JP2004359660A - METHOD FOR PREPARING alpha-HYDROXYCARBOXYLIC ACID ESTER - Google Patents
METHOD FOR PREPARING alpha-HYDROXYCARBOXYLIC ACID ESTER Download PDFInfo
- Publication number
- JP2004359660A JP2004359660A JP2003304548A JP2003304548A JP2004359660A JP 2004359660 A JP2004359660 A JP 2004359660A JP 2003304548 A JP2003304548 A JP 2003304548A JP 2003304548 A JP2003304548 A JP 2003304548A JP 2004359660 A JP2004359660 A JP 2004359660A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxycarboxylic acid
- acid ester
- reaction
- metal halide
- present
- 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
- 238000000034 method Methods 0.000 title abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 18
- 150000005309 metal halides Chemical class 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 150000004820 halides Chemical class 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002772 monosaccharides Chemical class 0.000 claims description 8
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 claims description 2
- 208000007976 Ketosis Diseases 0.000 abstract description 16
- 150000001323 aldoses Chemical class 0.000 abstract description 16
- 150000002584 ketoses Chemical class 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 235000000346 sugar Nutrition 0.000 abstract description 9
- 150000008163 sugars Chemical class 0.000 abstract description 6
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 235000014633 carbohydrates Nutrition 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 239000010815 organic waste Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 16
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 12
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 8
- 235000014655 lactic acid Nutrition 0.000 description 8
- 239000004310 lactic acid Substances 0.000 description 8
- -1 aldose or ketose Chemical class 0.000 description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229940116333 ethyl lactate Drugs 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- 150000003903 lactic acid esters Chemical class 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229910007926 ZrCl Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229940120503 dihydroxyacetone Drugs 0.000 description 4
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-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
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 2
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose 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)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 150000002402 hexoses Chemical class 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Chemical class 0.000 description 2
- 150000002972 pentoses Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 150000004043 trisaccharides Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 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 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
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- WQZGKKKJIJFFOK-CBPJZXOFSA-N D-Gulose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-CBPJZXOFSA-N 0.000 description 1
- WQZGKKKJIJFFOK-WHZQZERISA-N D-aldose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-WHZQZERISA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-NQXXGFSBSA-N D-ribulose Chemical compound OC[C@@H](O)[C@@H](O)C(=O)CO ZAQJHHRNXZUBTE-NQXXGFSBSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-UHFFFAOYSA-N D-threo-2-Pentulose Natural products OCC(O)C(O)C(=O)CO ZAQJHHRNXZUBTE-UHFFFAOYSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-WUJLRWPWSA-N D-xylulose Chemical compound OC[C@@H](O)[C@H](O)C(=O)CO ZAQJHHRNXZUBTE-WUJLRWPWSA-N 0.000 description 1
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- SRBFZHDQGSBBOR-STGXQOJASA-N alpha-D-lyxopyranose Chemical compound O[C@@H]1CO[C@H](O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-STGXQOJASA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 239000000543 intermediate Substances 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
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- BJHIKXHVCXFQLS-PQLUHFTBSA-N keto-D-tagatose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-PQLUHFTBSA-N 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- NVLRFXKSQQPKAD-UHFFFAOYSA-N tricarbon Chemical compound [C]=C=[C] NVLRFXKSQQPKAD-UHFFFAOYSA-N 0.000 description 1
- 150000003641 trioses Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、α−ヒドロキシカルボン酸エステルの製造方法に関し、更に詳しくは、金属ハロゲン化物の存在下で、糖類とアルコールを反応させることにより、α−ヒドロキシカルボン酸エステルを製造する方法に関する。 The present invention relates to a method for producing an α-hydroxycarboxylic acid ester, and more particularly, to a method for producing an α-hydroxycarboxylic acid ester by reacting a saccharide with an alcohol in the presence of a metal halide.
糖類を原料として生産される乳酸エステルなどのα−ヒドロキシカルボン酸エステルは、医薬品、化粧品、香料、農薬などの各種製品の中間原料あるいはポリマー原料として極めて有用である。
そのため、従来から、乳酸や乳酸エステル等を工業的に製造する方法がいくつか提案されている。
Α-Hydroxycarboxylic acid esters such as lactic acid esters produced from sugars as raw materials are extremely useful as intermediate raw materials or polymer raw materials for various products such as pharmaceuticals, cosmetics, fragrances, and agricultural chemicals.
Therefore, several methods for industrially producing lactic acid, lactic acid ester, and the like have been proposed.
現在、工業的に実施されている糖類からの乳酸製造法は主として発酵によるものである(特許文献1参照)。
しかし、このような生体反応や酵素反応のような生物的な方法は反応速度が遅く、生成する乳酸の濃度が低いため、精製のためのエネルギー消費量が大きいという問題がある。
Currently, the method of producing lactic acid from sugars that is industrially implemented is mainly based on fermentation (see Patent Document 1).
However, such a biological method such as a biological reaction or an enzymatic reaction has a problem in that the reaction speed is slow and the concentration of lactic acid generated is low, so that energy consumption for purification is large.
これに対し、化学的合成法は反応速度が大きく、一般に生成物の濃度が高いという利点がある。
このような化学的合成法による乳酸の製造方法としては、糖類を当量のアルカリで処理することにより、乳酸等を塩の形で製造する方法が知られている。
On the other hand, the chemical synthesis method has the advantage that the reaction rate is high and the concentration of the product is generally high.
As a method of producing lactic acid by such a chemical synthesis method, a method of producing lactic acid or the like in the form of a salt by treating a saccharide with an equivalent amount of an alkali is known.
例えば、グルコースやグルコースのアルカリ溶液を蒸留することにより得られるグリセルアルデヒドを強アルカリで処理すれば、メチルグリオキサールあるいは乳酸やギ酸の塩等が得られることが知られている(非特許文献1、2参照)。 For example, it is known that if glyceraldehyde obtained by distilling glucose or an alkaline solution of glucose is treated with a strong alkali, methylglyoxal or a salt of lactic acid or formic acid can be obtained (Non-Patent Document 1, 2).
しかし、この方法により得られる乳酸塩から乳酸エステルを製造するためには、何らかの酸で処理する必要があり、そのためのコストと副生する塩の処理等が問題となる。
また、水溶液中で反応が行われるために、乳酸を分離するためのエネルギー消費が大きくなるという問題がある。
However, in order to produce a lactic acid ester from a lactate obtained by this method, it is necessary to treat the lactate with some kind of acid, and the cost and treatment of by-produced salts are problematic.
In addition, since the reaction is performed in an aqueous solution, there is a problem that energy consumption for separating lactic acid increases.
一方、チタニウムイソプロポキシド、塩化ジルコニウム、塩化クロム等の遷移金属化合物、あるいは遷移金属化合物を担持したイオン交換樹脂の存在下で、ジヒドロキシアセトン等のα−ヒドロキシカルボニル化合物とアルコールとを反応させることにより、α−ヒドロキシカルボン酸エステルを製造する方法が知られている(特許文献2、3参照)。
この方法によれば、ポリ乳酸製造における中間体である乳酸ブチルエステル等のα−ヒドロキシカルボン酸エステルを一段で合成することができる。
On the other hand, by reacting an alcohol with an α-hydroxycarbonyl compound such as dihydroxyacetone in the presence of a transition metal compound such as titanium isopropoxide, zirconium chloride, or chromium chloride, or an ion exchange resin supporting the transition metal compound. And methods for producing α-hydroxycarboxylic acid esters are known (see Patent Documents 2 and 3).
According to this method, an α-hydroxycarboxylic acid ester such as lactic acid butyl ester, which is an intermediate in the production of polylactic acid, can be synthesized in one step.
しかし、最も有利な原料であるジヒドロキシアセトンを用いても、短時間の反応では収率が低く、80%以上の収率を得るためには15時間以上の加熱が必要という問題がある。
このように、糖類からα−ヒドロキシカルボン酸エステルを安価且つ一段で合成することができる工業的に有利な合成方法が未だ確立していないのが現状である。
However, even when dihydroxyacetone, which is the most advantageous raw material, is used, the yield is low in a short-time reaction, and there is a problem that heating for 15 hours or more is required to obtain a yield of 80% or more.
As described above, at present, an industrially advantageous synthesis method capable of inexpensively synthesizing an α-hydroxycarboxylic acid ester from a saccharide in a single step has not yet been established.
ところで、グルコースのような糖類の大部分は、アルドース又はケトース、もしくはその誘導体で占められており、人体や環境に対して優しい物質である。
また、反応条件下でアルドース又はケトースを形成するこれらの前駆体の一つである多糖類は自然界に多量に存在しこれも人体や環境に対して優しい物質である。
By the way, most of sugars such as glucose are occupied by aldose or ketose, or derivatives thereof, and are substances that are friendly to the human body and the environment.
In addition, polysaccharides, one of these precursors that form aldose or ketose under the reaction conditions, are present in large amounts in nature and are also substances that are friendly to the human body and the environment.
更に、他のアルドース又はケトースの前駆体である炭水化物、特に有機性廃棄物由来のものは、その再資源化を強く要請されているものである。
従って、これらを化学的な方法により直接α−ヒドロキシカルボン酸エステルに変換できれば、その工業的な意義は計り知れないものがある。
Furthermore, carbohydrates that are precursors of other aldoses or ketoses, particularly those derived from organic wastes, are strongly demanded to be recycled.
Therefore, if these can be directly converted into α-hydroxycarboxylic acid esters by a chemical method, their industrial significance is immense.
本発明は、かかる実状を背景に、上記の問題点を克服するためになされたものである。
すなわち、本発明の目的は、自然界に多量に存在し、環境に優しい糖類、特にアルドース又はケトース、あるいはその再資源化の要望されているこれらを含有する有機性炭素資源(炭水化物など)から高収率でα−ヒドロキシカルボン酸エステルを製造する方法を提供することである。
The present invention has been made in order to overcome the above-mentioned problems against the background of the actual situation.
That is, an object of the present invention is to obtain high yields from environmentally friendly saccharides, especially aldose or ketose, or organic carbon resources (such as carbohydrates) containing these, which are required to be recycled, which are present in large amounts in nature. It is an object of the present invention to provide a method for producing an α-hydroxycarboxylic acid ester at a high rate.
かくして、本発明者は、このような課題背景に対して鋭意研究を重ねた結果、金属ハロゲン化物触媒の存在下で、糖類、特にアルドース又はケトースをアルコールと反応させると、α−ヒドロキシカルボン酸エステルが生成することを見出し、この知見に基づいて本発明を完成させたものである。 Thus, the inventor of the present invention has conducted intensive studies on such a background, and as a result, when a saccharide, particularly aldose or ketose, is reacted with an alcohol in the presence of a metal halide catalyst, an α-hydroxycarboxylic acid ester is obtained. Are generated, and the present invention has been completed based on this finding.
即ち、本発明は、(1)、金属ハロゲン化物触媒の存在下で糖類とアルコールを反応させるα−ヒドロキシカルボン酸エステルの製造方法に存する。 That is, the present invention resides in (1) a method for producing an α-hydroxycarboxylic acid ester in which a saccharide and an alcohol are reacted in the presence of a metal halide catalyst.
また、(2)、金属ハロゲン化物が、スズ、インジウム、銅、亜鉛いずれかのハロゲン化物又はこれらのハロゲン化物を2つ以上組み合わせたものであるα−ヒドロキシカルボン酸エステルの製造方法に存する。 (2) The method for producing an α-hydroxycarboxylic acid ester in which the metal halide is a halide of any of tin, indium, copper, and zinc or a combination of two or more of these halides.
そしてまた、(3)、糖類が、単糖類であるα−ヒドロキシカルボン酸エステルの製造方法に存する。 Also, (3) a method for producing an α-hydroxycarboxylic acid ester in which the saccharide is a monosaccharide.
そしてまた、(4)、単糖類が、三炭糖であるα−ヒドロキシカルボン酸エステルの製造方法に存する。 Also, (4) the method for producing an α-hydroxycarboxylic acid ester in which the monosaccharide is a tricarbonate exists.
本発明はこの目的に沿ったものであれば、上記1〜4の中から選ばれた2つ以上を組み合わせた構成も当然採用可能である。 As long as the present invention meets this purpose, a configuration combining two or more selected from the above 1 to 4 can be naturally adopted.
本発明によれば、自然界に多量に存在し、環境に優しく、また再資源化の要望されている、糖類好ましくはアルドース又はケトースから、医薬品、化粧品、香料、農薬などの各種製品の中間原料あるいはポリマー原料として極めて有用なα−ヒドロキシカルボン酸エステルを一段で簡便かつ安価に製造することが可能となる。 According to the present invention, a large amount of naturally occurring, environmentally friendly, and is demanded for recycling, from sugars, preferably aldose or ketose, pharmaceuticals, cosmetics, fragrances, intermediate raw materials of various products such as agricultural chemicals or It becomes possible to produce an α-hydroxycarboxylic acid ester which is extremely useful as a polymer raw material in one step simply and inexpensively.
また、アルドース又はケトースの前駆体として、例えば有機性炭素資源を利用することが可能となるので、環境浄化、資源の有効利用及び省エネルギーの観点からみても極めて有効なα−ヒドロキシカルボン酸エステルの合成プロセスということができる。 In addition, as a precursor of aldose or ketose, for example, organic carbon resources can be used, and therefore, synthesis of α-hydroxycarboxylic acid ester which is extremely effective from the viewpoint of environmental purification, effective use of resources and energy saving. It can be called a process.
以下、本発明のα−ヒドロキシカルボン酸エステルの製造方法について述べる。 Hereinafter, the method for producing the α-hydroxycarboxylic acid ester of the present invention will be described.
(本発明の製造方法における反応について)
本発明のα−ヒドロキシカルボン酸エステルの製造方法は、金属ハロゲン化物触媒の存在下で、糖類、特にアルドースやケトース等の単糖類とアルコールを反応させることを特徴とする。
この一段の反応により、乳酸エステルなどのα−ヒドロキシカルボン酸エステルが得られるが、この合成反応は、通常、下記のように一般的に表される反応式によって示すことができる。
(Reaction in the production method of the present invention)
The method for producing an α-hydroxycarboxylic acid ester of the present invention is characterized by reacting a saccharide, particularly a monosaccharide such as aldose or ketose, with an alcohol in the presence of a metal halide catalyst.
An α-hydroxycarboxylic acid ester such as a lactic acid ester is obtained by this one-stage reaction, and this synthesis reaction can be generally represented by a reaction formula generally represented as follows.
因みに、上記の反応式中、本発明の目的物であるα−ヒドロキシカルボン酸エステルは、HOCH(CH3)CO2R(乳酸エステル)及びHOCH2CO2R(グリコール酸エステル)である。 Incidentally, in the above reaction formula, the α-hydroxycarboxylic acid ester which is the object of the present invention is HOCH (CH 3 ) CO 2 R (lactic acid ester) and HOCH 2 CO 2 R (glycolic acid ester).
(金属ハロゲン化物触媒について)
本発明方法においては、金属ハロゲン化物触媒を用い、糖類好ましくはアルドース又はケトースを上記反応条件で反応させることにより、所望とするα−ヒドロキシカルボン酸エステルを得ることができる。
(About metal halide catalyst)
In the method of the present invention, a desired α-hydroxycarboxylic acid ester can be obtained by reacting a saccharide, preferably aldose or ketose, under the above reaction conditions using a metal halide catalyst.
このような金属ハロゲン化物触媒としては、スズ、インジウム、銅、あるいは亜鉛のハロゲン化物又はこれらのハロゲン化物を2つ以上組み合わせたものが好ましく使用される。
具体的には、例えば、塩化スズ、臭化スズ、ヨウ化スズ、塩化インジウム、塩化銅、塩化亜鉛等の金属ハロゲン化物を挙げることができる。
As such a metal halide catalyst, a tin, indium, copper, or zinc halide or a combination of two or more of these halides is preferably used.
Specifically, examples thereof include metal halides such as tin chloride, tin bromide, tin iodide, indium chloride, copper chloride, and zinc chloride.
金属ハロゲン化物触媒の使用量は、糖類あるいはその前駆体に対して1/10000〜1/1、好ましくは1/100〜1/10である。
金属化合物の使用量が少な過ぎると反応が進行せず、逆に多過ぎると副反応のため、α−ヒドロキシカルボン酸エステル収率が低下するので好ましくない。
The amount of the metal halide catalyst used is 1/10000 to 1/1, preferably 1/100 to 1/10, based on the saccharide or its precursor.
If the amount of the metal compound used is too small, the reaction does not proceed, while if it is too large, a side reaction is undesirably caused because the yield of α-hydroxycarboxylic acid ester decreases.
(糖類について)
本発明の原料として用いる糖類は特に限定されるものではないが、単糖類、少糖類、多糖類などが好ましく使用される。
単糖類としては、グリコールアルデヒド、グリセルアルデヒド、ジヒドロキシアセトン等のアルドース又はケトースが使用可能である。
(About sugars)
The saccharide used as a raw material of the present invention is not particularly limited, but monosaccharides, oligosaccharides, polysaccharides and the like are preferably used.
Aldose or ketoses such as glycolaldehyde, glyceraldehyde and dihydroxyacetone can be used as the monosaccharide.
具体的には、アルドースとしては、グルコース、マンノース、ガラクトース、タロース、グロースなどのヘキソース、キシロース、アラビノース、リボース、リキソースなどのペントース等を挙げることができる。
また、ケトースとしては、フルクトース、ソルボース、タガトースなどのヘキソース、リブロース、キシルロースなどのペントース等を挙げることができる。
Specifically, examples of aldoses include hexoses such as glucose, mannose, galactose, talose, and gulose, and pentoses such as xylose, arabinose, ribose, and lyxose.
Examples of ketose include hexoses such as fructose, sorbose, and tagatose, and pentoses such as ribulose and xylulose.
少糖類としてはしょ糖(スクロース)、麦芽糖(マルトース)、乳糖(ラクトース)、セロビオースなどの二糖類、ラフィノース、バノース等の三糖類等を挙げることができる。
また、多糖類としてはでんぷん、セルロース、イヌリン、あるいはこれらを含有する有機性廃棄物等を挙げることができる。
Examples of oligosaccharides include sucrose (sucrose), maltose (maltose), lactose (lactose), disaccharides such as cellobiose, and trisaccharides such as raffinose and banose.
Examples of polysaccharides include starch, cellulose, inulin, and organic wastes containing these.
本発明で好ましく使用される糖類は、単糖類であり、その中でもアルドースやケトースが好ましく、グリコールアルデヒド(二炭糖)、グリセルアルデヒド、ジヒドロキシアセトン(いずれも三炭糖。トリオースともいう)等のアルドース又はケトースがより好ましく使用される。
特に、三炭糖は、炭素数が乳酸(CH3CHOHCOOH)と同じく3つであるため、乳酸エステルの製造には好ましく用いられる。
The saccharides preferably used in the present invention are monosaccharides, and among them, aldose and ketose are preferable, and glycol aldehyde (bicarbon sugar), glyceraldehyde, dihydroxyacetone (all trisaccharides, also referred to as triose) and the like. Aldose or ketose is more preferably used.
In particular, tri-carbon sugar is preferably used in the production of lactic acid esters because it has three carbon atoms, as in lactic acid (CH 3 CHOHCOOH).
(アルコールについて)
また、原料であるアルコールは特に制約されないが、炭素数1〜8の脂肪族アルコールを用いることが好ましい。
このようなアルコールとしては、例えばメタノール、エタノール、プロパノールなどを挙げることができる。
(About alcohol)
Further, the alcohol as a raw material is not particularly limited, but it is preferable to use an aliphatic alcohol having 1 to 8 carbon atoms.
Examples of such alcohols include methanol, ethanol, propanol and the like.
糖類とアルコールの使用割合は特に制約されるものではないが、通常、1/1〜1/100、好ましくは1/5〜1/50である。
反応条件は、原料である糖類やアルコールの種類などによって異なるが、反応圧力は、1気圧以上、好ましくは20〜60気圧であり、また、反応温度は、室温〜250℃、好ましくは150〜200℃である。
The usage ratio of the saccharide and the alcohol is not particularly limited, but is usually 1/1 to 1/100, preferably 1/5 to 1/50.
The reaction conditions vary depending on the types of the saccharides and alcohols as the raw materials, but the reaction pressure is 1 atm or more, preferably 20 to 60 atm, and the reaction temperature is room temperature to 250 ° C, preferably 150 to 200 atm. ° C.
(製造方法の具体例について)
本発明方法によりα−ヒドロキシカルボン酸エステルを得るには、例えばオートクレーブ中に金属ハロゲン化物触媒、原料であるアルドース又はケトース、及びアルコールを仕込み、反応条件を例えば圧力100気圧、温度170℃に設定し、原料を攪拌しながら所定時間反応させる。
そして、その後、得られる生成物から所望のα−ヒドロキシカルボン酸エステルを分離すればよい。
(About specific examples of manufacturing method)
In order to obtain an α-hydroxycarboxylic acid ester by the method of the present invention, for example, a metal halide catalyst, a raw material aldose or ketose, and an alcohol are charged in an autoclave, and the reaction conditions are set to, for example, a pressure of 100 atm and a temperature of 170 ° C. The raw materials are reacted for a predetermined time while stirring.
Then, the desired α-hydroxycarboxylic acid ester may be separated from the obtained product.
以上、本発明を説明してきたが、本発明は実施形態にのみ限定されるものではなく、その本質を逸脱しない範囲で、他の種々の更なる変形例が可能であることは言うまでもない。
例えば、上記の説明及び後述する実施例では、α−ヒドロキシカルボン酸エステルとして主に乳酸エステル(乳酸エチル)やグリコール酸エチルを製造する場合を例示した。
しかし、他の種類のα−ヒドロキシカルボン酸エステルの製造に対しても同様に説明でき、本発明によれば、製造条件等を調整することにより他の種類のα−ヒドロキシカルボン酸エステルを製造することも当然可能である。
The present invention has been described above. However, the present invention is not limited to the embodiment, and it goes without saying that various other modifications can be made without departing from the essence of the present invention.
For example, in the above description and the examples described later, the case of mainly producing lactate ester (ethyl lactate) or ethyl glycolate as the α-hydroxycarboxylic acid ester has been exemplified.
However, the same can be said for the production of other types of α-hydroxycarboxylic acid esters, and according to the present invention, other types of α-hydroxycarboxylic acid esters are produced by adjusting the production conditions and the like. Of course it is also possible.
また、糖類は種々のものを用いることが可能であり、目的とするα−ヒドロキシカルボン酸エステルにあわせて適宜選択されて用いられる。
更に、反応を効果的に進行させるために、金属ハロゲン化物触媒以外に他の添加剤を加えることが可能であることは言うまでもない。
Various saccharides can be used, and they are appropriately selected and used according to the target α-hydroxycarboxylic acid ester.
Further, it goes without saying that other additives besides the metal halide catalyst can be added in order to make the reaction proceed effectively.
以下、実施例により更に詳細に説明する。
尚、本発明は、これらの実施例に限定されるものでないことは言うまでもない。
Hereinafter, the present invention will be described in more detail with reference to examples.
Needless to say, the present invention is not limited to these examples.
[実施例1]
50mL容のオートクレーブ中に、38.6%の炭素分を含有する可溶性澱粉0.47g(炭素15mg原子を含む)、エタノール8mL、及び塩化スズ0.5mmolを仕込み、オートクレーブの蓋を閉めた後、アルゴンガス(室温で60気圧)加圧下、170℃で2時間反応を行った。
この反応で得られた生成物を、ガスクロマトグラフィーにより定量分析した。
[Example 1]
In a 50 mL autoclave, 0.47 g (including 15 mg carbon atoms) of soluble starch containing 38.6% carbon, 8 mL of ethanol, and 0.5 mmol of tin chloride were charged, and after closing the autoclave lid, The reaction was carried out at 170 ° C. for 2 hours under a pressure of argon gas (60 atm at room temperature).
The product obtained by this reaction was quantitatively analyzed by gas chromatography.
その結果、α−ヒドロキシカルボン酸エステルとして、乳酸エチル(1.72mmol)及びグリコール酸エチル(0.18mmol)が生成した。
α−ヒドロキシカルボン酸エステル以外の生成物としては、高分子量化合物の他、エチラール(0.12mmol)、ジエチルアセタール(0.13mmol)、及びレブリン酸エチル(0.07mmol)等が生成していることが判った。
また、α−ヒドロキシカルボン酸エステルのトータル収率は炭素基準で36%、スズ化合物基準で372%であった。
As a result, ethyl lactate (1.72 mmol) and ethyl glycolate (0.18 mmol) were produced as α-hydroxycarboxylic acid esters.
As products other than the α-hydroxycarboxylic acid ester, in addition to a high molecular weight compound, ethylal (0.12 mmol), diethyl acetal (0.13 mmol), ethyl levulinate (0.07 mmol) and the like are generated. I understood.
The total yield of α-hydroxycarboxylic acid ester was 36% based on carbon and 372% based on tin compound.
[実施例2]
50mL容のオートクレーブ中に、グルコース0.45g(炭素15mg原子を含む)、エタノール8mL、及び表1に記載の金属ハロゲン化物0.5mmolを仕込み、オートクレーブの蓋を閉めた後、アルゴンガス(室温で60気圧)加圧下、170℃で2時間反応を行った。
この反応で得られた生成物を、ガスクロマトグラフィーにより定量分析した。
[Example 2]
In a 50 mL autoclave, 0.45 g of glucose (containing 15 mg carbon atoms), 8 mL of ethanol, and 0.5 mmol of a metal halide described in Table 1 were charged. After closing the autoclave lid, argon gas (at room temperature) was used. The reaction was carried out at 170 ° C. for 2 hours under pressure.
The product obtained by this reaction was quantitatively analyzed by gas chromatography.
その結果、乳酸エチル及びグリコール酸エチルが表1に示す収率で生成することが判った。
なお、収率は炭素基準である。
As a result, it was found that ethyl lactate and ethyl glycolate were produced in the yields shown in Table 1.
The yield is based on carbon.
[比較例1]
50mL容のオートクレーブ中に、グルコース0.45g(炭素15mg原子を含む)、エタノール8mL、及び表2に記載の金属化合物0.5mmolを仕込み、オートクレーブの蓋を閉めた後、アルゴンガス(室温で60気圧)加圧下、170℃で2時間反応を行った。
この反応で得られた生成物を、ガスクロマトグラフィーにより定量分析した。
[Comparative Example 1]
In a 50 mL autoclave, 0.45 g of glucose (containing 15 mg atoms of carbon), 8 mL of ethanol, and 0.5 mmol of a metal compound described in Table 2 were charged, and the autoclave was closed. The reaction was carried out at 170 ° C. for 2 hours under pressure.
The product obtained by this reaction was quantitatively analyzed by gas chromatography.
その結果、乳酸エチル及びグリコール酸エチルが表2に示す収率で生成することが判った。
表2に記載された金属化合物は、概して表1に記載された金属ハロゲン化物の場合と比較して、特に乳酸エチルでは収率が低かった。
前述した従来技術(欧州特許出願公開第0460831号明細書)で特記されている触媒の内、特に有効であったのはZrCl4、CrCl3・6H2O、及びZrCl2O・8H2Oであるが、ZrCl4及びCrCl3・6H2Oは毒性が高く、実用的ではないため、ここでは使用しなかった。また、ZrCl2O・8H2Oを触媒として用いた場合にも、乳酸エチルの収率は4%と低かった。
なお、収率は炭素基準である。
As a result, it was found that ethyl lactate and ethyl glycolate were produced in the yields shown in Table 2.
The metal compounds listed in Table 2 generally had lower yields, especially with ethyl lactate, than the metal halides listed in Table 1.
Of the catalysts that are otherwise in the above-mentioned prior art (EP 0460831 Pat), especially which was valid ZrCl 4, CrCl 3 · 6H 2 O, and at ZrCl 2 O · 8H 2 O However, ZrCl 4 and CrCl 3 .6H 2 O were not used here because they are highly toxic and impractical. Also, when ZrCl 2 O · 8H 2 O was used as a catalyst, the yield of ethyl lactate was as low as 4%.
The yield is based on carbon.
[実施例3]
50mL容のオートクレーブ中に、炭素15mg原子を含有する量の表3に記載のアルドース又はケトース、あるいはその前駆体、メタノール8mL、及び塩化スズ0.5mmolを仕込み、オートクレーブの蓋を閉めた後、アルゴンガス(室温で60気圧)加圧下、170℃で2時間反応を行った。
この反応で得られた生成物を、ガスクロマトグラフィーにより定量分析した。
[Example 3]
In a 50 mL autoclave, aldose or ketose described in Table 3 containing 15 mg atoms of carbon or a precursor thereof, 8 mL of methanol, and 0.5 mmol of tin chloride were charged, and the autoclave was closed with a lid. The reaction was performed at 170 ° C. for 2 hours under gas (room temperature, 60 atm) pressure.
The product obtained by this reaction was quantitatively analyzed by gas chromatography.
その結果、乳酸メチル及びグリコール酸メチルが表3に示す収率で生成することが判った。
なお、収率は炭素基準である。
As a result, it was found that methyl lactate and methyl glycolate were produced in the yields shown in Table 3.
The yield is based on carbon.
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