DE961625C - Process for the production of oxazolidines substituted on the nitrogen by organic sulfosaic acid residues - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

ISSUED APRIL 11, 1957

GERMAN PATENT OFFICE

PATENT LETTERING

CLASS 12p GROUP 3 INTERNAT. CLASS C 07 d

B 2I00IIV b / 12 p

Dr. Rudi Ratz, Düsseldorf-Holthausen

has been named as the inventor

Böhme Fettchemie G.m.b.H., Düsseldorf

Process for the preparation of oxazolidines substituted on nitrogen by organic sulfonic acid residues

Patented in the territory of the Federal Republic of Germany on August 14, 1952

Patent application published October 18, 1956

Patent issued March 28, 1957

It has been found that novel, nitrogen-substituted oxazolidines are obtained if one N - (/ S-oxyalkyl) sulfonamides of the formula

R_SO ₂ - NH - CH ₂ - CH (OH) —R '

in which R is an alkyl, aryl, aralkyl or cycloalkyl radical and R 'is hydrogen or a hydrocarbon radical means with aldehydes of the formula R "CHO, in which R "denotes hydrogen or a hydrocarbon radical, or with corresponding aldehyde-releasing agents Substances in the presence of gaseous hydrogen halide and inert solvents brings to implementation with the exclusion of water. One obtains the nitrogen by organic Sulphonic acid radicals substituted oxazolidines, those of the general formula

R-SO ₂ -N CH ₂

R "- CH CH - R '

correspond, in which R is an alkyl, aryl, aralkyl or cycloalkyl radical and R 'or R "is hydrogen or means a hydrocarbon residue. The carbon skeletons of R 'and R "can, provided that these are not mean a hydrogen atom, as well as that of

R be interrupted by heteroatoms or heteroatom groups or carry substituents.

The reaction takes place at temperatures below 100 ° C, preferably at room temperature, and is in an inert anhydrous solvent, for example in benzene, toluene, tetrahydronaphthalene, decahydronaphthalene, chlorinated hydrocarbons, carried out. Apparently, a chloromethyl ether is initially formed as an intermediate product ίο which reacts immediately to form oxazohdin with ring closure.

The starting materials used for the above process For example, the following oxyalkylated sulfonamides can be considered: N- (ß-oxyethyl) butanesulfonamide, N- (jS-Oxyäthyl) -dodecansulfonamid, N- (0-Oxyäthyl) -4-toluenesulfonamid, N - (^ 0xyäthyl) -4-alkylbenzenesulfonamide, N- (jS-Oxyäthyl) -4-nitrobenzenesulfonamide, N, N'-Di - ((S-Oxyethyl) -benzene-i, 3-disulfamide, N ^ Dioxypropyl) dodecylbenzenesulfonamide. As aldehydes or aldehyde-releasing substances come primarily formaldehyde, paraformaldehyde, trioxymethylene, hexamethylenetetramine, furthermore Acetaldehyde, benzaldehyde, and the like. As hydrogen halide it is primarily drier Hydrogen chloride used. However, the process can also be carried out with the other hydrogen halides.

In the case of those produced according to the present invention on nitrogen by organic sulfonic acid residues substituted oxazolidines are relatively sparingly soluble in water and in organic solvents on the other hand, easily soluble compounds. These disintegrate in acidic solution with regression of the too N- (jS-oxyalkyl) sulfonamides used in their preparation and the corresponding aldehyde compound, however, are stable in alkaline solution. One can use these compounds as intermediates in the construction of pesticides, textile finishing agents and pharmaceutical agents. Under certain conditions they show the character of disinfectants. Unless they are higher molecular weight Containing hydrocarbon residues, the compounds have plasticizer properties.

It is known that one can choose from N-alkylated or N-arylated oxyethylamines and formaldehyde in aqueous alkaline solution by ring closure to the corresponding N-alkylated or N-arylated oxazolidines can arrive. This implementation is in use of N- (j5-OxyaIkyl) -sulfonamiden not feasible. It was therefore surprising that the reaction among those used according to the invention Conditions is possible.

example 1

21.5 g of N- (18-oxyethyl) -4-toluenesulfonamide ( ¹ _{l 10} mol) and 3.3 g of paraformaldehyde are ^{suspended in 250 cm 3 of} dry benzene. A stream of dry hydrogen chloride is passed into the suspension with stirring. The reactants go into solution with the separation of water.

The water of reaction is separated from the benzene layer and discharged from it a dry air stream displaces the dissolved hydrogen chloride gas. After drying with calcium chloride the solvent is distilled off in vacuo, leaving an oil behind, which after some time crystalline solidified. The N- (4-toluenesulfonyl) oxazolidine is obtained in almost quantitative yield. The compound can be recrystallized from water and then has a melting point of 105 ° to 106 °.

Example 2

According to Example 1, 47 g of N - (/ 3-0xyethyl) -4-chlorobenzenesulfonamide ( ¹ Z ₅ mol) are reacted with 6.6 g of paraformaldehyde in 200 cm ^{3 of} dry benzene while passing in hydrogen chloride gas. The oil obtained after the benzene has been distilled off changes to crystal form after washing with water until it reacts neutral and drying in vacuo. The resulting N- (4-chlorobenzenesulfonyl) oxazolidin falls after recrystallization from water in the form of colorless fine needles of mp. 83-84 to ^0.

Example 3

12.8 g of N - (^ - oxyethyl) dodecanesulfonamide (melting point 63 to 64 °) are dissolved in 100 cm ^{3 of} dry benzene. After adding 1.44 g of paraformaldehyde, hydrogen chloride gas is passed into the solution with stirring. After the reaction has ended, the water of reaction is separated off and, as described in Example 1, worked up. The oil obtained after the benzene has been distilled off is carefully washed with water until it reacts neutral. Drying is carried out in vacuo at 50 °, a pale yellowish oil being obtained which, after standing for several days, turns into a semi-solid, ointment-like mass. The N- (dodecanesulfonyl) -oxazolidine formed is obtained in almost quantitative yield.

Example 4

In the same way as in the preceding examples, 6.46 g of N - (/? - γ-dioxypropyl) -dodecanesulfonamide are obtained (M.p. 109 to 100 °) and 0.66 g Paraformaldehyde N- (dodecanesulfonyl) -5-oxymethyl-oxazolidine in the form of an almost colorless, semi-solid mass.

Example 5

24.6 g of N- (j5-Oxyäthyl) -4-nitrobenzenesulfonamide (Vi ₀ MoI; mp. 126.5 to 127.5 °), 3.3 g of paraformaldehyde and hydrogen chloride gas in benzene solution gives the N- (4- nitrobenzenesulfonyl) oxazolidin in about 8o ° / ₀ yield. The clear, yellow οί obtained after the benzene has been distilled off is washed with water until it has a neutral reaction, during which it gradually solidifies. After drying in vacuo, it can be ground to a fine powder which can be recrystallized from a water-acetone mixture. The pale yellowish N- (4-nitrobenzenesulfonyl) oxazolidine obtained melts at about 10 ° with prior sintering.

Example 6

176.5 g ( ¹ Za mol) of an alkylbenzenesulfochloride mixture (average alkyl chain length

C ₁₃ ) and N- (/ S-oxyethyl) -alkylbenzenesulfonamides prepared from monoethanolamine are reacted with 16.5 g of paraformaldehyde in 400 cm ^{3 of} benzene while passing in hydrogen chloride gas. The residual in vacuo after evaporation of the benzene viscous reaction product is washed until neutral with io ° / ₀ saline. The product is taken up in ether and dried with sodium sulfate. After filtration and removal of the solvent, the N- (alkylbenzenesulfonyl) oxazolidine formed is obtained in the form of a brown-colored clear syrup.

Example 7

43 S / 3-oxethyl-p-toluenesulfonamide (0.2 mol) and 12 g of acetaldehyde are suspended in 200 ecm of dry benzene. A stream of dry hydrogen chloride gas is passed into the suspension with stirring. The reactants go into solution with the separation of water. When the reaction has ended, the reaction product crystallizes out as a white powder. This is suctioned off and washed several times with water to remove excess hydrogen chloride gas. The dry reaction product can easily be recrystallized from alcohol, with N- (p-toluenesulfonyl) -2-methyl-oxazolidine being obtained in almost quantitative yield as colorless prisms with a melting point of 127 ° to 128 °.

Example 8

22.9 g ( ^× / ₁₀ mol) of N-isopropanol-p-toluenesulfonamide (melting point 59 to 60 °) and 3.3 g of paraformaldehyde are suspended in about 250 ecm of dry benzene. A stream of dry hydrogen chloride is passed into the suspension with stirring. The reactants dissolve with the separation of water. The water of reaction is separated from the benzene layer and the excess hydrogen chloride gas is displaced therefrom by introducing a stream of dry air. After drying with calcium chloride, the benzene is distilled off in vacuo. A light yellow oil is obtained which quickly solidifies in the cold. After recrystallization from alcohol, white, approximately isometric crystals of N- (p-toluenesulfonyl) -5-methyl-oxazolidine with a melting point of 78 ° to 79 ° are obtained in almost quantitative yield.

Claims (1)

PATENT CLAIM: Process for the production of substituted on nitrogen by organic sulfonic acid residues Oxazolidines, characterized in that N- (j8-oxyalkyl) sulfonamides of the formula R-SO ₂ -NH-CH ₂ -CH (OH) -R ' in which R is an alkyl, aryl, aralkyl or cycloalkyl radical and R 'denotes hydrogen or a hydrocarbon radical, with aldehydes of the formula R "CH0, in which R" denotes hydrogen or a hydrocarbon radical, or with the corresponding aldehyde-releasing substances in the presence of gaseous hydrogen halide and inert solvents with the exclusion of water to the reaction, wherein the carbon skeletons of the radicals R, R 'or R "also by heteroatoms or heteroatom groups be interrupted or can carry substituents. @ 609 658/452 10.56 (609 855 4. 57)