WO2007023814A1 - Phosphonium-type ionic compounds containing amino acids as constituent ion - Google Patents
Phosphonium-type ionic compounds containing amino acids as constituent ion Download PDFInfo
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- WO2007023814A1 WO2007023814A1 PCT/JP2006/316418 JP2006316418W WO2007023814A1 WO 2007023814 A1 WO2007023814 A1 WO 2007023814A1 JP 2006316418 W JP2006316418 W JP 2006316418W WO 2007023814 A1 WO2007023814 A1 WO 2007023814A1
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- WIPO (PCT)
- Prior art keywords
- cation
- amino acid
- added
- reduced pressure
- under reduced
- Prior art date
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- 239000000470 constituent Substances 0.000 title abstract description 4
- 150000001413 amino acids Chemical class 0.000 title description 14
- 150000008040 ionic compounds Chemical class 0.000 title description 2
- -1 amino- carboxylate anion Chemical class 0.000 claims abstract description 28
- 150000001768 cations Chemical group 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 150000003018 phosphorus compounds Chemical group 0.000 claims abstract 2
- 229940024606 amino acid Drugs 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 235000001014 amino acid Nutrition 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 7
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 7
- 229960003767 alanine Drugs 0.000 claims description 7
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 6
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 6
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 6
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 6
- 229960002429 proline Drugs 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229960000310 isoleucine Drugs 0.000 claims description 5
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 4
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 4
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 claims description 4
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 4
- 239000004473 Threonine Substances 0.000 claims description 4
- 229960005261 aspartic acid Drugs 0.000 claims description 4
- 229960002989 glutamic acid Drugs 0.000 claims description 4
- 229960002885 histidine Drugs 0.000 claims description 4
- 229960001153 serine Drugs 0.000 claims description 4
- 229960002898 threonine Drugs 0.000 claims description 4
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims description 3
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- QNAYBMKLOCPYGJ-UWTATZPHSA-N L-Alanine Natural products C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 claims description 3
- 229930182844 L-isoleucine Natural products 0.000 claims description 3
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 3
- 229930182821 L-proline Natural products 0.000 claims description 3
- 235000008206 alpha-amino acids Nutrition 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229960001230 asparagine Drugs 0.000 claims description 3
- 229960004452 methionine Drugs 0.000 claims description 3
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 claims description 2
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 claims description 2
- 229930182816 L-glutamine Natural products 0.000 claims description 2
- 229930195722 L-methionine Natural products 0.000 claims description 2
- 235000009582 asparagine Nutrition 0.000 claims description 2
- IFGCUJZIWBUILZ-UHFFFAOYSA-N sodium 2-[[2-[[hydroxy-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyphosphoryl]amino]-4-methylpentanoyl]amino]-3-(1H-indol-3-yl)propanoic acid Chemical compound [Na+].C=1NC2=CC=CC=C2C=1CC(C(O)=O)NC(=O)C(CC(C)C)NP(O)(=O)OC1OC(C)C(O)C(O)C1O IFGCUJZIWBUILZ-UHFFFAOYSA-N 0.000 claims description 2
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 claims 1
- 235000014852 L-arginine Nutrition 0.000 claims 1
- 229930064664 L-arginine Natural products 0.000 claims 1
- 229960002743 glutamine Drugs 0.000 claims 1
- 229960002449 glycine Drugs 0.000 claims 1
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical compound CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 claims 1
- 239000002608 ionic liquid Substances 0.000 abstract description 29
- 239000002904 solvent Substances 0.000 abstract description 12
- 150000001450 anions Chemical group 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 90
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 90
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000004472 Lysine Substances 0.000 description 3
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 3
- 235000004279 alanine Nutrition 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- DJMUYABFXCIYSC-UHFFFAOYSA-N 1H-phosphole Chemical compound C=1C=CPC=1 DJMUYABFXCIYSC-UHFFFAOYSA-N 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 2
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000006911 enzymatic reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 235000018977 lysine Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Chemical compound OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 2
- UNQNIRQQBJCMQR-UHFFFAOYSA-N phosphorine Chemical compound C1=CC=PC=C1 UNQNIRQQBJCMQR-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- IOJBCRTXLWMJAL-UHFFFAOYSA-N C1=CPC2=CC=C3C=CN=C3C2=C1 Chemical compound C1=CPC2=CC=C3C=CN=C3C2=C1 IOJBCRTXLWMJAL-UHFFFAOYSA-N 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
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- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 235000019766 L-Lysine Nutrition 0.000 description 1
- 150000008575 L-amino acids Chemical class 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- 235000019454 L-leucine Nutrition 0.000 description 1
- 239000004395 L-leucine Substances 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 102100025036 Norrin Human genes 0.000 description 1
- 101710085992 Norrin Proteins 0.000 description 1
- BHVZIJYIEPPRKR-UHFFFAOYSA-N P1(CCCCCCC1)C1CCCCCCC1 Chemical compound P1(CCCCCCC1)C1CCCCCCC1 BHVZIJYIEPPRKR-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000012042 active reagent Substances 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
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- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
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- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000003505 heat denaturation Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
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- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 229960003136 leucine Drugs 0.000 description 1
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- 229930182817 methionine Natural products 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0045—Room temperature molten salts comprising at least one organic ion
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- ionic liquids include a very wide temperature range for maintaining a liquid state! In addition, since they are liquids, there is almost no vapor pressure, so they are non-volatile and non-flammable, and liquids that only have ions. Therefore, it has high ionic conductivity, has high solubility in various organic compounds, and can provide a liquid phase that depends on the combination of ions but is not miscible with water or general-purpose organic solvents. . Based on these characteristics, ionic liquids can be used not only as synthetic solvents, separation / extraction solvents, and enzyme reaction solvents, but also as energetic materials for electrolyte materials such as knotteries and fuel cells (for example, Patent Document 1). Has been studied.
- Asymmetric synthesis occupies an extremely important position not only in the field of organic chemistry but also in the fields of biochemistry and pharmacology. So far, as chiral derivatives, chiral ionic liquids that have chirality in the chiral cation or the cation, in which chiral catalysts have been used as optically active reagents, have already been studied. When a chiral ionic liquid is used in the Diels-Alder reaction, the reaction time is shortened, the yield is improved, and the selectivity of the reaction position is improved, even though an asymmetric derivative is not added. The result is obtained. However, there are many points that have been reported to date, and there are many points that should be improved for chiral ionic liquids.
- Examples of the substituent of the lower alkyl group include hydroxy, lower alkoxy having 1 to 4 carbon atoms, a lower alkyl group having 1 to 4 carbon atoms substituted by the alkoxy group, an amino group, and the like.
- a lower alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 3 to 6 carbon atoms, hydroxy, 1 carbon atom is preferable.
- the lower alkyl group having 4 to 4 carbon atoms, the lower alkyl group having 1 to 4 carbon atoms substituted by the same alkoxy group, and the amino group are applicable.
- propyl and butyl are particularly preferred.
- the 4-membered to 7-membered ring that R may constitute with NH—Y is a nitrogen-containing heterocyclo ring, and as such aminocarboxylic acid, proline, particularly L-proline is preferred.
- the aminocarboxylic acid of the cation moiety is not limited to hyaminic acid, but is not particularly limited as long as it is an optically active aminocarboxylic acid, but natural ⁇ -amino acids are preferred, with a-amino acids being preferred.
- the present invention provides an organic ionic liquid that is a quaternary phosphorus compound having an amino acid, particularly a natural amino acid that is inexpensive and easily available, as a constituent ion.
- an organic ionic liquid that is a quaternary phosphorus compound having an amino acid, particularly a natural amino acid that is inexpensive and easily available, as a constituent ion.
- a low-viscosity and optically active environment that has been difficult to synthesize in the past can be easily obtained at low cost.
- a salt is formed together with an appropriate phosphonium cation using a natural amino acid or the like, so that the optical purity is 100% and the liquid is obtained in a wide temperature range from below freezing to 300 ° C.
- the present invention provides a chiral ionic liquid that maintains the state and has a low viscosity. This ionic liquid can be used in all application fields of ordinary ionic liquids, and also has the potential to be used for the creation of various functional molecules as reaction precursors of amino
- tetrabutylphospho-mulanine salt can dissolve 1 to 2% by weight of cellulose at 100 ° C. Solubility varies depending on the type of amino acid.
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Abstract
Quaternary phosphorus compounds represented by the general formula (I): [wherein Ph+ as the cation moiety is (R1R2R3R4)P+ (wherein R1, R2, R3 and R4 are each independently substituted or unsubstituted lower alkyl) or a cation derived from a substituted or unsubstituted heterocycle containing one or more phosphorus atoms as ring constituent(s) by bonding one proton or one alkyl group to the phosphorus atom; and the anion moiety is an amino- carboxylate anion (wherein R is hydrogen or forms a four- to seven-membered ring together with NH-Y; and Y is a residue derived from an aminocarboxylic acid by removing the amino and carboxyl groups)]. The invention provides low environment load type chiral derivatives which can be easily prepared at low cost and low-viscosity ionic liquids useful as novel solvents.
Description
アミノ酸を構成イオンとするホスホニゥム型イオン化合物 Phosphonium-type ionic compounds containing amino acids as constituent ions
技術分野 Technical field
[0001] 本発明は一般式 Iで示される第 4級燐化合物である有機イオン液体に関する。 The present invention relates to an organic ionic liquid that is a quaternary phosphorus compound represented by general formula I.
背景技術 Background art
[0002] イオン液体とはイオン性液体とも呼ばれる融点が 100°C程度以下の塩の総称であり 、水、有機溶媒に次ぐ第三の溶媒として注目を集めている (例えば、非特許文献 1)。 イオン液体はイオン液体形成に有利なカチオンとァ-オンを組み合わせて合成され る。これまで用いられてきたカチオンにはイミダゾリウムカチオン、ピリジ-ゥムカチォ ン、ァノレキノレアンモユウムカチオンなどがあり、ァ-オンとしては、 BF _、 PF _、 CF [0002] An ionic liquid is a generic term for salts having a melting point of about 100 ° C or less, which is also called an ionic liquid, and is attracting attention as a third solvent after water and organic solvents (for example, Non-Patent Document 1). . An ionic liquid is synthesized by combining a cation and a key which are advantageous for forming an ionic liquid. The cations that have been used so far include imidazolium cations, pyridinium cations, and anorequinoleum ammonium cations. Examples of cation are BF _ , PF _ , CF
4 6 3 4 6 3
SO _、イミドア-オン((CF SO ) N_)、 CH COO", CF COO", NO―、(CN)SO _, imido-one ((CF SO) N_), CH COO ", CF COO", NO-, (CN)
3 3 3 2 3 3 3 23 3 3 2 3 3 3 2
N—などがある。 N—etc.
[0003] これらのイオン液体の特徴として、液体状態を保つ温度範囲が極めて広!、こと、液 体でありながら蒸気圧がほとんどないため、不揮発性 ·不燃性であること、イオンのみ 力 なる液体であるため高いイオン伝導度を有すること、種々の有機化合物に対して 高い溶解性を有すること、イオンの組み合わせに依存するが水や汎用の有機溶媒と 混和しない液相を提供できることなどがあげられる。これらの特徴に基づき、イオン液 体は各種合成溶媒や分離'抽出溶媒、酵素反応溶媒としての応用はもちろんのこと 、ノ ッテリーや燃料電池などの電解質材料 (例えば、特許文献 1)としても精力的に研 究されている。 [0003] The characteristics of these ionic liquids include a very wide temperature range for maintaining a liquid state! In addition, since they are liquids, there is almost no vapor pressure, so they are non-volatile and non-flammable, and liquids that only have ions. Therefore, it has high ionic conductivity, has high solubility in various organic compounds, and can provide a liquid phase that depends on the combination of ions but is not miscible with water or general-purpose organic solvents. . Based on these characteristics, ionic liquids can be used not only as synthetic solvents, separation / extraction solvents, and enzyme reaction solvents, but also as energetic materials for electrolyte materials such as knotteries and fuel cells (for example, Patent Document 1). Has been studied.
[0004] これらの応用の中でも、各種合成溶媒としての報告は群を抜く。イオン液体の特徴 は、生活環境への拡散を最小限にとどめるうえで有用であり、繰り返し利用する上で も優れているため、環境に優しい溶媒として、従来の溶媒の代替材料として適切と考 えられている。これまでに、フリーデル 'クラフト(Friedel— Crafts)反応、ディールス' アルダー(Diels— Alder)反応、ヘック(Heck)反応、スズキ(Suzuki)カップリング反 応、ベックマン (Beckmann)転移反応などに関して報告がなされている(例えば、特 許文献 2)。これらはほんの一例に過ぎず、極めて多くの反応に検討が及んでいる。
いずれもイオン液体が反応用の溶媒として繰り返し利用できること、反応によっては 従来の溶媒よりも優れた収率や反応選択性が得られることが明らかとなっている。 [0004] Among these applications, reports as various synthetic solvents are outstanding. The characteristics of ionic liquids are useful for minimizing diffusion into the living environment and are excellent for repeated use. Therefore, they are considered to be suitable as environmentally friendly solvents and substitutes for conventional solvents. It has been. So far, there have been reports on Friedel-Crafts reaction, Diels-Alder reaction, Heck reaction, Suzuki coupling reaction, Beckmann transfer reaction, etc. (For example, Patent Document 2). These are just a few examples, and a very large number of reactions are under consideration. In both cases, it has been clarified that ionic liquid can be repeatedly used as a reaction solvent, and that yields and reaction selectivity superior to conventional solvents can be obtained depending on the reaction.
[0005] これら有機合成の中でも最も重要な反応の一つは不斉合成反応である。不斉合成 は有機化学分野にとどまらず、生化学、薬理学の分野においても極めて重要な位置 を占める。これまで、不斉誘導体としては、光学活性な試薬ゃキラル触媒が用いられ てきた力 カチオンまたはァ-オン部に不斉を有するキラルイオン液体の合成もすで に検討されている。ディールス 'アルダー(Diels— Alder)反応にキラルイオン液体を 用いた場合、不斉誘導体を添加していないにも関わらず、反応時間の短縮、収率の 向上、反応位置の選択性向上など顕著な結果が得られている。しかし、現在までに 報告されて 、るキラルイオン液体にも改善すべき点は多 、。 [0005] One of the most important reactions among these organic syntheses is an asymmetric synthesis reaction. Asymmetric synthesis occupies an extremely important position not only in the field of organic chemistry but also in the fields of biochemistry and pharmacology. So far, as chiral derivatives, chiral ionic liquids that have chirality in the chiral cation or the cation, in which chiral catalysts have been used as optically active reagents, have already been studied. When a chiral ionic liquid is used in the Diels-Alder reaction, the reaction time is shortened, the yield is improved, and the selectivity of the reaction position is improved, even though an asymmetric derivative is not added. The result is obtained. However, there are many points that have been reported to date, and there are many points that should be improved for chiral ionic liquids.
[0006] 従来のキラルイオン液体の欠点としては、(1)イミダゾリウムカチオンやアンモ-ゥム カチオンのようなカチオン構造にキラル部位を有する系は、合成手順が煩雑で高純 度物を得るのは容易ではな ヽ;(2)キラルな塩を用いたイオン液体の合成は従来の 系と同様にァ-オン交換反応により合成するため出発物質が高価である;(3)光学 純度が 100%でない;(5)融点が室温よりも高い系が多い;(6)粘度が高い (熱処理 を必要とするためラセミ化ゃ熱変性するなどの欠点がある)などが挙げられる。 [0006] The disadvantages of conventional chiral ionic liquids are as follows: (1) A system having a chiral moiety in a cation structure such as an imidazolium cation or an ammonium cation has a complicated synthesis procedure and yields a highly pure product. (2) The synthesis of ionic liquids using chiral salts is expensive, since it is synthesized by a key-on exchange reaction as in the conventional system; (3) Optical purity is 100% (5) Many systems have a melting point higher than room temperature; (6) High viscosity (there is a problem such as heat denaturation if racemicization occurs because heat treatment is required).
[0007] これまでに天然アミノ酸を出発物質とするキラルイオン液体の合成を試みた報告は ある (例えば、非特許文献 2)が、目的物質の合成に多段階の操作を経つ必要がある こと、前駆体の合成時に官能基がカルボキシル基力 アルコールに置換されること、 イミダゾリウムカチオンの側鎖に嵩高いアミノ酸誘導体が導入されるため、得られた塩 の融点が比較的高くなり、イオン液体とは言えな力つた。また、天然アミノ酸をォ-ゥ ムカチオンと組み合わせて合成したイオン液体 (特許文献 3)は、アミノ酸の側鎖構造 によっては粘度が非常に高くなる場合があった。 [0007] There have been reports of attempts to synthesize chiral ionic liquids starting from natural amino acids (for example, Non-Patent Document 2), but the synthesis of the target substance requires a multi-step operation, When the precursor is synthesized, the functional group is substituted with a carboxyl group alcohol, and a bulky amino acid derivative is introduced into the side chain of the imidazolium cation, so that the melting point of the resulting salt becomes relatively high, and the ionic liquid I couldn't say anything. In addition, an ionic liquid synthesized by combining a natural amino acid with an organic cation (Patent Document 3) may have a very high viscosity depending on the side chain structure of the amino acid.
特許文献 1:特開 2000— 3620号公報 Patent Document 1: Japanese Patent Laid-Open No. 2000-3620
特許文献 2:特開 2002— 275118号公報 Patent Document 2: Japanese Patent Laid-Open No. 2002-275118
特許文献 3:特開 2004— 269414号公報 Patent Document 3: Japanese Patent Application Laid-Open No. 2004-269414
非特許文献 1 :大野弘幸、「有機イオン性液体 蒸発しない極性液体 未来材料 2002年、第 2卷第 9号 6〜: L 1頁
非特許文献 2 : Weiliang Bao, Zhimiang Wang and Yuxia Li, Journal of Organic Chemi stry, 2003, 68(2), 591—593. Non-patent document 1: Hiroyuki Ohno, “Organic ionic liquid, polar liquid that does not evaporate, future materials 2002, No. 2 No. 9, 6-: L 1 page Non-Patent Document 2: Weiliang Bao, Zhimiang Wang and Yuxia Li, Journal of Organic Chemi stry, 2003, 68 (2), 591-593.
発明の開示 Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
[0008] 新たなイオン液体を提供することが本発明の目的である。 [0008] It is an object of the present invention to provide a new ionic liquid.
課題を解決するための手段 Means for solving the problem
[0009] 本発明は、一般式 I: [0009] The present invention provides compounds of the general formula I:
[化 1] [Chemical 1]
0 0
Ph+ RNH Y GO— (I) Ph + RNH Y GO— (I)
[式中、カチオン部 Ph+は、(Κ 4) Ρ+ (ここで、
R2、 R3、および R4は、それ ぞれ独立して、非置換もしくは置換された低級アルキル基)であるカゝ、または 1もしく はそれ以上の燐原子を環員として含む、非置換もしくは置換されたへテロ環の燐原 子にプロトンもしくはアルキル基が 1つ結合したカチオンであり、ァ-オン部は、ァミノ カルボン酸ァ-オン (ここで、 Rは水素原子を表すか、または NH— Yとともに 4員環か ら 7員環を構成し、 Yはァミノカルボン酸のアミノ基およびカルボキシル基を除 、た構 成部分を表す。)である] [Wherein the cation moiety Ph + is (Κ 4 ) Ρ + (where R 2 , R 3 , and R 4 are each independently a non-substituted or substituted lower alkyl group) or a ring member containing one or more phosphorus atoms as ring members. A cation in which a proton or an alkyl group is bonded to a substituted or substituted hetero ring phosphorus atom, and the cation is an amino carboxylate cation (where R represents a hydrogen atom, Or NH—Y together with a 4-membered to 7-membered ring, where Y represents a component other than the amino and carboxyl groups of an aminocarboxylic acid.]
で示される第 4級燐化合物である有機イオン液体を提供する。 An organic ionic liquid which is a quaternary phosphorus compound represented by the formula:
[0010] ここで低級アルキル基とは、飽和の直鎖または分岐上の炭素数 1〜12の炭化水素 残基をいい、好ましくは炭素数 2〜6、より好ましくは炭素数 2〜4の炭化水素残基を いう。例えばメチル、ェチル、プロピル、イソプロピル、ブチル、 s—ブチル、 t—ブチル 、ペンチル、へキシルなどが挙げることができ、好ましくは、ェチル、プロピル、イソプ 口ピル、ブチル、ペンチル、へキシルであり、より好ましくは、プロピルおよびブチルで ある。 Here, the lower alkyl group refers to a saturated linear or branched hydrocarbon residue having 1 to 12 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. This refers to a hydrogen residue. For example, methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, pentyl, hexyl and the like can be mentioned, preferably ethyl, propyl, isopropyl, butyl, pentyl, hexyl, More preferred are propyl and butyl.
[0011] 低級アルキル基の置換基としては、ヒドロキシ、炭素数 1〜4の低級アルコキシ、同 アルコキシ基が置換した炭素数 1〜4の低級アルキル基、アミノ基等が例示される。
式 Iのへテロ環の置換基としては、炭素数 1〜12、好ましくは、炭素数 1〜6、より好 ましくは、炭素数 3〜6の低級アルキル基の他、ヒドロキシ、炭素数 1〜4の低級アルコ キシ、同アルコキシ基が置換した炭素数 1〜4の低級アルキル基、アミノ基等が該当 する。低級アルキル基の中では、プロピルおよびブチルが特に好ましい。 [0011] Examples of the substituent of the lower alkyl group include hydroxy, lower alkoxy having 1 to 4 carbon atoms, a lower alkyl group having 1 to 4 carbon atoms substituted by the alkoxy group, an amino group, and the like. As the substituent of the heterocyclic ring of formula I, a lower alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 3 to 6 carbon atoms, hydroxy, 1 carbon atom is preferable. The lower alkyl group having 4 to 4 carbon atoms, the lower alkyl group having 1 to 4 carbon atoms substituted by the same alkoxy group, and the amino group are applicable. Of the lower alkyl groups, propyl and butyl are particularly preferred.
Rが NH— Yとともに構成することのある 4員環から 7員環とは含窒素へテロシクロ環 であり、そのようなアミノカルボン酸としてはプロリン、特に L—プロリンが好ましい。 ァ-オン部のアミノカルボン酸はひ -アミ酸のみならず、光学活性なアミノカルボン 酸であれば特に限定はされないが、 a -アミノ酸が好ましぐ特に天然の α -アミノ酸 が好ましい。 The 4-membered to 7-membered ring that R may constitute with NH—Y is a nitrogen-containing heterocyclo ring, and as such aminocarboxylic acid, proline, particularly L-proline is preferred. The aminocarboxylic acid of the cation moiety is not limited to hyaminic acid, but is not particularly limited as long as it is an optically active aminocarboxylic acid, but natural α-amino acids are preferred, with a-amino acids being preferred.
発明の効果 The invention's effect
[0012] 本発明は、アミノ酸、特に安価で容易に入手できる天然アミノ酸を構成イオンとする 第 4級燐ィ匕合物である有機イオン液体を提供するものである。本発明によって、従来 は合成が困難であった低粘度で光学活性な環境を安価かつ容易に入手できる。す なわち、本発明によって、天然アミノ酸などを用いて適切なホスホニゥムカチオンと共 に塩とすることで、光学純度が 100%で、氷点下から 300°Cを越す広い温度範囲に おいて液体状態を保ち、低粘度となるキラルなイオン液体を提供するものである。こ のイオン液体は通常のイオン液体の応用分野全てに用いることができ、しかもァミノ 酸の反応前駆体として各種機能分子の創製に利用できる可能性も併せ持つ。 [0012] The present invention provides an organic ionic liquid that is a quaternary phosphorus compound having an amino acid, particularly a natural amino acid that is inexpensive and easily available, as a constituent ion. According to the present invention, a low-viscosity and optically active environment that has been difficult to synthesize in the past can be easily obtained at low cost. In other words, according to the present invention, a salt is formed together with an appropriate phosphonium cation using a natural amino acid or the like, so that the optical purity is 100% and the liquid is obtained in a wide temperature range from below freezing to 300 ° C. The present invention provides a chiral ionic liquid that maintains the state and has a low viscosity. This ionic liquid can be used in all application fields of ordinary ionic liquids, and also has the potential to be used for the creation of various functional molecules as reaction precursors of amino acids.
図面の簡単な説明 Brief Description of Drawings
[0013] [図 l]n—テトラブチルホスホ-ゥムァラニン塩(実施例 1)の1 H—NMRチャートである 発明を実施するための最良の形態 FIG. 1 is a 1 H-NMR chart of n-tetrabutylphospho-mualanine salt (Example 1). BEST MODE FOR CARRYING OUT THE INVENTION
[0014] 低級アルキル基のカチオン 4) P+の例としては、低級アルキルホスホ-ゥ ムが挙げられ、ヘテロ環のカチオンの例としては、ホスホラ-ゥム、ホスホリウム、ジべ ンゾホスホリウム、ホスフィンドリゥム、ホスホリナ二ゥム、ジベンゾホスホニナ二ゥム、ホ スホリノインドリウム、ホスホニアビシクロオクタン、ホスホリノホスフイノリジニゥム、ホス ホリノピリミジ-ゥム、ホスホリニゥム、ホスフィノリ-ゥム、ホスフイノドリジ-ゥムを挙げる ことができるが、好ましくは、ホスホリウム、ホスホリナリウムである。
[0015] ァ-オンは、 D—または L—アミノ酸のァ-オンが好ましぐより好ましくは天然の oc —アミノ酸であり、さらに好ましくは、 L ァスパラギン、 L ァスパラギン酸、 L ァラ ニン、 L アルギニン、 L—イソロイシン、グリシン、 L グルタミン、 L グルタミン酸、 L システィン、 L セリン、 L チロシン、 L トリプトファン、 L トレオニン、 L ノ リ ン、 L ヒスチジン、 L フエ二ルァラニン、 L プロリン、 L—メチォニン、 L リジンま たは L ロイシン力も選ばれるアミノ酸のァ-オンである。 [0014] Examples of lower alkyl group cations 4 ) P + include lower alkyl phosphorous, and examples of heterocyclic cations include phosphorium, phospholium, dibenzophospholium, and phosphine dream. , Phosphorinium, Dibenzophosphoninium, Phosphorinoindolium, Phosphoniabicyclooctane, Phospholinophosphinoridinum, Phosphorinopyrimidium, Phosphorinium, Phosphinolymeum, Phosphinodridium Among them, preferred are phospholium and phosphorinalium. [0015] The cation is preferably a natural oc-amino acid, more preferably a cation of D- or L-amino acid, and more preferably L-asparagine, L-aspartic acid, L-alanine, L Arginine, L—Isoleucine, Glycine, L Glutamine, L Glutamic acid, L Cystein, L Serine, L Tyrosine, L Tryptophan, L Threonine, L Norrin, L Histidine, L Phenylalanin, L Proline, L—Methionine, L Lysine or L-leucine is also a key amino acid chosen.
[0016] 本発明の第 4級燐ィ匕合物の一般的な製造方法 [0016] General method for producing quaternary phosphorus compound of the present invention
カチオン部の Ph+のヒドロキシ化合物の水性溶媒に、ァ-オン部 RNH— Y—C ( = O)— 0_となるアミノ酸約 1〜1. 4重量部、好ましくは、約 1. 0重量部を添加し、得ら れた混合溶液を氷冷下攪拌し、溶媒を減圧留去し、残渣から適切な方法によって未 反応のアミノ酸を除去し、所望のイオン液体としての第 4級燐化合物を得る。 About 1 to 1.4 parts by weight, preferably about 1.0 part by weight of an amino acid to form a cation RNH—Y—C (═O) —0_ in an aqueous solvent of a Ph + hydroxy compound in the cation part. The resulting mixed solution is stirred under ice-cooling, the solvent is distilled off under reduced pressure, and unreacted amino acids are removed from the residue by an appropriate method to obtain a quaternary phosphorus compound as a desired ionic liquid. .
尚、 Ph+のヒドロキシィ匕合物は、市販品を用いるか、或いは、例えば、相当するホス ホ -ゥムハライドのハロゲンイオンをイオン交換することにより容易に調製できる。 実施例 The hydroxy compound of Ph + can be easily prepared by using a commercially available product or by ion-exchange of the halogen ion of the corresponding phosphor halide. Example
[0017] イオン液体の応用のひとつとして、セルロース等難溶性多糖類の溶媒としての利用 がある。そこで、本発明のイオン液体のセルロース溶解度を試験した。 [0017] One application of ionic liquids is the use of poorly soluble polysaccharides such as cellulose as solvents. Thus, the cellulose solubility of the ionic liquid of the present invention was tested.
試験例 Test example
テトラブチルホスホ-ゥムァラニン塩(下記実施例 1参照) 5gを 80°Cで 24時間加熱 真空乾燥し、窒素雰囲気下でセルロース (ろ紙) 50mgと混合し、密閉した後、加熱し ながらセルロースの溶解温度を記録した。その結果、セルロース 50mgが完全に溶解 する温度は 100°Cであつた。 Tetrabutylphospho-mulanine salt (see Example 1 below) 5g heated at 80 ° C for 24 hours, vacuum dried, mixed with 50mg cellulose (filter paper) under nitrogen atmosphere, sealed, and heated while dissolving cellulose Was recorded. As a result, the temperature at which 50 mg of cellulose was completely dissolved was 100 ° C.
この試験結果にもあるとおり、テトラブチルホスホ-ゥムァラニン塩は、 100°Cで 1〜 2重量%のセルロースを溶解することができる。アミノ酸の種類により溶解度は変化す る。 As shown in this test result, tetrabutylphospho-mulanine salt can dissolve 1 to 2% by weight of cellulose at 100 ° C. Solubility varies depending on the type of amino acid.
以下、実施例によってこの発明を具体的に説明する。いずれの実施例においても 目的物が室温下液状物質として得られたが、本発明はこれらに限定されるものでは ない。なお、これらの実施例におけるテトラアルキルホスホ-ゥム水酸ィ匕物とアミノ酸 の中和反応の進行は、ェ!! NMR測定によって行!、確認された。
[0018] 実施例 1 Hereinafter, the present invention will be described specifically by way of examples. In any of the Examples, the target product was obtained as a liquid substance at room temperature, but the present invention is not limited to these. In these examples, the progress of neutralization reaction between tetraalkylphosphoric acid hydroxide and amino acid is! Confirmed by NMR measurement! [0018] Example 1
41. 6wt%テトラブチルホスホ-ゥムハイドロキサイド水溶液 26. 6gに Lーァラニン 5gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニトリル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過剰に カロえた未反応のァラニン)を除去し、濾液を減圧加熱乾燥してァセトニトリルとメタノー ルを除去し、テトラブチルホスホ-ゥムァラニン l lg (収率 80%)を得た。本品の1 H— NMR測定を行った結果は図 1に示されたとおりであり、プロトンの化学シフトと積分 強度から反応の進行が確認された。41. 5 g of L-alanine was added to 26.6 g of 6 wt% tetrabutylphosphonium hydroxide aqueous solution, and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. After that, the crystals precipitated by filtration (unreacted unreacted alanine) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol, and tetrabutylphospho-mualanin l lg (yield 80%) was obtained. Obtained. The results of 1 H-NMR measurement of this product are as shown in Fig. 1. The progress of the reaction was confirmed from the chemical shift of proton and the integrated intensity.
— NMR(DMSO, δ /ppm TMS基準):0. 917 (t, 12H, J= 14. 5Hz) , 0. 982 (t, 3H, J = 7Hz) , 1. 369— 1. 503 (m, 16H) , 2. 214 (m, 8H, J = 30H z) , 2. 769 (q, 1H, J = 20Hz) — NMR (DMSO, δ / ppm TMS standard): 0.917 (t, 12H, J = 14.5 Hz), 0.982 (t, 3H, J = 7 Hz), 1. 369— 1. 503 (m, 16H), 2.214 (m, 8H, J = 30Hz), 2.769 (q, 1H, J = 20Hz)
[0019] 実施例 2 [0019] Example 2
41. 6 %テトラブチルホスホ-ゥムハイドロキサイド水溶液 26. 6gに L—グリシン 4 gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニトリル 6 Omlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過剰にカロ えた未反応のグリシン)を除去し、濾液を減圧加熱乾燥してァセトニトリルとメタノール を除去し、テトラブチルホスホ-ゥムグリシン l lg (収率 83%)を得た。本品の 1H— N MR測定を行った結果、プロトンの化学シフトと積分強度力 反応の進行が確認され た。 41. 4 g of L-glycine was added to 26.6 g of 6% tetrabutylphosphonium hydroxide aqueous solution, and the excess water was removed by drying under reduced pressure while stirring. Acetonitrile 6 Oml and methanol 40ml were added thereto and stirred. Thereafter, the crystals precipitated by filtration (unreacted unreacted glycine) were removed, and the filtrate was heated and dried under reduced pressure to remove acetonitrile and methanol to obtain tetrabutylphospho-umglycine l lg (yield 83%). It was. As a result of 1H-N MR measurement of this product, it was confirmed that the chemical shift of the proton and the progress of the integrated intensity force reaction progressed.
— NMR (DMSO, δ /ppm TMS基準):0. 918 (t, 12H, J= 14 Hz) , 1. 3 68 - 1. 500 (m, 16H) , 2. 200 (m, 8H, J = 30 Hz) , 2. 630 (q, 1H, J = 6. 5 Hz) — NMR (DMSO, δ / ppm TMS standard): 0.918 (t, 12H, J = 14 Hz), 1. 3 68-1. 500 (m, 16H), 2. 200 (m, 8H, J = 30 Hz), 2.630 (q, 1H, J = 6.5 Hz)
[0020] 実施例 3 [0020] Example 3
41. 6wt%テトラブチルホスホ-ゥムハイドロキサイド水溶液 26. 6gに Lーァスパラ ギン酸 7gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセト 二トリル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶( 過剰に加えた未反応のァスパラギン酸)を除去し、濾液を減圧加熱乾燥してァセトニ トリルとメタノールを除去し、テトラブチルホスホ-ゥムァスパラギン酸 10g (収率 65%)
を得た。本品の1 H— NMR測定を行った結果、プロトンの化学シフトと積分強度から 反応の進行が確認された。41. 7 g of L-aspartic acid was added to 26.6 g of 6 wt% tetrabutylphosphonium hydroxide aqueous solution and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted aspartic acid added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol, and 10 g of tetrabutylphospho-muaspartic acid (yield 65%). Got. As a result of 1 H-NMR measurement of this product, the progress of the reaction was confirmed from the chemical shift of proton and the integrated intensity.
— NMR(DMSO, δ/ppm TMS基準):0.917 (t, 12H, J=14.5 Hz), 1 .369-1.502 (m, 16H), 2.191 (m, 8H, J = 29.5 Hz), 2.188 (m, 2H, J = 139 Hz), 3.170 (t, 1H, J=14 Hz) — NMR (DMSO, δ / ppm TMS standard): 0.917 (t, 12H, J = 14.5 Hz), 1.369-1.502 (m, 16H), 2.191 (m, 8H, J = 29.5 Hz), 2.188 (m , 2H, J = 139 Hz), 3.170 (t, 1H, J = 14 Hz)
[0021] 実施例 4 [0021] Example 4
41.6wt%テトラブチルホスホ-ゥムハイドロキサイド水溶液 26.6gに Lーグルタミ ン酸 7.6gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセト 二トリル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶( 過剰に加えた未反応のグルタミン酸)を除去し、濾液を減圧加熱乾燥してァセトニトリ ルとメタノールを除去し、テトラブチルホスホ-ゥムグルタミン酸 10g (収率 65%)を得 た。本品の1 H— NMR測定を行った結果、プロトンの化学シフトと積分強度力も反応 の進行が確認された。7.6 g of L-glutamic acid was added to 26.6 g of 41.6 wt% tetrabutylphosphonium hydroxide aqueous solution, and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted glutamic acid added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol. Tetrabutylphospho-umglutamic acid 10 g (yield 65%) Got. As a result of 1 H-NMR measurement of this product, the progress of the reaction was confirmed in terms of the chemical shift of the proton and the integrated intensity force.
— NMR(DMSO, δ/ppm TMS基準):0.918 (t, 12H, J=14 Hz), 1.3 68-1.498 (m, 16H), 2.179(m, 8H, J = 30 Hz), 1.620— 2.131 (m, 4H — NMR (DMSO, δ / ppm TMS standard): 0.918 (t, 12H, J = 14 Hz), 1.3 68-1.498 (m, 16H), 2.179 (m, 8H, J = 30 Hz), 1.620— 2.131 ( m, 4H
) )
[0022] 実施例 5 [0022] Example 5
41.6 %テトラブチルホスホ-ゥムハイドロキサイド水溶液 26.6gに L—リシン 5g を加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニトリル 60 mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過剰にカロ えた未反応のリシン)を除去し、濾液を減圧加熱乾燥してァセトニトリルとメタノールを 除去し、テトラブチルホスホ-ゥムリシン 13g (収率 78%)を得た。本品の1 H— NMR 測定を行った結果、プロトンの化学シフトと積分強度力 反応の進行が確認された。To 26.6 g of 41.6% tetrabutylphosphonium hydroxide aqueous solution, 5 g of L-lysine was added and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted unreacted lysine) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol to obtain 13 g of tetrabutylphospho-umricin (yield 78%). . As a result of 1 H-NMR measurement of this product, it was confirmed that the chemical shift of the proton and the progress of the integrated intensity force reaction progressed.
— NMR(DMSO, δ/ppm TMS基準):0.917 (t, 12H, J=14.5 Hz), 1 .245-1.878 (m, 22H), 2.216 (m, 8H, J = 30 Hz), 2.679 (q, 1H, J=12 — NMR (DMSO, δ / ppm TMS standard): 0.917 (t, 12H, J = 14.5 Hz), 1.245-1.878 (m, 22H), 2.216 (m, 8H, J = 30 Hz), 2.679 (q , 1H, J = 12
Hz) Hz)
[0023] 実施例 6 [0023] Example 6
41.6wt%テトラブチルホスホ-ゥムハイドロキサイド水溶液 26.6gに Lーァスパラ
ギン 7. 6gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセト 二トリル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶( 過剰に加えた未反応のァスパラギン)を除去し、濾液を減圧加熱乾燥してァセトニトリ ルとメタノールを除去し、テトラブチルホスホ-ゥムァスパラギン 10g (収率 70%)を得 た。本品の1 H— NMR測定を行った結果、プロトンの化学シフトと積分強度力も反応 の進行が確認された。Add 41.6wt% tetrabutylphosphonium hydroxide aqueous solution to 26.6g 7.6 g of gin was added and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted asparagine added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol to obtain 10 g of tetrabutylphospho-muasparagine (yield 70%). It was. As a result of 1 H-NMR measurement of this product, the progress of the reaction was confirmed in terms of the chemical shift of the proton and the integrated intensity force.
— NMR (DMSO, δ /ppm TMS基準):0. 917 (t, 12H, J= 14. 5 Hz) , 1 . 369- 1. 501 (m, 16H) , 2. 198 (m, 8H, J = 23 Hz) , 1. 910— 2. 389 (m, 2H) , 3. 037 (s, 1H) , 6. 557 (s, 1H) , 8. 213 (s, 1H) — NMR (DMSO, δ / ppm TMS standard): 0.917 (t, 12H, J = 14.5 Hz), 1.369- 1. 501 (m, 16H), 2. 198 (m, 8H, J = 23 Hz), 1. 910— 2. 389 (m, 2H), 3. 037 (s, 1H), 6. 557 (s, 1H), 8. 213 (s, 1H)
[0024] 実施例 7 [0024] Example 7
41. 6wt%テトラブチルホスホ-ゥムハイドロキサイド水溶液 26. 6gに Lーグルタミ ン 7. 5gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニ トリル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過 剰に加えた未反応のグルタミン)を除去し、濾液を減圧加熱乾燥してァセトニトリルと メタノールを除去し、テトラブチルホスホ-ゥムグルタミン l lg (収率 72%)を得た。本 品の1 H—NMR測定を行った結果、プロトンの化学シフトと積分強度力 反応の進行 が確認された。41. 7.5 g of L-glutamin was added to 26.6 g of 6 wt% tetrabutylphosphonium hydroxide aqueous solution, and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted glutamine added excessively) are removed, and the filtrate is heated and dried under reduced pressure to remove acetonitrile and methanol, and tetrabutylphospho-mummglutamine l lg (yield 72%) is obtained. Obtained. As a result of 1 H-NMR measurement of this product, it was confirmed that the chemical shift of the proton and the progress of the integrated intensity force reaction progressed.
— NMR (DMSO, δ /ppm TMS基準):0. 915 (t, 12H, J = 20 Hz) , 1. 3 69 - 1. 685 (m, 18H) , 2. 042 (m, 2H, J = 80 Hz) , 2. 236 (m, 8H, J = 30 Hz) , 2. 764 (q, 1H, J= 12. 5 Hz) — NMR (DMSO, δ / ppm TMS standard): 0.915 (t, 12H, J = 20 Hz), 1. 3 69-1. 685 (m, 18H), 2.042 (m, 2H, J = 80 Hz), 2.236 (m, 8H, J = 30 Hz), 2.764 (q, 1H, J = 12.5 Hz)
[0025] 実施例 8 [0025] Example 8
41. 6 %テトラブチルホスホ-ゥムハイドロキサイド水溶液 26. 6gに L—ヒスチジ ン 7gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニトリ ル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過剰 に加えた未反応のヒスチジン)を除去し、濾液を減圧加熱乾燥してァセトニトリルとメタ ノールを除去し、テトラブチルホスホ-ゥムヒスチジン 13g (収率 80%)を得た。本品の ^—NMR測定を行った結果、プロトンの化学シフトと積分強度力 反応の進行が確 f*i¾ れ 。
H— NMR(CDC13, δ /ppm TMS基準): 0.968 (t, 12H, J=14 Hz), 1.5 00 (m, 16H, J=15 Hz), 2.331 (m, 8H, J = 29.5 Hz), 2.958 (m, 2H, J = 335 Hz), 3.417(q, 1H, J=17 Hz), 6.754 (s, 1H) , 7.430 (s, 1H) 41. To 66.6 g of 6% tetrabutylphosphonium hydroxide aqueous solution, 7 g of L-histidine was added and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted histidine added in excess) were removed, and the filtrate was heated and dried under reduced pressure to remove acetonitrile and methanol to obtain 13 g of tetrabutylphospho-humhistidine (yield 80%). It was. As a result of ^ -NMR measurement of this product, the chemical shift of the proton and the progress of the integrated intensity force reaction were confirmed f * i. H—NMR (CDC13, δ / ppm TMS standard): 0.968 (t, 12H, J = 14 Hz), 1.5 00 (m, 16H, J = 15 Hz), 2.331 (m, 8H, J = 29.5 Hz), 2.958 (m, 2H, J = 335 Hz), 3.417 (q, 1H, J = 17 Hz), 6.754 (s, 1H), 7.430 (s, 1H)
[0026] 実施例 9 [0026] Example 9
41.6wt%テトラブチルホスホ-ゥムハイドロキサイド水溶液 26.6gに L—イソロイ シン 8gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニト リル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過 剰に加えた未反応のイソロイシン)を除去し、濾液を減圧加熱乾燥してァセトニトリル とメタノールを除去し、テトラブチルホスホ-ゥムイソロイシン 13g (収率 83%)を得た。 本品の1 H—NMR測定を行った結果、プロトンの化学シフトと積分強度力 反応の進 行が確認された。8 g of L-isoleucine was added to 26.6 g of a 41.6 wt% tetrabutylphosphonium hydroxide aqueous solution, and the mixture was dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Then, the crystals precipitated by filtration (unreacted isoleucine added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol, and 13 g of tetrabutylphospho-isoleucine (yield 83%) Got. As a result of 1 H-NMR measurement of this product, the chemical shift of the proton and the progress of the integrated intensity force reaction were confirmed.
— NMR(DMSO, δ/ppm TMS基準):0.750— 0.783 (m, 6H), 0.917 (t, 12H, J=14 Hz), 0.9845 (m, 1H, J = 30.5 Hz), 1.309— 1.585 (m, 18H), 2.228 (m, 8H, J = 30 Hz), 2.612(d, 1H, J=4.5 Hz) — NMR (DMSO, δ / ppm TMS standard): 0.750— 0.783 (m, 6H), 0.917 (t, 12H, J = 14 Hz), 0.9845 (m, 1H, J = 30.5 Hz), 1.309— 1.585 (m , 18H), 2.228 (m, 8H, J = 30 Hz), 2.612 (d, 1H, J = 4.5 Hz)
[0027] 実施例 10 [0027] Example 10
41.6 %テトラブチルホスホ-ゥムハイドロキサイド水溶液 26.6gに L一口イシン 6 .8gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニトリ ル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過剰 に加えた未反応のァラニン)を除去し、濾液を減圧加熱乾燥してァセトニトリルとメタノ ールを除去し、テトラブチルホスホ-ゥムロイシン llg (収率 70%)を得た。本品の1 H —NMR測定を行った結果、プロトンの化学シフトと積分強度力 反応の進行が確認 された。 To 26.6 g of 41.6% tetrabutylphosphonium hydroxide aqueous solution, 6.8 g of L-necked isine was added and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted alanine added in excess) were removed, and the filtrate was heated and dried under reduced pressure to remove acetonitrile and methanol, and tetrabutylphospho-muleucine llg (70% yield) was obtained. Obtained. As a result of 1 H-NMR measurement of this product, it was confirmed that the chemical shift of protons and the progress of the integrated strength force reaction proceeded.
— NMR(DMSO, δ/ppm TMS基準): 0.819 (q, 6H, J = 25 Hz), 0.91 8(t, 12H, J=14.5 Hz), 1.006 (m, 1H, J=42.5 Hz), 1.359— 1.500 ( m, 16H), 1.680 (m, 1H, J = 33.5 Hz), 2.205 (m, 8H, J = 29.5 Hz), 2. 699 (s, 1H) — NMR (DMSO, δ / ppm TMS standard): 0.819 (q, 6H, J = 25 Hz), 0.91 8 (t, 12H, J = 14.5 Hz), 1.006 (m, 1H, J = 42.5 Hz), 1.359 — 1.500 (m, 16H), 1.680 (m, 1H, J = 33.5 Hz), 2.205 (m, 8H, J = 29.5 Hz), 2. 699 (s, 1H)
[0028] 実施例 11 [0028] Example 11
41.6 %テトラブチルホスホ-ゥムハイドロキサイド水溶液 26.6gに L—フエ-ル
ァラニン 8. 5gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァ セトニトリル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結 晶(過剰に加えた未反応のフエ-ルァラニン)を除去し、濾液を減圧加熱乾燥してァ セトニトリルとメタノールを除去し、テトラブチルホスホ-ゥムフエ-ルァラニン 13g (収 率 75%)を得た。本品の1 H— NMR測定を行った結果、プロトンの化学シフトと積分 強度から反応の進行が確認された。41.6% Tetrabutyl Phosphorum Hydroxide Aqueous Solution 26.6g Alanine (8.5 g) was added and dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Then, the crystals precipitated by filtration (unreacted ferrolanine added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol, and 13 g of tetrabutyl phosphomuferallanine (yield). 75%) was obtained. As a result of 1 H-NMR measurement of this product, the progress of the reaction was confirmed from the chemical shift and integrated intensity of proton.
— NMR (DMSO, δ /ppm TMS基準):0. 916 (t, 12H, J= 14. 5 Hz) , 1 . 367—1. 487 (m, 16H) , 2. 208 (m, 8H, J = 29. 5 Hz) , 2. 365 (q, 1H, J = 22. 5 Hz) , 2. 983 (m, 2H, J=45. 5 Hz) , 7. 107— 7. 236 (m, 5H) — NMR (DMSO, δ / ppm TMS standard): 0.916 (t, 12H, J = 14.5 Hz), 1.367—1. 487 (m, 16H), 2. 208 (m, 8H, J = 29.5 Hz), 2. 365 (q, 1H, J = 25.5 Hz), 2. 983 (m, 2H, J = 45.5 Hz), 7. 107— 7. 236 (m, 5H )
[0029] 実施例 12 [0029] Example 12
41. 6 %テトラブチルホスホ-ゥムハイドロキサイド水溶液 26. 6gに Lーセリン 5. 5gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニトリル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過剰に 加えた未反応のセリン)を除去し、濾液を減圧加熱乾燥してァセトニトリルとメタノール を除去し、テトラブチルホスホ-ゥムセリン l lg (収率 73%)を得た。本品の1 H— NM R測定を行った結果、プロトンの化学シフトと積分強度力 反応の進行が確認された — NMR (DMSO, δ /ppm TMS基準):0. 917 (t, 12H, J= 14 Hz) , 1. 3 69— 1. 500 (m, 16H) , 2. 191 (m, 8H, J = 29. 5 Hz) , 2. 775 (q, 1H, J= l 5. 5 Hz) , 3. 133 (q, 1H J = 30. 5 Hz) , 3. 255 (q, 1H, J= 15. 5 Hz) [0030] 実施例 13 41. 5.5 g of L-serine was added to 26.6 g of 6% tetrabutylphosphonium hydroxide aqueous solution, and the excess water was removed by drying under reduced pressure while stirring. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Then, the crystals precipitated by filtration (unreacted serine added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol to obtain tetrabutylphospho-muselin l lg (yield 73%). It was. As a result of 1 H— NM R measurement of this product, it was confirmed that the chemical shift of proton and the progress of the integrated intensity force reaction — NMR (DMSO, δ / ppm TMS standard): 0.917 (t, 12H, J = 14 Hz), 1. 3 69— 1. 500 (m, 16H), 2. 191 (m, 8H, J = 29.5 Hz), 2. 775 (q, 1H, J = l 5.5 Hz ), 3. 133 (q, 1H J = 30.5 Hz), 3. 255 (q, 1H, J = 15.5 Hz) [0030] Example 13
41. 6wt%テトラブチルホスホ-ゥムハイドロキサイド水溶液 26. 6gに Lートレオ- ン 6. 2gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニ トリル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過 剰に加えた未反応のトレオニン)を除去し、濾液を減圧加熱乾燥してァセトニトリルと メタノールを除去し、テトラブチルホスホ-ゥムトレオニン l lg (収率 70%)を得た。本 品の1 H—NMR測定を行った結果、プロトンの化学シフトと積分強度力 反応の進行 が確認された。
H— NMR(DMSO, δ /ppm TMS基準):0.880 (d, 3H, J = 6 Hz), 0.918 (t, 12H, J=14 Hz), 1.383-1.488 (m, 16H), 2.193 (m, 8H, J = 30.5 Hz), 2.842 (d, 1H, J=4 Hz), 3.443 (m, 1H, J=ll Hz) 41. 6.2 g of L-threon was added to 26.6 g of 6 wt% tetrabutylphosphonium hydroxide aqueous solution, and the mixture was dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted threonine added excessively) are removed, and the filtrate is heated and dried under reduced pressure to remove acetonitrile and methanol, and tetrabutylphospho-mu-threonine l lg (yield 70%) is obtained. Obtained. As a result of 1 H-NMR measurement of this product, it was confirmed that the chemical shift of the proton and the progress of the integrated intensity force reaction progressed. H—NMR (DMSO, δ / ppm TMS standard): 0.880 (d, 3H, J = 6 Hz), 0.918 (t, 12H, J = 14 Hz), 1.383-1.488 (m, 16H), 2.193 (m, 8H, J = 30.5 Hz), 2.842 (d, 1H, J = 4 Hz), 3.443 (m, 1H, J = ll Hz)
[0031] 実施例 14 [0031] Example 14
41.6wt%テトラブチルホスホ-ゥムハイドロキサイド水溶液 26.6gに Lーメチォ- ン 7.7gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニ トリル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過 剰に加えた未反応のメチォニン)を除去し、濾液を減圧加熱乾燥してァセトニトリルと メタノールを除去し、テトラブチルホスホ-ゥムメチォニン 12.2g (収率 75%)を得た。 本品の1 H—NMR測定を行った結果、プロトンの化学シフトと積分強度力 反応の進 行が確認された。 7.7 g of L-methione was added to 26.6 g of 41.6 wt% tetrabutylphosphonium hydroxide aqueous solution, and the mixture was dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted methionine added in excess) were removed, and the filtrate was dried by heating under reduced pressure to remove acetonitrile and methanol, and 12.2 g of tetrabutylphospho-ummethionine (75% yield) was obtained. Obtained. As a result of 1 H-NMR measurement of this product, the chemical shift of the proton and the progress of the integrated intensity force reaction were confirmed.
'H-NMRCCDCl , δ/ppm TMS基準): 0.918 (t, 12H, J=14.5 Hz), 1. 'H-NMRCCDCl, δ / ppm TMS standard): 0.918 (t, 12H, J = 14.5 Hz), 1.
3 Three
511-1.549 (m, 16H), 1.721— 2.148 (m, 5H), 2.413 (m, 8H, J = 29.5 Hz), 2.666 (m, 8H, J = 29.5 Hz), 3.218 (q, 1H, J=12.5 Hz) [0032] 実施例 15 511-1.549 (m, 16H), 1.721— 2.148 (m, 5H), 2.413 (m, 8H, J = 29.5 Hz), 2.666 (m, 8H, J = 29.5 Hz), 3.218 (q, 1H, J = 12.5 Hz) [0032] Example 15
41.6 %テトラブチルホスホ-ゥムハイドロキサイド水溶液 26.6gに L—プロリン 4 .6gを加え、撹拌しながら、減圧乾燥を行い余分な水を除去した。これにァセトニトリ ル 60mlとメタノール 40mlを加え、撹拌した。その後、濾過により析出した結晶(過剰 に加えた未反応のプロリン)を除去し、濾液を減圧加熱乾燥してァセトニトリルとメタノ ールを除去し、テトラブチルホスホ-ゥムプロリン llg (収率 77%)を得た。本品の1 H —NMR測定を行った結果、プロトンの化学シフトと積分強度力 反応の進行が確認 された。4.6 g of L-proline was added to 26.6 g of 41.6% tetrabutylphosphonium hydroxide aqueous solution, and the mixture was dried under reduced pressure with stirring to remove excess water. To this, 60 ml of acetonitrile and 40 ml of methanol were added and stirred. Thereafter, the crystals precipitated by filtration (unreacted proline added in excess) are removed, and the filtrate is heated and dried under reduced pressure to remove acetonitrile and methanol, and tetrabutylphosphomproline llg (yield 77%) is obtained. Obtained. As a result of 1 H-NMR measurement of this product, it was confirmed that the chemical shift of protons and the progress of the integrated strength force reaction proceeded.
— NMR(CDC1 , δ/ppm TMS基準): 0.976 (t, 12H, J=14 Hz), 1.52 — NMR (CDC1, δ / ppm TMS standard): 0.976 (t, 12H, J = 14 Hz), 1.52
3 Three
7(m, 16H, J=19 Hz), 1.657 (m, 2H, J = 51 Hz), 1.870 (m, 1H, J = 32. 5 Hz), 2.082 (m, 1H, J = 36 Hz), 2.395 (m, 8H, J=29 Hz), 2.784 (m , 1H, J=17.5 Hz), 3.097 (m, 1H, J = 23 Hz), 3.511 (m, 1H, J=14.5 Hz) 7 (m, 16H, J = 19 Hz), 1.657 (m, 2H, J = 51 Hz), 1.870 (m, 1H, J = 32.5 Hz), 2.082 (m, 1H, J = 36 Hz), 2.395 (m, 8H, J = 29 Hz), 2.784 (m, 1H, J = 17.5 Hz), 3.097 (m, 1H, J = 23 Hz), 3.511 (m, 1H, J = 14.5 Hz)
産業上の利用可能性
本発明により提供されるイオン液体は、各種合成反応の溶媒や分離 ·抽出溶媒、酵 素反応溶媒としての応用はもちろんのこと、ノ ッテリーや燃料電池などの電解質材料 として禾 IJ用することができる。
Industrial applicability The ionic liquid provided by the present invention can be used not only as a solvent for various synthetic reactions, as a separation / extraction solvent, and as an enzyme reaction solvent, but also as an electrolyte material for knotters and fuel cells. .
Claims
[化 1] [Chemical 1]
0 0
D + DMU V A" /了、 D + DMU V A "/ End,
ΓΠ 1 Π— 1— UU ( [ ) ΓΠ 1 Π — 1 — UU ([)
[式中、カチオン部 Ph+は、(Κ 4) Ρ+ (ここで、
R2、 R3および R4は、それぞ れ独立して、非置換もしくは置換された低級アルキル基)であるカゝ、または 1もしくは それ以上の燐原子を環員として含む、非置換もしくは置換されたへテロ環の燐原子 にプロトンもしくはアルキル基が 1つ結合したカチオンであり、ァ-オン部は、アミノカ ルボン酸ァ-オン (ここで、 Rは水素原子を表すか、または NH— Yとともに 4員環から 7員環を構成し、 Yはァミノカルボン酸のアミノ基およびカルボキシル基を除 、た構成 部分を表す。)である]で示される第四級燐化合物。 [Wherein the cation moiety Ph + is (Κ 4 ) Ρ + (where R 2 , R 3 and R 4 are each independently an unsubstituted or substituted lower alkyl group), or an unsubstituted or substituted group containing one or more phosphorus atoms as ring members A cation in which a proton or an alkyl group is bonded to the phosphorus atom of the heterocyclic ring, and the cation is an aminocarboxylic acid cation (where R represents a hydrogen atom or NH—Y And a 4- to 7-membered ring, and Y represents a component other than the amino group and carboxyl group of the aminocarboxylic acid.)].
[2] Ph+力 (R1) P+ (ここで、 R1は、非置換もしくは置換された低級アルキル基)である [2] Ph + force (R 1 ) P + (where R 1 is an unsubstituted or substituted lower alkyl group)
4 Four
請求項 1の第四級燐化合物。 The quaternary phosphorus compound according to claim 1.
[3] R1がブチル基である、請求項 2に記載の第四級燐化合物。 [3] R 1 is a butyl group, a quaternary phosphorous compound according to claim 2.
[4] 上記アミノ酸ァ-オンが、 α アミノ酸ァ-オンである、請求項 1〜3のいずれか 1項 に記載の第 4級燐化合物。 [4] The quaternary phosphorus compound according to any one of claims 1 to 3, wherein the amino acid ion is an α amino acid ion.
[5] 上記アミノ酸ァ-オンが、天然の α—アミノ酸ァ-オンである、請求項 1〜4のいず れカ 1項に記載の第 4級燐化合物。 [5] The quaternary phosphorus compound according to any one of [1] to [4], wherein the amino acid ion is a natural α-amino acid ion.
[6] 上記アミノ酸ァ-オンが、 L一口イシン、 L—フエ-ルァラニン、 L—イソロイシン、グリ シン、 L グルタミン酸、 L—パリン、 L ァスパラギン酸、 L トリプトファン、 L ァラ ニン、 L アルギニン、 L ァスパラギン、 L システィン、 L グルタミン、 L ヒスチジ ン、 L リジン、 L メチォニン、 Lーセリン、 Lートレオニン、 L プロリンおよび Lーチ 口シンからなる群から選ばれるアミノ酸のァ-オンである、請求項 1〜5のいずれか 1 項に記載の第 4級燐化合物。
[6] The above amino acid cation is L-sip Ishin, L-Fe-alanine, L-isoleucine, glycine, L-glutamic acid, L-parin, L-aspartic acid, L-tryptophan, L-alanine, L-arginine, L The amino acid--one selected from the group consisting of asparagine, L-cysteine, L-glutamine, L-histidine, L-lysine, L-methionine, L-serine, L-threonine, L-proline and L-orchicin. The quaternary phosphorus compound according to any one of 5 above.
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WO2009014270A1 (en) * | 2007-07-26 | 2009-01-29 | Ajinomoto Co., Inc. | Resin composition |
JP2010285398A (en) * | 2009-06-12 | 2010-12-24 | Jx Nippon Oil & Energy Corp | Super heat-resistant ionic liquid |
JP2014139150A (en) * | 2013-01-21 | 2014-07-31 | Ajinomoto Co Inc | Method for producing n-acylamino acid or n-acylpeptide by using amino acid ionic liquid |
US8871954B2 (en) | 2011-01-10 | 2014-10-28 | Reliance Industries Limited | Process for the preparation of alditol acetals |
US8969595B2 (en) | 2011-01-10 | 2015-03-03 | Reliance Industries Limited | Method of making diacetal compound in aqueous medium |
US9029575B2 (en) | 2011-01-10 | 2015-05-12 | Reliance Industries Limited | Process for preparation of acetals |
CN110845417A (en) * | 2019-11-27 | 2020-02-28 | 中国科学院兰州化学物理研究所 | Amino acid ionic liquid water-based additive and preparation method and application thereof |
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JP2004269414A (en) * | 2003-03-07 | 2004-09-30 | Hiroyuki Ono | Organic ionic liquid having amino acid as constituting ion |
WO2005012599A1 (en) * | 2003-07-31 | 2005-02-10 | Kaneka Corporation | Method for forming oxide film on metal surface using ionic liquid, electrolytic capacitor and electrolyte thereof |
JP2005200359A (en) * | 2004-01-16 | 2005-07-28 | Tosoh Corp | Ionic compound |
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WO2002076924A1 (en) * | 2001-03-26 | 2002-10-03 | Nisshinbo Industries, Inc., | Ionic liquid, electrolyte salt for storage device, electrolytic solution for storage device, electric double layer capacitor, and secondary battery |
JP2004269414A (en) * | 2003-03-07 | 2004-09-30 | Hiroyuki Ono | Organic ionic liquid having amino acid as constituting ion |
WO2005012599A1 (en) * | 2003-07-31 | 2005-02-10 | Kaneka Corporation | Method for forming oxide film on metal surface using ionic liquid, electrolytic capacitor and electrolyte thereof |
JP2005200359A (en) * | 2004-01-16 | 2005-07-28 | Tosoh Corp | Ionic compound |
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WO2009014270A1 (en) * | 2007-07-26 | 2009-01-29 | Ajinomoto Co., Inc. | Resin composition |
JP2010285398A (en) * | 2009-06-12 | 2010-12-24 | Jx Nippon Oil & Energy Corp | Super heat-resistant ionic liquid |
US8871954B2 (en) | 2011-01-10 | 2014-10-28 | Reliance Industries Limited | Process for the preparation of alditol acetals |
US8969595B2 (en) | 2011-01-10 | 2015-03-03 | Reliance Industries Limited | Method of making diacetal compound in aqueous medium |
US9029575B2 (en) | 2011-01-10 | 2015-05-12 | Reliance Industries Limited | Process for preparation of acetals |
JP2014139150A (en) * | 2013-01-21 | 2014-07-31 | Ajinomoto Co Inc | Method for producing n-acylamino acid or n-acylpeptide by using amino acid ionic liquid |
CN110845417A (en) * | 2019-11-27 | 2020-02-28 | 中国科学院兰州化学物理研究所 | Amino acid ionic liquid water-based additive and preparation method and application thereof |
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