Process for the selective catalytic hydrogenation of dienones

Patent metadata

Field	Value
Publication number	US-2025074854-A1
Application number	US-202318728126-A
Country	US
Kind code	A1
Filing date	Jan 12, 2023
Priority date	Jan 13, 2022
Publication date	Mar 6, 2025
Grant date	—

Abstract

The present disclosure provides a catalyst system that is capable of selectively hydrogenating (2,3)/(4,5) and (2,3)/(5,6) dienones with hydrogen gas. Specifically, the present disclosure provides catalysts capable of providing high selectivity for the reduction even in the absence of catalyst poisons such as pyridine, pyrazine, quinoline, and quinoxaline

First claim

1 - 31 . (canceled)

32 . A process for the selective mono hydrogenation of dienones with hydrogen, the method comprising:
1. combining a dienone with one or more solvents or without solvent; 2. adding a catalyst to the mixture of dienone and solvent or to the pure dienone to provide a reaction mixture; 3. contacting the reaction mixture with an atmosphere comprising hydrogen (H 2 ); wherein the catalyst comprises a transition metal and one or more phosphine ligands and/or one or more neutral and/or anionic ligands; and wherein the reaction is performed in the absence of pyridine, pyrazine, quinoline, and quinoxaline.

33 . The process of claim 32 , wherein the catalyst comprises a rhodium or ruthenium metal complex.

34 . The process of claim 32 , wherein the catalyst is formed by reacting a transition metal containing precursor with the ligand to form a transition metal-ligand complex, wherein the metal containing precursor comprises Rh(CO) 2 acac, Rh(III)acetate, or [Ru(COD)(2-methylallyl) 2 ].

35 . The method of claim 34 , wherein the transition metal containing precursor is Rh(CO) 2 acac.

36 . The method of claim 34 , wherein the transition metal containing precursor is [Ru(COD)(2-methylallyl) 2 ].

37 . The method of claim 32 , wherein the one or more ligand is selected from the group consisting of 4,5-bis(dipenylphosphino)-9,9-dimethylxanthene (xantphos), 1,2-bis(diphenylphosphino)ethane (dppe), 1,4-bis(diphenylphosphino)butane (dppb), 1,1′-bis(diphenylphosphino)ferrocene (dppf), (3,5-dioxa-4-phosphacyclohepta[2,1-a:3,4-a′]dinaphthalene-4-yl)dimethylamine (MonoPhos), (R,R) Chiraphos, (S,S) Chiraphos, and triphenylphosphite, and triphenylphosphine (PPh 3 ).

38 . The method of claim 32 , wherein the one or more ligand is selected from the group consisting of 1,1′-bis(diisopropylphosphino)ferrocene (dippf) and 1,4-bis(diphenylphosphino)butane (dppb).

39 . The method of claim 32 , wherein the one or more ligands is combined with the transition metal or transition metal complex in a molar ratio of about 1:1 to about 10:1.

40 . The method of claim 32 , wherein the transition metal complex is present in the reaction in an amount of about 0.01 mol % to about 1.0 mol %.

41 . The method of claim 32 , wherein the ligand is present in the reaction in an amount of about 0.01 mol % to about 10.0 mol %.

42 . The method of claim 32 , wherein the one or more solvents are selected from the group consisting of methanol, 1-butanol, 1-propanol, 2-propanol, tetrahydrofuran, toluene, ethyl acetate, and ethanol.

43 . The method of claim 32 , further comprising one or more co-solvents.

44 . The method of claim 43 , wherein the co-solvent comprises an alkyl benzene.

45 . The method of claim 32 , wherein the atmosphere comprising hydrogen is at a pressure of about 1 bar to 100 bar.

46 . The method of claim 32 , wherein the reaction is performed at a temperature of about 10° C. to about 100° C.

47 . The method of claim 45 , wherein the atmosphere comprising hydrogen further comprises carbon monoxide in an amount of about 1 ppm to about 2000 ppm.

48 . The method of claim 32 , wherein the dienone is a (2,3)/(4,5) unsaturated dienone of Formula I

wherein R 1 is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or a bond to form an optionally substituted 5- or 6-membered ring with R 2 ;
R 2 is hydrogen, C 1 -C 6 alkyl, or a bond to form an optionally substituted 5- or 6-membered ring with R 1 ;
R 3 is hydrogen, C 1 -C 6 alkyl, C 1 -C 10 alkenyl, or aryl;
R 4 is hydrogen, C 1 -C 6 alkyl, C 1 -C 10 alkenyl, aryl, or a bond to form an optionally substituted 5- or 6-membered ring with R 5 ; and
R 5 is hydrogen, C 1 -C 6 alkyl, C 1 -C 10 alkenyl, aryl, or a bond to form an optionally substituted 5- or 6-membered ring with R 4 .

49 . The method of claim 48 , wherein the (2,3)/(4,5) unsaturated dienone comprises β-ionone, 6-methyl-3,5-heptadien-2-one or pseudoionone.

50 . The method of claim 32 , wherein the dienone is a (2,3)/(5,6) unsaturated dienone of Formula II, shown below.

wherein R 6 is C 1 -C 6 alkyl, or C 1 -C 6 alkoxy;
R 7 is hydrogen, or C 1 -C 6 alkyl;
R 8 is hydrogen, C 1 -C 6 alkyl, C 1 -C 10 alkenyl, or aryl;
R 9 is hydrogen, C 1 -C 6 alkyl, C 1 -C 10 alkenyl, or aryl;
R 10 is hydrogen, C 1 -C 6 alkyl, C 1 -C 10 alkenyl, aryl, or a bond to form an optionally substituted 5- or 6-membered ring with R 11 ; and
R 11 is hydrogen, C 1 -C 6 alkyl, C 1 -C 10 alkenyl, aryl, or a bond to form an optionally substituted 5- or 6-membered ring with R 10 .

51 . The method of claim 50 , wherein the (2,3)/(5,6) unsaturated dienone comprises α-ionone.

52 . The method of claim 32 , wherein the active catalyst comprises Rh(CO) 2 acac or Ru(COD)met 2 and one or more of 4,5-bis(dipenylphosphino)-9,9-dimethylxanthene (xantphos), bis[(2-diphenylphosphino)phenyl]ether (DPEphos), bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), 1,1′-bis(diphenylphosphino)ferrocene (dppf), 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP), (4,4,4′,4′,6,6′-hexamethyl-3,3′,4,4′-tetrahydro-2,2′-spirobi[[1]benzopyran]-8,8′-diyl)bis(diphenylphosphane) (SPANPhos), triphenyl phosphite (P(OPh) 3 ), trimethyl phosphite (P(OMe) 3 ), (3,5-dioxa-4-phosphacyclohepta[2,1-a:3,4-a′] dinaphthalene-4-yl) dimethylamine (MonoPhos), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), triphenylphosphine (PPh 3 ), tris(4-methoxyphenyl)phosphane, tris(3,5-bis(trifluoromethyl)phenyl)phosphane, 1,1′-bis(diisopropylphosphino)ferrocene (dippf), and methyldiphenylphosphane.

53 . The method of claim 32 , wherein the catalyst is pre-formed by mixing Rh-precursor and ligand in a solvent under inert atmosphere or under an atmosphere of hydrogen or carbon monoxide or a mix of hydrogen and carbon monoxide in any ratio in a pressure range of 1 bar to 100 bar.

54 . The method of claim 32 , wherein the catalyst is a carbonyl containing Rh-phosphine-catalyst of type L 2 Rh(CO)H or L 3 Rh(CO)H, wherein L is a monodentate phosphine or monodentate phosphite.

Assignees

• Basf Se
• Univ Of Alberta

Inventors

• Schelwies Mathias
• Lundgren Rylan
• Paciello Rocco
• Lizandara Pueyo Carlos

Classifications

• C07C2531/20

  Carbonyls · CPC title

• C07C2531/18

  containing nitrogen, phosphorus, arsenic or antimony · CPC title

• C07C2523/46

  Ruthenium, rhodium, osmium or iridium · CPC title

• C07C2601/16

  the ring being unsaturated · CPC title

• C07C67/303

  by hydrogenation of unsaturated carbon-to-carbon bonds · CPC title