Use of novel cyclic carbaldeydes as an aromatic substance

Patent metadata

Field	Value
Publication number	US-10112882-B2
Application number	US-201515514902-A
Country	US
Kind code	B2
Filing date	Sep 30, 2015
Priority date	Sep 30, 2014
Publication date	Oct 30, 2018
Grant date	Oct 30, 2018

Abstract

The present invention relates to new types of cyclic carbaldehydes, the preparation thereof and the use as aromachemical, in particular as fragrance, and to aroma substance compositions and products comprising these carbaldehydes.

First claim

The invention claimed is:

1. A carbaldehyde of the formula X

wherein A is a cycloaliphatic, monocyclic unsubstituted hydrocarbon radical, the carbaldehyde selected from isomeric formulae I, II or III,

and the stereoisomeric forms thereof.

2. A composition comprising at least one carbaldehyde according to claim 1 .

3. An aromachemical composition comprising at least one carbaldehyde of the formula X

wherein A is a cycloaliphatic, monocyclic, unsubstituted hydrocarbon radical with 15 ring carbon atoms, and n C═C double bonds, where n is 1, 2 or 3.

4. The aromachemical composition according to claim 3 , wherein n is 1.

5. The aromachemical composition according to claim 3 , where the compound is selected from the isomeric compounds of formulae I, II, or III

and the stereoisomeric forms thereof.

6. A product selected from the group consisting of perfumes, detergents, cleaners, cosmetic products, body care products, hygiene articles, foods, food supplements, air fresheners, scent substances, pharmaceutical products and crop protection products that contains the aromachemical composition according to claim 3 .

7. The aromachemical composition according to claim 3 comprising trans-cyclopentadec-8-enylcarbaldehyde of the formula (I).

8. The aromachemical composition according to claim 7 further comprising trans-cyclopentadec-7-enylcarbaldehyde of the formula (II) and cis-cyclopentadec-8-enylcarbaldehyde of the formula (III), where the fraction of trans-cyclopentadec-8-enylcarbaldehyde in the composition, based on a total sum of the formulae I, II and III is at least 65%.

9. The aromachemical composition according to claim 7 comprising the compounds of the formulae I, II and III, where the weight ratio of I:II:III is in the range from 0.3-0.5:0.2-0.3:0.3-0.4.

10. The aromachemical composition according to claim 9 , wherein the weight ratio of I:II:III is about 43:24:33.

11. A process for preparing a compound of formula X

wherein A is a cycloaliphatic, hydrocarbon radical with in ring carbon atoms and n C═C double bonds, where in is an integer selected from 13, 14, 15, 16 or 17, and n is selected from 1, 2 or 3, where

a) reacting a cycloaliphatic compound of the formula XII

wherein A′ is a cycloaliphatic hydrocarbon radical with m+1 ring carbon atoms, where m is an integer selected from 13, 14, 15, 16 or 17, and optionally has n+1 C═C double bonds, where n is selected from 1, 2 or 3, with NaH and methyl formate to give the corresponding cyclic formyl ketone XIII

in which A′ is as defined above;

b) reacting the cyclic formyl ketone with triethylamine and 4-acetamidobenzyl azide to provide the corresponding diazoketone XIV

in which A′ is as defined above;

c) removing the N 2 from the diazoketone under the conditions in a Wolff rearrangement, N 2 is cleaved off in the presence of an alkanol to provide the corresponding ester of formula XV

in which A is as defined above;

d) reducing the ester of formula XV to the corresponding alcohol of formula XVI

in which A is as defined above;

e) oxidizing the alcohol of formula XVI to give the carbaldehyde of the formula X; and
f) optionally, isolating the carbaldehyde of the formula X from the reaction mixture.

12. The process according to claim 11 , wherein the compound of the formula XII in stage a) is cis-/trans-cyclohexadec-8-enone, and trans-cyclopentadec-8-enylcarbaldehyde (I), trans-cyclopentadec-7-enylcarbaldehyde (ii) and cis-cyclopentadec-8-enylcarbaldehyde (III) are obtained in stage a).

13. The process according to claim 11 , where compounds of the formulae (I), (II), or (III), or mixtures thereof, are obtained in stage f) by chromatic purification of a reaction mixture from stage e), wherein the total amount of (I), (II) and (III) in a mixture following stage e) is at least 50% by weight.

14. The aromachemical composition according to claim 2 comprising 0.01 to 99.9% by weight of the carbaldehyde of the formula X

wherein A is a cycloaliphatic, monocyclic unsubstituted hydrocarbon radical, the carbaldehyde selected from isomeric formulae I, II or III,

and the stereoisomeric forms thereof, based on the total weight of the composition.

Assignees

• Basf Se

Inventors

• Thrun Frauke
• Teles Joaquim Henrique
• Werner Albert
• Dehn Richard
• Pelzer Ralf
• Maurer Stephan

Classifications

• C11B9/0038

  the ring containing more than six carbon atoms · CPC title

• C07C47/38 Primary

  Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings · CPC title

• C07C2601/18

  with a ring being at least seven-membered · CPC title

• C07C45/29

  of hydroxy groups · CPC title

• C07C45/27

  by oxidation (with ozone C07C45/40) · CPC title