DE1593442C - - Google Patents

Description

H ₃ C CH ₃ O

CH ₃ CH ₃

or of its lower enol ethers, enol esters or ketals with 1 to 5 carbon atoms in the ether, Ester or ketal groups as fragrances.

and its lower enol ethers, lower enol esters

or lower ketals with 1 to 5 carbon atoms in the ether, ester or ketal groups. . *

2. 4 - (1-Ethoxy vinyl) -3,3,5,5-tetramethyl- The invention relates to a cyclic diketone cyclohexanone. formula

3. 4 - Acetyl - 1 - ethoxy - 3,3,5,5 - tetramethyl- H ₃ C cyclohexene (1).

4. l-ethoxy-4- (l-ethoxy-vinyl) -3,3,5,5-tetra-25 H methyl-cyclohexene-t 1).

5. 4 - acetyl - 1,1 - ethylenedioxy - 3,3,5,5 - tetramethyl-cyclohexane.

6. Process for the preparation of a cyclic

Diketons of the formula 30 O

CH,

H H

(D

CH,

and of its lower enol ethers, enol esters with its lower enol ethers, esters or ketals 1 to 5 carbon atoms, processes for their production and their use as fragrances. The mentioned lower enol ethers, enol esters or ketals contain 1 to 5 carbon atoms in the ether, ester or Ketal groups.

The compound of the formula I and its enol ethers, enol esters and ketals are distinguished by interesting olfactory qualities, especially woody notes; and can accordingly be used as fragrances used, for example in perfumes,

or ketals with 1 to 5 carbon atoms in ether, soaps, detergents, cleaning agents and others Ester or ketal groups, which characterize cosmetic products.

net that one has a ketone of the formula The process according to the invention is thereby ge

indicates that one has a ketone of the formula

H ₃ C

C = C-CO-CH ₃ y (II) ■ H ₃ CH

H, C

H
= C-CO-CH ₃

H, C

Reacts in the presence of a Lewis acid as an acidic catalyst with a lower alkyl orthoformate and, if desired, the reaction product in the usual manner of hydrolysis, ketalization, Subjects to enol etherification or enol esterification.

7. The method according to claim 6, characterized in that the Lewis acid used is boron trifluoride etherate used.

8. Process according to Claims 6 and 7, characterized in that there is ethyl orthoformate used as a lower alkyl orthoformate.

Reacts in the presence of a Lewis acid as an acidic catalyst with a lower alkyl orthoformate and, if desired, the reaction product in

Usually subjected to hydrolysis, ketalization, enol etherification or enol esterification.

The α, / 5-unsaturated used as starting materials Ketone of the formula II substances, namely the mesityl oxide, is known. It can be produced by self-condensation of acetone by known methods have been.

The alkyl group of the above-mentioned alkyl orthoformate is a lower primary alkyl group with

1 to 5 carbon atoms, such as methyl, ethyl, n-prop'yl, butyl, isobutyl, amyl or isoamyl. As acidic catalysts come z. B. Lewis acids into consideration, such as boron trifluoride ether.

The reaction of the ketone of the formula II with the alkyl orthoformate generally gives in a mixture of several enol ethers, which differ in the different positions of the enol ether group. The enol ether group can z. B. are in the'Seitenkette, as is the case with the monoenolethers the general formula

H ₃ C,

CH ₃ CH ₂

(III)

CH,

wherein R is a lower alkyl group having 1 to 5 carbon atoms means.

On the other hand, the enol ether group can also be located in the ring, as is the case with the monoenol ethers the general formula

CH ₃ CH ₃

(IV)

CH ₃

where R has the above meaning.

Finally, enol ether groups can be present both in the side chain and in the ring, such as this the case is with the bis-eno ethers of the general formula

H ₁ C

RO

OR

CH ₃ CH ₂

(V)

CH ₃

where R has the above meaning.

The quantitative ratio of these different enol ethers depends on the reaction conditions and before everything depends on the ratio of the two starting components. When using a strong Excess of the ketone of the formula II over the alkyl orthoformate is predominantly obtained as the monoenol ethers of the general formula III. If, on the other hand, the two starting components are used roughly equimolar amounts, the bis-enol ethers of the general formula V are mainly obtained.

The reaction products can be isolated from the reaction mixture by customary methods, for example by repeated fractional distillation. Completely pure products can e.g. obtained by chromatography.

The enol ethers obtained of the general formulas III, IV or V can be hydrolysed, preferably acid hydrolysis, converted into the corresponding diketone of the formula I.

If, for example, the enol ethers are subjected to the general formula

OR

(IHa)

(IVa)

(Va)

where R has the above meaning, at room temperature the action of dilute hydrochloric acid, 4-acetyl-3,3,5,5-tetramethyl-cyclohexanone (I) is thus formed.

The diketone obtained in this way can be subjected to ketalization by methods known per se are, for example, by reaction with a lower alkylene glycol, such as ethylene or Propylene glycol, in the presence of an acidic agent. It can be mono-ketals of general formula

RO

CH ₃ CH ₃

(VI)

CH,

wherein the two symbols R are a lower alkyl group, with 1 to 5 carbon atoms, or together a lower one Means alkylene group with 2 to 4 carbon atoms.

For example, the diketone of the formula I can be converted into ketals of the general formula

(Via)

where R has the above meaning, obtained, for example, the ^ acetyl-U-dimethoxy-S ^^ S-tetramethyl-cyclohexane or the 4-acetyl-l, l-ethylenedi-

The diketone of the formula I can also be converted into the corresponding ones by methods known per se Convert enol ethers or enol esters. For example, it is suitable for conversion into an enol ether the reaction with a lower alkyl orthoformate, such as methyl or ethyl orthoformate, in the presence

a Lewis acid such as boron trifluoride etherate. To the Conversion into an enol ester, as in the 1-acetoxy-4 - Acetyl - 3,3,5,5 - tetramethyl - cyclohexene - (1), you can said diketone with a conventional esterifying agent, z. With a functional derivative of a lower alkanecarboxylic acid, for example with a React anhydride or ester of such an acid, for example with isopropenyl acetate.

The following compounds, for example, are distinguished by their special smell qualities:

The mono-ethylenol ether of the formula

OCH,

(HIb)

29

d. H. 4- (l-ethoxy-vinyl) -3,3,5,5-tetramethyl-cyclohexanone, has a woody odor with an animal note.

The bis-ethylenol ether of the formula

OC ₂ H ₅

CH,

(Vb)

30th

H ₅ C ₂ O

ie the l-ethoxy-4- (l-ethoxy-vinyl) -3,3,5,5-tetramethyl-cyclohexene (l) has a pleasant woody odor.
The mono-ethylenol ether of the formula

(IVb)

H ₅ C ₂ O

40

45

d. H. the l-ethoxy ^ -acetyl ^^^^ - tetramethyl-cyclohexen- (l) has a very fine woody odor, like the ethylene ketal of the formula

sches is increased to 50 °, whereupon 148 g (1 mol) of ethyl orthoformate are added in the course of 4 hours. The temperature is kept at 50 ° for 4 hours, after which 5 g of powdered sodium carbonate are added and the mixture is stirred for a further 30 minutes. The resulting mass is then washed with 100 ml of a 10% sodium carbonate solution and twice more with 100 ml of 30% salt water each time. A mixture of ethyl alcohol, ethyl formate and excess mesityl oxide is obtained by distillation at normal pressure. Rectification gives about 70 g of a mixture boiling between 75 and 84 °, from which 4- (l-ethoxy-vinyl) -3,3,5,5-tetramethyl-cyclohexanone (cf. formula IIIb) can be isolated . Boiling point: 80 to 82 ° / 2 mm Hg; n ¹ _D ^s : 1.4758; Carbonylindex: 245 (theoretical value for a function = 250).

Example 2

ImI boron trifluoride etherate is added to 117.6 g (1.2 mol) of mesityl oxide. The temperature of the reaction mixture is increased to 50 °, whereupon 148 g (1 mol) of ethyl orthoformate are added in the course of 2 hours. The temperature is ^{held at 30 1} for 24 hours, after which it is worked up as described in Example 1. The following compounds are obtained as the main products in practically the same quantities:

a) 1 - ethoxy - 4 - (1 - ethoxy - vinyl) - 3,3,5.5 - tetramethyl-cyclohexen- (l) (cf. the formula V b): boiling point: 74 to 76 ° / 2 mm Hg; njf: 1.4744: Carbonylindex: 220 (theoretical value for a function = 222).

b) The 4- (l-ethoxyvinyl) -3,3,5,5-tetramethyl-cyclohexanone described in Example 1 the formula IHb.

Example 3

One of the enol ethers obtained according to Example 1 or 2 is hydrolyzed with 10 times the amount by weight of 0.5% strength aqueous hydrochloric acid by the The mixture is stirred for 24 hours at room temperature (about 20 to 25 °). Obtained from 100 g of starting material thus about 75 g of a crude product, which is purified by fractional distillation. That's how you get it 4-acetyl-3,3,5,5-tetramethyl-cyclohexanone (cf. formula Ia). Boiling point: 10872mm Hg; iijf: 1.4786.

H, C

ie <
cyclohexane.

In the following examples, the temperatures are given in degrees Celsius. "

example 1

1 ml of boron trifluoride etherate is added to 490 g (4 mol) of mesityl oxide. The temperature of the reaction mixture

Example 4

1 mol of 4-acetyl-3,3,5,5-tetramethyl-cyclohexanone is mixed with 1 mol of ethylene glycol in a benzene solution reacted in the presence of p-toluenesulfonic acid. After the reaction has ended, the benzene solution is washed and, after the benzene has been removed, the 4-acetyl -1,1- äthy lendioxy- 3,3,5,5 - tetramethyl - cyclo- (VIb) 55 hexane (cf. the formula VIb) in crystallized form with a melting point of 113 to 113.5 °.

Example 5

To 196 g (l mol) of 4-acetyl-3,3,5,5-tetramethyl-cyclohexanone, containing 1 ml of boron trifluoride etherate. adds 132.5 g (1.25 mol) of methyl orthoformate are added dropwise at 35 ± 5 ° over the course of one hour. After completion After the addition, the reaction mixture is kept at the stated temperature for a further 24 hours. Then add 8 g of powdered sodium carbonate, stir for 15 minutes, dilute with 11 petroleum ether and washes as usual. After repeated distillations one obtains with an overall yield of approximately

20th

80% and in a ratio of 1: 4 the following two Links:

a) 4-acetyl-1-methoxy-S ^ S-tetramethyl-cyclohexene (1); Boiling point: 78 to 80 ° / l mm Hg; ng: 1.4780;

b) 4 - acetyl - 1,1 - dimethoxy - 3,3,5,5 - tetramethylcyclohexane; Boiling point: 90 to 9371mm Hg; Melting point: 59 to 60 °.

Both compounds have an intense cork odor, the second with a clear caryophyllenol note.

Example 6

The following monoenol ethers are obtained in an analogous manner:

4 - acetyl - 1 - ethoxy - 3,3,5,5 - tetramethyl - cyclohexene (1); Boiling point 90 ° / l mm Hg; ng: 1.4745; Smell of cork and cloves with a geranium component.

4-acetyl-ln-propoxy-S ^ .S ^ tetramethyl-cyclohexen (l); Siedepunkt92 ^o / 0.4 mm Hg; "": 1.4749; moldy note of the patchquli type.

4 -acetyl -1 - η - butoxy- 3,3,5,5 - tetramethyl - cyclo-

hexen- (l); Boiling point 97 to 9970.4 mm Hg; ng: 1.4735; intense woody smell of the sandalwood type with a moldy note.

4-acetyl-1-isobutoxy-S ^^^ - tetramethyl-cyclohexen-(1); Boiling point 107-10970.5 mm Hg;

/ ijf: 1.4712; intense moldy smell of the Patschquli type.

4 - acetyl - 1 - η - amyloxy - 3,3,5,5 - tetramethylcyclohexene (1); Boiling point 101-1047 0.3 mm Hg; ng: 1.4630; Smell weaker than

in the previous examples, but of the same ■ woody-moldy character.

4 - acetyl - 1 - isoamyloxy - 3,3,5,5 - tetramethylcyclohexene (1); Boiling point 106 to 1087 0.2 mm Hg; ng = 1.4658; same type of odor as the substances described above.

4-acetyl -1 - allyloxy - 3,3,5,5 - tetramethyl - cyclohexene (1); Boiling point 95 to 10070.5 mm Hg; ng: 1.4846; woody odor with clove notes.

In addition, the corresponding ketals can be obtained, e.g. B .:

35

40

4-acetyl!,

hexane; Boiling point 10471 mm Hg; ng: 1.4676.

4-acetyl-1,1-di-n-propoxy-3,3,5,5-tetramethylcyclohexane; Boiling point 11870.4 mm Hg; ng:

1.4676.

4-acetyl-1,1-di-n -butoxy -3,3,5,5-tetramethylcyclohexane; Boiling point 125 to 12770.4 mm Hg; JiJf: 1.4662; weak woody note.

4 - acetyl -1,1- di-isobutoxy -3,3,5,5-tetramethylcyclohexane; Boiling point 125 to 12870.5 mm Hg; M.p. 48 °.

Example 7

By implementing ^ acetyl-S ^^
Cyclohexanone with isopropenyl acetate gives 1 - acetoxy - 4 - acetyl - 3,3,5,5 - tetramethyl - cyclohexene (1) ″ with a boiling point of 92 to 9470.3 mm Hg; ng: 1.4785. This compound is distinguished characterized by a very fine but weak woody and amber-like odor.

Example 8

According to the method described in Example 1, starting from mesityl oxide and methyl orthoformate, a mixture of substances with a boiling point of 80 to 9071 mm Hg (the smell of which is similar to that of the corresponding mixture of Example 1), from which the 4- (l-methoxy-vinyl) -3,3,5,5-tetramethyl-cyclohexanone is derived can isolate from boiling point 90 to 927 1 mm Hg (melting point 45 °).

If one works under the reaction conditions given in Example 2, one can, starting from mesityl oxide and methyl orthoformate, also obtain the corresponding bis-enol ether, namely 1-methoxy-4- (1-methoxy-vinyl) -3,3,5 , 5 - tetramethylcyclohexen-il); Boiling point 82 to 847 lmm Hg; ng: 1.4872.

Example 9

The process described in Example 1 gives, starting from mesityl oxide and n-propyl orthoformate, a mixture of the corresponding n-propyl enol ethers with a boiling point of 95 to 1007 lmm Hg; ng: 1.4795. The odor is similar to that of the corresponding mixture from Example 1.

Example 10

According to the process described in Example 1, starting from mesityl oxide and isobutyl orthoformate, a mixture of the corresponding isobutyl enol ethers with a boiling point of 110 to 1207 1 mm Hg is obtained; ng: 1.4775. The odor is similar to that of the corresponding mixture from Example 1, but is less strong.

11th

example

According to the process described in Example 1, starting from mesityl oxide and isoamyl orthoformate, a mixture of the corresponding isoamyl enol ethers with a boiling point of 110 to 1207 1 mm Hg is obtained; ng: 1.4780. The odor is similar to that of the corresponding mixture from Example 1, but is weaker.

209 536/573

Claims (1)

Patent claims:
1. Diketone of the formula CH, O (D 9. Use of a cyclic diketone of the formula