FRAGRANCES WITH CYCLOPROPYL STRUCTURE

Abstract

SUMMARY

Suggested are cyclopropyl derivative according to formula (I)

##STR00001## wherein R.sup.1 represents a cyclopropyl or C.sub.1-C.sup.6-alkylcyclopropyl residue; R.sup.2 stands for a COR.sup.3 or (CH.sub.2).sub.nR.sup.4 radical; R.sup.3 stands for linear or branched C.sub.1-C.sub.6 alkyl; R.sup.4 stands for CH.sub.2OH or CHO; and n stands for an integer of from 1 to 12. The derivatives are characterized by very intense, but also very different scents, depending on their structure.

Claims

1. A cyclopropyl derivative according to formula (I): ##STR00014## wherein R.sup.1 represents a cyclopropyl or C.sub.1-C.sub.6-alkylcyclopropyl residue; R.sup.2 stands for a COR.sup.3 or (CH.sub.2).sub.nR.sup.4 radical; R.sup.3 stands for linear or branched C.sub.1-C.sub.6 alkyl; R.sup.4 stands for CH.sub.2OH or CHO; and n stands for an integer of from 1 to 12.

2. The cyclopropyl derivative according to claim 1, wherein R.sup.2 stands for COR.sup.3 and R.sup.3 for a linear or branched alkyl group with 3 or 4 carbon atoms.

3. The cyclopropyl derivative according to claim 1, wherein R.sup.2 stands for (CH.sub.2).sub.nR.sup.4, R.sup.4 stands for CHO and n for an integer of from 8 to 10.

4. The cyclopropyl derivative according to claim 1, represented by formula (II): ##STR00015##

5. The cyclopropyl derivative according to claim 1, represented by formula (III) or (IV): ##STR00016## or mixtures thereof.

6. A process for obtaining cyclopropyl derivatives according to formula (I) of claim 1; by a Johnson-Corey-Chaykovsky reaction, wherein an enone according to formula (V) ##STR00017## in which R.sup.2 has the above-referenced meaning, is subjected to cyclopropanation in the presence of a sulfur ylide having the structure Me.sub.3S.sup.Hal.sup.+, wherein Hal stands for bromine, chlorine or iodine.

7. The process of claim 6, wherein the reaction is conducted in the presence of DMSO and sodium hydride.

8. A process for obtaining cyclopropyl derivatives according to formula (I) of claim 1; by a Simmons-Smith reaction, wherein (a) in a first step an -unsaturated aliphatic alcohol according to formula (VI): ##STR00018## in which n has the above-referenced meaning, is subjected to cyclopropanation in the presence of an organozinc carbenoid having the structure Hal-ZnCH.sub.2-Hal and wherein Hal stands for bromine, chlorine or preferably iodine, and optionally (b) the hydroxyl group of the reaction product obtained from step (i) is subjected to oxidation to form an aldehyde group.

9. The process of claim 8, wherein the reaction is conducted in the presence of an organozinc carbenoid having the structure Hal-ZnCH.sub.2-Hal, wherein Hal stands for bromine, chlorine or iodine.

10. The process of claim 6, wherein the reaction is carried out in dichloromethane or chloroform as a solvent.

11. A perfume mixture comprising (a) at least one cyclopropyl derivative according to formula (I) of claim 1 as the primary fragrance, and (b) at least one secondary fragrance different from (a).

12. The mixture of claim 11, wherein said components (a) and (b) are present in a ration by weight of from about 0.01:99.99 to 10:90.

13. The mixture of claim 11 further comprising a solvent.

14. A cosmetic, personal care or detergent composition comprising the cyclopropyl derivative of claim 1.

15. (canceled)

16. The process of claim 8, wherein the reaction is carried out in dichloromethane or chloroform as a solvent.

Description

EXAMPLES

Example 1

Synthesis of 2-methyl-1-(2-methylcyclopropyl)butan-1-one (isomers of 1:1)

[0509] Cyclopropanation of 5-Methylhept-2-en-4-one (via Johnson-Corey-Chaykovsky reaction) following the procedure known in literature providing the title compound.

##STR00010##

[0510] MS: 140, 125, 112, 98, 83, 69, 55, 41, 29.

[0511] .sup.1H NMR (400 MHz, CDCl.sub.3) 2.57 (dtq, J=10.6, 6.7, 3.2 Hz, 2H), 1.80-1.65 (m, 4H), 1.45 (dqt, J=13.3, 6.3, 3.1 Hz, 2H), 1.38-1.28 (m, 2H), 1.29-1.17 (m, 2H), 1.16-1.08 (m, 12H), 0.90 (t, J=7.4 Hz, 3H), 0.89 (t, J=7.5 Hz, 3H), 0.74-0.62 (m, 2H).

[0512] .sup.13C NMR (101 MHz, CDCl.sub.3) 213.97, 213.96, 48.73, 48.66, 28.35, 28.27, 26.06, 25.98, 20.08, 20.02, 19.08, 19.06, 18.14, 18.10, 15.82, 15.71, 11.71, 11.68.

[0513] Odor: minty, fresh, nutty

Example 2

Two-Step Synthesis of 9-cyclopropylnonanal

##STR00011##

(1) Synthesis of 9-cyclopropylnonan-1-ol

##STR00012##

[0514] Under N.sub.2 atmosphere, to a suspension of Et.sub.2Zn (99.4 mL, 89.42 mmol) and DCM (90 mL), between 0 and 5 C. pre-dissolved solution of Trifluoroacetic acid (6.64 mL, 89.42 mmol) in DCM (45 mL) was very slowly added and reaction maintained at same temperature for 30 min. Later added CH.sub.2I.sub.2(7.21 mL, 89.42 mmol) in DCM (45 mL) and maintained for 30 min, followed by addition alcohol (9 mL, 44.71 mmol) in DCM (45 mL). Reaction maintained at room temperature for over the night (20 h) and quenched with sat. NH.sub.4Cl (200 mL), compound extracted from aqueous layer using cyclohexane (100 mL3). Combined Organic layer washed with sat. NaHCO.sub.3, water, brine and dried over Na.sub.2SO.sub.4, filtered and evaporated to the crude (10.6 g). Purification by classical column chromatography (cyclohexane: Ethyl Acetate) gave the title compound as colorless oil (6.54 g, 79%)

(2) Synthesis of 9-cyclopropylnonanal

##STR00013##

[0515] To a suspension of Dess-Martin periodinane (22.56 g, 53.19 mmol) in DCM (395 mL) was added pre-dissolved solution of 9-cyclopropylnonan-1-ol (6.54 g, 35.46 mmol) in DCM (40 mL) and reaction maintained at room temperature for over the night (20 h). To this added Et.sub.2O (400 mL) and washed with 1M NaOH (500 mL2), dried over Na.sub.2SO.sub.4, filtered and evaporated to the crude (6.3 g). Purification by classical column chromatography (cyclohexane: Diethyl ether) gave the title compound as colorless oil (4.99 g, 77%) with a very strong odor note.

[0516] MS: 182, 135, 126, 111, 97, 81, 67, 55, 41, 29

[0517] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) 9.34 (t, J=1.7 Hz, 1H), 1.82 (td, J=7.3, 1.7 Hz, 2H), 1.45-0.99 (m, 14H), 0.61 (dddt, J=13.0, 8.2, 6.9, 3.4 Hz, 1H), 0.46-0.34 (m, 2H), 0.06-0.00 (m, 2H).

[0518] .sup.13C NMR (101 MHz, C.sub.6D.sub.6) 6 200.71, 43.91, 35.15, 30.06, 29.86, 29.72, 29.72 29.41, 22.25, 11.32, 4.86, 4.86.

[0519] Odor: strong aldehyde, soapy, green, watery