JPH0249761A - Production of organic monochlorosulfonate - Google Patents

Abstract

PURPOSE:To obtain the title substance useful as an alkylsulfonating agent in high selectivity, purity and yield by reacting an organic dichloride with a sulfite in an aqueous solution containing a water-miscible polar solvent at a temperature above the boiling point thereof. CONSTITUTION:An organic dichloride (e.g., dichloromethane) is reacted with a sulfite (e.g., Na2SO3) at >=1.1 molar ratio in an aqueous solution containing 10-45wt.% polar solvent (preferably methanol, ethanol, n-and isopropanol) miscible with water at ordinary temperature to 130 deg.C at a temperature above the boiling point thereof to afford the title substance. The volume ratio of the sulfite/reaction medium is <=0.67mol/l. If the methanol or ethanol is used as the polar solvent, the above-mentioned volume ratio is preferably 0.33-0.56mol/l and the molar ratio of organic dichloride/sulfite is preferably 1.5-5.0.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for selectively producing organic monochlorosulfonate.

This organic monochlorosulfonate is a useful compound that is used as an alkyl sulfonating agent in the production of surfactants, pharmaceutical ingredients, and the like.

[Prior Art] It is generally well known that organic monohalogen compounds react with sulfites in aqueous media to produce organic sulfonates (The Merck Index 8t
h Ed 1968 1), 1218). but,
Formation of disulfonate is predominant from organic dihalogen compounds. For example, when 1,2-dichloroethane and sodium sulfite are reacted at 100°C, ethanedisulfonate is formed as shown in equation (1) below. Becomes dominant (
J.

Am, Chem, Soc,, Vo167.157g (1
945), JP-A No. 50-101325), the yield of ethanedisulfonate based on sodium sulfite is 42
%, and the yield of chloroethanesulfonate shown in the following formula (2) was extremely low at 55%.

CIC2H4C1+2Na2S03→ Na0a 5c2H4So3Na+2NaCl (1
)CIC2H4C10Na2SO3→ CIc2H4So3Na10NaCl (2)
Up until now, practical methods for synthesizing organic monohalogen sulfonates have been the following methods (a) and (b), which use bromine-containing compounds, which are more expensive than chlorine compounds, as raw materials.
There is only one known method.

That is, (a) a method in which a 1a compound containing two types of halogens is reacted with a sulfite and the difference in reactivity of the halogen species is utilized. As an example of this method, there is U.S. Pat. No. 2,797,239, and according to the described method, 1-bromo-2-chloroethane is used as a bromine-containing compound, and 12.8 wt% sodium sulfite is added at 80°C. This method is a method of reacting an aqueous solution, and according to the following formula (3), sodium monochloroethanesulfonate is obtained at a yield of 90% based on sodium sulfite.

BrCHC1+Na2S○3→ CI C2H4S Oa Na + Na Br
(3> Also, (b) is a method of reacting organic dibromide and sulfite in an ethanol aqueous solution. Examples of this method include Org, 5ynth, C.

11, Vol II, p. 558, 1 at the boiling point of the reaction solution in a 50 wt% aqueous ethanol solution.
, 2-dibromoethane and sodium sulfite are reacted. According to this method, sodium bromoethanesulfonate is obtained with a yield of 88% based on sodium sulfite.

BrC2H4Br+Na2SO3→ B r C2H4S O3N a + N a Br
(4) However, Ind, Eng, Chem, ,V
o139.906 (1947), when Br was replaced with CI in the above formula (4), that is, the reaction was performed using 12-dichloroethane as the starting material instead of 1,2-dibromoethane. In this case, the reaction takes a long time, approximately 72 hours at 72°C, to complete, and the yield of sodium chloroethanesulfonate based on the sulfite is at most 78%.

In this way, when a bromine-containing compound was used as a starting material, it was possible to obtain an organic monohalogen sulfonate with a reasonably high yield, but it was possible to obtain an organic monochlorosulfonate from an organic dichloride. At present, a method for producing it efficiently with high selectivity has not yet been established.

[Problems to be Solved by the Invention] The present invention uses an inexpensive organic dichloride as a starting material instead of a bromine-containing compound, and moreover, achieves high yield and high selectivity through a short reaction time. The object of the present invention is to provide a method for producing pure monochlorosulfonate.

In general, the monochlorosulfonates and disulfonates synthesized from the above-mentioned organic dichlorides do not exhibit a boiling point, or even if they do have a boiling point, they are extremely high, so it is difficult to purify them by normal distillation operations, and it is difficult to react. High selectivity is an important condition for obtaining high purity products.

Furthermore, increasing the volumetric efficiency of the reactor is also an important issue for industrial equipment.

[Means for Solving the Problems] As a result of intensive study on these issues, the present inventors found that by carrying out the reaction in an aqueous solution containing a polar solvent that is miscible with water at a temperature equal to or higher than the boiling point of the reaction aqueous solution. The present invention, which is an industrial manufacturing method, has been completed.

That is, the present invention is an organic compound characterized in that an organic dichloride and a sulfite are reacted in an aqueous solution containing 10 to 45 wt% of a polar solvent that is miscible with water at room temperature to 130°C at a temperature higher than the boiling point of the reaction aqueous solution. A method for producing a monochlorosulfonate is provided.

The details will be explained below.

The organic dichloride used in the present invention is an alkane or alkene group represented by the formula %, where n represents an integer from 1 to 6.
Specific compounds include dichloromethane, 1.1
-dichloroethane, 1.2-dichloroethane, 1.2-
Dichloropropane, 1゜2-dichlorobutane, 2,3-
Dichlorobutane, 1.2-dichlorobencune, 1.2-
Dichlorohexane, 1,2-dichloroethylene, 1.4
-dichlorobutene-2 and the like.

In addition, sulfites are sulfites represented by M S03, M
It refers to hydrogen sulfite represented by H8O3, etc., and mixtures thereof, and M is % Rb −, Cs in Li1.
Alkali metals such as -valent Cu.

NH, further refers to an alkylamine group represented by the formula CHNH. For example, as a sulfite, Na
So, NaH3O, KS03, KHSO,
LiSo, LiHSO3, CuSO-(
N H) S O1 (CHa NH) So, or a mixture thereof.

In addition, examples of polar solvents that are miscible with water at a temperature of 7H to 130°C include alcohols such as methanol, ethanol, n-propatool, isopropatool, ethylene glycol, propylene glycol, 1,4-butanediol, , 3-butanediol and other glycols, sulfolanes, and mixtures thereof. Among these, it is particularly preferable to use metatool, ethanol, n-propatool, and isopropatool.

In the present invention, selection of the type of reaction medium and its concentration is important. That is, the present inventors found that when the concentration of the aqueous polar solvent solution was less than 10 wt%, the production of disulfonate as a by-product increased significantly, and when the concentration of the aqueous polar solvent solution was less than 10 wt%,
It has been found that if the content exceeds wt%, the reaction rate decreases and is not practical.

Therefore, the concentration of the aqueous solution of the polar solvent is 10W [%
As mentioned above, 45 wt% or less is appropriate.

When methanol or ethanol is used as the polar solvent, the reaction is preferably carried out in a 20 wt% to 40 wt% aqueous solution.

Furthermore, in the present invention, the molar ratio and concentration of each component in the reaction solution are also important factors that affect the selectivity.

That is, the ratio of sulfite/reaction medium volume is 0.67 m o
1/l or less, the organic dichloride/sulfite ratio is 1
．． It is desirable to react at 1 mol/mol or more.

The reason is that the ratio of sulfite/reaction medium volume is 0.67 m
If it exceeds ol/1, the by-product of disulfonate increases and the selectivity of monochlorosulfonate decreases. A small sulfite/reaction medium volume ratio reduces the volumetric efficiency of the reactor, and an organic dichloride/sulfite ratio below 1.1 mol/mol reduces the yield of monochlorosulfonate; This is because if this value is too large, the volumetric efficiency of the reactor will decrease. And when methanol or ethanol is used as the polar solvent, the ratio of sulfite/reaction medium volume is 0.33-0.56 mo 1
/1. The organic dichloride/sulfite ratio is between 1.5 and 5.
It is more preferable to carry out the reaction at 0 mol/mol.

Furthermore, in the present invention, it is necessary to carry out the reaction at a temperature equal to or higher than the boiling point of the reaction solution. That is, below the boiling point of the reaction liquid, the reaction rate is slow, the volume of the reactor becomes excessive, and
If the reaction temperature is made too high, undesirable side reactions will increase, while the reaction pressure will increase, resulting in disadvantages such as the need to take measures such as increasing the pressure resistance of the reactor. When methanol or ethanol is used as the polar solvent, it is desirable to carry out the reaction at a temperature above the boiling point of the reaction solution and below 130°C.

The reactor is not particularly limited, but may be an autoclave, a tubular reactor, or a multitubular reactor. A batch method in which the organic dichloride, polar solvent, and all or part of the water are charged in at the beginning, a semi-batch method in which the sulfite is fed alone or as an aqueous solution over a fixed period of time, or It is also possible to adopt either a continuous method in which all raw materials, polar solvents, and water are fed all at once or in portions and continuously.

[Examples] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 A pressure-resistant glass autoclave with an internal volume of 11 immersed in an oil bath was charged with 630 ml of an ethanol aqueous solution with a concentration of 40 wt% at room temperature and 99 g of 1,2-dichloroethane with a purity of 99 wt%, and after sealing the lid, The temperature is raised while stirring, and the internal temperature of the autoclave is maintained at 100°C. Next, an aqueous solution of 43.75 g of reagent-grade sodium sulfite having a purity of 9[wt%] dissolved in 166 ml of distilled water is injected into the autoclave over a period of about 15 minutes using a constant flow bomb.

The concentration of the alcohol aqueous solution (alcohol/alcohol+water) at the time of completion of raw material input was 31 wt%, and the sulfite/reaction medium volume ratio was 0.42 mol/l.

The autoclave contents were cloudy for 15 minutes after the completion of feeding the sodium sulfite aqueous solution, but became colorless and transparent after that.

After further stirring at 100°C for 45 minutes, the autoclave was taken out from the oil bath, immersed in a water bath, and cooled under stirring until the internal temperature reached 30°C. Next, the lid of the autoclave was opened and the contents were transferred to a separable flask, which was immersed in a water bath and heated to distill off excess 1,2-dichloroethane and ethanol, and then water was added under reduced pressure. Evaporate and transfer the residue to an evaporating dish.8
When dried overnight in a constant temperature dryer at 0° C., 79.6 g of solid matter was obtained.

This solid substance was analyzed for inorganic chlorine and inorganic sulfur, and the total chlorine and total sulfur containing melon was analyzed by the Schieniger method, and the following results were obtained.

Inorganic chlorine 11.8wt96 Inorganic sulfur 0.4 Total chlorine 22.7 Total sulfur 11.1 On the other hand, when the above solid matter was Soxhlet extracted with 95wt% ethanol and the extract was left at room temperature overnight, needle-like particles Aggregated plate-like crystals precipitated.

This was filtered under suction, and the solid material was dried in a constant temperature dryer at 60° C. overnight, and then an infrared absorption spectrum was measured. As a result, it was confirmed that it was thorium 2-chloroethanesulfonate. Separately, when this solid was quantified by ion chromatography, it was found that it contained 63.5 wt% of sodium 2-chloroethanesulfonate and 2.4 wt% of sodium ethanedisulfonate.

Based on the above analysis values, the reaction rate of sodium sulfite is 97.5
%, the yield of sodium 2-chloroethanesulfonate based on sodium sulfite was 91.1%, and the yield of tetrium ethanedisulfonate was 4.95%.

Example 2 The amount of 1,2-dichloroethane used was 116 g, 40 wt.
% ethanol aqueous solution 630ml, 53wt%
Example 1 except that 650 ml of methanol aqueous solution of
The reaction was carried out under the same conditions.

The concentration of alcohol aqueous solution at the time of completion of raw material input is 41w
t%, the ratio of sulfite/reaction medium volume is 0°41 mol/
1. The organic dichloride/sulfite ratio is 3.0 mol
/mol. The reaction temperature was 100°C and the autoclave pressure was 3.5 kg/cm2G.

After the reaction was completed, the same treatment as in Example 1 was carried out, and the result was
80.2 g of dry solid was obtained. According to the analytical values of this solid, the reaction rate of sodium sulfite is 98.5%, and the yield of sodium 2-chloroethanesulfonate relative to sodium sulfite and 2-chloroethanesulfonic acid is 93.
5%, yield of sodium ethanedisulfonate is 1.75
%Met.

Example 3 Dichloromethane 85 instead of 1.2 dichloroethane
The reaction was carried out under the same conditions as in Example 2, except that the reaction temperature was 85° C. and the reaction time was 90 minutes. After the reaction was completed, the same treatment as in Example 1 was carried out, and the amount of dry solid obtained was 76.5 g.

According to the analytical values, the yield of sodium chloromethane sulfonate based on sodium sulfite was 95.3%.

Example 4 A reaction was carried out under the same conditions as in Example 2, except that 125 g of 1,4-dichlorobutene-2 was used instead of 1,2-dichloroethane, and the reaction temperature was 110°C and the reaction time was 120 minutes. Ta.

After the reaction was completed, the same treatment as in Example 1 was carried out to obtain 88.1 g of dry solid matter.

From the analytical values, 1-chloro-2 relative to sodium sulfite
The yield of sodium -butenylsulfonate was 87%.

Comparative Example 1 Instead of 630ml of 40wt% ethanol aqueous solution, 9
Instead of 360 g of 5 wt% ethanol aqueous solution and 43.75 g of sodium sulfite, 87°5 g and 166 m of distilled water were added.
The reaction was carried out under the same conditions as in Example 1, except that 324 g was used instead of 1 and the reaction time was 24 hours.

Even after 24 hours had passed, the autoclave contents remained cloudy. After cooling the autoclave contents to 30°C, it was centrifugally filtered and the filter residue was analyzed, and the content of inorganic sulfur was found to be 22.
It was wt%. This indicates that most of the filter cake is sodium sulfite.

When the above filtrate was treated in the same manner as in Example 1, 71.6 g of dry solid was obtained.

From the analysis value of this solid, 2
-The yield of sodium chloroethanesulfonate is 31.2
%, and the yield of sodium ethanedisulfonate was 1.7%.

Comparative Example 2 1,2-dichloroethane 198 was added to the same apparatus as in Example 1.
g, 5 g of tetrabutylammonium bromide as a phase transfer catalyst, and 96 wt% purity of sodium sulfite 1
Pour an aqueous solution of 31g dissolved in 600g of distilled water,
The reaction was carried out at 110°C for 1 hour.

After the reaction, no cloudiness was observed in the content liquid, but when stirring was stopped, it separated into two liquid layers.

The autoclave was immersed in a water tank and cooled to 30'C, the contents were put into a separating funnel to separate the lower layer, and the two layers were dried in the same manner as in Example 1.
5 g of solid was obtained.

From the analysis value of this solid, 2
-Yield of sodium chloroethanesulfonate is 34.5
%, the yield of sodium ethanedisulfonate is 61.5%
It became.

Patent applicant: Tosoh Corporation Procedure Ne City Official Book August 25, 1986

Claims (1)

[Claims] 10 to 45% of polar solvents that are miscible with water at room temperature to 130°C
A method for producing an organic monochlorosulfonate, which comprises reacting an organic dichloride and a sulfite in an aqueous solution containing wt% at a temperature higher than the boiling point of the reaction aqueous solution.