WO2011114954A1 - 新規ジアリールスルホン化合物、及びその製造方法 - Google Patents
新規ジアリールスルホン化合物、及びその製造方法 Download PDFInfo
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- WO2011114954A1 WO2011114954A1 PCT/JP2011/055452 JP2011055452W WO2011114954A1 WO 2011114954 A1 WO2011114954 A1 WO 2011114954A1 JP 2011055452 W JP2011055452 W JP 2011055452W WO 2011114954 A1 WO2011114954 A1 WO 2011114954A1
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- 0 Cc(c(*)c(c(*)c1*)S*)c1S(c(c(*)c1*)c(*)c(*)c1S*)(=O)=O Chemical compound Cc(c(*)c(c(*)c1*)S*)c1S(c(c(*)c1*)c(*)c(*)c1S*)(=O)=O 0.000 description 1
- FZCFOMHRAYQRIO-UHFFFAOYSA-N Sc(cc1)ccc1Sc1ccscc1 Chemical compound Sc(cc1)ccc1Sc1ccscc1 FZCFOMHRAYQRIO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/06—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols from sulfides, hydropolysulfides or polysulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
- C07C323/65—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/02—Monothiocarboxylic acids
- C07C327/04—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C327/06—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of an acyclic saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
- C07D331/02—Three-membered rings
Definitions
- the present invention relates to a novel diarylsulfone compound useful as a monomer for forming a resin for organic optical materials, a production method thereof, and a production method of a raw material compound used in the production method.
- Optical materials made of synthetic resins are light in weight compared to inorganic materials such as glass, are excellent in moldability, etc., and are easy to handle, and thus have been widely used in various applications in recent years.
- polystyrene resins, polymethyl methacrylate resins, polycarbonate resins, diethylene glycol diallyl carbonate resins, and the like have been used as such resins for organic optical materials.
- diethylene glycol diallyl carbonate resin (CR-39) used as a lens material has a refractive index as low as 1.50. Have the disadvantages of worsening the appearance and increasing the weight.
- R 1 and R 2 are a hydrogen atom or a methyl group.
- diaryl sulfide compounds are monomers that give a resin having a high refractive index and excellent transparency, but are expensive compounds for the production of the following chemical formula:
- the present invention has been made in view of the current state of the prior art described above, and its main purpose is as a monomer that gives a synthetic resin having a high refractive index and excellent transparency, compared with conventional compounds. It is to provide a compound that is inexpensive and has at least equivalent performance, and further to provide a production method thereof.
- Another object of the present invention is to provide a method capable of producing the raw material compound used in the above-mentioned novel compound production method under economically advantageous conditions with little environmental load.
- the present inventor has intensively studied to achieve the above-mentioned purpose. As a result, it has been found that a novel diarylsulfone compound having a specific substituent has excellent performance as a monomer capable of forming a resin having high refractive index and high hardness and good transparency. It was. And it discovered that this diaryl sulfone compound can be easily manufactured on the economically advantageous conditions from the dimercapto diaryl sulfone compound which is an inexpensive substance.
- the present inventor used a dimethylthiodiaryl sulfone compound represented by a specific general formula as a raw material for the dimercaptodiaryl sulfone compound that is a raw material used in the above production method, and after reacting it with a halogenating agent, It has been found that according to the hydrolysis method, it can be produced in a simple and inexpensive process.
- the present invention has been completed as a result of further research based on these findings.
- the present invention provides the following novel diarylsulfone compound, a production method thereof, and a production method of a raw material compound used in the production method.
- Item 1 General formula (1):
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R 5 represents the following formula:
- R 6 represents an alkylene group having 1 to 4 carbon atoms, and A represents an oxygen atom or a sulfur atom
- A represents an oxygen atom or a sulfur atom
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom).
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R 6 represents one to 1 carbon atom) 4) and at least one compound selected from the group consisting of thiourea and thiocyanate in an organic solvent. ⁇ 1-b):
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and M represents a cation site of the base.
- 4,4′-dimercaptodiaryl sulfone salt represented by the general formula (5):
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom).
- a diarylsulfone compound is reacted with a halogenating agent to give a general formula (7):
- a diarylsulfone compound which is then hydrolyzed, has the general formula (2):
- the diaryl sulfone compound of the present invention has the following general formula (1):
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R 5 represents the following formula:
- R 6 represents an alkylene group having 1 to 4 carbon atoms, and A represents an oxygen atom or a sulfur atom
- A represents an oxygen atom or a sulfur atom
- R 7 represents an alkenyl group having 2 to 5 carbon atoms. It is a novel compound not yet described in literature.
- the diaryl sulfone compound is a useful compound as a monomer that gives a synthetic resin for optical materials having a high refractive index and good transparency, for example.
- examples of the alkyl group having 1 to 4 carbon atoms represented by R 1 to R 4 and R 1 ′ to R 4 ′ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. And a linear or branched alkyl group such as n-butyl group, sec-butyl group, and tert-butyl group, and a methyl group is particularly preferable. Moreover, as a halogen atom, a chlorine atom, a bromine atom, an iodine atom etc. can be illustrated, and especially a chlorine atom is preferable.
- R 5 represents the following formula:
- R 6 represents an alkylene group having 1 to 4 carbon atoms, and A represents an oxygen atom or a sulfur atom
- A represents an oxygen atom or a sulfur atom
- R 1 to R 4 , R 1 ′ to R 4 ′ , R 6 and A are as defined above
- an alkylene group having 1 to 4 carbon atoms represented by R 6 examples thereof include linear alkylene groups such as methylene, ethylene, trimethylene and tetramethylene, and branched alkylene groups such as ethylethylene and 1,2-propylene.
- R 1 to R 4 and R 1 ′ to R 4 ′ are all hydrogen atoms
- R 6 is Examples thereof include compounds in which methylene group and A is O; compounds in which R 1 to R 4 and R 1 ′ to R 4 ′ are all hydrogen atoms, R 6 is a methylene group, and A is S.
- R 5 represents the following formula:
- R 7 represents an alkenyl group having 2 to 5 carbon atoms
- an alkenyl group having 2 to 5 carbon atoms represented by R 7 is preferably Is a straight-chain or branched alkenyl group having 2 to 5 carbon atoms having one or two carbon-carbon double bonds.
- Specific examples thereof include a vinyl group, an allyl group, an isopropenyl group, 1 -Butenyl group, isobutenyl group and the like can be mentioned.
- a vinyl group, an isopropenyl group, etc. are preferable.
- R 1 to R 4 and R 1 ′ to R 4 ′ are all hydrogen atoms
- R 7 is Examples thereof include compounds that are vinyl groups, compounds in which R 1 to R 4 and R 1 ′ to R 4 ′ are all hydrogen atoms, and R 7 is an isopropenyl group.
- R 1 to R 4 , R 1 ′ to R 4 ′ , R 6 and A are the same as above
- R 6 and A are the same as above
- the compound represented by the formula includes, for example, the following general formula (2):
- the 4,4′-dimercaptodiarylsulfone compound represented by the general formula (2) is a known compound, and specific examples of R 1 to R 4 and R 1 ′ to R 4 ′ in the formula are It is the same as that of Formula (1).
- Specific examples of the 4,4′-dimercaptodiarylsulfone compound include 4,4′-dimercaptodiphenylsulfone, 3,3′-dimethyl-4,4′-dimercaptodiphenylsulfone, and 2,2′-dimethyl.
- halide represented by the general formula (3) specific examples of the alkylene group represented by R 6 are the same as those in the general formula (1-1).
- halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is particularly preferable.
- halogen compound represented by the general formula (3) examples include epichlorohydrin and epibromohydrin, and epichlorohydrin is particularly preferable.
- the amount of the halide represented by the general formula (3) should be about 2 to 10 moles relative to 1 mole of the 4,4′-dimercaptodiarylsulfone compound represented by the general formula (2).
- the amount is preferably about 2 to 2.4 mol.
- lithium salts such as lithium chloride and lithium bromide can be used.
- lithium chloride is preferable in terms of reactivity and economy.
- the amount of the catalyst used is preferably about 0.001 to 0.2 mol per mol of the 4,4′-dimercaptodiarylsulfone compound represented by the general formula (2), and 0.01 to 0 More preferably, it is about 1 mol.
- examples of the solvent include n-hexane, n-heptane, and cyclohexane. It is preferable to use organic solvents such as hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene and o-dichlorobenzene, alcohols such as methanol, ethanol and isopropanol, and particularly toluene and methanol are used. It is preferable.
- organic solvents such as hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene and o-dichlorobenzene, alcohols such as methanol, ethanol and isopropanol, and particularly toluene and methanol are used. It is preferable.
- the specific reaction method is not particularly limited, and the 4,4′-dimercaptodiaryl sulfone compound represented by the general formula (2) and the general formula (3) in the above solvent in the presence of a catalyst. And a halide represented by (2) may be mixed uniformly. There is no particular limitation on the order of addition of each component, and any method can be adopted.
- the concentration of the 4,4′-dimercaptodiaryl sulfone compound in the reaction solution is preferably about 1 to 30% by weight, and more preferably about 5 to 15% by weight.
- the reaction temperature is not particularly limited, but is preferably about 0 to 70 ° C, more preferably about 30 to 60 ° C.
- the reaction time may be, for example, about 0.5 to 20 hours.
- the compound of the general formula (4) obtained in the first stage reaction may be used in the subsequent reaction with a base in a state dissolved in the reaction solvent after completion of the reaction.
- the compound of the general formula (4) may be used. You may make it react with a base, after isolate
- Examples of the base used for the reaction with the compound of the general formula (4) include metal hydroxides such as sodium hydroxide and potassium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, sodium hydride and potassium hydride. A metal hydride or the like can be used. Sodium hydroxide is preferred in terms of reactivity and economy.
- the amount of the base used is preferably about 0.1 to 10 mol, more preferably about 2.0 to 2.4 mol, relative to 1 mol of the compound of the general formula (4).
- the reaction of the compound of the general formula (4) and the base can be usually performed by mixing both in a solvent.
- a solvent an organic solvent, a mixed solvent of water and an organic solvent, or the like can be used.
- the organic solvent a solvent similar to the solvent used in the first stage reaction can be used.
- the amount of water used is preferably about 0.1 to 100 parts by weight with respect to 1 part by weight of the organic solvent.
- the concentration of the compound of the general formula (4) in the reaction solution is preferably about 1 to 30% by weight, more preferably about 10 to 20% by weight.
- the reaction is preferably performed in the presence of a phase transfer catalyst.
- a phase transfer catalyst tetrabutylammonium bromide, tetramethylammonium bromide, tetrabutylammonium tetrafluoroborate or the like can be used.
- tetrabutylammonium bromide is preferable from the viewpoints of reactivity and economy.
- the amount of the phase transfer catalyst used is preferably about 0.001 to 0.1 mol, more preferably about 0.03 to 0.07 mol, relative to 1 mol of the compound of the general formula (4). preferable.
- the reaction temperature is preferably about 0 to 70 ° C, more preferably about 30 to 60 ° C.
- the reaction time may be about 0.5 to 20 hours, for example.
- the organic layer and the aqueous layer are separated, the organic layer is washed with water, and then the solvent is distilled off to obtain the compound represented by the general formula (1-1-a).
- the diaryl sulfone compound obtained can be obtained.
- the target compound of the general formula (1-1-a) can be easily separated by adding water after completion of the reaction and using the same method as the above mixed solvent. .
- R 1 to R 4 , R 1 ′ to R 4 ′ , and R 6 are the same as above
- at least one compound selected from the group consisting of thiourea and thiocyanate Can be obtained by reacting in an organic solvent.
- thiocyanate potassium thiocyanate, ammonium thiocyanate, or the like can be used.
- Thiourea and thiocyanate can be used singly or in combination of two or more.
- the amount of at least one compound selected from the group consisting of thiourea and thiocyanate is about 2 to 8 moles per mole of the compound represented by the general formula (1-1-a). It is preferable to use about 2 to 6 moles.
- organic solvent examples include halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene, hydrocarbons such as n-hexane, n-heptane, cyclohexane, toluene and xylene, tetrahydrofuran , Ethers such as 1,4-dioxane, and alcohols such as methanol, ethanol and isopropanol can be used.
- concentration of the compound represented by the general formula (1-1-a) in the reaction solution is preferably about 1 to 30% by weight, and more preferably about 5 to 15% by weight.
- the reaction temperature is preferably about 0 to 80 ° C., more preferably about 10 to 60 ° C.
- the reaction time may be about 0.5 to 20 hours, for example.
- R 1 to R 4 , R 1 ′ to R 4 ′ , and R 6 are the same as described above.
- R 7 represents an alkenyl group having 2 to 5 carbon atoms
- R 1 to R 4 , R 1 ′ to R 4 ′ , and R 7 are the same as described above.
- R 1 to R 4 and R 1 ′ to R 4 are the same as described above, M represents a cation part of a base), and a 4,4′-dimercaptodiaryl sulfone salt represented by Formula (5):
- the 4,4′-dimercaptodiaryl sulfone salt represented by the general formula (2-1) is represented by the following general formula (2):
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same as above
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same as above
- Bases include metal hydroxides such as sodium hydroxide and potassium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and tributylamine, metals such as sodium hydride and potassium hydride Of the hydrides.
- metal hydroxides such as sodium hydroxide and potassium hydroxide
- metal carbonates such as sodium carbonate and potassium carbonate
- tertiary amines such as triethylamine and tributylamine
- metals such as sodium hydride and potassium hydride
- hydrides include sodium hydroxide or sodium hydride in terms of reactivity and economy.
- the cation moiety represented by M is a cation moiety corresponding to the base to be used. It becomes.
- M + represents Na + , K + , N + R 3 H (R is an alkyl group such as an ethyl group or a butyl group), and the like.
- the reaction between the 4,4′-dimercaptodiarylsulfone compound represented by the general formula (2) and the base can be usually performed by mixing both in a solvent.
- a solvent water or an organic solvent can be used.
- the organic solvent include hydrocarbons such as n-hexane, n-heptane, cyclohexane, toluene and xylene, halogen hydrocarbons such as chlorobenzene and o-dichlorobenzene, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like.
- aprotic polar solvents In the case of using an organic solvent, it is preferable to use a non-aqueous base such as the above-mentioned tertiary amine or metal hydride as the base.
- the amount of base used is preferably about 1 to 10 moles, more preferably about 2 to 2.4 moles per mole of 4,4'-dimercaptodiarylsulfone compound.
- the concentration of the 4,4′-dimercaptodiaryl sulfone compound in the solvent is preferably about 1 to 30% by weight, more preferably about 5 to 15% by weight.
- the reaction temperature of the reaction between the 4,4′-dimercaptodiarylsulfone compound and the base is preferably about 0 to 70 ° C., more preferably about 30 to 60 ° C.
- the reaction time may be about 0.5 to 20 hours, for example.
- the 4,4′-dimercaptodiaryl sulfone compound represented by the general formula (2) is reacted with a base by the above-described method to produce the 4,4′-dimercapto represented by the general formula (2-1).
- a 4,4′-dimercaptodiarylsulfone salt represented by the general formula (2-1) may be obtained and used as it is.
- the reaction with the halide represented by the formula (wherein R 7 and X are the same as above) can be carried out in a solvent such as water, an organic solvent, or a mixed solvent of water and an organic solvent.
- a solvent such as water, an organic solvent, or a mixed solvent of water and an organic solvent.
- the organic solvent a solvent similar to the solvent used for the reaction between the 4,4′-dimercaptodiarylsulfone compound represented by the general formula (2) and the base can be used.
- the 4,4′-dimercaptodiaryl sulfone salt represented by the general formula (2-1) is obtained using water as a solvent by the above-described method
- the 4,4′-dimercaptodiaryl sulfone salt is obtained.
- the halide represented by the general formula (5) may be mixed as it is in the aqueous solution containing the solution, or a solution in which the halide represented by the general formula (5) is dissolved in an organic solvent, and the general formula (2- You may mix with the aqueous solution containing the 4,4'- dimercapto diaryl sulfone salt represented by 1).
- the 4,4′-dimercaptodiaryl sulfone salt represented by the general formula (2-1) is obtained using an organic solvent as a solvent
- the halogen represented by the general formula (5) in the solvent is obtained.
- the compound may be mixed as it is, or a solution obtained by dissolving the halide represented by the general formula (5) in an organic solvent may be added and mixed.
- the 4,4′-dimercaptodiarylsulfone compound represented by the general formula (2), the base, and the halide represented by the general formula (5) may be simultaneously added to the organic solvent to cause the reaction.
- the 4,4′-dimercaptodiarylsulfone compound represented by the general formula (2) reacts with the base in an organic solvent, and the 4,4′-form represented by the general formula (2-1). Dimercaptodiaryl sulfone salt is formed, which is considered to react with the halide represented by the general formula (5).
- halide represented by the general formula (5) specific examples of the alkenyl group having 2 to 5 carbon atoms represented by R 7 are the same as those in the general formula (1-2).
- halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is particularly preferable.
- halogen compound represented by the general formula (5) examples include acrylic acid chloride, acrylic acid bromide, methacrylic acid chloride, and methacrylic acid bromide.
- acrylic acid chloride, methacrylic acid chloride and the like are preferable.
- the amount of the halide represented by the general formula (5) is about 2 to 10 moles with respect to 1 mole of the 4,4′-dimercaptodiaryl sulfone salt represented by the general formula (2-1). It is preferably about 2 to 2.4 mol.
- the reaction between the 4,4′-dimercaptodiaryl sulfone salt represented by the general formula (2-1) and the halide represented by the general formula (5) is performed in a mixed solvent of water and an organic solvent.
- the amount of water used is preferably about 0.1 to 100 parts by weight with respect to 1 part by weight of the organic solvent.
- N-methylpyrrolidone is preferable.
- a mixed solvent of an organic solvent and water is used, a mixed solvent of toluene / cyclohexane / water is preferable.
- the concentration of 4,4'-dimercaptodiaryl sulfone salt in the reaction solution is preferably about 1 to 30% by weight, more preferably about 5 to 15% by weight.
- the reaction temperature is not particularly limited, but is preferably about 0 to 70 ° C, more preferably about 30 to 60 ° C.
- the reaction time may be about 0.5 to 20 hours, for example.
- R 1 to R 4 , R 1 ′ to R 4 ′ , and R 7 are the same as described above.
- the target diaryl sulfone compound represented by general formula (1-2) can be easily separated by a method such as filtration.
- the 4,4'-dimercaptodiarylsulfone compound represented by the general formula (2) used as a raw material in the production of the diarylsulfone compound described above is
- the dimethylthiodiarylsulfone compound represented by the general formula (6) is used as a raw material, and can be produced in a simple and inexpensive process by reacting it with a halogenating agent and then hydrolyzing it. This will be specifically described.
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom).
- a diaryl sulfone compound is reacted with a halogenating agent to give the following general formula (7):
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same as above, X represents a halogen atom, and m and n each represents an integer of 1 to 3).
- a diaryl sulfone compound is used.
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same as those in the general formula (1).
- Specific examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. From an economical point of view, R 1 to R 4 and R 1 ′ to R 4 ′ are preferably hydrogen atoms.
- halogenating agent examples include chlorine, sulfuryl chloride, phosphorus pentachloride, phosphorus trichloride, hypochlorous acid, bromine and the like.
- the amount of the halogenating agent used is preferably about 2 to 12 moles per mole of the 4,4′-dimethylthiodiaryl sulfone compound represented by the general formula (6), and is about 2 to 4 moles. More preferably.
- reaction solvent examples include polar solvents such as dimethylsulfoxide, N-methylpyrrolidone, N, N-dimethylformamide, methylene chloride, 1,2 It is preferable to use halogenated hydrocarbons such as dichloroethane, chlorobenzene and o-dichlorobenzene, hydrocarbons such as n-hexane, n-heptane, cyclohexane, toluene and xylene. From an economical viewpoint, toluene is more preferable.
- the amount of the reaction solvent used is preferably about 10 to 5000 parts by weight, more preferably about 100 to 1000 parts by weight with respect to 100 parts by weight of the 4,4′- dimethylthiodiarylsulfone compound.
- the reaction temperature is preferably about 30 to 120 ° C, more preferably about 40 to 70 ° C.
- the reaction time is usually about 1 to 30 hours.
- the halogen atom represented by X corresponds to the halogenating agent used, and examples thereof include a chlorine atom, a bromine atom, and an iodine atom.
- the value of m and the value of n can vary in the range of 1 to 3, respectively, but are usually values according to the amount of halogenating agent used.
- the amount of the halogenating agent is 2 moles of the 4,4′-dimethylthiodiarylsulfone compound represented by the general formula (6)
- the values of m and n in the general formula (7) In the case where the diarylsulfone compound, which is also 1 is the main product, and the amount of the halogenating agent is 4 moles of the 4,4′-dimethylthiodiarylsulfone compound represented by the general formula (6),
- a diaryl sulfone compound in which the values of m and n are both 2 is the main product.
- the diarylsulfone compound thus obtained can be obtained by washing with water and separating as necessary. Moreover, after distilling off the solvent, it can be isolated with increased purity by recrystallization.
- a solvent obtained by adding water to the organic solvent used in the above halogenation reaction for example, a mixed solvent of polar solvent such as dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylformamide and water; methylene chloride
- halogenated hydrocarbons such as 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene, mixed solvents of hydrocarbons such as n-hexane, n-heptane, cyclohexane, toluene and xylene with water Can do.
- the mixed solvent of polar solvent and water becomes a homogeneous solvent
- the mixed solvent of halogenated hydrocarbons or hydrocarbons and water becomes a two-phase solvent.
- a two-phase solvent of toluene and water is preferable from an economical viewpoint.
- the amount of water used for hydrolysis is preferably about 2 to 200 mol, more preferably about 10 to 50 mol, per 1 mol of the diaryl sulfone compound.
- the reaction temperature is preferably about 30 to 150 ° C., more preferably about 70 to 120 ° C.
- the reaction time is usually about 1 to 30 hours.
- the dimercaptodiarylsulfone compound represented by the general formula (2) can be obtained.
- the dimercaptodiarylsulfone compound thus obtained can be obtained by separating the organic phase and the aqueous phase when the two-phase solvent is used, washing the organic phase with water, and then distilling off the solvent. Moreover, when a uniform solvent is used, it can be easily obtained by a method such as filtration.
- diaryl sulfone compound obtained in the present invention examples include 4,4'-dimercaptodiphenyl sulfone.
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom).
- the diaryl sulfone compound is a novel compound and can be obtained, for example, by the following method.
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and X represents a halogen atom.
- MSCH 3 wherein M represents an alkali metal.
- the 4,4′-dihalodiarylsulfone compound of the general formula (8) used as a raw material is a known compound and is a relatively inexpensive substance.
- examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is particularly preferable.
- R 1 to R 4 and R 1 ′ to R 4 ′ are the same as those in the general formula (1).
- examples of the alkali metal represented by M include sodium, potassium, and lithium.
- thiol salt compound of the general formula (9) examples include sodium methanethiolate.
- the thiol salt compound of the general formula (9) is added directly to the reaction solvent as an alkali metal salt, and the thiol represented by the general formula: HSCH 3 and an alkali metal hydride (MH) or alkali metal hydroxide (MOH) ) May be added to the solvent to form a salt in the solvent.
- HSCH 3 and an alkali metal hydride (MH) or alkali metal hydroxide (MOH) May be added to the solvent to form a salt in the solvent.
- the amount of the thiol salt compound of the general formula (9) used is preferably about 2 to 6 moles relative to 1 mole of the 4,4′-dihalodiaryl sulfone compound of the general formula (8). More preferably, it is about a mole.
- the reaction of the 4,4′-dihalodiaryl sulfone compound represented by the general formula (8) with the thiol salt compound represented by the general formula (9) is, for example, dimethyl sulfoxide, N-methylpyrrolidone, N, Carried out in a polar solvent such as N-dimethylformamide, or halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chlorobenzene, o-dichlorobenzene, n-hexane, n-heptane, cyclohexane, toluene, It is preferably carried out in a two-phase solvent of an organic solvent such as hydrocarbons such as xylene and water. In particular, from an economic viewpoint, it is preferable to use N-methylpyrrolidone alone or a two-phase solvent of toluene and water.
- the reaction solvent is used in an amount of about 10 to 5000 parts by weight per 100 parts by weight of the 4,4′-dihalodiarylsulfone compound represented by the general formula (8).
- the amount is preferably about 100 to 1000 parts by weight.
- both the organic solvent and water should be about 10 to 5000 parts by weight with respect to 100 parts by weight of the 4,4′-dihalodiarylsulfone compound represented by the general formula (8).
- the amount is preferably about 100 to 1000 parts by weight.
- phase transfer catalyst When performing the reaction in a two-phase solvent, it is preferable to use a phase transfer catalyst.
- the phase transfer catalyst include quaternary ammonium salts such as benzyltriethylammonium bromide, benzyltrimethylammonium bromide, dodecyltrimethylammonium chloride, tetra-n-butylammonium bromide, tetraethylammonium bromide and trioctylmethylammonium bromide; hexadodecyltriethyl Quaternary phosphonium salts such as phosphonium bromide, hexadodecyltributylphosphonium chloride and tetra-n-butylphosphonium chloride can be used.
- tetra-n-butylammonium bromide is preferred from the viewpoint of yield improvement and economy.
- the amount of the phase transfer catalyst used is preferably about 0.1 to 100 parts by weight with respect to 100 parts by weight of the 4,4′-dihalodiarylsulfone compound of the general formula (8), More preferably, it is about the weight part.
- the reaction temperature is preferably about 30 to 150 ° C., more preferably about 60 to 150 ° C.
- the reaction time is usually about 1 to 30 hours.
- the specific reaction method is not particularly limited, and a 4,4′-dihalodiarylsulfone compound represented by the general formula (8) can be added to the above-described solvent by adding a catalyst as necessary. What is necessary is just to mix uniformly with the thiol salt compound represented by Formula (9). There is no particular limitation on the order of addition of each component, and any method can be adopted.
- the diaryl sulfone compound thus obtained can be obtained by washing with water and separating as necessary. Moreover, after distilling off the solvent, it can be isolated with increased purity by recrystallization.
- a 4,4′-dimercaptodiarylsulfone compound represented by the general formula (2) which is an inexpensive substance, is used as a raw material, and the target is obtained in a high yield by a relatively simple production process.
- a diaryl sulfone compound can be obtained.
- the diaryl sulfone compound obtained by this method is a compound useful as a monomer or the like that provides a synthetic resin for optical materials having a high refractive index and good transparency.
- optical materials having a high refractive index and good transparency.
- plastic lenses for glasses, Fresnel lenses, lenticular lenses It can be effectively used as a raw material for optical materials such as optical disk substrates and plastic optical fibers.
- the 4,4′-dimercaptodiarylsulfone compound represented by the general formula (2) used as a raw material in the above method can be easily and inexpensively manufactured by the manufacturing method of the present invention. it can.
- Example 1 Production of bis [(4-glycidylthio) phenyl] sulfone 4,4'-dimercaptodiphenylsulfone was placed in a 100 ml flask equipped with a stirrer, thermometer, cooling tube and gas introduction tube. After adding 9.88 g (35.0 mmol), lithium chloride 0.07 g (1.8 mmol), toluene 20.00 g and methanol 10.00 g, the liquid temperature was raised to 50 ° C., and epichlorohydrin 6. 70 g (72.0 mmol) was added and reacted at 50 ° C. for 2 hours with stirring.
- the liquid temperature was cooled to 30 ° C., 9.8 g of water, 1.0 g of 50 wt% tetrabutylammonium bromide and 9.70 g (72.8 mmol) of 30 wt% aqueous sodium hydroxide were added and stirred. The reaction was allowed to proceed at 35 ° C. for 1 hour.
- Example 3 Production of bis (4-acryloylthiophenyl) sulfone 4,4'-dimercaptodiphenyl sulfone was added to a 10 ml internal flask equipped with a stirrer, a thermometer, a condenser tube and a gas introduction tube. After adding 95 g (6.9 mmol) and 10 wt% aqueous sodium hydroxide solution (6.00 g, 15.0 mmol), the mixture was cooled to a liquid temperature of 10 ° C. (reaction liquid A).
- reaction solution was filtered to obtain 1.08 g of bis (4-acryloylthiophenyl) sulfone as a white powder.
- the yield based on 4,4′-dimercaptodiphenyl sulfone was 40%.
- Example 4 Production of bis (4-acryloylthiophenyl) sulfone 4,4'-dimercaptodiphenyl sulfone was placed in a 10 ml flask equipped with a stirrer, thermometer, condenser and gas inlet tube. After adding 95 g (6.9 mmol) and 6.0 wt. G (15.0 mmol) of a 10% by weight aqueous sodium hydroxide solution, the solution was cooled to 10 ° C. Then, acrylic acid chloride 1.31g (14.5mmol) was dripped in 30 seconds, and it was made to react at 20 degreeC for 1 hour, stirring.
- reaction solution was filtered to obtain 0.95 g of bis (4-acryloylthiophenyl) sulfone as a white powder.
- the yield based on 4,4′-dimercaptodiphenyl sulfone was 35%.
- Example 5 Production of bis (4-methacryloylthiophenyl) sulfone 4,4'-dimercaptodiphenyl sulfone was added to a 10 ml internal flask equipped with a stirrer, thermometer, cooling pipe and gas introduction pipe. After adding 95 g (6.9 mmol) and 10 wt% aqueous sodium hydroxide solution (6.00 g, 15.0 mmol), the mixture was cooled to a liquid temperature of 10 ° C. (reaction liquid A).
- reaction solution was filtered to obtain 2.58 g of bis (4-methacryloylthiophenyl) sulfone as a white powder.
- the yield based on 4,4′-dimercaptodiphenylsulfone was 90%.
- Example 6 Production of bis (4-methacryloylthiophenyl) sulfone 4,4'-dimercaptodiphenyl sulfone was added to a 10 ml internal flask equipped with a stirrer, thermometer, cooling pipe and gas introduction pipe. After adding 95 g (6.9 mmol), 0.36 g (15.2 mmol) of sodium hydride and 6.00 g of N-methylpyrrolidone, the solution was cooled to 10 ° C. Thereafter, 1.52 g (14.5 mmol) of methacrylic acid chloride was dropped in 30 seconds, and the mixture was reacted at 20 ° C. for 1 hour with stirring.
- Example 7 Production of 4,4′-dimercaptodiphenylsulfone 8.4 g (27 mmol) of 4,4′-dimethylthiodiphenylsulfone was placed in a 100 ml flask equipped with a stirrer, thermometer, cooling pipe and gas introduction pipe. Then, 50.0 g of toluene was added, the temperature was raised, and while maintaining the liquid temperature at 75 ° C., 4.8 g (68 mmol) of chlorine gas was blown in, and the mixture was reacted for 1 hour with stirring. As a result, bis (4-chloromethylsulfanylphenyl) sulfone was produced in the system.
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Abstract
Description
項1. 一般式(1):
項2. 一般式(1-1):
項3. 一般式(1-2):
項4. R1~R4及びR1’~R4’がいずれも水素原子である上記項1~3のいずれかに記載のジアリールスルホン化合物。
項5. 一般式(2):
項6.一般式(1-1-a):
項7. 一般式(2-1):
項8. 一般式(6):
本発明のジアリールスルホン化合物は、下記一般式(1):
(1)第一方法
一般式(1):
一般式(1―1)において、Aが硫黄原子である化合物、即ち、一般式(1―1-b):
一般式(1):
上記したジアリールスルホン化合物の製造において原料として用いる一般式(2)で表される4,4’-ジメルカプトジアリールスルホン化合物は、下記一般式(6)で表されるジメチルチオジアリールスルホン化合物を原料として、これをハロゲン化剤と反応させた後、加水分解する方法によって、簡便にかつ安価な工程で製造できる、以下、この方法について具体的に説明する。
本発明方法では、まず、第一工程として、下記一般式(6):
次いで、上記工程で得られた一般式(7):
上記したジメチルチオジアリールスルホン化合物とハロゲン化剤との反応工程で用いる、一般式(6):
攪拌機、温度計、冷却管およびガス導入管を備えた内容積100mlのフラスコに、4,4’-ジメルカプトジフェニルスルホン9.88g(35.0mmol)、塩化リチウム0.07g(1.8mmol)、トルエン20.00gおよびメタノール10.00gを加えた後、液温を50℃まで昇温し、エピクロロヒドリン6.70g(72.0mmol)を添加し、攪拌しながら50℃で2時間反応させた。
1H NMR d 2.65(dd,J=2.4Hz、4.8Hz,2H)、2.83(dd, J=3.6Hz、4.4Hz,2H)、3.15-3.21(m, 6H)、7.41(d, J=8.8Hz,4H)、7.80(d, J=8.8Hz,4H);
元素分析(C18H18O4S3として);
計算値 C:54.80%、H:4.60%、O:16.22%、S:24.38%
実測値 C:54.76%、H:4.62%、O:16.14%、S:24.48%
屈折率 ;1.645
攪拌機、温度計、冷却管およびガス導入管を備えた内容積100mlのフラスコに、ビス[(4-グリシジルチオ)フェニル]スルホン6.00g(15.0mmol)、塩化メチレン23.40gおよびメタノール31.00gを加えた後、液温を45℃まで昇温し、チオ尿素9.10g(120.0mmol)を添加し、攪拌しながら45℃で4時間反応させた。
1H NMR d 2.23(dd,J=1.2Hz、5.2Hz,2H)、2.83(m, 2H)、2.94-3.21(m, 6H)、7.41(d, J=8.8Hz,4H)、7.82(d, J=8.4Hz,4H);
元素分析(C18H18O2S5として);
計算値 C:50.67%、H:4.25%、O:7.50%、S:37.58%
実測値 C:50.76%、H:4.22%、O:7.45%、S:37.57%
屈折率 ;1.664
攪拌機、温度計、冷却管およびガス導入管を備えた内容積10mlのフラスコに、4,4’-ジメルカプトジフェニルスルホン1.95g(6.9mmol)及び10重量%の水酸化ナトリウム水溶液6.00g(15.0mmol)を加えた後、液温10℃に冷却した(反応液A)。一方で、攪拌機、温度計、冷却管およびガス導入管を備えた内容積25mlのフラスコに、アクリル酸クロリド1.31g(14.5mmol)、シクロヘキサン5.00g及びトルエン2.00gを加えた後、液温を10℃に冷却し、反応液Aを30秒で滴下し、攪拌しながら20℃で1時間反応させた。
1H NMR d 5.70(d,J=9.2Hz,2H)、6.34-6.49(m, 4H)、 7.55(d,J=6.8Hz,4H)、7.88(d,J=6.8Hz,4H);
元素分析(C18H14O4S3として) ;
計算値 C:55.36%、H:3.61%、O:16.39%、S:24.63%
実測値 C:55.28%、H:3.58%、O:16.43%、S:24.70%
屈折率 ;1.639
攪拌機、温度計、冷却管およびガス導入管を備えた内容積10mlのフラスコに、4,4’-ジメルカプトジフェニルスルホン1.95g(6.9mmol)及び10重量%の水酸化ナトリウム水溶液6.00g(15.0mmol)を加えた後、液温10℃に冷却した。その後、アクリル酸クロリド1.31g(14.5mmol)を30秒で滴下し、攪拌しながら20℃で1時間反応させた。反応終了後、反応液を濾過することにより、白色粉末として、ビス(4-アクリロイルチオフェニル)スルホン0.95gを得た。4,4’-ジメルカプトジフェニルスルホンに対する収率は、35%であった。
攪拌機、温度計、冷却管およびガス導入管を備えた内容積10mlのフラスコに、4,4’-ジメルカプトジフェニルスルホン1.95g(6.9mmol)及び10重量%の水酸化ナトリウム水溶液6.00g(15.0mmol)を加えた後、液温10℃に冷却した(反応液A)。一方で、攪拌機、温度計、冷却管およびガス導入管を備えた内容積25mlのフラスコに、メタクリル酸クロリド1.52g(14.5mmol)、シクロヘキサン5.00g及びトルエン3.00gを加えた後、液温を10℃に冷却し、反応液Aを30秒で滴下し、攪拌しながら20℃で1時間反応させた。
1H NMR d 2.00(s, 6H)、5.77(s,2H)、6.21(s,2H)、7.60(d, J=6.8Hz,4H)、7.98(d, J=6.8Hz,4H);
元素分析(C20H18O4S3として) ;
計算値 C:57.39%、H:4.33%、O:15.29%、S:22.98%
実測値 C:57.30%、H:4.38%、O:15.35%、S:22.96%
屈折率 ;1.631
攪拌機、温度計、冷却管およびガス導入管を備えた内容積10mlのフラスコに、4,4‘-ジメルカプトジフェニルスルホン1.95g(6.9mmol)、水素化ナトリウム0.36g(15.2mmol)及びN-メチルピロリドン6.00gを加えた後、液温10℃に冷却した。その後、メタクリル酸クロリド1.52g(14.5mmol)を30秒で滴下し、攪拌しながら20℃で1時間反応させた。反応終了後、反応液に水5.0gを加えた後、濾過することにより、白色粉末として、ビス(4-メタクリロイルチオフェニル)スルホン2.44gを得た。4,4‘-ジメルカプトジフェニルスルホンに対する収率は、85%であった。
攪拌機、温度計、冷却管およびガス導入管を備えた内容積100mlのフラスコに、4,4’-ジメチルチオジフェニルスルホン8.4g(27mmol)およびトルエン50.0gを加え、昇温して、液温を75℃に保ちながら、塩素ガス4.8g(68mmol)を吹き込み、攪拌しながら1時間反応させた。その結果、系内でビス(4-クロロメチルスルファニルフェニル)スルホンが生成した。
攪拌機、温度計、冷却管およびガス導入管を備えた内容積300mlのフラスコに、4,4’-ジクロロジフェニルスルホン61.0g(212mmol)、トルエン75.0gおよび50重量%テトラ-n-ブチルアンモニウムブロミド水溶液1.0gを加え、昇温し、液温を60℃に保ちながら、32重量%ナトリウムメタンチオラート水溶液97.5g(445mmol)を滴下し、攪拌しながら5時間反応させた。
1H NMR d 2.48(s,6H)、7.27(d,J=8.4Hz,4H)、7.79(d,J=8.8Hz,4H);
元素分析(C14H14O2S3として) ;
計算値 C:54.16%、H:4.55%、O:10.31%、S:30.99%
実測値 C:54.19%、H:4.61%、O:10.27%、S:30.94%
屈折率 ;1.644
Claims (8)
- R1~R4及びR1’~R4’がいずれも水素原子である請求項1~3のいずれかに記載のジアリールスルホン化合物。
- 一般式(2):
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CN104245684B (zh) * | 2012-04-16 | 2016-01-06 | 三菱瓦斯化学株式会社 | 含硫环氧化合物的制造方法 |
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US20130005993A1 (en) | 2013-01-03 |
TWI555725B (zh) | 2016-11-01 |
TW201144267A (en) | 2011-12-16 |
EP2548861A4 (en) | 2013-09-04 |
EP2548861A1 (en) | 2013-01-23 |
CN102812002A (zh) | 2012-12-05 |
US9040724B2 (en) | 2015-05-26 |
KR20130030257A (ko) | 2013-03-26 |
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