CS263174B1 - Process for preparing d-glycero-d-galactoheptose and d-glycero-d-taloheptose - Google Patents
Process for preparing d-glycero-d-galactoheptose and d-glycero-d-taloheptose Download PDFInfo
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- CS263174B1 CS263174B1 CS865666A CS566686A CS263174B1 CS 263174 B1 CS263174 B1 CS 263174B1 CS 865666 A CS865666 A CS 865666A CS 566686 A CS566686 A CS 566686A CS 263174 B1 CS263174 B1 CS 263174B1
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- heptose
- galacto
- taloheptose
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- BGWQRWREUZVRGI-UHFFFAOYSA-N D-glycero-altro-Heptose Natural products OCC(O)C1OC(O)C(O)C(O)C1O BGWQRWREUZVRGI-UHFFFAOYSA-N 0.000 title claims abstract description 18
- BGWQRWREUZVRGI-MKHROBFTSA-N D-mannoheptopyranose Chemical compound OC[C@@H](O)[C@@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O BGWQRWREUZVRGI-MKHROBFTSA-N 0.000 title claims abstract description 18
- YPZMPEPLWKRVLD-UHFFFAOYSA-N L-glycero-D-manno-heptose Natural products OCC(O)C(O)C(O)C(O)C(O)C=O YPZMPEPLWKRVLD-UHFFFAOYSA-N 0.000 title claims abstract description 18
- YPZMPEPLWKRVLD-NYMZXIIRSA-N (2s,3s,4s,5r,6r)-2,3,4,5,6,7-hexahydroxyheptanal Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H](O)C=O YPZMPEPLWKRVLD-NYMZXIIRSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 molybdenum ions Chemical class 0.000 claims abstract description 6
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 5
- 235000014633 carbohydrates Nutrition 0.000 claims abstract description 5
- 150000001304 aldoheptoses Chemical class 0.000 claims abstract description 4
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims abstract 2
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract 2
- 239000011733 molybdenum Substances 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- PCNAHKWQSJSICA-CQOGJGKDSA-N (2r,3r,4r,5r,6s)-7-nitroheptane-1,2,3,4,5,6-hexol Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H](O)C[N+]([O-])=O PCNAHKWQSJSICA-CQOGJGKDSA-N 0.000 claims description 2
- OXQKEKGBFMQTML-UHFFFAOYSA-N D-glycero-D-gluco-heptitol Natural products OCC(O)C(O)C(O)C(O)C(O)CO OXQKEKGBFMQTML-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 238000000855 fermentation Methods 0.000 claims description 2
- 230000004151 fermentation Effects 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000005445 natural material Substances 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- OXQKEKGBFMQTML-KVTDHHQDSA-N volemitol Chemical compound OC[C@@H](O)[C@@H](O)C(O)[C@H](O)[C@H](O)CO OXQKEKGBFMQTML-KVTDHHQDSA-N 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 2
- BGWQRWREUZVRGI-GVUNPQSCSA-N (2S,3R,4S,5R,6R)-6-[(1R)-1,2-dihydroxyethyl]oxane-2,3,4,5-tetrol Chemical compound OC[C@@H](O)[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O BGWQRWREUZVRGI-GVUNPQSCSA-N 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 claims 1
- 238000004255 ion exchange chromatography Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HSNZZMHEPUFJNZ-SHUUEZRQSA-N sedoheptulose Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO HSNZZMHEPUFJNZ-SHUUEZRQSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HAIWUXASLYEWLM-UHFFFAOYSA-N D-manno-Heptulose Natural products OCC1OC(O)(CO)C(O)C(O)C1O HAIWUXASLYEWLM-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 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 1
- HSNZZMHEPUFJNZ-UHFFFAOYSA-N L-galacto-2-Heptulose Natural products OCC(O)C(O)C(O)C(O)C(=O)CO HSNZZMHEPUFJNZ-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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- Saccharide Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Účelom riešenia je zlepšenie spósobu přípravy D-glycero-D-galaktoheptózy a D- glyoero- -D-taloheptózy. Uvedeného účelu sa dosiahne tak, že tuhé sodné soli 1-deoxy-l-nitroheptitolov sa rozkladajú peroxidom vodíka za katalýzy molybdénanovými iónmi na odpovedajúce aldoheptózy. Spósob přípravy D-glycero-D-galaktoheptózy a D-glycero- -D-taloheptózy má použitie v organickej chémii a biochémii pri príprave sacharidov.The purpose of the solution is to improve the method the preparation of D-glycero-D-galacto-heptose and D- \ t D-taloheptózy. This purpose is achieved so that the solid sodium salts of 1-deoxy-1-nitroheptitols are decomposed by hydrogen peroxide under catalysis with molybdenum ions at corresponding aldoheptoses. Method of preparation D-glycero-D-galacto-heptose and D-glycero -D-taloheptose has use in organic chemistry and biochemistry in the preparation of carbohydrates.
Description
Vynález sa týká spůsobu přípravy D-glycero-D-galaktoheptózy a D-glycero-D-taloheptózy.The invention relates to a process for the preparation of D-glycero-D-galactoheptose and D-glycero-D-taloheptose.
Na přípravu D-glycero-D-galaktoheptózy a D-glycero-D-taloheptózy sa využívajú reakcie založené na predlžovaní uhlíkatého reťazca D-manózy. Kyanhydrínovou syntézou a následnou hydrolýzou získané C-epimérne heptónové kyseliny sa rozdeíujú vo formě ich vápenatých resp. bárnatých solí, ktoré po redukcii poskytujú D-glycero-D-galaktoheptózu resp. D-glycero-D-taloheptózu [h. S. Isbell: J. Res. Nat. Bur. Stand. 20, 97 (1938),· Ε. M. Montgomery,Reactions based on the carbon chain extension of D-mannose are used to prepare D-glycero-D-galactoheptose and D-glycero-D-taloheptose. The C-epimeric heptonic acids obtained by cyanohydrin synthesis and subsequent hydrolysis are separated in the form of their calcium and resp. barium salts which, after reduction, yield D-glycero-D-galacto-heptose, respectively. D-glycero-D-taloheptose [h. S. Isbell, J. Res. Nat. Bur. Stand. 20, 97 (1938); M. Montgomery,
C. S. Hudson: J. Amer. Chem. Soc. 64, 247 (1942)3- Nitrometánová syntéza sa uskutočňuje v prostředí metanolového roztoku metanolátu sodného £j. C. Sowden, R. Schaffer: J. Amer.Hudson, C. S. J. Amer. Chem. Soc. 64, 247 (1942). The 3-nitromethane synthesis is carried out in a medium of methanolic sodium methoxide solution. C. Sowden, R. Schaffer, J. Amer.
Chem. Soc. 73, 4 662 (1951)], alebo vodnom roztoku hydroxydu sodného [j. C. Sowden,Chem. Soc. 73, 4,662 (1951)], or aqueous sodium hydroxide solution [i. C. Sowden,
R. R. Thomson: J. Amer. Chem. Soc. 80, 2 236 (1958)], získané C(2-epimérne 1-deoxy-l-nitroheptitoly sa rozdeíujú frakčnou kryštalizáciou a nakoniec sa izolované nitroheptitoly vo formě ich sodných solí rozkladajú Neffovou reakciou (kyselinou sírovou) na odpovedajúce aldoheptózy. Pre přípravu L-glycero-L-galaktoheptózy a L-glycero-L-taloheptózy sa tiež uplatnila reakcia nitrometánu a L-manózy v metanolovom roztoku za přítomnosti metanolátu sodného a získané sodné soli nitroheptitolov sa rozpustia vo vodě a rozkladajú sa peroxidom vodíka za katalýzy molybdénanovými iónmi na odpovedajúce aldoheptózy, ktoré sa izolujú chromatografiou na štipci iónomeniča s funkčnými sulfoskupinami v bárnatom cykle [v. Bílik,RR Thomson J. Amer. Chem. Soc. 80, 2 236 (1958)], obtained the C ( 2- epimeric 1-deoxy-1-nitroheptitols) by fractional crystallization and finally the isolated nitroheptitols in the form of their sodium salts are decomposed by the Neff reaction (sulfuric acid) to the corresponding aldoheptoses. -glycero-L-galactoheptose and L-glycero-L-taloheptose were also reacted with nitromethane and L-mannose in methanolic solution in the presence of sodium methoxide and the sodium nitroheptitol salts obtained dissolved in water and decomposed with hydrogen peroxide to catalyze the molybdenum ions to the corresponding aldoheptoses, which are isolated by chromatography on an ion-exchange column with functional sulfo groups in a barium cycle [v. Bílik,
D. Anderle, J. Alfoldi: Chem. zvěsti 28, 668 (1974)]. Pri nitrometánovej syntéze sa sodné soli nitroheptitolov vo vodnom roztoku rozkladajú na východiskové zložky a tým sa znižuje výťažok požadovaných aldoheptóz.D. Anderle, J. Alfoldi: Chem. rumors 28, 668 (1974)]. In nitromethane synthesis, sodium salts of nitroheptitols in aqueous solution decompose to the starting components, thereby reducing the yield of the desired aldoheptoses.
Podstata spůsobu přípravy D-glycero-D-galaktoheptózy a D-glycero-D-taloheptózy reakciou D-manózy a nitrometánu v metanolovom roztoku hydroxydu sodného, oxidačným rozkladom vo vodnom roztoku, deionizáciou roztoku vymieňačmi iónov, skvasením D-manózy, kryštalizáciou časti D-glycero-D-galaktoheptózy z roztoku metanolu a kyseliny octovej a delením matečného roztoku chromatografiou na iónomeniči s funkčnými sulfoskupinami vo vápenatom alebo bárnatom cykle spočívá v tom, že tuhé sodné soli 1-deoxy-l-nitro-D-glycero-D-galaktoheptitolu a 1-deoxy-1-nitro-D-glyoero-D-taloheptitolu sa rozkladajú peroxidom vodíka za katalýzy molybdénanovými iónmi.Principle of the preparation of D-glycero-D-galactoheptose and D-glycero-D-taloheptose by reaction of D-mannose and nitromethane in methanolic sodium hydroxide solution, oxidative decomposition in aqueous solution, deionization of the solution with ion exchangers, fermentation of D-mannose, crystallization of part D- glycero-D-galacto-heptose from a methanol / acetic acid solution and separating the mother liquor by calcium or barium cyclic ion exchange chromatography by means of calcium or barium cyclic ion exchange chromatography is characterized in that the solid sodium salts of 1-deoxy-1-nitro-D-glycero-D-galacto-heptitol; The 1-deoxy-1-nitro-D-glyoero-D-taloheptitol is decomposed with hydrogen peroxide under catalysis with molybdenum ions.
Výhodou navrhovaného spůsobu přípravy D-glycero-D-galaktoheptózy a D-glycero-D-taloheptózy je, že je v technickom prevední velmi jednoduchý, všetky potřebné chemikálie sú bežne dostupné a nenáročný je na technologické zariadenie. Ďalšou výhodou je, že pri použití pevných sodných solí 1-deoxy-l-nitroheptitolov sú výťažky vyššie. Přidaná kyselina octová rozkládá dusitany na oxidy dusíka, ktoré sa uvolnia a odstránia a tým sa predíží životnosť používaných iónomeničov.The advantage of the proposed process for the preparation of D-glycero-D-galacto-heptose and D-glycero-D-taloheptose is that it is very simple in the technical design, all the necessary chemicals are commercially available and easy to process. A further advantage is that when solid sodium salts of 1-deoxy-1-nitroheptitols are used, the yields are higher. The added acetic acid decomposes the nitrites into nitrogen oxides, which are released and removed, thereby extending the life of the ion exchangers used.
Příklad 1Example 1
V 500 ml metanolu sa rozpustí 100 g D-mánózy, přidá sa 200 ml nitrometánu a po častiach (t.j. po 30 ml) za miešania 750 ml 1,3 mol.l-^ metanolového roztoku hydroxydu sodného a reakčná zmes sa mieša počas 7 hodin a potom nechá stáť počas 20 hodin pri teplote 23 °C. Vylúěené sodné soli 1-deoxy-l-nitro-D-glycero-D-galaktoheptitolu a 1-deoxy-l-nitro-D-glycero-D-taloheptitolu sa odfiltrujú a premyjú metanolom. Do zmesi 1 000 ml 0,05 mol.l 1 vodného roztoku hydroxydu sodného, 100 ml 30 % hmot. vodného roztoku peroxidu vodíka a 2 g molybdénanu amonného sa v priebehu 7 minút za miešania po častiach (t.j. 1 g) přidávájú sodné soli nitroheptitolov. Oxidačný rozklad nitroheptitolov na aldoheptózy je reakcia mierne axotarmická a preto reakčná zmes sa chladl, aby teplota nepresiahla 30 °C. Reakčná zmes sa nechá stát pri teplote 23 °C počas 20 hodin. Potom sa přidá 10 ml 100 % hmot. kyseliny octovej a roztok prebubláva vzduchom. Roztok sa potom nechá stáť 20 hodin a po přidaní 0,1 g 5 % hmot. paládia na uhlí sa nechá stáť dalších 20 hodin. Roztok sa přefiltruje a deonizuje prídavkom 500 ml iónomeniča s funkčnými sulfoskupinami (Ostion KS 0 210) a potom 500 ml iónomeniča s funkčnými skupinami na báze terciálnych amínov (Ostion AT 0 209) v karbonátovom cykle. Deionizovaný roztok sa zahustí na 1 000 ml objem, přidá sa 1 000 ml pitnej vody, g pekárskych kvasnic (Saccharpmyces cerevisiae) a zmes sa nechá stáť pri teplote 23 °C počas 1 až 2 dní do úplného skvasenía D-manózy. Roztok sa přefiltruje, zahustí a destilačný zvyšok rozpustí v zmesi 30 ml 100 % hmot. kyseliny octovéj a 90 ml metanolu a nechá krystalizovat, čím sa získá 36 g D-glycero-D-galaktoheptózy. Matečný roztok sa chromatografuje na štipci iónomeniča s funkčnými sulfoskupinarai vo vápenatom cykle o priemere 3,6 cm a dlžke 110 cm elúciou vodou o prietoku 150 ml.h-^ prvých 1 000 ml a potom o prietoku 250 ml.h 1. Frakoia I (elučný objem 480 až 940 ml) obsahuje 16 g D-glycero-D-galaktoheptózy a frakcia II (elučný objem 1 000 až 2 2000 ml) 19 g D-glyoero-D-taloheptózy. Celkový výtažok D-glycero-D-galaktoheptózy je 44,5 % a D-glycero-D-taloheptózy 16,2 % počítané na východiskovú D-manózu. Kryštalizácia resp. rekryštálizácia sa uskutočňuje v zmesi metanolu a 100 % hmot. kyseliny octovéj v objemovom pomere 2:1, čím sa získá D-glyoero-D-galaktoheptóza o teplote topenia 139 až 141 °c a optickej otáčavosti [a] D + 67,5° (c 1,5, voda) a D-glycero-D-taloheptóza o teplote topenia 106 až 108 °C a optickej otáčavosti + 13,5° (c 1,5, voda).Dissolve 100 g of D-mannose in 500 ml of methanol, add 200 ml of nitromethane and add in portions (ie 30 ml) with stirring 750 ml of a 1,3 mol / l methanolic sodium hydroxide solution and stir the reaction mixture for 7 hours and then allowed to stand for 20 hours at 23 ° C. The precipitated sodium salts of 1-deoxy-1-nitro-D-glycero-D-galactoheptitol and 1-deoxy-1-nitro-D-glycero-D-taloheptitol are filtered off and washed with methanol. To a mixture of 1000 ml 0.05 mol / l aqueous sodium hydroxide solution, 100 ml 30 wt. of an aqueous solution of hydrogen peroxide and 2 g of ammonium molybdate, sodium nitroheptitols are added in portions (i.e. 1 g) with stirring over 7 minutes. The oxidative decomposition of nitroheptitols to aldoheptoses is a slightly axotarmic reaction and therefore the reaction mixture was cooled so that the temperature did not exceed 30 ° C. The reaction mixture was allowed to stand at 23 ° C for 20 hours. 10 ml of 100 wt. acetic acid and the solution is bubbled through the air. The solution is then allowed to stand for 20 hours and after addition of 0.1 g of 5 wt. The palladium on charcoal is allowed to stand for a further 20 hours. The solution is filtered and deonized by the addition of 500 ml of sulfonated ion exchanger (Ostion KS 0 210) and then 500 ml of tertiary amine functional ion exchanger (Ostion AT 0 209) in a carbonate cycle. The deionized solution is concentrated to 1000 ml volume, 1000 ml of drinking water, g of baker's yeast (Saccharpmyces cerevisiae) are added and the mixture is allowed to stand at 23 ° C for 1-2 days until complete fermentation of D-mannose. The solution is filtered, concentrated and the residue is dissolved in a mixture of 30 ml of 100 wt. of acetic acid and 90 ml of methanol and crystallized to give 36 g of D-glycero-D-galactoheptose. The mother liquor is chromatographed on a column of sulfonic acid ion exchangers in a calcium cycle of 3.6 cm in diameter and 110 cm in length, eluting with water at a flow rate of 150 ml.h - 1 for the first 1000 ml and then at a flow rate of 250 ml.h 1 . Frakoia I (480-940 mL elution volume) contains 16 g of D-glycero-D-galactoheptose and Fraction II (1000-2000 mL elution volume) of 19 g of D-glyoero-D-taloheptose. The total yield of D-glycero-D-galactoheptose is 44.5% and D-glycero-D-taloheptose is 16.2% calculated on the initial D-mannose. Crystallization respectively. recrystallization is carried out in a mixture of methanol and 100 wt. acetic acid in a 2: 1 by volume ratio to give D-glyoero-D-galacto-heptose with a melting point of 139-141 ° C and an optical rotation of [α] D + 67.5 ° (c 1.5, water) and D-glycero D-Taloheptose, m.p. 106-108 ° C and optical rotation +13.5 ° (c 1.5, water).
J. C. Sowden a R. Schaffer udávajú pre alfa-D-glycero-D-galaktoheptózu teplotu topeniaJ. C. Sowden and R. Schaffer report melting point for alpha-D-glycero-D-galacthoheptosis
135 až 137 °C a špecifickú otáčavosť + 68,1° (c 3,5, voda) a pre D-glycero-D-talo·· u o 2 5 o heptózu monohydrát teplotu topenia 83 až 84 °C a optickú otáčavosť [aJD + 15,8° (c 3,5, voda) £j. C. Sowden, R. Schaffer: J. Amer. Chem. Soc. 80, 2 236 (1958)J. Zloženie reakčných zmesi ako i čistota izolovaných aldoheptóz sa sledovala chromatografiou na ohromatografiokom papíeri (Whatman No 1) elučným systémom n-butanol:etanol:voda v objemovom pomere 5:1:4 (detekciou kyslým ftalátom anilínu), o prietoku 18 až 22 h, kde pohyblivost vtahovaná na D-glukózu 1,00 (hnědá) je pre D-manózu 1,36 (hnědá), D-glyoero-D-galaktoheptžu 0,63 (hnedočervená) a pre D-glycero-D-taloheptózu 1,29 (hnedočervená).135 DEG-137 DEG C. and a specific rotation of + 68.1 DEG (c 3.5, water) and for D-glycero-D-talo-o-heptose monohydrate melting point 83-84 DEG C. and optical rotation [α] D + 15.8 ° (c 3.5, water). C. Sowden, R. Schaffer, J. Amer. Chem. Soc. 80, 2236 (1958) J. The composition of the reaction mixtures as well as the purity of the isolated aldoheptoses were monitored by chromatography on chromatography (Whatman No 1), eluting with an n-butanol: ethanol: water (5: 1: 4 by volume) (detection by aniline acid phthalate), flow rate 18-22 h, where the mobility drawn on D-glucose 1.00 (brown) is 1.36 (brown) for D-mannose, 0.63 (brown-red) for D-glyoero-D-galactohept, and 1.29 for D-glycero-D-taloheptose (brown-red).
Vynález móže nájsť široké uplatnenie pre přípravu D-glycero-D-galaktoheptózy a D-glycero-D-taloheptózy, ktoré sú súčasne východiskové zlúčeniny pre přípravu v prírode sa nachádzajúeich sacharidov t.j. D-pesitolu, D-volemitolu, D-manoheptulózy, D-altroheptulózy, L-galaktoheptulózy a tiež ako Standardně zlúčeniny pri sledovaní sacharidov v prírodnom materiáli.The invention can find wide application for the preparation of D-glycero-D-galacto-heptose and D-glycero-D-thaloheptose, which are simultaneously the starting compounds for the preparation of naturally occurring carbohydrates, i. D-pesitol, D-volemitol, D-manoheptulose, D-altroheptulose, L-galactoheptulose and also as standard compounds in the monitoring of carbohydrates in natural material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS865666A CS263174B1 (en) | 1986-07-28 | 1986-07-28 | Process for preparing d-glycero-d-galactoheptose and d-glycero-d-taloheptose |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS865666A CS263174B1 (en) | 1986-07-28 | 1986-07-28 | Process for preparing d-glycero-d-galactoheptose and d-glycero-d-taloheptose |
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| CS566686A1 CS566686A1 (en) | 1988-09-16 |
| CS263174B1 true CS263174B1 (en) | 1989-04-14 |
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| CS865666A CS263174B1 (en) | 1986-07-28 | 1986-07-28 | Process for preparing d-glycero-d-galactoheptose and d-glycero-d-taloheptose |
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