CN1180355A - Pyrazole derivatives - Google Patents
Pyrazole derivatives Download PDFInfo
- Publication number
- CN1180355A CN1180355A CN 96193076 CN96193076A CN1180355A CN 1180355 A CN1180355 A CN 1180355A CN 96193076 CN96193076 CN 96193076 CN 96193076 A CN96193076 A CN 96193076A CN 1180355 A CN1180355 A CN 1180355A
- Authority
- CN
- China
- Prior art keywords
- formula
- pyrazole derivatives
- alkyl
- compound
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 150000003217 pyrazoles Chemical class 0.000 title claims abstract description 51
- 229910052731 fluorine Chemical group 0.000 claims description 47
- 125000005843 halogen group Chemical group 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- MHBLQZYBQMZPCT-UHFFFAOYSA-N O1CCCC2=CC=CC=C12.[S] Chemical group O1CCCC2=CC=CC=C12.[S] MHBLQZYBQMZPCT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 3
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 3
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000005425 toluyl group Chemical group 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- CJFOKWNHNZBRRU-UHFFFAOYSA-N Base A Natural products CC1CC2NC(C)NC3NC(C)CC(N1)C23 CJFOKWNHNZBRRU-UHFFFAOYSA-N 0.000 claims 1
- 239000002689 soil Substances 0.000 abstract description 21
- WPWNEKFMGCWNPR-UHFFFAOYSA-N 3,4-dihydro-2h-thiochromene Chemical group C1=CC=C2CCCSC2=C1 WPWNEKFMGCWNPR-UHFFFAOYSA-N 0.000 abstract 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 75
- 238000006243 chemical reaction Methods 0.000 description 61
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 46
- 239000011737 fluorine Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 40
- 239000002904 solvent Substances 0.000 description 32
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- 241000196324 Embryophyta Species 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 25
- ROFMCPHQNWGXGE-SFHVURJKSA-N (3s)-n-[2-[2-(dimethylamino)ethoxy]-4-(1h-pyrazol-4-yl)phenyl]-6-methoxy-3,4-dihydro-2h-chromene-3-carboxamide Chemical compound O=C([C@@H]1COC2=CC=C(C=C2C1)OC)NC(C(=C1)OCCN(C)C)=CC=C1C=1C=NNC=1 ROFMCPHQNWGXGE-SFHVURJKSA-N 0.000 description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- -1 suberyl Chemical group 0.000 description 22
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- 235000002639 sodium chloride Nutrition 0.000 description 20
- 239000003513 alkali Substances 0.000 description 19
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
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- 125000000217 alkyl group Chemical group 0.000 description 12
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
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- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 6
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
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Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to novel pyrazole derivatives having thiochroman ring bonded via a carbonyl group, which exhibit excellent crop-weed selectivity in foliage treatment and soil treatment.
Description
Technical field
The present invention relates to pyrazole derivatives reaches with its weedicide as effective constituent.
Background technology
In order to protect important crops such as paddy rice, wheat, barley, corn, soybean, cotton, beet not to be subjected to weeds harm, to seek to increase income, it is indispensable using weedicide.Particularly in recent years, expect to have such weedicide, promptly mix the arable land that exists,, crop is not shown poisoning, the selective herbicide of only selectively cutting weeds extremely yet even the leaves and stems of crop and weeds is handled simultaneously above-mentioned useful crop and weeds.
In the past, when the cultivation of corn etc., mainly using triazine is that herbicide atrazine and anilide are that weedicide alachlor and metolachlor are as processing soil treatment agent, still, these weedicides must use with high dose, therefore cause environmental problems such as groundwater pollution.
In addition, in recent years, encouraging to save from damage with soil is the not tillage and cultivation of purpose.So-called " not tillage and cultivation " is with respect to common tillage and cultivation, not farming field and the method for raise crop.In tillage and cultivation, because arable land (farming) and rainwater etc. run off fertile table soil, become the big problem on the agricultural, also become a reason of Desertification simultaneously.Tillage and cultivation is not shown the problem that soil runs off, and still, owing to do not carry out farming, it is fixed that soil becomes, and medicament is difficult for infiltrating in the soil, and the effect of processing soil treatment agent is reduced.Therefore, in tillage and cultivation not, in soil treatment, need such weedicide especially, even promptly can show also that with low dose high herbicidal effect and single agent also can use as the cauline leaf treatment agent.
In the open WO93/18031 communique in the world, announced to have pyrazole derivatives weeding activity, that represent with following structural formula with sulphur chroman ring.
(in the formula, R
1Be C
1-C
6Alkyl.Other symbol omits explanation.)
Representation compound (A) (compound N o.66 in the international publication) in the open communique in the above-mentioned world is shown below.
Above-claimed cpd (A) to raise crops such as corn, wheat, barleys, carries out not producing when cauline leaf is handled poisoning in the 1-2 leaf phase, show good crops and weeds selectivity, but, when carrying out the cauline leaf processing, can not fully satisfy security to crop in the 3-4 leaf phase.
Disclosure of an invention
The 1st purpose of the present invention is, when being provided at cauline leaf processing, soil treatment, promptly extensive weeds had the strong especially careless power of killing with low dose, and important crop wheat, barley, corn, soybean, cotton, beet, paddy rice etc. are had high security, show the pyrazole derivatives that good crops and weeds is optionally novel.
And then the 2nd purpose of the present invention is, provides and contains with the weedicide of above-mentioned novel pyrazole derivatives as effective constituent.
The inventor finds the novel pyrazole derivatives that can achieve the above object to carry out further investigation repeatedly, found that, with the R in the pyrazole derivatives structural formula in the open communique in the above-mentioned world
1From C
1-C
6Alkyl is replaced to the C with 1 above halogen atom
1-C
6The compound of haloalkyl shows good crop weeds selectivity, thereby has finished the present invention.
That is, the 1st purpose of the present invention is to reach by the pyrazole derivatives with formula (I) expression,
In the formula, R
1Be C with 1 above halogen atom
1-C
6Haloalkyl; R
2, R
3, R
4And R
5Be hydrogen atom or C independently of one another
1-C
4Alkyl;
R
6Be C
1-C
4Alkyl;
R
7Be hydrogen atom or C
1-C
4Alkyl;
X is C
1-C
4Alkyl or halogen atom;
P and n are 0,1 or 2 integer independently of one another;
Q is hydrogen atom or base-A-B
[in the formula, A is-SO
2-,-(CH
2)
k-CO-or-CR
8R
9-
(in the formula, k be 0 or the integer of 1-3,
R
8And R
9Be hydrogen atom or C independently of one another
1-C
4Alkyl);
B is C
1-C
12Alkyl, C
3-C
12Cycloalkyl or base-Ph-Y
m(Y that in the formula, Ph is phenyl, replace on Ph is C
1-C
4Alkyl, C
1-C
4Alkoxyl group, has the C of 1 above halogen atom
1-C
4Haloalkyl, nitro or halogen atom, m be 0 or the integer of 1-2)].
And then the 2nd purpose of the present invention is by reaching with the pyrazole derivatives of above-mentioned formula (I) the expression weedicide as effective constituent.
Implement best mode of the present invention
The novel pyrazole derivatives that reaches the 1st purpose of the present invention is the compound that has with structure shown in the following formula (I).
In above-mentioned formula (I), R
1Be C with 1 above halogen atom
1-C
6Haloalkyl.As forming R
1The C of skeleton
1-C
6Alkyl can comprise methyl, ethyl, propyl group, butyl, amyl group and hexyl, and alkyl is C
3When above, can have straight chain and side chain.Preferable methyl, ethyl.As R
1The C of skeleton
1-C
6Replacement halogen atom on the alkyl can comprise chlorine atom, fluorine atom, bromine atoms and iodine atom, preferred chlorine atom and fluorine atom.Halogen atom can replace R
1C
1-C
6Any hydrogen atom of alkyl, it replaces the preferred 1-7 of number, more preferably 1.
R
1The example of haloalkyl can comprise Z-CH
2-(Z is a halogen atom, below identical; Replace 1 halogen atom), Z-CH
2CH
2-(replacing 1 halogen atom), (CZ
3)
2CH (replacing 6 halogen atoms), Z (CZ
2)
q(CH
2)
s-(q is the integer of 1-3, and s is the integer of 0-5; Replace 3-7 halogen atom) or H (CZ
2)
r(CH)
s-(r is the integer of 1-5, and s is the integer of 0-5; Replace 2-10 halogen atom) etc.
R
1Preferably has C
1-C
4The haloalkyl of straight or branched, for example, can comprise chloromethyl, methyl fluoride, 2-chloroethyl, 2-fluoro ethyl etc., more preferably 2-chloroethyl, 2-fluoro ethyl.
In above-mentioned formula (I), R
2, R
3, R
4And R
5Be hydrogen atom or C independently of one another
1-C
4Alkyl.As C
1-C
4Alkyl for example can comprise methyl, ethyl, propyl group and butyl, and propyl group and butyl also can have straight or branched.
As R
2, R
3, R
4And R
5Preferred example, for example, can comprise hydrogen atom or methyl independently of one another, more preferably be hydrogen atom independently of one another.
In above-mentioned formula (I), R
6Be C
1-C
4Alkyl, R
7Be hydrogen atom or C
1-C
4Alkyl.C
1-C
4The object lesson of alkyl with at above-mentioned R
2, R
3, R
4And R
5Middle illustrate identical.
R
6Preferred object lesson be methyl and ethyl, more preferably ethyl.
R
7Preferred object lesson be hydrogen atom or methyl, more preferably hydrogen atom.
In above-mentioned formula (I), X is C
1-C
4Alkyl or halogen atom.C
1-C
4The object lesson of alkyl and halogen atom is identical with above-mentioned explanation.
The preferred object lesson of X is methyl, chlorine atom and fluorine atom, more preferably methyl.In addition, the position of substitution of X can be 5,7 and 8 of sulphur chroman ring, preferred 5 and/or 8.
In above-mentioned formula (I), p represents the replacement number of X, is 0,1 or 2 integer, preferred 1 or 2, more preferably 2.
In above-mentioned formula (I), n is illustrated in bonded oxygen atomicity on the sulphur chroman ring, is 0,1 or 2 integer.That is, n is 0 o'clock, expression sulphur; N is 1 o'clock, the expression sulfoxide; N is 2 o'clock, the expression sulfone.Preferred n=2 promptly is a sulfone.
In above-mentioned formula (I), Q is hydrogen atom or base-A-B.
A when Q is a base-A-B is-SO
2-,-(CH
2)
k-CO or CR
8R
9-.Here, in the general formula of A, k is 0 or the integer of 1-3, R
8And R
9Be hydrogen atom or C independently of one another
1-C
4Alkyl.
A is-(CH
2)
kObject lesson during-CO-can comprise-CO-base (k=0) ,-CH
2CO-base (k=1) ,-(CH
2)
2CO-base (k=2) and-(CH
2)
3CO-(k=3), preferred-CO-base (k=0) or-CH
2CO-base (k=1).
A is-CR
8R
9The time object lesson can comprise-CH
2-Ji ,-CH (CH
3) base ,-C (CH
3)
2-Ji ,-CH (C
2H
5)-Ji ,-C (C
2H
5)
2-Ji, preferred-CH
2-Ji ,-CH (CH
3)-Ji.
A is preferred-SO
2-Ji or-CO-base (k=0).
When Q was a base-A-B, B was C
1-C
12Alkyl, C
3-C
12Cycloalkyl or base-Ph-Y
m
B is C
1-C
12Object lesson during alkyl removes the C of above-mentioned explanation
1-C
4Outside the alkyl, also can comprise amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, when alkyl is 3 above carbon atoms, can be straight or branched.
B is C
3-C
12Object lesson during cycloalkyl can comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl.As mentioned above, the carbonatoms of cycloalkyl is 3-12, and still, carbonatoms is the occasion more than 4, and cycloalkyl can have alkyl to be substituted on ring.For example, the cycloalkyl of 4 carbon atoms being arranged can be methyl substituted cyclopropyl.
B is base-Ph-Y
mThe time, the Y in the formula is C
1-C
4Alkyl, C
1-C
4Alkoxyl group, has the C of 1 above halogen atom
1-C
4Haloalkyl, nitro or halogen atom, m are 0 or the integer of 1-2.What is called m is 0, and expression Y does not go up at Ph (phenyl) and replaces, and promptly is the phenyl that does not have replacement.When m was the integer of 1-2, Y replaced on 2-, the 3-of Ph (phenyl), 4-, 5-, 6-position 1 or 2 positions.
B is a kind of above-mentioned base-Ph-Y of form
mThe time, Y is C
1-C
4The object lesson of alkyl is identical with above-mentioned explanation.Y is C
1-C
4During alkoxyl group, can comprise methoxyl group, oxyethyl group, propoxy-and butoxy, propoxy-and butoxy also can have straight or branched.C with 1 above halogen atom
1-C
4The object lesson of haloalkyl with at above-mentioned R
1Explanation in represent identical.Halogen atom can comprise fluorine atom, chlorine atom, bromine atoms and iodine atom.
The preferred C of B
1-C
4Alkyl, C
3-C
8Cycloalkyl or base-Ph-Y
m, more preferably ethyl, n-propyl, cyclohexyl, phenyl are (at base-Ph-Y
mIn m be 0) or the toluoyl base (at base-Ph-Y
mMiddle Y is 4 methyl, and m is 1).
The preferred hydrogen atom of Q or base-A-B, wherein the combination of A and B is as follows.
That is, preferred A is-SO
2-Ji, B are C
1-C
4Alkyl or base-Ph-Y
mCombination, more preferably A is SO
2-Ji, B are that ethyl, n-propyl or toluoyl base are (at base-PhY
mIn, Y is the 4-methyl, m is 1) combination.In addition, preferred A is-(CH
2)
k-CO-base, B are C
3-C
8Cycloalkyl or base-Ph-Y
mCombination, more preferably A be-the CO-base is (at-(CH
2)
kAmong-the CO-, k=0) or-CH
2The CO base (-(CH
2)
kAmong-the CO-, k=1), B is that phenyl is (at base-Ph-Y
mIn, m is 0) or the combination of cyclohexyl.
In general formula (I), Q is the pyrazole derivatives of hydrogen atom, i.e. formula (Ia) (in the formula, each symbol is identical with definition in (I))
Be shown below, obtain with the structure shown in formula (Ib), formula (Ic) and the formula (Id), but pyrazole derivatives of the present invention comprises all these compounds and composition thereof by tautomerism.
(in the formula, each symbol is identical with definition in (I).)
In addition, the pyrazole derivatives of representing with formula (Ia) is acidic substance, can easily form salt by handling with alkali, and this salt is also contained in the pyrazole derivatives of the present invention.
At this, alkali can be known alkali, and does not have any restriction, for example can comprise organic bases and mineral alkalis such as sodium compound and potassium compound such as amine and phenyl amines.Amine can comprise monoalkylamine, dialkylamine, trialkylamine etc.Alkyl in the alkyl amine is C normally
1-C
4Phenyl amines can comprise aniline and monoalkyl aniline, dialkyl aniline etc.Alkyl in the alkylbenzene amine is C normally
1-C
4Alkyl.As sodium compound is sodium hydroxide, yellow soda ash etc., is potassium hydroxide, salt of wormwood etc. as potassium compound.
Moreover, in pyrazole derivatives, there is unsymmetrical carbon with (I) expression, there are various isomer, pyrazole derivatives of the present invention comprises all these isomer and composition thereof.
Weedicide of the present invention is to contain with the of the present invention novel pyrazole derivatives of formula (I) expression and/or its salt weedicide as effective constituent, these compounds can be mixed with solid carriers such as liquid vehicles such as solvent or mineral substance micro mists, preparation changes into uses such as wettable powder, emulsion, pulvis, granula.When carrying out preparation, can add tensio-active agent in order to give emulsifying property, dispersiveness, plate-out ability.
The occasion of using with the wettable powder form at weedicide of the present invention can cooperate with the ratio of pyrazole derivatives of the present invention and/or its salt 10-55% (weight), solid carrier 40-88% (weight), tensio-active agent 2-5% (weight) to be modulated into composition and to use usually.In addition, in the occasion of using with the emulsion form, can cooperate with the ratio of pyrazole derivatives of the present invention and/or its salt 20-50% (weight), solvent 35-57% (weight), tensio-active agent 5-15% (weight) usually and modulate.
On the other hand, in the occasion of using with powder form, can cooperate with the ratio of pyrazole derivatives of the present invention and/or its salt 1-15% (weight), solid carrier 80-97% (weight), tensio-active agent 2-5% (weight) usually and modulate.In addition, in the occasion of using with the granula form, can cooperate with the ratio of pyrazole derivatives of the present invention and/or its salt 1-15% (weight), solid carrier 80-97% (weight), tensio-active agent 2-5% (weight) usually and modulate.Here, solid carrier can use the micro mist of mineral substance, and the micro mist of mineral substance can comprise silicate such as vitriol such as phosphoric acid salt such as oxide compounds such as diatomite, white lime, calcium phosphate, gypsum, talcum, pyrophyllite, clay, kaolin, wilkinite, acidic white earth, colloided silica, silica powder, ground silica etc.
In addition, solvent can be with an organic solvent, specifically can comprise aromatic hydrocarbonss such as benzene,toluene,xylene, chlorinated hydrocarbons such as ortho-chlorotolu'ene, trichloroethane, trieline, alcohol such as hexalin, amylalcohol, ethylene glycol, different Buddhist and ketone such as ketone, pimelinketone, cyclohexenyl-pimelinketone, ethers such as butyl glycol-ether, diethyl ether, methyl ethyl ether, esters such as isopropyl acetate, jasmal, phthalic acid methyl esters, acid amides or their mixtures such as DIMETHYL FORMAMIDE.
As tensio-active agent, anionic, non-ionic type, cationic or amphoteric ion type (amino acid, trimethyl-glycine etc.) can use.
In weedicide of the present invention, when containing with the pyrazole derivatives of above-mentioned general formula (I) expression and/or its salt, can contain other herbicidal active component as required as effective constituent.As other herbicidal active component of this class; can comprise existing known weedicide; for example benzene oxygen system, phenyl ether system, triazine system, urea system, carbamate system, thiol carbamate system, N-anilide system, pyrazoles system, phosphoric acid system, sulfonylurea system, oxadiazon system etc. can suitably select from these weedicides and use.
And then weedicide of the present invention can mix use with sterilant, sterilant, plant-growth regulator, fertilizer etc. as required.
Compound of the present invention can use in any treatment process during soil treatment, mixing with soil processing, cauline leaf are handled as the field weedicide.Field weeds as the object of The compounds of this invention, for example can comprise black nightshade (Solanum nigrum), thorn apple (Daturastramonium) etc. is the Solanaceae weeds of representative, piemarker (Abutilon theophrasti), America Radix sidae acutae (Side spinosa) etc. is the Malvaceae weeds of representative, Pharbitis purpurea sweet potato classes such as (Ipomoeapurpurea) and bindweed are the convolvulaceae weeds of representative, recessed amaranth (Amaranthuslividus) etc. is the Amaranthaceae weeds of representative, Siberian cocklebur (Xanthium strumarium), artemisiifolia (Ambrosia artemisiaefolia), Sunflower Receptacle (Helianthus annus), bristle Herba galinsogae parviflorae (Galinsoga ciliata), the Silk Road Ji (Cirsium arvense), Herba Senecionis Vulgaris (Senecio vulgaris), Herba Erigerontis Annui (Erigeronannus) etc. is the composite family weeds of representative, river Herba clinopodii confinis (Herba Clinopodii Gracilis) (Rorippa indica), wild Europe sinapsis alba (Sinapis arvensis), shepherd's purse (Capsella bursa-pastoris) etc. is the cruciferous weed of representative, knotweed (Polygonumblumei), volume stem knotweed (Polygonum convolvulus) etc. is the knotweed of representative, purslane (Portulaca oleracea) etc. is the Portulacaceae weeds of representative, white lamb's-quarters (Chenopodium album), banyan leaf lamb's-quarters (Chenopodium ficifolium), summer cypress (Kochia scoparia) etc. is the Chenopodiaceae weeds of representative, chickweed (Stellaria media) etc. is the Caryophyllaceae weeds of representative, Arabic veronica (Veronica persica) etc. is the scrophulariaceae weeds of representative, Herba Commelinae (Commelina communis) etc. is the Commelianaceae weeds of representative, benbie (Lamium amplexicaule), deaf nettle (Lamium purpureum) etc. is the Labiatae weeds of representative, variegated leaf humid euphorbia (Euphorbia supina), american euphorbia herb (Euphorbia maculata) etc. is the Euphorbiaceae weeds of representative, climb and draw rattan (Galuimspurium), Tender Catchweed Bedstraw Herb (Galium aparine), madder (Rubia akane) etc. is the Rubiaceae weeds of representative, arable land violet (Viola arvensis) etc. is the Violaceae weeds of representative, big fruit sesbania (Sesbania exaltata), blunt leaf Cassia tora (Cassia obtusifolia) etc. is the wide leaf weeds of pulse family weeds of representative, wild dichromatism chinese sorghum (Sorgham bicolor), ocean wild broomcorn millet (Panicum dichotomiflorum), Johnson grass (Sorghum halepense), barnyard grass (Echinochloa crus-galli), rise lady's-grass (Digitaria adscendens), wild avena sativa (Avena fatua), Shuai Xi grass (Eleusine indica), herba setariae viridis grass (Setariaviridis), amur foxtail (Alopecurus aegualis) etc. is the gramineous weeds of representative, nutgrass flatsedge (Cyperus rotundus, Cyperus esculentus) etc. for the sedge weed of representative etc.
In addition, compound of the present invention is as the paddy field weedicide, and soil treatment under the retaining situation and cauline leaf can use in handling.As paddy land weed, can comprise alisma canaliculatum (Alismacanaliculatum), arrowhead (Sagittaria trifolia), short arrowhead (Sagittariapygmaea) etc. is the Alismataceae weeds of representative, Herba Cyperi Difformis (Cyperus difformis), Herba Cyperi Glomerati (Cyperus serotinus), firefly Lin (Scirpus juncoides), pin Lin (Eleocharis kuroguwai) etc. is the sedge weed of representative, Herba Linariae Vulgaris (Lindeniapyxidaria) etc. is the scrophulariaceae weeds of representative, Sheathed Monochoria (monochoria vaginalis) etc. is the Potenderiaceae weeds of representative, Herba potamogetonis distincti (Potamogeton distinctus) etc. is the Potamogetonaceae weeds of representative, mexicana (Rotala indica) etc. is the Lythraceae weeds of representative, and barnyard grass (Echinochloa crus-galli) etc. are the gramineous weeds of representative etc.
In addition, The compounds of this invention also can be applicable to preventing and kill off of various weeds in the non-agricultural arable lands such as playground, vacant lot, road edge beyond agriculture scopes such as dry land, paddy field, fruit tree garden.
Novel pyrazole derivatives with formula of the present invention (I) expression can adopt the whole bag of tricks synthetic, for example adopts following method to make.
(in the formula, each symbol is identical with definition in formula (I), and Hal represents halogen atom.)
In the presence of dehydrating condensation agent and alkali, the carboxylic acid derivative of formula (II) and the pyrazole compound of formula (III) are reacted in inert solvent, can access the middle Q of formula (I) is the pyrazole derivatives of the present invention (process 1) of the formula (Ia) of hydrogen atom.
And then, making the pyrazole derivatives of formula (Ia), the halogenide with formula (IV) in inert solvent reacts, and can access that Q is the pyrazole derivatives of the present invention (process 2) of base-A-B in the formula (I).
Below, describe each process respectively in detail.
Process 1
With respect to the carboxylic acid derivative of formula (II), the pyrazole compound of formula (III) is preferably with doubly mole use of 1.0-3.0.
The dehydrating condensation agent that uses in this reaction can comprise N, N-dicyclohexylcarbodiimide (DCC), 1,1-carbonyl dimidazoles (CDI), 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide (EDC) etc., preferred DCC.With respect to the carboxylic acid derivative of formula (II), dehydrating condensation agent is preferably with doubly mole use of 1.0-1.5.
Kind to the alkali that uses in this reaction is not done special restriction, but preferred salt of wormwood, yellow soda ash etc.With respect to the carboxylic acid derivative of formula (II), alkali is preferably with doubly mole use of 0.5-2.0.
The reaction solvent that uses in this reaction, so long as keep inertia in reaction, just not restriction especially can comprise acetonitrile, tertiary amyl alcohol, the trimethyl carbinol, Virahol etc., the preferred tertiary amylalcohol.
Can be in the scope of boiling point from 0 ℃ to solvent the selective reaction temperature, but preferred about 80 ℃.Reaction times is 1-48 hour, but normally about 8 hours.
After reaction ended, decompression was heated up in a steamer and is desolvated, and adds weak alkaline aqueous solution such as yellow soda ash, salt of wormwood and dissolve the filtering insolubles in residue.Behind the clean water layer of organic solvents such as ethyl acetate, chloroform, methylene dichloride, ethylene dichloride, add dilute hydrochloric acid, dilute sulphuric acid etc. and carry out acidifying.Solid that leaching generates or oily matter or extract with organic solvents such as ethyl acetate, chloroform, methylene dichloride, ethylene dichloride obtain the pyrazole derivatives of required formula (Ia).
Process 2
With respect to the pyrazole derivatives of formula (Ia), the halogenide of formula (IV) is preferably with doubly mole use of 1-3.
In order to catch the by-product hydrogen halide that produces by this reaction, with respect to the pyrazole derivatives of formula (Ia), preferably to wait above alkali such as yellow soda ash, salt of wormwood, triethylamine, pyridine that use of mole.
The solvent that uses in this reaction is so long as keep inertia, just not restriction especially in reaction, can comprise aromatic hydrocarbonss such as benzene, toluene, ether based compounds such as diethyl ether, ketone based compounds such as methyl ethyl ketone, halon such as methylene dichloride, chloroform etc., preferred methylene dichloride.In addition, also can use the two-phase solvent of forming by these solvents and water, at this moment, in reaction system,, obtain gratifying result for example by adding phase-transfer catalysts such as crown ether, benzyltriethylammoinium chloride.
Temperature of reaction preferably is defined in the scope of the boiling point from room temperature to solvent.Reaction times is 0.5-48 hour, but is generally 0.5-3 hour.
After reaction ends, in reaction mixture, add organic solvents such as weak alkaline aqueous solutions such as yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus and diethyl ether, methylene dichloride, chloroform, ethylene dichloride, ethyl acetate and carry out separatory, behind the dry organic layer, decompression is heated up in a steamer and is desolvated.As required the residue that obtains is carried out recrystallize, perhaps carry out purifying by column chromatography, can access in formula (I) Q is base
The pyrazole derivatives of the present invention of A-B.
The pyrazole compound of the formula of using as reaction reagent in aforesaid method (III), it is synthetic for example can to open the method for putting down in writing in the clear 61-257974 communique according to the spy.
In addition, the another kind of reaction reagent that uses in aforesaid method is that it can adopt the whole bag of tricks manufacturing with the carboxylic acid derivative of formula (II) expression.A part of manufacture method is shown below.
(each symbol is with defined identical in formula (I) in the formula)
(in the formula, each symbol is identical with definition in formula (I), R
8Expression hydrogen, C
1-C
4Alkyl, C
1-C
6Haloalkyl.)
Below, describe each process respectively in detail.
The alcoholization process
This reaction is reduction formula V or ketone (VIII), forms the process of formula (VI) or alcohol (IX).
Can for example, can comprise the method for putting down in writing in the international open WO88/06155 communique with the ketone of the whole bag of tricks manufacturing as the formula V of starting raw material.
Reductive agent as using in this reaction can comprise various reductive agents, but preferred sodium borohydride etc.
Normally 20 ℃~50 ℃ of temperature of reaction.
Etherification procedure
This reaction is in the presence of catalyzer and solvent, make formula (VI), (IX) or alcohol (VII) with general formula R
1The alcohol that OH represents carries out dehydrating condensation, forms the process of formula (VII), (X) or ether (XI) respectively.In addition, also there are the situation of carrying out esterification simultaneously in formula (XII) and carboxylic acid (IX).
Catalyzer as using in this reaction for example can comprise an acidic catalysts such as sulfuric acid, aromatic sulphonic acid, sulfonic acid halide, boron trifluoride, aluminum chloride.By adding catalyzer, reaction can successfully be carried out.
Solvent as using in this reaction for example can comprise aromatic hydrocarbons series solvents such as benzene,toluene,xylene, 1, and halon series solvents such as 2-ethylene dichloride, tetracol phenixin.In addition, general formula R
1The alcohol that OH represents can be used as the excessive use of solvent.
Carboxylated process
This reaction is that the compound and the magnesium of formula (VII) are reacted, and produces Grignard reagent, makes itself and carbon dioxide reaction, obtains the carboxylic acid derivative (n=0, sulfide) of formula (II-0).
Solvent as using in this reaction preferably can comprise diethyl ether, tetrahydrofuran (THF) etc.
Normally 0~50 ℃ of temperature of reaction.
Oxidising process
This process is the oxidized sulfur atom that makes in formula (II-0) or the carboxylic acid derivative (X), obtain formula (II-1), formula (II-2) or (XI-1), the process of the carboxylic acid derivative of formula (XI-2).
Multiple oxygenant can use in this reaction, but preferred oxygenant is a hydrogen peroxide.
Multiple solvent can use in this reaction, but acetate more preferably.
For obtaining the compound (sulfoxide) of n=1 in formula 2 (II),, can use 1 normal oxygenant, react at 0~30 ℃ with respect to the carboxylic acid derivative of formula (ID-0).In addition, for obtaining the compound (sulfone) of n=2 in formula (II), can use the above oxygenant of 2 equivalents, react at 50~100 ℃.
(X) is also identical for formula.
Hydrolytic process
This process is compound and alkali or the acid-respons that makes formula (XI), makes the ester hydrolysis obtain the compound of formula (II).
The alkali that in this reaction, uses, preferred sodium hydroxide, potassium hydroxide etc.The acid of in this reaction, using, preferred hydrochloric acid, sulfuric acid etc.
With respect to ester, can use 1~5 times of mole above alkali and acid to react.
Employed solvent, particular methanol, ethanol, ethylene glycol etc.
Normally 0 ℃~100 ℃ of temperature of reaction.
Below, illustrate and make reference example, make embodiment and weedicide embodiment, specifically describe the present invention, still, the present invention is not subjected to the qualification of above-mentioned example.
Synthesizing of the carboxylic acid derivative of manufacturing reference example 1-formula (II)
(I) alcoholization process
At 10g (36.9mmol) 5, add 100ml methyl alcohol and 30ml methylene dichloride in 8-dimethyl-6-bromine sulphur chroman-4-on-.Use salt solution, ice bath, keep the temperature of this mixture to be no more than 0 ℃, to wherein slowly adding 0.70g (18.4mmol) borane reducing agent sodium hydride.
After room temperature is carried out reaction in 3 hours, reaction mixture is injected 5% hydrochloric acid, extract with methylene dichloride.With the resulting dichloromethane layer of anhydrous sodium sulfate drying, concentrate then, obtain 9.2g (yield 91%) 5,8-dimethyl-4-hydroxyl-6-bromine sulphur chroman (compound that is equivalent to formula (VI)).
(2) etherification procedure
9.2g (33.7mmol) in above-mentioned (1), obtain 5, in 8-dimethyl-4-hydroxyl-6-bromine sulphur chroman, add 17g 2-fluoroethanol and 3 vitriol oils, carry out reaction in 4 hours at 70 ℃.Put cold after, reaction mixture is injected ice bath, extract with methylene dichloride.After water, saturated aqueous common salt are cleaned resulting dichloromethane layer, carry out drying, use column chromatography (silica gel with anhydrous sodium sulphate; Solvent hexane: ethyl acetate=20: 1) carry out purifying, obtain 9.35g (yield 87%) 5,8-dimethyl-4-(2-fluorine oxyethyl group)-6-bromine sulphur chroman (compound that is equivalent to formula (VII)).
1H-NMR (solvent: CDCl
3, internal standard: tetramethylsilane, ppm): 1.5-2.0 (1H, m), 2.19 (3H, s), 2.44 (3H, s), 2.5-2.9 (2H, m), 3.1-3.4 (1H, m), 3.5-3.8 (1H, m), 3.84.1 (1H, m), 4.30 (1H, t, J=4.2Hz), 4.68 (1H, m), 4.83 (1H, t, J=4.2Hz), 7.3 (1H, s)
(3) carboxylated process
In 9.35g (29.3mmol) above-mentioned (2), obtain 5, in tetrahydrofuran (THF) (THF) solution of 8-dimethyl-4-(2-fluorine oxyethyl group)-6-bromine sulphur chroman and 1.48g (60.8mmol) magnesium, splash into 5.43g (49.8mmol) monobromoethane, reflux 2 hours.With the reaction mixture cool to room temperature, carry out carbonic acid gas and bubbled 1 hour.In reaction mixture, inject 5% hydrochloric acid and frozen water, use ethyl acetate extraction.In resulting ethyl acetate layer, add 5% aqueous sodium carbonate and carry out separatory.In resulting aqueous sodium carbonate layer, add concentrated hydrochloric acid, pH is adjusted to 1.The solid that leaching is separated out carries out drying, obtains 5.37g (yield 64%) 4-(2-fluorine oxyethyl group)-5, and 8-dimethyl sulphide chroman-6-carboxylic acid (is equivalent to (compound of formula (II-0)).
1H-NMR (solvent: CDCl
3, internal standard: tetramethylsilane, ppm): 1.6-2.0 (1H, m), 2.26 (3H, s), 2.5-2.9 (3H, s), 2.64 (3H, s), 3.1-3.5 (1H, m), 3.5-3.8 (1H, m), 3.8-4.1 (1H, m), 4.32 (1H, t, J=4.2Hz), 4.7-4.9 (2H, m), 7.71 (1H, s)
(4) oxidising process
The 4-that obtains in above-mentioned (3) of 5.37g (18.9mmol) (2-fluorine oxyethyl group)-5 in 8-dimethyl sulphide chroman-6-carboxylic acid, added 4ml acetate and oxygenant 30% aquae hydrogenii dioxidi 6.24g (56.7mmol), 80 ℃ of reactions 2 hours.Put cold after, in reaction mixture, add 2% aqueous solution of sodium bisulfite, remove superfluous hydrogen peroxide, the crystallization that leaching is separated out, carry out drying, obtain the 4-(2-fluorine oxyethyl group)-5 of 5.08g (yield 85%), 8-dimethyl sulphide chroman-6-carboxylic acid-1, the 1-dioxide (is equivalent to (compound of formula (II-2)).
1H-NMR (solvent: CDCl
3, internal standard: tetramethylsilane, ppm): 2.5-2.8 (2H, m), 2.61 (3H, s), 2.78 (3H, s), 3.1-3.4 (1H, m), 3.6-4.1 (3H, m), 4.33 (1H, t, J=4.1Hz), 4.7-4.9 (2H, m), 7.81 (1H, s)
Make reference example 2
(1) etherification procedure
In the 4-hydroxy-5-methyl base sulphur chroman-1 of 4.3g (16.7mmol), (be equivalent in (compound of formula (XII-2)), add 2 fluoroethanols and 3 vitriol oils of 5ml, reflux is 17 hours then for 1-dioxide-6-carboxylic acid.Put cold after, reaction mixture is injected ice bath, with twice of ethyl acetate extraction.After cleaning organic layer with saturated aqueous common salt, use anhydrous sodium sulfate drying, heat up in a steamer desolvate after, use column chromatography (silica gel; Solvent hexane: ethyl acetate=5: 3) carry out purifying, obtain 1.2g (yield 13%) 4-(2-fluorine oxyethyl group)-6-(2 fluorine ethoxy carbonyl)-5-methyl sulphur chroman-1, the 1-dioxide (compound that is equivalent to formula (XI-2).
1H-NMR (solvent: CDCl
3, internal standard: tetramethylsilane, ppm): 2.58 (3H, s), 2.6-2.8 (2H, m), 3.1-3.4 (1H, m), 3.5-4.1 (3H, m), 4.2-4.5 (3H, m), 4.6-5.1 (4H, m), 7.80 (1H, d), 7.92 (1H, d)
(2) hydrolytic process
In the 4-of 1.2g (3.3mmol) (2-fluorine oxyethyl group)-6-(2-fluorine ethoxy carbonyl)-5-methyl sulphur chroman-1, in the 1-dioxide (compound that is equivalent to formula (XI-2)), add 0.4g potassium hydroxide, 5ml ethanol, 2ml water, 60 ℃ of heated and stirred 2 hours.Reaction is heated up in a steamer and is desolvated after finishing, and adds 5ml water, adds 2N hydrochloric acid and makes pH reach 1.Then use twice of ethyl acetate extraction.Behind the clean organic layer of saturated aqueous common salt, use anhydrous sodium sulfate drying, heat up in a steamer then and desolvate, obtain 4-(2-fluorine the oxyethyl group)-5-methyl sulphur chroman-1 of 1.0g (yield 100%), 1-dioxide-6-carboxylic acid (compound that is equivalent to formula (II-2)).
1H-NMR (solvent; Acetone-d6, internal standard; Tetramethylsilane): 2.62 (3H, s), 2.6-2.7 (1H, m), 2.8-3.1 (1H, m), 3.2-4.5 (5H, m), 4.8-5.1 (2H, m), 7.80 (1H, d), 7.98 (1H, d), 8.80 (1H, bs)
Make reference example 3
(1) etherification procedure
In the 4-hydroxy-5-methyl base sulphur chroman-1 of 2.3g (9.0mmol), 1-dioxide-6-carboxylic acid (is equivalent in (compound of formula (XII-2)), adds the ethylene chlorhydrin and the 0.1ml vitriol oil of 15ml, reflux 5 hours.Put cold after, reaction mixture is injected ice bath, with twice of ethyl acetate extraction.After cleaning organic layer with saturated aqueous common salt, use anhydrous sodium sulfate drying, heat up in a steamer desolvate after, use column chromatography (silica gel; Solvent hexane: ethyl acetate=2: 1) carry out purifying, obtain 4-(2-chloroethoxy)-6-(2-chloroethoxy the carbonyl)-5-methyl sulphur chroman-1 of 0.7g (yield 20%), 1-dioxide (compound that is equivalent to formula (XI-2)).
1H-NMR (solvent; CDCl
3, internal standard; Tetramethylsilane): 2.61 (3H, s), 2.6-2.7 (2H, m), 3.0-3.4 (1H, m), 3.5-4.0 (7H, m), 4.59 (2H, t), 4.76 (1H, t), 7.83 (1H, d), 7.96 (1H, d)
(2) hydrolytic process
In the 4-of 0.7g (1.8mmol) (2-chloroethoxy)-6-(2-chloroethoxy carbonyl)-5-methyl sulphur chroman-1, in the 1-dioxide (compound that is equivalent to formula (XI-2)), add 0.15g potassium hydroxide, 3ml ethanol, 1ml water, 60 ℃ of heated and stirred 2 hours.Reaction is heated up in a steamer and is desolvated after finishing, and adds 5ml water, adds 2N hydrochloric acid again and makes pH reach 1.Then use twice of ethyl acetate extraction.Behind the clean organic layer of saturated aqueous common salt, use anhydrous sodium sulfate drying, heat up in a steamer then and desolvate, obtain 0.6g (yield 100%) 4-(2-chloroethoxy)-5-methyl sulphur chroman-1,1-dioxide-6-carboxylic acid (compound that is equivalent to formula (II-2)).
1H-NMR (solvent; Acetone-d6, internal standard; Tetramethylsilane): 2.63 (3H, s), 2.6-3.1 (2H, m), 3.2-4.2 (6H, m), 4.91 (1H, t), 7.79 (1H, d), 7.98 (1H, d)
Make reference example 4
(1) alcoholization process
In the 5-chloro-6-of 7.4g (25.6mmol) ethoxycarbonyl-8-fluorine sulphur chroman-4-on-(compound that is equivalent to formula (VIII)), add 30ml methyl alcohol and 20ml methylene dichloride.Use salt solution, ice bath, keep the temperature of this mixture to be no more than 0 ℃, to wherein slowly adding 0.97g (25.6mmol) sodium borohydride.After 3 hours, reaction mixture is injected 5% hydrochloric acid at room temperature reaction, use dichloromethane extraction.With the resulting organic layer of anhydrous sodium sulfate drying, after concentrating, with column chromatography (silica gel; Solvent hexane: ethyl acetate=2: 1) carry out purifying, obtain 4-hydroxyl-5-chloro-6-ethoxycarbonyl-8-fluorine sulphur chroman (compound that is equivalent to formula (IX)) of 2.9g (yield 40%).
1H-NMR (solvent: CDCl
3, internal standard; Tetramethylsilane): 1.39 (3H, t), 1.5-2.1 (1H, m), 2.4-3.6 (4H, m), 4.38 (2H, q), 5.28 (1H, m), 7.44 (1H, d)
(2) etherification procedure
In the 4-of 2.4g (8.2mmol) hydroxyl-5-chloro-6-ethoxycarbonyl-8-fluorine sulphur chroman (compound that is equivalent to formula (IX)), add 2-fluoroethanol and 3 vitriol oils of 5ml, reflux is 5 hours then.Put cold after, reaction mixture is injected ice bath, with twice of ethyl acetate extraction.Behind the clean organic layer of saturated aqueous common salt, use anhydrous sodium sulfate drying, heat up in a steamer and desolvate, obtain 4-(2-fluorine the oxyethyl group)-5-chloro-6-ethoxycarbonyl-8-fluorine sulphur chroman (compound that is equivalent to formula (X)) of 2.2g (yield 79%).
1H-NMR (solvent: CDCl
3, internal standard; Tetramethylsilane): 1.38 (3H, t), 1.5-2.0 (1H, m), 2.5-3.0 (2H, m), 3.1-4.3 (6H, m), 4.82 (1H, t), 5.00 (1H, bs), 7.44 (1H, d)
(3) oxidising process
In the 4-of 2.1g (7.2mmol) (2-fluorine oxyethyl group)-5-chloro-6-ethoxycarbonyl-8-fluorine sulphur chroman (compound that is equivalent to formula (X)), add 4ml acetate and 2.2ml (21.7mmol) 30% hydrogen peroxide, 80 ℃ of reactions 3 hours as oxygenant.Put cold after, in reaction mixture, add 2% aqueous solution of sodium bisulfite, remove superfluous hydrogen peroxide, with twice of ethyl acetate extraction.Behind the clean organic layer of saturated aqueous common salt, use anhydrous sodium sulfate drying, obtain 4-(2-fluorine the oxyethyl group)-5-chloro-6-ethoxycarbonyl-8-fluorine sulphur chroman-1 of 3.4g (yield 100%) thus, 1-dioxide (compound that is equivalent to formula (XI-2)) raw product.
1H-NMR (solvent: CDCl
3, internal standard; Tetramethylsilane): 1.41 (3H, t), 2.3-3.0 (2H, m), 3.1-3.5 (1H, m), 3.6-4.6 (6H, m), 4.7-5.1 (2H, m), 7.57 (1H, d)
Fusing point: 87-89 ℃
(4) hydrolytic process
In the 4-of 3.4g (9.2mmol) (2-fluorine oxyethyl group)-5-chloro-6-ethoxycarbonyl-8-fluorine sulphur chroman-1, in the 1-dioxide (compound that is equivalent to formula (XI-2)), add 0.77g potassium hydroxide, 15ml ethanol, 5ml water, stirring at room 3 hours.Reaction is heated up in a steamer and is desolvated after finishing, and behind the interpolation 5ml water, adds 2N hydrochloric acid, makes pH reach 1.Then use twice of ethyl acetate extraction.Behind the clean organic layer of saturated aqueous common salt, use anhydrous sodium sulfate drying, heat up in a steamer and desolvate, obtain 4-(2-fluorine the oxyethyl group)-5-chloro-8-fluorine sulphur chroman-1 of 2.9g (yield 92%) thus, 1-dioxide-6-carboxylic acid (compound that is equivalent to formula (II-2)).
1H-NMR (solvent: acetone-d6, internal standard; Tetramethylsilane): 2.3-3.2 (2H, m), 3.3-4.5 (5H, m), 4.88 (1H, t), 5.07 (1H, m), 7.79 (1H, d)
Fusing point: 163-165
Make embodiment 1
4-(2-fluorine oxyethyl group)-5,8-dimethyl-6-(1-ethyl-5-hydroxypyrazoles-4-yl) carbonylsulfide chroman-1, synthetic (being equivalent to process 1) of 1-dioxide (compound N is o.1)
In tertiary amyl alcohol, dissolving 5.08g (16.1mmol) makes the 4-(2-fluorine oxyethyl group)-5 that reference example 1 obtains, 8-dimethyl sulphide chroman-6-carboxylic acid-1,1-ethyl-5-hydroxypyrazoles (compound that is equivalent to formula (III)) of 1-dioxide (carboxylic acid derivative that is equivalent to formula (II)) and 1.98g (17.7mmol).Add the dehydrating condensation agent N of 3.65g (17.7mmol) in this solution, N '-dicyclohexyl carbodiimide (DCC) after 2 hours, adds the Anhydrous potassium carbonate of 1.67g (12.1mmol) as alkali in stirring at room, carries out reaction in 8 hours at 80 ℃.After reaction finished, decompression was heated up in a steamer and is desolvated, and residue is dissolved in 3% sodium carbonate solution, removes by filter insolubles, cleaned with ethyl acetate again.After making resulting water layer acidifying with 5% hydrochloric acid, the oily matter that generates with ethyl acetate extraction.Under reduced pressure heat up in a steamer ethyl acetate, obtain the compound of 4.71g (yield 71%) topic head.
Make embodiment 2
4-(2-fluorine oxyethyl group)-5,8-dimethyl-6-(positive third sulfonyloxy pyrazoles of 1-ethyl-5--4-yl) carbonylsulfide chroman-1, synthetic (being equivalent to process 2) of 1-dioxide (compound N is o.2)
In the 10ml methylene dichloride, dissolving 1.00g (2.44mmol) makes the 4-(2-fluorine oxyethyl group)-5 that embodiment 1 obtains, 8-dimethyl-6-(1-ethyl-5-hydroxypyrazoles-4-yl) carbonylsulfide chroman-1,1-dioxide (pyrazole derivatives that is equivalent to formula (I-a))).Be dissolved in the solution that forms in the 10ml water to wherein adding the salt of wormwood of 0.67g (4.87mmol) as alkali.In this mixing solutions, add positive third SULPHURYL CHLORIDE (compound that be equivalent to formula (IV)) of 0.42g (2.93mmol), add 0.05g (0.2mmol) phase-transfer catalyst benzyltriethylammoinium chloride again as reaction reagent.After room temperature made it carry out reaction in 2 hours, reflux was 2 hours again.After reaction finishes, reaction mixture is put cold, carried out separatory to wherein adding entry and methylene dichloride.After using distilled water, saturated sodium bicarbonate aqueous solution, salt solution that resulting organic layer is cleaned successively, use anhydrous sodium sulfate drying, after concentrating, carry out purifying with flash column chromatography again, obtain the compound of 0.79g (yield 63%) topic head.
Make embodiment 3
4-(2-fluorine oxyethyl group)-5,8-dimethyl-6-(1-ethyl-5-tolysulfonyl oxygen base pyrazoles-4-yl) carbonylsulfide chroman-1, synthetic (being equivalent to process 2) of 1-dioxide (compound N is o.3)
Except using Tosyl chloride to replace positive third SULPHURYL CHLORIDE of using (compound that is equivalent to formula (IV)) in making embodiment 2, embodiment 2 carries out identical reaction with manufacturing, obtains the compound of 0.45g (yield 65%) topic head.
Make embodiment 4
4-(2-fluorine oxyethyl group)-5,8-dimethyl-6-(1-ethyl-5-cyclohexyl carbonyl oxygen base pyrazoles-4-yl) carbonylsulfide chroman-1, synthetic (being equivalent to process 2) of 1-dioxide (compound N is o.4)
The 4-(2-fluorine oxyethyl group)-5 that the above-mentioned manufacturing embodiment 1 of 0.50g (1.22mmol) is obtained, 8-dimethyl-6-(1-ethyl-5-hydroxypyrazoles-4-yl) carbonylsulfide chroman-1,1-dioxide and 0.16g (0.58mmol) are cooled to 0 ℃ as the dichloromethane solution of the triethylamine of alkali, to wherein splashing into 0.21g (1.46mmol) hexamethylene carbonyl chlorine (compound that is equivalent to formula (IV)), room temperature reaction 2 hours.Reaction is injected saturated sodium bicarbonate aqueous solution with reaction mixture after finishing, and extracts with ethyl acetate.Clean resulting organic layer with saturated aqueous common salt, use anhydrous sodium sulfate drying, after concentrating, use flash column chromatography to carry out purifying, obtain the compound of 0.36g (yield 56%) topic head.
Make embodiment 5
4-(2-fluorine oxyethyl group) 5-methyl-6-(1-ethyl-5-hydroxypyrazoles 4-yl) carbonylsulfide chroman-1, synthetic (being equivalent to process 1) of 1-dioxide (compound N is o.5)
In tertiary amyl alcohol, 4-(2-fluorine oxyethyl group)-5 methyl sulphur chromans-1 of dissolving 1.0g (3.3mmol), 1-ethyl-5-hydroxypyrazoles (compound that is equivalent to formula (III)) of 1-dioxide-6-carboxylic acid (carboxylic acid that is equivalent to formula (II)) and 0.45g (4.0mmol).Add 0.83g (4.0mmol) dehydrating condensation agent N in this solution, N '-dicyclohexyl carbodiimide after 2 hours, adds the Anhydrous potassium carbonate of 0.34g (2.5mmol) as alkali in stirring at room, 80 ℃ of reactions 8 hours.After reaction finished, decompression was heated up in a steamer and is desolvated, and with 3% aqueous sodium carbonate dissolved residue, removes by filter insolubles, cleaned with ethyl acetate again.After making resulting water layer acidifying with 5% hydrochloric acid, the oily matter that generates with ethyl acetate extraction.Under reduced pressure heat up in a steamer ethyl acetate, obtain the compound of 1.2g (yield 90%) topic head.
Make embodiment 6
4-(2-fluorine oxyethyl group)-5-methyl-6-(positive third sulfonyloxy pyrazoles of 1-ethyl-5--4-yl) carbonylsulfide chroman-1, synthetic (being equivalent to process 2) of 1-dioxide (compound N is o.6)
In the 5ml methylene dichloride, dissolving 0.63g (1.6mmol) makes 4-(2-fluorine oxyethyl group)-5-methyl-6-(1-ethyl-5-hydroxypyrazoles-4-yl) carbonylsulfide chroman-1 that embodiment 5 obtains, 1-dioxide (pyrazole derivatives that is equivalent to formula (Ia)).Be dissolved in the solution that forms in the 5ml water to wherein adding the salt of wormwood of 0.4g (3.2mmol) as alkali.In this mixing solutions, add positive third SULPHURYL CHLORIDE (compound that be equivalent to formula (IV)) of 0.4ml (3.2mmol), add 0.05g (0.2mmol) phase-transfer catalyst benzyltriethylammoinium chloride again as reaction reagent.Make its reaction one day in room temperature.Reaction adds entry and methylene dichloride and carries out separatory after finishing.After cleaning resultant organic layer with distilled water, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt successively, use anhydrous sodium sulfate drying, concentrate, with column chromatography (silica gel; Solvent, hexane: ethyl acetate=1: 1) carry out purifying, obtain the compound of 0.55g (yield 68%) topic head.
Make embodiment 7
4-(2-chloroethoxy)-5-methyl-6-(1-ethyl-5-hydroxypyrazoles-4-yl) carbonylsulfide chroman-1, synthetic (being equivalent to process 1) of 1-dioxide (compound N is o.7)
In the 4ml tertiary amyl alcohol, dissolving 0.6g (1.9mmol) 4-(2-chloroethoxy)-5-methyl sulphur chroman-1,1-dioxide-6-carboxylic acid (carboxylic acid that is equivalent to formula (II)) and 0.24g (2.1mmol) 1-ethyl-5-hydroxypyrazoles (compound that is equivalent to formula (III)).Add 0.39g (2.1mmol) dehydrating condensation agent N in this solution, N '-dicyclohexyl carbodiimide after 2 hours, adds the Anhydrous potassium carbonate of 0.20g (1.4mmol) as alkali in stirring at room, 80 ℃ of reactions 8 hours.After reaction finished, decompression was heated up in a steamer and is desolvated, and with 3% aqueous sodium carbonate dissolved residue, removes by filter insolubles, cleaned with ethyl acetate again.Make the water layer acidifying that obtains with 5% hydrochloric acid, with the oily matter of ethyl acetate extraction generation.Under reduced pressure heat up in a steamer ethyl acetate, obtain the compound of 0.34g (yield 43%) topic head.
Make embodiment 8
4-(2-chloroethoxy)-5-methyl-6-(positive third sulfonyloxy pyrazoles of 1-ethyl-5--4-yl) carbonylsulfide chroman-1, synthetic (being equivalent to process 2) of 1-dioxide (compound N is o.8)
In the 3ml methylene dichloride, 4-(2-chloroethoxy)-5-methyl-6-(1-ethyl-5-hydroxypyrazoles-4-yl) carbonylsulfide chroman-1 that the above-mentioned manufacturing embodiment 7 of dissolving 0.34g (0.8mmol) obtains, 1-dioxide (pyrazole derivatives that is equivalent to formula (Ia)).In wherein being added on 2ml water, dissolve the solution of 0.23g (1.6mmol) as the salt of wormwood formation of alkali.In this mixing solutions, add positive third SULPHURYL CHLORIDE (compound that be equivalent to formula (IV)) of 0.2ml (1.6mmol), add 0.01g (0.05mmol) phase-transfer catalyst benzyltriethylammoinium chloride again as reaction reagent.Make it room temperature reaction one day.Reaction adds entry and methylene dichloride and carries out separatory after finishing.After cleaning resulting organic layer with distilled water, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt successively, use anhydrous sodium sulfate drying, concentrate, with column chromatography (silica gel; Hexane: ethyl acetate=1: 1) carry out purifying, obtain the compound of 0.23g (yield 54%) topic head.
Make embodiment 9
4-(2-fluorine oxyethyl group)-5-chloro-6-(1-ethyl-5-hydroxypyrazoles-4-yl) carbonyl-8-fluorine sulphur chroman-1, synthetic (being equivalent to process 1) of 1-dioxide (compound N is o.9)
In the 4ml tertiary amyl alcohol, dissolving 1.5g (4.3mmol) 4-(2-fluorine oxyethyl group)-5-chloro-8-fluorine sulphur chroman-1,1-dioxide-6-carboxylic acid (carboxylic acid that is equivalent to formula (II)) and 0.53g (4.7mmol) 1-ethyl-5-hydroxypyrazoles (compound that is equivalent to formula (III)).Add 0.97g (4.7mmol) dehydrating condensation agent N in this solution, N '-dicyclohexyl carbodiimide after 2 hours, adds the Anhydrous potassium carbonate of 0.20g (1.4mmol) as alkali in stirring at room, 80 ℃ of reactions 8 hours.After reaction finished, decompression was heated up in a steamer and is desolvated, and with 3% aqueous sodium carbonate dissolved residue, removes by filter insolubles, cleaned with ethyl acetate again.Make the water layer acidifying that obtains with 5% hydrochloric acid, with the oily matter of ethyl acetate extraction generation.Under reduced pressure heat up in a steamer ethyl acetate, obtain the compound of 0.90g (yield 48%) topic head.
Make embodiment 10
4-(2-fluorine oxyethyl group)-5-chloro-6-(positive third sulfonyloxy pyrazoles of 1-ethyl-5--4-yl) carbonyl-8-fluorine sulphur chroman-1, synthetic (being equivalent to process 2) of 1-dioxide (compound N is o.10)
In the 5ml methylene dichloride, 4-(2-fluorine oxyethyl group)-5-chloro-6-(1-ethyl-5-hydroxypyrazoles-4-yl) carbonyl-8-fluorine sulphur chroman-1 that the above-mentioned manufacturing embodiment 9 of dissolving 0.69g (1.6mmol) obtains, 1-dioxide (pyrazole derivatives that is equivalent to formula (Ia)).In wherein being added on 2ml water, dissolve the solution of 0.26g (1.9mmol) as the salt of wormwood formation of alkali.In this mixing solutions, add positive third SULPHURYL CHLORIDE (compound that be equivalent to formula (IV)) of 0.21ml (1.9mmol), add 0.05g (0.2mmol) phase-transfer catalyst benzyltriethylammoinium chloride again as reaction reagent.Make it room temperature reaction one day.Reaction adds entry and methylene dichloride and carries out separatory after finishing.After cleaning resultant organic layer with distilled water, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt successively, use anhydrous sodium sulfate drying, concentrate, with column chromatography (silica gel; Hexane: ethyl acetate=1: 1) carry out purifying, obtain the compound of 0.52g (yield 60%) topic head.
The structure of the compound that above embodiment 1~10 obtains and physics value are shown among the table 1-4.Table 1
Table 2
Table 3
Table 4
Weedicide embodiment
(1) modulation of weedicide
With the talcum (trade(brand)name of 97 parts by weight as carrier; ジ-Network ラ イ ト), 1.5 parts by weight tensio-active agent alkyl aryl sulphonic acid (trade(brand)names; ネ オ ペ レ Star Network ス, flower king ア ト ラ ス (strain) make) and the non-ionic type of 1.5 parts by weight and the surfactant mixture (trade(brand)name of anionic; ソ Le Port-Le 800A, eastern nation chemical industry (strain) are made) evenly pulverize and mix, obtain the wettable powder carrier.
The compound of the present invention (for comparative example, with the following compound (A) of 10 parts by weight) that this wettable powders of 90 parts by weight is obtained with carrier and the above-mentioned manufacturing embodiment of 10 parts by weight is evenly pulverized and is mixed, and obtains weedicide.
The compound (A) of medicament use has following structure as a comparison.
Then, in following test, specify the purposes of compound of the present invention as weedicide.
(2) biological test (cauline leaf Processing Test)
In 1/5000 are the Wagner basin of filling field soil, sow the seed of weed seeds such as rising lady's-grass, barnyard grass, herba setariae viridis grass, Siberian cocklebur, piemarker, ア オ PVC ユ and corn, wheat, barley, behind the overburden soil, in the greenhouse, cultivate, in 3~4 leaf phases of these plants, the phytocide suspension of the specified amount that above-mentioned (1) is obtained floats over the suspension that forms in the water and sprays leaves and stems equably with suitable 2000 liters/hectare amount.After this in the greenhouse, cultivate, after processing, judged herbicidal effect on the 30th day and the poisoning of crop.The results are shown in table 5 (1) and (2).
In addition, herbicidal effect and chemical injury of crops are represented according to following benchmark.
Benchmark
The heavy non-processor of the residual grass of herbicidal effect is than [%]
0?????????????????????81~100
1?????????????????????61~80
2?????????????????????41~60
3?????????????????????21~40
4?????????????????????1~20
5?????????????????????0
The heavy non-processor of the residual grass of chemical injury of crops is than [%]
-??????????????????????100
±????????????????????????????????????????????95~99
+??????????????????????90~94
++?????????????????????80~89
+++????????????????????0~79
At this, the heavy non-processor ratio of residual grass=(it is residual careless heavy that the residual grass of treatment zone weigh/is untreated and distinguishes) * 100
Table 5 (1)
The compound N o. that uses | Dose (g a.i./ hectare) | Weeding activity | Chemical injury of crops | |||||||
Rise lady's-grass | Barnyard grass | Herba setariae viridis grass | Siberian cocklebur | Piemarker | アオビユ | Corn | Wheat | Barley | ||
????(1) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ?????- | ????- | ????- |
????(2) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ?????- | ????- | ????- |
????(3) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ?????- | ????- | ????- |
????(4) | ??300 | ????5 | ????4 | ????5 | ????5 | ????5 | ????5 | ?????- | ????- | ????- |
????(A) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ?????++ | ????± | ????+ |
The abbreviation of a.i.=effective constituent (active ingredient).
N.d.=does not obtain the abbreviation of data (not detected).
Table 5 (2)
The compound N o. that uses | Dose (g a.i./ hectare) | Weeding activity | Chemical injury of crops | |||||||
Rise lady's-grass | Barnyard grass | Herba setariae viridis grass | Siberian cocklebur | Piemarker | アオビユ | Corn | Wheat | Barley | ||
????(5) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????- | ??????- | ????- |
????(6) | ??300 | ????4 | ????5 | ????4 | ????5 | ????5 | ????5 | ????- | ??????- | ????- |
????(7) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????n.d. | ????- | ??????- | ????- |
????(8) | ??300 | ????5 | ????5 | ????4 | ????5 | ????4 | ????4 | ????- | ??????- | ????- |
????(9) | ??300 | ????5 | ????4 | ????4 | ????5 | ????4 | ????5 | ????- | ??????- | ????- |
????(10) | ??300 | ????5 | ????5 | ????4 | ????5 | ????4 | ????4 | ????- | ??????- | ????- |
????(A) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????++ | ?????± | ????+ |
The abbreviation of a.i.=effective constituent (active ingredient).
N.d.=does not obtain the abbreviation of data (not detected).
Can know that from the result of table 5 (1) and (2) in the cauline leafs of 3~4 leaf phases is handled, cause poisoning opposite with weedicide relatively to crop, weedicide of the present invention does not cause poisoning to crop, safe to crop.In addition, weedicide of the present invention shows excellent herbicidal to various weeds, has extremely good crops and weeds selectivity.
(3) biological test (soil treatment test)
Sowing rises the seed of the weed seed of lady's-grass, barnyard grass, herba setariae viridis grass, Siberian cocklebur, piemarker, ア オ PVC エ and corn, wheat, barley, cotton in 1/5000 are the Wagner basin of filling field soil, behind the overburden soil, the phytocide suspension of the specified amount that above-mentioned (1) is obtained floats over the suspension that forms in the water and is sprayed at soil surface equably with suitable 2000 liters/hectare amount.After this in the greenhouse, cultivate, after processing, judged herbicidal effect on the 20th day and the poisoning of crop.The results are shown in the table 6.
Table 6
The compound N o. that uses | Dose (g a.i./ hectare) | Weeding activity | Chemical injury of crops | ||||||||
Rise lady's-grass | Barnyard grass | Herba setariae viridis grass | Siberian cocklebur | Piemarker | アオビユ | Corn | Wheat | Barley | Cotton | ||
????(1) | ??300 | ????5 | ????5 | ????4 | ????5 | ????5 | ????4 | ????- | ????- | ????- | ??- |
????(2) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????- | ????- | ????± | ??- |
????(3) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????- | ????- | ????- | ??- |
????(4) | ??300 | ????5 | ????5 | ????4 | ????4 | ????5 | ????5 | ????- | ????- | ????- | ??- |
????(5) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????- | ????- | ????- | ??- |
????(6) | ??300 | ????5 | ????5 | ????5 | ????3 | ????5 | ????4 | ????- | ????- | ????- | ??- |
????(7) | ??300 | ????5 | ????5 | ????3 | ????5 | ????5 | ????5 | ????- | ????- | ????- | ??- |
????(8) | ??300 | ????5 | ????4 | ????4 | ????5 | ????5 | ????5 | ????- | ????- | ????- | ??- |
????(9) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????4 | ????- | ????- | ????- | ??- |
????(10) | ??300 | ????5 | ????5 | ????5 | ????4 | ????5 | ????3 | ????- | ????- | ????- | ??- |
????(A) | ??300 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????- | ????- | ????± | ??+++ |
The abbreviation of a.i.=effective constituent (active ingredient).
As can be known from the results of Table 6, in soil treatment test, cause poisoning opposite with weedicide relatively to crop, weedicide of the present invention does not cause poisoning to crop, safe to crop.In addition, weedicide of the present invention shows excellent herbicidal to various weeds, has extremely good crops and weeds selectivity.
As discussed above, according to the present invention, can be provided at that cauline leaf is handled and soil treatment in the extremely good optionally novel pyrazole derivatives of crops and weeds of demonstration and with the weedicide of this derivative as effective constituent.
Claims (13)
In the formula, R
1Be C with 1 above halogen atom
1-C
6Haloalkyl; R
2, R
3, R
4And R
5Be hydrogen atom or C independently of one another
1-C
4Alkyl;
R
6Be C
1-C
4Alkyl;
R
7Be hydrogen atom or C
1-C
4Alkyl;
X is C
1-C
4Alkyl or halogen atom;
P and n are 0,1 or 2 integer independently of one another;
Q be hydrogen atom or base-A ,-B
[in the formula, A is-SO
2-, (CH
2)
k-CO-or-CR
8R
9-
(in the formula, k be 0 or the integer of 1-3,
R
8And R
9Be hydrogen atom or C independently of one another
1-C
4Alkyl);
B is C
1-C
12Alkyl, C
3-C
12Cycloalkyl or base-Ph-Y
m(Y that in the formula, Ph is phenyl, replace on Ph is C
1-C
4Alkyl, C
1-C
4Alkoxyl group, has the C of 1 above halogen atom
1-C
4Haloalkyl, nitro or halogen atom, m be 0 or the integer of 1-2)].
2. the described pyrazole derivatives of claim 1, wherein, R
1Be C with straight or branched
1-C
4Haloalkyl.
3. the described pyrazole derivatives of claim 2, wherein, R
1Be 2-chloroethyl or 2-fluoro ethyl.
4. the described pyrazole derivatives of claim 1, wherein, R
2, R
3, R
4And R
5Be hydrogen atom or methyl independently of one another.
5. the described pyrazole derivatives of claim 1, wherein, R
6Be methyl or ethyl.
6. the described pyrazole derivatives of claim 1, wherein, R
7Be hydrogen atom or methyl.
7. the described pyrazole derivatives of claim 1, wherein, X is methyl, chlorine atom or fluorine atom.
8. the described pyrazole derivatives of claim 7, wherein, the position of substitution of X is 5 and/or 8 of sulphur chroman ring.
9. the described pyrazole derivatives of claim 1, wherein, n is 2.
10. the described pyrazole derivatives of claim 1, wherein, Q is a hydrogen atom.
11. the described pyrazole derivatives of claim 1, wherein, when Q was base-A-B, A was-SO
2-or-(CH
2)
k-CO-, B are C
1-C
4Alkyl, C
3-C
8Cycloalkyl or base-Ph-Y
m(in the formula, Ph is a phenyl, and the Y that replaces on Ph is C
1-C
4Alkyl, C
1-C
4Alkoxyl group, has the C of 1 above halogen atom
1-C
4Haloalkyl, nitro or halogen atom, m are 0 or 1~2 integers).
12. the described pyrazole derivatives of claim 11, wherein, when Q was base-A-B, A was-SO
2-, B is that ethyl, n-propyl or toluyl are (at-Ph-Y
mIn, Y is that 4-methyl, m are 1); Perhaps
A is-CO-or-CH
2CO-[is at-(CH
2)
kAmong-the CO-, k is 0 or 1], B is that cyclohexyl or phenyl are (at-Ph-Y
mIn, m is 0).
13. with each described pyrazole derivatives among the claim 1-12 as the weedicide of effective constituent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 96193076 CN1180355A (en) | 1995-04-05 | 1996-03-28 | Pyrazole derivatives |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP80059/95 | 1995-04-05 | ||
CN 96193076 CN1180355A (en) | 1995-04-05 | 1996-03-28 | Pyrazole derivatives |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1180355A true CN1180355A (en) | 1998-04-29 |
Family
ID=5128624
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 96193076 Pending CN1180355A (en) | 1995-04-05 | 1996-03-28 | Pyrazole derivatives |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1180355A (en) |
-
1996
- 1996-03-28 CN CN 96193076 patent/CN1180355A/en active Pending
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