WO2009102034A1 - Procédé de fabrication d'un composé fluoré - Google Patents

Procédé de fabrication d'un composé fluoré Download PDF

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Publication number
WO2009102034A1
WO2009102034A1 PCT/JP2009/052434 JP2009052434W WO2009102034A1 WO 2009102034 A1 WO2009102034 A1 WO 2009102034A1 JP 2009052434 W JP2009052434 W JP 2009052434W WO 2009102034 A1 WO2009102034 A1 WO 2009102034A1
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Prior art keywords
group
compound
reaction
substituted
solvent
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PCT/JP2009/052434
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English (en)
Japanese (ja)
Inventor
Shoji Hara
Masanori Sawaguchi
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Asahi Glass Co., Ltd.
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Application filed by Asahi Glass Co., Ltd. filed Critical Asahi Glass Co., Ltd.
Publication of WO2009102034A1 publication Critical patent/WO2009102034A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Definitions

  • the present invention relates to a method for producing a fluoro compound. More specifically, the present invention relates to a method for producing a fluoro compound having a carbon atom to which two fluorine atoms are bonded.
  • a fluorinating agent when producing a fluoro compound by fluorinating an organic compound, a fluorinating agent is used.
  • a compound having a carbonyl group a method of fluorinating with SF 4 or DAST (diethylaminosulfur trifluoride) is known.
  • SF 4 or DAST diethylaminosulfur trifluoride
  • a fluorination method using IF 5 has been proposed as a fluorinating agent that is easy to handle (Patent Document 1).
  • Patent Document 1 specific examples represented by the following formulas (a) to (c) are given as a method for producing a fluoro compound having a carbon atom to which two fluorine atoms are bonded using IF 5. Yes.
  • Et used in the formulas (a) to (c) represents an ethyl group
  • Me represents a methyl group
  • rt represents a reaction at room temperature (23 ° C.)
  • hr represents a reaction time.
  • Hexane is hexane as the reaction solvent
  • CH 2 Cl 2 indicates that using CH 2 Cl 2 as the reaction solvent.
  • the fluoro compound obtained by the formulas (a) and (b) has a sulfide group in the molecule, and a further reaction step is required to obtain a compound excluding this sulfide group.
  • the raw material has a special structure with a heterocycle containing two sulfur atoms. Therefore, it is difficult to obtain other than the specific raw material in the reaction of the formula (c), and the structure of the resulting fluoro compound is limited. Further, in order to synthesize the raw material of the formula (c), it was necessary to use HS—CH 2 CH 2 —SH having a strong odor.
  • the present invention has been made in view of such problems of the prior art, and efficiently produces fluoro compounds having various molecular structures having carbon atoms to which two fluorine atoms are bonded by a one-step reaction, Moreover, it is an object to provide a manufacturing method suitable for industrialization.
  • the present inventors have reacted monosulfides with IF 5 to form a one-step reaction between a sulfide group and a hydrogen atom bonded to the ⁇ -position carbon atom of the sulfide group. It discovered that it could substitute by a fluorine atom by reaction. That is, the gist of the present invention is as follows.
  • a method for producing a fluoro compound represented by the following formula (B), comprising reacting a compound represented by the following formula (A) with IF 5 .
  • X represents a group selected from an aryl group, a monovalent heterocyclic group, and an alkyl group, or a group in which one or more hydrogen atoms in the selected group are substituted
  • Y represents an aryl group, a monovalent group, or a monovalent group.
  • R represents a group selected from a heterocyclic group, an alkyl group, an acyl group, and an aryloxy group, or a group in which one or more of hydrogen atoms in the selected group are substituted, a cyano group, or an alkoxycarbonyl group.
  • X is a group selected from an aryl group and a monovalent heterocyclic group, or a group in which at least one hydrogen atom in the selected group is substituted
  • Y is a cyano group, an alkoxycarbonyl group, an acyl group
  • R is an aryl group, an alkyl group, or a halogenated aryl group.
  • Monosulfides which are the raw material compounds of the present invention are easy to produce. Moreover, there is almost no restriction on the structure of the group bonded to the sulfide group. Therefore, fluoro compounds having various molecular structures can be easily obtained.
  • IF 5 which is a fluorinating agent has no problem in handling such as explosiveness and is inexpensive. Therefore, the production method of the present invention is suitable for industrialization. Moreover, the production method of the present invention can introduce two fluorine atoms in one step with respect to one carbon atom. Therefore, according to this invention, the fluoro compound which has a carbon atom which two fluorine atoms couple
  • the compound represented by the formula (A) is also referred to as “compound (A)”.
  • the production method of the present invention is a method for producing compound (B) by reacting compound (A) with IF 5 as shown below.
  • X represents a group selected from an aryl group, a monovalent heterocyclic group, and an alkyl group, or a group in which one or more hydrogen atoms in the selected group are substituted
  • Y represents an aryl group, a monovalent group, or a monovalent group.
  • R represents a group selected from a heterocyclic group, an alkyl group, an acyl group, and an aryloxy group, or a group in which one or more of hydrogen atoms in the selected group are substituted, a cyano group, or an alkoxycarbonyl group.
  • Compound (A) is a compound in which one hydrogen atom is bonded to the ⁇ -position carbon atom of the sulfide group and two substituents represented by X and Y are bonded.
  • X in the compound (A) is a group selected from an aryl group, a monovalent heterocyclic group, and an alkyl group, or a group in which one or more hydrogen atoms in the selected group are substituted.
  • Examples of the aryl group constituting X include a phenyl group and a naphthyl group.
  • Examples of the monovalent heterocyclic group constituting X include a thienyl group and a furanyl group.
  • the alkyl group constituting X may be a linear structure, a branched structure, a ring structure, a group having a partially branched structure, and / or a group having a partially ring structure.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. Is mentioned.
  • X may be a group in which one or more hydrogen atoms in the above groups are substituted.
  • substituent with hydrogen atoms in the group is preferably selected from inert groups in the fluorination reaction using IF 5.
  • the inert group in the fluorination reaction include a halogen atom, a nitro group, and a cyano group.
  • a halogen atom a chlorine atom, a fluorine atom, or a bromine atom is preferable.
  • a substituent that substitutes for a hydrogen atom an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms is also preferable.
  • the substituted aryl group constituting X is preferably a halogenated aryl group, and examples thereof include a chlorophenyl group, a bromophenyl group, and a 2,3-difluorophenyl group. It is done.
  • the substituted monovalent heterocyclic group constituting X includes a 5-methyl-2-thienyl group and a 4-methyl-2-thienyl group Etc.
  • X and Y in the compound (A) become X and Y in the compound (B) while maintaining the structure. Therefore, X and Y in the compound (A) may be selected from those of the target compound (B).
  • X and Y in the compound (A) may be selected from those of the target compound (B).
  • the compound (A) in which X is a phenyl group and Y is an ethoxycarbonyl group has an unshared electron pair on a sulfur atom.
  • the reaction is initiated by the sharing of this unshared electron pair by the sulfur atom and IF 4 + .
  • F ⁇ formed from IF 5 pulls out the hydrogen atom bonded to the carbon atom at the benzyl position, and generates a stable cation shown in the following formula (III). F ⁇ reacts with this cation again, and first, one fluorine atom is bonded to the carbon atom at the benzyl position.
  • the cation represented by the formula (VIII) is F - and react to produce the mono-fluoro body shown in formula (IX) by side reaction resulting in progress simultaneously. Therefore, the yield of the target difluoro compound (VI) is considered to be low.
  • Y is an “electron-withdrawing group”
  • the cation represented by the formula (III) which is an intermediate substance of the reaction, is more stable than the cation similar to the cation represented by the formula (VIII).
  • the reaction of II) ⁇ (III) ⁇ (IV) occurs preferentially, and the side reaction is considered to be suppressed.
  • X preferable from the viewpoint of reactivity includes a group selected from an aryl group and a monovalent heterocyclic group, or a group in which one or more hydrogen atoms in the selected group are substituted.
  • the substituent that replaces the hydrogen atom in the “group in which one or more hydrogen atoms are substituted” is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. 1 or more selected from nitro groups.
  • R from the viewpoint of reactivity with IF 5 includes an aryl group, an alkyl group, a halogenated aryl group, and a halogenated alkyl group.
  • R is more preferably an aryl group, an alkyl group, or a halogenated aryl group, and particularly preferably an alkyl group or a halogenated aryl group.
  • the halogen atom in the halogenated aryl group is preferably a fluorine atom or a chlorine atom.
  • R is an alkyl group or a halogenated aryl group, the electron density on the sulfur atom will not be extremely reduced, so it is considered preferable for the progress of the fluorination reaction.
  • R is more preferably an aryl group or an alkyl group from the viewpoint of easy availability of the compound (A), and particularly preferably an alkyl group. More preferred R is a methyl group.
  • the compound (A) in which R is a methyl group is easy to obtain and synthesize.
  • the compound (A) in which R is a methyl group has good reactivity with IF 5 .
  • the manufacturing method of a compound (A) is mentioned later, it can also obtain as a commercial item.
  • the amount of IF 5 is preferably 1 to 10-fold mol amount, particularly preferably 1.5 to 2.0-fold mol amount based on Compound (A). From the viewpoint of ease of handling, it is preferable to add IF 5 previously dissolved in a solvent to the reaction system.
  • the solvent may be the same as or different from the solvent that can be used in the fluorination reaction described below.
  • the solvent used for dissolving IF 5 can be selected from the same solvents that can be used for the fluorination reaction described below. Among these, methylene chloride (CH 2 Cl 2 ) is particularly preferable from the viewpoint of solubility.
  • the amount of the solvent is preferably 1 to 10 times the molar amount relative to IF 5 and more preferably 3 to 5 times the molar amount.
  • the reaction temperature of the fluorination reaction is preferably ⁇ 50 to 100 ° C., particularly preferably ⁇ 20 to 30 ° C. If the reaction temperature is 100 ° C. or lower, it is preferable that the loss of IF 5 can be prevented by being lower than the boiling point of IF 5 (100.5 ° C.). Moreover, if it is 30 degrees C or less, since reaction other than the objective (for example, side reactions, such as another fluorination reaction), is suppressed, it is preferable. On the other hand, a reaction temperature of ⁇ 50 ° C. or higher is preferable because the reaction can be carried out in the liquid phase. Further, it is more preferable that the temperature is ⁇ 20 ° C. or higher because precipitation of most raw materials can be prevented.
  • the reaction time is not particularly limited, and is preferably the time until the raw material disappears or the reaction does not proceed.
  • the fluorination reaction may be performed in the absence of a solvent or in the presence of a solvent, and is preferably performed in the presence of a solvent.
  • the compound (A) When the compound (A) is in a liquid state, the compound (A) serves as a solvent, so that the reaction can be carried out without using a solvent.
  • the solvent include chlorinated solvents such as methylene chloride and chloroform, hydrocarbon solvents such as toluene, hexane, and pentane, fluorine-based solvents such as tetrahydrofuran, diethyl ether, and t-butyl ethyl ether.
  • ether solvents such as dimethylformamide, dimethyl sulfoxide, and acetonitrile. Of these, hexane and methylene chloride are preferred.
  • the reaction crude product containing the compound (B) obtained by the fluorination reaction is diluted by adding water as a normal post-treatment, and then neutralized, extracted, dried, and the like.
  • the neutralizing agent used for the neutralization operation include aqueous solutions of sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, and the like, and sodium hydrogen carbonate is preferably used from the viewpoint of handling.
  • the solvent for extraction the same solvent as used for the reaction can be used, but diethyl ether and methylene chloride are preferable.
  • the desiccant used for drying include anhydrous magnesium sulfate and anhydrous sodium sulfate.
  • the purification treatment include methods such as column chromatography, distillation, and recrystallization.
  • Compound (A) which is a starting material for the reaction of the present invention can be produced by applying a method described in Y. Tamura et al. Tetrahedron Lett., 1980, 21, 2547-2548. .
  • the production method of the compound (A) is preferably one of the following methods 1 to 3.
  • the chlorinating agent examples include N-chlorosuccinimide, sulfuryl chloride and the like, and it is preferable to use 1 to 1.5 times the molar amount of the compound (1).
  • the reaction with the chlorinating agent is preferably carried out in the presence of a solvent such as carbon tetrachloride, chloroform or methylene chloride.
  • the reaction temperature between the compound (1) and the chlorinating agent is preferably 0-100 ° C, more preferably 10-30 ° C.
  • the reaction between compound (2) and compound (3) is preferably carried out in the presence of a solvent such as methylene chloride.
  • a solvent such as methylene chloride.
  • the reaction temperature of the compound (2) and the compound (3) is preferably 0 to 100 ° C, more preferably 0 to 20 ° C.
  • Method 2 A method of obtaining a compound (A) by reacting a compound represented by the following formula (4) with a compound represented by the formula (5).
  • R, Y, and X in a formula represent the same meaning as the above.
  • X-CHCl-Y (4) RSNa (5) The reaction is preferably carried out by reacting an aqueous solution of the compound (5) with the compound (4).
  • the reaction temperature is preferably 0 to 100 ° C., more preferably 0 to 20 ° C.
  • Method 3 A method of obtaining a compound (A) by reacting a compound represented by the following formula (6), a compound represented by the following formula (7) and a compound represented by the following formula (8) in the presence of a Lewis acid.
  • R, Y, and X in a formula represent the same meaning as the above.
  • the reaction is preferably carried out in the presence of a solvent such as methylene chloride, and the reaction temperature is preferably 0 to 100 ° C., more preferably 0 to 20 ° C.
  • the Lewis acid used include boron trifluoride-diethyl ether.
  • the structure of the produced compound was determined by comparison with known NMR data.
  • the yield of the compound was determined by quantifying the raw materials used and the mass of the product.
  • the meanings of symbols used in the examples are as follows. Ph represents a phenyl group, Et represents an ethyl group, Bu represents a butyl group, t-Bu represents a tertiary butyl group, and n-Bu represents normal butyl. Rt indicates that the reaction was performed at room temperature (23 ° C.).
  • Example 1-2 to Example 1-7 The following compounds (A-2), (A-3), (A-5) to (A-7) were synthesized using the same method as in Example 1-1 except that the starting material was changed. Table 1 shows the relationship between the starting material and the produced compound (A). Further, the following compound (A-4) was synthesized using the same method as in Example 1-1 except that the starting material was changed. Table 1 shows the relationship between the starting material and the resulting compound (A).
  • IF 5 was a CH 2 Cl 2 solution of the IF 5 as a mixture of 5-fold molar amount of methylene chloride IF 5 (hereinafter referred to as "IF 5 / 5CH 2 Cl 2".).
  • a container made of tetrafluoroethylene was charged with 1 g of IF 5 / 5CH 2 Cl 2 (1.5 mmol as IF 5 ) and 2 ml of hexane, and 210 mg (1) of ethyl methylthiophenylacetate (A-1) at 0 ° C. 0.0 mmol) was added and stirred at room temperature for 2 hours.
  • the obtained mixture was poured into 20 ml of water placed in a tetrafluoroethylene beaker, neutralized with an aqueous sodium hydrogen carbonate solution, extracted with diethyl ether, and the organic layer was washed with aqueous sodium thiosulfate.
  • the extract was dried over anhydrous magnesium sulfate, concentrated by a rotary evaporator, and purified by silica gel column chromatography to obtain 146 mg (0.73 mmol) of ethyl 2,2-difluorophenylacetate (B-1). The yield was 73%.
  • Example 3 to 11 The compound (A) described in Table 2 was used as a raw material. The reaction was carried out in the same manner as in Example 2 except that the reaction conditions were changed to those described in Table 2. The obtained compound (B) and yield are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)

Abstract

L'invention porte sur un procédé industriellement approprié pour produire avec un haut rendement des composés fluorés ayant diverses structures moléculaires, dans lesquelles deux atomes de fluor sont liés à un atome de carbone, dans une réaction à une seule étape. De façon spécifique, l'invention porte sur un procédé de fabrication d'un composé fluoré représenté par la formule (B), qui est caractérisé en ce qu'un composé représenté par la formule (A) est mis à réagir avec IF5.
PCT/JP2009/052434 2008-02-15 2009-02-13 Procédé de fabrication d'un composé fluoré WO2009102034A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-034626 2008-02-15
JP2008034626A JP5305321B2 (ja) 2008-02-15 2008-02-15 フルオロ化合物の製造方法

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Publication Number Publication Date
WO2009102034A1 true WO2009102034A1 (fr) 2009-08-20

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KR102466415B1 (ko) 2016-01-20 2022-11-15 삼성전자주식회사 이미지 센서

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001096263A1 (fr) * 2000-06-13 2001-12-20 Daikin Industries, Ltd. Procedes pour la production de composes organiques fluores et agents de fluoration
JP2002338517A (ja) * 2001-05-18 2002-11-27 Asahi Glass Co Ltd ｇｅｍ−ジフッ化物の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001096263A1 (fr) * 2000-06-13 2001-12-20 Daikin Industries, Ltd. Procedes pour la production de composes organiques fluores et agents de fluoration
JP2002338517A (ja) * 2001-05-18 2002-11-27 Asahi Glass Co Ltd ｇｅｍ−ジフッ化物の製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
AYUBA,S. ET AL.: "Selective trifluorination of alkyl aryl sulfides using IF5", TETRAHEDRON, vol. 60, no. 50, 2004, pages 11445 - 11451 *
FURUTA,S. ET AL.: "Facile Synthesis of a- Fluoroalkyl Sulfides under Oxidative Desulfurization-Fluorination Conditions", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 71, no. 11, 1998, pages 2687 - 2694 *
KUROBOSHI M. ET AL.: "Oxidative Fluorination reaction ni yoru Yuki Fluorine Compound no Gosei", JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY, JAPAN, vol. 51, no. 12, 1993, pages 1124 - 1133 *
MANABU KUROBOSHI ET AL.: "Oxidative desulfurization-fluorination of 1-substituted 2, 2,2-tris(methylthio)ethanol induces difluorination under oxidation or rearrangement", TETRAHEDRON LETTERS, vol. 36, no. 34, 1995, pages 6121 - 6122 *

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JP2009191031A (ja) 2009-08-27

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