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WO2014046244A1 - Procédé de production d'un composé trifluorométhanesulfonanilide - Google Patents

Procédé de production d'un composé trifluorométhanesulfonanilide Download PDF

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Publication number
WO2014046244A1
WO2014046244A1 PCT/JP2013/075511 JP2013075511W WO2014046244A1 WO 2014046244 A1 WO2014046244 A1 WO 2014046244A1 JP 2013075511 W JP2013075511 W JP 2013075511W WO 2014046244 A1 WO2014046244 A1 WO 2014046244A1
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alkyl
formula
hydrogen atom
group
atom
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PCT/JP2013/075511
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English (en)
Japanese (ja)
Inventor
隆生 工藤
宇都宮　朋久
義之 楠岡
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日産化学工業株式会社
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Priority to JP2014536937A priority Critical patent/JP6429016B2/ja
Publication of WO2014046244A1 publication Critical patent/WO2014046244A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no 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
    • C07D211/40—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings
    • C07D265/08—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D265/10—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with oxygen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
    • C07D265/32—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings with oxygen atoms directly attached to ring carbon atoms

Definitions

  • the present invention relates to a method for producing a trifluoromethanesulfonanilide compound useful as a selective herbicide for rice, corn, wheat, beet, and soybean, and a trifluoromethanesulfinanilide compound useful as an intermediate thereof, and the production thereof. It is about the method.
  • Certain trifluoromethanesulfonanilide compounds are known to have herbicidal activity (see, for example, Patent Documents 1 to 2), and some methods for producing trifluoromethanesulfonanilide are also known (for example, Patent Documents 1 to 6). On the other hand, some methods for producing trifluoromethanesulfinanilide compounds are also known (see, for example, Patent Document 3, Non-Patent Document 1 to Non-Patent Document 2).
  • Patent Document 1 Patent Document 2
  • Patent Document 5 Patent Document 6 disclose a production method using a trifluoromethanesulfonylating agent, but expensive trifluoromethanesulfonic anhydride. Only a production method using a product, trifluoromethanesulfonyl chloride, trifluoromethanesulfonyl fluoride or the like as a trifluoromethanesulfonylating agent is disclosed.
  • Patent Document 3 describes that magnesium monoperoxyphthalate or m-chloroperbenzoic acid is used as an oxidizing agent to produce a corresponding trifluoromethanesulfonanilide compound from a certain trifluoromethanesulfinanilide compound.
  • the trifluoromethanesulfinanilide compound according to the present invention there is no disclosure regarding the trifluoromethanesulfinanilide compound according to the present invention.
  • the method for producing the trifluoromethanesulfinanilide compound is described in Non-Patent Document 1 and Non-Patent Document 2, but 2 equivalents of sodium trifluoromethanesulfinate are used for 1 equivalent of the starting aniline compound.
  • the present inventor has found that a trifluoromethanesulfinyl compound that is advantageous as an industrial production intermediate of a trifluoromethanesulfonanilide compound, a method for producing the compound, and an industrially related trifluoromethanesulfonanilide compound.
  • a useful manufacturing method was found and the present invention was completed. That is, the present invention relates to the following [1] to [19].
  • A represents —CH ⁇ CH— or a sulfur atom
  • R 1 represents a hydrogen atom or C 1 -C 12 alkoxycarbonyl
  • Q represents a ring represented by any one of Q-1 to Q-10
  • W represents an oxygen atom or a sulfur atom
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, C 1 -C 6 alkyl, halo (C 1 -C 6 ) alkyl
  • C Re represents 3 -C 6 cycloalkyl, phenyl optionally substituted by one or more Y or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl
  • R 2 and R 3 , R 4 and R 5 , R 6 and R 7 and R 8 and R 9 can be bonded to each other to form an optionally substituted 3- to 7-membered ring
  • Y represents a halogen atom.
  • A represents —CH ⁇ CH—
  • R 1 represents a hydrogen atom or C 1 -C 6 alkoxycarbonyl
  • Q represents a ring represented by any of Q-1, Q-2, Q-6, Q-7, Q-8 or Q-9
  • W represents an oxygen atom
  • R 2 and R 3 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 4 and R 5 each independently represent a hydrogen atom, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl
  • R 6 and R 7 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 8 and R 9 are each a method for producing a trifluoromethanesulfonanilide compound according to [1] above, which represents a hydrogen atom.
  • A represents —CH ⁇ CH— or a sulfur atom
  • R 1 represents a hydrogen atom or C 1 -C 12 alkoxycarbonyl
  • Q represents a ring represented by any one of Q-1 to Q-10
  • W represents an oxygen atom or a sulfur atom
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, C 1 -C 6 alkyl, halo (C 1 -C 6 ) alkyl, C Represents 3 -C 6 cycloalkyl, phenyl optionally substituted by one or more Y or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl; R 2 and R 3 , R 4 and R 5 , R 6 and R 7 and R 8 and R 9 can be bonded to each other to form an optionally substituted 3- to 7-membered ring, Y represents a halogen atom],
  • A represents —CH ⁇ CH—
  • R 1 represents a hydrogen atom or C 1 -C 6 alkoxycarbonyl
  • Q represents a ring represented by any of Q-1, Q-2, Q-6, Q-7, Q-8 or Q-9
  • W represents an oxygen atom
  • R 2 and R 3 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 4 and R 5 each independently represent a hydrogen atom, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl
  • R 6 and R 7 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 8 and R 9 are each a method for producing a trifluoromethanesulfinanilide compound according to [8] above, which represents a hydrogen atom.
  • [10] The method for producing a trifluoromethanesulfinanilide compound according to [8] or [9], wherein the reaction is performed in the presence of a base.
  • the compound represented by formula (4) is produced by reacting the compound represented by formula (4) with the halogenating agent, and the produced compound represented by formula (4) is used. Or the manufacturing method of the trifluoromethanesulfine anilide compound as described in [10].
  • [12] The method for producing a trifluoromethanesulfinanilide compound according to the above [11], wherein the reaction of the compound represented by the formula (5) and the halogenating agent is carried out in the presence of a base.
  • A represents —CH ⁇ CH— or a sulfur atom
  • R 1 represents a hydrogen atom or C 1 -C 12 alkoxycarbonyl
  • Q represents a ring represented by any one of Q-1 to Q-10
  • W represents an oxygen atom or a sulfur atom
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, C 1 -C 6 alkyl, halo (C 1 -C 6 ) alkyl, C Represents 3 -C 6 cycloalkyl, phenyl optionally substituted by one or more Y or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl; R 2 and R 3 , R 4 and R 5 , R 6 and R 7 and R 8 and R 9 can be bonded to each other to form an optionally substituted 3- to 7-membered ring, Y represents a halogen atom],
  • A represents —CH ⁇ CH—
  • R 1 represents a hydrogen atom or C 1 -C 6 alkoxycarbonyl
  • Q represents a ring represented by any of Q-1, Q-2, Q-6, Q-7, Q-8 or Q-9
  • W represents an oxygen atom
  • R 2 and R 3 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 4 and R 5 each independently represent a hydrogen atom, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl
  • R 6 and R 7 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 8 and R 9 represents a hydrogen atom, trifluoromethanesulfinate anilide compound or a salt thereof according to [14].
  • Q represents a ring represented by any of Q-1, Q-2, Q-6, Q-7, Q-8 or Q-9
  • W represents an oxygen atom
  • R 2 and R 3 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 4 and R 5 each independently represent a hydrogen atom, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl
  • R 6 and R 7 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 8 and R 9 represents a hydrogen atom, nitrobenzyl amide compound according to [16].
  • Q represents a ring represented by any of Q-1, Q-2, Q-6, Q-7, Q-8 or Q-9
  • W represents an oxygen atom
  • R 2 and R 3 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 4 and R 5 each independently represent a hydrogen atom, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl
  • R 6 and R 7 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 8 and R 9 represents a hydrogen atom, an amino benzyl amide compound or salt thereof according to [18] above.
  • the present invention relates to an industrially useful production method of a trifluoromethanesulfonanilide compound having high selectivity for rice, corn, wheat, beet and soybean and having an excellent herbicidal effect, and a trifluoromethanesulfinyl compound useful as an intermediate thereof. And a method for manufacturing the same.
  • the present invention includes all optically active substances, racemates or diastereomers.
  • n- means normal
  • i- means iso
  • s- means secondary and t- means tertiary
  • o- means ortho
  • m- means meta.
  • a halogen atom in this invention a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
  • the notation “halo” also represents these halogen atoms.
  • those that can be converted into a salt according to a conventional method are, for example, salts of hydrogen halides such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, sulfuric acid , Inorganic acid salts such as phosphoric acid, chloric acid, perchloric acid, sulfonic acid salts such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, formic acid, acetic acid, propionic acid, trifluoroacetic acid, fumaric acid, tartaric acid , Succinic acid, maleic acid, malic acid, succinic acid, benzoic acid, mandelic acid, ascorbic acid, carboxylic acid salts such as lactic acid, gluconic acid, citric acid, amino acid salts such as glutamic acid, aspartic acid, lithium, sodium, potassium Alkali metal salts such as alkaline
  • C a -C b alkyl represents a linear or branched hydrocarbon group having a to b carbon atoms, such as a methyl group, an ethyl group, or n-propyl.
  • C a -C b alkoxy represents the C a -C b alkyl-O— group having the above-mentioned meaning, for example, methyl-O-group, ethyl-O-group, n-propyl -O- group, i-propyl-O- group, n-butyl-O- group, i-butyl-O- group, t-butyl-O- group, s-butyl-O- group, pentyl-O- group 1-methylbutyl-O-group, 2-methylbutyl-O-group, 3-methylbutyl-O-group, 1-ethylpropyl-O-group, 1,1-dimethylpropyl-O-group, 1,2-dimethyl Propyl-O- group, neopentyl-O- group, n-hexyl-O- group, 1-methylpentyl-O- group, 2-methylpentyl-O- group, 3-
  • C a -C b alkoxy (C a -C b ) alkyl is represented by the above-mentioned meaning that a hydrogen atom bonded to a carbon atom is optionally substituted by C a -C b alkoxy as defined above.
  • C a -C b alkyl which means, for example, methyl-O-methyl group, ethyl-O-methyl group, n-propyl-O-methyl group, i-propyl-O-methyl group, n-butyl- O-methyl group, i-butyl-O-methyl group, t-butyl-O-methyl group, s-butyl-O-methyl group, pentyl-O-methyl group, 1-methylbutyl-O-methyl group, 2- Methylbutyl-O-methyl group, 3-methylbutyl-O-methyl group, 1-ethylpropyl-O-methyl group, 1,1-dimethylpropyl-O-methyl group, 1,2-dimethylpropyl-O-methyl group, Neopentyl-O-methyl group, n-hexyl-O-methyl group, 1-methylpentyl-O-methyl Group, 2-methylpentyl-O-methyl group, 3-methylpentyl-O-
  • C a -C b alkoxycarbonyl represents a C a -C b alkyl-O—C (O) — group having the above-mentioned meaning, for example, methyl-O—C (O) — Group, ethyl-O-C (O)-group, n-propyl-O-C (O)-group, i-propyl-O-C (O)-group, n-butyl-O-C (O)-group Group, i-butyl-O-C (O)-group, t-butyl-O-C (O)-group, s-butyl-O-C (O)-group, n-pentyl-O-C (O )-Group, 1-methylbutyl-O-C (O)-group, 2-methylbutyl-O-C (O)-group, 3-methylbutyl-O-C (O)-group, 1-ethylpropyl-
  • C a ⁇ C b alkyl hydrogen atoms bonded to carbon atoms by halogen atoms is the meaning of is as defined above is optionally substituted
  • cyclo C a -C b alkyl in the present specification represents a cyclic hydrocarbon group having a carbon number of a to b, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclo A heptyl group etc. are mentioned as a specific example, and it selects in the range of each designated carbon number.
  • “R 2 and R 3 , R 4 and R 5 , R 6 and R 7, and R 8 and R 9 are bonded to each other to form an optionally substituted 3- to 7-membered ring.
  • R 2 and R 3 , R 4 and R 5 , R 6 and R 7 or R 8 and R 9 each containing a carbon atom to which they are bonded, cyclopropyl, cyclobutyl, cyclopentyl, It represents that a cyclohexyl or cycloheptyl ring can be formed.
  • the trifluoromethanesulfine anilide compound represented by Formula (1) of this invention is demonstrated.
  • R 1 represents a substituent other than a hydrogen atom
  • the trifluoromethanesulfinanilide compound represented by the formula (1) can be produced, for example, by the following method.
  • Reaction formula 1 That is, Formula (8) [In the Formula, A and Q represent the same meaning as the above.
  • R 1 represents C 1 -C 12 alkoxycarbonyl
  • T represents a halogen atom.
  • the amount of the reaction substrate 1 to 5 equivalents of the compound represented by the formula (9) can be used with respect to 1 equivalent of the compound represented by the formula (8).
  • Examples of the base to be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, calcium carbonate and potassium carbonate, and alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate.
  • Organic bases such as triethylamine, tributylamine, N, N-dimethylamine, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, The compound represented by 8) can be used in an amount of 1 to 5 equivalents.
  • the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, benzene, xylene, toluene, etc.
  • Halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chloroform, 1,2-dichloroethane, chlorobenzene, trifluoromethylbenzene, alcohols such as methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • Ketones such as acetonitrile and propionitrile, carboxylic acid esters such as ethyl acetate and ethyl propionate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone
  • nitrogen-containing aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, water and the like, preferably hydrocarbons such as xylene and toluene, halogenated hydrocarbons such as dichloromethane and dichloroethane, water Can be used. These solvents can be used by mixing two or more kinds.
  • the reaction temperature is usually -90 to 200 ° C, preferably 0 to 150 ° C.
  • the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually 10 minutes to 100 hours, preferably 10 minutes to 24 hours.
  • the trifluoromethanesulfine anilide compound represented by the formula (1) and the trifluoromethanesulfone anilide compound represented by the formula (2) obtained by oxidizing the compound are as follows: Preferred are trifluoromethanesulfinanilide compounds and trifluoromethanesulfonanilide compounds in which each substituent is as follows.
  • A represents —CH ⁇ CH—
  • R 1 represents a hydrogen atom or C 1 -C 6 alkoxycarbonyl
  • Q represents a ring represented by any of Q-1, Q-2, Q-6, Q-7, Q-8 or Q-9
  • W represents an oxygen atom
  • R 2 and R 3 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 4 and R 5 each independently represent a hydrogen atom, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl
  • R 6 and R 7 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 8 and R 9 represent a hydrogen atom.
  • a solvent can be used as necessary.
  • the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, benzene, xylene, toluene, dichloromethane, tetrachloride
  • Halogenated hydrocarbons such as carbon, chloroform, 1,2-dichloroethane, chlorobenzene and trifluoromethylbenzene
  • nitriles such as acetonitrile and propionitrile
  • alcohols such as methanol, ethanol and 2-propanol, formic acid and acetic acid Acid, water, etc.
  • hydrocarbons such as xylene, toluene, halogenated hydrocarbons such as dichloromethane, chloroform
  • the method for producing the trifluoromethanesulfonanilide compound can be carried out by adding an acid as necessary.
  • the acid used is not particularly limited, but for example, fatty acids such as formic acid, acetic acid and trifluoroacetic acid, sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and 4-methylbenzenesulfonic acid, and carboxylic acids such as benzoic acid Phosphonic acids such as aminomethylphosphonic acid and phenylphosphonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid.
  • fatty acids such as formic acid, acetic acid and trifluoroacetic acid
  • sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and 4-methylbenzenesulfonic acid
  • carboxylic acids such as benzoic acid Phosphonic acids such as aminomethylphosphonic acid and phenylphospho
  • acetic acid Preferably, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phenylphosphonic acid and the like are used.
  • the acid is usually used in an amount of 100 equivalents or less, preferably 2 equivalents or less, more preferably 0.01 to 2 equivalents, relative to 1 equivalent of the compound represented by formula (1) or formula (3).
  • oxidizing agent in the above method for producing a trifluoromethanesulfonanilide compound include m-chloroperbenzoic acid, magnesium monoperoxyphthalate, peracid such as peracetic acid, iodine peroxidation such as sodium periodate and iodosobenzene.
  • peracid such as peracetic acid
  • iodine peroxidation such as sodium periodate and iodosobenzene.
  • Products, persulfates such as potassium hydrogen persulfate, hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide.
  • the oxidizing agent is preferably one selected from the group consisting of peracids, iodine peroxides and hydroperoxides.
  • m-chloroperbenzoic acid magnesium monoperoxyphthalate, periodate.
  • One type selected from the group consisting of sodium acid and hydrogen peroxide is preferable.
  • hydrogen peroxide it is preferable to use 1 to 50% by weight hydrogen peroxide solution, urea hydrogen peroxide, etc., more preferably 30 to 36% by weight hydrogen peroxide solution.
  • the oxidizing agent is generally used in an amount of 0.5 to 100 equivalents, preferably 1 to 2 equivalents, relative to 1 equivalent of the compound represented by the formula (1).
  • the reaction is preferably carried out in the presence of ruthenium trichloride.
  • Ruthenium trichloride is usually used in an amount of 0.001 to 100 equivalents, preferably 0.01 to 2 equivalents, per 1 equivalent of the compound represented by the formula (1).
  • hydrogen peroxide used as the oxidizing agent
  • the reaction is preferably performed in the presence of sodium tungstate and / or a phase transfer catalyst.
  • sodium tungstate is usually used in an amount of 0.001 to 100 equivalents, preferably 0.01 to 2 equivalents, relative to 1 equivalent of the compound represented by formula (1). .
  • phase transfer catalyst examples include tetrabutylammonium chloride, tetrabutylammonium bromide, tetramethylammonium hydrogensulfate, tetraethylammonium hydrogensulfate, tetrapropylammonium hydrogensulfate.
  • Quaternary ammonium salts such as tetrabutylammonium hydrogensulfate, tetrahexylammonium hydrogensulfate, methyltrioctylammonium hydrogensulfate, methyltrioctylammonium chloride, pyridinium salts such as cetylpyridinium chloride, tetrabutylphosphonium bromide, tributylhexa Examples thereof include phosphonium salts such as decylphosphonium chloride and tetraphenylphosphonium chloride.
  • phase transfer catalyst is generally used in an amount of 100 equivalents or less, preferably 2 equivalents or less, more preferably 0.01 to 1 equivalent, per 1 equivalent of the compound represented by the formula (1).
  • the reaction in the above method for producing a trifluoromethanesulfonanilide compound can be carried out in a pressure range of 0.001 to 100 MPa, preferably 0.1 to 10 MPa.
  • the reaction temperature is usually ⁇ 20 to 100 ° C., preferably 0 to 80 ° C.
  • the reaction time is usually 10 minutes to 100 hours, preferably 10 minutes to 24 hours. If necessary, it can be carried out in an inert gas atmosphere such as nitrogen or argon.
  • the treatment method after the reaction is not particularly limited, but the reaction mixture after completion of the reaction is directly concentrated or dissolved in an organic solvent, and then poured into water, separated, concentrated as necessary, or poured into water.
  • the post-treatment such as extraction and concentration as necessary can be carried out to obtain the produced compound.
  • reaction mixture and the solution obtained by the reaction treatment can be treated with a reducing agent, an acid, a base and the like.
  • finish of reaction can be used for the following process as it is.
  • the manufactured compound can also be used for the following process with the solution obtained by the post-process.
  • it can be separated and purified by any purification method such as distillation, recrystallization, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.
  • the manufacturing method of the trifluoromethanesulfine anilide compound represented by Formula (1) of this invention is demonstrated.
  • the amine compound represented by the formula (3) used in the method for producing the trifluoromethanesulfinanilide compound an amine compound in which each substituent is as follows is preferable. This production method is applicable not only to the amino group on the benzene ring where A is —CH ⁇ CH— but also to the amino group on the heterocycle where A is a sulfur atom.
  • A represents —CH ⁇ CH—
  • R 1 represents a hydrogen atom or C 1 -C 6 alkoxycarbonyl
  • Q represents a ring represented by any of Q-1, Q-2, Q-6, Q-7, Q-8 or Q-9
  • W represents an oxygen atom
  • R 2 and R 3 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 4 and R 5 each independently represent a hydrogen atom, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl
  • R 6 and R 7 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 8 and R 9 represent a hydrogen atom.
  • Examples of the compound represented by the formula (4) used in the method for producing the trifluoromethanesulfinylide compound include trifluoromethanesulfinyl fluoride, trifluoromethanesulfinyl chloride, trifluoromethanesulfinyl bromide, and trifluoromethanesulfinyl iodide.
  • Trifluoromethanesulfinyl chloride can be synthesized according to a general synthesis method described in the literature. For example, it can be produced by the method described in JP-A-10-218857, Chemiche Beirichte 1974, 107, 508, Tetrahedron 1999, Vol. 55, Vol. 7243, or Tetrahedron, 1976, Vol. 32, 1627. is there.
  • the compound represented by the formula (4) is usually used in an amount of 0.5 to 2 equivalents with respect to 1 equivalent of the compound represented by the formula (3).
  • Examples of the salt of trifluoromethanesulfinic acid represented by the formula (5) in the method for producing the trifluoromethanesulfinanilide compound include alkali metal salts such as lithium, sodium, and potassium.
  • alkali metal salts such as lithium, sodium, and potassium.
  • sodium trifluoromethanesulfinate which is a sodium salt of trifluoromethanesulfinic acid
  • potassium trifluoromethanesulfinate which is a potassium salt of trifluoromethanesulfinic acid
  • the salt of trifluoromethanesulfinic acid represented by the formula (5) is usually used in an amount of 0.5 to 2 equivalents per 1 equivalent of the compound represented by the formula (3).
  • a solvent can be used as necessary.
  • the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, n-heptane, benzene, xylene, and toluene
  • Halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chloroform, 1,2-dichloroethane, chlorobenzene, trifluoromethylbenzene
  • ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, nitriles such as aceton
  • the reaction between the amine compound represented by the formula (3) and the compound represented by the formula (4) is preferably performed in the presence of a base.
  • the base to be used is not particularly limited, but examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium phosphate, pyridine, 4 -Dimethylaminopyridine, triethylamine, tributylamine, 5-ethyl-2-methylpyridine, 2-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, N, N-dimethylaniline, N, N-diethylaniline, Organic bases such as 1,8-diazabicyclo [5.4.0] -7-undecene, organic lithium compounds such as n-butyllithium and s-butyllithium, lithium diisopropylamide, lithium bis (tri
  • metal alkoxides such as ethoxide, sodium i-propoxide, potassium t-butoxide and the like.
  • triethylamine, tributylamine, 5-ethyl-2-methylpyridine, 2-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine and pyridine are used.
  • the base is generally used in an amount of 10 equivalents or less, preferably 4 equivalents or less, more preferably 0.01 to 2 equivalents, relative to 1 equivalent of the compound represented by Formula (1) or Formula (3).
  • the compound represented by the formula (4) is preferably a compound produced by reacting the compound represented by the formula (5) with a halogenating agent. This reaction can also be carried out in the presence of a base.
  • a base examples include organic bases such as triethylamine, tributylamine, pyridine, 4-dimethylaminopyridine, 5-ethyl-2-methylpyridine, 2-methylpyridine, 4-methylpyridine, and 2,6-dimethylpyridine.
  • the base is usually used in an amount of 10 equivalents or less based on 1 equivalent of the compound represented by the formula (5).
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, and phosphorus oxychloride.
  • thionyl chloride is used.
  • the halogenating agent is generally used in an amount of 0.5 to 100 equivalents, preferably 1 to 10 equivalents, relative to the compound represented by the formula (3).
  • an amide compound can be added as an additive.
  • N, N-dimethylformamide is preferably used.
  • the additive is generally used in an amount of 100 equivalents or less, preferably 10 equivalents or less, particularly preferably 0.001 to 1 equivalent, based on the compound represented by the formula (3).
  • the reaction in the method for producing the trifluoromethanesulfinanilide compound can be carried out in the pressure range of 0.001 to 100 MPa, preferably 0.1 to 10 MPa.
  • the reaction temperature is usually -90 to 200 ° C, preferably 0 to 150 ° C.
  • the reaction time is usually 10 minutes to 100 hours, preferably 10 minutes to 24 hours. If necessary, it can be carried out in an inert gas atmosphere such as nitrogen or argon.
  • the treatment method after the reaction is not particularly limited, but the reaction mixture after completion of the reaction is directly concentrated or dissolved in an organic solvent, and then poured into water, separated, concentrated as necessary, or poured into water.
  • the post-treatment such as extraction and concentration as necessary can be carried out to obtain the produced compound.
  • reaction mixture and the solution obtained by the reaction treatment can be treated with a reducing agent, an acid, a base and the like.
  • finish of reaction can be used for the following process as it is.
  • the manufactured compound can also be used for the following process with the solution obtained by the post-process.
  • it can be separated and purified by any purification method such as distillation, recrystallization, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.
  • the acid, base, additive, oxidizing agent, halogenating agent, sodium tungstate, ruthenium trichloride and phase transfer catalyst related to the production method of the present invention described above can be used in solvates such as hydrates, Diluted ones can also be used.
  • the present invention is also a trifluoromethanesulfinanilide compound represented by the formula (1) or a salt thereof.
  • the preferable substituents in the trifluoromethanesulfinanilide compound represented by the formula (1) are also as described above.
  • the salt of the trifluoromethanesulfinanilide compound represented by the formula (1) is also as described above.
  • the present invention is also a synthetic intermediate of a compound in which A is —CH ⁇ CH— among the trifluoromethanesulfinanilide compounds represented by the formula (1). That is, the present invention is also a nitrobenzylamide compound represented by formula (6) and an aminobenzylamide compound represented by formula (7) or a salt thereof.
  • the trifluoromethanesulfinanilide compound represented by the above formula (1) (where A is —CH ⁇ CH—) is preferably produced from an aminobenzylamide compound represented by the formula (7).
  • the aminobenzylamide compound represented by 7) is preferably produced from the nitrobenzylamide compound represented by formula (6).
  • a nitrobenzylamide compound in which each substituent is as follows is preferable.
  • Q represents a ring represented by any of Q-1, Q-2, Q-6, Q-7, Q-8 or Q-9
  • W represents an oxygen atom
  • R 2 and R 3 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 4 and R 5 each independently represent a hydrogen atom, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl
  • R 6 and R 7 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 8 and R 9 represent a hydrogen atom.
  • the nitrobenzylamide compound represented by the above formula (6) is produced, for example, by the method shown in the following reaction formula 2.
  • Reaction formula 2 That is, formula (10) [wherein L represents a leaving group such as a halogen atom.
  • the nitrobenzylamide compound represented by the formula (6) can be produced by reacting the lactam compound represented by formula (6) in the presence of a base.
  • 0.5 to 5 equivalents of the compound represented by the formula (11) can be used with respect to 1 equivalent of the compound represented by the formula (10).
  • Examples of the base used in Step 2 include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, calcium carbonate and potassium carbonate, and alkali metals such as sodium hydrogen carbonate and potassium hydrogen carbonate.
  • An organic base such as bicarbonate, triethylamine, tributylamine, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, and the like are represented by the formula (10). 1 to 5 equivalents can be used with respect to the compound to be obtained.
  • the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, benzene, xylene, toluene, etc.
  • Halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chloroform, 1,2-dichloroethane, chlorobenzene, trifluoromethylbenzene, alcohols such as methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • Ketones such as acetonitrile and propionitrile, carboxylic acid esters such as ethyl acetate and ethyl propionate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolide
  • Nitrogen-containing aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, water and the like, preferably hydrocarbons such as benzene, xylene and toluene, and halogen-based carbonization such as dichloromethane and dichloroethane.
  • Hydrogen, diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, ethers such as tertiary butyl methyl ether, and water can be used. These solvents can be used in a mixture of two or more.
  • the reaction temperature is usually -90 to 200 ° C, preferably 0 to 150 ° C.
  • the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually 10 minutes to 100 hours, preferably 10 minutes to 24 hours.
  • the compound represented by the formula (10) used here is a known compound, and a part thereof is also available as a commercial product.
  • other compounds can be synthesized according to a general synthesis method described in literatures concerning known compounds.
  • the compound in which Q is represented by Q-1, Q-2 or Q-6 is, for example, the method represented by the following reaction formula 3 or It is produced by the method shown in Reaction Scheme 4.
  • Reaction formula 3 That is, formula (10) [wherein L represents the same meaning as described above. And a nitrobenzyl compound represented by formula (12) [wherein n represents 0, 1 or 2 and R 2 , R 3 , R 4 and R 5 represent the same meaning as described above].
  • the nitrobenzylimide compound represented by the formula (13) can be produced by reacting with an imide compound in the presence of a base. Subsequently, the nitrobenzylamide compound represented by the formula (14) can be produced by reducing the carbonyl group of the compound represented by the formula (13). Furthermore, the benzylamide compound represented by Formula (15) can be manufactured by reducing the hydroxyl group of the compound represented by Formula (14).
  • 1 to 5 equivalents of the compound represented by the formula (12) can be used with respect to 1 equivalent of the compound represented by the formula (10).
  • Examples of the base used in Step 3 include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, calcium carbonate and potassium carbonate, and alkali metals such as sodium hydrogen carbonate and potassium hydrogen carbonate.
  • An organic base such as bicarbonate, triethylamine, tributylamine, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, and the like are represented by the formula (10). 1 to 5 equivalents can be used with respect to the compound to be obtained.
  • Step 4 for example, a method using a metal hydride such as sodium borohydride, lithium borohydride, lithium aluminum hydride, or the like can be used.
  • Step 5 for example, a method using triethylsilane / trifluoroacetic acid, a dehydration using an acid catalyst, and a subsequent hydrogenation in the presence of a metal catalyst such as palladium can be used.
  • the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, benzene, xylene, toluene, etc.
  • Halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chloroform, 1,2-dichloroethane, chlorobenzene, trifluoromethylbenzene, alcohols such as methanol, ethanol, 2-propanol, diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, Examples include ethers such as tertiary butyl methyl ether, water, etc., preferably alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and cyclopentyl methyl ether, It can be used. These solvents can be used in a mixture of two or more.
  • the reaction temperature is usually -90 to 200 ° C, preferably 0 to 150 ° C.
  • the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually 10 minutes to 100 hours, preferably 10 minutes to 24 hours.
  • the compound represented by the formula (12) used here is a known compound, and a part thereof is also available as a commercial product.
  • other compounds can be synthesized according to a general synthesis method described in literatures concerning known compounds.
  • Reaction formula 4 That is, the nitrobenzylamine represented by the formula (16) and the formula (17) [wherein n represents 0 or 1, and L, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 Represents the same meaning as described above. ] Is reacted using a condensing agent or the like to formula (18) [wherein n represents 0 or 1, and L, R 2 , R 3 , R 4 , R 5 , R 6 and R 7 have the same meaning as described above.
  • the nitrobenzylamide compound represented by the formula (19) is produced by cyclizing the compound represented by the formula (18) with a base or the like. I can do it.
  • Examples of the reagent used in Step 6 include dehydrating condensing agents such as WSC (Water Soluble Carbideimide) and N, N-dicyclohexylcarbodiimide, and acid chloride compounds such as oxalyl chloride and thionyl chloride.
  • dehydrating condensing agents such as WSC (Water Soluble Carbideimide) and N, N-dicyclohexylcarbodiimide
  • acid chloride compounds such as oxalyl chloride and thionyl chloride.
  • the amount of the reaction substrate 0.5 to 5 equivalents of the compound represented by the formula (17) can be used with respect to 1 equivalent of the compound represented by the formula (16).
  • Examples of the base used in Step 7 include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, calcium carbonate and potassium carbonate, and alkali metals such as sodium hydrogen carbonate and potassium hydrogen carbonate.
  • An organic base such as bicarbonate, triethylamine, tributylamine, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, and the like are represented by formula (17). 1 to 5 equivalents can be used with respect to the compound to be obtained.
  • the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, benzene, xylene, toluene, etc.
  • Halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chloroform, 1,2-dichloroethane, chlorobenzene, trifluoromethylbenzene, alcohols such as methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • Ketones such as acetonitrile and propionitrile, carboxylic acid esters such as ethyl acetate and ethyl propionate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolide
  • Nitrogen-containing aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, water and the like, preferably hydrocarbons such as benzene, xylene and toluene, and halogen-based carbonization such as dichloromethane and dichloroethane.
  • Hydrogen, diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, ethers such as tertiary butyl methyl ether, and water can be used. These solvents can be used in a mixture of two or more.
  • the reaction temperature is usually -90 to 200 ° C, preferably 0 to 150 ° C.
  • the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually 10 minutes to 100 hours, preferably 10 minutes to 24 hours.
  • the compound represented by the formula (17) used here is a known compound, and a part thereof is also available as a commercial product.
  • other compounds can be synthesized according to a general synthesis method described in literatures concerning known compounds.
  • an aminobenzylamide compound in which each substituent is as follows is preferable.
  • Q represents a ring represented by any of Q-1, Q-2, Q-6, Q-7, Q-8 or Q-9
  • W represents an oxygen atom
  • R 2 and R 3 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 4 and R 5 each independently represent a hydrogen atom, C 1 -C 6 alkyl or C 1 -C 6 alkoxy (C 1 -C 6 ) alkyl
  • R 6 and R 7 each independently represents a hydrogen atom or C 1 -C 6 alkyl
  • R 8 and R 9 represent a hydrogen atom.
  • the salt of the aminobenzylamide compound represented by the formula (7) is as described above.
  • the aminobenzylamide compound represented by the above formula (7) is produced, for example, by the method shown in the following reaction formula 5.
  • Reaction formula 5 That is, the formula (6) [wherein Q represents the same meaning as described above.
  • Q represents the same meaning as described above.
  • the aminobenzylamide compound represented by this can be manufactured.
  • Examples of the reduction method used in Step 8 include a method using a metal hydride such as sodium borohydride, lithium borohydride, and lithium aluminum hydride, a method using hydrogenation in the presence of a palladium catalyst, iron, zinc chloride, tin chloride, and the like.
  • the metal reduction method can be used.
  • the amount of the reducing agent used can be 0.01 to 5 equivalents with respect to 1 equivalent of the compound represented by the formula (6).
  • the solvent used is not particularly limited as long as it does not inhibit the progress of the reaction.
  • hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, benzene, xylene, toluene, etc.
  • Halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chloroform, 1,2-dichloroethane, chlorobenzene, trifluoromethylbenzene, alcohols such as methanol, ethanol, 2-propanol, diethyl ether, tetrahydrofuran, cyclopentyl methyl ether, Examples include ethers such as tertiary butyl methyl ether, water, etc., preferably alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and cyclopentyl methyl ether, It can be used. These solvents can be used in a mixture of two or more.
  • the reaction temperature is usually -90 to 200 ° C, preferably 0 to 150 ° C.
  • the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually 10 minutes to 100 hours, preferably 10 minutes to 24 hours.
  • the obtained organic layer was washed with water and saturated brine in this order, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • Synthesis example 2 Synthesis of 4,4-dimethyl-1- (2-trifluoromethanesulfonylaminobenzyl) piperidin-2-one 4,4-dimethyl-1- (2-trifluoromethanesulfinylaminobenzyl) piperidin-2-one 300 mg of toluene 3 g To the solution were added 292 mg of 30 wt% aqueous hydrogen peroxide, 28 mg of sodium tungstate dihydrate and 29 mg of tetrabutylammonium hydrogen sulfate, and the mixture was stirred at 50 ° C. for 7 hours.
  • Synthesis example 3 Synthesis of 4,4-dimethyl-1- (2-trifluoromethanesulfonylaminobenzyl) piperidin-2-one 4,4-dimethyl-1- (2-trifluoromethanesulfinylaminobenzyl) piperidin-2-one 300 mg of chloroform 3 g To the slurry, 340 mg of m-chloroperbenzoic acid was added and stirred at 80 ° C. for 5 hours. After completion of the stirring, the reaction solution was analyzed by an internal standard analysis method using high performance liquid chromatography (hereinafter also referred to as HPLC), and it was found that the target product was contained in a yield of 77.0%. .
  • HPLC high performance liquid chromatography
  • Synthesis example 4 Synthesis of 4,4-dimethyl-1- (2-trifluoromethanesulfonylaminobenzyl) piperidin-2-one 300 mg of 4,4-dimethyl-1- (2-trifluoromethanesulfinylaminobenzyl) piperidin-2-one was added to acetonitrile / It melt
  • dissolved in 3 g of mixed solvents of water 1/1, 29 mg of ruthenium (III) chloride hydrate and 414 mg of sodium periodate were added, and it stirred at room temperature for 10 hours. After completion of the stirring, the reaction solution was analyzed by an internal standard analysis method using the same analysis conditions as in Synthesis Example 3, and it was found that the target product was contained in a yield of 63.6%.
  • Synthesis example 5 Synthesis of 4,4-dimethyl-1- (2-trifluoromethanesulfonylaminobenzyl) piperidin-2-one 4,4-dimethyl-1- (2-trifluoromethanesulfinylaminobenzyl) piperidin-2-one 200 mg of methanol 3 g To this, 444 mg of magnesium monoperoxyphthalate hexahydrate was added and stirred at room temperature for 3 hours. After completion of the stirring, the reaction solution was analyzed by the internal standard analysis method using the same analysis conditions as in Synthesis Example 3, and it was found that the target product was contained in a yield of 58.0%.
  • Synthesis example 7 Synthesis of 1- [2- (N-ethoxycarbonyl-N-trifluoromethanesulfonyl) aminobenzyl] -4,4-dimethylpiperidin-2-one 1- [2- (N-ethoxycarbonyl-N-trifluoromethanesulfinyl) Aminobenzyl] -4,4-dimethylpiperidin-2-one To a solution of 300 mg of toluene in 3 g of toluene, 292 mg of 30 wt% aqueous hydrogen peroxide, 28 mg of sodium tungstate dihydrate and 29 mg of tetrabutylammonium hydrogen sulfate were added, The mixture was stirred at 50 ° C. for 7 hours.
  • the purity of the target product is calculated from the relative percentage of the peak area of HPLC, and the analysis conditions are shown below.
  • Synthesis example 8 Synthesis of 3,3-dimethyl-1- (2-trifluoromethanesulfinylaminobenzyl) pyrrolidin-2-one To a mixed slurry of 400 mg of sodium trifluoromethanesulfinate 1.5 g of toluene and 1.0 g of dichloromethane was added 330 g of thionyl chloride and N, 50 mg of N-dimethylformamide was added dropwise under ice cooling. The reaction mixture was warmed to room temperature and stirred for 1 hour.
  • reaction mixture was ice-cooled again, and a mixed solution of 4,4-dimethyl-1- (2-aminobenzyl) pyrrolidin-2-one (1090 mg), toluene (1310 mg) and dichloromethane (870 mg), and then triethylamine (760 mg) were added. Stirring was continued for an hour. After completion of the reaction, ethyl acetate and water were added to the reaction mixture, and the organic layer was separated. The obtained organic layer was washed with water and then with saturated brine, dehydrated with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed with water and saturated brine in this order, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • Reference example 1 Synthesis of 1- (2-aminobenzyl) -4,4-dimethylpiperidin-2-one To a solution of 200 mg of 2-aminobenzylamine in 5 ml of N, N-dimethylformamide, Methyl pentenoate (437 mg) and potassium carbonate (270 mg) were added, and the mixture was stirred at 50 ° C. for 4 hours. After completion of the reaction, ethyl acetate and water were added to the reaction mixture, and the organic layer was separated. The obtained organic layer was washed with water and saturated brine in this order, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed successively with water and saturated brine, dehydrated with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give 4.11 g of 2-nitrobenzylamine as a yellow oil.
  • the obtained oil was dissolved in a mixed solvent of 5 g of water and 10 g of methanol, 3.93 g of 2,2-dimethylsuccinic acid was added, and the mixture was stirred at room temperature for 1 hour.
  • the solvent of the obtained reaction mixture was distilled off under reduced pressure. After adding 80 g of o-xylene to the resulting residue, a Dean-Stark tube was attached to the reaction vessel, and the mixture was heated to reflux for 9 hours while removing generated water.
  • Step 2 5-hydroxy-3,3-dimethyl-1- (2-nitrobenzyl) pyrrolidin-2-one and 5-hydroxy-4,4-dimethyl-1- (2-nitrobenzyl) pyrrolidin-2-one
  • Preparation of 2.63 g of 3,3-dimethyl-1- (2-nitrobenzyl) pyrrolidine-2,5-dione in 40 g of tetrahydrofuran, 1.9 g of sodium borohydride and 4.5 g of water were added under ice cooling. The mixture was added and stirred for 2 hours under ice cooling. After completion of the reaction, water and ethyl acetate were added to the reaction mixture, and the organic layer was separated.
  • the obtained organic layer was washed with water and saturated brine in this order, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • 0.73 g of pyrrolidin-2-one and 1.44 g of 5-hydroxy-4,4-dimethyl-1- (2-nitrobenzyl) pyrrolidin-2-one were obtained as white crystals, respectively.
  • Step 3 Preparation of 3,3-dimethyl-1- (2-nitrobenzyl) pyrrolidin-2-one 0.73 g of 5-hydroxy-3,3-dimethyl-1- (2-nitrobenzyl) pyrrolidin-2-one was dissolved in 2 g of trifluoroacetic acid, 0.39 g of triethylsilane was added under ice cooling, and the mixture was stirred for 2 hours under ice cooling. After completion of the reaction, the reaction mixture was poured into a saturated aqueous sodium hydrogen carbonate solution, ethyl acetate was further added, and the organic layer was separated.
  • Step 4 Preparation of 1- (2-aminobenzyl) -3,3-dimethylpyrrolidin-2-one 1.28 g of 3,3-dimethyl-1- (2-nitrobenzyl) pyrrolidin-2-one was added to 20 g of ethanol and It melt
  • Step 2 Preparation of 1- (2-aminobenzyl) -4,4-dimethylpyrrolidin-2-one 2.1 g of 4,4-dimethyl-1- (2-nitrobenzyl) pyrrolidin-2-one was added to 40 g of ethanol and It melt
  • Step 2 Preparation of 3,3-dimethyl-1- (2-nitrobenzyl) azetidin-2-one 1.4 g of 3-chloro-2,2-dimethyl-N- (2-nitrobenzyl) propanamide was added to 15 g of acetone. The solution was dissolved in 1.43 g of potassium carbonate and stirred at 80 ° C. for 3 days. After completion of the reaction, ethyl acetate and water were added to the reaction mixture, and the organic layer was separated. The obtained organic layer was washed with water and saturated brine in this order, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • Step 3 Preparation of 1- (2-aminobenzyl) -3,3-dimethylazetidin-2-one 0.73 g of 3,3-dimethyl-1- (2-nitrobenzyl) azetidin-2-one was added to 10 g of ethanol. And dissolved in a mixed solvent of 5 g of water, 0.75 g of reduced iron and 80 mg of ammonium chloride were added, and the mixture was stirred at 80 ° C. for 1 hour. After completion of the reaction, insoluble matters in the reaction mixture were removed by Celite filtration, and the filtrate was concentrated under reduced pressure. Ethyl acetate and water were added to the residue, and the organic layer was separated.
  • Step 2 Preparation of 2-chloro-N- (2-hydroxypropyl) -N- (2-nitrobenzyl) acetamide 1.00 g of 1- (2-nitrobenzylamino) propan-2-ol and 480 mg of triethylamine 15 ml of tetrahydrofuran To the solution, 540 mg of chloroacetyl chloride was added dropwise under ice cooling, and the mixture was stirred for 2 hours. After completion of the reaction, ethyl acetate and water were added and the organic layer was separated.
  • Step 3 Preparation of 4- (2-nitrobenzyl) -6-methyl-1,4-oxazinan-3-one 63% by weight sodium hydride (dispersed in mineral oil) 300 mg of tetrahydrofuran in 20 ml A solution of 1.15 g of -chloro-N- (2-hydroxypropyl) -N- (2-nitrobenzyl) acetamide in 15 ml of tetrahydrofuran was added dropwise over 30 minutes, and the mixture was stirred for 3 hours and 30 minutes. After completion of the reaction, ethyl acetate and water were added to the reaction mixture, and the organic layer was separated.
  • the obtained organic layer was dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • Step 4 Preparation of 4- (2-aminobenzyl) -6-methyl-1,4-oxazinan-3-one 4- (2-nitrobenzyl) -6-methyl-1,4-oxazinan-3-one 380 mg was dissolved in 15 ml of ethanol and 8 ml of water, 420 mg of reduced iron and 40 mg of ammonium chloride were added, and the mixture was stirred at 80 ° C. for 1 hour. After completion of the reaction, insoluble matters in the reaction mixture were removed by Celite filtration, and the filtrate was concentrated under reduced pressure. Ethyl acetate and water were added to the residue, and the organic layer was separated.
  • the reaction was terminated by adding an aqueous ammonium chloride solution to the reaction mixture. Further, ethyl acetate was added to the reaction mixture, and the organic layer was separated. The obtained organic layer was washed with water and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 1.60 g of the desired product as a colorless transparent liquid.
  • Step 2 Preparation of 3-hydroxy-4-methoxy-3-methylbutyric acid Ethyl 3-hydroxy-4-methoxy-3-methylbutanoate 1.60 g in ethanol 10 ml solution, sodium hydroxide 0.44 g dissolved in water 10 ml The solution was added dropwise at 0 ° C. The mixture was warmed to room temperature and stirred overnight. After completion of the reaction, ethyl acetate and dilute hydrochloric acid were added to the reaction mixture, and the organic layer was separated. The obtained organic layer was washed with water and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 1.3 g of the objective product as a colorless transparent oil.
  • Step 3 Preparation of 3-hydroxy-4-methoxy-3-methyl-N- (2-nitrobenzyl) butanamide
  • 2-nitro 0.63 g of benzylamine hydrochloride, 0.41 g of triethylamine and 1.12 g of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride were added at room temperature. And stirred overnight. After completion of the reaction, ethyl acetate and dilute hydrochloric acid were added to the reaction mixture, and the organic layer was separated.
  • the obtained organic layer was washed with water and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • Step 4 Preparation of 3- (2-nitrobenzyl) -6-methoxymethyl-6-methyl-1,3-oxazinan-4-one 3-hydroxy-4-methoxy-3-methyl-N- (2-nitro
  • Step 5 Preparation of 3- (2-aminobenzyl) -6-methoxymethyl-6-methyl-1,3-oxazinan-4-one 3- (2-nitrobenzyl) -6-methoxymethyl-6-methyl- 0.60 g of 1,3-oxazinan-4-one was dissolved in 10 ml of ethanol and 5 ml of water, 0.60 g of reduced iron and 60 mg of ammonium chloride were added, and the mixture was stirred at 80 ° C. for 2 hours. After completion of the reaction, insoluble matters in the reaction mixture were removed by Celite filtration, and the filtrate was concentrated under reduced pressure. Ethyl acetate and water were added to the residue, and the organic layer was separated.
  • the obtained organic layer was dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed with water and saturated brine in this order, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed with water and saturated brine in this order, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed with water and then with saturated brine, dehydrated with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed with water and then with saturated brine, dehydrated with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed with water and then with saturated brine, dehydrated with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed with water and then with saturated brine, dehydrated with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed with water and saturated brine in this order, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed with water and saturated brine in this order, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained organic layer was washed with water and saturated brine in this order, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the trifluoromethanesulfinanilide compound according to the present invention is a very useful compound as a novel production intermediate of a trifluoromethanesulfonanilide compound having high selectivity for rice, corn, wheat, beet and soybean and having an excellent herbicidal effect. is there.
  • the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2012-207432 filed on September 20, 2012 are incorporated herein as the disclosure of the specification of the present invention. It is.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un nouveau procédé de production et un nouvel intermédiaire de production pour un herbicide. L'invention concerne : en rapport avec un herbicide de type trifluorométhanesulfonanilide représenté par la formule (2) : [dans la formule, A représente -CH=CH- ou un atome de soufre, R1 représente un atome d'hydrogène ou un alcoxycarbonyle en C1 à C12, et Q représente un composé cyclique tel qu'un lactame ou une morpholin-3-one], un procédé de production industriellement utile qui utilise un agent oxydant ; un composé trifluorométhanesulfinyle utile en tant qu'intermédiaire dans ledit procédé de production ; et un procédé de production dudit composé trifluorométhanesulfinyle.
PCT/JP2013/075511 2012-09-20 2013-09-20 Procédé de production d'un composé trifluorométhanesulfonanilide WO2014046244A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014175206A1 (fr) * 2013-04-23 2014-10-30 石原産業株式会社 Composé de type heteroarylsulfonamide ou sel de celui-ci
WO2015060402A1 (fr) * 2013-10-25 2015-04-30 日産化学工業株式会社 Procédé de production d'un composé trifluorométhanesulfonanilide
CN106699615A (zh) * 2016-12-28 2017-05-24 江苏托球农化股份有限公司 一种三氟甲基亚磺酰氯的生产工艺
CN108003105A (zh) * 2018-01-02 2018-05-08 上海克琴科技有限公司 一种合成小分子氨基酸衍生物依克多因的方法

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JPH10218857A (ja) * 1995-12-07 1998-08-18 Sumitomo Chem Co Ltd トリフルオロメタンスルフィンアニリド化合物およびその用途
JP2008143895A (ja) * 2006-11-17 2008-06-26 Nippon Nohyaku Co Ltd ハロアルキルスルホンアニリド誘導体又はその塩類、及びこれを有効成分とする除草剤並びにその使用方法
WO2010026989A1 (fr) * 2008-09-02 2010-03-11 日産化学工業株式会社 Dérivé halogénoalkylsulfonanilide ortho-substitué et herbicide
WO2010119906A1 (fr) * 2009-04-14 2010-10-21 日産化学工業株式会社 Dérivés d'haloalkylsulfonanilide
JP2010280638A (ja) * 2009-06-08 2010-12-16 Nippon Nohyaku Co Ltd ハロアルキルスルホンアニリド誘導体又はその塩類及びこれを有効成分とする除草剤並びにその使用方法
JP2011037746A (ja) * 2009-08-10 2011-02-24 Nissan Chem Ind Ltd ハロアルキルスルホンアニリド化合物の製造方法

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JPH10218857A (ja) * 1995-12-07 1998-08-18 Sumitomo Chem Co Ltd トリフルオロメタンスルフィンアニリド化合物およびその用途
JP2008143895A (ja) * 2006-11-17 2008-06-26 Nippon Nohyaku Co Ltd ハロアルキルスルホンアニリド誘導体又はその塩類、及びこれを有効成分とする除草剤並びにその使用方法
WO2010026989A1 (fr) * 2008-09-02 2010-03-11 日産化学工業株式会社 Dérivé halogénoalkylsulfonanilide ortho-substitué et herbicide
WO2010119906A1 (fr) * 2009-04-14 2010-10-21 日産化学工業株式会社 Dérivés d'haloalkylsulfonanilide
JP2010280638A (ja) * 2009-06-08 2010-12-16 Nippon Nohyaku Co Ltd ハロアルキルスルホンアニリド誘導体又はその塩類及びこれを有効成分とする除草剤並びにその使用方法
JP2011037746A (ja) * 2009-08-10 2011-02-24 Nissan Chem Ind Ltd ハロアルキルスルホンアニリド化合物の製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014175206A1 (fr) * 2013-04-23 2014-10-30 石原産業株式会社 Composé de type heteroarylsulfonamide ou sel de celui-ci
WO2015060402A1 (fr) * 2013-10-25 2015-04-30 日産化学工業株式会社 Procédé de production d'un composé trifluorométhanesulfonanilide
JPWO2015060402A1 (ja) * 2013-10-25 2017-03-09 日産化学工業株式会社 トリフルオロメタンスルホンアニリド化合物の製造方法
CN106699615A (zh) * 2016-12-28 2017-05-24 江苏托球农化股份有限公司 一种三氟甲基亚磺酰氯的生产工艺
CN108003105A (zh) * 2018-01-02 2018-05-08 上海克琴科技有限公司 一种合成小分子氨基酸衍生物依克多因的方法
CN108003105B (zh) * 2018-01-02 2021-09-07 上海克琴科技有限公司 一种合成小分子氨基酸衍生物依克多因的方法

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