TWI713520B - 從糖類及其衍生物製備甲硫胺酸α-羥基類似物的方法 - Google Patents
從糖類及其衍生物製備甲硫胺酸α-羥基類似物的方法 Download PDFInfo
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- TWI713520B TWI713520B TW105113422A TW105113422A TWI713520B TW I713520 B TWI713520 B TW I713520B TW 105113422 A TW105113422 A TW 105113422A TW 105113422 A TW105113422 A TW 105113422A TW I713520 B TWI713520 B TW I713520B
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- hydroxy
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- methionine
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- 238000000034 method Methods 0.000 title claims abstract description 68
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 title claims abstract description 45
- 229930182817 methionine Natural products 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 235000000346 sugar Nutrition 0.000 claims abstract description 38
- 150000008163 sugars Chemical class 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- -1 alkyl mercaptan Chemical compound 0.000 claims description 34
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 32
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 229910052914 metal silicate Inorganic materials 0.000 claims description 17
- JBKTVPSFVUFSAO-UHFFFAOYSA-N methyl 2-hydroxybut-3-enoate Chemical compound COC(=O)C(O)C=C JBKTVPSFVUFSAO-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 claims description 13
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
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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 9
- 229930006000 Sucrose Natural products 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
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- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
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- 239000005720 sucrose Substances 0.000 claims description 9
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- 239000005715 Fructose Substances 0.000 claims 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 claims description 7
- 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 7
- 239000008103 glucose Substances 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 6
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- ZNICVDUAZVFBFJ-UHFFFAOYSA-N methyl 2-hydroxy-4-methylsulfanylbutanoate Chemical compound COC(=O)C(O)CCSC ZNICVDUAZVFBFJ-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- YTBSYETUWUMLBZ-QWWZWVQMSA-N D-threose Chemical compound OC[C@@H](O)[C@H](O)C=O YTBSYETUWUMLBZ-QWWZWVQMSA-N 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 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 claims description 5
- 229930182830 galactose Natural products 0.000 claims description 5
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 claims description 4
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002952 polymeric resin Substances 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 claims description 4
- FWIBCWKHNZBDLS-UHFFFAOYSA-N 3-hydroxyoxolan-2-one Chemical compound OC1CCOC1=O FWIBCWKHNZBDLS-UHFFFAOYSA-N 0.000 claims description 3
- 206010056474 Erythrosis Diseases 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 241000206572 Rhodophyta Species 0.000 claims description 2
- 238000011437 continuous method Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- UQPHVQVXLPRNCX-UHFFFAOYSA-N erythrulose Chemical compound OCC(O)C(=O)CO UQPHVQVXLPRNCX-UHFFFAOYSA-N 0.000 claims description 2
- MCEPYJYPIASGNF-UHFFFAOYSA-N ethyl 2-hydroxy-4-methylsulfanylbutanoate Chemical compound CCOC(=O)C(O)CCSC MCEPYJYPIASGNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 4
- VBWPSWWDYVWZKA-UHFFFAOYSA-N 2-hydroxybut-3-enoic acid Chemical compound C=CC(O)C(O)=O VBWPSWWDYVWZKA-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 4
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- 229940057867 methyl lactate Drugs 0.000 description 4
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
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- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
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- 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
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Abstract
一種製備甲硫胺酸α-羥基類似物及其衍生物之方法,其包含使一或多種糖或其衍生物與金屬矽酸鹽組成物在包含硫之化合物及溶劑存在下接觸。
Description
一種用於在沸石類化合物存在下從糖製備甲硫胺酸α-羥基類似物及其衍生物之方法。
碳水化合物代表最大部分的生質且已確定多種將其有效用作製備市售化學物質之原料的策略。生質由於其補充且最終將替代石油作為此類目的之原料之潛力而尤其受關注。由生質獲得之碳水化合物包含C2至C6糖且由於其為高官能化短鏈碳化合物之潛在來源而在工業上尤其受關注。
本發明係關於在沸石類化合物存在下由糖製備甲硫胺酸α-羥基類似物及其衍生物。甲硫胺酸α-羥基類似物為2-羥基-4-(甲硫基)丁酸。甲硫胺酸α-羥基類似物及其衍生物可用作動物飼料組成物/調配物中之食物/營養補充劑。
已知C2-C6糖可在沸石類材料(諸如Sn-BEA)存在下轉換成乳酸甲酯及乙烯基羥乙酸甲酯(MVG)。EP 2 184 270 B1及Science(2010)第328卷第602-605頁報導在160℃下,在Sn-BEA及甲醇存在下,來自蔗糖、葡萄糖及果糖之乳酸甲酯之平均產率分別為64%、43%及44%。乙烯基羥乙
酸甲酯(MVG)為主要副產物,其所報導之產量為3-11%。MVG可由C4糖D-赤藻糖以至多56%之產率生產。
WO 98/32735揭示經由甲基硫醇對非共軛烯受質(亦即乙烯基羥乙酸甲酯(MVG))之自由基加成來以85%產率製備甲硫胺酸α-羥基類似物甲酯,2-羥基-4-(甲硫基)丁酸甲酯之方法。儘管產率較高,但基團反應有可能形成區域異構副產物。
WO 98/32735亦揭示替代性、多步驟、商業上可實行的用於製備甲硫胺酸α-羥基類似物,2-羥基-4-(甲硫基)丁酸之方法。該方法包含在有機胺催化劑存在下,甲硫醇對丙烯醛(共軛烯受質)之邁克爾加成(Michael addition)以產生3-(甲硫基)-丙醛,接著進行腈加成且水解成酸。儘管該方法為工業上可實行的,但應避免使用有毒且昂貴的試劑,諸如HCN及丙烯醛。
ChemCatChem(2013)第5卷第569-575頁揭示四碳糖(C4糖)在均質催化條件下轉化成MVG及MMHB。MMHB在均質氯化錫催化劑存在下由赤藻酮糖(C4糖)選擇性產生。
因此,需要提供用於製備甲硫胺酸α-羥基類似物及其衍生物之替代性方法。特定言之,需要提供工業上可實行的方法,因此需要該方法具有較高產率、引導性及選擇性。需要該方法在工業上可實行的條件下用易於製備之試劑或催化劑進行,且減少有毒廢料,諸如使用可再生之非均質催化劑。此外,需要提供其中之受質來自於可再生來源(諸如C2-C6糖)之方法。尤其因為糖受質與例如丙烯醛及HCN試劑相比毒性明顯更低且明顯更便宜,因此使用糖受質可顯著降低生產成本。
意外發現,可藉由使一或多種糖與金屬矽酸鹽組成物在包含硫之化合物及溶劑存在下接觸來獲得甲硫胺酸α-羥基類似物及其衍生物。
甲硫胺酸α-羥基類似物及其衍生物可由式R'-S-CH2-CH2-CHOH-COO-R表示,其中R選自由以下各者組成之群:H、C1-C8烷基或鹼金屬或鹼土金屬;及R'選自由以下各者組成之群:H及甲基。
意外發現,可根據本發明之方法獲得高產率之甲硫胺酸α-羥基類似物及其衍生物。
包含硫之化合物較佳為式RSR'之化合物,其中R及R'選自由H、C1-C5烷基或鹼金屬或鹼土金屬組成之群。包含硫之化合物較佳選自由以下各者組成之群:C1-C5烷基硫醇、C1-C5烷基硫醇鹽、二甲硫醇、二甲基二硫化物及硫化氫。在本文中,C1-C5烷基硫醇指經包含直鏈或分支鏈飽和脂族烷基之取代基單取代或雙取代之硫醇,該烷基包含一個、兩個、三個、四個或五個碳。在本文中,C1-C5烷基硫醇意指選自由以下各者組成之群的烷基硫醇:甲烷硫醇、乙烷硫醇、直鏈或分支鏈丙烷硫醇、直鏈或分支鏈丁烷硫醇及直鏈或分支鏈戊烷硫醇。
在本文中,C1-C5烷基硫醇鹽意指C1-C5烷基硫醇之鹼金屬或鹼土金屬鹽。特定言之,在本文中,C1-C5烷基硫醇鹽意指呈鹽形式之C1-C5
烷基硫醇,其中陽離子選自由以下各者組成之群:鈉、鉀、鋰、鎂及鈣。特定言之,在本文中,C1-C5烷基硫醇鹽意指選自由以下各者組成之群中之一或多者的C1-C5烷基硫醇:NaSCH3、KSCH3、Ca(SCH3)2及Mg(SCH3)2。
可使用硫化氫作為硫化合物以產生2-羥基-4-巰基-丁酸或其酯,其可藉由與甲醇反應而進一步轉換成甲硫胺酸α-羥基類似物。或者,可使用硫化氫在糖、醇及酸性催化劑存在下形成C1-C5烷基硫醇,如Roberts,J.S(2000)。Kirk-Othmer Encyclopedia of Chemical Technology中之Thiols章節所描述。
甲硫胺酸α-羥基類似物及其衍生物選自由2-羥基-4-(C1-5烷硫基)丁酸、其鹽及酯組成之群。C1-5烷硫基對應於該方法中存在之包含硫之C1-5烷基硫化合物。甲硫胺酸α-羥基類似物及其衍生物較佳選自由以下各者組成之群:2-羥基-4-(甲硫基)丁酸、其鹽及酯。甲硫胺酸α-羥基類似物及其衍生物較佳選自由以下各者組成之群:2-羥基-4-(甲硫基)丁酸、其鹼金屬及鹼土金屬鹽及C1-8烷基酯。甲硫胺酸α-羥基類似物及其衍生物較佳選自由以下各者組成之群:2-羥基-4-(甲硫基)丁酸、其鹼金屬及鹼土金屬鹽及C1-8烷基酯。
在本文中,C1-8烷基酯意指包含選自由以下各者組成之群之烷基的酯:甲基、乙基、丙基、丁基、異丙基、異丁基、戊基、己基、庚基、辛基及2-乙基己基。鹼金屬及鹼土金屬鹽意謂酸之鹽,其中鹽陽離子選自第I族及第II族金屬。
在本發明之一個具體實例中,甲硫胺酸α-羥基類似物及其衍生物為2-羥基-4-(甲硫基)丁酸。
在本發明之另一具體實例中,甲硫胺酸α-羥基類似物及其衍生物選自由以下各者組成之群:2-羥基-4-(甲硫基)丁酸甲酯、2-羥基-4-(甲硫基)丁酸乙酯、2-羥基-4-(甲硫基)丁酸丙酯、2-羥基-4-(甲硫基)丁酸丁酯、2-羥基-4-(甲硫基)丁酸異丙酯、2-羥基-4-(甲硫基)丁酸戊酯、2-羥基-4-(甲硫基)丁酸己酯、2-羥基-4-(甲硫基)丁酸庚酯、2-羥基-4-(甲硫基)丁酸辛酯及2-羥基-4-(甲硫基)丁酸2-乙基己酯。
一或多種糖係選自由以下各者組成之群:C2-C6糖或其衍生物。在本文中,C2-C6糖或其衍生物意指選自由以下各者組成之群的在生質中常見的碳水化合物:葡萄糖、果糖、半乳糖、甘露糖、蔗糖、木糖、赤藻糖、赤藻酮糖、蘇糖、乙二醇醛及2-羥基-γ-丁內酯。
該方法較佳為一步驟方法,其中可藉由使一或多種糖與金屬矽酸鹽組成物在包含硫之化合物及溶劑存在下接觸而直接從糖受質獲得甲硫胺酸α-羥基類似物及其衍生物。
在本發明之另一具體實例中,可在存在其他C1-C3氧化物(諸如丙酮醇、丙酮醛、甲醛及乙二醛)情況下使用糖。根據US 7,094,932 B2及PCT/EP2014/053587中所描述之程序,藉由糖之水合熱分解,乙二醇醛(C2糖)可與少量其他C1-C3氧化物一起產生。
亦可藉由使一或多種糖或其衍生物經歷熱分解步驟以獲得熱分解產物,且接著使熱分解產物與金屬矽酸鹽組成物在包含硫之化合物及溶劑存在下接觸來獲得甲硫胺酸α-羥基類似物及其衍生物。
金屬矽酸鹽組成物指一或多種固體材料,其包含氧化矽及金
屬及/或金屬氧化物組分,其中金屬及/或金屬氧化物組分併入氧化矽結構中及/或接枝至氧化矽結構之表面上(亦即氧化矽結構包含M-O-Si鍵)。氧化矽結構亦稱為矽酸鹽。金屬矽酸鹽組成物可為結晶或非結晶。非結晶金屬矽酸鹽包括有序中孔非晶形或其他中孔非晶形形式。金屬矽酸鹽組成物選自由以下各者組成之群中之一或多者:沸石類材料及有序中孔非晶形矽酸鹽。
金屬及/或金屬氧化物組分中之活性金屬較佳選自由以下各者組成之群中之一或多者:Ge、Sn、Pb、Ti、Zr及Hf。沸石類材料之種類涵蓋沸石材料類。沸石類材料較佳具有選自由以下各者組成之群的構架結構:BEA、MFI、FAU、MOR及FER。有序中孔非晶形矽酸鹽較佳具有選自由以下各者組成之群的結構:MCM-41及SBA-15。在一個較佳具體實例中,金屬矽酸鹽組成物為沸石類材料。金屬矽酸鹽組成物更佳為沸石類材料且選自由以下各者組成之群:Sn-BEA、Sn-MFI、Sn-FAU、Sn-MCM-41及Sn-SBA-15。
溶劑選自由以下各者組成之群中之一或多者:甲醇、乙醇、1-丙醇、1-丁醇、2-丙醇、2-丁醇、DMSO及水。
WO 2015/024875揭示在某些條件下,反應溶液中存在金屬離子對產率有利。WO 2015/024875提供實驗細節,其描述方法中金屬離子之來源及添加,其經由催化劑自身或與催化劑無關。
本發明之另一具體實例為鹼性反應溶液。可藉由添加一或多種鹼性組分來獲得鹼性溶液。鹼性組分可選自試劑中之一或多者,該等試劑選自金屬鹽及鹼性聚合物樹脂。鹼性聚合物樹脂可為例如鹼性大孔樹脂。
金屬鹽包含金屬離子。金屬離子較佳選自由以下各者組成之群:鉀、鈉、鋰、銣及銫。金屬鹽較佳為鹼土金屬或鹼金屬之鹽且陰離子選自由以下各者組成之群:碳酸根、硝酸根、乙酸根、乳酸根、氯離子、溴離子及氫氧根離子。金屬離子甚至更佳來源於鹼土金屬或鹼金屬之一或多種鹽且選自由以下各者組成之群:K2CO3、KNO3、KCl、乙酸鉀(CH3CO2K)、乳酸鉀(CH3CH(OH)CO2K)、Na2CO3、Li2CO3及Rb2CO3。
將方法中所使用之反應容器/溶液加熱至低於250℃之溫度。容器較佳加熱至50℃至180℃、60℃至170℃、80℃至150℃;更佳為60℃至140℃。
根據本發明之方法,本發明人意外發現甲硫胺酸α-羥基類似物及其衍生物之產率大於MVG之產率。若C4糖為受質,則MVG之產率小於5%、4%、3%、2%、1%。
又,本發明人意外發現根據本發明之方法製備之甲硫胺酸α-羥基類似物及其衍生物之產率大於15%。
用於製備甲硫胺酸α-羥基類似物及其衍生物之方法可在批次規模反應或連續流反應中進行。
實施例
製備催化劑
根據US 4,933,161中所描述之程序之改良版製備Sn-BEA(Si/Sn=125)。煅燒(550℃保持6小時)市售沸石Beta(Zeolyst,Si/Al 12.5,銨形式)以獲得H形式(脫鋁酸鹽形式)且每公克沸石Beta粉末在80℃下用10公克濃硝酸(Sigma-Aldrich,65%)處理12小時。過濾所得固體,用足夠的水洗滌且煅燒(550℃保持6小時)以獲得脫鋁酸鹽之Beta。藉由初期潤濕法以125之Sn/Si比率浸泡此固體。出於此目的,將氯化錫(II)(0.128g,Sigma-Aldrich,98%)溶解於水(5.75mL)中且添加至脫鋁酸鹽之Beta(5g)中。在浸泡過程之後,樣品在110℃下乾燥12小時且再次煅燒(550℃保持6小時)。
實施例1:分批反應中之催化反應
將15.0g甲醇(Sigma-Aldrich,>99.8%)、0.450g蔗糖(Fluka,>99.0%)及0.150g催化劑裝入不鏽鋼壓力容器(40cc,Swagelok)中。接著在1.7巴下用75mL甲硫醇填充反應器,用N2在11巴下加壓且封閉。反應器在油浴中,在170℃下在攪拌(700rpm)下加熱。反應持續所需時間且在此時段之後,藉由將容器浸沒於冷水中來淬滅反應。過濾來自反應容器之樣品且藉由HPLC(Agilent 1200,Biorad Aminex HPX-87H管柱,在65℃
下,0.05M H2SO4,0.6ml min-1)分析以定量未經轉化之己糖及二羥基丙酮(DHA)、甘油醛(GLA);且使用GC(具有Phenomenex Solgelwax管柱之Agilent 7890)進行定量:乳酸甲酯(ML)、乙烯基羥乙酸甲酯(MVG,2-羥基-3-丁烯酸甲酯)、乙二醇醛二甲基縮醛(GADMA)及MHA(甲硫胺酸α-羥基類似物及其衍生物)。
根據實施例1製備之甲硫胺酸α-羥基類似物可在鹼性水溶液(諸如NaOH或KOH水溶液)或酸性水溶液(諸如HCl水溶液)或固體酸催化劑中反應以產生甲硫胺酸α-羥基類似物酯之鹽及酸衍生物。
溶劑A:MeOH+0.13mmol K2CO3
溶劑B:MeOH+0.06mmol K2CO3
溶劑C:MeOH+0.3mmol K2CO3
GA=乙二醇醛
如表1中所觀測,C4及C2糖(赤藻酮糖及乙二醇醛)提供最高產率之甲硫胺酸α-羥基類似物及其衍生物。甲醇及乙醇提供類似產率之相應酯。
實施例2:連續流反應中之催化反應
可在C1-C3氧化化合物存在下藉由生質或C5-C6糖(諸如葡萄糖、蔗糖、果糖或木糖)之熱分解來製備包含乙二醇醛之組成物。例示性熱分解反應提供於US 7,094,932 B2及PCT/EP2014/053587中。
包含乙二醇醛或C1-C3氧化化合物之組成物與814g/L乙二醇醛一起在室溫下溶解於甲醇(Sigma-Aldrich,99.9%)中達到10.9g/l之濃度。此外,向饋料溶液中添加甲硫醇(Sigma,1.7巴)及(若需要)水。根據以上製備方法製備之催化劑Sn-Beta(Si:Sn 125)經細分(0.25g,300-600μm)且裝載至不鏽鋼0.25吋反應器中。使用玻璃絨將催化劑保持在適當位置。將反應器引入烘箱中且反應器之溫度升高至160℃。當溫度超過140℃時,以0.05ml/min之流動速率開始泵送。
如從圖1及圖2所觀測,使用Sn-Beta作為催化劑,從含乙二醇醛之水及甲醇獲得穩定產率之2-羥基-4-(甲硫基)丁酸甲酯(超過30%)。存在其他C1-C3氧化化合物(圖2)不會影響甲硫胺酸α-羥基類似物甲酯之製備反應。
具體實例
亦可根據以下具體實例描述本發明:
具體實例1. 一種用於製備甲硫胺酸α-羥基類似物之方法,其包含使一或多種糖或其衍生物與金屬矽酸鹽組成物在包含硫之化合物及溶劑存在下接觸。
具體實例2. 如具體實例1之方法,其中該包含硫之化合物選自由以下各者組成之群:C1-C5烷基硫醇、C1-C5烷基硫醇鹽、二甲硫醇、二甲基二硫
化物及硫化氫。
具體實例3. 如具體實例1及具體實例2中任一項之方法,其中該包含硫之化合物選自由以下各者組成之群:甲烷硫醇、二甲硫醇、二甲基二硫化物及硫化氫。
具體實例4. 如具體實例1至3中任一項之方法,其中該一或多種糖或其衍生物選自由以下各者組成之群:葡萄糖、果糖、半乳糖、甘露糖、蔗糖、木糖、赤藻糖、赤藻酮糖、蘇糖、乙二醇醛及2-羥基-γ-丁內酯。
具體實例5. 如具體實例1至3中任一項之方法,其中該一或多種糖或其衍生物為藉由使一或多種選自由以下各者組成之群的糖經歷熱分解步驟以獲得熱分解產物且接著使該熱分解產物與金屬矽酸鹽組成物在包含硫之化合物及溶劑存在下接觸而獲得的衍生物:葡萄糖、果糖、半乳糖、甘露糖、蔗糖、木糖、赤藻糖、赤藻酮糖、蘇糖。
具體實例6. 如具體實例1至5中任一項之方法,其中該金屬矽酸鹽組成物為沸石類材料。
具體實例7. 如具體實例6之方法,其中該沸石類材料為一或多種選自由以下各者組成之群的材料:Sn-BEA、Sn-MFI、Sn-FAU、Sn-MCM-41及Sn-SBA-15。
具體實例8. 如具體實例1至7中任一項之方法,其中該溶劑選自由以下各者組成之群中之一或多者:甲醇、乙醇、1-丙醇、1-丁醇、2-丙醇、2-丁醇、DMSO及水。
具體實例9. 如具體實例1至8中任一項之方法,其中甲硫胺酸α-羥基類似物選自由以下各者組成之群:2-羥基-4-(甲硫基)丁酸、其鹽及酯。
具體實例10. 如具體實例1至9中任一項之方法,其中甲硫胺酸α-羥基類似物選自由以下各者組成之群:2-羥基-4-(甲硫基)丁酸、2-羥基-4-(甲硫基)丁酸甲酯及2-羥基-4-(甲硫基)丁酸乙酯。
具體實例11. 如具體實例1至10中任一項之方法,其中該方法之溫度低於200℃,較佳在50℃至200℃範圍內。
具體實例12. 如具體實例1至11中任一項之方法,其中該反應溶液包含一或多種選自由以下各者組成之群的鹼性組分:金屬鹽及聚合物樹脂。
具體實例13. 如具體實例1至12中任一項之方法,其中該等甲硫胺酸α-羥基類似物之產率大於乙烯基羥乙酸甲酯(MVG)。
具體實例14. 如具體實例1至13中任一項之方法,其中該等甲硫胺酸α-羥基類似物之產率大於15%。
具體實例15. 如具體實例1至14中任一項之方法,其中該方法為連續方法。
具體實例16. 如具體實例1至15中任一項之方法,其中該等甲硫胺酸α-羥基類似物藉由蒸餾純化。
具體實例17. 如具體實例9之方法,其中該等2-羥基-4-(甲硫基)丁酸酯經水解。
具體實例18. 一種藉由如申請專利範圍第9項至第17項之方法製備之2-羥基-4-(甲硫基)丁酸、其鹽及酯之用途,其用於營養補充劑中。
圖1. 在連續流反應中,使用乙二醇醛作為糖時甲硫胺酸α-羥基類似物之甲酯(2-羥基-4-(甲硫基)丁酸甲酯)之產率,其中Sn-Beta作為催化劑。饋料組成物:作為溶劑之9g/L含乙二醇醛之甲醇、10.7重量%水、0.9g/L甲硫醇。
圖2. 在連續流反應中,在C1-C3氧化化合物存在下,使用乙二醇醛時甲硫胺酸α-羥基類似物之甲酯(2-羥基-4-(甲硫基)丁酸甲酯)之產率,其中Sn-Beta作為催化劑。饋料組成物:作為溶劑之10.9g/L含乙二醇醛之甲醇、8重量%水、0.7g/L甲硫醇。
Claims (22)
- 一種用於製備甲硫胺酸α-羥基類似物之方法,其中該甲硫胺酸α-羥基類似物具有下式:R'-S-CH2-CH2-CHOH-COO-R (I)其中R選自由以下各者組成之群:H、C1-C8烷基、鹼金屬或鹼土金屬;且R'選自由以下各者組成之群:H及甲基;且其中該方法包含使一或多種糖與金屬矽酸鹽組成物在包含硫之化合物及溶劑存在下接觸之步驟,該包含硫之化合物具有式RSR',其中R和R'具有如以上所述相同的定義。
- 如申請專利範圍第1項之方法,其中該包含硫之化合物選自由以下各者組成之群:C1-C5烷基硫醇、C1-C5烷基硫醇鹽、二甲硫醇、二甲基二硫化物及硫化氫。
- 如申請專利範圍第2項之方法,其中該包含硫之化合物選自由以下各者組成之群:甲烷硫醇、甲硫醇鹽鹼性鹽、二甲硫醇、二甲基二硫化物及硫化氫。
- 如申請專利範圍第1項至第3項中任一項之方法,其中該一或多種糖選自由以下各者組成之群:葡萄糖、果糖、半乳糖、甘露糖、蔗糖、木糖、赤藻糖、赤藻酮糖、蘇糖、乙二醇醛、甲基乙烯基乙醇酸酯、乙烯基乙醇酸及2-羥基-γ-丁內酯。
- 如申請專利範圍第1項至第3項中任一項之方法,其中該糖為乙二醇醛,其係藉由以下方式獲得:使一或多種選自由葡萄糖、果糖、半乳糖、甘露糖、蔗糖、木糖、赤藻糖、赤藻酮糖和蘇糖組成之群的糖經 歷熱分解步驟,以獲得包含乙二醇醛之熱分解產物,且接著使該熱分解產物與該金屬矽酸鹽組成物在該包含硫之化合物及該溶劑存在下接觸。
- 如申請專利範圍第1項之方法,其中該金屬矽酸鹽組成物為沸石類材料。
- 如申請專利範圍第6項之方法,其中該沸石類材料為一或多種選自由以下各者組成之群的材料:Sn-BEA、Sn-MFI、Sn-FAU、Sn-MCM-41及Sn-SBA-15。
- 如申請專利範圍第1項之方法,其中該溶劑選自由以下各者組成之群中之一或多者:甲醇、乙醇、1-丙醇、1-丁醇、2-丙醇、2-丁醇、DMSO及水。
- 如申請專利範圍第1項之方法,其中該甲硫胺酸α-羥基類似物選自由以下各者組成之群:2-羥基-4-(甲硫基)丁酸、其鹽及酯。
- 如申請專利範圍第9項之方法,其中該甲硫胺酸α-羥基類似物選自由以下各者組成之群:2-羥基-4-(甲硫基)丁酸、2-羥基-4-(甲硫基)丁酸甲酯及2-羥基-4-(甲硫基)丁酸乙酯。
- 如申請專利範圍第1項之方法,其中在加熱下使該一或多種糖與該金屬矽酸鹽組成物在該包含硫之化合物和溶劑存在下接觸。
- 如申請專利範圍第11項之方法,其中加熱的溫度為50℃與200℃之間。
- 如申請專利範圍第11項之方法,其中加熱的溫度為80℃與120℃之間。
- 如申請專利範圍第11項之方法,其中加熱持續10分鐘至12小時之時段。
- 如申請專利範圍第1項之方法,其中使該一或多種糖與該金屬矽酸鹽組成物在該包含硫之化合物及溶劑存在下以及在一或多種鹼性組分存在下接觸,該一或多種鹼性組分選自由金屬鹽及聚合物樹脂組成之群。
- 如申請專利範圍第1項之方法,其中該甲硫胺酸α-羥基類似物之產率大於乙烯基羥乙酸甲酯(MVG)之產率。
- 如申請專利範圍第1項之方法,其中該甲硫胺酸α-羥基類似物之產率大於15%。
- 如申請專利範圍第1項之方法,其中該方法為連續方法。
- 如申請專利範圍第1項至第3項中任一項之方法,其中該甲硫胺酸α-羥基類似物係經回收的。
- 如申請專利範圍第1項之方法,其中該甲硫胺酸α-羥基類似物係藉由純化回收。
- 如申請專利範圍第20項之方法,其中該甲硫胺酸α-羥基類似物藉由蒸餾純化。
- 如申請專利範圍第9項之方法,其中該等2-羥基-4-(甲硫基)丁酸酯經水解。
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EP2184270A1 (en) * | 2008-11-11 | 2010-05-12 | Haldor Topsoe A/S | Zeolite-catalyzed preparation of alpha-hydroxy carboxylic acid compounds and esters thereof |
US20110229626A1 (en) * | 2008-11-20 | 2011-09-22 | Arkema France | Method for Manufacturing Methylmercaptopropionaldehyde and Methionine Using Renewable Raw Materials |
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JP2018517678A (ja) | 2018-07-05 |
WO2016174231A1 (en) | 2016-11-03 |
CA2983397A1 (en) | 2016-11-03 |
CA2983397C (en) | 2023-04-04 |
US10189778B2 (en) | 2019-01-29 |
CN107531619B (zh) | 2020-07-07 |
RU2017141609A3 (zh) | 2019-10-21 |
BR112017020877B1 (pt) | 2020-12-08 |
KR20180002647A (ko) | 2018-01-08 |
MX2017012457A (es) | 2018-01-30 |
EP3288920A1 (en) | 2018-03-07 |
JP6908529B2 (ja) | 2021-07-28 |
RU2719517C2 (ru) | 2020-04-20 |
TW201702220A (zh) | 2017-01-16 |
KR102673087B1 (ko) | 2024-06-10 |
RU2017141609A (ru) | 2019-05-30 |
SG11201708637RA (en) | 2017-11-29 |
AR104498A1 (es) | 2017-07-26 |
US20180118673A1 (en) | 2018-05-03 |
ZA201706480B (en) | 2021-01-27 |
CN107531619A (zh) | 2018-01-02 |
DK3288920T3 (da) | 2019-11-25 |
EP3288920B1 (en) | 2019-09-25 |
BR112017020877A2 (pt) | 2018-07-24 |
ES2751048T3 (es) | 2020-03-30 |
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