Note: Descriptions are shown in the official language in which they were submitted.
~z~
--3--
This invention relates to certain cyclohexadienyl
butanone derivatives having the generic structure:
~ 11 V
wherein X is:
11 ~ or
`and mixtures of same.
1. Field of the Invention
. This application relates to the specific compounds
:having the genus:
n
10 ~ ~Y~,X~
wherein X is:
C ~ ~r
and the use thereof to augment, enhance or impart flavor
and/or aroma to foodstuffs, chewing gums, toothpastes,
8~i
--4--
medicinal products, perfumes, perfumed articles, tobaccos
and tobacco flavoring compositions. The application
also relates to a process for producing such cyclohexadien-
l-yl-l-butanone compounds comprising the steps of:
(i) intimately admixing methyl magnesium halide
having the structure:
CH3~1g
with l-acetyl-2,6,6-trimethyl-1,3-cyclohexa-
diene having the structure:
~3'
whereby a first organometallic compound having
the structure:
c X
I ~
is formed;
(li) intimately admixing said first organometallic
compound having the structure:
1 X
1 ~
\ ~ ~
11
~\
with an acetyl halide having the structure:
o
~-JC X
~2~
--5--
whereby a second organometallic compound is
formed having the structure:
D~t),~X
~~
(iii) hydrolyzing in the presence of acid, said
second organometallic compound having the
structure:
OJ~ X
whereby said equilibrium mixture comprising
: compound having the structures:
O C
and ~ / 1l f
,
is formed, wherein X is halogen selected from
the group consisting of chloro, bromo and iodo,
and X' is halogen selected from the group
consisting of chloro and bromo.
2. Description of the Prior Art
3-Hydroxy-l-(2,6,6-trimethyl-1,3-cyclohexadien-l-
yl)-l-butanone having the structure:
o OH
~,~
28~
has heretofore been indicated by Ayyar, Cookson and
Kagi, J. Chem. Soc., Perkin I, 1727 (1975) (Title:
"Synthesis of ~-Damascone [trans-l-(2,6,6-trimethyl-
cyclohex-3-enyl)but-2-en-1-one] and ~-Damascenone
[trans-1-(2,6,6-trimethylcyclohexa-1,3-dienyl)but-2-
en-l-one]") to be useful as an intermediate in preparing
"Damascenone" the '~' isomer of which has the structure:
o
Ayyar, Cookson and Kagi do not, however, teach the
usefulness of 3-hydroxy-l-(2,6,6-trimethyl-1,3-cyclo-
hexadien-l-yl)-l-butanone for its organoleptic properties.
Schulte-Elte, U.K. Patent Specification 1,391,736
discloses and claims a genus of compounds which include
3-hydroxy-1(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-
butanone and uses of their organoleptic properties butdoes not specifically teach any specific cyclohexadien
compounds per se or their uses for their organoleptic
properties. Thus, U.K. Patent Specification 1,391,736
states:
"The compounds to which the invention relates
have the formula: ~,
R~ , X
R4i ii
wherein:
X represents the group:
O OH
- c - c = 1 - c~2p,
l2
P~
O O
- C - CH - C - CH2R
R2
J`2~
01~ 0
11
- C = C - C - CH2R
R
O OH
Il I
- C - CH - CH - CH2R
R2
.
.
OH OH
- C = C - CH - CH2R
R2
'.
OH OH
1 '
- CH - CH - CH - CH2R
R2
R , R , R , R and R may be the same or
different, and each represents a hydrogen
atom or a lower alkyl group having from 1
: to 6 carbon atoms; and the ring is saturated
or contains one endocyclic double bond in
position 1, 2, 3 or 4, or an exocyclic double
bond in position 2, or two conjugated double
bonds in positions 1 and 3
The new compounds of formula (I) include the
following specific examples:
2,6,6-trimethyl-1-(1,3-dioxo-but-1-yl)-
cyclohex-l-ene;
2-methylene-6,6-dimethyl-1-(1,3-dioxo-but-
l-yl)-cyclohexane;
2,6,6-trimethyl-1-(3-hydroxy-butan-1-oyl)-
cyclohex-l-ene;
2,6,6-trimethyl-1-(3-hydroxy-butan-1-oyl)-
cyclohex-2-ene;
2,6,6-trimethyl-1-(2-methyl-1,3-dioxo-
but-l-yl)-cyclohex-l-ene;
2,6,6-trimethyl-1-(2-methyl-1,3-dioxo-
but-l-yl)-cyclohex-2-ene;
2-methylene-6,6-dimethyl-1-(2-methyl-1,3-
dioxo-but-l-yl)-cyclohexane;
2~
--8--
2,6,6-trimethyl-1-(2-methyl-3-hydroxy-
butan-1-oyl)-cyclohex-2-ene;
2-methylene-6,6-dimethyl-1-(2-methyl-3-
hydroxy-butan-l-oyl)-cyclohexane;
2,6,6-trimethyl-1-(2-methyl-1,3-dihydroxy-
but-l-yl)-cyclohex-2-ene;
2,66-trimethyl-1-(2-methyl-1,3-dihydroxy-
but-1-yl)-cyclohex-1-ene;
- 2,6,6-trimethyl-1-(1,3-dioxo-but-1-yl)-
cyclohexane;
2,6,6-trimethyl-1-(1,3-dihydroxy-but-1-
yl)-cyclohexane;
2,6,6-trimethyl-1-(1,3-dihydroxy-but-1-yl)-
cyclohex-2-ene; and
2,6,5-trimethyl-1-(1,3-dihydroxy-but-1-yl)-
cyclohex-l-ene".
Compounds similar to 1-(2,6,6-trimethyl-1,3-
cyclohexadien-l-yl)-1,3-butanedione having the structure:
O C'
20. have been reported in the literature, but their uses
for their organoleptic properties have not been reported
:nor are such uses implied. Thus, the diketones having
the structures:
C <~
~ \ and
I i
J
l~lZ8~i
or their corresponding enolates having the generic ~-
structure: `
,. ~f
C
~, 11 J
'I
~`
wherein a double bond could be situated at the Al or ~2
positions in the ring, or at the methylene group exocyclic
to the ring, are reported by Schulte-Elte, Muller and
Ohloff at Helv. Chim. Acta, Vol. 56, FASC 1 (1973)
- page 310 [Title: "Synthetische Ubergange von der Jonon-
in die Damasconreihe"]. These compounds are, however,
indicated to be useful as intermediates in synthesizing
compounds of the "Damascone" series having the generic
structure:
~;
,. `
wherein one of the dashed lines is a pi double bond
and each of the other dashed lines represents single
bonds, and, individually, the structures:
'~ ~ r
\
and C ~ ~ ~ ~
$
,,
--10--
which are, in turn, useful for their organoleptic proper-
ties. However, the organoleptic properties of the
members of the "Damascone" series are different in kind
from the organoleptic properties of l-(2,6,6-trimethyl-
1,3-cyclohexadien-1-yl)-1,3-butanedione.
A sulfur analogue of 3-hydroxy-1-(2,6,6-trimethyl-
1,3-cyclohexadien-1-yl)-1-butanone, which sulfur analogue
has the structure:
O SH
"\
is disclosed as having useful organoleptic properties
in U.S. Patent 3,979,422.
In addition, the diketone having the structure:
C
\~ 11 1
is indicated to be useful as a chemical intermediate at
15 Helv. Chim. Acta 31, 2135-42 (1948) [V. Prelog and
;Frick, "Uber einige Oxo-tetrahydro-jonone"].
Description of the Preferred Embodiments
The invention concerns the newly discovered cyclo-
hexadienyl butanone compounds having the structure:
n
~X~
b,~
wherein X is:
o ~ o~~l
~ 1~ ~ or l l
-~ t
~or mixtures of same and the organoleptic uses thereof
in consumable materials.
. Thus, it has now been discovered that novel solid
and liquid foodstuff, chewing gum, medicinal product
and toothpaste compositions and flavoring compositions
therefor having tea-like, tobacco-like, apple-juice-
like and dried fruit-like aromas and tastes; novel
perfume compositions and colognes having floral, fruity
and tobacco aromas with rose and grape notes and hay-
like and menthane-like undertones; as well as novel
smoking tobacco and smo]cing tobacco flavoring compositions
having sweet, dried fruit-like, floral and woody aromas
prior to smoking and sweet and dried fruit aroma character-
istics in the main stream and in the side stream onsmoking, may be provided by the utilization of 3-hydroxy-
1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone
having the formula:
O OH
.~1
-12-
in foodstuffs, chewing gums, toothpastes, medicinal
products, perfume compositions, perfumed articles,
colognes and smoking tobaccos as well as smoking tobacco
substitutes.
5 It has also been discovered that novel solid and
liquid perfume compositions, colognes and perfumed
articles having sweet, honey-like, fruity, grape-like,
rose-like, ionone-like, hay-like and floral aromas
with sea-amber and ambergris-like undertones and sweet-
floral topnotes as well as novel tobacco and flavoring
compositions having sweet, fruity, berry-like, fresh
squeezed fruit (apple and grape) juice-like, hay-like
and tea-like aromas prior to smoking with sweet, hay/tea
aromas in the main stream on smoking and sweet, tobacco-
like and "fresh cigarette pack" aromas in the sidestream on smoking may be provided by l-(2,6,6-trimethyl-
1,3-cyclohexadien-l-yl)-1,3-butanedione which may be
represented either by the structure: C~
11
~/'~
or by the equilibrium relationship:
:
or by the enolate having the structure:
~" `C`
\,/ 11 1
f ~
~i~
- 13 -
in perfume compositions, perfumed articles, colognes
and tobaccos as well as tobacco substltutes.
3-Hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-
l-yl)-l-butanone may be produced according to the
procedure set forth by Ayyar Cookson and Kagi at pages
1727-1736 of J.Chem.Soc. Perkin I (1975) (Title:
"Synthesis of Q-Damascone[trans-1-(2,6,6-trimethyl-
cyclohex-3-enyl) but-2-en-1-one] and ~-Damascone
[trans-1-(2,6,6-trimethylcyclohexa-1,3-dienyl) but-
2-en-1-one]") (see particularly column 1 at page 1735,
first paragraph).
1-(2,6,6-Trimethyl-1,3-cyclohexadien-1-yl)-1,3-
butanedione, useful as indicated supra, may be produced
by first reacting l-acetyl-2,6,6-trimethyl-1,3-
cyclohexadiene having the structure:
X,~W~
with a methyl magnesium halide having the structure:
CH3MgX
(X - halogen)
wherein X is halogen which may either be chloro, bromo
or iodo, thereby -forming an organometallic compound
having the structure:
~X
~`
1~ .
-14~
with the evolution of methane. The said organometallic
compound having the structure:
. ~X
may then be reacted with an acetyl hàlide having the
structure:
11
,
1-1 C /' \ X'
wherein X' is chloro or bromo, thereby forming a second
organometallic compound having the structure:
~,
l~ ~
This second organometallic compound is a novel compound.
The said second organometallic compound may then be
hydrolyzed using dilute acid such as dilute organic acid,
e.g., dilute acetic acid or dilute formic acid, or dilute
aqueous mineral acid such as dilute hydrochloric acid,
dilute sulfuric acid, dilute phosphoric acid or dilute
paratoluenesulfonic acid.
The reaction of the methyl magnesium halide with
the l-acetyl-2,6,6-trimethyl-1,3-cyclohexadiene takes
place at a temperature in the range of from -10C up to
tlOC, preferably from 0-5C at atmospheric pressure in
~2~
- 15 -
the presence of an inert anhvdrous solvent such as
tetrahydrofuran or diethyl ether. The reaction of the
first organometallic compound having the structure:
~X
~ .
with the acetyl halide having the structure:
O
Il
C
~ C/ \X'
takes place at a temperature in the range of from
0-30C, preferably at about 20C. It is preferred that
the acetyl halide be in slight molar excess with respect
to the first organometallic compound having the structure:
df~X
XJ`~
~ ' :
The hydrolysis of the second organometallic compound
having the structure:
O~X
J;~
- 16 -
preferably takes place using aqueous acetie acid (in
excess) at a temperature of between 5C and 20C,
preferably at about 10C at atmospherie pressure.
Following the hydrolysis of the seeond organometallie
eompound having the structure:
I In~ O
.'. ~J~'
'.
~,
to l-(2,6,6-trimethyl-1,3-eyelohexadien-1-yl)-1,3-
butanedione having the strueture:
O O
~,J'~
~ '
whieh is aetually in equillibrium with the enolate
having the strueture:
,H~
O C
according to the equilibrium:
2~
- 17 -
The reaction mass is worked up using standard extraction
and distillation procedures.
The aforementioned reaction sequence is illustrated
as follows:
o OMgX
+ CH3MgX > ~ + CH~
OMgX
+ H~C X ~ ~ + HX~
OMgX o ~H~
~ ~ ob
wherein X is halogen selected from the group consisting
of chloro, bromo, and iodo and X' is halogen selected from
the group consisting of chloro and bromo.
When it was attempted to oxidize the hydroxyketone
having the structure:
X~
11,
using a standard oxidizing agent, no 1-(2,6,6-trimethyl-
1,3-cyclohexadien-1-yl)-1,3-butanedione was formed but
- 18 -
~ Z~
~-damascenone having the structure:
was formed according to the reaction:
~,
H C~O3~1
Accordingly, the reaction sequence which was found to be
workable is not easily replaceable with an alternative
reaction sequence.
When the 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclo-
hexadien-l-yl)-l-butanone of our invention is used as
a food flavor adjuvant, the nature of the co-ingredients
included with the 3-hydroxy-1-(2,6,6-trimethyl-1,3-
cyclohexadien-l-yl)-l-butanone in formulating the
product composition will also serve to alter, modify,
augment or enhance the organoleptic characteristics of
the ultimate foodstuff treated therewith.
As used herein in regard to flavors, the terms
"alter", "modify", and "augment" in their various forms
mean "supplying or imparting flavor character or note
to otherwise bland, relatively tasteless substances or
augmenting the existing flavor characteristic where a
natural flavor is deficient in some regard or supple-
menting the existing flavor impression to modify its
quality, character or taste".
The term "enhance" is used herein to mean the
intensification of a flavor or aroma characteristic or
note without the modification of the quality thereof.
Thus, "enhancement" of a flavor or aroma means that the
~u ~
--19--
enhancement agent does not add any additional flavor
note.
As used herein, the term "foodstuff" includes both
solid and liquid ingestible materials which usually do,
but need not, have nutritional value. Thus, foodstuffs
include soups, convenience foods, beverages, dairy
products, candies, vegetables, cereals, soft drinks,
snacks and the like.
As used herein, the term "medicinal product"
includes both solids and liquids which are ingestible,
non-toxic materials which have medicinal value such as
cough syrups, cough drops, aspirin and chewable medicinal
tablets.
The term "chewing gum" is intended to mean a
composition which comprises a substantially water-
insoluble, chewable plastic gum base such as chicle, or
substitutes therefor, including jelutong, guttakay,
rubber or certain comestible natural or synthetic
resins or waxes. Incorporated with the gum base in
admixture therewith may be plasticizers or softening
agents, e.g., glycerine; and a flavoring composition
which incorporates the 3-hydroxy-1-(2,6,6-trimethyl-1,3-
cyclohexadien-l-yl)-l-butanone of our invention, and
in addition, sweetening agents which may be sugars,
including sucrose or dextrose and/or artificial sweet-
eners such as cyclamates or saccharin. Other optional
ingredients may also be present.
Substances suitable for use herein as co-ingredients
or flavoring adjuvants are well known in the art for
such use, being extensively described in the relevant
literature. It is a requirement that any such material
-be "ingestibly" acceptable and thus non-toxic and other-
wise non-deleterious particularly from an organoleptic
standpoint whereby the ultimate flavor and/or aroma of
the consumable material used is not caused to have
unacceptable aroma and taste nuances. Such materials
may in general be characterized as flavoring adjuvants
or vehicles comprising, broadly, stabilizers, thickeners,
surface active agents, conditioners, other flavorants
and flavor intensifiers.
~3Z~
-20-
Stabilizer compounds include preservatives, e.g.,
sodium chloride; antioxidants, e.g., calcium and
sodium ascorbate, ascorbic acid, butylated hydroxyanisole
(mixture of 2- and 3- tertiary-butyl-4-hydroxyanisole),
butylated hydroxy toluene (2,6,-di-tertiarybutyl-4-
methylphenol), propyl gallate and the like and seques-
trants, e.g., citric acid.
Thickener compounds include carriers, binders,
protective colloids, suspending agents, emulsifiers
and the like, e.g., agar agar, carrageenan; cellulose
and cellulose derivatives such as carboxymethyl cellulose
and methyl cellulose; natural and synthetic gums such
as gum arabic, gum tragacanth; gelatin, proteinaceous
materials; lipids, carbohydrates; starches, pectins
and emulsifiers, e.g., mono- and diglycerides of fatty
acids, shim milk powder, hexoses, pentoses, disaccharides,
e.g., sucrose, corn syrup and the like.
Surface active agents include emulsifying agents,
e.g., fatty acids such as capric acid, caprylic acid,
palmitic acid, myristic acid and the like, mono- and
diglycerides of fatty acids, lecithin, defoaming and
flavor dispersing agents such as sorbitan monostearate,
potassium stearate, hydrogenated tallow alcohol and the
like.
Conditioners include compounds such as bleaching
and maturing agents, e.g., benzoyl peroxide, calcium
peroxide, hydrogen peroxide and the like; starch
modifiers such as peracetic acid, sodium chlorite,
sodium hypochlorite, propylene oxide, succinic anhydride
and the like, buffers and neutralizing agents, e.g.,
sodium acetate, ammonium bicarbonate, ammonium phosphate,
citric acid, lactic acid, vinegar and the like; colorants,
e.g., carminic acid, cochineal, tumeric and curcuma and
the like; firming agents such as aluminum sodium sulfate,
calcium chloride and calcium gluconate; texturizers,
anti-caking agents, e.g;, aluminum calcium sulfate and
tribasic calcium phosphate; enzymes; yeast foods, e.g.,
calcium lactate and calcium sulfate; nutrient supple-
ments, e.g., iron salts such as ferric phosphate, ferrous
gluconate and the like, riboflavin, vitamins, zinc
sources such as zinc chloride, ~inc sulfate and the
like.
Other flavorants and flavor intensifiers include
organic acids, e.g., acetic acid, formic acid, 2-hexenoic
acid, benzoic acid, n-butyryl acid, caproic acid,
caprylic acid, cinnamic acid, isobutyric acid, isovaleric
acid, alpha-methyl-butyric acid, propionic acid, valeric
acid, 2-methyl-2-pentenoic acid and 2-methyl-3-pentenoic
acid; ketones and aldehydes, e.g., acetaldehyde, aceto-
phenone, acetone, acetyl methyl carbinol, acrolein,
n-butanal, crotonal, diacetyl, 2-methyl butanal, beta,
beta-dimethylacrolein, methyl-n-amyl ketone, n-hexenal,
2-hexenal, isopentanal, hydrocinnamic aldehyde, cis-
3-hexenal, 2-heptenal, nonyl aldehyde, 4-(p-hydroxy-
~phenyl)-2-butanone, alpha-ionone, beta-ionone, 2-methyl-
3-butanone, benzaldehyde,~,~ and ~-damascones, ~-damas-
cenone, acetophenone, 2-heptanone, o-hydroxy-acetophenone,
2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-
phenyl-4-pentenal, 2-phenyl-2-hexenal, 2-phenyl-2-
:pentenal, furfural, 5-methyl furfural, cinnamaldehyde,
beta-cyclohomoeitral, 2-pentanone, 2-pentenal and
propanal; alcohols, sueh as l-butanol, benzyl alcohol,
l-borneol, trans-2-buten-1-ol, ethanol, geraniol, l-hexanal,
2-heptanol, trans-2-hexenol-1, eis-3-hexen-1-ol, 3-methyl-
3-buten-1-ol, l-pentanol, 1-penten-3-ol, p-hydroxyphenyl-
2-ethanol, isoamyl aleohol, isofenehyl alcohol, phenyl-
2-ethanol, alpha-terpineol, cis-terpineol hydrate, eugenol,
linalool, 2-heptanol, acetoin; esters, such as butyl
acetate, ethyl acetate, ethyl acetoacetate, ethyl benzo-
ate, ethyl butyrate, ethyl eaprate, ethyl eaproate, ethyl
eaprylate, ethyl einnamate, ethyl erotonate, ethyl
formate, ethyl isobutyrate, ethyl isovalerate, ethyl
laurate, ethyl myristate, ethyl alpha-methylbutyrate,
ethyl propionate, ethyl salicylate, trans-2-hexenyl
acetate, hexyl acetate, 2-hexenyl butyrate, hexyl butyrate,
isoamyl aeetate, isopropyl butyrate, methyl acetate,
methyl butyrate, methyl eaproate, methyl isobutyrate,
alpha-methylphenylglycidate, ethyl succinate, isobutyl
-22-
cinnamate, cinnamyl formate, methyl cinnamate and
;terpenyl acetate; hydrocarbons such as dimethyl naph-
thalene, dodecane, methyl naphthalene, myrcene, naph-
thalene, octadecane, tetradecane, tetramethylnaphthalene,
tridecane, trimethyl naphthalene, undecane, caryophyllene,
l-phellandrene, p-cymene, l-alpapinene; pyrazines such
as 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-
dimethylpyrazine, 3-ethyl-2,5-dimethylpyrazine, 2-
ethyl-3,5,6-trimethylpyrazine, 3-isoamyl-2,5-dimethyl-
pyrazine, 5-isoamyl-2,3-dimethylpyrazine, 2-isoamyl-
3,5,6-trimethylpyrazine, isopropyl dimethyl pyrazine,
methylethylpyrazine, tetramethylpyrazine, trimethyl-
pyrazine; essential oils, such as jasmine absolute,
cassia oil, cinnamon bark oil, rose absolute, orris
absolute, lemon essential oil, Bulgarian rose, yara
yara and vanilla; lactones, such as ~-nonalactone;
sulfides, e.g., methyl sulfide and other materials
~such as maltol; acetoin and acetals (e.g., l,l-diethoxy-
ethane, l,1-dimethoxyethane and dimethoxymethane).
The specific flavoring adjuvant selected for use
may be either solid or liquid depending upon the desired
physical form of the ultimate product, i.e., foodstuff,
whether simulated or natural, and should, in any event,
~(i) be organoleptically compatible with the 3-hydroxy-
~(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone of
our invention by not covering or spoiling the organo-
leptic properties (aroma and/or taste) thereof; (ii)
be nonreactive with the 3-hydroxy-(2,6,6-trimethyl-1,3-
cyclohexadien-l-yl)-l-butanone of our invention and
(iii) be capable of providing an environment in which
the 3-hydroxy-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-
l-butanone can be dispersed or admixed to provide a
homogeneous medium. In addition, selection of one or
more flavoring adjuvants, as well as the quantities thereof
will depend upon the precise organoleptic character
desired in the finished product. Thus, in the case of
flavoring compositions, ingredient selection will vary
-23-
in accordance with the foodstuff, chewing gum, medicinal
product or toothpaste to which the flavor and/or aroma
are to be imparted, modified, altered or enhanced. In
contradistinc-tion, in the--preparation of solid products,
e.g., simulated foodstuffs, ingredients capable of pro-
viding normally solid compositions should be selected,
such as various cellulose derivatives.
As will be appreciated by those skilled in the
art, the amount of 3-hydroxy-l-(2,6,6-trimethyl-1,3-
cyclohexadien-l-yl)-l-butanone employed in a particular
instance can vary over a relatively wide ranse, depending
upon the desired organoleptic effects to be achieved.
Thus, correspondingly, greater amounts would be necessary
in those instances wherein the ultimate food composition
to be flavored is relatively bland to the taste, whereas
relatively minor quantities may suffice for purposes of
enhancing the composition merely deficient in natural
flavor or aroma. The primary requirement is that the
amount selected be effective, i.e., sufficient to alter,
modify or enhance the organoleptic characteristics of
the parent composition, whether foodstuff per se, chewing
gum per se, medicinal product per se, toothpaste per se,
or flavoring composition.
The use of insufficient quantities of 3-hydroxy-l-
25 (2,6,6-trimethyl-1,3-cyclohexadien-l-yl)-l-butanone will,
of course, substantially vitiate any possibility of
obtaining the desired results while excess quantities
prove needlessly costly and in extreme cases may disrupt
the flavor-aroma balance, thus proving self-defeating.
3Q Accordingly, the terminology "effective amount" and
"sufficient amount" is to be accorded a significance
in the context of the present invention consistent with
the obtention of desired flavoring effects.
Thus, and with respect to ultimate food compositions,
chewing gum compositions, medicinal product compositions
and toothpaste compositions, it is found that quantities
of 3-hydroxy-l-(2,6,6-trimethyl-1,3-cyclohexadien-l-yl)-
l-butanone ranging from a small but effective amount,
e.g., 0.05 parts per million up to about lO0 parts per
million based on total composition are suitable. Con-
Z~
-24-
centrations in excess of the maximum quantity stated
are not normally recommended since they fail to prove
commensurate enhancement of organoleptic properties.
In those instances wherein the 3-hydroxy-1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1-butanone is added
to the foodstuff as an integral component of a
flavoring composition, it is, of course, essential
that the total quantity of flavoring composition employed
be sufficient to yield an effective 3-hydroxy-1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1-butanone concen-
tration in the foodstuff product.
Food flavoring compositions prepared in accordance
with the present invention preferably contain the 3-
hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-
butanone in concentrations ranging from about 0.01% upto about 15% by weight based on the total weight of the
said flavoring composition.
The composition described herein can be prepared
according to conventional techniques well known as
typified by cake batters and fruit drinks and can be
formulated by merely admixing the involved ingredients
within the proportions stated in a suitable blender to
obtain the desired consistency, homogeneity of dispersion,
etc. Alternatively, flavoring compositions in the form
of particulate solids can be conveniently prepared by
mlxing the 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-
l-yl)-l-butanone with, for example, gum arabic, gum
tragacanth, carageenan and the like, and thereafter
spray-drying the resultant mixture whereby to obtain
the particular solid product. Pre-prepared flavor mixes
in powder form, e.g., fruit-flavored powder mix, are
obtained by mixing the dried solid components, e.g.,
starch, sugar and the like and 3-hydroxy-1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1-butanone in a dry
blender until the requisite degree of uniformity is
achieved.
It is presently preferred to combine with the
3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-
l-butanone of our invention the following adjuvants:
Z~
-25-
p-Hydroxybenzyl acetone; geraniol; cassia oil; acet-
aldehyde; maltol, ethyl methyl phenyl glycidate, benzyl
acetate; dimethyl sulfide; eugenol; vanillin; caryophy-
llene; methyl cinnamate; guiacol; ethyl pelargonate,
cinnamaldehyde; methyl anthranilate; 5-methyl furfural;
isoamyl acetate; isobutyl acetate; cinnamaldehyde; alpha
ionone; cinnamyl formate; ethyl butyrate; methyl cinna-
mate; acetic acid; gamma-undecalactone; naphthyl ethyl
ether; diacetyl; furfural; ethyl acetate; anethole;
2,3-dimethyl pyrazine; 2-ethyl-3-methyl pyrazine; 3-
~phenyl-4-pentenal; 2-phenyl-2-hexenal; 2-phenyl-2-
pentenal; 3-phenyl-4-pentenal diethyl acetal; ~-damas-
cone (l-crotonyl-2,2,6-trimethyl-cyclohex-1-one);
~-damascenone (l-crotonyl-2,2,6-trimethyl-cyclohexa-
15 1,5-diene); beta-cyclohomocitral (2,2,6-trimethyl-
~cyclohex-l-ene carboxyaldehyde); isoamyl butyrate;
cis-3-hexenol-1; 2-methyl-2-pentenoic acid; elemecine
~(4-allyl-1,2,6-trimethoxy benzene); isoelemecine (4-
propenyl-1,2,6-trimethoxy benzene); and 2-(4-hydroxy-
4-methylpentyl) norbornadiene prepared according to
U.S. Patent 3,886,289.
An additional aspect of our invention provides
an organoleptically improved smoking tobacco product
and additives therefor, as well as methods of making
the same which overcome specific problems heretofore
encountered in which specific dried fruit-like flavor
characteristics of natural tobacco (prior to smoking
:and on smoking, in the main stream and in the side
stream) are created or enhanced or modified or aug-
mented, and may be readily controlled and maintainedat the desired uniform level regardless of variations
in the tobacco components of the blend.
According to another aspect of our invention an
organoleptically improved smoking tobacco product and
additives therefor, as well as methods of making the
same which overcome specific problems heretofore
encountered in which specific desired sweet, fruity,
berry, fresh squeezed fruit (apple and grape) juice-
like, hay-like and tea-like aromas prior to smoking
and improved body, enhanced tobacco character and
-26-
sweet, pronounced hay/tea characteristics in the main
stream on smoking and sweet, tobacco-like and "fresh
cigarette pack" aromas in the side stream on smoking,
are created or enhanced or modified or augmented and
may be readily controlled and maintained at the desired
- uniform level regardless of variations in the tobacco
components of the blend. In particular, low-grade
Virginia type tobaccos may be upgraded using the
1-(2,6,6-trimethyl-1,3-eyclohexadien-1-yl)-1,3-
butanedione of our invention.
This invention further provides improved tobaeeo
additives and methods whereby various desirable
natural aromatie tobaeco flavoring characteristics
with sweet,floral and fruity notes may be imparted to
15 smoking tobacco products and may be readily varied
and controlled to produce the desired uniform flavoring
eharaeteristies.
In earrying out this aspeet of our invention, we
add to smoking tobaeeo materials or a suitable substitute
therefor (e.g., dried lettuce leaves) an aroma and flavor
additive eontaining as an aetive ingredient the 1-~2,6,6-
trimethyl-1,3-eyelohexadien-1-yl)-1,3-butanedione and/or
the 3-hydroxy-1-(2,6,6-trimethyl-1,3-eyelohexadien-1-
yl)-l-butanone of our invention.
In addition, other flavoring and aroma additives
may be added to the smoking tobaeeo material or sub-
stitute therefor either separately or in mixture with
the 3-hydroxy-1-(2,6,6-trimethyl-1,3-eyelohexadien-1-
yl)-l-butanone as follows: I. Synthetie Materials:
Beta-ethyl-einnamaldehyde; eugenol, dipentene; ~-damas-
eenone; maltol; ethyl maltol; delta undeealaetone; delta
decalactone; benzaldehyde; amyl acetate; ethyl butyrate;
ethyl valerate; ethyl acetate; 2-hexenal-1; 2-methyl-
5-isopropyl-1,3-nonadiene-8-one; 2,6-dimethyl-2,6-
undecadiene-10-one; 2-methyl-5-isopropyl acetophenone;
2-hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-
deeahydronaphthalene; dodecahydro-3a,6,6,9a-tetramethyl
naphtho-(2,6-b)-furan; 4-hydroxy hexanoic acid, gamma
laetone; and polyisoprenoid hydroearbons defined in
Example V of U.S. Patent 3,589, 273 issued on June 29,
-27-
1971 and II. Natural Oils: celery seed oil; coffee
extract; bergamot oil; cocoa extract; nutmeg oil; and
origanum oil.
An aroma and flavoring concentrate containing one
or both cyclohexadien-l-yl-l-butanone derivatives and,
- if desired, one or more of the above-indicated additional
flavoring additives may be added to the smoking tobacco
material, to the filter or to the leaf or paper wrapper.
The smoking tobacco material may be shredded, cured,
cased and blended tobacco material or reconstituted
tobacco material or tobacco substitutes (e.g., lettuce
leaves) or mixtures thereof. The proportions of
flavoring additives may be varied in accordance with
taste, but insofor as enhancement or the imparting of
natural and/or sweet notes, we have found that satis-
factory results are obtained if the proportion by
weight of the sum total of cyclohexadien-l-yl-l-
butanone derivatives to smoking tobacco material is
between 50 ppm and 1,500 ppm t0.005% - 0.15%) of the
active ingredients to the smoking tobacco material. We
have further found that satisfactory results are obtained
if the proportion by weight of the sum total of cyclo-
hexadien-l-yl-l-butanone derivatives used to flavoring
material is between 500 and 15,000 ppm (0.05% - 1.5%).
Any convenient method for incorporating the cyclo-
hexadien-l-yl-l-butanone derivatives into the tobacco
product may be employed. Thus, the cyclohexadien-l-yl-
l-butanone derivatives taken alone or along with other
flavoring additives may be dissolved in a suitable
solvent such as ethanol, diethyl ether and/or volatile
organic solvents and the resulting solutions may either
be spread on the cured, cased and blended tobacco
material or the tobacco material may be dipped into
such solution. Under certain circumstances, a solution
of the cyclohexadien-l-yl-l-butanone derivatives taken
alone or taken together with other flavoring additives
as set forth above, may be applied by means of a suitable
applicator such as a brush or roller on the paper or
-28-
leaf wrapper for the smoking product, or it may be
applied to the filter by either spraying, or dipping
or coating.
Furthermore, it will be apparent that only a
portion of the tobacco or substitute therefor need be
treated and the thus-treated tobacco may be blended
with other tobaccos before the ultimate tobacco product
is formed. In such cases, the tobacco treated may have
the cyclohexadien-l-yl-l-butanone derivatives in excess
of the amounts of concentrations above indicated so
that when blended with other tobaccos, the final product
will have the percentage within the indicated range.
In accordance with one specific example of our
invention, an aged, cured and shredded domestic burley
tobacco is spread with a 20% ethyl alcohol solution of
3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-
butanone having the structure:
O OH
in an amount to provide a tobacco composition containing
150 ppm by weight of 3-hydroxy-1-(2,6,6-trimethyl-1,3-
cyclohexadien-l-yl)-l-butanone on a dry basis. There-
after, the alcohol is removed by evaporation and the
tobacco is manufactured into cigarettes by the usual
techniques. The cigarette when treated as indicated
has a desired and pleasing aroma which is detectable in
the main and side streams when the cigarette is smoked.
The aroma is described as being sweeter, more aromatic,
more tobacco-like and having sweet, floral and dried
fruit-like notes.
In accordance with another specific example of our
invention, an aged, cured and shredded domestic Virginia
tobacco is spread with a 20% ethyl alcohol solution of
1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanedione
Z~
-29-
in an amount to provide a tobacco composition containing
100 ppm by weight of 1-(2,6,6-trimethyl-1,3-cyclohexadien-
l-yl)-1,3-butanedione on a dry basis. Thereafter, the
alcohol is removed by evaporation and the tobacco is
manufactured into cigarettes by the usual techniques.
The cigarette when treated as indicated has a desired
and pleasing aroma which is detectable in the main and
side streams when the cigarette is smoked. This aroma
is described as being sweeter with more pronounced
hay/tea character with improved body and enhanced tobacco
character in the main stream and sweeter, more tobacco-
like with a "fresh cigarette pack" aroma in the side
stream. Prior to smoking the cigarette has a sweet,
fruity, berry-like, fresh squeezed fruit (apple and
grape) juice-like, hay-like and tea-like aroma character-
istic.
While our invention is particularly useful in the
manufacture of smoking tobacco, such as cigarette tobacco,
cigar tobacco and pipe tobacco, other tobacco products
formed from sheeted tobacco dust or fines may also be
used. Likewise, the cyclohexadien-l-yl-l-butanone
derivatives of our invention can be incorporated with
materials such as filter tip materials, seam paste,
packaging materials and the like which are used along
with tobacco to form a product adapted for smoking.
Furthermore, the cyclohexadien-l-yl-l-butanone deriva-
~tives can be added to certain tobacco substitutes ofnatural or synthetic origin (e.g., dried lettuce leaves)
and, accordingly, by the term "tobacco" as used through-
30 ;out this specification is meant any composition intendedfor human consumption by smoking or otherwise, whether
composed of tobacco plant parts or substitute materials
or both.
One or both cyclohexadien-l-yl-l-butanone deriva-
tives of our invention and one or more auxiliary perfumeingredients, including, for example, alcohols, aldehydes,
ketones other than the cyclohexadien-1-yl-1-butanone
derivatives of our invention, nitriles, esters, cyclic
esters (lactones), dialkyl ethers, alkyl alkenyl ethers,
~L~ $
-30-
thioethers, thiols, carboxylic acids and natural
essential oils may be admixed so that the comhined
odors of the individual components produce a pleasant
and desired fragrance, particularly and preferably in
rose 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 sub-
stances which retard evaportion; 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
- 15 characteristics, however, the over-all sensory effect
of the perfume composition will be at least the sum total
of the effects of each of the ingredients. Thus, one
or both of the cyclohexadien-l-yl-l-butanone derivatives
can be used to alter, modify or enhance the aroma character-
istics of a perfume composition, for example, by utilizing
or moderating the olfactory reaction contributed by other
ingredients in the composition.
The amount of cyclohexadien-l-yl-l-butanone deriva-
tives of our invention which will be effective in
perfume compositions as well as in perfumed articles and
colognes 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 0.01% of cyclohexadien-l-yl-l-
butanone derivatives or even less (e.g., 0.005%) can beused to impart a floral, fruity, tobacco aroma with rose
notes and hay, menthane undertones can be used to
impart a sweet, honey-like, fruity, grape-like, rose-
like, ionone-like, hay-like and floral aroma with sea-
amber, and ambergris-like undertones and sweet-floral
topnotes to soaps, cosmetics and 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
~ ~3~
finished product and the particular fragrance sought.
The cyclohexadien-l-yl-l-butanone derivatives of
our invention are useful as olfactory components in
detergents and soaps, fabric softener compositions
(especially for clothes drier uses), space odorants and
deodorants, perfumes, colognes, toilet water, bath
preparations, such as lacquers, brilliantines, pomades
and shampoos; cosmetic preparations, such as creams,
deodorants, hand lotions and sun screens; powders, such
as talcs, dusting powders, face powders and the like.
When used as an olfactory component as little as 0.25%
~of cyelohexadien-l-yl-l-butanone derivative(s) will
~suffice to impart an intense floral note to rose formu-
lations. Generally, no more than 5% of cyclohexadien-
l-yl-l-butanone derivative(s) based on the ultimate end
product, is required in the perfume composition.
In addition, the perfume composition or fragrance
eomposition of our invention ean eontain a vehicle or
earrier for the eyelohexadien-l-yl-l-butanone derivative.
The vehiele ean be a liquid sueh as a non-toxie aleohol
(e.g., ethyl alcohol), a non-toxie glycol (e.g., propy-
lene glycol), or the like. The carrier can also be an
absorbent solid, such as a gum, e.g., gum arabic, or
eomponents for encapsulating the eomposition (such as
gelatin) as by means of coacervation.
It will thus be apparent that the eyclohexadien-
~l-yl-l-butanone derivatives of our invention ean be
utilized to alter, modify or enhanee sensory properties,
partieularly organoleptic properties, such as flavor(s)
and/or fragranee(s) of a wide variety of consumable
materials.
Example I (A) serves to illustrate a process for
preparing the 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclo-
hexadien-l-yl)-l-butanone of our invention.
Example I also serves to illustrate the unworkability
of a process which was at first thought to have the
ability to yield l-(2,6,6-trimethyl-1,3-cyclohexadien-
l-yl)-1,3-butanedione. Example II, following, serves
to illustrate the process for specifically producing
40 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butane-
dione useful in our invention. Examples III and the
z~
-32-
following examples serve to illustrate the utilities
of the l-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-
butanedione of our invention.
It will be understood that these exa~ples are
illustrative, and the 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.
AL~
--3--
EXAMPLE I (A)
PREPARATION OF 3-HYDROXY-1-(2,6,6-TRIMETHYL
1,3-CYCLOHEXADIEN-l-YL)-l-BUTANONE
Reactions:
-
O Or~13Cl
~ \ + C ~ C ~
Y\f~ ,~, ' X~
~ ~ H3C
.
or~c~ o ~ c.~ ~
~ J~ o 1~i~3 \~
Into a 2- liter reaction flask equipped with a
mechanical stirrer, cooling bath, 250 ml addition funnel,
nitrogen purge, water-cooled condenser, gas bubbler and
thermometer, is placed 427 ml (1.3 moles) of a 3-molar
solution of methyl magnesium chloride in tetrahydrofuran.
~ 328~
-34-
200 Grams (1.22 r,loles) of 2,6,6-trimethyl-1-acetylcyclo-
hexa-1,3-diene are added dropwise from the addition
funnel at a rate sufficient to produce methane. Cooling
is applied as necessary t-o-maintain the reaction temperature
between 30 and 35C. Following completion of the addition
of the 2,6,6-trimethyl-1-acetylcyclohexa-1,3-diene, the
reaction mass is stirred until no further methane is
evolvea. The reaction mass is then cooled to a temperature
in the range of from 0C to 5C, and 59 grams of acet-
aldehyde is added dropwise with stirring while maintainingthe reaction mass temperature at about 10C. The reaction
is slightly exothermic. 15 ~inutes after the completion
of the addition of acetaldehyde, acetic acid is added
dropwise while maintaining the temperature of the reaction
mass at about 10C. Following the addition of acetic acid,
the reaction mass is permitted to reach room temperature.
The reaction mass is then washed into a separatory funnel
with water to dissolve the salt therein. The resulting
organic layer is washed with saturated sodium chloride,
saturated sodium bicarbonate, and then saturated sodium
chloride. The washed organic layer is then dried over
anhydrous magnesium sulfate and concentrated on a rotovap
yielding 256 grams of residue.
The resulting hydroxyketone having the structure:
O
25 ~
is distilled under vacuum in order to separate it from
other impurities. 70 Grams of th~ distilled material is
combined with 80 grams of Primol ~ and distilled under
0.25-0.60 mm Hg pressure into nine fractions. The
distillation data is as follows:
Wei~ht of
Vapor Temp. Liquid Temp. Fraction Fraction
22-40.5 24-85 3.~6
40.0 94 6.50 2
44 105 2.90 3
88 114 4.24 4
89.5 116.5 ~.50 5
90.75 120.0 8.01 6
93.0 128.0 ~.34 7
88.5 '147.0 7.93 8
87.0 147.0 3.51 . 9
Frastion X6 is found to be substantially pure and
is submitted for mass spectral, NMR, IR and UV analyses.
The NMR spectrum is set forth in Figure 1. The infra-
red spectrum is set forth in Figure 2. The mass spectrumis set forth in Figure 3. The ultraviolet absorption
spectrum (using a methanol solvent) is set forth in
Figure 4. max ~ 1 cm = 176.65 in methyl
alcohol. The NMR analysis is as follows:
-36-
Chem. Shift Signal Type ~ssignment Quantity
1.10 - S 6H
H3C~ CI~3
1.23 d 3H
: O OH
ll 1
CH3
1.74 S ~ 3H
~ 1
`~ ~ C_3
2.11 d ~ ~ 2H
H2~'~
2.71 m 1 IOH 2H
/~
H~
-
3.20 Broad O O~I lH
~V,
4.30 ~5 O OH lH
ll 1
`~ I
H
5.82 ~ ~ 2H
~1~
~ ~1
~J2~
-37-
The infra-red analysis is as follows: 3400-3500
(strong); 3000 (moderate); 2950 (strong);
2800Cm~l(moderat ) 1680Cm-l( t ) 1580cm-l( k)
1460 (strong); 1360-1400C l(strong); 1280-1330C~ 1
(strong); 1185 (moderate); 1160 (strong); 1125Cm 1
(moderate); 1040 (moderate); 1005 m l(moderate);
935-980cm l(moderatej; 850cm l(weak); 820cm l(weak);
:783 (moderate); 723-737cm l(moderate); and 690cm 1
(moderate).
The mass spectral analysis is (~I/E Ratio followed by
relative intensity): 43,100; 69,18; 77,13; 79,11; 91,18;
105,30; 121,81; 122,10; 149,9; 164,12; 190,2 and 208p,1.
. .
EXAMPLE I (B)
~ ABORTED RUN
. Attempted synthesis of 1-(2,6,6-trimethyl-1,3-
cyclohexadien-l-yl)-1,3-butanedione (actual production
of "~-Damascenone").
Reaction:
H CrO3Cl
It was attempted to oxidize the keto alcohol, the
product of the process of Example I(A) to a diketone
according to the procedure of Cory and Suggs, Tetrahedron
Letters No. 31, pages 2647-2650 (1975). The Cory and
Suggs reagent is pyridinium chlorochromate. However,
~-damascenone, having the structure:
O'
X~
,
, ~z~g~
-38-
was produced rather than l-(2,6,6-trimethyl-1,3-cyclo-
hexadien-l-yl)-1,3-butanedione, having the structure:
O C~,
W~ '
~ Into a 250 ml three-necked, round-bottom flask
equipped with water cooled condenser and magnetic
stirrer is placed 12.30 grams of pyridinium chlorochro-
mate slurried in 100 ml methylene dichloride (CH2C12).
The product of the process of Example I(A) having the
structure:
o C~
,~
(7.93 grams [0.038 moles] is dissolved in 20 ml methylene
dichloride and is added to the reaction mass with stirring.
The resulting mixture is permitted to stir at room
temperature for a period of two hours during which time
the color of the solution changes from orange to black.
The reaction mass is removed from the reaction flask
using 100 ml diethyl ether. The reaction flask is then
washed three times with diethyl ether leaving a black
"tar-like" substance behind. The organic layer is then
washed twice with sodium bicarbonate and saturated
sodium chloride solution, and is then concentrated on
a rotovap yielding 7.06 grams of crude material. A
5 microliter injection is made on a 20' SE-30 GLC
column and run from 100-225C at 4C/min. The major
peak is analyzed using infrared analysis and found to
be ~-Damascenone having the structure:
~nz~
- 39 -
EXAMPLE II
PREPARATION OF 1-(2,6,6-TRIMETHYL-1,3-CYCLOHEXADIEN-
1,3-BUTANEDIONE
., _
Reaction:
_
O OMgCl
+ CH3MgCl------3~ + CH~
OMgCl OMgCl o
+ H3C Cl ---3 ~ + HCl
+ H
o a,~H~
Into a 250 ml three-necked, round-bottom flask
equipped with a mechanical stirrer, an immersion thermo-
meter, a nitrogen purge, a dry ice/isopropanol cooling
bath, a 125 ml addition funnel and a water-cooled condenser
with gas bubbler, is placed 42.7 ml of a tetrahydrofuran
,,
12~
-40-
solution of methyl magnesium chloride (3 molar). The
methyl magnesium chloride/TllF solution is chilled to
0-5C with stirring, and 20 grams (0.122 moles) of
acetyl-2,6,6-trimethyl-1,~3-cyclohexadiene is added
dropwise over a minute period. Following completion of
the addition, the reaction mass is stirred at about
20C until no further methane is observed to evolve
(approximately a 30 minute period). The reaction
mass is then chilled to 0C and 10.14 grams (0.13 moles)
of freshly distilled acetyl chloride is added dropwise
over a 20 minute period. Following the addition of
the acetyl chloride, the reaction mass is stirred at
a temperature of 20C for 15 minutes and then once more
chilled to 10C, and a solution of 8.1 grams of acetic
acid in 10 ml water is added dropwise during a 5-
minute period. Following the addition of the acid, water
is added to dissolve salts, and the reaction mass is
transferred to a separatory funnel. Diethyl ether is
added and the ether layer is separated and washed twice
with saturated sodium bicarbonate solution and then twice
with saturated sodium chloride solution; dried and con-
centrated in vacuo. The concentrate is then analyzed
using GLC (Conditions: 20' x 1/4" 5~ SE-30 column).
NMR, IR and mass spectral data confirm that the last
eluting major peak is 1-(2,6,6-trimethyl-1,3-cyclohexa-
dien-l-yl)-1,3-butanedione. The residue is then submitted
to fractional distillation after adding thereto 50 grams
Primol . The fractional distillation is carried out on
a 14" x 3/4" Vigreaux column yielding the following
fractions.
FractionVaporLiquidVacuum Weight
No. Temp. Temp.(mm ~Ig) (grams)
1 23-39 24-114.50.175 7.81
2 67 143 0.20 5.92
3 61 194 0.28 3.90
4 94 225 0.25 5.56
Fraction 3 contains 95.4~ 1-(2,6,6-trimethyl-1,3-
cyclohexadien-1-yl)-1,3-butanedione.
NMR spectrum for 1-(2,6,6-trimethyl-1,3-cyclohexa-
dien-l-yl)-1,3-butanedione of fraction 3 is set forth
in Figure 5. The IR spectrum for 1-(2,6,6-trimethyl-
1,3-cyclohexadien-1-yl)-1,3-butanedione of fraction 3
is set forth in Figure 6. The UV absorption curve
for l-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-
butanedione of fraction 3 is set forth in Figure 7
(~ 1 cm = 473 04; ~ max = 284 nm).
The infra-red analysis (in carbontetrachloride
solution) is as follows: lOOOcm 1; 1160 cm 1; 1175cm 1;
1225cm ; 1250cm 1; 1295cm 1; 1360cm 1; 1440cm 1;
1600cm (broad); 2920cm 1; and 2970cm 1.
The NMR analysis (in C C13 solution) is as follows:
Interpretation
1.10 (s) gem dimethyl protons 6H
1.75 (s) CH3 - C = C - IC - 3H
o
.
2.30 (s) O 3H
20 5.45 (s) olefinic proton lH
5.80 (s) olefinic protons 2H
15.67 (broad) bonded H
The mass spectral analysis for l-(2,6,6-trimethyl-
1,3-cyclohexadien-1-yl)-1,3-butanedione is as follows
(M/E Ratio followed by relative intensity): 39,30;
41,24; 43,100; 77,10; 85,77; 91,11; 105,11; 121,21; 191,
11 and 206p,12.
~ Z~6
-4Z-
E~AMPLE III
ROSE FORMULATION
To demonstrate the use of 1-(2,6,6-trimethyl-1,3-
cyclohexadien-l-yl)-1,3-butanedione in a rose formu-
lation, the following formula is provided:
Ingredient Parts by Weight
Phenylethyl alcohol......................... 200
Geraniol.................................... 400
Trichloromethylphenyl carbinyl acetate....... 20
10 Phenylethyl acetate........................... 60
Undecylenic aldehyde (10% in diethyl.......... 5
phthalate)
n-Nonyl aldehyde (10% in diethyl.............. 2
phthalate)
15 Musk ketone................................... l0
Musk ambrette................................ l0
Eugenol phenyl acetate....................... 20
Citronellol................................. 100
Vanillin (10% in diethyl phthalate)........... 6
20 Eugenol....................................... 30
Citronellyl formate.......................... 30
Geranyl acetate.............................. l0
~Linalool.................................... 40
Geranyl phenyl acetate....................... 50
25 Cis beta, ~-hexenyl acetate.................... 2
1-(2,6,6-trimethyl-1,3-cyclohexadien-......... 5
1-yl)-1,3-butanedione prepared according
to Example II
The addition of 0.5% of 1-(2,6,6-trimethyl-1,3-
cyclohexadien-1-yl)-1,3-butanedione lends a great
deal of strength and character to the rose fragrance.
It contributes great floralcy and the heady natural
sweetness of the red rose flower together with honey-
like, fruity, grape-like, and hay-like nuances and
sea-amber undertones with sweet-floral topnotes.
At lower concentrations (0.01Q~) its contribution
is more subtle; however, it still gives an interesting
natural effect with the ambergris-like undertone.
~Z1~
-43-
This product may normally be used from approximately
0.01% to 10% in perfume compositions. For special effects,
however, higher concentrations (50~- plus) can be used.
E~A~PLE IV
PREPARATION OF A SOAP COMPOSITION
One hundred grams of soap chips are produced according
to Example V of U.S. Patent 4,058,487 issued on November
15, 1977, as follows:
The sodium salt of an equal mixture of C10/Cl4
alkane sulfonate (95% active), 40 pounds, is
dissolved in a mixture of 80 pounds of anhydrous
isopropanol and 125 pounds of deionized water
at 150F. In this mixture is dissolved 10 pounds
of partially hydrogenated cocoanut oil fatty
acids and 15 pounds of sodium mono-C14 alkyl
maleate, and the pH of this solution is
adjusted to 6.0 by the addition of a small amount
of 50% aqueous solution of sodium hydroxide.
The isopropanol is distilled off, and the
remaining aqueous solution is drum dried.
The resulting solid actives are then blended
in a chip mixture with 10 pounds water, 0.2
- pounds titanium hydroxide and 0. 7 pounds of
the material, l-(2,6,6-trimethyl-1,3-cyclo-
hexadien-1-yl)-1,3-butanedione. The chips
are then plotted into logs, cut to size and
~ finally stamped into bars having a pH of
; approximately 6.9.
The perfumed soap manifests an excellent rose character
with excellent sweet, honey-like, fruity, hay-like and
floral nuances with a sea-amber and ambergris-like under-
tone and sweet-floral topnotes.
~)2~6
-44-
EXAMPLE V
PREPARATION OF A DETERGENT COMPOSITION
A total of 100 grams of a detergent powder pre-
pared according to United States Patent 4,058,472 and
containing 5% by weight of the sodium salts of a mixture
of sulfonated C14-C18 alkyl catechol as a surface active
component, the mixture being 60 parts by weight of
mono-C14-C18 alkyl catechol and 40 parts by weight of
di-C14-C18 alkyl catechol, 35% of sodium tetrapyrophos-
phate, 30o of sodium silicate, 20% of sodium carbonate,3% of sodium carboxymethyl cellulose and 7~ of starch
is mixed with 0.15 grams of 1-(2,6,6-trimethyl-1,3-
cyclohexadien-l-yl)-1,3-butanedione of Example II until
a substantially homogeneous composition is obtained.
This composition has an excellent rose aroma with sweet,
honey-like, fruity, grape-like, hay-like and floral
nuances and a sea-amber/ambergris-like undertone with
sweet-floral topnotes.
EXAMPLE VI
TOBACCO FORMULATION
A tobacco mixture is produced by admixing the
following ingredients:
Ingredient Parts by Weight
Bright..................................... . 40.1
25 Burley....................................... 24.9
Maryland..................................... l.l
Turkish..................................... 11.6
Stem (flue-cured)........................... 14.2
Glycerine.................................... 2.8
30 Water......................................... 5.3
Cigarettes are prepared from this tobacco.
-45-
The following flavor formulation is prepared:
Ingredient- Parts by Weight
Ethyl butyrate.............................. .05
Ethyl valerate.............................. .05
5 Maltol...................................... 2.00
Cocoa extract............................. 26.00
Coffee extract............................ 10.00
Ethyl alcohol............................. 20.00
Water..................................... 41.90
The above-stated tobacco flavor formulation is
applied at a rate of 0.1~ to all of the cigarettes
produced using the above tobacco formulation. Half
of the cigarettes are then treated with 50 or 150 ppm
of l-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butane-
dione produced according to the process of Example II.
The control cigarettes not containing the 1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione and
the experimental cigarettes which contain the 1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione
produced according to the process of Example II are
evaluated by paired comparison, and the results are as
follows:
The experimental cigarettes are found, on smoking,
to have improved "body", enhanced tobacco character,
to be sweeter, and to have more pronounced hay/tea
character in the main stream. The experimental ciga-
rettes are also found, on smoking, to be sweeter, more
tobacco-like, having a "fresh cigarette pack" aroma in
the side stream.
The tobacco of the experimental cigarettes, prior
to smoking, has sweet, fruity, berry-like, fresh
squeezed fruit tapple and grape) juice-li]ce, hay-li]ce,
and tea-like aroma characteristics.
All cigarettes are evaluated for smoke flavor with
a 20 mm cellulose acetate filter.
The 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-
butanedione produced according to Example II enhances
the tobacco-like taste and aroma of the blended cigarettes
imparting to it sweet, natural tobacco "fresh cigarette
pack" notes as well as hay/tea notes.
-46-
EXAMPLE VII
PREPARATION OF A COSMETIC-POWDER CO~POSITION
A cosmetic powder is prepared by mixing in a ball
mill, 100 grams of talcum powder with 0.25 grams of
1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butane-
dione prepared according to Example II. It has an
excellent sweet, honey-like, fruity, grape-like, rose-
like, ionone-like, hay-like and floral-like aroma with
a sea-amber/ambergris-like undertone and sweet-floral
10 topnotes.
EX~-IPLE VIII
PERFUMED LIQUID DETERGENT
Concentrated liquid detergents with sweet, honey-
like, fruity, grape-like, rose-like, ionone-like, hay-
15 like and floral aromas with sea-amber/ambergris-like
undertones and sweet-floral topnotes are prepared by
adding 0.10%, 0.15% and 0.20% of 1-(2,6,6-trimethyl-
1,3-cyclohexadien-1-yl)-1,3-butanedione prepared
according to Example II. They are prepared by adding -
20and homogeneously mixing the appropriate quantity of :
1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-butane-
dione in the liquid detergent. The detergents all
possess sweet, honey-like, fruity, grape-like, rose-
like, ionone-like, hay-like and floral aromas with
25sea-amber/ambergris-like undertones, the intensity
increasing with greater concentrations of 1-(2,6,6- .
trimethyl-1,3-cyclohexanedien-1-yl)-1,3-butanedione. :
,. ..
EXAMPLE IX
PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUr~E
~ .,
1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1,3-
butanedione prepared according to E~ample II is incorpo-
rated into colognes of several strengths at concentrations
of 2.0%, 2.5%, 3.0%, 3.5%, 4.0% and 5.0% in 85% aqueous
ethanol; and into several concentrations of handkerchief
35perfumes at the rate of 15%, 20% and 25% (in 95~ aqueous
eth~nol). DistiDct and definite sweet, hone~-like,
~ ~Q281~
-47-
fruity, grape-like, rose-like, ionone-like, hay-like
and floral aromas with sea-amber/ambergris-like under-
tones and sweet-floral topnotes are imparted to the
colognes and to the handkerchief perfumes of the
several concentrations set forth above.
E~IPLE X
PREPARATION OF A COLOGNE AND EIA21DRERCHIEF PERFU~E
The composition of Example III is incorporated into
colognes of several concentrations, 2.0%, 2.5go~ 3.0gO~
3.5%, 4.0% and 5.0%, in 85% aqueous ethanol; and into
~handkerchief perfumes at concentrations of 15%, 20% and
25% (in 95% aqueous ethanol). The use of the 1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione in the
. composition of Example III affords a distinct and definite
strong rose aroma with sweet, fruity, hay-like, and
floral aromas and sea-amber/ambergris-like undertones
with sweet-floral topnotes to the handkerchief perfumes
and the colognes at all of the concentrations set
forth above.
EXA~lPLE YI
PREPARATION OF A SOAP CO~lPOSITION
One hundred grams of soap chips are intimately
admixed with one gram of l-(2,6,6-trimethyl-1,3-cyclo-
hexadien-l-yl)-1,3- butanedione until a substantially
homogeneous composition is obtained. The perfumed
soap composition manifests an excellent sweet, honey-
like, fruity, grape-like, rose-like, ionone-like, hay-
like and floral aroma with sea-amber/ambergris-like
undertones and sweet-floral topnotes.
EXAMPLE XII
PREPARATION OF A DETERGENT COMPOSITION
A total of 100 grams of a detergent powder is
intirnately admixed with 0.15 grams of 1-(2,6,6-trimethyl-
1,3-.cyclohexadien-1-yl)-1,3-butanedione prepared accord-
ing to Example II until a substantially homogeneous
2~
-48-
composition is obtained. This composition has an
excellent sweet, honey-like, fruity, grape-like, rose-
like, ionone-like, hay-like and floral aroma with sea-
amber/ambergris-like undertones and sweet-floral topnotes.
EXAMPLE XIII
RASPBERRY FLAVOR
The following basic raspberry flavor formulation is
prepared:
Ingredient Parts by Weight
10 Vanillin..................................... 2.0
Maltol...................................... 5.0
Parahydroxybenzylacetone.................... 5.0
Alpha-ionone (10% in propylene glycol)...... 2.0
Ethyl butyrate.............................. 6.0
15 Ethyl acetate............................... l6.0
Dimethyl sulfide............................ l.0
Isobutyl acetate........................... 13.0
Acetic acid................................ 10.0
Acetaldehyde............................... 10.0
20 Propylene glycol........................... 930.0
To half of the above formulation, at the rate of
0.2%, 3-hydroxy-1-(2,6,6-trimethyl-1,3-cy clohexadien-
l-yl)-l-butanone prepared according to Example I (A)
is added. Nothing is added to the other half of the
above formulation. The raspberry flavor formulation
with and without the addition of 3-hydroxy-1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1-butanone are
compared at the rate of 0.01% (100 ppm) in water and
evaluated by a bench panel of five members.
The flavor containing 3-hydroxy-1-(2,6,6-trimethyl-
1,3-cyclohexadien-1-yl)-1-butanone has a very pleasing
characteristic raspberry juice aroma. It is natural
juice-like whereas the flavor without 3-hydroxy-1-
(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone
has ionone-like notes dominating. The taste of the
flavor formul~tion containing the 3-hydroxy-1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1-butanone is also
raspberry juice-like, round and pleasant as distinct
from the flavor without the 3-hydroxy-1-(2,6,6-trimethyl-
--d~9--
1,3-cyclohexadien-1-yl)-1-butanone which is unbalanced,
ionone-like. Therefore, the panel prefers, unanimously,
the flavor formulation containing the 3-hyclroxy-1-
(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone.
EXAMPLE XIV
A. POWDER FLAVOR COMPOSITION
20 Grams of the flavor composition of Example XIII
is also emulsified in a solution containing 300 gm gum
acacia and 700 gm water. The emulsion is spray-dried
with a Bowen Lab Model Drier utilizing 260 c.f.m. of air
with an inlet temperature of 500F, an outlet temperature
of 200F, and a wheel speed of 50,000 rpm.
- B. SUSTAINED RELEASE FLAVOR
The following mixture is prepared:
Ingredient Parts by Weight
- Liquid Raspberry Flavor............... 20
Composition of Example II
Propylene glycol...................... .9
Cab-O-Sil M-5......................... .5.00
(Brand of Silica produced by the
Cabot Corporation of 125 High Street,
Boston, Mass. 02110
Physical Properties:
Surface area: 200 m2/gm
Nominal particle size: 0.012 microns
Density: 2.3 lbs/cu.ft.)
The Cab-O-Sil is dispersed in the liquid raspberry
flavor composition of Example XIII with vigorous
stirring, thereby resulting in a viscous liquid.
71 Parts by weight of the powder flavor composition
of Part A, supra, is then blended into the said viscous
liquid, with stirring, at 25C for a period of 30 minutes
resulting in a dry, free flowing sustained release
flavor powder.
-50- ~ J~
EXAMPLE XV
10 Parts by weight of 50 Bloom pigskin gelatin
is added to 90 parts by weight of water at a temperature
of 150F. The mixture is~agitated until the gelatin is
completely dissolved and the solution is cooled to
120F. 20 Parts by weight of the liquid flavor composition
of Example XIII is added to the solution which is then
homogenized to form an emulsion having particle size
typically in the range of 2-5 microns. This material
is kept at 120F under which conditions the gelatin will
not gel.
Coacervation is induced by adding, slowly and
uniformly, 40 parts by weight of a 20% aqueous solution
of sodium sulphate. During coacervation, the gelatin
molecules are deposited uniformly about each oil droplet
as a nucleus.
Gelation is effected by pouring the heat coacervate
mixture into 1,000 parts by weight of 7% aqueous solution
of sodium sulphate at 65F. The resulting jelled coacer-
vate may be filtered and washed with water at temperaturesbelow the melting point of gelatin, to remove the salt.
Hardening of the filtered cake, in this example, is
effected by washing with 200 parts by weight of 37%
solution of formaldehyde in water. The cake is then
washed to remove residual formaldehyde.
EXAMPLE XVI
CHEWING GUM
100 Parts by weight of chicle are mixed with 4
parts by weight of the flavor prepared in accordance
with Example XIV. 300 Parts of sucrose and 100 parts
of corn syrup are added. Mixing is effected in z
ribbon blender with jacketed side walls of the type
manufactured by the Baker Perkins Co.
The resultant chewing gum blend is then manu-
factured into strips 1 inch in width and 0.1 inchesin thickness. The strips are cut into lengths of 3
inches each. On chewing, the chewing gum has a
pleasant, long-lasting raspberry flavor.
-51-
EXAMPLE XVII
CHE~ING GUM
100 Parts by weight of chicle are mixed with 18
parts by weight of the flavor prepared in accordance
with E~ample XV. 300 Parts of sucrose and 100 parts
of corn syrup are then added. Mixing is effected in a
ribbon blender with jacketed side walls of the type
manufactured by the Baker Perkins Co.
The resultant chewing gum blend is then manufactured
into strips 1 inch in width and 0.1 inches in thickness.
The strips are cut into lengths of 3 inches each. On
chewing, the chewing gum has a pleasant, long-lasting
raspberry flavor.
- EXAMPLE XVIII
15TOOTHPASTE FO~ULATION
The following separate groups of ingredients are
~prepared:
Parts by Weight Ingredient
Group "A"
30.200......................... Glycerin
15.325......................... Distilled water
.100......................... Sodium benzoate
.125......................... Saccharin Sodium
.400......................... Stannous Fluoride
Grou~ "B"
-
12.500......................... Calcium carbonate
37.200......................... Dicalcium phosphate
(dihydrate)
Group "C"
2.000.......................... Sodium N-lauroyl sar-
cosinate (foaming agent)
Group "D"
1.200.......................... Flavor Material of
Example XV
100.000 (Total)
-52
PROCEDURE:
1. The ingredients in Group "~" are stirred and heated
in a steam jacketed kettle to 160F.
2. Stirring is continued for an additional three to
five minutes to form a homogeneous gel.
3. The powders of Group "s" are added to the gel, while
mixing until a homogeneous paste is formed.
4. With stirring, the flavor of "D" is added and lastly
the sodium n-lauroyl sarcosinate.
5. The resultant slurry is then blended for one hour.
The completed paste is then transferred to a three
roller mill and then homogenized, and finally tubed.
The resulting toothpaste when used in a normal
toothbrushing procedure yields a pleasant raspberry
flavor, of constant strong intensity throughout said
procedure (1-1.5 minutes).
EXAMPLE XIX
CHEWABLE VITAMIN TABLETS
The flavor material produced according to the
process of Example XIII is added to a chewable vitamin
tablet formulation at a rate of 10 gm/Kg which chewable
vitamin tablet formulation is prepared as follows:
In a Hobart Mixer, the following materials are
blended to homogeneity:
Gms/1000
In~redients Tablets
Vitamin C (ascorbic acid)........... 70.0
as ascorbic acid-sodium
ascorbate mixture 1:1
30 Vitamin Bl (thiamine mononitrate).... 4.0
as Rocoat thiamine mononitrate
33 1/3% (Hoffman La Roche)
Vitamin B2 (riboflavin) as........... 5.0
Rocoat riboflavin 33 1/3%
35 Vitamin B6 (pyridoxine hydro-........ 4.0
chloride) as Rocoat pyridoxine
hydrochloride 33 1/3~
Niacinamide as Rocoat niacinamide... 33.0
33 1/3~
40 Calcium pantothenate................ ll.5
~U2~
-53-
Gms/1000
Ingredients Tablets
Vitamin B 2 (cyanocobalamin)............... ..3.5
as Merck a.1~ in gelatin
Vitain E (dl-alpha tocopheryl.............. ..6.6
acetate) as dry Vitamin E
acetate 33 1/3% Roche
d-Biotin................................... .Ø044
Certified lake color....................... ..5.0
10 Flavor of Example XIII..................... (as indicated
above)
Sweetener - sodium saccharin............... ..l.0
Magnesium stearate lubricant............... .l0.0
Mannitol q.s. to make...................... 500.0
Preliminary tablets are prepared by slugging with flat-
faced punches and grinding the slugs to 14 mesh. 13.5
g dry Vitamin A acetate and 0.6 Vitamin D are then added
as beadlets. The entire blend is then compressed using
concave punches at 0.5 g each.
; Chewing of the resultant tablets yields a pleasant,
long-lasting, consistently strong raspberry flavor for
a period of 12 minutes.
EXAMPLE XX
CHEWI~IG TOBACCO
-
Onto lOO pounds of tobacco for chewing (85%
Wisconsin leaf and 15% Pennsylvania leaf) the following
casing is sprayed at a rate of 30%:
Ingredients Parts by Weight
Corn Syrup................................. ....60
30 Licorice.................................... ....10
Glycerine.................................. ....20
Fig Juice.................................. .....4.6
Prune Juice................................ .....5
Flavor Material of Example XIV............. ....Ø4
The resultant product is redried to a moisture
content of 20%. On che~ing, this tobacco has an
excellent, substantially consistent, long-lasting
raspberry (20 minutes) nuance in conjunction with the
main fruity tobacco note.
``` 1~ Z~l~
-54-
EXAMPLE ~I
ROSE FOR~ULATIO~
To demonstrate the use of 3-hydroxy-1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1-butanone in a rose
formulation, the following formula is provided:
Ingredient Parts bv Weight
Phenyl ethyl alcohol................... 200
Geraniol............................... 400
Trichloromethylphenyl carbinyl.......... 20
10 acetate
~Phenyl ethyl acetate.................... 60
Undecylenic aldehyde (10% in diethyl..... 5
phthalate)
n-Nonyl aldehyde (10g~ in diethyl........ 2
15 phthalate)
Musk ketone............................. l0
Musk ambrette........................... l0
Eugenol phenyl acetate.................. 20
Citronellol............................ 100
20 Vanillin (10% in diethyl phthalate)....... 6
Eugenol................................. 30
Citronellyl formate..................... 30
Geranyl acetate......................... l0
Linalool................................ 40
25 Geranyl phenyl acetate................... 50
Cis beta, y-hexenyl acetate.............. 2
3-hydroxy-1-(2,6,6-trimethyl-1,3-........ 5
cyclohexadien-l-yl)-l-butanone
prepared according to
30 Example I (A)
1000
The addition of 0.5% of 3-hydroxy-1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1-butanone lends
a great deal of strength and character to the rose
fragrance. It contributes floralcy and fruitiness
with hay-like and menthane-like undertones.
At lower concentrations (0.01%) its contribution
is more subtle, however, it gives an interesting natural
effect.
l~Z~
-55--
This product may normally be used from approximately
0.01% to 10% in perfume compositions. For special
effects, however, higher concentrations (50%) can be
used.
5 EXAMPLE XXII
PREPARATION OF A SOAP CO~OSITION_
100 Grams of soap chips are produced according to
Example V of United States Patent 4,058,487 issued on
November 15, 1977, as follows:
The sodium salt of an equal mixture of C10/C14
alkane sulfonates (95~ active), 40 lbs., is
dissolved in a mixture of 80 lbs. of anhydrous
isopropanol and 125 lbs. of deionized water
at 150F. In this mixture is dissolved 10
lbs. of partially hydrogenated coconut oil
fatty acids and 15 lbs. of sodium mono-C14-
alkyl maleate, and the pH of this solution
is adjusted to 6.0 by the addition of a
small amount of a 50% aqueous solution of
NaOH. The isopropanol is distilled off and
the remaining aqueous solution is drum dried.
The resulting solid actives are then blended
in a chip mixer with 10 lbs. water 0.2 lb.
titanium hydroxide and 0.75 lb. of the perfume
composition of Example XXI. The chips are
then plodded into logs, cut to size and
finally stamped into bars, having a pH of
approximately 6.9.
The perfumed soap manifests an excellent rose character
with excellent sweet, floral and fruity notes.
-56-
EX~MPLE XXIII
PREPARATION OF A DETERGENT COMPOSITION
A total of 100 grams of a detergent powder prepared
according to U.S. Patent 4,058,472 and containing 5% by
weight of the sodium salts of a mixture of sulfonated
C14-C18 alkyl catechol as a surface active component,
the mixture being 60 parts by weight of mono-C14-C18
alkyl catechol and ~0 parts by weight of di-C14-C18 alkyl
catechol, 35~ of sodium tetrapyrophosphate, 30% of sodium
silicate, 20% of sodium carbonate, 3% of sodium carboxy-
methylcellulose and 7% of starch, is mixed with 0.15
grams of the perfume composition of Example XXI until
a substantially homogeneous composition is obtained.
This composition has an excellent rose aroma with sweet,
floral and fruity notes.
EXAMPLE XXIV
PREPARATION OF A COSr~ETIC POWDER COMPOSITION
A cosmetic powder is prepared by mixing in a ball
mill, 100 g of talcum powder with 0.25 g of 3-hydroxy-
20 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone
prepared according to Example I (A). It has an excel-
lent floral, fruity, tobacco-like fragrance having
rose, hay and menthane undertones.
EXAr~PLE XXV
PERFUMED LIQUID DETERGENT
Concentrated liquid detergents with floral, fruity,
tobacco-like fragrances having rose, hay and menthane
undertones are prepared containing 0.10%, 0.15% and
0.20% of 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexa-
dien-l-yl)-l-butanone prepared according to Example I (A).
They are prepared by adding and homogeneously mixing the
appropriate quantity of 3-hydroxy-1-(2,6,6-trimethyl-
1,3-cyclohexadien-1-yl)-1-butanone in the liquid deter-
gents. The detergents all possess a floral, fruity,
tobacco-like fragrance having rose, hay and menthane
undertones, the intensity increasing with greater con-
centrations of 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclo-
hexadien-l-yl)-l-butanone.
-57-
EXAMPLE ~XVI
PREPAR~TION OF A COLOGNE AND HANDKERCHIEF PERFUME
3-Hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-
l-yl)-l-butanone prepared according to the process of
Example I (A) is incorporated in a cologne at a concen-
tration of 2.5% in 85~ aqueous ethanol; and into a
handkerchief perfume at a concentration of 20~ (in 95~ -
aqueous ethanol). A distinct and definite floral,
fruity, tobacco-like fragrance having rose, hay and
menthane undertones is imparted to the cologne and
to the handkerchief perfume.
EXAMPLE XXVII
PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME
The composition of Example XXI is incorporated in
a cologne at a concentration of 2.5% in 85~ aqueous
ethanol; and into a handkerchief perfume at a concen-
tration of 20~ (in 95% aqueous ethanol). The use of
3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-
l-butanone in the composition of Example XXI affords
a distinct and definite strong, floral, fruity, tobacco-
like fragrance having rose, hay and menthane undertones
to the handkerchief perfume and cologne.
EXA~IPLE XXVIII
PREPARATION OF SOAP C02qPOSITION
One hundred grams of soap chips produced according
to Example V of U.S. Patent 4,058,487 are mixed with one
gram of 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-
l-yl)-l-butanone until a substantially homogeneous com-
position is obtained. The perfumed soap composition
m~nifests an excellent floral, fruity, tobacco-like
fragrance having rose, hay and menthane undertones.
-58-
EXAMPLE XXIX
PRÆPARATION OF A DETERGENT COMPOSITION
A total of 100 g of a detergent powder prepared
as in Example XII, supra,~ is mixed with 0.15 g of the
3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-
l-butanone of Example I (A) until a substantially
homogeneous composition is obtained. This composition
has an excellent floral, fruity, tobacco-like fragrance
having rose, hay and menthane undertones.
EXAMPLE XXX
TOBACCO FORMULATION
A tobacco mixture is produced by admixing the
following ingredients:
Ingredient Parts by Weight
15 Bright........................................ 40.1
Burley....................................... 24.9
Maryland...................................... l.l
Turkish...................................... 11.6
Stem (flue-cured)..................... ,....... 14.
20 Glycerine.................................. .... 2.8
Water..................................... .... 5.3
;Cigarettes are prepared from this tobacco.
The following flavor formulation is prepared:
Ingredient Parts by Weight
25 Ethyl butyrate............................. .... .05
Ethyl valerate............................ .... .05
Maltol.................................... ... 2.00
Cocoa extract............................. .. 26.00
Coffee extract............................ .. l0.Q0
30 Æthyl alcohol.............................. .. 20.00
Water..................................... .. 41.90
The above-stated tobacco flavor formulation is
applied at the rate of 0.1% to all of the cigarettes
produced using the above tobacco formulation. Half
of the cigarettes are then treated with 150 or 300
ppm of 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-
-59- ~Z8~
l-yl)-l-butanone produced according to the process of
Example I -(A). The control cigarettes not containing
the 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-
yl)-l-butanone produced according to the process of
Example I (A) and the experimental cigarettes which
contain the 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclo-
hexadien-l-yl)-l-butanone produced according to the
process of Example I (A) are evaluated by paired com-
parison and the results are as follows:
The experimental cigarettes are found to have more
body and to be sweeter, more aromatic, more tobacco-like
~and less harsh with sweet, distinctive dried fruit-like,
floral and woody notes. The tobacco of the experimental
cigarettes, prior to smoking, has sweet, distinctive
dried fruit-like, floral and woody notes. All cigarettes
are evaluated for smoke flavor with a 20 mm cellulose
acetate filter.
The 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclohexadien-
l-yl)-l-butanone produced according to the process of
Example I (A) enhances the tobacco-like taste and aroma
of the blended cigarettes, imparting to it, sweet,
dried fruit-like, floral and woody notes. In addition,
the smoke flavor is cleaner.
EXAMPLE XXXI
Utilizing the procedure of Example I of column
15 of United States Patent 3,632,396, a nonwoven cloth
substrate useful as a dryer-added fabric-softening
~article of manufacture is prepared wherein the substrate,
the substrate coating and the outer coating and the
perfuming material are as follows:
1. A water "dissolvable" paper ("Dissolvo
Paper"):
2. Adogen 448 (m.p. about 140F) as the substrate
coating; and
3. An outer coating having the following formu-
lation (m.p. about 150F):
Z~
-60-
57 percent C20 22 HAPS
22 percent isopropyl alcohol
20 percent antistatic agent
1 percent of the cyclohexadien-l-yl-l-
butanone derivative for mixtures thereof
of our invention as set forth in the
Table I below and giving rise to the
aroma nuances set forth in the Table I
below:
TABLE I
NAME OF COMPOUND(OR MIXTURE) FRAGRANCE CHARACTERISTIC
3-hydroxy-1-(2,6,6-trimethyl- A floral, fruity, tobacco
1,3-cyclohexadien-1-yl)-1- aroma with rose notes and
butanone hay, menthane undertones.
15 1-(2,6,6-trimethyl-1,3- Imparts a sweet, honey-
cyclohexadien-l-yl)-1,3- like, fruity, grape-like,
butanedione rose-like, ionone-like,
hay-like and floral aroma
with sea-amber and amber-
gris-like undertones and
sweet-floral topnotes.
50:50 mixture of 3-hydroxy- Imparts a floral, fruity,
1-(2,6,6-trimethyl-1,3- tobacco, sweet, honey-like,
cyclohexadien-l-yl)-l- fruity, grape-like, rose-
25 ~butanone and 1-(2,6,6- like, ionone-like, hay-
trimethyl-1,3-cyclohexa- like and floral aroma with
dien-1-yl)-1,3-butanedione strong sea-amber and amber-
i(mole ratio: 1:1) gris undertones and rose,
hay, floral and menthane
topnotes.
Fabric-softening compositions prepared as set forth
above having the above aroma characteristics essentially
consist of a substrate having a weight of about 3 grams
per 100 square inches, a substrate coating of about
1.85 grams per 100 square inches of substrate and an
outer coating of about 1.4 grams per 100 square inches
of substrate, thereby providing a total aromatized
substrate and outer coating weight ratio of about 1:1
by weight of the substrate. The aromas as set forth
in Table I above are imparted in a pleasant manner to
the head space in the dryer on operation thereof using
the said dryer added fabric softening nonwoven fabric.
2~
-61-
BRIEF DESCRIPTION OF TIIE DRA~INGS
Figure 1 is the nuclear magnetic resonance (NMR)
spectrum for 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyclo-
hexadien-l-yl)-l-butanone~produced according to
~xample I (A).
Figure 2 is the infra-red (IR) spectrum for 3-
hydroxy-l-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-
butanone produced according to Example I (A).
Figure 3 is the mass spectrum (MS) for 3-hydroxy-
1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-1-butanone
~produced according to Example I (A).
Figure 4 is the ultraviolet (UV) absorption spec-
trum for 3-hydroxy-1-(2,6,6-trimethyl-1,3-cyelohexadien-
l-yl)-l-butanone produced according to Example I ~A)
using a methanol solvent.
Figure 5 is the NMR spectrum for 1-(2,6,6-tri-
methyl-1,3-cyclohexadien-1-yl)-1,3-butanedione produced
according to Example II.
Figure 6 is the infra-red spectrum for 1-(2,6,6-
trimethyl-1,3-cyclohexadien-1-yl)-1,3-butanedione
produced according to Example II.
Figure 7 is the UV absorption curve [ElCml~ =
473.04; Lamda = 284nm] for 1-(2,6,6-trimethyl-1,3-
cyclohexadien-l-yl)-1,3-butanedione produced according
to Example II.
