Method for making end compounds from internal ketones issued from the decarboxylative ketonization of fatty acids or fatty acid derivatives

Patent metadata

Field	Value
Publication number	US-11267781-B2
Application number	US-201716347977-A
Country	US
Kind code	B2
Filing date	Nov 8, 2017
Priority date	Nov 8, 2016
Publication date	Mar 8, 2022
Grant date	Mar 8, 2022

Abstract

Method (M) for the preparation of an end compound from an internal ketone, said method comprising: —synthesizing the internal ketone by a process (P) for the decarboxylative ketonization of a fatty acid, a fatty acid derivative or a mixture thereof in a liquid phase with a metal compound as catalyst in the substantial absence of added solvent, wherein the fatty acid, fatty acid derivative or mixture thereof is added in sequential steps, the first step taking place at a temperature sequentially at a temperature from 100° C. to 270° C., —causing the internal ketone to react in accordance with a single or multiple chemical reaction scheme involving at least one reagent other than the internal ketone, wherein at least one product of the chemical reaction scheme is the end compound that is not further caused to be chemically converted into another compound.

First claim

The invention claimed is:

1. A method M for the preparation of at least one end compound from at least one internal ketone, said method M comprising:
synthesizing the internal ketone by a process P for the decarboxylative ketonization of at least one fatty acid, at least one fatty acid derivative or a mixture thereof in a liquid phase with a metal compound as catalyst, wherein
a) in a first step, elementary metal or a metal compound and the fatty acid, fatty acid derivative or mixture thereof comprising at least 10 mol %, based on the entire amount of fatty acid or fatty acid derivative, of fatty acid having 12 carbon atoms or less or derivative of fatty acid having 12 carbon atoms or less, are mixed in a molar ratio of from 1:0.8 to 1:3.5 (molar ratio metal:carboxyl group equivalent) and reacted for a period P 1 of from 5 min to 24 h at a temperature T 1 of from 100° C. to 270° C. in the substantial absence of added solvent, and
b) thereafter the temperature is raised to a temperature T 2 which is strictly above 270° C. and up to 400° C., and additional fatty acid, fatty acid derivative or a mixture thereof comprising at least 10 mol %, based on the entire amount of fatty acid or fatty acid derivative, of fatty acid having 12 carbon atoms or less or derivative of such fatty acid, is added over a period of time P 2 of from 5 min to 24 h in the substantial absence of added solvent until the molar ratio of fatty acid, fatty acid derivative or mixture thereof to metal is in the range of from 6:1 to 99:1,

and
causing the internal ketone to react in accordance with a single or multiple chemical reaction scheme involving at least one reagent other than the internal ketone, wherein at least one product of the chemical reaction scheme is the end compound that is not further caused to be chemically converted into another compound,

with the proviso that
when the internal ketone is caused to react by being subjected to a hydrogenation reaction to obtain a secondary alcohol, the so-obtained secondary alcohol is an intermediate that is in turn caused to react in accordance with a single or multiple reaction scheme that does not include a dehydration reaction that would convert said internal secondary alcohol into an internal olefin as an other intermediate or as the end compound, and
the end compound differs from an α-sulfocarbonyl compound C1* of formula (1)

from an α-sulfocarbonyl compound C2* of formula (2)

and from a mixture thereof,
wherein in above formulae (1) and (2)
R 1 , R 3 and R 5 , which may be the same or different at each occurrence, are hydrogen or a linear or branched alkyl chain having 1 to 20 carbon atoms,
R 2 and R 4 , which may be the same or different at each occurrence, are a linear or branched alkyl group having 4 to 24 carbon atoms and in which the alkyl chain may comprise one or more cycloaliphatic groups, and
X is H or a cation forming a salt with the sulfonate group, and

the end compound further differs from a surfactant C3* of formula (3)

from a diamine C4* of formula (4)

and from a mixture thereof,
wherein in above formulae (3) and (4)
each of R a and R b , which are identical or different, is a linear or branched, saturated or unsaturated, hydrocarbon chain that may be interrupted and/or substituted by at least a monocyclic or polycyclic group
each of R c and R d , which are identical or different, is a linear or branched, alkyl chain having 1 to 10 carbon atoms
each of (E 1 ) and (E 2 ) is a divalent hydrocarbon radical linear or branched, not substituted or substituted,
A is: a carboxylate group —COO − , optionally in all or part in its protonated form —COOH; or a sulfonate group —SO 3 − , optionally in all or part in its protonated form —SO 3 H.

2. The process according to claim 1 wherein temperature T 1 is from 230° C. to 270° C.

3. The process according to claim 1 wherein temperature T 2 is from 280° C. to 320° C.

4. The method according to claim 1 wherein step a) is carried out at a temperature T 1 of from 190° C. to 260° C. for a duration of from 15 min to 120 min and the fatty acid, fatty acid derivative or mixture thereof in step b) is added over a period P 2 of from 2 hours to 12 hours.

5. The method according to claim 1 wherein, after the temperature has been raised to T 2 and before the additional fatty acid, fatty acid derivative or mixture thereof is added over period of time P 2 , said temperature is maintained at temperature T 2 during a period of time P 12 of from 30 min to 300 min.

6. The method according to claim 1 wherein, after the additional fatty acid, fatty acid derivative or mixture thereof has been added over period of time P 2 , the temperature is maintained at temperature T 2 during a period of time P 23 of from 30 min to 300 min.

7. The method according to claim 1 wherein the internal ketone is caused to react directly with at least one reagent selected from the group consisting of ammonia, primary or secondary amines, mixtures of at least one aldehyde with ammonia or with at least one primary or secondary amine, and alkylating agents; and wherein the end compound is selected from the group consisting of twin tail primary, secondary or tertiary amines, twin-tail tertiary amines themselves substituted by one or two primary, secondary or tertiary amino groups, internal ketone monoamines, internal ketone diamines, (poly)aminocarboxylates twin-tail amines, twin tail quaternary ammonium salts, internal ketone mono-quaternary ammonium salts, internal ketone di-quaternary ammonium salts, aminoxide twin-tail amines, aminoxide Gemini compounds, dibetaine or disultaine twin-tail amines and betaine or sultaine Gemini compounds.

8. The method according to claim 1 wherein the internal ketone is caused to react directly with at least one reagent selected from the group consisting of diesters derived from tartaric acid, phenol and other aromatic mono- or polyalcohols, formaldehyde, pentareythritol, acrylates derivatives and hydrogen; and wherein the end compound is selected from the group consisting of dicarboxylate salt derivatives, non-ionic surfactants having a Gemini structure and ethylenically unsaturated monomers.

9. The method according to claim 1 wherein the end compound has a twin-tail Gemini structure.

10. The method according to claim 1 wherein the end compound is a surfactant.

11. The method according to claim 1 wherein the at least one internal ketone synthesized by the process P is a compound of formula (I)

wherein R n and R m independently represent a C 3 -C 27 aliphatic group.

12. The method according to claim 11 , wherein the at least one internal ketone of formula (I) is reacted with at least one amine of formula (II) under reductive amination conditions to afford the at least one twin-tail amine of formula (III)

wherein in the above amine formula (II), R 1 and R 2 independently represent:
hydrogen or a linear or branched hydrocarbon radical having 1 to 24 carbon atoms which can be optionally

Assignees

• Rhodia Operations

Inventors

• Back Olivier
• Leroy Rémy
• Marion Philippe

Classifications

• C07C41/03

  by reaction of oxirane rings with hydroxy groups · CPC title

• C07C45/48 Primary

  involving decarboxylation · CPC title

• C07C29/145

  with hydrogen or hydrogen-containing gases · CPC title

• C07C67/03

  by reacting an ester group with a hydroxy group · CPC title

• C07C225/06

  and acyclic · CPC title