the compound of methyl.
Equally, particularly preferably be such compound: R wherein 10Be C 1-C 8-alkyl, preferred C 1-C 4-alkyl, C 3-C 6-cycloalkyl, phenyl, the phenyl or the naphthyl that replace by halogen; R 11Be C 3-C 8-cycloalkyl, benzyloxy, by halogen, C 1-C 4-alkyl, C 1-C 4Benzyloxy or naphthyloxy that-haloalkyl or phenoxy group replace; And R 13Be C 3-C 7-cycloalkyl or cyano group-C 1-C 6-alkyl.
Other particularly preferred compound be those wherein Y and Z are NR 12Compound.In these compounds, particularly preferably be those wherein R 12Be hydrogen or C 1-C 4The compound of-alkyl.
Equally, particularly preferred compound is such compound: R wherein 8And R 9Be hydrogen or methyl independently of each other; And p is 1 or 2; R 10Be C 1-C 4-alkyl, C 3-C 6-cycloalkyl, phenyl, the phenyl or the naphthyl that replace by halogen; R 11Be C 3-C 6-cycloalkyl, benzyloxy, by halogen, C 1-C 4-alkyl, C 1-C 4Benzyloxy or naphthyloxy that-haloalkyl or phenoxy group replace; Y and Z are NR 12R 12Be hydrogen or C 1-C 4-alkyl; And R 13Be C 3-C 8-cycloalkyl or cyano group-C 1-C 6-alkyl.
Preferred compound is such compound: R wherein 1It is group
Figure A9519765200281
R 4Be fluorine, chlorine or C 1-C 4-alkyl; N is 1,2 or 3; And m is 0; R 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-, (CH 2) 4-or-(CH 2) 3-; G is group-CO-A (a); A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10,-(CR 8R 9) p-R 11Or-N (R 10) R 13, or replacement or unsubstituted naphthyl; R 8And R 9Be hydrogen or methyl independently of each other; And p is 1 or 2; R 10Be C 1-C 4-alkyl, C 3-C 6-cycloalkyl, phenyl, the phenyl or the naphthyl that replace by halogen; R 11Be C 3-C 8-cycloalkyl, benzyloxy, by halogen, C 1-C 4-alkyl, C 1-C 4Benzyloxy or naphthyloxy that-haloalkyl or phenoxy group replace; And R 13Be C 3-C 8-cycloalkyl or cyano group-C 1-C 6-alkyl.
For herbicidal performance, preferred formula I compound is those wherein R 1It is group
Figure A9519765200291
And m is 0 compound.In these compounds, particularly preferably be wherein R 4Be C 1-or C 2-alkyl; And n is 1,2 or 3 compound.
In these formulas I compound, very particularly preferably be R wherein 4Be to be 2,4 and 6 C for the connection site of phenyl 1-or C 2-alkyl; And n is 3 compound.
Other preferred compound is those wherein R 1It is group
Figure A9519765200292
And m is 0; R 4Be C 1-or C 2-alkyl; N is 1,2 or 3; R 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-compound.
Equally preferably such compound: wherein G is group-CO-A (a); And A is C 1-C 8-alkyl, it is by nitro, cyano group, Si (C 1-C 4-alkyl) 3, amino, C 1-C 4-alkylamino, two (C 1-C 4-alkyl) amino, replacement or unsubstituted benzyloxy or group
Figure A9519765200293
Replace, or A is C 3-C 8-cycloalkyl, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it can be by C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-alkyl sulphinyl, C 1-C 4-alkyl sulphonyl or replacement or unsubstituted phenyl replace, or A is C 3-C 8-cycloalkyl oxy, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it is unsubstituted or by C 1-C 4-alkyl replaces, or A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10Or-(CR 8R 9) p-R 11Other preferred compound is such compound: R wherein 1It is group
Figure A9519765200301
R 4Be C 1-or C 2-alkyl; N is 1,2 or 3; M is 0; R 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-; G is group-CO-A (a); And A is C 1-C 8-alkyl, it is by nitro, cyano group, Si (C 1-C 4-alkyl) 3, amino, C 1-C 4-alkylamino, two (C 1-C 4-alkyl) amino, replacement or unsubstituted benzyloxy or group
Figure A9519765200302
Replace, or A is C 3-C 8-cycloalkyl, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it can be by C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-alkyl sulphinyl, C 1-C 4-alkyl sulphonyl or replacement or unsubstituted phenyl replace, or A is C 3-C 8-cycloalkyl oxy, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it is unsubstituted or by C 1-C 4-alkyl replaces, or A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10Or-(CR 8R 9) p-R 11
Particularly preferably be formula I compound, wherein R 1Be 2,4,6-trimethylphenyl, R 2With R 3Be together-(CH 2) 4-and G be-C (=O)-N (CH 3) CH 2CH 2CN.
Particularly preferred formula I compound, wherein R in addition 1Be 2,4,6-trimethylphenyl, R 2With R 3-N is-CH together 2CH 2CH (CH 3) CH 2-N and G be-C (=O)-N (CH 3) CH 2CH 2CN.
Also particularly preferably be formula I compound, wherein R 1Be 2,6-dichlorophenyl, R 2With R 3Be together-(CH 2) 4-and G be-C (=O)-N (CH 3) CH 2CH 2CN.
Method according to preparation I compound of the present invention is undertaken by being similar to known method, and described method is when comprising the 4-aryl of a) preparation formula I and 4-heteroaryl-5-oxopyrazoline derivatives
Figure A9519765200311
R wherein 1, R 2And R 3Suc as formula defined under the I, G is that group-CO-A (a) and A are suc as formula defined under the I but be not group-N (R 10) R 13, with formula II compound and the reaction of formula III compound
Figure A9519765200312
R wherein 1, R 2And R 3As defined above, Wherein A as defined above, and E 1Be leaving group, halogen chlorine particularly preferably; B) when the 4-aryl of preparation formula I and 4-heteroaryl-5-oxopyrazoline derivatives
Figure A9519765200314
R wherein 1, R 2And R 3Suc as formula defined under the I, G is that group-CO-A (a) and A are group-N (R 10) R 13, R wherein 10And R 13Define but R suc as formula I is following 10Not hydrogen, with formula II compound and the reaction of formula IV compound
Figure A9519765200315
R wherein 1, R 2And R 3As defined above,
Figure A9519765200321
R wherein 10And R 13As defined above, and E 1Be leaving group, halogen chlorine particularly preferably; Perhaps c) when the 4-aryl of preparation formula I and 4-heteroaryl-5-oxopyrazoline derivatives
Figure A9519765200322
R wherein 1, R 2And R 3Suc as formula defined under the I, G is that group-CO-A (a) and A are group-NHR 13, R wherein 13Define suc as formula I is following, with formula II compound and formula V isocyanate reaction
Figure A9519765200323
R wherein 1, R 2And R 3As defined above,
R 13-N=C=O (V) is R wherein 13As defined above.
Method according to preparation I compound of the present invention
Figure A9519765200324
R wherein 1, R 2And R 3Suc as formula defined under the I, G is group-SO 2-B (b) and B define suc as formula I is following, are to be undertaken by being similar to described currently known methods (for example method described in the EP-A-0 508 126), and described method comprises makes formula II compound R wherein 1, R and R 3Suc as formula defined under the I, react with formula VI compound
B-SO 2-E 1(VI) wherein B as defined above, and E 1Be leaving group such as halogen, particularly chlorine, if desired, be reflected in the solvent and have or alkali-free in the presence of carry out.
Can be similar to known method according to scheme (a) and (b) and (c) reaction carries out, advantageously in solvent to reactionlessness, no hydroxyl, at organic bases such as pyridine, 4-methylamino pyridine, lutidine, collidine, trialkylamine, N, the N-dialkyl aniline, or two the ring non-nucleophilic base as 1,4-diazabicylo [2.2.2] octane (DABCO), 1, in 5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene (DBN) or 1, carry out in 8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU).Reaction is normally carried out under 0 to 120 ℃ temperature, preferred 20 to 90 ℃, advantageously carries out in to the solvent of reactionlessness or solvent mixture.These examples of solvents that are suitable for this purpose are aliphatic series or aromatic hydrocarbon such as benzene, toluene, sherwood oil or hexane; Halohydrocarbon such as chlorobenzene, methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin and tetrachloroethane; Ethers and ether sample compound, as dialkyl ether, for example ether, diisopropyl ether and t-butyl methyl ether, and methyl-phenoxide , diox and tetrahydrofuran (THF); Nitrile such as acetonitrile and propionitrile; Ester class such as ethyl acetate, propyl acetate and butylacetate; Ketone such as acetone, diethyl ketone and methylethylketone; And the mixture of these solvents.
Advantageously under 0 to 150 ℃, preferably under 20 to 70 ℃, equimolar amount ground carries out in the reaction of the reactive sulfonic acid of formula II compound and formula VI.The solvent that is fit to is the conventional polar organic solvent to reactionlessness, for example ethers, amides, nitrile, alcohols, sulfone class or sulfoxide class, particularly dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) or N, dinethylformamide.The acid binding agent that is fit to is known inorganic and organic bases such as sodium hydroxide, yellow soda ash, salt of wormwood or pyridine.Reaction can be carried out under pressurization or particularly normal pressure.If desired, also can carry out under condition of phase transition, in this case, every mole formula II compound is under 0 to 150 ℃, preferably at 20 to 70 ℃ of reactive sulfonic acids that adopt 0.3 to 1.5 mole formula VI down.Operable phase-transfer catalyst is common quaternary ammonium salt such as bromination four octyl group ammonium or benzyltriethylammonium chlorides.In this case, the organic solvent of Shi Heing is all inert non-polar solvent such as benzene or toluene.
Formula II compound, wherein R 1, R 2And R 3Defining suc as formula I is following, is known by EP-A-0 508 126 and WO 92/16510, and can be by disclosed method preparation.
Required formula III, IV, V and VI compound is that commerical prod maybe can be similar to known standard method preparation among the preparation method.
Formula I end product can be used conventional mode, by concentrating and/or the evaporating solvent separation, purifying in the following way: solid residue is difficult in the molten solvent at them, as recrystallization or grinding in ethers, alkanes, aromatic hydrocarbons or the chlorinated hydrocarbons, or through silica gel column chromatography.
The salt of formula I compound can prepare with known mode itself.For example, the acid salt of formula I compound obtains by using acid that is fit to or the ion-exchange agent treated that is fit to, and the salt that is become with alkali then is to obtain by the ion-exchange agent treated of using suitable acid or be fit to.
The salt of formula I compound can be changed the free cpds of accepted way of doing sth I with the mode of routine; For example acid salt is by with alkali reagent that is fit to or suitable ion-exchange agent treated, and the salt that forms with alkali, then by realizing with acid that is fit to or the ion-exchange agent treated that is fit to.
The salt of formula I compound can be used other salt of own known mode conversion type I compound; Acid salt, for example, can change into other acid salt, for example use a kind of suitable metal salt such as sodium, barium or silver salt of acid, for example use silver acetate, handle the salt of mineral acid example hydrochloric acid, processing is to carry out in the solvent that is fit to, and in this solvent formed inorganic salt for example silver chloride be insoluble, therefore and can from reaction mixture, separate.
According to response procedures and condition, the formula I compound that has the salt formation performance can form free with it or salt obtain.
Except separating pure isomer specific synthetic, the product that is obtained can be two or multiple mixture of isomers.Isomer can separate by known method itself.
For comprising formula I compound compositions, the preferable range that is fit to is identical with formula I compound.
The invention still further relates to the dogstail that is used for preventing and treating in plant, particularly corn and the cereal crop and the selective herbicidal composition of weeds, said composition comprises weedicide and safener (counteragent, toxinicide).The plant that the safener protection is useful make it to resist the poisoning effect of weedicide, but it does not have this effect for weeds.The invention still further relates to the application of this composition controlling weeds in crop.
When using weedicide, also may for example depend on the character and time, temperature or the rainfall amount etc. of weather condition of the consumption of weedicide and method of application, crop, soil as being exposed to light, crop there is to a certain degree infringement.
In order to tackle this and similar problem, advised using various materials already as safener.Safener can the antagonism weedicide to the detrimental effect of crop, in other words, safener is implemented protection to crop, make it to preserve from, and with it simultaneously, safener does not but hinder the weeds herbicide effect of weedicide to being intended to prevent and treat.At this on the one hand, have found that the safener of the usefulness of advising has very special effect for crop with for weedicide, and in some cases, depend on the mode of using; In other words, some safeners only are suitable for a concrete crop and weedicide or a kind of concrete weedicide of a particular type usually.For example; EP-A-0 094 349 discloses quinoline; described quinoline cover crop is resisted the poisoning effect of the weedicide of particular type, and the weedicide type is chloroacetanilide, phenoxy propionic acid class, ureas, triazines, amino formate or diphenylether for example.
EP-A-0 558 448 has described 1, and 5-diphenylpypazole-3-carboxylic acid derivative is used to resist the poisoning of sulfonylurea.
Have now found that the safener compounds that is selected from quinoline, pyrazoles or triazole derivative class is suitable for cover crop, make it to resist the 4-aryl of formula I-and the poisoning effect of 4-heteroaryl-5-oxopyrazoline derivatives.
Therefore, according to the present invention, a kind of such selective herbicidal composition is proposed, said composition also comprises following active material admixture: a) as defined above the formula I herbicidal compound and the b of herbicidally effective amount except comprising conventional inertia processing aids such as carrier, solvent and wetting agent) the formula X quinoline of weedicide antagonism significant quantity
Figure A9519765200361
R wherein 15Be hydrogen, C 1-C 8-alkyl or by C 1-C 6-alkoxyl group or C 3-C 6The C that-alkenyloxy replaces 1-C 8-alkyl; And X 2Be hydrogen or chlorine; Or the 1-of formula XI phenylpyrrole-3-carboxylic acid derivative E is nitrogen or methyne; R 16Be-CCl 3Or do not replace or halogenated phenyl; R 17And R 18Be hydrogen or halogen independently of each other; And R 19Be C 1-C 4-alkyl.
Preferred formula I compound is R wherein in composition of the present invention 1It is group
Figure A9519765200371
And m is 0 compound.In these compounds, particularly preferably be radicals R 4Be C 1-or C 2-alkyl; And n is 1,2 or 3 compound.Particularly, in these compounds, particularly preferably be radicals R 4Be to be 2,4 and 6 C for the connection site of phenyl 1-or C 2-alkyl; And n is 3 compound.
Equally, the preferred present composition is in its Chinese style I compound, R 1It is group
Figure A9519765200372
R 4Be C 1-or C 2-alkyl; N is 1,2 or 3; M is 0; R 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-.
Preferably also have such composition, wherein G is group-CO-A (a); And A is C 1-C 8-alkyl, it is by nitro, cyano group, Si (C 1-C 4-alkyl) 3, amino, C 1-C 4-alkylamino, two (C 1-C 4-alkyl) amino, replacement or unsubstituted benzyloxy or group
Figure A9519765200373
Replace, or A is C 3-C 8-cycloalkyl, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it can be by C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-alkyl sulphinyl, C 1-C 4-alkyl sulphonyl or replacement or unsubstituted phenyl replace, or A is C 3-C 8-cycloalkyl oxy, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it is unsubstituted or by C 1-C 4-alkyl replaces, or A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10Or-(CR 8R 9) p-R 11
In addition, preferably such composition, wherein R 1It is group R 4Be C 1-or C 2-alkyl; N is 1,2 or 3; M is 0; R 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-; G is group-CO-A (a); And A is C 1-C 8-alkyl, it is by nitro, cyano group, Si (C 1-C 4-alkyl) 3, amino, C 1-C 4-alkylamino, two (C 1-C 4-alkyl) amino, replacement or unsubstituted benzyloxy or group
Replace, or A is C 3-C 8-cycloalkyl, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it can be by C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-alkyl sulphinyl, C 1-C 4-alkyl sulphonyl or replacement or unsubstituted phenyl replace, or A is C 3-C 8-cycloalkyl oxy, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it is unsubstituted or by C 1-C 4-alkyl replaces, or A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10Or-(CR 8R 9) p-R 11
In addition, preferably such composition, it comprises formula Xa safener
Figure A9519765200383
Equally, preferably such composition, it comprises formula Xb safener
Figure A9519765200391
Preferably also have such composition, it comprises the safener of formula XIa
Figure A9519765200392
Preferred formula X and XI compound are also listed in table 8 and 9.
The quinoline of formula X scope and preparation thereof are known, or they can be by being similar to the preparation of known method, as are described in the method among the EP-A-0 094 349.
1-phenylpyrrole-3-the carboxylic acid derivative of formula XI scope is known and for example is described among the EP-A-0268 554 and EP-A-0 174 562.
In field of pest control, formula I compound of the present invention, even when under lower concentration, using, also be have prevent and/or therapeutic value, have and very advantageously kill biological spectrum and by the well tolerable active substance of warm-blooded animal, fish and plant.Active substance of the present invention is not only to normal responsive animal pest, and all or independent etap of antagonism insect is all effective, the kind of described animal pest such as insect or acarina.The desinsection of active substance of the present invention or acaricidal action can directly kill significantly promptly occurred at that time or over time, the insect that for example between exuvial period, occurs, perhaps indirectly reduce and lay eggs and/or hatching rate, its favourable effect is corresponding at least 50 to 60% (death) rate of killing.
The animal pest that can mention for example comprises: lepidopteran, for example, Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., cotton leaf ripple noctuid (Alabama argillaceae), Amylois spp., Anticarsia (Anticarsia gemmatalis), Archips spp (Archips spp.), Argyrotaenia belongs to (Argyrotaenia spp.), Autographa spp., corn pattern noctuid (Busseolafusca), meal moth (Cadra cautella), peach post fruit moth (Carposinanipponensis), straw borer spp (Chilo spp.), Choristoneura spp., grape codling moth (Clysia ambiguella) (Clysia ambiguella), Cnaphalocrocis spp., Cnephasiaspp., Cochylisspp belongs to (Cochylis spp.), casebearer moth (Coleophora spp.), Crocidolomia binotalis, Cryptophlebia leucotreta (Cryptophlebialeucotreta), Cydia spp., different crambid belongs to (Diatraea spp.), Diparopsis castanea (Diparopsis castanea), Earias spp., meal moth belongs to (Ephestia spp.), the flower steinernema belongs to (Eucosma spp.), Eupoecillia ambiguella, pornography and drug moth (Euproctis spp.), Euxoa spp., Grapholita spp., Hedyanubiferana, genus heliothis (Heliothis spp.), Oeobia undalis (Hellula undalis), fall webworms (Hyphantria cunea), the moth-eaten moth (Keiferia lycopersicella) of tomato, pear leaf blister moth (Leucoptera scitella), thin moth belongs to (Lithocollethis spp.), Lobesia botrana, Euproctis (Lymantria spp.), lyonetid belongs to (Lyonetiaspp.), tent caterpillar (Malacosoma spp.), lopper worm (Mamestra brassicae), maduca sexta (Manduca sexta), winter geometrid moth genus (Operophtera spp.), Pyrausta nubilalis (Hubern). (Ostrinia nubilalis), super steinernema belongs to (Pammene spp.), brown epiblema (Pandemis spp.), small noctuid (Panolis flammea), pink bollworm (Pectinophora gossypiella), potato tuberworm (Phthorimaeaoperculella), small white (Pieris rapae), Pier (Pieris spp.), small cabbage moth (Plutella xylostella), Prays spp., Scirpophaga spp., pink rice borer belongs to (Sesamia spp.), long palpus volume moth belongs to (Sparganothis spp.), mythimna separata belongs to (Spodopteraspp.), Synanthedon spp., the band moth belongs to (Thaumetopoea spp.), Tortixspp., cabbage looper (Trichoplusia ni) and Yponomeuta (Yponomeuta spp.); Coleoptera, for example, click beetle belongs to (Agriotes spp.), Anthonomus spp belongs to (Anthonomus spp.), Atomaria linearis (Atomaria linearis), beet shin flea beetle (Chaetocnema tibialis), root weevil belongs to (Cosmopolites spp.), Curculio (Curculio spp.), khapra beetle belongs to (Dermestesspp.), the chrysomelid genus of bar (Diabrotica spp.), plant ladybug and belong to (Epilachna spp.), Eremnus spp., colorado potato bug (Leptinotarsa decemlineata), Lissorhoptrus spp., Phyllophaga (Melolontha spp.), Orycaephilusspp., the ear beak resembles genus (Otiorhynchus spp.), Phlyctinus spp., rutelian belongs to (Popillia spp.), Psylliodes spp., lesser grain borer belongs to (Rhizopertha spp.), Scarabeidae (Scarabeidae), Sitophilus (Sitophilus spp.), Sitotroga spp., intend ground beetle and belong to (Tenebrio spp.), Tribolium (Tribolium spp.) and spot khapra beetle belong to (Trogoderma spp.); Orthoptera, for example, blattaria belongs to (Blatta spp.), Blatella (Blattella spp.), Gryllotalpa spp (Gryllotalpaspp.), leucophaea maderae (Leucophaea maderae), migratory locusts genus (Locusta spp.), Periplaneta (Periplaneta spp.) and grasshopper and belongs to (Schistocerca spp.); Isoptera, for example, Reticulitermes (Reticulitermes spp.); Corrodentia, for example booklice belongs to (Liposcelis spp.); Anoplura, for example, Haematopinus (Haematopinus spp.), Linognathus (Linognathus spp.), lice belong to (Pediculus spp.), the goitre woolly aphid belongs to (Pemphigus spp.) and Phylloxera spp (Phylloxeraspp.); Mallophaga, for example, Damalinea spp. and Trichodectes (Trichodectes spp.); Thysanoptera, for example, flower thrips belongs to (Frankliniella spp.), Hercinothrips spp belongs to (Hercinothrips spp.), Taeniothrips (Taeniothrips spp.), pale brown thrips (Thrips palmi), cotton thrips (Thripstabaci) and African balloonflower root thrips (Scirtothrips aurantii); Hemiptera, for example, Cimex (Cimex spp.), Distantiella theobroma (Distantiella theobroma), red stinkbug genus (Dysdercus spp.), Euchistus spp., Eurygasterspp genus (Eurygaster spp.), Leptocorisa spp genus (Leptocorisa spp.), Bemisia spp (Nezara spp.), plan lace bug belong to (Piesmaspp.), red abdomen is hunted stinkbug (Phodnius spp.), Sahlbergella singularis (Sahlbergellasingularis), scotinophora lurida genus (Scotinophara spp.) and Triatoma (Triatomaspp.); Homoptera, for example, wolly whitefly (Aleurothrixus floccosus), wild cabbage aleyrodid (Aleyrodesbrassicae), circle helmet a red-spotted lizard belongs to (Aonidiella spp.), Aphidiadae (Aphididae), Aphis (Aphisspp.), Aspidiotus belongs to (Aspidiotus spp.), sweet potato whitefly (Bemisia tabaci), lecanium belongs to (Ceroplaster spp.), Chrysomphalus aonidium (Chrysomphalus aonidium), dictyospermum scale (Chrysomphalus dictyospermi), mango Coccushesperidum (Coccushesperidum), Empoasca spp belongs to (Empoasca spp.), eriosoma lanigerum (Eriosomalarigerum), the erythema leafhopper belongs to (Erythroneura spp.), Gascardia spp., small brown-back rice plant-hopper belongs to (Laodelphax spp.), the hard a red-spotted lizard (Lecanium corni) of water and soil, lepidosaphes belongs to (Lepidosaphes spp.), long tube Aphis (Macrosiphus spp.), knurl volume Aphis (Myzusspp.), rice green leafhopper belongs to (Nephotettix spp.), brown paddy plant hopper belongs to (Nilaparvataspp.), Paratoria spp., the goitre giant coccid belongs to (Pemphigus spp.), Planococcusspp., Pseudaulacaspis spp., mealybug belongs to (Pseudococcus spp.), Psylla spp (Psylla spp.), giant coccid belongs to (Pulvinaria aethiopica), armored scale belongs to (Quadraspidiotus spp.), Rhopalosiphum (Rhopalosiphum spp.), the helmet a red-spotted lizard belongs to (Saissetia spp.), leafhopper belongs to (Scaphoideus spp.), y-bend Aphis (Schizaphisspp.), Sitobion spp., greenhouse whitefly (Trialeurodes vaporariorum), Trioza erytreae and Unaspis citri (Unaspis citri); Hymenoptera, for example, Acromyrmex, leaf cutting ant belong to (Atta spp.), the stem honeybee belongs to (Cephus spp.), saw joint tenthredinidae (Diprion spp.), Diprionidae (Diprionidae), Gilpinia polytoma (Gilpiniapolytoma), real tenthredinidae (Hoplocampa spp.), field ant genus (Lasius spp.), MonomoriumMayr (Monomorium pharaonis), Neodiprion spp., Solenopsis spp. and wasp (Vespa spp.); Diptera, for example, Aedes (Aedes spp.), Antherigona soccata, garden march fly (Bibiohortulanus), calliphora erythrocephala (Calliphora erythrocephala), Ceratitisspp., Carysomyia (Chrysomyia spp.), Culex (Culex spp.), cuterbrid belongs to (Cuterebra spp.), Anastrepha (Dacus spp.), drosophila yellow gorilla (Drosophilamelanogaster), Fannia (Fannia spp.), Gasterophilus (Gastrophilus spp.), Glossina (Glossina spp.), Hypoderma (Hypoderma spp.), Hippobosca (Hyppoboscaspp.), Liriomyza belongs to (Liriomyza spp.), Lucilia (Lucilia spp.), black Hippelates (Melanagromyza spp.), fly belongs to (Musca spp.), Oestrus (Oestrus spp.), Orseolia spp., Sweden's wheat stem chloropid fly (Oscinella frit), spinach leaf mining flowerfly (Pegomyiahyoscyami), Phorbia spp., apple trypetid (Rhagoletis pomonella), the gill fungus fly belongs to (Sciara spp.), Genus Stomoxys (Stomoxys spp.), Gadfly (Tabanus spp.), Tannia spp. and Tipula spp.; Siphonaptera, for example, Ceratophyllus (Ceratophyllus spp.) and Xanthopsyllacheopis (Xenopsylla cheopis); Thysanura, for example, silverfiss (Lepisma saccharina).Acarina, for example, Acarus siro (Acarus siro), tangerine bud goitre mite (Aceria sheldoni), apple thorn goitre mite (Aculus schlechtendali), Amblyomma (Amblyomma spp.), latent beak tick belongs to (Argasspp.), Boophilus (Boophilus spp.), short whisker Acarapis (Brevipalpus spp.), Bryobia praetiosa (Bryobia praetiosa), Calipitrimerus spp., Chorioptes (Chorioptesspp.), thorn Chorioptes (Dermanyssusgallinae), carpinus turczaninowii beginning Tetranychus (Eotetranychuscarpini), Eriophyes (Eriophyes spp.), glass eye tick belongs to (Hyalomma spp.), hard tick belongs to (Ixodes spp.), meadow unguiculus mite belongs to (Olygonychus spp.), blunt beak tick belongs to (Ornithodoros spp.), Panonychus citri belongs to (Panonychus spp.), citrus rust mite (Phyllocoptruta oleivora), Polyphagotarsonemus latus Banks (Polyphagotarsonemuslatus), the scabies mite belongs to (Psoroptes spp.), Rh (Rhipicephalus spp.), the root mite belongs to (Rhizoglyphus spp.), itch mite belongs to (Sarcoptes spp.), tarsonemid mite belongs to (Tarsonemus spp.) and Tetranychus (Tetranychus spp.).
Use active substance of the present invention; can prevent and treat the insect that appears at the type of mentioning on the plant; on the crop and ornamental plant of particularly control agricultural, gardening and forest aspect; or the part of these plants; as these insects on fruit, flower, leaf, stem, stem tuber or the root; in this respect the meaning of control is restriction or kills, and is in some cases growing plants is subsequently partly protected.
The target body crop that is fit to is cereal class such as wheat, barley, rye, oat, rice, corn or jowar particularly; Beet such as sugar beet and fodder beet; Fruit is the operatic circle, drupe and pulpy fruit for example, as apple, pears, plum, peach, almond, cherry and berry such as strawberry, rasp berry or blackberry, blueberry; Bean is as Kidney bean, Lens culinaris, pea or soybean; Oil crops such as rape, mustard, opium poppy, olive, Sunflower Receptacle, coconut, castor-oil plant, cocoa or peanut; Melon as pumpkin, cucumber or watermelon; Fibre crops such as cotton, flax, hemp or jute; Citrus fruit, as citrus, lemon, grape or tangerines; Greengrocery such as spinach, lettuce, Radix Asparagi, wild cabbage, Radix Dauci Sativae, green onion, tomato, potato or big capsicums; Bay section such as avocado, cassia bark or rubber; And tobacco, nut, coffee, eggplant, sugarcane, tea, pepper, grape, hops, Lowiaceae, latex plant and ornamental plant.
Other field that active substance of the present invention is used is protection livestock, warehouse and material and aspect health, particularly protects domestic and the productivity animal, makes it to resist the infringement of the animal pest of described type.
The invention still further relates to agricultural chemicals, described agricultural chemicals is according to target that is intended to and current condition, but missible oil, suspension agent, directly sprays or diluting soln are processed in selection, but but the capsule of brushing paste, dilution emulsion, wettable powder, soluble powder dispersion powder, pulvis, granule or polymkeric substance, and described agricultural chemicals comprises at least a active substance of the present invention.
In these compositions, the active substance that adopts is a purified form, solid active agents for example is specific particle diameter form, or preferably, with at least a auxiliary that is usually used in manufacture field (as weighting agent, for example solvent or solid carrier) or surface active cpd (tensio-active agent) together.
The example of the solvent that is fit to is unmodified or partially hydrogenated aromatic hydrocarbon, the C of preferred alkyl benzene 8To C 12Fraction, as xylene mixture, alkylated naphthalene or tetraline, aliphatic series or cycloaliphatic hydrocarbon such as paraffin or hexanaphthene, alcohols such as ethanol, propyl alcohol or butanols, glycols and ethers thereof and ester class, as propylene glycol, dipropylene glycol, ethylene glycol or ethylene glycol monomethyl ether or single ether, ketone such as pimelinketone, isophorone or Pyranton, intensive polar solvent such as N-methylpyrrolidin-2-ketone, dimethyl sulfoxide (DMSO) or N, dinethylformamide, water, unmodified or the vegetables oil of epoxy groupization such as the rapeseed oil of unmodified or epoxy groupization, Viscotrol C, Oleum Cocois or soybean oil, and polysiloxane oil.
Solid carrier, but for example be used for the solid carrier of pulvis and dispersion powder, and normally used is the natural mineral matter that grinds, as calcite, talcum, kaolin, montmorillonite or attapulgite.For improving the material performance, also can add the silicon-dioxide of high dispersive or the absorbable polymer of high dispersive.Particulate state, the absorbent particles carrier that is fit to be multi-hole type as float stone, brickbat, sepiolite or montmorillonite, and the non-sorptive carriers material that is fit to is calcite or sand.And, can use many inorganic or the granulate material, particularly rhombspar of organic type or the plant residues of grinding.
According to the character of active substance to be processed, suitable surface active cpd is nonionic, positively charged ion and/or anion surfactant, or has the surfactant mixture of well emulsify, dispersion and wettability.The tensio-active agent of listing in hereinafter only should be regarded example as; Pertinent literature has been described many other tensio-active agents, and these tensio-active agents are that manufacture field is used always, and are suitable for the present invention.
The nonionogenic tenside that is fit to mainly is the polyglycol ether derivative of aliphatic series or cycloaliphatic alcohol, saturated or unsaturated fatty acids and alkylphenol, can have 3 to 30 ethylene glycol ether groups in the described derivative and has 8 to 20 carbon atoms and have 6 to 18 carbon atoms at the moieties of alkylphenol on (aliphatic series) alkyl.What be fit to equally is water-soluble affixture, this affixture is the affixture that polyethylene oxide and polypropylene glycol, quadrol polypropylene glycol and alkyl chain have the alkyl polypropylene glycol of 1 to 10 carbon atom, and they contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol groups.For each propylene glycol unit, the compound of being mentioned contains 1 to 5 ethylene glycol unit usually.The example that can mention is nonylphenol polyethoxyethanols, Viscotrol C polyglycol ether, poly(propylene oxide)-polyethylene oxide affixture, tributyl phenoxy group polyethoxyethanols, polyoxyethylene glycol and octylphenoxy polyethoxy ethanol.The fatty acid ester of polyoxyethylene sorbitol acid anhydride, for example polyoxyethylene sorbitan trioleate also is suitable.
Cats product mainly is a quaternary ammonium salt, and they have the alkyl of at least a 8 to 22 carbon atoms and remaining is that rudimentary unmodified or halogenated alkyl, benzyl or rudimentary hydroxyalkyl are as substituting group.These preferred salt are halogenide, Methylsulfate or sulfovinate.Example is chlorination stearyl trimethyl ammonium and bromination benzyl two (2-chloroethyl) ethyl ammonium.
The anion surfactant that is fit to can be water-soluble soap and water-soluble synthetic surface active compound.The soap that is fit to is higher fatty acid (C 10-C 22) basic metal, alkaline-earth metal and replacement or unsubstituted ammonium salt, as oleic acid or stearic sodium or sylvite, or the sodium or the sylvite of (for example obtaining) natural acid mixture that can obtain by coconut or animal oil; Also can should be mentioned that the fatty acid methyl taurate.Yet normally used is synthetic surfactant, particularly fatty sulfonate, fat sulphate, Sulfonated benzimidizole derivatives or alkylaryl sulphonate.Fat sulfonate and fat sulphate be basic metal, alkaline-earth metal or replacement or unsubstituted ammonium salts normally, and has the alkyl of 8 to 22 carbon atoms usually, and alkyl also can comprise the moieties of acyl group; The example that can mention is for example lignosulfonic acid, laurilsulfate or by the sodium or the calcium salt of the fatty alcohol sulphuric acid admixture of natural acid preparation.Also comprise the sulfuric ester of Fatty Alcohol(C12-C14 and C12-C18) ethylene oxide adduct and the salt of sulfonic acid.Sulfonated benzimidizole derivatives preferably contains 2 sulfonic acid groups, and fatty acid group has about 8 to 22 carbon atoms.Alkylaryl sulphonate is sodium, calcium or the tri ethanol ammonium salt of for example Witco 1298 Soft Acid, dibutyl naphthene sulfonic acid or naphthene sulfonic acid-formaldehyde condensation products.Same what be fit to is the phosphoric acid salt that suits, for example to the salt of the phosphide of ethylene oxide adduct of nonylphenol-(4-14) or phosphatide.
Composition contains 0.1 to 99% usually, 0.1 to 95% active substance and 1 to 99.9% particularly, particularly 5 to 99.9% at least a solid or liquid auxiliary agent, usually can have 0 to 25% in the composition, 0.1 to 20% tensio-active agent (% is meant by weight in each case) particularly.Though trending towards in the commerical prod is spissated composition, the end user is then normally used to be the low diluted composition of active material concentration.Preferred compositions (particularly) is by making up following composition the (%=weight percent): missible oil: active substance: 1 to 90%, preferred 5 to 20% tensio-active agents: 1 to 30%, preferred 10 to 20% solvents: 5 to 98%, preferred 70 to 85% pulvis: active substance: 0.1 to 10%, preferred 0.1 to 1% solid carrier: 99.9 to 90%, preferred 99.9 to 99% suspension agents: active substance: 5 to 75%, preferred 10 to 50% water: 90 to 24%, preferred 88 to 30% tensio-active agents: 1 to 40%, preferred 2 to 30% wettable powders: active substance: 0.5 to 90%, preferred 1 to 80% tensio-active agent: 0.5 to 20%, preferred 1 to 15% solid carrier: 5 to 99%, preferred 15 to 98% granules: active substance: 0.5 to 30%, preferred 3 to 15% solid carriers: 99.5 to 70%, preferred 97 to 85%
By adding other sterilant or miticide, the present composition can extensively be adapted to the environment that passes through basically.In this respect, desinsection that be fit to add or acaricidal activity material are the active substances of following type for example: organo phosphorous compounds, nitrophenols and derivative thereof, formamidine, acyl group ureas, amino formate, pyrethroid, Nitroenamine and derivative, pyroles, thiourea and derivative thereof, chlorinated hydrocarbon and thuricade-1.The present composition also can comprise solid or liquid auxiliary agent such as stablizer, unmodified or epoxidised vegetables oil (for example epoxidised Oleum Cocois, rapeseed oil or soybean oil), defoamer polysiloxane oil for example for example, sanitas, viscosity modifier, tackiness agent and/or caking agent, and chemical fertilizer or be used to obtain other active substance of special-effect, for example bactericide, nematocides, invertebrate poison or selective herbicide.
The present composition prepares in a known manner: for example when no auxiliary, by being ground, sieve and/or compress (for example), solid active agents or active material admixture become specific granular size, and when at least a auxiliary exists, for example pass through active substance or active material admixture and one or more auxiliary uniform mixing and/or grinding.These are used to produce the method for the present composition and use Compound I and produce these method for compositions, are theme of the present invention equally.
The invention still further relates to the application process of composition, promptly, the method of the insect of the type that dispensary mentions, these methods are to select according to purpose that is intended to and current environment, and these methods comprise spraying, are fuming, dust, brush, dress seed, spread fertilizer over the fields or water, and also relate to the insect that type is put forward by set of applications compound dispensary.In this respect, typical application concentration is 0.1 to 1000ppm, preferred 0.1 to 500ppm active substance.The amount of application of per hectare is 1 to 200g active substance per hectare normally, and particularly 10 to 1000g/ha, and preferred 20 to 600g/ha.
In the preferred application process in plant protection field is that plant leaf surface is used (foliage applying), and number of times of using and amount of application depend on the degree of indivedual insect infringements.Yet, by with liquid composition the plant site being soaked into or solid-state active substance being mixed the site of plant,, for example mixing soil (soil application) with the particulate form, active substance also can enter plant (systemic action) through root system.In rice terrace, after can weighing up, these particles apply in the rice field of pouring water.
The present composition also is suitable for the protective plant propagulum, and for example seed such as fruit, stem tuber or cereal, or plant rice shoot make it to resist animal pest.In this case, propagulum can be used compositions-treated before plantation; Seed (for example) can be dressed seed prior to seeding.Active substance of the present invention also can be used seed (coating) by seed being soaked in liquid composition or seed being applied with solids composition.Composition also can be applied to the plantation site when propagulum is planted, for example use in the seed drill for sowing in lines under the situation of sowing.These are used for the treatment process of propagulum and the propagulum of handling like this, are another themes of the present invention.
Formula I compound of the present invention also can be a weeding activity.Be used for formula I compound of the present invention or comprise the suitable application process used of the weeding of composition be ordinary method on all agricultural, such as use before the bud, the inoculation of postemergence application and seed, and also can be the whole bag of tricks and technology, for example sustained release of active substance.For this purpose, the active substance in solution is coated on mineral grain carrier or polymeric particle (urea/formaldehyde), be dried afterwards.If desired, all right coated (coating particle agent) makes active substance discharge in the time period that limits with the amount of regulating.
Formula I compound can use with unaltered form, promptly, the form that is obtained when synthetic according to it, but, preferably process with conventional mode, use is common in the auxiliary of manufacture field, but for example provides missible oil, can directly spray or emulsion, wettable powder, soluble powder, pulvis, granule or the capsule of diluting soln, dilution.Method of using such as spraying, atomizing, dust, moistening, spread fertilizer over the fields or pour, the same with the character of composition, be to select according to purpose that is intended to and current condition.
Preparation, promptly comprise formula I active substance or at least a formula I active substance and composition, prepared product or the combination of one or more solid or fluid additive if desired, produce in a known manner, for example by with active substance and additive as solvent or solid carrier uniform mixing and/or grind and produce, in addition, also may in producing preparation, use surface active cpd (tensio-active agent).The solvent, solid carrier and the surface active cpd that are fit to are for example hereinafter described types.
Herbicidal formulations contains 0.1 to 99% usually, 0.1 to 95% formula I active substance particularly, 1 to 99% solid or liquid processing aids and 0 to 25%, particularly 0.1 to 25% tensio-active agent.
Though commerical prod trends towards preferably comprising concentrate composition, the final user uses diluted composition usually.
Composition also can comprise for example unmodified or epoxidised vegetables oil of other additive such as stablizer (epoxidised Oleum Cocois, rapeseed oil or soybean oil), defoamer for example polysiloxane oil, sanitas, viscosity modifier, tackiness agent, caking agent and chemical fertilizer or be used to obtain other active substance of certain effects.
Specifically, preferred preparation is by following combination (%=weight percent) missible oil: active substance: 1 to 90%, preferred 5 to 50% tensio-active agents: 5 to 30%, preferred 10 to 20% solvents: 15 to 94%, preferred 70 to 85% pulvis: active substance: 0.1 to 50%, preferred 0.1 to 1% solid carrier: 99. to 90%, preferred 99.9 to 99% suspension agents: active substance: 5 to 75%, preferred 10 to 50% water: 94 to 24%, preferred 88 to 30% tensio-active agents: 1 to 40%, preferred 2 to 30% wettable powders: active substance: 0.5 to 90%, preferred 1 to 80% tensio-active agent: 0.5 to 20%, preferred 1 to 15% solid carrier: 5 to 95%, preferred 15 to 90% granules: active substance: 0.1 to 30%, preferred 0.1 to 15% solid carrier: 99.5 to 70%, preferred 97 to 85%
Formula I active substance is with 0.001 to 2kg/ha, and particularly 0.005 to 1kg/ha amount of application uses normally effective.For the amount of application that obtains required effect can be determined by the mode of test.Amount of application depend on effect character, crop and weeds vegetative period and depend on use (site, time, method), and can in quite wide scope, change according to these parameters.
The salient point of formula I compound is its herbicidal performance, and it is particularly very remarkable in the application on cereal class, cotton, soybean, rape, corn, rice and the plantation crops crop that its herbicidal performance makes it.They can also adopt and do the burn-down agent and for example be used for potato, or as defoliant.
Cultivation thing that relates to or crop are intended to comprise that those are by conventional breeding method or gene treatment process and weedicide or classes of herbicides are had the cultivation thing or the crop of tolerance.
The invention still further relates to the broadleaf weeds optionally prevented and treated in the crop and the method for gramineous weeds, described method comprises with the formula I weedicide of herbicidally effective amount with the formula X or the XI safener of weedicide antagonism significant quantity, while or handle crop, its seed or seedling or its cultivation area independently of each other.
Can be with formula X and XI protection, the crop (especially) that makes it to resist the infringement effect of described weedicide is corn and cereal class.
The weeds that can prevent and treat are unifacial leaf or broadleaf weed.
The zone that is considered to the cultivation area is the known plantation of a crop soil region thereon, or with the soil region of the planting seeds of these crops, and also can be the zone that is intended to these arable farmings.
Depend on the application that is intended to, formula X or XI safener can be used for the seed (seed or rice shoot are mixed medicine) of pre-treatment crop, or prior to seeding or be placed in the soil.Yet safener also can be used with itself or with weedicide after crop emerges.Can be independent of the time of application point of weedicide on the safener treatment principle of crop or seed.Yet the crop processing also can be used (for example as the mixed thing of bucket) by weedicide and safener simultaneously and be carried out.
The safener that is intended to use is used than roughly depending on application process with weedicide.Comprise the mixed thing of bucket of safener and weedicide or by using respectively during land for growing field crops that safener and weedicide carry out handles, the ratio of weedicide and safener normally 100: 1 to 1: 10 is preferably 20: 1 to 1: 1 in use.
Usually, in handle in the land for growing field crops, use 0.001 to 5.0kg safener/ha, preferred 0.001 to 0.5kg safener/ha.
The amount of application of weedicide is usually 0.001 and 2kg/ha, but preferably between 0.005 to 1kg/ha.
The present composition is suitable for the application process that all routines are used for agricultural, for example uses postemergence application and seed dressing before the bud.
Under the situation of seed dressing, use 0.001 to 10g safener/kg seed usually, preferred 0.05 to 2g safener/kg seed.If safener with the form of liquid prior to seeding soon, following seed soaking to use, then preferably use to comprise 1 to 10000ppm, the safener solution of preferred 100 to 1000ppm active substances.
When using, the safener of formula X or XI, or the combination of these safeners and formula I weedicide, advantageously process with the auxiliary that is common in manufacture field, provide specific formulation, but for example provide missible oil, the paste that can brush, can directly spray or emulsion, wettable powder, soluble powder, pulvis, granule or the capsule of diluting soln, dilution.Preparation prepares in a known manner, for example by with active substance and liquid or solid prescription auxiliary as solvent or solid carrier uniform mixing and/or grind and produce, in addition, also may in producing preparation, use surface active cpd (tensio-active agent).Solvent, solid carrier and the surface active cpd that is fit to is the type described in the preamble for example.
Pesticide preparation contains by weight 0.1 to 99% usually, 0.1 to 95% safener or safener/herbicidal active compounds mixture by weight particularly, by weight 1 to 99%, particularly 5 to 99.8% solid or liquid processing aids and by weight 0 to 25% by weight, particularly 0.1 to 25% tensio-active agent by weight.
Though commerical prod trends towards preferably comprising concentrate composition, the final user uses diluted composition usually.
Composition also can comprise other additive such as stablizer, defoamer, viscosity modifier, tackiness agent, caking agent and chemical fertilizer or other active substance.
With formula X and XI safener or comprise composition be used for cover crop; when making it to resist the detrimental effect of formula I weedicide; the whole bag of tricks and technology are fit to; embodiment is as follows: i) seed dressing is a) in container; by seed is shaken with formula X that is processed into wettable powder or XI active substance, be uniformly distributed in seed-coat dress seed (dry type seed dressing) until active substance.In this case, every 100kg seed uses about 1 to about 500g formula X or XI active substance (4g to 2kg wettable powder).B) with the high density emulsion of the active substance of formula X or XI according to method a) dress seed (wet type seed dressing).C) by being immersed, seed contains in 100-1000ppm formula X or the XI active substance 1 to 72 hour, and if desired it drying is dressed seed afterwards (seed soaking).
Seed dressing and handle seedling when beginning to sprout, preferred application process that yes is directly facing to whole target body crop because handle with active substance.Generally speaking, every 100kg seed uses 1 to 1000g toxinicide, preferred 5 to 250g toxinicides, and these bounds also might be because of the deviation to some extent of dressing seed repeatedly, and this point depends on used method, and may add other active substance or trace element.Ii) bucket mixes and uses
Use the liquid preparation (mutual mass ratio is 10: 1 to 1: 100) of the mixture of toxinicide and weedicide, the amount of application of weedicide is 0.005 to 5.0kg/ha.These barrels mixture prior to seeding or after use.Iii) the seed drilling is used
Safener is mixed in the seed drill for sowing in lines that contains seed of opening with the form of emulsion, wettable powder or granule.After the seed drill for sowing in lines built, carry out using before the bud with conventional mode.The iv) sustained release of active substance
Formula X or XI active substance are coated on mineral grain carrier or polymeric particle (urea/formaldehyde) with solution, afterwards with it drying.If desired, can coated (coating particle agent), it can guarantee that active substance discharges with the amount of regulating in the time period that limits.
The following example illustrates in greater detail the present invention, but does not limit the present invention.The temperature that provides is ℃.The temperature that provides in " physical data " hurdle of form is the melting temperature of respective compound, unless otherwise.Preparation embodiment: the preparation of embodiment H1:2-cyclohexyl-2 Methylpropionic acid { 3-oxo-2-(2,4, the 6-trimethylphenyl)-5,6,7,8-tetrahydrochysene-3-H-pyrazolo [1,2-a] pyridazine-1-yl } ester
Figure A9519765200541
With 1.09g 3-hydroxyl-4-_ base-5-oxo-1,2-tetramethylene pyrazoline and 1.4ml triethylamine are bathed in the 25ml tetrahydrofuran (THF), and add 0.75g2-cyclohexyl-2 Methylpropionic acid down at 20 ℃.Reaction mixture was stirred 3 hours down at 40 ℃, on Rotary Evaporators, concentrate afterwards.Residue toluene and water treatment.Toluene is through dried over sodium sulfate, and concentrates.Residue stirs with hexane, and suction filtration provides required compound afterwards, is white powder, fusing point 172-173 ℃.Embodiment H2:(2-cyano ethyl) methyl carbamic acid { 3-oxo-2-(2,4, the 6-trimethylphenyl)-5,6,7, the preparation of 8-tetrahydrochysene-3-H-pyrazolo [1,2-a] pyridazine-1-} ester
Figure A9519765200551
With 1.22g 3-hydroxyl-4-_ base-5-oxo-1,2-tetramethylene pyrazoline and 1.14g triethylamine are dissolved in the 25ml tetrahydrofuran (THF), and add 0.7g (2-cyano ethyl)-methylamino formyl chloride while stirring.Reaction mixture was stirred 3 hours down at 40 ℃, on Rotary Evaporators, concentrate afterwards.Add methylene dichloride and frozen water to residue.The organic phase dried over sodium sulfate, and concentrate, the residue that is obtained stirs with hexane, and suction filtration provides required compound afterwards, is white powder, fusing point 151-153 ℃.Embodiment H3: the preparation of cyclohexyl methyl thionamic acid { 3-oxo-2-(2,4, the 6-trimethylphenyl)-5,6,7,8-tetrahydrochysene-3-H-pyrazolo [1,2-a] pyridazine-1-yl } ester
With 2.7g 3-hydroxyl-4-_ base-5-oxo-1,2-tetramethylene pyrazoline and 3.0g triethylamine are dissolved in the 30ml tetrahydrofuran (THF), at room temperature add 2.1g cyclohexyl methyl sulfamic acid chloride.Afterwards reaction mixture was stirred 8 hours down at 40 ℃.To ly concentrate, residue is handled with t-butyl methyl ether and frozen water.The organic phase dried over sodium sulfate, and concentrate.Crude product is dissolved in ethyl acetate, and solution concentrates filtrate through filtered through silica gel, and residue stirs with hexane.Suction filtrate is also dry, provides required compound, is white powder, fusing point 171-173 ℃.
The compound of table 1-9 can be similar to the foregoing description and prepare with the preparation method who describes.
Table 1-7 hereinafter lists the compound as formula Ia to Ig, as the compound of the preferred formula I of sterilant and miticide and weedicide.
Table 8 and 9 is listed preferred compound as formula X and XI safener.
Table 1
Figure A9519765200571
Compound R2 R 3A physical data numbering 1.1-(CH2) 4-    
Figure A9519765200572
                125-127° 1.2     -(CH 2) 4-              65-67° 1.3     -(CH 2) 4-          103-106° 1.4     -(CH 2) 4-    
Figure A9519765200575
          111-113° 1.5     -(CH 2) 4-                  106-108° 1.6     -(CH 2) 4-             102-104° 1.7     -(CH 2) 4-    
Figure A9519765200578
                80-82° 1.8     -(CH 2) 4-      -N(CH 3)CH 2CH 2CN              151-153° 1.9     -(CH 2) 4-    
Figure A9519765200579
              101-103° 1.10    -(CH 2) 4-      -N(CH 2CH 2CN)-(CH 2) 3OC 2H 5 1.11    -(CH 2) 4-     90-92 ° of compound R2 R 3A physical data numbering 1.12-(CH2) 4-                           
Figure A9519765200581
      150-152° 1.13      -(CH 2) 4-                            -CH(C 6H 5)OCOCH 3                  145-146° 1.14      -(CH 2) 4-                            -C(CH 3) 2OCOCH 3                   104° 1.15      -(CH 2) 4-                                                  179-180° 1.16      -(CH 2) 4-                                           172-173° 1.17    
Figure A9519765200584
                   137-139° 1.18      -(CH 2) 4-                                         172-173° 1.19      -(CH 2) 4-adamantane-1-base 204-205 ° 1.20              134-136° 1.21      -(CH 2) 4-                           
Figure A9519765200587
                     120-121° 1.22      CH 3  CH 3                            -C(CH 3) 2OCOCH 3148-149 ° of compound R2 R 3A physical data numbering 1.23 CH3  CH 3                                       135-136° 1.24    -(CH 2) 4-                
Figure A9519765200592
Amorphous 1.25-(CH2) 4-                -CH 2CH 2CH 2COOC 2H 5Shu Zhi 1.26-(CH2) 4-                -C(CH 3) 2OCO-t-C 4H 9                149-150° 1.27    -(CH 2) 4-                -C(CH 3) 2OCO-C 6H 5                  143-145° 1.28    -(CH 2) 4-                
Figure A9519765200593
Shu Zhi 1.29 CH3  CH 3                
Figure A9519765200594
              160-161° 1.30    -(CH 2) 4-                -CH 2Si(CH 3) 3 1.31    -(CH 2) 4-                 1.32    -(CH 2) 4-                -C(CH 3) 2COOCH 3 1.33    -(CH 2) 4-                
Figure A9519765200596
                     135-137° 1.34    -(CH 2) 4-                                              120° 1.35    -(CH 2) 4-                
Figure A9519765200598
Oily Wu 1.36-(CH2) 3-                 -C(CH 3) 2OC(=O)CH 3Shu Zhi 1.37-CH2CH 2CH(CH 3)CH 2-    -C(CH 3) 2C(=O)CH 3Shu Zhi 1.38-CH2CH 2CH(CH 3)CH 2-Nai-170-171 ° of 1.39-CH of 2-base2CH 2CH(CH 3)CH 2-    -N(CH 3)CH 2CH 2CN                       105-106° 1.40    C 2H 5 CH 3Nai-139-142 ° of compound R of 2-base2 R 3A physical data numbering 1.41
Figure A9519765200601
Nai-2-base 1.42     -C(CH 3) 2OC(=O)CH 3Shu Zhi 1.43 CH3 C 2H 5                           -C(CH 3) 2OC(=O)CH 3              70-82° 1.44    CH 3 C 2H 5                           -N(CH 3)CH 2CH 2CN Shu Zhi 1.45-(CH2) 3-                             -N(CH 3)CH 2CH 2CN Shu Zhi 1.46-(CH2) 3-Nai-82-83 ° of 1.47-CH (CH of 2-base3)-(CH 2) 3-                   -C(CH 3) 2OC(=O)CH 3Shu Zhi 1.48-CH (CH3)-(CH 2) 3-                   -N(CH 3)CH 2CH 2CN Shu Zhi 1.49-CH (CH3)-(CH 2) 3-Nai-2-base amorphous 1.50-CH2(CH(CH 3)) 2CH 2-Nai-186-187 ° of 1.51-CH of 2-base2(CH(CH 3)) 2CH 2-                -C(CH 3) 2OC(=O)CH 3Shu Zhi 1.52-CH2(CH(CH 3)) 2CH 2-                -N(CH 3)CH 2CH 2CN amorphous 1.53-(CH2) 4-cyclopentyloxy 1.54
Figure A9519765200603
           -N(CH 3)CH 2CH 2CN Shu Zhi 1.55-(CH2) 4-                           
Figure A9519765200604
Shu Zhi 1.56 CH3  CH 3                            -N(CH 3)CH 2CH 2CN                   83-83° 1.57    CH 3  CH 3                            -N(C 2H 5)CH 2CH 2CN                 112-113° 1.58    -(CH 2) 4-                            -N(C 3H 7-n)CH 2CH 2CN               109-110° 1.59    -(CH 2) 4-                            -N(C 2H 5)CH 2CH 2CN                 106-107° 1.60    -CH 2(CH(CH 3)) 2CH 2-               -N(C 2H 5)CH 2CH 2CN                  122-123° 1.61    -(CH 2) 4-                            -N(CH 2CH 2CN) 2                      173-175° 1.62    -(CH 2) 4-                            -N(CH 2CH 2CN)C 4H 9(n)               87-89° 1.63    -(CH 2) 4-                             162-163 ° of compound R2 R 3A physical data numbering 1.64-(CH2) 4-                    
Figure A9519765200611
      148-150° 1.65    -(CH 2) 4-                     -N(CH 2CH 2CN)CH 2CH 2OCH 3 1.66    -(CH 2) 4-                               111-113° 1.67    -(CH 2) 4-                    
Figure A9519765200613
      126-128° 1.68    -(CH 2) 4-                    
Figure A9519765200614
  138-140° 1.69    -(CH 2) 4-                     -N(CH 2CH 2CN)C 6H 13(n)             79-81° 1.70    -(CH 2) 5-                     -N(CH 3)CH 2CH 2CN 1.7 1   -(CH 2) 5-                     -N(C 2H 5)CH 2CH 2CN 1.72    -(CH 2) 5-                     1.73    -(CH 2) 5-                     -N(CH 2CH 2CN)C 6H 13(n) 1.74    -(CH 2) 5-                     1.75    -CH 2CH 2CH(CH 3)CH 2CH 2-    -N(CH 3)CH 2CH 2CN 1.76    -CH 2CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)C 6H 13(n) 1.77    -CH 2CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200617
1.78    -CH 2CH 2CH(CH 3)CH 2CH 2-    -N(C 2H 5)CH 2CH 2CN 1.79    -(CH 2) 5-Nai-2-base 1.80-(CH2) 5-                     
Figure A9519765200618
1.81    -CH 2CH 2CH(CH 3)CH 2CH 2-Nai-2-base 1.82-CH2CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200619
1.83    -CH 2CH(CH 3)CH 2CH 2-       -N(C 2H 5)CH 2CH 2CN 1.84    -CH 2CH(CH 3)CH 2CH 2-       -N(C 3H 7-n)CH 2CH 2The CN compound R2 R 3A physical data numbering 1.85-CH2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)C 4H 9(n) 1.86   -CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)C 6H 13(n) 1.87   -CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)C 8H 17-n 1.88   -CH 2CH(CH 3)CH 2CH 2-     1.89   -CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200622
1.90   -CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200623
1.91   -CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200624
1.92   -CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN) 2 1.93   -CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)CH 2CH 2OCH 3 1.94   -(CH 2) 3CH(CH 3)-        -N(C 2H 5)CH 2CH 2CN 1.95   -(CH 2) 3CH(CH 3)-        -N(C 3H 7-n)CH 2CH 2CN 1.96   -(CH 2) 3CH(CH 3)-        -N(CH 2CH 2CN)C 4H 9(n) 1.97   -(CH 2) 3CH(CH 3)-        -N(CH 2CH 2CN)C 6H 13(n) 1.98   -(CH 2) 3CH(CH 3)-        
Figure A9519765200625
1.99   -(CH 2) 3CH(CH 3)-         1.100  -(CH 2) 5-                -N(C 3H 7-n)CH 2CH 2CN 1.101  -(CH 2) 5-                -N(CH 2CH 2CN)C 4H 9(n) 1.102  -(CH 2) 5-                -N(CH 2CH 2CN)C 6H 13(n) 1.103  -(CH 2) 5-                -N(CH 2CH 2CN)C 8H 17-n 1.104  -(CH 2) 5-                 Compound R2 R 3A physical data numbering 1.105-(CH2) 5-                       
Figure A9519765200631
1.106  -(CH 2) 5-                       
Figure A9519765200632
1.107  -(CH 2) 5-                       
Figure A9519765200633
1.108  -(CH 2) 5-                       
Figure A9519765200634
1.109  -(CH 2) 5-                        -N(CH 2CH 2CN) 2 1.110  -(CH 2) 5-                        -N(CH 2CH 2CN)CH 2CH 2OCH 3 1.111  -CH 2CH 2CH(CH 3)CH 2CH 2-       -N(C 3H 7-n)CH 2CH 2CN 1.112  -CH 2CH 2CH(CH 3)CH 2CH 2-       -N(CH 2CH 2CN)C 4H 9(n) 1.113  -CH 2CH 2CH(CH 3)CH 2CH 2-      
Figure A9519765200635
1.114  -CH 2CH 2CH(CH 3)CH 2CH 2-      
Figure A9519765200636
1.115  -CH 2CH 2CH(CH 3)CH 2CH 2-       1.116  -CH 2CH 2CH(CH 3)CH 2CH 2-       -N(CH 2CH 2CN) 2 1.117  -CH 2CH(CH 3)CH 2CH 2-           1.118  CH 3 CH 3                             172-174° 1.119  -CH 2(CH(CH 3)) 2CH 2-           155-157° 1.120  -CH 2(CH(CH 3)) 2CH 2-           -N(CH 2CH 2CN)C 4H 9(n)           104-106° 1.121  -(CH 2) 4-                      
Figure A95197652006311
164-166 ° of compound R2 R 3A physical data numbering 1.122-(CH2) 4-    -N(CH 2CH 2CN)C 8H 15-c 1.123  -(CH 2) 4-    -N(CH 2CH 2CN)C 7H 13-c 1.124  -(CH 2) 4-    -N(CH 2CH 2CN)C 12H 23-c       154-156° 1.125  -(CH 2) 4-    -N(CH 2CH 2CN)-(CH 2) 3OCH 3
Table 2Compound R2 R 3          A                     R 4Physical data numbering 2.1-(CH2) 4-  
Figure A9519765200652
       6-Cl   142-143° 2.2    -(CH 2) 4-  
Figure A9519765200653
  6-Cl   106-108° 2.3    -(CH 2) 4-   6-F Shu Zhi 2.4-(CH2) 4-   6-F Shu Zhi 2.5-(CH2) 4-  
Figure A9519765200656
6-F Shu Zhi 2.6-(CH2) 4-  
Figure A9519765200657
            6-Cl   208° 2.7    -(CH 2) 4-  
Figure A9519765200658
     6-Cl   220° 2.8    -(CH 2) 4-  
Figure A9519765200659
6-Cl 136-139 ° compound R2 R 3                  A                        R 4Physical data numbering 2.9-(CH2) 4-      
Figure A9519765200661
                  6-Cl   106-109° 2.10    -(CH 2) 4-      
Figure A9519765200662
                6-C1   97-100° 2.11    -(CH 2) 4-      -C(CH 3) 2OCOCH 3                      6-Cl    113-116° 2.12    -(CH 2) 4-      -CH(C 6H 5)-OCOCH 3                    6-Cl    156-158° 2.13    -(CH 2) 4-      -CH 2OCH 2C 6H 5                       6-Cl    230° 2.14    -(CH 2) 4-      
Figure A9519765200663
              6-Cl    117-119° 2.15    -(CH 2) 4-      -C(CH 3) 2-OCO-t-C 4H 9                6-Cl    151-153° 2.16    -(CH 2) 4-      -C(CH 3) 2-OCO-C 6H 56-Cl amorphous 2.17-(CH2) 4-      -N(CH 3)CH 2CH 2CN                     6-Cl    156-158° 2.18    -C 2H 5 -C 2H 5 -C(CH 3) 2-OCO-t-C 4H 9               6-Cl    90-91° 2.19    -C 2H 5 -C 2H 5                6-Cl    141-142° 2.20    -(CH 2) 4-      -N(C 2H 5)CH 2CH 2CN                   6-Cl    147-148° 2.21    -(CH 2) 4-      -N(C 3H 7-n)CH 2CH 2CN                 6-Cl    134-135° 2.22    -(CH 2) 4-      -N(CH 2CH 2CN)C 6H 13(n)               6-Cl    78-80° 2.23    -(CH 2) 4-            6-Cl    159-161° 2.24    -(CH 2) 4-      -N(CH 2CH 2CN)C 4H 9(n)                6-Cl    127-129° 2.25    -(CH 2) 4-                6-Cl    223-225° 2.26    -(CH 2) 4-      -N(CH 2CH 2CN)C 8H 17-n                 6-Cl 2.27    -(CH 2) 4-      -N(C 3H 7-n)CH 2CH 2CN                  6-F 2.28    -(CH 2) 4-      -N(CH 2CH 2CN) 2                        6-Cl    188-190° 2.29    -(CH 2) 4-       6-Cl 125-127 ° compound. R2 R 3                  A                                 R 4Physical data numbering 2.30-(CH2) 4-                      6-Cl  155-157° 2.31  -(CH 2) 3-                -N(CH 3)CH 2CH 2CN                 6-Cl 2.32  -(CH 2) 3-                -N(CH 3)CH 2CH 2CN                 6-F 2.33  -(CH 2) 3-                 6-Cl 2.34  -(CH 2) 3-                
Figure A9519765200673
 6-F 2.35  -(CH 2) 3-                -N(CH 2CH 2CN)C 6H 13(n)            6-Cl 2.36  -(CH 2) 3-                -N(CH 2CH 2CN)C 6H 13(n)            6-F 2.37  -CH 2CH(CH 3)CH 2CH 2-    -N(CH 3)CH 2CH 2CN                  6-Cl 2.38  -CH 2CH(CH 3)CH 2CH 2-    -N(C 2H 5)CH 2CH 2CN                6-Cl 2.39  -CH 2CH(CH 3)CH 2CH 2-    -N(C 3H 7-n)CH 2CH 2CN              6-Cl 2.40  -CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)C 4H 9(n)             6-Cl 2.41  -CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)C 6H 13(n)            6-Cl 2.42  -CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200674
          6-Cl 2.43  -CH 2CH(CH 3)CH 2CH 2-          6-Cl 2.44  -CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200676
 6-Cl 2.45  -CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200677
      6-Cl 2.46  -CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN) 2                    6-Cl 2.47  -CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)CH 2CH 2OCH 3        6-Cl 2.48  -(CH 2) 3CH(CH 3)-        -N(CH 3)CH 2CH 2CN                  6-Cl 2.49  -(CH 2) 3CH(CH 3)-        -N(C 2H 5)CH 2CH 2CN                6-Cl 2.50  -(CH 2) 3CH(CH 3)-        -N(C 3H 7-n)CH 2CH 2CN              6-Cl 2.51  -(CH 2) 3CH(CH 3)-        -N(CH 2CH 2CN)C 4H 9(n) 6-Cl compound. R2 R 3                       A                                R 4Physical data numbering 2.52-(CH2) 3CH(CH 3)-           -N(CH 2CH 2CN)C 6H 13(n)          6-Cl 2.53    -(CH 2) 3CH(CH 3)-                    6-Cl 2.54    -(CH 2) 3CH(CH 3)-               6-Cl 2.55    -(CH 2) 3CH(CH 3)-           6-Cl 2.56    -(CH 2) 3CH(CH 3)-                6-Cl 2.57    -(CH 2) 3CH(CH 3)-           -N(CH 2CH 2CN) 2                  6-Cl 2.58    -(CH 2) 3CH(CH 3)-           -N(CH 2CH 2CN)CH 2CH 2OCH 3       6-Cl 2.59    -(CH 2) 5-                   -N(CH 3)CH 2CH 2CN                 6-Cl 2.60    -(CH 2) 5-                   -N(C 2H 5)CH 2CH 2CN               6-Cl 2.61    -(CH 2) 5-                   -N(C 3H 7-n)CH 2CH 2CN             6-Cl 2.62    -(CH 2) 5-                   -N(CH 2CH 2CN)C 4H 9(n)            6-Cl 2.63    -(CH 2) 5-                   -N(CH 2CH 2CN)C 6H 13(n)           6-Cl 2.64    -(CH 2) 5-                             6-Cl 2.65    -(CH 2) 5-                        6-Cl 2.66    -(CH 2) 5-                    6-Cl 2.67    -(CH 2) 5-                         6-Cl 2.68    -(CH 2) 5-                   -N(CH 2CH 2CN) 2                    6-Cl 2.69    -(CH 2) 5-                   -N(CH 2CH 2CN)CH 2CH 2OCH 3        6-Cl 2.70    -CH 2CH 2CH(CH 3)CH 2CH 2-  -N(CH 3)CH 2CH 2CN                  6-Cl 2.71    -CH 2CH 2CH(CH 3)CH 2CH 2-  -N(C 2H 5)CH 2CH 2CN 6-Cl compound R2 R 3                            A                            R 4Physical data numbering 2.72-CH2CH 2CH(CH 3)CH 2CH 2-    -N(C 3H 7-n)CH 2CH 2CN             6-Cl 2.73    -CH 2CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)C 4H 9(n)            6-Cl 2.74    -CH 2CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)C 6H 13(n)           6-Cl 2.75    -CH 2CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200691
         6-Cl 2.76    -CH 2CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200692
    6-Cl 2.77    -CH 2CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200693
 6-Cl 2.78    -CH 2CH 2CH(CH 3)CH 2CH 2-    
Figure A9519765200694
      6-Cl 2.79    -CH 2CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN) 2                    6-Cl 2.80    -CH 2CH 2CH(CH 3)CH 2CH 2-    -N(CH 2CH 2CN)CH 2CH 2OCH 3        6-Cl 2.81    -CH 2CH 2CH(CH 3)CH 2CH 2-Nai-2-base 6-Cl 2.82-(CH2) 5-Nai-2-base 6-Cl 2.83-CH2CH(CH 3)CH 2CH 2-Nai-2-base 6-Cl 2.84-(CH2) 3CH(CH 3)-Nai-2-base 6-Cl 2.85 CH3    CH 3Nai-2-base 6-Cl 2.86-(CH2) 4-                    -N(CH 3)CH 2CH 2CN                   6-F 2.87    -(CH 2) 4-                    -N(C 2H 5)CH 2CH 2CN                 6-F 2.88    -(CH 2) 4-                    -N(CH 2CH 2CN)C 6H 13(n)             6-CH 3 2.89    -(CH 2) 4-                    -N(CH 2CH 2CN)C 4H 9(n)              6-F 2.90    -(CH 2) 4-                    -N(CH 2CH 2CN)C 6H 13(n)             6-F 2.91    -(CH 2) 4-                    
Figure A9519765200695
           6-F 2.92    -(CH 2) 4-                    
Figure A9519765200696
      6-F 2.93    -(CH 2) 4-                     The 6-F compound R2 R 3            A                         R 4Physical data numbering 2.94-(CH2) 4-          6-F 2.95   -(CH 2) 4-    -N(CH 2CH 2CN) 2                   6-F 2.96   -(CH 2) 4-    -N(CH 2CH 2CN)CH 2CH 2OCH 3       6-F 2.97   -(CH 2) 4-Nai-2-base 6-F 2.98-(CH2) 4-    -N(CH 3)CH 2CH 2CN                 6-CH 3 2.99   -(CH 2) 4-    -N(C 2H 5)CH 2CH 2CN               6-CH 3 2.100  -(CH 2) 4-    -N(C 3H 7-n)CH 2CH 2CN             6-CH 3 2.101  -(CH 2) 4-    -N(CH 2CH 2CN)C 4H 9(n)            6-CH 3 2.102  -(CH 2) 4-    
Figure A9519765200702
6-Cl 2.103  -(CH 2) 4-     6-CH 3Table 3
Figure A9519765200711
Compound R2 R 3        A                    R 4N physical data numbering 3.1-(CH2) 4-     2-CH 3,6-CH 3  2 77-79° 3.2    CH 3 CH 3    
Figure A9519765200713
 2-CH 3          1 98-100° 3.3    CH 3 CH 3    -C(CH 3) 2-OCOCH 3  2-CH 3          1 118-120° 3.4    -(CH 2) 4-Nai-2-base 2-CH3,3-CH 3
6-CH 333.5-(CH 2) 4--N (CH 3) CH 2CH 2CN 2-CH 3, 6-CH 323.6-(CH 2) 5--N (CH 3) CH 2CH 2CN 2-CH 3, 6-CH 323.7-(CH 2) 3--N (CH 3) CH 2CH 2CN 2-CH 3, 6-CH 323.8-(CH 2) 4-naphthalene-2-base 2-CH 3, 6-CH 323.9-(CH 2) 4-naphthalene-2-base 2-CH 3, 6-C 2H 523.10-(CH 2) 5-naphthalene-2-base 2-CH 3, 6-CH 323.11-(CH 2) 3-naphthalene-2-base 2-CH 3, 6-CH 32 compound Rs 2R 3A R 4N physical data numbering 3.12-CH 2CH (CH 3) CH 2CH 2-naphthalene-2-base 2-CH 3,
6-CH 323.13-CH (CH 3)-(CH 2) 3-naphthalene-2-base 2-CH 3,
6-CH 323.14-CH 2CH 2CH (CH 3) CH 2CH 2-naphthalene-2-base 2-CH 3,
6-CH 3???23.15??-(CH 2) 4-????????????????????-N(CH 2CH 2CN)C 6H 13(n)???2-CH 3
6-CH 3???23.16??-CH 2CH(CH 3)CH 2CH 2-???????-N(CH 3)CH 2CH 2CN??????????2-CH 3
6-CH 3???23.17??-CH(CH 3)-(CH 2) 3-???????????-N(CH 3)CH 2CH 2CN?????????2-CH 3
6-CH 3???23.18??-CH 2CH 2CH(CH 3)CH 2CH 2-???-N(CH 3)CH 2CH 2CN?????????2-CH 3
6-CH 3???23.19??-(CH 2) 4-????????????????????-N(CH 3)CH 2CH 2CN?????????2-CH 3
3-CH 3
6-CH 3???33.20??-(CH 2) 3-????????????????????-N(CH 3)CH 2CH 2CN?????????2-CH 3
3-CH 3
6-CH 3???33.21??-(CH 2) 5-????????????????????-N(CH 3)CH 2CH 2CN?????????2-CH 3
3-CH 3
6-CH 3???33.22??-CH 2CH(CH 3)CH 2CH 2-???????-N(CH 3)CH 2CH 2CN??????????2-CH 3
3-CH 3
6-CH 3???33.23??-CH 2CH 2CH(CH 3)CH 2CH 2-???-N(CH 3)CH 2CH 2CN?????????2-CH 3
3-CH 3
6-CH 33 tables 4
Figure A9519765200731
Compound R 2R 3A physical data numbering 4.1-(CH 2) 4-
Figure A9519765200732
4.2-(CH 2) 4- 4.3-(CH 2) 4--CH (C 6H 5) OCOCH 34.4-(CH 2) 4--CH (C 6H 5) OCO-i-C 3H 74.5-(CH 2) 4--CH (C 6H 5) OCO-t-C 4H 94.6-(CH 2) 4--C (CH 3) 2OCOCH 34.7-(CH 2) 4--C (CH 3) 2OCO-i-C 3H 74.8-(CH 2) 4--C (CH 3) 2OCO-t-C 4H 94.9-(CH 2) 4--C (CH 3) 2OCOC 6H 54.10-(CH 2) 4- 4.11-(CH 2) 4-
Figure A9519765200735
4.12-(CH 2) 4-
Figure A9519765200736
119-120 ° of compound. R 2R 3A physical data numbering 4.13-(CH 2) 4- 4.14-(CH 2) 4-
Figure A9519765200742
4.15-(CH 2) 4-
Figure A9519765200743
132-134 ° of 4.16-(CH 2) 4- Oily matter 4.17 CH 3CH 3-CH (C 6H 5) OCOCH 34.18 CH 3CH 3-C (CH 3) 2OCOCH 34.19 CH 3CH 3
Figure A9519765200745
4.20 CH 3CH 3
Figure A9519765200746
4.21 CH 3CH 3
Figure A9519765200747
82-83 ° of 4.22-(CH 2) 4-cyclohexyloxy oily matter 4.23-(CH 2) 5-cyclohexyloxy 4.24-CH (CH 3)-(CH 2) 4-cyclohexyloxy 4.25-(CH 2) 3-cyclohexyloxy
Table 5
Figure A9519765200751
Compound R2 R 3B physical data numbering 5.1-(CH2) 4-    -NH(c-C 3H 5) 5.2     -(CH 2) 4-    -NH(c-C 6H 11) 5.3     -(CH 2) 4-    -NH(c-C 8H 15) 5.4     -(CH 2) 4-    -N(CH 2-c-C 3H 5) 2 5.5     -(CH 2) 4-    -N(c-C 3H 5) 2 5.6     -(CH 2) 4-    -N(c-C 6H 11) 2 5.7     -(CH 2) 4-    -N(CH 3)(c-C 3H 5) 5.8     -(CH 2) 4-    -N(CH 3)(c-C6H 11)           171-173° 5.9     -(CH 2) 4-    -N(C 2H 5)(c-C 6H 11) 5.10    -(CH 2) 4-    -N(n-C 3H 7)(c-C 6H 11) 5.11    -(CH 2) 4-    -N(n-C 3H 7)(CH 2-c-C 3H 5) 5.12    -(CH 2) 4-    -N(CH 3)(CH 2CH 2OCH 3) 5.13    -(CH 2) 4-    -N(C 2H 5)(CH 2CH 2OCH 3) 5.14    -(CH 2) 4-    -N(n-C 3H 7)(CH 2CH 2OCH 3) 5.15    -(CH 2) 4-    -N(CH 2CH 2OCH 3) 2Shu Zhi 5.16-(CH2) 4-    -N(CH 2CH 2SCH 3) 2 5.17    -(CH 2) 4-    -N(CH 2CH 2OC 2H 5) 2 5.18    -(CH 2) 4-    -N(CH 2CH 2OCH 2CH 2OCH 3) 2 5.19    -(CH 2) 4-    -N(CH 2CH 2OCH 2CH 2OC 2H 5) 2 5.20    -(CH 2) 4-    -N(CH 2CH=CH 2) 2 5.21    -(CH 2) 4-    -N(CH 3)(CH 2CH=CH 2) 5.22    -(CH 2) 4-    -N(C 2H 5)(CH 2CH=CH 2) 5.23    -(CH 2) 4-    -N(n-C 3H 7)(CH 2CH=CH 2) 5.24    -(CH 2) 4-    -N(i-C 3H 7)(CH 2CH=CH 2) 5.25    -(CH 2) 4-    -N(c-C 3H 5)(CH 2CH=CH 2) 5.26    -(CH 2) 4-    -N(c-C 6H 11)(CH 2CH=CH 2) compound R2 R 3B physical data numbering 5.27-(CH2) 4-    -N(CH 3)(CH 2-C≡CH) 5.28    -(CH 2) 4-    -N(C 2H 5)(CH 2-C≡CH) 5.29    -(CH 2) 4-    -N(n-C 3H 7)(CH 2-C≡CH) 5.30    -(CH 2) 4-    -N(n-C 4H 9)(CH 2-C≡CH) 5.3l    -(CH 2) 4-    -N(CH 3)[CH(CH 3)C≡CH] 5.32    -(CH 2) 4-    -N(C 2H 5)[CH(CH 3)C≡CH] 5.33    -(CH 2) 4-    -N(n-C 3H 7)[CH(CH 3)C≡CH] 5.34    -(CH 2) 4-    -NH-CH 2-C≡CH 5.35    -(CH 2) 4-    -NH-CH(CH 3)-C≡CH 5.36    -(CH 2) 4-    -NH-C(CH 3) 2-C≡CH 5.37    -(CH 2) 4-    -NH-CH(C 2H 5)-C≡CH 5.38    -(CH 2) 4-    -NH-C(C 2H 5) 2-C≡CH 5.39    -(CH 2) 4-    -NH-CH(CH 3)-CH=CH 2 5.40    -(CH 2) 4-    -NH-C(CH 3) 2-CH=CH 2 5.4l    -(CH 2) 4-    -NH-C(C 2H 5) 2-CH=CH 2 5.42    -(CH 2) 4-    -N(CH 3)CH 2CH 2CN 5.43    -(CH 2) 4-    -N(C 2H 5)CH 2CH 2CN 5.44    -(CH 2) 4-    -N(n-C 3H 7)CH 2CH 2CN 5.45    -(CH 2) 4-    -N(CH 2CH 2CN) 2 5.46    -(CH 2) 4-    -N(CH 3)(CH 2C 6H 5) 5.47    -(CH 2) 4-    -N(C 2H 5)(CH 2-C 6H 5) Shu Zhi 5.48-(CH2) 4-    -N(n-C 3H 7)(CH 2-C 6H 5) 5.49    -(CH 2) 4-    -N(i-C 3H 7)(CH 2-C 6H 5) 5.50    -(CH 2) 4-    -N(CH2-C6H5)2 5.51    -(CH 2) 4-    -N(CH 3)(CH 2-C 6H 4-4-Cl) 5.52    -(CH 2) 4-    -N(CH 3)(CH 2-C 6H 3-3,4-Cl 2) 5.53    -(CH 2) 4-    -N(CH 3)(CH 2-C 6H 4-4-CH 3) 5.54    -(CH 2) 4-    -N(CH 3)(CH 2-C 6H 4-4-CF 3) 5.55    -(CH 2) 4-    -N(C 2H 5)(CH 2-C 6H 4-4-Cl) 5.56    -(CH 2) 4-    -NH-C 6H 5 5.57    -(CH 2) 4--NH-(Nai base-1) 5.58-(CH2) 4--NH-(Nai base-2) 5.59-(CH2) 4-    -NH-C 6H 4-4-Cl compound R2 R 3B physical data numbering 5.60-(CH2) 4-    -NH-C 6H 4-4-CH 3 5.61    -(CH 2) 4-    -NH-C 6H 4-4-OCH 3 5.62    -(CH 2) 4-    -NH-C 6H 4-4-NO 2 5.63    -(CH 2) 4-    -NH-C 6H 4-4-CN 5.64    -(CH 2) 4-    -NH-C 6H 4-4-CF 3 5.65    -(CH 2) 4-    -NH-C 6H 3-3,4-(CH 3) 2 5.66    -(CH 2) 4-    -NH-C 6H 3-3,4-Cl 2 5.67    -(CH 2) 4-    -NH-C 6H 3-3,5-(CF 3) 2 5.68    -(CH 2) 4-    -NH-C 6H 4-3-CF 3 5.69    -(CH 2) 4-    -NH-C 6H 4-4(O-C 6H 5) 5.70    -(CH 2) 4-    -NH-C 6H 4-4(S-C 6H 5) 5.71    -(CH 2) 4-    -NH-C 6H 4-2-CH 3 5.72    -(CH 2) 4-    -NH-C 6H 4-2-C 2H 5 5.73    -(CH 2) 4-    -NH-C 6H 4-2-(i-C 3H 7) 5.74    -(CH 2) 4-    -NH-C 6H 3-2,6-(CH 3) 2 5.75    -(CH 2) 4-    -NH-C 6H 3-2,6-(C 2H 5) 2 5.76    -(CH 2) 4-    -NH-C 6H 3-2,6-(i-C 3H 7) 2 5.77    -(CH 2) 4-    -NH-C 6H 4-4-F 5.78    -(CH 2) 4-    -N-(C 6H 5)2 5.79    -(CH 2) 4-    -N(CH 3)(C 6H 5) 5.80    -(CH 2) 4-    -N(C 2H 5)(C 6H 5)               166-168° 5.81    -(CH 2) 4-    -N(CH 3)(C 6H 4-4-Cl) 5.82    -(CH 2) 4-    -N(CH 3)(C 6H 4-4-CH 3) 5.83    -(CH 2) 4-    -N(CH 3)(C 6H 4-4-F) 5.84    -(CH 2) 4-    -N(CH 3)(C 6H 3-3,4-Cl 2) 5.85    -(CH 2) 4-    -N(CH 3)[C 6H 3-3,4-(CH 3) 2] 5.86    -(CH 2) 4-    -N(CH 3)[C 6H 4-4(O-C 6H 5)] 5.87    -(CH 2) 4-    -N(CH 3)[C 6H 4-4(S-C 6H 5)] 5.88    -(CH 2) 4-Ma Lin-4-base Shu Zhi 5.89-(CH2) 4-4-thiomorpholine base 5.90-(CH2) 4-2,6-dimethyl-4-morpholinyl 5.91-(CH2) 4-2,6-dimethyl sulphur-based-4-morpholinyl 5.92-(CH2) 4-1-piperidyl compound R2 R 3B physical data numbering 5.93-(CH2) 4-1-pyrrolidinyl 5.94-(CH2) 4-4-methyl-Pai Qin-1-base 5.95-(CH2) 4-4-phenyl-Piperazine-1-base 5.96-(CH2) 4-4-(2-methoxyphenyl)-Pai Qin-1-base 5.97-(CH2) 4-4-(4-fluorophenyl) Pai Qin-1-base 5.98-(CH2) 4-4 (4-nitrobenzophenone) Pai Qin-1-base 5.99-(CH2) 4-(4-ethyoxyl Tang yl) Pai Qin-1-base 5.100-(CH2) 4-4-Bian base-Pai Qin-1-base 5.101-(CH2) 4-4-(2-Bi Ding yl) Pai Qin-1-base 5.102-(CH2) 4-4-(3,4-dichlorophenyl) Pai Qin-1-base 5.103-(CH2) 4-4-(4-methoxyphenyl) Pai Qin-1-base 5.104-(CH2) 4-4-Yi base Pai Qin-1-base 5.105-(CH2) 4-1,2,3,4-tetrahydroquinoline-1-base 5.106-(CH2) 4-1,2,3,4-Qing isoquinolin-2-yl, 5.107-(CH2) 4-indoline-139-141 ° of 5.108-(CH of 1-base2) 4-2-methyl isophthalic acid-piperidyl 5.109-(CH2) 4-2,6-dimethyl-1-piperidyl 5.110-(CH2) 4-3,3-dimethyl-1-piperidyl 49-51 ° 5.111-(CH2) 4-Nai-185-188 ° of 5.112-(CH of 1-base2) 4-Nai-163-165 ° of 5.113-(CH of 2-base2) 4-Nai-1-Xian base 5.114-(CH2) 4-Nai-2-Xian base 5.115-(CH2) 4-    -NH(c-C 5H 9) 5.116    -(CH 2) 4-    -NH(c-C 7H 13) 5.117    -(CH 2) 4-    -NH(c-C 8H 15) 5.118    -(CH 2) 4-    -NH(c-C 3H 5) 5.119    -(CH 2) 4--NH-adamantane-1-base 5.120-(CH2) 4-    -NH-C 6H 4-(4-c-C 6H 11) 5.121    -(CH 2) 4-     NH-C 6H 4-(4-C 6H 5) 5.122    -CH 3 - CH 3184-185 ° of 5.123-CH of 1-Nai base3  -CH 32-Nai base 5.124-CH3  -CH 3  -N(CH 3)-c-C 6H 11 5.125    -CH 3  -CH 3  -N(CH 2CH 2OCH 3) 2Compound R2       R 3B physical data numbering 5.126-CH3    -CH 3     N(CH 2CH 3)C 6H 5 5.127  -CH 3    -CH 3     
Figure A9519765200791
5.128  -CH 3    -CH 3      5.129  -CH 3    -CH 3      5.130  -CH 3    -C 2H 51-Nai base 5.131-CH3    -C 2H 52-Nai base 5.132-CH3    -C 2H 5   -N(CH 3)-c-C 6H 11 5.133  -CH 3    -C 2H 5   -N(CH 2CH 2OCH 3) 2 5.134  -CH 3    -C 2H 5   N(CH 2CH 3)C 6H 5 5.135  -CH 3    -C 2H 5   
Figure A9519765200794
5.136  -CH 3    -C 2H 5   
Figure A9519765200795
5.137  -CH 3    -C 2H 5   
Figure A9519765200796
5.138  -C 2H 5  -C 2H 51-Nai base 5.139-C2H 5  -C 2H 52-Nai base 5.140-C2H 5  -C 2H 5   -N(CH 3)-c-C 6H 11 5.141  -C 2H 5  -C 2H 5   -N(CH 2CH 2OCH 3) 2 5.142  -C 2H 5  -C 2H 5   N(CH 2CH 3)C 6H 5Compound R2       R 3B physical data numbering 5.143-C2H 5  -C 2H 5      5.144  -C 2H 5  -C 2H 5     
Figure A9519765200802
5.145  -C 2H 5  -C 2H 5      5.146  
Figure A9519765200804
1-Nai base 5.147
Figure A9519765200805
2-Nai base 5.148  -N(CH 3)-c-C 6H 11 5.149  
Figure A9519765200807
  -N(CH 2CH 2OCH 3) 2 5.150     N(CH 2CH 3)C 6H 5 5.151  
Figure A9519765200809
  
Figure A95197652008010
5.152  
Figure A95197652008011
5.153  
Figure A95197652008012
5.154    -(CH 2) 3-1-Nai based compound R2        R 3B physical data numbering 5.155-(CH2) 3-2-Nai base 5.156-(CH2) 3-    -N(CH 3)-c-C 6H 11 5.157    -(CH 2) 3-    -N(CH 2CH 2OCH 3) 2 5.158    -(CH 2) 3-    N(CH 2CH 3)C 6H 5 5.159    -(CH 2) 3-    
Figure A9519765200811
5.160    -(CH 2) 3-     5.161    -(CH 2) 3-    
Figure A9519765200813
5.162    -(CH 2) 4-2-Yi base-1-piperidyl 5.163-(CH2) 4-3-methyl isophthalic acid-piperidyl 5.164-(CH2) 4-4-methyl isophthalic acid-piperidyl 125-127 °
Table 6
Figure A9519765200821
Compound R2      R 3        B                     R 4Physical data numbering 6.1-(CH2) 4235 ° of (decomposition) 6.2-(CH of-1-Nai base 6-Cl2) 4193-195 ° of (decomposition) 6.3-(CH of-2-Nai base 6-Cl2) 4-     -N(CH 3)-c-C 6H 11        6-Cl       155-158° 6.4    -(CH 2) 4-     -N(CH 2CH 2OCH 3) 26-Cl Shu Zhi 6.5-(CH2) 4-     -N(CH 2CH 3)C 6H 5       6-Cl 6.6    -(CH 2) 4-     
Figure A9519765200822
        6-Cl 6.7    -(CH 2) 4-        6-Cl    163-166° 6.8    -(CH 2) 4-     
Figure A9519765200824
            6-Cl 6.9    -(CH 2) 3-1-Nai base 6-Cl 6.10-(CH2) 3-2-Nai base 6-Cl 6.11-(CH2) 3-     -N(CH 3)-c-C 6H 11         6-Cl 6.12   -(CH 2) 3-     -N(CH 2CH 2OCH 3) 2       6-Cl 6.13   -(CH 2) 3-     -N(CH 2CH 3)C 6H 5        6-Cl 6.14   -(CH 2) 3-     
Figure A9519765200825
The 6-Cl compound R2  R 3                 B                             R 4Physical data numbering 6.15-(CH2) 3-             
Figure A9519765200831
       6-Cl 6.16  -(CH 2) 3-                              6-Cl 6.17  -CH 3  -CH 31-Nai base 6-Cl 6.18-CH3  -CH 32-Nai base 6-Cl 6.19-CH3  -CH 3           -N(CH 3)-c-C 6H 11             6-Cl 6.20  -CH 3  -CH 3           -N(CH 2CH 2OCH 3) 2           6-Cl 6.21  -CH 3  -CH 3           N(CH 2CH 3)C 6H 5             6-Cl 6.22  -CH 3  -CH 3                         6-Cl 6.23  -CH 3  -CH 3                 6-Cl 6.24  -CH 3  -CH 3           
Figure A9519765200835
              6-Cl 6.25  -CH 3  -C 2H 51-Nai base 6-Cl 6.26-CH3  -C 2H 52-Nai base 6-Cl 6.27-CH3  -C 2H 5        -N(CH 3)-c-C 6H 11           6-Cl 6.28  -CH 3  -C 2H 5        -N(CH 2CH 2OCH 3) 2         6-Cl 6.29  -CH 3  -C 2H 5        N(CH 2CH 3)C 6H 5           6-Cl 6.30  -CH 3  -C 2H 5         The 6-Cl compound R2    R 3           B                            R 4Physical data numbering 6.31-CH3    -C 2H 5    
Figure A9519765200841
    6-Cl 6.32  -CH 3    -C 2H 5                   6-Cl 5.33  -C 2H 5  -C 2H 5181-183 ° of 6.34-C of 1-Nai base 6-Cl2H 5  -C 2H 52-Nai base 6-Cl 5.35-C2H 5  -C 2H 5    -N(CH 3)-c-C 6H 11            6-Cl 6.36  -C 2H 5  -C 2H 5    -N(CH 2CH 2OCH 3) 2          6-Cl 6.37  -C 2H 5  -C 2H 5    N(CH 2CH 3)C 6H 5            6-Cl 6.38  -C 2H 5  -C 2H 5                  6-Cl 6.39  -C 2H 5  -C 2H 5            6-Cl 6.40  -C 2H 5  -C 2H 5                      6-Cl 6.41  
Figure A9519765200846
1-Nai base 6-Cl 6.42
Figure A9519765200847
2-Nai base 6-Cl 6.43
Figure A9519765200848
  -N(CH 3)-c-C 6H 11              6-Cl 6.44  
Figure A9519765200849
  -N(CH 2CH 2OCH 3) 2            6-Cl 6.45     N(CH 2CH 3)C 6H 5The 6-Cl compound R2 R 3               B                           R 4Physical data numbering 6.46
Figure A9519765200851
         6-Cl 6.47      6-Cl 6.48               6-Cl 6.49  -(CH 2) 4-1-Nai base 6-F 6.50-(CH2) 42-Nai base 6-F 6.51-(CH2) 4               -N(CH 3)-c-C 6H 11        6-F 6.52  -(CH 2) 4               -N(CH 2CH 2OCH 3) 2       6-F 6.53  -(CH 2) 4               N(CH 2CH 3)C 6H 5         6-F 6.54  -(CH 2) 4               
Figure A9519765200854
       6-F 6.55  -(CH 2) 4               
Figure A9519765200855
6-F   156-158° 6.56  -(CH 2) 4               
Figure A9519765200856
         6-F 6.57  -(CH 2) 3-1-Nai base 6-F 6.58-(CH2) 3-2-Nai base 6-F 6.59-(CH2) 3-              -N(CH 3)-c-C 6H 11       6-F 6.60  -(CH 2) 3-              -N(CH 2CH 2OCH 3) 2     6-F 6.61  -(CH 2) 3-              N(CH 2CH 3)C 6H 5The 6-F compound R2   R 3      B                        R 4Physical data numbering 6.62-(CH2) 3-             6-F 6.63  -(CH 2) 3-     
Figure A9519765200862
6-F 6.64  -(CH 2) 3-               6-F 6.65  -CH 3  -CH 3175-176 ° of 6.66-CH of 1-Nai base 6-F3  -CH 32-Nai base 6-F 6.67-CH3  -CH 3   -N(CH 3)-c-C 6H 11      6-F 6.68  -CH 3  -CH 3   -N(CH 2CH 2OCH 3) 2     6-F 6.69  -CH 3  -CH 3   N(CH 2CH 3)C 6H 5       6-F 6.70  -CH 3  -CH 3   
Figure A9519765200864
       6-F 6.71  -CH 3  -CH 3     6-F         156-158° 6.72  -CH 3  -CH 3               6-F 6.73  -CH 3  -C 2H 51-Nai base 6-F 6.74-CH3  -C 2H 52-Nai base 6-F 6.75-CH3  -C 2H 5 -N(CH 3)-c-C 6H 11         6-F 6.76  -CH 3  -C 2H 5 -N(CH 2CH 2OCH 3) 2       6-F 6.77  -CH 3  -C 2H 5 N(CH 2CH 3)C 6H 5The 6-F compound R2  R 3          B                            R 4Physical data numbering 6.78-CH3    -C 2H 5            6-F 6.79  -CH 3    -C 2H 5  
Figure A9519765200872
  6-F 6.80  -CH 3    -C 2H 5               6-F 6.81  -C 2H 5  -C 2H 51-Nai base 6-F 6.82-C2H 5  -C 2H 52-Nai base 6-F 6.83-C2H 5  -C 2H 5  -N(CH 3)-c-C 6H 11         6-F 6.84  -C 2H 5  -C 2H 5  -N(CH 2CH 2OCH 3) 2       6-F 6.85  -C 2H 5  -C 2H 5  N(CH 2CH 3)C 6H 5         6-F 6.86  -C 2H 5  -C 2H 5  
Figure A9519765200874
         6-F 6.87  -C 2H 5  -C 2H 5     6-F 6.88  -C 2H 5  -C 2H 5  
Figure A9519765200876
           6-F 6.89  
Figure A9519765200877
1-Nai base 6-F 6.902-Nai base 6-F 6.91 -N(CH 3)-c-C 6H 11The 6-F compound R2   R 3             B                     R 4Physical data numbering 6.92
Figure A9519765200881
      -N(CH 2CH 2OCH 3) 2  6-F 6.93
Figure A9519765200882
      N(CH 2CH 3)C 6H 5    6-F 6.94
Figure A9519765200883
      6-F 6.95 6-F 6.96
Figure A9519765200885
         6-F
Table 7
Figure A9519765200891
Compound R 2R 3B R 4N physical data numbering 7.1-(CH 2) 4-1-naphthyl 2-CH 3, 6-CH 327.2-(CH 2) 4-2-naphthyl 2-CH 3, 6-CH 327.3-(CH 2) 4--N (CH 3)-c-C 6H 112-CH 3, 6-CH 327.4-(CH 2) 4--N (CH 2CH 2OCH 3) 22-CH 3, 6-CH 327.5-(CH 2) 4--N (CH 2CH 3) C 6H 52-CH 3, 6-CH 327.6-(CH 2) 4- 2-CH 3, 6-CH 327.7-(CH 2) 4-
Figure A9519765200893
2-CH 3, 6-CH 327.8-(CH 2) 4-
Figure A9519765200894
2-CH 3, 6-CH 327.9-(CH 2) 4-1-naphthyl 2-C 2H 5, 4-C 2H 5, 3
6-C 2H 57.10-(CH 2) 4-2-naphthyl 2-C 2H 5, 4-C 2H 5, 3
6-C 2H 57.11??-(CH 2) 4-????-N(CH 3)-c-C 6H 11?????????2-C 2H 5,4-C 2H 5,3
6-C 2H 57.12??-(CH 2) 4-????-N(CH 2CH 2OCH 3) 2????????2-C 2H 5,4-C 2H 5,3
6-C 2H 57.13??-(CH 2) 4-????-N(CH 2CH 3)C 6H 5?????????2-C 2H 5,4-C 2H 5,3
6-C 2H 5Compound R 2R 3B R 4N physical data numbering 7.14-(CH 2) 4- 2-C 2H 5, 4-C 2H 5, 3
6-C 2H 57.15???-(CH 2) 4-? 2-C 2H 5,4-C 2H 5,????3
6-C 2H 57.16???-(CH 2) 4-? ??????????2-C 2H 5,4-C 2H 5,????3
6-C 2H 57.17 CH 3CH 31-naphthyl 2-CH 3, 6-CH 327.18 CH 3CH 32-naphthyl 2-CH 3, 6-CH 327.19 CH 3CH 3-N (CH 3)-c-C 6H 112-CH 3, 6-CH 327.20 CH 3CH 3-N (CH 2CH 2OCH 3) 22-CH 3, 6-CH 327.21 CH 3CH 3-N (CH 2CH 3) C 6H 52-CH 3, 6-CH 327.22 CH 3CH 3 2-CH 3, 6-CH 327.23 CH 3CH 3
Figure A9519765200905
2-CH 3, 6-CH 327.24 CH 3CH 3
Figure A9519765200906
2-CH 3, 6-CH 327.25 CH 3CH 31-naphthyl 2-C 2H 5, 4-C 2H 5, 3
6-C 2H 57.26 CH 3CH 32-naphthyl 2-C 2H 5, 4-C 2H 5, 3
6-C 2H 57.27 CH 3CH 3-N (CH 3)-c-C 6H 112-C 2H 5, 4-C 2H 5, 3 compound Rs 2R 3B R 4N physical data numbering
6-C 2H 57.28????CH 3?CH 3??-N(CH 2CH 2OCH 3) 2?????2-C 2H 5,4-C 2H 5,???3
6-C 2H 57.29????CH 3?CH 3??-N(CH 2CH 3)C 6H 5??????2-C 2H 5,4-C 2H 5,???3
6-C 2H 57.30????CH 3?CH 3??
Figure A9519765200911
???????2-C 2H 5,4-C 2H 5,????3
6-C 2H 57.31????CH 3?CH 3??
Figure A9519765200912
?2-C 2H 5,4-C 2H 5,????3
6-C 2H 57.32????CH 3?CH 3??
Figure A9519765200913
??????????2-C 2H 5,4-C 2H 5,????3
6-C 2H 57.33-(CH 2) 3-1-naphthyl 2-CH 3, 6-CH 327.34-(CH 2) 3-2-naphthyl 2-CH 3, 6-CH 327.35-(CH 2) 3--N (CH 3)-c-C 6H 112-CH 3, 6-CH 327.36-(CH 2) 3--N (CH 2CH 2OCH 3) 22-CH 3, 6-CH 327.37-(CH 2) 3--N (CH 2CH 3) C 6H 52-CH 3, 6-CH 327.38-(CH 2) 3- 2-CH 3, 6-CH 327.39-(CH 2) 3-
Figure A9519765200915
2-CH 3, 6-CH 327.40-(CH 2) 3- 2-CH 3, 6-CH 32 compound Rs 2R 3B R 4N physical data numbering 7.41-(CH 2) 3-1-naphthyl 2-C 2H 5, 4-C 2H 5, 3
6-C 2H 57.42-(CH 2) 3-2-naphthyl 2-C 2H 5, 4-C 2H 5, 3
6-C 2H 57.43????-(CH 2) 3-????-N(CH 3)-c-C 6H 11????2-C 2H 5,4-C 2H 5,????3
6-C 2H 57.44????-(CH 2) 3-????-N(CH 2CH 2OCH 3) 2??2-C 2H 5,4-C 2H 5,????3
6-C 2H 57.45????-(CH 2) 3-????-N(CH 2CH 3)C 6H 5???2-C 2H 5,4-C 2H 5,????3
6-C 2H 57.46????-(CH 2) 3-
Figure A9519765200921
???????2-C 2H 5,4-C 2H 5,????3
6-C 2H 57.47????-(CH 2) 3- ?2-C 2H 5,4-C 2H 5,????3
6-C 2H 57.48????-(CH 2) 3-
Figure A9519765200923
??????????2-C 2H 5,4-C 2H 5,????3
6-C 2H 5
Table 8
Figure A9519765200931
Compound
X 2R 15Number 8.1 Cl-CH (CH 3)-C 5H 11-n8.2 Cl-CH (CH 3)-CH 2OCH 2CH=CH 28.3 Cl H8.4 Cl C 4H 9-n table 9
Figure A9519765200932
Compound o.
R 19R 16R 17R 18E numbers 9.1 CH 3Phenyl 2-Cl H CH9.2 CH 3Phenyl 2-Cl 4-Cl CH9.3 CH 3Phenyl 2-F H CH9.4 CH 32-chloro-phenyl-2-F H CH9.5 C 2H 5CCl 32-Cl 4-Cl N9.6 CH 3Phenyl 2-Cl 4-CF 3N9.7 CH 3Phenyl 2-Cl 4-CF 3The example of formulations F1 to F10 of N formula I desinsection and acaricidal activity material, (%=weight percent) embodiment F 1: missible oil is b a)) c) according to the active substance of table 1 to 7 25% 40% 50% calcium dodecylbenzene sulphonates 5% 8% 6% Viscotrol C polyglycol ethers, (36mol 5%--EO) the poly-second two-alcohol ether of tributyl phenol-12% 4%, (30mol EO) pimelinketone-15% 20% dimethylbenzene mixes 65% 25% 20%
The active substance that grinds is very carefully mixed with additive, provide missible oil, the missible oil dilute with water provides the emulsion of desired concn.Embodiment F 2: solution is b a)) c) d) and according to the active substance of table 1 to 7 80% 10% 5% 95% ethylene glycol monomethyl ethers 20%---polyoxyethylene glycol, (MW400)-70%--N-methylpyrrolidin-2-ketone-20%--epoxidised Oleum Cocois--1% 5% industrial naptha, (boiling point: 160-190--94%-℃)
The active substance that grinds is very carefully mixed with additive, provide and be suitable for the solvent used with the form of very little droplet.Embodiment F 3: granule is b a)) c) d) according to the active substance of table 1 to the 7 5% 10% 8% 21% kaolin 94%-79% 54% high dispersive silica 1 %-13% 7% U.S. soil-90%-18% of silicon
Active substance is dissolved in the methylene dichloride, solution is applied on the carrier mixture by spraying, and vaporising under vacuum is except that desolvating.Embodiment F 4: pulvis is b a)) according to the active substance of table 1 to 7 2% 5% high dispersive silica 1 % 5% talcum 97%-kaolin-90%
Active substance mixed with carrier provide direct available pulvis. Shi Shi example F5: wettable powder is b a)) c) according to table 1 Zhi 7 active material 25% 50% 75% lignosulphonic acid Na 5% 5%-NaLS, 3%-5% diisobutyl Nai sodium sulfonates-6% 10% octyl phenol polyglycol ether (7--2%-8mol EO) high dispersive silica 5% 10% 10% kaolin 62% 27%-
Active substance is mixed with additive, and mixture is ground in the mill that is fit to.Obtain wettable powder, it can dilute with water, provides the suspension of desired concn.Embodiment F 6: missible oil is according to active substance 10% octylphenol polyethylene glycol ether (4-3%5mol EO) calcium dodecylbenzene sulphonate 3% Viscotrol C polyglycol ether (36mol 4%EO) pimelinketone 30% xylene mixture 50% of table 1 to 7
The active substance that grinds is very carefully mixed with additive, provide missible oil, the missible oil dilute with water provides the emulsion of desired concn.Embodiment F 7: pulvis is b a)) slide 95%-kaolin-92% according to table 1 to 7 active substance 8%
Active substance is mixed with carrier, and in the mill that is fit to, grind, provide the pulvis that directly to use.Embodiment F 8: the extrusion type granule is according to active substance 10% sodium lignosulfonate 2% carboxymethyl cellulose 1% kaolin 87% of table 1 to 7
Active substance is mixed with carrier, and mixture is ground, use water-wet, extruding and granulation, particle is dry under airflow.Embodiment F 9: the coating-type granule is according to active substance 3% polyoxyethylene glycol (MW 200) 3% kaolin 94% of table 1 to 7
Active substance is applied on the kaolin equably, wetting with polyoxyethylene glycol, in mixing machine, provide non-dusting coating-type granule.Embodiment F 10: suspension agent is according to active substance 40% ethylene glycol 10% Nonoxynol-9 (15mol 6%EO) sodium lignosulfonate 10% carboxymethyl cellulose 1% formalin (37%) 0.2% moisture polysiloxane oil-emulsion (75%) 0.8% water 32% of table 1 to 7
The active substance that grinds is very carefully mixed with additive, provide suspension agent, its dilute with water can provide the suspension of desired concn.The example of formulations F11 to F18 of formula I herbicidal active compounds, (%=weight percent) embodiment F 11: missible oil is b a)) c) d) according to the active substance of table 1 to 7 5% 10% 25% 50% calcium dodecylbenzene sulphonates 6% 8% 6% 8% Viscotrol C polyglycol ethers, (36mol 4%-4% 4%EO) octylphenol polyethylene glycol ether, (7--4%-2%8mol EO) pimelinketone--10% 20% aromatic hydrocarbons mixture C 9-C 1285% 78% 55% 16%
By these missible oil,, can prepare the emulsion of any desired concn by dilute with water.Embodiment F 12: solution is b a)) c) d) and according to the active substance of table 1 to 7 5% 10% 50% 90% dipropylene glycol methyl ether-20% 20%-polyoxyethylene glycol (MW4 00) 20% 10%--N-N-methyl-2-2-pyrrolidone N---30% 10% aromatic hydrocarbons mixture C 9-C 1275% 60%--
These solution are suitable for using with the form of very little droplet. Shi Shi example F13: wettable powder is b a)) c) d) active material 5% 25% 50% 80% lignosulphonic acid Na 4%-3%-NaLS 2% 3%-4% diisobutyl Nai sodium sulfonates-6% 5% 6% octyl phenol polyglycol ether (7--1% 2%-8mol EO) high dispersive silica 1 % 3% 5% 10% kaolin 88% 62% 35% according to table 1 Zhi 7
Active substance is thoroughly mixed with additive, and mixture is thoroughly ground in the mill that is fit to.Obtain wettable powder, it can dilute with water, provides required suspension.Embodiment F 14: the coating-type granule is b a)) c) according to the active substance of table 1 to 7 0.1% 5% 15% high dispersive silicon-dioxide 0.9% 2% 2% inorganic carrier materials (Φ 0.1-1mm) 99.0% 93% 83% as CaCO 3Or SiO 2
Active substance is dissolved in methylene dichloride, this solution is applied on the carrier by spraying, subsequently the vaporising under vacuum solvent.Embodiment F 15: the coating-type granule is b a)) c) according to the active substance of table 1 to 7 0.1% 5% 15% polyethylene glycol MW 200 1.0% 2% 3% high dispersive silicon-dioxide 0.9% 1% 2% inorganic carrier materials (Φ 0.1-1mm) 98.0% 92% 80% as CaCO 3Or SiO 2
In mixing machine, active substance is applied on the solid support material equably, wetting with polyoxyethylene glycol.Obtain non-dusting coating-type granule in this way.Embodiment F 16: the extrusion type granule is b a)) c) d) according to the active substance of table 1 to 7 0.1% 3% 5% 15% sodium lignosulfonates 1.5% 2% 3% 4% carboxymethyl celluloses 1.4% 2% 2% 2% kaolin 97.0% 93% 90% 79%
With active substance and additives mixed, and this mixture ground and uses water-wet.This mixture is extruded, dry in airflow subsequently.Embodiment F 17: pulvis is b a)) c) according to the active substance of table 1 to 7 0.1% 1% 5% talcums 39.9% 49% 35% kaolin 60.0% 50% 60%
Active% 20substance% 20and% 20mixed% 20being% 20incorporated% 20in% 20the% 20suitable% 20mill% 20of% 20carrier% 20are% 20ground% 2C% 20obtain% 20direct% 20available% 20pulvis.% E5% AE% 9E% E6% 96% BD % E4% BE% 8BF18% EF% BC% 9A% E6% 82% AC% E6% B5% AE% E5% 89% 82% 20a% 20% 20)% 20% 20b% 20% 20)% 20% 20c % 20% 20)% 20% 20d% 20% 20)% 20% 20% E6% A0% B9% E6% 8D% AE% E8% A1% A81% E8% 87% B37% E7% 9A% 84% E6 % B4% BB% E6% 80% A7% E7% 89% A9% E8% B4% A8% 203% EF% BC% 85% 2010% EF% BC% 85% 2025% EF% BC% 85% 2050% EF % BC% 85% E4% B9% 99% E4% BA% 8C% E9% 86% 87% 205% EF% BC% 85% 205% EF% BC% 85% 205% EF% BC% 85% 205% EF % BC% 85% E5% A3% AC% E5% 9F% BA% E8% 8B% AF% E9% 85% 9A% E8% 81% 9A% E4% B9% 99% E4% BA% 8C% E9% 86 % 87% E9% 86% 9A% 20% 20% 20 (% 20% 2015mol-1% EF% BC% 85% 202% EF% BC% 85-EO% 20% 20)% 20% 20% E6% 9C % A8% E7% B4% A0% E7% A3% BA% E9% 85% B8% E9% 92% A0% 203% EF% BC% 85% 203% EF% BC% 85% 204% EF% BC% 85 % 205% EF% BC% 85% E7% BE% A7% E7% 94% B2% E5% 9F% BA% E7% BA% A4% E7% BB% B4% E7% B4% A0% 201% EF% BC % 85% 201% EF% BC% 85% 201% EF% BC% 85% 201% EF% BC% 8537% EF% BC% 85% E7% 94% B2% E9% 86% 9B% E6% B0% B4 % E6% BA% B6% E6% B6% B2% 200.2% EF% BC% 85% 200.2% EF% BC% 85% 200.2% EF% BC% 85% 200.2% EF% BC% 85% E8% 81% 9A % E7% A1% 85% E6% B0% A7% E7% 83% B7% E6% B2% B9% E4% B9% B3% E5% 89% 82% 200.8% EF% BC% 85% 200.8% EF% BC % 85% 200.8% EF% BC% 85% 200.8% EF% BC% 85% E6% B0% B4% 2087% EF% BC% 85% 2079% EF% BC% 85% 2062% EF% BC% 85% 2038 % EF% BC% 85
The active substance that grinds is very carefully mixed with additive.Obtain suspension agent in this way, its dilute with water can provide the suspension of desired concn. Herbicidal active substances of formula I with a mixture of safener Formulation Example F19 to F26 (% = percentage by weight) Example F19: EC a) b) c) d) active substance mixture 5% 10% 25% 50% calcium dodecylbenzenesulfonate 6% 8% 6% 8% castor oil polyethylene glycol ether (36mol 4% -4% 4% EO) octylphenol polyethylene glycol ether (7 - 4% -2% 8mol EO) cyclohexanone - 10% 20% aromatics mixture C9-C 1285% 78% 55% 16%
By these missible oil,, can prepare the emulsion of any desired concn by dilute with water.Embodiment F 20: solution is b a)) c) d) active material admixture 5% 10% 50% 90% dipropylene glycol methyl ether-20% 20%-polyoxyethylene glycol (MW4 00) 20% 10%--N-N-methyl-2-2-pyrrolidone N---30% 10% aromatic hydrocarbons mixture C 9-C 1275% 60%--
These solvents are suitable for using with the form of very little droplet. Shi Shi example F21: wettable powder is b a)) c) d) active material admixture 5% 25% 50% 80% lignosulphonic acid Na 4%-3%-NaLS 2% 3%-4% diisobutyl Nai sodium sulfonates-6% 5% 6% octyl phenol polyglycol ether (7--1% 2%-8mol EO) high dispersive silica 1 % 3% 5% 10% kaolin 88% 62% 35%-
Active substance is thoroughly mixed with additive, and mixture is thoroughly ground in the mill that is fit to.Obtain wettable powder, it can dilute with water, provides the suspension of desired concn.Embodiment F 22: the coating-type granule is b a)) c) active material admixture 0.1% 5% 15% high dispersive silicon-dioxide 0.9% 2% 2% inorganic carrier materials (Φ 0.1-1mm) 99.0% 93% 83% are as CaCO 3Or SiO 2
Active substance is dissolved in methylene dichloride, this solution is applied on the carrier by spraying, subsequently the vaporising under vacuum solvent.Embodiment F 23: the coating-type granule is b a)) c) active substance mixes 0.1% 5% 15% polyethylene glycol MW 200,1.0% 2% 3% high dispersive silicon-dioxide, 0.9% 1% 2% inorganic carrier materials (Φ 0.1-1mm) 98.0% 92% 80% as CaCO 3Or SiO 2
In mixing machine, the active substance of porphyrize is applied on the solid support material equably, wetting with polyoxyethylene glycol.Obtain non-dusting coating-type granule in this way.Embodiment F 24: the extrusion type granule is b a)) c) d) active material admixture 0.1% 3% 5% 15% sodium lignosulfonates 1.5% 2% 3% 4% carboxymethyl celluloses 1.4% 2% 2% 2% kaolin 97.0% 93% 90% 79%
With active substance and additives mixed, and this mixture ground and uses water-wet.This mixture is extruded, dry in airflow subsequently.Embodiment F 25: pulvis is b a)) c) active material admixture 0.1% 1% 5% talcums 39.9% 49% 35% kaolin 60.0% 50% 60%
Active substance and mixed being incorporated in the suitable mill of carrier are ground, obtain direct available pulvis. Example F26: Suspension a) b) c) d) active substance mixture 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenol polyethylene glycol ether (15mol-1% 2%-EO) sodium ligninsulfonate 3% 3% 4% 5% carboxymethylcellulose 1% 1% 1% 1% 37% aqueous formaldehyde solution 0.2% 0.2% 0.2% 0.2% silicone oil emulsion 0.8% 0.8% 0.8% 0.8% water 87% 79% 62% 38%
The active substance that grinds is very carefully mixed with additive.Obtain suspension agent in this way, its dilute with water can provide the suspension of desired concn.Biological Examples (%=weight percent, A. insecticidal action Embodiment B 1 unless otherwise): to the effect of black peach aphid
To put black peach aphid on the pea seedlings, cultivate down subsequently with the spray mixing thing spraying that comprises the 400ppm activeconstituents, and at 20 ℃.After 3 days and 6 days test is estimated.By the dead borer population on the comparison process plant and the plant of being untreated, determine that population reduces percentage (effect %).
Table 1 to 7 compound demonstrates good effect in this test.Embodiment B 2: to the effect of Nilaparvata lugen (brown planthopper)
Handle the rice strain with the aqueous emulsion spraying fluid that comprises the 400ppm activeconstituents, after the spraying liquid layer drying, in the rice strain, put 2 and 3 instar larvaes.After 21 days,, determine that population reduces percentage (effect %) by the survival larva number on the comparison process plant and the plant of being untreated.
Table 1 to 7 compound demonstrates good effect in this test.Embodiment B 3: to the effect (interior suction) of Nilaparvata lugen (brown planthopper)
The basin of plantation rice strain is positioned in the aqueous emulsion that comprises the 400ppm activeconstituents.In the rice strain, put 2 and 3 instar larvaes afterwards.After 6 days,, determine that population reduces percentage (effect %) by the survival larva number on the comparison process plant and the plant of being untreated.
Table 1 to 7 compound demonstrates good effect in this test.B. the acaricidal action Embodiment B 4: to the effect of boophilus microplus
Complete full female one-tenth tick is drawn on the PVC plate, and builds, on these ticks, pour the test water solution that 10ml contains the 125ml activeconstituents with cotton mattress.Remove cotton mattress, the ox tick was cultivated for 4 weeks, allow it lay eggs.No matter be, cause it dead or sterile, or on the ovicidal action to ovum, the effect of activeconstituents be tangible female tick.
Table 1 to 7 compound demonstrates good effect in this test.Embodiment B 5: to the effect of T.urticae Koch
On bean seedlings, put different worms and mix the T.urticae Koch colony of giving birth to age, after 1 day,, bean seedlings were cultivated 6 days down at 25 ℃, estimate subsequently with the aqueous emulsions spraying fluid spraying that contains the 400ppm activeconstituents.By ovum, larva dead on comparison process plant and the plant of being untreated with become borer population, determine that population reduces percentage (effect %).
Table 1 to 7 compound demonstrates good effect in this test.Particularly following compounds demonstrates greater than 80% effect: compound 1.1 to 1.9,1.11 to 1.28,1.33 to 1.40,1.44 to 1.49,1.51,1.53,1.55 to 1.61,2.2,2.6 to 2.14,2.16,2.17,2.20,2.21,3.1,5.15,5.47,5.80,5.88,5.107,5.110,5.112,5.122,6.2 to 6.4 and 6.7.C. the herbicide effect Embodiment B 6: the herbicide effect (before the bud) before the plant germination
Unifacial leaf and dicotyledonous test plant in the standard soil of plastic tub, sowing.After planting, use at once by the aqeous suspension of 25% wettable powder (embodiment F 13, b)) preparation test compound with 2kg AS/ha (the amount spraying of 500 l water/ha).Grow in the greenhouse under the top condition with the relief test plant.Test lasted for 3 weeks, and experiment is marked with 9 grades (1=damages fully, and 9=does not have effect).Grade 1 to 4 (particularly 1 to 3) refers to have good in extraordinary herbicide effect.
In this experiment; the compound exhibits of table 1-7 goes out strong herbicide effect, and this point for example is found in shown result in the table 10. TABLE 10 Compound No. Avena Setaria genus Brassica chickweed 1.5 313 81.9 222 71.13 213 91.14 212 91.19 212 51.21 213 71.24 313 71.25 313 71.26 112 81.27 313 71.33 212 91.35 211 64.15 119 94.16 1 19 84.22 1299 Example B7: plants after germination herbicidal action (contact with herbicides)
Unifacial leaf and dicotyledonous test plant on planting in the greenhouse standard soil in plastic tub.And use by the aqeous suspension of 25% wettable powder (embodiment F 13, b)) preparation formula I test compound with 2kg AS/ha (the amount spraying of 500 l water/ha) in 4 to 6 leaf phases.Grow in the greenhouse under the top condition with the relief test plant.Behind about 18 days trial period, experiment is marked with 9 grades (1=damages fully, and 9=does not have effect).Grade 1 to 4 (particularly 1 to 3) refers to have good in extraordinary herbicide effect.
In this experiment; The compound exhibits of table 1-7 goes out strong herbicide effect, and this point for example is found in shown result in the table 11. table 11 compound sequence number Avena setaria mustard belong to Stellaria 1.5 122 51.9 112 41.13 122 31.14 123 51.19 122 41.21 233 61.24 113 41.25 113 41.26 112 31.27 112 71.33 112 41.35 112 54.15 133 94.16 123 74.22 122 9D. safener effect Embodiment B 8: the safener effect
Under greenhouse experiment, allow test plant in plastic tub, grow to for 4 leaf phases.In this stage, be applied on the test plant with independent weedicide and weedicide and as the mixture of the substances of safener test.Using what take is that spray amount is 500 l water/ha by the substances aqeous suspension spraying of 25% wettable powder (embodiment F 21, b)) preparation.After using for 3 weeks, adopt the percentage classification to estimate weedicide to for example poisoning of corn and cereal class of crop.100% is meant test plant death, and 0% is meant no poisoning effect.
This experiment shows, with the compound of formula X or XI, for example uses compound 8.1, can make formula I herbicidal compound for example the infringement of the such crop of 1.13 pairs of compounds such as corn or cereal class reduce greatly.

Claims (58)

1. Yi Zhong Xia Shi compoundQi Zhong R1The Shi groupQu is for basic R4Xiang is basic, the C of Shi halogen, Xiao base, Qing independently mutually1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 10-alcoxyl base, C1-C 4-halogenated alkoxy, C3-C 6-alkenyloxy, C1-C 4-alcoxyl base-C2-C 4-alcoxyl base, C3-C 6-Que Yang base, C1-C 4-Wan base Tang base, C1-C 4-alcoxyl Tang base, C1-C 4-Wan sulfenyl, C1-C 4-Wan base sulfinyl, C1-C 4-Wan base sulfonyl, amino, C1-C 4-Wan base amino or two (C1-C 4-Wan yl) amino; R5The Shi group
Figure A9519765200023
N Shi 0,1,2,3 or 4; M Shi 0 or 1, Qie m is Yu n Zhi and Shi 0,1,2,3 or 4; Q Shi 0,1,2 or 3; X1Shi Yang, sulphur ,-CH2-or-N (R7)-; Qu is for basic R6Xiang is Shi C independently mutually1-C 4-Wan base, halogen, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, Xiao base, Qing are basic, C1-C 4-alcoxyl base Tang base, amino, C1- C 4-Wan base amino or two (C1-C 4-Wan yl) amino; R7Shi Qing, C1-C 4-Wan base, formoxyl or C1-C 4-alcoxyl Tang base; R2And R3Xiang is Shi Qing, C independently mutually1-C 8-Wan base, C3-C 8-alkenyl, C3-C 8-alkynyl, C1-C 8-alcoxyl base Wan base, C1-C 8-Wan sulfenyl Wan base, C3-C 8-cycloalkyl or Qu generation or unsubstituted aryl; Or R2And R3That Yi Qi Xing becomes is saturated or unsaturated, Wei Qu generation or Qu generation single, two, the divalent group of San or polycyclic system, Zhe Xie Ti Xi can Ren Xuan Zai not Yu the nitrogen-atoms Xiang neighbour's of Shi Yu Shi I Wei Zhi Shang contain Yi or a plurality of ring hetero atom; G Shi group-CO-A (a) or-SO2-B (b); A Shi C1-C 8-Wan base, Ta You Xiao is basic, Qing is basic, Si (C1-C 4-Wan yl)3, amino, C1-C 4-Wan base is amino, two (C1-C 4-Wan yl) amino, Qu generation or unsubstituted benzyloxy or groupOr A Shi C3-C 8-cycloalkyl, Ru fruit Xu Yao, Ta can contain Za elemental oxygen, sulphur or nitrogen, and this cycloalkyl of Qie can You C1-C 4-Wan base, C1-C 4-alcoxyl base, C1-C 4-Wan sulfenyl, C1-C 4-Wan base sulfinyl, C1-C 4-Wan base sulfonyl or Qu generation or unsubstituted phenyl substituted, or A Shi C3-C 8-cycloalkyl oxy, Ru fruit Xu Yao, Ta can contain Za elemental oxygen, sulphur or nitrogen, and this cycloalkyl oxy of Qie can You C1-C 4-Wan base Qu generation, or A Shi gold steel Wan base, Nai are basic, You halogen, C1-C 4-Wan base, C1-C 4-haloalkyl or C1-C 4The Nai base in-alcoxyl base Qu generation, or A Shi group-(CR8R 9) p-(Y) o-CO-(Z) r-R 10、-(CR 8R 9) p-R 11Or-N (R10)R 13;R 08、R 09And R010Xiang is Shi Qing or C independently mutually1-C 6-Wan base; R8And R9Xiang is Shi Qing, C independently mutually1-C 6-Wan base or phenyl; R10Shi Qing, C1-C 10The C in-Wan base, You halogen Qu generation1-C 10-Wan base, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, C3-C 12-cycloalkyl, Qing base, aryl or aryloxy group, C3-C 8-cycloalkyl, You halogen or C1-C 4The C in-Wan base Qu generation3-C 8-cycloalkyl, C3-C 10-alkenyl, C3-C 10-alkynyl, C3-C 10-halogenated alkenyl, C3-C 10-halo alkynyl, aryl, You Xia row Qu are for the basic Qu aryl in generation: halogen, C1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 6-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, the phenoxy group halogenated phenoxy; O and r Xiang be Shi 0 or 1 independently mutually; Y and Z Xiang be Shi Yang or NR independently mutually12 P Shi 1 is Zhi 10; R11Shi C3-C 8-cycloalkyl, You halogen or C1-C 4The C in-Wan base Qu generation3-C 8-cycloalkyl, aryloxy group, You halogen, C1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, phenoxy group or aryloxy group, benzyloxy, You halogen, the C in halogenated phenoxy Qu generation1-C 4-Wan base, C1-C 4-substituted alkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, phenoxy group or benzyloxy, norborny or the golden steel Wan base in halogenated phenoxy Qu generation, Qi Zhong aryloxy group except phenoxy group, the aryloxy group that each can what Suo Xu of Shi Ren; R12Shi Qing, C1-C 4-Wan base, C3-C 8-cycloalkyl, C3-C 10-alkenyl or C3-C 10-alkynyl; R13Shi C3-C 8-cycloalkyl, You halogen or C1-C 4The C in-Wan base Qu generation3-C 8-cycloalkyl or Qing base-C1-C 6-Wan base; B Shi C1-C 10-Wan base, Ta You Xia row Qu is for basic Qu generation: C1-C 4-alcoxyl base, C1-C 6-alcoxyl base-C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, C1-C 4-halogenated alkylthio, C1-C 4-Wan base sulfinyl, C1-C 4-Wan base sulfonyl, C1-C 4-Wan base sulfonyloxy, C1-C 4-Wan base Tang base, C1-C 4-alcoxyl base Tang base, C1-C 4-Wan base Tang Yang base, two (C1-C 4-Wan yl) amino, C3-C 8-cycloalkyl, aryl, aryloxy group, arylthio, aryl sulfonyl, aryl sulfonyl kia, aryl-sulfonyl oxygen, aryl carbonyl or Bi Ding base, Ru fruit Xu Yao, aryl or Bi Ding base can You Xia row Qu for basic Qu generation: halogen, C1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, phenoxy group, halogenated phenoxy, thiophenyl or halogeno-benzene sulfenyl, or B Shi C3-C 10-alkenyl, C3-C 10-halogenated alkenyl, C3-C 10-alkynyl, C3-C 10-halo alkynyl, C3-C 8-cycloalkyl, You halogen or C1-C 4The C in-Wan base Qu generation3-C 8-cycloalkyl, Bian base, You halogen, C1-C 4-Wan base, C1-C 4-haloalkyl or C1-C 4The Bian base in-alcoxyl base Qu generation, Nai are basic, You halogen or the Nai base in Xiao base Qu generation, or B Shi group-N (R21)R 22; R 21Shi C1-C 10-Wan base, Ta You Xia row Qu is for basic Qu generation: C1-C 4-alcoxyl base, C1-C 6-alcoxyl base-C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, C1-C 4-halogenated alkylthio, C1-C 4-Wan base sulfinyl, C1-C 4-Wan base sulfonyl, C1-C 4-Wan base sulfonyloxy, C1-C 4-Wan base Tang base, C1-C 4-alcoxyl base Tang base, C1-C 4-Wan base Tang Yang base, two (C1-C 4-Wan yl) amino, C3-C 8-cycloalkyl, aryl, aryloxy group, arylthio, aryl sulfonyl, aryl sulfonyl kia, aryl-sulfonyl oxygen, aryl carbonyl or Bi Ding base; Ru fruit Xu Yao, aryl or Bi Ding base can You Xia row Qu for basic Qu generation: halogen, C1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, phenoxy group, halogenated phenoxy, thiophenyl or halogeno-benzene sulfenyl, or R21Shi C3-C 20-alkenyl, C3-C 20-halogenated alkenyl, C3-C 20-alkynyl, C3-C 20-halo alkynyl, C3-C 8-cycloalkyl, You halogen or C1-C 4The C in-Wan base Qu generation3-C 8-cycloalkyl, Bian base or aryl, Ru fruit Xu Yao, but Bian base and aryl You Xia row Qu for basic Qu generation: halogen, C1-C 4-Wan base, C1-C 4-haloalkyl, C1-C 4-alcoxyl base, C1-C 4-halogenated alkoxy, C1-C 4-Wan sulfenyl, Xiao base, Qing are basic, benzoyl, halogeno-benzene formoxyl, phenoxy group or halogenated phenoxy; R22As R21Zhi definition, or Shi C in addition1-C 10-Wan base; Or R21And R22Yu the nitrogen-atoms Yi Qi that Zhi Suo Xiang connects, Xing becomes unsubstituted or single Zhi is trisubstituted, non-aromatic, list or bicyclic heterocycles, and Qi Zhong Qu can Shi C for base1-C 4-Wan base, You halogen, C1-C 4The C of-alcoxyl base, phenyl, benzo dioxo base or trifluoromethyl phenyl substituted1-C 4-Wan base, C1-C 4-alcoxyl base, C1-C 4-alcoxyl base Tang base, C1-C 4-Wan base Tang base, phenyl, You halogen, C1-C 4-Wan base, C1-C 4Phenyl or Bi Ding base, Mi Ding base or the formoxyl in-alcoxyl base, Xiao base or trifluoromethyl Qu generation, and Yan and the diastereoisomer of Shi I compound, Qi Qian Ti Tiao spare Shi, Ru fruit R21And R22Shi Wan base, the Wan base in Ze Zhi Shao Zhe Xie group Zhi Yi Wei Qu generation.
2. according to the compound of claim 1, R wherein 1It is group
3. according to the compound of claim 2, R wherein 4Be fluorine, chlorine or C 1-C 4-alkyl; N is 1,2 or 3; And m is 0.
4. according to the compound of claim 3, R wherein 4Be fluorine, chlorine or methyl; N is 2 or 3.
5. according to the compound of claim 1, R wherein 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-.
6. according to the compound of claim 1, wherein G is group-CO-A (a).
7. according to the compound of claim 6, wherein A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10,-(CR 8R 9) p-R 11Or-N (R 10) R 13, replace or unsubstituted naphthyl.
8. according to the compound of claim 7, R wherein 8And R 9Be hydrogen or methyl independently of each other; And p is 1 or 2.
9. compound according to Claim 8, wherein R 8And R 9It is methyl.
10. according to the compound of claim 7, R wherein 10Be C 1-C 8-alkyl, C 3-C 6-cycloalkyl, phenyl, the phenyl or the naphthyl that replace by halogen; R 11Be C 3-C 8-cycloalkyl, benzyloxy, by halogen, C 1-C 4-alkyl, C 1-C 4Benzyloxy or naphthyloxy that-haloalkyl or phenoxy group replace; And R 13Be C 3-C 7-cycloalkyl or cyano group-C 1-C 6-alkyl.
11. according to the compound of claim 7, wherein Y and Z are NR 12
12. according to the compound of claim 11, wherein R 12Be hydrogen or C 1-C 4-alkyl.
13. according to the compound of claim 7, wherein R 8And R 9Be hydrogen or methyl independently of each other; And p is 1 or 2; R 10Be C 1-C 4-alkyl, C 3-C 6-cycloalkyl, phenyl, the phenyl or the naphthyl that replace by halogen; R 11Be C 3-C 6-cycloalkyl, benzyloxy, by halogen, C 1-C 4-alkyl, C 1-C 4Benzyloxy or naphthyloxy that-haloalkyl or phenoxy group replace; Y and Z are NR 12R 12Be hydrogen or C 1-C 4-alkyl; And R 13Be C 3-C 8-cycloalkyl or cyano group-C 1-C 6-alkyl.
14. according to the compound of claim 1, wherein R 1It is group R 4Be fluorine, chlorine or C 1-C 4-alkyl; N is 1,2 or 3; M is 0; R 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-; G is group-CO-A (a); A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10,-(CR 8R 9) p-R 11Or-N (R 10) R 13, or replacement or unsubstituted naphthyl; R 8And R 9Be hydrogen or methyl independently of each other; And p is 1 or 2; R 10Be C 1-C 4-alkyl, C 3-C 6-cycloalkyl, phenyl, the phenyl or the naphthyl that replace by halogen; R 11Be C 3-C 8-cycloalkyl, benzyloxy, by halogen, C 1-C 4-alkyl, C 1-C 4Benzyloxy or naphthyloxy that-haloalkyl or phenoxy group replace; And R 13Be C 3-C 7-cycloalkyl or cyano group-C 1-C 6-alkyl.
15. according to the compound of claim 1, wherein R 1It is group
Figure A9519765200071
And m is 0.
16. according to the compound of claim 15, wherein R 4Be C 1-or C 2-alkyl; And n is 1,2 or 3.
17. according to the compound of claim 16, wherein R 4Be to be 2,4 and 6 C for the connection site of phenyl 1-or C 2-alkyl; And n is 3.
18. according to the compound of claim 1, wherein R 1It is group
Figure A9519765200072
And m is 0; R 4Be C 1-or C 2-alkyl; N is 1,2 or 3; R 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-.
19. according to the compound of claim 1, wherein G is group-CO-A (a); And A is C 1-C 8-alkyl, it is by nitro, cyano group, Si (C 1-C 4-alkyl) 3, amino, C 1-C 4-alkylamino, two (C 1-C 4-alkyl) amino, replacement or unsubstituted benzyloxy or group Replace, or A is C 3-C 8-cycloalkyl, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it can be by C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-alkyl sulphinyl, C 1-C 4-alkyl sulphonyl or replacement or unsubstituted phenyl replace, or A is C 3-C 8-cycloalkyl oxy, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it is unsubstituted or by C 1-C 4-alkyl replaces, or A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10Or-(CR 8R 9) p-R 11
20. according to the compound of claim 1, wherein R 1It is group
Figure A9519765200081
R 4Be C 1-or C 2-alkyl; N is 1,2 or 3; M is 0; R 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-; G is group-CO-A (a); And A is C 1-C 8-alkyl, it is by nitro, cyano group, Si (C 1-C 4-alkyl) 3, amino, C 1-C 4-alkylamino, two (C 1-C 4-alkyl) amino, replacement or unsubstituted benzyloxy or group
Figure A9519765200082
Replace, or A is C 3-C 8-cycloalkyl, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it can be by C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-alkyl sulphinyl, C 1-C 4-alkyl sulphonyl or replacement or unsubstituted phenyl replace, or A is C 3-C 8-cycloalkyl oxy, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it is unsubstituted or by C 1-C 4-alkyl replaces, or A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10Or-(CR 8R 9) p-R 11
21. a method for preparing following formula: compound, R wherein 1, R 2And R 3As definition in the claim 1, and G be group-CO-A (a) and A as defined in claim 1, different is not to be group-N (R 10) R 13, described method comprises formula II compound and the reaction of formula III compound R wherein 1, R 2And R 3As defined above, Wherein A is as defined above and E 1It is leaving group.
22. method for preparing following formula: compound
Figure A9519765200093
R wherein 1, R 2And R 3As according to defined in the claim 1, G is that group-CO-A (a) and A are group-N (R 10) R 13, R wherein 10And R 13As defined in claim 1, be R 10Be not hydrogen, described method comprises formula II compound and the reaction of formula IV compound
Figure A9519765200094
R wherein 1, R 2And R 3As defined above,
Figure A9519765200095
R wherein 10And R 13As defined above, and E 1It is leaving group.
23. a method for preparing following formula: compound,
Figure A9519765200101
R wherein 1, R 2And R 3As defined in claim 1, G is that group-CO-A (a) and A are group-NHR 13, R wherein 13As defined in claim 1, this method comprises formula II compound and formula V isocyanate reaction
Figure A9519765200102
R wherein 1, R 2And R 3As defined above,
R 13-N=C=O (V) is R wherein 13As defined above.
24. a method for preparing following formula: compound,
Figure A9519765200103
R wherein 1, R 2And R 3As according to defined in the claim 1, G is group-SO 2-B (b) and B as defined in claim 1, described method comprises makes the reaction of formula II compound and formula VI compound R wherein 1, R and R 3As defined in claim 1,
B-SO 2-E 1(VI) wherein B as defined above, and E 1Be leaving group, be reflected at if desired in the solvent and have or alkali-free in the presence of carry out.
25. a pesticide composition, it comprises the formula I compound of at least a claim 1 as activeconstituents and conventional processing aids.
26. pesticide composition control insect, the representative insect of acarina or the application of broadleaf weeds and dogstail according to claim 25.
27. a method of preventing and treating broadleaf weeds and dogstail, described method comprise the crop that makes it to resist broadleaf weeds and dogstail infringement that the compositions-treated with claim 25 is intended to protect, or handle broadleaf weeds and dogstail.
28. according to the pesticide composition of claim 25, it is used to prevent and treat the representative insect of insect or acarina.
29. according to the pesticide composition of claim 25, it is used for optionally preventing and treating broadleaf weeds and the dogstail of crop.
30. the composition of claim 26 is used to prevent and treat the application of the representative insect of insect or acarina.
31. the composition of claim 26 is used for optionally preventing and treating the application of broadleaf weeds and dogstail.
32. a method of preventing and treating the representative insect of insect or acarina, it comprises the composition according to claim 28 is applied to insect or its dried rhizome of rehmannia of dwelling.
33. resist the method for the representative insect infringement of insect or acarina according to the protective plant propagulum of claim 32, described method comprises the site of handling propagulum or propagulum plantation.
34. the propagulum of handling with the method for claim 33.
35. a method of preventing and treating green bristlegrass grass growth, described method comprise the crop that makes it to resist broadleaf weeds and dogstail infringement that the compositions-treated with claim 25 is intended to protect, and/or processing broadleaf weeds and dogstail.
36., wherein contain 0.1 to 99% active substance by weight according to the composition of claim 28.
37. according to the method for claim 32, wherein per hectare is used 0.001 to 2kg active substance.
38., wherein contain 0.1 to 95% formula I active substance by weight according to the composition of claim 29.
39. according to the method for claim 35, described method comprises with the amount of per hectare 0.001 to 2kg uses formula I compound.
40. a selective herbicidal composition, it comprises the formula I compound of herbicidally effective amount and safener mixture as active substance and conventional inertia processing aids.
41. according to the herbicidal composition of claim 40, wherein safener is quinoline, pyrazole derivatives or triazole derivative.
42. according to the composition of claim 41, wherein safener is a formula X quinoline
Figure A9519765200121
R wherein 15Be hydrogen, C 1-C 8-alkyl or by C 1-C 6-alkoxyl group or C 3-C 6The C that-alkenyloxy replaces 1-C 8-alkyl; And X 2Be hydrogen or chlorine; Or the 1-of formula XI phenylpyrrole-3-carboxylic acid derivative Wherein E is nitrogen or methyne; R 16Be-CCl 3Or do not replace or halogenated phenyl; R 17And R 18Be hydrogen or halogen independently of each other; And R 19Be C 1-C 4-alkyl.
43. according to the composition of claim 40, wherein in formula I compound, R 1It is group
Figure A9519765200132
And m is 0.
44. according to the composition of claim 43, wherein radicals R 4Be C 1-or C 2-alkyl; And n is 1,2 or 3.
45. according to the composition of claim 44, wherein radicals R 4Be with respect to the connection site of phenyl and
45. according to the composition of claim 44, wherein radicals R 4Be to be 2,4 and 6 C for the connection site of phenyl 1-or C 2-alkyl; And n is 3.
46. according to the composition of claim 40, wherein in formula I compound, R 1It is group
Figure A9519765200141
M is 0; R 4Be C 1-or C 2-alkyl; N is 1,2 or 3; R 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-.
47. according to the composition of claim 40, wherein in formula I compound, G is group-CO-A (a); And A is C 1-C 8-alkyl, it is by nitro, cyano group, Si (C 1-C 4-alkyl) 3, amino, C 1-C 4-alkylamino, two (C 1-C 4-alkyl) amino, replacement or unsubstituted benzyloxy or group
Figure A9519765200142
Replace, or A is C 3-C 8-cycloalkyl, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it can be by C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-alkyl sulphinyl, C 1-C 4-alkyl sulphonyl or replacement or unsubstituted phenyl replace, or A is C 3-C 8-cycloalkyl oxy, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it is unsubstituted or by C 1-C 4-alkyl replaces, or A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10Or-(CR 8R 9) p-R 11
48. according to the composition of claim 40, wherein in formula I compound, R 1It is group
Figure A9519765200143
R 4Be C 1-or C 2-alkyl; N is 1,2 or 3; M is 0; R 2And R 3Be C 1-C 6-alkyl; Or R 2With R 3Form together and replace or unsubstituted alkylidene chain-(CH 2) 5-,-(CH 2) 4-or-(CH 2) 3-; G is group-CO-A (a); And A is C 1-C 8-alkyl, it is by nitro, cyano group, Si (C 1-C 4-alkyl) 3, amino, C 1-C 4-alkylamino, two (C 1-C 4-alkyl) amino, replacement or unsubstituted benzyloxy or group
Figure A9519765200144
Replace, or A is C 3-C 8-cycloalkyl, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it can be by C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-alkyl sulphinyl, C 1-C 4-alkyl sulphonyl or replacement or unsubstituted phenyl replace, or A is C 3-C 8-cycloalkyl oxy, it can contain heteroatoms oxygen, sulphur or nitrogen if desired, and it is unsubstituted or by C 1-C 4-alkyl replaces, or A is group-(CR 8R 9) p-(Y) o-CO-(Z) r-R 10Or-(CR 8R 9) p-R 11
49. according to the composition of claim 42, it comprises formula Xa safener
Figure A9519765200151
50. according to the composition of claim 42, it comprises formula Xb safener
Figure A9519765200152
51. according to the composition of claim 42, it comprises the safener of formula XIa
52. optionally prevent and treat broadleaf weeds in the crop and the method for dogstail for one kind, described method comprises with the formula I weedicide of herbicidally effective amount and weedicide antagonism amount according to the formula X of claim 42 or the safener of XI, simultaneously or handle crop, its seed or its cultivation area independently of each other.
53. according to the method for claim 52, described method comprises to handle with the formula X of 0.001 to 2kg/ha formula I weedicide and 0.001 to 0.5kg/ha or XI safener does object or arable farming district.
54. according to the method for claim 52, wherein crop is corn and cereal class.
55. according to the formula I compound of claim 1, wherein R 1Be 2,4,6-trimethylphenyl, R 2With R 3Be together-(CH 2) 4-and G be-C (=O)-N (CH 3) CH 2CH 2CN.
56. according to the formula I compound of claim 1, wherein R 1Be 2,4,6-trimethylphenyl, R 2With R 3-N is-CH together 2CH 2CH (CH 3) CH 2-N and G be-C (=O)-N (CH 3) CH 2CH 2CN.
57. according to the formula I compound of claim 1, wherein R 1Be 2,6-dichlorophenyl, R 2With R 3Be together-(CH 2) 4-and G be-C (=O)-N (CH 3) CH 2CH 2CN.
CN95197652A 1995-01-13 1995-12-29 4 -aryl -and 4 -heteroaryl -5 -oxopyrazoline derivatives having pesticidal properties Pending CN1175248A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH10895 1995-01-13
CH00108/95 1995-01-13

Publications (1)

Publication Number Publication Date
CN1175248A true CN1175248A (en) 1998-03-04

Family

ID=4179456

Family Applications (1)

Application Number Title Priority Date Filing Date
CN95197652A Pending CN1175248A (en) 1995-01-13 1995-12-29 4 -aryl -and 4 -heteroaryl -5 -oxopyrazoline derivatives having pesticidal properties

Country Status (12)

Country Link
EP (1) EP0804422A1 (en)
JP (1) JPH10512248A (en)
CN (1) CN1175248A (en)
AR (1) AR002020A1 (en)
AU (1) AU4435396A (en)
BR (1) BR9600088A (en)
CA (1) CA2210286A1 (en)
IL (1) IL116697A0 (en)
MX (1) MX9705247A (en)
TR (1) TR199600024A2 (en)
WO (1) WO1996021652A1 (en)
ZA (1) ZA96243B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101580489B (en) * 2008-05-14 2011-07-20 中国中化股份有限公司 Nitrogenous heterocyclic ring compound and preparation method and application thereof

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19808261A1 (en) 1998-02-27 1999-10-28 Bayer Ag Arylphenyl substituted cyclic ketoenols
DE69908568T2 (en) 1998-03-13 2004-05-06 Syngenta Participations Ag HERBICIDE ACTIVE 3-HYDROXY-4-ARYL-5-OXOPYRAZOLINE DERIVATIVES
DE19813354A1 (en) 1998-03-26 1999-09-30 Bayer Ag Arylphenyl substituted cyclic ketoenols
DE19818732A1 (en) 1998-04-27 1999-10-28 Bayer Ag New aryl substituted cyclic ketoenol compounds useful for control of insects and as herbicides
AU2623399A (en) * 1999-02-11 2000-08-29 Novartis Ag 3-hydroxy-4-aryl-5-pyrazoline derivatives as herbicides
WO2001017352A1 (en) * 1999-09-07 2001-03-15 Syngenta Participations Ag Herbicide agent
ATE282597T1 (en) 1999-09-07 2004-12-15 Syngenta Participations Ag P-TOLYL HETEROCYCLES AS HERBICIDES
HU228800B1 (en) * 1999-09-07 2013-05-28 Syngenta Participations Ag Synergistic herbicidal composition and use thereof
RU2249352C2 (en) 1999-09-07 2005-04-10 Зингента Партисипейшнс Аг Herbicidal composition of selective action, method for selective control against weed plants and grasses
DE10139465A1 (en) * 2001-08-10 2003-02-20 Bayer Cropscience Ag Herbicidal composition, especially for selective weed control in crops such as cereals, containing cyclic keto enol derivative herbicide and safener, e.g. cloquintocet-mexyl or mefenpyr-diethyl
WO2003067984A1 (en) * 2002-02-13 2003-08-21 Syngenta Participations Ag Herbicidal composition
TWI313676B (en) 2002-12-05 2009-08-21 Syngenta Participations Ag Process for the preparation of phenylmalonic acid dinitriles
DE10311300A1 (en) 2003-03-14 2004-09-23 Bayer Cropscience Ag New 2-alkoxy-4-halo-6-alkylphenyl-substituted (hetero)cyclic ketoenols, useful as total or selective herbicides and pesticides, e.g. insecticides, acaricides and nematocides for plant protection
DE10326386A1 (en) 2003-06-12 2004-12-30 Bayer Cropscience Ag N-heterocyclyl-phenyl-substituted cyclic ketoenols
DE10331675A1 (en) * 2003-07-14 2005-02-10 Bayer Cropscience Ag Hetaryl-substituted pyrazolidinedione derivatives
DE10337497A1 (en) 2003-08-14 2005-03-10 Bayer Cropscience Ag 4-biphenyl-pyrazolidine-3,5-dione derivatives
DE102004014620A1 (en) 2004-03-25 2005-10-06 Bayer Cropscience Ag 2,4,6-phenyl-substituted cyclic ketoenols
DE102004035133A1 (en) 2004-07-20 2006-02-16 Bayer Cropscience Ag Selective insecticides based on substituted cyclic ketoenols and safeners
DE102004044827A1 (en) 2004-09-16 2006-03-23 Bayer Cropscience Ag Iodine-phenyl-substituted cyclic ketoenols
AU2006212397B2 (en) 2005-02-09 2011-05-12 Syngenta Participations Ag Process for the preparation of intermediates
DE102005059469A1 (en) 2005-12-13 2007-06-14 Bayer Cropscience Ag Insecticidal compositions having improved activity
DE102006007882A1 (en) 2006-02-21 2007-08-30 Bayer Cropscience Ag New cyclic keto enol derivatives useful for controlling animal pests and/or unwanted plant growth
GB0900641D0 (en) 2009-01-15 2009-02-25 Syngenta Ltd Novel herbicides
GB0901086D0 (en) 2009-01-22 2009-03-11 Syngenta Ltd Novel herbicides
GB0901835D0 (en) 2009-02-04 2009-03-11 Syngenta Ltd Novel herbicides
GB0901834D0 (en) 2009-02-04 2009-03-11 Syngenta Ltd Novel herbicides
PL2406216T3 (en) 2009-03-11 2017-09-29 Bayer Intellectual Property Gmbh Halogenalkylmethylenoxy-phenyl-substituted ketoenols
DE102010008644A1 (en) 2010-02-15 2011-08-18 Bayer Schering Pharma Aktiengesellschaft, 13353 Cyclic ketoenols for therapy
RU2570900C2 (en) * 2010-12-02 2015-12-20 Оно Фармасьютикал Ко., Лтд. Novel compound and its application in medicine
JP6212503B2 (en) 2012-01-26 2017-10-11 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングBayer Intellectual Property GmbH Phenyl-substituted ketoenols for combating fish parasites
JPWO2014142308A1 (en) * 2013-03-15 2017-02-16 公益財団法人相模中央化学研究所 Bicyclic pyrazolinone derivatives and herbicides containing them as active ingredients
CA2906431A1 (en) 2013-03-15 2014-09-18 Sagami Chemical Research Institute Polycyclic pyrazolinone derivative and herbicide comprising same as effective component thereof
JP2017214289A (en) * 2014-09-12 2017-12-07 公益財団法人相模中央化学研究所 Pyrazolinone derivative, method for producing the same and herbicide containing the same as an active ingredient
EP4159039A1 (en) 2019-07-18 2023-04-05 Adama Agan Ltd. Stable formulation comprising pinoxaden
CN115720487A (en) 2020-04-06 2023-02-28 安道麦阿甘有限公司 Co-crystals of an antioxidant and an active ingredient and use of an antioxidant as a stabilizer
CN114106016A (en) * 2020-08-29 2022-03-01 海利尔药业集团股份有限公司 Phenylpyrazoline derivative or salt thereof, composition and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4985063A (en) * 1988-08-20 1991-01-15 Bayer Aktiengesellschaft 3-aryl-pyrrolidine-2,4-diones
DE4109208A1 (en) * 1991-03-21 1992-09-24 Bayer Ag 3-HYDROXY-4-ARYL-5-OXO-PYRAZOLINE DERIVATIVES
DE4413669A1 (en) * 1993-07-05 1995-01-12 Bayer Ag Substituted aryl ketoenol heterocycles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101580489B (en) * 2008-05-14 2011-07-20 中国中化股份有限公司 Nitrogenous heterocyclic ring compound and preparation method and application thereof

Also Published As

Publication number Publication date
AR002020A1 (en) 1998-01-07
IL116697A0 (en) 1996-05-14
EP0804422A1 (en) 1997-11-05
AU4435396A (en) 1996-07-31
BR9600088A (en) 1998-01-27
WO1996021652A1 (en) 1996-07-18
MX9705247A (en) 1997-10-31
ZA96243B (en) 1996-08-19
JPH10512248A (en) 1998-11-24
TR199600024A2 (en) 1996-08-21
CA2210286A1 (en) 1996-07-18

Similar Documents

Publication Publication Date Title
CN1175248A (en) 4 -aryl -and 4 -heteroaryl -5 -oxopyrazoline derivatives having pesticidal properties
JP3487614B2 (en) Oxadiazine derivatives
CN1220578A (en) Pesticidal compositions
CN1216900A (en) Pesticidal composition
KR100216159B1 (en) Picoline oxides and their preparations
EP0483055A1 (en) Triazacyclohexane derivatives
BG60863B1 (en) Nitroguanadine derivatives, method for their preparation and application
WO1994005642A1 (en) Indazole derivatives
JPH07224015A (en) Vinylcarboxylic acid derivative
US5358957A (en) Butyric acid derivatives
JP2000514815A (en) Pesticide composition
JP3374245B2 (en) Novel 2-nitromethylidene / 2-cyanimid / 2-nitro-imino-pyrrolidines and piperidines, intermediates and their use as pesticides
JPH06184084A (en) Carbamic acid derivative
CA2130503A1 (en) Process for the manufacture of phenoxyphenoxyalkyl derivatives
CN1069264A (en) Butyramide
US5192803A (en) Sulfenylated carbamic esters and their use in pesticides
JPH0625073A (en) Carboxymethyl cyclopropane derivative
JPH06234748A (en) Imidazole derivative
WO1995029889A1 (en) Perhaloalkoxybenzenophenone hydrazones and their use as pesticides
CN1089594A (en) Butyramide
HRP950136A2 (en) Novel herbicidally, acaricidally and insecticidally active compounds

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication