DE1618410A1 - Process for the preparation of sulfonyldicarbonylimides - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKU SEN-Bayerwerk Fy / gb PATENT REPORT April 26, 196?

METHOD FOR MANUFACTURING YON SULFONYLDICARBOHYLIMIDEN

(Addition to patent. .., ... (German Patentaas # i4 * Hig g- -Vi £ o))

Subject of the main patent, "... ... (German Patent Application Έ 51170 IVb / L2O) is a process for preparing Sulfonyldicarbonylimiden to give SuIfonamide the formula ·

R (SO ₃ -NH ₂ ) n
in which

η stands for 1 or 2 and

R is an n-valent, optionally substituted alley l- _f cycloalkyl, aralkyl or aryl radical,

with the equimolar amount of an alkali hydroxide in alcohol and one that boils higher than alcohol, and one that is aaseotropic with water aromatic hydrocarbons which form emiseh, at normal pressure to remove the water up to Reaching the boiling point of the aromatic hydrocarbon then heated · »so much of the same type of anhydrous

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Alcohol yields to the aromatic hydrocarbon about 5 to about 60 vol. 56 of the total amount of the diluent then with the stoichiometrically required amount of an oxalic acid derivative of the formula

X-C-G-O-Y

Il Il
0 0

wherein
X stands for the radicals -OE ₁ and -N and where

the radicals R ₁ , R ₈ , R _{8 have} the same scope of meanings as R, but can be identical to or different from R, R ₂ and R _{3 can} also stand for hydrogen and Y is an aliphatic or cyel © aliphatic hydrocarbon radical,

brings to implementation at elevated temperature and after acidification the sulfonyldicarbonylimide of the general formula

R (SO ₂ HHCOCOX) n

la which

R, X and η have the meaning given above, isolated.

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In further processing of the main patent on which the main patent is based The idea of the invention has now been found that one sulfonyl " dicarbonylimide is obtained if, according to the ¥ erfahrenbeälngungen of the main patent. ...... (German patent application P 51 170 IVb / 120) a sulfonamide of the formula

R (SO ₂ HH ₂ ) n ■ ".. ■ · ■

in which

η stands for 1 or 2, R is optionally an n-valent substituted alkyl, cycloalkyl, aralkyl © the aryl radical means with an oxalic acid derivative of the general Formula-,

XC - C - 0 - T

■ ii tf ^: ■■■ - ■

whereby '

- - - ■% "■: .-. ■; ■ = ■" ■■■ "■: ■; ■■■■■■■

X stands for the remainder -N ^ and

■. "- ^ R _a ■■■■: - ^: .: ■

whereby

R ₁ and R _{2 represent the} same or different radicals such as what β erstoff optionally substituted alkyl, aryl, cycloalkyl, aralkyl radicals and where at least one of the two radicals R ₁ or R _{2 is} at least one double bond containing at least one unsaturated radical, Y stands for an aliphatic or © ycloaliphatic hydrocarbon residue, which brings about reaction at an elevated temperature.

As alkyl radicals R are those with 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, mentioned, the given

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if they can also contain a double or triple bond. The substituents on these alkyl radicals are NO ₂ , halogens (fluorine, chlorine, bromine, iodine) and alkoxy groups with 1 to 4 carbon atoms. Both partially halogenated and perhalogenated alkyl radicals are to be understood as halogen substitution products.

Cycloalkyl radicals E which may be mentioned are those having 5 to 12 carbon atoms, preferably 5 and 6 carbon atoms in the ring system. Possible substituents on the cycloalkyl _{radical are: NO 8} , halogen (fluorine, chlorine, bromine, iodine), alkoxy having 1 to 4 carbon atoms and alkyl radicals having 1 to 4 carbon atoms.

Aryl radicals R are those with up to 20 carbon atoms, preferably 10 carbon atoms, in the ring system. In the case of the aralkyl radical, the aryl radical has the aforementioned scope of meanings; the alkyl bridge should include 1 to 4 carbon atoms. Substituents in the aryl or on the aromatic part of the aralkyl radical may be mentioned * NO ₈ , halogen (fluorine, chlorine, bromine, iodine), alkoxy and alkyl with 1 to 4 carbon atoms each.

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Aliphatic radicals Y include those with 1 to 4, preferably 1 to 2, carbon atoms and cycloaliphatic ones Y radicals are those with preferably 5 or 6 carbon atoms in the ring system.

The sulfonyldicarbonylimides obtainable by the process according to the invention have the general formula

R (SO ₃ NHCOCOX) η
in which R, X and η have the meaning given above. -

_{As unsaturated radicals R 1} or R ₂ containing at least one double bond, straight-chain © or branched, optionally substituted alkyl radicals having 2 to 20, preferably 2 to 10 carbon atoms, which contain 1, 2 or 3, preferably one double bond; but also partially hydrogenated aryl radicals and their SubstitutiOns products in the scope of meaning mentioned above for the aryl radical. Ala partially hydrogenated aryl radicals are preferably the di- and tetrahydrophenyl and naphthyl radicals.

. 5

The production of these new sulfonyldicarbonylimides takes place according to the embodiment described in the main patent

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1 0 9 8 1 3/1 9 7 p

The sulfonamides are in alcohols with alkyl hydroxides in the corresponding alkali compounds transferred by adding hydrocarbons, such as. B. toluene, xylene, chlorobenzene etc. the water is removed by distilling off part of the solvent and after further addition of anhydrous Alcohol and addition of the unsaturated oxamidester leads to the reaction at an elevated temperature to the end.

The sulfonamides mentioned in the main patent come as sulfonamides into consideration; Methanesulfonamide, chloromethanesulfonamide, Benzenesulfonamide and its substitution products such as m-nitrobenzenesulfonamide, p-toluenesulfonamide, etc. With the oxamide esters compounds can also be implemented which contain several sulfonamide groups in the molecule, such as. B. benzene-1,3-disulfonamide, 1,6-naphthalene-bi3-sulfonamide.

As unsaturated oxamides, for. B. Use:

DH ₂ -C-CONHCH ₈ NHCOCOOC ₂ H ₆ ; CH ₂ = CHCH ₈ NHCOCOOC ₂ H ₆ j (CH ₈ = CHCH ₂ ) ₂ NHGOCOOC ₂ H ₅ CH ₈

In accordance with the procedure of the main patent, the reaction takes place by reacting the sulfonamides in question with alkali metal hydroxide in alcohols, preferably methanol _t adding one

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1818410

aromatic hydrocarbon, the boiling point being this Must be higher than the boiling point of the diluent used alcohol, distilling off the alcohol and one Part of the aromatic hydrocarbon at normal pressure. It is then diluted with the same type of anhydrous alcohol, the proportion of the aromatic hydrocarbon in the total amount of the diluent about 5 to 60 vol .- 9S, preferably 10 to 35 vol .- #.

2. B, can be used as aromatic hydrocarbons be: toluene, xylene, o-diclorobenzene, benzene.

After adding the Oxamidesters the reaction is at a temperature of about 50 to 1QO ^Q C, preferably 60 to 140 ° C, completed within about 15 minutes to about 12 hours.

The molar ratio sulfonamide / oxamide ester is about 1: Of course, a small excess can also be used Oxamide esters can be taken.

If necessary, it can be expedient to use a demction mixture one of the usual polymerisation inhibitors, * rie E.g. Phenothiazine or ihioaeaic azide in amounts of about

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0.1 Ms about 1.5% by weight based on the amount of the starting compounds to add.

The reaction product obtained in the form of the alkali salt is acidified with hydrochloric acid, sulfuric acid and the like. transferred into the free connection.

It must be seen as surprising that no accumulation of the sulfonamides takes place on the double bond of the unsaturated oxamide ester.

The new unsaturated sulfonyldicarbonylimides obtainable by the process according to the invention are intermediate products for further reactions, especially for addition reactions, and can also be used as additives in aqueous and solvent polymerization of acrylonitrile can be used, whereby the dyeability of the polymers with basic dyes * * improve fabrics.

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Example · 1 "

40 parts by weight (1 mol) of sodium hydroxide are dissolved in 300 parts by volume of methanol. 95 parts by weight (1 mole) methanesulfonamide are added. After a few minutes, 700 parts by volume of toluene are added. At normal pressure Methanol and part of the toluene distilled off. After diluting with 900 parts by volume of absolute methanol and adding of 236 parts by weight (1.2 mol) of methacrylamidomethylene-N-oxamidethyl ester

CH ₂ = C-CONHCH ₂ NHCOCOOc ₂ H ₈

. ■ ■ -. 'CH ₈

and of 1.5 parts by weight of phenothiazine is taking 3 hours Reflux · heated. Subsequently, the cooled solution acidified with hydrochloric acid. That which is unusual in its pure form product

CH ₂ = C-CONHGH ₂ NHCOCONHSO ₂ Ch ₈ CH ₈

is sucked off; the yield is quantitative. F .: 208 ° C (from water).

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Example 2

16 parts by weight (0.4 mol) of sodium hydroxide are dissolved in 150 parts by volume of methanol and, after 62 parts by weight (0.4 mol) of benzenesulfonamide have been added, 350 parts by volume of toluene are added. As indicated in Example 1, methanol and some of the toluene are distilled off at normal pressure. It is then diluted with methanol and toluene so that at diluents about 450 parts by volume of methanol and 150 parts by volume of toluene there 'lad · 88 parts by weight (0.45 mole) of NN-Diallyloxamidsäureäthyleater and 1 part by weight Thiosemicarbazide are added. After refluxing for 3 hours, the mixture is concentrated in vacuo, the residue is taken up in about 500 parts by volume of water and acidified with hydrochloric acid while warm. The resulting precipitate soon becomes crystalline. The product can be reprecipitated from sodium bicarbonate solution / hydrochloric acid. The yield of N- (benzenesulfonyl) -N'-Ν · - (diallyl) -oxamide is 87 #. F .: 95 ° C.

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Example 3

36 parts by weight (0.9 mol) of sodium hydroxide, 300 parts by volume of methanol, 180 parts by weight (0.9 mol) of m-nitrobenzenesulfonamide and 700 parts by volume of toluene are combined. At normal pressure. Methanol and part of the toluola distilled off. After dilution with methanol and toluene so that *. ~ ^{E P} art of methanol and about 900 volume 300 parts by volume toluene are present, (1.1 moles) after adding of 168 wt ..- parts of N-allyl-oxamidsäureäthylester 3 hours heated under reflux * It is concentrated in vacuo and the residue with about 1000 parts by volume. Water absorbed * When heated, the solution is acidified with hydrochloric acid. The precipitating N- (allyl) -JS '' (m-nit r ob enzol sulphonyl) -oxamide is sucked off in quantitative yield. F .: 178 ° C.

Example 4

In the solution of 20 parts by weight (0.5 mol) of sodium hydroxide in 150 parts by volume of methanol are 78 parts by weight (0.5 mol) Benzenesulfonamide and 300 parts by volume of toluene were added. Methanol and part of the toluene are removed at normal pressure

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distilled, with 450 parts by volume of methanol and about 100 parts by volume of toluene is diluted. After adding 130 parts by weight (0.6 mol) of methacrylamidomethylene-N-oxamidethyl ester and 1 part by weight of thiosemicarbazide, the mixture is refluxed for 2 1/2 hours. It is concentrated in vacuo, taken up in water and the solution is acidified with hydrochloric acid. The precipitated N- (methylenemethacrylic ^{acid amide) -N l} - (beniolsulfonyl) -oxamide is isolated in quantitative yield by suction.
P .: 217 ° C.

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Claims (3)

- 13 - 1818410 patent claims 1.) Process for the preparation of sulfonyldicarbonylimides by reacting sulfonamides with oxalic acid derivatives, according to the main patent. ... ... (German patent application F 51 170 IVb / l2ο), characterized in that sulfonamides of the formula 'R (SO ₂ NH ₂ ) n in which . ^: * ^! . η stands for 1 or 2 and R is an n-valued en., Optionally substituted Denotes alkyl, cycloalkyl, aralkyl or aryl radical, with the equimolar amount of an alkali hydroxide in alcohol and an aromatic hydrocarbon boiling higher than the alcohol and forming an azeotropic mixture with water, at normal pressure to remove the water up to Reaching the boiling point of the aromatic hydrocarbon distilled, then so much similar anhydrous Alcohol yields that the aromatic hydrocarbon is about 5 to about 60 vol. # Of the total amount of diluent, then at the stoichiometrically required amount Amount of an oxalic acid derivative of the formula Le A 10 715 109813/1975 X-C-C-OY Il Il 0 0 whereby Ri
X stands for the radical -N and where the radicals -R ₂
R ₁ and R _{2 represent the} same or different radicals such as hydrogen, optionally substituted alkyl, aryl, cycloalkyl, aralkyl radicals and where at least one of the two radicals R ₁ or R _{2 is} an unsaturated radical containing at least one double bond, Y stands for an aliphatic or cycloaliphatic hydrocarbon radical at an elevated temperature brings to implementation and, after acidification, the sulfonyldicarbonylimide isolated. 2.) The method according to claim 1, characterized in that is carried out in the presence of a polymerization inhibitor. 3.) SuIfonyIdicarbonylimide of the general formula R (SÖ ₂ NHC0C0X) n wherein R, X and η have the meaning given in claim 1. Le A 10 715 ä13 / 1975