Cyclopropyl ring opening by alpha alkylation of an aldehyde with a polycyclic olefin

Patent metadata

Field	Value
Publication number	US-11267776-B2
Application number	US-201916972081-A
Country	US
Kind code	B2
Filing date	Oct 14, 2019
Priority date	Oct 16, 2018
Publication date	Mar 8, 2022
Grant date	Mar 8, 2022

Abstract

Described herein is a process including alpha alkylation of an aldehyde with a polycyclic olefin followed by a ring opening step in order to provide a compound of formulain a form of any one of its stereoisomers or a mixture thereof and where n represents 1 to 4 and R2 to R5 represent independently of each other, a hydrogen atom or a C1-6 linear alkyl group or a C3-6 branched alkyl group; and R3 and R4 or R5 or, alternatively, R2 and R3 when taken together form a saturated or unsaturated optionally substituted 5 or 6 membered carbocyclic ring.

First claim

The invention claimed is:

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

in a form of any one of its stereoisomers or a mixture thereof and wherein
n represents 1 to 4,
R 1 represents a hydrogen or a C 1-8 linear alkyl group;
R 2 to R 5 represent independently of each other, a hydrogen atom or a C 1-6 linear alkyl group or a C 3-6 branched alkyl group; and
R 3 and R 4 or R 5 or, alternatively, R 2 and R 3 when taken together form a saturated or unsaturated optionally substituted 5 or 6 membered carbocyclic ring;
comprising the step of an alpha alkylation of an aldehyde of formula R 1 —CH 2 —CHO wherein R 1 has the same meaning as described above with an olefin compound being a fused or bridged bicyclic or tricyclic compound with a methylene group in alpha position of a cyclopropyl ring junction;
said step being performed in the presence of a photoredox catalyst, a hydrogen atom transfer donor, a secondary amine and light.

2. The process according to claim 1 , wherein the aldehyde is propanal.

3. The process according to claim 1 , wherein the olefin is a compound of formula

in a form of any one of its stereoisomers or a mixture thereof; and wherein n represents 1 to 4 and R 2 to R 5 represent independently of each other, a hydrogen atom or a C 1-6 linear alkyl group or a C 3-6 branched alkyl group; and R 3 and R 4 or R 5 or, alternatively, R 2 and R 3 when taken together form a saturated or unsaturated optionally substituted 5 or 6 membered carbocyclic ring.

4. The process according to claim 1 , wherein the photoredox catalyst is an organic photocatalyst, an iridium complex, or a ruthenium complex.

5. The process according to claim 1 , wherein the hydrogen atom transfer donor is a thiophenol of formula

wherein each R a represents, independently from each other, a hydrogen atom, a halogen atom, a C 1-2 linear alkyl group, a C 3-4 linear or branched alkyl group, a phenyl group optionally substituted by one to five halogen atoms and/or C 1-4 alkyl or alkoxyl groups or a silyl group trisubstituted with C 1-4 alkyl groups or an aryl group; provided that at most two R a group represent a hydrogen atom.

6. The process according to claim 1 , wherein the compound of formula (I) is selected from the group consisting of 2-methyl-3-(2,3,4,4-tetramethylcyclohex-1-en-1-yl)propanal, 2-methyl-3-(3-methyl-2-pentylcyclopent-1-en-1-yl)propanal, 3-(3-isopropyl-3-methylcyclopent-1-en-1-yl)-2-methylpropanal, and 3-((R)-3-isopropyl-3-methylcyclopent-1-en-1-yl)-2-methylpropanal.

7. A compound of formula

in a form of any one of its stereoisomers or a mixture thereof and wherein n represents 1 to 4; R 1 represents a hydrogen or a C 1-8 linear alkyl group and R 2 to R 5 represent independently of each other, a hydrogen atom or a C 1-6 linear alkyl group or a C 3-6 branched alkyl group; and R 3 and R 4 or R 5 or, alternatively, R 2 and R 3 when taken together form a saturated or unsaturated optionally substituted 5 or 6 membered carbocyclic ring.

8. A method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of the compound of formula (I) as defined in claim 7 .

9. A perfuming composition comprising
i) at least one compound of formula (I) as defined in claim 7 ;
ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and
iii) optionally at least one perfumery adjuvant.

10. A perfumed consumer product comprising at least one compound of formula (I) as defined in claim 7 .

11. The perfumed consumer product according to claim 10 , wherein the product is a perfume, a fabric care product, a body-care product, a cosmetic preparation, a skin-care product, an air care product or a home care product.

12. The perfumed consumer product according to claim 11 , wherein the perfumed consumer product is a fine perfume, a splash or eau de perfume, a cologne, an shave or after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain-care product, a shampoo, a coloring preparation, a color care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair spray, a vanishing cream, a deodorant or antiperspirant, a hair remover, a tanning or sun product, a nail product, a skin cleansing, a makeup, a perfumed soap, shower or bath mousse, oil or gel, or a foot/hand care products, a hygiene product, an air freshener, a “ready to use” powdered air freshener, a mold remover, a furnisher care, a wipe, a dish detergent or hard-surface detergent, a leather care product, or a car care product.

13. The process according to claim 1 , wherein the photoredox catalyst is an iridium complex.

14. The process according to claim 1 , wherein the compound of formula (I) is 3-((R)-3-isopropyl-3-methylcyclopent-1-en-1-yl)-2-methylpropanal.

15. A perfumed consumer product comprising a perfuming composition as defined in claim 9 .

16. The perfumed consumer product according to claim 15 , wherein the product is a perfume, a fabric care product, a body-care product, a cosmetic preparation, a skin-care product, an air care product, or a home care product.

17. The perfumed consumer product according to claim 16 , wherein the perfumed consumer product is a fine perfume, a splash or eau de perfume, a cologne, an shave or after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain-care product, a shampoo, a coloring preparation, a color care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair spray, a vanishing cream, a deodorant or antiperspirant, a hair remover, a tanning or sun product, a nail product, a skin cleansing, a makeup, a perfumed soap, shower or bath mousse, oil or gel, or a foot/hand care products, a hygiene product, an air freshener, a “ready to use” powdered air freshener, a mold remover, a furnisher care, a wipe, a dish detergent or hard-surface detergent, a leather care product, or a car care product.

Assignees

• Firmenich & Cie

Inventors

• Quintaine Julie

Classifications

• C07C2601/10

  the ring being unsaturated · CPC title

• C11B9/003

  the ring containing less than six carbon atoms · CPC title

• C07C47/225

  containing rings other than six-membered aromatic rings · CPC title

• C07C2601/16

  the ring being unsaturated · CPC title

• C11B9/0026

  compounds containing an alicyclic ring not condensed with another ring · CPC title