CS224904B1 - The preparation of the 1-deoxy-nitro-d-talitol and the 1-deoxy-1-nitro-d-galactitole - Google Patents

The preparation of the 1-deoxy-nitro-d-talitol and the 1-deoxy-1-nitro-d-galactitole Download PDF

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CS224904B1
CS224904B1 CS476382A CS476382A CS224904B1 CS 224904 B1 CS224904 B1 CS 224904B1 CS 476382 A CS476382 A CS 476382A CS 476382 A CS476382 A CS 476382A CS 224904 B1 CS224904 B1 CS 224904B1
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Czechoslovakia
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deoxy
nitro
talitol
preparation
galactitol
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CS476382A
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Czech (cs)
Slovak (sk)
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Jozef Ing Kubala
Jan Ing Caplovic
Jozef Ing Svec
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Kubala Jozef
Caplovic Jan
Svec Jozef
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Priority to CS476382A priority Critical patent/CS224904B1/en
Publication of CS224904B1 publication Critical patent/CS224904B1/en

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Description

Vynález sa týká spósobu přípravy 1-deoxy-l-nitro-L-talitolu a 1-deoxy-l-nitro-L-galaktitolu z L-lyxózy.The invention relates to a process for the preparation of 1-deoxy-1-nitro-L-talitol and 1-deoxy-1-nitro-L-galactitol from L-lyxose.

Příprava l-deoxy-l-nitro-alditolov sa uskutočňuje pomocou nitrometanovej syntézy. Táto sa prevádza tak, že sa pósoZ bí nitrometénom a metylátom sodným na aldozu kratšiu o jeden uhlíkový atom. Vzniká zmes sodných solí dvoch epimérnych 1-deoxy-l-nitro-alditoloV. Táto zmes sa rozpustí vo vodě a roztok sa zbaví sodných iónov na koloně vymieňača katiónov eluát z kolony sa zahustí a z alkoholického roztoku sa získajú krystalické látky 45 až 50& výtažku. /J.C.Sowden, H.O.L. Fischer, J.Am.Chem.Soc. 67,1963/1947^ Této reakcia bola niekoTkokrát preskúraaná za účelom zvýšenia výťažnosti produktov ale bez úspěchu. ,/H.H.Baer, Adv. Carbohyd.Chem.Biochem. 24, /1969/; J.C.Sowden, Adv.Carbohyd.Chem. 6, 291 /1951^The preparation of 1-deoxy-1-nitro-alditols is carried out by nitromethane synthesis. This is accomplished by beating nitromethene and sodium methylate to an aldose shorter by one carbon atom. A mixture of sodium salts of two epimeric 1-deoxy-1-nitro-alditol was formed. This mixture was dissolved in water and the solution was freed of sodium ions on a cation exchange column and the eluate from the column was concentrated and crystalline 45-50% yield was obtained from the alcoholic solution. /J.C.Sowden, H.O.L. Fischer, J. Am. This reaction was reviewed several times to increase the yield of the products but without success. , H. H. Baer, Adv. Carbohyd.Chem.Biochem. 24 (1969); J.C.Sowden, Adv.Carbohyd.Chem. 6, 291 (1951)

Zistili sme, že sodné soli 1-deoxy-l-nitró-L-talitol a 1-deoxy-l-nitro-L-galaktitol sa vo vodnom roztoku rozkladajú za vzniku L-lyxózy. Tento rozklad začne prebiehať akonáhle sa sodné soli rozpustia vo vodě a trvá pokial* celé množstvo roztoku nepretečie cez ionexovú kolonu. Vzniklá nižšia aldóza /L-lyxóza/, zťažuje kryštalizáciu a samozřejmé znižuje výtažnosť reakcie. Uvedení autoři pokládali přítomnost L-lyxózy za nezřeagováný zbytok východzej látky. Navrhovaný spósob prí pravý 1-deoxy-l-nitro-L-talitolu a 1-deoxy-l-nitro-L-galakti/ ř tolu zabraňuje uvoTneniu L-lyxozy a podstatné zvýši výtažnosť produktov, ktoré sú medziproduktami pri príprave L-talózy a L-galaktózy.We have found that the sodium salts of 1-deoxy-1-nitro-L-talitol and 1-deoxy-1-nitro-L-galactitol decompose in aqueous solution to form L-lyxose. This decomposition begins as soon as the sodium salts have dissolved in water and continue until the entire amount of solution has passed through the ion exchange column. The resulting lower aldose (L-lyxose) hinders crystallization and, of course, reduces the yield of the reaction. These authors considered the presence of L-lyxose as an unreacted residue of the starting material. The proposed manner at right 1-deoxy-L-nitro-L-talitolu and 1-deoxy-L-nitro-L-galacto / R Tolu prevents uvoTneniu L-lyxose and significantly increases the yield of products, which are intermediates in the preparation of L-talose and L-galactose.

Podstata vynálezu je, že sa zabráni rozkladu sodných solí 1-deoxy-l-nitro-L-talitolu a 1-deoxy-l-nitro-L-galaktitolu na L-lyxózu tak, že sa sodné soli před deionizáciou rozpustia v zriedenej kyselině octovej. Tento roztok sa podrobí deionizécii cez vymieňač katiónov. Po zahuštění eluétu z kolony io-Jj224 904 nexu vykrystalizuje zmes 1-deoxy-l-nitro-L-talitolu a 1-deoxy-1-nitro-L-galaktitolu okolo 70 %, pričom neobsahuje žiadnu východziu L-lyxózu.The principle of the invention is to prevent the decomposition of the sodium salts of 1-deoxy-1-nitro-L-talitol and 1-deoxy-1-nitro-L-galactitol into L-lyxose by dissolving the sodium salts in dilute acetic acid prior to deionization . This solution is subjected to deionization through a cation exchanger. After concentrating the eluate from the io-J224 904 nex column, a mixture of 1-deoxy-1-nitro-L-talitol and 1-deoxy-1-nitro-L-galactitol crystallized to about 70%, containing no starting L-lyxose.

Výhodou navrhovaného spósobu přípravy 1-deoxy-l-nitro-L-talitolu a 1-deoxy-l-nitro-L-galaktitolu je lepšia kryštalizácia nových produktov. Vzniklá reakčná zmes neobsahuje L-lyxózu, čím odpadne proces jej izolácie. Poskytuje přípravu výrobku o vysokej čistotě a výtažku, čím sa zlacňuje spósob přípravy.The advantage of the proposed process for the preparation of 1-deoxy-1-nitro-L-talitol and 1-deoxy-1-nitro-L-galactitol is that the new products are better crystallized. The resulting reaction mixture does not contain L-lyxose, thereby eliminating the process of isolation. It provides the preparation of a high purity product and an extract, thereby reducing the cost of preparation.

Příklad 1Example 1

Zmes L-lyxózy /50 g/ sa mieša s roztokom metylátu sodného připraveného rozpuštěním /10,5 g/ sodíka /450 g/ metylalkoholu a s nitrometanom /180 g/ pri 20°C po dobu 16 hodin. Vylúčené sodné soli 1-deoxy-l-nitro-L-talitolu a 1-deoxy-l-nitro-L-galaktitolu áa odfiltruji!, premyjú raetylalkohom /100 ml/ a rozpustia v 10% kyselina octovéj /650 ml/. Roztok sa deionizuje cez kolonu naplnenú ionexom /vymienačoa katiónov/ o rozmeroch kolony dížky 60 a priemeru 4 centimetre. Eluát z kolony sa zahustí na kašovitý zvyšok, ktorý sa rozpustí za varu v 96% etylalkohole /200 ml/. Po ochladení roztoku na 0°C vykryštalizuje 39 g zmesi 1-deoxy-l-nitro-L-talitolu a 1-deoxy-l-nitro-L-galaktitolu. Po dalšej kryštalizácii matečného lúhu sa zíaka dalších 10 g produktu. Celkove sa získalo 49 g zmesi 1-deoxy-l-nitro-L-talitolu a 1-deoxy-l-nitro -L-galaktitolu, ktoré neobsahovali žiadnu L-lyxózu. Výťažok na L-lyxózu je 70%.The mixture of L-lyxose (50 g) is mixed with a solution of sodium methylate prepared by dissolving (10.5 g) sodium (450 g) methanol and nitromethane (180 g) at 20 ° C for 16 hours. The precipitated sodium salts of 1-deoxy-1-nitro-L-talitol and 1-deoxy-1-nitro-L-galactitol are filtered, washed with diethyl alcohol (100 ml) and dissolved in 10% acetic acid (650 ml). The solution is deionized through a column packed with an ion exchange resin (cation exchanger) having a column size of length 60 and a diameter of 4 centimeters. The eluate from the column is concentrated to a slurry which is dissolved in boiling in 96% ethyl alcohol (200 ml). After cooling the solution to 0 ° C, 39 g of a mixture of 1-deoxy-1-nitro-L-talitol and 1-deoxy-1-nitro-L-galactitol crystallize. After further crystallization of the mother liquor, an additional 10 g of product is collected. In total, 49 g of a mixture of 1-deoxy-1-nitro-L-talitol and 1-deoxy-1-nitro-L-galactitol were obtained which contained no L-lyxose. The yield on L-lyxose is 70%.

Vynález má rozsiahle využitie pri přípravě 1-deoxy-l-nitro-Ltalitolu a l-deoxy-l-nitro-L-galaktitolu, ktoré sú medziproduktom pri príprave L-talózy, L-galaktózy, ktoré sa používajú' pri štúdiu biochemických pochodov a v medecíne.The invention has extensive application in the preparation of 1-deoxy-1-nitro-L -talitol and 1-deoxy-1-nitro-L-galactitol, which are intermediates in the preparation of L-talose, L-galactose, used in the study of biochemical processes and medecine.

Claims (1)

-ύPREDMET VYNÁLEZUINVENTION OF THE INVENTION 224 904224 904 Spósob přípravy 1-deoxy-l-nitro-L-talitolu a 1-deoxy-1-nitro-L-galaktitolu z L-lyxózy sa vyznačuje tým, že sa zabráni uvoTňovaniu L-lyxózy tak, že sa sodné soli 1-deoxy-1-nitro-L-talitolu a 1-deoxy-l-nitro-L-galaktitolu rozpustia v kyselině octovej a tento roztok sa podrobí deionizácii na vymieňači katiónov kde sa uvoTňia voTné 1-deoxy-l-nitro-L-talitol a 1-deoxy-l-nitro-L-galaktitol a kryštalizáciou sa získajú v 70 % výtažku·A process for the preparation of 1-deoxy-1-nitro-L-talitol and 1-deoxy-1-nitro-L-galactitol from L-lyxose is characterized by preventing the release of L-lyxose by treating the sodium salts of 1-deoxy- 1-nitro-L-talitol and 1-deoxy-1-nitro-L-galactitol are dissolved in acetic acid and this solution is deionized on a cation exchanger to release free 1-deoxy-1-nitro-L-talitol and 1- deoxy-1-nitro-L-galactitol and crystallization are obtained in 70% yield · Cena: 2,40 KčsPrice: 2,40 Kčs Vytiskly Moravské tiskařské závody,Printed by Moravian Printing Works,
CS476382A 1982-06-25 1982-06-25 The preparation of the 1-deoxy-nitro-d-talitol and the 1-deoxy-1-nitro-d-galactitole CS224904B1 (en)

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