US 12,441,700 B2
Hydrogenation of imines with RU complexes
Lionel Saudan, Satigny (CH)
Assigned to FIRMENICHI SA, Satigny (CH)
Appl. No. 17/601,296
Filed by FIRMENICH SA, Satigny (CH)
PCT Filed Jul. 30, 2020, PCT No. PCT/EP2020/071564
§ 371(c)(1), (2) Date Oct. 4, 2021,
PCT Pub. No. WO2021/023627, PCT Pub. Date Feb. 11, 2021.
Claims priority of application No. 19190783 (EP), filed on Aug. 8, 2019.
Prior Publication US 2022/0162181 A1, May 26, 2022
Int. Cl. C07D 333/20 (2006.01); B01J 31/18 (2006.01); B01J 31/24 (2006.01); C07F 15/00 (2006.01)
CPC C07D 333/20 (2013.01) [B01J 31/189 (2013.01); B01J 31/2404 (2013.01); C07F 15/0053 (2013.01); B01J 2231/643 (2013.01); B01J 2531/821 (2013.01)] 15 Claims
 
1. A process for the reduction by hydrogenation, using molecular H2, of a C5-C20 substrate of formula

OG Complex Work Unit Chemistry
wherein Ra and Rc represent, independently from each other, a hydrogen atom or a C1-C15 hydrocarbon group optionally comprising one to three oxygen atoms and/or one to two nitrogen atoms and/or one sulphur or halogen atom; Rb represent a C1-C15 hydrocarbon group optionally comprising one to three oxygen atoms and/or one to two nitrogen atoms and/or one sulphur or halogen atom, a hydrogen atom, a SO2Rb′, a ORb″, or a PORb′2 group, wherein Rb′ represents a C1-C6 alkyl group or a phenyl or tolyl group and Rb″ represents a hydrogen atom, a C1-C6 alkyl group, or a phenyl or tolyl group; or Ra and Rc represent, when taken together, a C1-C10 alkanediyl or alkenediyl group; provided than at least one Ra, Rb, or Rc is not a hydrogen atom;
into the corresponding amine, characterized in that said process is carried out in the absence of base and in the presence of at least one catalyst or pre-catalyst of formula absence of base and in the presence of at least one catalyst or pre-catalyst of formula
[Ru(PP)(P)m(NN)n(Y)2]  (1) or
[Ru(P)2(P)m(NN)n(Y)2]  (1′)
wherein m is 0 when n is 0 or 1 or m is 1 when n is 0;
PP represents a C5-C50 bidentate ligand wherein the coordinating groups are two phosphino groups;
each P, simultaneously or independently, represents a C3-C30 monodentate ligand;
NN represents a C2-C20 bidentate ligand wherein the coordinating atoms are two nitrogen atoms; and
each Y represents, simultaneously or independently, a hydrogen or halogen atom.