JP2007022953A - MANUFACTURING METHOD OF alpha-FLUOROCYCLIC SULFONES - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a practical method for selectively manufacturing α-fluorocyclic sulfones exhibiting excellent stability. <P>SOLUTION: The cyclic sulfones having a fluorine atom selectively introduced into its α-position is manufactured by causing cyclic sulfoxides or cyclic sulfides having at least one hydrogen atom in the α-position to react with fluorine and water in a liquid phase. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing α-fluoro cyclic sulfones. Specifically, the present invention relates to a method for producing an α-fluoro cyclic sulfone having a fluorine atom selectively introduced at the α-position by reacting a corresponding cyclic sulfoxide or cyclic sulfide with fluorine and water. The α-fluoro cyclic sulfones produced according to the present invention are useful as various solvents, particularly as a medium for immersion exposure in semiconductor production.

The cyclic sulfone compound has a high boiling point, excellent thermal stability, high polarity, and high dielectric constant. Furthermore, since it has a high refractive index as optical characteristics, it is used as an application that requires these characteristics, for example, as a reaction solvent. In the future, it is also promising as a medium for immersion exposure in semiconductor manufacturing.
However, cyclic sulfone compounds generally have a high melting point and viscosity, and their use as a medium is limited. As a method of solving this problem, there is a method of introducing a fluorine atom into a cyclic sulfone compound. In general, by introducing a fluorine atom into a solvent molecule, a decrease in melting point and viscosity can be expected.

  Conventionally, as a method for producing α-fluoroalkylphenyl sulfones, a method in which fluorine gas is allowed to act on a corresponding sulfoxide is known (Non-Patent Documents 1 to 3). In addition, as a method for producing fluorocyclic sulfones, a synthesis method of 3,4-difluorosulfolane in which sulfolene and fluorine gas are reacted (Non-patent Document 4) and a method in which sulfolane is directly contacted with fluorine gas (Patent Document 1). In any case, a compound in which the β-position is fluorinated with respect to the sulfur atom is obtained as the main product. Due to the high electron-withdrawing property of the sulfone group, β-fluoro cyclic sulfones are unstable because the α-position hydrogen atom and β-position fluorine atom, which have high acidity, are easily removed as hydrogen fluoride. Although α-fluoro cyclic sulfones are excellent in stability, no method for selectively producing them has been known.

Japanese Patent Laid-Open No. 2002-47286 Chem. Lett. , 581 (1995) Chem. Pharm. Bull. 44,703, (1996) Tetrahedron Lett. , 37, 8507, (1996) J. et al. Fluorine Chem. 93, 27 (1999).

  The present invention provides a method for selectively producing α-fluoro cyclic sulfones.

  The present invention provides the following method for producing an α-fluoro cyclic sulfone characterized by reacting a cyclic sulfoxide or a cyclic sulfide with fluorine and water.

[1] A method for producing an α-fluoro cyclic sulfone, comprising reacting cyclic sulfoxides and / or cyclic sulfides having at least one hydrogen atom at the α-position with fluorine and water in a liquid phase.
[2] A cyclic sulfoxide is a compound represented by the following formula (I), a cyclic sulfide is a compound represented by the following formula (II), and an α-fluoro cyclic sulfone is represented by the following formula (III): The production method according to the above [1], which is a compound represented.

However, R < ¹ > -R < ⁴ > shows a hydrogen atom or a C1-C10 alkyl group each independently, and at least one is a hydrogen atom.
R ^1F to R ^4F is ^R 1F ^{to R 4F} corresponding to ^R 1 to R ⁴ is an alkyl group having 1 to 10 carbon atoms ^is an R 1 to R ⁴ the same alkyl group having 1 to 10 carbon atoms , ^R 1F ^{to R 4F} corresponding to ^R 1 to R ⁴ is a hydrogen atom is a fluorine atom or a hydrogen atom, and the number of ^R 1F ^{to R 4F} is a fluorine atom is 1 or 2.
Q represents a group represented by the formula — (CH ₂ ) _m —, or a group in which at least one hydrogen atom of the group is substituted with an alkyl group. Here, m is an integer of 0-4. However, when m is 0, Q represents a single bond.
[3] The production method according to the above [2], wherein Q is a group represented by the formula — (CH ₂ ) ₂ — or a group in which at least one hydrogen atom of the group is substituted with an alkyl group.
[4] The production method according to any one of the above [1] to [3], wherein a fluorine gas is passed through a solution in which cyclic sulfoxides and / or cyclic sulfides are dissolved in a solvent to cause the reaction with fluorine.
[5] The production method according to the above [4], wherein the solvent has a lone electron pair and has a functional group.
[6] The production method according to the above [4] or [5], wherein the functional group is selected from the group consisting of a nitrile group, an ether group, a hydroxyl group, a tertiary amino group, a halogen group, a nitro group and an amide group.
[7] The production method according to any one of [4] to [6], wherein the solvent is a nitrile solvent.
[8] The production method according to any one of [4] to [7], wherein the fluorine gas is diluted with nitrogen or helium.
[9] The production method according to any one of [1] to [8], wherein a metal salt is present when reacting with fluorine and water.
[10] The production method of the above-mentioned [9], wherein the metal salt is an alkali metal fluoride or a transition acid strong acid salt.
[11] The method according to [9] or [10], wherein the metal salt is a metal salt selected from the group consisting of sodium fluoride, potassium fluoride, cesium fluoride, copper nitrate, nickel nitrate, and cobalt nitrate. .

  The novel method for producing α-fluorocyclic sulfones of the present invention is useful as a method for selectively producing cyclic sulfones in which the α-position is fluorine-substituted. α-Fluorocyclic sulfones are particularly useful as an immersion exposure medium in semiconductor production.

The cyclic sulfoxides and cyclic sulfides in the present invention are cyclic sulfoxides and cyclic sulfides having at least one hydrogen atom at the α-position or a substituted product thereof. The substituent is a compound in which a substituent is bonded to a carbon atom forming a ring of cyclic sulfoxide and cyclic sulfide, and the substituent is preferably an alkyl group having 1 to 10 carbon atoms. Although 1 to 4 hydrogen atoms may exist at the α-position of the cyclic sulfoxides and cyclic sulfides, the number of hydrogen atoms present at the α-position is not limited in the present invention.
In general, the cyclic sulfoxide structure or the cyclic sulfide structure is preferably a 3- to 7-membered ring. When the product is used as a solvent, a 3- to 5-membered ring is preferable. As the cyclic sulfoxide, a compound represented by the formula (I) is preferable, and as the cyclic sulfide, a compound represented by the formula (II) is preferable. (Hereinafter referred to as compounds (I) and (II). Similarly, a compound represented by formula (X) will be referred to as compound (X).)

However, R < ¹ > -R < ⁴ > shows a hydrogen atom or a C1-C10 alkyl group each independently, and at least one is a hydrogen atom.
In the compounds (I) and (II), the alkyl group as R ^{1 to} R ⁴ may be linear or branched and has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Moreover, when there are a plurality of alkyl groups, they may be the same or different. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and the like.

Q represents a group represented by the formula — (CH ₂ ) _m —, or a group in which at least one hydrogen atom of the group is substituted with an alkyl group. Here, m is an integer of 0-4. However, when m is 0, Q represents a single bond. The number of alkyl groups that Q may have as a substituent is preferably 1-2. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and the like.

Specific examples of cyclic sulfoxides include cyclic sulfoxides in which the alkyl group is not substituted, monoalkyl substituted products, dialkyl substituted products in which the alkyl group is substituted with the same carbon atom, dialkyl substituted products in which the alkyl group is substituted with a different carbon atom Etc.
Examples of the cyclic sulfoxides in which the alkyl group is not changed include ethylene sulfoxide, trimethylene sulfoxide, tetramethylene sulfoxide, pentamethylene sulfoxide, hexamethylene sulfoxide and the like.

  Examples of monoalkyl-substituted cyclic sulfoxides include the following. 2-methylethylene sulfoxide, 2-ethylethylene sulfoxide, 2-methyltrimethylene sulfoxide, 2-ethyltrimethylene sulfoxide, 3-methyltrimethylene sulfoxide, 3-ethyltrimethylene sulfoxide, 2-methyltetramethylene sulfoxide, 2-ethyl Tetramethylene sulfoxide, 3-methyltetramethylene sulfoxide, 3-ethyltetramethylene sulfoxide, 2-methylpentamethylene sulfoxide, 2-ethylpentamethylene sulfoxide, 3-methylpentamethylene sulfoxide, 3-ethylpentamethylene sulfoxide, 4-methylpenta Methylene sulfoxide, 4-ethylpentamethylene sulfoxide, 2-methylhexamethylene sulfoxide, 2-ethylhexamethylene sulfoxide, 3 Hexamethylene sulfoxide, 3-ethyl-hexamethylene sulfoxide, 4-methyl hexamethylene sulfoxide, 4-ethyl-hexamethylene sulfoxide.

  Examples of dialkyl-substituted cyclic sulfoxides in which an alkyl group is substituted on the same carbon atom include the following examples. 2,2-dimethylethylene sulfoxide, 2,2-diethylethylene sulfoxide, 2-ethyl-2-methylethylene sulfoxide, 2,2-dimethyltrimethylene sulfoxide, 2,2-diethyltrimethylene sulfoxide, 2-ethyl-2- Methyltrimethylene sulfoxide, 3,3-dimethyltrimethylene sulfoxide, 3,3-diethyltrimethylene sulfoxide, 3-ethyl-3-methyltrimethylene sulfoxide, 2,2-dimethyltetramethylene sulfoxide, 2,2-diethyltetramethylene Sulfoxide, 2-ethyl-2-methyltetramethylene sulfoxide, 3,3-dimethyltetramethylene sulfoxide, 3,3-diethyltetramethylene sulfoxide, 3-ethyl-3-methyltetramethylene sulfoxide, 2,2 Dimethylpentamethylene sulfoxide, 2,2-diethylpentamethylene sulfoxide, 2-ethyl-2-methylpentamethylene sulfoxide, 3,3-dimethylpentamethylene sulfoxide, 3,3-diethylpentamethylene sulfoxide, 3-ethyl-3-methyl Pentamethylene sulfoxide, 4,4-dimethylpentamethylene sulfoxide, 4,4-diethylpentamethylene sulfoxide, 4-ethyl-4-methylpentamethylene sulfoxide, 2,2-dimethylhexamethylene sulfoxide, 2,2-diethylhexamethylene sulfoxide 2-ethyl-2-methylhexamethylene sulfoxide, 3,3-dimethylhexamethylene sulfoxide, 3,3-diethylhexamethylene sulfoxide, 3-ethyl-3-methylhexamethyl Nsuruhokishido, 4,4-dimethyl hexamethylene sulfoxide, 4,4-diethyl hexamethylene sulfoxide, 4-ethyl-4-methyl hexamethylene sulfoxide.

  Examples of the dialkyl-substituted cyclic sulfoxides in which the alkyl group is substituted with a different carbon atom include the following examples. 2,3-dimethylethylene sulfoxide, 2,3-diethylethylene sulfoxide, 2-ethyl-3-methylethylene sulfoxide, 2,3-dimethyltrimethylene sulfoxide, 2,3-diethyltrimethylene sulfoxide, 2-ethyl-3- Methyl trimethylene sulfoxide, 3-ethyl-2-methyl trimethylene sulfoxide, 2,4-dimethyl trimethylene sulfoxide, 2,4-diethyl trimethylene sulfoxide, 2-ethyl-4-methyl trimethylene sulfoxide, 2,3-dimethyl Tetramethylene sulfoxide, 2,3-diethyltetramethylene sulfoxide, 2-ethyl-3-methyltetramethylene sulfoxide, 3-ethyl-2-methyltetramethylene sulfoxide, 2,4-dimethyltetramethylene sulfoxide, 2 4-diethyltetramethylene sulfoxide, 2-ethyl-4-methyltetramethylene sulfoxide, 2,5-dimethyltetramethylene sulfoxide, 2,5-diethyltetramethylene sulfoxide, 2-ethyl-5-methyltetramethylene sulfoxide, 2,3 -Dimethylpentamethylene sulfoxide, 2,3-diethylpentamethylene sulfoxide, 2-ethyl-3-methylpentamethylene sulfoxide, 3-ethyl-2-methylpentamethylene sulfoxide, 2,4-dimethylpentamethylene sulfoxide.

  2,4-diethylpentamethylene sulfoxide, 2-ethyl-4-methylpentamethylene sulfoxide, 4-ethyl-2-methylpentamethylene sulfoxide, 2,5-dimethylpentamethylene sulfoxide, 2,5-diethylpentamethylene sulfoxide, 2, -Ethyl-5-methylpentamethylene sulfoxide, 5-ethyl-2-methylpentamethylene sulfoxide, 2,6-dimethylpentamethylene sulfoxide, 2,6-diethylpentamethylene sulfoxide, 2-ethyl-6-methylpentamethylene sulfoxide, 2,3-dimethylhexamethylene sulfoxide, 2,3-diethylhexamethylene sulfoxide, 2-ethyl-3-methylhexamethylene sulfoxide, 3-ethyl-2-methylhexamethylene sulfoxide, 2,4- Methylhexamethylene sulfoxide, 2,4-diethylhexamethylene sulfoxide, 2-ethyl-4-methylhexamethylene sulfoxide, 4-ethyl-2-methylhexamethylene sulfoxide, 2,5-dimethylhexamethylene sulfoxide, 2,5-diethyl Hexamethylene sulfoxide, 2-ethyl-5-methylhexamethylene sulfoxide, 5-ethyl-2-methylhexamethylene sulfoxide, 2,6-dimethylhexamethylene sulfoxide, 2,6-diethylhexamethylene sulfoxide, 2-ethyl-6- Methylhexamethylene sulfoxide, 6-ethyl-2-methylhexamethylene sulfoxide, 2,7-dimethylhexamethylene sulfoxide, 2,7-diethylhexamethylene sulfoxide, 2-ethyl-7-methyl Hexamethylene sulfoxide.

  Specific examples of sulfides include sulfides in which> S═O is replaced by —S— in each of the exemplified compounds of the sulfoxides.

  The cyclic sulfoxides and / or cyclic sulfides of the present invention (hereinafter collectively referred to as a substrate) react with fluorine and water to fluorinate an α-position hydrogen atom and sulfonate a sulfur atom. Occurs and is converted to α-fluoro cyclic sulfones. As the substrate, cyclic sulfoxides and cyclic sulfides may be used alone or in combination.

In the present invention, the substrate is reacted in the liquid phase. That is, when the substrate itself is a liquid under the reaction conditions, the substrate may be used as it is, or a substrate obtained by dissolving the substrate in a solvent may be used.
As the solvent in the case of using a solvent, a solvent having a low reactivity with respect to fluorine as compared with the substrate and a solvent that polarizes fluorine molecules is preferable. Moreover, even if it is a solvent that can react with fluorine, a solvent (for example, an alcohol solvent) in which the compound formed by the reaction of the solvent and fluorine can be a fluorinating agent that fluorinates the substrate is preferable. Further, as the solvent, a solvent having a lone electron pair and a functional group is preferable, and a solvent having a high dielectric constant is preferably selected from the solvents. Examples of functional groups include nitrile groups, ether groups, hydroxyl groups, tertiary amino groups, halogen groups, nitro groups, and amide groups.

Examples of the solvent having a lone electron pair and a functional group include nitrile solvents, ether solvents, alcohol solvents, amine solvents, chlorine solvents, nitro solvents, and alkylformamide solvents, and nitrile solvents are preferred. . 1 type (s) or 2 or more types can be used for a solvent.
Specific examples of the solvent include the following examples. Acetonitrile, propanenitrile, tert-butyl methyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2,2 , 2-trifluoroethanol, perfluorotriethylamine, perfluorotri-n-butylamine, methylene chloride, chloroform, nitromethane, nitroethane and dimethylformamide. In particular, acetonitrile and propanenitrile are preferable.
The amount of the solvent used depends on the solubility of the substrate in the solvent, but is preferably 0.1 times or more, more preferably 1 to 1000 times the weight of the substrate.

  As fluorine, it is preferable to use fluorine gas as it is or fluorine gas diluted with an inert gas. As the inert gas, nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable for economical reasons. The ratio of the fluorine gas in nitrogen gas is not specifically limited, 0.5 to 50% is preferable and 2 to 25% is more preferable. Fluorine is considered to react with a substrate after being dissolved in a liquid substrate or a liquid containing the substrate.

  The reaction type of the fluorination reaction may be a batch type or a continuous type. For example, there is a method in which a substrate and a solvent are charged into a reactor, and the reaction is carried out while continuously supplying fluorine gas to the solution while stirring. Further, this reaction may be carried out by a method in which a substrate solution and fluorine gas are continuously supplied and reacted at a constant ratio using an apparatus such as a microreactor.

  The amount of fluorine gas used in this reaction is preferably from 0.1 to 20 times mol, particularly preferably from 1 to 10 times mol to the substrate.

  Since this reaction involves a large exotherm, it is necessary to carry out the reaction while sufficiently removing heat. Therefore, the lower limit of the reaction temperature is preferably around the melting point of the solvent when a solvent is used, and around the melting point of the substrate when no solvent is used. In the usual case, the reaction temperature is preferably −100 ° C. to + 50 ° C., particularly preferably −50 to + 20 ° C., from the viewpoint of reaction yield, selectivity, and ease of industrial implementation.

In the reaction of the present invention, a substrate is reacted with fluorine and water. When the substrate is a cyclic sulfoxide, the amount of water is preferably 1 to 1000-fold mol with respect to the substrate, and when the substrate is a cyclic sulfide, it is preferably 2 to 1000-fold mol with respect to the substrate. Water may be present in the reaction system from the beginning of the reaction, or may be added to the reaction system after the reaction with fluorine is completed, and the reaction is divided into two stages after the reaction and after the reaction with fluorine. It may be added to the system.
When the substrate is a cyclic sulfoxide, it is preferable to add water to the reaction system after the reaction with fluorine is completed. When the substrate is a cyclic sulfide, it is preferably present in the reaction system from the beginning of the reaction. The amount of water in the case of adding at the beginning of the reaction is preferably a small amount, and preferably 0.5 to 1.5 moles relative to the substrate. Moreover, when the metal salt mentioned later is a hydrate, the water as a hydrate also becomes water involved in the reaction. Water can also act as a reaction solvent.

  In the reaction of the present invention, when a metal salt is allowed to coexist in the reaction system, it is preferable because by-product of a tar-like substance that causes a decrease in yield can be suppressed. Examples of the metal salt include alkali metal fluorides or strong transition metal salts. As the alkali metal fluoride, sodium fluoride, potassium fluoride and cesium fluoride are preferable, and sodium fluoride and potassium fluoride are particularly preferable from an economical viewpoint. As the strong acid salt of the transition metal, copper, nickel, cobalt nitrate, perchlorate, trifluoromethanesulfonate, sulfate, tetrafluoroborate, and perchlorate are preferable. Specifically, copper (II) nitrate, copper (II) perchlorate, copper (II) trifluoromethanesulfonate, copper (II) sulfate, copper (II) tetrafluoroborate, nickel (II) nitrate, nickel sulfate ( II), cobalt nitrate (II), cobalt perchlorate (II), cobalt sulfate (II), cobalt tetrafluoroborate (II) and the like are preferable, copper nitrate (II), nickel nitrate (II), cobalt nitrate (II) Is particularly preferred. Further, the strong acid salt of the transition metal may be used in the form of a hydrate. In the case of an alkali metal fluoride, the amount of the metal salt to be used is preferably 1 to 30-fold mol, particularly preferably 5 to 20-fold mol based on the substrate. In the case of a strong transition metal salt, a catalytic amount may be used, and it is preferably 0.01 to 0.5-fold mol, particularly preferably 0.02 to 0.2-fold mol based on the substrate.

The α-fluorocyclic sulfones generated by the reaction of the present invention are sulfonic acids having at least one fluorine atom at the α-position or a substituted product thereof. The substituent is a compound in which a substituent is bonded to a carbon atom forming a ring of sulfonic acid, and the substituent is preferably an alkyl group having 1 to 10 carbon atoms. Although a maximum of 4 fluorine atoms can exist at the α-position, the number of fluorine atoms present at the α-position is preferably 1 or 2 in the present invention. Furthermore, α, α′-difluorocyclic sulfones are preferable as the α-fluoro cyclic sulfones having two fluorine atoms.
When the reaction of the present invention is carried out in the aforementioned compound (I) and / or compound (II), the following compound (III) is produced as α-fluoro cyclic sulfones.

In the formula, the meaning of Q is the same as in the compounds (I) and (II). R ^1F to R ^4F is ^R 1F ^{to R 4F} corresponding to ^R 1 to R ⁴ is an alkyl group having 1 to 10 carbon atoms ^is an R 1 to R ⁴ the same alkyl group having 1 to 10 carbon atoms , ^R 1F ^{to R 4F} corresponding to ^R 1 to R ⁴ is a hydrogen atom is a fluorine atom or a hydrogen atom, and the number of ^R 1F ^{to R 4F} is a fluorine atom is 1 or 2. Only when R ^{1 to} R ⁴ are hydrogen atoms, substitution with fluorine atoms occurs. The alkyl group does not change before and after the reaction. That is, R ^{1F to} R ^4F corresponding to R ^{1 to} R ⁴ , which is an alkyl group having 1 to 10 carbon atoms, represents the same alkyl group as R ^{1 to} R ⁴ .

Here, the number of hydrogen atoms at the α-position in the above cyclic sulfoxides or cyclic sulfides is a maximum of 4, so that the obtained α-fluoro cyclic sulfones have various substitutions from monofluoro, difluoro to tetrafluoro forms. The body is considered. In the method of the present application, a monofluoro form and / or a difluoro form are mainly obtained. Therefore, when ^{1 to 4} of R ^{1 to} R ⁴ are hydrogen atoms, 1 or 2 of the hydrogen atoms are fluorinated. Fluorine substitution tends to occur easily on a hydrogen atom bonded to a carbon atom substituted by an alkyl group having 1 to 10 carbon atoms.

There are two types of difluoro compounds: α, α-difluoro compounds and α, α′-difluoro compounds for which no conventional production method has been known. According to the method of the present application, α, α′-difluorocyclic sulfones can be obtained with high selectivity by adjusting the reaction conditions. Specifically, when α, α, α ′, α′-tetrahydro form (—CH ₂ —S (O) —CH ₂ —) is used as a substrate, α, α′-difluoro form (—CHF—S (O ) _2- CHF-) is the main product. When α, α, α′-trihydro-α′-monoalkyl (—CH ₂ —S (O) —CHR—) is used as a substrate, α, α′-difluoro (—CHF—S (O) ₂ -CFR-) is the main product. The α, α′-difluoro product is thought to be formed because it is difficult for the remaining hydrogen atoms to escape when one fluorine atom is substituted.
In addition, the reaction of the present invention does not have stereoselectivity but has regioselectivity. Thus, if the product contains cis / trans, enantiomers, all of them are included.

Specific examples of the α-fluoro cyclic sulfones produced by the reaction of the present invention are shown below.
Examples of α-monofluorocyclic sulfones obtained from cyclic sulfoxides and cyclic sulfides in which the alkyl group is not substituted include the following compounds.
2-fluoroethylene sulfone, 2-fluorotrimethylene sulfone, 2-fluorotetramethylene sulfone, 2-fluoropentamethylene sulfone, 2-fluorohexamethylene sulfone and the like.

Examples of α-monofluorocyclic sulfones obtained from monoalkyl-substituted cyclic sulfoxides and cyclic sulfides include the following.
2-Fluoro-2-methylethylenesulfone, 2-fluoro-3-methylethylenesulfone, 2-ethyl-2-fluoroethylenesulfone, 2-ethyl-3-fluoroethylenesulfone, 2-fluoro-2-methyltrimethylenesulfone 2-fluoro-4-methyltrimethylenesulfone, 2-ethyl-2-fluorotrimethylenesulfone, 2-ethyl-4-fluorotrimethylenesulfone, 2-fluoro-3-methyltrimethylenesulfone, 2-fluoro-3 -Ethyltrimethylenesulfone, 2-fluoro-2-methyltetramethylenesulfone, 2-fluoro-5-methyltetramethylenesulfone, 2-ethyl-2-fluorotetramethylenesulfone, 2-ethyl-5-fluorotetramethylenesulfone, 2-Fluoro-3-methyltetra Tylene sulfone, 2-fluoro-4-methyltetramethylene sulfone, 3-ethyl-2-fluorotetramethylene sulfone, 4-ethyl-2-fluorotetramethylene sulfone, 2-fluoro-2-methylpentamethylene sulfone, 2-fluoro -6-methylpentamethylenesulfone, 2-ethyl-2-fluoropentamethylenesulfone.

  2-ethyl-6-fluoropentamethylenesulfone, 2-fluoro-3-methylpentamethylenesulfone, 2-fluoro-5-methylpentamethylenesulfone, 3-ethyl-2-fluoropentamethylenesulfone, 5-ethyl-2- Fluoropentamethylenesulfone, 2-fluoro-4-methylpentamethylenesulfone, 4-ethyl-2-fluoropentamethylenesulfone, 2-fluoro-2-methylhexamethylenesulfone, 2-fluoro-7-methylhexamethylenesulfone, 2 -Ethyl-2-fluorohexamethylenesulfone, 2-ethyl-7-fluorohexamethylenesulfone, 2-fluoro-3-methylhexamethylenesulfone, 2-fluoro-6-methylhexamethylenesulfone, 3-ethyl-2-fluoro Hexamethylenesulfur 6-ethyl-2-fluorohexamethylene sulfone, 2-fluoro-4-methylhexamethylene sulfone, 2-fluoro-5-methylhexamethylene sulfone, 4-ethyl-2-fluorohexamethylene sulfone, 5-ethyl- 2-fluorohexamethylene sulfone and the like.

Examples of α-monofluorocyclic sulfones obtained from cyclic sulfoxides and cyclic sulfides in which two alkyl groups are dialkyl-substituted at the same carbon atom include the following.
3-fluoro-2,2-dimethylethylenesulfone, 2,2-diethyl-3-fluoroethylenesulfone, 2-ethyl-3-fluoro-2-methylethylenesulfone, 4-fluoro-2,2-dimethyltrimethylenesulfone 2,2-diethyl-4-fluorotrimethylenesulfone, 2-ethyl-4-fluoro-2-methyltrimethylenesulfone, 2-fluoro-3,3-dimethyltrimethylenesulfone, 3,3-diethyl-2- Fluorotrimethylene sulfone, 3-ethyl-2-fluoro-3-methyltrimethylene sulfone, 5-fluoro-2,2-dimethyltetramethylene sulfone, 2,2-diethyl-5-fluorotetramethylene sulfone, 2-ethyl- 5-Fluoro-2-methyltetramethylene sulfone, 2-fluoro-3,3-di Tyltetramethylenesulfone, 2-fluoro-4,4-dimethyltetramethylenesulfone, 3,3-diethyl-2-fluorotetramethylenesulfone, 4,4-diethyl-2-fluorotetramethylenesulfone, 3-ethyl-2- Fluoro-3-methyltetramethylene sulfone, 4-ethyl-2-fluoro-4-methyltetramethylene sulfone.

  6-fluoro-2,2-dimethylpentamethylenesulfone, 2,2-diethyl-6-fluoropentamethylenesulfone, 2-ethyl-6-fluoro-2-methylpentamethylenesulfone, 2-fluoro-3,3-dimethyl Pentamethylene sulfone, 2-fluoro-5,5-dimethylpentamethylene sulfone, 3,3-diethyl-2-fluoropentamethylene sulfone, 3,3-diethyl-6-fluoropentamethylene sulfone, 3-ethyl-2-fluoro -3-methylpentamethylene sulfone, 3-ethyl-6-fluoro-3-methylpentamethylene sulfone, 2-fluoro-4,4-dimethylpentamethylene sulfone, 4,4-diethyl-2-fluoro-pentamethylene sulfone, 4-ethyl-2-fluoro-4-methylpentamethylenes Hong, 7-fluoro-2,2-dimethylhexamethylenesulfone, 2,2-diethyl-7-fluorohexamethylenesulfone, 2-ethyl-7-fluoro-2-methylhexamethylenesulfone, 2-fluoro-3,3 -Dimethylhexamethylene sulfone, 7-fluoro-3,3-dimethylhexamethylene sulfone, 3,3-diethyl-2-fluorohexamethylene sulfone, 3,3-diethyl-7-fluorohexamethylene sulfone, 3-ethyl-2 -Fluoro-3-methylhexamethylenesulfone, 3-ethyl-7-fluoro-3-methylhexamethylenesulfone, 2-fluoro-4,4-dimethylhexamethylenesulfone, 2-fluoro-5,5-dimethylhexamethylenesulfone 4,4-Diethyl-2-fluorohexamethylenes Hong, 5,5-diethyl-2-fluoro-hexamethylene sulfone, 4-ethyl-2-fluoro-4-methyl-hexamethylene sulfone, 5-ethyl-2-fluoro-5-methyl-hexamethylene sulfone.

Examples of α-monofluorocyclic sulfones obtained from cyclic sulfoxides and cyclic sulfides in which two alkyl groups are dialkyl-substituted on different carbon atoms include the following.
2-fluoro-2,3-dimethylethylenesulfone, 2,3-diethyl-2-fluoroethylenesulfone, 2-ethyl-2-fluoro-3-methylethylenesulfone, 3-ethyl-2-fluoro-2-methylethylene Sulfone, 2-fluoro-2,3-dimethyltrimethylenesulfone, 2-fluoro-3,4-dimethyltrimethylenesulfone, 2,3-diethyl-2-fluorotrimethylenesulfone, 2,3-diethyl-4-fluoro Trimethylenesulfone, 2-ethyl-2-fluoro-3-methyltrimethylenesulfone, 2-ethyl-4-fluoro-3-methyltrimethylenesulfone, 3-ethyl-2-fluoro-2-methyltrimethylenesulfone, 3 -Ethyl-2-fluoro-4-methyltrimethylene sulfone, 2-fluoro-2,4- Methyltrimethylenesulfone, 2,4-diethyl-2-fluorotrimethylenesulfone, 2-ethyl-2-fluoro-4-methyltrimethylenesulfone, 4-ethyl-2-fluoro-2-methyltrimethylenesulfone, 2- Fluoro-2,3-dimethyltetramethylene sulfone.

  5-fluoro-2,3-dimethyltetramethylenesulfone, 2,3-diethyl-2-fluorotetramethylenesulfone, 2,3-diethyl-5-fluorotetramethylenesulfone, 2-ethyl-2-fluoro-3-methyl Tetramethylenesulfone, 2-ethyl-5-fluoro-3-methyltetramethylenesulfone, 3-ethyl-2-fluoro-2-methyltetramethylenesulfone, 3-ethyl-5-fluoro-2-methyltetramethylenesulfone, 2 -Fluoro-2,4-dimethyltetramethylenesulfone, 2-fluoro-3,5-dimethyltetramethylenesulfone, 2,4-diethyl-2-fluorotetramethylenesulfone, 3,5-diethyl-2-fluorotetramethylenesulfone 2-Ethyl-2-fluoro-4-methyltetramethyle Sulfone, 5-ethyl-2-fluoro-3-methyltetramethylenesulfone, 2-fluoro-2,5-dimethyltetramethylenesulfone, 2,5-diethyl-2-fluorotetramethylenesulfone, 2-ethyl-2-fluoro -5-methyltetramethylenesulfone, 5-ethyl-2-fluoro-2-methyltetramethylenesulfone, 2-fluoro-2,3-dimethylpentamethylenesulfone, 6-fluoro-2,3-dimethylpentamethylenesulfone, 2 , 3-Diethyl-2-fluoropentamethylene sulfone, 2,3-diethyl-6-fluoropentamethylene sulfone, 2-ethyl-2-fluoro-3-methylpentamethylene sulfone, 2-ethyl-6-fluoro-3- Methyl pentamethylene sulfone.

  3-ethyl-2-fluoro-2-methylpentamethylenesulfone, 3-ethyl-6-fluoro-2-methylpentamethylenesulfone, 2-fluoro-2,4-dimethylpentamethylenesulfone, 2-fluoro-4,6 -Dimethylpentamethylenesulfone, 2,4-diethyl-2-fluoropentamethylenesulfone, 2,4-diethyl-6-fluoropentamethylenesulfone, 2-ethyl-2-fluoro-4-methylpentamethylenesulfone, 2-ethyl -6-fluoro-4-methylpentamethylenesulfone, 4-ethyl-2-fluoro-2-methylpentamethylenesulfone, 4-ethyl-2-fluoro-6-methylpentamethylenesulfone, 2-fluoro-2,5- Dimethylpentamethylene sulfone, 2-fluoro-3,6-dimethylpenta Tylene sulfone, 2,5-diethyl-2-fluoropentamethylene sulfone, 3,6-diethyl-2-fluoropentamethylene sulfone, 2-ethyl-2-fluoro-5-methylpentamethylene sulfone, 6-ethyl-2- Fluoro-3-methylpentamethylenesulfone, 5-ethyl-2-fluoro-2-methylpentamethylenesulfone, 3-ethyl-2-fluoro-6-methylpentamethylenesulfone, 2-fluoro-2,6-dimethylpentamethylene Sulfone, 2,6-diethyl-2-fluoropentamethylenesulfone, 2-ethyl-2-fluoro-6-methylpentamethylenesulfone, 6-ethyl-2-fluoro-2-methylpentamethylenesulfone, 2-fluoro-2 , 3-Dimethylhexamethylene sulfone, 7-fluoro-2 -Dimethylhexamethylene sulfone, 2,3-diethyl-2-fluorohexamethylene sulfone, 2,3-diethyl-7-fluorohexamethylene sulfone, 2-ethyl-2-fluoro-3-methylhexamethylene sulfone, 2-ethyl -7-Fluoro-3-methylhexamethylene sulfone, 3-ethyl-2-fluoro-2-methylhexamethylene sulfone, 3-ethyl-7-fluoro-2-methylhexamethylene sulfone, 2-fluoro-2,4- Dimethylhexamethylenesulfone, 7-fluoro-2,4-dimethylhexamethylenesulfone, 2,4-diethyl-2-fluorohexamethylenesulfone, 2,4-diethyl-7-fluorohexamethylenesulfone, 2-ethyl-2- Fluoro-4-methylhexamethylene sulfone, 2-ethy Lu-7-fluoro-4-methylhexamethylene sulfone.

  4-ethyl-2-fluoro-2-methylhexamethylene sulfone, 4-ethyl-7-fluoro-2-methylhexamethylene sulfone, 2-fluoro-2,5-dimethylhexamethylene sulfone, 2-fluoro-4,7 -Dimethylhexamethylene sulfone, 2,5-diethyl-2-fluorohexamethylene sulfone, 4,7-diethyl-2-fluorohexamethylene sulfone, 2-ethyl-2-fluoro-5-methylhexamethylene sulfone, 7-ethyl -2-Fluoro-4-methylhexamethylenesulfone, 5-ethyl-2-fluoro-2-methylhexamethylenesulfone, 4-ethyl-2-fluoro-7-methylhexamethylenesulfone, 2-fluoro-2,6- Dimethylhexamethylene sulfone, 2-fluoro-3,7-dimethylhexa Tylene sulfone, 2,6-diethyl-2-fluorohexamethylene sulfone, 3,7-diethyl-2-fluorohexamethylene sulfone, 2-ethyl-2-fluoro-6-methylhexamethylene sulfone, 7-ethyl-2- Fluoro-3-methylhexamethylenesulfone, 6-ethyl-2-fluoro-2-methylhexamethylenesulfone, 3-ethyl-2-fluoro-7-methylhexamethylenesulfone, 2-fluoro-2,7-dimethylhexamethylene Sulfone, 2,7-diethyl-2-fluorohexamethylene sulfone, 2-ethyl-2-fluoro-7-methylhexamethylene sulfone, 7-ethyl-2-fluoro-2-methylhexamethylene sulfone and the like.

Examples of α, α′-difluorocyclic sulfones obtained from cyclic sulfoxides and cyclic sulfides in which the alkyl group is not substituted include the following examples.
2,3-difluoroethylene sulfone, 2,4-difluorotrimethylene sulfone, 2,5-difluorotetramethylene sulfone, 2,6-difluoropentamethylene sulfone, 2,7-difluorohexamethylene sulfone and the like.

Examples of α, α′-difluorocyclic sulfones obtained from monoalkyl-substituted cyclic sulfoxides and cyclic sulfides include the following examples.
2,3-difluoro-2-methylethylene sulfone, 2-ethyl-2,3-difluoroethylene sulfone, 2,4-difluoro-2-methyltrimethylene sulfone, 2-ethyl-2,4-difluorotrimethylene sulfone, 2,4-difluoro-3-methyltrimethylenesulfone, 2,4-difluoro-3-ethyltrimethylenesulfone, 2,5-difluoro-2-methyltetramethylenesulfone, 2-ethyl-2,5-difluorotetramethylene Sulfone, 2,5-difluoro-3-methyltetramethylene sulfone, 3-ethyl-2,5-difluoro-tetramethylene sulfone, 2,6-difluoro-2-methylpentamethylene sulfone, 2-ethyl-2,6- Difluoropentamethylene sulfone, 2,6-difluoro-3-methylpenta Tylene sulfone, 3-ethyl-2,6-difluoropentamethylene sulfone, 2,6-difluoro-4-methylpentamethylene sulfone, 4-ethyl-2,6-difluoropentamethylene sulfone, 2,7-difluoro-2- Methylhexamethylenesulfone, 2-ethyl-2,7-difluorohexamethylenesulfone, 2,7-difluoro-3-methylhexamethylenesulfone, 3-ethyl-2,7-difluorohexamethylenesulfone, 2,7-difluoro- 4-methylhexamethylene sulfone, 4-ethyl-2,7-difluorohexamethylene sulfone and the like.

Examples of α, α′-difluorocyclic sulfones obtained from cyclic sulfoxides and cyclic sulfides in which two alkyl groups are dialkyl-substituted at the same carbon atom include the following examples.
2,4-difluoro-3,3-dimethyltrimethylene sulfone, 3,3-diethyl-2,4-difluorotrimethylene sulfone, 3-ethyl-2,4-difluoro-3-methyltrimethylene sulfone, 2,5 -Difluoro-3,3-dimethyltetramethylene sulfone, 3,3-diethyl-2,5-difluorotetramethylene sulfone, 3-ethyl-2,5-difluoro-3-methyltetramethylene sulfone, 2,6-difluoro- 3,3-dimethylpentamethylene sulfone, 3,3-diethyl-2,6-difluoropentamethylene sulfone, 3-ethyl-2,6-difluoro-3-methylpentamethylene sulfone, 2,6-difluoro-4,4 -Dimethylpentamethylene sulfone, 4,4-diethyl-2,6-difluoro-pentamethylenes Hong, 4-ethyl-2,6-difluoro-4-methylpentamethylenesulfone, 2,7-difluoro-3,3-dimethylhexamethylenesulfone, 3,3-diethyl-2,7-difluorohexamethylenesulfone, 3, -Ethyl-2,7-difluoro-3-methylhexamethylene sulfone, 2,7-difluoro-4,4-dimethylhexamethylene sulfone, 4,4-diethyl-2,7-difluorohexamethylene sulfone, 4-ethyl- 2,7-difluoro-4-methylhexamethylene sulfone and the like.

Examples of α, α′-difluorocyclic sulfones obtained from cyclic sulfoxides and cyclic sulfides in which two alkyl groups are dialkyl-substituted on different carbon atoms include the following examples.
2,3-difluoro-2,3-dimethylethylenesulfone, 2,3-diethyl-2,3-difluoroethylenesulfone, 2-ethyl-2,3-difluoro-3-methylethylenesulfone, 2,4-difluoro- 2,3-dimethyltrimethylene sulfone, 2,3-diethyl-2,4-difluorotrimethylene sulfone, 2-ethyl-2,4-difluoro-3-methyltrimethylene sulfone, 3-ethyl-2,4-difluoro -2-Methyltrimethylenesulfone, 2,4-difluoro-2,4-dimethyltrimethylenesulfone, 2,4-diethyl-2,4-difluorotrimethylenesulfone, 2-ethyl-2,4-difluoro-4- Methyltrimethylenesulfone, 2,5-difluoro-2,3-dimethyltetramethylenesulfone, 2,3-diethi -2,5-difluorotetramethylene sulfone, 2-ethyl-2,5-difluoro-3-methyltetramethylene sulfone, 3-ethyl-2,5-difluoro-2-methyltetramethylene sulfone, 2,5-difluoro- 2,4-dimethyltetramethylene sulfone, 2,4-diethyl 2,5-difluorotetramethylene sulfone, 2-ethyl-2,5-difluoro-4-methyltetramethylene sulfone, 4-ethyl-2,5-difluoro- 2-methyltetramethylenesulfone, 2,5-difluoro-2,5-dimethyltetramethylenesulfone, 2,5-diethyl-2,5-difluorotetramethylenesulfone, 2-ethyl-2,5-difluoro-5-methyl Tetramethylene sulfone, 2,6-difluoro-2,3-dimethylpentamethylenes Hong, 2,3-diethyl-2,6-difluoro-pentamethylene sulfone.

2-ethyl-2,6-difluoro-3-methylpentamethylenesulfone, 3-ethyl-2,6-difluoro-2-methylpentamethylenesulfone, 2,6-difluoro-2,4-dimethylpentamethylenesulfone, 2, , 4-diethyl-2,6-difluoropentamethylene sulfone, 4-ethyl-2,6-difluoro-2-methylpentamethylene sulfone, 2,6-difluoro-2,5-dimethylpentamethylene sulfone, 2,5- Diethyl-2,6-difluoropentamethylenesulfone, 2-ethyl-2,6-difluoro-5-methylpentamethylenesulfone, 5-ethyl-2,6-difluoro-2-methylpentamethylenesulfone, 2,6-difluoro -2,6-dimethylpentamethylene sulfone, 2,6-diethyl-2,6-difluoro Ntamethylene sulfone, 2-ethyl-2,6-difluoro-6-methylpentamethylene sulfone, 2,7-difluoro-2,3-dimethylhexamethylene sulfone, 2,3-diethyl-2,7-difluorohexamethylene sulfone 2-ethyl-2,7-difluoro-3-methylhexamethylene sulfone, 3-ethyl-2,7-difluoro-2-methylhexamethylene sulfone, 2,7-difluoro-2,4-dimethylhexamethylene sulfone, 2,4-Diethyl-2,7-difluorohexamethylene sulfone, 2-ethyl-2,7-difluoro-4-methylhexamethylene sulfone.
4-ethyl-2,7-difluoro-2-methylhexamethylenesulfone, 2,7-difluoro-2,5-dimethylhexamethylenesulfone, 2,5-diethyl-2,7-difluorohexamethylenesulfone, 2-ethyl -2,7-difluoro-5-methylhexamethylenesulfone, 5-ethyl-2,7-difluoro-2-methylhexamethylenesulfone, 2,7-difluoro-2,6-dimethylhexamethylenesulfone, 2,6- Diethyl-2,7-difluorohexamethylenesulfone, 2-ethyl-2,7-difluoro-6-methylhexamethylenesulfone, 6-ethyl-2,7-difluoro-2-methylhexamethylenesulfone, 2,7-difluoro -2,7-dimethylhexamethylene sulfone, 2,7-diethyl-2,7-difluoro Hexamethylene sulfone, 2-ethyl-2,7-difluoro-7-methyl-hexamethylene sulfone.

  The product of the reaction of the present invention usually includes a plurality of products having different substitution rates of fluorine. The product is preferably separated and purified as necessary. Separation and purification are preferably by distillation or column chromatography.

  Examples of the present invention will be described below, but the present invention is not limited thereto. In the following, gas chromatography is referred to as GC, and gas chromatography mass spectrometry is referred to as GC-MS.

[Example 1] Synthesis of α-fluorosulfolanes using tetramethylene sulfoxide as a substrate Tetramethylene dissolved in acetonitrile (750 ml) in a 1000 ml nickel reaction vessel provided with a gas inlet and a gas outlet into the liquid phase Sulfoxide (15.0 g) and copper nitrate · 2.5 hydrate (3.35 g) were charged. The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into the reactor at a rate of 52.3 mmol / h for 5.5 hours. The reaction solution was added to water (750 g), neutralized with sodium hydrogen carbonate, and extracted with chloroform. The product (22.6 g) obtained by distilling off the solvent was subjected to GC analysis, GC-MS analysis and ¹⁹ F-NMR analysis. As a result, 2,5-difluorosulfolane was found to have a yield of 21.2% and 2-fluoro Sulfolane was produced at a yield of 13.5%. It was subjected to silica gel column chromatography to isolate 2,5-difluorosulfolane (4.1 g) and 2-fluorosulfolane (2.2 g).

Spectral data of 2,5-difluorosulfolane;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.39-2.59 (m, 4H, CH ₂ ), 5.30 (dm, 2H, J = 53 Hz) , CHF).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm):-174.0 (dt, 2F, J = 53, 24 Hz).
Mass (EI method)
m / z: 156, 92, 91, 77, 64 (calculated value as C ₄ H ₆ F ₂ O ₂ S: 156.01)

Spectral data of 2-fluorosulfolane;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.17-2.59 (m, 4H), 2.99-3.20 (m, 2H, CH _{2 SO 2), 5.30 (dm,} 1H, J = 52Hz, CHF).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm):-174.0 (m, 1F).
Mass (EI method)
m / z: 138, 74, 73, 59, 46 (calculated value as C ₄ H ₇ FO ₂ S: 138.02)

[Example 2] Synthesis of α-fluorosulfolanes using tetramethylene sulfoxide as substrate Tetramethylene dissolved in acetonitrile (300 ml) in a 500 ml nickel reaction vessel provided with a gas inlet and a gas outlet into the liquid phase Sulfoxide (6.0 g) and sodium fluoride (24.2 g) were charged. The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into the vessel at a rate of 52.3 mmol / h for 2.1 hours. The reaction solution was added to water (300 g), neutralized with sodium hydrogen carbonate, and extracted with chloroform. The solvent was distilled off, and the obtained product (8.22 g) was analyzed by GC, GC-MS and ¹⁹ F-NMR. As a result, it was found that the yield of 2,5-difluorosulfolane was 14.4%, Fluorosulfolane was produced with a yield of 0.8%.

[Example 3] Synthesis of α-fluorosulfolanes using tetrahydrothiophene as a substrate Tetrahydrothiophene dissolved in acetonitrile (100 ml) in a 200 ml nickel reaction vessel provided with a gas inlet and a gas outlet into the liquid phase 1.00 g), copper nitrate · 2.5 hydrate (0.265 g), and water (0.155 g) were charged. The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into the reactor at a rate of 26.1 mmol / h for 1.3 hours. The reaction solution was added to water (100 g), neutralized with sodium hydrogen carbonate, and extracted with chloroform. The solvent was distilled off, and the obtained product (1.11 g) was analyzed by GC, GC-MS and ¹⁹ F-NMR. As a result, the yield of 2,5-difluorosulfolane was 8.1%, Fluorosulfolane was produced in a yield of 13.4%.

[Example 4] Synthesis of α-fluoroethylene sulfones using ethylene sulfoxide as a substrate Using the same reaction vessel as in Example 1, ethylene sulfoxide (15.0 g) dissolved in acetonitrile (750 ml), copper nitrate · 2 Charge pentahydrate (4.58 g). The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into it at a rate of 52.3 mmol / h for 7.5 hours. The reaction solution was added to water (750 g), and hydrogen carbonate. After neutralizing with sodium, extract with chloroform. The solvent is distilled off to obtain 2,3-difluoroethylenesulfone and 2-fluoroethylenesulfone.

[Example 5] Synthesis of α-fluoroethylenesulfones using ethylene sulfide as a substrate Using the same reaction vessel as in Example 1, ethylene sulfide (15.0 g) dissolved in acetonitrile (750 ml), copper nitrate-2 Charge pentahydrate (5.80 g), water (3.37 g). The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into it at a rate of 52.3 mmol / h for 14.3 hours. The reaction solution was added to water (750 g), and hydrogen carbonate. After neutralizing with sodium, extract with chloroform. The solvent is distilled off to obtain 2,3-difluoroethylenesulfone and 2-fluoroethylenesulfone.

[Example 6] Synthesis of α-fluorotrimethylene sulfones using trimethylene sulfoxide as a substrate Using the same reaction vessel as in Example 1, trimethylene sulfoxide (15.0 g) dissolved in acetonitrile (750 ml), nitric acid Charge copper.2.5 hydrate (3.87 g). The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into the vessel at a rate of 52.3 mmol / h for 6.4 hours. The reaction solution was added to water (750 g), and hydrogen carbonate. After neutralizing with sodium, extract with chloroform. The solvent is distilled off to give 2,4-difluorotrimethylene sulfone and 2-fluorotrimethylene sulfone.

[Example 7] Synthesis of α-fluorotrimethylene sulfones using trimethylene sulfide as a substrate Using the same reaction vessel as in Example 1, trimethylene sulfide (15.0 g) dissolved in acetonitrile (750 ml), nitric acid Copper 2.5 hydrate (4.71 g) and water (2.73 g) are charged. The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into it at a rate of 52.3 mmol / h for 11.6 hours. The reaction solution was added to water (750 g), and hydrogen carbonate. After neutralizing with sodium, extract with chloroform. The solvent is distilled off to give 2,4-difluorotrimethylene sulfone and 2-fluorotrimethylene sulfone.

[Example 8] Synthesis of α-fluoropentamethylene sulfones using pentamethylene sulfoxide as a substrate Using the same reaction vessel as in Example 1, pentamethylene sulfoxide (15.0 g) dissolved in acetonitrile (750 ml), nitric acid Charge copper 2.5 hydrate (2.95 g). The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into the vessel at a rate of 52.3 mmol / h for 4.9 hours. The reaction solution was added to water (750 g), and hydrogen carbonate. After neutralizing with sodium, extract with chloroform. The solvent is distilled off to obtain 2,6-difluoropentamethylene sulfone and 2-fluoropentamethylene sulfone.

[Example 9] Synthesis of α-fluoropentamethylene sulfones using pentamethylene sulfide as a substrate Using the same reaction vessel as in Example 1, pentamethylene sulfide (15.0 g) dissolved in acetonitrile (750 ml), nitric acid Copper 2.5 hydrate (3.41 g) and water (1.98 g) are charged. The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into the reaction vessel at a rate of 52.3 mmol / h for 8.4 hours. The reaction solution was added to water (750 g), and hydrogen carbonate. After neutralizing with sodium, extract with chloroform. The solvent is distilled off to obtain 2,6-difluoropentamethylene sulfone and 2-fluoropentamethylene sulfone.

[Example 10] Synthesis of α-fluorohexamethylene sulfones using hexamethylene sulfoxide as a substrate Using the same reaction vessel as in Example 1, hexamethylene sulfoxide (15.0 g) dissolved in acetonitrile (750 ml), nitric acid Charge copper 2.5 hydrate (2.67 g). The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into it at a rate of 52.3 mmol / h for 4.3 hours. The reaction solution was added to water (750 g), and hydrogen carbonate. After neutralizing with sodium, extract with chloroform. The solvent is distilled off to give 2,7-difluorohexamethylene sulfone and 2-fluorohexamethylene sulfone.

[Example 11] Synthesis of α-fluorohexamethylene sulfones using hexamethylene sulfide as a substrate Using the same reaction vessel as in Example 1, hexamethylene sulfide (15.0 g) dissolved in acetonitrile (750 ml), nitric acid Copper.2.5 hydrate (3.00 g) and water (1.74 g) are charged. The reaction vessel was cooled to −40 ° C., and fluorine gas diluted to 20% with nitrogen gas was blown into the reaction vessel at a rate of 52.3 mmol / h for 7.4 hours. The reaction solution was added to water (750 g), and hydrogen carbonate. After neutralizing with sodium, extract with chloroform. The solvent is distilled off to give 2,7-difluorohexamethylene sulfone and 2-fluorohexamethylene sulfone.

  The present invention provides a selective method for producing α-fluoro cyclic sulfones. α-Fluorocyclic sulfones are useful as various solvents, particularly as a medium for immersion exposure in semiconductor production.

Claims (11)

  A method for producing an α-fluoro cyclic sulfone, comprising reacting cyclic sulfoxides and / or cyclic sulfides having at least one hydrogen atom at α-position with fluorine and water in a liquid phase. The cyclic sulfoxides are compounds represented by the following formula (I), the cyclic sulfides are compounds represented by the following formula (II), and the α-fluoro cyclic sulfones are represented by the following formula (III) The manufacturing method of Claim 1 which is a compound.

However, R < ¹ > -R < ⁴ > shows a hydrogen atom or a C1-C10 alkyl group each independently, and at least one is a hydrogen atom.
R ^1F to R ^4F is ^R 1F ^{to R 4F} corresponding to ^R 1 to R ⁴ is an alkyl group having 1 to 10 carbon atoms ^is an R 1 to R ⁴ the same alkyl group having 1 to 10 carbon atoms , ^R 1F ^{to R 4F} corresponding to ^R 1 to R ⁴ is a hydrogen atom is a fluorine atom or a hydrogen atom, and the number of ^R 1F ^{to R 4F} is a fluorine atom is 1 or 2.
Q represents a group represented by the formula — (CH ₂ ) _m —, or a group in which at least one hydrogen atom of the group is substituted with an alkyl group. Here, m is an integer of 0-4. However, when m is 0, Q represents a single bond. The production method according to claim 2, wherein Q is a group represented by the formula — (CH ₂ ) ₂ — or a group in which at least one hydrogen atom of the group is substituted with an alkyl group.   The production method according to any one of claims 1 to 3, wherein the reaction is conducted with fluorine by passing fluorine gas through a solution in which cyclic sulfoxides and / or cyclic sulfides are dissolved in a solvent.   The production method according to claim 4, wherein the solvent has a lone electron pair and has a functional group.   The production method according to claim 4 or 5, wherein the functional group is selected from the group consisting of a nitrile group, an ether group, a hydroxyl group, a tertiary amino group, a halogen group, a nitro group, and an amide group.   The production method according to any one of claims 4 to 6, wherein the solvent is a nitrile solvent.   The production method according to any one of claims 4 to 7, wherein the fluorine gas is diluted with nitrogen or helium.   The production method according to any one of claims 1 to 8, wherein a metal salt is present when reacting with fluorine and water.   The production method according to claim 9, wherein the metal salt is an alkali metal fluoride or a strong acid salt of a transition metal.   The method according to claim 9 or 10, wherein the metal salt is a metal salt selected from the group consisting of sodium fluoride, potassium fluoride, cesium fluoride, copper nitrate, nickel nitrate, and cobalt nitrate.