CN1065660A - Herbicidal pyrones - Google Patents
Herbicidal pyrones Download PDFInfo
- Publication number
- CN1065660A CN1065660A CN 92101624 CN92101624A CN1065660A CN 1065660 A CN1065660 A CN 1065660A CN 92101624 CN92101624 CN 92101624 CN 92101624 A CN92101624 A CN 92101624A CN 1065660 A CN1065660 A CN 1065660A
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- Prior art keywords
- alkyl
- group
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- phenyl
- alkylthio
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/10—Spiro-condensed systems
-
- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to general formula (I) compound and isomer thereof and/or its tautomer, wherein, A, X, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9Such as in the specification sheets definition, the method and the selectivity that contain the weeding of this compound and plant growth regualting composition and coordinate plant growth suppress, and destroy or kill method for weed in the wide leaf farm crop.
Description
The present invention relates to have the organic compound of herbicidal properties and plant growth regulating character; Method and plant growth regualting composition and these method for compositions of application of herbicidal composition and these compounds of application.
With some hexanaphthene-1, the 3-derovatives is known as weedicide in the prior art." Agricultural Chemicals-Book II Herbicides 1983-84 Revision " (W.T.Thomson Editor for example, Thomson Publications, California U.S.A) described in the summary commercial known withered (3-(1-(allyloxy imino-) the butyl)-4-hydroxyl-6 that reaches extremely, 6-dimethyl-2-oxygen hexamethylene-3-olefinic carboxylic acid methyl esters), Cycloproxydim((E, E)-2-(1-(1-((3-chloro-2-propenyl) oxygen base) imino-) butyl)-5-(2-(ethylmercapto group) propyl group)-3-hydroxyl-2-tetrahydrobenzene-1-ketone) and Sethoxydim(2-(1-(ethoxy imino) butyl)-5-(2-ethylmercapto group) propyl group-3-hydroxyl-2-tetrahydrobenzene-1-ketone) etc. hexanaphthene-1, the 3-derovatives is as the selectivity herbicide after seedling.Withered reaching extremely gone up for No. 35314/78 open in No. the 464th, 655, Australian Patent and Australian patent application respectively with Sethoxydim.
By No. the 560th, 716, the Australian Patent (work such as watson, application number 27196/84) of ICI Australia company limited application, open on November 22nd, 1984, the following formula: compound with weeding activity is disclosed:
Wherein
R is the phenyl that replaces;
R
1Be H, alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthio alkyl, alkyl sulphonyl, alkoxyl group, alkylthio, acyl group, phenylalkyl or phSO that (not) replaces
2;
R
2Be alkyl, alkenyl, halogenated alkenyl, alkynyl, halo alkynyl, haloalkyl, alkoxyalkyl, the phenylalkyl that alkylthio alkyl or (not) replace; And
R
3Be alkyl, fluoroalkyl, alkenyl, alkynyl or phenyl.
People such as watson point out on 6 the tetrahydropyrans-2 that replaced by the phenyl of a replacement, and the 4-derovatives has useful especially weeding activity.
United States Patent (USP) No. 4008067 (announcement on February 15th, 1977) by people such as Hirono application discloses the following formula amylene oxide derivative with weeding activity.
Wherein:
R
1It is low alkyl group;
R
2Be low alkyl group, low-grade alkenyl or low-grade alkynyl;
A is
Wherein
R
3Be H or low alkyl group;
R
4Be low alkyl group or phenyl; Or
R
3With R
4Form the cycloalkenyl group of 4 to 5 carbon atoms together;
Or
Wherein
R
5And R
7Be selected from H and low alkyl group;
R
6It is low alkyl group;
Or
Wherein
R
8Be H or low alkyl group; And
R
9It is low alkyl group.
Above-claimed cpd can be replaced by one or two alkyl 5 and/or 6 of pyranoid ring.
By the applicant in the open WO8800945 of the International Patent Application PCT/AU 87/00236(international monopoly of on July 27th, 1887 application) and No. the 77583/87th, Australian patent application accordingly, No. the 87904820th, european patent application, No. the 504646th, Japanese patent application and U.S. Patent application disclose the following formula pyrone with weeding activity No. 4939278:
Wherein, partly,
R
1Be H;
R
2It is the substituted alkyl that replaces of the phenyl that is optionally substituted of alkyl and the heterocyclic radical that replaces arbitrarily wherein;
R
3It is alkyl;
R
4And R
5With coupled carbon form together replace or unsubstituted saturated or fractional saturation contain 3 or the heterocycle or the carbocyclic ring of more a plurality of annular atomses.This only is the concise and to the point guide look of relevant group.
Volution analogue above-mentioned is considered to a kind of preferred subgenus.R wherein further preferably
1Be H, R
2Be alkyl, alkenyl or halogenated alkenyl (particularly ethyl, allyl group, 2-chlorallyl and 3-chlorallyl) and R
3It is the compound of ethyl or n-propyl.
The table 1-4 of WO8800945 has listed 91 independent spirocyclic compounds, all R
2Only be ethyl, allyl group or chloro allyl group.Point out " The compounds of this invention is more more effective than anti-dicotyledons or wide leaf class aspect anti-monocotyledons or the careless class " at specification sheets 23A page or leaf.Though " have selective herbicidal activity aspect the weeds of some compound in anti-unifacial leaf farm crop and therefore can be used for weeds in the selective control gramineae farm crop " in the 23A of this specification sheets and 25 pages of also explanations, this application has emphasized that the weeds that disclosed compound is used for controlling wide leaf farm crop do not destroy wide leaf farm crop simultaneously.
International Patent Application PCT/the AU89/00191 of the applicant application has also described and the similar Herbicidal pyrones of those compounds described in the WO8800945, but they have an additional substituent R on pyranoid ring
6The compound of describing in PCT/AU89/00191 has general formula:
Substituent R wherein
1To R
5To describe among the WO8800945 similar, and
R
6Be selected from alkyl, alkoxyl group, alkylthio, halogen or substituted alkyl, wherein alkyl is selected from alkoxyl group, and the substituting group of alkylthio or halogen replaces.
The capping group R of preferred oxime
2Be alkyl, alkenyl, alkynyl and halogenated alkenyl; Particularly preferably be ethyl, propargyl, allyl group, 2-chlorallyl and 3-chlorallyl.
This specification sheets is pointed out " weeds that some compound of general formula 2 can be used for the selective control gramineous crop ".Yet do not specialize which kind of compound or the purposes on rice class crop.
The specification sheets of PCT/AU89/00191 comprises 15 embodiments relevant with Spirocyclic derivatives, but the capping group of listed oxime is defined as ethyl, allyl group or chloro allyl group.
International Patent Application PCT/the AU91/00019 that is proposed by the applicant is also claimed a series ofly to have optionally compound to the weeds in the rice, wherein capping group R
2Be:
R wherein
7, R
8And R
9Be H independently of one another, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl, C
1-C
4Halogenated alkoxy, nitro, cyano group, C
1-C
4Carbalkoxy, C
1-C
4Alkyl amino-carbonyl, C
2-C
6Dialkyl amino carbonyl, aminocarboxyl, phenyl, amino, C
1-C
4Alkylamino or C
2-C
6Dialkyl amido.
We have found that and International Patent Application WO 8800945 the similar wherein R of compound that describes among PCT/AU89/00191 and the PCT/AU91/00019
2Comprise that self is replaced arbitrarily by one, directly or by a little group such as methylene radical, the compound of the phenyl that phenyl replaced that oxygen or sulphur bridge connect is before high reactivity and the highly selective seedling and/or herbicide after seedling or plant-growth regulator, and they are used in particular for controlling some weeds in the rice of arid area and rice terrace.
Therefore, the invention provides logical formula I compound:
Wherein
A is arbitrarily by 1-4 C
1-C
3The C that alkyl substituent replaces arbitrarily
1-C
3Alkylidene group or C
1-C
3Alkylene group;
X is O, S, SO, SO
2, NR
10Or singly-bound;
R
1Be H, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
5-C
6Cycloalkyl, C
5-C
6Cycloalkenyl group, C
1-C
4Alkyl-carbonyl, phenylcarbonyl group at random is selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, nitro, cyano group, C
1-C
4Haloalkyl, amino and C
1-C
4The phenyl that the substituting group of halogenated alkoxy replaces, C
1-C
4Alkyl sulphonyl, phenyl sulfonyl, C
1-C
4Alkyl-carbonyl, C
2-C
8Alkoxyalkyl, C
2-C
8Alkylthio alkyl, C
7-C
10Phenylalkyl or M;
R
2Be C
1-C
6Alkyl, C
2-C
6Alkenyl, C
2-C
6Alkynyl, C
1-C
4Haloalkyl, C
1-C
4Alkylthio, C
3-C
6Cycloalkyl, C
5-C
6Cycloalkenyl group at random is selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkylthio, nitro, cyano group, C
1-C
4Haloalkyl, amino and C
1-C
4The phenyl that the substituting group of halogenated alkoxy replaces, C
2-C
8Alkoxyalkyl, C
2-C
8Alkylthio alkyl or quilt are selected from phenyl, the C that the substituting group of phenoxy group and sulfo-phenoxy group replaces
1-C
4Alkyl, wherein said substituent aromatic nucleus is selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, nitro, cyano group, amino, C
1-C
4Haloalkyl and C
1-C
4The substituting group of halogenated alkoxy replaces;
R
3And R
4Be H or C independently of one another
1-C
4Alkyl;
R
5And R
6Be H independently of one another, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
6Alkylthio alkyl, C
1-C
4Haloalkyl, C
2-C
4Halogenated alkenyl or C
3-C
6Cycloalkyl, alkyl wherein, alkenyl and cycloalkyl at random are selected from OR by 1-3
12, NR
13R
14, NR
15C(O) (C
1-C
4Alkyl), NR
18SO
2(C
1-C
4Alkyl), NR
21C(O) (C
1-C
4Alkyl), C(OR
16) (OR
17) R
22,
C(SR
19) (SR
20) R
23, C
1-C
4The substituting group of carbalkoxy and phenyl replaces, and phenyl wherein is selected from halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, nitro, cyano group, C
1-C
4Haloalkyl and C
1-C
4Halogenated alkoxy replaces; Or
R
5And R
6Can form saturated or undersaturated 3 to 7 yuan of carbocyclic rings fully with coupled carbon, or complete saturated the or undersaturated 1-3 of containing is selected from 0-3 nitrogen, heteroatomic 5 to 7 yuan of heterocycles of 0-2 oxygen and 0-2 sulphur atom; Said ring can be selected from halogen, C by 1-4
1-C
4Alkyl, C
1-C
4Haloalkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
1-C
4Alkyl-carbonyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Carbalkoxy ,-COOH, C
2-C
8Alkoxyalkyl, C
2-C
8The substituting group of alkylthio alkyl and phenyl replaces, and wherein phenyl can at random be selected from halogen, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Haloalkyl, nitro, cyano group and C
1-C
4The substituting group of halogenated alkoxy replaces; A carbon atom of said ring can be carbonyl or its corresponding dimethyl, the form of diethyl or ethylidene or propylidene ketal.
R
7, R
8And R
9Can be H independently, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl, C
1-C
4Halogenated alkoxy, nitro, cyano group, C
1-C
4Carbalkoxy, C
1-C
4Alkyl amino-carbonyl, C
2-C
6Dialkyl amino carbonyl, aminocarboxyl; Amino; C
1-C
4Alkylamino, C
2-C
6Alkylamino; Or phenyl sulfonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy group, thiophenyl, phenylamino or phenyl, said group at random are selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkoxyl group and CF
3Substituting group replace;
Condition is: work as R
5And R
6All be C independently
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
6Alkylthio alkyl, C
1-C
4Haloalkyl, C
2-C
4Halogenated alkenyl or at random be selected from C
1-C
4The C that the substituting group of carbalkoxy and substituted-phenyl replaces
3-C
6Cycloalkyl, wherein the substituting group on the phenyl is selected from halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, nitro, cyano group, C
1-C
4Haloalkyl and C
1-C
4Halogenated alkoxy, or work as R
5And R
6When saturated or unsaturated carbocyclic that common formation is optionally substituted or heterocycle, R
7, R
8Or R
9In at least one is the phenyl sulfonyl that is optionally substituted, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy group, thiophenyl or phenylamino, perhaps R
7, R
8Or R
9In at least one be selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkyl, C
1-C
4Alkoxyl group and CF
3The phenyl that replaces of substituting group;
R
10Be H, C
1-C
4Alkyl or at random be selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Haloalkyl and C
1-C
4The phenyl that the substituting group of halogenated alkoxy replaces;
M is Li
+, Na
+, K
+, NH
4 +, or N(R
11)
4 +, R wherein
11Be C
1-C
4Alkyl;
R
12Be H, C
1-C
4Alkyl, C(O) (C
1-C
4Alkyl) or CO
2(C
1-C
4Alkyl);
R
13, R
15, R
18, R
21, R
22And R
23Be H or C independently of one another
1-C
3Alkyl;
R
14, R
16, R
17, R
19And R
20Be C independently
1-C
3Alkyl;
R
16And R
17Can be together-(CH
2)
2-or-(CH
2)
3-; And
R
19And R
20Can be together-(CH
2)
2-or-(CH
2)
3-.
In the definition, the alkyl that uses separately or use in the compound speech as " alkylthio " or " haloalkyl " is meant the straight or branched alkyl in the above, as methyl, and ethyl, just-and propyl group, sec.-propyl or different butyl, amyl group or hexyl isomer.
Alkoxyl group is meant methoxyl group, oxyethyl group, just-propoxy-, isopropoxy and different butoxy isomer.
Alkenyl is meant straight or branched alkene, as vinyl, and 1-propenyl, 2-propenyl, 3-propenyl or the like.
Alkynyl is meant the straight or branched alkynyl, as ethynyl, and 1-proyl, 2-propynyl and different butynyl isomer.
Alkyl sulphonyl is meant methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base and different butyl alkylsulfonyl isomer.
Alkylthio, alkyl sulphinyl, alkylamino or the like defines by similar mode.
Cycloalkyl is meant cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl.
No matter be that halogen independent or in " haloalkyl " such compound is meant fluorine, chlorine, bromine or iodine.Furtherly, when the compound that is used for as " haloalkyl ", said alkyl can be by identical or different halogen atom part halo or is replaced fully.The example of haloalkyl comprises CH
2CH
2F, CF
2CF
3And CH
2CHFCl.
Alkyl-carbonyl is meant ethanoyl, propionyl and different butyryl radicals isomer.
Carbalkoxy is meant methoxycarbonyl, ethoxycarbonyl, the third oxygen carbonyl, different third oxygen carbonyl and different butoxy carbonyl isomer.
Carbonatomss all in the substituting group represent that with the Ci-Cj prefix wherein i and j are from 1 to 10 numbers.For example, C
2-C
3Alkylthio alkyl is represented-CH
2SCH
3,-CH
2SC
2H
5,-CH
2CH
2SCH
3Or-CH(CH
3) SCH
3, C
2-C
5Alkoxyalkyl representative-CH
2OCH
3To-(CH
2)
4OCH
3Or-CH
2O(CH
2)
3CH
3And the isomer of various structures is included.
Alkylidene group is meant methylene radical (CH
2-), ethylidene (CH
2CH
2-), propylidene and butylidene; Alkylene group refers to-CH=CHCH
2-,-CH=CHCH
2CH
2One and-CH
2CH=CHCH
2-.
We know and work as R
1The compounds of this invention can carry out tautomerism when being hydrogen.All tautomers all comprise within the scope of the invention.
In view of synthetic simplification and stronger herbicidal effect, the preferred group of logical formula I compound comprises as follows:
(1) logical formula I compound wherein
R
1Be H or M; And
R
2Be C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
2-C
4Alkenyl or C
2-C
4Alkynyl.
(2) 1 compound wherein above
A is arbitrarily by CH
3Or C
2H
5The C that replaces
1-C
2Alkylidene group or C
3-C
4Alkylene group;
R
7, R
8And R
9Be H independently of one another, Cl, Br, F, C
1-C
3Alkyl, C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Haloalkyl, C
1-C
3Halogenated alkoxy, nitro, cyano group or C
1-C
3Carbalkoxy; Or at random be selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkoxyl group or CF
3The benzenesulfonyl that replaces of substituting group, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl, thiophenyl or phenylamino;
Condition is: R
7, R
8Or R
9In at least one is the benzenesulfonyl that is optionally substituted, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl, thiophenyl or phenylamino; And
R
10Be H or CH
3
(3) above 2 compound wherein X be O.
(4) above 2 compound wherein X be S, SO or SO
2
(5) above 2 compound wherein X be NR
10
(6) above 2 compound wherein X be a singly-bound.
(7) 6 compound is wherein above:
A is-CH
2-,-CH
2CH
2-or-CH
2CH=CH-;
R
1Be H, Li
+, Na
+Or K
+;
R
2Be CH
3, C
2H
5, just-C
3H
7Or just-C
4H
9;
R
3And R
4Be H independently of one another, CH
3Or C
2H
5; And
R
7, R
8And R
9Be H independently of one another, Cl, Br, F, CH
3, C
2H
5, OCH
3, OC
2H
5, SCH
3, SC
2H
5, CF
3, CHF
2, CF
2CF
3, OCHF
2, OCF
3, OCH
2CF
3, NO
2, CN, CO
2CH
3, Ph, SO
2Ph, COPh, CH
2Ph, OCH
2Ph, OPh, SPh, NHPh or N(Me) Ph, condition is: R
7, R
8Or R
9In at least one is the benzenesulfonyl that is optionally substituted, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl, thiophenyl or phenylamino.
(8) 6 compounds R wherein above
5And R
6Be C independently of one another
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
1-C
4Alkylthio or C
2-C
6Alkylthio alkyl.
(9) 6 compounds R wherein above
5And R
6With connected carbon form together one saturated or unsaturated at random by 1-4 CH
35,6 or 7 yuan of carbocyclic rings that replace.
(10) 9 compound wherein above
A is-CH
2-,-CH
2CH
2-or-CH
2CH=CH-;
R
1Be H, Li
+, Na
+Or K
+;
R
2Be CH
3, C
2H
5, just-C
3H
7Or just-C
4H
9;
R
3And R
4Be H or CH independently of one another
3; And
R
7, R
8And R
9Be H independently of one another, Cl, Br, F, CH
3, C
2H
5, OCH
3, OC
2H
5, SCH
3, SC
2H
5, CF
3, CHF
2, CF
2CF
3, OCHF
2, OCF
3, OCH
2CF
3, NO
2, CN, CO
2CH
3, Ph, SO
2Ph, COPh, CH
2Ph, OCH
2Ph, OPh, SPh, NHPh or N(Me) Ph, condition is: R
7, R
8Or R
9In at least one be the benzenesulfonyl that is optionally substituted, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl, thiophenyl or phenylamino.
(11) 6 compounds wherein above
R
5And R
6Form the saturated or unsaturated 1-2 of containing together with connected carbon and be selected from 0-2 nitrogen, heteroatomic 5,6 or 7 yuan of heterocycles of 0-1 oxygen and 0-2 sulphur atom; Said ring is at random by 1-4 CH
3Replace.
(12) 11 compounds above, wherein
A is-CH
2-,-CH
2CH
2-or-CH
2CH=CH-;
R
1Be H, Li
+, Na
+Or K
+;
R
2Be CH
3, C
2H
5, just-C
3H
7Or just-C
4H
9;
R
3And R
4Be H independently of one another, CH
3Or C
2H
5; And
R
7, R
8And R
9Be H independently of one another, Cl, Br, F, CH
3, C
2H
5, OCH
3, OC
2H
5, SCH
3, SC
2H
5, CF
3, CHF
2, CF
2CF
3, OCHF
2, OCF
3, OCH
2CF
3, NO
2, CN, CO
2CH
3, Ph, SO
2Ph, COPh, CH
2Ph, OCH
2Ph, OPh, SPh, NHPh or N(Me) Ph, condition is: R
7, R
8Or R
9In at least one be the benzenesulfonyl that is optionally substituted, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl, thiophenyl or phenylamino.
In view of the strongest herbicidal effect, maximum selectivity acts on rice and/or the optimum simplification of synthetic, and particularly preferred compound is:
9-hydroxyl-8-(1-((3-(phenoxy group) phenyl) butyl methoxyimino))-and 6-oxaspiro (4,5) last of the ten Heavenly stems-8-alkene-7-ketone, its structural formula is:
8-(1-((4-(4-fluorophenyl) phenyl) butyl methoxyimino))-and 9-hydroxyl-6-oxaspiro (4,5) last of the ten Heavenly stems-8-alkene-7-ketone, its structural formula is:
9-hydroxyl-8-(1-((4-(phenyl) phenyl) butyl methoxyimino))-and 6-oxaspiro (4,5) last of the ten Heavenly stems-8-alkene-7-ketone, its structural formula is:
6,6-dimethyl-4-hydroxyl-3-(1-((4-(phenyl) phenyl) methoxyimino) butyl) pyran-2-one, its structural formula is:
And 6,6-dimethyl-3-(1-((4-(4-fluorophenyl) phenyl) methoxyimino) butyl)-4-hydroxyl pyran-2-one, its structural formula is:
The specific examples of the logical formula I compound of the present invention comprise those list in below compound among the table 1-4.Unless specify in table, X represents a singly-bound.
Table 1
R
9=H, the X=singly-bound
10
Compound n A R R
2R
3R
4R
7R
8
15
1.7 1 CH
2H Pr H H 3-NHPh H
20 1.8 1 CH
2H Pr H H 4-NHPh H
1.9 1 CH
2H Pr H H 3-NMePh H
1.10 1 CH
2H Pr H H 4-NMePh H
1.11 1 CH
2H Et H H 3-CH
2Ph H
25 1.13 1 CH
2H Pr Me H 3-CH
2Ph 4-F
1.15 1 CH
2Me Pr H H 3-CH
2Ph 4-Cl
1.17 1 CH
2H Pr H H 4-CH
2Ph H
30
1.19 1 CH
2H Pr Me Me 3-F 4-CH
2Ph
1.20 1 CH
2Me Pr H H 4-CH
2Ph H
5
1.31 1 CH
2H Et H H 3-OPh H
1.32 1 CH
2H Pr H H 3-OPh H
1.33 1 CH
2H Pr Me H 3-OPh H
1.34 1 CH
2Me Pr H H 3-（4-F）PhO H
10 1.35 1 CH
2H Pr Me Me 3-OPh H
1.36 1 CH
2Me Pr H H 3-OPh H
1.39 1 CH
2H Pr Me H 4-OPh H
15 1.40 1 CH
2H Pr Me Me 4-OPh H
1.41 1 CH
2Me Pr H H 4-OPh H
1.43 1 CH
2H Pr H H 3-SPh H
1.44 1 CH
2H Pr Me H 3-SPh H
20 1.45 1 CH
2H Pr Me Me 3-SPh H
1.46 1 CH
2Me Pr H H 3-SPh H
1.48 1 CH
2H Pr H H 4-SPh H
1.49 1 CH
2H Pr Me H 4-SPh H
25 1.50 1 CH
2H Pr Me Me 4-SPh H
1.51 1 CH
2Me Pr H H 4-SPh H
1.52 2 CH
2H Pr Me H 3-OPh H
1.53 2 CH
2H Pr H H 4-OPh H
1.54 2 CH
2H Pr Me H 3-OPh H
30 1.55 2 CH
2H Pr Me H 4-OPh H
1.56 3 CH
2H Pr H H 3-OPh H
1.57 1 CH
2H Me H H 4-Ph H
1.58 1 CH
2H Et H H 4-Ph H
1.59 1 CH
2H Pr H H 4-Ph H
35 1.60 1 CH
2H Pr H H 2-F 4-Ph
1.62 1 CH
2H Pr H H 4-F 3-Ph
1.63 1 CH
2H Pr H H 4-（4-F）Ph H
1.64 1 CH
2Me Pr H H 4-（4-F）Ph H
1.65 1 CH
2H Pr H H 4-（4-CN）Ph H
5
1.68 1 CH
2H Pr H H 4-（4-SO
2Me）Ph H
1.69 1 CH
2H Pr H H 3-（4-F）PhO H
1.70 1 CH
2H Pr H H 3-（4-CN）PhO H
1.71 1 CH
2H Pr H H 4-（4-CN）PhO H
10 1.72 1 CH
2H Pr H H 3-（4-CF3）PhO H
1.73 1 CH
2H Pr H H 3-（4-CF
3）PhO H
1.74 1 CH
2H Pr H H 3-（4-NO
2）PhO H
1.75 1 CH
2H Pr H H 4-（4-NO
2）PhO H
1.76 1 CH
2H Pr H H 3-（4-SO
2）PhO H
15 1.77 1 CH
2Me Pr H H 3-PhO H
1.78 1 CH
2H Pr Me H 2-Cl 3-Ph
1.79 1 CH
2H Pr Me H 4-Ph H
1.80 1 CH
2H Pr Me H 4-（4-F）Ph H
1.81 1 CH
2H Pr Me H 4-（4-CN）Ph H
20
1.84 1 CH
2H Pr Me H 3-（4-F）PhO H
1.85 1 CH
2H Pr Me H 3-（4-CN）PhO H
1.86 1 CH
2H Pr Me H 3-（4-CF
3）PhO H
25 1.87 1 CH
2H Pr Me Me 3-Ph H
1.88 1 CH
2H Pr Me Me 3-F 4-Ph
1.89 1 CH
2H Pr Me Me 4-（4-F）Ph H
1.90 1 CH
2H Pr Me Me 4-（4-CN）Ph H
30 1.92 1 CH
2H Pr Me Me 3-（4-F）PhO H
1.93 1 CH
2H Pr Me Me 3-（4-CN）PhO H
1.95 1 CH
2Me Pr H H 4-Ph H
1.96 1 CH
2Me Pr H H 4-（4-F）Ph H
35 1.97 2 CH
2Me Pr H H 4-（4-F）Ph H
1.98 2 CH
2H Pr H H 4-Ph H
1.99 2 CH
2Me Pr H H 4-Ph H
1.100 2 CH
2H Pr H H 4-（4-F）Ph H
1.102 2 CH
2H Pr H H 4-（4-CN）Ph H
5 1.104 2 CH
2H Pr H H 3-（4-SO2Me）Ph H
1.105 2 CH
2H Pr H H 3-（4-F）Ph H
1.106 2 CH
2H Pr H H 3-（4-CN）PhO H
1.107 2 CH
2H Pr H H 4-（4-CN）PhO H
1.108 2 CH
2H Pr Me H 4-Ph H
10 1.109 2 CH
2H Pr H H 3-（4-CF
3）PhO H
1.110 2 CH
2H Pr Me Me 4-（4-F）Ph H
1.111 3 CH
2H Pr H H 4-Ph H
1.112 3 CH
2H Pr Me H Ph H
1.113 3 CH
2H Pr H H 4-（4-F）Ph H
15 1.114 3 CH
2H Pr H H 4-（4-CN）Ph H
1.116 3 CH
2H Pr H H 3-（4-F）PhO H
Table 2
R
9=H, the X=singly-bound
10Compd A R
2R
3R
4R
7R
8
2.1 CH
2Pr Me H 3-OPh H
2.2 CH
2Et H H 4-Ph H
2.3 CH
2Pr H H 3-Ph H
15 2.4 CH
2Pr H H 4-Ph H
2.5 CH
2Et Me H 4-Ph H
2.6 CH
2Pr Me H 3-Ph H
2.7 CH
2Pr Me H 4-Ph H
2.8 CH
2Pr Me Me 3-Ph H
20 2.9 CH
2Pr Me Me 4-Ph H
Table 3
5
R
9=H, the X=singly-bound
Compd A R
2R
3R
4R
5R
6R
7R
8
3.1 CH2 Pr H H Me Me 3-NHPh H
10 3.2 CH
2Pr H H Me Me 4-NMePh H
3.4 CH
2Pr H H Me Et 3-CH
2Ph H
3.6 CH
2Pr H H Me Me 4-CH
2Ph H
15
3.8 CH
2Pr H H Me iso-Pr 4-CH
2Ph H
20
3.15 CH
2Et H H Me Me 3-OPh H
3.16 CH
2Pr H H Me Me 3-OPh H
25 3.17 CH
2Pr H H Me Et 3-OPh H
3.18 CH
2Pr H H Me iso-Pr 3-OPh H
3.19 CH
2Pr H H Me Me 4-OPh H
3.20 CH
2Pr H H Me Et 4-OPh H
3.21 CH
2Pr H H Me iso-Pr 4-OPh H
30
35
3.28 CH
2Pr H H Me H 4-Ph H
3.29 CH
2Pr H H Me H 4-（4-Ph）Ph H
3.30 CH
2Pr H H Me H 4-（4-F）Ph H
3.31 CH
2Pr H H Me H 4-（4-CN）Ph H
5 3.34 CH
2Pr H H Me H 3-（4-FPh）O H
3.35 CH
2Pr H H Me H 3-（4-CN）PhO H
3.36 CH
2Pr H H Me H 3-（4-CF
3）PhO H
3.37 CH
2Pr H H Et H 4-Ph H
3.38 CH
2Pr H H Et H 4-（4-Ph）Ph H
10 3.39 CH
2Pr H H Et H 4-（4-F）Ph H
3.40 CH
2Pr H H Et H 4-（4-CN）Ph H
3.43 CH
2Pr H H Et H 3-（4-F）PhO H
15 3.44 CH
2Pr H H Et H 3-（4-CN）PhO H
3.45 CH
2Pr H H Et H 3-（4-CF
3）PhO H
3.46 CH
2Pr H H Pr H 4-Ph H
3.47 CH
2Pr H H Pr H 4-（4-F）Ph H
3.48 CH
2Pr H H Pr H 4-（4-CN）Ph H
20
3.51 CH
2Pr H H Pr H 3-（4-F）PhO H
3.52 CH
2Pr H H Pr H 3-（4-CN）PhO H
3.53 CH
2Pr H H Pr H 3-（4-CF
3）PhO H
25 3.54 CH
2Pr H H isoPr H 4-Ph H
3.55 CH
2Pr H H isoPr H 4-（4-F）Ph H
3.56 CH
2Pr H H isoPr H 4-（4-CN）Ph H
30 3.59 CH
2Pr H H isoPr H 3-（4-F）PhO H
3.60 CH
2Pr H H isoPr H 3-（4-CN）PhO H
3.61 CH
2Pr H H isoPr H 3-（4-CF
3）PhO H
3.62 CH
2Pr H H s-Bu H 4-Ph H
3.63 CH
2Pr H H s-Bu H 4-（4-F）Ph H
35 3.64 CH
2Pr H H t-Bu H 4-Ph H
3.65 CH
2Pr H H t-Bu H 4-（4-F）Ph H
3.66 CH
2Me H H Me Me 4-Ph H
3.67 CH
2Pr H H Me Me 3-Ph H
3.68 CH
2Pr H H Me Me 4-Ph H
3.69 CH
2Pr H H Me Me 2-F 4-Ph
3.70 CH
2Pr H H Me Me 3-F 4-Ph
5 3.71 CH
2Pr H H Me Me 4-F 3-Ph
3.72 CH
2Pr H H Me Me 4-Ph H
3.73 CH
2Pr H H Me Me 4-（4-Ph）Ph H
3.74 CH
2Pr H H Me Me 4-（4-F）Ph H
3.75 CH
2Pr H H Me Me 4-（4-CN）Ph H
10
3.78 CH
2Pr H H Me Me 4-（4-SO
2Me）Ph H
3.79 CH
2Pr H H Me Me 3-（4-F）PhO H
3.80 CH
2Pr H H Me Me 3-（4-CN）PhO H
15 3.81 CH
2Pr H H Me Me 3-（4-CF
3）PhO H
3.82 CH
2Pr H H Me CF
34-Ph H
3.83 CH
2Pr H H Me CF
34-（4-Ph）Ph H
3.84 CH
2Pr H H Me Et 4-Ph H
3.85 CH
2Pr H H Me Et 4-（4-Ph）Ph H
20 3.86 CH
2Pr H H Me Et 4-（4-F）Ph H
3.87 CH
2Pr H H Me Et 4-（4-CN）Ph H
3.90 CH
2Pr H H Me Et 4-（4-SO
2Me）Ph H
25 3.91 CH
2Pr H H Me Et 3-（4-F）PhO H
3.92 CH
2Pr H H Me Et 3-（4-CN）PhO H
3.94 CH
2Pr H Me isoPr H 4-Ph H
3.95 CH
2Pr H Me isoPr H 4-（4-F）Ph H
30 3.96 CH
2Pr H Me isoPr H 4-（4-CN）Ph H
3.99 CH
2Pr H Me isoPr H 3-（4-F）PhO H
3.100 CH
2Pr H Me isoPr H 3-（4-CN）PhO H
35 3.101 CH
2Pr H Me isoPr H 4-（4-CF
3）PhO H
3.102 CH
2Pr Me H Me Me 4-Ph H
3.103 CH
2Me H H Me Me 4-（4-F）Ph H
3.104 CH
2Me Me H Me Me 4-（4-F）Ph H
3.105 CH
2Pr Me H Me Et 4-Ph H
3.106 CH
2Pr Me H Me Et 4-（4-F）Ph H
3.107 CH
2Pr Me H Me iso-Pr 4-Ph H
5 3.108 CH
2Pr Me H Me iso-Pr 4-（4-F）Ph H
3.109 CH
2Pr Me Me Me Me 4-Ph H
3.110 CH
2Me Me Me Me Me 4-（4-F）Ph H
3.111 CH
2Pr Me Me Me Me 4-（4-F）Ph H
3.112 CH
2Pr Me Me Me Me 3-（4-F）PhO H
10 3.113 CH
2Pr Me Me Me Et 4-Ph H
3.114 CH
2Pr Me Me Me iso-Pr 4-Ph H
3.115 CH
2Pr H H CH
2OMe H 4-Ph H
3.116 CH
2Pr H H CH
2OMe H 4-（4-F）Ph H
3.117 CH
2Pr H H CH
2OMe H 3-（4-F）PhO H
15 3.118 CH
2Pr H H CH
2OEt H 4-Ph H
3.119 CH
2Pr H H CH
2OEt H 4-（4-F）Ph H
3.120 CH
2Pr H H CH
2OPh H 4-Ph H
3.121 CH
2Pr H H CH
2OPh H 4-（4-F）Ph H
3.122 CH
2Pr H H Me CH（OMe）
24-Ph H
20 3.123 CH
2Pr H H Me CH（OMe）
24-（4-F）Ph H
3.124 CH
2Pr H H Me CH（OMe）
23-PhO H
3.125 CH
2Pr H H Me CH（OMe）
23-（4-F）PhO H
3.126 CH
2Pr H H Me CH（OMe）
24-（4-CN）PhO H
3.127 CH
2Pr H H Me CH（OEt）
24-Ph H
25 3.128 CH
2Pr H H Me CH（OEt）
24-（4-F）Ph H
3.129 CH
2Pr H H CH
2CH
2OMe H 4-Ph H
3.130 CH
2Pr H H CH
2CH
2OMe H 4-（4-F）Ph H
3.131 CH
2Pr H H CH
2CH
2OEt H 4-Ph H
3.132 CH
2Pr H H CH
2CH
2OEt H 4-（4-F）Ph H
30 3.133 CH
2Pr H H CH
2CH
2OCH
2CH＝CH
2
H 4-Ph H
3.134 CH
2Pr H H CH
2CH
2OCH
2CH＝CH
2
H 4-（4-F）Ph H
3.135 CH
2Pr H H CH
2CH
2OPh H 4-Ph H
35 3.136 CH
2Pr H H CH
2CH
2OPh H 4-（4-F）Ph H
Table 4
R
9＝H，X＝-
10Compound n A R2 R3 R4 R7 R8
4.1 1 CH
2Pr H H 3-Ph H
4.2 1 CH
2Pr H H 4-Ph H
15 4.3 1 CH
2Pr Me H 3-Ph H
4.4 1 CH
2Pr Me H 4-Ph H
4.5 2 CH
2Pr H H 3-Ph H
4.6 2 CH
2Pr H H 4-Ph H
4.7 2 CH
2Pr Me H 3-Ph H
20 4.8 2 CH
2Pr Me H 4-Ph H
4.9 1 CH
2Me H H 4-Ph H
4.10 1 CH
2Pr H H 4-Ph H
4.11 1 CH
2Pr H H 4-（4-F）Ph H
4.12 1 CH
2Pr H H 2-F 4-Ph
25 4.13 1 CH
2Pr H H 3-F 4-Ph
4.14 1 CH
2Pr H H 4-F 3-Ph
4.15 1 CH
2Pr H H 4-（4-CN）Ph H
30 4.18 1 CH
2Pr H H 4-（4-SO
2Me）Ph H
4.19 1 CH
2Pr H H 4-（4-F）Ph H
4.20 1 CH
2Pr H H 3-PhO H
4.21 1 CH
2Pr H H 3（4-CN）PhO H
4.22 1 CH
2Pr Me H 4-Ph H
35 4.23 1 CH
2Pr Me H 4-（4-F）Ph H
4.24 2 CH
2Pr H H 4-Ph H
4.25 2 CH
2Me H H 4-（4-F）Ph H
4.26 2 CH
2Pr H H 4-（4-F）Ph H
4.28 2 CH
2Pr H H 4-（4-CN）Ph H
5 4.30 2 CH
2Pr H H 3-PhO H
4.31 2 CH
2Pr Me H 4-（4-F）Ph H
4.32 2 CH
2Pr Me H 4-（4-CN）Ph H
10 4.35 2 CH
2Pr Me H 3-（4-F）PhO H
4.36 2 CH
2Pr Me Me 4-（4-F）Ph H
4.37 2 CH
2Pr Me Me 4-（4-CN）Ph H
4.39 2 CH
2Pr Me Me 3-（4-F）PhO H
15 4.40 3 CH
2Pr H H 4-Ph H
4.41 3 CH
2Pr H H 4-（4-F）Ph H
The compounds of this invention can use with WO8800945 in disclosed similar methods, with appropriate change initial reagent prepared.For example, The compounds of this invention can by with a kind of dianion of acetylacetic ester with a kind of suitable ketone condensation (with reference to Hukin, S.N., and Weller, L.Can J Chem, 1974.52,2157), in the intermediate hydrolysis or do not have that cyclisation obtains new tetrahydrochysene-2H-pyrans-2 under the situation of hydrolysis, the 4-diketone prepares then.Pyrans diketone or its tautomeric 4-hydroxyl-5,6-dihydro-2H-pyran-2-one Equivalent also can be obtained by the ordinary method of describing in the document.Can with obtain like this 6,6-two substituted pyranes 2,4-diketone carry out acidylate and obtain new C-substitution product on the enol ester of oxygen and isomerization (Fries. rearrangement).The C-acylated derivatives can obtain R with the O-substituted hydroxylamine reaction that produces successively on the spot from suitable precursor
1It is the derivative of the logical formula I of hydrogen.
R
1The logical formula I compound of the present invention that is not hydrogen can make with the standard synthetic method.For example, R
1Be that the logical formula I compound of the cationic the present invention of organic or inorganic can be from R
1The logical formula I compound of the present invention that is hydrogen makes by itself and suitable inorganic or organic bases are reacted.
R
1Be that the esterification of vinylogy acid further provides weeding and growth regulating derivative in the logical formula I compound of the present invention of hydrogen.
The universal method of preparation The compounds of this invention part is below described in detail.
The general preparation method of The compounds of this invention.
(a) pyrans-2,4-diketone synthetic
In nitrogen atmosphere and be chilled under 0 ℃ of situation, sodium salt (about 55mmol to (alkyl) acetylacetic ester that stirs, can prepared beforehand or on the spot from (alkyl) acetylacetic ester (55mmol) and sodium hydride (55mmol) according to Huckin, S.N. and Weiler, L.Can.J.Chem., 1974,52,2157 method makes) in the solution of anhydrous tetrahydro furan (50ml), drip n-butyllithium solution (21.2ml, the hexane solution of 2.6M, 55mmol).After 1 hour, stirred 120 minutes down, then it is used methyl alcohol (2.4ml, 60mmol) quenching with suitable ketone (50mmol) (before adding solid ketone being dissolved in the tetrahydrofuran (THF)) treating mixture and at 0 ℃.After further adding methyl alcohol (20ml) and water (10ml) (and in acid that certain exemplifies) mixture was seethed with excitement about 30 minutes, further water (40ml) dilution also under reduced pressure concentrates (to about 40ml) then.Cooling also adds that (2 * 100ml) extract with ether with mixture after the entry (about 150ml).Ether extraction liquid is washed with water (50ml); And the water-soluble liquid phase that will merge is acidified to pH1-2 with concentrated hydrochloric acid, uses extracted with diethyl ether (100ml) then.(in this step of some reactions, first pyrans diketone crystallizes out in diethyl ether solution, it is filtered collect).Remove from reaction mixture with ethanol/benzene and benzene successively by component distillation with the diethyl ether solution evaporation and with resistates then.Resistates is carried out chromatography (SiO
2, methylene dichloride) or in some example,, with the method for vigorous stirring the pyrans diketone is carried out crystallization then by carefully the dense benzole soln (about 20ml) of resistates being diluted to very little turbidity with hexanaphthene.When crystallization begins, mixture is used more hexanaphthene (about 20ml) dilution carefully and continued stirring 4 hours, collecting precipitation also obtains the pyrans diketone with hexanaphthene/benzene (4: 1) washing then.
Method B:
((15.6ml is in tetrahydrofuran (THF) 111mmol) (50ml) solution 110mmol) to join the diisopropylamine that remains on 0 ℃ of stirring for 45ml, the hexane solution of 2.45M with n-butyllithium solution under argon atmospher.At room temperature continue to stir 15 minutes; Then with mixture quenching in ice.Add (alkyl) acetylacetic ester (52.5mmol) then and the gained mixture is descended stirring 30 minutes at 0 ℃, again to wherein adding a kind of suitable ketone (50mmol, be dissolved in the tetrahydrofuran (THF) of minimum to form homogeneous solution) and continue to stir 90 minutes (or lose lustre to light orange look or yellow until reaction mixture), use methyl alcohol (4.8ml, 120mmol) quenching then.Then reaction mixture is handled by method A and obtained the pyrans diketone.
(b) acidylate of pyrans diketone
To 0 ℃ of pyrans diketone (6.10mmol) and DBU (1 that also stirs, 8-diazabicylo (5.4.0)-7-undecylene) (0.99g, 6.5mmol) toluene (20ml) solution in add suitable acyl chlorides (6.6mmol) and mixture stirred 2 hours down at 0 ℃, at room temperature stirred then 24 hours.Water (50ml) and toluene (30ml) dilute and shake mixture and obtains orange form and aspect, and it is rapid in 5% salt acid elution, dry (using sodium sulfate) and vacuum-evaporation.With resistates and 4-Dimethylamino pyridine (40mg, 0.3mmol) in toluene (10ml) 3 hours (or till thin-layer chromatography shows that reaction has been finished) of reflux then vacuum remove toluene and with resistates chromatography (SiO
2, methylene dichloride: sherwood oil (b.p.40-60 ℃): ethyl acetate (4: 4: 1)) obtain the C-acylated compounds.
(c) oximate of acylated compounds
With C-acylated compounds (3.75mmol), suitable O-substituted hydroxylamine hydrochloride (4.00mmol), triethylamine (0.41g, 4.0mmol) and the mixture of methyl alcohol (5ml) at room temperature stirred 48 hours, then with in its impouring water (50ml).With 5M hydrochloric acid mixture is acidified to pH4, with diethyl ether or ethyl acetate extraction (2 * 50ml), with organic phase evaporation and chromatography (SiO
2, methylene dichloride or methylene dichloride: sherwood oil (b.p.40-60 ℃): ethyl acetate (4: 4: 1)) resistates obtains the present invention's (I) examples for compounds.
The activity of The compounds of this invention.
Test-results shows that The compounds of this invention is before the highly active seedling and/or herbicide after seedling or plant-growth regulator.These compounds are used in particular for controlling some grass and the width leaf weed in nonirrigated farmland and the rice terrace, and these examples include, but are not limited to Indica and the various farm crop of japonica.Chemical compound lot of the present invention is used in particular for controlling some selectivity weeds in the paddy rice field, as barnyard grass (Echinochloa crusgalli).
Suitable using under the ratio, these compounds also can be used for before the geographic wide spectrum seedling that all plant-growths all need control and/or the control of weeds behind the seedling.In addition, these compounds can be used for coordinate plant growth.
The ratio that The compounds of this invention is used is determined by many factors.These factors comprise dosage form selection, the method for using, the amount of plant, growth conditions or the like.Generally speaking, the purpose compound should be with 0.05 to 10kg/ha, and preferred 0.1 to 2kg/ha ratio is used.Those skilled in the art can determine to use ratio according to desirable weeds controlled levels at an easy rate.
The compounds of this invention can use separately or with other commodity weedicide, sterilant or mycocide are united use.The catalogue of these commodity compounds provides in the appendix A of the PCT/AU91/00019 of the present invention's document incorporated by reference.Therefore, further specific embodiments the invention provides the herbicidal composition of the mixture of the herbicidal compound that comprises at least a logical formula I as defined above and at least a other weedicide.
Specific embodiment further the invention provides the method for coordinate plant growth that the growth medium that comprises to the seed of plant, plant or plant imposes the defined above logical formula I compound of significant quantity.
The ratio of using of these compounds also should be determined according to real working conditions by many Effect of Environmental.When usefulness was less than 0.1 to about 20kg active ingredient/ha rate process, the weeds in the gramineous crop can be killed.
The compounds of this invention can mix with the shortest time of usefulness with mycocide, sterilant, miticide, nematocides, sterilant or other bioactive compounds, minimum effort, and minimum material is obtained required result.The amount that these biologically active substances join in the present composition of every part of weight can be 0.05 to 25 part of weight.This type of suitable reagent is well known to a person skilled in the art.
Preparation
The useful preparation of the compound that is included in the scope of the present invention can prepare according to a conventional method.They comprise pulvis, granule, pill, solution, emulsion, wettable powder, emulsification enriched material or the like.Wherein many can directly the use.Sprayable preparation can be dispersed in the suitable medium and be raised to the sprinkling volume use of several hectolitres with per hectare 1.The high strength composition at first is used as the intermediate of further preparation.Said preparation includes the active ingredient of about 1% to 99% weight and at least a (a) about tensio-active agent of 0.1% to 20% and (b) about 5% to 99% solid-state or liquid inert diluent in very wide scope.Particularly, they contain these compositions with following proximate ratio:
Weight percent
Active ingredient thinner tensio-active agent
Wettable powder 20-90 0-74 1-10
Oily suspension, emulsion, 5-50 40-95 0-15
Solution (but comprises emulsification
Enriched material)
Aqueous suspension 10-50 40-84 1-20
Pulvis 1-25 70-99 0-5
Granule and pill 1-95 5-99 0-15
High strength composition 90-99 0-10 0-2
The active ingredient of lower or higher level can be provided according to the physical properties of application target and compound certainly.Usually tensio-active agent is higher to the ratio of active ingredient is ideal, and they can obtain by being mixed into to mix in preparation or the container.
Composition can be powder or the particle that comprises active ingredient and solid diluent or carrier (as kaolin, bentonite, diatomite, rhombspar, lime carbonate, talcum, magnesium powder, Fuller's earth, gypsum, Hewitt soil, diatomite and potter's clay).Composition also can be dispersible powder or the particulate that comprises wetting agent, and wetting agent wherein can conveniently be diffused into and contain solid diluent, in the powder of weighting agent and suspension agent or the liquid of particulate.
People such as typical solid thinner such as Watkins work " Handbook of Insecticide Dust Diluents and Carriers ", 2nd Ed., Dorland Books, Caldwell, N.J. is described.Wettable powder preferably has better absorbefacient thinner, and pulvis is preferably than the heavy-gravity thinner.All preparations can contain a small amount of additive to reduce foam, caking, corrosion, microbial growth etc.The composition that is applied to seed for example can contain a kind of reagent (as mineral oil) and invest on the seed to help composition.
The dispersion or the emulsion aqueous solution can by active ingredient is dissolved in contain wetting, disperse or the organic solvent of emulsification reagent in then mixture is joined also contain wetting, disperse or the water of emulsification reagent in prepare.Suitable solvent has acetone, ethylene dichloride, Virahol, propylene glycol, Pyranton, toluene, kerosene, methylnaphthalene, dimethylbenzene and trieline and other.Solubleness 0.1% below better for suspending concentrate; The solution concentration thing can be very stable and be not separated at 0 ℃." McCutcheon ' S Detergents and Emulsifiers Annual ", MC Publishing Corp., Ridgewood, N.J., and Sisely and Wood, " Encyclopedia of Surface Actiye Agents ", Chemical Publishing Co.Inc., New York, 1964, listed the purposes of tensio-active agent and recommendation.
It is known preparing these method for compositions.Solution can be by mixed with various compositions simply.Meticulous solids composition can make by fusion and grinding in hammer or in the active mill of fluid.Suspension makes by wet-milling (sees Littler, U.S.Pat.No.3060084).Particle and pill make by active substance is sprayed on the ready particulate vector or by agglomeration technique.
Synthesizing of The compounds of this invention further by following embodiment explanation.
Embodiment 1(compound 1.32)
9-hydroxyl-8-(1-(3-(benzene oxygen) phenyl) butyl methoxyimino))-preparation of 6-oxaspiro (4.5) last of the ten Heavenly stems-8-alkene-7-ketone
To at the O-(3-(of 20 ℃ of stirrings benzene oxygen) phenyl) add 8-butynyl-6-oxaspiro (4.5) last of the ten Heavenly stems-7,9-diketone (0.48g) in methyl hydroxylamine hydrochloride (0.63g) and the mixture of triethylamine (0.25g) in ethanol (10.0ml).20 ℃ transfer 24 hours after, with mixture water (100ml) dilution, extract to pH3 and with diethyl ether with the 5N hcl acidifying.Evaporate organic phase and resistates obtained lark oily product (0.41g) by silica gel column chromatography,
1H n.m.r. δ (CDCl
3) 0.97, wide t, J7Hz, CH
3; 1.2-2.4, m, 10H, cyclopentyl and CH
2CH
3; 2.65, s, COCH
22.94, wide t, J8Hz, CH
2CH
2CH
3; 4.98, s, OCH
2And 7.0-7.5, s, fragrant H.
Other compound of the present invention is by the logical method preparation that provides above, and their feature is by their proton nmr spectrum and fusing point (if solid) expression.Select following the providing of physical data of compound.
Compound 1.31: pale yellow oily matter,
1H n.m.r. δ (CDCl
3) 1.12, t, J7Hz, CH
3; 1.4-2.2 m encircles penta H; 2.65, s, COCH
2; 2.9, q, J7Hz, CH
2CH
3; 4.98, s, OCH
2And 6.9-7.4, m.ArH compound 1.33: colorless oil,
1H n.m.r. δ (CDCl
3) 0.92, t, J7Hz, CH
2CH
3; 1.15, d, J6Hz, CHCH
3; 1.3-2.1 m encircles penta H and CH
2CH
2CH
3; 2.42, q, J6Hz; CHCH
3; 2.85-3,2, m, CH
2CH
2CH
3; 4.98, s, OCH
2And 6.8-7.4, m, ArH
Compound 1.34: pale yellow oily matter,
1H n.m.r. δ (CDCl
3) 0.95, t, J7Hz, CH
3; 1.4-2.2 m encircles penta H and CH
2CH
2CH
3; 2.64, s, COCH
2; 2.96, q, J7Hz, CH
2CH
3; 4.98, s, OCH
2And 7.0-7.5, m, ArH
Compound 1.52 yellow oil.
1H n.m.r. δ (CDCl
3) 0.92, t, J7Hz, CH
2CH
3; 1.15, d, J6Hz, CHCH
3; 1.2-2.0, m, hexamethylene H and CH
2CH
2CH
3; 2.40, q, J6Hz; CHCH
3; 2.87, t, J7Hz, CH
2CH
2CH
3; 4.88, s, OCH
2And 6.8-7.3, m, ArH
Compound 1.56 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.92, t, J7Hz CH
2CH
3; 1.1-2.1, m, ring H in heptan and CH
2CH
2CH
3; 2.51, s, OCH
2; 2.91, t, J7Hz, CH
2CH
2CH
3; 4.88, s, OCH
2And 6.8-7.4, m, ArH
Compound 1.59 m.p.70,
1H n.m.r. δ (CDCl
3) 0.93, t, J7Hz, CH
3; 1.2-2.0 m encircles penta H and CH
2CH
2CH
3; 2.65, s, COCH
2; 2.93, q, J7Hz, CH
2CH
2CH
3; 5.06, s, OCH
2And 7.2-7.7, m, ArH
Compound 1.63 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.88, t, J7Hz, CH
3; 1.3-2.1 m encircles penta nt.H and CH
2CH
3; 2.62, s, COCH
2; 2.92, q, J7Hz, CH
2CH
2CH
3; 5.02, s, OCH
2And 6.9-7.7, m, ArH
Compound 1.66 light yellow oil
1H n.m.r. δ (CDCl
3) 0.94, t, J7Hz.CH
3; 1.5-2.1 m encircles penta H and CH
2CH
3; 2.62, s, COCH
2; 2.94, q, J7Hz, CH
2CH
2CH
3; 5.08, s, OCH
2And 7.1-7.7, m, ArH
Compound 1.70 m.p.100,
1H n.m.r. δ (CDCl
3) 0.83, t, J7Hz, CH
3; 1.3-2.1 m encircles penta H and CH
2CH
3; 2.62, s, COCH
2; 2.94, q, J7Hz, CH
2CH
2CH
3; 5.14, s, OCH
2And 6.7-7.6, m, ArH
Compound 1.77 colorless oil,
1H n.m.r. δ (CDCl
3) 0.80-1.1, m, 2xCH
3; 1.2-2.2 m encircles penta ent H and CH
2CH
2CH
3; 2.61, s, COCH
2; 2.94, q, J7Hz, CH
2CH
2CH
3; 5.06, s, OCH
2And 6.9-7.4, m, ArH
Compound 1.79 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.92, t, J7Hz.CH
2CH
3; 1.14, d, J6Hz, CHCH
3; 1.3-2.1 m encircles penta H and CH
2CH
2CH
3; 2.36, q, J6Hz; CHCH
3; 2.80-3.15, m, CH
2CH
2CH
3; 5.06, s, OCH
2And 7.2-7.7, m, ArH
Compound 1.80 m.p.69,
1H n.m.r. δ (CDCl
3) 0.97, t, J7Hz.CH
2CH
3; 1.25, d, J6Hz, CHCH
3; 1.4-2.1 m encircles penta H and CH
2CH
2CH
3; 2.42, q, J6Hz; CHCH
3; 2.85-3.1, m, CH
2CH
2CH
3; 5.05, s, OCH
2And 7.1-7.65, m, ArH
Compound 1.89 m.p.109,
1H n.m.r. δ (CDCl
3) 0.92, t, J7Hz, CH
2CH
3; 1.2, s, 2xCH
3; 1.3-2.0 m encircles penta H and CH
2CH
2CH
3; 3.0, t, J7Hz, CH
2CH
2CH
3; 5.08, s, OCH
2And 7.0-7.7, m, ArH
Compound 1.95 light yellow oil,
1H n.m.r.v(CDCl
3) 0.8-1.1, m, CH
2CH
3And CHCH
3; 1.4-2.3 m encircles penta H, CH
2CH
2CH
3And CHCH
3; 2.85-3.2, m, CH
2CH
2CH
3; 5.07, s, OCH
2And 7.2-7.8, m, ArH
Compound 1.97 m.p.57,
1H n.m.r. δ (CDCl
3) 0.8-1.1, m, CH
2CH
3And CHCH
3; 1.3-2.1, m, hexamethylene H, CH
2CH
2CH
3And CHCH
3; 2.68, s, COCH
2; 3.0, t, J7Hz, CH
2CH
2CH
3; 5.08, s, OCH
2And 6.9-7.7, m, ArH
Compound 1.98 m.p.61,
1H n.m.r. δ (CDCl
3) 0.96, t, J7Hz, CH
3; 1.1-2.0, m, hexamethylene H and CH
2CH
2CH
3; 2.52, s, COCH
2; 3.0, q, J7Hz, CH
2CH
2CH
3; 5.03, s, OCH
2And 7.2-7.7, m, ArH
Compound 1.99 m.p.107,
1H n.m.r. δ (CDCl
3) 0.8-1.1, m, CH
2CH
3And CHCH
3; 1.2-2.2, m, hexamethylene H, CH
2CH
2CH
3And CHCH
3; 2.50, s, COCH
2; 2.97, t, J7Hz, CH
2CH
2CH
3; 5.05, s, OCH
2And 7.2-7.7, m, ArH
Compound 1.100 m.p.78,
1H n.m.r. δ (CDCl
3) 0.95, t, J7Hz, CH
3; 1.1-2.0, m, hexamethylene H and CH
2CH
2CH
3; 2.53, s, COCH
2; 3.04, q, J7Hz, CH
2CH
2CH
3; 5.06, s, OCH
2And 6.9-7.7, m, ArH
Compound 1.111 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.96, t, J7Hz, CH
3; 1.2-2.0, m, ring H in heptan and CH
2CH
2CH
3; 2.51, wide s, COCH
2; 2.98, t, J7Hz, CH
2CH
2CH
3; 5.03, s, OCH
2And 6.9-7.7, m, ArH
Compound 1.112 colorless oil,
1H n.m.r. δ (CDCl
3) 0.98, t, J7Hz, CH
2CH
2CH
3; 1.16, d, J6Hz, CHCH
3; 1.3-2.1m, ring H in heptan and CH
2CH
2CH
3; 2.41, q, J6Hz, CHCH
3; 2.98, t, J7Hz, CH
2CH
2CH
3; 5.09, s, OCH
2And 7.3-7.8, m, ArH
Compound 1.113 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.96, t, J7Hz CH
3; 1.2-2.1, m, ring H in heptan and CH
2CH
2CH
3; 2.51, wide s, COCH
2; 2.98, q, J7Hz, CH
2CH
2CH
3; 5.03, s, OCH
2And 6.9-7.7, m, ArH.
Compound 3.16 colorless oil,
1H n.m.r. δ (CDCl
3) 0.92, t, J7Hz, CH
3; 1.46s, 2xCH
3; 2.56, s, COCH
2; 2.95, q, J7Hz, CH
2CH
2CH
3; 5.02, s, OCH
2And 6.9-7.4, m, ArH
Compound 3.25 m.p.61,
1H n.m.r. δ (CDCl
3) 0.95, t, J7Hz.CH
3; 1.44, s, 2xCH
3; 1.6-2.1 m encircles penta H and CH
2CH
3; 2.56, s, COCH
2; 3.0, q, J7Hz, CH
2CH
2CH
3; 4.8, wide s, OCH; 5.02, s, OCH
2And 6.8-7.4, m, ArH
Compound 3.64 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.94, t, J7Hz, CH
3; 0.97, s, 3xCH
3; 1.4-3.1, m, CH
2CH
2CH
3And COCH
2; 5.06, s, OCH
2And 7.2-7.7, m, ArH
Compound 3.66 m.p.96,
1H n.m.r. δ (CDCl
3) 0.91, t, J7Hz, CH
3; 1.42, s, 2xCH
3; 1.4-1.8, m, CH
2CH
3; 2.51, s, COCH
2; 3.02, q, J7Hz, CH
2CH
2CH
3; 5.04, s, OCH
2And 7.3-7.7, m, ArH
Compound 3.67 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.98, t, J7Hz, CH
3; 1.42, s, 2xCH
3; 1.4-1.8, m, CH
2CH
3; 2.52, s, COCH
2; 3.02, q, J7Hz, CH
2CH
2CH
3; 5.08, s, OCH
2And 7.3-7.7, m, ArH
Compound 3.74 m.p.82,
1H n.m.r. δ (CDCl
3) 0.94, t, J7Hz, CH
3; 1.44, s, 2xCH
3; 1.4-1.7, m, CH
2CH
3; 2.55, s, COCH
2; 2.98, q, J7Hz, CH
2CH
2CH
3; 5.06, s, OCH
2And 7.0-7.6, m, ArH
Compound 3.77 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.97, t, J7Hz, CH
3; 1.42, s, 2xCH
3; 1.4-1.8, m, CH
2CH
3; 2.53, s, COCH
2; 2.98, q, J7Hz, CH
2CH
2CH
3; 5.08, s, OCH
2And 7.4-8.3, m, ArH
Compound 3.80 m.p.97,
1H n.m.r. δ (CDCl
3) 0.86, t, J7Hz.CH
3; 1.45, s, 2xCH
3; 1.4-1.8, m, CH
2CH
3; 2.58, s, COCH
2; 2.95, q, J7Hz, CH
2CH
2CH
3; 5.12, s, OCH
2And 6.8-7.7, m, ArH. and
Compound 3.82 m.p.82,
1H n.m.r. δ (CDCl
3) 0.98, t, J7Hz, CH
3; 1.51, s, CH
3; 1.54, m, CH
2CH
3; 2.3-3.1, m, COCH
2And CH
2CH
2CH
3; 5.02, s, OCH
2And 7.3-7.7, m, ArH
Compound 3.84 colorless oil oil,
1H n.m.r. δ (CDCl
3) 0.8-1.0,2t, J7Hz, J7Hz, 2xCH
3; 1.27, s, CH
3; 1.4-1.8, m, CH
2CH
3And CH
2CH
2CH
3; 2.2-2.7, m, COCH
2; 2.97, q, J7Hz, CH
2CH
2CH
3; 5.06, s, OCH
2And 7.2-7.7, m, ArH
Compound 3.94 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.8-1.1, m .CH
2CH
2CH
3And CH(CH
3)
2; 1.3, s, CH
3; 1.53, q, J7Hz, CH
2CH
2CH
3; 1.93, q, J7Hz, CH(CH
3)
2; 2.2-3.2, m, COCH
2And CH
2CH
2CH
3; 5.07, s, OCH
2And 7.3-7.7, m, ArH
Compound 3.103 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.98, t, J7Hz, CH
3; 1.07, d, J6Hz, CHCH
3; 1.3,1.42, s, s,, s, 2xCH
3; 1.5-1.8, m, CH
2CH
2CH
3; 2.5, q, J8Hz, CHCH
3; 3.03, t, J7Hz, CH
2CH
2CH
3; 5.05, s, OCH
2And 7.0-7.7, m, ArH
Compound 3.104 m.p.57,
1H n.m.r. δ (CDCl
3) 0.97, t, J7Hz, CH
3; 1.13,1.37, s, s, 4xCH
3; 1.5-1.8, m, CH
2CH
2CH
3; 3.02, t, J7Hz, CH
2CH
2CH
3; 5.06, s, OCH
2And 6.9-7.7, m, ArH
Compound 3.122 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.9, t, J7Hz, CH
2CH
2CH
3; 1.35, s, CH
3; 1.45-1.7, q, J7Hz, CH
2CH
2CH
3; 2.2-3.1, m, CH
2CH
2CH
3And COCH
2; 3.53, s, 2xOCH
3; 4.2, s, CH; 5.08, s, OCH
2And7.3-7.7, m, ArH
Compound 3.123 colorless oil,
1H n.m.r. δ (CDCl
3) 0.95, t, J7Hz, CH
2CH
2CH
3; 1.36, s, CH
3; 1.45-1.7, q, J7Hz, CH
2CH
2CH
3; 2.2-3.1, m, CH
2CH
2CH
3And COCH
2; 3.5, s, 2xOCH
3; 4.18, s, CH; 5.03, s, OCH
2And 6.9-7.7, m, ArH
Compound 3.124 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.91, t, J7Hz, CH
2CH
2CH
3; 1.41, s, CH
3; 1.4-1.7, q, J7Hz, CH
2CH
2CH
3; 2.2-3.1, m, CH
2CH
2CH
3DCOCH
2; 3.52, s, 2xOCH
3; 4.17, s, CH; 4.98, s, OCH
2And 6.9-7.5, m, ArH
Compound 4.10 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.96, t, J7Hz, CH
2CH
3; 1.2-3.2, m, CH
2CH
2CH
3With assorted H; 5.0, s, OCH
2And 7.2-7.7, m, ArH
Compound 4.11 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.91, t, J7Hz, CH
2CH
3; 1.3-3.2, m, CH
2CH
2CH
3With assorted H; 5.04, s, OCH
2And 6.9-7.7, m, ArH
Compound 4.20 light yellow oil,
1H n.m.r. δ (CDCl
3) 0.93, t, J7Hz, CH
2CH
3; 1.2-3.2, m, CH
2CH
2CH
3With assorted H; 4.96, s, OCH
2And 6.7-7.5, m, ArH
Compound 4.24 m.p.114,
1H n.m.r. δ (CDCl
3) 0.96, t, J7Hz, CH
2CH
3; 1.3-3.3, m, CH
2CH
2CH
3With assorted H; 5.08, s, OCH
2And 7.2-7.7, m, ArH
Compound 4.30 m.p.85,
1H n.m.r. δ (CDCl
3) 0.92, t, J7Hz, CH
2CH
3; 1.2-3.2, m, CH
2CH
2CH
3With assorted H; 5.02, s, OCH
2And 6.9-7.6, m, ArH
Because they are closely similar with rice, barnyard grass is the most difficult grass of removing in the farm crop of rice field, and now the weedicide that uses does not have the selectivity of being satisfied with to the barnyard grass in the rice farm crop.For the logical formula I compound of the present invention being described as the validity of selective herbicide with weeds in the control rice farm crop, with table 1 Chinese style 1.32 and 1.59 compound administration barnyard grass grass and rice.With people such as US4008067(Hirono work) and AU560716(27196/84) compound in people's works such as () Watson also be applied to barnyard grass grass and rice as a comparison, the weeding data are listed in the table 4.In this table, 0 representative is invalid, and 10 represent plant withered.
As what seen from table 4, The compounds of this invention obviously is better than the prior art compound aspect the control of selectivity weeds in to the rice farm crop.
Table 4: the comparison of The compounds of this invention and known compound
0.4kg/Ha weeding rate
Compound (0-10 level, 10 expression plants are withered)
Before the Miao Houmiao
Barnyard grass grass rice barnyard grass grass rice
1.32 10 0 10 0
1.59 10 3 10 0
A 9 9 9 6
B 10 9 10 9
C 0 5 0 0
People such as Hirono are open,
The amino fourth pyridine (butylidine) of A:8-(1-allyl oxygen)-6,10-dioxo spiro (4.5) decene-7,9-diketone;
The amino fourth pyridine (butylidine) of B:9-(1-allyl oxygen)-7,11-dioxo spiro (5,5)-4-methyl hendecene-8,10-diketone; People such as Watson are open:
The amino butyl of C:3-(1-allyl oxygen)-the 6-(4-chloro-phenyl-)-4-hydroxyl pyran-2-one.
In order to further specify the effect of the logical formula I compound of the present invention as weedicide, the logical formula I compound of listing among the table 1-4 is applied to rice behind barnyard grass grass and the seedling with 0.1kg/ hectare and 0.4kg/ hectare, the weeding data are listed in the table 5.In table 0 the representative invalid, 10 represent plant death.As what we saw, the barnyard grass grass of logical formula I compound in can the selective control rice field.
Table 5
Compound barnyard grass grass rice barnyard grass grass rice
Table 1-4 (0.1kg/Ha) (0.4kg/Ha)
1.32 9 0 10 0
1.33 4 0 8 1
1.34 9 3 10 1
1.52 3 1 9 2
1.56 8 0 10 1
1.58 8 4 9 5
1.59 9 1 10 3
1.63 10 1 10 1
1.77 5 0 10 2
1.95 6 0 10 3
1.99 1 0 10 0
1.111 9 0 10 1
1.113 10 2 10 3
3.16 6 0 10 2
3.66 6 0 9 2
3.67 9 0 9 1
3.74 2 0 10 5
3.82 2 0 7 0
3.94 6 0 10 3
3.122 9 0 10 2
3.124 8 1 10 2
3.127 9 1 10 1
4.10 10 0 10 0
4.11 10 2 10 4
4.24 9 0 10 1
4.30 9 2 10 2
Claims (25)
1, general formula (I) compound, its isomer and/or its tautomer:
Wherein:
A is by 1-4 C
1-C
3The C that alkyl substituent replaces arbitrarily
1-C
3Alkylidene group or C
1-C
3Alkylene group;
X is O, S, SO, SO
2, NR
10Or singly-bound;
R
1Be H, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
5-C
6Cycloalkyl, C
5-C
6Cycloalkenyl group, C
1-C
4Alkyl-carbonyl, phenylcarbonyl group are selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, nitro, cyano group, C
1-C
4Haloalkyl, amino and C
1-C
4The phenyl that the substituting group of halogenated alkoxy replaces arbitrarily, C
1-C
4Alkyl sulphonyl, phenyl sulfonyl, C
1-C
4Alkyl-carbonyl, C
2-C
8Alkoxyalkyl, C
2-C
8Alkylthio alkyl, C
7-C
10Phenylalkyl or M;
R
2Be C
1-C
6Alkyl, C
2-C
6Alkenyl, C
2-C
6Alkynyl, C
1-C
4Haloalkyl, C
1-C
4Alkylthio, C
3-C
6Cycloalkyl, C
5-C
6Cycloalkenyl group is selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkylthio, nitro, cyano group, C
1-C
4Haloalkyl, amino and C
1-C
4The phenyl that the substituting group of halogenated alkoxy replaces arbitrarily, C
2-C
8Alkoxyalkyl, C
2-C
8Alkylthio alkyl or be selected from the C that the substituting group of phenyl, phenoxy group and sulfo-phenoxy group replaces
1-C
4Alkyl, wherein said substituent aromatic nucleus is selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, nitro, cyano group, amino, C
1-C
4Haloalkyl and C
1-C
4The substituting group of halogenated alkoxy replaces;
R
3And R
4Be H or C independently of one another
1-C
4Alkyl;
R
5And R
6Be H independently of one another, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
6Alkylthio alkyl, C
1-C
4Haloalkyl, C
2-C
4Halogenated alkenyl or C
3-C
6Cycloalkyl, wherein alkyl, alkenyl and cycloalkyl at random are selected from OR by 1-3
12, NR
13R
14, NR
15C (O) (C
1-C
4Alkyl), NR
18SO
2(C
1-C
4Alkyl), NR
21C (O) (C
1-C
4Alkyl), C (OR
16) (OR
17) R
22,
C (SR
19) (SR
20) R
23, C
1-C
4The substituting group of carbalkoxy and substituted-phenyl replaces, and the substituting group on the phenyl is selected from halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, nitro, cyano group, C
1-C
4Haloalkyl and C
1-C
4Halogenated alkoxy;
Perhaps
R
5And R
6Form saturated or undersaturated 3 to 7 yuan of carbocyclic rings fully with coupled carbon, or complete saturated the or undersaturated 1-3 of containing is selected from 0-3 nitrogen, heteroatomic 5 to 7 yuan of heterocycles of 0-2 oxygen and 0-2 sulphur; Said ring can be selected from halogen, C by 1-4
1-C
4Alkyl, C
1-C
4Haloalkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
1-C
4Alkyl-carbonyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Carbalkoxy ,-COOH, C
2-C
8Alkoxyalkyl, C
2-C
8The substituting group of alkane sulfane base and phenyl replaces, and wherein phenyl can be selected from halogen, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Haloalkyl, nitro, cyano group and C
1-C
4The substituting group of halogenated alkoxy replaces arbitrarily; A carbon atom of said ring can be carbonyl or its corresponding dimethyl, the form of diethyl or ethylidene or propylidene ketal;
R
7, R
8And R
9Be H independently of one another, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl, C
1-C
4Halogenated alkoxy, nitro, cyano group, C
1-C
4Carbalkoxy, C
1-C
4Alkane aminocarbonyl, C
2-C
6Dialkylamino carbonyl, aminocarboxyl; Amino; C
1-C
4Alkylamino, C
2-C
6Alkylamino; Or benzenesulfonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy group, thiophenyl, phenylamino or phenyl, said group is selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkoxyl group and CF
3Substituting group replace arbitrarily;
Condition is: work as R
5And R
6All be C independently
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
6Alkylthio alkyl, C
1-C
4Haloalkyl, C
2-C
4Halogenated alkenyl or quilt are selected from C
1-C
4The C that the substituting group of carbalkoxy and substituted-phenyl replaces arbitrarily
3-C
6Cycloalkyl, wherein the substituting group on the phenyl is selected from halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, nitro, cyano group, C
1-C
4Haloalkyl and C
1-C
4Halogenated alkoxy, or work as R
5And R
6When forming the saturated or unsaturated carbocyclic be optionally substituted or heterocycle together, R then
7, R
8Or R
9In at least one is phenyl sulfonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy group, thiophenyl or the phenylamino that is optionally substituted, or R
7, R
8Or R
9In at least one is selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkyl, C
1-C
4Alkoxyl group and CF
3The phenyl that replaces of substituting group;
R
10Be H, C
1-C
4Alkyl or be selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylthio, C
1-C
4Haloalkyl and C
1-C
4The phenyl that the substituting group of halogenated alkoxy replaces arbitrarily;
M is Li
+, Na
+, K
+, NH
4 +, or N (R
11)
4 +, R wherein
11Be C
1-C
4Alkyl;
R
12Be H, C
1-C
4Alkyl, C (0) (C
1-C
4Alkyl) or CO
2(C
1-C
4Alkyl);
R
13, R
15, R
18, R
21, R
22And R
23Be H or C independently of one another
1-C
3Alkyl;
R
14, R
16, R
17, R
19And R
20Be C independently of one another
1-C
3Alkyl;
R
16And R
17Can be together-(CH
2)
2-or-(CH
2)
3-and
R
19And R
20Can be together-(CH
2)
2-or-(CH
2)
3-.
2, the compound of logical formula I is characterized in that:
R
1Be H or M; And
R
2Be C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
2-C
4Alkenyl or C
2-C
4Alkynyl.
3, according to the compound of claim 2, it is characterized in that:
A is by CH
3Or C
2H
5Any C that replaces
1-C
2Alkylidene group or C
3-C
4Alkylene group;
R
7, R
8And R
9Be H, Cl, Br, F, C independently of one another
1-C
3Alkyl, C
1-C
3Alkoxyl group, C
1-C
3Alkylthio, C
1-C
3Haloalkyl, C
1-C
3Halogenated alkoxy, nitro, cyano group or C
1-C
3Carbalkoxy; Perhaps be selected from halogen, C by 1-3
1-C
4Alkyl, C
1-C
4Alkoxyl group or CF
3The substituting group phenyl sulfonyl, benzoyl, benzyl, benzyloxy, phenoxy group, thiophenyl or the phenylamino that replace arbitrarily;
Condition is: R
7, R
8Or R
9In at least one is benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl, thiophenyl or the phenylamino that is optionally substituted; And
R
10Be H or CH
3
4,, it is characterized in that X is O according to the compound of claim 3.
5,, it is characterized in that X is S, SO or SO according to the compound of claim 3
2
6,, it is characterized in that X is as the defined NR of claim 1 according to the compound of claim 3
10
7,, it is characterized in that X is a singly-bound according to the compound of claim 3.
8, according to the compound of claim 7, it is characterized in that:
A is-CH
2-,-CH
2CH
2-or-CH
2CH=CH-;
R
1Be H, Li
+, Na
+Or K
+;
R
2Be CH
3, C
2H
5, just-C
3H
7Or just-C
4H
9;
R
3And R
4Independent separately is H, CH
3Or C
2H
5; And
R
7, R
8And R
9Independent separately is H, Cl, Br, F, CH
3, C
2H
5, OCH
3, OC
2H
5, SCH
3, SC
2H
5, CF
3, CHF
2, CF
2CF
3, OCHF
2, OCF
3, OCH
2CF
3, NO
2, CN, CO
2CH
3, Ph, SO
2Ph, COPh, CH
2Ph, OCH
2Ph, OPh, SPh, NHPh or N(Me) Ph, condition is: R
7, R
8Or R
9In at least one is benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl, thiophenyl or the phenylamino that is optionally substituted.
9, according to the compound of claim 7, it is characterized in that R
5And R
6Be C independently of one another
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
1-C
4Alkylthio or C
2-C
6Alkylthio alkyl.
10, according to the compound of claim 7, it is characterized in that R
5And R
6With coupled carbon form together one saturated or undersaturated by 1-4 CH
3Any 5,6 or 7 yuan of carbocyclic rings that replace.
11, according to the compound of claim 10, it is characterized in that:
A is-CH
2-,-CH
2CH
2-or-CH
2CH=CH-;
R
1Be H, Li
+, Na
+Or K
+;
R
2Be CH
3, C
2H
5, just-C
3H
7Or just-C
4H
9;
R
3And R
4Be H or CH independently of one another
3; And
R
7, R
8And R
9Be H, Cl, Br, F, CH independently of one another
3, C
2H
5, OCH
3, OC
2H
5, SCH
3, SC
2H
5, CF
3, CHF
2, CF
2CF
3, OCHF
2, OCF
3, OCH
2CF
3, NO
2, CN, CO
2CH
3, Ph, SO
2Ph, COPh, CH
2Ph, OCH
2Ph, OPh, SPh, NHPh or N(Me) Ph, condition is: R
7, R
8Or R
9In have at least one to be benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl, thiophenyl or the phenylamino that replaces arbitrarily.
12, according to the compound of claim 7, it is characterized in that R
5And R
6Form the saturated or undersaturated 1-2 of containing heteroatomic 5, the 6 or 7 yuan of heterocycles that are selected from 0-2 nitrogen, a 0-1 oxygen and 0-2 sulphur together with coupled carbon; Said ring is by 1-4 CH
3Replace arbitrarily.
13, according to the compound of claim 12, it is characterized in that:
A is-CH
2-,-CH
2CH
2-or-CH
2CH=CH-;
R
1Be H, Li
+, Na
+Or K
+;
R
2Be CH
3, C
2H
5, just-C
3H
7Or just-C
4H
9;
R
3And R
4Be H, CH independently of one another
3Or C
2H
5; And
R
7, R
8And R
9Be H, Cl, Br, F, CH independently of one another
3; C
2H
5, OCH
3, OC
2H
5, SCH
3, SC
2H
5, CF
3, CHF
2, CF
2CF
3, OCHF
2, OCF
3, OCH
2CF
3, NO
2, CN, CO
2CH
3, Ph, SO
2Ph, COPh, CH
2Ph, OCH
2Ph, OPh, SPh, NHPh or N(Me) Ph, condition is R
7, R
8Or R
9In at least one is benzenesulfonyl, benzoyl, benzyl, benzyloxy, phenoxy group, phenyl, thiophenyl or the phenylamino that replaces arbitrarily.
14, butyl methoxyimino 9-hydroxyl-8-(1-((3-phenoxy group) phenyl)))-6-oxaspiro (4.5) last of the ten Heavenly stems-8-alkene-7-ketone.
15, butyl methoxyimino 8-(1-((4-(4-fluorophenyl) phenyl)))-9-hydroxyl-6-oxaspiro (4.5) last of the ten Heavenly stems-8-alkene-7-ketone.
16, butyl methoxyimino 9-hydroxyl-8-(1-((4-(phenyl) phenyl)))-6-oxaspiro (4.5) last of the ten Heavenly stems-8-alkene-7-ketone.
17,6,6-dimethyl-4-hydroxyl-3-(1-((4-(phenyl) phenyl) methoxyimino) butyl) pyran-2-one.
18,6,6-dimethyl-3-(1-((4-(4-fluorophenyl) phenyl) methoxyimino) butyl)-4-hydroxyl pyran-2-one.
19, listed arbitrary compound in the previous table 1 to 4.
20, a plant growth suppresses, plant is destroyed or plant kills composition, it is characterized in that it comprises a kind of logical formula I compound and a kind of inert support as claim 1 definition.
21, a kind of method of coordinate plant growth is characterized in that to plant, and seed of plant or plant growth medium impose the logical formula I compound as definition in the claim 1 of significant quantity.
22, a kind of selectivity suppresses, and destroys or kill method for weed in the wide leaf farm crop, it is characterized in that to crop or its location impose significant quantity as the defined formula I compound of claim 1.
23, a kind of herbicidal composition, it is a kind of as the defined logical formula I compound of claim 1 and at least a other weedicide to it is characterized in that it comprises.
24, a kind of plant growth regualting composition, it is a kind of as the defined logical formula I compound of claim 1 and a kind of inert support to it is characterized in that it comprises.
25, logical formula I compound is as weedicide or plant-growth regulator.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPK462091 | 1991-02-15 | ||
| AUPK4620/91 | 1991-02-15 | ||
| AUPK9973/91 | 1991-12-11 | ||
| AUPK997391 | 1991-12-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1065660A true CN1065660A (en) | 1992-10-28 |
Family
ID=25644004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92101624 Pending CN1065660A (en) | 1991-02-15 | 1992-02-15 | Herbicidal pyrones |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0573460A4 (en) |
| JP (1) | JPH06505240A (en) |
| CN (1) | CN1065660A (en) |
| BR (1) | BR9205641A (en) |
| PT (1) | PT100129A (en) |
| TW (1) | TW221430B (en) |
| WO (1) | WO1992014736A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19716591A1 (en) * | 1996-08-05 | 1998-03-05 | Bayer Ag | 2- and 2,5-substituted phenylketoenols |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3560789A (en) * | 1988-05-04 | 1989-11-29 | Dunlena Pty. Limited | Selective pyrone herbicides |
| AU7161391A (en) * | 1990-01-22 | 1991-08-05 | Dunlena Pty. Limited | Herbicidal pyrones |
-
1992
- 1992-02-14 JP JP4504784A patent/JPH06505240A/en active Pending
- 1992-02-14 WO PCT/AU1992/000053 patent/WO1992014736A1/en not_active Application Discontinuation
- 1992-02-14 TW TW81101064A patent/TW221430B/zh active
- 1992-02-14 EP EP19920904717 patent/EP0573460A4/en not_active Withdrawn
- 1992-02-14 BR BR9205641A patent/BR9205641A/en not_active Application Discontinuation
- 1992-02-14 PT PT10012992A patent/PT100129A/en not_active Application Discontinuation
- 1992-02-15 CN CN 92101624 patent/CN1065660A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| PT100129A (en) | 1993-08-31 |
| JPH06505240A (en) | 1994-06-16 |
| TW221430B (en) | 1994-03-01 |
| BR9205641A (en) | 1994-06-07 |
| WO1992014736A1 (en) | 1992-09-03 |
| EP0573460A1 (en) | 1993-12-15 |
| EP0573460A4 (en) | 1994-03-17 |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
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