DE1518867C - Process for the preparation of iminocarbonate derivatives - Google Patents

Description

in which R is a haloalkyl radical or an aromatic radical which can also be linked to a heterocyclic radical and optionally by one or more identical or different radicals from the group consisting of alkyl, cycloalkyl, aryl, acylamino, dialkylamino, nitro, halogen -, alkoxy, aroxy, acyloxy, alkylcarbonyl, arylcarbonyl, carboxylic acid esters, alkylsulfonyl, arylsulfonyl, sulfonic acid esters, alkyl mercapto, aryimercapto and acyl mercapto, and χ denotes an integer from 1 to 3, where two OCN groups are not in the o-position to one another, with N-substituted sulfonic acid amides of the general formula

or

R ²

-R ¹

in which R, R ¹ , R ² , χ and y have the meaning given above.

R ¹ -SO ₇ -NH-R ²

in which R ¹ and R ² stand for an aliphatic, aromatic or heterocyclic radical, where R ¹ and R ^{2 can be} identical or different and can be substituted by one or more identical or different radicals from the group specified above, or cyanic acid esters of the general formula

ROCN

in which R has the meaning given above, with N-substituted sulfonic acid amides of the general Formula.

R ¹ - (SO ₂ - NHR ² X,

in which R ¹ and R ² have the meaning given above and y is an integer of 1 to 3. wherein two sulfonamide groups are not in the o-position to each other, at temperatures between -20 and +200 ⁰ C, preferably from O to 150 ⁰ C, if appropriate in a diluent and if appropriate in the presence of a base.

Those producible by the process according to the invention Compounds are new and have the general formula

NH

- O —C

NSO ₂ R ¹
R ²

or.

NH

■ ■■ I

ROC-NSO ₂
R ²

It has been found that novel iminocarbonic acid esters are obtained if cyanic acid esters in which R, R ¹ , R ² , χ and y have the meaning given above ..

Halogenaikylreste R are z. B. hydrocarbon residues with up to 12 carbon atoms, which are preferably fluorine, chlorine, bromine or iodine atoms in the / I position carry.

Preferred aliphatic radicals R ¹ and R ² are

straight-chain or branched alkyl radicals with 1 to carbon atoms called. Possible aromatic radicals R, R ¹ and R ² are aromatic hydrocarbon radicals with up to 20 carbon atoms in the ring system. The aromatic radicals R can also be linked to a heterocyclic ring system. Suitable heterocyclic radicals R ¹ and R ² are 5- or 6-membered ring systems with one or more heteroatoms, such as oxygen, sulfur or nitrogen, in the ring system. The aromatic or heterocyclic radicals R, R ¹ and R ² can have, for example, as substituents: alkyl, aryl, alkylamino, acylamino, nitro, halogen, alkoxy, aroxy, acyloxy, carbonyl, carboxyl , Carbon ester, amide, sulfonyl, sulfonic acid ester, amide, acyl, cyano, rhodanide, alkyl mercapto, aryl mercapto or acyl mercapto groups.

The cyanic acid esters used as starting compounds are known.

It can be used for the inventive method, for. B. the following cyanic acid esters are used:

Phenyl cyanate, mono- and polyalkylphenyl cyanates, such as

3-methyl-, 4-isododecyl-, 4-cyclohexyl-, 2-tert.-, Butyl, 3-trifluoromethyl, 2,4-dimethyl, 3,5-dimethyl-, 2,6-diethyl-, 4-allyl-2-methoxy-

phenyl cyanate;
Arylphenylcyanates, such as 4-cyanatodiphenyl,

4,4'-biscyanatodiphenyl;
Dialkylaminophenylcyanates, such as 4-dimethylamino-, 4-dimethylamino-3-methylphenyl-

cyanate;
Acylaminophenyl cyanates, such as acetylamino-

phenyl cyanate;
Nitrophenylcyanates, such as 4-nitro-, 3-nitro-, 4-nitro-3-methyl, S-nitro-o-methyl-phenyl-

cyanate;
Halophenyl cyanates, such as 2-chloro, 3-chloro, 4-chloro, 2,4-dichloro, 2,6-dichloro, 3-bromine,

2-chloro-6-methyl-phenylcyanate; Cyanatophenylcarboxylic acid, esters, amides, such as 4-cyanatobenzoic acid, 2-cyanatobenzoic acid ethyl ester, 2-cyanatobenzoic acid-

morpholide and diethylamide; Cyanatophenylsulfonic acid, esters, amides, such as

4-cyanatobenzenesulfonic acid; Alkoxyphenyl cyanates, such as 2-methoxy,

3-methoxy, 4-cyanatodiphenyl ethers; Acyloxyphenyl cyanates such as 3-acetoxyphenyl cyanate;

Acylphenyl cyanates such as 4-acetylphenyl cyanate; Cyanophenylcyanates, such as 2,3-dicyano-l, 4-di-

cyanatobenzene;
α- and / S-naphthyl cyanate, anthrachinyl cyanate,

such as 1,4-dicyanatoanthraquinone; Quinoline cyanates such as 5-cyanatoquinoline; 1,4-phenylene dicyanate, 1,5-naphthylene dicyanate, 1,3,5-tricyanatobenzene, 4,4'-biscyanatodiphenyldimethylmethane, 4,4'-biscyanatodi-

phenyl-cyclohexane-1,1;
2,2'-biscyanato-dinaphthyl, 4-methyl mercaptophenyl cyanate, S-NjN-dimethylcarbamylphenyl cyanate and the cyanic acid esters of the following alcohols:
ft / S ^ -trichloroethanol, / S, /?, / 3-trifluoroethanol, ft3-tribromoethanol, β-dichloroethanol and H (CF ₂ -CF ₂ ) ₅ -CH ₂ OH.

Examples of N-substituted sulfonic acid amides that can be used are: The N-methyl, -ethyl, -Isopropyl, -tert-butyl, -dodecyl, -stearyl, -phenyl, -Naphthyl, -Nitrophenyl, -Methylphenyl, -Halogen- ■ 5 (fluorine, chlorine, bromine, iodine) -phenyl, methoxyphenyl derivatives of the following sulfonic acid amides:

Methanesulphonamide, ethanesulphonamide, isopropanesulphonamide, hexanesulphonamide ,. Cyclohexanesulphonamide, phenylmethanesulforiamide,

Benzenesulfonamide, Benzoldisulfonsäurediamid, Benzoltrisulfontriamid,
a- or ß-naphthalenesulfonamide, '

2-, 3- or 4-toluenesulfonamide, 2-, 3- or 4-chlorine (bromine, fluorine) benzene sulfone

amide,. , ·

2-, 3- or 4-hydroxybenzenesulfonamide, '; ' 2-, 3- or 4-Dimethylaminobenzolsulfoiiamid, ' 2-, 3- or 4-nitrobenzenesulfonamide, V 2-, 3- or 4-acetylbenzenesulfonamide, 2-, 3- or 4-methoxy- (ethoxy-, isopropoxy-) - benzenesulfonamide,

2-, 3- or 4-methylmercaptobenzenesulfonamide, 2r, 3- or 4-cyanobenzenesulfonamide,

further benzenesulfonamides ^"v with more than one, for example, the above-enumerated substituents Naphthylsulfonamide which carry one or more times those enumerated in the benzene derivatives substituent Chinolinsulfonamide, Carbazolsulfonamide, Phenylpyrazolonsulfonamide, Imidazolsulfonamide.

As a solvent, for. B. organic solvents such as alcohols, ketones, ethers, nitriles, Esters, amides, aromatic and aliphatic, optionally nitrated or halogenated hydrocarbons or water. Examples include: methanol, ethanol, acetone, diethyl ether, Acetonitrile, ethyl acetate, dimethylformamide, benzene, petroleum ether, nitrobenzene, nitromethane, chloroform, Carbon tetrachloride, chlorobenzene.

The following can be added as bases promoting the reaction, for example in catalytic to molar amounts: alkali hydroxides, carbonates, amides, hydrides, alcoholates, metals, e.g. NaOH, KOH, Na ₂ CO ₃ , NaNH ₂ , NaH, NaOCH ₃ , Na or tert-amines, such as. B. triethylamine.

The reaction is made by adding the Components, preferably in a liquid medium, in a ratio of cyanate group to sulfamide group as 1: 1, optionally in the presence of a base, carried out. An excess of a reactant does not generally interfere. The reaction products usually precipitate, if appropriate after concentration of the solvent, and can, if appropriate after neutralization, are isolated.

The N-aryl- (alkyl) -sulfonyl-N-aryl (alkyl) -iminocarbonic acid ester-amides are new and can be used as valuable intermediates for pharmaceuticals.

example 1

23.3 g (0.1 mol) of benzenesulfonic anilide are placed in 60 ml of acetone, first 20 ml of 0.1 N aqueous sodium hydroxide solution, then 13.3 g (0.1 mol) of 4-methylphenyl cyanate, dissolved in 10 ml of acetone, admitted. After 1 hour of heating to about 40 ^° C., the reaction has ended. Two phases are formed, of which the organic one soon begins to crystallize.

The raw booty at

NH
Ο —CN-SO ₂

QH ₅ is 20 g (= 55% of theory). M.p. 121 to 122 ° C.

Analysis: C ₂₀ H ₁₈ N ₂ O ₃ S (molecular weight 366). Calculated ... 65.6, 4.93, 7.65, 13.1, 8.75%; found ... 65.51, 5.08, 7.94, 13.59, 8.69%.

'Example 2

Analogously to Example 1, N-methylamide and 4-methylphenyl cyanate are obtained from 4-chloro-3-nitrobenzenesulfonic acid that

Example 3

Analogously to Example 1, benzoisulphonic acid anilide is obtained and ^, / S-Trichloräthylcyanat das

NH
Cl ₃ C - CH ₂ - O - C - N - SO ₂

ίο

from m.p. 107 to 109 ° C [mixed m.p. with benzenesulfanilide (F. HO ⁰ C) is 87 to 89 ° C].

Example 4

Analogously to Example 1, benzenesulfonic acid anilide is obtained and phenyl cyanate that

NH

/ V-O-C-N-

QH ₅

from m.p. 110 to IH ⁰ C [mixed m.p. with benzenesulfanilide (F. HO ⁰ C) is 81 to "83 ⁰ C].

Claims (1)

Claim: Process for the production of iminocarbonic acid esters, characterized in that that one cyanate of the general formula R (OCN) _x in which R is a haloalkyl radical or an aromatic radical, which is also with a heterocyclic Remainder be connected and optionally by one or more identical or different Radicals from the group of alkyl, cycloalkyl, aryl, acylamino, dialkylamino, nitro, halogen, Alkoxy, aroxy, acyloxy, alkylcarbonyl, arylcarbonyl, carboxylic acid esters, alkylsulfonyl, Arylsulfonyl, sulfonic acid esters, alkyl mercapto, aryimercapto and acyl mercapto substituted can, and χ is an integer from 1 to 3, two OCN groups not in the o-position stand to one another, with N-substituted sulfonic acid amides of the general formula ■ R ¹ -SO ₂ NH-R ² in which R ¹ and R ² stand for an aliphatic, aromatic or heterocyclic radical, where R ¹ and R ^{2 can be} identical or different and can be substituted by one or more identical or different radicals from the group specified above, or cyanic acid esters of the general formula ROCN in which R has the meaning given above, with N-substituted sulfonic acid amides of the general formula R ^ SO ₂ -NHR ² ) ,, in which R ¹ and R ^{2 have} the meaning given above and y is an integer from 1 to 3, where two sulfonamide groups are not in the o-position to one another, at temperatures between -20 and +200 ⁰ C, preferably from 0 to 150 ^° C., if appropriate in a diluent and if appropriate in the presence of a base, to give the iminocarbonic acid esters of the formula NH
R-O-C-NSO ₂ R ¹ R ²
NH Il ROC-NSO ₂ - the general formula R (OCN) _x