Method for the homogeneous catalytic reductive amination of carbonyl compounds

• US 10,450,261 B2
• Filed: 05/27/2016
• Issued: 10/22/2019
• Est. Priority Date: 05/28/2015
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Schaub, Thomas, Gallardo Donaire, Joan, Ernst, Martin
• Primary Examiner(s): Ward, Paul V
• Application Number:
  US15/577,393
• Publication Number:
  US 20180186725A1
• Time in Patent Office: 1,243 Days
• CPC Class Codes: B01J 2231/4283 using N nucleophiles, e.g. Buchwald-Hartwig amination
• CPC Class Codes: B01J 2231/44 Allylic alkylation, amination, alkoxylation or analogues
• CPC Class Codes: B01J 2231/643 of R2C=O or R2C=NR (R= C, H)
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 31/185 Phosphites ((RO)3P) , their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
• CPC Class Codes: B01J 31/20 Carbonyls
• CPC Class Codes: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: B01J 31/2409 with more than one complexing phosphine-P atom
• CPC Class Codes: B01J 31/2414 comprising aliphatic or saturated rings
• CPC Class Codes: B01J 31/2433 comprising aliphatic or saturated rings
• CPC Class Codes: C07B 2200/07 Optical isomers
• CPC Class Codes: C07C 209/26 by reduction with hydrogen
• CPC Class Codes: C07C 211/03 Monoamines
• CPC Class Codes: C07C 211/27 having amino groups linked to the six-membered aromatic ring by saturated carbon chains
• CPC Class Codes: C07C 211/29 the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
• CPC Class Codes: C07C 211/30 the six-membered aromatic ring being part of a condensed ring system formed by two rings
• CPC Class Codes: C07C 211/42 with six-membered aromatic rings being part of the condensed ring systems
• CPC Class Codes: C07C 213/02 by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
• CPC Class Codes: C07C 217/58 with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
• CPC Class Codes: C07C 2602/08 the other ring being five-membered, e.g. indane
• CPC Class Codes: C07D 265/30 : not condensed with other rings
• CPC Class Codes: C07D 317/58 : Radicals substituted by nitrogen atoms nitro radicals C07D317/52
• CPC Class Codes: C07F 17/02 : of metals of Groups 8, 9 or 10 of the Periodic System

Abstract

The present invention relates to a method for the reductive amination of a carbonyl compound, comprising one or more carbonyl groups amenable to reductive amination, forming the corresponding primary amine, characterized in that the reaction is carried out in the presence of a homogeneously dissolved catalyst complex K, comprising at least one metal atom from Group 8, 9 or 10 of the periodic table, bearing a bidentate phosphane ligand, a carbonyl ligand, a neutral ligand and a hydride ligand, and also an acid as co-catalyst.

Claims

1. A method for the reductive amination of a carbonyl compound, comprising one or more carbonyl groups amenable to reductive amination, characterized in that the reaction is carried out in the presence of a homogeneously dissolved catalyst K and an acid as co-catalyst, in which the catalyst K is a ruthenium catalyst, comprising, a bidentate phosphane ligand, a carbonyl ligand, a hydride ligand and optionally a neutral ligand.

2. The method according to claim 1, wherein the bidentate phosphane ligand has the following formula III:

3. The method according to claim 2, wherein the bidentate phosphane ligand is selected from compounds of the formula III,

where

X¹, X², X³, X⁴, X⁵ and X⁶ are mutually independently optionally substituted C₁-C₆-alkylene, O, —

(C═

O)—

NE⁷-ferrocenyl, ferrocenyl-NE⁷-(C═

O)—

, —

(C═

O)—

NE⁷- or —

NE⁷-(C═

O)—

, where E⁷ is as defined above;

Y, a, b, c, d, e and f are as defined above;

R^A, R^B, R^C and R^D are residues mutually independently selected from C₁-C₃₀-alkyl, C₄-C₁₀-cycloalkyl, C₃-C₁₀-heterocyclyl, C₅-C₁₄-aryl or C₅-C₃₀-hetaryl, wherein said residues are mutually independently optionally mono- or polysubstituted, wherein the substituents are mutually independently selected from C₁-C₁₀-alkyl, C₄-C₁₀-cycloalkyl, C₃-C₁₀-heterocycloalkyl, C₅-C₁₄-aryl, C₅-C₃₀-hetaryl, C₁-C₁₀-alkoxy, C₃-C₁₀-cycloalkoxy, C₃-C₁₀-heterocycloalkoxy, C₅-C₁₄-aryloxy, C₅-C₃₀-hetaryloxy, hydroxyl, mercapto, poly-C₂-C₆-alkylene oxide, poly-C₂-C₆-alkylenimine, COOH, carboxylate, SO₃H, sulfonate, halogen, nitro, formyl, C₁-C₁₀-acyl, cyano, NE¹E², and NE¹E²E³⁺X⁻

, where E¹, E² and E³ are each identical or different residues selected from hydrogen, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl, or C₅-C₁₀-aryl and X³¹ is an anion equivalent;

or

R^A and R^B and/or R^C and R^D together with the phosphorus atom and, if present, the groups X¹, X², X⁵ and X⁶ to which they are bound, are a 4- to 8-membered heterocycle or heterobicycle, which is optionally additionally fused to C₄-C ₁₀-cycloalkyl, C₃-C₁₀-heterocycloalkyl, C₅-C₁₄-aryl or C₅-C₃₀-hetaryl, wherein the heterocycle or heterobicycle and, if present, the fused groups, are mutually independently optionally substituted, wherein the substituents are selected from C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl, C₃-C₁₀-heterocycloalkyl, C₅-C₁₄-aryl, C₅-C₃₀-hetaryl, hydroxyl, mercapto, poly-C₂-C₆-alkylene oxide, poly-C₂-C₆-alkylenimine, C₁-C₁₀-alkoxy, halogen, COOH, carboxylate, SO₃H, sulfonate, NE⁴E⁵, NE⁴E⁵E⁶⁺X³¹ , nitro, C₁-C₁₀-alkoxycarbonyl, formyl, C₁-C₁₀-acyl and cyano, where E⁴, E⁵ and E⁶ are each identical or different residues selected from hydrogen, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl and C₅-C₁₄-aryl and X⁻

is an anion equivalent;

or

one of the residues R^A and R^B and/or one of the residues R^C and R^D together with the phosphorus atom and, if present, the groups X¹, X², X⁵ and X⁶ to which they are bound, and together with a bridging group atom of the bridging group Y, are a 5- to 8-membered heterocycle, which is optionally additionally fused to C₃-C₁₀-cycloalkyl, C₃-C₁₀-heterocycloalkyl, C₅-C₁₄-aryl or C₅-C₃₀-hetaryl, wherein the heterocycle and, if present, the fused groups, are in addition mutually independently optionally substituted, wherein the substituents are selected from C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl, C₃-C₁₀-heterocycloalkyl, C₅-C₁₄-aryl, C₅-C₃₀-hetaryl, hydroxyl, mercapto, poly-C₂-C₆-alkylene oxide, poly-C₂-C₆-alkylenimine, C₁-C₁₀-alkoxy, halogen, COOH, carboxylate, SO₃H, sulfonate, NE⁴E⁵, NE⁴E⁵E⁶⁺X⁻

, nitro, C₁-C₁₀-alkoxycarbonyl, formyl, C₁-C₁₀-acyl and cyano, where E⁴, E⁵ and E⁶ are each identical or different residues selected from hydrogen, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl and C₅-C₁₄-aryl and X⁻

is an anion equivalent.

4. The method according to claim 1, wherein the group Y in the bidentate phosphane ligand of the general formula III is a bridging group selected from the group consisting of:

straight-chain or branched alkylene,

straight-chain or branched alkenylene,

cycloalkylene optionally comprising at least one ring heteroatom selected from the group consisting of N, O and S,

cycloalkenylene optionally comprising at least one ring heteroatom selected from the group consisting of N, O and S,

bi-, tri- and tetracyclic bridging groups;

arylene,

heteroarylene comprising at least one ring heteroatom selected from the group consisting of N, O and S,

heteroalkylene comprising at least one chain heteroatom selected from the group consisting of N, O and S,

heteroalkenylene comprising at least one chain heteroatom selected from the group consisting of N, O and S,

polycyclic bridging groups comprising at least two mutually bound aromatic, heteroaromatic, carbocyclic or heterocyclic, 4- to 8-membered rings; and

metallocene bridging groups comprising at least one metallocene group of the formula

5. The method according to claim 1, wherein the group Y in the bidentate phosphane ligand of the general formula III is a polycyclic bridging group selected from groups of the formulae III.a to III.k

6. The method according to claim 1, wherein the group Y in the bidentate phosphane ligand of the general formula III is a bridging group selected from polycyclic groups III.m to III.o

7. The method according to claim 1, wherein the group Y in the bidentate phosphane ligand of the general formula III is a bridging group selected from the heterocyclic groups V.a to V.h

8. The method according to claim 1, wherein the two phosphane end groups in the bidentate phosphane ligand of the general formula III are mutually independently selected from groups of the formulae VI.a to VI.k

9. The method according to claim 1, wherein the acid co-catalyst is a Lewis acid.

10. The method according to claim 1, wherein the acid co-catalyst is selected from the group consisting of:

[NH₄]TFA, [NH₄]Cl, [NH₄]₂[SO₄], [NH₄]Br, Al(OTf)₃, Sc(OTf)₃, AlCl₃, AlBr₃, BR₃, BCl₃, BBr₃, BF₃, and Al(NO₃)₃.

11. The method according to claim 1, wherein the catalyst K is a ruthenium catalyst having the following formula IV:

12. The method according to claim 1, wherein the amination is carried out enantioselectively by using a catalyst K bearing at least one chiral bidentate phosphane ligand according to formula III above.

13. The method according to claim 1, wherein the carbonyl compound to be aminated is a compound of the following formula II,

14. The method according to claim 1, wherein the catalyst K is formed from a catalyst precursor selected from the following compounds:

[Ru(PPh₃)₃(H)(Cl)(CO)], [Ru(PPh₃)₃(H)₂(CO)], [Ru(PPh₃)₃(Cl)_{2], [Ru(PPh3})₃(Cl)₂(CO)], [Ru(p-cymene)(Cl)₂], [Ru(benzene)Cl₂],_n, [Ru(CO)₂Cp]_n [Ru(CO)₃(Cl)₂][Ru(COD)(allyl)], [Ru(COD)(2-methylallyl)_{2], [RuCl3}*H₂O], [Ru(acetylacetonate)₃], [Ru(DMSO)₄(Cl)₂], Ru₃CO₁₂,[Ru(cyclopentadienyl)(PPh₃)₂(CI)], Ru(cyclopentadienyl)(CO)₂(CI)], [Ru(cyclopentadienyl)(CO)₂H], [Ru(cyclopentadienyl)(CO)₂]₂, [Ru(pentamethylcyclopentadienyl)(CO)₂(CI)], [Ru(pentamethylcylcopentadienyl)(CO)₂H], [Ru(pentamethylcyclopentadienyl)(CO)₂]₂, [Ru(indenyl)(CO)₂(CI)], [Ru(indenyl)(CO)₂(H)], [Ru(indenyl)(CO)₂]₂, ruthenocene, [Ru(binap)Cl₂], [Ru(bipyridine)₂Cl₂*2H₂O], [Ru(COD)Cl₂]₂, [Ru(pentamethylcyclopentadienyl)(COD)(CI)], [Ru₃(CO)₁₂], [Ru(tetraphenylhydroxycyclopentadienyl)(CO)₂(H)], [Ru(PPh₃)₄(H)₂].

15. The method according to claim 1, wherein the catalyst K is used in an amount of 1 to 5000 ppm by weight, based on the total weight of the liquid reaction medium used.

16. The method according to claim 1, wherein the reaction is carried out under the following reaction conditions:

a) temperature in the range of 20 to 250°

C. and/or

b) total pressure in the range of 0.1 to 30 MPa and/or

c) reaction time of 0.1 to 100 h and/or

d) ammonia;

1.5 to 250-fold molar excess, based on the moles of reactant used and/or

e) 1.5 to 250-fold molar excess of hydrogen based on the moles of reactant used.