JP2008169161A - Method for producing methylene disulfonate compound - Google Patents
Method for producing methylene disulfonate compound Download PDFInfo
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- JP2008169161A JP2008169161A JP2007005007A JP2007005007A JP2008169161A JP 2008169161 A JP2008169161 A JP 2008169161A JP 2007005007 A JP2007005007 A JP 2007005007A JP 2007005007 A JP2007005007 A JP 2007005007A JP 2008169161 A JP2008169161 A JP 2008169161A
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- methylene disulfonate
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- -1 methylene disulfonate compound Chemical class 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 125000005843 halogen group Chemical group 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical group O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- IQLZWWDXNXZGPK-UHFFFAOYSA-N methylsulfonyloxymethyl methanesulfonate Chemical compound CS(=O)(=O)OCOS(C)(=O)=O IQLZWWDXNXZGPK-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BPGDAMSIGCZZLK-UHFFFAOYSA-N acetyloxymethyl acetate Chemical compound CC(=O)OCOC(C)=O BPGDAMSIGCZZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical class OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229910001958 silver carbonate Inorganic materials 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LEXULLPDKRNGQG-UHFFFAOYSA-N (4-methylphenyl)sulfonyloxymethyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCOS(=O)(=O)C1=CC=C(C)C=C1 LEXULLPDKRNGQG-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- MGWIVXXTDAHZPB-UHFFFAOYSA-N benzenesulfonyloxymethyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OCOS(=O)(=O)C1=CC=CC=C1 MGWIVXXTDAHZPB-UHFFFAOYSA-N 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- YGNOYUCUPMACDT-UHFFFAOYSA-N dimethylsulfamic acid Chemical compound CN(C)S(O)(=O)=O YGNOYUCUPMACDT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- BLUWFHDXYDEUDP-UHFFFAOYSA-N trifluoromethylsulfonyloxymethyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)OCOS(=O)(=O)C(F)(F)F BLUWFHDXYDEUDP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、メチレンジスルホネート化合物の製造方法に関する。 The present invention relates to a method for producing a methylene disulfonate compound.
メチレンジスルホネート化合物は、白血病動物治療薬等の医薬品として有用な化合物である。 A methylene disulfonate compound is a compound useful as a pharmaceutical product such as a leukemia animal therapeutic agent.
メチレンジスルホネート化合物の製造方法としては、種々の方法が知られている。例えば、スルホニルクロリドと炭酸銀とを反応させて得られるスルホン酸銀をジヨードメタンと反応させる方法（特許文献１参照）、 Various methods are known for producing methylene disulfonate compounds. For example, a method of reacting silver sulfonate obtained by reacting sulfonyl chloride and silver carbonate with diiodomethane (see Patent Document 1),
アルカンジスルホン酸等とメチレンジアセテート等とを反応させる方法（特許文献２参照） Method of reacting alkanedisulfonic acid or the like with methylene diacetate or the like (see Patent Document 2)
等が知られている。 Etc. are known.
これらの方法と同様にして、種々のメチレンジスルホネート化合物を製造することができるが、これらの方法には不具合な点がある。例えば、特許文献１に記載の製造方法によると、使用する炭酸銀やジヨードメタンが高価であり、反応速度が遅いという問題がある。また、特許文献２に記載の製造方法によると、使用するメチレンジアセテート等は入手が必ずしも容易ではなく、また高価であるという問題がある。 Various methylene disulfonate compounds can be produced in the same manner as these methods, but these methods have drawbacks. For example, according to the production method described in Patent Document 1, there is a problem that silver carbonate and diiodomethane to be used are expensive and the reaction rate is slow. Further, according to the production method described in Patent Document 2, there is a problem that methylene diacetate to be used is not always easy to obtain and is expensive.
本発明は、メチレンジスルホネート化合物を工業的に安価で容易に製造する方法を提供することを目的とする。 An object of this invention is to provide the method of manufacturing a methylene disulfonate compound industrially cheaply and easily.
本発明は、一般式（１）： The present invention relates to a general formula (1):
（式中、Ｒ１は、水素原子、ハロゲン原子、水素原子がハロゲン原子で置換されていてもよい炭素数１〜４のアルキル基、置換基を有してもよい芳香環基、または一般式（２）： (Wherein R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom, an aromatic ring group that may have a substituent, or a general formula; (2):
（式中、Ｒ２およびＲ３は、それぞれ独立して、水素原子、または水素原子がハロゲン原子で置換されていてもよい炭素数１〜３のアルキル基を示す。）で表される基を示す。）で表されるスルホン酸化合物と、ホルムアルデヒド化合物とを脱水剤の存在下で反応させることを特徴とする、一般式（３）： (Wherein R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms in which the hydrogen atom may be substituted with a halogen atom). Show. ) And a formaldehyde compound are reacted in the presence of a dehydrating agent, general formula (3):
（式中、Ｒ１は、前記一般式（１）におけるＲ１と同じ基を示す。）で表されるメチレンジスルホネート化合物の製造方法に関する。 (In the formula, R 1,. Showing the same group as R 1 in the general formula (1)) The method for producing a methylene disulfonate compound represented by.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明に用いられるスルホン酸化合物は、下記一般式（１）で表される化合物である。 The sulfonic acid compound used in the present invention is a compound represented by the following general formula (1).
一般式（１）において、Ｒ１は、水素原子、ハロゲン原子、水素原子がハロゲン原子で置換されていてもよい炭素数１〜４のアルキル基、置換基を有してもよい芳香環基、または一般式（２）： In General Formula (1), R 1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom, an aromatic ring group that may have a substituent, Or general formula (2):
（式中、Ｒ２およびＲ３は、それぞれ独立して、水素原子、または水素原子がハロゲン原子で置換されていてもよい炭素数１〜３のアルキル基を示す。）で表される基を示す。 (Wherein R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms in which the hydrogen atom may be substituted with a halogen atom). Show.
Ｒ１で示されるハロゲン原子としては、例えば、フッ素原子、塩素原子および臭素原子等が挙げられる。 Examples of the halogen atom represented by R 1 include a fluorine atom, a chlorine atom, and a bromine atom.
Ｒ１で示される、水素原子がハロゲン原子で置換されていてもよい炭素数１〜４のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、クロロメチル基、ブロモメチル基、フルオロメチル基およびトリフルオロメチル基等が挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms in which the hydrogen atom optionally substituted with a halogen atom represented by R 1 include, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl. Group, iso-butyl group, sec-butyl group, tert-butyl group, chloromethyl group, bromomethyl group, fluoromethyl group, trifluoromethyl group and the like.
Ｒ１で示される、置換基を有してもよい芳香環基としては、例えば、フェニル基、ナフチル基、ピリジル基、トリル基、ドデシルフェニル基およびクロロフェニル基等が挙げられる。 Examples of the aromatic ring group which may have a substituent represented by R 1 include a phenyl group, a naphthyl group, a pyridyl group, a tolyl group, a dodecylphenyl group and a chlorophenyl group.
Ｒ１が一般式（２）で表される基において、Ｒ２およびＲ３で示される水素原子がハロゲン原子で置換されていてもよい炭素数１〜３のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基およびｉｓｏ−プロピル基等が挙げられる。一般式（２）で表される基の具体例としては、Ｎ−メチルアミノ基、Ｎ，Ｎ−ジメチルアミノ基等が挙げられる。 In the group in which R 1 is represented by the general formula (2), as the alkyl group having 1 to 3 carbon atoms in which the hydrogen atom represented by R 2 and R 3 may be substituted with a halogen atom, for example, a methyl group , Ethyl group, n-propyl group, iso-propyl group and the like. Specific examples of the group represented by the general formula (2) include an N-methylamino group and an N, N-dimethylamino group.
これらの中で、Ｒ１の好ましい例としては、メチル基、トリル基およびＮ，Ｎ−ジメチルアミノ基が好ましい。 Among these, preferred examples of R 1 are a methyl group, a tolyl group, and an N, N-dimethylamino group.
一般式（１）で表されるスルホン酸化合物の具体例としては、例えばメタンスルホン酸、トリフルオロメタンスルホン酸、ベンゼンスルホン酸、パラトルエンスルホン酸およびＮ，Ｎ−ジメチルスルファミン酸等を挙げることができる。 Specific examples of the sulfonic acid compound represented by the general formula (1) include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, paratoluenesulfonic acid and N, N-dimethylsulfamic acid. .
本発明において、前記スルホン酸化合物は、市販のものを使用することができる。 In the present invention, a commercially available sulfonic acid compound can be used.
本発明に用いられるホルムアルデヒド化合物としては、例えば、パラホルムアルデヒド、パラホルムアルデヒドを加熱処理して得られる無水ホルムアルデヒド、パラホルムアルデヒドを酸処理して得られるトリオキサン、および、メチラール等のホルムアルデヒドのアセタール化物等が挙げられる。これらの中でも、パラホルムアルデヒド、無水ホルムアルデヒドおよびトリオキサンが好適に用いられる。これらホルムアルデヒド化合物は、それぞれ単独で、あるいは２種以上を組み合わせて用いてもよい。 Examples of the formaldehyde compound used in the present invention include paraformaldehyde, anhydrous formaldehyde obtained by heat treatment of paraformaldehyde, trioxane obtained by acid treatment of paraformaldehyde, and acetalized formaldehyde such as methylal. It is done. Among these, paraformaldehyde, anhydrous formaldehyde and trioxane are preferably used. These formaldehyde compounds may be used alone or in combination of two or more.
ホルムアルデヒド化合物の使用割合は、スルホン酸化合物１モルに対して、０．１〜１０モルの割合であることが好ましく、０．２〜３モルの割合であることがより好ましい。ホルムアルデヒド化合物の使用割合が０．１モル未満である場合、反応が完結しないおそれがあり、１０モルを超える場合、使用量に見合う効果がなく経済的でない。 The use ratio of the formaldehyde compound is preferably 0.1 to 10 mol, and more preferably 0.2 to 3 mol, per 1 mol of the sulfonic acid compound. When the use ratio of the formaldehyde compound is less than 0.1 mol, the reaction may not be completed, and when it exceeds 10 mol, there is no effect corresponding to the use amount and it is not economical.
本発明に用いられる脱水剤としては、特に限定されるものではなく、例えば、五酸化リン、五塩化リン、オキシ塩化リン、塩化チオニル、塩化アセチルおよび無水酢酸等を挙げることができる。これら脱水剤の中でも、反応性が高い観点から、五酸化リンが好適に用いられる。なお、これら脱水剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いてもよい。 The dehydrating agent used in the present invention is not particularly limited, and examples thereof include phosphorus pentoxide, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, acetyl chloride, and acetic anhydride. Among these dehydrating agents, phosphorus pentoxide is preferably used from the viewpoint of high reactivity. These dehydrating agents may be used alone or in combination of two or more.
脱水剤の使用割合は、スルホン酸化合物１モルに対して、０．３〜１０モルの割合であることが好ましく、０．４〜３モルの割合であることがより好ましい。脱水剤の使用割合が０．３モル未満である場合、反応が完結しないおそれがあり、１０モルを超える場合、使用量に見合う効果がなく経済的でない。 The use ratio of the dehydrating agent is preferably 0.3 to 10 moles, more preferably 0.4 to 3 moles per mole of the sulfonic acid compound. If the use ratio of the dehydrating agent is less than 0.3 mol, the reaction may not be completed, and if it exceeds 10 mol, the effect is not commensurate with the amount used and it is not economical.
本発明において、必要に応じて反応に不活性な溶媒を用いてもよい。反応に不活性な溶媒としては、例えば、トルエン、キシレン、モノクロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、ヘキサン、ヘプタン、デカン等の炭化水素系溶媒；ジエチルエーテル、エチレングリコールジメチルエーテル、ジイソプロピルエーテル、ジフェニルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒；アセトン、メチルエチルケトン等のケトン系溶媒；ジメチルホルムアミド、ヘキサメチル燐酸トリアミド等のアミド系溶媒；酢酸エチル等の酢酸エステル系溶媒；アセトニトリル等のニトリル系溶媒；ジメチルスルホキシド、スルホラン等のスルホキシド・スルホン系溶媒等が挙げられる。 In the present invention, if necessary, a solvent inert to the reaction may be used. Examples of the solvent inert to the reaction include hydrocarbon solvents such as toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, hexane, heptane, decane; diethyl ether, ethylene glycol dimethyl ether, diisopropyl ether, diphenyl ether, tetrahydrofuran, Ether solvents such as dioxane; ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as dimethylformamide and hexamethylphosphoric triamide; acetate solvents such as ethyl acetate; nitrile solvents such as acetonitrile; dimethyl sulfoxide, sulfolane and the like Examples thereof include sulfoxide and sulfone solvents.
溶媒の使用量は、スルホン酸化合物１００重量部に対して、通常、１０００重量部以下である。 The amount of the solvent used is usually 1000 parts by weight or less with respect to 100 parts by weight of the sulfonic acid compound.
本発明の反応温度は、通常、０〜２００℃であり、好ましくは５０〜１５０℃である。また、反応時間は反応温度により異なるが、通常、０．１〜１０時間である。 The reaction temperature of this invention is 0-200 degreeC normally, Preferably it is 50-150 degreeC. Moreover, although reaction time changes with reaction temperature, it is 0.1 to 10 hours normally.
かくして得られるメチレンジスルホネート化合物は、下記一般式（３）で表される化合物である。 The methylene disulfonate compound thus obtained is a compound represented by the following general formula (3).
一般式（３）において、Ｒ１は、前記一般式（１）におけるＲ１と同じ基を示す。 In the general formula (3), R 1 represents the same group as R 1 in the general formula (1).
一般式（３）で表されるメチレンジスルホネート化合物の具体例としては、例えばメチレンジメタンスルホネート、メチレンジトリフルオロメタンスルホネート、メチレンジベンゼンスルホネートおよびメチレンジパラトルエンスルホネート等を挙げることができる。 Specific examples of the methylene disulfonate compound represented by the general formula (3) include methylene dimethane sulfonate, methylene ditrifluoromethane sulfonate, methylene dibenzene sulfonate, and methylene diparatoluene sulfonate.
本発明で得られるメチレンジスルホネート化合物は、例えば、反応液から溶媒等を用いて抽出後、水洗等を経て晶析させる方法、反応液を濾過し、濾液を濃縮する方法、および、反応液から昇華精製させる方法等により単離することができる。 The methylene disulfonate compound obtained in the present invention is extracted from, for example, a reaction solution using a solvent or the like, then crystallized through washing with water, the method of filtering the reaction solution and concentrating the filtrate, and the reaction solution. It can be isolated by a method such as sublimation purification.
本発明によれば、メチレンジスルホネート化合物を安価で容易に製造することができる。 According to the present invention, a methylene disulfonate compound can be easily produced at low cost.
以下、実施例を挙げ、本発明を具体的に説明するが、本発明はこの実施例によってなんら限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited at all by this Example.
実施例１
撹拌機、冷却管および温度計を備え付けた２００ｍｌ容の四つ口フラスコにメタンスルホン酸９．６ｇ（０．１モル）および五酸化リン７．１ｇ（０．０５モル）を仕込み、撹拌下、室温でトリオキサン１．８ｇ（０．０２モル）を添加した。添加終了後、１２０℃まで昇温して１時間撹拌した。その後、室温まで冷却し、水と塩化メチレンを添加して分液し、得られた有機層を濃縮することにより、前記一般式（３）におけるＲ１がメチル基であるメチレンジメタンスルホネートの淡褐色結晶５．９ｇを得た。得られたメチレンジメタンスルホネートの収率は、メタンスルホン酸に対して５７．８モル％であった。
Example 1
A 200 ml four-necked flask equipped with a stirrer, a condenser and a thermometer was charged with 9.6 g (0.1 mol) of methanesulfonic acid and 7.1 g (0.05 mol) of phosphorus pentoxide. At room temperature, 1.8 g (0.02 mol) of trioxane was added. After completion of the addition, the temperature was raised to 120 ° C. and stirred for 1 hour. After cooling to room temperature, water and methylene chloride were added and the mixture is separated, by concentrating the obtained organic layer, wherein R 1 in the general formula (3) as a pale methylenedioxy methanesulfonate is a methyl group 5.9 g of brown crystals were obtained. The yield of the obtained methylene dimethanesulfonate was 57.8 mol% with respect to methanesulfonic acid.
なお、この淡褐色結晶がメチレンジメタンスルホネートであることを下記の分析結果により確認した。
１Ｈ−ＮＭＲ（４００ＭＨｚ、ＣＤ３ＣＮ）δ（ｐｐｍ）：３．２２（ｓ，６Ｈ），５．８３（ｓ，２Ｈ）
In addition, it confirmed from the following analysis result that this light brown crystal | crystallization was a methylene dimethanesulfonate.
1 H-NMR (400 MHz, CD 3 CN) δ (ppm): 3.22 (s, 6H), 5.83 (s, 2H)
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| JP2012131724A (en) * | 2010-12-21 | 2012-07-12 | Central Glass Co Ltd | Method for producing cyclic disulfonic acid ester |
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