Water-soluble carboxymethylcellulose derivatives of cellulose and method of production thereof

 

(57) Abstract:

The invention relates to new biologically active derivative of cellulose and methods of producing cellulose derivatives. Water-soluble carboxymethylcellulose derivatives of cellulose (VCAPS) with the General formula of elementary link6H8-xABOUT5-y-(NR)y(CH2COOH)xwhere x >of 0.13, y>0, x+y<3, produced by interaction of oxycellulose containing oxidized groups of no more than 20%, soluble in water or organic solvents by aminoguanidinium General formula NH2-R, where R is the residue of the amino compounds selected from the group consisting of 5-amino-1,2,4-triazole, -aminopyridine, aminobenzoyl, -amino amber acid, to obtain the azomethine derivatives and subsequent carboxyethylgermanium. Also described is a method of obtaining VCAPS. The technical result consists in the fact that the method allows to obtain water-soluble biologically active derivatives of cellulose with a degree of substitution of the bases 5-6, and carboxymethyl about 14. 2 S. p. f-crystals, 1 table.

The invention relates to new derivatives of cellulose and methods of producing cellulose derivatives.

Known 2,3-disintegration-cellulose and pic is Savoy pulp periodates sodium, with the subsequent interaction of dialdehydes with aminoguanidinium (5-amino-1,10-phenanthroline) [BGN 24123, A, C 08 B 15/06, publ. 10.01.78].

Known 2,3-di-(5-Azino-1,3,4-triazole)-cellulose and method of reception [BG N 24468, A, C 08 B 15/06, publ. 10.03.78].

The basis of this method is also expected to interact dialdehydes with nitrogenous heterocyclic amines. Valdecaballeros received controllable periodic destruction by oxidation of powdered cellulose.

The main purpose of obtaining the above compounds is to obtain nitrogen-containing cellulose derivatives having biological activity. However, the expression of biologically active properties of these compounds is difficult because they are insoluble in water and organic solvents.

The present invention is the extension of a number of cellulose derivatives having biological activity, and obtaining water-soluble biologically active derivatives of cellulose, for which the effect of modifying cellulose biologically active compounds will be more pronounced.

This is achieved with new water-soluble carboxymethylcellulose derived cellulose (VCAPS) and storemyr in water or organic solvents by aminoguanidinium General formula NH2-R, where R is the residue of the amino compounds selected from the group consisting of 5-amino-1,2,4-triazole, - -aminopyridine, aminobenzoyl, - amino amber acid, to obtain the azomethine derivatives and subsequent carboxyethylgermanium by processing monochloracetic acid.

This is a new technical result, which is in causal connection with the essential features of the invention.

The essential features of the invention

Water-soluble carboxymethylcellulose cellulose derivatives with the General formula of elementary-level C6H8-xO5-y(NR)y(CH2COOH)xwhere x>of 0.13, y>0, x+y<3, obtained by the interaction of oxycellulose containing oxidized groups of no more than 20% soluble in water or organic solvents by aminoguanidinium General formula NN2-R, where R is the residue of the amino compounds selected from the group including: 5-amino-1,2,4-triazole, -aminopyridine, aminobenzoyl, -amino amber acid, to obtain the azomethine derivatives and subsequent carboxyethylgermanium by processing monochloracetic acid.

The method of obtaining water-soluble carboxymethylamino compounds is in the interaction oxie 3 h at a ratio of 1 mol of amino compounds on 1 mol of the aldehyde groups of the cellulose with the following carboxyethylgermanium by processing monochloracetic acid.

Analogues VCAPS currently not identified.

Scheme for vodorastvorimogo carboxymethylamino derived cellulose

< / BR>
where x>0,13, because this restriction is the condition of the water solubility of the resulting compounds; y>0, x+y<3, R is a residue of amino compounds selected from the group consisting of 5 - amino-1,2,4-triazole, -aminopyridine, aminobenzoyl, -amino amber acid.

The oxidation of hydroxyl groups of cellulose to aldehyde is conducted in various ways: by ozonation [Demin C. A., Sharesave centuries, Osipova, I., Kabalnov N. N. The depolymerization of cellulose in the ozonation // Ukr. go active. chemistry - 1993. - T. 66, vol. 11. - S. 2562-2567], controllable periodic destruction by oxidation to dialdehydes or by oxidation with bichromate, potassium permanganate, nitrogen dioxide and other oxidants [Practical work in chemistry of wood and cellulose / Obolenskaya A. C., Shchegolev C. P., Mayor, L., Mayor E. L., Kossovich N. L., Emelyanova, I. H. - M.: Forest industry. - 1965. - 412 c.].

All these methods of oxidation of the cellulose yield of oxycellulose containing not more than 20% of oxidized groups and this allows karboksimetilirovaniya azomethine derivatives.

Carboxylat.In., Shchegolev C. P., Mayor, L., Mayor E. L., Kossovich N. L., Emelyanova, I. H. - M.: Forest industry. - 1965. - 412 S. ] by processing monochloracetic acid-azomethine derivative of cellulose. Characteristics of the obtained products are shown in the table.

There were experiments on the production of mixed esters of cellulose with a different order of operations: the interaction of amino compounds with preexisting carboxymethylcellulose. However, the resulting products had a very low degree of substitution (Sz) bases (PL., PP 5 and 6).

VCAPS obtained as follows.

Powdered cellulose production Kaysk PPM with a degree of polymerization 255-270 viscosity in catocene treated with bichromate of potash in the acidic environment [Rogovin H. A. , galbraikh HP Chemical transformations and modification of cellulose. M. : Chemistry. - 1979. - 206 S.]. Processing of cellulose is carried out in 1% aqueous solution of nitric acid when heated to 90-100oC with vigorous stirring for 1 h the Bichromate of potash take the rate of 3 mol/mol of cellulose. The resulting product is washed on a glass filter with distilled water, then with alcohol (ethanol), dried at 50-60oC and analysed. The content of carbonyl golensky A. C., Shchegolev C. P. , Mayor, L., Mayor E. L., Kossovich N. L., Emelyanova, I. H. - M.: Forest industry. - 1965. - 412 S.].

Azomethine derivatives of cellulose obtained as follows. Into a solution of amino compounds when heated to 97-100oC add powdered preparation of oxidized cellulose in the ratio of 1 mol of amino compounds on 1 mol of the aldehyde (carbonyl) groups. The process is conducted by heating and vigorous stirring for 3 hours Identification of patterns of the final products and the degree of substitution by the bases performed according to IR-spectroscopy and elemental analysis.

Karboksimetilirovaniya carried out by treatment with monochloracetic acid. The degree of substitution on carboxymethyl groups is determined on the basis of the functional analysis of COOH-groups according to the method of Wilson.

The degree of substitution of the obtained cellulose ethers are given in the table.

Example 1

In a three-neck round bottom flask equipped with a thermometer, mechanical stirrer and reflux condenser, is dissolved in the calculated amount of water at a temperature of 60-70oC hitch 5-amino - 1,2,4-triazole. The solution is heated up to 97-100oC and add to it the powdered drug MCC is padou water bath and hold the exposure of the reaction mixture with vigorous stirring for 3 hours After aging the resulting product is filtered through a cloth filter on a Buechner funnel from the hot solution, which has not entered into cooperation with the ICC 5-amino-1,2,4-triazole, and repeatedly washed in a beaker with stirring, warm (50-60oC) water to the lack of traces of 5-amino-1,2,4-triazole. The product is dried at a temperature of 102-104oC to constant weight and analyzed.

To button 5 g of the synthesized 5-amino-1,2,4-triazolinone in 100 ml of isopropyl alcohol under stirring slowly for 30 minutes add 15 ml of 30% aqueous sodium hydroxide solution at room temperature. Then the mixture is intensively stirred for further 1 h, and then gradually over 30 min add 6 g of monochloracetic acid. The mixture was incubated for 3.5 hours at a temperature of 50-55oC. the Liquid is decanted, and the derivative of cellulose is stirred with 100 ml of 70% methyl alcohol. Then the liquid is again decanted, the product is washed on a glass filter absolute methyl alcohol, dried at a temperature of 45-50oC and analyzed (Table, p. 1).

Getting VCAPS on PP 2-4 table differs only used by aminoguanidinium.

The reduction degree for the azomethines by heating in an acidic environment. Heating at temperatures up to 100oC leads to the complete hydrolysis of Schiff bases, but relatively mild conditions karboksimetilirovaniya (temperature 50-55oC) only lead to partial hydrolysis of azomethines.

As follows from the data presented in the table, the sequential reactions of condensation of amino compounds with carbonyl groups of the cellulose allows to obtain a water-soluble derivative of cellulose with a degree of substitution of the bases 5-6, and carboxymethyl about 14. It is known that the carboxymethyl cellulose having Sz>10-13 (i.e., more than 0.1 to 0.13 carboxymethyl group at one elementary link) is a water-soluble substance. Solubility obtained VCAPS check filtration of 0.1% aqueous solution through a glass filter # 1. The insoluble fraction was 0.5-1% by weight of the synthesized compounds.

1. Water-soluble carboxymethylcellulose cellulose derivatives with the General formula of elementary link

WITH6H8-xABOUT5-y-(NR)y(CH2COOH)x,

where x>of 0.13, y>0, x+y<3
to obtain the azomethine derivatives and subsequent carboxyethylgermanium by processing monochloracetic acid.

2. The method of obtaining compounds on p. 1 interaction of oxycellulose containing oxidized groups of no more than 20%, with aminoguanidinium at a temperature of 97 - 100oC for 3 h at a ratio of 1 mol of amino compounds on 1 mol of the aldehyde groups of the cellulose and the subsequent carboxyethylgermanium by processing monochloracetic acid.

 

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