CN100586934C - Process for the preparation of trifluoromethylthioether - Google Patents
Process for the preparation of trifluoromethylthioether Download PDFInfo
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- CN100586934C CN100586934C CN200480031631A CN200480031631A CN100586934C CN 100586934 C CN100586934 C CN 100586934C CN 200480031631 A CN200480031631 A CN 200480031631A CN 200480031631 A CN200480031631 A CN 200480031631A CN 100586934 C CN100586934 C CN 100586934C
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Abstract
A process for the preparation of a trifluoromethylthioether of the formula (I) by reaction of a thiocyanate of the formula (II) with a trifluromethyl halide in the presence of a reducing system comprising a dithionite salt or a hydroxymethansulfinate salt or comprising one or more reducing agents with sulphur dioxide.
Description
The present invention relates to the method for the trifluoromethyl thioether of preparation formula (I),
This method is included in the reduction system that contains hyposulfite or hydroxyl methyl-sulfinic acid salt or contain one or more reductive agents and sulfurous gas and exists down, makes the thiocyanic acid of formula (II):
React with trifluoromethyl halogen.
Background technology
Known several method preparation comprises the perfluoroalkyl thioether of compound (I).Method by perfluoroalkyl halide and disulphide preparation is disclosed in the prior art:
Following method is disclosed in United States Patent (USP) no.5082945: use perfluoroalkyl halide, wherein by being selected from the reductive agent that metal in zinc, cadmium, aluminium and the manganese and sulfurous gas are formed, the perhaps reductive agent of forming by basic metal hyposulfite or basic metal or alkaline-earth metal or metal hydroxy methyl-sulfinic acid salt, perhaps the reductive agent of being made up of formate anion and sulfurous gas exists down, and described perfluoroalkyl halide is contacted with disulphide.
International patent application no.WO01/30760-A1 discloses a kind of similar method.European patent application no.295117-A1 discloses in the mixture of water-containing organic solvent such as ethanol or alcohol and water and has used V-Brite B or sodium borohydride.
People such as Clavel are at Phosphorus, Sulfur and Silicon and the RelatedElements (1991), 59 (1-4), 423-6; Journal of the ChemicalSociety, Chemical Communications (1991), (15), and 993-4 and Journalof the Chemical Society, Perkin Transactions 1 (1992), (24), 3371-5.Use hydrazine and/or the metal borohydride method as reductive agent is disclosed among the international patent application no.WO 02/066423-A1.
Really advantageously directly use compound (II), and needn't be before the compound of preparation formula (I), at first the rhodan-compound by formula (II) prepares disulphide, as described in the above reference.
People such as Tordeux are at Journal of Fluorine Chemistry, and 43 (1989), disclose among the 27-34 in the presence of zinc, by making the reaction of thiocyanic acid and perfluoroalkyl halide, prepare the method for perfluoroalkyl sulfide.It is reported that productive rate is moderate when using perfluoro butyl or perfluoro octyl iodide.Yet, observe poor productive rate when using the trifluoromethyl bromine.In european patent application no.295117-A1, suggestion is reacted under preferred sodium borohydride exists at alkali or reductive agent.When the compound of use formula (II), methyl-iodide and potassium hydroxide, productive rate moderate (embodiment 15).In same application, organometallic reagent, for example Grignard reagent are used in suggestion.In addition, when the compound of use formula (II) and tertiary butyl chlorination magnesium, observe low-yield (embodiment 16).In addition, be difficult to handle on a large scale Grignard reagent, and be not easy to prepare the trifluoromethyl magnesium halide.People such as Langlois disclose among the 65-68 in the presence of tetrabutyl ammonium fluoride (TBAF) in Tetrahedron Letters38 (1997), use the trifluoromethyl trimethyl silane, are prepared the method for trifluoromethyl sulfide by thiocyanic acid.These two kinds of reagent costlinesses Just because of this, are not ideal using on commercial size.According to viewed result, when comparing with the straight-chain paraffin substrate, use when replacing the aromatics thiocyanic acid with simple aromatic hydrocarbons (aromate), productive rate significantly descends.In United States Patent (USP) no.5756849, benzyl thiocyanide is contacted with the sylvite of trifluoroacetic acid, thereby obtain 36% benzyl trifluoromethyl sulfide.In United States Patent (USP) no.6316636, find to use benzyl thiocyanide to prepare the method for benzyl trifluoromethyl sulfide, and involve use pyridine hydrofluoric acid complex compound for three chlorine atoms and fluorine atom exchange as parent material.Although productive rate is higher, use hydrofluoric acid to have serious risk really.
Although in this field, have progress recently, but still need and to use the material that obtains easily and to avoid complicated and extra middle process step with high costs for the alternate method, make the compound of formula (I) by the direct high productivity of the compound of formula (II).
The compound of formula (I) is a kind of known compound, can be used as the initiator that is for example prepared sterilant Fipronil and related compound by known method in the method described in the European patent no.295117-A1.
The compound of formula (II) also is a kind of known compound, and it can for example prepare in the method described in the EP295117A1 according to known operation.
Invention description
The present invention relates to the method for the trifluoromethyl thioether of preparation formula (I):
This compound is 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfo--1H-pyrazoles, described method comprises the steps: at the reduction system that contains hyposulfite or hydroxyl methyl-sulfinic acid salt or contains in the presence of the reduction system of one or more reductive agents and sulfurous gas, in solvent, make the sulfocyanic ester compound of formula (II)
(it is 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-thiocyano-1H-pyrazoles-3-nitrile) and the reaction of trifluoromethyl halogen.
Trifluoromethyl halogen can be selected from CF
3Cl, CF
3I and CF
3Br.Consider from economic angle, preferably select CF
3Br.The mol ratio of the thiocyanic acid of trifluoromethyl halogen and formula (II) preferably is higher than 1.
When use contained the reduction system of hyposulfite or hydroxyl methyl-sulfinic acid salt, with respect to the thiocyanic ester of formula (II), employed salt compound consumption was generally the 1-15mol equivalent, preferred 2-11mol equivalent.With salt compound or with solid form, perhaps dissolution (preferably identical with reaction solvent solvent) in solvent is incorporated in the reaction vessel.
Hyposulfite are metal or amine salt preferably, for example sodium, potassium, calcium or ammonium, wherein V-Brite B most preferably.Hydroxyl methyl-sulfinic acid salt is metal-salt preferably, for example sodium (being called Rongalite) or zinc (being called Decroline), wherein hydroxyl methyl-sulfinic acid sodium most preferably.
When use contained the reduction system of sulfurous gas and reductive agent, reductive agent for example was selected from the metal such as zinc, cadmium, aluminium and manganese; Hydrazine; Formic acid, formate be metal or amine salt for example, the basic metal of preferable formic acid or ammonium salt and even the more preferably sodium or the sylvite of formic acid, most preferably sodium formiate; Aluminum hydride, for example chemical formula R
3R
4AlH, M[R
3R
4AlH
2] or MAlH
4Those, R wherein
3And R
4Represent C separately independently of one another
1-4Alkyl and M are lithium or sodium, and comprise (i-C
4H
9)
2AlH and LiAlH
4Hydroborate, for example metal or amine hydroborate, for example NaBH
4, LiBH
4, (CH
3)
4NBH
4, NaBH
3CN; The compound of formula (III):
Wherein X represents O or S;
Y
1And Y
2Can be identical or different, represent H or O-R separately, wherein R represents the straight or branched alkyl chain or the alkali metal atom of hydrogen atom, a 1-5 carbon atom; Condition is Y
1And Y
2In at least a be not hydrogen atom.Preferred wherein X represents those of O.More preferably Y wherein
1Represent H or OH and Y
2Represent OH or O-alkali-metal those, wherein sodium is preferred basic metal.Even be more preferably phosphoric acid (H
3PO
3), Hypophosporous Acid, 50 (H
3PO
2) and sodium hypophosphite (NaH
2PO
2), wherein Hypophosporous Acid, 50 and sodium hypophosphite are most preferred selections.Be appreciated that the reductive agent that can use formula (III) with one or more hydrated forms, preference is as a hydration sodium hypophosphite (NaH
2PO
2, 1H
2O) and sodium hypophosphite hydrate (NaH
2PO
2, xH
2O), sodium hypophosphite hydrate most preferably wherein.With respect to the thiocyanic acid of formula (II), the consumption of employed reductive agent is generally the 1-15mol equivalent, preferred 2-11mol equivalent.With reductive agent former state ground, for example or solid or liquid form be incorporated in the reaction vessel, perhaps dissolution/absorbtion is at solvent, in preferably identical with the reaction solvent solvent or water.Step by step, continuously, perhaps before reaction, introduce reductive agent, and people can be incorporated into this reagent in the reaction mixture as last reagent.
Sulfurous gas can exist with catalytic amount, but with respect to the thiocyanic acid of formula (II), preferably is higher than 1 normal consumption, more preferably between 1-7 and even more preferably between 1.5-4.5, but the upper limit is not crucial.Step by step, continuously, perhaps before reaction, add sulfurous gas, and people can be incorporated into sulfurous gas in the reaction mixture as last reagent.Be incorporated in the reaction vessel with sulfurous gas or with gas form, perhaps be dissolved in solvent, in the preferably identical solvent with reaction solvent.
Reaction solvent can be any solvent in principle, described solvent inertia, and can be at solubilizing reaction thing under the reaction conditions.About this point, the term 'inertia' intend referring to solvent not on significant degree with mixture in component reaction.Preferred solvent is a polar solvent, for example methane amide, pyridine, dimethyl formamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMA), hexamethyl phosphoric triamide (HMPT), N-Methyl pyrrolidone (NMP), methyl-sulphoxide (DMSO), tetramethylene sulfone and ether, for example dme, diox, tetrahydrofuran (THF) and glycol dimethyl ether (DME) or its mixture, wherein DMF is preferred selection.Small amount of water can be joined in the solvent, for example volume is that maximum 35% and preferable amount of employed solvent volume are 5-30%.Temperature of reaction is usually in 20-110 ℃ of scope or be equal to or less than the boiling point of solvent, preferably between 30-80 ℃ with even more preferably between 40-60 ℃.Because the gaseous state character of trifluoromethyl halogen therefore at the suitable device of being made by non-reactive material, for example in the reactor of glass reactor or teflon coating, is reacted under pressure.Preferably between 1 to 30bar pressure.
Can before the reaction or among, by adding damping fluid, the variation of pH in the realization response mixture.The example of sort buffer liquid can be the organic or inorganic type, and comprises pyridine, amine (for example, ammoniacal liquor, triethylamine), alkali metal hydroxide and faintly acid salt, for example alkali-metal carbonate, phosphoric acid salt, sulphite, citric acid and acetate (for example, NaHCO
3, Na
2CO
3, NaH
2PO
4, Na
2HPO
4, NaHSO
3).
Last in reaction, separate solvent and reaction product, and before any synthesis procedure subsequently purifying trifluoromethyl thioether, compound (I).
Setting forth the present invention by following embodiment, in any case described embodiment is not intended to be limiting the present invention, and only is to provide with the purpose that exemplifies:
Embodiment 1.1
In the Teflon bushing pipe (insert) of 200ml Berghof autoclave, add the 5-amino-1-(2 in the mixture that is dissolved in 50ml DMF and 5ml water, 6-dichlor-4-trifluoromethyl phenyl)-4-thiocyano-1H-pyrazoles-3-nitrile (14.3mmol, 5.04g) and sodium formiate (71.5mmol, 5.01g) and sulfurous gas (43mmol, 2.75g).Airtight this autoclave, and at room temperature stirred 5 minutes, CF used
3Br pressurizes to autoclave.Up to pressure is 11.5bar.Add the CF of total amount 34.1g
3Br.Heated this autoclave to 50 ℃ then through 3.5 hours.Cool off this autoclave to room temperature, and after relief pressure, open.Wash with water and with the methyl tertiary butyl ether extraction product after, analyze this product (GC in mark method).The productive rate of 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfo--1H-pyrazoles is 4.7g (theoretical value 78%).
The serial experiment that uses aforesaid method is provided in the table 1.
Embodiment 2.1
In the Teflon bushing pipe of 50ml Berghof autoclave, add the 5-amino-1-(2 in the mixture that is dissolved in 10ml DMF and 2.8ml water, 6-dichlor-4-trifluoromethyl phenyl)-4-thiocyano-1H-pyrazoles-3-nitrile (2.86mmol, 1.08g) and sodium formiate (20mmol, 1.40g) and sulfurous gas (5.94mmol, 0.38g).Cool off this Teflon bushing pipe to-60 ℃, CF
3Br (58mmol, 8.7g) condensation in this bushing pipe, airtight this autoclave, and be heated to 55 ℃ through 3 hours.Cool off this autoclave to room temperature, and after relief pressure, open.Wash with water and with the methyl tertiary butyl ether extraction product after, analyze this product (GC in mark method).The productive rate of 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfo--1H-pyrazoles is 1.05g (theoretical value 87%).
The serial experiment that uses aforesaid method is provided in the table 2.
Embodiment 3.1
In the Teflon bushing pipe of 50ml Berghof autoclave, add 10ml DMF with 2.8g water, 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-thiocyano-1H-pyrazoles-3-nitrile (2.88mmol, 1.104g), V-Brite B (4.32mmol, 0.886g) and Na
2HPO
4, 12H
2O (1.54g).Cool off this Teflon bushing pipe to-60 ℃, CF
3Br (58mmol, 8.7g) condensation in this bushing pipe, airtight this autoclave, and be heated to 45 ℃ through 3 hours.Cool off this autoclave to room temperature, and after relief pressure, open.Wash with water and with the methyl tertiary butyl ether extraction product after, analyze this product (GC in mark method).The productive rate of 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfo--1H-pyrazoles is 62%.
Embodiment 3.2
In the Teflon bushing pipe of 50ml Berghof autoclave, add the 10ml DMF with 2.7g water, 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-thiocyano-1H-pyrazoles-3-nitrile (1.106g) and Rongalite (4.29g).Cool off this Teflon bushing pipe to-60 ℃, CF
3Br (6.58g) condensation in this bushing pipe, airtight this autoclave, and be heated to 45 ℃ through 3 hours.Cool off this autoclave to room temperature, and after relief pressure, open.Wash with water and with the methyl tertiary butyl ether extraction product after, analyze this product (GC in mark method).The productive rate of 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfo--1H-pyrazoles is 41%.
Embodiment 4.1
In teflon is in the autoclave of lining, at room temperature, 14.5mmol (5.52g) 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-thiocyano-1H-pyrazoles-3-nitrile is joined in the mixture of 50ml DMF and 37.5mmol (2.4g) sulfurous gas.Seal this reactor, and, then add CF with nitrogen purging 2 minutes
3Br (16.8g).Reactor heating to 30 ℃, and during 80 minutes time period, slowly add the 7.0g sodium formiate that is dissolved in the 10g water, simultaneously during adding with through extra 60 minutes time period holding temperature between 50 ℃ to 54 ℃.Cool off this autoclave to room temperature, and after relief pressure, open.Wash with water and with the methyl tertiary butyl ether extraction product after, analyze this product (GC in mark method).The productive rate of 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfo--1H-pyrazoles is 84.7%.
Embodiment 5.1
In teflon is in the autoclave of lining, at room temperature, 14.5mmol (5.52g) 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-thiocyano-1H-pyrazoles-3-nitrile and 63mmol (6.67g) yellow soda ash are joined in the mixture of 50ml DMF and 37.5mmol (2.4g) sulfurous gas.Seal this reactor, and, then add CF with nitrogen purging 2 minutes
3Br (16.8g).Reactor heating to 30 ℃, and during during 45 minutes time period, slowly adding 132mmol (6.07g) sodium formiate that is dissolved in the 10ml DMF and adding simultaneously with through extra 60 minutes time period holding temperature between 55 ℃ to 60 ℃.Cool off this autoclave to room temperature, and after relief pressure, open.Wash with water and with the methyl tertiary butyl ether extraction product after, analyze this product (GC in mark method).The productive rate of 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfo--1H-pyrazoles is 76.5%.
Embodiment 6.1
In the autoclave of the 1000ml teflon coating of being with the PVDF agitator, 100mmol 5-amino-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-thiocyano-1H-pyrazoles-3-nitrile (42.25g, purity 89.5%) is joined 14.24g (222mmol) SO
2In the solution in 312ml DMF.Seal this reactor, and use CF
3Br purged 2 minutes, then added 61.5g CF
3Br.Heat this reactor to 65 ℃ then.When the content of autoclave reaches 50 ℃ temperature, during 50 minutes time period, slowly add the solution of 152.6g 46.5% (w/w) sodium formiate in water, simultaneously during adding and maximum 68 ℃ of the extra 60 minutes time period holding temperature of 65 ℃ of warps.In adding the formate process, cause pressure significantly to increase owing to form carbonic acid gas, and the pressure that reduces in the reactor for 2 times, then 2 CF with new system
3Br recharges (each 6g) limitedly.Cool off this autoclave to room temperature, and by oxidation alkalescence scrubber relief pressure.The effluent air logistics is substantially free of non-required gas from this scrubber, and it contains 95% the CF of having an appointment
3Br is with its compression and collect for re-using.
Open autoclave, and product is transferred in 750ml water and the 250ml isopropyl acetate.Separate each phase, wherein twice usefulness 100ml isopropyl acetate aqueous phase extracted and throwing aside.
The isopropyl acetate phase that merges with the 100ml water washing for 2 times, and remove and desolvate, thereby cause 41.73g to contain the thick product (this analyzes spectrometry by HPLC) of 92.9% product.The productive rate of 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfo--1H-pyrazoles (I) is 92%.
By from suitable solvent or solvent mixture, for example recrystallization in toluene or the toluene heptane mixture is further purified thick product.
The serial experiment that uses aforesaid method is provided in the table 3.
Table 1
The DMF=dimethyl formamide
The quantity of solvent of being added except water is 50ml
Table 2
The DMF=dimethyl formamide, DMA=N, N-N,N-DIMETHYLACETAMIDE, HMPT=hexamethyl phosphoric triamide, DMSO=methyl-sulphoxide, DME=glycol dimethyl ether (ethan)
The quantity of solvent of being added except water is 10ml
Table 3
| Numbering | 6.2 | 6.3 | 6.4 | 6.5 | 6.6 | 6.7 | 6.8 |
| Consumption (II) (mmol) | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Purity (II) (%) | 90.8 | 90.8 | 92.6 | 92.6 | 89.5 | 91.3 | 91.3 |
| CF 3Br (g)(a) | 64.6+6.1 | 64.6+10.8 | 64.6+15.4 | 70.8+12.3 | 61.5+12.3 | 61.5+15.4 | 61.5+12.3 |
| The interpolation time (min) | 77 | 64 | 73 | 72 | 64 | 85 | 58 |
| Reaction times (h) | 60 | 60 | 60 | 60 | 60 | 60 | 60 |
| (I) productive rate (%) | 80.4 | 82.2 | 85.9 | 87.0 | 87.3 | 87.7 | 89.9 |
| CF 3The supply of Br | A | A | B | B | B | B | B |
| Solvent in the comprehensive treating process | (1) | (1) | (1) | (1) | (2) | (2) | (2) |
Remarks:
(1) methyl tertiary butyl ether
(2) isopropyl acetate
(a) first consumption is CF
3The initial amount of Br, second consumption adds subsequently
A only adds the CF that replenishes after adding all formate solutions
3Br
B adds the CF that replenishes in the process of adding formate solution
3Br
Claims (17)
1. the method for the compound of a preparation formula (I):
Described method comprises the steps: at the reduction system that contains hyposulfite or hydroxymethanesulfinate or contains in the presence of the reduction system of one or more reductive agents and sulfurous gas, in solvent, makes the compound and the reaction of trifluoromethyl halogen of formula (II):
2. the process of claim 1 wherein that reduction system comprises hyposulfite or hydroxymethanesulfinate.
3. the method for claim 2, wherein reduction system comprises hyposulfite.
4. the method for claim 3, wherein reduction system comprises V-Brite B.
5. the process of claim 1 wherein that reduction system comprises one or more reductive agents and sulfurous gas.
6. the method for claim 5, wherein reductive agent is selected from metal; Hydrazine; Formic acid; Formate; Aluminum hydride; Hydroborate, and the compound of formula (III):
Wherein X represents O or S;
Y
1And Y
2Can be identical or different, represent H or O-R separately, wherein R represents the straight or branched alkyl chain or the alkali metal atom of hydrogen atom, a 1-5 carbon atom; Condition is Y
1And Y
2In at least a be not hydrogen atom.
7. the method for claim 6, wherein reductive agent is the alkali metal salts or ammonium salt of formic acid.
8. the method for claim 7, wherein reductive agent is sodium, potassium or the ammonium salt of formic acid.
9. the method for claim 8, wherein reductive agent is a sodium formiate.
10. the method for claim 6, wherein reductive agent is selected from the compound of formula (III), and wherein X represents O, Y
1Represent H or OH, and Y
2Represent OH or O-basic metal.
11. the method for claim 10, wherein reductive agent is selected from phosphorous acid, Hypophosporous Acid, 50 and sodium hypophosphite.
12. the method for claim 5, wherein reductive agent is the sodium hypophosphite of hydrate forms.
13. the process of claim 1 wherein that trifluoromethyl halogen is CF
3Br.
14. the process of claim 1 wherein that temperature of reaction is between 20-110 ℃.
15. the method for claim 14, wherein temperature is between 30-80 ℃.
16. the method for claim 15, wherein temperature is between 40-60 ℃.
17. the process of claim 1 wherein that solvent is a dimethyl formamide.
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| DKPA200401244 | 2004-08-18 |
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| CN102911087A (en) * | 2012-11-19 | 2013-02-06 | 江西国化实业有限公司 | Preparation method of trifluoro methanesulfonic acid |
| CN103910678B (en) * | 2014-03-19 | 2016-06-15 | 安徽美诺华药物化学有限公司 | A kind of preparation method of ethiprole intermediate |
| CN104557358B (en) * | 2015-02-02 | 2017-11-07 | 中国科学院上海有机化学研究所 | A kind of alkyl trifluoromethyl sulfide compound and preparation method thereof |
| CN107033044B (en) * | 2017-06-13 | 2019-02-12 | 江苏凌云药业股份有限公司 | A kind of preparation method of pair of trifluoromethylthio phenol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88103601A (en) * | 1987-06-12 | 1988-12-28 | 梅·贝克有限公司 | N-phenylpyrazole derivatives |
| CN1043499A (en) * | 1988-12-13 | 1990-07-04 | 罗纳-普朗克农业化学公司 | The method for preparing the whole haloalkyl thioether |
| CN1332730A (en) * | 1999-10-22 | 2002-01-23 | 阿方蒂农科股份有限公司 | Process for preparing insecticide |
-
2004
- 2004-11-05 CN CN200480031631A patent/CN100586934C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88103601A (en) * | 1987-06-12 | 1988-12-28 | 梅·贝克有限公司 | N-phenylpyrazole derivatives |
| CN1043499A (en) * | 1988-12-13 | 1990-07-04 | 罗纳-普朗克农业化学公司 | The method for preparing the whole haloalkyl thioether |
| CN1332730A (en) * | 1999-10-22 | 2002-01-23 | 阿方蒂农科股份有限公司 | Process for preparing insecticide |
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