PL175563B1 - Novel salts of sulphates constituting derivatives of 1,3-dioxanes and method of obtaining them - Google Patents

Abstract

1. New sodium salts of sulfates of (57) 1,3-dioxane derivatives named cis-2-alkyl-5-hydroxy-1,3-dioxanes and general formula 1 or trans-2-alkyl-5-hydroxy-1,3-dioxanes and general formula 2, in which n is 7-13. 2. A method for preparing new sodium salts of cis- and/or trans-2-alkyl-5-hydroxy-1,3-dioxane derivatives of general formulae 1 and 2, where n is 7-13, characterized in that cis- and/or trans-2-alkyl-5-hydroxy-1,3-dioxanes of general formulae 3 and 4, where n has the meaning given above, in a solvent solution, preferably in the form of carbon tetrachloride with the addition of pyridine, are reacted with chlorosulfonic acid, then the solvent is evaporated and the residue is added to an alcoholic-aqueous solution of sodium hydroxide or sodium carbonate or sodium bicarbonate, the solvent is evaporated and the residue is purified.

Description

The subject of the invention is new sodium salts of 1,3-dioxane derivatives of sulfates named cis- and trans-2-alkyl-5-hydroxy-1,3-dioxanes and the general formulas shown in the figure by the formulas 1 and 2, respectively, in which n is 7-13.

The new salts show surface activity at interfaces and are intended for use as active ingredients of washing, wetting, foaming, emulsifying, washing, dispersing agents, alone or in mixtures with other surface-active substances, in products for household chemicals and the textile industry.

Alkyl sulfates obtained by the sulfation of long-chain aliphatic alcohols or by the addition of sulfuric acid to unsaturated hydrocarbons and then neutralization of the resulting alkyl sulfuric acids with generally available hydroxides or with gaseous ammonia, constitute one of the important groups of anionic surfactants with multiple practical applications, described in the monograph: WM Linfield (Ed.), Anionie Surfactants, Part I and II, M. Dekker Inc., New York, 1976.

U.S. Patent Nos. 3,949,460 and 3,948,953 describe ammonium salts of sulfates obtained from 5-membered acetals, 2-monosubstituted or 2,2-disubstituted 4-hydroxymethyl-1,3-dioxolanes used as hydrophobic intermediates. A production method is known from the Polish patent specification No. 162 441

175,563 surface-active sodium sulfates, obtained from 6-membered cyclic acetals: 2,5-disubstituted and 2,2,5-trisubstituted 5-hydroxymethyl-1,3-dioxanes used as hydrophobic intermediates.

The invention relates to new sodium salts of 1,3-dioxane derivatives of sulfates with the names cis- and trans-2-alkyl-5-hydroxy-1,3-dioxanes and the general formulas shown in the figure with formulas 1 and 2, respectively, in which n is 7- 13.

The invention also relates to a process for the preparation of new sodium sulfate salts of cis- and / or trans-2-alkyl-5-hydroxy-1,3-dioxane derivatives of general formulas 1 and 2 in which n is 7-13.

The essence of the invention consists in that cis- and / or trans-2-alkyl-5-hydroxy-1,3-dioxanes of general formulas 3 and 4, in which n is as defined above, in a solvent solution, preferably in the form of tetrachloride carbon with the addition of pyridine, reacted with chlorosulfonic acid, then the solvent was evaporated and the residue was taken up in an alcohol-water solution of sodium hydroxide or sodium carbonate or sodium bicarbonate, the solvent was evaporated and the residue was purified. It is preferred that the molar ratio of the 1,3-dioxane derivative or derivatives to chlorosulfonic acid to pyridine is in the range from 1: 1.1: 2.3 to 1: 1.2: 2.5.

The essence of the invention consists in the fact that cis- and / or trans-2-alkyl-5-hydroxy-1,3-dioxanes of general formulas 3 and 4, in which n is as defined above, in a solvent solution, preferably in the form of Carbon tetrachloride is reacted with sulfur trioxide, preferably in the form of a sulfur trioxide-pyridine complex, then the solvent is evaporated and the residue is taken up in an alcohol-water solution of sodium hydroxide or sodium carbonate or sodium bicarbonate, the solvent is evaporated and the residue is purified. It is preferred that the molar ratio of the 1,3-dioxane derivative or derivatives to the complex is from 1: 1.1 to 1: 1.2.

The main advantages of the invention are the production of anionic surfactants with high surface activity, the stability of the sulfates produced in a neutral environment and their susceptibility to hydrolysis in an acidic environment to products not showing surface activity, which makes the produced sulfates less harmful to the natural environment.

The main advantages of the process according to the invention are the easy availability of hydrophobic intermediates, obtained in particular from four-component mixtures of cis- and trans-2-alkyl-5-hydroxy-1,3-dioxanes and cis- and trans-2-alkyl-4-hydroxymethyl-1,3-dioxolanes , the ease of carrying out the sulfation reaction, the ease of obtaining sodium sulfate salts and the ability to obtain compounds with a defined geometric structure.

The invention is prepared according to the following examples by the reactions shown in schemes 1 and 2.

Example I

To a solution of 0.01 kg, i.e. 0.043 mol, of cis-2-nonyl-5-hydroxy-1,3-dioxane in 0.070 dm ^{3 of} dried carbon tetrachloride and 2103 dm3 of dried pyridine, under intensive stirring, at room temperature, several portions, 8.310 ^'3 kg, ie. 0.052 mol, of sulfur trioxide-pyridine. Stirring is continued at this temperature for 1 hour, and then for 6-8 hours at the temperature of 310 K. After evaporation of the solvent, the residue is gradually introduced at room temperature to 0.1 liters of water-alcohol / 3: 1 v / v / solution. containing 5.8-10.3 kg, i.e. 0.055 mol, of sodium carbonate. After evaporation of the solvents and crystallization of the residue from ethyl alcohol, 0.013 kg, i.e. 91% -mol, of the surface-active sodium salt of the cis-2-nonyl-5-hydroxy-1,3-dioxane derivative of the general formula I are obtained, = 9.

Summary formula CnIfeSOeNa: C, H, S content calculated respectively: 46.98.7.58, 9.63 wt%; determined, respectively, 47.0.7.6.9.6% by weight; melting point 476-470K.

Example II

To a solution of 0.019 kg, i.e. 0.0387 mol, of trans-2-undecyl-5-hydroxy-1,3-dioxane in 0.070 dm3 of dried carbon tetrachloride and 2 · 10'3 dm3 of dried pyridine, are introduced with intensive stirring, room temperature, in several portions, 7.4-10 kg, i.e. 0.0465

175,563 moles of sulfur trioxide-pyridine complex. Proceeding further like Example I, you get

0.013 kg, i.e. 93 mol%, of the surface-active sodium salt of the trans-2-undecyl-5-hydroxy-1,3-dioxane derivative of the general formula where n = 11.

Sum formula of CuIfeSOeNa; C, H, S content calculated respectively; 49.99, 8.69, 8.89% w / w, assigned respectively to 50.1, 8.7, 8.9% w / w; melting point 476-477 K.

Example III

To a solution of 0.050 kg, i.e. 0.217 mol, a mixture of cis- and trans-2-nonyl-5-hydroxy-1,3-dioxanes in 0.35 dm ^{3 of} dried carbon tetrachloride and 0.044 dm ^{3 of} dried pyridine is added dropwise at a temperature of 280-285 K, during 1 hour, 0.0278 kg, i.e. 0239 mol, of chlorosulfonic acid, while vigorously stirring the reaction mixture. After all the chlorosulfonic acid had been added dropwise, stirring was continued for 1 hour at room temperature, and then for 6-8 hours at 310K. After evaporating the solvent, the residue was gradually introduced into 0.4 liters of aqueous alcohol 3: 1 v / v / a solution containing 0.0192 kg, i.e. 0.48 mol, of sodium hydroxide at room temperature. After evaporation of the solvents and crystallization from ethyl alcohol, 0.671 kg, i.e. 93% -mol, of a mixture of surface active sodium sulphates, cis- and ¹ -trans-2-nonyl-5-hydroxy-1,3-dioxane derivatives of general formulas is obtained 1 and 2, where n = 9.

Summary formula: CnHąSOsNa; C, H, S content calculated 46.98.7.58, 9.63 wt%, respectively: determined respectively 47.0.7.7, 9.55; melting point 482-488 K.

OSO-jNa H ^C n ^H 2n.l ^ 2toi ^ AH ^C n ^H 2n4l ^ Z <3 ^ / ^lx OSO ₃ Na

A 'H pattern 1 pattern 2

OH H formula 3 formula 4

Cntyrwl C _n H _2nl1 0 ^ OSO ^ HgC6 + 0-Λ

cn ^H 2rw 1 0 - \ pSO ₃ Na

Λ> -Λ diagram 1

CnH2n _ł yO-A, 0S0 ₃ H-NH ₅ C ₅ ηΥΛ scheme 2

Publishing Department of the UP RP. Circulation of 90 copies. Price PLN 2.00

Claims (5)

Patent claims 1. New sodium salts of sulfates of 1,3-dioxane derivatives with the names cis-2-alkyl-5-hydroxy-1,3-dioxanes and the general formula 1 or trans-2-alkyl-5-hydroxy-1,3-dioxanes and the general formula 2 where n is 7-13. 2. A method for the preparation of new sodium salts of cis- and / or trans-2alkyl-5-hydroxy-1,3-dioxane derivatives of general formulas 1 and 2, in which n 'is 7-13, characterized in that cis- and / or the trans-2-alkyl-5-hydroxy-1,3-dioxanes of general formulas 3 and 4, in which n is as defined above, in a solvent solution, preferably in the form of carbon tetrachloride with the addition of pyridine, is reacted with chlorosulfonic acid and then the solvent is evaporated and the residue is taken up in an alcohol-water solution of sodium hydroxide or sodium carbonate or sodium bicarbonate, the solvent is evaporated and the residue is purified. 3. The method according to p. 2. The process of claim 2, wherein the molar ratio of the 1,3-dioxane derivative or derivatives to chlorosulfonic acid and to pyridine ranges from 1: 1, 1: 2.3 to 1: 1.2: 2.5. Process for the preparation of new sodium salts of cis- and / or trans-2-alkyl-5-hydroxy-1,3-dioxane derivatives of general formulas 1 and 2, in which n is 7-13, characterized in that cis- and / or trans-2-alkyl-5-hydroxy-1,3-dioxanes of general formulas 3 and 4 in which n is as defined above are reacted in a solvent solution, preferably in the form of carbon tetrachloride, with sulfur trioxide, preferably in the form of sulfur trioxide-pyridine complex, the solvent is evaporated off and the residue is taken up in an alcohol-water solution of sodium hydroxide or sodium carbonate or sodium bicarbonate, the solvent is evaporated and the residue is purified. 5. The method according to p. 8. The process of claim 4, wherein the molar ratio of the 1,3-dioxane derivative or derivatives to the complex ranges from 1: 1.1 to 1: 1.2.