Acetylated alpha methyl styrene dimers or derivatives in perfumes

A process is described for providing clear extended compositions of essential oils which comprises a composition of an essential oil and an extender material miscible with said essential oil which does not appreciably alter the aroma of the essential oil insofar as its quality or strength is concerned, the proportion of essential oil in extender material being from about 70% up to about 99%, said extender material being an acylated dimerization product of an alpha methyl styrene or a methyl or other C.sub.2 -C.sub.4 lower alkyl homologue thereof or hydrogenated derivative thereof or mixture of same.

BACKGROUND OF THE INVENTION 
Compounded perfumery compositions contain a number of ingredients which may 
be of natural or synthetic origin. The ingredients are blended by the 
perfumer to create the desired odor effect. Such essential oils which 
contain high percentages of hydrocarbon constituents such as patchouli oil 
(an essential oil derived from Pogostemon Patchouli) have, for example, 
warm aromatic spicey odors. When the perfumer wishes to include this type 
of note for example in a perfumery composition of an oriental type, he 
will use patchouli oil. However, such natural oils as oil of patchouli are 
expensive essential oils and are of limited availability. Even more 
extreme examples are natural sandalwood oil and natural vetiver oil. 
Although, attempts have been made to simulate the odor of patchouli oil, 
sandalwood oil and vetiver oil by use of blends of synthetic perfumery 
chemicals, the creation of such oils having identical aromas with 
reference to the natural oils has not been achieved. 
In U.S. Pat. No. 3,673,120 issued on June 27, 1972, 8-camphene carbinol was 
indicated to be useful as a perfumery extender for patchouli oil in 
perfumery compositions when present in a concentration of from 1 to 200 
parts by weight per 100 parts by weight of the patchouli oil. However, 
8-camphene carbinol has the disadvantage of significantly decreasing the 
aroma strength of the patchouli oil and is not versatile for use with oils 
other than patchouli oil, for example, vetiver oil and sandalwood oil in 
the genus of natural oils, and synthetic oils, for example, geranonitrile 
and cinnamonitrile. 
In U.S. Pat. No. 2,422,145 issued on June 10, 1947, water-soluble hydroxy 
polyoxyethylene ethers of partial higher fatty acid esters of low 
molecular weight polyhydroxylic compounds were found to form clear 
extended solutions with essential oils which could be used as such or 
which would be diluted with water to form stable dispersions or solutions 
of essential oils. Specifically disclosed are compositions containing 
clear, stable solutions of a quantity of an essential oil and at least an 
equal quantity of such ethers as mannitan monopalmitate hydroxy 
polyoxyethylene ether with about 20 oxyethylene units per mole with such 
solution being capable, upon dilution with water, of forming a clear, 
stable aqueous dispersion of essential oil and hydroxy polyoxyethylene 
ether. U.S. Pat. No. 2,422,145, however, does not disclose the formation 
of solutions of essential oil in organic solvents which are immiscible 
with water. Furthermore, the ethers of U.S. Pat. No. 2,422,145 
significantly reduce the strength of the perfumery material when used in 
conjunction with same. 
Cyclohexane dicarboxylic acid diesters having the structure: 
##STR1## 
wherein R.sub.1 and R.sub.2 are less than 13 carbon aliphatic or alicyclic 
hydrocarbon moieties are disclosed to be useful "perfume harmonizing 
agents" in Japanese Published Application at J 52136927 issued on Nov. 15, 
1977 to Asahi Denka Kogyo. However, such materials as these cyclohexane 
dicarboxylic acid diesters detract from the strength of the perfume 
material with which it is used. 
Processes for preparing alpha methyl styrene dimers and methyl homologues 
thereof are broadly disclosed in the prior art, for example, 
French Pat. No. 1,317,412 assigned to Socony Mobil Oil Company dated Feb. 
8, 1963; 
U.S. Pat. No. 3,161,692 issued on Dec. 15, 1964 assigned to Socony Mobil 
Oil Company; 
U.S.S.R. Pat. No. 191,511 issued on Jan. 26, 1967; 
U.S. Pat. No. 3,523,981 assigned to Olin Corporation, issued on Aug. 11, 
1970; 
Deutsche Offenlengungschrift No. 2,101,089 issued on Aug. 10, 1972; 
U.S. Pat. No. 3,890,402 assigned to Phillips Petroleum Company issued on 
June 17, 1975; 
Petropoulos and Fisher, J.Am.Chem.Soc., 80, 1938-41 (1958); and 
U.S. Pat. No. 4,081,489 issued on Mar. 28, 1978. 
U.S. Pat. No. 4,081,489 disclosed an improved process for the production of 
compounds having the formula: 
##STR2## 
wherein R is independently hydrogen or methyl by contracting a compound of 
Formula I: 
##STR3## 
where mixture of compounds of Formula I, wherein R is hydrogen or methyl, 
with a sulfuric acid catalyst at a temperature of 100.degree. to 
225.degree. C. which comprises a catalyst consisting essentially of about 
0.05 up to about 3 weight percent based on the weight of the compound or 
mixture of compounds of Formula I, of 90 to 98% concentrated sulfuric 
acid. 
Our U.S. Application for Letters Patent, Ser. No. 902,565 filed on May 3, 
1978 (now U.S. Pat. No. 4,142,997 issued on Mar. 6, 1979) teaches the 
process for providing a clear extended composition of essential oils which 
comprises a composition of an essential oil and an extender material 
miscible with said essential oil which does not appreciably alter the 
aroma of the essential oil insofar as its quality or strength is 
concerned, the proportion of essential oil in extender material being a 
dimerization product of an alpha methyl styrene or a methy or other 
C.sub.2 -C.sub.4 lower alkyl homologue thereof or hydrogenated derivative 
thereof or mixture of same, having one of the generic structures: 
##STR4## 
wherein R.sub.3 and R.sub.4 are the same or different and each represents 
hydrogen or methyl or other C.sub.2 -C.sub.4 lower alkyl and wherein the 
dashed lines and wavy lines represent carbon-carbon single bonds or 
carbon-carbon double bonds with the proviso that when there is one double 
bond present only the wavy line is a double bond and when there is more 
than one double bond present, the ring containing the dashed lines and the 
wavy line is a benzene ring and wherein the line represents either a 
carbon-carbon single bond or no bond. 
Nothing in the prior art teaches the use of acetylated alpha methyl styrene 
dimers, methyl homologues thereof or hydrogenated derivatives thereof as 
perfume diluents or as perfume extenders. Furthermore, nothing in the 
prior art teaches the use of hydrogenated derivatives of such acetylated 
alpha methyl styrene dimers or methyl homologues thereof.

THE INVENTION 
Surprisingly, it has been found that acetylated alpha methyl styrene 
dimerization products, acetylated dimerization products of methyl or other 
C.sub.2 -C.sub.4 lower alkyl homologues thereof and hydrogenated 
derivatives thereof may be used as diluents or extenders of various 
perfumery materials without appreciable loss of the characteristic odor 
effect of such perfumery materials. Such dimerization products are 
produced by first dimerizing alpha methyl styrene having the structure: 
##STR5## 
or by dimerizing a methyl or other C.sub.2 -C.sub.4 lower alkyl homologue 
thereof having, for example, the structure: 
##STR6## 
in the presence of Lewis Acid catalysts, Bronstedt acid catalysts such as 
sulfuric acid or in the presence of acid clay catalysts such as Japanese 
Acid Clay or Fullers earth or acidic cation exchange resin catalysts. The 
dimerization product of alpha methyl styrene so produced have the 
structures: 
##STR7## 
wherein one of R.sub.5 or R'.sub.5 is methyl or other C.sub.2 -C.sub.4 
lower alkyl and the other of R.sub.5 or R'.sub.5 is hydrogen or each of 
R.sub.5 and R'.sub.5 are the same or different C.sub.1 -C.sub.4 lower 
alkyl, e.g., methyl. 
The resulting dimerization products are then acetylated using acetyl 
chloride or acetyl bromide in the presence of a Lewis acid catalyst, such 
as aluminum chloride. 
Hydrogenation products thereof have the structures: 
##STR8## 
(wherein R.sub.3 and R.sub.4 are the same or different and each represents 
hydrogen, methyl or other C.sub.2 -C.sub.4 lower alkyl and wherein G is 
one of the moieties: 
##STR9## 
with at least one of G being a moiety having the structure: 
##STR10## 
wherein one or both of R.sub.5 and R'.sub.5 is methyl or other C.sub.2 
-C.sub.4 lower alkyl and wherein n=0 or 1 and m=0 or 1 and the sum of m+n 
is such that the inequality: 
EQU 0&lt;m+n.ltoreq.2 
is in effect. Such hydrogenation products can be represented by the generic 
structure: 
##STR11## 
wherein R.sub.3 and R.sub.4 are the same or different and represent 
hydrogen or methyl or other C.sub.2 -C.sub.4 lower alkyl; wherein the 
dashed lines and wavy line represent carbon-carbon single bonds or 
carbon-carbond double bonds with the proviso that when there is one double 
bond present, only the wavy line is a double bond and when there is more 
than one double bond present, the ring containing the dashed lines and the 
wavy line is a benzene ring and where the line represents either a 
carbon-carbon single bond or no bond. 
Contemplated in this case are geometric isomers of the hydrogenation 
products of our invention. Thus, in the case of the hydrogenation product, 
when R.sub.3 and/or R.sub.4 are lower alkyl, for example, methyl, the 
methyl groups may be in a "cis" or "trans" relationship to one another and 
with respect to the hydroxy alkyl group or groups. 
A significant property of the above-said dimerization products and 
hydrogenated dimerization products is that they have a broad range of 
solubilities for various types of perfumery materials including complete 
solubility for certain alcohols, esters, pyrans, aldehydes, ketones, 
cyclic ethers, cyclic amines, nitriles and natural oils. Thus, for 
example, the following materials are completely miscible with the dimers 
which are the subject of our invention. 
Phenyl Ethyl Alcohol 
Geraniol 
Terpineol 
Citronellyl Acetate 
Decyl Acetate 
Rose Oxide 
n-Decanal 
Citral 
Alpha Ionone 
Eugenol 
Galaxolide 
2-Methyl-2-Pentenoic Acid 
Isobutyl Quinoline 
Lemon Oil 
Rosemary Oil 
Patchouli Oil 
Cinnamonitrile 
Geranonitrile 
Thus, it has been discovered that the dimers of our invention can be used 
as partial replacements for certain essential oils and synthetic 
substitutes therefor in compounded single phase liquid perfumery 
compositions. 
Accordingly, the present invention comprises a compounded single phase 
liquid perfumery composition which comprises one or more synthetic perfume 
oils or natural perfume oils or mixtures of natural perfume oils and 
synthetic perfume oils with which there has been incorporated from about 1 
up to about 30 parts of an acetylated alpha methyl styrene or alpha methyl 
styrene methyl or other C.sub.2 -C.sub.4 lower alkyl homologue 
dimerization product or hydrogenated derivative thereof or mixture of 
acetylated alpha methyl styrene or alpha methyl styrene methyl (or other 
C.sub.2 -C.sub.4 lower alkyl) homologue dimerization product and one or 
more hydrogenated derivatives thereof which have at least one of the 
following structues: 
##STR12## 
wherein one or both of R.sub.5 and R'.sub.5 is methyl or other C.sub.2 
-C.sub.4 lower alkyl and these compounds may be represented collectively 
by the generic structures: 
##STR13## 
in the case of acetylated alpha methyl styrene dimerization products and 
dimerization products of methyl or other C.sub.2 -C.sub.4 lower alkyl 
homologues thereof and the structures: 
##STR14## 
wherein m=0 or 1 and n=0 or 1 and m+n are further defined by the 
mathematical inequality: 
EQU 0&lt;m+n.ltoreq.2; 
wherein one of R.sub.5 and R'.sub.5 is methyl or other C.sub.2 -C.sub.4 
lower alkyl and the other is hydrogen, or both R.sub.5 and R'.sub.5 are 
methyl or other C.sub.2 -C.sub.4 lower alkyl in the case of the 
hydrogenated derivatives thereof wherein the dashed lines and wavy lines 
represent carbon-carbon single bonds or carbon-carbon double bonds with 
the proviso that when there is one double bond present in the ring 
containing the dashed lines and wavy lines, only the wavy line is a double 
bond and when there is more than one double bond present, the ring 
containing the dashed lines and the wavy lines is a benzene ring; and 
wherein the line represents either a carbon-carbon single bond or no 
bond; and wherein the line+++++represents a carbon-carbon single bond or a 
carbon-carbon double bond with the proviso that when the line++++is a 
carbon-carbon double bond, the line is no bond and when the line+++++is 
a carbon-carbon single bond, the line is a carbon-carbon single bond, 
per 100 parts of compounded single phase liquid perfumery composition. 
Each of these acylated dimerization products and hydrogenated derivatives 
thereof by themselves have no odor which is perceptible to the human 
olfactory sense of smell at ambient conditions and do not by themselves 
impart any alteration of odor to any of the perfumery materials to which 
they are added alone or in combination with one another. The above-stated 
acylated dimerization products and hydrogenated derivatives thereof may be 
produced according to any of the known methods in the prior art and 
according to any one of the following reaction schemes: 
##STR15## 
wherein n=0 or 1 and m=0 or 1 and the sum of m+n is such that the 
inequality: 
EQU 0&lt;m+n.ltoreq.2 
is in effect; wherein G is one of the moieties: 
##STR16## 
with at least one of G being a moiety having the structure: 
##STR17## 
and wherein R.sub.3 and R.sub.4 are the same or different and repesent 
hydrogen or methyl or other C.sub.2 -C.sub.4 lower alkyl and wherein the 
dashed lines, the wavy lines, and the line and the line++++are as 
defined above. 
In the dimerization reaction, the catalysts that may be used are Lewis Acid 
such as borontrifluoride-aluminum trichloride or Bronstedt Acids such as 
sulfuric acid or phosphoric acid or such acids on carriers such as 
alumina, silica or cation exchange resin catalysts such as Amberlyst.RTM. 
15, or acid clay catalysts such as Japanese Acid clay or Fullers earth. 
The dimerization reaction is carried out in the presence of a solvent such 
as cyclohexane, or in the absence of solvent. The temperature range for 
the dimerization may be from about 20.degree. C. up to about 250.degree. 
C. with a preferred temperature range when using borontrifluoride etherate 
of 0.degree.-100.degree. C. or when using acid clays of from 
80.degree.-200.degree. C. The presence at which the reaction may be 
carried out is conveniently atmospheric pressure but higher pressures or 
pressures lower than atmospheric may also be used without adversely 
affecting the yield of product. The weight ratio of alpha methyl styrene 
or alphe methyl styrene methyl homologue:catalyst is from about 1:0.005 up 
to about 1:0.2 when using an acid clay catalyst and from about 1:0.1 up to 
about 1:3 when using, for example, a Bronstedt acid catalyst such as 
sulfuric acid. 
The hydrogenation reaction may be carried out at standard hydrogenation 
conditions using standard hydrogenation catalysts. Thus, for example, the 
hydrogenation reaction is carried out in the presence of a palladium on 
carbon catalyst or a Raney nickel catalyst at temperatures of from about 
80.degree. C. up to about 150.degree. C. at pressures of from about four 
atmospheres up to about thirty atmospheres. Such catalysts such as 
palladium (from 1% up to 10%) on calcium carbonate in the presence of an 
inert solvent, such as ethyl acetate, and catalyst promoter, such as 
quinoline, or palladium (from 1% up to 10%) on barium sulfate are 
particularly preferred. The mole ratio of catalyst:catalyst promoter, 
e.g., palladium on barium sulfate-quinoline is preferaby about 1:1 
(weight:weight) but ratios of catalyst:promoter may vary from about 0.25:1 
up to about 1:0.25. The weight ratio of material to be hydrogenated:inert 
solvent (e.g., ethyl acetate) may vary from about 1:1 up to about 1:20 
with a ratio of about 1:10 (weight:weight) being preferred. At the end of 
the reaction, the reaction product may, if desired, be separated by means 
of such physical separation techniques as fractional distillation. 
The extended perfumery oils and chemicals of our invention may be used in 
compositions where the natural oils or chemicals would have been used, for 
example, in combination with sandalwood oil, vetiver oil, oakmoss, ionone, 
labdanum, methyl ionone, patchouli oil and other synthetic substitutes 
therefor. 
The extended perfumery materials of our invention will find use as 
constituents of compounded perfumery compositions in which a number of 
perfumery materials of natural and/or synthetic origin will be blended 
together to produce a particular desired odor effect. Such compositions 
may then be used in space sprays or can be blended in soap, detergent or 
deodorant compositions, including bath salts, shampoos, toilet waters, 
face creams, talcum powders, body lotions, sun cream preparations and 
shave lotions and creams. The perfumery compositions can also be used to 
perfume sub-straights such as fibers, fabrics and paper products. 
The following examples are given to illustrate embodiments of the invention 
as it is presently preferred to practice it. It will be understood that 
these examples are illustrative and the invention is not to be considered 
as restricted thereto except as indicated in the appended claims. 
EXAMPLE I 
PREATION OF ALPHA METHYL STYRENE DIMERIZATION PRODUCT 
Reaction: 
##STR18## 
Into a two-liter reaction flask equipped with thermometer, reflux 
condenser, cooling bath, addition funnel, stirrer and gas bubbler is 
placed 100 g of water. Over a sixteen-minute period, 318 g of concentrated 
sulfuric acid is added to the water. The contents of the flask is then 
brought to 30.degree. C. Over a period of two hours after the sulfuric 
acid is added, while maintaining the temperature of the reaction mass at 
20.degree.-33.degree. C., 500 g of alpha methyl styrene is added. After 
the addition of the alpha methyl styrene, the reaction mass is maintained 
at a temperature of 30.degree. C. for a period of four hours. 500 g of 
water is then added followed by 250 g of cyclohexane. The reaction mass is 
then stirred for a period of fifteen minutes and heated to 70.degree. C. 
The layers are separated and the organic layer is washed neutral (at 
70.degree. C.) with a 5% sodium hydroxide solution (two 250 ml volumes) 
and a 5% sodium chloride solution (three 250 ml volumes). 650 g of crude 
product is recovered and redistilled after adding to the mixture 15 g of 
Primol.RTM. and 0.2 g of Ionox.RTM. through a 12" Vigreaux column as 
follows: 
______________________________________ 
Vapor Liquid Weight of 
Fraction 
Temp. Temp. Vac. mm. 
Fraction 
______________________________________ 
1 69 101/135 760/760 102.2 
2 132 145 2.3 2.8 
3 132 146 2.3 26.4 
4 132 147 2.3 16.0 
5 132/134 148/148 2.2/2.2 19.4 
6 132 149 2.2 26.2 
7 132 149 2.2 21.6 
8 132 142 2.2 25.4 
9 132 150 2.2 24.2 
10 133 150 2.2 29.6 
11 133 151 2.5 28.2 
12 133 151 2.4 25.5 
13 133 152 25.0 
14 133 152 2.3 23.7 
15 133 155 31.5 
16 135 162 2.3 29.4 
17 137 169 2.3 23.1 
18 139 176 2.3 12.5 
19 142 202 13.2 
20 141 221 2.3 10.3 
21 188 230 10.5 
22 187 242 2.3 8.1 
______________________________________ 
FIG. 1 sets forth a GLC profile for Fraction 19. This fraction is primarily 
the alpha methyl styrene dimer having the structure: 
##STR19## 
FIG. 2 is the infrared spectrum for Fraction 19. FIG. 3 is the NMR spectrum 
for Fraction 19. The mass spectrum for Fraction 19 which is the compound 
having the structure: 
##STR20## 
is as follows: 
______________________________________ 
M/E Relative Intensity 
______________________________________ 
39 23.sup.5 
41 27.sup.4 
51 18 
77 19 
91 42.sup.2 
103 14 
119 100.sup.1 
143 20 
221 32.sup.3 
236 20.sup.6 
______________________________________ 
The GLC profile for Fraction 3 which is primarily the compound having the 
structure: 
##STR21## 
is set forth in FIG. 4. FIG. 5 sets forth the infrared spectrum for 
Fraction 3. FIG. 6 sets forth the NMR spectrum for Fraction 3. 
FIGS. 4, 5 and 6 also represent, respectively, the GLC, IR and NMR spectra 
for the product produced according to Example III, infra. 
EXAMPLE II 
PREATION OF ALPHA METHYL STYRENE DIMERIZATION PRODUCT 
Reaction: 
##STR22## 
Into a one-liter reaction flask equipped with thermometer, addition funnel, 
heating mantle, reflux condenser, stirrer, Y-adapter and distillation head 
is added 100 g of cyclohexane followed by 5 g of p-toluene sulfonic acid. 
The resulting mixture is heated to 50.degree. C. and over a one-hour 
period, 500 g of alpha metal styrene is added to the reaction flask. The 
reaction mass is then heated to 100.degree. C. and maintained at that 
temperature for a period of four hours. 529.3 g of crude product is then 
recovered which is then mixed with 15 g of Primol.RTM. and 0.2 g of Ionox 
.RTM.. The resulting mixture is distilled through a "Y" adapter 
distillation column yielding the following distillation data: 
______________________________________ 
Vapor Liquid Weight of 
Fraction 
Temp. Temp. Vac. mm. 
Fraction 
______________________________________ 
1 21/80 90/149 2.6/2.5 6.4 
2 139 155 2.5 7.0 
3 139 155 2.5 21.4 
4 140 157 2.5 34.0 
5 142 160 2.4 49.6 
6 144 170 2.4 100.4 
7 164 195 2.4 58.5 
8 174 203 2.2 8.0 
9 200 215 3.5 70.0 
10 202 215 2.2 31.3 
11 206 215 2.2 27.1 
12 214 225 2.2 18.1 
13 210 250 2.2 41.6 
______________________________________ 
EXAMPLE III 
PREATION OF ALPHA METHYL STYRENE DIMER 
Reaction: 
##STR23## 
Into a 1,000 ml reaction flask equipped with thermometer, addition funnel, 
heating mantle, reflux condenser and stirrer is added 20 g of Filgrol 25 
(a 10-20 mesh granular acid activated clay produced by the Filtrol 
Corporation of 5959 West Century Boulevard, Los Angeles, California 90045) 
having the following properties: 
______________________________________ 
Particle size analysis by Tyler Standard Sieve 
______________________________________ 
Through 10 Mesh, Wt. % 100 
Through 20 Mesh, Wt. % 5 
Free Moisture, Wt. % 10 
Free and Combined Moisture, Wt. 
15 (Max.) 
(Los at 1700.degree. F.) 
Bulk Density, lbs./cu. ft. 
43.0 
Particle Density 1.3 
Surface Area, N.sub.2 adsorbent (Bet Method) M.sup.2 /gm 
______________________________________ 
280-300 
50 g of alpha methyl styrene is added to the Filtrol and the reaction mass 
is heated to 100.degree. C. Another 450 g of alpha methyl styrene is then 
slowly added to the reaction mass over a period of two hours. The reaction 
mass is then heated to 150.degree. C. and maintained at that temperature 
for a period of four hours. The reaction mass is then filtered yielding 
470 g of crude product which is then mixed with 12 g Primol.RTM. and 0.3 g 
Ionox.RTM. and distilled through a 10" Vigreaux column, yielding the 
following fractions and the following distillation data: 
______________________________________ 
Vapor Liquid Weight of 
Fraction 
Temp. Temp. Vac. mm. 
Fraction (gm) 
______________________________________ 
1 38/88 135/140 2.5/2.5 1.2 
2 133 142 2.0 7.0 
3 134 142 2.0 12.0 
4 134 142 2.0 17.1 
5 134 145 1.8 53.5 
6 134 146 1.8 31.0 
7 135 147 1.8 49.2 
8 135 148 1.8 51.5 
9 136 149 1.8 46.2 
10 137 151 1.8 52.3 
11 137 159 1.8 43.2 
12 139 170 1.8 17.5 
13 185 225 1.8 21.6 
(Residue 40.3 g) 
______________________________________ 
FIG. 4 is the GLC profile for Fractions 9-12. FIG. 5 is the infrared 
spectrum for Fractions 9-12 . FIG. 6 is the NMR spectrum for Fractions 
9-12. FIG. 7 is the mass spectrum for Fractions 9-12. FIG. 8 is a second 
GLC profile for Fractions 9-12. 
EXAMPLE IV 
DIACETYLATION OF ALPHA METHYL STYRENE DIMER 
Reaction: 
##STR24## 
Into a two liter reaction flask equipped with stirrer, thermometer, reflux 
condenser, "Y" adapter, nitrogen addition tube, addition funnel and 
two-liter separatory funnel is placed 600 ml CH.sub.2 Cl.sub.2 and 238 g 
of aluminum chloride. Over a fifteen-minute period, 160 g of acetyl 
chloride is added while maintaining the reaction mass at room temperature. 
The resulting reaction mass is then cooled to 15.degree.-20.degree. C. and 
186 g of alpha methyl styrene dimer prepared according to the process of 
Example I is added over a three-hour and ten minute period. Much gas 
evolution is observed. The resulting mixture is stirred at 
15.degree.-20.degree. C. for an additional 1.5 hours whereupon the GLC 
analysis indicates that the reaction has gone to "near" completion. 
The resulting reaction mass is then poured into a 4 liter beaker containing 
1000 g of chopped ice and 300 g of concentrated hydrochloric acid. The 
reaction mass is then covered overnight followed by separation of the 
resulting mixture in a two-liter separatory funnel. The organic layer is 
washed with two volumes (250 ml each) 10% hydrochloric acid solution and 
two 250 volumes of water. The resulting mixture is then transferred to a 
500 ml distillation flask while stripping CH.sub.2 Cl.sub.2 at atmospheric 
pressure to a pot temperature of 100.degree. C. The reaction mass is then 
distilled on a "Y" adapter column yielding the following fractions: 
______________________________________ 
Vapor Liquid Weight of 
Fraction 
Temp. Temp. Vac. mm. 
Fraction (gm) 
______________________________________ 
1 48/209 217/231 2.0 2.3 
2 211 233 1.9 4.4 
3 215 234 1.8 18.7 
4 215 234 1.8 19.7 
5 215 234 1.9 11.5 
6 218 235 2.0 20.1 
7 218 236 2.0 16.3 
8 216 236 1.8 18.7 
9 216 235 1.8 21.9 
10 216 235 1.8 23.1 
11 216 236 1.8 26.6 
12 220 250 2.0 27.8 
______________________________________ 
The reaction product is then analyzed via GLC (Conditions: 8'.times.1/8" 
column, programmed at 80.degree.-250.degree. C. at 8.degree. C. per 
minute). (Material: OV 101). 
FIG. 9 sets forth the GLC profile for the reaction product of this Example 
IV. 
EXAMPLE V 
PREATION OF MONOACETYLATED ALPHA METHYL STYRENE DIMER 
Reaction: 
##STR25## 
Into a 2,000 ml reaction flask equipped with stirrer, thermometer, 
condenser, "Y" adapter, addition funnel and nitrogen inlet tube is placed 
the following materials: 
500 ml CH.sub.2 Cl.sub.2 
119.0 g AlCl.sub.3 
At room temperature, 80.0 g of acetyl chloride is added over a 
fifteen-minute period. This addition is exothermic to less than 30.degree. 
C. changing the color of the solution from milk white to muddy green. The 
resulting mixture is then cooled to 3.degree. C. and 186.0 g of alpha 
methyl styrene dimer prepared according to Example II is added over a two 
hour and forty-five minute period. This addition causes evolution of much 
gas. The mixture is stirred at 0.degree. C. for 5.5 hours after addition. 
The resulting mixture is then poured into a beaker containing 200 g of 
concentrated hydrochloric acid solution and 750 g of chopped ice and the 
beaker is covered. 
The resulting mixture is then separated in a 2 liter separatory funnel and 
the organic layer is washed with two 250 ml volumes of 10% hydrochloric 
acid and two 250 ml volumes of water. The resulting mixture is then 
transferred to a distillation flask (500 ml) while stripping the CH.sub.2 
Cl.sub.2 at atmospheric pressure to a pot temperature of 100.degree. C. 
The resulting mixture is distilled yielding the following fractions: 
______________________________________ 
Vapor Liquid Weight of 
Fraction 
Temp. Temp. Vac. mm. 
Fraction (gm) 
______________________________________ 
1 125/127 158/158 3.0 5.5 
2 127 158 3.0 5.5 
3 128 168 3.0 12.6 
4 130 178 2.9 17.0 
5 137 196 2.9 14.1 
6 155 206 1.5 7.1 
7 176 216 2.0 15.9 
8 182 224 2.0 13.6 
9 185 233 2.0 7.4 
10 208 238 1.7 2.8 
11 210 240 1.6 8.3 
12 212 242 1.6 21.5 
13 212 243 1.6 15.9 
14 213 258 1.6 19.1 
15 209 258 1.6 11.0 
16 155 271 1.6 11.4 
______________________________________ 
FIG. 10 sets forth the GLC profile for the reaction product of this 
Example. It will be seen from FIG. 10 that both the monoacylated and 
diacylated product is obtained. The monacylated and diacylated product may 
be separated from one another or they may be used in admixture. In the 
following examples depending upon this Example V, the monoacylated and 
diacylated products are used in conjunction with one another. 
EXAMPLE VI 
PREATION OF MONOACETYLATED ALPHA METHYL STYRENE DIMER 
Reaction: 
##STR26## 
Into a 2,000 ml reaction flask equipped with stirrer, thermometer, 
condenser, "Y" adapter, addition funnel and nitrogen inlet tube is placed 
the following materials: 
500 ml CH.sub.2 Cl.sub.2 
119.0 g AlCl.sub.3 
At room temperature, 80.0 g of acetyl chloride is added over a 
fifteen-minute period. This addition is exothermic to less than 30.degree. 
C. changing the color of the solution from milk white to muddy green. The 
resulting mixture in then cooled to 3.degree. C. and 186.0 g of alpha 
methyl styrene dimerization product produced according to Example III is 
added over a two hour and forty-five minute period. This addition causes 
evolution of much gas. The mixture is stirred at 0.degree. C. for 5.5 
hours after addition. The resulting mixture is then poured into a beaker 
containing 200 g of concentrated hydrochloric acid solution and 750 g of 
chopped ice and the beaker is covered. 
The resulting mixture is then separated in a 2 liter separatory funnel and 
the organic layer is washed with two 250 ml volumes of 10% hydrochloric 
acid and two 250 ml volumes of water. The resulting mixture is then 
transferred to a distillation flask (500 ml) while stripping the CH.sub.2 
Cl.sub.2 at atmosperic pressure to a pot temperature of 100.degree. C. The 
resulting mixture is distilled yielding the following fractions: 
______________________________________ 
Vapor Liquid Weight of 
Fraction 
Temp. Temp. Vac. mm. 
Fraction (gm) 
______________________________________ 
1 125/127 158/158 3.0 5.5 
2 127 158 3.0 5.5 
3 128 168 3.0 12.6 
4 130 178 2.9 17.0 
5 137 196 2.9 14.1 
6 155 206 1.5 7.1 
7 176 216 2.0 15.9 
8 182 224 2.0 13.6 
9 185 233 2.0 7.4 
10 208 238 1.7 2.8 
11 210 240 1.6 8.3 
12 212 242 1.6 21.5 
13 212 243 1.6 15.9 
14 213 258 1.6 19.1 
15 209 258 1.6 11.0 
16 155 271 1.6 11.4 
______________________________________ 
FIG. 10 sets forth the GLC profile for the reaction product of this 
Example. It will be seen from FIG. 10 that both the monoacylated and 
diacylated product is obtained. The monoacylated and diacylated product 
may be separated from one another or they may be used in admixture. In the 
following examples depending upon this Example VI, the monoacylated and 
diacylated products are used in conjunction with one another. 
EXAMPLE VII 
Patchouli oil (80 parts) obtained from the Seychelle Islands is blended 
with the acylated alpha methyl styrene dimerization product produced 
according to any one of Examples IV, V or VI (20 parts). The acylated 
alpha methyl styrene dimerization product is found to act as an extender 
for the patchouli oil in that the characteristics odor effect of the 
latter is substantially not modified. 
EXAMPLE VIII 
The extended patchouli oil prepared according to Example VII is 
successfully incorporated into a compounded composition of the Chypre type 
by blending the following ingredients: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Cinnamic Aldehyde 1 
Ethyl Methyl Phenyl Glycidate 
1 
Methyl Nonyl Acetaldehyde 
2 
Oakmoss (Absolute) 20 
Sandalwood Oil (East Indian) 
20 
Vetiveryl Acetate 20 
Ylang Oil 20 
Benzoin Resoin (Sumatra) 
30 
Alpha Ionone (100%) 30 
Clove Stem Oil (Zanzibar) 
36 
Bergamot Oil 40 
Hydroxycitronellal 40 
Iso Eugenol 50 
Extended Patchoiuli Oil 
40 
(Example VII) 
Coumarin 50 
Musk Ketone 50 
Amyl Salicylate 60 
Cedarwood Oil (American) 
60 
Citronellol 60 
Benzyl Acetate 80 
Phenyl Ethyl Alcohol 150 
Terpinyl Acetate 150 
TOTAL 1000 
______________________________________ 
A satisfactory chypre perfume containing extended patchouli oil is thus 
provided. 
EXAMPLE IX 
A patchouli oil extender base is prepared by blending the following 
ingredients: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Acylated Dimerization 38 
Product of Alpha Methyl 
Styrene (produced according 
to any one of Examples IV, 
V or VI) 
Galaxolide.RTM. (Registered 
27 
trademark of International 
Flavors & Fragrances Inc. 
identifying a tricyclic 
isochroman) 
Isolongifolene Oxidate 
20 
Omega-Hydroxymethyl 10 
Longifolene 
Cedrol 3 
Sandalwood Oil (East Indian) 
2 
TOTAL 100 
______________________________________ 
This mixture (46 parts) is then blended with natural patchouli oil 
(Seychelles) (60 parts) to provide a satisfactory extended patchouli oil. 
EXAMPLE X 
The extended patchouli oil prepared in Example IX is incorporated into a 
compounded perfumery composition of the Fougere type containing the 
following ingredients: 
______________________________________ 
Ingredients Parts by Weight 
______________________________________ 
Balsam Peru 30 
Labdanum Resin 30 
Oakmoss Absolute 30 
Sandalwood Oil (East Indian) 
30 
Linalyl Acetate 40 
Terpinyl Acetate 40 
Geranium Oil (Bourbon) 50 
Musk Ambrette 50 
Coumarin 60 
Amyl Salicylate 60 
Methyl Ionone 70 
Cedarwood Oil (American) 
80 
Clove Stem Oil (Zanzibar) 
80 
Vetivert Oil (Bourbon) 80 
Extended Patchouli Oil 130 
of Example IX 
Lavandin Oil 140 
TOTAL 1000 
______________________________________ 
A satisfactory patchouli perfume containing extended patchouli oil is 
thusly provided.