DE1219939B - Process for the preparation of substituted dihydro-s-triazines - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Int. Cl .:

C07d

GERMAN

PATENT OFFICE

EDITORIAL

German class: 12 ρ -10/05

Number: 1219 939

File number: F 46269IV d / 12 ρ

Filing date: June 5, 1965

Opening day: June 30, 1966

It has been found that substituted dihydros-triazines are obtained when using a cyano ester of the general formula

ROCN

in which R denotes an optionally substituted aromatic radical, with a ketone of the general formula

Rl -CR ²

Il ο

in which Ri and R ² should stand for hydrocarbon radicals with 1 to 12 carbon atoms, with ammonium thiocyanate at temperatures between 0 and 10O ⁰ C to 2 - aroxy - 4 - mercapto - 6,6 - dialkyl - dihydrotriazines-1,3,5 of the general formula

Ri R ²

/ ^C \

N N

RO-C

SH

in which R, R ¹ and R ^{2 have} the meanings given above.

The process is based on the example of the reaction of phenyl cyanate with acetone, ammonia and hydrofluoric acid explained by the following equation:

35 C ₆ H ₅ OCN + CH ₃ - CO - CH ₃ + NH ₃ + HSCN

H ₃ C

Il

C ₆ H ₅ O-C

CH ₃

N C-SH

As aromatic radicals R, aromatic hydrocarbon radicals with up to 14 carbon atoms in the ring system come into consideration, which can have as substituents, for example: alkyl, aryl, alkylamino, acylamino, nitro, alkoxy, aroxy, processes for the preparation of substituted
Dihydro-s-triazines

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Ernst Grigat, Cologne-Stammheim;

Dr. Rolf Pütter, Düsseldorf

Acyloxy, carbonyl, carboxyl, carbon ester, amide, sulfonyl, ester, amide, acyl, cyano, alkyl mercapto, Aryl mercapto, acyl mercapto groups or halogen atoms.

The hydrocarbon radicals R ¹ and R ² are straight-chain or branched hydrocarbon radicals having 1 to 12 carbon atoms.

The cyanic acid esters used as starting compounds can be prepared by reacting hydroxyl-containing compounds with halogen cyanides at temperatures, preferably below 65 ^° C., optionally in a solvent, in the presence of a base.

For example, the following cyanic acid esters can be used for the process according to the invention: 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- ^ o-diethyl- ^ - allyl ^ -methoxyphenylcyanate; Arylphenyl cyanates such as 4-cyanatodiphenyl, 4,4'-biscyanatodiphenyl; Dialkylaminophenyl cyanates such as 4 - dimethylamine, 4 - dimethylamine - 3 - methylphenyl cyanate; Acylaminophenyl cyanates such as acetylaminophenyl 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 acid, esters, amides such as 4-cyanatobenzoic acid, 2-cyanatobenzoic acid ethyl ester, 2 - cyanatobenzoic acid morpholide and diethylamide; Cyanatophenylsulfonic acid,

609 587/437

esters, amides such as 4-cyanatobenzenesulfonic acid; Alkoxyphenylcyanate such as 2 - methoxy, 3 - methoxy, 4-cyanatodiphenyl ethers; Acyloxyphenylcyanate like

3 - acetoxyphenyl cyanate; Acylphenylcyanates such as

4 - acetylphenyl cyanate; Cyanatophenyl cyanates such as 2,3-dicyano-1,4-dicyanatobenzene; α- and / 3-naphthyl cyanate, Quinoline cyanates such as 5-cyanato-quinoline and 4 - methyl mercapto - phenyl cyanate as well 2-cyanato-anthracene-3-carboxylic acid ester (C 1 to 4).

For example, ίο can be used as ketones den: acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, Methyl tert-butyl ketone, methyl vinyl ketone, di-n-propyl ketone, methyl undecyl ketone. The ammonium rhodanide can be added as such or else generated in the reaction mixture be e.g. B. by introducing ammonia and hydrofluoric acid.

The ketone to be converted is preferably used in excess as the solvent.

The reaction is very simple to carry out. One gives the components in any Sequence, preferably in an excess of the ketone to be converted. After the easy exothermic reaction precipitate the desired dihydrotriazine derivatives, and all by-products stay in solution. Isolation is therefore possible by simple suction. The yields are with up to 25% of theory for a four-component reaction is satisfactory.

The new dihydrotriazine derivatives obtainable according to the invention are valuable intermediates, e.g. B. for pharmaceuticals.

example 1

35

7.7 g (= 0.05 mol) 3-chlorophenyl cyanate and 7.6 g (= 0.1 mol) ammonium thiocyanate are combined in 35 ml of acetone. The temperature is rising from 15 to 40 ° C and is kept there. After a short time everything goes into solution, then it falls

45

60

and is isolated after stirring for half an hour by suction. Yield:. 3.2 g (= 24% of Theory). Mp 227-228 ° C (decomposition).

Analysis: CiiHi ₂ ClN ₃ OS (269.5).
Calculated

C 49.0, H 4.46, Cl 13.2, O 5.94, S 11.85%; Molecular weight 269.5; found

C 49.22, H 4.55, Cl 13.30, O 6.21, S 12.03%; Molecular weight 262.

Example 2

Analogously to Example 1, 6 g (0.05 mol) of phenyl cyanate and 7.6 g (0.1 mol) of ammonium rhodanide are obtained

2.9 g (= 25% of theory) of the H ₃ C CH _{3 in 35 ml of acetone}

/ ^C \

N N

Il Il

O - C C-SH

from melting point 223 to 224 ^° C. (decomposition). Analysis: CuHi ₃ N ₃ OS (235).
Calculated

C 56.2, H 5.53, N 17.8, O 6.80, S 13.6%; Molecular weight 235; found

C 56.76, H 5.61, N 17.68, O 7.06, S 13.43%; Molecular weight 229.SH group titration:

Calculated ... 14.1%;
found ... 13.9%.

Example 3

7.6 g (0.1 mol) of ammonium thiocyanate are introduced into a solution of 14 ^ 7 g (0.1 mol) of 2,4-dimethylphenyl cyanate in 50 ml of acetone. The temperature rises from 20 to 40 ° C, first it creates a smooth solution, then drops at 40 C the ⁰

- H ₃ C CH ₃

CH ₃

H ₃ C

Il
o - c

Ii C-SH

which is suctioned off after cooling down and standing overnight. Yield: 4.95 g (= 19% of theory); Mp 226-227 ° C (decomposition).

Analysis: Ci ₃ Hi ₇ N ₃ OS (263).
Calculated

C 59.4, H 6.45, N 15.97, O 6.08, S 12.2%; found

C 59.21, H 6.45, N 15.75, O 6.46, S 11.90%.

Example 4

A similar approach to Example 3, only with 40 ml of methyl ethyl ketone instead of 50 ml of acetone, gave this

H ₃ CC ₂ H ₅

CH ₃

H ₃ C

-O —C

Il

C-SH

from m.p. 237 to 238 ° C (decomposition). Analysis: Ci ₄ Hi ₉ N ₃ OS (277). .
Calculated

C 60.7, H 6.9, N 15.2, O 5.8, S 11.5%; found

C 60.74, H 7.23, N 15.09, O 5.99, S 11.53%.

Example 5

7.6 g (0.1 mol) of ammonium thiocyanate are dissolved in acetone and 10 g (0.075 mol) of 4-methylphenyl cyanate are added at 10 ° C. Temperature increase to 3O ⁰ C, held there. After 4 hours of stirring, the precipitated

H ₃ C CH ₃

IO

H ₃ C-

N
O -C

N C-SH

isolated by suction. Yield: 4.3 g (= 23% of theory); Mp. 225 ^° C. (decomposition). ^

Analysis: Ci ₂ Hi ₅ N ₃ OS (249). *

Calculated

C 57.8, H 6.02, N 16.85, O 6.42, S 12.84%; Molecular weight 249;

found _{2 <;}

C 57.75, H 6.14, N 16.76, O 6.71, S 12.89%; Molecular weight 252.

Analysis: Ci ₃ Hi ₅ N ₃ O ₂ S (277).
Calculated

C 56.3, H 5.42, N 15.15, O 11.55, S 11.55%; found

C 56.54, H 5.63, N 15.18, O 11.72, S 11.41%.

Claims (2)

Patent claims: 1. A process for the preparation of substituted dihydro-s-triazines, characterized in that that one has a cyanic acid ester of the general formula ROCN in which R denotes an optionally substituted aromatic radical, with a ketone of general formula Ri - C - R2 Il ο should be in the R ¹ and R ² are hydrocarbon radicals having 1 to 12 carbon atoms, with ammonium thiocyanate at temperatures between 0 and 100 ⁰ C to 2-aroxy-4-mercapto-6,6-diaflcyldihydrotriazinen-1,3,5 of the general formula Example 6 Analogously to Example 1, 1.4 g (= 20% of theory) of des is obtained from 4 g (0.025 mol) of 4-acetylphenyl cyanate and 3.8 g (0.05 mol) of NH _{4 SCN in acetone} 30th Il H ₃ CC H ₃ C Il o -c CH ₃ Il C-SH ^X N 'H from melting point 215 to 216 ^° C. (decomposition). 35 40 R ¹ R ² N N Il Il RO-C C-SH in which R, R ¹ and R ^{2 have} the meanings given above. 2. The method according to claim 1, characterized in that the reaction with a Carries out excess of the ketone to be converted. 609 587/437 6.66 © Bundesdruckerei Berlin