CS253443B1 - Process for preparing methyl-3,4-0-isopropyliden-alpha-d-galaktopyranoside - Google Patents
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Abstract
Zlepšeme sposobu přípravy metyl-3,4- -O-izoproipylidén-a-D-galaktopyranozidu sa dosiahne tak, že metyl-a-D-galaktopyranozid sa kondenzuje s bezvodým acetónom pri teplote 60 až 150 CC za katalýzy 0,4 až 4 mmól. .I-1 komplexom chloridu cínatéhos pyridínom v roztoku po· dobu 16 až 48 h. Spůsob přípravy metyl-3,4-0-izopropylidén- -α-D-galaktopyranozidu má použitie v organických syntézách.We will improve the preparation of methyl-3,4- -O-isoproipylidene-α-D-galactopyranoside is achieved by methyl-α-D-galactopyranoside is condensed with anhydrous acetone at room temperature at a temperature of 60 to 150 ° C under catalysis of 0.4 to 4 mmol. .I-1 complex of stannous chloride pyridine in solution for 16 to 48 h. Process for preparing methyl-3,4-O-isopropylidene- -α-D-galactopyranoside has uses in organic syntheses.
Description
Vynález sa týika spůsobu přípravy metyl-3,4-O-izopropylidén-a-D-galuktopyiranozidu.The invention relates to a process for the preparation of methyl-3,4-O-isopropylidene-α-D-galuctopyiranoside.
Metyl-3,4-0-izopropylidé'n-a-D-galaktopyranozid sa připravoval kondenzáciou acetonu s metyl-a-D-galáktopyranozidom v bezvodom prostředí za prítomnoisti katalyzátorov ako je kyselina chlorovodíková, kyselina sírová a sušidiel aiRo je síran maďnatý a síran sodný [A. N. de Belder: Adv. Carhohydr. Chem. 20, 219 (1965)]. Reakcia prebiehala pri teplote 15 až 25 °C a koncentrácia katalyzátora (0,1 až 0,4 % hmot.) ovplyvňovala výťažok produktu. Pre dosiahnutie rovnovážného stavu sa optimálna koncentrácia katalyzátora stanovovala polkusne, makolko' v dano/m úzkom koncentračním rozmedzí jeho množstvo iné než optimálně málo za následok zníženie výtažku metyl-3,4-O-izopropylidén-a-D-galaktopyranozidu. Pozorovalo sa, že vyššia koncentrácia katalyzátora než optimálna iniciovala hydrolýzu a tiéž izomerizáciou metyl-3,4-0-izropropylidén-a-D-galaktopyranozidu a nižšia koncentrácia zase negativné ovplyvňovala fconverziu východzieho metyl-a-D-galaktopyrainozidu. V oboch prípadoch holi výtažky metyl-3,4-0-izopropylidén-a-D-galaktopyranpzidu nízké (40 až 60 %).Methyl-3,4-O-isopropylidene-α-D-galactopyranoside was prepared by condensation of acetone with methyl-α-D-gallactopyranoside in anhydrous medium in the presence of catalysts such as hydrochloric acid, sulfuric acid and desiccants and iRo is copper sulfate and sodium sulfate [A. N. de Belder: Adv. Carhohydr. Chem. 20, 219 (1965)]. The reaction was carried out at a temperature of 15 to 25 ° C and the concentration of the catalyst (0.1 to 0.4% by weight) influenced the product yield. In order to achieve equilibrium, the optimum catalyst concentration was determined by the polysaccharide at a narrow concentration range other than optimally resulting in a reduction in the yield of methyl-3,4-O-isopropylidene-α-D-galactopyranoside. It was observed that a higher catalyst concentration than optimal initiated hydrolysis and also isomerization of methyl-3,4-O-isopropylpropylidene-α-D-galactopyranoside, and a lower concentration negatively affected the conversion of the starting methyl α-D-galactopyrainoside. In both cases, methyl-3,4-O-isopropylidene-α-D-galactopyranpidide yields were low (40-60%).
Uvedené nevýhody v podstatnej miere odstraňuje sposob přípravy metyl-3,4-O-izopropylidén-a-D-galaktapyranozidu kondernzáciou s bezvodým acetonem podta vynálezu, ktorého podstata spočívá v tom, že metyl-a-D-galaktopyranozid sa kondenzuje pri teplote 60 až 150 °C za katalýzy 0,3 až 4 mmól. I*1 komplexem chloridu cínatého s pyridínom v roztoku po dobu 16 až 48 h.The above disadvantages are substantially eliminated by the process for the preparation of methyl-3,4-O-isopropylidene-αD-galactapyranoside by anhydrous acetone condensation according to the invention, which is characterized in that the methyl α-D-galactopyranoside is condensed at 60 to 150 ° C at catalysis of 0.3 to 4 mmol. I * 1 with stannous chloride complex with pyridine in solution for 16 to 48 h.
Výhodou navrhovaného sposobu přípravy metyl-3,4-0-izopropylidén-a-D-galaiktopyranozidu oproti doterajším postupom přípravy je že je jednoduchší a efektivnější, dává výťažok produktu až 85 % v široikom koncentračnom rozmedzí katalyzátora 0,4 až 4 mmól. I-1. Ďalšou výhodou je, že neprebiehajú hydrolyticiké a izomerizačné reaikcie, získá sa čistý metyl-3,4-0-izopropylidén-a-D-galaktopyranozid.The advantage of the proposed process for the preparation of methyl-3,4-O-isopropylidene-α-D-galactopyranoside over prior art processes is that it is simpler and more efficient, yielding a product yield of up to 85% over a wide catalyst concentration range of 0.4 to 4 mmol. I -1 . A further advantage is that no hydrolytic and isomerization reactions take place, and pure methyl-3,4-O-isopropylidene-α-D-galactopyranoside is obtained.
Příklad 1Example 1
Metyl-a-D-galaktopyranozid (2 g) sa suspenduje v bezvodom acetone (80 ml) a přidá sa komplex chloridu cínatého s pyridínom v koncentrácií 0,4 mmól. I-1. Reakčná zmes sa zahrieva v zatavenej sklenej bamke pri teplote 150 °C po· dobu 16 ih. Po přefiltrovaní sa roztok odpaří pri tlalku 5 ikPa na malý objem (20 ml) a čtyřikrát vytrepáva medzi chloroformem (15 ml) a vodou (10 ml). Zahuštěním organickéj vrstvy sa získá sirupovitý produkt, ktorý sa krystalizuje 96 °/o obj. etanolu a petroléteru v celikovoim výtažku 2 g, t. j. 85 °/o. Metyl-3,4-O-izropropylidén-a-D-galaktopyranozid má teplotu topenia 102 až 103 °C, optickú otáčavosť [a]D 20 +162,5° (c· = 1,5; voda).Methyl-α-D-galactopyranoside (2 g) was suspended in anhydrous acetone (80 ml) and the tin (II) chloride-pyridine complex was added at a concentration of 0.4 mmol. I -1 . Heat the reaction mixture in a sealed glass jar at 150 ° C for 16 ih. After filtration, the solution was evaporated to a small volume (20 ml) at 5 mbar and shaken four times between chloroform (15 ml) and water (10 ml). Concentration of the organic layer yielded a syrupy product which was crystallized at 96% v / v. ethanol and petroleum ether in a total yield of 2 g, i.e. 85%. Methyl-3,4-O-isropropylidene-α-D-galactopyranoside has a melting point of 102-103 ° C, an optical rotation of [α] D 20 + 162.5 ° (c = 1.5; water).
Příklad 2Example 2
Postupuje sa ako v příklade 1 s tým rozdielom, že reakčná zmes sa zahrieva v zatavenej sklenej banike pri teplote 100 CC po dobu 24 h. pri koncentrácií komplexu chloridu cínatého s pyridínom v roztoku 2 mmól. I1. Výťažok je 2 g, t. j. 85 %. Metyl-3,4-O-izopropylidén-a-D-galaktopyra'nozid má teplotu topenia 102 až 103 °C, optickú otáčavosť [a]D 20 +162,5° (c = 1,5; voda). Příklad 3The procedure was as in Example 1 except that the reaction mixture was heated in a sealed glass flask at 100 ° C for 24 h. at a concentration of the stannous chloride / pyridine complex in a solution of 2 mmol. I 1 . The yield is 2 g, i.e. 85%. Methyl-3,4-O-isopropylidene-α-D-galactopyranoside has a melting point of 102-103 ° C, an optical rotation of [α] D 20 + 162.5 ° (c = 1.5; water). Example 3
Postupuje sa ako v příklade 1 s tým rozdielom, že reakčná zmes sa zahrieva v zatavenej sklenej banke pri teplote 60 °C po dobu 48 hod. pri koncentrácii komplexu chloridu cínatého s pyridínom v roztoku 4 mmól. 1_1. Výťažok je 1,9 g, t. j. 81 %. Metyl-3,4-0-izropropylidén-«-D-galakto|pyranozid má teplotu topenia 102 až 103 °C, optickú otáčavosť [a]D 20 +162,5° (c = 1,5; voda).The procedure is as in Example 1 except that the reaction mixture is heated in a sealed glass flask at 60 ° C for 48 hours. at a concentration of the stannous chloride / pyridine complex in a solution of 4 mmol. 1 _1 . Yield 1.9 g, i.e. 81%. Methyl-3,4-O-isopropyl-β-D-galactopyranoside has a melting point of 102-103 ° C, an optical rotation of [α] D 20 + 162.5 ° (c = 1.5; water).
Východzí metyl-a-D-galaktopyranozid pre přípravu metyl-3,4-O-izopropylidén-a-D-galaiktopyranozidu sa získá nasledujúcim sposohom [J. K. Dále, C. S. Hudison: J. Amer. Chem. Soc. 52, 2 534 (1930)]:The starting methyl-α-D-galactopyranoside for the preparation of methyl-3,4-O-isopropylidene-α-D-galactopyranoside is obtained as follows [J. K. Further, C.S. Hudison: J. Amer. Chem. Soc. 52, 2,534 (1930)]:
Příklad 4Example 4
D-galaktóza (10 g) sa suspenduje v 4 % hmot. hezvodej metanolickej ikyselíne chlorovodíkové j (200 ml) a reakčná zmes sa refluxuje pod spatným chladičem, pričom priebeh glykozidácie sa sleduje chromatografiou na tenkých vrstvách silikagélu v sústave chloroform a metanol v objemovom pomere 6:1. Po dosiahnuti rovnovážného' stavu (15 hod.) sa roztok zneutralizuje iónomeničom s funkčnými trimetylamóniummetylovými skupinami (Amber lite IRA-402 pract., 0,3 až 1,5 mm) přefiltruje a odpaří pri tlaku 5 kPa na sirup. Sirup sa pri teplote 60CC rozpustí v 2-propanole (50 ml] a ochladením na teplotu 0 °C vykrystalizuje metyl-a-D-galaktopyranozid monohydrát (5,7 g, 48,4 %), ktorý sa oddělí odsáním matečného roztoku na frite (Si), filtrát sa zahustí pri tlaku 5 kPa a kryštalizáciou sa získá další metyl-a-D-galaktopyranozid monohydrát (1,2 g). Celkový výťažok krystalického produktu je 6,9 g, t. j. 58,6 %. Po vysušení do konštantnej váhy pri teplote 80 °C a tlaku 1,33 kPa sa získá krystalický metyl-a-D-galaktopyranozid (6,3 g) s teplotou topenia 111 až 112 °C, s optickou otáčavoisťou [a]D20 +168,9° (c = 1,5; etanol).D-galactose (10 g) was suspended in 4 wt. The reaction mixture was refluxed under reflux, monitoring the progress of glycosidation by thin layer chromatography on silica gel in chloroform / methanol (6: 1 v / v). After reaching equilibrium (15 h), the solution is neutralized with a trimethylammonium methyl functional ion exchanger (Amber Lite IRA-402 pract., 0.3-1.5 mm), filtered and evaporated at 5 kPa to a syrup. The syrup was dissolved in 2-propanol (50 mL) at 60 ° C and, upon cooling to 0 ° C, methyl α-D-galactopyranoside monohydrate crystallized (5.7 g, 48.4%) which was separated by suction of the mother liquor on a frit. (Si), the filtrate was concentrated at 5 kPa and crystallized to give additional methyl-α-D-galactopyranoside monohydrate (1.2 g), yielding a total crystalline product of 6.9 g, ie 58.6%. at a temperature of 80 ° C and a pressure of 1.33 kPa, a crystalline methyl-α-D-galactopyranoside (6.3 g) is obtained with a melting point of 111-112 ° C, with an optical rotation of [α] D 20 + 168.9 ° (c = 1.5; ethanol).
Metyl-3,4-0-izopropylidén-a-D-galaktO'pyranozid připravený podta príkladov 1 až 3 je medziproduktom pri príprave 2,6-di-O-metyl-D-galaktózy. Možno postupovat známým spůsobom [R. L. Whistler, J. N. BeMiller: Methods Caríbohydr. Chem. 6, 361 (1972)]:The methyl-3,4-O-isopropylidene-α-D-galacto-pyranoside prepared according to Examples 1 to 3 is an intermediate in the preparation of 2,6-di-O-methyl-D-galactose. It is possible to follow the known method [R. L. Whistler, J. N. BeMiller: Methods Carbohydr. Chem. 6, 361 (1972)]
Příklad 5Example 5
K chladenému roztoku (teplota 5°C) metyl-3-,4-O-izopropylidé,n-a-D-galaktopyranozidu (2 g) v bezvodo,m 1,2-dimetoxyetáne (20· mí) sa po· malých dávkách přidává hydrid sodný (0,85 g) a zmes sa mieša pri teplete 20 CC po dobu 2 hod. Potom sa přidá metyl jod d (4 ml) a priebeh reaikcie sa sleduje chromatografiou na tenkých vrstvách silikagélu v sústave chloroform a aceton v objemovom pomere 9:2. Po uplynutí 15 hodin prebehne metylácia úplné, ik reaikčnej zmesi sa přidá voda (15 ml), roztok sa odpaří pri tlaku 5 kPa na malý objem (15 mlj a štyrikrát vytrepáva medzi chloroformom (20 ml) a vodou (15 ml). Zahuštěním organickej vrstvy sa získá metyl-3,4-0-izropropylidén-2,6-di-O-meityla-D-galaktopyranozid (2,1 g, 92 %), ktorý sa ihydrolyzuje 5 % hmot. vodným rozíokom. kyseliny chlorovodíkové j (30 ml) pod spatným cibladičom pri 100 °C po dobu 3 hod. Reakčná zmes sa zneutralizuje iónomeničom s funkčnými trimetylamóniummetylovými skupinami (Amberlite IRA-402 prací., 0,3 až 1,5 mm), preG filtruje a odpaří pri tlaku 5 kPa na sirup. Sirup sa pri teplote 65 °C rozpustí v octane etylovom (40 ml) a ochladením na teplotu —5 °C vykrystalizuje 2,6-di-O-metyl-D-galaiktóza (0,9 g, 53 %), ktorá sa oddělí odsáním matečného roztoku na frite (Si), filtrát sa zahustí pri fláku 5 kPa a ikryštalizáciou sa získá ďalšia 2,6-di-O-metyl-D-gaíaktóza (0,5 g). Celkový výťažok ikryštalickej látky je 1,4 g, t. j. 82 %. 2,6-di-O-metyl-D-galaktóza imá teplotu topenia 127 až 128 CC a optickú otáčavoisť [a]D 20 +48,8° po' době 5 min. a +86,0° po době 17 hod. (c = 1,25; voda).To a cooled solution (5 ° C) of methyl-3-, 4-O-isopropylidene, na-D-galactopyranoside (2 g) in anhydrous 1,2-dimethoxyethane (20 ml) was added sodium hydride in small portions (20 ml). 0.85 g) and the mixture was stirred at 20 ° C for 2 h. Methyl iodine d (4 ml) was then added and the reaction was monitored by thin layer chromatography on silica gel (chloroform / acetone 9: 2). After 15 hours, methylation is complete, water (15 ml) is added to the reaction mixture, the solution is evaporated to a small volume of 15 kPa (15 ml) and shaken four times between chloroform (20 ml) and water (15 ml). methyl 3,4-O-isopropyl-2,6-di-O-meityla-D-galactopyranoside (2.1 g, 92%) was obtained, which was hydrolyzed with 5% by weight aqueous solution of hydrochloric acid. 30 ml) under a dark bulb at 100 ° C for 3 hours. The reaction mixture is neutralized with a trimethylammonium methyl functional ion exchanger (Amberlite IRA-402 wash, 0.3-1.5 mm), preG filtered and evaporated at 5 kPa. The syrup was dissolved in ethyl acetate (40 ml) at 65 ° C and 2,6-di-O-methyl-D-galactose (0.9 g, 53%) crystallized upon cooling to -5 ° C, which is separated by suction of the mother liquor on a frit (Si), the filtrate is concentrated at a pressure of 5 kPa and crystallized to give further 2,6-di-O-methyl-D-gaia The total yield of the crystalline substance is 1.4 g, i.e. 82%. 2,6-di-O-methyl-D-galactose has a melting point of 127 DEG -128 DEG C. and an optical rotation of [.alpha.] D @ 20 + 48.8 DEG for 5 min. and + 86.0 ° after 17 hours. (c = 1.25; water).
Metyl-3,4-0-izopropy]idén-a-D-galaktopyranozid má široké použitie ako medziprodukt pri chemických syntézách biologicky aiktívnych di- a oligosacharidov akoi například 2-O-a-L-fukoipyranozyl-D-galáktózy, 6-0-(S-D-galaktopyranozyl-D-galáktózy, N-acetylovamej 6-0-/3-D-glukopyranozylamín-D-galaiktózy, 2,6-dl-O-metyl-D-galakitózy, připadne dalších derivátov. V našom případe sme ho využili na přípravu 2,6-di-O-metyl-0-gala'któzy, doležitej látky pri určovaní štruik túry polysachar idov.Methyl-3,4-O-isopropylidene-α-D-galactopyranoside is widely used as an intermediate in the chemical synthesis of biologically aictive di- and oligosaccharides such as 2-OaL-fucoipyranosyl-D-galactose, 6-O- (SD-galactopyranosyl- D-galactose, N-acetyl-6-O- / 3-D-glucopyranosylamine-D-galactose, 2,6-dl-O-methyl-D-galakitose, or other derivatives, in our case we used it to prepare 2, 6-di-O-methyl-O-galactose, an important substance in the determination of the polysaccharide trekking.
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