US2809996A - Compounds having an ambergris scent and their preparation - Google Patents

Compounds having an ambergris scent and their preparation Download PDF

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US2809996A
US2809996A US191939A US19193950A US2809996A US 2809996 A US2809996 A US 2809996A US 191939 A US191939 A US 191939A US 19193950 A US19193950 A US 19193950A US 2809996 A US2809996 A US 2809996A
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aldehyde
ambergris
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Stoll Max
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Firmenich SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/225—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/19—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups
    • C07C47/192—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups containing rings
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
    • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
    • C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms
    • C11B9/0053—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms both rings being six-membered

Definitions

  • sclareol the diterpenic glycol, which is the principal constituent of the essential oil from clary sage, is always accompanied by a faint scent of ambergris although it is scentless in the pure state.
  • the present invention relates to new chemical compounds havingan ambergris scent and to the chemical process for the preparation of these new cmopounds of the general Formula VIII to be found below. More particularly, the invention relates to the A -2,5,5,9-tetramethyl-octalyl acetic aldehyde, to the A 2,5,5,9-tetramethyl-octalyl-ethanol, to,
  • the chemical process for preparing such compounds is characterized in that a substance presenting the 2,5,5,9- tetramethyl-decalyl group, comprising in the position 2 an eliminable radical, and in the position 1 one of the follow ing radicals:
  • x denotes an eliminable radical such as a hydroxy-acyl group (e. g.. the group O.CO.CH3) or the hydroxy radical or a halogen atom,
  • R indicates a functional radical such as alcohol, aldehyde, acid or ester.
  • R indicates an alcohol or aldehyde radical.
  • R of the Formula VII is an alcoholor aldehyderadical, it is not necessary to transform it in order to obtain the new compound according to the Formula VIII. If on the contrary R is an acidor ester-radical, it has to be transformed into an alcoholor aldehyde-radical; this transformation may take place before or after the elimination of the radical x; if it takes place before, the case is reestablished where R of the Formula VII is an alcoholor aldehyde-radical.
  • the eliminable radical x is a hydroxyl group
  • the above transformation is preponderant in respect of the one indicated by the Formulae VII and VIII, even in the case where R" is a chain of three carbon atoms.
  • the hydrocarbon radical comprising the hydroxyl group, represented by R"-OH may for example be one of the following groups:
  • the epoxides according to the Formula X are characterized by a very fine and pronounced ambergris scent. These epoxides are new substances and of evident interest for perfumery.
  • the present invention also relates to these new epoxides.
  • acetylated hydroxy-aldehyde (Formula IV) or the acetoxyacid (Formula II) indicated above.
  • These materials may preferably be obtained by the ozonolysis of the anhydride of 1 butylone 2 hydroxy 2,5,5,9-tetramethyl-decaline (Formula I) (Ruzicka, Seidel, Engel, Helveticazia acta 25, 621 (1942)), which yields conjointly the aldehyde of the Formula IV and the acid of the Formula II.
  • Such an ester can for example be obtained by the saponification of the acid of the Formula II alone or in admixture with the aldehyde of the Formula IV (in the latter case in thepresence of air) which yields the lactone of the 2-hydroxy-2,5,5,9- tetramethyl-decalyl acetic acid. This lactone is subsequently transformed into an ester by transesterification.
  • the ester may alternatively be obtained by the transesterification of the acid of the Formula II.
  • the hydroxy-aldehyde of the Formula XI (enolic form) does not yield the epoxides of Formula X, but yields along with unsaturated aldehyde of Formula VIII other substances of undetermined composition and not of interest.
  • These substances may be prepared by the ozonolysis of the anhydride of the 1-butylone-2-hydroxy-2,5,5,9-tetramethyl-decaline (Formula I) followed by an appropriate treatment which yields inter alia a monoacetylated -glycol, to wit the 2-acetoxy-2,5,S,9-tetramethyl-decalyl-ethanol (Formula III) and an acetylated hydroxy-aldehyde: the 2-acetoxy2,5,5,9-tetramethyl-decalyl-ethanal (Formula IV).
  • a hydroxy-aldehyde of the Formula XI is obtained.
  • the elimination of the radical x may be effected by distillation of the substance in question under a reduced pressure, and according to the case in the presence of a catalyst, such as powdered copper bronze, aluminium oxide, sebacic acid, fl-naphthalenesulphonic acid, alcoholic sulphuric acid, etc.
  • a catalyst such as powdered copper bronze, aluminium oxide, sebacic acid, fl-naphthalenesulphonic acid, alcoholic sulphuric acid, etc.
  • the said elimination may be effected at the same time and in the same reaction medium as the transesterification of the lactone or of the ester as mentioned hereabove since the same reagent is used for each of these operations.
  • Example 1 The neutral fraction of the products resulting from the ozonolysis of the sclareol oxide (Formula I), which contains accordingly the aldehyde of the Formula IV, is distilled in the presence of a little copper bronze or sebacic acid under 15 mm. vacuum. The distillate is refractionated under 15 mm. vacuum and the fractions which distil off above C. are submitted to a new treatment with copper until a practically complete elimination of the acetic acid is achieved. After separation of the acidic fraction, the new compound thus prepared, which is the aldehyde of Formula V, possesses an ambergris scent and has the following physical constants:
  • the said deacylation can also be carried out on the mixture of both said fractions and the neutral and respectively acidic fractions may afterwards be separated.
  • Example 2 The acid fraction of the products resulting from the ozonolysis of the sclareol oxide (Formula I), or the product resulting from the oxidation by means of permanganate of the neutral fraction of the said oxonolysis (this fraction or this product containing the acid ofthe Formula II), is heated in a weak vacuum at 160200 C. in the presence of copper bronze. After 40 minutes the elimination of the acetic acid is almost quantitative. The unsaturated acid thus obtained distils under 0.01 mm. at 135l45 C. This is reduced in ethereal solution by means of LiAlH4, and the unsaturated alcohol of ambergris scent (Formula VI) having Ebo.o1 mm. 116117 C. is directly obtained.
  • the methanol used hereabove contains more than 5% of sulphuric acid, a dehydration of 'the acid of the Formula II-is effected which yields directly the unsaturated ester; the treatment with iodine is then unnecessary.
  • Example 4 The acid fraction of the products resulting from the ozonolysis of the sclareol oxide (Formula I) which accordingly contains the acid of the Formula H, is saponified by means of alcoholic potash.
  • This ester is dehydrated into an unsaturated ester which is then reduced, as in the Example 3, to an alohol of the Formula VI.
  • Example 7 11.2 g. of glycol of the Formula XII are heated in the presence of 40 mg. of .9-naphthalene sulphonic acid at 135 C. in vacuo; the reaction mixture is then distilled, and the fraction boiling under 10 mm. Hg between 168 and 173 C. is recovered. By the treatment of this fraction with petrol ether, 8 g. of epoxide melting at 75-76 C.
  • the chlorinated alcohol of Formula IX is transformed into the unsaturated alcohol of Formula VI and into the epoxide of the Formula X.
  • the latter is a stereoisorner of the one described in the Examples 1 and 2. and melts at 6062 C. All these products have an ambergris scent and can be utilized pure or in admixture with one another. By distillation followed by saponification with caustic potash this mixture can be transformed into a strongly scented mixture of the epoxide and of the unsaturated alcohol. These two substances can be ery easily separated. by c r ma o rap 11 lum n um. id
  • T he invention wm r ses e se the u i izat n o he new compound having anarnbergris scent as a perfume or as a primary material 'in perfumery.
  • this perfume or this material contains at least one compound presenting the 2,5,5,9-tetramethyhoctalyl grcup, the carbon atom in the position 2 of which participates either in a double bond or in an epoxide.
  • the perfume or the primary material comprising these two compounds can very easily be obtained by carrying out the process of the present invention during which both transformations indicated on the one hand by the Formulae VII and VIII, and on the other hand by the Formulae IX and X are jointly executed.
  • the composition of a perfume containing inter alia these two compounds will now be' given by way of example:

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Description

United States Patent COMPOUNDS HAVING AN AMBERGRIS SCENT AND THEIR PREPARATION Max Stoll, Geneva, Switzerland, assignor to Firmenich & Co., successenrs de la Societe Anonyme M. Naef & Cie, Geneva, Switzerland, a corporation of Switzerland No Drawing. Application October 24, 1950, Serial No. 191,939
Claims. (Cl. 260-598) It is still completely unknown What the fragrant components of ambergris are. Its principal constituent, the tri-terpenic alcohol ambrein, is scentless in the pure state and yields by degradation a single fragrant product, namely dihydro-y ionone which does not truly smell like ambergris, and several other, scentless, products.
It is, on the other hand, known that sclareol, the diterpenic glycol, which is the principal constituent of the essential oil from clary sage, is always accompanied by a faint scent of ambergris although it is scentless in the pure state. The ozonolysis of one of its neutral degradation products, namely the anhydride of the l-butylone-2- hydroxy-2,5,5,9-tetramethyl-decaline which is also called sclareol oxide (Formula I), followed by a hydrolysis or by a reduction of the .ozonide formed, yields a mixture of at least four products, all .of which are scentless in the pure state, viz.:
(1) 2 acetoxy 2,5,5',9 tetramethyl decalyl acetic acid (Formula II); i
(2) A mono-acetylated -glycol, namely the Z-acetoXy- 2,5,5,9-tetramethyl-decalyl-ethylol (Formula III);
(3) An acetylated hydroxy-aldehyde, namely the 2- acetoxy-2,5 ,5 ,9-tetramethyl-decalyl-ethanal (Formula IV);
(4) A neutral product of unknown constitution of the empirical formula CmHsoOz.
' The unexpected discovery has now been made that by transforming either the acid of the Formula II, or the glycol of the Formula III, or the aldehyde of the Formula IV, by the loss of acetic acid, into an unsaturated aldehyde, a product is obtained, namely, the A -2,5,5,9-tetramethyl octalyl acetic aldehyde (Formula V), which has a powerful and clinging ambergris scent. It has also been ascertained that the corresponding alcohol, the A 2,5,5,9-tetramethyl octalyl-ethanol (Formula VI) possesses likewise a strongly clinging scent of an ambergris character. These two unsaturated substances, which have 2,809,996 Patented Oct. 15, 1957 never before been synthetically produced, may advanta geously replace the unknown fragrant substances of the ambergris. They form therefore new and valuable compounds which can be used in the perfumery and cosmetics trade wherever a scent of an ambergris character is desired;
CH3 CH3 C53 /CH3 9 on, on;
CH2 I Q32 H3 0110 Ha 0112011 V VI atom 2 and presenting an aldehydicor alcoholic radical in the side chain attached to the carbon atom 1, have been found to be new scent products of interest for perfumery.
The present invention, based on the discoveries stated hereabove, relates to new chemical compounds havingan ambergris scent and to the chemical process for the preparation of these new cmopounds of the general Formula VIII to be found below. More particularly, the invention relates to the A -2,5,5,9-tetramethyl-octalyl acetic aldehyde, to the A 2,5,5,9-tetramethyl-octalyl-ethanol, to,
their isomers and in general to the unsaturated compounds presenting either a 2,5,5,9-tetramethyl-octaly1 group or a 5,5,9-trimethyl-2-methylene-decalyl group, all having a double bond at the carbon atom 2 and presenting an aldehydicor alcoholic radical in the side chain attached to the carbon atom 1.
The chemical process for preparing such compounds is characterized in that a substance presenting the 2,5,5,9- tetramethyl-decalyl group, comprising in the position 2 an eliminable radical, and in the position 1 one of the follow ing radicals:
is transformed, by the elimination of the eliminable radical and by the formation of a double link at the carbon atom in the position 2, into a mixture of compounds having 16 to 17 carbon atoms and presenting the 2,5,5,9- tetramethyl-octalyl group or the 5,5,9-trimethyl-2-methylene-decalyl group.
The above transformation may be represented in its general form as follows:
In the Formula VII, x denotes an eliminable radical such as a hydroxy-acyl group (e. g.. the group O.CO.CH3) or the hydroxy radical or a halogen atom,
3 and R indicates a functional radical such as alcohol, aldehyde, acid or ester. In the Formula VIII the unsaturatedness of the new compound results from the double bond between the carbon atom in the position 2 and one of its adjacent carbon atoms, and R indicates an alcohol or aldehyde radical.
If R of the Formula VII is an alcoholor aldehyderadical, it is not necessary to transform it in order to obtain the new compound according to the Formula VIII. If on the contrary R is an acidor ester-radical, it has to be transformed into an alcoholor aldehyde-radical; this transformation may take place before or after the elimination of the radical x; if it takes place before, the case is reestablished where R of the Formula VII is an alcoholor aldehyde-radical.
It has also been ascertained that when in the starting material the hydrocarbon radical in .the position 1 presents a hydroxyl group, the elimination of the eliminable radical (x) does not only provoke the formation of an unsaturated product such as the one of the Formula VIII, but likewise the formation of an epoxide (Formula X) by the formation of a third ring. This latter transformation is represented as follows:
CH3 CH3 st /CH3 CH3 CH3 When the eliminable radical x is a hydroxyl group, the above transformation is preponderant in respect of the one indicated by the Formulae VII and VIII, even in the case where R" is a chain of three carbon atoms. In fact, in the above Formula IX, the hydrocarbon radical comprising the hydroxyl group, represented by R"-OH may for example be one of the following groups:
(enolic forms of the corresponding aldehydes).
The same as the unsaturated alcohols or aldehydes indicated by the Formula VIII, the epoxides according to the Formula X are characterized by a very fine and pronounced ambergris scent. These epoxides are new substances and of evident interest for perfumery.
The present invention also relates to these new epoxides.
As a starting material for the preparation of the compounds of Formula VIII, one may advantageously use the acetylated hydroxy-aldehyde (Formula IV) or the acetoxyacid (Formula II) indicated above. These materials may preferably be obtained by the ozonolysis of the anhydride of 1 butylone 2 hydroxy 2,5,5,9-tetramethyl-decaline (Formula I) (Ruzicka, Seidel, Engel, Helvetica chimica acta 25, 621 (1942)), which yields conjointly the aldehyde of the Formula IV and the acid of the Formula II.
One may alternatively use as a-starting material the alcohol of the Formula III or an ester of the Formula VII in which R is an ester-radical. Such an ester can for example be obtained by the saponification of the acid of the Formula II alone or in admixture with the aldehyde of the Formula IV (in the latter case in thepresence of air) which yields the lactone of the 2-hydroxy-2,5,5,9- tetramethyl-decalyl acetic acid. This lactone is subsequently transformed into an ester by transesterification. The ester may alternatively be obtained by the transesterification of the acid of the Formula II. One may still use as a starting material the 'y-glycol of the Formula VII in which x=OH, and R=CH2OH.
As a starting material for the preparation of the epoxides of Formula X, one may advantageously utilize the glycol of the Formula XII:
The hydroxy-aldehyde of the Formula XI (enolic form) does not yield the epoxides of Formula X, but yields along with unsaturated aldehyde of Formula VIII other substances of undetermined composition and not of interest.
These substances may be prepared by the ozonolysis of the anhydride of the 1-butylone-2-hydroxy-2,5,5,9-tetramethyl-decaline (Formula I) followed by an appropriate treatment which yields inter alia a monoacetylated -glycol, to wit the 2-acetoxy-2,5,S,9-tetramethyl-decalyl-ethanol (Formula III) and an acetylated hydroxy-aldehyde: the 2-acetoxy2,5,5,9-tetramethyl-decalyl-ethanal (Formula IV). By the acetalisation of the last-mentioned compound and by subsequent saponification of the acetal obtained, a hydroxy-aldehyde of the Formula XI is obtained.
The elimination of the radical x (see Formulae VII and IX), whether the latter is a hydroxy-acyl group, a hydroxy radical or a halogen may be effected by distillation of the substance in question under a reduced pressure, and according to the case in the presence of a catalyst, such as powdered copper bronze, aluminium oxide, sebacic acid, fl-naphthalenesulphonic acid, alcoholic sulphuric acid, etc. The said elimination may be effected at the same time and in the same reaction medium as the transesterification of the lactone or of the ester as mentioned hereabove since the same reagent is used for each of these operations.
Since all the products resulting from the elimination of the radical x in the position 2 have an ambergris scent, whether they be unsaturated alcohols, unsaturated aldehydes, saturated or unsaturated epoxides, one may utilize them raw and in admixture with one another. In this manner a costly purification is dispensed with.
Some examples of the process according to the invention will be given:
Example 1 The neutral fraction of the products resulting from the ozonolysis of the sclareol oxide (Formula I), which contains accordingly the aldehyde of the Formula IV, is distilled in the presence of a little copper bronze or sebacic acid under 15 mm. vacuum. The distillate is refractionated under 15 mm. vacuum and the fractions which distil off above C. are submitted to a new treatment with copper until a practically complete elimination of the acetic acid is achieved. After separation of the acidic fraction, the new compound thus prepared, which is the aldehyde of Formula V, possesses an ambergris scent and has the following physical constants:
This compound yields a semicarbazone melting at 223225 C. 7
Instead of carrying out the deacylation separately on the neutral fraction and on the acidic fraction resulting from the ozonolysis, the said deacylation can also be carried out on the mixture of both said fractions and the neutral and respectively acidic fractions may afterwards be separated.
Example 2 The acid fraction of the products resulting from the ozonolysis of the sclareol oxide (Formula I), or the product resulting from the oxidation by means of permanganate of the neutral fraction of the said oxonolysis (this fraction or this product containing the acid ofthe Formula II), is heated in a weak vacuum at 160200 C. in the presence of copper bronze. After 40 minutes the elimination of the acetic acid is almost quantitative. The unsaturated acid thus obtained distils under 0.01 mm. at 135l45 C. This is reduced in ethereal solution by means of LiAlH4, and the unsaturated alcohol of ambergris scent (Formula VI) having Ebo.o1 mm. 116117 C. is directly obtained.
This alcohol yields a 3,5-dinitrobenzoate melting at 133-135" c.
Example 3 The same fraction or the same starting material as in Example 2 is heated during several days to boiling point with'methanol to which 5% by weight of concentrated sulphuric acid has been added. By this treatment the acid of Formula II is transesterified. The ester obtained is of the Formula VII in which x=OH'and and is dehydrated by heating at l-130 C. in the presence of a little iodine. The unsaturated ester resulting from this dehydration is reduced in ethereal solution by means of LiAlH4 to the alcohol of the Formula VI. If the methanol used hereabove contains more than 5% of sulphuric acid, a dehydration of 'the acid of the Formula II-is effected which yields directly the unsaturated ester; the treatment with iodine is then unnecessary.
Example 4 The acid fraction of the products resulting from the ozonolysis of the sclareol oxide (Formula I) which accordingly contains the acid of the Formula H, is saponified by means of alcoholic potash. The lactone which results from this saponification is then transesterified into a saturated ester of the Formula VII in which x=OH, and R is an ester radical. This ester is dehydrated into an unsaturated ester which is then reduced, as in the Example 3, to an alohol of the Formula VI.
Example 5 The lactone obtained by the saponification of the acid fraction of the ozonolysis of the sclareol oxide or of the product of the oxidation by means of permanganate of the neutral fraction of the ozonolysis, is reduced, in ethereal solution, by means of LlAlH4 or in alcoholic solution by means of sodium, to a saturated primarytertiary glycol of the Formula VII in which x=-OH and R=-CH2OH. By the distillation of this glycol in a good vacuum over aluminium oxide at a temperature in the negihbourhood of 200 C., it is transformed into the unsaturated alcohol of the Formula VI.
Example 6 The lactone mentioned at the beginning of the Example 5 is treated at 20 C. with ethanol saturated with dry gaseous hydrochloric acid. After the reaction-mixture is filtered, the filtrate is poured into water; the rest of the chlorinated ester formed (Formula VI in which x=Cl and R is an ester radical) is extracted by means of a solvent which is immiscible with water. Once this ester is crystallized (melting point 7879 C.), it is distilled in vacuo according to the process of the invention. A yield of 90% of unsaturated ester is obtained which is then reduced to the unsaturated alcohol (of Formula VI) by any known method, for example by means of LiAlHi.
Example 7 11.2 g. of glycol of the Formula XII are heated in the presence of 40 mg. of .9-naphthalene sulphonic acid at 135 C. in vacuo; the reaction mixture is then distilled, and the fraction boiling under 10 mm. Hg between 168 and 173 C. is recovered. By the treatment of this fraction with petrol ether, 8 g. of epoxide melting at 75-76 C.
of the Formula X are recovered in which R"=-CH2CH2- This epoxide possesses a good ambergris scent, particularly in solution and after a certain time of exposure to the an.
Example 8 Example 9 12.7 g. of sclareol oxide C1sHsoO (Helv. chim. acta 25, 625 (1942)) dissolved in 250 cc. of hexane (pure and dry) are subjected to ozonolysis at 30. After saturation, the ozonide is reduced by adding to it in small batches 310 g. of a filtered ethereal solution titrating 2.5% of LiAlH4. Finally one heats up to boil. After the usual treatment, one obtains of a glycol of the Formula XII and a small quantity of epoxideof the Formula X (R-=-CHzCH2-) which are separated by treatment with petrol ether. In order to increase the yield in epoxide, the raw reduction product may be treated according to Examples 7 or 8.
Example 10 The acetoxy-aldehyde of the Formula IX in which x OOCCI-I3 and R '=-CH=CH' originating from the ozonolysis of the sclareol oxide (see Example 9) is saponified in an absolutely oxygen-free medium. In order not to have to avoid the oxygen, one may transform the aldehyde into acetal or into Schifis base by a known method, and saponify it subsequently. These two methods lead finally to the hydroxy-aldehyde of the Formula XI. By distillation or by simple heating in vacuo at or C., the hydroxy-aldehyde in its enol form is transformed by the elimination of water into unsaturated epoxide of the Formula X in which R=-CH=CH At the same time the unsaturated aldehyde of Formula VIII (in which R'=CHO) is formed, which is an isomer of the epoxide. The mixture obtained has the following characteristics: Ebo.o05 mm. 100-110 C.; C16H260; calculated C 82.1%, H 11.1%; found C 82.3%, H 11.4%. By means of alkaline oximation 28% of unsaturated aldehyde is determined and by means of acid oximation 65% of epoxide. The oil possesses a very good ambergris scent.
Example 11 1.9 g. of glycol prepared by reduction of the ambrenolid of the Formula IX, in which x=OH and R=CH2CH2CH2, is dissolved in 80 cc. of methanol containing 7.2 cc. of concentrated sulphuric acid, and the whole is heated under reflux for 3 days. After the habitual treatment 1.75 g. of neutral parts are obtained. When recrystallized in alcohol or petrol ether, the epoxide thus obtained melts at 83 C., yield 70%.
Example 12 The glycol of the Formula IX, in which x=OH and R"=CH2CH2 is treated in the cold by a coldsaturated solution of hydrochloric acid in absolute ether. After some days a mixture is formed of the epoxide of the Formula X, in which R=-CHzCH2-, of the chlorinated alcohol of the Formula IX in which x=-Cl .7 and R"=CHz ?CH2 of the unsaturated alcohol of Formula VI and of its chloride. The proportions of these four products vary according to the reaction period, the temperature, the concentration and the excess of the hydrochloric acid. By simple heating to 100 in vacuo, the chlorinated alcohol of Formula IX is transformed into the unsaturated alcohol of Formula VI and into the epoxide of the Formula X. The latter is a stereoisorner of the one described in the Examples 1 and 2. and melts at 6062 C. All these products have an ambergris scent and can be utilized pure or in admixture with one another. By distillation followed by saponification with caustic potash this mixture can be transformed into a strongly scented mixture of the epoxide and of the unsaturated alcohol. These two substances can be ery easily separated. by c r ma o rap 11 lum n um. id
T he invention wm r ses e se the u i izat n o he new compound having anarnbergris scent as a perfume or as a primary material 'in perfumery. When used in such a mapper, this perfume or this material contains at least one compound presenting the 2,5,5,9-tetramethyhoctalyl grcup, the carbon atom in the position 2 of which participates either in a double bond or in an epoxide.
The perfume or the primary material comprising these two compounds can very easily be obtained by carrying out the process of the present invention during which both transformations indicated on the one hand by the Formulae VII and VIII, and on the other hand by the Formulae IX and X are jointly executed. The composition of a perfume containing inter alia these two compounds will now be' given by way of example:
Parts by weight Unsaturated alcohols comprising 16 carbon atoms and presenting the 2,5,5,9-tetramethyl-octalyl group Saturated epoxide comprising 16 carbon atoms and presenting the 2,5 ,5,9-tetramethyl-decalyl group 5 Amyrine, a and B 80 Dihydro ionone 'y 5 V octalyl- 1- ethanol,
What I claim is;
1. A compound having an ambergris scent and selected from the group consisting of A -2,5 5.9-tetramethyl- A 2,5,5 ,9- tetramethyloctalyl- 1- ethanol. A -2,5,5,94etramethyl-octalyl-l-ethanal and N -2,5,5,9-tetramethyl-octalyl-1-ethanal, and mixtures thereof.
2. The la -2,5,.5,9-tetramethyl-octalyl-1-ethanol having an ambergris scent, boiling at 116-117 C. under 0.01 Hg pressure and yielding a 3,5-dinitrobenzoate melting at 133-135" C.
3. The A -2,5,5,9-tetramethyl-octalyl-1-ethanol having an ambergris scent, boiling at 116-1 17 C. under 0.01 mm. Hg pressure and yielding 3,5-dinitrobenzoate melting at 133135 C.
4. The A -2,5,5,9-tetramethyl1octalyl-1:ethanal having an ambergris scent, presenting the following physical constants: EbD.01mrn.Hg 1007.105" C. d =0.993-.0.995; I1-D2:1.512:1.51.4 and yielding a semicarbazone melting at 223225 C.
5. The A -2,5,5,9-tetramethyl-octalyl-l-ethanal having an ambergris scent, presenting the following physical constants: Ebom mm. Hg 100-105 C.; d =0.9930.995; n 3=1.5l2l.514 and yielding a semicarbazone melting at 223-225 C.
References Cited in the file of this patent Ruzicka: Helv. Chim. Acta 21,364-70 (1938).

Claims (1)

1. A COMPOUND HAVING AN AMBERGRIS SCENT AND SELECTED FROM THE GROUP CONSISTING OF $(1,2)-2,5,5,9-TETRAMETHYLOCTALYL-1- ETHANOL, $(2,3)- 2,5,5,9- TETRAMETHYL- OCTALYL- 1ETHANOL, $(1,2)-2,5,5,9-TETRAMETHYL-OCTALYL-1-ETHANAL AND $(2,3)-2,5,5,9-TETRAMETHYL-OCTALYL-1ETHANAL, AND MIXTURES THEREOF.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2914565A (en) * 1954-07-16 1959-11-24 Dragoco Gerberding Co Gmbh Products having ambergris aroma and a process of making same
US3029255A (en) * 1950-10-24 1962-04-10 Firmenick & Co Compounds having an ambergris scent and their preparation process
US3050532A (en) * 1959-06-19 1962-08-21 Reynolds Tobacco Co R Two stage oxidation of sclareol
US3072709A (en) * 1957-05-21 1963-01-08 Hoffmann La Roche Octahydronaphthaleneones, alcohols and their acyl derivatives
US3096346A (en) * 1961-09-11 1963-07-02 Reynolds Tobacco Co R Oxidation of manoyl oxide
US3927083A (en) * 1972-06-15 1975-12-16 Int Flavors & Fragrances Inc Bicyclic compounds and processes for making and using same
US5292902A (en) * 1991-08-02 1994-03-08 Givaudan-Roure Corporation Process for the manufacture of odorants and intermediates used therein
US5883074A (en) * 1995-02-08 1999-03-16 Microcide Pharmaceuticals, Inc. Potentiators of antibacterial agents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029255A (en) * 1950-10-24 1962-04-10 Firmenick & Co Compounds having an ambergris scent and their preparation process
US2914565A (en) * 1954-07-16 1959-11-24 Dragoco Gerberding Co Gmbh Products having ambergris aroma and a process of making same
US3072709A (en) * 1957-05-21 1963-01-08 Hoffmann La Roche Octahydronaphthaleneones, alcohols and their acyl derivatives
US3050532A (en) * 1959-06-19 1962-08-21 Reynolds Tobacco Co R Two stage oxidation of sclareol
US3096346A (en) * 1961-09-11 1963-07-02 Reynolds Tobacco Co R Oxidation of manoyl oxide
US3927083A (en) * 1972-06-15 1975-12-16 Int Flavors & Fragrances Inc Bicyclic compounds and processes for making and using same
US5292902A (en) * 1991-08-02 1994-03-08 Givaudan-Roure Corporation Process for the manufacture of odorants and intermediates used therein
US5883074A (en) * 1995-02-08 1999-03-16 Microcide Pharmaceuticals, Inc. Potentiators of antibacterial agents

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