DE1695119A1 - Fluorescent 1,3-diarylpyrazole compounds and their use as whiteners - Google Patents

Description

JR G ei-g y- AG, Basel 3-2551 *

Dr. R.-Koanig Merger
Dipt.PKy5.ii.Hoitbaüe

Poienlanwciie , _m

Munich 2, Bräuhau «** · 4 / lU

end 1., 3-diarylpyrazo

Münch

Fluorescent 1., 3-diarylpyrazole compounds

and their use as whiteners

The present invention relates to new fluorescent 1,3-diarylpyrazole compounds which are valuable as ¥ ice creamers for ¥ ash agents, paper, textiles and plastics, and processes for their production. ^ k

1,3-diphenylpyrazolines, the simple ring substituents, such as halogen, lower alkyl, alkylsulfonyl, carboxyl, 'carbalkoxy or contain sulfonic acid amide groups, are characterized by very lively fluorescence and have therefore achieved great industrial importance as Yeisstö'ner despite certain disadvantages.

As, disadvantages of these monosubstituted pyrazolines. have a relatively low affinity for cellulose fibers, to mention a poor lightfastness and a limited resistance to oxidative influences.

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'The new 1,3-diarylpyrazoles according to the invention are on the other hand, they are remarkably stable to oxidation and have a very good affinity for textile fibers. They excel in compounds of similar composition known to this property, which only in the 1-position one accordingly contain substituted phenyl radical.

The present invention accordingly provides Pyrazo compounds of the general formula I.

I NR ₄

R - Γ - f / (!)

R ₃

In this formula mean

R, and R independently of one another each represent the remainder of one or polynuclear, uncondensed or condensed aromatic Carbo- or Heteroeyclus, which by a ring carbon atom of an aromatic nucleus with connected to the pyrazole ring, of which residues

R. and R ₄ an optionally substituted styryl radical in conjugation to the pyrazole bond

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Rp hydrogen or a monovalent Substi

do it, especially one if necessary substituted hydrocarbon radical, and

Ro preferably hydrogen or a monovalent one

Substituents, in this case especially the methyl group, where R-, and R _? together with the associated ring members of the pyrazole ring can also form a fused ring. Within the scope of this broadest definition of the invention

result in the following preferred embodiments, each individually or in combination with each other, particularly interesting and valuable realizations of the subject of the invention:

In a first preferred embodiment of the invention means the radical R ^ or R *, which optionally contains substituted styryl radical in conjugation to the pyrazole bond, an optionally further substituted 4-stilbyl radical.

In a further preferred embodiment of the invention this 4-stilbyl radical is in the 1-position of the Pyrazole ring and in "its 3-position an optionally

■ i

substituted phenyl radical, where as substituents in particular ~ Halogen, alkyl, alkoxy and sulfonic acid groups come into question.

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In a further preferred embodiment of the Invention contains the 4-stilbyl radical in the p-position to Vinyl group is a common one there in white speakers of the stilbene series Substituents.

In a further preferred embodiment of the invention, the p-substituent of the stilbyl group is a 3-phenylpyrazolyl (I) group.

A particularly valuable combination of preferred embodiments of the invention relates to 4,4'-bis [3-phenylpyrazolyl- (l)] stilbene-2,2'-disulfonic acids and their salts with inorganic and organic bases.

In the compounds of formula I and also in the to. The starting materials used for their preparation can be the rings, especially the free or condensed aromatic carbocycles, apart from or in addition to characteristic ones

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Bonds, unsubstituted or single or multiple, equally or be variously substituted by in such structures common, non-chromophoric ring substituents.

As non-chromophoric ring substituents are embossed: Normal or branched "alkyl groups with 1 to 20 carbon atoms, but preferably lower alkyl groups with up to 4 carbon atoms in the main chain, such as the methyl, isopropyl, n- or tert. Butyl or iso-octyl groupj halogen up to atomic number 35, preferably chlorine; Cyanj ether groups, such as alkoxy, benzyloxy odex optionally substituted Phenoxy groups, carboxyl and sulfonic acid groups, as well as their functional derivatives such as esters and amide groups, especially carbalkoxy, aryloxysulfonyl and sulfonic acid amide groups, which latter differs from ammonia, aliphatic or cycloaliphatic primary or secondary amines, especially those of hydroxy, alkoxy and tert. Aminoalkylamines, of primary and secondary araliphatic amines, from aromatic amines and from mixed aliphatic-aromatic amines; Alkyl, sulfonated alkyl, hydroxyalkyl, sulfated hydroxyalkyl and arylsulfonyl groups, acylamide groups, such as especially aroylamide groups, for example benzoylamide, alkoxybenzoylamide, Phenylureide, acroylamide, alkanoylamide, such as acetyl, chloroacet, phenylacetyl, phenoxyacetyl, phenylpropionyl and bromopropionylamide groups, alkoxyalkanoylamide and carbalkoxyamide groups, also derivatives of cyclic imide chlorides of carbonic acid, such as diazinyl and especially triazinylamino

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groups, including those in optical brighteners of the stilbene series customary s-triazinylamino groups with chlorine, primary, secondary or tertiary amino groups or alkoxy groups as further substituents of the s.-triazine ring, furthermore, if appropriate, also acyloxy groups, for example tosyloxy and carbalkoxy groups. However, starting materials can also be used in the production of 1,3-marylpyrazoles according to the invention, which contain undesirable substituents in the end product if these ..._ are eliminated at any stage of the manufacturing process or convert it appropriately. Examples are the chromophoric nitro and arylazo groups which lead to amino groups reduced and subsequently acylated or with reactive cyclic imide chlorides of carbonic acid are implemented. Such non-chromophoric substituents are used in the preceding and following explanations. only mentioned, if exclusion provisions, preferred choices and preferred positions are to be observed; otherwise they should be without further information should usually be understood when mentioning the ring systems.

R, apart from those highlighted above Meaning as optionally characteristically substituted Fhenyl radical, also a polynuclear uncondensed substituent, for example a diphenyl group, as a condensed polynuclear Radical, for example a 1- or 2-naphthyl radical, an acenaphthyl radical, a tetrahydronaphthyl radical, as hetero-

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cyclic radical, for example a thienyl, thionaphthenyl, Diphenylene oxide, diphenylene dioxide radical, a Beiizimidazol- (2) -yl-phenyl-, Benzoxazole- (2) -yl-phenyl-, naphthotriazole- (2) -ylphenyl radical mean.

R preferably denotes hydrogen, if appropriate as a monovalent substituent, for example, a lower alkyl radical, cyano, an optionally modified gaboxyl group or a preferably mononuclear aromatic carbocycle, then especially a phenyl radical.

¥ enn R-, and R „together with the bonding carbon- ^ atoms of the pyrazole ring form a fused ring, then it is, for example, the 3,4-dihydronaphthylene (l, 2) - or the naphthylene (1,2) radical.

R- is preferably hydrogen or a monovalent one Substituent such as Rp.Phenylsubstitution can be in this position possibly affect the fluorescence intensity, for example when R- is a stilbyl radical.

As a rule, R. is a phenyl radical with ρ-position,

optionally substituted styryl substituents. The latter Λ phenyl radical can also have an acylamino group, especially a phenylcarbamoylamino, an aroylamino, such as benzoylamino, in particular in the p-position to the vinylene group

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or alkoxybenzoylamino, a chlorotriazinylamino, chlordiazinylamino, primary, secondary or tertiary aniinotriazinyl - amino, alkoxytriazinylamino, chloraminotriazinylamino, aminoalkyltriazinylamino or aminoalkoxytriazinylamino group, f a 2,3-dichloroquinoxalinyl-6-carbonylamino groupjj in this position it can also have an azolyl or arenoazolyl substituent have, preferably a 3-phenylpyrazolyl (l) radical, or then, for example, a 4-phenyl, 2,3-triazolyl- (l) -, a benzo- or naphtho-1,2,3-triazolyl- (2) radical.

The 4-stilbyl radical in position R. advantageously contains in 2-position has a negative substituent, especially a sulfonic acid, Sulfonic acid amide, sulfonic acid mono- or dialkyl amide, Sulfonic acid phenyl ester, alkyl sulfonyl, cyano, carboxyl, Carbalkoxy, trifluoromethyl group. The 4-stilbyl radical preferably represents the radical of stilbene-2,2'-disulfonic acid.

For the direct preparation of pyrazole compounds according to the invention Various processes known per se are available, and it is only a matter of choosing the starting materials to take into account the characteristic substitution condition of the end substances by adding either the radical R-, or the radical R. in conjugation is an optionally substituted one Styryl residue or one that can be converted into one Must contain substituents. ' ''

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As in optionally substituted styryl convertible Substltuenten R, as well as R can. In the starting as well as in the end products in the critical position, for example, the methyl group, an activated methylene group (with, for example, carbalkoxy or cyano group as activating substituents of the same), which can be converted into corresponding compounds with formyi compounds or corresponding anils or acetals, for example benzaldehyde styryl groups condensed, if necessary saponified and deearboxyliert; or in the case of the methyl group ^ | treated with oxidizing agents, or, for example, can R, as well as R ₄ is a formyl group or how such a reactive derivative of this group, for example a reactive Formanil- or acetal group, which are condensed with benzene derivatives containing active methyl substituents to give the corresponding styryl groups

The direct method for the preparation of pyrazole compounds according to the invention consists in the condensation of a suitable one substituted arylhydrazine of the general formula II,

H ₂ N - NH - R ₄ (II)

or one under the reaction conditions such as such reactive derivative of such a compound.

a) with a 1,3-dicarbonyl compound of the general por-

^{mel IIIa} '108815/2151

R _n -C-CH-Ce

-because of the formation of undesired isomers- but better b) with a reactive derivative of the corresponding formula IHb,

(HIb)

in which X is an esterified or etherified hydroxyl group, especially also means chlorine or bromine; or '

c) with a reactive derivative of a hydration product of such a 1,3-diketone of the formula IHc,

0 R ₀ R _v

| 2 13

ft R ₁ - C - CH - C * ■ (HIc)

^X 2

in the X-. and Xp denotes, for example, esterified or etherified hydroxyl groups _I which can also be linked in a ring, if appropriate also

Halogen or one under the influence of the keto condensation favoring accelerators resulting group, for example the remainder of a secondary aliphatic, optionally cyclic imino group or a thiol or alkylthio group; or d) with an aroylalkynyl compound of the formula IHd,

0 R ₃
R ₁ - C - C = C (HId)

according to methods known per se and under the property

^ of the components, especially the solubility properties

co-establish professionally adapted conditions, to one Pyrazole compound of the formula I.

^ Starting materials of the formula II are

φ known methods, for example from the diazonium compound of aromatic primary amines of the formula H ₀ N - R ₄ by Re-

- li -.

Reduction of the diazonium to the hydrazino group obtained. It is

only to ostracize that in the event that not R,

in conjugation to carbonylbinching the critical optionally substituted styryl radical or which contains a group that can be converted into such a group, R. is so substituted in a suitable position. Otherwise, the substitution conditions already discussed apply. Examples of hydrazines of the formula II which have the critical substituent include: 4-hydrazinostilbenes, especially those which have a negative substituent in at least one of the benzene rings in the o-position to the vinylene bridge, such as cyano, carbalkoxy or sulfonyl substituents , especially 4,4'-bis- [hydrazino] -stilbene-2,2 ¹ -disulfonic acid and 4'-nitro-4-hydrazinostilbene-2,2 ¹ -disulfonic acid and 4'-acyl and 4 ^f -Triazinylamino-4-hydrazino-stilbene-2,2'-disulfonic acids, the 4'-benzotriazolyl- and naphthotriazolyl-4-hydrazino-stilbene-2,2'-disulfonic acids. The usual ones are not mentioned in particular

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Aryl hydrazines and aryl hydrazine sulfonic acids which can be used arrive when R contains the critical substituent.

Derivatives which can also be used according to the invention of hydrazine compounds of the formula II which can react like these under suitable reaction conditions are, for example the be, i of the reduction of corresponding diazonium compounds with sulphurous acid and their salts occurring Hydrazine-N-sulfonic acids, which split off the sulfonic acid group on condensation in an acidic agent, also for the purpose Stabilized against oxidative influences of the atmosphere corresponding acylhydrazides of lower fatty acids and Arylhydrazorte.niederer ketones, which with displacement of the Protection group can react.

The starting materials of the formulas UIa to d come in primarily the benzoylacetaldehyde acetals under formula IIIc and the ß-chlorovinyl aryl ketones under formula IHb, which latter according to Darzens can be prepared from aroyl halides and alkynes or vinyl halides under the influence of Lewis acids, into consideration.

As a further direct method for the preparation of the invention 1,3-Diarylpyrazole is the Huisgen method (Angewandte Chemistry Volume 7.5, p. 609) mentioned, which consists of that one can add a 1,3-diaryl-nitrilimine to a Adds alkyne compound by, for example, an aroyl

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hydrazide of the general formula IV

β τ - C ~ °

NH - NH - E- (IV)

transferred with a halogenating agent, as which acid chlorides of inorganic acids, such as phosphorus chlorides are considered to Hydrazidchlorid and this binding of a strong tertiary amine with an addition capable Alkinver- A in the presence of, for example, a Acetylendiearbonsäure-ester is reacted, then, if desired, saponifies the carbalkoxy and the resulting 1, 3-D'iarylpyraz.o 1-4, 5-dicarboxylic acid partially or completely decarboxylated. It goes without saying that the provisions relating to substitution discussed several times are also included here
of Rj and R ^ to be observed.

Because of the easy accessibility of the after several
Methods from cheap starting materials in good yields
1, 3-diarylpyras5oline that can be produced comes from dehydration ^

such, suitably substituted compounds to corresponding Pyrazoles are of much greater importance.

The preferred process for the production of end products according to the invention is therefore that one
such pyrazoline compound of the formula V ,.

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_ 14 -

R ₁ - C = N 'R ₀ -CH -GH

. ² 1

R ₃

In which R and R _{4 are} aromatic radicals as defined under formula I, at least one of which is an optionally substituted styryl radical

contains in conjugation for binding to the pyrazoline ring, preferably in the p-position an optionally substituted one Benzene ring, which preferably forms the radical R., and in the Rp and R .. have the meaning given under formula I, with Hydrogen acceptors, especially with suitable oxidizing agents with removal of hydrogen in the 4,5-position of the pyrazoline ring to form a pyrazo compound of the formula I implements.

Hydrogen acceptors are used in this process the most varied of active ingredients known per se are suitable, for example Raney nickel, chloranil in inert organic Solution of the pyrazolines, for example when heating the pyrazolines in aromatic hydrocarbons, such as xylene with Chloranil; Sulfur, for example when heating the pyramid

in the sulfur melt or /
zoline / in inert organic solution or in aqueous solution in the form of soluble polysulfides, for example alkali or ammonium polysulfides of the formula Me ₂ S with values from η to 5; Salts of oxidizing acids, e.g. soluble alkali or alkaline earth

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potassium salts of hypochlorous or hypobromous acid; Oxygen, in an aqueous solution of the pyrazolines in the presence of heavy metal oxidation catalysts, vie Manganese salts ,. Gupritetrammine saltsj metal compounds higher oxidation levels such as lead dioxide, lead tetraacetate; Potassium ferricyanide compounds, such as hydrogen superoxide, Persulfates, percarbonates and perborates for water-soluble pyrazolines. The appropriate dosage of dehydrating agents and ending dehydration are very easy ™

the disappearance of the natural color of the pyrazolines recognizable * For halogen or oxydationsempfindliche substances, especially for certain styryl, the selection of a suitable dehydrating agent requires the appropriate care.

For the pyrazoline compounds used of the formula V all apply mutatis mutandis to pyrazole compounds of the formula I established substitution rules and conditions. and preferred structural features, on their repetition here

can be dispensed with. · Λ

Only briefly to convey the overview

the more interesting production methods for the pyrazoline starting materials referring to Formula V:

The most common method is implementation

of hydrazine compounds of the formula II with aryl vinyl ketones of the formula VIa,

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U Xl ₀ Xt _o

! II ² I ³

R ₁ - C - C = CH (Via)

wherein R ,, R ₀ and R- have the meaning given under formula I, or with arylalky! ketonen.der formula VIb,

0 R ₀ R ,,

Il I ² I ³

-C-CH-CH-X (VIb)

den precursors of vinyl ketones VIa, wherein X is one of Entrainment of the pair of binding electrons, easily removable substituents, especially chlorine or bromine or an amino or an onium, preferably an ammonium group. For the preparation of the halogen compounds, the introduction of the ß-halopropionyl radical in aromatics comes after Method of Friedel-Crafts and for the production of amino or ammonium compounds the condensation of the corresponding Acetyl-aryl compounds with formaldehyde and a secondary nitrogen base according to the Mannich method in Consideration. ''

These starting materials of the formulas VIa and VIb condense very easy when heated in inert organic, aqueous-organic and water solubility of a component also in aqueous solution or suspension in the presence of acidic or basic reaction accelerators to the internal

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siv yellowish to yellow colored starting materials of the formula V.

A notable variant of the invention consists in first condensing a halocarbon compound of the formulas Ulis or VIb with a sufficiently basic amine of the formula I ^ N-S to give the corresponding arylamine acetone, then nitrosating the secondary amino group by the action of nitrous acid, and the nitroso group is reduced to the amino stage by methods known per se, the pyrazoline A of the formula V or the pyrazole of the formula I being formed immediately.

Finally, in view of the oxidation sensitivity of the preferred critical styryl groups, use can be made of the fact that 1-phenylpyrazolines with a free para position of the preferably otherwise unsubstituted 1-phenyl radical according to Vilsmeyer with formyl-N-alkylanilines and phosphoroxychloride or with dimethylformamide and phosgene form the corresponding 1 - Let (4'-formylphenyl) pyrazolines condense, which one with suitable hydrogen acceptors to the corresponding ,

Dehydrate l- (4'-formylphenyl) -3-aryl-pyrazoles and then condense with compounds containing activated methyl or methylene groups to give corresponding vinyl compounds can. One can use the formyl group for stabilization or relief the condensation before or after the dehydration acetalizing or converting with a primary aromatic amine into the corresponding anil and reactive with these Carry out the styryl condensation directly on descendants.

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1695

G-suitable condensable methyl or methylene compounds are for example the phenylacetic acids; their alkyl esters and the corresponding nitrile., which may have a carbo- or heterocyclic aryl radical, and

activated p-nitrotoluenes. ■ By saponification of the cyan and Carboxylic ester groups and decarboxylation of the substituted acrylic acids formed can, if desired, be the corresponding Manufacture vinylene compounds.

Unsulfated pyrazo compounds of the formula I according to the invention are suitable in the usual ways. Quantities of about 0.001 to .1.0 $ of the polymer to improve the appearance of yellowed polymeric plastics, soluble salts of monosulfonic acids can be used in usual amounts for whitening synthetic polyamide and polyurethane fibers in an acidic aqueous bath, compounds containing sulfamide groups for tinting the same types of fibers in water 'öhflotten and the particularly valuable nouns 4,4'-bis [a-phenylpyrazolyVCl) -] - stilbene ^ 2,2 · - disulfonic acids can be used in usual amounts of about 0.001 to 0.5 % _y based on the fiber weight, for catfish tinting of cellulose serve. Detergents according to the invention contain approximately 0.005 to 0.5 % of the new pyrazole compounds. The white tone that can be produced on textiles with the new pyrazoles according to the invention is distinguished by good chlorine-

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resistance and lightfastness.

It is also possible to use the colored pyrazolines To dye formula V on textile fibers and then to subject the dyed ¥ are to an oxidation bleaching process, whereby they be chemically and optically bleached at the same time. This method is suitable, among other things, for strength comparisons, because the color strength of the staining can be figured out. A reductive aftertreatment on the fiber oxydatlv produced white tint is often advantageous.

The following examples illustrate the Er-r. finding ·. The temperatures are given in degrees Celsius.

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example 1

SOoH

CH = CH - <Ξ> - Ν

40g 4.4 ^? Dihydrazinostilbene-2,2'-disulfonic acid (German patent 46'321) are dissolved with 8g sodium hydroxide at 65 ° in 700ml water. This solution is mixed with a solution of 34 g of phenyl-2-chlorovinyl ketone [Chemical Abstracts 5JL, page 15 * 449 (1957)] in 50 ml of ethylene glycol monomethyl ether at 30 ° with stirring. The mixture is first stirred for 4 hours at 30 and then for 3 hours at 55-60 ° and the liberated hydrochloric acid with an aqueous solution vo h 9g Natriumcar-

bonät gradually dulled. To stop the reaction the mixture is refluxed with stirring for a further 2 hours. Then let it cool down. The unusual one The product is then separated off and purified by recrystallization from water pyridine with the addition of sodium hypochlorite. ■

The disodium salt of 4,4 ¹ -bis jj> -phenylpyrazoIyI- (IJ] -stilbene-2,2'-disulfonic acid is thus obtained as a hydrate which crystallizes in yellowish, flat needles. The dilute aqueous solution of the new pyrazole derivative fluoresces in daylight blue-violet.

The product has a good affinity for cellulose fibers and good resistance to chemical bleaching agents,

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BATHROOM OBlGlNAL

such as alkali hypochlorites and perborates. The new Binding can be used to "brighten cellulose substrates." such as cotton, rayon rayon, pulp, paper and pulp can be used. Acid baths also become polyamide substrates lightened. The textiles tinted white using the new pyrazole derivative are relatively lightfast. The new Veisstöner is also effective in detergents. The ones with such Cellulose textiles washed with white ash are cleaned and at the same time visually brightened. ^

Thanks to the good resistance of the new Feisstö'ners to chlorine-releasing chemical bleaching agents, the product can also be incorporated into such detergent compositexones which, for example, alkali or alkaline earth salts of dichloroisocyanuric acid, as for example in the American patents V 072 * 054 and V 1.50 * 132 are included.

The product can also be incorporated into polyamide spinning masses. Obtained in this way in the mass m up gehellte brilliant white polyamide threads.

If, with otherwise the same procedure, the phenyl-2-chlorovinyl ketone is replaced in this example by the corresponding amount of one of the following aryl-2-chlorovinyl ketones: (o-methoxyphenyl) -2-chlorovinyl ketone
(m-Methylphenyl) -2-chloroviny! ketone. (m-Chlorophenyl) -2-chloroviny! ketone

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(p-Chlorophenyl) -2-chlorovinyl acetone (p-methyl-phenyl) -2-chlorovinyl ketone (p-methoxyphenyl) -2-chlorovinyl ketone Phenyl (1-methyl 1-2 chlorovinyl) ketone Phenyl (1- ^ phenyl-2-chlorovinyl) ketone (3,4-dimethylphenyl) -2-chlorovinyl ketone (2,4-dimethoxyphenyl) -2-chlorovinyl ketone (3,4-methylenedioxyphenyl) -2-chlorovinyl ketone (2-furyl) -2-chloromyl ketone and (2-thienyl) -2-chlorovinyl ketone,

the 4,4 ¹ -bis- | j> yrazQlyl- (1) Jc = üstilben-2, 2 * -disulphonic acids or their disodium salts are obtained in this way.

Table I.

Bexspxel 2: example 3: example 4: example 5: example 6: example 7;

4,4'-bis [3- (2-methoxyphenyl) pyrazolyl- (1)] stilbene-2,2 ¹ -disulfonic acid

4,4 * -Bis [3- (3-methylphenyl) pyrazolyl- (1)] stilbene-2,2'-disulfonic acid

4,4'-Bi s- [3- (3-chlorophenyl) -pyrazoIyI- (1)] - stilbene-2,2 * -disulfonic acid

4, 4 ¹ -bis- [3- (4-chlorophenyl) -pyrazolyl- (l)] - stilbene-2,2'-disulfonic acid

4,4'-bis [3- (4-raethylphenyl) pyrazolyl- (l}] stilbene-2,2'-disulfonic acid

4,4 * -Bis- [3- (4-methoxyphenyl) -pyrazolyl- (l)] -stilbene-2,2'-disulfonic acid

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example 8th: example 9: example 10: example 11: example 12: example 13: example 14:

4,4'-bis- [3-phenyl-4-methyl-pyrazolyl- (1)] -stilbene-2,2'-disulfonic acid

4,4'-BiS - (^, 4-diphenyl-pyrazolyl- (l)] - stilbene-2,2'-disulfonic acid

4,4'-818- [3- (3J 4-dimethylphenyl) pyrazolyl- (1)] stilbene-2,2'-disulfonic acid

4,4 * -Bis- [3- (2,4-dimethoxyphenyl) pyrazolyl- (1) J-stilbene-2,2'-disulfonic acid

4, 4 ^r -Bis- [3- (3, 4-methylenedioxyplienyl} -pyrazolyl- (1)] - stilbene-2,2'-disulfonic acid

4,4 ^T -Bis- [3-furyl- (2) -pyrazolyl- (1)] -stilbene-2,2'-disulfonic acid

4, 4 ¹ -Bis- [3-thienyl- (2) -pyrazolyl- (1) -] - stilbene-2,2'-disulfonic acid.

These compounds are also valuable brighteners for cellulose and polyamide substrates.

The required aryl-2-chlorovinyl ketones can be obtained, for example, from aroyl acetaldehydes or the tautoic hydroxymethylene ketones and thionyl chloride (G-azz. Chim. Ital. 77, 549-56 [1947]) or "from aroyl chlorides and alkynes or vinyl chloride ( Chemical Abstracts ^ i »page 15 * 449 g [1957]) j Chemical Abstracts _54, page 10 ^f 930 f [i960]), in the presence of Lewis acids, with 1 mol of HCl in any 3,3-dichloropropiophenones formed is split off.

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-24-

• Example 15

20g of 4,4'-dihydrazinostilbene-2, 2'-disulfonic acid

• dissolved with 4g sodium hydroxide at 55 in 350ml water. The solution obtained is mixed with a solution of 25 g of 3> 3-dimethoxypropiophenone (Chemical Abstracts 54, page 10,930 g [1960]) in 50 ml of ethylene glycol monomethyl ether while stirring for 20-25 times. 15 ml of 10% acetic acid are then added and the mixture is stirred first for 1 1/2 hours at 20-25 ° and then for 3 hours at 55-60. After this time, the clear, dark yellow solution practically no longer contains any free hydrazine. By adding about 5ml 2 — n. Hydrochloric acid, the pH of the reaction mixture is now lowered to 2. The mixture is then stirred for 14 hours at 55-60 ° and then for another hour at 85-90 °. The mixture brightens after the addition of acid, and after 30 minutes a light yellow precipitate begins to separate out. Which is filtered off with suction after the reaction has ended. The crude product is dissolved in hot water, made alkaline with sodium carbonate, clarified while hot and the filtrate is allowed to cool. The disodium salt of Example 1

• described pyrazole separates here in yellowish, Crystals that are relatively difficult to dissolve in cold water. The product has the same properties as the example 1 connection received.

In a very analogous way, the pyrazoles listed in Examples 2 to 14 can be obtained using the

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BATH ORIGINAL

Making talking dialkoxypropiophenones instead of aryl chlorovinyl ketones. The substituted 3,3-dimethoxypropiophenones required for this synthesis can be prepared from the corresponding 2-chlorovinyl ketones and methanol in the presence of alkali methylate or alkali hydroxide (Chemical Abstracts Ag ₉ page 5878 i [19 48] and Chemical Abstracts, 54 _T page 10 ' 930 g [I960]).

The 25 g of 3,3-dimethoxypropiophenone are replaced by durcja 25 g of 2-phenacyl-1,3-dioxolane (Kochetkov, Ch em. Abstract, 52, Page 4603 [1958]) the disodium salt of the one described in Example 1 is also obtained with otherwise the same procedure Pyrazole.

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Example 16

8g sodium hydroxide and 5g disodium salt of 4 ', 4 ^f -Bis-L3-phenyl-pyrazolinyl- (I)] -stilbene-, 2,2 * -disulfonic acid of. formula

-C = N \ ^ SO ₃ H CH - ^ f ^ - / N = c - <Ξ3 I. N ■ -Cj ^ - gh = SO ₃ H ■ N I. H ₂ C - < ^N CH ₂ -CH ₂

are dissolved in 1000ml Yasser at 35. You move these Solution with stirring over the course of 20 minutes with 70ml of a Sodium hypochlorite solution containing 15% active chlorine. That The reaction mixture is then kept at a temperature of 30-40 ° for 30 minutes, then diluted with 500 ml of water, heated to 90-and clarified.

The sodium salt of 4,4'-bis- [3-phenylpyrazolyl- (1) j- «* 4aestilbene-2, 2 ^f -disulfonic acid, described in Example 1, separates out of the filtrate on cooling

^ Unlkr.istallisierung from Yasser with the addition of sodium hydro-

sulfite is cleaned.

The pyrazoline derivative of the above formula used in this example is prepared as follows: 9g disodium salt of 4,4'-dihydrazinostilbene-2, 2 * -disulfonic acid are dissolved in 200ml water, with 2g sodium hydroxide added and heated to 90. An aqueous solution of 9gtO-dimethylaminopropiophenone hydrochloride is left at this temperature add dropwise and heat the orange-colored solution

, ■ η ^ 109815/2153

28 hours to 90-100. When the clarified reaction mixture cools, the pyrazoline derivative separates out as a strong yellow colored precipitate from «This bis-pyrazoline stilbene results on cellulose fibers bright yellow dyeings that are "not very lightfast are, *.,.."

The sodium salt of 4,4 * -bis- [3-phenyl-pyrazolyl ~ (1)] stilbene-2,2 ^! -disulfonic acid can also be obtained in the following ways:

6.7g disodium salt of 4,4'-bis- [3-phenyl-pyrazolinyl- (l)] - stilbene-2, 2'-disulfonic acid are dissolved in 70ml 70ml of aqueous Pyridine dissolved at 75 ° and with a solution of 0.5 g copper sulfate pentahydrate in 5ml 4-n. aqueous monoethanolamine solution offset. A stream of air is passed into the mixture thus obtained at 70-75 with thorough stirring for 40 hours. The dark yellow solution is then mixed with 100 ml of water and expelled the pyridine with steam. After adding 4g of sodium hydroxide, it is allowed to cool and the filter is filtered brown precipitate, dissolve it in 200ml hot water, added with excess sodium sulfide, cools down, filtered off, washes with 2% aqueous sodium carbonate solution until the piltrate is only faintly colored, dissolves in 250 ml of boiling water, filtered hot and the filtrate is mixed with 2.5 g of sodium carbonate. After cooling, the crystallized disodium salt becomes the

4,4'-bis [3-phenyl-pyrazolyl- (l)], stilbene-2,2'-disulfonic acid

filtered off ', washed with cold water and dried.

109815/2159 ^BA D original

Example 1.7

3.75 g of 1- [2 ~ cyano-4'-chloro-stilbenyl- (4)] -3-phenyl-pyrazoline are in 100ml xylene with 3.0g chloranil for 24 hours under rest

ren boiled on the reflux condenser. The yellow reaction solution will then briefly boiled with 5g of basic aluminum oxide, then filtered hot and the piltrate cooled to 10. Here, the new pyrazole derivative of the "above crystallizes Formula in the form of pale yellowish crystals. By repeated recrystallization from xylene with the addition of decolorizing charcoal, the product becomes almost colorless crystals obtained of m.p. 152 °.

The new pyrazolyl-stilbene derivative fluoresces violet in organic solution. The connection brightens in the usual levels Polyamide or polyester fibers.

For the preparation of the aforementioned 1-L 2-cyano-4-chloro-stilbenyl- (4)] -3-phenylpyrazolines become 25.5g of 4-amino-.4 ·· -chlor-2-cyanosilbene in a mixture of 66ml 37% hydrochloric acid and 500ml water at 8 - 12 ° with 6% sodium nitrite diazotized, the resulting yellow paste of the diazonium salt with a Solution of 70g tin chloride dihydrate in 40ml 37% hydrochloric acid reduced, after adding another 50ml 37% salt

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;,.> .: ■; ■: BAD ORIGINAL

acid held at 25 ° for 1 hour to improve the
Filterability heated to 80 ° for 1 hour, the tin-containing one
Sucked off the hydrazine salt at room temperature, suspended in 600 ml. Water, treated with 60 ml of 30% aqueous sodium hydroxide solution, stirred for -30 minutes at 65 °, ^{sucked off the 4-hydrazino-4 l} -chloro-2-cyanosilbene while warm and recrystallized
purified from alcohol,

13.5g of 2 ~ cyano-4-hydrazino- .. 4 ¹ -chlorstilbene, which melts at 173 °, are stirred in 150ml of ethylene glycol methyl ether with 8.5g of (β- chloropropiophenone and 10ml of pyridine for 16 hours at 90-95 °, the yellow crystallized out) 1- [2-cyano-4'-ehlorstilbenyl- (4)] -3-phenylpyrazoline is filtered off with suction and washed with ethylene glycol monomethyl ether and ethanol
at 223-24 ° and fluoresces blue-green in organic solution.

1098 1 5/2159

Example 18

^ - CH = CH - ^ J- Cl

H ₂ H ^ N

13.5g of the 2-cyano- * 4-hydrazino-4'-chlorostilbene described in Example 17 are heated to 65-70 ° in a mixture of 200ml butanol, 75ml Yasser and 7.5g sodium carbonate, at this temperature in the course of 15 minutes an aqueous solution of 12.5 g of 2-dimethylaminomethyl-1-tetralone hydrochloride added and the mixture refluxed for 18 hours with stirring. The resulting pyrazoline derivative of the formula

^{= CH}

Cl

is filtered off after cooling and washed with ethanol.

The yellow pyrazoline, which fluoresces blue-green in organic solution, is described in accordance with that in Example 17

Method in xylene solution with chloranil to the pyrazole of the beginning mentioned formula dehydrated and through. Recrystallize from Ethylene glycol monomethyl ether purified. The new pyrazole derivative melts at 190, fluoresces in organic solution purple and can be used to lighten polyamide "and polyester fibers. -.

109815 / 21Si

Example 19

41.5 g of 4-hydrazino-4 ¹ -nitrostilbene-2,2 ¹ -disulfonic acid are dissolved as disodium salt in 800 ml of water and stirred at 35-40 ° with a solution of 24.2 g of 3,3-dimethoxypropiophenone in 50 ml of ethylene glycol. monoinethylether added. After adding 20 ml of 10% acetic acid, the hybrid is first stirred for 2 hours at 20-25 °, then for 4 hours at 60-70 °, and after adding 10 ml of 2N hydrochloric acid for 10 more hours at 60-70 ° and 2 hours 90-100 ° heated. After adding 40 g of sodium chloride, the mixture is allowed to cool, the 4- [3-phenyl-pyrazolyl- (l)] ~ 4'-nitrostilbene-2,2 ^ disulfonSaUTe sodium formed is filtered off and purified

by dissolving from water with the addition of a little sodium carbonate and Na "fc ^r i ^umn yP ^oc kl ° ^r i" k-

15 g of cast iron powder are suspended in 500 ml of water and, after adding 2 ml of 80% acetic acid, heated to 80-90 ° for 30 minutes. In the thus prepared iron suspension are put at 90-100 ° in Yerlaufe of 30 minutes 28.6 g of-Dina "fcriumsalzes the above described 4- [3-Phenylpyrazolyl- (l)] - 4 ¹ -nitrostilben-2,2 ¹ -disulphonic acid and then heated the mixture while stirring at reflux temperature until an alkaline sample spotted on filter paper is very pale yellow in color and no longer becomes lighter after prolonged stirring

109815/2159 ■

SAD ORIGINAL

set the pH to 9-10 and filter off the egg sens chi aiiim. As a yellowish, griinstichig in ultraviolet light blue fluorescent solution is obtained of disodium salt of 4-amino-4 '- [3-phenyl-pyrazolyl (l)] - stilbene-2, 2-disulfonic acid ^r. Without isolation, the product is converted into s-triazinyl derivatives which can be used as brighteners, as described below. The amine content of the solution is in the usual way

determined by titration with NaO-. 9.25 g of cyanuric chloride are dissolved in 100 ml of acetone at room temperature and poured into a mixture of 200 g of ice and 50 ml of water while stirring. An aqueous solution of the disodium salt of 25 g of 4-amino-4 ^r - [3 ^ phenylpyrazolyl- (1) I-stilbene-2,2'-disulfonic acid is allowed to drip into this cyanuric chloride suspension, and ice is added to ensure that the temperature remains below 0 °. After the addition of the amine, a pH of 3-4 is set with aqueous sodium carbonate solution and held until no more diazotizable amine can be detected. As soon as this is the case, 4.6 g of aniline are added, the temperature is gradually increased to .25 and the hydrochloric acid released is neutralized with 15% sodium carbonate solution. The mixture is then kept at a pH of 6-7 at 20-30 ° until all the aniline has disappeared. 11.0 g of morpholine are now entered, the mixture is heated to 90-95 ° for 2 hours and the disodium salt of 4- [3-phenyl-pyrazolyl- (l)] - 4 "- [4-phenylamino-6-morpholino-s- triazinyl- (2) -amino] -stilbene-

109815/2159

Salted out 2,2'-disulfonic acid by adding sodium chloride. After drying, the new whitening agent forms a yellowish, water-soluble powder that is used to whiten Cellulose fibers can be used.

Quite similarly effective products are obtained, if one, with otherwise the same procedure, the 11.0g morpholine by 5.6g monoethylamine, 7.5g monoethanolamine, 9.3g '2-hydroxypropylamine, 9.3g 2-methoxyethylamine, 9.3g N-methyl-2-hydroxyethylamine, 13.0g N.N-bis (2-hydroxyethyl) -amine, 17.0g N.N- ™ Bis- (2-hydroxypropyl) -amine, 13, Og 2- (2-hydroxyethoxy) -ethylamine, 14.3 g of 2,6-dimethylmorpholine or 10.6 g of piperidine replaced.

If the 11.0 g of morpholine is replaced by 6.0 g of aniline, the addition of 2-n. Hydrochloric acid has a pH of 5, heated for 6 hours to 90-100 and then neutralized with sodium hydroxide solution, this gives the relatively poorly water-soluble disodium salt of 4- [3-phenyl-pyrazolyl- (l)] - 4 · - [4,6-bis-phenylamino-s-triazinyl- (2) amino] stilbene-2, 2 ¹ A -disulfon- acid.

This product can also be used especially in combination with detergents to lighten cellulose fibers. .

109815/2159

ORlSiNAL INSPECTED

Example 20 - ■ -.

If the 4.6 g of aniline in Example 19 is replaced by 8.6 g of 3- or 4-sulfophenylamine or their sodium salts, the trisodium salts of 4- [3-phenyl-pyrazolyl- (l )] - 4 ¹ - [3 - or. 4-sulfophenylamino-6-morpholino-s-triazinyi- (2) -amino] -stilbene-2,2'-disulfonic acids. These products are relatively soluble in water and are particularly suitable for lightening paper or cellulose textiles. Here too, the morpholine can be replaced by the amines mentioned in Example 19.

In this way you also get very effective ice speakers for Cellulosic substrates.

These compounds can also be used in acidic baths Lightening polyamide materials can be used.

Thanks to their good acid stability, these products can also in acidic synthetic resin baths and in cellulose fiber suspensions containing alum can be used with success in paper production.

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1695111

Example 21

9.5 g of 2,4-dichloro-6-methoxy- "S-triazine (Am. Soc- 79 . 2989 [1951]) are added to a solution of 27.1 g of 4-amino-4'-£ 3-phenyl-pyrazolyl- {l)] -stilbene-2,2 ¹ -disulfonic acid sodium entered and stirred at 20-30 ° at a pH of 5-6 until no more aromatic amine can be detected Hydrochloric acid released is successively neutralized with aqueous sodium carbonate solution.

4.6 aniline is then added to the mixture, the pH is kept at 7 with 15% sodium carbonate solution and the mixture is heated to 90-95 for 6 hours. By adding sodium chloride, the disodium salt of the 4-ί 3-phenylpyrazolyl- (1)] -4 ¹ - [4-methoxy-6-phenylamino-s-triazinyl- (2) -amino] -stilben-2,2 ' -disulfonic acid excreted as a yellowish precipitate- * The new stilbene derivative forms a yellowish, water-soluble powder. The compound can be used to lighten cellulose and polyamide substrates. Products with similar effectiveness are obtained when the 2,4-diehlor-6-methoxys-triazine is replaced by equivalent amounts of 2,4-dichloro-6-ethoxy-s-triazine or 2 , 4-DIchlor-6-isopropyloxy-s-triazine is replaced.

109815/2159

Example 22

Phosgene is introduced at 0-10 into a solution of 10 g of 4-amino-4 ^t .- [3-phenyl-pyrazolyl- (l)] - stilbene-, 2'-disulfonic acid sodium in 300 ml of water and, by successive addition of 10 ^ iger aqueous sodium carbonate solution maintain a pH value of 6-7 until no more diazotizable amide can be detected. By adding sodium chloride and warming it slightly, the product of the above formula is converted into a form which can be filtered easily as the tetrasodium salt, filtered off with suction, washed with sodium chloride solution and dried. A yellowish, water-soluble powder is obtained which can be used to lighten cellulose fibers.

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1695115

Example 23 .

An aqueous acetone solution of 10.0g 4-amino-4 '- [3-phenyl-pyrazolyl- (l) J-stiben-2,2'-disulfonic acids
Sodium is added dropwise at 10-15 with stirring with 2,4-diraethoxybenzoyl chloride and the acid liberated is neutralized by successive addition of sodium carbonate until the mixture no longer contains any free amino groups. After the acetone has been distilled off, 5 $ sodium chloride is added and, after cooling, the product of the above formula is filtered off as the disodium salt. After drying, a yellowish powder is obtained, the aqueous solution of which is used to lighten
Cellulose fibers can be used. Whiteners which can also be used are obtained if the 2,4-dimethoxybenzoyl chloride is replaced by 4-methoxybenzoyl chloride or 2-ethoxy-4-methylbenzoyl chloride.

105815/2159

1695111

Example 24

9.25. g 4,4'-diaminostirbene-2,2'-disulfonic acid are in Usually tetrazotized, the tetrazo compound is isolated at 0-10 ° in a solution of 8.1 g of 1-phenylpyrazoline in: added 110 ml of pyridine and 50 ml of water. After 15 hours, 4 g of sodium hydroxide are added to the red-brown mixture and the pyridine is expelled with water vapor. The solution obtained is used to form the 4,4'-bis- [1-phenylpyrazolinyl- (3)] stilbene-2,2'-disulfonic acid with sodium chloride as the disodium salt salted out. The deep brown colored pyrazoline dissolves in water with a yellow color and dyes cotton in reddish yellow tones, which have poor lightness.

For the oxidation, the pyrazoline compound obtained is dissolved in 500 ml of water and the solution is made up with sodium hydroxide solution set a pH value of 10-11. The alkaline solution is added dropwise with enough sodium hypochlorite solution at 70-80 ° while stirring added until the reaction mixture shows a permanent excess of chlorine on potassium iodine starch paper. It is now allowed to cool, and the precipitated product is filtered

109815/2159

- ■ 39 -

1695111

and cleans it by dissolving it from hot water, which has something Sodium dithionite was added. This is how the disodium salt is obtained of 4,4'-bis [1-phenylpyrazolyl- · (3)] -diet ~ 2,2'-disulfonic acid as a yellow, water-soluble powder. The product can be used for optical Lightening cellulose fibers can be used.

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169511

Example 25

15 g of the disodium salt of '4,4 ¹ -Bis- [3-phenylpyrazolyl- (l)] - stilbene-2,2'-disulfonic acid are dissolved as dihydrate in 120 ml of dimethylformamide and cooled to 10 °. The yellowish solution is then mixed with 40 g of thionyl chloride while stirring. The reaction mixture becomes cloudy and the temperature rises spontaneously to 60 ° -70 °. The temperature is kept at 60 ° by cooling. After the exothermic reaction has subsided, the yellow suspension is cooled to room temperature and filtered off. The disulfochloride obtained in this way is washed with a little dilute alcohol and dried _{over PnO 5 at 20-30 °.}

For the production of those listed in the tables below Amide is the disulfochloride with excess amine Heated 80-100 ° and the amides isolated in the usual way. = • 1 * 3 C "Z

HG. = CH

-NH,

NHC 2 ^H 5 2V2 12 ^H 25 OH NHCH ₂ CH ₂ NHCH ₂ CH ₂ 18 ^H 37 N (C NHC CH ₂ N (CH ₃ ) NHC

H = Cn

Melting point 305 ° 265 ° 248 ° 212 ° 207 ° 216 ° 210 °

109815/2159

SAD ORIGINAL

The sulfamides obtained in this way form pale yellow crystals. In organic solution, the products fluoresce vividly blue and in the form of their aqueous dispersions can be used for optical Lightening of cellulose acetate or polyamide substrates used will.

. The products can also be made in transparent or. Work in opaque PVC foils. You get so beautifully brightened Plastic films.

109815/2159

Example 26

14 g of l- (4'-methyl-phenyl) -3-phenyl-pyrazoline with a melting point of 132 ° -134 ° are mixed with 3.1 g of sulfur powder and, while stirring, in a Pyrex flask, immersed in a metal bath, to 310 ° -320 ° heated, this temperature being maintained for 4 hours. After cooling, the glass-like brown mass is pulverized in a mortar and then boiled with 150 ml of chlorobenzene. After it has been filtered off while hot, the residue is the ^4,4'-1- bis [3-phenyl-pyrazolyl- (l)] -stilbene of the formula

HC = C ¹ H

return. This compound can be made from dimethylformamide Recrystallize. In this way, 1.3 g of the pure compound from the F. 279-282 ° are obtained, "which in hot Dimethylformamidlösuhg an intense purple in daylight Shows fluorescence. * ■ ■

The product can be incorporated into polyamide spinning masses will. In this way, brilliant white polyamide threads lightened in the mass are obtained.

The starting material used in this example 1- (4 ¹ -methyl-phenyl) -3-phenyl-pyrazoline is obtained in the usual way by condensation of ρ-tolylhydrazine hydrochloride with «'^ -dimethylaminopropiophenone hydrochloride in 70% ethanol with the addition of sodium carbonate , whereby the precipitated pyrazoline can be recrystallized from ligroin. ^{: i} 109815/2159

1695111

Example 27 SO,

40 g of 4,4'-bis [3-phenyl-pyrazolyl- (l)] - stIlben-2,2'-

Sodium disulfonic acid are concentrated in 400 ml at 20-30 °. Λ sulfuric acid dissolved and mixed with 270 g of fuming sulfuric acid containing sulfur trioxide of 26 $. The brownish solution is then heated to 90-95 ° for 5 hours and then poured onto 3000 g of ice water. The precipitated yellow product is filtered off, stirred in 2000 ml of water at 50-60 °, made weakly alkaline (pH 7.5-.8) with about 50 g of sodium carbonate, clarified and the slightly yellowish, blue fluorescent solution in vacuo evaporated to dryness. >

The tetrasodium salt of the sulfation product of The above formula is readily water-soluble and acid-resistant. Since the product still has a good cellulose affinity, it can be used to lighten cotton from the synthetic resin bath.

10 9 8 15/2159

BAD ORlGfN _AL

1695111

- AA -

Example 28

10g of a pale yellowish staple fiber fabric Nylon (from E.J. Du Pont de Nemours, Vilmington, Del. U.S.A.) are in a bath in a liquor ratio of 1:30, the Contains 0.01g of the Veissöner described in Example 1 and 1.2ml of formic acid, treated for 30 minutes at 75 °, rinsed and dried. The nylon fabric treated in this way appears much whiter in daylight than an untreated one Comparison sample.

109815/2159

¹ _45-

Example 29

¥ Ice cotton poplin is at a liquor ratio of 1:30 15 minutes at 60-70 ° in an aqueous Treated bath, the O, O33g of Example 1 available Pyrazole derivative and 2g sodium sulfate per liter. After rinsing and drying you get a brilliant; lightened Tissue.

If the same operation is carried out in the presence of Ig NaOCl in the liter of treatment liquor: a chemically and optically bleached fabric.

109815/2159

Example 30

An ash liquor containing 3.5 g of soap powder per liter and

Contains 1.5 g of sodium carbonate, is at 70 with a solution of 0.02 g of the disodium salt of 4,4'-bis [3- (p-chlorophenyl) -

pyrazolyl- (l)] -stilbene-2,2'-disulfanoic acid in 20 ml ¥ water and then with
8 ml of an aqueous sodium hypochlorite solution containing 15 $ active chlorine are added.

After 10 minutes, 31 g of a cotton cretonne fabric are added and holds at 70 for 20 minutes. It is then rinsed and dried.

A brilliant white cotton fabric is obtained, which Appears significantly whiter than a fabric pattern, which under the same conditions, but with the addition of inventive ¥ was washed.

Very similar ice effects are obtained if one with otherwise the same procedure, replace the aforementioned brightener with the same amounts

4, 4 '-Bis- [3> -phenyl-pyrazolyl- (I)] - stilbene-2, 2 ¹ -disulfonic acid,

4,4'-bis- [3- (4-methyl-phenyl) -pyrazolyl- (1) -)] - stilbene-2,2'-disulf on acid,

4, 4 '-Bis- [3- (4-metho> xy-, phenyl) -pyrazolyl- (1)] -stilbene-2, 2' -disulf on acid

4,4 '-Bis- [3- (3, .4-dimethyl-phenyl) -pyrazolyl- (1)] -stilbene-2,2' -di

• sulfonic acid

replaced.

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1695115

-47-

Example 31

3Gg of chemically bleached cotton cretonne fabric are in a dye bath of the composition: 1000 ml of water,

1 g sodium sulfate,

0.03 g of 4.4 ^1- bis [3-phenyl-pyrazolinyl- (T)] -stilbene-2, 2 ^r disulfonic acid sodium (Example 16, follow-up)

the formula

SO-Na _Λτ "y = \

CH = CH -CI ^ - ^N I

cr \ vr CH ₀ GH—

S0v, Na 2 2

Dyed for 30 minutes and rinsed cold. A bright, light yellow colored cotton is obtained which, on irradiation, with lights up yellow with ultraviolet light.

The cotton fabric dyed in this way is still damp Conditions in a liquor ratio of 1:30 in a bleach bath, the per liter Ig sodium sulfate, Ig sodium carbonate, as well an amount of sodium hypo- ν corresponding to 1.5g of active chlorine

contains chlorite, treated at 70 for 20 minutes. Here is ^

the yellow pyrazoline on the fiber is dehydrated to the colorless, blue-violet fluorescent pyrazole and is obtained nach.dem rinsing and drying a cotton fabric, the opposite a comparison sample that has only been chemically bleached has a significantly whiter aspect, which is caused by a reductive Post-treatment with sodium hydrosulfite can be improved can.

1098 15/2 159 construction

Example 32

10g of a slightly yellowish-looking fabric made of poly-

• "(S)
terephthalic acid glycol ester, e.g. from DACRON (the company

Du Pont de Nemours, Vilmington, Del. USA) are in an aqueous bath containing 0.01 g of the pyrazole derivative described in Example 18 and 0.3 g of an oleic alcohol-pentadecyl glycol ether, at a liquor ratio of 1:50
Dyed for 30 minutes at 95-100 °, rinsed and dried. The fabric treated in this way has a significantly whiter appearance than an untreated reference sample. To ensure that the Veissöner is well dispersed in the treatment bath, the product is dissolved in 5 ml of ethylene glycol monomethyl ether before it is added.

109815/2159

Example 33

10g of undyed acetyl cellulose yarn are heated to 75 in a bath of liquor ratio 1:30, the 0.2g octadecyl alcohol pentadecaglycol ether and 0.08g of the Veisstö'ners described in Example 18 in finely dispersed form, Stained for 30 minutes. The yarn treated in this way has a significantly whiter appearance after rinsing and drying than before treatment.

1098 15/2159

Beispitjl 3 4 ■

100 parts of undyed nylon fabric are at 70 in a wash liquor, which 0.05 parts of the according to Example 17 obtained pyrazole in finely dispersed form, as well as 8g of a synthetic ¥ ash agent contains, with a liquor ratio Washed from 1: 10.30 minutes, rinsed and dried. The fabric treated in this way has a more brilliant appearance as a fabric washed without the addition of whitening agent,

10 9 8 15/2159

1695111

Example 35

100g of a Syndet heavy detergent, consisting of: 15.2 g dodecylbenzenesulfonate,

3.8 g sodium salt of laurel alcohol / sulfuric acid ester, 25.6 g sodium polyphosphate,

7.6g tetrasodium pyrophosphate,

4.8 g water glass (sodium silicate),

1.9 g magnesium silicate,
5.0 g sodium carbonate,

1.4g carboxymethyl cellulose, -

0.3 g tetrasodium salt of ethylenediaminetetraacetic acid, 34.4 g sodium sulfate,

verden mixed with 100g ¥ water to a homogeneous paste, with 0.1g 4, 4 ¹ -Bis- [3-phenyl-pyrazolyl- (I)] -stilbene-2, 2'-disulfonic acid sodium and 0.05g l- [ 3-phenylcoumarinyl- (7)] -3-phenyl-pyrazole (P ^). 202, prepared by dehydrogenation with chloranil in xylene, of the yellow 1- [3-phenylcoumarinyl- (7)] -3-phenyl-pyrazoline obtainable from o-chloropropiophenone and 3-phenyl-7-hydrazinocoumarin in the presence of pyridine, analogously to Information in Swiss patent specification No. 405 * 327) dissolved, added to 5ml of ethylene glycol monoethyl ether, mixed well and then sprayed in a spray dryer.

100g of an ash material consisting of 30g of undyed nylon fabric and 70g of undyed cotton fabric are included in 85 in a Vaschflotte, which 8g of the above-described

109815/2159 ^; .

ben, containing ¥ ash agent containing brightener, for one Washed liquor ratio of 1:10 for 10 minutes, rinsed and dried. In this fasching process both will Types of fabric nicely brightened.

109815/2159

Example 3α

1000g of normal household linen, consisting of polyglycol terephthalate fiber fabrics, from synthetic polyamide fiber fabrics and from cotton fabrics, or corresponding Blended fabrics are made at a temperature of .85-90 in 1 of a washing liquor entered, which g of a detergent, consisting of:

25 parts of sodium dodecylbenzenesulfonate, 15 parts of pentasodium tripolyphosphate ^; 0.3 parts of lanolin, ■

0.1 part melamine,
0.2 parts perfume,
1.5 parts of water and
57.9 parts of sodium sulfate and 0.15 g of optical brightener of the formula

SO ₃ Na

= CH and 0 »20g optical brightener of the formula

contains.

The fabric is then washed at 90 ° for 15 minutes with gentle mechanical agitation. After this

1098 15/2159

Wash the fabric first with lukewarm, then with cold ¥ rinsed water. During this washing process there is a lightening of all 3 types of fabric.

109815/2159

. 169511g

Example 37

9 parts of dodecyl sulfate, /

11 parts of dodecylbenzenesulfonate, 11 parts of sodium tripolyphosphate, 17 parts of tetrasodium pyrophosphate, 37 parts of sodium sulfate and 0.2 part of the lightening agent of Example .1

are made into a paste with 170 parts of water 60 dried and then ground.

6 parts of this washing powder are dissolved in 1000 parts of water at 70-80 and a 0.5 part active Chlorine corresponding amount of sodium hypochlorite solution is added. After a dwell time of 30 minutes, the washing liquor thus obtained is an undyed cotton fabric Washed in an elot ratio of 1:30 for 30 minutes at 80 ° ", then rinsed and dried. A very "beautifully lightened fabric" is obtained.

10981572159

Example 38

A cotton cretonne fabric is used in the liquor ratio. 1:30 at 60 for 20 minutes in a ¥ asch-. washed liquor, which per liter 5g of a detergent of the Composition:. .

"55 parts of sodium pyrophosphate, 30 parts of dodecylbenzenesulfonate, 15 parts of sodium dichloroisocyanurate (chlorine content

$) and

0.33 parts of the brightener mentioned in Example 1 contains. A fabric is obtained after rinsing and drying of neutral white aspects

«AD

10 9815/2159. ^tin

Claims (10)

Claims in which
R-, and R. independently of each other a mononuclear or polynuclear, condensed or: uncondensed aromatic carbo- or heterocycle, which is connected to the pyrazole ring by a ring carbon atom of an aromatic ring, of which radicals R-, and R. one in conjugation to the pyrazole bond '' a - optionally substituted styryl radical { and each is hydrogen or a monovalent substituent mean, where R-, and Rp together with the associated ring members of the pyrazole ring can also form a fused ring. 2. Fluorescent pyrazole compounds according to claim 1, characterized in that one of R and R _{4 is} an optionally further substituted 4-stirby group. 1 0 9 8 1 5/2 1 5 9 BATH ORIGINAL ■ 169511. 3. Fluorescent pyrazole compounds according to claims and 2, characterized in that R ^ an optionally substituted Phehylrest and R. is an optionally further substituted "4-S'tilbylgruppe." 4. pyrazole compounds according to claims 1 to 3, characterized marked that the R-. or R, embodying 4-stilbyl radical in the p-position to the vinylene group still an aroylamide or contains ring-substituted s-triazinylamine substituents. 5. Pyrazole compounds according to Claims 1 to 3, characterized in that the _{4-stilbyl radical embodying R or R 4} also contains a 3-phenylpyrazolyl (l) radical in the p-position to the vinylene group. 6. pyrazole compounds according to claims 1 to 5, characterized in that R _? and R-, denotes hydrogen. 7. · 4, 4 ¹ -bis- [3-phenyl-pyrazolyl (l)] stilbene-2,2 'disulphonic acids, and their salts with inorganic and organic bases. 8. Detergents and dishwashing detergents, paper, textiles and plastics, characterized by a content of pyrazole compounds of claims 1 to 6. 10 9 8 15/2159 9. Process for the preparation of fluorescent pyrazole compounds of the formula I, characterized in that a hydrazine compound of the general formula II, " H ₂ N - NH - R ₄ (II). or one under the reaction conditions such as such a hydrazine compound reactive derivative of this compound, with a 1,3-diketone compound of the general formula III a, 0 R ₂ R ₃ . . . . R ₁ - C - CH - G = G (purple) with the reactive derivative of such a compound of the general formula III b, · 0 R ₂ R ₃
RC-C = CX (IHb) in which X is the esterified or etherified enolic hydroxyl group, especially chlorine or bromine, means with the reactive Derivative of a 1,3-diketone of the general formula III c, - 0 R ₂ R ₃ ti ι ■ ι / 1 R _n -C- CH - α (HIc) in which X ^ and X ₂ denote hydroxyl groups which are etherified or esterified, optionally with ring formation, or with the aroylalkynyl compound of the general formula III d, OR M I -3 R ₁ - C - C Ξ G _(IIId) 10 9 815/2159 BAD condensed by methods known per se to give a pyra oil compound of the general formula I, in which formulas. -R-,, R ₂ , R ₃ and R. have the meaning given in claim 1. - 10. Modification of the method according to claim 9, characterized in that one. Pyrazoline compound of general formula V, R ₁ - C = N. R ₂ CH-CH R ₃ in which R-,, R _? , R ₃ and R _{4 have} the meaning given in claim 1, according to what is known per se. Reacts methods with a hydrogen acceptor in such a way that, with elimination of the hydrogen in the 4- and 5-positions of the pyrazole ring, the corresponding pyrazole compound of the formula I, R ₁ - C = N- ¹ I ^ NR ₄ (I) R ₂ - J = C is formed. 3l.l2.KS / wi / l9.l.l96 £ 09 81 5/2159