WO2013084860A1 - ペンタフルオロスルファニル安息香酸の製造方法 - Google Patents
ペンタフルオロスルファニル安息香酸の製造方法 Download PDFInfo
- Publication number
- WO2013084860A1 WO2013084860A1 PCT/JP2012/081329 JP2012081329W WO2013084860A1 WO 2013084860 A1 WO2013084860 A1 WO 2013084860A1 JP 2012081329 W JP2012081329 W JP 2012081329W WO 2013084860 A1 WO2013084860 A1 WO 2013084860A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- general formula
- atom
- represented
- acid
- group
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/04—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/68—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings containing halogen
- C07C63/70—Monocarboxylic acids
Definitions
- the present invention relates to a method for producing pentafluorosulfanylbenzoic acid.
- Pentafluorosulfanyl benzoic acid is a compound useful as an intermediate raw material for medical and agrochemical products (for example, Patent Documents 1 and 2).
- Patent Documents 1 and 2 Conventionally, as a process for producing pentafluorosulfanylbenzoic acid, 4-nitropentafluorosulfanylbenzene is reduced to obtain 4-aminopentafluorosulfanylbenzene, the compound is reacted with butyl nitrite to diazotize, and then brominated.
- Non-patent Document 1 Bromination with copper (II) to give 4-bromopentafluorosulfanylbenzene, lithiation of the compound with t-butyllithium followed by formylation to give 4-pentafluorosulfanylbenzaldehyde, oxidation of the compound
- a method comprising a step of obtaining 4-pentafluorosulfanylbenzoic acid by oxidation using silver is known (Non-patent Document 1).
- a Grignard reaction reagent is prepared by allowing metal magnesium and methyl iodide to act on 4-bromopentafluorosulfanylbenzene, and the reagent is reacted with carbon dioxide to produce 4-pentafluorosulfanylbenzoic acid.
- a method for obtaining an acid is known (Non-patent Document 2).
- Non-Patent Document 1 has many reaction steps, requires a low-safety diazo compound, and further requires the use of t-butyllithium that easily ignites in air. Therefore, it is not an industrially suitable method. Further, the method described in Non-Patent Document 2 has problems such as complicated preparation of the Grignard reaction reagent and low yield. Furthermore, the method described in Patent Document 1 has a problem that it is necessary to use an expensive catalyst and organotin which is complicated in processing, and the yield is low.
- the present invention provides a simple and safe industrially suitable process for producing pentafluorosulfanylbenzoic acid, and also provides a novel trichloromethylpentafluorosulfanylbenzene suitable for use in the present process. Is an issue.
- (A) A preparation step of preparing trihalomethylpentafluorosulfanylbenzene represented by the general formula (1), (B1) In the presence of an acid other than carboxylic acid, the trihalomethylpentafluorosulfanylbenzene is reacted with carboxylic acid, water, or disiloxane represented by the general formula (b), and the general formula (2a) And (B2) obtaining pentafluorosulfanylbenzoic acid represented by the general formula (2) from the pentafluorosulfanylbenzoic acid halide.
- a method for producing fluorosulfanylbenzoic acid is a method for producing fluorosulfanylbenzoic acid.
- a simple and safe manufacturing method of industrially suitable pentafluorosulfanylbenzoic acid and a novel trichloromethylpentafluorosulfanylbenzene suitable for use in the present manufacturing method can be provided.
- the first manufacturing method is (A) a preparation step of preparing trihalomethylpentafluorosulfanylbenzene represented by the general formula (1); (B1) In the presence of an acid other than a carboxylic acid, the trihalomethylpentafluorosulfanylbenzene is reacted with disiloxane, carboxylic acid, or water represented by the general formula (b) to give a general formula (2a) And (B2) obtaining a pentafluorosulfanylbenzoic acid represented by the general formula (2) from the pentafluorosulfanylbenzoic acid halide.
- a scheme of this production method is shown below.
- X is a halogen atom
- n is an integer of 1 ⁇ n ⁇ 3.
- n is preferably 1.
- the hydrogen atom on the benzene ring may be substituted with a group containing an oxygen atom, a group containing a nitrogen atom, or a halogen atom.
- the hydrogen atom on the benzene ring is a hydrogen atom directly bonded to the carbon atom constituting the benzene ring to which the F 5 S group is bonded.
- each step will be described.
- Trihalomethylpentafluorosulfanylbenzene represented by the general formula (1) is prepared.
- Trihalomethylpentafluorosulfanylbenzene is a general term for compounds having a pentafluorosulfanyl group and a trihalomethyl group on a benzene ring. There may be 1 to 3 trihalomethyl groups. However, since the trihalomethyl group is electron withdrawing and a large number of the group causes steric hindrance, the number of the group is preferably 1 to 2 in view of ease of production and the like. More preferably.
- the halogen atom in the trihalomethyl group is not limited, but a fluorine atom or a chlorine atom is preferable in view of availability of raw materials.
- trichloromethylpentafluorosulfanylbenzene in which the halogen atom is a chlorine atom and n is 1 to 3 is a novel substance.
- the benzene ring in the trihalomethylpentafluorosulfanylbenzene may have a substituent other than the pentafluorosulfanyl and trihalomethyl groups, but is preferably not present from the viewpoint of ease of production.
- trihalomethylpentafluorosulfanylbenzene examples include monotrihalomethylpentafluorosulfanylbenzene such as 4-trihalomethylpentafluorosulfanylbenzene and 3-trihalomethylpentafluorosulfanylbenzene; 3,4-bistrihalomethylpentafluoro Bistrihalomethylpentafluorosulfanylbenzene such as sulfanylbenzene and 3,5-bistrihalomethylpentafluorosulfanylbenzene; 2,4,5-tristrihalomethylpentafluorosulfanylbenzene, 3,4,5-tristrihalomethylpentafluorosulfanyl And tristrihalomethylpentafluorosulfanylbenzene such as benzene.
- monotrihalomethylpentafluorosulfanylbenzene such as 4-trihalomethylpentafluorosulfanylbenzene and 3-tri
- the hydrogen atom on the benzene ring of trihalomethylpentafluorosulfanylbenzene may be substituted with a group containing an oxygen atom, a group containing a nitrogen atom, or a halogen atom.
- the halogen atom is not particularly limited.
- the halogen atom as a substituent may be in the range of 1 to 4, and may be two or more.
- the hydrogen atom on the benzene ring of trihalomethylpentafluorosulfanylbenzene may be substituted with a group containing an oxygen atom.
- groups include hydroxy groups; oxocarbonylalkyl groups such as oxocarbonylmethyl groups and oxocarbonylethyl groups; alkoxyl groups such as methoxy groups, ethoxy groups, and benzyloxy groups; aryloxyl groups such as phenoxy groups and naphthoxy groups.
- the oxocarbonylalkyl group preferably has 2 to 5 carbon atoms, more preferably 2 to 3 carbon atoms.
- the alkoxyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms.
- the aryloxyl group preferably has 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms.
- the hydrogen atom on the benzene ring of trihalomethylpentafluorosulfanylbenzene may be substituted with a group containing a nitrogen atom.
- groups include primary amino groups such as amino group, monomethylamino group, monoethylamino group, monobenzylamino group, phenylamino group; dimethylamino group, diethylamino group, dibenzylamino group, methylethylamino group, Secondary amino group such as phenylmethylamino group and diphenylamino group; primary amide group such as N-acetylamide group, N-benzoylamide group and N-methanesulfonyl group or primary sulfonamide group; N-methyl-N-acetamide Group, secondary amide group such as N-methyl-N-methanesulfonyl group or secondary sulfonamide group.
- the carbon number of the primary amino group is preferably from 0 to 10, and more preferably from 0 to 7.
- the secondary amino group has preferably 2 to 20 carbon atoms, more preferably 2 to 14 carbon atoms.
- the primary amide group or sulfonamide group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
- the carbon number of the secondary amide group or secondary sulfonamide group is preferably 2 to 5, and more preferably 2 to 3.
- the total number of the group containing an oxygen atom and the group containing a nitrogen atom as a substituent may be 1 to 4.
- trihalomethylpentafluorosulfanylbenzenes may be prepared by any method, but are preferably prepared by reacting methylpentafluorosulfanylbenzene represented by the general formula (1a) with a halogenating agent. The scheme of this reaction is shown below.
- n is defined as described above.
- the hydrogen atom on the benzene ring may be substituted with the aforementioned group or atom.
- X in the general formula (1) is a halogen atom.
- the halogenating agent is a compound having an action of substituting hydrogen with halogen.
- halogen molecules such as chlorine molecule, bromine molecule, iodine molecule; sulfuryl chloride, sulfuryl bromide, sulfuryl iodide, etc.
- N-halogenosuccinimide such as N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide
- 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethyl 1,3-dihalogeno-5,5-dimethylhydantoin such as hydantoin and 1,3-diiodo-5,5-dimethylhydantoin
- a chlorine molecule or a bromine molecule is preferable because it is inexpensive, and a chlorine molecule is particularly preferable.
- halogenating agents two or more halogenating agents having the same halogen atom can be used in combination.
- the amount of the halogenating agent to be used is preferably 0.1 to 30 mol, more preferably 3 to 20 mol, per 1 mol of methyl group of methylpentafluorosulfanylbenzene.
- This reaction is preferably carried out under ultraviolet irradiation.
- To carry out the reaction under ultraviolet irradiation is to carry out the reaction in a situation where natural light or light containing ultraviolet rays is irradiated. Halogen radicals are generated by ultraviolet rays, and the reaction proceeds smoothly.
- This reaction does not particularly require a solvent, but a solvent can be used as long as the reaction is not inhibited.
- a solvent include inert solvents such as hydrocarbons such as hexane and heptane, and alkyl halides such as methylene chloride and 1,2-dichloroethane.
- a catalyst may be used.
- radical initiators such as dibenzoyl peroxide and azobisisobutyronitrile
- metal halides such as aluminum chloride, aluminum bromide, aluminum iodide, zinc chloride, zinc bromide and zinc iodide
- Boron halides such as boron, boron bromide and boron iodide
- phosphorus halides such as phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and phosphorus pentabromide can be used, but they are inexpensive and react smoothly.
- phosphorus trichloride or phosphorus pentachloride can be promoted.
- These catalysts may be used alone or in combination of two or more.
- the amount of the catalyst used is preferably 0.001 to 10 mol, preferably 0.005 to 1.0 mol, more preferably 0.01 to 0.3 mol, per 1 mol of methylpentafluorosulfanylbenzene.
- the reaction temperature of this reaction is preferably room temperature to 200 ° C, more preferably 40 to 140 ° C.
- trihalomethylpentafluorosulfanylbenzene represented by the general formula (1) is obtained.
- the compound can be isolated or purified by a general method such as neutralization, extraction, filtration, concentration, distillation, recrystallization, crystallization, sublimation, column chromatography and the like.
- X in the general formula (1) is derived from the halogen atom of the halogenating agent.
- Step (B1) In this step, trihalomethylpentafluorosulfanylbenzene represented by the general formula (1) is reacted with disiloxane, water, or carboxylic acid in the presence of an acid other than the carboxylic acid, and represented by the general formula (2a). The resulting pentafluorosulfanylbenzoic acid halide.
- the scheme of this step is shown below.
- X in the general formula (1) is a fluorine atom
- X in the general formula (2a) is a fluorine atom
- X in the general formula (2a) is a fluorine atom or a halogen atom other than a fluorine atom. That is, in the case where X in the general formula (1) is Cl, X in the general formula (2a) is F or Cl.
- the F atom in this case is considered to be due to the fact that X of the generated compound of the general formula (2a) is fluorinated by HF derived from the compound of the general formula (1).
- the acid other than the carboxylic acid Blensted acid and Lewis acid can be used, but Lewis acid is preferable from the viewpoint of allowing the reaction to proceed efficiently.
- metal chlorides such as aluminum chloride, antimony chloride, ferric chloride, titanium tetrachloride, tin tetrachloride and zinc chloride are preferable, and ferric chloride and zinc chloride are particularly preferable.
- the amount of catalyst added may be any amount that exhibits sufficient activity, but is preferably 0.01 to 50 mol%, more preferably 5 to 30 mol%, relative to trihalomethylpentafluorosulfanylbenzene.
- the amount of water used in this step is preferably 50 to 200 mol% with respect to the compound of general formula (1).
- the concentration of water in the reaction system is rapidly increased, an acid other than the carboxylic acid may be deactivated. Therefore, it is preferable to add water slowly by dropping.
- the reaction temperature is preferably 30 to 180 ° C, more preferably 50 to 120 ° C.
- an acid represented by R ′′ COOH can be used as the carboxylic acid.
- R ′′ is an alkyl group having 1 to 3 carbon atoms or a phenyl group.
- Acetic acid and benzoic acid are preferred as the carboxylic acid because they are easily available, and among them, acetic acid is more preferred because of easy distillation separation.
- the amount of the carboxylic acid is preferably 5 to 120 mol% with respect to the compound of the general formula (1). However, when the concentration of the carboxylic acid in the reaction system rapidly increases, an acid anhydride may be produced as a by-product, so it is preferable to add the carboxylic acid slowly by dropping.
- the reaction temperature is preferably 50 to 140 ° C.
- Carboxylic acid also has an effect of easily dissolving the compound of the general formula (1).
- the specific reaction scheme is as follows.
- the disiloxane used in this step is represented by the general formula (b).
- R is an alkyl group, but from the viewpoint of availability, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is more preferable.
- the usage-amount of disiloxane should just be 50 mol% or more of the compound of General formula (1), and can also be used as a solvent amount.
- Disiloxane also has the advantage of dissolving the raw material in the reactor and allowing the reaction to proceed smoothly.
- the reaction scheme is as follows.
- a halide represented by the general formula (2b) may be generated in addition to the pentafluorosulfanylbenzoic acid halide represented by the general formula (2a).
- the halide represented by the general formula (2b) is considered to be a precursor of the halide represented by the general formula (2a).
- X is defined as described above, and is preferably a chlorine atom.
- R is an alkyl group derived from R of the disiloxane of the general formula (b).
- water and carboxylic acid may be used in combination.
- Water can convert the acid anhydride produced as a by-product when carboxylic acid is used as a reactant into pentafluorosulfanylbenzoic acid which is the object of the present invention.
- carboxylic acid makes it easy to dissolve the compound of the general formula (1) that is difficult to dissolve in water.
- Disiloxane is highly reactive with water, R 3 SiOSiR 3 + H 2 O ⁇ 2R 3 SiOH This is because there is a possibility that disiloxane may be deactivated.
- R 3 SiOH and R 3 SiX produced above regenerate disiloxane of general formula (b) by the following reaction.
- water may be present as long as the amount is small.
- the specific amount of water is preferably 70 mol% or less, more preferably 50 mol% or less, based on disiloxane.
- the halide produced in step (B1) may be subjected to the next step (B2) without isolation or purification.
- the purification step includes distillation or recrystallization, but distillation is preferred.
- the halide represented by the general formula (2a) has a lower boiling point than the pentafluorosulfanylbenzoic acid represented by the general formula (2) and can be easily distilled. Therefore, once the compound of the general formula (2a) is obtained and purified and then subjected to the step (B2), pentafluorosulfanylbenzoic acid having a higher purity can be obtained more efficiently.
- Step (B2) pentafluorosulfanylbenzoic acid is obtained from the halide of the general formula (2a).
- the scheme of this reaction is shown below.
- the target compound of the general formula (2) can be obtained by hydrolyzing the halide of the general formula (2a) using water.
- the amount of water may be at least the stoichiometric amount of pentafluorosulfanylbenzoic acid halide, and may be the amount of solvent.
- the pH of the reaction system is not particularly limited. When the reaction system is alkaline, pentafluorosulfanyl benzoate can be obtained. Therefore, pentafluorosulfanyl benzoic acid can be obtained by adding Bronsted acid to the reaction mixture containing the salt to make it acidic.
- an organic solvent that does not inhibit the reaction can be used in combination.
- organic solvents that can be used include ether solvents such as diethyl ether and tetrahydrofuran, nitrile solvents such as acetonitrile, and alcohol solvents such as methanol and ethanol.
- the reaction temperature is not particularly limited but is preferably 0 to 100 ° C.
- pentafluorosulfanylbenzoic acid can also be obtained from the compound in the step (B2).
- the obtained pentafluorosulfanylbenzoic acid can be isolated or purified by a general method such as neutralization, extraction, filtration, concentration, distillation, recrystallization, crystallization, sublimation, column chromatography and the like.
- Second manufacturing method is: (A) a preparation step of preparing trihalomethylpentafluorosulfanylbenzene represented by the general formula (1); (B1) In the presence of an acid other than a carboxylic acid, the trihalomethylpentafluorosulfanylbenzene is reacted with disiloxane, carboxylic acid, or water represented by the general formula (b) to give a general formula (2a) Producing a pentafluorosulfanylbenzoic acid halide represented by: (C1) an esterification step of reacting the pentafluorosulfanylbenzoic acid halide with an alcohol to produce an ester represented by the general formula (2c), and (C2) from the ester represented by the general formula (2) Obtaining pentafluorosulfanylbenzoic acid.
- Processes (A) and (B1) are as already described.
- the compound represented by the general formula (2b) may be generated.
- the halide is reacted with an alcohol to obtain an ester represented by the general formula (2c).
- R ′ is a linear or branched alkyl group having 1 to 5 carbon atoms.
- the hydrogen atom on the benzene ring may be substituted with a group containing an oxygen atom, a group containing a nitrogen atom, or a halogen atom.
- the alcohol is preferably an alcohol having a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include lower alcohols such as methanol, ethanol, propanol, butanol and pentanol. Of these, methanol and ethanol are preferable from the viewpoint of handleability.
- the esterification reaction is preferably carried out by reacting the pentafluorosulfanylbenzoic acid halide with an excess of alcohol.
- the produced ester can be isolated by purification by distillation or recrystallization.
- it is preferable to add an excess alcohol to the halide and subject it to distillation because pentafluorosulfanyl benzoate can be easily isolated, that is, synthesis and purification of the ester can be performed simultaneously.
- pentafluorosulfanyl benzoic acid with higher purity can be obtained by subjecting the ester to the step (C2).
- this method has an advantage that it can be carried out with a simple apparatus because it is not necessary to purify the compound of the general formula (2a) having high reactivity and corrosivity.
- Step (C2) can be performed by reacting the ester obtained in step (C1) with water and hydrolyzing it. Hydrolysis conditions are as described in the first production method. The scheme of this step is shown below.
- Pentafluorosulfanylbenzoic acid is a compound represented by the general formula (2).
- X is a halogen atom
- n is an integer of 1 ⁇ n ⁇ 3.
- n is preferably 1.
- the hydrogen atom on the benzene ring in the formula may be substituted with a group containing an oxygen atom, a group containing a nitrogen atom, or a halogen atom. This compound is useful as an intermediate for pharmaceuticals and agricultural chemicals.
- Monotrichloromethylpentafluorosulfanylbenzene is a novel substance represented by the formula (5).
- a hydrogen atom on the benzene ring may be substituted with the aforementioned group or atom.
- Monotrichloromethylpentafluorosulfanylbenzene is useful as an intermediate for pentafluorosulfanylbenzoic acid.
- bistrichloromethyl-pentafluorosulfanylbenzene and tristrichloromethylpentafluorosulfanylbenzene are also novel substances.
- Example 1 Synthesis of 4-trichloromethylpentafluorosulfanylbenzene A 100 mL flask equipped with a stirrer was prepared, the inside was replaced with N 2 gas, and then 1.4 g (0.10 mol) of PCl 3 (Sigma-) was added to the flask. Aldrich), followed by 44.1 g (0.20 mol) of 4-methylpentafluorosulfanylbenzene (Ube America). The flask contents were heated to 130 ° C. in an oil bath while stirring, and the reaction vessel was irradiated with light using an incandescent lamp (100 W) (manufactured by ACE GLASS).
- an incandescent lamp 100 W
- the supply of chlorine gas (manufactured by LINWELD) into the flask was started, and the supply of chlorine gas was stopped when 120 L (5.3 mol) was supplied.
- the temperature of the oil bath was set to 50 ° C., and 100 g of 2-propanol was slowly added with stirring.
- 50 g of water was added and stirred while cooling using an ice bath. A white precipitate was obtained immediately upon addition of water.
- the contents were stirred for 30 minutes while the eggplant flask was immersed in an ice bath, and then filtered. The filtrate was washed with 30 g of a cooled mixture of 2-propanol and water (weight ratio 2: 1).
- Example 2 Synthesis of 4-pentafluorosulfanylbenzoic acid (using disiloxane)
- a 100 mL flask equipped with a stirrer 40.0 g (111 mmol) of 4-trichloromethylpentafluorosulfanylbenzene obtained in Example 1, 18.6 g (114 mmol) of hexamethyldisiloxane (manufactured by Sigma-Aldrich), FeCl 3 0.89 g (5 mol%) (manufactured by Sigma-Aldrich) was charged. Under N 2 atmosphere, the bath temperature was set to 70 ° C., and the contents were heated and stirred for 2 days.
- Example 3 Synthesis of 4-pentafluorosulfanylbenzoic acid (using water) To a 50 mL flask equipped with a stirrer was charged 16.08 g (50 mmol) of 4-trichloromethylpentafluorosulfanylbenzene obtained in Example 1 and 406 mg (5 mol%) of FeCl 3 . The bath temperature was raised to 70 to 75 ° C., and 900 mg (50 mmol) of water was slowly added dropwise over 2 hours. HCl gas was generated as it was added. After completion of dropping, the contents were heated and stirred for 1 hour.
- the resulting reaction mixture was transferred to a 200 mL flask, 100 mL of water was added, the oil bath temperature was 90 ° C., and the mixture was stirred overnight. After cooling, the mixture was filtered and the solid was washed 3 times with 20 mL of water. The filtrate was transferred to a flask, 100 mL of 1M NaOH was added, and 50 ml of toluene was added and stirred. Liquid separation was performed, and the aqueous phase was washed again with 50 mL of toluene. After adding 20 mL of 6M HCl to the aqueous phase, the precipitate was dissolved in 50 mL of ethyl acetate and further separated.
- Example 4 Synthesis of 4-pentafluorosulfanylbenzoic acid (via ester)
- 105.8 g (329 mmol) of 4-trichloromethylpentafluorosulfanylbenzene obtained in Example 1, 80.13 g (494 mmol) of hexamethyldisiloxane, and 5.34 g (10 mol%) of FeCl 3 were used.
- the bath temperature was raised to 70 to 75 ° C., and the mixture was heated and stirred for 3 hours.
- 5.34 g (10 mol%) of FeCl 3 was added, and the mixture was further heated and stirred for 16 hours.
- the resulting reaction mixture was cooled to room temperature and 26 ml of ethyl acetate was added.
- a 500 ml flask was charged with 170 ml of ethanol and cooled on ice.
- the reaction mixture was added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and heated to reflux for 2 hours. After cooling to room temperature, 106 ml of hexane was added and ice-cooled. After adding 212 ml of water and stirring well, liquid separation was performed. The aqueous phase was extracted with hexane, combined with the organic phase and washed with 20% brine. The mixture was further washed with saturated aqueous sodium hydrogen carbonate, and concentrated under reduced pressure.
- a 500 ml flask equipped with a stirrer was charged with 76 g (275 mmol) of ethyl 4-pentafluorosulfanylbenzoate, 138 ml of methanol, and 41.2 g (330 mmol) of 45% aqueous potassium hydroxide. After stirring at room temperature for 4 hours, concentration under reduced pressure was performed. After adding 83 ml of water and 83 ml of toluene and stirring well, the liquids were separated. The aqueous phase was ice-cooled, and 152 ml of ethyl acetate and 64 ml of 6M hydrochloric acid were added.
- Example 5 Synthesis of 4-trichloromethylpentafluorosulfanylbenzene (no catalyst) A 100 mL flask equipped with a stirrer was prepared, and the inside was replaced with N 2 gas. Then, 66.1 g (0.30 mol) of 4-methylpentafluorosulfanylbenzene (manufactured by Ube America) was charged into the flask. The flask contents were heated to 90 ° C. in an oil bath while stirring, and the reaction vessel was irradiated with light using a mercury lamp (450 W) (manufactured by ACE GLASS).
- a mercury lamp 450 W
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
[1](A)一般式(1)で表されるトリハロメチルペンタフルオロスルファニルベンゼンを準備する準備工程、
(B1)カルボン酸以外の酸存在下で、当該トリハロメチルペンタフルオロスルファニルベンゼンと、カルボン酸、水、または一般式(b)で表されるジシロキサンとを反応させて、一般式(2a)で表されるペンタフルオロスルファニル安息香酸ハロゲン化物を生成する工程、ならびに
(B2)当該ペンタフルオロスルファニル安息香酸ハロゲン化物から一般式(2)で表されるペンタフルオロスルファニル安息香酸を得る工程、を含む、ペンタフルオロスルファニル安息香酸の製造方法。
[2](A)一般式(1)で表されるトリハロメチルペンタフルオロスルファニルベンゼンを準備する準備工程、
(B1)カルボン酸以外の酸存在下で、当該トリハロメチルペンタフルオロスルファニルベンゼンと、カルボン酸、水、または一般式(b)で表されるジシロキサンとを反応させて、一般式(2a)で表されるペンタフルオロスルファニル安息香酸ハロゲン化物を生成する工程、
(C1)当該ペンタフルオロスルファニル安息香酸ハロゲン化物をアルコールと反応させて、一般式(2c)で表されるエステルを生成する工程、ならびに
(C2)当該ペンタフルオロスルファニル安息香酸エステルから一般式(2)で表されるペンタフルオロスルファニル安息香酸を得る工程、を含む、ペンタフルオロスルファニル安息香酸の製造方法。
1.製造方法
1-1.第一の製造方法
第一の製造方法は、
(A)一般式(1)で表されるトリハロメチルペンタフルオロスルファニルベンゼンを準備する準備工程、
(B1)カルボン酸以外の酸存在下で、当該トリハロメチルペンタフルオロスルファニルベンゼンと、一般式(b)で表されるジシロキサン、カルボン酸、または水、とを反応させて、一般式(2a)で表されるペンタフルオロスルファニル安息香酸ハロゲン化物を生成する工程、ならびに
(B2)当該ペンタフルオロスルファニル安息香酸ハロゲン化物から一般式(2)で表されるペンタフルオロスルファニル安息香酸を得る工程を備える。
本製造方法のスキームを以下に示す。
以下、各工程について説明する。
本工程では、一般式(1)で表されるトリハロメチルペンタフルオロスルファニルベンゼンを準備する。トリハロメチルペンタフルオロスルファニルベンゼンとは、ベンゼン環上にペンタフルオロスルファニル基とトリハロメチル基とを有する化合物の総称である。トリハロメチル基は1~3個存在してよい。しかしながら、トリハロメチル基は電子吸引性であり、また当該基の数が多いと立体障害を引き起こすので、製造容易性等を考慮すると、当該基の数は1~2個であることが好ましく、1個であることがより好ましい。トリハロメチル基におけるハロゲン原子は限定されないが、原料入手容易性等を考慮するとフッ素原子または塩素原子が好ましい。特に、ハロゲン原子が塩素原子でありnが1~3であるトリクロロメチルペンタフルオロスルファニルベンゼンは新規物質である。
置換基としての酸素原子を含む基および窒素原子を含む基の合計の数は1~4個であってよい。
これらのハロゲン化剤としては、同じハロゲン原子を有する二種以上のハロゲン化剤を併用できる。ハロゲン化剤の使用量は、メチルペンタフルオロスルファニルベンゼンのメチル基1モルに対して好ましくは0.1~30モル、さらに好ましくは3~20モルである。
本反応の反応温度は、室温~200℃が好ましく、40~140℃がより好ましい。
本工程では、カルボン酸以外の酸存在下において、一般式(1)で表されるトリハロメチルペンタフルオロスルファニルベンゼンと、ジシロキサン、水、またはカルボン酸を反応させて、一般式(2a)で表されるペンタフルオロスルファニル安息香酸ハロゲン化物を生成する。本工程のスキームを以下に示す。
R3Si-O-SiR3 (b)
式中Rはアルキル基であるが、入手容易性の観点から、炭素数1~5のアルキル基が好ましく、炭素数1~3のアルキル基がより好ましく、メチル基またはエチル基がさらに好ましい。ジシロキサンの使用量は、一般式(1)の化合物の50モル%以上であればよく、溶媒量として用いることもできる。ジシロキサンは反応器内の原料を溶かし、反応を円滑に進行させるという利点もある。反応スキームは以下のとおりである。
R3SiOSiR3 +H2O →2R3SiOH
の反応が生じてジシロキサンが失活される恐れがあるからである。しかし、R3SiOHと上記で生成したR3SiXは以下の反応により、一般式(b)のジシロキサンを再生する。
R3SiOH +R3SiX → R3SiOSiR3 +HX
よって、微量であれば水が存在していてもよい。この場合、具体的な水の量は、ジシロキサンに対して70モル%以下が好ましく、50モル%以下がより好ましい。
本工程では、一般式(2a)のハロゲン化物からペンタフルオロスルファニル安息香酸を得る。本反応のスキームを以下に示す。
前記工程(B1)において、一般式(2b)のハロゲン化物が生成している場合は、工程(B2)において当該化合物からもペンタフルオロスルファニル安息香酸を得ることができる。
第二の製造方法は、
(A)一般式(1)で表されるトリハロメチルペンタフルオロスルファニルベンゼンを準備する準備工程、
(B1)カルボン酸以外の酸存在下で、当該トリハロメチルペンタフルオロスルファニルベンゼンと、一般式(b)で表されるジシロキサン、カルボン酸、または水、とを反応させて、一般式(2a)で表されるペンタフルオロスルファニル安息香酸ハロゲン化物を生成する工程、
(C1)当該ペンタフルオロスルファニル安息香酸ハロゲン化物をアルコールと反応させて、一般式(2c)で表されるエステルを生成するエステル化工程、ならびに
(C2)当該エステルから、一般式(2)で表されるペンタフルオロスルファニル安息香酸を得る工程、を備える。
ペンタフルオロスルファニル安息香酸は、一般式(2)で表される化合物である。
モノトリクロロメチルペンタフルオロスルファニルベンゼンは式(5)で示される新規な物質である。
この他、ビストリクロロメチル-ペンタフルオロスルファニルベンゼンおよびトリストリクロロメチルペンタフルオロスルファニルベンゼンも新規な物質である。
撹拌装置を備える100mLフラスコ準備し、内部をN2ガスで置換した後、フラスコ内にPCl3 1.4g(0.10mol)(Sigma-Aldrich社製)、続いて4-メチルペンタフルオロスルファニルベンゼン44.1g(0.20mol)(ウベアメリカ社製)を仕込んだ。フラスコ内容物を攪拌しながら油浴で130℃に加熱し、白熱灯(100W)(ACE GLASS社製)を用いて反応容器に光を照射した。
1H-NMR (CDCl3):7.84(2H, d, J=9Hz), 8.04(2H, d, J=9Hz)
19F-NMR (CDCl3):62.77(4F, d, J=147Hz), 82.78(1F, quin, J=147Hz)
13C-NMR (CDCl3): 95.9(s), 126.3(s), 126.4(t, JCF=5Hz), 49.2(quin, JCF=20Hz), 147.2(s), 154.8(quin, JCF=18.7Hz)
撹拌装置を備えた100mLフラスコに、実施例1で得た4-トリクロロメチルペンタフルオロスルファニルベンゼン40.0g(111mmol)、ヘキサメチルジシロキサン18.6g(114mmol)(Sigma-Aldrich社製)、FeCl3 0.89g(5mol%)(Sigma-Aldrich社製)を仕込んだ。N2雰囲気下、バス温度を70℃とし、2日間、内容物を加熱撹拌した。内容物を室温まで冷却した後、減圧蒸留を行い、沸点87~94℃(9mmHg)の蒸留物24gを得た。これをGC(Agilent製、6890シリーズ)で分析したところ、4-ペンタフルオロスルファニル安息香酸クロリドと4-ペンタフルオロスルファニル安息香酸フルオリドの混合物(74:24(面積比))であることが分かった。
1H-NMR(CD3CN): 7.91(2H, d, J=8.9Hz), 8.11(2H, d, J=7.9Hz), 9.56(1H, brs, OH)
19F-NMR(CD3CN): 61.78(4F, d, J=147Hz), 82.83(1F, quin, 148Hz)
撹拌装置を備えた50mLフラスコに、実施例1で得た4-トリクロロメチルペンタフルオロスルファニルベンゼン16.08g(50mmol)、FeCl3 406mg(5mol%)を仕込んだ。バス温度を70~75℃に昇温し、水900mg(50mmol)を2時間以上かけてゆっくり滴下した。滴下に従い、HClガスが発生した。滴下終了後、内容物を1時間、加熱撹拌した。得られた反応混合物を200mLフラスコに移し、水100mLを添加し、油浴温度を90℃にして一晩撹拌した。放冷後、濾過し、水20mLを用いて3回固体を洗浄した。ろ過物をフラスコに移し、1MのNaOH 100mLを添加し、トルエン50mlを加えて撹拌した。分液し、水相を再度、トルエン50mLで洗浄した。水相に6MのHCl 20mLを添加した後、酢酸エチル50mLに析出物を溶かし、さらに分液した。水相から有機物を酢酸エチルで抽出し、有機相を飽和食塩水で洗浄した後、無水MgSO4で乾燥した。ろ過後、ろ液を濃縮し、4-ペンタフルオロスルファニル安息香酸10.1gを白色固体として得た(収率81%)。
撹拌装置を備えた500mLフラスコに、実施例1で得た4-トリクロロメチルペンタフルオロスルファニルベンゼン105.8g(329mmol)、ヘキサメチルジシロキサン80.13g(494mmol)、FeCl3 5.34g(10mol%)を仕込んだ。バス温度を70~75℃に昇温し、3時間加熱撹拌した。反応混合物にFeCl3 5.34g(10mol%)を加え、さらに16時間加熱撹拌した。得られた反応混合物を室温まで冷却し、酢酸エチル26mlを加えた。500mlフラスコにエタノール 170mlを仕込み、氷冷した。これに反応混合物を滴下した。滴下終了後、室温で1時間、加熱還流で2時間撹拌した。室温まで冷却後、ヘキサン106mlを添加し、氷冷した。これに水 212mlを添加してよく撹拌した後、分液した。水相をヘキサンで抽出し、有機相と合わせ20%食塩水で洗浄した。さらに飽和重曹水で洗浄した後、減圧濃縮した。得られた褐色油状物を減圧蒸留し、沸点106℃(6mmHg)の蒸留物77gを得た。これをGC分析したところ、エチル4-ペンタフルオロスルファニル安息香酸エステルであった(収率85%)。
撹拌装置を備える100mLフラスコを準備し、内部をN2ガスで置換した後、フラスコ内に4-メチルペンタフルオロスルファニルベンゼン66.1g(0.30mol)(ウベアメリカ社製)を仕込んだ。フラスコ内容物を攪拌しながら油浴で90℃に加熱し、水銀灯(450W)(ACE GLASS社製)を用いて反応容器に光を照射した。
フラスコ内へ塩素ガス(LINWELD社製)の供給を開始し、24時間かけて38L(1.7mol)を供給した時点で塩素ガスの供給を停止した。冷却後、50mlの塩化メチレンを添加し、飽和炭酸ナトリウム水溶液および飽和亜硫酸ナトリウム水溶液で洗浄した。有機相を減圧濃縮し、得られた濃縮物をメタノールと水の混合溶媒から再結晶した。結晶物を減圧乾燥し、4-トリクロロメチルペンタフルオロスルファニルベンゼン 66.7gを得た(収率68%)。
撹拌装置を備えた100mLフラスコに、実施例1で得た4-トリクロロメチルペンタフルオロスルファニルベンゼン 30.0g(93mmol)、ヘキサメチルジシロキサン16.7g(103mmol)、FeCl3 0.75g(5mol%)を仕込んだ。N2雰囲気下、油浴温度を100℃として、2日間、内容物を加熱撹拌した。内容物を室温まで冷却後、減圧蒸留を行った。沸点94℃(6.3mmHg)の蒸留物13.8gを得た。これをGC分析したところ、4-ペンタフルオロスルファニル安息香酸クロリドであることが分かった(収率59%)。本反応においては下記式(2b’)で表されるクロリドも生成していると考えられる(Journal of the Chemical Society, Chemical Communications 1977, 808-809)。R3はメチル基、Xは塩素原子である。
1H-NMR(CDCl3): 7.89(2H, d, J=8.9Hz), 8.21(2H, d, J=8.3Hz)
19F-NMR(CDCl3): 62.16(4F, d, J=147Hz), 81.51(1F, quin, J=150Hz)
撹拌装置を備えた25mLフラスコに、実施例1で得た4-トリクロロメチルペンタフルオロスルファニルベンゼン 10.0g(31.2mmol)、FeCl3 0.15g(3mol%)を仕込んだ。N2雰囲気下、油浴温度を70℃として、酢酸 1.87g(31.2mmol)を3時間かけて滴下した。滴下終了後、油浴温度70℃で17時間、内容物を加熱撹拌した。内容物を室温まで冷却後、トリフェニルホスフィン0.49g(6mol%)を添加し、3時間撹拌した。この混合物を減圧蒸留し、4-ペンタフルオロスルファニル安息香酸クロリド4.67gを得た(収率56%)。
撹拌装置を備えた50mLフラスコに、実施例1で得た4-トリクロロメチルペンタフルオロスルファニルベンゼン16.08g(50mmol)、FeCl3 406mg(5mol%)を仕込んだ。バス温度を70~75℃に昇温し、水900mg(50mmol)を2時間以上かけてゆっくり滴下した。滴下に従い、HClガスが発生した。滴下終了後、内容物を1時間、加熱撹拌した。この混合物を減圧蒸留し、4-ペンタフルオロスルファニル安息香酸クロリド5.59gを得た(収率42%)。
Claims (10)
- (A)一般式(1)で表されるトリハロメチルペンタフルオロスルファニルベンゼンを準備する準備工程
(B1)カルボン酸以外の酸存在下で、当該トリハロメチルペンタフルオロスルファニルベンゼンと、カルボン酸、水、または一般式(b)で表されるジシロキサン
R3Si-O-SiR3 (b)(式中R3はアルキル基を示す)
とを反応させて、一般式(2a)で表されるペンタフルオロスルファニル安息香酸ハロゲン化物を生成する工程
(B2)当該ペンタフルオロスルファニル安息香酸ハロゲン化物から一般式(2)で表されるペンタフルオロスルファニル安息香酸を得る工程
を含む、ペンタフルオロスルファニル安息香酸の製造方法。 - 前記準備工程(A)を紫外線照射下で実施する、請求項2に記載の製造方法。
- 前記工程(B2)の前に、前記工程(B1)で生成したペンタフルオロスルファニル安息香酸ハロゲン化物を含む反応混合物を精製する工程をさらに含む、請求項1~3のいずれかに記載の製造方法。
- (A)一般式(1)で表されるトリハロメチルペンタフルオロスルファニルベンゼンを準備する準備工程
(B1)カルボン酸以外の酸存在下で、当該トリハロメチルペンタフルオロスルファニルベンゼンと、カルボン酸、水、または一般式(b)で表されるジシロキサン
R3Si-O-SiR3 (b)(式中Rはアルキル基を示す)
とを反応させて、一般式(2a)で表されるペンタフルオロスルファニル安息香酸ハロゲン化物を生成する工程
(C1)当該ペンタフルオロスルファニル安息香酸ハロゲン化物をアルコールと反応させて、一般式(2c)で表されるエステルを生成する工程
(C2)当該ペンタフルオロスルファニル安息香酸エステルから一般式(2)で表されるペンタフルオロスルファニル安息香酸を得る工程
を含む、ペンタフルオロスルファニル安息香酸の製造方法。 - 前記準備工程(A)を紫外線照射下で実施する、請求項6に記載の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013548235A JP6124015B2 (ja) | 2011-12-06 | 2012-12-04 | ペンタフルオロスルファニル安息香酸の製造方法 |
US14/362,779 US9102608B2 (en) | 2011-12-06 | 2012-12-04 | Method for producing pentafluorosulfanyl benzoic acid |
CN201280060189.2A CN103974935B (zh) | 2011-12-06 | 2012-12-04 | 五氟硫基苯甲酸的制造方法 |
CA2858157A CA2858157A1 (en) | 2011-12-06 | 2012-12-04 | Method for producing pentafluorosulfanyl benzoic acid |
EP12855616.4A EP2789603B1 (en) | 2011-12-06 | 2012-12-04 | Method for producing pentafluorosulfanyl benzoic acid |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161567474P | 2011-12-06 | 2011-12-06 | |
US61/567474 | 2011-12-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013084860A1 true WO2013084860A1 (ja) | 2013-06-13 |
Family
ID=48574227
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/081329 WO2013084860A1 (ja) | 2011-12-06 | 2012-12-04 | ペンタフルオロスルファニル安息香酸の製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9102608B2 (ja) |
EP (1) | EP2789603B1 (ja) |
JP (1) | JP6124015B2 (ja) |
CN (1) | CN103974935B (ja) |
CA (1) | CA2858157A1 (ja) |
WO (1) | WO2013084860A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019044215A1 (ja) * | 2017-08-29 | 2019-03-07 | 富士フイルム株式会社 | ガス分離膜、ガス分離モジュール、ガス分離装置、ガス分離方法、及びポリイミド化合物 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0532617A (ja) * | 1990-02-28 | 1993-02-09 | Minnesota Mining & Mfg Co <3M> | ペンタフルオロスルフアニル−フルオロ脂肪族カルボニル及びスルホニルフツ化物類、並びにそれら誘導体 |
JP2004067525A (ja) * | 2002-08-01 | 2004-03-04 | Asahi Glass Co Ltd | ペンタフルオロサルファー置換アントラニル酸誘導体の製造方法およびペンタフルオロサルファー置換アントラニル酸誘導体 |
JP2005526138A (ja) * | 2002-05-18 | 2005-09-02 | アベンティス・ファーマ・ドイチユラント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | ペンタフルオロスルファニルベンゾイルグアニジン、それらの製造法、医薬または診断剤としてのそれらの使用、およびそれらを含有する医薬 |
US7622500B2 (en) | 2007-02-21 | 2009-11-24 | Pfizer Limited | Antiparasitic agents |
JP2010518067A (ja) * | 2007-02-09 | 2010-05-27 | ファイザー・リミテッド | 抗寄生虫剤 |
WO2010063767A1 (en) | 2008-12-03 | 2010-06-10 | Novartis Ag | Amidoacetonitrile compounds and pesticidal composition thereof |
WO2011044181A1 (en) * | 2009-10-08 | 2011-04-14 | Schering Corporation | Iminothiadiazine dioxide compounds as bace inhibitors, compositions, and their use |
US20110301382A1 (en) * | 2009-12-07 | 2011-12-08 | Ube Industries, Ltd. | Processes for Preparing 1,3-Dinitro-5-(Pentafluorosulfanyl)Benzene and its Intermediates |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9515599D0 (en) * | 1995-07-29 | 1995-09-27 | British Nuclear Fuels Plc | The preparation of fluorinated organic compounds |
JP4493805B2 (ja) * | 2000-06-27 | 2010-06-30 | 日本軽金属株式会社 | 高純度安息香酸誘導体の製造方法 |
JP5647782B2 (ja) * | 2009-11-09 | 2015-01-07 | 東ソ−・エフテック株式会社 | ハロメチルベンゼン誘導体の製造方法 |
-
2012
- 2012-12-04 EP EP12855616.4A patent/EP2789603B1/en not_active Not-in-force
- 2012-12-04 CA CA2858157A patent/CA2858157A1/en not_active Abandoned
- 2012-12-04 US US14/362,779 patent/US9102608B2/en not_active Expired - Fee Related
- 2012-12-04 CN CN201280060189.2A patent/CN103974935B/zh not_active Expired - Fee Related
- 2012-12-04 JP JP2013548235A patent/JP6124015B2/ja active Active
- 2012-12-04 WO PCT/JP2012/081329 patent/WO2013084860A1/ja active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0532617A (ja) * | 1990-02-28 | 1993-02-09 | Minnesota Mining & Mfg Co <3M> | ペンタフルオロスルフアニル−フルオロ脂肪族カルボニル及びスルホニルフツ化物類、並びにそれら誘導体 |
JP2005526138A (ja) * | 2002-05-18 | 2005-09-02 | アベンティス・ファーマ・ドイチユラント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | ペンタフルオロスルファニルベンゾイルグアニジン、それらの製造法、医薬または診断剤としてのそれらの使用、およびそれらを含有する医薬 |
JP2004067525A (ja) * | 2002-08-01 | 2004-03-04 | Asahi Glass Co Ltd | ペンタフルオロサルファー置換アントラニル酸誘導体の製造方法およびペンタフルオロサルファー置換アントラニル酸誘導体 |
JP2010518067A (ja) * | 2007-02-09 | 2010-05-27 | ファイザー・リミテッド | 抗寄生虫剤 |
US7622500B2 (en) | 2007-02-21 | 2009-11-24 | Pfizer Limited | Antiparasitic agents |
WO2010063767A1 (en) | 2008-12-03 | 2010-06-10 | Novartis Ag | Amidoacetonitrile compounds and pesticidal composition thereof |
WO2011044181A1 (en) * | 2009-10-08 | 2011-04-14 | Schering Corporation | Iminothiadiazine dioxide compounds as bace inhibitors, compositions, and their use |
US20110301382A1 (en) * | 2009-12-07 | 2011-12-08 | Ube Industries, Ltd. | Processes for Preparing 1,3-Dinitro-5-(Pentafluorosulfanyl)Benzene and its Intermediates |
Non-Patent Citations (4)
Title |
---|
JOURNAL OF FLUORINE CHEMISTRY, vol. 128, 2007, pages 1449 - 1453 |
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 84, 1962, pages 3064 - 3072 |
JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, 1977, pages 808 - 809 |
See also references of EP2789603A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019044215A1 (ja) * | 2017-08-29 | 2019-03-07 | 富士フイルム株式会社 | ガス分離膜、ガス分離モジュール、ガス分離装置、ガス分離方法、及びポリイミド化合物 |
Also Published As
Publication number | Publication date |
---|---|
CN103974935B (zh) | 2017-02-22 |
CN103974935A (zh) | 2014-08-06 |
EP2789603A4 (en) | 2015-08-05 |
US9102608B2 (en) | 2015-08-11 |
EP2789603A1 (en) | 2014-10-15 |
CA2858157A1 (en) | 2013-06-13 |
EP2789603B1 (en) | 2016-08-10 |
JPWO2013084860A1 (ja) | 2015-04-27 |
JP6124015B2 (ja) | 2017-05-10 |
US20140336404A1 (en) | 2014-11-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5578809B2 (ja) | 3−メチル−2−チオフェンカルボン酸の製造方法 | |
JP6124015B2 (ja) | ペンタフルオロスルファニル安息香酸の製造方法 | |
JP4511359B2 (ja) | 殺虫剤用の合成中間体を調製するための新規方法 | |
JP4641839B2 (ja) | 4−メチル−3−トリフルオロメチル安息香酸の製造方法 | |
JP2003335735A (ja) | パーフルオロイソプロピルアニリン類の製造方法 | |
JP6086163B2 (ja) | 2’−トリフルオロメチル基置換芳香族ケトンの製造方法 | |
JP3918883B2 (ja) | ベンゾイルクロライド類の製造方法 | |
CN116425623B (zh) | 一锅法合成3,5-二氯-4-甲基苯甲酸的方法 | |
JP4489532B2 (ja) | 3−ホルミル−5−トリフルオロメチルベンゾニトリル誘導体とその製造方法 | |
JP3857369B2 (ja) | 塩素化炭化水素の製造方法 | |
EP1122234A2 (en) | Production methods of alpha, alpha, alpha-trifluoromethylphenyl-substituted benzoic acid and intermediate therefor | |
JP3677786B2 (ja) | アリールオキシプロピオン酸の製造法 | |
JP2996780B2 (ja) | フルオロ置換ベンズアルデヒドの分離方法 | |
JP2008297234A (ja) | ブロモテトラフルオロアルカノール類の製造方法 | |
JP4303685B2 (ja) | 2−シクロペンテン−1−オンの製造方法 | |
JPS62223141A (ja) | アリルエ−テル類の製法 | |
JPH07126198A (ja) | アリルブロミド類の製造方法 | |
JP4956760B2 (ja) | 3−ブロモ安息香酸またはそのアルキルエステルの製造方法 | |
JP2001181228A (ja) | ポリ−(フルオロアルキル)−アセトフェノンの製造方法 | |
JP2004067595A (ja) | トリフルオロメチルフェニル安息香酸エステル誘導体の製造方法 | |
JP2004010486A (ja) | フッ化アリール基含有化合物の製造方法 | |
JP2002069038A (ja) | トリフルオロメチル基含有ベンゾイルギ酸アルキル類、その製造方法およびトリフルオロメチル基含有フェニル酢酸の製造方法 | |
JP5649288B2 (ja) | フタル酸ジクロリド化合物の製造方法及びこの製造方法に用いられる触媒 | |
JPH07165638A (ja) | 新規フルオロベンゾトリクロリド化合物 | |
JP2010159223A (ja) | ヨウ素化合物の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12855616 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2858157 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14362779 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2013548235 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2012855616 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012855616 Country of ref document: EP |