Novel dibenzofuranylbiphenyl compounds of the formula (I) ##STR1## which are unsubstituted or are monosubstituted or polysubstituted by radicals R=hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, halogen, phenoxy and benzyloxy and in which R.sub.3 is C.sub.1 -C.sub.4 alkyl, halogen or phenyl and M is hydrogen and/or one equivalent of a non-chromophoric cation and the preparation and use thereof for fluorescent whitening are described.

The present invention relates to dibenzofuranylbiphenyl compounds which are 
selectively sulfonated, to their preparation and to their use as 
fluorescent whitening agents for the fluorescent whitening of textile 
materials or paper or to their use in detergents containing a peracid. 
Mixtures of sulfonated benzofuranylbiphenyl compounds of undefined 
composition and structure and their use as fluorescent whitening agents 
have been known for a long time (DE-A 22 38 734, DE-A 22 38 628, DE-A 23 
61 338 and DE-A 28 43 850). However, it has hitherto not been possible to 
prepare individual compounds of these mixtures having uniform structures. 
It has now been found, surprisingly, that sulfonated dibenzofuranylbiphenyl 
compounds having a definite structure can be prepared selectively by 
specific processes. 
The invention therefore relates to novel dibenzofuranylbiphenyl compounds 
of the formula (I) 
##STR2## 
which are unsubstituted or are monosubstituted or polysubstituted by 
radicals R=hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, 
halogen, phenoxy and benzyloxy and in which is C.sub.1 -C.sub.4 alkyl, 
halogen or phenyl and M is hydrogen and/or one equivalent of a 
non-chromophoric cation. 
Suitable halogens are, in particular, fluorine, chlorine and bromine, but 
especially chlorine. 
Suitable C.sub.1 -C.sub.4 alkyl radicals (or C.sub.1 -C.sub.4 alkoxy 
radicals) are unbranched or branched alkyl (or alkoxy, respectively) 
radicals. These alkyl (or alkoxy, respectively) radicals can in turn be 
substituted by, for example, aryl (phenyl or tolyl), C.sub.1 -C.sub.4 
alkyl, C.sub.1 -C.sub.4 alkoxy, OH or CN groups. On the other hand, the 
phenyl radicals can be substituted by alkyl, alkoxy or halogen. 
When M is a non-chromophoric cation, it is, for example, an alkaline earth 
metal, such as magnesium and calcium, but is preferably an alkali metal, 
such as lithium, sodium or potassium, and substituted or unsubstituted 
ammonium, such as ammonium, mono-, di- or tri-ethanolammonium, mono-, di- 
or tri-propanolammonium or mono-, di-, tri- or tetra-methylammonium. 
Compounds of the formula (II) 
##STR3## 
in which R.sub.1 is hydrogen, C.sub.1 -C.sub.4 alkyl, chlorine or C.sub.1 
-C.sub.4 alkoxy, R.sub.2 is hydrogen, C.sub.1 -C.sub.4 alkyl, chlorine or 
C.sub.1 -C.sub.4 alkoxy, R.sub.3 ' is C.sub.1 -C.sub.4 alkyl, chlorine or 
phenyl, and M is hydrogen and/or one equivalent of a non-chromophoric 
cation are preferred. 
Compounds of the formula (III) 
##STR4## 
in which R.sub.2, R.sub.3 ' and M are as defined above are, however, of 
particular interest. R.sub.2 is preferably hydrogen, 5-methyl, 5-ethyl or 
5-chlorine and R.sub.3 ' is preferably methyl, ethyl or phenyl. 
This invention also relates to processes for the preparation of the 
compounds of the formula (I) which comprise reacting one mole of the 
compound of the formula (X) 
##STR5## 
which is unsubstituted or is monosubstituted or polysubstituted by 
radicals R=hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, 
halogen, phenoxy and benzyloxy and in which R.sub.3 is C.sub.1 -C.sub.4 
alkyl, halogen or phenyl, with 
a) at least stoichiometric mounts of an SO.sub.3 /base complex, in an inert 
organic solvent, at temperatures from 20.degree. C. up to the boiling 
point of the solvent used, or 
b) treating the compound of the formula (X) with chlorosulfonic acid at 
0.degree.-80.degree. C. or 
c) treating the compound of the formula (X) with glacial acetic acid and 
concentrated sulfuric acid or oleum at temperatures from 80.degree. to 
140.degree. C. and neutralizing the resulting sulfonic acids, if 
appropriate, with suitable bases, such as aqueous alkali, ammonia or 
amines. Sulfochlorides which may be formed as a by-product are saponified 
previously or at the same time with water at elevated temperatures. 
The compounds of the formula (X) are in part known and can be prepared by a 
known method. 
The novel starting compounds of the formula (X) in which R.sub.3 is Cl are 
obtained by chlorinating compounds of the formula (X) in which R.sub.3 is 
H by means of phosphorus pentachloride at 100.degree. to 200.degree. in 
suitable solvents, such as chlorobenzene or dichlorobenzene. 
SO.sub.3 /base complexes are to be understood as meaning addition compounds 
of SO.sub.3 with organic bases, for example dioxane, preferably 
nitrogen-containing bases, for example triethylamine, 
N-ethyldiisopropylamine, dimethylformamide (DMF) and pyridine. The 
stability of these addition compounds is decisive for the degree of 
sulfonation. Thus 2 to 6, in particular 3 to 5, moles of SO.sub.3 
/pyridine complex (relative to the SO.sub.3 content) are used per mole of 
the compound of the formula (X), or 2 to 6, in particular 3 to 5, moles of 
SO.sub.3 /DMF complex (relative to the SO.sub.3 content) are used per mole 
of the compound of the formula (X). SO.sub.3 /base complexes are known and 
can be prepared by known methods (E. E. Gilbert, E. P. Jones, Ind. Enging. 
Chem. 49, No. 9, Part II, pages 1553 et seq (1957); Beilstein 20, III/IV, 
2232). 
In process b) especially one mole of the compound of the formula (X) is 
reacted with 2 to 20, in particular 2 to 4, moles of chlorosulfonic acid 
at temperatures from 0.degree. C. to 80.degree. C., in particular 
5.degree. C. to 40.degree. C., in the absence, or preferably in the 
presence, of an inert organic solvent. 
Examples of inert organic solvents are saturated aliphatic hydrocarbons, 
such as gasoline, petroleum ether and ligroin, halogenated aliphatic 
hydrocarbons, such as chloroform, carbon tetrachloride, dichloroethane, 
trichloroethane, tetrachloroethane, dichloropropane, trichloropropane, 
dichlorodifluoromethane and dichlorotetrafluoroethane, chlorobenzenes, 
such as mono-, di- and tri-chlorobenzene, nitrobenzenes, such as 
nitrobenzene and nitrotoluene, and monocyclic or dicyclic hydrocarbons, 
such as cyclohexane, methylcyclohexane and decalin. 
Compounds of the formula (I) are used for the fluorescent whitening of 
textile materials, in which connection polyamides, wool and cotton should 
be singled out particulary, and of paper. 
Based on the increased proportion of synthetic fibres or mixed fibres in 
the textiles produced nowadays, and the desire to give up washing coloured 
laundry separately, as well as from measures for saving energy, laundry is 
no longer washed at 90.degree. C.-95.degree. C. or at the boil in many 
countries, but at lower temperatures. This had the result that the 
perborates hitherto mostly contained in detergents and acting as bleaching 
agents have had to be activated by assistants, for example 
tetraacetylethylenediamine (TAED), in order to obtain acceptable bleaching 
effects even at washing temperatures of 60.degree.-80.degree. C. At even 
lower washing temperatures the perborate/activator systems no longer give 
satisfactory results either. 
For some time, therefore, detergents containing stronger bleaching agents, 
for example peracids, are described (German Offenlegungsschrift 27 56 583, 
EP-A 145 438, GB 2 141 754, GB 2 141 755, U.S. Pat. No. 4,028,263 and GB 
59 272). On the one hand these novel bleaching agents admittedly display 
excellent bleaching effects even at temperatures down to 20.degree. C., 
but, on the other hand, they destroy the customary fluorescent whitening 
agents present in detergents. 
The special dibenzofuranyl compounds described above exhibit an excellent 
stability in detergents containing such strong bleaching agents. Under 
average conditions of storage and even under more rigorous conditions 
(temperatures of over 30.degree. C. and over 60% humidity), these special 
dibenzofuranyl fluorescent whitening agents are completely stable in the 
detergent for several months or, at the most, are degraded to an extent 
which does not interfere in practice. 
The invention also relates, therefore, to detergents which are stable on 
storage and contain 0.5 to 30% of an inorganic or organic peracid or salts 
thereof or mixtures of peracids or salts thereof and also 0.03 % to 0.8% 
of a fluorescent whitening agent or a mixture of fluorescent whitening 
agents, in which the fluorescent whitening agents are 
dibenzofuranylbiphenyl compounds of the formula (I) 
##STR6## 
which are unsubstituted or are monosubstituted or polysubstituted by 
radicals R=hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, 
halogen, phenoxy and benzyloxy and in which R.sub.3 is C.sub.1 -C.sub.4 
alkyl, halogen or phenyl and M is hydrogen and/or one equivalent of a 
non-chromophoric cation. 
Compounds of the formula (II) 
##STR7## 
in which R.sub.1 is hydrogen, C.sub.1 -C.sub.4 alkyl, chlorine or C.sub.1 
-C.sub.4 alkoxy, R.sub.2 is hydrogen, C.sub.1 -C.sub.4 alkyl, chlorine or 
C.sub.1 -C.sub.4 alkoxy, R.sub.3 ' is C.sub.1 alkyl, chlorine or phenyl 
and M is hydrogen and/or one equivalent of a non-chromophoric cation, are 
preferred. 
Compounds of the formula (III) 
##STR8## 
in which R.sub.2, R.sub.3 ' and M are as defined above are, however, of 
particular interest. R.sub.2 is preferably hydrogen, 5-methyl, 5-ethyl or 
5-chlorine and R.sub.3 ' is preferably methyl, ethyl or phenyl. 
The peracids or salts thereof are the organic or inorganic compounds 
described in the literature or available on the market which bleach 
textiles at temperatures as low as 20.degree. C. In particular, the 
organic peracids are, for example, monoperacids or polyperacids having 
alkyl chains of at least 3, preferably 6 to 20, carbon atoms, but 
particularly diperoxydicarboxylic acids having 6 to 12 C atoms, such as 
diperoxyperazelaic acid, diperoxypersebacic acid, diperoxyphthalic acid 
and/or diperoxydodecanedioic acid (DPDDA) are of interest. It is also 
possible, however, to employ very active inorganic peracids, such as 
persulfate and/or percarbonate. The amount of organic peracids to be 
employed is preferably 0.5% to 10%, in particular 1% to 5%, and of 
inorganic peracids preferably 1% to 30%, in particular 10% to 20%, 
relative to the total weight of detergent and, if appropriate, in 
combination with small amounts of compounds which enhance the bleaching 
action of the peracids, such as divalent metal salts having a catalytic 
action, such as are described in U.S. Pat Nos. 4,655,782 and 4,655,953. It 
is preferable to use metal salts of copper and/or manganese. 
It is, of course, also possible to employ mixtures of organic and/or 
inorganic peracids and/or persalts. 
The addition of the peracids to the detergent is effected, in particular, 
by mixing the components, for example by means of screw-metering systems 
and/or fluidized bed mixers. 
The detergents are dry detergents of customary compositions. As a rule, in 
addition to the combination according to the invention of peracid and 
fluorescent whitening agent, they contain, for example, anionic, nonionic, 
amphoteric and/or cationic surfactants, builders, for example pentasodium 
tripolyphosphate, or substitute products, such as phosphonates, 
polycarboxylates, acrylic/maleic copolymers, zeolites, nitrilotriacetate 
or ethylenediaminotetraacetic acid, soil suspending agents, for example 
sodium carboxymethylcellulose, salts for adjusting the pH, for example 
alkali or alkaline earth metal silicates, foam regulators, for example 
soap, salts for adjusting the spray drying and granulating properties, for 
example sodium sulfate, perfumes, and also, if appropriate, antistatic and 
softening agents, enzymes, photobleaching agents, pigments and/or shading 
agents. These constituents should, of course, be stable to the bleaching 
system employed. 
Thanks to the combination according to the invention it is possible to 
provide detergents which meet the conventional standard, for example with 
regard to detergent power, stain removal and reviving the appearance of 
the washed articles, even when washing is carried out at temperatures from 
20.degree. C. to 60.degree. C. Coloured laundry and white laundry can 
advantageously thus be washed together, independently of the fibre.

The following examples serve to illustrate the invention; parts and 
percentages are by weight. 
EXAMPLE 1 
65 ml of 65% oleum in 200 ml of glacial acetic acid are initially 
introduced. 13.7 g of the compound of the formula 
##STR9## 
are then added with stirring, and the mixture is heated to 
100.degree.-105.degree. C. and stirred at this temperature for 1 hour. 
After cooling to 60.degree. C. 25 g of sodium acetate in 40 ml of water 
are added, the mixture is allowed to cool to room temperature and the 
product which has crystallized out is filtered off with suction. After 
recrystallization from a mixture of 800 ml of water and 400 ml of 
methylcellosolve and a second recrystallization from a mixture of 500 ml 
of water and 500 ml of methylcellosolve, 12 g of the compound of the 
formula 
##STR10## 
are obtained in the form of a pale yellow crystalline powder. UV 
absorption: .lambda.max=351 nm; .epsilon.=74,450 (in 1:1 DMF/H.sub.2 O). 
The compound of the formula 
##STR11## 
is obtained analogously as a pale yellow crystalline powder. UV absorption 
spectrum: .lambda..sub.max :353 nm; .epsilon.=76,300 (in 1:1 DMF/H.sub.2 
O). 
The compound of the formula (101) can be obtained as specified in DE-A 22 
38 628. 
EXAMPLE 2 
62.1 g of the compound of the formula (101) and 50 g of 
sulfurtrioxide/dimethylformamide complex are initially introduced with 
stirring in 370 ml of nitrobenzene, and the mixture is heated to 
115.degree. C. and stirred for 2 hours at this temperature. After cooling 
to 60.degree. C. the pH is adjusted to 9 with 10% sodium hydroxide 
solution, the nitrobenzene is removed by steam distillation and the 
aqueous suspension is cooled to 10.degree. C., the product is filtered off 
with suction and washed with 5% sodium chloride solution and dried in 
vacuo at 100.degree. C. This gives 86.3 g of a pale yellow product 
containing 94.6% of the compound (102). 
EXAMPLE 3 
18.5 ml of 65% oleum are initially introduced into 450 ml of glacial acetic 
acid. 44.2 g of the compound of the formula 
##STR12## 
melting point: 190.degree.-191.degree. C., are then introduced, with 
stirring, and the mixture is heated to 100.degree. C. and stirred for 1 
hour at this temperature. 
After cooling to room temperature the reaction mixture is poured into a 
solution of 100 g of sodium acetate in 450 mi of water, and the mixture is 
heated to 100.degree. C., 7 g of active charcoal are added and the mixture 
is filtered while hot. After cooling to room temperature the product which 
has crystallized out is filtered off with suction and dried in vacuo. The 
product thus obtained is recrystallized twice from a mixture of 150 ml of 
ethanol and 150 ml of water, with the addition of active charcoal. This 
gives 45 g of the compound of the formula 
##STR13## 
as a pale yellow crystalline powder, UV absorption spectrum: 
.lambda..sub.max :350 nm; .epsilon.=69,864 (1:1 DMF/H.sub.2 O). 
The compound of the formula (104) can be obtained analogously to the 
compound of the formula (101). 
EXAMPLE 4 
19.4 g of the compound of the formula 
##STR14## 
and 25.0 g of phosphorus pentachloride are stirred in 150 ml of 
chlorobenzene, and the suspension is heated to reflux temperature. When 
the starting material has dissolved completely and the evolution of 
hydrochloric acid gas is complete (approx. 1 hour), the mixture is allowed 
to cool and 50 ml of methanol are added cautiously. The precipitated 
product is filtered off with suction, washed with methanol and dried in 
vacuo. This gives 19.6 g of the compound of the formula 
##STR15## 
in the form of nearly colourless crystals. Melting point 
210.degree.-11.degree. (recrystallized from xylene). 
The compound of the formula 
##STR16## 
is obtained by sulfonation with chlorosulfonic acid in tetrachloroethane 
in accordance with Example 6. 
EXAMPLE 5 
A solution of 1.4 ml of chlorosulfonic acid in 20 ml of tetrachloroethane 
is added dropwise in the course of 1/4 hour, with stirring and at 
90.degree. C., to a suspension of 4.6 g of the compound of the formula 
(107) and 4.8 g of thionyl chloride in 30 ml of tetrachloroethane. When 
the reaction is complete (90.degree.-120.degree. C.), the mixture is 
allowed to cool and the precipitated product is filtered off with suction 
and dried in vacuo at 90.degree. C. This gives 5.3 g of the 
disulfochloride [melting point 297.degree.(decomposition) recrystallized 
from chlorobenzene]. 3.3 g of disulfochloride in 18 ml of pyridine and 2 
ml of water are heated at reflux temperature for 20 minutes. The solution 
is evaporated to dryness in vacuo and the residue is recrystallized from 
7:3 to 9:1 n-propanol/water, using active charcoal for clarification by 
filtration. This gives 2.4 g of the compound of the formula 
##STR17## 
EXAMPLE 6 
5.24 g of chlorosulfonic acid are added dropwise in the course of 1/2 hour, 
with stirring and at 5.degree. C., to a fine dispersion of 7.7 g of the 
compound of the formula 
##STR18## 
in 100 ml of tetrachloroethane. Stirring is continued for a further 2 
hours at room temperature, and the dark product is filtered off with 
suction, washed with tetrachloroethane and suspended in 150 ml of water. 
The residual tetrachloroethane is removed by azeotropic distillation with 
water at elevated temperature and, at the same time, the mixture is 
neutralized with 30% sodium hydroxide solution until a constant pH of 9 is 
reached. The mixture is evaporated to dryness in vacuo on a rotary 
evaporator, the residue is dissolved in a mixture of 3:2 n-propanol/water, 
n-propanol is added until a ratio of 2:1 is reached, the mixture is 
filtered while hot with active charcoal, and the filtrate is concentrated 
while adding further n-propanol until the product crystallizes out. This 
product is filtered off with suction at 0.degree. C, washed with 
n-propanol and dried in vacuo. This gives 8.8 g of the compound of the 
formula 
##STR19## 
which still contains 1 mole of water of crystallization. The compound of 
the formula (110) used as the starting material is prepared as follows: 36 
g of 30% sodium methylate solution are added dropwise, with stirring and 
at room temperature, to a solution of 36.9 g of 
5-chloro-2-hydroxypropiophenone in 100 ml of DMF. After 2 hours 26 g of 
4,4'-bischloromethylbiphenyl are added and the mixture is heated for 3 
hours at 100.degree., in the course of which methanol may distill off. The 
mixture is cooled to 5.degree. C. and the precipitated product is filtered 
off with suction, washed with ethanol and water and dried in vacuo at 
100.degree. C. This gives 47.6 g of the compound of the formula 
##STR20## 
melting point 167.degree.-8.degree. (toluene). 
2.7 g of sodium methylate are added in portions in the course of 1/2 hour 
at 130.degree. C. to a solution of 27.4 g of the compound of the formula 
(112) in 70 ml of dimethyl sulfoxide. After 2 hours the mixture is allowed 
to cool to room temperature and is diluted with 60 ml of methanol, and the 
precipitated product is filtered off with suction, washed with methanol 
and water and dried in vacuo at 100.degree.. This gives 22.8 g of the 
compound of the formula (110); melting point 233.degree.-5.degree. C. 
(xylene). 
EXAMPLE 7 
The following bisphenol ethers (A.sub.1), dibenzofuranes (A.sub.2) and 
dibenzofuranedisulfonic acids (A.sub.3) are prepared from the 
corresponding components in the manner described above: 
______________________________________ 
##STR21## 
##STR22## 
##STR23## 
(A.sub.2) m.p. 
(A.sub.3) m.p. 
R.sub.2 
R.sub.3 
(A.sub.1) m.p. (.degree.C.) 
(.degree.C.) 
(.degree.C.) 
No. 
______________________________________ 
Cl CH.sub.3 
159-60 232-4 &gt;300 (113) 
CH.sub.3 
C.sub.2 H.sub.5 
166-68 214-5 &gt;300 (114) 
OCH.sub.3 
CH.sub.3 
145-46 240-2 &gt;300 (115).sup. 1) 
H C.sub.6 H.sub.5 
170-71 264-6 &gt;300 (116).sup.2) 
CH.sub.3 
C.sub.6 H.sub.5 
208-10 256-7 &gt;300 (117).sup.2) 
______________________________________ 
.sup.1) In order to obtain the more soluble ammonium salt, neutralization 
is carried out with ammonia instead of sodium hydroxide solution, after 
the mixture has been boiled and the residual tetrachloroethane distilled 
off. 
.sup.2) Sulfonation with SO.sub.3 -dimethylformamide complex (20% excess) 
in nitrobenzene at 120.degree. C. overnight. 
EXAMPLE 8 
A piece of polyamide 66 (nylon warpknit fabric) is heated from 40.degree. 
C. to 98.degree. C. in the course of 30 minutes at a liquor ratio of 1:20 
in soft water containing 0.1% of the compound of the formula (102) 
(percent by weight relative to the textile material) and 3 g/l of 
stabilized bisulfite and 1 ml/l of 80% acetic acid, then subjected to 
treatment at 98.degree. C. for 30 minutes, cooled again to 40.degree. C. 
in the course of 15 minutes, given a cold rinse and dried in a drying 
cabinet at 60.degree. C. 
A high, brilliant degree of whiteness results. When exposed to light in a 
.RTM.Xenotest apparatus by the customary standard method, this white 
effect displays a very good fastness to light. 
EXAMPLE 9 
The procedure followed is analogous to that in Example 8, but the compound 
(103) or the compound (108) or the compound (116) is used instead of the 
compound (102). 
High, brilliant white effects having very good to excellent fastness to 
light also result in this case. 
EXAMPLE 10 
Detergent granules having a residual moisture content of approx. 5% are 
prepared by spray drying a slurry consisting of 1 part of water and 1 part 
of a detergent of the following composition: 
8.4 g of linear dodecylbenzenesulfonate, 
3.1 g of tallow alcohol tetradecaneethylene glycol ether (14 EO), 
3.7 g of Na soap (mainly composed of behenic acid and C.sub.14 -C.sub.20 
-acids), 
45.8 g of Na tripolyphosphate, 
7.9 g of Na silicate, 
2.0 g of Mg silicate, 
1.2 g of carboxymethylcellulose, 
0.2 g of ethylenediaminetetraacetate, 
22.2 g of Na sulfate and 
0.1 g of the compound (102) 
4 g of this detergent are dissolved in 1 l of water (12.degree. of German 
hardness) at a temperature of 30.degree. C. Five pieces of bleached 
cotton, each 10 g, are washed for 15 minutes at 30.degree. C. in this 
bath, then rinsed under cold running water and spun for 30 seconds in a 
spin-dryer at a speed of approx. 1,000 revolutions/minute. This washing 
process is carried out three times and the pieces of cotton are then dried 
and their degree of whiteness is determined by the Ganz method using a 
colorimeter (Zeiss RFC 3). A high degree of whiteness of over 175 is 
obtained. The Ganz method is described in detail in the Ciba-Geigy Review, 
1973/1, and also in the article "Whiteness Measurement", ISCC Conference 
on Fluorescence and the Colorimetry of Fluorescent Materials, 
Williamsburg, February 1972, published in the Journal of Color and 
Appearance, 1, No.5 (1972). 
EXAMPLE 11 
The procedure followed is analogous to that in Example 10, but the compound 
(103) is used instead of the compound (102). A high white effect is 
obtained after washing three times. 
If washing is carried out at 60.degree. C. or 90.degree. C. instead of at 
30.degree. C. under otherwise identical conditions, the resulting white 
effects are even higher. 
EXAMPLE 12 
A washing powder is prepared as described under Example 10. 3 g of 
diperoxydodecanedioic acid (DPDDA) are then homogeneously admixed to 100 g 
of these granules in the dry state. 
STORAGE TEST 
Samples of the detergent W thus obtained (granules A+peracid B) are treated 
as follows: firstly, to monitor the initial value, the content of FWA 
(fluorescent whitening agent) is determined immediately by extraction and 
spectrophotometric measurement of extinction (theoretical value: 0.1% of 
FWA relative to the weight of the granules A); secondly, the granules are 
stored for definite periods of time in cardboard packets as used for 
commercial washing powders, i.e. with a coating,and under selected and 
monitored conditions of temperature and humidity. The FWA content of each 
detergent is determined immediately after storage. The difference from the 
initial value, expressed as a percentage, is a measure of the stability of 
the FWA to the appropriate bleaching agent in the washing powder. 
The determination of FWA mentioned above is carried out as follows: the 
washing powder is thoroughly homogenized by grinding and 200 ml of 
solvent, consisting of 9 parts of dimethyl sulfoxide and 1 part of water, 
are added to 1 g of the washing powder, and the mixture is stirred for 30 
minutes at room temperature. It is then centrifuged for 30 minutes. A 
sample of the clear solution thus obtained is transferred by means of a 
pipette into a 1 cm quartz cell and its extinction in the UV range is 
determined at the absorption maximum against a standard solution of the 
FWA concerned. The extinction is proportional to the concentration of FWA. 
The packet is stored in the opened state at a temperature of 30.degree. C. 
and a relative humidity of 80-85% for 8 weeks, as can occur in household 
use, for example in a washroom. Quantitative determination of the FWA 
shows that the fluorescent whitening agent has excellent stability. 
EXAMPLE 13 
Detergents are prepared as in Example 12. The packets are stored under 
identical conditions, but in the closed state and for 6 months, as can 
occur in practice between the production of the detergent and its use in 
the home. Here too the compound (102) displays a very good stability. 
EXAMPLE 14 
A detergent is prepared as described under Example 10. 100 g of these 
granules are then homogeneously mixed in the dry state with 14 g of K 
monopersulfate and 0.4 mg of CuSO.sub.4 (anhydrous). 
After 3 months storage in a closed packet at room temperature 
(20.degree.-25.degree. C.) only a very small proportion of the compound 
(102), not detectable in the practical use of the detergent, has been 
destroyed. 
EXAMPLE 15 
Detergents are prepared and treated as under Example 10, but 0.1 g of the 
compounds (103) or (108) or (113) is employed in each case instead of the 
compound (102). 
The storage tests are carried out as described in Examples 12 and 13. Here 
too the compounds (103), (108) and (113) display an excellent stability. 
EXAMPLE 16 
Detergents are prepared and treated as described in Example 14, but the 
compound (102) is replaced in each case by 0.1 g of the compounds (103) or 
(108) or (113). Under these conditions too the compounds display a very 
good stability. 
EXAMPLE 17 
The following washing composition is prepared: 
7.8% sodium alkanebenzenesulfonate 
2.8% tallow alcohol tetradecanethylene glycol ether (14EO) 
3.4% sodium soap 
42.5% sodium triphosphate 
7.3% sodium silicate 
1.85% magnesium silicate 
1.15% carboxymethylcellulose 
0.2% ethylenediamine tetraacetate 
20.5% sodium sulfate 
3.0% diperoxydicarboxylic acid 
9.5% water. 
A polyamide 6 textile is washed 5 times, at 55.degree. C. with a 
liquor-to-goods ratio of 20:1, in a solution containing 4 g/l of the above 
washing composition and 0.09% by weight, based on the amount of washing 
composition of, as optical brightener, the compound of formula (103) of 
the application. 
For the purpose of comparison, the test is repeated using, as optical 
brightener, compound 160 according to Sahm et at. U.S. Pat No. 4,002,423, 
namely the compound having the formula: 
##STR24## 
After washing, the textile is dried in the dark and then the degree of 
whiteness is determined, using a Zeiss RFC3-Photometer according to Ganz. 
The following results are obtained: 
______________________________________ 
optical brightener whiteness 
______________________________________ 
compound of formula (103) 
190 
Sahm compound 160 180 
______________________________________ 
A difference in Ganz whiteness between 190 and 180 is substantial. This 
difference of 10 Ganz units is clearly perceivable by an untrained 
observer, and denotes that 30-50 at % more of an optical brightener with a 
Ganz whiteness of 180 will be needed relative to an optical brightener 
having a Ganz whiteness of 190. 
EXAMPLE 18 
A cotton textile is washed 5 times, at 60.degree. C. with a liquor-to-goods 
ratio of 20:1, in a solution containing 4 g/l of the washing composition 
of Example 17, and a specified amount (see Table below), based on the 
weight of the washing composition, of an optical brightener of the 
application. After washing, the textile is dried in the dark, and then the 
degree of whiteness is determined using a Zeiss RFC3-Photometer according 
to Ganz. 
For the purpose of comparison, the test is repeated using, as optical 
brightener, compound 102 of Sahm et al. U.S. Pat. No. 4,002,423, namely 
the compound having the formula: 
##STR25## 
The following results are obtained. 
______________________________________ 
optical brightener 
amount (%) whiteness 
______________________________________ 
compound of formula (103) 
0.10 190 
compound of formula (111) 
0.10 195 
Sahm compound 102 0.20 180 
______________________________________ 
These results show the compounds of the instant application provide a 
better degree of whiteness than twice the mount of compound 102 according 
to Sahm. 
EXAMPLE 19 
A cotton textile is washed 5 times, at 60.degree. C. with a liquor-to-goods 
ratio of 20:1, in a solution containing 4 g/l of the washing solution of 
Example 17, and a certain amount (see Table below), based on the weight of 
washing composition, of an optical brightener of the application. After 
washing, the textile is dried in the dark and then the degree of whiteness 
is determined using a Zeiss RFC3-Photometer according to Ganz. For the 
purpose of comparison, the test is repeated using, as optical brightener, 
compound A, namely the compound having the formula: 
##STR26## 
or compound (3), namely the compound having the formula: 
##STR27## 
each according to Clements U.S. Pat. No. 5,089,166. 
The following results are obtained. 
______________________________________ 
optical brightener 
amount (%) whiteness 
______________________________________ 
compound of formula (103) 
0.10 190 
compound of formula (111) 
0.10 195 
Clements compound A 
0.15 190 
Clements compound (3) 
0.30 190 
______________________________________ 
In order to achieve the degree of whiteness attained with compound (103) of 
the application, 50% more of Clements' compound A must be used, or 3 times 
as much of Clements' compound 3. Even using such excess amounts, the 
Clements' compounds do not reach the whiteness level of compound (111) of 
the application.