CA1071191A

CA1071191A - Azo dyestuffs

Info

Publication number: CA1071191A
Application number: CA259,287A
Authority: CA
Inventors: Brian Parton
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Imperial Chemical Industries Ltd
Priority date: 1975-08-26
Filing date: 1976-08-17
Publication date: 1980-02-05
Also published as: CH602883A5; AU1641476A; FR2322178B1; BR7605522A; TR19733A; JPS5227432A; ES451000A1; AR210149A1; IT1119703B; NL7609157A; DE2638051A1; FR2322178A1

Abstract

ABSTRACT OF THE DISCLOSURE
Azo dyestuffs devoid of carboxylic acid and sulphonic acid groups and of the formula (I)

Description

Dd.28160/28345 ' I
!

!

., . I
7~9~. ~

.
. .
This invention relate6 to new water-soluble azo Ij dye6tuffR, to their manufacture and to the use of such dyestuffs for the colouration of synthetic polymeric materials in the form of ribbons, tape6, fibres, films, threads and textile materials generally. The dyestuffs are particularly valuable for the colouration of polymers and copoly~ers of acrylonitrile and of dicyanoethylene and also acid-modified polyesters and polyamides.
Accordin~ to the present invention there are provided azo dye6tuffs devoid of carboxylic acid and '!
sulphonic acid groups and of the formula (I) s ., ,

- 2 - l ,~

~d.28160/2834~
~, , cooR2 R .

~J = N--~ X(3 (I) Rl I

whereln R is a hydrogen atom, halogen atom, cyano, nitro, hydroxy or amino group or an organic radical, . R1 is a hydroeen atom, an optionally substituted hydrocarbon or heterocyclic radical or an amino group which may be substituted, R i8 an optionally substituted alkyl group with three or more carbon .
atoms, an optionally substituted aryl group or an aralkyl group~ K+ i8 a cationic group, X an anion and the rinB A may carry additional substituents or have a benz ring fused thereon.
The azo dyestuffs of the invention can exist in a number of tautomeric forms; for convenience the dyestuffs have only been formulated in one of these tautomeric forms, but it is to be understood that this invention includes within its scope the dyestuffs in any of the possible tautomeric forms.

~ ':

.. . .

107~191 Where the term lower alkyl is used in this specifica-tion it means alkyl containing from one to four carbon atoms.
R may be a hydrogen atom, halogen atom, cyano, nitro, hydroxy or amino group or an organic radical~ examples of such organic radicals including optionally substituted alkyl, aryl, aralkyl, cycloalkyl and heterocyclic radlcals, carboxylic acid ester and carboxylic acid amide, substituted amino and hydro-carbyloxy groups.
Specific examples of R include methyl, ethyl, n-propyl, n-butyl, ~-hydroxyethyl,~-methoxy (or ethoxy)-ethyl, ~cyanoethyl~
carbethoxymethyl, acetylmethyl, phenyl, chlorophenyl, methoxy-phenyl, benzyl, phenylethyl, cyclohexyl, 2-pyridyl, 2-thiazolyl, l-piperidyl, 2-morpholinyl, methoxycarbonyl, ethoxycarbonyl, carbamyl, N,N'-dimethylcarbamyl, N,N'-diethylcarbonamido, chloro, cyano, nitro, amino, hydroxy, bromo, methoxy, ethoxy, diethyl-amino, N-methylbenzylamino, N-methylanilino, anilino, methoxy-carbonylmethyl, methylsulphonylmethyl, anilinocarbonylmethyl, cyanomethyl, N,N-dimethylaminocarbonylmethyl, N-nonylcarbamyl, nonyloxycarbonyl, N-phenylcarbamyl, N-benzylcarbamyl, N,N-di-benzylcarbamyl, 2-furyl, 2-thienyl, 2-pyrryl and phenoxymethyl.
` R is preferably lower alkyl of one to four carbon atoms, especially methyl.
Rl may be a hydrogen atom, an optionally substituted hydrocarbon or heterocyclic radical or an amino group which may be substituted.
Specific examples of Rl include methyl, ethyl, n-propyl, n-butyl, amino, ~-hydroxyethyl, ~-methoxy (or ethoxy)-` ethyl, ~-cyanoethyl, carbethoxymethyl, ~-methoxypropyl, acetyl-methyl, phenyl, tolyl, chlorophenyl, methoxyphenyl, benzyl, 107~19~

phenylethyl, cyclohexyl, 2-pyridyl, 2-thiazolyl, l-piperidyl, l-morpholinyl, dimethylamino, 2-ethylhexyl, nonyl, dodecyl, p-butylphenyl and _-dodecyl-phenyl.
Rl is preferably hydrogen or lower alkyl.
R2 may be an optionally substituted alkyl group with three or more carbon atoms, an optionally substituted aryl group or an aralkyl group. When R is an alkyl group it may be straight chain or branched.
Specific examples of R2 include n~propyl, iso-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl, n-dodecyl, tert-butyl, lso-butyl, sec-butyl, iso-pentyl, 2-methylbutan-l-yl, neo-pentyl, pentan-2-yl, pentan-3-yl, 3-methylbutan-2-yl, tert-pentyl, _-heptyl, n-nonyl, _-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n~hexadecyl, n-hepta-decyl, octadecyl, phenyl, o, m or ~-tolyl, benzyl, phenylethyl, p-tert-butyl phenyl, p-nonyl phenyl, p-n-pentyl and 3,5,5-trimethylhexyl.
R may also be derived from a mixture of isomericalcohols or a mixture of alcohols of different chain lengths, in particular it may be derived rom commercial mixtures of long chain alcohols.
It is preferred that R2 be an alkyl group of five or more carbon atoms especially an alkyl group of six to twelve carbon atoms.
The group -COOR2 may be in the ortho, meta or para position with respect to the azo group but is preferably in the ortho position, i.e. the preferred dyestuffs have a diazo component which is an anthranilate.

As examples of cationic groups which are represented by K are included quaternary ammonium, cyclammonium, hydrazinium, sulphonium, isothiouronium, etherified hydroxylammonium and phosphonium groups which may be associated with any anion X .
As quaternary ammonium groups are meant groups of the formula ~ 3 wherein R , R and R represent optionally substituted alkyl or cycloalkyl groups or one may be a phenyl group or wherein R4 and R5 taken together with the nitrogen atom form a 5 or 6 membered ring.

As optionally substituted alkyl groups R , R
and R5 there may be mentioned methyl, ethyl, benzyl, cyclohexyl, ~-hydroxyethyl.

1(~711~31 As 5 or 6 membered rings which may be formed from R4 and R5 together with the nitrogen atom there may be mentioned piperidine and morpholine (as in piperidinium and morpholinium salts), in this case the group R3 is optionally substituted alkyl or cycloalkyl.
These latter can also be described as cyclammonium groups.
As,cyclammonium groups there are meant heterocyclic systems containing in the ring a quaternised nitrogen atom ; which is preferably the point of attachment of the ring to the remainder of the molecule, for example N-methylpiperidinium and N-methylmorpholinium, but more particularly aromatic heterocyclic quaternary systems such as pyridinium, ~-picolinium, 8-picolinium, y-picolinium, quinolinium, iso-quinolinium, and including heterocyclic systems containing heteroatoms additional to the quaternised nitrogen atom and substituted derivatives of the foregoing.
As sulphonium groups there are meant groups of the formula R6 _~ /
\ 7 wherein R6 stands for an alkyl or substituted alkyl radical such as methyl or ethyl, R7 stands for an alkyl or substituted alkyl radical such as methyl, ethyl, and -hydroxy-ethyl, a cycloalkyl radical such as cyclohexyl, an aralkyl radical such as benzyl and an aryl radical such as phenyl and p-tolyl.
As isothiouronium groups there are meant groups which in one of their resonating forms may be represented by the formula ,~R8R9 --S=C
\NRl ORl 1 wherein R8, R9, R10 and Rll represent hydrogen atoms or hydro-carbon or substituted hydrocarbon radicals or R8 and R10 may together form an alkylene radical.
As examples of hydrocarbon and substituted hydro-carbon radicals which may be represented by R8, R9, R10 and Rll there may be mentioned alkyl radicals such as methyl and ethyl, substituted alkyl radicals such as ~-hydroxyethyl, cycloalkyl radicals such as cyclohexyl, aralkyl radicals such as benzyl and aryl radicals such as phenyl and p-toly As an example of an alkylene radical which may be formed by R8 and R10 together there may be mentioned ethylene. In this case an imidazoline ring is formed.
As hydrazinium groups there are meant groups of the formula ~12R13-NR14 R15 wherein R12 represents an optionally substituted alkyl, cycloalkyl, aralkyl or phenyl radical or together with R13 and the adjacent nitrogen atom a heterocyclic system.
R13 represents an optionally substituted alky~, cycloalkyl, aralkyl or phenyl radical or together with R12 and the adjacent nitrogen atom a heterocyclic system.

:
.
.

R14 represents a hydrogen atom or an optionally substituted alkyl radical or an acyl radical which may form a ring with R15 and N or when R12 and R13 are other than phenyl, a phenyl radical t R15 represents a hydrogen atom or an optionally substituted alkyl radical or an acyl radical.
As phosphonium groups there are meant groups of the formula --i~; Rl 7 ~R18 wherein R , R and R 8 are organic radicals, which may be the same or different, each having a carbon atom linked directly . .
to the phosphorus atom. As examples of organic radicals which may be represented by R16, R 7 and R18 there may be mentioned aliphatic radicals, for example methyl, ethyl, propyl, butyl, alkyl, chloromethyl, hydroxymethyl and ~-hydroxymethyl, aro-matic radicals, for example, phenyl, naphthyl, p-tolyl, ~-chloro-phenyl, aralkyl(ra.dicals, for example benzyl and heterocyclic radicals, for example -2-thienyl.
Preferably the cationic group K~ is a cyclammonium group.
The anion X may be any anion of an inorganic or organic acid capable of forming a salt with a quaternary nitro-gen cation.
Examples of the anion X include inorganic anions such as chloride, bromide, iodide, tetrachlorozincate, bisul-phate, nitrate, sulphate, sulphamate, phosphate, borate, tetrafluoroborate, - ' .

Dd.2816Q/28345 - ~

~071191 i perchlorate, phosphomolybdate and organic ions such as acetate, propionate, oxalate, moleate, lactate, succinate, chloroacetate, benzoate, methyl sulphate, p^tolyl sulphonate and methane 6ulphonate. In the cases where the anion i8 polyvalent the , dyestuff will contain a corresponding molar proportion of the cationic part of the dyestuff.
The ring A may carry additional substituents or ha~e a benz ring fused thereon.
Examples of additional substituents which may be present in the ring A include halogen atoms for example chloro, bromo and fluoro, alkoxy for example methoxy and ethoxy, alkyl for example methyl, acylamino for example acetylamino, alkoxycarbonyl for example methoxycarbo~yl or an alkoxycarbonyl group -COOR where R iB as hereinbefore defined, nitro, acyloxy for example acetoxy, aryloxy for example phenoxy, carbamyl for example diethylamino-carbonyl, amino for example methylamino, alkylsulphonyl~ phenoxy sulphonyl, trifluoromethyl~ alkoxycarbonylamino~ dialkylam$nosulphamyl, monoalkylaminosulphamyl, sulphamyl, acyl for example acetyl, cyano, arylazo~ aryl for example phenyl, substituted aryl for example 4-[2~-hydroxy-3-pyridinium-4'-methylpyrid-6'-one-5'-ylazo]-3-alkoxy-carbonylphenyl.
If additional substituents are present in the ring A it is preferred that such sub6tituents be a methyl or methoxy group, a chlorine atom or an alkoxycarbonyl group of the formula -COOR2, _ 10-, ~

: . :

' ' '~ ~ ' , ' ~

Dd.28160/28345 1(~71~9i A benz ring may be fused on to the ring A in the positions 2, 3; 3,4; 4,5; or 5,6 in relation to the azo group as 1 but the position of any such benz ring will be dependent on the positi.on.
of the group -COOR2.
One preferred class of dyestuff is that of the formula:

N = ~ X
o 7 OH

3 4 wherein R i~ a lower alkyl group~ R is hydrogen or a lower alkyl group, R5 is an alkyl group of more than 5 carbon atoms, K1 ~3 is a cyclammonium group and A ~ is an anion.
10Particularly preferred members of this class are those wherein R3 is methyl, R4 i8 hydrogen, R5 is alkyl .
of from six to twelve carbon atoms and K1 ~ is pyridinium or an ~ j ~- or r-picolinium group, especially when the group -CooR5 is ortho to the azo group.
' ~
.
i .' , . ~
- 11 _ .~
., : : ` ' ~ . -: ~ . :
': : : ' ~ :. :
., : :
, 10711~1 As a further feature of the present invention there is provided a process for the manufacture of the dyestuffs of the inventlon which comprises diaxotising an aromatic amine of the formula COOR

~NH2 wherein A and R are as hereinbefore defined and coupling the diazonium salt with a pyridone of the formula ~ I ~ H
Rl wherein R, Rl and K are as hereinbefore defined.
The diazotisation and coupling steps of the process may be carried out in conventional manner, for example by mixing a solution of the diazotised amine, obtained in known manner, with an aqueous solution of the coupling component.
Examples of aromatic amines which may be used as the diazo component include n-butyl anthranilate sec-butyl anthranilate n-hexyl anthranilate iso-pentyl anthranilate n-octyl anthranilate 2-methyl-butane-1-yl anthranilate n-decyl anthranilate neo-pentyl anthranilate n-dodecylanthranilate pentan-2-yl anthranilate tert-butyl anthranilate pentan-3-yl anthranilate p-nonylphenyl anthranilate 3-methyl-butan-2-yl anthranilate iso-butyl anthranilate tert-pentyl anthranilate ~ - :

n-heptyl anthranilate _-heptadecyl anthranilate _-nonyl anthranilate octadecyl anthranilate n-undecyl anthranilate phenyl anthranilate n-tridecyl anthranilate benzyl anthranilate n-pentadecyl anthranilate p-tert-butylphenyl anthranilate n-hexadecyl anthranilate p-n-pentylphenyl anthranilate 2,5-bis-hexyloxycarbonyl- 2-nonyloxycarbonyl-5-chloro-aniline aniline 2-hexyloxycarbonyl-4-nitro- 2-dodecyloxycarbonyl-4-diethyl-aniline aminoaniline 2-nonyloxycarbonyl-4-methoxy- 2-dodecyloxycarbonyl-4-acetoxy-aniline aniline 2-propyloxycarbonyl-4-phenyl- 2-propyloxycarbonyl-4-phenylazo-ani.line aniline m-aminopropyl benzoate m-aminobutyl benzoate m-aminoamyl benzoate m-aminohexyl benzoate m-amino-octyl benzoate m-aminononyl benzoate m-aminododecyl benzoate ~-aminohexyl benzoate p-aminononyl benzoate ~-aminododecyl benzoate p-aminophenyl benzoate m-aminobenzyl benzoate m-aminophenyl benzoate _-aminobenzyl benzoate 3,5,5-trimethylhexylanthranilate .

. - 13 - :

Examples of pyridone coupling components which may be used include:
2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydro-pyridine, 1,2'-4-trimethyl-2-keto-3-pyridinium chloride-6-hydroxy-1,2-dihydropyridine, 1-(3"-methoxy)-n-propyl-2-keto-3-(2'-chloro)-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, l-n-butyl-2-keto-3-t4'-ethyl)-pyridinium chloride-4-methyl-6-10hydroxy-1,2-pyridine, 1-(2"-ethyl)-hexyl-2-keto-3-(3'-cyano)-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, 1-(2"-hydroxy)-ethyl-2-keto-3-(2'-methoxy)-pyridinium chloride-

4-methyl-6-hydroxy-1,2-dihydropyridine, 1-(2"-N"'-methylpiperazinyl)-ethyl-2-keto-3-(2'-methyl)-pyridinium chloride-4-ethoxycarbonyl-6-hydroxy-1,2-dihydropyridine, 1-(2"-hydroxyethylamino)-ethyl-2-keto-3-(3'-methyl)-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, 1-(2"-ethyl)hexyl-2-keto-3-quinolinium chloride-4-methyl-6-20hydroxy-1,2-pyridine, 107~

l-methyl-2-keto-3-isoquinolinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, l-phenyl-2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, 1-(2"-chloro)-phenyl-2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, 1-(3"-methyl)-phenyl-2-keto-3(2'-methyl)-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, l-dime`thylamino-2-keto-3-pyridinium chloride-4-methyl-6 hydroxy-1,2-dihydropyridine, l-amino-2-keLo-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, l-pyrrolidinyl-2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, l-(N-methyl)-piperazinyl-2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, l-morpholinyl-2-keto-3-pyrldinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, 1-(4'-dimethylamino)-phenyl-2-keto-3(2"-methyl)-pyridinium chloride- methyl-6-hydroxy-1,2-dihydropyridine, l-amino-2-keto-3-pyridinium chloride-4-ethoxycarbonyl-6-hydroxy-1,2-dihydropyridine, l-dimethylamino-2-keto-3-pyridinium chloride-4-phenyl-6-- hydroxy-1,2-dihydropyridine, 1-(3'-dibutylamino)-n-propyl-2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, .. ~

1-~2'-diethylamino)ethyl-2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, 1-(2'-hydroxyethylamino)-ethyl-2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, 1-[2'-(2"-hydroxyethoxy)-ethylamino]-2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridone, 1-(2'-morpholinyl)-ethyl-2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, 1-(2'-N-methylpiperazinyl)-ethyl-2-keto-3-pyridinium chloride-104-methyl-6-hydroxy-1,2-dihydropyridine, 2-keto-3-pyridinium chloride-4-ethoxycarbonyl-6-hydroxy-1,2-dihydropyridine, 2-keto-3-pyridinium chloride-4-N",N"-dimethylcarbamoyl-6-hydroxy-1,2-dihydropyridine, 2-keto-3-pyridinium chloride-4-phenyl-6-hydroxy-1,2-dihydro-pyridine, l-ethyl-2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2 dihydropyridine, l-methyl-2-keto-3-trimethylammonium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, 0 2-keto-3-dimethylbenzylammonium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, l-ethyl-2-keto-3-[N-methyl-l-piperidinium chloride]-4-methyl-6-hydroxy-1,2-dihydropyridine, 2-keto-3-lN-methyl-l'-pyrrolidinium chloride]-4-methyl-6-hydroxy-1,2-dihydropyridine, 2-keto-3-[N-methyl-l'-morpholinium chloride]-4-methyl-6-hydroxy-1,2-dihydropyridine, 2-keto-3-dimethylsulphonium chloride-4-ethyl-6-hydroxy-1,2-dihydropyridine, 302-keto-3-dimethylhydrazinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine, 2-keto-3-trimethylphosphonium chloride-4-ethyl-5-hydroxy-1,2-dihydropyridine.

Dd.28160/28~45 ~071~91 There may also be used pyridDn~ compounds similar to those listed above but wherein the cationic group i8 an a~ or y-picolinium group.
An anion present in a dyestuff of the invention may be replaced by known methods, for example, by metathesi6.
An alternative method of producing the dyestuff6 of the invention ifi by diazotising an amine of formula:

~ NH2 and coupling the diazo compound with an acylacetic ester, for example, ethyl acetoacetate by a known method and then reacting the product with a salt of an acetic acid amide containing a cationic group in the presence of a catalyst and a solvent such as methanol, The dye6tuffs of the invention are valuable for the colouration of synthetic polymeric materi~l6 by application from an aqueous bath. The dyestuffs have a rapid rate of dyeing and may therefore be advantageously used in admixture with known commercial dyestuff6. The present dye6tuffs give valuable bright shade6 of high tinctorial strength.
In particular the dye6tuff6 of the invention are valuable for colourin~ polyacrylonitrile material6 or blend6 thereof and may ' ' .

Dd.28160/28345 be applied thereto from acid, neutral or slightly alkaline dyebaths (ire~ pH from 3 - 8) at temperatures between, for example, 40~C and 120C, preferably between 800C and 120C or by printing techniques using thickened printing pa6tes. Bright yellow to orange dyeings of excellent fastness properties to washing, perspiration, steam-pleating and light are obtained, The dyestuffs of the invention have an advantage in that they have compatibil1ty value~ in the range 2~5 to 3.5, i.e.
about 3 as assessed by the method for the determination of compatibility values described in the Journal of the Society of Dyers and Colourists, Volume 87, No.2, page 60 (1971).
Compatibility is asse6sed on a scale of 1 to 5 and dyers engaged in the dyeing of polyacrylonitrile materials show a strong preference for dyestuffs having a compatibility value or C.V.
i ` 15 value as it i8 known, of 2.5 to 3.5. Additionally, dyestuffs of C.V. 2.5 to 3.5 are compatible in dyeing properties with the large majority of mainstream commercial dye~ used in the dyeing of polyacrylonitrile.
The dyestuffs of this invention also have the valuable advantage that they provide bright yellow shades which, even in pale shade6, have excellent light fastness.
Commercial yellow dyestuffs such as Basic Yellow 13 (Colour Index) possess the disadvantage that they are unstable in aqueous solution and decompose with loss of colour during the dyeing process or on storage in aqueous solution. The dyestuffs of the present invention are not sub~ect to this disadvantage.

., ' ' :'' ': ', . ' ~'' ' Dd.28160/28345 !

107119i ~j .' . i The dyestuffs of the invention may also be applied by a wet transfer printing process in which a support 6uch a6 paper is printed wlth an i ink containing a dyestuff, the printed support is placed in contact with a textile material and the `
whole then 6ubjected to heat and pre6sure under 11 humid~wet conditions.
The invention i6 illustrated by the following examples in which all parts and percentages ,~
are by weight except where otherwise indicated.
i, Example 1 4.22 Parts of n-hexyl anthranilate in ¦
25 parts of 2N hydrochloric acid is stirred at 0-5C and 10.4 parts of 2N sodium nitrite added dropwise over 15 minutes. After stirring at 0-5C
for 15 minutes, exces6 nitrous acid is removed by the addition of a little 20% sulphamic acid solution.
A solution of 4.8 parts of 2-keto-3-pyridinium ~ -chloride-4-methyl-6-hydroxy-1,2-dihydropyridino in 100 parts of water is stirred at 0-5C and the above ,~ .

19 - ~
i7 107~19~
diazo solution is then added over 5 minutes. After stirring for 1 hour at 0-5C the bright yellow solid is filtered off, washed with 10% brine then dried at 60C to yield 10.6 parts of a yellow powder which dyes polyacrylonitrile and acrylonitrile co-polymer in greenish-yellow shades of outstanding light-fastness and wash-fastness and has the structure (I) ~_OnC6H13~N13 Ci ~) (I) O H OH
Further greenish-yellow dyestuffs can be obtained by similar methods and are described in the following table. The first column shows the diazo component corresponding to D, the second column the substituent Rl and the third column the sub-stituent -K+. The anion is shown in the final column.
Where not indicated otherwise the alkyl group of the ester group in the diazo component is normal, i.e. straight chain.

D - N = N ~ K +
~ N ~

Rl .

107~'191 Example Diazo component No. corresponding to r A

~ 2 ~ COOC8Hl7 H ~ ~ Cl ; 3 ~1 ll -~N ~ - CH3 ~H3S04-4 u CH3 n Cl 6 ll CH2-CH-CH2CH2CH2CH3 ~ ~ SO =

. CH3 _ ; 7 ~ NH2 n n N03 . 8 ll H 1~ ~H3S04-9 .l CH3 - ~ CH3 C

0 ~ C12H25 H CH3 Cl 11 2H5 +N ~ CH3 Cl Dd.28160/28345 ~07~9~ i Example 12

5.0 Parts of 4-aminononyl benzoate iB dissolved in 20 part6 of glacial acetic acid and 5 parts of , concentrated hydrochloric acid. 10 Parts of 2N sodium nitrite are then added whilst maintaining the temperature at 0-5C and the mixture is then stirred at 0-5C for i ;~ hour. Exces6 of nitrous acid is removed by the addition of a few drops of 20% sulphamic acid solution.
A solution of 4.58 parts of 2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-dihydropyridine in 150 parts of water i8 ~tirred at 0-5C and the above diazo 601ution is then -added over 10 minutes. After stirring for 1 hour at room temperature, salt i8 added to 15% weight/volume then the mixturé i6 stirred for 15 minutes. The bright yellow solid is filtered off and washed with 50 parts of 10% brine then dried at 60C to yield a reddish-yellow powder which dyes polyacrylonitrile and acrylonitrile copolymer in greenish-yellow 6hades of outstanding light fastness and wash fastness and has the structure (I):

C913190C~N = N~ Cl H

(I) ~
- 2Z - ~j ..
~. .
' ' " " ~ . , .' :, ' .~ . , i Dd.28160/28~45 107~9~ ~;
;' , .
The 4-aminononyl benzoate used in this Example wa~
made by reaction of isatoic anhydride with 3,5~5-trimethyl-hexan-1-ol, the nonyl group having the formula:

Similar dyestuffs may be prepared by replacing the 4-aminononyl benzoate by equivalent amounts of the 6traight chain or branched chain hexyl or dodecyl esters of p-amino-benzoic acid.
Further dyestuffs can be obtained by methods similar to those described in the previous Examples and are shown in Table II. The first column shows the diazo component corresponding to D~ the ~econd column shows the substituent R1~ the third column shows the substituent K ~ and the final column the shade imparted by the dyestuff to polyacrylonitrile fibres. The anion is shown in the fourth column.
Where the alkyl group of the ester in the diazo component is not shown as branched it is the normal, iOe. straight chain aIkyl group.
.

' :

. .

Dd . 28160/28345 107119~ ~
~ .

(3 ~ (9 11 3~

C~ b~ a~ c~
~,, .`.
~.-.
. ~

- 24 - i .

:' : ' -:' - ' ~ . . : .- :
.

Dd.281~/28~l.5 10~1191 11 __ o~ I ~

~ ~ _ _ _ ~;
_ _ __ .

~; = _ ~
. : - .

O ~-- DN ~

''~C~N . .
~"~ mON ~ : ~

_ _ ~ ~ ~ . ~ N N N ~i ~a.~o ~ s~

. _ OF~ i~ 3 o 0 p, ,~
u~ ~ . I
~-~ o h ~
:d C~) ~ h .
_ ~ .

. ~ ~ :
r~ -~ I' 13~ ~
. _ . _ . . I j - O~ . 1 ~ P~ , ~ U z(~J
.

1~ ' . . .
.

~/ ~O N N ~ ~` N
~: C ) ~
J !~
o o~ ~ 8 Z 8 Z; ~ ~ ~ 8 Z o 5? 0 r ¦ o ~ ~ \ O ~r~ ~ ~
. . ' ~ ''.
~ , . ~,, . ~' x u~ ~o ~ oo a~ o ~ ,.
r-~ ~
. . .
I !

.

. . . I
, .

- . : ~ .. , . :
~:

- ~ , .

' ` - ~ ' ! '~ ~ i Dd. 28160/28345 o ~ .
a~ ~ ~ o ~ ~ . ~.
~ ~I) U~¦ ~I) 0 ~ a - ~ - _ 0 C~

d ~1 ~ _ ~ _ . . ,_. .~

. . li L~
. .
.. '. ~

a a ;'!

o ~ ~ m_o ~ _ l, ~ ~ ~ CO .
W ~ ~ r~
_ , ~, - 27 - :~

, Dd. 2~1 60/2~3345 ~071191 ~i j~ ~ --R

= = O ` IN

_ ~ . i !
. t~

~ ~ a ~ ~ o ~ 8`~' N ~ ~

~ ~ .
~ h ~
~, .` ' .' .

l _ !
1~ t~
_ : - 28 -. ' , .
. .

.:
:: :

~07~191 Dd.28160/28345 Example 45 ~¦
4.22 Parts of n-hexyl anthranilate in 25 parts of 2N hydrochloric acid is stirred at 0-5C and 10.4 parts of 2N sodium nitrite is added dropwise over 15 minutes. A solution of 5.0 parts of 2-keto-3-pyridinium chloride-4-ethyl-6-hydroxy-1,2-dihydropyridine in 100 parts of water is stirred at 0-5C and the above diazo solution iB added over 10 minutes. The bright yellow solid ;
which separates i6 filtered off and dried to yield a reddish-yellow powder which dyes polyacylonitrile and acrylonltrile copolymer in greenish-yellow shades of outstanding light fastness and wash fastness and has the structure:- , . ,' COOnC6H13 C2H5 ~) N = N ~ Cl

Claims

The embodiments of the invention in which an exclusive property of privilege is claimed are defined as follows:

1. Azo dyestuffs devoid of carboxylic acid and sulphonic acid groups and of the formula (I) x? (I) wherein R is ahydrogen atom, halogen atom, cyano, nitro, hydroxy, amino, aryl, alkyl, aralkyl or cycloalkyl group, R1 is a hydrogen atom, alkyl, aryl, aralkyl or cycloalkyl group, R2 is an alkyl group of six to twelve carbon atoms or an aryl or an aralkyl group, K? is a cationic group, x? is an anion and the ring A
may carry as additional substituents, halogen, alkoxy, alkyl, acylamino, alkoxycarbonyl, nitro, acyloxy, aryloxy, carbamyl or acyl groups.

2. Azo dyestuffs as claimed in Claim 1 wherein R is lower alkyl of from one to four carbon atoms

3. Azo dyestuffs as claimed in Claim 2 wherein R
is methyl.

4. Azo dyestuffs as claimed in Claim 1, 2 or 3 wherein R1 is hydrogen or a lower alkyl group.

5. Azo dyestuffs as claimed in Claim 1, 2 or 3 wherein the group -COOR2 is in the ortho position with respect to the azo group.

6. Azo dyestuffs as claimed in Claim 1, 2 or 3 wherein the ring A contains as an additional substituents, a methyl or methoxy group, a chlorine atom of a group of the formula -COOR2 wherein R2 is as defined in Claim 1.

7. Azo dyestuffs as claimed in Claim 1 of the formula X ?

wherein R3 is a lower group, R4 is hydrogen or a lower alkyl group, R5 is an alkyl group of from 6 to 12 carbon atoms, K1 ? is a cyclammonium group and x? is an anion.

8. Azo dyestuffs as claimed in Claim 7 wherein R3 is methyl, R4 is hydrogen or methyl and K1? is pyridinium or an .alpha., .beta.- or ?-picolinium group.

9. Azo dyestuffs as claimed in Claim 8 wherein the -COOR5 group is ortho to the azo group.

10. Process for the manufacture of azo dyestuffs as claimed in Claim 1 which comprises diazotising an aromatic amine of the formula and coupling the resulting diazonium salt with a pyridone of the formula X ?

wherein A, R, R1, R2, K? and X? are as defined in Claim 1.

11. Process for the colouration of synthetic polymeric materials which comprises applying a dyestuff as claimed in Claim 1 thereto from an aqueous bath.

12. Process as claimed in Claim 11 wherein the synthetic polymeric material is polyacrylonitrile or a blend thereof which comprises applying the dyestuff from an acid, neutral or slightly alkaline dyebath at a pH of from 3 to 8 at a temperature of from 40-120°C or by a printing technique using a thickened printing paste.