DE2336798A1 - PROCESS FOR THE MANUFACTURING OF SESQUITERPENKETONE - Google Patents

Description

PATENTANWAtTE 9 ^ Ί fi 7 9

DIPL-ING.DIETERJANDER " ^{ÄJJU / V}

DR.-ING. MANFRED BÖNING

1 BER IN 15

KURFÜRSTENDAMM 66

TELEPHONE 883 50 71

97/15 078 DE 17th July 1973

Patent application

of the company

NAARDEN INTERNATIONAL N.V.,

Huizerstraatweg 28,

Naarden-Bussum,

Netherlands

"Process for the production of sesquiterpene ketones"

The invention relates to a method of manufacture of sesquiterpene ketones. In particular, it relates to the oxidation of sesquiterpene hydrocarbons, welclie

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contain a single ethylene bond, by means of Hydrogen peroxide. Here are the sesquiterpene ketones obtained free of isomeric ketones.

Although oxygen-containing sesquiterpene derivatives are of growing interest in the perfume and fragrance industries found, the number of sesquiterpene ketones that are actually used is very small. S. Arctander describes in "Perfume and Flavor Chemicals", Montclair, N.J. (1969) only Cedranon (Monograph No. 596), Germacron (No. 1463), Nootkaton (No. 2382) and Vetivon (No. 3089).

The increasing interest in the compounds is reflected in some more recent patent applications. In the British U.S. Patent 1,197,579 is the use of an oxidation product of isolongifolene as a perfume ingredient specified. The product obtained by oxidizing isolongifolene with sodium dichromate in an acidic medium consists of a mixture of at least three ketones. Also the oxidation with hydrogen peroxide and vanadium (V) oxide in acetone leads to a mixture of ketones with unreacted isolongifolene. Yields won't specified.

In British Patent 1,216,048, the production of new Thuyopsanonen from Thuyopsen and their use indicated as a fragrance material. According to this patent, the oxidation of Thuyopsen is preferred with peracetic acid or chromyl chloride carried out, but it can also

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Reagents v / ie manganese dioxide, potassium permanganate and oxygen can be used in conjunction with actinic radiation. The yield of thuyopsanone isomers is $ 70 of theory when using peracids. Used one chromyl chloride or oxygen, yields are Earned from 35 »$ 4 and $ 30.

It has now been found that high yields of sesquiterpene ketones can be obtained if the oxidation is carried out under certain conditions. Thereby finds no allyl oxidation takes place.

The invention relates to a process for the preparation of sesquiterpene ketones, which 'consists in that Sesquiterpene hydrocarbons, which have an olefinic bond in an endocyclic position, with hydrogen peroxide be reacted in the presence of a lower alkyl formate.

In the new process, 1 mole of sesquiterpene hydrocarbon, about 1.3-1.5 moles of hydrogen peroxide in a concentration of about 20-50 percent by weight and 120-200 mol percent (based on the hydrocarbon) of a lower alkyl formate are reacted with one another. Suitable alkyl formates are methyl, propyl, butyl and especially ethyl formate. The reaction is usually carried out between 40 and 100 ⁰ G, and usually takes 6 - 12 hours.

From US patent 2,555,927 it is already known ' that unsaturated organic compounds are treated with hydrogen peroxide and an alkyl format whose boiling point

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point below 100 ° G, vicinal moles as a catalyst deliver. According to this US patent, the preferred exist Conditions for the reaction in that one hol of olefin with 1.1-1.2 moles of hydrogen peroxide in a concentration of 5-15 percent by weight in 50-100 Mol percent (based on hydrogen peroxide) of a low-boiling alkyl formate, preferably methyl formate, at a temperature of 25-100 ° C for 12-4-8 hours lets react. This reaction can be used for the hydroxylation of olefinic bonds in monoolefins, diolefins, unsaturated ones Fatty acids, unsaturated alcohols, olefins substituted with a cyclic structure, and use cyclic olefins substituted with a saturated group.

It is therefore surprising that sesquiterpene hydrocarbons _{G ^ 1 -Hp 2} ,, which have an olefinic double bond in the endocyclic position, on treatment with hydrogen peroxide and a lower alkyl formate under reaction conditions which are similar to those of US Pat. No. 2,555,927 vicinal diols but are converted to sesquiterpene ketones.

Examples of sesquiterpene hydrocarbons CL cHp ^, the one Have olefinic double bonds and can be implemented according to the invention are cedrene, isolongifolene, Thuyopsen i.a. (cf. formulas 1, 2 and 3).

Sesquiterpene hydrocarbons, which are more than one olefinic Contain bond, such as ß-caryophyllene, form under the Reaction conditions of the invention a mixture of as yet unidentified products in addition to a large one Amount of polymeric material.

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Sesquiterpene hydrocarbons, which have an olefinic bond in the exocyclic position, do not form any [ carbony] compounds.

If one compares compounds with a related structure (for example Thuyopsen with oaiior Δ ^D - Garen-, cf. Formula 4) in the process according to the invention, it is found that with monoterpenes negative reactions, such as opening of the cyclopropane ring and polymerization, take place, while sesquiterpenes take place give ketones in high yield.

The invention therefore relates to the use of sesquiterpenes hydrocarbons with an olefinic bond in the endocyclic position.

The following examples illustrate the invention.

example 1

In a 6 liter glass flask equipped with a stirrer, dropping funnel and reflux condenser were 150 g (6.6 moles) isolongifolene and 975 g (13j2 mol) ethyl formate. The content was reduced to about Heated at 57 ° C. There were 975 6 hydrogen peroxide (concentration 30 weight percent, 8.6 moles) at such rate admitted that excessive foaming did not occur. That lasted 1-2 hours, followed by 6 hours heated to reflux. During the reaction, the temperature in the soil gradually rose to about 73 ° C. That

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The reaction mixture was cooled to about 25 ° C. Me \ ~ Boaenschicht was peeled off and discarded. The upper layer was successively washed with 900 ml of saturated sodium hydrogen. carbonate solution and 900 ml of water and then dried over magnesium sulfate. By vacuum fractionation obtained 1014 g of isolongifolanone, boiling point 113-117 ° C / 2 Torr,

changed α · ΓΠΑβ input

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'S «

ι:

-Ii.6 -

η ψ- = 1.5011, IR spectrum see Fig. 1.

A group of 6 skilled perfumers agreed unanimously Opinion that the smell of the isolongxfolanone thus obtained is preferable to that which the mixture is more isomeric Ketones, which as Isolongifolenoxxdat from the GB-PS 1 197 579 is known.

Example 2

Analogously to Example 1, 204 g (1 mole) cedrene, 165 g (1.45 moles) 30 # hydrogen peroxide and 150 g of ethyl formate reacted. The temperature in that Soil rose from 58 to 82 ° C in the course of 6 hours. Man received 154 g of Cedranon, bp 124-126 ° C / 0.2 Torr; η ^ = 1.5026, I.R. spectrum see Fig. 2.

Example 3

Thuyopsen was implemented as in Example 2. The temperature rose from 57 to 78 ^° C. in the course of 10 hours. 195 g of thuyopsanone were obtained, boiling point 116-122 ° C./1.8 torr; η ^ = 1.5022, IR spectrum see Fig. 3.

Example 4

Example 3 was repeated, but instead of the Ethyl formate used 1.5 mol of butyl formate. 182 thuyopanon were received.

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ORlGiNAL INSPECTED

Claims (6)

. ! 2336 738 Patent claims: ! Process for the production of sesquiterpene ketones, characterized in that sesquiterpene hydrocarbons, which have an olefinic bond in the endocyclic position with hydrogen peroxide be reacted in the presence of a lower alkyl formate. 2. The method according to claim 1, characterized in that 1 mole of sesquiterpene hydrocarbon 1 j 3-1 j 5 moles of hydrogen peroxide, which is a concentration of 20-50 weight percent, and 120-200 mole percent of a lower alkyl formate is reacted. 9. The method according to claim 1 or 2, characterized in that the reaction is carried out at about 40-100 ⁰ C in the course of 6-12 hours. 4. The method according to claims 1-3 »thereby g e k e η η indicates that methyl, ethyl, propyl or butyl formate is used as the alkyl formate. 5. The method according to claim 4, characterized in that the alkyl formate is ethyl formate verier ends. 6. Sesquiterpene ketones, obtainable according to claim 1, in pure form. DJ: J} G 309885/1439 OPöGINAL INSPECTED