US 12,410,114 B2
Process for the preparation of α-functionalized ketones
Reinhard Sommerlade, Neuenburg am Rhein (DE); and Thomas Loerzer, Landau-Godramstrein (DE)
Assigned to IGM GROUP B.V., Waalwijk (NL)
Appl. No. 16/603,533
Filed by IGM GROUP B.V., Waalwijk (NL)
PCT Filed Apr. 19, 2018, PCT No. PCT/EP2018/060012
§ 371(c)(1), (2) Date Oct. 7, 2019,
PCT Pub. No. WO2018/197325, PCT Pub. Date Nov. 1, 2018.
Claims priority of application No. 17167814 (EP), filed on Apr. 24, 2017.
Prior Publication US 2020/0055806 A1, Feb. 20, 2020
Int. Cl. C07C 45/64 (2006.01); C07C 319/20 (2006.01); C07D 295/108 (2006.01)
CPC C07C 45/64 (2013.01) [C07C 319/20 (2013.01); C07D 295/108 (2013.01); C07C 2601/14 (2017.05); C07C 2601/16 (2017.05); C07C 2602/10 (2017.05)] 19 Claims
 
1. A process for the preparation of an α-functionalized ketone of the general formula I,

OG Complex Work Unit Chemistry
wherein R1 and R2 are the same or different and are independently selected from H, linear or branched C1-C8-alkyl, C3-C8-cycloalkyl, linear or branched C2-C8-alkenyl, C5-C8-cycloalkenyl, linear or branched C2-C8-alkynyl, C6-C14-aryl or form C3-C12-cycloalkyl or C5-C12-cycloalkenyl together with the connecting C atom;
R3, R4, R5, R6 and R7 are the same or different and are independently selected from H, linear or branched C1-C8-alkyl, linear or branched C2-C8-alkenyl, C1-C8-alkoxy, C2-C8-alkenyloxy, C3-C8-cycloalkyl, C6-C14-aryl, C3-C8-cycloalkoxy, C7-C15-arylalkoxy, C9-C15-alkenylarylalkoxy, N(R8)2 or SR8 with R8 being selected from linear or branched C1-C8-alkyl, linear or branched C2-C8-alkenyl, C6-C14-aryl, C1-C8-alkoxy, C2-C8-alkenyloxy, C3-C8-cycloalkyl, C3-C8-cycloalkoxy, C7-C15-arylalkoxy, C9-C15-alkenylarylalkoxy, or R8 form a C3-C9-alicyclic system together with the connecting N atom, optionally one or more carbon atoms are replaced with O, or two adjacent R form an aromatic system together with the benzene ring of formula I;
Z is selected from OR9, NHR9 and NR10R11 with R9, R10 and R11 being independently selected from H, linear or branched C1-C8-alkyl, linear or branched C2-C8-alkenyl, C1-C8-alkoxy, C2-C8-alkenyloxy, C3-C8-cycloalkyl, C3-C8-cycloalkoxy, C6-C14-aryl, C7-C15-arylalkyl, C7-C15-arylalkoxy, C9-C15-alkenylarylalkoxy, C9-C15-alkenylarylalkyl; or R10 and R11 form a C3-C9-alicyclic system together with the connecting N or C atom, optionally one or more carbon atoms are replaced with O;
the process comprising:
contacting under phase-transfer conditions a ketone of the general formula II

OG Complex Work Unit Chemistry
wherein R1, R2, R3, R4, R5, R6 and R7 are as defined above;
with an at least partially halogenated C2-C8-alkane and/or C2-C8-alkene selected from hexachloroethane, tetrachloroethylene and mixtures thereof, and
a base selected from the group comprising alkali metal hydroxide, earth alkali metal hydroxide, alkali metal C1-C8-alkoxide, earth alkali metal C1-C8-alkoxide and mixtures thereof, or a base selected from the group comprising alkali metal hydroxide, earth alkali metal hydroxide, alkali metal C1-C8-alkoxide, earth alkali metal C1-C8-alkoxide and mixtures thereof together with the protonated form of Z as defined above,
wherein the base is added in form of an aqueous solution or the base is added in an organic solvent selected from the group consisting of methanol, ethanol, n-propanol, tert.-butanol, dichloromethane, tetrachloroethylene, ethyl acetate, acetone, N,N-dimethylformamide, dimethylsulfoxide, 1,2-dimethoxyethane, diethyleneqlycol dimethyl ether, triethyleneglycol dimethyl ether, and mixtures thereof.