DE2241717C2 - 3-Amino-thieno [2,3-b] pyridines, process for their preparation and their use - Google Patents

Description

IO

in which R ^{1 is} hydrogen, methyl or ethoxycarbonyl, R ^{2 is} hydrogen or nitro

R ^{3 is} hydrogen, methyl or phenyl and R ^{4 is} cyano, nitro, acetyl, benzoyl, nitrobenzoyl, methoxycarbonyl or ethoxycarbonyl.

2. Process for the preparation of compounds according to claim 1, characterized in that one compounds of the general formula

25th

R ¹ R ² I CN

30th

R ¹

S-CH ₂ -R ⁴

cyclized in the presence of a base

3. Use of the compounds according to claim 1 or 2 as diazo components for Manufacture of azo dyes.

(H)

S-CH ₁ -R ⁴

in the presence of a base.

Compounds of the general formula Π are 1. B. by reacting compounds of the general formula III

(Hl)

with compounds of the general formula IV

Hal-CH ₂ -R ⁴ (IV)

Hal: Cl, Br. J

or by reaction of compounds of the general Formula V

(V)

The invention relates to compounds of the general formula

with compounds of the general formula VI

NH ₂

HS-CH ₂ -R ⁴

(Vl)

(I)

in the

R ^{1 is} hydrogen, methyl or ethoxycarbonyl or R ^{2 is} hydrogen or nitro,
R ^{3 is} hydrogen, methyl or phenyl, R ^{4 is} cyano, nitro, acetyl, benzoyl, nitrobenzoyl, methoxycarbonyl or ethoxycarbony! mean. Preferred radicals are, for example: for R ¹ hydrogen, methyl,
for R ² hydrogen, nitro,
for R ³ hydrogen, methyl,
for R ⁴ cyan, nitro.

₆ ■> accessible. R ¹ to R ⁴ in the general formulas II to VI have the meanings given.

Compounds of general formula III can be, for. B. according to a regulation by U. Schmidt and H. Kubitzek, Chem. Ber. 93, 1559 (1960).

For example, the following compounds are listed:

2,4-dimethyl-5-cyano-6-thio-pyridone,
4-methyl-2-phenyl-5-cyano-6-thio-pyridone,
5-cyano-6-thio-pyridone,
2-methyl-5-cyano-6-thio-pyridonecarboxylic acid

(4) ethyl ester,

2-methyl-5-cyano-6-thio-pyridone,
S-nitro-S-cyano-δ-thio-pyridone.
Compounds of the general formula V are, for. B. from J. Chem. Soc. (1962), page 1976, or from Heterocyclic

Compounds, Pyridines and Derivatives, Part II (1961) or from DE-PS 21 27 521 known. Examples include: 2-chloro-3-cyano-pyridine,
2-chloro-3-cyano-6-methyl-pyridine, 2-chloro-3-cyano-6-dimethyl-pyridine, 2-chloro-3-cyano-4-methyl-6-phenyl-pyridine, 2-chloro-3- cyano-6-methyl-pyridine-carboxylic acid (4) ethyl ester.

Examples of compounds of the general formula IV include:

Chloroacetonitrile, chloroacetic acid alkyl ester (1 to 2 carbon atoms), chloroacetone, bromo-nitro-methane or Phenacyl chloride and p-nitro-phenacyl chloride. Instead of the chlorine, the corresponding bromine derivatives or instead of the bromine the chlorine derivatives can also be used be used.

Examples of compounds of the general formula VI are:

Thioglycolic acid / e-methyl ester, thioglycolic acid ethyl ester,
Mercaptoacetone and
Mercapto-acetonitrile.

The cyclization of the compounds of general formula II is expediently carried out in a solvent or suspension medium in the presence of a base at temperatures from 20 to 150 ⁰ C, preferably 50 to 120 ° C. The isolation of the compounds of the general formula I is very simple. They can often be obtained directly from the reaction mixture by filtration or centrifugation. In the case of easily soluble compounds, the solvent is distilled off and / or diluted with water and filtered off with suction.

Possible solvents or suspending agents are:

Alcohols such as methanol, ethanol, propanol, butanol;

Glycols such as B. 0-hydroxyethyl methyl ether; Acid amides, such as. B. formamide, dimethylformamide, N-methyl-pyrrolidone;
Ether, such as B. tetrahydrofuran or dioxane; Dimethyl sulfoxide, water and mixtures of the solvents listed with water. The bases are:

Sodium or potassium carbonate, sodium or Potassium hydroxide, sodium methylate and ethylate and organic amines such as trimethyl, triethyl, Tri-hydroxyethyl or diethylamine. The reactions can be carried out with catalytic, Carry out equivalent or excess amounts of base.

A simplification of the process is that, without isolating intermediate stages, the general Formulas II and III in a kind of "one-pot reaction" either starting from 0-dicarbonyl compounds, Cyanoacetamide and compounds of the general formula IV or starting from compounds of the general formulas V and VI, the end products of general formula I are produced directly. The connections of the general formula I are valuable diazo components for the preparation of, in particular, disperse dyes.

Details can be found in the examples. Unless otherwise noted, all data relate to about parts and percentages in the following examples by weight.

example 1
NH ₂

COCH,

2-acetyl-3-aminothieno [2,3-b] pyridine

In a sodium ethylate solution, which was prepared from 2.4 parts of sodium and 70 parts of ethanol, carries 13.6 parts of 3-cyano-2-thio-pyridone are introduced at room temperature with stirring and the mixture is stirred for about 15 minutes Almost everything has dissolved. 9.25 parts of chloroacetone are then added dropwise, the temperature rising rises approx. 50 ° C. To complete the reaction, the mixture is refluxed for a further hour. That The reaction mixture is cooled, the solid is filtered off with suction, washed with water and dried at 60 ° C in a vacuum.

Yield:
F.

i 4.8 parts (78%)
195 and 196 ° C

After adding 100 Part water isolate another 2.5 parts.

Overall yield 173 parts (90%)

Melts recrystallized into a sample of methyl glycol at 208 to 210 ° C.

Analysis: C ₉ H ₈ N ₂ OS ^ G 192.17

Calc .: C 56.25, H 4.20, N 14.58, 0 8.33, S 16.66;
r> Found: C55.9, H 4.1, N 15.0, 0 8.6, S 16.7.

NH,

COCH ₃

2-acetyl-3-amino-4,6-dimethyl-thieno [2,3-b] pyridine

4.4 parts of 3-cyano-2- (acetyl-methylene) mercapto-4,6-dimethyl-pyridine v / earth together with 2 parts of potassium carbonate in 30 parts of methyl glycol and 5 parts of water Heated under reflux for 2 hours. The crystals separated out on cooling are suctioned off with water washed and dried in vacuo at 60.degree.

Yield:
F.

3.7 parts (84%)
184 to 187 ⁰ C

S; MW 220.22

Calculated: C 59.99, H 5.49, N 12.72, 0 7.26, S 14.53;
Found: C60.1, H 5.5, N 12.7, 0 7.8, S 14.6.

Example 3

The procedure described in Example 2 is followed, but 1.5 parts are used instead of potassium carbonate Triethanolamine too. In addition, you work without the addition of water.

Yield:
F.

3.8 parts (86.5%)
184-187 ° C

Example 4

You proceed as in Baispie! 2 described. Instead of 'of potassium carbonate and water are added 2.5 parts of a 30% sodium methylate solution.

Yield:
F.

0-, N

4.0 parts (91%)
185 to 187 ° C

Example 5

NH ₂

Yield:
F.

19.2 parts (72%)

198 to 200 ⁰ C:

from ethanol 206 to 207 °

9.0 parts of mercaptoacetone are first added, the mixture is stirred for 10 minutes and then 16.65 parts of 2-chloro-3-cyano-4,6-dimethylpyridine are added ^{a little at a time.} Parts of water are added and the solid is filtered off with suction

OCH ₅

3-Amino-5-nitro-thieno [2,3-b] pyridinecarboxylic acid (2) ethyl ester

15.7 parts of the sodium salt of nitro-malondialdehyde. 10.0 parts of cyanthioacetamide and 10 drops /? - diethylamino-ethanol are dissolved in 50 parts of ethanol 15 Heated to reflux for minutes. The mixture is left to stir for 30 minutes, and 12.25 is added at a temperature of 40.degree Parts of ethyl chloroacetate and 4 parts of triethylamine are added and the mixture is refluxed for a further hour. The reaction mixture is cooled, 80 parts of water are added and the mixture is filtered off with suction. The residue is with Washed with water and then dried in vacuo at 60.degree.

Analysis: CoH ₉ N ₃ O ₄ S; MG 267.20

Calc .: C 44.95, H 3.40, N 15.73, 0 23.96, S 11.98;
Found: C45.2, H 3.5, N 15.5, O 23.8, S 12.2.

NH ₂

H ₃ C COCH ₃

2-Acetyl-3-amino-4,6-dimethylthieno [2,3-b] pyridine

In a sodium methylate solution, which was prepared from 2.4 parts of sodium and 120 parts of methanol, yields:
F.

16.5 parts (75%)

173-175 ° C;

from ethanol 184 to 187 "

Analysis: CH, 3N2OS; MW 220.22

Ben: C 59.99, H 5.49, N 12.72, 0 7.26, S 14.53;
Found: C60.1, H 5.5, N 12.7, 0 7.4, S 14.6.

Example 7
CH ₃

H ₃ C

! I Π

NH,

COOCH ₃

3-Amino-4,6-dimethyl-thieno [23-b] pyridinecarboxylic acid (2) methyl ester

10.6 parts of thioglycolic acid metayl ester, 16.6 parts 2-Chloro-3-cyano-4,6-dimethyl-pyridine and 10 parts of triethylamine are dissolved in 100 parts of methanol for 2 hours r, heated to reflux. First a clear solution forms, from which a solid gradually develops ruled out. It is cooled, suctioned off and washed with water.

Yield:
F.

18 pieces (76.5%)

187 to 189 ° C;

from methanol 189 to 190 ° C

Analysis: C ₁₁ H ₁₂ N ₂ O ₂ S; MW 236.22

Calc .: C 55.93, H 5.12, N 11.86, O 13.55, S 13.55;
Found: C56.2, H 5.2, N 12.2, O14.0. S 13.5.

Analogously to the methods given in Examples 1 to 7, those in the table below can also be used Compounds characterized by specifying the substituents, the melting points and the elemental analyzes produce:

C O ^. η O O O £ C C

'*' - - γ τ *% T 7> i Zm ζ, rs ^ o -71-- ^, ^ c - / \ c ^ 'r, "" ί, --Γ οι "^ - _J oj ^ - _J οι _7 fN _7 (^ i, - _; n, - - η _Γ

! υ Ρ! υ - υ 'P) ΰ - , -m - c -Tco .7 ^ c .'s .-> / -,, -ri Un Um U - Un ο π U ri Un

-t - ri - irj π -to OO - τ -t 3C oc η οι ^ o vo ^ - η ir, > -c «c - *

- π ri

3Cw ir, t οι - -tr-

tr, .C ri οι - - OC -
ir, ir, -t 'r,

£ X - ir, ir ', ir',

CC-C - - -t -t -CC

ο οι τ, O οι οι - -—

ir, cc cc r ~~ r-- r-

r. ir. ir, ir, ir. -C

τ] ι / - | r- r—

-f- -t ir, ir,

CC Ol OC

Γ. τη OC T A. -

-τ r- \ I.
-t - χ ir. -τ Oil r-i Γ ΟΟ i
Ό OC

ΟΙ

ίο

■ Si

IS)

O 'Ol

■ j)

_ - '- co ~ οι' i - '-; ο

"Γ-Ι y -« Γ Ol .JT Ol _. " Ol ^ C7 ro fc «7 ro« "" Ol

, 01 "C ro '" ¹ ^ oo'" ¹ ^, oo '■"", --ι ^;" V oi ^ i oi

■ oo, 'oi, 70, Tr—, "vo, 7-r, 7—, ~ 00

o * 01 v_ / η v »/ ro vj ro ν- / in

C _r 7 oo, * cn, TO ri ν- / cn vj (N vJ ro

Ol V ^ / ro V- / ro On

in ro η OO
CO CO in ro in η Tf
η Oil - O Oil 01 OO cc O Oil -r ir, ■ n ir Tf Tf 0 O - - · η Oil Oil ''! QO OO - ~ ro rO ro
1 ro - 1 - -'

τ, r— r- οι - οι r ~ - C- οι

^. t -f -f ~ -r-r- oi r ι tr, Ti - · - Ol Ol - · - ■ - -

■ - ■ - · - · - ir, <r,

οι -τ οι

ir, - - - - οι oi

oi c: ^r o ro

ro oil

r ~ - cc r ^ r -r '-t r' r- '

-tc ο ro
-f -r ir. ir,

oi ro 3C: oi oi rr ^ - - - - c: - - in ir, ir, ir, t 'τ -T -f ir' ir, ir! ir!

ac

ccoi

ro '-r

-f -r -f -f -f -f

- Ol CT: ro

-r - r- ~ cNr ~ -r ~

i / o CT- - O - Ol 'n CT- ro -f C: CT-

O 3 π r,

OO oc oc OO OC * "f Tf -OO ir, ir, ro ro ir, ir, oc r- ι- cc ro ro 'r, ir, OO -f -f ir, ir, ir, ir, ir, ir , OO OO co OO r- r-

CT- ir, ir, ol

oc oc> r, ο

ir, ir, -τ τ

οι

OC Oil

- r-

r-

OO

cc

ro OO Oil O Oil Oil

υ ο

CJ O CJ

CJ

CJ

rn = ζ

CJ

CJ

ft

CJ

CJ

CJ

WHERE

CN CN

ro CN

OJ

VO O- OO O O

CN CN CN Ol CO

CN

continuation

Example R ¹ No.

R-

NO, NO, NO.

CH,

K ' 220-56
/ CIS. Aiulyse
Her .:
Ciel '.: 43.64
43.6 Il .S3
.9 25.45
25.4 ι) S. Siiinmonl'ormel
Molecule NJ
NJ CN 223 -25 56.19
55.9 1
1 .03 04/14
14.2 14.54
! 4.9 14.54
14.7 CsII ₁ N ₁ OjS
220.14 -vj CO- C ₁₁ IK 18 (1-81 46.9S
47 I) 3 .94
I) 14.94 1 6.03
16.0 10.69
10.5 299.24 C'O.C'H, 3
4th 22. "(I. 11.38
1 1.6 C ₁₁ H ₁₁ N ₁ O ₁ S

Claims (1)

Patent claims: 1. 3-Amino-thieno [2,3-b] pyridines of the general formula NH, To prepare the compounds of the general formula I, compounds of the general formula I are cyclized Formula II