Organic compounds

Details Organic compounds Organic compounds

2001-10-02

2002-06-18

Klemanski, Helene (Department: 1755)

Compositions: coating or plastic

Coating or plastic compositions

Marking

C106S498000, C008S549000, C008S638000, C544S075000, C544S076000

Reexamination Certificate

active

06406525

ABSTRACT:

The invention relates to dioxazine compounds containing sulphonic acid groups and salts thereof and mixtures of these compounds which may be in internal or external salt form. They are suitable for use as dyestuffs.
According to the invention there are provided compounds of formula (I)
wherein
R
1
signifies —NH
2
or
 wherein
R
5
signifies hydrogen or C
1-4
-alkyl,
X and Y independently signify halogen or hydroxy or C
1-3
-alkoxy or phenoxy or the radical of a cyclic, an aliphatic, an araliphatic or an aromatic amine linked over the amine-nitrogen and optionally substituted by hydroxy, carboxy, alkoxy, alkyl and/or sulphonic acid groups or the rest of a heterocyclic amine linked over the amine-nitrogen,
Z signifies halogen or the radical of a cyclic, an aliphatic or an araliphatic amine linked over the amine-nitrogen and optionally substituted by hydroxy, carboxy, alkoxy and/or sulphonic acid groups or the rest of a heterocyclic amine linked over the amine-nitrogen,
R
2
signifies —NH
2
or
 with the same definitions for R
5
, X and Y as above or
R
2
is the moiety (b)
 wherein
P signifies —SO
3
H, —COOH or —OH,
Q signifies a —NH— radical or a group selected from
 wherein the asterisk marks the bond attached to the phenyl ring,
Z signifies the same as above,
n has the value 0, 1, 2,
R
3
signifies —NR
6
in which R
6
signifies hydrogen or a C
1-4
-alkyl radical or
R
3
is the rest (a)
 wherein all substituents have the same meanings as defined above,
R
4
signifies hydrogen or C
1-4
-alkyl,
T
1
and T
2
independently from each other signify hydrogen, halogen, C
1-6
-alkyl or C
1-4
-alkoxy,
M signifies hydrogen or a cation;
salts thereof and mixtures of such compounds and/or salts.
Preferred compounds of formula (I), wherein all substituents have same meanings as defined above, have the provisos that
(i) when R
1
and R
2
is —NH
2
then R
3
is
 wherein P, Q, Z and n have the same meanings as defined above,
(ii) when R
1
is —NH
2
and R
2
is
 wherein P, Q, Z and n have the same meaning as defined above, then R
3
is —NH—;
salts thereof and mixtures of such compounds and/or salts.
In further preferred compounds of formula (I) both R
1
and R
2
signify
wherein
R
5
signifies hydrogen or C
1-4
-alkyl, and
R
3
signifies —NR
6
in which R
6
signifies hydrogen or a C
1-4
-alkyl radical and all the other substituents have the definition as defined above,
salts thereof and mixtures of such compounds and/or salts.
In further preferred compounds the radicals X, Y and Z contain no chromophoric group.
In other preferred,compounds any amine H—X, H—Y or H—Z has a molecular weight in the range of 50 to 500, preferably 50 to 400. Where such an amine contains ring systems, it preferably contains 1 to 4 rings and most preferably has only 1 or 2 rings. Such amine preferably contains at least one hydrophilic group which independently can be anionic, cationic or non-ionogenic. Examples of anionic hydrophilic groups are carboxy or sulphonic acid groups. Examples of cationic hydrophilic groups are mono-(C
1-4
-alkyl)- or di(C
1-4
-alkyl)amino groups comprising a protonatable nitrogen atom or a quaternary ammonium group, wherein each C
1-4
-alkyl group can be substituted by halogen, hydroxy, C
1-4
-alkoxy, phenyl or phenoxy. Any phenyl or naphthyl ring present in the amine may be unsubstituted or substituted by one, two or three groups selected from halogen, hydroxy, C
1-4
-alkyl, C
1-4
-alkoxy, phenoxy, carboxy or sulphonic acid. Any heterocyclic ring present in the amine is a 5- or 6-membered ring containing one or two hetero atoms selected from N, O or S, which heterocyclicring is unsubstituted or substituted by one or two C
1-4
-alkyl groups.
Preferred H—Z are ammonia and aliphatic amines, preferably substituted with a hydroxy, carboxy, alkoxy or sulphonic acid group, e.g. ethanolamine, diethanolamine, isopropanolamine, diisopropanolamine, 2-amino-hydroxypropane, glycine, N-methyl-ethanolamine, 3-methoxy-propylamine, l-aminoethyl-2-sulfonic acid and most preferably, 1-methylamino-ethyl-2-sulfonic acid; heterocyclic amines, e.g. morpholine, piperazine or hydroxy-ethylpiperazine; or N,N-diethylaminopropylamine and 1,2-diaminopropane.
Most preferred H—Z is 1-methylamino-ethyl-2-sulfonic acid.
In a further preferred compound or mixture M is hydrogen or a colorless cation or M is a cationic portion in a substituent X, Y or Z containing a cationic charge, to form an inner salt.
In a further aspect of the present invention there are provided mixtures containing
a) a compound of formula (Ia) C
 wherein R
3
′ is a divalent radical of formula (a), R
2
′ is —NH
2
and Z has the same meaning as defined above;
b) a compound of the above formula (Ia) wherein R
3
′ is —NH—, R
2
′ is a radical of formula (b) and Z has the same meaning as defined above;
c) a compound of formula (II)
 wherein Q, P and n have the same meaning as defined above and Z′ has the same definition as Z, additionally Z′ can be an aromatic amine, preferably for the component c) Z′ is a radical of formula (c)
d) a compound of formula (II), wherein Z has the same meanings as defined above, except halogen, preferably for the component d) Z′ is a radical of formula (d)
e) a compound of formula (III)
 wherein Z′ has the definition as defined above,
or salts of such compounds.
The present invention further provides a process for the preparation of a compound of formula (Ib)
according to formula (I) with the same definitions of the substituents as defined above,
wherein one mole of a compound of formula (IV)
or a mixture of compounds of formula (IV) with the same definitions of the substituents as in formula (Ib) is reacted with two moles of at least one compound of formula (V)
wherein Hal signifies halogen, preferably chlorine, and X and Y independently have the same meanings as defined above, under dehydrohalogenating conditions, and, if in formula (Ib) anyone of X and Y has a significance other than halogen while in formula (V) the corresponding X or Y signifies halogen, and/or if in formula (Ib) Z has a significance other than halogen, the obtained condensation product of formula (VI)
with the same definitions of the substituents as in formula (Ib) is reacted, with at least one corresponding amine of formula H—X H—Y and/or H—Z, which have the same definitions as above and/or an alkali metal C
1-3
-alcoholate or phenolate, as required. The oxidation of the leuco form to the dioxazine form takes place after the condensation step(s) or simultaneously with the exchange of halogen for amine.
The compounds of formula (Ib) thus obtained may be isolated in accordance with known methods.
The compounds of formula (Ib) containing free basic groups may be converted wholly or in part into water-soluble salts by reacting with any inorganic or organic acids. The compounds of formula (Ib) containing carboxy or sulphonic acid groups may also be converted into water-soluble salts by reacting with any basic compound.
The starting compounds, the amines of formula (IV) in the leuco form may be prepared by step-wise replacement of the chlorine atoms of cyanuric chloride whereby in a first and second step cyanuric chloride is reacted with a dioxazine compound of formula (VII)
which can be identical or different, depending on the meanings of R
5
.
Before the reaction with a compound of the formula (V), the intermediately obtained dyestuff is brought into the leuco form of formula (IV) by reduction. This reduction process can be performed catalytically with hydrogen (and the usual catalysts palladium, platinum or nickel) or with other metals like iron, tin or zinc in the presence of acids. Alternatively, the reduction can be performed with sodium dithionite in water at pH values from 6 to 9, preferably 6.5 to 7.5, and temperatures from 15 to 45° C., preferably 20 to 30° C. The reducing agent is suitably used in double or triple molar amounts of the dyestuff to be reduced and all reduction and condensation reactions are performed in inert a

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