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    • 专利摘要:
    A compound of formula (3): (wherein R 1 represents a C1-C6 perfluoroalkyl group, R 2 represents a C1-C6 alkyl group and m represents an integer from 0 to 3) or a salt thereof, which is an intermediate in the Preparation of pharmaceuticals and agrochemicals can be prepared by reacting an alkali metal salt or zinc salt of a C1-C6 perfluoroalkanesulfinic acid with 2-aminophenol, optionally substituted with 1 to 3 C1-C6 alkyl groups, or a salt thereof in the presence of an oxidizing agent ,
    公开号:CH712709B1
    申请号:CH01456/17
    申请日:2016-06-01
    公开日:2020-01-15
    发明作者:Ishikawa Junichi；Hagiya Koji；Kawamura Mitsunobu
    申请人:Sumitomo Chemical Co；
    IPC主号:
    专利说明:

    description
    Technical Field The present invention relates to a process for producing a perfluoroalkanesulfonylphenol compound which is useful as an intermediate in the manufacture of pharmaceuticals and agrochemicals.
    PRIOR ART Perfluoroalkanesulfonylphenol compounds serve as intermediates in the production of pharmaceuticals and agrochemicals (see WO 2014/104 407).
    For their preparation, a process is usually used for the preparation of a perfluoroalkanesulfanylphenol compound from a phenol compound with subsequent oxidation of the perfluoroalkanesulfanylphenol compound (see WO 2014/104 407 and Journal of Organic Chemistry, 1964, Volume 29, pages 898 to 900) ,
    Summary of the Invention The present invention provides a new process for the preparation of a perfluoroalkanesulfonylphenol compound.
    According to the present invention, an alkali metal salt or zinc salt of a C1-C6-perfluoroalkanesulfinic acid and 2-aminophenol, which is optionally substituted with 1 to 3 C1-C6-alkyl groups, or a salt thereof are reacted in the presence of an oxidizing agent, whereby a compound of the formula (3):
    OH
    Ri-S (O) 2 (3) (wherein R 1 represents a C1-C6 perfluoroalkyl group, R 2 represents a C1-C6 alkyl group and m represents an integer from 0 to 3), (hereinafter referred to as Compound (3) referred to) or a salt thereof can be produced.
    Mode for Carrying Out the Invention The alkali metal salt of a C1-C6 perfluoroalkanesulfinic acid used in the present invention is a sulfinate of the formula (1a):
    R 1 -S (O) OM (1a) (where R 1 represents a C1-C6 perfluoroalkyl group and M represents an alkali metal) and a zinc salt of a C1-C6 perfluoroalkanesulfinic acid is a sulfinate of the formula (1b):
    R 1 -S (O) O- 2 Zn (1b).
    (where R 1 has the same meaning as described above).
    Examples of the C1-C6 perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a perfluoropentyl group and a perfluorohexyl group, of which the C1-C3 perfluoroalkyl group is preferred.
    The alkali metals are lithium, sodium, potassium, rubidium and cesium.
    Examples of the alkali metal salt of a C1-C6-perfluoroalkanesulfinic acid include sodium trifluoromethanesulfinate, potassium trifluoromethanesulfinate, sodium pentafluoroethanesulfinate, potassium pentafluoroethanesulfinate, sodium heptafluoropropane sulfinate, potassium heptafluoropropane sulfonate, sodium sulfonate sodium sulfonate. The sulfinate can be obtained by purchasing a commercially available product, synthesis according to the method described in WO 2011/108 622 and the like.
    Examples of the zinc salt of a C1-C6 perfluoroalkanesulfinic acid include zinc bis (trifluoromethanesulfinate), zinc bis (pentafluoroethanesulfinate) and zinc bis (tridecafluorohexanesulfinate). The sulfinate can be obtained by purchasing a commercial product, synthesis according to the method described in Nature (London, United Kingdom (2012), 492 (7427), 95-99) and the like.
    CH 712 709 B1 [0011] The 2-aminophenol optionally substituted with 1 to 3 C1-C6-alkyl groups is a compound of the formula (2):
    OH
    (2) (wherein R 2 represents a C1-C6 alkyl group and m represents an integer from 0 to 3) (hereinafter referred to as Compound (2)), where the C1-C6 alkyl group may be linear or branched, and Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a 2-pentyl group, a neopentyl group, a 4-methyl-2pentyl group, a hexyl group and one 3-methylpentyl.
    Examples of compound (2) include 2-aminophenol, 2-amino-3-methylphenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-3-ethylphenol, 2-amino- 5-ethylphenol and 2-amino-6-ethylphenol.
    The salt of 2-aminophenol optionally substituted with a C1-C6 alkyl group means an acid addition salt of the compound (2), and specific examples thereof include addition salts of inorganic acids such as hydrochloric acid and sulfuric acid, and addition salts of organic acids such as organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, and organic carboxylic acids such as acetic acid and trifluoroacetic acid. The addition salt of an inorganic acid is obtained by adding 1 to 10 mol of an inorganic acid, such as hydrochloric acid or sulfuric acid, to 1 mol of the compound (2) in an organic solvent (for example an alcohol such as ethanol) and can also be in Reaction system are generated.
    The addition salt of an organic acid is by adding 1 to 10 mol of an organic acid, such as an organic sulfonic acid such as methanesulfonic acid or p-toluenesulfonic acid, or an organic carboxylic acid, such as acetic acid or trifluoroacetic acid, to 1 mol of compound (2) in an organic solvent (for example an alcohol such as ethanol) and can also be generated in the reaction system.
    The acid addition salt of the compound (2) can be conducted to the compound (2) by neutralization with a base such as an aqueous sodium hydroxide solution.
    In the present invention, examples of the oxidizing agent include oxygen; Persulfates such as potassium persulfate and ammonium persulfate; Peroxides such as hydrogen peroxide and tert-butyl hydroperoxide; Transition metal compounds such as trivalent iron compounds, divalent copper compounds and manganese compounds; hypervalent iodine compounds such as sodium periodate; Quinone compounds such as benzoquinone, naphthoquinone, anthraquinone and chloranil; and salts of halogen oxo acids such as sodium hypochlorite and sodium chlorite. These can also be used in combination of two or more.
    [0018] Examples of the trivalent iron compounds include iron (III) chloride, potassium hexacyanoferrate (III) and iron (III) oxide; and examples of the divalent copper compounds include copper (II) sulfate and copper (II) chloride. Examples of the manganese compound include manganese dioxide.
    Among the above oxidizing agents, oxidizing agents are selected from the group consisting of potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, iron (III) chloride, iron (III) oxide, manganese dioxide and copper (II) sulfate, and iron (III) are preferred oxide (α crystal, β crystal, γ crystal, e crystal) is particularly preferred.
    If oxygen is used as the oxidizing agent, the reaction can be carried out in air, and other oxidizing agents can be used in combination.
    The reaction for producing the compound (3) or a salt thereof by reacting the alkali metal salt or zinc salt of a C1-C6 perfluoroalkanesulfinic acid with the compound (2) or a salt thereof in the presence of an oxidizing agent is usually carried out in a solvent. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, cumene, monochlorobenzene and tetralin; aliphatic hydrocarbons such as hexane, heptane, octane, nonane and cyclohexane; sulfur-containing compounds such as dimethyl sulfoxide and sulfolane; Ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether, tert-butyl methyl ether, monoglyme and diglyme; organic carboxylic acids such as acetic acid, propionic acid, butanoic acid and ethylhexanoic acid; Amides such as N, N-dimethylacetamide, Ν, Ν-dimethylformamide and N-methylpyrrolidone; Nitriles such as acetonitrile and propyl nitrile; Esters such as methyl acetate and ethyl acetate; Ketones such as acetone and methyl isobutyl ketone; Alcohols such as methanol, ethanol and propanol and mixtures thereof. Of these, organic carboxylic acid and nitrile are preferred.
    The amount of the solvent is usually 1 to 100 times, preferably 1 to 30 times, based on the weight of the compound (2).
    CH 712 709 B1 The sulfinate is usually used in a proportion of 1 mol to 5 mol, based on 1 mol of the compound (2).
    The oxidizing agent is usually used in a proportion of 1 mol to 5 mol, based on 1 mol of the compound (2).
    The reaction temperature is usually in the range of -20 ° C to 200 ° C, and the reaction time is usually in the range of 1 minute to 24 hours.
    It is preferred to carry out the reaction by adding a strong acid. Examples of the strong acid include sulfuric acid, methanesulfonic acid and hydrochloric acid, and the strong acid is usually used in an amount of 1 mol to 10 mol based on 1 mol of the compound (2).
    After completion of the reaction, the compound (3) can be isolated by subjecting the reaction mixture to crystallization or the like. The obtained compound (3) can be purified by distillation, recrystallization, extraction, chromatography and the like.
    In addition, when a trivalent iron compound (e.g. iron (III) chloride, iron (III) oxide) is used as the oxidizing agent, a reducing agent such as a metal hydride is added to the reaction system after the reaction is completed, with iron in the system resulting from the trivalent iron compound results, can be filtered off.
    Examples of the metal hydride include lithium aluminum hydride, lithium borohydride, sodium borohydride, lithium hydride, potassium hydride and calcium hydride, and lithium aluminum hydride, lithium borohydride and sodium borohydride are preferred.
    The metal hydride is preferably added in a proportion of 0.1 mol to 5 mol, based on 1 mol of the trivalent iron compound to be added.
    The compound (3) can also be isolated in the form of an acid addition salt. Specific examples of the acid addition salt include addition salts of inorganic acids such as hydrochloric acid and sulfuric acid, and addition salts of organic acids such as organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, and organic carboxylic acids such as acetic acid and trifluoroacetic acid. In order to isolate these acid addition salts, residues derived from the oxidizing agent used are removed from the reaction mixture after the end of the reaction and then an acid is added in order to crystallize the acid addition salt.
    Examples of the compound (3) to be obtained include 2-amino-4-trifluoromethanesulfonylphenol, 2-amino-3methyl-4-trifluoromethanesulfonylphenol, 2-amino-5-methyl-4-trifluoromethanesulfonylphenol, 2-amino-6 -methyl-4-trifluoromethanesulfonyl-phenol, 2-amino-3-ethyl-4-trifluoromethanesulfonylphenol, 2-amino-5-ethyl-4-trifluoromethanesulfonylphenol, 2A-amino-6-ethyl-4-trifluoromethanesulfonylphenol and 2-amino-4-sulfonylphenol ,
    Examples of embodiments of the present invention include the following embodiments.
    In a method of the present invention, the oxidizing agent is one or more oxidizing agents selected from the group consisting of persulfates, peroxides, trivalent iron compounds, divalent copper compounds and manganese compounds.
    In a method of the present invention, the oxidizing agent is one or more oxidizing agents selected from the group consisting of persulfates, peroxides, trivalent iron compounds, divalent copper compounds and manganese compounds, and a strong acid is added.
    In a method of the present invention, the oxidizing agent is one or more oxidizing agents selected from the group consisting of persulfates, peroxides, trivalent iron compounds, divalent copper compounds and manganese compounds, and one or more strong acids selected from the group are added from sulfuric acid, methanesulfonic acid and hydrochloric acid.
    In a method of the present invention, the oxidizing agent is one or more oxidizing agents selected from the group consisting of potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, iron (III) chloride, iron (III) oxide, manganese dioxide and copper (II) sulfate ,
    In a method of the present invention, the oxidizing agent is one or more oxidizing agents selected from the group consisting of potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, iron (III) chloride, iron (III) oxide, manganese dioxide and copper (II) sulfate , and a strong acid is added.
    In a method of the present invention, the oxidizing agent is one or more oxidizing agents selected from the group consisting of potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, iron (III) chloride, iron (III) oxide, manganese dioxide and copper (II) sulfate , and one or more strong acids selected from the group consisting of sulfuric acid, methanesulfonic acid and hydrochloric acid are added.
    In a method of the present invention, the oxidizing agent is iron (III) oxide.
    In a method of the present invention, the oxidizing agent is iron (III) oxide and a strong acid is added.
    In one method of the present invention, the oxidizing agent is iron (III) oxide and sulfuric acid is added.
    CH 712 709 B1 In a method of the present invention, the oxidizing agent is iron (III) oxide and methanesulfonic acid is added.
    In a process of the present invention, the oxidizing agent is iron (III) oxide and the process is carried out in acetonitrile.
    In one method of the present invention, the oxidizing agent is iron (III) oxide and sulfuric acid in acetonitrile is added.
    In one method of the present invention, the oxidizing agent is iron (III) oxide and methanesulfonic acid in acetonitrile is added.
    In a method of the present invention, the oxidizing agent is manganese dioxide.
    In one process of the present invention, the oxidizing agent is manganese dioxide and a strong acid is added.
    In one method of the present invention, the oxidizing agent is manganese dioxide and methanesulfonic acid in acetonitrile is added.
    In one method of the present invention, the oxidizing agent is iron (III) chloride.
    In a method of the present invention, the oxidizing agent is iron (III) chloride and a strong acid is added.
    In one process of the present invention, the oxidizing agent is iron (III) chloride and methanesulfonic acid is added.
    In one method of the present invention, the oxidizing agent is oxygen.
    [0051] In a method of the present invention, the oxidizing agent is oxygen and iron (III) chloride.
    Examples Hereinafter, the present invention will be described using examples and the like, but the present invention is not limited to these examples only.
    The analysis conditions of the internal standard method using high performance liquid chromatography in the examples are as follows.
    - Analysis instrument: CBM-20A manufactured by Shimadzu Corporation
    - Mobile phase (A / B): 0.1% aqueous phosphoric acid / acetonitrile
    - Column: SUMIPAX ODS Z-CLUE o 4.6 mm x 100 mm (3 μm), manufactured by Sumika Chemical Analysis Service, Ltd.
    - Column temperature: 40 ° C
    - Flow rate: 1.0 ml / min
    - UV wavelength: 250 nm
    - Injection quantity: 10 μΙ
    - Internal standard: acetanilide
    - Time program
    Time (min) Concentration (%) 0 10 40 90 50 90 50.1 10 60 10
    Example 1-1 Under a nitrogen atmosphere, 0.14 mol (15.00 g) 2-aminophenol, 0.21 mol (32.17 g) sodium trifluoromethanesulfinate, 60 g acetonitrile and 0.41 mol (40.41 g ) Stir sulfuric acid at room temperature for 15 minutes. To the resulting mixture, 0.27 mol (43.73 g) of iron oxide (Fe 2 O 3 ) and 90 g of acetonitrile were added, followed by stirring at 70 ° C for 7 hours. After the reaction mixture was cooled to room temperature, 0.08 mol (3.12 g) of sodium borohydride was added and the mixture was stirred for 30 minutes. 50 g of water were then added, the mixture was filtered through Gellte (registered trademark) and the filtrate was washed with acetonitrile. The yield was calculated by adding a portion of the combined solution of the filtrate and the washing liquid using the internal standard procedure below
    CH 712 709 B1
    Use of high performance liquid chromatography was analyzed. The yield of 2-amino-5-trifluoromethanesulfonylphenol was 54%.
    Example 1-2 Under a nitrogen atmosphere, 0.09 mol (10.00 g) of 2-aminophenol, 0.08 mol (12.9 g) of sodium trifluoromethanesulfinate, 100 g of acetonitrile and 0.33 mol (32.33 g ) Sulfuric acid stirred for 15 minutes at room temperature. To the resulting mixture, 0.18 mol (29.16 g) of iron oxide (Fe 2 O 3 ) and 50 g of acetonitrile were added, followed by stirring at 73 ° C for 2 hours. After the reaction mixture was cooled to room temperature, 0.05 mol (2.08 g) of sodium borohydride was added and the mixture was stirred for 30 minutes. Then 10 g of water were added, the mixture was filtered through Gellte (registered trademark) and the filtrate was washed with acetonitrile. The yield was calculated by analyzing part of the combined solution of the filtrate and the washing liquid by the internal standard method using high performance liquid chromatography. The yield of 2-amino5-trifluoromethanesulfonylphenol was 78%.
    The filtrate and the washing liquid were combined and concentrated, and 75 g of 1N hydrochloric acid and 100 g of methyl t-butyl ether were added to the resulting oily substance, and the mixture was then separated into an organic phase and an aqueous phase. The aqueous phase was extracted with 100 g of methyl t-butyl ether, the resulting organic phases were combined and 7 g of activated carbon were added. The mixture was stirred for 30 minutes and then filtered, and the filtrate was concentrated. To the resulting oily substance, 10 g of methanol was added, and the mixture was added to a solution of 35 g of sodium sulfate in 200 g of water while stirring at room temperature, whereby crystals were precipitated. The crystals obtained by filtration were dried, and 18.1 g of 2-amino-5-trifluoromethanesulfonylphenol with a purity of 73% was obtained. Extraction yield 60%.
    The crude crystals (18 g) were stirred with 160 g 50% aqueous methanol and 5 g activated carbon for 30 minutes at 60 ° C, and then the mixture was filtered at 60 ° C and methanol was distilled off from the filtrate to to get the failed crystals. The crystals were cooled to room temperature and filtered and dried.
    12 g of 2-amino-5-trifluoromethanesulfonylphenol were obtained with a purity of 90.7%. Isolated yield 50%.
    Example 1-3 Iron oxide (Fe 3 O 4 ) was heated in air at 250 ° C for 2 hours to obtain the iron oxide (Fe 2 O 3 ) subsequently used.
    Under a nitrogen atmosphere were 0.09 mol (10.00 g) 2-aminophenol, 0.08 mol (12.9 g) sodium trifluoromethanesulfinate, 100 g acetonitrile and 0.33 mol (32.33 g) sulfuric acid for 15 minutes long stirred at room temperature. To the resulting mixture was added 0.18 mol (29.16 g) of the iron oxide (Fe 2 O 3 ) prepared above and 50 g of acetonitrile, and the mixture was stirred at 73 ° C for 5 hours. After the reaction mixture was cooled to room temperature, 0.05 mol (2.08 g) of sodium borohydride was added and the mixture was stirred for 30 minutes. 50 g of water were then added, the mixture was filtered through Gellte (registered trademark) and the filtrate was washed with acetonitrile. The yield was calculated by analyzing part of the combined solution of the filtrate and the washing liquid by the internal standard method using high performance liquid chromatography. The yield of 2-amino-5-trifluoromethanesulfonyl-phenol was 69%.
    Example 2 30.2 mmol (4.72 g) of sodium trifluoromethanesulfinate, 27.5 mmol (3.0 g) of 2-aminophenol and 60 g of acetonitrile were mixed under a nitrogen atmosphere and 13.27 g of methanesulfonic acid were added dropwise at 5 ° C. , To the resulting mixture was added 55.3 mmol (4.81 g) of manganese dioxide at 5 ° C over 8 hours, and the mixture was stirred at 5 ° C for 1 hour. A 10% aqueous hydrosulfite solution (30 g) was added to the reaction mixture, and the mixture was stirred and separated to obtain an organic phase containing 2-amino-5-trifluoromethanesulfonylphenol. The yield was calculated by collecting a portion of the organic phase and analyzing the organic phase by the internal standard method using high performance liquid chromatography. Yield 64%.
    Example 3 A mixture obtained by mixing 22.9 mmol (2.50 g) 2-aminophenol, 25.2 mmol (3.90 g) sodium trifluoromethanesulfinate, 25.2 mmol (4.09 g) anhydrous iron (III) chloride and 25 g of acetic acid was obtained, was heated and stirred at 70 ° C in air for 5 hours. A portion of the reaction mixture was collected and analyzed by high performance liquid chromatography to confirm the formation of 2-amino-5-trifluoromethanesulfonylphenol. Yield 50%.
    Example 4-1 To a mixture obtained by adding 2-aminophenol and 20.2 mmol (3.15 g) sodium trifluoromethanesulfinate to 20 g acetic acid, 20.2 mmol (1.94 g) methanesulfonic acid was added dropwise , and it became 30 minutes at
    CH 712 709 B1
    Room temperature stirred. To the resulting mixture was added 40.4 mmol (9.21 g) of ammonium persulfate, and the mixture was heated to 50 ° C and stirred for 10 hours. A portion of the reaction mixture was collected and analyzed by high performance liquid chromatography to confirm the formation of 2-amino-5-trifluoromethanesulfonylphenol.
    Example 4-2 The procedure described in Example 4-1 was carried out with copper (II) sulfate instead of ammonium persulfate and the formation of 2-amino-5-trifluoromethanesulfonylphenol was confirmed.
    Example 5-1 Under a nitrogen atmosphere, 2.75 mmol (450 mg) of anhydrous iron (III) chloride and 3 g of acetonitrile were mixed under cooling with an ice bath, and to the resulting mixture was added 2.75 mmol (300 mg) 2-Aminophenol, 4.1 mmol (650 mg) sodium trifluoromethanesulfinate and 5.5 mmol (530 mg) methanesulfonic acid are added in this order and the mixture is then stirred for 15 minutes. To this mixture was added 6.88 mmol (1.57 g) of ammonium persulfate, then the ice bath was removed and the mixture was stirred at 20 ° C for 6 hours. To the reaction mixture was added 1.58 mmol (60 mg) sodium borohydride, the mixture was stirred for 30 minutes, and then 3 g of water and 10 g of ethyl acetate were added and the mixture was stirred and to obtain an organic phase, the 2-amino Contained 5-trifluoromethanesulfonylphenol, separated. Part of this organic phase was collected and analyzed by the internal standard analysis method using high performance liquid chromatography to calculate the yield of 2-amino-5-trifluoromethanesulfonylphenol. Yield 30%.
    Example 5-2 The procedure described in Example 5-1 was carried out with potassium persulfate instead of ammonium persulfate and the formation of 2-amino-5-trifluoromethanesulfonylphenol was confirmed.
    Example 6-1 A mixture obtained by adding 0.5 mmol (0.078 g) sodium trifluoromethanesulfinate, 0.25 mmol (0.027 g) 2Aminophenol and 0.5 mmol (0.081 g) anhydrous iron (III) chloride to 1 ml of acetic acid was obtained, was heated at 70 ° C for 5 hours and stirred. A portion of the reaction mixture was collected and analyzed by high performance liquid chromatography to confirm the formation of 2-amino-5-trifluoromethanesulfonylphenol.
    Example 6-2 The procedure described in Example 6-1 was carried out using the solvent, sulfinate and oxidizing agent described in Table 1 below. The results are shown below.
    In Table 1, Table 2 and Table 3, CF 3 S (O) ONa is sodium trifluoromethanesulfinate, CF 3 S (O) OK is potassium trifluoromethanesulfinate and (CF 3 S (O) O) 2 Zn is zinc bis (trifluoromethanesulfinate) ).
    [Table 1] [0068]
    solvent sulfinate oxidant ethyl acetate CF 3 S (O) ONa ammonium persulfate 2-ethylhexanoic CF 3 S (O) ONa potassium persulfate 2-ethylhexanoic CF 3 S (O) ONa anhydrous iron (III) chloride acetic acid CF 3 S (O) OK Iron (III) oxide acetic acid (CF 3 S (O) O) 2 Zn 70% tert-butyl hydroperoxide acetic acid (CF 3 S (O) O) 2 Zn anhydrous iron (III) chloride
    Example 6-3 When the same procedure as in Example 6-1 was carried out using the combinations of solvent, sulfinate and oxidizing agent described in Table 2, 2-amino-5-trifluoromethanesulfonylphenol was obtained in each reaction.
    CH 712 709 B1 [Table 2] [0070]
    solvent sulfinate oxidant acetic acid CF 3 S (O) Na 30% hydrogen peroxide 2-ethylhexanoic CF 3 S (O) Na 70% tert-butyl hydroperoxide acetic acid CF 3 S (O) Na 70% tert-butyl hydroperoxide acetic acid CF 3 S (O) Na Iron (III) chloride (hexahydrate) acetic acid CF 3 S (O) Na Iron (III) oxide acetic acid CF 3 S (O) Na manganese dioxide acetic acid CF 3 S (O) Na Potassium hexacyanoferrate (III) aqueous 10% sulfuric acid CF 3 S (O) Na anhydrous iron (III) chloride aqueous 3.5% hydrochloric acid CF 3 S (O) Na anhydrous iron (III) chloride DMF CF 3 S (O) Na anhydrous iron (III) chloride acetonitrile CF 3 S (O) Na anhydrous iron (III) chloride ethanol CF 3 S (O) Na anhydrous iron (III) chloride acetic acid CF 3 S (O) Na anhydrous iron (III) chloride ethyl acetate CF 3 S (O) Na anhydrous iron (III) chloride aqueous 10% sulfuric acid CF 3 S (O) Na ammonium persulfate 2-methyltetrahydrofuran CF 3 S (O) Na ammonium persulfate tert-butyl methyl ether CF 3 S (O) Na ammonium persulfate acetonitrile CF 3 S (O) Na ammonium persulfate ethanol CF 3 S (O) Na ammonium persulfate cyclopentyl CF 3 S (O) Na ammonium persulfate methyl isobutyl ketone CF 3 S (O) Na ammonium persulfate acetic acid CF 3 S (O) Na ammonium persulfate acetic acid CF 3 S (O) Na 70% tBuOOH aqueous 10% sulfuric acid CF 3 S (O) Na potassium persulfate 2-methyltetrahydrofuran CF 3 S (O) Na potassium persulfate tert-butyl methyl ether CF 3 S (O) Na potassium persulfate acetonitrile CF 3 S (O) Na potassium persulfate xylene CF 3 S (O) Na potassium persulfate cyclopentyl CF 3 S (O) Na potassium persulfate dimethylformamide CF 3 S (O) Na potassium persulfate methyl isobutyl ketone CF 3 S (O) Na potassium persulfate Monochlorobenzene CF 3 S (O) Na potassium persulfate acetic acid CF 3 S (O) Na potassium persulfate
    CH 712 709 B1
    solvent sulfinate oxidant ethyl acetate CF 3 S (O) Na potassium persulfate acetic acid CF 3 S (O) Na sodium hypochlorite acetic acid CF 3 S (O) OK 70% tert-butyl hydroperoxide acetic acid CF 3 S (O) OK potassium persulfate acetic acid (CF 3 S (O) O) 2 Zn potassium persulfate
    Example 7-1 A mixture obtained by adding 13.7 mmol (2.00 g) 2-aminophenol hydrochloride, 15.1 mmol (2.36 g) sodium trifluoromethanesulfinate and 30.2 mmol (6.90 g) Ammonium persulfate to 20 g of acetic acid was obtained, was heated and stirred at 70 ° C for 10 hours under a nitrogen atmosphere. A portion of the reaction mixture was collected and analyzed by high performance liquid chromatography to confirm the formation of 2-amino-5-trifluoromethanesulfonylphenol.
    Example 7-2 The procedure described in Example 7-1 was carried out with potassium persulfate instead of ammonium persulfate and the formation of 2-amino-5-trifluoromethanesulfonylphenol was confirmed.
    Example 8-1 A mixture obtained by adding 0.25 mmol (0.047 g) 2-amino-3-methylphenol, 0.5 mmol (0.086 g) sodium trifluoromethanesulfinate and 0.5 mmol (0.081 g) anhydrous iron (III) chloride to 1 ml of acetic acid was heated and stirred at 70 ° C for 5 hours. A portion of the reaction mixture was collected and analyzed by high performance liquid chromatography to confirm the formation of 2-amino-3-methyl-4-trifluoromethanesulfonylphenol.
    Example 8-2 When the same procedure as in Example 8-1 was carried out using the sulfinate and oxidizing agent described in Table 3, the formation of 2-amino-3-methyl-4-trifluoromethanesulfonylphenol was confirmed in each reaction.
    [Table 3] [0075] sulfinate oxidant CF 3 S (O) ONa CF 3 S (O) ONa potassium persulfate70% tert-butyl hydroperoxide
    Reference Example 1 A mixture obtained by adding 0.25 mmol (0.035 g) 2-nitrophenol, 0.50 mmol (0.078 g) sodium trifluoromethanesulfinate and 0.5 mmol (0.081 g) anhydrous iron (III) chloride to 1 ml of acetic acid was obtained was heated at 70 ° C for 5 hours and stirred. When part of the reaction mixture was collected and analyzed by high performance liquid chromatography, the formation of 2-amino-3-methyl-4-trifluoromethanesulfonylphenol was not confirmed.
    Reference Example 2 A mixture obtained by adding 0.25 mmol (0.038 g) 2-acetylaminophenol, 0.078 g (0.50 mmol) sodium trifluoromethanesulfinate and 0.5 mmol (0.081 g) anhydrous iron (III) chloride to 1 ml of acetic acid was obtained was heated at 70 ° C for 5 hours and stirred. When part of the reaction mixture was collected and analyzed by high performance liquid chromatography, the formation of 2-amino-3-methyl-4-trifluoromethanesulfonylphenol was not confirmed.
    Industrial Applicability The present invention can produce a perfluoroalkanesulfonylphenol compound which can be used as an intermediate in the manufacture of pharmaceuticals and agrochemicals.
    CH 712 709 B1
    权利要求:
    Claims (7)
    [1]
    claims
    1.
    Process for the preparation of a compound of formula (3):
    OH
    R 2

    nh 2
    R 1 -S (O) 2 (3) wherein R 1 represents a C1-C6 perfluoroalkyl group, R 2 represents a C1-C6 alkyl group and m represents an integer of 0 to 3, or a salt thereof, comprising reacting one Alkali metal salt or zinc salt of a C1-C6-perfluoroalkanesulfinic acid with 2-aminophenol, which is optionally substituted with 1 to 3 C1-C6-alkyl groups, or a salt thereof in the presence of an oxidizing agent.
    [2]
    Second
    [3]
    Third
    [4]
    4th
    [5]
    5th
    [6]
    6th
    The method of claim 1, wherein the oxidizing agent is one or more oxidizing agents selected from the group consisting of persulfates, peroxides, trivalent iron compounds, divalent copper compounds and manganese compounds.
    The method of claim 1, wherein the oxidizing agent is one or more oxidizing agents selected from the group consisting of potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, iron (III) chloride, iron (III) oxide, manganese dioxide and copper (II) sulfate.
    A method according to any one of claims 1 to 3, wherein R 1 is a C1-C3 perfluoroalkyl group.
    A method according to any one of claims 1 to 3, wherein R 1 is a trifluoromethyl group.
    A method according to any one of claims 1 to 3, wherein the metal of the alkali metal salt of C1-C6 perfluoroalkanesulfinic acid is sodium or potassium.
    [7]
    7th
    The method of claim 5, wherein the alkali metal salt or zinc salt of trifluoromethanesulfinic acid is the sodium salt or the potassium salt of trifluoromethanesulfinic acid.
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    CN107709292B|2019-08-20|
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    US10160722B2|2018-12-25|
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    WO2021213978A1|2020-04-21|2021-10-28|Bayer Aktiengesellschaft|2-aryl-substituted condensed heterocyclic derivatives as pest control agents|
    法律状态:
    2022-01-31| PL| Patent ceased|
    优先权:
    申请号 | 申请日 | 专利标题
    JP2015113690|2015-06-04|
    PCT/JP2016/066128|WO2016194929A1|2015-06-04|2016-06-01|Method for producing perfluoroalkanesulfonyl phenol compounds|
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