Process for preparing 1-indanone compounds by intramolecular Friedel-Crafts reaction of alpha,alpha-dialkylmalonate derivatives

Patent metadata

Field	Value
Publication number	US-11952335-B2
Application number	US-202017761016-A
Country	US
Kind code	B2
Filing date	Dec 8, 2020
Priority date	Dec 13, 2019
Publication date	Apr 9, 2024
Grant date	Apr 9, 2024

Abstract

Described herein are valuable new chemical intermediates for producing perfuming ingredients, and a process for producing compound of formula (I).

First claim

The invention claimed is:

1. A process for the preparation of a compound of formula

in the form of any one of its stereoisomers or a mixture thereof, and wherein n is an integer between 0 and 2, each R 1 , independently from each other, represents a substituent of the aromatic ring and is a C 1-6 alkyl group, a C 2-6 alkenyl group or a C 1-6 alkoxy group; R 2 represents a C 1-3 alkyl group; and R 3 represents a hydrogen atom, a C 1-6 alkyl group or a C 2-6 alkenyl group;
comprising the cyclisation of a compound of the formula (II)

in the form of any one of its stereoisomers or a mixture thereof, and wherein n, R 1 , R 2 and R 3 have the same meaning as defined in formula (I); and
A represents a C(O)OC(O)R 4 group, a C(O)Cl group or a COOH group wherein R 4 represents a C 1-6 alkyl group substituted by one or more chlorine or fluorine atoms;
in a presence of a Friedel-Crafts acylation reagent.

2. The process according to claim 1 , wherein the compound of formula (I) is of formula

wherein each R 1 , R 2 and R 3 have the same meaning as defined in claim 1 ;
and said compound of formula (II) is of formula

wherein each R 1 , R 2 , R 3 and A have the same meaning as defined in claim 1 .

3. The process according to claim 1 , wherein A is a COOH group.

4. The process according to claim 1 , wherein R 2 is a methyl group.

5. The process according to claim 1 , wherein R 3 represents a C 1-3 alkyl group.

6. The process according to claim 1 , wherein R 1 , independently from each other, is a C 1-4 alkyl group.

7. The process according to claim 1 , wherein the Friedel-Crafts acylation reagent is an inorganic acid or a Lewis acid.

8. The process according to claim 7 , wherein the inorganic acid is selected from the group consisting of polyphosphoric acid, Eaton's reagent, and perfluorinated ion-exchange resin.

9. The process according to claim 7 , wherein the Lewis acid is of formula M(Y)n, wherein M is a metal selected from the group consisting of Al, B, Bi, Fe, Sn, Zn, In, n represents an integer between 2 and 4, and Y represents a halogen atom or a triflate or acetylacetone.

10. The process according to claim 9 , wherein the Lewis acid is selected from the group consisting of BF 3 ·OEt 2 , Bi(OTf) 3 , AlCl 3 , FeCl 2 , FeCl 3 , FeCl 3 on silica gel 0.4 mmol/g, FeCl 3 ·6H 2 O, InCl 3 , SnCl 4 , Zn(acac) 2 , ZnBr 2 , ZnCl 2 and ZnI 2 .

11. The process according to claim 1 , wherein the cyclisation is performed in a presence of a Lewis acid and an acid anhydride, an organic acid or phosphoryl chloride.

12. The process according to claim 11 , wherein the acid anhydride is selected from the group consisting of trifluoroacetic anhydride, trichloroacetic anhydride, dichloroacetic anhydride, monochloroacetic anhydride and methanesulfonic anhydride.

13. The process according to claim 1 , further comprising the step of converting compound of formula (I) to compound of formula (IV)

wherein each R 1 and n have the same meaning as defined in claim 1 .

14. A compound of formula

in the form of any one of its stereoisomers or a mixture thereof, and wherein n is an integer between 0 and 2, each R 1 , independently from each other, represents a substituent of the aromatic ring and is a C 1-6 alkyl group, a C 2-6 alkenyl group or a C 1-6 alkoxy group; R 2 represents a C 1-3 alkyl group; and R 3 represents a hydrogen atom, a C 1-6 alkyl group or a C 2-6 alkenyl group; provided that 5-methoxy-2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylic acid, methyl 2-ethyl-5-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, methyl 2-ethyl-6-methoxy-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, ethyl 1-oxo-2-propyl-2,3-dihydro-1H-indene-2-carboxylate, methyl 2-ethyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, methyl 2-isopropyl-1-oxo-2,3-dihydro-1H-indene-2-carboxyl ate, methyl 6-methoxy-1-oxo-2-propyl-2,3-dihydro-1H-indene-2-carboxylate, 2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylic acid, methyl 2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, ethyl 2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, allyl 2-methyl-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate, methyl 6-methoxy-2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, tert-butyl 2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, methyl 4-methoxy-2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, methyl 5,6-dimethoxy-2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, methyl 6-isobutyl-2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, ethyl 5-(tert-butyl)-2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate, ethyl 2,5,7-trimethyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate and tert-butyl 5-methoxy-2-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate are excluded.

15. A compound of formula

in the form of any one of its stereoisomers or a mixture thereof, and wherein n is an integer between 0 and 2, each R 1 , independently from each other, represents a substituent of the aromatic ring and is a C 1-6 alkyl group, a C 2-6 alkenyl group or a C 1-6 alkoxy group; R 2 represents a C 1-3 alkyl group; R 3 represents a hydrogen atom, a C 1-6 alkyl group or a C 2-6 alkenyl group and A represents a C(O)Cl group; a C(O)OC(O)R 5 group, and R 5 represents a C 1-6 alkyl group provided that ethyl 3-chloro-2-(4-m ethoxy-3-methylbenzyl)-2-methyl-3-oxopropanoate is excluded.

Assignees

• Firmenich & Cie

Inventors

• Basset Jean-François
• Dupau Philippe
• Magpantay Iris
• Haldimann Sanchez Murielle

Classifications

• C07C61/13 Primary

  having two rings · CPC title

• C07C57/30

  containing six-membered aromatic rings · CPC title

• C07C67/313 Primary

  by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups · CPC title

• C07C2602/08

  the other ring being five-membered, e.g. indane · CPC title

• C07C67/333 Primary

  by isomerisation; by change of size of the carbon skeleton (introduction or elimination of carboxyl groups C07C67/313, C07C67/32) · CPC title