CS224908B1 - The o-/2-oxoethyl/ cellulose and the method of its preparation - Google Patents

Description

The invention relates to the preparation of a new type of aldehyde derivative of oelulose O- (2-oxoethyl) cellulose by the base catalyzed elimination of nitromethane from O- (3-nitro-2-hydroxypropyl) cellulose derived from O- (3-iodo-2-hydroxypropyl) oelulose substitution of iodine with nitro by the action of an alkali nitrite.

The most accessible aldehyde cellulose derivative is 2,3-dialdehyde cellulose, which is prepared by periodate oxidation of oellulose / evel · Ρ · Not; Methods Carbohyd Chem. 3 »164 (1963)

However, if the process is applied to macroporous spherical cellulose from a certain relatively low degree of oxidation, its spherical shape is destroyed. elevated temperature, Hamuro, Jap., Patent 75 54, 684, C, A, 83, 166, 084 (1975 V or by photolysis of 6-azido-6-deoxyoellulose in a mixture of 2-methoxyethanol and benzene, followed by hydrolysis of 6- aldimino-6-deoxyoeluloses in weakly acidic environment / b »Horton> AELuetzow and O.Theander. 'Carbohyd · Res ·

26, 1 (1973 λ7 · 6-Aldehydo-2,3,3-di-O-phenylcarbamoylcellulose) was prepared by reacting a mixture of dioylchexylcarbodiimide »pyridinium triohorooroacetate and dry dimethylsulfoxide or a mixture of phosphorus pentoxide and dry dimethylsulfoxide to 2» 3-di- J224 908 moylcellulose / ZIKuzneoova, Izv * Akad * Nauk USSR, Ser Chimilil, 1979 ^ Reaction of 4-isothiocyanate-benzaldehyde with cellulose amino derivatives prepared benzaldehyde cellulose derivatives (V.Marko, P.Geraeiner, A. Breier and M. .Uher, PV 9364-81) · The proposed process extends the range of cellulose derivatives containing aldehyde groups ·

SUMMARY OF THE INVENTION The present invention is characterized in that the starting O- (3-iodo-2-hydroxypropyl) cellulose is converted in the first step by treatment with an alkali nitrite, preferably sodium nitrite, in an organic solvent, preferably dimethylformamide in the presence of a polyhydric phenol, preferably floroglucine. to O- (3-nitro-2-hydroxypropyl) cellulose, which after isolation, preferably by filtering the solid phase from the reaction mixture diluted with water and washing it with methanol, acetone and water, is reacted in a second step in an alkaline aqueous solution, preferably in sodium hydroxide solution under nitrogen * The resulting O- (2-oxoethyl) cellulose is isolated from the reaction mixture preferably by filtering off the solid phase and washing it with water until neutral.

The advantage of the proposed process for the preparation of O- (2-oxoethyl) oellulose is that it does not cause unwanted changes in the physical properties of cellulose * This advantage is particularly important when applying the process to spherical macroporous cellulose which retains spherical particle shape in the final product and pores of starting material * The advantage of O- (2-oxoethyl) cellulose compared to the previously prepared aldehyde cellulose derivatives is that it contains more accessible aldehyde groups in the side chain stiffened to the basic anhydroglucose retazeo cellulose through oxamethylene

A further advantage of said process for preparing O- (2-oxoethyl) cellulose is that from the intermediate, O- (3-nitro-2-dihydroxypropyl) cellulose, which can be stored for a longer period of time, the desired aldehyde derivative may be desired. loose just before use ·

The starting O- (3-iodo-2-hydroxypropyl) cellulose is an accessible cellulose derivative (L.Petruš and P. Gemeiner, PV 8653-81). The nitro-iodine substitution has been applied in the preparation of methyl-2,3,4- tri-O-acetyl-6-deoxy-6-nitro-o-D-glucopyranoside or 2,3,4,5-di-O-benzylidene-1,6-dideoxy-1,6-dinitro-D-raanitol from the corresponding iodo derivatives (J.M. Sugihara, W.J.Teerlink, R.MacLeod, S.M. Dorrenee and C.H. Springer, J. · Org., Chem., 28, 2079 (1963)) · Base-catalyzed decomposition of οέ-hydroxynitroalkanes into Aldehyde lower by one carbon per ellmine of nitromethane molecule represents a new approach to nitromethane synthesis by using its reversibility ·

Example 1

O- (3-Nitro-2-hydroxypropyl) oelulose · Spherical O- (3-iodo-2-hydroxypropyl) cellulose (2.5 g, 19.5% dry matter, 17.4% iodine, degree of substitution with iodohydropropyl groups 0, 30) and washed with methanol (3 x 5 ml) and dimethylformamide (3 x 5 ml). To the aspirated O- (3-iodo-2-hydroxypropyl) oelulose were added dimethylformamide (10 ml), sodium nitrite (1 g) and florogluoin dihydrate (1, 5 g) and the mixture was slowly stirred at room temperature in a sealed vessel under nitrogen for 48 hours. Then water (20 ml) was added to the reaction mixture, after stirring the solid phase was filtered and washed with methanol, acetone (both 5 x 10 ml) and water to a negative reaction

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224 908 nitrite · Light brown spherical O- (3-nitro-2-hydroxypropyl) cellulose (2.4 g, 16.8% dry matter, 0.8% nitrogen, 0.8% iodine, degree of substitution by nitrohydroxypropyl groups 0) , 10) · In the infrared spectrum of the prepared O- (3-nitro-2-hydroxypropyl) eelulose, characteristic bands are present for the aliphatic nitro group at 1382 and 1550 cm ^{@ -1} .

O- (2-0xoethyl) eelulose · A mixture of aspirated spherical O- (3-nitro-2-hydroxypropyl) oelulose (2 g) and 1 M aqueous sodium hydroxide solution (10 ml) was slowly stirred at room temperature under nitrogen for 1 hour · The solid phase was filtered and washed with water until neutral. · White spherical O- (2-oxoethyl) cellulose (1.9 g, 15.0% dry matter, 0.3% nitrogen) insoluble in water and common organic solvents was obtained. reactions typical of aliphatic aldehydes and cellulose · It is stored in the form of an intermediate, O- (3-nitro-2-hydroxypropyl) oelulose, from which it is released just before use ·

Determination of aldehyde groups in O- (2-oxoethyl) cellulose. The aspirated spherical O- (2-oxoethyl) cellulose (0.3 g) was washed with ethanol (5 x 2 ml) and after suction was heated, with a mixture of ethanol (5 ml) and 4-nitrophenylhydrazine (0.1 g) at temperature 80 ° C for 4 hours · The solid phase was filtered and extracted with acetone · 4-nitrophenylhydrazone O- (2-oxoethyl) cellulose was obtained as red-brown beads containing 2.0% nitrogen, which after deduction of residual nitrogen in the aldehyde derivative corresponds to the degree of substitution 2-oxoethyl groups of 0.07, i prepared spherical O- (2-oxoethyl) cellulose contains 70 mmol of aldehyde groups per mole of anhydroglucose units ·

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The invention has utility in the preparation of activated matrices for the covalent binding of bioohemicals with application in all areas of enzyme engineering and in organic synthesis in the preparation of polymeric reagents.

Claims (2)

1. O- (2-0xoethyl) oeluloza of formula, R-O-CHg-CH 2 O, wherein R represents cellulose · 2. A process according to claim 1, characterized in that the starting O- (3-iodo-2-hydroxypropyl) oellulose is first treated with a solution of an alkaline nitrite, preferably sodium nitrite, in an organic solvent, preferably dimethylformamide, in the presence of phenol, preferably floroglucine at room temperature for 40 to 50 hours at a 5 to 25 molar excess of nitrite and floroglucine per bound iodine, with the intermediate, O- (3-nitro-2-hydroxypropyl) cellulose, preferably isolated after cooling the reaction mixture with water, filtering off the solid phase and washing it; methanol, acetic acid and water to give a negative reaction to nitrites in the second step are treated with an alkaline aqueous solution, preferably 1 M sodium hydroxide solution at room temperature under nitrogen for 0.5 to 2 hours to give 0- (2- cellulose, which is preferably isolated from the reaction mixture by filtration and washing the solid phase with water to a neutral reaction;