JPS5911583B2 - Process for producing substituted sulfone diimines - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides sulfone diimine intermediates, N-substituted sulfonylsulfilimines (hereinafter abbreviated as substituted sulfone diimines), which are useful as surfactants and various synthetic intermediates.

). 15 Specifically, sulfinimines have the formula R3-502N<(wherein R3 is alkyl, substituted alkyl, aryl, substituted aryl, cycloa20
alkyl, substituted cycloalkyl, X represents a halogen, and A represents a metal atom or optionally an ammonium group.

) (hereinafter abbreviated as chloramines) 2 | and the formula R
3-502N<A (in the formula, R3 represents alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, and A represents a metal atom or optionally an ammonium group) (hereinafter abbreviated as sulfonamides) This invention relates to a method for producing substituted sulfonimines, which comprises reacting them in the coexistence of 30% with .). Conventionally, sulfone diimines have been produced by a method in which dialkyl or diaryl sulfide is reacted with tertiary butoxy chloride in liquid ammonia (Chemische Berch 35).
ichte, Vol. 99, p. 3103, 1966) and the 3゜q-method in which dialkyl sulfide is reacted with chloramine and ammonia (Journal of the American
Chemical Society, p. 89, p. 2435-2443).

However, the former produces a large amount of chlorinated alkyl groups and benzene nuclei as by-products, resulting in extremely low product yields, while the latter has operational difficulties and requires a long reaction time, resulting in low yields. There are various drawbacks such as low oxidation rate and the fact that it can only be applied to the synthesis of specific sulfone diimines such as dialkyl derivatives, all of which are extremely difficult to adopt as an industrial production method.
An easy industrial synthesis method has been long awaited. The inventors of the present invention have conducted extensive studies in view of the drawbacks of the traditional rice methods as described above, and have developed a method for achieving high yields by reacting sulfuimines with chloramines or in the coexistence of chloramines and sulfonamides. The present invention was completed by discovering a process for producing substituted sulfone diimines at a low industrial cost.

The thus obtained substituted sulfone diimines are reacted with concentrated sulfuric acid and then treated with alkali to easily give industrially useful sulfone diimines in quantitative yields. The reaction formula of the method of the present invention is as follows.

That is, if sulfuimines [1] are mixed with chloramines [] and reacted in methanol at around room temperature,
Substituted sulfone diimines [ ] are obtained. If sulfonamides [ ] are used in combination during the reaction, substituted sulfone diimines [ ] can be obtained in even higher yields. The sulfinimines used in the present invention are i♂1 formula》S→M {in the formula, R1, R
2 represents alkyl, aryl, substituted alkyl, and substituted aryl.

Further, R1 and R2 may form a ring. ), such as dimethylsulfuimine, dibutylsulfuimine, bis(paramethoxyphenyl)sulfuimine, dimethylsulfuimine, pentamethylenesulfuimine, phenylmethylsulfuimine, phenylethyl Sulfuilimine, p-tolylphenylsulfuimine, p-chlorophenylphenylsulfuimine, p-nitrophenylphenylsulfuimine, phenylcyclopropylsulfuimine, p
-Tolylmethylsulfilimine and the like. The chloramines used in the present invention have the formula R3-SO2N (where R3 is alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, X is halogen, and A is a metal atom or optionally Represents an ammonium group.

), such as N-chlorobenzenesulfonamide sodium, tosylchloramide sodium, N-
Examples include potassium bromomethanesulfonamide.
Sulfonamides used in combination with chloramines have the formula R3
-SO2N( (wherein R3 is alkyl, substituted alkyl,
In aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, A represents a metal atom or optionally an ammonium group.

Examples of the compounds include sodium benzenesulfonamide, sodium toluenesulfonamide, and potassium methanesulfonamide. The chloramines used in the reaction are preferably used in an equivalent amount to a slight excess amount relative to the sulfindiimines, and when sulfonamides are used together, it is preferable to use the sulfonamides in large excess relative to the chloramines. .

The reaction temperature depends on the type of compound. Although the optimum conditions are appropriately selected depending on t, the reaction is usually carried out at room temperature or at a temperature under reflux of the reaction solvent. If the thus obtained substituted sulfone diimines are reacted with concentrated sulfuric acid and then neutralized with an alkali, the sulfone diimines can be obtained almost quantitatively.

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 neutralizing alkali, ordinary organic or inorganic bases can be used without any problem. As described above, by using the method of the present invention, it is possible to easily provide sulfone diimines, which are extremely useful as surfactants and various synthetic intermediates, in high yields. Yes, the contribution to this industry is extremely large.

The present invention will be further explained below with reference to Examples and Reference Examples.

In the examples and reference examples, parts indicating quantities are parts by weight. Example 20 parts of diphenylsulfyl imine, 40 parts of sodium tosyl chloramide and 400 parts of sodium toluene-p-sulfonamide were mixed in methanol at 40-50°C for 3 hours.
Allowed time to react.

After distilling off the solvent, N-tosyldiphenylsulfonediimine 3
I got 4 copies. M. p. l5l. 5-152°C. IRν
3270 (NH), ν10901ν1040, ν960
(N-S-N), elemental analysis values are as shown in the table below. Reference Example 1 Diphenylsulfuilimine (1) (200) and chloramine T (400~) are reacted in methanol at room temperature.

When the solvent is distilled off, sulfonediimine () and sulfoximine () are obtained in yields of 54% and 39%, respectively. A compound () with a melting point of 151.5-152° C. separates and is recrystallized from benzene. The yield of () increases to 92% when using a large excess of sodium toluene p-sulfonamide. The structure of () is based on elemental analysis, I
R. n. m. r Determined by means such as spectroscopic analysis. N of phenyl proton in (). m. The r chemical shift is N-p-
The chemical shift is similar to that of N-p-tosylsulfoximine or sulfone, rather than tosylsulfoylimine. Furthermore, () is stable in both acids and alkalis, proving that it has a tetravalent S structure () instead of the trivalent S structure Ph2S-N-NHTs.

Treatment of () with concentrated sulfuric acid gives diphenylsulfonediimine () quantitatively. Reference Example 2 Mix 40 parts of pentamethylene sulfyl imine, 40 parts of sodium tosyl chloramide, and 300 parts of methanol, and heat at 30-40°C.
The mixture was allowed to react for 4 hours.

After distilling off the solvent, 48 parts of N-tosylpentamethylenesulfone diimine was obtained. M. p. l45.5l46°C,. I
Rν3170 (NH), ν1090, ν1040, ν9
60 (N-S-N), elemental analysis values are as shown in the table below. Reference Example 3 12 parts of 90% concentrated sulfuric acid was added to 37 parts of N-toluene-p-sulfonyldiphenylsulfone diimine, and the mixture was heated at 50°C for 12 parts.
heated for an hour.

Next, the mixture was neutralized with 20 parts of a 50% caustic soda aqueous solution to obtain 21 parts of diphenylsulfone diimine. M. p. 88
-89℃, elemental analysis values are as shown in the table below.

Claims (1)

[Claims] 1. A compound with the formula ▲, which includes mathematical formulas, chemical formulas, tables, etc., and a compound with the formula ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ There are formulas, chemical formulas, tables, etc. that are characterized by reactions with compounds that are carried out in the presence of a compound that is a formula ▼ A method for producing a compound.