Organic compounds -- part of the class 532-570 series – Organic compounds – Sulfonic acids or salts thereof
Reexamination Certificate
2000-09-15
2001-08-14
Gitomer, Ralph (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Sulfonic acids or salts thereof
C562S405000, C585S435000, C585S657000
Reexamination Certificate
active
06274761
ABSTRACT:
The present invention relates to a new process for the preparation of salts of sulphonated distyryl-biphenyl compounds.
Distyryl-biphenyl sulphonic acid salts, their preparation and use as optical brightening agents have been described, for example in British Patent Specification 1,247,934 and in French Patent Specification 2,168,210. However, due to the method of synthesis of these compounds, the resulting bis-stilbene sulphonic acids are produced in the form of their sodium salts. Despite the inherent fluorescence of these systems, which render them useful as optical brightening agents, such sodium salts may also be disadvantageous with regard to properties such as water solubility and colouration. Hence, a simple method for the interconversion of such sodium salts into those possessing more desirable properties would be advantageous.
Methods for the interconversion of such salts are, for example, by way of the free acid, whereby the free acid must be far more insoluble than the sodium salt and also readily filterable, which, in general, is not the case with such bis-stilbene sulphonic acids. The free acid may also be converted into other salts by the use of a solid ion exchange resin, but, in the case, the free acid must be readily water soluble, which again is not the case with such compounds. Direct ion exchange can only be performed in order to convert a readily soluble salt into a far less soluble derivative, which is not a requirement in the present case.
Surprisingly, by way of ion pair extraction, a process has now been found for the preparation of salts of sulphonated distyryl-biphenyl compounds of formula:
in which R
1
and R
2
, independently, are hydrogen, C
1
-C
5
-alkyl, C
1
-C
5
-alkoxy or halogen, and M represents Li, K, an alkaline earth metal, ammonium, a mono-, di- or trialkylammonium or a tetraalkylammonium, all containing 1-4 carbon atoms in each alkyl group; a mono-, di- or tri (C
2
-C
4
)alkanolammonium, morpholinium, piperidinium or pyrrolidinium by, firstly, reacting a compound of formula:
with a di- or trialkylamine containing 6-12 carbon atoms in each alkyl group, in a two-phase system consisting of strong aqueous mineral acid and a water immiscible organic solvent and, secondly, reacting the resulting lypophilic ammonium salt with LiOH, KOH, an alkaline earth metal hydroxide, ammonia, a mono-, di- or trialkylamine or a tetraalkylammonium hydroxide, all containing 1-4 carbon atoms in each alkyl group; a mono-, di- or tri(C
2
-C
4
)alkanolamine, morpholine, piperidine or pyrrolidine.
When, in formula (1), R
1
and R
2
represent C
1
-C
5
-alkyl, these may be methyl, ethyl, n- or isopropyl, n-, sec-,or t-butyl, n-pentyl, iso-amyl or sec-amyl groups. When, in formula (1), R
1
and R
2
represent C
1
-C
5
-alkoxy, these may be methoxy, ethoxy, n- or isopropoxy, n-, sec-,or t-butoxy, n-pentyloxy, iso-amyloxy or sec-amyloxy groups. When, in formula (1), R
1
and R
2
represent halogen, these may be fluorine, chlorine, bromine, or iodine, preferably chlorine.
When M represents an alkaline earth metal these are preferably Ca or Mg, whilst when M represents ammonium these may be NH
4
, mono-, di-, tri- or tetramethylammonium, mono-, di-, tri- or tetraethylammonium, mono, di-, tri- or tetra-n- or isopropylammonium, mono, di-, tri- or tetra-n-, sec- or t-butylammonium, mono-, di- or triethanolammonium, mono-, di- or tri-n- or isopropanolammonium, mono-, di- or tri-n- sec- or t-butanolammonium, morpholinium, piperidinium or pyrrolidinium.
As di- or trialkylamines containing 6-12 carbon atoms in each alkyl group, utilised in the first reaction step, these may be any of the isomers of di- or trihexylamine, di or triheptylamine, di- or trioctylamine, di- or trinonylamine, di- or tridecylamine, di- or triundecylamine or di- or tridodecylamine, but are preferably tri-n-octylamine or triisooctylamine.
The process of the present invention is particularly useful for the preparation of compounds of formula (1), whereby, R
1
and R
2
both represent hydrogen, C
1
-C
3
-alkyl, C
1
-C
3
-alkoxy, bromine or chlorine, and M represents Li, K, Mg, Ca or an ammonium group.
The process of the present invention is preferably used for the preparation of compounds of formula (1) in which R
1
and R
2
both represent hydrogen and M represents Li, K, Mg, Ca, —N(R
3
)
4
, whereby R
3
represents hydrogen or C
1
-C
4
-alkyl, all R
3
groups not necessarily being identical, or C
2
-C
4
alkanolammonium.
The process of the present invention is most particularly useful for the preparation of compounds of the formula
whereby M
1
represents Li, K, —N(R
3
)
4
, where R
3
, represents hydrogen, C
1
-C
4
-alkyl, or C
2
-C
4
-alkanol and also for the preparation of compounds of formula
whereby M
2
represents Li, K or —N(n-C
4
H
9
)
4
.
The molar ratios of these amines to that of compound (2) lies in the range of from about 2 to about 4, preferably being in the range of 2.2 to 4.
Any strong mineral acid may be utilised in the initial reaction step, specific examples being hydrochloric acid, phosphoric acid or, in particular, sulphuric acid, the amount used being such that the pH of the aqueous layer lies within the range of from 1 to 5, especially within the range of from 2 to 3.
The water immiscible organic solvent utilised in the first reaction step may be a substituted or unsubstituted benzene, alkane or cycloalkylene, or mixtures thereof, specific examples of such being benzene, toluene, mono- or dichlorobenzenes, nitrobenzene, anisole, xylenes, pentane, hexane, cyclopentane or cyclohexane, isomeric mixtures of xylenes being especially preferred.
The temperature at which the initial reaction step is carried out may lie within the range of from about 10 to about 90° C., preferably between 50 and 80° C.
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 limitabon 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 undergoing a condensation reaction, such as hexamethylenediamine adipate and
(c) natural textile organic materials of animal or vegetable origin, for example based on cellulose or proteins, such as cotton or wool, linen or silk.
The organic materials to be optically brightened can be in diverse stages of processing and are preferably finished textile products. They can, for example be in the form of hank goods, textile filaments, yarns, twisted yarns, nonwovens, felts, textile fabrics, textile composites or knitted fabrics.
The brighteners defined above are of particular importance for the treatment of textile fabrics. The treatment of textile substrates is advantageously carried out in an aqueous medium in which the particular optical brighteners are present in a finely divided form (suspensions, so-called microdispersions and in some cases solutions). Dispersing agents, stabilisers, wetting agents and further auxiliaries can optionally be added during the treatment.
The treatment is usually carried out at temperatures of from about 20° to 140° C., for example at the boiling point of the bath, or in the region thereof (about 90° C.). For the finishing, according to the invention, of textile substrates it is also possible to use solutions or emulsions in organic solvents, as are used in dyeing practice in so-called solvent dyeing (pad-thermofix method and the exhaustion dyeing process in dyeing machines).
The optical brighteners which can be used according to the present invention can also be employed, for example, in the following u
Basler Roger Wolfgang
Eliu Victor Paul
Rohringer Peter
Sereinig Brigitte Gerhild
Volkel Julia
Ciba Specialty Chemicals Corporation
Gitomer Ralph
Khare D
Mansfield Kevin T.
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