WO2005044806A1 - Process for the preparation of a trifluoromethylthioether - Google Patents
Process for the preparation of a trifluoromethylthioether Download PDFInfo
- Publication number
- WO2005044806A1 WO2005044806A1 PCT/DK2004/000766 DK2004000766W WO2005044806A1 WO 2005044806 A1 WO2005044806 A1 WO 2005044806A1 DK 2004000766 W DK2004000766 W DK 2004000766W WO 2005044806 A1 WO2005044806 A1 WO 2005044806A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- salt
- sodium
- formula
- reducing agent
- Prior art date
Links
- 0 CI*C(*(*=C1*)c(c(N)cc(*=C)c2)c2N)=C1NN1NC1 Chemical compound CI*C(*(*=C1*)c(c(N)cc(*=C)c2)c2N)=C1NN1NC1 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
Definitions
- the present invention relates to a process for the preparation of a trifluoromethyl thioether of the formula (I)
- perfluoroalkylthioethers including the compound (I).
- Preparation from perfluoroalkyl halides and 5 disulphides has been described in the prior art:
- a process is described using a perfluoroalkyl halide which is brought into contact with a disulphide in the presence of a reducing agent consisting of a metal chosen among zinc, cadmium, aluminium and manganese, with sulphur dioxide or consisting of an
- alkali metal dithionite or of an alkali or alkali-earth metal or metal hydroxymethanesulphinate or consisting of a formate anion and sulphur dioxide.
- International patent application no. WO 01/30760-A1 describes a similar method.
- European patent application no. 295117-A1 describes the use of sodium dithionite or sodium borohydride in an aqueous-organic solvent such as ethanol
- the compound (I) is a well known compound, which is useful as the starting material in the preparation of the insecticide Fipronil and related compounds by known methods, e.g. as described in European patent no. 295117-A1.
- the compound (II) is also a well known compound, which may be prepared according to well known procedures e.g. as disclosed in EP 295 117 Al.
- the present invention relates to a process for the preparation of a trifluoromethyl thioether of the formula (I)
- the trifluoromethylhalide may be chosen among CF 3 C1, CF 3 I and CF 3 Br. From an economical point of view the preferred choice is CF 3 Br.
- the molar ratio of trifluoromethylhalide to thiocyanate of formula (II) is preferably higher than 1.
- the amount of salt compound used is generally 1-15 molar equivalents relative to the thiocyanate of formula (II), preferably 2-11 molar equivalents.
- the salt compound is introduced into the reaction vessel either in solid form or dissolved/suspended in a solvent, preferably the same as the reaction solvent.
- the dithionite salt is preferably a metal or amine salt, such as sodium, potassium, calcium or ammonium with sodium dithionite being most preferred.
- the hydroxymethansulfinate salt is preferably a metal salt such as sodium (known as Rongalite) or zinc (known as Decroline) with sodium hydroxymethansulfinate being most preferred.
- the reducing agent(s) is by example chosen between metals such as zinc, cadmium, aluminium and manganese; hydrazine; formic acid, salts of formate such as metal or amine salts, preferred are alkali metal or ammonium salts of formate and even more preferably the sodium or potassium salt of formate with sodium formate being most preferred; aluminium hydrides e.g.
- R 3 R 4 A1H, M ⁇ t AlEy or MA1H 4 wherein R 3 and R 4 each independently of the other represents C 1- alkyl, and M is lithium or sodium and include (i-C 4 H 9 ) 2 AlH and LiAlH 4 ; borohydrides e.g. metal or amine borohydrids such as NaBH , LiBH 4 , (CH 3 ) 4 NBH 4 , NaBH 3 CN; compounds of the formula
- X represents O or S
- Yi and Y which may be identical or different, each represent H or O-R, where R represents a hydrogen atom, a linear or branched alkyl chain of 1-5 carbon atoms or an alkali metal atom; with the provisio that at least one of Y ⁇ and Y 2 is other than a hydrogen atom.
- R represents a hydrogen atom, a linear or branched alkyl chain of 1-5 carbon atoms or an alkali metal atom; with the provisio that at least one of Y ⁇ and Y 2 is other than a hydrogen atom.
- Preferred are those where X represent O. More preferred are those where Y represents H or OH; and Y represent OH or O- alkali metal, with sodium being the preferred alkali metal.
- Even more preferred are phosphorous acid (H 3 P0 3 ), hypophosphorous acid (H 3 P0 ) and sodium hypophosphorous acid (NaH 2 P0 2 ), with hypophosphorous acid and sodium hypophosphorous acid being
- the reducing agent of formula (III) may be employed in one or more of its hydrated forms, preferably such as sodium hypophosphorous acid monohydrate (NaH 2 P0 2 , 1H 2 0) and sodium hypophosphorous acid hydrate (NaH 2 P0 2 , xH 2 0) with sodium hypophosphorous acid hydrate being most preferred.
- the amount of reducing agent used is generally 1-15 molar equivalents relative to the thiocyanate of formula (II), preferably 2-11 molar equivalents.
- the reducing agent(s) is introduced into the reaction vessel as is e.g. either in solid or liquid form or dissolved/suspended in a solvent, preferably the same as the reaction solvent or water.
- the reducing agent(s) may be introduced portion wise, continuously or prior to the reaction and one may introduce the agent(s) as the last reagent to the reaction mixture.
- the sulphur dioxide may be present in a catalytic quantity but amounts higher than 1 equivalent relative to the thiocyanate of formula (II) is preferred, more preferably between 1-7 and even more preferably between 1.5 - 4.5 although the upper limit is not critical.
- the sulphur dioxide is added portion wise, continuously or prior to the reaction and one may introduce the sulphur dioxide as the last reagent to the reaction mixture.
- the sulphur dioxide is introduced to the reaction vessel either in gaseous form or dissolved in a solvent, preferably the same as the reaction solvent.
- the solvent for the reaction may in principle be any solvent that is inert and which is capable of dissolving the reactants under the reaction conditions.
- the term "inert” is intended to mean that the solvent does not in a substantial degree react with the components of the mixture.
- the solvent is a polar solvent such as formamide, pyridine, dimethylformamide (DMF), N,N-dimethylacetamide (DMA), Hexamethylphosphoric triamide (HMPT), N-methylpyrrolidone (NMP), dimethyl sulphoxide .
- DMSO dimethyl ether, dioxane, tetrahydrofuran and dimethoxyethane
- DME dimethoxyethane
- Small amounts of water maybe added to the solvent, e.g. a volume of up to 35% of the volume of solvent(s) used, and preferably in an amount of 5-30%.
- the reaction temperature is usually within the range of 20-110°C or at or below the boiling temperature of the solvent, preferably between 30-80°C, and even more preferably between 40-60°C. Due to the gaseous nature of the trifluoromethylhalide the reaction is performed under pressure in a suitable apparatus made of a non-reactive material e.g.
- Variation of the pH in the reaction mixture may be achieved by adding a buffer prior to or during the reaction.
- buffer can be of the organic or inorganic type and include pyridine, amines (e.g. aqueous ammonia, triethylamine), alkali metal hydroxides and salts of weak acids such as alkali metal salts of carbonates, phosphates, sulphites, citrates and acetates (e.g. NaHC0 3 , Na 2 C0 3 , NaH 2 P0 4 , Na 2 HP0 4 , NaHS0 3 ).
- Example 2.1 To a 50 ml Teflon insert to a Berghof autoclave was added 5-Amino-l-(2,6- dichloro-4-trifluoromethyl-phenyl)-4-thiocyanato-lH-pyrazole-3-carbonitrile (2.86 mmol 1.08g), and sodium formate (20 mmol 1.40g) and sulphur dioxide (5.94 mmol 0.38g) dissolved in a mixture of 10 ml DMF and 2.8 ml water. Then the Teflon insert was cooled to -60°C, CF 3 Br (58 mmol 8.7g) condensed into the insert and the autoclave closed and heated to 55°C for 3 hours.
- Teflon insert to a Berghof autoclave was added 10 ml DMF with 2.7 g water, 5-Amino-l-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-thiocyanato-lH- pyrazole-3-carbonitrile (1.106g) and Rongalite (4.29g).
- the teflon insert was cooled to -60°C, CF 3 Br (6.58g) condensed into the insert and the autoclave closed and heated to 45°C for 3 hours.
- the autoclave was cooled to room temperature and opened after release of pressure.
- Example 4.1 14.5 mmol (5.52g) of 5-Amino-l-(2,6-dichloro-4-trifluoromethyl-phenyl)-4- thiocyanato-lH-pyrazole-3-carbonitrile was added to a mixture of 50 ml of DMF and 37.5 mmol (2.4g) sulphur dioxide in a teflon lined autoclave at room temperature. The reactor was sealed and purged with nitrogen for 2 minutes followed by addition of CF 3 Br (16.8g). The reactor was heated to 30°C and 7.0g sodium formate dissolved in lOg of water added slowly during a 80 minutes period with maintenance of the temperature between 50°C and 54°C during the addition and for a further 60 minute period.
- the reactor was heated to 30°C and 132 mmol (6.07g) formic acid dissolved in 10 ml of DMF was added slowly during a 45 minutes period with maintenance of the temperature between 55°C and 60°C during the addition and for a further 60 minute period.
- the autoclave was cooled to room temperature and opened after release of pressure. After washing with water and extracting the product with methyl-t-butylether the product was analyzed (GC internal standard method). Yield of 5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethyl-phenyl)-4- trifluoromethylthio-lH-pyrazole was 76.5%.
- Example 6.1 100 mmol 5-Amino-l-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-thiocyanato- lH-pyrazole-3-carbonitrile (42,25g of purity 89,5 %) was added to a solution of 14,24g (222 mmol) S0 2 in 312 ml DMF in a 1000 ml teflon-coated autoclave with stirrer of PVDF. The reactor was sealed and purged for 2 min with CF 3 Br, followed by addition of 61, 5g CF 3 Br. The reactor was then heated to 65°C.
- the autoclave was cooled to room temperature and the pressure released through a oxidizing basic scrubber.
- the gas stream coming out from this scrubber was essentially free from undesired gases, containing ca. 95 % CF 3 Br, which was compressed and collected for reuse.
- the autoclave was opened and the product transferred to 750 ml water and 250 ml isopropylacetate.
- the phases were separated, the aquous phase extracted twice with 100 ml isopropylacetate and discarded.
- the crude product could be further purified by recrystallization from a suitable solvent or solvent-mixture, e.g. toluene or a toluene-heptane-mixture.
- a suitable solvent or solvent-mixture e.g. toluene or a toluene-heptane-mixture.
- DMF Dimethylformamide
- DMA N.N-dimethylacetamide
- HMPT Hexamethylphosphoric triamide
- DMSO Dimethyl sulphoxide
- DME Dimethoxyethan The amount of solvent besides water added was 10 ml.
- Methyl-t-butylether (2) Isopropylacetate (a) First amount was the initial amount of CF 3 Br, the second was added later A Supplementary CF 3 Br added only after all formate-solution had been added. B Supplementary CF 3 Br added during addition of formate-solution.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0416107-6A BRPI0416107A (en) | 2003-11-07 | 2004-11-05 | process of preparation of a trifluoromethyl thioether |
IL174980A IL174980A0 (en) | 2003-11-07 | 2006-04-11 | Process for the preparation of a trifluoromethylthioether |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DKPA200301656 | 2003-11-07 | ||
DKPA200301656 | 2003-11-07 | ||
DKPA200401244 | 2004-08-18 | ||
DKPA200401244 | 2004-08-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005044806A1 true WO2005044806A1 (en) | 2005-05-19 |
Family
ID=34575573
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DK2004/000766 WO2005044806A1 (en) | 2003-11-07 | 2004-11-05 | Process for the preparation of a trifluoromethylthioether |
Country Status (3)
Country | Link |
---|---|
BR (1) | BRPI0416107A (en) |
IL (1) | IL174980A0 (en) |
WO (1) | WO2005044806A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011051284A1 (en) | 2009-10-30 | 2011-05-05 | Basf Se | Process for the preparation of 4-sulfinyl-pyrazole derivatives |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0295117A1 (en) * | 1987-06-12 | 1988-12-14 | Rhone-Poulenc Agriculture Limited | Derivatives of N-phenylpyrazoles |
US5082945A (en) * | 1988-12-13 | 1992-01-21 | Rhone-Poulenc Agrochimie | Process for the preparation of perhaloalkylthioethers |
-
2004
- 2004-11-05 WO PCT/DK2004/000766 patent/WO2005044806A1/en active Application Filing
- 2004-11-05 BR BRPI0416107-6A patent/BRPI0416107A/en active Search and Examination
-
2006
- 2006-04-11 IL IL174980A patent/IL174980A0/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0295117A1 (en) * | 1987-06-12 | 1988-12-14 | Rhone-Poulenc Agriculture Limited | Derivatives of N-phenylpyrazoles |
US5082945A (en) * | 1988-12-13 | 1992-01-21 | Rhone-Poulenc Agrochimie | Process for the preparation of perhaloalkylthioethers |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011051284A1 (en) | 2009-10-30 | 2011-05-05 | Basf Se | Process for the preparation of 4-sulfinyl-pyrazole derivatives |
Also Published As
Publication number | Publication date |
---|---|
IL174980A0 (en) | 2006-08-20 |
BRPI0416107A (en) | 2007-01-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPS58201779A (en) | Novel n-alkyl-norscopine | |
PL206482B1 (en) | Process for preparing 4−trifluoromethylsulphinylpyrazole derivative | |
KR100642098B1 (en) | Process for the synthesis of aryl sulfurpentafluorides | |
US20010021790A1 (en) | Process for producing sulfonylimide compound | |
JPH0463060B2 (en) | ||
EP0119274B1 (en) | Process for producing aminoalkylsulfonic acids | |
JP2010159242A (en) | Fluorine-containing n-alkylsulfonylimide compound and method for producing the same, and method for producing ionic compound | |
KR100916974B1 (en) | A process for the production of chlorine dioxide | |
WO2005044806A1 (en) | Process for the preparation of a trifluoromethylthioether | |
CN110256352A (en) | A kind of preparation method of high-purity Fipronil | |
CN100586934C (en) | Process for the preparation of trifluoromethylthioether | |
JP4836352B2 (en) | Synthesis of diacyl peroxide in aprotic solvents. | |
EP1035118B1 (en) | Method for preparing 5,5'-bi-1H-tetrazole salt | |
TWI564292B (en) | For the preparation of N-substituted pyrazole compounds | |
RU2346934C2 (en) | Method of derivative synthesis with hydrofluoromethylenesulfonyl radical | |
WO2005023774A1 (en) | Process for the preparation of a trifluoromethylthioether | |
EP1919863A1 (en) | Process for the production of bicalutamide | |
US5068336A (en) | Process for producing 2-(4'-hydroxphenoxy)-3-chloro-5-trifluoromethylpyridine | |
JP2961457B2 (en) | Method for producing fluorinated organic quaternary ammonium salts | |
JPS6372661A (en) | Production of alkylhydrazines | |
KR100287364B1 (en) | Method for producing difluoromethylmethyl ether | |
KR20010021949A (en) | Method for Producing 3-Hydroxy-2-Methylbenzoic Acid | |
JPH03157358A (en) | Production of o-methylisourea salt | |
US5705701A (en) | Process for producing trimethylsulfoxonium bromide | |
MXPA02007606A (en) | Method of making 3,5 difluoroaniline from 1,3,5 trichlorobenzene. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200480031631.4 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 174980 Country of ref document: IL |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1567/CHENP/2006 Country of ref document: IN |
|
122 | Ep: pct application non-entry in european phase | ||
ENP | Entry into the national phase |
Ref document number: PI0416107 Country of ref document: BR |