Process for the preparation of triazine intermediates and a process for the preparation of UV absorbers thereof

Patent metadata

Field	Value
Publication number	US-12378205-B2
Application number	US-202017421301-A
Country	US
Kind code	B2
Filing date	Jan 2, 2020
Priority date	Jan 8, 2019
Publication date	Aug 5, 2025
Grant date	Aug 5, 2025

Abstract

The presently claimed invention relates to a novel, highly efficient and general process for the preparation of the triazine intermediates and their use in the preparation of UV absorbers.

First claim

The invention claimed is:

1. A process for preparing a compound of formula (A):

wherein Ar 1 and Ar 2 are independently a moiety of the formula (B):

wherein
R 1 , R 2 , R 3 , Rand R 5 are independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted, linear or branched C 1 -C 24 alkyl, substituted or unsubstituted, linear or branched C 2 -C 24 alkenyl, substituted or unsubstituted C 5 -C 24 cycloalkyl, substituted or unsubstituted C 5 -C 24 cycloalkenyl, substituted or unsubstituted C 6 -C 24 aryl, substituted or unsubstituted C 7 -C 24 arylalkyl, C(═O)R, OR, NRR′, C(═O)NRR′, CN, SR, S(═O) 2 R, S(═O) 2 OH and S(═O) 2 OM; wherein M is an alkali metal; or
R 1 and R 2 together with the carbon atoms to which they are bonded or
R 2 and R 3 together with the carbon atoms to which they are bonded or
R 3 and R 4 together with the carbon atoms to which they are bonded or
R 4 and R 5 together with the carbon atoms to which they are bonded form an unsaturated or aromatic 5- to 20-membered carbocyclic ring that optionally contains 1, 2 or 3 heteroatom(s) selected from O, N or S as ring member(s); and
R and R′ are independently selected from the group consisting of hydrogen, substituted or unsubstituted, linear or branched C 1 -C 24 alkyl, substituted or unsubstituted, linear or branched C 2 -C 24 alkenyl, substituted or unsubstituted C 5 -C 24 cycloalkyl, substituted or unsubstituted C 5 -C 24 cycloalkenyl, substituted or unsubstituted C 6 -C 24 aryl and substituted or unsubstituted C 7 -C 24 arylalkyl;
comprising at least the steps of reacting at least one compound of formula (C)

wherein LG is halogen, O—S(═O) 2 CF 3 or O—S(═O) 2 CH 3 ;
and at least one compound of formula (B2)

wherein
R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted, linear or branched C 1 -C 24 alkyl, substituted or unsubstituted, linear or branched C 2 -C 24 alkenyl, substituted or unsubstituted C 5 -C 24 cycloalkyl, substituted or unsubstituted C 5 -C 24 cycloalkenyl, substituted or unsubstituted C 6 -C 24 aryl, substituted or unsubstituted C 7 -C 24 arylalkyl, C(═O)R, OR, NRR′, C(═O)NRR′, CN, SR, S(═O) 2 R, S(═O) 2 OH and S(═O) 2 OM; wherein M is an alkali metal; or
R 1 and R 2 together with the carbon atoms to which they are bonded or
R 2 and R 3 together with the carbon atoms to which they are bonded or
R 3 and R 4 together with the carbon atoms to which they are bonded or
R 4 and R 5 together with the carbon atoms to which they are bonded form an unsaturated or aromatic 5- to 20-membered carbocyclic ring that optionally contains 1, 2 or 3 heteroatom(s) selected from O, N or S as ring member(s); and
R and R′ are independently selected from the group consisting of hydrogen, substituted or unsubstituted, linear or branched C 1 -C 24 alkyl, substituted or unsubstituted, linear or branched C 2 -C 24 alkenyl, substituted or unsubstituted C 5 -C 24 cycloalkyl, substituted or unsubstituted C 5 -C 24 cycloalkenyl, substituted or unsubstituted C 6 -C 24 aryl and substituted or unsubstituted C 7 -C 24 arylalkyl;
in the presence of at least one acid.

2. The process according to claim 1 , wherein the at least one acid is selected from the group consisting of inorganic acids, Lewis acids, and organic acids.

3. The process according to claim 2 , wherein the Lewis acids are selected from the group consisting of AsX 3 , GaX 3 , BX 3 , BX 3 —(C 2 H 5 ) 2 O, BX 3 —S(CH 3 ) 2 , AlX 3 , (C 2 H 5 ) 2 AlX, SbX 3 , SbX 5 , SnX 2 , MgX 2 , MgX 2 —O(C 2 H 5 ) 2 , ZnX 2 , BiX 3 , FeX 2 , TiX 2 , TiX 4 , NbX 5 , NiX 2 , CoX 2 , HgX 2 , PbX 2 , MnX 2 , CuX, CuX 2 whereby X in each case denotes F, Cl, Br, CF 3 —S(═O) 2 O, CH 3 —S(═O) 2 O, or I; BH 3 , B(CH 3 ) 3 , GaH 3 , AlH 3 , Al(acetate)(OH) 2 , Al[OCH(CH 3 ) 2 ] 3 , Al(OCH 3 ) 3 , Al(OC 2 H 5 ) 3 , Al 2 O 3 , (CH 3 ) 3 Al, Ti[OCH(CH 3 ) 2 ] 3 Cl, Ti[OCH(CH 3 ) 2 ] 4 , methylaluminum di-(2,6-di-tert-butyl-4-methylphenoxide), methylaluminum di-(4-brom-2,6-di-tert-butylphenoxide), LiClO 4 ; Mg(acetate) 2 , Zn(acetate) 2 , Ni(acetate) 2 , Ni(NO 3 ) 2 , Co(acetate) 2 , Co(NO 3 ) 2 , Cu(acetate) 2 , Cu(NO 3 ) 2 , Li(acetate), Zr(acetylacetonate) 4 , Si(acetate) 4 , K(acetate), Na(acetate), Cs(acetate), Rb(acetate), Mn(acetate) 2 , Fe(acetate) 2 , Bi(acetate) 3 , Sb(acetate) 3 , Sr(acetate) 2 , Sn(acetate) 2 , Zr(acetate) 2 , Ba(acetate) 2 , Hg(acetate) 2 , Ag(acetate), Tl(acetate) 3 , Sc(trifluoromethanesulfonate) 3 , Ln(trifluoromethanesulfonate) 3 , Ni(trifluoromethanesulfonate) 2 , Ni(tosylate) 2 , Co(trifluoromethanesulfonate) 2 , Co(tosylate) 2 , Cu(tri-fluoromethanesulfonate) 2 and Cu(tosylate) 2 .

4. The process according to claim 3 , wherein the at least one Lewis acid is selected from the group consisting of BX 3 , BX 3 —(C 2 H 5 ) 2 O, BX 3 —S(CH 3 ) 2 , AlX 3 , ZnX 2 , FeX 3 and TiX 4 , whereby X in each case denotes F, Cl, or Br.

5. The process according to claim 1 , wherein R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted, linear or branched C 1 -C 24 alkyl, substituted or unsubstituted C 6 -C 24 aryl, C(═O)R and OR, wherein R is selected from the group consisting of hydrogen, substituted or unsubstituted, linear or branched C 1 -C 24 alkyl, substituted or unsubstituted, linear or branched C 2 -C 24 alkenyl, substituted or unsubstituted C 5 -C 24 cycloalkyl, substituted or unsubstituted C 5 -C 24 cycloalkenyl, substituted or unsubstituted C 6 -C 24 aryl and substituted or unsubstituted C 7 -C 24 arylalkyl.

6. The process according to claim 1 , wherein the molar ratio of the at least one acid to the at least one compound of formula (C) is in the range of 1:10 to 10:1.

7. The process according to claim 1 , wherein the molar ratio of the at least one compound of formula (B2) to the at least one compound of formula (C) is in the range of 1:1 to 5:2.

8. The process according to claim 1 , wherein the at least one compound of formula (C) and the at least one compound of formula (B2) are reacted in the presence of at least one solvent selected from the group consisting of aliphatic hydrocarbons, aliphatic acyclic ether, aliphatic cyclic ether and carbon disulfide.

9. The process according to claim 8 , wherein the molar concentration of the at least one compound of formula (C) in the at least one solvent is in the range of 0.5 M to 8.0 M.

10. The process according to claim 8 , wherein the molar concentration of the at least one compound of formula (B2) in the at least one solvent is in the range of 0.5 M to 8.0 M.

11. The process according to claim 8 , wherein the aliphatic cyclic ether is dioxane.

12. A process for preparing a compound of formula (D),

wherein Ar 1 and Ar 2 are defined as in claim 1 , and
W is selected from the group consisting of F, Cl, and Br,
comprising at least the steps of
i) reacting a compound of formula (A) obtai

Assignees

• Basf Se

Inventors

• Garg Rahul
• Kolambkar Prachin
• Patel Mushtaq

Classifications

• C07D251/24 Primary

  to three ring carbon atoms · CPC title

• C09B57/00 Primary

  Other synthetic dyes of known constitution · CPC title