CN1036202A - The improvement of organic compound or relevant organic compound - Google Patents

The improvement of organic compound or relevant organic compound Download PDF

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Publication number
CN1036202A
CN1036202A CN89101743A CN89101743A CN1036202A CN 1036202 A CN1036202 A CN 1036202A CN 89101743 A CN89101743 A CN 89101743A CN 89101743 A CN89101743 A CN 89101743A CN 1036202 A CN1036202 A CN 1036202A
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group
alkyl
compound
phenyl
replaces
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理查德·詹姆斯·安东逊
扬纳斯·格林纳
弗雷德·库伦
李诗妇
加里·韦恩·卢阿
赫曼·施奈德
卡尔·塞金杰
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Sandoz AG
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Sandoz AG
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    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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Abstract

The invention provides the ring-type 1 of novel formula I, the 3-dicarbonyl compound Y wherein, A 2, R 1, R 2, R 3, R 4And A 3 A 4Such as in open definition, this compound go out in cutting weeds purposes and comprise the herbicidal composition of this compound.

Description

The improvement of organic compound or relevant organic compound
The present invention relates to novel cyclohexadione compounds, this compounds contains the method for the herbicide composition and this novel cpd of preparation of this class dione compounds in the application of going out on cutting weeds.
Or rather, the present invention relates to the novel cpd of formula I
Figure 891017437_IMG11
R wherein 1, R 2, R 3And R 4It is respectively the aliphatic hydrocarbyl group of undersaturated maximum 6 carbon atoms; The group of naphthene base of maximum 6 carbon atoms; Ar or (A 1) the nX group; R thus 1, R 2, R 3And R 4In one also can be C 2-5Carbalkoxy; R 1, R 2, R 3And R 4In at least one be (A 1) nX; R 1With R 2Together or R 3With R 4Also can be C together 2-5Alkylidene group, R 1And R 2Also can generate oxo or C together 1-5Alkylidene group,
Ar does not replace or replaces, by being selected from O, and the 1-3 among N and the S 5 yuan or 6 yuan of heteroaryls that heteroatoms is formed, and be connected on the ring A by ring carbon atom,
N is 0 or 1,
X is H, OR 6, SR 7, NR 8R 9, NO 2Halogen, CN, CF 3, CHF 2, S(O) mR 10, CO-NHR 11, CO-R 12, CR 13R 14-COO(C 1-6Alkyl) or benzyl,
A 1Be unsubstituted or by one or more C 1-5Methylene radical or ethylidene that alkyl replaces,
R 6And R 7Be respectively H, alkyl, haloalkyl, heteroaryl or CO-R 15Group,
R 8Be H, alkyl, heteroaryl or CO-R 15Group,
R 9, R 10, R 13And R 14Be respectively H, C 1-6Alkyl or aryl,
R 11Be H or alkyl,
R 12And R 15Be respectively H, alkyl or heteroaryl,
M is 1 or 2,
A 2Be a key, CR 16R 17, CR 16R 17-CR 18R 19, O, S, NR 20Or CO,
R 16And R 18Be respectively H, the carboxylic group of alkyl or free state, salt shape or esterification form, R thus 16And R 1On contiguous carbon atom, can generate a key together,
R 17And R 19Be respectively H, alkyl or (A 1) nX group, wherein A 1, n and x are as mentioned above.R thus 16And R 17Or R 18And R 19Also can represent (CH together 2) 2-5Group, thereby generate a kind of spirocyclic compound and/or R 16And R 1Be close on carbon atom or R at it together 18And R 3On its contiguous carbon atom, can generate (CH together 2) 1-5, thereby generate a dicyclo,
R 20Be H, alkyl or CO-R 15, R wherein 15Define as above,
A 3
Figure 891017437_IMG12
A 4Be C=C(ORa) (group A) or C(X 1)-C(O) (group B)
X is F or Cl,
Ra is H, a salifiable part or be the part of ether or ester with the oxygen bonding,
Y or by R 21, R 22And R 23The phenyl or the Ar ' that replace
Ar ' is the heteroaryl of 5 yuan or 6 yuan, and it comprises that 1,2 or 3 is selected from O, and the heteroatoms of S and N, this assorted aromatic group be unsubstituted or replace, and is connected on the CO-group that it is bonded by a ring carbon atom,
R 21And R 22Be respectively H, halogen, C 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Haloalkyl, CN, NO 2, CF 3O, R bS(O) p, NR cR d, C(O) R e, SO 2-NR cR dOr NR c-C(O)-R d, R thus 21And R 22Can form the (methylenedioxy) group together,
P is 0,1 or 2
R bBe arbitrarily by halogen, cyano group, the C that phenyl or benzyl replace 1-4Alkyl,
R cAnd R dBe respectively H, or C 1-4Alkyl,
R eBe C 1-4Alkyl or C 1-4Alkoxyl group,
R 23Be halogen, NO 2, CN, C 1-2Alkyl, C 1-2Alkoxyl group, C 1-2Haloalkyl or C 1-4The q of alkyl-S(O),
Q is 0,1 or 2,
Thus, when Y is not the pyrimidyl that replaces arbitrarily, R 1, R 2, R 3And R 4In one also be the phenyl of phenyl or replacement, but its condition is:
A) at R 1, R 2, R 3And R 4One in, X only is H, at this moment, following at least a kind of situation is suitable for:
ⅰ) CR 1R 2-A 2Be C(R 2)=C(R 17) or CR 1R 2-CR 16R 17-CR 18R 19,
ⅱ) Y is not phenyl that replaces arbitrarily or the pyrimidyl that replaces arbitrarily,
ⅲ) R 1And R 2Be oxo or C together 1-5Alkylidene group,
ⅳ) other at least substituent R 1, R 2, R 3And R 4In one be undersaturated aliphatic hydrocarbyl group, naphthene group, unsubstituted or the phenyl or the Ar that replace,
ⅴ) other at least substituent R 1, R 2, R 3, R 4, R 17And R 19In one be (A 1) the nX group, wherein X is not H, or
ⅵ) A 3
Figure 891017437_IMG13
A 4Be C(X 1)-C(O),
B) at CR 1R 2-A 2Be C(R 2)=C(R 17) time, R 3And R 4Both are not H entirely,
And c) R 1And R 2When being oxo together, A 2Not O, S, NR 20Or CO, the compound of the compound through type II of formula I
(R wherein 1, R 2, R 3, R 4And A 2Definition as above)
Obtain with the compound reaction of formula III
(wherein Y defines as above, and Hal is a halogen)
Reset the ester of the formula IV that obtains subsequently
(Y wherein, R 1, R 2, R 3, R 4And A 2Definition as above).
Obtain the compound of formula I b
(Y wherein, A 2, R 1, R 2, R 3And R 4Define as above, M is the salifiable part of H or shape, any etherificate, the compound of the resulting formula I of esterification or halogenation b can obtain corresponding 2-(Y-CO)-2-alkene-1-ketone-3-alcohol ether, 2-(Y-CO)-2-alkene-1-ketone-3-alcohol ester or 2-X 1-2-(YCO)-1, the 3-dione compounds).
For preparing ester with a kind of known method from a kind of pure and mild a kind of carboxylic acid halides, 1-ketone-3-alkylol cpd and halid esterification may be effective.
This reaction is suitable for carrying out in solvent, and used solvent should be inert (as methylene dichloride) under reaction conditions, and preferably at a kind of acid binding agent, for example triethylamine carries out under existing.The suitable reaction temperature scope is 0-40 ℃, for example 20 ℃.
Under for the known conditions for preparing from β-ketone enol ester alpha-acyl-beta-diketone, the ester of the formula IV that obtains thus can be rearranged into the compound of required formula I.For this reason, needn't from the reaction mixture that generates them, separate ester in general.
This rearrangement reaction can be finished in the presence of catalyzer, and this catalyzer for example is the 4-Dimethylamino pyridine, and the catalyzer of Lewis acid catalyst or a kind of cyanide source closes the alkali that cyanalcohol adds medium tenacity as acetone, for example the such tertiary amine base of triethylamine.
The suitable Lewis acid catalyst of this rearrangement reaction for example is an aluminum chloride, zinc chloride or tin tetrachloride (IV).
The suitable solvent for example is methylene dichloride, acetonitrile or toluene.Suitable reaction temperature be 0 ℃ between the reflux temperature, room temperature (about 20 ℃) preferably
The compound of formula I can reclaim from the mixture that forms them by the method that has been formulated.
According to reaction conditions, the form (M is H) that formula I b compound can free acid or obtain with the form of salt.
When formula I b compound was the form of free acid, they can exist with various tautomeric forms.This acid can be transformed into corresponding salt in a kind of known mode, vice versa.
When formula I b compound is the form of salt (M be give birth to salifiable part), M inorganicly (for example is equivalent to Na, Ca, a kind of metal of Fe or Cu) or organically, the ammonium salt of amine part (as 1-(methylamino-methyl) naphthalene for example), sulfonium, the part of sulfoxonium or phosphorus.According to the character of M, this salt can chelated forms exist.
Equally, use known method, can obtain the formula I compound of ester and ether shape from the formula I compound of corresponding free acid or salt shape.
Thereby, the compound of formula I a
Figure 891017437_IMG17
(wherein OR ' a is the part of ether or ester, Y, A 2And R 1, R 2, R 3And R 4Definition is as above),
Can and obtain from the corresponding compounds of formula I b and following arbitrary compound reaction:
A) compound R ' aOH and a kind of catalyzer,
B) compound R ' aThe alkali of Q and a kind of medium tenacity, wherein Q be halogen atom or,
C) compound R 11NHCOCl or its functional response derivative.
Above-mentioned reaction a) is carried out in the presence of the catalyzer such as the vitriol oil, and reaction suits to finish under (as the methyl alcohol) and intensification condition in the also solvent as reactant.
Above-mentioned reaction b) suit in the presence of the alkali such as triethylamine or pyridine of medium tenacity, in room temperature or be lower than under the ambient temperature and carry out, for preparation ether shape compound, above-mentioned reaction b) can use the formula I b compound of silver salt form, finish in known manner.
Above-mentioned reaction c) be under for known condition, to carry out by a kind of substituted-amino formyl chloride of N-arbitrarily or a kind of corresponding isocyanate and pure prepared in reaction carbamate.We know that this carbamate also can pass through corresponding carbonate and NH 3Or primary amine reaction obtains.
Suitable ether moiety OR ' aExample be-oxyl group, as O-C 1-6Alkyl, O-C 2-6Alkenyl, O-C 2-6Alkynyl group, O-benzyl, O-phenyl, O-tolyl and benzoyl methoxyl group.
Suitable ester moiety OR ' aExample be the acyl-oxygen group, O-COO-hydrocarbyl group for example, O-CO-hydrocarbyl group and O-SO 2-hydrocarbyl group, as the O-ethanoyl, O-methylsulfonyl, O-tosyl group, O-benzoyl, O-COOC 1-6Alkyl (O-COOCH for example 3), OCOO-phenyl, O-COO-benzyl and O-CONHR 11(O-CONH for example 2And O-CONHC 1-6Alkyl).
Can obtain A with chlorizating agent or fluorizating agent chlorination or the compound of fluoridizing formula I b 3
Figure 891017437_IMG18
A 4It is the formula I compound of group B.
The selection of chlorizating agent or fluorizating agent will be by the concrete substituting group decision in the formula I b compound.The chlorizating agent that is suitable for comprises that the chlorine positively charged ion is to body, as alkaline metal hypochlorite (for example NaClO or KClO) or N-Cl-succinimide.Any substituent chlorization in the formula I b compound, it is desirable adopting the formula I b compound of anionic form.
The fluorizating agent that is suitable for is that the fluorine positively charged ion is given body, as FClO 3Or the CH of ptoluene-sulfonyl-N(F) 3, it is suitable fluoridizing with the formula I b compound of anionic form.
Formula I compound obtains with the form of suitable/trans isomer mixture usually, when this compound has one or more chiral centre, obtains with the form of racemize or non-enantiomer mixture.
The example of the preferred group of formula I compound is:
The compound of-Shi I, wherein R 1Be (A 1) nX ', X ' are defined as the X except H, A 1, n, R 2, R 3, R 4, A 2, A 3 A 4Define as above (the hereinafter compound of formula I z) with Y.
The compound of-Shi I, wherein R 1Be the unsaturated aliphatic alkyl group of 6 carbon atoms at the most, the group of naphthene base of maximum 6 carbon atoms or Ar; (Ar, R 2, R 3, R 4, A 2, A 3
Figure 891017437_IMG20
A 4Define as above (the hereinafter compound of formula I y) with Y)
The compound of-Shi I, wherein CR 1R 2-A 2Be C(R 2)=CR 17(R 2, R 17, R 18, R 19, R 3, R 4, A 3
Figure 891017437_IMG21
A 4Define as above (the hereinafter compound of formula I x) with Y);
The compound of-Shi I, wherein R 1And R 2Be oxo or C together 1-5Alkylidene group (A 2, A 3
Figure 891017437_IMG22
A 4, R 3, R 4Define as above (the hereinafter compound of formula I w) with Y)
The compound of-Shi I, wherein A 3
Figure 891017437_IMG23
A 4Be C(X 1)-C(O), (X 1, R 1, R 2, R 3, R 4, A 2Define as above (the hereinafter compound of formula I v) with Y)
The compound of-Shi I, wherein A 2Be C(CF 3) R 16Or C(CF 3) R 16-CR 18R 19; (R 16, R 18, R 19, R 1, R 2, R 3, R 4, A 3
Figure 891017437_IMG24
A 4Define as above (the hereinafter compound of formula I u) with Y)
The compound of-Shi I, wherein Y is the thienyl that replaces arbitrarily, pyridyl, pyrazolyl, isothiazolyl, 1,2,3-thiadiazolyl group or piperazinyl, (be the thienyl that replaces arbitrarily, pyridyl or pyrazolyl are better, particularly pyridyl or the pyrazolyl that replaces arbitrarily, preferably 1-CH 3-4-NO 2-pyrazoles-5-base or 1-CH 3-4-NO 2-pyrazole-3-yl) (R 1, R 2, R 3, R 4, A 2And A 3 A 4Definition is (the hereinafter compound of formula I t) as above)
The compound of-Shi I, wherein Y is by R 21, R 22And R 23The phenyl that replaces or except the pyrimidyl of any replacement is selected from O, and 5 yuan or 6 yuan of heteroaryls of the 1-3 of N and S heteroatomic any replacement, this heteroaryl are linked by ring carbon atom and encircle on the A R 1, R 2, R 3And R 4In one be the phenyl of phenyl or replacement, and other substituent R 1, R 2, R 3And R 4Be respectively the aliphatic hydrocarbyl of undersaturated maximum 6 carbon atoms, the group of naphthene base of maximum 6 carbon atoms, Ar or (A 1) nThe X group; (R thus 1A 3
Figure 891017437_IMG26
A 4, R 3And R 4Definition is (the hereinafter compound of formula I s) as above)
The compound of-Shi I, wherein CR 1R 2-A 2Be CR 1R 2-CR 16R 17-CR 18R 19(R 1R 2, R 16, R 17, R 18, R 19, R 3, R 4A 3
Figure 891017437_IMG27
A 4Define as above (the hereinafter compound of formula I r) with Y)
At formula I r, I u, I v, I w, I x, in the compound of I y and I z, preferred Y is the phenyl that replaces, pyridyl, thienyl, pyrazolyl, or pyrimidyl; Be the phenyl that replaces, pyridyl, pyrimidyl or pyrazolyl are better; The phenyl of Qu Daiing preferably, pyridyl or pyrazolyl, the especially phenyl of Qu Daiing, 1-CH 3-4-NO 2-pyrazoles-5-base or 1-CH 3-4-NO 2-pyrazole-3-yl.
In the compound of formula I s, Y is preferably by R 21, R 22, and R 23The phenyl that replaces, the pyridyl of replacement, thienyl or pyrazolyl; Be the phenyl that replaces, pyridyl or pyrazolyl are better; The phenyl of Qu Daiing preferably, 1-CH 3-4-NO 2-pyrazoles-5-base or 1-CH 3-4-NO 2-pyrazole-3-yl.
In formula I s compound, work as R 1When being the phenyl of phenyl or replacement, any (A 1) nX group preferably H or C 1-4Alkyl.
At one or more R 1, R 2, R 3And R 4When being the aliphatic hydrocarbyl group of undersaturated maximum 6 carbon atoms, it has two keys or triple bond to suit.
At one or more R 1, R 2, R 3And R 4When being the undersaturated aliphatic hydrocarbyl group of maximum 6 carbon atoms, it preferably contains 4 carbon atoms at the most, and the example of this class preferred group is a vinyl, allyl group and propargyl.
R 1, R 2, R 3And R 4In any one when being cycloalkyl, cyclopropyl preferably.
At R 1, R 2, R 3And R 4In any one when being the phenyl that replaces, this phenyl is selected from C 1-4Alkyl, C 1-4Alkoxyl group, halogen and CF 3In 1,2 or 3 substituting group be suitable; A preferred replacement or dibasic, preferably monobasic is particularly replaced by halogen.
R 1, R 2, R 3, R 4, R 6, R 7, R 8, R 12And R 15In any one when being heteroaryl, such group is suitable to be selected from thienyl, furyl, pyrryl, isoxazolyl, isothiazolyl, pyrazolyl, 1,2,3-thiadiazolyl group, pyridyl, pyrimidyl, pyrazinyl and pyridazinyl, these groups can be unsubstituted or replace.
The example of the suitable substituents of such heteroaryl group and Ar ' (Ar ' be the heteroaryl of replacement) is halogen (as F, Cl, or Br); Unsubstituted or by halogen (as F, Cl or Br), phenyl, S-C 1-4Alkyl or C 1-4The C that alkoxyl group replaces 1-4Alkyl; NO 2; CN; C 1-4Alkoxyl group; Formyl radical or C 2-4Alkanoyl and as oxime, the such functional derivatives of acetal and its ketal (C(=NOC for example 1-4Alkyl)-C 1-2Alkyl, C(O-C 1-4Alkyl) 2-C 1-3Alkyl, CH(O-C 1-4Alkyl) 2Deng); C 1-4Alkyl-S, C 1-4Alkyl-SO; C 1-4Alkyl-SO 2; C 1-5Alcoxyl-carbonyl.
R 1, R 2, R 3, R 4, R 6, R 7, R 8, R 12And R 15In any one when being heteroaryl, preferred unsubstituted or by halogen, NO 2, C 1-4Alkyl, C 1-4Alkoxyl group or C 1-4Mono-substituted thienyl of alkylthio or furyl, preferably unsubstituted.
Work as R 1, R 2, R 3, R 4In any one when being the phenyl that replaces arbitrarily, it is preferably unsubstituted.
R 1And R 2Generate C together 1-5During alkylidene group, preferably contain 1-4 carbon atom, preferably 1 or 2 carbon atom.
R 1, R 2, R 3And R 4In no more than one be that heteroaryl or the phenyl that replaces arbitrarily are preferred, preferably encircle A and be not selected from aryl radical, fragrant aliphatic radical, or more than one substituting group replaces in the heteroaryl.
R 6, R 7, R 8, R 11, R 12, R 15, R 16, R 17, R 18, R 19, R 20In one or more when being alkyl, such alkyl can be aliphatic, and is fragrance or araliphatic, and suitablely contains 8 carbon atoms at most.Such hydrocarbon be aliphatic series the time, preferred maximum 5 carbon atoms, it can be saturated or unsaturated, when being undersaturated situation, its suitable 1 two key or 1 triple bond of containing; When such hydrocarbon is aromatic or araliphatic, can be replaced by one or more substituting groups on aromatic nucleus, such substituting group is suitable to halogen, C 1-4Alkoxyl group and C 1-4Alkyl and CF 3The middle selection.
Work as R 6And R 7In any one when being haloalkyl, it for example can be the chloro alkyl, and preferred 1-4 carbon atom.
R 9, R 10, R 13And R 14In one or more are C 1-6During alkyl, preferred C 1-4Alkyl, for example CH 3
R 6To R 20In any one when being aryl, phenyl preferably, and be unsubstituted or be selected from halogen, C 1-4Alkoxyl group, C 1-4Alkyl and CF 3In 1-3 substituting group replace, it is better to be less than 3 substituting groups.
R 6, R 7, R 8, R 11, R 12, R 15To R 20In any one when being the araliphatic alkyl, preferably unsubstituted benzyl or α-Jia Jibianji, or on phenyl ring, be selected from halogen, C 1-4Alkoxyl group, C 1-4Alkyl and CF 3In 1-3,1 or 2 benzyl or α-Jia Jibianji that substituting group replaces preferably.
When Ar ' was the heteroaryl that replaces, such heteroaryl can be selected from halogen, CF 3, NO 2, C 1-4Alkyl, C 1-4Alkoxyl group (substituting group of 2 vicinities can generate methylene-dioxy together thus) C 1-4Alkyl-S, C 1-4Alkyl-S-C 1-4Alkyl, C 1-4Alkyl-SO 2With 1-3 substituting group in the benzyl, it is preferred that so substituent moieties has 1 or 2 carbon atom, and 1 carbon atom is preferably arranged.
Ar ' is preferred for the heteroaryl that replaces.
Preferred significant Ar ' comprises the thienyl of replacement, pyrazolyl, isothiazolyl, 1,2,3-thiadiazolyl group, pyridyl, pyrazinyl and pyrimidyl; The thienyl that replaces, pyrazolyl, pyrimidyl and pyridyl are better, preferably the pyrazolyl of Qu Daiing, pyrimidyl and pyridyl.
The substituting group of Ar ' preferably is in the ortho position of the CO of Ar ' institute's bonding, and/or is methylene-dioxy, thus, additional 1 or 2 substituting group can be arranged.The example of the aryl that suitable methylene-dioxy replaces is 5,6-(methylenedioxy)-3-pyridyl, 4,5-(methylenedioxy)-3-pyridyl and 4,5-(methylenedioxy) pyrimidyl.
The preferred examples of Ar ' ortho-substituent is (removing methylene-dioxy) NO 2, halogen, CN, CF 3, CH 3SO 2And CH 3SCH 2
Preferred additional substituting group example is halogen and the C that links on the ring carbon atom 1-4Alkyl, C 1-4Alkyl, benzyl and link a C on the ring N-atom 1-4Alkyl-sulfo--C 1-4Alkyl.
Particularly preferred significant Ar ' comprises 1-CH 3-4-NO 2-pyrazoles-5-base and 1-CH 3-4-NO 2-pyrazole-3-yl.
When Ar ' is the pyridyl that replaces, it preferably 3,5-two chloro-2-pyridyl.
A 1By one or more C 1-5When methylene radical that alkyl group replaces or ethylidene, this alkyl substituent preferably has 4 carbon atoms and methyl preferably at the most.
R 21Be C 1-6Alkoxyl group or C 1-6During alkylthio, it suits to contain 1-4 carbon atom, preferably contains 1 carbon atom.
R 21, R 22And R 23In one or more are C 1-6During alkyl sulphonyl, it suits to contain 1-4 carbon atom, preferably contains 1 carbon atom.
R 22Be preferably in the contraposition of carbonyl, R 23Be preferably in the ortho position of carbonyl.
R 22H preferably, and halogen (F, Cl, Br), C 1-4Alkyl-S, C 1-4Alkyl-SO 2Or and R 21Methylene-dioxy together, R 21H preferably, halogen or CH 3
R 23Halogen (for example Cl) preferably, CF 3, NO 2, CN or CH 3-SO 2
Preferred group CR 1R 2-A 2Example be CR 1R 2, CR 1R 2-CH 2, CR 1R 2-CH(CH 3), CR 1R 2-C(CH 3) 2, CR 1R 2-CO, CR 1R 2-O, CR 1R 2-CHCF 3, CR 1R 2-CH 2CH 2, CR 1R 2-CH(CH 3)-CH(CH 3) and C(R 2)=CH.
R 1Vinyl preferably; Allyl group; Propargyl; Cyclopropyl; Any phenyl that replaces; Furyl or thienyl; CH 2OH; CH(OH) CH 3; CH 2CH 2OH; Group (A 1) nX ', wherein A 1Define as above with n, X ' is defined as the X except H; Or and R 2Oxo together, CH 2Or CHCH 3Group; Or and R 16A key together.In addition, R 1Preferred C 1-4Alkyl is CH 3Or C 2H 5Better, when Y is not the phenyl that replaces arbitrarily or pyrimidyl, CH especially 3Better.
R 1Be (A 1) X ' time, A 1Preferably arbitrarily by one or 2 CH 3The CH that group replaces 2Or (CH 2) 2
A 1By one or more C 1-5When methylene radical that alkyl group replaces or ethylidene, such alkyl substituent preferably has 4 carbon atoms at the most, is that methyl is better.
Preferred radicals X ' example is C 1-4Alkylthio, thiophenyl, C 1-4Alkoxyl group, phenoxy group, CHO, C 2-5Alkanoyl, OH and it and C 2-5Aliphatic carboxylic acid or the ester that forms with the phenylformic acid of any replacement, C 2-5Carbalkoxy-CH 2, C 2-5Carbalkoxy-CH(CH 3), cyano group, F, Cl, CHF 2, CF 3, NO 2, CONH 2, CO-NH(C 1-4Alkyl), two (C 1-4Alkyl) N or benzyl, especially C 1-4Alkylthio.
(A 1) X ' C preferably 1-4Alkylthio.
Preferred radicals R 2, R 3And R 4Example be H, C 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Alkylthio, OH, C 1-4Alkyl-CO-O, C 2-5Carbalkoxy, thienyl and furyl, especially H, CH 3, OCH 3, SCH 3, OH, CH 3CO-O and COOCH 3, most preferably H or CH 3
A 2CR preferably 16R 17Or O.
Preferred significant R 16Example is H; C 1-4Alkyl; Any phenyl or benzyl that replaces; Thienyl; Furyl; COOH(is with acid, and the formation of salt or ester exists), and as above be pointed out that and R 1A key together; Especially H and CH 3, H most preferably.
Preferred significant R 17Example is H, C 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Alkylthio, C 1-4Alkylthio-C 1-4Alkyl and CF 3, H especially, SCH 3, CH 3And CF 3, most preferably H or CF 3
R 18And R 19Be respectively H or C 1-4Alkyl is better, preferably H or CH 3
Particularly preferred formula I compound has one or more features described as follows:
R 1Be H, CH 3, S-CH 3, S(O) CH 3, SO 2CH 3, phenyl or by C 1-4Alkyl, C 1-4Alkoxyl group, halogen or CF 3Mono-substituted phenyl, or the alkenyl or the alkynyl group of 4 carbon atoms at the most.
R 2, R 3And R 4Be respectively H or CH 3, R thus 2, R 3And R 4In one also be SCH 3, S(O) CH 3Or SO 2CH 3, its condition is R 1To R 4In only one be SCH 3, S(O) CH 3Or SO 2CH 3
A 2Be CH(CF 3), CH 2Or O.
Y is 3,5-two chloro-2-pyridyl, 1-CH 3-4-NO 2-pyrazoles-5-base, 1-CH 3-4-NO 2-pyrazole-3-yl or by R 21, R 22And R 23The phenyl that replaces, described thus phenyl substituent is the preferred significant group that provides above.
Particularly preferred formula I examples for compounds like this comprises:
The compound of formula I, wherein R 1Be SCH 3, S(O) CH 3Or SO 2CH 3; R 2, R 3And R 4Be respectively H or CH 3; A 2Be CH 2, O or CH(CF 3); Y is 3,5-two chloro-2-pyridyl, 1-CH 3-4-NO 2-pyrazoles-5-base, 1-CH 3-4-NO 2-pyrazole-3-yl.Or by R 21, R 22, R 23The phenyl that replaces.
The compound of formula I, wherein R 1Be SCH 3, S(O) CH 3Or SO 2CH 3; R 2, R 3And R 4Be respectively H or CH 3; A 2Be CH(CF 3) or O; Y is by R 21, R 22And R 23The phenyl that replaces.
The compound of formula I, wherein R 1Be the alkenyl or the alkynyl group of maximum 4 carbon atoms; R 2, R 3And R 4Be respectively H, CH 3, SCH 3, S(O) CH 3Or SO 2CH 3, its condition is R 2To R 4In only have one to be to be selected from SCH 3, S(O) CH 3And SO 2CH 3Group; A 2Be CH 2, O or CH(CF 3); Y is 3,5-two chloro-2-pyridyl, 1-CH 3-4-NO 2-pyrazoles-5-base, 1-CH 3-4-NO 2-pyrazole-3-yl or by R 21, R 22And R 23The phenyl that replaces.
The compound of formula I, wherein R 1It is phenyl or by C 1-4Alkyl, C 1-4Alkoxyl group, halogen, or CF 3Mono-substituted phenyl; R 2, R 3And R 4Be respectively H, or CH 3; A 2Be CH(CF 3), CH 2Or O; Y is 3,5-two chloro-2-pyridyl, 1-CH 3-4-NO 2-pyrazoles-5-base, 1-CH 3-4-NO 2-pyrazoles-3 base or by R 21, R 22And R 23The phenyl that replaces is preferably by R 21, R 22And R 23The phenyl that replaces.
Formula II compound as raw material; Can obtain with a kind of known method.
The compound of many formula II a, the tautomeric forms that they also can formula II b exists:
N wherein, A 1, A 2, X, R 2, R 3And R 4Definition as above.They can use and be suitable for importing (A 1) electrophilic reagent of nX group obtains from the anionic γ of two valencys-position metalepsy of the beta-dicarbonyl compound of formula V easily
Figure 891017437_IMG29
A wherein 2, R 2, R 3And R 4Definition as above.
The γ-position metalepsy of dianion that is suitable for the beta-dicarbonyl compound of through type V imports (A 1) electrophilic reagent of nX group knows that from document its character will depend on (A 1) connotation of nX.
The electrophilic reagent suitable to γ-position metalepsy for example is:
-replaced by Cl: Cl 3C-CCl 3Or N-Cl-succinimide.
-replaced by Br: Br 2
-replaced by the S-alkyl: disulphide such as alkyl-S-S-alkyl and phenyl-S-S-phenyl.
-replaced by SH: Sulfur
-replaced by OH: O 2
-replaced by COOH: carbonic acid gas
-by C(OH) RR ' (for example C(OH) (phenyl) 2) replacing: aldehydes or ketones is (as (phenyl) 2CO), by the carbonyl addition.
-by NO 2Replace: isoamyl nitrate.
-replaced by aliphatic series or araliphatic hydrocarbon: corresponding hydrocarbyl halide.
Thereby, if necessary, can be transformed into other functional group to the functional group that introduces with a kind of known method.
R wherein 1And R 16The compound that generates the formula II of a key together can remove hydrogen halide by corresponding halogenide and obtain.Like this formula II compound of Huo Deing with for example methyl alcohol, for example can obtain by methoxyl group the saturated compound of the formula II that acetoxyl group replaces in the addition reaction of acetate etc.
Use the Dieckman condensation reaction, can obtain the compound of many formula V by cyclic action
Provided the example of the reaction scheme of preparation formula VI compound below.
Figure 891017437_IMG32
(n=0.1,2) X=halogen
R 1The formula II compound that is vinyl for example can be from corresponding R 1Be CH 2CH 2The formula R of OH 1Compound obtains by dehydration, is easily with the toluenesulphonic acids dehydration of salt.
For example use Zn/CH according to Simmon/Smith 2I 2Such vinyl compound can be transformed into corresponding cyclopropyl compounds.
R 1And R 2Be CH together 2Formula II compound can pass through R 1And R 2Be the corresponding formula II compound and the ClCH of the dianion form of H 2S-CH 3Reaction, that continues makes resulting R 1Be CH 2SCH 3Formula II compound carry out the S-oxidation, with above-mentioned CH 2S(O) CH 3Group is transformed into CH 2Group and obtaining.
R 1And R 2Be C together 2-5The formula II compound of alkylidene group can pass through R 1And R 2Be the corresponding formula II compound and the aliphatic C of the dianion form of H 2-5Aldehyde or C 3-5Reactive ketone, the dehydration by resulting alcohol obtains subsequently.
Can know,, therefore must select suitable reaction scheme and only reactions steps order because preparation formula II compound will depend primarily on the rational combination of each substituting group.The chemist in present technique field is easy to make this selection.
So far also do not address the preparation of raw material, this starting compound is known, is under the new compound situation at them perhaps, can by be similar in this literary composition, describe or be similar to the preparation of known method.
The free acid form of formula I compound, ether, ester or agricultural go up acceptable salt form and show significant broad-spectrum weed-killing activity.For known dione herbicides, consider for example its favourable crop safety and/or environmental acceptability, (for example optimum soil movability) compound of the present invention provides valuable alternative.
The method that the present invention also relates to go out and cut weeds, this method comprise that the formula I compound of herbicidally effective amount is gone up acceptable salt with free acid form or agricultural is administered to the weed growth place.
In greenhouse test, be 0.33,1.0 and the test dose of 3kg/ha is represented before the bud and weeding activity behind the bud with being equivalent to amount of application.The specific weeds that the amount of used formula I compound will be removed according to going out, employed compound, this compound use-pattern, decisions such as the envrionment conditions during processing.Those of ordinary skill in the art is by conventional steps, perhaps for example in the greenhouse activity and the known amount of application standard of required formula I compound compared the suitable amount of application that decides this compound.In general, when formula I compound is used the plant growth place with 0.03 to 3kg/ha amount, can obtain satisfied herbicidal effect.Various formula I compounds have shown favourable optionally weeding activity in this amount ranges.Thereby, the compound 2.82(Table A that sees below) approximately when using behind 1 to the 2kg/ha amount of application bud, it shows weeding selectivity excellent in beans, and can prevent and kill off various broadleaf weedss well.
Formula I compound can and also preferably with agricultural on acceptable diluent combine with herbicidal composition and use.The preparation of this suitable compound contains 0.01% to 99% effective ingredient, the tensio-active agent of 0-20% and the solid of 1-99% or liquid diluent by weight.Sometimes need be for the tensio-active agent of active ingredient higher proportion, this can be by mixing tensio-active agent in the preparation or jar mixed obtaining.Composition applied agents shape generally contains the effective ingredient of weight 0.01-25%.Certainly, effective ingredient higher or low consumption depend on and give fixed purposes, the physical properties of this compound and use-pattern.Plan to use the conc forms of preceding dilute compositions generally to contain weight and be 2-90%, preferably contain the active ingredient of 10-80%.
The preparation of useful formula I compound comprises pulvis, granule, strong suspending agent, wettable powder, missible oil, flowing agent etc.By usual method, as with formula I compound and mixing diluents, and at random mix and to obtain these preparations with other composition.
In addition, formula I compound can use with microencapsulation form.
For the result of use and for example foaming of minimizing that improve active ingredient, caking and erosion can be used acceptable various additives on the agricultural in this Herbicidal mixtures.
" tensio-active agent " is acceptable material on a kind of agricultural as used herein, and they have emulsifying property, diffustivity, and wettability, dispersiveness or other improve the performance on surface.The example of tensio-active agent is sodium lignosulfonate and sodium lauryl sulphate.
" thinner " is acceptable liquid or solid material on a kind of agricultural as used herein, is used to make concentrated medicament to be diluted to a kind of suitable or required concentration.For pulvis and granule, thinner for example is a talcum, kaolin or diatomite, and for liquid concentrate, thinner for example is that hydrocarbon (as dimethylbenzene) or alcohol (as Virahol) they are water or diesel oil for the liquid application form.
Compound of the present invention also can include bioactive other compound, the compound of similar or additional weeding activity is for example arranged or detoxifcation is arranged, the compound of sterilization or insecticidal activity.
The following examples are used for illustrating practice of the present invention.Temperature is degree centigrade, and RT is a room temperature, and umber and percentage ratio are by weight.
Herbicidal composition
Embodiment A: wettable powder
With 25 parts of formula I compounds that hereinafter provide, as the compound of embodiment 1 and 25 parts of synthetic particulate silica gel, 2 parts of sodium lauryl sulphate, the kaolin of 3 parts of sodium lignosulfonates and 45 parts of meticulous screenings mixes also and grinds, and reaches about 5 microns until fineness.
Embodiment B: missible oil
With 25 parts of formula I compounds that hereinafter provide, as the compound of embodiment 1 and 50 parts of dimethylbenzene, 15 parts of dimethyl formamides and 10 parts of emulsifying agent thorough mixing until obtaining uniform solution.
The herbicidal performance screening
Experimental example 1: bud pre-treatment
Fill up kind of a basin with the matrix that is equivalent to sandy loam, the seed of piemarker (At hereinafter), Amaranthus retroflexus (Ar), Europe sinapsis alba (Sa), black nightshade (Sn), downy brome (Bt), Herba Setariae Viridis (Sv), wild avena sativa (Af), barnyard grass (Ec) under in every basin, planting.
Then the substances of formula I is used with the amount that per hectare is equivalent to 0.25,1 and/or 4 kilogram of active constituent, applied volume is equivalent to 1000 liters of per hectares; (reagent of use test(ing) liquid preparation such as Embodiment B sprays).After using, seed is covered with thin-layer matrix (about 0.5 centimetre), plant basin and kept 21 days illumination every day 14-17 hour (daylight or equivalent) in room temperature (30-24 °).
Carry out the mensuration of herbicidal effect after 21 days.Mensuration comprises the visual evaluation to various phanerogamous degree of damage and character.
Observe weeding activity
Experimental example 2: bud aftertreatment
According to carrying out with experimental example 1 similar step, be that the 2-4 leaf is used the invention compound during phase just plant, other test conditions (using ratio, applied volume, temperature, illumination) and evaluation method (after using 21 days) are all described in experimental example 1.
Observe weeding activity
Experimental example 3
According to similar in appearance to experimental example 1 and 2 described methods, experimental liquid with various concentration, carry out the shaker test of formula I compound to various seeds, these plants are: the grass seed leaf and the dicotyledonous careless class that are selected from broad-leaf weeds: piemarker, shepherd's purse, Cassia tora, lamb's-quarters, thorn apple, Tender Catchweed Bedstraw Herb, Yin Ye lead a cow, Binzhou genus, purslane, Europe squaw weed, thorn Radix sidae acutae, black nightshade, chickweed, Siberian cocklebur; Grass tree section grass class: fast sward, Rhizoma Cyperi, mouse tail amur foxtail, Apera spica-Venti, wild avena sativa, arm shape grass, downy brome, lady's-grass, barnyard grass, knucklegrass, annual bluegrass, Fu Shi Herba Setariae Viridis and Johnson grass; And farm crop, as broad leaf crop: cotton, soybean, sugar beet, Sunflower Receptacle and grass tree section crop: rice, corn (Zea mays) and its concentration of milo/sorghum are selected from required using than (be equivalent to 0.11,0.33 and 0.1 kilogram of formula I compound of per hectare).Applied volume is equivalent to 600 liters of per hectares.
Use after 28 days and estimate, observe and use the weeding activity that scope is a 30-1000 gram/hectare.
To note observing the interesting weeding activity of following array type I compound especially.
Formula I b compound, wherein A 2Be CH 2, R 1Be phenyl or substituted-phenyl (being preferably phenyl, 2-fluoro phenyl or 4-fluoro phenyl), R 2-R 4Can at random be hydrogen or methyl, and y be R 21, R 22And R 23The phenyl that replaces is as compound 2.82,2.88 and 2.89 hereinafter.
Formula I b compound, wherein A 2Be CH(CF 3), R 1-R 4At random be hydrogen or methyl, for example formula I b compound, wherein A 2Be CH(CF 3), R 1-R 4Be hydrogen or methyl, y is R 21, R 22And R 23The phenyl that replaces is as compound 2-177,2-192,2-195 and 2-248 hereinafter.
Formula I b compound, wherein y is substituted pyrazolecarboxylic base (particularly 1-methyl-4-nitro-pyrazoles-5-base or 1-methyl-4-nitro-pyrazole-3-yl, and A 2Be methylene radical or oxygen, comprise wherein R 1-R 4At random be compound and their ester or the salt of hydrogen or methyl, following cultural compound 2-165,2-167,2-169,2-172,2-173,2-174,8-21,9-1 and 9-2.
Formula I b compound, wherein A 3
Figure 891017437_IMG34
A 4Be C(Cl)=C(O), A 2Be methylene radical, comprise that y is R 21, R 22And R 23The phenyl and the R that replace 1-R 4At random be those compounds of hydrogen or methyl, as compound 10.1 and 10.2 hereinafter.
Formula I f compound, wherein A 2Be CH, comprise that wherein y is R 21, R 22And R 23The phenyl and the R that replace 2-R 4At random be those compounds of hydrogen or methyl, for example compound 2-156.
Test-results 1
Below the data sheet of table 1 understand according to the formula I compound solutions of above experimental example 1 and 2 tests at the weeding activity of using when being equivalent to 1 kilogram/hectare.
The evaluation of weeding activity is by the decimal system, and 1 is equivalent to weeding activity 0-10%, and 10 are equivalent to weeding activity 90-100%.
The table I
Behind the preceding bud of bud
Cpd.??At??Ar??Sa??Sn??Bt??Sv??Af??Ec??At??Ar??Sa??Sn??Bt??Sv??Af??Ec
2.1????9????10????10????10????10????10????10????10????9????9????9????9????10????9????9????8
2.5????10????10????9????9????5????7????1????9????8????6????9????10????1????1????1????8
2.9????10????10????9????10????4????10????1????10????9????10????10????10????4????8????6????9
2.15????10????10????9????10????9????10????7????9????9????8????8????9????6????7????7????8
2.24????10????10????8????10????4????9????4????9????9????9????9????9????1????1????9????3
2.65????10????10????10????10????10????9????7????10????8????7????7????10????5????5??6??8
2.82????10????10????10????10????1????9????2????9????10????8????10????9????1????3????6????9
2.84????9????9????9????9????1????1????1????1????9????9????9????9????1????1????1????8
2.85????9????5????9????9????1????1????1????1????9????9????9????9????3????1????1????8
2.168????10????10????9????10????8????9????1????9????9????9????9????9????8????8????1????9
2.170????10????10????1????9????6????9????1????9????9????9????9????9????1????4????1????7
2.171????10????9????8????10????1????8????1????8????9????9????9????10????10????9????8????9
2.172????10????9????3????10????4????9????1????9????9????8????7????9????4????4????3????6
2.173????10????10????10????10????10????10????4????10????9????9????9????10????10??9??9??9
2.174????10????10????6????10????8????9????1????9????9????9????9????9????9????8????8????9
2.203????9????8????8????8????3????9????1????9????9????8????9????9????1????1????1????9
2.204????10????9????8????9????4????9????1????9????9????4????9????9????3????3????1????8
8.21????10????10????10????9????1????5????1????9????9????8????8????9????1????1????1????4
Test-results 2
The following table II shows the weeding activity according to the formula I compound solution of test in the experimental example 3 above, its use than and the time (before the bud or behind the bud) illustrate that in table the same with the table I, its evaluation is represented with the decimal system.
Use following abbreviation in the table II:
Piemarker Abutilon theophrasti ABUTH
Shepherd's purse Capsella bursa pastoris CAPBP
Cassia tora Cassia obtusiflolia CASOB
Lamb's-quarters Chenopodium album CHEAL
Thorn apple Datura stramonium DATST
Tender Catchweed Bedstraw Herb Galium aparine GALAP
The garden leaf Ipomoea purpurea IPOMO that leads a cow
Binzhou few Polygonium pensylvanicum POLPY
Purslane Portulaca oleracea POROL
Herba Senecionis Vulgaris Senecio vulgaris SENVU
Thorn Radix sidae acutae Sida spinosa SIDSP
Black nightshade Solanum nigrum SOLNI
Chickweed Stellaria media STEME
Siberian cocklebur Xanthium strumarium XANSP
Speed sward Agropyron repens AGRRE
Rhizoma Cyperi Cyperus rotundus CYPRO
Mouse tail amur foxtail Alopecurus myosuroides ALOMY
Apera????spica-venti????AGSSV
Wild avena sativa Avena fatua AVEFA
Arm shape grass Brachiaria plantaginea BRAPL
Downy brome Bromus tectorum BROTE
Lady's-grass Digitaris sanguinalis DIGSA
Barnyard grass Echinochloa crus-galli ECHCG
Knucklegrass Panicum dichotomiflorum PANDI
Annual bluegrass Poa annua POAAN
Fu Shi Herba Setariae Viridis Setaria faberi SETFA
Johnson grass Sorghum halepense SORHA
Barnyard grass (wetting) Echinochloa crus-galli wet ECHwet
Soybean
Sugar beet
Sunflower Receptacle
Use Pre before the bud
Use Po behind the bud
Table II weeding activity
Time of application pre po po pre po po pre po pre po
Use than 0.33 0.33 1 0.3 111111
(kilogram/hectare)
Compound number 2.1 2.1 2.82 11 11 2.203 2.173 2.173 1.174 2.175
Test plant
ABUTH????10????10????10????10????10????10????10????10????10????10
CAPBP????10????10????10????9????10????10????10????10????10????10
CASOB????1????7????5????6????6????4????1????7????2????8
CHEAL????10????10????9????10????10????9????10????10????10????10
DATST????10????10????10????10????4????10????10????10????9????10
GALAP????4????5????6????10????10????5????7????9????6????9
IPOMO????6????7????10????10????8????6????5????9????6????9
POLPY????10????10????10????10????10????10????10????10????10????10
POROL????10????10????10????10????6????10????10????10????10????10
SENVU????10????10????10????10????10????10????10????10????10????10
SIDSP????10????9????9????10????10????8????9????6????10????10
SOLNI????10????10????10????10????10????10????10????10????10????10
STEME????10????10????9????8????8????10????10????10????10????10
XANSP????-????-????9????10????10????8????-????-????-????-
cotton????1????3????5????8????8????4????3????5????4????4
soybea????5????9????0????2????6????4????8????10????7????7
sugarb????10????10????10????10????10????10????10????10????10????10
sunflo????6????7????6????-????-????2????7????9????7????9
AGRRE????9????3????-????10????8????1????8????1????2????1
CYPRO????9????1????6????-????-????2????10????5????10????3
ALOMY????8????3????1????8????10????0????8????3????5????2
AGSSV????10????9????3????10????4????2????10????10????10????9
AVEPA????8????7????1????6????4????0????7????4????4????1
BRAPL????10????8????6????10????10????3????10????9????10????10
BROTE????10????7????0????4????6????1????9????9????6????1
DIGSA????10????10????9????10????10????8????10????10????10????10
ECHCG????10????7????6????10????8????3????10????6????10????9
PANDI????10????10????1????10????10????2????10????9????7????9
POAAN????9????4????1????10????8????1????9????9????3????2
SETFA????10????10????1????4????8????2????10????9????7????8
SORHA????10????10????1????4????10????2????6????9????6????4
ECHwe：????10????10????9????-????-????10????10????10????10????10
rice????10????10????5????2????8????1????10????10????10????10
corn????6????1????0????2????6????0????3????0????1????1
wheat????8????1????0????4????2????0????6????1????5????1
milo????9????8????2????4????5????2????10????7????10????2
Final compound
Embodiment 1
2-((4-chloro-2-nitro) benzoyl)-4,4,6-trimethylammonium-6-methylthio group-hydroresorcinol
With 8.07 gram (0.021mol) 3-((4-chloro-2-nitro)-benzoyl oxygen base)-4; 4; 6-trimethylammonium-6-methylthio group-2-tetrahydrobenzene-1-ketone is dissolved in 3.5ml(0.025mol) in warm (45 °) mixture of triethylamine, 0.4ml acetone cyanohydrin and 60ml anhydrous acetonitrile; stir after 3 hours and dilute with the 200ml ether in room temperature reaction solution; and use 35ml 10%HCl and 150ml water washing successively, use anhydrous sodium sulfate drying then.
Solvent is rotated the resistates that stays after the evaporation and handles with silica gel chromatographic column, obtains analytically pure title compound with hexane-ether (1: 1) wash-out, fusing point 111-112 °.
Embodiment 2
Method similar to Example 1 obtains following formula I compound (free acid form) by corresponding formula IV compound rearrangement: Table A, B, C and D.
Table A: formula I c compound
Figure 891017437_IMG36
Figure 891017437_IMG37
Figure 891017437_IMG38
Figure 891017437_IMG40
Figure 891017437_IMG43
Figure 891017437_IMG44
Figure 891017437_IMG45
Figure 891017437_IMG48
Figure 891017437_IMG49
Figure 891017437_IMG52
Figure 891017437_IMG55
Embodiment 3
The 2-(2-nitro benzoyl)-4-phenoxy group-hydroresorcinol
With 4.1 gram (0.02mol) 4-phenoxy groups-1, hydroresorcinol, 3.7g(0.02mol) 2-nitrobenzoyl chloride, 2.0g(0.02mol) mixture of triethylamine and 60ml toluene refluxes and stirred 1 hour, with mixture cooling and adding 200ml ether, suction filtration goes out sedimentary Triethylammonium chloride and washs with ether then.Filtrate is successively with 10ml 2N hydrochloric acid, 20ml water, 10ml 2N sodium hydroxide and the extraction of 50ml water, the organic layer dried over mgso, at 30 ° of vacuum-evaporation ether, stay the toluene solution of intermediate product, add 1g(0.012mol) acetone cyanohydrin and 2g(0.02mol) triethylamine and at room temperature stirring 3 hours, this intermediate product is rearrangeable.
Reaction mixture is dissolved in the 200ml ether, successively with 15ml 2N hydrochloric acid, 20ml water, 20ml 2N sodium hydroxide and the extraction of 50ml water, merge back two kinds of water extracts,, add 30ml 2N hydrochloric acid then while stirring and carry out acidifying with the ether washing, suction filtration goes out throw out after 30 minutes, and use methanol wash, the 2.8g fusing point is 109-115 ° a white powder, use ethyl alcohol recrystallization, get the 1.7g title crystal, fusing point 115-116 ℃.
Embodiment 4
Similar in appearance to the method for embodiment 3, by corresponding formula II and III compound, the ester of separate type IV compound does not obtain the above compound of Table A, B, C and D.
Embodiment 5
2-(2,4-dichloro-benzoyl base)-3-methoxyl group-4-allyl group-4,6,6-trimethylammonium-2-tetrahydrobenzene-1-ketone
With 3.67g(0.01mol) 2-((2; the 4-dichloro) benzoyl)-and 4-allyl group-4,6,6-trimethylammonium-1; hydroresorcinol is dissolved in the 10ml 0.1N sodium hydroxide, then formed sodium salt solution is used the 1.7g(0.01mol in the 10ml water) the Silver Nitrate processing.
Formed silver salt precipitation is diluted with 10ml water, and suction filtration is also used P in vacuum drier 2O 5Dry.To obtain anhydrous silver salt like this and be suspended in the 100ml anhydrous diethyl ether, and use 1ml(0.016mol) the methyl-iodide processing.
Reflux after 3 hours, reaction mixture is cooled to room temperature and filtration.
Rotary evaporation filtrate stays the title compound raw product, is faint yellow viscosity oily matter, can be on silica gel chromatography purification (with 1: 5 wash-out of ether/hexane).
Embodiment 6
2-((2-chloro-4-methylsulfonyl) benzoyl)-3-acetoxyl group-4-methylthio group-4,6,6-trimethylammonium-2-tetrahydrobenzene-1-ketone
At 4.87g(0.0117mol) 2-((2-chloro-4-methylsulfonyl) benzoyl)-4-methylthio group-4; 6; 6-trimethylammonium-hydroresorcinol adds 0.35g(0.0117mol in well-beaten solution in the 25ml anhydrous dimethyl formamide) sodium hydride (80% is scattered in the mineral oil)-must all add immediately.
After thermopositive reaction (42 °) finishes, the gained sodium salt solution at room temperature stirred 1 hour again, use 0.93ml(0.013mol then) the Acetyl Chloride 98Min. processing, after at room temperature reacting 18 hours, add 300ml water, the suction of formed flaxen enol acetic ester precipitation leaches, and washes with water, fully drainage water and 60 ° of dryings.
The rough title ester compounds chromatographic separation on silicagel column that so makes,, obtain analytically pure title compound, fusing point 126-128 ° (R with 4: 1 wash-outs of ether/hexane f=0.4, silica gel, eluent ether).
Embodiment 7
With method, with corresponding initial substance formula I b compound and compound R similar in appearance to embodiment 5 ' aI obtains following formula I a compound: table E.
Embodiment 8
With method, with corresponding initial substance formula I b compound and acyl halides R similar in appearance to embodiment 6 ' aCl obtains following formula I a compound: table F.
Figure 891017437_IMG58
Figure 891017437_IMG59
Embodiment 9
2-((2-nitro-4-chlorine)-benzoyl)-4-methylthio group-4-methyl isophthalic acid, the preparation of hydroresorcinol ammonium salt.
With 0.96g(0.0056mol) 1-(methylamino methyl)-the 10ml dichloromethane solution of naphthalene adds 2.0g(0.0056mol) 2-((2-nitro-4-chlorine)-benzoyl)-4-methylthio group-4-methyl isophthalic acid; in the 30ml methylene dichloride suspension of hydroresorcinol; after 1 hour solvent is steamed; solid residue is in 40 ° of drying under reduced pressure; obtain 2.95g yellow crystal shape salt, fusing point 75-80 ℃.
Use similar in appearance to the method for embodiment 9 and obtain
9.1-2-(1-methyl-4-nitro-pyrazoles-5-acyl)-and the hydroresorcinol triethylammonium salts, fusing point 87-99 °,
9.2-2-(1-methyl-4-nitro-pyrazoles-5-acyl)-4,4,6,6-tetramethyl--hydroresorcinol triethylammonium salts, fusing point 144-145 °.
Embodiment 10
2-chloro-2-((2-nitro-4-chlorine) benzoyl)-5,5-dimethyl-hydroresorcinol
With 3.25g(0.01mol) 2-((2-nitro-4-chlorine) benzoyl)-5,5-dimethyl-hydroresorcinol and 1,3g(0.01mol) mixture of N-chlorosuccinimide in the 40ml methylene dichloride refluxed two days, steamed solvent then.In resistates, add ether, and insolubles is leached (crystallization of 0.5g succinimide, fusing point 123-125 ℃).Filtrate is through rotary evaporation, and result product with 8: 2 chromatographic separation of cyclohexane/ethyl acetate, provides the yellow crystal title compound, fusing point 135-138 ℃ on silicagel column.
Use similar in appearance to the method for embodiment 10, with required 2-aroyl-1,3-cyclic diketones and N-chloro-succinimide obtain
10.1-2-chloro-2-(4-chloro-2-nitro benzoyl)-4,4,6-trimethylammonium-hydroresorcinol, fusing point 77-78 ℃,
10.2-2-chloro-2-(4-chloro-2-nitro benzoyl)-4,4,6,6-tetramethyl--hydroresorcinol, fusing point 87-99 ℃.
Embodiment 11
2-(4-chloro-2-nitro benzoyl)-1,3-encircles heptadione
At 5.95g suberane-1,3-diketone (0.472mol) is in 50mlCH 2Cl 2Solution in once add 9.51g4-chloro-2-nitrobenzoic acid (0.472mol), then drip 6.21g triethylamine (1.3eq.) again, reaction mixture at room temperature stirred 2 hours, used CH 2Cl 2Dilution, and water (30ml) washing, providing after the evaporation almost is the 3-(4-chloro-2-nitrobenzoyl acyloxy of pure enol ester)-2-suberene-1-ketone.
Above-mentioned 14.62g(0.0472mol) enol ester is dissolved in the 50ml acetonitrile and once adds the 9.55g triethylamine.
Add the 1.5ml acetone cyanohydrin with syringe, mixture at room temperature stirs and spends the night, remove acetonitrile under the vacuum, resistates is dissolved in ether, this solution washs, separates, uses dried over mgso through 2N HCl, and the resistates that provides after the evaporation provides title compound through chromatographic separation, 112 ℃ of fusing points again.
Embodiment 12
2-((2-nitro-4-chlorine) benzoyl)-4-chloro methylthio group-4-methyl isophthalic acid, hydroresorcinol
With 3.6g(0.01mol) 2-((2-nitro-4-chlorine) benzoyl)-4-methylthio group-4-methyl isophthalic acid; hydroresorcinol and 1; 3g(0.01mol) mixture heating up of N-chlorosuccinimide in the 50ml methylene dichloride refluxed 5 days; steam solvent; resistates is used the methylene dichloride chromatographic separation on silicagel column; generate yellow crystal shape title compound, fusing point 143-144 ℃.
Intermediate (formula IV compound)
Embodiment 13
3-((4-chloro-2-nitro) benzoyloxy)-4,4,6-trimethylammonium-6-methylthio group-2-tetrahydrobenzene-1-ketone
0 ° with time of 5 minutes with 6ml(0.043mol) anhydrous triethylamine is added drop-wise to through well-beaten, refrigerative 7.05g(0.032mol) 4-chloro-2-nitrobenzoyl chloride and 6.4g(0.032mol) 4-methylthio group-4,6,6-trimethylammonium-hydroresorcinol is in the solution of 70ml anhydrous methylene chloride.
Remove water-bath after being added dropwise to complete, make reaction mixture be warming up to room temperature, under this temperature, kept 3 hours, and then use the 150ml water treatment.Organic phase is separated, use 100ml 2N hydrochloric acid, 150ml water, 100ml 5%K successively 2CO 3Anhydrous Na is used in solution and the water washing of 150ml salt then 2SO 4Dry.
Remove the viscosity oily matter that stays behind the solvent and be solidified into ingot immediately, generate analytically pure enol ester, fusing point 120-122 ℃ with hexane development back.
Embodiment 14
With method,, obtain following formula IV a compound: table G with corresponding starting raw material formula II and III compound similar in appearance to embodiment 13.
Figure 891017437_IMG65
Figure 891017437_IMG66
Embodiment 15
With method,, obtain following formula IV compound: table H with corresponding starting raw material formula II and III compound similar in appearance to embodiment 13.
Figure 891017437_IMG67
Figure 891017437_IMG68
Figure 891017437_IMG69
Embodiment 16
4-methylthio group-4,6,6-trimethylammonium-hydroresorcinol
In the exsiccant nitrogen atmosphere, on one side stir, on one side with 300ml 1.6M just-hexane solution (0.48mol) of butyllithium is added dropwise to 48.5g(0.48mol) Diisopropylamine is at 420ml tetrahydrofuran (THF) (THF; Use the 4A molecular sieve drying) solution in, rate of addition will make temperature not raise above-68 °.
After being added dropwise to complete, reaction mixture (comprising diisopropyl amide base lithium) is being used 30.9g(0.2mol then-70 ° of following restir 30 minutes under same temperature) 4,4, the solution-treated of 6-trimethylammonium-hydroresorcinol in the anhydrous THF of 200ml.
After all diketone all added, reaction soln kept 30 minutes at-70 °.
At last at-70 °, dripping 45.2g(0.48mol with 15 fens clock times) dimethyl disulphide is in the solution of the anhydrous THF of 150ml.
Remove dry ice/acetone batch then, make reaction mixture be warming up to-9 °, and handle with the 100ml concentrated hydrochloric acid.
Rotary evaporation THF(30 °) after the resistates that stays with the dilution of 200ml water, and with 500ml extracted with diethyl ether secondary.
Merging, dry (Na 2SO 4) after the ether extract, vacuum concentration is to original volume 1/3rd, sedimentary then crystallization suction leaches.
Obtain analytically pure title compound diketone with the Virahol recrystallization, 147 ° of fusing points.(R f=0.24, silica gel, elutriant ether/hexane 2: 1)
Embodiment 17
4-methylthio group-4-methyl isophthalic acid, hydroresorcinol
Stir on one side, on one side in 30 minutes 43g(0.5mol) methyl acrylate and 59g(0.5mol) mixture of 3-methylthio group butanone-2, joining 100ml 5.4M(0.54mol) sodium methylate of methanolizing is in the solution of 200ml methyl-sulphoxide, thermopositive reaction remains on below 40 ° to be carried out, and at room temperature continuously stirring is spent the night.Then ice cube and 60ml concentrated hydrochloric acid are added reaction mixture and generate lurid precipitation, its suction is leached and, 120-122 ℃ of product fusing point 50 ° of vacuum-dryings.
Embodiment 18
4-methoxyl group-4-methoxycarbonyl-hydroresorcinol
Stir on one side, on one side in 20 minutes 58g(0.358mol) methoxyl group dimethyl malonate and 25g(0.357mol) mixture of methyl vinyl ketone joins 66ml 5.4M(0.356mol) sodium methylate of methanolizing is in the solution of 120ml methyl-sulphoxide, make thermopositive reaction remain on 35 ℃ with the water-bath cooling, add 200ml water after 1 hour, mixture dichloromethane extraction secondary, water layer is with the 80ml20% hcl acidifying and use dichloromethane extraction.Extract washes with water, uses dried over mgso, and vacuum-evaporation obtains viscosity oily matter, handles to such an extent that fusing point be 122-124 ℃ yellow crystal with ether it.
Embodiment 19
4-methylthio group-6,6-dimethyl-4-tetrahydrobenzene-1,3-diketone
Need not cool off, at 2.8g(0.015mol) 4-methylthio group-6,6-dimethyl-hydroresorcinol adds 5.3g(0.0169mol in batches in the solution of 50ml methylene dichloride) between-chlorine peroxybenzoic acid (55%).
When peracid all adds, add 1ml(0.0175mol) glacial acetic acid, and reaction mixture reflux 18 hours.
Be cooled to room temperature and filtration then.
The filtrate rotary evaporation provides the block title compound of crystallization, this compound silica gel column chromatography purifying (with 3: 1 wash-outs of ether/hexane); R f=0.28(silica gel is used the ether wash-out); Fusing point 163-165 ℃.
Embodiment 20
Compounds by embodiment 17 begins, and obtains following compound with addition reaction:
-4-methoxyl group-4-methylthio group-6,6-dimethyl-hydroresorcinol (addition of methyl alcohol)
-4-acetoxyl group-4-methylthio group-6,6-dimethyl-hydroresorcinol (addition of acetate)
Embodiment 21
Use similar in appearance to the method for embodiment 17, as initial substance, obtain the compound of following formula II: table J with suitable methyl ketone and carboxylicesters.
Figure 891017437_IMG71
Embodiment 22
With with embodiment 16 similar methods, use suitable formula V initial substance and electrophilic reagent (table K), obtain showing the formula II compound of L.
Figure 891017437_IMG75
Figure 891017437_IMG76
Embodiment 23
4,4-dimethyl-6-methylene radical-hydroresorcinol (a) and 4,4-dimethyl-6-methoxymethyl-hydroresorcinol (b)
Under agitation 26g(0.2mol) 2-methylol-2-ethyl propenoate and 17.2g(0.2mol) mixture of 3-methyl-2-butanone be added drop-wise to 40ml 5.4M methanolizing sodium methylate in the solution of 80ml anhydrous dimethyl sulfoxide, the speed of adding should make temperature be no more than 40 °.
Add finish after, brown reaction soln is restir 2 hours at room temperature, uses the 300ml water treatment then.
Aqueous solution 100ml CH 2Cl 2The extraction secondary, organic extract anhydrous sodium sulfate drying, vaporising under vacuum.The crude mixture of two title compounds of gained is made moving phase with hexane-ether and separated with chromatography: (hexane-ether 3: 1) that at first washes out is that the 6-methylene radical replaces 144-146 ℃ of diketone a(fusing point; R f=0.35, silica gel, ether wash-out), anti-Michael (Michael) reaction product of the 6-hydroxymethyl derivative that forms when it is beginning; (hexane-ether 2: 1) continues to wash out the cyclohexanedione b that obtains the replacement of 6-methoxymethyl, fusing point 108-110 ℃ (R on silicagel column f=0.24, silica gel, ether wash-out).
Embodiment 24
4-methyl-5-Trifluoromethyl-1, hydroresorcinol
Under agitation, with 30 minutes times 7.2g(0.1mol) 2-butanone and 16.8g(0.1mol) β-(trifluoromethyl) ethyl propenoate is added drop-wise in 20ml methyl alcohol and 60ml anhydrous dimethyl benzene and is dissolved with in the solution of 2.7g Na, reaction mixture refluxed 3 hours also is evaporated to dried, resistates is dissolved in 50ml water, handles with concentrated hydrochloric acid.Sedimentary crystal suction is leached water and ether washing and dry, fusing point 122-128 ℃.
With method, obtain the 5-Trifluoromethyl-1, hydroresorcinol, fusing point 143-144 ℃ similar in appearance to embodiment 24; 4.4-dimethyl-5-Trifluoromethyl-1, hydroresorcinol, fusing point 122-128 ℃.

Claims (33)

1, a kind of method of preparation I compound
R wherein 1, R 2, R 3And R 4It is respectively the aliphatic hydrocarbyl group of undersaturated maximum 6 carbon atoms; The group of naphthene base of maximum 6 carbon atoms; Ar or (A 1) nThe X group; R thus 1, R 2, R 3And R 4In one also can be C 2-5Carbalkoxy; R 1, R 2, R 3And R 4In at least one be (A 1) nX; R 1With R 2Together or R 3With R 4Also can be C together 2-5Alkylidene group, R 1And R 2Also can generate oxo or C together 1-5Alkylidene group,
Ar be unsubstituted or replace by being selected from O, 5 yuan or 6 yuan of heteroaryls that 1 to 3 heteroatoms among N and the S is formed, and be connected on the ring A by ring carbon atom,
N is 0 or 1,
X is H, OR 6, SR 7, NR 8R 9, NO 2, halogen, CN, CF 3, CHF 2, S (O) mR 10, CO-NHR 11, CO-R 12, CR 13R 14-COO (C 1-6Alkyl) or benzyl,
A 1Be unsubstituted or by one or more C 1-5Methylene radical or ethylidene that alkyl replaces,
R 6And R 7Be respectively H, alkyl, haloalkyl, heteroaryl or CO-R 15Group,
R 8Be H, alkyl, heteroaryl or CO-R 15Group,
R 9, R 10, R 13And R 14Be respectively H, C 1-6Alkyl or aryl,
R 11Be H or alkyl,
R 12And R 15Be respectively H, alkyl or heteroaryl,
M is 1 or 2,
A 2Be a key, CR 16R 17, CR 16R 17-CR 18R 19, O, S, NR 20Or CO;
R 16And R 18Be respectively H, the carboxylic group of alkyl or free state, salt shape or esterification form, R thus 16And R 1On contiguous carbon atom, can generate a key together,
R 17And R 19Be respectively H, alkyl or (A 1) nX group, wherein A 1, n and X are as mentioned above.R thus 16And R 17Or R 18And R 19Also can represent (CH together 2) 2-5Group, thereby generate a kind of spirocyclic compound; And/or R 16And R 1Be close on carbon atom or R at it together 18And R 3On its contiguous carbon atom, can generate (CH together 2) 1-5, thereby generate a dicyclo,
R 20Be H, alkyl or CO-R 15, R wherein 15Define as above,
A 3
Figure 891017437_IMG4
A 4Be C=C (OR a) (group A) or C (X 1)-C (O) (group B),
X 1Be F or Cl,
R aBe H, a salifiable part or be the part of ether or ester with the oxygen bonding,
Y or by R 21, R 22And R 23The phenyl or the A ' that replace r
A ' rBe the heteroaryl group of 5 yuan or 6 yuan, it comprises that 1,2 or 3 is selected from O, the heteroatoms of S and N, and this heteroaryl group is unsubstituted or replaces, and is connected on the CO-group that it is bonded by a ring carbon atom;
R 21And R 22Be respectively H, halogen, C 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Haloalkyl, CN, NO 2, CF 3O, R bS (O) p, NR cR d, C (O)-R e, SO 2-NR cR dOr NR c-C (O)-R d, R thus 21And R 22Can form the (methylenedioxy) group together,
P is 0,1 or 2,
R bBe arbitrarily by halogen, cyano group, the C that phenyl or benzyl replace 1-4Alkyl;
R cAnd R dBe respectively H or C 1-4Alkyl,
R eBe C 1-4Alkyl or C 1-4Alkoxyl group,
R 23Be halogen, NO 2, CN, C 1-2Alkyl, C 1-2Alkoxyl group, C 1-2Haloalkyl or C 1-4Alkyl-S (O) q
Q is 0,1 or 2,
Thus, when Y is not the pyrimidyl that replaces arbitrarily, R 1, R 2, R 3And R 4In one also be the phenyl of phenyl or replacement, condition is:
A) at R 1, R 2, R 3And R 4One in, X only is H, this moment, following at least a kind of situation was suitable for:
I) CR 1R 2-A 2Be C (R 2)=C (R 17) or CR 1R 2-CR 16R 17-CR 18R 19,
Ii) Y is not phenyl that replaces arbitrarily or the pyrimidyl that replaces arbitrarily,
Iii) R 1And R 2Be oxo or C together 1-5Alkylidene group,
Iv) other at least substituent R 1, R 2R 3And R 4In one be undersaturated aliphatic hydrocarbyl group, naphthene group, unsubstituted or the phenyl or the Ar that replace,
V) other at least substituent R 1, R 2, R 3, R 4, R 17And R 19In one be (A 1) nThe X group, wherein X is not H,
Or vi) A 3
Figure 891017437_IMG5
A 4Be C (X 1)-C (O),
B) at CR 1R 2-A 2Be C (R 2)=C (R 17) time, R 3And R 4Both are not H entirely
And c) R 1And R 2When being oxo together, A 2Not O, S, NR 20Or CO
The compound that comprises the formula II
Figure 891017437_IMG6
R wherein 1, R 2, R 3, R 4And A 2Definition as above
Compound reaction with the formula III
Wherein Y defines as above, and Hal is a halogen
Reset the ester of the formula IV that obtains subsequently
Y wherein, R 1, R 2, R 3, R 4And A 2Definition as above
Obtain the compound of formula I b
Figure 891017437_IMG8
Y wherein, A 2, R 1, R 2, R 3And R 4Define as above, M is the salifiable part of H or shape, any etherificate, and the formula Ib compound that esterification or halogenation obtain thus becomes corresponding 2-(Y-CO)-2-alkene-1-ketone-3-alcohol ether, 2-(Y-CO)-2-alkene-1-ketone-3-alcohol ester or 2-X 1-2-(YCO)-1, the 3-dione compounds.
2, the process of claim 1 wherein R 1Be the undersaturated aliphatic group of 6 carbon atoms at the most, the group of naphthene base of 6 carbon atoms or Ar at the most, Ar defines as claim 1.
3, the process of claim 1 wherein CR 1R 2-A 2Be C(R 2)=CR 17, R wherein 2And R 17Definition is as claim 1.
4, the process of claim 1 wherein R 1And R 2Be oxo or C together 1-5Alkylidene group.
5, the process of claim 1 wherein A 3
Figure 891017437_IMG9
A 4Be C(X 1)-C(O), X wherein 1Definition is as claim 1.
6, the process of claim 1 wherein R 1Be CH 3, C 2H 5, vinyl, allyl group, propargyl, cyclopropyl, the phenyl that replaces arbitrarily; Furyl; Thienyl, (A 1) nX ', or R 1With R 2Be oxo together, CH 2Or CH-CH 3Group, or R 1With R 16Be a key together; N is 0 or 1; A 1By one or two CH 3The CH that group replaces arbitrarily 2Or (CH 2) 2, X ' is C 1-4Alkylthio; Thiophenyl; C 1-4Alkoxyl group; Phenoxy group; CHO; C 2-5Alkyloyl; OH and it and C 2-5Aliphatic carboxylic acid or the ester that generates with the phenylformic acid of any replacement; (C 2-5Carbalkoxy)-CH 2; (C 2-5Carbalkoxy)-CH(CH 3); Cyano group, F, Cl, CHF 2, CF 3, NO 2, CONH 2, CONH(C 1-4Alkyl), two (C 1-4Alkyl) N or benzyl; R 2, R 3And R 4In one be H, C 1-4Alkyl, C 1-4Alkoxyl group, C 1-4Alkylthio, OH, C 1-4Alkyl-CO-O, C 2-5Carbalkoxy, thienyl or furyl; R 2, R 3And R 4In any remaining substituting group be H or CH 3
7, the method for claim 6, wherein or A 2Be a key, CH 2, CH(CH 3), C(CH 3) 2, CO, O, CH(CF 3), CH 2-CH 2Or CH(CH 3)-CH(CH 3), perhaps A 2With CR 1R 2Be C(R together 2)=C(R 17), R wherein 17Be H, SCH 3, CH 3Or CF 3
8, the method for claim 7, wherein A 2Be CH 2, CH(CH 3) or C(CH 3) 2; (A 1) nX ' is NO 2, thienyl or furyl, and Y is by R 21, R 22And R 23The phenyl that replaces.
9, the method for claim 7, wherein n be 1 or 2 and Y by R 21, R 22And R 23The phenyl that replaces.
10, the method for claim 1 to 7, wherein Y is by R 21, R 22And R 23The phenyl that replaces, or thienyl, pyrazolyl, isothiazolyl, pyridyl, pyrazinyl or pyrimidyl, this heteroaryl are rolled into a ball by methylene-dioxy, NO 2, halogen, CN, CF 3, CH 3-SO 2Or CH 3SCH 2The ortho position replaces and it has 1 or 2 additional substituting group arbitrarily, and this additional substituting group is selected from halogen and the C that links a ring carbon atom 1-4Alkyl also is selected from the C that links theheterocyclic nitrogen atom 1-4Alkyl, benzyl and C 1-4Alkylthio-C 1-4Alkyl; R 22Be in the contraposition of carbonyl group and be H, halogen, C 1-4Alkyl-S, C 1-4Alkyl-SO 2, R 23Be at the ortho position of carbonyl group and be halogen, CF 3, NO 2, CN or CH 3SO 2And R 21Be H, halogen or CH 3
11, the method for claim 10, wherein Y is by R 21, R 22And R 23The phenyl that replaces.
12, the method for claim 10, wherein Y is pyrazolyl, pyrimidyl or the pyridyl that replaces.
13, the method for claim 12, wherein Y is the pyrazolyl that replaces.
14, the method for claim 12, wherein Y is the pyridyl that replaces.
15, the process of claim 1 wherein R 1Be H, CH 3, SCH 3, S(O) CH 3, SO 2CH 3, phenyl or by C 1-4Alkyl, C 1-4Alkoxyl group, halogen or CF 3Mono-substituted phenyl, perhaps R 1Be the alkenyl or the alkynyl group of maximum 4 carbon atoms.
16, claim 1 or 15 method, wherein R 2, R 3And R 4Be respectively H or CH 3, R thus 2, R 3And R 4In one also be SCH 3, S(O) CH 3Or SO 2CH 3, condition is R 2To R 4In only have one to be SCH 3, S(O) CH 3Or SO 2CH 3
17, the method for claim 16, wherein A 2Be OH(CF 3), CH 2Or O.
18, the method for claim 17, wherein Y is 3,5-two chloro-2-pyridyl.
19, the method for claim 17, wherein Y is 1-CH 3-4-NO 2-pyrazoles-5-base or 1-CH 3-4-NO 2-pyrazole-3-yl.
20, the method for claim 17, wherein Y is by R 21, R 22And R 23The phenyl that replaces, wherein R 21, R 22And R 23According to claim 1.
21, the method for claim 15, wherein R 1Be SCH 3, S(O) CH 3Or SO 2CH 3; R 2, R 3And R 4Be respectively H or CH 3; A 2Be CH 2, O or CH(CF 3); And Y is 3,5-two chloro-2-pyridyl, 1-CH 3-4-NO 2-pyrazoles-5-base, 1-CH 3-4-NO 2-pyrazole-3-yl or by R 21, R 22And R 23The phenyl that replaces.
22, the method for claim 21, wherein A 2Be CH(CF 3) or O and Y by R 21, R 22And R 23The phenyl that replaces.
23, the method for claim 15, wherein R 1Be the alkenyl or the alkynyl group of 4 carbon atoms at the most; R 2, R 3And R 4Be respectively H, CH 3, SCH 3, S(O) CH 3Or SO 2CH 3, condition is R 2To R 4In only 1 be selected from SCH 3, S(O) CH 3And SO 2CH 3, A 2Be CH 2, O or CH(CF 3); And Y is 3,5-two chloro-2-pyridyl, 1-CH 3-4-nitro-pyrazoles-5-base, 1-CH 3-4-NO 2-pyrazoles-5-base or by R 21, R 22And R 23The phenyl that replaces.
24, the method for claim 15, wherein R 1It is phenyl or by C 1-4Alkyl, C 1-4Alkoxyl group, halogen or CF 3Mono-substituted phenyl; R 2, R 3And R 4Be respectively H or CH 3; A 2Be CH(CF 3), CH 2Or O; Y is 3,5-two chloro-2-pyridyl, 1-CH 3-4-NO 2-pyrazoles-5-base, 1-CH 3-4-NO 2-pyrazole-3-yl or by R 21, R 22And R 23The phenyl that replaces.
25, the method for claim 24, wherein Y is by R 21, R 22And R 23The phenyl that replaces.
26, any one method in the claim 1 to 25, wherein A 3
Figure 891017437_IMG10
A 4Be C=C(ORa).
27, the method for claim 1 is used for preparation
A.2-(1-methyl-4-nitro-5-pyrazolyl carbonyl)-hydroresorcinol.
B.2-(1-methyl-4-nitro-3-pyrazolyl carbonyl)-hydroresorcinol.
C.2-(1-methyl-4-nitro-3-pyrazolyl carbonyl)-and the 5-methyl isophthalic acid, hydroresorcinol.
D.2-(1-methyl-4-nitro-3-pyrazolyl carbonyl)-4,4,6-trimethylammonium-hydroresorcinol
E.2-(1-methyl-4-nitro-3-pyrazolyl carbonyl)-4,4,6,6-tetramethyl--hydroresorcinol.
F.4-(1-methyl-4-nitro-3-pyrazolyl carbonyl) 2,2,6,6-tetramethyl--3,6-dihydro-2H-pyrans-3-ketone.
G.2-(4-chloro-2-nitro benzoyl)-4-phenyl-hydroresorcinol.
H.2-(4-chloro-2-nitro benzoyl)-and the 5-Trifluoromethyl-1, hydroresorcinol.
I.2-(4-chloro-2-nitro benzoyl)-and 4-methyl-5-Trifluoromethyl-1, hydroresorcinol.
J.2-(4-chloro-2-nitro benzoyl)-4,4-dimethyl-5-Trifluoromethyl-1, hydroresorcinol.
K.2-(4-chloro-2-nitro benzoyl)-the 4-(2-fluorophenyl)-hydroresorcinol.
L.2-(4-chloro-2-nitro benzoyl)-the 4-(4-fluorophenyl)-hydroresorcinol.
M.2-(2-chloro-4-methyl sulphonyl benzoyl)-and the 5-Trifluoromethyl-1, hydroresorcinol.
N.2-(4-chloro-2-nitro benzoyl)-4,6,6-trimethylammonium-4-tetrahydrobenzene-1,3-diketone.
O.2-chloro-2-(4-chloro-2-nitro benzoyl)-4,4,6,6-tetramethyl--1,3-hexamethylene-1,3-diketone.
P.2-chloro-2-(4-chloro-2-nitro benzoyl)-4,4,6-trimethylammonium-1,3-hexamethylene-1,3-diketone.
Q.2-(3,5-two chloro-2-pyridyl carbonyls)-hydroresorcinol.
R.2-(1-methyl-4-nitro-3-pyrazolyl carbonyl-3-(phenoxy group carbonyl oxygen base)-2-tetrahydrobenzene-1-ketone.
28, the method for claim 26 is used for the compound of preparation formula I, and wherein Ra is the part of a kind of ether or ester with the oxygen bonding.
29, according to the compound of the whenever resulting formula I of method of claim 1 to 28.
30, a kind of herbicidal composition comprises the compound of any one described formula I in the claim 1 to 28.
31, the herbicidal composition of claim 30 comprises a kind of compound of claim 29.
32, a kind of method of going out and cutting weeds comprises the formula I compound administration of the herbicidally effective amount described in any one in the claim 1 to 28 to weeds or weed growth place.
33, the method for going out and cutting weeds comprises the compound administration of effective weeding amount in the claim 29 to weeds or weed growth place.
CN89101743A 1988-02-01 1989-01-31 The improvement of organic compound or relevant organic compound Pending CN1036202A (en)

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CN106187866B (en) * 2016-07-12 2019-04-16 李为忠 Pyridine acyl class compound and its preparation and application

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