US 12,291,509 B2
Process for the preparation of UV absorbers
Rahul Garg, Navi Mumbai (IN); Mushtaq Patel, Navi Mumbai (IN); Prachin Kolambkar, Mumbai (IN); Mileen Kadam, Mumbai (IN); Deepak Makade, Mumbai (IN); and Ramraj Bhatta, Mumbai (IN)
Assigned to BASF SE, Ludwigshafen am Rhein (DE)
Appl. No. 17/421,326
Filed by BASF SE, Ludwigshafen am Rhein (DE)
PCT Filed Jan. 2, 2020, PCT No. PCT/EP2020/050010
§ 371(c)(1), (2) Date Jul. 7, 2021,
PCT Pub. No. WO2020/144094, PCT Pub. Date Jul. 16, 2020.
Claims priority of application No. 19150636 (EP), filed on Jan. 8, 2019.
Prior Publication US 2022/0064129 A1, Mar. 3, 2022
Int. Cl. C07D 251/24 (2006.01)
CPC C07D 251/24 (2013.01) 14 Claims
 
1. A process for preparing a compound of formula (A)

OG Complex Work Unit Chemistry
wherein Ar1 and Ar2 are independently a moiety of the formula (B),

OG Complex Work Unit Chemistry
wherein
R1, R2, R3, R4 and R5 are independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted, linear or branched C1-C24 alkyl, substituted or unsubstituted, linear or branched C2-C24 alkenyl, substituted or unsubstituted C5-C24 cycloalkyl, substituted or unsubstituted C5-C24 cycloalkenyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C7-C24 arylalkyl, C(═O)R, OR, NRR′, C(═O) NRR′, CN, SR, S(═O)2R, S(═O)2OH and S(═O)2OM; wherein M is an alkali metal; or
R1 and R2 together with the carbon atoms to which they are bonded or
R2 and R3 together with the carbon atoms to which they are bonded or
R3 and R4 together with the carbon atoms to which they are bonded or
R4 and R5 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);
Q is selected from hydrogen and OH;
R6 is selected from the group consisting of hydrogen, substituted or unsubstituted, linear or branched C1-C24 alkyl, substituted or unsubstituted, linear or branched C2-C24 alkenyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C7-C24 arylalkyl, substituted or unsubstituted C5-C24 cycloalkyl and substituted or unsubstituted C5-C24 cycloalkenyl, and C(═O)R;
R7, R8 and R9 are independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted, linear or branched C1-C24 alkyl, substituted or unsubstituted, linear or branched C2-C24 alkenyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C7-C24 arylalkyl, substituted or unsubstituted C5-C24 cycloalkyl, substituted or unsubstituted C5-C24 cycloalkenyl, C(═O)R, OR, NRR′, C(═O) NRR′, OC(═O)R, CN, SR, S(═O)2R, S(═O)2OH and S(═O)2OM, wherein M is an alkali metal, or
R7 and R8 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);
Y is selected from the group consisting of hydrogen, halogen, O, —NR″, or S, wherein R″ is selected from the group consisting of hydrogen, substituted or unsubstituted, linear or branched C1-C24 alkyl, substituted or unsubstituted, linear or branched C2-C24 alkenyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C7-C24 arylalkyl, substituted or unsubstituted C5-C24 cycloalkyl and substituted or unsubstituted C5-C24 cycloalkenyl; with the proviso that in case Y is hydrogen or halogen, then R6 is not present; and
R and R′ are independently selected from the group consisting of hydrogen, substituted or unsubstituted, linear or branched C1-C24 alkyl, substituted or unsubstituted, linear or branched C2-C24 alkenyl, substituted or unsubstituted C5-C24 cycloalkyl, substituted or unsubstituted C5-C24 cycloalkenyl, substituted or unsubstituted C6-C24 aryl and substituted or unsubstituted C7-C24 arylalkyl;
comprising at least the steps of:
i) reacting at least one compound of formula (C)

OG Complex Work Unit Chemistry
wherein LG is halogen, O—S(═O)2CF3 or O—S(═O)2CH3;
with at least one compound of formula (B1)

OG Complex Work Unit Chemistry
wherein R1, R2, R3, R and R5 are defined as above;
in the presence of at least one acid to obtain a compound of formula (D)

OG Complex Work Unit Chemistry
wherein Ar1 and Ar2 are defined as above;
ii) reacting the compound of formula (D) obtained according to step i) with at least one metal hydroxide to obtain a compound of formula (E)

OG Complex Work Unit Chemistry
wherein Ar1 and Ar2 are defined as above;
iii) reacting the compound of formula (E) obtained according to step ii) with at least one halogenating reagent to obtain a compound of formula (F)

OG Complex Work Unit Chemistry
wherein Ar1 and Ar2 are defined as above, and
W is selected from the group consisting of F, Cl, and Br; and
iv) reacting at least one compound of formula (F) obtained according to step iii) and at least one compound of formula (G),

OG Complex Work Unit Chemistry
wherein Y, Q, R6, R7, R8 and R9 are defined as above,
in the presence of an at least one acid to obtain a compound of formula (A).