WO2008131921A1 - Silylated, substituted benzotriazolylphenol compounds - Google Patents

Silylated, substituted benzotriazolylphenol compounds Download PDF

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Publication number
WO2008131921A1
WO2008131921A1 PCT/EP2008/003356 EP2008003356W WO2008131921A1 WO 2008131921 A1 WO2008131921 A1 WO 2008131921A1 EP 2008003356 W EP2008003356 W EP 2008003356W WO 2008131921 A1 WO2008131921 A1 WO 2008131921A1
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unsubstituted
alkyl
radical
substituted
mono
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PCT/EP2008/003356
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French (fr)
Inventor
Olga Gorchs Capa
Oscar Jimenez Alonso
Carlos Ramón Trullas Cabanas
Jordi Corbera Arjona
David Panyella Costa
Lajos Novak
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Isdin S.A.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/16—Emollients or protectives, e.g. against radiation

Definitions

  • the present invention relates to silylated substituted benzotriazolylphenol compounds of general formula (I)
  • a process for their preparation, a pharmaceutical and/or cosmetic composition comprising these compounds, their use for the preparation of a pharmaceutical composition for the prophylaxis and/or treatment of diseases caused by and/or associated with exposure to ultraviolet radiation, their use for the prophylaxis and/or care against non-desired skin conditions, as well as their use as a light-stabilizer in polymer compositions.
  • UV radiation is part of the electromagnetic spectrum emitted by the sun.
  • UV-A and UV-B radiation is of considerable concern to human health.
  • UV-A radiation penetrates the human skin more deeply than UV-B radiation
  • action spectra for biological responses indicate that it is radiation in the UV-B range that is absorbed by DNA - subsequent damage to DNA appears to be a key factor in the initiation of the carcinogenic process in skin.
  • UV-A not only may be an important factor in photoaging but also causes genetic damage to skin cells that can lead to skin cancer.
  • sunscreens which are preferably effective in the UV-A and/or the UV-B and/or optionally in the UV-C radiation range, more preferably in the UV-A and the UV-B and in the UV-C radiation range, since the sunlight radiation intensity, and in consequence the UV radiation, has been increasing continuously.
  • sunscreens which are preferably effective in the UV-A and/or the UV-B and/or optionally in the UV-C radiation range, more preferably in the UV-A and the UV-B and in the UV-C radiation range, since the sunlight radiation intensity, and in consequence the UV radiation, has been increasing continuously.
  • a sufficient protection against such increased UV radiation in order to reduce the risk of suffering of diseases such as e.g.
  • UV- A and/or UV-B radiation and optionally UV-C radiation skin cancer, malignant melanoma, polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis caused by UV- A and/or UV-B radiation and optionally UV-C radiation.
  • UV-absorbing properties in the UV-A and/or the UV-B and/or optionally in the UV-C radiation range, preferably in the UV-A and UV-B radiation and optionally in the UV-C radiation range, in order to provide sufficient protection against these UV radiations, especially in order to provide sufficient care and prophylaxis against diseases caused by or associated with the exposure to UV radiation.
  • substituted, silylated benzotriazolylphenol compounds of general formula (I) given below show remarkable absorption capacities in the UV-A and/or the UV-B and/or UV-C radiation range. These compounds are therefore particularly suitable as UV protecting agents in pharmaceutical and/or cosmetic compositions as well as light-stabilizers in polymer compositions, preferably in textile fibers.
  • the present invention refers to at least one silylated substituted benzotriazolylphenol compound of general formula (I)
  • an unsubstituted or at least mono-substituted aryl radical which may be bonded via a linear or branched, unsubstituted or at least mono-substituted alkylene group and/or which may be condensed with an unsubstituted or at least mono- substituted, saturated or aromatic mono- or bicyclic ring system;
  • R 1 and R 2 are fused to form together an additional aromatic mono- or polycyclic ring system having from 4 to 10 carbon atoms;
  • R 3 represents an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical, which may be condensed with an unsubstituted or at least mono-substituted saturated or aromatic mono- or bicyclic ring system;
  • an unsubstituted or at least mono-substituted aryl or heteroaryl radical which may be condensed with an unsubstituted or at least mono-substituted, saturated or aromatic mono- or bicyclic ring system;
  • R 4 represents a hydrogen atom; a linear or branched, saturated, unsubstituted or at least mono-substituted CM S aliphatic radical;
  • R 5 and R 6 and R 7 independently from one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted CM S aliphatic radical; a linear or branched, saturated, unsubstituted or at least mono-substituted -O-Ci-18 aliphatic radical;
  • an unsubstituted or at least mono-substituted, saturated cycloaliphatic radical an unsubstituted or at least mono-substituted aryl radical, which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
  • R 5 , R 6 and R 7 independently from one another, each represents a radical of general formula (II)
  • R 25 , R 26 , R 27 , R 28 and R 29 independently from one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted C MS aliphatic radical; a linear or branched, saturated, unsubstituted or at least mono-substituted -O-Ci- 18 aliphatic radical; an unsubstituted or at least mono-substituted aryl radical; or an -O-Si(R 30 ) 3 radical, with R 30 representing a linear or branched, unsubstituted or at least mono-substituted C-MS alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-Ci-i 8 alkyl radical or an unsubstituted or at least mono-substituted aryl radical;
  • radicals R 5 , R 6 and R 7 represents a radical of general formula (II) as defined above;
  • R 7 represents a radical of general formula (III)
  • n 0, 1 , 2, 3, 4 or 5;
  • X represents an oxygen atom or an unsubstituted or at least mono-substituted
  • Ci- 6 alkylene radical Ci- 6 alkylene radical
  • R 31 , R 32 , R 33 and R 34 independently of one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted Ci-i 8 aliphatic radical; a linear or branched, saturated, unsubstituted or at least mono-substituted -O-Ci-1 8 aliphatic radical;
  • an unsubstituted or at least mono-substituted aryl radical which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
  • R 30 representing a linear or branched, unsubstituted or at least mono-substituted Ci-i 8 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-Ci-i 8 alkyl radical or an unsubstituted or at least mono-substituted aryl radical; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 23 and R 24 , independent of one another, each represents a hydrogen atom; a linear or branched, saturated, unsubstituted or at least mono-substituted Ci-i 8 aliphatic radical, an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloalipha
  • R 20 and R 21 independently of one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted C M8 aliphatic radical, an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical or an unsubstituted or at least mono-substituted aryl radical;
  • R 22 independent of one another, each represents a hydrogen atom; or an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical or an unsubstituted or at least mono-substituted aryl radical;
  • any of the substituents in any of the herein defined formulae represents a saturated Ci -18 -aliphatic radical, i.e. an alkyl radical
  • said aliphatic radical is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1, 2, 3, 4 or 5 substituent(s).
  • said substituent(s) is/are preferably independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH 2 , -CN, -CF 3 , -OCF 3 , -SCF 3 , -SO 3 Na, -SO 3 K, -SO 3 H, -O-CH 3 , -0-C 2 H 5 , -0-CH 2 -CH 2 -CH 3 , -O-CH(CH 3 ) 2 , -O-C(CH 3 ) 3 , -S-CH 3 , -S-C 2 H 5 , -S-CH 2 -CH 2 -CH 3 , -S-CH(CH 3 ) 2 , -S-C(CH 3 ) 3 , -O-Si-(CH 3 ) 3l -O-Si-(CH 2 -CH 3 ) 3 , -O-Si-[CH(-CH 3 ) 2 ]
  • Suitable alkyl radicals which may be substituted by one or more substituents are preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.
  • any of the substituents in any of the herein defined formulae represents an -0-Ci -I8 alkyl radical
  • said -O-Ci-i 8 alkyl radical is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s).
  • substituent(s) are preferably independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH 2 , -CN, -CF 3 , -OCF 3 , -SCF 3 , -SO 3 Na, -SO 3 K, -SO 3 H, -0-CH 3 , -0-C 2 H 5 , -0-CH 2 -CH 2 -CH 3 , -O-CH(CH 3 ) 2 , -O-C(CH 3 ) 3) -S-CH 3 , -S-C 2 H 5 , -S-CH 2 -CH 2 -CH 3 , -S-CH(CH 3 J 2 , -S-C(CH 3 ) 3 , -O-Si-(CH 3 ) 3 , -O-Si-(CH 2 -CH 3 ) 3 , -O-Si-[CH(-CH 3 ) 2 ] 3 ,
  • any of the substituent(s) in any of the herein defined formulae represents or comprises a (hetero)cycloaliphatic radical, i.e. a cycloaliphatic radical or a heterocycloaliphatic, including a C 3 .g (hetero)cycloalkyl radical, i.e. a C 3- g cycloalkyl or a C 3- 9 heterocycloalkyl radical
  • said (hetero)cycloaliphatic radical is - if not defined otherwise - unsubstituted or optionally substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s).
  • substituent(s) are preferably independently selected from the group consisting Of -CH 3 , -C 2 H 5 , -CH 2 -CH 2 -CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3> F, Cl, Br, I, -OH, -SH, -NH 2 , -CN, -CF 3 , -OCF 3 , -SCF 3 , -SO 3 Na, -SO 3 K, -SO 3 H, -0-CH 3 , -0-C 2 H 5 , -0-CH 2 -CH 2 -CH 3 , -O-CH(CH 3 ) 2 , -O-C(CH 3 ) 3 , -S-CH 3 , -S-C 2 H 5 , -S-CH 2 -CH 2 -CH 3 , -S-CH(CHa) 2 , -S-C(CH 3 ) 3 , -O-Si
  • any of the substituent(s) in any of the herein defined formulae represents or comprises a (hetero)cycloaliphatic radical, i.e. a cycloaliphatic or a heterocycloaliphatic radical, including a C 3-g (hetero)cycloalkyl radical, i.e. a C 3-9 cycloalkyl radical or a C 3- g heterocycloalkyl radical, which contains one or more, preferably 1 , 2 or 3 heteroa- tom(s) as ring member(s), unless defined otherwise, each of these heteroatom(s) is/are preferably independently selected from the group consisting of nitrogen, oxygen and sulphur.
  • a (hetero)cycloaliphatic radical i.e. a cycloaliphatic or a heterocycloaliphatic radical
  • a C 3-g (hetero)cycloalkyl radical i.e. a C 3-9 cycloalkyl radical or a C 3- g heterocycl
  • any of the substituent(s) in any of the herein defined formulae represents or comprises a C 3-9 (hetero)cycloalkyl radical, i.e. a C 3-9 cycloalkyl or a C 3-9 heterocycloalkyl radical, which contains optionally 1 or 2 additional heteroatom(s) as ring member(s), unless defined otherwise, each of these heteroatom(s) is/are preferably independently selected from the group consisting of nitrogen, oxygen and sulphur.
  • C 3-9 cycloalkyl or C 3-9 heterocycloalkyl radicals are preferably selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, pyrrolidinyl, piperidinyl, piperazinyl, homopiperazinyl, morpholinyl, azetidinyl, tetrahydrofuranyl, azepanyl, diazepanyl and azocanyl.
  • any of the substituents in any of the herein defined formulae represents an alkylene group, including an C- ⁇ - 6 alkylene group said alkylene group or C-i- ⁇ alkylene group, is unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s).
  • Said substituent(s) is/are preferably independently selected from the group consisting of -O-C 1-5 -alkyl, -S-Ci -5 - alkyl, -F, Cl, Br, I 1 -CN, -CF 3 , -OCF 3 , -SCF 3 , -OH, -SH, -NH 2 , -NH(C 1-5 -alkyl) and -N(Ci -5 -alkyl) 2 , whereby in each occurrence C- ⁇ -5-alkyl may be linear or branched.
  • Suitable alkylene groups include -(CH 2 )-, -CH(CH 3 )-, -(CH 2 J 2 -, -(CH 2 ) 3 -, -(CH 2 J 4 -, -(CH 2 J 5 and -(CH 2 J 6 -.
  • any of the substituents in any of the herein defined formulae represents or comprises an aryl radical, including a 6-membered aryl radical such as phenyl or a 10- membered aryl radical such as naphthyl or a 14-membered aryl radical such as an- thracenyl radical, said aryl radical is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s).
  • aryl radical including a 6-membered aryl radical such as phenyl or a 10- membered aryl radical such as naphthyl or a 14-membered aryl radical such as an- thracenyl radical
  • said aryl radical is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with
  • said substituent(s) is/are preferably independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH 2 , -CN, -CF 3 , -OCF 3 , -SCF 3 , -SO 3 Na, -SO 3 K, -SO 3 H, -O-CH 3 , -0-C 2 H 5 , -0-CH 2 -CH 2 -CH 3 , -O-CH(CH 3 ) 2 , -O-C(CH 3 ) 3 , -S-CH 3 , -S-C 2 H 5 , -S-CH 2 -CH 2 -CH 3 , -S-CH(CH 3 ) 2 , -S-C(CH 3 ) 3 , -O-Si-(CH 3 ) 3 , -O-Si-(CH 2 -CH 3 ) 3 , -O-Si-[CH(-CH 3 ) 2
  • Preferred aryl radicals which are unsubstituted or at least mono-substituted, are phenyl and naphthyl.
  • any of the substituents in any of the herein defined formulae represents or comprises a heteroaryl radical, including a monocyclic 5- or 6-membered heteroaryl radical or a bi- or tricyclic 8-, 9-, 10-, 11-, 12-, 13- or 14- membered heteroaryl radical
  • said heteroaryl radical is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s).
  • said substituent(s) is/are preferably independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH 2 , -CN, -CF 3 , -OCF 3 , -SCF 3 , -SO 3 Na, -SO 3 K, -SO 3 H, -CH 3 , -C 2 H 5 , -CH 2 -CH 2 -CH 3 , -0-CH 3 , -O-C 2 H 5 , -0-CH 2 -CH 2 -CH 3 , -O-CH(CH 3 ) 2 , -O-C(CH 3 ) 3 , -S-CH 3 , -S-C 2 H 5 , -S-CH 2 -CH 2 -CH 3 , -S-CH(CH 3 ) 2) -S-C(CH 3 J 3 , -O-Si-(CH 3 ) 3 , -O-Si-(CH 2 ) 2
  • 8 -alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, - CF 3 , -OCF 3 , -SCF 3 , -SO 3 Na, -SO 3 K, -SO 3 H, -OH, -SH, -NH 2 and -NO 2 .
  • heteroatom(s), which are present as ring member(s) in the heteroaryl radical may, unless defined otherwise, independently be selected from the group consisting of nitrogen, oxygen and sulphur.
  • the heteroaryl radical comprises 1 , 2, 3 or 4 heteroatom(s).
  • Suitable heteroaryl radicals which are optionally at least mono-substituted, are preferably selected from the group consisting of pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, benzotriazolyl, quinolyl and isoquinolyl.
  • Suitable monocyclic 5- or 6-membered heteroaryl radicals which are unsubstituted or at least mono-substituted, are preferably selected from the group consisting of pyridinyl, pyrrolyl, imidazolyl and pyrazolyl.
  • a mono-, bi-, or polycyclic ring system according to the present invention - if not defined otherwise - means a mono-, bi-, or polycyclic hydrocarbon ring system that is saturated or aromatic.
  • each of the rings of the mono- or bicyclic ring system may contain one or more, preferably 1 , 2 or 3, heteroatom(s) as ring member(s), which may be independent from one another and which can preferably be selected from the group consisting of nitrogen, oxygen and sulphur.
  • the rings of the mono- or bicyclic ring system are preferably 5-, 6- or 7-membered.
  • an aromatic mono-or bicyclic ring system is a phenyl or naphthyl ring system.
  • condensed means that a ring or ring system is attached to another ring or ring system, whereby the terms “annulated” or “annelated” are also used by those skilled in the art to designate this kind of attachment.
  • Such a mono-, bi-, or polycyclic ring system is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s).
  • said substituent(s) is/are preferably independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH 2 , -CN, -CF 3 , -OCF 3 , -SCF 3 , -SO 3 Na, -SO 3 K, -SO 3 H, -CH 3 , -C 2 H 5 , -CH 2 -CH 2 -CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -0-CH 3 , -0-C 2 H 5 , -0-CH 2 -CH 2 -CH 3 , -O-CH(CH 3 ) 2 , -O-C(CH 3 ) 3 , -S-CH 3 , -S-C 2 H 5 , -S-CH 2 -CH 2 -CH 3 , -S-CH(CH 3 ) 2 , -S-C(CHa) 3 , -O
  • R 1 and R 2 independently from one another, each represents a hydrogen atom; a halogen atom; -NO 2 ; -OR 8 ; -SR 9 ; -CN; -NR 10 R 11 ; -COOR 12 ; -COR 13 ; -CONR 14 R 15 ; -OCOR 16 ; -NR 17 -COR 18 ; -NR 19 -COO-R 20 ; -SO 2 -R 21 ; -SO 2 -O-R 22 ; -SO 2 -NR 23 R 24 ;
  • an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl radical which may be bonded via a linear or branched, unsubstituted or at least mono-substituted group and/or which may be condensed with an unsubstituted or at least mono-substituted, saturated or aromatic mono- or bicyclic ring system; or
  • R 1 and R 2 are fused to form together an additional aromatic mono- or polycyclic ring system having from 4 to 10 carbon atoms;
  • R 3 represents an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing C 3-9 (hetero)cycloalkyl radical, which may be condensed with an unsubstituted or at least mono-substituted saturated or aromatic mono- or bicyclic ring system;
  • R 4 represents a hydrogen atom; a linear or branched, unsubstituted or at least mono- substituted C- 1 - 6 alkyl radical;
  • R 5 , R 6 and R 7 independently from one another, each represents a linear or branched, unsubstituted or at least mono-substituted Ci- 6 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-C- ⁇ -6 alkyl radical;
  • an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl radical which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
  • R 5 , R 6 and R 7 independently from one another, each represents a radical of general formula (II)
  • R 25 , R 26 , R 27 , R 28 and R 29 independently from one another, each represents a linear or branched, unsubstituted C 1-6 alkyl radical; a linear or branched, unsubstituted -O-Ci- 6 alkyl radical; an unsubstituted or at least mono-substituted 6-, 10- or 14- membered mono-, bi- or tricyclic aryl radical; or an -O-Si(R 30 ) 3 radical, with R 30 representing a linear or branched, unsubstituted or at least mono-substituted C-i- 6 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-C 1-6 alkyl radical; an unsubstituted or at least mono-substituted 6-, 10- or 14- membered mono-, bi- or tricyclic aryl radical;
  • radicals R 5 , R 6 and R 7 represents a radical of general formula (II) as defined above;
  • R 7 represents a radical of general formula (III)
  • n 0, 1 , 2, 3, 4 or 5;
  • X represents an oxygen atom or an unsubstituted or at least mono-substituted C- ⁇ - 4 alkylene radical
  • R 31 , R 32 , R 33 and R 34 independent of one another, each represents a linear or branched, unsubstituted or at least mono-substituted C- ⁇ - 6 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-Ci- ⁇ alkyl radical;
  • an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl radical which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
  • R 30 representing a linear or branched, unsubstituted or at least mono-substituted C-i- ⁇ alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -0-C 1-6 alkyl radical or an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl radical;
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 , independent of one another, have the above-defined meaning;
  • heterocycloalkyl radicals contain in each case optionally 1 , 2 or 3 additional heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen as ring member(s);
  • C 3-9 cycloalkyl radicals contain in each case optionally 1 , 2 or 3 heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen as ring member(s);
  • the aforementioned d ⁇ alkylene preferably -(CH 2 )-, -(CH 2 ) 2 -, -(CH 2 ) 3 - and -(CH 2 ) 4 - groups are in each case linear or branched, unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of F, Cl, Br 1 I, -CN, -CF 3 , -OCF 3 , -SCF 3 , -OH, -SH, -NH 2 , -O-C 1-6 -alkyl, -S-C 1-6 -alkyl, -NH(Ci -6 -alkyl) and -N(C 1-6 -alkyl) 2 ;
  • Ci -6 alkylene preferably -(CH 2 )-, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 - , -(CH 2 ) 5 - and -(CH 2 ) 6 - groups are in each case unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -CN, -CF 3 , -OCF 3 , -SCF 3 , -OH, -SH, -NH 2 , -O-C 1-6 -alkyl, -S-C 1-6 -alkyl, -NH(C 1-6 -alkyl) and -N(C 1-6 -alkyl) 2 ;
  • the rings of the aforementioned ring systems are in each case independently of each other 5-, 6-, 7-, 8-, 9,- or 10-membered and may in each case independently of one another optionally contain 1 , 2, 3 or 4 heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 have the above-defined meaning
  • radicals R 5 , R 6 and R 7 represents a radical of general formula (II) as defined above;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 30 , R 31 , R 32 , R 33 and R 34 have the above-defined meaning;
  • enantiomers or diastereomers optionally in the form of one of its stereoisomers, preferably enantiomers or diastereomers, its racemate or in the form of a mixture of at least two of its stereoi- somers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 20 , R 21 , R 22 , R 23 , R 24 , R 30 , R 31 , R 32 , R 33 and R 34 have the above-defined meaning
  • enantiomers or diastereomers optionally in the form of one of its stereoisomers, preferably enantiomers or diastereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 20 , R 21 , R 22 , R 23 , R 24 , R 30 , R 31 , R 32 , R 33 and R 34 have the above-defined meaning
  • enantiomers or diastereomers optionally in the form of one of its stereoisomers, preferably enantiomers or diastereomers, its racemate or in the form of a mixture of at least two of its stereoi- somers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 20 , R 21 , R 22 , R 23 , R 24 , R 30 , R 31 , R 32 , R 33 and R 34 have the above-defined meaning
  • enantiomers or diastereomers optionally in the form of one of its stereoisomers, preferably enantiomers or diastereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 20 , R 21 , R 22 , R 23 , R 24 , R 30 , R 31 , R 32 , R 33 and R 34 have the above-defined meaning
  • enantiomers or diastereomers optionally in the form of one of its stereoisomers, preferably enantiomers or diastereomers, its racemate or in the form of a mixture of at least two of its stereoi- somers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 1 and R 2 independently from one another, each represents a a hydrogen atom; F; Cl; Br; I; -NO 2 ; -OR 8 ; -SR 9 ; -CN; -NR 10 R 11 ; -COOR 12 ; -COR 13 ; -CONR 14 R 15 ; -OCOR 16 ; -NR 17 -COR 18 ; -NR 19 -COO-R 20 ; -SO 2 -R 21 ; -SO 2 -O-R 22 ; -SO 2 -NR 23 R 24 ;
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 have the above-defined meaning;
  • radicals R 5 , R 6 and R 7 represents a radical of general formula (II) as defined above;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 have the above-defined meaning;
  • radicals R 5 , R 6 and R 7 represents a radical of general formula (II) as defined above;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 have the above-defined meaning;
  • radicals R 5 , R 6 and R 7 represents a radical of general formula (II) as defined above;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • a linear or branched, unsubstituted or at least mono-substituted -0-C M8 alkyl radical which is unsubstituted or substituted with 1 , 2, 3, 4, 5, 6, 7, 8 or 9 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -CN, -CF 3 , -OCF 3 , -SCF 3 , -SO 3 Na, -SO 3 K, -SO 3 H, -OH, -SH, -NH 2 , -O-C 1-8 -alkyl, -O-Si-(C 1-8 -alkyl) 3 , -Si-(Ci -8 -alkyl) 3 , -S-C 1-8 -alkyl, -NH(C 1-8 -alkyl), -N(C 1-8 -alkyl) 2 , -N(Ci -8 -alkyl) 3 + , phenyl, benz
  • R 5 , R 6 and R 7 independently from one another, each represents a radical of general formula (II)
  • radicals R 5 , R 6 and R 7 represents a radical of general formula (II) as defined above;
  • R1 , D ⁇ 17 , D ⁇ 18 , Dr ⁇ 19 , Dr ⁇ 20 , Dr ⁇ 21 , Dr ⁇ 22 , r D ⁇ 23 and R 24 have the above-defined meaning
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 7 represents a radical of general formula (III)
  • n 0, 1 , 2, 3, 4 or 5;
  • X represents an oxygen atom or an unsubstituted or at least mono-substituted Ci -4 alkylene radical
  • a linear or branched, unsubstituted or at least mono-substituted -0-C-M 8 alkyl radical which is unsubstituted or substituted with 1 , 2, 3, 4, 5, 6, 7, 8 or 9 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -CN, -CF 3 , -OCF 3 , -SCF 3 , -SO 3 Na, -SO 3 K, -SO 3 H, -OH, -SH, -NH 2 , -O-C 1-8 -alkyl, -O-Si-(Ci -8 -alkyl) 3 , -Si-(Ci -8 -alkyl) 3 , -S-C 1-8 -alkyl, -NH(C 1-8 -alkyl), -N(C 1-8 -alkyl) 2 , -N(Ci -8 -alkyl) 3 + , phenyl,
  • R1 D2 D3 D4 D8 D9 D10 D 2 3 1 R 1 R 1 K 1 FX i H i R , and R 24 have the above-defined meaning;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 3 represents a (hetero)cycloaliphatic radical selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, pyrrolidinyl, piperidinyl, piperazinyl, homopiperazinyl, morpholinyl, azetidinyl, tetrahydrofuranyl, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, -O-CH 3 , -0-C 2 H 5 , -0-CH 2 -CH 2 -CH 3 , -O-
  • an aryl or heteroaryl radical selected from the group consisting of phenyl, naphthyl, pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, benzotriazolyl, quinolyl and isoquinolyl, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, -0-CH 3 , -0-C 2 H 5 , -0-CH 2 -CH 2 -CH 3 , -O-CH(CH 3 ) 2 , -O-C(CH 3 ) 3 , -S-CH 3 , -S-C 2 H 5 , -S-CH 2 -CH 2 -CH
  • R 4 represents a hydrogen atom; or a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
  • R 5 , R 6 and R 7 independently from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted or substituted with 1 , 2, 3, 4, or 5 substituents independently selected from the group consisting of F, Cl, Br, I 1 -OH, -SH, -NH 2 , -CN, -CF 3 , -OCF 3 , -SCF 3 , -SO 3 Na, -SO 3 K, -SO 3 H, -0-CH 3 , -0-C 2 H 5 , -S-CH 3 , -O-Si-(CH 3 ) 3 , -0-Si-(CH 2 -
  • R 5 , R 6 and R 7 independently from one another, each represents a radical of general formula (II)
  • R 25 , R 26 , R 27 , R 28 and R 29 independently from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
  • a radical selected from the group consisting of -0-CH 3 , -0-CH 2 -CH 3 , -0-CH 2 -CH 2 -CH 3 , -0-CH 2 -CH 2 -CH 3 , -0-CH 2 -CH 2 -CH 2 -CH 3 , -0-CH 2 -CH 2 -CH 2 -CH 3 , -0-CH 2 -CH 2 -CH 2 -CH 2 -CH 3 and -0-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 3 ; whereby in each occurrence the alkyl chain of these radicals is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
  • R 7 represents a radical of general formula (III)
  • n 0, 1 or 2;
  • X represents an oxygen atom or an unsubstituted or at least mono-substituted
  • R 31 , R 32 , R 33 and R 34 independently of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
  • a radical selected from the group consisting of -CH 2 -Phenyl and -CH 2 - CH 2 -Phenyl;
  • an unsubstituted phenyl or naphthyl radical a radical selected from the group consisting of -O-CH 3l -O-CH 2 -CH 3 , -0-CH 2 -CH 2 -CH 3 , -0-CH 2 -CH 2 -CH 2 -CH 3 , -0-CH 2 -CH 2 -CH 2 -CH 31 -0-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 3 and -0-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 3 ; whereby in each occurrence the alkyl chain of these radicals is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
  • R 30 represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, pentyl and hexyl;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • R 4 represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
  • R 5 , R 6 and R 7 independently from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
  • a radical selected from the group consisting of -CH 2 -Phenyl and -CH 2 - CH 2 -Phenyl;
  • radicals R 5 , R 6 and R 7 independently from one another, each represents a radical of general formula (II)
  • R 25 , R 26 , R 27 , R 28 and R 29 independently from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
  • a radical selected from the group consisting of -CH 2 -Phenyl and -CH 2 - CH 2 -Phenyl;
  • R 7 represents a radical of general formula (III)
  • n 0, 1 or 2;
  • X represents an oxygen atom or an unsubstituted or at least mono-substituted
  • C- I-4 alkylene radical preferably an oxygen atom or an unsubstituted Ci -4 alkylene radical
  • R 31 , R 32 , R 33 and R 34 independently of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
  • a radical selected from the group consisting of -CH 2 -Phenyl and -CH 2 -CH 2 -Phenyl; an unsubstituted phenyl or naphthyl radical;
  • R 30 represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, pentyl and hexyl, which is unsubstituted;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • At least one silylated substituted benzotriazolylphenol compound of general formula (IB) is particularly preferred.
  • R 4b represents a radical selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, which is unsubstituted;
  • R 5b , R 6b and R 7b independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
  • R 5b , R 6b and R 7b independently of one another, each represents a radical of general formula (Mb)
  • R 25b , R 26b , R 27b , R 28b and R 29b independently from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
  • R >7b represents a radical of general formula (IMb)
  • nr ,fb _ O 1 1 or 2, preferably O;
  • X b represents an oxygen atom or an unsubstituted or at least mono-substituted C 1 - 4 alkylene radical; preferably an oxygen atom or an unsubstituted C 1 - 4 alkylene radical;
  • R 31b , R 32b , R 33b and R 346 independently of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
  • a radical selected from the group consisting of -CH 2 -Phenyl and -CH 2 - CH 2 -Phenyl;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • At least one silylated substituted benzotriazolylphenol compound of general formula (IC) is also preferred.
  • n 0, 1 , or 2; preferably 1 ;
  • R 4c represents a radical selected from the group consisting of methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, which is unsubstituted;
  • R 5c , R 6c and R 7c independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
  • a radical selected from the group consisting of -CH 2 -Phenyl and -CH 2 - CH 2 -Phenyl;
  • R 5c , R 6c and R 7c independently of one another, each represents a radical of general formula (lie)
  • a radical selected from the group consisting of -CH 2 -Phenyl and -CH 2 - CH 2 -Phenyl;
  • a radical selected from the group consisting of -O-Si-(CH 3 ) 3 , -O-Si-(C 2 H 5 ) 3 , -0-Si-(C 4 Hg) 3 , -0-Si-(Ph) 3 , -CH 2 -Si-(CH 3 ) 3 and -CH 2 -Si-(C 2 Hs) 3 ;
  • R represents a radical of general formula (MIc)
  • m c 0, 1 or 2, preferably 0;
  • X c represents an oxygen atom or an unsubstituted or at least mono-substituted
  • Ci- 4 alkylene radical preferably an oxygen atom or an unsubstituted Ci-4 alkylene radical
  • en t of one another each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
  • a radical selected from the group consisting of -CH 2 -Phenyl and -CH 2 - CH 2 -Phenyl;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • silylated substituted benzotriazolylphenol compounds of general formulae (ID), (IE) and (IF)
  • R 4b represents a radical selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, which is unsubstituted;
  • m b O, 1 , 2, 3, 4 or 5;
  • en t of one another each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
  • a radical selected from the group consisting of -CH 2 -Phenyl and -CH 2 - CH 2 -Phenyl;
  • a radical selected from the group consisting of -O-Si-(CH 3 ) 3 , -O-Si-(C 2 H 5 ) 3 , -0-Si-(C 4 Hg) 3 , -0-Si-(Ph) 3 , -CH 2 -Si-(CH 3 ) 3 and -CH 2 -Si-(C 2 Hs) 3 ;
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoi- somers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • silylated substituted benzotriazolylphenol compounds of general formulae (IG), (IH) and (IJ)
  • m c , R 1c , R 2c , R 40 , R 31c , R 32c , R 33c and R 34c have the same meaning as the above defined m b , R 1b , R 2b , R 4b , R 31b , R 32b , R 33b and R 34b for the silylated substituted benzotriazolylphenol compounds of general formulae (ID), (IE) and (IF);
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • enantiomers or di- astereomers optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
  • Another aspect of the present invention relates to a process for the preparation of at least one silylated substituted benzotriazolylphenol compound of general formula (I), which comprises the step of reacting at least one compound of general formula (P9)
  • R 1 , R 2 , R 3 and R 4 have the above-defined meaning, with at least one suitable silyl derivative of general formula (P10)
  • a catalyst comprising an electron-rich complex of a late transition metal such as e.g. Co(I), Rh(I), Ni(O), Pd(O), or Pt(O), preferably with Speier catalyst (H 2 [PtCI 6 ]
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 have the above-defined meaning.
  • At least one silylated substituted benzotriazolylphenol compound of general formula (I) is obtained by reacting at least one compound of general formula (P1 )
  • R 1 and R 2 have the above-defined meaning, with sodium nitrite (NaN ⁇ 2) in a suitable reaction media, preferably an aqueous reaction media, preferably in the presence of a mineral acid such as e.g. HCI, at usual temperatures, preferably at a temperature ranging from -20 to 2O 0 C, more preferably at a temperature between O 0 C and 5 0 C until the reaction is completed to yield at least one compound of general formula (P2)
  • a suitable reaction media preferably an aqueous reaction media, preferably in the presence of a mineral acid such as e.g. HCI, at usual temperatures, preferably at a temperature ranging from -20 to 2O 0 C, more preferably at a temperature between O 0 C and 5 0 C until the reaction is completed to yield at least one compound of general formula (P2)
  • R 3 has the above-defined meaning, in the presence of a base, preferably a mineral base such as e.g. sodim hydroxide (NaOH), to activate the phenol in the form of a phenoxide ion, in a suitable solvent, preferably in a protic and/or aqueous solvent such as e.g. H 2 O, ethanol (EtOH), isopropanol or mixtures thereof, at usual temperatures, preferably at a temperature ranging from -20° to 5O 0 C, more preferably at a temperature between O 0 C and room temperature until the reaction is completed to yield at least one compound of general formula (P4)
  • a base preferably a mineral base such as e.g. sodim hydroxide (NaOH)
  • a suitable solvent preferably in a protic and/or aqueous solvent such as e.g. H 2 O, ethanol (EtOH), isopropanol or mixtures thereof, at usual temperatures, preferably at a temperature
  • a base preferably an alkaline base such as e.g. NaOH, preferably in suitable solvent, more preferably a protic and/or aqueous solvent such as e.g. H 2 O, EtOH, isopropanol or mixtures thereof, at usual temperatures, preferably at a temperature ranging from O 0 C to the boiling point of the solvent, more preferably at a temperature between 5O 0 C and the boiling point of the solvent, until the reaction is completed to yield at least one compound of general formula (P6)
  • a base more preferably an alkaline base such as e.g. NaOH
  • suitable solvent more preferably a protic and/or aqueous solvent such as e.g. H 2 O, EtOH, isopropanol or mixtures thereof
  • R 4 has the above-defined meaning and X represents a leaving group preferably chorine, bromine, methanesulfonyl or toluenesulfonyl, more preferably chlorine, preferably in the presence of a base, preferably a mineral base, more preferably K 2 CO 3 , optionally in the presence of iodine salt, preferably Kl 1 in a suitable solvent, preferably an organic solvent such as e.g. ketone or 2-butanone, more preferably 2-butanone, preferably at a temperature ranging from O 0 C to the boiling point of the solvent, more preferably at a temperature between 5O 0 C and the boiling point of the solvent until the reaction is completed to yield at least one compound of general formula (P8)
  • a suitable solvent preferably an organic solvent such as e.g. ketone or 2-butanone, more preferably 2-butanone, preferably at a temperature ranging from O 0 C to the boiling point of the solvent, more preferably at a temperature between 5
  • R 1 , R 2 , R 3 and R 4 have the above-defined meaning, which is preferably reacted according to typical Aromatic Claisen Rearrangement conditions, preferably with the presence of a catalyst, preferably in the presence of a solvent, preferably in the presence of an amine such as e.g. N.N-diethylaniline, preferably at a temperature ranging from O 0 C to 200 0 C 1 more preferably at a temperature between 5O 0 C and 17O 0 C until the reaction is completed to yield at least one compound of general formula (P9)
  • a catalyst preferably in the presence of a solvent, preferably in the presence of an amine such as e.g. N.N-diethylaniline, preferably at a temperature ranging from O 0 C to 200 0 C 1 more preferably at a temperature between 5O 0 C and 17O 0 C until the reaction is completed to yield at least one compound of general formula (P9)
  • R 1 , R 2 , R 3 and R 4 have the above-defined meaning, which is preferably reacted with at least one suitable silyl derivative of general formula (P10)
  • a catalyst comprising an electron-rich complex of a late transition metal such as e.g. Co(I), Rh(I), Ni(O) 1 Pd(O), or Pt(O), preferably with Speier catalyst (H 2 [PtCIe]
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 have the above-defined meaning.
  • the compounds of general formula P6 can be prepared according to the disclosure Of DE 2727386, JP 52113974, CH 476745, US 3399173, GB 991630 or GB 980886.
  • the respective parts of the literature are hereby incorporated by reference.
  • Aromatic Claisen Rearrangement conditions are known to those of ordinary skill in the art and are e.g. described in Tarbell et al., Organic Reactions, Vol. 2 , John Willey, NY, 1944, page 1 or EP 0 392 883.
  • Microwave assisted organic synthesis provides processes of efficiently preparing these compounds in a short time by using microwave irradiation.
  • Microwave assisted chemistry is relatively new compared to some other techniques; however, it has become well established and accepted.
  • Microwave assisted chemical synthesis refers to the use of electromagnetic radiation within the microwave frequencies to provide the energy required to initiate, drive, or accelerate certain chemical reactions. As chemists have long been aware, the application of heat energy is one of the most significant factors in increasing the rate of a wide variety of chemical reactions. Microwave assisted reactions can be completed in a much shorter period of time than conventional thermal-treatment techniques requiring long reaction time.
  • pressure is not critical unless otherwise indicated. Pressures from about 0.5 atmospheres to about 5 atmospheres are generally acceptable, and ambient pressure, i.e. about 1 atmosphere, is preferred as a matter of convenience. Under microwave-assisted heating, sealed reactors are indicated, resulting in high-pressure reactions up to as much as 350 psi.
  • the microwave irradiation may be performed at a power level of 1 to 1600 W 1 preferably 1 to 300 W, and particularly preferably about 70 W.
  • the duration for the microwave irradiation may vary according to conditions such as the amount or reactant but may be in the range from 20 seconds to 60 minutes, preferably from 1 minute to 20 minutes.
  • the reaction can be carried out at a temperature of 50-280 0 C, preferably 80-200 0 C, and more preferably 120-150 0 C, with of without solvent, under microwave irradiation.
  • a presently preferred microwave furnace is commercially available from CEM, Inc., as model Discover ® .
  • the Discover ® System incorporates temperature and pressure feedback systems, for example, an infrared temperature sensor positioned below the reaction vessel, for complete control of the reaction.
  • the compounds of general formula (I), including compounds of general formulae (IA), (IB), (IC), (ID), (IE), (IF), (IG), (IH) and (IJ), in the following only referred to as compounds of general formula (I) herein given above may be purified and/or isolated according to methods well known to those skilled in the art.
  • the compounds of general formula (I) may be isolated by evaporating the reaction medium, addition of water and adjusting the pH value to obtain the compound in form of a solid that can be isolated by filtration, or by extraction with a solvent that is not miscible with water such as chloroform and purification by chromatography or recrystallization from a suitable solvent.
  • the protection of sensitive or reactive groups may be necessary and/or desirable. This can be performed by using conventional protective groups like those described in Protective groups in Organic Chemistry, ed. J. F. W. McOmie, Plenum Press, 1973; T.W. Greene & P. G. M. Wuts and Protective Groups in Organic Chemistry, John Wiley & sons, 1991. The respective parts of the description are hereby incorporated by reference and forms part of the disclosure.
  • the protective groups may be eliminated when convenient by means well known to those skilled in the art.
  • silylated substituted benzotriazolylphenol compounds of general formula (I) are obtained in form of a mixture of stereoisomers, particularly enantiomers or diastereomers, said mixtures may be separated by standard procedures known to those skilled in the art, e.g. chromatographic methods or crystallization with chiral reagents.
  • silylated substituted benzotriazolylphenol compounds of general formula (I) and in each case stereoisomers thereof may be obtained in form of a corresponding salt according to methods well known to those skilled in the art, e.g. by reacting said compound with at least one inorganic and/or organic acid, preferably in a suitable reaction medium.
  • suitable reaction media include, for example, any of the ones given above.
  • Suitable inorganic acids include but are not limited to hydrochloric acid, hydrobromic acid, phosphoric acid, oxalic acid, sulfuric acid, nitric acid
  • suitable organic acids include but are not limited to citric acid, maleic acid, fumaric acid, tartaric acid, or derivatives thereof, p-toluenesulfonic acid, methanesulfonic acid or camphersulfonic acid.
  • salt is to be understood as meaning any form of the silylated substituted benzotriazolylphenol compounds in which they assume an ionic form or are charged and are coupled with a counter-ion (a cation or anion) or are in solution.
  • a counter-ion a cation or anion
  • physiologically acceptable salt is understood in particular, in the context of this invention, as salt (as defined above) formed either with a physiologically tolerated acid, that is to say salts of the particular active compound with inorganic or organic acids which are physiologically tolerated - especially if used on humans and/or mammals - or with at least one, preferably inorganic, cation which are physiologically tolerated - especially if used on humans and/or mammals.
  • physiologically tolerated salts of particular acids are salts of: hydrochloric acid, hydrobromic acid, sulfuric acid, hydrobromide, monohydrobromide, monohydrochloride or hydrochloride, methiodide, methanesulfonic acid, formic acid, acetic acid, oxalic acid, succinic acid, malic acid, tartaric acid, mandelic acid, fumaric acid, lactic acid, citric acid, glutamic acid, hippuric acid picric acid and/or aspartic acid.
  • physiologically tolerated salts of particular bases are salts of alkali metals, such as e.g. sodium or potassium and alkaline earth metals such as e.g. magnesium or calcium and with NH 4 .
  • Particularly preferred are silylated substituted benzotriazolylphenol compounds in form of a sodium, potassium or triethanolamine salt.
  • Solvates, preferably hydrates, of the silylated substituted benzotriazolylphenol compounds of general formula (I) and in each case of corresponding stereoisomers may also be obtained by standard procedures known to those skilled in the art.
  • solvate is to be understood as meaning any form of the silylated substituted benzotriazolylphenol compounds in which they have attached to it via non-covalent binding another molecule (most likely a polar solvent) especially including hydrates and alcoholates, e.g. methanolate.
  • a further aspect of the present invention relates to a pharmaceutical composition
  • a pharmaceutical composition comprising at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above, optionally in form of one of its stereoisomers, preferably enantiomers or diasteromers, a racemate or in form of a mixture of at least two stereoisomers, preferably enantiomers and/or diastereomers, in any mixing ratio, or a physiologically acceptable salt thereof, or a corresponding solvate thereof, and optionally at least one physiologically acceptable auxiliary agent.
  • silylated substituted benzotriazolylphenol compound of general formula (I) given above optionally in form of one of its stereoisomers, preferably enantiomers or diasteromers, a racemate or in form of a mixture of at least two stereoisomers, preferably enantiomers and/or diastereomers, in any mixing ratio, or a physiologically acceptable salt thereof, or a corresponding solv
  • a further aspect of the present invention relates to a cosmetic composition
  • a cosmetic composition comprising at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above, optionally in form of one of its stereoisomers, preferably enantiomers or diasteromers, a racemate or in form of a mixture of at least two stereoisomers, preferably enantiomers and/or diastereomers, in any mixing ratio, or a physiologically acceptable salt thereof, or a corresponding solvate thereof, and optionally at least one physiologically acceptable auxiliary agent.
  • silylated substituted benzotriazolylphenol compound of general formula (I) given above optionally in form of one of its stereoisomers, preferably enantiomers or diasteromers, a racemate or in form of a mixture of at least two stereoisomers, preferably enantiomers and/or diastereomers, in any mixing ratio, or a physiologically acceptable salt thereof, or a corresponding solv
  • inventive silylated benzotriazolylphenol compounds of general formula (I) given above also show remarkable absorption capacities in UV- C radiation range. Since the sunlight radiation intensity continuously increases due to the continuous reduction of stratospheric ozone, the importance of pharmaceutical/cosmetic compositions having such UV-C protecting properties is growing.
  • Said pharmaceutical and/or cosmetic composition is particularly suitable for the prophylaxis and/or care and/or treatment of diseases caused by and/or associated with exposure to ultraviolet radiation, preferably of the lips, the face and/or of the body of mammals, preferably human beings, more preferably for the prophylaxis and/or care and/or treatment of/against non-desired skin conditions comprising polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis.
  • the amount of at least one silylated substituted benzotriazolylphenol compound for the inventive pharmaceutical or cosmetical composition is preferably in each case in the range of 0.01 % to 30% per weight, more preferably 0.01 % to 20% per weight, most preferably 0.1 % to 15% per weight, with respect to the total weight of the composition.
  • At least one of the inventive silylated substituted benzotriazolylphenol compound(s) may be preferably used in micronized form, wherein the size of the particles is preferably in the range of 0.01 to 4 ⁇ m, more preferably in the range of 0.05 to 2 ⁇ m, most preferably in the range of 0,05 to 1 ⁇ m.
  • auxiliary agents can independently from each other be present in either the inventive pharmaceutical or the inventive cosmetical composition: gelling agents, oils, waxes, thickening agents, hydrophilic or hydrophobic polymers, emulsifying agents, emollients, fatty acids, organic solvents, antioxidants, stabilizers, sequestering agents, acidifying or basifying agents, emulsifiers, emollients, surfactants, film formers, biological additives to enhance performance and/or consumer appeal such as amino acids, proteins, vanilla, aloe extract or bioflavinoids, buffering agents, chelating agents such as ethylenediaminetetra-acetic acid (EDTA) or oxalic acid, colorants, dyes, propellants, antifoaming agents, wetting agents, vitamins, emulsion stabilizers, pH adjusters, thickening agents, fragrances, preservatives, opacifying agents, water and/or alcohols.
  • EDTA ethylenediaminetetra-acetic acid
  • oils for the inventive compositions oils from animal or vegetable sources or synthetic are preferably used. Particularly preferred are oils selected from the group comprising liquid petrolatum, liquid paraffin, volatile and non-volatile silicone oils, isoparaffins, polyalphaolefins, fluorated and perfluorated oils.
  • non-ionic, anionic, cationic and amphiphilic tensides can be used, which are preferably selected from the group comprising polyethylenglycol (PEG) and derivatives thereof, tweens, tritons, spans, polygycerines, polyalkyl glycerides, alkyl sulfonates, aryl sulfonates, alkyl phosphates, derivatives of alkyl-betaine and phosphatidylglycerole.
  • PEG polyethylenglycol
  • Emulsifiers are preferably used in certain formulations of the inventive compositions in amounts effective to provide uniform blending of ingredients of the composition.
  • Useful emulsifiers include anionics such as fatty acid soaps, e.g., potassium stearate, sodium stearate, ammonium stearate, and triethanolamine stearate; polyol fatty acid monoesters containing fatty acid soaps, e.g., glycerol monostearate containing either potassium or sodium salt; sulfuric esters (sodium salts), e.g., sodium lauryl 5 sulfate, and sodium acetyl sulfate; and polyol fatty acid monoesters containing sulfuric esters, e.g., glyceryl monostearate containing sodium lauryl surfate; (ii) cationics chloride such as N(stearoyl colamino formylmethyl) pyridium; N-soya-N-eth
  • Emollients may be used in the formulations of the inventive compositions in such amounts to prevent or relieve dryness.
  • Useful emollients include, without limitation hydrocarbon oils and waxes; silicone oils; triglyceride esters; acetoglyceride esters; ethoxylated glyceride; alkyl esters; alkenyl esters; fatty acids; fatty alcohols; fatty alcohol ethers; etheresters; lanolin and derivatives; polyhydric alcohols (polyols) and polyether derivatives; polyhydric alcohol (polyol) esters; wax esters; beeswax derivatives; vegetable waxes; phospholipids; sterols; and/or amides.
  • Surfactants can be used in certain formulations of the inventive compositions. Suitable surfactants are for example those surfactants generally grouped as cleansing agents, emulsifying agents, foam boosters, hydrotropes, solubilizing agents, suspending agents and non-surfactants, which facilitate the dispersion of solids in liquids.
  • Suitable film formers which are preferably used in the formulations of the inventive compositions should keep the composition smooth and even and are preferably, without limitation, at least one substance selected from the group comprising acrylamide/sodium acrylate copolymer; ammonium acrylates copolymer; Balsam Peru; cellulose gum; ethylene/maleic anhydride copolymer; hydroxyethylcellulose; hydroxypropylcellulose; polyacrylamide; polyethylene; polyvinyl alcohol; pvm/MA copolymer (vinyl methylether/maleic anhydride copolymer); PVP (polyvinylpyrrolidone); maleic anhydride polymer, vinylpyrrolidon/hexadecene copolymer; acryliclacrylate copolymer and the like.
  • pH adjusters may also be used in certain formulations of the inventive compositions. These pH adjusters preferably comprise, but are not limited to ammonium hydroxide, triethanolamine or citric acid.
  • Thickening agents used for the formulations of the inventive compositions preferably are, but are not limited to candelilla, carnauba, and microcrystalline waxes, crosslinked acrylic-acid polymers, carbomer, methylhydroxyethylcellulose, hydroxypropylmethylcellulose or hydroxyethylcellulose. and polyethylene thickeners.
  • Examples of preferred organic solvents for the inventive compositions include lower aliphatic alcohols and polyols.
  • Suitable antioxidants suitable for the inventive compositions are preferably selected from the group comprising ascorbic acid (vitamin C), sodium-L-ascorbate, calcium-L- ascorbate, ascorbyl palmitate, butylhydroxyanisole, butylhydroxytoluene, calcium- disodium-EDTA, isoascorbic acid, lecitine, lactic acid, polyphosphate, tocopherol (vitamin E), like ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, propylgallate, octylgallate, dodecylgallate, sodium-isoascorbate, citric acid, sodium citrate, potassium citrate and tin-ll-chloride.
  • Gelling agents which are preferably used in the formulations of the inventive compositions, can be natural or synthetic polymers. Natural polymers are preferably selected from the group comprising Agar-Agar, alginate, pectin, carbomer, carrageenan, casein, dextrine, gelatine, arabic gum, keratine, locust bean gum, xanthan gum and the like. Preferred synthetic polymers, which can be used in the formulations of the inventive compositions are selected from the group comprising acylic acid polymers, polyacryl amides and alkylene oxide polymers.
  • the respective components shall be used in amounts which are in compliance with the Council Directives 76/768/EEC and Commission Directive 95/17/EC on the approximation of the laws of the Member States relating to cosmetic products.
  • the inventive pharmaceutical or cosmetic composition is preferably adapted at least for a once a day, twice or three, four or five times a day, preferably for twice a day application.
  • the inventive pharmaceutical or cosmetical composition may be formulated in liquid or in semi-solid form, preferably as liquid, fluid, foam, cream, gel, paste, balsam, spray, ointment, lotion, conditioner, tonic, milk, mousse, emulsion, serum, oil, stick, shampoo, jelly, suspension, dispersion, lacquer, paint, elixir, drop or aerosol.
  • inventive pharmaceutical or cosmetical compositions are suitable for protecting the skin of UV radiation, either in the range of UV-A or UV-B or UV-C or in the whole UV-A and UV-B range and optionally UV-C range.
  • a further aspect of the present invention relates to the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above for the preparation of a pharmaceutical composition for the prophylaxis and/or treatment of diseases caused by and/or associated with exposure to ultraviolet radiation, preferably of the lips, the face and/or of the body of mammals, preferably human beings.
  • a preferred embodiment of the present invention is related to the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above for the preparation of a pharmaceutical composition for the prophylaxis and/or care and/or treatment against non-desired skin conditions comprising polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis.
  • At least one silylated substituted benzotriazolylphenol compound of general formula (I) given above for the prophylaxis and/or care against non-desired skin conditions comprising polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis.
  • At least one silylated substituted benzotriazolylphenol compound of general formula (I) given above for protecting the skin preferably of the lips, the face and/or of the body of a mammal, preferably a human, against ultraviolet radiation, preferably UV-A and/or UV-B radiation and optionally UV-C radiation.
  • Another aspect of the present invention relates to the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above as a light-stabilizer in polymer compositions, preferably in textile fibers.
  • Such polymer compositions comprising the inventive silylated substituted benzotriazolylphenol compounds of general formula (I) given above as light stabilizers may be in form of articles, moulds, sheets, foils, paintings, coatings, fibers or films.
  • the films comprising the inventive silylated substituted benzotriazolylphenol compounds of general formula (I) given above as light stabilizers are single-layer or multilayer films, which can be used for medical or agricultural applications.
  • the articles, moulds, sheets, foils or films comprising the inventive silylated substituted benzotriazolylphenol compounds of general formula (I) given above as light stabilizers are preferably suitable for outdoor carpeting, awnings, tarps, umbrellas, non-food or food-packaging applications such as rice, corn and flour bags, tapes, ropes, artificial turf, stretch-films, shrink wraps, heavy-duty bags, pool covers, garden furniture, trash cans, bottle and fruit crates, toys, interior and exterior automotive parts such as auto bumpers and interior or exterior trim, outdoor sporting and leisure goods, roofings and window shutters.
  • light stabilizer means, according to the present invention a chemical compound that protects the material like a polymer composition against photodegradation against deterioriating and/or decomposing effects caused by its exposure to light.
  • photostabilizer also referred to as "photostabilizer” or “photoprotecting agent”
  • photoprotecting agent means, according to the present invention a chemical compound that protects the material like a polymer composition against photodegradation against deterioriating and/or decomposing effects caused by its exposure to light.
  • IUPAC International Union of Pure and Applied Chemistry
  • light stabilizers can also be classified according to their special possibility of stabilizing against the impact of light into absorbers, quenchers, peroxide decomposers or free radical scavengers.
  • So called absorbers and quenchers are preferably agents that reduce the impact caused by exposure to light either by absorbing, extincting, filtering, scattering, deflecting or reflecting light.
  • a peroxide decomposer is preferably an agent that transforms peroxides into stable compounds without the formation of free radicals and a free radical scavenger is preferably an agent that eliminates free radicals by binding.
  • the inventive light-stabilized polymer composition comprises as the light- stabilizing component at least one absorber, quencher, peroxide decomposer and/or free radical scavenger.
  • absorption means any of the following means of reducing the exposure to UV radiation like absorbing, extincting, filtering, scattering, deflecting or reflecting of radiation, since absorption only means the ratio of transmitted radiation to the incident radiation, without determining the mechanism according to which the radiation is reduced.
  • Polymers can be preferably classified into four main groups:
  • thermoplastic polymers made of thermoplastic polymers is deformable, melts to a liquid when heated and freezes to a brittle, glassy state when cooled sufficiently.
  • Most thermoplastic polymers are high molecular weight polymers whose chains associate through weak van der Waals forces (polyethylene), stronger dipole-dipole interactions and hydrogen bonding (nylon) or even stacking of aromatic rings (polystyrene). Thermoplastic polymers can be remelted and remolded.
  • thermosets are materials that cure, through the addition of energy, to a stronger form.
  • the energy may be in the form of heat (generally above 200°C), through a chemical reaction (two-part epoxy, for example), or irradiation.
  • Thermoset materials are usually liquid, powder, or malleable prior to curing, and designed to be moulded into their final form, or used as adhesives.
  • the curing process transforms the resin into a plastic or rubber by a cross-linking process.
  • Energy and/or catalysts are added that cause the molecular chains to react at chemically active sites (unsaturated or epoxy sites, for example), linking into a rigid, 3-D structure.
  • the cross-linking process forms a molecule with a larger molecular weight, resulting in a material with a higher melting point.
  • the material forms into a solid material.
  • Subsequent uncontrolled reheating of the material results in reaching the decomposition temperature before the melting point is obtained.
  • a thermoset material cannot be melted and re-shaped after it is cured.
  • Thermoset materials are generally stronger than thermoplastic materials due to this 3-D network of bonds and are also better suited to high-temperature applications up to the decomposition temperature of the material.
  • elastomer is often used interchangeably with the term rubber, and is preferred when referring to vulcanisates. They are amorphous polymers existing above their glass transition temperature, so that considerable segmental motion is possible. At ambient temperatures rubbers are thus relatively soft and deformable. Their primary uses are for seals, adhesives and molded flexible parts. 4. Coordination polymers
  • Coordination polymers are compounds where the metals are bridged by polyatomic ligands, such as e.g. cyanide or carboxylates.
  • thermoplastic polymer is preferably at least one thermoplastic polymer selected from the group comprising acrylonitrile-butadiene-styrene (ABS) copolymer; cellulose derivatives such as cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate, cellulose ether, methyl cellulose, ethylcellulose, propyl- cellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethyl- cellulose and carboxy methylcellulose; ethylene-vinyl acetate (EVA) copolymer; ethylene vinyl alcohol (EVAL) copolymer; polyolefines such as ethylen-propylen copolymer, ethylene-buten-1 copoly
  • styrene-isopren-styrene block copolymer polysulfone (PSU); polyurethane (PU); polyvinyl ether; polyvinylalcohol; polyvinylidenechloride; polyvinylpyrrolidone; polyvinyl chloride (PVC); vinyl chloride- vinyl acetate copolymer; vinyl chloride-vinylidene dichloride copolymer and vinyl pyrrolidon-ethylen-vinylacetate copolymer.
  • Another preferred embodiment of the present invention relates to the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above as a light-stabilizer in elastomer compositions, whereby the elastomer is preferably at least one elastomer selected from the group comprising homo-, co- or block polymer of butadiene; natural rubber (NR); polyisoprene (IR); butyl rubber; halogenated butyl rubbers such as chloro butyl rubber or bromo butyl rubber; polybutadiene (BR); styrene-butadiene rubber (SBR); nitrile rubber; hydrated nitrile rubbers (HNBR); chloroprene rubber (CR); polychloroprene; neoprene; ethylene propylene rubber (EPM); ethylene propylene diene rubber (EPDM); epichlorohydrin rubber (ECO); polyacrylic rubber; silicone rubber; silicone; silcone
  • thermosetting polymer is preferably at least one polymer selected from the group comprising vulcanized rubber; polyoxybenzylmethylenglycolanhydride; duroplast; urea-formaldehyde resins; melamine; cured polyester resins and epoxy resins.
  • Polymer compositions usually comprise additives, which improve the properties of these compositions.
  • Suitable additives used in the inventive light-stabilized composition preferably include, but are not limited to anti-blocking-agents, anti- fogging agents, antistatic agents, antioxidants, biocides, blowing agents, defoamers, dyes, emulsifiers, fillers, flame retardants, heat stabilizers, impact modifiers, lubricants, metal deactivators, hydrocalcites, mould-release agents, optical brighteners, plastisizers, processing agents, pigments, phosphites, phosphonites, reinforcing agents, rheology additives, slip agents and surfactants, whereby each of these aforementioned additives is used in usual amounts known by those skilled in the art.
  • example compound 1 absorbs more than half of the amount of the radiation in the UV-C radiation range, when compared with Mexoryl XL ® (compare: figure 2). Moreover it can be seen that example compound 1 absorbs more amounts of UV radiation at ⁇ max values of approx. 300 nm (UV-B) and approx. 340 nm (UV-A), respectively in comparison to Mexoryl XL ® (compare: figure 2).
  • Example 3 Procedure for synthesis of 2-(2/-/-benzotriazol-2-yl)-4-cyclohexyl-6-[2- methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]-phenol
  • Example 4 Procedure for synthesis of 2-(2/-/-benzotriazol-2-yl)-4-cyclohexyl-6-[2- methyl-S-ti .S.S.S-tetramethyl-i- ⁇ trimethylsilyOoxyJdisiloxany ⁇ propylj-phenol
  • Example 7 2- ⁇ 4-Hydroxy-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]- biphenyl-3-yl ⁇ -2/-/-benzotriazole-5-carbonitrile
  • Example 8 2- ⁇ 4-Hydroxy-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]- biphenyl-3-yl ⁇ -2/-/-benzotriazole-5-carboxylic acid
  • Example 9 2- ⁇ 4-Hydroxy-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]- biphenyl-3-yl ⁇ -2/-/-benzotriazole-5-carboxylic acid
  • a cream formulation with the composition % by weight
  • % by weight of the respective components are based on the total weight of the composition.
  • a polymer composition comprising 3-(5-Methoxy-2H-benzotriazol-2-yl)-5-[2- methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]-biphenyl-4-ol (example compound 6) as light stabilizer.
  • the composition is extruded through a flat nozzle to obtain a film with a thickness adjusted to the requirements of the accelerated weathering test according to ASTM D-5208.
  • the film is then exposed to such weathering test.
  • the light stability of the sample is assessed by measuring the extent of carbonyl oxidation of the polymer by means of infrared spectroscopy. The measurement is carried out after 1000 hours exposition to accelerated weathering (UV-A).
  • UV-A accelerated weathering
  • Mexoryl XL ® absorbs less than half of the amount of the radiation in the UV-C radiation range, when compared with the inventive example compound 1 (compare: figure 1 ). Moreover it can be seen that Mexoryl XL ® absorbs less amounts of UV radiation at ⁇ max values of approx. 300 nm (UV-B) and approx. 340 nm (UV-A), respectively in comparison to example compound 1 (compare: figure 1 ).

Abstract

The present invention relates to silylated substituted benzotriazolylphenol compounds of general formula (I) a process for their preparation, a pharmaceutical and/or cosmetic composition comprising these compounds, their use for the preparation of a pharmaceutical composition for the prophylaxis and/or treatment of diseases caused by and/or associated with exposure to ultraviolet radiation, their use for the prophylaxis and/or care against non-desired skin conditions, as well as their use as a light-stabilizer in polymer compositions.

Description

Silylated, substituted benzotriazolylphenol compounds
The present invention relates to silylated substituted benzotriazolylphenol compounds of general formula (I)
Figure imgf000003_0001
(I)
a process for their preparation, a pharmaceutical and/or cosmetic composition comprising these compounds, their use for the preparation of a pharmaceutical composition for the prophylaxis and/or treatment of diseases caused by and/or associated with exposure to ultraviolet radiation, their use for the prophylaxis and/or care against non-desired skin conditions, as well as their use as a light-stabilizer in polymer compositions.
Ultraviolet (UV) radiation is part of the electromagnetic spectrum emitted by the sun. UV-C radiation (λ = 100-280 nm) is to a great extent absorbed by atmospheric ozone and has minimal penetration to the surface of the earth. 90% or more of UV-B radiation (λ = 280-320 nm) is absorbed by atmospheric ozone, while UV-A radiation (λ = 320-400 nm) passes through the atmosphere without being absorbed substantially. Thus, mainly UV-A and UV-B radiation is of considerable concern to human health. While UV-A radiation penetrates the human skin more deeply than UV-B radiation, action spectra for biological responses indicate that it is radiation in the UV-B range that is absorbed by DNA - subsequent damage to DNA appears to be a key factor in the initiation of the carcinogenic process in skin. In recent years, however, there is increasing evidence that UV-A not only may be an important factor in photoaging but also causes genetic damage to skin cells that can lead to skin cancer.
Evidence of harm associated with overexposure to UV radiation has been demonstrated in many studies. Skin cancer and malignant melanoma are among the most severe health effects, but a series of other health impacts, such as polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis have been identified.
Despite the great diversity of commercially available sunscreens, there still exists a need for sunscreens, which are preferably effective in the UV-A and/or the UV-B and/or optionally in the UV-C radiation range, more preferably in the UV-A and the UV-B and in the UV-C radiation range, since the sunlight radiation intensity, and in consequence the UV radiation, has been increasing continuously. As a consequence there exists a need for a sufficient protection against such increased UV radiation in order to reduce the risk of suffering of diseases such as e.g. skin cancer, malignant melanoma, polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis caused by UV- A and/or UV-B radiation and optionally UV-C radiation.
Therefore, it was an object of the present invention to provide new compounds having UV-absorbing properties in the UV-A and/or the UV-B and/or optionally in the UV-C radiation range, preferably in the UV-A and UV-B radiation and optionally in the UV-C radiation range, in order to provide sufficient protection against these UV radiations, especially in order to provide sufficient care and prophylaxis against diseases caused by or associated with the exposure to UV radiation.
It has surprisingly found that substituted, silylated benzotriazolylphenol compounds of general formula (I) given below show remarkable absorption capacities in the UV-A and/or the UV-B and/or UV-C radiation range. These compounds are therefore particularly suitable as UV protecting agents in pharmaceutical and/or cosmetic compositions as well as light-stabilizers in polymer compositions, preferably in textile fibers.
Thus, in one of its aspects the present invention refers to at least one silylated substituted benzotriazolylphenol compound of general formula (I)
Figure imgf000005_0001
(I)
wherein
k= 0 or 1 ; q = 1 or 2;
R1 and R2, independent from one another, each represents a hydrogen atom; a halogen atom; -NO2; -OR8; -SR9; -CN; -NR10R11; -C(=O)-OR12; -C(=O)R13; -C(=O)-NR14R15; -OC(=O)R16; -NR17-C(=O)R18; -NR19-C(=O)-O-R20; -S(=O)2-R21; -S(=O)2-O-R22; -S(=O)2-NR23R24;
a linear or branched, saturated, unsubstituted or at least mono-substituted CMS aliphatic radical;
an unsubstituted or at least mono-substituted aryl radical, which may be bonded via a linear or branched, unsubstituted or at least mono-substituted alkylene group and/or which may be condensed with an unsubstituted or at least mono- substituted, saturated or aromatic mono- or bicyclic ring system;
or
R1 and R2 are fused to form together an additional aromatic mono- or polycyclic ring system having from 4 to 10 carbon atoms;
R3 represents an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical, which may be condensed with an unsubstituted or at least mono-substituted saturated or aromatic mono- or bicyclic ring system;
or
an unsubstituted or at least mono-substituted aryl or heteroaryl radical, which may be condensed with an unsubstituted or at least mono-substituted, saturated or aromatic mono- or bicyclic ring system;
R4 represents a hydrogen atom; a linear or branched, saturated, unsubstituted or at least mono-substituted CMS aliphatic radical;
with the provision that if q = 1 , then
k = 1 ;
R5 and R6 and R7, independent from one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted CMS aliphatic radical; a linear or branched, saturated, unsubstituted or at least mono-substituted -O-Ci-18 aliphatic radical;
an unsubstituted or at least mono-substituted, saturated cycloaliphatic radical; an unsubstituted or at least mono-substituted aryl radical, which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
or
R5, R6 and R7, independent from one another, each represents a radical of general formula (II)
Figure imgf000007_0001
(") wherein
p = 0, 1 , 2 or 3;
R25, R26, R27, R28 and R29, independent from one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted CMS aliphatic radical; a linear or branched, saturated, unsubstituted or at least mono-substituted -O-Ci-18 aliphatic radical; an unsubstituted or at least mono-substituted aryl radical; or an -O-Si(R30)3 radical, with R30 representing a linear or branched, unsubstituted or at least mono-substituted C-MS alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-Ci-i8 alkyl radical or an unsubstituted or at least mono-substituted aryl radical;
with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
or, with the provision that if q = 2, then k = 0;
R7 represents a radical of general formula (III)
Figure imgf000008_0001
(III) wherein
m = 0, 1 , 2, 3, 4 or 5;
X represents an oxygen atom or an unsubstituted or at least mono-substituted
Ci-6 alkylene radical;
R31, R32, R33 and R34, independent of one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted Ci-i8 aliphatic radical; a linear or branched, saturated, unsubstituted or at least mono-substituted -O-Ci-18 aliphatic radical;
an unsubstituted or at least mono-substituted, saturated cycloaliphatic radical;
an unsubstituted or at least mono-substituted aryl radical, which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
or an -O-Si(R30)3 radical, with R30 representing a linear or branched, unsubstituted or at least mono-substituted Ci-i8 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-Ci-i8 alkyl radical or an unsubstituted or at least mono-substituted aryl radical; R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R23 and R24, independent of one another, each represents a hydrogen atom; a linear or branched, saturated, unsubstituted or at least mono-substituted Ci-i8 aliphatic radical, an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical or an unsubstituted or at least mono- substituted aryl radical;
R20 and R21, independent of one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted CM8 aliphatic radical, an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical or an unsubstituted or at least mono-substituted aryl radical;
and
R22 independent of one another, each represents a hydrogen atom; or an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical or an unsubstituted or at least mono-substituted aryl radical;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, preferably enantiomers or diastereomers, in any mixture ratio, or a salt, preferably a corresponding, physiologically acceptable salt, or a corresponding solvate.
If any of the substituents in any of the herein defined formulae represents a saturated Ci-18-aliphatic radical, i.e. an alkyl radical, said aliphatic radical is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1, 2, 3, 4 or 5 substituent(s). Said substituent(s) is/are preferably independently selected from the group consisting of oxo (=0), F, Cl, Br, I1 -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-d-β-alkyl, -O-Si-(Ci-8-alkyl)3, -Si-(Ci-8-alkyl)3, -Si-(phenyl)3, -S-C1-8-alkyl, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy, whereby in each occurrence Ci-i8-aliphatic and/or Ci-8-alkyl is linear or branched. More preferably said substituent(s) is/are preferably independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -O-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3)2, -S-C(CH3)3, -O-Si-(CH3)3l -O-Si-(CH2-CH3)3, -O-Si-[CH(-CH3)2]3, -Si-(CH3)3, -Si-(CH2-CH3)3> -Si-[CH(-CH3)2]3, -NH-CH3, -NH-C2H5, -NH-CH2-CH2-CH3, -NH-CH(CH3)2, -NH-C(CH3)3, -N(CH3)2, -N(C2H5)2, phenyl, benzyl, phenethyl and phenoxy.
Suitable alkyl radicals, which may be substituted by one or more substituents are preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.
If any of the substituents in any of the herein defined formulae represents an -0-Ci-I8 alkyl radical, said -O-Ci-i8 alkyl radical is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s). Said substituent(s) is/are preferably independently selected from the group consisting of oxo (=0), F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-Ci-8-alkyl, -0-Si-(C1-8- alkyl)3, -Si-(Ci-8-alkyl)3, -Si-(phenyl)3, -S-C1-8-alkyl, -NH(Ci-8-alkyl), -N(Ci-8-alkyl)2, -N(Ci-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy, whereby in each occurrence the alkyl chain of the aforementioned -O-Ci-i8-alkyl and/or Ci-8-alkyl radicals is linear or branched. More preferably said substituent(s) are preferably independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -0-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3) -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3J2, -S-C(CH3)3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3, -O-Si-[CH(-CH3)2]3, -NH-CH3, -NH-C2H5, -NH-CH2-CH2-CH3, -NH-CH(CH3)2, -NH-C(CHg)3, -N(CH3)2, -N(C2Hs)2, phenyl, benzyl, phenethyl and phenoxy.
If any of the substituent(s) in any of the herein defined formulae represents or comprises a (hetero)cycloaliphatic radical, i.e. a cycloaliphatic radical or a heterocycloaliphatic, including a C3.g (hetero)cycloalkyl radical, i.e. a C3-g cycloalkyl or a C3-9 heterocycloalkyl radical, said (hetero)cycloaliphatic radical is - if not defined otherwise - unsubstituted or optionally substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s). Said substituent(s) are preferably independently selected from the group consisting of oxo (=0), d-8-alkyl, -O-Ci-8-alkyl, -S-C1-8-alkyl, -C(=O)-OH, -C(=O)-Ci-8-alkyl, -C(=O)-O-C1-8-alkyl, -O-C(=O)-C1-5-alkyl> F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(Ci-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(C1-8-alkyl)2, -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl, whereby in each occurrence Ci-8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2.
More preferably said substituent(s) are preferably independently selected from the group consisting Of -CH3, -C2H5, -CH2-CH2-CH3, -CH(CH3)2, -C(CH3)3> F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -0-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CHa)2, -S-C(CH3)3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3, -O-Si-[CH(-CH3)2]3, -NH-CH3, -NH-C2H5, -NH-CH2-CH2-CH3, -NH-CH(CH3)2, -NH-C(CH3)3, -N(CH3)2, -N(C2H5)2, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain in these radicals is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, - SH, -NH2 and -NO2.
If any of the substituent(s) in any of the herein defined formulae represents or comprises a (hetero)cycloaliphatic radical, i.e. a cycloaliphatic or a heterocycloaliphatic radical, including a C3-g (hetero)cycloalkyl radical, i.e. a C3-9cycloalkyl radical or a C3-g heterocycloalkyl radical, which contains one or more, preferably 1 , 2 or 3 heteroa- tom(s) as ring member(s), unless defined otherwise, each of these heteroatom(s) is/are preferably independently selected from the group consisting of nitrogen, oxygen and sulphur. If any of the substituent(s) in any of the herein defined formulae represents or comprises a C3-9(hetero)cycloalkyl radical, i.e. a C3-9 cycloalkyl or a C3-9 heterocycloalkyl radical, which contains optionally 1 or 2 additional heteroatom(s) as ring member(s), unless defined otherwise, each of these heteroatom(s) is/are preferably independently selected from the group consisting of nitrogen, oxygen and sulphur.
Suitable saturated, optionally at least one heteroatom as ring member containing (hetero)cycloaliphatic radicals, i.e. cycloaliphatic or heterocycloaliphatic radicals, C3-9 (hetero)cycloalkyl radicals, i.e. C3-9 cycloalkyl or C3-9 heterocycloalkyl radicals are preferably selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, pyrrolidinyl, piperidinyl, piperazinyl, homopiperazinyl, morpholinyl, azetidinyl, tetrahydrofuranyl, azepanyl, diazepanyl and azocanyl.
If any of the substituents in any of the herein defined formulae represents an alkylene group, including an C-ι-6 alkylene group said alkylene group or C-i-β alkylene group, is unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s). Said substituent(s) is/are preferably independently selected from the group consisting of -O-C1-5-alkyl, -S-Ci-5- alkyl, -F, Cl, Br, I1 -CN, -CF3, -OCF3, -SCF3, -OH, -SH, -NH2, -NH(C1-5-alkyl) and -N(Ci-5-alkyl)2, whereby in each occurrence C-ι-5-alkyl may be linear or branched.
Suitable alkylene groups include -(CH2)-, -CH(CH3)-, -(CH2J2-, -(CH2)3-, -(CH2J4-, -(CH2J5 and -(CH2J6-.
If any of the substituents in any of the herein defined formulae represents or comprises an aryl radical, including a 6-membered aryl radical such as phenyl or a 10- membered aryl radical such as naphthyl or a 14-membered aryl radical such as an- thracenyl radical, said aryl radical is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s). Said substituent(s) is/are preferably independently selected from the group consisting of oxo (=O), Ci-8-alkyl, -O-Ci-8-alkyl, -S-Ci-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-Ci.8-alkyl, -O-C(=O)-C1-8-alkyl, F, Cl, Br1 I, -CN1 -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H1 -OH, -SH, -NH2, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H1 -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(C1-8-alkyl)2, -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, -O-Si-(C1-8-alkyl)3, -CH2-Si-(C1-8-alkyl)3, -Si-(Ci-8-alkyl)3, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence Ci-8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, - CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2.
More preferably said substituent(s) is/are preferably independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -O-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3)2, -S-C(CH3)3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3, -O-Si-[CH(-CH3)2]3, -Si-(CH3)3, -CH2-Si-(CH3)3, -NH-CH3, -NH-C2H5, -NH-CH2-CH2-CH3, -NH-CH(CH3)2, -NH-C(CH3)3, -N(CH3)2, -N(C2H5)2, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain in these radicals is linear or branched the cyclic part(s) of said substituent(s) is/are unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2.
Preferred aryl radicals, which are unsubstituted or at least mono-substituted, are phenyl and naphthyl.
If any of the substituents in any of the herein defined formulae represents or comprises a heteroaryl radical, including a monocyclic 5- or 6-membered heteroaryl radical or a bi- or tricyclic 8-, 9-, 10-, 11-, 12-, 13- or 14- membered heteroaryl radical, said heteroaryl radical is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s). Said substituent(s) is/are preferably independently selected from the group consisting of oxo (=0), Ci-8-alkyl, -O-Ci-8-alkyl, -S-Ci-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-Ci-8-alkyl, -O-C(=O)-C1-8-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(Ci-8-alkyl), -N(C1-8-alkyl)2l -N(C1-8-alkyl)3\ -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2> -C(=O)-NH(C1-8-alkyl), -C(=O)-N(Ci-8-alkyl)2, -S(=O)2-C1-8-alkyl, -S(=O)2-phenyl, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence Ci-β-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2.
More preferably said substituent(s) is/are preferably independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -CH3, -C2H5, -CH2-CH2-CH3, -0-CH3, -O-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3)2) -S-C(CH3J3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3, -O-Si-[CH(-CH3)2]3, -NH-CH3, -NH-C2H5, -NH-CH2-CH2-CH3, -NH-CH(CHa)2, -NH-C(CH3)3, -N(CH3)2, -N(C2H5)2, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence Ci.8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, - CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2.
The heteroatom(s), which are present as ring member(s) in the heteroaryl radical, may, unless defined otherwise, independently be selected from the group consisting of nitrogen, oxygen and sulphur. Preferably the heteroaryl radical comprises 1 , 2, 3 or 4 heteroatom(s).
Suitable heteroaryl radicals, which are optionally at least mono-substituted, are preferably selected from the group consisting of pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, benzotriazolyl, quinolyl and isoquinolyl.
Suitable monocyclic 5- or 6-membered heteroaryl radicals, which are unsubstituted or at least mono-substituted, are preferably selected from the group consisting of pyridinyl, pyrrolyl, imidazolyl and pyrazolyl.
A mono-, bi-, or polycyclic ring system according to the present invention - if not defined otherwise - means a mono-, bi-, or polycyclic hydrocarbon ring system that is saturated or aromatic. Optionally each of the rings of the mono- or bicyclic ring system may contain one or more, preferably 1 , 2 or 3, heteroatom(s) as ring member(s), which may be independent from one another and which can preferably be selected from the group consisting of nitrogen, oxygen and sulphur. The rings of the mono- or bicyclic ring system are preferably 5-, 6- or 7-membered.
Preferably an aromatic mono-or bicyclic ring system according to the present invention is a phenyl or naphthyl ring system.
The term "condensed" according to the present invention means that a ring or ring system is attached to another ring or ring system, whereby the terms "annulated" or "annelated" are also used by those skilled in the art to designate this kind of attachment.
Such a mono-, bi-, or polycyclic ring system is - if not defined otherwise - unsubstituted or substituted with one or more substituents, preferably unsubstituted or optionally substituted with 1 , 2, 3, 4 or 5 substituent(s). Said substituent(s) is/are preferably independently selected from the group consisting of oxo (=O), Ci-8-alkyl, -O-d-8-alkyl, -S-C1-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-Ci-8-alkyl, -O-C(=O)-C1-8-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3\ -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(Ci-8-alkyl), -C(=O)-N(C1-8-alkyl)2> -S(=O)2-C1-8-alkyl, -S(=O)2-phenyl, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence Ci-8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2.
More preferably said substituent(s) is/are preferably independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -CH3, -C2H5, -CH2-CH2-CH3, -CH(CH3)2, -C(CH3)3, -0-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3)2, -S-C(CHa)3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3l -O-Si-[CH(-CH3)2]3, -Si-(CH3)3, -CH2-Si-(CH3)3, -NH-CH3, -NH-C2H5, -NH-CH2-CH2-CH3, -NH-CH(CH3)2, -NH-C(CH3)3, -N(CH3)2, -N(C2Hs)2, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain in these radicals is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl1 Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2.
Preferred is a compound of general formula (I),
wherein
R1 and R2, independent from one another, each represents a hydrogen atom; a halogen atom; -NO2; -OR8; -SR9; -CN; -NR10R11; -COOR12; -COR13; -CONR14R15; -OCOR16; -NR17-COR18; -NR19-COO-R20; -SO2-R21; -SO2-O-R22; -SO2-NR23R24;
a linear or branched, unsubstituted or at least mono-substituted CMS alkyl radical;
an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl radical, which may be bonded via a linear or branched, unsubstituted or at least mono-substituted
Figure imgf000016_0001
group and/or which may be condensed with an unsubstituted or at least mono-substituted, saturated or aromatic mono- or bicyclic ring system; or
R1 and R2 are fused to form together an additional aromatic mono- or polycyclic ring system having from 4 to 10 carbon atoms;
R3 represents an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing C3-9(hetero)cycloalkyl radical, which may be condensed with an unsubstituted or at least mono-substituted saturated or aromatic mono- or bicyclic ring system;
or an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl or a 5-, 6-, 8-, 9-, 10-, 11 -, 12-, 13- or 14-membered mono-, bi- or tricyclic heteroaryl radical, which may be condensed with an unsubstituted or at least mono-substituted saturated or aromatic mono- or bicyclic ring system;
R4 represents a hydrogen atom; a linear or branched, unsubstituted or at least mono- substituted C-1-6 alkyl radical;
with the provision that if q = 1 , then
k = 1 ;
R5, R6 and R7, independent from one another, each represents a linear or branched, unsubstituted or at least mono-substituted Ci-6 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-C-ι-6 alkyl radical;
an unsubstituted or at least mono-substituted C3-g cycloalkyl radical;
an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl radical which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
or R5, R6 and R7, independent from one another, each represents a radical of general formula (II)
Figure imgf000017_0001
(H) wherein P = O, 1 , 2 or 3;
R25, R26, R27, R28 and R29, independent from one another, each represents a linear or branched, unsubstituted C1-6 alkyl radical; a linear or branched, unsubstituted -O-Ci-6 alkyl radical; an unsubstituted or at least mono-substituted 6-, 10- or 14- membered mono-, bi- or tricyclic aryl radical; or an -O-Si(R30)3 radical, with R30 representing a linear or branched, unsubstituted or at least mono-substituted C-i-6 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-C1-6 alkyl radical; an unsubstituted or at least mono-substituted 6-, 10- or 14- membered mono-, bi- or tricyclic aryl radical;
with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
or, with the provision that if q = 2, then
k = 0;
R7 represents a radical of general formula (III)
Figure imgf000018_0001
(III) wherein
m = 0, 1 , 2, 3, 4 or 5;
X represents an oxygen atom or an unsubstituted or at least mono-substituted C-ι-4 alkylene radical; R31, R32, R33 and R34, independent of one another, each represents a linear or branched, unsubstituted or at least mono-substituted C-ι-6 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-Ci-β alkyl radical;
an unsubstituted or at least mono-substituted C3-9 cycloalkyl radical;
an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl radical which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
or an -O-Si(R30)3 radical, with R30 representing a linear or branched, unsubstituted or at least mono-substituted C-i-β alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -0-C1-6 alkyl radical or an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl radical;
R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 and R24, independent of one another, have the above-defined meaning;
whereby
the aforementioned CMS alkyl radicals are in each case unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=0), F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-d-β-alkyl, -O-Si-(Ci-8-alkyl)3, -Si-(C1-8-alkyl)3, -Si-(phenyl)3, -S-C1-8-alkyl, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(Ci-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain of the aforementioned Ci-i8- alkyl and/or Ci-8-alkyl radicals is linear or branched;
the aforementioned Ci-β alkyl radicals are in each case unsubstituted or substituted with 1 , 2, 3, 4 or 5, substituent(s) independently selected from the group consisting of oxo (=0), F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-C1-6-alkyl, -O-Si-(Ci-6-alkyl)3 ,-S-Ci-6-alkyl, -Si-(Ci-6-alkyl)3, -Si-(phenyl)3, -NH(C1-6-alkyl), -N(Ci-6-alkyl)2) -N(d-6-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain of the aforementioned Ci-6-alkyl radicals is linear or branched;
the aforementioned -O-C1-6 alkyl radicals are in each case unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=0), F, Cl, Br, I1 -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-d-e-alkyl, -O-Si-(C1-6-alkyl)3, -S-d-e-alkyl, -Si-(C1-6-alkyl)3l -Si-(phenyl)3, -NH(C1-6-alkyl), -N(C1-6-alkyl)2, -N(C1.6-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain of the aforementioned Ci-6-alkyl radicals is linear or branched;
the aforementioned C3-g (hetero)cycloalkyl radicals are in each case unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=0), Ci-8-alkyl, -O-Ci-8-alkyl, -S-Ci-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-Ci-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -NCd^-alky!^, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(Ci-8-alkyl)2, -S(=O)2-C1-8-alkyl, -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl, whereby in each occurrence C-i-8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2;
the aforementioned C3-g heterocycloalkyl radicals contain in each case optionally 1 , 2 or 3 additional heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen as ring member(s);
the aforementioned C3-9 cycloalkyl radicals contain in each case optionally 1 , 2 or 3 heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen as ring member(s);
the aforementioned d^ alkylene, preferably -(CH2)-, -(CH2)2-, -(CH2)3- and -(CH2)4- groups are in each case linear or branched, unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of F, Cl, Br1 I, -CN, -CF3, -OCF3, -SCF3, -OH, -SH, -NH2, -O-C1-6-alkyl, -S-C1-6-alkyl, -NH(Ci-6-alkyl) and -N(C1-6-alkyl)2;
the aforementioned Ci-6 alkylene, preferably -(CH2)-, -(CH2)2-, -(CH2)3-, -(CH2)4- , -(CH2)5- and -(CH2)6- groups are in each case unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -OH, -SH, -NH2, -O-C1-6-alkyl, -S-C1-6-alkyl, -NH(C1-6-alkyl) and -N(C1-6-alkyl)2;
the rings of the aforementioned ring systems are in each case independently of each other 5-, 6-, 7-, 8-, 9,- or 10-membered and may in each case independently of one another optionally contain 1 , 2, 3 or 4 heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen;
and the rings of the aforementioned mono-, bi- or polycyclic ring systems are in each case unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=0), Ci-8-alkyl, -O-Ci-8-alkyl, -S-C1-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-C1-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br1 I, -CN, -CF3, -OCF3, -SCF3, -SO3Na1 -SO3K1 -SO3H1 -OH1 -SH1 -NH2, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(Ci-8-alkyl)3 +, -NO2, -CHO1 -CF2H1 -CFH2, -C(=O)-NH2l -C(=O)-NH(C1-8-alkyl), -C(=O)-N(C1-8-alkyl)2, -S(=O)2-C1-8-alkyl, -S(=O)2-phenyl, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence Ci-8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl1 Br1 I -CN, -CF3, -OCF3, -SCF3, -SO3Na1 -SO3K1 -SO3H1 -OH1 -SH1 -NH2 and -NO2;
the 6-, 10- or 14-membered, mono-, bi- or tricyclic aryl or 5-, 6-, 8-, 9-, 10-, 11-, 12-, 13- or 14-membered mono-, bi- or tricyclic heteroaryl radicals are unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=0), C1-8-alkyl, -O-C1-8-alkyl, -S-C1-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-C1-8-alkyl, -O-C(=O)-C1-8-alkyl, F, Cl1 Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(Ci-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(Ci-8-alkyl)2, -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence Ci-8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2;
the aforementioned aromatic mono- or polycyclic ring system having from 4 to 10 carbon atoms are in each case unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=O), C1-8-alkyl, -O-C1-8-alkyl, -S-Ci-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-C1-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2> -C(=O)-NH(C1-8-alkyl), -C(=O)-N(C1-8-alkyl)2> -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence Ci-β-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN1 -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2;
and the aforementioned 5-, 6-, 8-, 9-, 10-, 11-, 12-, 13- or 14-membered mono-, bi- or tricyclic heteroaryl radicals in each case contain 1 , 2, 3 or 4 heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen as ring member(s);
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I), wherein
q = 1 ; k= 1 ;
and
r P>1 K D1 1 DK2 1 DK3 1 I CX?4 1 DK5 1 D(A6 I DrA7 1 DK8i DK9i DK10 , CK?1 1 , DK12 , DK13 , DK14 , OK15 , DK16 , EK?17 , OK18 , DK19 ,
R20, R21, R22, R23, R24, R25, R26, R27, R28, R29 and R30 have the above-defined meaning;
with the condition that at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
q = 2; k = 0;
and
m, p, X, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R30, R31, R32, R33 and R34 have the above-defined meaning;
optionally in the form of one of its stereoisomers, preferably enantiomers or diastereomers, its racemate or in the form of a mixture of at least two of its stereoi- somers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
q = 2; k = 0; m = 0;
and
r-» V D1 D2 D3 D4 D5 nδ D? D8 O9 D1O D-H D12 D"I3 D14 D1S D16 D1? D18 D19 p, Λ, r\ , ι\ , Γ\ , IX , Γ\ , r\ I IΛ I IΛ , IΛ , Γ\ , r\ , r\ i r\ , r\ , r\ , r\ , r\ , r\ , r\ ,
R20, R21, R22, R23, R24, R30, R31, R32, R33 and R34 have the above-defined meaning;
optionally in the form of one of its stereoisomers, preferably enantiomers or diastereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
q = 2; k = 0; m = 1;
and
r% V D-I D2 D3 D4 D5 D6 D? D8 D9 D1O D11 D12 D13 CS14 D1S D16 T~>W D18 D19 P, Λ, R 1 R 1 R I rX 1 R i R 1 R i R 1 R 1 R , R , R , R , R , R , R , R , R , R ,
R20, R21, R22, R23, R24, R30, R31, R32, R33 and R34 have the above-defined meaning;
optionally in the form of one of its stereoisomers, preferably enantiomers or diastereomers, its racemate or in the form of a mixture of at least two of its stereoi- somers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
q = 2; k = 0; m = 2;
and
r P>, Λ Y, P1 R2 D3 P4 P5 P6 P7 P8 P9 P10 , P R11 , P R12 , PR13 , P R14 , P R15 , PPA16 , PIA17 , PR18 , P R19 ,
R20, R21, R22, R23, R24, R30, R31, R32, R33 and R34 have the above-defined meaning;
optionally in the form of one of its stereoisomers, preferably enantiomers or diastereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
q = 2; k = 0; m = 3;
and
n V D1 D2 D3 D4 D5 D6 D7 D8 D9 p10 D11 p12 D13 D-I4 p15 D16 D17 D18 D19 P, Λ, R , R , R , R , R , R , R , R 1 R , R , R , R , R , R , R , R , R , R , R ,
R20, R21, R22, R23, R24, R30, R31, R32, R33 and R34 have the above-defined meaning;
optionally in the form of one of its stereoisomers, preferably enantiomers or diastereomers, its racemate or in the form of a mixture of at least two of its stereoi- somers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
R1 and R2, independent from one another, each represents a a hydrogen atom; F; Cl; Br; I; -NO2; -OR8; -SR9; -CN; -NR10R11; -COOR12; -COR13; -CONR14R15; -OCOR16; -NR17-COR18; -NR19-COO-R20; -SO2-R21; -SO2-O-R22; -SO2-NR23R24;
a linear or branched, unsubstituted or at least mono-substituted Ci--I8 alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=0), F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-C1-8-alkyl, -O-Si-(C1-8-alkyl)3, -Si-(C1-8-alkyl)3, -S-C1-8-alkyl, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(Ci-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy;
a phenyl or naphthyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of Ci-8-alkyl, -O-C1-8-alkyl, -S-C1-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-C1-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(Ci-8-alkyl)2, -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl;
or
R1 and R2 are fused to form together a phenyl or naphthyl radical which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of C1-8-alkyl, -O-Ci-8-alkyl, -S-Ci-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-Ci-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(C1-8-alkyl), -N(Ci-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(Ci-8-alkyl)2, -S(=O)2-Ci-8-alkylI -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl; and
m, k, p, q, X, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33 and R34 have the above-defined meaning;
with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
R3 represents a (hetero)cycloaliphatic radical selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, pyrrolidinyl, piperidinyl, piperazinyl, homopiperazinyl, morpholinyl, azetidinyl, tetrahydrofuranyl, azepanyl, diazepanyl and azocanyl, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=O), Ci-8-alkyl, -O-Ci-8-alkyl, -S-d-β-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-C1-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(C1-8-alkyl), -N(Ci-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(C1-8-alkyl)2, -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl;
or an aryl or heteroaryl radical selected from the group consisting of phenyl, naphthyl, pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, benzotriazolyl, quinolyl and isoquinolyl, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 sub- stituent(s) independently selected from the group consisting of Ci-8-alkyl, -O-d-β-alkyl, -S-Ci-8-alkyl, -C(=O)-OH, -C(=O)-Ci^-alkyl, -C(=O)-O-C1-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(Ci-8-alkyl)2, -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl;
and
m, k, p, q, X, R1, R2, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26R27, R28, R29, R30, R31, R32, R33 and R34 have the above-defined meaning;
with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
R4 represents a hydrogen atom; a linear or branched, unsubstituted or at least mono- substituted Ci-i8 alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4, 5, 6, 7, 8 or 9 substituent(s) independently selected from the group consisting of oxo (=0), F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-C1-8-alkyl, -O-Si-(Ci-8-alkyl)3, -Si-(C1-8-alkyl)3, -S-Ci-8-alkyl, -NH(Ci-8-alkyl), -N(Ci-8-alkyl)2) -N(C1-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy; and
m, k, p, q, X, R1, R2, R3, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26R27, R28, R29, R30, R31, R32, R33 and R34 have the above-defined meaning;
with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
q = 1 k = 1 ;
R5, R6 and R7, independent from one another, each represents a linear or branched, unsubstituted or at least mono-substituted Ci--I8 alkyl radical which is unsubstituted or substituted with 1 , 2, 3, 4, 5, 6, 7, 8 or 9 substituent(s) independently selected from the group consisting of oxo (=O), F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-C1-8-alkyl, -O-Si-(Ci-8-alkyl)3, -O-Si-(phenyl)3) -Si-(C-i-8-alkyl)3, -Si-(phenyl)3,-S-Ci-8-alkyl, -NH(Ci-8-alkyl), -N(Ci-8-alkyl)2, -N(Ci-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy;
a linear or branched, unsubstituted or at least mono-substituted -0-CM8 alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4, 5, 6, 7, 8 or 9 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-C1-8-alkyl, -O-Si-(C1-8-alkyl)3, -Si-(Ci-8-alkyl)3, -S-C1-8-alkyl, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(Ci-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy;
a phenyl or naphthyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of Ci-8-alkyl, -O-C1-8-alkyl, -S-C1-8-alkyl, -C(=O)-OH, -C(=O)-Ci-8-alkyl, -C(=O)-O-Ci-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br1 I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3\ -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(C1-8-alkyl)2, -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl;
or
R5, R6 and R7, independent from one another, each represents a radical of general formula (II)
Figure imgf000030_0001
("I) wherein
P = O, 1 , 2 or 3;
R25, R26, R27, R28 and R29, independent from one another, each represents a linear or branched, unsubstituted Ci-i8 alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4, 5, 6, 7, 8 or 9 substituent(s) independently selected from the group consisting of oxo (=0), F, Cl, Br, I1 -CN, -CF3, -OCF3, -SCF3, -SO3Na1 -SO3K1 -SO3H, -OH1 -SH1 -NH2, -O-C1-8-alkyl, -O-Si-(C1-8-alkyl)3> -O-Si-(phenyl)3l -Si-(C1-8- alkyl)3, -Si-(phenyl)3, -S-C1-8-alkyl, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3\ phenyl, benzyl, phenethyl and phenoxy; a linear or branched, unsubstituted or at least mono-substituted -O-C-MS alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4, 5, 6, 7, 8 or 9 substituent(s) independently selected from the group consisting of F1 Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-C1-8-alkyl,
Figure imgf000031_0001
-Si-(Ci-8-alkyl)3, -Si-(phenyl)3, -S-Ci-8-alkyl, -NH(C1-8-alkyl), -N(Ci-8-alkyl)2, -N(Ci-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy;
a phenyl or naphthyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of C-i-8-alkyl, -O-Ci-8-alkyl, -S-Ci-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-C1-8-alkyl, -O-C(=O)-Ci-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(Ci-8-alkyl), -N(C1-8-alkyl)2, -N(Ci-8-alkyl)3\ -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(C1-8-alkyl)2, -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl;
or an -O-Si(R30)3 radical, with R30 representing a linear or branched, unsubstituted or at least mono-substituted Ci-6 alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5, substituent(s) independently selected from the group consisting of oxo (=0), F, Cl, Br, I, -CN1 -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H1 -OH1 -SH1 -NH2, -O-C1-6-alkyl, -O-Si-(C1-6-alkyl)3, -S-C1-6-alkyl, -Si-(Ci-6-alkyl)3l -NH(Ci-6-alkyl), -N(Ci-6-alkyl)2, -N(C1-6-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain of the aforementioned C-ι-6-alkyl radicals is linear or branched; a linear or branched, unsubstituted or at least mono-substituted -O-Ci-β alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5, substituent(s) independently selected from the group consisting of F1 Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na1 -SO3K, -SO3H, -OH1 -SH1 -NH2, -O-C1-6-alkyl, -O-Si-(C1-6-alkyl)3l -S-C1-6-alkyl, -Si-(C1-6-alkyl)3, -NH(Ci-6-alkyl), -N(C1-6-alkyl)2, -Ntd-e-alkyl)^, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain of the aforementioned Ci-6-alkyl radicals is linear or branched;
with the condition that at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above; and
R1 ,
Figure imgf000032_0001
, Dι\17 , D ΓΛ18 , Dr\19 , Dr\20 , Dr\21 , Dr\22 , r D\23 and R24 have the above-defined meaning;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
q = 2; k = 0;
R7 represents a radical of general formula (III)
Figure imgf000032_0002
(III) wherein
m = 0, 1 , 2, 3, 4 or 5;
X represents an oxygen atom or an unsubstituted or at least mono-substituted Ci-4 alkylene radical; R31, R32, R33 and R34, independent of one another, each represents a linear or branched, unsubstituted or at least mono-substituted CMS alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4, 5, 6, 7, 8 or 9 substituent(s) independently selected from the group consisting of oxo (=0), F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-Ci-8-alkyl, -O-Si-(C1-8-alkyl)3, -Si-(Ci-8-alkyl)3, -S-C1-8-alkyl, -NH(Ci-8-alkyl), -N(C1-8-alkyl)2, -N(Ci-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy;
a linear or branched, unsubstituted or at least mono-substituted -0-C-M8 alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4, 5, 6, 7, 8 or 9 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-C1-8-alkyl, -O-Si-(Ci-8-alkyl)3, -Si-(Ci-8-alkyl)3, -S-C1-8-alkyl, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(Ci-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy;
a C3-9 cycloalkyl radical selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of Ci-8-alkyl, -O-Ci-8-alkyl, -S-Ci-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-Ci-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH1 -NH2, -NH(C1-8-alkyl), -N(Ci-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2) -C(=O)-NH(Ci-8-alkyl), -C(=O)-N(C1-8-alkyl)2, -S(=O)2-C1-8-alkyl, -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl, whereby in each occurrence Ci-8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2;
a phenyl or naphthyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of Ci-8-alkyl, -O-d-β-alkyl, -S-C1-8-alkyl, -C(=O)-OH, -C(=O)-Ci-8-alkyl, -C(=O)-O-C1-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(Ci-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO1 -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(Ci-8-alkyl), -C(=O)-N(C1-8-alkyl)2, -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl;
or an -O-Si(R30)3 radical, with R30 representing a linear or branched, unsubstituted or at least mono-substituted Ci-6 alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5, substituent(s) independently selected from the group consisting of oxo (=O), F, Cl, Br, I1 -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-C1-6-alkyl, -O-Si-(C1-6-alkyl)3, -S-d-β-alkyl, -Si-(C1-6-alkyl)3, -NH(Ci-6-alkyl), -N(C1-6-alkyl)2, -N(C1-6-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain of the aforementioned Ci-6-alkyl radicals is linear or branched; a linear or branched, unsubstituted or at least mono-substituted -O-d-β alkyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5, substituent(s) independently selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-Ci-6-alkyl, -O-Si-(C1-6-alkyl)3, -S-d-6-alkyl, -Si-(Ci-6-alkyl)3, -NH(d-6-alkyl), -N(C1-6-alkyl)2, -N(Ci-6-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain of the aforementioned d-6-alkyl radicals is linear or branched;!
and
R1 D2 D3 D4 D8 D9 D10 D23 1 R 1 R 1 K 1 FX i H i R ,
Figure imgf000034_0001
and R24 have the above-defined meaning;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
q = 1 or 2; k = 0 or 1 ;
R1 and R2, independent from one another, each represents a hydrogen atom; F; Cl; Br; I; -NO2; -NH2; -SH; -OH; -CN; -C(=O)-OH; -C(=O)-OCH3, -C(=O)-OCH2CH3, -C(=O)-NH2; -S(=O)2-OH; -S(=O)2-NH2; -S(=O)2-Phenyl;
a radical selected from the group consisting of -0-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -OH1 -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -0-CH3, -0-C2H5, -S-CH3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3> -Si-[CH(-CH3)2]3, -Si-(CH3)3) -Si-(CH2-CH3)3, -Si-[CH(-CH3)2]3, -NH-CH3 and -N(-CH3)2; and whereby in each occurrence the alkyl chain of these radicals is linear or branched; or
a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted or substituted with 1 , 2, 3, 4, or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K1 -SO3H, -0-CH3, -0-C2H5, -S-CH3, -O-Si-(CH3)3) -O-Si-(CH2-CH3)3, -O-Si-[CH(-CH3)2]3, -Si-[CH(-CH3)2]s, -Si-(CH3)3, -Si-(CH2-CH3)3, -Si-[CH(-CH3)2]3, -NH-CH3 and -N(-CH3)2; whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
R3 represents a (hetero)cycloaliphatic radical selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, pyrrolidinyl, piperidinyl, piperazinyl, homopiperazinyl, morpholinyl, azetidinyl, tetrahydrofuranyl, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, -O-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3> -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CHa)2, -S-C(CH3)3, -C(=O)-OH, -C(=O)-CH3, -C(=O)-C2H5, -C(=O)-CH2-CH2-CH3, -C(=O)-CH(CH3)2, -C(=O)-C(CH3)3> F, Cl, Br1 I, -CN, -CF3, -OCF3, -SCF3, -S(=O)2-Phenyl, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH-CH3, phenyl, phenethyl, phenoxy and benzyl;
or
an aryl or heteroaryl radical selected from the group consisting of phenyl, naphthyl, pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, benzotriazolyl, quinolyl and isoquinolyl, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, -0-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3)2, -S-C(CH3)3, -C(=O)-OH, -C(=O)-CH3, -C(=O)-C2H5, -C(=O)-CH2-CH2-CH3, -C(=O)-CH(CH3)2, -C(=O)-C(CH3)3, F, Cl, Br1 I, -CN, -CF3, -OCF3, -SCF3, -S(=O)2-Phenyl, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH-CH3, phenyl, phenethyl, phenoxy and benzyl;
R4 represents a hydrogen atom; or a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
with the provision that if q = 1 , then
k = 1 ;
R5, R6 and R7, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted or substituted with 1 , 2, 3, 4, or 5 substituents independently selected from the group consisting of F, Cl, Br, I1 -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -0-CH3, -0-C2H5, -S-CH3, -O-Si-(CH3)3, -0-Si-(CH2-CHa)3, -O-Si-[CH(-CH3)2]3, -Si-[CH(-CH3)2]3, -Si-(CH3)3, -Si-(CH2-CH3)3, -Si-[CH(-CH3)2]3, -NH-CH3, -N(-CH3)2 and phenyl; whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
a radical selected from the group consisting Of -O-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -0-CH3, -0-C2H5, -S-CH3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3, -O-Si-[CH(-CH3)2]3, -Si-[CH(-CH3)2]3, -Si-(CH3)3, -Si-(CH2-CH3)3, -Si-[CH(-CH3)2]3, -NH-CH3 and -N(-CH3)2; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a phenyl or naphthyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, -0-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2> -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3)2, -S-C(CH3)3, -C(=O)-OH, -C(=O)-CH3> -C(=O)-C2H5, -C(=O)-CH2-CH2-CH3, -C(=O)-CH(CH3)2, -C(=O)-C(CH3)3) F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K1 -SO3H, -OH, -SH, -NH2, -NH-CH3, phenyl, phenethyl, phenoxy and benzyl;
or
R5, R6 and R7, independent from one another, each represents a radical of general formula (II)
Figure imgf000038_0001
CD wherein
P = O, 1 or 2;
R25, R26, R27, R28 and R29, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
a radical selected from the group consisting Of -CH2-Ph and -CH2- CH2-Ph;
a radical selected from the group consisting of -0-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain of these radicals is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
an unsubstituted phenyl or naphthyl radical;
or
an -O-Si(R30)3 radical, with R30 representing a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, pentyl and hexyl, which is unsubstituted; with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
or, with the provision that if q = 2, then
k = 0;
R7 represents a radical of general formula (III)
Figure imgf000039_0001
(III) wherein
m = 0, 1 or 2;
X represents an oxygen atom or an unsubstituted or at least mono-substituted
C-1-4 alkylene radical;
R31, R32, R33 and R34, independent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
an unsubstituted phenyl or naphthyl radical; a radical selected from the group consisting of -O-CH3l -O-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH31 -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain of these radicals is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
or
an -O-Si(R30)3 radical, with R30 representing a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, pentyl and hexyl;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is a compound of general formula (I),
wherein
q = 1 or 2; k = 0 or 1 ;
R1 and R2, independent from one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -CH2-C≡N; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Phenyl, -0-CH3; or -0-CH2-CH3;
R3 represents a radical selected from the group consisting of phenyl, naphthyl, cyclopentyl, cyclohexyl and cycloheptyl, which is 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, -0-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CHa)2, -S-C(CHa)3, -C(=O)-OH, -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Phenyl, -C(=O)-CH3, -C(=O)-C2H5, -C(=O)-CH2-CH2-CH3, -C(=O)-CH(CH3)2, -C(=O)-C(CH3)3, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH-CH3, phenyl, phenethyl, phenoxy and benzyl;
R4 represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
with the provision that if q = 1 , then
k = 1 ;
R5, R6 and R7, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting of -0-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
an unsubstituted phenyl or naphthyl radical;
or at least one of the radicals R5, R6 and R7, independent from one another, each represents a radical of general formula (II)
Figure imgf000042_0001
(») wherein
p = 0 or 1 ;
R25, R26, R27, R28 and R29, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting of -0-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
or
an -O-Si(R30)3 radical, with R30 representing a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, pentyl and hexyl, which is unsubstituted; with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
or, with the provision that if q = 2, then
k = 0;
R7 represents a radical of general formula (III)
Figure imgf000043_0001
(III) wherein
m = 0, 1 or 2;
X represents an oxygen atom or an unsubstituted or at least mono-substituted
C-I-4 alkylene radical; preferably an oxygen atom or an unsubstituted Ci-4 alkylene radical;
R31, R32, R33 and R34, independent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
a radical selected from the group consisting of -CH2-Phenyl and -CH2-CH2-Phenyl; an unsubstituted phenyl or naphthyl radical;
a radical selected from the group consisting of -O-CH3, -0-CH2-CH3, -0-CH2-CH2-CHs, -O-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CHs, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain of these radicals is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
or
an -O-Si(R30)3 radical, with R30 representing a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- butyl, pentyl and hexyl, which is unsubstituted;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is at least one silylated substituted benzotriazolylphenol compound of general formula (IB)
Figure imgf000045_0001
wherein
qb = 1 or 2; kb = 0 or 1 ;
R1b and R2b, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Phenyl, -0-CH3; or -0-CH2-CH3;
R3b and R3bb, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Phenyl, -0-CH3; or -0-CH2-CH3;
R4b represents a radical selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, which is unsubstituted;
with the provision that if q b _ = 1, then
kb = 1 ; R5b, R6b and R7b, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -0-CH3, -O-C2H5, -O-C3H7, -0-C-1H9, -0-C5H11 and -O-CeH^; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
an unsubstituted phenyl or naphthyl radical;
or R5b, R6b and R7b, independent of one another, each represents a radical of general formula (Mb)
Figure imgf000046_0001
(Hb)
wherein
pb = O or 1 ;
R25b, R26b, R27b, R28b and R29b, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl; a radical selected from the group consisting of -0-CH3; -0-C2H5; -0-C3H7; -O-C4H9; -O-C5H11; and -O-C6H13; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3; -O-Si-(C2H5)3; -0-Si-(C4Hg)3; -O-Si-(Phenyl)3; -CH2-Si-(CH3)3 and -CH2-Si-(C2Hs)3;
an unsubstituted phenyl or naphthyl radical;
with the condition that if qb = 1 and at the same time kb =1 , at least one of the radicals R5b, R6b and R7b represents a radical of general formula (Mb) as defined above;
or, with the provision that if q b _ = 2, then
k ,bD _ = 0;
R >7b represents a radical of general formula (IMb)
Figure imgf000047_0001
(HIb)
wherein
nr ,fb _ = O1 1 or 2, preferably O; Xb represents an oxygen atom or an unsubstituted or at least mono-substituted C1-4 alkylene radical; preferably an oxygen atom or an unsubstituted C1-4 alkylene radical;
R31b, R32b, R33b and R346, independent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting of -O-CH3; -0-C2H5; -O-C3H7; -O-C4H9; -O-C5H11; and -0-CeH13; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3; -O-Si-(C2H5)3; -0-Si-(C4Hg)3; -O-Si-(Phenyl)3; -CH2-Si-(CH3)3 and -CH2-Si-(C2Hs)3;
or
an unsubstituted phenyl or naphthyl radical;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred is at least one silylated substituted benzotriazolylphenol compound of general formula (IC)
Figure imgf000049_0001
wherein
n = 0, 1 , or 2; preferably 1 ;
R1c and R2c, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Ph, -O-CH3; or -0-CH2-CH3;
R3c and R3cc, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Ph, -0-CH3; or -0-CH2-CH3;
R4c represents a radical selected from the group consisting of methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, which is unsubstituted;
with the provision that if q = 1, then
kc = 1 ; R5c, R6c and R7c, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting of -O-CH3, -0-C2H5, -O-C3H7, -O-C4H9> -0-C5H11, and -0-CeH13; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
an unsubstituted phenyl or naphthyl radical;
or
R5c, R6c and R7c, independent of one another, each represents a radical of general formula (lie)
Figure imgf000050_0001
(lie)
wherein
pc = O or 1 ; R25c R 26Cj R 27c R 28c and R 29c jnc|epencjent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting of -0-CH3, -0-C2H5, -O-C3H7, -O-C4H9, -O-C5H11, and -O-C6Hi3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3, -O-Si-(C2H5)3, -0-Si-(C4Hg)3, -0-Si-(Ph)3, -CH2-Si-(CH3)3 and -CH2-Si-(C2Hs)3;
an unsubstituted phenyl or naphthyl radical;
with the condition that if qc = 1 and at the same time kc =1 , at least one of the radicals R 5c R 6c and R 7c represents a radical of general formula (lie) as defined above;
or, with the provision that if qc = 2, then
kc = 0;
R represents a radical of general formula (MIc)
Figure imgf000051_0001
(MIc) wherein
mc = 0, 1 or 2, preferably 0;
Xc represents an oxygen atom or an unsubstituted or at least mono-substituted
Ci-4 alkylene radical; preferably an oxygen atom or an unsubstituted Ci-4 alkylene radical;
R 3ic R 32c R 33c and R 34c jncjepenc|ent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting Of -O-CH3, -0-C2H5, -0-C3H7, -O-C4H9, -O-C5H11 and -0-C6Hi3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3, -O-Si-(C2H5)3> -0-Si-(C4Hg)3, -0-Si-(Ph)3, -CH2-Si-(CH3)3 and -CH2-Si-(C2Hs)3;
an unsubstituted phenyl or naphthyl radical;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred are silylated substituted benzotriazolylphenol compounds of general formulae (ID), (IE) and (IF)
Figure imgf000053_0001
(ID)
Figure imgf000053_0002
(IE)
Figure imgf000053_0003
(IF) wherein
R1b and R2b, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3; -C(=O)-OCH2CH3; -S(=O)2-Phenyl; -0-CH3; or -0-CH2-CH3;
R3b and R3bb, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3; -C(=O)-OCH2CH3; -S(=O)2-Phenyl; -O-CH3; or -0-CH2-CH3;
R4b represents a radical selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, which is unsubstituted;
mb = O, 1 , 2, 3, 4 or 5;
R 3ib R 32b ^ R 33b and R 34b 7 jncjepenc|ent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting of -0-CH3, -0-C2H5, -0-C3H7, -O-C4H9, -O-C5H11 and -O-C6Hi3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3, -O-Si-(C2H5)3, -0-Si-(C4Hg)3, -0-Si-(Ph)3, -CH2-Si-(CH3)3 and -CH2-Si-(C2Hs)3;
an unsubstituted phenyl or naphthyl radical;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoi- somers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Also preferred are silylated substituted benzotriazolylphenol compounds of general formulae (IG), (IH) and (IJ)
Figure imgf000055_0001
(IG)
Figure imgf000055_0002
(IH)
Figure imgf000056_0001
(IJ)
wherein
mc, R1c, R2c, R40, R31c, R32c, R33c and R34c have the same meaning as the above defined mb, R1b, R2b, R4b, R31b, R32b, R33b and R34b for the silylated substituted benzotriazolylphenol compounds of general formulae (ID), (IE) and (IF);
and
R3c and R3cc, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Phenyl, -0-CH3; Or -O-CH2-CH3;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Particularly preferred is at least one silylated substituted benzotriazolylphenol compound of general formula (I) selected from the group consisting of
[1 ] 3-(2H-benzotriazol-2-yl)-5-[2-methyl-3-[1 ,3,3,3-tetramethyM - [(trimethylsilyl)oxy]disiloxanyl]propyl]biphenyl-4-ol, [2] 3-(2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)- propyl]-biphenyl-4-ol,
[3] 2-(2H-benzotriazol-2-yl)-4-cyclohexyl-6-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl- disiloxanyl)-propyl]-phenol,
[4] 2-(2H-benzotriazol-2-yl)-4-cyclohexyl-6-[2-methyl-3-[1 ,3,3,3-tetramethyl-i - [(trimethylsilyl)oxy]disiloxanyl]propyl]-phenol,
[5] 3-(5-Chloro-2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl- disiloxanyl)-propyl]-biphenyl-4-ol,
[6] 3-(5-Methoxy-2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl- disiloxanyl)-propyl]-biphenyl-4-ol,
[7] 2-{4-Hydroxy-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]- biphenyl-3-yl}-2/-/-benzotriazole-5-carbonitrile,
and
[8] 2-{4-Hydroxy-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]- biphenyl-3-yl}-2/-/-benzotriazole-5-carboxylic acid,
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
Another aspect of the present invention relates to a process for the preparation of at least one silylated substituted benzotriazolylphenol compound of general formula (I), which comprises the step of reacting at least one compound of general formula (P9)
Figure imgf000058_0001
wherein R1, R2, R3 and R4 have the above-defined meaning, with at least one suitable silyl derivative of general formula (P10)
Figure imgf000058_0002
wherein R5, R6, R7 and k have the above-defined meaning, following typical hydrosilylation of carbon-carbon double bonds conditions, according to general methods known for the person skilled in the art, preferably in the presence of a catalyst, more preferably in the presence of a catalyst comprising an electron-rich complex of a late transition metal such as e.g. Co(I), Rh(I), Ni(O), Pd(O), or Pt(O), preferably with Speier catalyst (H2[PtCI6]), PtO2 or Karstedt catalyst (Pt2[(CH2=CH)Me2Si]2O)3), more preferably using Karstedt catalyst, preferably in the presence of an organic solvent, more preferably an aromatic solvent such as e.g. xylene, preferably at a temperature ranging from O0C to the boiling point of the solvent, more preferably at a temperature between 5O0C and the boiling point of the solvent, even more preferably at 1000C until the reaction is completed to yield at least one compound of general formula (I)
Figure imgf000059_0001
wherein R1, R2, R3, R4, R5, R6 and R7 have the above-defined meaning.
At least one silylated substituted benzotriazolylphenol compound of general formula (I) is obtained by reacting at least one compound of general formula (P1 )
Figure imgf000059_0002
(P1)
wherein R1 and R2 have the above-defined meaning, with sodium nitrite (NaNθ2) in a suitable reaction media, preferably an aqueous reaction media, preferably in the presence of a mineral acid such as e.g. HCI, at usual temperatures, preferably at a temperature ranging from -20 to 2O0C, more preferably at a temperature between O0C and 50C until the reaction is completed to yield at least one compound of general formula (P2)
Figure imgf000060_0001
(P2)
wherein R1 and R2 have the above-defined meaning, which is reacted with at least one compound of general formula (P3)
Figure imgf000060_0002
(P3)
wherein R3 has the above-defined meaning, in the presence of a base, preferably a mineral base such as e.g. sodim hydroxide (NaOH), to activate the phenol in the form of a phenoxide ion, in a suitable solvent, preferably in a protic and/or aqueous solvent such as e.g. H2O, ethanol (EtOH), isopropanol or mixtures thereof, at usual temperatures, preferably at a temperature ranging from -20° to 5O0C, more preferably at a temperature between O0C and room temperature until the reaction is completed to yield at least one compound of general formula (P4)
Figure imgf000060_0003
(P4) wherein R1, R2 and R3 have the above-defined meaning, which is preferably reacted with at least one reducing agent such as e.g., ammonium sulphide, hydroxylamine, sodium dithionite or formamidinesulfinic acid (P5)
Figure imgf000061_0001
(P5)
preferably in the presence of a base, more preferably an alkaline base such as e.g. NaOH, preferably in suitable solvent, more preferably a protic and/or aqueous solvent such as e.g. H2O, EtOH, isopropanol or mixtures thereof, at usual temperatures, preferably at a temperature ranging from O0C to the boiling point of the solvent, more preferably at a temperature between 5O0C and the boiling point of the solvent, until the reaction is completed to yield at least one compound of general formula (P6)
Figure imgf000061_0002
(P6)
wherein R1, R2 and R3 have the above-defined meaning, which is reacted with at least one compound of general formula (P7)
Figure imgf000062_0001
(P7)
wherein R4 has the above-defined meaning and X represents a leaving group preferably chorine, bromine, methanesulfonyl or toluenesulfonyl, more preferably chlorine, preferably in the presence of a base, preferably a mineral base, more preferably K2CO3, optionally in the presence of iodine salt, preferably Kl1 in a suitable solvent, preferably an organic solvent such as e.g. ketone or 2-butanone, more preferably 2-butanone, preferably at a temperature ranging from O0C to the boiling point of the solvent, more preferably at a temperature between 5O0C and the boiling point of the solvent until the reaction is completed to yield at least one compound of general formula (P8)
Figure imgf000062_0002
wherein R1, R2, R3 and R4 have the above-defined meaning, which is preferably reacted according to typical Aromatic Claisen Rearrangement conditions, preferably with the presence of a catalyst, preferably in the presence of a solvent, preferably in the presence of an amine such as e.g. N.N-diethylaniline, preferably at a temperature ranging from O0C to 2000C1 more preferably at a temperature between 5O0C and 17O0C until the reaction is completed to yield at least one compound of general formula (P9)
Figure imgf000063_0001
wherein R1, R2, R3 and R4 have the above-defined meaning, which is preferably reacted with at least one suitable silyl derivative of general formula (P10)
Figure imgf000063_0002
k
(P10)
wherein R5, R6, R7 and k have the above-defined meaning, following typical hydrosilylation of carbon-carbon double bonds conditions, according to general methods known for the person skilled in the art, preferably in the presence of a catalyst, more preferably in the presence of a catalyst comprising an electron-rich complex of a late transition metal such as e.g. Co(I), Rh(I), Ni(O)1 Pd(O), or Pt(O), preferably with Speier catalyst (H2[PtCIe]), PtO2 or Karstedt catalyst (Pt2I(CH2=CH)Me2Si]2O)3), more preferably using Karstedt catalyst, preferably in the presence of an organic solvent, more preferably an aromatic solvent such as e.g. xylene, preferably at a temperature ranging from O0C to the boiling point of the solvent, more preferably at a temperature between 5O0C and the boiling point of the solvent, even more preferably at 1000C until the reaction is completed to yield at least one compound of general formula (I)
Figure imgf000064_0001
(I)
wherein R1, R2, R3, R4, R5, R6 and R7 have the above-defined meaning.
The compounds of general formulae P1 , P2, P3, P4, P5, P7, P8, P9 and P10 are commercially available or may be prepared according to standard methods known in the prior art, as e.g. according to JP 4046333, JP 61054982 or EP 0 031 302. The respective parts of the literature are hereby incorporated by reference.
The compounds of general formula P6 can be prepared according to the disclosure Of DE 2727386, JP 52113974, CH 476745, US 3399173, GB 991630 or GB 980886. The respective parts of the literature are hereby incorporated by reference.
The aforementioned hydrosilylation of carbon-carbon double bonds with a suitable silyl derivative is known to those skilled in the art and described e.g. in Organic Reactions, Vol. 13 , John Willey, NY, 1963, page 209 or in Organic Letters, 2002, Vol. 4(13), page 2117-9.
The aforementioned Aromatic Claisen Rearrangement conditions are known to those of ordinary skill in the art and are e.g. described in Tarbell et al., Organic Reactions, Vol. 2 , John Willey, NY, 1944, page 1 or EP 0 392 883.
Any of the aforementioned steps, which requires heating, can also be carried out in a microwave oven, employing a typical procedure of MAOS (microwave assisted organic synthesis). The present invention provides processes of efficiently preparing these compounds in a short time by using microwave irradiation. Microwave assisted chemistry is relatively new compared to some other techniques; however, it has become well established and accepted. Microwave assisted chemical synthesis refers to the use of electromagnetic radiation within the microwave frequencies to provide the energy required to initiate, drive, or accelerate certain chemical reactions. As chemists have long been aware, the application of heat energy is one of the most significant factors in increasing the rate of a wide variety of chemical reactions. Microwave assisted reactions can be completed in a much shorter period of time than conventional thermal-treatment techniques requiring long reaction time. In each of the reactions discussed or illustrated above, pressure is not critical unless otherwise indicated. Pressures from about 0.5 atmospheres to about 5 atmospheres are generally acceptable, and ambient pressure, i.e. about 1 atmosphere, is preferred as a matter of convenience. Under microwave-assisted heating, sealed reactors are indicated, resulting in high-pressure reactions up to as much as 350 psi.
Common microwave equipment may be used in preparation processes according to the present invention. The microwave irradiation may be performed at a power level of 1 to 1600 W1 preferably 1 to 300 W, and particularly preferably about 70 W. The duration for the microwave irradiation may vary according to conditions such as the amount or reactant but may be in the range from 20 seconds to 60 minutes, preferably from 1 minute to 20 minutes. The reaction can be carried out at a temperature of 50-280 0C, preferably 80-200 0C, and more preferably 120-1500C, with of without solvent, under microwave irradiation. A presently preferred microwave furnace is commercially available from CEM, Inc., as model Discover®. The Discover® System incorporates temperature and pressure feedback systems, for example, an infrared temperature sensor positioned below the reaction vessel, for complete control of the reaction.
The general process for the preparation of compounds of general formula (I) as described above, is also depicted in general scheme (I): Scheme (I)
Figure imgf000066_0001
The compounds of general formula (I), including compounds of general formulae (IA), (IB), (IC), (ID), (IE), (IF), (IG), (IH) and (IJ), in the following only referred to as compounds of general formula (I) herein given above may be purified and/or isolated according to methods well known to those skilled in the art. Preferably, the compounds of general formula (I) may be isolated by evaporating the reaction medium, addition of water and adjusting the pH value to obtain the compound in form of a solid that can be isolated by filtration, or by extraction with a solvent that is not miscible with water such as chloroform and purification by chromatography or recrystallization from a suitable solvent.
During some synthetic reactions described above or while preparing the compounds of general formula (I) the protection of sensitive or reactive groups may be necessary and/or desirable. This can be performed by using conventional protective groups like those described in Protective groups in Organic Chemistry, ed. J. F. W. McOmie, Plenum Press, 1973; T.W. Greene & P. G. M. Wuts and Protective Groups in Organic Chemistry, John Wiley & sons, 1991. The respective parts of the description are hereby incorporated by reference and forms part of the disclosure. The protective groups may be eliminated when convenient by means well known to those skilled in the art.
If the silylated substituted benzotriazolylphenol compounds of general formula (I) are obtained in form of a mixture of stereoisomers, particularly enantiomers or diastereomers, said mixtures may be separated by standard procedures known to those skilled in the art, e.g. chromatographic methods or crystallization with chiral reagents.
The silylated substituted benzotriazolylphenol compounds of general formula (I) and in each case stereoisomers thereof may be obtained in form of a corresponding salt according to methods well known to those skilled in the art, e.g. by reacting said compound with at least one inorganic and/or organic acid, preferably in a suitable reaction medium. Suitable reaction media include, for example, any of the ones given above. Suitable inorganic acids include but are not limited to hydrochloric acid, hydrobromic acid, phosphoric acid, oxalic acid, sulfuric acid, nitric acid, suitable organic acids include but are not limited to citric acid, maleic acid, fumaric acid, tartaric acid, or derivatives thereof, p-toluenesulfonic acid, methanesulfonic acid or camphersulfonic acid.
The term "salt" is to be understood as meaning any form of the silylated substituted benzotriazolylphenol compounds in which they assume an ionic form or are charged and are coupled with a counter-ion (a cation or anion) or are in solution. By this are also to be understood complexes of the active compound with other molecules and ions, in particular complexes which are complexed via ionic interactions.
The term "physiologically acceptable salt" is understood in particular, in the context of this invention, as salt (as defined above) formed either with a physiologically tolerated acid, that is to say salts of the particular active compound with inorganic or organic acids which are physiologically tolerated - especially if used on humans and/or mammals - or with at least one, preferably inorganic, cation which are physiologically tolerated - especially if used on humans and/or mammals. Examples of physiologically tolerated salts of particular acids are salts of: hydrochloric acid, hydrobromic acid, sulfuric acid, hydrobromide, monohydrobromide, monohydrochloride or hydrochloride, methiodide, methanesulfonic acid, formic acid, acetic acid, oxalic acid, succinic acid, malic acid, tartaric acid, mandelic acid, fumaric acid, lactic acid, citric acid, glutamic acid, hippuric acid picric acid and/or aspartic acid. Examples of physiologically tolerated salts of particular bases are salts of alkali metals, such as e.g. sodium or potassium and alkaline earth metals such as e.g. magnesium or calcium and with NH4. Particularly preferred are silylated substituted benzotriazolylphenol compounds in form of a sodium, potassium or triethanolamine salt.
Solvates, preferably hydrates, of the silylated substituted benzotriazolylphenol compounds of general formula (I) and in each case of corresponding stereoisomers may also be obtained by standard procedures known to those skilled in the art.
The term "solvate" according to this invention is to be understood as meaning any form of the silylated substituted benzotriazolylphenol compounds in which they have attached to it via non-covalent binding another molecule (most likely a polar solvent) especially including hydrates and alcoholates, e.g. methanolate.
A further aspect of the present invention relates to a pharmaceutical composition comprising at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above, optionally in form of one of its stereoisomers, preferably enantiomers or diasteromers, a racemate or in form of a mixture of at least two stereoisomers, preferably enantiomers and/or diastereomers, in any mixing ratio, or a physiologically acceptable salt thereof, or a corresponding solvate thereof, and optionally at least one physiologically acceptable auxiliary agent.
A further aspect of the present invention relates to a cosmetic composition comprising at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above, optionally in form of one of its stereoisomers, preferably enantiomers or diasteromers, a racemate or in form of a mixture of at least two stereoisomers, preferably enantiomers and/or diastereomers, in any mixing ratio, or a physiologically acceptable salt thereof, or a corresponding solvate thereof, and optionally at least one physiologically acceptable auxiliary agent.
It has surprisingly found that the inventive silylated benzotriazolylphenol compounds of general formula (I) given above also show remarkable absorption capacities in UV- C radiation range. Since the sunlight radiation intensity continuously increases due to the continuous reduction of stratospheric ozone, the importance of pharmaceutical/cosmetic compositions having such UV-C protecting properties is growing.
Said pharmaceutical and/or cosmetic composition is particularly suitable for the prophylaxis and/or care and/or treatment of diseases caused by and/or associated with exposure to ultraviolet radiation, preferably of the lips, the face and/or of the body of mammals, preferably human beings, more preferably for the prophylaxis and/or care and/or treatment of/against non-desired skin conditions comprising polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis.
The amount of at least one silylated substituted benzotriazolylphenol compound for the inventive pharmaceutical or cosmetical composition is preferably in each case in the range of 0.01 % to 30% per weight, more preferably 0.01 % to 20% per weight, most preferably 0.1 % to 15% per weight, with respect to the total weight of the composition.
For the inventive pharmaceutical or cosmetical composition at least one of the inventive silylated substituted benzotriazolylphenol compound(s) may be preferably used in micronized form, wherein the size of the particles is preferably in the range of 0.01 to 4 μm, more preferably in the range of 0.05 to 2 μm, most preferably in the range of 0,05 to 1 μm.
The following auxiliary agents mentioned below can independently from each other be present in either the inventive pharmaceutical or the inventive cosmetical composition: gelling agents, oils, waxes, thickening agents, hydrophilic or hydrophobic polymers, emulsifying agents, emollients, fatty acids, organic solvents, antioxidants, stabilizers, sequestering agents, acidifying or basifying agents, emulsifiers, emollients, surfactants, film formers, biological additives to enhance performance and/or consumer appeal such as amino acids, proteins, vanilla, aloe extract or bioflavinoids, buffering agents, chelating agents such as ethylenediaminetetra-acetic acid (EDTA) or oxalic acid, colorants, dyes, propellants, antifoaming agents, wetting agents, vitamins, emulsion stabilizers, pH adjusters, thickening agents, fragrances, preservatives, opacifying agents, water and/or alcohols. The aforementioned auxiliary agents for the inventive compositions are used in the usual amounts known by those skilled in the art.
As oils for the inventive compositions oils from animal or vegetable sources or synthetic are preferably used. Particularly preferred are oils selected from the group comprising liquid petrolatum, liquid paraffin, volatile and non-volatile silicone oils, isoparaffins, polyalphaolefins, fluorated and perfluorated oils.
As stabilizers for the inventive compositions preferably non-ionic, anionic, cationic and amphiphilic tensides can be used, which are preferably selected from the group comprising polyethylenglycol (PEG) and derivatives thereof, tweens, tritons, spans, polygycerines, polyalkyl glycerides, alkyl sulfonates, aryl sulfonates, alkyl phosphates, derivatives of alkyl-betaine and phosphatidylglycerole.
Emulsifiers are preferably used in certain formulations of the inventive compositions in amounts effective to provide uniform blending of ingredients of the composition. Useful emulsifiers include anionics such as fatty acid soaps, e.g., potassium stearate, sodium stearate, ammonium stearate, and triethanolamine stearate; polyol fatty acid monoesters containing fatty acid soaps, e.g., glycerol monostearate containing either potassium or sodium salt; sulfuric esters (sodium salts), e.g., sodium lauryl 5 sulfate, and sodium acetyl sulfate; and polyol fatty acid monoesters containing sulfuric esters, e.g., glyceryl monostearate containing sodium lauryl surfate; (ii) cationics chloride such as N(stearoyl colamino formylmethyl) pyridium; N-soya-N-ethyl morpholinium ethosulfate; alkyl dimethyl benzyl ammonium chloride; diisobutylphenoxytheoxyethyl dimethyl benzyl ammonium chloride; and acetyl pyridium chloride; and (iii) nonionics such as polyoxyethylene fatty alcohol ethers, e.g., monostearate; polyoxyethylene lauryl alcohol; polyoxypropylene fatty alcohol ethers, e.g., propoxylated oleyl alcohol; polyoxyethylene fatty acid esters, e.g., polyoxyethylene stearate; polyoxyethylene sorbitan fatty acid esters, e.g., polyoxyethylene sorbitan monostearate; sorbitan fatty acid esters, e.g., sorbitan; polyoxyethylene glycol fatty acid esters, e.g., polyoxyethylene glycol monostearate; and polyol fatty acid esters, e.g., glyceryl monostearate and propylene glycol monostearate; and ethoxylated lanolin derivatives, e.g., ethoxylated lanolins, ethoxylated lanolin alcohols and/or ethoxylated cholesterol.
Emollients may be used in the formulations of the inventive compositions in such amounts to prevent or relieve dryness. Useful emollients include, without limitation hydrocarbon oils and waxes; silicone oils; triglyceride esters; acetoglyceride esters; ethoxylated glyceride; alkyl esters; alkenyl esters; fatty acids; fatty alcohols; fatty alcohol ethers; etheresters; lanolin and derivatives; polyhydric alcohols (polyols) and polyether derivatives; polyhydric alcohol (polyol) esters; wax esters; beeswax derivatives; vegetable waxes; phospholipids; sterols; and/or amides.
Surfactants can be used in certain formulations of the inventive compositions. Suitable surfactants are for example those surfactants generally grouped as cleansing agents, emulsifying agents, foam boosters, hydrotropes, solubilizing agents, suspending agents and non-surfactants, which facilitate the dispersion of solids in liquids.
Suitable film formers which are preferably used in the formulations of the inventive compositions should keep the composition smooth and even and are preferably, without limitation, at least one substance selected from the group comprising acrylamide/sodium acrylate copolymer; ammonium acrylates copolymer; Balsam Peru; cellulose gum; ethylene/maleic anhydride copolymer; hydroxyethylcellulose; hydroxypropylcellulose; polyacrylamide; polyethylene; polyvinyl alcohol; pvm/MA copolymer (vinyl methylether/maleic anhydride copolymer); PVP (polyvinylpyrrolidone); maleic anhydride polymer, vinylpyrrolidon/hexadecene copolymer; acryliclacrylate copolymer and the like.
pH adjusters may also be used in certain formulations of the inventive compositions. These pH adjusters preferably comprise, but are not limited to ammonium hydroxide, triethanolamine or citric acid. Thickening agents used for the formulations of the inventive compositions preferably are, but are not limited to candelilla, carnauba, and microcrystalline waxes, crosslinked acrylic-acid polymers, carbomer, methylhydroxyethylcellulose, hydroxypropylmethylcellulose or hydroxyethylcellulose. and polyethylene thickeners.
Examples of preferred organic solvents for the inventive compositions include lower aliphatic alcohols and polyols.
Suitable antioxidants suitable for the inventive compositions are preferably selected from the group comprising ascorbic acid (vitamin C), sodium-L-ascorbate, calcium-L- ascorbate, ascorbyl palmitate, butylhydroxyanisole, butylhydroxytoluene, calcium- disodium-EDTA, isoascorbic acid, lecitine, lactic acid, polyphosphate, tocopherol (vitamin E), like α-tocopherol, γ-tocopherol, δ-tocopherol, propylgallate, octylgallate, dodecylgallate, sodium-isoascorbate, citric acid, sodium citrate, potassium citrate and tin-ll-chloride.
Gelling agents, which are preferably used in the formulations of the inventive compositions, can be natural or synthetic polymers. Natural polymers are preferably selected from the group comprising Agar-Agar, alginate, pectin, carbomer, carrageenan, casein, dextrine, gelatine, arabic gum, keratine, locust bean gum, xanthan gum and the like. Preferred synthetic polymers, which can be used in the formulations of the inventive compositions are selected from the group comprising acylic acid polymers, polyacryl amides and alkylene oxide polymers.
For the inventive cosmetic composition marketed in Europe the respective components shall be used in amounts which are in compliance with the Council Directives 76/768/EEC and Commission Directive 95/17/EC on the approximation of the laws of the Member States relating to cosmetic products.
The inventive pharmaceutical or cosmetic composition is preferably adapted at least for a once a day, twice or three, four or five times a day, preferably for twice a day application. For the application, preferably topical application, the inventive pharmaceutical or cosmetical composition may be formulated in liquid or in semi-solid form, preferably as liquid, fluid, foam, cream, gel, paste, balsam, spray, ointment, lotion, conditioner, tonic, milk, mousse, emulsion, serum, oil, stick, shampoo, jelly, suspension, dispersion, lacquer, paint, elixir, drop or aerosol.
Preferably the inventive pharmaceutical or cosmetical compositions are suitable for protecting the skin of UV radiation, either in the range of UV-A or UV-B or UV-C or in the whole UV-A and UV-B range and optionally UV-C range.
A further aspect of the present invention relates to the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above for the preparation of a pharmaceutical composition for the prophylaxis and/or treatment of diseases caused by and/or associated with exposure to ultraviolet radiation, preferably of the lips, the face and/or of the body of mammals, preferably human beings.
Human exposure to solar ultraviolet radiation has important public health implications. Evidence of harm associated with overexposure to UV radiation has been demonstrated in many studies (see e.g. Environmental Burden of Disease Series, No. 13, 2006; Solar Ultraviolet Radiation - Global burden of disease from solar ultraviolet radiation, World Health Organization). Skin cancer and malignant melanoma are among the most severe health effects, but a series of other health effects, such as polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn, chronic actinic dermatitis or sunburn have been identified.
Thus, a preferred embodiment of the present invention is related to the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above for the preparation of a pharmaceutical composition for the prophylaxis and/or care and/or treatment against non-desired skin conditions comprising polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis. Also particularly preferred is the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above for the prophylaxis and/or care against non-desired skin conditions comprising polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis.
Also particularly preferred is the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above for protecting the skin preferably of the lips, the face and/or of the body of a mammal, preferably a human, against ultraviolet radiation, preferably UV-A and/or UV-B radiation and optionally UV-C radiation.
Yet, another aspect of the present invention relates to the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above as a light-stabilizer in polymer compositions, preferably in textile fibers.
Such polymer compositions comprising the inventive silylated substituted benzotriazolylphenol compounds of general formula (I) given above as light stabilizers may be in form of articles, moulds, sheets, foils, paintings, coatings, fibers or films. The films comprising the inventive silylated substituted benzotriazolylphenol compounds of general formula (I) given above as light stabilizers are single-layer or multilayer films, which can be used for medical or agricultural applications.
The articles, moulds, sheets, foils or films comprising the inventive silylated substituted benzotriazolylphenol compounds of general formula (I) given above as light stabilizers are preferably suitable for outdoor carpeting, awnings, tarps, umbrellas, non-food or food-packaging applications such as rice, corn and flour bags, tapes, ropes, artificial turf, stretch-films, shrink wraps, heavy-duty bags, pool covers, garden furniture, trash cans, bottle and fruit crates, toys, interior and exterior automotive parts such as auto bumpers and interior or exterior trim, outdoor sporting and leisure goods, roofings and window shutters.
The term "light stabilizer" (also referred to as "photostabilizer" or "photoprotecting agent") means, according to the present invention a chemical compound that protects the material like a polymer composition against photodegradation against deterioriating and/or decomposing effects caused by its exposure to light. With respect to the definition of "light stabilizer" reference is made to the International Union of Pure and Applied Chemistry (IUPAC) Definitions of terms relating to polymer chemistry, Pure and Appl. Chem., Vol. 68, No.12, pp. 2313-2323, 1996.
Preferably, light stabilizers can also be classified according to their special possibility of stabilizing against the impact of light into absorbers, quenchers, peroxide decomposers or free radical scavengers.
So called absorbers and quenchers are preferably agents that reduce the impact caused by exposure to light either by absorbing, extincting, filtering, scattering, deflecting or reflecting light. A peroxide decomposer is preferably an agent that transforms peroxides into stable compounds without the formation of free radicals and a free radical scavenger is preferably an agent that eliminates free radicals by binding.
Preferably, the inventive light-stabilized polymer composition comprises as the light- stabilizing component at least one absorber, quencher, peroxide decomposer and/or free radical scavenger.
The term "absorption" according to the present invention means any of the following means of reducing the exposure to UV radiation like absorbing, extincting, filtering, scattering, deflecting or reflecting of radiation, since absorption only means the ratio of transmitted radiation to the incident radiation, without determining the mechanism according to which the radiation is reduced.
Polymers can be preferably classified into four main groups:
1. Thermoplastic polymers
2. Thermosetting polymers/thermosets
3. Elastomers
4. Coordination polymers 1. Thermoplastic polymers
Plastics made of thermoplastic polymers is deformable, melts to a liquid when heated and freezes to a brittle, glassy state when cooled sufficiently. Most thermoplastic polymers are high molecular weight polymers whose chains associate through weak van der Waals forces (polyethylene), stronger dipole-dipole interactions and hydrogen bonding (nylon) or even stacking of aromatic rings (polystyrene). Thermoplastic polymers can be remelted and remolded.
2. Thermosetting polymers
Thermosetting polymers ("thermosets") are materials that cure, through the addition of energy, to a stronger form. The energy may be in the form of heat (generally above 200°C), through a chemical reaction (two-part epoxy, for example), or irradiation. Thermoset materials are usually liquid, powder, or malleable prior to curing, and designed to be moulded into their final form, or used as adhesives. The curing process transforms the resin into a plastic or rubber by a cross-linking process. Energy and/or catalysts are added that cause the molecular chains to react at chemically active sites (unsaturated or epoxy sites, for example), linking into a rigid, 3-D structure. The cross-linking process forms a molecule with a larger molecular weight, resulting in a material with a higher melting point. During the reaction, when the molecular weight has increased to a point so that the melting point is higher than the surrounding ambient temperature, the material forms into a solid material. Subsequent uncontrolled reheating of the material results in reaching the decomposition temperature before the melting point is obtained. A thermoset material cannot be melted and re-shaped after it is cured. Thermoset materials are generally stronger than thermoplastic materials due to this 3-D network of bonds and are also better suited to high-temperature applications up to the decomposition temperature of the material.
3. Elastomers
The term elastomer is often used interchangeably with the term rubber, and is preferred when referring to vulcanisates. They are amorphous polymers existing above their glass transition temperature, so that considerable segmental motion is possible. At ambient temperatures rubbers are thus relatively soft and deformable. Their primary uses are for seals, adhesives and molded flexible parts. 4. Coordination polymers
Coordination polymers are compounds where the metals are bridged by polyatomic ligands, such as e.g. cyanide or carboxylates.
A preferred embodiment of the present invention relates to the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above as a light-stabilizer in thermoplastic polymer compositions, whereby the thermoplastic polymer is preferably at least one thermoplastic polymer selected from the group comprising acrylonitrile-butadiene-styrene (ABS) copolymer; cellulose derivatives such as cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate, cellulose ether, methyl cellulose, ethylcellulose, propyl- cellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethyl- cellulose and carboxy methylcellulose; ethylene-vinyl acetate (EVA) copolymer; ethylene vinyl alcohol (EVAL) copolymer; polyolefines such as ethylen-propylen copolymer, ethylene-buten-1 copolymer, ethylene-hexene copolymer, ethylene- methylpentene copolymer, ethylene-heptene copolymer, ethylene octene copolymer, polybutylene (PB), polymethylpentene (PMP), polypropylene (PP) and polyethylene (PE) such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and metallocene-PE (mPE); ethylen- alkylacrylate copolymer such as ethylen-ethylacrylate copolymer; ethylene- alkylmethylacrylate copolymer; fluoro resins such as polytetrafluoroethylene (PTFE) or perfluoro (ethylene-propylene) copolymer (FEP); chloro-trifluoroethylene (CTFE), ethylene-chlorotrifluoroethylene (ECTFE); ethylene-tetrafluorethylene copolymer (ETFE) and tetrafluoroethylene-propylene copolymer; ionomer; liquid crystal polymer (LCP); polyacetal; polyacrylate; polymethacrylate; polyacrylonitrile; polyamide (PA); polyamide-imide; polyesters such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and polycyclohexylene dimethylene terephthalate (PCT); polycarbonate (PC); polyhydroxyalkanoate; polyketone (PK); polyetheretherketone (PEEK); polyetherimide (PEI); polyethersulfone (PES); polyimide (Pl); polylactic acid (PLA); polyphenylene oxide (PPO); polyphenylene sulfide (PPS); polyphthalamide (PPA); homo- or copolymers of styrene such as e.g. styrene-isopren-styrene block copolymer; polysulfone (PSU); polyurethane (PU); polyvinyl ether; polyvinylalcohol; polyvinylidenechloride; polyvinylpyrrolidone; polyvinyl chloride (PVC); vinyl chloride- vinyl acetate copolymer; vinyl chloride-vinylidene dichloride copolymer and vinyl pyrrolidon-ethylen-vinylacetate copolymer.
Another preferred embodiment of the present invention relates to the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above as a light-stabilizer in elastomer compositions, whereby the elastomer is preferably at least one elastomer selected from the group comprising homo-, co- or block polymer of butadiene; natural rubber (NR); polyisoprene (IR); butyl rubber; halogenated butyl rubbers such as chloro butyl rubber or bromo butyl rubber; polybutadiene (BR); styrene-butadiene rubber (SBR); nitrile rubber; hydrated nitrile rubbers (HNBR); chloroprene rubber (CR); polychloroprene; neoprene; ethylene propylene rubber (EPM); ethylene propylene diene rubber (EPDM); epichlorohydrin rubber (ECO); polyacrylic rubber; silicone rubber; silicone; silcone derivatives such as siloxane-methacrylate polymers; fluorosilicone rubber; fluoroelastomers; perfluoroelastomers (FFKM); tetrafluoro ethylene/propylene rubbers (FEPM); chlorosulfonated polyethylene (CSM); ethylene-vinyl acetate (EVA) copolymers; thermoplastic elastomers (TPE); polyurethane rubber and polysulfide rubber.
Another preferred embodiment of the present invention relates to the use of at least one silylated substituted benzotriazolylphenol compound of general formula (I) given above as a light-stabilizer in thermosetting polymer compositions, whereby the thermosetting polymer is preferably at least one polymer selected from the group comprising vulcanized rubber; polyoxybenzylmethylenglycolanhydride; duroplast; urea-formaldehyde resins; melamine; cured polyester resins and epoxy resins.
Polymer compositions usually comprise additives, which improve the properties of these compositions. Suitable additives used in the inventive light-stabilized composition preferably include, but are not limited to anti-blocking-agents, anti- fogging agents, antistatic agents, antioxidants, biocides, blowing agents, defoamers, dyes, emulsifiers, fillers, flame retardants, heat stabilizers, impact modifiers, lubricants, metal deactivators, hydrocalcites, mould-release agents, optical brighteners, plastisizers, processing agents, pigments, phosphites, phosphonites, reinforcing agents, rheology additives, slip agents and surfactants, whereby each of these aforementioned additives is used in usual amounts known by those skilled in the art.
The present invention is illustrated below with the aid of examples. These illustrations are given solely by way of example and do not limit the general spirit of the present invention.
EXAMPLES
Abbreviations:
H hour
0C °Celsius ml milliliter
Min minute
M molar (concentration) mol moles
N normal
HCI hydrogen chloride
NaNO2 sodium nitrite
NaOH sodium hydroxide
Mp melting point
RT room temperature
K2CO3 potassium carbonate
Kl potassium iodide
CH2CI2 dichloromethane
MgSO4 magnesium sulphate Example 1: Procedure for synthesis of 3-(2H-benzotriazol-2-yl)-5-[2-methyl-3- [1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]biphenyl-4-ol
Figure imgf000080_0001
techn. Xylene, Ar
Karstedt cat.
Figure imgf000080_0003
Figure imgf000080_0002
(Ex.1) 3-(2H-1 ,2,3-Benzotriazol-2-yl)biphenyl-4-ol (P6)
To a cold (0-5 0C) suspension of 6.9 g 2-nitroaniline (0.05 mol; P1) in 25 ml concentrated HCI, 50 g crashed ice and 50 ml water was added dropwise 10 ml of a 5N solution of NaNO2. The resulting mixture was stirred at 0 0C until it turned to a clear, yellow solution (P2). This solution was then added dropwise to a cold (<5 0C) solution of 8.51 g biphenyl-4-ol (0.05 mol; P3) in 45 ml 10% aqueous NaOH solution with stirring. The reaction mixture was stirred at 00C for 1 h and at RT the precipitated pale brown crystalline compound was collected by filtration (P4). The biphenyl-4-ol (P3) did not run out completely. Yield: 17 g (100%) Mp: 1000C. Rf = 0.58 (hexane-acetone 10:4).
The suspension of 10 g (P4) (0.031 mol) in 100 ml, 4N NaOH was refluxed in the presence of 7.5 g formamidinesulphinic acid (0,069 mol; P5) for 1 h. The brown- purple color changed into pale yellow. The resulting mixture was cooled to RT and then poured into a 200 ml mixture of ice and water. The mixture was acidified with concentrated HCI (pH = 6) and the precipitated crystals were collected by filtration (P6). Impurities were dissolved with hot methanol. P6: Yield: 5.3g (67%). Mp 152- 153°C. Rf = 0.85 (hexane-acetone 10:4).
P6:
1H -NMR (CDCl3): 7.26 (d, J= 8.5 Hz, IH, C5-H), 7.35 (t, J= 7.3, IH, Ci0-H), 7,46 (t, J= 7.3, 2H, C9-H and Cu-H), 7.49 (dd, J= 6.5 and 3.0 Hz, 2H, C5-H and C6-H), 7.59 (dd, J= 8.6 and 1.9 Hz, IH, C6-H), 7.66 (d, J= 7.5 Hz, 2H, C8-H and Ci2-H), 7.93 (dd, J= 6.5 and 3.0 Hz, 2H, C4-H and C7-H), 8.65 (d, J= 1.8 Hz, IH, C2-H), 11.37 (s, IH, OH).
13C-NMR (CDCl3): 117.71 (C-4' and C-7'), 119.42 (C-5), 119.48 (C-2), 125.44 (C-3), 126.79 (C-8 and C- 12), 127.24 (C-IO), 127.81 (C-51 and C-6'), 128.86 (C-9 and C-I l), 129.04 (C- 6), 133.48 (C-I), 139.72 (C-7), 142,87 (C-3a' and C-7a'), 149.17 (C-4).
2-{4-[(2-Methylprop-2-en-1-yl)oxybiphenyl-3-yl}-2H-1,2,3-benzotriazole (P8)
To a stirred mixture of 5 g of compound P6 (0.017 mol), 2.4 g K2CO3 (0.017 mol), and 5.8 g Kl (0.035 mol.) in 120 ml butan-2-one was added dropwise 3.7 ml 3-chloro-2- methylprop-1-ene (0.035 mol) and the resultant mixture was heated at reflux for 8 h. After cooling to RT, the reaction mixture was filtered and the solvent was evaporated in vacuo. The residue was purified by column chromatography (using toluene as eluent). Yield: 3.7 g (62%), Mp 94-95.5°C, Rf = 0.67 (hexane-acetone 10:4)
P8:
1H-NMR (CDCI3): 1.71 (s, 3H, CH3), 4.55 (s, 2H, CH2), 4.90 (s, IH, =C-H), 5.00 (s, IH, =C- H), 7.19 (d, J= 8,7 Hz, IH, C5-H), 7.33 (t, J= 7.5, IH, Ci0-H), 7.43 (m, 2H, C9-H and Cn- H, 7.45 (m, 2H, C5-H and C6-H), 7.60 (d, J= 8.5 Hz, 2H, C8-H and Ci2-H), 7.70 (dd, J= 8.7 and 2.3 Hz, IH, C6-H), 7.94 (d, J= 2.3 Hz, IH, C2-H), 7.98 (m, 2H, C4-H and C7-H).
13C-NMR (CDCl3): 19.17 (CH3), 72.78 (CH2), 112.90 (=C-H), 1 14.72 (C-51), 1 18.44 (C-4 and C-7), 126.12 (C-21), 127.37 (C- IO'), 126.82 (C-5, C-6, C-8 and C- 12'), 128.87 (C-9' and C- 10'), 129.28 (C-6'), 130.91 (C-31), 134.31 (C-I1), 139.33 (C-71), 139.87 (C=), 144.85 (C-3a and C-7a), 152.00 (C-4 ).
3-(2H-1 ,2,3-Benzotriazol-2-yl)-5-(2-methylprop-2-en-1 -yl)biphenyl-4-ol (P9)
A solution of compound P8 (3.7 g; 0.011 mol) in Λ/,Λ/-diethylaniline was heated at reflux for 3 h. After cooling to RT the reaction mixture was treated with 75 ml 15% aqueous HCI and extracted with CH2CI2 (three times, 100 ml each). The combined organic extracts were dried (MgSO4), solvent evaporated in vacuo, and the residue was recrystallized from hexane. Yield: 3.3g (86%), Mp 115.5-116,5°C, Rf = 0.88 (hexane-acetone 10:4).
P9:
1H-NMR (CDCl3): 1.84 (s, 3H, CI l3), 3.58 (s, 2H, CH2), 4.80 (s, IH, =C-H), 4.89 (s, IH, =C-H), 7.35 (t, J= 7,5 Hz, IH., Ci0-H), 7.46 (m, 3H, C6-H, C9-H and Cn- H ) , 7.49 (m, 2H, C5-H and C6-H, 7.67 (d, J= 8.5 Hz, 2H, C8-H and Ci2-H), 7.94 (m, 2H, C4-H and C7-H), 8.56 (d, J= 2,3 Hz, IH, C2-H), 11.67 (s, IH, OH).
13C-NMR (CDCl3): 22.57 (CH3), 38.07 (CH2), 111.92 (=C-H), 117.67 (C=), 117.75 (C-2), 125.39 (C-3), 126.83 (C-8 and C- 12), 127.14 (C- 10), 127.74 (C-5' and C-6 ), 128.81 (C-9 and C- 12), 129.91 (C-9' and C-10 ), 130.10 (C-5), 132,67 (C- I), 139.96 (C-7), 142.82 (C-3a' and C-7a'), 144.25 (C=), 147.52 (C-4). 3-(2H-benzotriazol-2-yl)-5-[2-methyl-3-[1,3,3J3-tetramethyl-1- [(trimethylsilyl)oxy]disiloxanyl]propyl]biphenyl-4-ol (Example compound 1)
Figure imgf000083_0001
To a mixture of compound P9 (3 g; 0.0088 mol) and 3.7 ml 1 ,1 ,1 ,3,5,5,5- heptamethyltrisiloxane (P10; 0.013 mol) in 50 ml xylene was added 10 drops of Karstedt's catalyst, and the resulting mixture was heated at 1000C for 9 h. After cooling to RT, the solvent was evaporated in vacuo and the residue was purified by column chromatography (using hexane as eluent). Yield: 4.7 g (95%). Rf = 0.91(hexane-acetone 10:4). λmax1 = 305 nm, εmaxi = 17573; λmaχ2 = 352 nm, εmaX2 = 11530.
1H NMR (CDCl3): 0.10 (s, 3H, CH3), 0.11 (s, 9H, 3CH3), 0.12 (s, 9H, 3CH3), 0.56 (dd, J= 14.8 and 9.2 Hz, IH, C3-H), 0.78 (dd, J= 14.8 and 4.7 Hz, IH, C3-H), 1.05 (d, J=6.6 Hz, 3H, CH3), 2.23 (m, IH, C2-H), 2.73 (dd, J= 13.2 and 8.2 Hz, IH, Cr-H), 2.89 (dd, J= 13.2 and 6,2 Hz, IH, Ci-H), 7.38 (t, J= 7.4 Hz, IH, C4-H), 7.49 (m, 3H, C5-H, C3 -H and Cs'-H), 7.52 (m, 2H, C5 -H and C6 -H), 7.71 (d, J= 7.5 Hz, 2H, C2-H and C6-H), 7.98 (m, 2H, C4-H and C7-H), 8.57 (d, J= 3.3 Hz, IH, C3-H), 11.60 (s, IH, OH).
13C NMR (CDCl3): 0.85 (CH3), 1.87 (CH3), 22.48 (CH3), 26.18 (C-3"'), 29.31 (C-2"'), 41.27 (C- I1"), 117.39 (C-3), 117.66 (C-41 and C-71), 125.34 (C-2), 126.83 (C-2" and C-6"), 127.03 (C-4"), 127.66 (C-5' and C-61), 128.77 (C-3" and C-5"), 130.56 (C-5), 132, 14 (C-6), 132.34 (C-4), 140.14 (C-I"), 142.81 (C-7a'), 147.66 (C-3a').
Determination of the UV-absorption profile of 3-(2H-benzotriazol-2-yl)-5-[2- methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]biphenyl- 4-ol (Example compound 1):
The UV-absorption spectrum of 3-(2H-benzotriazol-2-yl)-5-[2-methyl-3-[1 ,3,3,3- tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]biphenyl-4-ol (dissolved in CHCI3, concentration: 4 μg/ml) was tested using a Hewlett Packard 8452A Diode Array Spectrophotometer.
In the chart of figure 1 it can be seen that example compound 1 absorbs more than half of the amount of the radiation in the UV-C radiation range, when compared with Mexoryl XL® (compare: figure 2). Moreover it can be seen that example compound 1 absorbs more amounts of UV radiation at λmax values of approx. 300 nm (UV-B) and approx. 340 nm (UV-A), respectively in comparison to Mexoryl XL® (compare: figure 2).
Example 2: 3-(2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl- disiloxanyl)-propyl]-biphenyl-4-ol
Figure imgf000084_0001
λmaxi = 305 nm, εmaxi = 21083; λmaX2 = 352 nm, εmax2 = 13946. Melting point: 41-44°C.
Η NMR (CDCb): 0.10 (s, 9H, 3 CH3), 0.14 (s, 3H2, CH3), 0.15 (s, 3H, CH3), 0.63 (dd, J= 14.7 and 9.9 Hz, IH, C3" -H), 0.83 (dd, J= 14.7 and 4.8 Hz, IH, C3-H), 1.04 (d, J= 6.6 Hz, 3H, CH3), 2,24 (m, IH, C2-H), 2.70 (dd, J= 13.1 and 8.3 Hz, IH, Ci -H), 2,92 ((dd, J= 13.1 and 6.0 Hz, IH, Cr-H), 7.39 (t, J= 7.5 Hz, IH, C4-H), 7.49 (m, 3H, C5-H, C3-H and C5-H), 7.52 (m, 2H, C5-H and C6-H), 7.71 (d, J=7.5 Hz, 2H, C2- -H and C6-H), 7.98 (m, 2H, C4 -H and C7-H), 8.57 (d, J= 2.2 Hz, IH, C3-H), 11.61 (s, IH, OH).
"C NMR (CDCI3): 1.31 (CH3), 1.42 (CH3), 1.99 (3 CH3), 22.68 (CH3), 27.01 (C-31"), 29.54 (C- 2'"), 41.53 (C-I1"), 1 17.41 (C-3), 117.66 (C-4' and C-71), 125.34 (C-2), 126.83(C-2" and C-6"), 127.05(C-4"), 127.65 (C-5' and C-6'), 128.79 (C-3" and C-5"), 130.57 (C-5), 132.12 (C-6), 132.33 (C-4), 140.13 (C-I"), 142.81 (C-7a'), 147.65 (C-3a'). Example 3: Procedure for synthesis of 2-(2/-/-benzotriazol-2-yl)-4-cyclohexyl-6-[2- methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]-phenol
Figure imgf000085_0001
techn. Xylene, Ar
Karstedt cat.
Figure imgf000085_0003
Figure imgf000085_0002
(Ex.3) 3-(2H-1 ,2,3-Benzo[d]triazol-2-yl)cyclohexylphenol (Q6)
To a cold (0-5 0C) suspension of 10.36 g 2-nitroaniline (0.075 mol; Q1) in 37.5 ml concentrated HCI, 75 g crashed ice and 75 ml water was added dropwise 15 ml of a 5N solution of NaNU2. The resulting mixture was stirred at 0 0C until it turned into a clear, yellow solution (Q2). This solution was then added dropwise to a cold (<5 0C) solution of 8.81 g 4-cyclohexylphenol (0.05 mol; Q3) in 45 ml 10% aqueous NaOH solution with stirring. The reaction mixture was stirred at 00C for 1 h and at RT the precipitated pale brown crystalline compound was collected by filtration (Q4). Yield: 17.72 g (=100%) Mp: «105°C. Rf = 0.53 (hexane-acetone 10:4).
The suspension of Q4 (17 g, 0.052 mol) in 100 ml, 4N NaOH was refluxed in the presence of 12.37 g formamidinesulphinic acid (0,12 mol; Q5) for 1 h. The brown- purple color changed into pale yellow. The resulting mixture was cooled to RT and then poured into a 200 ml mixture of ice and water. The mixture was acidified with concentrated HCI (pH = 6) and the precipitated crystals were collected by filtration (Q6). Q6: Yield: 15 g (98%) Mp: 135-136.5°C. Rf = 0.8 (hexane-acetone 10:4).
Q6:
1H-NMR (CDCb): 1.29 (m, IH, C4-H), 1.43 (m, 2H, C3-H and C5-H), 1.47 (m, 2H, C2-H and C6-H), 1.76 (d, J= 12.5 Hz, IH, C4-H), 1.86 (d, J= 12.5 Hz, 2H, C3-H and C5-H), 1.94 (d, J= 12.5 Hz, 2H, C2-H and C6-H), 2.57 (m, I H, Ci-H), 7.12 (d, J= 8.5 Hz, IH, C6-H), 7.20 (dd, J= 8.5 and 0.9 Hz, IH, C5-H), 7.47 (dd, J= 6.5 and 2.9 Hz, 2H, C5-H and C6-H), 7.93 (dd, J= 6.5 and 2.9 Hz, 2H, C4-H and C7-H), 8.24 (d, J= 0.8 Hz, IH, C3-H), 11.13 (s, IH, OH).
13C-NMR (CDC13): 26.09 (C-4"), 26.88 (C-3" and C-5"), 34.58 (C-2" and C-6"), 43.74 (C- I"), 117.67 (C-4' and C-7'), 118.75 (C-6), 119.03 (C-3), 124.95 (C-2), 127.61 (C-5' and C-6'), 129.12 (C-5), 140.20 (C-4), 142.81 (C 3a and C-7a), 147.75 (C- I).
2-(2-(Methylallyloxy)-5-cyclohexylphenyl)-2H-benzo[d][1,2,3]triazole (Q8)
To a stirred mixture of compound Q6 (17.5 g, 0.06 mol), 8.3 g K2CO3 (0.06 mol), and 20 g Kl (1.16 mol.) in 260 ml butan-2-one was added dropwise 13 ml 3-chloro-2- methylprop-1-ene (0.12 mol) and the resultant mixture was heated at reflux for 9 h. After cooling to RT, the reaction mixture was filtered and the solvent was evaporated in vacuo. The residue was purified by column chromatography (using toluene as eluent). Yield: 12.5 g (60%), Rf = 0.7 (hexane-acetone 10:4)
2-(2H-Benzo[d][1,2,3]triazol-2-yl)-4-cyclohexyl-6(2-methylallyl)phenol (Q9)
A solution of compound Q8 (12 g; 0.035 mol) in Λ/,Λ/-diethylaniline (80 ml) was heated at reflux for 9 h. After cooling to RT the reaction mixture was treated with 100 ml 3% aqueous HCI. The brown precipitate was passed through a short column (using toluene as eluent). Yield: 11.3g (94%), Mp 125 - 126°C, Rf = 0.83 (hexane-acetone 10:4).
Q9:
1H-NMR (CDCl3): 1.29 (m, IH, C4-H), 1.40 (m, 2H, C3-H and C5-H), 1.47 (m, 2H, C2 -H and C6-H), 1,76 (d, J= 12.5 Hz, I H, C4-H), 1.81 (s, 3H, CH3), 1.87 (d, J= 12.5 Hz, 2H, C3- H and C5-H), 1.94 (d, J= 12.5 Hz, 2H, C2-H and C6-H), 2.55 (m, IH, Ci-H), 3.49 (CH2), 4.74 (s, IH, C=C-H), 4.86 (s, IH, C=C-H), 7.09 (d, J= 1.7 Hz, IH, C5-H), 7.46 (dd, J= 6.5 and 3.0 Hz, 2H, C5-H and C6-H), 7.92 (dd, J= 6.5 and 3.0 Hz, 2H, C4-H and C7-H), 8.13 (d, J= 1.9 Hz., IH, C3-H), 11.42 (s, IH, OH).
13C-NMR (CDCl3): 22.55 (CH3), 26.11 (C-4"), 26.90 (C-3" and C-5"), 34.60 (C-2" and C-6"), 43.78 (C-I"), 111.58 (=C), 117.19 (C-3), 117.61 (C-4' and C-7'), 124.88 (C-2), 127.53 (C-5' and C-6'), 129.26 (C-6), 130.24 (C-5), 139.39 (C-4), 142,75 (C-3a* and C-7a'), 144.56 (C=), 146,04 (C-I).
2-(2H-benzotriazol-2-yl)-4-cyclohexyl-6-[2-methyl-3-(1,1,3,3>3-pentamethyl- disiloxanyl)-propyl]-phenol (Example compound 3)
Figure imgf000087_0001
To a mixture of compound Q9 (5.5 g; 0.016 mol) and 4.83 ml pentamethyltrisiloxane (0.024 mol) in 100 ml xylene 10 drops of Karstedt's catalyst were added and the resulting mixture was heated at 1000C for 6 h. After cooling to RT the solvent was evaporated in vacuo and the residue was purified by column chromatography (using hexane as eluent). Yield: 4 g (50%). Rf = 0.87(hexane-acetone 10:0.4). λmaxi = 306 nm, εmaxi = 16180; λmaX2 = 345 nm, εmaX2 = 14924.
1H-NMR (CDCI3): 0.09 (s, 9H, 3 CH3), 0.13 (s, 6H, 2 CH3), 0.59 (dd, J = 14.8 and 8.9 Hz, IH, C3 -H), 0.79 (dd, J= 14,8 and 4.8 Hz, IH, C3 -H), 1.01 (d, J= 6.6 Hz, 3H, CH3), 1.33 (m, IH, C4-H), 1.44 (m, 2H, C3-H and C5'-H), 1.52 (m, 2H, C2-H and C6-H), 1.80 (m-d, J= 12.9 Hz, IH, C4-H), 1.90 (m-d, J= 12.5 Hz, 2H, C3-H and C5-H), 1.97 (m-d, ,J= 12.6 Hz, 2H, C2- H and C6-H), 2.16 (m, IH, C2 -H), 2.58 (m, IH, Cr-H), 2.60 (dd, J= 13.0 and 8.3 Hz, IH, Cr-H), 2.83 (dd, J= 13.0 and 6.5 Hz, IH, Cf-H), 7.07 (d, J= 1.6 Hz, IH, C5-H), 7.49 (dd, J = 6.5 and 3.0 Hz, 2H, C5-H and C6-H), 7.96 (dd, J= 6.5 and 3.0 Hz, 2H, C4-H. and C7-H), 8.13 (d, J= 1.6 Hz, IH, C3-H), 11.34 (s, IH, OH).
"C-NMR (CDCl3): 1.32 (CH3), 1.39 (C:H3), 1.99 (3 CH3), 22.70 (CH3), 26.12 (C-4"), 26.90 (C-3" and C-5"), 29.48 (C-2"'), 34.58 (C-2"), 34.62 (C-6"), 41.44 (C-I "'), 43.77 (C-I"), 116.78 (C-3), 117.59 (C-4' and C-7'), 124.79 (C-2), 127.42 (C-5' and C-6'), 130.80 (C-5), 131.31 (C- 6), 138.97 (C-4), 142.73(C-3a' and C-7a'), 146.11 (Cl).
Example 4: Procedure for synthesis of 2-(2/-/-benzotriazol-2-yl)-4-cyclohexyl-6-[2- methyl-S-ti .S.S.S-tetramethyl-i-^trimethylsilyOoxyJdisiloxany^propylj-phenol
Figure imgf000088_0001
For obtaining 2-(2H-benzotriazol-2-yl)-4-cyclohexyl-6-[2-methyl-3-[1 ,3,3,3- tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-phenol the essentially the same synthesis steps as for Example compound 3 described above were employed. To a mixture of 5.5 g compound Q9 (0.016 mol) and 1 ,1 ,1 ,3,5,5,5- heptamethyltrisiloxane (6.7 ml, 0.024 mol) in 100 ml xylene 10 drops of Karstedt's catalyst were added and the resulting mixture was heated at 1000C for 4 h. After cooling to RT the solvent was evaporated in vacuo and the residue was purified by column chromatography (using hexane as eluent). Yield: 5 g (55%). Rf = 0.87 (hexane-acetone 10:0.4). λmaxi = 306 nm, εmaxi = 14872; Kmax2 = 344 nm, εmaχ2 = 13727.
iH-NMR (CDCl3): 0.08 (s, 311, CH3), 0.11 (s, 18H, 6 CH3), 0.51 (dd, J= 14.8 and 9.3 Hz, IH, C3-H), 0.74 (dd, J= 1.4.8 and 9.3 Hz, IH, C3-H), 1.02 (d, J= 6.6 Hz, 3H, CH3), 1.33 (m, IH, C4), 1.44 (m, 2H, C3-H and C5-H), 1.52 (m, 2H, C2-H and C6-H), 1.80 (m-d, J= 12.5 Hz, IH, C4-H), 1.90 (m-d, J= 12.5 Hz, 2H, C3-H and C5-H), 1.97 (m-d, J= 12.5 Hz, 2H, C2- H and C6-H), 2.16 (m, IH C2-H), 2.58 (m, IH, Cr-H), 2.65 (dd, J= 13.1 and 7.9 Hz, IH, Cr-H), 2.78 (dd, J= 13.1 and 6.3 Hz, IH, Ci-H), 7.07 (d, J= 1.6 Hz, IH, C5-H), 7.49 (dd, J= 6.6 and 3.0 Hz, 2H, C5-H and C6-H), 7.96 (dd, J= 6,6 and 3.0 Hz, 2H, C4-H and C7-H), 8.13 (d, J= 1.6 Hz, IH, C3-H), 11.34 (s, IH, OH).
13C-NMR (CDCl3): 0.82 (CH3), 1.86 (6 CH3), 22.51 (CH3), 26.04 (C-3m), 26.12 (C-4"), 26.90 (C-3" and C-5"), 29.26 (C-2'"), 34.62 (C-2" and C-6"), 41.22 (C-I"), 43.78 (C-I"), 116.78 (C-3), 117.60 (C-4' and C-71), 124.79 (C-2), 127.41 (C-5' and C-6'), 130.77 (C-5), 131.34 (C-6), 138.96 (C-4), 142.72 (C-3a' and C-7a'), 146.15 (C-I).
Example 5: 3-(5-Chloro-2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl- disiloxanyl)-propyl]-biphenyl-4-ol
Figure imgf000089_0001
Example 6: 3-(5-Methoxy-2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 ,1 ,3,3,3- pentamethyl-disiloxanyl)-propyl]-biphenyl-4-ol
Figure imgf000090_0001
Example 7: 2-{4-Hydroxy-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]- biphenyl-3-yl}-2/-/-benzotriazole-5-carbonitrile
Figure imgf000090_0002
Example 8: 2-{4-Hydroxy-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]- biphenyl-3-yl}-2/-/-benzotriazole-5-carboxylic acid
Figure imgf000090_0003
Example 9:
A cream formulation with the composition: % by weight
A) 3-(2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 ,1 ,3,3,3- pentamethyl-disiloxanyl)-propyl]-biphenyl-4-ol [λmaxi = 305 nm, λmaX2 = 352 nm] 5%
Figure imgf000091_0001
B) stearyl alcohol (Nacol 18-98 (Sasol)) 1.2%
C) PEG-40 stearate (Simulsol M52 (Seppic)) 2.5%
D) cetearyl ethylhexanoate (DUB Liquide 85) 2.5%
E) caprylic/capryc triglyceride (Miglyol 812N (Sasol) 3.0%
F) CM2-I5 alkyl benzoate (Tegosoft TN (Goldschmidt)) 5.0%
G) phenoxyethanol (and) methylparaben (and) ethylparaben (and) propylparaben (and) isobutylparaben (and) butylparaben (Phenonip (Clariant)) 0.6%
H) polyacrylamide (and) Ci3-14 isoparaffin (and) Laureth-7 (Sepigel 305 (Seppic)) 2%
I) cellulose gum (Blanose Cellulose Gum 7H3SF (Hercules)) 0.25% J) water ad 100%
is prepared.
In example 9 given above the % by weight of the respective components are based on the total weight of the composition.
The inventive formulations according to the examples are prepared by standard techniques known by those skilled in the art. Example 10:
A polymer composition comprising 3-(5-Methoxy-2H-benzotriazol-2-yl)-5-[2- methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]-biphenyl-4-ol (example compound 6) as light stabilizer.
Abbreviations:
MFI melt flow index
PP polypropylene
Ex.2 3-(2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl- disiloxanyl)-propyl]-biphenyl-4-ol (melting point: 41-44°C)
A master batch of polypropylene (MFI=OJ g/10 min at 2300C and 2.16 kg) and 2% by weight of Ex.2, related to the total weight of the masterbatch, are prepared by dry blending the polypropylene granulate with the aforementioned components and the mixture is further processed under melting in a Brabender kneader at 2000C during 10 minutes and at a rotation speed of 75 rounds/min and under a nitrogen atmosphere.
The master batch is mixed in such an amount with polypropylene (MFI=O.7 g/10 min at 2300C and 2.16 kg) to achieve a light-stabilized PP composition containing 0.15% by weight, based on the total weight of the composition, of the light-stabilizing component and with 0 1 % by weight calcium stearate and 0.05% by weight of a phenolic antioxidant (Irganox 1010) in an extruder equipped with a double screw. The composition is extruded through a flat nozzle to obtain a film with a thickness adjusted to the requirements of the accelerated weathering test according to ASTM D-5208. The film is then exposed to such weathering test. The light stability of the sample is assessed by measuring the extent of carbonyl oxidation of the polymer by means of infrared spectroscopy. The measurement is carried out after 1000 hours exposition to accelerated weathering (UV-A). Example 11 :
5,5'-(3,3<-(dimethylsilanediyl)bis(propane-3,1-diyl))bis(3-(2H -benzo[d][1,2,3]triazol-2-yl)biphenyl-4-ol)
Figure imgf000093_0001
= 400nm
Comparative Example 1
The UV-absorption spectrum of (2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3- [1 ,3)3>3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-phenol) Mexoryl XL® (dissolved in CHCb, concentration: 4 μg/ml) was tested using a Hewlett Packard 8452A Diode Array Spectrophotometer.
In the chart of figure 2 it can be seen that Mexoryl XL® absorbs less than half of the amount of the radiation in the UV-C radiation range, when compared with the inventive example compound 1 (compare: figure 1 ). Moreover it can be seen that Mexoryl XL® absorbs less amounts of UV radiation at λmax values of approx. 300 nm (UV-B) and approx. 340 nm (UV-A), respectively in comparison to example compound 1 (compare: figure 1 ).

Claims

Claims:
1. At least one silylated substituted benzotriazolylphenol compound of general formula (I)
Figure imgf000094_0001
(I)
wherein
k= 0 or 1 ; q = 1 or 2;
R1 and R2, independent from one another, each represents a hydrogen atom; a halogen atom; -NO2; -OR8; -SR9; -CN; -NR10R11; -C(=O)-OR12; -C(=O)R13; -C(=O)-NR14R15; -OC(=O)R16; -NR17-C(=O)R18; -NR19-C(=O)-O-R20; -S(=O)2-R21; -S(=O)2-O-R22; -S(=O)2-NR23R24;
a linear or branched, saturated, unsubstituted or at least mono-substituted CM8 aliphatic radical;
an unsubstituted or at least mono-substituted aryl radical, which may be bonded via a linear or branched, unsubstituted or at least mono-substituted alkylene group and/or which may be condensed with an unsubstituted or at least mono- substituted, saturated or aromatic mono- or bicyclic ring system;
or
R1 and R2 are fused to form together an additional aromatic mono- or polycyclic ring system having from 4 to 10 carbon atoms;
R3 represents an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical, which may be condensed with an unsubstituted or at least mono-substituted saturated or aromatic mono- or bicyclic ring system;
or
an unsubstituted or at least mono-substituted aryl or heteroaryl radical, which may be condensed with an unsubstituted or at least mono-substituted, saturated or aromatic mono- or bicyclic ring system;
R4 represents a hydrogen atom; a linear or branched, saturated, unsubstituted or at least mono-substituted C-i-iβ aliphatic radical;
with the provision that if q = 1 , then
k = 1 ;
R5 and R6 and R7, independent from one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted Ci-Ie aliphatic radical; a linear or branched, saturated, unsubstituted or at least mono-substituted -O-C-ι-18 aliphatic radical;
an unsubstituted or at least mono-substituted, saturated cycloaliphatic radical; an unsubstituted or at least mono-substituted aryl radical, which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
or
R5, R6 and R7, independent from one another, each represents a radical of general formula (II)
Figure imgf000096_0001
(") wherein
P = O, 1 , 2 or 3;
R25, R26, R27, R28 and R29, independent from one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted CM8 aliphatic radical; a linear or branched, saturated, unsubstituted or at least mono-substituted -0-C1-I8 aliphatic radical; an unsubstituted or at least mono-substituted aryl radical; or an -O-Si(R30)3 radical, with R30 representing a linear or branched, unsubstituted or at least mono-substituted CMS alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-C-|.i8 alkyl radical or an unsubstituted or at least mono-substituted aryl radical;
with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
or, with the provision that if q = 2, then k = 0;
R7 represents a radical of general formula (III)
Figure imgf000097_0001
(III)
wherein
m = 0, 1 , 2, 3, 4 or 5;
X represents an oxygen atom or an unsubstituted or at least mono-substituted
Ci-6 alkylene radical;
R31, R32, R33 and R34, independent of one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted C-M8 aliphatic radical; a linear or branched, saturated, unsubstituted or at least mono-substituted -O-C-1-18 aliphatic radical;
an unsubstituted or at least mono-substituted, saturated cycloaliphatic radical;
an unsubstituted or at least mono-substituted aryl radical, which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
or an -O-Si(R30)3 radical, with R30 representing a linear or branched, unsubstituted or at least mono-substituted CMS alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -0-C1-I8 alkyl radical or an unsubstituted or at least mono-substituted aryl radical; R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R23 and R24, independent of one another, each represents a hydrogen atom; a linear or branched, saturated, unsubstituted or at least mono-substituted Ci--I8 aliphatic radical, an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical or an unsubstituted or at least mono-substituted aryl radical;
R20 and R21, independent of one another, each represents a linear or branched, saturated, unsubstituted or at least mono-substituted Ci--I8 aliphatic radical, an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical or an unsubstituted or at least mono-substituted aryl radical;
and
R22 independent of one another, each represents a hydrogen atom; or an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing cycloaliphatic radical or an unsubstituted or at least mono-substituted aryl radical;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, preferably enantiomers or diastereomers, in any mixture ratio, or a salt, preferably a corresponding, physiologically acceptable salt, or a corresponding solvate.
2. At least one silylated substituted benzotriazolylphenol compound according to anyone of claim 1 , characterized in that
R1 and R2, independent from one another, each represents a hydrogen atom; a halogen atom; -NO2; -OR8; -SR9; -CN; -NR10R11; -COOR12; -COR13; -CONR14R15; -OCOR16; -NR17-COR18; -NR19-COO-R20; -SO2-R21; -SO2-O-R22; -SO2-NR23R24;
a linear or branched, unsubstituted or at least mono-substituted CMS alkyl radical;
an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono- , bi- or tricyclic aryl radical, which may be bonded via a linear or branched, unsubstituted or at least mono-substituted C1^ alkylene group and/or which may be condensed with an unsubstituted or at least mono-substituted, saturated or aromatic mono- or bicyclic ring system; or
R1 and R2 are fused to form together an additional aromatic mono- or polycyclic ring system having from 4 to 10 carbon atoms;
R3 represents an unsubstituted or at least mono-substituted, saturated, optionally at least one heteroatom as ring member containing C3-g (hetero)cycloalkyl radical, which may be condensed with an unsubstituted or at least mono-substituted saturated or aromatic mono- or bicyclic ring system;
or
an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono- , bi- or tricyclic aryl or a 5-, 6-, 8-, 9-, 10-, 11 -, 12-, 13- or 14-membered mono-, bi- or tricyclic heteroaryl radical, which may be condensed with an unsubstituted or at least mono-substituted saturated or aromatic mono- or bicyclic ring system;
R4 represents a hydrogen atom; a linear or branched, unsubstituted or at least mono-substituted Ci-6 alkyl radical;
with the provision that if q = 1, then k = 1 ;
R5, R6 and R7, independent from one another, each represents a linear or branched, unsubstituted or at least mono-substituted Ci-β alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-Ci-6 alkyl radical;
an unsubstituted or at least mono-substituted C-3-g cycloalkyl radical;
an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono- , bi- or tricyclic aryl radical which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
or
R5, R6 and R7, independent from one another, each represents a radical of general formula (II)
Figure imgf000100_0001
(H) wherein
P = O, 1 , 2 or 3;
R25, R26, R27, R28 and R29, independent from one another, each represents a linear or branched, unsubstituted Ci-6 alkyl radical; a linear or branched, unsubstituted -0-Ci-6 alkyl radical; an unsubstituted or at least mono- substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl radical; or an -O-Si(R30)3 radical, with R30 representing a linear or branched, unsubstituted or at least mono-substituted C1-6 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-C-i-β alkyl radical; an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono-, bi- or tricyclic aryl radical;
with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
or, with the provision that if q = 2, then
k = 0;
R7 represents a radical of general formula (III)
Figure imgf000101_0001
(III) wherein
m = 0, 1 , 2, 3, 4 or 5;
X represents an oxygen atom or an unsubstituted or at least mono- substituted C-I-4 alkylene radical;
R31, R32, R33 and R34, independent of one another, each represents a linear or branched, unsubstituted or at least mono-substituted Ci-6 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -0-Ci-6 alkyl radical; an unsubstituted or at least mono-substituted 03.9 cycloalkyl radical;
an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono- , bi- or tricyclic aryl radical which may be condensed with an unsubstituted or at least mono-substituted aromatic mono- or bicyclic ring system;
or an -O-Si(R30)3 radical, with R30 representing a linear or branched, unsubstituted or at least mono-substituted Ci-6 alkyl radical; a linear or branched, unsubstituted or at least mono-substituted -O-d-β alkyl radical or an unsubstituted or at least mono-substituted 6-, 10- or 14-membered mono- , bi- or tricyclic aryl radical;
R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23 and R24, independent of one another, have the above-defined meaning;
whereby
the aforementioned CMS alkyl radicals are in each case unsubstituted or substituted with 1 , 2, 3, 4, 5, 6, 7, 8 or 9 substituent(s) independently selected from the group consisting of oxo (=O), F, Cl, Br, I1 -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-Ci-8-alkyl, -O-Si-(C1-8-alkyl)3, -Si-(C1- 8-alkyl)3, -Si-(phenyl)3, -S-C1-8-alkyl, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(Ci-8-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain of the aforementioned Ci-i8-alkyl and/or Ci-8-alkyl radicals is linear or branched;
the aforementioned Ci-6 alkyl radicals are in each case unsubstituted or substituted with 1 , 2, 3, 4 or 5, substituent(s) independently selected from the group consisting of oxo (=O), F, Cl, Br, I1 -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-Ci-6-alkyl, -O-Si-(Ci-6-alkyl)3 ,-S-Ci-6-alkyl, -Si-(Ci-6-alkyl)3, -Si-(phenyl)3, -NH(d-6-alkyl), -N(C1-6-alkyl)2, -N(C1-6-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain of the aforementioned C-ι-6-alkyl radicals is linear or branched; the aforementioned -O-C-ι-6 alkyl radicals are in each case unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=0), F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -O-d-β-alkyl, -O-Si-(C1-6-alkyl)3, -S-C1-6-alkyl, -Si-(Ci-6-alkyl)3, -Si-(phenyl)3, -NH(C1-6-alkyl), -N(C1-6-alkyl)2, -N(C1.6-alkyl)3 +, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence the alkyl chain of the aforementioned d-β-alkyl radicals is linear or branched;
the aforementioned C3-g (hetero)cycloalkyl radicals are in each case unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=0), Ci-8-alkyl, -O-C1-8-alkyl, -S-Ci-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-C1.8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(Ci-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1-8-alkyl), -C(=O)-N(Ci-8-alkyl)2, -S(=O)2-C1-8-alkyl, -S(=O)2-phenyl, phenyl, phenethyl, phenoxy and benzyl, whereby in each occurrence Ci-8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and - NO2;
the aforementioned C3.g heterocycloalkyl radicals contain in each case optionally 1 , 2 or 3 additional heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen as ring member(s);
the aforementioned C3-9cycloalkyl radicals contain in each case optionally 1 , 2 or 3 heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen as ring member(s);
the aforementioned C1-4 alkylene, preferably -(CH2)-, -(CH2)2-, -(CH2)3- and -(CH2)4- groups are in each case linear or branched, unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of F, Cl, Br, I1 -CN, -CF3, -OCF3, -SCF3, -OH, -SH, -NH2, -O-C1-6-alkyl, -S-Ci-6-alkyl, -NH(Ci.6-alkyl) and -N(C1-6-alkyl)2;
the aforementioned Ci-6 alkylene, preferably -(CH2)-, -(CH2J2-, -(CH2)3-, -(CH2)4- , -(CH2)5- and -(CH2)6- groups are in each case unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -OH, -SH, -NH2, -O-Ci-6-alkyl, -S-Ci-6-alkyl, -NH(Ci-β-alkyl) and -N(d-6-alkyl)2;
the rings of the aforementioned ring systems are in each case independently of each other 5-, 6-, 7-, 8-, 9,- or 10-membered and may in each case independently of one another optionally contain 1 , 2, 3 or 4 heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen;
and the rings of the aforementioned mono-, bi- or polycyclic ring systems are in each case unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=O), C1-8-alkyl, -0-Ci-β-alkyl, -S-C1-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-Ci-8-alkyl, -O-C(=O)-C1-5-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(C1-8-alkyl), -N(C1-8-alkyl)2, -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(Ci-8-alkyl), -C(=O)-N(C1-8-alkyl)2, -S(=O)2-Ci-8-alkyl, -S(=O)2-phenyl, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence Ci-8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F, Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2;
the 6-, 10- or 14-membered, mono-, bi- or tricyclic aryl or 5-, 6-, 8-, 9-, 10-, 11-, 12-, 13- or 14-membered mono-, bi- or tricyclic heteroaryl radicals are unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of oxo (=O), Ci-8-alkyl, -O-C-i-8-alkyl, -S-Ci-8-alkyl, -C(=O)-OH, -C(=O)-C1-8-alkyl, -C(=O)-O-C1-8-alkyl, -O-C(=O)-C1-8-alkyl, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH(Ci-β-alkyl), -N(C1-8-alkyl)2l -N(C1-8-alkyl)3 +, -NO2, -CHO, -CF2H, -CFH2, -C(=O)-NH2, -C(=O)-NH(C1.8-alkyl), -C(=O)-N(Ci-8-alkyl)2, -S(=O)2-C1-8-alkyl, -S(=O)2-phenyl, phenyl, benzyl, phenethyl and phenoxy; whereby in each occurrence Ci-8-alkyl is linear or branched and whereby the cyclic part(s) of said substituent(s) is unsubstituted or substituted with 1 , 2 or 3 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, F1 Cl, Br, I -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2 and -NO2;
and the aforementioned 5-, 6-, 8-, 9-, 10-, 11-, 12-, 13- or 14-membered mono-, bi- or tricyclic heteroaryl radicals in each case contain 1 , 2, 3 or 4 heteroatom(s) independently selected from the group consisting of nitrogen, sulphur and oxygen as ring member(s);
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
3. At least one silylated substituted benzotriazolylphenol compound according to claim 1 or 2, characterized in that
q = 1 ; k= 1 ;
and
^ P, D1 D2 C?3 D4 D5 D6 D7 D8 D9 D10 , DIA11 , f DA12 , DΪA13 , DIA14 , C IA?15 , F DA16 , DIA17 , DIA18 , CIA?19 ,
R20, R21, R22, R23, R24, R25, R26, R27, R28, R29 and R30 have the meaning according to claim 1 ;
with the condition that at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above; optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
4. At least one silylated substituted benzotriazolylphenol compound according to claim 1 or 2, characterized in that
q = 2; k = 0;
and
„ m,, ~ p, Λ Y, D r\1 , Dr\2, DrΛ4, Drx8, Dr\11 , Drs12 , DIΛ13 , Dl"\14 , DΓ\15
Figure imgf000106_0001
, DΓ\16 , Dr\17 ,
R18, R19, R20, R21, R22, R23, R24, R30, R31, R32, R33 and R34 have the meaning according to claim 1.
5. At least one silylated substituted benzotriazolylphenol compound according to claim 1 or 2, characterized in that
q = 2; k = 0; m = 0;
and
n Y D1 D2 O3 C?4 D5 D6 D7 D8 D9 D10 D11 R12 P13 D14 D15 R16 D17 D18
R19, R20, R21, R22, R23, R24, R30, R31, R32, R33 and R34 have the meaning according to claim 1.
6. At least one silylated substituted benzotriazolylphenol compound according to claim 1 or 2, characterized in that
q = 2; k = 0; m = 1;
and
^ V D1 D2 D3 D4 D5 D6 D7 D8 D9 O10 nil D12 D13 D"I4 D15 D"I6 D-I? D18 P, Λ, IΛ , IΛ , ΓΛ , ΓΛ , IΛ , Γ\ , Γ\ , IΛ , Γ\ , Γ\ , IΛ , r\ , r\ , r\ , r\ , r\ , r\ , r\ ,
R19, R20, R21, R22, R23, R24, R30, R31, R32, R33 and R34 have the meaning according to claim 1.
7. At least one silylated substituted benzotriazolylphenol compound according to claim 1 or 2, characterized in that
q = 2; k = 0; m = 2;
and
„ v D-I D2 D3 D4 D5 D6 D7 D8 O9 D10 D11 D12 O13 D14 D1S D16 C317 D18 P, Λ, fΛ j iΛ j rΛ j lΛ j lΛ j rΛ j rΛ j rΛ j rΛ j rΛ , r\ ,
R19, R20, R21, R22, R23, R24, R30, R31, R32, R33 and R34 have the meaning according to claim 1.
8. At least one silylated substituted benzotriazolylphenol compound according to claim 1 or 2, characterized in that
q = 2; k = 0; m = 3;
and
r. V D-I D2 D3 D4 D5 D6 D7 Dδ D9 D10 D11 D12 D13 D14 D15 D16 D17 D18 P, Λ, IΛ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , r\ , Γ\ , Γ\ , Γ\ , Γ\ , ΪΛ , IΛ , ΓΛ , Γ\ , Γ\ , ΪΛ , ΪΛ ,
R19, R20, R21, R22, R23, R24, R30, R31, R32, R33 and R34 have the meaning according to claim 1. optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
9. At least one silylated substituted benzotriazolylphenol compound according to one or more of claims 1 to 8, characterized in that
q = 1 or 2; k = 0 or 1 ;
R1 and R2, independent from one another, each represents a hydrogen atom; F; Cl; Br; I; -NO2; -NH2; -SH; -OH; -CN; -C(=O)-OH; -C(=O)-OCH3> -C(=O)-OCH2CH3, -C(=O)-NH2; -S(=O)2-OH; -S(=O)2-NH2; -S(=O)2-Phenyl;
a radical selected from the group consisting of -O-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -0-CH3, -0-C2H5, -S-CH3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3, -Si-[CH(-CH3)2]3, -Si-(CH3)3, -Si-(CH2-CH3)3, -Si-[CH(-CH3)2]3, -NH-CH3 and -N(-CH3)2; and whereby in each occurrence the alkyl chain of these radicals is linear or branched; or
a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted or substituted with 1 , 2, 3, 4, or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -0-CH3, -0-C2H5, -S-CH3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3, -O-Si-[CH(-CH3)2]3, -Si-[CH(-CH3)2]3, -Si-(CH3)3, -Si-(CH2-CH3)3, -Si-[CH(-CH3)2]3, -NH-CH3 and -N(-CH3)2; whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
R3 represents a (hetero)cycloaliphatic radical selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, pyrrolidinyl, piperidinyl, piperazinyl, homopiperazinyl, morpholinyl, azetidinyl, tetrahydrofuranyl, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec- butyl, isobutyl, n-pentyl, -O-CH3l -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3)2, -S-C(CH3)3, -C(=O)-OH, -C(=O)-CH3> -C(=O)-C2H5, -C(=O)-CH2-CH2-CH3, -C(=O)-CH(CH3)2, -C(=O)-C(CH3)3, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -S(=O)2-Phenyl, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH-CH3, phenyl, phenethyl, phenoxy and benzyl;
or
an aryl or heteroaryl radical selected from the group consisting of phenyl, naphthyl, pyridinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, benzotriazolyl, quinolyl and isoquinolyl, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, n- pentyl, -O-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3)2, -S-C(CH3)3, -C(=O)-OH, -C(=O)-CH3, -C(=O)-C2H5, -C(=O)-CH2-CH2-CH3, -C(=O)-CH(CH3)2, -C(=O)-C(CH3)3, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -S(=O)2-Phenyl, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH-CH3, phenyl, phenethyl, phenoxy and benzyl;
R4 represents a hydrogen atom; or a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
with the provision that if q = 1, then
k = 1 ;
R5, R6 and R7, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted or substituted with 1 , 2, 3, 4, or 5 substituents independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na1 -SO3K, -SO3H, -0-CH3, -0-C2H5, -S-CH3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3, -O-Si-[CH(-CH3)2]3, -Si-[CH(-CH3)2]3, -Si-(CH3)3, -Si-(CH2-CH3)3, -Si-[CH(-CH3)2]3, -NH-CH3, -N(-CH3)2 and phenyl; whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
a radical selected from the group consisting of -0-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of F, Cl, Br, I, -OH, -SH, -NH2, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H1 -0-CH3, -0-C2H5, -S-CH3, -O-Si-(CH3)3, -O-Si-(CH2-CH3)3, -O-Si-[CH(-CH3)2]3) -Si-[CH(-CH3)2]3> -Si-(CH3J3, -Si-(CH2-CH3)3, -Si-[CH(-CH3)2]3, -NH-CH3 and -N(-CH3)2; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a phenyl or naphthyl radical, which is unsubstituted or substituted with 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, n- pentyl, -0-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3)2, -S-C(CH3)3, -C(=O)-OH, -C(=O)-CH3, -C(=O)-C2H5l -Cf=O)-CH2-CH2-CH3, -C(=O)-CH(CH3)2, -C(=O)-C(CH3)3, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH-CH3, phenyl, phenethyl, phenoxy and benzyl;
or
R5, R6 and R7, independent from one another, each represents a radical of general formula (II)
Figure imgf000111_0001
wherein
P = O, 1 or 2;
R25, R26, R27, R28 and R29, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopro- pyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
a radical selected from the group consisting Of -CH2-Ph and -CH2- CH2-Ph;
a radical selected from the group consisting Of -O-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain of these radicals is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched; an unsubstituted phenyl or naphthyl radical;
or
an -O-Si(R30)3 radical, with R30 representing a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and hexyl, which is unsubstituted;
with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
or, with the provision that if q = 2, then
k = 0;
R7 represents a radical of general formula (III)
Figure imgf000112_0001
(III) wherein
m = 0, 1 or 2;
X represents an oxygen atom or an unsubstituted or at least mono-substituted C-I-4 alkylene radical; R31, R32, R33 and R34, independent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
an unsubstituted phenyl or naphthyl radical;
a radical selected from the group consisting of -0-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain of these radicals is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
or
an -O-Si(R30)3 radical, with R30 representing a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and hexyl;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
10. At least one silylated substituted benzotriazolylphenol compound according to one or more of claims 1 to 9, characterized in that
q = 1 or 2; k = 0 or 1 ; R1 and R2, independent from one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -CH2-C≡N; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Phenyl, -0-CH3; or -0-CH2-CH3;
R3 represents a radical selected from the group consisting of phenyl, naphthyl, cyclopentyl, cyclohexyl and cycloheptyl, which is 1 , 2, 3, 4 or 5 substituent(s) independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, -O-CH3, -0-C2H5, -0-CH2-CH2-CH3, -O-CH(CH3)2, -O-C(CH3)3, -S-CH3, -S-C2H5, -S-CH2-CH2-CH3, -S-CH(CH3J2, -S-C(CH3)3, -C(=O)-OH, -C(=O)-OCH3) -C(=O)-OCH2CH3, -S(=O)2-Phenyl, -C(=O)-CH3) -C(=O)-C2H5, -C(=O)-CH2-CH2-CH3, -C(=O)-CH(CH3)2, -C(=O)-C(CH3)3, F, Cl, Br, I, -CN, -CF3, -OCF3, -SCF3, -SO3Na, -SO3K, -SO3H, -OH, -SH, -NH2, -NH-CH3, phenyl, phenethyl, phenoxy and benzyl;
R4 represents a radical selected from the group consisting of methyl, ethyl, n- propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
with the provision that if q = 1, then
k = 1 ;
R5, R6 and R7, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting Of -O-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
an unsubstituted phenyl or naphthyl radical;
or at least one of the radicals R5, R6 and R7, independent from one another, each represents a radical of general formula (II)
Figure imgf000115_0001
(") wherein
P = O oM ;
R25, R26, R27, R28 and R29, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopro- pyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting of -O-CH3, -0-CH2-CH3, -0-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH3, -0-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched; or
an -O-Si(R30)3 radical, with R30 representing a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and hexyl, which is unsubstituted;
with the condition that if q = 1 and at the same time k = 1 , at least one of the radicals R5, R6 and R7 represents a radical of general formula (II) as defined above;
or, with the provision that if q = 2, then
k = 0;
R7 represents a radical of general formula (III)
Figure imgf000116_0001
(III) wherein
m = 0, 1 or 2;
X represents an oxygen atom or an unsubstituted or at least mono-substituted C-ι-4 alkylene radical;
R31, R32, R33 and R34, independent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which is unsubstituted; and whereby in each occurrence the pentyl, hexyl, heptyl, octyl, nonyl or decyl radical is linear or branched;
a radical selected from the group consisting of -CH2-Phenyl and -CH2-CH2-Phenyl;
an unsubstituted phenyl or naphthyl radical;
a radical selected from the group consisting of -O-CH3, -O-CH2-CH3, -O-CH2-CH2-CH3, -O-CH2-CH2-CH2-CH3, -O-CH2-CH2-CH2-CH2-CH3, -O-CH2-CH2-CH2-CH2-CH2-CH3 and -0-CH2-CH2-CH2-CH2-CH2-CH2-CH3; whereby in each occurrence the alkyl chain of these radicals is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
or
an -O-Si(R30)3 radical, with R30 representing a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and hexyl, which is unstubstituted;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
11. At least one silylated substituted benzotriazolylphenol compound according to claim 1 with the general formula (IB)
Figure imgf000118_0001
wherein
qb = 1 or 2; kb = 0 or 1 ;
R1b and R2b, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Phenyl, -0-CH3; Or -O-CH2-CH3;
R3b and R3bb, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Phenyl, -0-CH3; or -0-CH2-CH3;
R4b represents a radical selected from the group consisting of methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, which is unsubstituted;
with the provision that if q b _ = 1, then
k ,bD _ = 1 ; R5b, R6b and R7b, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -0-CH3, -O-C2H5, -O-C3H7, -O-C4H9, -O-C5H11 and -O-C6Hi3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
an unsubstituted phenyl or naphthyl radical;
or
R 5b R 6b and R 7b jn(jepenc|ent of one another, each represents a radical of general formula (Mb)
Figure imgf000119_0001
(lib)
wherein
pb = O or 1 ;
R 25b R 26b R 27b_ R 2βb and R 29b jndependent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -Chb-Phenyl and -CH2- CH2-Phenyl; a radical selected from the group consisting of -0-CH3; -0-C2H5; -0-C3H7; -0-C4H9; -O-C5H11; and -O-CβH13; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3; -O-Si-(C2H5)3; -0-Si-(C4Hg)3; -O-Si-(Phenyl)3; -CH2-Si-(CH3)3 and -CH2-Si-(C2Hs)3;
an unsubstituted phenyl or naphthyl radical;
with the condition that if qb = 1 and at the same time kb =1 , at least one of the radicals R5b, R6b and R7b represents a radical of general formula (lib) as defined above;
or, with the provision that if q b _ = 2, then
k ,bD - = 0;
represents a radical of general formula (MIb)
Figure imgf000120_0001
(MIb)
wherein
m ,bD _ = 0, 1 or 2; Xb represents an oxygen atom or an unsubstituted or at least mono- substituted C-1-4 alkylene radical;
R31b, R32b, R33b and R34b, independent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting of -0-CH3; -0-C2H5; -O-C3H7; -O-C4H9; -O-C5Hn; and -0-CeH13; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3; -O-Si-(C2H5)3; -0-Si-(C4Hg)3; -O-Si-(Phenyl)3; -CH2-Si-(CH3)3 and -CH2-Si-(C2Hg)3;
or
an unsubstituted phenyl or naphthyl radical;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
12. At least one silylated substituted benzotriazolylphenol compound according to claim 1 with the general formula (IC)
Figure imgf000122_0001
wherein
n = 0, 1 , or 2;
R1c and R2c, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Ph, -O-CH3; or -0-CH2-CH3;
R3c and R3cc, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3, -C(=O)-OCH2CH3, -S(=O)2-Ph, -0-CH3; Or -O-CH2-CH3;
R4c represents a radical selected from the group consisting of methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, which is unsubstituted;
with the provision that if qc = 1, then
kc = 1 ; R5c, R6c and R7c, independent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting Of -O-CH3, -O-C2H5> -0-C3H7, -O-C4H9, -O-C5H11, and -0-C6Hi3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
an unsubstituted phenyl or naphthyl radical;
or
R 5c R 6c and R 7c jnc|epenc|ent of one another, each represents a radical of general formula (lie)
Figure imgf000123_0001
(lie)
wherein
pc = 0 or 1 ; R 25c R 26c R 27c R 28c and R 29c jncjepenc|ent from one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting Of -O-CH3, -0-C2H5, -0-C3H7, -O-C4H9, -0-C5H11, and -0-C6H13; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3, -O-Si-(C2H5)3l -0-Si-(C4Hg)3, -0-Si-(Ph)3, -CH2-Si-(CH3)3 and -CH2-Si-(C2Hs)3;
an unsubstituted phenyl or naphthyl radical;
with the condition that if qc = 1 and at the same time kc =1 , at least one of the radicals R5c, R6c and R7c represents a radical of general formula (lie) as defined above;
or, with the provision that if qc = 2, then
kc = 0;
R7c represents a radical of general formula (MIc)
Figure imgf000125_0001
(HIc) wherein
mc = 0, 1 or 2;
Xc represents an oxygen atom or an unsubstituted or at least mono- substituted C-1-4 alkylene radical;
R 3ic R 32c R 33c and R 34c jn(jepenc|ent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopro- pyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Phenyl and -CH2- CH2-Phenyl;
a radical selected from the group consisting of -0-CH3, -0-C2H5, -O-C3H7, -O-C4H9, -O-C5H11 and -O-C-6Hi3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3l -O-Si-(C2H5)3, -0-Si-(C4Hg)3, -0-Si-(Ph)3, -CH2-Si-(CH3)3 and -CH2-Si-(C2Hs)3;
an unsubstituted phenyl or naphthyl radical;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corre- sponding, physiologically acceptable salt, or a corresponding solvate.
13. At least one silylated substituted benzotriazolylphenol compound according to claim 1 with the general formulae (ID), (IE) and (IF)
Figure imgf000126_0001
(ID)
Figure imgf000126_0002
(IE)
Figure imgf000127_0001
("F)
wherein
R1b and R2b, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3; -C(=O)-OCH2CH3; -S(=O)2-Ph; -0-CH3; or -0-CH2-CH3;
R3b and R3bb, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3; -C(=O)-OCH2CH3; -S(=O)2-Ph; -O-CH3; or -0-CH2-CH3;
R4b represents a radical selected from the group consisting of methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, which is unsubstituted;
mb = 0, 1 , 2, 3, 4 or 5;
R 3ib R 32b R 33b and R 34b jnc|epenc|ent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting of -CH2-Ph and -CH2- CH2-Ph;
a radical selected from the group consisting of -O-CH3, -0-C2H5, -0-C3H7, -O-C4H9, -O-C5H11 and -0-C6Hi3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3, -O-Si-(C2H5)3, -0-Si-(C4Hg)3, -0-Si-(Ph)3, -CH2-Si-(CH3)3 and -CH2-Si-(C2Hs)3;
an unsubstituted phenyl or naphthyl radical;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
14. At least one silylated substituted benzotriazolylphenol compound according to claim 1 with the general formulae (IG), (IH) and (IJ)
Figure imgf000128_0001
(IG)
Figure imgf000129_0001
(IH)
Figure imgf000129_0002
(IJ)
wherein
R1c and R2c, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; Cl; Br; I; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3; -C(=O)-OCH2CH3; -S(O)2-Ph; -0-CH3; Or -O-CH2-CH3;
R3c and R3cc, independent of one another, each represents a hydrogen atom; methyl; ethyl; F; -OH; -CN; -CF3; -C(=O)-OH; -C(=O)-OCH3l -C(=O)-OCH2CH3, -S(=O)2-Ph, -0-CH3; or -0-CH2-CH3; R4c represents a radical selected from the group consisting of methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, which is unsubstituted;
mc = 0, 1 , 2, 3, 4 or 5;
R 3ic R 32 Cj R 33c and R 34c jnc|epenc|ent of one another, each represents a radical selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, which is unsubstituted;
a radical selected from the group consisting Of -CH2-Ph and -CH2- CH2-Ph;
a radical selected from the group consisting of -0-CH3, -0-C2H5, -O-C3H7, -O-C4H9, -0-C5Hn and -O-CβHi3; whereby in each occurrence the alkyl chain is unsubstituted; and whereby in each occurrence the alkyl chain of these radicals is linear or branched;
a radical selected from the group consisting of -O-Si-(CH3)3, -O-Si-(C2H5)3, -0-Si-(C4Hg)3, -0-Si-(Ph)3, -CH2-Si-(CHa)3 and -CH2-Si-(C2Hs)3;
an unsubstituted phenyl or naphthyl radical;
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
15. At least one silylated substituted benzotriazolylphenol compound according to one or more of claims 1 to 14 selected from the group consisting of
[1 ] 3-(2H-benzotriazol-2-yl)-5-[2-methyl-3-[1 ,3,3,3-tetramethyl-1 - [(trimethylsilyl)oxy]disiloxanyl]propyl]biphenyl-4-ol,
[2] 3-(2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 , 1 ,3,3,3-pentamethyl- disiloxanyl)-propyl]-biphenyl-4-ol, [3] 2-(2H-benzotriazol-2-yl)-4-cyclohexyl-6-[2-methyl-3-(1 ,1 ,3,3,3- pentamethyl-disiloxanyl)-propyl]-phenol,
[4] 2-(2H-benzotriazol-2-yl)-4-cyclohexyl-6-[2-methyl-3-[1 ,3,3,3-tetramethyl- 1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-phenol,
[5] 3-(5-Chloro-2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl- disiloxanyl)-propyl]-biphenyl-4-ol,
[6] 3-(5-Methoxy-2H-benzotriazol-2-yl)-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl- disiloxanyl)-propyl]-biphenyl-4-ol,
[7] 2-{4-Hydroxy-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]- biphenyl-3-yl}-2/-/-benzotriazole-5-carbonitrile,
and
[8] 2-{4-Hydroxy-5-[2-methyl-3-(1 ,1 ,3,3,3-pentamethyl-disiloxanyl)-propyl]- biphenyl-3-yl}-2H-benzotriazole-5-carboxylic acid,
optionally in the form of one of its stereoisomers, preferably enantiomers or di- astereomers, its racemate or in the form of a mixture of at least two of its stereoisomers, enantiomers or diastereomers, in any mixture ratio, or a salt, a corresponding, physiologically acceptable salt, or a corresponding solvate.
16. A process for the preparation of at least one silylated substituted benzotriazolylphenol compound according to one or more of claims 1 to 15, characterized in that it comprises the step of reacting at least one compound of general formula (P9)
Figure imgf000131_0001
wherein R1, R2, R3 and R4 have the meaning according to claim 1 , with at least one suitable silyl derivative of general formula (P10)
Figure imgf000132_0001
k (P10)
wherein R5, R6, R7 and k have the meaning according to claim 1 , following typical hydrosilylation of carbon-carbon double bonds conditions, preferably in the presence of a catalyst, more preferably in the presence of a catalyst comprising an electron-rich complex of a late transition metal such as e.g. Co(I), Rh(I), Ni(O), Pd(O), or Pt(O), preferably with Speier catalyst (H2[PtCI6]), PtO2 or Karstedt catalyst (Pt2KCH2=CH)Me2Si]2O)3), more preferably using Karstedt catalyst, preferably in the presence of an organic solvent, more preferably an aromatic aprotic solvent such as e.g. xylene, preferably at a temperature ranging from O0C to the boiling point of the solvent, more preferably at a temperature between 5O0C and the boiling point of the solvent, even more preferably at 1000C until the reaction is completed to yield at least one compound of general formula (I)
Figure imgf000132_0002
wherein R1, R2, R3, R4, R5, R6 and R7 have the meaning according to claim 1.
17. A pharmaceutical composition comprising at least one silylated substituted benzotriazolylphenol compound according to anyone of claims 1 to 15, and optionally at least one pharmacologically acceptable auxiliary agent.
18. A cosmetic composition comprising at least one silylated substituted benzotriazolylphenol compound according to anyone of claims 1 to 15, and optionally at least one cosmetical vehicle.
19. Use of at least one silylated substituted benzotriazolylphenol compound according to anyone of claims 1 to 15 for the preparation of a pharmaceutical composition for the prophylaxis and/or treatment of diseases caused by and/or associated with exposure to ultraviolet radiation, preferably of the lips, the face and/or of the body of mammals, preferably human beings.
20. Use of at least one silylated substituted benzotriazolylphenol compound according to anyone of claims 1 to 15 as an agent for the preparation of a pharmaceutical composition for the prophylaxis and/or care and/or treatment against non-desired skin conditions comprising polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis.
21. Use of at least one silylated substituted benzotriazolylphenol compound according to anyone of claims 1 to 15 as an agent for the prophylaxis and/or care against non-desired skin conditions comprising polymorphous light eruption, actinic keratosis, solar urticaria, xeroderma pigmentosum, photoageing, sunburn and/or chronic actinic dermatitis.
22. Use of at least one silylated substituted benzotriazolylphenol compound according to anyone of claims 1 to 15 for protecting the skin preferably of the lips, the face and/or of the body of a mammal, preferably a human, against ultraviolet radiation, preferably UV-A and/or UV-B radiation.
23. Use of at least one silylated substituted benzotriazolylphenol compound according to anyone of claims 1 to 15 as a light-stabilizer in polymer compositions.
24. Use of at least one silylated substituted benzotriazolylphenol compound according to anyone of claims 1 to 15 as a light-stabilizer in textile fibers.
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WO2003039507A1 (en) * 2001-11-09 2003-05-15 Beiersdorf Ag Cosmetic and dermatological anti-uv formulations containing hydroxybenzophenone and triazine and/or benzotriazol derivatives

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