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Description  |
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BACKGROUND OF THE INVENTION
The present invention relates to dimethyl substituted alkyl nitriles of our
invention defined according to the generic structure:
##STR6##
wherein N represents 0 or 1 and uses thereof to alter, modify or enhance
the aroma of consumable materials.
There has been considerable work performed relating to substances which can
be used to impart (modify, augment or enhance) fragrances to (or in)
various consumable materials. These substances are used to diminish the
use of natural materials, some of which may be in short supply and to
provide more uniform properties in the finished product.
Long-lasting and substantive orris-like, cinnamon-like, sweet, citrus,
lemony, fatty, coconut-like, rhodinol-like, minty, geranium-like and
scorched linen aromas with floral undertones are desirable in several
types of perfume compositions, perfumed articles and colognes.
Furthermore, considerable difficulties have heretofore been encountered in
using compounded hypochlorite bleach or sterilizing solutions with perfume
oils so that a stable long-lasting, single phase commercially feasible
bleach or sterilizing solution has been difficult to obtain, particularly
wherein the desired aroma of the article bleached or sterilized (e.g.,
clothing) has a pleasant and stable and consistent aroma on drying (and
not the usual "hypochlorite-bleached-article" aroma). The problem has been
defined in United Kingdom patent specification No. 886,084 published on
Jan. 3, 1962 wherein it is stated that a stable "dispersion" of
hypochlorite-resistant perfume in aqueous solutions of hypochlorites was
formulated. United Kingdom patent specification No. 886,084 discloses the
preparation of an aqueous "solution" of a hypochlorite containing a
hypochlorite resistant perfume and a surface active quaternary ammonium
compound of the betaine type soluble in the hypochlorite solution. Such
ammonium compounds have the generic structure:
##STR7##
wherein each of R.sub.1 ", R.sub.2 ", R.sub.3 " and R.sub.4 " are alkyl.
One of the features of the perfumed solutions produced in accordance with
said United Kingdom patent specification No. 886,084 is indicated to be
that the solution exhibits foaming properties. Another feature of United
Kingdom patent specification No. 886,084 is stated to be that the perfumed
solutions covered by the patent are found to be clear and homogeneous
after eight weeks of storage at room temperature. Nevertheless, betaines
such as "Ambiteric D" as are discussed therein are not so broadly useful
when used in concentrations of from 0.15% up to 4.0% (based on total
weight of bleach or sterilizing solution) as to have the ability to be
used in conjunction with perfume oils which should be incorporated into
thickened, high viscous hypochlorite bleaches or sterilizers having
excellent surface tension properties so that long lasting stable soluble
single phase thickened perfumed aqueous alkali metal hypochlorite bleach
or sterilizing solutions having long lasting pleasant stable aromas are
obtained, particularly where the quantity of perfume oil in the bleach or
sterilizing substance is at levels of between 0.02% and 0.8% by weight of
the total bleach or sterilizing solution. The need for such aromas (e.g.,
"citrusy") to be present in such bleach or sterilizing solutions exists so
that the disagreeable characteristic "hypochlorite" aroma is substantially
eliminated from aromas of the product to which the bleach or sterilizing
solution is applied; particularly on dry-out, as well as from the aroma of
the hands of the user when they are in direct contact with such bleach or
sterilizing solutions.
U.S. Pat. No. 3,560,389 also discloses the feasibility of using perfume
oils in hypochlorite bleaches or sterilizers at column 3, lines 37-40 but
the disclosure is limited to inclusion of various detergents in addition
to amine oxides, such as lithium lauryl sulfate and sodium lauryl ether
sulfate and/or is further limited to include hydrotropes such as sodium
xylene sulfonate in addition to the amine oxide. Exclusion of such
hydrotropes and detergents additional to the amine oxides and diphenyl
oxide derivatives is desirable not only to cause the dimethyl substituted
alkyl nitriles of our invention to function properly, but also from an
ecological standpoint.
European Chemical News, Volume 13, Jan. 18, 1968, sets forth a synopsis of
South African Pat. No. 67/4667 which corresponds to U.S. Pat. No.
3,560,389, but the reference also states at page 42:
"Alternatively, a detergent with bleaching or bacteriocidal properties can
be formulated. Perfuming bleaching solutions is now possible."
Neither the South African nor the United States Patents, however, indicate
the advantages and usefulness of limiting the detergents either to (a)
compounds having the generic structure:
##STR8##
wherein at least one of R.sub.1 and R.sub.2 represents C.sub.10 -C.sub.12
straight chain or branched chain alkyl and when one of R.sub.1 or R.sub.2
is C.sub.10 -C.sub.12 branched or straight chain alkyl, the other of
R.sub.1 or R.sub.2 is pH-adjusted hydrogen and wherein M.sub..alpha. and
M.sub..beta. are the same or different and each represents alkali metal
which may be sodium, lithium or potassium, or (b) to mixtures of compounds
having the structure:
##STR9##
with at least one amine oxide defined according to the structure:
##STR10##
of excluding from the formulation a hydrotrope or of specifying the nature
of the perfume oil useful in the perfumed bleach or sterilizing solution
(wherein A and B are each separately methyl or taken together, complete a
morpholino ring and wherein R.sub.3 '" is straight chain alkyl having from
11 up to 13 carbon atoms).
U.S. Pat. No. 3,876,551, in attempting to solve the foregoing problem
discloses a stable single phase aqueous alkali metal hypochlorite liquid
perfume bleach or sterilizing composition comprising an aqueous mixture of
(1) an amine oxide composition consisting essentially of at least one
morpholino- and/or dimethyl (C.sub.11 -C.sub.13 straight chain alkyl)
amine oxide in an amount greater than 55% of said amine oxide composition,
(2) at least one alkali metal hydroxide, (3) at least one alkali metal
hypochorite, and (4) a perfume oil compatible with the mixture capable of
imparting a "woody" or a "floral" or a "clean fresh" or a "citrusy" note
to the bleach or sterilizing composition; the mixture having a pH in the
range of from 12 to 13.5 and the mixture excluding hydrotropes as well as
all surfactants except the amine oxide.
Included in the perfume compositions of U.S. Pat. No. 3,876,551 are:
(i) at column 6, lines 5 and 6: long chain aliphatic nitriles such as
n-dodecyl nitriles; and
(ii) at column 6, line 29: n-undecyl nitrile.
U.S. Pat. No. 3,876,551 also attempts to solve the foregoing problem by
setting forth a process for producing the above-named mixture comprising
the steps of combining an amine oxide composition consisting essentially
of one or more morpholino and/or dimethyl C.sub.11 -C.sub.13 straight
chain alkyl amine oxide(s) with the perfumed oil to form an amine
oxide-perfume oil premix; admixing the amine oxide-perfumed oil premix
with an aqueous alkali metal hypochlorite solution, and combining the
alkali metal hydroxide with the solution whereby the final pH of the
mixture is from 12 up to 13.5. In a further effort to solve the foregoing
problem U.S. Pat. No. 3,876,551 also discloses adjustment of the pH of the
aqueous metal hypochlorite solution initially to the range of 12-13.5 and
then combining the resulting aqueous hypochlorite solution with the
aforementioned premix. The resulting composition is indicated to cause
products to which said composition is applied to have eliminated therefrom
the disagreeable characteristics "hypochlorite" aroma and instead to have
a "clean fresh" or "floral" or "woody" or "citrusy" aroma to be imparted
to the treated products. In addition, it is stated that the hands of the
individual user after using and being in direct contact with the
hypochlorite composition will not have the disagreeable characteristics
"hypochlorite" aroma but instead will have a pleasant "clean fresh" or
"floral" or "woody" or "citrusy" aroma.
The disadvantage of the system of U.S. Pat. No. 3,876,551 however, concerns
(a) the inability to use a thickener in the system whereby the resulting
liquid has a viscosity of 5-25 centipoises at 20.degree.-40.degree. C. and
(b) the relatively low degree of chemical stability and substantive
stability of the perfume oil and of the single liquid phase system.
Nothing in U.S. Pat. No. 3,876,551 indicates such a high degree of
stabilities of the perfume-hypochlorite system as exists in the system of
the present invention; wherein there is also included a thickener. Indeed,
the stabilities using the system of the instant invention are far greater
even at levels as low as 3% hypochlorite and are also relatively stable
(from a standpoint of chemical stability of perfume oil, substantive
stability of perfume oil and phase separation stability taken in
combination with one another) at levels of as high as 10% hypochlorite in
aqueous solution. Thus, the instant system gives rise to unexpected,
unobvious and advantageous properties over the systems taught in the prior
art.
Furthermore, nothing in the prior art including the teaching of U.S. Pat.
No. 3,876,551 states either explicitly or implicitly the compatability of
a thickener in the instant system, such as sodium palmitate, sodium
stearate, potassium palmitate, potassium stearate, lithium palmitate,
lithium stearate, lithium laurate, potassium laurate or sodium laurate
whereby a stable gel (as opposed to a liquid) phase perfumed hypochlorite
system or perfumed oil stabilizer emulsifier system "premix" may be
produced.
The combination of the compound group having the structure:
##STR11##
(wherein R.sub.1, R.sub.2, M.sub..alpha. and M.sub..beta. are defined,
supra) with perfume and hypochlorite bleach in general, is set forth in
the Kao Soap Company, Japanese Patent No. 25514/79 filed on Nov. 2, 1973
and opened for public inspection on June 19, 1975. Thus, on page 2, at
column 4, line 15, the compound:
##STR12##
is disclosed for use in conjunction with the perfumed hypochlorite
bleaches. The claim of the Kao Soap Patent is as follows:
Claim: An aromatic liquid bleaching composition containing, as active
ingredient, sodium hypochlorite, which comprises one or more of simple
perfumes or compounded perfumes selected from the group consisting of
anisole, benzophenone, benzylphenyl ether, bromelia, cedrenyl acetate,
p-tertiary butylcyclohexanol, dimethylbenzylcarbinyl acetate,
dihydroterpinyl acetate, diphenyl oxide, dimethylbenzylcarbinol,
dimethylphenylcarbinol, dihydroterpineol, fenchyl acetate, fenchyl
alcohol, p-methyldimethylbenzylcarbinol, methylphenylcarbinyl acetate,
methyl-n-valerate, muskmoskene, muscarone, methylamyl ketone,
phenylethyldimethylcarbinyl acetate, rose phenone, styrallyl propionate,
tetrahydromuguol, tetrahydromugyl acetate, tetrahydrolinalool,
tetrahydrolinalyl acetate, verool, velveton, verdox, coniferan and yara
yara, and a surface active agent which can stably be dissolved in an
aqueous solution of sodium hypochlorite.
Furthermore, the use of such compounds as those having the structure:
##STR13##
(wherein R.sub.1, R.sub.2, M.sub..alpha. and M.sub.62 have been
previously defined) with hypochlorite bleaches is documented in the
brochure of Dow Chemical entitled "DOWFAX Surfactants" and is covered in
the Dow Chemical Company Pat. No. 3,172,861 issued on Mar. 9, 1965.
Nothing in the prior art discloses, however, the utility of the thickeners
of the instant application taken together with a perfume oil (e.g.,
"diisoamylene" or "diisoamylene epoxide") and one of the compounds defined
according to the generic structure:
##STR14##
(wherein R.sub.1, R.sub.2, M.sub.60 and M.sub..beta. have been defined,
supra) in hypochlorite bleaches, particularly where the hypochlorite
concentration is greater than 7%. More particularly, nothing in the prior
art discloses the use of such systems in conjunction with a thickener such
as sodium palmitate, potassium palmitate, sodium stearate, potassium
stearate, sodium laurate, potassium laurate, lithium laurate, lithium
stearate or lithium palmitate, whereby a stable gelled perfumed
hypochlorite mixture is formed or whereby a "premix" gel-phase perfume
oil-stabilizing/emulsifying agent is formed.
The dimethyl substituted alkyl nitriles of our invention are unique insofar
as the aforementioned systems are concerned for use in hypochlorite
bleaches. Nothing in the prior art discloses any organic compounds even
remotely similar to the dimethyl substituted alkyl nitriles of our
invention for use as a stable aroma augmenting or enhancing agent in
hypochlorite bleaches.
However, the use of nitriles in perfumery is well known in the prior art as
will be seen by reference to the following publications:
(i) U.S. Pat. No. 3,325,369 issued on June 13, 1967 and reissue Pat. No.
27332 disclose the compound having the structure:
##STR15##
for use in perfumery; (ii) U.S. Pat. Nos. 3,553,110 issued on Jan. 5,
1971 and 3,655,722 issued on Apr. 11, 1972 disclose the compound having
the structure:
##STR16##
for use in perfumery. (iii) Dutch published application No. 76/08847
discloses the compound having the structure:
##STR17##
for use in perfumery; (iv) Arctander "Perfume And Flavor Chemicals"
(Aroma Chemicals) published by the author in 1969 discloses:
(a) at Monograph No. 764, the perfumery use of the compound having the
structure:
##STR18##
(b) at Monograph No. 839, the perfumery use of the compound having the
structure:
##STR19##
(c) at Monograph No. 1121, the perfumery use of the compound having the
structure:
##STR20##
(d) at Monograph No. 2292, the perfumery use of the compound having the
structure:
##STR21##
Furthermore, available to the industry is a compound entitled "MNA" nitrile
having the structure:
##STR22##
Furthermore, "Perfumer & Flavorists International" published in 1980 by
Allured Publishing Corporation, Volume 4, No. 6, commencing on page 1, an
article by Dr. Robert DeSimone entitled "Nitriles in perfumery" wherein a
number of nitriles are disclosed as having perfumery properties.
Nothing in the prior art however discloses the perfumery use, particularly
for uses in bleaches of the dimethyl substituted alkyl nitriles of our
invention.
Biostein, Volume II, at page 153, discloses that the compound having the
structure:
##STR23##
has a "citrus aroma" (translated from "Riecht Citronenartig").
The dimethyl substituted alkyl nitriles of our invention are unique with
respect to hypochlorite bleach systems. Nothing in the prior art discloses
any organic compounds even remotely similar to the dimethyl substituted
alkyl nitriles of our invention for use as stable aroma augmenting or
enhancing agents in hypochlorite bleaches. Furthermore, nothing in the
prior art implies the dimethyl substituted alkyl nitriles of our invention
are useful in augmenting or enhancing the aroma of perfume compositions,
colognes or perfumed articles.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is the GLC profile for the reaction product of Example I, containing
the compound having the structure:
##STR24##
(Conditions: OV-1 column programmed at 80.degree.-220.degree. C. at
2.degree. C. per minute)
FIG. 2 is the GLC profile for the reaction product of Example II,
containing the compound having the structure:
##STR25##
(Conditions: Methyl silicone column programmed at 80.degree.-220.degree.
C. at 2.degree. C. per minute).
FIG. 3 is the GLC profile for the crude reaction product of Example III,
containing the compound having the structure:
##STR26##
(Conditions: SE-30 column programmed at 150.degree. C. isothermal).
FIG. 4 is the GLC profile for the reaction product of Example III,
containing the compounds having the structures:
##STR27##
FIG. 5 is the NMR spectrum for the compound having the structure:
##STR28##
produced according to Example III.
FIG. 6 is the NMR spectrum for the compound having the structure:
##STR29##
produced according to Example IV.
FIG. 7 is the GLC profile for the reaction product of Example V, containing
the compound having the structure:
##STR30##
FIG. 8 is the GLC profile for the reaction product of Example V, containing
the compound having the structure:
##STR31##
FIG. 9 is the NMR spectrum for the compound having the structure:
##STR32##
produced according to Example V.
FIG. 10 represents a cut-away side elevation view of apparatus used in
forming perfumed polymers which contain imbedded therein at least one of
the dimethyl substituted alkyl nitriles of our invention.
FIG. 11 is a front view of the apparatus of FIG. 10 looking in the
direction of the arrows.
DETAILED DESCRIPTION OF THE DRAWINGS
FIG. 1 is the GLC profile for the reaction product of Example I
(Conditions: bonded methyl silicone (OV-1) column programmed at
80.degree.-220.degree. C. at 2.degree. C. per minute). The peak indicated
by reference numeral 10 is the peak for the isopropyl alcohol solvent. The
peak indicated by reference numeral 12 is the peak for the reaction
product having the structure:
##STR33##
FIG. 2 is the GLC profile for the crude reaction product of Example II
(Conditions: Methyl silicone column programmed at 80.degree.-220.degree.
C. at 2.degree. C. per minute). The peak indicated by reference numeral 21
is the peak for the toluene solvent. The peak indicated by reference
numeral 22 is the peak for the compound which is a byproduct of the
reaction having the structure:
##STR34##
The peak indicated by reference numeral 23 is the peak for the compound
having the structure:
##STR35##
FIG. 3 is the GLC profile for the crude reaction product of Example III
((Conditions: SE-30 column programmed at 150.degree. C. isothermal). The
peak indicated by reference numeral 31 is the peak for the solvent. The
peak indicated by reference numeral 33 is the peak for the reaction
product which is the compound having the structure:
##STR36##
FIG. 4 is the GLC profile for the oxime intermediate reaction product of
Example III. The peak indicated by reference numeral 41 is the peak for
the compound having the structure:
##STR37##
The peak indicated by reference numeral 42 and the peak indicated by
reference numeral 43 are for the compound having the structure:
##STR38##
FIG. 7 is the GLC profile for the reaction product of Example V
(Conditions: SE-30 column programmed at 180.degree. C. isothermal). The
peak indicated by reference numeral 91 is the peak for the compound having
the structure:
##STR39##
FIG. 8 is the GLC profile for the reaction product of Example V. The peak
indicated by reference numeral 82 is the peak for the compound having the
structure:
##STR40##
Referring to FIGS. 10 and 11, there is provided a process for forming
scented polymer elements (wherein the polymer may be a thermoplastic
polymer such as low density polyethylene or polypropylene or copolymers of
ethylene and vinyl acetate or mixtures of polymers and copolymers such as
copolymers of ethylene and vinyl acetate and polyethylene) such as pellets
useful in the formation of plastic particles useful in fabricating certain
articles which may be perfumed (and, further, which may be exposed to
chlorine bleaches). This process comprises heating the polymer or mixture
of polymers to the melting point of said polymer or mixture of polymers,
e.g., 250.degree. C. in the case of low density polyethylene. The lower
most portion of the container is maintained at a slightly lower
temperature and the material in the container is taken off at such
location for delivery through the conduit. Thus, referring to FIGS. 10 and
11, in particular, the apparatus used in producing such elements comprises
a device for forming the polymer containing the perfume, e.g.,
polyethylene or polyethylene-polyvinyl acetate or mixtures of same or
polypropylene, which comprises a vat or container 212 into which the
polymer taken alone or in admixture with other copolymers and the
perfuming substance which is at least one of the dimethyl substituted
alkyl nitriles of our invention or mixtures of dimethyl substituted alkyl
nitriles of our invention and other compatible perfumes is placed. The
container is closed by means of an air-tight lid 228 and clamped to the
container by bolts 265. A stirrer 273 traverses the lid or cover 228 in an
air-tight manner and is rotatable in a suitable manner. A surrounding
cylinder 212A having heating coils which are supplied with electric
current through cable 214 from a rheostat or control 216 is operated to
maintain the temperature inside the container 212 such that the polymer in
the container will be maintained in the molten or liquid state. It has
been found advantageous to employ polymers at such a temperature that the
viscosity will be in the range of 90-100 sayboldt seconds. The heater 218
is operated to maintain the upper portion of the container 212 within a
temperature range of, for example, 220.degree.-270.degree. C. in the case
of low density polyethylene. The bottom portion of the container 212 is
heated by means of heating coils 212A regulated through the control 220
connected thereto through a connecting wire 222 to maintain the lower
portion of the container 212 within a temperature range of
220.degree.-270.degree. C.
Thus, the polymer or mixture of polymers added to the container 212 is
heated from 10-12 hours, whereafter the perfume composition or perfume
material which contains one or more of the dimethyl substituted alkyl
nitriles of our invention is quickly added to the melt. Generally, about
10-45 percent by weight of the resulting mixture of the perfumery
substance is added to the polymer.
After the perfume material is added to the container 212, the mixture is
stirred for a few minutes, for example, 5-15 minutes and maintained within
the temperature ranges indicated previously by the heating coil 212A. The
controls 216 and 220 are connected through cables 224 and 226 to a
suitable supply of electric current for supplying the power for heating
purposes.
Thereafter, the valve "V" is opened permitting the mass to flow outwardly
through conduit 232 having a multiplicity of orifices 234 adjacent to the
lower side thereof. The outer end of the conduit 232 is closed so that the
liquid polymer in intimate admixture with one or more of the dimethyl
substituted alkyl nitriles of our invention or mixture of dimethyl
substituted alkyl nitriles of our invention and one or more other
substances (optionally), will continuously drop or drip through the
orifices 234 downwardly from the conduit 232. During this time, the
temperature of the polymer intimately admixed with the perfumery substance
in the container 212 is accurately controlled so that a temperature in the
range of from about 240.degree.-250.degree. C., for example, (in the case
of low density polyethylene) will exist in the conduit 232. The regulation
of the temperature through the controls 216 and 220 is essential in order
to insure temperature balance to provide for the continuous dripping or
dropping of molten polymer intimately admixed with the perfume substance
which is all of or which contains one or more of the dimethyl substituted
alkyl nitriles of our invention through the orifices 234 at a rate which
will insure the formation of droplets 236 which will fall downwardly onto
a moving conveyor belt 238 caused to run between conveyor wheels 240 and
242 beneath the conduit 232.
When the droplets 236 fall onto the conveyor 238, they form pellets 244
which harden almost instantaneously and fall off the end of the conveyor
238 into a container 250 which is advantageously filled with water or some
other suitable cooling liquid to insure the rapid cooling of each of the
pellets 244. The pellets 244 are then collected from the container 250 and
utilized for the formation of functional products, e.g., garbage bags and
the like.
THE INVENTION
The invention provides dimethyl substituted alkyl nitriles of our invention
defined according to the generic structure:
##STR41##
wherein N represents 0 or 1.
The dimethyl substituted alkyl nitriles of our invention produced according
to the process of our invention are capable of augmenting or enhancing
orris-like, cinnamon-like, sweet, citrus, lemony, fatty, coconut-like,
rhodinol-like, minty, geranium-like and scorched linen aromas with floral
undertones in perfume compositions, colognes and perfumed articles
including soaps, bleaches, nonionic, cationic, anionic and zwitterionic
detergents, fabric softener articles and perfumed articles.
The present invention also relates to process intermediates for producing
said dimethyl substituted alkyl nitriles of our invention which process
intermediates are defined according to the generic structure:
##STR42##
wherein N is 0 or 1
The dimethyl substituted alky nitriles of our invention are produced using
as starting materials compounds defined according to the generic
structure:
##STR43##
wherein N is 0 or 1. These aldehydes are selectively hydrogenated whereby
the carbon-carbon double bond moiety is reduced to a carbon-carbon single
bond and the aldehyde moiety is retained intact thereby forming the group
of compounds defined according to the structure:
##STR44##
The compounds defined according to the structure:
##STR45##
are then reacted with a hydroxyl amine salt defined according to the
structure:
##STR46##
where Y represents an anion such as sulfate, chloride or bromide and P is
1 or 2 followed by reaction with base to form an aldoxime composition
defined according to the structure:
##STR47##
The resulting aldoxime having the structure:
##STR48##
is then reacted with an appropriate conversion reagent to form the desired
nitrile having the structure:
##STR49##
The resulting nitrile is then fractionally distilled from the reaction mass
or otherwise separated in order to form the desired material useful in
augmenting or enhancing the aroma of perfume compositions, colognes or
perfumed articles.
In carrying out the reaction of the compounds defined according to the
structure:
##STR50##
in order to form the compounds defined according to the structure:
##STR51##
this reaction takes place at a temperature of from about 75.degree. C. up
to about 130.degree. C. and a pressure of from about 100 up to about 1000
psig (pounds per square inch gauge) in the presence of a hydrogenation
catalyst with hydrogen according to the reaction:
##STR52##
The hydrogenation catalyst must be such that it will selectively reduce
the carbon-carbon double bond but not reduce the aldehyde moiety. Thus, we
have found that the following palladium-containing catalysts are useful in
the practice of this aspect of our invention:
(i) Palladium on calcium carbonate;
(ii) Palladium on carbon;
(iii) Palladium (II) acetate;
(iv) Palladium (II) acetylacetonate;
(v) Palladium (II) bromide;
(vi) Palladium (II) chloride;
(vii) Palladium hydroxide on carbon;
(viii) Palladium (II) iodide;
(ix) Palladium (II) nitrate hydrate;
(x) 1% Palladium on activated carbon;
(xi) 3% Palladium on activated carbon;
(xii) 5% Palladium on activated carbon;
(xiii) 10% Palladium on activated carbon;
(xiv) 1% Palladium on alumina;
(xv) 5% Palladium on alumina;
(xvi) 0.5% Palladium on alumina;
(xvii) 5% Palladium on barium carbonate;
(xviii) 5% Palladium on barium sulfate;
(xix) 5% Palladium on calcium carbonate;
(xx) 5% Palladium on calcium carbonate poisoned with lead (Lindar
catalyst);
(xxi) 0.5% Palladium on 4 to 8-mesh carbon;
(xxii) 1% Palladium on 4 to 8-mesh carbon;
(xxiii) 5% Palladium sulfide on carbon;
(xxiv) Palladium (II) oxide;
(xxv) Palladium (II) oxide hydrate;
(xxvi) 20-40 Mesh Palladium-poly(ethylenimine);
(xxvii) 40-200 Mesh Palladium-poly(ethylenimine);
(xxviii) Palladium (II) sulfate; and
(xxix) Palladium (II) trifluoroacetate.
In carrying out the reaction of the aldehydes defined according to the
structure:
##STR53##
in order to form the aldoximes having the structure:
##STR54##
which reaction is set forth, thusly:
##STR55##
this reaction is carried out at 0.degree.-40.degree. C. at atmospheric
pressure. The reaction is a two-stage reaction with the first stage being
the reaction of the aldehyde having the structure:
##STR56##
with the hydroxylamine salt having the structure:
##STR57##
(e.g., hydroxylamine hydrochloride or hydroxylamine sulfate). The second
stage of the reaction is reaction with base with or without inert solvent.
The base can be sodium hydroxide or calcium hydroxide (with e being 1 or
2).
In carrying out the dehydration of the aldoxime to form the nitrile the
reaction is as follows:
##STR58##
This reaction is carried out in refluxing inert solvent at a temperature
in the range of from about 80.degree. C. up to about 150.degree. C. The
dehydrating reagent "R" may be acetic anhydride, phosphorous trichloride,
phosphorous oxychloride or thionylchloride. In place of acetic anhydride
other organic anhydrides may be used such as propionic anhydride or mixed
acetic-propionic anhydride defined according to the structure:
##STR59##
wherein R.sub.1 and R.sub.2 are the same or different methyl or ethyl.
Specific examples of the dimethyl substituted alkyl nitriles of our
invention produced according to the foregoing process and useful for the
practice of our invention are set forth in Table I below:
TABLE I
______________________________________
Description of Composition
With Structures: Perfumery Evaluation
______________________________________
##STR60## An orris-like, cinnamon-like aroma profile with floral
undertones.
prepared according
to Example V, bulked
distillation fractions
8-12.
##STR61## A sweet, citrus (tart-lemon), cinnamic, fatty, lactonic
coconut) aroma profile.
prepared according
to Example V, distillation
fraction 11.
##STR62## A rhodinal, minty, geranium- like profile.
prepared according
to Example II, bulked
distillation fractions
8-20.
##STR63## A citrusy, fatty, scorched linen aroma profile.
prepared according
to Example III, bulked
distillation fractions
5-15.
______________________________________
The dimethyl substituted alkyl nitriles of our invention and one or more
auxiliary perfume ingredients, including, for example, hydrocarbons,
alcohols, ketones, aldehydes, nitriles other than the nitriles of our
invention, esters, lactones, ethers, synthetic essential oils and natural
essential oils may be admixed so that the combined odors of the individual
components produce a pleasant and desired fragrance, particularly and
preferably in the citrusy and/or green, woody fragrances.
Such perfume compositions usually contain (a) the main note or the
"bouquet" or foundation stone of the composition; (b) modifiers which
round off and accompany the main note; (c) fixatives which include odorous
substances which lend a particular note to the perfume throughout all
stages of evaporation and substances which retard evaporation; and (d)
topnotes which are usually low boiling fresh smelling materials.
In perfume compositions, it is the individual components which contribute
to their particular olfactory characteristics, however the overall sensory
effect of the perfume composition will be at least the sum total of the
effects of each of the ingredients. Thus, one or more of the dimethyl
substituted alkyl nitriles of our invention can be used to alter, modify
or enhance the aroma characteristics of a perfume composition, for
example, by utilizing or moderating the olfactory reaction contributed by
another ingredient in the composition.
The amount of one or more of the dimethyl substituted alkyl nitriles of our
invention which will be effective in perfume compositions as well as in
perfumed articles and colognes depends upon many factors, including the
other ingredients, their amounts and the effects which are desired. It has
been found that perfume compositions containing as little as 0.05% of one
or more of the dimethyl substituted alkyl nitriles of our invention or
even less (e.g., 0.02%) can be used to impart orris-like, cinnamon-like,
sweet, citrus, lemony, fatty, coconut-like, rhodinol-lik | | |
