5-thio-substituted benzotriazole UV-absorbers

• US 5,278,314 A
• Filed: 02/05/1992
• Issued: 01/11/1994
• Est. Priority Date: 02/12/1991
• Status: Expired due to Term

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Ravichandran, Ramanathan, Stevenson, Tyler A., Holt, Mark S., Winter, Roland A. E., von Ahn, Volker H.
• Primary Examiner(s): Morris, Patricia L.
• Application Number:
  US07/828,290
• Time in Patent Office: 706 Days
• Field of Search: 548/259
• US Class Current: 548/259
• CPC Class Codes: C07D 249/20 with aryl radicals directly attached in position 2
• CPC Class Codes: C07F 9/65188 condensed with carbocyclic rings or carbocyclic ring systems
• CPC Class Codes: C08F 220/387 and containing nitrogen and oxygen
• CPC Class Codes: C08K 5/3475 condensed with carbocyclic rings
• CPC Class Codes: C08K 5/378 containing heterocyclic rings

Abstract

2-(2-Hydroxyphenyl)-2H-benzotriazole UV-absorbers substituted at the 5-position of the benzo ring by a thioether group exhibit enhanced absorption in the near visible range (over 350 nm) allowing said compounds to be particularly effective in protecting polymer systems which are prone to degradation caused by actinic irradiation with wavelengths over 350 nm.

Claims

1. A compound of formula I, II or III ##STR9## wherein R₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,

R₂ is straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms;

said alkyl substituted by one or more --OH, --OR₄ or --NH₂ groups where R₄ is alkyl of 1 to 12 carbon atoms;

n is 1;

R₅ is --OR₆ or --NH₂ ;

R₆ is hydrogen or alkyl of 1 to 24 carbon atoms;

or said alkyl substituted by one or more --OH groups;

or --OR₆ is --(OCH₂ CH₂)_W OH or --(OCH₂ CH₂)_W OR₂₁ where w is 1 to 12 and R₂₁ is alkyl of 1 to 12 carbon atoms,

R₃ is alkyl of 8 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms, and

T is --S--, --S--S-- or --S--E--S--,

where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms, and

with the proviso that, when R₁ is sec-butyl and R₂ is tert-butyl, R₃ is not methyl.

2. A compound according to claim 1 wherein

R₁ is hydrogen, branched alkyl of 3 to 12 carbon atoms, cyclohexyl or phenylalkyl of 7 to 9 carbon atoms,

R₂ is straight or branched chain alkyl of 1 to 12 carbon atoms, cyclohexyl or phenylalkyl of 7 to 9 carbon atoms;

R₃ is alkyl of 8 to 18 carbon atoms, allyl, cyclohexyl, phenylalkyl of 7 to 9 carbon atoms, phenyl or said phenyl substituted by one or two methyl groups, and

T is --S-- or --S--E--S,

where E is alkylene of 2 to 6 carbon atoms, cycloalkylene of 6 to 8 carbon atoms or alkylene terminated by cyclohexylene of 8 to 10 carbon atoms.

3. A compound according to claim 1 wherein

R₁ is hydrogen, branched alkyl of 4 to 8 carbon atoms, cyclohexyl, benzyl, α

-methylbenzyl or α

,α

-dimethylbenzyl,

R₂ is straight or branched chain alkyl of 1 to 8 carbon atoms, cyclohexyl, benzyl, α

-methylbenzyl or α

,α

-dimethylbenzyl,

R₃ is phenyl, and

T is --S-- or --S--E--S--,

where E is alkylene of 4 to 6 carbon atoms, cycloalkylene of 6 to 8 carbon atoms or dihydrolimonenediyl.

4. The compound according to claim 1 which is

(a) 5-n-dodecylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(b) 5-phenylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(c) 5-phenylthio-2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole;

(d) 5-benzylthio-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

(e) 5-phenylthio-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

(f) 5-n-octylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(g) 5-tridecylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

(h) 5,5'"'"'-(1,8-dithiaoctane-1,8-diyl)bis[2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole];

(i) 5,5'"'"'-(dithiadihydrolimonenediyl)bis[2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole];

(j) 5-phenylthio-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

(k) 5-phenylthio-2-(2-hydroxy-3,5-di-α

-cumylphenyl)-2H-benzotriazole;

(l) 5,5'"'"'-thiobis[2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole];

(m) 5-phenylthio-2-[2-hydroxy-3-tert-butyl-5-(β

-carboxyethyl)phenyl]-2H-benzotriazole;

(n) 5-phenylthio-2-[2-hydroxy-3-tert-butyl-5-(β

-octyloxycarbonylethyl)phenyl]-2H-benzotriazole;

(o) 5-phenylthio-2-{2-hydroxy-3-tert-butyl-5-[2-(ω

-hydroxyocta(ethyleneoxy)-carbonylethyl]phenyl}-2H-benzotriazole;

(p) 5-phenylthio-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

(q) 3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid;

(r) 3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamamide;

(t) ω

-hydroxy-poly(ethyleneoxy) 3-(5-phenylthio-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate; and

(u) poly(ethyleneoxy) bis[3-(5-phenylthio-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate].