Patent Document

THE INVENTION 
     This invention is concerned with novel compounds of the formula ##STR1## wherein: R 1  is chosen from the group consisting of alkyl radicals having one to four carbon atoms and alkenyl radicals having two to four carbon atoms, and 
     R 2  is chosen from the group consisting of hydrogen, alkyl radicals having one to three carbon atoms, alkenyl radicals having two to three carbon atoms, methoxy and ethoxy. 
     The invention is also concerned with fragrance compositions containing these novel compounds of formula I and a process for the manufacture of the compounds. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The alkyl and alkenyl radicals represented by R 1  and R 2  can be normal straight-chain radicals or branched radicals. Typical examples of such radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, vinyl, allyl, propenyl, methallyl, and the like. It should also be understood that formula I is intended to embrace all geometric isomers which are possible. 
     The compounds I have particularly valuable organoleptic properties and are especially useful as odorant substances. This invention is, therefore, also concerned with the use of the compounds as odorant substances. 
     Among the especially preferred compounds are ethyl 6-acetoxyhexanoate, ethyl 6-isobutyryloxy-hexanoate and allyl 6-propionyloxy-hexanoate. Also preferred are methyl 6-formyloxy-hexanoate, allyl 6-formyloxy-hexanoate, isobutyl 6-formyloxy-hexanoate, allyl 6-acetoxy-hexanoate, isobutyl 6-acetoxy-hexanoate and ethyl 6-ethoxycarbonyloxy-hexanoate. 
     The invention is also concerned with a process for the manufacture of the compounds I. Said process comprising the esterification of a compound of the formula 
     
         HO--(CH.sub.2).sub.5 --COOR.sub.1                          (II) 
    
     wherein R 1  has the above significance. 
     The esterification of the alcohols II is carried out by using the usual acylating agents, e.g. acyl halides or acid anhydrides. The procedure using the acid anhydrides is preferred. The procedure using the acid anhydrides is preferably carried out in the presence of phosphoric acid. The reaction using acyl halides is preferably carried out in the presence of tertiary amines such as pyridine or N,N-dimethylaniline. 
     The carbonate esters I (R 2  =methoxy or ethoxy) are manufactured in a manner similar to methods known in the art by reacting the alcohols II with chloroformic acid esters in the presence of tertiary amines such as pyridine or N,N-dimethylaniline. 
     The esters I are conveniently purified by distillation under reduced pressure. They are colorless to slightly yellow colored liquids. They are insoluble in water, but soluble in organic solvents such as e.g. alcohols, ethers, ketones, esters, hydrocarbons and halogenated hydrocarbons. 
     As mentioned above, the compounds of general formula I have particularly valuable organoleptic properties and are distinquished, in particular, by a combination of fruity notes and pronounced tenacity. They also can be used to intensify woody musk notes of odorant substance compositions without, at the same time, interfering with their individual odor. 
     Of particular interest are the raspberry notes, which are particularly pronounced in ethyl 6-acetoxy-hexanoate and ethyl 6-isobutyryloxy-hexanoate. While a number of substances having a raspberry odor are already known, e.g. piperonylacetone or p-hydroxybenzylacetone, these are, without exception, compounds which are many times more expensive to produce based on structural considerations. 
     It is a surprising and unexpected finding that in the case of ethyl 6-acetoxy-hexanoate and ethyl 6-ethoxycarbonyloxy-hexanoate the woody note characteristic of conventional raspberry compositions is now intensified and a pronounced fixative effect occurs without at the same time, having a detrimental effect on the fruity notes. 
     The other compounds of structure I are also distinquished by fruity notes, although in certain cases flowery side-notes are also noted. Of special interest are methyl 6-propionyloxy-hexanoate (narcissus) and isobutyl 6-acetoxy-hexanoate (after nerolidol). 
     Based on their olfactory notes, the compounds of formula I are particularly suitable for the intensification of fruity notes and as intensifiers of musk notes. Moreover, they are suitable for modifying an extremely wide range of known compositions, e.g. 
     (a) flowery compositions in which e.g. the warm musk notes are to be intensified (e.g. for men&#39;s colognes), 
     (b) chypre compositions (extract types, compositions of the feminine direction), 
     (c) tobacco and woody and fougere compositions (extract types of the masculine direction), and 
     (d) compositions with green notes, where especially a desired intensification and rounding-off and harmonizing effect are achieved. 
     As odorant substances the compounds of formula I are particularly suitable, in combination with a series of natural and synthetic odorant substances, such as e.g. 
     Natural Products 
     Such as angelica root oil, galbanum oil, vetiver oil, patchouli oil, sandalwood oil, mandarin oil, muscatel sage, ylang-ylang oil, cedar oil, pine oil, lavendar oil, bergamot oil, lemon oil, orange oil, coriander oil, oak moss, castoreum, ciste labdanum, calmus oil, geranium oil, jasmine absolute, rose oil, cassis absolute, narcissus absolute, verveine absolute, grapefruit extracts, etc. 
     Aldehydes 
     Such as C 10  -, C 11  -, C 14  -aldehyde, hydroxycitronellal, cyclamen aldehyde, benzaldehyde, p-tert.-butyl-α-methyl-hydrocinnamaldehyde, citral, citronellal, 2,6-dimethyl-5-hepten-1-al, isovaleraldehyde, trans-2-hexenal, trans-2-octenal, n-octanal, n-nonanal, trans-2-cis-6-nonadienal, 2,4-decadienal, methylnonyl-acetaldehyde, Cyclal C (1,3-dimethylcyclohex-1-ene 4(and 5)-carboxaldehyde), 3 and 4-(4-methyl-4-hydroxyamyl)-Δ3-cyclohexenecarboxaldehyde, etc. 
     Ketones 
     Such as alpha-ionone, beta-ionone, methylionone, allylionone, acetanisole, 4-(para-hydroxyphenyl)-2-butanone, camphor, menthone, carvone, pulegone, p-methylacetophenone, methyl amyl ketone, etc. 
     Acetals and ketals 
     Such as phenylacetaldehyde dimethyl acetal, phenylacetaldehyde glycerine acetal, 2-methyl-1,3-dioxolan-2-ethyl acetate, caproic aldehyde dimethyl acetal, Acetal R (mixed acetal of acetaldehyde with phenylethyl alcohol and n-propanol), etc. 
     Ethers 
     Such as eugenol methyl ether, methyl 1-methyl-cyclododecyl ether, anethol, estragol, rosantolene (methylethylsaligenin), etc. 
     Phenolic substances 
     Such as vanillin, eugenol, creosol, chavicol, etc. 
     Alcohols 
     Such as butanol, n-hexanol, cis-3-hexenol, trans-2-cis-6-nonadienol, cis-6-nonenol, linalool, geraniol, rhodinol, nerol, citronellol, nerolidol, farnesol, benzyl alcohol, phenylethyl alcohol, cinnamylalcohol, terpineol, Patchone (4-tert.-butylcyclohexanol), etc. 
     Esters 
     Such as ethyl formate, ethyl acetate, isoamyl acetate, t-butylcyclohexyl acetate, Myraldylacetat® (Givaudan), benzyl acetate, styrallyl acetate, ethyl α-methyl-phenylglycidate, maltyl isobutyrate, dimethylbenzylcarbinyl acetate and butyrate, linalyl acetate, isobutyl acetate, n-amyl butyrate, n-amyl valerate, ethyl palmitate, cinnamyl formate, terpenyl acetate, geranyl acetate, hexyl salicylate, linalyl anthranilate, amyl salicylate, methyl dihydrojasmonate, benzyl salicylate. 
     Lactones 
     Such as γ-undecalactone, γ-decalactone, γ-nonalactone, δ-decalactone, δ-octalactone, coumarin, etc. 
     Acids 
     Such as geranylic acid, citronellylic acid, cinnamic acid, phenylacetic acid, etc. 
     Sulphur-containing compounds 
     Such as p-menthane-8-thiol-3-one, dimethyl sulphide and other sulphides and disulphides, etc. 
     Nitrogen-containing compounds 
     Such as methyl anthranilate, indole, isobutylquinoline, various pyrazines, 5-methyl-heptan-3-one oxime, nitromusk, etc. 
     Various additional components often used in pefumery 
     Such as musk ketone, macrocyclic musk substances such as Musk 174® (12-oxahexadecanolide), Sandela (isocamphylcyclohexanol), polycyclic musk substances such as Fixolid, Galaxolid. 
     The compounds of formula I can be used in wide limits which can extend in compositions, for example, from 0.1 (detergents)-50% (alcoholic solutions). It will be appreciated that these values are not limiting values, as the experienced perfumer can also achieve effects with even lower concentrations or can synthesize novel complexes with even higher amounts. The preferred concentrations range between 0.5 and 20%. The compositions manufactured with compounds I can be used for all kinds of perfumed consumer goods (eau de cologne, eau de toilette, extracts, lotions, creams, shampoos, soaps, salves, powders, deodorants, detergents, air fresheners, etc). 
     The compounds I can accordingly be used in the manufacture of compositions and, as will be evident from the above compilation, a wide range of known odorant substances can be used. In the manufacture of such compositions the known odorant substances enumerated above can be used according to methods known to the perfumer, such as e.g. from W. A. Poucher, Perfumes, Cosmetics and Soaps 2, 7th Edition, Chapman and Hall, London, 1974. 
    
    
     EXAMPLE 1 
     240 g of ethyl 6-hydroxy-hexanoate are placed in a round flask which is provided with a dropping funnel, a thermometer and a stirrer. A mixture of 180 g of acetic anhydride and 3 g of 85% phosphoric acid is added dropwise thereto within a half hour while stirring. During the addition the temperature is held at 25° C. by cooling. Thereafter, the reaction mixture is heated slowly to 50° C. and held at this temperature for 3 hours. After cooling the mixture is treated with ice-water and taken up in 500 ml of hexane. The hexane solution is washed with water, with 100 ml of a 10% sodium carbonate solution and thereupon neutral with water. After drying over sodium sulphate the solvent is distilled off. 282 g of crude product are obtained. Fractional distillation gives 223 g (yield 73.7% of theory) of chemically pure ethyl 6-acetoxy-hexanoate; 190 g thereof can be used as an olfactorily pure product without further treatment. 
     Further acyloxy-hexanoates R 2  COO(CH 2 ) 5  COOR 1  (I) are manufactured in an analogous manner starting from the hydroxyesters HO(CH 2 ) 5  COOR 1  (II). 
     The hydroxyesters HO(CH 2 ) 5  COOR 1  (II) are accessible from ε-caprolactone and the corresponding R 1  -alcohol R 1  OH in the presence of, e.g., sodium bisulphate (NaHSO 4 ): 
     
         ______________________________________           B.p. [°C./mmHg]                      n.sub.D.sup.20______________________________________Methyl 6-hydroxy-hexanoate             105°/7                          1.4385Ethyl 6-hydroxy-hexanoate              65°/0.001                          1.4365Propyl 6-hydroxy-hexanoate             80°/0.09                          1.4400Isopropyl 6-hydroxy-hexanoate             75°/0.06                          1.4462Butyl 6-hydroxy-hexanoate             85°/0.05                          1.4412Isobutyl 6-hydroxy-hexanoate             92°/0.2                          1.4396Allyl 6-hydroxy-hexanoate             98°/0.25                          1.4535Methallyl 6-hydroxy-hexanoate             99°/0.05                          1.4580______________________________________ 
    
     The novel products I and their properties are compiled in the Table A hereinafter. 
     
                                           TABLE A__________________________________________________________________________Starting material II Product IR.sup.1   Reagent    R.sub.2                       R.sub.1   B.p. (mmHg)                                        n.sub.D.sup.20                                            d.sub.4.sup.20                                                Odour__________________________________________________________________________--CH.sub.2 CH.sub.3     Acetic anhydride                CH.sub.3 --                       --CH.sub.2 CH.sub.3                                 65/0.1 1.4292                                            1.0081                                                Fruity     phosphoric acid                            (raspberries)--CH.sub.3     Acetic anhydride/                H      --CH.sub.3                                 107/7  1.4310                                            1.0545                                                Fruity, after     formic acid                                chocolate, iris--CH.sub.3     Acetic anhydride/                CH.sub.3 --                       --CH.sub.3                                 58/0.08                                        1.4285                                            1.0327                                                Fruity     phosphoric acid                            (raspberries),                                                flowery--CH.sub.3     Propionic anhydride/                CH.sub.3 CH.sub.2 --                       --CH.sub.3                                 122/7  1.4318                                            1.0148                                                Fruity     phosphoric acid                            (raspberries,                                                strawberries),                                                narcissus--CH.sub.2 CH.sub.3     Acetic anhydride/                H      --CH.sub.2 CH.sub.3                                 47/0.04                                        1.4302  Fruity     formic acid                                (raspberries)--CH.sub.2 CH.sub.3     Propionic anhydride/                CH.sub.3 CH.sub.2 --                       --CH.sub.2 CH.sub.3                                 114/7  1.4304                                            0.9937                                                Fruity     phosphoric acid                            strawberries,                                                rasberries)--CH.sub.2 CH.sub.2 CH.sub.3     Acetic anhydride/                H      --CH.sub.2 CH.sub.2 CH.sub.3                                 52/0.03                                        1.4323                                            1.0104                                                Slightly fruity     formic acid--CH.sub.2 CH.sub.2 CH.sub.3     Acetic anhydride/                CH.sub.3 --                       --CH.sub.2 CH.sub.2 CH.sub.3                                 66/0.05                                        1.4310                                            0.9928                                                Slightly fruity     phosphoric acid--CH.sub.2 CH.sub.2 CH.sub.3     Propionic anhydride/                CH.sub.3 CH.sub.2                       --CH.sub.2 CH.sub.2 CH.sub.3                                 85.5/0.22                                        1.4335  Slightly fruity     phosphoric acid                            (raspberries),                                                powdery--CH(CH.sub.3).sub.2     Acetic anhydride/                H      --CH(CH.sub.3).sub.2                                 68.5/0.2                                        1.4288                                            1.0011                                                Fruity     formic acid                                (pineapple),                                                flowery--CH(CH.sub.3).sub.2     Acetic anhydride/                CH.sub.3 --                       --CH(CH.sub.3).sub.2                                 78.5/0.2                                        1.4270                                            0.9847                                                Fruity,     phosphoric acid                            (raspberries),                                                powdery--CH(CH.sub.3).sub.2     Propionic anhydride/                CH.sub.3 CH.sub.2 --                       --CH(CH.sub.3).sub.2                                 67/0.01                                        1.4290                                            0.9733                                                Fruity after     phosphoric acid                            birch, leather--CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3     Acetic anhydride/                CH.sub.3 --                       --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                 86/0.09                                        1.4330                                            0.9812                                                Slightly     phosphoric acid                            aldehydic--CH.sub.2 CH(CH.sub.3).sub.2     Acetic anhydride/                H      --CH.sub.2 CH(CH.sub.3).sub.2                                 66/0.11                                        1.4309                                            0.9910                                                After hexyl     formic acid                                salicylate--CH.sub.2 CH(CH.sub.3).sub.2     Acetic anhydride/                CH.sub.3 --                       --CH.sub.2 CH(CH.sub.3).sub.2                                 74/0.15                                        1.4307                                            0.9765                                                Somewhat     phosphoric acid                            flowery, after                                                nerolidol--CH.sub.2 CH═CH.sub.2     Acetic anhydride/                H      --CH.sub.2 CH═CH.sub.2                                 69/0.1 1.4434                                            1.0344                                                Fruity, allylic     formic acid--CH.sub.2 CH═CH.sub.2     Acetic anhydride/                CH.sub.3 --                       --CH.sub.2 CH═CH.sub.2                                 94/0.09                                        1.4430                                            1.0158                                                Fruity     phosphoric acid--CH.sub.2 CH═CH.sub.2     Propionic anhydride/                CH.sub.3 CH.sub.2 --                       --CH.sub.2 CH═CH.sub.2                                 87/0.15                                        1.4423                                            1.0014                                                Fruity     phosphoric acid                            (raspberries),                                                good adhesion--CH.sub.2 CH.sub.3     Isobutyric anhydride                (CH.sub.3).sub.2 CH--                       --CH.sub.2 CH.sub.3                                 72/0.1 1.4305                                            0.9748                                                Fruity     phosphoric acid                            (raspberries)__________________________________________________________________________ 
    
     EXAMPLE 2 
     160 g of ethyl 6-hydroxy-hexanoate, 145.4 g of N,N-dimethylaniline and 200 ml of anhydrous toluene are placed in a round flask which is provided with a dropping funnel, a thermometer and a stirrer. 119.4 g of ethyl chloroformate are added dropwise at 25° C. within a half hour while stirring. The reaction mixture is held under reflux for 3 hours. After cooling the reaction mixture is poured on to ice-water, the organic phase is washed twice with water, with 100 ml of a 5% hydrochloric acid solution and then neutral with water. After drying over sodium sulphate the solvent is distilled off. 173 g of crude product are obtained. Fractional distillation gives 112 g (yield 48.3% of theory) of chemically pure ethyl 6-ethoxycarbonyloxy-hexanoate; 75 g thereof can be used as an olfactorily pure product without further treatment. 
     Further alkoxycarbonyloxy-hexanoates R 2  COO(CH 2 ) 5  COOR 1  (I) with R 2  =methoxy and ethoxy are manufactured in an analogous manner starting from the hydroxyesters HO(CH 2 ) 5  COOR 1  (II). 
     The novel products and their properties are compiled in Table B hereinafter. 
     
                                           TABLE B__________________________________________________________________________Startingmaterial II        Product I        B.p.R.sup.1   Reagent  R.sup.2                     R.sup.1   [°C./mmHg]                                      n.sub.D.sup.20                                          Odour__________________________________________________________________________--CH.sub.2 CH.sub.3     ClCOOCH.sub.2 CH.sub.3              CH.sub.3 CH.sub.2 O--                     --CH.sub.2 CH.sub.3                               102°/0.5                                      1.4300                                          Fruity, reminiscent                                          of raspberry ketone--CH.sub.2 CH.sub.3     ClCOOCH.sub.3              CH.sub.3 O--                     --CH.sub.2 CH.sub.3                               70°/0.02                                      1.4293                                          Slightly fruity,                                          after raspberry--CH.sub.3     ClCOOCH.sub.2 CH.sub.3              CH.sub.3 CH.sub.2 O--                     --CH.sub.3                               68°/0.05                                      1.4292                                          Fruity, after rasp-                                          berry, oily--CH.sub.3     ClCOOCH.sub.3              CH.sub.3 O--                     --CH.sub.3                               63°/0.02                                      1.4290                                          Fruity, after Ver-                                          dylacetat, slight-                                          ly reminiscent of                                          green apples, oily--CH.sub.2 CH.sub.2 CH.sub.3     ClCOOCH.sub.2 CH.sub.3              CH.sub.3 CH.sub.2 O--                     --CH.sub.2 CH.sub.2 CH.sub.3                               88°/0.07                                      1.4310                                          Slightly reminis-                                          cent of raspberry,                                          oily--CH.sub.2 CH.sub.2 CH.sub.3     ClCOOCH.sub.3              CH.sub.3 O--                     --CH.sub.2 CH.sub.2 CH.sub.3                               78°/0.09                                      1.4308                                          Oily, metallic--CH.sub.2 --CH═CH.sub.2     ClCOOCH.sub.2 CH.sub.3              CH.sub.3 CH.sub.2 O--                     --CH.sub.2 --CH═CH.sub.2                               96°/0.15                                      1.4410                                          After raspberry                                          confectionery__________________________________________________________________________ 
    
     EXAMPLE 3 
     A. Fruity base in the direction of apple 
     
         ______________________________________                Parts by weight______________________________________Galaxolid 50 (IFF) (1,3,4,6,7,8-                  100hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-γ-2-benzopyran) indiethyl phthalateFraise pure (ethyl methyl-phenyl-                  100glycidate) [50% in ethyl phthalate]                  60Agrumex (Haarmann &amp; Reimer) (2-tert.-                  30butylcyclohexyl acetate)Maltyl isobutyrate     60cis-3-Hexenyl isobutyrateDimethylbenzylcarbinyl butyrate                  40Givescone (Giv) (2-ethyl-6,6-                  20dimethyl-2-cyclohexene-1-carboxylicacid ethyl ester)Cyclal C (Giv) (1,3-dimethyl-cylohex-                  101-ene 4(and 5)-carboxaldehyde)(10% DPG)Ethyl acetoacetate     40Dipropylene glycol (DPG)                  440                  900______________________________________ 
    
     When 100 parts of ethyl 6-acetoxy-hexanoate are added to the above generally fruity base, the fruity note is brought very clearly in the direction of apple. Moreover, the powdery-fruity note of the Galaxolid-Agrumex complex is underlined in an advantageous manner, which confers to the base a character which is very natural and which has good adhesion. 
     B. Fruity base in the direction of melon 
     
         ______________________________________               Parts by weight______________________________________Myraldylacetat (Giv) (5-[3-and                 1004-(acetoxymethy)-1-cyclohexenyl]-2-methyl-2-pentene)Linalyl acetate       100Dimethylbenzylcarbinyl butyrate                 50Cyclamen aldehyde     30Fraise pure (ethyl methyl-phenyl-                 30glycidate)Undecalactone         30Ethyl acetoacetate    30Acetal R (Giv) (acetaldehyde phenyl-                 10ethyl-propyl acetal)Melonia (3,7-dimethyl-7-methoxy-1-                 5octanal)Dipropylene glycol (DPG)                 350                 750______________________________________ 
    
     By the addition of 100 parts of ethyl 6-acetoxy-hexanoate the above base of general fruity character is brought in the direction of muskmelon. The lactone-like sweet note is clearly intensified, which confers to the base more volume and substantially improved tenacity. 
     C. Perfumery base in the direction of apricot 
     
         ______________________________________             Parts by weight______________________________________α-Ionone      80Dimethylbenzylcarbinyl butyrate               50Allylionone         40Fructone.sup.R (IFF) (2-methyl-1,3-               30dioxolan-2-ethyl acetate)Palmarosa oil       20Undecalactone       15Dipropylene glycol (DPG)               665               900______________________________________ 
    
     An addition of 100 parts of ethyl 6-acetoxy-hexanoate produces in the above conventional apricot base the typical pronounced velvety-soft note of overripe apricots; the resulting formulation is already well suited for the perfuming of cosmetic preparations; in other words; the base which results is now a true, complete perfume base. In the case of the conventional apricot base this is not the case as, although it can also produce an apricot nuance in a composition, the sweet, velvety note of the ripe fruit is subsequently missing in the composition. 
     D. Flowery-green base 
     
         ______________________________________                Parts by weight______________________________________Phenoxyethyl alcohol   205Linalool               150Terpineol              100Dimethylbenzylcarbinyl butyrate                  60Calaxolid (IFF) (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-γ-2-benzopyran)Hedione (Firmenich) (methyl                  60dihydrojasmonate)Verdylacetat (dihydro-nor-dicyclo-                  50pentadienyl acetate)Citronellol            40Acetal R (Giv) (acetaldehyde phenyl-                  30ethyl n-propyl acetal)Geranyl acetate        30Lilial (Giv) (p-tert.butyl-α-                  15methylhydrocinnamaldehyde)Cyclamen aldehyde (10% DPG)                  10Cyclal C (Giv) (1,3-dimethyl-                  10cyclohex-1-ene 4(and 5)-carboxaldehyde) (10% DPG)Phenylacetaldehyde dimethyl acetal                  10Corps cassis (Giv) (p-menthane-8-thiol-                  103-one (10% DPG)Eugenol                10Diphenyl oxide          5Indole (10% DPG)        5Dipropylene glycol (DPG)                  40                  900______________________________________ 
    
     When 100 parts of ethyl 6-acetoxy-hexanoate are added to the above flowery-green base, there results a base which is very much greener, more powdery and substantially stronger in odour. The novel ester combines the musk and the green notes (Galaxolid-Acetal R) with one another very advantageously. The base is very well suited for the perfuming of cosmetic preparations. 
     E. Herby-green base 
     
         ______________________________________                Parts by weight______________________________________Linalyl acetate        150Madrox (Giv) (1-methyl-1-methoxy-                  100cyclododecane)Linalool               150Tetrahydrolinalool     80Hedione (Firmenich) (methyl dihydro-                  100jasmonate)Bergamot oil           80Hyssop oil             60Patchouli oil (anhydrous)                  60Galaxolid (IFF) (1,3,4,6,7,8-                  40hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-α-2-benzopyran)Allylionone            20Eugenyl phenylacetate  20Acetal E (Giv) (1-phenyl-4-methyl-                  153,5-dioxyheptane)Cyclal C (Giv) (1,3-dimethyl-                  10cyclohex-1-ene 4(and 5)-carboxaldehyde) (10% DPG)Corps cassis (Giv)     10(p-methane-8-thio-3-one) (10% DPG)Fixateur 404 (Firmenich) (8-α, 12-                   5oxido-13,14,15,16-tetranorlabdane)                  900______________________________________ 
    
     By the addition of 10% of ethyl 6-acetoxy-hexanoate the herby-green note of the above base is clearly intensified. Ethyl 6-acetoxy-hexanoate underlines the somewhat powdery, spicy note of the basic composition in an unsuspected manner, which brings more warmth and volume to the base. The novel formulation can now be used very well for men&#39;s colognes. 
     On the other hand, in not one of the above bases A to E can the effects specified be realized by replacing ethyl 6-acetoxy-hexanoate by the same amounts of the structurally similar compounds diethyl adipate or 1,6-diacetoxyhexane. 
     EXAMPLE 4 
     A. Herby-green base 
     
         ______________________________________             Parts by weight______________________________________Fixateur 404         5Corps Cassis DC (10% DPG)               10Cyclal C (10% DPG)  10Acetal E            15Eugenyl phenylacetate               20Ketone V (allyl-α-ionone)               20Galaxolid 50        40Patchouli anhydrous 60Hyssop oil          60Bergamot oil        80Tetrahydrolinalool  80Madrox              100Hedione             100Linalool            150Linalyl acetate     150               900______________________________________ 
    
     The addition of 100 parts of ethyl 6-ethoxycarbonyloxy-hexanoate intensifies the fruity-hesperidin aspect of the base and confers remarkable freshness to the novel composition. Compared with the composition without the addition, the novel composition is quite clearly preferred. 
     B. Fruity base 
     
         ______________________________________             Parts by weight______________________________________Cyclal C (10% DPG)  10Givescone           20Maltyl isobutyrate  30Dimethylbenzylcarbinyl butyrate               40Ethyl acetate       40cis-3-Hexenyl isobutyrate               60Agrumex             60Galaxolid 50        100Fraise pure         100Dipropylene glycol (DPG)               440               900______________________________________ 
    
     An addition of 100 parts of ethyl 6-ethoxycarbonyloxy-hexanoate leads to an unequivocal preference for the thus-prepared novel composition, as in it the desired effect in the direction of apple can be recognized substantially clearer than in the original base without the addition. A desired stylizing of a primary general-fruity note is therefore brought about by the addition of the novel compound I, the strawberry aspect (&#34;fraise pure&#34;) changing into an apple note. Furthermore, this effect is unexpected, as the novel compound I has a fruity smell in the direction of raspberry, and therefore rather an intensification of the fruity-berry like note would have been expected. 
     Base in the direction of melon 
     
         ______________________________________               Parts by weight______________________________________Melonia                5Acetal R              10Ethyl acetate         30Geranyl acetate       30Peche Pure (γ-n-heptylbutyrolactone)                 30Fraise Pure           30Cyclamen aldehyde     30Dimethylbenzylcarbinyl butyrate                 50Myraldylacetate       100Linalyl acetate       100Dipropylene glycol (DPG)                 350                 765______________________________________ 
    
     The addition of 100 parts of ethyl 6-ethoxycarbonyloxy-hexanoate to the above base is extraordinarily favourable from the organoleptic point of view, as the fruity-juicy melon character is thereby significantly accentuated.

Technology Category: 8