JP6826225B2 - 糖から乳酸及び2−ヒドロキシ−3−ブテン酸又はα−ヒドロキシメチオニン類似体のエステルを製造する方法 - Google Patents
糖から乳酸及び2−ヒドロキシ−3−ブテン酸又はα−ヒドロキシメチオニン類似体のエステルを製造する方法 Download PDFInfo
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- JP6826225B2 JP6826225B2 JP2020070960A JP2020070960A JP6826225B2 JP 6826225 B2 JP6826225 B2 JP 6826225B2 JP 2020070960 A JP2020070960 A JP 2020070960A JP 2020070960 A JP2020070960 A JP 2020070960A JP 6826225 B2 JP6826225 B2 JP 6826225B2
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- Prior art keywords
- lewis acid
- water
- hydroxy
- group
- sugar
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- 235000000346 sugar Nutrition 0.000 title claims description 37
- AQPJRTNUBAWORL-RXMQYKEDSA-N (2r)-2-amino-2-hydroxy-4-methylsulfanylbutanoic acid Chemical class CSCC[C@@](N)(O)C(O)=O AQPJRTNUBAWORL-RXMQYKEDSA-N 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title description 69
- 239000004310 lactic acid Substances 0.000 title description 34
- 235000014655 lactic acid Nutrition 0.000 title description 34
- VBWPSWWDYVWZKA-UHFFFAOYSA-N 2-hydroxybut-3-enoic acid Chemical compound C=CC(O)C(O)=O VBWPSWWDYVWZKA-UHFFFAOYSA-N 0.000 title description 19
- 238000000034 method Methods 0.000 claims description 96
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
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- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 59
- 239000011968 lewis acid catalyst Substances 0.000 claims description 45
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- -1 dimethyl mercaptan Chemical compound 0.000 claims description 28
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
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- 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 claims description 7
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- 239000008103 glucose Substances 0.000 claims description 6
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- 150000003839 salts Chemical class 0.000 claims description 6
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 claims description 5
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 claims description 5
- 206010056474 Erythrosis Diseases 0.000 claims description 5
- 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 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- 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 claims description 4
- YTBSYETUWUMLBZ-QWWZWVQMSA-N D-threose Chemical compound OC[C@@H](O)[C@H](O)C=O YTBSYETUWUMLBZ-QWWZWVQMSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
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- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004386 Erythritol Substances 0.000 claims description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 2
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- 238000002156 mixing Methods 0.000 claims description 2
- 150000004652 butanoic acids Chemical class 0.000 claims 1
- JBKTVPSFVUFSAO-UHFFFAOYSA-N methyl 2-hydroxybut-3-enoate Chemical compound COC(=O)C(O)C=C JBKTVPSFVUFSAO-UHFFFAOYSA-N 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 44
- 239000003054 catalyst Substances 0.000 description 39
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 16
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 16
- 229940057867 methyl lactate Drugs 0.000 description 16
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 235000020357 syrup Nutrition 0.000 description 9
- 239000006188 syrup Substances 0.000 description 9
- NYPNCQTUZYWFGG-UHFFFAOYSA-N 2,2-dimethoxyethanol Chemical compound COC(CO)OC NYPNCQTUZYWFGG-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000005112 continuous flow technique Methods 0.000 description 8
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
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- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 5
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- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
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- QRTJEZQSJSURPR-UHFFFAOYSA-N methyl 2-hydroxy-4-methoxybutanoate Chemical compound COC(C(CCOC)O)=O QRTJEZQSJSURPR-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 3
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ATFVTAOSZBVGHC-UHFFFAOYSA-N Glycolaldehyde dimer Chemical compound OC1COC(O)CO1 ATFVTAOSZBVGHC-UHFFFAOYSA-N 0.000 description 3
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- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- VTLKDFNQWKCQQH-UHFFFAOYSA-N heptyl 2-hydroxy-4-methylsulfanylbutanoate Chemical compound C(CCCCCC)OC(C(CCSC)O)=O VTLKDFNQWKCQQH-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- YWWBUZVHTWILSP-UHFFFAOYSA-N hexyl 2-hydroxy-4-methylsulfanylbutanoate Chemical compound CCCCCCOC(=O)C(O)CCSC YWWBUZVHTWILSP-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000019534 high fructose corn syrup Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PODDEHMTBTUCGO-UHFFFAOYSA-N octyl 2-hydroxy-4-methylsulfanylbutanoate Chemical compound CCCCCCCCOC(=O)C(O)CCSC PODDEHMTBTUCGO-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 description 1
- 239000001521 potassium lactate Substances 0.000 description 1
- 235000011085 potassium lactate Nutrition 0.000 description 1
- 229960001304 potassium lactate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HTDCLHZBSWMJGI-UHFFFAOYSA-N propan-2-yl 2-hydroxy-4-methylsulfanylbutanoate Chemical compound CSCCC(O)C(=O)OC(C)C HTDCLHZBSWMJGI-UHFFFAOYSA-N 0.000 description 1
- YDGMCDVJRISRAU-UHFFFAOYSA-N propyl 4-methylsulfanylbutanoate Chemical compound CCCOC(=O)CCCSC YDGMCDVJRISRAU-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C319/26—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
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- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
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- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
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Description
触媒の製造
Sn−BEA(Si/Sn=125)は、米国特許第4,933,161号明細書(特許文献3)に記載された手順の変更に従って製造される。市販のゼオライトベータ(Zeolyst、Si/Al 12.5、アンモニウム型)を、H型(脱アルミニウム化形態)を得るためにか焼して(550℃で6時間)、そして、80℃で12時間、ゼオライトベータ粉末1グラム当たり10グラムの濃硝酸(Sigma−Aldrich、65%)で処理する。得られた固体をろ過し、十分な水で洗浄し、か焼し(550℃で6時間)、脱アルミニウムベータを得る。この固体にSn/Si比125のインシピエントウェットネス法で含浸させる。この目的のために、塩化スズ(II)(0.128g、Sigma−Aldrich、98%)を水(5.75ml)に溶解し、脱アルミニウムベータ(5g)に添加する。含浸処理後、試料を110℃で12時間乾燥し、再びか焼する(550℃で6時間)。
フルクトース(Sigma−Aldrich、99%)を室温でメタノール(Sig−ma−Aldrich、99.9%)に溶解して12.5g/lの濃度にした。さらに、脱イオン水(0、10、50又は100ml/l)及び炭酸カリウム(Sigma−Aldrich、99%、2.5mg/l)を供給溶液に添加した。上記の製法に従って製造した触媒(Sn−ベータSi:Sn 125)を分画し(0.25g、300−600μm)、ステンレス鋼製0.25インチ反応器に充填した。触媒を適所に保持するためにガラスウールを使用した。反応器を炉に導入して、反応器の温度を160℃に上昇させた。温度が140℃を超えた時に、フルクトース溶液1.25重量%を0.15ml/分の流速でメタノール中へポンプ注入を開始した。
液状媒体中の可溶性スズの総量の測定:
可溶性スズ(Sn)の総量の測定は、誘導結合プラズマ質量分析法(ICP−MS)を用いて行った。メタノール試料を重量で80/20のxylene/2−プロパノール混合物で希釈した。Snの総含有量は、ICP−MS(Agilent 7500ce ICP−MS装置)により、Sn同位体の質量118および120で、キシレンで希釈した900ppmのコノスタン有機金属Sn標準から作成した較正曲線と比較して定量する。インジウムは、ドリフト及びマトリックス効果を補正するための内部標準として使用される。ICP−MS分析における分子干渉の除去は、ヘリウムの運動エネルギー弁別を用いて行われる。Sn(305mg/kg)の情報価値を示すEnviroMAT“使用油”認定基準を、各試料バッチで分析して、方法の精度を検証する。
この実施例は、バッチ実験における水の影響によって増加した収率で、C2−糖(グリコールアルデヒド)のMVGへの転化率を説明している。
15.0gのメタノール(Sigma−Aldrich、>99.8%)、必要量の水、0.200gのグリコールアルデヒド(グリコールアルデヒド二量体、Sigma)及び0.150gの触媒をステンレス鋼製圧力容器(40cm3、Swagelok)に仕込んだ。反応器を閉じ、撹拌しながら160℃に加熱した(900rpm)。反応を16時間続け、この期間後、容器を冷水に浸すことにより反応を停止させた。反応容器からの試料をろ過し、HPLC(Agilent 1200, Biorad Aminex HPX−87Hカラム、65℃、0.05M H2SO4、0.5ml/分)により分析して、未転化のグリコールアルデヒド(GA)を定量し;そして、GC (Phenomenex Solgelwaxカラムを備えたAgilent 7890)を使用して、次を定量した:乳酸メチル(ML)、ビニルグリコール酸メチル(MVG、メチル−2−ヒドロキシ−3−ブテノエート)、グリコールアルデヒドジメチルアセタール(GLAD)及び4−メトキシ−2−ヒドロキシブタン酸メチル(MMHB)。
この例は、C2−糖(グリコールアルデヒド)から、硫黄−ビニルグリコール酸メチル(S−MVG、2−ヒドロキシ−4−(メチルチオ)−ブタン酸メチル)及び硫黄−ビニルグリコール酸エチル(S−EVG、2−ヒドロキシ−4−(メチルチオ)−ブタン酸エチル)を製造するバッチにおける触媒反応に関する。
(1)
固体ルイス酸触媒並びに有機溶媒及び水を含む溶媒の存在下で、糖から乳酸及び2−ヒドロキシ−3−ブテン酸又はα−ヒドロキシメチオニン類似体の一種又は二種以上のエステルを製造するための連続フロー方法であって、水が、有機溶媒の10体積%以下の量で存在している、上記の方法。
(2)
α−ヒドロキシメチオニン類似体が望ましい場合に、固体ルイス酸触媒並びに有機溶媒及び水を含む溶媒に加えて硫黄を含む化合物が存在する、前記(1)に記載の方法。
(3)
前記硫黄を含む化合物が、C 1 −C 5 アルキルチオール、C 1 −C 5 アルキルチオール塩、ジメチルメルカプタン及びジメチルジスルフィドからなる群から選択される、請求項(2)に記載の方法。
(4)
前記乳酸の一種又は二種以上のエステルの収率が、平均して1時間当たりストリーム当たり0.25%まで減少する、前記(1)に記載の方法。
(5)
前記乳酸の一種又は二種以上のエステルの収率が、平均して1時間当たり0.10%まで減少する、前記(1)又は(4)に記載の方法。
(6)
前記乳酸の一種又は二種以上のエステルの収率が、50時間のオンストリーム後に最大5%減少する、前記(1)、(4)又は(5)に記載の方法。
(7)
前記乳酸の一種又は二種以上のエステルの収率が、50時間のオンストリーム後に40%超である、前記(1)〜(6)のいずれか一つに記載の方法。
(8)
前記固体ルイス酸触媒を450時間後に焼成する、前記(1)〜(7)のいずれか一つに記載の方法。
(9)
前記固体ルイス酸触媒の骨格構造が、BEA、MFI、FAU、MOR、FER、MWW、MCM−41及びSBA−15からなる群から選択される、前記(1)〜(8)のいずれか一つに記載の方法。
(10)
前記固体ルイス酸が、Sn、Ti、Pb、Zr、Ge及びHfからなる群の一つ又は二つ以上から選択される活性金属を含む、前記(1)〜(9)のいずれか一つに記載の方法。
(11)
前記固体ルイス酸触媒が、Sn−BEA、Sn−MFI、Sn−FAU、Sn−MOR、Sn−MWW、Sn−MCM−41及びSn−SBA−15からなる群から選択される、前記(1)〜(10)のいずれか一つに記載の方法。
(12)
前記固体ルイス酸触媒がSnを含み、その固体ルイス酸触媒からのSnの損失が、オンストリームの1時間当たり、Snの初期量の0.11%以下である、前記(1)〜(11)のいずれか一つに記載の方法。
(13)
前記固体ルイス酸触媒がSnを含み、その固体ルイス酸触媒からのSnの損失が、オンストリームの50時間後にSnの初期量の8%未満である、前記(1)〜(12)のいずれか一つに記載の方法。
(14)
2−ヒドロキシ−3−ブテン酸エステルの収率が、オンストリームの50時間後に12%超である、前記(1)〜(13)のいずれか一つに記載の方法。
(15)
α−ヒドロキシメチオニン類似体エステルの収率が、オンストリームの10時間後に20%超である、前記(1)〜(13)のいずれか一つに記載の方法。
(16)
前記糖が、グルコース、フルクトース、マンノース、スクロース、キシロース、エリトロース、エリスリトール、トレオース及びグリコールアルデヒドからなる群の一種又は二種以上から選択される、前記(1)〜(15)のいずれか一つに記載の方法。
(17)
アルカリ土類金属イオン又はアルカリ金属イオンがプロセス中に存在する、前記(1)〜(16)のいずれか一つに記載の方法。
(18)
前記溶剤が、メタノール、エタノール、1−プロパノール、1−ブタノールおよびイソプロパノールからなる群の一種又は二種以上から選択される、前記(1)〜(17)のいずれか一つに記載の方法。
(19)
プロセスの温度が140℃−200℃である、前記(1)〜(18)のいずれか一つに記載の方法。
(20)
有機溶媒を糖水溶液と混合することによって、水の少なくとも一部が溶媒に導入される、前記(1)〜(19)のいずれか一つに記載の方法。
(21)
前記糖水溶液が、30%以上の乾燥糖度の糖シロップである、前記(1)〜(20)のいずれか一つに記載の方法。
Claims (16)
- 硫黄を含む化合物、固体ルイス酸触媒、並びに有機溶媒及び水を含む溶媒の存在下で、糖から、2−ヒドロキシ−4−(C 1−5 アルキルチオ)ブタン酸、その塩及びエステルからなる群から選択されるα−ヒドロキシメチオニン類似体を製造するための連続フロー方法であって、水が、有機溶媒の10体積%以下の量で存在している、上記の方法。
- 前記硫黄を含む化合物が、C1−C5アルキルチオール、C1−C5アルキルチオール塩、ジメチルメルカプタン及びジメチルジスルフィドからなる群から選択される、請求項1に記載の方法。
- 有機溶媒中に存在する水の体積%が0.25−10体積%である、請求項1に記載の方法。
- 前記固体ルイス酸触媒を450時間後に焼成する、請求項1〜3のいずれか一つに記載の方法。
- 前記固体ルイス酸触媒の骨格構造が、BEA、MFI、FAU、MOR、FER、MWW、MCM−41及びSBA−15からなる群から選択される、請求項1〜4のいずれか一つに記載の方法。
- 前記固体ルイス酸が、Sn、Ti、Pb、Zr、Ge及びHfからなる群の一つ又は二つ以上から選択される活性金属を含む、請求項1〜5のいずれか一つに記載の方法。
- 前記固体ルイス酸触媒が、Sn−BEA、Sn−MFI、Sn−FAU、Sn−MOR、Sn−MWW、Sn−MCM−41及びSn−SBA−15からなる群から選択される、請求項1〜6のいずれか一つに記載の方法。
- 前記固体ルイス酸触媒がSnを含み、その固体ルイス酸触媒からのSnの損失が、オンストリームの1時間当たり、Snの初期量の0.11%以下である、請求項1〜7のいずれか一つに記載の方法。
- 前記固体ルイス酸触媒がSnを含み、その固体ルイス酸触媒からのSnの損失が、オンストリームの50時間後にSnの初期量の8%未満である、請求項1〜8のいずれか一つに記載の方法。
- α−ヒドロキシメチオニン類似体エステルの収率が、オンストリームの10時間後に20%超である、請求項1〜9のいずれか一つに記載の方法。
- 前記糖が、グルコース、フルクトース、マンノース、スクロース、キシロース、エリトロース、エリスリトール、トレオース及びグリコールアルデヒドからなる群の一種又は二種以上から選択される、請求項1〜10のいずれか一つに記載の方法。
- アルカリ土類金属イオン又はアルカリ金属イオンがプロセス中に存在する、請求項1〜11のいずれか一つに記載の方法。
- 前記溶剤が、メタノール、エタノール、1−プロパノール、1−ブタノールおよびイソプロパノールからなる群の一種又は二種以上から選択される、請求項1〜12のいずれか一つに記載の方法。
- プロセスの温度が140℃−200℃である、請求項1〜13のいずれか一つに記載の方法。
- 有機溶媒を糖水溶液と混合することによって、水の少なくとも一部が溶媒に導入される、請求項1〜14のいずれか一つに記載の方法。
- 前記糖水溶液が、30%以上の乾燥糖度の糖シロップである、請求項1〜15のいずれか一つに記載の方法。
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