CS224998B1

CS224998B1 - The preparation of 1-deoxy-1-nitro-d-gulithole and 1-deoxy-1-nitro-d-iditol

Info

Publication number: CS224998B1
Application number: CS722382A
Authority: CS
Inventors: Jozef Ing Kubala; Jan Ing Caplovic; Jozef Ing Svec
Original assignee: Kubala Jozef; Caplovic Jan; Svec Jozef
Priority date: 1982-10-11
Filing date: 1982-10-11
Publication date: 1984-02-13

Description

Vynález sa týká sposobu přípravy 1-deoxy-l-nitro-D-gulitolu a 1-deoxy-l-nitro-D-iditolu.The invention relates to a process for the preparation of 1-deoxy-1-nitro-D-gulitol and 1-deoxy-1-nitro-D-iditol.

1-deoxy-l-nitroalditoly připravili nitrometenovou syntézou [ J.C.Sowden, H.O.L.Fischer: J.Am.Chem.Soc. 67, 1713 (1945) J.C.Sowden: Adv.Carbohyd.Chem. 6, 291 (1951), J.C.Sowden: Carbohyd.Chem· Vol, I. 132 (1962) 7, ^*H,H.Baer: Carbohyd.Chem. Biochem. 24,67 (1969)J, pósobením nitrometanu a metylátu sodného na D-xylózu připravil zmes sodných solí 1-deoxy-l-nitro-D-gulitolu a 1-deoxy-l-nitro-D-iditolu, ktorú po rozpuštění vo vodě deionizoval a získal 45 až .50 % výtažok 1-deoxy-l-nitro-D-gulitolu a 1-deoxy-l-nitro-D-iditolu. Podía nášho zistenia sodné soli 1-deoxy-l-nitro-D-gulitolu a 1-deoxy-l-nitro-D-iditolu sa hydrolyzujú vodou na D-xylózu, čím sa stažuje kryštalizácia a znižuje výtažok 1-deoxy-l-nitro-P-gulitolu a 1-deoxy-1-nitro-D-iditolu.1-Deoxy-1-nitroalditols were prepared by nitromethene synthesis [J.C.Sowden, H.O.L.Fischer: J.Am.Chem.Soc. 67, 1713 (1945) J.C.Sowden: Adv.Carbohyd.Chem. 6, 291 (1951), J.C.Sowden: Carbohyd.Chem. Vol., I. 132 (1962) 7, 1H, H. Baer: Carbohyd.Chem. Biochem. 24.67 (1969) by treating N-xylose with nitromethane and sodium methylate to prepare a mixture of sodium salts of 1-deoxy-1-nitro-D-gulitol and 1-deoxy-1-nitro-D-iditol, which when dissolved in water deionized and obtained a 45-50% yield of 1-deoxy-1-nitro-D-gulitol and 1-deoxy-1-nitro-D-iditol. According to our findings, the sodium salts of 1-deoxy-1-nitro-D-gulitol and 1-deoxy-1-nitro-D-iditol are hydrolyzed with water to D-xylose, thereby precipitating crystallization and reducing the yield of 1-deoxy-1-nitro -Β-gulitol and 1-deoxy-1-nitro-D-iditol.

Uvedené nevýhody v podstsitnej miere odstraňuje sposob přípravy 1-deoxy-l-nitro-D-gulitolu a 1-deoxy-l-nitro-D-iditolu podía vynálezu, ktorého podstata spočívá v tom, že sa sodné soli 1-deoxy-l-nitro-N-gulitolu a 1-deoxy-l-nitro-L-iditolu před deionizáciou rozpustia v zriedenej kyselině octovéj. Roztok sa podrobí deionizácii cez vymieňač katiónov a zahustí na sirup.The above-mentioned disadvantages are substantially eliminated by the process of preparing 1-deoxy-1-nitro-D-gulitol and 1-deoxy-1-nitro-D-iditol according to the invention, which consists in the fact that the sodium salts of 1-deoxy-1- nitro-N-gulitol and 1-deoxy-1-nitro-L-iditol are dissolved in dilute acetic acid prior to deionization. The solution is deionized through a cation exchanger and concentrated to a syrup.

Výhodou navrhovaného spósobu přípravy .1-deoxy-l-nitro-Ngulitolu a 1-deoxy-l-nitro-D-iditolu oproti doterajším postupom přípravy je, že předmětný sposob je hospodárnější lebo dává až 84 % výtažky 1-deoxy-l-nitro-D-gulitolu a 1-deoxy-l-nitro-Diditolu.The advantage of the proposed process for the preparation of 1-deoxy-1-nitro-N-gulitol and 1-deoxy-1-nitro-D-iditol over the prior art processes is that the present process is more economical since it yields up to 84% 1-deoxy-1-nitro yield. -D-gulitol and 1-deoxy-1-nitro-Diditol.

Příklad 1Example 1

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Zmes D-xylózy /150 g/ sa mieša v sulfonačnej barnve, Kuorá je opatřená chladičom, chlorkalciovým uzáverom s roztokom metylátu sodného /připraveného rozpuštěním/31,5 g/ sodíka v 1350 ml metylalkoholu a s nitrometanom /540 ml/ pri 20°C po dobu l2 h. Vylúčené sodné soli 1-deoxy-l-nitro-D-gulitol a 1deoxy-l-nitro-D-iditol sa odfiltrujú na frite Sla premyjúThe mixture of D-xylose (150 g) is stirred in a sulphonation dye, Kuorá is equipped with a condenser, a chloro-calcium cap with a solution of sodium methylate (prepared by dissolution) (31.5 g) sodium in 1350 ml of methanol and nitromethane (540 ml) at 20 ° C. l2 h. The precipitated sodium salts of 1-deoxy-1-nitro-D-gulitol and 1-deoxy-1-nitro-D-iditol are filtered off on a frit S1 and washed.

I metylalkoholom /250 ml/ a rozpustia sa v 10 % kyselině octovéj /2θ00 ml/. Roztok sa deionizuje cez kolonu vymieňača kationov o rozmeroch s dížkou 60 cm a priemerom 4 cm. Eluát z kolony sa vákuovo zahustí a lyofilizuje. Získá m/l75,l g/zmesi 1-deoxy-1-nitro-D-gulitol a l-deoxy-l-nitro-D4iditol v 84 % výtažku.I with methanol (250 ml) and dissolved in 10% acetic acid (200 ml). The solution is deionized through a cation exchanger column having a length of 60 cm and a diameter of 4 cm. The eluate from the column is concentrated in vacuo and lyophilized. There was obtained m / 17.1 g / mixture of 1-deoxy-1-nitro-D-gulitol and 1-deoxy-1-nitro-D4iditol in 84% yield.

Vynález má rozsiahle využitie pri príprave 1-deoxy-l-nitro-D-gulitolu a 1-deoxy-l-nitro-E-iditolu, ktoré sú medzi produktami pri príprave ťažko dostupných vzácných sacharidov D-gulózy a D-idózy. '^ieto látky sa používajú v medicíně a pri štúdiu biochemických pochodov.The invention has extensive application in the preparation of 1-deoxy-1-nitro-D-gulitol and 1-deoxy-1-nitro-E-iditol, which are among the products in the preparation of the scarce D-cellulose and D-idose rare carbohydrates. These substances are used in medicine and in the study of biochemical processes.

Claims

Process for the preparation of 1-deoxy-1-nitro-D-gulitol and 1-deoxy-1-nitro-D-iditol from D-xylose by nitromethane synthesis, characterized in that their sodium salts are dissolved in dilute acetic acid percolated through a cation exchanger concentrate in vacuo and lyophilize.

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