PL162441B1 - Method for manufacturing new, surface-active sodium sulphate derivatives of 2,5-di and 2,2,5-tri substituted 5-hydroxymethyl-1,3-dioxanes - Google Patents

Abstract

1. The method of producing new surface active sodium sulfates of 2,5-dlorase derivatives 2,2,5-trisubstituted 5-hydroxymethyl-1,3-dloxanes of the general formula I wherein R 1 is straight or a branched chain hydrocarbon C aH2a + 1 in which a is a number from 5 to 15 or substituents of alkylphenyl R4CeH4. wherein R4 is straight or branched hydrocarbon chain CbH'zb + 1, in which b is from 0 to 12, R2 is H, straight or CcHac + i branched hydrocarbon chain, in which c is from 1 to 8, or R and R2 are together cycloalkyl CdH2d, where d is from 5 to 12, R3 is a hydrocarbyl chain CeH2e + i. wherein e is the number 1 or 2, characterized in that the 1,3-dioxane derivatives of general formula II, w wherein R 1, R, R 3 are as defined above, r a solution of a solvent, preferably carbon tetrachloride, containing added pyridine, at a temperature of 260 320K, preferably 270-280K, reacted with acid chlorosulfonate, the molar ratio of the derivative 1,3-dioxane to chlorosulfonic acid and to pyridine ranges from 1: 1: 2.1 to 1. 1. 1: 2.5, a after completion of the reaction, evaporate from the reaction mixture the solvent is taken up and the residue is taken up in alcohol-water solution of NaOH, NaHCO3 or NaaCOto, and upon evaporation of the solvent, formed the surface-active sodium sulphates are purified.

Description

The subject of the invention is a process for the preparation of new 2,5-di- and 2,2,5-trisubstituted 5-hydroxymethyl-1,3-dioxane surface-active sodium sulfates of the general formula I, in which R1 is a straight or branched hydrocarbon chain CaH2a + i, wherein a is a number from 5 to 15 or a substituent of an alkyl phenyl R ⁴ CóH4, wherein r4 is a straight or branched hydrocarbon chain CbH2b + i, where ^{b t} s oceans ^and HCz ^b e o ^{d 0} to ^12, R ² states ^and H lu simple ^b rozgafcztóny ańcuc ^{wit h hydrocarbon yc} c ^H 2c + b in which cs ^t oceans ^and HCz ^b e ¹ <to ^{8, or r1 and R2} stanowU Uczme ^ dstawmk

162,441 cycloalkyl CJFhd where d is a number from 5 to 12, R is the CeFhe + hydrocarbon chain and where e is a number 1 or 2.

These derivatives show surface activity at interfacial boundaries and therefore can be used as active ingredients in washing, wetting, foaming, emulsifying, washing, dispersing agents, alone or in mixtures with other surface-active compounds.

The essence of the invention consists in the fact that the 1,3-dioxane derivative of the general formula 2, in which R ¹ , R ² , R ³ are as defined above, is reacted with an acid in a solvent solution, preferably carbon tetrachloride, containing the addition of pyridine. chlorosulfonic acid, where the molar ratio of the 1,3-dioxane derivative to chlorosulfonic acid and to pyridine is in the range from 1: 1: 2.1 to 1: 1.1: 2.5, or the 1,3-dioxane derivative in a solvent solution, preferably carbon tetrachloride, is subjected to is reacted with sulfur trioxide, preferably in the form of a sulfur trioxide-pyridine complex, the molar ratio of the 1,3-dioxane derivative to the sulfur trioxane-pyridine complex ranges from 1: 1 to 1: 1.1, preferably at a temperature of 270 ° C. 280 K, and after the completion of the reaction, the solvent is evaporated and the residue is taken up in an alcohol-water solution of NaOH, NaHCO3 or N2CO3, and after evaporation of the solvent, surface-active sodium sulfates of derivatives 1 are formed, The 3-dioxane is optionally purified by generally accepted methods.

The main advantages of using the method for the preparation of new, surface-active sodium sulphates of 1,3-dioxane derivatives of the general formula 1 according to the invention are: the production of easily chemically degradable surfactants due to the presence of an acetal bond in their molecules, which makes them less burdensome for environment, high surface activity of products, availability of raw materials, ease of sulphation reaction, high and often quantitative reaction efficiency and easy purification of end products

The subject matter of the invention is explained in the examples of the new 1,3-dioxane derivative surfactant sodium sulphates and in the figure where Scheme 1 shows the reaction of a 1,3-dioxane derivative with chlorosulfonic acid, while Scheme 2 shows the reaction of a 1,3-dioxane derivative with sulfur trioxide-pyridine complex, leading, after basification with NaOH, NaHCO3 or NaCO3, to diastereomeric mixtures of surface-active sodium sulfates of 1,3-dioxane derivatives.

EXAMPLE I To a solution of 0.050 kg (0.217 mol) of a mixture of diastereomeric poc ^{h d h} ^ nyc heptytó ^{Stydroteymetytó--5} - methyl-l ^ -dmksanu at ⁰ .4 ^{d 3} m czterocMorku atoms and 0,044 days of pyridine is added dropwise at 270 -275 K in 1 hour 0.0265 kg (0.228 mol) of chlorosulfonic acid while vigorously stirring the reaction mixture. After all the chlorosulfonic acid has been added dropwise, stirring is continued for an additional 3-4 hours. gradually increasing the reaction temperature to room temperature. After evaporation of the solvent, the residue is gradually poured into 0.4 dm of an alcohol-water (3: 1) solution containing 0.0185 kg (0.463 mol) of NaOH at 270-275 K. After evaporation of the solvent, the solid residue is washed with 4x0.15 dm3 of boiling alcohol. ethyl. After evaporation of the solvent and / or crystallization from the system ethyl alcohol: isopropyl alcohol = 1: 3, 0.0703 kg (97.5 mol%) of a mixture of diastereometric surface-active sodium sulphates 2-heptyl-5-h are obtained; ^ <^ and ^ (^ 1 ^ cis ^ r ^^ t ^ 2 ^ 1 (^^ 5 ^ r ^^ t ^ t ^ ll ^ -1,3-dioxane of og ^ol NYM formula 1 wherein ^r1 = n-C 7 ^H i5, ^R = ^H , ^r3 = CH3. Equ (5r total ^C i3H2iSONa ^; C, H, S content calculated, respectively, 46.98.7.58.9.63%; determined respectively 46.8, 7.8, 9.7%; mp 436.5 - 438.5 K (decomposition ); surface tension of a 1% aqueous solution of 49.1 mNm'1

Example Π. To a solution of 0.050 kg (0.1745 mol) of a mixture of diastereomeric p ^ochod nyc ^{h 2-} undecytó- ⁵ - ^ droksymetylo-Smetylo-S-dioxane at ^{0. 4} dm ³ of carbon tetrachloride are introduced with vigorous stirring at the temperature of 275-280 K, in portions, over 1.5 hours, 0.0306 kg (0.192 mol) of the sulfur trioxide-pyridine complex. After move in

After 162,441 of the total complex, mixing is continued for an additional 5-6 hours. gradually increasing the reaction temperature to room temperature. After evaporation of the solvent, the residue is gradually introduced into 0.4 g of an alcohol-water (3: 1) solution containing 0.1 mole of Na2COb at a temperature of 270-275 K. After evaporation of the solvent and pyridine, 0.0672 kg (99.1% mole) of a mixture of diastereomeric surface-active sodium sulphates are obtained. 2-undecyl-5-hydroxymethyl-5-methyl - ^ - oo dmksanu ^shave NYM formula 1 kt ^yellow wherein R ¹ = n-Cnlfo, R ² = H, R ³ = CH 3. Total windage Cp ^ SO ^ Na; C, H, S content calculated 52.56, 8.56, 8.24% respectively; determined, respectively, 52.8,8.9,8.2%; melting point 433-437 K (decomposition); surface tension of 0.1% aqueous solution of 42.8 mNm ⁴ .

Example ΠΙ. To a solution of 0.050 kg (0.217 mol) of a mixture of diastereomeric oc ^{p h} o n ^{y d} c ^{2 h 2} -amylo- eth ^yl o- ⁵ - ^{hyd y} roks ^{methyl-5-methyl-1,3-dioxane} in a ^0.4 m ^{3 d} Carbon tetrachloride is introduced with vigorous stirring at a temperature of 275-280 K, in portions, over 2 hours, 0.0363 (0.228 mol) of the sulfur trioxide-pyridine complex. Next, the procedure as described in Example U is obtained 0.055 kg (76.2 mol%) of diastereomeric mixture of surface-active sulfates, sodium ^{2-amyl-2-ethyl-5-hydroxymethyl-5} -met ^l o o ^{yl 1,3-shave} doksanu oo n ^{y is the} formula I, wherein R ¹ = NC 2 N, ^{R 2} = C ^{5, R 3} = ^{CH 3} . Summary formula CnHosSCón; C, H, S content calculated 46.98.7.58.9.63% respectively; determined, respectively, 47.0,7.4,9.5%; melting point 468-472 K (decomposition); connection powterzchmowe ^1% solution of beef ^d nego ⁵⁴ .2 m ^N m \

Example IV. To a solution of 0.050 kg (0.216 mol) of a mixture of diastereomeric ^p arts ^{h y} ref ch ^2/4 -met ^y is ^{the y} lofen / - ⁵ - ^{dihydro k} s ^{y y} meth LO ^{5-ethyl-l, 3} - ^di oxane in O. ⁴ dm ³ of carbon tetrachloride and 0.64 dm 3 of pyridine, are added dropwise at 270-275 K over 1.5 hours. 0.0264 kg (0.227 mol) of chlorosulfonic acid while vigorously stirring the reaction mixture. By proceeding analogously to Example 1, 0.0373 kg (51.0 mol%) of a mixture of diastereomeric, surface-active sodium sulphates 2- (4-methylphenyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane of the general formula I are obtained, wherein R 1 = R ⁴ C ⁶ H ⁴ , R 2 = H, R 3 = C2 H 5, R ⁴ = 4 - CH 3. Summary formula CuHiSOONa; C, H, S content calculated 49.70, 5.66, 9.46%, respectively, determined 49.4.5, 9.5%, respectively; melting point 471.5-476 K (decomposition); surface tension of 1% aqueous solution of 58.5 mNm \

162 441 _z 0-CH _{2 /} R ⁵ Cl S0 ₃ H. 2 c ₅ h ₅ n_ fR ^ O-HH ^ OH R * ^X 0-CH2 ^x CH20S0 ₃ H.NH ₅ C ₆ ♦ C ₃ H ₅ N- HCl

-10-00¾

-NaCl -2C ₅ H _S N ^R X

R ² ^ '0-CH2 ^x CH20S0 ₃ In diagram 1 ^R k _zO-CH? / ^R3 C ₅ H ₅ N. ^S O ^a ~ ^R k © ⁰ _ ^C tV ^R3 _ "

R ^{2 /} 'q- ^ C ^h 2 ^x CH ₂ QH ^r2 ° -C ^h 2 ^CH 2 ^0S0 a ^HNH 5 ^C 5

NaOH ^R \ / ^r3

-C ₅ HsN, -HiO * R ² ''> D-cH2 ^X 'CH20S0 ₃ For diagram 2

162 441/0-CH ^ R ^{3 R x} 0-CH ^2X CH ₂ 0S0 ₃ For formula 1

R ² o-ch _{2 /} rc τ ^x O-CH2 ^X CH2OH formula 2

Department of Publishing of the UP RP. Circulation of 90 copies. Price: PLN 10,000

Claims (2)

Patent claims 1. A method for the preparation of new 2,5-di- and 2,2,5-trisubstituted 5-hydroxymethyl-1,3-dioxane surface-active sodium sulfates of the general formula 1, in which R ¹ is a straight or branched chain hydrocarbon CcHaa + and wherein the states ^and HCz ^BE of ^{d 5 d 15 l} with ^{b b a} substituent ałkdofen ^ mid ^r4 C "H4, wherein ^r4 states ^and a straight or branched hydrocarbon chain CbH2b + i, where b is a number from 0 ^12, the ^{r2 state, and} H ^p rosty ^l in ^{b PG} and ^{LE and} located ^{EXAMPLE ñ} chain narrower ^gl owodorowy C _c H2c + a, wherein c is a number from 1 to 8, or R1 and r2 together constitute a substituent cycloalkyl CdKfed, wherein d states ^and HCz ^BE of ^{d 5 d 12, r3} conditions ^and tańcuch hose ^gl word ^d Hydrogen Masers ^{s C} s ^H2 s + b where e is the count ^BE 1 ^l in ^b 2, characterized in that ^f e orig ^d ne L ^ oo thoteanu ^{shave n} n m formula 2 ^k tórym ^{r1, r2, r?} May ^{and P} head ^YZ defined above are dissolved in a solution of ^ najkpiej czteroctóorku atoms, comprising the addition of pyridine, at a temperature of 260-320 K, preferably 270-280 K, is subjected to -reakcji with chlorosulfonic acid, wherein the molar ratio of the derivative to 1,3dioksanu chlorosulfonic acid and pyridine ranges from 1: 1: 2.1 to 1: 1.1: 2.5, and after the reaction is completed, the solvent is evaporated from the reaction mixture and the residue is taken up in an alcohol-water solution of NaOH, NaHCOb or Na2COj, and after evaporation In the solvent, the surface-active sodium sulphates formed are purified. 2. A process for preparing surface-active sodium sulfate derivative of 2,5-di- and trisubstituted 2,2,5-5-hydroxymethyl-l, 3-dioxanes of the general formula 1 wherein ^R1 is ^p rost ^{yl PG b} u Oh ^and a ^{y EXAMPLE s} cuc ^h under ^g towo ^d orowy Catha + a, wherein a is HCz ^BE of ^{d 5 d 15 l} in ^b basal ^ alkitó ^f en ^yl head ^y RTO ^ in lctór ^y m ^r4 conditions ^and a straight or branched hydrocarbon chain Cbftb + i, where b is a number from 0 to l ^2, R ² states ^and H ^p rosty ^l in ^b branched ^ ztóny teńcuch narrower ^g towo ^d orowy Cc ^ c + b in which c states ^and the number of 1 to 8, or R1 and R2 together represent a CdH2d cycloalkyl substituent in which d is from 5 to 12, R ³ is a CeH2e + i hydrocarbon chain, in which e is 1 or 2, characterized in that derivatives 1,3 - dioxane of the general formula II, in which ^R 1, R 2, ^R 3 are as defined above, in a solvent solution, preferably carbon tetrachloride, at a temperature of 260-320 K, preferably 270-280 K, is reacted with trioxide sulfur, preferably in the form of a sulfur trioxane-pyridine complex, the molar ratio of the 1,3-dioxane derivative to this complex ranges from 1: 1 to 1: 1, and after the reaction is completed, the solvent is evaporated from the mixture and the residue is introduced to an alcoholic aqueous solution of NaOH, NaHCO3 or Na2CO3, and the surface-active sodium sulphates produced are optionally purified after evaporation of the solvent.