JPH02115147A - Novel aminoalkane derivative - Google Patents
Novel aminoalkane derivativeInfo
- Publication number
- JPH02115147A JPH02115147A JP63266762A JP26676288A JPH02115147A JP H02115147 A JPH02115147 A JP H02115147A JP 63266762 A JP63266762 A JP 63266762A JP 26676288 A JP26676288 A JP 26676288A JP H02115147 A JPH02115147 A JP H02115147A
- Authority
- JP
- Japan
- Prior art keywords
- group
- amino
- acid
- compound
- formula
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- 125000006239 protecting group Chemical group 0.000 claims abstract description 7
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000003884 phenylalkyl group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Chemical group 0.000 claims abstract description 5
- 150000002367 halogens Chemical group 0.000 claims abstract description 5
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 claims abstract description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 4
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 15
- -1 sulfo, mesyl Chemical group 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 11
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 abstract description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008635 plant growth Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 235000010265 sodium sulphite Nutrition 0.000 abstract description 4
- 238000003328 mesylation reaction Methods 0.000 abstract description 3
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006277 sulfonation reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000012359 Methanesulfonyl chloride Substances 0.000 abstract 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract 1
- 235000011130 ammonium sulphate Nutrition 0.000 abstract 1
- 238000003898 horticulture Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000008719 thickening Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 29
- 230000008018 melting Effects 0.000 description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229940024606 amino acid Drugs 0.000 description 5
- 235000001014 amino acid Nutrition 0.000 description 5
- 150000001413 amino acids Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-DYCDLGHISA-M Sodium hydroxide-d Chemical compound [Na+].[2H][O-] HEMHJVSKTPXQMS-DYCDLGHISA-M 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OAZUHBHKEZYYSU-NUBCRITNSA-N (2S)-1-bromo-3-methylbutan-2-amine hydrochloride Chemical compound CC(C)[C@@H](CBr)N.Cl OAZUHBHKEZYYSU-NUBCRITNSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 238000007070 tosylation reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- WVIVEABPZNXWQX-RXMQYKEDSA-N (2S)-2-amino-3-methylbutane-1-sulfonic acid Chemical compound N[C@H](CS(=O)(=O)O)C(C)C WVIVEABPZNXWQX-RXMQYKEDSA-N 0.000 description 1
- GAFNJFRXWWDEMG-SECBINFHSA-N (2r)-2-amino-3-phenylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)C[C@H](N)CC1=CC=CC=C1 GAFNJFRXWWDEMG-SECBINFHSA-N 0.000 description 1
- JBULSURVMXPBNA-RXMQYKEDSA-N (2s)-2-amino-3,3-dimethylbutan-1-ol Chemical compound CC(C)(C)[C@H](N)CO JBULSURVMXPBNA-RXMQYKEDSA-N 0.000 description 1
- GAFNJFRXWWDEMG-VIFPVBQESA-N (2s)-2-amino-3-phenylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)C[C@@H](N)CC1=CC=CC=C1 GAFNJFRXWWDEMG-VIFPVBQESA-N 0.000 description 1
- XDZZQMNDCFNREN-VKHMYHEASA-N (2s)-2-aminopropane-1-sulfonic acid Chemical compound C[C@H](N)CS(O)(=O)=O XDZZQMNDCFNREN-VKHMYHEASA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- KJIGZLDDTOVUGH-UHFFFAOYSA-N 1-aminopropyl methanesulfonate Chemical compound CCC(N)OS(C)(=O)=O KJIGZLDDTOVUGH-UHFFFAOYSA-N 0.000 description 1
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 description 1
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenylpropanol Natural products OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HGNGPTUJFKAAKN-HNCPQSOCSA-N CS(=O)(=O)OC[C@@H](CC1=CC=CC=C1)N.Cl Chemical compound CS(=O)(=O)OC[C@@H](CC1=CC=CC=C1)N.Cl HGNGPTUJFKAAKN-HNCPQSOCSA-N 0.000 description 1
- HGNGPTUJFKAAKN-PPHPATTJSA-N CS(=O)(=O)OC[C@H](CC1=CC=CC=C1)N.Cl Chemical compound CS(=O)(=O)OC[C@H](CC1=CC=CC=C1)N.Cl HGNGPTUJFKAAKN-PPHPATTJSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- YFMUSJRRIGAMNW-FYZOBXCZSA-N Cl.CS(=O)(=O)OC[C@H](C(C)C)N Chemical compound Cl.CS(=O)(=O)OC[C@H](C(C)C)N YFMUSJRRIGAMNW-FYZOBXCZSA-N 0.000 description 1
- XYXPUYLCUPSSDS-WCCKRBBISA-N Cl.CS(=O)(=O)OC[C@H](C)N Chemical compound Cl.CS(=O)(=O)OC[C@H](C)N XYXPUYLCUPSSDS-WCCKRBBISA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FXOAPDMKKFVOGK-ZCFIWIBFSA-N [(2S)-2-amino-3-methylbutyl] methanesulfonate Chemical compound CC(C)[C@H](N)COS(C)(=O)=O FXOAPDMKKFVOGK-ZCFIWIBFSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- WOYXQCUBRRZMPN-UHFFFAOYSA-N ethene;hydrochloride Chemical compound Cl.C=C.C=C.C=C WOYXQCUBRRZMPN-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010647 peptide synthesis reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 125000000612 phthaloyl group Chemical group C(C=1C(C(=O)*)=CC=CC1)(=O)* 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002054 transplantation Methods 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規アミノアルカン誘導体及びその薬学的に許
容される塩に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to novel aminoalkane derivatives and pharmaceutically acceptable salts thereof.
（従来の技術）
アミノ酸のカルボキシル基にあたる部分がスルホ基であ
るタウリン等のアミノ酸類縁体は、医薬、化粧品など種
々の用途に有用な化合物として知られている。本発明者
らは、これらアミノ酸類縁体に関して研究を行った結果
、植物生長調整作用を有する新規アミノアルカン誘導体
並びに該化合物を製造する際に合成中間体として有用な
新規化合物を見出し、本発明を完成した。(Prior Art) Amino acid analogs such as taurine, in which the carboxyl group of the amino acid is a sulfo group, are known as compounds useful for various uses such as medicine and cosmetics. As a result of conducting research on these amino acid analogs, the present inventors discovered a novel aminoalkane derivative having a plant growth regulating effect and a new compound useful as a synthetic intermediate in the production of the compound, and completed the present invention. did.
（発明が解決しようとする問題点）
本発明の目的は、植物生長調整作用を有する新規アミノ
アルカン＝ｉ体及びその合成中間体を提供することにあ
る。(Problems to be Solved by the Invention) An object of the present invention is to provide a novel aminoalkane i-form having a plant growth regulating effect and a synthetic intermediate thereof.
（問題点を解決するための手段）
本発明化合物は、下記−数式（１）で表される新規アミ
ノアルカン誘導体である。(Means for Solving the Problems) The compound of the present invention is a novel aminoalkane derivative represented by the following formula (1).
１式中、Ｒは水素又はアミノ基の保３Ｎ基、Ｙは低級ア
ルキル基、フェニル基、フェニルアルキル基、ヒドロキ
シアルキル基又はフェニルアルキルオキ、ジアルキル基
、Ｘはスルホ基、メシル基、トシル基又はハロゲンを表
す。〕
上記−数式（＋）において、Ｒの表すアミノ基の保護基
としては、ベブチ１′合成化学の分野で用いられている
通常の保護基が利用でき、即ち、【−ブトキシカルボニ
ル、（−ペントキシカルボニル基等の低級アルコキシカ
ルボニル
ル基、ｏ−クロロヘンジルオキン力ルボニル、ｐ−ニト
ロヘンジルオキシ力ルポニル、ｐ−メトキシベンジルオ
キシカルボニル基等の置換基を有するヘンシルオキシカ
ルボニル基、トシル基、トリチル基、ホルミル基、フタ
ロイル基、０−ニトロフェニルスルフェニＢｙ１５．９
−フルオレニルメチルオキシカルボニル基などが挙げら
れる。In formula 1, R is hydrogen or an amino group, Y is a lower alkyl group, phenyl group, phenylalkyl group, hydroxyalkyl group, or phenylalkyloxy, dialkyl group, and X is a sulfo group, mesyl group, tosyl group, or Represents halogen. ] In the above formula (+), as a protecting group for the amino group represented by R, a usual protecting group used in the field of bebuty 1' synthetic chemistry can be used, that is, [-butoxycarbonyl, (-pen Lower alkoxycarbonyl groups such as toxycarbonyl groups, henzyloxycarbonyl groups having substituents such as o-chlorohenzyloxycarbonyl, p-nitrohenzyloxycarbonyl, p-methoxybenzyloxycarbonyl groups, tosyl groups , trityl group, formyl group, phthaloyl group, 0-nitrophenylsulfenyl By15.9
-fluorenylmethyloxycarbonyl group and the like.
Ｙは水素、低級アルキル基、好ましくはメチル、エチル
、プロピル、イソプロピル、ブチル、イソブチル、５ｅ
ｃ−ブチル、ｔｅｒ ｔ−ブチル基等の直鎖又は分枝状
の炭素数１乃至４のアルキル基、フェニル基、フェニル
アルキル基、好ましくはメチル、エチル、プロピル基等
の炭素数１乃至３のアルキル基にフェニル基が結合した
フェニルアルキル基、ヒドロキノアルキル基、好ましく
はヒドロキシメチル、ヒドロキシエチル、ヒドロキシプ
ロピル基等の炭素数１乃至３のヒドロキシアルキル基或
いはフェニルアルキルオキシアルキル基、好ましくはメ
チル、エチル、プロピル基等の炭素数１乃至３のアルキ
ル法にフェニル基が結合したフェニルアルキル基を有す
るフェニルアルキルオキソメチル、フェニルアルキルオ
キシエチル、フェニルアルキルオキンプロピル基等を表
す。Y is hydrogen, a lower alkyl group, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 5e
Straight-chain or branched alkyl groups having 1 to 4 carbon atoms such as c-butyl and tert-butyl groups; phenyl groups and phenylalkyl groups; preferably methyl, ethyl, and propyl groups having 1 to 3 carbon atoms; A phenylalkyl group in which a phenyl group is bonded to an alkyl group, a hydroquinoalkyl group, preferably a hydroxyalkyl group having 1 to 3 carbon atoms such as hydroxymethyl, hydroxyethyl, hydroxypropyl group, or a phenylalkyloxyalkyl group, preferably methyl, It represents phenylalkyloxomethyl, phenylalkyloxyethyl, phenylalkyloquinpropyl groups, etc., which have a phenylalkyl group in which a phenyl group is bonded to an alkyl group having 1 to 3 carbon atoms such as ethyl or propyl group.
Ｘはスルホ基、メシル基、トシル基又は塩素、臭素、沃
素等のハロゲンを表す。X represents a sulfo group, mesyl group, tosyl group, or a halogen such as chlorine, bromine, or iodine.
本発明アミノアルカン誘導体はその薬学的に許容される
塩を包含し、例えば、塩酸、硫酸、硝酸、臭化水素酸、
リン酸、過塩素酸、チオシアン酸、ホウ酸等の無ｉ酸、
ギ酸、酢酸、ハロ酢酸、プロピオン酸、グリコール酸、
クエン酸、酒石酸、コハク酸、グルコン酸、乳酸、マロ
ン酸、フマール酸、アントラニル酸、安息香酸、ケイ皮
酸、ｐ−）ルエンスルホン酸、ナフタレンスルホン酸、
スルフアニル酸等の有機酸との酸付加塩、或いはナトリ
ウム、カリウム等のアルカリ金属、かルシウム、バリウ
ム等のアルカリ土類金属、その他のアルミニウム等の金
属との塩、又はアンモニウム、有機アミンとの塩などが
挙げられろ。The aminoalkane derivatives of the present invention include pharmaceutically acceptable salts thereof, such as hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid,
Non-acid such as phosphoric acid, perchloric acid, thiocyanic acid, boric acid,
Formic acid, acetic acid, haloacetic acid, propionic acid, glycolic acid,
Citric acid, tartaric acid, succinic acid, gluconic acid, lactic acid, malonic acid, fumaric acid, anthranilic acid, benzoic acid, cinnamic acid, p-)luenesulfonic acid, naphthalenesulfonic acid,
Acid addition salts with organic acids such as sulfanilic acid, salts with alkali metals such as sodium and potassium, alkaline earth metals such as calcium and barium, other metals such as aluminum, or salts with ammonium and organic amines. There are many things that can be mentioned.
又、本発明化合物はその金属１７１４ヒ合物を包含し、
例えば亜鉛、ニッケル、コバルト、銅、鉄等との錯化合
物が挙げられる。The compounds of the present invention also include metal 1714 compounds,
Examples include complex compounds with zinc, nickel, cobalt, copper, iron, etc.
これらの塩並びに金属錯化合物は公知の方法により遊離
の本発明アミノアルカン誘導体より製造でき、或いは相
互に変換することができる。These salts and metal complex compounds can be produced from the free aminoalkane derivative of the present invention by known methods, or can be converted into each other.
本発明化合物において光学異性体が存在する場合には、
本発明はそのいずれをも包含する。When optical isomers exist in the compound of the present invention,
The present invention includes both of them.
次に、本発明化合物の製造方法の一例を述べる。Next, an example of a method for producing the compound of the present invention will be described.
ｔｌ＋原料物質として、前記−数式（＋）中のＸが水酸
基である化合物を用いる。該原料物質は、試薬として入
手可能なものも多く、又、アラニン、バリン、ロイシン
、イソロイシン、フェニルアラニン、セリン等のアミノ
酸を通常の方法により還元して得ることもできる。これ
らアミノ酸類は０体、Ｌ体の分割された光学異性体が多
く製造されており、本発明化合物の各々の異性体を得る
際には便１１１である。As the tl+ raw material, a compound in which X in the formula (+) is a hydroxyl group is used. Many of these raw materials are available as reagents, and they can also be obtained by reducing amino acids such as alanine, valine, leucine, isoleucine, phenylalanine, and serine using conventional methods. Many of these amino acids are produced as resolved optical isomers of 0-form and L-form, and stool 111 is used to obtain each isomer of the compound of the present invention.
まず、出発物質アミノアルコール化合物のメシル化、ト
シル化、ハロゲン化を行う。例えば、塩化メチレン等の
反応を阻害しない適当な溶媒中、トリエチＪＬ、アミン
等のｌの存在下、塩化メタンスルホン酸を反応させるこ
とによりメシル化反応を行うことができ、又、塩化トル
エンスルホン酸等の試薬を用いることにより、トシル化
することができる。First, the starting amino alcohol compound is mesylated, tosylated, and halogenated. For example, the mesylation reaction can be carried out by reacting methanesulfonic acid chloride in the presence of triethylene chloride, amine, etc. in a suitable solvent that does not inhibit the reaction such as methylene chloride, or toluenesulfonic acid chloride. Tosylation can be achieved by using reagents such as
ハロゲン化法としては、テトラブロモメタンとトリフェ
ニルホスフィンを反応させる方法や臭化水素等でハロゲ
ン化する方法などが挙げられ、又、メシル化した化合物
を臭化リチウム等の試薬によりハロゲン化する方法も利
用できる。これらのメシル化、トシル化、ハロゲン化に
際しては、出発物質のアミノ基は上述したアミノ基の保
護基により保護しておくのが好ましいが、反応の種類に
応じて保護する必要のない場合もある。Examples of halogenation methods include a method of reacting tetrabromomethane with triphenylphosphine, a method of halogenating with hydrogen bromide, etc., and a method of halogenating a mesylated compound with a reagent such as lithium bromide. Also available. During these mesylation, tosylation, and halogenation, it is preferable to protect the amino group of the starting material with the above-mentioned amino group protecting group, but depending on the type of reaction, protection may not be necessary. .
（２）次に、上記（１）で得られたアミノアルカン化合
物のメシルオキシ、トシルオキシ、ハロゲン誘導体のス
ルホン化を行う。(2) Next, the mesyloxy, tosyloxy, and halogen derivatives of the aminoalkane compound obtained in the above (1) are sulfonated.
スルホン化反応の前に、ｔ−ブトキシカルボニル等でア
ミノ基を保護されている化合物に関しては、該保護基を
除去しておくのが好ましい。保護基の種類によってそれ
ぞれ好ましい脱保護基反応が適用できるが、ペプチド合
成化学で用いられる接触還元、酸分解等の通常の方法に
より行うことができる。For compounds whose amino groups are protected with t-butoxycarbonyl or the like, it is preferable to remove the protecting group before the sulfonation reaction. Depending on the type of protecting group, a preferable deprotection reaction can be applied, but it can be carried out by conventional methods such as catalytic reduction and acid decomposition used in peptide synthesis chemistry.
スルホン化反応は、水等の反応を阻害しない適当な溶媒
中、亜硫酸ナトリウム、亜硫酸アンモニウム等と室温で
数時間乃至数十時間反応させることにより実施でき、−
１式（１）中のＸがスルホ基である本発明化合物を得る
ことができる。The sulfonation reaction can be carried out by reacting with sodium sulfite, ammonium sulfite, etc. at room temperature for several hours to several tens of hours in a suitable solvent such as water that does not inhibit the reaction, -
1 A compound of the present invention in which X in formula (1) is a sulfo group can be obtained.
上述した本発明化合物の製造方法に従えば、分割された
光学異性体を出発物質として使用することにより、ラセ
ミ化することなく最終のアミノアルカンスルホン酸誘導
体の光学異性体を各々製造することができる。According to the method for producing the compound of the present invention described above, each of the final optical isomers of the aminoalkanesulfonic acid derivative can be produced without racemization by using the resolved optical isomers as starting materials. .
得られた本発明化合物は、クロマトグラフィー、再結晶
等の通常の手段により精製し、元素分析、融点、ＩＲ，
ＮＭＩ？ＳＵＶ、マススペクトル等により同定を行った
。面、比旋光度はナトリウムのＤ線を用いて測定した。The obtained compound of the present invention is purified by conventional means such as chromatography and recrystallization, and subjected to elemental analysis, melting point, IR,
NMI? Identification was performed using SUV, mass spectrometry, etc. The plane and specific rotation were measured using sodium D line.
以下に、本発明製造方法の実施例を示す。Examples of the manufacturing method of the present invention are shown below.
（実施例）
実施例１゜
ｆｘｌ１８．９ｇの（Ｓ） −２−（Ｎ−ブトキシカル
ボニル）アミノプロピオン酸と２０ｇの炭酸水素カリウ
ムをジメチルホルムアミドに溶かし、１０−のヨウ化メ
チルを室温で加えた。 ２０時間かき混ぜた後、水３０
０ｄに反応混合物を加え、ベンゼン−酢酸エチルの混合
溶媒で抽出した。抽出液を水、５％炭酸水素ナトリウム
水）８液、１０％クエン酸水溶液、飽和食塩水で順次洗
浄した後、無水硫酸ナトリウム上で乾燥した。溶媒を減
圧下に溜去して、（Ｓ）−２−（Ｎ−Ｌ−ブトキシカル
ボニル）アミノプロピオン酸メチルエステル
得た。(Example) Example 1゜18.9 g of fxl (S)-2-(N-butoxycarbonyl)aminopropionic acid and 20 g of potassium hydrogen carbonate were dissolved in dimethylformamide, and 10-methyl iodide was added at room temperature. . After stirring for 20 hours, water 30
The reaction mixture was added to 0d and extracted with a mixed solvent of benzene-ethyl acetate. The extract was washed successively with water, 8 liquids of 5% aqueous sodium bicarbonate, 10% aqueous citric acid, and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain (S)-2-(N-L-butoxycarbonyl)aminopropionic acid methyl ester.
（２１ （Ｓ）−２−（Ｎ−ｔブトキシカルボニル）ア
ミノプロピオン酸メチルエステルと８．４８ｇの塩化リ
チウムをテトラヒドロフラン１４０−に溶かし、７．５
７ ｇの水素化ホウ素ナトリウムを加えた．室温でさら
に２８０ 、ｄのエタノールを加え２０時間かき混ぜた
。反応混合物に１０％クエン酸水溶液を加えて約ｐＨ４
とした後、有機溶媒を減圧下に溜去した。残渣水層を塩
化メチレンで抽出処理を行い、水、１０％クエン酸水溶
液、飽和食塩水で順次洗浄し、無水硫酸ナトリウム上で
乾燥した。溶媒を減圧下に溜去し、析出した白色結晶を
エーテル、石油エーテルから濾取して、１６．３ ｇの
（Ｓ） −２− （Ｎ− ｔ−ブトキシカルボニル）ア
ミノプロパン１−オールを得た。(21 (S)-2-(Nt-butoxycarbonyl)aminopropionic acid methyl ester and 8.48 g of lithium chloride were dissolved in tetrahydrofuran 140-7.5
7 g of sodium borohydride was added. At room temperature, 280.d of ethanol was further added and stirred for 20 hours. Add 10% citric acid aqueous solution to the reaction mixture to adjust the pH to approximately 4.
After that, the organic solvent was distilled off under reduced pressure. The residual aqueous layer was extracted with methylene chloride, washed successively with water, a 10% aqueous citric acid solution, and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the precipitated white crystals were collected by filtration from ether and petroleum ether to obtain 16.3 g of (S)-2-(N-t-butoxycarbonyl)aminopropane-1-ol. Ta.
収率：９３％
融 点： ５６ − ５７℃
（α） ”−−１０．５ （ｃ＝１， ＣＩＩＣｌ＋）
１１）及び（２）の方法と同様にして、以下の化合物を
得た。Yield: 93% Melting point: 56-57℃ (α)''--10.5 (c=1, CIICl+)
The following compounds were obtained in the same manner as in methods 11) and (2).
（Ｒ）−２− （Ｎ− ｔ−ブトキノカルボニル）アミ
ノプロパンニーオール
収 率：９５％
融点：（ｉ０６１′ｃ
〔α］ ”−十１０．６ （ｃ−Ｌ Ｃ．ｌｌ（：ＩＪ
（Ｓ） −２− （Ｎ−ｔ−ブトキシカルボニル）７ミ
ノー３−メチルブタン−１−オール
（Ｒ）−２−（Ｎ−ｔ−ブトキシカルボニル）アミノ−
３−メチルブタン−■ーオール
（Ｓ）−２−（Ｎ−ｔ−ブトキシカルボニル）アミノ−
３−フェニルプロパン−１−オール
（Ｒ） −２− （Ｎ− ｔ−ブトキシカルボニル）ア
ミノ−３−フェニルプロパン〜トオール
（Ｒ） −２− （Ｎ− ｔ−ブトキシカルボニル）ア
ミノ−２−フェニルエタノール
（Ｓ）−３−ベンジルオキシ−２−（Ｎ−ｔ−ブトキシ
カルボニル）アミノプロパン−■ーオール
＋３１１４．９ｇの（Ｓ）−２〜（Ｎ−ｔ−ブトキシカ
ルボニル）アミノプロパン−１−オールと９．１１ｇの
トリエチルアミンを３００−の塩化メチレンに溶かし、
−５℃にて９０ｍ１Ｍｏｌの塩化メタンスルホン酸の塩
化メチレン溶液を徐々に滴下して加えた。）８媒を減圧
下に溜去した後、残渣を酢酸エチルと水に溶かした。有
機層を分離して水と飽和食塩水で洗浄した後、無水硫酸
ナトリウム上で乾燥し、溶媒を減圧下に溜去して２０．
６ｇの（Ｓ）２− （Ｎ− ｔ−ブトキシカルボニル）
アミノ−１−（メタンスルホニル）オキシプロパンを得
た。(R)-2-(N-t-butoquinocarbonyl)aminopropane niol Yield: 95% Melting point: (i061'c[α]''-110.6 (c-L C.ll(:IJ
(S) -2- (N-t-butoxycarbonyl)7minor 3-methylbutan-1-ol (R)-2-(N-t-butoxycarbonyl)amino-
3-Methylbutan-■-ol (S)-2-(N-t-butoxycarbonyl)amino-
3-phenylpropan-1-ol (R) -2- (N-t-butoxycarbonyl)amino-3-phenylpropane to tool (R)-2- (N-t-butoxycarbonyl)amino-2-phenylethanol (S)-3-benzyloxy-2-(N-t-butoxycarbonyl)aminopropan-■-ol + 3114.9 g of (S)-2-(N-t-butoxycarbonyl)aminopropan-1-ol and 9 .11 g of triethylamine was dissolved in 300 methylene chloride,
A solution of 90 ml of methanesulfonic acid chloride in methylene chloride was gradually added dropwise at -5°C. ) After distilling off the solvent under reduced pressure, the residue was dissolved in ethyl acetate and water. The organic layer was separated, washed with water and saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give 20.
6g of (S)2-(N-t-butoxycarbonyl)
Amino-1-(methanesulfonyl)oxypropane was obtained.
収率；９６％
融点： ７５ − ７６℃
ｒα） ”＝ −３０．２ （Ｃ＝Ｉ， ＣＩＩＣＩ３
）ＮＭＲ （ＤＭＳＯ−ｄａ） ： １．０６（３１
１ ｄ，Ｊ＝７１１ｚ）、 １．３９（９１１，ｓ）、
３．１６（３１１，ｓ）、 ３．６９−３．８０（Ｉ
ＩＩ，ｍ）、 ４．０４（２Ｈ，ｄ，Ｊ＝６Ｈｚ）、
６．９３（ｌｉｔ，ｄ．Ｊ＝８１１ｚ）同様にして、以
下の化合物を得た。Yield: 96% Melting point: 75-76°C rα) ”= −30.2 (C=I, CIICI3
) NMR (DMSO-da): 1.06 (31
1 d, J=711z), 1.39 (911,s),
3.16 (311, s), 3.69-3.80 (I
II, m), 4.04 (2H, d, J=6Hz),
6.93 (lit, d.J=811z) The following compound was obtained in the same manner.
（Ｒ）−２−（Ｎ−ｔ−ブトキシカルボニル）アミノ−
１−（メタンスルホニル）オキシプロパン
収 率：９８％
融 点： ７５−７６℃（分解）
（α） ”−十２９−９ （ｃ＝１， ＣＨＣＬ３
）（Ｓ）−２−（Ｎ− Ｌ−ブトキシカルボニル）アミ
ノ−１−（メタンスルホニル）オキシ−３−メチルブタ
ン収率：８９％
融 点： Ｔ５ − １１°Ｃ（分解）〔α） ”−３
４．９ （ｃ＝１， ＣＩＩＣｈ）ＮＭｒン （ＤＭＳ
Ｏ−ｄ４） ： ０．８４（３１１，ｄ，Ｊ＝７１１
ｚ）、 ０．８７（３１Ｌｄ，Ｊ＝７１１２）、 １．
３９（９Ｈ，ｓ）、 １．７５（ＩＩＩ，ｄｑｑ，Ｊ＝
７７ ７１１ｚ）、 ３．１６（３１１．ｓ）、 ３
．５０（１１１．ｄｄｄｄ，Ｊ＝４． ７。(R)-2-(N-t-butoxycarbonyl)amino-
1-(methanesulfonyl)oxypropane Yield: 98% Melting point: 75-76°C (decomposition) (α) ”-129-9 (c=1, CHCL3
)(S)-2-(N-L-butoxycarbonyl)amino-1-(methanesulfonyl)oxy-3-methylbutane Yield: 89% Melting point: T5 - 11°C (decomposition) [α) ”-3
4.9 (c=1, CIICh) NMr (DMS
O-d4): 0.84 (311, d, J=711
z), 0.87 (31Ld, J=7112), 1.
39 (9H, s), 1.75 (III, dqq, J=
77 711z), 3.16 (311.s), 3
．． 50 (111.dddd, J=4.7.
７ ９１１ｚ）、 ４．０７（ＩＩＩ，ｄｄ．Ｊ＝７
， １０１１ｚ）、 ４．１８（ＩＩＩ。7 911z), 4.07 (III, dd. J=7
, 1011z), 4.18 (III.
ｄｄ，Ｊ＝４， １９１１ｚ）、 ６．９ＨＩＩＩ，ｄ
．Ｊ＝９１１ｚ）（Ｒ）−２− （Ｎ− ｔ−ブトキシ
カルボニル）アミノ−１−（メタンスルホニル）オキシ
−３−メチルブタン収率：９０％
融 点： ７３ − ７５℃（分解）
（α） ”＝ ＋３３．０ （ｃ・ｌ， ＣＩｌＣｈ）
（Ｓ）−２−（Ｎ−ｔ−ブトキシカルボニル）アミノ−
１−（メタンスルホニル）オキシ−３−フェニルプロパ
ン収 率；９３％
融 点： １１６ − １１７℃（分解）（α）
”＝−１７，４（ｃ・Ｉ、、 Ｃ）ＩＣｈ）ＮＭＲ（
口ＭＳＯ−ｄＪ ： １．３Ｈ９１１，ｓ）、
２．６７（ＩＨ，ｄｄＪ＝９． １４１（ｚ）、 ２
．７９（ＩＨ，ｄｄ、Ｊ＝５． １４１１ｚ）、 ３．
１７（３１１，ｓ）、 ３．８４−３．９３（ＩＩ−
１，ｗ）、 ４．０８（１Ｂ、ｄｄ、Ｊ＝６１０１１
ｚ）、 ４．１５（ＩＨ，ｄｄ、Ｊ＝５． １０１１
ｚ）、 ７．０１（ｌｆｔ、ｄ。dd, J=4, 1911z), 6.9HIII, d
．． J=911z)(R)-2-(N-t-butoxycarbonyl)amino-1-(methanesulfonyl)oxy-3-methylbutane Yield: 90% Melting point: 73-75°C (decomposition) (α)” = +33.0 (c・l, CIlCh)
(S)-2-(N-t-butoxycarbonyl)amino-
1-(Methanesulfonyl)oxy-3-phenylpropane Yield: 93% Melting point: 116-117°C (decomposition) (α)
”=-17,4(c・I,,C)ICh)NMR(
Mouth MSO-dJ: 1.3H911,s),
2.67 (IH, ddJ=9.141(z), 2
．． 79 (IH, dd, J=5.1411z), 3.
17 (311, s), 3.84-3.93 (II-
1, w), 4.08 (1B, dd, J=61011
z), 4.15 (IH, dd, J=5.1011
z), 7.01 (lft, d.
Ｊ＝９）１ｚ）、、 ７．１７−７．３１（５Ｈ，ｍ
）（Ｒ） −２−（Ｎ−ｔ−ブトキシカルボニル）アミ
ノ−１−（メタンスルホニル）オキシ−３−フェニルプ
ロパン収 率：９５％
融 点： １１６−１１７℃（分解）（α） ”−＋
１８．０ （ｃｍｌ、 ＣＩＩＣｈ）（Ｒ）−２−（
Ｎ−ｔ−ブトキシカルボニル）アミノ−２−フェニル−
１−（メタンスルホニル）オキシエタン収率；９８％
融点： １０７−１０９℃
（α） ”−１１，２（ｃ・１． ＣＩＣｌｌＣｌ５）
Ｎ （ＤＭＳＯ−ｄ６） ： １．３８（９１１，ｓ
）、 ３．１５（３１１，ｓ）４．２４（ＩＨ，ｄｄ、
Ｊ＝８．１０１１２）、 ４．２７（ＩＩｌ、ｄｄ、Ｊ
＝５．５１０ＩＩｚ） ４．８５−４．９１ （ＬＨ
，ｍ） 、 ７．２６−７．４０（５１１，ｍ）７．６
５（Ｉｌｌ、ｄ Ｊ＝９Ｈｚ）
（Ｓ）−３−ヘンシルオキシ−２−（Ｎ−ｔ−ブトキシ
カルボニル）アミノ−１−（メタンスルホニル）オキシ
プロパンｆ４１２０．６ｇの（Ｓ） −２−（Ｎ−ｔ−
ブトキシカルボニル）アミノ−１−（メタンスルホニル
）オキシプロパンを３００−の４Ｎ塩化水素／ジオキサ
ンで室温にて１時間処理した。減圧下に溶媒を溜去した
後、残渣結晶状物をエーテルより濾取し、水酸化ナトリ
ウム上減圧下に乾燥して、１４．２ｇの（Ｓ）−２−ア
ミノ−１−（メタンスルホニル）オキシプロパン塩酸塩
を得た。J=9)1z),, 7.17-7.31(5H, m
)(R) -2-(N-t-butoxycarbonyl)amino-1-(methanesulfonyl)oxy-3-phenylpropane Yield: 95% Melting point: 116-117°C (decomposition) (α) ”-+
18.0 (cml, CIICh)(R)-2-(
N-t-butoxycarbonyl)amino-2-phenyl-
1-(Methanesulfonyl)oxyethane Yield: 98% Melting point: 107-109°C (α) ”-11,2(c・1.CICllCl5)
N (DMSO-d6): 1.38 (911,s
), 3.15 (311, s) 4.24 (IH, dd,
J=8.10112), 4.27(IIl, dd, J
=5.510IIz) 4.85-4.91 (LH
, m), 7.26-7.40 (511, m) 7.6
5 (Ill, d J = 9Hz) (S) -3-hensyloxy-2-(N-t-butoxycarbonyl)amino-1-(methanesulfonyl)oxypropane f4120.6g of (S) -2-(N- t-
Butoxycarbonyl)amino-1-(methanesulfonyl)oxypropane was treated with 300-4N hydrogen chloride/dioxane for 1 hour at room temperature. After distilling off the solvent under reduced pressure, the residual crystalline material was filtered from ether and dried under reduced pressure over sodium hydroxide to give 14.2 g of (S)-2-amino-1-(methanesulfonyl). Oxypropane hydrochloride was obtained.
収率：１００％
融点： １３２−１３３℃
〔α） ！４−＋１０．３ （ｃｍｌ ＤＭＦ）Ｎ Ｍ
Ｒ（ＤＭＳＯ−ｄａ） ： １．２５（３Ｈ，ｄ、
Ｊ□７１１ｚ）１３．３０（３ｔｌ ｓ）、 ３．
４９−３．５８（１１１，ｍ）、 ４．３１（ＩＨ，
ｄｄ、Ｊ＝７゜１１１１ｚ） ８．５３（３１１，ｂ
ｒｓ）同様にして、以下の化合物を得た。Yield: 100% Melting point: 132-133℃ [α)! 4-+10.3 (cml DMF)NM
R(DMSO-da): 1.25(3H,d,
J□711z) 13.30 (3tl s), 3.
49-3.58 (111, m), 4.31 (IH,
dd, J=7°1111z) 8.53(311,b
rs) The following compounds were obtained in the same manner.
（Ｓ）−２−アミノ−１−（メタンノ、ルホニル）オキ
シプロパン塩酸塩
収率：９９％
融点： １３５−１３（ｉ℃
〔α） ”−−１０，３（ｃｍｌ、 ＤＭＦ）（Ｓ）−
２−アミノ−１−（メタンスルホニル）オキシ３−メチ
ルブタン塩酸塩
収 率：９９％
融点： １２６−１２８℃
〔α） ”＝ ＋６−６ （ｃｍｌ ＤＭＦ）ＮＭＲ（
ＤＭＳＯ−ｄｉ）： ０．９７（３１，ｄ、Ｊ＝７１
１ｚ）、０．９９（３１１，ｄ、Ｊ＝７１１ｚ）、
１．９９（１１−１，ｄｑｑ、Ｊ＝７．７，７１１ｚ）
、 ３．２３３．２８（Ｅ、ｓ）、 ３．３１（３
Ｈ，ｓ）、 ４．３４（１Ｂ、ｄｄ、Ｊ＝６１１１１
ｚ）、 ４．４６（Ｉｌｌ、ｄｄ、Ｊ＝３． １ｌＨ
ｚ）、 ８．４５（３１１，ｂｒｓ）（Ｒ）−２−ア
ミノ−１−（メタンスルホニル）オキシ−３−メチルブ
タン塩酸塩
収 率：９８％
融点： １２９−１３１ ’ｃ
Ｃα） ２４＝ −６，７（ｃｍｌ、 ＤＭＦ）（Ｓ）
−２−アミノ−１−（メタンスルホニル）オキシ−３−
フェニルプロパン塩酸塩
収 率：１００％
融点： １３３−１３４℃
〔α） ”＝ ＋７．７ （ｃｍｌ、 ＤＭＦ）ＮＭＲ
（ＤＭＳＯ−ｄａ） ： ２．８９（ＩＩＩ、ｄｄ、
Ｊ２９．１４１１ｚ）。(S)-2-amino-1-(methano, sulfonyl)oxypropane hydrochloride Yield: 99% Melting point: 135-13 (i°C [α)”--10,3 (cml, DMF) (S)-
2-Amino-1-(methanesulfonyl)oxy-3-methylbutane hydrochloride Yield: 99% Melting point: 126-128°C [α) ”= +6-6 (cml DMF) NMR (
DMSO-di): 0.97 (31, d, J=71
1z), 0.99 (311, d, J=711z),
1.99 (11-1, dqq, J=7.7,711z)
, 3.233.28(E,s), 3.31(3
H, s), 4.34 (1B, dd, J=61111
z), 4.46 (Ill, dd, J=3.1lH
z), 8.45(311,brs)(R)-2-amino-1-(methanesulfonyl)oxy-3-methylbutane hydrochloride Yield: 98% Melting point: 129-131'c Cα) 24=-6 ,7 (cml, DMF) (S)
-2-amino-1-(methanesulfonyl)oxy-3-
Phenylpropane hydrochloride Yield: 100% Melting point: 133-134°C [α) ”= +7.7 (cml, DMF) NMR
(DMSO-da): 2.89 (III, dd,
J29.1411z).
３．１０（ｌＨ，ｄｄｊ＝６．１４Ｈｚ）、 ３．２８
（３Ｈｓ） ３．７２３．７８（ＩＩＩ、＋ｓ）、
４．１９（３１１，ｄｄ、Ｊ＝５．５．１ｌｌｌｚ）
４．３４（ｌｉｌ、ｄｄ、Ｊ＝３．１ｌｌｌｚ）、
７．２６−７．３９（５ｔ１．ｍ） ８．６９（３１
１，ｂｒｓ）
（Ｒ）−２−アミノ−１−（メタンスルホニル）オキシ
−３−フェニルプロパン塩酸塩
収 率：１００％
融点： １２８−１３０℃
［α］”−−７，４（ｃｍｌ、ＤＭＦ）（Ｂ）−２−ア
ミノ−２−フェニル−１−（メタンスルホニル）オキソ
エタン塩酸塩
収 率：１００％
融点： １４４−１４６℃
〔α） ”＝ −９，４（ｃｍｌ、 ＤＭＦ）ＮＭＲ（
ＤＭＳＯ−ｄａ） ： ３．５６（３１１，ｓ）、
４．５３（ｌｉｔ、ｄｄ。3.10 (lH, ddj=6.14Hz), 3.28
(3Hs) 3.723.78 (III, +s),
4.19 (311, dd, J=5.5.1lllz)
4.34 (lil, dd, J=3.1lllz),
7.26-7.39 (5t1.m) 8.69 (31
1,brs) (R)-2-amino-1-(methanesulfonyl)oxy-3-phenylpropane hydrochloride Yield: 100% Melting point: 128-130°C [α]”--7,4 (cml, DMF ) (B) -2-amino-2-phenyl-1-(methanesulfonyl)oxoethane hydrochloride Yield: 100% Melting point: 144-146°C [α)'' = -9,4 (cml, DMF) NMR (
DMSO-da): 3.56 (311,s),
4.53 (lit, dd.
Ｊ＝４．５．１１．５Ｈｚ）、 ４．６２（ＩＩＩ、ｄ
ｄ、Ｊ＝７．５．１１．５ｔｌｚ）４．７］（ＩＨ，ｄ
ｄ、Ｊ＝４．５．７．５１１ｚ）、 ７．４０−７．４
９（３８，ｍ）７．６１−７．６５（２１１，Ｉｍ）、
９．０９（３１１，ｂｒｓ）（Ｓ）−２−アミノ−３
−ヘンシルオキシ−１−（メタンスルホニル）オキシプ
ロパン塩酸塩
収 率：９７％
融点： １１２−１１４℃
゛〔α） ”＝ ＋３．１ （ｃｍｌ、 ＤＭＦ）ＮＭ
Ｒ（ＤＭＳＯ，ＴＭＳ） ： ３．２８（３１１，ｓ
）、 ３．６３−３．７４（３１１，ｍ）、 ４．４０
（ｌＩｌ、ｄｄ、Ｊ＝５．１．１Ｉｌｚ）、 ４．４８
（ＩＨ，ｄｄ。J=4.5.11.5Hz), 4.62(III, d
d, J=7.5.11.5tlz)4.7](IH,d
d, J=4.5.7.511z), 7.40-7.4
9 (38, m) 7.61-7.65 (211, Im),
9.09(311,brs)(S)-2-amino-3
-hensyloxy-1-(methanesulfonyl)oxypropane hydrochloride Yield: 97% Melting point: 112-114°C ゛[α) ”= +3.1 (cml, DMF) NM
R (DMSO, TMS): 3.28 (311,s
), 3.63-3.74 (311, m), 4.40
(lIl, dd, J=5.1.1Ilz), 4.48
(IH, dd.
Ｊ＝３．５．１ｌｌｌｚ）、 ４．５５．４．５６（２
＋１．ＡＢＱ、Ｊ＝１２１１２）７．２８−７．４１（
５）１．ｍ）、 ８．６３（３ｔｌ、ｂｓ）ｆ５１７．
５９ｇの（Ｓ）−２−アミノ−１−（メタンスルホニル
）オキシプロパン塩酸塩と１．５６Ｂの亜硫酸ナトリウ
ムを水に熔かし、室温で２０時間かき混ぜた。反応混合
物を強酸性イオン交換樹脂に通し、溶出液を減圧下に溜
去して析出した結晶を再び水に溶かした。これを強塩基
性イオン交換樹脂に通した後、減圧下に水を溜去して析
出した白色結晶にエタノールを加えて濾取し、４．５６
ｇの（Ｓ）−２−アミノプロパン−１−スルホン酸を得
た。J=3.5.1lllz), 4.55.4.56(2
+1. ABQ, J=12112) 7.28-7.41(
5)1. m), 8.63 (3tl, bs) f517.
59 g of (S)-2-amino-1-(methanesulfonyl)oxypropane hydrochloride and 1.56 B of sodium sulfite were dissolved in water and stirred at room temperature for 20 hours. The reaction mixture was passed through a strongly acidic ion exchange resin, the eluate was distilled off under reduced pressure, and the precipitated crystals were again dissolved in water. After passing this through a strongly basic ion exchange resin, the water was distilled off under reduced pressure, and ethanol was added to the precipitated white crystals, which were collected by filtration.
g of (S)-2-aminopropane-1-sulfonic acid was obtained.
収 率：８２％
融点：＞３３０℃
〔α） ”＝ ＋ １８．５ （ｃ＝ｌ、 ＨｚＯ）元
素分析： Ｃ＊ Ｈｑ Ｎ Ｏ３Ｓとして０％ ８
％ Ｎ％
計算値： ２５．８９ ６．５２ １０．１６
実測値： ２６．１１ ６．８６ １０．２５
ＮＭＲ（０，２ＮＮａＯＤ、 ｔ−ＢｕＯＤ） ：
１．１５（３１１ｄＪ＝６．５Ｈｚ）、 ２．８６（
ｉｌｌ、ｄｄ、Ｊ＝８． １４１１ｚ）、 ２．９７
（ＩＩＩ。Yield: 82% Melting point: >330°C [α) ”= + 18.5 (c=l, HzO) Elemental analysis: 0% as C* Hq N O3S 8
% N% Calculated value: 25.89 6.52 10.16
Actual value: 26.11 6.86 10.25
NMR (0,2N NaOD, t-BuOD):
1.15 (311dJ=6.5Hz), 2.86(
ill, dd, J=8. 1411z), 2.97
(III.
ｄｄ、Ｊ・４．１４１１ｚ）、 ３．３１−３．３９（
ＩＩＩ鋼）同様にして、以下の化合物を得た。dd, J・4.1411z), 3.31-3.39(
III Steel) The following compounds were obtained in the same manner.
（１７）−２−アミノプロパン−１−スルホン酸敗 率
：６７％
融点：＞３３０℃
〔α） ” ＝ １８．３ （ｃ＝１． ｌ１ｚＯ）
元素分析： Ｃｘ Ｈ９Ｎ Ｏｚ Ｓとして０％
８％ Ｎ％
計算値： ２５．８９ ６．５２ １０．Ｊ６
実測値： ２６．０３ ６．８０ １０．４０（
Ｓ）−２−アミノ−３−メチルブタン−１〜スルホン酸
収 率＝８９％
融 点：３２５℃（分解）
〔α） ”＝ ”２９．８ （Ｃ＝ＩＩ Ｈ２Ｏ）元素
分析： Ｃｓ ＨＩ３Ｎ Ｏ２Ｓとして０％ ８
％ Ｎ％
計算値： ３５．９１ ？、８４ ８．３
８実測値： ３５．９４ ７．９８ ８．１９
ＮＭＲ（０，２ＮＮａＯＤ、 ｔ−ＢｕＯＤ） ：
０．８９（３１１ｄＪ＝７１１２）、 ０．９０（３１
，ｄ、Ｊ＝７Ｈｚ）、 １．６６−１．７８（ＩＨ，１
１）２．７６（１！Ｉ、ｄｄ、Ｊ＝９．５．１４．５ｔ
ｌｚ）、 ３．０３−３．０９（２１１，ｍ）（Ｒ＞−
２−アミノ−３−メチルブタン−１−スルホン酸敗 率
二６７％
融 点：３２５℃（分解）
〔α） ”−−２９，７（ｃ−１，ＩＩＪ）元素分析：
Ｃｓ Ｈｌ ：ｌ Ｎ Ｏｙ Ｓとして０％
１１％ Ｎ％
計算値： ３５．９１ ７．８４ ８．３８
実測値： ３５．９６ ７．９１ ８．７０
（Ｓ）−２−アミノ−３−フェニルプロパン−１−スル
ホン酸敗 率ニア２％
融点：＞３３０℃
（α） ”＝ −３，５（ｃ・１． １ｈｏ）元素分
析： Ｃ，Ｈ，ｆｆＮ０．Ｓとして０％ ］（％
Ｎ％
計算値： ５０．２２ ６．０９ ６．５１
実測値；５０゜４４ ６．３０ ６．３ＯＮＭＲ
（０，２ＮＮａＯＤ、 Ｌ−ＢｕＯＤ） ＋ ２．（
ｉ８（ＩＩＩ、ｄＪ。(17)-2-Aminopropane-1-sulfonic acid decomposition rate: 67% Melting point: >330°C [α)” = 18.3 (c=1.l1zO)
Elemental analysis: 0% as Cx H9N Oz S
8% N% Calculated value: 25.89 6.52 10. J6
Actual value: 26.03 6.80 10.40 (
S)-2-amino-3-methylbutane-1 to sulfonic acid Yield = 89% Melting point: 325°C (decomposition) [α) ”= ”29.8 (C=II H2O) Elemental analysis: As Cs HI3N O2S 0% 8
% N% Calculated value: 35.91 ? ,84 8.3
8 Actual measurement value: 35.94 7.98 8.19
NMR (0,2N NaOD, t-BuOD):
0.89 (311 dJ=7112), 0.90 (31
, d, J=7Hz), 1.66-1.78 (IH, 1
1) 2.76 (1!I, dd, J=9.5.14.5t
lz), 3.03-3.09 (211, m) (R>-
2-Amino-3-methylbutane-1-sulfonic acid decomposition rate 267% Melting point: 325°C (decomposition) [α)''--29,7 (c-1, IIJ) Elemental analysis:
Cs Hl: 0% as l N Oy S
11% N% Calculated value: 35.91 7.84 8.38
Actual value: 35.96 7.91 8.70
(S)-2-amino-3-phenylpropane-1-sulfonic acid failure rate near 2% Melting point: >330°C (α) ”= -3,5(c・1.1ho) Elemental analysis: C, H, ffN0 0% as .S](%
N% Calculated value: 50.22 6.09 6.51
Actual measurement value; 50°44 6.30 6.3ONMR
(0,2NNaOD, L-BuOD) +2. (
i8(III, dJ.
Ｊ＝８．１３ｔｌｚ）、 ２．８５（ＩＨ，ｄｄ、Ｊ＝
９．１４１１ｚ）、 ２．８６（ｉｌｌ、ｄｄ、Ｊ＝５
．５．１３１１ｚＬ ３．０５（ＩＨ，ｄｄ、Ｊ＝３．
１４１１ｚ）３．４８−３．５５（ＩＩＩ、ｍ） ７
．２８−７．４１（５１１，ｍ）（Ｒ）−２−アミノ−
３−フェニルプロパン−１−スルボン酸収 率：８３％
融点：＞３３０℃
〔α］ ” ＝ ４３．６ （ｃ＝Ｉ、 １ｌｚＯ）元
素分析’ Ｃ９Ｈ１３ＮＯ３Ｓとして０％ １４
％ Ｎ％
計算値・ ５０．２２ ６．０９ ６．５１実
測値： ５０．０３ ６．３８ ６．４５（
Ｒ）−２−アミノ−２−フェニルエタン−１−スルホン
酸敗 率；７９％
融点：＞３３０℃
〔α） ”−＋ １．３ （ｃ＝１．１Ｌ２０）元素分
析： Ｃｓ Ｈ＋ ＋ Ｎ Ｏ３Ｓとして０％ １
１％ Ｎ％
計算値： ４７．７５ ５．５１ ６．９６
実測値： ４７．８０ ５．４４． ６．９
６Ｎ Ｍ Ｒ（０，２ＮＮａＯＤ、 ｔ−ＢｕＯＤ）
： ３．２３（ＩＩＩ、ｄｄＪ＝１０． １３１１ｚ
）、 ３．４３（ＬＨ，ｄｄ、Ｊ＝５．５． １３１
１７．）４．０８（ＩＩＩ、ｄｄ、Ｊ・５．５． １０
１１ｚ）、 ７゜４０−７．４６（５１１ｍ）（Ｓ）
、２−アミノ−３−ヘンシルオキシプロパン暑−スル
ホン酸
収率・７６％
融点： ２４２−２４３℃
（α） ”−８，４（ｃ−１，ＨＪ）
元素分析： Ｃ，、Ｈ，ＳＮＯ，Ｓとして０％
１１％ Ｎ％
計算値： ４８．９７ ６．１６ ５．７１
実測値： ４８．９５ ５．８８ ５．７８
ＮＭＲ（０，２ＮＮａＯＤ、 ｔ−ＢｕＯＤ） ：
２．８３（ＩＨｄｄＪ＝８．１４１１ｚ）、 ３．０５
（ＩＨ，ｄｄ、Ｊ＝３．５．１４１１ｚ）３．４２−３
．５１（２ｔｌ、＋ｉ）、 ３．５５−３．６Ｈ１１１
，ｍ）４．５９（２！Ｉ、ｓＬ ７．３６−７．４６（
５１１，ｍ）実施例２゜
９．８１ ｇの（Ｓ）〜２−アミノー３−ヘンシルオキ
シプロパン−１−スルホン酸を水、酢酸、メタノールの
混合溶媒１４０．ｔに溶かし、１ｇの１０％パラジウム
−炭素の存在Ｆ、常圧室温にて２０時間接触還元を行っ
た。触媒を濾去した後、濾液を減圧下に溜去した。残漬
にトルエンを加えて減圧下で溜去することにより、残留
する酢酸を共沸除去した。析出した白色結晶をエタノー
ルを加えて濾取した。これをエタノール水より再結晶し
て４．３９ｇの（Ｓ）−２−アミノ−３−ヒドロキンプ
ロパン−１−スルホン酸を得た。J=8.13tlz), 2.85(IH, dd, J=
9.1411z), 2.86(ill, dd, J=5
．． 5.1311zL 3.05 (IH, dd, J=3.
1411z) 3.48-3.55 (III, m) 7
．． 28-7.41(511,m)(R)-2-amino-
3-Phenylpropane-1-sulfonic acid Yield: 83% Melting point: >330°C [α]” = 43.6 (c=I, 1lzO) Elemental analysis' 0% as C9H13NO3S 14
% N% Calculated value ・ 50.22 6.09 6.51 Actual value: 50.03 6.38 6.45 (
R)-2-amino-2-phenylethane-1-sulfonic acid loss rate; 79% Melting point: >330°C [α) ”-+ 1.3 (c=1.1L20) Elemental analysis: As Cs H+ + N O3S 0% 1
1% N% Calculated value: 47.75 5.51 6.96
Actual value: 47.80 5.44. 6.9
6N MR (0,2N NaOD, t-BuOD)
: 3.23(III, ddJ=10.1311z
), 3.43 (LH, dd, J=5.5.131
17. ) 4.08 (III, dd, J.5.5.10
11z), 7°40-7.46 (511m) (S)
, 2-amino-3-hensyloxypropane heat-sulfonic acid yield 76% Melting point: 242-243°C (α) "-8,4 (c-1, HJ) Elemental analysis: C,, H, SNO , 0% as S
11% N% Calculated value: 48.97 6.16 5.71
Actual value: 48.95 5.88 5.78
NMR (0,2N NaOD, t-BuOD):
2.83 (IHddJ=8.1411z), 3.05
(IH, dd, J=3.5.1411z)3.42-3
．． 51 (2tl, +i), 3.55-3.6H111
, m) 4.59 (2! I, sL 7.36-7.46 (
511, m) Example 2 9.81 g of (S) - 2-amino-3-hensyloxypropane-1-sulfonic acid was dissolved in a mixed solvent of water, acetic acid, and methanol at 140 g. Catalytic reduction was carried out in the presence of 1 g of 10% palladium-carbon at normal pressure and room temperature for 20 hours. After filtering off the catalyst, the filtrate was distilled off under reduced pressure. The remaining acetic acid was azeotropically removed by adding toluene to the residue and distilling it off under reduced pressure. The precipitated white crystals were collected by filtration after adding ethanol. This was recrystallized from ethanol water to obtain 4.39 g of (S)-2-amino-3-hydroquinepropane-1-sulfonic acid.
収率ニア９％
融 点： ２７９−２８１℃（分解）
（α） ”＝ ＋７．５ （Ｃ＝１． ）１２０）元素
分析： ’ Ｃｓ Ｈｑ Ｎ Ｏ４Ｓとして０％
８％ Ｎ％
計算値： ２３．２２ ５．８４ ９０３実
測値： ２３．５０ ６．ｉ４ ８．９１Ｎ
ＭＲ（０，２ＮＮａＯＤ、 ｔ−ＢｕＯＤ） ： ２
．８３（］１Ｌｄｄ。Yield near 9% Melting point: 279-281℃ (decomposition) (α) ”= +7.5 (C=1.) 120) Elemental analysis: 0% as Cs Hq N O4S
8% N% Calculated value: 23.22 5.84 903 Actual value: 23.50 6. i4 8.91N
MR (0,2NNaOD, t-BuOD): 2
．． 83(]1Ldd.
Ｊ＝９．１４１１ｚ）、 ３．０７（ｉｌｌ、ｄｄ、Ｊ
＝３．５．１４１１ｚ）。J=9.1411z), 3.07(ill, dd, J
=3.5.1411z).
３．２３−３．３４（Ｅ、１１）、 ３．５１（ｌｔｌ
、ｄｄ、Ｊ＝６．５． ｌ１ｌｌｚ）３．５８（ＩＩＩ
、ｄｄ、Ｊ・５．５．１ｌＨｚ）実施例３゜
４．３５ｇの（Ｓ）−２−アミノ−１−（メタンスルホ
ニル）オキシ−３−メチルブタンと４．０２ｇの亜硫酸
アンモニーラムを水に溶かし、室温で２０時間がき７Ｈ
ｌ′た。反応混合物を、強酸性イオン交換樹脂に通し、
溶出液を減圧下に溜去して析出した結晶を再び水に溶が
した。3.23-3.34 (E, 11), 3.51 (ltl
, dd, J=6.5. l1llz) 3.58 (III
, dd, J・5.5.1 lHz) Example 3 4.35 g of (S)-2-amino-1-(methanesulfonyl)oxy-3-methylbutane and 4.02 g of ammonium sulfite are dissolved in water, 20 hours at room temperature 7H
l'ta. Pass the reaction mixture through a strongly acidic ion exchange resin;
The eluate was distilled off under reduced pressure, and the precipitated crystals were again dissolved in water.
これを強塩基性イオン交換樹脂に通した後、減圧下に水
を溜去して析出した白色結晶にエタノールを加えて濾取
し、２．８７ｇの（Ｓ）−２−アミノ−３−メチルブタ
ン−１−スルホン酸を得た。After passing this through a strongly basic ion exchange resin, the water was distilled off under reduced pressure, and ethanol was added to the precipitated white crystals, which were collected by filtration. -1-sulfonic acid was obtained.
収 率；８６％
実施例４゜
ｆｔ１１３．２ｇの（Ｓ）−２−（Ｎ−ｔ−ブトキシカ
ルボニル）アミノ−１−（メタンスルホニル）オキシ−
３−メチルブタンとトＩ２．３ ｇの臭化リチウムを１
００−の無水アセトンに溶かし、室温で２０時間かき混
ぜた。水、５％炭酸水素ナトリウム水溶液、飽和食塩水
で順次洗浄した後、硫酸ナトリウム上で乾燥した。溶媒
を減圧下で溜去し、得られた粗生成物をシリカゲルカラ
ムクロマトグラフィーで精製し、て７．１９ｇの（Ｓ）
−２−（Ｎ−ｔ−ブ［キンカルボニル
得た。Yield: 86% Example 4 113.2 g of (S)-2-(N-t-butoxycarbonyl)amino-1-(methanesulfonyl)oxy-
3-Methylbutane and 2.3 g of lithium bromide in 1
00- in anhydrous acetone and stirred at room temperature for 20 hours. After sequentially washing with water, 5% aqueous sodium hydrogen carbonate solution, and saturated brine, it was dried over sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to yield 7.19 g of (S).
-2-(Nt-bu[quincarbonyl) was obtained.
収率＝５７％
融点： ７０ − ７１ ’Ｃ
〔α） ”−３５．６ （Ｃ＝１， ＣＩＩＣＩ３）Ｎ
Ｍ １２ （ＤＭＳＯ−ｄ６） ： ０．８４（６
１１，ｔ，Ｊ＝７１−１ｚ）、 １．３９（９＋１．
ｓ）、 １．７２−１．８４（ＩＩＩ，ｍ）、 ３．
４０−３．４９（２１１，ｍ）３、５４−３．６１（１
８，ｍ）、 ６．８４（１Ｂ，ｄ．Ｊ＝８１１ｚ）＋２
＋６．１２ｇの（Ｓ） −２− （Ｎ− ｔ−ブトキシ
カルボニル）アミノ−ｌ−ブロモ−３−メチルブタンと
４Ｎ塩化水素／ジオキサンを室温で１時間かき混ぜた．
溶媒を減圧下に溜去し、析出した結晶をエタノールを加
えて濾取し、４、３７ ｇの（Ｓ）−２−アミノ−ｌ−
ブロモ−３−メチルブタン塩酸塩を得た。Yield = 57% Melting point: 70-71'C[α)''-35.6 (C=1, CIICI3)N
M12 (DMSO-d6): 0.84 (6
11,t,J=71-1z), 1.39(9+1.
s), 1.72-1.84 (III, m), 3.
40-3.49 (211, m) 3, 54-3.61 (1
8, m), 6.84 (1B, d.J=811z)+2
+6.12 g of (S)-2-(N-t-butoxycarbonyl)amino-l-bromo-3-methylbutane and 4N hydrogen chloride/dioxane were stirred at room temperature for 1 hour.
The solvent was distilled off under reduced pressure, and the precipitated crystals were collected by filtration after adding ethanol to give 4.37 g of (S)-2-amino-l-
Bromo-3-methylbutane hydrochloride was obtained.
収率；９４％
融 点： ２０８ − ２０９℃（分解）（α） ”
＝ ＋ １７．０ （ｃ＝ｌ， ＨｚＯ）ＮＭＩ？
（ＤＭＳＯ−ｄａ） ： ０．９４（３１Ｌｄ，Ｊ＝
７１１ｚ）、 ０．９９（３１１．ｄ，Ｊ＝７ｉ１ｚ）
、 １．９５−２．０７（ｌ１１．ｏ＋） ３．１５
−３．２２（ＩＩＩ，＋ａ）、 ３．７５（Ｉｌｌ，ｄ
ｄ，Ｊ□５，ｌｌｌｌｚ） ３．８９（ｉｌｌ ｄｄ
Ｊ＝４． １１Ｈｚ）、 ８．５１（３１１，ｂｒｓ）
（３１３．４４ｇの（Ｓ）−２−アミノ−ｌ−ブロモ−
３−メチルブタン塩酸塩と３．２１ ｇの亜硫酸ナトリ
ウムを水に溶かし、室温で２０時間かき混ぜた。反応混
合物を、強酸性イオン交換樹脂に通し、溶出液を減圧下
に溜去して析出した結晶を再び水に溶かした。これを強
塩基性イオン交換樹脂に通した後、減圧下に水を溜去し
て析出した白色結晶にエタノールを加えてｄＣ取し、２
．５２ｇの（Ｓ）−２−アミノ−３−メチルブタン−１
−スルホン酸を得た（収率；８９％）。Yield: 94% Melting point: 208-209℃ (decomposition) (α)
= + 17.0 (c=l, HzO) NMI?
(DMSO-da): 0.94 (31Ld, J=
711z), 0.99 (311.d, J=7i1z)
, 1.95-2.07(l11.o+) 3.15
-3.22 (III, +a), 3.75 (Ill, d
d, J□5,llllz) 3.89(ill dd
J=4. 11Hz), 8.51 (311,brs)
(313.44 g of (S)-2-amino-l-bromo-
3-Methylbutane hydrochloride and 3.21 g of sodium sulfite were dissolved in water and stirred at room temperature for 20 hours. The reaction mixture was passed through a strongly acidic ion exchange resin, the eluate was distilled off under reduced pressure, and the precipitated crystals were again dissolved in water. After passing this through a strongly basic ion exchange resin, the water was distilled off under reduced pressure, and ethanol was added to the precipitated white crystals to collect dC.
．． 52 g of (S)-2-amino-3-methylbutane-1
-Sulfonic acid was obtained (yield: 89%).
同様にして、 （＋１）−２−アミノ−３〜メチルブタ
ン−１スルホン酸を得た（収率：６７％）。Similarly, (+1)-2-amino-3-methylbutane-1 sulfonic acid was obtained (yield: 67%).
（作用及び効果）
４℃で保存した稲（日本晴）を使用し、前記一般弐（１
）中のＸがスルホ基である本発明化合物の植物生育調整
作用を調べた。(Action and effect) Using rice (Nipponbare) stored at 4°C,
), in which X is a sulfo group, the plant growth regulating effect of the compound of the present invention was investigated.
被検茶水溶液（Ｉ ＸＩＯ−６Ｍ＞で浸した濾紙をペト
リ皿中に入れて発芽床とし、供試種子を播種した。A filter paper soaked with a test tea aqueous solution (I XIO-6M>) was placed in a Petri dish to serve as a germination bed, and test seeds were sown.
３ローに発芽した種子を同濃度の被検薬木）８故を含む
植物培養試験管に移して生育試験を行った。移植後７日
経過したものの地上部及び地下部の長さと重量を測定し
た。−群３０個体とし、試験は２０℃の暗所で行った。A growth test was performed by transferring the germinated seeds in 3 rows to a plant culture test tube containing the same concentration of the test medicinal tree 8). Seven days after transplantation, the length and weight of the aboveground and underground parts were measured. - The test was conducted in a dark place at 20°C with a group of 30 individuals.
その結果、本発明化合物を含む培地で発芽させた群では
、地上部の重量は変化させないが背丈を抑制する作用が
、対照群に比べ有意に認められた。即ち、本発明化合物
は植物の地上部を太く充実させる植物生長調整作用を有
し、農園芸用薬剤等として有用なものである。As a result, in the group germinated in the medium containing the compound of the present invention, the effect of suppressing the height of the plants without changing the weight of the aerial part was observed significantly compared to the control group. That is, the compound of the present invention has a plant growth regulating effect that makes the above-ground part of the plant thick and full, and is useful as an agricultural and horticultural agent.
Claims (1)
キル基、フェニル基、フェニルアルキル基、ヒドロキシ
アルキル基又はフェニルアルキルオキシアルキル基、Ｘ
はスルホ基、メシル基、トシル基又はハロゲンを表す。 〕 で表される化合物及びその薬学的に許容される塩。(1) The following general formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is hydrogen or a protecting group for an amino group, Y is a lower alkyl group, phenyl group, phenylalkyl group, Hydroxyalkyl group or phenylalkyloxyalkyl group, X
represents a sulfo group, mesyl group, tosyl group or halogen. ] A compound represented by these and its pharmaceutically acceptable salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63266762A JP2733511B2 (en) | 1988-10-22 | 1988-10-22 | New aminoalkane derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63266762A JP2733511B2 (en) | 1988-10-22 | 1988-10-22 | New aminoalkane derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02115147A true JPH02115147A (en) | 1990-04-27 |
| JP2733511B2 JP2733511B2 (en) | 1998-03-30 |
Family
ID=17435356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63266762A Expired - Fee Related JP2733511B2 (en) | 1988-10-22 | 1988-10-22 | New aminoalkane derivatives |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2733511B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0467856A2 (en) * | 1990-07-19 | 1992-01-22 | Nippon Zoki Pharmaceutical Co. Ltd. | Aminoalkanesulfonic acid derivatives and pharmaceutical compositions for use in preventing or treating heart diseases |
| WO2010014943A2 (en) * | 2008-08-01 | 2010-02-04 | Bioxiness Pharmaceutics, Inc. | Methionine analogs and methods of using same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3925360A (en) * | 1972-12-21 | 1975-12-09 | Wyeth John & Brother Ltd | 2-Benzyl aziridines |
| JPS5654314A (en) * | 1979-10-09 | 1981-05-14 | Yamatake Honeywell Co Ltd | Flow-rate measuring method by electromagnetic flow meter |
| JPS58907A (en) * | 1981-06-11 | 1983-01-06 | アメリカン・サイアナミド・カンパニ− | Method and composition for increasing crop of stalk, root or bean |
| JPS58965A (en) * | 1981-06-09 | 1983-01-06 | インペリアル・ケミカル・インダストリ−ズ・ピ−エル・シ− | Quinoline derivative, manufacture and pharmaceutical composition containing same and 5-hydroxytriptamine antagonistic activity |
| JPS5879971A (en) * | 1981-11-09 | 1983-05-13 | Takeda Chem Ind Ltd | Preparation of 1-phenylthio-2-aminopropane derivative |
| JPS58118596A (en) * | 1981-12-24 | 1983-07-14 | イ−・ア−ル・スクイブ・アンド・サンズ・インコ−ポレイテツド | Phosphorus-containg compound |
| US4513009A (en) * | 1980-04-17 | 1985-04-23 | Societe Civile Bioprojet | Aminoacid derivatives and their therapeutic applications |
| JPS60215678A (en) * | 1984-04-10 | 1985-10-29 | Sankyo Co Ltd | 6-amino-4-aza-5-oxo-1-thiacycloheptane derivative |
-
1988
- 1988-10-22 JP JP63266762A patent/JP2733511B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3925360A (en) * | 1972-12-21 | 1975-12-09 | Wyeth John & Brother Ltd | 2-Benzyl aziridines |
| JPS5654314A (en) * | 1979-10-09 | 1981-05-14 | Yamatake Honeywell Co Ltd | Flow-rate measuring method by electromagnetic flow meter |
| US4513009A (en) * | 1980-04-17 | 1985-04-23 | Societe Civile Bioprojet | Aminoacid derivatives and their therapeutic applications |
| JPS58965A (en) * | 1981-06-09 | 1983-01-06 | インペリアル・ケミカル・インダストリ−ズ・ピ−エル・シ− | Quinoline derivative, manufacture and pharmaceutical composition containing same and 5-hydroxytriptamine antagonistic activity |
| JPS58907A (en) * | 1981-06-11 | 1983-01-06 | アメリカン・サイアナミド・カンパニ− | Method and composition for increasing crop of stalk, root or bean |
| JPS5879971A (en) * | 1981-11-09 | 1983-05-13 | Takeda Chem Ind Ltd | Preparation of 1-phenylthio-2-aminopropane derivative |
| JPS58118596A (en) * | 1981-12-24 | 1983-07-14 | イ−・ア−ル・スクイブ・アンド・サンズ・インコ−ポレイテツド | Phosphorus-containg compound |
| JPS60215678A (en) * | 1984-04-10 | 1985-10-29 | Sankyo Co Ltd | 6-amino-4-aza-5-oxo-1-thiacycloheptane derivative |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0467856A2 (en) * | 1990-07-19 | 1992-01-22 | Nippon Zoki Pharmaceutical Co. Ltd. | Aminoalkanesulfonic acid derivatives and pharmaceutical compositions for use in preventing or treating heart diseases |
| WO2010014943A2 (en) * | 2008-08-01 | 2010-02-04 | Bioxiness Pharmaceutics, Inc. | Methionine analogs and methods of using same |
| WO2010014943A3 (en) * | 2008-08-01 | 2011-01-13 | Bioxiness Pharmaceutics, Inc. | Methionine analogs and methods of using same |
| US8580859B2 (en) | 2008-08-01 | 2013-11-12 | Bioxiness Pharmaceuticals, Inc. | Methionine analogs and methods of using same |
| US9695119B2 (en) | 2008-08-01 | 2017-07-04 | Bioxiness Pharmaceuticals, Inc. | Methionine analogs and methods of using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2733511B2 (en) | 1998-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4121215B2 (en) | Sulfostin analog, and method for producing sulfostine and its analog | |
| CZ292579B6 (en) | Process for preparing pure enantiomers of tropic acid esters | |
| ES2296131T3 (en) | PROCEDURE FOR THE PREPARATION OF 1- (2S, 3S) -2-BENCIDRIL-N- (5-TERC-BUTIL-2-METOXIBENCIL) QUINUCLIDIN-3-AMINA. | |
| JP6347396B2 (en) | Novel heterocycle-containing amino acid compounds and uses thereof | |
| ES2201019T3 (en) | NEW PROCEDURE FOR THE PREPARATION OF 11-AMINO-3-CHLORO-6,11-DIHIDRO-5,5-DIOXO-6-METHYL-DIBENZO- (C, F) - (1,2) -TIACEPIN AND ITS APPLICATION TO SYNTHESIS OF TIANEPTINE. | |
| CN108003105B (en) | Method for synthesizing micromolecular amino acid derivative ectoin | |
| DE3927049A1 (en) | HALOGENALKYL-PHENYL-KETONE AND THEIR HYDRATES, THEIR PRODUCTION AND USE | |
| JPWO2003024930A1 (en) | Method for producing pipecolinamide derivative | |
| JPH02115147A (en) | Novel aminoalkane derivative | |
| SE452318B (en) | AMINO ACIDS FOR USE AS INTERMEDIATES IN THE PRODUCTION OF BESTATIN | |
| JPH0421691A (en) | Production of phosphatidylcholine derivative and its analog and their intermediate | |
| KR20150066777A (en) | Indoline derivatives and method of preparing the same | |
| JP3174566B2 (en) | Aminoalkane derivatives | |
| EP0475071B1 (en) | 2-acyloxy-4-morpholinyl anthracycline | |
| JPS5936914B2 (en) | Cephalosporin analogs | |
| CN110437137A (en) | A kind of synthetic method of AVM hereinafter Batan midbody compound | |
| US4238622A (en) | D,L-2-Amino-4-(2-aminoethoxy)-trans-but-3-enoic acid derivatives | |
| US4908464A (en) | Process for the production of 1,3,2-oxazaphosphorinanes | |
| US5463075A (en) | Process for preparing 1,2-pyrazolidine-4-yl-disulfide compound | |
| HU180288B (en) | Process for preparing deoxystreptamine aminoglycoside derivatives | |
| EP0079125A1 (en) | 3-Substituted spectinomycin analogues and their preparation | |
| JPS6163677A (en) | Antibacterial-v | |
| KR800000627B1 (en) | Process for preparing derivatives of antibiotic xk-62-2 | |
| JPS6018678B2 (en) | Method for producing 4-0-(2-amino-2-deoxy-α-D-glucopyranosyl)-2,5-dideoxystreptamine | |
| IE903145A1 (en) | Threonine derived asymmetric chemical synthesis and¹intermediates for making antifungal compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |