CN1277606A - Substituted aryloxy alkyl amino triazines - Google Patents

Substituted aryloxy alkyl amino triazines Download PDF

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Publication number
CN1277606A
CN1277606A CN98810521A CN98810521A CN1277606A CN 1277606 A CN1277606 A CN 1277606A CN 98810521 A CN98810521 A CN 98810521A CN 98810521 A CN98810521 A CN 98810521A CN 1277606 A CN1277606 A CN 1277606A
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group
alkyl
methyl
ethyl
replacement
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S·莱尔
H·J·里贝尔
U·斯特尔策
R·基尔斯滕
A·伦德
K·沃伊格特
M·多林格
M·W·德鲁斯
I·维特肖洛夫斯基
渡边幸喜
R·A·迈尔斯
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Bayer AG
Bayer CropScience KK
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Bayer AG
Nihon Bayer Agrochem KK
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to novel substituted aryloxy alkyl amino triazines of formula (I) wherein R<1> stands, for example, for H or C1-C6 alkyl; R<2> stands, for example, for H, C1-C6-alkyl or C1-C6 alkyl carbonyl; R<3> stands, for example, for C2-C6 alkyl, R<4> stands for example for H or C1-C4 alkyl; AR stands, for example, for substituted or unsubstituted phenyl and Z stands, for example, halogen, C1-C6 alkyl, C1-C6 hydroxy alkyl, C1-C6 halogen alkyl or C3-C6 cyclo alkyl. The invention also relates to a method for the production and use thereof as herbicides.

Description

The aryloxy alkyl amino triazines that replaces
The present invention relates to the aryloxy alkyl amino triazines, its preparation of novel substituted and as herbicide applications.
The aryloxy alkyl amino triazines of many replacements by (patent) document known (referring to, EP 273328, EP 411153/WO 90/09378).Yet these compounds do not obtain any special importance so far.
Therefore, the invention provides the aryloxy alkyl amino triazines of the replacement of novel general formula (I)
Figure A9881052100091
R wherein 1Represent hydrogen, or representative optional by hydroxyl-, cyano group-, halogen-or C 1-C 4The alkyl with 1 to 6 carbon atom of-alkoxyl group-replacement, R 2Represent hydrogen, represent formyl radical or all can choose wantonly by cyano group-, halogen-or C 1-C 4The alkyl, alkyl-carbonyl or the alkoxy carbonyl that respectively have 1 to 6 carbon atom of-alkoxyl group-replacement at moieties, R 3Representative optional by hydroxyl-, cyano group-, halogen-or C 1-C 4The alkyl with 2 to 6 carbon atoms of-alkoxyl group-replacement, or representative optional by cyano group-, halogen-or C 1-C 4The cycloalkyl with 3 to 6 carbon atoms of-alkyl-replacement, R 4Represent hydrogen or have the alkyl of 1 to 4 carbon atom, the Ar representative all can be chosen substituted phenyl, naphthyl, tetrahydro naphthyl or heterocyclic radical wantonly,
Wherein possible heterocyclic radical is preferably selected from following groups:
Furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzothiazolyl,
Oxazolyl, benzoxazolyl, thiadiazolyl group, oxadiazole base, pyrazolyl, pyrryl, pyridine
Base and pyrimidyl,
And wherein possible substituting group respectively is preferably selected from following groups:
Hydroxyl, cyano group, formamyl, thiocarbamoyl, nitro, halogen all can be appointed
Choosing is by the alkyl or the alcoxyl that respectively have 1 to 6 carbon atom of hydroxyl, cyano group or halogen-replacement
Base all can be chosen the alkyl that respectively has 1 to 6 carbon atom on alkyl by halogen-replacement wantonly
Carbonyl, alkoxy carbonyl, alkylthio, alkyl sulphinyl, alkyl sulphonyl, dialkyl group
Amino, alkyl-carbonyl-amino, alkyl sulfonyl-amino, two-alkyl-carbonyl-amino, two-alkane
Base alkylsulfonyl-amino, N-alkyl-N-alkyl-carbonyl-amino or N-alkyl-N-alkyl sulphonyl-
Amino, each optional by hydroxyl-, cyano group-, nitro-, halogen-, C 1-C 4-alkyl-, C 1-C 4-
Haloalkyl-, C 1-C 4-alkoxyl group-or C 1-C 4The phenyl of-halogenated alkoxy-replacement or benzene oxygen
Base and all can choose methylene-dioxy or ethylenedioxy wantonly by halogen-replacement,
Represent halogen with Z, the representative all can choose wantonly by hydroxyl-, cyano group-, halogen-, C 1-C 4-alkoxyl group-, C 1-C 4-alkyl-carbonyl-, C 1-C 4-alkoxyl group-carbonyl-, C 1-C 4-alkylthio-, C 1-C 4-alkyl sulphinyl-or C 1-C 4Each of-alkyl sulphonyl-replacement has alkyl, alkoxyl group, alkyl-carbonyl, alkoxy carbonyl, alkylthio, alkyl sulphinyl or the alkyl sulphonyl of 1 to 6 carbon atom on alkyl, or representative optional by cyano group-, halogen-or C 1-C 4The cycloalkyl with 3 to 6 carbon atoms of-alkyl-replacement.
The following acquisition of alkoxyalkyl aminotriazine class of the replacement of novel general formula (I):
(a) if make alkoxyalkyl two guanidines of general formula (II) with being adapted under the thinner existence down if be adapted at reacting the auxiliary existence
Figure A9881052100101
R wherein 1, R 2, R 3, R 4With Ar as defined above ,-and/or the acid adduct of general formula (II) compound-with the alxoxycarbonyl compounds reaction of general formula (III)
Z-CO-OR ' (III) wherein Z as defined above, and R ' represents alkyl, if if or (b) be adapted at reacting auxiliary and exist down and be adapted at thinner and exist down, make the halo triazine of the replacement of general formula (IV)
Figure A9881052100111
R wherein 3, R 4, Ar and Z as defined above and X represent halogen, with the nitrogenous compound reaction of logical formula V
Figure A9881052100112
R wherein 1And R 2As defined above, if if or (c) be adapted at reacting auxiliary and exist down and be adapted at thinner and exist down, make the aminotriazine of the replacement of general formula (VI) R wherein 1, R 2With Z as defined above, and Y 1Represent halogen or alkoxyl group, with the aryloxyalkylamines reaction of general formula (VII) Wherein Ar, R 3And R 4As defined above, or (d) prepare wherein R 2When not being formula (I) compound of hydrogen, if make the aryloxy alkyl amino triazine of general formula (Ia) with being adapted under the thinner existence down if be adapted at reacting the auxiliary existence
Wherein
R 1, R 3, R 4, Ar and Z as defined above,
Alkylation or acylting agent reaction with general formula (VIII)
Y 2-R 2 (VIII)
Wherein
R 2As defined above, but outside the dehydrogenation and
Y 2Represent halogen ,-O-R 2Or-O-CO-R 2,
And if be fit to, by ordinary method, with method (a) and (b), (c) or (d) obtain
General formula (I) further transforms in the above-mentioned substituting group range of definition.
The aryloxy alkyl amino triazine of the replacement of novel general formula (I) has by force and weeding activity selectively.
General formula of the present invention (I) compound contains the carbon atom of at least one asymmetric replacement and therefore can have different enantiomorph (R-and S-configuration) or diastereomer.The present invention relates to the different possible independent enantiomorph or the stereoisomer form of general formula (I) compound, and the mixture that relates to these isomeric compounds.
In definition, hydrocarbon chain, as alkyl-and when making up with heteroatoms, as in alkoxyl group-respectively be straight or branched.
Halogen is represented fluorine, chlorine, bromine or iodine usually, preferred fluorine, chlorine or bromine, particularly fluorine or chlorine.
The present invention preferably provides formula (I) compound, wherein R 1Represent hydrogen, or representative all can choose wantonly by hydroxyl-, cyano group-, fluoro-, chloro-, methoxyl group-or the methyl of oxyethyl group-replacements, ethyl, just-or different-propyl group, just-, different-, the second month in a season-or the tertiary butyl, R 2Represent hydrogen, represent formyl radical, or representative all can choose wantonly by cyano group-, fluoro-, chloro-, bromo-, methoxyl group-or the methyl of oxyethyl group-replacement, ethyl, ethanoyl, propionyl, just-or isobutyryl, methoxycarbonyl or ethoxy carbonyl, R 3Representative all can choose wantonly by hydroxyl-, cyano group-, fluoro-, chloro-, methoxyl group-or the ethyl of oxyethyl group-replacements, just-or different-propyl group, just-, different-, the second month in a season-or the tertiary butyl, or representative all can choose wantonly by cyano group-, fluoro-, chloro-, methyl-or cyclopropyl, cyclobutyl, cyclopentyl or the cyclohexyl of ethyl-replacement, R 4Represent hydrogen or methyl, the Ar representative all can be chosen substituted phenyl, naphthyl, tetrahydro naphthyl or heterocyclic radical wantonly,
Wherein possible heterocyclic radical is preferably selected from following groups:
Furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzothiazolyl,
Oxazolyl, benzoxazolyl, thiadiazolyl group, oxadiazole base, pyrazolyl, pyrryl, pyridine
Base and pyrimidyl,
And wherein possible substituting group respectively is preferably selected from following groups:
Hydroxyl, cyano group, formamyl, thiocarbamoyl, nitro, fluorine, chlorine, bromine,
All can choose wantonly by hydroxyl-, cyano group-, the methyl that replaces of fluoro-or chloro-, ethyl, just-or different third
Base, just-, different-, secondary-or the tertiary butyl, methoxyl group, oxyethyl group, just-or isopropoxy,
Just-, different-, secondary-or tert.-butoxy, all can choose the ethanoyl, third that replaces by fluoro-or chloro-wantonly
Acyl group, just-or isobutyryl, methoxycarbonyl, ethoxy carbonyl, just-or isopropoxy
Carbonyl, methylthio group, ethylmercapto group, just-or different-rosickyite base, methylsulfinyl, ethyl Asia
Alkylsulfonyl, just-or sec.-propyl sulfinyl, methyl sulphonyl, ethylsulfonyl, just-or
Sec.-propyl alkylsulfonyl, dimethylamino, diethylamino, acetylamino, propionyl ammonia
The base, methyl sulphonyl is amino, ethylsulfonyl is amino, diacetyl group is amino, two-methyl sulphur
Acyl group-amino, N-methyl-N-acetylamino or N-methyl-N-methyl sulphonyl amino, each
Optional by hydroxyl-, cyano group-, nitro-, fluoro-, chloro-, bromo-, methyl-, ethyl-, just-
Or sec.-propyl, just-, different-, secondary-or tertiary butyl, trifluoromethyl, methoxyl group-, oxyethyl group-,
Just-or isopropoxy-, just-, different-, secondary-or tert.-butoxy-, difluoro-methoxy-or trifluoro
The phenyl of methoxyl group-replacement or phenoxy group and all can choose the methylene two that replaces by fluoro-or chloro-wantonly
Oxygen base or ethylenedioxy; represent fluorine with Z; chlorine; bromine; the representative all can choose wantonly by hydroxyl-; cyano group-; nitro-; fluoro-; chloro-; methoxyl group-; oxyethyl group-; just-or isopropoxy-; just-; different-; secondary-or tert.-butoxy-; methylthio group-; ethylmercapto group-; just-or different-rosickyite base-; methylsulfinyl-; the ethyl sulfinyl-; just-or the sec.-propyl sulfinyl-; methyl sulphonyl-; ethylsulfonyl-; just-or the methyl of sec.-propyl alkylsulfonyl-replacement; ethyl; just-or sec.-propyl; just-; different-; secondary-or the tertiary butyl; methoxyl group; oxyethyl group; just-or isopropoxy; just-; different-; secondary-or tert.-butoxy; methylthio group; ethylmercapto group; just-or the iprotiazem base; methylsulfinyl; the ethyl sulfinyl; just-or the sec.-propyl sulfinyl; methyl sulphonyl; ethylsulfonyl; just-or sec.-propyl alkylsulfonyl, or representative all can choose wantonly by cyano group-; fluoro-; chloro-; methyl-or the cyclopropyl of ethyl-replacement; cyclobutyl; cyclopentyl or cyclohexyl.
Ben in as above general formula (I) compound as preferred definition is following compounds:
(A) formula (I) compound, wherein R 1, R 2, R 3, R 4As above define with Z and the Ar representative all can be chosen substituted wherein possible substituting group phenyl or naphthyl as defined above wantonly;
(B) formula (I) compound, wherein R 1, R 2, R 3, R 4As above define with Z and the Ar representative all can be chosen wantonly and is substituted heterocyclic radical, wherein possible heterocyclic group and substituting group as above define.
The present invention especially preferably relates to formula (I) compound, wherein R 1Represent hydrogen, or representative all can choose wantonly by cyano group-, fluoro-, methoxyl group-or the methyl or the ethyl of oxyethyl group-replacement, R 2Represent hydrogen, or representative all can choose wantonly by cyano group-, fluoro-, chloro-, methoxyl group-or methyl, ethyl, ethanoyl or the propionyl of oxyethyl group-replacement, R 3Representative all can choose wantonly by fluoro-, chloro-, methoxyl group-or the ethyl of oxyethyl group-replacement, just-or different-propyl group, R 4Represent hydrogen, the Ar representative all can be chosen substituted phenyl or naphthyl wantonly,
Each especially is selected from following groups wherein possible substituting group:
Hydroxyl, cyano group, nitro, fluorine, chlorine, bromine, all can choose wantonly by hydroxyl-, cyano group-, fluoro-or
The methyl that chloro-replaces, ethyl, just-or sec.-propyl, just-, different-, secondary-or tertiary butyl, first
Oxygen base, oxyethyl group, just-or isopropoxy, just-, different-, secondary-or tert.-butoxy, all can
The optional ethanoyl that replaces by fluoro-or chloro-, propionyl, just-or isobutyryl, methoxyl group carbonyl
Base, ethoxy carbonyl, just-or isopropoxy carbonyl, methylthio group, ethylmercapto group, just-or different-
Rosickyite base, methylsulfinyl, ethyl sulfinyl, just-or sec.-propyl sulfinyl, first
Base alkylsulfonyl, ethylsulfonyl, just-or sec.-propyl alkylsulfonyl, each optional by hydroxyl-, cyanogen
Base-, nitro-, fluoro-, chloro-, bromo-, methyl-, ethyl-, just-or sec.-propyl, just-,
Different-, secondary-or tertiary butyl, trifluoromethyl, methoxyl group-, oxyethyl group-, just-or isopropoxy
-, just-, different-, secondary-or tert.-butoxy-, difluoro-methoxy-or trifluoromethoxy-replacement
Phenyl or phenoxy group and all can choose methylene-dioxy or the inferior second two that replaces by fluoro-or chloro-wantonly
The oxygen base,
With Z representative all can choose wantonly by hydroxyl-, cyano group-, fluoro-, chloro-, methoxyl group-, oxyethyl group-, just-or isopropoxy-, methylthio group-, ethylmercapto group-, just-or different-rosickyite base-, methylsulfinyl-, the ethyl sulfinyl-, just-or sec.-propyl sulfinyl-, methyl sulphonyl-, ethylsulfonyl-, just-or the methyl of sec.-propyl alkylsulfonyl-replacements, ethyl, just-or sec.-propyl, just-, different-, secondary-or the tertiary butyl, or represent all can choose wantonly by cyano group-, fluoro-, chloro-, methyl-or cyclopropyl, cyclobutyl, cyclopentyl or the cyclohexyl of ethyl-replacement.
Ben in as above general formula (I) compound as special preferred definition is following compounds:
(A ') formula (I) compound, wherein R 1, R 2, R 3, R 4As above define with Z and the Ar representative all can be chosen substituted wherein possible substituting group phenyl or naphthyl as defined above wantonly, its condition is R 3Substituting group on the carbon atom that is connected is the R configuration;
(B ') formula (I) compound, wherein R 1, R 2, R 3, R 4As above define with Z and the Ar representative all can be chosen substituted wherein possible substituting group phenyl or naphthyl as defined above wantonly, its condition is R 3Substituting group on the carbon atom that is connected is the S configuration.
General or preferred group definition above-mentioned is suitable for formula (I) end product, and correspondingly, also is suitable for starting raw material or intermediate required under each preparation situation.These group definition can mutually combine as required,, comprise the combination between preferable range above-mentioned that is.
The grouping of formula of the present invention (I) examples for compounds is listed in hereinafter.Herein, general formula is all represented R enantiomorph, S enantiomorph and racemic modification under each situation.
Group 1
Figure A9881052100161
(a: racemic modification; the b:R enantiomorph; the c:S enantiomorph) Z has the implication that for example hereinafter provides herein: methyl; ethyl; just-or sec.-propyl; just-; different-; secondary-or the tertiary butyl; methyl fluoride; difluoromethyl; trifluoromethyl; chloromethyl; dichloromethyl; the chlorine methyl fluoride; the chlorine brooethyl; chlorodifluoramethyl-; the fluorine dichloromethyl; bromine difluoro methyl; trichloromethyl; 1-fluoro-ethyl; 2-fluoro-ethyl; 1-chloro-ethyl; 2-chloro-ethyl; 1-bromo-ethyl; 1-chloro-1-fluoro-ethyl; 1-fluoro-propyl group; 2-fluoro-propyl group; 3-fluoro-propyl group; 1-chloro-propyl group; 2-chloro-propyl group; 3-chloro-propyl group; 1-bromo-propyl group; 1-fluoro-1-methyl-ethyl; 2-fluoro-1-methyl-ethyl; 1-chloro-1-methyl-ethyl; 1-fluoro-1-methyl-propyl group; 1-chloro-1-ethyl-propyl group; 1-fluoro-1-ethyl-propyl group; 1-fluoro-2-methyl-propyl group; 1-chloro-2-methyl-propyl group; 2-chloro-1-methyl-ethyl; 1; 1-two fluoro-ethyls; 1; 2-two fluoro-ethyls; 1; 1-two chloro-ethyls; 2; 2; 2-three fluoro-ethyls; 1; 2; 2; 2-tetrafluoro-ethyl; pentafluoroethyl group; 1; 1-two fluoro-propyl group; 1; 1-two chloropropyls; five fluoropropyls; 1-fluoro-butyl; 1-chloro-butyl; perfluoro butyl; the perfluor amyl group; perfluoro hexyl; 1-hydroxyl-ethyl; 1-hydroxyl-1-methyl-ethyl; 1-hydroxyl-propyl group; methoxymethyl; ethoxyl methyl; dimethoxy-methyl; the 1-methoxy ethyl; 2-methoxyl group-ethyl; 1; 1-dimethoxy-ethyl; the 1-ethoxyethyl group; the 2-ethoxyethyl group; 2; 2-dimethoxy-ethyl; 2; 2-diethoxy-ethyl; 2-methoxyl group-1-methyl-ethyl; 2-methoxyl group-1-ethyl-ethyl; 2-oxyethyl group-1-methyl-ethyl; 2-oxyethyl group-1-ethyl-ethyl; 2; 2-bi-methoxy-methyl; methylthiomethyl; the ethylmercapto group methyl; 1-methylthio group-ethyl; 2-methylmercaptoethyl; 1-ethylmercapto group-ethyl; 2-ethylmercapto group ethyl; the methylsulfinyl methyl; ethyl sulfinyl methyl; the sulfonyloxy methyl ylmethyl; the ethylsulfonyl methyl; cyclopropyl; 1-cyano group-cyclopropyl; 1-fluorine cyclopropyl; 1-chlorine cyclopropyl; 2-cyano group cyclopropyl; 2-fluorine cyclopropyl; 2-chloro-cyclopropyl; 2; 2-difluoro cyclopropyl; 2; 2-two chloro-cyclopropyl; cyclobutyl; 2; 2-two fluoro-cyclobutyl; 2; 2; 3-three fluoro-cyclobutyl; 2,2-two fluoro-3-chloro-cyclobutyl; cyclopentyl; cyclohexyl.
Group 2
Figure A9881052100171
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 3 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 4
Figure A9881052100173
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 5
Figure A9881052100181
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 6
Figure A9881052100182
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 7
Figure A9881052100183
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 8
Figure A9881052100191
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 9 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 10 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 11
Figure A9881052100201
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 12 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 13
Figure A9881052100203
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 14
Figure A9881052100211
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 15
Figure A9881052100212
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 16
Figure A9881052100213
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 17
Figure A9881052100221
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 18 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 19 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 20
Figure A9881052100231
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 21 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 22
Figure A9881052100233
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 23 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 24
Figure A9881052100242
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 25
Figure A9881052100243
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 26
Figure A9881052100251
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 27
Figure A9881052100252
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 28
Figure A9881052100253
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 29 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 30
Figure A9881052100262
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 31
Figure A9881052100263
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 32 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 33
Figure A9881052100272
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 34
Figure A9881052100273
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 35
Figure A9881052100281
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 36
Figure A9881052100282
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 37
Figure A9881052100283
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 38
Figure A9881052100291
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 39
Figure A9881052100292
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 40 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 41
Figure A9881052100301
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 42
Figure A9881052100302
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 43 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 44 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 45 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 46 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 47
Figure A9881052100321
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 48
Figure A9881052100322
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 49 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 50
Figure A9881052100331
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 51
Figure A9881052100332
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 52
Figure A9881052100333
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 53 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 54 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 55 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 56
Figure A9881052100351
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 57
Figure A9881052100352
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 58 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 59
Figure A9881052100361
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 60
Figure A9881052100362
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 61
Figure A9881052100363
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 62 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 63
Figure A9881052100372
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 64
Figure A9881052100373
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 65 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 66 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 67
Figure A9881052100383
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 68
Figure A9881052100391
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 69
Figure A9881052100392
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 70
Figure A9881052100393
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 71
Figure A9881052100401
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 72
Figure A9881052100402
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 73
Figure A9881052100403
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 74 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 75
Figure A9881052100412
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 76
Figure A9881052100413
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 77 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 78
Figure A9881052100422
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 79
Figure A9881052100423
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 80
Figure A9881052100431
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 81
Figure A9881052100432
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 82 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 83 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 84
Figure A9881052100442
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 85 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 86 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 87
Figure A9881052100452
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 88
Figure A9881052100453
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 89
Figure A9881052100461
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 90 (a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 91
Figure A9881052100463
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Group 92
Figure A9881052100471
(a: racemic modification, b:R enantiomorph, c:S enantiomorph) Z herein has and for example organizes the implication that provides in 1.
Use, for example, 1-(1-phenoxymethyl-propyl group)-biguanides and trifluoro-acetate are as starting raw material, and the reaction path in the inventive method (a) can illustrate with following reaction formula:
Figure A9881052100472
Use, for example, 2-chloro-4-(1-phenoxymethyl-propyl group amino)-6-Trifluoromethyl-1,3,5-triazine and ethamine are as starting raw material, and the reaction path in the inventive method (b) can illustrate with following reaction formula:
Use, for example, 2-amino-4-methoxyl group-6-Trifluoromethyl-1,3,5-triazine and 1-phenoxy group-propylamine are as starting raw material, and the reaction path in the inventive method (c) can illustrate with following reaction formula:
Figure A9881052100481
Use, for example, 2-amino-4-(1-phenoxymethyl-propyl group amino)-6-Trifluoromethyl-1,3,5-triazine and Acetyl Chloride 98Min. are as starting raw material, and the reaction path in the inventive method (d) can illustrate with following reaction formula:
Figure A9881052100482
Formula (II) is provided at the General Definition that is used as the aryloxy alkyl biguanides of starting raw material in the inventive method (a) for preparing formula of the present invention (I) compound.In formula (II), R 1, R 2, R 3, R 4Each preferably or particularly has the R that had mentioned already in the description of relevant formula of the present invention (I) compound above with Ar 1, R 2, R 3, R 4Preferred or particularly preferred implication with Ar.
Formula (II) starting raw material is still unexposed so far in document; As novel substance, their constitute more early but not the part of the theme of previous disclosed patent application (referring to, DE-A-19641691, October 10 1996 applying date-LeA31995).
The acid adduct that is fit to of formula (II) compound is the adduct of they and protonic acid.Protonic acid such as hydrogenchloride, hydrogen bromide, sulfuric acid, methylsulfonic acid, Phenylsulfonic acid and tosic acid.
The following acquisition of aryloxy alkyl biguanides of general formula (II):
Make the aryloxyalkylamines of the replacement of general formula (VII) R wherein 3, R 4With Ar as defined above ,-and/or the acid adduct of general formula (VII) compound, as, hydrochloride-with dicyanodiamide (" the dicyanogen methyl isophorone diamide of formula (IX) ") reaction
Figure A9881052100491
Exist down if be adapted at reacting auxiliary such as hydrogenchloride, if be adapted at thinner such as n-decane or 1,2-two chloro-benzene exist down, react under 100 ℃ to 200 ℃ temperature.(referring to, EP 492615, preparation embodiment).
The aryloxyalkylamines of general formula (VII) is to be used for this purpose precursor, they be known and/or can by known method preparation itself (referring to, Acta Pol.Pharm.53 (1996), 47-52-quote from the 126:46897 in Chem.Abstracts; Angew.Chem.106 (1994), 1041-1043; Bull.Soc.Chim.Belg.85 (1976), 421-425; Ditto, 86 (1977), 1003-1007; J.Med.Chem.10 (1967), 7 17-724; J.Am.Chem.Soc.97 (1975), 6900-6901; Tetrahedron Lett.35 (1994), 3745-3746; DE 3222152; DE 3221540; EP 355351; EP 601486; ZA 6903772; Preparation embodiment).
General formula (III) is provided in the inventive method (a) another General Definition as the alxoxycarbonyl compounds of starting raw material.In formula (III), Z preferably or particularly has the preferred or particularly preferred implication of the Z that had mentioned already in the relevant description of formula of the present invention (I) compound above; The preferred representative of R ' has alkyl, particularly methyl or the ethyl of 1 to 4 carbon atom.
Formula (III) starting raw material is the known synthetic compound of using.
Formula (IV) is provided at the General Definition of the halo triazine of the replacement that is used as starting raw material in the inventive method (b).In formula (IV), R 3, R 4, Ar and Z preferably or particularly have the R that had mentioned already in the description of relevant formula of the present invention (I) compound above 3, R 4, Ar and Z preferred or particularly preferred implication; X preferably represents fluorine or chlorine, particularly chlorine.
General formula (IV) starting raw material is still unexposed so far in document; As novel substance, their constitute more early but not the part of the theme of previous disclosed patent application (referring to, DE-A-19641691, October 10 1996 applying date-LeA31995).
The following acquisition of halo triazine of the replacement of general formula (IV):
Make the dihalo triazine of corresponding general formula (X)
Figure A9881052100501
Wherein X and Z as defined above, and X 1Represent halogen, with the aryloxyalkylamines reaction of the replacement of general formula (VII)
Figure A9881052100502
R wherein 3, R 4With Ar as defined above, exist down if be adapted at acid acceptor such as ethyl diisopropylamine, if be adapted at thinner such as tetrahydrofuran (THF) Huo diox exists down, under the temperature between-50 ℃ to+50 ℃, react (referring to preparing embodiment).
Formula (VI) is provided at the General Definition of the aminotriazine of the replacement that is used as starting raw material in the inventive method (c).In formula (VI), R 1, R 2Preferably or particularly has the R that in the description of relevant formula of the present invention (I) compound above, had mentioned already with Z 1, R 2Preferred or particularly preferred implication with Z.Y preferably represents fluorine, chlorine, methoxy or ethoxy, particularly chlorine or methoxyl group.
Formula (VI) starting raw material is known and/or can be by known method preparation (referring to WO95/11237) itself.
Formula (VII) is provided at the General Definition of the aryloxyalkylamines of the replacement that is used as starting raw material in the inventive method (c).In formula (VII), R 3, R 4Preferably or particularly has the R that in the description of relevant formula of the present invention (I) compound above, had mentioned already with Ar 3, R 4Preferred or particularly preferred implication with Ar.
Formula (VII) starting raw material is known and/or can prepares (referring to DE 3426919 by known method itself; DE 4000610; DE 4332738, and EP 320898; EP 443606; Tetrahedron:Asymmetry 5 (1994), 817-820; Tetrahedron Lett.29 (1988), 223-224; Ditto, 36 (1995), 3917-3920; Preparation embodiment).
Formula (Ia) is provided at according to the General Definition that is used as the aryloxy alkyl amino triazine of starting raw material in the inventive method (d) preparation formula (I) compound.In formula (Ia), R 1, R 3, R 4, Ar and Z preferably or particularly have the R that had mentioned already in the description of relevant formula of the present invention (I) compound above 1, R 3, R 4, Ar and Z preferred or particularly preferred implication.
As novel substance, the raw material of general formula (Ia) constitutes the application's part theme, but some in them also constitute more early not the part of the theme of previous disclosed patent application (referring to, DE-A-19641691, October 10 1996 applying date-LeA31995); They can be by the inventive method (a) and (b) or (c) preparation (referring to this preparation embodiment).
Formula (VIII) is provided at according to another is used as the alkylation of starting raw material or the General Definition of acylting agent in the inventive method (d) preparation formula (I) compound.In formula (VIII), R 2Preferably or particularly has the R that in the relevant description of formula of the present invention (I) compound above, had mentioned already 2Preferably or especially preferred but implication outside the dehydrogenation; Y preferably represents fluorine, chlorine, bromine, methoxyl group, oxyethyl group, acetoxyl group or propionyloxy, particularly chlorine, methoxyl group or acetoxyl group.
Formula (VIII) starting raw material is the synthetic known chemical of.
Formula produced according to the present invention (I) is if the method for compound is fit to using the reaction auxiliary to carry out.Be suitable for method (a) and (b), (c) and reaction auxiliary (d) normally conventional inorganic or organic bases or acid acceptor.These materials preferably include acetate, amide, carbonate, supercarbonate, hydride, oxyhydroxide or the alkoxide of basic metal or alkaline-earth metal, as sodium acetate, potassium acetate or lime acetate, lithamide, ammonification sodium, ammonification potassium or ammonification calcium, yellow soda ash, salt of wormwood or lime carbonate, sodium bicarbonate, salt of wormwood or lime carbonate, lithium hydride, sodium hydride, potassium hydride KH or hydrolith, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methylate, sodium ethylate, just or sodium isopropylate, just-, different-, secondary-or sodium tert-butoxide; Also has alkaline organic nitrogen compound in addition, as, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, ethyl-Diisopropylamine, N, N-dimethyl-cyclo-hexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, accelerine, N, N-dimethyl-benzyl amine, pyridine, the 2-methyl-, the 3-methyl-, the 4-ethyl-, 2, the 4-dimethyl-, 2, the 6-dimethyl-, 3, the 4-dimethyl-and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidines, 1,4-diazabicylo [2,2,2]-octane (DABCO), 1,5-diazabicylo [4,3,0]-ninth of the ten Heavenly Stems-5-alkene (DBN) or 1,8-diazabicylo [5,4,0]-11-7-alkene (DBU).
Be suitable for carrying out the inventive method (a) and (b), (c) and thinner (d) inert organic solvents particularly except water.These materials comprise the optional halogenated hydrocarbon of aliphatics particularly, alicyclic or aromatics, as, as gasoline, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin; Ethers is as ether, diisopropyl ether, diox, tetrahydrofuran (THF) or glycol dimethyl ether or ethylene glycol diethyl ether; Ketone is as methyl isopropyl ether or mibk; Nitrile is as acetonitrile, propionitrile or butyronitrile; Amides, as N, dinethylformamide, N,N-dimethylacetamide, N-methyl-formylaniline, N-Methyl pyrrolidone or HMPA; The ester class is as methyl acetate or ethyl acetate; The sulfoxide class is as dimethyl sulfoxide (DMSO); Alcohols, as methyl alcohol, ethanol, just-or Virahol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the mixture of they and water, or pure water.
Carry out the inventive method (a) and (b), (c) and (d) time, temperature of reaction can be carried out in the scope of broad.Usually, reaction is at-20 ℃ to+300 ℃, preferably carries out under the temperature between-10 ℃ to+250 ℃.
Method (a) and (b) of the present invention, (c) and (d) normally under normal pressure, carry out.Yet, the inventive method also can the pressurization or the decompression under---normally 0.1 the crust to 10 the crust between pressure under carry out.
When carrying out the inventive method, adopt the roughly starting raw material of equimolar amount usually.One of yet, also can excessive relative to the earth employing reactive component.Reaction carry out in the presence of the reaction auxiliary, and reaction mixture was stirred several hours under required temperature usually normally in the thinner that is fit to.Aftertreatment be with ordinary method carry out (referring to, the preparation embodiment).
Active compound of the present invention can be used as defoliating agent, siccative, kill the cane agent and in particular as weedicide.So-called weeds with regard to it the most in the broadest sense, are interpreted as being grown in all plants in the place that should not grow.Material of the present invention is as steriland herbicide or selective herbicide depends on used amount basically.
The compounds of this invention can relevant use with for example following plants: the broadleaf weed of following dependent of dead military hero: mustard belongs to, the grass of walking alone belongs to, Bedstraw, Stellaria, Matricaria, Anthemis, Achyranthes, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, japanese bearbind belongs to, sweet potato genus, Polygonum, Daubentonia, Ambrosia, Cirsium, bristlethistle, sonchus L, Solanum, the weldering Lepidium, Herba Clinopodii Polycephali belongs to, Vandellia, lamium, Veronica, abutilon, the thorn Rumex, Datura, Viola, the weasel hemp nettle belongs to, papaver, bachelor's-button, Trifolium, Ranunculus and Dandelion, the dicotyledonous crops of following dependent of dead military hero: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, linum, sweet potato genus, vetch, Nicotiana, tomato belongs to, Arachis, Btassica, Lactuca, Cucumis and Cucurbita, the monocotyledon weed of following dependent of dead military hero: Echinochloa, setaria, Panicum, knotgrass, ladder forage spp, annual bluegrass belongs to, festuca, yard grass belongs to, Brachiaria, lolium, Brome, Avena, Cyperus, jowar belongs to, Agropyron, Cynodon, Monochoria, genus fimbristylis, arrowhead belongs to, Eleocharis, grass belongs to, Paspalum, ischaemum, the cusp Pittosporum, talon eria, Agrostis, amur foxtail belongs to and the wind grass belongs to the monocot crops of following dependent of dead military hero: Oryza, Zea, Triticum, Hordeum, Avena, Secale, jowar belongs to, Panicum, saccharum, Ananas, Asparagus and allium.
Yet the application of active compound of the present invention never is limited to these genus, and also can extend to other plant in an identical manner.
Depend on compound concentrations, the compound natural disposition controlling weeds that is suitable for going out, for example industrial region and railway line, and the road and the square that have or do not have the plantation woods.Equally, compound can be used for preventing and treating the weeds of perennial crop, for example the weeds in forest, the decoration woods, orchard, vineyard, citrus woods, nut garden, any of several broadleaf plants plantation, cafetal, tea place, rubber plantation, oil palm plantation, cocoa plantation, mushy fruit woods and hops field, grassland, stadium and the pasture.And The compounds of this invention can also be used for optionally preventing and treating the weeds of annual crop.
Formula of the present invention (I) compound is particularly suitable for optionally preventing and treating unifacial leaf and broadleaf weed in the monocot crops in two kinds of modes before the bud and behind the bud.
Active compound can change into conventional preparation, as solution, emulsion, wettable powder, suspension agent, pulvis, the agent of dusting, paste, soluble powder, granule, suspended emulsion agent, with the natural or synthetic materials of active compound dipping, and wrap in micro-fine capsule in the polymkeric substance.
These preparations can be produced in a known manner, for example, with active compound with expand agent, i.e. liquid and/or mixes, and optional use tensio-active agent, i.e. emulsifying agent and/or dispersion agent and/or pore forming material with solid carrier.
Using water as under the situation that expands agent, also can make solubility promoter with organic solvent.The liquid solvent that is fit to mainly contains: aromatic substance, and as dimethylbenzene, toluene or alkylnaphthalene, chloro aromatic substance or chlorinated aliphatic hydrocarbon are as chlorinated benzene class, polyvinyl chloride-base or methylene dichloride, aliphatic hydrocrbon, as hexanaphthene or paraffin, for example petroleum cuts, mineral and vegetables oil, alcohols, as butanols or glycol with and ether and ester, ketone is as acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone, intensive polar solvent, as dimethyl formamide or dimethyl sulfoxide (DMSO), and water.
The solid carrier that is fit to is: for example ammonium salt and ground natural mineral matter, as kaolin, clay, talcum, chalk, quartz, attapulgite, montmorillonite or diatomite, with ground synthetic mineral matter, as high dispersive silicon-dioxide, alumina and silicate, the solid carrier that is suitable for granule has: for example crush and fractionated natural mineral matter such as calcite, marble, float stone, sepiolite and rhombspar, and the synthetic particle of organic and inorganic powder and following organic particle: wood sawdust, coconut husk, corn cob and tobacco stem; The emulsifying agent and/or the pore forming material that are fit to are: for example nonionic and anionic emulsifier, as polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, for example, the alkaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate and albumin hydrolysate; The dispersion agent that is fit to is: for example, and lignin sulfite waste liquor and methylcellulose gum.
Can use the natural and synthetic polymer of tackiness agent such as carboxymethyl cellulose and powdery, particle or latex form in the preparation, as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipid, as kephalin and Yelkin TTS, and synthetic phospholipid.Other possible additive can be mineral oil and vegetables oil.
Also may use tinting material, as mineral dye, for example ferric oxide, titanium oxide and Prussian blue, and organic dye are as the salt of alizarine dyestuff, azoic dyestuff and metal phthalocyanine dyestuff and micronutrient element such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Usually contain 0.1 to 95% active compound by weight in the preparation, preferred 0.5 to 90%.
Be controlling weeds, active compound of the present invention, its former state or with its dosage form also can be used as the mixture with known weedicide, whole preparation or the possible mixed thing of bucket and uses.
The possible common component of mixture is known weedicide, for example, acetochlor, acifluorfen (sodium salt), aclonifen, alachlor, alloxydim (sodium salt), ametryn, amidochlor, the acyl ethyl methyl, the spirit of sulphur grass, atrazine, the tetrazolium ethyl methyl, benazolin, benfuresate, benzyl ethyl methyl (methyl esters), bentazone, benzofenap, benzoylpropethyl (ethyl ester), two alanyl phosphorus, bifenox, bromobutide, bromofenoxim, bromoxynil, Butachlor technical 92, the fourth grass is special, cafenstrole, block careless amine, chlomethoxyfen, weed eradication is flat, pyrazon, chlorimuron (ethyl ester), chlornitrofen, chlorsulfuron, chlorotoluron, cinmethylin, ether is yellow grand, clethodim, alkynes oxalic acid clomazone, difluoro pyridine acid, clopyrasulfuron (methyl), cloransulam (methyl), cumyluron, cyanazine, the weed eradication spy, AC322140, cycloxydim, cyhalofop-butyl, 2,4-drips, 2, the 4-Embutox, 2,4-drips propionic acid, desmedipham, di_allate, dicamba 98, diclofop-methyl (methyl esters), two benzene azoles are fast, diflufenican Ding Evil is grand, dimepiperate, dimethachlor, diformazan third second is clean, dimethenamid, the spirit of amino second fluorine, diphenamide, diquat, dithiopyr, Diuron Tech, daimuron, EPTC, esprocarb, ethalfluralin, Ethanetsulfuron (methyl esters), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid oxazole diclofop-methyl ethyl ester, wheat straw volt (isopropyl ester), the wheat straw volt (isopropyl ester-L), wheat straw volt (methyl esters), the pyridine ethyl methyl, fluazifop (butyl ester), flumetsulam, methylarsonic acid, flumioxazin, flumipropyn, fluometuron, the fluorine cisanilide, fluoroglycofenethyl (ethyl ester), amine grass azoles, flupropacil, the fluorenes butyric acid, the fluorine butanone, fluroxypyr, flurprimidol, flurtamone, Fomesafen, Glufosinate (ammonium salt), glyphosate (isopropyl ammonium salt), halosafen, pyrrole fluorine chlorine standing grain spirit (ethoxy ethyl ester), hexazinone, miaow grass ester (methyl esters), imzamethapyr, imazamox, the weed eradication cigarette, the weed eradication quinoline, Imazethapyr, imidazoles is yellow grand, ioxynil, isopropalin, isoproturon Yi Evil acyl grass, isoxaflutole Evil grass ether, lactofen, lenacil, methoxydiuron, 2 first, 4 chlorine, Vi par, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metsulfuron-methyl (methyl esters), the piperazine humulone, Hydram, monolinuron, naproanilide, napropamide, neburon, nicoculsfuron, norflurazon, orbencarb, oryzalin Evil humulone, oxyfluorfen, Paraquat, pendimethalin, phenmedipham, piperophos, the third careless amine, Fluoropyrimidinesulfuron (methyl esters), prometryn, propachlor, Stam F-34, propaquizafop, pentyne grass amine, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron (ethyl ester), pyrazoxyfen, pyributicarb, pyridate, pyrithiobacsodium, quinclorac, quinmerac, quizalofop (ethyl ester), quizalofop (tetrahydrochysene chaff ester), the sulfone ethyl methyl, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, ethyl methyl (methyl esters), grass sulphur phosphorus, tebutam, terbufos benzthiazuron, terbuthylazine, terbutryn, P DimethenamidP, thifluzamide, thrizopyr, thidiazimin, thiophene methyl (methyl esters), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron-methyl (methyl esters), TRICLOPYR ACID, tridiphane, trifluralin and fluorine amine are yellow grand.
It also can be mixture with other known activity compound such as mycocide, sterilant, miticide, nematocides, bird repellent, plant food and soil conditioner.
Active compound can with itself, with its preparation or by further dilution and the type of service of preparation uses of warp, as direct available solution, suspension, emulsion, pulvis, paste and granule.They use with ordinary method, for example pour, spraying, atomizing or spread fertilizer over the fields or the like.
Active compound of the present invention can be used before or after plant germination.They also can mix in the soil prior to seeding.
The amount of used active compound can change in the scope of broad.Consumption depends on required effect basically.Usually, usage quantity is between per hectare soil surface-area restrains to 10 kilograms with 1, and preferred per hectare 5 grams are to 5 kilograms.
The preparation of active compound of the present invention and use can be referring to the following example.
Preparation embodiment:
Embodiment 1
Figure A9881052100561
(method (a))
Will-10 ℃ down preparation 3.2g (10mmol) (R/S)-1-[1-ethyl-2-(3,5-dimethyl-phenoxy group)-ethyl]-biguanide hydrochloride (racemic modification), 1.3g (10.6mmol) trifluoro-acetate, 1.0g (20mmol) sodium methylate, 2.75g zeolite molecular sieve and 20ml methanol mixture stirred about 15 hours down at about 0 ℃.With the mixture suction filtration, filtrate water is diluted to about three times of its volume afterwards, shakes with the ethyl acetate shake, and isolates organic layer, washes with water, with dried over sodium sulfate and filtration.Under pump vacuum, carefully distill solvent.
Provide thus 2.0g (the HPLC purity assay is 92%, promptly 52% of theoretical value) (R/S)-2-amino-4-trifluoromethyl-6-[1-(3,5-dimethyl-phenoxymethyl)-third amino]-1,3,5-triazines (racemic modification), be the amorphous residue; LogP:3.77b).
Be similar to preparation embodiment 1, and the general description of method produced according to the present invention also can be prepared formula (I) compound of for example listing in the table 1 hereinafter. Table 1: formula (I) examples for compounds
Figure A9881052100571
Figure A9881052100591
Figure A9881052100611
Figure A9881052100621
Figure A9881052100631
Figure A9881052100641
Figure A9881052100651
Figure A9881052100671
Figure A9881052100681
Figure A9881052100691
Figure A9881052100701
Figure A9881052100721
Figure A9881052100731
Figure A9881052100741
Figure A9881052100751
Figure A9881052100761
Figure A9881052100781
Figure A9881052100791
Figure A9881052100801
Figure A9881052100821
Figure A9881052100831
Figure A9881052100841
Figure A9881052100851
Figure A9881052100861
Figure A9881052100871
Figure A9881052100881
LogP in the table 1 is by HPLC (high performance liquid chromatography), uses reversed-phase column (C18) to measure with EEC Directive79/831 Annex.43 ℃ of temperature.(a) the mensuration moving phase in acid range: 0.1% phosphate aqueous solution, acetonitrile; Be denoted as a) table 1 from the linear gradient liquid-corresponding test-results of 10% acetonitrile to 90% acetonitrile.(b) the mensuration moving phase in neutral range: the 0.01 mole of phosphoric acid salt buffer aqueous solution, acetonitrile; Table 1, be denoted as b from the linear gradient liquid-corresponding test-results of 10% acetonitrile to 90% acetonitrile).Proofread and correct and adopt non-branched alkane-2-ketone (having 3 to 16 carbon atoms) to carry out with known logP value.The logP of this non-branched alkane-2-ketone measures by using linear interpolation to survey retention time between two back to back alkane ketone.Use the UV spectrum of 200 nanometer to 400 nanometers to measure the λ maximum value at maximum chromatographic signal place.Formula (II) starting raw material: embodiment (II-1)
Figure A9881052100891
The 12g that in mortar, ground (52mmol) (R, S)-1-ethyl-2-(3, the 5-dimethyl phenoxy)-mixture (" pure state " promptly do not add thinner) of ethylamine hydrochloride (racemic modification) and 4.3g (52mmol) dicyanodiamide (dicyano diamide) is heated to 160 ℃ in the round bottom beaker.Under magnetic agitation, the molten mass of gained was remained under this temperature about 30 minutes.After cooling a little,, afterwards solvent is carefully distilled under pump vacuum still molten mass being dissolved in the 70ml methyl alcohol when warm.
Provide 16.2g (theoretical value 100%) 1-[1-(3,5-dimethyl-phenoxymethyl)-propyl group thus]-biguanide hydrochloride (racemic modification), be solid product.
Be similar to preparation embodiment (II-1), also can prepare formula (II) compound of for example listing in the table 2 hereinafter.
Figure A9881052100892
Table 2: formula (II) examples for compounds-(hydrochloride)
Figure A9881052100901
Figure A9881052100911
Figure A9881052100921
Formula (VII) starting raw material: embodiment (VII-1) Step 1
Figure A9881052100932
With 21.6g (0.20mol) meta-cresol, 20.0g (0.26mol) 1, the mixture of 2-oxyethyl group-butane and 0.5g (0.02mol) lithium hydroxide stirred 20 hours down at 180 ℃.Mixture is used the 1N aqueous sodium hydroxide solution with the long-pending toluene digestion of about diploid, washes with water afterwards, with dried over sodium sulfate and filtration.Filtrate concentrates under pump vacuum, and residue is being distilled under top temperature is approximately 160 ℃ bath temperature under the pressure of strong relatively reduction, product at condenser in crystallization.
Provide 1-(3-methyl-phenoxymethyl)-propyl alcohol of 28g (theoretical value 78%) thus, 84 ℃ of boiling points (at 0.4 crust).Step 2
Figure A9881052100933
At room temperature 177g (0.98mol) 1-(3-methyl-phenoxymethyl)-propyl alcohol is added in the 980ml pyridine earlier, and under agitation slowly be metered into 112g (0.98mol) methylsulfonyl chloride.Reaction mixture stirred 15 hours down at 20 ℃, concentrated under pump vacuum.The concentrated hydrochloric acid acidifying is used in the digestion of residue water, and shakes with methylene dichloride, and organic phase washes with water, uses dried over sodium sulfate, and filters.Under pump vacuum, carefully solvent is distilled from filtrate.
Provide 227g (theoretical value 90%) 1-(3-methyl-phenoxymethyl)-propyl group methanesulfonates thus, be the oily residue.H-NMR(CDCl 3，δ)：3.08ppm(s，SO 2CH 3)。Step 3
Figure A9881052100941
210g (0.81mol) 1-(3-methyl-phenoxymethyl)-propyl group methanesulfonates is dissolved in the 500ml methyl alcohol, and in autoclave, under about 100 ℃ of temperature and the highest about 2 crust, be metered into ammonia, obviously finish up to absorption by the internal pressure measuring ammonia.Open autoclave, its inclusion is transferred in the round-bottomed flask, and concentrate under pump vacuum, residue mixes with 400ml 2N aqueous sodium hydroxide solution, and shakes with methylene dichloride.Organic phase is also filtered with dried over sodium sulfate.Filtrate concentrates under pump vacuum, and residue distills (it is the highest about 150 ℃ to bathe temperature) under strong relatively decompression.
Provide 102g (theoretical value 72%) 1-(3-methyl-phenoxymethyl)-propylamine (0.7 millibar following boiling point 80-82 ℃) thus.Step 4:
Earlier 101g (0.57mol) 1-(3-methyl-phenoxymethyl)-propylamine is added in the 1500ml tetrahydrofuran (THF), and under 0 ℃ to 20 ℃ temperature, under agitation hydrogenchloride (chlorine body) is imported, saturated up to solution.The crystalline product of gained is separated by suction filtration.
Provide 83g (theoretical value 67%) 1-(3-methyl-phenoxymethyl)-propylamin hydrochloride thus.The fractionation of the enantiomorph of formula (VII) compound:
Figure A9881052100951
Earlier 74.2g (0.45mol) 1-phenoxymethyl-propylamine and 51.5g (0.50mol) methoxy menthyl acetate are added 450ml methyl-tert-butyl ether.Under 40 ℃, add 3.7g Novozym 435 (deriving from Novo Nordisk), and under this temperature, stirred 150 minutes.The mixture suction leaches, and filtrate is mixed with 250ml ice-water and 39ml concentrated hydrochloric acid, and stirs 20 minutes.Afterwards organic solvent is distilled under pump vacuum, and after adding 200ml water, with dichloromethane extraction three times (" extraction solution A ").
Water is adjusted to pH=13 with the 2N aqueous sodium hydroxide solution, and uses dichloromethane extraction.Extraction liquid is with dried over sodium sulfate and filter, and filtrate concentrates under pump vacuum, provide 35.1g (S)-1-phenoxymethyl-propylamine (94.5% of theoretical value, ee88.3%).
Extraction solution A also filters with dried over sodium sulfate; Filtrate concentrates under pump vacuum.The raw product of gained (R)-N-methoxyl group ethanoyl-1-phenoxymethyl-propylamine is with 300ml water and the digestion of 60ml concentrated hydrochloric acid, and under boiling point reflux 20 hours.The mixture dichloromethane extraction, extraction liquid is with dried over sodium sulfate and filter, filtrate concentrates under pump vacuum, provide 30.7g (R)-1-phenoxymethyl-propylamine (79.5% of theoretical value, 93.2%ee).
As stating, similarly, also can prepare formula (VII) compound of for example listing in the table 3 hereinafter as top specific embodiment.
Figure A9881052100952
Table 3: formula (VII) examples for compounds
Figure A9881052100961
The additional embodiment 26a of table 1 and 26f have prepared in the above-mentioned table 1 two kinds of optical isomers (enantiomorph) itself contained in 26 times described racemic modifications of embodiment respectively: S-enantiomorph-logP:2.86 (pH 7.5) Application Example a) R-enantiomorph-logP:2.86 (pH 7.5) b):
In the Application Example that is described below, the known compound of formula (A) is as contrasting material:
Figure A9881052100992
N-[2-(3,5-dimethyl-phenoxy group)-1-methyl-ethyl]-6-(1-fluoro-1-methyl-ethyl)-1,3,5-triazines-2,4-diamines-known by EP 411153.Test solvent before the embodiment A bud: 5 parts of weight acetone emulsifying agents: the alkaryl polyglycol ether of 1 part of weight
When preparing the active agent preparations that is fit to, with the active compound of 1 part of weight and the solvent of described amount, with the emulsifying agent adding of described amount, and water is diluted to desired concn with this missible oil.
The seed of test plant is broadcast in the common soil, and after 24 hours, soil is sprayed with active agent preparations, uses the activeconstituents of specified quantitative on per unit area.Select the concentration of spraying fluid, the specified quantitative of required active compound is used with the spray amount of 1000 premium on currency/hectares.
After three weeks, the degree of damage of plant is compared with the development of untreated control, infringement % is made in range estimation.
The implication of numerical value is as follows:
0%=do not have effect (be untreated identical)
100%=damages fully
In this test, preparation embodiment 1,2,3,4,5,6,37 and 38 pairs of weeds demonstrate strong activity, and they some can be tolerated (referring to Table A) well by crop such as corn." ai. " expression activeconstituents in the table.Table A: test before the greenhouse bud
The active compound of the following preparation embodiment of using dosage corn Herba Setariae Viridis amaranth Tender Catchweed Bedstraw Herb
(g?ai./ha)
Figure A9881052101011
(2) 1000 0 95 80 -
(38) 1,000 20 70 90 100 Table As: (continuing)
The active compound of the following preparation embodiment of using dosage corn Herba Setariae Viridis piemarker amaranth mustard
(g?ai./ha)
(3) 1000 0 100 60 70 80
Figure A9881052101022
(6) 1,000 20 80 70 80 100 Table As: (continuing)
The active compound of the following preparation embodiment of using dosage amur foxtail Herba Setariae Viridis piemarker amaranth Tender Catchweed Bedstraw Herb mustard
(g?ai./ha)
Figure A9881052101031
(5) 1,000 80 90 70 90 80 100 Table As: (continuing)
The active compound of the following preparation embodiment of using dosage corn amur foxtail Herba Setariae Viridis piemarker amaranth mustard
(g?ai./ha)
(1) 1000 20 80 95 80 80 70
(4) 1,000 0 80 100 90 70-Table As: (continuing)
The active compound of the following preparation embodiment of using dosage lady's-grass barnyard grass Cassia tora thorn apple black nightshade veronica
(g?ai./ha)
Figure A9881052101051
Test solvent behind (37) the 500 95 95 100 95 100 100 Embodiment B buds: 5 parts of weight acetone emulsifying agents: the alkaryl polyglycol ether of 1 part of weight
When preparing the active agent preparations that is fit to, with the active compound of 1 part of weight and the solvent of described amount, with the emulsifying agent adding of described amount, and water is diluted to desired concn with this missible oil.
Press a certain amount of required active agent preparations of unit surface spray application to plant height 5-15 centimetre test plant.Select the concentration of spraying fluid, the specified quantitative of required compound is used with the amount of 1,000 premium on currency/hectare.
After three weeks, the degree of damage of plant is compared with untreated control, make infringement %.
The implication of numerical value is as follows:
0%=do not have effect (be untreated identical)
The 100%=completely destroy
In this test, preparation embodiment 1,2,3,4,5,6,37 and 38 pairs of weeds demonstrate strong activity, and they some can be tolerated (referring to table B) well by crop such as corn and wheat.Table B: test behind the greenhouse bud
The active compound of the following preparation embodiment of using dosage piemarker german chamomile chickweed violet Siberian cocklebur
(g?ai./ha)
Figure A9881052101071
(A) 250 80 50 70 70 70
Figure A9881052101072
(37) 250 100 95 90 100 90 table B:(are continuous)
The active compound of the following preparation embodiment of using dosage Herba Setariae Viridis piemarker german chamomile chickweed violet
(g?ai./ha)
(A) 250 70 80 50 70 70
(38) 250 80 95 70 80 100 table B:(are continuous)
The active compound of the following preparation embodiment of using dosage corn amur foxtail Herba Setariae Viridis piemarker amaranth mustard
(g?ai./ha)
(1) 1,000 20 70 95 100 100 100 table B:(is continuous)
The active compound of the following preparation embodiment of using dosage amur foxtail Herba Setariae Viridis piemarker amaranth Tender Catchweed Bedstraw Herb mustard
(g?ai./ha)
Figure A9881052101101
(2) 1000 90 95 80 95 100 95
Figure A9881052101102
(3) 1,000 80 100 95 100 90 100 table B:(are continuous)
The active compound of the following preparation embodiment of using dosage amur foxtail Herba Setariae Viridis piemarker amaranth Tender Catchweed Bedstraw Herb mustard
(g?ai./ha)
Figure A9881052101111
(4) 1000 70 80 - 80 90 100
Figure A9881052101112
(5) 1,000 80 100 95 100 95 100 table B:(are continuous)
The active compound of the following preparation embodiment of using dosage amur foxtail Herba Setariae Viridis piemarker amaranth Tender Catchweed Bedstraw Herb mustard
(g?ai./ha)
(6) 1,000 90 100 100 100 95 100 table B:(are continuous)
The lead a cow active compound of the following preparation embodiment of black nightshade of using dosage wheat amaranth thorn apple
(g?ai./ha)
(37) 125 0 95 95 100 95 table B:(are continuous)
The active compound of the following preparation embodiment of using dosage wheat and corn Herba Setariae Viridis Cassia tora lamb's-quarters thorn apple black nightshade
(g?ai./ha)
Figure A9881052101141
(38) 125 0 0 70 95 100 95 95

Claims (8)

1. the aryloxy alkyl amino triazines of the replacement of general formula (I)
Figure A9881052100021
R wherein 1Represent hydrogen, or representative optional by hydroxyl-, cyano group-, halogen-or C 1-C 4The alkyl with 1 to 6 carbon atom of-alkoxyl group-replacement, R 2Represent hydrogen, represent formyl radical or all can choose wantonly by cyano group-, halogen-or C 1-C 4The alkyl, alkyl-carbonyl or the alkoxy carbonyl that respectively have 1 to 6 carbon atom of-alkoxyl group-replacement at moieties, R 3Representative optional by hydroxyl-, cyano group-, halogen-or C 1-C 4The alkyl with 2 to 6 carbon atoms of-alkoxyl group-replacement, or representative optional by cyano group-, halogen-or C 1-C 4The cycloalkyl with 3 to 6 carbon atoms of-alkyl-replacement, R 4Represent hydrogen or have the alkyl of 1 to 4 carbon atom, the Ar representative all can be chosen substituted phenyl, naphthyl, tetrahydro naphthyl or heterocyclic radical wantonly,
Wherein possible heterocyclic radical is preferably selected from following groups:
Furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzothiazolyl,
Oxazolyl, benzoxazolyl, thiadiazolyl group, oxadiazole base, pyrazolyl, pyrryl, pyridine
Base and pyrimidyl,
And wherein possible substituting group respectively is preferably selected from following groups:
Hydroxyl, cyano group, formamyl, thiocarbamoyl, nitro, halogen all can be appointed
Choosing is by the alkyl or the alcoxyl that respectively have 1 to 6 carbon atom of hydroxyl, cyano group or halogen-replacement
Base all can be chosen the alkyl that respectively has 1 to 6 carbon atom on alkyl by halogen-replacement wantonly
Carbonyl, alkoxy carbonyl, alkylthio, alkyl sulphinyl, alkyl sulphonyl, dialkyl group
Amino, alkyl-carbonyl-amino, alkyl sulfonyl-amino, two-alkyl-carbonyl-amino, two-alkane
Base alkylsulfonyl-amino, N-alkyl-N-alkyl-carbonyl-amino or N-alkyl-N-alkyl sulphonyl-
Amino, each optional by hydroxyl-, cyano group-, nitro-, halogen-, C 1-C 4-alkyl-, C 1-C 4-
Haloalkyl-, C 1-C 4-alkoxyl group-or C 1-C 4The phenyl of-halogenated alkoxy-replacement or benzene oxygen
Base and all can choose methylene-dioxy or ethylenedioxy wantonly by halogen-replacement,
Represent halogen with Z, the representative all can choose wantonly by hydroxyl-, cyano group-, halogen-, C 1-C 4-alkoxyl group-,
C 1-C 4-alkyl-carbonyl-, C 1-C 4-alkoxyl group-carbonyl-, C 1-C 4-alkylthio-, C 1-C 4-alkane
The base sulfinyl-or C 1-C 4Each of-alkyl sulphonyl-replacement has 1 to 6 carbon on alkyl
The alkyl of atom, alkoxyl group, alkyl-carbonyl, alkoxy carbonyl, alkylthio, the inferior sulphur of alkyl
Acyl group or alkyl sulphonyl, or representative optional by cyano group-, halogen-or C 1-C 4-alkyl-replacement
The cycloalkyl with 3 to 6 carbon atoms.
2. the formula of claim 1 (I) compound, wherein R 1Represent hydrogen, or representative all can choose wantonly by hydroxyl-, cyano group-, fluoro-, chloro-, methoxyl group-or the methyl of oxyethyl group-replacements, ethyl, just-or different-propyl group, just-, different-, the second month in a season-or the tertiary butyl, R 2Represent hydrogen, represent formyl radical, or representative all can choose wantonly by cyano group-, fluoro-, chloro-, bromo-, methoxyl group-or the methyl of oxyethyl group-replacement, ethyl, ethanoyl, propionyl, just-or isobutyryl, methoxycarbonyl or ethoxy carbonyl, R 3Representative all can choose wantonly by hydroxyl-, cyano group-, fluoro-, chloro-, methoxyl group-or the ethyl of oxyethyl group-replacements, just-or different-propyl group, just-, different-, the second month in a season-or the tertiary butyl, or representative all can choose wantonly by cyano group-, fluoro-, chloro-, methyl-or cyclopropyl, cyclobutyl, cyclopentyl or the cyclohexyl of ethyl-replacement, R 4Represent hydrogen or methyl, the Ar representative all can be chosen substituted phenyl, naphthyl, tetrahydro naphthyl or heterocyclic radical wantonly,
Wherein possible heterocyclic radical is preferably selected from following groups:
Furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzothiazolyl,
Oxazolyl, benzoxazolyl, thiadiazolyl group, oxadiazole base, pyrazolyl, pyrryl, pyridine
Base and pyrimidyl,
And wherein possible substituting group respectively is preferably selected from following groups:
Hydroxyl, cyano group, formamyl, thiocarbamoyl, nitro, fluorine, chlorine, bromine,
All can choose wantonly by hydroxyl-, cyano group-, the methyl that replaces of fluoro-or chloro-, ethyl, just-or different third
Base, just-, different-, secondary-or the tertiary butyl, methoxyl group, oxyethyl group, just-or isopropoxy,
Just-, different-, secondary-or tert.-butoxy, all can choose the ethanoyl, third that replaces by fluoro-or chloro-wantonly
Acyl group, just-or isobutyryl, methoxycarbonyl, ethoxy carbonyl, just-or isopropoxy
Carbonyl, methylthio group, ethylmercapto group, just-or different-rosickyite base, methylsulfinyl, ethyl Asia
Alkylsulfonyl, just-or sec.-propyl sulfinyl, methyl sulphonyl, ethylsulfonyl, just-or
Sec.-propyl alkylsulfonyl, dimethylamino, diethylamino, acetylamino, propionyl ammonia
The base, methyl sulphonyl is amino, ethylsulfonyl is amino, diacetyl group is amino, two-methyl sulphur
Acyl group-amino, N-methyl-N-acetylamino or N-methyl-N-methyl sulphonyl amino, each
Optional by hydroxyl-, cyano group-, nitro-, fluoro-, chloro-, bromo-, methyl-, ethyl-, just-
Or sec.-propyl, just-, different-, secondary-or tertiary butyl, trifluoromethyl, methoxyl group-, oxyethyl group-,
Just-or isopropoxy-, just-, different-, secondary-or tert.-butoxy-, difluoro-methoxy-or trifluoro
The phenyl of methoxyl group-replacement or phenoxy group and all can choose the methylene two that replaces by fluoro-or chloro-wantonly
Oxygen base or ethylenedioxy,
Represent fluorine with Z; chlorine; bromine; the representative all can choose wantonly by hydroxyl-; cyano group-; nitro-; fluoro-; chloro-; methoxyl group-; oxyethyl group-; just-or isopropoxy-; just-; different-; secondary-or tert.-butoxy-; methylthio group-; ethylmercapto group-; just-or different-rosickyite base-; methylsulfinyl-; the ethyl sulfinyl-; just-or the sec.-propyl sulfinyl-; methyl sulphonyl-; ethylsulfonyl-; just-or the methyl of sec.-propyl alkylsulfonyl-replacement; ethyl; just-or sec.-propyl; just-; different-; secondary-or the tertiary butyl; methoxyl group; oxyethyl group; just-or isopropoxy; just-; different-; secondary-or tert.-butoxy; methylthio group; ethylmercapto group; just-or the iprotiazem base; methylsulfinyl; the ethyl sulfinyl; just-or the sec.-propyl sulfinyl; methyl sulphonyl; ethylsulfonyl; just-or sec.-propyl alkylsulfonyl, or representative all can choose wantonly by cyano group-; fluoro-; chloro-; methyl-or the cyclopropyl of ethyl-replacement; cyclobutyl; cyclopentyl or cyclohexyl.
3. the formula of claim 1 (I) compound, wherein R 1Represent hydrogen, or representative all can choose wantonly by cyano group-, fluoro-, methoxyl group-or the methyl or the ethyl of oxyethyl group-replacement, R 2Represent hydrogen, or representative all can choose wantonly by cyano group-, fluoro-, chloro-, methoxyl group-or methyl, ethyl, ethanoyl or the propionyl of oxyethyl group-replacement, R 3Representative all can choose wantonly by fluoro-, chloro-, methoxyl group-or the ethyl of oxyethyl group-replacement, just-or different-propyl group, R 4Represent hydrogen, the Ar representative all can be chosen substituted phenyl or naphthyl wantonly,
Wherein possible substituting group respectively is preferably selected from following groups:
Hydroxyl, cyano group, nitro, fluorine, chlorine, bromine, all can choose wantonly by hydroxyl-, cyano group-, fluoro-or
The methyl that chloro-replaces, ethyl, just-or sec.-propyl, just-, different-, secondary-or tertiary butyl, first
Oxygen base, oxyethyl group, just-or isopropoxy, just-, different-, secondary-or tert.-butoxy, all can
The optional ethanoyl that replaces by fluoro-or chloro-, propionyl, just-or isobutyryl, methoxyl group carbonyl
Base, ethoxy carbonyl, just-or isopropoxy carbonyl, methylthio group, ethylmercapto group, just-or different-
Rosickyite base, methylsulfinyl, ethyl sulfinyl, just-or sec.-propyl sulfinyl, first
Base alkylsulfonyl, ethylsulfonyl, just-or sec.-propyl alkylsulfonyl, each optional by hydroxyl-, cyanogen
Base-, nitro-, fluoro-, chloro-, bromo-, methyl-, ethyl-, just-or sec.-propyl, just-,
Different-, secondary-or tertiary butyl, trifluoromethyl, methoxyl group-, oxyethyl group-, just-or isopropoxy
-, just-, different-, secondary-or tert.-butoxy-, difluoro-methoxy-or trifluoromethoxy-replacement
Phenyl or phenoxy group and all can choose methylene-dioxy or the inferior second two that replaces by fluoro-or chloro-wantonly
The oxygen base,
With Z representative all can choose wantonly by hydroxyl-, cyano group-, fluoro-, chloro-, methoxyl group-, oxyethyl group-, just-or isopropoxy-, methylthio group-, ethylmercapto group-, just-or different-rosickyite base-, methylsulfinyl-, the ethyl sulfinyl-, just-or sec.-propyl sulfinyl-, methyl sulphonyl-, ethylsulfonyl-, just-or the methyl of sec.-propyl alkylsulfonyl-replacements, ethyl, just-or sec.-propyl, just-, different-, secondary-or the tertiary butyl, or represent all can choose wantonly by cyano group-, fluoro-, chloro-, methyl-or cyclopropyl, cyclobutyl, cyclopentyl or the cyclohexyl of ethyl-replacement.
4. the method for formula (I) compound of preparation claim 1 is characterized in that,
(a) if make alkoxyalkyl two guanidines of general formula (II) with being adapted under the thinner existence down if be adapted at reacting the auxiliary existence
Figure A9881052100051
Wherein
R 1, R 2, R 3, R 4With Ar as defined in claim 1,
-and/or the acid adduct of general formula (II) compound-
Alxoxycarbonyl compounds reaction with general formula (III)
Z-CO-OR’ (III)
Wherein
Z as defined in claim 1, and R ' represents alkyl, if if or (b) be adapted at reacting auxiliary and exist down and be adapted at thinner and exist down, make the halo triazine of the replacement of general formula (IV) R wherein 3, R 4, Ar and Z as defined above and X represent halogen, with the nitrogenous compound reaction of logical formula V
Figure A9881052100062
R wherein 1And R 2As defined above, if if or (c) be adapted at reacting auxiliary and exist down and be adapted at thinner and exist down, make the aminotriazine of the replacement of general formula (VI)
Figure A9881052100063
R wherein 1, R 2With Z as defined above, and Y 1Represent halogen or alkoxyl group, with the aryloxyalkylamines reaction of general formula (VII)
Figure A9881052100071
Wherein Ar, R 3And R 4As defined above, or (d) prepare wherein R 2When not being formula (I) compound of hydrogen, if make the aryloxy alkyl amino triazine of general formula (Ia) with being adapted under the thinner existence down if be adapted at reacting the auxiliary existence
Figure A9881052100072
Wherein
R 1, R 3, R 4, Ar and Z as defined above,
Alkylation or acylting agent reaction with general formula (VIII)
Y 2-R 2 (VIII)
Wherein
R 2As defined above, but outside the dehydrogenation and
Y 2Represent halogen ,-O-R 2Or-O-CO-R 2,
And if be fit to by ordinary method, will be according to method (a) and (b), (c) or (d) acquisition
General formula (I) compound in the above-mentioned substituting group range of definition, further transform.
5. herbicidal composition is characterized in that, they comprise formula (I) compound of at least a claim 1.
6. the application of the formula of claim 1 (I) compound control noxious plant.
7. method of controlling weeds is characterized in that, formula (I) compound effects that makes claim 1 is in weeds or its dried rhizome of rehmannia of dwelling.
8. prepare the method for herbicidal composition, it is characterized in that, with formula (I) compound of claim 1 with expand agent and/or tensio-active agent and mix.
CN98810521A 1997-10-24 1998-10-14 Substituted aryloxy alkyl amino triazines Pending CN1277606A (en)

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US4844731A (en) * 1986-12-27 1989-07-04 Idemitsu Company Co., Ltd. Triazine derivatives
HUT55605A (en) * 1989-02-20 1991-06-28 Idemitsu Kosan Co Herbicide compositions containing diamino-triazine derivatives as active componentsand process for producing the active components
DE19531084A1 (en) * 1995-08-24 1997-02-27 Hoechst Schering Agrevo Gmbh 2,4-diamino-1,3,5-triazines, process for their preparation and their use as herbicides and plant growth regulators
DE19641694A1 (en) * 1996-10-10 1998-04-16 Bayer Ag Substituted 2,4-diamino-1,3,5-triazines

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