4-Heterocyclyl-4'-vinylstilbenes

The invention relates to 4-heterocyclyl-4'-vinylstilbenes of the formula ##STR1## wherein Q is a monocyclic 5- or 6-membered aromatic heterocyclic ring which is unsubstituted or substituted by non-chromophoric groups and which contains no fused benzene rings or 1 or 2 fused benzene rings, or is a bicyclic 9-membered aromatic heterocyclic ring, phenyl which is unsubstituted or substituted by non-chromophoric groups, or is cyano, carboxyl, alkoxycarbonyl or alkylsulfonyl or arylsulfonyl, R.sub.o is hydrogen, alkyl which is unsubstituted or substituted by non-chromophoric groups, R.sub.1 is hydrogen, alkyl, alkoxycarbonyl, carbamoyl or sulfonamide, each of which is unsubstituted or substituted by non-chromophoric groups, or is alkenyl, carboxyl, alkylsulfonyl, arylsulfonyl or aralkylsulfonyl, cyano, sulfo or phosphonic acid dialkyl ester, and R.sub.2 is hydrogen, alkyl or alkenyl, each of which is unsubstituted or substituted by non-chromophoric groups, with the proviso that at most one of R.sub.1 and R.sub.2 is hydrogen. These compounds are used for whitening organic material of high molecular weight, especially polyester. They can be employed in admixture with other fluorescent whitening agents.

 

What is claimed is:

1. A 4-heterocyclyl-4'-stilbene of the formula ##STR197## wherein Q is a monocyclic 5- or 6-membered aromatic heterocyclic ring containing nitrogen or containing nitrogen and oxygen, which is unsubstituted or substituted by non-chromophoric groups and which contains 0, 1 or 2 fused benzene rings, or is a bicyclic 9-membered aromatic heterocylic ring, phenyl which is unsubstituted or substituted by non-chromophoric groups, or is cyano, carboxyl, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl, R.sub.0 is hydrogen, or alkyl which is unsubstituted or substituted by non-chromophoric groups, R.sub.1 is hydrogen, or is alkyl, alkoxycarbonyl, carbamoyl or sulfonamide, each of which is unsubstituted or substituted by non-chromophoric groups, or is alkenyl, carboxyl, alkylsulfonyl, arylsulfonyl, aralkylsulfonyl, cyano, sulfo or phosphonic acid dialkyl ester, and R.sub.2 is hydrogen, or is alkyl or alkenyl, each of which is unsubstituted or substituted by non-chromophoric groups, with the proviso that at most one of R.sub.1 and R.sub.2 is hydrogen.

2. A 4-heterocyclyl-4'-vinylstilbene according to claim 1 of the formula ##STR198## wherein Q.sub.1 is phenyl which is unsubstituted or substituted by non-chromophoric groups, or is cyano, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl, or a radical of the formula ##STR199## in which formulae R.sub.3 is hydrogen, chlorine, C.sub.1 -C.sub.4 alkyl, phenyl(C.sub.1 -C.sub.3)alkyl, cyclohexyl, phenyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylsulfonyl, C.sub.1 -C.sub.4 alkoxycarbonyl, cyano or carboxyl, or together with R.sub.4 is a fused 1-cyclopentene, 1-cyclohexene or benzene ring, each of which is unsubstituted or substituted by 1 to 4 methyl groups,

R.sub.4 is hydrogen, chlorine or C.sub.1 -C.sub.4 alkyl or, together with R.sub.3, forms a 1-cyclopentene, 1-cyclohexene or benzene ring, each of which is unsubstituted or substituted by 1 to 4 methyl groups,

R.sub.5 is hydrogen, C.sub.1 -C.sub.4 alkyl, cyano, COOR, wherein R is C.sub.1 -C.sub.4 alkyl, phenyl or styryl or, together with R.sub.6, forms a fused benzene ring which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or chlorine, or a fused naphthalene ring,

R.sub.6 is hydrogen, C.sub.1 -C.sub.4 alkyl, phenyl or, together with R.sub.5 forms a fused benzene ring which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or chlorine, or a fused naphthalene ring,

R.sub.7 is C.sub.1 -C.sub.4 alkyl which is unsubstituted or substituted by non-chromophoric groups, phenyl, styryl, biphenylyl or naphthyl, each of which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkoxycarbonyl, cyano or chlorine,

R.sub.8 is hydrogen, C.sub.1 -C.sub.4 alkyl or phenyl which is unsubstituted or substituted by chlorine or methyl,

R.sub.9 and R.sub.10, each independently of the other, is hydrogen, C.sub.1 -C.sub.4 alkyl, phenyl which is unsubstituted or substituted by chlorine or methyl, or is C.sub.1 -C.sub.4 alkoxy, C.sub.3 -C.sub.8 alkoxyalkoxy, phenoxy which is unsubstituted or substituted by chlorine or methyl, or is chlorine, C.sub.1 -C.sub.4 alkylthio, phenylthio, C.sub.1 -C.sub.4 alkylamino, di(C.sub.1 -C.sub.4)alkylamino, morpholino, piperidino, piperazino, pyrrolidino or anilino,

R.sub.11 is hydrogen, C.sub.1 -C.sub.4 alkyl or phenyl which is unsubstituted or substituted by chlorine or methyl,

R.sub.12 is C.sub.1 -C.sub.4 alkoxy, C.sub.3 -C.sub.8 alkoxyalkoxy, C.sub.1 -C.sub.4 alkylthio, phenoxy which is unsubstituted or substituted by chlorine or methyl, or is cycloalkoxy, C.sub.1 -C.sub.4 alkylthio, phenylthio which is unsubstituted or substituted by chlorine or methyl, or is C.sub.1 -C.sub.4 alkylamino, di(C.sub.1 -C.sub.4)alkylamino, morpholino, piperidino, piperazino, pyrrolidino or anilino,

R.sub.13 and R.sub.14 are hydrogen, halogen, C.sub.1 -C.sub.4 alkoxy, phenyl, aralkoxy, cycloalkoxy, aryloxy, C.sub.1 -C.sub.4 alkylmercapto, C.sub.1 -C.sub.4 -alkylamino, di(C.sub.1 -C.sub.4)alkylamino, morpholino, piperidino, piperazino, pyrrolidino, arylamino or C.sub.1 -C.sub.4 alkyl,

R.sub.15 is phenyl which is unsubstituted or substituted by chlorine or C.sub.1 -C.sub.4 alkyl,

R.sub.16 is hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.17 is phenyl which is unsubstituted or substituted by chlorine or C.sub.1 -C.sub.4 alkyl,

R.sub.18 is hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.19 is phenyl which is unsubstituted or substituted by chlorine or C.sub.1 -C.sub.4 alkyl,

R.sub.20 is hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.21 is hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.22 is phenyl which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkoxy,

R.sub.23 is hydrogen, C.sub.1 -C.sub.4 alkyl or phenyl which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, halogen or cyano, and

Z is O, S or NX, wherein X is hydrogen, C.sub.1 -C.sub.4 alkyl, acetyl, benzoyl or phenyl.

3. A 4-heterocyclyl-4'-vinyl stilbene according to claim 2 of the formula ##STR200## wherein R.sub.1 ' is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkyl which is substituted by C.sub.1 -C.sub.4 alkoxy or C.sub.2 -C.sub.5 alkoxycarbonyl, or is C.sub.2 -C.sub.4 alkenyl, cyano, COOR.sup.o, wherein R.sup.o is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, tetrahydro-2-furylmethyl, 1,4-dioxa-2-cyclohexylmethyl, allyl, C.sub.1 -C.sub.4 -alkylamino-C.sub.1 -C.sub.4 alkyl or di(C.sub.1 -C.sub.4)alkylamino-C.sub.1 -C.sub.4 alkyl, -CON(R')(R"), wherein R' is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.6 hydroxyalkoxy, -SO.sub.3 M or di(C.sub.1 -C.sub.4)alkylamino, or is cyclohexyl, benzyl or phenethyl, and R" is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy or C.sub.2 -C.sub.6 hydroxyalkoxy, -SO.sub.2 N(R')(R"), wherein R' and R" are as defined above, -SO.sub.3 M, R.sub.x -SO.sub.2 -, wherein R.sub.x is C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.6 alkoxy, or is phenyl or benzyl or phosphonic acid dialkyl ester;

R.sub.2 ' is hydrogen or C.sub.1 -C.sub.6 alkyl,

M is hydrogen or a non-chromophoric cation

Q.sub.2 is phenyl, phenyl which is substituted by halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, carboxyl, C.sub.2 -C.sub.5 alkoxycarbonyl or cyano, or is cyano, carboxyl, C.sub.2 -C.sub.5 alkoxycarbonyl or R.sub.x -SO.sub.2 -, wherein R.sub.x is as defined above, or is a radical of the formula ##STR201## in which formulae R.sub.3 ' is hydrogen, methyl, chlorine or C.sub.1 -C.sub.4 alkoxy,

R.sub.4 ' is hydrogen, chlorine, C.sub.1 -C.sub.4 alkyl, phenyl, C.sub.1 -C.sub.4 alkoxy or phenoxy,

R.sub.5 ' is hydrogen, C.sub.1 -C.sub.4 alkyl, phenyl or styryl or, together with R.sub.6, forms a fused unsubstituted benzene ring or a fused benzene ring which is substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or chlorine, or a fused naphthalene ring,

R.sub.6 ' is hydrogen, C.sub.1 -C.sub.4 alkyl, phenyl or, together with R.sub.5 ', forms a fused unsubstituted benzene ring or a fused benzene ring which is substituted by C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkoxy or chlorine, or a fused naphthalene ring,

R.sub.7 is C.sub.1 -C.sub.4 alkyl which is unsubstituted or substituted by non-chromophoric substituents, phenyl, styryl, biphenyl or naphthyl, each of which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkoxycarbonyl, cyano or chlorine,

R.sub.8 ' is unsubstituted C.sub.1 -C.sub.4 alkyl or phenyl,

R.sub.9 ' is hydrogen, unsubstituted C.sub.1 -C.sub.4 alkyl, phenyl which is unsubstituted or substituted by chlorine or methyl, or is chlorine, C.sub.1 -C.sub.4 alkoxy, C.sub.3 -C.sub.5 alkoxyalkoxy, phenoxy which is unsubstituted or substituted by chlorine or methyl, or is C.sub.1 -C.sub.4 alkylthio or phenylthio,

R.sub.10 ' is hydrogen, unsubstituted C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, phenyl which is unsubstituted or substituted by chlorine or methyl, phenoxy which is unsubstituted or substituted by chlorine or methyl, or is C.sub.1 -C.sub.4 alkylthio, phenylthio or chlorine,

R.sub.13 ' and R.sub.14 ' are hydrogen, C.sub.1 -C.sub.4 alkylamino, di(C.sub.1 -C.sub.4)alkylamino, phenyl, morpholino, piperidino, phenylamino or a radical -(OCH.sub.2 -CH.sub.2).sub.q -OY, wherein Y is hydrogen, C.sub.1 -C.sub.4 alkyl, benzyl or phenyl, and q is an integer from 0 to 7,

R.sub.15 is phenyl which is unsubstituted or substituted by chlorine or C.sub.1 -C.sub.4 alkyl,

R.sub.16 is hydrogen or C.sub.1 -C.sub.4 alkyl, and

R.sub.17 ' is C.sub.1 -C.sub.4 alkyl.

4. A 4-heterocyclyl-4'-vinylstilbene according to claim 3 of the formula ##STR202## wherein R.sub.1 " is cyano, COOR, wherein R is C.sub.1 14 C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 14 C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, 2,3,4,5-tetrahydro-2-furylmethyl, 1,4-dioxa-2-cyclohexylmethyl, CON(R')(R"), wherein R' is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.6 hydroxyalkoxy, -SO.sub.3 M or mono- or di(C.sub.1 -C.sub.4)alkylamino, or is cycloalkyl, benzyl or phenethyl, and R" is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 -alkyl which is substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy or C.sub.2 -C.sub.6 hydroxyalkoxy, R.sub.x -SO.sub.2 -, wherein R.sub.x is C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.6 alkoxy, or is phenyl or benzyl or phosphonic acid dialkyl ester; and R.sub.2 " is hydrogen or C.sub.1 -C.sub.4 alkyl.

5. A 4-heterocyclyl-4'-vinylstilbene according to claim 4 of the formula ##STR203## wherein Q.sub.3 is phenyl, C.sub.2 -C.sub.5 alkoxycarbonyl, cyano or a radical of the formula ##STR204## in which formulae R.sub.3 ' is hydrogen, methyl, chlorine or C.sub.1 -C.sub.4 alkoxy, R.sub.4 " is hydrogen, methyl, chlorine or C.sub.1 -C.sub.4 alkyl, R.sub.9 " is hydrogen, methyl, phenyl, C.sub.1 -C.sub.3 alkoxy, methoxyethoxy or phenoxy, R.sub.10 " is unsubstituted alkyl of 1 or 2 carbon atoms, C.sub.1 -C.sub.3 alkoxy or phenoxy, and each of R.sub.13 " and R.sub.14 " is hydrogen or a radical -(OCH.sub.2 -CH.sub.2).sub.r -OY', wherein Y' is C.sub.1 -C.sub.4 alkyl and r is an integer from 0 to 2.

6. A 4-heterocyclyl-4'-vinylstilbene according to claim 5 of the formula ##STR205## wherein R.sub.1 "' is cyano, COOR, wherein R is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 -alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, 2,3,4,5-tetrahydro-2-furylmethyl or 1,4-dioxa-2-cyclohexylmethyl or R.sub.x -SO.sub.2 -, wherein R.sub.x is C.sub.1 -C.sub.4 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.6 alkoxy, or is phenyl or benzyl, and R.sub.2 "' is hydrogen or C.sub.1 -C.sub.4 alkyl.

7. A 4-heterocyclyl-4'-vinylstilbene according to claim 5 of the formula ##STR206## wherein R.sub.1 '.sup.v is cyano or COOR', and wherein R' is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.6 alkyl.

8. The 4-heterocyclyl-4'-vinylstilbene according to claim 6 of the formula ##STR207##

9. The 4-heterocyclyl-4'-vinylstilbene according to claim 6 of the formula ##STR208##

10. The 4-heterocyclyl-4'-vinylstilbene according to claim 6 of the formula ##STR209##

11. The 4-heterocyclyl-4'-vinylstilbene according to claim 6 of the formula ##STR210##

12. The 4-heterocyclyl-4'-vinylstilbene according to claim 6 of the formula ##STR211##

13. A process for the production of 4-heterocyclyl-4'-vinylstilbene of the formula ##STR212## wherein Q is a monocyclic 5- or 6-membered aromatic heterocyclic ring, containing nitrogen or containing nitrogen and oxygen, which is unsubstituted or substituted by non-chromophoric groups and which contains 0, 1 or 2 fused benzene rings, or is a bicyclic 9-membered aromatic heterocyclic ring, phenyl which is unsubstituted or substituted by non-chromophoric groups, or is cyano, carboxyl, alkoxycarbonyl, alkylsulfonyl or aryl sulfonyl, R.sub.0 is hydrogen, or alkyl which is unsubstituted or substituted by non-chromophoric groups, R.sub.1 is hydrogen, or is alkyl, alkoxycarbonyl, carbamoyl or sulfonamide, each of which is unsubstituted or substituted by non-chromophoric groups, or is alkenyl, carboxyl, alkylsulfonyl, arylsulfonyl, aralkylsulfonyl, cyano, sulfo or phosphonic acid dialkyl ester, and R.sub.2 is hydrogen, or is alkyl or alkenyl, each of which is unsubstituted or substituted by non-chromophoric groups, with the proviso that at most one of R.sub.1 and R.sub.2 is hydrogen, which process comprises condensing, in the presence of an organic solvent and of a basic condensation agent, a compound of the formula ##STR213## with a compound of the formula ##STR214## in which formulae, Q, R.sub.0, R.sub.1 and R.sub.2 are as defined above and one of Z.sub.1 and Z.sub.2 is the OHC group and the other is a grouping of the formula ##STR215## wherein D.sub.1 is an unsubstituted or a substituted alkyl, aryl, cycloalkyl or aralkyl radical.

14. A process for whitening man-made, regenerated man-made and natural organic material of high molecular weight, which comprises incorporating in or applying to the surface of said material a 4-heterocyclyl-4'-vinylstilbene as defined in any one of claims 1 to 7, in an amount of 0.001 to 2%, based on the weight of said material.

15. A process according to claim 14, wherein the material to be whitened is organic material of high molecular weight.

16. A process according to claim 14, wherein the material to be whitened is polyester.

17. A mixture containing a 4-heterocyclyl-4'-vinylstilbene according to any one of claims 1 to 7, and a fluorescent whitening agent suitable for polyester, in the ratio of 1:9 to 9:1.

18. A mixture according to claim 17 containing a 4-heterocyclyl-4'-vinylstilbene of the formula ##STR216## wherein Q.sub.4 is a benzoxazol-2-yl radical, a pyrimidin-2-yl radical, a 4-methylpyrimidin-2-yl radical or a 4,6-dimethylpyrimidine-2-yl radical, and R.sup.v is C.sub.2 -C.sub.4 alkoxycarbonyl or cyano, and, as fluorescent whitening agent suitable for polyester, 1,4-bis(benzoxazol-2'-yl)-naphthalene, 4,4'-bis-(ethoxycarbonylvinyl)-stilbene, 4,4'-bis-(cyanovinyl)-stilbene, 1,4-bis(2'-cyanostyryl)-benzene, 1,5-bis(benzoxazole-2'-yl)-thiophene, 1-phenyl-4-(5',7'-dimethylbenzoxazol-2'-yl)-stilbene, 1,2-bis-(5'-methylbenzoxazol-2'-yl)-vinylene, 4-(benzoxazol-2'-yl)-4'-(3"-methyl-1",2",4"-oxadiazol-5"-yl)-stilbene and 2,4-dimethoxytriazine-6-ylpyrene in the ratio 1:2 or 2:1.

19. A mixture according to claim 18 containing the fluorescent whitening agent of the formula ##STR217## and the fluorescent whitening agent of the formula ##STR218## in the ratio 1:2 or 2:1.

20. A mixture according to claim 17 containing the fluorescent whitening agent of the formula ##STR219## and the fluorescent whitening agent of the formula ##STR220## in the ratio 1:2 or 2:1.

The present invention relates to 4-heterocyclyl-4'-vinylstilbenes, to a process for the production thereof, and to the use thereof for whitening natural and synthetic organic material.

The invention has for its object to provide novel fluorescent whitening agents with improved exhaustion properties. It has been found that heterocyclyl-stilbenes containing a vinyl substituent at one of the terminal phenyl radicals are more productive than hitherto known heterocyclyl-stilbenes.

The novel 4-heterocyclyl-4'-vinylstilbenes have the formula ##STR2## wherein Q is a monocyclic 5- or 6-membered aromatic heterocyclic ring which is unsubstituted or substituted by non-chromophoric groups and which contains no fused benzene rings or 1 or 2 fused benzene rings, or is a bicyclic 9-membered aromatic heterocyclic ring, phenyl which is unsubstituted or substituted by non-chromophoric groups, or is cyano, carboxyl, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl, R.sub.o is hydrogen, alkyl which is unsubstituted or substituted by non-chromophoric groups, R.sub.1 is hydrogen, alkyl, alkoxycarbonyl, carbamoyl or sulfonamide, each of which is unsubstituted or substituted by non-chromophoric groups, or is alkenyl, carboxyl, alkylsulfonyl, arylsulfonyl, aralkylsulfonyl, cyano, sulfo or phosphonic acid dialkyl ester, and R.sub.2 is hydrogen, alkyl or alkenyl, each of which is unsubstituted or substituted by non-chromophoric groups, with the proviso that at most one of R.sub.1 and R.sub.2 is hydrogen.

Examples of non-chromophoric substituents are: halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, aryl or aralkyl, unsubstituted or substituted alkoxy, alkoxycarbonyl, unsubstituted or substituted aminocarbonyl, cyano, alkylsulfonyl, alkoxysulfonyl, unsubstituted or substituted aminosulfonyl, acyl, acylamino, hydroxyl, aryloxy, aralkyloxy, alkenyloxy, aryloxycarbonyl, aralkyloxycarbonyl, carboxyl, acyloxy or trifluoromethyl.

Alkyl is preferably C.sub.1 -C.sub.4 alkyl which can be monosubstituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy, cyano, carboxyl, C.sub.1 -C.sub.4 alkoxycarbonyl, aminocarbonyl, or chlorine.

Alkenyl is preferably C.sub.2 -C.sub.5 alkenyl which can be monosubstituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy, cyano, carboxyl, C.sub.1 -C.sub.4 alkoxycarbonyl or chlorine.

Halogen is preferably fluorine, chlorine or bromine, with chlorine being most preferred. Aryl is preferably phenyl which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, chlorine, bromine or C.sub.1 -C.sub.4 alkoxy.

Aralkyl is preferably phenyl(C.sub.1 -C.sub.4)alkyl which can be additionally substituted in the phenyl nucleus by chlorine, methyl or methoxy.

Alkoxy is preferably C.sub.1 -C.sub.4 alkoxy or a radical of the formula --(OCH.sub.2 --CH.sub.2).sub.m --OR, wherein R is hydrogen or C.sub.1 -C.sub.4 alkyl and m is an integer from 1 to 20.

Cycloalkyloxy is preferably cyclopentyloxy and cyclohexyloxy.

Acyl is preferably C.sub.1 -C.sub.4 alkylcarbonyl, C.sub.1 -C.sub.4 alkylsulfonyl, benzoyl which is unsubstituted or substituted by methyl, methoxy or chlorine, or benzenesulfonyl which is unsubstituted or substituted by methyl, methoxy or chlorine.

Eligible substituents of the aminocarbonyl and aminosulfonyl radicals are, in particular, C.sub.1 -C.sub.4 alkyl, phenyl or phenyl(C.sub.1 -C.sub.4)alkyl, each of which is unsubstituted or substituted by methyl, methoxy or chlorine.

Interesting compounds within the scope of the compounds of the formula I are those of the formula ##STR3## wherein R.sub.1 and R.sub.2 are as defined above and Q.sub.1 is phenyl which is unsubstituted or substituted by non-chromophoric groups, or is cyano, alkoxycarbonyl, alkylsulfonyl or arylsulfonyl, or a radical of the formula ##STR4## in which formulae R.sub.3 is hydrogen, chlorine, C.sub.1 -C.sub.4 alkyl, phenyl(C.sub.1 -C.sub.3)alkyl, cyclohexyl, phenyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylsulfonyl, C.sub.1 -C.sub.4 alkoxycarbonyl, cyano or carboxyl, or together with R.sub.4 is a fused 1-cyclopentene, 1-cyclohexene or benzene ring, each of which is unsubstituted or substituted by 1 to 4 methyl groups,

R.sub.4 is hydrogen, chlorine or C.sub.1 -C.sub.4 alkyl or, together with R.sub.3, forms a 1-cyclopentene, 1-cyclohexene or benzene ring, each of which is unsubstituted or substituted by 1 to 4 methyl groups,

R.sub.5 is hydrogen, C.sub.1 -C.sub.4 alkyl, cyano, COOR, wherein R is C.sub.1 -C.sub.4 alkyl, phenyl or styryl or, together with R.sub.6, forms a fused benzene ring which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or chlorine, or a fused naphthalene ring,

R.sub.6 is hydrogen, C.sub.1 -C.sub.4 alkyl, phenyl or, together with R.sub.5, forms a fused benzene ring which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or chlorine, or a fused naphthalene ring,

R.sub.7 is C.sub.1 -C.sub.4 alkyl which is unsubstituted or substituted by non-chromophoric groups, phenyl, styryl, biphenylyl or naphthyl, each of which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkoxycarbonyl, cyano or chlorine.

R.sub.8 is hydrogen, C.sub.1 -C.sub.4 alkyl or phenyl which is unsubstituted or substituted by chlorine or methyl,

R.sub.9 and R.sub.10, each independently of the other, is hydrogen, C.sub.1 -C.sub.4 alkyl, phenyl which is unsubstituted or substituted by chlorine or methyl, or is C.sub.1 -C.sub.4 alkoxy, C.sub.3 -C.sub.8 alkoxyalkoxy, phenoxy which is unsubstituted or substituted by chlorine or methyl, or is chlorine, C.sub.1 -C.sub.4 alkylthio, phenylthio, C.sub.1 -C.sub.4 alkylamino, di(C.sub.1 -C.sub.4)alkylamino, morpholino, piperidino, piperazino, pyrrolidino or anilino,

R.sub.11 is hydrogen, C.sub.1 -C.sub.4 alkyl or phenyl which is unsubstituted or substituted by chlorine or methyl,

R.sub.12 is C.sub.1 -C.sub.4 alkoxy, C.sub.3 -C.sub.8 alkoxyalkoxy, C.sub.1 -C.sub.4 alkylthio, phenoxy which is unsubstituted or substituted by chlorine or methyl, or is cycloalkoxy, C.sub.1 -C.sub.4 alkylthio, phenylthio which is unsubstituted or substituted by chlorine or methyl, or is C.sub.1 -C.sub.4 alkylamino, di(C.sub.1 -C.sub.4)alkylamino, morpholino, piperidino, piperazino, pyrrolidino or anilino,

R.sub.13 and R.sub.14 are hydrogen, halogen, C.sub.1 -C.sub.4 alkoxy, phenyl, aralkoxy, cycloalkoxy, aryloxy, C.sub.1 -C.sub.4 alkylmercapto, C.sub.1 -C.sub.4 -alkylamino, di(C.sub.1 -C.sub.4)alkylamino, morpholino, piperidino, piperazino, pyrrolidino, arylamino or C.sub.1 -C.sub.4 alkyl,

R.sub.15 is phenyl which is unsubstituted or substituted by chlorine or C.sub.1 -C.sub.4 alkyl,

R.sub.16 is hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.17 is phenyl which is unsubstituted or substituted by chlorine or C.sub.1 -C.sub.4 alkyl,

R.sub.18 is hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.19 is phenyl which is unsubstituted or substituted by chlorine or C.sub.1 -C.sub.4 alkyl,

R.sub.20 is hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.21 is hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.22 is phenyl which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkoxy,

R.sub.23 is hydrogen, C.sub.1 -C.sub.4 alkyl or phenyl which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, halogen or cyano, and Z is O, S or NX, wherein X is hydrogen, C.sub.1 -C.sub.4 alkyl, acetyl, benzoyl or phenyl.

Preferred compounds are those of the formula ##STR5## wherein R.sub.1 ' is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkyl which is substituted by C.sub.1 -C.sub.4 alkoxy or C.sub.2 -C.sub.5 alkoxycarbonyl, or is C.sub.2 -C.sub.4 alkenyl, cyano, COOR.degree., wherein R.degree. is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, tetrahydro-2-furylmethyl, 1,4-dioxa-2-cyclohexylmethyl, allyl, C.sub.1 -C.sub.4 -alkylamino-C.sub.1 -C.sub.4 alkyl or di(C.sub.1 -C.sub.4)alkylamino-C.sub.1 -C.sub.4 alkyl, --CON(R')(R"), wherein R' is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.6 hydroxyalkoxy, --SO.sub.3 M or di(C.sub.1 -C.sub.4)alkylamino, or is cyclohexyl, benzyl or phenethyl, and R" is hydrogen, C.sub. 1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 -alkyl which is substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy or C.sub.2 -C.sub.6 hydroxyalkoxy, --SO.sub.2 N(R')(R"), wherein R' and R" are as defined above, --SO.sub.3 M, R.sub.x --SO.sub.2 --, wherein R.sub.x is C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.6 alkoxy, or is phenyl or benzyl or phosphonic acid dialkyl ester;

R.sub.2 ' is hydrogen or C.sub.1 -C.sub.6 alkyl,

M is hydrogen or a non-chromophoric cation common to fluorescent whitening agents, and

Q.sub.2 is phenyl, phenyl which is substituted by halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, carboxyl, C.sub.2 -C.sub.5 alkoxycarbonyl or cyano, or is cyano, carboxyl, C.sub.2 -C.sub.5 alkoxycarbonyl or R.sub.x --SO.sub.2 --, wherein R.sub.x is as defined above, or is a radical of the formula ##STR6## in which formulae R.sub.3 ' is hydrogen, methyl, chlorine or C.sub.1 -C.sub.4 alkoxy,

R.sub.4 ' is hydrogen, chlorine, C.sub.1 -C.sub.4 alkyl, phenyl, C.sub.1 -C.sub.4 alkoxy or phenoxy,

R.sub.5 ' is hydrogen, C.sub.1 -C.sub.4 alkyl, phenyl or styryl or, together with R.sub.6, forms a fused unsubstituted benzene ring or a fused benzene ring which is substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or chlorine, or a fused naphthalene ring,

R.sub.6 ' is hydrogen, C.sub.1 -C.sub.4 alkyl, phenyl or, together with R.sub.5 ', forms a fused unsubstituted benzene ring or a fused benzene ring which is substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or chlorine, or a fused naphthalene ring,

R.sub.7 is C.sub.1 -C.sub.4 alkyl which is unsubstituted or substituted by non-chromophoric substituents, phenyl, styryl, biphenyl or naphthyl, each of which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkoxycarbonyl, cyano or chlorine.

R.sub.8 ' is unsubstituted C.sub.1 -C.sub.4 alkyl or phenyl,

R.sub.9 ' is hydrogen, unsubstituted C.sub.1 -C.sub.4 alkyl, phenyl which is unsubstituted or substituted by chlorine or methyl, or is chlorine, C.sub.1 -C.sub.4 alkoxy, C.sub.3 -C.sub.5 alkoxyalkoxy, phenoxy which is unsubstituted or substituted by chlorine or methyl, or is C.sub.1 -C.sub.4 alkylthio or phenylthio,

R.sub.10 ' is hydrogen, unsubstituted C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, phenyl which is unsubstituted or substituted by chlorine or methyl, phenoxy which is unsubstituted or substituted by chlorine or methyl, or is C.sub.1 -C.sub.4 alkylthio, phenylthio or chlorine,

R.sub.13 ' and R.sub.14 ' are hydrogen, C.sub.1 -C.sub.4 alkylamino, di(C.sub.1 -C.sub.4)alkylamino, phenyl, morpholino, piperidino, phenylamino or a radical --(OCH.sub.2 --CH.sub.2).sub.q --OY, wherein Y is hydrogen, C.sub.1 -C.sub.4 alkyl, benzyl or phenyl, and q is an integer from 0 to 7,

R.sub.15 is phenyl which is unsubstituted or substituted by chlorine or C.sub.1 -C.sub.4 alkyl,

R.sub.16 is hydrogen or C.sub.1 -C.sub.4 alkyl, and

R.sub.17 ' is C.sub.1 -C.sub.4 alkyl.

Further preferred compounds of the formula (1) are those of the formula ##STR7## wherein R.sub.1 " is cyano, COOR, wherein R is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, 2,3,4,5-tetrahydro-2-furylmethyl, 1,4-dioxa-2-cyclohexylmethyl, CON(R')(R"), wherein R' is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy, C.sub.2 -C.sub.6 hydroxyalkoxy, --SO.sub.3 M or mono- or di(C.sub.1 -C.sub.4)alkylamino, or is cycloalkyl, benzyl or phenethyl, and R" is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by hydroxyl, C.sub.1 -C.sub.4 alkoxy or C.sub.2 -C.sub.6 hydroxyalkoxy, R.sub.x --SO.sub.2 --, wherein R.sub.x is C.sub.1 -C.sub.6 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.6 alkoxy, or is phenyl or benzyl or phosphonic acid dialkyl ester; R.sub.2 " is hydrogen or C.sub.1 -C.sub.4 alkyl, M is hydrogen or a non-chromophoric cation common to fluorescent whitening agents, and Q.sub.2 has the above meaning.

M is preferably hydrogen, an alkali metal cation or an unsubstituted or substituted ammonium cation, e.g. mono-, di- or tri(C.sub.1 -C.sub.4 alkyl)ammonium or mono-, di- or tri(C.sub.2 -C.sub.4 alkanol)ammonium, e.g. mono-, di- or triethanolammonium or mono-, di- or triisopropanolammonium, but preferably hydrogen or sodium.

Especially preferred compounds of the invention are (A) those of the formula ##STR8## wherein R.sub.1 " and R.sub.2 " have the above meanings and Q.sub.3 is phenyl, C.sub.2 -C.sub.5 -alkoxycarbonyl, cyano or a radical of the formula ##STR9## in which formulae R.sub.3 ' is hydrogen, methyl, chlorine or C.sub.1 -C.sub.4 alkoxy, R.sub.4 " is hydrogen, methyl, chlorine or C.sub.1 -C.sub.4 alkyl, R.sub.9 " is hydrogen, methyl, phenyl, C.sub.1 -C.sub.3 alkoxy, methoxyethoxy or phenoxy, R.sub.10 " is unsubstituted alkyl of 1 or 2 carbon atoms, C.sub.1 -C.sub.3 alkoxy or phenoxy, and each of R.sub.13 " and R.sub.14 " is hydrogen or a radical --(OCH.sub.2 --CH.sub.2).sub.r --OY', wherein Y' is C.sub.1 -C.sub.4 alkyl and r is an integer from 0 to 2; and

(B) those of the formula ##STR10## wherein R.sub.1 "' is cyano, COOR, wherein R is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 -alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkoxy-C.sub.2 -C.sub.4 alkyl, 2,3,4,5-tetrahydro-2-furylmethyl or 1,4-dioxa-2-cyclohexylmethyl or R.sub.x --SO.sub.2 --, wherein R.sub.x is C.sub.1 -C.sub.4 alkyl, C.sub.2 -C.sub.6 alkyl which is substituted by C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.6 alkoxy, or is phenyl or benzyl, and R.sub.2 "' is hydrogen or C.sub.1 -C.sub.4 alkyl, and Q.sub.3 has the above meaning; and also

(C) those of the formula ##STR11## wherein R.sub.1 '.sup.v is cyano or COOR', wherein R' is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy-C.sub.2 -C.sub.6 alkyl, and Q.sub.3 has the above meaning.

The 4-heterocyclyl-4'-vinylstilbenes of the formula (1) can be obtained by condensing, in the presence of an organic solvent and of a basic condensation agent, a compound of the formula ##STR12## with a compound of the formula in which formulae Q, R.sub.o, R.sub.1 and R.sub.2 are as defined for formula (1), and one of Z.sub.1 and Z.sub.2 is the OHC group and the other is a grouping of the formula ##STR13## wherein D.sub.1 is an unsubstituted or a substituted alkyl, aryl, cycloalkyl or aralkyl radical.

The solvents employed are advantageously inert solvents, e.g. hydrocarbons such as toluene or xylene, or alcohols such as methanol, ethanol, isopropanol, butanol, glycol, glycol ethers such as 2-methoxyethanol, hexanol, cyclohexanol or cyclooctanol, and also ethers such as diisopropyl ether, dioxane or tetrahydrofurane, and also formamides or N-methylpyrrolidone. Dipolar organic solvents such as dimethyl formamide and dimethyl sulfoxide are particularly suitable.

Suitable condensation agents are strongly basic compounds such as alkali metal hydroxides and alkaline earth metal hydroxides, alkali metal amides and alkaline earth metal amides, alkali metal alcoholates and alkaline earth metal alcoholates, for example potassium hydroxide, sodium hydroxide, potassium tert-butylate, sodium amide or sodium methylate, and also the alkali metal compounds of dimethyl sulfoxide and alkali metal hydrides and, if appropriate, alkali metal dispersions.

The reaction is preferably carried out in the temperature range from 0.degree. to 100.degree. C. The compounds of the invention are also obtained by using the corresponding quaternary phosphonium salts, for example the triphenylphosphonium salts, instead of the phosphono compounds (8) and (9), and condensing these salts with the aldehydes (9) or (8) via the phosphorylene intermediates.

It is, of course, also possible to subject the reaction products obtained from the above processes to further conversion reactions which are known per se, such as halogenating reactions, functional modifications of carboxyl groups, the introduction of chloromethyl groups of the replacement of halogen atoms by cyano groups.

However, compounds of the formula (1) can also be prepared by other processes which are known per se. For example, it is possible to react a Schiff's base of the formula ##STR14## wherein R.sub.o, R.sub.1 and R.sub.2 have the above meanings and h is preferably hydrogen or chlorine, with a methyl compound of the formula ##STR15## wherein Q is as defined above, in the presence of a strongly basic alkali metal compound in dimethyl formamide as the reaction medium. In this context, strongly basic alkali metal compounds are to be understood as meaning those compounds of the alkali metals which have a strength at least approximately equal to that of lithium hydroxide. The compounds can accordingly be compounds of lithium, sodium, potassium, rubidium or caesium of the alcoholate, hydroxide or strongly basic ion exchanger type. It is advantageous to use potassium compounds having the composition

KOC.sub.m-1 H.sub.2m-1

in which m is an integer from 1 to 6, for example potassium hydroxide or potassium tertiary butylate. If alkali metal alcoholates are used, the reaction must be carried out in a virtually anhydrous medium; but when using alkali metal hydroxides, water contents of up to 25% (for example contents of water of crystallisation) are permissible. A water content of up to about 10% is advantageous when using potassium hydroxide. Examples of other alkali metal compounds which can be used are: sodium methylate, sodium hydroxide, lithium hydroxide, rubidium hydroxide, caesium hydroxide and the like. It will be understood that mixtures of such bases can also be used in the reaction.

The compounds of the formula (11), wherein Q is a radical of the formula ##STR16## wherein R.sub.9 "' is hydrogen, C.sub.3 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 alkylthio, and R.sub.21 ' is hydrogen or methyl, are novel and likewise constitute an object of the present invention.

The compounds of the formula (11) are advantageously reacted with the Schiff's base of the formula (10) in equivalent amounts, so that there is no substantial excess of either component. It is advantageous to use at least the equivalent amount of the alkali metal compound, i.e. at least 1 mole of a compound containing e.g. a KO group per mole of Schiff's base. If potassium hydroxide is used, it is preferably present in the 4-fold to 8-fold amount. In general, the reaction can be carried out in the temperature range from about 10.degree. to 150.degree. C. If an alcoholate is used as the potassium compound for the reaction, it is generally not necessary to apply heat. The procedure is, for example, to add the Schiff's base of the formula (10) to the mixture of the compound of the formula (11), the solvent and the potassium alcoholate, advantageously with stirring and with the exclusion of air, in the temperature range from 15.degree. to 30.degree. C., whereupon the reaction takes place straightaway, accompanied by a slight rise in temperature. When potassium hydroxide is employed, it is frequently necessary to carry out the reaction at a higher temperature. For example, the reaction mixture is slowly warmed to 30.degree. to 100.degree. C. and then kept at this temperature for some time, for example 1/2 hour to 2 hours. The final products can be isolated from the reaction mixture by conventional methods which are known per se.

The compounds of the formula (1) can also be obtained by Heck's reaction, by reacting an aromatic halide with an acrylic acid derivative in the presence of a palladium derivative, e.g. palladium acetate, as catalyst [cf. R. F. Heck and J. -P. Nolley, Jr., J. Org. Chem., 37, 2320-2322 (1972)].

The novel compounds defined above exhibit a more or less pronounced fluorescence in the dissolved or finely divided state. They can be used for whitening and/or brightening a wide variety of synthetic, regenerated man-made or natural organic materials or substances which contain such organic materials.

Without any restriction being implied by the following classification, examples of organic materials which can be treated with fluorescent whitening agents are:

I. Man-made organic material of high molecular weight:

(a) polymerisation products based on organic compounds containing at least one polymerisable carbon-carbon double bond, that is to say their homopolymers of copolymers as well as their aftertreatment products, for example, crosslinking, grafting or degradation products, polymer blends, or products obtained by modification of reactive groups, for example polymers based on .alpha.,.beta.-unsaturated carboxylic acids or derivatives of such carboxylic acids, especially on acrylic compounds, for example acrylates, acrylic acid, acrylonitrile, acrylamides and their methacrylic analogues, of olefin hydrocarbons (for example ethylene, propylene, styrenes or dienes and also ABS polymers), and polymers based on vinyl and vinylidene compounds (for example vinyl chloride, vinyl alcohol and vinylidene chloride);

(b) polymerisation products which can be obtained by ring opening, for example, polyamides of the polycaprolactam type, and also polymers which are obtained both by polyaddition and by polycondensation, for example polyethers or polyacetals;

(c) polycondensation products or precondensates based on bifunctional or polyfunctional compounds with condensable groups, their homocondensation and co-condensation products, and aftertreatment products, for example polyesters, especially saturated polyesters (for example ethylene glycol, terephthalic acid polyester) or unsaturated polyesters (for example maleic acid-dialcohol polycondensates as well as their crosslinking products with copolymerisable vinyl monomers), unbranched and branched polyesters (also including those based on polyhydric alcohols, for example alkyd resins), polyamides (for example hexamethylenediamine adipate), maleic resins, melamine resins, their precondensates and and analogues, polycarbonates and silicones;

(d) polyadducts, such as polyurethanes (crosslinked and uncrosslinked) and epoxy resins.

II. Regenerated man-made organic material, for example, cellulose esters of varying degrees of esterification (so-called 21/2-acetate or triacetate) or cellulose ethers, regenerated cellulose (viscose or cuprammonium cellulose), or their aftertreatment products, and casein plastics.

III. Natural organic material of animal or vegetable origin, for example based on cellulose or proteins, such as cotton, wool, linen, silk, natural film-forming resins, starch and casein.

The organic material to be whitened and/or brightened can be in the most diverse states of processing (raw materials, semi-finished goods or finished goods). On the other hand, it can be in the form of structures of the most diverse shapes, for example predominantly three-dimensional structures such as sheets, profiles, injection mouldings, various machined articles, chips, granules or foams, and also predominantly two-dimensional structures, such as films, sheets, lacquers, coatings and impregnations; or predominantly one dimensional bodies such as filaments, fibres, flocks and wires. The above materials can, on the other hand, also be in an unshaped state, in the most diverse homogeneous or inhomogeneous forms of division, as for example in the form of powders, solutions, emulsions, dispersions, latices, pastes or waxes.

Fibrous material can be, for example, in the form of endless filaments (stretched or unstretched), staple fibres, flocks, hanks, textile filament yarns, threads, nonwovens, felts, waddings, flocked structures or woven textile or bonded textile fabrics, knitted fabrics, and papers, cardboards or paper pulps.

The compounds to be used in the practice of this invention are of importance, inter alia, for the treatment of organic textile fabric, especially woven textile fabrics. If it is intended to whiten fibres which can be in the form of staple fibres or endless filaments or in the form of hanks, woven fabrics, knitted fabrics, fleeces, flocked substrates or bonded fabrics, this is advantageously effected in an aqueous medium in which the compounds of the invention are finely dispersed (suspensions, so-called microdispersions, or, optionally, solutions). If desired, dispersing agents, stabilisers, wetting agents and further assistants can be added during the treatment.

Depending on the type of fluorescent whitening agent used, it can be advantageous to carry out the treatment in a neutral or alkaline or acid bath. The treatment is usually carried out in the temperature range from 20.degree. to 140.degree. C., for example at the boiling point of the bath or near it (about 90.degree. C.).

Solutions or emulsions in organic solvents can also be used for the finishing according to the invention of textile substrates, as is practised in the dyeing industry in so-called solvent dyeing (pad-thermofixation application, or exhaust dyeing methods in dyeing machines).

The fluorescent whitening agents of the present invention can further be added to, or incorporated in, the materials before or during their shaping. They can thus be added to the moulding or injection moulding compound in the manufacture of films, sheets (e.g. rolling into polyvinyl chloride at elevated temperature) or moulded articles.

If man-made or regenerated man-made organic materials are formed by spinning processes or from spinning solutions/melts, the fluorescent whitening agents can be applied by the following methods:

addition to the starting materials (for example monomers) or intermediates (for example precondensates or prepolymers), that is to say before or during the polymerisation, polycondensation or polyaddition,

sprinkling in powder form on polymer chips or granules for spinning solutions/melts;

bath dyeing of polymer chips or granules for spinning solutions/melts;

metered addition to spinning melts or spinning solutions; and

application to the spun tow before stretching.

The fluorescent whitening agents of the present invention can also be employed e.g. in the following formulations:

(a) in mixtures with dyes (shading) or pigments (coloured pigments or especially, for example, white pigments), or as an additive to dyebaths, printing pastes, discharge pastes or reserve pastes, or for the aftertreatment of dyeings, prints or discharge prints;

(b) in mixtures with carriers, wetting agents, plasticisers, swelling agents, antioxidants, ultraviolet absorbers, heat stabilisers and chemical bleaching agents (chlorite bleach or bleaching bath additives);

(c) in admixture with crosslinking agents or finishing agents (for example starch or synthetic finishes), and in combination with a wide variety of textile finishing processes, especially synthetic resin finishes (for example creaseproof finishes such as wash-and-wear, permanent-press or non-iron), as well as flameproof finishes, soft finishes, anti-soiling finishes or antistatic finishes, or antimicrobial finishes;

(d) incorporation of the fluorescent whitening agent in polymer carriers (polymerisation, polycondensation or polyaddition products, in dissolved or dispersed form, for use e.g. in coating agents, impregnating agents or binders (solutions, dispersions and emulsions) for textiles, nonwovens, papers and leather;

(e) as additives to master batches;

(f) as additives to a wide variety of industrial products in order to render these more marketable (for example improving the appearance of soaps, detergents, pigments);

(g) in spinning bath preparations, that is to say as additives to spinning baths which are used for improving the slip for the further processing of synthetic fibres, or from a special bath before the stretching of the fibre;

(h) as scintillators for various purposes of a photographic nature, for example for electrophotographic reproduction or supersensitising;

(i) depending on the substitution, as laser dyes.

The compounds of the invention can also be employed in combination with other fluorescent whitening agents. Examples of suitable compounds which can be mixed with the compounds of the invention are: 1,4-bis-(benzoxazol-2'-yl)-naphthalene, 4,4'-bis-(ethoxycarbonylvinyl)-stilbene, 4,4'-bis-(cyanovinyl)-stilbene, 1,4-bis(2'-cyanostyryl)-benzene, 1,5-bis-(benzoxazole-2'-yl)-thiophene, 1-phenyl-4-(5',7'-dimethylbenzoxazol-2'-yl)-stilbene, 1,2-bis-(5'-methylbenzoxazol-2'-yl)-vinylene, 4-(benzoxazol-2'-yl)-4'-(3"-methyl-1",2",4"-oxadiazol-5"-yl)-stilbene and 2,4-dimethoxytriazine-6-yl-pyrene. These compounds are advantageously mixed with compounds of the formula ##STR17## wherein Q.sub.4 is a benzoxazol-2-yl radical, a pyrimidin-2-yl radical, a 4-methylpyrimidin-2-yl radical or a 4,6-dimethylpyrimidine-2-yl radical, and R.sup.v is C.sub.2 -C.sub.4 alkoxycarbonyl or cyano.

The fluorescent whitening agent mixtures so obtained contain the compound of the invention and the known compound in the ratio of 1:9 to 9:1, preferably 1:2 or 2:1.

If the whitening process is combined with textile treatment or finishing methods, the combined treatment can in many cases advantageously be carried out with the aid of appropriate stable preparations which contain the fluorescent whitener compounds in a concentration such that the desired white effect is achieved.

In certain cases, the fluorescent whitening agents are made fully effective by an aftertreatment. This can be, for example, a chemical treatment (for example acid treatment), a thermal treatment or a combined chemical/thermal treatment. Thus, for example, the appropriate procedure to follow in whitening a number of fibre substrates, for example polyester fibres, with the fluorescent whitening agents of the present invention, is to impregnate these fibres with the aqueous dispersions (or optionally also solutions) of the whitening agents at temperatures below 75.degree. C., for example at room temperature, and to subject them to a dry heat treatment at temperatures above 100.degree. C., it being generally advisable additionally to dry the fibrous material beforehand at a moderately elevated temperature, for example in the range from at least 60.degree. C. to about 130.degree. C. The heat treatment in the dry state is then advantageously carried out at a temperature between 120.degree. and 225.degree. C., for example by heating in a drying chamber, by ironing within the specified temperature range or by treatment with dry, superheated steam. The drying and dry heat treatment can also be carried out in immediate succession or be combined in a single procedure.

The amount of fluorescent whitening agent of the present invention to be used, based on the weight of the material to be whitened, can vary within wide limits. A marked and lasting effect can be obtained even with very insignificant amounts, in certain cases 0.0001 percent by weight. But it is also possible to use amounts of up to 0.8 percent by weight and on occasion, up to 2 percent by weight. For most practical purposes, it is preferred to use amounts between 0.0005 and 0.5 percent by weight.

For various reasons it is often advantageous not to use the fluorescent whitening agents by themselves, i.e. pure, but in admixture with a wide variety of assistants and extenders, for example anhydrous sodium sulfate, sodium sulfate decahydrate, sodium chloride, sodium carbonate, alkali metal phosphates, such as sodium or potassium orthosphosphate, sodium or potassium pyrophosphate and sodium or potassium tripolyphosphates or alkali metal silicates.

The fluorescent whitening agents of this invention are also particularly suitable for use as additives for wash liquors or heavy duty and domestic detergents, to which they can be added in various ways. They are advantageously added to wash liquors in the form of their solutions in water or organic solvents, or, in dispersed form, as aqueous dispersions. They are advantageously added to domestic or heavy duty detergents in any stage of the production of the detergents, for example to the slurry before the washing powder is atomised, or during the preparation of liquid detergent combinations. They can be added either in the form of a solution or dispersion in water or other solvents or, without assistants, as a dry powder. For example, the whitening agents can be mixed, kneaded or ground with the surface-active substances and, in this form, admixed with the finished powder. However, they can also be sprayed in a dissolved or pre-dispersed form onto the finished detergent.

Suitable detergents are the known mixtures of active detergents, for example soap in the form of chips and powders, synthetics, soluble salts of sulfonic acid hemiesters of higher fatty alcohols, arylsulfonic acids with higher and/or multiple alkyl substituents, sulfocarboxylic acid esters of medium to higher alcohols, fatty acid acylaminoalkyl- or acylaminoaryl-glycerol sulfonates and phosphoric acid esters of fatty alcohols. Suitable builders which can be used are, for example, alkali metal polyphosphates and polymetaphosphates, alkali metal pyrophosphates, alkali metal salts of carboxymethyl cellulose and other soil redeposition inhibitors, and also alkali metal silicates, alkali metal carbonates, alkali metal borates, alkali metal perborates, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and foam stabilisers, such as alkanolamides of higher fatty acids. The detergents can further contain for example: antistatic agents, fat restorative skin protectives, such as lanolin, enzymes, antimicrobial agents, perfumes and colourants.

The novel fluorescent whitening agents have the particular advantage that they are also active in the presence of active chlorine donors, for example, hypochlorite, and can be used without significant loss of effect in wash liquors containing non-ionic washing agents, for example alkylphenolpolyglycol ethers.

The compounds of the invention are added in amounts of 0.005 to 1% or more, based on the weight of the liquid or powdered finished detergent. Wash liquors which contain the indicated amounts of the claimed fluorescent whitening agents impart a brilliant appearance in daylight when used to wash textiles made from cellulose fibres, polyamide fibres, cellulose fibers with a high quality finish, polyester fibers or wool.

The washing treatment is carried out e.g. as follows: The textiles are treated for 1 to 30 minutes at 20.degree. to 100.degree. C. in a wash liquor which contains 1 to 10 g/kg of a built-up composite detergent and 0.05 to 1%, based on the weight of the detergent, of the fluorescent whitening agent. The liquor ratio can be 1:3 to 1:50. After they have been washed, the textiles are rinsed and dried in the usual manner. The wash liquor can contain 0.2 g/l of active chlorine (for example in the form of hypochlorite) or 0.1 go 2 g/l of sodium perborate.

In the following Examples, percentages are always by weight. Unless otherwise stated, melting and boiling points are uncorrected.

EXAMPLE 1

27.5 g of 2-(4-diethoxyphosphorylmethylphenyl)-4,6-dimethoxypyrimidine and 14.3 g of methyl 4-formylcinnamate are dissolved in 150 ml of dimethyl formamide and to this solution are added 4.9 g of sodium methylate, in small portions, in the course of 30 minutes. The reaction mixture is stirred for 30 minutes at room temperature and then for 21/2 hours at 40.degree.-45.degree. C. The reaction mixture is cooled to room temperature, acidified with formic acid, and stirred into 800 ml of water and ice. The precipitated product is collected by filtration and dried at 80.degree. C. in vacuo, affording 28 g of the compound of the formula ##STR18##

The product crystallises from toluene with the addition of bleaching agents to yellow crystals which have a melting point of 169.degree.-170.degree. C.

The compounds of the formula (102) ##STR19## are obtained from the corresponding starting materials listed in Table 1 by repeating the above procedure.

                  TABLE 1
    ______________________________________
                             melting point
    Compound     R.sub.1 = R.sub.2
                             .degree.C.
    ______________________________________
    103          OCH.sub.3   167-170
    104          OC.sub.2 H.sub.5
                             192-193
    105          OC.sub.3 H.sub.7n
                             190-192
    106
                  ##STR20##  216-127
    107          SC.sub.2 H.sub.5
                             172-173
    108          CH.sub.3    193-194
    ______________________________________

The 2-(4-bromomethylphenyl)pyrimidines substituted in 4,6-position and required as starting materials for the synthesis of the phosphonates are prepared in the following manner: 102.3 g of p-tolylamidine hydrochloride and 99.3 g of diethyl malonate are suspended in 520 ml of anhydrous ethanol. With efficient stirring and cooling, 323.7 g of a 30% sodium methylate solution is introduced. The reaction mixture is then heated to reflux and stirred for 4 to 5 hours under reflux. The solvent is distilled off and the residue is taken up in 1000 ml of water. After heating to 80.degree. C., the somewhat turbid solution is filtered over silica gel. After cooling and acidifying with 15% hydrochloric acid, the dense crystal slurry is filtered and the filter cake is washed with water and dried at 100.degree. C., affording 100 to 110 g of the compound of