DE1962353A1 - Styrofoam brightener - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKUSEN-Bayeiwerk Jt, DβΖ P «ent department Κ / Pr

Styrofoam brightener

The invention relates to new styryl compounds formula

(I)

in which R- and Rp independently represent hydrogen, halogen, an optionally substituted alkyl, alkoxy, cycloalkyl, aryl, aryloxy, alkoxycarbonyl or carbamoyl radical, the cyano or carboxy group, R. and R "together can form a fused aromatic or non-aromatic carbocyclic ring system, R, for hydrogen, halogen atoms, lower alkyl groups and the sulfonic acid group, R. for hydrogen, halogen, an optionally substituted alkyl, cycloalkyl, aryl, alkoxycarbonyl, or carbamoyl radical, the cyano - or carboxy group, Rc stands for hydrogen, an optionally substituted alkyl or aryl radical, and R, and R ₁ - together with the two carbon atoms of the triazole ring can form an optionally further substituted non-aromatic carbocyclic ring system, X for oxygen or a substituted one Imino group NRg, where Rg is hydrogen, an optionally substituted alkyl

Le A 12 707

1 0 ⁽ i '\ Ί ^r >I') 1 9 3

<A . Ο Γ -> O C ^

Cycloalkyl, aryl or carbamoyl radical, sinsn Ä'cyi-i ³ "" means alkoxy carbonyl, alkyl or arylsulfonyl radical *, 'and the preparation of the compounds I and their use as optical brightening agents.

Suitable alkyl radicals R ₁ , R ₂ , R ^, R ^ and Rg are: saturated or unsaturated alkyl groups with 1-4 C atoms, which are replaced by substituents such as halogen atoms, for example fluorine, chlorine or bromine, hydroxyl - »- cyano- or acyl groups, alkoxy groups with 1 - 4 carbon atoms ,. Alkqxycarbonylgruppen with 2-4 C _r atoms in the alkyl group, carboxyl groups, and the Phenylreßt optionally halogen ', lower alkyl and alkoxy groups bears, may be substituted. _of ,

Suitable aryl radicals R ₁ , R ₂ , R-, R, - and Rg are: Phenyl radicals which can carry one or more substituents, ■>. ··. for example halogen atoms such as fluorine, chlorine or bromine, as well as cyano, lower alkyl and alkoxy groups with 1 - 4 carbon atoms, which in turn can be further substituted z. B. by phenyl radicals, hydroxyl groups, halogen and phenoxy groups, also the carboxyl group, alkoxycarbonyl groups with 2-5 carbon atoms, alkylsulfonyl groups with 1-4 carbon atoms and the sulfonamide group. "'"'. ΐ

Suitable alkoxy and aryloxy radicals R ₁ and R ₂ are alkoxy groups with 1-4 carbon atoms or phenoxy groups.

A suitable cycloalkyl ^radical _{R 1} , R ₂ *% ^ ^R 6 is ζ · Β · the cyclohexyl radical,

Among acyl radicals R ^. should be understood to mean acyl groups with 1-4 carbon atoms, which in turn can be further substituted by halogen atoms, for example fluorine, chlorine and bromine, lower alkyl groups with 1-4 carbon atoms and phenyl groups, _. , can carry further substituents.

Le A 12 707 ■ - 2 -

1O 9 8 2 5/7 19

Alkoxycarbonyl radicals R ₁ J, R ₂ * R ^ »and Rg are to be understood as meaning ester groups with 2-4 carbon atoms. ; -

Under a possibly ^

R ₂ , R * and R ₆ should be an optionally Mt alkyl radicals 1 «4 carbon atoms mono- or disubstituted carboxylic acid amldgroupge ₍ ^ * '"'"'■''■.''"''"'

Among substituted Alkylsulfonylregten ^^ IHD lower alkyl "- ■ res'te having 1 - 4 'C-atoms, which in turn ·· ^r ireiter may be substituted with halogen atoms, s' siue adjust B. ^ ludrv chlorine or bromine, while under optionally ^; s substituted arylsulfonyl radicals aryl radicals with lower alkyl groups, with "1-4 carbon atoms, lower ^{alkoxy groups 1} or 4 carbon atoms, halogen atoms, s. B. fluorine, chlorine or bromine are understood *

Condensed aromatisehe ^; or non-aromatic earbo »cyclic rings which R ^ and Rg can form have 5 or 6 ring members» - ■. · ..

Examples are:

η ■ '■

KichtaromatxBche on the viö-iEriazolrlng fused ring systems, which R ₄ and R ₅ can symbolize together with the two C-Ätömerides vic -iriazolringes, are in particular cyclopenta « - uno, cyclohexane rings, which in turn are fused with a benzene ring, can »As examples of ' ^! these connected systems are highlighted as follows:

-BAD ORIGINAL

18Ü2353

Among the new, inconsistent compounds, those of the formula II should be emphasized in particular:

GH- = CH

wherein "R ¹ and R ^r p independently hydrogen _$ chloro, alkyl and alkoxy groups each having 1-4 C atoms, cyano _r Oarbalkoxygruppen with 1 - 4 C atoms in the alkyl group _for phenyl, R ¹ -, and R 'together can form a fused-on bensol ring, RU is hydrogen and the sulfonic acid group, R ¹ , hydrogen, an alkyl group with 1-4 C atoms, phenyl, which can be substituted by chlorine or cyano, cyano, the carbalkoxy group with 1-4 C Atoms in the alkyl group and the carbonamide group, RU an alkyl group with 1-4 carbon atoms, the Al-allyl, styryl, phenyl radical, one optionally substituted by alkyl and alkoxy groups each with 1-4 carbon atoms or a phenyl radical Phenyl radical means, X stands for oxygen or a group NR / -, where Rg stands for hydrogen, one optionally with cyano, carbalkoxy groups with 1 to 4 carbon atoms in the alkyl group, alkoxy groups with 1 to 4 carbon atoms, hydroxyl groups, acyloxy groups with 1 to 3 carbon atoms in the alkyl group, s Substituted alkyl group with 1 to 4 carbon atoms, the cyclohexyl, methylcyclohexyl or benzyl radical, acyl groups with 1 to 3 carbon atoms, Le A 12 707 - 4 -

1 O S 8 2 5/719? BATH ORIGINAL

Carbalkoxy groups with 1-4 carbon atoms *! in the alkyl group © or the phenyl radical

The new O ^ iazolylbenzaao! Derivatives can be based on ve ^ ehAedene Catfish are produced.

Those compounds of formula (I)> in eggs Rj, and; Rj- for Hydrogen, optionally substituted alkyl or aryl groups or in which Rj, and R_ together with the two C atoms of the triazole ring form a 5 "or 6-membered ring system; they can be obtained, for example, as a result that one oximinohydrazones of the formula

CH = CH

, -IH

(H)

OH

in which R ₁ , R ₂ »R3 and X have the meaning given above,

₁ , ₂ »3

either cyclized directly to (I) by the action of suitable dehydrating agents ,. or with the aid of dehydrating agents first into the 2-styrylbenzazolyltriazole-I-Qxides of the formula ■

(III)

Le A 12 707

1.Q982.5 / 219: *

1 Ü ö 2 3 Ii 3

in which R ₁ , Rp, Rz and X have the meaning given above, and these are then converted into the triazoles of the formula (I) by reduction.

The cyclodehydration of the oximinohydrazones (II) to the triazoles (I) can be carried out with the aid of processes known per se, 3, B, by the action of acid chlorides or anhydrides, such as acetic anhydride, without or in solvents, as such are, for example, excess acetic anhydride, Dimethyl sulfoxide, dimethylformamide, H-methylpyrrolidone, tetraethylurea, pyridine and technical pyridine bases are suitable alone or in mixtures with one another. The addition of bases such as sodium acetate, tri-diethylamine, triethylamine, dirnethylbenzylamine, pyridine or higher pyridine homologues is usually expedient _. however, the desired ring closure can also be carried out with acid catalysis.

Oximinohydrazones (ΙΪ) are also accessible by various methods. A preferred process of (II) is that d -oximinoketones of the formula (IV) with 4-hydrazinostyrylbenzazoles of the formula (V)

Vf- ⁰

R ₅ -G = NOH

(IV)

VcH =

Le A 12 707

(V)

- 6

BATH ORIGINAL

10 9 8 2 5/7193

19V.2353

in which R ₁ , Rp, R-, and X the meaning given above h condensed.

Suitable oximinoketones IV include: oximinoacetone, diacetyl _{monoxime f} 1-oximinobutanone, 2-oximino- 1 ~ phenylbutanone- (3) _f 1,3-biphenyl-1-oximinopropanone ~ (2) _f oximinobenzyl-cyclohexyl ketone, 1-oximino- 4-plienyl-buten ~ (3) -one- (2), 2-0ximinopentanon- (3), 3 ™ 0ximino-4-methyl-pentanone- (2), 1-oximino-4-ethylpentene- (3) - one- (2), 3-oximino ~ pentanal- (5) -one- (2), 3-oximinoheptanone- (4), "4-" oximino-honanon ~ (5), Qximino ™ acetophenone, p-fluoro, ρ-bromo and p-chlorooximinoacetophenone, p-methyl- and p-kethoxyoximinoacetophenonef 2,4- and 3,4-dimethyloxyainoacetophenone, oximinopropiophenone, o ~, m- and p ~ fluoro-, -chloro- and -broiaoximinopropiophenonef 3 _f 4-BichIoroximinopropiophenon, p-methyl- p _f ~ benzyl and p-Äthyloximincpro "piophenon, p-Benzyloxyoximinopropiophenon, p-phenoxy-oxiiainopropiophenoii; 2,4-methoxy-methyl-oximinopropinphenone, 2,4-dimethoxy-oximinopiopiophenone, 2,5-dimethyloximinopropicphenone, 2-0ximino-1 _f 3-diphenylpropanone- (i), 1-phenyl-1-oximinoacetone, 1-0ximino ~ l ~ o ~, -m- and -p-tolylacetone, 1-oximino-lo-, -m- and -p-anipylacetone, T-oximino-1-o-, -m- and -p-chloroplienj ^ lacetone , 1-oximino-im- and -p-cyanophenylacetone, 1-oximino »1-m- and -p-carbethoxyphenylacetone, 1-oximino-im- and -p-methanesulfonylphenylacetone, l-oximino-1,3-diphenylacetone, 4 -Phenyloximinopropiophenon, Oximinobutyrophenon, / ^ - ^ -oximino-benzoyl buttersäuremethyl- and ethyl esters, Oximinovalerophenon, oximino-1- and -2-propionaphthon, benzil monoxime, Tolilmonoxim, Anisilmonoxim _s 4-methoxy-oxIminodesoxybenzoin, Oximinocyclopentanon, Oximinocyclohexanon, 2- 0ximinoindanone- (1), 2-oximinotetralone- (1).

Oximino hydrazones of the formula (II) in which .ILj, R ₂ , R ,, R., R ^ and X have the meaning mentioned, can also be obtained by mixing approximately equal molar amounts of the hydrazinostyrylbenzazole of the formula (V) with hydroxylamine or its salts in any order with glyoxal or the (IV)

Le A 12 707 ~ 7 -

10 9825/2193

basic ot-diketones of the formula (VI) condensed.

R _x -C = O

⁴ I.

R ₅ -C = O

(VI)

The hydrazino compounds (V) to be used for the condensation can be derived from the corresponding nitro compounds. (VII.) ,. . . , win, which one first by known methods, eg
according to Bechamp using iron and hydrochloric acid or using hydra-ζin in the presence of Raney-Niekel to the amino compounds
Formula (VIII) is reduced, this is diazotized and the diazonium salts obtained are reduced by conventional methods.

VII: - ■ 'Y = NO

VIII:

The nitrostyrylbenzazole derivatives (VII) used as starting materials can be p-nitrobenzaldehydes substituted by condensation the formula

OHC - (/ Λ -NO

(IX)

in which R has the meaning mentioned at the beginning; e.g.
p-Nitrobenzaldehyde, 2-methyl-4-nitrobenzaldehyde, 2-chloro-4-nitrobenzaldehyde, 4-nitrobenzaldehyde-2-sulfonic acid and their functional derivatives such as bisulfite compounds, acetals, anilene, etc. with 2-methylbenzaz'ol derivatives of the formula

Le A 12 7Ö7 · ¹ "

1 0 S! "Ί- / S /? 1. 9

D ORIGINAL

(χ)

.in which S ₁ , Rp ^{and χ have the} meaning given by 0 ^ e * ^1.

Examples of 2-methylbenzoxazole derivatives (X; X = O) are the following:

2-methylbenzoxazene; 2.5; 2,6- and 2,7-dimethylbenzoxazole; 2-methyl-5-benzylbenzoxazole / 2-methyl-5-t * » ^Q k-dimethylbenzylbenzoxazole; 2-methyl-5-ethylbenzoxazole; 2-methyl-5-propylbenzoxazole; 2-methyl-5-isobutylbenzoxazole; 2-methyl-5-tert-butylbenzoxazole; 2-methyl-5-phenylbenzoxazole; 2-methyl-5-oyclohexylbenzoxazole; 2-methyl-4,5-cyclotetra-methylenebenzoxazolej 2-methyl-5-chlorobenzoxazolej 2,5,6-trimethylbenzoxazole; 2,5,7-trimethylbenzoxazole; 2-methyl-5-methoxybenzoxazole; 2-methyl-5-ethoxybenzoxazole; 2-methyl-5-cyanobenzoxazole; ^ -Methyl-S-carbethoxybenzoxazole; 2-methyl-5-carbonamidobenzoxazole, 2-methylbenzoxazole-5-carbonic acid diethylamide and 2-methylnaphthoxazole.

Examples of 2-methyl-benzimidazole derivatives (X; X = N-Rg) are the following:

2-methylbenzimidazole, 2,5-dimethylbenzimidazole, 2,7-dimethyl benzimidazole, 2-methyl-5-lIlethoxybenziπlidazol, 2-methyl-5-äthoxybenzimidazol, 2-methyl-5-chlorbenzimida _ι zol, 2-methyl-6-chlorobenzimidazole, 2-methyl-benzimidazole ^ -carboxylic acid methyl ester,

1- carboxyethyl-2-methylbenzimidazole; 1,2-dimethylbenzimidazole; 1-benzyl-2-methylbenzimidazole} 1-p-chlorobenzyl-2-methylbenzimidazole; 1- / d> r methylbenzyl / ^ - methylbenzimidazole} 1-ethyl-2-methylbenzimidazole; 1- / B-chloroethyl7-2-methylbenzimidazolej 1-vinyl-2-methylbenzimidazole ; 1- / B ~ phenylethyl / -2-methylbenziBidazolj 1- _l / 2-0yanäthyl7-2-methylbenzimidazole} 1- / B-hydroxyethyl / -2-methylbenzimidazole; ■ ^ - / ß-Acβtoxyäthyl / -2-mβthylbenz-

L A 12 707 - 9 -

40 1 Bo ^ yJ b 3

imidazole; 2-methyl- / benzimidazolyl "- (1) y ~ e 2-methyl-zbenzimidazolyl- (1 ^ / - acetic acid ethyl ester; 2 - methyl- '· ■ / benzimidazolyl- (1) 7-acetic acid propyl ester j 2-methyl / benz- · ^; - · ~ imidazolyl- (i) / - e3-acetic acid amide; 2-methyl- / tenzimida20lyl- (1) / -acetic acid ethylamide, 1-n ~ propyl-2 ~ methylbeii2; iiaidazOl; 1-isopropyl-2 = methylbenzimidazole; i- / β-hydroxypropyl / -2-methylbenzf «imidazole, 1- / 13-acetoxypropyl / -2-methylbenzimidazole, 1-allyl-"2-methyltienimidazole; 1- / ß-methallyl / -2 ~ methylbenzimidazole; ·: "■ 2-methyl- / benzimidazolyl- (i) / propionic acid methyl ester; 2-methyl- / benzimidazolyl- (1) _ / -. propionic acid dimethylaniid; I -n-butyl-2-methyibenzimidazole; 1 -Isobutyl-2-methylberiziiaidazole; 1-cyclohexyl-2-methylbenzimidazole; 1 - / δ-methylcyclohexyl / -2-methyl>benzimidazole; 1- / m-methylcyclohexyl / ~ 2-methylbenzimidazole; 1- / p-methylcyelohexylZ-benzimidazole; i.-Phenyl-2-niethylbenzimidazole; 1- / p-chlorophenyl7-2-methylbenzimidazole; 1,2,5-trimethylbenzimidazole; 1-BerLzyl-2,5-dimethylbenzimidazΌl, 1- / ß-phenethy l / -2,5-dimethylbenzimidazole, 1- / ß-methoxyeth l / -2,5-dimethylbenzimidazole, 1- / ß-cyanoethyl / -2,5-dimethylo9nzimidazole, 2,5-dimethyl- / benzimidazolyl- (i) ^ -acetic acid ethyl ester, 1,2-dimethyl-5-trifluo-methylbenzimidazole, 1,2-di; ethyl-5-methoxybenzimidazole, 2-methyl-5-methoxy- / benzimidazolyl - <- (1 \ J ~ ethyl acetate, 1 ^ -Dimethyl-S-chlorobenzimidazole, 1,2-dimethyl-5-cyanobenzimidazole, i-ethyl - ^ - methyl - ^ - cyanobenzimidazole, T- / ß-acetoxyethyl / ~ 2- methyl-5-cyanobenzimidazal, 1- Ethyl-2-methyl-6-cyanobenzimidazole, 1,2-dimethyl-benz ₁ iraidazole-5-carboxylic acid ethyl ester, 1- / ß-acetoxyethyl 7-2-methyl-benzimidazole-S-carboxylic acid ethyl ester, 1,2-di-methylbenzimidazole ~ 5-carboxylic acid dimethylamide , i-acetyl-2-methylbenzimidazole, 1-dichloroacetyl-2-methylbenzimidazole, 1-propionyl-2-iaethylbenzimidazole, 1-acetyl-2,5-dimethylbenzimidazole, 1-acetyl-2-methyl-5- methoxybenzimidazole μnd! , a-DImethyl-naphth- ^ Silig ^ - imidazole

The condensation of the benzazole derivatives (X) with the nitrobenzene aldehydes (IX) or their functional derivatives can be carried out by methods known from the literature sB, by

Le A 12 707 ν - 10 -

1O9825 /? 19 ^ BADORiGINAL

1ÜS2353

warm the components in equivalent amounts in the presence of acidic condensing agents such as ■ boric acid, phosphoric acid or Zinc chloride in the melt, or more appropriately in one Mixture of acetic anhydride and glacial acetic acid.

Compounds of formula (I) in which R ^ is optionally substituted alkyl or aryl radical, while R. is cyano, the carboxylic acid group, a carboxylic acid ester group or denotes an optionally substituted carboxamide group can be obtained by adding amino compounds of the formula VIII diazotized, the diazonium compounds obtained with relevant enamines of the formula. ·

R \ - CH

4 I ·. - {fry

■ R » ₅ - C-IiH ₂ . - ■ ■ ■

in the R ^f j. Cyan, a carboxylic ester or amide group and R'p- denotes an optionally substituted alkyl or aryl radical, or couples with their tautomeric ketimides, ζ · Β. with ß-aminocrotonic acid nitrile, ester or amides, the resulting azo compounds of the formula:

with dehydrating agents, such as complex copper (II) salts, lead tetraacetate, etc., by warming in suitable solvents such as alcohols, pyridine, bimethylformamide and mixtures thereof with water, to give the desired triazolylstyrylbenzazoles of the formula (I).
Further processes for the preparation of the Triazolylstyrylbenz-

Le A 12 707 - 11 -

- .; T362353 ν

azoles (T) which are particularly suitable when R, for Hydrogen, the sulfonic acid group, R. and R, - for hydrogen, Alkyl or aryl radicals are the condensation of triazolebenzaldehydes of the formula

OHC-T Vli '(XIII)

e.g. 4- / 4-methyl-vic-triazolyl- (2) / -benzaldehyde, 4- / 4-methyl-5-ethyl-vic <-triazolyl- (2) ./- benzaldehyde, 4- / 4-styryl-victriazolyl- (2) _ / - benzaldehyde, 4- / 4-phenyl-vic-triazolyl- (2) / - benzaldehyde, 4 - / "4-phenyl-5-methyl-vic-triazolyl- (2 ^ -benzaldehyde j 4- / 4 - phenyl-vic-triazole- (2) / - benzaldehyde-2-sulfonic acid, 4- / 4,5-diphenyl-vic-triazolyl- (2) / - benzaldehyde-2-sulfonic acid, as well as their functional derivatives, such as bisulfite compounds, Acetals, anils, etc. with 2-methylbenzazole derivatives of the formula X in the presence of acidic or basic condensing agents.

The new triazolyl (2) benzaldehydes (XIII) can also be prepared by known processes (le A 12 177). ^ Another way of representing the lightening agents of the formula (i), in which R ₁ , R "and X have the meaning given above, while R- for hydrogen, R. and R ₁ -for hydrogen, optionally substituted alkyl or aryl radicals stand consists in the condensation of the aniline derivatives of the formula

(XIV)

with 4-vic-triazolyl- (2) -cinnamic acid derivatives of the formula

Le A 12 707 - 12 - '

10 9 8 2 5/2193

ORIGINAL SNSPEGTiD

ή π ς ο q

I c! O c <- ⁵ ZOC-GH = CH- ( ^{/ x} VN Γ ^ (XV)

in Z a hydroxyl, alkoxy, amino or halogen radical means in the presence or absence of solvents to the derivatives of the formula

FH _x

00OH = CH - // \\ - Έ T-. (XVI)

in which the substituents R-, R ₂ , R *, Rc and X have the meaning given above, which are subsequently converted into the lightening agents of the formula '(I) using dehydrating agents either in the melt or, if appropriate, in the presence of high-boiling solvents. Suitable condensing agents are phosphorus oxychloride, phosphorus pentachloride, polyphosphoric acid, boric acid, zinc chloride, zinc bromide and sodium hydrogen sulfate or an org. Acid such as, for example, p-toluenesulfonic acid called. Suitable solvents are mono-, di- and trichlorobenzene, xylene and cumene. The water or alcohol formed in the reaction is expediently distilled off during the reaction, possibly with the aid of solvents.

Examples of 4-vic-trlazolyl- (2) -cinnamic acids of the formula (XVI) include the following:

4- / 4 - methyl-vic-triazolyl- (2! / - cinnamic acid, 4- / 4-methyl-5-ethylvic-triazolyl- (2! / - cinnamic acid, 4- / 4 ~ styryl-vic-triazolyl- (2) / - cinnamic acid, 4- / 4-phenyl-vic-triazolyl- (2! / - cinnamic acid, 4- / 4-phenyl-5-methyl-v-ic-triazolyl- (2) / - cinnamic acid and 4- / 4,5-diphenyl-viG-triazolyl- (2X7-cinnamic acid.

Compounds of the general formula (I) in which R, halogen,

Le A 12 707.: ■ ".- Ö -

1 0 3 B ? ^r > / 7 1 9 ■ "* BAD ORIGINAL

1982353

Cyan and Rj- for hydrogen or the heny-lgroupjse * "rend R ₁ , R ₂ > Rz and X have the meaning given, can be produced, for example, thereby» 3a3 one diazo verb in- * · - ■ fertilize 2- / 4 - aminostyryl / -benzazoles £ 3Γ formula (VIII) with ■ -oxynes of the formula

O ₉ N-CH

R » ₅ - C = NOH

in which R ', - is hydrogen or a phenyl radical, ■ -ζ. B. with Nitroacetaldoxim or <* / - iTitroaeetophenonp-xim "couples, azo compounds obtained to form the corresponding 2- / 4- (4-Nitrotriazolyl- (cyclized 2) -styryl7benzazolverbindtingen, the nitro group reduced to the amino nnä this by Sandmeyer in Transferred to chlorine or cyan.

Compounds of general formula (I) _t in which X G roup N-Rg group, can also be prepared by alkylation or Aralkylierurig the compounds of formula.

X-CH = CH-T ^X ) -NJ (XVIII)

/ V4 = / ^N

with alkyl-, oxalkyl- or arylalky! halideη in solvents, expediently with the addition of acid-binding agents. Dialkyl sulfates such as e.g. Dimethyl sulfate or vinyl compounds are used%;

The new compounds of the formula (I) are yellow-green to almost colorless compounds that turn blue in solution when irradiated fluoresce strongly blue with UV light. It is • very suitable for lightening a wide variety of materials s, B. "From

Le A 12.707 _{r 1ψ} „■■■■ _ ■■

1 0 9 8 ■? B / ν l 9 *?

BATH ORIGINAL

1 Q ρ '. Q ζ ^

Cotton, paper and other cellulose materials as well as wool, and also for lightening fibers, threads, fabrics, foils and other structures made of synthetic polyamides, polyesters, polyvinyl chloride, cellulose acetates, etc. Detergents are used. They can be used in the usual way, for example in the form of aqueous solutions or dispersions or as solutions in organic solvents such as glycol monomethyl ether, diglycol, thiodiglycol, tri-, tetra- and polyglycols, dimethylformamide, formamide, triethanolamine, etc. They can also be used in conjunction with detergents are, and melt and spinning masses can be added, which are used for the production of fibers, films or moldings. The quantities to be used can easily be determined by preliminary tests; In general, additions of 0.1 to 1 fo, based on the weight of the material to be lightened, prove to be sufficient.

example 1

26.5 g (0.1 mol) of 5-methyl-2- / 4-hydrazinostyry! / - benzoxazole are mixed with 19.6 g (0.12 mol) of oximinopropiophenone and 10 ml of 50 percent strength. Acetic acid in 250 ml of glycol monomethyl ether heated to 80-90 °. After a spot test with o-naphthoquinone-4-sulfonic acid no longer shows free hydrazine after stirring for 2½ hours at 90 °, 150 ml of solvent are distilled off in a weak water jet vacuum, the mixture is cooled and the precipitated condensation product is suctioned off and dried. 35 g of the condensation product obtained in this way are then stirred in 200 ml of anhydrous dimethylformamide with 13 ml of acetic anhydride and 10 g of anhydrous sodium acetate for 5 hours at 80 ° and 1 hour at 100 °, the inorganic salts are suctioned off while hot and the dimethylformamide is largely distilled off in a water jet vacuum remaining residue is stirred with 50 ml of methanol, the mixture is cooled and the formed

Le A 12 707 ■. - 15 -

1 0 H 3? S / '? 1 9?

GAD OBiGiNAL

1Ü62353

dete triazole sucked off. Recrystallize twice from Di ο:

keep.

light yellow crystals with a melting point of 196 ° -197 ° are obtained from dioxane

The table below is obtained in an analogous manner lightening agents of the formula listed under b to i

Lightening
middle ^ß 1 ^R 4 H ■ ^H 5 Melting point
⁰ C a CH ₃ P-Cl-C ₆ H ₄
CH, ^C 6 ^H 5 196-197 b CH ₃ CH, ^C 6 ^H 5 C.
d - CH ₃ H CH ₃ 224-225
179-180 e
f Cl
H P-Cl-C ₆ H ₄ • CH ₃
^C 6 ^H 5 266.5-267.5
199.5-200.5 H C ₂ H ₅ ^C 6 ^H 5 209-210 H H CH ₃ 210-211 i H C ₃ H ₇ 142-143

Here, instead of the oximinopropiophenone, which is used for Preparation of the lightening agent described under a and f is used, oximinoacetophenone (b; g), 1-oximino-ip-chlorophenyl acetone (ei h); Oximinodiethylketone (d) | 1-oximino-1-m-cyanophenyl acetone (e) or oximinodipropy! ketone (1) used; in addition, for those listed under d to g Lightening agent instead of the 5-methyl-2- ^ r-hydrazinostyryl7-

Le A 12 707 ■ - 16 -

. 1 0 £ B 2 5 /? 19 ^

'INSPECTS *

benzoxazole the 5-chloro-2- / 4-hydrazinostyryl / ~ benzoxazole or 2- / 4-hydrazinostyryl / benzoxazole is used.

Example 2

.25 g (0.1 mol) of 5-methyl-2- / 4-aminostyry! / - benzoxazole in a mixture of 250 ml of glacial acetic acid and 25 ml of propionic acid dissolved and with 70 ml conc. Hydrochloric acid added. After cooling down the resulting clear, deep red solution is diazotized to 0 ° with a solution of 6.9 g of sodium nitrite in 25 ml of water to a solution of 22 g (0.11 mol) ß-amino cinnamon ester in 100 ml Pyridine was added dropwise at pH 5.5. After the coupling has ended, the azo dye is filtered off with suction, washed with water and added to 45 ° dissolved in 400 ml of pyridine. The red solution is at 45 ° with a solution of 48 g of copper acetate in 400 ml of water and then stirred for 4 hours at 60 ° and 1 hour at 90 °. After cooling, the precipitated iriazolylstyrylbenzoxazole is filtered off with suction and washed with hot water. To After drying, the brightening agent obtained is recrystallized once from dimethylformamide and subsequently from dioxane. A slightly yellow colored powder with a melting point of 193 ° -194 ° is obtained.

The lightening agents of the formula - listed in the following table under b to h

are represented in an analogous way.

Le A 12 707 - 17 -

ORIGINAL INSPECTED

Whitening
middle R ₁ H COOC ₂ H ₅ ^C 6 ^H 5 1962353
Melting point
⁰ C a GH ₃ H CN C ₆ H ₅ 193-194 b CH ₃ H C CN ^C 6 ^H 5 236-237 C. (CH ₃ ) ₃ H C COOC ₂ H ₅ CH ₃ 267 d (CH ₃ ) ₃ CN ° 6 ^H 5 178-180 e COHH ₂ ^C 6 ^H 5 224 f COOC ₂ H ₅ GH ₃ 284 G CN CH, 196 H 273

In this case, instead of the ß-Aminoζimtsäureäthylesters, which is used for the preparation of the lightening agent described under a, ß-Aminozimtsäurenitril ("bj" cj e)} ß-Aminocrotonsäureäthylester (d; g) or S-Amino cinnamic acid amide (f) is used ; in addition, for the lightening agents listed under c to h, 5-tert-butyl-2- / 4-aminostyryl _i 7-benzoxazoi or 2- / 4 -Aminostyryl / -benzoxazole used.

Example 3

A fabric made of polyester fibers is in a liquor ratio of 1 * 40 placed in a bath containing 1.5 g of sodium oleyl sulfate per liter, 0.75 g of formic acid and 0.1 g of one of those listed in Example 1 under a to i or in Example 2 under a to h Lightening agents of the formula I contains. The bath is heated to the boil within 30 minutes and then on for about 45 minutes Maintained boiling temperature, whereby the fabric is moderately agitated. The fabric is then rinsed and dried. It then has a good brightening and good lightfastness.

Le A 12 707 "18" "

1 Π ^c ; ^p «2 B / '"? ¹ 9 ^ ■ · ^v ■'''"ORlGiWALINSPEGTED

Compared to the next comparable 5-methyl-2- / 3 - (3'-methyl-5'-phenyl-pyrazole- (1 O-s'tyrylZ-benzoxazole (NE 6 515 601 Ex. yill) has that with the lightening agent of Example 1a treated tissue a stronger lightening.

Example 4

Fabric made from fibers made from poly-έ-caprolactarn were, 30 minutes in the liquor ratio 1t40 at 80 in treated in an aqueous bath containing 0.3 g of one of the liters in Example 1 under a to i and in Example 2 under a to h contains designated whitening agent. After rinsing and drying, the fabrics show a good lightening of good Lightfastness.

Compared to the next comparable 5-methy 1-2- / 4 · (3'-methyl- 5'-phenyl-pyrazole- (1 ') -styryl / -benzoxazole (Hl 6 576 601 Ex. YIII) has that with the lightening agent of Example 1 a treated tissue a stronger lightening.

Example 5

11.8 g (0.05 mol) of 1-benzyl-2,5-dimethylbenzimidazole are mixed with 12.45 g (0.05 mol) of Af \ ~? HenYl-vlc- ~ tTeiZolyl- (2) J-benz aldehyde, 10 ml acetic anhydride and 7.5 ml anhydrous acetic acid heated to 130-140 for 48 hours. After cooling, the contents of the flask are stirred with 100 ml of methanol, and the product which has precipitated is filtered off with suction and dried. After recrystallization from dimethylformamide, yellow-green crystals with a melting point of 245 ° -246 ° are obtained. The lightening agents of the formula listed in the table below under b to ο

are represented in an analogous way.

Le A 12 707 - 19 -

1 0 2 S / ^ / '- ■ ι 9

ORIGINAL INSPECTED

On- R ₁

brightening

middle

Melting point

⁰ C

CH,

(GH ₂ )

245-246

192.5-193.5

CH ₃

Cl

C ₂ H ₅ -OCO

H H.

CH,

CH,

CH

CH,

^C 6 ^H 5

^G 6 ^H 5

^C 6 ^H 5

^C 6 ^H 5

^: 2 ^H 5

^C 6 ^H 5

183-184

215-216

187.5-188

187-188 157-158

224.5-225

H H H

Le A 12

CH ₂ CH ₂ OH

° 6 ^H

6 ^H 5

° 6 ^H 5

CH-,

- 20th
B 1 ^ / 7

^C 6 ^H 5

225-227 165-166 153-154

ORiGiMAL INSPECTED

Here, instead of the 4- / 4-phenyl-vic-triazolyl- (2) ^ / ~ benzdehyde, for the production of the under a; bj cj d; ej f | hj kj 1 and m listed lightening agent is used, 4- / 4-phenyl-5-methyl-vic-triazolyl- (2) _ / - benzaldehyde (g) or 4- / 4-ethyl-5-methyl-vic-triazolyl- (2) / benzaldehyde or 4- / 4- styryl-vic-triazolyl- (2 ^ -benzaldehyde (o) used} also 'is used for the lightening agents listed under b to ο instead of 1-benzyl-2,5-dimethylbenzimidazole (a), 1- / ß-phenethyl / -2,5-dimethylbenzimidazole (b), 1-ethyl-2,5-dimethylbenzimidazole (c) $ i-benzyl ^ -methyl ^ -ehlorbenzimidazole (d), 1-benzyl-2-methyl-benzimidazole-5-carboxylic acid ethyl ester (e), 1-Benzyl-2-methyl-5-cyanobenzimidazole (f), 1,2-dimethylbenzimidazole (gj hj i;), i-benzyl-2-methylbenzimidazole (k), 1- / S-hydroxyethyl / -2-methylbenzimidazole (1) or 1-phenyl-2-methylbenzimidazole (m; nj o) are used.

Example 6

A fabric made of polyester fibers is padded with an aqueous liquor containing 1 g of a commercial dispersant based on fatty alcohol polyglycol ethers, 1 g of a commercial wetting agent based on alkylnaphthalenesulfonic acids, 4 g of alginate thickening and a solution of 1 g of one of the lightening agents in a liter Contains 20 g of triethanolamine, which are listed in Example 1 under a to i, in Example 2 under a to h and in Example 5 under a to ο. The fabric is then squeezed off to a weight increase of $ 100, then dried, heated to 180 ° for 1 minute and then washed hot. Compared to untreated fabric, the ao-treated fabric shows a clear, extremely bright lightening of good lightfastness.

Example 7

1000 g of opaque polyvinyl chloride are used on the WaIas 1 g one of those listed in d-: a: Example 5 under a bia ο

Le A 12 707 «2.1

1do2353

Lightening agent incorporated. The material is then outstandingly lightened and shows a reddish-tinged white shade of ^: good lightfastness.

Example 8

7.5 S l., 2 "M-methylbenzimidazole (0.05 mol) are in a Mixture of 150 ml of diethyl sulfoxide and 50 ml of tert-butanol dissolved and mixed with 14 g of potassium tert-butoxide, while passing through of nitrogen becomes a solution of 16.5 g at 30-35 ° (0.05 mol) 4- / 4-ihenyl-vic-triazolyl- (2) / »benzaldehyde-2-sulfonic acid added dropwise in 150 ml of dirnethyl sulfoxide. After finished Addition is continued for a further 6 hours while bubbling through nitrogen stirred and the mixture with stirring in 1000 ml of 10-pros, saline solution registered. After briefly stirring it is suctioned off, the iriazole obtained was washed twice with 20 ml of ice-cold, saturated sodium chloride solution.

Subject recrystallization once from 50-pro2, aqueous dimethylformamide the lightening agent is obtained as a yellow-green powder.

Is used instead of 1,2 ~ dimethylbenzimidazole for Condensation the 2 * »methylbenzimida ^ ole listed in the table, the following triazolyl-3-tilbene varnishes are obtained in an analogous manner the formula

H JR, -

e A V-:

bath

Aufhel- R ₁
l-
middle

13G2353

H H H HS H H H HS H H H HS πττ
\ - / Xx * v H ^C 6 ^H 5 HS H CH ₃ H HS H CH ₃ H HS CH ₃ H H HS CH ₃ H H HS CH ₃ O H H HS

Cl

Cl

Cl

CK

ο Η
PH

q H

Le A 12 707

H ^C 6 ^H 5 ° 6 ^H 5

H H

Cl H

^C 6 ^H 5

^C 6 ^H 5

H H

CN C ₆ H ₅ C ₆ H ₅

HS

- 23 - ■

CH,

C ₂ H ₅ C ₂ H ₅ CH ₂ CH ₂ -OH

CH ₂ CH ₂ OCOCH ₃ CH,

CH,

C ₂ H ₅

Example 9 . ■

1 kg of curd soap is mixed with 1 g of the whitening agent of the formula

mixed to a homogeneous mass. Soap treated in this way has a much whiter appearance in daylight than the untreated one Soap.

Similar results are obtained when using as a whitening agent the sodium al ze in Table 8 under b to q. cited lightening agent used. "

Le A 12 707. 24 -

1 0 I V S /> 1 9 ^ ■

OfIfGlNAL

Claims (1)

Claims CH = CH- in which R- ^ and R- independently represent hydrogen, halogen, an optionally substituted alkyl, alkoxy, cycloalkyl, aryl, aryloxy, alkoxycarbonyl or carbamoyl radical, - the cyano or carboxy group, R- ^ and Rp together can form a fused aromatic or non-aromatic carbocyclic ring system, R, for hydrogen, halogen atoms, lower alkyl groups and the sulfonic acid group, R. for hydrogen, halogen, an optionally substituted alkyl, cycloalkyl, aryl, alkoxycarbonyl, or Carbamoyl radical, the cyano or carboxy group, Rc stands for hydrogen, an optionally substituted alkyl or aryl radical, and R. and R ^ together with the two carbon atoms of the triazole ring can form optionally further substituted non-aromatic carbocyclic ring system, α for oxygen or a substituted imino group NRg, where Rg is hydrogen, an optionally substituted alkyl, cycloalkyl, aryl or Carbamoyl radical, an acyl, alkoxycarbonyl, alkyl or arylsulfonyl radical. Le A 12 707 - 25 - 5/219? 193235 3 2.) StyryI compounds of the formula CH = CH- wherein R'- and R'p independently represent hydrogen, chlorine, alkyl and alkoxy groups each with 1-4 carbon atoms, cyano, carbalkoxy groups with 1-4 carbon atoms in the alkyl group, phenyl, R ¹ - ^ and R 'together can form a fused benzene ring, Ri, hydrogen and the sulfonic acid group, RJ, hydrogen, an alkyl group with 1-4 carbon atoms, phenyl, which can be substituted by chlorine or cyano, cyano, the carbalkoxy group with 1-4 C atoms in the alkyl group and the carbonamide group, Rl an alkyl group with 1-4 C atoms, _s the alkyl _} styryl, phenyl radical, a phenyl radical optionally substituted by alkyl and alkoxy groups each with 1-4 C atoms or a phenyl radical X denotes oxygen or a group N-Rg _a where Rg denotes hydrogen, one optionally represented by cyano, carbalkoxy groups with 1 to 4 carbon atoms in the alkyl group, alkoxy groups with 1 to 4 carbon atoms, hydroxyl groups, acyloxy groups with 1 to 3 carbon atoms in the alkyl group, substituted e alkyl group with 1 to 4 carbon atoms, the cyclohexyl, methylcyclohexyl or benzyl radical, acyl groups with 1 to 3 carbon atoms, carbalkoxy groups with 1-4 carbon atoms in the alkyl group or the phenyl radical, Le A 12 707 - 26 "- 1 0 S 3 2 5/2 I 9 3 ORfGfNAL INSPECTED 19G235 3 ·) Process for the production of the JStyry! Connections the formula wherein E _{1 r} R ₂ , · R ₃ and X have the meaning given in claim 1, while R ₄ and R _{5 are} hydrogen or. a ^ optionally substituted alkyl or aryl group, where R ₄ and R ₅ together with the two carbon atoms of the triazole ring can also form a 5- or 6-membered non-aromatic ring system, characterized in that oximinohydrazones of the formula: . ■ CR ₄ wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and X have the meaning given above,
treated with dehydrating agent. ' 4.) Process for the production of Styry! Compounds of the formula Le A 12 707 ORIGINAL INSPECTED wherein R _1, Rg # R- * and X ^ are as defined in claim 1, Rh and R is hydrogen or an optionally ■ - ■■ are substituted alkyl or aryl, wherein R ^ and R _c together with the two C atoms of the triazole ring can also form a 5- or 6-membered non-aromatic ring system, characterized in that triazole-N-oxides of the formula GH = CH- ( ^X ) -N R * -O wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and X have the meaning given above,
reduced. 5.) Process for the production of Styry! Connections the formula where R ₁ * R ₂ and X have the meaning given in claim 1 * R ^ is hydrogen, R _{5 is} an optionally substituted alkyl or aryl radical and R _{1 is} cyano, the carboxyl group, a carbalkoxy group or an optionally substituted carbonamide group Le A 12 707 '- 28 1 0 .S..W .1 /? 1 9 ■? OBKSINAL INSPECTED represents, by using aminoazo compounds of the formula ' where B ^, H ₂ , ^ a »^ 4« ^R s ¹ ^ Ad X have the meaning given,
triazolized * 6.) Process for the preparation of styryl compounds of formula where I _{4 stands} for halogen, Öyan Ig for ¥ aaaeratoff or a phenyl group and E ₃ for Wasaeratoff, while R ₁ , Rg and X have the meaning given in Änsprueh 1 »characterized in that the Eupoppelaproaukte diazotized 2- [4-AminoS ; tyryll-benzazQle cyclized on a-litroaximen ^ the nitro group reduced to the amino group and converted into chlorine or oyan by known methods. 7 ·) Process for the preparation of styryl compounds the formula ORIGINAL INSPECTED where R ₄ and E _{5 represent} hydrogen or an optionally substituted alkyl or aryl radical, where ^: R ₄ and R ₆ together with the two carbon atoms of the tr.iazo.lring also form a non-aromatic 5- or 6-membered ring system can form, and R _{3 is} hydrogen, Slne ~ 13f * üp ~ pe SO ^ M, "where M is hydrogen or an organic or inorganic cation , while R ,, Rp and X have the meaning given in claim 1» characterized * that one triazolbenzaldehydes of the formula. OHO- in which R ₃ , R ₄ and R _{6 have} the meanings given above, with 2-methylbenzene of the formula in which R ₁ and R ₂ are as defined above. 8.) Process for the production of styryl compounds formula R ₆ where R ₅ denotes hydrogen, R ₄ and R ₉ denote hydrogen, an optionally substituted alkyl or aryl radical, R ₁ , B ₂ and X denote the meaning given in Anapruoh 1 A IZ 7OT -3 0- ORIGINAL INSPECTED- possess, characterized in that 4-vic.-triazolyl- (2 ' ) -cinnamic acid amides of the formula in which R ₁ , R ₂ , R ₃ , - R ₄ , R ₅ and X have the meaning given above, treated with dehydrating agents in the melt or in the presence of high-boiling solvents. 9 ·) Process for the preparation of styryl compounds of the formula
CH = CH- / ⁷ \\ - N w ^ V ~ ^iV "^ R ₄ in which R, represents hydrogen, halogen or alkyl groups and Rg represents substituted alkyl, aralkyl or carboxylic acid ester groups, while R ^, R ₂ , R ₁ ^ and R ₁ - have the meaning given in claim 1, by alkylation or aralky »* Lation of a compound of the formula with alkyl, oxyalkyl or aralkyl halides and vinylveT "° bonds expediently in solvents in the presence of acid-binding agents. 10,) Use of the Styry! Compounds of claim 1 as a lightening agent. Le A 12 70? - 31 -. 10 1.; ■■; / ν 1 9