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Description  |
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BACKGROUND OF THE INVENTION
This invention relates to tertiary hydroxyl carboxaldehydes defined
according to the structure:
##STR9##
wherein the lines
##STR10##
represent covalent carbon-carbon bonds when m does not=0; and wherein the
lines
##STR11##
do not represent any bonds when m=0; wherein R represents hydrogen or
methyl; wherein p and q each represents 0 or 1 with the proviso that p=1
when q=0 and p=0 when q=1; wherein X and Z each represent one or more
carbon atoms required to complete a bicyclo ring with the lines
##STR12##
representing carbon-carbon bonds; wherein X and Z complete a phenyl moiety
when the line
##STR13##
represents no bond; wherein X and Z complete a cycloalkyl ring moiety with
the lines
##STR14##
represent carbon-carbon bonds and with the line
##STR15##
representing no bond; and wherein when m is 0, X represents an alkylene
moiety, produced according to an oxo reaction on a member of the
unsaturated genus having the structure:
##STR16##
and organoleptic uses thereof particularly augmenting or enhancing the
aroma of perfume compositions, colognes and perfumed articles.
Inexpensive chemical compounds which can provide woody, nutty, floral,
lilac, green, peach-like, balsamic and fresh air dried linen aromas with
minty, floral, cinnamon-like and green topnotes 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
and perfumed articles 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 replace, 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 the
compositions.
U.S. Pat. No. 4,357,247 issued on Nov. 2, 1982 discloses aliphatic C.sub.11
branched chain aldehydes and alcohols, defined according to the generic
structure:
##STR17##
wherein one of X.sub.1 or X.sub.2 is hydrogen and the other of X.sub.1 or
X.sub.2 is methyl; and wherein one of Z.sub.1 or Z.sub.2 is hydrogen and
the other of Z.sub.1 or Z.sub.2 is hydroxymethyl having the structure:
##STR18##
or carboxaldehyde having the structure:
##STR19##
for use in augmenting or enhancing the aroma of perfume compositions,
colognes and perfumed articles. The resulting compounds and compositions
of matter provide citrusy, green, melony, woody, peanut oil-like and
vetiver-like aroma nuances. The compounds of U.S. Pat. No. 4,357,247 are
different in kind insofar as their structure and organoleptic properties
are concerned from the compounds of the instant application.
Furthermore, C.sub.11 aliphatic alcohols and aldehydes are well known in
the art of perfumery, e.g., n-undecanal and n-undecanol. Oxo reaction
products on hydrocarbon compounds are also well known in the perfumery
industry aside from U.S. Pat. No. 4,357,247. Thus, U.S. Pat. No. 4,146,505
discloses the formation of hydroxymethyl-formyl-tricyclo[5,2,1,0.sup.2,6
]decane having the structure:
##STR20##
wherein R.sub.1 and R.sub.2 are the hydroxymethyl group, CH.sub.2 OH or
the formyl group CHO and R.sub.1 represents CH.sub.2 OH when R.sub.2 is
CHO and vice versa. This polycyclic carboxaldehyde alcohol is indicated to
be useful as a musk aroma imparting or augmenting material. The material
is indicated to be produced by reaction of carbon monoxide and hydrogen
with dicyclopentadiene. Other oxo reaction products on unsaturated
hydrocarbons are known in the perfumery industry, for example, "Vandor-B",
which is the oxo reaction product of carbon monoxide and hydrogen on
diiosbutylene. This material has been produced by International Flavors &
Fragrances Inc., the assignee of the instant patent application, for
several years.
Nothing in the prior art however, discloses the compounds defined according
to the structure:
##STR21##
produced by oxo reaction on compounds defined according to the structure:
##STR22##
wherein the lines
##STR23##
represent covalent carbon-carbon bonds when m does not=0; and wherein the
lines
##STR24##
do not represent any bonds when m=0; wherein R represents hydrogen or
methyl; wherein p and q each represents 0 or 1 with the proviso that p=1
when q=0 and p=0 when q=1;
wherein X and Z each represent one or more carbon atoms required to
complete a bicyclo ring with the lines
##STR25##
representing carbon-carbon bonds; wherein X and Z complete a phenyl moiety
when the line
##STR26##
represents no bond; wherein X and Z complete a cycloalkyl ring moiety with
the lines
##STR27##
represent carbon-carbon bonds and with the line
##STR28##
representing no bond; and wherein when m is 0, X represents an alkylene
moiety.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is the GLC profile for fraction 6 of the distillation product of the
reaction product containing the compounds having the structures:
##STR29##
FIG. 2 is the NMR spectrum for the peak indicated by reference numeral "11"
of the GLC profile of FIG. 1 for the compound having the structure:
##STR30##
(Conditions: Field strength 100 MHz; Solvent: CFCl.sub.3).
FIG. 3 is the NMR spectrum for the peak indicated by reference numeral "12"
of the GLC profile of FIG. 1 for the compound having the structure:
##STR31##
(Conditions: Field strength: 100 MHz; Solvent: CFCl.sub.3).
FIG. 4 is the NMR spectrum for the peak indicated by reference numeral "
13" of the GLC profile of FIG. 1 containing the compounds having the
structures:
##STR32##
(Conditions: Field strength: 100 MHz; Solvent: CFCl.sub.3).
FIG. 5 is the GLC profile for the crude reaction product produced according
to Example II containing the compounds having the structures:
##STR33##
FIG. 6 is the GLC profile for Fraction 1 of the re-distillation product of
Example II containing the compounds defined according to the structures:
##STR34##
FIG. 7 is the NMR spectrum for a mixture of compounds having the
structures:
##STR35##
produced according to Example II. (Conditions: Field strength: 100 MHz;
Solvent: CFCl.sub.3).
FIG. 8 is the infra-red spectrum for the mixture of compounds having the
structures:
##STR36##
produced according to Example II.
FIG. 9 is the GLC profile for bulked fractions 5 and 6 of the first
distillation of the reaction product of Example III containing the
compound having the structure:
##STR37##
FIG. 10 is the NMR spectrum for Fraction 6 of the first distillation of the
reaction product of Example III containing the compound having the
structure:
##STR38##
(Conditions: Field strength: 100 MHz; Solvent: CFCl.sub.3).
FIG. 11 is the infra-red spectrum for Fraction 6 of the first distillation
of the reaction product of Example III containing the compound having the
structure:
##STR39##
FIG. 12 is the GLC profile for the crude reaction product of Example IV
containing the compounds defined according to the structures:
##STR40##
FIG. 13 is the GLC profile for Fraction 6 of the second distillation of
Example IV containing the compound having the structure:
##STR41##
FIG. 14 is the NMR spectrum for Fraction 4 of the second distillation of
Example IV containing the compound having the structure:
##STR42##
(75%) and the compound having the structure:
##STR43##
(25%). (Conditions: Field strength: 100 MHz; Solvent: CFCl.sub.3).
DETAILED DESCRIPTION OF THE DRAWINGS
FIG. 1 is the GLC profile for fraction 6 of the distillation product of the
reaction product of Example I. The peak indicated by reference numeral
"11" is the peak for the compound having the structure:
##STR44##
The peak indicated by reference numeral "12" is the peak for the compound
having the structure:
##STR45##
The peak indicated by reference numeral "13" is the peak for the compound
having the structure:
##STR46##
in admixture with the compound having the structure:
##STR47##
(conditions of GLC operation: Carbowax column programmed at
100.degree.-220.degree. C., isothermal).
FIG. 5 is the GLC profile for the crude reaction product of Example II. The
peak indicated by reference numeral "51" is the peak for the mixture of
compounds defined according to the structures:
##STR48##
The peak indicated by reference numeral "52" is the peak for the starting
material having the structure:
##STR49##
The peak indicated by reference numeral "53" is the peak for the reaction
solvent, toluene.
FIG. 12 is the GLC profile for the crude reaction product of Example IV.
The peak indicated by reference numerals "122" and "123" are the peaks for
the compounds defined according to the structures:
##STR50##
The peak indicated by reference numeral "121" is the peak for the reaction
solvent, toluene.
THE INVENTION
It has now been determined that tertiary hydroxyl carboxaldehydes defined
according to the generic structure:
##STR51##
wherein the lines
##STR52##
represent covalent carbon-carbon bonds when m does not=0; and wherein the
lines
##STR53##
do not represent any bonds when m=0; wherein R represents hydrogen or
methyl; wherein p and q each represents 0 or 1 with the proviso that p=1
when q=0 and p=0 when q=1; wherein X and Z each represent one or more
carbon atoms required to complete a bicyclo ring with the lines
##STR54##
representing carbon-carbon bonds; wherein X and Z complete a phenyl moiety
when the line
##STR55##
represents no bond; wherein X and Z complete a cycloalkyl ring moiety with
the lines
##STR56##
represent carbon-carbon bonds and with the line
##STR57##
representing no bond; and wherein when m is 0, X represents an alkylene
moiety, are capable of imparting, augmenting or enhancing a variety of
fragrances in or to consumable materials.
Briefly, our invention contemplates augmenting or enhancing fragrances of
such consumable materials as perfumes, perfumed articles, (e.g., solid or
liquid anionic, cationic, nonionic or zwitterionic detergents, cosmetic
powders, fabric softener compositions, drier-added fabric softener
articles and perfumed polymers) and colognes by adding thereto a small,
but effective, amount of at least one of the compounds defined according
to the generic structure:
##STR58##
wherein the lines
##STR59##
represent covalent carbon-carbon bonds when m does not=0; and wherein the
lines
##STR60##
do not represent any bonds when m=0; wherein R represents hydrogen or
methyl; wherein p and q each represents 0 or 1 with the proviso that p=1
when q=0 and p=0 when q=1; wherein X and Z each represent one or more
carbon atoms required to complete a bicyclo ring with the lines
##STR61##
representing carbon-carbon bonds; wherein X and Z complete a phenyl moiety
when the line
##STR62##
represents no bond; wherein X and Z complete a cycloalkyl ring moiety with
the lines
##STR63##
represent carbon-carbon bonds and with the line
##STR64##
representing no bond; and wherein when m is 0, X represents an alkylene
moiety.
More specifically, the structures of the compounds useful in practicing our
invention are as follows:
##STR65##
The tertiary hydroxyl carboxaldehydes of our invention augment or enhance
woody, nutty, floral, lilac, peach-like, green, balsamic and fresh air
dried linen aromas adding thereto minty, floral, cinnamon-like and green
topnotes to perfumes, perfumed articles and colognes thereby causing one
or more of said tertiary hydroxyl carboxaldehydes to be useful
particularly in vetiver type and "fresh air dried linen" type fragrances.
The tertiary hydroxyl carboxaldehydes of our invention may be prepared by
first (i) reacting unsaturated compounds defined according to the generic
structure:
##STR66##
with carbon monoxide and hydrogen in the presence of a "oxo" reaction
catalyst according to the reaction:
##STR67##
wherein the lines
##STR68##
represent covalent carbon-carbon bonds when m does not=0; and wherein the
lines
##STR69##
do not represent any bonds when m=0; wherein R represents hydrogen or
methyl; wherein p and q each represents 0 or 1 with the proviso that p=1
when q=0 and p=0 when q=1; wherein X and Z each represent one or more
carbon atoms required to complete a bicyclo ring with the lines
##STR70##
representing carbon-carbon bonds; wherein X and Z complete a phenyl moiety
when the line
##STR71##
represents no bond; wherein X and Z complete a cycloalkyl ring moiety with
the lines
##STR72##
represent carbon-carbon bonds and with the line
##STR73##
representing no bond; and wherein when m is 0, X represents an alkylene
moiety. The reaction is carried out at temperatures of between 110.degree.
C. and 300.degree. C. at pressures of between 15 and 250 atmospheres; with
the ratio of partial pressure of carbon monoxide:hydrogen being from 0.1:1
up to 1:0.1. Any oxo type reaction catalyst may be used, but, most
preferably, the catalyst to yield the best perfume mixtures are as
follows:
Dicobalt octacarbonyl;
Cobalt octanoate;
Palladium chloride;
Rhodium trichloride;
Iron pentacarbonyl;
Nickel tetracarbonyl;
Polymer-bonded rhodium catalyst (e.g., rhodium bonded on a polystyrene
substrate);
Tris-triphenyl phosphine rhodium-1-chloride;
Rhodium acetoacetate dicarbonyl;
Rhodium-acetoacetate-triphenylphosphene.
Depending upon the conditions of reaction including, temperature, partial
pressures of carbon monoxide and hydrogen, mole ratio of alcohol having
the structure:
##STR74##
to catalyst, concentration of alcohol having the structure:
##STR75##
in solvent, concentration of catalyst in solvent and time of reaction, the
nature of the isomers of the aldehydes defined according to the structure:
##STR76##
wherein the lines
##STR77##
represent covalent carbon-carbon bonds when m does not=0; and wherein the
lines
##STR78##
do not represent any bonds when m=0; wherein R represents hydrogen or
methyl; wherein p and q each represents 0 or 1 with the proviso that p=1
when q=0 and p=0 when q=1; wherein X and Z each represent one or more
carbon atoms required to complete a bicyclo ring with the lines
##STR79##
representing carbon-carbon bonds; wherein X and Z complete a phenyl moiety
when the line
##STR80##
represents no bond; wherein X and Z complete a cycloalkyl ring moiety with
the lines
##STR81##
represent carbon-carbon bonds and with the line
##STR82##
representing no bond; and wherein when m is 0, X represents an alkylene
moiety will vary. The variation of the conditions of reaction is a
function of the nature of the perfumery product desired. Accordingly, the
organoleptic qualities of the product desired can be varied in a
tailor-made fashion as a function of the conditions of the reaction.
Exemplary of the reactants and products produced in their organoleptic
properties are the following:
TABLE I
__________________________________________________________________________
Alcohol Reactant Aldehyde Reaction Product
Organoleptic
__________________________________________________________________________
Property
##STR83##
##STR84## A woody and nutty aroma with
minty and floral topnotes.
##STR85##
and
##STR86##
##STR87##
##STR88## A floral (lilac) aroma with
cinnamon-like topnotes.
and
##STR89##
##STR90##
##STR91## A green, woody, peach- like
and balsamic aroma profile
with green floral topnotes.
##STR92## A mixture of compounds having the
A fresh air dried linen
aroma.
##STR93##
and
##STR94##
__________________________________________________________________________
As olfactory agents, the tertiary hydroxyl carboxaldehydes taken alone or
in admixture, of our invention, can be formulated into, or used as
components of a "perfume composition" or can be used as components of a
"perfumed article", or the perfume composition may be added to perfumed
articles.
The term "perfume composition" is used herein to mean a mixture of organic
compounds including, for example, mono alcohols, aldehydes (other than the
tertiary hydroxyl carboxaldehydes of our invention), ketones, nitriles,
ethers, lactones, natural essential oils, synthetic essential oils and
hydrocarbons which are admixed so that the combined odors of the
individual components produce a pleasant or desired fragrance. Such
perfume compositions usually contain (a) the main note or the "bouquet" or
foundation stone of the compositions; (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, the individual component will contribute its
particular olfactory characteristics, but the overall effect of the
perfume composition will be the sum of the effects of each of the
ingredients and in certain instances, a synergistic effect as a result of
the addition of certain ingredients. Thus, the individual compounds of
this invention, or mixtures thereof, can be used to alter the aroma
characteristics of a perfume composition, for example, by highlighting or
moderating the olfactory reaction contributed by another ingredient in the
composition.
The amount of the tertiary hydroxyl carboxaldehydes of our invention which
will be effective in perfume compositions depends on 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 the tertiary hydroxyl carboxaldehydes of this invention, or
even less, can be used to impart an interesting, woody, nutty, floral,
lilac, green, peach-like, balsamic and fresh air dried linen aromas with
minty, floral, cinnamon-like and green topnotes to soaps, liquid or solid
anionic, cationic, nonionic or zwitterionic detergents, cosmetics,
cosmetic powders, liquid and solid fabric softeners, drier-added fabric
softener articles, (e.g., BOUNCE.RTM. a registered trademark of the
Procter & Gamble Company of Cincinnati, Ohio), optical brightener
compositions and other products. The amount employed can range up to 70%
or even higher, and will depend on considerations of cost, nature of the
end product, and the effect desired on the finished product and particular
fragrance sought. Thus, for example, when fragrancing liquid bleach
compositions containing alkalihypochlorite such as, for example, sodium
hypochlorite, for example CLOROX.RTM., (registered trademark of Clorox,
Inc.), the amount employed can be as high as 100% of the fragrance
involved in the liquid bleach. Indeed, a distinctive aspect of our
invention is the use of one or more of the tertiary hydroxyl
carboxaldehydes of our invention in a stable liquid bleach composition.
The tertiary hydroxyl carboxaldehydes of this invention, taken alone or in
admixture, can be used alone, or in a perfume composition as an olfactory
component in detergents, soaps, space odorants and deodorants; perfumes;
colognes, toilet waters; bath salts; hair preparations, such as lacquers,
brilliantines, pomades and shampoos; cosmetic preparations, such as
creams, deodorants, hand lotions, sunscreens; powders, such as talcs,
dusting powders, face powders and the like; liquid bleaches, such as
sodium hypochlorite-containing bleaches; floor waxes; automobile aromas
and automobile polish compositions; and perfumed polymers and perfumed
polymer articles of manufacture such as perfumed garbage bags.
When used as an olfactory component of a perfumed article, as little as
0.01% of one or more of the tertiary hydroxyl carboxaldehydes of our
invention will suffice to impart an interesting, woody, nutty, floral,
lilac, green, peach-like, balsamic and fresh air dried linen aromas with
minty, floral, cinnamon-like and green topnotes. Generally, no more than
0.5% is required to impart such aromas, however, in view of the rather low
cost of the tertiary hydroxyl carboxaldehydes of our invention, up to 100%
of the perfume composition can be one or more of the tertiary hydroxyl
carboxaldehydes of our invention.
Accordingly, the range of use in perfumed articles of the tertiary hydroxyl
carboxaldehydes of our invention is from about 0.01% up to about 0.5%.
In addition, the perfume composition of our invention can contain a vehicle
or carrier for the tertiary hydroxyl carboxaldehydes taken alone, or taken
together with other ingredients. The vehicle can be a liquid such as a
non-toxic alcohol such as ethanol, a glycol such as propylene glycol, or
the like. The carrier can be an absorbent solid, such as a gum or
components (e.g., gum arabic, xanthan gum or guar gum or combinationa
thereof) or components for encapsulating the composition such as gelatin
which can be used to form a capsule wall surrounding the perfume oil, as
by means of coacervation, or a polymer such as the ureformaldehyde polymer
which can be used to surround a perfume liquid center.
It will thus be apparent that the tertiary hydroxyl carboxaldehydes 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 serve to illustrate our invention, and this
invention is to be considered restricted thereto only as indicated in the
appended claims.
All parts and percentages given herein are by weight unless otherwise
specified.
EXAMPLE I
Preparation of 8-hydroxy-p-methane-2-carboxaldehyde
Reaction:
##STR95##
Into a high pressure autoclave in placed 1232 grams (8 moles) of terpinol
having the structure:
##STR96##
and 0.45 grams of rhodium aceto acetate-dicarbonyl. The autoclave is
sealed and pressurized to 1000 psig and heated to a temperature of
150.degree.-160.degree. C. with a 50:50 mole:mole mixture of carbon
monoxide and hydrogen. The autoclave contents are maintained at a pressure
of 1000 psig and a temperature in the range of 150.degree.-160.degree. C.
for a period of forty one hours.
At the end of this time period, the autoclave contents are cooled and the
contents are removed from the autoclave filtered and distilled on a 1"
splash column yielding the following fractions:
______________________________________
Vapor Liquid Vacuum
Fraction Temp. Temp. mm/Hg.
No. (.degree.C.) (.degree.C.)
Pressure
______________________________________
1 /74 /100 4:0
2 88 110 5:5
3 94 115 5:5
4 105 130 5:5
5 128 130 5:5
6 124 158 2:6
7 149 220 2:6
______________________________________
Fractions 2-7 are bulked and redistilled on an 18" Goodloe column yielding
the following fractions:
______________________________________
Vapor Liquid Vacuum Weight
Fraction Temp. Temp. mm/Hg. of
No. (.degree.C.)
(.degree.C.)
Pressure
Fraction
______________________________________
1 78/83 118/124 3:2/3:3
11.2
2 82 127 2:7 14.9
3 83 129 2:7 12.5
4 83 135 3:6 14.1
5 119 135 3:0 25.3
6 123 137 3:0 25.8
7 123 137 3:0 6.7
8 128 144 3:0 12.1
9 128 145 3:2 9.6
10 127 150 3:2 19.9
11 130 162 3:4 15.0
12 131 181 3:8 8.5
13 128 188 3:6 2.4
______________________________________
Fractions 8-10 are bulked and determined to have a woody and nutty aroma
with minty and floral topnotes.
FIG. 1 is the GLC profile of Fraction 6 of the foregoing distillation.
(Conditions: Carbowax column programmed at 100.degree.-220.degree. C.
isothermal). The peak indicated by reference numeral "11" is the peak for
the compound having the structure:
##STR97##
The peak indicated by reference numeral "12" is the peak for the compound
having the structure:
##STR98##
The peak indicated by reference numeral "13" is the peak for the mixture of
compounds defined according to the structure:
##STR99##
FIG. 2 is the NMR spectrum for the peak indicated by reference numeral "11"
on FIG. 1 for the compound defined according to the structure:
##STR100##
(conditions: Field strength: 100 MHz; Solvent: CFCl.sub.3).
FIG. 3 is the NMR spectrum for the peak indicated by reference numeral "12"
on the GLC profile of FIG. 1 for the compound having the structure:
##STR101##
(conditions: Field strength: 100 MHz; Solvent: CFCl.sub.3).
FIG. 4 is the NMR spectrum for the peak indicated by reference numeral "13"
on the GLC profile of FIG. 1 and is for a mixture of compounds defined
according to the structures:
##STR102##
EXAMPLE II
Preparation of 5-(1-hydroxy-1-methylethyl)-6,6-dimethyl-(1 and 2)
Norbornane Carboxaldehyde
Reaction:
##STR103##
Into a 500 cc autoclave is placed 205.5 grams of the compound having the
structure:
##STR104##
0.1 grams of rhodium aceto acetate and 7 grams of triphenyl phosphine, and
100 cc toluene.
The autoclave is sealed and pressurized to 1000 psig and heated to a
temperature of 120.degree. C. using a 50:50 mole:mole mixture of carbon
monoxide and hydrogen. The autoclave contents are maintained at 1000 psig
and 120.degree. C. for a period of four hours.
At the end of the four hour period, the autoclave contents are cooled and
the autoclave is opened and the contents are filtered and then distilled
through a 2" splash column yielding the following fractions:
______________________________________
Vapor Liquid Vacuum
Fraction Temp. Temp. mm/Hg.
No. (.degree.C.) (.degree.C.)
Pressure
______________________________________
1 26/94 48/129 1:8/0:75
2 99 129 0:7
3 125 139 2:1
4 104 138 0:55
5 132 142 2:1
6 126 198 2:2
______________________________________
Fractions 2-6 are then bulked and redistilled on an 18" Goodloe column
yielding the following fractions:
______________________________________
Vapor Liquid Vacuum Weight
Fraction Temp. Temp. mm/Hg. of
No. (.degree.C.)
(.degree.C.)
Pressure
Fraction
______________________________________
1 128/135 147/148 3:5/3:6
8.1
2 137 149 3:3 14.1
3 140 150 3:7 13.4
4 140 149 3:4 15.0
5 140 152 3:4 31.2
6 140 150 3:4 15.9
7 140 150 3:4 26.4
8 140 154 3:4 19.7
9 140 175 3:4 13.4
10 135 230 3:4 10.3
______________________________________
Fractions 5-8 are bulked and the bulked fractions have a floral (lilac)
aroma with cinnamon-like topnotes.
FIG. 5 is the GLC profile for the crude reaction product prior to
distillation. The peak indicated by reference numeral "51" is the peak for
the mixture of compounds defined according to the structures:
##STR105##
The peak indicated by reference numeral "52" is the peak for the staring
material having the structure:
##STR106##
The peak indicated by reference numeral "53" is the peak for the reaction
solvent, toluene.
FIG. 6 is the GLC profile for Fraction 1 of the redistillation.
FIG. 7 is the NMR spectrum for the mixture of compounds having the
structures:
##STR107##
produced according to this example. (Conditions: Field strength: 100 MHz;
Solvent: CFCl.sub.3).
FIG. 8 is the infra-red spectrum for the mixture of compounds having the
structures:
##STR108##
produced according to this example.
EXAMPLE III
Preparation of
p-(1-hydroxy-1-methylethyl-).beta.-methyl-hydrocinnamaldehyde
Reaction:
##STR109##
Into a 700 cc autoclave is placed the following ingredients: (i) 110 grams
p-isopropyl phenyl dimethyl carbinol having the structure:
##STR110##
(ii) 8 grams--triphenyl phosphine; (iii) 0.1 grams--rhodium aceto acetate;
(iv) 300 ml--toluene
The autoclave is closed and pressured with a 50:50 mole:mole mixture of
carbon monoxide and hydrogen to a pressure of 1000 psig and heated to a
temperature in the range of 120.degree.-150.degree. C. and maintained at
120.degree.-150.degree. C. and at a pressure of 1000 psig for a period of
fifteen hours.
At the end of the fifteen hour period, the autoclave is cooled and opened
and the contents are filtered. The resulting filtrate is then distilled
through a 6" Miller column yielding the following fractions:
______________________________________
Vapor Liquid Vacuum
Fraction Temp. Temp. mm/Hg.
No. (.degree.C.) (.degree.C.)
Pressure
______________________________________
1 /24 /27 1:0
2 24 31 2:1
3 25 87 1:0
4 108 152 0:5
5 122 154 0:5
6 130 200 0:5
______________________________________
Fractions 5-6 are bulked and redistilled on an 18" Goodloe column yielding
the following fractions:
______________________________________
Vapor Liquid Vacuum Weight
Fraction Temp. Temp. mm/Hg. of
No. (.degree.C.)
(.degree.C.)
Pressure
Fraction
______________________________________
1 /65 /165 2:3 2.5
2 94 156 2:3 5.7
3 55 158 2:4 5.3
4 80 156 2:3 7.4
5 82 157 2:2 7.9
6 113 163 2:0 8.6
7 120 168 2:0 12.0
8 106 187 2:0 7.3
9 53 200 2:0 9.4
______________________________________
Fractions 5-8 are bulked. The bulked fractions have an interesting green,
woody, peach-like and balsamic aroma profile with green and floral
topnotes.
FIG. 9 is the GLC profile of bulked Fractions 5-6 of the first
distillation.
FIG. 10 is the NMR spectrum for Fraction 6 of the first distillation
containing the compound having the structure:
##STR111##
(Conditions: Field strength: 100 MHz; Solvent: CFCl.sub.3).
FIG. 11 is the infra-red spectrum for Fraction 6 of the first distillation
containing the compound having the structure:
##STR112##
EXAMPLE IV
Preparation of 12-hydroxy-12-methyl Tridecanal
Reaction:
##STR113##
Into a 1000 cc autoclave is placed the following ingredients: (i) 302
grams of the alcohol having the structure:
##STR114##
(ii) 0.1 grams of rhodium aceto acetate; (iii) 6.5 grams of
triphenylphosphine;
(iv) 200 ml--toluene.
The autoclave is sealed and the pressure is increased to 700 psig using a
50:50 mole:mole mixture of carbon monoxide and hydrogen. The temperature
of the contents in raised to a 120.degree.-140.degree. C. and maintained
at a temperature of 120.degree.-140.degree. C. at a pressure of 700 psig
for a period of twenty five hours. At the end of the twenty five hour
period, the autoclave is cooled and the contents are filtered. The
filtrate is then distilled on a 2" splash column yielding the following
fractions:
______________________________________
Vapor Liquid Vacuum Weight
Fraction Temp. Temp. mm/Hg. of
No. (.degree.C.)
(.degree.C.)
Pressure
Fraction
______________________________________
1 /132 /160 3:6 1.3
2 154 167 4:8 26.8
3 150 162 3:0 96.7
4 152 162 1:6 77.3
5 152 260 3:0 101.6
______________________________________
Fractions 2-5 are bulked and redistilled on a 18" Goodloe column yielding
the following fractions:
______________________________________
Vapor Liquid Vacuum Weight
Fraction Temp. Temp. mm/Hg. of
No. (.degree.C.)
(.degree.C.)
Pressure
Fraction
______________________________________
1 142/ 160/ 2:0 7.2
2 145 162 7:0 23.8
3 146 162 2:0 30.5
4 146 163 2:0 30.2
5 146 165 2:0 29.3
6 146 167 2:0 19.0
7 146 170 2:0 21.4
8 146 180 2:0 18.6
9 146 195 2:0 13.4
10 144 230 2:0 9.9
11 140 245 2:0 3.4
______________________________________
Fractions 4-8 of the foregoing distillation are bulked and have a fresh air
dried linen aroma.
FIG. 12 is the GLC profile for the crude reaction product prior to the
first distillation. The peaks indicated by reference numerals "122" and
"123" are the peaks for the compounds defined according to the structures:
##STR115##
The peak indicated by reference numeral "121" is the peak for the toluene
solvent used in the reaction mass.
FIG. 13 is the GLC profile for Fraction 6 of the second distillation.
FIG. 14 is the NMR spectrum for Fraction 4 of the second distillation
(conditions: Field strength: 100 MHz; Solvent: CFCl.sub.3). This material
contains 25% by weight of the compound having the structure:
##STR116##
and 75% by weight of the compound having the structure:
##STR117##
EXAMPLE V
Preparation of Pine Formulation
The following pine formulations are prepared:
______________________________________
Ingredients V-A V-B V-C V-D
______________________________________
Isoburnyl acetate 100 100 100 100
Camphor 10 10 10 10
Terpineol 25 25 25 25
Fir balsam absolute 20 20 20 20
(50% in diethyl phthalate)
Coumarin 4 4 4 4
Linalool 30 30 30 30
Anethol 2 2 2 2
Fenchyl alcohol 10 10 10 10
Lemon terpenes washed
50 50 50 50
Borneol 5 5 5 5
Galbanum oil 5 5 5 5
Turpentine Russian 150 150 150 150
Pinus pumilionus 50 50 50 50
Eucalyptol 50 50 50 50
2,2,6-trimethyl-1-cyclohexene-
5 5 5 5
1-carboxaldehyde
Maltol (1% in diethyl
5 5 5 5
phthalate)
Bulked Fractions 8-10 of
479 000 000 000
the distillation product
of Example I containing
the compounds having the
structures:
##STR118##
Mixture of compounds 0 479 0 0
having the structures:
##STR119##
produced according to
Example II, bulked
Fractions 5-8
Compound having the 0 0 479 0
structure:
##STR120##
produced according to
Example III, bulked
Fractions 5-8
Mixture of compounds 0 0 0 479
having the structures:
##STR121##
prepared according to
Example IV, bulked
distillation
Fractions 4-8
______________________________________
The perfume formulation containing the mixture of compounds having the
structures:
##STR122##
can be described as "piney having woody and nutty undertones and minty and
floral topnotes".
The formulation containing the mixture of compounds defined according to
the structures:
##STR123##
produced according to Example II can be described as "piney having lilac
undertones and floral (lilac-like) and cinnamon-like topnotes".
The formulation containing the compound having the structure:
##STR124##
produced according to Example III can be described as "piney with green,
woody, peach-like and balsamic undertones and green, floral topnotes".
The formulation containing the mixture of compounds having the structures:
##STR125##
produced according to Example IV can be described as "piney with a fresh
air dried linen-like undertone".
EXAMPLE VI
Preparation of Cosmetic Powder Compositions
Cosmetic powder compositions are prepared by mixing in a ball mill, 100
grams of talcum powder (per compositions) with 0.25 grams of the substance
set forth in Table II below (per composition). Each of the cosmetic powder
compositions has an excellent aroma as described in Table II below:
TABLE II
______________________________________
Substance Aroma Description
______________________________________
Mixture of compounds having
A woody, nutty aroma
the structures: with minty and floral
topnotes.
##STR126##
produced according to
Example I, bulked
distillation
Fractions 4-6.
Mixture of compounds A floral (lilac) aroma
having the structures:
with floral (lilac-like)
and cinnamon-like top-
notes.
##STR127##
produced according to
Example II, bulked
distillation
Fractions 5-8
Compound having the A green, woody, peach-
structure: like and balsamic aroma
with green and floral
topnotes.
##STR128##
produced according to
Example III, bulked
distillation
Fractions 5-8
Mixture of compounds A fresh air dried
having the structures:
linen aroma.
##STR129##
produced according to
Example IV, bulked
distillation
Fractions 4-8
Perfume composition of
Piney, having woody
Example V-A and nutty undertones
and minty and floral
topnotes.
Perfume composition of
Piney, having lilac
Example V-B undertones and floral
(lilac-like) and cinna-
mon-like topnotes.
Perfume composition of
Piney, with green,
Example V-C woody, peach-like and
balsamic undertones and
green, floral topnotes.
Perfume compositions of
Piney, with a fresh air
Example V-D dried linen-like under-
tone.
______________________________________
EXAMPLE VII
Perfumed Liquid Detergents
Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonic
acid as more specifically described in U.S. Pat. No. 3,948,818 issued on
Apr. 6, 1976 incorporated by reference herein) with aroma nuances as set
forth in Table II of Example VI, are prepared containing 0.10%, 0.15%,
0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in Table II of
Example VI. They are prepared by adding and homogeneously mixing the
appropriate quantity of substance set forth in Table II of Example VI in
the liquid detergent. The detergents all possess excellent aromas as set
forth in Table II of Example VI, the intensity increasing with greater
concentrations of substance as set forth in Table II of Example VI.
EXAMPLE VIII
Preparation of Colognes and Handkerchief Perfumes
Compositions as set forth in Table II of Example VI are incorporated into
colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and 5.0%
in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions; and into
handkerchief perfumes at concentrations of 15%, 20%, 25% and 30% (in 80%,
85%, 90% and 95% aqueous food grade ethanol solutions). Distinctive and
definitive fragrances as set forth in Table II of Example VI are imparted
to the colognes and to the handkerchief perfumes at all levels indicated.
EXAMPLE IX
Preparation of Soap Compositions
One hundred grams of soap chips (per sample) (IVORY.RTM., produced by the
Procter & Gamble Company of Cincinnati, Ohio), are each mixed with one
gram samples of substances as set forth in Table II of Example VI until
homogeneous compositions are obtained. In each of the cases, the
homogeneous compositions are heated under 8 atmospheres pressure at
180.degree. C. for a period of three hours and the resulting liquids are
placed into soap molds. The resulting soap cakes, on cooling, manifest
aromas as set forth in Table II of Example VI.
EXAMPLE X
Preparation of Solid Detergent Compositions
Detergents are prepared using the following ingredients according to
Example I of Canadian Pat. No. 1,007,948 (incorporated herein by
reference):
______________________________________
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.
______________________________________
The detergent is a phosphate-free detergent. Samples of 100 grams each of
this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams of each of
the substances as set forth in Table II of Example VI. Each of the
detergent samples has an excellent aroma as indicated in Table II of
Example VI.
EXAMPLE XI
Utilizing the procedure of Example I at column 15 of U.S. Pat. No.
3,632,396 (the disclosure of which is incorporated herein by reference),
nonwoven cloth substrates useful as drier-added fabric softening articles
of manufacture are prepared wherein the substrate, the substrate coating,
the outer coating and the perfuming material are as follows:
1. A water "dissolvable" paper ("Dissolvo Paper")
2. Adogen 448 (m.p. about 140.degree. F.) as the substrate Coating; and
3. An outer coating having the following formulation (m.p. about
150.degree. F.):
57% C.sub.20-22 HAPS
22% isopropyl alcohol
20% antistatic agent
1% of one of the substances as set forth in Table II of Example VI.
Fabric softening compositions prepared according to Example I at column 15
of U.S. Pat. No. 3,632,396 having aroma characteristics as set forth in
Table II of Example VI, supra, consist of a substrate coating having a
weight of about 3 grams per 100 square inches of substrate; a first
coating located directly on the substrate coating consisting | | |
