DE2022216C3 - 04/17/70 Switzerland 5725-70 Cycloaliphatic unsaturated ketones, process for their production and their use as fragrances and flavorings - Google Patents

Description

2 '.3' R "\ / CO-CH _n -C-CH ₂ ^ _n R ¹

^Tl R ³ R ² (VIII)

where n, the symbols R ¹ to R ⁷ and the dashed lines have the above meaning, oxidizes and this further converts as under h)

3. Use of the compounds according to claim 1 as fragrances or fragrance additives in Fragrance compositions.

4. Use of the compounds according to claim 1 as flavorings or flavor additives in flavorings.

5. Embodiment according to claim 4, characterized in that the flavorings or Flavoring agents used for flavoring food for humans and animals, beverages, tobacco products and pharmaceutical products will.

The present invention relates to a new class of cycloaliphatic unsaturated ketones the general formula

2 '

/ CO-CH ,,

- C-CH ^ _n R ¹

with one double bond in the 2 'or 3' position of the acyl side chain and either one double bond in position 1 or 2 or two double bonds in positions 1 and 3 of the ring and where η denotes the number O or 1, R ¹ , R ² and R ³ denotes hydrogen or one of these symbols a methyl or ethyl radical and the others denote hydrogen, R ⁴ , R ^s , R ⁶ and R ⁷ denote hydrogen or one of these symbols a methyl or ethyl radical and the others denote hydrogen and the double bonds are represented by dashed lines , where the symbols R ¹ to R ⁷ all simultaneously denote hydrogen only if either the ring has an exocyclic double bond or is η - 1

The invention further relates to processes for the preparation of the compounds of the general formula I and the use of the compounds mentioned as fragrances or fragrance additives in fragrance compositions and as flavorings or flavor additives in flavorings.

It has been found that the compounds of the invention are particularly interesting and useful Have organoleptic properties and therefore as fragrances in the perfume industry, as flavors in aromas and as taste-changing substances Additives for food for humans and animals, beverages, pharmaceutical preparations and tobacco products can be used.

The term "food" is used in the broadest sense and is also intended to include indulgence, such as coffee, tea and cocoa and chocolate, respectively.

The new ketones can be used in particular as fragrances in concentrated or diluted perfumes and in perfumed products, e.g. soaps, detergents, cosmetic products, waxes and other products, which can be perfumed to increase their marketability can be used.

The new compounds are also used as components in the manufacture of artificial essential oils in the direction of jasmine oil, geranium bourbon oil, Rose oil and others, very useful.

The compounds according to the invention increase the odor intensity and the emissivity of Perfume compositions and give the latter a natural scent note.

The compounds according to the invention also have interesting taste properties. Develop depending on the nature of the products into which the compounds mentioned are incorporated the latter have fruity, herbaceous, wine-like, woody, floral or waxy flavors or combinations of the latter a In certain cases the new compounds develop redberry-like Flavor notes and can therefore improve the taste and aroma of artificial Strawberry, cranberry, cherry or currant aromas can be used. Surprisingly, you can the new ketones even improve the taste and aroma of products like honey and red wine can be used.

The amounts in which the new compounds are used to achieve the desired olfactory effects vary within wide limits. In the manufacture of perfume compositions you can interesting effects even with very small amounts, for example from about 100 ppm to about 5% on the total weight of a perfume composition. Depending on the desired effects the new ketones can be added in larger amounts, for example up to about 10% or more will.

When the new ketones are used as flavorings or additives to change the organoleptic properties of food for humans and animals, beverages, pharmaceutical preparations and tobacco products, those to be used vary Quantities also within wide limits. Interesting organoleptic effects can, for example with amounts of 0.1 to 10 ppm of the new ketones, based on the weight of the to be flavored Products. However, these amounts can be increased, for example up to 100 ppm if special taste effects are desired. In the production of aromatic compositions by Mixing the new compounds with other flavorings can use the compounds mentioned for example in amounts of about 0.1% to about 15%, based on the total weight of the aroma composition. In many cases, with medium amounts of about 1 to about 10 wt .-% achieved the desired results.

However, the numerical values given above are not to be regarded as absolute limit values. To achieve Special smell or taste effects can also be lower or higher concentrations be used.

According to the invention, the compounds of the general formula

CO-C = C-CH ₂ R ¹
R ³ R ²

a subclass of the compounds of general formula I in which the radicals R ¹ - R ^{7 are} as defined above, obtained by

a) an organometallic propene derivative of the general formula

Γ 2 '3'

R ³ R ²

wherein the symbols R ¹ , R ² and R ^{3 have} the meaning given above and ME is a metallic or metal-containing radical, ζ. B. Li, Zn, Cd or Mg — halogen represents, in a manner known per se with a cyclogeranoyl or safranyl derivative of the general formula

R ⁷

a. = endocyclic double bond in position 2,
β - endocyclic double bond in position 1,
γ = exocyclic double bond in position 2,
<5 = two conjugated double bonds, in positions 1 and 3,

wherein the symbols R ⁴ , R ⁵ , R ⁶ and R ⁷ and the dashed lines have the meaning given above and X is halogen, —O — alkyl, —Ο — aryl, —O — CO — aryl or —O — CO — alkyl means, implements.

According to a preferred procedure, the cyclogeranoyl derivative used is, for example, cyclogeranyl halides, such as chlorides, bromides or iodides, or cyclogeranates, e.g. B. methyl, ethyl or Lithiumcyclogeraniat The Cyclogeranoyl- and Safranylderivate can according to different methods can be synthesized, some of which are described below.

1. The cyclogeranoyl derivatives with α and ^ structure can be obtained from the corresponding cyclogeranic acids by customary methods. The cyclogeranic acids can be obtained from the corresponding citral derivatives by known methods (see Gildemeister & Hoffmann, "Die Aetherischen Oele", Volume III d, pages 137-138, Akademie-Verlag Berlin [1966]). These syntheses are illustrated in topic A below, in which the symbols R ¹ to R ⁷ and the dashed lines have the meaning given above.

oxidation

Cyclization

Geranic acid derivatives

R " \ / COOH

Halogenation
or esterification

COX

2. The cyclogeranoyl derivatives with <x and / ^ structure can also be achieved by cyclizing the corresponding citral derivatives according to known methods (see e.g. Bedoukian, "Perfumery and Flavoring Synthetics", Elsevier, New York [1967]), while the cyclogeranoyl derivatives with the y structure are produced by isomerization from /? - Cyclocitralen are accessible. the

Scheme B

(IV a -. [I-)

The aldehyde group of the cyclocitrals is converted by oxidation into the carboxyl group, which is converted into the -COX group by customary methods. This synthesis is illustrated in scheme B below, in which the symbols R ¹ to R ⁷ and the dashed lines have the meaning given above.

R ⁵

CHO

R ⁴

Cyclization

! Isomerization

oxidation

(IV _n -. Β-.γ.)

709 607/163

3. The Cydogeneranoylderivate with y-structure, wherein χ «_ Ο — Alkyl is must according to HeIv. Chim. Acta, 41.1359 (19:58) from a Λ-alkoxycarbonyl derivative of Cyclohexanone can be obtained. By condensing these derivatives with an ethyl haloacetate a diester is obtained in the presence of zinc.

from which the desired y-compound is produced by dehydration, partial saponification and monodecarboxylation. This synthesis is illustrated in scheme C below, in which the symbols R ¹ to R ⁷ and the dashed lines have the meanings already given above.

Scheme C

\ / COX R "/ COX

HaICH ₂ -COOEt "Av ⁷ '! H ₂ O

R ⁵ IOR ⁴

Zn

R ⁵

2) saponification

R ⁴ COOEt

R ⁴ COOH

Decarboxylation

, IVj-)

The Λ-alkoxycarbonyl derivatives of cyclohexanone can after the in HeIv. Chim. Acta, 35, 1753 (1952) method described can be obtained from methylheptenone.

4. The Safranylderivate can in a simple manner by dehydration of the corresponding / J-Cyclogeranoylderivate, as illustrated in Scheme D can be obtained.

R ⁶ \ / COX

Scheme D.

-H ₂

COX

(IVA) The ketones of the general formula

ψ 2 · ν

R ⁶ \, CO-CH _n - C-CH, .. R ¹

R ³ R ²

with a double bond in the 2 'or 3' position of the acyl side chain and a double bond in the 1 position (^ structure) or 2 position («structure, endocyclic double bond; y structure, exocyclic double bond) of the ring and in which π denotes the number O or 1 and the radicals Ri - R? and η are as defined above, are further obtained according to the invention by
b) an alcohol of the general formula

60

The symbols R ¹ to R ⁷ have the meaning already given above. The dehydrogenation can be carried out in the same way as in the process according to the invention, in which the compounds Iβ are converted into the compounds Ιδ . This procedure is described below.

R ⁷ 2 '

3 '

R ⁶ \ / CH-CH _n -C-CH ₂ ^ R ¹

II ^{0H R} '

AA.

I. R *

worm the symbols Ri to R ?, π and the dashed

ME - CH _n - C -

(UIb)

(IHbI

«-./I-.y-Cyclocitrale

Lines have the same meaning as in general formula I, in a manner known per se with chromium trioxide or manganese dioxide according to the z. B. in J. Org. Chem, 26, 4814 (1961) described method oxidized in an inert solvent. Manganese dioxide is an inexpensive oxidizing agent which can be dissolved at room temperature in an inert solvent, e.g. B. pentane or hexane can be used.

If manganese dioxide is used, the geometric configuration of the substance subjected to oxidation (cis or trans alcohols of the general formula V or mixtures thereof) is practically completely retained. If chromium trioxide is used, preferably in the presence of an organic base such as pyridine, the ketone obtained has the trans configuration, regardless of whether the starting alcohol has the cis or trans configuration the general formula

1' T

"Organic Chemistry", McGraw Hill, New York [1959], p. 294).

Scheme F

R ⁷
ME R ⁷

OH

15 ME

ME

OH

OH

R ⁵

ME

OH

with a double bond in the V or 2 'position (dashed lines), in the ME a metallic or metal-containing radical, e.g. B. lithium or BrMg, denotes net, π represents the number O or 1 and the symbols R ¹ , R ² and R ^{3 have} the meaning given above, can be obtained from λ-, ß- or y-cyclocitrals and subsequent hydrolysis of the addition product .

The above process is illustrated by the following scheme E , in which the dashed lines and the symbols R ¹ to R ^{7 have} the meaning already given.

R ⁷

35

40

+ ME - CH _n -C-CH ₂ ^ R ¹

R ³ R ²

55

«-, ß- and γ-cyclocitrals can be prepared from citral derivatives, as illustrated in Scheme B (see above). Schemes F and G show some examples of reactions of this type. In these schemes, the symbols R ¹ to R ^{7 have} the meanings given above, ME represents a metallic or metal-containing radical, and a means an addition reaction of an organometallic reagent to a ketone (see e.g. Cram & Hammond, Scheme G.

b: implementation according to Carroll (see ζ. BJ Chem. Soc, pages 704, 1266 [1940]; page 507 [1941])

c: conversion for the conversion of methylheptenones into the corresponding citrals (see e.g. Bedoukian, "Perfumery and Flavoring Synthetics", Elsevier, New York [1967], pp. 102-103).

R ⁷ R ⁷

O I

R ⁴ Il R ^h \ /

γ ν ^X A _b \ J O

II OH + I -

Methylheptenone derivative

CHC

R ⁴ citral derivative

The alcohol of the general formula R ⁷

R ⁶ V / CH-C = C-CH ₂ R ¹

Wl I I

TT OH R ³ R ² (Vj-a)

R ⁵ Y ^X R ⁴

where R ^{2 is} hydrogen, Ri and R * are hydrogen or eir

of these symbols denote a methyl or ethyl radical and the other denote hydrogen and R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meaning given above, can also be carried out by isomerization and simultaneous reduction of an epoxide of the general formula

CH - C -CO-CH,! * ¹

CC -CH-R ¹

R- R ^:

in which the symbols R ¹ and R ³ to R 'have the meaning given above, are prepared (see Tetrahedron. 19, 1091 [1963] and] .Org.Chem, 26. 3055 [196I]).

The ketones of the general formula I1 and I3, in which the double bond of the acyl side chain is present in the 2'-sterile, are according to the invention

c) by cyclization, known per se, of a "pseudo" · ketone of the general formula

wherein the symbols R * to R ^{r have} the same meaning as in general formula 1 produced in the presence of an acidic Cydisierungsmitteb. The cyclization can be carried out under the same conditions as the cyclization of the 1,5-diene compounds, for example the cyclization of citral to cyclocitrai or of geranic acid to cyclogeranic acid (see, for example, Bedoukian, "Perfumery and Flavoring Synthetics", Elsevier, New York [1967]), be performed:

If protic acids are used as cyclizing agents for the cyclization, this indicates formed ketone of the general formula I in the general ο nen ^ structure, d. h that the double bond in the ring is conjugated to the carbonyl group (position 1 in the ring). B. Boron trifluoroetherate or tin tetrachloride, used, see above if the ketone formed of the general formula I has a general α-structure, d. H. with the double bond in position 2 of the ring. The cyclization is preferably carried out using tin tetrachloride in an inert Solvents, e.g. B. benzene or toluene

The »pseudo« ketones used as starting materials. Which as such are new fragrances and can therefore be used in the perfume industry can easily be achieved by reacting a citral derivative (see Scheme G) with an organometallic propene derivative (see Formula III) under conditions which are used in the preparation of the alcohols of general formula V. Conditions are similar, and subsequent oxidation of the alcohol formed can be produced. The same oxidizing agents and reaction conditions as for the oxidation of the alcohols of the general formula V can be used for this oxidation. The “pseudo” ketones of the general formula VI can also be prepared from methylheptenone derivatives (see scheme G) by the process illustrated in scheme H below. In this scheme, the symbols ° 'to R ^{7 have} the meaning described above.

Scheme H

R "

R "

OH

1 »alkyl -MsBt

21 R'CH = CR ^; - CHXR ³

X = haloses. KOH

R 'R' \

\ K CH-C = CHR "

CH-C = CHR ¹

\ I I

R ³ R-

OAc

1 Cu-Ac,

Ac = CHjCO

CO-C = C-CH ₁ R ¹

R ⁴

R ³ R ²

(Vl)

According to the invention, the compounds of the general formula

R ⁷
R ⁶ Χ / CO-C = C-CH ₂ R ¹

R ³ R ² (l, ia, / ia)

R ⁵

in which the double bonds and the radicals R ¹ to R ^{7 have} the above meaning, also obtained by the fact that
d) a ketone of the general formula

CO-CsC-CH ₂ R '

(VIl)

in which the symbols R ¹ to R ⁷ and the dashed lines have the same meaning as in formula I, partially hydrogenated on the triple bond in a manner known per se in the presence of a Lindlar catalyst. Such catalysts, ie deactivated palladium on carbon catalysts, are, for. B. in HeIv. Chim. Acta, 35,446 (1952). The resulting ketones of the general formulas I «-a and I, 8-a have the cis configuration. The corresponding trans isomers are according to the invention
e) produced by isomerization of the cis isomers by means of an acid in an inert solvent. B. p-toluenesulfonic acid, hydrochloric acid and trifluoroacetic acid can be carried out. One can also use Lewis acids, e.g. B. boron trifluoride or iodine, use. The isomerization is expediently carried out in an inert solvent, e.g. B. an aromatic hydrocarbon such as benzene or toluene, an aliphatic or cycloaliphatic hydrocarbon such as heptane or cyclohexane, or an ether such as glycol mono- or dimethyl ether or dioxane, carried out. The temperature at which the isomerization is carried out is not critical. For example, the isomerization can be carried out in such a way that the substance to be isomerized is mixed with the solvent and a catalytic amount of the acidic isomerizing agent and the mixture is kept at room temperature for several hours, e.g. B. 12 hours, leave to stand At temperatures below room temperature, the reaction time can be considerably lengthened, while at temperatures above room temperature, the reaction time can be shortened. · When at 100 "C lying temperatures unwanted side reactions can occur, therefore, the isomerization is preferably carried out below 100 ⁰ C.

The ketones of general formula VII used as starting materials are new compounds. SU can be prepared by reacting α- or / J-cyclocitralei with organometallic propyne derivatives, followed by hydrolysis of the reaction products and oxidation of the acetylene alcohols obtained in this way. This synthesis is shown in the following scheme
illustrated.

20th

22216 / fl)

lchema 1

ME-C = C-CH ₂ R ¹ + H ₂ O

R ^h \, · 'CO-C = C-CH ₂ R ¹

V V i I

i J R- ¹ R ² (Ic-a./ia)

R ⁴

6o

f> 5 K ⁶ \ / CH-C = C-CH ₂ R ¹

CO-C = C-CH ₁ R ¹

(VII)

In this scheme, the symbols R ¹ to R ⁷ and the dashed lines have the meaning already defined above. The symbol ME denotes a metallic or metallic residue of the usual type, e.g. B. an alkali metal, mercury, zinc, cadmium or magnesium. In those cases in which ME represents a divalent metal, e.g. B. Mg, the second valence can be replaced by a negative substituent, e.g. B. bromine, chlorine or iodine, be satiated. For the oxidation of the acetylene alcohols to the ketones of the general formula VII, the same oxidizing agents and reaction conditions as for the oxidation of the alcohols of the general formula V to the ketones of the general formula I can be used. A favorable way of working is durin, the oxidation with manganese dioxide in an inert solvent, ζ. B. hexane, cyclohexane or petroleum ether to perform.

The aoetylene ketones of the general formula VII can also be obtained by organometallic propyne derivatives of the general formula

ME-CsC-CH2R>

in which ME a metallic or metal-containing Remainder, e.g. Li, Na or K, according to known ones Methods directly with cydogeranoyl derivatives of the general formulas IVa- or IVjJ- (see scheme A) aeylated The compounds of the general formula

Have the above meaning, are obtained according to the invention by
f) compounds of the general formula

R ⁷

CO-CH-C = CHR '

ι ι

R ³ R ²

R ⁵

R ⁴

wherein the symbols R ¹ to R ⁷ and the dashed lines have the above meaning, isomerized by means of an acidic or basic isomerizing agent or by means of heat.

As the acidic isomerizing agent, one can use a strong mineral acid or organic acid, e.g. Use sulfuric, phosphoric, gaseous hydrochloric, perchloric, p-toluenesulphonic or trifluoroacetic acid. p-Toluenesulfonic acid is particularly suitable Isomerization by means of an acidic isomerizing agent can be carried out in organic solvents will. Most of the usual solvents are suitable for this purpose, e.g. B. aliphatic or cycloaliphatic Hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, esters or Ether, benzene is expediently used. Alkalis are suitable basic isomerizing agents, alkaline buffers or organic bases.

The compounds of the general formula

2 '3'

CO - CH _n - C n - CH ₂ . "R ¹

R ³ R ² (I Λ)

in which the dashed lines and the radicals R ¹ -R ⁷ with a double bond in the 2 'or 3' position of the

Lcylseitenkette and in the π and the radicals R ¹ - R ^{7 have} the> bige meaning, are obtained according to the invention by that
g) compounds of the general formula

IO

(I ti, Ii)

"5

CO - CC CH ₂ R ¹
R ³ R ²

where the symbols R ¹ to R ⁷ , η and the dashed lines have the meaning defined above, in a manner known per se by reacting with N-bromosuccinimide, N-bromoacetamide or N-dimethyldibromohydantoin in an inert solvent at temperatures between about 20 ⁰ C and about 100 ⁰ C, if desired in the presence of an initiator, and subsequent Dyhydrohalogenierung by means of a tertiary amine, such as diethylaniline, at about 100 ° to about 150 ⁰ C dehydrated as the halogenating agent is N-bromosuccinimide particularly well suited (see Chem. Rev, 63 , 21 [1963]). Suitable inert solvents are, for example, chlorinated solvents such as CCU, CHCl ₃ , CH2Cl2, dichloroethane, tetrachloroethane or trichlorethylene or a mixture of the solvents mentioned. The allyl halogenation is preferably carried out in a mixture of CCU and CH2Cl2 or CHCb at a temperature of 40 to 70.degree

The presence of a free radical initiator, e.g. B. OA'-azo-bis-isobutyronitrile or benzoyl peroxide, in the reaction mixture or the use of actinic rays has a beneficial effect as one Can keep the temperature at the beginning of the reaction much lower than in the absence of the above Initiator or actinic rays. Furthermore, the course of the reaction can be controlled more easily.

The dehydrohalogenation of the halogenation product can without its prior isolation and / or Purification carried out and by adding an organic base, e.g. B. a tertiary amine, such as Piperidine, morpholine, tributylamine, diethylamine or dimethylaniline. Diethylaniline is suitable particularly good because of its low volatility.

The compounds of the general formula

h) an epoxy compound of the general formula

2 '3'
-CH _n -C-CH ₂ ^ R ¹

R ³ R- (VIII)

with a double bond in the 2 'or 3' position of the acyl side chain and in which π and the symbols R ¹ to R ^{7 have} the meaning defined above and the double bond in the side chain is represented by a dashed line, and the oxygen atom of the epoxy ring with the positions 1 and 2 or 2 and 3 of the six-membered ring is linked, is treated with a mineral acid or organic acid, for example hydrochloric, phosphoric, sulfuric, p-toluenesulfonic or trifluoroacetic acid, acidic diatomaceous earth or at about 20 to about 100 ⁰ C. The treatment of the epoxy compound with the acidic agent is conveniently carried out in an organic solvent, e.g. B. benzene, toluene, tetrahydrofuran, dioxane or ethyl acetate, carried out. Preferably, phosphoric acid in dioxane or tetrahydrofuran is used and the reaction is carried out at the boiling point of these solvents.

In the treatment of the epoxy compounds of the general formula VIII, intermediate products are formed Hydroxy compounds of the general formula

CO-CH _n -C-CH, _ "R

(IX α. Il-

with a double bond in the 2 'or 3' position of the acyl side chain and in which the symbols R ¹ to R ^{7 have} the meaning defined above, and the hydroxyl group is linked to the 1-, 2- or 3-position of the six-membered ring

The compounds of the formula W-a are finally obtained according to the invention by

i) a compound of the general formula

s

60 CH-CH _n -C-CH, .. "R ¹

V "

in which the radicals R ¹ - R ^{7 have} the above meaning are furthermore obtained according to the invention by

J-O

with a double bond in the 2'- or 3'-position of the acyl side chain and a double bond in the 1- or 2-position of the six-membered ring, in which η and the symbols R ¹

to R 'have the same meaning as in the formula Io-a and the double bonds are shown by dashed lines, first epoxidized with a peracid in a manner known per se in a buffered anhydrous solvent to give the epoxide of the general formula X, this then with an acidic aqueous solution of CrCb is oxidized to the epoxide of the general formula VIII and this reacted as under h)
The peracid can be, for. B. peracetic acid, peramei-

Scheme J

sensic acid, perbenzoic acid, perphthalic acid or Use m-chloroperbenzoic acid. As a solvent, for. B. chloroform, methylene chloride, benzene or Trichlorethylene in the presence of a buffer, i_ B. one Alkali metal acetate can be used. Preferably CrO3 is used in acidified with H2SO4 aqueous solution.

This step-wise oxidation of the compounds Va, j3 is illustrated in reaction scheme J below

Peracid

CK - CH "- C- ^ CH ^" R ¹

R ³

R ²

(X)

CrO ₃₅ H

ι ⁴ CO-CH / - / \ _λ I.
R ² ϊ R.

(VIII)

H ⁺

R ³ R ²

(1 Λ-a)

In this scheme, the meaning of n, symbols R ¹ to R ⁷ and the dashed lines are the same as described above.

In the process illustrated by Scheme J, the epoxides formed as intermediates are not isolated. The starting materials used for process h) can be known per se Epoxidation of compounds of the general formula

CO

2 '3'

CH _n - C-CH ₂ _ "R ^!

R ³ R ²

55

60

obtained, wherein n, the symbols R ¹ to R ⁷ and the dashed lines have the meaning defined above. It is described in detail under i).

The compounds of general formula I have cis or trans configurations in the side chain.

In some of the above-described inventive Processes are generally obtained mixtures in which the quantitative ratio of the two isomers can fluctuate within wide limits. As a rule, these mixtures are used for reasons of economy Used directly in the fragrance and flavor industry without further purification or separation. However, the isomers can per se by customary methods, for. B. by column or Gas phase chromatography. In the presence of acids, the cis isomers zi isomerize the corresponding trans isomers. Under the one When actinic rays are affected, an equilibrium is established between the two forms. Durcl Irradiation of one or the other isomer or a mixture of the two results in a mixture, ii which the quantitative ratio of the two isomers is constant. This quantitative ratio changed not even if the irradiation time is extended.

General formula 1 includes, for example, the following substances:

cis- and trans-2,3,6,6, -Tetramethyl-

1 - (2-methyl-buten- (2) -oyl) -cyclohexadiene- (1,3),

23,6,6-tetramethyM - (3-methylbutene- (2) -oyl) -cyclohexadiene- (13),

cis- and trans-23.6.6-tetramethyll- (penten- (2) -oyl) -cyclohexadiene- (l, 3), cis- and trans-23.6,6-tetramethyl-1-crotonoyl-cyclohexadiene-vl, 3), cis- and trans-2,4,6,6-tetramethyl-l- (2-methylbutene- (2) -oyl) -cyclohexadiene- ( 1,3), 2,4,5,6-tetramethyl-1 - (3-methylbutene- (2) -oyl) -cyclohexadiene- (1,3), cis-2,4,6,6-tetramethyl-1-crotonoylcyclohexadiene- (l , 3).

cis- and trans-2,4,6,6-tetramethyl-1-penten- (2) -oyl) -cyclohexadiene- (1,3), cis- and trans-2,5,6,6-tetramethyl-1- (2-methyl-buten- (2) -oyl) -cyclohexadiene- (13).

2,5,6,6-tetramethyl-1 - (3-methylbutene- (2) -oyl) -cyclohexadiene- (1,3).

cis- and trans- ^ S & e-tetramethyll-pentene- (2) -oyl) -cyclohexadiene- (13).

cis-2 _I 5,6,6-tetramethyl-1 -crotonoylcyclohexadiene- {13).

cis- and trans-2,6-dimethyl-6-ethyl-l- (2-methyl-buten- (2) -oyl) -cyclohexadiene- (13),

2,6-Dimethyl-6-ethyl-1 - (3-methyl-buten- (2) -oyl) -cyclohexadiene- (l 3),

cis and trans-2,6-dimethyl-6-ethylt - (penten- (2) -oyl) -cyclohexadiene- (l 3),

cis and trans-2,6-dimethyl-6-ethyl-1-crotonoyl-cyclohexadiene-O 3), cis- and trans-2,6,6-trimethyl-l- (2-methylbuten- (2) -oyl) -cyclohexadiene- (13),

cis- and trans-2,6,6-trimethyl-l- (penten- (2) -oyl) -cyclohexadiene- (l 3).

cis- and trans-23.6,6-tetramethyll- (2-methyl-buten- (2) -oyl) -cyclohexen- (2), 23,6,6-tetramethyl-1 - (3-methylbutene- (2) -oyl) -cyclohexen- (2), cis- and trans-23,6,6-tetramethyl-1-pentene - ^ - oyl-cyclohexen- ^),

cis- and trans-2,4,6,6-tetramethyl-l- (2-methyl-buten- (2) -oyl) -cyclohexen- <2), 2,4,6,6-tetramethyl-1 - (3-methylbutene- (2) -oyl) -cyclohexen- (2),

cis- and trans-2,4,6,6-tetramethyl-1-penten- (2) -oyl) -cyclohexen- (2),

cis- and trans-2,4,6,6-tetramethyll-crotonoyl-cyclohexene ^), cis- and trans-2 ^, 6,6-tetramethyll- (2-methyl-buten-{2) -oyl) -cyclohexene - {2),

2 ^, 6,6-tetramethyl-l - (3-methyl- buten- {2) -oyI) -cyclohexen- (2),

cis and trans-23,6,6-tetramethyl penten- (2) -oyl-cydohexen- (2), ds and trans-2A6,6-tetramethyl- 1 -crotonoyl-cyclohexen- ^), ds- and trans-2, 6-dimethyl-6-ethyl 1- <2-methyl-buten- {2) -oyi) -cyclohexen- {2),

2 ^ -Dimethyl-6-ethyl-1- {3-methyl buten- (2) -oyl) -cydohexen- (2),

ds- and trans-2J6-Diinethyl-6-ethyl- 1 -pentene ^ Voyl-cyclohexene ^),

ds- and trans ^ e-Dimethyi-e-äthyl l-crotonoyl-cydohexen- {2), ds- and trans-24,6,6-tetramethyl l- (2-methyl-buten- (2) -oyl) - cydohexen- (1), 23,6,6-tetramethyl-1 - (3-methyl- buten- {2) -oyl) -cyclohexen- (1), cis- and trans-23,6,6-tetramethyl-1 - (pentene- ( 2) -oyl) -cyclohexen- (l), cis- and trans-23,6,6-tetramethyl-1 -crotonoyl-cyclohexen-i 1), cis- and trans-2,4i6,6-tetramethyl-1 - (2-methyl-buten- (2) -oyl) -cyclohexene (1), 2,4,6,6-tetraniethyl-1- (3-methylbutene- (2) -oyl) -cyclohexene (1), cis- and trans-2,4,6,6-tetramethyl-ο 1 -pentene- (2) -oyl-cyclohexene (l), cis- and trans-2,5,6,6-tetramethyl l- (2- methyl-buten- {2) -oyl) -cyclohexen- {l), cis- and trans-2,5,6,6-tetramethyll- (penten- (2) -oyl) -cyclohexen- {l), cis- 2,5,6,6-tetramethyl- \ -crotonoylcyclohexen-il),

cis and trans-2,6-dimethyl-6-ethyl-1 - (2-methyl-buten- (2) -oyl) -cyclohexen- (l), 2,6-dimethyl-6-ethyl-l- (3-methylbutene- (2) -oyl) -cyclohexen- (l), cis- and trans-2,6-dimethyl-6-ethyl- (penten- (2) -oyl) -cyclohexen- (l), cis- and trans-2,6-trimethyl-l- (2-methylbutene- (2) -oyl) -cyclohexen- (l), cis- and trans-2,6,6-trimethyl-1 - {penten- (2) -oyl) -cyclohexen- (1),

cis- and trans-S ^^ - trimethyl-i-methylenl- (3-methyl-buten- (2) -oyl) -cyclohexane, cis- and trans-3,6,6-trimethyl-2-methylene-1 - (penten- (2) -oyl) -cyclohexane, cis- and trans-3,6,6-trimethyl-2-methylene-1-crotonoyl-cyclohexane,

cis- and trans-4,6,6-trimethyl-2-methylenl- (2-methyl-buten- (2) -oyl) -cyclohexane, 4,6,6-trimethyl-2-methylene-1 - (3-methylbutene- (2) -oyl) -cyclohexane, cis- and trans-4,6,6-trimethy! -2-methylen-1 - (penten- (2) -oyl) -cyclohexane, cis- and trans-4,6,6-trimethyl-2-methylene-1-crotonoyl-cyclohexane,

cis- and trans-Sii-trimethyl ^ -methylenel- (2-methyl-buten- (2) -oyl) -cyclohexane, 5,6,6-trimethyl-2-methylene-1 - (3-methylbutene- (2) -oyl) -cyclohexane, cis- and trans-SÄe-trimethyl ^ -methylene-1 - (penten- (2) -oyl) -cyclohexane, cis- and trans-S ^^ - trimethyl ^ -methylene-1 -crotonoyl- cyclohexane,
cis and trans-e-ethyl-e-methyW-methylen-1 - ^ - methyl-buten-pyoyty-cyclohexane, 6-ethyl-6-methyl-2-methylene-1 - (3-methylbutene- (2) - oyl) -cydohexane, cis- and trans-6-ethyl-6-methyl-2-methylene- 1 - (pentene- (2) -oyI) -cyclohexane, ds- and trans-6-ethyl-6-methyl-2 -methylene-1 -crotonoyl-cyclohexane,
ds- and trans-6,6-methylene-1-methylene-1 - (2-methyl-buten- (2) -oyl) -cydohexane, 6,6-dimethyl-2-methylene-1- (3-methyl buten- {2) -oyl) -cyclohexane, ds- and ΐΓβηβ-β, β-ΟίιηβαιγΙ-Σ-ηιβΛγΙεη-1 - <pentene- <2) -oyl) -cydohexane, 2,6,6-trimethyl-t- {3-methyl-buten- {3) -oyl) -cyclohcxen- (2) and

ice and trans ^ e-dimethyl-e-ethyl-

1-crotonoyl-cydohexen-il). Further connections according to the invention are described in the following exemplary embodiments

which the temperatures are given in degrees Celsius.

example 1

2,4,6,6-tetramethyl-l-trans-crotonoyI-cyclohexen- (l)

A mixture of 10 g of 2,4,6,6-tetramethyl-l ^ (l-hydroxy-buten- (2) -yl) -cyclohexen- (l), 100 g of activated manganese dioxide and 300 ml of pentane were stirred for 45 hours at 20 ° in an argon atmosphere. The reaction mixture was filtered and the solid residue was washed with pentane. The clear filtrate turned to dryness evaporated. The residue was dissolved in 100 ml of dry benzene. After addition of 160 mg of p-toluenesulfonic acid the solution became itself in an argon atmosphere at room temperature for 16 hours left. The reaction mixture was washed with ether in the presence of 5% aqueous sodium bicarbonate solution 7.96 g of 2,4,6,6-tetramethyl-1-trans-crotonoyl-cyclohexene (I. receive. Bp = 60-62 ° / 0.001 Torr. For analytical purposes this was a sample Product purified by column chromatography (KhSiCh, benzene). The purified product had the the following physical properties:

t / 2 ⁰ = 0.9223; ni ° = 1.4919.

IR spectrum: ν = 970 (-CH = CH-trans), 1615, 1645, 1670 cm- ¹ (C = CC = O).

Mass spectrum: M ⁺ = 206.

NMR spectrum:

0.80 - 1.05 (6H, m, 2 CHs-),

1.09

3 H. see CH ₃ -C

1.48 13 H. see CH ₃

1.88 (. 3 H d, d J = 6.5 and about 1 cps, -CH = CH-CH _3), 1.2 to 2.2 (5H, m), 6.00 (1 H .dq.J = 16 and approx. 1 cps, -CO-CH = CH-CHs).
6, (53 (1H, dq, J = 16 & 6.5 cps, -CO-CH = CH-CH ₃ ).
UV spectrum: A _ma x = 225πιμ (ε = 12390 in alcohol).

Analysis for Ci4H22O:

Named: C = 81.50; H = 10.75%; Found: C-81.49; H = 1039.

The 2,4,6,6-tetramethyl-1 used as starting material <1 -hydroxy-buten- ^ VyO-cyclohexene-O) was manufactured as follows:

a) 4-methyl-pentene- (3) -ol- (2)

This alcohol was after the in HeIv. Chim. Acta, 30, 2216 (1947) described method prepared 245 g of mesityl oxide were dissolved in 1200 ml of dry ether. This solution was added to a mixture of 30 g of LiAlFU and 200 ml of dry ether at reflux temperature over the course of one hour NH4C1 in 1 liter of water. Extraction with ether and work-up by customary methods gave 221 g of 4-methyl-pentene- {3) -ol- (2), b.p. -50 ° / 11 Torr. The product obtained in moist form was dried by treatment with anhydrous K2CO3 in petroleum ether (30-50 °)

c / 7-0.8421; / ?; -1.4383.

IR spectrum: ν = 1050 (CO), 1670 (C = C), 3350 cm- '(OH).

Mass spectrum: M ⁺ = 100.

NMR Spectrum: 1.11 (3H, d, J = 6 cps), 1.64 (6H, m), 4.04 (1H, s), 4.15-4.65 (1H , m). 5.10 (1H, d,] = ca. 8 cps). δ ppm.

Analysis for C6H12O:
Calculated: C = 71.95; H = 12.08%; found: C = 71.83; H = 12.19%.

b) 4- bromo-2-methyl-pentene- (2)

This bromide was after the in HeIv. Chim. Acta, 30, 2216 (1947) described method prepared a solution of 220 g of 4-methyl-pentene- (3) -ol- (2) in 250 ml

Petroleum ether (30-50 °) and dry pyridine (41 g) was freshly distilled to a mixture of 233 g PBn and 10 drops of dry pyridine added at -20 ° over the course of one hour by direct distillation of the reaction mixture were 274 g of 4-bromo-2-

methyl-pentene- (2) obtained. Because of its inconsistency, this product was processed immediately.

c) 4,6-dimethyl-hepten- (5) -one- (2)

This ketone was after the in HeIv. Chim. Acta, 30, 2216 (1947) described method produced The 274 g of the bromide obtained in paragraph b) were at a temperature of -5 ° to -10 ° of a solution of sodium acetylacetate (obtained by reacting 40.7 g of sodium and 230 g of ethyl acetate in 670 ml of anhydrous ethanol) were added. The reaction mixture was allowed to react for 2 days at 2u ". Extraction and work-up of the reaction mixture by customary methods gave 252 g of keto ester intermediate. This product was dissolved in 928 ml of ethanol. This solution was added a solution of 444 g of Ba (OH) 2 · 8 HjO in 3280 ml of water and the reaction mixture was heated under reflux for 2 hours.The precipitate formed in the course of the reaction was dissolved in 10% hydrochloric acid ethereal extract, 142 g of a product boiling at 53-57 ° / 10 Torr were obtained, 70% of which was 4,6-dimethyl-hepten- (5) -one- (2) and 30% of which corresponded to The two compounds were separated by preparative gas phase chromatography and had the following physical properties:

4,6-dimethyl-hepten- (5) -one- (2)

55 IR spectrum: ν - 830, 1360 (CHsCO), 1710 cm "(CO).

Mass spectrum: M ⁺ - 14a
Nuclear Magnetic Resonance Spectrum: 039 ( 3H, d, J- 6.5 cps), 1.62 (6Hs), 2.00 (3Hs), 2 ^ 2 (2ad, J- 7cps.), W- 3.2 (1 H, m. 60 433 (1 H, d, J - 8cps) ippm.

4,4-dimethyl-hepten- (5) -one- (2)

Mass spectrum: M ⁺ - 14a

Nuclear Magnetic Resonance Spectrum: 1.07 (6 H, A 1.63 (3 R < 65 I - 4.5 cps), 139 (3H, s), 238 (2R s), 5.40 (2H, π oppm.

The mixture of isomers was used directly for the next step without separation

d) 2,4,6-trimethyl-octadiene- (2,6) -al

This dienal was prepared according to the method described in Tetrahedron SuppU No. 8, Part I, 347 (1966) manufactured

A solution of 44.8 g of diisopropylamine in 100 ml of dried ether of a solution of butyllithium was added (14% in hexane) in 200 ml of dry ether in an argon atmosphere and left the reaction mixture react at 20 ° for 2 hours. 55 g of ethylidenecyclohexylamine were added to the reaction mixture at 0 ° and then added at -70 ° 70 g of the ketone mixture obtained in accordance with paragraph c). The reaction mixture was left 1/2 hours at -70 ° and then a Stand at 20 ° at night. 800 ml of 20% strength acetic acid were added to the reaction mixture at 0 ° and the mixture was stirred the mixture for 3 hours at 20 ° in an argon atmosphere. By extracting the reaction mixture and Working up the extract by customary methods gave 44.6 g by distilling the crude product obtained from a fraction boiling at 52 - 70 ° / 03 Torr, which was purified by renewed distillation. In this way, a mixture of 2,4,6-trimethyloctadien- (2,6) -al was obtained and 4,4,6-trimethyl-octadien- (2,6) -al in a weight ratio of about 3: 2. This mixture was used directly for the next reaction stage without prior separation.

e) 4-methyl-jS-cyclocitral

A solution of 36.5 g of the aldehyde mixture prepared in accordance with paragraph b), 21.4 g of aniline and 20 g anhydrous sodium sulfate in 55 ml of ether was stirred for one night at 20 °. The reaction solution was washed and concentrated and then concentrated with vigorous stirring into a mixture of 221 ml. sulfuric acid and poured 22.1 g of ice. The mixture was kept between -20 ° and -25 ° for 1 hour and then at 300 g Poured ice. The reaction mixture was then subjected to steam distillation. The The distillate was saturated with common salt and extracted with ether. The extract was worked up in the usual way 36 g of a mixture of crude «- and ^ -Cydocitral were obtained. This cyclocitral mixture was at -10 ° to 120 ml of an 8.5% ethanolic KOH solution (80% ethanol). One let the reaction mixture react for 3 hours in an argon atmosphere, then diluted it with petroleum ether (30 - 50 °), poured it into 400 ml of saturated aqueous sodium chloride solution and extracted the mixture with petroleum ether. Obtained by working up the extract by customary methods and distilling the crude product 18 g of a fraction boiling at 90 to 95 ° / 10 Torr and consisting of 4-methyl- | 3-cyclocitral. This Product had the following physical properties:

rf? » 03564 ^? = 1.4847.

IR spectrum: ν - 1610, 1670, 1720 (C = C; C = O) 2760.2820 cm- '(CHO).

Mass spectrum: M ⁺ - 166.

Nuclear Magnetic Resonance Spectrum: 032 (3 H, d, J - approx. 4 cps), 1.13 (6 H, sX 2.05 (3 H, s), 1.0-2PO (5 H, m \ 10.22 ( t H, s) d ppm.

UV spectrum: ASS "- 248 mn (s - 9416).

f) 2,4A6-tetramethyl-l- {l-hydroxy-

buten- (2) -yl) -cyclohexen- (l) _6j

A solution of 16.4 g of 4-methyl-ß-cydodtral in 20 ml of dry ether was added to a propenyllithim solution at -20 ° within 35 minutes, which by adding a solution of 9.7 g of 1-chloropropene in 80 ml of dry ether at -10 ° to 1.85 g of granulated Lithium (sodium content 1%) was freshly made. After 3 hours of standing at 20 ° this was Lithium salt solution for addition to the 4-methyl-j9-cydocitral ready After the addition was complete, the reaction mixture was left at -15 "to -20 ° for 5 hours react and then stand at 20 ° for one night. The reaction mixture was then dissolved in 60 g of NH4Cl Poured containing ice water. The mixture was extracted with ether and the extract was concentrated at 40 ° -50 ° in a vacuum. Distillation of the residue gave 18.6 g of a 55-58 "/ 0.0Ol Torr boiling fraction, which consists of a mixture of ice and trans isomers of 2,4,6,6-tetramethyl-1- (I-hydroxybutene- (2) -yl) -cycIohexen- (l) duration. This product had the following physical characteristics:

df = 03300; n ¥ = 1.4933.

IR spectrum: ν = 970 (-CH = CH-trans), 1030 (CO), 1645 (C = C), 3400 cm- »(OH).

Mass spectrum: M ⁺ = 208.

Nuclear Magnetic Resonance Spectrum: 0.8-1.2 (9H, m), 1.5-1.8 (6H, m), 1.0-23 (5 H, m), 2.4 (1 H, s, wide band), 4.65 (1 H, m), 5.55 (2 H, m) δ ppm.

Example 2

2,4,6,6-tetramethyl-1-trans-crotonoylcyclohexadiene- (l 3)

4.86 g of 2,4,6,6-tetramethyl-1-trans-crotonoyl-cydohexene-O) prepared according to Example 1 were combined with 5.85 g of N-bromosuccinimide, 0.6 g of bis-azo-isobutyronitrile, 40 ml CH2Cl2 and 40 ml CCU stirred in a moisture-free vessel at 50 ° Minutes the solution was clear as a result of dissolution of the N-bromosuccinimide, while succinimide as Precipitation separated off. The reaction mixture was stirred for a further 5 minutes at 50 ° and then afterwards Cooling to 20 °, while stirring with 10.6 g of diethylamine The reaction mixture was mixed with 100 ml of petroleum ether (30-50 °) and homogenized filtered by evaporating the filtrate at 40 ° in vacuo and then heating the for 1 hour Residue at 135-145 °, 3.6 g of a mixture were obtained, which consists of the starting ketone and

2,4,6,6-tetramethyl-1-trans-crotonoyl-cyclohexadiene- (13) was composed in a weight ratio of 45:55. 2,4,6,6-Tetramethyl-1-trans-crotonoyl-cydohexadiene- (13) was determined by column chromatography (40 parts by weight S1O2 in the presence of benzene) separated It had the following physical properties:

df- O343I, π? = 13115.

IR spectrum: ν - 970 (-CH = CH-trans), 1620 1670 cm- '(C-CC = O).

Mass spectrum: M ⁺ = 204.

Nuclear Magnetic Resonance Spectrum: 1.00 (6 H, s), 1.60 (3 H, s), Iv89 (3 H, dd, J = 63 and approx. 1 cps), 1.80 (3 H, s) , approx. 1.7 - 13 (2 H, m), 532 (1 H, s wide, 6.05 (1 H, dq "J = 16 and approx. 1 cps), 6.72 (1 H, dq , J - 16 and 63 cps) δ ppm.

UV spectrum: λ ££ ^Η - 227 mn (s - 15,090).

Example 3

23,6,6-tetramethyl-l -trans-crotonoylcydohexen- (l)

A mixture of 8.0 g of 2A6,6-tetramethyl-l- (l-hydroxy-buten- (2) -yl) -cydohexen- (l) (manufactured according to

Paragraph e) of this example), 80 g of activated manganese dioxide and 250 ml of pentane was in an argon atmosphere Stirred at 20 ° for 21 hours. The reaction mixture was filtered and the residue was mixed well with pentane washed out. The clear filtrate was concentrated to dryness. The residue (8 g) was dissolved in 80 ml dissolved in dry benzene. After adding 160 mg of p-toluenesulfonic acid, the mixture was left in a React in an argon atmosphere for 16 hours at room temperature. By extraction of the reaction mixture ι ο with ether in the presence of sodium bicarbonate (5% aqueous solution) and work up the essential Extract according to customary methods were, by vacuum distillation of the crude product, 6.83 g of 2,5,6,6-tetramethyl-1-trans-crotonoyl-cyclohexene-fl), Bp = 64-67 ° / 0.001 Torr. This product rejected the the following physical properties:

df = 0.9426; nl ° = 1.5016.

TR spectrum: ν = 970, 1615, 1640, 1670 cm ¹ .

Mass spectrum: M ⁺ = 206.

Nuclear Magnetic Resonance Spectrum: 0.8-1.0 (9H, m); 1.47 (3H, s); 1.87 (3 H, d. D, J = 6.5 and about 1 cps); 6.58 (1H, i.e. q, J = 16 and 6.5 cps) δ ppm.

UV spectrum: λ ™ ° ^Η = 227πιμ (ε = 11.545).

The 2,5,6,6-tetramethyl-1 used as the starting material - (I-hydroxy-buten- (2) -yl) -cyclohexen- (l) became manufactured as follows:

a) l-bromo-2,3-dimethyl-butene (2)

This bromide was after the in HeIv. Chim. Acta, 23,964 (1940) described method prepared 600 g of a 30% solution of hydrobromic acid in Acetic acid was added to 200 g in the course of 1/2 hour at a temperature of -25 ° to -15 ° with stirring Dimethylbutadiene given. The mixture was allowed to react at room temperature for 2 days. The reaction mixture was then poured into ice water and extracted with ether Extract by customary methods and fractional distillation of the crude product gave 261 g of a fraction boiling at 42-44 ° / 10 torr and consisting of 1-bromo-23-dimethyl-butene (2).

b) 5,6-dimethyl-hepten- (5) -one- (2)

This ketone was after the in HeIv. Chim. Acta, 23, 964 (1940) described method prepared 261 g of the bromide obtained according to paragraph a) were at 6-10 ° of a solution of sodium acetylacetate (prepared from 38.8 g sodium and 219 g acetylacetate) in 600 ml anhydrous ethanol added, the reaction mixture was allowed overnight at 20 ° and then react IV2 hours at reflux temperature. After dilution of the reaction mixture with 5 times the volume of water, extraction and work-up of the extract by customary methods gave 263 g of ketoester intermediate. This product was dissolved in 960 ml of ethanol and a solution of 460 g of Ba (OH); 8 H2O in 3400 ml of water were added. The reaction mixture was heated to boiling for 22 hours. The precipitate formed during the reaction was dissolved in 10% hydrochloric acid, the solution was extracted with ether and the ethereal extract was worked up using customary methods. 144 g of 5,6-dimethyl-hepten- {5) -one- (2) were obtained, which boiled at 70-71 ° / 10 Torr and had the following physical properties:

rf? - 03661 χ η? - 1.4500.

IR spectrum: v = 1350.1710 cm- '. Mass spectrum: M ⁺ = 140.

Nuclear Magnetic Resonance Spectrum: 1.63 (9H, s); 2.07 (3H, s); 2.30 (4H, m) <5 ppm.

c) 3,6,7-trimethyl-octadiene- (2,6) -al

This dienal was prepared according to the method described in Tetrahedron Suppl, No. 8, Part I, 347 (1966) A suspension of 7.77 g of lithium in 150 ml of dry ether was mixed with a solution of 79.8 g of methyl iodide in 250 ml of dry ether at -15 ° and let the mixture for 24 hours at 20 ° react. A solution of 55.7 g of diisopropylamine in 100 ml was then added to the reaction mixture dry ether and let it react for 2 hours at 20 °. Deir. The reaction mixture was then 68.7 g Ethylidenecydohexylamine (see Bull. Soc. Chim. France, 1947, 715) and then at -70 ° 70 g Dimethylheptenone added. The reaction mixture was in the manner described in Example 1 further processed Fractional distillation gave 46.1 g of a mixture boiling at 65-69 ° / 0.001 Torr Fraction consisting of a mixture of the cis and trans isomers of 3,6,7-trimethyl-octadien- (2,6) -al im Weight ratio of about 1: 2 existed. This mixture had the following physical properties on:

c /; = 0.8912; nf = 1.4919.

IR spectrum: ν = 1630, 1660, 1715 (C = C, C = O), 2730, 2860 cm- '(CHO).

Mass spectrum: M ⁺ = 166.

Nuclear Magnetic Resonance Spectrum: 1.62 (9 H. s), 1.8-2.7 (7H, complex band), 5.67 (1H, d, J = 7.5 cps), 10.05 ( 1 H, almost t, J = 7.5 cps, as a result of mixing the two d) δ ppm.

d) S-methyl - ^ - cyclocitral

A mixture of 38 g of the aldehyde mixture obtained in accordance with paragraph c), 223 g of aniline, 20 g of anhydrous sodium sulfate and 23 ml of ether was concentrated using 230 ml. Sulfuric acid and 23 g of ice reacted. By steam distillation, saturation with common salt and extraction, 32 g of a mixture of 5-methyl-α-cyclocitral and 5-methyl-0-cyclocitral in a weight ratio of 2: 3 were obtained. The isomerization was carried out at -10 ° in 120 ml of an 8.5% strength ethanolic KOH solution (80% strength ethanol). By treating the reaction product in the manner described in Example 2, paragraph e), 27.6 g of a were obtained 48 to 5470.001 sound boiling product containing about 3 - 5-methyl-cyclocitral was 97% of the ^ -isomer of - 4% of the α-isomer and 96th This product had the following physical characteristics:

d? = 0 $ 528 _; n? = 1.4990.

IR spectrum: v-1610, 1670, 1710, 2760, 2860 cm- '. Mass spectrum: M + - 166. NMR Spectrum: 0.89 (3H, m); 1.03 (3H, s); 1.18 (3H,

^s) i? P ¹ Ii ^u ^ ⁴ * ⁵ "* ¹ W ¹ "> *

P Ii ^u , ^ a ⁴ * ⁵ "·" * ¹ W ¹ "·«> *

-Spectrum: ASS ^H - 248 mm (s - 10546).

e) 2A6,6-tetrameftyl-l- {i-hydroxy-

buten- {2) -yl) -cyclohexen- (l) A solution of 16.6 g of S-methyl-JJ-cyclocitral prepared according to paragraph d) in 20 ml of dry ether was in the course of 35 minutes at -20 ° a solution of PropenyiUthium added This solution was in Example 1. Paragraph f),

described manner freshly prepared By working up the reaction mixture in the manner described in Example 1, Paragraph f), described Weisi. were 93 g one at 54-67 ° / 0.001 Torr boiling fraction obtained, the from 2A6,6-tetramethyl-l- {l-hydroxy-buten- {2) -yr) -cyclohexen- (l) duration. This product had the following physical characteristics:

d? = 0 ^ 656; ^ ° = 1.5055.

IR spectrum:? = 970, 1670, 3400 cm- '.

Mass spectrum: M ⁺ = 208.

NMR spectrum: 0.8-0.9 (3H, m); 0.95 (6H, s); 1.0 2.2 (12H, m); 4.80 (1H, s); 5.70 (2H, m) δ ppm.

Example 4

2,5,6,6-tetramethyl-1-trans-crotonoylcyciohexadiene- ( 1.3)

2,5,6,6-tetramethyl-1 - (3-methylbutene- (2) -oyl) -cyclohexen- (l) 6.4 g of the alcohol obtained were left together with 64 g of manganese dioxide in 190 ml of pentane in an argon atmosphere React for 42 hours at 20 °. The reaction product was prepared in the manner described in Example 1 treated and worked up 53 g of crude product were obtained, which was purified by column chromatography on H2S1O3. Pure was obtained in this way 2,5,6,6-tetramethyl-1 - (3-methylbutene- (2) -oyl) -cyclohexen- (l), that had the following physical properties ίο:

Kp. = 80 ° / 0.001 Torr; c /? = 0.9353; n'i = 1.5040. IR spectrum: v = 1605.1665 cm- ¹ . Mass spectrum: M ⁺ = 220.

Nuclear Magnetic Resonance Spectrum: 0.80-1.10 (9H, m); 1.53 (3H, s): 2.14 (3H, s); 1.39 (3H, s); U - 23 (5H, m); 6.06 (1H, s) ό ppm.

UV spectrum: λ ™ ° ^Η = 2.44 mn (ε = 13510).

4.86 g of 2,5,6,6-tetramethyl-1-trans-crotonoyl-cyclohexen- (l) (prepared according to Example 3) was in the manner described in Example 2 with 5.85 g of N-bromosuccinimide, 0.6 mg bis-azo-isobutyronitrile, 40 ml CH2Cl2 and 40 ml CCU brought to reaction by working up of the reaction product in the manner described in Example 2 were 3.71 g of 2,5,6,6-tetramethyll-trans-crotonoyl-cyclohexadiene- ^) of bp = 75 ° / 0.001 Torr. This product had the following physical characteristics:

d <= 0.9863; n < = 1.5139.

IR spectrum: v = 970, 1610, 1630, 1670 cm- '.

Mass spec: M ⁺ = 204.

NMR Spectrum: 0.89 (3H, s); 1.02 (3H, s); 0.97 (3 H, d, J = about 8 cps); 1.58 (3H, s); 1.88 (3 H, dd, J = 6.5 and approx. 1 cps); 1.8 - 2.3 (1H, m); 5.60 (2H, m); 6.0 (1H, d. Q., ] = 16 and approx. 1 cps); 6.70 (1H, d. Q, J = 16 and 6.5 cps) ο ppm.

UV spectrum: λ ™ ° ^Η = 228 mn (ε = 11,640).

Example 5

45

11.0g S-methyl-ß-cyclocitral [obtained according to example 3, paragraph d) j, dissolved in 30 ml of tetrahydrofuran, were at -10 ° a by reaction of 2.4 g Magnesium and 13.5 g of 1-bromo-2-methyl-propene in 30 ml of dry tetrahydrofuran Grignard solution The reaction mixture was allowed to react for 2 hours at -5 to 0 ° and then for one night stand at room temperature. By treating the reaction product with NH4Cl at 0 ° in the in the previous examples described manner, extraction, work-up of the extract according to the usual Methods and fractional distillation of the crude product were 8.7 g of a 70-72 ° / 0.001 Torr the boiling fraction obtained from 2,5,6,6-tetrame- fm ethyl-1 - (1-hydroxy-3-methyl-buten- (2) -yl) -cyclohexen- (1) duration. This product had the following physical characteristics:

IR spectrum: v = 1020.3400 cm- '.

Mass spectrum: M ⁴ = 222, h <

Nuclear Magnetic Resonance Spectrum: 0.65-1.10 (9H, m); 1.6-2.0 (9H); 2.45 (1H, s); 1.0-2.2 (5H, m); 4.9 (1 H; almost d, J = approx. 8 cps); 5.50 (1 H, fast d, J - about 8 cps) ό ppm.

ICE PIECE 6

2,6,6-trimethyl-1 - (3-methyl-buten- (2) -oyl) -cyclohexen- (l)

a) A solution of 1-chloro-2-methyl-propene (47.5 g) in 50 ml of dry ether was in an argon atmosphere at -10 ° in the course of half an hour of a suspension of 7.6 g lithium (sodium content 1%) added in dry ether. The reaction mixture was left at room temperature for 3 hours react. 63 g of iS-cyclocitral were added to the reaction mixture at -15 ° over the course of 5 hours -15 ° and kept at 20 ° overnight and then in an ice-cold aqueous solution of NH4Cl poured and finally extracted with ether. By evaporation of the ether in a vacuum at a temperature below 40 °, 76 g of crude product were obtained. By careful distillation of the latter in the presence of Traces of sodium carbonate were obtained in 21.4 g of a fraction boiling at 55-60 ° / 0.001 Torr, which in the Cooling solidified and was recrystallized from petroleum ether (30-50 °) at -10 °. One received on this Way pure 2,6,6-trimethyl-l- (1-hydroxy-3-methyl-buten- (2) -yl) -cyclohexen- (l), which had the following physical properties:

M. p. 55 - 56.5 °

MS: M ⁺ = 208.

IR: 1020, 1650, 3400-3600 cm- '.

NMR: 0.87 (3H, s), 1.13 (3H, s), 1.70-1.80 (9H, m), 1.20-2.30 (6H, m), 3.27 (1H, s), 4.85 (1H, d, J = 8 cps), 5.46 (1H, fast d, J = 8 cps) <5 ppm.

b) 1.0 g of 2,6,6-trimethyl-1 - (I-hydroxy-3-methyl-buten- (2) -yl) -cyclohexen- (l) react with 10 g of activated manganese dioxide in 30 ml of pentane for 63 hours at room temperature. By filtration of the The reaction mixture and work-up of the filtrate by the customary methods gave 630 mg of 67 ° / 0.01 torr of boiling 2,6,6-trimethyl- 1- (3-methylbutene- (2) -oyl) -cyclohexen- (l), which had the following physical properties:

dt = 0.9310; / 20 ° = 1.5029.
IR: k = 16.05.1665 cm- '.
MS: M ⁺ = 206.

NMR: 1.04 (6 H, s), 1.55 (3 H, s), 1.89 (3 H, d, J = ca 1 cps), 2.15 (3 H, s), 1.20-2.20 (6 H, m), 6.09 (1 H, s) <5 ppm. UV: λ, ^{1;, 1} ,,? ¹ = 244 mn (f = 12,840).

709 607/163

33
Example 7

2,6,6-trimethyl-1- (3-methyl-2-buten- (2) -oy!) -Cycidohexadiene- (l 3)

Eu) Genriisch of 2.1 g 2,6,6-trimethyl- (3-methyI-buten (2) -oyl) -cyclohexen- (l), 2.18 g N-bromosuccinimide, 20.4 ml CH2Ch and 20 , 4 ml of CCl ₄ was heated at 45-50 ° with exclusion of moisture. The mixture was allowed to react until the succinimide completely precipitated (about 1 hour). 3.46 ml of diethylamine were then added to the reaction mixture at 20 ° and then 51 ml of petroleum ether (30-50 °). The reaction mixture was filtered and the clear filtrate was concentrated (40 °). The residue was heated in an argon atmosphere at 130-150 ° for 1 hour and, after cooling, poured into an excess of 10% hydrochloric acid in the presence of petroleum ether. The mixture was finally extracted with a further amount of petroleum ether 1.38 g of a product boiling at 70 ° / 0.001 Torr and consisting of a mixture of starting material and the desired end product in a weight ratio of about 1: 1. Column chromatography on silica in the presence of benzene gave pure 2,6,6-trimethyl-1 - (3-methyl-buten- (2) -oyl) -cyclohexadiene- (13), which had the following physical properties:

d ^! . = 0.31566; n? = 1.5169.

IR spectrum: v = 1602.1660 cm- '.

Mass spectrum: M ⁺ = 204.

Nuclear Magnetic Resonance Spectrum: 1.03 (6 H, s), 1.67 (3 H, s), 1.85 (3 H ₁ d, J = approx. 1 cps), 2.02 (2 H, s) , 6.01 (1H, s), δ ppm.

UV spectrum: A ^ "= 246 mn (ε = 12,490); 309 mn (ε = 2980).

Example 8
2,3,6,6-tetramethyl-1-crotonoyl-cyclohexen- ^)

8.4 g of 2,3,6,6-tetramethyl-1 - (1-hydroxy-buten- (2) -yl) -cyclohexen- {2) was oxidized and isomerized in the manner described in Example 1. The reaction product was purified by column chromatography on silica in the presence of benzene. 131 g were obtained 23,6,6-tetramethyl-l-crotonoyl-cyclohexene (2), which the had the following physical properties:

d'f - 0.9330; n? - 1.4976.

IR spectrum: v-970.1620-1680cm- '.

Mass spectrum: M ⁺ - 206.

Nuclear Magnetic Resonance Spectrum: 0.80 (3 H, s), 0.90 (3 Hs), 1.50 (3 H, s), 1.55-2.40 (10 H, complex band), 2.82 (1 H, s), 6.19 (1 H, d. Q,] - 16 and approx. 1 cps), 6.80 (1 H, d. Q, J - 16 and 6.5 cps), δ ppm

UVSλ

) pp
UV spectrum:

: λ

227 mn (e - 10,810).
f

The carbinol used as the starting material was produced as follows:

a) l-bromo-3-methyl-butene

This bromide was after the in HeIv. Chim. Acta, 5, 750 (1922) described method produced to 200 g Isoprene was a 30% solution of hydrobromic acid (815 g) in Glacial acetic acid. The mixture was kept at 0 ° for 3 days and then poured into 4 liters of cold water. The organic phase was decanted off over CaCb dried and distilled 312 g of the at 24 - 28 ° / 10 Torr boiling Brcmids.

b) 3,6-dimethyl-hepten- (5) -one- (2)

This ketone was used in the HeIv. Chim. Acta, 30, 2213 (1947). Wise prepared The 312 g of bromide obtained in accordance with paragraph a) were at a Temperature from -5 ° to -10 ° of a solution of sodium-Ä-methyl-acetyl-acetic acid ethyl ester (prepared from 383 g of sodium and 250 g of a-methyl-acetyl acetic acid ethyl ester) added in 940 ml of Aethanoi The ίο reaction mixture was kept at 20 ° for 2 days and then worked up in the manner described in Example 1, paragraph c). 219 g of the at 65 ° 70 ° / 0.001 were obtained Torr Boiling Ketoester Intermediates A mixture of 160 g of this product, 307 g Ba (OH> - 8 H20.2130 ml of water and 665 ml of Aetharol was heated to boiling for 22 hours Paragraph c), as described, 79.6 g of 3,6-dimethyl-hepten- (5) -one- (2) boiling at 55 - 58 ° / 8 Torr obtained that had the following physical properties:

d? - 03495JiJo ¹ - 1.4414.

IR spectrum: v = 1350.1710 cm- '.

Mass spectrum: M ⁺ - »140.

Nuclear Magnetic Resonance Spectrum: 1.00 (3 H, d, J - 6.5 cps); 1.58 (3 H s); 1.66 (3H, s); 2.03 (3H, s); 1.7 - 2.7 (3H, m); 5.00 (1 H t, J = 7 cps) δ ppm.

c) 3,4J-trimethyl-octadiene (2,6) - al

This dienal was described in Tetrahedron Su ppi., No. 8, Part I, 347 (1966) described manner prepared A solution of 56.1 g of diisopropylamine in 100 ml! dry ether was under argon a solution of butyllithium (275 g of a 14% solution in hexane) in 200 ml of dry ether were added. The mixture was left to react for 2 hours at 20 °.

70 g of the one prepared in accordance with paragraph b) of this example Ketones were in the manner described in Example 1, paragraph d) with 68.7 g of ethylidenecyclohexyl amine reacted. 57 g of at 52-62 ° / 0.001 were obtained Torr boiling 3,4,7-trimethyl-octadien- (2,6) -al, which had the following physical properties:

df - 03883; π "- 1.4866.
IR spectrum: v-1620, 1670, 1710 cm- '. Mass spectrum: M ⁺ · »166.
Nuclear Magnetic Resonance Spectrum: 1.06 (3 H, d, J - 6 cps); 1.57 (3H, s) 1.65 (3H, s); 2.08 (3H, s); 1.8-2.5 (3H, m); 4.95 (1H, t J - about 7 cps); 5.68 (1H, d, J - 7.5 cps); 9.79 (1 H, d J - 74 cps) δ ppm.

UV spectrum: λ ™, - 241 mn (e - 14,250).

d) S-methyl-Ä-cyclocitral

From 46.6 g of 3,4,7-trimethyl-octadien- (2,6) -al were ir in the manner described in example 1, paragraph c), £ 36 obtained raw S-methyl-cyclocitral, which is a fraction was subjected to ned distillation. 20.6 g of a fraction boiling at 81-83.5 ° / 8 torr were obtained which contain about 91% 3-methyl-a-cyclocitra exhibited. This product had the following physical properties:

(/ 7 -0.925O; / ?? - 1.4805.

IR spectrum: i> - 1670,1710,2710,2860cm- '.

Mass spectrum: M ⁺ «166.

NMR Spectrum: 0.87 (3H ₁ s); 0.95 (3H, s); 1.52 (3H, s); 1.68 (3H, s); 1.0-2.4 (5H, m); 9.28 (1 H, d J - 5 cps) δ ppm

Ä ™ ° ^H - 238 mu, (e - 2850).

e) 23,6,6-tetramethyl-1 - (1-hydroxybutene- (2) -yl) -cyclohexen- (2)

20.5 g of a-methyl-a-cydocitral, 2 ^ 9 g of lithium and 113 g of 1 -chloroprene were in the example 1, paragraph F), as described, reacted in 125 ml of dry ether by fractional distillation 163 g of that boiling at 56-59 ° / 0.001 Torr 23,6,6-tetramethyl-l- (l-hydroxy-buten- (2) -yl) -cycIohexen- (2) receive. This product was used directly to produce 2,3,6,6-tetramethyl-1 without further purification -crotonoyl-cyclohexen- ^) used

Example 9
2,6,6-trimethyl-1-crotonoyl-cycluhexen- (1) ' ⁵

A mixture of 2,6,6-trimethyl-1-vinylacetylcydohexene (lX 0.2 g of p-toluene-sulfonic acid and 100 ml of benzene was heated at 80 ° for 30 minutes. After cooling, the reaction solution was treated with concentrated aqueous Sodium bicarbonate solution neutralized, washed with water, dried and worked up in the usual way In this way, 2,6,6-trimethyl-1-trans-crotonoyl-cydohexen- (l), Bp = 84-85 ° /

0.001 Torr; d? = 03374; n% = 1.4989.

The 2,6,6-trimethyl-1-vinylacetyl-cydohexen- (l) used as starting material was prepared in the manner described in Example 10 below

Example 10

2,6,6-trimethyl-1-vinylacetyl-cydohexene (1) and
2,6,6-trimethyl-1 - (3-methyl-buten- (3) -oyl) -

cyc! ohexen- (l)
(see J. Am. Chem. Soc, 75,422 [1953])

41 g of pure chromic anhydride were added in portions at 0 ° to 450 ml of dry pyridine. A solution of 2,6,6-trimethyl-l- (l-hydroxy-buten- (3) -yl) -cyclohexene (l) was then added dropwise to this solution at 0 °. The reaction mixture was stirred at 0 ° and for 30 minutes then held at 20 ° for 10 hours. The reaction solution was then poured into 1 liter of water and extracted with ether. The combined ethereal extracts were washed with 10% aqueous hydrochloric acid, neutralized with 5% aqueous sodium bicarbonate solution and finally washed with water. By working up the extracts by the customary methods and distillation, 2,6,6-trimethyl-1-vinyl-acetyl-cyclohexene (l) was obtained in 60% yield, λ? - 1.4897; df - 0.9361.

By using 2,6,6-trimethyl-1- (I-hydroxy-3-methyl-buten- (3) -yl) -cyclohexen- (l) (n ™ = 1.4939; d * i - 03270) Instead of 2,6,6-trimethyl-1- (I-hydroxy-buten- (3) -yl) -cyclohexen- (t), 2,6,6-trimethyl-1- (3 -methylbutene- (3) -oyl) -cyclohexen- (l) obtained. πΌ ° = 1.4862; dT - 03307.

The hydroxy compounds used as starting materials were followed by a <*> Grignard reaction between 0-cydocitral and allyl bromide or between j3-cydocitral and methallyl chloride prepared for example in the following described way.

10.7 magnesium turnings and 5 g of allyl bromide were made to react in 70 ml of dry ether The reaction was exothermic, so that the temperature of the reaction mixture rose to the boiling point of the

35 means rose. To the Grignard solution obtained, 46 g of allyl bromide and 61 g of / 3-cydocitral in 16C ml of ether were added with vigorous stirring at such a rate that the ether was obtained at the boil. The reaction mixture was then refluxed for 6 hours and, after cooling, poured into an ice-cold concentrated aqueous solution of NH4Cl. The ethereal layer was separated off and worked up according to the usual methods. 44.5 g of ^, e-trimethyl-l ^ l-hydroxybutene- ^ yO-cyclohexene (1) were obtained. Bp = 60-62 ° / 0.001 torr; n ™ = 1.4964;

df = 0.9398. This product had the following spectroscopic data:

NMR Spectrum (CCl ₄ ): 038 (3 H, s); 1.10 (3H, s); 1.82 (3H, s); 1.20-2.80 (9H, m); 4.22 (1H, m); 5.04 (2H, d, J = 15 cps); 538 (1 rLmjdppm.

By using the equivalent amount of methallyl chloride instead of allyl bromide, after the above procedure, the corresponding carbinol obtained in practically the same yields.

Example 11
2,6,6-trimethyl-1-penten- (2) -oyl-cyclohexen- (2)

a) 75 g 7, ll-dimethyl-5-oxo-dodecatriene :-( 3,6,10) [with a low content of 7,1 l-dimethyl-5-oxo-dodecatriene- (3,6,10) and II-methyl ^ -methylene-S-oxo-dodecadiene- (3,10)] were added dropwise under nitrogen at 0-5 ° to a vigorously stirred solution of 30 g of tin tetrachloride in 350 ml of dry benzene. The reaction mixture was stirred at 30.degree.-35.degree. C. until the complete disappearance of the starting strienes was found by gas phase chromatography (about 2 to 3 hours). The reaction mixture was then poured onto crushed ice and extracted with ether. The essential extracts were washed with water until they were neutral to litmus paper. The extracts were then dried and concentrated. The residue (72 g) was subjected to fractional distillation. In this way, 22.6 g of trans-2,6,6-trimethyl-1-pentene- (2) -oyI-cyclohexene (2) were obtained. B.p. = 75-77 ° / 0.1 torr; n " = 1.4925; d? = 0.9281.

The 7, ll-dimethyl-5-oxo-dodecatrien- (3,6,10) used as starting material was manufactured in the manner described below:

b) 456 g of dehydrolinalol were added at 20 ° to a freshly prepared solution of 220 g of KOH, 30 g of K ₂ CO ₃ and 20 g of Cu ₂ Cl ₂ in 1500 ml of methanol. The resulting solution was admixed dropwise with 352 g of 3-chloro-butene (l) with vigorous stirring, the temperature of the reaction mixture being kept below 50 °. After stirring for 3 hours, the methanol was evaporated under reduced pressure. The residue was mixed thoroughly with 1 liter of water. The mixture was extracted with ether and the ethereal extract was worked up according to the usual methods. Fractional distillation of the crude product gave 44 g of dehydrolinalol as well as 530 g of a mixture of 7,11-dimethyldodecadiene (2,10) -in- (5) -ol- (7) (A) and 3,6,10- Trimethyl-undecadiene- (l, 9) -in- (4) -ol- (6) (B) in a weight ratio of about 85:15. These two alcohols were separated by distillation on a spinning band column. They exhibited the following physical properties:

Compound A (400 g): b.p. 84-85 ° / 0.1 torr; n'o ° - 1.4824; d? - = 0.8872.
IR spectrum: 3380, 2235 and 960cm- ¹ .

Compound B (80g): b.p. = 80 ° / 0.1 torr; riZ - 1.4739; <ίΐ - 03944. IR spectrum: 3380, 2235, 1640 and 915 era- '.

c) 400 g of the 2 £, 6-trimethyl-l- (l-hydroxy-butenH (3> -yl) -cyclohexen- {2) A were in the presence of 700 g of acetic anhydride and 60 g of sodium acetate for 3 hours 130 ° heated. The excess acetic anhydride was distilled off under reduced pressure at 50 °, whereupon the residue was mixed with water and the mixture was extracted with petroleum ether. The extract was washed with aqueous sodium carbonate and worked up in the usual way. 414 g of the acetate of alcohol A, which had the following physical properties, were obtained by distillation:

Kp. - 88-90 ° / 0, l Τογτ-, π? = 1.4732; d? = 05122. IR spectrum: 2240, 1740 and 965 cm- ¹ .

d) 248 g of the acetate prepared in accordance with paragraph c) were heated in the presence of 500 ml of acetic acid and 10 g of copper acetate for 5 hours at 90 °. The reaction mixture was concentrated in vacuo, whereupon the residue was mixed with 300 ml of water and the mixture was extracted with petroleum ether . By working up the extract according to the usual methods, 190 g of a mixture of 7,11-dimethyl-2-, 5-oxo-dodecatriene- (3,6.10), 7,1 l-dimethyl-5-oxo-dodecatriene-3, 7.10) and II-methyl ^ -methylene-S-oxo-dodecadiene- (3.10), which had the following constants: b.p. = 88-97 ° / 0.1 Torr; nf = 1.4932; d ', = 0.8919. This mixture was used directly for the cyclization described in o \ paragraph a).

Example 12

2.b.b-Ti imethyl-1 - (2-methyl-crotonoyl) -

cyclohexene (2) ^3>

a) 25 g of 3,6,10-trimethyl-4-oxo-undeeatriene- (2,5,9) (which contains small amounts of the isomeric ketones 3,6,10-trimethyl-4-oxo-undecatriene- (2, b.9) and 3,10-dimethyl-6-methylene-4-oxo-undecadiene- {2,9) contained) were in the presence of 50 ml of dry benzene and

10 g of tin tetrachloride cyclized. By distilling the crude product (22 g), 12.8 g of an oily substance were raised. Another distillation gave 8.8 g of 2, ^< \ 6-trimethyl-1- (2-methyl-crotonoyl) -cyclohexene (2), the physical constants of which were as follows:

Kp. = 7Ο-7Γ / Ο.1 Tomn? = 1.4818: dV = 0.9249.

IR spectrum: 1720.1630.825.810 cm - ·.

The ketone mixture used as the starting material was prepared in the manner described below manufactured:

b) 50 g of alcohol B (prepared in accordance with paragraph b) of Example 11 was used in that in paragraph c) of Example

11 described manner acetylated by means of 84 g of acetic anhydride _5S in the presence of 8 g of sodium acetate. 54 g of the acetate of 3,6,10-trimethyl-undecadi () i were obtained

IR spectrum: 2245, 1745, 1640 and 915 cm- '.

c) 37 g of this acetate were in the presence of 75 ml of acetic acid and 1.5 g of copper acetate for 5 hours heated at 90 °. 26 g of 3,6,10-trimethyl-4-oxoundegatriene- (2,5,9) (which had a low content of two other isomeric ketones). This Mixture was used directly for the cyclization described in paragraph a). The ketone mixture had the the following physical constants:

Bp = 75-77 ° / 0.1 Tornno ⁰ = 1.4889; d- = 0.8890.

Example! 13th

2,6,6-trimethyl-l- {3-methyl-crotorioyl) -cyclohexen- {2)

a) 20 g of 2,6,1 0-trimethyl-4-oxo-undecatriene {2,5,9) were in the manner described in paragraph a) of Example 11 in the presence of 7 g of tin tetrachloride in 100 ml of dry benzo! cyclized. During the addition of the ketone, the temperature was kept below 150 ° . The reaction mixture was then kept at 40 ° for 4 hours with stirring. By working up the reaction mixture according to the usual methods, 63 g of pure 2,6,6-trimethyl-i- (3-methylcrotonoyl} -cyclohexen-{2) were obtained, which had the following physical constants:

Kp. = 67-68%, 1 Torr; / !? = 1.4818; di = 0.924 '-> IR spectrum: 1670, 1615, 826 and 805 cm- '. The ketone used as the starting material was prepared in the manner described below:

b) 100 g of methallyl chloride were added in portions: under nitrogen to a solution of 60 g of KOH, 10 g of K2CO3 and 7 g of Cu ₂ Cl ₂ in 500 ml of methanol. During the addition of the chloride, the temperature was maintained at about 40 °. The reaction mixture v>.; V. Stirred for a further 3 hours. After removing: ■ volatile substances, the residue was mixed with y / j π · \ water and extracted with 300 ml of petroleum ether! The extracts were purified and worked up in the manner described in paragraph b) of Example 12. 152 g of 2,6,6-trimethyl-undecadiene- {2,10) -in- (7) ol- (6) and 35 g were obtained Dehydrolinalol. The more physical. Inol's constants were the following:

Kp. = 70-72 ° /0.1 Torri / J? = 1.4818; c / '/ = 0.8941 IR spectrum: 3350, 2245, 1650 and <i 890 cm - '.

c) 103 g of the Inols anhydride were as described in paragraph c) of Example 12 with 200 g of acetic acid and 20 g of sodium acetate icetyliert Man erhv ^'. 112 g of the acetate of 2,6.10-methyl-undecadiene (2,10) -in- (7) -ol- {6). This Aceta! had the following physical constants:

Bp = 30 ° / 0.01 torr: n% = 1.4709: ^ = 0.917: IR spectrum: 2245.1740.1645.890 cm '.

d) 248 g of the acetate prepared in accordance with paragraph c) were obtained using 400 ml of acetic acid and 15 g of copper acetate isomerized This isomerization was carried out in the manner described in paragraph d) of Example 12 accomplished. 187 g of 2,6,10-trimethyl-4-oxoundecatriene- (2,5,9) [with a content of two other isomeric ketones: 2,6,10-trimethyl-4-oxo-undecatriene- (2,6,9) and 2,10-dimethyl-6-methylene-4-oxo-undecadiene- (2,9)]. This ketone mixture had the following physical constants:

Kp = 90-97 ° / ^{0.1 Torr: / 7c 0} = 1.5075; d'f = 0.8915.

Example 14 2.6, b-Tnmethyl-1-vinylacetyl-cyclohexen- (2)

a) 2.6,6-Trimethyl-1 - (1-hydroxy-buten- (3) -yl) -

cyclohexene (2)

5 ml of allyl chloride were under nitrogen a suspension of 28.8 g of magnesium in 300 ml of dry Ether added. Under the usual conditions for carrying out Grignard reactions then a solution of 85 g of allyl chloride and 152 g of Λ-Cyciocitral in 100 ml of dry ether mi "so.Jier Added dropwise at a rate that the solvent remained in the boiling state. The reaction mixture was Heated under reflux for a further 3 hours and then poured into an aqueous NH 4 Cl solution. The essential Layer was worked up according to the usual methods.

By distilling the residue, 182 g of a Mixture of the two diastereomers of 2,6,6-trimethyl-l- (l-hydroxy-buten- (3) -yl-cyclohexen- {2) receive. The diastereomers were separated by gas phase chromatography (polyethylene glycol 170 °, 3 m). she had the following physical constants:

Peak 1: approx. 70%; Bp = 62 ° / 0.1 torr; n'S = 1.4878; df = 0.9276.

IR spectrum: 3400,3060.1820,1635,988,910cm- ¹ .

NMR Spectrum: 0.85 and 0.98 (6H, 2z ); 1.75 (3H, s); 3.75 (1 H, I); 5.6 (1 H.in); 4.88-6.0 (3 H) O ppm.

The mass spectrum was practically identical to that of the product corresponding to peak 2.

Peak 2: approx. 30%; Bp = 62 ° / 0.1 torr; n'S = 1.4922; df = 0.9319.

IR spectrum: 3420,3070,1815,1630,985,910cm- '.

NMR Spectrum: 0.91 and 1.05 (6 H, 2 s); 1.78 (3H, m); 4.82 (m); 5.45 (1 H.m); 4.86-6.2 (3 H) O ppm.

Mass spectrum: M + = 194 (0.1); m / e: 176 (0.1); 161 (0.1); 153 (2); 135 (2); 124 (64); 109 (100); 95 (13); 81 (27.5);

68 (31); 55 (10); 41 (30); 27 (8).

b) 2,6,6-trimethyl-1-vinylacetyl-cyclohexen- (2)

A solution of 191.4 g of 2,6,6-trimethyl-1- (1-hydroxybutene- (3) -yl) -cyclohexene (2) in 310 ml of toluene was converted into a solution at 0-5 ° with vigorous stirring of 365 g Na ₂ Cr ₂ O ₇ 2 H ₂ O in 300 g conc. Sulfuric acid and 1800 ml of water were added dropwise over the course of Vh hours. The reaction mixture was allowed to stand at room temperature for 10 hours. After the organic phase had been separated off, the aqueous phase was extracted with 300 ml of petroleum ether. The combined organic extracts were worked up by customary methods. By distilling the residue, 170 g of a product boiling at 50-53 ° / 0.1 torr and containing 90% of 2,6,6-trimethyl-1-vinyl acetyl-cyclohexene (2) were obtained.

A sample of this product purified by gas phase chromatography had the following physical properties Constants on:

Kp. = 50 ° / 0.1 Torr; / 7? = 1.4 830; di = 0.9371.

IR spectrum: 3080, 1820, 1710, 1640, 990, 900, 808 cm- ¹ .

NMR Spectrum: 0.88 and 0.93 (6 H, 2 s); 1.58 (3H, s); 3.17 and 3.27 (2H, 2m); 535 (1 H. m); 4.85-63 (3 H) <5 ppm.

Mass spectrum: M ⁺ = 192 (5); m / e: 177 (0.1); 166 (0.1): 151 (12); 135 (1); 123 (100); 107 (6); 95 (10); 81 (80);

69 (60); 55 (10); 41 (44); 27 (5).

Example 15

A floral olfactory composition was produced by mixing the following components:

Components

Parts by weight

Decanal. 10% solution *)

Undecanal, 10% solution '*)

DodecanaL 10% solution *)

Methylnonylacetaldehyde,

10% solution *)

Synthet. lily of the valley

SyntheL down

Synthet. rose

Synthet jasmine

Bergamot

Tarragon, 10% solution *)

1
2
1

0.5
16.5

7th
12th

Components Weight share Ylang extra 9 5 synthet. clove 6th Methylionone 6th Vetiveryl acetate 4th Santalol 2 Decolorized oak moss abs .. ίο 10% solution *) 3 Natural defatted civet, 10% solution *) 3 Lily abs, 1% solution *) 2 Orange blossom abs .. 10% solution *) 2 15 jasmine abs. 2 Rose abs. 1 Ketone musk 4th Trichloromethylphenylcarbinylacetate 2 Colorless tolu resin abs .. 2o 10% solution *) 1.5

99 5
*) In phthalic acid diets.

By adding 0.5 g of 2,6,6-trimethyl-i-vinylacetylcyclohexen- (i) (in the form of a 10% solution in phthalic acid diethyl ester) to 99.5 g of the above odorant mixture a fragrance composition was obtained with a more intense fragrance than the additive-free one Fragrance mixture. In addition, the addition improved the charisma and the olfactory composition given a very natural fullness.

Example 16

A chypre type fragrance composition was obtained by mixing the following components manufactured:

Components

G ^p weight

Bergamot 21 Portugal 0.5 Synth. Neroli 1 Synth. rose 9 Synth. jasmine 9 Ylang extra 6th Methylionone 6th Hydroxycitronellal 6th Oriental santal 3 Patchouli 1.5 Vetiverylaceiai 4.5 Naturally defatted civet, 10% solution *) 3 Labdanum Cistc abs, 10% solution *) 2 Ketone musk 4th !, 1 -Dimethji-6 <tert-) butyl- 4-acetylindane 03 Coumarin 3 Trichloromethylphenylcarbinylacetate \ 5 Tarragon. 10% solution *) 3 Oak moss abs, 50% solution *) 6th Benjoin resin, 10% solution *) U Styrax cinnamon alcohol U Jasmine abs. 1.5 Cyclopentadecanolide, 10% solution *) 2 Rose. Section. 1 Methylnonylacelaldehyde 99.5 *) In phthalic acid diethyl ester. 709 607/163

By adding 0.5 g of trans ^ Aö.ö-tetramethyl-lcrotonyl-cyclohexene (l) (in Form of a 10% solution in phthalic acid diethyl ester) to 99.5 g of the above The mixture obtained a fragrance composition with a more intense fragrance note than the additive-free fragrance mixture. In addition, the emittance and the fragrance composition were improved by the addition given a very natural fullness.

Example 17

By mixing the substances listed below, a Chartreuse-Ari liqueur flavor was obtained manufactured:

Components

Parts by weight

Neroli oil

Clove oil

Cardamon oil

Nutmeg oil

Cinnamon oil

Lemon oil

Orange oil (sweet)

Angelica seed oil

peppermint oil

Orange oil (bitter)

Angelica Root Oil

20th

25th

25th

25th

35

65

75

75

200

445

995

Components

Parts by weight

Drinking alcohol (96%)
Wine alcohol (74%)
Sugar syrup (65%)
water

325 ml

100 m!

10 ml

565 ml

1000 ml 42

The advantageous properties of the compounds of general formula 1 emerge from the following Test report shows:

The odor properties and odor effects of the compounds according to the invention listed below, were with the odor properties and odor effects of those described in DT-OS 18 07 568 and other known isomeric or analogous fragrances.

IO DT-OS 20 22 236

according to the invention
connection

20th

30th

By adding 5 g of 2,4,6,6-tetramethyl-l-lranscrotonyl-cyclohexene (l) A "test" composition was made up to 995 g of the above mixture. A »comparison κ-composition was made by adding 5 g Angelicawuirzelö! to 995 g of the above mixture receive.

A liqueur base was prepared by mixing the substances listed below:

35

40

45

This liqueur base was on the one hand with the "test" composition and on the other hand with the "comparison" Composition flavored, both flavor compositions in a proportion of 10 g per 100 kg Liqueur base were used. The finished liqueurs were given to a group of tasters Assessment submitted. The taste testers stated that it was flavored with the "test" composition Liqueur differs from the liqueur flavored with the »Vergteichs« composition with a more rounded one Taste and differed by a flavor note reminiscent of red berries.

When using 2,4,6,6-tetramethyl-i-transcrotonyl-cyclohexadiene- (13) instead of 2,4,6,6-tetramethyl-1-trans crotonyl-cyclohexene (i) in the one described above "Test" composition, similar results were obtained The taste of the with this modified "test" composition of flavored liqueur was more floral and less fruity.

Abbreviated!

(a)

(b)

(c)

(d)

(e)

(0

(G)

(H)

(i)

continuation

DT-OS 20 22 2.16 according to the invention
connection

Kur / .bcxcichnung

(k)

(D

(m)

(n)

(O)

(P)

In the present report, the following chemical names are used for those from the DT-OS 18 07 568 known compounds are used:

a-damascone for the connection

/ S-Damascone for the connection

ß-Damascenon for the connection

1. The new connections (1). (m) and (n) were used with compared to the known isomeric methyl ionones. To carry out the tests, a commercially available available under the brand name »IRALIA«

Product used, which is about 60% iso-methyl - «- jonon, about 30% from n-methyl-ot-jonon and about 10% consisted of the remaining isomers (iso-methyl-j3-ionone and n-methyl-jS-ionone).

While the methyljonones and their mixtures develop an iris-like odor, they have Compounds (I), (m) and (n) have a distinctly sweet-fruity odor, which is reminiscent of the aroma of reminiscent of dried plums and, moreover, one

ίο has a clear woody note.

The odor differences between the compounds (I), (m) and (n), on the one hand, and the methyl ionones, on the other hand, they especially appear in practical use in perfume compositions.

A perfume base I of the following formula was prepared:

I.

Weight share Benzyl alcohol 120 Undecenylaldehyde 10% *) 60 Decylaldehyde, 10% *) 15th Nonylaldehyde, 10%) 5 Isobutyl salicylate 50 Hydroxycitronellal 120 Ylang 50 Citronellol 100 Phenylethyl alcohol 70 Linalol 40 unalylacetate 80 Neroli oil 10 Methylphenylcarbinyiacetate 20th Citronellyl acetate 35 Sandalwood, East Indian 60 Jasmine oil, artificial * 0 Bergamot oil 60 1, l-dimethyl-6-tert-butyl-4- acetylindane 20th Rose oil, artificial 55 Eugenol 20th 1000 *) ln diethyl phthalate.

This perfume base was used to produce the perfume compositions Ia and Ib:

I. a

Weight*
share Perfume base I
Methyl jonone mixture (»IRALIA«) 900
100
1000 Lb Weight
share Perfume base I 900 Connection (I) 100

1000

Base I is a flowery fantasy composition π emphasis on rose and lily of the valley fragrance. D. Parfümkoi position Ia obtained by adding methyljonon has a fragrance with pronounced Iris character and is suitable e.g. B. to the perfumer of hair sprays. The perfume composition Ib obtained by adding the compound to the base I is völ

different from the perfume composition la, since the former completely lacks the iris note, which through a strangely warm, fruity and woody fragrance is replaced. The perfume composition Ib is for Perfuming hair sprays is unsuitable and belongs more to the class of men's perfumes.

If the compound (m) or (n) is used instead of the compound (I) in the perfume composition Ib, so a similar odor effect is achieved.

In general, it should be noted that by introducing methyl groups into the ring and / or the side chain of a-Damascons, 0-Damascons and 0-Damascenons the olfactory character of these compounds is profoundly changed. While the Damascone and the Damascenon have a fresh minty and develop a rosy scent note, the methylated derivatives generally have a sweet-fruity, woody note Olfactory character. If the compound (1) in formula Ib is replaced by one of the compounds (a), (b), (c), (e), (f). (g) or (h), similar odor effects are achieved.

2. The odor quality of the new compound (c) was compared with that of the known ß- or Λ-Damascons and the «-Iron. For this purpose, a perfume base II was prepared with the following composition:

Vetyvery acetate

Geraniol

Citronellol

Citronellyl acetate

Phenylethyl alcohol

U-Dimethy! -6-tert.butyl-4-

acetylindane

Methyl dihydrojasmonate. lO ° / oig *) Neroli oil

Hydroxycitronellal

jasmine oil, artificial

Linalol

Linalyl acetate

Ylang

Nonylaldehyde, 10% ^# )

Undecenyl aldehyde. 10% ^# )

Methylnonylacetaldehyde, 10% *) Heliotropin

Phenyimethylcarbinylacetat, 1 OVoig *) Hexyl cinnamyl aldehyde

Eugenol

Sandalwood, East Indian

Oak moss abs, 50% *)

Dimethylbenzylcarbinylacetate

*) In diallyl phthalate.

Parts by weight

50

50 150

50 100

10 50 10 70 100 70 50 20 10 20 5

20 10 40 15 10 40 50

1000

This perfume base was used for the production of the perfume compositions Ha. Hb and Hc used:

! la

Perfume base Π

λ- or 0-damascone, 10% ig ·)

Gcwichuteiic

900

100

1000 II.b

■ ^s Perfume Base II
Λ-lron, 10% ^# )

II. C

Perfume base Il
Compound (c), 10% *)

5 *) In diethyl phthalate.

Part by weight c

900 JOO 1000

Weight line

900

100

1ÖÖÖ

The perfume base Il is a floral composition with a jasmine scent and a fresh top note loosened by the aldehydes. The perfume composition Ha obtained by adding ß- or α-damascone to this perfume base has a very pronounced fresh? raisin odor nuance. If the ß- or ft-damascone is replaced by Λ-lron in this perfume composition, the odor of the composition (Hb) changes into a refined fantasy iris note. The perfume composition Ic. which contains the compound (c) instead of ß- or Λ-damascone or Λ-iron, now has a smell with a peculiar tint of sweet, fruity character and extraordinary adhesive strength.

3. The odor properties of the new compound (d) were compared with those of the / J-damascenone. For this purpose a perfume base Hi was made:

111

Pentadecanolide, 10% *)

Geraniol

Phenylethyl alcohol

Ciironellal

Benzyl acetate

Methyl dihydrojasmonate, 10% *) ylang

Hydroxycitronellal

fx-methylionone

Bergamot oil

Sandalwood oil, East Indian

Decanal, 10% »)

UndecenallO% ig ·)

Nonanal, 1% *)

Isobutyl salicylate

Linalol

') In diallyl phthalate.

Gcv. i share

50 100! 00 150 100

50

30th

70

SO

50

20th

20th

30th

30th

50

70

1000

This perfume base was used to produce the fragrance compositions HIa and IHb according to de use the following formulas:

111. a

Perfume base St.

£ Damascenon. 10% *)

Weight parts

900 100

1000

ULb

Perfume Base 111 Connection (d). 10% *)

*) In diallyl phthalate.

Weight levels

900 100

1000

The perfume base IH is a flowery composition with an iridescent note. The by adding ß-Damascenon to This base obtained perfume composition UIa has an increased flowery odor and also a rosy note, which partially covers the iris note. Is the ß-Damascenon in the perfume composition UIa Replaced by the compound (d), the perfume composition IUb is obtained, the odor of which is compared with that of the perfume composition HIa is substantially different. The composition IHb points an original woody and even fruity note, which strongly weakens the iris note.

4. The odor properties and odor effects of the compound (p) were compared with those of the α-damascons and 0-damascons. To this end a perfume base IV was prepared according to the following formula:

Weight share Linalyl acetate 200 Linalol 150 oc-methyloctylacetaldehyde, 10% *) 10 Lemongrass oil 10 Lime oil, artificial 20th (-) - rose oxide, 10% *) 10 Pentadecanolide, 10% *) 50 Geranyl acetate 50 Benyl acetate 50 Bergamot oil, artificial 100 Geraniol 100 Sweet orange oil 200 Lemon oil 50 lOOC *) In diethyl phthalate.

The addition of α- or 0-damascone to the base IV causes a change in their odor character. The perfume composition IVa has a fresher one Smell and a rosy note, which the base IV lacks. If the <x- or O-Damascone through the compound (p), the perfume composition IVb is obtained, which is the rosy one Fragrance note is missing and which now has a bitter, almost wine-like odor note

The odor quality of compound (p) is completely different from that of a-Damascons and des ß-Damascons. While the latter two compounds smell fresh, slightly minty, and rosy, this is the one The odor of the compound (p) is slightly camphor-like and is reminiscent of the odor of wine yeast.

5. The odor properties and odor effects of the compound (o) were compared with those of the α-Damascon. For this purpose a Perfume base V made according to the following formula:

V.

Undecenal, 10% *) Methylnonylacetaldehyde, 10% *) Phenylethyl alcohol

Citronellol Linalyl acetate

Linalol

Sandalwood oil, East Indian Hexyl cinnamaldehyde

Benzyl acetate Methyl dihydrojasmonate, 10% *)

Indan musk

Ylang

Coumarin

Heliotropin Bergamot oil, artificial

Citronellyl acetate Hydroxycitronellal Vetyvery acetate

Anisaldehyde Benzyl alcohol

*) In diethyl phthalate.

Weight parts

80

20th

80

70

50 100

20 100

50

60

10

20th

20th

40 100

30th

50

50

10

40

1000

This perfume base was used for the preparation of the perfume composites IVa and IVb according to the following formulas:

IV. A

Perfume Base IV

λ- or jS-Damascone, 10% ig *)

IV. B

Perfume Base IV Connection (p)

In diallyl phthalate.

Parts by weight

900 100

1000

Weight parts

900 100

1000 These z. B. for perfuming skin creams usable perfume base was used for the preparation of the perfume compositions Va and Vb according to the following formulas:

V. a

Perfume Base V Λ-damascone

V.b

Perfume Base V Connection (o)

Parts by weight

900 100

1000

Parts by weight

900 100

1000

709 607/163

5ö

By adding Λ-damascone to the perfume base V their odor character is fundamentally changed. The perfume composition Va has a minty-fruity note, in which the rosy-flowery note of the base dominates in the perfume composition Va the a-Damascone through the connection (o) replaced, the perfume composition Vb is obtained, the odor impression of which in comparison with both the base V and the perfume composition Va is clearly different. The compound (o) gives the base V a fuller, rounder and more original odor note.

6. The odor effects of compounds (f) and (k) were similar to those of α-damascons and 0-damascons compared. For this purpose a perfume base Vl was produced:

Undecenylaldehyde, OK% *)

Methylnonylacetaldehyde, 1% *) Decanal, 10% *)

Dodecanal, 1%)

Ylang

Bergamot oil, artificial

Lavender oil

Linalyl acetate

Linalol

Citronellol

Jasmine oil, artificial

Methyl dihydrojasmonate

Coriander oil

Oak moss, absolutely 10% ^# )

Cedryl acetate

Petitgrain bigairade

Pentadecanolide, 10% *)

Isobutylquinoline, 10% *)

Geranium Bourbon

Vetyvery acetate

Rose oil, artificial

Patchouli

*) In diallyl phthalate.

This perfume base was used to produce the perfume compositions Via, VIb and VIc:

Parts by weight

80

20th

20th

10

20th

70

50 100

50

80 100

15th

20th

50

30th

30th

80

10

20th

40

50

25 1000

VLa

Perfume Base VI

α- or 0-damascone

Vl. b

Perfume Base VI
Connection (k)

VI. c

Perfume Base VI
Connection (noun)

Parts by weight

900

100

1000

Parts by weight

900

100

1000

Parts by weight

900

100

1000

The perfume composition obtained by adding α- or β-damascone to the perfume base VIa has the odor character of the base VI is completely lost and is due to the odor of the <x- or 0-Damascons mastered. To a reasonably harmonious To achieve an odor impression, the concentration of α- or 0-damascone would have to be reduced to about 1-3% will. If the «- or /? - Damascone is replaced by the compound (k) in the perfume composition VIa, so the perfume composition VIb is obtained, its odor compared to that of the base VI and the fragrance composition VIa is noticeably refined. The perfume composition VIb has a fruity-woody note, which unites the different odor elements of Base VI into a harmonious whole. The perfume composition VIc has a noticeable deepening of the olfactory impression and a additional "tobacco" -like note.

Claims (2)

Patent claims:
1. Compounds of the general formula 2 '3'
CO - CH _n - C - CH ₂ _ "R ¹ R ³ R ² with a double bond in 2 'or 3' control of the acyl side chains and either one double bond in position 1 or 2 or two double bonds in positions 1 and 3 of the ring and where π denotes the number 0 or 1, R ¹ , R ² and R ³ denotes hydrogen or one of these symbols a methyl or ethyl radical and the other hydrogen denotes R ⁴ , R ⁵ , R ⁶ and R ⁷ hydrogen or one of these symbols denotes a methyl or ethyl radical and the others denote hydrogen and the double bonds are represented by dashed lines are, where the symbols R> to R ⁷ all simultaneously denote hydrogen only if either the ring has an exocydic double bond or π = 1 2. Process for the preparation of the compounds according to claim 1, characterized in that man a) Cyclogeranic acid derivatives or safranyl derivatives the general formula COX wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ and the dashed lines have the meaning given above and X is halogen, -O-alkyl, -O-aryl, -O-CX) -alkyl or -O-CO-aryl , in a manner known per se with a propene compound of the general formula r τ y ME-C = C-CH ₂ R ¹ R ³ R ² (III) converts, in which R ¹ , R ² and R ^{3 have} the above meaning and ME is a metallic or metal-containing radical, such as Li, Zn, Cd or Mg — halogen, or
b) an alcohol of the general formula 2 '.V CH _{- CH n} - C - CH ₂ . "R ¹ : C OH R- ¹ R ² and η have the meaning given above, oxidized in a manner known per se with manganese dioxide or chromium trioxide in an inert solvent, or
c) a ketone of the general formula CO-C = C-CH ₂ R 'R ³ R ² (VI) wherein the symbols R ¹ to R ^{7 have} the meaning given above, cyclized in a manner known per se in the presence of an acidic cyclizing agent, or
d) a ketone of the general formula CO-C = C-CH ₂ R ¹ (Viii in which the symbols R ¹ to R ⁷ and the dashed lines have the same meaning as in formula I, partially hydrogenated on the triple bond in a manner known per se in the presence of a "Lmdlar" catalyst, e) the cis isomers obtained by isomerization with an acid in an inert solvent converted into the corresponding trans isomers, or f) compounds of the general formula CO-CH-C = CHR ¹ R ³ R ² (Ia-b, /; - b) R ⁵ I. R ⁴ in which the symbols R ¹ to R ⁷ and the dashed lines have the meaning given above, isomerized by means of an acidic or basic isomerizing agent or by means of heat, or g) compounds of the general formula R "\ / CO-CH _n -C-CH ₂ " R ¹ R ³ R ² (\ u.fi) wherein the dashed lines, the symbols R ¹ to R ⁷ wherein the symbols R ¹ to R ⁷ and π and the dotted lines have the meaning indicated above, in a conventional manner by reaction with N-Bromsuccin- or -acetamide, or N-Dimethyldibromhydantoin in an inert solvent at a temperature between about 20 ° C and about 100 ⁰ C, if desired in the presence of a initiator, and subsequent dehydrohalogenation by means of a tertiary amine, such as diethylaniline, dehydrated at about 100 to about 150 ⁰ C, or h) epoxide compounds of the general formula 2 ' 3 ' R ³ R ² (VIII) with a double bond in 2 'or 3' control of the acyl side chain and in which π and the symbols R ¹ to R ^{7 have} the meaning defined above, and the oxygen atom of the epoxy ring is linked to positions 1 and 2 or 2 and 3 of the six-membered ring , the double bonds are represented by dashed lines, with a mineral acid or organic acid such as hydrochloric, phosphoric, sulfuric, p-toluenesulfonic or trifluoroacetic acid, or acidic diatomaceous earth in an organic solvent such as dioxane or tetrahydrofuran, at about 20 ° treated to about 100 ° C, or i) a compound of the general formula CH-CH _n -C-CH ₂ _ "R ' (Va, l with a double bond in the 2'- or 3'-position of the acyl side chain and a double bond in the 1- or 2-position of the six-membered ring, where η and the symbols R ¹ to R ^{7 have} the above meaning and the double bonds are represented by dashed lines, first with a peracid in a manner known per se in a buffered anhydrous solvent to form the epoxide of the general formula OH CH - CH _n - C ^ CH ₂ _ "R 'R ³ R ² (X) wherein n, the symbols R ¹ to R ⁷ and the dashed lines have the above meaning, epoxidized, this then with an acidic aqueous Solution of CrCb to epoxy of the more general = formula