Method for the preparation of omega-amino-carboxylic acids and derivatives thereof

Patent metadata

Field	Value
Publication number	US-12486468-B2
Application number	US-202218686577-A
Country	US
Kind code	B2
Filing date	Aug 9, 2022
Priority date	Aug 25, 2021
Publication date	Dec 2, 2025
Grant date	Dec 2, 2025

Abstract

A Method for the synthesis of ω-amino acids or derivatives thereof, includes the following steps synthesis of an ω-oxoester/linear acid by hydroformylation by CO/H 2 mixture of at least one monounsaturated acid/ester, the monounsaturated acid/ester preferably resulting from a reaction of metathesis of oils/fats from renewable sources; synthesis of a linear ω-amino acid/ester and/or ω-aminoamide, subjecting the aforementioned ω-oxoester/linear acid to reductive amination; and possible synthesis of a linear ω-amino acid, subjecting the aforementioned linear ω-aminoester and/or ω-aminoamide to hydrolysis.

First claim

The invention claimed is:

1 . A process for the preparation of an ω-aminocarboxylic acid or a derivative thereof of formula (III), starting from an ω-unsaturated carboxylic compound with the following formula (I):
H 2 C═CR′-(Q)-COR″  (I)

wherein R′ is H or an aliphatic hydrocarbon group, possibly substituted, with 1 to 10 carbon atoms;
R″ is an OR or NR 1 R 2 group, wherein R is selected from between H, ammonium, a monovalent M metal, a C1-C15 alkyl group and a C6-C15 aryl group;
R 1 and R 2 are independently selected from between H, a C1-C15 alkyl group and a C6-C15 aryl group;
Q is a divalent, aliphatic, optionally substituted hydrocarbon group with 1 to 12 carbon atoms,
and, furthermore, said R′ and Q groups can be linked together to form an aliphatic carbocyclic structure with 5 to 7 carbon atoms;
said process comprising the following stages in sequence:
(A) making said compound of formula (I) react under the hydroformylation conditions with a mixture of hydrogen and carbon monoxide in the presence of a hydroformylation catalyst, based on rhodium (I) and phosphine binders and, optionally, a solvent, to obtain the corresponding ω-oxocarboxylic derivative with the following formula (II):
HOC—CH 2 —CHR′-(Q)-COR″  (II)

with R′, R″ and Q correspondingly having the meaning specified above,
(B) subjecting said compound of formula (II) as obtained in step (A), in the absence of intermediate purification steps of the compound of formula (II) from the other reaction products, to reductive amination by reaction with hydrogen and ammonia in the presence of a catalyst to obtain the ω-aminocarboxylic derivative of formula (III):
H 2 N—CH 2 —CH 2 —CHR′-(Q)-COR″  (III)

and separating it from any reaction solvent;
(C) optionally subjecting said compound of formula (III) to hydrolysis to obtain the corresponding ω-aminocarboxylic acid wherein R″ in formula (III) is OH.

2 . The process according to claim 1 , wherein the hydroformylation reaction in said step (A) is carried out at a temperature of between 6° and 140° C. and at a pressure of between 1.5 and 6 MPa, in a solvent selected from between an ether, an alcohol or an aromatic solvent.

3 . The process according to claim 1 , wherein the hydroformylation reaction in said step (A) is carried out in the presence of a catalyst comprising a ligand comprising at least one phosphine and a soluble salt or complex of a metal selected from the group consisting of Rhodium, Cobalt, Iridium, and Ruthenium.

4 . The process according to claim 3 , wherein said catalyst comprises a rhodium complex selected from between HRh(CO)(PPh 3 ) 3 , (acac)Rh(CO) 2 , [Rh(COD)Cl] 2 and a bidentate or polidentate phosphine.

5 . The process according to claim 1 , wherein the reaction mixture obtained in step (A) is transferred to step (B) without carrying out any separation step except for the evaporation of at least a part of the possible solvent and recovery of the catalyst with one of the methods known in literature.

6 . The process according to claim 1 , wherein said reductive amination stage (B) is carried out with ammonia in the presence of hydrogen at a temperature of between 30 and 200° C., and at a pressure between 3 and 15 MPa.

7 . The process according to claim 1 , wherein said reductive amination step (B) is carried out in the presence of a catalyst comprising cobalt or nickel.

8 . The process according to claim 1 , wherein, in said stage (B), ammonia and hydrogen are in an NH 3 /H 2 molar ratio of between 5 and 25.

9 . The process according to claim 1 , wherein, in the compound of formula (III) obtained in step (B), R″ is an —OR group with R═C1-C5 alkyl and said hydrolysis step (C) is carried out in an aqueous environment, in the presence of an acidic or basic catalyst.

10 . The process according to claim 1 , wherein said ω-unsaturated carboxylic compound of formula (I) is an ester of 9-decenoic acid.

11 . The process according to claim 1 , for the preparation of 11-aminoundecanoic acid.

12 . A lubricating composition comprising a base oil and at least one additive wherein said additive and/or said base oil is a ω-aminocarboxylic acid of formula (III) or a derivative thereof of formula (III), said ω-aminocarboxylic acid of formula (III) and/or said derivative thereof of formula (III) being obtained according to the process recited in claim 1 .

13 . The lubricating composition according to claim 12 , wherein said ω-aminocarboxylic acid or a derivative thereof of formula (III) derives from an ω-unsaturated carboxylic compound of formula (I) of renewable origin, starting from methyl 9-decenoate (9-DAME) obtained from the reaction of metathesis of vegetable oils and fats from renewable sources.

14 . A bio-lubricant according to claim 13 , where a percentage content of carbon from renewable raw materials on the entire formulation is at least one percent (1%) by weight and derives from ω-aminocarboxylic acid of formula (III) or a derivative thereof of formula (III).

15 . A bio-lubricant according to claim 13 , where a percentage content of carbon from renewable raw materials is at least 25% by weight on a single component from ω-aminocarboxylic acid and derives from the ω-aminocarboxylic acid of formula (III) or a derivative thereof of formula (III).

16 . The bio-lubricant according to claim 15 , wherein said percentage content of carbon from renewable raw materials is at least 50%.

17 . A method for the preparation of a lubricating or biolubricating composition comprising the preparation of an ω-aminocarboxylic acid of formula (III) or a derivative thereof of formula (III) according to the process according to claim 1 and, in addition, the additional step and subsequent to introduce said ω-aminocarboxylic acid, a derivative thereof of formula (III) or a further derivative of one of the above, in a composition comprising at least one lubricating base (base oil).

18 . The process according to claim 1 , wherein the hydroformylation catalyst is based on rhodium (I) and phosphine binders.

19 . The process according to claim 1 , wherein step (B) is in the absence of intermediate purification steps of the compound of formula (II) from the other reaction products.

20 . The process according to claim 2 , wherein the hydroformylation reaction is carried out in a solvent selected from between an ether, an alcohol or an aromatic solvent.

21 . The lubricating composition according to claim 13 , wherein said ω-aminocarboxylic acid or a derivative thereof of formula (III) derives from methyl 9-decenoate (9-DAME) obtained from the reaction of metathesis of vegetable oils and fats from renewable sources.

Assignees

• Versalis Spa

Inventors

• Vecchini Nicola
• Nodari Mirco
• Galeotti Armando
• Delledonne Daniele

Classifications

• C10M169/04

  Mixtures of base-materials and additives · CPC title

• C10M2203/003

  used as base material · CPC title

• C10M2215/26

  Amines · CPC title

• C07C227/08

  by reaction of ammonia or amines with acids containing functional groups · CPC title

• C10M133/04

  Amines, e.g. polyalkylene polyamines; Quaternary amines (polyalkylene polyamines with eleven or more monomer units C10M149/22) · CPC title