Synthesis of alkyl 2-acetyl-5,9,13-trimethyltetradeca-4,8,12-trienoates and derivatives by a non-continuous production process

Patent metadata

Field	Value
Publication number	US-11274071-B2
Application number	US-201816954671-A
Country	US
Kind code	B2
Filing date	Dec 11, 2018
Priority date	Dec 20, 2017
Publication date	Mar 15, 2022
Grant date	Mar 15, 2022

Abstract

The present invention relates to the manufacturing of a process of alkyl 2-acetyl-5,9,13-trimethyltetradeca-4,8,12-trienoates and alkyl 2-acetyl-9,13-di-methyl-5-methylenetetradeca-8,12-dienoate as well as 6,10,14-trimethylpenta-deca-5,9,13-trien-2-one and 10,14-dimethyl-6-methylenepentadeca-9,13-dien-2-5 one and 6,10,14-trimethylpentadecan-2-one.

First claim

The invention claimed is:

1. A process for manufacturing a compound of formula (I):

wherein the dotted line in formula (I) indicates a carbon-carbon double bond which is located at one of the two indicated positions, wherein
the process comprises reacting at temperature of 77° C. to 87° C. a compound of formula (II) and a compound of formula (Ill):

in a non-continuous process in the presence of either:
i) a mixture of a rhodium complex and water-soluble phosphine salt of formula (IV-a) or (IV-b), or
ii) a rhodium complex obtained from a reaction of a rhodium complex and water-soluble phosphine salt of formula (IV-a) or (IV-b):

and in the presence of water and an organic solvent selected from the group consisting of C 1 -C 5 alcohols, alkylethers of C 1 -C 5 alcohols, C 2 -C 6 alkane diols, monoalkylethers of C 2 -C 6 alkane diols, dialkylethers of C 2 -C 6 alkane diols, esters of C 1 -C 6 carboxyl acids or diacids, lactones and lactames; wherein R 1 is a C 1-10 -alkyl group, n is an integer of 1-4, and M n+ is an organic or inorganic cation having a charge +n, and
wherein

the process achieves conversions and selectivities of the compound of formula (I) of higher than 90%.

2. The process according to claim 1 , wherein the water-soluble phosphine salt is of formula (IV-a).

3. The process according to claim 1 , wherein the rhodium complex is a rhodium (I) complex coordinating two alkenes or a diene as ligand.

4. The process according to claim 1 , wherein the rhodium complex is [Rh(COD)X] 2 wherein COD stands for cycloocta-1,5-diene and X is a halide.

5. The process according to claim 1 , wherein the rhodium complex and water-soluble phosphine salt of formula (IV-a) or (IV-b) are present in a molar ratio of the rhodium complex to the water-soluble phosphine salt of formula (IV-a) or (IV-b) which is 3-50.

6. The process according to claim 1 , wherein the compound of formula (III) and the compound of formula (II) are present in a molar ratio of the compound of formula (III) to the compound of formula (II) which is 1-5.

7. The process according to claim 1 , wherein the rhodium complex and the compound of formula (II) are present in molar amounts such that the molar amount of the rhodium complex is between 0.01-0.5 mol-%, with respect to the molar amount of the compound of formula (II).

8. The process according to claim 1 , wherein the step of reacting the compound of formula (II) and the compound of formula (III) is performed in the presence of water and an alcohol in a volume ratio of the water to the alcohol of 5:1-1:10.

Assignees

• Dsm Ip Assets Bv

Inventors

• Joray Marcel
• Stemmler René Tobias

Classifications

• C07C45/676

  by elimination of carboxyl groups · CPC title

• C07C45/65 Primary

  by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups · CPC title

• C07C45/62 Primary

  by hydrogenation of carbon-to-carbon double or triple bonds · CPC title

• C07C49/04

  Saturated compounds containing keto groups bound to acyclic carbon atoms · CPC title

• C07C51/373

  by introduction of functional groups containing oxygen only in doubly bound form · CPC title