Schiff base reaction products of mixtures of aldehydes including helional and alkyl anthranilates; derivatives thereof; and organoleptic uses thereof

Described are schiff base reaction products of alkyl anthranilates having the structure: ##STR1## wherein R.sub.3 represents methyl or ethyl; helional having the structure: ##STR2## and aldehydes having the generic structure: ##STR3## wherein R represents a hydrocarbyl or hydroxy hydrocarbyl moiety including the aldehydes: PA0 (a) pinoacetaldehyde having the structure: ##STR4## (b) pinoisobutyraldehyde having the structure: ##STR5## and (c) lyral, a mixture of compounds having the structures: ##STR6## and derivatives there and organoleptic uses thereof in augmenting or enhancing the aroma or taste of consumable materials including perfume compositions, colognes, perfumed articles, foodstuffs, chewing gums and beverages. Also described are processes for deodorizing articles and compositions of matter and axillary regions of mammalian species comprising the step of treating such articles, compositions or axillary regions with schiff base reaction products of such alkyl anthranilates and helional; or schiff base reaction products of such alkyl anthranilates, helional and aldehydes defined according to the structure: ##STR7##

BACKGROUND OF THE INVENTION 
Our invention relates to reaction products which are schiff bases of 
aldehydes and alkyl anthranilates and uses thereof in (i) augmenting or 
enhancing the aroma or taste of perfume compositions, colognes, perfumed 
articles, foodstuffs, chewing gums and beverages and (ii) effecting 
deodorization of skin surfaces, compositions and articles having 
undesirable or aesthetically displeasing aromas. 
Inexpensive chemical compositions of matter which can provide green, orange 
flower, fruity, ozoney, sweet, anisic, melony, herbaceous, balsamic, 
walnut and floral aromas with grape, fruity, green, flower, anisic, 
ozoney, piney, meloney and lemony topnotes are highly desirable in the art 
of perfumery. Many of the natural materials which provide such fragrances 
and contribute desired nuances to perfumery compositions as well as 
perfumed articles including solid or liquid anionic, cationic, nonionic or 
zwitterionic detergents, fabric softener compositions and fabric softener 
articles are high in cost, vary in quality from one batch to another 
and/or are generally subject to the usual variations of natural products. 
By the same token, materials which can provide intense floral, oriental, 
citrus, lemony, meloney, watermelon, green and concord grape aromas with 
watermelon, floral, oriental, citrus, lemony, meloney, green, raspberry 
and concord grape tastes are highly useful and well known in the art of 
flavoring for foodstuffs, toothpastes, chewing gums, medicinal products 
and chewing tobaccos. Many of the natural materials which provide such 
flavor nuances and contribute desired nuances to flavoring compositions 
are high in cost, 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 essential flavor and 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 else contribute undesirable 
or unwanted odor to the compositions. The search for materials which 
provide, for example, a more refined grape-like flavor or more refined 
lemon flavor or more refined watermelon flavor, for example, has been 
difficult and relatively costly in the areas of both natural products and 
synthetic products. By the same token, the search for materials which can 
provide a more refined green, orange flower, fruity, ozoney, sweet, 
anisic, melony, herbaceous, balsamic, walnut and floral aromas with grape, 
fruity, green, flower, anisic, ozoney, piney, meloney and lemony topnotes 
has been difficult and relatively costly in the areas of both natural 
perfumery products and synthetic perfumery products. 
Artificial flavoring agents for foodstuffs have received increasing 
attention for many years. For many years such food flavoring agents have 
been preferred over natural flavoring agents at least in part due to their 
diminished costs and their reproducible flavor qualities. For example, 
natural food flavoring agents such as extracts, concentrates and the like 
are often subject to wide variations due to changes in quality and type 
and treatment of the raw materials. Such variations can be reflected in 
the end products and result in unfavorable flavor characteristics in the 
end product. Additionally, the presence of the natural product in the 
ultimate food may be undesirable because of increasing tendency to spoil. 
This is particularly troublesome in food and food uses where such products 
as dips, soups, chips, sausages, gravies and desserts and the like are apt 
to be stored prior to use. 
Even more desirable are products that can serve to substitute for 
difficult-to-obtain natural perfumery oils and, at the same time, 
substitute for natural flavoring ingredients in foodstuffs, chewing gums, 
medicinal products, toothpastes and chewing tobaccos. 
Reaction products of carbonyl-containing compounds and amine-containing 
compounds are well known in the art of flavoring and in the art of of 
perfumery. Thus, U.S. Pat. No. 4,618,501 issued on Oct. 21, 1986 discloses 
the flavoring of foodstuffs with alpha,beta-keto-amines and states that an 
alpha,beta-keto-amine having a nutty corn, cereal aroma may be used for 
flavoring compositions for foods having the structure: 
##STR8## 
wherein R.sub.1, R.sub.2 and R.sub.3 are selected from the group 
consisting of a saturated or unsaturated alkyl straight or branched chain 
hydrocarbons having from 1-3 carbon atoms. 
U.S. Pat. No. 3,625,710 issued on Dec. 7, 1971 discloses the use of 
aldimines as chocolate-like flavors which aldimines are resulting from the 
reaction product of amines and aldehydes, for example, 
N-isobutylidenefurfurylamine, N-isopentylidenefurfurylamine, 
N-isopentylideneisopentylamine. 
Schiff bases are also well known in the art of perfumery. Thus, for 
example, Chemical Abstracts Volume 103, 1985, No. 123134z (Abstract of 
Japan Kokai No. 60/78951 discloses the use in perfumery of compounds 
having the structure: 
##STR9## 
The book "Flavor & Fragrance Materials-1987" published by Allured 
Publishing Corporation, P.O. Box 318, Wheaton, Ill. 60189-0318 discloses 
on page 154 the commercial availability of the following schiff bases: 
Methyl anthranilate and amyl cinnamic aldehyde; 
Methyl anthranilate and hydroxy citronellal; 
Methyl anthranilate and lilial; 
Methyl anthranilate and anisic aldehyde; 
Methyl anthranilate and decanal; 
Methyl anthranilate and lyral; 
Methyl anthranilate and iso-nonylaldehyde; 
Methyl anthranilate and phenylacetaldehyde; 
Schiff bases are also known to be useful as intermediates in producing 
other fragrance materials. Thus, U.S. Pat. No. 3,898,283 issued on Aug. 5, 
1975 discloses novel schiff base intermediates used in producing 4 or 5 
phenylpentenals having the structure: 
##STR10## 
wherein X is a moiety selected from the group consisting of: 
##STR11## 
and wehrein R.sub.a is hydrogen or methyl. 
Nothing in the prior art however discloses the novel reaction products or 
reaction product mixtures of our invention having unobvious, unexpected 
and advantageous organoleptic properties. 
Indeed, nothing in the prior art is indicative of the novel schiff base 
reaction products of our invention having deodorizing properties that is, 
having a deodorant value of 0.50 up to 3.5 as measured by the deodorant 
value test described in U.S. Pat. No. 4,304,679 incorporated by reference 
herein or having a Lipoxidase-inhibiting capacity of at least 50% and a 
Malodour reduction value of from 0.25 up to 3 as measured by the Malodour 
reduction value test disclosed in U.S. Pat. No. 4,663,068 incorporated by 
reference herein.

DETAILED DESCRIPTION OF THE DRAWINGS 
Referring to FIG. 18, FIG. 18 is a schematic cut-away elevation diagram of 
the extrusion and pelletizing apparatus useful in carrying out a process 
for incorporation of the schiff base compositions of our invention into 
polymers during the operation of said apparatus. Motor 15 drives the 
extruder screws located at 23A in barrel 16, the extruder being operated 
at temperatures in the range of about 150.degree. up to about 250.degree. 
C. At the beginning of the barrel resin at source 12 together with 
additives, e.g., opacifiers, processing aids, colors, pearlescent agents 
and densifiers at location 13 is added via addition funnel 14 into the 
extruder. Simultaneously (when the operation reaches "steady state", one 
or more of the schiff base compositions of our invention is added to the 
extruder at one, two or more of barrel segments 3-8 of the extruder (which 
may be a twin screw or single screw extruder) at locations 18a, 18b, 18c 
and 18d by means of gear pump 23 from source 17. From source 19 into 
barrel segments 5-10, the gaseous or liquid blowing agents, e.g., 
nitrogen, carbon dioxide and the like are added simultaneously with the 
addition of the schiff base compositions of our invention. The feed rate 
range of the resin is about 80-300 pounds per hour. The feed rate range of 
the schiff base compositions taken alone or further together with other 
perfumant is between 1 and 45% of the feed rate range of the resin. The 
blowing agent rate range is such that the pressure of the gas or the 
pressure over the liquid being fed into the extruder is between about 50 
and 200 psig. If desired, the extruded ribbon or cylinder may be passed 
through water bath 20 and pelletizer 21 into collection apparatus 21a. 
Referring to FIGS. 19 and 20, there is provided a process for forming 
scented polymer pellets (wherein the polymer may be a thermoplastic 
polymer such as low density polyethylene or polypropylene or a copolymer 
of ethylene and vinyl acetate or mixtures of polymers and copolymers such 
as copolymers of ethylene and vinyl acetate and polyethylene) such as 
pellets useful in the formation of plastic particles useful in fabricating 
cetain articles which may be perfumed. This process comprises heating the 
polymer or mixture of polymers to the melting point of said polymer or 
mixture of polymers, e.g., 250.degree. C. in the case of low density 
polyethylene. The lower most portion of the container is maintained at a 
slightly lower temperature and the material in the container is taken off 
at such location for delivery through the conduit. Thus, referring to 
FIGS. 20 and 21, in particular, the apparatus used in producing such 
elements comprises a device for forming the polymer containing perfume, 
e.g., polyethylene or polyethylene-polyvinyl acetate or mixtures of same 
or polypropylene, which comprises a vat or container 212 into which the 
polymer taken alone or in admixture with other copolymer and the perfuming 
substance which is at least one of the schiff base compositions of our 
invention or mixtures of schiff base compositions and other compatible 
perfumes is placed. The container is closed by means of an air-tight lid 
228 and clamped to the container by bolts 265. A stirrer 273 traverses the 
lid or cover 228 in an air-tight manner and is rotatable in a suitable 
manner. A surrounding cylinder 212A having heating coils which are 
supplied with electric current through cable 214 from a rheostat or 
control 216 is operated to maintain the temperature inside the container 
212 such that the polymer in the container will be maintained in the 
molten or liquid state. It has been found advantageous to employ polymers 
at such a temperature that the viscosity will be in the range of 90-100 
sayboldt seconds. The heater 218 is operated to maintain the upper portion 
of the container 212 within a temperature range of, for example, 
220.degree.-270.degree. C. in the case of low density polyethylene. The 
bottom portion of the container 212 is heated by means of heating coils 
212A regulated through the control 220 connected thereto through a 
connecting wire 222 to maintain the lower portion of the container 212 
within a temperature range of 220.degree.-270.degree. C. 
Thus, the polymer or mixture of polymers added to the container 212 is 
heated from 10-12 hours, whereafter the perfume composition or perfume 
material which contains one or more of the schiff base compositions of our 
invention is quickly added to the melt. Generally, about 10-45 percent by 
weight of the resulting mixture of the perfumery substance is added to the 
polymer. 
After the perfume material containing the schiff base compositions of our 
invention is added to the container 212 the mixture is stirred for a few 
minutes, for example, 5-15 minutes and maintained within the temperature 
ranges indicated previously by the heating coil 212A. The controls 216 and 
220 are connected through cables 224 and 226 to a suitable supply of 
electric current for supplying the power for heating purposes. 
Thereafter, the valve "V" is opened permitting the mass to flow outwardly 
through conduit 232 having a multiplicity of orifices 234 adjacent to the 
lower side thereof. The outer end of the conduit 232 is closed so that the 
liquid polymer in intimate admixture with one or more of the schiff base 
compositions of our invention or mixture of perfume substance and one or 
more of the shiff base compositions of our invention, will continuously 
drop through the orifices 234 downwardly from the conduit 232. During this 
time, the temperature of the polymer intimately admixed with the perfumery 
substance in the container 212 is accurately controlled so that a 
temperature in the range of from about 240.degree.-250.degree. C., for 
example, (in the case of low density polyethylene) will exist in the 
conduit 232. The regulation of the temperature through the controls 216 
and 220 is essential in order to insure temperature balance to provide for 
the continuous dropping or dripping of molten polymer intimately admixed 
with the perfume substance which is all or which contains one or more of 
the schiff base compositions of our invention, through the orifices 234 at 
a rate which will insure the formation of droplets 236 which will fall 
downwardly onto a moving conveyor belt 238 caused to run between conveyor 
wheels 240 and 242 beneath the conduit 232. 
When the droplets 236 fall onto the conveyor 238, they form pellets 244 
which harden almost instantaneously and fall off the end of the conveyor 
238 into a container 250 which is advantageously filled with water or some 
other suitable cooling liquid to insure the rapid cooling of each of the 
pellets 244. The pellets 244 are then collected from the container 250 and 
utilized for the formation of other functional products, e.g., garbage 
bags and the like. 
THE INVENTION 
Our invention provides schiff base compositions and compositions of matter 
produced by means of the reaction of alkyl anthranilates having the 
structure: 
##STR40## 
wherein R.sub.3 is methyl or ethyl, for example, methyl anthranilate 
having the structure: 
##STR41## 
with aldehydes having the structure: 
##STR42## 
and helional having the structure: 
##STR43## 
wherein the compound having the structure: 
##STR44## 
may be pinoacetaldehyde having the structure: 
##STR45## 
pinoisobutyraldehyde having the structure: 
##STR46## 
or lyral which is a mixture of compounds having the structures: 
##STR47## 
Our invention also relates to the deodorizing use of the reaction product 
of helional having the structure: 
##STR48## 
and alkyl anthranilates defined according to the structure: 
##STR49## 
wherein R.sub.3 is methyl or ethyl. 
The reaction products of helional having the structure: 
##STR50## 
with the alkyl anthranilates have the structures: 
##STR51## 
When the aldehydes of the structure: 
##STR52## 
(wherein R is defined, supra) are reacted with methyl anthranilate and 
helional, compounds having the structures: 
##STR53## 
are produced along with one of the following groups of compounds: 
(Group A): The mixture of compounds having the structures: 
##STR54## 
(Group B): The compounds having the structures: 
##STR55## 
(Group C): The compound having the structure: 
##STR56## 
The reaction products of our invention are collectively termed "schiff base 
compositions"; but not all of the products produced according to the 
"schiff base" reaction set forth, supra, and specifically set forth, 
infra, contain the moiety: 
##STR57## 
Thus, as will be seen, infra, the reaction of "helional" structure: 
##STR58## 
with the compound having the structure: 
##STR59## 
yields three compounds having the structures: 
##STR60## 
The resulting schiff base compositions of our invention produced according 
to the process of our invention are capable of augmenting or enhancing 
floral, oriental, citrus, lemony, melony, watermelon, green and concord 
grape aromas with watermelon, floral, oriental, citrus, lemony, melony, 
green, raspberry and concord grape tastes of foodstuffs, chewing gums, 
toothpastes, medicinal products and chewing tobaccos. 
The schiff base compositions of our invention produced according to the 
process of our invention are also capable of modifying or enhancing the 
aroma characteristics of perfurme compositions, colognes and perfumed 
articles (including soaps, anionic, cationic, nonionic or zwitterionic 
detergents, fabric softener compositions, optical brightener compositions 
and drier-added fabric softener articles) and perfumed polymers by 
imparting thereto intense and substantive green, orange flower, fruity, 
ozoney, sweet anisic, melon, herbaceous, balsamic, walnut and floral 
aromas with grape, fruity, green, floral, anisic, ozoney, piney, melony 
and lemony topnotes, thus fulfilling a number of needs in the fields of 
perfumery and detergent and cosmetics manufacture. 
The schiff base compositions of our invention are also capable of 
deodorizing detergent powders suitable for use in the washing of fabrics 
as well as detergent powders as well as hand soaps. Such detergent powders 
include bleaching compositions, for example, bleaching compositions 
comprising a peroxy bleach compound. The schiff base compositions of our 
invention have deodorancy as measured by having a Lipoxidase-inhibiting 
capacity of at least 50% and a Raoult Variance ratio of at least 1.1 and a 
malodour reduction value of between about 0.25 up to 3.0 as measured by 
the malodour reduction value test disclosed in U.S. Pat. No. 4,663,068 the 
specification for which is incorporated by reference herein; and in 
addition, a deodorant value of from 0.50 up to 3.5 as measured by the 
deodorant value test disclosed in U.S. Pat. No. 4,304,679 the 
specification for which is incorporated by reference herein. 
The reaction conditions to form the schiff base composition between the 
helional having the structure: 
##STR61## 
and/or aldehyde having the structure: 
##STR62## 
(wherein R is defined, supra) and the alkyl anthranilate having the 
structure: 
##STR63## 
wherein R.sub.3 is methyl or ethyl are as follows: 
(i) the temperature of the reaction is in the range of from about 
90.degree. C. up to about 150.degree. C.; 
(ii) the pressure over the reaction mass may vary from about 3 mm/Hg. 
(vacuum) up to about 1 atmosphere with a preferable pressure of between 
about 5 and about 100 mm/Hg. pressure when no additional solvent is used 
and with a preferable pressure of about 1 atmosphere (reflux conditions) 
when a solvent inert to the reaction mass is used whereby water of 
reaction is azeotrope from the reaction mass during the course of the 
reaction; 
(iii) the time of reaction may vary from about 5 up to about 15 hours with 
a preferred time of reaction of between about 6 and about 12 hours; 
(iv) the mole ratio of helional having the structure: 
##STR64## 
and/or aldehyde having the structure: 
##STR65## 
to alkyl anthranilate having the structure: 
##STR66## 
may vary from about 1:1 up to about 1.25:1 of total aldehyde:alkyl 
anthranilate with a preferred mole ratio of between about 1:1 and about 
1.1:1 aldehyde:alkyl anthranilate; and 
(v) the reaction mass may be solvent free or a solvent may be used (e.g., 
toluene) which is inert to the reactants and reaction products and which 
is useful to cause azeotropic distillation of water of reaction from the 
reaction mass. However, a solvent free reaction mass is preferred. 
At the end of the reaction, the reaction mass may be separated into its 
individual components and the reaction product may be purified as by 
fractional distillation of the schiff base composition or schiff base 
reaction product. From a practical standpoint, when a reaction mixture is 
created which gives rise to preferred perfumery properties or preferred 
deodorization properties or preferred flavor properties subsequent 
fractional distillation to the point of yielding an odor acceptable 
product and/or a flavor acceptable product and/or a deodorizing acceptable 
product is what is desired. 
The following Table I sets forth reactants, schiff base reaction product 
structures (to the extent known) and organoleptic properties (from both a 
flavor and fragrance standpoint) of the resulting products. 
TABLE I 
__________________________________________________________________________ 
Schiff Base Reaction 
Product Structures Perfumery and 
Reactants (to the extent known) 
Flavor Properties 
__________________________________________________________________________ 
Helional having Product produced Perfumery 
the structure: according to Example 
Properties 
##STR67## 
##STR68## A green orange flower, fruity, 
ozoney, sweet and anisic aroma 
with grape, fruity, green, 
floral, anisic and ozoney 
topnotes. 
##STR69## 
##STR70## 
and 
##STR71## 
Pinoisobutylral- Product produced Perfumery 
dehyde:helional: according to Example 
Properties 
methyl anthranilate III(A) containing the 
A walnut, green, 
in a mole ratio compounds having the 
melony, ozoney 
of 1:1:2 with structures: aroma with 
##STR72## 
##STR73## floral, woody, animalic, 
walnut, green and ozoney top- 
notes. 
Flavor 
Properties 
##STR74## A floral, oriental aroma with 
watermelon, floral and oriental 
taste nuances at 1 ppm. 
##STR75## 
and 
##STR76## 
Pino isobutyraldehyde: 
Product produced Perfumery 
helional:methyl according to Properties 
anthranilate in a mole ratio of 1:2:3. 
##STR77## A green, floral, anisic, ozoney 
nd fruity aroma with green, 
melon, ozoney, floral, anisic 
and animalic top- notes. 
Flavor 
Properties 
##STR78## A lemony and oriental aroma and 
taste profile at 1 ppm. 
##STR79## 
and 
##STR80## 
Pino acetaldehyde: Product produced Perfumery 
helional:methyl according to Properties 
##STR81## 
##STR82## A melony, herbaceous, sweet and 
alsamic aroma with piney, 
fruity and ozoney topnotes. 
Flavor 
Properties 
##STR83## A melony, citrus, watermelon, 
green aroma with melony, 
citrus, green and raspberry 
taste nuances at 0.1 ppm. 
##STR84## 
##STR85## 
and 
##STR86## 
Helional:lyral:methyl Product produced Perfumery 
anthranilate in a mole 
according to Example 
Properties 
##STR87## 
##STR88## A green, floral, ozoney aroma 
with green, floral, ozoney and 
lemony topnotes. 
and Flavor 
Properties 
##STR89## 
##STR90## A floral and concord grape 
aroma and taste profile at 1 
ppm. 
##STR91## 
##STR92## 
##STR93## 
and 
##STR94## 
Helional:lyral:methyl Product produced Perfumery 
anthranilate in a according to Properties 
mole ratio of 1:2:3. Example IV(B) A green, floral, 
containing the and ozoney aroma 
compounds having with green and 
the structures: floral topnotes. 
##STR95## 
##STR96## 
##STR97## 
##STR98## 
##STR99## 
and 
##STR100## 
__________________________________________________________________________ 
When one or more of the schiff base compositions of our invention is used 
as a food flavor adjuvant, the nature of the co-ingredients included with 
said schiff bases in formulating the product composition will also serve 
to alter the organoleptic characteristics of the ultimate foodstuffs 
treated therewith. As used herein in regard to flavors the term "alter" in 
its various forms means "supplying or imparting flavor character or notes 
to otherwise bland relatively tasteless substance or augmenting the 
existing flavor characteristic where a natural flavor is deficient in some 
regard or supplementing the existing flavor impression to modify its 
quality, character or taste". 
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, fruit cereals, soft drinks, snacks and the like. 
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. Apart from the requirement that any such material be 
"ingestibly" acceptable and thus non-toxic or otherwise non-deleterious 
nothing particularly critical resides in selection thereof. Accordingly, 
such materials which may in general be characterized as flavoring 
adjuvants or vehicles comprise broadly stabilizers, thickeners, surface 
active agents, conditoners, other flavorants and flavor intensifiers. 
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-tertiary-butyl-4-methyl phenol), propyl 
gallate and the like, and sequestrants, e.g., citric acid. 
Thickener compounds include carriers, binders, protective colloids, 
suspending agents, emulsifiers and the like, e.g., agaragar; carrageenan; 
cellulose and celluslose 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 emulisifiers, e.g., mono- and diglycerides of fatty 
acids, skim milkl powder, hexoses, pentoses, disaccharides, e.g., sucrose, 
corn syrup solids 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, turmeric and curcumin 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 supplements, e.g., iron salts such as ferric 
phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc 
sources such as zinc chloride, zinc sulfate and the like. 
Other flavorants and flavor intensifiers include organic acids, e.g., 
acetic acid, butyric acid, caproic acid, caprylic acid, formic acid, 
2-hexenoic acid, 3-hexenoic acid, isobutyric acid, isovaleric acid, 
propionic acid and valeric acid; ketones and aldehydes, e.g., 
acetaldehyde, acetone, acetyl methyl carbinol, acrolein, diacetyl, 
.beta.,.beta.-dimethylacrolein, hexanal, 2-hexenal, cis-3-hexenal, 
4(p-hydroxyphenyl)-2-butanone, alpha-ionone, .beta.-ionone, and 
2-pentenal; alcohols, such as 1-butanol, trans-2-buten-1-ol, ethanol, 
geraniol, 1-hexanol, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 
1-penten-3-ol; esters, such as butyl acetate, ethyl acetate, ethyl 
butyrate, ethyl crotonate, ethyl propionate, 2-hexenyl acetate, 2-hexenyl 
butyrate, hexyl acetate, hexyl butyrate, isoamyl acetate, isopropyl 
butyrate, methyl butyrate, methyl caproate, methyl caprylate, propyl 
acetate, amyl acetate, amyl butyrate, benzyl salicylate, dimethyl 
anthranilate, ethyl methylphenylglycidate, ethyl succinate, isobutyl 
cinnamate, and terpenyl acetate; essential oils such as jasmine absolute, 
rose absolute, orris absolute, lemon essential oil and vanilla; lactones; 
sulfides, e.g., methyl sulfide and other materials such as maltol and 
citral as well as natural raspberry oil, orange oil, mango extract, 
pickled mango extract, natural cranberry juice, strawberry juice 
concentrate and grape juice concentrate. 
The specific flavoring adjuvants 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, 
be capable of providing an environment in which the schiff bases of our 
invention can be disbursed or admixed to provide a homogeneous medium. In 
addition, selection of one or more adjuvants, as well as the quantities 
thereof, will depend upon the precise organoleptic grape character desired 
in the finished product. Thus, in the case of flavoring compositions, 
ingredient selection will vary in accordance with the foodstuff to which 
the flavor and aroma are to be impaired. In contradistinction, in the 
preparation of solid products, e.g., simulated foodstuffs, ingredients 
capable of providing normally solid compositions should be selected such 
as various cellulose derivatives. 
As will be appreciated by those skilled in the art, the amount in which the 
schiff base compositions of our invention employed in a particular 
instance can vary over a relatively wide range whereby its desired 
organoleptic effects (having reference to the nature of the product) are 
achieved. All parts and percentages given herein are by weight unless 
otherwise specified. 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 the purposes of enhancing the composition 
merely deficient in natural flavor or aroma. Thus, the primary 
requirements is that amount which is effective, i.e., sufficient to alter 
the organoleptic characteristics of the parent composition, whether 
foodstuff per se or flavoring composition. Thus, the use of insufficient 
quantities in which the schiff base compositions of our invention 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 flaovr-aroma balance, thus proving self-defeating. 
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, it has been found that 
quantities in which the schiff base compositions of our invention ranging 
from a small but effective amount, e.g., 0.02 parts per million up to 
about 50 parts per million by weight based on total composition are 
suitable. Concentrations in excess of the maximum quantity stated are not 
normally recommended since they fail to provide commensurate enhancement 
of organoleptic properties. In those cases wherein in which the schiff 
bases of our invention is added to the foodstuff as an integral component 
of the flavoring composition, it is, of course, essential that the total 
quantity of flavoring composition employed be sufficient to yield an 
effective schiff base concentration in the foodstuff product. 
The composition described herein can be prepared according to conventional 
techniques well known as typified by cake batters and fruit juices 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 admixing the schiff bases of our invention with, for example, 
gum arabic, gum tragacanth, carrageenan and the like and thereafter 
spray-drying the resultant mixture whereby to obtain the particulate solid 
product. Prepared flavor mixes in powder form, e.g., a raspberry flavored 
powder are obtained by mixing dried solid, components, e.g., starch, sugar 
and the like and the schiff bases of our invention in a dry blender until 
the requisite degree of uniformity is achieved. 
It is presently preferred to combine the schiff base compositions of our 
invention with the following adjuvants: 
Parahydroxybenzyl acetone; 
Vanilin; 
Maltol; 
Alpha-Ionone; 
Beta-Ionone; 
Isobutyl acetate; 
Ethyl butyrate; 
Dimethyl sulfide; 
Acetic acid; 
Acetaldehyde; 
4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanone; 
4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanone; 
2-(4-hydroxy-4-methylpentyl)norbornadiene produced according to Example I 
of U.S. Pat. No. 3,911,028; 
Beta-Damascone(1-crotonyl-2,6,6-trimethylcyclohex-1-ene) 
Beta-Damascenone(1-crotonyl-2,6,6-trimethylcyclohexa-1,3-diene); 
Beta-cyclohomocitral(2,6,6-trimethylcyclohex-1-ene carboxaldehyde); 
Isoamyl butyrate; 
Cis-3-hexenol-1; 
Elemecine(4-allyl-1,2,6-trimethoxybenzene); 
Isoelemecine(4-propenyl-1,2,6-trimethoxybenzene); 
Ethyl ester of 2-hydroxy butyric acid; 
Ethyl-2-methyl-3-pentenoate; 
Ethyl ester of 3-hydroxy butyric acid; 
Orange oil; 
Lemon oil; 
Grape juice concentrate; 
Cranberry juice concentrate; 
Mango extract; and 
Pickled mango extract. 
The schiff base compositions prepared in accordance with the process of our 
invention and one or more auxiliary perfume ingredients including, for 
example, alcohols other than any alcohols existing in the schiff base 
compositions of our invention, aldehydes, ketones, terpinic hydrocarbons, 
nitriles esters other than any existing in the schiff base compositions of 
our invention, lactones, natural essential oils and synthetic essential 
oils may be admixed so that the combined odors of the individual 
components produce a pleasant and desired fragrance, particularly, and 
preferably, in pine, floral, lavender and "fresh air" fragrances. Such 
perfume compositions usually contain (a) the main note or the "bouquet" or 
foundation stone of the composition; (b) modifiers which round off and 
accompany the main note; (c) fixatives which include odorous substances 
which lend a particular note to the perfume throughout all stages of 
evaporation and substances which retard evaporation; and (d) topnotes 
which are usually low boiling, fresh smelling materials. 
In perfume compositions, it is the individual components which contribute 
to their particular olfactory characteristics, however, the over-all 
sensory effect of the perfume composition will be at least the sum total 
of the effects of each of the ingredients. Thus, schiff base compositions 
prepared in accordance with the process of our invention can be used to 
alter, modify or enhance the aroma characteristics of a perfume 
composition, for example, by utilizing or moderating the olfactory 
reaction contributed by another ingredient in the composition. 
The amount of schiff base composition prepared in accordance with the 
process of our invention which will be effective in perfume compositions 
as well as in perfumed articles (e.g., anionic, nonionic, cationic and 
zwitterionic solid or liquid detergents, soaps, fabric softener 
compositions, drier-added fabric softener articles, optical brightener 
compositions, perfumed polymers and textile sizing agents) 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 schiff base compositions 
prepared in accordance with the process of our invention and less than 50% 
of schiff base derivatives prepared in accordance with the process of our 
invention or even less (e.g., 0.005%) can be used to impart green, orange 
flower, fruity, ozoney, sweet anisic, melony, herbaceous, balsamic, walnut 
and floral aromas with grape, fruity, green, floral, anisic, ozoney, 
piney, melony and lemony topnotes to solid or liquid anionic, cationic, 
nonionic or zwitterionic detergents, fabric softener compositions, fabric 
softener articles, optical brightener compositions, textile sizing 
compositions, perfumed polymers or other products. The amount employed can 
range up to 70% of the fragrance components and will depend on 
considerations of cost, nature of the end product, the effect desired on 
the finished product and the particular fragrance sought. 
The schiff base compositions prepared in accordance with the process of our 
invention is useful (taken alone or together with other ingredients in 
perfume compositions) as (an) olfactory component(s) in detergents and 
soaps, space odorants and deodorants perfumes, colognes, toilet water, 
bath preparations, such as creams, deodorants, hand lotions and sun 
screens; powders, such as talcs, dusting powders, face powders, and 
perfumed polymers and articles of manufacture produce from said perfumed 
polymers. When used as (an) olfactory component(s) as little as 0.2% of 
schiff base compositions prepared in accordance with the process of our 
invention will suffice to impart an intense and substantive green, orange 
flower, fruity, ozoney, sweet anisic, melony, herbaceous, balsamic, walnut 
and floral aromas with grape, fruity, green, floral, anisic, ozoney, 
piney, melony and lemony topnotes to floral, piney, lemony, rose and 
"fresh air" formulations. Generally, no more than 6% of one or more schiff 
base compositions of our invention based on the ultimate end product is 
required in the perfumed article composition. Accordingly, the range of 
schiff base compositions in the perfumed articles is from about 0.2% by 
weight of the schiff bases up to about 6% by weight based on the perfumed 
article. In addition, the perfume composition or fragrance composition of 
our invention can contain a vehicle or carrier for one or more of the 
schiff base compositions prepared in accordance with the process of our 
invention. The vehicle can be a liquid, such as a non-toxic alcohol, e.g., 
ethyl alcohol, a non-toxic glycol, e.g., propylene glycol or the like. The 
carrier can also be an absorbent solid, such as a gum (e.g., gum arabic, 
guar gum or xanthan gum) or components for encapsulating the composition 
(such as gelatin) as by coacervation; or such as urea-formaldehyde polymer 
forming a capsule shell around a liquid perfumed center). 
Our invention also relates to the utilization of controlled release 
technology for the controlled release of perfumes into gaseous 
environments from polymers such as mixtures of epsilon polycaprolactone 
polymers and polyethylene which polyepsilon caprolactone polymers are 
defined according to at least one of the structures: 
##STR101## 
wherein "n" is from about 50 up to about 1,200 with the proviso that the 
average "n" in the system varies from about 150 up to about 700 according 
to the mathematical statement: 
EQU [700 .gtoreq.n.gtoreq.150] 
with the term "n" being the average number of repeating monomeric units for 
the epsilon polycaprolactone polymer. The perfumed material's release rate 
from such polymer mixture is close to "zero order". As a general rule, the 
release rate in a polymeric matrix is proportional to t.sup.-1/2 until 
about 60% of the functional fluid is released from the polymeric matrix. 
The release rate thereafter is related exponentially to time as a general 
rule according to the equation: 
EQU dM.sub.1 /dl=k.sub.1 e.sup.- k.sub.2 t 
wherein k.sub.1 and k.sub.2 are constants. According to Kydonieus, 
"Controlled Release Technologies: Methods, Theory, and Applications" 
(cited, supra, the amount of perfume composition released is proportional 
to time as long as the concentration of perfume material present, e.g., 
the schiff base compositions of our invention is higher than the 
solubility of the agent in the matrix. Thus, such dispersed systems are 
similar to the dissolved systems except that instead of a decreased 
release rate after 60% of the perfume material has been emitted, the 
relationship holds almost over the complete release curve. Kydonieus 
further states, that if one assumes that the release of functional fluid 
by diffusion is negligible in monolithic erodible systems, the speed of 
erosion will control the release rate and release by erosion by a 
surface-area-dependent phenomenon, the release constant (zero order) as 
long as the surface area does not change during the erosion period. This 
is the case with the polymers containing the schiff base compositions of 
our invention. 
The polyepsilon caprolactone polymers useful in practicing our invention 
are more specifically described in the brochure of the Union Carbide 
Corporation, 270 Park Avenue, New York, N.Y. 10017, entitled "NEW 
POLYCAPROLACTONE TERMOPLASTIC POLYMERS PCL-300 AND PCL-700". These 
polyepsilon caprolactone polymers are composed of a repeating sequence of 
non-polar methylene groups and relatively polar ester groups. The average 
number of repeating monomeric units varies between 150 and 700 depending 
on the particular "PCL" number. Thus, regarding PCL-300 the average number 
of repeating monomeric units is about 300. Regarding PCL-700, the average 
number of repeating monomeric units is 700. 
The polyepsilon caprolactone homopolymers which are ultimately taken in 
admixture with such materials as polyethylene useful in the practice of 
our invention may also be stabilized using stabilizers as defined in U.S. 
Pat. No. 4,360,682 issued on Nov. 23, 1982, the specification for which is 
incorporated herein by reference. The stabilizing materials which 
stabilize the polyepsilon caprolactone useful in conjunction with our 
invention against discoloration are dihydroxybenzenes such as hydroquinone 
or compounds having the formula: 
##STR102## 
in which R.sub.1 is alkyl of from 1 to 8 carbon atoms, and R.sub.2 is 
hydrogen or alkyl of 1 to 8 carbon atoms. It is preferable to have such 
stabilizer in the polyepsilon caprolactone homopolymer in an amount of 
from about 100 to 500 ppm. Such stabilizers do not interfer with the 
functional fluids dissolved and/or adsorbed into the polymeric matrix. 
The method of incorporating the schiff base compositions of our invention 
or perfume compositions containing same into the polymers may be according 
to the technique of U.S. Pat. No. 3,505,432 issued on Apr. 7, 1970 (the 
specification for which is incorporated by reference herein) or U.S. Pat. 
No. 4,247,498 issued on Jan. 27, 1981, the disclosure of which is 
incorporated by reference herein. 
Thus, for example, a first amount of liquid polyethylene-polyepsilon 
caprolactone polymer mixture (50:50) is mixed with one of the schiff base 
compositions of our invention. Drops are formed from the mixture and the 
drops are solidified. The solidified drops are then melted, if desired, 
with a second amount of unscented low density polyethylene, for example, 
or polypropylene, for example. Usually, but not necessarily, the second 
amount of polymer is larger than the first amount. The resulting mixture 
thus obtained is solidified subsequent to or prior to ultimate casting 
into a utilitarian shape. 
Thus, in accordance with one aspect of our invention the imparting of scent 
is effected in two stages. In a first stage, a 50:50 (weight:weight) 
polyepsilon caprolactone, e.g., PCL-700: polyethylene in molten form is 
admixed with a high percentage of one of the schiff base compositions of 
our invention and the mixture is solidified in the form of pellets or 
beads. These pellets or beads thus contain a high percentage of schiff 
bases (e.g., up to 45% by weight of the entire mixture) and may be used as 
"master pellets" which thereafter, in a second stage, if desired, may be 
admixed and liquified with additional polymers such as additional 
polyethylene or mixtures of polyethylene and polyepsilon caprolactone in 
an unscented state, or unscented polypropylene. In addition, additional 
polymers or copolymers may be used, for example, copolymers specified and 
described in United Kingdom Patent Specification No. 1,589,201 published 
on May 7, 1981, the specification for which is incorporated by reference 
hererin. 
In accordance with the present invention at least one of the schiff base 
compositions of our invention is added to the polymer in a large closed 
container or drum which is maintained under controlled temperature 
conditions while the polymer in a melted condition is mixed with at least 
one of the schiff bases under agitation. 
In order that the perfume be added uniformly to the polymer, the 
temperature of the melt is constantly controlled during the process. The 
polymer-perfume mixture is then directed through an elongated conduit or 
pipe element having a plurality of orifices adjacent to the lower most 
portion thereof. The polymer enriched by at least one of the schiff base 
compositions of our invention is permitted to drip through the orifices 
onto a continuously moving, cooled conveyor upon which the polymer 
containing at least one of the schiff base compositions of our invention 
solidifies into small size pellets with the perfume imprisoned therein. 
The apparatus useful in conjunction with this process advantageously 
includes a conveyor of a material which will not adhere to the polymer 
which contains at least one of the schiff base compositions of our 
invention. 
In order that the droplets form into uniform pellets or beads, the conveyor 
is continuously washed with a liquid such as water to maintain the surface 
relatively cool. The pellets are delivered by the conveyor into a 
container and packaged for shipment. 
The following Examples I-IV serve to illustrate processes for preparing the 
schiff base compositions of our invention. The examples following Example 
IV are illustrative of the organoleptic utilities of the schiff base 
compositions as well as te deodorizing utilities of the schiff base 
compositions of our invention and the deodorizing capabilities of the 
reaction product of helional and methyl anthranilate which is also part of 
our invention. 
All parts and percentages given herein are by weight unless otherwise 
specified. 
EXAMPLE I 
Preparation of Schiff Base of Methyl Anthranilate and Helional 
Reaction: 
##STR103## 
Into a 1 liter 3 neck reaction flask equipped with stirrer, thermometer, 
heating mantle and aziotropic take-off apparatus is placed 192.2 grams of 
helional (1.0 moles) having the structure: 
##STR104## 
and 300 ml of dry toluene. The reaction mass is heated to reflux and 18 ml 
of water (1 mole) was aziotroped off over a period of 3 hours. By the same 
manner most of the remaining toluene is removed. A 100 grams of the crude 
reaction product is then molecular distilled up to a pot temperature of 
200.degree. C. Four fractions are obtained. NMR analysis indicates that 
the reaction mass contains the isomers having the structures: 
##STR105## 
The resulting product has a green, orange flower, fruity, ozoney, sweet and 
anisic aroma with grape, fruity, green, floral, anisic and ozoney 
topnotes. 
FIG. 1 is the GC spectral scan for the resulting product (Conditions: 50 
m.times.0.32 mm OV-1 fused silica column programmed at 225.degree. C. 
isothermal). 
FIG. 2 is the mass spectrum for one of the isomers of the resulting 
reaction product. 
FIG. 3 is the NMR spectrum for the compound having the structure: 
##STR106## 
prepared according this example. 
EXAMPLE I(A) 
Preparation of Schiff Base of Methyl Anthranilate and Helional (Alternative 
Preparation) 
Into a 500 ml reaction flask equipped with mechanical stirrer, thermometer 
and vacuum attachment is placed 75.5 grams of methyl anthranilate and 96.0 
grams of helional. The reaction mass is heated at 90.degree. C. with 
stirring for 3.5 hours at a vacuum of 30 mm/Hg. 
NMR analysis and GLC analysis yield the information that the resulting 
structures are: 
##STR107## 
The resulting product has a green, orange flower, fruity, ozoney, sweet and 
anisic aroma with grape, fruity, green, floral, anisic and ozoney topnotes 
and is useful for its deodorizing properties as set forth in the following 
examples. 
EXAMPLE II 
Preparation of Schiff Base Reaction Product of Methyl Anthranilate, 
Pinoacetaldehyde and Helional 
Reaction: 
##STR108## 
Into a 2 liter reaction flask equipped with thermometer, mechanical 
stirrer, addition funnel, vacuum apparatus and heating mantle are placed 
377.5 grams (2.50 moles) of methyl anthranilate. The methyl anthranilate 
is heated to 50.degree. C. and while maintaining the methyl anthranilate 
at 50.degree. C., 153 grams of pino acetaldehyde and 288 grams of helional 
is added dropwise over a period of 15 minutes with stirring. After 
addition is complete the reaction mass is placed under 50 mm/Hg. vacuum 
and heated to 125.degree. C. for a period of 7 hours. At the end of the 7 
hour period, the reaction mass is removed and frationally distilled 
yielding the following reaction products: 
##STR109## 
The resulting reaction product has from a fragrance standpoint a melony, 
herbaceous, sweet, balsamic aroma with piney, fruity and ozoney topnotes. 
From a flavor standpoint the resulting reaction product has a melony, 
citrus, watermelon, green aroma with a melony, citrus, watermelon, green 
and raspberry taste profile at 0.1 ppm. 
FIG. 4 is the GC spectral scan for the resulting reaction product. 
FIGS. 5 and 6 are mass spectra of the compounds (individually) having the 
structures: 
##STR110## 
FIG. 7 is the mass spectrum for one of the compounds having one of the 
structures: 
##STR111## 
EXAMPLE III(A) 
Preparation of Schiff Base Reaction Product of 
Pinoisobutylraldehyde:Helional:Methyl Anthranilate with a Mole Ratio of 
Pinoisobutyraldehyde:Helional:Methyl Anthranilate Being 1:1:2 
Reaction: 
##STR112## 
Into a 2 liter reaction flask equipped with stirrer, thermometer, heating 
mantle, vacuum apparatus and addition funnel is placed 2 moles of methyl 
anthranilate (302 grams). The methyl anthranilate is heated to 50.degree. 
C. at atmospheric pressure. While maintaining the reaction mass at 
50.degree. C., one mole (142 grams) of helional and one mole (206 grams) 
of pino acetaldehyde are added to the reaction mass. When all the aldehyde 
is added the reaction mass is placed under 50 mm/Hg. vacuum and heated to 
125.degree. C. for seven hours. At the end of the seven hour period, the 
reaction mass is cooled. 
The reaction product contains the compounds having the structures: 
##STR113## 
From a fragrance standpoint the resulting reaction product has a walnut, 
green, melony and ozoney aroma with floral, woody, animalic, walnut, green 
and ozoney topnotes. 
FIG. 8 is the GC spectral scan for the resulting reaction product 
(Conditions: 50 m.times.0.32 mm OV-1 fuse silica column programmed at 
225.degree. C. isothermal). 
FIG. 9 is the mass spectrum for the compound having the structure: 
##STR114## 
FIG. 10 is the mass spectrum for one of the compounds having one of the 
structures: 
##STR115## 
EXAMPLE III(B) 
Preparation of Schiff Base Reaction Product of Methyl Anthranilate, 
Helional and Pinoisobutyraldehyde with the Mole Ratio of 
Pinoisobutyraldehyde:Helional:Methyl Anthranilate Being 1:2:3 
A reation is in conditions the same as that of Example III(A) was carried 
out with the exception that the mole ratio of 
pinoisobutyraldehyde:helional:methyl anthranilate is 1:2:3. 
The resulting reaction product from a fragrance standpoint has a green, 
floral, anisic, ozoney and fruity aroma with green, melony, ozoney, 
floral, anisic and animalic topnotes. From a flavor standpoint the 
resulting product has a lemony and oriental aroma and taste profile at 1 
ppm. 
EXAMPLE IV(A) 
Preparation of Schiff Base of Methyl Anthranilate, Lyral and Helional with 
the Mole Ratio of Lyral:Helional:Methyl Anthranilate Being 2:1:3 
Reaction: 
##STR116## 
Into a 2 liter reaction flask equipped with vacuum apparatus and ice trap, 
mechanical stirrer, thermometer, fraction cutter and heating mantle is 
placed 453 grams of methyl anthranilate. The methyl anthranilate is heated 
to 50.degree. C. Over a 15 minute period while maintaining the reaction 
mass at 50.degree. C., 2 moles of lyral weighing 420 grams and one mole of 
helional weighting 192 grams is placed into the reaction vessel. The 
reaction mass is then closed and placed under 50 mm/Hg. vacuum and heated 
to 125.degree. C. for a period of 7 hours. 
##STR117## 
From a perfumery standpoint the resulting product has a green, floral and 
ozoney aroma with green, floral, ozoney and lemony topnotes. 
From a flavor standpoint the resulting product has a concord grape and 
floral aroma and taste profile at 1 ppm. 
FIG. 11 is the GC spectral scan for the resulting product (Conditions: 50 
m.times.0.32 mm OV-1 fused silica column programmed at 225.degree. C. 
isothermal). 
FIGS. 12, 13, 14, 15, 16 and 17 are mass spectra of the various compounds 
(individually) produced as a result of the reaction in the instant 
example. 
EXAMPLE IV(B) 
Preparation of Schiff Base Reaction Productof Methyl Anthranilate, Helional 
and Lyral with the Mole Ratio of Lyral:Helional:Methyl Anthranilate Being 
1:2:3 
A reaction is carried out under conditions substantially identical to those 
of Example IV(A) with the exception that the mole ratio of 
lyral:helional:methyl anthranilate is 1:2:3. 
From a perfumery standpoint the resulting product has a green, floral and 
ozoney aroma with grape and floral topnotes. 
EXAMPLE V 
Floral Perfume Compositions 
The schiff base compositions of Examples II, III(A) and III(B) have melony, 
herbaceous, sweet, balsamic, walnut, green, ozoney and fruity aromas with 
piney, fruity, ozoney, floral, woody, animalic, walnut, green, melony and 
anisic topnotes. These materials have great warmth and richness and blend 
well with many floral concepts. Each of the schiff base compositions have 
rather unique floral notes of great value of perfumery. They may be 
demonstrated by the following floral fragrances whereby the schiff base 
compositions of Examples II, III(A) and III(B) are used to the extent of 
5% by weight. 
All three of these products perform quite well in fragrances and are judged 
to be very valuable fragrance materials: 
TABLE II 
______________________________________ 
FLORAL FRAGRANCE 
"V(A)" "V(B)" "V(C)" 
______________________________________ 
Citronellol 12.3 12.3 12.3 
Geraniol 2.5 2.5 2.5 
Amyl Cinnamic Aldehyde 
24.6 24.6 24.6 
Galaxolide .RTM.50 (Trademark 
9.8 9.8 9.8 
for the Tricyclic Isochroman 
of International Flavors & 
Fragrances Inc.) 
Vertenex High Cis (Cis-t- 
7.4 7.4 7.4 
Butylcyclohexenyl Acetate; 
Para Isomer) 
Rose Oxide 0.7 0.7 0.7 
Cinnamic Alcohol 19.6 19.6 19.6 
Aldehyde C-11 (n-Undecylenic 
0.5 0.5 0.5 
Aldehyde) 
Aldehyde C-12 (n-Dodecyl 
0.5 0.5 0.5 
Aldehyde in 10% solution 
in diethyl phthalate) 
Citronellal (10% solution 
0.5 0.5 0.5 
in diethyl phthalate) 
Phenyl Ethyl Acetate 
2.5 2.5 2.5 
Ylang Oil 1.2 1.2 1.2 
Indisan (Hydrogenated 
3.7 3.7 3.7 
derivative of reaction 
product of Camphene and 
Resorcinol) 
Musk Ketone 5.0 5.0 5.0 
Oakmoss Resin 0.5 0.5 0.5 
Liatrix Absolute (10% in 
2.5 2.5 2.5 
diethyl phthalate) 
Vetiver Acetate 1.2 1.2 1.2 
Diethyl Phthalate 
5.0 5.0 5.0 
The schiff base 5.0 0 0 
reaction product of 
methyl anthranilate, 
helional and pino 
acetaldehyde of 
Example II. 
The Schiff base 0 5.0 0 
reaction product 
of methyl anthranilate, 
helional and pino 
isobutyraldehyde with 
the mole ratio of methyl 
anthranilate:helional:pino 
isobutyraldehyde being 
1:1:2 produced according 
to Example III(A). 
The schiff base reaction 
0 0 5.0 
product of methyl 
anthranilate, helional 
and pino isobutyraldehyde 
with the mole ratio of 
methyl anthranilate:helional: 
pino isobutyraldehyde being 
1:2:3. 
______________________________________ 
The schiff base reaction product of Example II imparts to this floral 
fragrance melony, herbaceous, sweet, balsamic undertones with piney, 
fruity and ozoney topnotes. Accordingly, the fragrance can be described as 
"floral with a melony, herbaceous, sweet and balsamic undertone and piney, 
fruity and ozoney topnotes". 
The schiff base composition of Example III(A) imparts to this floral 
formulation walnut, green, melony and ozoney undertones with floral, 
woody, animalic, walnut green and ozoney topnotes. Accordingly, the 
fragrance thus produced can be described as "floral with walnut, green, 
melony and ozoney undertones and floral, woody, animalic, walnut, green 
and ozoney topnotes". 
The schiff base composition produced according to Example III(B) imparts to 
this floral formulation green, floral, anisic, ozoney and fruity 
undertones with green, melony, ozoney, floral, anisic and animalic 
topnotes. Accordingly, the fragrance thus produced can be described as 
"floral with green, floral, anisic, ozoney and fruity undertones and 
green, melony, ozoney, floral, anisic and animalic topnotes". 
EXAMPLE VI 
Floral Perfume Compositions 
The schiff base reaction product of lyral, methyl anthranilate and helional 
with the mole ratio of lyral;helional:methyl anthranilate being 2:1:3 
produced according to Example IV(A) has a green, floral and ozoney aroma 
with green, floral, ozoney and lemony topnotes. The schiff base reaction 
product of lyral, helional and methyl anthranilate with the mole ratio of 
lyral:helional:methyl anthranilate being 1:2:3 has a green, floral and 
ozoney aroma with grape and floral topnotes. Each of these materials of 
Examples IV(A) and IV(B) have great warmth and richness and blend well 
with many floral concepts. They have rather unique floral notes of great 
value to perfumery. 
The two of these products perform quite well in fragrances and are judged 
to be very valuable fragrance materials. 
TABLE III 
______________________________________ 
FLORAL FRAGRANCE 
Ingredients VI(A) VI(B) 
______________________________________ 
Citronellol 12.3 12.3 
Geraniol 2.5 2.5 
Amyl Cinnamic Aldehyde 
24.6 24.6 
Galaxolide .RTM.50 (Trademark 
9.8 9.8 
for the Tricyclic Isochroman 
of International Flavors & 
Fragrances Inc.) 
Vertenex High Cis (Cis-t- 
7.4 7.4 
Butylcyclohexenyl Acetate; 
Para Isomer) 
Rose Oxide 0.7 0.7 
Cinnamic Alcohol 19.6 19.6 
Aldehyde C-11 (n-Undecylenic 
0.5 0.5 
Aldehyde) 
Aldehyde C-12 (n-Dodecyl 
0.5 0.5 
Aldehyde in 10% solution 
in diethyl phthalate) 
Citronellal (10% solution 
0.5 0.5 
in diethyl phthalate) 
Phenyl Ethyl Acetate 
2.5 2.5 
Ylang Oil 1.2 1.2 
Indisan (Hydrogenated 
3.7 3.7 
derivative of reaction 
product of Camphene and 
Resorcinol) 
Musk Ketone 5.0 5.0 
Oakmoss Resin 0.5 0.5 
Liatrix Absolute (10% in 
2.5 2.5 
diethyl phthalate) 
Vetiver Acetate 1.2 1.2 
Diethyl Phthalate 5.0 5.0 
Schiff base reaction 
5.0 0 
product of lyral: 
helional:methyl 
anthranilate 
with the mole ratio 
of lyral:helional:methyl 
anthranilate being 
2:1:3 prepared 
according to 
Example IV(A). 
Schiff base reaction 
0 5.0 
product of lyral, helional 
and methyl anthranilate 
with the mole ratio of 
lyral:helional:methyl 
anthranilate being 
1:2:3 prepared according 
to Example IV(B). 
______________________________________ 
The schiff base reaction product of lyral, helional and methyl anthranilate 
with the mole ratio of lyral:helional:methyl anthranilate being 2:1:3 
prepared according to Example IV(A) imparts to this floral fragrance 
green, floral and ozoney undertones with green, floral, ozoney and lemony 
topnotes. Accordingly, the fragrance can be described as "floral with 
green, floral and ozoney undertones and green, floral, ozoney and lemony 
topnotes". 
The schiff base reaction product of lyral, helional and methyl anthranilate 
with the mole ratio of lyral:helional:methyl anthranilate being 1:2:3 
prepared according to Example IV(B) imparts to this floral formulation a 
green, floral and ozoney undertones with grape and floral topnotes. 
Accordingly, the fragrance thus produced can be described as "floral with 
green and ozoney undertones and grape topnotes". 
EXAMPLE VII 
Preparation of Cosmetic Powder Compositions 
Cosmetic powder compositions are prepared by mixing in a ball mill 100 
grams of talcum powder with 0.25 grams of each of the substances set forth 
in Table IV below. Each of the cosmetic powder compositions has an 
excellent aroma as described in Table IV below: 
TABLE IV 
______________________________________ 
Substance Aroma Description 
______________________________________ 
The schiff base reaction product of 
A green, orange flower 
helional and methyl anthranilate 
fruity, ozoney and sweet, 
prepared according to Example I. 
anisic aroma with grape, 
fruity, green, floral, 
anisic and ozoney 
topnotes. 
The schiff base reaction product of 
A melony, herbaceous 
methyl anthranilate, helional and 
sweet, balsamic aroma 
pino acetaldehyde prepared according 
with piney, fruity and 
to Example II. ozoney topnotes. 
The schiff base reaction product of 
A walnut, green, melony 
methyl anthranilate and helional 
and ozoney aroma with 
and pino isobutyraldehyde with 
floral, woody, animalic, 
the mole ratio of pino 
walnut, green and ozoney 
isobutyraldehyde:helional:methyl 
topnotes. 
anthranilate being 1:1:2. 
The schiff base reaction product of 
A green, floral, anisic, 
methyl anthranilate, helional and 
ozoney and fruity aroma 
pino isobutyraldehyde with the 
with green, melony, 
mole ratio of pino isobutyraldehyde: 
ozoney, floral, anisic 
helional:methyl anthranilate 
and animalic topnotes. 
being 1:2:3. 
The schiff base reaction product of 
A green, floral and 
lyral, helional and methyl 
ozoney aroma with green, 
anthranilate with the mole ratio 
floral, ozoney and 
of lyral:helional:methyl 
lemony topnotes. 
anthranilate being 2:1:3 prepared 
according to Example IV(A). 
The schiff base reaction product of 
A green, floral and 
lyral, helional and methyl 
ozoney aroma with grape 
anthranilate with the mole ratio 
and floral topnotes. 
of lyral:helional:methyl anthranilate 
being 1:2:3 prepared according 
to Example IV(B) 
The perfume composition of 
A floral with a melony 
Example V(A). herbaceous, sweet and 
balsamic undertone and 
piney, fruity and ozoney 
topnotes. 
The perfume composition of 
A floral with walnut 
Example V(B). green, melony and ozoney 
undertones and floral, 
woody, animalic, walnut, 
green and ozoney 
topnotes. 
The perfume composition of 
A floral with green, 
Example V(C). floral, anisic, ozoney 
and fruity undertones 
and green, melony, 
ozoney, floral, anisic 
and animalic topnotes. 
The perfume composition of 
A floral with green, 
Example VI(A). floral and ozoney 
undertones and green, 
floral, ozoney and 
lemony topnotes. 
The perfume composition of 
A floral with green and 
Example VI(B). ozoney undertones and 
grape topnotes. 
______________________________________ 
EXAMPLE VIII 
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 IV of Example VII are prepared containing 0.10%, 0.15%, 
0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in Table IV of 
Example VII. They are prepared by adding and homogeneously mixing the 
appropriate quantity of substance in Table IV of Example VII in the liquid 
detergent. The detergents all possess excellent aromas as set forth in 
Table VI of Example XIV, the intensity increasing with greater 
concentrations of substance as set forth in Table IV of Example VII. 
EXAMPLE IX 
Preparation of Colognes and Handkerchief Perfumes 
Compositions as set forth in Table IV of Example VII 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 IV of Example VII are imparted 
to the colognes and to the handkerchief perfumes at all levels indicated. 
EXAMPLE X 
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 sample of substances as set forth in Table IV of Example VII 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 liquid are 
placed into soap molds. The resulting soap cakes, on cooling, manifest 
aromas as set forth in Table IV of Example VII. 
EXAMPLE XI 
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 IV of Example VII. Each of the 
detergent samples has an excellent aroma as indicated in Table IV of 
Example VII. 
EXAMPLE XII 
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), 
non-woven 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 IV of Example VII. 
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 IV of Example VII, 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 of about 1.85 
grams per 100 square inches of substrate; and an outer coating coated on 
the first coating consisting of about 1.4 grams per 100 square inches of 
substrate. One of the substances of Table IV of Example VII is admixed in 
each case with the outer coating mixture, thereby providing a total 
aromatized outer coating weight ratio to substrate of about 0.5:1 by 
weight of the substrate. The aroma characteristics are imparted in a 
pleasant manner to the head space in a dryer on operation thereof in each 
case using said drier-added fabric softener non-woven fabrics and these 
aroma characteristics are described in Table IV of Example VII, supra. 
EXAMPLE XIII 
Hair Spray Formulations 
The following hair spray formulation is prepared by first dissolving PVP/VA 
E-735 copolymer manufactured by the GAF Corporation of 140 West 51st 
Street, New York, N.Y., in 91.62 grams of 95% food grade ethanol. 8.0 
Grams of polymer is dissolved in the alcohol. The following ingredients 
are added to the PVP/VA alcoholic solution: 
______________________________________ 
Ingredients Weight Percent 
______________________________________ 
Dioctyl sebacate 0.05 
Benzyl alcohol 0.10 
Dow Corning 473 fluid 
0.10 
(prepared by the Dow 
Corning Corporation) 
Tween 20 surfactant 
0.03 
(prepared by ICI America 
Corporation) 
One of the perfumery 
0.10 
substances as set forth 
in Table IV of Example VII, 
supra. 
______________________________________ 
The perfume substances as set forth in Table IV of Example VII add aroma 
characteristics as set forth in Table IV of Example VII which are rather 
intense and aesthetically pleasing to the users of the soft-feel, 
good-hold pump hair sprays. 
EXAMPLE XIV 
Conditioning Shampoos 
Monamid CMA (prepared by the Mona Industries Company ) (3.0 weight percent) 
is melted with 2.0 weight percent coconut fatty acid (prepared by Procter 
& Gamble Company of Cincinnati, Ohio); 1.0 weight percent ethylene glycol 
distearate (prepared by the Armak Corporation) and triethanolamine (a 
product of Union Carbide Corporation) (1.4 weight percent). The resulting 
melt is admixed with Stepanol WAT produced by the Stepan Chemical Company 
(35.0 weight percent). The resulting mixture is heated to 60.degree. C. 
and mixed until a clear solution is obtained (at 60.degree. C.). This 
material is "COMPOSITION A". 
GAFQUAT.RTM. 755N polymer (manufactured by GAF Corporation of 140 West 51st 
Street, New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weight 
percent sodium sulfite and 1.4 weight percent polyethylene glycol 6000 
distearate produced by Armak Corporation. This material is "COMPOSITION 
B". 
The resulting "COMPOSITION A" and "COMPOSITION B" are then mixed in a 50:50 
weight ratio of A:B and cooled to 45.degree. C. and 0.3 weight percent of 
perfuming substance as set forth in Table IV of Example VII is added to 
the mixture. The resulting mixture is cooled to 40.degree. C. and blending 
is carried out for an additional one hour in each case. At the end of the 
blending period, the resulting material has a pleasant fragrance as 
indicated in Table IV of Example VII. 
EXAMPLE XV 
Each of the fragrance materials of Table IV of Example VII, supra, are 
added to a 50:50 weight:weight mixture of low density 
polyethylene:polyepsilon caprolactone PCL-700 forming pellets with scents 
as set forth in Table IV of Example VII, supra. 
75 Pounds of a 50:50 mixture of PCL-700 polyepsilon caprolactone 
(manufactured by the Union Carbide Corporation of New York, N.Y. having a 
melting point of about 180.degree.-190.degree. F.):Low density 
polyethylene, are heated to about 250.degree. F. in a container of the 
kind illustrated in FIGS. 20 and 21. 25 Pounds of each of the fragrance 
materials as set forth in Table IV of Example VII, is then quickly added 
to the liquified polymer mixture, the lid 228 is put in place and the 
agitating means 273 are actuated. The temperature is then raised to about 
260.degree. F.and the mixing is continued for 5-15 minutes. The valve "V" 
is then opened to allow flow of the molten polymer enriched with perfume 
ingredient to exit through the orifices 234. The liquid falling through 
the orifices 234 solidifies almost instantaneously upon impact with the 
moving cooled conveyor 238. Polymer beads or pellets 244 having pronounced 
scents as described in Table IV of Example VII, supra, are thus formed. 
Analysis demonstrates that the pellets contain about 25 % of the perfume 
material so that almost no losses in the scenting substance did occur. 
These pellets may be called "master pellets". 
50 Pounds of each batch of the scent containing "master pellets" are then 
added to one thousand pounds of unscented polypropylene and the mass is 
heated to the liquid state. The liquid is molded into thin sheets of 
films. The thin sheets of films have pronounced aromas as set forth in 
Table IV of Example VII, supra. The sheets of films are cut into strips of 
0.25" in width.times.3" in length and placed into room air fresheners. 
On operation of the room air freshener, after four minutes, the room in 
each case has an aesthetically pleasing aroma with no foul odor being 
present, the aroma being described in Table IV of Example VII, supra. 
EXAMPLE XVI 
Citrus/Grape Flavor Formulations 
The following citrus/grape flavor formulations are prepared: 
______________________________________ 
Parts by Weight 
Ingredients XVI(A) XVI(B) VI(C) 
______________________________________ 
The schiff base reaction 
26.0 0 13.0 
product of pino 
acetaldehyde, helional 
and methyl anthranilate 
prepared according 
to Example II. 
The schiff base reaction 
0 26.0 13.0 
product of Example IV(A), 
the Schiff base reaction 
product of helional, 
lyral and methyl 
anthranilate with the mole 
ratio of helional:lyral: 
methyl anthranilate being 
1:2:3. 
Natural Lemon Oil Terpeneless 
10.0 10.0 10.0 
Acetaldehye 0.6 0.6 0.6 
Alpha-Terpineol 2.1 2.1 2.1 
Citral 1.8 1.8 1.8 
Carvone 0.24 0.24 0.24 
Terpinolene 1.2 1.2 1.2 
Alpha-Terpinene 0.25 0.25 0.25 
Diphenyl 0.25 0.25 0.25 
Alpha-Fenchyl Alcohol 
0.25 0.25 0.25 
Limonene 0.35 0.35 0.35 
Linalool 0.25 0.25 0.25 
Geranyl Acetate 0.25 0.25 0.25 
Nootkatone 0.25 0.25 0.25 
Nryl Acetate 0.25 0.25 0.25 
Cyclohexyldisulfide 
2.5 0 2.5 
______________________________________ 
The flavor formulation of Example "A" (hereinafter referred to as Example 
XVI(A) has an intense citrusy and "natural" grape aroma and taste profile. 
The flavor formulation of Example XVI(B) has an intense citrusy "natural 
lemon" aroma and taste profile due to the presence of the schiff base 
reaction product of helional, lyral and methyl anthranilate. 
The flavor formulation of Example XVI(C) has a "natural" grape and lemony 
aroma profile with the lemon nuances augmenting and enhancing the grape 
nuances and this is primarily due to the presence of the mixture of the 
schiff base reaction product of lyral, helional and methyl anthranilate of 
Example IV(A) and of the schiff base reaction product of helional, pino 
acetaldehyde and methyl anthranilate of Example II. 
EXAMPLE XVII 
A. Powder Flavor Compositions 
20 Grams of each of the flavor compositions of Examples XVI(A), XVI(B) and 
XVI(C) containing schiff base reaction products of methyl anthranilate 
with helional and pino acetaldehyde and/or lyral is emulsified in a 
solution containing 300 grams gum acacia and 700 grams water. The emulsion 
is spray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air 
with an inlet temperature of 500.degree. F., an outlet temperature of 
200.degree. F., and a wheel speed of 50,000 rpm. 
B. Sustained Release Flavors 
The following mixtures are prepared: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Liquid Citrus/Grape Flavor 
20.0 
Compositions of one 
of Examples XVI(A), 
XVI(B) or XVI(C). 
Propylene glycol 9.0 
CAB-O-SIL .RTM.M-5 5.0 
Brand of Silica produced by 
the Cabot Corporation of 
125 High Street, Boston, 
Massachusetts 02110: 
Physical Properties: 
Surface area: 200 m/.sup.2 /gm 
Nominal particle size: 0.012 microns 
Density: 2.3 lbs./cu.ft. 
______________________________________ 
The Cab-O-Sil is dispersed in each of the liquid citrus/grape flavor 
compositions of Examples XVI(A), XVI(B) and XVI(C) with vigorous stirring, 
thereby resulting in a viscous liquid. 71 Parts by weight of each of the 
powder flavor compositions of Part A, supra, is then blended into the said 
viscous liquids, with stirring at 25.degree. C. for a period of 30 minutes 
resulting in dry free flowing sustained release flavor powders. 
EXAMPLE XVIII 
10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts by 
weight of water at a temperature of 150.degree. F. The mixture is agitated 
until the gelatin is completely dissolved and the solution is cooled to 
120.degree. F. 20 Parts by weight of each of the liquid flavor 
compositions of Examples XVI(A), XVI(B) and XVI(C) are separately added to 
the solution which is then homogenized to form an emulsion having particle 
size in the range of 5-40 microns. The material is kept at 120.degree. F. 
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. 
Gelatin is effected by pouring the heated coacervate mixture into 1,000 
parts by weight of 7% aqueous solution of sodium sulfate at 65.degree. C. 
The resulting gelled coacervate may be filtered and washed with water at 
temperatures below 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 XIX 
Chewing Gums 
100 Parts by weight of chicle are mixed with 4 parts by weight of each of 
the flavors prepared in accordance with Example XVII(B). 300 Parts of 
sucrose and 100 parts of corn syrup are added. Mixing is effected in a 
ribbon blender with jacketed side walls of the type manufactured by the 
Baker Perkins Company. 
The resultant chewing gum 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 
citrus/grape flavor. 
EXAMPLE XX 
Chewing Gums 
100 Parts by weight of chicle are mixed with 18 parts by weight of each of 
the flavors prepared in accordance with Example XVIII. 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 Company. 
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 
citrus/grape flavor. 
EXAMPLE XX 
Toothpaste Formulations 
The following separate groups of ingredients are prepared: 
______________________________________ 
Parts by Weight 
Ingredients 
______________________________________ 
Group "A" 
30.200 Glycerine 
15.325 Distilled Water 
0.100 Sodiium Benzoate 
0.125 Saccharin Sodium 
0.400 Stannous Fluoride 
Group "B" 
12.500 Calcium Carbonate 
37.200 Dicalcium Phosphate (Dihydrate) 
Group "C" 
2.000 Sodium N--Lauroyl Sarcosinate 
(foaming agent) 
Group "D" 
1.200 Each of the Flavor Materials of 
Example XVII(B). 
______________________________________ 
Procedure 
1. The ingredients in Group "A" are stirred and heated in a steam jacketed 
kettle to 160.degree. F.; 
2. Stirring is continued for an additional three to five minutes to form a 
homogeneous gel; 
3. The powders of Group "B" 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 tooth brushing procedure 
yields a pleasant citrus/grape flavor, of constant strong intensity 
throughout said procedure (1-1.5 minutes). 
EXAMPLE XXI 
Chewable Vitamin Tablets 
Each of the flavor materials produced according to the process of Example 
XVII(B) is added to a Chewable Vitamin Tablet Formulation at a rate of 10 
gm/Kg which chewable vitamin tablet formultion is prepared as follows: 
In a Hobart Mixer the following materials are blended to homogeneity: 
______________________________________ 
Gms/1000 Tablets 
______________________________________ 
Vitamin C (ascorbic acid) as ascorbic 
70.00 
acid-sodium ascorbate mixture 1:1 
Vitamin B.sub.1 (thiamine mononitrate) as 
4.0 
ROCOAT .RTM. thiamine mononitrate 331/3% 
(Hoffman La Roche) 
Vitamin B.sub.2 (riboflavin) as ROCOAT .RTM. 
5.0 
riboflavin 331/3% 
Vitamin B.sub.6 (pyridoxine hydrochloride) 
4.0 
as ROCOAT .RTM. pyridoxine hydrochloride 
331/3% 
Niacinamide as ROCOAT .RTM. niacinamide 
33.0 
331/3% 
Calcium pantothenate 11.5 
Vitamin B.sub.12 (cyanocobalamin) as 
3.5 
Merck 0.1% in gelatin 
Vitamin E (dl-alpha tocopheryl 
6.6 
acetate) as dry Vitamin E 
acetate 331/3% ROCHE .RTM. 
d-Biotin 0.044 
Each of the flavor formulations 
(as indicated 
of Example XVII(B) above) 
Certified lake color 5.0 
Sweetener - sodium saccharin 
1.0 
Magnesium stearate lubricant 
10.0 
Mannitol q.s. to make 500.0 
______________________________________ 
Preliminary tablets are prepared by slugging with flatfaced punches and 
grinding the slugs to 14 mesh. 13.5 g dry Vitamin A Acetate and 0.6 g 
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 citrus/grape flavor for a period of 12 minutes. 
EXAMPLE XXII 
Chewing Tobacco 
Onto 100 pounds of tobacco for chewing (85% Wisconsin lead and 15% 
Pennsylvania leaf) the following casing is sprayed at a rate of 30%: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Corn Syrup 60.0 
Licorice 10.0 
Glycerin 20.0 
Fig Juice 4.6 
Prune Juice 5.0 
Each of the Flavor Materials 
0.4 
of Example XVII(B) 
______________________________________ 
The resultant product is redried to a moisture content of 20%. On chewing, 
this tobacco has an excellent substantially consistent, long-lasting 
citrus/grape and licorice aroma and taste profile in conjunction with the 
tobacco note. 
EXAMPLE XXIII 
To 100 parts by weight of GOYA.RTM. mango nectar (produced by the Goya 
Corporation of New York, N.Y.) is added 10 ppm of the schiff base reaction 
product of Example III(B), the schiff base reaction product of helional, 
pino isobutyraldehyde and methyl anthranilate with the mole ratio of pino 
isobutyraldehyde:helional:methyl anthranilate being 1:2:3. The resulting 
schiff base reaction product adds to the mango nectar a very natural 
lemony which causes the resulting mango nectar to be aesthetically 
pleasing and to a 25 member panel to be preferred over the standard mango 
nectar. 
EXAMPLE XXIV 
A fabric washing deodorant detergent powder product is prepared by admixing 
the following ingredients: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Linear alkylbenzene sulfonate 
9.0 
C.sub.13 -C.sub.15 straight chain 
4.0 
alcohols (30:30:40 mixture of 
C.sub.13, C.sub.14, and C.sub.15 straight 
chain alcohol) 
Sodium tripolyphosphate 
16.0 
ZEAOLIGHT 8.0 
Sodium silicate 4.0 
Magnesium silicate 0.8 
Ethylene diamine 0.6 
N,N,N',N'--[tetra(methylene 
0.9 
phosphonic acid)] sodium carboxy 
methyl cellulose 
Anti-foam 1.5 
Sodium Perborate tetrahydrate 
14.0 
N,N,N',N'--Tetraacetyl 
4.2 
Glycoluril 
Schiff base reaction product 
0.35 
of helional and methyl anthranilate 
produced according to Example I. 
Water 45.0 
Sodium sulfate 5.0 
______________________________________ 
The resulting fabric washing deodorant detergent powder on use gives rise 
to a very pleasant "fresh air" aroma without any aesthetically displeasing 
aromas subsequent to the washing of the fabrics in the standard washing 
machine cycle. 
When the foregoing composition is created wherein the helional-methyl 
anthranilate schiff base is replaced in the same quantity by any of the 
following schiff bases, identical results are achieved: 
(i) The schiff base reaction product of methyl anthranilate, helional and 
pino acetaldehyde prepared according to Example II; 
(ii) The schiff base reaction product of methyl anthranilate, helional and 
pino isobutyraldehyde prepared according to Example III(A); 
(iii) The schiff base reaction product of methyl anthranilate, helional and 
pino isobutyraldehyde prepared according to Example III(B); 
(iv) The schiff base reaction product of lyral, helional and methyl 
anthranilate prepared according to Example IV(A); and 
(v) The schiff base reaction product of lyral, helional and methyl 
anthranilate prepared according to Example IV(B). 
Deodorant detergent products have also been prepared according to Examples 
I-IX of U.S. Pat. No. 4,304,679 incorporated by reference herein. 
Thus, exemplified herein by reference are the following deodorant detergent 
products comprising: 
(i) from 0.5 to 99.99% by weight of a non-soap detergent active compound; 
and 
(ii) from 0.01 to 10% by weight of a deodorant composition comprising from 
45 to 100% by weight of at least one of the schiff bases or schiff base 
compositions exemplified by Examples I-IV(B), supra, said schiff base 
components having a lipoxidase-inhibiting capacity of at least 50% or a 
Raoult variance ratio of at least 1.1 as stated in said U.S. Pat. No. 
4,304,679, with the schiff base composition having a deodorant value of 
from 0.5 to 3.5 as measured by the deodorant value test as specifically 
set forth in said U.S. Pat. No. 4,304,679 and exemplified therein. 
Furthermore, the examples of U.S. Pat. No. 4,663,068 are also incorporated 
herein by reference. 
Thus, exemplified herein are detergent powder products suitable for the 
washing of fabrics comprising: 
(i) from 5 to 40% by weight of a non-soap detergent active compound 
comprising an anionic detergent active compound; 
(ii) from 1 to 90% of a non-soap detergency builder; 
(iii) from 1 to 30% by weight a peroxy bleach compound together with an 
activator therefor; 
(iv) from 0.1 up to 10% by weight of a bleach stable perfume which 
comprises 50-100% by weight of a bleach stable schiff base component as 
exemplified by any one of Examples I-IX or mixtures thereof, having a 
Lipoxidase-inhibiting capacity of at least 50% or a Raoult variance ratio 
of at least 1.1 as defined according U.S. Pat. No. 4,663,068 incorporated 
by reference herein, with the schiff base reaction product as defined in 
any one of Examples I-IV(B), supra being stable in the presence of sodium 
perborate tetrahydrate or any other alkali metal perborate tetrahydrate 
and N,N,N',N'-tetraacetyl ethylenediamine (TEAD) according to the bleach 
stability test as defined in said U.S. Pat. No. 4,663,068 incorporated by 
reference herein, the bleach stable deodorant schiff base having a Malodor 
Reduction Value of from 0.25 up to 3.0 as measured by the Malodor 
Reduction Value test defined in said U.S. Pat. No. 4,663,068 incorporated 
by reference herein. 
The peroxy bleach activator may be exemplified by the following peroxy 
bleach activators: 
N,N,N',N'-tetracetyl ethylenediamine; 
N,N,N',N'-tetracetyl glycoluril; 
Glucose pentaacetate; 
Sodium acetoxybenzene sulphonate; 
Sodium nonanoyloxybenzene sulphonate; 
Sodium octanoyloxybenzene sulphonate; and 
mixtures thereof. 
The non-soap anionic detergent active compound may be selected from the 
group consisting of sodium and potassium alkyl sulphates, sodium potassium 
and ammonium alkyl benzene sulphonates, sodium alkyl glyceryl ether 
sulphates, sodium coconut oil fatty acids monoglyceride sulphates and 
sulphonates, sodium and potassium salts of sulphuric acid esters of higher 
(C.sub.9 -C.sub.18) fatty alcohol-alkylene oxide, the reaction products of 
fatty acids esterified with isethionic acid and neutralized with sodium 
hydroxide, sodium and potassium salts of fatty acid amides of methyl 
taurine, alkane monosulphonates, olefin sulphonates and mixtures thereof. 
The nonionic detergent active compound may be selected from the group 
consisting of reaction products of alkylene oxides with alkyl (C.sub.6 
-C.sub.22) phenols, the condensation products of aliphatic (C.sub.8 
-C.sub.18) primary or secondary linear or branched alcohols with ethylene 
oxide, products made by condensation of ethylene oxide with the reaction 
products of propylene oxide and ethylene diamine, long-chain tertiary 
amine oxides, long-chain phosphine oxides and dialkyl sulphoxides and 
mixtures thereof.