DE1793710C3 - Cis and trans epoxyocimes, processes for their production and their use - Google Patents

Description

Epoxy rings

trans-ocimen

trans-epoxyocimes

sec-ocimenol

CHO

1. CH ₃ -CH ₂ -CH = NR

Z hydrolysis / H ⁺

OR

CHO

«-Sinensal

The following examples, in which the temperatures are given in degrees Celsius, show how the Invention can be carried out.

Example I.
Manufacture of trans-epoxyccimes

A solution of 204 g of trans-Ocimen and 150 g of sodium acetate in 750 ml of methylene chloride was stirred for 1 hour at room temperature and then cooled to 0 ° over about 15 minutes. A solution of 3 g of sodium acetate in 315 g of 42% strength peracetic acid was then added dropwise at such a rate that the temperature of the reaction mixture rose to 20-25 °. By maintaining a suitable rate of addition, but without removing the cooling device, the temperature was held constant until the addition of the peracetic acid was complete. Under these conditions, the addition of the peracetic acid took about 1 hour. The reaction mixture was stirred for a further 4 hours at room temperature, after which the solid by-product was filtered off and washed with methylene chloride. The combined methylene chloride solutions were poured into ice water, the mixture was shaken vigorously and the organic layer was separated. The latter was washed with 125 ml portions of the following solvents: water (once), saturated sodium bicarbonate solution (twice) and water (once). After drying and concentration, the residue was distilled. 205 g of trans-epoxyocimen were obtained (90% yield), b.p. = 45-47 ° / 0.1 Torr, df = 0.9082; ng ¹ = 1.4802.

Example 2
Manufacture of cis-Ocimenepoxide

cis-Ocimen was epoxidized in the manner described in Example 1 for trans-Ocimen. The cis-Ocimenepoxide had the following constants: df = 0.8996; «ϊ" = 1.4721. The yield was about 90%.

Example 3

A perfume composition with a scent of lavender was prepared by mixing the following components:

Components Parts by weight Lavender essence 515 Rosemary essence 20th Sage essence 30th Bergamot essence 90 Lemon essence 40 Geranium Bourbon 40 Nonanal, 1% *) 10 Undecanal, 1% *) 20th Dodecanal, 1% *) 10 Methyl phenyl ketone, 10% *) 5 Phenylethyl alcohol 40 Citronellyl acetate 10 Coumarin 50 Ambrette musk 10 Ketone musk 30th Lavender absolutely 40 Oak moss absolutely 5 Pentadecanolide 25th

1 In phthalic acid diethyl ester.

985

By adding 15 parts by weight of Irans epoxy oils The top note of this fragrance composition has been significantly strengthened and improved.

Claims (4)

Patent claims:
L cis-epoxyocimen 2. trans-epoxyocimes 3. Process for the preparation of the compounds according to Claim 1 and 2, characterized in that that the non-conjugated double bond of Ocimen in a known manner by means of a Peracid epoxidized in a buffered medium. 4. The use of the compounds according to claim 1 and / or 2 as a fragrance component in fragrance compositions. The invention relates to cis- and trans-epoxyocimes of the formulas O cis-epoxyocime O trans-epoxyocimes a process for their production and their use. The new compounds are prepared by epoxidizing the non-conjugated double bond of ocimen in a manner known per se using a peracid in a buffered medium.
The peracid used for the epoxidation can, for example, peracetic acid, perbenzoic acid; Be monochloroperbenzoic acid or perphthalic acid. Chlorinated hydrocarbons, for example chloroform, methylene chloride, trichlorethylene or dichloroethane, can be used as solvents. The use of peracetic acid in methylene chloride is advantageous. Organic alkali salts such as sodium or potassium formate, acetate, propionate, butyrate, oxalate, citrate or tartrate are suitable as buffer substances. Sodium acetate is advantageously used. The selective epoxidation of the nichiconjugated double bond of the ocimene while avoiding attack on the other double bonds is a critical operation and must be carried out under carefully regulated conditions if good yields of the desired epoxide are to be achieved. It was z. B. found that the control of the reaction temperature by the usual methods is inadequate. The cooling capacity of the temperature control device (cooling apparatus) should be such that after the start of the addition of the epoxidizing agent at a certain rate, the temperature rises rapidly to a certain level and remains practically constant until the addition of the epoxidizing agent is complete. To achieve optimal yields it is advisable, for example, to cool the reaction vessel to about 0 ° C. and to add the epoxidizing agent drop by drop at such a rate that the temperature first rises to 20-25 ° C. and then remains practically constant at this level without the cooling device must be put out of operation.
The monoepoxides of cis-Ocimen and trans-Ocimen are fragrances that have interesting olfactory properties. They are particularly suitable for enhancing the top note of perfume compositions and are expediently used in amounts of about 0.5 to 3%, based on the total weight of a perfume composition. However, these figures are not to be taken as limit values, since the epoxides mentioned can also be used in larger quantities, depending on the desired odor effects. The monoepoxides of cis-ocimes and trans-ocimes are also interesting starting compounds for the production of, x-Sinensal (Sesquiterpenaldehyde, that has been found in one type of orange, Citrus sinensis (see J. Org. Chem. 30, 1690 [1965]) - 55, according to the method illustrated in the following scheme for trans-Ocimene: Peracid opening of the