BACKGROUND OF THE INVENTION

The instant invention relates to norbornyloxy butanal defined according to the structure: ##STR4## as well as a novel process for preparing such a hydrocarbyloxy alkanal by first reacting camphene having the structure: ##STR5## with allyl alcohol having the structure: ##STR6## in order to form norbornyl allyl ether having the structure: ##STR7## and then reacting the resulting norbornyl allyl ether via an oxo reaction using carbon monoxide and oxygen to form the compound having the structure: ##STR8##

Inexpensive chemical compounds which can provide natural pine, cypress-like and fir-balsam-like aroma nuances are highly desirable in the art of perfumery. Many of the natural materials which provide such fragrances and contribute such desired nuances to perfumery compositions are high in cost, unobtainable at times, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.

There is, accordingly, a continuing effort to find synthetic materials which will provide, enhance or augment the fragrance notes provided by natural essential oils or compositions thereof. Unfortunately, many of the synthetic materials either have the desired nuances only to a relatively small degree or they contribute undesirable or unwanted odor to perfume compositions, perfumed articles and colognes.

Norbornyl oxyacetaldehydes have been previously made the subject of application for U.S. Letters Patent Ser. No. 303,012 filed on Sept. 17, 1981. This compound has the structure: ##STR9## and it is disclosed in said application for U.S. Letters Patent Ser. No. 303,012 filed on Sept. 17, 1981 that the compound has intense and long-lasting woody, lavender-like, rosemary-like, green aromas with rosemary-like, lavandin-like, woody and natural pine oil-like and fresh herbaceous nuances on dry-out.

The compound of the instant invention defined according to the structure: ##STR10## has properties in the perfumery field which are unexpectedly, unobviously and advantageously superior over the properties of the product having the structure: ##STR11##

Furthermore, although norbornyl derivatives are known in the art for producing piney aromas such as, for example, those disclosed in U.S. Pat. No. 4,153,811 issued on May 8, 1979, the inexpensive norbornyl oxybutyraldehyde type of compound has heretofore been unknown.

Thus U.S. Pat. No. 4,153,811 discloses the use of substituted norbornane derivatives of the genus of compounds having the structure: ##STR12## wherein each of the dashed lines represents a carbon-carbon single bond or a carbon-carbon double bond with the proviso that at least one of the dashed lines is a carbon-carbon single bond; wherein n is 0 or 1 with the proviso that n is 1 when both dashed lines are carbon-carbon single bonds and n is 0 when one of the dashed lines is a carbon-carbon double bond; wherein R.sub.1 and R.sub.2 are each the same or different hydrogen or lower alkyl; wherein Y is: ##STR13## wherein Z is one of the moieties: ##STR14## wherein R.sub.3 and R.sub.4 are each alkyl; wherein R.sub.7, R.sub.8 and R.sub.10 are each the same or different hydrogen or lower alkyl; wherein R.sub.9 and R.sub.9 ' taken separately are the same or different lower alkyl, or taken together is lower alkylene; wherein the dotted line represents a carbon-carbon single bond or a carbon-carbon double bond; and wherein each of the wavy lines represents, in the alternative, exo or endo isomers.

U.S. Pat. No. 3,852,358 issued on Dec. 3, 1974 discloses a process for producing 2-acetyl-3,3-dimethyl-5-norbornene in both the exo and endo forms which have uses in perfumery and other fragrance applications. These compounds have the structures: ##STR15## These compounds, produced by reaction of cyclopentadiene with mesityl oxide, are starting materials for producing a number of the compound of our invention. However, the compound of our invention has unexpected, unobvious and advantageous properties when compared with the 2-acetyl-3,3-dimethyl-5-norbornene of U.S. Pat. No. 3,852,358.

U.S. Pat. No. 3,942,761 discloses the use in perfumery of 4-(2'-norbornyl)-2-butanones having the structure: ##STR16## wherein R.sub.1 is hydrogen or methyl and R is hydrogen or lower alkyl containing from 1 to 8 carbon atoms. Such compounds have structures which are different in kind from the structures of the compounds of our invention. Also disclosed as intermediates for producing the foregoing compounds are compounds having the generic structure: ##STR17## wherein the dotted line is a carbon-carbon single bond or a carbon-carbon double bond. In addition, the following reaction sequence is set forth therein: ##STR18##

Arctander, "Perfume and Flavor Chemicals", 1969, Vol. 1, discloses the use in perfume compositions and in foodstuff flavors of "fenchone", "fenchyl alcohol", "camphene carbinol", and "camphene carbinyl acetate", thus:

(i) "1385: FENCHONE laevo-Fenchone (dextro- is known but less common as a fragrance material). 1,3,3-trimethyl-2-norbornanone. 1,3,3-trimethyl bicyclo-1,2,2-heptanone-2. ##STR19## Warm-camphoraceous, powerful and diffusive, basically sweet odor. Warm, somewhat burning and bitter taste with a medicinal note. This ketone finds some use as a masking odor in industrial fragrances. It is also used in the reconstruction of fennel oil and a few other essential oils. In spite of its rather unpleasant taste, it is used in various berry complex flavors, in spice complexes and in certain types of liquor flavoring. The concentration used is about 0.1 to 5 ppm in the finished product."

(ii) "1387: FENCHYL ALCOHOL 1,3,3-trimethyl-2-norbornanol. 1,3,3-trimethyl bicyclo-1,2,2-heptanol-2. 2-fenchanol. Fenchol. ##STR20## The racemic alpha-fenchol has a somewhat lower melting point, and the beta-fenchols are all liquid at room temperature. Fenchol made by reduction of fenchone from cedarleaf oil is usually a mixture of several isomers, including the crystalline alpha-isomers. The beta-isomer forms a crystalline hydrate which may be sold at room temperature. Almost insoluble in water, soluble in alcohol, miscible with oils. Powerful and diffusive, camphor-like but sweeter and more citrus-like almost lime-like color with more or less of an earthy-dry character, according to the composition and isomer-ratio. The taste is somewhat bitter-lime-like, camphoraceous and slightly woody-musty. This interesting alcohol (or mixed alcohols) finds use in perfume compositions ranging from woody or herbaceous to citrus-lime and even certain floral types. It produces power and "lift" to floral fragrances, and solid background to lime and other citrus bases, having the advantage over the terpenes in being very stable in soap. Fenchyl alcohol is also used in flavor compositions such as strawberry and other berries, lime and spice, etc. The concentration is normally low, e.g. 0.2 up to 5 ppm in the finished product."

(iii) "1028: 3,3-DIMETHYL-.DELTA..sup.2, beta-NORBORNANE-2-ETHANOL. "Camphene carbinol". ##STR21## Sweet, camphoraceous, warm and soft odor with a woody undertone. Upon standing it may develop an odor resembling that of celluloid.

Although rarely offered commercially, this chemical could find some use in perfume compositions of the woody, oriental and orissy type, in new variations of pine fragrances, and in various soap and detergent perfumes".

(iv) "1029: 3,3-DIMETHYL-.DELTA..sup.2 -beta-NORBORNANE-2-ETHYLACETATE "Camphene carbinyl acetate". ##STR22## Mild and sweet-woody odor with a floral-piney undertone. The commercial products are probably not well-defined single chemicals, and great variations in odor have been observed.

This ester has been developed in line with the research on sandalwood type odors. The parent alcohol "camphene carbinol" was once considered useful as a sandalwood type material, but it has found more use as a sweetening and enriching ingredient in sophisticated pine fragrances. The title ester finds limited use in perfume compositions of woody character, fougeres, pine fragrances, etc. and it blends very well with the cyclohexanol derivatives, ionones, isobornylacetate, nitromusks, etc.".

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the distillation product of the reaction product of Example I, first distillation, bulked fractions 1-7 (conditions: SE-30 column programmed at 150.degree.-220.degree. C. at 8.degree. C. per minute). This reaction product contains the compounds having the structures: ##STR23##

FIG. 2 is the GLC profile for fraction 7 of the redistillation product of the reaction product of Example I containing the compound having the structure: ##STR24##

FIG. 3 is the GLC profile for the redistillation product (bulked fractions 2-7) of the reaction product of Example I containing the compound having the structure: ##STR25##

FIG. 4 is the NMR spectrum for bulked fractions 2-7 of the redistillation product of the reaction product of Example I containing the compound having the structure: ##STR26##

FIG. 5 is the infra-red spectrum for bulked fractions 2-7 of the redistillation product of the reaction product of Example I containing the compound having the structure: ##STR27##

FIG. 6 is the GLC profile for the crude reaction product of Example II containing the compounds having the structures: ##STR28##

FIG. 7 is the GLC profile for fraction 1 of the distillation product of the reaction product of Example II containing the compound having the structure: ##STR29##

FIG. 8 is the GLC profile for fraction 2 of the distillation product of the reaction product of Example II containing the compound having the structure: ##STR30##

FIG. 9 is the GLC profile for fraction 3 of the distillation product of the reaction product of Example II containing the compound having the structure: ##STR31##

FIG. 10 is the GLC profile for fraction 4 of the distillation product of the reaction product of Example II containing the compound having the structure: ##STR32##

FIG. 11 is the GLC profile for fraction 5 of the distillation product of the reaction product of Example II containing the compound having the structure: ##STR33##

FIG. 12 is the GLC profile for fraction 6 of the distillation product of the reaction product of Example II containing the compound having the structure: ##STR34##

FIG. 13 is the GLC profile for fraction 7 of the distillation product of the reaction product of Example II containing the compound having the structure: ##STR35##

FIG. 14 is the NMR spectrum for fraction 5 of the distillation product of the reaction product of Example II which is the compound having the structure: ##STR36##

FIG. 15 is the infra-red spectrum for fraction 5 of the distillation product of the reaction product of Example II which is for the compound having the structure: ##STR37##

THE INVENTION

The present invention provides the family of hydrocarbyloxy alkanals defined according to the structure: ##STR38## wherein R.sub.1 is a moiety selected from the group consisting of: ##STR39## which are useful in augmenting or enhancing the aroma or taste of consumable materials including perfumes, perfumed articles and colognes. The present invention also provides methods for synthesizing such hydrocarbyloxy alkanals by reacting allylic alcohol defined according to the structure: ##STR40## with a chemical compound having an electrophilic center which is a hydrocarbon or hydrocarbyl halide defined according to the structure:

R.sub.1 '--X

wherein R.sub.1 ' is a saturated hydrocarbyl moiety or an unsaturated hydrocarbyl moiety and X is hydrogen or halogen; with the provisos that:

when X is halogen, R.sub.1 ' is saturated hydrocarbyl and

when X is hydrogen, R.sub.1 ' is unsaturated hydrocarbyl;

and wherein R.sub.2 represents hydrogen or methyl. The resulting compound formed has the structure: ##STR41## wherein R.sub.1 and R.sub.2 are defined supra. This compound is then reacted via an oxo reaction with carbon monoxide and hydrogen to form the hydrocarbyloxy alkanals defined according to the structure: ##STR42## according to the reaction sequence: ##STR43##

More specifically, our invention relates to the compound having the structure: ##STR44## This compound of our invention produced according to the process of our invention is capable of augmenting, enhancing or providing natural pine, cypress-like and fir-balsam-like aroma nuances in perfume compositions, colognes and perfumed articles (e.g. perfumed polymers, solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softener articles, drier-added fabric softener articles, fabric softener compositions, cosmetic powders, hair preparations, shampoos and the like).

The compound having the structure: ##STR45## may exist in either the "exo" or "endo" form, that is, having the structures: ##STR46## or the compound shown by the structure: ##STR47## can represent mixtures of both compounds having the structures: ##STR48##

The compound of our invention is produced by first reacting allyl alcohol having the structure: ##STR49## with camphene having the structure: ##STR50## thereby producing a mixture of allyl ethers having the structures: ##STR51## which mixture is primarily the compound having the structure: ##STR52## The mixture is fractionally distilled yielding substantially all compound having the structure: ##STR53## The compound having the structure: ##STR54## is then reacted via an oxo reaction with carbon monoxide and hydrogen to yield a mixture of compounds containing the compound having the structure: ##STR55##

The reaction of the camphene with the allyl alcohol is shown thusly: ##STR56## The reaction of the resulting allyl ether via the oxo reaction with carbon monoxide and hydrogen is shown thusly: ##STR57## wherein the term [K] represents the oxo reaction catalyst.

The reaction of the allyl alcohol with the camphene takes place at a temperature in the range of from about 70.degree. C. up to about 120.degree. C. in the presence of a Lewis acid catalyst such as boron trifluoride etherate, stannic chloride, zinc chloride or aluminum chloride; preferably boron trifluoride etherate. The mole ratio of camphene:allyl alcohol may vary from about 0.5:1 up to about 1:0.5 with a preferred mole ratio of about 1:1.1 camphene:allyl alcohol (the allyl alcohol being in a slight molar excess). The amount of Lewis acid catalyst in the reaction mixture may vary from about 3 grams per liter of reaction mass up to about 15 grams per liter of reaction mass. The time of reaction may vary from about 2 hours up to about 15 hours; but when maintaining the temperature at about 80.degree. C., the time of reaction is about 6 hours when using a boron trifluoride etherate catalyst.

At the end of this reaction, the reaction mass is worked-up by first neutralizing the acid catalyst, e.g. boron trifluoride etherate with an aqueous basic solution, e.g. aqueous sodium carbonate, then washing with water to neutral. The resulting product is then distilled and the distillation product (e.g. via fractional distillation) is used for the second reaction which involves the reaction of the compound having the structure: ##STR58## with a mixture of carbon monoxide and hydrogen via a "oxo" reaction.

The oxo reaction is carried out in the presence of a "oxo reaction catalyst" such as rhodium, Co.sub.2 (CO).sub.8, or an organophosphorous polydentate ligand such as those described in European Published Application No. 33,554 published on Aug. 12, 1981, the specification for which is incorporated herein by reference. Examples of which are: ##STR59## at pressures of from about 3 atmospheres up to about 1,000 atmospheres and at temperatures in the range of from about 30.degree. C. up to about 150.degree. C. Preferably when using a rhodium catalyst, the temperature of reaction is between 70.degree. and 110.degree. C.; when using a Co.sub.2 (CO).sub.8 catalyst, the temperature is between 110.degree. and 120.degree. C.; and when using a ligand such as those exemplified in European Published Application No. 33,554, the temperature may vary from 95.degree. C. up to 120.degree. C. as is set forth in the following table:

                  TABLE A
    ______________________________________
    Ligand           Reaction Temperature
    ______________________________________
    .phi..sub.2 P(CH.sub.2).sub.2 P.phi..sub.2
                      95-120.degree. C.
     ##STR60##       120.degree. C.
     ##STR61##       120.degree. C.
     .phi..sub.2 PCHCHP.phi..sub.2
                     120.degree. C.
     ##STR62##        95.degree. C.
     .phi..sub.2 P(CH.sub.2).sub.4 P.phi..sub.2
                      95.degree. C.
    .phi..sub.2 P(CH.sub.2).sub.3 P.phi..sub.2
                      95.degree. C.
    P.phi..sub.3     120.degree. C.
    .phi..sub.2 P(CH.sub.2).sub.10 P.phi..sub.2
                     120.degree. C.
    .phi..sub.2 PCH.sub.2 P.phi..sub.2
                     120.degree. C.
    (CH.sub.3).sub.2 P(CH.sub.2).sub.2 P(CH.sub.3).sub.2
                     120.degree. C.
    ______________________________________

The amount of norbornyl oxybutyraldehyde prepared in accordance with the process of our invention which will be effective in perfume compositions as well as in perfumed articles (e.g. perfumed polymers, anionic, nonionic, cationic or zwitterionic detergents, soaps, fabric softener compositions, fabric softener articles and hair preparations) and colognes depends upon many fabrics including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 0.01% of the norbornyl oxybutyraldehyde composition prepared in accordance with the process of our invention or even less (e.g. 0.005%) can be used to impart a natural pine, cypress-like, fir-balsam-like aroma to soaps, cosmetics, anionic, cationic, nonionic or zwitterionic detergents, perfumed polymers, fabric softener compositions, fabric softener articles or other products. The amount employed can range up to 70% of the fragrance components and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.

The norbornyl oxybutyraldehyde composition prepared in accordance with the process of our invention is useful (taken alone or taken together with other ingredients in perfume compositions) as an olfactory component in detergents and soaps, space odorants and deodorants, perfumes, colognes, toilet water, bath preparations such as creams, deodorants, hand lotions and sun screens; powders such as talcs, dusting powders, face powders, microporous "perfumed" slow release polymers, (e.g. polyurethane microporous polymers) and the like. When used as an olfactory component in perfumed articles, as little as 0.05% of the norbornyl oxybutyraldehyde prepared in accordance with the process of our invention will suffice to impart a natural pine, cypress-like, fir-balsam-like aroma to pine or lavender formulations. Generally no more than 6% of the norbornyl oxybutyraldehyde composition of our invention based on the ultimate end product is required in the perfumed article.

In addition, the perfume composition or fragrance composition of our invention can contain a vehicle or carrier for the norbornyl oxybutyraldehyde composition prepared in accordance with the process of our invention. The vehicle can be a liquid, such as a non-toxic alcohol (e.g. ethyl alcohol), a non-toxic glycol (e.g. 1,2-propylene glycol) or the like. The carrier can also be an absorbent solid such as a gum (e.g. gum arabic or xanthan gum) or components for encapsulating the composition (such as gelatin) as by coacervation or polymers such as urea formaldehyde polymers.

It will thus be apparent that the norbornyl oxybutyraldehyde prepared in accordance with the process of our invention can be utilized to alter, modify or enhance sensory properties, particularly organoleptic properties such as fragrances of a wide variety of consumable materials.

The following Examples I and II set forth a means for synthesizing the norbornyl oxybutyraldehyde of our invention. The examples following Example II serve to illustrate the organoleptic utilities of the norbornyl oxybutyraldehyde of our invention.

All parts and percentages given herein are by weight unless otherwise specified.

EXAMPLE I

Preparation of isobornyl allyl ether

Reaction: ##STR65##

Into a 2 liter reaction flask equipped with stirrer, thermometer, reflux condenser and addition funnel is placed 201.6 grams of allyl alcohol and 8 grams of boron trifluoride diethyl etherate. The resulting mixture is heated to 80.degree. C. and 680 grams of camphene (5.0 moles) and 100 grams of allyl alcohol in admixture are added to the reaction mass. The reaction mass is then stirred for a period of 6 hours while maintaining same at 80.degree. C. At the end of the reaction, the reaction mass is washed with a sodium carbonate aqueous saturated solution until the pH is 9. The resulting product is then washed with water to neutral and distilled. The first fractional distillation yields the following fractions:

    ______________________________________
              Vapor   Liquid           Weight of
    Fraction  Temp    Temp.     Pressure
                                       Fraction
    Number    (.degree.C.)
                      (.degree.C.)
                                mm/Hg  (grams)
    ______________________________________
    1          49      82       65
    2          64      89       12      41.1
    3         100     105       12     160.8
    4         107     112       12     192.3
    5         109     113       12     199.8
    6         109     114       12
    7         110     143       12
    ______________________________________

    ______________________________________
              Vapor        Liquid
    Fraction  Temp.        Temp.   Pressure
    Number    (.degree.C.) (.degree.C.)
                                   mm/Hg
    ______________________________________
    1         63            93     35
    2         65           106     35
    3         70           109     25
    4         68           106     23
    5         98            99     16
    6         99           100     17
    7         99           100     17
    8         95            95     12
    9         95            95     11
    10        96            96     12
    11        94            96     12
    12        94           100     12
    13        96           210     12
    ______________________________________

    ______________________________________
              Vapor   Liquid           Weight of
    Fraction  Temp.   Temp.     Pressure
                                       Fraction
    Number    (.degree.C.)
                      (.degree.C.)
                                mm/Hg  (grams)
    ______________________________________
    1         119     165       4      13.9
    2         125     175       3      16.1
    3         150     244       3      17.7
    4         195     264       3      13.0
    ______________________________________

    ______________________________________
              Vapor   Liquid           Weight of
    Fraction  Temp.   Temp.     Pressure
                                       Fraction
    Number    (.degree.C.)
                      (.degree.C.)
                                mm/Hg  (grams)
    ______________________________________
    1         94      134       2.8    9.7
    2         95      110       2.6    8.7
    3         62      147       2.6    3.5
    4         102     163       2.4    2.8
    5         114     178       2.4    3.3
    6         70      194       2.8    5.9
    7         64      240       2.9    4.4
    ______________________________________

    ______________________________________
    Ingredients           Parts by Weight
    ______________________________________
    Isobornyl acetate     100
    Camphor               10
    Terpineol             25
    Fir balsam absolute   20
    (50% in diethyl phthalate)
    Coumarin              4
    Linalool              30
    Fenchyl alcohol       10
    Anethol               12
    Lemon terpenes washed 50
    Borneol               5
    Galbanum oil          5
    Turpentine Russian    150
    Eucalyptol            50
    2,2,6-trimethyl-1-cyclohexene-1-
                          12
    carboxaldehyde
    Maltol (1% in diethyl phthalate
                          5
    Bulked fractions 3-5 of the final
                          28
    distillation product of Example II
    consisting essentially of the
    compound having the structure:
     ##STR81##
    ______________________________________

                  TABLE I
    ______________________________________
    Substance           Aroma Description
    ______________________________________
     ##STR82##          A natural pine, cypress- like, fir balsam-like aroma
                        profile.
     (bulked fractions 3-5 of the
    distillation product of the
    reaction product of Example II).
    Perfume composition produced
                        A natural piney aroma
    according to Example II.
                        with cypress and fir
                        balsam-like undertones.
    ______________________________________

    ______________________________________
    Ingredient          Percent by Weight
    ______________________________________
    Neodol .RTM. 45-11 (a C.sub.14 -C.sub.15
                        12
    alcohol ethoxylated with
    11 moles of ethylene oxide)
    Sodium carbonate    55
    Sodium citrate      20
    Sodium sulfate, water brighteners
                        q.s.
    ______________________________________

    ______________________________________
    Dioctyl sebacate   0.05 weight percent
    Benzyl alcohol     0.10 weight percent
    Dow Corning 473 fluid
                       0.10 weight percent
    (prepared by the Dow Corning
    Corporation)
    Tween 20 surfactant
                       0.03 weight percent
    (prepared by ICI America
    Corporation)
    One of the perfumery sub-
                       0.10 weight percent
    stances as set forth in
    Table I of Example IV
    ______________________________________