Triazinylaminostilbene compounds

Details Triazinylaminostilbene compounds Triazinylaminostilbene compounds

2000-09-21

2001-12-18

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

C008S919000, C008S119000, C252S301210, C252S301230

Reexamination Certificate

active

06331626

ABSTRACT:

The present invention relates to the novel hydrates of the salts of a specific 4.4′-di-triazinylamino-2,2′-di-sulfostilbene compound, characterised by their water of hydration content; to the crystal forms which are associated with the new hydrates and which are characterised by their X-ray diffraction pattern; to processes for the preparation of the new hydrates; and to the use of the new hydrates for the preparation of concentrated formulations of fluorescent whitening agents.
According to recent practice, fluorescent whitening agents are preferably put on the market in the form of aqueous solutions or suspensions. To this end, for example, the moist filtercakes or dry powders of the fluorescent whitening agents are suspended in water. Dispersants and thickeners are added to the suspension in order to increase the homogeneity, wettability and shelf life of the suspension. Frequently, an electrolyte is also added together with these auxiliaries. Despite the presence of these additives, there are concentration limits for the fluorescent whitening agent suspension, above which the suspension is often unstable on storage and has poor metering characteristics. These concentration limits are often difficult to reproduce, since they can be affected by the nature of a pretreatment which may have been applied to the suspension of the fluorescent whitening agent. In particular, depending on the nature of a pretreatment, a variety of hydrates of the fluorescent whitening agent, having different crystal forms, may be obtained.
Surprisingly, it has now been found that formulations of a specific fluorescent whitening agent, which have an active substance concentration of more than 30% by weight, which are stable on storage and the viscosity of which can be selectively set at a value within a wide range, can be prepared if a specific hydrate or mixtures of hydrates of the fluorescent whitening agent used, having a specific crystal form, or several specific crystal forms, are present. The new formulations contain only low amounts of formulation auxiliaries and are useful for the fluorescent whitening of a wide range of substrates, including textiles and paper.
Accordingly, the present invention provides a hydrate of the 4,4′-di-triazinylamino-2,2′-di-sulfostilbene compound having the formula:
in which M and M
1
independently represent hydrogen, an alkaline-, an alkaline earth metal or ammonium, x is a number within the range of from 1to 30, and the crystal form of the hydrate (I) being characterised by an X-ray diffraction pattern which is essentially as set out in the accompanying
FIGS. 1
to
11
; or a mixture containing one or more of the hydrates of the 4,4′-di-triazinylamino-2,2′-di-sulfostilbene compound having the formula (I).
Preferred hydrates of formula (I) are compounds in which M and M
1
both represent hydrogen or sodium, the hydrates being characterised by an X-ray diffraction pattern which is essentially as set out in the accompanying
FIGS. 1
to
7
; or a mixture containing one or more of the hydrates of the di-sodium salt of the 4,4′-di-triazinylamino-2,2′-di-sulfostilbene compound having the formula (I).
Further preferred hydrates of the 4,4′-di-triazinylamino-2,2′-di-sulfostilbene compound (I) are those in which M and M
1
both represent potassium, the hydrate being characterised by an X-ray diffraction pattern which is essentially as set out in the accompanying FIG.
8
and in which x represents 9 to 17 and those in which M and M
1
both represent lithium, the hydrates being characterised by an X-ray diffraction pattern which is essentially as set out in the accompanying
FIGS. 9
to
11
; or a mixture containing one or more of the hydrates of the 4,4′-di-triazinylamino-2,2′-di-sulfostilbene compound having the formula (I), M and M
1
representing lithium and in which x represents 9 to 30.
Further hydrates of interest are such hydrates of the 4,4′-di-triazinylamino-2,2′-di-sulfostilbene compound (I) in which M and M
1
both represent calcium or magnesium and also those in which M and M
1
both represent ammonium.
In compounds of formula (I) in which M and M
1
both represent ammonium these may be represented by the formula -N(R)
4
,whereby R represents hydrogen or C
1
-C
4
-alkyl, all R-groups not necessarily being identical, or C
2
-C
4
-alkanolammonium.
The respective X-ray diffraction patterns,
FIGS. 1
to
11
, are obtained using an X'Pert powder diffractometer (Philips, Almelo) in reflexion geometry and Cu radiation. The reference patterns for crystal forms B (
FIG. 1
) and C (
FIG. 2
) are measured in suspensions in an atmosphere of air, without control of relative humidity. The measurement of the reference patterns for crystal form D (FIG.
3
), E (FIG.
4
), F (
FIG. 6
) and G (
FIG. 7
) and also that of the di-potassium salt (
FIG. 8
) are also conducted in suspensions, under nitrogen, while maintaining the relative humidity at a level of 80-90%, as are those of the three crystal forms of the di-lithium salt (FIGS.
9
-
11
), whilst that of crystal form A (
FIG. 5
) was conducted in the solid state. In each of the accompanying
FIGS. 1
to
11
, there is shown the part of the measurements in the 20-area between 1° and 30°.
Each of the novel hydrates of formula (I) has a characteristic X-ray diffraction pattern.
The crystal forms A, B, C, D, E, F and G and also those of the di-potassium and lithium salts consist for the most part of one or more hydrates of the formula (I) in which x is a number between 1 and 30.
The amount of water of hydration may be determined via
differential thermal analysis or dynamic differential calorimetry in which the proportion of the unbound water, that is the water melting at 0° C., is measured, or by subsequent water analysis by methods such as Karl Fischer titration, thermogravimetric analysis or loss on drying at elevated temperature.
The di-sodium salt of 4,4′-di-triazinylamino-2,2′-di-sulfostilbene possessing the (A) hydrate form may be produced by successively reacting cyanuric chloride with 4,4′-diaminostilbene disulphonic acid di-sodium salt, aniline and diethanolamine, adjusting the pH of the mixture to 9.0 to 9.5 with concentrated sodium hydroxide solution and evaporating the mixture to dryness. If, prior to treatment with sodium hydroxide, the compound is isolated in the form of the free acid, a hydrate results possessing the (F) crystal form.
The (C) hydrate crystal form may be obtained by neutralization of the free acid of 4,4′-di-triazinylamino-2,2′-di-sulfostilbene possessing the (A) hydrate form with dilute sodium hydroxide solution, homogenising and allowing to stand at room temperature; the (D) hydrate crystal form by treatment of the sodium salt of 4,4′-di-triazinylamino-2,2′-di-sulfostilbene possessing the (A) hydrate form aqueous sodium chloride solution, stabilizing and homogenising; and the (E) hydrate crystal form by treatment of the free acid of 4,4′-di-triazinylamino-2,2′-di-sulfostilbene possessing the (A) hydrate form with concentrated sodium hydroxide solution and homogenising. The (G) crystal form of the hydrate may be obtained from the (E) form by equilibration in a closed vessel at elevated temperature.
The (C) hydrate can further be prepared by seeding an aqueous suspension of the corresponding free acid, with (C) seed crystals. This technique has the advantage that active substance concentrations of more than 30% by weight, preferably 30 to 50% by weight, can be used and thus the suspension obtained is formed in the desired concentration and does not have to be concentrated.
The hydrate of crystal form (D) in accordance with
FIG. 3
, or the hydrate of crystal form which is designated as (E) form and characterised by an X-ray diffraction pattern which is essentially as in
FIG. 4
, may also be prepared by the seeding technique described in relation to the production of the (C) form.
In a preferred embodiment, a mixture of one or more of the novel hydrates

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