DE2336978A1 - Iso-thi-azolo-pyrimidin-dione dyes - for dyeing polyamides, cellulose esters and polyesters - Google Patents

Abstract

Isothiazolo-pyrimidin-dione dyes of formula (where R is opt. substd. (cyclo) alkyl, aralkyl, or (hetero)aryl; R' is H or opt. substd. alkyl; and K is the radical of a coupling component) are used in prepns. contg. the other usual constituents, for dyeing polyamides, cellulose esters or esp. synthetic linear polyesters. Strong red to blue dyeing is obtd. with very good fastness, esp. in the red range. Dyeing can be carried out by the high temp. method and often with carriers.

Description

BASF Aktiengesellschaft

our reference: 0.Z. 30 015 Bg

6700 Ludwigshafen, July 18, 1973 Isothiazolo-pyrimidinedione paring agents

The invention relates to dyes of the formula I.

R.
I.

O. II IT

0 N = Ii-K

in the

R optionally substituted alkyl, cycloalkyl, aralkyl, aryl or heteroaryl,

R is hydrogen or optionally substituted alkyl and K mean the remainder of a coupling component.

Examples of alkyl radicals for R and R are: methyl, ethyl, n- and i-propyl, n- and i-butyl, n-hexyl, as examples of an unsaturated alkyl radical, allyl or lethallyl, as examples for a substituted alkyl radical y-IIethoxypropyl, tert-butoxypropyl ^ ß-dimethylaminoethyl.

466/73 - 2 -

409886/1181

- 2 - O.Z. 30 015

Aralkyl radicals are benzyl, Phenyläthy1 and y-phenylpropyl ge

called.

The cycloaliphatic radicals are preferably derived from cycloaliphatic rings with 3 to 6 carbon atoms in the ring and can optionally be substituted by alkyl radicals, such as methyl or ethyl. Mention may be made of cyclohexyl or cyclohexyl substituted by methyl.

Examples of heterocyclic radicals are the puryl or the Thienyl radical called, which can be substituted, for example, in the usual way.

The preferred aromatic radical is the phenyl group, which can optionally be substituted by chlorine, bromine, methoxy, ethoxy, methyl or ethyl, such as p-chlorophenyl, p-methylphenyl, p-methoxyphenyl.

Radicals of the coupling components K are derived for example from aminonaphthalenes, indoles, pyrazoles, phenols, naphthols ethylheterocyclen, acetoacetarylides, cyano _"t methyl bases, malononitrile, barbituric., Quinolones, Homophthalimiden, pyridines and, in particular aniline derivatives.

409886/1181

- 5 - O.Z. 30 015

Individual coupling components are in addition to the "3 already mentioned: 2-Ilethyl-indole, 2-phenyl-indole, 1-methyl-2-phenyl-indole, 4-methylphenol, phenol, 1-II-hydroxynaphthalene, β-haphthol, 2 -Amino-7-hydro :: ynaphthalene, 1-Amino-5-hydroxy-naphthalene, 1-phenyl-3-methyl-pyrazolone, Acetesßigsnilid, 2-Cyanmethyrbenzimidazol, 1,3 »3- ^ 2? Imethj'-l- 2-meth; rlenindoline, 2-cyanomethyl-benzothiazole, 1-phenyl-3-cs.rboxy-pjTazolon-5, 2,4-di-hydroxyquinoline, 1-phenyl-5-amino-pyrazole, 1-aminonaphthalene, 2-N- Ethylamino-naphthalene, S-hydroxy - ^ - methyl-naphthalene, 1f5-dihydroxy-naphthalene, 1,6-dihydroxy-naphthalene, 1,7-dihydro; cy-naphthalene, 2,7-mhydroxy-naphthalene, 1-ethylamino- naphthalene, 1-phenylaiainonaphthalene, 1-cyclohexylamino-naphthalene, 1-ß-hydroxy-ethylaminonaphthalene, 2-ß-hydroxyethylamino-naphthalene, 8-hydroxyquinoline, 1-methyl-A-hydroxyquinoline-S, 2-hydroxy-3-carboxyoline naphthalene, 2-hydroxy-3-β-hydroxyl ^r- ethylamino-carl) onyl-naphthalene , 1-oxo-2-methyl-3-hydroxy-dihydroisoquinoline, 2,4-6-trioxo -hexahydro-p; rriniidin, 2-benzimidazolyl-acetanilide, 2,6-dihydrox3 ^r -5-cyano-4-methyl-pyridine, 1,2-dihydroxybenzene, 1,3-dihydro., qr-dexxzol.

The coupling components of the aniline series correspond to the ioimel II

in the

R ² optionally substituted by hydroxy, alkoxy, cyano, alkoxycarbonyl, halogen, acyloxy or acylamino alkyl, cycloalkyl, aralkyl or aryl,

409886/1181 " ⁴ "

- A - ο.Z. 20 C15

R is hydrogen or optionally by hydroxy, alkoxy, cyano, Alkoxycarbonyl, halogen, acyloxy or acylamino substituted alkyl or aralkyl,

R is hydrogen, methoxy, ethoxy or methyl and

R is hydrogen, chlorine, bromine, methyl, methoxy, ethoxy or optionally mean substituted acylamino.

Individual radicals R ^ are for example: ß-hydroxyethyl, ß-methoxyethyl, fl-cyanoethyl, methoxycarbonylethyl, ethoxycarbonylethyl, propoxycarbonylethyl, ß-chloroethyl, ß-hydroxypropyl, ß-acetoxyethyl, γ-acetoxypropyl, ß-propionyloxyethyl, ß-butyroxyethyl, ß-acetylaminoethyl, γ-acetylamino-propyl, benzyl, ß-phenylethyl, 1,2-dihydroxypropyl, aceto-acetoxyethyl, w-phenoxy-aoetoxyethyl.

2 5

For R, the radicals mentioned for R are as well as the following

Groups to be listed: cyclohexyl, methylcyclohexyl, phenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl or methylphenyl.

Acyl amino radicals R are for example: acetylamino, propionylamino, Benzoylamino, chloroacetylamino, chlorobenzoylamino, methylsulfonylamino, ethylsulfonylamino, aminocarbonylaasino, methoxy- or ithoxycarbonylamino, methylaminocarbonylamino or phenylaminocarbonylamino.

A09886 / 1181

- 5 - O.Z. 30th

Dyes of the formula I a are of particular interest

in which A is alkyl with 1 to 4 carbon atoms or phenyl,

A ¹ alkyl with 1 to 4 carbon atoms,

2 A alkyl with 1 to 4 carbon atoms, ß-hydroxyethyl, ß-hydroxypropyl, ß-cyanoethyl, methoxy carbonylethyl, ethoxycarbonylethyl, Ac et oxy—

ethyl or propyl or aoetylaainopropyl, hr alkyl with 1 to 4 carbon atoms, ß-hydroxyethyl or -propyl, ß-acetoxy, ß-propionyloxy or ß-butyroxyethyl or -propyl, ß-methoxy or

ithoxyethyl, benzyl or phenylethyl, A ^ hydrogen or methoxy, vaaä. k ^J hydrogen, methyl, chlorine, acetyllamino , propionylamino, methyl sulfonylamino or methoxycarbonylamino .

^{A 1} methyl is particularly preferred for A methyl

A ² methyl, ethyl, propyl, butyl, ß-hydroxyethyl

A ⁵ methyl, ethyl, propyl, butyl, fl-hydroxyethyl, β-cyanoethyl, ß- methoxycarbonylethyl or ß-ithoxycarbonylethyl,

409888/1181

- 6 - O.Z. 30 015

Ar hydrogen

A ^{5 is} hydrogen, chlorine, acetylamino.

Diazo compounds can be used to prepare the dyes of the formula I of amines of the formula III

with coupling components of the formula IV

H-K IY

realize.

Diazotization and coupling are carried out according to known methods Methods.

Compounds of formula III and their preparation are from the

^Patenfc (patent application P 22 48 231.1) known,

The new dyes are red to blue and are suitable for dyeing polyamides, cellulose esters and especially synthetic ones linear polyesters. Very strong red to blue dyeings with, as a rule, very good fastness properties, especially im Red area. As a dyeing method is also suitable in many cases HT dyeing also includes dyeing with Carriera.

409886/1181

- T - O. Z. 30 015

Parts and percentages in the following examples relate to unless otherwise noted, based on weight.

example 1

9, η parts of 3-amino-7-phenyl-isothiazolo p, 4-djpyrimidin-dione (4.6) are dissolved in 100 parts of concentrated sulfuric acid at room temperature. It is then cooled and parts of a glacial acetic acid / propionic acid mixture (17: 3) are added dropwise at 0-5 C h0 parts and then diazotized by adding 13 parts of nitrosylsulfuric acid with a content of 14.7% N ₂ O. After 3 hours of stirring at 0-5 ° C., the diazo solution is slowly poured into a coupling solution aas b, J parts of N-β-cyanoethyl-N-ethyl-aniline, 7 parts of concentrated hydrochloric acid, 1 part of sulfamic acid, 500 parts of ice and 250 parts Pour in parts of sodium acetate solution (23 #ig). The dye precipitates in crystalline form, is filtered off with suction, washed well with water and dried at 50 ° C. under reduced pressure. He dyes polyester material in a bordo color.

11 N.

• ο

- δ -4 0 9 8 8 6/1 HM

- 8 - C.E. ; 50 015

Example 2

The procedure is as in Example 1 and instead of 8.7 parts of N-ß-cyanoethyl-N-ethyl-aniline, 10.35 parts are used N-methoxycarbonylethyl-N-ethylaniline, one obtains a Dye, the polyester, polyamide and cellulose 2 l / 2 acetate colors in red-violet tones:

CEL

The same procedure gives those identified below by specifying diazo and coupling components Dyes:

409886/1181

ο. δ. ^ o υΐί> -

example

Diazo component coupling component e

Shade au?

CE-

V ¹ V ¹

O bra ₂

C _o H.0H ⁴

Cl

ITHCOCH

C II, OH ⁴

⁵

^N c η

⁵

HNCOCH,

C _o H.0H

CH.OH ⁴

HIiCOCH

OCH ₅ C ₀ H.OH

^N C H. CII ^ ⁴

OCH,

G ₀ H.OH C ₂ H OH

HHCOCH ₇

red-violet

blue-violet

red-violet

red-violet

red-violet

blue

blue

- 10 -

40988 6/1181

- ίο - o.z ;; o 015

Example 10

10.6 parts of 3-amino-7-phenyl-isothLazolo [3,4-c are dissolved in 100 parts of concentrated sulfuric acid at room temperature, the solution is cooled to 0-5 ° C. and 30 parts of a glacial acetic acid propionic acid are left at this temperature -Ms solution 17: add dropwise. Is then diazotized by iigibe of 13 parts of nitrosylsulphuric acid with a content of 14.7 '> to U ^ O ,. After 3 hours of stirring at 0-5 ° C., the diazo solution is slowly added to 8.7 parts of N-β-cyanoethyl-N-ethyl-aniline, 7 parts of concentrated hydrochloric acid, 1 part of sulfamic acid, 300 parts of ice and 250 parts of sodium acetate solution (23 > 5i-ς) flow. The dye precipitates in crystalline form. jir is washed aogesa.igt, _r -ut: niu water and at 50 ⁰ C with reduced jrusk ge ^ -Oc-knead. ßr colors polyester material and cellulose-2 1 / - "ii-acetate in bluish red tones.

- 11 -

BATH ORIGINAL

409886/118 1

- 11 - O.Z. 30 015

Example 11

If uie is described in Example 10 and used instead of h, 7 parts of N-ß-cyanoethyl-N-ethylaniline 10.35 parts N-ß-Methoxycarbonylbthyl-IJ-ethylaniline, one obtains a Dye, the I olyamld, cellulose- ^ l / 2-acetate and polyester colors in red violet tones.

bath 409886/1181

- 1 O

mm jt,

ο.ζ. ; 30 015

example

Diazo component coupling component j color shade

12th

15th

16

17 18

0 HH ₂ C ₂ H ₄ OH

GIL

Cl

CHOH ^ ⁴

C ₀ H.OH

^{2 4}

CHOH ^{2 4}

V = / ^N CH

NHCOCH,

NHCOCH ₂
5

C ₀ H.OH ^{2 4}

C ₀ H. OH ^ 4

IiHCOCH

CH OH ⁴

C H OH

^{2 4} C ₂ H ₄ OH

NHCOCH ₅

blue-violet

blue-violet

red-violet

red-violet

red-violet

blue

blue

409886/1181

Example 19

OZ, 30 015

13 parts of 3-amino-7-phenyl-isothiazolol3i4-dJpyrirriidiri-dione (4.6) are dissolved in 100 parts of concentrated sulfuric acid at room temperature. This solution is cooled and 30 parts of a glacial acetic acid / propionic acid mixture 1? : 3 to. It is then diazotized by adding 13 parts of nitrosylsulfuric acid containing 14.7 % of N ₂ O. At 0 - 5 ⁰ C., stirred for 3 hours, then allowed to the clear diazo solution thus obtained 10.3 parts of 3-diethylamino-acetanllid, 7 parts of concentrated hydrochloric acid, 1 part of sulfamic acid, 500 parts of
Ice and 250 parts of sodium acetate solution (23 #ig) pour in. The dyestuff, which is obtained in crystalline form, is filtered off with suction, washed well with water and ^{dried at 50 °} C. in a vacuum. It dyes polyester material in red-violet tones.

NHCOCH ₃

-U-

ORSGINAL INSPECTED

409886/1181

example

O.'2. * 0

Diazo component coupling component

20th

22nd

25 24

25th

IiECOCH ₃

C ₀ H.OE

* C ⁴

C ₀ H-OH ⁴

9 ^CH

C ₀ H.OH

^4th

HHGOCH,
5

C ₀ H. CK 4

MCOCH ₅

C ₉ H ₄ OH

red-violet

red-violet

red-violet

red-violet

"blue

"blue

409886/1181

Example 26

0.2.30 01ί>

2336378

Γ "1

10.6 parts ^ -amino ^ jT-dimethyl-isothiazolo Γ3> 4-dJpyriraidin-

dione (4.6) are dissolved in 100 parts of 85> ^ sulfuric acid at 10 - 15 ° C, cooled to 0 - 5 ° ^ and at this temperature by the slow addition of 15 parts of nitrosylsulphuric acid with a content of 12.7 % on NpO ^, diazotized. After four hours: !!

Stirring at 0 - 5 ° C, the resulting clear diazo solution is added to 8.25 parts of N-ß-oxethyl-N-ethyl-aniline, 7 parts of concentrated hydrochloric acid, 1 part of sulfamic acid, 500 parts of ice and 250 parts of sodium acetate solution (2J> # ig) flow. The resulting crystalline dye is filtered off with suction after prolonged stirring, ater washed well with V / and dried at 5O ⁰ C in vacuo. It dyes polyester, polyamide and cellulose 2 1/2 acetate in purple tones.

C ₂ E ₄ OH

- 16 -

409886/1181

- 16 - ΰ. Ζ. χ, 015.

Example 27

The procedure described in Example 26 is followed and instead oxethylethylaniline is used 11.4 parts of IT-ß-C & rboraethoxyethyl-K-raethyl-m-chloroaniline a dye is obtained which dyes polyester, polyamide and cellulose-2 1/2 acetate in strong red-violet tones.

?H

⁰ X ¹ YS

II-fe ^ -W ^T

r-. C ₀ H-GO ₀ CII

0 H = H / T ^ ^ ²⁴ *

Cl

- 17 -

409886/1181

10 υ χ%

2336378

example

Di c? .Z okOEToonent e coupling component I color

33

34 35

CH-

CE,

C-JL-ITHCOCH,

CH.OH
^{2 4}

V- / N

C ₀ H.OCH,
■ 24 *

C ₂ H ₄ OH

° 2 ^H ;

C ₀ H. ClI
■ 2 4

C _o H.0CCH,

^ά 4 μ -0

C ₂ H ₄ H

C H OH

violet

red-violet

red-violet

red-violet

red-violet

Red

violet

violet

reddish purple

- 18 -

409886/1181

example

Mazokoinponent e coupling component e

hue

37

38

39 40

42

43

44

45

VVS

0 ITH ₂

C ₉ H, CN ^{2 4}

C ₉ H.OCH, 2 4

C ₀ H.OH

^{2 4th}

^C 2 ^H 4 ^C1

C H OH

* ⁴

NHCOCH ₅

NHCOCH ₅

^C 2 ⁿ

C ₀ H-OH

C ₉ HOH

OCH ₂

C ₂ H ₄ OH

C ₂ H ₄ CN

NHCOCH ₅

bor do

red-violet

red-violet

bordo

red-violet

red-violet

red-violet

violet

blue

409886/1181

O.Z. 30 013

At; ι. Lt

Diazo component

Coupling component

hue

46

CH,

Υ'-Λ W

C ₀ H.CN

"bordo

47

CH OH
^{2 4}

blue-violet

CH,

48

red-violet

CH ₂

50

Example 51

red-violet

bordo

Parts of J-Aminp-SiT-di-n-propyl-isothiazolol ^ * ² * -djpyrimidindione (4.6) are dissolved at 10-15 ° C in 100 parts of 85 # sulfuric acid and at 0-5 ° C by adding 15 parts of nitrosylsulfuric acid with a content of 12.7 % of N ₂ O, diazotized.
The diazo solution is allowed to stir for 3 hours while cooling and then combined with a solution of 11 parts of N-ß-cyanoethyl-N-ß-oxethyl aniline, 25 parts of water, 7 parts of concentrated
Hydrochloric acid, 1 part sulfamic acid, 500 parts ice and 250 parts sodium acetate solution (23 #ig). The crystalline accumulating
Dyestuff is stirred for 3 hours, filtered off with suction, washed well with water and ^{dried at 50 °} C. under reduced pressure.
He dyes polyester material in a bordo color.

'- 20 -

409886/1181

J b j / c

CpH ₄ OH
0 ^ ' ^{2 4}

Example 52

Proceed as described in Example 51 "and use 11 parts instead of 11 Oxäthyl-cyanoethylaniline 13.4 parts of N-ethyl-N-ß-oxäthyl-m-toluidine, so one obtains a dye, the polyester and polyamide in violet Tones colors.

₃₇

VA

^C 3 WV

0 MA-Bf ^{2 5}

C ₂ H ₄ OH

- 21 -

ORIGINAL INSPECTED

409886/1181

example

Diazo component Rupplungskomponent e

015

2336378

hue

54

58

C ₅ H ,, -:

«Over

C ₂ H ₄ CO ₂ CH ₅

OH

C ₂ II ₄ OH

HKOOCH,

C ₂ H ₅ C ₂ H ₅

C _o H.0H

^{2 4}

ITHCOCIL

"3 C ₀ H.OH

r ⁴

NHCOCIL

C ₂ H ₄ ClT

C _o H.0H

CpH .0H ⁴

ITHCOCH,

C ₂ H ₄ OH

C ₉ H ₁ OH ^{2 4}

Red

bordo

"bordo

red-violet

rofc violet

blue

blue

5 / ioletb

, iolefcfc

- 22 -

409886/1181

233t

example

62 65

68

70

Yl

Diazo component

U ₃ H ₇

Yt-S

O NIL

Coupling component color

CH ₃

G H.CN ^{2 4}

C ₀ H, OCH, '24 3

'C ₂ H ₄ CO ₂ CH ₃

C ₀ H, CN '2 4

'C ₂ H ₄ OCH ₃

C ₂ H ^ NHCOCH-.

^ C ₂ H ₄ OH

^V C ₂ H ₄ CO ₂ CH ₃

C ₀ H, OH (/ \\ _Ή ' 2 4

C ₂ H ₄ OCH ₃

Λ-π

, C ₂ H ₄ OCH ₃

'C ₀ H-OC-CH, ² 4 H 3 0

J ₀ H-OC-CH,

^ 4 ti ?

4 κ 3 ο

red-violet

red violebfc

bordo

blue violet. 9 bt

robviole bb

violebb

robviols b b

rofcvLol.

bordo

violetb

409886/1181

- 23 -

; \, ■ '..' Ioile 3-amino-5,7-di-n-butyl-isothiazolo [3, ² I-OJpyrimidin-31 η (J \, 6) is dissolved at room temperature in 100 parts of 85 $ strength i ' Nefelsäure, this solution cools and diazot: "(rl · at 0-5 ° C by adding 15 parts of nitrosylsulfuric acid with a content of] 2.7 % of H ₂ O. After three hours of stirring, iio diazo solution is left slowly flow in to 8.7 parts of N-β-cyanoethyl-N-äthylli-ün, 25 parts of water, 7 parts of concentrated hydrochloric acid, 1 part of ammonium sulfonic acid, 500 parts of ice and 250 parts of sodium hydroxide solution (2%) . crystalline form It is stirred, filtered with suction, washed well with water and b i 50 ⁰ C in vacuum-dried It dyes polyester material.

409886/1 181

ο. ζ. 30 o: -. 5

example

Diazo component

Coupling component color

73 74

76 77

C ₄ H ₉ 0. N

0 NH ₂

C ₉ H. OH 4

CJOH ⁴

NHCOCH ₅

NHCOCH ₅

C_H.0H

CJOH ⁴

NHCOCH

CH.CN ^ ⁴

red-violet

red-violet

red-violet

red-violet

blue

- 25 -

409886/1181

- 25 - O. Z, 30 015

10.6 parts of ^ -amino-S ^ Y-dimethyl-isothiazoloF5,4-djpyrimidindione (4.6) are added to the mixture of 15 parts of nitrosylsulfuric acid with a content of 12.7 % of NpO at 0-5 ° C Entered 100 parts of 88% sulfuric acid and stirred at 0-5 C for 4 hours. The solution of 6.6 parts of 2-methylindole in 55 parts of concentrated sulfuric acid is then added to the diazo solution, the mixture is then stirred for 15 minutes and the mixture is slowly poured onto 500 parts of ice. After several hours. Stirring, the dyestuff formed is filtered off with suction, washed neutral with water and ^{dried at 50 °} C. in vacuo. The dye dyes polyester fabric in real orange tones.

f ^H 3

O N = K

- 26 -

409886/1181

O.Z. 30 015

Example diazo component, coupling component, color shade

0..H

OH,-

0 KH,

HO

HO

HO

H ₂ N

\ / r oh

CH,

HO

CH ₃ -C-CH ₀ -C -NH

5 Il A ^ M

O 'O

reddish yellow

reddish yellow reddish yellow

Red orange

bordo

blue (perlon)

orange

Ib

409886/1181

- 27 -

O.Z.; O 015

example Di azo component Coupling component hue 87 0 NN ^
CH-- ^^^^
0 HH ₂ 0 H valid 88 I! orange cn I 89 Il CN yellow

40988 6/1181

Claims (1)

Claims £ J J O 9/8 in the R optionally substituted alkyl, cycloalkyl, aralkyl, aryl or heteroaryl, R is hydrogen or optionally substituted alkyl and K mean the remainder of a coupling component. 2. Dyestuffs according to Claim 1 of the formula Yes, in the A alkyl with 1 to 4 carbon atoms or phenyl, A ¹ alkyl with 1 to 4 carbon atoms, A alkyl with 1 to 4 carbon atoms, ß-hydroxyethyl, ß-hydroxypropyl, ß-cyanoethyl, methoxycarbonylethyl, ethoxycarbonylethyl, Acetoxyethyl or -propyl or acetylaminopropyl, A ^ alkyl with 1 to 4 carbon atoms, ß-hydroxyethyl or -propyl, ß-acetoxy, ß-propionyloxy or ß-butyroxyethyl or -propyl, ß-methoxy or ethoxyethyl, benzyl or phenylethyl, 409886/1 181 - 29 - O.Z. 3C 015 A is hydrogen or methoxy and 2336978 A ^ hydrogen, methyl, chlorine, acetylamino, propionylamino, Mean methylsulfonylamino or methoxycarbonylamino. Process for the preparation of dyes according to Claim 1, characterized in that diazo compounds of amines of the formula III R.
t with coupling components of the formula IV HK IV
implements. 4. Dye preparations for dyeing polyamides, cellulose esters or polyesters containing, in addition to customary constituents, dyes according to claim 1 or 2. BASF Aktiengesellschaft 409886/1181