METHOD FOR SYNTHESIZING NOVEL COMPOUNDS DERIVED FROM 3-HYDROXY-CYLOPENTYL ACETIC ACID

• US 20200131108A1
• Filed: 12/31/2019
• Published: 04/30/2020
• Est. Priority Date: 03/13/2015
• Status: Active Grant

• Current Assignee: L'Oreal SA
• Original Assignee: L'Oreal SA
• Inventors: DALKO, Maria, MARAT, Xavier, HITCE, Julien, LI, Chao-Jun
• Granted Patent: US 10,995,051 B2
• Time in Patent Office: Days
• CPC Class Codes: A61K 8/365 Hydroxycarboxylic acids; Ketocarboxylic acids
• CPC Class Codes: A61P 17/00 Drugs for dermatological disorders
• CPC Class Codes: A61Q 17/00 Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: C07C 2601/08 the ring being saturated
• CPC Class Codes: C07C 2601/10 the ring being unsaturated
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 45/54 of compounds containing doubly bound oxygen atoms, e.g. esters
• CPC Class Codes: C07C 45/69 by addition to carbon-to-carbon double or triple bonds
• CPC Class Codes: C07C 47/27 containing six-membered aromatic rings
• CPC Class Codes: C07C 47/273 containing halogen
• CPC Class Codes: C07C 49/747 containing six-membered aromatic rings
• CPC Class Codes: C07C 51/09 from carboxylic acid esters or lactones
• CPC Class Codes: C07C 51/38 by decarboxylation
• CPC Class Codes: C07C 59/11 containing rings
• CPC Class Codes: C07C 59/48 containing six-membered aromatic rings
• CPC Class Codes: C07C 59/54 containing six-membered aromatic rings and other rings
• CPC Class Codes: C07C 59/56 containing halogen
• CPC Class Codes: C07C 59/72 containing six-membered aromatic rings and other rings
• CPC Class Codes: C07C 67/347 by addition to unsaturated carbon-to-carbon bonds
• CPC Class Codes: C07C 69/675 : of saturated hydroxy-carboxylic acids
• CPC Class Codes: C07C 69/716 : Esters of keto-carboxylic acids or aldehydo-carboxylic acids
• CPC Class Codes: C07C 69/732 : of unsaturated hydroxy carboxylic acids
• CPC Class Codes: C07C 69/734 : Ethers
• CPC Class Codes: C07C 69/738 : Esters of keto-carboxylic acids or aldehydo-carboxylic acids
• CPC Class Codes: C07C 69/757 : having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
• CPC Class Codes: C07D 213/30 : Oxygen atoms

Abstract

The present invention relates to compounds of formula (I):

in which R1 is a hydrogen atom, a phenyl radical, or a straight or branched, saturated or unsaturated hydrocarbon radical having 1 to 8 carbon atoms.

Claims

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

2. The process as claimed in claim 1 for preparing a compound of formula (I), wherein R1 is as defined in claim 1, and

R2 denotes a linear, saturated hydrocarbon-based radical containing 3 to 12 carbon atoms, substituted with 1 to 3 groups, which may be identical or different, chosen from —

OR31, —

NHR31, —

COOR31, —

OCOR31 and halogens, with R31 representing a hydrogen atom, a phenyl radical or a linear or branched, saturated or unsaturated alkyl radical containing 1 to 4 carbon atoms, or

R2 denotes a radical chosen from a cyclic, saturated hydrocarbon-based radical containing 5 to 7 carbon atoms, possibly substituted with 1 to 3 groups, which may be identical or different, chosen from —

OR31, —

NHR31, —

COOR31, —

OCOR31 and halogens, with R31 representing a hydrogen atom, a phenyl radical or a linear or branched, saturated or unsaturated alkyl radical containing 1 to 4 carbon atoms;

R2 denotes a branched, saturated hydrocarbon-based radical containing 3 to 12 carbon atoms, optionally substituted with 1 to 3 groups, which may be identical or different, chosen from —

OR31, —

NHR31, —

COOR31, —

OCOR31 and halogens, with R31 representing a hydrogen atom, a phenyl radical or a linear or branched, saturated or unsaturated alkyl radical containing 1 to 4 carbon atoms.

3. The process as claimed in claim 1, wherein the compound of formula (I) is chosen from the following compounds:

4. The process as claimed in claim 1 for preparing a compound of formula (I), wherein R1 is as defined in claim 1, and R2 denotes a radical —

Ar—

R22 with Ar being a phenyl or pyridyl aromatic nucleus and

R22 represents a substituent of the aromatic nucleus Ar chosen from hydrogen, —

OR′

, —

NO₂, —

F, —

Br, —

NH₂, —

CF₃ and —

R′

, with R′

representing a hydrogen atom, a linear, branched or cyclic, saturated hydrocarbon-based radical containing 1 to 4 carbon atoms or a phenyl radical.

5. The process as claimed in claim 1 for preparing a compound of formula (I), wherein R1 is as defined in claim 1, and R2 is a radical —

R23Ph with R23 representing a linear saturated or unsaturated hydrocarbon-based radical containing 1 to 6 carbon atoms, optionally substituted with 1 —

OH group and/or optionally interrupted with 1 oxygen atom, with the exclusion of the compounds

6. The process as claimed in claim 1 for preparing a compound of formula (I), wherein R1 is as defined in claim 1, and R2 is a radical —

R24-NH—

R34 with R24 representing a linear, saturated divalent hydrocarbon-based radical containing 1 to 4 carbon atoms and R34 representing a substituent —

COOR′

or a linear saturated hydrocarbon-based radical containing 1 to 4 carbon atoms, optionally interrupted with an oxygen atom, R′

representing a linear or branched, saturated hydrocarbon-based radical containing 1 to 4 carbon atoms.

7. The process as claimed in claim 1 for preparing a compound of formula (I), wherein R1 is as defined in claim 1, and R2 is a radical —

CO—

O—

R25 and —

R25 represents a hydrogen atom or a linear or branched, saturated hydrocarbon-based radical containing 1 to 4 carbon atoms, with the exclusion of the compound

8. The process as claimed in claim 1, wherein step a) is carried out in the presence of a catalyst which is a palladium complex.

9. The process as claimed in claim 1, wherein step a) is carried out in the presence of a catalyst chosen from Pd(OAc)₂, Pd(TFA)₂, Pd(OPiv)₂, PdCl₂ and Pd₂dba₃ optionally combined with a phosphine or a rhodium complex optionally combined with a phosphine.

10. The process as claimed in claim 1, wherein, in step a), the alkyne and the acrolein are heated to a temperature of between 30°

C. and 140°

C. in an organic solvent.

11. The process as claimed in claim 1, wherein step a) is carried out in the presence of a catalyst which is Pd(OAc)₂ combined with a phosphine of formula PMe₃, brought into contact in a Pd(OAc)₂/PMe₃ mole ratio of approximately 1/3.

12. The process as claimed in claim 1, wherein, in step a), the alkyne and the acrolein are heated to a temperature of between 30°

C. and 140°

C. in an organic solvent which is a mixture of at least 2 miscible or immiscible solvents chosen from toluene, benzene, water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, THF, Me-THF, diethyl ether, diisopropyl ether, dichloromethane and acetonitrile.