DE1289526B - Process for the preparation of aromatic sulfonyl isocyanates - Google Patents

Description

It is known to convert anthracene with N-carbonylsulfamic acid chloride to give 9-chlorosulfonyl-N-carbonylimidoanthracene implement (A., 661, p. 116 [1963]).

It is also known to use benzene or its derivatives with N-carbonylsulfamic acid chloride in the presence of aluminum chloride to the corresponding aromatic chlorosulfonyl-N-carbonylimido substitution products implement (A., 661, p. 116 [1963]).

It is also known to use alkoxy-substituted benzene compounds Reaction with N-carbonylsulfamic acid chloride at temperatures between 0 and 120 "C. into the corresponding aromatic chlorosulfonyl-N-carbonylimido substitution products to be transferred (German Auslegeschrift 1 210 792).

In contrast, it has now surprisingly been found that aromatic Sulphonyl isocyanates can be prepared by using the general sulphonyl isocyanates Formula XSO2N = C = O in which X is an isocyanate group or a chlorine atom, with mono- or binuclear aromatic hydrocarbons, which are represented by alkyl, alkoxy or isocyanate groups or halogen atoms may be substituted at temperatures between about 120 and 160 "C to compounds of the general formula R-SO2-N = C = O in which R is the radical of a mono- or binuclear aromatic hydrocarbon means substituted by alkyl, alkoxy or isocyanate groups or halogen atoms can be implemented.

The process is usually carried out at normal pressure. It kar; n can, however, also be carried out at increased pressure.

If the process is carried out with chlorosulfonyl isocyanate, then it is advantageous to remove the hydrogen chloride formed with the aid of an inert gas which is passed through the reaction mixture to remove. Used with sulfuryl diisocyanate worked, so there is no need to pass an inert gas, since the formed Isocyanic acid is trimerized to cyanuric acid and as such from the reaction mixture fails.

As far as the proportions of the reaction components are concerned, so it is advantageous to use the aromatic present in a 2- to 10-fold molar excess React hydrocarbon with 1 mole of chlorosulfonyl isocyanate or sulfuryl diisocyanate.

After completion of the reaction, the excess aromatic hydrocarbon becomes distilled in vacuo and the aromatic sulfonyl isocyanates formed in known Way also worked up by distillation under reduced pressure.

The aromatic sulfonyl isocyanates obtainable according to the process of the formula (1) mentioned represent valuable intermediates for the preparation of Textile auxiliaries or pesticides.

Example 1 250 parts by weight of naphthalene are melted in a flask and heated to 1500 C while passing nitrogen through. Over the course of 2 hours 141.5 parts by weight of chlorosulfonyl isocyanate are added dropwise. After the addition is held at 1500C for a further 24 hours. The excess naphthalene is in vacuo distilled off and the remaining sulfonyl isocyanate distilled in a high vacuum. 128 parts by weight of 2-naphthalenesulfonyl- isocyanate (bp 10-4T0rr 108 " C), which corresponds to a yield of 55% of theory, based on the chlorosulfonyl isocyanate used, is equivalent to.

Example 2 520 parts by weight of m-xylene and 71 parts by weight of chlorosulfonyl isocyanate are mixed and stirred in a flask. The solution makes a stronger one Passed a stream of nitrogen and the mixture heated to reflux. After 120 hours the reaction is terminated and the solution of some precipitated solid material filtered off. The filtrate is freed from excess m-xylene in vacuo and the remaining sulfonyl isocyanate distilled in a high vacuum.

84 parts by weight of 2,4-dimethylbenzene-1-sulfonyl isocyanate are obtained (KP.10-8 Torr 84 "C), which corresponds to a yield of 79.5010 of theory, based on the Chlorsulfonylis ocyanat, corresponds.

Example 3 520 parts by weight of p-xylene and 71 parts by weight of chlorosulfonyl isocyanate are mixed and stirred in a flask. The solution makes a stronger one Passed a stream of nitrogen and the mixture heated to reflux. After 120 hours the reaction is terminated and the solution of some precipitated solid material filtered off. The filtrate is freed from excess p-xylene in vacuo and that remaining sulfonyl isocyanate distilled in a high vacuum. 79 are won Parts by weight of 2,5-dimethylbenzene-1-sulfonyl isocyanate (Kp. Lo-3Torr 81 "C), what a Yield of 750 / o of theory, based on the chlorosulfonyl isocyanate used, is equivalent to.

Example 4 520 parts by weight of o-xylene and 71 parts by weight of chlorosulfonyl isocyanate are mixed and stirred in a flask. The solution makes a stronger one Passed a stream of nitrogen and the mixture heated to reflux. After 120 hours the reaction is terminated and the solution of some precipitated solid material filtered off. The filtrate is freed from excess o-xylene in vacuo and that remaining sulfonyl isocyanate distilled in a high vacuum. You win 81 Parts by weight of 3,4-dimethylbenzene-1-sulfonyl isocyanate (bp. ,, B Torr 900 C), what a Yield of 77% of theory, based on the chlorosulfonyl isocyanate used, is equivalent to.

Example 5 600 parts by weight of 3-chloroanisole and 71 parts by weight of chlorosulfonyl isocyanate are mixed in a flask and stirred while nitrogen is bubbled through. It is heated to 150 "C. and held at this temperature for 120 hours. Thereafter some solid material precipitated is filtered off.

The filtrate is freed from excess 3-chloroanisole in vacuo and the remaining sulfonyl isocyanate is distilled in a high vacuum. Be won 61 parts by weight of 2-chloro-4-methoxybenzene-1-sulfonyl isocyanate (KP. ,, - 4Torr 110 ° C), which is a yield of 49.5% of theory, based on the chlorosulfonyl isocyanate used, is equivalent to.

Example 6 150 parts by weight of anisole are in a stirred flask for Boiling heated. To this end, 71 parts by weight are then added over the course of 4 hours with stirring Chlorosulfonyl isocyanate added dropwise, with evolution of hydrogen chloride takes place. After all, chlorosulfonyl isocyanate is added dropwise, the mixture is refluxed for a further 20 minutes. Then will filtered off some precipitated material and the excess anisole in vacuo distilled off. The remaining sulfonyl isocyanate is distilled in a high vacuum. 58 parts by weight of 4-methoxybenzene-1-sulfonyl isocyanate (boiling point 0.005) are obtained Torr 97 "C), which corresponds to a yield of 54.50 /, of theory, based on the amount used Corresponds to chlorosulfonyl isocyanate.

Example 7 500 parts by weight of ethylbenzene are mixed with 71 parts by weight Chlorosulfonyl isocyanate mixed. The solution passes nitrogen through it with stirring passed and the mixture heated to reflux. After 120 hours the reaction will broken off and the solution filtered off from some precipitated solid material. The excess ethylbenzene is distilled off in vacuo and the remaining Sulfonyl isocyanate distilled in a high vacuum. 49 parts by weight of 4-ethylbenzene-1-sulfonyl isocyanate are obtained (Bp 0.02 T0rr 840 C), which corresponds to a yield of 46.5 0 / o of theory, based on the used Chlorosulfonyl isocyanate.

Example 8 500 parts by weight of mesitylene are passed through Nitrogen heated to the boil. There are 71 parts by weight of chlorosulfonyl isocyanate added dropwise over half an hour. The mixture is then used for 30 hours Heated to reflux. The excess mesitnyl is then distilled off in vacuo and the remaining sulfonyl isocyanate is distilled in a high vacuum. Be won 51 parts by weight of 2,4,6-trimethylbenzene-1-sulfonyl isocyanate (bp 10-4 T0rr 75 "C), which is a yield of 45 ° / 0 of theory, based on the chlorosulfonyl isocyanate used, is equivalent to.

Example 9 200 parts by weight of m-xylene are mixed with 74 parts by weight Sulfuryl diisocyanate mixed and heated to reflux. After 12 hours the precipitated cyanuric acid is filtered off and the solution is distilled in vacuo freed from excess m-xylene. The remaining sulfonyl isocyanate is im Distilled under high vacuum. 85 parts by weight of 2,4-dimethylbenzene-1-sulfonyl isocyanate are obtained (Kp.10-3 Torr 840 C), which corresponds to a yield of 80.5 0 / o of theory, based on the used Sulfuryl diisocyanate.

Example 10 200 parts by weight of toluene are mixed with 74 parts by weight Sulfuryl diisocyanate mixed and heated in an autoclave to 160 ° C. After 20 hours will the Removed reaction mixture and filtered off from the precipitated cyanuric acid. The filtrate is freed from excess toluene in vacuo and the remaining toluene Sulfonyl isocyanate distilled in a high vacuum. 46 parts by weight of 4-methylbenzene-1-sulfonyl isocyanate are obtained (Kp. 002 Torr 77 "C), which corresponds to a yield of 46.5% of theory, based on the Sulfuryl diisocyanate.

Example 11 200 parts by weight of phenyl isocyanate are mixed with 74 parts by weight Sulfuryl diisocyanate mixed and heated to 1500 C for 8 hours. Then will filtered off from the cyanuric acid and the solution in vacuo from excess phenyl isocyanate freed. The remaining sulfonyl isocyanate is distilled in vacuo. Won 28 parts by weight of 4-isocyanatobenzene-1-sulfonyl isocyanate (boiling point 0.01 Torr 1050 C; M.p. 43 "C).

Example 12 300 parts by weight of i-propylbenzene are mixed with 71 parts by weight Chlorosulfonyl isocyanate mixed. Then nitrogen is passed through the resulting solution passed and heated to reflux. The reaction is terminated after 120 hours. After some solid material has been filtered off, the excess i-propylbenzene becomes distilled off in vacuo and the remaining sulfonyl isocyanate also in vacuo distilled. 47 parts by weight of 4-i-propyl-1-sulfonyl isocyanate are obtained from Boiling point bp 002 Torr 87 "C.

Claims (2)

Claims: 1. Process for the preparation of aromatic sulfonyl isocyanates characterized in that sulfonyl isocyanates of the general formula X-SO2-N = C = Q in which X is an isocyanate group or a chlorine atom, with one or binuclear aromatic hydrocarbons, by alkyl, alkoxy or Isocyanate groups or halogen atoms may be substituted at temperatures between about 120 and 160 "C to compounds of the general formula RSO2N = C = O in which R denotes a mono- or binuclear aromatic radical which is substituted by alkyl, alkoxy or Isocyanate groups or halogen atoms can be substituted. 2. The method according to claim 1, characterized in that the Carries out reaction with chlorosulfonyl isocyanate while passing through an inert gas.