CA1039279A - Vat dyestuffs containing a pyridyl or pyrimidyl radical bonded to an s-triazine ring through a carbon bond - Google Patents

Abstract

Abstract of the Disclosure " Vat dyestuffs of the formula

Description

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The present illvention provides new vat dyestuffs of the general formula ~N~
A - N - C C - N - A
1 " , 2 (i) Rl N~`C'N R2 X ' ~' wherein X is pyridyl optionally substituted by alkyl of 1 to 4 carbon atoms or halogen, or pyrimidyl which is bonded through a carbon atom, Rl and R2 each is a hydrogen atom or alkyl of 1 to 4 carbon atoms, and Al and A2 each is independently anthraquinonyl optionally substituted by halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkanoyl .., o 1 to 4 carbon atoms, amino, phenylamino, benzoylamino, halobenzoylamino and phenylmercapto, or is phthaloylacridonyl.
Possible radicals Rl and R2 are alkyl groups with 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl, or isopropyl groups, as well as preferably hydrogen atoms.
Possible radicals Al and A2 are preferably 3,4-phthaloyl-., .
acridones bonded in 2- or 8-position as well as radicals of anthraquinones bonded in 1- or 2-position. These radicals can carry the above named substituents for vat dyestuffs.
Examples of such substituents are: halogen atoms, in partic-ular chlorine, fluorine or bromine, methyl, methoxy, acetyl,benzoylamino and p-chlorobenzoylamino.
Rxamples of substituents of the pyridyl radical X are:
methyl, ethyl, propyl, chloro and bromo.

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-~3 ~J7 Preferred dyestuEfs are those of the general formula (lj, wherein X is 2- 9 3- or 4-pyridyl which is bonded through a carbon atom, Rl and R2 each is hydrogen, and Al and A2 is anthraquinonyl which-is bonded in 1- or 2-position and which S is optionally substitut~d by halogen, alkyl of 1 ~o 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkanoyl of 1 to 4 carbon atoms, amino, phenylamino, benzoylamino, halobenzoyl-- amino and phenylmercapto, or is 3,4-phthaloylacridonyl which is bonded in 2- or 8-position.
~ lo The dyestuffs are manufactured by a process, wherein a - compound o the formula Al-Zl or A2-Z2, or a mixture of the two, is condensed in the molar ratio: 2:1 with a triazine of the formula "
Rl N~ ,N R2 X
in which formulae Zl and Z2 each is a halogen atom and Al, A2, X, Rl and R2 have the meanings indicated under formula (1).
: The preferred dyestuffs are manufactured by the process as defined above, wherein a triazine is used as starting material in which X is 2-, 3- or 4-pyridyl which is bonded through a carbon atom and Rl and R2 each is hydrogen, and :
; compounds of the formulae Al-Zl and A2-Z2 are used as starting material in which Al and A2 is anthraquinonyl which is bonded ln 1- or 2-position and which is optionally substituted by ; halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon ., .

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atoms, alkanoyl of 1 to 4 carbon atoms, amino, phenylamino, benzoylamino, haloben~oylamino and phenylmercapto, or is phthaloylacridonyl which is bonded in 2- or 8-position, and Zl and Z2 each is a halogen atom.
Bromine and, preferably, chlorine are suitable halogen atoms Zl and Z2 The mixture of the vattable compounds can be used simultaneously or stepwise. By means of such combinations it is possible to obtain mixed shades.
- 10 The method of manufacture is widely known. It is adavantageous to use a CuJ-pyridine catalyst as described in French Patent 1 603 058 (Case 1-6247/E). Examples of s~litable starting materials Al-halogen and A2-halogen are, for example:
l-chloroanthraquinone, l,3-dichloroanthraquinone, 1,5-dichloroanthraquinone, 1,6-dichloroanthraquinone, 1~8-dichloroanthraquinone, l-bromoanthraquinone, 1,5-dibromoanthraquinone, 1,8-dibromoanthraquinone, 2-chloroanthraquinone, 2,6-dichloroanthraquinone, 2,7-dichloroanthraquinone, 2-bromoanthraquinone, .~ .

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2,6-dibromoanthraquinone, ~ 2,7-dibromoanthraquinone, ` l-chloro-4-benzoylaminoanthraquinone, ~ l-chloro-4-(p-chlorobenzoylamino)-anthraquinone, : 5 1-bromo-4-benzoylaminoanthraquinone, ` l-chloro-5-benzoylaminoanthraquinone~
l-chloro-5-(p-chlorobenzoylamino)-anthraquinone, l-bromlo-S-benzoylaminoanthraquinone, . l-chloro-2-methylanthraquinone, lo l-chloro-4-methylanthraquinone, l-chloro-4-methoxyanthraquinone, : l-bromo-2-methoxyanthraquinone, l-bromo-4-methoxyanthraquinone, . l-chloro-3-acetyl-4 amino-anthraquinone, 1-chloro-4-anilido-anthraquinone, . ~:
l-chloro-4-phenylmercaptoanthraquinone, l-chloro-5-phenylmercaptoanthraquinone, :.
2-chloro-3,4-phthaloylacridone, 2,5,7-trichloro-3,4-phthaloylacridone.
Suitable diaminotriazines are e.g. those of the formula ~N~ :
H2N - C C Nnl2 ;
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3-pyridyl, ~ _ 5_ ', .~ .

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4-pyridyl,

5 ethyl-2-pyridyl, 2-chloro-3-pyridyl, 4-methyl-3-pyridyl, 2-chloro-4-pyridyl, 2-methyl-4-pyridyl, 2,6-dimethyl-4-pyridyl, 2-propyl-6-chloro-4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, ` 5-pyrimidyl.
The products according to the invention are suitable for dyeing and printing the most varied materials, in particular for dyeing and printing fibres made from natural or regenerated cellulose in the presence of reducing agents, e.g. dithionite.
` The dyeings which are obtained are characterised by outstanding levelling properties. The fastness properties are in general very good, in particular the fastness to light, water, chlorine, and to boiling soda. The new dyestuffs reserve polyester fibres well or stain them tone in tone, which makes them suitable for dyeing fibre blends in ad-mixture with disperse dyestuffs.
Compared with known comparable dyestuffs, which instead of a heterocyclic radical, in particular the pyridyl radical, contain a phenyl radical bonded to the s-triazine ring, the

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f~g dyestuffs of the present invention are characterised by a reduced fibre damaging actlon in light.
The new dyestuffs can also be used as pigments. On account of their favourable properties, they can be used for the most diverse forms of pigment application, e.g. in finely divided form for colouring rayon and viscose, or cellulose ethers or esters, or polyamides or polyurethanes or poly-es~ers in the spinning melt, as well as for the production of coloured lacquers or lake formers, solutions of products from acetyl cellulose, nitrocellulose, natural resins or artificial resins, such as polymerisation resins or condensation resins, e.gO aminoplasts, alkyd resins, phenolic plastics, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, ru~ber, casein, silicone and silicone resins. Furthermore, it is also possible to use them with advantage in the manufacture of coloured pencils,cosmetic preparations, or laminated sheets.
The following Examples illustrate the invention, the parts being parts by weight unless otherwise stated.

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EXAMPLE I
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A solution of 0.55 parts of copper (I) iodide in 3 parts of pyridine isadded to a suspension consisting of 10 parts of l-chloroanthraquinone, 3.75 parts of 2,4-diamino- -6-(4'-pyridyl)-s-triazine, and 5.3 parts of sodium carbonate , 5 in 70 parts of nitrobenzene &nd the whole is stirred over the course of 1 hour at 180-185C. The mixture is subsequently stirred for 4 hours at this temperature. The reaction mass is ~;
cooled to 80C, filtered, and the res-idue is thoroughly washed with nitrobenzene, then with methanol and water. Any copper present is removed by st:Lrring the yellow dyestuff in ; dilute nitric acid ~or ~ hour at 80C. It is then f-iltered of~, washed neutral, and dried. Yield: 11.2 parts o~ a yellow dyestuff of the formula ;~

- O ~-- ~ C- N 0 It dyes cotton from a hydrosulphite vat in yellow shades with good fastness properties. `
Dyestuffs with similar properties are obtained by ;
substituting for the 3.75 parts of 2,4-diamino-6-(4'-pyridyl)-s-triazine the number of parts indicated in column I of the . ! ~
`i 20 following Table of the compounds listed in column II.

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_ ~ . _ _ __ ''' ''; ,' 3,75 2,4-diamino-6-(2'-pyridyl)-s-triazine 3,75 2,4-diamino-6-(3'-pyridyl)-s-triazine .-;
4,1 2,4-diamino-(4'-Methyl-3'-pyridyl)-s-triazine 4,4 2,4-diamino-(2'--chloro~3'-pyridyl)-s-triazine 3,8 2,4-diamino-(5'-pyrimidyl)-s-triaz:Lne ~ :
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,, :, ~ ' "' By substituting for the 10 parts of l-chloroanthraquinone in Example 1 the amount indicated in column I of the following Table of the anthraquillones listed in column II, there are `;
obtained dyestuffs which from the vat dye cotton in the shades `
listed in column III .
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TABLE II

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___ . . ,", ~, 11,2 l-bromoanthraquinone yellow ; 10,0 2-chloroanthraquinone yellow 15,1 l-chloro~4-benzoylamino-anthraquinone red 15,35 1-chloro-4-(p-chlorobenzoylamino)- " red 15,1 1-chlorv-5-benzoylamino-anthraquinone yellow 15,35 1-chloro-5-(p-chlorobenzoylam.lno)- " yge~ow 10,6 1-chloro-4-methyl-anthraquinone yellow 11,2 1-chloro-4-methoxy-anthraquinone orange `
12,4 1-bromo-4-methoxy-anthraquinone orange 12,4 1-chloro-3-acetyl-4-amino-anthraquinone blue : 13,8 1-chloro-4-anilido-anthraquinone blue 14,5 l-chloro-S-phenylmercapto-anthraquinone yellow 14,8 2-chloro-3,4-phthaloylacridone ` blue 16,25 1-bromo-4-benzoylamino-anthraquinone red _ _ "~
., , ` In place of the diaminotriazine mentioned in Example ~ 1, it is also possible to use with equal success ~he compounds -~
: listed in Table 1.

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EXAMPLE 3 ~ :

: 11.4 parts of 1,3-dichloroanthraquinone and 3.75 parts uf 2,4-diamino-6-(3'-pyridino)-s-triazine are stirred for 4 hours at 185C in the prasence of 5.3 parts of sodium ; ~: :
S carbonate, 1 part of copper(I) iodide and 4 parts of pyridine -in 70 parts of nitrobenzene. The resuLting yellow clyestuf .; . ~ ~ , is filtered off at-80C and processed as described in Example 1 to yield 12 parts of the dyestuff of the formula H
0 N - - C b ~ N 0 N N
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. 10 The dyestuff, which is treated in the conventional ; :. manner with sodium hypoch:Lorite, dyes cotton ~rom the vat in ~.`
brilliant greenish yellow shades which are fast to light and ~:
wet treatments.
A dyestuff is obtained which dyes cotton from the vat ;` 15 in neutral yellow shades by substituting 11.4 parts of 1,6- or 1,7-dichloroanthraquinone for thP 11.4 par~s oft1,3-dichloro- :`.
` anthraquinone.

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Dyeing Instruction 1 Part of dyestuf is vatted at 50-70C with 10 -~
parts by volume of sodium hydroxide having a specific gravity of 36 Bé and 5 parts of sodium hydrosulphite in 200 parts of water. The above stock vat is added to a dyebath which contains in 2000 parts of water 5 parts by volume of sodium hydroxide solution with a specific gravity of 36 Bé and 3.7 parts of sodium hydrosulphite. 100 parts of cotton are put ~-into this dyebath at 40C. After 10 minutes, 15 parts of -.j, .
sodium chloride are added and after 20 minutes, a further 15 parts and dyeing is carrled out for 45 minutes at 40C. The`~ ;
cotton is then squeezed out, oxidised, and flnished in the i~
conventional manner.

Dyeing Instruction II

1 part of the dyestuff obtained accordlng to Example . ", 1 and 0.5 part of CI Disperse Yellow 84 are ground wet with ~;
2.5 parts of a 50% aqueous solution of the sodium salt of dinaphi~hylmethane-disulphonic acid. A dyebath is prepared with this dyestuff preparation, 2 parts of ammonium sulphate, and ~-1000 parts of water~ and the pH is adjusted to 6.0-6.9 with monosodium phosphate.

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100 parts of a blended fabric of cotton/polyester ~-(67% polyester) are put into this bath, which i5 heated to ~;
120-125C over the course of 45 minutes. Dyeing is carried out at this temperature for 60 minutes in a sealed vessel.
The dyebath is then cooled to 60-70C and 20 parts by volume of sodium hydroxide solution of ~é 36 and 5 parts of sodium hydrosulphite are added. After 45 minutes, the fabric is squeezed out, oxidised, and finished in the usual manner. `~
A blended fabric dyed yellow is obtained.
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Plgment coloration ~
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5 rarts of the d~estuff mentioned in Example l are .
mixed with 95 parts of dioctyl phthalate and ground in a ball `
mill until the dyestuff particles are smaller than 3~
`3 0.8 part of this dioctyl phthalate paste is mi~ed l ~5 with 13 parts ofpolyvinyl chloride, 7 parts of dioctyl i: phthalate and 0.1 part of cadmium stearate, and this mixture is then rolled to and fro for 5 minutes in a twin roller mill ~-at 140C. ;~
A yellow coloured material having good migration properties and good fastness to light is obtained.
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1 V3 ~ ~7 Coloration of lacquers a) Nitrocellulose lacquer `
40 Parts of a nitrocellulose lacquer, 2.375 parts of .
titanium dioxide and 0.125 part of the dyestuff of Example 1 were ground in a rod mill for 16 hours. The resulting lacquer `~
is applied in a thin layer to aluminium foil. It gives a ~ ;
golden yellow coloration having excellent fastness to light.
b) Alkyd varnish ;~
; 10 g of titanium dioxide and 2 g of the pigment 1-~
! manufactured according to Ex2mple 2 ~No. 3 o~ the Table) are ground for 48 hours in a ball mill with a mixture consisting of 26.~ g o~ coconut alkyd resin, 24.0 of melamine formaal dehyde resin (50% solids content), 8.8 g of ethylene glycol monomethyl ether~ and 28.8 g of xylene. ~. -By spraying this varnish on an aluminium sheet, ;
drying it or 30 minutes at room temperature and then stoving ,. ..
it for 30 minutes at 120C, there is obtained a clear red finish of good tinctorial s~rength which is characterised by good fastness to crosslacquering, outstanding fastness to li.ght, and good resistance to weathering.
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Claims (6)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Vat dyestuffs of the formula wherein X is pyridyl optionally substituted by alkyl of 1 to 4 carbon atoms or halogen, or pyrimidyl which is bonded through a carbon atom, R1 and R2 each is a hydrogen atom or alkyl of 1 to 4 carbon atoms, and A1 and A2 each is independently anthra-quinonyl optionally substituted by halogen, alkyl of 1 to 4 car-bon atoms, alkoxy of 1 to 4 carbon atoms, alkanoyl of 1 to 4 carbon atoms, amino, phenylamino, benzoylamino, halobenzoyl-amino and phenylmercapto, or is phthaloylacridonyl.

2. Vat dyestuffs according to claim 1, wherein X is 2-, 3- or 4-pyridyl which is bonded through a carbon atom, R1 and R2 each is hydrogen, and A1 and A2 is anthraquinonyl which is bonded in 1- or 2-position and which is optionally substituted by halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkanoyl of 1 to 4 carbon atoms, amino, phenylamino, benzoylamino, halobenzoylamino and phenylmercapto, or is 3,4-phthaloylacridonyl which is bonded in 2- or 8-position.

3. A vat dyestuff according to claim 2 of the formula

4. A process for the manufacture of vat dyestuffs accor-ding to claim 1, wherein a compound of the formula A1-Z1 or A2-Z2, or a mixture of the two, is condensed in the molar ratio:
2:1 with a triazine of the formula in which formulae Z1 and Z2 each is a halogen atom and A1, A2, X, R1 and R2 have the meanings indicated in claim 1.

5. A process according to claim 4, wherein a triazine is used as starting material in which X is 2-, 3- or 4-pyridyl which is bonded through a carbon atom and R1 and R2 each is hydro-gen, and compounds of the formulae A1-Z1 and A2-Z2 are used as starting material in which A1 and A2 is anthraquinonyl which is bonded in 1- or 2-position and which is optionally substituted by halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkanoyl of 1 to 4 carbon atoms, amino, phenylamino, benzoylamino, halobenzoylamino and phenylmercapto, or is phthaloyl-acridonyl which is bonded in 2- or 8-position, and Z1 and Z2 each is a halogen atom.

6. A process according to claim 5 wherein 1-chloro-anthraquinone is condensed in the molar ratio: 2:1 with 2,4-diamino-6-(4'-pyridyl)-s-triazine to form a vat dyestuff of the formula