DE1287242B - Fragrances - Google Patents

Description

The present invention relates to fragrances with a musky odor.

There are already various classes of compounds in the literature Described musk odor, for example macrocyclic lactones and ketones, aromatic Nitro compounds, acylated indanes, acylated tetralins, aromatic ketones and Aldehydes.-The present invention provides a new class of musk fragrances, which have a pure and strong musk odor, excellent durability, have high stability and no tendency to discolour under the conditions which are the compounds with a musky odor or the fragrances of which they are a part represent, come to use, for example as perfumes, creams, cosmetic Liquids, such as beauty tonic, powders, soaps, detergents, and aerosols.

The new compounds with a musk odor which are contained in the fragrances according to the invention are tricyclic isochromanes of the general formula I. in which R1 and R2 are either methyl or hydrogen, the radicals R3 and R4 are either both hydrogen or one is hydrogen and the other is a methyl group and A is a methylene group (- CH2 -), an ethylene group (H2CH2-), an ethylidene group (CH3 -HC <), a 1,2-propylene group (-CHCH3-CH2-) or a 2,3-butylene group (-CHCH3-CHCH3-).

In the preparation of the compounds of the above formula 1, angled tricyclic isomers of the formula II are used in smaller amounts educated.

The tricyclic isochromanes of the in The structure described in the present invention are in addition to that previously mentioned The fact that a new class of musk fragrances is available to the interested party is also valuable because it is compared to the well-known nitro muskets greater stability and have color fastness and are much more soluble than these, its durability is greater than that of macrocyclic musk, such as the oxalactones hexa- and pentadecanolide, and that they are cheaper to manufacture than, for example, cyclopentadecanone, cyclohexadecanone, muscone and the macrocyclic ones Lactones. The tricyclic isochromans used in the present invention are durable also superior to musk fragrances based on the indane structure.

Some of the strongest musky odor compounds of these Series are 2-oxa-4,5,5 ,.

8.8 - pentamethyl - 1,2,3,4,5,6,7,8-octahydroanthracene (formula IV), 6-oxa- 1,1,2,3,3,8 -hexamethyl-2,3, 5,6, 7,8-hexahydro-1 H -benz [fjinden (Formula V) and 6-Oxa-I, 1,1,1,3,3-PENTAMETHYL-2,3,5,6,7,8 -hexahydro-1H-benz [f] indene (formula VI), but isochromanes of the formulas VII to XV are also musk fragrances.

The compounds of the formula XVI which no longer fall under the general formula of the tricyclic isochromanes used according to the invention have only a very weak musk odor, probably due to the reduced accessibility of the functional group.

The compounds of formula 1 can be used in several ways are obtained, with compounds of the general formula II and III usually are obtained as by-products. The tricyclic used according to the invention Isochromanes can be obtained: 1. By cycloalkylation of isochromans of the Formula XVI II with suitable dihalides of the formula XIX, in which A, R1, R2, R3 and R4 have the above meanings, as indicated by the formulas given below, mata reproduced, under the influence of a suitable alkylation catalyst, z. B. after H. A. Brus 0 n et al, J. Amer.

Chem. Soc., 62, p. 36 (1940).

Instead of the dihalides of the formula XIX, the corresponding Diols, 1,3-, 1,4- or 1,5-dienes can be used. The isochromanes are easy too by reacting the corresponding phenylethyl alcohol homologues with formaldehyde, for example according to the method described by P. M aitte in Ann. Chim.

(12), 9, p. 431 (1954), and A.Rieche and E. 5 c h m i t z in Chem. Ber., 89, 5. 1254 (1956), specified procedure accessible.

2. By reacting polymethyltetralines and polymethylindanes with epoxies and subsequent condensation of the alcohols formed with formaldehyde, the desired tricyclic isochromanes being obtained in moderate to good yields will.

An example of this is: The required polymethyltetralins and polymethylindanes -of the formula XX can be obtained by many procedures given in the literature, e.g. B. by 1,2-cyclialkylation of aromatic hydrocarbons according to HABruson et al, loc. Cit., By condensation of styrene and homologues with alkenes or tertiary alcohols, eg. B. according to DB Sp o els tra et al, Rec., 82, p. 1100 (1963), or according to Swiss patent 353 003, and by cyclodehydration of suitable tertiary alcohols. z. B. accordingly Related compounds which, however, have no musky odor are: 1. The corresponding practically odorless chroman derivatives, such as, for example, XXII (melting point: 74.0 to 74.7 ° C.).

The compound with structure XXIII (melting point: 77.9 to 78.7 ° C) is also odorless.

2. homologues with fewer methyl groups in the alicyclic ring; the compound with structure XXIV (m.p. = 88.6 to 89.9 ° C) is odorless.

Preparation of the tricyclic isochromanes used according to the invention A. 2-Oxa-5,5,8 8-tetramethyl-1, 2,3,4,5,6,7,8-octahydroanthracene (VIII) A suspension of 1000 g of aluminum chloride in 21 of dry CCI, was cooled to -100C.

A solution became a solution over the course of one and a half hours with vigorous stirring of 402 g of isochroman and 549 g of 2,5-dichloro-2,5-dimethylhexane in 1250 ml of dry CCI, admitted.

During the addition, the temperature was kept at -5 to -10 ° C an ice-salt bath while a vigorous stream of nitrogen flows through it the reaction mixture was blown. After further stirring for half a The reaction product was poured onto a mixture of 5 kg of ice and 600 hours at 0 ° C. ml of concentrated HCl poured.

The oil layer was separated and with it for 2 1/2 hours at 50 ° C 600 ml of a 50% alcoholic KOH solution was stirred. The solution was then in 6 l of water was poured, and the Ulschicht was separated. The solvent was distilled off, and the crude product, 720g, was at 3 mm Hg under a nitrogen atmosphere distilled to separate the residue yielding the following fractions: I. b.p. = 60 to 123 ° C ... .... 180g II. B.p. = 130 to 170 ° C .... . 356 g III. Kp. = 170 to 180 ° C. ....... 17 g and a residue ..... .......... # 166 g The raw Musk fragrance from fractions II and III was made by crystallization purified an equal volume of ethanol to give 260.5 g of one apparently pure product of white crystals with a strong musky odor; F. = 65.5 to 66.2 ° C, i.e. 35.6% of theory, with recrystallization of 10 g of this material from 10 ml of ethanol were obtained 8.5 g with a mp of 65.5 to 66.3 ° C.

Column chromatography of the product on A1203 with benzene as the eluent and gas chromatography on a 1.20 m glass column, which is equipped with 30010 Reoplex-400 was packed on Embacel at 155 ° C indicated the product was pure. The gas chromatography results are in Fig. 1 shown. This was confirmed by the CH analysis.

C17H24O: Calculated ... C 83.55, H 9.00; found ... C 83.57, H 9.94, 83.61, 9.87.

The linear structure was determined by mass spectrometry, N.M.R. and I.R., confirmed.

The I.R spectrum in KBr is shown in FIG. 3 shown.

B. 2-Oxa4, 5,5,8,8-penthamethyl-1,2,3,4,5, 6,7,8-octahydroanthracene (W) 4-Methylisochroman was prepared from hydratropin alcohol and formaldehyde according to the method of R i e c h e and S c h m i t z; Chem. Ber., 89, p. 1254 (1956), stated procedure in a yield of 88% as a colorless liquid with a boiling point of 70 ° C at 3 mm Hg, n4 @@ = 1.5361, d200 = 1.0411, synthesized.

The cycloalkylation of 4-methylisochroman was carried out according to the Procedure A with 444 g (3.0 mol) of 4-methylisochroman, 549 g (3.0 mol) of 2,5-dicloro-2,5-dimethylhexane, 1000 g (7.5 mol) AlCl3 carried out in dry CCl4 at a temperature of -5 to -10 ° C. After distilling off the solvent, the crude product, 650 g. at 3 mm Hg distilled under nitrogen, whereby 466 g of distillate with a boiling point = 130 to 200 ° C and 173 g of residue were obtained. When fractionating the distillate by a Vigreux column with eight theoretical plates at 0.1 mm Hg under nitrogen were made 276 g. i.e. 35.7% of theory, of 2-oxa-4,5,5,8,8-pentamethyl-1,2,3,4,5,6,7,8-octahydroanthracene as a viscous liquid, bp = 126 to 128 ° C at 0.1 mm Hg and n200 1.5378 to 1.5380, obtained, which slowly crystallized on standing. The recrystallization from Ethanol gave the pure compound, white crystals with very strong and persistent Musk odor; M.p. = 44.7 to 45.4 ° C.

CH Analysis (CisH26O): Calculated. C 83.66, H 10.14; found ... C 83.63, H 10.21, 83.74, 10.16.

The structure was determined by mass spectrometry, N.M.R. and I.R., confirmed. The I.R. spectrum is shown in FIG. 4 shown. The N.M.R. spectrum is shown in FIG. 5 given.

C. 2-Oxa-4,4,5,5,8,8-hexamethyl-1,2,3,4,5,6,7,8-octahydroanthracene (XIII) 4,4-Dimethylisochroman was made from 2-methyl-2-phenylpropanol by cyclization produced with formaldehyde under the influence of HCl in a yield of 79010. It is a colorless liquid with a musty, camphor-like odor, bp. = 74 ° C at 3 mm Hg, n200 1.5278, d-- 1.0191.

The cycloalkylation of 4,4-dimethylisochroman was, as in the Production method A described, carried out using a suspension of 333 g (2.5 mol) of aluminum chloride in 800 ml of dry CCl4 and a solution of 162 g (1 mol) 4,4-dimethylisochroman and 183 g (1 mol) 2,5-dichloro-2,5-dimethylhexane in 600 ml of dry CCl4 was assumed.

After a rapid distillation, 239 g of distillate with a bp. from 150 to 185 ° C at 5 mm Hg which partially crystallized on standing.

Recrystallization from twice the volume of ethanol gave the pure compound, m.p. = 71.8-72.7 ° C; the product consisted of white crystals with a moderately strong musk odor.

CH Analysis (C1 9H28O): Calculated ... C 83.77, H 10.36; found ... C 83.85, H 10.33, 83.89, 10.35.

Gas chromatography on Reoplex-400 at 174 ° C showed the presence of two very low levels of impurities, about 0.11% each. The gas chromatogram is in Fig. 2 shown.

D. 6-Oxa-1,1,3,3-tetramethyl-2,3,5,6,7,8-hexahydro-1 H -benz [f] indene (IX) a) Tetramethylindane was obtained by the Grignard reaction of 2-methyl-2-phenylpentanone-4 with me- methyl magnesium bromide and subsequent cyclization of the alcohol obtained made with concentrated sulfuric acid.

The hydrocarbon obtained in an overall yield of 86.80% in the form of a colorless liquid had a b.p. of 65 ° C at 5 mm Hg, n200 1.5022, d420 = 0.8982, m.p. = 19 to 20 ° C. b) A suspension of 17.8 g (1.33 mol) of aluminum chloride in 870g (5 mol) of 1,1,3,3-tetramethylindane and 265 ml of petroleum ether, b.p. = 65 bis 68 ° C, was cooled to 0 ° C, and this temperature was increased over the course of hours a solution of 66 g (1.5 mol) of ethylene oxide in 472 g (2.7 mol) of 1,1,3,3-tetramecthylindane and 137 ml of petroleum ether, b.p. = 65 to 68 ° C., were added. The reaction mixture was stirred for a further hour at 5 to 10 ° C and then on a mixture poured from 1000 g of ice and 200 ml of concentrated HCl.

The DI layer was separated and the water layer was salted saturated and extracted twice with 250 ml of benzene. The oil layer and the benzene extract were combined, the solvents were distilled off, and the residue, 1338 g, became distilled under a nitrogen atmosphere, 1. 927 g of distillate, b.p. = 50 up to 85 ° C at 14 mm Hg, 2,375 g distillate, b.p. = 88 to 1700C at 3 mm Hg, and 21 g of residue were obtained.

When fractionating the second fraction of the distillate were 267.5 g of recovered tetramethylindane and 111.0 g of almost pure 5-hydroxyethyl-1,1,3,3-tetramethylindane, Bp = 135 to 136 ° C obtained at 3 mm Hg. Crystallization from ethanol gave the pure alcohol, m.p. = 47.9 to 48.8 ° C CH analysis (C15H22O): Calculated ... C 82.51, H 10.16; Found ... C 82.69, H 10.17, 82.66, 10.24. c) 65 g (0.3 mol) of 5-hydroxyethyl-1,1,3,3-tetramethylindane was converted into the corresponding isochroman by reaction with 0.4 mol of paraformaldehyde and hydrochloric acid according to that of A. R i e c h e and R. S c h m i t z: a. a. O. stated Working method transferred. The crude product was distilled in a nitrogen atmosphere and resulted in 61 g of distillate, b.p. = 137 to 1900 ° C. at 3 mm Hg and 6 g of residue. That Distillate slowly crystallized on standing and was recrystallized from ethanol, 55 g of pure 6-oxa-1,1,3,3-tetramethyl-2,3,5,6,7,8-hexahydro-1H-benz [f] indene in the form of white crystals, m.p. 66.2 to 66.7 ° C, with a fine musky odor were obtained.

CH Analysis (C16H22O): Calculated ... C 83.43, H 9.63; found ... C 83.55, H 9,60, 83.55, 9.58.

The structure was determined by mass spectrometry, N.M.R. and 1.R., confirmed. Gas chromatography showed the product to be pure. The I.R. spectrum is in F i g. 6 shown.

E. SOxa-1, 3,3,8-pentamethyl-2,3,5,6,7,8-hexahydro-1H-benz; nd 9VII) The cycloalkylation of 4-methylisochroman with 2,4-dichloro-2,4-dimethylpentane was carried out according to procedure A, 148 g (1 mol) of 4-methyl-isochroman, 169 g (1 mol) 2,4-dichloro-2,4-dimethylpentane and 333 g (2.5 mol) AlCl3 in dry CCl4 were used at a temperature of -5 to -10 ° C.

The crude product, 235 g, was distilled at 6 mm under nitrogen, 194 g of distillate with a boiling point of 60 to 210 ° C. and 37 g of residue being obtained became.

When fractionating the distillate through a Vigreux column of seventeen theoretical plates at 0.15 mm under nitrogen, the desired product was in Form of a colorless, viscous liquid, bp = 88 ° at 0.15 mm and nD20 = 1.5272, which slowly crystallized on standing.

After recrystallization from ethanol, it was found by gas chromatography pure connection in the form of white crystals with very strong and lasting tandem Musk odor, m.p. = 57.7 to 58, 3DC.

CH Analysis (C17H24O): Calculated ... C 83.55, H 9.90; found... C83.61, H9, X, 83, 71, 9, 82.

The structure was determined by mass spectrometry, N.M.R. and I.R., 13confirmed. The LR spelled strand is shown in FIG. 7, the N.M.R. spectrum in F i g 8.

F. 6-Oxa-1,1,2,3,3-pentamethyl-2,3,5,6,7,8-hexahydro-1H-benz [f] indene (VI) a) 2- (1 ', 1', 2 ', 3', 3'-Pentamethylindanyl-5 ') - ethanol While stirring well to a mixture of 1504 g (8 moles) of 1,1,2,3,3-pentamethylindam and 1066 g s Moles) of aluminum chloride held at -10 to -5 ° C for a period of time of 9 hours a solution of 352 g (8 mol) of ethyl chloride dissolved in 13 536 g (72 Mol), 1,1,2,3,3-pentamethylindane were added. The ethylene oxide hydrocarbon solution became below the surface of the aluminum chloride-hydrocarbon slurry added. Upon completion of the E; The reaction mass was given at B ° C during stirred for a further 21/2 hours. The reaction mixture was then poured into 21 ice water poured and the oil which separated became more saturated with equal volumes of (a) sodium chloride solution, (b) 5% sodium hydroxide solution and (c) saturated sodium chloride solution washed. The unreacted pentametllylindane, 13 g, g, was removed by vacuum distillation removed until a distillation pot temperature of 1ZDC at 3 mm was reached.

The residual oil, tlMg, was carefully fractionated, and 910 g of one constant boiling viscous liquid, b.p. = 121 ° C at 0.7 mm, was obtained nD20 = 1.5279, d @@@ = 1.0388. The structure of this compound became the NM. N.M.R. spectrum, that in Fig. 13 is confirmed. b) 6-oxal-1,1,2,3,3-pentamethyl-2,3,5,6,7,8-hexahydro-1H-benz [f] indene 630 g of dry hydrogen chloride gas became a slurry with good stirring vDn 910 g Alcohol, which was obtained according to a), and 127 g of paraformaldehyde held at 16 ° C.

The gas was introduced below the surface of the liquid. Upon completion of the HCl addition, the reaction mass became completely liquid, which is an indication of the completion of the reaction. The structure of chloromethyl ether was confirmed by the N.M.R. spectrum. 900 g of the crude chloromethyl ether were heated at 120 ° C for 2 hours. The reaction mass was then in the appropriate Way, as described in the procedure G, worked up.

Distillation of the egg (825 g) gave a clear viscous liquid, Bp = 148 to 150 ° C at 1 mm with a strong musk odor, nD20 = 1.5390, d420 = 0.9882. The I.R. spectrum is shown in FIG. 14 and the N.M.R. spectrum in F i g. 15. The oil crystallized on standing and can be recrystallized from ethanol will. M.p. = 53.4 to 54.3 ° C.

G. GOxa-1, 1,2,3,3,8-hexamethyl-2,3,5,6,7,8-hexahydro-1H-benz [f] indene (V) a) 1,1,2,3,3-Pentamethylindane Crude 3,4-dimethyl-4-chloropentanone-2 was made according to that of J. C o l o n g e; Bull., 5, p. 339 (1939) a Kondakov acetylation of trimethylethylene with acetyl chloride in the presence of Synthesized SnCl4.

A suspension of 106.8 g (0.8 mol) of aluminum chloride in 312 g of dry Benzene was cooled to 10 ° C and was stirred under vigorous over the course of an hour Stir a solution of 165 g (1.1 MoL0 3,4-dimethyl-4-chloropentanone-2 in 78 g dry Benzene was added, maintaining a temperature at 10 ° C by cooling in an ice bath became. The mixture was stirred for an additional 2 hours, the temperature increasing to 20 ° C rise.

The reaction mixture was based on a mixture of 1 kg Bis and 80 ml of concentrated HCl poured.

The oil layer was separated and washed with a like Volume of 5% HCl, 10% NaOH and water processed further. The solvent was distilled off. When the crude product was distilled, 1133 g of distillate, b.p. = 60 obtained up to 150 ° C at 3 mm and 40 g of residue.

Fractionation of the distillate through an 8 tray Vigreux column gave 2,3-Dimethyl-2-phenylpentanone-4-with a b.p. = 95 ° C at 3 mm, nD20 = 1.5120.

The structure was confirmed by I.R. and N.M.R.

To a solution of 0.2 moles of methylmagnesium bromide in ether was in the course of one hour at a temperature of 5 to 10 ° C 38 g (0.2 mol) 2,3-Dimethyl-2-phenylpentanone-4 was added. The mixture was for a further 3 Stirred for hours, the temperature being allowed to rise to 20 ° C. The reaction mixture was decomposed with dilute sulfuric acid and according to the standard procedure worked up.

A rapid distillation of the crude product gave 37 g of distillate from Bp. 110 to 115 ° C with 3 mm and 2 g residue.

That essentially consists of pure 2-phenyl-2,3,4-trimethylpentanol-4 Existing distillate was converted into 50 ml of 85% strength by adding over the course of lj2 hours Sulfuric acid cyclized. The mixture was during another 11/2 Stirred for hours, the temperature being kept at 10 ° C.

The reaction mixture was with a mixture of 50 ml of benzene and 50 ml of ice-cold water diluted. The Cllschicht was separated and with 5% igen NaHCO3 and water washed. The solvent was distilled off and the crude product was separated from the residue by distillation, yielding 28 g of a distillate with a boiling point of 78 to 100 ° C. at 3 mm Hg and 6 g of residue. Fractionation of the distillate through a 14 tray Vigreux column gave 1,1,23,3-pentamethylindane as a colorless liquid with bp = 73 ° C at 3 mm, n20 = 1.5114, d420 = 0.9169. b) 2- (1 ', 1 ', 2', 2 ', 3'-Pentamethylindanyl-5') -propanol-1 To a mixture of 1504 g (8 mol) of 1,1,2,3,3-pentamethylindane and 1066 g (8 mol) of anhydrous aluminum chloride powder, which was held at -10 to -5 ° C, with good stirring for a period of time of 9 hours a solution of 465 g (8 mol) of propylene oxide in 13 535 g (72 mol) of 1,1,2,3,3-pentamethylindane added. The propylene oxide hydrocarbon solution became below the surface of the aluminum chloride-hydrocarbon slurry admitted. Upon completion of the addition, the reaction mass immediately became one equal volume of ice water was added with thorough stirring.

The organic top layer was separated with 1/3 volume sodium hydroxide solution (5%) and then three times with equal volumes of saturated sodium chloride solution washed. The unreacted pentamethylindane, 13,290 g, was removed by vacuum distillation removed until a distillation temperature of 98 ° C / 3 mm Hg was reached in the vessel; the residual oil, 1338 g, was distilled to leave 1162 g of a viscous Uls obtained, which crystallized on standing, bp = 120 to 123 ° C at 0.2 mm, M.p. = 53 to 53.5 ° C. The compound was identified by its N.M.R. spectrum, which in Fig. 10 is shown. c) 6-oxa-1,1,2,3,3, -8-hexamethyl-2,3,5,6,7,8-hexahydro- 1 H-benz [f] inden To 3656 g of the alcohol obtained under b), which is above his When the melting point was heated, HCl gas became saturated in sufficient quantity added to the solution. When saturated, the mixture was cooled with stirring 25 ° C, and about 500 g of dry hydrogen chloride were introduced into the reaction mass and at the same time 512 g of paraformaldehyde were added, these additions in total took place over 6 hours.

In this way the chloromethyl ether of alcohol was formed, as can be seen from its N.M.R. spectrum. This can be used for without cleaning the next stage to apply. The crude chloromethyl ether, about 4200g, was heated at 1200C for 2 hours. The reaction mass was cooled to 80 ° C, and an equal volume of 10% aqueous sodium hydroxide was added. The mixture was stirred at 80 ° C. for 2 hours. When cooled, the mass became Poured into water, washed neutral and distilled the Ul; 3806 g of a viscous Materials, Kp.

129 "C at 0.8 mm, were collected.

The product obtained had a strong musky odor, n200 1.5342; d420 = 1.0054.

The I.R. spectrum is shown in FIG. 11 and the N.M.R. spectrum in Fig. 12th

It can also be a mixture of 2-oxa-5,5,6, (7), 8,8-pentamethyl -1,2,3,4,5,6,7,8 - octahydroanthracene (X) and 2-oxa-5,5,6,7,8,8-hexamethyl-1,2,3,4,5,6,7,8-octahydroanthracene (XV) with a bp = 138 ° C / 0.3 mm Hg used in the fragrances according to the invention will. Likewise, 6-oxa-1,1,3,3,8,8-hexamethyl-2,3,5,6,7,8-hexahydro-1 H-benz [f] indene (XIV) with a m.p. = 99.6 to 100.4 ° C, the N.M.R. spectrum in FIG. 9 shown is useful.

The following examples are intended to further illustrate the present invention: Example 1 Incorporation of Compound VIII into a Perfume Composition 2-oxa-5,5,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydroanthracene 10 coumarin. 2 lavender oil. 18 citronellyl acetate. . 3 rosewood oil (bois de rose Oil) .. .. to 7 a-amylcinnamaldehyde .. 15 phenylethyl alcohol .. 12 benzyl acetate .. ............ 13 Terpineol .. 15 Cinnamon alcohol .. .. 5 100 Example 2 Incorporation of the Compound IV in a soap perfume 2-oxa-4,5,5,8,8-pentamethyl-1,2,3,4,5,6,7,8-octahydroanthracene . . 9 cinnamyl acetate. . 1 phenylethyl acetate .. ............. 1.5 benzyl acetate . .. 11 rosewood oil. 15 amyl salicylate ........................ 7 phenylethyl alcohol ........................ 12.5 terpineol ........ .............. ... 7.5 cinnamon alcohol . ........... 3 guaiyl acetate ................... ................. 2 cedarwood oil 8 Geraniol ................. 10 Eugenol ............................. ... 2.5 lavender .......... ..................... 10 100

Claims (5)

Example 3 Incorporation of the compound V into a perfume 6-oxa-1,1,2,3,3,8-hexamethyl-1,2,3,5, 6,7,8-hexahydro-1H-benzffjinden .. 2 , 5 coumarin. 3.0 bergamot oil .... .. 4.0 Geraniol .... ......... .. 15.0 Citronellol ........... .. 15.0 Phenylethyl alcohol ...: .. 12.0 Geranium oil Bourbon. 3.0 patchouli oil .... 1.0 Styrax .... 2.0 benzoin. 2.0 oak moss ... 1.0 terpineol. 3.0 amylcinnamaldehyde .. 8.0 benzyl acetate ................ 10.0 methyl ionone 1000/0. 6.5 East Indian sandalwood oil ... 2.0 Amyl salicylate .. .. 5.0 Lavandin oil ... .... 5.0 100.0 Claims: 1. Fragrances, characterized by a content of one or more tricyclic isochromanes of the general structure in which R1 and R2 are either methyl or hydrogen, the radicals R3 and R4 are either both hydrogen or one is hydrogen and the other is a methyl group and A is a methylene group (- CH2 -), an ethylene group (- CH2CH2 -), an ethylidene group ( CH3-HC <), a 1,2-propylene group (-CH3CH3-CH2-) or a 2,3-butylene group (-CHCH3-CHCH3-). 2. Fragrances according to Claim 1, characterized by a content of a compound of the formula 3. Fragrances according to Claim 1, characterized by a content of a compound of the formula 4. Fragrances according to Claim 1, characterized by a content of a compound of the formula 5. Fragrances according to Claim 1, characterized by a content of a compound of the formula Considered publications: German Auslegeschriften Nos. 1015798, 1019300, 1035826, 1037622.