RU2231524C2 - Method for preparing alkanesulfochlorides - Google Patents

Abstract

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing alkanesulfochlorides by reaction of sulfochlorination of (C₁₂-C₁₈)-n-alkanes by effect with a gas mixture SO₂ and Cl₂ taken in the mole ratio = 1.1:1 in the presence of organic peroxides as initiating agents of the process and showing the broad range of effective effect providing the process intensifying, high quality of reaction products and simplifying the initiating stage. Technical results are provides by using in the sulfochlorination reaction of mono- and diperoxyacetals of the formula

R'CH[OOC(CH₃)₃]₂ or R'CH(OR')OOC(CH₃)₃ or

wherein R' means -CH₃, -C₂H₅; n = 3, 4 that are added to alkanes in the amount 0.05-0.15% before onset of the process or prepared inside of sulfochlorator immediately (in situ) at temperature 25-35 C, specific consumption (1.54-4.33) x 10^-3 g Cl₂/g of alkanes per a minute in periodical or continuous regimen for time of reaction mass contact from 75 to 25 min and in feeding mixing gases SO₂ and Cl₂ by 22-30% for alkane conversion. In preparing alkanesulfochlorides in the presence of peroxyacetals formed inside of sulfochlorator (in situ) the sulfochlorination reaction is carried out by using tert.-butyl hydroperoxide solutions in simple aliphatic or cyclic ester, for example, tetrahydrofuran taken in the amount 0.5% of alkane level.

EFFECT: improved preparing method.

2 cl

Description

The invention relates to a method for producing alkanesulfonyl chlorides of liquid n-alkanes of predominantly composition C ₁₂ -C ₁₈ (RH) under the influence of a mixture of gases - sulfur dioxide (SO ₂ ) and chlorine (Cl ₂ ) - in a molar ratio of 1.1: 1 in the presence of organic peroxides as initiators of the process.

The free-radical sulfochlorination of alkanes of normal structure is implemented in the technique with the aim of obtaining sulfonates - important ionic surfactants (emulsifying, washing and wetting substances):

Sulfochlorides are labile when heated (SO _{2 is released} ), hence the temperature as a process initiator is not applicable. The industrial activator of the process at a temperature of 30-35 ° C is ultraviolet (UV) light [N.N Lebedev. Chemistry and technology of basic organic petrochemical synthesis. M., "Chemistry", 1988, S. 323-326].

The use of organic peroxides to initiate a free radical reaction is known. Acyl peroxides, for example benzoyl, lauryl, etc., are not effective in the process of sulfochlorination. Acetylcyclohexylsulfonyl peroxide, trimeric acetone peroxide, propanal dioxide peroxide have proven themselves [F. Azinger. Chemistry and technology of paraffin hydrocarbons. M., Gostoptekhizdat, 1959, p. 369]. In their presence, a high substitution rate is achieved in the series of n-alkanes of composition C ₁₀ -C ₁₈ , however, these initiators require special storage conditions or work with them in connection with the observed loss of active oxygen (O _act ) and high sensitivity to shock and friction.

It is known to use chloral dioxide completely safe to handle for processing hydrocarbons of the composition C ₁₂ -C ₁₈ dark tones (and so-called “unsaponifiable”) to sulfochlorides [Auth. testimonial. No. 186459, cl. 120 23/03, 1966]. However, a detailed check of its initiating ability showed that the results of sulfonation of pure paraffins by the depth of substitution (by accumulation of Cl _washed over time), by the achieved conversion of RH and gases, by the yield of alkanesulfonyl chlorides as a whole are worse than the performance of the process under illumination.

The high efficiency of initiating the process of sulfonation of alkanes of normal structure in the presence of oxymethyl-tert-butyl peroxide (CH ₃ ) ₃ C-OO-CH ₂ OH is known. Oxyperoxide provides a high substitution rate and allows one to obtain practically pure monosulfonyl chlorides by sulfochlorination, for example, pentane or hexane with a gas supply of 20% or more (even 100% in CCl ₄ medium), RH conversion at a temperature of 5-30 ° С and initiator flow rate 0 , 01-0.2% of RH [Aut. testimonial. No. 516683 C 07 C 143/70, 1976].

The reactivity of n-alkanes of the composition C ₁₀ -C ₁₈ and higher and, as a result, the formation of by-products, especially undesirable for the production of surfactants disulfochlorides, increases. So, under UV light, it is practically impossible to carry out the process with an RH conversion of 25% or higher, since when supplying gases by 22-24%, the RH conversion in the final product contains more than 25% disulfochlorides.

Closest to the claimed is a method of producing alkanesulfonyl chloride by the reaction of sulfochlorination of n-alkanes of the composition C ₁₂ -C ₁₈ under the influence of a mixture of gases SO ₂ and Cl ₂ in a ratio of 1.1: 1, filed per 30% conversion of RH in the presence of the indicated hydroxymethyl-tert -butyl peroxides 0.1% of RH [A.I. Rakhimov. Chemistry and technology of organic peroxide compounds. M., "Chemistry", 1979, p. 340]. The depth of sulfochlorination (in terms of the hydrolyzable chlorine Сl _washed ) of dodecane for the same interaction time exceeds the results obtained under illumination with a PRK-2 lamp, while the fraction of disulfochlorides is less.

However, the range of effective operation of the initiator when using synthine was limited. At high gas flow rates, for example about 4 × 10 ^-3 g Cl ₂ / g RH per min, oxyperoxide is inferior to UV light. Those. using it for the purpose of intensifying the production of alkanesulfonyl chlorides is problematic. In a countercurrent column with a reagent residence time of about 20-25 minutes, its effect on the system is negligible.

The use of peroxides as initiators of the process of sulfonation of alkanes requires the cost of their production and mandatory purification, which in some cases is quite specific. It is not possible to simplify the initiation stage by using the reaction mixture of initiator production (without isolating it). For example, these peroxides based on carbonyl compounds (including hydroxy and dioxiperoxides) are prepared using aqueous hydrogen peroxide (30% H ₂ O ₂ ) or formalin (40% H ₂ CO). The presence of water in the sulfochlorrator is unacceptable.

The lack of a simple and affordable and at the same time effective, superior UV light chemical initiator is an important search task. The foregoing, probably, limits the introduction of organic peroxides into the practice of the process of sulfochlorination of n-alkanes of the composition C ₁₂ -C ₁₈ . In the technique, UV light is preferred [US Pat. GDR No. 220583, C 07 C 139/02, 143/70, 1985], including in the cascade of reactors [US Pat. GDR No. 147844, C 07 C 139/02, 143/70, 1981].

With all its advantages, the photochemical process has a number of serious drawbacks. It is limited in the possibilities of creating devices of large unit power with a uniform photoelectric effect throughout the volume, it requires the use of raw materials only in light colors (pollution increases the optical density of the solution and reduces the photoelectric effect), and fire hazard increases. Even with a relatively long contact time of the reactants in a countercurrent continuous reactor (about 75 minutes), the degree of chlorine conversion is about 90%, about 30% of the initial hydrocarbon is not involved in the process of producing sulfonyl chlorides. The quality of the emulsifier is extremely low (due to the high content of disulfochlorides).

A known method of producing alkanesulfonyl chloride from n-alkanes C ₁₂ -C ₁₈ in the presence of UV light with the addition of 0.5 × 10 ^-3 % iodine [Auth. testimonial. No. 1685929, C 07 C 309/80, 1991]. Such an improvement in the photochemical process leads to a certain increase in the conversion of RH to monosulfochlorides, but does not fundamentally solve the problem of the chemical initiation of the reaction.

в водной среде, т.е. используют реакцию и исходные вещества, отличные от реакции сульфохлорирования алканов.Unacceptable for alkanesulfonyl chloride method [Auth. testimonial. No. 1558900, C 07 C, 1990] due to a Cl ₂ : SO ₂ : RH ratio of 2.2-6.5: 1: 1, and a high temperature of 50-90 ° C in the presence or absence of dimethylformamide (DMF ) using UV light or DAC. It should be borne in mind that there are also known methods for producing alkanesulfonyl chlorides of similar composition using one of the features, for example, gaseous Cl ₂ [Auth. testimonial. No. 1563591, C 07 C 309/00, 309/70, 1990], but dithiocarbonates are chlorinated

in the aquatic environment, i.e. use a reaction and starting materials other than the alkane sulfochlorination reaction.

The proposed method for producing alkanesulfonyl chlorides allows us to solve the problems that accompany the process of sulfochlorination of n-alkanes such as synthine and paraffin with an average composition of C ₁₂ -C ₁₈ .

The objective of the invention is to expand the range of effective initiators of the process of peroxide nature, ensuring the intensification of production, high quality sulfonates and at the same time significantly simplifying the initiation stage.

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The technical result is achieved by the fact that the production of alkanesulfonyl chlorides by sulfochlorination of n-alkanes of the composition C ₁₂ -C ₁₈ under the influence of a mixture of gases SO ₂ and Cl ₂ in a molar ratio of 1.1: 1 in the presence of an initiator — organic peroxide — is carried out in the presence of mono- and di-oxyacetals the structure

or

or

where R ′ = - CH ₃ , -C ₂ H ₅ , n = 3.4,

which are added to the alkane in an amount of 0.05-0.15% before the start of the process or obtained directly inside the sulfochlorinator (in situ) at a temperature of 25-35 ° C, at a specific flow rate (1.54-4.33) x10 ^-3 g Cl ₂ / g RH in min periodically or continuously during a residence time of the reaction mixture from 75 to 25 min when a mixture of SO ₂ and Cl ₂ gases is supplied at 22-30% alkane conversion.

If alkanesulfonyl chlorides are obtained in the presence of peroxyacetals formed inside the sulfonyl chloride (in situ), then the process of sulfonyl chloride is carried out using solutions of tert-butyl hydroperoxide in simple aliphatic or cyclic ether, for example tetrahydrofuran, in the amount of 0.5% of alkane.

Mono- and di-hydroxyacetals are storage stable and are distilled in vacuo at moderate temperatures without any complications. Initiate free radical sulfonation of alkanes in a wide range of contact time of the reagents and the specific consumption of gases.

They can be obtained in various ways, but the most affordable and fastest method for synthesizing peroxyacetals is based on the reaction of ethers with hydroperoxides under the influence of sulfuryl chloride according to the scheme, for example, for di-tert-butyl peroxy acetal of acetaldehyde (1,1-di-tert-butyl peroxyethane) with a yield of 90 % at low temperature:

When evaporated chlorine is passed through a solution of tert-butyl hydroperoxide in ether, monoperoxy acetal (along with di-peroxide) is predominantly formed according to the scheme, for example, for 1-ethoxy-1-tert-butyl peroxyethane:

Based on monoperoxyacetal, the product yield is about 70-80% in the temperature range from 0 to 25 ° C [Auth. testimonial. No. 1796621, C 07 C 407/00, 409/20, 1993]. Within an hour of interaction, a certain part of hydroperoxide is not converted.

Without opening the ring, tetrahydrofuran and other cyclic ethers react with hydroperoxide and sulfuryl chloride or chlorine.

However, the method for preparing peroxyacetals using a mixture of Cl ₂ and SO ₂ in a 1: 1 ratio turned out to be more appropriate. Under mild conditions, at a moderate temperature, with a high conversion, hydroperoxides are rapidly obtained in high yield from diperoxyacetal ethers and peroxyacetal from simple cyclic ethers [Auth. testimonial. No. 1668361, C 07 D 307/20, 1991], for example 2-tert-butyl peroxytetrahydrofuran, according to the scheme:

The described way for the synthesis of peroxyacetals is successfully combined with the process of sulfonation of alkanes by reagents and temperature. Due to the higher rate of interaction of the ester with hydroperoxide mixed with SO ₂ Cl ₂ (or a mixture of SO ₂ and Cl ₂ gases), the initiator is formed inside the sulfochlorator (in situ) with the subsequent effect on free radical substitution according to the final results, which are not inferior to purified peroxy acetals.

Peroxyacetals provide intensive management of the process of sulfochlorination of n-alkanes with a high conversion of all reagents, which is quite close to theoretically possible, while alkanesulfonyl chlorides are obtained with high quality indicators.

The invention is illustrated by the following examples on sulfonation of synthine (synthetic paraffin with an average molecular weight of 198 composition C ₁₂ -C ₁₈ ) under periodic and continuous conditions in the presence of the proposed peroxyacetals in comparison with UV light, oxymethyl tert-butyl peroxide and other additives.

Example 1. In a darkened glass reactor equipped with a stirrer, a thermometer and a reflux condenser, 97.50 g (127.3 ml) of synthine are added with the addition of freshly prepared (97.8%, O _act iodometry) di-tert-butyl peroxy acetal acetaldehyde in the amount of 0.1286 g, which corresponds to 0.13% of RH and [Jnc ₂ ] = 0,0048 mol / L.

A mixture of SO ₂ and Cl ₂ gases vaporized from cylinders in an amount of 0.15 g / min each by rheometer for 71 min to a molar ratio of RH is fed into a synthine solution with an initiator, maintaining the reaction temperature of 30 ± 2 ° С: SO ₂ : Cl ₂ equal to 3.28: 1.1: 1 (1: 0.33: 0.30). The specific consumption of Cl ₂ was 1.54 × 10 ^-3 g / g RH per minute. The sulfochlorination depth was estimated by the value of Сl _washed (according to Folhard) during the half-transformation (τ _1/2 ) and the end of the process (see table 1).

After nitrogen stripping, the reaction mass (without stratification) had the following indicators: Сl _washed 4.03%, n $\genfrac{}{}{0ex}{}{\text{20}}{\text{D}}$ 1.4458, d $\genfrac{}{}{0ex}{}{\text{20}}{\text{4}}$ 0.856, weight gain 10.5 g. Conversion of Cl ₂ 81.2% ( _{washed with Сl} ); RH conversion 24.9% (Cl _washed ).

Examples 2-6. Sulfin chlorination was carried out analogously to example 1 in the presence of monoperoxy acetal 1-ethoxy-1-tert-butyl peroxyethane (pr. 2) and to compare additives: oxymethyl-tert-butyl peroxides (pr. 3), tert-butyl hydroperoxide (pr. 4), DAK (D.5), as well as in the presence of UV light from an OKN-11 ultrahigh pressure lamp at a distance of 10 cm from the wall of the sulfochlorrator (D.6).

The depth of sulfochlorination in all examples (see table 1) is given for initiator samples with a purity of 98-100%.

Example 7. Sulfochlorination of synthine in an amount of 73 g (95.5 ml) was carried out with the supply of gases SO ₂ and Cl ₂ at 0.30 g / min each at a temperature of 30 ± 2 ° C for 30 min under illumination with a OKN-11 lamp ( 10 cm from the wall) to a molar ratio of RH: SO ₂ : Cl ₂ equal to 2.9: 1.1: 1 (1: 0.38: 0.34). In this case, the specific consumption of each of the gases was 4.10 × 10 ^-3 g / g RH per min.

After nitrogen stripping, the reaction mass had the following indicators: Сl _washed 3.77%, n $\genfrac{}{}{0ex}{}{\text{20}}{\text{D}}$ 1.4456, d $\genfrac{}{}{0ex}{}{\text{20}}{\text{4}}$ 0.8737, weight gain 8.90 g. Conversion of Cl ₂ 68.5% ( _washed with Cl); RH conversion 23.5% (Cl _washed ).

During storage during the day, the mass exfoliated, 1.47 g (1.8% of the total mass with Cl _omel 14.5%) of disulfochlorides poorly soluble in hydrocarbon were separated by decantation.

Examples 8-13. At a similar feed rate, as in example 7, in a darkened reactor, as in example 1, the depth (see table 1) of sulfochlorination without initiator (pr. 8), in the presence of oxymethyl-tert-butyl peroxide (pr. 9), and also in the presence of peroxyacetals of the structure of 1,1-di-tert-butylperoxypropane (pr.10), 2-tert-butylperoxytetrahydrofuran (pr.11), tert-butyl peroxydioxane-1,4 (pr.12), 1,1- di-tert-butyl peroxyethane (D.13).

Under process conditions similar to Example 9 (according to [Jnc ₂ ]), the conversion of RH and Cl ₂ in the presence of tert-butyl hydroperoxide or DAC was worse than when using oxymethyl tert-butyl peroxide.

Example 14. Sulfochlorination of synthine in an amount of 106 g (138.4 ml) was carried out analogously to example 1, in the presence of peroxyacetal structure of 2-tert-butyl peroxytetrahydrofuran with a purity of 98.9% (O _act iodometry) in an amount of 0.1485 g (which corresponds to 0 , 14% of RH and [Jnc ₂ ] = 0.0067 mol / L), feeding a mixture of SO ₂ and Cl ₂ gases at 0.30 g / min each for 33 minutes to a molar ratio of RH: SO ₂ : Cl ₂ , equal to 3.85: 1.1: 1 (1: 0.30: 0.26). The specific consumption of each gas was 2.83 × 10 ^-3 g / g RH per min.

After nitrogen stripping, the reaction mass (without separation) had the indices: Cl _washed. 3.83%, n $\genfrac{}{}{0ex}{}{\text{20}}{\text{D}}$ 1.4452, d $\genfrac{}{}{0ex}{}{\text{20}}{\text{4}}$ 0.8456, weight gain 14.19 g. Conversion RH 24.2% (Cl _washed ). Conversion of Cl ₂ 92.9% (by Cl _washed ).

Example 15. Sulfo chlorination of synthine in an amount of 72.0 g (94 ml) in the presence of peroxyacetal of the structure of 2-tert-butyl peroxytetrahydrofuran obtained inside the in situ sulfochlorator was carried out analogously to example 1 (see also pr.11) with the addition of 0.062 g of hydroperoxide tert-butyl (70% purity, iodometry) in 0.5 ml of tetrahydrofuran when applying SO ₂ and Cl ₂ gases at 0.28 g / min each to a molar ratio of RH: SO ₂ : Cl ₂ equal to 3.07: 1, 1: 1 (1: 0.36: 0.32). The reaction time is 30 minutes

The specific consumption of each gas was 3.88 × 10 ^-3 g / g RH per min. Initiator concentration (calculated) 0.0051 mol / L or 0.1% of RH, assuming 100% purity.

After nitrogen stripping, the reaction mass had the following indicators: Сl _washed 4.98%, n $\genfrac{}{}{0ex}{}{\text{20}}{\text{D}}$ 1,4446, d $\genfrac{}{}{0ex}{}{\text{20}}{\text{4}}$ 0.8597, weight gain 10.57 g. Conversion RH 31.8% (for Cl _omelet ), conversion of Cl ₂ 97.9% (for Cl _omelet ).

When stored for two days from the reaction mass, 0.94 g of poorly soluble in synthine products were isolated by decantation.

Example 16. Sulfonation of synthine was carried out analogously to example 15 using 0.062 g of technical tert-butyl hydroperoxide with a basic substance content of 70% (without THF). The concentration of hydroperoxide in the hydrocarbon is 0.06% of RH or 0.00513 mol / L, assuming 100% purity.

Obtained after nitrogen stripping 75.86 g of a mass with Сl _washed 2.42%, n $\genfrac{}{}{0ex}{}{\text{20}}{\text{D}}$ 1,4355, d $\genfrac{}{}{0ex}{}{\text{20}}{\text{4}}$ 0.8164. The conversion of RH is 14.2% (by Cl _omethyl ), the conversion of Cl _{2 by} 43.6% (by Cl _omel ).

Example 17. Sulfochlorination with a prohibitive specific gas flow rate was carried out analogously to example 1, feeding in 84 ml (64.36 g) of synthine with the addition of 0.0772 g of 1,1-di-tert-butyl peroxyethane, a mixture of gases SO ₂ and Сl ₂ at 0, 30 g / min to a molar ratio of RH: SO ₂ : Cl ₂ equal to 3.6: 1.1: 1 (1: 0.30: 0.27). The reaction time is 21 minutes The specific consumption of each of the gases was 4.67 × 10 ^-3 g per 1 g of RH per min. The initiator concentration is 0.12% of RH or 0.00446 mol / L.

Obtained after nitrogen stripping, 70.44 g of a mass with Сl _washed 2.48%, n $\genfrac{}{}{0ex}{}{\text{20}}{\text{D}}$ 1,4387, d $\genfrac{}{}{0ex}{}{\text{20}}{\text{4}}$ 0.8268. The conversion of RH is 15.2% (Cl _washed ), the conversion of Cl _{2 is} 55.4%.

Example 18. Continuous sulfochlorination was carried out in a countercurrent column with a jacket 300 mm high, with an inner diameter of 20 mm. The fill factor did not exceed 0.7. The hydrocarbon was supplied continuously by the dispenser through the top of the column at a rate (4.6 ml / min), depending on the residence time and the ratio of reagents. A mixture of gases was fed down the column. The selection of products was carried out from the bottom of the column at the crossflow established at the level of the reaction mass in the sulfochlorinator. The reaction temperature of 30 ° C was maintained by an UT-15 ultra-thermostat.

The “seed” of the process was carried out by supplying SO ₂ and Cl ₂ at 0.38 g / min for each of the gases through 114 ml of synthine containing 0.15% of the RH of pure 1,1-di-tert-butyl peroxyethane dihydroxy acetal structure min to a molar ratio of RH: SO ₂ : Cl ₂ equal to 3.29: 1.1: 1 (1: 0.33: 0.30). The specific consumption of each gas was 4.33 × 10 ⁻³ g / g RH per min. The mass indicators during the “seed” Сl _washed 4.10%, n $\genfrac{}{}{0ex}{}{\text{20}}{\text{D}}$ 1.4460 d $\genfrac{}{}{0ex}{}{\text{20}}{\text{4}}$ 0.856.

Maintaining the indicated ratio for several hours, with a hydrocarbon residence time of 25 minutes in the sulfochlorrator (while monitoring the given parameters for each hour), a reaction mass with the total Сl _{washes was} obtained at 4.28%, Сl _{total at} 6.67%, n $\genfrac{}{}{0ex}{}{\text{20}}{\text{D}}$ 1,4454, d $\genfrac{}{}{0ex}{}{\text{20}}{\text{4}}$ 0.852, weight gain 1.18 g / g RH. Conversion of Cl ₂ 93.79%, conversion of RH 28.6%.

For comparison, under similar process conditions (without the addition of peroxide), only in scattered light are the reaction mass indices: n $\genfrac{}{}{0ex}{}{\text{20}}{\text{D}}$ 1,4446, d $\genfrac{}{}{0ex}{}{\text{20}}{\text{4}}$ 0.846, Cl _washed 3.71%, Cl _total 6.07%, weight gain 1.07 g / g RH. Conversion of Cl ₂ 75.4%, conversion of RH 22.8%.

The calorimetric determination of the composition of sulfochlorination products at RH conversion close to 24 ± 05% achieved during the experiment is shown in Table 2.

The experimental results indicate that peroxyacetals at a flow rate of 0.1 ± 0.05% of RH are effective initiators of synthine chlorochlorination in a wide range of reaction conditions, with a specific flow rate of each gas from 1.54 × 10 ^-3 to 4.33 × 10 ^-3 g / g RH per min or contact time of reagents from 75 to 25 min inclusive.

It makes no sense to discuss the effect of the initiator with a lower specific gas flow rate from the point of view of process intensification. An increase in [SO ₂ ] and [Cl ₂ ] contributes to an increase in the rate of substitution. But at a SO ₂ flow rate greater than 4.33 × 10 ⁻³ g / g RH per min, a noticeable decrease in the initiation efficiency is observed in the presence of peroxy acetal. The results (see pr.17, time 21 min) are apparently due to the unproductive ionic decomposition of peroxide. Sulfuric anhydride is known to be an OO bond reductant. It should be borne in mind that the intensification of the process in the direction of reducing the contact time of the reagents (less than 25 min) is hardly advisable due to the high exothermicity of the process (there are problems with heat removal.)

The effect of peroxyacetal on the system is also confirmed during the process in a countercurrent column (see pr. 18, in an unshaded reactor). All other additives (oxyperoxide, DAC, lauryl peroxide, hydroperoxide) do not significantly affect the depth of sulfochlorination in the column, including at a residence time of 40 min, (the results are close to the effect of scattered light).

Of particular value is the possibility of obtaining the initiator inside the sulfochlorinator (in situ) from available technical products, for example, demonstrated in Project 15 from tert-butyl and tetrahydrofuran (THF) hydroperoxides. In this case, unreacted THF, taken in a small excess of hydroperoxide, will not contribute in any way to contamination of the final product, the sulfonate, due to the good solubility of THF in water during the processing of alkanesulfonyl chlorides.

The ratio of reacting substances and the degree of alkane conversion achieved has a decisive influence on the composition of free radical substitution products. With a close conversion of RH (see table 2), organic peroxides of the indicated structure are undoubtedly more preferred as initiators of the process than UV light. In their presence, the reaction mass contains significantly less undesirable disubstitution products (as well as the products of chlorination formed in parallel, as indicated by the nature of the change in the chlorine of the chain according to Cl _total , pr. 18). Visually, separation of the reaction mass (separation of disulfochlorides) is observed at an RH conversion of more than 28%, while under illumination (especially in a countercurrent column) even at a conversion of 22%.

Comparative data on sulfochlorination of saturated hydrocarbons of normal structure with a composition of C ₁₂ -C ₁₈ , the claimed and known methods that are closest in goals and objectives, are shown in table 3.

Claims (2)

1. The method of producing alkanesulfonyl chlorides by sulfochlorination of n-alkanes of composition C ₁₂ -C ₁₈ under the influence of a mixture of gases SO ₂ and Cl ₂ in a molar ratio of 1.1: 1 in the presence of an initiator - organic peroxide, characterized in that mono-organic peroxide is used - and diperoxyacetal formulas

or

or

where R ′ = —CH ₃ —C ₂ H ₅ ; n = 3.4, which are added to the alkanes in an amount of 0.05-0.15% before the start of the process or obtained directly inside the sulfochlorinator (in situ) at a temperature of 25-35 ° C, at a specific flow rate (1.54-4.33) x10 ^-3 g Cl ₂ / g alkanes in 1 min periodically or continuously with a residence time of the reaction mixture from 75 to 25 min when a mixture of SO ₂ and Sl ₂ gases was fed to a 22-30% alkane conversion. 2. The method of producing alkanesulfonyl chloride according to claim 1, characterized in that the sulfonation of alkanes in the presence of peroxyacetal obtained inside the sulfonyl chloride (in situ) is carried out using solutions of tert-butyl hydroperoxide in simple aliphatic or cyclic ether, for example tetrahydrofuran, in an amount of 0, 5% of alkane.