DE2545644A1 - PROCESS FOR THE PRODUCTION OF SULPHONIC ACIDS - Google Patents

Description

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Process for the production of sulfonic acids

The invention relates to a new process for the production of sulfonic acids or their salts.

It is already known halides of the formula

R - shark

with alkali or ammonium sulfites in aqueous or aqueous-organic Implement media; the reaction proceeds according to the equation

R - Hai + Me ₂ SO ₃ -> R-SO ₃ Me + Me Hai.

In the equation:

R is an optionally substituted alkyl,

Alkenyl, alkynyl or aralkyl radical, Me sodium, potassium or ammonium.

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However, this reaction has the disadvantage that it is mostly used very reactive halides, i.e. bromides and iodides, in order to largely avoid side reactions. (see e.g. Gilbert "SuIfonation and Related Reactions", Interscience Publ. Inc. New York 1965, pages 137-138). Benzyl chlorides, for example, are converted into iodides before they are reacted with sulfite convicted. In order to get the chlorides to react, very drastic reaction conditions usually have to be used.

It has now surprisingly been found that the implementation improve significantly and under ethoaenden reaction conditions can perform if you do it in the presence of quaternary ammonium salts.

Examples of quaternary ammonium salts are those of the formula

-H-

R ₁ -NO

into consideration in the

Around

independently of one another represent an optionally substituted alkyl, cycloalkyl or aryl radical or two adjacent radicals R ₁ , R ₂ , R- * and R ₄ together with the nitrogen atom form a heterocycle and X "is an anion.

Those quaternary ammonium salts of the formula given in which R ₁ , E ₂ and R ₃ independently of one another are C ₁ -C 4 -alkyl and R _{4 are} C _{1 -C 14} -alkyl or phenyl have proven particularly useful.

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By adding the quaternary ammonium salts of the formula I to be used according to the invention, the reaction rate is increased to such an extent that one is no longer dependent on the use of the bromides and iodides, but that the chlorides can also be used without the need for drastic reaction conditions and disruptive ones Side reactions occur. With the aid of the quaternary ammonium salts to be used according to the invention, it is possible to carry out the reaction in a significantly shorter time and / or at lower temperatures. An increase in the space-time yield and, as a result of the lack of side reactions, an increase in the yield is achieved. Because of the low reaction temperature, there is usually no need to work under excess pressure, so that work can be carried out in normal vessels. According to prior art, the implementation of non-activated chlorides, for example reaction temperatures required of 100 ⁰ C and reaction times of 60 hours, and temperatures of 180 ⁰ C and times of 8 hours (see Fig. Organic Synthesis Coll. Vol.4, 1963, page 529). The implementation of long-chain n-alkyl chlorides, e.g. dodecyl chloride, required

Prior art measured a reaction temperature of 200 ° C. and a reaction time of 10 hours (Chem. Ber. 89, 1108 (1956)). In the presence of the inventive quaternary ammonium salts to be used, however, a significantly improved yield is obtained already at a temperature of 150 ⁰ C. According to the prior art, the conversion of methylene chloride required a reaction ^{temperature of 155 °} C. and a reaction time of 4 hours (J. Am. Chem. Soc. 75, 3567 (1953)). With the aid of the ammonium salts to be used according to the invention, however, the conversion is already successful at 90 ^° C. in 6 hours. Methallyl chloride, and propargyl chloride, which react only at temperatures from 55 to 80 ⁰ C (s. DT-PS 1,086,693 and J. Am. Chem. Soc 63, 1596 (1941)), in the presence of the quaternary ammonium salts at room temperature implemented. The conversion of n-octyl halide to n-octyl sulfonate has hitherto only been carried out with n-octyl bromide and required a reaction time of 9 hours at reaction temperatures of 180 to 200.degree. The yield was 60 to 70 % (see J. Am. Ghem. Soc. 57, 570). In the presence of the quafctarian

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Ammonium salts can be, however, the reaction with n-octyl and do this at 90 ⁰ C and without application of pressure and gets the sulfonate still in yields of over 90 jC.

Examples of R ₁ , R ₂ , Rz and R ^ are: as optionally substituted alkyl radicals C ₁ -C ₁ Q such as methyl, ethyl, propyl, η-butyl, sec-butyl, hexyl, _{Dodecyl and octadecyl radicals and especially C 1} -C _1Q -alkyl radicals substituted by the hydroxy or cyano group or aryl radicals, such as 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, 2-phenylethyl and 3- Phenylpropyl radical.

As optionally substituted cycloalkyl radicals, especially Cc-Cg-cycloalkyl radicals such as the cyclopentyl and cyclohexyl radical and the _{cyclopentyl and cyclohexyl radicals substituted by C 1} -C 4 -alkyl groups or halogen atoms.

As optionally substituted aryl radicals, especially _{phenyl radicals optionally substituted by C 1} -C ^ -AUCyI, C ₁ -C ^ -AIkOXy, or halogen atoms such as chlorine or bromine atoms, such as the phenyl, tolyl, methoxyphenyl and chlorophenyl radical.

The anion X ″ is mainly halide ions such as the chloride, bromide or iodide ion, and also the oyanide ion or the hydroxyl ion into consideration.

Examples of heterocycles that can form two adjacent radicals R ₁ , Rp, Rz »R /, together with the nitrogen atom, are above all 5- and 6-membered heterocycles such as the pyrrolidine, piperidine or morpholine ring.

Representatives of the ammonium salts to be used according to the invention include, for example: tetraethylammonium chloride, tetrabutylammonium chloride, Tetrabutylammonium bromide, triethyl-phenylammonium chloride, methyl-butyl-piperidinium iodide, tetrabutylammonium iodide, Tetraethylammonium cyanide, dodecyl-trimethylammonium hydroxide, Cyclohexyl-dodecyl-diaethylammonium chloride.

The amount of quaternary ammonium salts of the formula I required for the reaction can vary within wide limits. In general

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Nene have amounts of 0.1 to 10 wt .-%, preferably 0.3 to 5% by weight based on the weight of the halide to be reacted.

Halide and sulfite can be used in the process according to the invention be used in approximately stoichiometric amounts. However, it has often proven advantageous to use halide to be used in excess in order to achieve complete conversion of the sulfite. This way of working is recommended when the halide can be easily recovered. This can then be used again in the reaction.

The alkali or ammonium sulfites are saturated or in the form Supersaturated aqueous solutions are also used in order to avoid unnecessarily large amounts of liquid. However, it is also possible to work with dilute solutions, e.g. 5% sulphite solutions. In general, it has proven advantageous to add a water-miscible solvent, for example an alcohol, as a solubilizer.

Water-miscible alcohols, for example, are used as solubilizers such as methanol, ethanol, propanol, glycol, glycol monomethyl ether, glycol monoethyl ether, diethylene glycol, diethylene glycol monomethyl ether into consideration. Methanol or ethanol are preferably used.

The reaction of the halides with the sulfites in the presence of the Quaternary ammonium salts to be used according to the invention are carried out in a manner known per se, in which, for example, all Reaction components, solvents and quaternary ammonium salts mixes and the mixture is heated with stirring. However, it is also possible to use one of the reactants, e.g. the sulphite solution to be added in the course of the reaction.

The salts resulting from the reaction can be converted into the transfer free sulfonic acids.

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With the help of the method according to the invention it is possible to obtain sulfonic acids the formula

R - SO-, Η II

in the

R for an optionally substituted alkyl,

Alkenyl, alkynyl or aralkyl radical,

or their alkali or ammonium salts to be prepared in a simple manner and in good yields.

For example, the following are mentioned for R:

as optionally substituted alkyl radicals C 1 -C 4 -alkyl radicals such as the methyl, ethyl, butyl, hexyl, octyl, dodecyl and octadecyl radical; also substituted by halogen atoms, hydroxy, cyano, alkoxy, carbalkoxy, carboxy, alkylsulfonyl, dialkylphosphine or amino groups or heterocycles, such as chloromethyl, dichloromethyl, fluoromethyl , 1- and 2-chloroethyl, 2,2,2-trifluoroethyl, 2-fluoro-ethyl, 4-chlorobutyl, 2-chlorooctyl, carboxymethyl, 2-cyanoethyl, 2-carboxyethyl, 3-carbonamidopropyl -, 2-ethylsulfonyl-ethyl, 4-butyl-sulfonylbutyl, dimethylphosphinylmethyl and the pyridyl - * (3) -methyl radical #

As optionally substituted alkenyl radicals, mono- or polyunsaturated C ₂ -C ^ -alkylene radicals such as the allyl, methallyl and oleyl radicals.

As optionally substituted alkynyl radicals, in particular the propargyl radical *

As optionally substituted aralkyl radicals, the benzyl radical and benzyl radicals substituted by halogen atoms, O ₁ -O, -alkyl, C ^ -O.-alkoxy, nitro or cyano groups, such as 3-chloro, 4-methyl, 4-cyano , 2-ethoxy-benzyl radical.

The process according to the invention has proven particularly useful for the preparation of sulfonic acids of the formula II,

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in the

R stands for an n-alkyl radical, one with halogen atoms substituted n-alkyl radical, especially the chloromethyl radical or an alkenyl radical, especially the Methallyl radical.

The sulfonic acid salts obtainable according to the invention, in particular the sulfonic acid salts with long alkyl chains can be used as detergents, emulsifiers and wetting agents (see Ulimann Encyclopedia of Industrial Chemistry, 3rd Edition, 1963, Vol. 16, Page 550.)

The sulfonic acid salts prepared according to the invention are of greater importance as intermediate products for the production of the corresponding sulfo chlorides, which in turn are important intermediate products for a wide variety of compounds (see Ulimann loc. cit., page 565). When using the manufactured according to the invention Sulphonic acid salts as intermediate products for the production of sulphochloride it has proven advantageous to use the crude sulfonic acid salts obtained in the process, if appropriate to be used immediately in a mixture with the salts obtained during the reaction. That way, it can often difficult isolation of the sulfonic acid salts from the reaction mixture can be avoided and one arrives in a simple manner the sulfonic acid chlorides. The method according to the invention opens up At the same time, this is an economical way of producing sulfochlorides, which were previously difficult to produce in any other way was.

The sulfonic acid salts are converted into the sulfonic acid chlorides according to known methods, e.g. with phosphorus pentachloride or phosphorus oxychloride (see Houben Weyl, 4th edition, vol. X, Page 390/391) or thionyl chloride / dimethylformamide (see HeIv. Ch. Acta 42, 1653 (1959)).

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example 1

The solutions of 74.2 g (0.5 mol) of n-octyl chloride in 200 ml of ethanol, 74 g of sodium sulfate and 3.5 g of tetrabutylammonium chloride in 500 mml of water are mixed with one another and heated to reflux temperature for 20 hours. After distilling off the solvent, the residual salt mixture at 120 ⁰ C is dried. 148 g of a salt mixture are obtained which contain 100 g (= 93% of theory) of n-octyl sulfonate.

Example 2

The solution of 126 g (1 mol) of sodium sulfite in 350 ml of water and 100 ml of methanol is mixed with 4 g of tetraethylammonium chloride and 170 g (2 mol) of methylene chloride. The mixture is heated to 80 to 90 ^° C. for 6 hours. Then methanol and excess methylene chloride are distilled off and the remaining solution is evaporated to dryness. The residual mixture of sodium chloride and the sodium salt of chloromethanesulfonic acid is dried at 120 ⁰ C. 191 g of salt mixture are obtained, from which 110 g (= 72 # of theory) of chloromethanesulfonate are isolated by extraction with ethanol.

Example 3

7 g of tetraethylammonium chloride and 140 g (1.12 mol) of benzyl chloride are added to the solution of 126 g (1 mol) of sodium sulfite in 150 ml of water. The reaction mixture is heated to reflux temperature for 2 hours. The benzyl sulfonate which crystallizes out on cooling is filtered off. To isolate the residue of benzyl sulfonate remaining in the mother liquor, the mother liquor is freed from the solvent and the resulting salt mixture is extracted twice with hot ethanol. The benzyl sulfonate obtained after the ethanol has been evaporated off under reduced pressure is combined with the fraction obtained first. 190 g (= 98 % of theory) of benzyl sulfonate are obtained.

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Example 4

The solution of 126 g (1 mol) of sodium sulfite in 350 ml of water is mixed with 205 g (1 mol) of n-dodecyl chloride, 150 ml of methanol and 3.5 g of dodecyltrimethylammonium chloride. The reaction mixture is ^{heated to 150 °} C. for 5 hours. After cooling, the precipitate is filtered off, washed with ether and dried at 10O ⁰ C. 234 g (= 86 % of theory) of n-dodecyl sulfonate are obtained.

Example 5

The solution of 252 g (2 mol) of sodium sulfite in 1000 ml of water is first mixed with 200 ml of methanol and 4 g of tetrabutylammonium bromide and then with 149 g (2 mol) of propargyl chloride within half an hour. The temperature of the reaction mixture is kept ^{at 30 ° C. during the addition.} The reaction mixture is stirred for a further 3 hours. The solvent is then distilled off in vacuo. The salt mixture obtained is ^{dried at 40 to 50 °} C. in vacuo.

400 g of phosphorus oxychloride are added to the salt mixture without further purification and the mixture is heated to reflux temperature for 5 hours. The excess phosphorus oxychloride is then distilled off under reduced pressure. The residue is taken up in 200 ml of chloroform, after 300 g of ice have been added, the chloroform solution is separated off, washed with water and fractionally distilled. After renewed distillation in a high vacuum, 192 g (= 6956 of theory) propargyl sulfonic acid chloride ₂ : 41-45 ° C.) are obtained.

Example 6

The solution of 126 g of sodium sulfite (1 mol) in 600 ml of water is mixed with 198 g (2 mol) of 1,2-dichloroethane and 5 g of tetrabutylammonium chloride. The reaction mixture is ^{heated to 110 °} C. for 1 hour. After cooling, the excess will

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YES

1,2-Diohloräthan separated in a separating funnel. The aqueous phase is concentrated on a rotary evaporator and dried the resulting residue at 110 ⁰ C. 205 g of salt mixture are obtained which contain 138 g (83% of theory) of 2-chloroethanesulphonate.

Example 7

The solution of 126 g (1 mol) of sodium sulfite in 500 ml of water is first mixed with 100 ml of methanol and 5'g of tetrabutylammonium chloride and then dropwise at room temperature with 90.5 g (1 mol) of 1-chloro-2-methyl-propene ( 2) offset. The reaction mixture warms up to 37 ° C. and is stirred until the temperature has fallen back to room temperature. The solvent is then distilled off under reduced pressure. The crude salt mixture that remains is dried at 50 ° C. in vacuo. 206 g of salt mixture are obtained which contain -142 g (90 % of theory) of methallyl sulfonate.

Example 8

The solution of 126 g (1 mol) of sodium sulfite in 200 ml of water is mixed with 8 g of tetraethylammonium chloride and 130 g (1.2 mol) of methyl chloroacetate. The reaction mixture is heated to reflux temperature for 3 hours. After cooling, the solvent and the excess methyl chloroacetate are distilled off under reduced pressure. The resulting salt mixture is dried at 100 ⁰ C. 245 g of salt mixture are obtained, from which 141 g (80% of theory) carbmethoxymethylsulphonate are obtained by extracting several times with a 1: 1 mixture of ethanol / ethyl acetate.

Example 9

The solution of 126 g (1 mol) of sodium sulfite in 300 ml of water is mixed with 100 ml of methanol, 120 g (1.1 mol) of β-chloropropionic acid amide and 8 g of tetraethylammonium chloride. The mixture is in the autoclave at 130 ^° C. for 2 hours and then for 2 hours

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heated to 170 ^{° C.} Subsequently, the reaction mixture is freed of solvent and the residue obtained at 120 ⁰ C dried. This gives * £ _{iSalzmischung>} contains löulfonät 25CL the 131 g (75% of theory) 2-carboxamide € ^ 2yH3?.

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Claims (2)

Claims; 1. Process for the preparation of sulfonic acids of the formula R - SO ₃ H in the
R. for an optionally substituted one Alkyl, alkenyl, alkynyl or aralkyl The rest is or their alkali or ammonium salts by reacting Halides of the formula R - shark,
in the
R has the meaning given above and Hai means a chlorine, bromine or iodine atom with alkali or ammonium sulfites in aqueous or aqueous-organic media, characterized in that the Implementation in the presence of quaternary ammonium salts. 2. The method according to claim 1, characterized in that the reaction in the presence of quaternary · ammonium salts formula makes in the
R ^, R ₂ , Rz and R Le A16726 R ₁ - N - R ₃ independently of one another for an optionally substituted alkyl, cycloalkyl or aryl radical or two adjacent radicals R ^, Rp »R, and R, together form a heterocycle with the nitrogen atom and X ^ is an anion. - 12 - 7 09815/1127 ORIGINAL INSPECTED 3 · Method according to claim 1 and 2, characterized in that that quaternary ammonium salts of the formula given in claim 2 are used in which R ₁ , R ₂ and R ^ independently of one another for C ₁ -C ^ - Alkyl and R ^ are Cm-C ₁ a -alkyl or phenyl. Le A 16 726 - 13 - 7098 15/1127