Abstract:
The invention is directed to a perfumery composition consisting essentially of at least one alkyl-substituted 1,3-dioxolane and customary constituents and to the use of such a perfumery composition to impart a pleasant odor to a product.

Description:
This is a continuation of co-pending U.S. patent application Ser. No. 226,201, filed Jan. 19, 1981, now abandoned. 
    
    
     FIELD OF THE INVENTION 
     This invention is directed to novel perfuming agents. More particularly, this invention is directed to the use of alkyl-substituted 1,3-dioxolanes as perfuming agents as well as perfuming compositions containing such compounds. 
     OBJECTS OF THE INVENTION 
     It is an object of the invention to provide for the use of alkyl-substituted 1,3-dioxolanes as perfuming agents. 
     It is also an object of the invention to provide perfuming compositions based upon alkyl-substituted 1,3-dioxolanes. 
     These and other objects of the invention will become more apparent in the discussion below. 
     DETAILED DESCRIPTION OF THE INVENTION 
     It has been found that alkyl-substituted 1,3-dioxolanes of the general formula ##STR1## wherein R 1  represents alkyl of from 4 to 12 carbon atoms; R 2  represents hydrogen, an alkyl of from 1 to 7 carbon atoms, a cycloalkyl or cycloalkenyl of from 5 to 8 carbon atoms, or an optionally alkyl-substituted aryl; and R 3  represents hydrogen or an alkyl of from 1 to 3 carbon atoms, can be used in an advantageous manner as perfumes or perfuming agents with a vigorous, mainly fruity note. At least one of the alkyl-substituted 1,3-dioxolanes is used as a perfuming agent in a perfume composition. 
     The R 1  group of the compounds of Formula I can be, for example, a butyl, hexyl, octyl, decyl, or dodecyl group, and the R 3  group can be hydrogen or a methyl, ethyl, propyl, or isopropyl group. R 2  is preferably hydrogen or a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, hexyl, heptyl, cyclohexyl, cyclohexenyl, or cyclooctyl group. R 2  can also be a phenyl, lower alkyl-substituted phenyl such as toluyl or ethylphenyl, naphthyl or lower alkyl substituted naphthyl, or furyl group. 
     The alkyl-substituted 1,3-dioxolanes to be used as perfuming agents according to the invention are prepared by a basic, known method of organic synthesis. One course of synthesis consists of the acetalization of carbonyl compounds having the radicals R 2  and R 3  with 1,2-alkane diols having a chain length of C 6  -C 14 , in the presence of acid catalysts, while the water of reaction is removed with a solvent by azeotropic distillation or by conversion of the water of reaction with a triester of orthoformic acid. The reaction proceeds according to the following scheme: ##STR2## In addition, a relatively large number of the alkyl-substituted 1,3-dioxolanes to be used as perfuming agents according to the invention has been prepared by special methods, as is described for 2,2-dimethyl-4-dodecyl-1,3-dioxolane by R. P. Hanzlik and M. Leinwetter in J. Org. Chem., Vol 43, 438 (1978); for 4-heptyl-, 4-octyl-, 4-decyl-, and 4-dodecyl-1,3-dioxolane by I. Rosenthal and D. Elad in J. Org. Chem., Vol. 33, 805 (1968); for 4-octyl-1,3-dioxolane by R. Lalende et al. in Tetrahedron Letters, 1969, 745; for 2,2-dimethyl-4-pentyl-1,3-dioxolane by S. Raucher in Tetrahedron Letters, 1976, 1161; for 2,2-dimethyl-4-undecyl-1,3-dioxolane by H. Nakada in Agric. Biol. Chem., Vol. 41, 1761 (1977); and for 2-methyl-4-hexyl-1,3-dioxolane by E. Tobler in Helv. Chim. Acta., Vol. 52, 408 (1969). However, none of these publications provides any information about the fragrance characteristics or that such alkyl-substituted 1,3-dioxolanes can be used advantageously as perfuming agents in the most widely varying perfuming compositions. 
     Alkyl-substituted 1,3-dioxolanes that can be used according to the invention are, for example, 4-hexyl-, 4-octyl-, 4-decyl-, 2-methyl-4-hexyl-, 2-methyl-4-octyl-, 2-methyl-4-decyl-, 2-ethyl-4-octyl-, 2-isopropyl-4-decyl-, 2-isopropyl-4-dodecyl-, 2-pentyl-4-hexyl-, 2-heptyl-4-butyl-, 2,2-dimethyl-4-hexyl-, 2,2-dimethyl-4-octyl-, 2-methyl-2-ethyl-4-butyl-, 2-methyl-2-ethyl-4-hexyl-, 2-cyclohexyl-4-butyl-, 2-cyclohex-3-enyl-4-butyl-, 2-cyclooctyl-4-butyl-, 2-α-furyl-4-butyl-, 2-cyclohex-3-enyl-4-hexyl-, 2-phenyl-4-hexyl-, 2-phenyl-4-octyl-, 2-isobutyl-4-butyl-, 2-isobutyl-4-hexyl-, 2-isobutyl-4-octyl-, 2-(2-pentyl)-4-butyl-, or 2-(2-pentyl)-4-hexyl-1,3-dioxolane. 
     The alkyl-substituted 1,3-dioxolanes to be used according to the invention represent valuable perfuming agents with characteristic, interesting perfume notes. A particular advantage is the fact that they combine readily into novel fragrance nuances. 
     The alkyl-substituted 1,3-dioxolanes to be used according to the invention can be mixed with other perfumes in various quantity ratios to provide new perfume compositions. Generally, the content of the alkyl-substituted 1,3-dioxolanes in the perfume compositions will range from about 1 to 50 percent by weight, based on the weight of the total composition. Such compositions can serve directly as perfume or also as perfuming agents in cosmetics, such as creams, lotions, toilet waters, aerosols, mouth-care products, toilet soaps, and the like. Also, they may be used to improve the odor of industrial and commercial products such as detergents and cleansing agents, disinfectants, softeners, textile treatment agents, and the like. To perfume the various products, the perfume compositions containing the alkyl-substituted 1,3-dioxolanes to be used according to the invention are added to the products generally in concentrations of from about 0.05 to 2 percent by weight, based on the total weight of the products. 
     The following examples are intended to illustrate the invention in greater detail and are not to be construed as limiting the invention thereto. 
    
    
     EXAMPLES 
     Examples 1 TO 27 
     Several alkyl-substituted 1,3-dioxolanes to be used according to the invention were prepared using a general preparation method. According to this method, 0.1 mol of the respective carbonyl compound, 0.1 mol of the respective 1,2-alkane diol, 0.1 mol of orthoformic acid triethyl ester, and 0.5 gm of p-toluene sulfonic acid were agitated for one hour at room temperature. Then, a mixture of ethyl formate and ethanol was distilled off slowly. The cooled residue was taken up in ether, washed with an aqueous sodium carbonate solution, dried over sodium sulfate, evaporated, and distilled under vacuum. 
     The compounds prepared and their characteristics are set forth in the following table: 
     
                                           TABLE__________________________________________________________________________                         Boiling Point                                Pressure                                     RefractiveExampleCompound     Perfume Note                         (°C.)                                (mbar)                                     Index (n.sub.D.sup.20)__________________________________________________________________________1    4-Hexyl-1,3-dioxolane             bitter nut note                         42     0.02 1.43352    4-Octyl-1,3-dioxolane             fatty aldehyde note     1.43813    4-Decyl-1,3-dioxolane             fresh geranyl acetate                         90     0.02 1.4430             note4    2-Methyl-4-hexyl-1,3-             fruity, cabbage-like                         --     --   1.4292dioxolane5    2-Methyl-4-octyl-1,3-             lovage note 69     0.02 1.4348dioxolane6    2-Methyl-4-decyl-1,3-             walnut-jasmone note                         80     0.02 1.4396dioxolane7    2-Ethyl-4-octyl-1,3-             lovage, walnut note                         78     0.02 1.4342dioxolane8    2-Isopropyl-4-decyl-1,3-             sweet St. John&#39;s                         135    0.65 1.4423dioxolane    bread note9    2-Isopropyl-4-dodecyl-             St. John&#39;s bread note                         155    0.65 1.44621,3-dioxolane10   2-Pentyl-4-hexyl-1,3-             flowery, green                         75     0.02 1.4389dioxolane11   2-Heptyl-4-butyl-1,3-             nut note, sweet                         140    20   1.4396dioxolane12   2,2-Dimethyl-4-hexyl-             jasmone note                         50     0.15 1.42511,3-dioxolane13   2,2-Dimethyl-4-octyl-             fresh laundry note                         122    20   1.43221,3-dioxolane14   2-Methyl-2-ethyl-4-             fruity, cabbage-like                         73     16   1.4240butyl-1,3-dioxolane15   2-Methyl-2-ethyl-4-             spicy       105    20   1.4308hexyl-1,3-dioxolane16   2-Cyclohexyl-4-butyl-1,3-             fruity      54     0.06 1.4602dioxolane17   2-Cyclohex-3-enyl-4-             fruity, raspberry,                         70     0.03 1.4702butyl-1,3-dioxolane             strawberry note18   2-Cyclooctyl-4-butyl-             sweet       91     0.02 1.47281,3-dioxolane19   2-α-Furyl-4-butyl-             jasmone, mushroom note                         63     0.02 1.47081,3-dioxolane20   2-Cyclohex-3-enyl-4-             raspberry, strawberry                         90     0.02 1.4699hexyl-1,3-dioxolane             note21   2-Phenyl-4-hexyl-1,3-             flowery, sweet,                         104    0.06 1.4952dioxolane    tobacco note22   2-Phenyl-4-octyl-1,3-             fatty alcohol note                         118    0.02 1.4920dioxolane23   2-Isobutyl-4-butyl-             pineapple note                         96     23   1.42951,3-dioxolane24   2-Isobutyl-4-hexyl-             dry fruity  125    23   1.43501,3-dioxolane25   2-Isobutyl-4-octyl-             blueberry note                         154    21   1.43951,3-dioxolane26   2-(2-Pentyl)-4-butyl-             sweet       109    21   1.43351,3-dioxolane27   2-(2-Pentyl)-4-hexyl-             strawberry note                         100    7    1.43851,3-dioxolane__________________________________________________________________________ 
    
     Several typical perfume compositions containing alkyl-substituted 1,3-dioxolanes are set forth below in Examples 28 and 29. The alkyl-substituted 1,3-dioxolane given in each example could readily be replaced by a similar such compound within the scope of the invention. 
     Example 28 
     
         ______________________________________Fruit Complex                AmountComponent            (parts by weight)______________________________________2-Cyclohex-3-enyl-4-butyl-                3001,3-dioxolanePhenylethyl alcohol  130Benzyl acetate       100Linalyl acetate      50Citronellol          50Lemon oil            50Orange oil, sweet    50Cyclovertal, 10%     50Phenylethyl acetate  40Aldehyde C.sub.18 (nonalactone), 10%                40Galaxolide           30Aurantesine          30Benzyl propionate    30Aldehyde C.sub.14 (undecalactone), 10%                20Phenylisobutyrate    20Cyclamen aldehyde    10                1000______________________________________ 
    
     Example 29 
     
         ______________________________________Jasmine Complex               AmountComponent           (parts by weight)______________________________________2,2-Dimethyl-4-hexyl-1,3-               100dioxolaneLinalool            350Benzyl acetate      100Lyral               100Dimethylbenzylcarbinyl acetate               50Benzylsalicylate    50Ethyl linalool      50Benzyl alcohol      40Ylang-Ylang oil     40Benzylphenyl acetate               20Citronellol         20Benzylbenzoate      20Cyclamen aldehyde   15α-Amylcinnamaldehyde               15Methylnaphthyl ketone               10Nerol               10Methyl eugenol       6Indoflor             1Hexenylbenzoate      1Methylheptenone, 20%                1Decanal, 10%        1               1000______________________________________ 
    
     The preceding 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.