JPH06263715A - Production of high-purity methanesulfonyl chloride - Google Patents

Abstract

PURPOSE:To produce a methanesulfonyl fluoride useful as an intermediate for medicines and agrochemicals or a raw material for trifluoromethanesulfonic acid in high yield. CONSTITUTION:A product obtained by reacting methanesulfonyl chloride with a fluoride and water is separated in the presence of water in an amount of >=0.7 the weight of methanevelforayl chloride by distillation. The resultant fraction is then separated into two phases.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an intermediate of medicines and agricultural chemicals or
Trifluoromethanesulfonic acid (CF₃SO ₃H) made
Methanesulfonylflora, a substance useful as a raw material
The present invention relates to a method for manufacturing an id.

[0002]

2. Description of the Related Art Although trifluoromethanesulfonic acid is produced by an electrolytic fluorination method, methanesulfonyl fluoride has higher current efficiency than methanesulfonyl chloride as a raw material. , Increase the yield. There is also an advantage that generation of chlorine can be suppressed.

The following method is generally known as a method for producing methanesulfonyl fluoride. A metal fluoride such as potassium fluoride or sodium fluoride is mixed with methanesulfonyl chloride, and water is added as a reaction solvent to carry out the reaction.

CH ₃ SO ₂ Cl + KF → CH ₃ SO ₂ F + KCl At the end of the reaction, the product is separated by distillation or separation by filtration to obtain methanesulfonyl fluoride.

In this reaction, the raw material methanesulfonyl chloride and the product methanesulfonyl fluoride are hydrolyzable, and methanesulfonyl fluoride is slightly soluble in water. The amount of is generally the minimum amount in consideration of the reaction rate.

Therefore, when the distillation method is used as a method for recovering the desired methanesulfonyl fluoride from the reaction product, a sufficient yield cannot be obtained. on the other hand,
After the reaction, methanesulfonyl fluoride can be obtained by separating the liquid by filtration, but since the by-products such as salts are mixed in the separated product, the treatment in the subsequent purification process becomes complicated. There is a problem such as becoming.

As a method for dehydration purification, Na ₂ SO ₄ ,
A method using a general dehydrating agent such as zeolite is known. However, in these methods, mass production has been difficult due to difficulty in handling due to problems such as treatment with a dehydrating agent or toxicity of methanesulfonyl fluoride.

[0008]

[Means for Solving the Problems] The inventors of the present invention have made earnest studies on a method for obtaining methanesulfonyl fluoride easily and in a high yield. It was found that methanesulfonyl fluoride can be obtained in a high yield by distilling a reaction product in a system in which water, which was considered to be good, is allowed to exist in a certain amount.

That is, according to the present invention, the product obtained by the reaction of methanesulfonyl chloride with fluoride and water is distilled in the presence of 0.7 weight times or more of water with respect to methanesulfonyl chloride, and the fraction is distillated. A method for producing methanesulfonyl fluoride, which comprises recovering methanesulfonyl fluoride after phase separation.

In the present invention, the fluoride is 1 to 3 equivalents, preferably 1 to 1 with respect to methanesulfonyl chloride.
A range of 1.5 times equivalent is preferable. If the amount of fluoride is less than the equivalent amount, the reaction rate becomes very slow and unreacted methanesulfonyl chloride remains. Further, if it exceeds this range, there is no particular advantage and it is not economical.

The fluoride used in the present invention includes alkali metal fluorides such as KF and NaF, and KF · n.
Acidic alkali metal fluorides such as HF, NaF / nHF,
NH ₄ F, (NH ₄ ) ₂ SiF ₆ , H ₂ SiF ₆ , Na
₂ SiF ₆ , HF or a mixture of the above substances can be used,
Alkali metal fluorides are particularly preferable. KF from the viewpoint of reaction rate, and NaF and Na ₂ Si from the viewpoint of economic efficiency.
F ₆ is preferred. The reaction conditions, particularly the preferable amount of water added, vary depending on the type of these fluorides. Although water is used as a reaction solvent in this reaction, the reaction proceeds in a state where the fluoride is dissolved in the reaction system. Therefore, when using a fluoride with a low solubility, even if the fluorine source required for the reaction is sufficiently present with respect to methanesulfonyl chloride as a whole, the undissolved fluorine source does not contribute to the reaction, so try to shorten the reaction time. If so, it is necessary to increase the amount of water added. In the case of NaF, the range of 2.0 to 10.0 times the weight of NaF is preferable.

When the amount is less than this range, the reaction time becomes long and the recovery rate of methanesulfonyl fluoride decreases in the distillation operation in the next stage. Further, even if it exceeds this range, there is no particular change in the recovery rate, and this range is preferable in consideration of device efficiency and the like.

On the other hand, when a substance such as KF that is sufficiently soluble in water and has a high reaction rate is used, the amount of water used for the reaction may be small. The reaction temperature is preferably in the range of room temperature to 60 ° C, and if it exceeds 60 ° C, the yield is lowered due to hydrolysis.

In the present invention, the reaction product is distilled to recover methanesulfonyl fluoride. At this time, methanesulfonyl fluoride and water are distilled at a vapor pressure ratio thereof. Therefore, in this sense, the amount of water added during distillation significantly affects the recovery rate of methanesulfonyl fluoride. This water may be added at the time when the reaction is completed, but it is preferable to add it before the reaction in view of the reaction rate. The amount of addition should be 0.7 times or more the weight of methanesulfonyl chloride. Although the upper limit is not particularly limited, it is preferably 3.0 times or less by weight from the economical point of view.

When the amount of water added is small, salts such as by-products are precipitated during the distillation, resulting in poor thermal efficiency and poor distillation efficiency. In addition, when a coil-type reactor is used as the heat transfer method, it is necessary to consider the type of reactor, such as products with high boiling points remaining.

In the present invention, distillation is preferably carried out under reduced pressure from the viewpoint of suppressing hydrolysis, usually 5
The pressure is 0 to 100 Torr or less. 50 Tor
On the other hand, below r, it becomes too low and loss occurs in the condenser.

The reactor used is not particularly limited, but those capable of mixing the raw materials in order to accelerate the reaction are preferable. For example, a jacket-type reaction vessel equipped with a stirrer (material: Teflon-coated SS material, etc.) can be used.

The distilled methanesulfonyl fluoride and water are separated into two phases, and the methanesulfonyl fluoride is on the lower layer side. This liquid separation operation can be easily performed by visual inspection and measurement of electric conductivity. In addition, methanesulfonyl fluoride was dissolved in the separated aqueous phase, which was a factor in lowering the yield. However, by using this aqueous phase in the next reaction, the methanesulfonyl fluoride dissolved in the aqueous phase was dissolved. Fluoride can be recovered.

The impurity of methanesulfonyl fluoride obtained in the present invention is only water, which facilitates the subsequent purification step. That is, the desired purified product can be obtained by performing the dehydration step by distillation and removing about 20% by weight of the initial distillation. The first distillation product is the reaction process of the next batch (distillation separation process)
Alternatively, it can be recovered by cycling the separation process. Thus, the purification step can be efficiently performed by a simple method such as distillation.

In the reaction of methanesulfonyl chloride, fluoride and water, some methanesulfonyl chloride may remain depending on the reaction conditions, but in the separation method by distillation according to the present invention, a mixture of methanesulfonyl fluoride and methanesulfonyl chloride is used. Even if there is, the purpose can be achieved sufficiently. In this case, after the reaction, methanesulfonyl chloride, methanesulfonyl fluoride and water will be distilled off by distillation.

[0021]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples.

Example 1 140 kg of methanesulfonyl chloride and 60 kg of sodium fluoride (1.m3) were placed in a jacket type reaction tank (1 m ³ ).
(2 times equivalent) and 420 kg of water (3.0 times by weight) were added and mixed well to react. The reaction was completed at a reaction temperature of 50 ° C. for 4 hours. After the reaction, simple distillation was performed at 60 Torr and 50 ° C. to distill off methanesulfonyl fluoride. Distillation was carried out until no distillate of methanesulfonyl fluoride was observed. After the distillation, the two phases were visually separated to obtain 113 kg of methanesulfonyl fluoride on the lower layer side. The yield was 94.2%. 5.0 kg of methanesulfonyl fluoride was contained in 75 kg of the upper side aqueous phase. The methanesulfonyl fluoride on the lower layer side is again 60 Tor
Single distillation was carried out at r and 50 ° C. for dehydration purification. The water content of methanesulfonyl fluoride in the reaction vessel was 150 ppm when the initial distillation cut was 20% by weight.
I got kg.

Example 2 To the same apparatus as in Example 1, 280 kg of methanesulfonyl chloride, 120 kg of sodium fluoride (1.2 times equivalent) and 420 kg of water (1.5 times by weight) were added and mixed well to cause a reaction. The reaction was completed at a reaction temperature of 50 ° C. for 4 hours. After the reaction, simple distillation was performed at 60 Torr and 50 ° C. to distill off methanesulfonyl fluoride. Distillation was carried out until no distillate of methanesulfonyl fluoride was observed. After the distillation, the two phases were visually separated to obtain 225 kg of methanesulfonyl fluoride on the lower layer side. Yield 9
It was 4.0%. Methanesulfonyl fluoride was contained in 9.5 kg in 140 kg of the upper aqueous phase. The methanesulfonyl fluoride on the lower layer side is again at 60 Torr,
Single distillation was carried out at 50 ° C. for dehydration purification. The initial distillate cut is 18% by weight, and the water content in methanesulfonyl fluoride in the reaction tank is 250 ppm.
g was obtained.

Example 3 In the same apparatus as in Example 1, 280 kg of methanesulfonyl chloride, 115 kg of sodium fluoride (1.1 times equivalent weight), and 300 kg of water were further separated into the aqueous phase 1 in Example 2.
40 kg (total 430 Kg: 1.5 times by weight) was added, and the reaction was carried out at a reaction temperature of 50 ° C. for 4 hours. 60 To after reaction
Single distillation was carried out at rr at 50 ° C., and after liquid separation, 233 kg of methanesulfonyl fluoride on the lower layer side was obtained. Yield 9
It was 7.2%. The upper side aqueous layer (145 kg) contained 9.8 kg of methanesulfonyl fluoride. The methanesulfonyl fluoride on the lower layer side is again at 60 Torr,
Single distillation was carried out at 50 ° C. for dehydration purification. The initial distillate cut is 18% by weight, and the water content in methanesulfonyl fluoride in the reaction tank is 250 ppm.
g was obtained.

Example 4 To the same apparatus as in Example 1, 280 kg of methanesulfonyl chloride, 120 kg of sodium fluoride (1.2 times equivalent), 200 kg of water (0.7 times by weight) were added, and reaction temperature was 50 ° C., 4 The reaction was carried out in time. After reaction, 60 Tor
Single distillation was performed at r and 50 ° C., and after liquid separation, 224 kg of methanesulfonyl fluoride on the lower layer side was obtained. Yield 93.
It was 4%. The upper aqueous layer (140 kg) contained methanesulfonyl fluoride (9.5 kg). The methanesulfonyl fluoride on the lower layer side was regenerated to 60 Torr, 50
Single distillation was performed at 0 ° C. to perform dehydration purification. First Tome Cut 18
In weight%, the water content in methanesulfonyl fluoride in the reaction tank was 250 ppm, and 180 kg of dehydrated purified product was obtained.

Comparative Example 1 280 kg of methanesulfonyl chloride, 120 kg of sodium fluoride (1.2 times equivalent) and 185 kg of water (0.65 times by weight) were added to the same apparatus as in Example 1, and the reaction temperature was 50 ° C., 4 The reaction was carried out in time. After reaction, 60 Tor
Single distillation was carried out at r and 50 ° C., and after liquid separation, 192 kg of methanesulfonyl fluoride on the lower layer side was obtained. Yield 80.
It was 0%. The upper side aqueous layer (130 kg) contained methanesulfonyl fluoride (8.8 kg). The methanesulfonyl fluoride on the lower layer side was regenerated to 60 Torr, 50
Single distillation was performed at 0 ° C. to perform dehydration purification. First Tome Cut 18
In weight%, the water content in methanesulfonyl fluoride in the reaction tank was 250 ppm, and 155 kg of dehydrated purified product was obtained.

Comparative Example 2 280 kg of methanesulfonyl chloride, 115 kg of sodium fluoride (1.1 times equivalent) and 170 kg of water (0.6 times by weight) were added to the same apparatus as in Example 1, and the reaction temperature was 50 ° C., 4 The reaction was carried out in time. 60 Torr after reaction,
Simple distillation at 50 ° C for methanesulfonyl fluoride 18
9 kg was obtained. The yield was 79.0%. Methanesulfonyl fluoride is 8.7k in 130kg of upper water layer
g was included. The methanesulfonyl fluoride on the lower layer side was again subjected to simple distillation at 60 Torr and 50 ° C. for dehydration purification. When the initial distillation cut was 18% by weight, the water content in methanesulfonyl fluoride in the reaction tank was 250 ppm, and 154 kg of dehydrated purified product was obtained.

Example 5 140 kg of methanesulfonyl chloride and 76 kg (1.1 of potassium fluoride) were added to a jacket type reaction tank (1 m ³ ).
(Double equivalent) and 420 kg of water (3.0 times by weight) were added and mixed well to react. The reaction was completed at a reaction temperature of 50 ° C. for 4 hours. After the reaction, simple distillation is performed at 60 Torr and 50 ° C.
Methanesulfonyl fluoride was distilled off. Distillation was carried out until no distillate of methanesulfonyl fluoride was observed. After the distillation, the two phases were visually separated to obtain 113 kg of methanesulfonyl fluoride on the lower layer side. Yield 9
It was 4.0%. Methanesulfonyl fluoride was contained in an amount of 5.1 kg in 75 kg of the upper aqueous phase. The methanesulfonyl fluoride on the lower layer side is again at 60 Torr, 5
Single distillation was performed at 0 ° C. to perform dehydration purification. First Tome Cut 1
At 8% by weight, the water content in methanesulfonyl fluoride in the reaction tank was 250 ppm, and 90 kg of dehydrated purified product was obtained.

Example 6 To the same apparatus as in Example 1, 280 kg of methanesulfonyl chloride, 156 kg of potassium fluoride (1.1 times equivalent) and 420 kg of water (1.5 times by weight) were added and mixed well to react. The reaction was completed at a reaction temperature of 50 ° C. for 4 hours. After the reaction, simple distillation was performed at 60 Torr and 50 ° C. to distill off methanesulfonyl fluoride. Distillation was carried out until no distillate of methanesulfonyl fluoride was observed. After the distillation, the two phases were visually separated to obtain 227 kg of methanesulfonyl fluoride on the lower layer side. Yield 9
It was 4.8%. Methanesulfonyl fluoride was contained in 9.5 kg in 140 kg of the upper aqueous phase. The methanesulfonyl fluoride on the lower layer side is again at 60 Torr,
Single distillation was carried out at 50 ° C. for dehydration purification. The water content in the methanesulfonyl fluoride in the reaction tank was 250 ppm when the initial distillation cut was 18% by weight.
g was obtained.

Example 7 To the same apparatus as in Example 1, 280 kg of methanesulfonyl chloride, 156 kg of potassium fluoride (1.1 times equivalent) and 150 kg of water were added, and the reaction was carried out at a reaction temperature of 50 ° C. for 4 hours. After the reaction, 50 kg of water (total 200 kg:
(0.7 times by weight), and simple distillation was performed at 60 Torr and 50 ° C. to obtain 228 kg of methanesulfonyl fluoride. The yield was 95.2%. 140 kg of upper water phase
9.5 kg of methanesulfonyl fluoride was contained therein. The methanesulfonyl fluoride on the lower layer side is again 60
A simple distillation was performed at Torr and 50 ° C. for dehydration purification.
When the initial distillation cut was 18% by weight, the water content in methanesulfonyl fluoride in the reaction tank was 250 ppm, and 187 kg of a dehydrated purified product was obtained.

Comparative Example 3 To the same apparatus as in Example 1, was added 280 kg of methanesulfonyl chloride, 156 kg of potassium fluoride (1.1 times equivalent), and 185 kg of water (0.65 times by weight), and the reaction temperature was 50 ° C., 4 The reaction was carried out in time. After reaction, 60 Tor
Single distillation was performed at r and 50 ° C. to obtain 201 kg of methanesulfonyl fluoride. The yield was 84.0%. Methanesulfonyl fluoride was added to 135 kg of the upper aqueous phase.
1 kg was included. The methanesulfonyl fluoride on the lower layer side was again subjected to simple distillation at 60 Torr and 50 ° C. for dehydration purification. The initial distillate cut was 18% by weight, and the water content in methanesulfonyl fluoride in the reaction tank was 250 ppm, and 164 kg of a dehydrated purified product was obtained.

Comparative Example 4 280 kg of methanesulfonyl chloride, 156 kg of potassium fluoride (1.1 times equivalent) and 170 kg of water (0.6 times by weight) were added to the same apparatus as in Example 1, and the reaction temperature was 50 ° C., 4 The reaction was carried out in time. After reaction, 60 Tor
Single distillation was performed at r and 50 ° C. to obtain 199 kg of methanesulfonyl fluoride. The yield was 83.0%. Methanesulfonyl fluoride was added to 135 kg of the upper aqueous phase.
It contained 2 kg. The methanesulfonyl fluoride on the lower layer side was again subjected to simple distillation at 60 Torr and 50 ° C. for dehydration purification. When the initial distillation cut was 20% by weight, the water content in methanesulfonyl fluoride in the reaction tank was 180 ppm, and 159 kg of dehydrated purified product was obtained.

Example 8 To the same apparatus as in Example 1, 280 kg of methanesulfonyl chloride, 115 kg of sodium fluoride (1.1 times equivalent) and 420 kg of water (1.5 times by weight) were added, and the reaction temperature was 50 ° C., 4 The reaction was carried out in time. After the distillation, the two phases were visually separated and the methanesulfonyl fluoride 2 on the lower layer side was separated.
27 kg was obtained. When the water content and purity in the distilled methanesulfonyl fluoride were analyzed, the water content was 1.2%, the purity was 98.8%, and the yield was 93.5%. 150 kg of the water layer on the upper layer side contained 10.2 kg of methanesulfonyl fluoride. The methanesulfonyl fluoride on the lower layer side was again subjected to simple distillation at 60 Torr and 50 ° C. for dehydration purification. The initial distillate cut is 20% by weight, and the water content in methanesulfonyl fluoride in the reaction tank is 150.
It became ppm, and 182 kg of dehydrated purified product was obtained. In addition, 42.7 kg of methanesulfonyl fluoride was contained in 45.4 kg of the cut fraction after the initial distillation.

Example 9 In an apparatus similar to that of Example 1, 280 kg of methanesulfonyl chloride, 115 kg of sodium fluoride (1.1 times equivalent), and 300 kg of water were further separated into the aqueous phase 1 in Example 8.
50 kg (including 10.2 kg of methanesulfonyl fluoride) and 45.4 kg of the first cut fraction of the dehydration purification process
(Containing 42.7 kg of methanesulfonyl fluoride) was added (total water 443 Kg: 1.6 times by weight), and the reaction temperature was 50.
The reaction was carried out at 4 ° C for 4 hours.

After the reaction, simple distillation was carried out at 60 Torr and 50 ° C., and after liquid separation, 277.6 kg of methanesulfonyl fluoride on the lower layer side was obtained. When the water content and the purity of the distilled methanesulfonyl fluoride were analyzed, the water content was 1.
The purity was 0% and the purity was 99.0%. Upper water layer 150
10.3 kg of methanesulfonyl fluoride was contained in kg. In addition, the methanesulfonyl fluoride 42.
The yield excluding 7 kg was 96.8%.

Example 10 The same apparatus as in Example 1 was charged with 280 kg of methanesulfonyl chloride and 115 kg of sodium silicofluoride (1.5 kg).
(Double equivalent) and 420 kg of water (1.5 times by weight) were added, and the reaction was carried out at a reaction temperature of 50 ° C. for 4 hours. 60 To after reaction
Single distillation was carried out at rr and 50 ° C. to obtain 228 kg of methanesulfonyl fluoride. The yield was 95.1%. Methanesulfonyl fluoride was contained in 9.5 kg in 140 kg of the upper aqueous phase. The methanesulfonyl fluoride on the lower layer side is again subjected to simple distillation at 60 Torr and 50 ° C,
It was dehydrated and purified. The initial distillate cut is 18% by weight, and the water content in the methanesulfonyl fluoride in the reaction tank is 250 pp.
m, and 187 kg of dehydrated purified product was obtained.

Comparative Example 5 The same apparatus as in Example 1 was charged with 280 kg of methanesulfonyl chloride and 115 kg of sodium silicofluoride (1.5 kg).
(Double equivalent) and 170 kg of water (0.6 weight times) were added, and the reaction was carried out at a reaction temperature of 50 ° C. for 4 hours. 60 To after reaction
Single distillation was carried out at rr and 50 ° C. to obtain 194 kg of methanesulfonyl fluoride. The yield was 81.1%. Methanesulfonyl fluoride was contained in 8.8 kg in 130 kg of the upper aqueous phase. The methanesulfonyl fluoride on the lower layer side is again subjected to simple distillation at 60 Torr and 50 ° C,
It was dehydrated and purified. The initial distillate cut is 18% by weight, and the water content in the methanesulfonyl fluoride in the reaction tank is 250 pp.
Then, 159 kg of dehydrated purified product was obtained.

[0038]

Industrial Applicability According to the present invention, methanesulfonyl fluoride, which is useful as an intermediate for medical and agricultural chemicals and a raw material for producing trifluoromethanesulfonic acid, can be easily produced with high purity and high yield.

Claims (3)

[Claims] 1. Methanesulfonyl chloride (CH ₃ S
The product obtained by the reaction of (O ₂ Cl) with fluoride and water is separated by distillation in the presence of 0.7 times by weight or more water of methanesulfonyl chloride, and the fraction is separated into two phases. Methanesulfonyl fluoride (CH ₃ SO
_A process for producing methanesulfonyl fluoride, which comprises recovering ₂ F). 2. The fluoride is an alkali metal fluoride, an acidic alkali metal fluoride, NH ₄ F or (NH ₄ ) ₂ Si.
The method for producing methanesulfonyl fluoride according to claim 1, which is F ₆ , H ₂ SiF ₆ , Na ₂ SiF ₆ , or HF. 3. The method for producing methanesulfonyl fluoride according to claim 1, wherein the methanesulfonyl fluoride containing water is separated by distillation as impurities.