# Patent

## Title
Merocyanine derivatives

## Abstract

Disclosed is the use of the compounds of formula




    
    
         wherein
    
    
    Q is —OH; —OR7; —NH2; —NHR7; —NR7R8; or —N═R9;
    T is —COR5; —CN; or —SO2—(C6-C12)aryl;
    R1 is hydrogen; —OR7, —SR7; —NHR7; —NR7R8; C1-C22alkyl; C2-C12Alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl, C2-C11heteroaralkyl; C6-C10aryl; or C1-C9heteroaryl;
    R2 and R3 independently from each other are C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl, C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl; C3-C12cycloheteroalkyl; C2-C11heteroaralkyl, C6-C10aryl; or C1-C9heteroaryl;
    R4 is cyano; COR7, COOR7; CONH2; CONHR7; CONR7R8; SO2(C6-C12)aryl, C2-C12alk-1 -enyl; C3-C12cycloalk-1-enyl; C2-C12alk-1-inyl; C2-C12heteroalkyl, C3-C5heterocycloalkyl, C6-C10aryl; or C1-C9heteroaryl;
    R5 is —COR7; —COOR7; —OR7; —SR7, —NHR7, —NR7R8; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12alkylphenyl; C1-C12alkoxy-C6-C10aryl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C3-C12cycloheteroalkyl; C6-C10aryl; C1-C12alkoxy-C6-C10aryl or C1-C9heteroaryl;
    R6, R7 and R8 independently from each other are hydrogen; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C6-C10aryl; o-C6-C10aryl; or C1-C9heteroaryl;
    R9 is a (C1-C6)alkylidene radical; or
    R1 and R2, R1 and Q, R1 and R4, R1 and R6, R2 and R3, R3 and Q, R6 and Q, T and Q, each independently, are linked together, so that 1, 2, 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings are formed, wherein each of them, independently from each other, may be condensed with an aromatic or heteroaromatic ring, and/or more N-, O- and/or S-heterocycic rings, and each N atom in a N-heterocyclic ring may be substituted by C1-C22alkyl; and
    n is a number from 1 to 4;
    for protecting of human hair and skin against the damaging effect of UV radiation.

## Background
The present invention relates to the use of the compounds of formula




    
    
         wherein
    
    
    Q is hydrogen; C1-C22alkyl; —OH; —OR7; —NR7R8; or —N═R9;
    R1 is hydrogen; C1-C22alkyl; —OR7, —SR7; —NR7R8; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl, C2-C11heteroaralkyl; C6-C10aryl; or C1-C9heteroaryl;
    R4 is cyano; COR7, COOR7; CONR7R8; SO2(C6-C12)aryl; C2-C12alk-1-enyl; C3-C12cycloalk-1-enyl; C2-C12alk-1-inyl; C2-C12heteroalkyl; C3-C5heterocycloalkyl; C6-C10aryl; or C1-C9heteroaryl;
    R5 is —COR7; —COOR7; —OR7; —SR7, —NHR7, —NR7R8; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12alkylphenyl; C1-C12alkoxy-C6-C10aryl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C3-C12cycloheteroalkyl; C6-C10aryl; C1-C12alkoxy-C6-C10aryl; or C1-C9heteroaryl;
    R6 is hydrogen; C1-C22alkyl; C1-C22alkoxy; or COR7;
    R7 and R8 independently from each other are hydrogen; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; —(CH2)tCOOH; C7-C12aralkyl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C6-C10aryl; C1-C9heteroaryl; Si—R10R11R12; Si(OR10)(OR11)(OR12); SiR10(OR11)(OR12); SiR10R11(OR12); —(CH2)u—O—(CH2)v—SiR10R11R12; or a radical X-Sil;
    t, u and v, independently from each other are a number from 1 to 5;
    R9 is a (C1-C6)alkylidene radical;
    R10, R11, R12 independently from each other are C1-C22alkyl;
    X is a linker;
    Sil is a silane-, oligosiloxane- or polysiloxane radical;
    R1 and R2, R1 and Q, R1 and R6, R1 and T, R2 and R3, R2 and R4, R2 and R6, R2 and Q, R4 and R6, R4 and T, R6 and Q, T and Q, each independently, are linked together, so that 1, 2, 3 or 4 carbocyclic or N, O and/or S-heterocylic rings are formed, wherein each of them, independently from each other, may be condensed with an aromatic or heteroaromatic ring, and/or more N-, O- and/or S-heterocyclic rings, and each N atom in a N-heterocyclic ring may be substituted by C1-C22alkyl;
    n is a number from 1 to 4; wherein at least one of the radicals R1, R6 or Q is different from hydrogen;
    if n=1
    T is —COR5; —CN; C6-C10aryl; —NHR5; or —SO2—(C6-C12)aryl;
    R2 and R3 independently from each other are C1-C22alkyl; hydroxy-C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl, C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl; C3-C12cycloheteroalkyl; C6-C10aryl; C1-C9heteroaryl; or a radical of formula






    p is a number from 5 to 100
    q is a number from 1 to 5;
    s is a number from 0 to 4;
    if n=2
    R2 and R3 are each C1-C5alkylene; and simultaneously T is defined as for n=1; or
    T is a bivalent radical of formula —NR7—V—NR7—, wherein
    V is phenylene; or C1-C5alkylene;
    R7 is hydrogen; or C1-C5alkyl; and R2 and R3 simultaneously are defined as for n=1;
    if n=3
    one of R2, R3 or T is a trivalent radical;
    if n=4
    one of R2, R3 or T is a tetravalent radical;
    for protecting of human hair and skin against the damaging effect of UV radiation.


Halogen ist chloro, bromo, fluoro or iodo, preferably chloro.
Alkyl, cycloalkyl, alkenyl, alkylidene or cycloalkenyl may be straight chained or branched, monocyclic or polycyclic.
Alkyl ist for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, n-octadecyl, eicosyl or dodecyl.
Alkenyl is for example straight-chain C2-C12alkenyl or preferably branched C3-C12alkenyl. C1-C12alkyl, like vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3buten-1-yl, 1,3-butadien-2-yl, 2-cyclobuten-1-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-thujen-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcaradien-3-yl oder die verschiedenen isomeren von hexenyl, octenyl, nonenyl, decenyl oder dodecenyl.
C3-C12-cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, trimethylcyclohexyl or preferably cyclohexyl.
C7-C18aralkyl is for example benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, 9-fluorenyl, α,α,-di-methylbenzyl, ω-phenyl-butyl, ω-phenyl-octyl, ω-phenyl-dodecyl oder 3-methyl-5-(1′,1′,3′,3′-tetramethyl-butyl)benzyl.
(C1-C6)alkylidene is for example methylene, ethyl-1-ene, propyl-2-ene. C6-C14ayrl is for example phenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl, anthracenyl or terphenylyl.
C1-C12heteroaryl is an unsaturated or aromatic radical having 4n+2 conjugated π-electrons, for example 2-thienyl, 2-furyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothiazolyl, tri-azolyl, tetrazolyl or another ring system from thiophene-, furan-, pyridine, thiazol, oxazol, imidazol, isothiazol, triazol, pyridine- and benzene rings, which are unsubstituted or substituted by 1 to 6 ethyl, methyl, ethylene and/or methylene, like benzotriazolyl, bei N-heterocycles optionally in the form of their N-oxides.
C2-C16heteroaralkyl is for example C1-C8alkyl substituted with C1-C8heteroaryl.
Preferably compounds of formula (1) are used, wherein

    Q is —OH; —OR7; —NR7R8; or —N═R9;
    T is —COR5; —CN; or —SO2—(C6-C12)aryl;
    R1 is hydrogen; —OR7, —SR7; —NR7R8; C1-C22alkyl; C2-C12alkenyl; C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C6-C10aryl; or C1-C9heteroaryl;
    R2 and R3 independently from each other are C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl, C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl; C3-C12cycloheteroalkyl; C2-C11heteroaralkyl, C6-C10aryl; or C1-C9heteroaryl;
    R4 is cyano; COR7, COOR7; CONR7R8; SO2(C6-C12)aryl, C2-C12alk-1-enyl; C3-C12cycloalk-1-enyl; C2-C12alk-1-inyl; C2-C12heteroalkyl, C3-C5heterocycloalkyl, C6-C10aryl; or C1-C9heteroaryl;
    R5 is —COR7; —COOR7; —OR7; —SR7; —NR7R8; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12alkylphenyl; C1-C12alkoxy-C6-C10aryl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C3-C12cycloheteroalkyl; C6-C10aryl; C1-C12alkoxy-C6-C10aryl or C1-C9heteroaryl;
    R6 is C1-C22alkyl; C1-C22alkoxy; or COR7;
    R7 and R8 independently from each other are hydrogen; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C6-C10aryl; o-C6-C10aryl; or C1-C9heteroaryl;
    R9 is a (C1-C6)alkylidene radical; or
    R1 and R2, R1 and Q, R1 and R4, R1 and R6, R2 and R3, R3 and Q, R6 and Q, T and Q, each independently, are linked together, so that 1, 2, 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings are formed, wherein each of them, independently from each other, may be condensed with an aromatic or heteroaromatic ring, and/or more N-, O- and/or S-heterocycic rings, and each N atom in a N-heterocyclic ring may be substituted by C1-C22alkyl; and
    n is 1.


More preferred is the use of the compounds of formula (1), wherein

    Q is —OH; —OR6; or —NR7R8;
    T is —COR5 —CN; or —SO2—(C6-C12)aryl;
    R1 is hydrogen; —OR7, —SR7; —NR7R8; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; or C6-C10aryl;
    R2 and R3 independently from each other are C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; or C6-C10aryl;
    R4 is cyano; —COR5, —COOR7; —CONR7R8; —SO2(C6-C12)aryl; —C1-C22alkylcarbonylamino-C6-C10aryl; or C6-C10aryl;
    R5 is —COR7; —COOR7; —CONR7R8, —OR7, —SR7, —NR7R8, C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C6-C10aryl; or C1-C12alkoxy-C6-C10aryl;
    R6, R7 and R8 independently from each other are hydrogen; C1-C22alkyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; or C6-C10aryl; or
    R1 and R2, R1 and Q, R1 and R4, R1 and R6, R2 and R3, R3 and Q, R6 and Q, T and Q are linked together pairwise, so that 1, 2, 3 or 4 carbocyclic or N-, O- and/or S-heterocyclic rings are formed, wherein each of them, independently from each other may be condensed with an aromatic or heteroaromatic ring, and/or more N, O and/or S-heterocycic rings, and each N atom in a N-heterocyclic ring may be substituted by C1-C22alkyl.


Even more preferred is the use of the compounds of formula (1), wherein

    R1 is hydrogen; —S—C1-C22alkyl; or R1 and R2, or R1 and R4 together with the linking nitrogen atom form an alkylene radical which my be interrupted by one or more —O— and/or —NR7— or may be condensed with an aromatic ring; and
    R7 is C1-C22alkyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; or C6-C10aryl.


Most preferred is the use of the compounds of formula (1), wherein

    R1 is hydrogen.


Furthermore, the use of compounds formula (1) is preferred, wherein

    R2 and R3 independently from each other are C1-C5alkyl; phenyl-C1-C3alkyl; hydroxy-C1-C12alkyl; or R2 and R3, or R2 and R4, or R2 and Q together with the linking nitrogen atom form an alkylene radical which my be interrupted by one or more —O— and/or —NR7— or may be condensed with an aromatic ring; and
    R7 is C1-C22alkyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; or C6-C10aryl;
    And most preferably the use of the compounds of formula (1), wherein
    R2 and R3 independently from each other are C1-C5alkyl; or R2 and R3 together with the linking nitrogen atom form a C2-C4alkylene radical which may be interrupted by —O— or —NR7; and
    R7 is hydrogen; or C1-C5alkyl.


Preferred is also the use of compounds of formula (1), wherein

    R4 is —COR5; phenyl, which is optionally substituted by C1-C5alkyl; —CN; or —SO2—(C6-C10)aryl; or
    R4 and T together with a bivalent C3-C7alkylene radical which my be interrupted by one or more —O— and/or —NR7— form a carbocyclic ring which may be condensed with an aromatic ring; and
    R7 is hydrogen; or C1-C5alkyl.


Furthermore the use of compounds of formula (1) is preferred, wherein

    R4 is —CN; or COR5;
    R5 is C1-C12alkyl; or C1-C12alkoxy; or
    R4 and T together with the bivalent radical of the formula






    
    
         wherein
    
    
    U1 and U3 independently from each other are a radical of formula —CHR7; —NHR7—; or —O—;
    U2 is —CH2; or —CO—; or the direct bond;
    R7 is hydrogen; or C1-C12alkyl; form an aromatic ring.


Most preferred is the use of compounds of formula (1), wherein

    T and R4 together with the bivalent radicals selected from






    
    
         form a heterocyclic ring.
    
    


Furthermore, the use of compounds of formula (1) is preferred, wherein

    R6 is hydrogen; C1-C5alkyl; C1-C5alkoxy; —O—(C6-C10aryl); or
    R6 and Q together with a bivalent C3-C7alkylene radical which may be interrupted by one or more —O— and/or —NR7— or may be condensed with an aromatic ring, form a heterocyclic ring; and
    R7 is hydrogen; or C1C12alkyl; and most preferably wherein
    R6 is hydrogen.


Furthermore, the use of compounds ofse according to any of formula (1) is preferred, wherein

    T is —CN; —COR5; or —SO2-phenyl;
    R5 is C1-C5alkyl; C1-C5alkoxy; or NR7R8;
    R7 and R8 independently from each other are hydrogen; or C1-C5alkyl; or
    T and Q together with the bivalent C3-C7alkylene radical which may be interrupted by one or more —O— and/or —NR7— or may be condensed with an aromatic ring, form a heterocyclic ring; and most preferably the use of compounds of formula (1), wherein
    T is —CN; or —COR5; and
    R5 is C1-C5alkyl; or C1-C6alkoxy.


Furthermore, the use of compounds of formula (1) is preferred, wherein.

    Q is hydroxy; C1-C5alkoxy; or —NR7R8; and
    R7 and R8 independently from each other are hydrogen; C1-C5alkyl; or phenyl, which may be substituted by one or more C1-C5alkyl or C1-C5alkoxy groups; and most preferably, wherein
    Q is hydroxy.


Furthermore, the use of compounds of formula




    
    
         is preferred, wherein
    
    
    U4, U5, U6, U7 and U8 independently of each other are —CHR5—; —CO—; —NR7—; —CS—; or —O—;
    R5 is hydrogen; or C1-C5alkyl; and
    R1, R2, R3, R6, R7 and Q are defined as in formula (1).


Furthermore, the use of compounds of formula




    
    
         is preferred, wherein
    
    
    R5 is hydrogen; or C1-C5alkyl; and
    R3, R4, and T are defined as in formula (1); more preferably, wherein
    R3 is C1-C22alkyl; C6-C10aryl; or C7-C12aralkyl; and most preferably, wherein
    R3 is C6-C10aryl.


Furthermore, the use of compounds of formula (1) is preferred, wherein at least one of the radicals R1, R6 or Q is different from hydrogen.
Preferred is also the use of compounds of formula (1), wherein

    Q is hydrogen; or C1-C22alkyl;
    T is —COR5; —CN; or —SO2—(C6-C12)aryl;
    R1 is hydrogen; or C1-C22alkyl;
    R2 and R3 independently from each other are C1-C22alkyl;
    R4 is CN; COR5; CONH2; or SO2(C6-C12)aryl,
    R5 is —OR7; —SR7, —NHR7, —NR7R8; C1-C22alkyl; C7-C12aralkyl;
    R7 and R8 independently from each other are hydrogen; C1-C22alkyl; —(CH2)m—Si—R10R11R12; Si(OR10)(OR11)(OR12); SiR10(OR11)(OR12); SiR10R11(OR12), or a radical X-Sil;
    R9 is a (C1-C6)alkylidene radical;
    R10, R11, R12 independently from each other are C1-C22alkyl;
    X is a linker;
    Sil is a silane-, oligosiloxane- or polysiloxane radical;
    R1 and R2, R1 and Q, R1 and R6, R1 and T, R2 and R3, R2 and R4, R2 and R6, R2 and Q, R4 and R6, R4 and T, R6 and Q, T and Q, each independently, are linked together, so that 1, 2, 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings are formed, wherein each of them, independently from each other, may be condensed with an aromatic or heteroaromatic ring, and/or more N-, O- and/or S-heterocycic rings, and each N atom in a N-heterocyclic ring may be substituted by C1-C22alkyl;
    n is a number from 1 to 4; and
    m is a number for 0 to 4; wherein at least one of the radicals R1, R6 or Q is different from hydrogen;


Preferred is the use of compounds of formula (I), wherein

    R1, R6 and Q, independently from each other are hydrogen; or C1-C22alkyl, wherein at least one of R1, R6 and Q is different from hydrogen; and most preferred the use of compounds of formula (1), wherein
    R1, R6 and Q, independently from each other are hydrogen; or C1-C5alkyl, wherein at least one of R1, R6 and Q is different from hydrogen.


Preferred is also the use according of compounds of formula (I), wherein

    T and R4 independently from each other are —COR5; —CN; or —SO2—(C6-C12)aryl; and
    R5 is —OR7; —NR7R8; C1-C22alkyl; C7-C12aralkyl;
    R7 and R8 independently from each other are hydrogen; C1-C22alkyl; —(CH2)m—Si—R10R11R12; and
    R10, R11, and R12 independently from each other are C1-C22alkyl.


Most preferred is the use of compounds of formula (1), wherein T and R4 independently from each other are —CN; SO2C6H5;




    
    
         or a radical of formula
    
    






    
    
         wherein
    
    
    R7 and R8, independently from each other are C1-C12alkyl; or a radical of formula —SiR10R11R12; and
    R10, R11 and R12 are C1-C5alkyl.


Furthermore the present invention relates to the use of monomeric and polymeric compounds having the structural element of formula




wherein at least one of the asterix-marked radicals are joint with the monomeric or polymeric radical; and

    R1, R2, R4 and R6 are defined as in formula (1).


Examples of merocyanine derivatives used in the present invention are listed in Table 1:







TABLE MC2a













 















R2
R3
Q
R6
R1
T
R4

















MC01
i-propyl
1-propyl
OH
H
H






 


MC02 λmax = 374 nm
CH3
CH3
OH
H
H






 


MC03 λmax = 375 nm
CH3
CH3
OH
H
H






 


MC04 λmax = 363 nm
CH3
CH3
OH
H
H






 


MC05 λmax = 371 nm




CH3
OH
H
—






 


MC06 λmax = 384 nm
CH3
CH3
OH
H
H






 












MC07




OH
H
H






 













MC08
CH3
n-butyl
OH
H
H






 


MC09
CH3
CH3
OH
H










 













MC10
CH3
CH3
OH




—CN
—(CO)—CH3


 














MC11
CH3
CH3
OH
H
H










 













MC12




OH
H
H










 














MC13




CH3
OH
H
—
—(CO)N(C2H5)2
—(CO)—CH3


 













MC14
CH3
CH3
OH





—(CO)—CH3


 












MC15




OH
H
H






 













MC16 λmax = 399 nm
CH3
CH3
OH
H
H






 


MC17 λmax = 373 nm
—CH3
i-propyl
OH
H
H






 


MC18
i-propyl
i-propyl
OH
H
H






 


MC19 λmax = 380 nm
CH3
CH3
OH
CH3
H






 


MC20 λmax = 368 nm
CH3
CH3
OH
H
H






 














MC21
CH3
CH3
—O—C6H5
H
H
—(CO)—CH3
CN


MC22
CH3
CH3
—O—CH3
H
H
—(CO)—O—CH3
CN


 












MC23




—OC2H5
H




—(CO)OCH3


 














MC24




C2H5
—OC2H5
H
—
—(CO)OC2H5
—(CO)OC2H5


 













MC25
CH3
CH3




H
—CO—O—C2H5
—CN


 














MC26
CH3
CH3




H
H
—
—(CO)OC2H5


 


MC27
CH3
CH3




H
—
—(CO)—O—CH3
—CN


 


MC28
CH3
CH3




H
—
—(CO)—O—CH3
—SO2—C6H5


 


MC29 λmax = 321 nm
CH3
CH3
—N(CH3)2
H
H
—(CO)—CH3
—(CO)OC2H5


 


MC30
CH3
CH3
—N(CH3)2
H
H
—CN
—(CO)—OCH3


MC31
CH3
CH3
—N(CH3)2
H
H
—(CO)OC2H5
—(CO)OC2H5


λmax =


321 nm


MC32
CH3
CH3
—NH2
H
H
—CN
—(CO)OC2H5


 


MC33
CH3
CH3




H
H
—CN
—(CO)OC2H5


 


MC34
CH3
CH3




H
H
—CN
—(CO)OC2H5


 


MC35
CH3
CH3




H
H
—CN
—(CO)OC2H5


 


MC36




CH3
—
H
H
—CN
—(CO)OC2H5


 


MC37








—
H
H
—CN
—(CO)OC2H5


 


MC38








—
H
H
—CN
—(CO)OC2H5


 


MC39




CH3
—
H
H
—CN






 


MC40








—
H
H
—CN
—(CO)—O—C2H5


 













MC41
CH3
CH3
OH
H
H






 














MC42
CH3
CH3




H
H
—
—(CO)—O—C2H5


 


MC43








—
H
H
—CN
—(CO)—O—C2H5


 


MC44




CH3
—
H
H
—(CO)—O—C2H5
—(CO)—O—C2H5


 


MC45 λmax = 364 nm








—
H
H
—CN
—(CO)—O—C2H5


 


MC46




H
—
H
H
—CN
—(CO)—O—C2H5


 


MC47








—
H
H
—CN






 


MC48








—
H
H
—CN
—(CO)—O—C2H5


 













MC49
CH3
CH3
OH
H
H






 














MC50
CH3
CH3
CH3
H
H
—COOCH3
—COOCH3


MC51
CH3
CH3
CH3
H
H
—COOC2H5
—COOC2H5


MC52
CH3
CH3
CH3
H
H
—COOC3H7-(n)
—COOC3H7-(n)


MC53
CH3
CH3
CH3
H
H
—COOC3H7(i)
—COOC3H7-(i)


MC54
CH3
CH3
CH3
H
H
—COOC4H9(n)
—COOC4H9-(n)


MC55
CH3
CH3
CH3
H
H
—COOC4H9(t)
—COOC4H9-(t)


MC56
CH3
CH3
CH3
H
H
—COOC2H5
—COOC4H9-(t)


MC57
CH3
CH3
CH3
H
H
—COOCH3
—COOC4H9-(t)


MC58
CH3
CH3
CH3
H
H
—COOC2H5
—COOSi(CH3)3


MC59
CH3
CH3
CH3
H
H
—COOSi(CH3)3
—COOSi(CH3)3


MC60
CH3
CH3
CH3
H
H
—CO2CH2)3Si(CH3)3
—CO2(CH2)3Si(CH3)3


MC61
CH3
CH3
CH3
H
H
—CONHC2H5
—CONHC2H5


MC62
CH3
CH3
CH3
H
H
—CON(C2H5)2
—CON(C2H5)2


MC63
CH3
CH3
CH3
H
H
CN
CN


MC64
CH3
CH3
CH3
H
H
CN
SO2C6H6


MC65
CH3
CH3
CH3
H
H
CN
COOC4H9-(n)


MC66
CH3
CH3
CH3
H
H
CN
COOC8H17-(i)


MC67
CH3
CH3
CH3
H
H
CN
COOCH3


MC68
CH3
CH3
CH3
H
H
CN
COOC2H5


MC69
CH3
CH3
CH3
H
H
CN
—CONHC2H5


MC70
CH3
CH3
CH3
H
H
CN
—CON(C2H5)2


MC71
CH3
CH3
CH3
H
H
SO2C6H6
COOCH3


MC72
CH3
CH3
CH3
H
H
SO2C6H6
COOC2H5


MC73
CH3
CH3
CH3
H
H
SO2C6H6
COOC3H7


MC74
CH3
CH3
CH3
H
H
SO2C6H6
COOC4H9


MC75
CH3
CH3
CH3
H
H
SO2C6H6
—COOC8H17(n)


MC76
CH3
CH3
CH3
H
H
SO2C6H6
COOC8H17(i)


MC77
CH3
CH3
CH3
H
H
SO2C6H6
—CONHC2H5


MC78
CH3
CH3
CH3
H
H
SO2tolyl
—COOC2H5


MC79
CH3
CH3
CH3
H
CH3
—COOCH3
—COOCH3


MC80
CH3
CH3
CH3
H
CH3
—COOC2H5
—COOC2H5


MC81
CH3
CH3
CH3
H
CH3
—COOC3H7(n)
—COOC3H7-(n)


MC82
CH3
CH3
CH3
H
CH3
—COOC3H7(i)
—COOC3H7-(i)


MC83
CH3
CH3
CH3
H
CH3
—COOC4H9-(n)
—COOC4H9(n)


MC84
CH3
CH3
CH3
H
CH3
—COOC4H9-(t)
—COOC4H9(t)


MC85
CH3
CH3
CH3
H
CH3
—COOC2H5
—COOC4H9-(t)


MC86
CH3
CH3
CH3
H
CH3
—COOCH3
—COOC4H9-(t)


MC87
CH3
CH3
CH3
H
CH3
—COOC2H5
—COOSi(CH3)3


MC88
CH3
CH3
CH3
H
CH3
—COOSi(CH3)3
—COOSi(CH3)3


MC89
CH3
CH3
CH3
H
CH3
—CONHC2H5
—CONHC2H5


MC90
CH3
CH3
CH3
H
CH3
—CON(C2H5)2
—CON(C2H5)2


MC91
CH3
CH3
CH3
H
CH3
CN
CN


MC92
CH3
CH3
CH3
H
CH3
CN
SO2C6H6


MC93
CH3
CH3
CH3
H
CH3
CN
COOC4H9-(n)


MC94
CH3
CH3
CH3
H
CH3
CN
COOC8H17-(i)


MC95
CH3
CH3
CH3
H
CH3
CN
COOCH3


MC96
CH3
CH3
CH3
H
CH3
CN
COOC2H5


MC97
CH3
CH3
CH3
H
CH3
CN
—CONHC2H5


MC98
CH3
CH3
CH3
H
CH3
CN
—CON(C2H5)2


MC99
CH3
CH3
CH3
H
CH3
SO2C6H6
COOCH3


MC100
CH3
CH3
CH3
H
CH3
SO2C6H6
COOC2H5


MC101
CH3
CH3
CH3
H
CH3
SO2C6H6
COOC3H7


MC102
CH3
CH3
CH3
H
CH3
SO2C6H6
COOC4H9


MC103
CH3
CH3
CH3
H
CH3
SO2C6H6
COOC8H17-(n)


MC104
CH3
CH3
CH3
H
CH3
SO2C6H6
COOC8H17-(i)


MC105
CH3
CH3
CH3
H
CH3
SO2C6H6
—CONHC2H5


MC106
CH3
CH3
CH3
H
CH3
SO2tolyl
—COOC2H5


MC107
CH3
CH3
CH3
H
CH3
SO2tolyl
—CONHC2H5


 













MC108 MC109 MC110 MC111 MC112 MC113




CH3 CH3 CH3 CH3 CH3 CH3
H H H H H H
H H H H H H
—COOC2H5 —COOSi(CH3)3 CN CN CN SO2C6H6
—COOC2H5 —COOSi(CH3)3 CN SO2C6H6 COOC2H5 COOCH3


MC114

CH3
H
H
SO2tolyl
COOC2H5


MC115

CH3
H
CH3
—COOC2H5
—COOC2H5


MC116

CH3
H
CH3
—COOSi(CH3)3
—COOSi(CH3)3


MC117

CH3
H
CH3
CN
CN


MC118

CH3
H
CH3
CN
SO2C6H6


MC119

CH3
H
CH3
CN
COOC8H17-(i)


MC120

CH3
H
CH3
SO2C6H6
COOCH3


 


MC121 MC122 MC123 MC124 MC125 MC126




CH3 CH3 CH3 CH3 CH3 CH3
H H H H H H
H H H H H H
—COOC2H5 —COOSi(CH3)3 CN CN CN SO2C6H6
—COOC2H5 —COOSi(CH3)3 CN SO2C6H6 COOC8H17-(i) COOCH3


MC127

CH3
H
CH3
—COOC2H5
—COOC2H5


MC128

CH3
H
CH3
—COOSi(CH3)3
—COOSi(CH3)3


MC129

CH3
H
CH3
CN
CN


MC130

CH3
H
CH3
CN
SO2C6H6


MC131

CH3
H
CH3
CN
COOC8H17(i)


MC132

CH3
H
CH3
SO2C6H6
COOCH3


MC133

CH3
H
CH3
SO2tolyl
—CONHC2H5


 













MC134
i-propyl
i-propyl
CH3
H
H






 


MC135
CH3
CH3
CH3
H
H






 


MC136
CH3
CH3
CH3
H
H






 












MC137




CH3
H
H






 













MC138




CH3
CH3
H
—






 














MC139
CH3
H
CH3
H
CH3
—(CO)OCH3
—(CO)OCH3


 












MC140




H
CH3
H






 














MC141
CH3
n-C4H9
CH3
H
CH3
—(CO)—O—C2H5
—(CO)—O—C2H5


MC142
CH3
CH3
CH3
H
CH3
—(CO)—O—Na
—(CO)—O—Na


 


MC143




H
CH3
H
—
—(CO)—O—Na
—(CO)—O—Na


 













MC144
CH3
CH3
H
H
CH3






 













MC145
CH3
CH3
H




—CN
—(CO)—CH3


 














MC146
CH3
CH3
CH3
H
H










 













MC147




CH3
H
CH3




—(CO)(CO)OC2H5


 














MC148




CH3
t-butyl
H
H
—(CO)N(C2H5)2
—CO—CH3


 













MC149
i-propyl
i-propyl




H
—CN
—CN


 


MC150
CH3
CH3




H
—CN
—CN


 













MC151
—(CH2)3—Si(CH3)3
CH3
H
H
—CO—C(CH3)3
—CO—O—C2H5


 


MC152




H
CH3
H
—(CO)OSi(CH3)3
—(CO)OSi(CH3)3


 


MC153
n-C3H7
CH3
H
H
—CO—CH33






 














MC154
CH3
CH3
C2H5
H
H
—NH(CO)C5H12
—CN


MC155
C2H5
C2H5
CH3
CH3
CH3
—(CO)—O—C2H5
—(CO)—O—C2H5


 


MC156
CH3
CH3




H
CH3
—(CO)—O—C2H5
—(CO)—O—C2H5


 


MC157
CH3
CH3
H




CH3
—(CO)—O—C2H5
—CN


 


MC158
CH3
CH3




H
phenyl
—(CO)—O—C2H5
—(CO)—O—C2H5


 


MC159
CH3
CH3
C6H5Br
H
CH3
—CN
—(CO)—O—C2H5


MC160
CH3
CH3
biphenyl
H
CH3
CN
—(CO)—O—C2H5


 













MC161
CH3
CH3




H
CN
—(CO)—O—C2H5


 














MC162
CH3
CH3
phenyl
H
CH3
CN
—(CO)—O—C2H5


 


MC163




CH3
H
H




CN
—(CO)—O—C2H5


 


MC164
n-butyl
n-butyl
CH3
H
H
—(CO)—O—C2H5
—SO2—C6H5


 


MC165
CH3
CH3
H
H
phenyl
—(CO)—CH3






 


MC166
CH3
CH3
H
H




—(CO)—CH3
—CN


 


MC167
CH3
CH3




H
H
—(CO)—O—CH3
—(CO)—O—CH3


 


MC168
CH3
CH3
H
H
phenyl
—CN
—(CO)OC(CH3)3


 


MC169
n-butyl
n-butyl
H
H




—CN
—(CO)OC(CH3)3


 


MC170
C2H5
C2H5
H
H




—CN






 


MC171
CH3
CH3




H
CH3
—CN






 













MC172




H
H




—CN






 














MC173
C2H5
C2H5
H
H




—CN
—(CO)—O—C2H5


 


MC174
CH3
CH3
H
H
—CN
—CN
—(CO)—O—CH3


 


MC175
—C2H5OH
—C2H5OH
H
H




—CN
—(CO)—O—C2H5


 


MC176
H
C2H5
H
H




—CN
—(CO)—O—C2H5


 













MC177
C2H5
n-butyl




H
—CN
—CN


 













MC178
C2H5
C2H5
C2H5
H
H






 














MC179
C2H5OH
C2H5OH
CH3
CH3
H
—CN






 


MC180
H




CH3
H
H




—(CO)CH3


 













MC181




C2H5
H
H
—CN






 


MC182




C2H5
H
H










 








MC183






 


MC184






 


MC185






 


MC186






 


MC187






 


MC188






 


MC189






 


MC190






 


MC191






 


MC192






 


MC193






 


MC194






 


MC195






 


MC196






 


MC197






 


MC198













The compounds of formula (1) are prepared according to known processes, as disclosed for example in J. Org. Chem. USSR (Engl. Transl.) 26(8), p. 1562f (1990); J. Heterocycl. Chem. 33(3), p. 763-766 (1996); Khimiya Geterotsiklicheskikh Soedinenii 11, p. 1537-1543 (1984); Khimiya Geterotsiklicheskikh Soedinenii 3, p. 397-404 (1982); Chem. Heterocycl. Comp. (Engl. Transl.) 24(8), 914-919 (1988).
The synthesis of the compounds used in the present invention is also disclosed in WO 0234710, Eur. J. Org. Chem. 2003, 2250-2253, J. Med. Chem. 1996, 39, 1112-1124 and J. Org. Chem., Vol. 37, No. 8, 1972, 1141-1145 as follows:




Vinylogene CH-acid compounds are reacted with acetales of amides.
In J. Heterocyclic Chem., 27, 1990, 1143-1151 aminoacrylic acid esters or aminoacrylnitriles are reacted with ethoxymethylenecyanoacetates in ethanol to the corresponding compounds used in the present invention.
In J. Prakt. Chem. 327 (1985) 4, 567-579 iminoformylation reactions are carried out on substituted crotonnitriles:




The compounds of the formula (1) according to the present invention are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations. These compounds can be used both in dissolved form and in the micronized state.
The UV absorbers according to the present invention can be used either in the dissolved state (soluble organic filters, solubelized organic filters) or in the micronised state (nano-scalar organic filters, particulate organic filters, UV-absorber pigments).
Any known process suitable for the preparation of microparticles can be used for the preparation of the micronised UV absorbers, for example wet-milling, wet-kneading, spray-drying from a suitable solvent, by the expansion according to the RESS process (Rapid Expansion of Supercritical Solutions) by reprecipitation from suitable solvents.
The micronised UV absorbers so obtained usually have an average particle size from 0.02 to 2, preferably from 0.03 to 1.5, and more especially from 0.05 to 1.0 micrometer.
A further object of the present invention is a UV absorber dispersion, comprising

    (a) a micronised UV absorber of formula (1), each of them having a particle size from 0.02 to 2 μm, and
    (b) a suitable dispersing agent.


The cosmetic formulations or pharmaceutical compositions according to the present invention may additionally contain one or more than one further conventional UV filter.
The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above-mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.
As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight und preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.
The compounds of formula (1) may also be used as an anti-wrinkle perception modifier (see Example 29). This is a further object of the present invention.
Preferably, the following combinations comprising UV absorbers are of special interest:
The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.
As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight und preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.
The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds like fatty alcohols, esters of fatty acids, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes:hydrocarbon oils:silicones or siloxanes (organosubstituted super-fatting agents, surfactantsconsistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, antioxidants, hydrotopic agents, preservatives and bacteria-inhibiting agents, perfume oils, colourants, polymeric beads or hollow spheres as spf enhancers,
Cosmetic or Pharmaceutical Preparations
Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations:

    
    
        skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless detergents or washing pastes,
        bath preparations, e.g. liquid. (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts;
        skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils;
        cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers;
        foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations;
        light-protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations;
        skin-tanning preparations, e.g. self-tanning creams;
        depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations;
        insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks;
        deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons;
        antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;
        preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks;
        hair-removal preparations in chemical form (depilation), e.g. hair-removing powders, liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams;
        shaving preparations, e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions;
        fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams;
        cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen per-oxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or chamomile.

Presentation Forms

    
    


The final formulations listed may exist in a wide variety of presentation forms, for example:

    
    
        in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions,
        in the form of a gel,
        in the form of an oil, a cream, milk or lotion,
        in the form of a powder, a lacquer, a tablet or make-up,
        in the form of a stick,
        in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol,
        in the form of a foam, or
        in the form of a paste.
    
    


Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.
Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.
A shampoo has, for example, the following composition: from 0.01 to 5% by weight of a UV absorber according to the invention, 12.0% by weight of sodium laureth-2-sulfate, 4.0% by weight of cocamidopropyl betaine, 3.0% by weight of sodium chloride, and water ad 100%.
Other typical ingredients in such formulations are preservatives, bactericides and bacteriostatic agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxidants, anti-irritants and anti-inflammatory agents etc.
The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.


PREPARATION EXAMPLES
Example 1
Preparation of the Compound of Formula




A mixture of 8.58 g of dehydroacetic acid with 7.63 g of N,N-Dimethylformamid-dimethyl-acetate in 100 ml of tert.-butylmethylether is stirred for 8 hours at room temperature. Then the product is filtered off, washed with minor amounts of tert.-butylmethylether and dried in vacuum at 40° C.
The yield is nearly quantitative. Fp: 159-161° C.
Example 2
Preparation of Compound of Formula




A mixture of 1 g of 1-Ethoxycarbonyl-1-cyano-2-(N-dimethylaminomethylen)amino-4-di-methylaminobutadiene (prepared according to Chem. Heterocycl. Compd. (Engl. Transl.), 24, 8, 1988, 918) with 0.43 g of p-toluidine in 10 ml of dimethylformamide is boiled for 1 hour. The solvent is evaporated, the residue is ground in ether, filtered and dried in vacuum at 40° C. yielding 0.75 g of colorless crystals. Fp: 210-216° C.
Example 3
Preparation of the Compound of Formula




A mixture of 8.62 g pyrrolidine, 16.34 g malonic acid-cycl.-isopropylidene ester and 14.68 g acetylacetaldehyd dimethylacetal in 100 ml Toluene are stirred for 45 minutes at room temperature an kept under reflux for 67 hours.
The reaction mixture is stirred for 4 h at 3° C. and finally for 16 h at room temperature.
The raw product is filtered off and washed with diethylether and finally 4 times with 10 ml methanol.
After drying in vacuo at 60° C. 2.70 g of the product of formula (1) are obtained as bright-orange crystals.
λmax=396 nm.
Example 4
Preparation of the Compound: of Formula




A mixture of 1.16 g of 1-Ethoxycarbonyl-1-cyano-2-(N-dimethylaminomethylen)amino-4-dimethylaminobutadiene (prepared according to Chem. Heterocycl. Compd. (Engl. Transl.), 24, 8, 1988, 918) with 0.47 g of aniline in 11 ml of acetic acid is boiled for 1 hour. After cooling to room temperature the product is filtered off, recrystallized from toluene/ethyl acetate (1:1) yielding yellow crystals which were dried in vacuum at 40° C. The yield is 25%. λmax=363 nm.
Application Examples
Example 5
UV-A/UV-B Daily Care UV Protection Lotion















% w/w



INCI-Name
(as supplied)


















Part A
Oleth-3 Phosphate
0.60



Steareth-21
2.50



Steareth-2
1.00



Cetyl Alcohol
0.80



Stearyl Alcohol
1.50



Tribehenin
0.80



Isohexadecane
8.00



Ethylhexyl Methoxycinnamate
5.00


Part B
Water
qs to 100



Glycerin
2.00



UV-absorber as described in examples 1 to 4
3.00



Disodium EDTA
0.10


Part C
Water
20.00 



Diazolidinyl Urea (and) Iodopropynyl
0.15



Butylcarbamate



Propylene Glycol
4.00


Part D
Sodium Acrylates Copolymer (and) Paraffinium
1.50



Liquidum (and) PPG-1 Trideceth-6



Cyclopentasiloxane
4.50



PEG-12 Dimethicone
2.00



Tocopheryl Acetate
0.45



Water (and) Citric Acid
qs


Part E
Fragrance
qs









Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part A is poured into part B under continuous stirring. Immediately after the emulsification, Cyclopentasiloxane and PEG-12 Dimethicone from part D are incorporated into the mixture. Afterwards the mixture is homogenized with an Ultra Turrax at 11000 rpm for 30 sec. After cooling down to 65° C. Sodium Acrylates Copolymer (and) Paraffinium Liquidum (and) PPG-1 Trideceth-6 are incorporated. Part C is added at a temperature <50° C. At a temperature ≦35° C. Tocopheryl Acetate is incorporated and subsequently the pH is adjusted with Water (and) Citric Acid. At room temperature part E is added.
Example 6
UV Day Lotion















% w/w



INCI-Name
(as supplied)


















Part A
Cetyl Phosphate
1.75



C12-C15 Alkyl Benzoate
5.00



Cetearyl Alcohol/PEG-20 Stearate
2.00



Ethoxydiglycol Oleate
2.00



Stearic Acid
1.50



Ethylhexyl Methoxycinnamate
3.00



Isononyl Isononanoate
2.00


Part B
Aqua
qs to 100



Xanthan Gum
0.35



UV-absorber as described in examples 1 to 4
5.00



Disodium EDTA
0.20



Propylene Glycol
2.00



Diazolidinyl Urea (and) Methylparaben (and)
0.70



Propylparaben (and) Propylene Glycol



Glycerin
1.50


Part C
Cyclopentasiloxane (and) Dimethiconol
1.00



Ethoxydiglycol
3.00



Dimethicone
2.00


Part D
Triethanolamine
qs









Manufacturing Instruction:

Part A is prepared by incorporating all ingredients, then stirred under moderate speed and heated to 75° C. Part B is prepared and heated to 75° C. At this temperature part B is poured into part A under progressive stirring speed. Then the mixture is homogenized (30 sec., 15000 rpm). At a temperature <55° C. the ingredients of part C are incorporated. The mixture is cooled down under moderate stirring, then the pH is checked and adjusted with triethanolamine.
Example 7
Sun Protection Emulsion















% w/w



INCI-Name
(as supplied)


















Part A
Cetearyl Alcohol (and) Dicetyl Phosphate10
4.00



(and) Ceteth-Phosphate



C12-15 Alkyl Benzoate
2.00



Dicaprylyl Ether
3.00



Ethoxydiglycol Oleate
2.00



Stearic Acid
1.00



Ethylhexyl Methoxycinnamate
3.00



Sodium Acrylates Copolymer (and) Glycine Soja
0.30



(and) PPG-1 Trideceth-6



Squalane
3.50


Part B
Aqua
qs to 100



UV-absorber as described in examples 1 to 4
5.00


Part C
Diazolidinyl Urea (and) Iodopropynyl
0.15



Butylcarbamate



Propylene Glycol
2.50



Aqua
10.00 


Part D
Cyclopentasiloxane, Dimethiconol
2.00



Ethoxydiglycol
5.00



Cyclopentasiloxane (and) Dimethicone/Vinyl-
2.00



dimethicone Crosspolymer


Part E
Sodium Hydroxide
0.10









Manufacturing Instruction:

Part A is prepared by incorporating all ingredients, then stirred under moderate speed and heated to 75° C. Part B is prepared and heated to 75° C. At this temperature, part B is poured into part A under progressive stirring speed. Below 65° C. the ingredients of part D are added separately. After cooling down under moderate stirring to 55° C. part C is added. The pH is then checked and adjusted with sodium hydroxide. The mixture is homogenized for 30 sec at 16000 rpm.
Example 8
Every Day Lotion















% w/w



INCI-Name
(as supplied)


















Part A
Stearyl Phosphate
5.00



Tricontanyl PVP
1.00



Ethoxydiglycol Oleate
3.00



Squalane
5.00



C12-15 Alkyl Benzoate
5.00



Ethylhexyl Methoxycinnamate
3.00



Glyceryl Stearate
2.00



Cetyl Alcohol
2.00


Part B
Aqua
20.00 



UV-absorber as described in examples 1 to 4
3.00


Part C
Aqua
qs to 100



Steareth-10 Allyl Ether/Acrylates Copolymer
0.50



Glycerin
2.50



Diazolidinyl Urea (and) Iodopropynyl
0.15



Butylcarbamate



Sodium Lauroyl Glutamate
0.70


Part D
Cyclopentasiloxane (and) Dimethiconol
1.50



Triethanolamine
1.85









Manufacturing Instruction:

Part A is prepared by incorporating all ingredients, then stirred under moderate speed and heated to 75° C. Part C is prepared and heated to 75° C. Part C is poured into the part A under moderate stirring. Immediately after the emulsification part B is added, then neutralized with a part of the triethanolamine. The mixture is homogenized for 30 sec. After cooling down under moderate stirring Cyclopentasiloxane (and) Dimethiconol are added. Below 35° C. the pH is checked and adjusted with triethanolamine.
Example 9
Sprayable Sunscreen Emulsion















% w/w



INCI-Name
(as supplied)


















Part A
Ceteareth-15 (and) Glyceryl Stearate
3.00



Stearyl Alcohol
1.00



Cetyl Ricinoleate
0.80



Dicaprylyl Ether
3.00



C12-15 Alkyl Benzoate
3.00



Isohexadecane
2.50



Stearyl Dimethicone
1.00



Ethylhexyl Methoxycinnamate
4.00



Cetyl Alcohol
0.80



Di-C12-13 Alkyl Tartrate
3.00


Part B
Aqua
qs to 100



Steareth-10 Allyl Ether/Acrylates Copolymer
0.45



PEG-7 Glyceryl Cocoate
2.50



Glycerin
2.00



Propylene Glycol
3.00


Part C
Diazolidinyl Urea (and) Iodopropynyl
0.15



Butylcarbamate



Aqua
20.00 



UV-absorber as described in examples 1 to 4
12.00 



Titanium Dioxide (and) Silica (and) Sodium8.00



Polyacrylate


Part D
Cyclopentasiloxane (and) Dimethiconol
0.85


Part E
Sodium Hydroxide (and) Water
qs to pH




6.50-7.00


Part F
Fragrance
qs









Manufacturing Instruction

Part A and part B are heated up to 80° C. Part A is blended into part B under stirring and homogenized with an UltraTurrax at 11000 rpm for 30 sec. Part C is heated to 60° C. and added slowly to the emulsion. After cooling down to 40° C. part D is incorporated at room temperature and part E is added.
Example 10
Daily Care Lotion















% w/w



INCI-Name
(as supplied)


















Part A
Polyglyceryl Methyl Glucose Distearate
2.50



Cetearyl Alcohol
2.00



Octyl Stearate
3.00



Caprylic/Capric Triglyceride
4.00



Isohexadecane
4.00



Ethylhexyl Methoxycinnamate
2.70


Part B
Aqua
64.80



Glycerin
5.00



Phenoxyethanol (and) Methylparaben (and)
0.50



Butylparaben (and) Ethylparaben (and)



Propylparaben



UV-absorber as described in examples 1 to 4
8.00


Part C
Cyclomethicone (and) Dimethicone
3.00


Part D
Steareth-10 Allyl Ether/Acrylates Copolymer
0.50









Manufacturing Instruction

Part A and B are heated to 75° C. Part A is added into part B under continuous stirring and homogenized with 11000 rpm for 1 minute. After cooling down to 50° C. part C is added under continuous stirring. After cooling further down to 30° C. part D is added. Afterwards the pH is adjusted between 6.00-6.50.
Example 11
Daily Care with UV Protection















% w/w



INCI-Name
(as supplied)


















Part A
Glyceryl Stearate SE
3.00



Glyceryl Stearate and PEG-100 Stearate
3.50



Cetyl Alcohol
1.50



Myristyl Myristate
2.00



Isopropyl Palmitate
2.50



Paraffinum Perliquidum
5.00



Octyl Dimethyl PABA
3.00


Part B
Aqua
qs to 100



Propylene Glycol
7.50



Phenoxyethanol (and) Methylparaben (and)
1.00



Butylparaben (and) Ethylparaben (and)



Propylparaben


Part C
Aqua
30.00 



UV-absorber as described in examples 1 to 4
10.00 


Part D
Sodium Acrylates Copolymer (and) Paraffinium
2.00



Liquidum (and) PPG-1 Trideceth-6


Part E
Citric Acid
0.30









Manufacturing Instruction:

Part A and B are heated separately to 75° C. After adding part B into part A the mixture is homogenized with Ultra Turrax for one minute at 11000 rpm. After cooling down to 50° C. part C is added. Afterwards the mixture is homogenized for one minute at 16000 rpm. At a temperature <40° C. part D is added. At room temperature the pH-value is adjusted with part E between 6.00 and 6.50.
Example 12
O/W Every Day UV Protection Lotion















% w/w



INCI-Name
(as supplied)


















Part A
Glyceryl Stearate (and) PEG-100 Stearate
5.00



Stearyl Alcohol
1.00



Tripalmitin
0.70



Dimethicone
2.00



C12-15 Alkyl Benzoate
5.00



Isopropyl Palmitate
5.00



Ethylhexyl Methoxycinnamate
3.00


Part B
Water
qs to 100



Polysorbate 60
0.50



Glycerin
3.00


Part C
Water
10.00 



UV-absorber dispersion as described in examples
8.00



1 to 4


Part D
Phenoxyethanol (and) Methylparaben (and)
0.70



Ethylparaben (and) Butylparaben (and)



Propylparaben (and) Isobutylparaben



Steareth-10 Allyl Ether/Acrylates Copolymer
1.50


Part E
Water (and) Sodium Hydroxide
qs


Part F
Fragrance
qs









Manufacturing Instruction:

Part A and B are heated separately up to 75° C., part C is heated to 60° C. Afterwards part B is poured into part A under stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at 11000 rpm and part C is incorporated. After cooling down to 40° C. part D is added. At room temperature the pH-value is adjusted with Sodium Hydroxide between 6.30 and 6.70 and part F is added.
Example 13
O/W Every Day UV Protection















% w/w



INCI-Name
(as supplied)


















Part A
Glyceryl Stearate (and) PEG-100 Stearate
5.00



Stearyl Alcohol
1.00



Tripalmitin
0.70



Dimethicone
2.00



C12-15 Alkyl Benzoate
5.00



Isopropyl Palmitate
5.00



Ethylhexyl Methoxycinnamate
3.00


Part B
Water
qs to 100



Polysorbate 60
0.50



Glycerin
3.00


Part C
Water
10.00 



UV-absorber dispersion as described in examples
8.00



1 to 4


Part D
Phenoxyethanol (and) Methylparaben (and)
0.70



Ethylparaben (and) Butylparaben (and)



Propylparaben (and) Isobutylparaben



Steareth-10 Allyl Ether/Acrylates Copolymer
1.50


Part E
Water (and) Sodium Hydroxide
qs


Part F
Fragrance
qs









Manufacturing Instruction:

Part A and B are heated separately up to 75° C., part C is heated to 60° C. Afterwards part B is poured into part A under stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at 11000 rpm and part C is incorporated. After cooling down to 40° C. part D is added. At room temperature the pH-value is adjusted with Sodium Hydroxide between 6.30 and 6.70 and part F is added.
Example 14
Sunscreen Cream















% w/w



INCI-Name
(as supplied)


















Part A
Cetearyl Alcohol (and) Dicetyl Phosphate (and)
4.50



Ceteth-10 Phosphate



C12-15 Alkyl Benzoate
6.00



Caprylic/Capric Triglyceride
7.00



Pentaerythritol Tetraisostearate
2.00



Ethylhexyl Methoxycinnamate
3.00



Isoamyl p-Methoxycinnamate
2.00


Part B
Aqua
qs to 100



Glycerin
2.00



Propylene Glycol
1.50



Magnesium Aluminium Silicate
1.20


Part C
Steareth-10 Allyl Ether/Acrylates Copolymer
0.50



UV-absorber dispersion as described in examples
12.00 



1 to 4


Part D
Phenyl Trimethicone
1.50



Phenoxyethanol (and) Methylparaben (and)
0.70



Butylparaben (and) Ethylparaben (and)



Propylparaben


Part E
Sodium Hydroxide
0.90









Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part B is added into part A under continuous stirring and afterwards homogenized with Ultra Turrax for 30 sec at 11000 rpm. After cooling down to 60° C. part C is added. At 40° C. part C is added and homogenized for 15 sec at 11000 rpm. At room temperature the pH-value is adjusted with part E.
Example 15
UVA/UVB Daily Care Lotion, Type O/W















% w/w



INCI-Name
(as supplied)


















Part A
Glyceryl Stearate (and) PEG-100 Stearate
5.00



Stearyl Alcohol
1.00



Tripalmitin
0.70



Mineral Oil
15.00


Part B
Water
qs to 100



Polysorbate 60
0.50



Glycerin
3.00


Part C
Water
10.00 



UV-absorber dispersion as described in examples
8.00



1 to 4


Part D
Steareth-10 Allyl Ether/Acrylates Copolymer
1.50



Phenoxyethanol (and) Methylparaben (and)
0.70



Ethylparaben (and) Butylparaben (and)



Propylparaben (and) Isobutylparaben


Part E
Water (and) Sodium Hydroxide
qs


Part F
Fragrance
qs









Manufacturing Instruction:

Part A and B are heated separately to 75° C.; part C to 60° C. Part B is poured into part A under stirring. After one-minute of homogenization at 11000 rpm part C is added to the mixture of A/B. After cooling down to 40° C. part D is incorporated. At room temperature the pH value is adjusted with part E between 6.3 and 7.0. Finally part F is added.
Example 16
UVA/UVB Daily Care Lotion, Type O/W















% w/w



INCI-Name
(as supplied)


















Part A
Oleth-3 Phosphate
0.60



Steareth-21
2.50



Steareth-2
1.00



Cetyl Alcohol
0.80



Stearyl Alcohol
1.50



Tribehenin
0.80



Isohexadecane
8.00


Part B
Water
qs to 100



Glycerin
2.00



Disodium EDTA
0.10


Part C
Cyclopentasiloxane
4.50



PEG-12 Dimethicone
2.00


Part D
Sodium Acrylates Copolymer (and) Mineral
1.50



Oil (and) PPG-1 Trideceth-6


Part E
UV-absorber dispersion as described in examples
10.00 



1 to 4


Part F
Tocopheryl Acetate
0.45



DMDM Hydantoin (and) Iodopropynyl
0.85



Butylcarbamate (and) Aqua (and) Butylene



Glycol


Part G
Water (and) Citric Acid
qs



Fragrance
qs









Manufacturing Instruction:

Part A and part B are heated separately to 75° C. Part A is poured into part B under stirring. Immediately after the emulsification, part C is added to the mixture and homogenized with an Ultra Turrax at 11000 rpm for 30 sec. After cooling down to 65° C. Sodium Acrylates Copolymer (and) Mineral Oil (and) PPG-1 Trideceth-6 At 50° C. is added slowly to the UV absorber dispersion. At about 35-30° C. part F is incorporated. The pH is adjusted with part G between 5.5 and 6.5.
Example 17
UV-A/UV-B Every Day Protection Lotion O/W















% w/w



INCI-Name
(as supplied)


















Part A
Glyceryl Dilaurate
2.00



Ethylhexyl Palmitate
6.00



Cetyl Alcohol
1.00



Glyceryl Stearate
2.00



Laureth-23
1.00



Isopropyl Palmitate
2.00



Tribehenin
0.80



Beeswax
1.50



Lanolin Oil
1.00


Part B
Water
qs to 100



Propylene Glycol
4.00



Water (and) Titanium Dioxide (and) Alumina
4.00



(and) Sodium Meta-phosphate (and)



Phenoxyethanol (and) Sodium Methylparaben


Part C
Steareth-10 Allyl Ether/Acrylates Copolymer
1.00


Part D
Phenoxyethanol (and) Methylparaben (and)
1.00



Ethylparaben (and) Butylparaben (and)



Propylparaben (and) Isobutylparaben



UV-absorber dispersion as described in examples
8.00



1 to 4


Part E
Water (and) Sodium Hydroxide
qs









Manufacturing Instruction:

Part A and part B are heated separately up to 80° C. Part A is poured into part B while stirring and homogenized with an Ultra Turrax by 11000 rpm for 30 sec. After cooling down to 60° C. part C is incorporated. At 40° C. part D is added slowly under continuous stirring. The pH is adjusted with part E between 6.50-7.00.
Example 18
Sprayable Sunscreen Lotion















% w/w



INCI-Name
(as supplied)


















Part A
Potassium Cetyl Phosphate
0.20



Isohexadecane
7.00



VP/Eicosene Copolymer
1.50



Di-C12-13 Alkyl Tartrate
6.00



Ethylhexyl Triazone
2.50



C12-15 Alkyl Benzoate
4.50


Part B
Water
qs to 100



Sorbeth-30
2.00



Sorbitan Stearate (and) Sucrose Cocoate
4.00



Titanium Dioxide (and) Alumina (and) Silica
2.50



(and) Sodium Polyacrylate


Part C
Water
30.00



UV-absorber dispersion as described in examples
12.00



1 to 4


Part D
Phenoxyethanol (and) Methylparaben (and)
0.70



Ethylparaben (and) Butylparaben (and)



Propylparaben (and) Isobutylparaben


Part E
Water (and) Citric Acid
qs









Manufacturing Instruction:

Part A and part B are heated separately up to 80° C., part C is heated to 50° C. Part B is poured into part A and homogenized with an Ultra Turrax for 1 minute at 11000 rpm. After cooling down to 50° C. part C is added under continuous stirring. At 40° C. part D is incorporated and homogenized again for 10 sec. at 11000 rpm. The pH is adjusted with part E.
Example 19
O/W Every Day UV Protection Lotion















% w/w



INCI-Name
(as supplied)


















Part A
Glyceryl Stearate (and) PEG-100 Stearate
5.00



Stearyl Alcohol
1.00



Tripalmitin
0.70



Dimethicone
2.00



Caprylic/Capric Triglyceride
5.00



Isopropyl Palmitate
5.00



Ethylhexyl Methoxycinnamate
3.00


Part B
Water
qs to 100



Polysorbate 60
0.50



Glycerin
3.00


Part C
Water
10.00



UV-absorber dispersion as described in examples
8.00



1 to 4


Part D
Phenoxyethanol (and) Methylparaben
0.70



(and) Ethylparaben (and) Butylparaben (and)



Propylparaben (and) Isobutylparaben



Steareth-10 Allyl Ether/Acrylates Copolymer
1.50


Part E
Water (and) Sodium Hydroxide
qs


Part F
Fragrance
qs









Manufacturing Instruction:

Part A and part B are heated separately up to 75° C., part C is heated to 60° C. Afterwards part B is poured into part A under stirring. The mixture is homogenized with an Ultra Turrax for 30 sec. at 11000 rpm and part C is incorporated. After cooling down to 40° C. part D is added. At room temperature the pH-value is adjusted with Sodium Hydroxide between 6.30 and 6.70 and part F is added.
Example 20
Water Resistant Sunscreen Emulsion















% w/w



INCI-Name
(as supplied)


















Part A
Polyglyceryl-10 Pentastearate (and) Behenyl
2.50



Alcohol (and) Sodium Stearoyl Lactylate



VP/Eicosene Copolymer
1.50



Stearyl Alcohol
1.50



Squalane
4.00



C12-15 Alkyl Benzoate
7.50



Octocrylene
1.50



4-Methylbenzylidene Camphor
3.00



Ethylhexyl Methoxycinnamate
2.00


Part B
Water
qs to 100



Glycerin
1.80



Steareth-10 Allyl Ether/Acrylates Copolymer
0.80


Part C
UV-absorber dispersion as described in examples
9.00



1 to 4


Part D
VP/Hexadecene Copolymer
2.70



Cyclomethicone
1.50



Phenoxyethanol (and) Methylparaben (and)
0.70



Ethylparaben (and) Butylparaben (and)



Propylparaben (and) Isobutylparaben


Part E
Aqua (and) Tocopheryl Acetate (and)
3.50



Caprylic/Capric Triglyceride (and)



Polysorbate 80 (and) Lecithin


Part F
Fragrance
qs



Water (and) Sodium Hydroxide
qs









Manufacturing Instruction:

Part A and part B are heated separately to 80° C. Part A is poured into part B under continuous stirring. Afterwards the mixture is homogenized with an Ultra Turrax at 11000 rpm for 1 min. After cooling down to 60° C. part C is incorporated. At 40° C. part D is added and the mixture homogenized for a short time again. At 35° C. part E is added and at room temperature Fragrance is added. Finally the pH is adjusted with Sodium Hydroxide.
Example 21
UVA/UVB Sun Protection Lotion, O/W Type















% w/w



INCI-Name
(as supplied)


















Part A
Potassium Cetyl Phosphate
2.00



Tricontanyl PVP
1.00



Caprylic/Capric Triglyceride
5.00



C12-15 Alkyl Benzoate
5.00



Cetearyl Isononanoate
5.00



Glyceryl Stearate
3.00



Cetyl Alcohol
1.00



Dimethicone
0.10



Ethylhexyl Methoxycinnamate
5.00


Part B
Water
qs to 100



Glycerin
3.00


Part C
Steareth-10 Allyl Ether/Acrylates Copolymer
0.50


Part D
UV-absorber dispersion as described in examples
8.00



1 to 4


Part E
Phenoxyethanol (and) Methylparaben
1.00



(and) Ethylparaben (and) Butylparaben (and)



Propylparaben (and) Isobutylparaben


Part F
Water (and) Sodium Hydroxide
qs to pH




7.00


Part G
Fragrance
qs









Manufacturing Instruction:

Part A and part B are heated separately up to 80° C. Part B is poured into part A under moderate stirring. The mixture is homogenized with an Ultra Turrax at 11000 rpm for 1 minute. After cooling down to 70° C. part C is added under stirring. After cooling further down to 50° C. part D is incorporated very slowly. At 40° C. part E is added. At room temperature the pH is adjusted with part F to 7.00 and part G is added.
Example 22
UVA/UVB Sun Protection Lotion, O/W Type















% w/w



INCI-Name
(as supplied)


















Part A
Potassium Cetyl Phosphate
2.00



Tricontanyl PVP
1.00



Caprylic/Capric Triglyceride
5.00



C12-15 Alkyl Benzoate
5.00



Cetearyl Isononanoate
5.00



Glyceryl Stearate
3.00



Cetyl Alcohol
1.00



Dimethicone
0.10



Ethylhexyl Methoxycinnamate
5.00


Part B
Water
qs to 100



Glycerin
3.00


Part C
Steareth-10 Allyl Ether/Acrylates Copolymer
0.50


Part D
UV-absorber dispersion as described in examples
20.00



1 to 4


Part E
Phenoxyethanol (and) Methylparaben
1.00



(and) Ethylparaben (and) Butylparaben (and)



Propylparaben (and) Isobutylparaben


Part F
Water (and) Sodium Hydroxide
qs to pH




7.00


Part G
Fragrance
qs









Manufacturing Instruction:

Part A and part B are heated separately up to 80° C. Part B is poured into part A under moderate stirring. The mixture is homogenized with an Ultra Turrax at 11000 rpm for 1 minute. After cooling down to 70° C. add part C is added under stirring. After cooling further down to 50° C. part D is incorporated very slowly. At 40° C. part E is added. At room temperature the pH is adjusted with part F to 7.00 and part G is added.
Example 23
Sunscreen Lotion















% w/w



INCI-Name
(as supplied)


















Part A
Cetearyl Alcohol (and) Dicetyl Phosphate
4.00



(and) Ceteth-10 Phosphate



C12-15 Alkyl Benzoate
2.00



Dicaprylyl Ether
3.00



Ethoxydiglycol Oleate
2.00



Stearic Acid
1.00



Ethylhexyl Methoxycinnamate
3.00



Sodium Acrylates Copolymer (and) Glycine Soja
0.30



(and) PPG-1 Trideceth-6



Squalane
3.50



VP/Eicosene Copolymer
2.00


Part B
Water
qs to 100



UV-absorber dispersion as described in examples
5.00



1 to 4


Part C
Diazolidinyl Urea (and) Iodopropynyl
0.15



Butylcarbamate



Propylene Glycol
2.50



Water
10.00


Part D
Cyclopentasiloxane (and) Dimethiconol
2.00



Ethoxydiglycol
5.00



Cyclopentasiloxane (and) Dimethicone/Vinyl
2.00



Dimethicone Crosspolymer


Part E
Aqua (and) Sodium Hydroxide
qs


Part F
Fragrance
qs









Manufacturing Instruction

Part A and part B are heated separately up to 75° C. Part B is poured into part A under progressive stirring speed. At a temperature <65° C. the ingredients of part D are added separately. After cooling down to 55° C. under moderate stirring part C is added. At a temperature <35° C. the pH is checked and adjusted with Sodium Hydroxide and homogenized with an Ultra Turrax for 30 sec. at 11000 rpm. Part F is added at room temperature.
Example 24
W/O Sunscreen Lotion















% w/w



INCI-Name
(as supplied)


















Part A
PEG-7 Hydrogenated Castor Oil
3.00



Polyglyceryl-3 Diisostearate
4.00



Microcrystalline Wax
1.00



Magnesium Stearate
1.50



Propylparaben
0.10



Mineral Oil
15.00



Octyldodecanol
8.00



Ethylhexyl Triazone
1.00



Ethylhexyl Methoxycinnamate
2.00


Part B
Water
qs to 100



Water (and) Citric Acid
0.05



Methylparaben
0.15



Magnesium Sulfate
0.50


Part C
UV-absorber dispersion as described in example
9.00



1 or 2



Fragrance
qs









Manufacturing Instruction:

Part A is heated to 80° C. whilst stirring. Part B is added into part A and homogenized with an Ultra Turrax at 11000 rpm for one minute. After cooling down to 30° C. part C is incorporated.
Example 25
Skin Protection Sunscreen Lotion W/O















% w/w



INCI-Name
(as supplied)


















Part A
Polyglyceryl-2 Dipolyhydroxystearate
3.00



Glyceryl Oleate
3.00



Cetearyl Isononanoate
7.00



Hexyl Laurate
6.00



Dicaprylyl Ether
6.00



Propylparaben
0.10



Hexyldecanol
3.00



Magnesium Stearate
1.00



Beeswax
1.00



Ethylhexyl Methoxycinnamate
4.00


Part B
Water
qs to 100



Methylparaben
0.15



Magnesium Sulfate
1.00


Part C
UV-absorber dispersion as described in examples
6.00



1 to 4









Manufacturing Instruction:

Part A is heated separately to 80° C. under gentle stirring. Part B is added to part A and homogenized for one minute at 11000 rpm. After cooling down to 30° C. part C is added under continuous stirring.
Example 26
O/W Emulsion















% w/w



INCI-Name
(as supplied)





















Part A
UV absorber of formula (MC 14)
3
g




sesame oil
10
g




glyceryl stearate
4
g




stearic acid
1
g




cetyl alcohol
0.5
g




polysorbate 20
0.2
g



Part B
propylene glycol
4
g




propylparaben
0.05
g




methylparaben
0.15
g




triethanolamine
0.1
g




carbomer 934
0.1
g




water
ad 100
ml










Preparation of the Emulsion

Phase (A):

Firstly, the UV absorber is dissolved in sesame oil. The other components of (A) are added thereto and combined.
Phase (B):
Propylparaben and methylparaben are dissolved in propylene glycol. 60 ml of water are then added, heating to 70° C. Is carried out and then carbomer 934 is emulsified therein.
Emulsion:
(A) is slowly added to (B) with vigorous application of mechanical energy. The volume is adjusted to 100 ml by the addition of water.
Example 27
Daily Care Cream, Type O/W















% w/w



INCI name
(as used)


















Part A
Glyceryl stearate (and) cetearyl alcohol (and)
4.0



cetyl palmitate (and) cocoglycerides



Ceteareth-12
4.0



Cetearyl alcohol
2.0



Dicaprylyl ether
4.5



Ethylhexyl stearate
4.0



Hexyl laurate
3.5



Ethylhexyl triazone
1.0



Benzylidene malonate polysiloxane
2.0



HDI/trimethylol hexyl-lactone crosspolymer (and)
5.0



silica



Stearyl dimethicone
1.0



Dimethicone
2.0



Cetyl alcohol
0.8



compound of formula (MC 14)
2.0


Part B
Water
q.s. to 100



Water (and) scleroglucan (and) phenoxyethanol
2.0



Glycerol
2.0


Part C
Steareth-10 allyl ether/acrylate copolymer
0.45



Phenoxyethanol (and) methylparaben (and)
0.7



ethylparaben (and) butylparaben (and)



propylparaben (and) isobutylparaben


Part D
Aqua (and) tocopheryl acetate (and) caprylic/capric
4.0



triglyceride (and) polysorbate 80 (and) lecithin


Part E
Water (and) sodium hydroxide
q.s.



Fragrance
q.s.









Preparation Procedure:

Part A and part B are heated separately to 80° C. Part A is poured into part B, whilst stirring continuously. Afterwards the mixture is homogenized with an Ultra Turrax at 11000 rpm for 20 sec. The mixture is cooled to 60° C. and part C is added. At a temperature below 30° C., part D is added and the pH value is adjusted with sodium hydroxide to between 6.5 and 7.0. Finally, fragrance is added.
Example 28
Sun-Protection Cream. Type O/W















% w/w



INCI name
(as used)


















Part A
Polyglyceryl-3 methylglucose distearate
2.0



Decyl oleate
5.7



Isopropyl palmitate
5.8



Caprylic/capric triglyceride
6.5



compound of formula (MC 14)
2.0



Ethylhexyl methoxycinnamate
5.0



Cetyl alcohol
0.7


Part B
Glycerol
3.0



Carbomer
0.3



Water
q.s. to 100


Part C
Phenoxyethanol (and) methylparaben (and)
0.5



ethylparaben (and) butylparaben (and)



propylparaben (and) isobutylparaben


Part D
Methylene bis-benzotriazolyl
8.0



tetramethylbutylphenol (and) aqua (and) decyl



glucoside (and) propylene glycol (and) xanthan gum



Water
20.0


Part E
Water (and) sodium hydroxide
q.s.



Fragrance
q.s.









Preparation Procedure

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11000 rpm for 15 sec. The mixture is cooled to 60° C. and part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11000 rpm) and further cooled, with moderate stirring. At room temperature, the pH is adjusted with sodium hydroxide solution to between 5.5 and 6.0. Finally, fragrance is added.
Example 29
Daily Care UV-Protection Lotion















% w/w



INCI name
(as used)


















Part A
Oleth-3 phosphate
0.6



Steareth-21
2.5



Steareth-2
1.0



Cetyl alcohol
0.8



Stearyl alcohol
1.5



Tribehenin
0.8



Isohexadecane
8.0



compound of formula (MC 14)
5.0


Part B
Water
q.s. to 100



Glycerol
2.0



Methylene bis-benzotriazolyl
3.0



tetramethylbutylphenol (and) aqua (and) decyl



glucoside (and) propylene glycol (and) xanthan gum



Disodium EDTA
0.1


Part C
Water
20.0



Diazolidinyl urea (and) iodopropynyl
0.15



butylcarbamate



Propylene glycol
4.0


Part D
Sodium acrylate copolymer (and) liquid paraffin
1.5



(and) PPG-1 trideceth-6



Cyclopentasiloxane
4.5



PEG-12 dimethicone
2.0



Tocopheryl acetate
0.45



Water (and) citric acid
q.s.


Part E
Fragrance
q.s.









Preparation Procedure

Heat part A and part B separately to 75° C. Pour part A into part B, whilst stirring continuously. Immediately after emulsification, incorporate in the mixture SF 1202 and SF 1288 from part D. Afterwards homogenise with an Ultra Turrax at 11000 rpm for 30 sec. Allow to cool to 65° C. and incorporate SALCARE® SC91. At a temperature below 50° C., add part C. At 35° C. or below, incorporate vitamin E acetate and subsequently adjust the pH with citric acid. At room temperature, add part E.
Example 30
Sun-Protection Cream, Type O/W















% w/w



INCI name
(as used)


















Part A
Polyglyceryl-3 methylglucose distearate
2.0



Decyl oleate
5.7



Isopropyl palmitate
5.8



Caprylic/capric triglyceride
6.5



compound of formula (MC 14)
2.0



Ethylhexyl methoxycinnamate
5.0



Cetyl alcohol
0.7


Part B
Glycerol
3.0



Carbomer
0.3



Water
q.s. to 100


Part C
Phenoxyethanol (and) methylparaben (and)
0.5



ethylparaben (and) butylparaben (and)



propylparaben (and) isobutylparaben


Part D
Methylene bis-benzotriazolyl
8.0



tetramethylbutylphenol (and) aqua (and) decyl



glucoside (and) propylene glycol (and) xanthan gum



Water
20.0


Part E
Water (and) sodium hydroxide
q.s.



Fragrance
q.s.









Preparation Procedure:

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11000 rpm for 15 sec. The mixture is cooled to 60° C., and part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11000 rpm). After further cooling, with moderate stirring, the pH is adjusted with sodium hydroxide at room temperature. A solution between pH 5.50 and 6.00 is obtained. Finally, fragrance is added.
Example 31
Sun-Protection Cream. Type O/W















% w/w



INCI name
(as used)


















Part A
Polyglyceryl-3 methylglucose distearate
2.0



Decyl oleate
5.7



Isopropyl palmitate
5.8



Caprylic/capric triglyceride
6.5



Mixture of the compound of formula (MC 14)
2.0



(50%) and Uvinul A Plus CAS Reg. No.



302776-68-7 (50%)



Ethylhexyl methoxycinnamate
5.0



Cetyl alcohol
0.7


Part B
Glycerol
3.0



Carbomer
0.3



Water
q.s. to 100


Part C
Phenoxyethanol (and) methylparaben
0.5



(and) ethylparaben (and) butylparaben (and)



propylparaben (and) isobutylparaben


Part D
Methylene bis-benzotriazolyl
8.0



tetramethylbutylphenol (and) aqua (and) decyl



glucoside (and) propylene glycol (and) xanthan gum



Water
20.0


Part E
Water (and) sodium hydroxide
q.s.



Fragrance
q.s.









Preparation Procedure:

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11000 rpm for 15 sec. After cooling 60° C., part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11000 rpm). After further cooling, with moderate stirring, the pH is adjusted at room temperature with sodium hydroxide solution to between 5.50 and 6.00. Finally, fragrance is added.
Example 32
Sun-Protection Cream, Type O/W















% w/w



INCI name
(as used)


















Part A
Polyglyceryl-3 methylglucose distearate
2.0



Decyl oleate
5.7



Isopropyl palmitate
5.8



Caprylic/capric triglyceride
6.5



Mixture of compound of formula (MC 14)
2.0



(50%) and benzylidene camphor,



CAS Reg. No. 36861-47-9 (50%)



Ethylhexyl methoxycinnamate
5.0



Cetyl alcohol
0.7


Part B
Glycerol
3.0



Carbomer
0.3



Water
q.s. to 100


Part C
Phenoxyethanol (and) methylparaben (and)
0.5



ethylparaben (and) butylparaben (and)



propylparaben (and) isobutylparaben


Part D
Methylene bis-benzotriazolyl
8.0



tetramethylbutylphenol (and) aqua (and) decyl



glucoside (and) propylene glycol (and) xanthan gum



Water
20.0


Part E
Water (and) sodium hydroxide
q.s.



Fragrance
q.s.









Preparation Procedure

Part A and part B are heated separately to 75° C. Part A is poured into part B whilst stirring. The mixture is homogenised with an Ultra Turrax at 11000 rpm for 15 sec. After cooling to 60° C., part C and part D are incorporated. The mixture is homogenised again for a short time (5 sec./11000 rpm). After further cooling, with moderate stirring, the pH is adjusted at room temperature with sodium hydroxide. A solution between pH 5.50 and 6.00 is obtained. Finally, fragrance is added.

## Claims

1. A method of protecting human hair and skin against the damaging effect of UV radiation, said method comprising applying to the hair and/or skin a cosmetic, pharmaceutical or veterinary preparation comprising compounds of formula



 wherein
Q is hydrogen; C1-C22alkyl; —OH; —OR7; —NR7R8; or —N═R9;
R1 is hydrogen; C1-C22alkyl; —OR7, —SR7; —NR7R8; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl, C2-C11heteroaralkyl; C6-C10aryl; or C1-C9heteroaryl;
R4 is cyano; COR7, COOR7; CONR7R8; SO2(C6-C12)aryl; C2-C12alk-1-enyl; C3-C12cycloalk-1-enyl; C2-C12alk-1-inyl; C2-C12heteroalkyl; C3-C5heterocycloalkyl; C6-C10aryl; or C1-C9heteroaryl;
R5 is —COR7; —COOR7; —OR7; —SR7, —NHR7, —NR7R8; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12alkylphenyl; C1-C12alkoxy-C6-C10aryl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C3-C12cycloheteroalkyl; C6-C10aryl; C1-C12alkoxy-C6-C10aryl; or C1-C9heteroaryl;
R6 is hydrogen; C1-C22alkyl; C1-C22alkoxy; or COR7;
R7 and R8 independently from each other are hydrogen; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; —(CH2)tCOOH; C7-C12aralkyl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C6-C10aryl; C1-C9heteroaryl; Si—R10R11R12; Si(OR10)(OR11)(OR12); SiR10(OR11)(OR12); SiR10R11(OR12); —(CH2)u—O—(CH2)v—SiR10R11R12; or a radical X-Sil;
t, u and v, independently from each other are a number from 1 to 5;
R9 is a (C1-C6)alkylidene radical;
R10, R11, R12 independently from each other are C1-C22alkyl;
X is a linker;
Sil is a silane-, oligosiloxane- or polysiloxane radical;
R1 and R2, R1 and Q, R1 and R6, R1 and T, R2 and R3, R2 and R4, R2 and R6, R2 and Q, R4 and R6, R4 and T, R6 and Q, T and Q, each independently, are linked together, so that 1, 2, 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings are formed, wherein each of them, independently from each other, may be condensed with an aromatic or heteroaromatic ring, and/or more N-, O- and/or S-heterocyclic rings, and each N atom in a N-heterocyclic ring may be substituted by C1-C22alkyl;
n is a number from 1 to 4; wherein at least one of the radicals R1, R6 or Q is different from hydrogen;
if n=1
T is —COR5; —CN; C6-C10aryl; —NHR5; or —SO2—(C6-C12)aryl;
R2 and R3 independently from each other are C1-C22alkyl; hydroxy-C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl, C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl; C3-C12cycloheteroalkyl; C6-C10aryl; C1-C9heteroaryl; or a radical of formula




p is a number from 5 to 100
q is a number from 1 to 5;
s is a number from 0 to 4;
if n=2
R2 and R3 are each C1-C5alkylene; and simultaneously T is defined as for n=1; or
T is a bivalent radical of formula —NR7—V—NR7—, wherein
V is phenylene; or C1-C5alkylene;
R7 is hydrogen; or C1-C5alkyl; and R2 and R3 simultaneously are defined as for n=1;
if n=3
one of R2, R3 or T is a trivalent radical; and
if n=4
one of R2, R3 or T is a tetravalent radical.

2. A method according to claim 1, wherein in formula (1)
Q is —OH; —OR7; —NR7R8; or —N═R9;
T is —COR5; —CN; or —SO2—(C6-C12)aryl;
R1 is hydrogen; —OR7, —SR7; —NR7R8; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C6-C10aryl; or C1-C9heteroaryl;
R2 and R3 independently from each other are C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl, C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl; C3-C12cycloheteroalkyl; C2-C11heteroaralkyl, C6-C10aryl; or C1-C9heteroaryl;
R4 is cyano; COR7, COOR7; CONR7R8; SO2(C6-C12)aryl, C2-C12alk-1-enyl; C3-C12cycloalk-1-enyl; C2-C12alk-1-inyl; C2-C12heteroalkyl, C3-C5heterocycloalkyl, C6-C10aryl; or C1-C9heteroaryl;
R5 is —COR7; —COOR7; —OR7; —SR7; —NR7R8; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12alkylphenyl; C1-C12alkoxy-C6-C10aryl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C3-C12cycloheteroalkyl; C6-C10aryl; C1-C12alkoxy-C6-C10aryl or C1-C9heteroaryl;
R6 is C1-C22alkyl; C1-C22alkoxy; or COR7;
R7 and R8 independently from each other are hydrogen; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C1-C12heteroalkyl; C2-C11heteroaralkyl; C6-C10aryl; o-C6-C10aryl; or C1-C9heteroaryl;
R9 is a (C1-C6)alkylidene radical; or
R1 and R2, R1 and Q, R1 and R4, R1 and R6, R2 and R3, R3 and Q, R6 and Q, T and Q, each independently, are linked together, so that 1, 2, 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings are formed, wherein each of them, independently from each other, may be condensed with an aromatic or heteroaromatic ring, and/or more N-, O- and/or S-heterocycic rings, and each N atom in a N-heterocyclic ring may be substituted by C1-C22alkyl; and
n is 1.

3. A method according to claim 2, wherein
Q is —OH; —OR6; or —NR7R8;
T is —COR5 —CN; or —SO2—(C6-C12)aryl;
R1 is hydrogen; —OR7, —SR7; —NR7R8; C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; or C6-C10aryl;
R2 and R3 independently from each other are C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12 aralkyl; or C6-C10aryl;
R4 is cyano; —COR5, —COOR7; —CONR7R8; —SO2(C6-C12)aryl; —C1-C22alkylcarbonylamino-C6-C10aryl; or C6-C10aryl;
R5 is —COR7; —COOR7; —CONR7R8, —OR7, —SR7, —NR7R8, C1-C22alkyl; C2-C12alkenyl; C2-C12alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; C6-C10aryl; or C1-C12alkoxy-C6-C10aryl;
R6, R7 and R8 independently from each other are hydrogen; C1-C22alkyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; or C6-C10aryl; or
R1 and R2, R1 and Q, R1 and R4, R1 and R6, R2 and R3, R3 and Q, R6 and Q, T and Q are linked together pairwise, so that 1, 2, 3 or 4 carbocyclic or N-, O- and/or S-heterocyclic rings are formed, wherein each of them, independently from each other may be condensed with an aromatic or heteroaromatic ring, and/or more N, O and/or S-heterocycic rings, and each N atom in a N-heterocyclic ring may be substituted by C1-C22alkyl.

4. A method according to claim 2, wherein in formula (1)
R1 is hydrogen; —S—C1-C22alkyl; or R1 and R2, or R1 and R4 together with the linking nitrogen atom form an alkylene radical which my be interrupted by one or more —O— and/or —NR7— or may be condensed with an aromatic ring; and
R7 is C1-C22alkyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; or C6-C10aryl.

5. A method according to claim 4, wherein in formula (1)
R1 is hydrogen.

6. A method according to claim 1, wherein in formula (1)
R2 and R3 independently from each other are C1-C5alkyl; phenyl-C1-C3alkyl; hydroxy-C1-C12alkyl; or R2 and R3, or R2 and R4, or R2 and Q together with the linking nitrogen atom form an alkylene radical which may be interrupted by one or more —O— and/or —NR7— or may be condensed with an aromatic ring; and
R7 is C1-C22alkyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C12aralkyl; or C6-C10aryl.

7. A method according to claim 6, wherein
R2 and R3 independently from each other are C1-C5alkyl; or R2 and R3 together with the linking nitrogen atom form a C2-C4alkylene radical which may be interrupted by —O— or —NR7; and
R7 is hydrogen; or C1-C5alkyl.

8. A method according to claim 1, wherein in formula (1)
R4 is —COR5; phenyl, which is optionally substituted by C1-C5alkyl; —CN; or —SO2—(C6-C10)aryl; or
R4 and T together with a bivalent C3-C7alkylene radical which my be interrupted by one or more —O— and/or —NR7— form a carbocyclic ring which may be condensed with an aromatic ring; and
R7 is hydrogen; or C1-C5alkyl.

9. A method according to claim 8 wherein
R4 is —CN; or COR5;
R5 is C1-C12alkyl; or C1-C12alkoxy; or
R4 and T together with the bivalent radical of the formula




 wherein
U1 and U3 independently from each other are a radical of formula —CHR7; —NHR7—; or —O—;
U2 is —CH2; or —CO—; or the direct bond;
R7 is hydrogen; or C1-C12alkyl; form an aromatic ring.

10. A method according to claim 9, wherein T and R4 together with the bivalent radicals selected from



 form a heterocyclic ring.

11. A method according to claim 10, wherein in formula (1)
R6 is hydrogen; C1-C5alkyl; C1-C5alkoxy; —O—(C6-C10aryl); or
R6 and Q together with a bivalent C3-C7alkylene radical which may be interrupted by one or more —O— and/or —NR7— or may be condensed with an aromatic ring, form a heterocyclic ring; and
R7 is hydrogen; or C1C12alkyl.

12. A method according to claim 11, wherein
R6 is hydrogen.

13. A method according to claim 1, wherein in formula (1)
T is —CN; —COR5; or —SO2-phenyl;
R5 is C1-C5alkyl; C1-C5alkoxy; or NR7R8;
R7 and R8 independently from each other are hydrogen; or C1-C5alkyl; or
T and Q together with the bivalent C3-C7alkylene radical which may be interrupted by one or more —O— and/or —NR7— or may be condensed with an aromatic ring, form a heterocyclic ring.

14. A method according to claim 13, wherein
T is —CN; or —COR5; and
R5 is C1-C5alkyl; or C1-C5alkoxy.

15. A method according to claim 1, wherein
Q is hydroxy; C1-C5alkoxy; or —NR7R8; and
R7 and R8 independently from each other are hydrogen; C1-C5alkyl; or phenyl, which may be substituted by one or more C1-C5alkyl or C1-C5alkoxy groups.

16. A method according to claim 15, wherein
Q is hydroxy.

17. A method according to claim 1, which comprises compounds of formula



 wherein
U4, U5, U6, U7 and U8 independently of each other are —CHR5—; —CO—; —NR7—; —CS—; or —O—;
R5 is hydrogen; or C1-C5alkyl; and
R1, R2, R3, R6, R7 and Q are defined as in claim 1.

18. A method according to claim 1, which comprises compounds of formula



 wherein
R5 is hydrogen; or C1-C5alkyl; and
R3, R4, and T are defined as in claim 1.

19. A method according to claim 18, which comprises compounds of formula (3), wherein
R3 is C1-C22alkyl; C6-C10aryl; or C7-C12aralkyl.

20. A method according to claim 18, which comprises compounds of formula (3), wherein
R3 is C6-C10aryl.

21. A method according to claim 1, wherein at least one of the radicals R1, R6 or Q is different from hydrogen.

22. A method according to claim 1 wherein
Q is hydrogen; or C1-C22alkyl;
T is —COR5; —CN; or —SO2—(C6-C12)aryl;
R1 is hydrogen; or C1-C22alkyl;
R2 and R3 independently from each other are C1-C22alkyl;
R4 is CN; COR5; CONH2; or SO2(C6-C12)aryl,
R5 is —OR7; —SR7, —NHR7, —NR7R8; C1-C22alkyl; C7-C12aralkyl;
R7 and R8 independently from each other are hydrogen; C1-C22alkyl; —(CH2)m—Si—R10R11R12; Si(OR10)(OR11)(OR12); SiR10(OR11)(OR12); SiR10R11(OR12), or a radical X-Sil;
R9 is a (C1-C6)alkylidene radical;
R10, R11, R12 independently from each other are C1-C22alkyl;
X is a linker;
Sil is a silane-, oligosiloxane- or polysiloxane radical;
R1 and R2, R1 and Q, R1 and R6, R1 and T, R2 and R3, R2 and R4, R2 and R6, R2 and Q, R4 and R6, R4 and T, R6 and Q, T and Q, each independently, are linked together, so that 1, 2, 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings are formed, wherein each of them, independently from each other, may be condensed with an aromatic or heteroaromatic ring, and/or more N-, O-and/or S-heterocycic rings, and each N atom in a N-heterocyclic ring may be substituted by C1-C22alkyl;
n is a number from 1 to 4; and
m is a number for 0 to 4; wherein at least one of the radicals R1, R6 or Q is different from hydrogen.

23. A method according to claim 22, wherein
R1, R6 and Q, independently from each other are hydrogen; or C1-C22alkyl, wherein at least one of R1,
R6 and Q is different from hydrogen.

24. A method according to claim 23, wherein
R1, R6 and Q, independently from each other are hydrogen; or C1-C5alkyl, wherein at least one of R1,
R6 and Q is different from hydrogen.

25. A method according to claim 22, wherein
T and R4 independently from each other are —COR5; —CN; or —SO2—(C6-C12)aryl; and
R5 is —OR7; —NR7R8; C1-C22alkyl; C7-C12aralkyl;
R7 and R8 independently from each other are hydrogen; C1-C22alkyl; —(CH2)m—Si—R10R11R12; and
R10, R11, and R12 independently from each other are C1-C22alkyl.

26. A method according to claim 25, wherein
T and R4 independently from each other are —CN; SO2C6H5;




 or a radical of formula




 wherein
R7 and R8, independently from each other are C1-C12alkyl; or a radical of formula —SiR10R11R12; and
R10, R11 and R12 are C1-C5alkyl.

27. Monomeric and polymeric compounds having the structural element of formula



wherein at least one of the asterix-marked radicals are joint with the monomeric or polymeric radical; and
R1, R2, R4 and R6 are defined as in claim (1).