DE1213415B - Process for the production of ammeline ethers - Google Patents

Description

BUNi) ESREPUBXIK GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int, Cl ,:

Number:
File number:
Registration date:
Display day:

C07d

German class: 12 ρ-10/05

1213415
F43499IVd / 12p
July 18, 1964
March 31, 1966

It is known that ammeline ether can be obtained from 2'-chloro-4i6-diamino'S-triazines by reaction with phenols or alcohols can be obtained. Through »further reaction of the NHa group, For example, with excess phenolate, by-products that contaminate the desired end product and are difficult to separate from it.

It has now been found that, in a targeted ring closure reaction, ammeline ether of the general formula

OR

/ λ

H ₂ NC

X ₁

C-NH ₂

wherein R is a haloalkyl radical or an optionally substituted aromatic radical means to produce can, if you have a cyanate of the general formula

ROCN
wherein R has the meaning given above, with

Method of making ammeline ether

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Ernst Grigat, Köm-Stammheim;

Dr. Rolf Pütter, Düsseldorf

about the equimolar amount of dicyandiamide in the presence of catalytic to molar amounts of alkali or with about the half molar amount of guanidine - which is preferably made free during the reaction from its salts by adding alkali - at temperatures between -50 and +100 ⁰ C in the presence of a solvent or a solvent mixture.

The method according to the invention is based on the examples the implementation of 2,4-dimethylphenyl cyanate explained with dicyandiamide or guanidine:

NHr

NH

CHs

respectively

- OCN + HaN- C - NH- CN

NH *

CH ₃

2CH ₃

OCN

NH

HaN "C -NH ₂

CH ₃

C-NH ₃ + CH ₃

CH ₃

CH ₃

CH ₃

Ali optionally substituted aromatic radicals 50 substituents of the aromatic radicals are at -R * teötHien arbrnaiisejie hydrocarbon radicals with, for example: alkyl, aryl, alkylamino, acylamino, tiis z ^^ O'Kdhlenstöffkorektiven in question. Nitro, halogen, alkoxy, aroxy, aeyloxy, car

609 540M14

bonyl, carboxyl, ester, amide, sulfonyl, ester, -amid, acyl, cyano, rhodanide, alkyl mercapto, acyl mercapto.

The cyanic acid esters used can, according to older proposals by the inventor, be prepared by reacting compounds containing hydroxyl groups 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, 2,6-diethyl, 4-allyl-2-methoxyphenyl cyanate; Arylphenylcyanates such as 4-cyanatodiphenyl, dialkylaminophenylcyanate such as 4-dimethylamino-, 4-dimethylamino-3-methyl-phenyl cyanate; Acylaminophenyl cyanates such as acetylaminophenyl cyanate; Nitrophenyl cyanates such as 4-nitro-, 3-nitro-, 4-nitro-3-methyl-, 3-nitro-6-methyl-phenyl cyanate; Halophenyl cyanates such as 2-chloro, 3-chloro, 4-chloro, 2,4-dichloro, 2,6-dichloro-, 3-bromo-, 2-chloro-6-methylphenyl cyanate; Cyanatophenylcarboxylic acid, esters, amides such as 4-cyanatobenzoic acid, 2-cyanatobenzoic acid ethyl ester, 2-cyanatobenzoic acid morpholide and diethylamide; Cyanatophenyl sulfonic acid, ester, -amides such as 4-cyanetobenzenesulphonic acid; Alkoxyphenyl cyanates such as 2-methoxy-, 3-methoxy-, 4-isopropoxyphenyl cyanate; Phenoxyphenyl cyanates such as 4-cyanatodiphenyl ether; Acyloxyphenyl cyanates such as 3 - acetoxyphenyl cyanate; Acylphenylcyanates such as 4-acetylphenyl cyanate; Cyanophenyl cyanates such as 4-cyanophenyl cyanate; α- and, S-naphthyl cyanate, Änthrachinylcyanate such as 4-cyanatoanthraquinone; 4-methyl mercaptophenyl cyanate, 3 -N, N - dimethylcarbamylphenyl cyanate, and the cyanic acid esters of the following alcohols: ^, / S-trichloroethanol, ß ^ -trifluoroethanol, ^, / J-tribromoethanol, jS ^ -dichloroethanol.

The liquid reaction media are ethers, ketones, Nitriles, esters, amides, aromatic or aliphatic, optionally nitrated or halogenated hydrocarbons, Alcohols, or water are suitable. Mixtures of the solvents mentioned can also be used be used.

The inventive method is carried out at temperatures between -50 and 100 ° C, with the use of guanidine preferably from -50 to 3O ⁰ C and with the use of dicyandiamide preferably from -20 to 80 ° C. .

In the case of the conversion of dicyandiamide with cyanic acid esters, the components are about used in a molar ratio of 1: 1. Expediently, dicyandiamide and cyanic acid ester are introduced in solution and dripping in alkali until no further alkali consumption can be determined. After peeling of the solvent, the end product is isolated from the residue. You can also use cyanate and let an alkali or alkaline earth salt of dicyandiamide act on each other.

In the case of the conversion of guanidine with cyanic acid esters, the components are approximately in the molar ratio 1: 2 implemented. The addition of a third mole of cyanate ester to trap the Hydroxyl compound can be beneficial for the reaction. Man. expediently specifies cyanic acid esters and guanidine salt and slowly releases the guanidine by adding alkali. Man

can also convert the cyanic acid ester into a solution of guanidine or this solution into a cyanic acid ester solution a drop. The end product is isolated as in the case of conversion with Dicyandiamide.

The triazine derivatives prepared according to the invention can be used for the preparation of polymers (cf. USA. Patent 2 560 825) can be used.

example 1

8.4 g (0.1 mol) of dicyandiamide are stirred in 20 ml of acetone and 20 ml of H2O, and A g (B mol) of NaOH (concentrated aqueous solution) is added (see table). 14.7 g (0.1 mol) of 2,4-dimethylphenyl cyanate are added dropwise at 0 to 5 ° C., the mixture is subsequently stirred for 20 minutes and sharply suctioned off. This is obtained after washing with ether

NH ₂

H ₃ C

No. 35 Ie Ag NaOH B moles Yield: C g 52.5% of the Fp .: D ° ^c 30 la 8th 0.2 2.1. theory 272 until 275 Ib 4th 0.1 6.0 277 until 278 Ic 2 0.05 9.1 277 until 278 Id 1 0.025 12.1 277 until 279 0.5 0.0125 4.0 275 until 276

. The products show no melting point depression with the product obtained according to Example 2. The IR spectra also agree with this. '

Example 2

5.4 g (0.025 mol) of guanidine sulfate and 11.1 g (0.075 mol) of 2,4-dimethylphenyl cyanate are dissolved in 50 ml of water and 30 ml of acetone. A solution of 2 g of NaOH in 10 ml of water is added dropwise at -10 ° C. After the reaction has ended, the mixture ^{is stirred for 1} hour at room temperature, after which an oily product is precipitated with water, from which 4 g (= 69.5% of theory) of 2- (2,4-dimethylphenoxy) -4 are obtained by trituration with ether. 6-diamino-triazines- (l, 3.5) in the form of a white powder with a fixed point of 277 to 279 ° C. Mp after recrystallization

Alcohol: 280 to 282 ⁰ C.. , -

Analysis: CuHi ₃ N ₅ O (231).
Calculated ... C 57.15, H 5.63, N 30.30, O 6.92%; Found ... C 57.04, H 5.80, N 30.08, O 7.15%.

The same product is obtained when using guanidine nitrate, carbonate or hydrochloride. The same product is also obtained when it is carried out in dimethylformamide as the solvent.

Example 3

4.2 g (0.05 mol) of dicyandiamide and 7.35 g (0.05 mol) of 2,4-dimethylphenyl cyanate are dissolved in 40 ml of acetone

and submitted 15 ml of water. 45% NaOH solution is added dropwise at 0 ^° C. until the pH value remains constant at 9 to 10 (about 8 drops). A temperature of 40 to 45 ° C occurs. The 2- (2,4-dimethylphenoxy) -4,6-diamino-triazine- (1,3,5) precipitates and is filtered off with suction after stirring for an hour. Yield 5.1g. ^After adding water to the filtrate, an oil is obtained from which another gram of the desired triazine precipitates.

Overall yield: 6.1 g (= 53% of theory); Mp. 277 to 278 ^° C. IR spectrum identical to that of the products obtained according to Examples 1 and 2.

B is ρ ie 1 4 ¹ p

Analogously to Example 3, 2- (4-methylphenoxy) - ■ is obtained from dicyandiamide and 4-methylphenylcyanate 4,6-diamino-triazine- (1,3.5), m.p. 288-289 ° C. Yield 55% of theory.

Analysis: G0H11N5O (217).

Calculated ... C 55.30, H 5.07, N 32.1 "", 'I 7.40%; Found ... C 55.34, H 5.19, N 31.58, O 7.84%.

Example 5

Analogously to Example 3, 2- (2-methylphenoxy) -4,6-diamino-triazine- (1,3,5) is obtained from dicyandiamide and 2-methylphenylcyanate from m.p. 231 to 232 ° C. Yield 48% of theory.

Analysis: CioHuNsO (217).

Calculated ... C 55.3, H 5.07, O 7.38%; found ... C 55.64, H 5.45, O 7.80%.

Example 9. ■

Analogously to Example 2, 2-phenoxy-4,6-diamino-triazine- (l, 3,5) is obtained from guanidine nitrate and phenyl cyanate from m.p. 258 to 259 ° C. The mixed melting point with that obtained according to Example 6 Product shows no depression, both IR spectra are identical. Yield 65% of theory.

Example 10

Analogously to Example 2, 2- (3-chlorophenoxy) -4,6-diamino-triazine- (1,3,5) is obtained from guanidine nitrate and 3-chlorophenyl cyanate from m.p. 242 to 244 ° C. That. The IR spectrum is that of Example 6 or 9 obtained substance very similar. Yield 45% of theory.

Example 11

6.1 g (0.05 mol) of guanidine are dissolved in 25 ml of dimethylformamide and a solution of 2 g of sodium hydroxide in 20 ml water were added at -2O ⁰ C. Then 16.9 g (0.1 mol) of a-naphthyl cyanate are added in portions at the same temperature. After stirring for half an hour, water is added. The pasty product is stirred with water, then ether and filtered off with suction. 6.7 g (= 52.5% of theory) of the

35

Example 6

To 259 Analogously to Example 3 obtained from dicyandiamide and phenyl cyanate 2-phenoxy-4,6-diamino-triazine (l, 3,5) of mp. To 26O ⁰ C.

Analysis: C ₉ H ₉ N ₅ O (203).
Calculated ... C 53.2, H 4.42, O 7.89, N 34.4%; Found ... C 53.32, H 4.74, O 8.00, N 34.25%.

Example 7

Analogously to Example 3, of dicyandiamide and 2-methoxyphenyl 2- (2-methoxyphenoxy) -4,6-diamino-triazine (l, 3,5) of mp. 267-268 ⁰ C. Yield 42% of theory. Analysis: C10H11N5O2 (233).

Calculated. C 51.5, H 4.72, N 30.02, O 13.76%; found .. C 52.00, H 4.99, N 29.50, O 13.89%.

Example 8

Analogously to Example 3, 2- (β, / S, / kinchloroethoxy) -4,6-diaminotriazinyl, 3.5) of melting point 205 to is obtained from dicyandiamide and (S, / 9, (S-trichloroethyl cyanate after evaporation of the acetone) 206 ⁰ C. Yield 40% of theory.

Analysis: C ₅ H ₆ Cl ₃ N ₅ O (258.5).

Calculated C 23.24, H 2.32, N 27.00, 0 6.20, Cl 41.3%;

found

C 23.89, H 2.76, N 26.95, O 6.67, Cl 40.1%. from a temperature of 290 to 291 ^° C. are obtained in this way.
Analysis: Ci3HuN ₅ O (molecular weight 253).

Calculated ... C 61.7, H 4.35, N 27.6, O 6.32%; Found ... C 61.77, H 4.55, N 27.45, O 6.58%.

Note: Analogously to Example 3, dicyandiamide is formed and α-naphthyl cyanate in the presence of sodium hydroxide the same product (identical IR spectrum).

Claims (2)

Patent claims: 1. Process for the preparation of ammeline ethers of the general formula OR N
H ₂ NC Il C-NH ₂ characterized in that a cyanic acid ester of the general formula ROCN where R is a haloalkyl radical or an optionally substituted aromatic radical, with about the equimolar amount of di- 7 s cyandiamide in the presence of catalytic to mola- 2. The method according to claim 1, characterized by lesser amounts of alkali or with about the half molar that one dicyandiamide and the Amount of guanidine — which is preferably provided during the cyanate ester and a lye is added dropwise. the reaction from its salts by alkali - additional is made free - at temperatures 5 Considered publications:
between -50 and + 10Q ⁰ C in the presence of a Smolin —- Rap ο port, s-Triazines and DeLösungsmittel or a Lösüngsrnittelgerni rivatives (1959), pp. 283 to 292;
implemented: J. Amer, Chem. Soc, 67 (1945), S, 1947/1948. 609 540/414 3.66 © Bundesdruckerei Berlin