DE1518823B - Process for the preparation of N-sulfonyl-iminocarbonic acid ester amides - Google Patents

Description

ROCN

in which R has the meaning given above, with sulfonic acid amides of the general formula

R ¹ C-SO ₂ -NH ₂ ),

in which R ^{1 has} the meaning given above and y is an integer from 1 to 3, two sulfonamide groups not being in the o-position to one another, at temperatures between -20 and + 200.degree. C., preferably from 0 to 150.degree , optionally in a diluent and optionally in the presence of a base.

The compounds that can be prepared by this process are new and have the general formulas

35

40

NH
- Ο — C-NHSO ₂ R ¹

45

It has been found that novel N-sulfonyliminocarbonic acid ester amides can be obtained obtained when cyanic acid esters of the general formula

R (OCN) _x

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

R ¹ -SO ₂ NH ₂

in which R ^{1 is} an aliphatic, aromatic or heterocyclic radical which is replaced by an or

VR-OC-NHSO ₂ ^ rR ¹

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

Haloalkyl radicals R are, for example, hydrocarbon radicals with up to 12 carbon atoms, which preferably carry halogen atoms in the a- or jS-position to the oxygen-carrying carbon atom. Aliphatic radicals R ¹ are preferably straight-chain or branched alkyl radicals having 1 to 12 carbon atoms. Possible aromatic radicals R and R ¹ are aromatic hydrocarbon radicals with up to 20 carbon atoms in the ring system. The aromatic radicals R or R ¹ can carry, for example, as substituents: alkyl, aryl, alkylamino, acylamino, nitro, halogen, alkoxy, aroxy, acyloxy, carbonyl, carboxyl, carbon esters, - amide, sulfonyl, sulfonic acid esters, amide, acyl, cyano, rhodanide, alkyl mercapto, aryl mercapto or acyl mercapto groups.

The cyanate ester used as starting compounds can be prepared according own earlier proposals by the reaction of hydroxyl-containing compounds at temperatures Halogencyaniden are preferably prepared below +65 ⁰ C, optionally in a solvent in the presence of a base.

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-methoxyphenyl cyanate;
Arylphenylcyanates, such as 4-cyanatodiphenyl,

4,4'-biscyanatodiphenyl;
Dialkylaminophenyl cyanates, such as 4-dimethyl

amino-, 4-dimethylamino-3-methylphenyl-

cyanate;
Acylaminophenyl cyanates, such as acetylamino-

phenyl cyanate;

Nitrophenyl cyanates, 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-bromo-, 2-chloro-6-methyl-phenyl cyanate;
Cyanatophenylcarboxylic acids, esters, amides, such as

4-cyanatobenzoic acid, 2-cyanatobenzoic acid

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;

Acylphenylcyabates such as 4-acetylphenylcyanate;
Cyanophenyl cyanates, such as 2,3-dicyano

1,4-dicyanatobenzene;
α- and / 3-naphthyl cyanate, anthrachinyl cyanate,

such as 1,4-dicyanetoanthraquinone;
Quinoline cyanates such as 5-cyanatoquinoline;
1,4-phenylene dicyanate, 1,5-naphthylene dicyanate,

1,3,5-tricyanatobenzene,
4,4'-biscyanatodiphenyldimethylmethane,

4,4'-biscyanatodiphenyl-cyclohexane-l, l;
2,2'-biscyanato-dinaphthyl, 4-methylmercapto-

phenylcyanate, 3-N, N-dimethylcarbamyl-

phenyl cyanate

and the cyanic acid esters of the following alcohols:

ft / S ^ -Trichloroethanol, ^, ß-Trifluoroethanol,
/ S, ^, / S-tribromoethanol, ft / S-dichloroethanol.

Na ₂ CO ₃ , NaNH ₂ , NaH, NaOCH ₃ , Na or tert-amines, such as. B. triethylamine.

The reaction is carried out by combining the components, preferably in a liquid medium, in a ratio of cyanate group to sulfamide group of 1: 1, optionally in presence a base. 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-sulfonyl-iminocarbonic acid ester amides according to the invention are new and can be used as valuable intermediates for pharmaceuticals

the. _π . · Ιι

Example I.

10 ml of an O, lnormal aqueous NaOH solution are added to a mixture of 7.6 g (0.05 mol) of benzenesulfonamide and 30 ml of acetone, and then 6.65 (0.05 mol) of 4-methylphenyl cyanate are added. Temperature rise from room temperature to 45 ^° C. The clear solution suddenly solidifies; After suctioning off, the residue is stirred with 4 to 5 times the volume of water, suctioned off again and washed until neutral. 10.2 g (= 71% of theory) of the

NH

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The following can be used as sulfonic acid amides, for example: methanesulfonamide, ethanesulfonamide, Isopropanesulfonamide, hexanesulfonamide, cyclohexanesulfonamide, phenylmethanesulfonamide, benzenesulfonamide, Benzoldisulfonsäurediamid, Benzoltrisulfontriamid, α- or / S-naphthalenesulfonamid, 2-, 3- or 4-toluenesulfonamide, 2-, 3- or 4-chlorine (bromine, fluorine) -benzenesulfonamide, 2-, 3- or 4-hydroxybenzenesulfonamide, 2-, 3- or 4-dimethylaminobenzenesulfonamide, 2-, 3- or 4-nitrobenzenesulfonamide, 2-, 3- or 4-acetylbenzenesulfonamide, 2-, 3- or 4-methoxy- (ethoxy-, Isopropoxy -) - benzenesulfonamide, 2-, 3- or 4-methylmercaptobenzenesulfonamide, 2-, 3- or 4-Cyanobenzenesulfonamide, also benzenesulfonamides with more than one of the substituents listed above, for example, with naphthylsulfonamides, the carry one or more of the substituents listed for the benzene derivatives, quinolinesulfonamides, Carbazole sulfonamides, phenylpyrazole sulfonamides, imidazole sulfonamides.

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, ben? zol, petroleum ether, nitrobenzene, nitromethane, chloroform, Carbon tetrachloride, chlorobenzene.

The bases which promote the reaction can be added, for example, in catalytic to molar amounts are: alkali hydroxides, carbonates, amides, hydrides, alcoholates, metals, e.g. NaOH, KOH,

30 with a mp of 165 ° C are obtained. C ₁₄ H ₁₄ N ₂ O ₃ S (290):

Calculated:

C 57.9, H 4.82, N 9.65, O 16.5, S 11.0%; found:

C 58.08, H 4.91, N 9.93, O 16.71, S 10.65%.

Example 2

Analogously to Example 1, 6.65 g (0.05 mol) of 4-methylphenyl cyanate are obtained from 10 g (0.05 mol) of 3-nitrobenzenesulfonamide and 8 ml! normal aqueous NaOH solution 12.8 g (= 77% of theory) des

NH

/ - * -KTXJ cn -ν \

H, C

from 162 to 64 ° C.
C ₁₄ H ₁₃ N ₃ O ₅ S (335):

Calculated:

C 50.1, H 3.88, N 12.53, O 23.9, S 9.55%; _: found:

C 50.50, H 4.19, N 12.50, O 23.95, S 9.70%. ~

Example * 3

Analogously to Example 1, benzenesulfonamide and 2,4-dimethylphenyl cyanate are obtained in a 74% yield that

from 146 to 147 ° C.

'/ 5

C ₁₅ H ₁₆ N ₂ O ₃ S (304):

Calculated:

C 59.3, H 5.25, N 9.2, O 15.8, S 10.5%;

Molecular weight 304;
found:

C 59.29, H 5.55, N 9.22, O 15.83, S 10.5%.

Molecular weight 313.

Example 4

Analogously to Example 1, 4-acetylphenyl cyanate is obtained and benzenesulfonamide that

Example 6

8.55 g (0.05 mol) of o-toluenesulfamide are dissolved in acetone, then 5 ml of n-NaOH and then 7.35 g (0.05 mol) 2,4-dimethylphenyl cyanate was added. Temperature rise to 38 ° C. After an hour, with 150 ml of water diluted. An oil separates out, that soon froze. Yield: 12.3 g (= 77% of theory) of the

CH,

H, C — C— <f V-O-C — NH-SO, -

^CH 3 _NH

V-o-C-NH-SO.

CH,

20th

from 173 to 175 ° C.
C ₁₅ H ₁₄ N ₂ O ₄ S (318):

Calculated ... C 56.6, H 4.40, N 8.80, O 20.15%; • Found .... C 56.54, H 4.45, N 9.02, O 20.26%.

Example 5

7.65 g (0.05 mol) 3-chlorophenyl cyanate and 8.55 g (0.05 mol) of o-toluenesulfamide are dissolved in 30 ml of acetone. Then normal aqueous NaOH is used for so long added until no more exothermicity is detected (50 ml in total). An oil separates with it Crystals. After a short time, the mixture is made neutral with a little HCl, filtered off with suction, washed and pressed onto clay. Yield: 8.1 g (= 50% of theory) of the

Cl

\. ^NH

/ ~ \ —O — C — NH — SO

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40

from 115 to 116 ° C.
C ₁₄ H ₁₃ ClN ₂ O ₃ S (324.5):

Calculated:

C 51.8, H 4.00, N 8.65, O 14.7, S 9.87, Cl 10.95%; found:

C 51.51, H 4.17, N 8.93, O 14.61, S 9.80, Cl 11.10%.

which is isolated by suction. F. 155 to 156 ° C. C ₁₆ H ₁₈ N ₂ O ₃ S (318):

Calculated:

C 60.4, H 5.66, N 8.80, O 15.1, S 10.05%;

Molecular weight 318.
found:

C 60.29, H 5.72, N 8.84, O 15.02, S 10.00%.

Molecular weight 322.

Example 7

Analogously to Example 6, 11.4 g (= 70%) are obtained from 8.7 g of trichloroethyl cyanate and 7.6 g of benzenesulfamide the theory) des

NH
Cl ₃ C-CH ₂ -OC-NHSO ₂

F. 156 to 157 ° C.
C ₉ H ₉ Cl ₃ N ₂ O ₃ S (331.5):

Calculated:

C 32.6, H 2.27, N 8.44, O 14.5, S 9.66%;
found:

C 32.17, H 2.73, N 8.52, O 14.40, S 9.38%.

Examples

Analogously to Example 6, 2 moles of benzenesulfamide and 1 mole of phenylene biscyanate (1,4) are obtained

from 265 to 267 ° C.

C ₂₀ -H ₁₈ N ₄ O ₆ S (474):

Calculated:

C 50.65, H 3.76, N 11.80, 0 20.30%; found:

C 50.77, H 4.01, N 11.92, 0 20.01%.

Example 9

held at 40 ^° C. After 1 hour, the mixture is stirred in water and the crystallized

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6o NH

r ¹ MU cn _ # Ni

obtained by suction. Yield: 13.5 g (= 76% of theory). F. 193 to 194 ° C.

Example 10

3.8 g (0.025 mol) of benzenesulfonamide are heated

10 g of 3-nitrobenzenesulfamide are dissolved in acetone and 3.3 g (0.025 mol) of 4-methylphenyl cyanate together with 5 ml of In-NaOH at 90 ^° C., an oil which ^{begins to crystallize at about 70 °} C. is formed.

suspended, 14 ml of triethylamine and then 7.65 g of 4-chlorophenyl cyanate were added. The temperature will

After filtering off with suction and washing neutral with water, 5.2 g (= 73% of theory) of the same are obtained Product as in Example 1 (identical IR spectrum, mp 163 to 164 ° C).

Example 11

Theory) of the same product as in Example 1 or 10 (identical IR spectrum).

Example 12

Analogously to Example 9, α-naphthyl cyanate and methanesulfonic acid amide give the

NH

-C-NH-SO ₃ -CH,

When 3.3 g (0.025 mol) of 4-methylphenyl cyanate and 3.8 g (0.025 mol) of benzenesulfonamide _{10 are} heated to 135 ° C. (within 2 hours) without a solvent and without the addition of a base, the mass solidifies on cooling, and after Stirring with alcohol, suction and neutral washing 5 g (= 70% of the temperature from 151 to 153 ° C (from alcohol).

Claims (1)

Claim: Process for the production of N-sulfonylimino-carbonic acid ester amides, characterized in that cyanic acid esters of the general formula R (OCN) _x in which R is a haloalkyl radical or an aromatic radical which is optionally substituted 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, aryl mercapto and acyl mercapto can be substituted, and χ denotes an integer from 1 to 3, with no two OCN groups are in the o-position to one another, with sulfonic acid amides of the general formula Ri-SO ₂ NH ₂ in which R ^{1 represents} an aliphatic, aromatic or heterocyclic radical which can be substituted by one or more identical or different radicals from the group indicated above, or cyanic acid esters of the general formula ROCN in which R has the meaning given above, with sulfonic acid amides of the general formula R ¹ C-SO ₂ -NH ₂ ), in which R ^{1 has} 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.degree. C., preferably from ^{0 to} 150.degree , optionally in a diluent and optionally in the presence of a base. several identical or different radicals of the group indicated above can be substituted, or cyanic acid esters of the general formula