Odoriferous cycloalkyl acetals

OBJECTS OF THE INVENTION
An object of the present invention is the development of an odoriferous acetal having the formula ##STR1## wherein R is a cycloalkyl having from 8 to 12 carbon atoms, R.sub.1 is a member selected from the group consisting of hydrogen and methyl, and R.sub.2 is a member selected from the group consisting of methyl, ethyl, propyl, isopropyl, allyl and propargyl.
Another object of the present invention is the development of a process for the preparation of the above odoriferous acetal which consists of the steps of reacting a cycloalkanol having the formula
R--OH
wherein R is a cycloalkyl having from 8 to 12 carbon atoms with an excess of an aldehyde having the formula
R.sub.1 --CHO
wherein R.sub.1 is a member selected from the group consisting of hydrogen and methyl and an excess of hydrogen chloride in an inert organic solvent under conditions whereby water is removed as it is produced, reacting the resulting chloroalkoxy-cycloalkane having the formula ##STR2## WHEREIN R and R.sub.1 have the above assigned values, with an alkali metal alcoholate having the formula
MeOR.sub.2
wherein Me is an alkali metal and R.sub.2 is a member selected from the group consisting of methyl, ethyl, propyl, isopropyl, allyl and propargyl, and recovering said odoriferous acetal.
A yet further object of the present invention is the development of odoriferous compositions of various odor giving compounds containing from 1 to 50% by weight of the above odoriferous acetal.
These and other objects of the invention will become more apparent as the description thereof proceeds.
DESCRIPTION OF THE INVENTION
The present invention provides compounds having the formula ##STR3## wherein R represents a cycloaliphatic group, preferably a cycloalkyl group, having 8 to 12 carbon atoms, R.sub.1 represents hydrogen or a methyl group and R.sub.2 represents a methyl, ethyl, propyl, isopropyl, allyl or propargyl group. These compounds are excellent odoriferous substances having a woody amber quality of scent.
The present invention also provides a process for the production of a compound of the present invention which comprises reacting a cycloalkanol having the formula R--OH with an aldehyde having the formula R.sub.1 --CHO and hydrogen chloride in an organic solvent with removal of water formed, to give the appropriate cycloalkyl-chloralkyl-ether or chloroalkoxycycloalkane having the formula ##STR4## which in the second stage is then reacted with an alkoxide having the formula MeOR.sub.2, in which Me preferably represents an alkali metal, particularly sodium, to give the odoriferous acetal having the formula ##STR5## In these formulae R, R.sub.1 and R.sub.2 are as defined above.
Suitable cycloaliphatic starting alkanols are cyclooctanol, cyclononanol, cyclodecanol, cycloundecanol and cyclododecanol. Of these, cyclooctanol and cyclododecanol are of the greatest importance in view of their availability.
The aldehydes which are to be reacted with the abovementioned cycloalkanols are formaldehyde and acetaldehyde, formaldehyde being of greater importance because the compounds derived therefrom have a stronger smell and are more suitable as odoriferous substances.
The alcoholates to be used in the second step of the process of the present invention particularly the sodium alcoholates, are obtained from methanol, ethanol, propanol, isopropanol, allyl alcohol and propargyl alcohol. Of these, methanol and ethanol are of the greatest importance since products having the most intensive smell are obtained when they are used.
Accordingly, the following constitute new odoriferous substances of the invention falling under the formula: formaldehyde-methyl-cyclooctyl-acetal, formaldehyde-methyl-cyclononyl-acetal, formaldehyde-methyl-cyclodecyl-acetal, formaldehyde-methyl-cycloundecyl-acetal, formaldehyde-methyl-cyclododecyl-acetal, formaldehyde-ethyl-cyclooctyl-acetal, formaldehyde-ethyl-cyclononyl-acetal, formaldehyde-ethyl-cyclodecyl-acetal, formaldehyde-ethyl-cycloundecyl-acetal, formaldehyde-ethyl-cyclododecyl-acetal, formaldehyde-propyl-cyclooctyl-acetal, formaldehyde-propyl-cyclononyl-acetyl, formaldehyde-propyl-cyclodecyl-acetal, formaldehyde-propyl-cycloundecyl-acetal, formaldehyde-propyl-cyclododecyl-acetal, formaldehyde-isopropyl-cyclooctyl-acetal, formaldehyde-isopropyl-cyclononyl-acetal, formaldehyde-isopropyl-cyclodecyl-acetal, formaldehyde-isopropyl-cycloundecyl-acetal, formaldehyde-isopropyl-cyclododecyl-acetal, formaldehyde-allyl-cyclo-octyl-acetal, formaldehyde-allyl-cyclononyl-acetal, formaldehyde-allyl-cyclodecyl-acetal, formaldehyde-allyl-cyclo-undecyl-acetal, formaldehyde-allyl-cyclododecyl-acetal, formaldehyde-propargyl-cyclooctyl-acetal, formaldehyde-propargyl-cyclononyl-acetal, formaldehyde-propargyl-cyclodecyl-acetal, formaldehyde-propargyl-cycloundecyl-acetal, formaldehyde-propargyl-cyclododecyl-acetal, acetaldehyde-methyl-cyclooctyl-acetal, acetaldehyde-methyl-cyclononyl-acetal, acetaldehyde-methyl-cyclodecyl-acetal, acetaldehyde-methyl-cycloundecyl-acetal, acetaldehyde-methyl-cyclododecyl-acetal, acetaldehyde-ethyl-cyclooctyl-acetal, acetaldehyde-ethyl-cyclononyl-acetal, acetaldehyde-ethyl-cyclodecyl-acetal, acetaldehyde-ethyl-cycloundecyl-acetal, acetaldehyde-ethyl-cyclododecyl-acetal, acetaldehyde-propyl-cyclooctyl-acetal, acetaldehyde-propyl-cyclononyl-acetal, acetaldehyde-propyl-cyclodecyl-acetal, acetaldehyde-propyl-cycloundecyl-acetal, acetaldehyde-propyl-cyclododecyl-acetal, acetaldehyde-isopropyl-cyclooctyl-acetal, acetaldehyde-isopropyl-cyclononyl-acetal, acetaldehyde-isopropyl-cyclodecyl-acetal, acetaldehyde-isopropyl-cycloundecyl-acetal, acetaldehyde-isopropyl-cyclododecyl-acetal, acetaldehyde-allyl-cyclooctyl-acetal, acetaldehyde-allyl-cyclononyl-acetal, acetaldehyde-allyl-cyclodecyl-acetal, acetaldehyde-allyl-cycloundecyl-acetal, acetaldehyde-allyl-cyclododecyl-acetal, acetaldehyde-propargyl-cyclooctyl-acetal, acetaldehyde-propargyl-cyclononyl-acetal, acetaldehyde-propargyl-cyclodecyl-acetal, acetaldehyde-propargyl-cycloundecyl-acetal and acetaldehyde-propargyl-cyclododecyl-acetal.
Of the above-mentioned compounds, which are suitable as new odoriferous substances, the products formaldehyde-methyl-cyclooctyl-acetal, formaldehyde-methyl-cyclododecyl-acetal, formaldehyde-ethyl-cyclooctyl-acetal and formaldehyde-ethyl-cyclododecyl-acetal are being the most important, and formaldehyde-methyl-cyclooctyl-acetal and formaldehyde-methyl-cyclododecyl-acetal are the most significant.
The odoriferous acetals of the invention are produced by reacting the cycloalkanol with the aldehyde and hydrogen chloride under conditions where the water formed is excluded from the reaction, and thereafter reacting the chloroalkoxy-cycloalkane with an alkali metal alcoholate. The first step is preferably conducted with an excess of the aldehyde and hydrogen chloride to avoid formation of a gem.-acetal. The amount of excess of the aldehyde is immaterial although amounts of from 2 to 15 mols per mol of cycloalkanol are often employed. The reaction is conducted in an inert organic solvent liquid at the temperatures employed, such as chlorinated hydrocarbon solvents and aromatic hydrocarbon solvents, at temperatures of from 10.degree. C down to the freezing point of the solvent mixture. Excess hydrogen chloride is introduced, preferably in a gas stream at such a rate that the upper temperature limit is not exceeded, for a time sufficient for at least the stoichiometric amount of HCl to be reacted. The reaction is conducted under anhydrous conditions and the water produced by the reaction is removed as it is produced. Preferably the water is removed by conducting the reaction in the presence of an inert, anhydrous, inorganic salt which combines with water to form a crystalline salt with water of crystallization, such as sodium sulfate.
The second step of the reaction is preferably conducted with the solution of the reaction product of the first step after separation of the solid inorganic salt combined with water. This solution is added to the alkali metal alcoholate, preferably in solution in the same alcohol at a low temperature, of from 25.degree. C down to the freezing point of the solvent mixture. Preferably, the solution is added to the alkali metal alcoholate solution at a rate whereby the reaction temperature does not exceed 20.degree. C. The alkali metal alcoholate is employed in excess of the stoichiometric amount.
After the addition to the alkali metal alcoholate has been completed, the reaction is continued at an elevated temperature of from 30.degree. C up to the reflux temperature for a further period of 0.25 to 5 hours. The sodium chloride formed is separated and the odoriferous acetal is obtained after distilling off the solvents.
The new odoriferous substances of the invention are marked by a particularly intensive and lingering woody amber type of scent of high quality and richness. Other advantageous properties of the new odoriferous acetals are their good combination with other odoriferous substances to give novel nuances of scent, and their special adhering capacity.
The new odoriferous acetals of the invention can be mixed with other odoriferous substances in the most diverse quantity ratios to give new odoriferous substance compositions. However, the proportion of the new odoriferous acetals in the odoriferous substance compositions will generally range from 1 to 50% by weight, based on the entire composition. Such compositions can be used as they are as perfume, or to perfume cosmetics, such as creams, lotions, toilet water, aerosols, toilet soaps etc. However, they can also be used, as is also possible in the case of the actual new compounds, to improve the smell of technical products, such as washing and cleaning agents, disinfectants, agents for treating textiles, etc.

The following examples are intended to describe the subject matter of the invention in greater detail without, however, restricting it to said examples.
The production of the new odoriferous acetals is to be described first of all.
EXAMPLE 1
Formaldehyde-methyl-cyclododecyl-acetal
368 gm of cyclododecanol (2.0 mols), 250 gm of anhydrous sodium sulfate and 66,0 gm of paraformaldehyde were dispersed in 600 ml of xylene and the mixture was cooled to a temperature of -20.degree. C. While the mixture was stirred energetically, as strong a flow as possible of hydrogen chlorine was introduced, the speed at which it was introduced being controlled such that the reaction temperature did not exceed +5.degree. C. After approximately one hour the speed of introduction was decreased and subsequent reaction was effected while hydrogen chloride was bubbled through gently. Water-jet vacuum was then applied gradually during energetic stirring in order to remove surplus hydrogen chloride. When the highest water-jet vacuum had been achieved, the mixture was heated to 30.degree. C over a period of one hour, and subsequent stirring was effected at this temperature for a further hour. The sodium sulfate was then drawn off by vacuum filtration and the solution of the chloromethoxy-cyclododecane thus obtained could be used for the next reaction without special processing.
The solution of the chloromethoxy-cyclododecane was added during stirring and in the course of 1 to 2 hours to 400 gm of a 33% sodium methoxide solution in methanol, which solution had been cooled to a temperature of -20.degree. C at a rate such that the temperature did not exceed 20.degree. C. Subsequent to this addition, stirring was effected for a further hour at 40.degree. to 50.degree. C. The majority of the sodium chloride which had separated out was dissolved and separated off by stirring briefly with 700 ml of cold water. The organic phase was then washed with 100 ml of a 20% sodium chloride solution. The separated organic solution was subsequently freed of solvent and the formaldehyde-methyl-cyclododecyl-acetal which was obtained was distilled at 0.01 torr. 433 gm i.e. 95% of theory, was obtained. The formaldehyde-methyl-cyclododecyl-acetal is a colorless liquid and has the following characteristic data:
Boiling point at 0.01 Torr = 86.degree. C Density d.sub.4.sup.20 = 0.9463
Refractive index n.sub.D.sup.20 = 1.4695
IR(Film): 1370, 1342, 1142, 1098, 1060, 1030/cm (C--O--CH.sub.2 --O--C)
NMR (CCl.sub.4): .DELTA. 4.56 (S) 2H (O--CH.sub.2 --O); 3.33 (S) 3H (OCH.sub.3)
MS: M+ = 228, m/e = 45 (CH.sub.3 --O--CH.sub.2 .sup.+)
The chloromethoxy-cyclododecane obtained as intermediate product is a colorless liquid having the following characteristic data:
Boiling point at 0.5 Torr = 110.degree. C
Density d.sub.4.sup.20 = 1.0142
Refractive index: n.sub.D.sup.20 = 1.4892
IR (film): 1120/cm (C--O--C); 645/cm (C--Cl)
NMR (CDCl.sub.3): .delta. 5.6 (S) 2H (C--O--CH.sub.2 --Cl)
MS: M.sup.+ = 233, M.sup.+-36 (HCl), M.sup.+-66 (HOCH.sub.2 Cl-elimination.fwdarw.cyclododecene.sup.+)
EXAMPLE 2
Formaldehyde-ethyl-cyclododecyl-acetal
The product was obtained by reacting chloromethoxy-cyclododecane with sodium ethoxide and is a colorless liquid having the following characteristic data;
Boiling point at a 0.001 Torr = 94.degree. C
Refractive index n.sub.D.sup.20 = 1.4665
NMR (CCl.sub.4): .delta. 4.7 (S) 2H (O--CH.sub.2 --O); 3.6 (q) 2H/J=7 Hz (O--CH.sub.2 --C); 1.2 (t) 3H/J = 7 Hz (O--C--CH.sub.3)
MS: M.sup.+ = 242, m/e = 59 (CH.sub.3 --CH.sub.2 --O--CH.sub.2 .sup.+)
EXAMPLE 3
Formaldehyde-propyl-cyclododecyl-acetal
The product was obtained by reacting chloromethoxy-cyclododecane with sodium propoxide, and is a colorless liquid having the following characteristic data;
Boiling point at 0.01 Torr = 97.degree. C
Refractive index n.sub.D.sup.20 = 1.4677
EXAMPLE 4
Formaldehyde-isopropyl-cyclododecyl-acetal
The compound, which is a colorless liquid, was obtained by reacting chloromethoxy-cyclododecane with sodium isopropoxide.
Boiling point at 0.01 Torr = 94.degree. C
Refractive index n.sub.D.sup.20 = 1.4657
EXAMPLE 5
Formaldehyde-allyl-cyclododecyl-acetal
The compound was produced by reacting chloromethoxycyclododecane with the sodium compound of allyl alcohol, and is a colorless liquid having the following characteristic data:
Boiling point at 0.01 Torr = 107.degree. C
Refractive index n.sub.D.sup.20 = 1.4760
EXAMPLE 6
Formaldehyde-propargyl-cyclododecyl-acetal
The product, which is a colorless liquid, was obtained by reacting chloromethoxy-cyclododecane with the sodium compound of propargyl alcohol, and has the following characteristic data:
Boiling point at 0.005 Torr + 104.degree. C
Refractive index n.sub.D.sup.20 = 1.4821
EXAMPLE 7
Formaldehyde-methyl-cyclooctyl-acetal
In accordance with the process given in Example 1, the chloromethoxy-cyclooctane was first of all produced from cyclooctanol, paraformaldehyde and hydrogen chloride, and was then reacted in the second stage with sodium methoxide to give formaldehyde-methyl-cyclooctyl-acetal, a colorless liquid having the following characteristic data:
Boiling point at 0.4 Torr = 75.degree. C
Density d.sub.4.sup.20 = 0.9557
Refractive index n.sub.D.sup.20 = 1.4570
IR (film): 1378, 1360, 1150, 1090, 1045/cm (C--O--CH.sub.2 --O--C)
NMR (CCl.sub.4): .delta. 4.6 (S) 2H (O--CH.sub.2 --O); 3.35 (S) 3H (OCH.sub.3)
MS: M.sup.+ = 172,M.sup.+ - 32 (CH.sub.3 OH), M.sup.+ - 61 (CH.sub.3 --O--CH.sub.2 --O) m/e = 45 (CH.sub.3 --O--CH.sub.2 .sup.+)
EXAMPLE 8
Formaldehyde-ethyl-cyclooctyl-acetal
The product was obtained by reacting chloromethoxy-cyclooctane with sodium ethoxide and is a colorless liquid having the following characteristic data:
Boiling point at 0.4 Torr = 82.degree. C
Density d.sub.D.sup.20 = 0.9399
Refractive index n.sub.D.sup.20 = 1.4548
NMR: (CCl.sub.4): .delta. 4.7 (S) 2H (O--CH.sub.2 --O): 3.6 (q) 2 H/J = 7 Hz (O--CH.sub.2 --C) 1.2 (t) 3 H/J = 7 Hz (O--C--CH.sub.3)
MS: M.sup.+ = 186, M.sup.+ - 29 (CH.sub.2 --CH.sub.3), M.sup.+ - 46 (CH.sub.3 --CH.sub.2 --O) M.sup.+ - 59 (CH.sub.3 --CH.sub.2 --O--CH.sub.2), m/e = 59 (CH.sub.3 --CH.sub.2 --O--CH.sub.2 .sup.+)
EXAMPLE 9
Formaldehyde-allyl-cyclooctyl-acetal
The compound was produced by reacting chloromethoxycyclooctane with the sodium compound of allyl alcohol. It is a colorless liquid having the following characteristic data:
Boiling point at 0.2 Torr = 101.5.degree. C
Refractive index n.sub.D.sup.20 = 1.4685
EXAMPLE 10
Formaldehyde-propargyl-cyclooctyl-acetal
The product, a colorless liquid, was obtained by reacting chloromethoxy-cyclooctane with the sodium compound of propargyl alcohol and has the following characteristic data:
Boiling point at 0.1 Torr = 104.degree. C
Refractive index n.sub.D.sup.20 = 1.4752
All the compounds mentioned in the above Examples have an persistant woody scent, which makes them suitable for the production of the most diverse odoriferous substance compositions. Such compositions can be used to perfume the most diverse products, such as cosmetics, washing agents, soaps, but also technical products, in concentrations of approx. 0.05 to 2% by weight. Several Examples of odoriferous substance compositions containing compounds of the invention are given hereinafter.
EXAMPLE 11
______________________________________Woody scent base composition parts by weight______________________________________Formaldehyde-methyl-cyclododecyl-acetal 500Oryclon 100Vetiveryl acetate 100Sandlewood oil 100Isoraldein 70 50Guaiyl acetate 50Coumarin 50Phenyl ethyl alcohol 50______________________________________
EXAMPLE 12
______________________________________Woody scent base composition parts by weight______________________________________Formaldehyde-methyl-cyclooctyl-acetal 140Bergamot oil 250Bulgarian rose oil 50Sandlewood oil 40Vetiver oil 110Cedar oil 50Cinnamyl acetate 40Coumarin 70Methylionone 150Peru balsam 40Benzyl acetate 60______________________________________
EXAMPLE 13
______________________________________Woody quality substance composition parts by weight______________________________________Formaldehyde-ethyl-cyclododecyl-acetal 250Sandlewood oil 355Bergamot oil 100Vetiver oil 50Coumarin 50Rose oil 50Amyl salicylate 75Heliotrepin 50Xylene musk 20______________________________________
EXAMPLE 14
______________________________________Imaginative perfuming composition parts by weight______________________________________Formaldehyde-propargyl-cyclododecyl-acetal 340Geranium oil 100Lavender oil 100Cedar oil 100Anisaldehyde 150Butylphenyl acetate 50Hydroxy-citronellal 50Methyl naphthyl ketone 50Benzyl acetate 40Xylene musk 20______________________________________
EXAMPLE 15
______________________________________Imaginative perfuming compositionwith a hay-like quality parts by weight______________________________________Formaldehyde-allyl-cyclooctyl-acetal 30Bergamot oil 250Lavender oil 200Hydroxy-citronellal 200Linalool 50Methyl salicylate 50Ylang-ylang oil 50Coumarin 60Tonka abs. 30Oak moss 20Ketone musk 20Vetiver oil 10Patchouli oil 10Benzyl acetate 10Vanillin 10______________________________________
In the above-listed odoriferous substance compositions it is also possible for the stated acetals to be replaced by other compounds of the invention, thus producing shifts in the scent nuances.
The proceeding specific embodiments are illustrative of the practice of the invention. It is to be understood however, that other expedients known to those skilled in the art or disclosed herein may be employed without departing from the spirit of the invention or the scope of the appended claims.

Number	Name	Date
3024284	Howard et al.	Mar 1962
3061649	Erickson et al.	Oct 1962
3876561	Naegeli	Apr 1975

Odoriferous cycloalkyl acetals

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