JPS633794A - Method for reducing alpha,beta-unsaturated carbonyl compound - Google Patents
Method for reducing alpha,beta-unsaturated carbonyl compoundInfo
- Publication number
- JPS633794A JPS633794A JP14644386A JP14644386A JPS633794A JP S633794 A JPS633794 A JP S633794A JP 14644386 A JP14644386 A JP 14644386A JP 14644386 A JP14644386 A JP 14644386A JP S633794 A JPS633794 A JP S633794A
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbonyl compound
- unsaturated carbonyl
- formula
- reducing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001728 carbonyl compounds Chemical class 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 10
- 241000193446 Thermoanaerobacterium thermosaccharolyticum Species 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- -1 -NHCHO Chemical group 0.000 claims description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 244000005700 microbiome Species 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- 125000002541 furyl group Chemical group 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000001544 thienyl group Chemical group 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000068 chlorophenyl group Chemical group 0.000 claims description 2
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 claims description 2
- 125000003106 haloaryl group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000005027 hydroxyaryl group Chemical group 0.000 claims description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims 1
- 125000006383 alkylpyridyl group Chemical group 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 claims 1
- 241000894006 Bacteria Species 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 150000001720 carbohydrates Chemical class 0.000 abstract description 3
- 235000013373 food additive Nutrition 0.000 abstract description 3
- 239000002778 food additive Substances 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 239000002609 medium Substances 0.000 description 15
- 241000193403 Clostridium Species 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000012258 culturing Methods 0.000 description 4
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- 230000000813 microbial effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
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- 239000002689 soil Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- UIERETOOQGIECD-ARJAWSKDSA-M 2-Methyl-2-butenoic acid Natural products C\C=C(\C)C([O-])=O UIERETOOQGIECD-ARJAWSKDSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 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
- 239000000543 intermediate Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- QIJRTFXNRTXDIP-UHFFFAOYSA-N (1-carboxy-2-sulfanylethyl)azanium;chloride;hydrate Chemical compound O.Cl.SCC(N)C(O)=O QIJRTFXNRTXDIP-UHFFFAOYSA-N 0.000 description 1
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 description 1
- IOCJWNPYGRVHLN-MMALYQPHSA-N (2r)-2-amino-3-[[(2r)-2-amino-2-carboxyethyl]disulfanyl]propanoic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CSSC[C@H](N)C(O)=O IOCJWNPYGRVHLN-MMALYQPHSA-N 0.000 description 1
- XUCIJNAGGSZNQT-JHSLDZJXSA-N (R)-amygdalin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O[C@@H](C#N)C=2C=CC=CC=2)O1 XUCIJNAGGSZNQT-JHSLDZJXSA-N 0.000 description 1
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- WMDBQMYVAIBBDH-NSCUHMNNSA-N (e)-2-chlorobut-2-enoic acid Chemical compound C\C=C(\Cl)C(O)=O WMDBQMYVAIBBDH-NSCUHMNNSA-N 0.000 description 1
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- YKIKDQYYTAOTPL-IHWYPQMZSA-N (z)-2-bromobut-2-enoic acid Chemical compound C\C=C(/Br)C(O)=O YKIKDQYYTAOTPL-IHWYPQMZSA-N 0.000 description 1
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- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
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- 229940024606 amino acid Drugs 0.000 description 1
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- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
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- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000025938 carbohydrate utilization Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 229960001305 cysteine hydrochloride Drugs 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- XQGPKZUNMMFTAL-UHFFFAOYSA-L dipotassium;hydrogen phosphate;trihydrate Chemical compound O.O.O.[K+].[K+].OP([O-])([O-])=O XQGPKZUNMMFTAL-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- YGHHWSRCTPQFFC-UHFFFAOYSA-N eucalyptosin A Natural products OC1C(O)C(O)C(CO)OC1OC1C(OC(C#N)C=2C=CC=CC=2)OC(CO)C(O)C1O YGHHWSRCTPQFFC-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000003890 fistula Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- QAOXMQCWUWZZNC-UHFFFAOYSA-N gamma-Methyl-alpha-butylen-alpha-carbonsaeure Natural products CC(C)C=CC(O)=O QAOXMQCWUWZZNC-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- QWIZNVHXZXRPDR-WSCXOGSTSA-N melezitose Chemical compound O([C@@]1(O[C@@H]([C@H]([C@@H]1O[C@@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)O)CO)CO)[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O QWIZNVHXZXRPDR-WSCXOGSTSA-N 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000006384 methylpyridyl group Chemical group 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PMOWTIHVNWZYFI-UHFFFAOYSA-N o-Coumaric acid Natural products OC(=O)C=CC1=CC=CC=C1O PMOWTIHVNWZYFI-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005344 pyridylmethyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- IVGPGQSSDLDOLH-UHFFFAOYSA-M sodium;10-oxido-7-oxophenoxazin-10-ium-3-olate Chemical compound [Na+].C1=CC(=O)C=C2OC3=CC([O-])=CC=C3[N+]([O-])=C21 IVGPGQSSDLDOLH-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BTYQWISIPUWRJR-UHFFFAOYSA-N tert-butyl 3-(2-methoxy-2-oxoethyl)piperidine-1-carboxylate Chemical compound COC(=O)CC1CCCN(C(=O)OC(C)(C)C)C1 BTYQWISIPUWRJR-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
- 125000005301 thienylmethyl group Chemical group [H]C1=C([H])C([H])=C(S1)C([H])([H])* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- PMOWTIHVNWZYFI-AATRIKPKSA-N trans-2-coumaric acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1O PMOWTIHVNWZYFI-AATRIKPKSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 description 1
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は、α、β−不爺和カルボニル化合物の還元方
法に関し、さらに詳しく言うと、微生物を用いて、α、
β−不飽和カルボニル化合物に水素添加して、光学活性
なカルボニル化合物を、高収率、高選択率で、容易に、
かつ、安価に製造することができるα、β−不飽和カル
ボニル化合物の還元方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for reducing α,β-unionized carbonyl compounds, and more specifically, the present invention relates to a method for reducing α,β-unionized carbonyl compounds, and more specifically, using microorganisms,
By hydrogenating β-unsaturated carbonyl compounds, optically active carbonyl compounds can be easily produced in high yield and high selectivity.
The present invention also relates to a method for reducing an α,β-unsaturated carbonyl compound that can be produced at low cost.
この発明の方法は、種々の飽和カルボン酸、とくに、高
純度光学活性（絶対配置Ｒ体）なカルボン酸やケトンの
製造分野に利用することができる。また、得られる光学
活性なカルボン酸やケトン等のカルボニル化合物は、た
とえば光学活性な化学薬品、溶媒、錯体もしくは触媒配
位子、食品添加物等として、あるいは、その他の−般化
学薬品、溶媒等として、また、他の光学活性な化学薬品
、錯体、触媒、溶媒、化成品原料、その中間体、重合体
、化成品、食品添加剤等の原料として好適に利用するこ
とができる。The method of the present invention can be used in the field of producing various saturated carboxylic acids, particularly high-purity optically active (absolute R configuration) carboxylic acids and ketones. In addition, the obtained optically active carbonyl compounds such as carboxylic acids and ketones can be used as optically active chemicals, solvents, complexes or catalyst ligands, food additives, etc., or as other general chemicals, solvents, etc. It can also be suitably used as a raw material for other optically active chemicals, complexes, catalysts, solvents, raw materials for chemical products, intermediates thereof, polymers, chemical products, food additives, etc.
［従来の技術およびその問題点］
従来、微生物を用いて、α、β−、β−カルポン酸を水
素により還元して光学活性なカルボン酸等のカルボン酸
を製造する方法は知られている［Ｈ，Ｓｉｍｏｎ ら
、 ＡｎｇｅｗｌＣｈｅｍ、Ｉｎｔｅｒｎａｔ、Ｅｄｉ
ｔ、 １−ジ（９） ６０８ （１９７４） 、
Ｈ，Ｇｉｅｓｅｌら、Ａｒｃｈ、Ｍｉ−ｃｒｏｂｉｏｌ
、上ユ１．５１ （１９８３）］ 、Ｌかしながら、
これらの方法では、生成する飽和カルボン酸の選択率、
とくに、光学活性なカルボン酸の選択率は、高いものの
、微生物として、たとえば、クロストリジウム令りルイ
ベリー（Ｃ１ｏｓｔｒｉ−ｄｉｕｍ Ｋｌｕｙｖｅｒｙ
（ＤＳ）ｌ−５５５）） 、クロストリジ１７Ａ−エス
ピー・Ｌａ −１（Ｃ１，ｓｐ、Ｌａ −１（ＤＳ）ｌ
−１４８０） ）等の中温菌（最適温度：たとえば３５
℃程度）を用いているので、反応速度が十分でなく、し
たがって、生成物の収率が十分でなかったり、培養（発
酵）時間が長かったり、また、雑菌汚染を受は易すがっ
たり、培養中に、冷却して温度制御を行なうことが必須
であったり、目的生成物の収率、活性の安定性、プロセ
スの操作性、経済性の点等において様々の問題点があっ
た。[Prior art and its problems] Conventionally, a method is known for producing carboxylic acids such as optically active carboxylic acids by reducing α, β-, and β-carboxylic acids with hydrogen using microorganisms [ H, Simon et al., AngewlChem, Internat, Edi
t, 1-di(9) 608 (1974),
H, Giesel et al., Arch, Mi-crobiol
, Kamiyu 1.51 (1983)], L.
In these methods, the selectivity of the saturated carboxylic acid produced,
In particular, although the selectivity of optically active carboxylic acids is high, as a microorganism, for example, Clostridium Kluyvery
(DS)l-555)), Clostridium 17A-SP La-1(C1, sp, La-1(DS)l
-1480) ) and other mesophilic bacteria (optimal temperature: e.g. 35
℃), the reaction rate is not sufficient, resulting in insufficient product yield, long culture (fermentation) time, and easy bacterial contamination. Among these, there are various problems such as the necessity of cooling and temperature control, the yield of the desired product, the stability of the activity, the operability of the process, and the economic efficiency.
［発ＩＪＪの目的］ この発明は、前記事情に基づいてなされたものである。[Purpose of IJJ] This invention has been made based on the above circumstances.
すなわち、この発明の目的は、前記問題点を解消し１反
応速度が大きく、雑菌汚染が少なく、活性が安定してお
り、生成するカルボン酸の選択率が高く、生成するカル
ボン酸が光学活性の場合にはその光学純度が高く、かつ
、その収率が著しく向上した。That is, an object of the present invention is to solve the above-mentioned problems. 1. The reaction rate is high, bacterial contamination is low, the activity is stable, the selectivity of the produced carboxylic acid is high, and the produced carboxylic acid has optical activity. In some cases, the optical purity was high and the yield was significantly improved.
「前記問題点を解決するための手段］
前記問題点を解決し、前記目的を達成するためのこの発
明のａ要は、微生物を用いてα、β−不飽和カルボニル
化合物る二重結合を水素により還元して飽和カルボニル
化合物を製造する方法において、微生物としてクロスト
リジウム拳サーモサツカロリテイカムを用いることを特
徴とするα、β−不飽和カルボニル化合物方法である。"Means for Solving the Problems" The key point of the present invention for solving the problems and achieving the objects is to use microorganisms to replace double bonds in α,β-unsaturated carbonyl compounds with hydrogen. This is a method for producing a saturated carbonyl compound by reduction using α,β-unsaturated carbonyl compounds, which is characterized in that Clostridium thermosatucaloriticum is used as a microorganism.
である。It is.
この発明で使用するクロストリジウム会サーモサツカロ
リテイカム（Ｃｌｏｓｔｒｉｄｉｕｍ ｔｈｅｒｅｍｏ
ｓａｃｃ−ｈａｒｏｌｙｔｉｃｕｍ ）は、通常、畑等
の土壌、堆肥中等に見出されるクロストリジウム屈の微
生物の１種でクロスドロリジウム屈の微生物の中でも、
通常、４５〜６５℃の高温で様気的に生育、培養するこ
とができる、いわゆる様気性高温閑に分類される微生物
である。このクロストリジウム働サーモサツカロリテイ
カムには、菌体学的性質を多少異にする種々の菌株が知
られている。Clostridium theremo used in this invention
sacc-harolyticum) is a type of Clostridium microorganism that is usually found in the soil of fields, compost, etc. Among the Clostridium microorganisms, it is one of the
It is a microorganism classified as a so-called aerobic microorganism that can normally be grown and cultured at a high temperature of 45 to 65°C. Various strains of Clostridium thermosatucaloriticum are known that have somewhat different mycological properties.
この発明において使用することのできるクロストリジウ
ム◆サーモサツカロリテイカムの菌株には特に制限はな
いが、たとえばクロストリジウム・サーモサツカロリテ
イカム（Ａ−４６株）、同（Ｂ −８９５７株）、同（
Ｂ −２５８株）、同（ＡＴＣＣ−７９５８株）、同（
ＡＴＧＣ−３１９２５株）等を好適に用いることができ
、中でも、クロストリジウム・サーモサツカロリテイカ
ム（Ａ−４６株）（Ｆｅｒｎ Ｐ−８７７９）が、特
に好適である。There are no particular restrictions on the strains of Clostridium thermosatucaroliticum that can be used in this invention, but examples include Clostridium thermosatucaroliticum (strain A-46), Clostridium thermosatucaroliticum (strain B-8957),
B-258 strain), same (ATCC-7958 strain), same (
ATGC-31925 strain) etc. can be suitably used, and among them, Clostridium thermosatucaroliticum (A-46 strain) (Fern P-8779) is particularly suitable.
該Ａ−４６株は、千ＩＪ県君津郡の畑土壌中に見出され
、採取、培養、分離されたものであり、その培養、分離
の例を、次に示す。The A-46 strain was found in field soil in Kimitsu District, Senji Prefecture, and was collected, cultured, and isolated. Examples of its culture and isolation are shown below.
すなわち、０Ｍ３培地（糖酵母エキス２ｇ、ＣＮＨｓ
）２ Ｓ０４ １．５ ｇ、 Ｋ２ ＨＰＯ４争３Ｈ２
０２，９ｇ、ＭｇＣ１？＋１６Ｈ２０１ｇ、ＣａＣＪＬ
２ １５０ｍｇ、Ｆ２５Ｏｓ＊７ＨｚＯ１，２５層８、
システィン塩酸塩５００ ｍｇ、レサズリンナトリウム
２ｓ＋ｇを純水１ｆＬに含み、ｐＨ７，０ニｍ！したも
の）に酢酸ナトリウム５１ｇ／ｍｕを添加したものを５
ｍ交試験管に分注し滅′ｃＮｖｋ、土壌を１気グローブ
ポ、ラス中で約０．３ｇ添加し、ブチルゴムで密栓後、
気相をＨ２／ＣＯ２（１： ｌ）の除菌混合ガスにてと
検し、６０℃で振とう培養を行ない、１日毎に植え継ぎ
を行なう０本集積培養を５回綴り返した後、ＲＯＭ平板
（オキソイド社製ＲＯＭに寒天を３０ ｇ ／ Ｈにし
た平板）上に塗布して６０℃で３日間培養後純粋分離す
ると、Ａ−４６株を得ることができる。That is, 0M3 medium (sugar yeast extract 2g, CNHs
)2 S04 1.5 g, K2 HPO4 conflict 3H2
02.9g, MgC1? +16H201g, CaCJL
2 150mg, F25Os*7HzO1, 25 layer 8,
Contains 500 mg of cysteine hydrochloride and 2 s+g of resazurin sodium in 1 fL of pure water, pH 7.0 nm! 51g/mu of sodium acetate was added to
Dispense the mixture into sterile test tubes, add about 0.3 g of soil in a glass tube, and seal with butyl rubber.
After testing the gas phase with a sterilizing mixed gas of H2/CO2 (1: l), culturing with shaking at 60°C, and repeating the 0-plant enrichment culture five times with subculture every day, The A-46 strain can be obtained by coating on a ROM plate (a ROM plate made by Oxoid Co., Ltd. and agar at 30 g/H) and culturing at 60°C for 3 days, followed by pure separation.
次に、該Ａ−４６株の菌学的性質を示す。Next, the mycological properties of the A-46 strain will be shown.
（ａ）大きさと形状：０．５路ｍ程度×３〜１０μｍ桿
形（桿菌）
（ｂ） Ｍ動性：有り、周鞭毛
（Ｃ）胞 子：有り、内生
（ｄ）ダラム染色：不定
（ｅ）ＧＣ含量：３２％
（ｆ）生育温度＝４５〜６５℃（最適生育温度６０℃）
（ｇ）糖の利用性
（１） アドニトール 利用せず。(a) Size and shape: about 0.5 m x 3-10 μm rod-shaped (bacillus) (b) M mobility: present, periflagellated (C) spores: present, endogenous (d) Durham staining: indeterminate (e) GC content: 32% (f) Growth temperature = 45-65°C (optimum growth temperature 60°C) (g) Utilization of sugar (1) Adonitol Not used.
（２） アミグダリン 利用する。(2) Use amygdalin.
（３） アテビノース 利用する。(3) Use atebinose.
（０セロビオース 利用する。(Use 0 cellobiose.
（５） セルロース 利用せず。(5) Cellulose is not used.
（８） ズルシトール 利用せず。(8) Dulcitol not used.
（７） エフ ス リ ン 利用する。(7) Use F-Srin.
（８） エリスリトール 利用せず。(8) Erythritol was not used.
（３） フラクトース 利用する。(3) Use fructose.
（１Ｇ） ガラクトース 利用する。(1G) Use galactose.
（１１） グルコース 利用する。(11) Utilize glucose.
（１２） グリセロール 利用せず。(12) Glycerol is not used.
（１３） グリコーゲン 利用する。(13) Use glycogen.
（１４） イノシトール 利用せず。(14) Inositol not used.
（１５） イ ヌ リ ン
利用せず。(15) Inu Lin
Not used.
（１６） ラ り ト − ス 利用する。(16) Utilize the space.
（１７） マル ト −ス 利用する。(17) Utilize the smartphone.
（１８） マンニトール 利用する。(18) Use mannitol.
（１３） マンノース 利用する。(13) Use mannose.
（２０） メレジトース 利用せず。(20) Melezitose not used.
（２］） メリビオース 利用せず。(2]) Melibiose not used.
（２２） ラフィノース 利用せず。(22) Raffinose not used.
（２３） ラ ムノ −ス 利用せず。(23) Lamuno-space not used.
（２４） リ ポ − ス 利用する。(24) Use repos.
（２５） サ リ シ ン 利用する
。(25) Use sarisin.
（２８） ソルビトール 利用せず。(28) Sorbitol not used.
（２７） ソルボース 利用せず。(27) Sorbose not used.
（２８） Ｗ 粉 利用する。(28) Use W powder.
（２３） シ ヨ 糖 利用する。(23) Utilize sugar.
（３Ｇ） ）レバロース 利用する。(3G) Utilize liverose.
（３１） キシロース 利用する。(31) Use xylose.
（ｈ）下記の第１表に示す組成の培地（０Ｍ３培地）も
しくはこれにペプトン、各種アミノ酸等を添加した培地
あるいはＲＯＭ培地等ですこぶる良好な生育を示す。(h) Shows good growth in a medium with the composition shown in Table 1 below (0M3 medium), a medium to which peptone, various amino acids, etc. have been added, or a ROM medium.
第 １ 表
酵母エキス ２ｇ硫硫酸アンソン
１．５ｇリン酸−水素カリ（３水塩
） ２．９ ｇリン酸二水素カリ
１．５ ｇ塩化マグネシウム（６水増） １ｇ
塩化カルシウム １５０ ｍｇｇ酸第
一鉄（７水塩） １．２５層ｇシスティン
塩酸塩 ５００ 鳳ｇレシズリン酸ナト
リウム ２ 濡８蒸留水 １ｆＬ
ｐＨ７，０
寒 天（固体培養のみ） ｇ上記Ａ−４
６株の糖の利用性を第２表に示す。Table 1 Yeast extract 2g Anthon sulfate 1.5g Potassium hydrogen phosphate (trihydrate) 2.9 g Potassium dihydrogen phosphate
1.5 g Magnesium chloride (6 water) 1 g
Calcium chloride 150 mg Ferrous acid (heptahydrate) 1.25 g Cystine hydrochloride 500 g Sodium phosphate 2 8 Distilled water 1 fL pH 7,0 Agar (solid culture only) g A-4 above
Table 2 shows the sugar utilization of the six strains.
第 ２ 表（糖の利用）
なお、木菌（Ａ−４６株）は、工業技術院微生物工業技
術研究所にＦＥＲＮ Ｐ−８７７９として受託されてい
る。Table 2 (Usage of sugar) The wood fungus (strain A-46) has been entrusted to the Institute of Microbial Technology, Agency of Industrial Science and Technology as FERN P-8779.
この発明において、通常、好適に使用できる前記α、β
−不飽和カルボニル化合物の第［１１式
％式％
［１１
または、次の第［２］式
および次の第［３］式
％式％
で表わされるα、β−不飽和カルボニル化合物。In this invention, the above-mentioned α and β which can be normally used suitably
- An α,β-unsaturated carbonyl compound represented by the following formula [2] and the following formula [3].
ここで、第［１１式中のＲ１は、たとえば水素原子：メ
チル基、エチル基、ｎ−プロピル基、イソプロピル基、
ブチル基等の低級アルキル基：フッ素原子、塩素原子、
臭素原子、ヨウ素原子等のハロゲン原子、−ＣＮ、−Ｎ
ＨＣＨＯ等の６基を意味し、特に好ましいＲ１として、
水素原子、メチル基、塩素原子、臭素原子、−ＣＮ、−
ＮＨＣＨＯ等を挙げることができる。Here, R1 in formula [11] is, for example, a hydrogen atom: methyl group, ethyl group, n-propyl group, isopropyl group,
Lower alkyl groups such as butyl groups: fluorine atoms, chlorine atoms,
Halogen atoms such as bromine atoms and iodine atoms, -CN, -N
It means 6 groups such as HCHO, and as a particularly preferable R1,
Hydrogen atom, methyl group, chlorine atom, bromine atom, -CN, -
Examples include NHCHO.
前記第［１］式のＲ２は、水素原子；メチル基、エチル
基、ｎ−プロピル基、イソプロピル基、１−ブチル基、
２−ブチル基、イソブチル基、ターシャリブチル基、ペ
ンチル基、ヘキシル基、オクチル基、デシル基、ウンデ
シル基、テトラデシル基、ヘキサデシル基、オクタデシ
ル基等のアルキル基ニジクロプロピル基、シクロブチル
基、シクロペンチル基、メチルシクロペンチル基、シク
ロヘキシル基、メチルシクロヘキシル基、二手ルシクロ
ヘキシル基等のシクロアル禁九基：ヒニル基、２−プロ
ペニル基、ｌ−プロペニル基、２−ブテニル基、３−ブ
テニル基、２−メチル−２−プロペニル基、ペンテニル
基、ヘキセニル基、シクロヘキセニル基、ビニルシクロ
ヘキシル基、オクテニル基、デセニル基、ヘキサデセニ
ル基等のフルケニル基；フェニル基、ビフェニル基、ナ
フチル基等のアリール基：メチルフェニル基、エチルフ
ェニル基、ジメチルフェニル基等のフルアリール基、フ
ェニルメチル基、フェニルエチル基、メチルフェニルメ
チル基、メチルフェニルエチル基等の７ラルキル基：メ
トキシフェニル基、エトキシフェニル基等のフルコキシ
フェニル基：ヒドロキシフェニル基、ジヒドロキシフェ
ニル基、メチルヒドロキシフェニル基等のヒドロキシア
リール基：クロロフェニル基、ジクロロフェニル基、フ
リルエチル基等のハロアリール基：ピリジルｉ！Ｊｉ；
メチルピリジル基等のフルキルピリジル基：ピリジルメ
チル基、ピリジルエチル基等のピリジルアルキル基：カ
ルボキシル基：ヒドロキシエチル基、ヒドロキシプロピ
ル基：ヒドロキシブチル基等のヒドロキシアルキル基；
メトキシカルボニル基、エトキシカルボニル基、ブトキ
シカルボニル基等のアルコキシカルボニル基：フェノキ
シ力ルポニル基；メトキシメチル基、メトキシエチル基
、メトキシブチル基、エトキシメチル基、エトキシエチ
ル基等のフルコキシアルキル基：フリル基、メチルフリ
ル基等のフリル基：フリルメチル基、フリルエチル基等
のフリルアルキル基：チエニル基、メチルチエニル基等
のチエニル基；チエニルメチル基等のチエニルアルキル
基等の基を意味する。これらの中でも、特に好ましいＲ
２としては、たとえば、水素原子；メチル基、エチル基
、ｎ−プロピル基、イソプロピル基等の低級アルキル基
、アリル基等の低級アルケニル基：フェニル基：２−ヒ
ドロキシフェニル基等のヒドロキシフェニル２！ｉ；４
−メトキシフェニル基等のメトキシフェニル基：４−ク
ロロフェニル基等のモノクロロフェニル基：カルポキシ
ル基；３−ピリジル基等のピリジル基：フルフリル基（
２−フリルメチル基）等のフリルメチル基：２−ヒドロ
キシエチル基等のヒドロキシエチル基：エトキシカルボ
ニル基等の低級アルコキシカルボニル基、２−チエニル
基等のチエニル基：等を挙げることができる。R2 in the formula [1] is a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, 1-butyl group,
Alkyl groups such as 2-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, undecyl group, tetradecyl group, hexadecyl group, octadecyl group, dichloropropyl group, cyclobutyl group, cyclopentyl group , methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, dicarboxylcyclohexyl group, and other cycloalkylene groups: hinyl group, 2-propenyl group, l-propenyl group, 2-butenyl group, 3-butenyl group, 2-methyl- Flukenyl groups such as 2-propenyl group, pentenyl group, hexenyl group, cyclohexenyl group, vinylcyclohexyl group, octenyl group, decenyl group, hexadecenyl group; Aryl groups such as phenyl group, biphenyl group, naphthyl group: methylphenyl group, ethyl Furaryl group such as phenyl group, dimethylphenyl group, heptaralkyl group such as phenylmethyl group, phenylethyl group, methylphenylmethyl group, methylphenylethyl group: Flucoxyphenyl group such as methoxyphenyl group, ethoxyphenyl group: hydroxy Hydroxyaryl groups such as phenyl group, dihydroxyphenyl group, methylhydroxyphenyl group: Haloaryl group such as chlorophenyl group, dichlorophenyl group, furylethyl group: Pyridyl i! Ji;
Furkylpyridyl group such as methylpyridyl group: pyridylalkyl group such as pyridylmethyl group, pyridylethyl group: carboxyl group: hydroxyethyl group, hydroxypropyl group: hydroxyalkyl group such as hydroxybutyl group;
Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group: phenoxyluponyl group; flukoxyalkyl group such as methoxymethyl group, methoxyethyl group, methoxybutyl group, ethoxymethyl group, ethoxyethyl group: furyl group , a furyl group such as a methylfuryl group: a furyl alkyl group such as a furylmethyl group or a furylethyl group; a thienyl group such as a thienyl group or a methylthienyl group; a thienylalkyl group such as a thienylmethyl group; Among these, particularly preferable R
2 is, for example, a hydrogen atom; a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group; a lower alkenyl group such as an allyl group; a phenyl group; a hydroxyphenyl group such as a 2-hydroxyphenyl group; i;4
-Methoxyphenyl group such as methoxyphenyl group: Monochlorophenyl group such as 4-chlorophenyl group: Carpoxyl group; Pyridyl group such as 3-pyridyl group: Furfuryl group (
(2-furylmethyl group), hydroxyethyl groups such as 2-hydroxyethyl groups, lower alkoxycarbonyl groups such as ethoxycarbonyl groups, and thienyl groups such as 2-thienyl groups.
前記第［１１式中のＲ３は、水素原子：メチル基、エチ
ル基等の低級アルキル基、メトキシ基、エトキシ基等の
低級アルコキシ基等を意味する。R3 in the formula [11] means a hydrogen atom: a lower alkyl group such as a methyl group or an ethyl group, or a lower alkoxy group such as a methoxy group or an ethoxy group.
これらの中でも、特に好ましいＲ３としては、水素原子
、メチル基、エトキシ基等を挙げることができる。Among these, particularly preferred R3 includes a hydrogen atom, a methyl group, an ethoxy group, and the like.
前記［２］式中のＲ４は前記第［１］式中のＲ３と同様
の基を表わし、好ましいＲ４として、水素原子、メチル
基、エトキシ基等を挙げることができる。R4 in the formula [2] represents the same group as R3 in the formula [1], and preferable examples of R4 include a hydrogen atom, a methyl group, and an ethoxy group.
前記第［２］式中のＲ４Ｇ：前記第［１１式中Ｒ３と同
様の基を表わし、好ましいＲ４として、水素原子、メチ
ル基、エトキシ基等を挙げることができる。R4G in the formula [2]: represents the same group as R3 in the formula [11], and preferable examples of R4 include a hydrogen atom, a methyl group, and an ethoxy group.
前記第［２］式中のＹは、アルキレン基すなわち→ＣＲ
’Ｒト升Ｔ〜を表わす、ここで、Ｒ５、Ｈｂは、水素原
子、メチル基、エチル基等の低級アルキル基：メトキシ
基、エトキシ基等の低級アルコシキ基：塩素原子等のハ
ロゲン原子：カルポキシル基：ブトキシカルボニル基等
の低級アルコキシカルボニル基等の基を表わし、特に好
ましいＲ５、Ｒ６は水素原子である。また、ｎは３〜１
６の整数を表わし、好ましいｎは、３〜８の整数、特に
好ましいｎは４である。Y in the formula [2] is an alkylene group, that is, →CR
R5, Hb represents a hydrogen atom, a lower alkyl group such as a methyl group or an ethyl group; a lower alkoxy group such as a methoxy group or an ethoxy group; a halogen atom such as a chlorine atom; carpoxyl Group: Represents a group such as a lower alkoxycarbonyl group such as a butoxycarbonyl group, and particularly preferred R5 and R6 are hydrogen atoms. Also, n is 3 to 1
It represents an integer of 6, preferably n is an integer of 3 to 8, and particularly preferably n is 4.
前記第［３］式中のＲ７およびＲ８は水素原子：メチル
基、エチル基、プロピル基、ｎ−プロピル基、イソプロ
ピル基、ｌ−ブチル基、２−ブチル基、イソブチル基、
ターシャリブチル基、ペンチル基、ヘキシル基、オクチ
ル基、デシル基、ウンデシル基、テトラデシル基、ヘキ
サデシル基、オクタデシル基等のアルキル基を表わし、
ｍは２〜４の整数を表わす、これらの中でも、Ｒ１−Ｒ
８が共に水素原子でり、ｍが３であるものが好ましい。R7 and R8 in the formula [3] are hydrogen atoms: methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, l-butyl group, 2-butyl group, isobutyl group,
Represents an alkyl group such as a tertiary butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, an undecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group,
m represents an integer of 2 to 4; among these, R1-R
Preferably, both 8's are hydrogen atoms and m is 3.
以上、第［１］弐〜第［３］式で表わされるα、β−不
飽和カルボニル化合物も、特に好ましいものの具体例と
しては、たとえば、アクリル酸、（Ｅ）−２−メチル−
２−ブテン酸、（Ｅ）−２−ブテン酸、３−メチル−２
−ブテン酸、（Ｅ）−２−ペンテン酸、（Ｅ）−２−ヘ
キセン酸、（Ｅ）−４−メチル−２−ペンテン酸、（Ｅ
）−２，５−ヘキサジエン酸、フマル酸、フマル酸モノ
エチル、（Ｅ）−３−フェニルアクリル酸、（Ｅ）−３
−（２−ヒドロキシフェニル）アクリル酸、（Ｅ）−３
−（Ｐ−メトキシフェニル）アクリル酸、（Ｅ）−３−
（Ｐ−クロロフェニル）アクリル酸、（Ｅ）−３−（３
−ピリジル）アクリル酸、（Ｅ）−３−フルフリルアク
リル酸、（Ｅ）−３−（２−チエニル）アクリル酸、メ
タクリル酸、（Ｚ）−２−メチル−２−ブテン酸、（Ｅ
）−５−ヒドロキシ−２−メチルー２−ペンテン酸、（
Ｅ）−３−フェニルメタクリル酸、（Ｚ）−３−エトキ
シ−２−シアノアクリル酸、（Ｚ）−３−７エニルー２
−ホルミルアミノアクリル酸、２−クロロアクリル酸、
（Ｅ） −２−クロロ−２−ブテン酸、２−ブロモアク
リル酸、（Ｚ）−２−ブロモ−２−ブテン酸、（Ｚ）−
２−ブロモ−３−フェニルアクリル酸、１−シクロへキ
センカルポン酸、２−シクロヘキセン−１−オン等の様
々の化合物を挙げることができる。As mentioned above, α,β-unsaturated carbonyl compounds represented by formulas [1]2 to [3] are also particularly preferred, such as acrylic acid, (E)-2-methyl-
2-butenoic acid, (E)-2-butenoic acid, 3-methyl-2
-butenoic acid, (E)-2-pentenoic acid, (E)-2-hexenoic acid, (E)-4-methyl-2-pentenoic acid, (E)
)-2,5-hexadienoic acid, fumaric acid, monoethyl fumarate, (E)-3-phenylacrylic acid, (E)-3
-(2-hydroxyphenyl)acrylic acid, (E)-3
-(P-methoxyphenyl)acrylic acid, (E)-3-
(P-chlorophenyl)acrylic acid, (E)-3-(3
-pyridyl)acrylic acid, (E)-3-furfurylacrylic acid, (E)-3-(2-thienyl)acrylic acid, methacrylic acid, (Z)-2-methyl-2-butenoic acid, (E
)-5-hydroxy-2-methyl-2-pentenoic acid, (
E)-3-phenylmethacrylic acid, (Z)-3-ethoxy-2-cyanoacrylic acid, (Z)-3-7enyl-2
-formylaminoacrylic acid, 2-chloroacrylic acid,
(E) -2-chloro-2-butenoic acid, 2-bromoacrylic acid, (Z)-2-bromo-2-butenoic acid, (Z)-
Mention may be made of various compounds such as 2-bromo-3-phenylacrylic acid, 1-cyclohexenecarboxylic acid, 2-cyclohexene-1-one, and the like.
この発明の方法においては、前記クロストリジウム・サ
ーモサツカロリテイカム（Ａ−４６株）等のクロストリ
ジウム争サーモサツカロリテイカムの存在下に前記α、
β−不飽和カルボニル化合物−炭素二重結合に水素分子
を付加（水素化）せしめて、α、β位が飽和しているカ
ルボニル化合物を製造する。In the method of the present invention, the α,
β-unsaturated carbonyl compound - A carbonyl compound with saturated α and β positions is produced by adding (hydrogenation) a hydrogen molecule to the carbon double bond.
ここで、生成するカルボニル化合物が、光学活性になり
得る場合には、上記水素化は不斉水素化となり、高い光
学純度のカルボニル化合物（通常、絶対配置Ｒ体）が生
成する。Here, when the carbonyl compound produced can be optically active, the above hydrogenation becomes asymmetric hydrogenation, and a carbonyl compound (usually R-form in absolute configuration) with high optical purity is produced.
前記水素化の温度は、使用するクロストリジウム争サー
モサツカロリテイカムの生育温度の範囲、好ましくは、
最適生育温度の範囲に設定する。したがって、その温度
範囲は、菌株の種類、培地の組成、ｐＨ等、他の条件等
によって異なるので一様に規定できないが、たとえば、
通常、４５〜６５℃、好ましくは、５５〜６２℃に設定
することができる。The hydrogenation temperature is within the range of the growth temperature of Clostridium thermosaccharolyticum used, preferably
Set within the optimal growth temperature range. Therefore, the temperature range cannot be uniformly defined because it varies depending on the type of bacterial strain, the composition of the culture medium, pH, etc., but, for example,
Usually, the temperature can be set at 45 to 65°C, preferably 55 to 62°C.
前記水素化に際しての１反応系のＰＨは、通常、８．０
〜８．０好ましくは８．５〜７．５の範囲に設定すれば
よい。The pH of one reaction system during the hydrogenation is usually 8.0.
It may be set in the range of 8.0 to 8.0, preferably 8.5 to 7.5.
前記水素化に際しての水系の圧力は、通常０．１〜２０
気圧、好ましくは、０．５〜３気圧の範囲に設定する。The pressure of the aqueous system during the hydrogenation is usually 0.1 to 20
Atmospheric pressure is preferably set in the range of 0.5 to 3 atm.
前記水素化に際しての反応時間は、他の様々の条件によ
って異なるので一様に規定できないが、通常、０．５〜
２時間程度で十分である。The reaction time during the hydrogenation cannot be uniformly defined because it varies depending on various other conditions, but it is usually 0.5 to
About 2 hours is sufficient.
なお、前記水素化反応は、必要に応じて反応系に、メチ
ルビオロゲン等のビオロゲン色素等の様々の添加剤を添
加して行うことができる。The hydrogenation reaction can be carried out by adding various additives such as viologen dyes such as methyl viologen to the reaction system, if necessary.
前記水素化に使用する水素は、純粋水素ガス、各種工業
用水素、水素分子を含有する不活性ガス等の水素含有ガ
ス等のいずれのものであ、ってもよい、該不活性ガスと
しては、たとえば、ヘリウム、アルゴン、窒素、二酸化
炭素、水蒸気、メタン、プロパン、ブタン等の炭化水素
ガス等または、これらの混合物を挙げることができる。The hydrogen used in the hydrogenation may be any hydrogen-containing gas such as pure hydrogen gas, various industrial hydrogen, or an inert gas containing hydrogen molecules. , for example, helium, argon, nitrogen, carbon dioxide, water vapor, hydrocarbon gases such as methane, propane, butane, etc., or mixtures thereof.
また、必要に応じてＤ２ （重水素）、ＨＤを用いて
、特定の位置に重水素を含有するカルボン酸を得ること
もできる。Furthermore, a carboxylic acid containing deuterium at a specific position can also be obtained by using D2 (deuterium) and HD as necessary.
前記水素化に使用するクロストリジウム・サーモサツカ
ロリテイカムは、該菌の培養によって得られた培養液と
して用いても、また、培養液から、たとえば遠心分離な
どの公知の分離方法で、分離して得られた菌体として用
いてもよい、また、鎖国もしくは菌体は、公知の様々の
方法によって固定化した状態で使用してもよい。Clostridium thermosatucaroliticum used in the hydrogenation can be used as a culture solution obtained by culturing the bacteria, or can be separated from the culture solution by a known separation method such as centrifugation. The obtained microbial cells may be used, or the microbial cells may be used after being immobilized by various known methods.
前記培養は、使用する菌が利用することのできる糖類も
しくは該糖類を含有する物質を含有する適切な培地を用
いて、所定の温度で曙気的に行うことができる。この培
養に際して、好適に用いることができる培地として、た
とえば、０Ｍ３培地（前記第１表の組成の培地等）、Ｒ
ＯＭ培地等を挙げることができる。培地の状態は、液体
培地、固体培地、スラリー状のいずれの状態でもよいが
、液体培地が生産性の点で好適である。The culture can be carried out in the morning at a predetermined temperature using an appropriate medium containing a saccharide or a substance containing the saccharide that can be utilized by the bacteria used. For this culture, examples of media that can be suitably used include 0M3 medium (medium with the composition shown in Table 1 above), R
Examples include OM medium. The state of the medium may be a liquid medium, a solid medium, or a slurry, but a liquid medium is preferable in terms of productivity.
培養温度は、通常、４５〜６５℃、好ましくは、５５〜
６２℃に設定する。培養時間は、菌の濃度が十分に向上
するのに必要な時間であればよく、たとえば通常４〜３
６時間、好ましくは、８〜１８時間程時間段定すれば十
分である。The culture temperature is usually 45-65°C, preferably 55-65°C.
Set to 62°C. The culture time may be any time necessary to sufficiently increase the concentration of bacteria, for example, usually 4 to 3 days.
A time period of 6 hours, preferably 8 to 18 hours is sufficient.
培養方法としては、静置培養、攪拌培養、液体培養、固
体培養など、いずれの方法を用いてもよい。As a culture method, any method such as static culture, agitation culture, liquid culture, solid culture, etc. may be used.
培養に際しては、ｐＨは、通常、５．０〜８．０、好ま
しくは、８．５〜７．５程度の範囲に設定する。During culture, the pH is usually set in a range of about 5.0 to 8.0, preferably about 8.5 to 7.5.
このようにして培養して得られた培養物はクロストリジ
ウム拳す−モサー２カロリティカムを高い濃度で含有す
るので、そのまま、前記水素化反応に使用することがで
きるが、通常、該培養物から、菌体を分離しで、水素化
反応に供するのが望ましい、この培養物からの菌体の分
離は、通常の様々の分離方法により行なうことができる
が、たとえば、遠心分離法を好適に使用することができ
る。Since the culture obtained by culturing in this way contains Clostridium fistula 2 calolyticum at a high concentration, it can be used as it is in the hydrogenation reaction, but usually, bacteria are extracted from the culture. It is desirable to separate the bacterial cells and subject them to the hydrogenation reaction. Isolation of the bacterial cells from this culture can be carried out by various conventional separation methods, but for example, centrifugation is preferably used. Can be done.
以上のような方法により、製造された、様々のカルボニ
ル化合物、とくに光学活性のカルボニル化合物は、その
ままもしくは、適当な化学処理を施して化学薬品、化成
品の原料や中間体や錯体や不斉水素化触媒の配位子等の
詰化剤、液晶の原料として、様々の用途に好適に利用す
ることができる。Various carbonyl compounds, especially optically active carbonyl compounds, produced by the above methods can be used as they are, or after being subjected to appropriate chemical treatments, to be used as raw materials for chemicals, chemical products, intermediates, complexes, and asymmetric hydrogen. It can be suitably used in a variety of applications, such as as a filler for ligands in chemical catalysts, and as raw materials for liquid crystals.
［発明の効果］ この発明によると、以下の効果を奏することができる。[Effect of the invention] According to this invention, the following effects can be achieved.
（１）種々のα、β−不飽和カルボニル化合物様々な飽
和カルボニル化合物を高い収率、高い選択率で、安定に
製造することができる。(1) Various α,β-unsaturated carbonyl compounds Various saturated carbonyl compounds can be stably produced in high yield and high selectivity.
特に、光学純度が著しく高い種々の光学活性なカルボニ
ル化合物を、効率よく得ることができる。したがって、
生産物の回収も容易で、かつ経済的である。In particular, various optically active carbonyl compounds with extremely high optical purity can be obtained efficiently. therefore,
Recovery of the product is also easy and economical.
（２）微生物として、好熱菌であるクロストリジウム舎
サーモサツカロリテイカムを使用しているので、培養お
よび、水素化反応を高温で行うことができるので、’Ｉ
ＩＧ汚染が少なく、活性が安定しており、かつ反応速度
が大きいので、生産性が著しく向上する。(2) Since the thermophilic bacterium Clostridium thermosaccharolyticum is used as the microorganism, culture and hydrogenation reactions can be carried out at high temperatures.
Since there is little IG contamination, the activity is stable, and the reaction rate is high, productivity is significantly improved.
すなわち、この発明よると、光学純度の高い、光学活性
なカルボニル化合物たとえばカルボン酸を容易に、かつ
安価に製造することができる、優れた、α、β−不飽和
カルボニル化合物方法を提供することができる。That is, according to the present invention, it is possible to provide an excellent method for producing an α,β-unsaturated carbonyl compound, which can easily and inexpensively produce an optically active carbonyl compound, such as a carboxylic acid, with high optical purity. can.
［実施例］
（実施例１）
クロストリジウム・サーモサツカロリテイカム（Ａ−４
６株）をＲＣＭ液体培地に接種し、６０℃で１８時間榎
気的に培養した。この培養液をＲＣＭ液体培＃Ａ５００
ｍＪＬに２％の割合で植菌し。[Example] (Example 1) Clostridium thermosatucaroliticum (A-4
6 strains) were inoculated into an RCM liquid medium and cultured under aerobic conditions at 60°C for 18 hours. Transfer this culture solution to RCM liquid medium #A500.
Inoculate mJL at a rate of 2%.
１１のメディアボトル中で６０℃で１２時間様気的に静
を培養を行なった。これを遠心分離して得た菌体３０■
ｇを０．１Ｍトリス緩衝液（ｐＨ７，０）に懸濁し、メ
チルビオロゲンを３．０■貝とチグリン酸［（Ｅ）−２
−メチル−２−ブテン酸〕を２ｍｇ／ｍ又添加し、１気
圧の水素雰囲気下に６０℃で２時間の反応をおこなった
。この反応液を遠心分離により除菌した後、リン酸酸性
にし、ガスクロマトグラフ（担体クロモソルブ１０１、
ガラスカラム２ｍ、２４０℃）により生成物の分析をお
こなった。また除菌した反応液について、旋光度針（株
式会社堀場製作所、５ＥＰＡ−２００，セル長１ ｃｍ
）により比旋光度を測定し光学純度を求めた。結果は、
第３表に示す。The culture was carried out under air for 12 hours at 60° C. in 11 media bottles. 30 microbial cells obtained by centrifuging this
g was suspended in 0.1 M Tris buffer (pH 7.0), and 3.0 μg of methyl viologen was added to the shellfish and tiglic acid [(E)-2
-Methyl-2-butenoic acid] was added at 2 mg/m, and the reaction was carried out at 60° C. for 2 hours in a hydrogen atmosphere of 1 atm. After sterilizing this reaction solution by centrifugation, it was made acidic with phosphoric acid, and then analyzed using a gas chromatograph (carrier Chromosolve 101,
The product was analyzed using a 2 m glass column (240° C.). In addition, for the sterilized reaction solution, an optical rotation needle (Horiba, Ltd., 5EPA-200, cell length 1 cm) was used.
) to measure the specific rotation and determine the optical purity. Result is,
It is shown in Table 3.
（実施例２〜３０）
実施例１においてチグリン酸の代りに第３表に示した基
質を用いたこと以外は実施例１と同様に行なった。なお
、ガスクロマトグラフで分析下を駈の化合物については
、高速液体クロマトグラフ（アニメックスＡ−２５．カ
ラム５０ｃ層）により分析した。結果を第３表にまとめ
て示す。(Examples 2 to 30) The same procedures as in Example 1 were conducted except that the substrates shown in Table 3 were used instead of tiglic acid. Compounds that were not analyzed by gas chromatography were analyzed by high performance liquid chromatography (Animex A-25 column 50c layer). The results are summarized in Table 3.
第 ３ 表
Ｉ ＣＨ３ＣＨ３ＨＯ，５８＞９８．Ｒ２ＨＨＨＯ，８
７
３ＨＣＨ３Ｈ１，２２
４ＨＣＨ３ＣＨ３０，２３
５“ＨＣｔ Ｈｓ ＨＯ，５２
６Ｈｎ−Ｃ３Ｈ７ＨＯ，５３
８Ｈｎ−Ｃ５Ｈｓ ＨＬ５８
９ ＨＣ０ＯＨＨ１００
１０ＨＣＯＯＣ２Ｈ５ＨＯ，５２
第 ３ 表 遣さ）
１８ ＣＨ３ＨＨ１，０８
１９ＣＨ３ＨＣＨ３０，２５＞９８．Ｒ２０ＣＨ３Ｃ２
Ｈ４ＯＨＨＯ，５５＞９８．Ｒ２２ＣＮ ＨＯＣ２
Ｈ５Ｏ，２４
２４Ｃ又 ＨＨ１，３２＞９６．Ｒ
２５０文 ＣＨ３ＨＯＪ３ ＞９８．Ｒ２６Ｂｒ
ＨＨ１，４４＞９８．Ｒ２７Ｂｒ ’ＣＨ３Ｈ１
，３８＞９８．Ｒ２９Ｙ；−（ＣＨ２）４− Ｒ４，
ＨＯ，１３本１：第［３］式で示される化合物、ｍ＝３
、Ｒ７，Ｒ８＝Ｈ手続補正書
昭和６１年７月 ３日Table 3 CH3CH3HO, 58>98. R2HHHO,8
7 3HCH3H1,22 4HCH3CH30,23 5"HCt Hs HO,52 6Hn-C3H7HO,53 8Hn-C5Hs HL58 9 HCOOHH100 10HCOOC2H5HO,52 Table 3) 18 CH3HH1,08 19C H3HCH30,25>98.R20CH3C2
H4OHHO, 55>98. R22CN HOC2
H5O,24 24C or HH1,32>96. R 250 sentences CH3HOJ3 >98. R26Br
HH1,44>98. R27Br 'CH3H1
,38>98. R29Y;-(CH2)4- R4,
HO, 13 pieces 1: Compound represented by formula [3], m = 3
, R7, R8 = H procedural amendment July 3, 1986
Claims (11)
における二重結合を水素により還元して飽和カルボニル
化合物を製造する方法において、微生物としてクロスト
リジウム・サーモサッカロリティカムを用いることを特
徴とするα，β−不飽和カルボニル化合物の還元方法。(1) A method for producing a saturated carbonyl compound by reducing the double bond in an α,β-unsaturated carbonyl compound with hydrogen using a microorganism, characterized in that Clostridium thermosaccharolyticum is used as the microorganism. A method for reducing α,β-unsaturated carbonyl compounds.
ムが、クリストリジウム・サーモサッカロリティカムＡ
−４６株（Ｆｅｒｍ Ｐ−８７７９）である前記特許請
求の範囲第１項に記載のα，β−不飽和カルボニル化合
物の還元方法。(2) The Clostridium thermosaccharolyticum is Clostridium thermosaccharolyticum A
-46 strain (Ferm P-8779), the method for reducing an α,β-unsaturated carbonyl compound according to claim 1.
［１］〜［３］式、 ▲数式、化学式、表等があります▼［１］ （但し、前記第［１］式中、Ｒ＾１は、水素原子、低級
アルキル基、−ＣＮ、−ＮＨＣＨＯ、ハロゲン原子の中
のいずれかの基を表わし、Ｒ＾２は、水素原子、アルキ
ル基、シクロアルキル基、アルケニル基、アリール基、
アルアリール基、アラルキル基、アルコキシフェニル基
、ヒドロキシアリール基、ハロアリール基、ピリジル基
、アルキルピリジル基、ピリジルアルキル基、カルボキ
シル基、ヒドロキシアルキル基、アルコキシアルキル基
、フェノキシカルボニル基、アルコキシカルボニル基、
フリル基、フリルアルキル基、チエニル基、チエニルア
ルキル基の中のいずれかの基を表し、Ｒ＾３は、水素原
子、低級アルキル基、アルコキシ基、の中のいずれかの
基を表わす。） ▲数式、化学式、表等があります▼［２］ （ただし、前記第［２］式中Ｒ＾４は、前記Ｒ＾３と同
様の基を表わし、Ｙは（ＣＲ＾５Ｒ＾６）＿ｎを表わす
。ここで、ｎは、３〜１６の整数を表わし、Ｒ＾５およ
びＲ＾６は、水素原子、低級アルコキシ基、低級アルキ
ル基、ハロゲン原子、カルボキシル基、低級アルコキシ
カルボニル基よりなる群から選択された１種または２種
以上の基を表わす。） ▲数式、化学式、表等があります▼［３］ （ただし、前記第［３］式中、Ｒ＾７およびＲ＾８は水
素原子またはアルキル基を示し、ｍは２〜４の整数を表
わす。） で表わされるα，β−不飽和カルボニル化合物である前
記特許請求の範囲第１項または第２項のいずれかに記載
のα，β−不飽和カルボニル化合物の還元方法。(3) The above α,β-unsaturated carbonyl compound has the following formulas [1] to [3], ▲ mathematical formula, chemical formula, table, etc. ▼ [1] (However, in the above formula [1], R^1 represents a hydrogen atom, a lower alkyl group, -CN, -NHCHO, or a halogen atom, and R^2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. ,
Araryl group, aralkyl group, alkoxyphenyl group, hydroxyaryl group, haloaryl group, pyridyl group, alkylpyridyl group, pyridylalkyl group, carboxyl group, hydroxyalkyl group, alkoxyalkyl group, phenoxycarbonyl group, alkoxycarbonyl group,
It represents any group among a furyl group, a furyl alkyl group, a thienyl group, and a thienyl alkyl group, and R^3 represents any group among a hydrogen atom, a lower alkyl group, and an alkoxy group. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [2] (However, in the formula [2] above, R^4 represents the same group as R^3 above, and Y is (CR^5R^6)_n Here, n represents an integer of 3 to 16, and R^5 and R^6 are a group consisting of a hydrogen atom, a lower alkoxy group, a lower alkyl group, a halogen atom, a carboxyl group, and a lower alkoxycarbonyl group. represents one or more groups selected from.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [3] (However, in the above formula [3], R^7 and R^8 are hydrogen atoms. or an alkyl group, and m represents an integer of 2 to 4. Method for reducing β-unsaturated carbonyl compounds.
基、−ＣＮ、−ＮＨＣＨＯ、塩素原子、臭素原子の中の
いずれかの基である前記特許請求の範囲第３項に記載の
α，β−不飽和カルボニル化合物の還元方法。(4) Claim 3, wherein R^1 in the formula [1] is any group among a hydrogen atom, a methyl group, -CN, -NHCHO, a chlorine atom, and a bromine atom. A method for reducing an α,β-unsaturated carbonyl compound as described in .
、エチル基、ｎ−プロピル基、イソプロピル基、アリル
基、フェニル基、ヒドロキシフェニル基、メトキシフェ
ニル基、クロロフェニル基、カルボキシル基、ピリジル
基、フルフリル基、（２−フリルメチル基）、ヒドロキ
シエチル基、エトキシカルボニル基（−ＣＯＯＣ＿２Ｈ
＿５）、２−チエニル基等の中から選ばれるいずれかの
基である前記特許請求の範囲第３項または第４項のいず
れかに記載のα，β−不飽和カルボニル化合物の還元方
法。(5) R^3 in the formula [1] above is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, phenyl group, hydroxyphenyl group, methoxyphenyl group, chlorophenyl group, carboxyl group group, pyridyl group, furfuryl group, (2-furylmethyl group), hydroxyethyl group, ethoxycarbonyl group (-COOC_2H
_5) A method for reducing an α,β-unsaturated carbonyl compound according to claim 3 or 4, which is any group selected from _5), 2-thienyl group, etc.
エトキシ基の中のいずれかの基である前記特許請求の範
囲第３項から第５項までのぃずれかに記載のα，β−不
飽和カルボニル化合物の還元方法。(6) The formula R^2 in [1] above is a hydrogen atom, a methyl group,
A method for reducing an α,β-unsaturated carbonyl compound according to any one of claims 3 to 5, which is any group among ethoxy groups.
エトキシ基の中のいずれかである前記特許請求の範囲第
３項に記載のα，β−不飽和カルボニル化合物の還元方
法。(7) R^4 in the formula [2] above is a hydrogen atom, a methyl group,
A method for reducing an α,β-unsaturated carbonyl compound according to claim 3, which is any ethoxy group.
範囲第３項または第７項に記載のα，β−不飽和カルボ
ニル化合物の還元方法。(8) The method for reducing an α,β-unsaturated carbonyl compound according to claim 3 or 7, wherein n in the formula [2] is 4.
ある前記特許請求の範囲第３項または第７項または第８
項に記載のα，β−不飽和カルボニル化合物の還元方法
。(9) Claim 3, 7 or 8, wherein R^5 and R^6 in the formula [2] are hydrogen atoms.
A method for reducing the α,β-unsaturated carbonyl compound described in 2.
が飽和したカルボン酸が、光学活性（絶対配置Ｒ体）カ
ルボン酸である前記特許請求の範囲第１項から第９項ま
でのいずれかに記載のα，β−不飽和カルボニル化合物
の還元方法。(10) Any of the above claims 1 to 9, wherein the saturated carboxylic acid or the carboxylic acid saturated at the α and β positions is an optically active (absolute configuration R configuration) carboxylic acid. A method for reducing an α,β-unsaturated carbonyl compound as described in .
前記特許請求の範囲第１項〜第１０項のいずれかに記載
のα，β−不飽和カルボニル化合物の還元方法。(11) The reduction is carried out at a temperature range of 45 to 65°C.
A method for reducing an α,β-unsaturated carbonyl compound according to any one of claims 1 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14644386A JPS633794A (en) | 1986-06-23 | 1986-06-23 | Method for reducing alpha,beta-unsaturated carbonyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14644386A JPS633794A (en) | 1986-06-23 | 1986-06-23 | Method for reducing alpha,beta-unsaturated carbonyl compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS633794A true JPS633794A (en) | 1988-01-08 |
Family
ID=15407764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14644386A Pending JPS633794A (en) | 1986-06-23 | 1986-06-23 | Method for reducing alpha,beta-unsaturated carbonyl compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS633794A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995026371A1 (en) * | 1994-03-28 | 1995-10-05 | Patrique Limited | Intermediates for the preparation of poly(cyanoacrylates) and applications of the poly(cyanoacrylates) so prepared |
| EP0979877A2 (en) * | 1998-08-06 | 2000-02-16 | Showa Denko Kabushiki Kaisha | Method of producing alpha-halo-alpha, beta-saturated carbonyl compounds |
| KR100358368B1 (en) * | 1999-11-03 | 2002-10-25 | 임영진 | Wooden door and manufacture method thereof |
| JP2005318858A (en) * | 2004-05-11 | 2005-11-17 | Mitsubishi Chemicals Corp | Method for producing optically active carboxylic acid |
-
1986
- 1986-06-23 JP JP14644386A patent/JPS633794A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995026371A1 (en) * | 1994-03-28 | 1995-10-05 | Patrique Limited | Intermediates for the preparation of poly(cyanoacrylates) and applications of the poly(cyanoacrylates) so prepared |
| EP0979877A2 (en) * | 1998-08-06 | 2000-02-16 | Showa Denko Kabushiki Kaisha | Method of producing alpha-halo-alpha, beta-saturated carbonyl compounds |
| EP0979877A3 (en) * | 1998-08-06 | 2003-10-15 | Showa Denko Kabushiki Kaisha | Method of producing alpha-halo-alpha, beta-saturated carbonyl compounds |
| KR100358368B1 (en) * | 1999-11-03 | 2002-10-25 | 임영진 | Wooden door and manufacture method thereof |
| JP2005318858A (en) * | 2004-05-11 | 2005-11-17 | Mitsubishi Chemicals Corp | Method for producing optically active carboxylic acid |
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