• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A compound of the formula (4): can be prepared by adding a heterogeneous transition metal catalyst to a solution containing the compound of the formula (3): which is obtained by performing a nitration reaction by adding a nitrating agent to a solution which is a compound of the formula (2) contains: which is obtained by oxidizing a compound of formula (1): with hydrogen peroxide in the presence of sodium tungstate and a saturated C8 carboxylic acid, then adding water to the resulting mixture and separating the resulting solution.
    公开号:CH712810B1
    申请号:CH00053/18
    申请日:2016-07-19
    公开日:2020-07-15
    发明作者:Honda Yuta；Tanaka Yohei；Ueki Kazuya
    申请人:Sumitomo Chemical Co；
    IPC主号:
    专利说明:

    TECHNICAL AREA
    The present invention relates to a process for the preparation of 4- (trifluoromethylsulfonyl) phenol, 4- (trifluoromethylsulfonyl) -2-nitrophenol and 4- (trifluoromethylsulfonyl) -2-aminophenol.
    STATE OF THE ART
    4- (Trifluoromethylsulfonyl) phenol, 4- (trifluoromethylsulfonyl) -2-nitrophenol and 4- (trifluoromethylsulfonyl) -2-aminophenol are used as intermediates in the production of pharmaceuticals and agrochemicals (see, for example, WO 2014/104407).
    A process for the production of 4- (trifluoromethylsulfonyl) phenol by oxidation of 4- (trifluoromethylsulfanyl) phenol with sodium tungstate and hydrogen peroxide in acetic acid is known, for example, from WO 2009/133107.
    SUMMARY OF THE INVENTION
    In contrast, the present invention provides a new process for the preparation of 4- (trifluoromethylsulfonyl) phenol. The present invention also provides a process for the preparation of 4- (trifluoromethylsulfonyl) -2-nitrophenol and 4- (trifluoromethylsulfonyl) -2-aminophenol.
    According to the present invention, a compound of formula (2): (hereinafter referred to as compound (2)) can be obtained by oxidizing the compound of formula (1): (hereinafter referred to as compound (1)) with hydrogen peroxide in the presence of sodium tungstate and a saturated C8 carboxylic acid.
    Further, a compound of formula (3): (hereinafter referred to as compound (3)) can be prepared by adding a nitrating agent to a solution containing compound (2) obtained by oxidizing compound (1 ) with hydrogen peroxide in the presence of sodium tungstate and a saturated C8 carboxylic acid, then adding water to the resulting mixture and separating the resulting solution.
    Further, a compound of the formula (4): (hereinafter referred to as compound (4)) can be prepared by performing a reduction reaction by adding a heterogeneous transition metal catalyst to a solution containing compound (3) obtained by Carrying out a nitration reaction by adding a nitrating agent to a solution containing Compound (2), which was obtained by oxidizing Compound (1) with hydrogen peroxide in the presence of sodium tungstate and a saturated C8 carboxylic acid, then adding water to the resulting mixture and Separating the resulting solution.
    MODE OF CARRYING OUT THE INVENTION
    First, a process for producing Compound (2) by oxidizing Compound (1) with hydrogen peroxide in the presence of sodium tungstate and a saturated C8 carboxylic acid will be explained.
    The amount of C8 saturated carboxylic acid used is usually 0.1 to 5.0 times, and preferably 0.5 to 2.0 times the weight of the compound (1).
    As the sodium tungstate, a hydrate such as a dihydrate can be used. The amount of sodium tungstate used is usually 0.001 to 0.1 mol, and preferably 0.01 to 0.1 mol based on 1 mol of the compound (1).
    Hydrogen peroxide is usually used in an aqueous solution, and its concentration is usually 10 to 70% by weight, and preferably 30 to 60% by weight.
    The amount of hydrogen peroxide used is usually 1.8 to 5 mol, preferably 2.0 to 3.5 mol, and particularly preferably 2.4 to 3.0 mol, based on 1 mol of the compound (1).
    The reaction temperature is in the range from 50 to 100 ° C and preferably from 60 to 80 ° C.
    The reaction time is usually 1 to 50 hours.
    From a safety point of view, it is preferred to add hydrogen peroxide at the end, in the mixing order compound (1), sodium tungstate, saturated C8 carboxylic acid and hydrogen peroxide.
    As the compound (1), a commercially available product can be used as it is, however, commercially available products often contain fluoride which adversely affects reaction vessels, so the compound (1) is preferably preliminarily treated with alkali water such as a 1% strength by weight aqueous sodium hydroxide solution is washed.
    Concrete examples of C8 saturated carboxylic acids include 2-ethylhexanoic acid, octanoic acid, 6-methylheptanoic acid and 2-propylpentanoic acid, and 2-ethylhexanoic acid is preferred.
    The reaction solvent is not essential in this oxidation reaction, but an inert solvent such as nitriles such as acetonitrile and propionitrile can be used; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; and sulfolane. In the preparation of the compound (3) or the compound (4), it is advantageous to use a saturated C8 carboxylic acid or a saturated C8 carboxylic acid and water as the reaction solvent in carrying out the nitration reaction and the reduction reaction after the oxidation reaction without using the compound ( 2) or to isolate connection (3).
    After completion of the reaction, for example, water, an aqueous sodium sulfite solution, an aqueous sodium bisulfite solution, an aqueous sodium thiosulfate solution or the like is added to the reaction mixture and, if necessary, a hydrophobic organic solvent is added and the organic phase is separated to make a solution obtained containing the compound (2). To the obtained organic phase, a solvent such as hexane is added to precipitate a solid, and the precipitated solid is filtered off, whereby the compound (2) can be isolated. The isolated compound (2) can also be purified by recrystallization or chromatography.
    In the case of the preparation of compound (3) or compound (4), the solution containing the compound (2) can also be used directly in the next step without isolating the compound (2).
    Next, a process for producing the compound (3) by adding a nitrating agent to the solution containing the compound (2), which is obtained by oxidizing the compound (1) with hydrogen peroxide in the presence of sodium tungstate and a saturated C8 -Carboxylic acid, then adding water to the resulting mixture and separating the resulting solution.
    The method for obtaining the compound (2) -containing solution from the compound (1) is as described above.
    The compound (3) can be prepared by adding a nitrating agent to the solution containing the compound (2). The nitrating agent can be added after concentrating the solution containing the compound (2).
    In the nitration reaction, a solvent can be added to the solution containing the compound (2). Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran and methyl tert-butyl ether; Nitriles such as acetonitrile and propionitrile; saturated C1-6 carboxylic acids; and sulfolane.
    The nitrating agent used is usually nitric acid. In general, a 60 to 98% strength by weight aqueous HNO3 solution or fuming nitric acid is used as nitric acid.
    As for the amount of HNO3, the amount of nitric acid used is usually 1.0 to 1.5 mol, and preferably 1.1 to 1.3 mol based on 1 mol of the compound (1).
    Furthermore, the nitration reaction is usually carried out in the presence of sulfuric acid. Concentrated sulfuric acid (90% by weight or more of an aqueous H2SO4 solution) is generally used as the sulfuric acid.
    The amount of sulfuric acid used is usually 0.1 to 20 times, and preferably 0.5 to 5 times the weight of the compound (1).
    For example, in the nitration reaction, sulfuric acid is added to the solution containing the compound (2) and then nitric acid is added.
    The reaction temperature is usually in the range from 0 to 100 ° C, and preferably from 5 to 50 ° C.
    The reaction time is usually 1 to 50 hours.
    After completion of the reaction, for example, water is added to the reaction mixture and, if necessary, a hydrophobic organic solvent is added and the organic phase is separated to obtain a solution containing the compound (3). To the obtained organic phase, a solvent such as hexane is added to precipitate a solid, and the precipitated solid is filtered off, whereby the compound (3) can be isolated. The isolated compound (3) can also be purified by recrystallization or chromatography.
    In the case of producing compound (4), the solution containing the compound (3) can be used directly in the next step without isolating the compound (3).
    Next, a process for producing the compound (4) will be explained, which process is carried out by oxidizing the compound (1) with hydrogen peroxide in the presence of sodium tungstate and a C8 saturated carboxylic acid, then adding water to the resulting mixture and separating the resulting solution containing the compound (2) by adding a nitrating agent to the obtained solution and separating the resultant solution containing the compound (3) and performing a reduction reaction by adding a heterogeneous transition metal catalyst to the obtained solution.
    The method for obtaining the solution containing compound (2) from the compound (1) and further obtaining the solution containing compound (3) is as described above.
    The compound (4) can be produced by adding a heterogeneous transition metal catalyst to a solution containing the compound (3) and performing a reduction reaction.
    The heterogeneous transition metal catalyst is a Raney catalyst such as Raney nickel or Raney cobalt and a heterogeneous platinum group catalyst such as palladium / carbon, palladium / silicon dioxide, palladium / aluminum oxide, platinum / carbon, platinum / silicon dioxide, platinum / aluminum oxide, Rhodium / carbon, rhodium / silicon dioxide, rhodium / aluminum oxide, iridium / carbon, iridium / silicon oxide or iridium / aluminum oxide.
    A heterogeneous platinum catalyst, i. a heterogeneous platinum group catalyst of palladium, platinum, ruthenium, rhodium, iridium or osmium, which is a platinum group element, is preferred, and in industrial production processes, platinum / carbon and palladium / carbon are particularly preferred.
    The amount of the heterogeneous transition metal catalyst used is usually 0.0001 to 0.05 mol, and preferably 0.0003 to 0.01 mol, based on 1 mol of the compound (1).
    Furthermore, in addition to the heterogeneous transition metal catalyst, a vanadium compound can be used as a cocatalyst. Examples of the vanadium compound used in the reaction include vanadium alone, inorganic vanadium compounds, organic complexes with oxalate or acetylacetonate, and the like.
    Inorganic salts, oxo salts and hydrates thereof, the oxidation state of which is 0, II, III, IV or V, and vanadium (V) oxide are preferred, vanadate (V) or hydrates of vanadate (V) being particularly preferred and ammonium vanadate (V) is very particularly preferred.
    In the reduction reaction, a solvent can be added to the solution containing the compound (3). Examples of the solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane and heptane; aliphatic halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and methyl tert-butyl ether; Esters such as ethyl acetate and butyl acetate; aliphatic C6 to C10 carboxylic acids; and water.
    The reduction reaction is carried out under a hydrogen atmosphere. The hydrogen partial pressure of the reaction is usually 0.01 to 5 MPa, and preferably 0.05 to 1 MPa.
    The reaction temperature is in the range of usually 0 to 100 ° C, and preferably 10 to 50 ° C.
    The reaction time is usually 1 to 50 hours.
    After completion of the reaction, the heterogeneous transition metal catalyst is removed by filtration, and the resulting filtrate is concentrated, crystallized and the like, whereby the compound (4) can be isolated. In the crystallization, in order to precipitate crystals, seed crystals can be added to the solution containing the compound (4) and then cooled, and the crystals obtained can be filtered off. The isolated compound (4) can also be purified by recrystallization or chromatography.
    EXAMPLES
    In the following, the present invention will be explained in more detail with reference to examples. In the following examples, the contents are all values obtained by means of HPLC under the following measuring conditions. Detector: Ultraviolet absorption photometer (measurement wavelength: 250 nm) Column: SUMIPAX ODS Z-CLUE, manufactured by Sumika Chemical Analysis Service, Ltd. (3 µm, 4.6 mm ID x 100 mm) Column temperature: constant temperature around 40 ° C Mobile phase A: 0.1% aqueous phosphoric acid solution Mobile phase B: acetonitrile Gradient condition: The concentration gradient is as follows by changing the mixing ratio of the mobile Phase B controlled. 0 10 40 90 50 90 50.1 10 60 10
    example 1
    [0048]
    To a mixture of 20.0 g of 4- (trifluoromethylsulfanyl) phenol, 10.0 g of water, 10.0 g of 2-ethylhexanoic acid and 1.70 g of sodium tungstate dihydrate were added over 10.5 hours at 75 ° C 30 .03 g of 35% strength by weight aqueous hydrogen peroxide was added dropwise and the mixture was stirred for 12 hours. A 22% strength by weight aqueous sodium sulfite solution was added dropwise to the reaction mixture and the phases were separated. The aqueous phase obtained was extracted with 10.0 g of 2-ethylhexanoic acid. The two organic phases obtained were combined, and 42.65 g (content: 53.0% by weight) of a solution which contained 4- (trifluoromethylsulfonyl) phenol were obtained.
    To precipitate crystals, 80.0 g of hexane were added to the solution obtained, and the solution was cooled to 0 ° C. and kept at this temperature for 3 hours. The precipitated crystals were filtered off and washed successively with water and xylene. The obtained crystals were dried under reduced pressure to obtain 19.16 g of 4- (trifluoromethylsulfonyl) phenol (content: 98.1% by weight).
    Example 2
    [0051]
    To a mixture of 75.0 g of 4- (trifluoromethylsulfanyl) phenol, 37.5 g of water, 37.5 g of 2-ethylhexanoic acid and 6.38 g of sodium tungstate dihydrate were added over 10.5 hours at 75 ° C 112 , 60 g of 35% strength by weight aqueous hydrogen peroxide were added dropwise and the mixture was stirred for 12 hours. A 22% strength by weight aqueous sodium sulfite solution was added dropwise to the reaction mixture and the phases were separated. The aqueous phase obtained was extracted with 37.5 g of 2-ethylhexanoic acid. The two organic phases obtained were combined, 7.5 g of water were added, then 214.63 g of 96% strength by weight sulfuric acid were added dropwise and furthermore 28.79 g of 98% by weight were added over 5 hours at 30.degree. -% nitric acid added dropwise. After stirring for 1 hour, the reaction mixture was brought to room temperature, 29.27 g of water were added, and then 120.01 g of a 28% strength by weight aqueous sodium hydroxide solution were added dropwise and the solution was separated off. 73.18 g of water were added to the organic phase obtained and the phases were separated. 187.16 g (content: 52.0% by weight) of a solution which contained 4- (trifluoromethylsulfonyl) -2-nitrophenol were obtained.
    In order to precipitate crystals, 150.0 g of hexane were added to the resulting solution and the solution was cooled to 0 ° C. and kept at this temperature for 3 hours. The precipitated crystals were filtered off and washed successively with water and hexane. The obtained crystals were dried under reduced pressure to obtain 79.04 g of 4- (trifluoromethylsulfonyl) -2-nitrophenol (content: 98.5% by weight).
    Example 3
    [0054]
    To a mixture of 80.0 g of 4- (trifluoromethylsulfanyl) phenol, 40.0 g of water, 40.0 g of 2-ethylhexanoic acid and 6.80 g of sodium tungstate dihydrate were 120 at 75 ° C over 10.5 hours , 11 g of 35 wt .-% aqueous hydrogen peroxide was added dropwise and the mixture was stirred for 12 hours. A 22% strength by weight aqueous sodium sulfite solution was added dropwise to the reaction mixture and the phases were separated. The aqueous phase obtained was extracted with 40.0 g of 2-ethylhexanoic acid. The two resulting organic phases were combined.
    8.0 g of water were added to 198.19 g of the organic phase obtained, followed by the dropwise addition of 228.94 g of 96% strength by weight sulfuric acid and further addition of 30.71 g of 98% by weight. nitric acid at 30 ° C for 5 hours. After stirring for 1 hour, the reaction mixture was brought to room temperature, 31.23 g of water were added, and then 128.05 g of a 28% strength by weight aqueous sodium hydroxide solution were added dropwise and the phases were separated. 78.06 g of water were added to the organic phase obtained and the solution was separated off. This gave 237.48 g (content: 41.6% by weight) of a solution which contained 4- (trifluoromethylsulfonyl) -2-nitrophenol.
    To 24.1 g of the solution obtained, 5.0 g of 2-propanol were added and then 0.29 g of platinum / carbon (amount of platinum supported: 3% by weight, water content: 61% by weight) were added and the solution was stirred under a hydrogen atmosphere (hydrogen partial pressure: 0.5 MPa) for 5 hours at 40 ° C. Platinum / carbon was filtered off from the reaction mixture and washed with 2-propanol. The filtrate and the washing solution were combined, and 24.8 g of a solution containing 4- (trifluoromethylsulfonyl) -2-aminophenol (content: 19.5% by weight) were obtained. The resulting solution was concentrated to 19.6 g and 5.0 g of heptane were added at 40 ° C. and the solution was then cooled. After confirming crystal precipitation at 34 ° C., the solution was cooled to 5 ° C., 15.0 g of heptane was further added at 5 ° C., and the mixture was kept at that temperature for 3 hours to precipitate crystals. The precipitated crystals were filtered off and washed with 12.5 g of a mixed solvent of 2-propanol / heptane = 1/2. The obtained crystals were dried under reduced pressure to obtain 4.8 g of 4- (trifluoromethylsulfonyl) -2-aminophenol (content: 98.7% by weight).
    Example 4
    [0058]
    21.6 mg of ammonium vanadate (V) were added to a mixture of 10.00 g of 4- (trifluoromethylsulfonyl) -2-nitrophenol, 15.11 g of methanol, 2.12 g of toluene and 7.26 g of 2-ethylhexanoic acid , and then 132.0 mg of platinum / carbon (amount of platinum supported: 3% by weight, water content: 55% by weight) were added and the solution was stirred under a hydrogen atmosphere (hydrogen partial pressure: 0.8 MPa) for 4 hours at 40 ° C stirred. Platinum / carbon was filtered off from the reaction mixture and washed with methanol. The filtrate and the washing solution were combined, and 40.09 g (content: 21.94% by weight) of a solution which contained 4- (trifluoromethylsulfonyl) -2-aminophenol were obtained.
    Example 5
    To a mixture of 24.99 g of 4- (trifluoromethylsulfanyl) phenol, 12.54 g of water, 12.49 g of octanoic acid (CH3 (CH2) 6COOH) and 0.84 g of sodium tungstate dihydrate were over at 75 ° C 52.07 g of 30% strength by weight aqueous hydrogen peroxide were added dropwise for 17 hours, and the mixture was stirred for 20 hours. A 22% strength by weight aqueous sodium sulfite solution was added dropwise to the reaction mixture and the phases were separated. 45.1 g (content: 57.9% by weight) of a solution which contained 4- (trifluoromethylsulfonyl) phenol were obtained.
    Industrial applicability
    According to the present invention, 4- (trifluoromethylsulfonyl) phenol, 4- (trifluoromethylsulfonyl) -2-nitrophenol and 4- (trifluoromethylsulfonyl) -2-aminophenol, which serve as intermediates in the production of pharmaceuticals and agrochemicals, can be produced.
    权利要求:
    Claims (10)
    [1]
    1. A process for the preparation of a compound of the formula (2): by oxidizing a compound of the formula (1): with hydrogen peroxide in the presence of sodium tungstate and a saturated C8 carboxylic acid.
    [2]
    2. The method according to claim 1, wherein the amount of the saturated C8 carboxylic acid used is 0.5 to 2.0 times the weight of the compound (1).
    [3]
    3. A process for the preparation of a compound of the formula (3): by oxidizing a compound of the formula (1): with hydrogen peroxide in the presence of sodium tungstate and a saturated C8 carboxylic acid, then adding water to the resulting mixture and separating the resulting solution, to obtain a solution containing a compound of the formula (2): and by adding a nitrating agent to the solution containing the compound of the formula (2).
    [4]
    4. The method according to claim 3, wherein the amount of the saturated C8 carboxylic acid used is 0.5 to 2.0 times the weight of the compound (1).
    [5]
    5. The method according to any one of claims 1 to 4, wherein the saturated C8 carboxylic acid is 2-ethylhexanoic acid.
    [6]
    6. A process for preparing a compound of formula (4): by oxidizing a compound of formula (1): with hydrogen peroxide in the presence of sodium tungstate and a saturated C8 carboxylic acid, then adding water to the resulting mixture and separating the resulting solution, to obtain a solution containing a compound of the formula (2): by performing a nitration reaction by adding a nitrating agent to the solution containing the compound of the formula (2), then adding water to the resulting mixture, and separating the resulting solution, to obtain a solution containing a compound of the formula (3): and by conducting a reduction reaction under a hydrogen atmosphere and adding a heterogeneous transition metal catalyst to the solution containing the compound of the formula (3).
    [7]
    7. The method according to claim 6, wherein the amount of the saturated C8 carboxylic acid used is 0.5 to 2.0 times the weight of the compound (1).
    [8]
    8. The method of claim 6, wherein the heterogeneous transition metal catalyst is a platinum group catalyst.
    [9]
    9. The method of claim 7, wherein the heterogeneous transition metal catalyst is a platinum group catalyst.
    [10]
    10. The method according to any one of claims 6 to 9, wherein the saturated C8 carboxylic acid is 2-ethylhexanoic acid.
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