Triphendioxazine compounds

Details Triphendioxazine compounds Triphendioxazine compounds

2000-05-31

2002-03-12

Raymond, Richard L. (Department: 1624)

Organic compounds -- part of the class 532-570 series

Organic compounds

Chalcogen in the nitrogen containing substituent

Reexamination Certificate

active

06355795

ABSTRACT:

GB 2284427 A describes chlorine-containing, symmetrically disubstituted triphendioxazine compounds of the following general formula
where
the rings labelled A carry rings which are fused linearly or angularly and consist of radical members, inter alia, of the formulae —NR
1
—(CO)
m
—NH—and —CR
1
═CH—CO—NH—wherein R
1
is hydrogen, C
1-4
alkyl or phenyl, preferably hydrogen, methyl or ethyl; and m is 1 or 2.
The preparation process disclosed in GB 2284427 A starts from intermediates i.e. amino compounds, which are ortho-substituted by an alkoxy group and are obtainable only by way of a relatively complex synthesis. The pigments disclosed in GB 2284427 A are difficultly dispersible and cannot easily be brought into pigment form.
The invention relates to novel chlorine-containing triphendioxazine compounds and to their use as pigments. The invention also relates to a particularly advantageous process for preparing these triphendioxazine compounds.
It is an object of the invention to provide new pigments possessing high fastness to solvents, migration and light, which have good thermal stabilities and a high tinting power and are also easily dispersible resp. easily to be brought into pigment form.
Another object of the invention is to provide a process by which the novel pigments are obtainable and which starts from readily available intermediates.
These objects are achieved by the novel triphendioxazine compounds according to claim
1
and their use for preparing pigments and by the process by which these novel triphendioxazine compounds are obtainable.
The present patent application therefore provides, firstly, compounds of the general formula (I)
in which the rings labelled A in positions 1,2-, 2,3- or 3,4- and 8,9-, 9,10- or 10,11- carry a linearly or angularly fused heterocyclic ring containing at least one nitrogen atom which is substituted or unsubstituted, with the proviso that compounds with only unsubstituted nitrogen atoms and symmetrically disubstituted compounds with C
1-2
alkyl and unsubstituted phenyl substituents are excluded. Examples of such fused heterocyclic rings are enumerated in GB 2284427 which is incorporated by reference.
Preferred compounds of formula (I) are those with formulae (Ia), (IIa), (IIIa) and (IIIb)
where R
1
, R
2
, R
3
and R
4
, independently of one another, are hydrogen, a C
1-8
alkyl radical, a substituted or unsubstituted phenyl, benzyl, benzanilide or naphthyl radical, a substituted or unsubstituted C
5-6
cycloalkyl radical or a radical of the formula
with the proviso that in the case of symmetrically disubstituted compounds the definitions hydrogen, C
1-2
alkyl radical and unsubstituted phenyl radical are excluded.
In view of the fact that only compounds having hydrogen substituents are capable of building hydrogen bridges (which is believed to be necessary for the pigmentary properties), it is surprising that even tetrasubstituted compounds possess pigmentary properties.
The substituents R
1
, R
2
, R
3
and R
4
, independently of one another, are preferably hydrogen, a methyl radical, an ethyl radical, an n- or i-propyl radical, an n-, i-, sec- or tert-butyl radical, a cyclohexyl radical, a substituted or unsubstituted benzanilide radical, a naphthyl radical, a radical of the formula (a)
an unsubstituted phenyl radical, a phenyl radical substituted one or more times by radicals selected from the group consisting of halogen, preferably chlorine, nitro groups, phenyl radicals, C
1-8
alkyl radicals, preferably C
1-4
alkyl radicals, and C
1-2
alkoxy radicals, with the abovementioned proviso for symmetrically disubstituted compounds.
The abovementioned substituted phenyl radical in the definition of R
1
to R
4
is preferably selected from the group consisting of o-, m-, p-methyl-, ethyl-, methoxyphenyl, 2,4- and 3,5-dimethylphenyl, 2,5-dichloro-, dimethoxy-, diethoxy-phenyl, m-, p-nitrophenyl, 2,5-dichloro-, 2,5-diethoxy-4-nitrophenyl, 2-methoxy-4-nitrophenyl, 3-chloro-4-methyl-, 3-chloro-4-methoxyphenyl, p-ethoxyphenyl and the radical
The abovementioned substituted benzanilide radical in the definition of R
1
to R
4
is preferably selected from the group consisting of radicals of the formulae (b) and (c)
Preferred triphendioxazine compounds are those for which R
2
and R
4
are hydrogen and R
1
is a methyl radical and R
3
is an ethyl radical (asymmetrically disubstituted compound) or in which R
1
and R
3
are each a 4-methylphenyl or 4-methoxyphenyl radical (symmetrically disubstituted compounds).
Preferred symmetrically tetrasubstituted compounds are the tetramethyl-, tetraethyl-, tetrapropyl (n- or i-) and tetrabutyl (n-, i-, sec- or tert-)substituted compounds.
Preferred asymmetrically tetrasubstituted compounds are those for which the definitions of R
1
and R
2
are selected from-the group consisting of the radicals methyl, ethyl, propyl (n- or i-) and butyl (n-, i-, sec- or tert-) and R
3
and R
4
can have any of the above definitions.
It has been found that even amino compounds which are not ortho-substituted are suitable as intermediates provided that the cyclization which follows the reaction with 2,3,5,6-tetra-chlorobenzoquinone (chloranil) is carried out with manganese dioxide and concentrated sulphuric acid, e.g. from 80 to 100% strength, preferably from 90 to 95% strength. The process for preparing the novel compounds of the formula (I) is therefore also an object of the present patent application. Following the reaction of 1 mol of chloranil with 2 mol of a compound of the general formula (IV)
in which ring A carries a fused heterocyclic ring containing at least one nitrogen atom which is substituted or unsubstituted with the abovementioned proviso, there follows the characterizing process step of the cyclization conducted with manganese dioxide (MnO
2
) and concentrated sulphuric acid, e.g. from 80 to 100% strength, preferably from 90 to 95% strength.
Preferred intermediates of formula (IV) are those of formulae (XVI) to (XVIc)
where R
1
and R
2
are as defined above.
The advantage of this process is that it is possible to start from the intermediates (XVI), (XVIa), (XVIb) and (XVIc) which, unlike the amino compounds which carry an alkoxy group in the ortho position, are relatively easy to obtain. For example, compounds of the formula (XVI) are obtainable by a process comprising the following steps:
In a first step, the reaction of 2,4-dinitrochlorobenzene (XI) with the corresponding primary amine, to give the N-substituted 2,4-dinitroaniline (XII)
In a second step, the reduction of the compound of the formula XII, preferably with hydrated sodium hydrogen sulphide, to give the 1,2-diamine compound (XIII)
In a third step, the cyclization of a compound of the formula (XIII), preferably with phosgene, chloroformic ester or urea, to give the l,3-dihydrobenzimidazol-2-one compound
where R
1
is as defined above.
The disubstituted intermediate required to prepare the tetrasubstituted triphendioxazine compounds is obtainable, for example, by N-alkylation of the compound of the formula (XIV) in which R
1
is as defined above, preferably using dialkyl sulphate, alkyl bromide or alkyl iodide or, respectively, benzyl bromide or benzyl chloride, to give the compound of the formula (XV)
In a further step, the nitro compound of the formula (XV) is reduced, preferably by the method of Bechamp, to give the amino compound of the formula (XVI)
where R
1
and R
2
are as defined above.
Compounds of the formula (XVIa) are obtainable, for example, by cyclizing the compound of the formula (XIII) with oxalic acid or oxalic ester.
Compounds of the formula (XVIb) (5-aminobenzoxazolones) are preferably prepared by a process comprising the following steps:
Compounds of the formula (XVIc) (6-aminobenzoxazolones) are obtainable, for example, by a comprising the following steps:
Compounds with angularly fused rings can be produced by similar methods using starting compounds having isomeric substitution, e.g. 3,4-dinitroaniline instead of 2,4-dinitro-aniline.
Triphendioxazine compounds of the formula (I) according to t

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