US 12,168,649 B2
Synthesis of chromanol and 2-methyl-1,4-naphthoquinone derivatives
Melanie Weingarten, Ludwigshafen am Rhein (DE); Wolfgang Siegel, Ludwigshafen am Rhein (DE); and Michael Puhl, Ludwigshafen am Rhein (DE)
Assigned to BASF SE, Ludwigshafen am Rhein (DE)
Appl. No. 17/269,080
Filed by BASF SE, Ludwigshafen am Rhein (DE)
PCT Filed Aug. 16, 2019, PCT No. PCT/EP2019/072034
§ 371(c)(1), (2) Date Feb. 17, 2021,
PCT Pub. No. WO2020/035601, PCT Pub. Date Feb. 20, 2020.
Claims priority of application No. 18189592 (EP), filed on Aug. 17, 2018.
Prior Publication US 2021/0171489 A1, Jun. 10, 2021
Int. Cl. C07D 311/72 (2006.01); B01J 21/16 (2006.01); B01J 35/61 (2024.01); B01J 37/06 (2006.01)
CPC C07D 311/72 (2013.01) [B01J 21/16 (2013.01); B01J 35/615 (2024.01); B01J 35/617 (2024.01); B01J 37/06 (2013.01)] 19 Claims
 
1. A process for preparing a compound of formula I or II

OG Complex Work Unit Chemistry
wherein
R1, R2 and R3 independently of each other are selected from hydrogen and methyl,
R4 is selected from hydrogen and C1-C6-alkanoyl,
X is selected from C1-C20-alkyl and an isoprenyl moiety of formula X.a

OG Complex Work Unit Chemistry
wherein
n is an integer of from 1 to 10 and
* indicates the attachment point to the rest of the molecule,
comprising the following steps:
a) providing a compound of formula III or IV.a or IV.b or IV.c,

OG Complex Work Unit Chemistry
wherein
R1, R2 and R3 are as defined above,
R4a independently of each other is selected from hydrogen and C1-C6-alkanoyl,
R5 independently of each other is selected from hydrogen, C1-C6-alkyl, C1-C6-alkanoyl and benzoyl, and
R6 independently of each other is selected from C1-C4-alkyl,
b) reacting the compound III or IV.a or IV.b or IV.c provided in step a) with an unsaturated compound of formula V.a or V.b

OG Complex Work Unit Chemistry
wherein
X is as defined above,
Y is selected from OH, halogen, —O—R11, —S—R12 and —SO2—R12,
R11 is selected from C1-C4-alkyl, C1-C4-alkanoyl and trifluoroacetyl, and
R12 is selected from C1-C6-alkyl, trifluoromethyl and phenyl, where phenyl is unsubstituted or substituted with 1, 2, 3, 4 or 5 radicals selected from halogen and methyl,
in the presence of an acid treated bentonite catalyst, and
c.1) in case a compound of the formula III, wherein both R4ª are hydrogen, is applied in step b), and in case R4 in compound I is selected from C1-C6-alkanoyl, reacting the condensation product obtained in step b) with a C2-C7-carboxylic acid or with a C2-C7-carboxylic acid anhydride in the presence of an esterification catalyst, or reacting the condensation product obtained in step b) with an activated C2-C7-carboxylic acid in the presence of a base,
or
c.2) in case a compound of the formula IV.a wherein at least one R5 is C1-C6-alkanoyl or benzoyl, is applied in step b),
treating the product obtained in step b) with a base and subsequently with an oxidizing agent,
or
c.3) in case a compound of the formula IV.a, wherein R5 independently of each other are selected from hydrogen and C1-C6-alkyl, is applied in step b),
treating the product obtained in step b) with an oxidizing agent,
or
c.4) in case a compound of the formula IV.b is applied in step b),
treating the product obtained in step b) with an acid.