Classifications

• • 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
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/12—Preparation of carboxylic acid esters from asymmetrical anhydrides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/86—Ring systems containing bridged rings containing four rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/90—Ring systems containing bridged rings containing more than four rings

Definitions

• the present invention relates to a method for industrially advantageously producing an alicyclic monoolefin carboxylic acid (meth) acryloyloxyalkyl ester in a high yield.
• Patent Document 2 discloses a hydroxyl compound and a carboxylic acid compound, a specific sulfonyl chloride compound, an aromatic organic base (first basic compound), and another basic compound (second A method for producing a carboxylic acid ester compound is disclosed in which the reaction is carried out in the presence of a basic compound.
• first basic compound an aromatic organic base
• second A method for producing a carboxylic acid ester compound is disclosed in which the reaction is carried out in the presence of a basic compound.
• the method described in this document cannot be said to be an industrially excellent method because it requires two types of bases, and by-products are produced and its removal is difficult.
• the present invention has been made in view of the above-described circumstances, and is useful as a monomer constituting a resin material such as an electronic device, and provides an alicyclic monoolefincarboxylic acid (meth) acryloyloxyalkyl ester in a high yield. It is an object of the present invention to provide a method for industrially advantageous production.
• the present inventor reacted an alicyclic monoolefin carboxylic acid and an alkylsulfonyl halide in an organic solvent in the presence of a first tertiary amine to produce a mixed acid anhydride.
• a high purity alicyclic monoolefin is obtained by further adding a second tertiary amine and n-hydroxyalkyl (meth) acrylate to the obtained reaction solution.
• the present inventors have found that a carboxylic acid (meth) acryloylalkyl ester can be obtained in a high yield, and have completed the present invention.
• n 1 represents 1 or 2
• R 1 , R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. .
• RSO 2 X (wherein R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen atom)
• n 2 represents an integer of 1 to 12
• R 4 represents a hydrogen atom or a methyl group
• r 1 and r 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• R ⁇ a> R ⁇ b> R ⁇ c> N R ⁇ a> , R ⁇ b> , R ⁇ c> is respectively independently carbon number which may have a substituent.
• the ester compound represented by the said Formula (1) useful as a monomer which comprises resin materials, such as an electronic device can be obtained with high purity and a high yield.
• the production method of the present invention does not require the use of a large amount of water during the post-treatment of the reaction solution, and is useful as an industrial production method from the economical and environmental protection viewpoints.
• (meth) acryl means acryl or methacryl
• (meth) acryloyloxy group means acryloyloxy group or methacryloyloxy group.
• the production method of the alicyclic monoolefin carboxylic acid (meth) acryloylalkyl ester (hereinafter sometimes referred to as “ester compound (1)”) represented by the formula (1) of the present invention comprises the following two steps. It is characterized by having. Step (I): To an organic solvent solution of the alicyclic monoolefin carboxylic acid represented by the formula (2) (hereinafter sometimes referred to as “carboxylic acid compound (2)”), the first tertiary amine and By adding an alkylsulfonyl halide represented by the formula: RSO 2 X and stirring the entire volume, the mixed acid anhydride represented by the formula (3) (hereinafter, referred to as “acid anhydride (3)” may be used.
• an organic solvent solution of the alicyclic monoolefin carboxylic acid represented by the formula (2) hereinafter sometimes referred to as “carboxylic acid compound (2)”
• RSO 2 X alkylsulfonyl halide represented
• Step (II) to obtain a reaction mixture comprising: a second tertiary amine and a hydroxyalkyl (meth) acrylate (meth) acrylate represented by the above formula (4) (into the reaction mixture obtained in the step (I)).
• a reaction mixture comprising: a second tertiary amine and a hydroxyalkyl (meth) acrylate (meth) acrylate represented by the above formula (4) (into the reaction mixture obtained in the step (I)).
• step (I) the first tertiary amine and the alkylsulfonyl halide are added to the organic solvent solution of the carboxylic acid compound (2), and the whole volume is stirred to thereby contain the mixed acid anhydride (3). This is a step of obtaining a mixture.
• n 1 represents 1 or 2
• 1 is preferable from the viewpoint of availability.
• R 1 , R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
• hydrocarbon group having 1 to 10 carbon atoms which may have a substituent include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, a t-butyl group, an alkyl group having 1 to 10 carbon atoms of an n-hexyl group; a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group; an aryl such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group Groups and the like.
• Examples of the substituent of the alkyl group having 1 to 10 carbon atoms which may have a substituent include halogen atoms such as fluorine atom and chlorine atom; alkoxy groups such as methoxy group, ethoxy group and isopropoxy group; It is done.
• Examples of the substituent of the cycloalkyl group having 3 to 10 carbon atoms which may have a substituent include alkyl groups such as methyl group and ethyl group; halogen atoms such as fluorine atom and chlorine atom; methoxy group, ethoxy group, An alkoxy group such as an isopropoxy group; and the like.
• substituent of the aryl group which may have a substituent include alkyl groups such as methyl group and ethyl group; halogen atoms such as fluorine atom and chlorine atom; alkoxy groups such as methoxy group, ethoxy group and isopropoxy group Nitro group; cyano group and the like.
• R 1 , R 2 and R 3 are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Or an alkyl group having 1 to 6 carbon atoms, more preferably R 1 and R 2 are hydrogen atoms, R 3 is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 , R 2 and R It is particularly preferred that all 3 are hydrogen atoms.
• carboxylic acid compound (2) examples include compounds represented by the following (2-1) and (2-2).
• R represents an alkyl group having 1 to 20 carbon atoms
• X represents a halogen atom.
• the alkyl group having 1 to 20 carbon atoms of R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
• the halogen atom for X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is prefer
• methylsulfonyl chloride ethylsulfonyl chloride, n-propylsulfonyl chloride, Alkylsulfonyl chlorides having 1 to 6 carbon atoms such as isopropylsulfonyl chloride, n-butylsulfonyl chloride, t-butylsulfonyl chloride, n-pentylsulfonyl chloride, n-hexylsulfonyl chloride and the like are preferable, and methylsulfonyl chloride is particularly preferable.
• the alkylsulfonyl halide is used in an amount of preferably 1 to 5 molar equivalents and more preferably 1 to 1.5 molar equivalents per 1 mole of the carboxylic acid compound (2).
• Examples of the first tertiary amine used in the present invention include aromatic tertiary amines, alicyclic tertiary amines, and aliphatic tertiary amines.
• Examples of the aromatic tertiary amine include pyridine, picoline ( ⁇ , ⁇ , ⁇ ), lutidine, 4- (dimethylamino) pyridine, N, N-dimethylaniline, N, N-diethylaniline, diphenylmethylamine, and the like. .
• Alicyclic tertiary amines include hexamethylenetetramine, 1,8-diazabicyclo [5.4.0] unde-7-cene (DBU), 1,4-diazabicyclo [2.2,2] octane (DABCO). 1,5-diazabicyclo [4.3.0] non-5-ene, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, N-methylpyrrolidine, N-ethylpyrrolidine, dimethyl Examples include cyclohexylamine, diethylcyclohexylamine, tricyclohexylamine and the like.
• the aliphatic tertiary amine is represented by the formula: R a R b R c N (wherein R a , R b , and R c each independently has 1 to 20 carbon atoms which may have a substituent) And an N, N, N ′, N′-tetramethylethylenediamine and the like.
• Examples of the alkyl group having 1 to 20 carbon atoms which may have a substituent for R a , R b and R c include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an amyl group, And alkyl groups having 1 to 20 carbon atoms such as hexyl group, octyl group and decyl group; alkyl groups having 1 to 20 carbon atoms having a substituent such as hydroxyethyl group and benzyl group. These can be used alone or in combination of two or more.
• a compound represented by the formula: R a R b R c N is used as the first tertiary amine from the viewpoint of easy handling and yield of the target product with good yield. preferable.
• R a R b R c N Specific examples of the tertiary amine represented by the formula: R a R b R c N include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine, triamylamine, diethyl -N-butylamine, methyldi-n-butylamine, methylethyl-n-butylamine, dodecyldimethylamine and the like.
• trimethylamine, triethylamine, and the like from the viewpoint that the target compound can be obtained in good yield, the amount of water used in the post-treatment operation is small and the operation is easy, and the production cost is low.
• Diisopropylethylamine is preferred and triethylamine is particularly preferred.
• the amount of the first tertiary amine used is preferably 1 to 5 molar equivalents, more preferably 1 to 1.5 molar equivalents, per 1 mol of the carboxylic acid compound (2).
• the reaction is performed in an organic solvent.
• organic solvent to be used include ester solvents such as ethyl acetate, propyl acetate and butyl acetate; halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene; tetrahydrofuran, tetrahydropyran, diethyl ether Ether solvents such as 1,4-dioxane, ethylene glycol dimethyl ether and cyclopentyl methyl ether; aliphatic hydrocarbon solvents such as hexane and heptane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; N, N— And amide solvents such as dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and the like. These solvents may be used alone or in combination of two or more
• the target compound can be obtained in good yield, the amount of water used in the post-treatment operation is small, the operation is easy, and the production cost is low.
• a solvent that is phase-separated from water is preferable, an ester solvent is more preferable, an alkyl ester having 1 to 10 carbon atoms of an aliphatic carboxylic acid having 2 to 6 carbon atoms is further preferable, and acetic acid is preferable. Ethyl is particularly preferred.
• the amount of the organic solvent used is not particularly limited, but is usually 1 to 30 times by mass, preferably 2 to 10 times by mass with respect to the carboxylic acid compound (2).
• step (I) the order of addition of the first tertiary amine and alkylsulfonyl halide to be added to the organic solvent solution of the carboxylic acid compound (2) is not particularly limited, and the organic solvent solution of the carboxylic acid compound (2) is not limited.
• the alkylsulfonyl halide may be added after the first tertiary amine is added, or after the first tertiary amine is added. Since the target product can be obtained with good yield, it is preferable to add the first tertiary amine after adding the alkylsulfonyl halide.
• the alkylsulfonyl halide and the first tertiary amine are preferably added little by little with stirring while cooling the reaction solution from the viewpoint of preventing the temperature of the reaction solution from rising and side reaction from proceeding.
• the reaction temperature is usually ⁇ 20 ° C. to + 50 ° C., preferably 0 ° C. to 30 ° C.
• the reaction time is usually 0.5 to 24 hours, preferably 0.5 to several hours.
• step (I) a reaction solution containing the mixed acid anhydride represented by the formula (3) is obtained.
• the completion of the reaction can be confirmed by gas chromatography, thin layer chromatography, liquid chromatography or the like.
• the mixed acid anhydride is isolated from the obtained reaction solution, and then may be subjected to the reaction in step (II) or the reaction solution obtained by the reaction in step (I). May be used as it is for the next step (II).
• the reaction solution obtained by the reaction in the step (I) is directly subjected to the reaction in the next step (II).
• Step (II) is a step of adding the second tertiary amine and hydroxy (meth) acrylate (4) to the reaction mixture obtained in step (I) and stirring the whole volume. That is, in step (II), the target ester is obtained by reacting the mixed acid anhydride obtained in step (I) with hydroxy (meth) acrylate (4) in the presence of the second tertiary amine. The reaction for obtaining the compound (1) is carried out.
• n 2 represents an integer of 1 to 12 in the formula (4).
• n 2 is preferably an integer of 1 to 6, more preferably an integer of 1 to 4, from the viewpoint of obtaining a polymer having a high glass transition point by using the ester compound (1) to be produced as a monomer.
• R 4 represents a hydrogen atom or a methyl group.
• r 1 and r 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, isopropyl group, n-propyl group, t-butyl group, n-butyl group, and n-hexyl group.
• r 1 and r 2 are hydrogen atoms.
• groups represented by —C (r 1 ) (r 2 ) — may be the same or different.
• hydroxy (meth) acrylate (4) include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy n-propyl acrylate, methacrylic acid Examples include 3-hydroxy n-propyl, 1-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1-hydroxyisopropyl acrylate, 1-hydroxyisopropyl methacrylate.
• the amount of the hydroxy (meth) acrylate (4) used is usually preferably 1 to 3 molar equivalents and more preferably 1 to 1.5 molar equivalents per 1 mol of the carboxylic acid compound (2). preferable.
• the second tertiary amine may be the same as or different from the first tertiary amine, but the target product can be obtained at a low cost and in a high yield. Both are particularly preferably triethylamine.
• the amount of the second tertiary amine used is preferably 1 to 5 molar equivalents, more preferably 1 to 1.5 molar equivalents per 1 mol of the carboxylic acid compound (2).
• step (II) the order of addition of the second tertiary amine and hydroxy (meth) acrylate (4) is not particularly limited, and the reaction mixture obtained in step (I) is added to hydroxy (meth) acrylate (4 ) May be added followed by the addition of the second tertiary amine or the addition of the second tertiary amine followed by the addition of the hydroxy (meth) acrylate (4). Since the target product can be obtained with good yield, it is preferable to add the hydroxy (meth) acrylate (4) after the second tertiary amine is added.
• the addition of the second tertiary amine and hydroxy (meth) acrylate (4) is a small amount with stirring while cooling the reaction solution from the viewpoint of preventing the temperature of the reaction solution from rising and side reaction from proceeding. It is preferable to add them one by one.
• the reaction temperature is usually ⁇ 10 ° C. to + 30 ° C., preferably ⁇ 5 ° C. to + 20 ° C.
• the reaction time is usually 0.5 to 24 hours, preferably 0.5 to several hours, depending on the reaction scale.
• reaction completion can be confirmed by gas chromatography, thin layer chromatography, liquid chromatography or the like.
• the target ester compound (1) can be isolated from the reaction mixture by a usual post-treatment operation in organic synthetic chemistry.
• the reaction mixture obtained in the step (II) is neutralized by adding an acid and separated, and the organic layer is separated, then an aqueous alkali solution is added to the obtained organic layer and stirred and separated. After separating the organic layer, the obtained organic layer is washed with saturated brine. Next, the organic layer is dried over anhydrous sodium sulfate, sodium sulfate is removed, and the solvent is distilled off under reduced pressure, followed by purification. Examples of the purification method include, but are not limited to, silica gel column chromatography and distillation.
• a target product having a yield of 70% or more, preferably 80% or more and a purity of 99% or more can be easily obtained.
• the production method of the present invention does not require a large amount of water, is simple in the post-treatment operation, and hardly generates by-products, so that it is suitable as an industrial production method in terms of cost and operation. Yes.
• the purity of the target product can be confirmed by gas chromatography or the like.
• Preferred specific examples of the resulting ester compound (1) include compounds represented by the following (1-1) and (1-2).
• ester compound (1) tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-8-ene-3-carboxylic acid (acryloyloxy) methyl ester, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-8-ene-3-carboxylic acid (methacryloyloxy) methyl ester, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-8-ene-3-carboxylic acid 2- (acryloyloxy) ethyl ester, tetracyclo [4.4.0.1 2,5 .
• the resulting ester compound (1) has a norbornene structure and can function as a monomer in the metathesis ring-opening polymerization reaction.
• Such an ester compound is suitably used as a monomer constituting a resin material such as an electronic device.
• Tetracyclo [4.4.0.1 2,5 . 16 g (0.14 mol) of methanesulfonyl chloride was gradually added to a solution of 25.0 g (0.12 mol) of 1 7,10 ] dodec-8-ene-3-carboxylic acid in 190 g of ethyl acetate under ice cooling.
• 15 g (0.15 mol) of triethylamine was slowly added, and the whole volume was stirred at room temperature (23 ° C.) for 1 hour.
• thin layer chromatography confirmed the disappearance of raw materials and the formation of mixed acid anhydrides.
• Example 1 a high-purity target product was obtained in good yield with almost no by-products. Even in Comparative Example 1, a high-purity target product can be obtained in a high yield. However, since this method requires a large amount of water, a large reaction kettle is required, post-treatment is complicated, and it is suitable as an industrial production method. It is hard to be. In Comparative Example 2, a sulfonic acid ester is by-produced. This can be removed by silica gel column chromatography, but it is difficult to remove by distillation because the boiling point is close to the boiling point of the target product. It is difficult to say that the method of Comparative Example 2 is suitable as an industrial production method.

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