Process for the preparation of stilbene compounds

Details Process for the preparation of stilbene compounds Process for the preparation of stilbene compounds

2000-08-17

2002-04-02

Raymond, Richard L. (Department: 1624)

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

Organic compounds

Four or more ring nitrogens in the bicyclo ring system

C544S113000

Reexamination Certificate

active

06365737

ABSTRACT:

The present invention relates to a new process for the preparation of 4,4′-bis-(triazinyl-amino)-stilbene-2,2′-disulphonic acid compounds and compositions containing them.
The preparation of 4,4′-bis-(triazinylamino)-stilbene-2,2′-disulphonic acid derivatives by primarily reacting 4,4-diaminostilbene-2,2′-disulphonic acid with cyanuric chloride and successively replacing the remaining chlorine atoms by nucleophiles has long been known (see, for example: “Fluorescent Whitening Agents”, R. Anliker and G. Müller, G. Thieme Publishers,1975, p.31 ff.), as has the use of such compounds as fluorescent whitening agents. However, as reported in the above citation, undesirable byproducts may often be formed, especially during the final reaction step (i.e. replacement of the third chlorine atom of cyanuric chloride), in which higher temperatures, longer reaction times, increased pressure and, possibly, excess of amines are required.
Surprisingly, it has now been found that this reaction step can be carried out more efficiently if the reaction is performed in a medium consisting of a of water and polyglycol mixture. A further advantage of this procedure is that the resulting reaction mixture is a stable formulation of the fluorescent whitening agent which, if required, may be directly utilised without intermediate isolation.
Correspondingly, the subject of the present invention is a process for the preparation of a 4,4′-bis-(triazinylamino)-stilbene-2,2′-disulphonic acid of the formula
characterised in that
(a) in a first reaction step cyanurchloride is reacted with the disodium salt of 4,4′-diaminostilbene-2,2′-disulfonic acid to give the intermediate of the formula
(b) in a second reaction step the compound of formula (2) is reacted with a compound of formula R
1
—H and/or R
2
—H to give the compound of the formula
(c) in a third step the compound of formula (3) is reacted with the compound of the formula R
3
H, and reaction step (a) and/or (c) are carried out in a medium consisting of a mixture of water and a polyglycol to give the compound of formula (1),
 wherein
R
1
, R
2
and R
3
, independently, are phenylamino; phenylamino substituted by C
1
-C
3
alkyl, halogen, cyano, COOR or COR; CONH—R; SO
2
NH—R; NH—COR; mono- or disulphonated phenylamino; morpholino; piperidino; pyrrolidino; —NH
2
; —NH(C
1
-C
4
alkyl); —N(C
1
-C
4
alkyl)
2
; —NH(C
2
-C
4
hydroxyalkyl); —N(C
2
-C
4
hydroxyalkyl)
2
; —N(C
1
-C
4
alkyl)(C
2
-C
4
hydroxyalkyl); NHC
2
-C
4
alkylsulphonic acid; —OC
1
-C
4
alkyl; an aminoacid or aminoacid amide or a polyethyleneglycol residue from which a hydrogen atom on the amino group has been removed; or a polyethyleneglycol from which a hydrogen atom of the —OH-group was removed;
R
1
and R
2
may further independently represent hydrogen; C
1
-C
4
alkyl; phenyl; naphthyl; phenyl or naphthyl substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy, halogen, C
2
-C
5
alkanoylamino, nitro, sulpho or C
1
-C
4
alkylated amino;
R is hydrogen; or C
1
-C
3
alkyl; and
M is H, Na, Li, K, Ca, Mg, ammonium, or ammonium that is mono-, di-, tri- or tetrasubstituted by C
1
-C
4
alkyl, C
2
-C
4
hydroxyalkyl or a mixture thereof.
Compounds of formula (1) in which M is H, Li, K, Ca, Mg, ammonium, or ammonium that is mono-, di-, tri- or tetrasubstituted by C
1
-C
4
alkyl, C
2
-C
4
hydroxyalkyl or a mixture thereof can be readily prepared from corresponding compounds of formula (1) in which M is Na by methods known per se, for example those disclosed in U.S. Pat. Nos. 4,737,240 and 5,288,294.
The final product of formula (1) can comprise 1 to 20%, preferably 1 to 10% b.w. of components wherein R
3
is a polyethyleneglycol from which a hydrogen atom of the —OH-group was removed.
As C
1
-C
4
alkyl, there are defined methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
The reactants are generally used in substantially the stoichometric proportions required to form the compounds of formula (1).
The polyglycol preferably has a molecular weight within the range of about 200 to 5000 and is more preferably a polyethyleneglycol of molecular weight of about 200 to 1500.
Further polyglycols that can be use for the present process are block copolymers of ethylene oxide and propylene oxide which may be represented by the formula
H—(OCH
2
CH
2
)
a
—(O—CH(CH
3
)—CH
2
)
b
—(OCH
2
CH
2
)
a
—OH
wherein
a is from 0.5 to 230; and
b is form 15 and 80.
These block copolymers are also suitable for different paper, textile, detergent and cosmetic applications.
The ratios of polyglycol to water, which may be used in the above process for the first and/or third reaction step, can lie between 90:10 and 10:90, but preferably lie within the range of 30:70 to 70:30.
The temperature at which the reaction is carried out may lie between 50° C. and the boiling point of the polyglycol-water mixture, but is preferably at the boiling point of the mixture.
The reaction may be carried out at a pH value of between 7.5 and 12.5, but is preferably performed at between pH 8.5 and 9.0.
The process is particularly suitable for the preparation of a compound of formula
wherein M and R
1
are as defined in claim
1
and n is 0, 1 or 2.
Especially preferred compounds are those of formula (4) in which each M is hydrogen, sodium or potassium and, furthermore, those in which R
1
represents morpholino, —NH
2
; N—(CH
2
—CH
3
)
2
; —NHCH
3
; —N(CH
3
)CH
2
CH
2
OH; NHCH
2
CH
2
OH, —N(CH
2
CH
2
OH)
2
, —N(CH
3
)(CH
2
CH
2
OH) or —NHCH
2
CH
2
SO
3
H and also those in which R
1
represents an amino acid residue from which a hydrogen atom on the amino group has been removed. Specific examples of aminoacids from which such preferred aminoacid residues R
1
are derived include glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylalanine), diiodotyrosine, tryptophan (&bgr;-indolylalanine), histidine ((&bgr;-imidazolylalanine), &agr;-aminobutyric acid, methionine, valine (&agr;-aminoisovaleric acid), norvaline, leucine (&agr;-aminoisocaproic acid), isoleucine (&agr;-amino-&bgr;-methylvaleric acid), norleucine (&agr;-amino-n-caproic acid), arginine, ornithine (&agr;,&dgr;-diaminovaleric acid), lysine (&agr;,&egr;-diaminocaproic acid), aspartic acid (aminosuccinic acid), glutamic acid (&agr;-aminoglutaric acid), threonine, hydroxyglutamic acid and taurine, as well as mixtures and optical isomers thereof. Of these aminoacids from which such preferred aminoacid residues R
1
are derived, sarcosine, taurine, glutamic acid and aspartic acid are particularly preferred.
In the final reaction step a reaction mixture of the compound of formula (1) and the corresponding polyglycol/water mixture is obtained. A further advantage of the present invention is that this mixture comprising polyglycol which has multi-functional properties as mentioned above can directly be used without further treatment for paper, textile, detergent and cosmetic applications.
An other aspect of the present invention is therefore a liquid composition containing the compounds of formula (1) in a polyglycol-water mixture.
Preferably the liquid composition contains 5 to 40% of compounds of formula (1) and 95 to 60% of a polyglycol-water mixture, whereby the ratio of polyglycol to water lies between 90:10 and 10:90 parts by weight.
In dissolved or finely divided states, the brighteners obtained by the above process display a more or less pronounced fluorescence. They are therefore used, according to the invention, for optically brightening synthetic or natural organic materials.
Examples of such materials which may be mentioned, without the review given below being intended to express any limitation thereto, are textile fibres from the following groups of organic materials, insofar as optical brightening thereof enters into consideration:
(a) Polyamides which are obtainable as polymerisation products by ring opening, for example those of the polycaprolactam type,
(b) polyamides which are obtainable as polycondensation products based on bifunctional or polyfunctional compounds capable of underg

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