DE1923223A1 - Derivatives of 1-Aethyl-3,3-dimethyl-cyclo-hexane and process for their preparation - Google Patents

Description

© r. ing. A. van der Werfii Dr. Franz Lederer

PATENT LAWYERS

6 ^Γ) 10/21

L.GIVAUDAN ^ CTS. Society Anonyme , Vernier-Geneve (Switzerland)

Derivatives dos I ^ -Äethyl-Ji, 3- ^ 1 "· βthyl-eyelohexans and process for their preparation

The invention relates to new derivatives of 1-ethyl-3,3-dimethyl-cyclohexane the general formula

where X is hydrogen and Y is the radical OR, where R is hydrogen, acetyl, propionyl or acetoacetyl or X and Y together represent oxygen.

The invention also relates to a method for producing the

new compounds of the general formula I. Ur / 4/15/69 809847/1 13S

ORIGINAL BATHROOM

The new compounds r.?ii in cor Rlechstofi'jndustrjo useful because of their unexpected, ur ^ evK'like uii: i .very desirable properties. They can be used in odorant compositions.

The new compounds of general formula I, wherein X represents hydrogen and Y represents the radical OR, where R represents acetyl or propionyl, there is a conversion of 2,6-dimethyl-2,7-octadiene obtained with acetic acid or propionic acid in the presence of a Lewis acid as a catalyst {process variant a).

The new compound of formula I wherein X is hydrogen and Y denote hydroxy, obtained ir.an by saponifying a compound of the formula I, in which X is hydrogen and Y is OR, where R is acetyl or propionyl (process variant b).

The new compound of the formula Z ₁ in which X and Y together denote oxygen is obtained by oxidation of a compound of the formula I in which X denotes hydrogen and Y denotes hydroxy (process variant c).

The new compound of formula I wherein X is hydrogen and

Y represent OR, where R denotes aeetoacetyl, is obtained by reacting a compound of the formula I in which X 'is hydrogen and

Y represent hydroxy, with a lower-alkylacetoaeetat in alkaline Medium (process variant d).

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In the case of the Pror. Fiss variant a, i according to the new l- (3. »J5-Diiiiethyl-l-cyelohxyl) - ithylacetat (R in the formula I = acetyl) and the corresponding propioiiate (Π in the formol I = propionyl) by conversion of ^, G-Djiucthy 1-2,7-octadiene with acetic acid or propionic acid in the presence of a Lewis acid as

Catalyst are obtained, reaction temperatures are expedient between about 0 C and about 150 C are possible. If desired, inert solvents can also be used. Reactive : <u ^ e £ _; become even.

The new l- (j5 * ^ - DiR'.othyl-l-oyclohexyl) -ethanol is obtained according to process variant b from the new esters by saponification in the usual way, for example by means of an alkali or Er d al Ic al i hy dr oxy d s.

The new ^. »! J-Dirr.ethyl-1-cyclohexyl-rp.ethylketon receives according to process variant c from l- (3,3-dimethyl-l-cyclohexyl) Ethanol by oxidation, polygamy, preferably by means of a hexavalent one Chromium compound is carried out.

The new l- (j5,3-dimethyl-l-cycloliexyl) -äthylacetoa.cetat is obtained according to process variant d by reacting 1- (j5,3i-dimethyl-1-cyclohexyl) ethanol with a leather alkylacetoacetate, preferably ethyl acetoacetate in an alkaline medium, preferably in the presence of aluminum isopropoxide.

As a catalyst for the production of the new esters

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any Lewis acid can be used. Examples of such.,. Lewis acids are boron trifluoride, aluminum chloride and tin chloride and zinc chloride.

The amount of Lewis acid used can be about one vary widely. Even the use of 1 / 100Q moles Boron trifluoride per mole of organic acid may suffice. Appropriately, however, about 1/100 to 1/10 moles of Lewis acid are used per mole of organic acid. .

When carrying out process variant a, satisfactory results are obtained if, per mole of 2,, 6-dimethyl-2,7-octa-,. 1 to 5 moles of acetic acid or propionic acid are used, however, 1 to 3 mol of these organic acids are preferred, used.

The addition of an inert solvent to the reaction. Mixture is usually desirable as the (usually exothermic) reaction can be better controlled. Examples of inert solvents, which if desired come into question in process variant a, are: benzene, ethyl ester, e.g. ethyl acetate, saturated hydrocarbons, e.g. hexane and heptane. The amount of solvent is not critical to them is for example 1/2 to 5 parts by weight to one part organic Acid. It is preferable to use approximately one part of solvent for one part of organic acid. The at the process.

Variant a of the temperatures in question can be —— .—, _

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RtGJNA ^ _rma

vary over a wide range, depending on the starting materials and solvents used, if the latter are used at all. Generally C when working between about 0 ⁰ and get about 15O ⁰ C satisfactory results; A range from approximately 25 ^° C. to approximately 100 ^° C. has proven to be preferred.

The reaction time in process variant a varies depending on the type and amount of reactants, catalysts and the reaction conditions used. For example, when converting with acetic acid at 55-60 ° C. and when using 15 $ boron trifluoride as a catalyst, the reaction is complete after about 90 minutes. At IQO-110 ⁰ C, on the other hand, the reaction is ended at 5-10 minutes. The preferred temperature range for each process variant is that in which the smallest amount of polymeric and other undesirable by-products occurs ...

As already said above, the new connections of the Invention unexpected, unusual and desirable Odor properties, which makes them useful in perfumery are.

The amounts of the new compounds of the general formula I used in the production of fragrance compositions can match the nature of the desired formulation, the ingredients the formulation, etc. vary greatly. In general,

909847/1135

that the new compounds of general Forn.ol I both "in.sehr your know as auJh as Hauptkoiv.poneiiten such ^grain: items may be present, such -compositions!.", for example, about 0.1 to 25 ^ of the new compounds . If it is desired to use the compound of general formula I as the predominant odor component, concentrations above 25 * are also possible.

In the following examples the temperatures are in Degree Ce3sius indicated, the percentages are by weight percent.

example 1

Production of 1-Q, 3-Dir ^ ethyl-1-cyclohex: / l) -äthylacetat A Use of boron trifluoride catalyst. To 138 g of 2,6-dir. Ethyl-2,7-octadiene (purity 90-95; O and 150 g of acetic acid, 20 ml of boron trifluoride etherate were added with stirring over the course of 5 minutes at room temperature -60 ⁰ and kept at this temperature for 90 minutes After adding an equivalent amount of water, the upper layer was covered with a

10 ^ -igen sodium carbonate solution neutralized and in a to

Goodloe column distilled; the following fractions were obtained:

· "...- ■, ■

** Fraction 1, boiling point 31-50 ° / 2 mm Hg, DO g product with

^ ■ -. n ^ ° 1,4495-1, Λ500 ■ '■. "'

- * Fraction 2, boiling point 75-80 ° / 2 ram Hg, 75-80 g of product with m n ^ L.4465-1.4475

ORUSINÄI: '

- r-

Residue I5 g *

Product 1 consisted of a mixture of hydrocarbons, where the proportion of 2,6-di ;; ethyl-2,7-octadiene and isomers cyclic alkenes 2O-25fj (gas chromatographic evidence) *

Action 2 consisted of 95-98 $ pure 1 ~ (j5>3-dimethyl-1-cyclO'-hexyl) ethyl acetate with a strong musk-angelica character with a woody note (gas chromatography has shown that 2 isomers in the ratio 4: 1 templates). The saponification;: ahl a purified one. Sample (ηί: 1.4465) was 280; the theoretical value for the corresponding compound with the sum formula C ₁₂ Hp _O 0 _? (Molecular weight 198) is 2 & J5.

B. Use of tin tetrachloride as a catalyst.

138 g of 2,6-D: imethyl-2,7-octadiene, 150 g of acetic acid and 15 ml of tin tetrachloride were kept at 75-80 ° for 2 hours with stirring. After cooling to 40 °, 250 ml v / water were added to the reaction mixture with stirring. The upper of the two resulting layers was separated and neutralized with sodium carbonate solution while stirring. The reaction mixture contained about 60 ^ l- (3i3-dimethyl-l-cyclohexyl) ethyl acetate _> which was identical to the product prepared under A *.

G. Use of zinc chloride as a catalyst.

69 g of 2 _i 6-dimethyl-2,7-octadiene _i 75 g of acetic acid and 40 g of zinc chloride were kept at 45-50 ° for 8 hours with stirring. 200 ml of water were added to the reaction mixture and then neutralized with 10 ^ sodium carbonate solution * The crude reaction product contained> 5 $! - (^^

§0 9 ^ 4 7/1135 BATH ORIGINAL

-Br-

acetate (determined by gas chromatography), which is associated with the under A. proved to be identical.

Example 2

69 g of 2,6-dimethyl-2,7-octadiene, 170 g of propionic acid and 5 ml of boron trifluoride etherate are heated ^{to 6O-70 0 for 2 hours.} The reaction mixture is decomposed with 250 ml of water and neutralized with sodium carbonate. By distillation, 10 gl (3 '3 ~ ^ri Dii ethyl-l-cyclohexyl) -äthylpropionat having a boiling point of 122 ° / lO mm, n 1.4470 _n.

Example 3

425 g of l- (3,3-dimethyl-l-cyclohexyl) -äthylace.tat are together with 425 g of 50% potassium hydroxide solution and 1000 ml of ethanol 2 Refluxed for hours; then about 8OO ml of ethanol are evaporated, the residue is washed with water and distilled him. 330-350 g of l- (3,3-dimethyl-l-cyclohexyl) - • ethanol with a boiling point of 95 ° / 5 mm Hg, n ^ 0.4626, odor are obtained intense, flowery-woody.

example 4th

To 78 g of 1- (3,3-dimethyl-l-cyclOhexyl) ethanol are added 150 ml of a chromic acid - with stirring within 45 minutes. Sulfuric acid mixture (made from 286 g of 70 # sodium

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bichromate 320 g of 62.5% sulfuric acid and 120 ml of water) 'given. After the addition, the mixture is stirred at 4-5-50 ° for a further 15 minutes further and then gives 150 ml of water at 50 ° to the reaction mixture and stir for another 5 minutes. The upper layer is then separated off and distilled; 63 g of 3,3-dimethyl-1-cyclohexyl methyl ketone are obtained with a boiling point of 98 ° / 20 mm Hg,

20th
n_ 1.4518, odor woody, smelling of mint, with a note of cedar and thujone. The semicarbazone melts at 192-192.5 °. The 2,4-dinitro-phenylhydrazone melts at 100-111 °.

Example 5

156 g of l- (3,3-dimethyl-l-cyclohexyl) ethanol, 150 g of ethyl acetoacetate and 5 g of aluminum isopropoxide are refluxed under a 30 cm Goodloe column. The temperature of the reaction mixture is gradually increased from 135 to 165 °, with ethanol from the boiling point 8θ-δ5 ° distilling over}. After about 2 hours, the remaining ethanol is removed under a vacuum of 50 mm of mercury. The obtained 1- (3 * 3-dimethyl-1-cyclohexyl) -äthylacetoacetat is distilled at a temperature of 115-118 ° / 2 mm Hg, n ^ ° = 1.4620, yield about 170 ^f g. Arrears about $ 40-45. The product has a fruity, floral note with a woody character.

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Example 6

Rose jasmine perfume. containing l- (3j3-dircethyl-l-c; / clohexyl) ethyl acetate

Parts by weight

ethyl acetate 50

C-10 aldehyde 3

Lauric aldehyde 1

7-undecalactone 1

AmyIsalicylate "70

Methyl-N-3,7-diniethyl-7-

hydroxyoctylidene anthranilate 1

Benzyl acetate 104

Bergamot Oil 4YY

Cassie absolus 5

Citronellol 100 Eugenol. 2

Geraniol 151

Hexyl cinnamaldehyde 30

Jonon 28

Hydroxycitronellal 100

Linalool 107

Phenylethyl alcohol 142

Peru balm 5

Phenylacetic acid 10J »in ethyl

phthalate. 1

«(Trichloromethyl benzyl acetate 22

Isoeainphyleyclohexanol 22

Ylang 14

1000

Addition of 5% l- (3i3-Din'''ethyl-l-cyclohexyl) ethyl acetate gives the perfume warmth and a pleasant natural musk nuance.

l- (3i3-Dimethyl-l-cyclohexyl) ethyl acetate can be used in most odorant substances in ranges of 0.1
to 25? - j and in amounts of over $ 25 in fragrance compositions in which it is the predominant component.

Example ? '

Wood-musk perfume, containing l- (j5,3-dimethyl-l-cyclo-

hexy1) ethyl acetate

Parts by weight

1- (5 * 3-dimethyl-1-cyclohexyl) ethyl acetate 500

cc-methylionone I50

Isoeainphyleyclohexanol 10Q

1,1,4,4-tetramethy1-6-äthy1-7-äthy1-

100

Cedrol 50

yiang oil 25

Vetiverol 50

Bergamot Oil , 25

1000

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Example 8 Rose perfume containing l- (3 »3-diniethyl-l-cyclohexyl) -

ethyl propionate

Parts by weight

1- (3,3-Dimethy1-1-cyclohexyl) ethyl

propionate 100

Citronellol 270

Phenylethyl alcohol 14o

Geraniol 270 hydroxycitronellal - l4o

α-ionone 30

Undecylenealdehyde 10

a- (rrichloririethyl) benzyl acetate 20

Guaiac wood 10

Citral 10

1000

The use of 10J & l- (3i3-dimethyl-l-cyclohexy3) ethyl propionate in the above formulation gives the composition warmth and an intensified rose nuance. Additionally gives this substance softens the rose bouquet.

L- (3i3-Dimethyl-l-cyclohexyl) ethyl propionate can be used in fragrance compositions usually added in amounts of $ 1-25 will. But higher concentrations are also possible to achieve special effects.

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Example 9

Lilac par film, contains 1- (3,3-dimethyl-1-cyclohexyl) -

ethanol 1- (3> 3-diniethyl-1-cyclohexyl) ethanol Weight level Benzyl alcohol 50 Terpineol 33 Phenylethyl alcohol 95 Anisaldehyde 230 Indole - lOfj in diethyl phthalate 10 Cinnamon alcohol 5 Isoeugenol 123 Phenylacetaldehyde 5 Heliotropin 1 Hydroxycitronellal 172 276
1000

The use of 5 $ 1- (3,3-dimethyl-l-cyclohexyl) ethanol in the above formulation improves the odor of the latter by enhancing the flowery character.

This fragrance is normally used in fragrance compositions used in amounts from 0.1 to 25 #. To achieve however, higher concentrations also come into play for special effects Consideration.

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Example 10

Cologne perfume containing 3 * 3-dimethyl-1-cyclohexylmethy! Ketone

The composition is composed like that of the example 11 infra, but in this example it is l- (3,3-dimethyl-1-cyclohexyl) -athylacetoacetate by 5,3-dimethyl-1-cyclohexyl methyl ketone substituted. .

The use of this odoriferous substance in the above formulation improves the quality of the perfume considerably. He harmonizes good with coumarin wood and citrus notes.

The ketone is commonly used in perfume seed positions in Amounts used from $ 0.1 to $ 25. To achieve more special However, effects can also be considered at higher concentrations.

Example 11

Cologne, containing l- (3> 3-dimethyl-l-cyclohexyl) -athylacetoacetate
Parts by weight

1- (3, ^ - Dimethyl-1-cyclohexyl) -ethylacetoacetate . 50

Bergamot oil l6l

Coumarin $ 10 in diethyl phthalate 2

Geraniol 64

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Peru Dalsam 32

β-ionone l6

Liinette oil 8θ

Linalool 96

Linalyl acetate 16l

Orange oil 97

Isocamphyl cyclohexanol 16l

48

Ylang Oil ■ 32

1000

5 $ l- (3> 3-Dlmethyl-l-cyclohexyl) -äthylacetoacetat give äev composition a softer touch "and a pleasant woody character. The ester also harmonizes well with citrus notes in conjunction with wood-musk notes. It's typically used in amounts ranging from $ 0.1-25. However, higher concentrations can also be used to achieve special effects.

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Claims (1)

Godparents speak 1 .. Fragrance compositions ₁ characterized by a content of a compound of the general formula where X is hydrogen and Y is the radical OR, where R is hydrogen, acetyl, propionyl or acetoacetyl or X and Y together represent oxygen. 2. Fragrance composition according to claim 1, characterized by a content of l- (3,3-dimethyl-l-cyclohexyl) ethyl acetate. 3. fragrance composition according to claim 1, characterized by a content of l- (j5,3-dimethyl-l-cyclohexyl) ethyl propionate. 4. fragrance composition according to claim 1, characterized due to a content of l- (3,3-dimethyl-l-cyclohexyl) ethanol. 909847 / T135 - ■ 17 - 5. fragrance composition according to claim 1, characterized by a content of 3,3-dimethyl-1-cyclohexylniethyl ketone. 6. fragrance conection according to claim 1, characterized by a content of l- (30-dimethyl-l-cyclohexyl) ethyl acetoacetate. 909847/1135 7 · A connection of the general: * Korr..el v / orin X is hydrogen and Y is the radical OR, where R is hydrogen, acetyl, propionyl or acetoacetyl or X and .Y together represent oxygen. 8. A compound of the general formula I according to claim J, in which X is hydrogen and Y is the radical OR, where R is acetyl. 9. A compound of the general formula I according to claim 7, v / orin X is hydrogen and Y is the radical CR, where R is propionyl. 10. A compound of the general formula I according to claim 7 »in which X is hydrogen and Y is hydroxy. 11. A compound of the general formula I according to claim J, wherein X and Y together represent oxygen. 12. A compound of the general formula I according to claim 7, wherein X is V. 'hydrogen and Y is the radical OR, where R is acetoacetyl. 909847/1135 BAO ORIGINAL l '/ j. Process only production of connections of the al! / - a 1 nc η Forma I. where X is hydrogen and Y is the radical OR, where R is hydrogen, acetyl, propionyl or acetoacetyl or X and Y together mean oxygen, characterized in that maxi a) 2,6-dimethyl-2,7-octadiene with acetic acid or propionic acid in the presence of a Lewis acid as a catalyst to give a compound of the formula I in which X is hydrogen and Y represent the radical OR, where R is acetyl or propionyl, or that one b) a compound of the formula I in which X is hydrogen and Y is the radical OR, where R is acetyl or Propionyl is saponified to a compound of the formula I in which X is hydrogen and Y is hydroxy, or that one c) a compound of the formula I, in which X is hydrogen and Y is hydroxy, to a compound of the formula I, where X and Y together mean oxygen, is oxidized, or that one 9098A7 / 1 13-5 d) a compound of the formula I in which X is hydrogen and Y is hydroxy, with a lower alkylacetoacetate in an alkaline medium to a compound of the formula I, where X is hydrogen and Y is the radical OR, where R is acetoacetyl. 14. The method 'according to claim 13, characterized in that 2 _j) 6-dimethyl-2,7-octadiene is reacted with acetic acid in the presence of a Lewis acid as a catalyst. 15. The method according to claim 13 *, characterized in that that 2,6-dimethyl-2,7-octadiene is reacted with propionic acid in the presence of a Lewis acid. 16. The method according to claim I3, characterized in that that a compound of the formula I, wherein X is V / hydrogen and Y represent the radical OR, where R is acetyl or propionyl, saponified. 17. The method according to claim 13 *, characterized in that a compound of the formula! »Wherein X is hydrogen Y represent hydroxyl, oxidized, 18. The method according to spoke I3, characterized in that that a compound of the formula I, wherein X is hydrogen and Y represent hydroxy, with a lower-alkylacetoacetate in in an alkaline environment. 909847/1135 19 · The method according to claim I3 or 18, characterized in that that a compound of formula I in which X is hydrogen and Y is hydroxy ^ with ethyl acetoacetate in Reacts presence of aluminum isopropoxide. 909847/1 1.3 p 20. Use of compounds of the general formula 1 where X is hydrogen and Y is the radical OR, where R is hydrogen, acetyl, propionyl or acetoacetyl or X and Y together represent oxygen, as fragrances. 909847 / 113S BATH ORIGINAL