IL24322A - Pyrazoline compounds and a process for their production - Google Patents

Description

'nilDl |Π3 TJini"! 'Π PATENT ATTORNEYS · D'QJD 3 PATENTS AND DESIGNS ORDINANCE SPECIFICATION Pyrazoline compounds and a process for their production I (we) j.R. GEIGY A.G., a Swiss company, of Schwarzwaldallee 215 I Basel, Switzerland do hereby declare the nature of this invention and in what manner the same i s to be performed, to be particularly described and ascertained in and by the following statement :- J. R. G E I G ¥ A.G. B A S E L 21 1988* -Ppooooo for tho production of pyranolino oompouft4a The present Invention concerns new pyrazoline compounds processes for the production thereof', their use for the optical brightening of high molecular organic material as well as, as industrial product, the high molecular organic material having a content of the new optical brighteners. 1,3-Diphenyl-pyrazolines which can be substituted in th 5-posltion by a low alkyl group or by a phenyl group which is unsubst ituted or contains non-ionogenic and non-colour imparting substituents , have relatively slight fluorescence and their blue fluorescence has an undesirable greenish tinge. They are thus not very suitable for the optical brightening of textiles, in particular of synthetic polyamide or polyacrylonitrile fibres. The 1-(H '-alkylsulphonyl)- and 1-( '-carbalkoxyphenyD-3-phenyl-pyrazolines have more favourable properties with regard to shade and intensity of the fluorescence. Thus, the substitution of the phenyl group in the 1-position by an alkylsulphonyl or carbalkoxy group in p-position to the nitrogen bond causes an improvement in the properties. Similar substitution in the m-position of this benzene ring however, has somewhat less of an influence. But the substitution of this phenyl group by halogen From these facts, it would be thought that the substitution of this phenyl group, by halogen in the m-rposition to the nitrogen bond would hardly lead to technically useful optical brighteners for textiles.

It has now been found, however, that surprisingly active optical brighteners having a neutral white shade are obtained with a v II) or with a ketone reacting in the same way as that vinyl ketone, of formula III ' ' W - CH - CH2 - CO - A (III) R wherein W represents chlorine, bromine or a tertiary amino group, to form a pyrazoline compound of formula IV in which formulae X. represents halogen or the tri'fluoromethyl ^group, Y represents hydrogen, halogen , a . low alkyl group or an optionally esterified carboxyl group, Z represents hydrogen, halogen or a low alkyl group, R represents hydrogen, a low alkyl group or a phenyl, halophenyl or fur.yl radical, and A represents a phenyl radical optionally mono- or di- -- .. substituted by halogen .atoms or alkyl, alkoxy, acylamido, alkoxycarbonylamido , benzamido or alkylsulphonylamido groups.

The new l-(3'-halogeno)-or l-( 3 ' -trifluoromethyl-phenyl) -3-phenyl-pyrazolines of formula IV have better fastness to light than the previously known l-(4'-carbalkoxyphenyl)-3-phehyl-pyrazolines . They are distinguished over ' the known 1-(4' -alkylsulphonyl)- and l-( 41 -sulphamoylphenyl) - 3-phenyl-pyrazolines by a neutral, i.e. less reddish, white shade and by better fastness to washing. They are also more easily accessible To attain a quite definite white shading, the use of mixtures of pyrazolines according to the invention has often proved to be advantageous. Such mixtures can be in the form of purely mechanical mixtures of the individual components or in the form of actual crystal compounds the crystal structure of which is different from that of the individual components. ' Such mixtures can be produced on the one hand by dry mixing, melting or recrystallising together the individual components. On the other hand, the desired pyrazoline mixtures can be obtained by using 'a starting material which is already in the form of a mixture, e.g. by reacting a hydrazine of formula I -4- 24322/2 with a ketone mixture of the formulae W - A' ·' wherein A und A' represent two different radicals of those defined above under A. Those mixtures which contain pyrazolines with and without halogen in the phenyl nucleus in the 3-position are particularly advantageous. The 3-( 4"-halogenophenyl) derivatives fluoresce blue to blue-greenish whilst the products without halogen in the 3-phenyl nucleus fluoresce violet to blue.

Valuable mixtures are, for example: l-(3'-chlorophenyl)-3-(4"-chiorophenyl)-pyrazoline) admixed with the following pyrazolines: l-( 31 -chlorophenyl)-3-phenyl-pyrazoline, · ■ ' l-( 3 ' -chlorophenyl) -3-( 4"-methoxyphenyl) -pyrazoline , l-( 3 ' -chlorophenyl) -3- ( 2" , 5"-dimethoxy henyl) -pyrazoline, l-(3l-chlorophenyl)-3-(4,,-acetylaminophenyl)-pyrazoline, : l-( 3 · -chlorophenyl) -3-( " -methylphenyl) -pyrazoline.

** When either X or Y or Z in formulae I and IV is halogen, then it is chiefly fluorine, chlorine .or bromine.

If Y or Z or R is a low alkyl group then this has preferably, 1 to 4 carbon atoms.

Esterified carboxyl groups in the position of Y are preferably derived from alkanols. Y can be, for example, the If R ie the phenyl radical it is optionally substituted by halogens, such as fluorine, chlorine or bromine* The principal non-ionogenic and non-colour imparting substituents in the phenyl radical A are halogens such as fluorine, chlorine or bromine, low alkyl and alkoxy groups or acylamido groups, i.e. carbacylamido, e.g. low alkanoylamido groups or alkoxy-carbonylamido groups, preferably containing a low alkoxy radical.

When W represents tertiary amino groups, it is especially a di-low-alkylamino group, preferably the dimethyl-amino group.

Compounds of formula IV wherein X is chlorine, Y, Z and R are each hydrogen and A is the phenyl or p-chlorophenyl group are preferred because of their relatively easy accessibility and their good fluorescence properties.

I The phenylhydrazines of formula I used as starting materials are obtained from the diazonium salts of correspon¬ dingly substituted anilines by reduction by the usual methods.

Starting materials of formula II. can be produced, for example, . by condensation of a ketone of the formula CH^CO-A with an aldehyde of the formula R-CH=0.

. Starting materials of formula III wherein W is chlorine or bromine are obtained, e.g. by condensation of an. acid chloride of the formula W-CH-CK2-C0-C1 such as β-chloro- or β-bromo- propionic acid chloride, with the desired aryl compound A-H -according to Friedel-Cra ts $ starting materials of the. formula III wherein W is a tertiary amino group are' obtained, e.g. from the corresponding methyl-aryl ketones ,■ aldehydes , chiefly formaldehyde, and secondary'amines , particularly dimethyl amine, by the known method according to ' annich.

For the production of pyrazoline compounds of formula IV wherein R is not hydrogen but is a low alkyl group and is particularly a phenyl, hal'ophenyl or iuryl radical, preferably vinyl' ketones of formula. II are used as starting materials, ■whilst pyrazolines of formula IV wherein R is hydrogen are produced advantageously by the use of a ketone of formula III.

The reaction of the phenylhydrazine"of formula I with* the ketone of formula II or III' is performed by methods known per se, advantageously at a raised temperature and in organic or aqueous organic solution, the organic part of the -solution preferably consisting of low alcohols such as methanol, ethanol, 'butanol or ethylene glycol mono-low-alkyl ether.

On using vinyl ketones of formula II as starting materials, acids in at least a catalytic amount are necessary. Both inorganic acids, e.g. halogen hydracids such as hydrochloric or hydrobromic acid or sulphuric acid, and organic acids, e„g acetic acid are suitable.

If ( β-chloro) -or (β-bromo- alkyl) -phenyl ketones of formula III are used as starting materials, then acid binding agents are necessary'. As such are suitable, e.g. organic tertiary nitrogen bases, such as pyridine or inorganic bases such as alkali carbonates or bicarbonates. On using ( β-tert.aminoalkyl) -phenyl ketones of formula III as starting materials, the presence of alkalies, e.g. alkali hydroxides, carbonates or bicarbonates is recommended.

Generally, the reaction occurs- easily and under, mild conditions and very good yields of end products are obtained.

The new pyrazoline compounds of formula IV are almost colourless to yellowish coloured, well crystallised substances' which are difficultly soluble to insoluble in hot water. They dissolve in organic solvents, e.g. in alkanols, low fatty acids, low fatty acid esters, low fatty acid amides, ' low ketones and in optionally halogenated aromatic hydrocarbons. The almost colou'rless organic solutions are distinguished by vivid violet to blue luorescence.

The new pyrazoline compounds are suitable for the optical brightening of high molecular organic material. By high molecular organic material is meant principally synthetic organic polyplastics , i.e. plastics obtained by polymerisation, polycondensation and polyaddition, e.g. polyolefins . such as polyethylene or polypropyle e, also polyvinyl chloride, polyacrylonitrile and copolymers thereof, polyamides and cellulose esters.

The high molecular organic material is optically brightened, for example, by incorporating thereinto slight amounts of optical brighteners according to the invention, preferably 0.001 to 0.3 calculated on the material to be brightened, optionally together with other substances such as plasticisers , pigments etc. Depending on the type of it- in the polymer mass or, together with the polymer, in solvents. The material is then brought into the desired form by the known process such as calendering, pressing, extruding, painting, pouring or injection moulding.

Preferably however, high molecular organic material is brightened in the form of fibres, for example, polyamide, poly-acrylonitrile and copolymers thereof, cellulose esters, such as cellulose acetate fibres. Advantageously an aqueous dispersion of pyrasolines of formula IV is used to brighten these fibres. Preferably the brightening dispersion contains 0.01 to 0,2% of pyrazoline according to the invention, calculated on the fibres. In addition, it can also contain auxiliaries such as dispersing agents, e.g. condensation products of fatty alcohols having 10 to 18 carbon atoms with 1 to mol of ethylene oxide, or condensation products of alkyl mono- or poly- amines having lo to 18 carbon atoms with at least 10 mol of ethylene oxide and, if polymeric or copolymeric acrylonitrile fibres are to be brightened, the dispersion can also contain acids, especially organic acids such as acetic, oxalic and, preferably, formic acid.

The fibres are brightened with the aqueous brightening dispersion either by the exhaustion process at temperatures of preferably 30 to 100°C, or in the foulard. In the latter .case, the goods are Impregnated with the. brightening dispersion and finished, for example, by steaming at 70 to 100°C with, preferably, saturated neutral' steam. The finished fibres are the High, molecular organic material opticall 'brightened according to the invention, particularly the synthetic fibres brightened by the exhaustion process, have a pleasant, pure white, blueish fluorescent . appearance .

Also soaps and detergents can be optically brightened with the pyrazolines according to the invention, for example, soaps, soluble salts of higher fatty alcohol . sulphates , higher and/or polyalkyl-substituted arylsulphonic acids, or ''. . ... . .". '.. ' sulphocarboxylic acid esters of medium to higher alkanols, higher alkanoylaminoalkyl- or alkanoylamino-aryl- carboxylic or sulphonic acids, or of fatty acid glycerin sulphates 5 also non-ionoid detergents such as higher alkyl-phenol polyglycol ethers. Such soaps and detergents containing pyrazolines of formula IV can also be used for the brightening of textiles.

Washing agents brightened according to the- invention can contain the usual fillers and auxiliaries, e g.. alkali poly- and polymeta- phosphates, alkali silicates, alkali borates, alkali salts of carboxymethyl celluloses, foam stabilisers such as alkanolamides of higher fatty acids, or complex compounds such as soluble salts of ethylenediamine tetraacetic acid.

The new pyrazolines are incorporated into the washing agents or into washing liquors advantageously in the form of their solutions in neutral, water miscible and/or easily volatile organic solvents such as low alkanols, low alkoxyalkanols dispersing agents. For example, they can be mix 3d, kneeded or milled with the wash-active substances and then the usual auxiliaries and fillers can be added. The brightening agents are stirred with the wash active substances, usual auxiliaries and fillers and water to form a slurry, for example, and this is then sprayed in.an atomising drier. Also, the new pyrazo-line derivatives can be admixed with prepared washing agents, e.g. by spraying a solution In an easily volatile and/or water soluble organic solvent onto the dry washing agent which is kept in continual movement.

' The content of optical brlghtener of formula IV in washing agents is advantageously 0.001 - 0. #> calculated on the solid content of the washing agent. Such washing agents containing optical brighteners of formula IV have a very much .improved, white appearance in daylight than those not containing brlghtener.

Textile fibres, e0g. synthetic -polyamide and cellulose ester fibres, washed in liquors containing the pyrazolines of formula IV are given a brilliant appearance in daylight. They can thus be used especially for the washing of these synthetic fibres or of textiles or components consisting of such fibres, and of household articles . For use in the household wash, they can also contain other optical brighteners having affinity to other fibres, for example, to cellulose.

Further details can be see from the following examples. The temperatures are given therei in degrees Centigrade.

Example 1 1 .7 g of 3-chlorophenylhydrazine hydrochloride are dissolved in a mixture of 300 ml of ethanol and 100 ml of water. 30 g of sodium carbonate are added to the solution and it is heated to 70 - 80°. A solution of 25 g of ( β-dimethykmino-ethyl)- (^-chlorophenyl) -ketone hydrochloride in 100 ml of water is added to this solution while stirring at this temperature 5 the addition being made dropwise within 1 hour. The reaction mixture is then refluxed for about l hours while stirring well. It is cooled, the precipitate is filtered off, washed until the washing water no longer has an alkaline reaction and dried. 28 g of 1- (3 ': -chlorophenyl)-3= (W "-chlorophenyl )-pyrazo-line, 96. 0 °- the ' theoretical calculated on the (β-dimethyl-amino-ethyl)- ( -chlorophenyl) -ketone used, are obtained, - It is a yellowish crystalline powder which melts at 121-122° (uncorrected) . On recrystallising from ethanol, the pyrazoline mentioned is obtained, in a form pure enough for analysis as pale yellowish needles. In organic solvents this product has an intensive blue to blue-violet fluorescence. It is suitable for the optical brightening of synthetic polyamide fibres.

If instead of the 19 „ 7 g of 3-chlorophenyl hydrazine hydrochloride, equivalent amounts of the hydrochloride of one of the phenyl hydrazines given in column II of the following Table is used and, instead of the 2 g of (β-dimethylamlno- ethyl)-(W-chlorophenyl)- ketone hydroride, corresponding amounts of the hydrochloride of one of the β-tert. aminoalkylphenyl ketones given in column III are used and the procedure describe in example 1 is followed, then corresponding end products are obtained, the melting points of which are given in column IV o -the Table. .

Table 1 II . Ill ... IV phenylhydrazine (|3-tert.aminoalkyl)^henyl)*etone K.P ° II III IV phenylh drazine (P-tert,aminoalkyl)-(phenyl)-ketone M.P HOO 257° (decomposition) 79 - 80° II III' IV phenylhydrazine (β-tert.aminoalky.(l-( phenyl)- Μ^ρ< ketone ° II III IV phenylhydrazine (β-ter .aminoalkyl)-(phenyl )- M.P. ketone II III IV . phenylhydrazine (β-tert.aminoalkyl)—(phenyl)- M.P. ' ketone II ΙΙΪ IV enylhydrazine (β-tert .aminoalkyl )-(phenyl )- M.P, ketone Example 48 12 g of 3-chlorophenyl hydrazine hydrochloride and 12 g of p-chlorophenyl-l-propenyl ketone are refluxed for 3 hours while stirring in 150 ml of ethanol. On cooling, the reaction product separates in the form of cream-colored lamellae. It is filtered, washed with water and recrystallis ed from ethanol. The l-( 35 -ehlorophenyl) -3-( "-chlorophenyl) -5-methyl pyrazoline thus obtained forms faintly yellow crystals melting at 117 to 118° and having a blue fluorescence in ultraviolet light.

The compound dissolves in ethyl- acetate with a deep blue-violet fluorescence. It can be used to brighten polyamide fibers.

When in this example the 12 g of p-chlorophenyl-1-propenyl-ketone are replaced by 13 g of p-chlorophenyl~l-butenyl-ketone, l-( 31 -ehlorophenyl) -3-( 4"-chlorophenyl) -5-ethyl-pyrazoline M.P.'85° is obtained which has very similar properties as the above-described 5-methyl derivative.

Example 49 19.7 g of 3-chlorophenylhydrazine hydrochloride, 17.0 g of β-chloropropiophenone and l6 g of pyridine are added to lWo ml of methanol. The mixture is refluxed for 2 hours.

After cooling the reaction mixture, the precipitate formed is filtered off, washed once with a little cold methanol and dried. 22g of l-(3 '-chlorophenyl)-3-phenyl-pyrazoline are obtained in the form of almost colourless needles which melt at 102° (uncorrected). The yield is thus 86$ of the theoretical (calculated o the 3-!-ehlorophenylhydrazine hydrochloride used). O recrystallislng from ethanol, the -product is obtained as pure white needles which have a blue fluorescence and is sufficiently pure for analysis. In daylight, the solutio of this pyrazollne in toluene has a vivid violet fluorescence. This compound also is suitable for the optical brightening of synthetic polyamide fibres. g.of 3-chlorophenyl hydrazine hydrochloride . and 12.2 g of benzal-H-chloroacetophenone in 120 ml of ethanol are refluxed for 10 hours while stirring. The reaction product -^separates as almost colourless precipitate. After cooling, . the product is filtered off, washed with ethanol and recrystal- lised from a mixture of 50 ml of chlorobenzene and 100 ml of ethanol. The so purified l-(3'-chlorophenyl)-3-(V'-chloro- phenyl)-5-phe yl-pyrazoline forms colourless crystals which fluoresce blue i UV light. M.P. 121-122°. The yield is l .8g The new compound dissolves in ethyl acetate with an intensive blue-violet fluorescence. The product can be used for the brightening of polyamide fibres.

If in this example the 12.2 g of benzal-H-chloroaceto- phenone are replaced by 13.8 g of -chlorobenzal- '-chloro- acetophenone or by 11.6 g of (3-furyl-(2)-vinyl)-(1+'-chloro- phenyD-ketone, then 17.5 g of 1-C3 '-chlorophenyl)- , 5-bis- (V'-chlorophenyl)-pyrazoline, M.P. 135°, or 13»8 g of l-(3'- c loro hen l ^-t '-chlorop e y^^- ur l-^' )-pyrazoline , M.P. 131-132° respectively are obtained. These products have . properties very similar to those of the 1- (3 ' -chlorophe yl)-3- (V-chlorophenyl)-.5-phenyl-pyrazoline described above.

Example 51 100 g of polyacrylonitrile yarn, e.g. COURTELLE (Courtaulds, London) are introduced at 50° into a bath consisting of 3000 ml of water, 1 g of the condensation product of 1 mol of stearyl alcohol and 22 mol of ethylene oxide, 3 g of 8$% formic acid and 0„1 g of 1- (3 '-chlorophe yl 3-( "-chlorophenyl)-pyrazoline. The bath is heated to 100° within 15 minutes and the yarn is left in the circulating liquor for 30 mi-nutes at 100°. Afterwards, the yarn is well rinsed with cold water, centrifuged and dried at 50-60°.

The fibres so treated have a pleasant, white appearance . , If instead of the brightener mentioned above, l-(3'-bromophenyl)-3- (W"-chlorophenyl)-pyrazoline is used and otherwise the procedure described in the example is followed, then similar brightening effects are obtained on the fibres mentioned.

Example 52 Polyacrylonltrile fabric such as ORLON (Du Pont de Nemours, Wilmington, Del. USA) is impregnated in a foulard with a bath containing 1 g of 1- (3 '-chlorophenyl)-3- (HM-chlorophenyl)-pyrazollne, 10 g of $0% acetic acid and 2 g of condensation product of 1 mol of N-stearyl-ethylenediamine and 2 mol of styrene oxide and 0 mol of ethylene oxide in 1000 ml of 30° warm water. The fabric is squeezed out to a moisture content of about 60 , rolled up and steamed in a pad-roll apparatus for k hours at 95°. Afterwards it is rinsed on a full width washing machine first. with 50° warm and then with cold water and dried. A fabric having a beautiful white appearance is obtained.

Similar brightening effects are attained if, instead of the brightener described above, l-(3 ' -fluorophenyl) -3-(V'-chlorophenyl)-pyrazoline, l-(3 '-chlorophenyl)-3- (2,! , 5"-dimethoxyphenyD-pyrazoline or 1- (31 -trlfluorometh lphenyl)-3- (H "-chlorophenyl)-pyra oline is used and otherwise the procedure described irx the example is followed..

Example 53., g of a pale yellowish Nylon staple fibre fabric (E.J. Du Pont de Nemours, Wilmington, Del. USA) are treated in a bath, liquor ratio l:*+0, which contains 0.01 g of 1-(31 -chlorophehyl)-3-phenyl-pyrazqline and 0.2 g of an olein alcohol pentadecaglycol ether. The goods are treated for 30 minutes at 75°, then rinsed and dried. Nylon fabric so treated has a much whiter appearance in daylight than the same but untreated fabric.

Example 54 g of undyed acetyl cellulose yarn are treated for 30 minutes at 75° in a bath, liquor ratio 1:30, which contains 0.01 g of l-(3 ,-chlorophenyl)-3-(1+"-chlorophenyl)-pyrazoline in a finely dispersed form. The yarn so treated, after rinsing and drying, has a considerably more white appearance than before treatment.

Example 55 0o2 "g of 1- (3 '-bromophenyl)-3-(V'-chlorophenyl)-pyrazollne, 5 g of titanium dioxide (Anatas), 75 S of cellulose acetate and 25 g of diethyl phthalate in 900 g of acetone are homogenised into an opaque solution and this is poured onto glass plates. After evaporating the acetone, a transferable opaque film is obtained which has a much clearer white aspect than a comparative sample produced without brlghtener.

Example 56 100 g of high pressure polyethylene in the form of a granulate and 0„006 g of l-(3 '-chlorophe yl)-5- (V*-chlorophenyD-pyrazoline are mixed dry at room temperature and then processed into a tube in an extruder at 120-130°. In daylight the tube obtained fluoresces blue-violet and has a considerably higher degree of whiteness than ;one made without brlghtener.

Example 57 0.05 g of l-(3 ' -·chlorophenyl)-3-(½',-c loro henyl)-pyΓazoline are gelatinised on a set of mixing rollers at l60° for 1 minutes with a mixture consisting of 67g of polyvinyl chloride powder,.33 g of dioctyl phthalate, 2 g of di-n-butyl dilauryl dloxystannate and 0„3 g of sodium pentaoctyl tripolyphosphate, and then drawn out into sheets. Polyvinyl chloride sheets so produced have a considerably more white< appearance in daylight than corresponding sheets which are produced- without the addition of this brightener., O.08 g of l-(3'-bromophenyl)-3~phenyl-pyrazoline and 7 g of titanium dioxide (Anatas), 67 g of polyvinyl chloride 33 g of dioctyl phthalate, 2 g of dibutyl-tin-dilaurate and 0.3 g of sodium pentaoctyl tripolyphosphate are processed as described above into an opaque sheet. The sheet so produced has a much more white appearance than a comparative sample produced without brightener.

Example 58 200 g of soap powder and 0.2 g of 1- (3 ' -chloro-phenyl)-3-phenyl-pyrazoline are processed with. OO ml of water at 80° into a homogeneous mass which is "then dried in vacuo at 70-80°. A clearly brightened soap is obtained which can be converted in the usual way into tablets or, by pulverising, into a powder. 4 Example 59 To produce a fine washing agent, g of sodium dodecyl benzene sulphonate and yi 8 g of sodium salt of laurifl. alcohol . sulphate , are stirre with 80 g of water and processed at 6o~70° with 0.1 g of l-(3 '-chlorophenyl)-3-(2t*, 5"-dimethoxyphenyl)- pyrazoline into a homogeneous mass. 2 g of lauric acid monoethanolamide , 8 g of sodium tripolyphosp ate , 1.5g of carboxymethyl cellulose and 60. g of sodium sulphate are added to the mixture, the whole is well mixed and is dried and pulverised. g of white nylon are washed for.1? minutes' at 35° in 200 g of an aqueous liquor which contains 1.0 g of the washin agent described above, rinsed and dried. The washed goods have clearly a more white appearance than similar nylon goods which in a similar way have been washed/wit a washing agent of analogous cqsoosi tio.i * but not containing brightener.

Fabrics or articles made of cellulose acetate can be washed and simultaneously optically brightened in the same way.

.Example 60 lOOg of a synthetic detergent, consisting of . g of dodecylbenzene sulphcnate, yi 3.8 g of sodium salt of lauri-a alcohol sulphuric acid ester, 2 .6 g of- sodium polyphosphate 7.6 g o tetrasodium pyrophosphate .8 g of water glass (sodium silicate) 1.9 g of magnesium silicate .0 g of sodium carbonate .1 g of carboxymeth l cellulose 0.3 g o tetrasodium salt of ethylenediami e tetraacetic acid 3^ g of sodium sulphate and 100 g o water are stirred into a homogeneous slurry, 0.1 g cf the sodium salt of h , "■ -bis- [ k" , 6,:-diphenylamino-l" ,3" , 5"-triazi-nyl- (2")-aminc]-stilbene-2525-disulphonic acid and 0.05 g of 1- ( 3 ' -fluorophenyl)-3- "-chloropheayl)-pyra2oline are added , well mixed in and the whole is then sprayed from- an atomising drier. ■ 100 g of goods consisting of 30 g of' undyed nylon fabric and 70 g of undyed cotton fabric, are washed for 10 minutes at 8 ° in a liquor, liquor ratio 1 : 10 , containing 8 g of the detergent containing brightener described above. The goods are then rinsed. and dried. Both types of fabric are beautifully brightened by this washing process.

Example 61 A non-ionoge ic washing agent is produced by veil . mixing the following components: 11 g of nonylphenol polyglycol ether having 15 ethyleneoxy groups , 11 g of water, . 33 g of sodium tripclyphosphate 11 g of sodium pyrophosphate g of sodium silicate / 20 g of Glaubers salt ~" . 2 g of sodium carbonate 2 g of carboxymethyl cellulose 0„ 2g of l-(3 ?-chlorophenyl)-3- (½':-chlorcphenyl)-pyrazoline „ Shirts made of ladder-proof nylon tricot material are washed for 20 minutes at 0° in a liquor, liquor ratio 1:15, 'which contains 5 g of this washing agent per litre. After rinsing and drying, shirts so washed have a brilliant white appearance.

Example 62 0.1 g or the sodium salt of H ! -bis . [ W"-phenylamino-6"- (N-methylethanolamino)-l" ,3" , 5"- r iaainyl- ( 2,t)-amiao J -s til-be ne-2 , 2s -disulphonic acid and 00θ6 g of 1- ( : -chiorcphenyl)-3~ ( '-chlorophenyD-pyrazoline are added, at 85-90° to a hot liquid washing composition of the following composition: o g of sodium soap based on lauric, myristic and- palmitic- acid, 31 g of sodium phosphate 9 ■ g of sodium pyrophosphate 6 g of water glass 3 g of magnesium silicate 0.5g of tetrasodium salt of ethyle ediamine tetraacetic ac id g of sodium carbonate « o οί' sodium sulphate 70 g of water.

The whole is well mixed and finally dried in an atomising drier, A washing agent which can be sprinkled is obtained. 100 g of undyed polyamide/cotton mixed fabric are washed for 20 minutes in a 6o° warm liquor, liquor ratio 1;209 which contains l6 g of the washing agent described above. After rinsing and drying, the washed mixed fabric appears brilliant Example 63 The. following components of a washing agent * 21. g of dodecylbenzene sulphonate , 32,6 g of sodium tripolyphosphate , 1„ 1 g of sodium carbonate, H°5 g °ί' sodium silicate and 19 o 2 g of sodium sulphate are processed at 8o° into a homogeneous mass with 75 g of water and, after the addition of 0o l g of sodium. salt of U , >-bis-[i+"-phenylamino~6,!-(i3- me hoxyethylamino)-!'1 , 3 " , 5"-triazinyl- ( 2" )-amino] - stilbene- 2 , 2 :-disulp.honic acid and 0. g of l- ( '-fluorophenyl) -3- "-chlcrophenyi ) -pyrasoline the whole is well mixed and dried in an atomising drier,- The powder obtained is then worked into 12 „ 7 g of sodium perborate „ O g of goods consisting of 10 'g of undyed polycapro-lactam fabric and 0 g of undyed cotton fabric are washed for 30 minutes at 35° with a solution of g of the washing agent described above in 1000 g of water. Dazzlingly white goods are obtained.

Example 64 A heavy duty detergent mixture consisting of dodecyl benzene sulfonate 15.2 parts lauryl sulfate 3.8 parts sodium tripolyphosphate 25.6 parts tetrasodium pyrophosphate 7.6 parts anhydrous sodium silicate 4.8 parts magnesium silicate 1.9 parts sodium carbonate 5.0 parts carboxymethyl cellulose 1.4 parts sodium ethylenediamine tetraacetate 0.3 parts sodium sulfate 24.0 parts water content 10.4 parts is mixed' with parts of l-( 3 ' -chlorophenyl) -3-( "-chlorophenyl) -pyrazoline in the following manner: The brightening agent is first thoroughly mixed' with 10 parts by volume of normal sodium hydroxide solution and then after addition of 250 parts by volume of water, worked together with the heavy duty detergent mentioned (200 parts) into a homogeneous smooth slurry. The paste obtained is dried for 10 hours at 100° and then crushed. The washing powder obtained is homogeneously mixed in the dry state with 10 parts of sodium perborate. A perborate washing powder is obtained which has a beautiful white effect. This white effect is maintained even when this mixture is stored with a water content of 5% for 14 hours at 35 to.40°.

Example 5 100 g of undyed cellulose acetate tricot underlinen are washed for 1 minutes at 30-35° in a liquor, liquor ratio 1:15} which contains 0„75 g of nonylphenol polyglycol ether, 2 g of sodium tripolyphosphate , 1 g of sodium pyrophosphate, 1*5 g of Glaubers salt and 0o01 g of l-( 1 -bromophe yl)-3- (V'-bromophenylj-'pyrazoline . The goods are then rinsed and dried. Fabric so treated has a much more brilliant appearance than that washed without the addition of brightener« Example 66 26 g of l-( 3 ' -chlorophenyl) -3-phenyl-pyrazoline and 30 g of l-( 3 ' -chlorophenyl) -3-( " -chlorophenyl) -pyrazoline are well mixed and the mixture is heated to 100° . A yellow homogeneous melt is obtained which solidifies into a pale yellow crystal mass on cooling The product, which melts at 85-90° , has a crystal structure different from that of the starting components and can also be used for the brightening of polyamide fibres „ Material brightened therewith has a less blue-greenish white effect than a comparative sample brightened with l-( 3 ' -chloro-phenyl) -3-( 4" -chlorophenyl) -pyrazoline „ Example 67 30g of l-( 3 ' -chlorophenyl) -3-phenyl-pyrazoline and 20 g of l-( 3 ' -chlorophenyl) -3-( " -chlorophenyl) -pyrazoline are dissolved in 1250 ml of ethanol and the solution, is left to cool. The product which crystallises out in almost colourless white needles melts at 80-83° and, in addition to pure crystals of l-( 3 ' -chlorophenyl) -3-phenyl-pyrazoline, it contains a crystal compound consisting of both components <> This crystal compound has the same structure as that obtained according to example 66» The product dissolves better in organic solvents than the individual components and is also suitable for the optical brightening of polyamide substrata „ Example 68 240 g of sodium carbonate are added to 197 g of 3-chlorophenyl hydrazine hydrochloride, 750 ml of butanol and 1000 ml of water and the whole is heated to 90°. A solution consisting of 125 g of ( β-dimethylamino-ethyl) -( -chlorophenyl) -ketone hydrochloride, 107 g of ( β-dimethylamino-ethyl) -phenyl ketone hydrochloride and 1000 ml of water is added dropwise to this mixture within 1 hour at 90-95° and then the whole is refluxed for' 12 hours while stirring. The brownish butanol solution is removed from the aqueous phase and allowed to cool. Pale yellowish crystals separate out which are filtered off, washed with methanol and dried at 70°.

The product has similar properties to that produced according to example 66» Example 69 A light duty detergent is produced by stirring 20 g of sodium dodecyl benzene sulphonate and 8 g of sodium salt of laur'in alcohol sulphate in 80 g of water, 0.06 g of l-(3'-chlorophenyl) -3-phenyl pyrazoline and 0.05 g of l-( 3 ' -chloro-phenyl) -3-( 4"-chlorophenyl) -pyrazolone are added and the whole is worked into a homogeneous mass at 60-70°. 2 g of lauric acid monoethanolamide, 8 g of sodium tripolyphosphate , 1.5 g of carboxymethyl cellulose and 60.49 g of sodium sulphate are added to the mixture, the components are well mixed, the mixture is dried and the particle size is made smaller.

Instead of the above mechanical mixture of 0.06 g of ·1-( 3 ' -chlorophenyl) -3-phenyl-pyrazoline and 0.05 g of l-( 3 ' -chlorophenyl) -3-( "-chlorophenyl)-pyrazoline, also 0.11. g of the brightening .mixture produced according to example 66, 67 or 68 can be used.

If 10 g of white nylon are washed for 15 minutes, at 35° in 200 g of an aqueous washing liquor which contains 1.0 g of the light duty detergent described above, then rinsed and dried, the nylon so washed has a considerably more white appearance than similar nylon which has been washed in the same way with a light duty detergent of analogous composition but which does not contain the brightening mixture.

Claims (10)

1. Compounds of formula IV R in which formulae X represents halogen of the trifluoromethyl group, Y represents hydrogen, halogen, a low alkyl group or an optionally esterified carboxyl group, Z represents hydrogen, halogen or a low alkyl group, R represents hydrogen, a low alkyl group or a phenyl, halophenyl or furyl radical, and A represents a phenyl radical optionally mono- or di- Bubstituted by halogen atoms or alkyl, alkoxy, acylamido alkoxycarbonylaraido,, benzamido or alkylsulphonylamiclo groups.

2. Process for the production of pyrazoline compounds of formula IV in Claim 1 characterised by reacting a phenyl hydrazine of formula I Z with a vinyl ketone of formula II R - CH m CH - CO - A (II) or with a ketone reacting like that above of formula III W - CH - CH - CO - A (III) E c m l e R ∑ and 2 h ve the s me me nin s in 24322/2

3. Process according to Claim 2, characterised by the φ use of a compound of formula I wherein X is chlorine and Y and Z are both hydrogen and by the use of a compound of formula II or III wherein R is hydrogen and A is the phenyl or p-chloro-phenyl group.

4. Process for the optical brightening of organic material characterised by the use of an optical brightener of formula IV in Claim 1.

5. Organic material characterised by a content of at least one optical brightener of formula IV, in Claim 1.

6. Washing agents and also liquors prepared therewith, characterised by a content of wash-active substances and at least one optical brightener of formula IV, in Claim 1.

7. Process for the optical brightening of organic material, characterised by the use of a mixture of optical brighteners of formula IV,: in Claim 1.

8. Process according to Claim 7, characterised by the use of a mixture of 1-(3'-chlorophenyl)-3-phenyl-pyrazoline and 1-(3'-chlorophenyl)-3-(4M-chlorophenyl)~pyrazoline.

9. Detergents and also washing liquors prepared therewith characterised by a content of wash-active substances and a mixture of optical brightening agents of formula IV in Claim 1

10. Detergents and washing liquors prepared therewith according to Claim 9, characterised by a content of wash-active substances and a mixture of 1-(3t-chlorophenyl)*3-phenyl-pyrazoline and 1-(3'-chlorophenyl)-3-(4"chlorophenyl)-pyrazoline.