DE2136974A1 - New cationic dyes - Google Patents

Description

FATENtANW ?. L7E

DR. E. WIEGAND DIPL-ING. W, NO MAN 0 1

DR. M. KÖHLER DIPL-ING. C. GERNHARDT * 1

MÖNCHEN HAMBURG TELEPHONE: 555476 "". 8000 MD NCH EN 15, TELEGRAMS: CARPATENT N USS8 AUMSTRASSE

July 23, 1971 W. 40618/71 Ko / D

Sumitomo Chemical Company Ltd, Osaka (Japan)

New cationic dyes

The subject of the invention are compounds of the general formula

A ^ "^ * - N = N - B:

I ₂ CH ₂ COMC (CH ₃ ) ₃ S

wherein A. ^ ~~ an unsubstituted or substituted in the 4-position and / or 5-position thiazole ring or an unsubstituted or substituted in 6-position benzothiazole ring, B an anilino group of the formula

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wherein R _{1 is} a hydrogen atom, an alkyl group with 1 to 2 carbon atoms, an alkoxy group with 1 "to 2 carbon atoms, a halogen atom, a cyano group or nitro group, Rp and R, each a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy alkyl group, an acyloxyalkyl group, a haloalkyl group, a cyanoalkyl group, a carbamoylalkyl group, a cycloalkyl group, an aralkyl group or an aryl group, where the benzene ring of the aralkyl group or aryl group can have one or 2 groups corresponding to R .. as substituents, and η represents an integer 1 or 2 , or an indolyl group of the formula

wherein R. is an alkyl group with 1 to 4 carbon atoms, an aralkyl group or an aryl group, the. Benzene ring of the aralkyl group or the aryl group as a substituent an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a halogen atom, a cyano group or nitro group, and R, - a Hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxyalkyl group, an acyl oxy alkyl group, a haloalkyl group, a cyanoalkyl group or a carboxyalkyl group represent, and Z represent an anion which is used for dyeing polyacrylonitrile, polyester or polyamide fibers are valuable with high authenticity and excellent luminosity.

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Due to the. Invention result in new "basic dyes" substances of the general formula

> - N = N]

W- '

CH ₂ CH ₂ CONHC (Ch ₃ ),

(D

wherein A ^ - an unsubstituted or in the 4-position and / or 5-position substituted thiazole ring or an unsubstituted or in 6-position substituted benzothiazole ring, B is an anilino group of the general formula

where R ^ is a hydrogen atom, an alkyl group with 1 to 2 carbon atoms, an alkoxy group with 1 to 2 carbon atoms, a halogen atom, a cyano group or nitro group, Rp and R »an alkyl group with 1 to 4 carbon atoms, an alkoxyalkyl group, an acyloxyalkyl group, a haloalkyl group, a cyanoalkyl group, a Corbamoylalkylgruppe, a cycloalkyl group, an aralkyl group or an aryl group, whereby the benzene ring of the aralkyl group or aryl group can have one or 2 substituents corresponding to the group R ₁ , and η represent the numbers 1 or 2, or an indolylgmppe the general formula

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wherein R is an alkyl group having 1 "to 4 carbon atoms, an aralkyl group or an aryl group, the benzene ring in the aralkyl group or aryl group being substituted by an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a halogen atom, a cyano group or May have nitro group, and IL · represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group, an aeyloxyalkyl group, a haloalkyl group, a cyanoalkyl group or a carbamoylalkyl group and Z "represents an anion. In particular, the invention relates to blue dyes of the general formula

CH ₂ CH ₂ COIIHC (CH ₃ )

) n

(11)

in which A, R ₁ , R ₂ , R-, η and Z "have the meanings given above, as well as red dyes corresponding to the general formula

R ₄

CH ₂ CH ₂ COIiHC (CHi)

(in)

where A, R ^,
own.

and Z "have the meanings given above

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Each of the above dyes has as a specific group an N-tert-butylearbamoylethyl group as a substituent, which is why the present dyes have valuable properties "that distinguish them from the usual dyes, as indicated below. One of the properties required of a basic dye for dyeing acrylic fibers is that the dye is used as a so-called three primary color dye can be, in other words, that he is together with others different dyes can be used to achieve intermediate colors.

Fäls a dye with too high a dyeing speed is used for dyeing acrylic fibers, the There is a risk of the dyeing becoming uneven, especially when dyeing acrylic fibers in intermediate colors or light colors Colors, as coloring begins abruptly when the temperature of the coloring bath rises above a fixed temperature will.

Objects dyed uniformly in intermediate colors when using dyes with different colors be obtained at the same time, it is necessary, that each Dye has a suitable dyeing rate and the difference in staining speed between dan Dyes is not great. According to the invention, dyes with appropriate dyeing speed for this case can be obtained.

The most important feature of the dyes according to the invention is that when acidic modified polyester with a cationic dye are dyed according to the invention, products with excellent lightfastness are obtained can be.

It is known that when dyeing acrylic fibers with

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cationic dyes the dyed material can have high lightfastness and excellent luminosity, especially when the so-called conjugated type cationic dyes are used.

However, when these dyes are used for dyeing others; synthetic fibers such as polyesters are used, the dyed material has luminosity, but the lightfastness is poor. On the other hand, a relatively high light fastness * is obtained when stained with Disperöfarbstoffen \, but it can be a luminance as in the case of. Application of cationic dyes can hardly be obtained. The dyes according to the invention have a higher: lightfastness than the usual cationic dyes of the thiazolezotype and this tendency is even more pronounced when the fibers are to be dyed in light colors.

Especially when fibers light blue with the known ^!

i thiazole azotype dyes, the pale Fibers dyed therewith considerably on the sun lounger, so that the dyeing is unsatisfactory.

On the other hand, the blue dyes according to the invention are of the thiazole azo type in this point of view all superior to known dyes of the thiazole azo type. Furthermore, the dyes according to the invention show the excellent Feature that when modified polyester fibers with a mixture of the dyes according to the invention and others different Dyes are dyed at the same time, each dye has the appropriate dyeing speed for the

properties

shows simultaneous staining. This excellent / the dyes According to the invention for acid-modified polyesters, the known dyes with carbamoylethyl groups can be used els quaternary group as they are e.g. in Japanese Patent Publication 14,934 / * 62 are, in other words, this is also excellent

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Property an important characteristic of the dyes according to of the invention, which is an N-tert. -Butylcarbamoylethyl group as a quaterary group "own.

The dyes according to the invention can by reaction a monoazo compound of the general formula

= NF ( _IV )

IS

vo, rin A ^> - and B have the meanings given above

"own, and IT-tert-butylaerylamide in an inert solvent in the presence of a Broensted acid.

The group A in the thiazole ring correspondingly

"means an alkene group," for example an ethene group, Propene group, butene group, cyclohexene group, haloalkene group, Cyanoalkene group, phenylalkene group, acylalkene group and the like. As examples of a substituting group in the 6-position of the benzothiazole ring are alkyl groups with 1 to 2 carbon atoms, alkoxy groups, aryloxy groups, Halogen atoms, nitro groups, cyano groups, thiocyanate groups, Sulfamoyl groups, alkylsulfonyl groups and the like groups are listed, but of these give the alkyl groups, for example Methyl groups or xethyl groups, and the alkoxy groups, methoxy groups or ethoxy groups, for example, give the best results.

Examples of the radicals R ₂ and R »in general formula II are alkyl groups with 1 to 4 carbon atoms, alkoxyethyl groups, hydroxyethyl groups, cyanoethyl groups, chloroethyl groups, carbamoylethyl groups, acetoxyethyl groups, cyclohexyl groups, benzyl groups and phenyl groups, where

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the phenyl groups with substituents according to Ord Rj can be substituted.

As examples of the group R * of the indole derivative the general formula III are methyl groups, ethyl groups, Butyl groups, phenyl groups, p-tolyl groups, m-tolyl groups, p-anisyl groups, p-chlorophenyl groups and the like are listed. As examples of the group Rc of the general formula III be methyl groups, thy! groups, hydroxyethyl groups, Butyl groups, cyanoethyl groups, carbamoylethyl groups, methoxyethyl groups, Chlorethyl groups and the like. Listed.

The Monoazo connection according to the general Pormel IV can be made by diazotizing the aminothiazoles in conventional Manner and subsequent coupling of the compound obtained with an aniline or an indole.

As a solvent for N-alkylation in formation of the quaternary ammonium group are given as examples: Ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, Ethylene glycol, methyleellosolve, methy läthy lke clay, methyl isobutyl ketone, Chlorobenzene, dioxane, formic acid, acetic acid, and the like.

As Broensted acid, which is to be added to the solvent, preferred examples are inorganic acids such as hydrochloric acid, Hydrobromic acid and sulfuric acid and organic acids such as benzenesulfonic acid and toluenesulfonic acid.

When carrying out the present process, a mixture of the monoazo compound of formula IV and 3 to 6 moles of tert-butyl acrylamide per mole of the monoazo compound in the specified solvent is mixed with 3 moles of the Broensted acid and the mixture obtained is mixed for 5 to 15 hours at elevated temperature, preferably 80 to 100 ⁰ C, stirred.

The reaction mixture may be post-treated in the usual ise W _G, so that the present dyes of the formula I are obtained.

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The anion corresponding to group Z "* is an anion which is derived from an inorganic or organic strong acid, examples of such anions are halogen ions, such as chlorine ions and bromine ions, sulfate ions, Bisulfate ions, p-toluenesulfate ions, benzenesulfate ions and the like

Furthermore, anions derived from a complex salt with zinc chloride and the like can also be used will.

The dyes according to the invention obtained in the above manner thus have various ones Advantages and are very valuable. The dyes according to the invention can be applied to acid-modified polyamide fibers and Polyacrylonitrile fibers and polyester fibers are used.

The following examples serve to further illustrate the invention; Parts are by weight.

example 1

A mixture of 32.5 parts of the monoazo compound of formula

50.8 parts of F-Uert.-butylacrylamide, .120 parts of isopropyl alcohol, 20 parts of glacial acetic acid and 20 parts of concentrated sulfuric acid was heated to 80 to 85 ⁰ C for 6 hours under stirring.

After the completion of the reaction, most of the solvent was recovered under reduced pressure, then that

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share
The residue was dissolved in 1000 / water and, after the undissolved material had been filtered off, 150 parts of sodium chloride were added to the solution to precipitate the dye seed. The dye salt was filtered off and dried, giving a dye of the formula which was readily soluble in water

^{lI =:} w

When polyacrylonitrile fibers with a weakly acidic bath of the dye thus prepared were dyed, the fibers became uniformly blue with high heat resistance and high lightfastness colored.

Example 2

A mixture of 37.9 parts of a monoazo compound the formula

\ _{/ Γ} ~ _Χ

V-H = N- / V-H

50.8 parts of li-tert-butyl acrylamide, 100 parts of dioxane and

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20 parts of concentrated sulfuric acid were ^{heated to 80 to 85 °} C. for 4 hours with stirring. After the reaction had ended, most of the solvent was recovered under reduced pressure and the residue was dissolved in 1000 parts of water. After filtration and undissolved material, 150 parts of sodium chloride was added to the pil step to precipitate the dye salt.

The dye salt was filtered off and dried, and an inventive salt was readily soluble in water Dye received. When polyacrylonitrile fibers from a weakly acidic bath were dyed with the dye, the fibers were stained uniformly blue and showed high Heat resistance and lightfastness.

Example 3

A mixture of 47.7 parts of the monoazo compound of the formula

N ^

CH2CHCH2OC4H9 OH

50.8 parts of IT-tert ^ butyl acrylamide, 60 parts of methyl ethyl ketone and 20 parts of concentrated hydrochloric acid were ^{heated to 75 to 80 °} C. for 5 hours with stirring. When the reaction was complete, most of the solvent was recovered under reduced pressure, the residue was dissolved in 1,000 parts of water and, after undissolved matter had been filtered off, 20 parts of zinc chloride and 150 parts of sodium chloride were added to precipitate the dye salt.

The dyestuff salt was filtered off and dried and a dyestuff which was readily soluble in water was obtained. If poly-

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acrylonitrile fibers from a weakly acidic bath of the dye were dyed, the pasers were dyed uniformly blue with high heat resistance and light fastness.

Example 4

A mixture of 89.9 parts of the monoazo compound of formula

CH ₂ CH ₂ OCH ₃

50.8 parts of N-tert-butyl acrylamide, 60 parts of monochlorobenzene and 20 parts of glacial acetic acid were mixed with 17.2 parts of p-toluenesulfonic acid and the resulting mixture was ^{heated to 90 °} C. for 5 hours with stirring. After the completion of the reaction, most of the solvent was recovered under reduced pressure, and after undissolved matter was filtered off, 150 parts of sodium chloride was added to the filtrate to precipitate the paraffin salt.

The product was filtered off and dried, and a paraffin which was readily soluble in water was obtained.

When polyacrylonitrile acidic from a weakly acidic Bath of the dye were dyed, the pasers became a uniform blue with high heat resistance and lightfastness colored.

Example 5

Approx. 25.6 parts of a compound of the formula were used in 200 parts of glacial acetic acid

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lind was dissolved 50.4 parts of N-tert-butylacrylamide, and after adding 10 parts of concentrated sulfuric acid to the solution under vigorous stirring the resulting mixture for 3 hours at 90 "heated to 95 ⁰ G. Nach'dem the" reaction is complete , acetic acid was distilled off under reduced pressure and the residue was dissolved in 500 parts of warm water, and after the solution was treated with activated charcoal, 50 parts of sodium chloride was added to the solution and the dye represented by the following formula

CH ₂ CH ₂ COIiHC (CH ₃ ) 3

he

salted out in the form of crystals. The dye obtained in this way also dyed polyacrylonitrile fibers yellowish excellent fastness to cleaning, light and heat.

Example 6

In a mixture of 100 parts of glacial acetic acid and 100 parts of 85% formic acid, 31.8 parts of a compound were obtained the formula

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Οι

CH,

50.4 parts of N-tert-butyl acrylamide were dissolved and the mixture was reacted at ^{95 ° C. for 2 hours.} After formic acid and acetic acid were distilled off under reduced bridging, the residue was dissolved in 700 parts of warm water and 70 parts of sodium chloride was added to the solution to precipitate the dye salt, which was filtered off. With the dye obtained, polyacrylonitrile fibers could be dyed red with excellent fastness to light, cleaning and heat.

Example 7

To 300 parts of monochlorobenzene there were 36.8 parts of a compound of the formula

and 50.4 parts of N-tert-Butylaerylamid added and, after further addition of 10 parts of concentrated sulfuric acid, the mixture for one hour at 95 was converted to 100 ⁰ C. After the monochlorobenzene was recovered under reduced pressure, 500 parts of warm water was added to the residue, and then 50 parts of sodium chloride was added to the solution to precipitate the dye salt, which was filtered off. With the dye obtained in this way, polyacrylonitrile fibers could be uniformly bluish

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can be colored red with excellent fastness to light, cleaning and heat.

Example 8

In 5000 parts of warm water there was 1.0 part of the dye the formula

■ + ·

^ ^ ^ N = IT-f V-N ^

⁵ 2 ^H 5

solved. Kach setting of the staining bath obtained by adding one part of acetic acid and 0.5 parts of sodium acetate and then heating the bath at 60 ⁰ C, 50 parts Cashimilon F were immersed (name of a product Asahi Kasei KK) in the bath and the bath to boiling by Heated for 40 to 50 minutes and kept in the boiling state for 1 hour to dye the article. The dyed article was washed with water and dried, and a dyed article having a uniformly clear blue color and excellent in fastness to light, heat and cleaning was obtained.

Example 9

In 5000 parts of warm water there was 1.0 part of the dye of the formula

S HcC ₂ Q _n "- ^C ? ^Hc i Vi *

Cl

r ■.

CH ₂ CH ₂ COUHC (Ch ₃ ) ₃
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dissolved and after setting the dye bath by adding 1.0 part of acetic acid and 0.5 part of sodium acetate 50 parts of Vonnel V (name of a product of the Mitsubishi Easei K.K.) immersed in the bath. The bath was then heated to a boil after 50 to 60 minutes and kept in the boiling state until the immersion dyeing is complete. After washing and drying, the item was uniformly clear green-blue colored with excellent fastness to light, heat and cleaning.

By repeating similar procedures as above, the valuable dyes indicated below were obtained and using these dyes, excellently colored articles were obtained in the same manner:

Structure color of the stained

Polyacrylonitrile

C ₂ H ₅
'CH ₂ - ^^ ^C1 ~ ⁵¹⁸ U

^ c H " ^blue

CH ₂ CH ₂ CONHC (Ch) '"

Green Blue

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CH ₃

CH ₃

¹ p

-.θ

blue

II

—Ο ¹ Cl ^.

Green Blue

H ₃ CO

S:

-.- Ο ¹ -

CH ₂ CH ₂ COHHC (CH ₃ ) 3 , CH ₃ CH ₂

Green Blue

CH ₂ CH ₂ CONHC (CH ₃ ) ₃

C ₂ H ₅

Cl '

-C ₂ H ₄ Cl blue

: p ₂ N

'CH ₂ Ch ₂ COIIHC (CH ₃ ). CH.

Rof blue

.COlIHC (CH).

_C1 0 Rof blue

CH

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CHgGH ₂ CONHC (CH ₃ )

Green Blue

N _β

'CHgCHgCOIlHC (CH ₃ ) C ₄ H ₉

n = ν- / V- ^N ^ - -

CHgCH ₂ COIiHC (CH) ₃

blue

CHgQHgCOIiHC (CH ₃ )

^{Red Blue}

H =

² » ^C1

V- N = N - / Υ— N ^

CH CH COHHC (CH)

VS Ci- CHgCHgCH

Green Blue

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2136374

CH CH COlIHC (CH)

Cl '

Blue red

Cl

Hot

CH

Cl "

Blue red

CHgCHgCOIiHC (CH ₃ )

3'3 blue red

-H

Cl

Blue red

~ 20 -

Cl "

lot

= ir

ft ca *

lot

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Claims (11)

Patent claim 1. Compounds according to the formula N = N-B CH ₀ CH ₀ COIiHC (CH ₀ ), ² - ^d _ .3-3- / S.
where A. J ^> - an unsubstituted or in 4- and / or 5-position substituted thiazole ring or one unsubstituted or a benzothiazole ring substituted in the 6-position, B an anilino group of the formula ir. wherein R _{1 is} a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a halogen atom, a cyano group or nitro group, R ₂ and R ^ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group, an acyloxyalkyl group , a haloalkyl group, a cyanoalkyl group, a carbamoylalkyl group, a cycloalkyl group, an aralkyl group. or an aryl group, where the benzene ring of the aralkyl group or the aryl group can have 1 or 2 groups R ₁ as substituents, and η represents the integer "1 or, or a Indolyl group of the formula 109886/1686 wherein R. is an alkyl group having 1 to 4 carbon atoms, an aralkyl group or an aryl group, the benzene ring of the aralkyl group or the aryl group being substituted by an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a halogen atom, a cyano group or a nitro group, and Rc represents a hydrogen atom, an alkyl group having 1 to A carbon atoms, an alkoxyalkyl group, an acyloxyalkyl group, a haloalkyl group, a cyanoalkyl group or a carboxyalkyl group, and Z "represents an anion. 2. Compound according to the formula 3. Compound according to the formula CH CE CONHC (CH). 4. Compound according to the formula 5. Compound according to the formula 'H co. - ^} [N ^ y \ CH CH OCII J CH ₂ CH ₂ COiJHC (CH) 109886/1686 - 23 6. Compound according to the formula XA, CH ₁ -CWCOIIHC (Ck,) 7. Connection according to the formula Cl " k / "CH ₃ > . v _U nnmiiTf-πτΓ V 8 «Compound according to the formula CI. " CH; L) _: 9 Process of manufacture; of remnants of the general formula where A- an unsupported or in 4-position and / or 5-position substituted thiazole ring or one unsubstituted or 6-substituted benzathia sol ring and B is an anilino group of the general formula 109886/1686 213697A -24- where R ^ is a hydrogen atom, an alkyl group with 1 and 2 carbon atoms *, an alkoxy group with 1 to 2 carbon atoms, a halogen atom »a cyano group or nitro group, R« ^and ^ ^ x ^e * - ⁿ hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group, an aeyloxyalkyl group, a haloalkyl group, a cyanoalkyl group, a carbamoylalkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, the benzene ring of the aralkyl group or the aryl group having one or 2 groups R ₁ as substituents. possess.kann, and η represents the integer 1 or 2, or an indolyl group of the formula where R ^ is an alkyl group with 1 to 4 carbon atoms, an aralkyl group or an aryl group with the benzene ring of the aralkyl group or the aryl group as a substituent an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a halogen atom, a May have cyano group or a nitro group, and R, - a Hydrogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxyalkyl group, an acyloxyalkyl group, a haloalkyl group, a cyanoalkyl group or a Represent a carboxyalkyl group, and Z "denotes an anion, characterized in that a monoazo compound of general formula 10 9 8 8 6/1686 wherein A ^ 7J >> - and B have the meanings given above ■ have, and N-tert-butyl acrylamide are reacted in an inert solvent in the presence of a Broensted acid. 10. A method for dyeing acid-modified polyacrylonitrile, polyester or polyamide fibers, characterized in that a compound according to claim 1 to 8 is used. 11. Acid-modified polyacrylonitrile, polyester or polyamide fibers, dyed with a compound according to Claims 1 to 8. 109886/1688