JPS6149303B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides sulfone diimine intermediates, N
-Regarding a method for producing substituted sulfonylsulfone diimines (hereinafter abbreviated as substituted sulfone diimines). Specifically, in the reaction between sulfyl imines [] and chloramines [], an alkyl cyanide [] is used as a reaction solvent, and the reaction is preferably carried out in the presence of a sulfonamide metal salt []. []Relating to the manufacturing method. Conventionally, methods for synthesizing substituted sulfone diimines include (1) a method of reacting a dialkyl sulfide with chloramines (J.Org.Chem. Vol. 29, p. 1397;
(1964), (2) Method of reacting dialkyl or diaryl sulfide with tertiary butoxychloride in the presence of excess ammonia (Chem.Ber.99
Vol. 3103, 1966). However, in (1), only dialkyl forms can be synthesized, and in (2), although alkyl forms and a small portion of alkyl/aryl forms can be synthesized, diaryl forms have not been synthesized. In addition, both (1) and (2) not only have poor yields but also have disadvantages such as operational difficulties and long reaction times, making it difficult to adopt them as industrial production methods and making them difficult to manufacture industrially. There was a strong desire for a new synthetic method. In view of the above-mentioned drawbacks, the present inventors have conducted intensive research and have already discovered a method for producing substituted sulfone diimines by reacting sulfyl imines with chloramines or in the coexistence of chloramines and sulfonamides. Initially, the invention was disclosed in Japanese Patent Application Laid-open No. 112321/1983, but after further study, the present invention was completed. That is, when sulfoylimines are reacted with chloramines, substituted sulfone diimines can be easily obtained, but at the same time sulfoximine and sulfoxides and sulfones are also produced as by-products. In order to reduce the amount of sulfoximine and by-products, we considered solvolysis and found that alkyl cyanide is extremely effective as a reaction solvent. That is, the present invention has the following formula: (In the formula, R ¹ and R ² represent alkyl, aryl, or substituted aryl.) Sulfoylimines represented by the formula (In the formula, R ³ represents alkyl, aryl, or alkyl-substituted aryl, X represents halogen, and A represents a metal atom.) When reacting with chloramines represented by the formula R ⁴ -CN [] ( In the formula, R ⁴ represents an alkyl group having 1 to 10 carbon atoms.) This is a method for producing N-substituted sulfonylsulfone diimines represented by the formula (wherein R ¹ , R ² , and R ³ are the same as above). formula (In the formula, R ⁵ represents alkyl, aryl, or alkyl-substituted aryl, and A' represents a metal atom.) When the reaction is carried out in the presence of a sulfonamide metal salt represented by It is preferable because it can be obtained. The reaction formula of the method of the present invention is as follows. Examples of the sulfuimines used in the present invention include dimethylsulfuimine, dibutylsulfuimine, bis(paramethoxyphenyl)sulfuimine, diphenylsulfuimine, phenylmethylsulfuimine, and phenylethylsulfuimine. , p-tolylphenylsulfuilimine, p-chlorophenylphenylsulfuimine, p-nitrophenylphenylsulfuimine, p-tolylmethylsulfuimine, and the like. Examples of the chloramines used in the present invention include sodium n-chlorobenzenesulfonamide, sodium tosylchloramide, potassium n-bromomethanesulfonamide, and the like. Examples of the alkyl cyanide used as a reaction solvent include acetonitrile, propionitrile, butyronitrile, amylonitrile, and the like. Examples of the sulfonamide metal salts include sodium benzenesulfonamide, sodium toluenesulfonamide, potassium methanesulfonamide, and the like. It is preferable to use the chloramines used in the reaction in an equivalent amount to a slight excess amount relative to the sulfyl imine. When the reaction is carried out in the presence of sulfonamide metal salts, the sulfonamide metal salts are used in an equivalent amount to a slight excess amount relative to the chloramines. It is preferable to use the amount. The reaction temperature is appropriately selected depending on the type of compound, but it is usually carried out at room temperature or at a temperature under reflux of the reaction solvent. The substituted sulfone diimines thus obtained,
If the reaction with concentrated sulfuric acid is followed by alkali treatment, for example, neutralization with an alkali, sulfonediimines can be easily obtained in quantitative yield. The concentration of sulfuric acid used is preferably 85% or higher; if the concentration is lower than that, the yield of the target product will be significantly reduced. As the alkali, ordinary organic and inorganic bases can be used without any problem. As mentioned above, the method of the present invention uses a surfactant,
This makes it possible to easily provide sulfone diimines, which are extremely useful as various synthetic intermediates, in high yields, and thus makes a huge contribution to this industry. The present invention will be further explained below with reference to Examples, Comparative Examples, and Reference Examples, but these are not intended to limit the present invention in any way. Examples 1 to 9 Diphenylsulfuimine 5.0g (25mmol)
5 times the mole of anhydrous sodium toluenesulfonamide and anhydrous sodium tosyl chloramide (chloramine-T) powder (10.0 g) were reacted in anhydrous acetonitrile (300 ml) at 40°C for 24 hours. After the reaction, the solvent was removed, a 10% aqueous sodium hydroxide solution was added to the residue, and the mixture was extracted with chloroform to obtain only N-tosyldiphenylsulfonediimine (Example 1). Various substituted sulfone diimines were obtained in a similar manner (Examples 2 to 9). The results are shown below.

【table】

[Table] Example 10 Diphenylsulfoylimine [5.0g
(25 mmol)] and 10.0 g of anhydrous sodium tosyl chloramide (chloramine-T) powder were reacted in 300 ml of anhydrous acetonitrile at 40°C for 24 hours.
After the reaction, the solvent was removed, a 10% aqueous sodium hydroxide solution was added to the residue, and the mixture was extracted with chloroform to obtain N-tosyldiphenylsulfonediimine. Yield 70
%. Example 11 Diphenylsulfuimine 5.0g (25mmol)
and 5 times the mole of anhydrous potassium methanesulfonamide and anhydrous N-bromomethanesulfonamide potassium
7.53g in 300ml of anhydrous acetonitrile at 40℃
The reaction was allowed to proceed for 24 hours. After the reaction, the solvent was distilled off, a 10% aqueous sodium hydroxide solution was added to the residue, and the mixture was extracted with chloroform to obtain only N-methyldiphenylsulfone diimines. Yield 88%. Example 12 Diphenylsulfuimine 5.0g (25mmol)
5 times the molar amount of anhydrous sodium toluenesulfonamide and 10.0 g of anhydrous sodium tosyl chloramide (chloramine-T) powder were reacted at 40° C. for 24 hours in 300 ml of anhydrous butyronitrile. After the reaction, the solvent was distilled off, a 10% aqueous sodium hydroxide solution was added to the residue, and the mixture was extracted with chloroform to obtain only N-tosyldiphenylsulfonediimine. Yield 93%. Comparative Examples 1 to 3 200 mg of diphenylsulfuimine and 400 mg of sodium tosyl chloramide in methanol at 40°C
The mixture was reacted for 6 hours. After removing the solvent, it was poured into a 10% sodium hydroxide solution and extracted with chloroform.
N-tosyldiphenylsulfoximine was separated using 6N-hydrochloric acid. Target N- from the chloroform layer
Tosyl diphenyl sulfone diimine was obtained. (Comparative Example 1). The same procedure as Comparative Example 1 was carried out except that 5 times the molar amount of sodium toluenesulfonamide was used (Comparative Example 2). After adding 200 mg of sodium toluenesulfonamide to methylene chloride and blowing chlorine gas under a nitrogen stream, excess chlorine gas was removed with nitrogen, and then excess sodium toluenesulfonamide and 200 mg of toluenesulfonamide were added. Add methanol to this and get 200mg of diphenylsulfuimine.
was added and reacted for 24 hours at room temperature in a nitrogen stream.
Post-treatment of the reaction solution was carried out in the same manner as in Comparative Example 1 (Comparative Example 3).

[Table] Comparative Examples 4 to 8 Using the solvents shown in the table below instead of methanol,
In the same manner as Comparative Example 2, the results shown in the table below were obtained.
In this case, the reaction was only followed by TLC.

[Table] Reference examples 1 to 5 N-tosyldiphenylsulfonediimine 1.0g
Add 5.0ml of concentrated sulfuric acid (95%) to (5mmol) and heat at 35℃.
The reaction was allowed to proceed for 48 hours. The reaction solution was poured into ice water and made alkaline with 50% sodium hydroxide solution under cooling. After extraction with chloroform, white crystals of diphenylsulfone diimine were obtained (Example 1). Various sulfone diimines were obtained in a similar manner (Examples 2 to 5). The results are shown below.

【table】

Claims (1)

[Claims] 1 formula (In the formula, R ¹ and R ² represent alkyl, aryl, or substituted aryl.) Sulfoylimines represented by the formula (In the formula, R ³ represents alkyl, aryl, or alkyl-substituted aryl, X represents halogen, and A represents a metal atom.) When reacting with chloramines represented by the formula R ⁴ -CN [] ( It is characterized by using an alkyl cyanide represented by the formula (in which R ⁴ represents an alkyl group having 1 to 10 carbon atoms). formula A method for producing N-substituted sulfonylsulfone diimines represented by the formula (wherein R ¹ , R ² , and R ³ are the same as above). 2 formulas (In the formula, R ⁵ represents alkyl, aryl, or alkyl-substituted aryl, and A' represents a metal atom.) A method for producing sulfonylsulfone diimines.