CN1079965A - Weedicide - Google Patents
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- CN1079965A CN1079965A CN93105215A CN93105215A CN1079965A CN 1079965 A CN1079965 A CN 1079965A CN 93105215 A CN93105215 A CN 93105215A CN 93105215 A CN93105215 A CN 93105215A CN 1079965 A CN1079965 A CN 1079965A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/20—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom three- or four-membered rings
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
-
- 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
- A01N47/00—Biocides, 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
- A01N47/08—Biocides, 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
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
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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)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A kind of compound contains monic acids A, monic acids B, and monic acids C, the ester of aeromonas tenuazonic acid and pseudomonic acid, acid amides, the herbicidal composition of aryl and heterocyclic radical derivative is with formula (Zymomonas mobilis base)-OC-XR
3The new monad acid ester of expression, wherein (Zymomonas mobilis base) is the residue of aeromonas acid compound (Mon)-COOH, X is O or S and R
3By-A-R " alkyl that replaces, wherein A is O or S (O) x base, and R " is alkyl, alkenyl, alkynyl group, phenyl, alkyl, carbonyl, cycloalkyl or the heterocyclic radical that replaces arbitrarily.
Description
The present invention relates to as compound of weedicide and preparation method thereof and relate to herbicidal composition and using method thereof.
The derivative of known many monic acids (monic acid) is used for medicine and veterinary drug, the compound of biologically active effect.These compounds especially are described in UK Patent Application GB1587058 number.
We have now found that some monic acids derivative comprises ester, and acid amides and salt have new unexpected weeding activity.
According to the present invention, provide and the formula I of weedicide acceptable carrier or mixing diluents or the herbicidal composition of (I A) or (I B) compound, wherein Y represents (I C) or (I D) or (I E) and R wherein
2Be CO-XR
3, wherein X is O or S and R
3Be acceptable one-tenth ester group on hydrogen or the agrochemistry; Or R
2For-R
4Base is R wherein
4Be aryl or the heterocyclic radical that replaces arbitrarily; Or R
2Be CO-NR
5R
6Base is R wherein
5And R
6For identical or different and represent acceptable one-tenth amide group on the agricultural separately; Or (I), the steric isomer and the formula I of (I A) and (I B) compound, the salt of (I A) and (I B) compound is R wherein
2Be COXR
3, X is O and R
3Be hydrogen.
According to a further aspect of the invention, grievous injury is provided or has killed the method for noxious plant, it comprises and imposes on plant, or the growing environment of plant, the formula I of herbicidally effective amount or (I A) compound, wherein Y represents (I C) or (I D) or (I E); R
2Be CO-XR
3Base wherein X is O or S and R
3Be acceptable one-tenth ester group on hydrogen or the agrochemistry; Or R
2For-R
4Base is R wherein
4Be the heterocyclic radical that replaces arbitrarily; Or R
2For-CO-NH-CH
2-CO-W base wherein W is a hydrogen, arbitrarily the phenyl that replaces, the C that replaces arbitrarily
1To C
20Alkyl is substituted with C arbitrarily
2To C
8Alkenyl, the C that replaces arbitrarily
2To C
8Alkynyl group, heterocyclic radical or the C that replaces arbitrarily
3To C
7Cycloalkyl; Or R
2For-CO-NH-NH
2Base or-CO-NH-NH-CO-Y wherein Y be any C of replacement
1To C
20, any C that replaces
2To C
8Alkenyl, the aryl that replaces, the aralkyl that replaces or any heterocyclic radical that replaces arbitrarily arbitrarily; Or R
2Be CO-NR
5 'R
6 'Base is R wherein
5 'And R
6 'Identical or different (a) hydrogen of expression separately, or (b) C
1-20Alkyl, C
2-8Alkenyl, both can be by C
3-7Cycloalkyl, halogen, hydroxyl, C
1-6Carbalkoxy, formamyl, aryl, heterocyclic radical, hydroxyl, C
1-6Chain triacontanol base oxygen, single or two (C
1-6) alkyl ammonia at random replaces; Or (C) by C
1-6The C that alkyl replaces arbitrarily
3-7Cycloalkyl; Or the aryl that (d) replaces arbitrarily; Or the heterocyclic radical that (e) replaces arbitrarily; Or (f) R
5 'And R
6 'Represent the C of replacement arbitrarily with the nitrogen-atoms that they link to each other
5-7Heterocycle; Or R
2For-CO-O-R
7R wherein
7Be C
3-20Alkyl, C
3-8Cycloalkyl, C
4-20Alkenyl, aralkyl, cycloalkylalkyl, heterocyclic radical or heterocyclic radical alkyl wherein group by carbonyl substituted; Or R
7For-CH
2-COR
13Base is R wherein
13Be acyl group, aralkyl, amino, the steric isomer of urea groups or carbamate residue and formula I compound and the salt of formula I compound wherein X are O and R
3Be hydrogen.
The term of Cai Yonging " aryl " comprises phenyl and the naphthyls that replaced by five substituting groups at the most herein, and substituting group can be to be selected from halogen, C respectively
1-6Alkyl, C
1-6Alkoxyl group, C
1-6Alkylthio, halo (C
1-6) alkyl, hydroxyl (C
1-6) alkyl, halo (C
1-6) alkoxyl group, C
2-8Alkenyl, C
2-8Alkenyloxy, C
2-8Alkenyl thio, C
2-8Alkynyl group, C
2-8Chain oxy-acetylene, C
2-8Sulfur-based chain acetylene, hydroxyl, cyano group, nitro, amino, single and two C
1-6Alkylamino, C
1-6Alkyl sulphinyl, C
1-6Alkyl sulphonyl, carboxyl, C
1-6Carbalkoxy and C
1-6Carbalkoxy (C
1-6) alkyl.
The term of Cai Yonging " aralkyl " comprises the phenyl that aryl moiety is wherein replaced arbitrarily by the substituting group of the aryl of above-mentioned definition herein, and wherein alkylidene group has the group of 1 to 4 carbon atom.
The term of Cai Yonging " heterocyclic radical " comprises and contains four heteroatomic aliphatic series or aromatics list or fused rings in the ring at the most herein, heteroatoms is selected from oxygen, nitrogen and sulphur, this ring is replaced by aryl arbitrarily, replaces by other heterocycle or by any substituent those substituting groups of one or more above-mentioned aryl.
R wherein
2Be CO-XR
6Base, X is O preferably.
The one-tenth ester group that is fit to, R
3, comprise the C of any replacement
1To C
20Alkyl, the C that replaces arbitrarily
2To C
20, C for example
2To C
8Alkenyl, the C that replaces arbitrarily
2To C
20, C for example
2To C
8Alkenyl, the C that replaces arbitrarily
3To C
7Cycloalkyl, the aryl that replaces or the heterocyclic radical of replacement arbitrarily arbitrarily.
Can be at the alkyl that replaces arbitrarily, engage in alkenyl or the alkynyl group with any substituting group, such as by R
3Those substituting groups of expression comprise C
3-7Cycloalkyl, C
1-10Alkoxyl group, C
1-10Alkylthio, C
2-8Alkenyloxy, C
2-8Chain oxy-acetylene, C
2-8Sulfur-based chain acetylene, halogen, halo C
1-10Alkoxyl group, halo C
2-8Alkenyloxy, halo C
2-8Chain oxy-acetylene, carboxyl, C
1-6The alcoxyl carboxyl, formamyl, aryl, heterocyclic radical, hydroxyl, cyano group, nitro, C
1-6Chain triacontanol base oxygen, amino, single and two (C
1-6) alkylamino.
Can be at C
3-7Any substituting group that occurs in the cycloalkyl is such as by R
3Those of expression comprise C
1-6Halogenated alkyl C
1-6Alkyl and above-listed and alkyl, those substituting groups that alkenyl is relevant with alkynyl group.
Work as R
3During for alkyl, replaced arbitrarily by aryl, it can be construed to the aralkyl as above-mentioned qualification.
The one-tenth ester group R that is fit to
3Also can comprise by hydroxyl halogen, the C that cyano group replaces arbitrarily
1To C
10Alkyl.The one-tenth ester group R that is fit to
3Also comprise C
2To C
10, C for example
2To C
4Alkenyl, vinyl for example, third-2-alkene-1-base, and but-1-ene-4-base, it can not be substituted or by hydroxyl (except under the situation of vinyl), is replaced arbitrarily by halogen or cyano group.
Further preferred R
3Base is C
1-10Alkyl, and preferred C
1-4Alkyl, quilt-A-R
‖Replacing wherein, A is O or S(O) the x base wherein X be 0,1 or 2 and R
‖Be the C that replaces arbitrarily
1To C
10, and the preferred C that replaces arbitrarily
1-6, C for example
1To C
4Alkyl, the C that replaces arbitrarily
2To C
8, and the preferred C that replaces arbitrarily
2-6, C for example
2To C
4Alkenyl, the C that replaces arbitrarily
2To C
8, and the preferred C that replaces arbitrarily
2-6, C for example
2To C
4Alkenyl or the phenyl that replaces arbitrarily, the C that replaces arbitrarily
1-6Alkyl-carbonyl or the C that replaces arbitrarily
3-7Cycloalkyl, for example C that replaces arbitrarily
3-6Cycloalkyl, or the C that replaces arbitrarily
3-7Heterocyclic radical, the aliphatic heterocyclic radical that replaces arbitrarily for example, what for example replace arbitrarily contains oxygen aliphatic series heterocyclic radical.R with this replacement
3The example of base is-(CH
2)
n,-A-CH=CH-R
12Wherein n ' is 1 to 4 integer and R
12Be hydrogen or C
1To C
4Alkyl, A is oxygen preferably.
Substituting group can be that those are above-mentioned respectively to alkyl arbitrarily, alkenyl, the substituting group of alkynyl group and aryl.
Unless specifically indicate in addition, alkyl, alkenyl and ingot alkynyl group comprise that those appear at R
3In example, can be the group of straight or branched.
The salt of formula I (I A) and (I B) compound, wherein R
2Be CO-XR
3Base wherein X is O or R
3Be hydrogen, comprise for example metal-salt, for example, aluminium, an alkali metal salt is as sodium or potassium, alkaline earth salt, as calcium or magnesium and ammonium or substituted ammonium salt for example those lower alkyl-ammoniums such as triethylamine, hydroxyl-low-alkylamine such as 2-ethylol amine, two (2-hydroxyethyl) amine, or three (2-hydroxyethyl) amine, Cycloalkyl amine such as dicyclohexylamine, or use PROCAINE HCL, PHARMA GRADE, benzhydryl amine, N, N-diphenyl-methyl-ethylene diamine, N-ethylpiperidine, N-phenmethyl-β-phenylethylamine, dehydroabietylamine, N, N '-two-dehydroabietic acid base ethylene diamine, or the alkali of pyridine type (as pyridine, collidine, or quinoline) or trimethylsulfonium.
Work as R
2Be the heterocyclic radical-R that replaces arbitrarily
4The time, preferred heterocyclic radical R
4The group that comprises formula II, wherein R
14And R
15, can be identical or different, be independently selected from hydrogen, arbitrarily the phenyl that replaces, the C that replaces arbitrarily
1To C
20Alkyl, the C that replaces arbitrarily
2To C
8Alkenyl, the C that replaces arbitrarily
2To C
8Alkynyl group, heterocyclic radical or the C that replaces arbitrarily
3To C
7Cycloalkyl or be selected from the substituting group commonly used of above-mentioned those heterocyclic radicals that list, X is a divalent radical ,-Y '-C=C-and Y ' they are oxygen or sulphur.
Preferred R
4Be the heterocycle of any formula III that replaces, wherein Y is O or S and R
14And R
15Has aforementioned given connotation.Particularly preferred R
4Base is to replace De oxazole-2-base, for example formula IV base, wherein R arbitrarily
14Has aforementioned given connotation.
Selectable R
4Can be formula IV base, wherein R
14Itself be the heterocyclic radical that replaces arbitrarily, formula (IV a), (IV b) or (IV c) base, its Chinese style R for example
16, R
17, and R
18Can be identical or different, be selected from hydrogen separately, the halogen, (C that replaces arbitrarily
1-6) alkyl, aryl, aralkyl, heterocyclic radical, (C
1-6) alkoxyl group, hydroxyl, carboxyl and salt thereof, (C
1-6) carbalkoxy, formamyl, single-and two-(C
1-6) alkyl-carbamoyl, sulfamyl, single-and two-(C
1-6) alkylsulfamoyl group, cyano group, nitro, urea groups, (C
1-6) alkoxycarbonyl amido, (C
1-6) alkoxyimino, 2,2,2-trichloro-ethoxycarbonyl amino, acyl group, (C
1-6) alkylthio, arylthio, (C
1-6) alkyl sulphinyl, aryl sulfonyl kia, (C
1-6) alkyl sulphonyl and aryl sulfonyl.
Compatibly, R
14Be formula (IV c) base and R
16, R
17And R
18Hydrogen preferably.
Further suitable one-tenth ester group R
3Be such R
7Base, wherein R
7The C that representative replaces arbitrarily
3-20Alkyl, for example C
3-10Alkyl, C
3-8Cycloalkyl, C
4-20Alkenyl, aralkyl, cycloalkylalkyl, heterocyclic radical or heterocyclic radical alkyl wherein group can be replaced by ketone group (oxygen) in addition.
Work as R
2Be-CO-OR
7The time, such R
2A subclass of base is formula (V) base, and wherein Z is the C that replaces arbitrarily
1To C
12Alkylidene group ((CH
2)
n" wherein n " is from 1 to 12) and R
8Represent C
1-10Alkyl, C
3-8Cycloalkyl, C
2-10Alkenyl, C
2-10Alkynyl group, aryl, aralkyl, cycloalkylalkyl or heterocyclic radical wherein can at random be replaced separately.Substituting group can be those above-mentioned concrete alkyl, cycloalkyl, alkenyl, aryl and heterocyclic radical groups respectively arbitrarily.
R
2The further subclass of base is CO-OR
7Base, and R
7Be-CH
2-CO-R
13, R wherein
13It is the carbamate groups that is fit to.Term " carbamate groups " means general formula-N(R
19)-CO-NR
20R
21Group, wherein R
19Be hydrogen or any C that replaces
1-6Alkyl, and R
20And R
21Independently be selected from hydrogen or the following R that provides
5And R
6Group.
The R of acceptable formation acid amides on the agrochemistry that is fit to
5And R
6Base (R wherein
5And R
6Can be identical or different) example have;
(a) hydrogen or
(b) C that replaces arbitrarily
1-20Alkyl replaces C arbitrarily
2-20, C for example
2-8Alkenyl or the C that replaces arbitrarily
2-20, C for example
2-8Alkynyl group or
(c) C that replaces arbitrarily
3To C
7Cycloalkyl or
(d) aryl that replaces arbitrarily or
(e) heterocyclic radical that replaces arbitrarily; Or
(f) R
5And R
6The nitrogen-atoms that links to each other with their is represented the C of any replacement
5-7Heterocycle or
(g) R
5Be hydrogen and R
6Be-NR
22R
23R
24R wherein
22Be hydrogen or C
1-6Alkyl, R
23And R
24Identical or different, can have above-mentioned R independently
5And R
6At (a), (b), (c), (d), (e) and the implication that (f) provides or
(h) R
6Be-NR
22-N=CR
23R
24Base is R wherein
22, R
23And R
24Have aforementioned given implication or
(i) R
5Be hydrogen and R
6Be-CR
25R
26-CO-W or-NR
27-CO-W base wherein W is phenyl that replaces arbitrarily or the heterocyclic radical that replaces arbitrarily,
R
25, R
26And R
27Be hydrogen or any C that replaces independently
1-6Alkyl.
Acceptable formation amide group R on the preferred agrochemistry
5And R
6Be those wherein R
5Be hydrogen or C
1-4Alkyl and R
6Be C
1-4The group of alkyl, wherein alkyl separately can be independently by C
3-7Cycloalkyl, C
1-14Alkoxyl group, halogen, carboxyl, C
1-6Carbalkoxy, formamyl, any aryl that replaces, any heterocyclic radical that replaces, hydroxyl, C
1-6Alkanol oxygen, amino, single-or two-(C
1-6) alkylamino replaces arbitrarily or R wherein
5And R
6The C of any replacement that the nitrogen-atoms that links to each other with their is represented
5-6The aliphatic series heterocycle.R wherein
5And R
6The nitrogen-atoms that links to each other with their forms the C of any replacement
5-6The example of the group that heterocyclic is fit to can should be mentioned that morpholinyl at this, piperidyl, and piperazinyl, or pyrrolidyl, wherein each group can be by halogen or C
1-4Alkyl at random replaces.
Work as R
5Be hydrogen and R
6Be-CR
25R
26-CO-W or-NR
27-CO-W, R
25, R
26And R
27Preferably the phenyl that preferably replaces arbitrarily of hydrogen and W or replacement contains 1 to 3 and is selected from oxygen, heteroatomic 5 or 6-unit heterocycle, for example thienyl or the furyl of nitrogen and sulphur.
When W was phenyl or heterocyclic radical, its substituting group that is fit to comprised those aforementioned groups of mentioning, and halogen particularly, C
1To C
6Alkyl, formamyl, single-and two-(C
1To C
6) alkyl-carbamoyl, sulfamyl, single-and two-(C
1To C
6) sulfamyl, cyano group, for example between-or right-cyano group, nitro, amino, single-and two-C
1To C
6Alkylamino, C
1To C
6Amido, urea groups, C
1To C
6Alkoxycarbonyl amido, 2,2,2-trichloro-ethoxycarbonyl amino, C
1To C
6Chain triacontanol base, C
1To C
6Alkylthio, C
1To C
6Alkyl sulfinyl, and C
1To C
6The alkane alkylsulfonyl.
Some formula I, (I A) or (I B) compound is new.
Further aspect provides above-mentioned formula I or (I A) or (I B) compound, wherein R according to the present invention
2Be CO-XR
3Base, X are O or S and R
3By-A-R
‖Any C that replaces
1To C
6Alkyl, wherein A is O or S(O) the x base, wherein X is 0,1 or 2 and R
‖Be the C that replaces arbitrarily
1To C
10Alkyl, the C that replaces arbitrarily
2To C
8Alkenyl, the C that replaces arbitrarily
2To C
8Alkynyl group, the phenyl that replaces, the C that replaces arbitrarily arbitrarily
1-6Alkyl-carbonyl replaces C arbitrarily
3-7Cycloalkyl heterocyclic radical, condition are to work as R
‖When being ethyl, R
3Be not-(CH
2)
2-Ji.
Substituting group can be that those aforementioned indicated references are suitable for alkyl, alkenyl, alkynyl group, phenyl, the group of cycloalkyl or heterocyclic radical arbitrarily.
Preferably, R
3By-A-R
‖The C that base replaces
1-4Alkyl, wherein A is O or S(O) the x base, wherein X is 0,1 or 2 and R
‖Be the C that replaces arbitrarily
1To C
6Alkyl replaces C arbitrarily
2To C
6Alkenyl replaces C arbitrarily
2To C
6Alkynyl group, any substituted-phenyl, or replace C arbitrarily
1-6Alkyl-carbonyl replaces C arbitrarily
3-6Cycloalkyl or replace aliphatic C arbitrarily
3-7Oxygen-containing heterocycle, condition are to work as R
‖When being ethyl, R
3Be not-(CH
2)
2-Ji.
In embodiments of the invention, R
3For-(CH2) n '-A-CH=CH-R
12Wherein n ' is 1 to 4 integer, and A is O or S(O) x, wherein x is 0,1 or 2 and R
12Be hydrogen or C
1To C
4Alkyl.
R wherein
2Be the COOH base and the formula I compound of Y representative (I C) or (I D) or (I E) wherein, be disclosed in Deutsches Reichs-Patent application 2726619, in No. 79300371.6,2726618 and No. 2848687 and the european patent application, the above-claimed cpd that has the two keys of three-replacement at the E-configuration is respectively referred to as monic acids C, monic acids A and monic acids B, the preferred compound of the present invention is the derivative of monic acids A,, The compounds of this invention three-replace can exist aspect two keys the E(natural) and Z(or different) geometric configuration.Therefore preferably the stereochemistry of formula I compound is defined as above-mentioned (VI) part, the popular name of this part is " positive Zymomonas mobilis base " (" normonyl ") 3-[(2S, 3R, 4R, 5S)-5-{ (2S, 3S, 4S, 5S)-2,3-epoxy-5-hydroxy-4-methyl hexyl }-3,4-dihydroxy tetrahydropyrans-2-yl]-the 2-methyl-(E)-alkenyl group), work as R
2Be-when COOH was basic, above-mentioned formula I compound was monic acids A.Therefore the formula I compound ester called after monic acids A ester easily of called after (the positive Zymomonas mobilis base of 1-) derivative and monic acids A easily.Be to be appreciated that in the formula I compound R
2Base can contain one or more chiral centre.The present invention comprises above-mentioned all possible isomery resultant.
The specific examples that is used for the compound of the present composition is shown in following table 1, and wherein compound is stereochemistry such as above-mentioned " positive Zymomonas mobilis base " group of logical formula I compound and VI part.Table 2 has listed the examples for compounds that is used for the present composition, and wherein compound is formula (I B) compound, is the pseudomonas acid derivative.Table 3 has listed the examples for compounds that is used for the present invention, wherein compound be logical formula I and Y be that the compound of formula (I C) is the derivative of monic acids C.
Those that should recognize easily that respective column is shown in Table 1 have the compound of R2 value, wherein formula I and Y are that compound (derivative of monic acids C) and its Chinese style (I B) (pseudomonas acid derivative) of formula (I C) can prepare, and can think that above-claimed cpd is in this article by specifically open.Formula (I A) or the corresponding derivative of formula I compound, wherein Y is that formula (I D) and (I E) can prepare easily, and can similarly think in this article by specifically open.
Table 1
Compound R
2
Sequence number
1 -COOH
2 -CO-O-CH
2-CH=CH
2
3 -CO-O-CH
2-CH
2-OH
4 -CO-S-CH
3
5 -CO-O-CH
2CH
2-O-CH=CH
2
6 -CO-O-(CH
2)
3-CO-CH
3
7-CO-O-(CH
2)
3-CO-phenyl
8 -CO-O-CH
2-CO-NH-CO-NH
2
9 -CO-O-CH
2CN
10-CO-O-CH
2-(3-cyano-phenyl)
11-CO-O-CH
2-(3-bromophenyl)
12-CO-O-CH
2-(3-aminomethyl phenyl)
13-CO-O-CH
2-(4-hydroxymethyl phenyl)
14-CO-NH-CH
2-CO-(4-cyano-phenyl)
15 structure VII
16 structure VIII
17 -CO-O-(CH
2)
8-Br
18 structure IX
19 structure X
20 -CO-O-(CH
2)
15CH
3
21 -CO-O-CH
3
22 structure XI
23 -CO-O-(CH
2)
2-O-CH
2-CH=CH
2
24 -CO-O-(CH
2)
2-O-CH=CH-CH
3
25 -CO-O-(CH
2)
3-CH=CH
2
26 -CO-O-(CH
2)
2-O-CH
2-CH
3
27-CO-O-(CH
2)
2-O-phenyl
28-CO-O-(CH
2)
2-O-(4-chloro-phenyl-)
29 -CO-O-(CH
2)
2-O-CO-CH
3
30 -CO-O-(CH
2)
2-O-CH
2-CO-OC
2H
5
31 -CO-O-(CH
2)
3-C≡CH
32 -CO-O-(CH
2)
4-O-CH=CH
2
33 -CO-O-(CH
2)
3-O-CH=CH
2
34 -CO-O-(CH
2)
2-O-CH=CH-(CH
2)
3-CH
3
35 -CO-O-C
2H
5
36 -CO-O-CH-(CH
3)
2
37 -CO-O-(CH
2)
3-CH
3
38 -CO-O-CH
2-C(CH
3)
3
39-CO-O-(cyclohexyl)
40-CO-O-(cyclopropyl)
42 -CO-O-(CH
2)
2-O-(CH
2)
2-O-CH
3
43 -CO-O-(CH
2)
2-O-CH
2-C≡CH
44 -CO-O-(CH
2)
2-O-CH
2-CH=CHCl
45 -CO-O-CH(CH
3)-CO-O-C
2H
5
46 -CO-O-CH
2-CO-NH
2
47 -CO-O-CH
2-CH=CHCl
48 -CO-O-CH(CH
3)-CH=CH
2
49 -CO-O-CH
2-CH=CHCH
3
50-CO-O-phenyl
51-CO-O-(4-chloro-phenyl-)
52-CO-O-(3-nitrophenyl)
53-CO-O-(4-methoxyphenyl)
54-CO-O-(4-(methoxycarbonyl)-phenyl
55-CO-O-CH
2-(4-methoxyphenyl)
56-CO-O-CH
2-(furans-2-yl)
57 -CO-O-CH
2-CH
2Cl
58-CO-NH-(2,4 dichloro benzene base)
59-CO-NH-(2, the 5-dichlorophenyl)
60-CO-N (CH
3)-(2,4 dichloro benzene base)
61 -CO-NH
2
62 -CO-NH-C
2H
5
63 -CO-N(C
2H
5)
2
64-CO-morpholine-N-base
65 -CO-NH-NH
2
66 -CO-NH-CH
2-CO-OC
2H
5
67 -CO-O-(CH
2)
2-S-CH=CH
2
68 -CO-S-(CH
2)
2-O-CH=CH
2
69 -CO-O-CH
2-O-CH=CH
2
70-CO-O-CH
2-(3-nitrophenyl)
71 -CO-O-CH
2-C≡CH
72 -CO-O-CH
2-CO-O-C
2H
5
73 -CO-O-(CH
2)
9CH
3
74-CO-S-phenyl
75 -CO-S-CH
2-CO-OCH
3
76 -CO-O-CH
2-O-C
2H
5
77 -CO-NH-(CH
2)
2-OH
78 -CO-NH-(CH
2)
2-O-C
2H
5
79 -CO-N(-CH
2-CH=CH
2)
2
80 structure XII
81 structure X III
82 -CO-NH-N(CH
3)
2
83 -CO-NH-N=C(CH
3)
2
84 structure X IV
85 structure X V
86 -CO-NH-CH
2-CH=CH
2
87 -CO-N(CH
2-CH
2-OH)
2
88 -CO-O
-(CH
3)
3S
+
93-CO-O-CH
2-cyclopropyl
94 -CO-O-(CH
2)
2-O-CH
2-CH=CH-CH
2-CH
2-CH
3
95 -CO-O-(CH
2)
2-O-C(C
3H
7)-CH=CH
2
96 -CO-O
- +NH3-CH(CH
3)-CH
3
97 -CO-O
- +NH-(C
2H
5)
3
99 -CO-O
- +Na
100 -CO-O-CH
2-CH
2-O-CH(CH
3)-CH
3
101 -CO-O-CH
2-CH
2-O-CH
3
102 -CO-O-CH
2-CH
2-O-CH
2-CH
2-CH
3
103 -CO-O-CH(CH
3)-CH
2-O-CH
2-CH
3
104-CO-O-CH
2-CH
2-O-(cyclopropyl)
105 -CO-O-CH
2-CH(CH
3)-O-CH
2-CH
3
106 -CO-NH-OCH
3
Table 2
The pseudomonas acid derivative
R
2
The compound sequence number
89 -CO-O-CH
2-CH
2-O-CH=CH
2
90 -CO-O-C
2H
5
91 -CO-O-(CH
2)
2-OH
92 -CO-N(C
2H
5)
2
98 -CO-O
- +NH-(C
2H
5)
3
Table 3
R
2
The compound sequence number
107 -CO-OH
108 -CO-O-CH
2-CH
2-O-C
2H
5
Be used for compound of the present invention or known compound, or be used to prepare the compound of the similar methods preparation of corresponding known compound by those.
This compound can be thought the derivative of monic acids, and monic acids can prepare by hydrolysis pseudomonic acid optionally.Further the initiator that adopts is a ketone, it by as GB1587060 described in, at-50 to-80 ℃ of following ozone decomposition pseudomonic acids and obtain, the derivative of pseudomonic acid certainly is that initiator directly prepares with the pseudomonic acid.
Usually at initial as monic acids or its derivative or accordingly in the reactive ketone, hydroxyl needs protection.Multiple suitable protecting group be known and case description in the embodiment of EP0399645.Particularly suitable protecting group is a silyl; because these substituting groups are removed under mild conditions easily; these groups are introduced into by the sillylation reagent that comprises halogenated silanes and silazane of routine; by method well known in the prior art; comprise enzymatic method; hydroxyl protecting group can be removed subsequently; for example; the silyl protecting group can be passed through the weak acid hydrolysis usually; the method of basic hydrolysis is subsequently removed, JPClayton for example, and Kluk and N H Rogers are at pseudomonic acid chemistry II part J.C.S.Perkin Trans I; described in 1979,308.
No. 1 compound in the table 1 is known compound and can prepares as above-mentioned embodiment.More detailed preparation method provides among 587,058 the embodiment 2,3,4 and 6 at GB1, and the salt of formula I compound wherein x is O and R
3Be that hydrogen (i.e. the salt of No. 1 compound in the table 1) also can pass through as GB 1,587, the ordinary method described in 058 embodiment prepares from monic acids.Typical method comprises monic acids and alkali, oxyhydroxide for example, and required positively charged ion carbonate or supercarbonate reaction then remove and anhydrate, and carry out ion-exchange with suitable resin, and react with amine.
No. 2 compounds and No. 21 compounds are compound known in the table 1, and can be by GB1 for example, and embodiment 24 and 3 described methods prepare respectively in 587,059.Preparation formula I compound is R wherein
2Be-COXR
3Base and X are O, and R
3The usual method that is the group of acceptable formation ester on the agrochemistry also is disclosed in GB1, in 587,059.
No. 3 compounds are known compounds in the table 1, and can adopt for example GB1, the usual method described in 587,059, or more specifically be described in J Antibiot 198841(5) in the method preparation.
No. 4 compounds are known compounds in the table 1, and for example can adopt disclosed method among the EP0 002 371, and wherein more specifically disclosed method preparation among the embodiment 5.R wherein
2In the compound of formula I be-CO-XR
3And X is that the compound of S can adopt that disclosed usual method similarly prepares among the EP 0 002 371.
No. 6 and No. 7 compounds are known compounds in the table 1, and can be for example described in EP 0 025 288 and wherein embodiment 2 and 5 described methods preparations more specifically.In the formula I compound, R wherein
2Be formula-CO-O-R
7Base and R
7Be C
3-20Alkyl, C
3-8Cycloalkyl, C
4-20Alkenyl, aralkyl, cycloalkylalkyl, the compound that heterocyclic radical or Heterocyclylalkyl group wherein can at random be replaced by formoxy can adopt the usual method preparation that is described among the EP 0 025 288.
No. 8 compounds are known compounds in the table 1, and for example can adopt disclosed method preparation in Japanese Patent 54-151132 number.
No. 10 compounds are known compounds in the table 1, and for example can adopt disclosed method preparation among the EP 0 052 437, and more specifically adopt the wherein method described in the embodiment 2.R wherein
2Be-CO-OR
3The formula I compound of base also can be by the preparation described in Japanese Patent 54-12376 or EP 0 052437.
No. 14 compounds are known compounds in the table 1.And for example can adopt disclosed method preparation among the EP 0 087 953, and more specifically adopt the wherein method described in the embodiment 21.Ding Yi wherein R as described above
2Be-CO-NH
2The formula I compound of-CO-W base can adopt the usual method among the EP0 087 953 to begin preparation, and it is to make wherein R in this patent
2Be heterocyclic radical-R with above-mentioned formula III
4The intermediate of compound, it can be similarly by preparing in the method described in the EP 0 087 953.Therefore for example, the similarity method preparation of (the positive Zymomonas mobilis of 5-methyl-2-(1-(1--2-yl) oxazole that No. 19 compounds can adopt to be described in EP 0 087 953 embodiment 14, or more specifically as J Chem Soc., Perkin Trans.I1989(11) the similarity method preparation described in the 2059-63.The preparation identical, that No. 22 compounds can be described in EP 0 087 953 embodiment 10 in the table 1.
Ether, the solvent of methylene dichloride or chloroform, the temperature of reaction that is fit to is in-10 ℃ to 70 ℃ scopes.
Other method that is fit to that preparation is used for the compound of the present composition is described in the document, specifically referring to aforementioned patent that lists and paper.
The compound that is used for the present composition has the activity that antagonism comprises the wide spectrum scope of unifacial leaf and broadleaf weed kind.Chemical compound lot demonstrates the good selectivity to crop, particularly to wheat, barley, corn, rape, and sugar beet and paddy rice.The compound that is used for the present composition preferably is directly applied for noxious plant (postemergence application), but they also can be applied to soil (preemergence application) before noxious plant is sprouted.
Therefore another aspect provides the method for seriously damaging or killing noxious plant according to the present invention, comprising the formula I of the definition as described above of the growing environment of plant or plant being used herbicidally effective amount or (I A) or (I B) compound R wherein
2Definition as described above.
The new compound of the present invention preferably uses with the carrier blended composition forms that contains the formula I compound.Carrier comprises the thinner of solid or liquid.
The composition that the present invention is fit to comprises diluted composition, and it can directly use, and also comprises concentrate composition, and it needs dilution before use, usually dilute with water.Preferred compositions contains the activeconstituents of 0.01% to 90% weight.The diluted composition that prepare to use preferably contains 0.01 to 2% activeconstituents, and concentrate composition can contain 20 to 90% activeconstituents, and usually preferably 20 to 70%.
Solids composition can be prepared into granule or pulvis, wherein activeconstituents and fine dispersed solids mixing diluents, thinner for example, kaolin, wilkinite, rhombspar, lime carbonate, talcum, magnesium oxide powder, Fuller's earth and gypsum, but they also can be prepared into dispersion powder or granula, wherein contain wetting agent and are distributed in the liquid to promote this pulvis and granula.The solid mixture of powder form can be used for the blade face and dusts and use.
Liquid composition can comprise solution or the dispersion liquid of activeconstituents in water, at random can contain tensio-active agent, maybe can comprise solution or the dispersion liquid of activeconstituents in water one organic solvent immiscible, and it is dispersed into drop in water.
Tensio-active agent can be a positively charged ion, negatively charged ion or non-ionic type or their mixture.Cats product is, for example, and quaternary ammonium compound (for example, cetrimonium bromide).The anion surfactant that is fit to is the soap class; Sulfonic acid fat monoester salt, for example sodium lauryl sulphate; Sulfonate with aromatics, Sodium dodecylbenzene sulfonate for example, xylogen sodium, calcium, and ammonium salt, the compound of butyl naphthalene sulfonate and di-isopropyl and triisopropyl naphthalene sulfonate salt, what be fit to nonionogenic tenside is oxyethane and Fatty Alcohol(C12-C14 and C12-C18) such as oleyl alcohol, or with alkylphenol such as octyl group-or the condensation product of nonyl phenol (for example Agral90) or octyl group-cresols.Other nonionogenic tenside is from longer chain fatty acid and hexitan deutero-half ester, sorbitan monolaurate for example, the condensation product of half ester and oxyethane; Yelkin TTS; And silicone surfactant (water soluble surfactant active of containing siloxane backbone, for example Silwet L77).The mineral oil mixture that is fit to is Atplus 411F.
The preparation of the aqueous solution or dispersion liquid can be by being dissolved in activeconstituents in water or containing arbitrarily in the organic solvent of moistening or dispersion agent.Then, when adopting organic solvent, it is joined mixture obtaining to contain arbitrarily the aqueous solution of wetting agent, suitable organic solvent comprises, for example ethylene dichloride, Virahol, propylene glycol, Pyranton, methylbenzene, kerosene, methylnaphthalene, dimethylbenzene and trieline.
As the composition of aqueous solution composition or dispersion, usually containing formulations of active ingredients supply at high proportion, and dilute with water enriched material before use.Enriched material need stand normal phase storage usually and behind storage, can form the liquid prepared product behind the dilute with water, and this prepared product should keep evenly making them to use by the spraying equipment of routine in the sufficiently long time.Conventional enriched material contains 20-90%, preferred 20-70%, activeconstituents by weight.Purpose as requested, the dilution prepared product of preparing to use can contain the activeconstituents of variable quantity; The amount of normally used activeconstituents by weight is 0.01% to 10.0%.And be preferably 0.1% to 2%.
Preferred concentrate composition preparation contains the activeconstituents through fine dispersion, and is scattered in tensio-active agent and the suspension agent water under existing.The suspension agent that is fit to is hydrophilic colloid and comprises, for example, and polyvinylpyrrolidone and Xylo-Mucine, and vegetable jelly, for example kordofan gum and tragacanth gum, the embodiment of preferred suspension agent comprises the gelationus mineral silicon ester of hydration, if you would take off stone, beidellite, nontronite, hectorite, talcum powder, and saucorite, wilkinite is particularly preferred, other suspension agent comprises derivatived cellulose and polyvinyl alcohol.
The amount of application of The compounds of this invention will be according to some factors, comprise, for example, select the compound of use, growth is with the individual character of repressed plant, and whether formulation and the compound selecting to use are administered to blade face or root absorption,, usually the suitable amount of application that instructs is 0.0001 to 20 kilogram of a per hectare, and for example per hectare is preferred for 0.001 to 2 kilogram.
Except that one or more The compounds of this invention, the present composition can contain the non-The compounds of this invention of one or more biologically actives.According to further embodiment the invention provides contain at least a as preceding as the definition formula I (I A) or the herbicidal composition of (I B) herbicidal compound and at least a other Herbicidal mixtures.
Other weedicide can be any be not the weedicide of formula I (I A) or (I B).In specifically using, this weedicide normally has the weedicide of complementary action.
Example as complementary weedicide comprises:
A, benzo-2,1,3-thiadiazine-4-ketone-2,2-dioxide such as bentazon;
B, hormone herbicide, special phenoxy alkane acid be as 2 first, 4 chlorine, phenothiol 2, and 4-drips propionic acid, and 2,4,5-tears, Thistrol; 2,4-drips, and 2,4-Embutox, Vi par, triclopyr, clopyralid and their derivative (for example, salt, ester and acid amides).
C, 1,3 dimethyl pyrazole oxazole derivatives such as pyrazoxyfen, pyrazolate, benzofenap;
D, dinitrophenol(DNP) and their derivative (for example acetic ester) be as dinoseb acetate phenol, dinoseb and its ester dinoseb acetate;
E, dinitraniline weedicide such as dinitramine, trifluralin fourth fluchloralin, pendimethalin, oryzalin;
F, phenylurea weedicide such as Diuron Tech
*, fluometuron, metoxuron, neburon, isoproturon
*, chlorotoluron
*, chlorxuron, methoxydiuron, monolinuron, chlorbromuron, daimuron, methabenzthiazuron;
G, phenyl amino formyl radical oxygen phenyl manthanoate such as phenmedipham and different phenmedipham;
H, 2-phenyl pyridazin-3-one such as pyrazon and monometflurazone;
I, uridylic weedicide such as lenacil
*, bromacil and terbacil;
J, triazine herbicide such as atrazine
*, simazine, aziprotryn, bladex, prometryn, penta grass is clean, simetryn, and terbutryn;
K, group thiophosphate weedicide such as piperophos, bensulide and Glufosinate ammonium;
L, thiocarbamate herbicide such as cycloate, vernolate, Hydram, thiobencarb, butylate
*, Eptam
*, tri_allate, di_allate, esprocarb, fourth grass prestige reaches grass and ends prosulfocarb
*, and dimepiperate.
M, 1,2,4-triazine-5-herbicides such as benzene piperazine grass and sencorex;
N, benzoic acid herbicides such as tribac, dicamba 98 and Amiben;
O, the agent of N-anilide grass are as the third careless amine, Butachlor technical 92, alachlor, propachlor, Stam F-34, metazachlor, metolachlor, acetochlor
*, and ethachlor;
P, dihalo-benzonitrile weedicide such as Niagara 5006, bromoxynil
*With sulphur benzene nitrile;
Q, halogenated alkane acid herbicide such as dalapon, Tricholroacetic Acid and its salt;
R, diphenyl ether herbicide are as restraining wealthy pleasure, fluoroglycofenethyl or its salt or ester, nitrofen, bifenox, acifluorfen and its salt or ester, Oxyfluorfen, fomesafen, chlornitrofen and chlomethoxyfen;
S, phenoxy group phenoxy propionic acid ester weedicide such as chloroformate grass and its ester such as methyl ester, diclofop-methyl and its ester, the spirit of pyrrole fluorine second grass
*With its ester, quizalofop and its ester and fe-noxaprop and its ester such as ethyl ester.
T, cyclohexanedione herbicide such as witheredly reach and its salt sethoxydim, cycloxydim, methoxyphenone extremely
*, and clethodim;
U, sulfonylurea herbicide such as chlorine sulphur are grand, sulfometuron-methyl, metsulfuronmethyl and its ester; Benbbensulfuronmethyl and its ester such as DPX-M6313, chlorimuronethyl and its ester such as ethyl ester, primisulfuronmethyl and its ester such as ethyl ester, 2-[3-(4-methyl isophthalic acid, 3, the 5-triazine-yl)-and 3-methyl urea groups sulfo group) benzoic ether such as its methyl ester (DPX-LS300) and pyrazosulfuronmethyl;
V, imidazolidinone weedicide such as imazaquin, imazamethabenz, imazapyr and its isopropyl ammonium salt, Imazethapyr;
W, aryl aniline weedicide such as FLAMPROP and its ester, benzoylpropethyl, diflufenican
*;
X, amino acid weedicide such as glyphosate and careless ammonium phosphine
*With their salt and ester, sulphosate (glyphosate trimesium)
*With two alanyl phosphorus;
Y, organoarsenic herbicide such as monsodium acid methanearsonate (MSMA) (MSMA);
Z, amide herbicide such as R-7465, pronamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide and alanap;
AA, triketone such as sulcotrione;
BB, various types of weedicide comprise careless ethofumesate, dislike the humulane in heptan, and benzene opposes soon and its salt such as Methylsulfate, and wide standing grain goes out oxadiazon, Faneron, Herba ainsliaeae yunnanensis, tridiphane, flurochloridone, quinclorac and mefanacet;
CC, comprise as the example of contact weedicide:
The activeconstituents that bipyridylium herbicide such as those wherein exist is the weedicide that paraquat and those activeconstituentss that wherein exist are diquat;
* these compounds tranquilizer best and as dichlormid is used in combination;
* is verified, and these compounds mix the synergism that has adduction and occasion out of the ordinary when using with The compounds of this invention.
Preferred compound of the present invention is, they can with as the mixe herbicide harmonious coexistence of above-mentioned illustrative those broad range, and said mixture may exist adduction or synergism.
By following embodiment illustration the present invention.
Embodiment 1
With the NMR spectrum of listing compound in the table 1, represent their characteristic.In each case, the derivative moiety of monic acids A (that is: " the positive Zymomonas mobilis base " of following structure VI) is by its characteristic of spectral representation of the easy title complex of differentiating, this spectrum is corresponding to No. 1 compound monic acids itself, although can comprise in order to differentiate that relatively the following table II has been listed by different R from the crucial peak of single bacterium acid derivative
2The visible features spectrum that base causes, the solvent of record spectrum usefulness also together provides.
The table II
1H NMRδ
The compound number solvent
2 CDCl
35.9(1H,m);5.2(2H,m);4.6(2H,d)
3 d
6-DMSO 4.0(2H,t);3.5(2H,m)
4 CDCl
32.3(3H,s)
5 CDCl
36.5(1H,t);4.3(2H,m);3.9(2H,m);3.8(2H,m)
6 CDCl
34.0(2H,t);2.2(3H,s)
7 CDCl
38.0-7.5(5H,m);4.2(2H,t);2.2(2H,t)
8 d
6-DMSO 4.6(2H,s)
9 CDCl
34.8(2H,s)
10 CDCl
37.7-7.4(4H,m);5.2(2H,s)
11 CDCl
37.6-7.2(4H,m);5.1(2H,s)
12 CDCl
37.3-7.1(4H,m);5.1(2H,s);2.2(3H,s)
13 CDCl
37.4(4H,s);5.1(2H,s);4.7(2H,d)
14 CDCl
38.1-7.8(4H,m);4.8(2H,d)
15 d
6-DMSO 10.2(1H,s);9.8(1H,s);7.9(1H,s);7.2(1H,d);
6.6(1H,s)
16 CDCl
39.8(1H,s);9.6(1H,s);7.6(2H,d);6.6(2H,d);
2.9(6H,s)
17 CDCl
34.1(2H,t);3.4(2H,t)
18 CDCl
37.8(1H,s);7.5(1H,s);7.1(1H,d);6.6(1H,s)
19 d
6-DMSO 6.8(1H,s);1.2(3H,t)
20 CDCl
34.1(2H,t)
21 CDCl
33.7(3H,s)
22 CDCl
38.0(2H,d);7.8(2H,d);7.6(1H,s)
Embodiment 2
The present embodiment illustration preparation of monic acids A2-vinyl oxygen ethyl ester (compound 5 in the table 1).
With monic acids A sodium (1g, 2mM) be dissolved in the dimethyl formamide (25ml) and with 2-chloroethyl vinyl ether (0.6ml, 6mM), hexamethylphosphoramide (3) and sodium iodide (0.9g), stirred 6 hours down at 80 ℃, residuum distributes in ethyl acetate and salt solution after the solvent removed in vacuo, and (3 * 50ml) further extract water with ethyl acetate.Use 10% hypo solution, the organic fraction that saturated sodium bicarbonate solution and salt water washing merge, dry and vacuum-evaporation with organic fraction.The silicon chromatographic separation (60 types, 20g), with 0 to 4% methyl alcohol/CHCl
3Wash-out obtains product, and product is left standstill crystallization, and to obtain fusing point be 78-80 ℃ solid, and the NMR spectral representation is in embodiment 1.
Embodiment 3
The present embodiment illustration preparation of monic acids A cyanomethyl ester (No. 9 compounds in the table 1).
(2.00g, 5.4mmol), (0.35ml 5.4mmol) and the solution of dimethyl formamide (50ml), stirred vacuum-evaporation then 1 hour at 80 ° to chloromethyl cyanide will to contain monic acids A sodium.The residuum up in ethyl acetate is used the salt water washing with it then with sodium bicarbonate aqueous solution, dry (MgSO
4), vacuum-evaporation, and obtain as the required product of limpid buttery with chromatogram purification (chloroformic solution of 0 to 4% methyl alcohol, 20g silica gel), the NMR spectral representation is in embodiment 1.
Embodiment 4
The present embodiment illustration preparation of monic acids A3-Brombenzyl ester (No. 11 compounds in the table 1).
To contain monic acids A sodium (1.1g 3mmol) ,-(0.75g 3mmol), and the solution of dimethyl formamide (35ml), stirs hour and vacuum-evaporation then at 20 ℃ the Brombenzyl bromide.Residuum absorbs with ethyl acetate/salt solution, and the organic layer sodium bicarbonate aqueous solution is used the salt water washing then, dry (MgSO
4), vacuum-evaporation obtains the required product as colorless oil with chromatogram purification (dichloromethane solution of 0 to 6% methyl alcohol, 20g silica gel), and with the white powder of its curing acquisition fusing point at 91 ℃-92 ℃, the NMR spectral representation is in embodiment 1.
Embodiment 5
The present embodiment illustration preparation of monic acids 3-methylbenzene methyl ester (No. 12 compounds in the table 1).
To contain monic acids A sodium (0.73g, 2mmol), between α-bromo--(0.37g 2mmol) and the solution of dimethyl formamide (25ml), stirs 17 hours and vacuum-evaporation then at 20 ℃ to xylyl.Residuum absorbs with ethyl acetate/salt solution, and organic phase is used the salt water washing then with sodium bicarbonate aqueous solution.Dry (MgSO
4) and vacuum-evaporation.Obtain the required product of colorless oil with the chromatogram remaining oil (dichloromethane solution of 0 to 4% methyl alcohol, 15g silica gel) of purifying.The NMR spectral representation is in embodiment 1.
Embodiment 6
The present embodiment illustration preparation of monic acids A4-methylol benzyl esters (No. 13 compounds in the table 1).
(13.6g's paratolunitrile 100mmol) refluxed 1 1/2 hours in the methyl alcohol (95ml) and the vitriol oil (5ml), and reactant is evaporated half volume, poured in the water, used ethyl acetate extraction, dry (MgSO
4), and vacuum-evaporation, (17.8g, 100mmol), benzoyl peroxide (100mg) and tetracol phenixin (50ml) also refluxed 2 1/2 hours, then with the reactant filtration, and vacuum-evaporation filtrate to adding N-bromine succinimide in the residuum.
This product, (9.2g 40mmol) is cooled to-30 ℃ to methyl-4-bromo methyl acid ester in toluene (80ml), and be added dropwise to the diisobutyl alanate toluene solution (60ml, 25%, 80mmol), and stirred 1 hour, make solution rise to room temperature and restir 2 hours.Then reactant is used the methyl alcohol quenching, filtered, and use the salt solution wash filtrate then with sodium bicarbonate aqueous solution.With organic layer drying (MgSO
4) and vacuum-evaporation acquisition 4-brooethyl phenmethyl ethanol.
Dimethyl formamide (60ml) solution that contains monic acids A sodium (4mmol) and 4-brooethyl phenmethyl ethanol (4mmol) at room temperature stirs and spends the night, and vacuum-evaporation then, residuum absorbs with ethyl acetate/salt solution, with sodium bicarbonate aqueous solution with use the salt water washing then, dry and evaporation.The residuum chromatogram purification with ethanol/methylene mixture wash-out, obtains colorless oil.The expression in embodiment 1 of NMR spectrum.
Embodiment 7
The present embodiment illustration 4-dimethylamino benzoyl Zymomonas mobilis hydrazides A(monh-ydrazide A) preparation.
Monic acids A(3.44g, 10mmol) be dissolved in the tetrahydrofuran (THF) (100ml) and be cooled to 0 ℃, add triethylamine (1.5ml, 11mmol) with isobutyl chloride formic acid (1.4ml, 11mmol) and stirred 30 minutes, (1.79g, 10mmol) stirred reaction mixture is 5 hours to add the dimethylaminophenyl hydrazides.Then reaction mixture is filtered and vapourisation under reduced pressure, residuum uses the ether recrystallization to obtain the required product of white solid, and fusing point 116-118 ℃, NMR composes expression in embodiment 1.
Embodiment 8
The present embodiment illustration preparation of monic acids A1-bromo-8-octyl group ester (No. 17 compounds in the table 1).
(1.0g, 2.7mmol) and 1, (0.75g, dimethyl formamide 2.7mmol) (5ml) solution at room temperature stir and spend the night 8-two bromooctanes, and vapourisation under reduced pressure then will to contain monic acids A sodium.Residuum is dissolved in ethyl acetate/water and organic layer washes with water, dry (MgSO
4) and vapourisation under reduced pressure.The residuum of gained obtains the required product of buttery with column chromatography purifying (silica gel is with the dichloromethane solution wash-out of 3% methyl alcohol).The NMR collection of illustrative plates is represented in embodiment 1.
Embodiment 9
The present embodiment illustration preparation of monic acids A cetyl ester (No. 20 compounds in the table 1).
With monic acids A(25.8g, 75mmol), salt of wormwood (10.5g, 76mmol), (15.0g is 100mmol) with hexadecyl bromide (45ml for sodium iodide, 147mmol) in dimethyl methyl acid amide (750ml) and hexamethylphosphoramide (150), stirred 24 hours, mixture is with ethyl acetate (1.5l) dilution, and water (4 * 0.5l) and the salt water washing, dry and evaporation.Residuum silicon (1200g) purifying, the chloroformic solution wash-out with 5% methyl alcohol obtains shallow white powder, and it is obtained required product with the ethyl acetate/hexane recrystallization.The expression in embodiment 1 of NMR spectrum.
Embodiment 10
The present embodiment illustration preparation of monic acids A penta-4-alkenyl esters (No. 25 compounds in the table 1).
(160mg 0.44mM) is dissolved in the dimethyl formamide (2ml), and (131mg, 0.88mM) and N, N-dimethylpropylene urea (0.38ml) at room temperature stirred 4 hours, and stirred 2 hours at 70 ℃ with 1-bromine penta-4-alkene with monic acids A sodium.Volatile component is removed in vacuum-evaporation.Silicon separated, and obtained the required product of colourless pulpous state with 55: 45 acetone/hexane wash-outs.
1H NMR δ （CDCl
3）：5.82（1H，m），5.77（1H，s），5.08（1H，d），5.00（1H，d），4.11（2H，t），2.21（3H，s），1.22（3H，d）0.95（3H，d）.
Embodiment 11 to 16
Adopt the ordinary method among the embodiment 10 to prepare following compound:
Monic acids A 4-methoxybenzyl ester (No. 55 compounds in the table 1)
1H NMR δ（CDCl
3） 7.30（2H，d），6.88（2H，d），5.79（1H，s），5.07（2H，s），3.90（3H，s），2.21（3H，s），1.22（3H，d），0.92（3H，d）.
Monic acids A3-oil of mirbane methyl ester (No. 70 compounds in the table 1)
1H NMR δ（CDCl
3） 8.28（1H，s），8.20（1H，d），7.70（1H，d），7.54（1H，t），5.80（2H，s），2.22（3H，s），1.21（3H，d），0.93（3H，d）。
Monic acids A propargyl ester (No. 71 compounds in the table 1)
1H NMR δ（CDCl
3） 5.80（1H，s），4.71（2H，s），2.22（3H，s），1.21（3H，d），0.94（3H，d）.
Monic acids A ethyl acetyl-2-base ester (No. 72 compounds in the table 1)
1H NMR δ（CDCl
3） 5.89（1H，s），4.63（2H，abp），4.22（2H，q），2.22（3H，s），1.29（3H，t），1.22（3H，d），0.91（3H，d）.
Monic acids A decyl ester (No. 73 compounds in the table 1)
1H NMR δ（CDCl
3） 5.78（1H，s），4.08（2H，t），2.21（3H，s），1.21（3H，d），0.95（3H，d），0.87（3H，t）.
Monic acids A2-benzene oxygen ethoxylated ester (No. 27 compounds in the table 1)
1H NMR δ（CDCl
3） 7.29（2H，t），6.91（3H，m）5.81（1H，s），4.46（3H，t），4.19（3H，t），2.22，（3H，s）1.21（3H，d），0.92（3H，d）.
Embodiment 17
The present embodiment illustration preparation of monic acids A third-2-base ester (No. 36 compounds in the table 1).
With monic acids A sodium (200mg, 0.55mM) be dissolved in the dimethyl formamide (2ml) and with 2-N-PROPYLE BROMIDE (136mg, 1.11mM), N, N-dimethylpropylene urea (0.476g) and sodium iodide (166mg, 1.11mM) at room temperature stirred 1.5 hours, left standstill then 4 days, organic composition is removed in vacuum-evaporation, and silicon separates, with 55: 45 acetone/hexane wash-outs, obtain the required product of colourless pulpous state.
1H NMR δ（CDCl
3）5.72（1H，s），5.02（1H，m），2.21（3H，s）1.24（6H，d），1.22（3H，d），0.94（3H，d）.
Embodiment 18 to 20
Employing prepares following compound corresponding to the method for embodiment 17:
Monic acids A2-ethoxyethyl ester (No. 26 compounds in the table 1)
1H NMR δ（CDCl
3） 5.81（1H，s），4.26（2H，t），3.66（2H，t），3.54（2H，t），2.21（3H，s），1.22（3H，m），1.21（3H，d），0.94（3H，d）.
Monic acids A penta-4-base alkynyl ester (No. 31 compounds in the table 1)
1H NMR δ（CDCl
3） 5.78（1H，s），4.20（2H，t），2.21（3H，s），1.22（3H，d），0.94（3H，d）.
Monic acids A ethyl propionyl-2-base ester (No. 45 compounds in the table 1), acquisition be the mixture of diastereomer.
1H NMR δ（CDCl
3） 5.86（1H，s），5.09（1H，m），4.21（2H，q），2.21（3H，s），1.50（3H，t），1.25（3H，t），1.22（3H，d），0.92（3H，d）.
Embodiment 21
The present embodiment illustration monic acids A2-(4-chlorobenzene oxygen) preparation of ethyl ester (No. 28 compounds in the table 1).
Monic acids A(200mg, 0.58mM) be dissolved in the dimethyl formamide (1ml) and with 2-(4-chlorobenzene oxygen) (273mg, 1.16mM) and N, (510mg 3.98mM) stirs the N-dimethylpropylene urea ethyl bromide together.(120mg 0.87mM) also at room temperature stirred 1 hour and stirred 1.5 hours at 80 ℃ to add salt of wormwood.Volatile component is removed in vacuum-evaporation, and silicon separates, and with 55: 45 acetone/hexane wash-outs, obtains gelationus required product.
1H NMR δ（CDCl
3） 7.25（2H，d），6.82（2H，d），5.80（1H，s），4.40（2H，m），4.16（2H，m），2.22（3H，s），1.21（3H，d），0.93（3H，d）.
Embodiment 22 to 33
Adopt the method for the routine among the embodiment 20 to prepare following compound:
Monic acids A2-((2-methoxyl group) ethyl ester (No. 42 compounds in the table 1) oxyethyl group)
1H NMR δ（CDCl
3） 5.81（1H，s），4.27（2H，t），3.72（2H，t），3.65（2H，m），3.55（2H，m），3.40（3H，s），2.21（3H，s），1.21（3H，d），0.95（3H，d）.
The mixture (1: 4) of monic acids A1-methyl-third 2-alkenyl esters (No. 49 compounds in the table I-itself be the mixture of diastereomer) and monic acids A but-2-ene base ester (in the table 1 No. 48 compound-itself be the mixture of geometrical isomer).
Monic acids A1-methyl-prop-2-alkenyl esters
1H NMR δ (CDCl
3) 5.78(1H, m), 5.39(1H, m), 5.25(1H, m), 5.15(1H, m), 2.21(3H, s), 1.70(3H, s), 1.21(3H, d), 0.99 and 0.80(3H, 2xd).
Monic acids A but-2-ene base ester
1H NMR δ (CDCl
3) 5.78(1H, m), 5.60(1H, m), 4.63 and 4.52(2H, 2xd), 2.21(3H, s), 1.21(3H, d), 0.95(3H, d).
Monic acids A2-(ethoxycarbonyl methoxyl group) ethyl ester (No. 30 compounds in the table 1)
1H NMR δ (CDCl
3) 5.80(1H, s), 4.29(2H, t), 4.23(2H, q), 4.14(2H, s), 3.80(2H, t), 2.23(3H, s), 1.28(3H, t), 1.23(3H, d), 0.94(3H, d).
Monic acids A2-(acetoxyl group) ethyl ester (No. 29 compounds in the table 1)
1H NMR （CDCl
3） 5.78（1H，s），4.28（4H，s）2.23（3H，s），2.08（3H，s），1.22（3H，d），0.94（3H，d）.
Monic acids A2-(carbamyl ylmethoxy) ethyl ester (No. 46 compounds in the table 1)
1H NMR δ（CDCl
3） 6.65（1H，s），6.50（1H，s），5.86（1H，d），4.54（2H，s），2.22（2H，s），1.21（3H，d），0.92（3H，d）.
Monic acids A3-chlorine third-second-alkene-1-base ester (No. 47 compounds in the table 1)
1H NMR δ (CDCl
3) 6.37-5.91(2H, m), 5.79(1H, s), 5.81 and 4.59(2H, 2xd), 2.21(3H, s), 1.22(3H, d), 0.94(3H, d).
Monic acids A ethyl ester (No. 35 compounds in the table 1)
1H NMR δ（CDCl
3） 5.75（1H，s），4.12（2H，q），2.21（3H，s），1.29（3H，t），1.21（3H，d），0.93（3H，d）.
Monic acids A butyl ester (No. 37 compounds in the table 1)
1H NMR δ（CDCl
3） 5.75（1H，s），4.10（2H，t），2.20（3H，s），1.65（2H，m），1.38（2H，m），1.21（3H，d），0.92（6H，m）
Monic acids A cyclohexyl (No. 39 compounds in the table 1)
1H NMR δ（CDCl）5.73（1H，s），4.78（1H，m），2.21（3H，s），1.80-1.20（10H，s），1.22（3H，d），0.94（3H，d）.
Monic acids A ethoxymethyl ester (No. 76 compounds in the table 1)
1H NMR δ （CDCl
3） 5.79（1H，s），5.30（2H，s），2.22（3H，s），1.22（3H，d），0.92（3H，d）.
Embodiment 34
The present embodiment illustration monic acids A2-(allyloxy) preparation of ethyl ester (No. 23 compounds in the table 1).
The preparation of step 1 1-methylsulfonyl oxygen-2-allyl oxidative ethane,
With 2-allyl oxyethanol (5.0g, 49mM) and triethylamine (5.2g 51mM) in methylene dichloride (25ml), stirs under 0 ℃ of condition of nitrogen gas.Follow stir slowly add methane sulfonyl chloride (5.61g, 49mM). remove cryostat restir mixture 1 hour at room temperature, volatile component is removed in vacuum-evaporation.Residuum ether and water dispenser.Organic fraction washes twice with water, and with the salt water washing once, dry (MgSO
4) and vacuum-evaporation.Product is a yellow oily.
Step 2 monic acids A2-(allyl group oxygen) preparation of ethyl ester.
With monic acids A sodium (165mg; 0.45mM) be dissolved in the dimethyl formamide (2ml), and with 1-methylsulfonyl oxygen-2-allyl group oxidative ethane (162mg, 0.90mM) and N; N-dimethylpropylene urea (0.39ml) at room temperature stirred 19 hours together, and volatile component is removed in vacuum-evaporation.Silicon separates, and with 55: 45 acetone/hexane wash-outs, obtains the required product of colorless oil.
1H NMR δ （CDCl
3） 5.90（1H，m），5.81（1H，s），5.27（1H，d），5.20（1H，d），4.27（2H，t），4.05（2H，d），3.75（2H，t），2.21（3H，s），1.22（3H，d），0.92（3H，s）.
Embodiment 35 to 38
Adopt the ordinary method among the embodiment 33 to prepare following compound:
Monic acids A3-vinyl oxygen propyl diester (No. 33 compounds in the table 1)
1H NMR δ（CDCl
3） 6.46（1H，dd），5.76（1H，s），4.19（3H，m），4.01（1H，dd），3.79（2H，t），2.21（3H，s），1.23（3H，d），0.95（3H，d）.
Monic acids A2-(3-chlorine third-2-alkene-1-base oxygen) ethyl ester (No. 44 compounds in the table 1)
1H NMR δ （CDCl） 6.20（1H，d），5.95（1H，q），5.81（1H，s），4.27（4H，m），3.70（2H，t），2.22（3H，s），1.22（3H，d），0.94（3H，d）.
Monic acids A4-vinyl oxygen fourth-1-base ester (No. 32 compounds in the table 1)
1H NMR δ（CDCl） 6.46（1H，abq），5.74（1H，s），4.11（2H，m），2.21（3H，s），1.20（3H，d），0.92（3H，d）.
Monic acids A2-(third-2-alkynes-1-base oxygen) ethyl ester (No. 43 compounds in the table 1)
1H NMR δ（CDCl
3） 5.80（1H，s），4.28（2H，t），4.21（2H，d），3.79（2H，t），2.48（1H，t），2.21（3H，s），1.21（3H，d），0.94（3H，d）.
Embodiment 39
The present embodiment illustration N, No. 63 compounds in the N-diethyl Zymomonas mobilis acid amides A(table 1) preparation
With monic acids A(200mg, 0.58mM) be dissolved in and be cooled to-10 ℃ in the tetrahydrofuran (THF) (5ml) and under condition of nitrogen gas, (59mg, 0.58mM) (80mg 0.58mM), and stirred 30 minutes with isobutyl chloride formic acid to add triethylamine.(47mg, tetrahydrofuran (THF) 0.58mM) (0.5ml) solution stir reaction mixture 1 hour, at room temperature stir then 2 hours to add diethylamide.Filter reaction mixture and vacuum-evaporation.Thin-layer chromatography shows reaction not exclusively, thus add the tetrahydrofuran solution (3ml) of diethylamide (20mg) again, and with mixture standing over night at room temperature.Volatile component is removed in vacuum-evaporation, and the residuum water absorbs (10ml) and uses chloroform extraction (3 * 10ml).With the organic extraction drying (MgSO that merges
4) and vacuum-evaporation.Obtain colourless gelationus required product with column chromatography purifying gained residuum (silica gel is with methyl alcohol/chloroform wash-out).
1H NMR δ（CDCl
3） 5.87（1H，s），1.91（3H，s），1.21（3H，d），1.12（6H，m），0.92（3H，d）.
Embodiment 40 to 57
Adopt the ordinary method among the embodiment 38 to prepare following compound:
Monic acids acyl A morpholine acid amides (No. 64 compounds in the table 1)
1H NMR δ（CDCl
3） 5.81（1H，s），3.67-3.47（8H，m）1.90（3H，s），1.21（3H，d），0.94（3H，d）.
N-(2,4-dichlorophenyl)-N-methyl monic acids acid amides A(table 1 in No. 60 compounds)
1H NMR δ（CDCl
3） 7.50-7.15（3H，m），5.49（1H，s），3.20（3H，s），2.18（3H，s），1.22（3H，d），0.95（3H，d）。
The N-(2-hydroxyethyl) monic acids acid amides (No. 77 compounds in the table 1)
1H NMR δ（CDCl
3） 7.89（1H，t），5.81（1H，s），4.51（4H，m），2.21（3H，s），1.21（3H，d），0.95（3H，d）.
The N-(2-ethoxyethyl) No. 78 compound in the Zymomonas mobilis acid amides A(table 1)
1H NMR δ（CDCl
3） 6.21（1H，t），5.68（1H，s），3.62-3.42（6H，m），2.20（3H，s），1.20（6H，m），0.92（3H，d）.
The N-(ethoxycarbonylmethyl group) No. 66 compound in the Zymomonas mobilis acid amides A(table 1)
1H NMR δ（CDCl
3） 6.24（1H，t）5.73（1H，s），4.23（2H，q），4.06（2H，d），2.19（3H，s），1.30（3h，t），1.22（3H，d），0.92（3H，d）.
No. 61 compounds in the Zymomonas mobilis acid amides A(table 1)
1H NMR δ（d
4-MeOH） 5.93（1H，s），2.29（3H，s），1.35（3H，d），1.10（3H，d）.
N-(2,4-dichlorophenyl) No. 58 compound in the Zymomonas mobilis acid amides A(table 1)
1H NMR δ（CDCl
3） 7.99（1H，d），7.63（1H，d），7.45（1H，dd），6.20（1H，s），2.38（3H，s），1.33（3H，d），1.10（3H，d）.
N, No. 79 compounds in the N-diallyl Zymomonas mobilis acid amides A(table 1).
1H NMR δ（CDCl
3） 5.89（1H，s），5.76（2H，m），5.16（4H，m），1.97（3H，s），1.22（3H，d），0.93（3H，d）.
Monic acids A piperidines acid amides (No. 80 compounds in the table 1)
1H NMR δ（CDCl
3） 5.81（1H，s）3.50（4H，m），1.85（3H，s），1.60（6H，m），1.21（3H，d），0.92（3H，d）
Monic acids A N methyl piperazine acid amides (No. 81 compounds in the table 1)
1H NMR δ（d
4-MeOH） 5.99（1H，s），3.72（4H，m），2.56（4H，t），2.44（3H，s），1.97（3H，s），1.32（3H，d），1.06（3H，d）.
N, No. 82 compounds in the N-dimethyl Zymomonas mobilis hydrazides A(table 1)
1H NMR δ（CDCl
3） 5.52（1H，s），2.40（6H，s），2.04（3H，s），1.10（3H，d），0.83（3H，d）.
No. 65 compounds in the Zymomonas mobilis hydrazides A(table 1)
1H NMR δ（d
4-MeOH） 5.80（1H，s），2.28（3H，s），1.30（3H，d），1.04（3H，d）.
N-(third-2-base subunit) No. 83 compound in the Zymomonas mobilis hydrazone A(table 1)
1H NMR δ（d
4-MeOH） 6.84（1H，s），5.76（1H，s），2.33（3H，s），2.20（3H，s），2.12（3H，s），1.35（3H，d），1.10（3H，d）.
The N-(2.5-dichlorophenyl) No. 59 compound in the Zymomonas mobilis acid amides A(table 1)
1H NMR δ（d
6-DMSO）9.42（1H，s），7.86（1H，d）7.46（1H，d），7.18（1H，dd），6.05（1H，s），2.21（3H，s）1.02（3H，d），0.80（3H，d）。
Monic acids A tetramethyleneimine acid amides (No. 84 compounds in the table 1)
1H NMR δ（CDCl
3） 5.88（1H，s），3.46（4H，m），2.08（3H，s），1.90（4H，m），1.21（3H，d），0.92（3H，d）
Monic acids A2,6-thebaine acid amides (No. 85 compounds in the table 1)
1H NMR δ（CDCl
3） 5.80（1H，s），3.50（6H，m），1.85（3H，s），1.20（9H，m），0.93（3H，d）.
N-allyl group Zymomonas mobilis acid amides (No. 86 compounds in the table 1)
1H NMR δ（CDCl
3） 5.92-5.72（2H，m），5.68（1H，s），5.22-5.10（2H，m），3.10（2H，m），2.18（3H，s），1.21（3H，d），0.92（3H，d）.
N, No. 87 compounds in two (2-hydroxyethyl) the Zymomonas mobilis acid amides A(tables 1 of N-)
1H NMR δ（d
6-DMSO） 5.90（1H，s），3.40（4H，m），3.30（4H，m），1.80（3H，s），1.10（3H，d），0.78（3H，d）
Embodiment 58
The present embodiment illustration S-(carbonyl methoxyl methyl) No. 75 compounds in the sulfo-monad acid ester A(table 1) and preparation
With monic acids A(80mg, 0.23mM) be dissolved in tetrahydrofuran (THF) (3ml) and under condition of nitrogen gas, be cooled to-10 ℃.Add triethylamine (24mg, 0.23mM) and isobutyl chloride formic acid (32mg, tetrahydrofuran (THF) 0.23mM) (0.7ml) solution, and stirring 20 minutes.Add methyl sulfo-glycolate (25mg, 0.23mM) tetrahydrofuran (THF) (0.5ml) solution, stirred reaction mixture 1 hour, at room temperature stirred then 3 hours, the vacuum-evaporation reaction mixture, and with gained residuum storage at room temperature 7 days, with column chromatography purification reaction thing (silica gel, with 1: 9 wash-out of methyl alcohol/chloroform) obtain colourless gelationus required product (67mg, 67%).
1H NMR δ（CDCl
3） 6.10（1H，s），4.76（3H，s），4.74（2H，s），2.21（3H，s），1.22（3H，d），0.93（3H，d）.
Embodiment 59 to 60
Adopt the ordinary method among the embodiment 58 to prepare following compound:
S-phenyl sulfo-monad acid ester (No. 74 compounds in the table 1)
1H NMR δ（CDCl
3） 7.42（5H，s），6.18（1H，s），2.20（3H，s），1.22（3H，d），0.92（3H，d）.
S-(2-vinyl oxygen ethyl) No. 68 compound in the sulfo-monad acid ester A(table 1)
1H NMR δ（CDCl
3） 6.45（1H，dd），6.07（1H，s），5.80（2H，s），3.18（2H，t），2.21（3H，s），1.73（2H，t），1.21（3H，d），0.95（3H，d）.
Embodiment 61
The present embodiment illustration preparation of monic acids A3-nitrophenyl ester (No. 52 compounds in the table 1)
With Zymomonas mobilis ester A(200mg, 0.58mM) be dissolved in tetrahydrofuran (THF) (5.5ml) and under nitrogen, be cooled to-10 ℃.Add triethylamine (59mg, 0.5mM) and isobutyl chloride formic acid (80mg 0.58mM) and stirred 10 minutes, at room temperature stirred solids removed by filtration and vacuum concentrated filtrate 1 hour then.Residuum absorb (2.5ml) with methylene dichloride and add the 2-nitrophenols (323mg, 2.32mM).Add methylene dichloride (0.5ml) solution of pyridine (35mg), obtain clarifying homogeneous solution, and with mixture agitation and filtration at room temperature.Solvent removed in vacuo is also separated with silicon, obtaining required product with acetone/hexane separation in 55: 45.
1H NMR δ（CDCl
3） 8.10（1H，d），8.02（1H，m），7.54（1H，t），7.47（1H，d），6.02（1H，s），2.19（3H，s），1.22（3H，d），0.95（3H，d）.
Embodiment 62 to 68
Adopt the ordinary method among the embodiment 60, prepare following compound:
Monic acids A phenylester (No. 50 compounds in the table 1)
1H NMR δ（CDCl
3） 7.39（2H，t），7.21（1H，t），7.10（2H，d），6.00（1H，s），2.28（3H，s），1.21（3H，d），0.93（3H，d）.
Monic acids A furfuryl group ester (No. 56 compounds in the table 1)
1H NMR δ（CDCl
3） 7.42（1H，s），6.41（1H，d），6.32（1H，t），5.79（1H，s），5.08（2H，s），2.22（3H，s），1.21（3H，s），0.94（3H，d）.
Monic acids A neo-pentyl ester (No. 38 compounds in the table 1)
1H NMR δ（CDCl
3） 5.78（1H，s），3.79（2H，s），2.21（3H，s），1.21（3h，d），0.95（12H，m）.
Monic acids A2-chloro-ethyl ester (No. 57 compounds in the table 1)
1H NMR δ（CDCl
3） 5.81（1H，s），4.37（2H，t），3.72（2H，t），2.24（3H，s），1.22（3H，d），0.98（3H，d）.
Monic acids A4-methoxyphenyl ester (No. 53 compounds in the table 1)
1H NMR δ（CDCl
3） 7.01（2H，d），6.88（2H，d），5.97（1H，s），3.80（3H，s），2.26（3H，s），1.22（3H，d），0.94（3H，d）.
Monic acids A2-(ethene sulfo-) ethyl ester (No. 67 compounds in the table 1)
1H NMR δ（CDCl
3） 6.33（1H，dd），5.78（1H，s），5.28（1H，d），5.20（1H，d），4.28（2H，t），2.95（2H，t），2.21（3H，s），1.21（3H，d），0.95（3H，d）.
Embodiment 69
Following embodiment illustration the preparation of Zymomonas mobilis ester A trimethylammonium sulfonium salt (No. 88 compounds in the table 1)
(59mg is 0.29mM) in water-soluble (5ml), and with Dowex 1 * 2(HO with the trimethylsulfonium iodide
-) plastic resin treatment 10 minutes.This solution is filled into unit cell acid A(100mg, in water 0.29mM) (10ml) solution.This solution of lyophilize obtains required product.
1H NMR δ（D
2O） 5.70（1H，s），2.83（9H，s），1.90（1H，s），1.16（3H，d），0.91（3H，d）.
Embodiment 70
Following embodiment illustration monic acids A4-(methoxycarbonyl) preparation of phenylester (No. 54 compounds in the table 1)
With monic acids A(250mg, 0.72mM) be dissolved in the methylene dichloride (3ml), add triethylamine (74mg, 0.73mM) methylene dichloride (1ml) solution, and mixture at room temperature stirred 5 minutes, reaction mixture in ice/water-bath, and slowly add isoprene chloroformic acid (88mg, 0.73mM) methylene dichloride (1ml) solution, and follow and stirred again cooling mixture 10 minutes.Adding the 4(methoxycarbonyl) (166mg, 1.09mM) and N, N-dimethyl aminopyridine (9mg) is followed cooling restir mixture 2 hours to phenol, separates crude product mixture with silicon, with 55: 45 acetone/hexane wash-outs, obtains required product.
1H NMR δ（CDCl
3）8.08（2H，d），7.18（2H，d），5.99（1H，s），3.91（3H，s），2.27（3H，s），1.21（3H，d），0.93（3H，d）.
Embodiment 71
Following embodiment illustration the preparation of Pseudomonic Acid A 2-vinyl oxygen ethyl ester (No. 89 compounds in the table 2).
With false unit cell acid A(200mg, 0.40nM) be dissolved in the acetone (2ml), and with 1-chloro-2-vinyl oxidative ethane (85mg, 0.60mM) and sodium iodide (132mg, 88mM) stirring together.(83mg 0.60mM) also at room temperature stirred the mixture 2 hours and refluxes and spend the night to add salt of wormwood.Volatile component is removed in vacuum-evaporation.Residuum absorbs with dimethyl formamide (1ml) and N, N-dimethylpropylene urea (0.5ml), and 80 ℃ of heating 4 hours, and (85mg 0.6mM) and sodium iodide (120mg), and continues to heat 8 hours to add part 1-chloro-2-vinyl oxidative ethane again.Reaction mixture is distributed between water and ether, and organic layer water and salt water washing, the sal epsom thorough drying used then.Separate with silicon,, obtain as gelationus required product with 55: 45 acetone/hexane wash-outs.
1H NMR δ（CDCl
3） 6.49（1H，m），5.76（1H，s），4.32（2H，t），4.20（1H，dd），4.08（2H，t），2.32（2H，t），2.20（3H，s），1.21（3H，d），0.95（3H，d）.
Embodiment 72 and 73
Adopt the ordinary method among the embodiment 71 to prepare following compound
Pseudomonic Acid A ethyl ester (No. 90 compounds in the table 2)
1H NMR δ（CDCl
3） 5.79（1H，s），4.15（2H，q），4.11（2H，t），2.28（2H，t），2.21（3H，s），0.95（3H，d）.
Pseudomonic Acid A second-hydroxyethyl ester (No. 91 compounds in the table 2)
1H NMR δ（CDCl
3） 5.78（1H，s），4.21（2H，t），4.08（2H，t），2.32（2H，t），2.21（3H，s），1.21（3H，d），0.95（3H，d），
Embodiment 74
Following embodiment illustration N, the preparation of the false single bacterium acid A acid amides of N-diethyl (No. 92 compounds in the table 2)
With Pseudomonic Acid A (200mg, 0.40mM) be dissolved in the tetrahydrofuran (THF) (4ml), and under nitrogen, be cooled to-10 ℃, add triethylamine (41mg, 0.40mM) and isobutyl chloride formic acid (55mg, 0.4mM) and stirred 30 minutes, with diethylamide (32mg, 0.40mM) tetrahydrofuran (THF) (2ml) solution add in the reaction mixture, reaction mixture was stirred 30 minutes, then in the room temperature standing over night.Filter reaction mixture and vacuum-evaporation.Residuum water (10ml) absorbs and (3 * 10ml) extract with chloroform.The organic extraction that merges obtains colourless gelationus product with sal epsom thorough drying and vacuum-evaporation with column chromatography purifying gained residuum (silica gel is with 55: 45 wash-outs of acetone/hexane).
1H NMR δ（CDCl
3） 5.78（1H，s），4.08（2H，t），3.31（4H，q），2.28（2H，t），2.21（3H，s），1.22（6H，t），0.95（3H，d）.
Embodiment 75
The present embodiment illustration preparation of monic acids A sec.-propyl amine salt (No. 96 compounds in the table 1).
With monic acids A(50mg, 0.15mM) be dissolved in the tetrahydrofuran (THF) (2ml) also with isopropylamine (8.6mg, 0.15mM) processing.After at room temperature 20 minutes, precipitation forms, and it is filtered to collect obtain required product.
1H NMR δ（CDCl
3） 5.76（1H，s），2.21（3H，s），1.21（3H，d），1.10（6H，d），0.93（3H，d）.
Embodiment 76 and 77
Adopt the ordinary method system among the embodiment 75 to prepare following compound:
Monic acids A triethylamine salt (No. 97 compounds in the table 1)
1H NMR δ（CDCl
3） 5.80（1H，s），2.88（6H，q），2.13（3H，s），1.20（12H，m），0.92（3H，d）.
Pseudomonic Acid A triethylamine salt (No. 98 compounds in the table 2)
1H NMR δ（CDCl
3） 5.78（1H，s），4.08（2H，t），3.00（6H，q），2.21（3H，s），1.25（9H，t），0.94（3H，d）.
Embodiment 78
The present embodiment illustration preparation of monic acids A sodium salt (No. 99 compounds in the table 1).
With monic acids A(1.2g, 3.48mM) be suspended in the water (35ml), and (34.8ml, 3.48mM) aqueous solution is handled with 0.1M sodium hydroxide.The solution lyophilize obtains the required product of white solid.
1NMR δ（D
20） 5.69（1H，s），1.85（1H，s），1.15（3H，d）0.90（3H，d）.
Embodiment 79
The present embodiment illustration from monic acids C(table 3 No. 107 compounds) preparation monic acids C2-ethoxyethyl ester (No. 108 compounds in the table 3).
With monic acids C(1.62g, 0.49mM) with dimethyl formamide (1ml) and N, the mixture of N-dimethylpropylene urea (0.43ml) absorbs, add salt of wormwood (0.102g, 0.74mM), and 80-90 ℃ of stirred reaction mixture 1 hour.Behind the cool to room temperature, add 2-chloroethyl ethyl ether (0.107g, 0.99mM) the solution of dimethyl formamide (0.5ml), mixture was at room temperature stirred 19 hours, stirred 6 hours, rest on ambient temperature overnight then at 90 ℃, vacuum is removed volatility, and residuum separates with silicon, with acetone/hexane (1: 1) wash-out, obtains as gelationus required product.
1H NMR δ（CDCl
3） 5.81（1H，s），5.45（2H，d），4.25（2H，t），3.75（2H，t），2.22（3H，t），1.23（3H，t），1.17（3H，d），1.00（3H，d）.
Embodiment 80 to 88
Adopt the ordinary method among the embodiment 20 to prepare following compound:
Monic acids A2-(oneself-2-alkene-1-yl) ethyl ester (No. 94 compounds in the table 1)
1H NMR δ（CDCl
3） 5.80（1H，s），5.30-5.60（2H，m），4.22（2H，t），2.21（3H，s），1.21（3H，d），0.95（6H，m）.
Monic acids A cyclopropyl methyl ester (No. 93 compounds in the table 1)
1H NMR δ（CDCl
3） 5.80（1H，s），3.92（2H，d），2.23（3H，s），1.23（3H，d），0.94（3H，d），0.57（2H，m），0.29（2H，m）.
Monic acids A(E/Z) ethyl ester (1: 1) (No. 24 compounds in the table 1) 2-third-1-alkene-1-base oxygen)
1H NMR δ (CDCl
3) 6.24 and 5.79(1H, 2xd), 5.80(1H, s), 4.81 and 4.44(1H, 2xm), 4.26(2H, m), 2.23(3H, s), 1.23(3h, d), 0.95(3H, d).
Monic acids A2-(third-2-base oxygen) ethyl ester (239075), (No. 100 compounds in the table 1)
1H NMR δ（CDCl
3） 5.81（1H，s），4.22（2H，m），3.63（2H，t），2.22（3H，s），1.23（3H，d），1.18（6H，d），0.95（3H，d）.
Monic acids A2-methoxyethyl ester (No. 101 compounds in the table 1)
1H NMR δ（CDCl
3） 5.83（1H，s），4.25（2H，t），3.60（2H，t），3.40（3H，s），2.22（3H，s），1.23（3H，d），0.95（3H，d）.
Monic acids A2-(third-1-base oxygen) mixture of ethyl ester (No. 102 compounds in the table 1) diastereomer.
1H NMR δ（CDCl
3） 5.80（1H，s），4.23（2H，t），3.65（2H，t），2.21（3H，s），1.60（2H，t），1.21（3H，d），0.90（6H，m）.
Monic acids A2-ethoxy-1-methylethyl ester (No. 103 compounds in the table 1)
1H NMR δ（CDCl
3）5.78（1H，s），5.09（1H，m），2.21（3H，s），1.20（9H，m），0.93（3H，d）.
No. 104 compounds in the monic acids A2-cyclopropyl oxygen ethyl ester table 1)
1H NMR δ（CDCl
3） 5.81（1H，s），4.21（2H，t），3.72（2H，t），2.21（3H，s），1.21（3H，d），0.95（3H，d），0.60（2H，m），0.50（2H，m）.
Monic acids A2-ethoxy-2-methylethyl ester (No. 105 compounds in the table 1), the mixture of diastereomer.
1H NMR δ（CDCl
3） 5.68（1H，s），4.02（2H，t），2.21（3H，s），1.15（6H，m），0.88（6H，m）.
Embodiment 89
Adopt the ordinary method among the embodiment 61 to prepare following compound.
A ⅰ) and ⅱ) mixture of (5: 2)
ⅰ) monic acids A2-(oneself-1-alkene-1-base oxygen) ethyl ester (No. 34 compounds in the table 1)
1H NMR δ（CDCl
3） 5.91（1H，d），5.79（1H，s），4.38（1H，q），2.20（2H，s），1.21（3H，d），0.92（3H，d）.
ⅱ) monic acids A2-(1-(vinyl)-and Ding-1-base oxygen) ethyl ester (No. 95 compounds in the table 1)
1H NMR δ（CDCl
3） 5.79（1H，s），5.62（1H，m），5.20（1H，d），2.20（2H，s），1.21（3H，d），0.92（3H，d）.
Embodiment 90 and 91
Adopt the ordinary method among the embodiment 39, prepare following compound:
No. 106 compounds in the N-methoxyl group Zymomonas mobilis acid amides A(table 1)
1H NMR δ（CDCl
3） 5.58（1H，s），3.70（3H，s），2.20（3H，s），1.21（3H，d），0.95（3H，d）.
No. 62 compounds in the N-ethyl Zymomonas mobilis acid amide A(table 1)
1H NMR δ（CDCl
3） 5.64（1H，s），5.54（1H，t），3.33（2H，q），2.18（3H，s），1.22（3H，d），1.17（3H，t），0.95（3H，d）.
Embodiment 92
The present embodiment illustration according to the herbicidal properties of The compounds of this invention.
Weeding activity as following test compounds.The preparation of every kind of chemical, be that its is sprayed in the mixture of solvent that volume is dissolved in appropriate amount according to final, this mixture contains that 78.2gm/ rises polysorbas20 and 21.8gm/ rises Span80, and transferring to 1 liter with methylcyclohexanone, polysorbas20 is the trade mark that contains the tensio-active agent of the oxyethane of 20 mol ratios and sorbitan laurate condenses.Span80 is the trade mark that contains the Arlacel-20 tensio-active agent.If compound does not dissolve, water is added to 5cm with volume
3Volume, add granulated glass sphere, this mixture that vibrates then dissolves chemical effectively or suspends, and removes granulated glass sphere then.In all cases, to required sprinkling volume, if spray separately, test needs 25cm respectively before the seedling and behind the seedling at dilute with water mixture after this
3And 30cm
3Volume; If spray together, need 45cm
3, contain in the spray water emulsion solvent/surface-active compounds come of 4% beginning and proper concn for the examination chemical.
The spray composition of so preparation is sprayed onto the tender basin of children carries on the plant and (tests behind the seedling), the sprinkling amount is higher than 1000 liter 1 to No. 22 compound of per hectare and 400 liter 23 to No. 94 compound of per hectare, spray after 13 days, by comparing with the plant of being untreated, evaluation is to the infringement of plant, standard is 0 to 9 wherein to be that 0% infringement 1 damages for 1-5%, 2 are the 6-15% infringement, 3 are the 16-25% infringement, 4 are the 26-35% infringement, 6 are the 60%-69% infringement, and 7 are the 70-79% infringement, and 8 damage and 9 are that 90-100% damages for 80-89%.
The plant species of this compound antagonism expression is not tested in symbol "-" expression.
Experimental result provides in following table III.
The table IV
Abbreviation to the test plant employing
BV-sugar beet Sugar beet
BN-rape Rape
GM-soybean Soybean
ZM-corn Maize
OS-paddy rice Rice
TA-winter wheat Winter wheat
PA-Armstrong Polygonum aviculare
CA-lamb's-quarters Chenopodium album
GA-Tender Catchweed Bedstraw Herb Galium aparine
AR-Amaranthus retroflexus Amaranthus retroflexus
BP-three leaf ghost leaf grass Bidens pilosa
EH -Euphorbia?heterophylla
IH-pharbitis nilChoisy Ipomoea hederacea (behind the seedling)
AT-Tong fiber crops Abutilon theophrasti
XT-Siberian cocklebur Xanthium strumarium
AF-wild avena sativa Avena fatua
AM-mouse tail amur foxtail Alopecurus myosuroides
AE-Agropyron repens Agropyron repens
SH-A Ci Bogao fine strain of millet Sorghum halepense
SV-Herba Setariae Viridis Setaria viridis
DS-lady's-grass Digitaria sanguinalis
EC-barnyard grass Echinochloa crus-galli
CE-chufa Cyperus esculentus
MI-german chamomile Matricaria perforata
LR-wimmera ryegrass Lolium rigidum
PD-knucklegrass Paniucum dicotomifirum
Chemical structural formula (diagram)
Chemical structural formula (diagram)
Chemical structural formula (diagram)
Chemical structural formula (diagram)
Claims (21)
1, contain formula I or (I A) or (I B) compound and the composition of blended weeding acceptable carrier or thinner with it:
And R wherein
2Be CO-XR
3Base wherein X is O or S and R
3Be acceptable one-tenth ester group on hydrogen or the agrochemistry; Or R
2Be-R
4Base is R wherein
4Be any substituted aryl or heterocyclic radical; Or R
2Be CO-NR
5R
6Base is R wherein
5And R
6Identical or different and represent acceptable formation amide group on the agrochemistry separately; Formula I, the steric isomer and the formula I of (I A) or (I B) compound, the salt of (I A) and (I B) compound, wherein R
2Be COXR
3, X is O and R
3Be hydrogen.
2, according to composition claimed in the claim 1 R wherein
2Be CO-XR
3Base and X are oxygen.
3, according to claim 1 or the claimed composition of claim 2, wherein R
2Be CO-XR
3Base and R
3Be the C that replaces arbitrarily
1To C
20Alkyl, the C that replaces arbitrarily
2To C
20Alkenyl, the C that replaces arbitrarily
2To C
20Alkynyl group replaces C arbitrarily
3To C
7Cycloalkyl, the aryl that replaces or the heterocyclic radical of replacement arbitrarily arbitrarily.
4, the composition claimed according to claim 3 wherein can be at any substituted alkyl, alkenyl or alkynyl group R
3The middle any substituting group that exists is C
3-7Cycloalkyl, C
1-10Alkoxyl group, C
1-10Alkylthio, C
2-8Alkenyloxy, C
2-8Alkenyl thio, C
2-8Chain oxy-acetylene, C
2-8Sulfur-based chain acetylene, halogen, halo-C
1-10Alkoxyl group, halo-C
2-8Alkenyloxy, halo-C
2-8Chain oxy-acetylene, carboxyl, C
1-6Carbalkoxy, formamyl, any aryl that replaces, any heterocyclic radical that replaces, hydroxyl, cyano group, nitro, C
1-6Chain triacontanol base oxygen, amino, single and two-(C
1-6) alkylamino; And wherein can be at C
3-7Cycloalkyl R
3The middle any substituting group that exists comprises C
1-6Alkyl, halo-C
1-6Alkyl, C
1-10Alkoxyl group, C
1-10Alkylthio, C
2-8Alkenyl, C
2-8Alkenyloxy, C
2-8Alkenyl thio, C
2-8Alkynyl group, C
2-8Chain oxy-acetylene, C
2-8Alkyne sulphur, halogen, carboxyl, C
1-6Carbalkoxy, formamyl, any aryl that replaces, any heterocyclic radical that replaces, hydroxyl, cyano group, nitro, C
1-6Chain triacontanol base oxygen, amino, single-and two-(C
1-6) alkylamino; And wherein any substituting group that can exist in aryl or heterocyclic radical is for being independently selected from C
1-6Alkyl, C
1-6Alkoxyl group, C
1-6Alkylthio, halo (C
1-6) alkyl, hydroxyl (C
1-6) alkyl, halo (C
1-6) alkoxyl group, C
2-8Alkenyl, C
2-8Alkenyloxy, C
2-8Alkenyl thio, C
2-8Alkynyl group, C
2-8Chain oxy-acetylene, C
2-8Sulfur-based chain acetylene, hydroxyl, cyano group, nitro, amino, single-and two-C
1-6Alkylamino, C
1-6The inferior acyl sulphur of alkyl, C
1-6The alkane alkylsulfonyl, carboxyl, C
1-6Carbalkoxy, and C
1-6Carbalkoxy (C
1-6) alkyl.
5, according to claim 3 or the claimed composition of claim 4, wherein R
3Be not to be substituted or by hydroxyl, the C that halogen or cyano group replace arbitrarily
1To C
10Alkyl.
6, according to claim 3 or the claimed composition of claim 4, wherein R
3Be not to be substituted or by hydroxyl, the C that halogen or cyano group replace arbitrarily
2To C
10Alkenyl.
7, the composition claimed, wherein R according to claim 1
2Be CO-XR
3Base and R
3By-A-R
‖The C that replaces
1-10Alkyl ,-A-R
‖A is O or S(O in the base) the x base wherein x be 0,1 or 2 and R
‖Be the C that replaces arbitrarily
1To C
10Alkyl, the C that replaces arbitrarily
2To C
8Alkenyl, the C that replaces arbitrarily
2To C
8Alkynyl group, the phenyl that replaces, the C that replaces arbitrarily arbitrarily
1-6Alkyl-carbonyl, the C that replaces arbitrarily
3-7Cycloalkyl or the C that replaces arbitrarily
3-7Heterocyclic radical.
8, according to the claimed combination of claim 7 and, R wherein
3By-A-R
‖The C that replaces
1-4Alkyl ,-A-R
‖Middle A is O or S and R
‖Be the C that replaces arbitrarily
1To C
6Alkyl, the C that replaces arbitrarily
2To C
6Alkenyl, the C that replaces arbitrarily
2To C
6Alkynyl group, the phenyl that replaces, the C that replaces arbitrarily arbitrarily
1-6Alkyl-carbonyl replaces C arbitrarily
3-6Cycloalkyl or replace aliphatic C arbitrarily
3-7Oxygen-containing heterocycle.
9, according to the claimed composition of claim 1 R wherein
2Be CO-XR
3Base and R
3Be (a CH
2) n '-A-CH=CH-R
12, wherein n ' is 1 to 4 integer, A be O or (S(O) the x base wherein x be 0,1 or 2 and R
12Be hydrogen or C
1To C
4Alkyl.
10, the composition claimed, wherein R according to claim 1
2Be heterocyclic radical-R
4And R
4Be the group of formula II:
R wherein
14And R
15Identical or different, be independently selected from hydrogen, the phenyl that replaces replaces C arbitrarily arbitrarily
1To C
20Alkyl replaces C arbitrarily
2To C
8Alkenyl replaces C arbitrarily
2To C
8Alkynyl group, substituted heterocyclic radical C arbitrarily
3To C
7Cycloalkyl, X is a divalent radical ,-Y '-C=C-and y ' they are oxygen or sulphur.
11, the composition claimed according to claim 10, its R
4It is any substituted oxazole-2-base group.
12, the composition claimed, wherein R according to claim 1
2Be CO-XR
3Base and R
3Be-Z-CO-R
8Base wherein Z is C
1To C
12Alkenyl and R
8The C that representative replaces arbitrarily
1-10Alkyl replaces C arbitrarily
3-8Cycloalkyl replaces C arbitrarily
2-10Alkenyl replaces C arbitrarily
2-10Alkynyl group, substituted aryl, substituted aralkyl, the cycloalkyl that replaces or any substituted heterocyclic radical arbitrarily arbitrarily arbitrarily.
13, according to the claimed composition of claim 1 R wherein
2Be CO-NR
5R
6Base and R wherein
5And R
6Identical or different and be independently of one another:
(a) hydrogen or
(b) replace C arbitrarily
1-20Alkyl replaces C arbitrarily
2-20Alkenyl or replace C arbitrarily
2-20Alkynyl group or
(c) replace C arbitrarily
3To C
7Cycloalkyl or
(d) arbitrarily substituted aryl or
(e) any substituted heterocyclic radical; Or
(f) R
5And R
6Represent any replacement C with the nitrogen-atoms that they link to each other
5-7Heterocycle or
(g) R
5Be hydrogen and R
6Be-NR
22-R
23R
24Base is R wherein
22Be hydrogen or C
1-6Alkyl, R
23And R
24Identical or different, can adopt independently above-mentioned any at (a), (b), (c), (d), (e) and (f) under to R
5And R
6The implication that provides, or
(h) R
6Be-NR
22-N=CR
23R
24Base is R wherein
22, R
23And R
24Have the aforementioned implication that provides, or
(i) R
5Be hydrogen and R
6Be-CR
25R
26-CO-W or-NR
27-CO-W base, wherein W is phenyl that replaces arbitrarily or the heterocyclic radical that replaces arbitrarily, R
25, R
26And R
27Be hydrogen or any C that replaces independently
1-6Alkyl.
14, according to the composition of claim 13, R wherein
5Be hydrogen or C
1-4Alkyl and R
6Be C
1-4Alkyl, each alkyl can be independently by C
3-7Cycloalkyl, C
1-4Alkoxyl group, halogen, carboxyl, C
1-6Carbalkoxy, formamyl, any aryl that replaces, any heterocyclic radical that replaces, hydroxyl, C
1-6Alkanol oxygen base, amino list-or two-(C
1-6) alkylamino at random replaces or R wherein
5And R
6With their link to each other C of any replacement that nitrogen-atoms represents
5-6The aliphatic series heterocycle.
15, according to the composition of claim 14 R wherein
5And R
6Represent morpholinyl with the nitrogen-atoms that they link to each other, piperidyl, piperazinyl, or pyrrolidyl, wherein each can be by halogen or C
1-4Alkyl at random replaces.
16, the compound of formula I or (I A) or (I B), wherein R in the claim 1
2Be CO-XR
3Base, X are O or S and R
3By-A-R
‖The C that base replaces arbitrarily
1-10Alkyl ,-A-R
‖In A be O or S(O) the x base, wherein X is 0,1 or 2 and R
‖Be the C that replaces arbitrarily
1To C
10Alkyl replaces C arbitrarily
2To C
8Alkenyl replaces C arbitrarily
2To C
8Alkynyl group, substituted-phenyl replaces C arbitrarily arbitrarily
1-6Alkyl-carbonyl replaces C arbitrarily
3-7Cycloalkyl or replace C arbitrarily
3-7Heterocyclic radical, condition are to work as R
‖When being ethyl, R
3Be not-(CH
2)
2Base.
17, claimed compound R wherein in the claim 16
3By-A-R
‖The C that replaces
1-4Alkyl, wherein A is O or S(O) the x base wherein x be 0,1 or 2 and R
‖Be the C that replaces arbitrarily
1To C
6Alkyl, the C that replaces arbitrarily
2To C
6Alkenyl, the C that replaces arbitrarily
2To C
6Alkynyl group, the phenyl that replaces, the C that replaces arbitrarily arbitrarily
1-6Alkyl-carbonyl replaces C arbitrarily
3-6Cycloalkyl or replace aliphatic C arbitrarily
3-7Oxygen-containing heterocycle.
18, according to the claimed compound of claim 17 R wherein
3Be-(CH
2)
n-A-CH=CH-R
12, wherein n ' is 1 to 4 integer, A be O or (S(O) the x base wherein x be 0,1 or 2 and R
12Be hydrogen or C
1To C
4Alkyl.
19、
R wherein
2Be selected from the following group that comprises.
20, formula (I B) compound
R wherein
2Be selected from the following group that comprises
21, seriously damage or kill the method for noxious plant, comprising the formula I in the claim 1 of the growing environment of plant or plant being used herbicidally effective amount or (I A) or (I B) compound, wherein R
2As any one definition in the claim 1 to 15, or use in the claim 16 to 19 of herbicidally effective amount each claimed compound.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB929207542A GB9207542D0 (en) | 1992-04-07 | 1992-04-07 | Herbicides |
| GB9207542.3 | 1992-04-07 | ||
| GB9226733.5 | 1992-12-22 | ||
| GB929226733A GB9226733D0 (en) | 1992-12-22 | 1992-12-22 | Herbicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1079965A true CN1079965A (en) | 1993-12-29 |
Family
ID=26300664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93105215A Pending CN1079965A (en) | 1992-04-07 | 1993-04-07 | Weedicide |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0634895A1 (en) |
| CN (1) | CN1079965A (en) |
| AU (1) | AU3759193A (en) |
| BG (1) | BG97605A (en) |
| CA (1) | CA2132746A1 (en) |
| GB (1) | GB9305238D0 (en) |
| IL (1) | IL105272A0 (en) |
| MA (1) | MA22867A1 (en) |
| TR (1) | TR27245A (en) |
| UY (1) | UY23567A1 (en) |
| WO (1) | WO1993019599A1 (en) |
| ZW (1) | ZW4393A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9320563D0 (en) * | 1993-10-06 | 1993-11-24 | Zeneca Ltd | Assay procedure and application in identification of herbicides |
| GB9320561D0 (en) * | 1993-10-06 | 1993-11-24 | Zeneca Ltd | Heterocyclic compounds |
| EP3772514A1 (en) | 2019-08-08 | 2021-02-10 | Basf Se | Herbicidal amides |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1587058A (en) * | 1976-06-15 | 1981-03-25 | Beecham Group Ltd | Oxiranylmethyltetrahydropyran derivatives |
| ZA814257B (en) * | 1980-06-24 | 1983-02-23 | Beecham Group Plc | Treating plant infections |
-
1993
- 1993-03-15 GB GB939305238A patent/GB9305238D0/en active Pending
- 1993-03-16 AU AU37591/93A patent/AU3759193A/en not_active Abandoned
- 1993-03-16 EP EP93906681A patent/EP0634895A1/en not_active Withdrawn
- 1993-03-16 WO PCT/GB1993/000542 patent/WO1993019599A1/en not_active Application Discontinuation
- 1993-03-16 CA CA002132746A patent/CA2132746A1/en not_active Abandoned
- 1993-03-18 ZW ZW43/93A patent/ZW4393A1/en unknown
- 1993-04-02 IL IL105272A patent/IL105272A0/en unknown
- 1993-04-05 MA MA23158A patent/MA22867A1/en unknown
- 1993-04-05 BG BG97605A patent/BG97605A/en unknown
- 1993-04-07 CN CN93105215A patent/CN1079965A/en active Pending
- 1993-04-07 UY UY23567A patent/UY23567A1/en unknown
- 1993-04-07 TR TR00306/93A patent/TR27245A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU3759193A (en) | 1993-11-08 |
| CA2132746A1 (en) | 1993-10-14 |
| BG97605A (en) | 1994-06-30 |
| EP0634895A1 (en) | 1995-01-25 |
| WO1993019599A1 (en) | 1993-10-14 |
| ZW4393A1 (en) | 1993-11-24 |
| IL105272A0 (en) | 1993-08-18 |
| MA22867A1 (en) | 1993-12-31 |
| UY23567A1 (en) | 1993-04-21 |
| GB9305238D0 (en) | 1993-05-05 |
| TR27245A (en) | 1994-12-21 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |