Note: Descriptions are shown in the official language in which they were submitted.
L3~93i~l~6
--3--
1. Field of the Invention
This invention relates to the discovery that certain odor-
less liquid hydrocarbons, specifically: (i) alpha methyl
styrene dimerization products, dimerization products of
methyl or other C2-C4 lower alkyl homologues thereof and
hydrogenated derivatives thereof or (ii) dimerization
~ products of (i) monocyclic terpenes containing two carbon-
; carbon double bonds, (ii) bicyclic terpenes containing
one carbon-carbon double bond and (iii) a monocyclic ter-
pene containing two carbon-carbon double bonds and a bicy-
clic terpene containing one carbon-car~on double bond or
mixtures of same or hycrogenation products thereof or
mixtures of said hydrogenation products and said dimeriza-
tion products may be used as diluents or extenders of
various perfumery materials without appreciable loss of
i l! the characteristic odor effect of such p~rfumery materials.
' 2. Description of the Prior Art
j, .. ... _
; Compounded perfumery compositions contai~ a number of
ingredients which may be of natural or synthetic origin.
The ingredients are blended by the perfumery to create the
desired odor effect. Such essential oils which contain
high percentages of hydrocarbon constituents such as pat-
chouli oil (an essential oil derived from Pogostemon Pat-
chouli) have, for example, warm aromatic spicy odors.When the perfumer wishes to include this type of note for
example in a perfumery composition of an oriental type,
i 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
,1 .
.
'I
. I .
.
~l l
: . . . . .
4 ~ 3~
oil, sandalwood oil, and vetiver oil bv use of b1en~s oE
svnthetic perfumery chemicals, the creation o such oil~
having iclentical aromas with reference to the natural oils
has not been achieved.
In United States Patenk 3,673,120 issued on June 27, 172,
8-camphene carblnol was indicated to be useful as a per-
fumery extender for patchouli oil in DerEumery compositions
when present in a concentration of from 1 to 200 part~ by
weight per 100 parts by weight of the patchouli oil. ~ow-
ever, 8-camphene carbinol has the disadvantage of signifi-
cantly decreasing the aroma s-trenyth oF the patchouli oil
and is not versatile for use with oils other th.an patchouli
oil, for example, vetiver oil and sandalwood oil in the
genus of natural oils, and synthetic oils, for examDle,
geranonitrile and cinnamonitrile.
In United States Patent 2,422,145 issued on June 10, 1947,
water-soluble hydroxy polyoxyethylene ethers of partial
higher fatty acid esters of low molecular weight polyhy-
~! droxylic-compounds were found to form clear extended solu-
¦ tions with essential oils which could be used as such or
I ! which could be diluted with water to form stable dispersions
I or solutions of essential oils. Specifically disclosed are
compositions containing clear, stable solutions of a quan-
tity of an essential oil and at least an equal quantity
I . of such ethers as mannitan monopalmitate hydroxy polyoxy-
, eLhylene ether with abou L 20 ~ ethylene 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. Patent
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.
35 Patent 2,422,145 significantly reduce the strength of the
'" perfumery material when used in conjunction with same.
i.
1,
i~ ' .
. I .
~i
.
3~ '3~;P3~ '~
Cyclohexane dicarboxyl:ic acid diesteLs h~viny th~ str~ct~re-:
~ \ O~
' ~?2?
where Rl and R2 are less than 13 carbon aliphatic Or
alicyelie hydroearbon moieties are disclosed -to be useful
"perfume harmonizing agents" in Japanese Pub]ished Appli~
cation at J 5213692.7 issued on November 15, 1977 to Asahi
Denka Kogyo. However, such materials as these cyclohexane `:
dicarboxylie aeid diesters detract from the strenght of
the perfume material with whieh it is used.
j.20 Proeesses for prepari.ng alpha methyl styrene dimers and
~ methyl homologues thereof are broadly diselosed in the
I : prior art, for example: .
''` . 'i.
. Freneh Patent 1,317,412 assigned to Socony Mobil Oil
Co~pany dated February 8, 1963;
U.S. Patent 3,161,692 issued on Deeember 15, 1964
, ¦ assigned to` Soeony Mobil Oil Company;
. , 1l
.~.: I ,30 Japanese Kokai 78-21149 (February 27,1978, based
on application 76/94045 of August 9, 1976); ~-
, U.S.S.R. Patent 191,511 issued on January 26, 1967;
!!35 u s. Patent 3,523,981 assigned to Olin Corporation, .
issued on August 11, 1970;
I' .
; ' ' , ' ' '.
11
.
- ,
6~ L'f~
Deutsche O~Eenlegungsschrift 2,101,0~9 i,sued on
~ugust 1.0, 1972;
U.S. Patent 3,890,402 assigned to Phil1i?s Petroleurn
Company, issued on June 17, 1975;
Petropoulos and Fisher, J. Am. Chem. Soc. 80,
1938-41 (195~); and
U.S. Patent 4,081,489 issued on March 28, 1978.
U.S. Patent 4,081,489 discloses am improved process for
the production of compounds having the formula:
R ~ ~ { ~ R
! CH3 CH3
. wherein R is independently hydrogen or methvl by contact-
i,20 ing a compound of Formula I:
R ~ C =
where mixture of compounds of Formula I, wherein R is
hydrogen or methyl, with a sulfuric acid catalyst at a
, temperature of 100 to 225C which comprises employing a
catalyst consisting essentially of about 0.05 up to about
: ¦30 3 weight percent based on the weight of the compound or .
mixture of compounds of Formula I, of 90 to 98~ concen- ' .
: ¦ trated sulfuric acid.
: l .
¦ Japanese Kokai 78/21149 discloses the production of unsat-
il35 urated dimers of alpha methyl styrene by contacti~g alpha
methyl styrene with montmorillonite preheated at greater
than 900C for a period of about 6 hours. A1so disclosed
~: ' ' ' '
~$
-7~
in the Japanese Kokai 78/211~9 is the ~lse o~ ;;entonite
as a catalyst.
Nothing in the prior art -teaches the use of alpha meth~1
styrene dimers, methvl homologues thereof or hydrogenate~
derivatives thereor as perfume diluents or as perfume
extenders. Furthermore, nothing in the prior art teac~es
the use of hydrogenated clerivat:ives of such alpha methyl
styrene dimers or methyl homologues -thereof.
In United States Paten-t 3,~15,893 issued on December 10,
1968~'synthetic pine otl, a material ~ell ]cnown -to he use-
ful in the perfumery arts was indica-ted to be s~nthesized
in such a manner that alpha pinene and aqueous sulfuric
acid containing emulsifier were agitated under controlled
temperature conditions until the content of terpene alco-
' hols reached a maximum The oil and aqueous phases, in
U.S. Patent 3,415,893, are then separated and the oil'phase
is washed with water containing basic materials to neutra-
lize any residual acid. The oil phase is then distilledto separate the pine oil product from "unreacted alpha
' pinene and other terpenes, if present as well as from the
by-products of the reaction". It is indicated that the by-
' products are primarily monocyclic hydrocarbons containing
some cineols, cyclic ethers and other undesirable products ;
' of the reaction and that the by-product portion is a use-
! ful solvent. Nothing in ~.S. Patent 3,145,893 discloses
; the usefulness of the diterpene - alpha methyl styrene
¦ dimer mixtures of our invention and the advantages thereof
l30 as extenders in perfumery.
~. . ....
Diterpenes and hydrogenated diterpenes resulting from the
' action of various acids on monoterpenes have been studied '
¦ by various investigators since the discovery over a century
35 ago of dipinene by Deville, Ann. Chim. Phys. (2) 75, 66
(1840) and Ann. Chim. 37, 192 (1840) who obtained dipinene
from te~pentlne oil and sulfur~c ac~d. These e~periments
3~
--8--
of ~eVil]e ~Jere r~vie~7ed as t,~as the litcr~ r~ of svn~'^r-
tic dipinenes in general, ~v 3ulou, Chimie et Inclu,trie,
27 (Special ~lumber) 651 (1932) ~herein comr,ounds havi,ng
the structuLes of dipinene, indicated to be:
i
~ ~ and ~ _
` ~ were stated to be produced ~rom alpha pinene having the
I structure: j ,
'i,20 Di-alpha pinene was also produced by Kuwata, J. Faculty
~ Eng. Tokyo Imp. Univ. 18 117-24 (1929) by the ~ction of
i ~ Japanese acid clay on d-alpha-pinene. In a two-stage
1~ 1 I reaction, Venable, J. Am. Chem. Soc. 45, 728-34 (1923)
i treated alpha pinene with Fullers earth causing it first
~25 to'undergo a molecular rearrangement and then causing a
¦ subsequent polymerization to dipineneO Kuwata, in
, J. Soc. Chem. Ind. Japan 36, Suppl. binding 256-8 (1933)
, (abstracted in Chem. Abstracts 27:3927) discloses the
, treatment of camphene in a benzene solution with Japanese
acid clay yielding dimer. Camphene dimers are also dis-
closed to be produced in Japanese Kokai 73 92,,355 of
November 30, 1973 wherein camphene is passed through a
, , strongly acidic cation exchange resin at one atmosphere
Ii and in vacuo at less than or equal to 130C to produce
- ~ 35 camphene dimers and trimers. Japanese Kokai 73 92,355
(Patent Application No. 27686/72) contains the following
,claim:
.. . .
,1 i.
g ~ 3~
"1'he process to manuEacture oligomer.s ot c~rnph~nk
by the pol~lmerization oE campllene at less than
130C and under atmospheric or reduced r~ressure
with the catalysts of ion e~change resin of
~5 strong acid type."
In addition, Japanese Kokai 73 92,355 also contains th~
` following relevant disclosure:
"By this invention, the produced oligomers are
removed from the reaction system, therefore elimin-
ating the chances of side reactions such as isomer-
ization, hydrolysis, dehydration and oxidation.
The products can be obtained in high yield without
tetramer or higher oligomers, and are colorless
'! and odorless which are suitable for use in fragrances,
, cosmetics and food additives."
i' .
The specific properties of the camphene dimers and their
i 20 utility in the manner described herein as perfumery ex.ten-
ders and diluents are not disclosed in Japanese Kokai
; ~ 1 73 92,355, however.
i The dimer of limonene is indicated to be prepared from
~25 d-limonene by Beilstein V. 509, page 246 (~o. 9). The
presence of the dimer of limonene is indicated to exist
¦ in the essence of Dictamnus Hispanicus in Chem. Abstracts
45:5880 (abstract of "The Essence of Dictamnus ~ispanicus",
J. Sistare (Inst. 'Alonso Barba' Barcelona, Spain) Anales
¦30 Real Soc. Espan. Fis. Ey Quim. 47 B, 171-4 (1951)).
~ " ~
In United States Patent 2,249,112 issued on July 15, 1941,
hydrogenated pinene polymers are indicated to be useful
for their "solubility-viscosity characteristics", making
, 35 them usable as impregnants, adhesive materials, and as a
vehicle for metallic paints. They are also indicated to
be competa~le with many~any mineral oils and can ~e blended
., .
.1 .
i, .
,! -
il i
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.
r3~
--~o--
~ith r-1~ber to produce soft tackv comt~ositions. T~.c
hydrosenated pinene ~olymers ln~licat~d to he so ?roclucecl
in U.S. Patent 2,249,112 are produced accordiny to the
fo1lowing reaction scheme:
lo ~ ~J ~ /r- -~?l
ll ~ .
`
1 2s . ¦ H2
~:, . '.
- ~ ~
, .
an~ stated to have ~he struct~r~s:
~ I a
The hydrogenated terpene polymers o:E 2,249,112 are not
taught to be useful as perfume ex-tenders and are no-t
indicated to have the p.roperti.es in conjunction with
certain per~ume essen-tial oils as is disclosed and clalmed
lS in the instant application.
Perfume extenders have been broadly used as "adulterants"
. in the art of perfumery. Thus, for example, in the text
entitled "The Art of Perfumery and Method of Obtaining
. 20 the Odors of Plants" authored by Piesse (Lindsay and
Blakiston, Publishers, Philadelphia, 1856) turpentine and
i spike oil are indicated to be adulterants for lavender oil.
. on page 255. In Poucher "Perfumes and Cosmetics" I ;
.~.. I Van Nostrand Company 1923 terpene residues obtained during
the manufacture of concentrated lemon oil are indicated
. to be adulterants for lemon oil. In Vol. 1 of "The Essen-
tial Oils", Guenther, Krieger Publishing Company 1975,
Vol. 1 Terpinyl Acetate, and Turpentine Oil (containing
d-alpha pinene) are indicated to be used as adulterants. ¦ i
. 30 In Vol. 2 of "The Essential Oils" camphorene, a "diterpene'l i
! is indicated to be widely applied as fixatives in the
I , sending of soaps. Alpha camphorene has the structure:
. CH~ .
1 11 ~CH3
~12~ ~CH ~113
"2~ ~1 H2 , C ~CH3
,~ ,C~2.
,, 1~2C Cll~
. .
11 1
,
-12~ rv~
U.S. Patent 3,50~,7G9 issued on i~arch 2~, ls70, (ru~uhara)
j discloses a toilet preparation containing a storase-
stabilizing ~mount or a h~idrocarbon which may he a mono-
cyclic hydrogenated terpene polymer of the formula (C~
5 and/or a bi-c~clic hydrogenated terpene polymer of ~he Lor-
mula (CloH17)n where n is a whole number of from 2 to 4
and a cosmetlc ~ase, such as a cold cream or a cleansing
cream base. In column 2 or U.',. Patent 3,502,769 at line
15, it is indicated tha-t the hydrogenated terpenes are
, 10 produced from alicyclic terpene hydroc~r~ons. It is rur-
t ther indicated that, for example, mono-c~clic terpenes
such as menthadienes (e.g., alpha-terpinene, gamma-ter-
pinene, alpha-phellandrene, beta-phellandrene, terpinolene,
; limonene, etc.) and bi-cyclic terpenes such as the cam--
15 phenes are first polymerized to form h~drocarbon compounds
the formula (CloHl6)n~ wherein n is a positive whole
number from 2 to 4. It is further specified that these
i polymers are either dimers, trimers, or tetramers, and that
the resultant polymers are then completely hydrogenated
20 and in the case of the menthadienes, form mono-cyclic
¦ polymers ofthe formula ~CloHlg~n~ wherein n is a whole
¦ number of from ~ to 4, and in the case of the bi-cyclic
i ; , terpenes, it is indicated that there are formed bi-cyclic !
¦ polymers of the formula ~CloH17)n wherein n is a whole
25 number of from 2 to 4. As an example, when using dipen-
, ' tene as the starting material, the following reaction
¦! sequence is stated to take place:
(I ) eH3 . CU~ Cf~3 CH3 ~ll3
30 '~ f~
~¦~C~ ~3~-C-c~-c- CH3 ~ C - ~ ~ I CH3
Di-pentene Dimer Reduced Dimer
~ cl~3 CH~ eH3 ~H3
> ~ '1~) .
C~ C~ ~H~ 3~ HjC CH3
Di-pentene Dimer Reduced Dimer
3~
--13-
Although perfumes are shown to be usable in conjunction
with the hydrogenated terpene polymer materials which are
fur-ther used for the purpose of storage-stabilization,
there is no teaching in U.S, Patent 3,502,769 that, in the
proportions indicated, the mixtures of (i) such terpene
dimerization products as dimerization products of camphene
or of alpha-pinene or beta-pinene and (i.i) alpha-methyl
styrene dimerization products of our invention are useful
in the manner described herein as perEumery extenders and
diluents.
,i
.
!
~
;
~1'1--
Description of the drawincJs:
Figure 1 is the GLC profile ~or the product produced
according to Example I, Fraction 1~.
Figure 2 is the infrared spectrum for the ~roduct produc-
"
ed according to Example I, Fraetion l.9.
Figure 3 is the NMR s~ectrum for the product produced
.
aeeording to Example I, E'raetion 19.
Figure 4 is the GLC profile for the product producedaeeording to Example I~, Fraetion 3.
Figure 5 is the infrared speetrum for the product produe-
ed aecording to Example I~ Fraetion 3 as well as Example
III.
Figure 6 is the NMR speetrum for the produçt produeed
aeeording to Example I, Fraetion 3 as well as the produet
produeed aeeording to Example III.
Figure 7 ls the mass speetrum for the produet produeed I I
aeeording to Example I, Fraetion 3 as well as the produet I
. ~25 produeed aeeording to Example III.
. Figure 8 is the GLC profile for the produet produeed
aeeording to Example III, Fraetions 9-12 wherein a
¦ Filtrol R eatalyst is used as the dimerizing agent.
'. '... 1 30 I '
Fig~re 9 is the GLC profile for the dimerization produet ¦
.; . I
of alpha-pinene produeed aeeording to Example IV~A).
,
Figure 10 is the GLC profile for the dimerization produet
i
, 35 of eamphene proclueed aeeording to Example IV (B) .
Figure 11 is the NMR speetrum for the produet produeed
i
,, .
`
-:l5- '~'r3
according to ~xample IV(A).
! Figure 12 is -the infrared spectrum for the product produc-
ed according to Example IV(A).
Figure 13 is the GLC profile i-or the product produced
according to Example IV(C), the dimerization product of
limonene.
Figure 14 is the NMR spectrum for the product produced
according to Example IV(C), -the dimer of limonene.
Figure 15 is the infrared spectrum Eor the product produc-
I
ed according to Example rv~c~ the dimer of limonene~
' 15
!
l'
.
,
' ` ~` 1, 25
, ~. .
~ ' ` . . . .
1 30
,: ~, ' , ' . `
~, l35
!
!
1' i
`
.
~1 I
Description of the Preferred Embodiments
Surprisingly, it has been found that either (i) in the
alternative; or (ii) mixtures of (A)-d'imerization products
of (i) monocyclic terpenes contalning two carbon-carbon
double bonds, (ii) bicyclic terpenes containing one carbon-
carbon double bond and (iii) a monocyclic terpene con-tain-
ing two carbon-carbon double bonds and a bicyclic terpene
containing one carbon-carbon double bond or mixtures of
same or hydroyenation products thereof or mi~tures of
said hydrogenation products and said dimerizati,on products
and/or (B) alpha methyl styrene dimerization products,
dimerization products of methyl or other C2-C~ lower alkyl
homologues thereof and hydrogenated derivatives thereof
may be used as diluents or extenders of various perfumer~
materials without appreciab]e loss of the characteristlc
odor effect of such perfumery materials.
I' .
ll Dimerization products (A) are produced by dimerizing
',20 such compounds as camphene having the structure:
or alpha pinene having the structure:
,35 or d-limonene having the strueture:
!1
I, .
,
-17~ 3 ~
~
or alpha-phellandrene ha~ing the structure:
~b
/~
or gamma-terpinene having the structure:
¦ or elca 3-carene heving the structure:
3Q
or beta phellandrene having the structure:
,Jl
~r3
.
I, . . . l
,
--18-- ~ A
or beta-terpi.nene havi.ng the s-lructure:
\~
~
or alpha-terpinene having the st.ructure:
lo h
;. ~
.. ,~,
, .
or terpinolene havihg the structure:
21) ~ ~
o eta pinene having the structure: ;
..
:: ~ ~ ;
: or by "dimerizing" mixtures of two or more of such com-
pounds, such as the mi~ture of C10 terpenes commonly known
as "sulfate t.urpentine" or by "dimerizing" a C10 terpene
and a dehydrogenated terpene ~e.g., cymene) in the presence
of acid catalysts, such as sulfuric acid and hydrofluroic
¦ acid or in the presence of acid clay catalysts, such as
. Japanese Acid Clay or Fullers earth or cation exchange
!¦ :
.I j
Il .
:
19-
resin catalysts. The said "dimerization" products are
compouncls having such posslble s-tructure~s as:
~ ~
:' ~< ~
,\~<
and the hydrogenation products t:hereof have such possible
structures as:
Insofar as the dimerization products (A) are concerned,
the terms "dimerization product" and "dimer" are intended
to cover reaction products containing 20 carbon atoms
. resulting from the reaction of a 10 carbon atom terpene
'- compound (monocyclic with two double or bicyclic with
. : . 25 one carbon-carbon double bond) with itself or with another
terpene compound which is monocyclic or bicyclic, without
~: : regard to the number of hydrogen atoms contained in any
molecules or said reaction products.
Dimerization products (B) produced by dimerizing alpha
. methyl styrene having the structure:
`, 1:
Ij
.
il . ' .
i, !
. ' .. . . . ' . ~
'~ ' :. '':' ~ " '
--20 ~ 3!~
or by dimerizing a methyl or other C~-C~ lower alkyl homo-
logue thereof having, for exam~le, the structure:
s
in the presence of Lewis Acid catalysts, Bronstedt acid
catalysts such as f~lfuric acid or in the presence of
acid clay catalysts such as Japanese Acid Clay or Fullers
,_ar~il or cation exchange resin catalysts. The dilrsri.~a-
tion product o.~ alpha methyl styrenP so useful have the
~15 Structures
,, ,
113C S ` ~ '
~ ~5
'¦ R5
. . '.
ii , i
' 1~ . . . 1
~ - . . . ~
:
~ ~21~ 3~
wherein orle of R5 or R5 is methyl or other C2-C4 lower
alkyl and the other of R5 or R5 is hydrogen or each of
; R5 and R5 are the same or different Cl-C4 lower alkyl,
e.g., methyl. Hydrogenation products thereof have the
5 struc-tures:
X~
10' 0 C"
i 'l15
~5
1~' , , , )
,!
.
- 2 2 ~ 3'r7
R5 R5
~> ~> i
R5 \ C) ~/~
R5
. - ;: . R5
., .:
.. .. .
- - 2 5
~ > ~ ~ \
~, , , j~
. R5
: 35 ~ J
, ' '
, ' '
., ~ -.
-23~ 3~
wherein one or both of R5 and T~.5 iS methyl or o-ther
C2-C4 lower al~yl. Such hydrogen~tion products can be
represented bv the generic structures:
10 , ' '~,X\ , 1"
--~ O\
, 4
\ /
"'"_~ ~
20 , I ~ \
: . /\ ~/~
; i R4
;~` 30 wherein R3 and R~ are the same or different and represent
. - hydrogen or methyl or other C2-C4 lower alkyl; wherein
- the dashed lines and wavy line represent carbon-carbon
single bonds or carbon-carbon double bonds with the pro-
viso 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 llne~
- .
,
-24~ ~q~
represents either a carbon-carbon single bond or no :~ond.
In the case of the hydrogenation product, when P~3 and/or
R~ are lower alkyl, for example, methyl, the methvl groups
. mav he in a "cis" or "-trans" relationship to one another
and with respect to the cyclohexyl moieties.
A significant property of the above-said mixtures OL
dimerization products and hydrogenated d;merization pro-
ducts is -tha-t they have a broad range of solubilities for
: 15 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 e~ample, the following materials
are completely miscible with the dimers which are the sub-
ject of our invention~
Phenyl Ethyl Alcohol
Geraniol
;...... Terpineol
Citronellyl Acetate
- Decyl Acetate
- Rose Oxide
n-Decanal
Citral
. 30 Alpha Ionone
.Eugenol
. Galaxolide
2-Methyl-2-Pentenoic Acid
Isobutyl Quinoline
, 35 Lemon Oil
Rosemary Oil
'.
,
,' : , ` :
3~ ~
-25-
Patchouli Oil
Cinnamoni-t:rile~
Geranonitrile
Thus, it has been discovered that the dimers of our
invention can be used as partial replacements for cer-
tain essential oils and synthetic substitutes therefor
in compounded single phase liquid perfumery comnositions.
- 10 Accordingly, the present invention comprises a compounded
single phase liquid perfumery cc~mposition which comprises
one or more synthe-tic perfume oils or natural perfume
oils or mixt7-res of natural perfume oils and synthetic
. perfume oils with which there has been incorporated from
about 1 up to about 30 parts of either (i) in the alterna-
tive or (ii) a mixture of (A) an alpha methyl st~rene or
alpha methyl styrene methyl or other C2-C4 lower alkyl
homologue dimerization product or hydrogenated derivative
thereof or mixture of alpha methyl styrene~or alpha methyl
styrene methyl (or other C2-C4 lower alkyl) homologue
dimerization product and one or more hydrogenated deriva-
tives thereof which have at least one oE -the following
- .; - - structures:
`"' '.'-' ` ~; ' ' -
:
~26~ 43~3~
5 1~
: ` 30 \/
R5 ~1 ~
R5
3~
S R5 ~,~ R5
R~ R5
S ~
R5
' ~. ~. '
~ ~,
: 25
R5
R5
-28~ {~
wherein one or both of ~5 and R5 is meth~l or other
C2-C4 lower al~:yl. (These cornpounds ~eing represented
collectively ~y the generic structures:
; R
.
in -the case of alpha methyl styrene dimerization products
and dimerization products of methyl or other C2-C4 lower
alkyl homologues thereof and the structures~:
', ' , "' ' '
, ~ .
-29
~ ~ ////h/~ -
lS wherein one of R5 and R5 is methyl or other C2-C4 lower
alkyl and the other is hydrogen, or botA ~5 and R5 are
methyl or other C2-C4 lower alkyl in the case of the
hydroyenated 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 linej~
represents either a carbon-carbon single bond or no bond;
:~ ~ and wherein the line + + ~t + -trepresents 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) and (B) a
.. . "dimerization" product of (i) a monocyclic terpene con-
: taining two carbon-carbon double bonds or (ii) a bicyclic
; 35 terpene containing one carbon-carbon double bond or (iii)
: a reaction product of a monocyclic terpene containing two
carbon-carbon double bo-ds and a blcyclic terpene contain-
~: ' ' ' .
,:
r~3 c~
-3q~
ing one carbon-carhon douhle bond ancl,/or h~drogenatecl
derivatives thereo~ per lOn parts of compounded single
phase liquid perfurnery compOsition. S~ecific e~ les
of such dimerization products and hydrogenated deriva-
tives thereof useful in the practice of our invention
are:
Dimerization products of alpha pinene;
Dimerization products of beta pinene;
Dimerization products of camphene;
Dimerization products of d-limonene;
Dimerization products of gamma terpinene;
Dimerization products of alpha phellandrene;
Dirnerization products of ~3-carene;
Dimerization products of beta phellandrene;
Dimerization products of terpinolene;
Mixed dimerization products of alpha phellandrene
and ~3-carene wherein a mixture of the two is
subjected to a dlmerization reaction'
Mixed dimerization products of alpha p~ellandrene
and gamma terpinene;
Mixed dimerization products of gamma terpinene
: and beta phellandrene;
-: . Mixed dimerization products of alpha pinene, beta
:~ ~-.............. pinene and camphene;
~-. Mixed dimerization products of alpha pinene and
. 25 ~3-carene;
Mixed dimerization products of sulfate turpentine;
' Mixed dimerization products of terpinolene and gamma
' terpinene;
I : Hydrogenated derivatives of any of the foregoing : or mixtures thereof.
:~ The dimerization products "A" and/or "B" and/or hydrogen-
ated derivatives thereof taken alone or taken together,
~ . by themselves, contains no odor and each does not by it-
- self impart any alteration of odor to any of the perfum-
e~y materials to which tl-y are added.
31-
The above stated dime~ization products, hydrogenatrd
derivatives thereof and mi;tures thercoE may be pro-
duced according to anv of the ~.nown methods in the
- prior art. Thus, a reaction scheme whereby a dimer-
iza-tion product (B) may be produced useful in our in-
ve~tion and whereby hydrogenated derivatives thereoE
also useful in our invention are produced and ~7hereby
mi~tures of such hydrogenated derivatives and dimeriza--
tion products are produced is exemplified below:
Reaction Scheme ~1:
possible structure;
and.manv ot~er
~ isomers)
.' ~ .
30~
~ possible structure; and
many other isomers)
.
-32- f~
The c~talysts useful in producing the climerization ~ro-
ducts of ten carbon atom containing terpenes o~ our
invention are Lewis acids such as borontrifluoricle, alum-
inum trichlori~e, sronstedt acids sucll as sulfuric ~ci~
and phosphoric acid, ion exchange resin catalysts such as
Amberlyst 15, acid clays such as Fullers earth and
Japanese Acid Clay. Such dimerization reactions will
proceed in the presence of solvents such as cyclohe~ane,
toluene and he~ahydro-1,1,2,3,3-pentamethyl-indane or in
the a~sence of solvents. The temperature of dimerization
may v~ry from 20C up to Z50C. A preferred cata]n~st
system with preferred temperatures range are borontri-
, flouride etherate at 0-100C or Acid Cl.ay at ~0-175C.
Atmospheric pressure may be used in the dimerization
reaction although higher or lower pressures may also be
used without adversely affecting the yield. The weight
, ratio of ten carbon atoms containing,terpene monomer:
catalyst may vary from 1:0.005 up to 1:0.2 with a pre-
ferred weight ratio of 1:0.05 up to 1:0.01.
"Turpentines" including-"sulfate turpentine", a by-product
. of the-Kraft (sulfate) pulping process for producing
:,,.. , . paper are described in a paper by John M. Derfer, entitled:
. . . .
: :: . - 'rTurpentine as a Source of Perfume and Flavor Materials",
. 25 Perfumer and Flavorist International, Vol. 3, No. 1 at
, pages 45-50. The composition of the "turpentines" in-
cluding the above-mentioned "sulfate turpentines" are
, described therein as follows:
.. , , "In all three types of turpentine produced in the
, 30 southern United States (which is the worlds's
~ , . largest producing region), alpha pinene is the most
; abundant constituent, varying from 60% to ~0%
(see Table I). Beta pinene is the second most
abundant constituent in gum and sulfate turpentine,
varying from 25% -to 35% in the former, and 20~ to
25% in the latter. Wood turpentine contains little,
if any, beta pinene. Of the two pinenes, beta
'
-33-
pinene is the moSt versatile chemically.
Gum turpentine contains 5Q~ to 3; of
monocyclic p-menthadienes, commcnl.y re.~erred
to as "~ipentene", the trivl.al name for
dl-limonene,
Takle I - Com~osi~ion of Southern TurDentines (~)
Component Sul.fate Gum Wood
Alpha Pinene 60-70 60-65 75-~0
Beta Pinene 20-25 25-35 0-2
Camphene Trace Trace 4-8
Others 6-12 5-8 15-20
which is the chief component of this p-menthadiene
mixture. Sulfate turpentine contains 6~ to 12%
of this mixture, while wood turpentine contains
somewhat more. Sulfate turpentine contains 5% to
10~ of oxygenated material from which "natural"
pine oil, mostly terpene alcohols, is separated.
- "Natural" pine oil is also produced in the pro-
. cessing of stumpwood to produce wood turpentine.
:: - Caryophyllene, methylchavicol, and anethole also
- .i . occur in small amounts in sulfate turpentine. The
composition of turpentine depends not only on the
: method of isolation, but also on the species and
the geographic location of the trees. For example,
.: . some western turpentines, as well as certain
- foreign turpentines, contain appreciable amounts of.
. 30 3-carene, which finds little other use than as a
solvent".
~: Accordingly, and more specifically, the species of tur-
pentines useful in the practice of.our invention, the ten
carbon containing terpene ingredients of which are capable
of being dimerized to form the dimerization products use-
ful in our invention are as follows:
`` ' .
.
~`" -3~ 3~~
Species of pine .~rom
which Turpentine is Chemical CGmposi~lon
DeriVed _ o~ Tur~entine _ _ _
(1~ Pinus albicaulis ~3-Carene (35~)
Engelmann (White- Other Terenes (10~)
bark pine) . A Sesquiterpene (73)
A Diterpene (30%)
(2) Pinus Aristata dl-andl-fi-Pinene (a6%)
Engélmann (Bristle- A m~ ricyclic Sesqui~er-
cone pine) pene (4~)
(3) Pinus attenuata OVer 95% d-~-Pinene
Lemmon ~Knobcone No ~-Pinene or Camphene
pine)
(4~ Pinus balfouriana dl-and l-~-Pinene (~0%)
. Grev~ and Balif. dl-and l-~-Pinene (2%)
~Foxtail pine) dl-and l-Limonene (2%)
A Tricyclic Sesquiter-
pene (4%)
,' :~ ,' .'. - . ' '. (5~ Pinus banksiana dl-and l-~-Pinene (85%)
Lambert (Jack dl-and l-~-Pinene (10%)
. pine)
: ~6) Pinus caribaea - l-q-Pinene ~61.5%)
i - Morelet (Slash l-~-Pinene (34%~
. 30 pine) Tailings (4.5%)
` ~
,1 ~ (7) Pinus clausa 1-~-Pinene (10%)
I . (Engelmann) Vasey l-Camphene (10%)
I (Sand pine) l-f~-Pinene (75%)
i 35 `
~ ' `
,
,,,
.
.
.
,
-35-
(8) Pinus contorta var. L~ hellandrene
Latifolia Engelmann
(Lodgepole pine)
(9) Pinus coulteri n-Heptane (5%)
(D. Don (Cou]ter l-~-Pinene (30-35~)
pine) l-~-Phellandrene (35-45~)
n-Undecane (10%)
(10) Pinus echinata d-~?-Pinene (85%)
I Miller (Snortleaf l-f-Pinene (11%)
¦ pine) Limonene
(11) Pinus edulis ~-Pinene (70-75~)
Engelmann ,(Pinyon, ~-Pinehe (5%)
Colorado pinyon ~-Cadiene (15-20%)
' pine)
C12~. Pinus flexilis dl- and l-q-Pinene (80%)
James CLimber Albicaulene-A Monocyclic
, pine~ Sesquiterpene (13~)
, . Bicyclic Sesquiterpene
7%~
,: ~ . . , ~ . , ,
~., ~,. .. . :,
: , .. . .
, ~ 25 C131.Pinus glabra l-Limonene
Walter CSpruce pine),
Cl4 1 Pinus lamhertiana . ~ -Pinene (65%)
t ~ ' : , Douglas (Sugar l-~-Pinene' (13%)
:' 30 . pine) Bicyclic Sesquiterpene
, of Cadalene Type (10%)
. ~, .
- Lambertol (Sesquiterpene
lcohol C15 26) ~ %)
'
-36- ~ 3~
(15) Pinus monoph~lla cl~ Pirlene (85~,)
- Torre~ and Fremont l-I.imonene or Dipentene
(Single-leaf pin~on) (4-5~) ,
d-Cadinene (4-6%)
(16) Pinus monticola ~-~-Plnene ~60%
Douglas (Western ~-Pinene (26~)
white pine) n-Undecane (1-2%)
Sesquiterpenes and
perhaps Limonene
(17) Pinus~muricata d-c7-Pinene (98-99%)
- D. Don (Bishop Camphene (less than 1%)
pine)
(18) Pinus palustris d-4-Pinene (65%)
Miller (Longleaf l-,~-Pinene (31.5~)
pine) Tailings (3%)
(19) Pinus ponderosa 1-~-Pinene (50~)
Lawson (Ponderosa 1-l~3-Carene (20%)
pine) 1-Limonene and Dipentene
~ 25%)
':~. ; . d-Cadinene (3%)
Ponderene (less than 1%)
, ~ ' ,
.,-' (20) Pinus ponderosa d-~-Pinene (60-70%)
- var. scopulorum ~g-Pinene (5%)
. " Engelmann (Rocky Lim~nene ~,20.~ 25%)
' , 30 Mountain ponderosa
-''~ ' ~-, , ' pine)
:~:: . '
(21) Pinus radiata dl-~-Pinene (75%)
D. ~on (Monterey l-~-Pinene (22%)
pine)
.
_37_ '~
(22) Pinus resinosa ~(-Pinene
~it. (Red pine)
(Norway pine)
(23~ Pinus rigida var. I.imonene
serotina (Michau~
Loudon (Pond pine)
(24) Pinus strobus dl-~-Pinene (75~)
Linnaeus (Eastern l--l-Pinene (15%)
white pine) Terpene Alcohol.s and
Ketones (4%)
A Tricyclic Sesquiter-
pene (0.3%)
(25) Pinus taeda d-~- Pinene (85%)
Linnaeus (Loblolly l ~-Pinene (12%)
pine)
(26) Pinus tor.reyana l-Limonene (75~)
: Parry (Torrey n-Decylaldehyde (10%)
: .: pine) n-Undecane (5%)
Longifolene (4%)
. Laurylaldehyde (0.2%)
- Heptane and Nonane (less
tha~ 0.1% of each)
.. .... . . .
. (27) Pinus virginiana dl-~-Pinene (90%)
Miller (Virginia l-q-pinene (8%)
- pine)
. ,~ . - . .
(28) Pinus washoensis d-~3-Carene (chiefly,
- Mason and Stoc~well ~-Pinene, Dipentene, A
. Cyclic Sesquiterpene,
. . l-J~-Pinene (if ~3-Carene
content is low)
-, 3~ L~3~
The dimeri.~atlon products "A" of our invention and h~-~ro-
genated derivati~es ma~ be ?roduced according to an~ f
the kno~n methods in the prior art ~nd according to one
of the follo~ing reaction schemes:
Reaction Scheme ~1:
10 ,2 /~ >~ I ~
(minor: cis
, ,, and trans
, isomer mixt,)
Reaction 'Scheme ~2:
2 ~
.
.
. ~ ., 30 Reacti'on Sch'eme ~3:
; 35 ~ ~
' -39-
Reaction Scheme "4:
__ .
, 2,~ >,J~ +~Q~;~
H3C H3C' ~ ~ H C
. 10 (minor: cis
i and trans
¦ isomer mixt~)
R'e'action Scheme #5:. ,.
20 / H~C ~
. CH3
': '''' ':
'~'' '~ ' 25
~,~' . R'e'a'ctio'n'S'cheme,$6:
~ C ~
' 35 ' H3 CH3
~~, , ' .
:
3~
-40-
Reaction Scheme "7:
R3
I 10 ' (Mixtures) (~linor: cis
i and trans
1 isomer mixt,)
' 15 Reaction Scheme ~8:
1 `
~ I .
R3 ~ ~ ~
-. R4
. 25 (~ixtures)
- - .
Reaction Scheme #9:
.
~ 30 ~ "~
: 35
(Mixtule) ~Mixt~re)
,
~` '
,1 1--
Wherein R3 and ~ are the same or (]ifferent and r~present
hyclrogen or methyl or o-ther C2-C4 lower al'~yl and ~,/her~in
the dashed lines, -the wavy lines, an~ the line~ ¦and
the line t ~ I are as defined above.
In this dimerization reaction, the catal~sts tha~ may be
used are Lewis ~cid such as borontriflouride aluminum tri-
chloride or Bronstedt Acids such as sulfuric acid or phos-
- phoric acid or such acids on carriers such as alumina, sil-
ica or cation exchange resin catalysts such as Amberlyst
15, or acid clay catalysts such as Ja~anese Acid Clay or
Fullers earch. 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
15 dimerization ~ay be from about 20C up to about 250C with
a preferred temperature range when using borontriflouride
etherate of 0-100C or when using acid clays of from 80-
200C~ The pressure 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 alpha methyl
styrene methyl homologue:catalyst is from about 1:0.005
up to about 1:0.2 when using an acid clay catalyst and
25 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 nickle catalyst at temperatures of
from about 80C up to about 150C at pressures of from
about four atmospheres up to about thirty atmospheres~
The extended perfumery oils and chemicals of our invention
may be used in compositions where the natural oils Or
.
-42~ 3~3~'~
chemicals ~ould have been usecl, for eYam~le, in com~ina-
tion with sandalwood oil, vetiver oil, oakmoss, ionone,
labdanum, methyl ionone, patchouli oil ancl other svnthe-
tic substitutes therefor.
The eXtended perfumery materials of our invention will
find use as constituents of compounded perfumer~ composi-
tions in which a number oE perfumerv materials of natural
~ and/or synthetic origin will be blended together to produce
! lo a particular desired odor effect. Such compositions may
, , then be used in space sprays or can be blended in soap,
I detergent or deodorant compositons, including bath salts,
i , shampoos, toilet wat2rs, face creams, talcum po~ders,
body lotions, sun cream preparations and shave lotions
, 15 and creams. The perf'umery compositions can also be used
to perfume substrates 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
t. It will be understood that these examples are illus-
, trative and the invention is not to be considered as
restricted thereto except as indicated in the appended
clai~s,
~~ , 25
.~ :
. . ' .
,..
~ 30
.. ,, ~ .
'
,
_
Exam~le I
Prevaration of al~a me hvl styrene cli~er~zation product
Reaction:
10 2 ~ ~> ~J~
~minor: cis and
trans isomer mixt~)
~ Into a two-liter reaction flask equipped with t~ermometer,
reflux condenser~ cooling ~ath, addition funnel, stirrer
and gas ~ub~ler 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 ;s then
rought to 3QC~ Over a period of two hours after the
- ~ sulfuric acid is added~ while maintainlng the temperature
of the reaction mass at 20-33~C~ 500 g of alpha met~yl
styrene is added. After the addition of the alpha methyl
styrene, the reaction mass is maintaIned at a temperature
-of 30C for a period of four hours, 500 g of water is
then added following ~y 250 g of cyclohexane. The reac-
tion mass is then stirred for a period of fifteen minu-tes
and heated to 70C~ The layers are separated and the
I organic layer is- washed neutral ~at 70~C~ wIth a 5% sodium
! hydroxide solution ~two 250 ml volumesl and a 5% sodium
chloride solution (three 250 ml volumesl~ 650 g of crude
, product is recovered and distilled after adding to the
j 35 mixture 15 g of Primol ~ and 0.2 g of ronox ~ through a
12" Yigreaux col~mn as fo1lows:
,
. ,.
.
~ 9
-44-
VaPOr LiaUid ~leight O f;
FraCtiOn Tem~ Tem~, VAC. mm.FraCt;On
____
1 69 101/135 760/760iJO2,2
2 132 1~5 2.3 2.8
3 132 146 2.3 ~6.4
4 132 147 2.3 16.0
132/134148/148 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.~
9 132 150 2.2 24.2
133 150 2.2 29.6
11 133 151 2.5 28.2
15 12 133 151 2.4 25.5
13 133 152 25.0
14 133 152 2.3 23.7
133 155 31.5
16 135 162 2.3 29.4
20 17 137 169 2.3 23.1
~ 18 ~39 176 2.3 12.5
- ~ 19 142 202 13.2
~. ~ , . . .
141 221 2,3 10.3
~;` - 21 - 188 - 230 10.5
25 22 187 242 2.3 8.1
:~ ~
I FigUre 1 SetS fOrth a GLC PrOfi1e fOr FraCtiOn 19~ ThiS
¦ fraCtiOn is Primari1Y the a1Pha methY1 StYrene dimer
¦~- haVing the StrUCtUre:
. ~ ~ ~ (cis and trans
somers)
,~'' ~'': '
' .
, .
.
'J~ 3
-45-
Fi~ure 2 is the infrared spectrum ~or Fraction 19. F'igure
3 is the NMR spec-trum fro Fraction 19. The mass spectrum
for Fraction 19 which is the compound having the structure:
S
~ (cis and trans
. isomers)
' is as follows: - -
. , .
M/E -Re'l'a'tlV`e 'I'n'te~sity
39 235
41 274
,51 ' 18'
'' 77 19
- ' ' ' . . 9 1 4 2 2
1 0 3 1 4 1
~ 119 100
, . 143 20
221 323
236 206
¦ ,~ 30 The GLC profile for Fraction 3 whic~ is primarily the
', ' 1:~ compound having the structure:
~ 35 , ' ~ ,
' .
.
,
- -~6-
is set forth in Figure 4. Figure 5 sets for~h t~e infra-
recl spectrum Eor Fr~ction 3 ~igure 6 sets for~h ~he ~P~
spectrum for Frac-tion 3
Figures 4, 5 and 6 also represent, respecti~ely, the GLC,
IR and NMP~ spectrum for -the procluct produced according
to Example III, infra.
Example II
Preparation of'alpha meth~l stYrene dimerization ~roduct
-- .
' React~ion:
' ' Cminor~ ~major: cis and
' trans isomer
, ,. ~ . .
~ mixture)
1: ~ ,: , .. . .
Into a one-liter reaction flask equipped with khermometer,
addition funnel', heating mantle, reflux condenser, stir,
I Y adapter and distillation head is added 100 g of cyclo-
hexane followed ~y 5 g of p-toluene sulfonic acid. The
resulting mixture ;s heated to 50C and over a one hour
'~ ~ 30 period, 500 g of alpha methyl styrene is added to the
i ~ ~- reaction flask. The'reaction mass is then heated to lOO~C
,
;~' ; - and maintained at that te~perature for a period of four
hours. 529~3 g of crude proauct is then recovered which
is then mixed with 15 f of Primol R and 0.2g of Ionox R
The resulting mixture is distilled through a "Y" adapter
distillation column yielding the follow;ng distillation
data:
, '
.
":
-~7-
Fraction Vapor l.iquid ~7ei~h-t of
Fraction Tem~. Tem~. Vac. mm~Fraction
1 21/8090/149 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
S 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
202 215 2.2 31.3
11 206 215 2.2 27.1
15 12 2].~ - 225 2.2 18.1
13 210 250 2.2 41.6
Exam~le III
Preparation of alpha methyl st~rene dimer
, ~. .' ' '
Reaction:
,... ... . .
5 2~1~
~- 30
.,~ ,~ ;., . ,
1';' ~'' ~ ' ' .
Into a 1,000 ml reaction flask equipped with thermometer,
addition funnel, heating mantle, reElux condenser and
; stirrer is added 20 g of Filtrol 25 ( a 10-20 mesh granular
acid activated clay produced by the Filtrol Corporation of
5959 West Century Boulevard, Los Angeles, California 90045
havi-g the following properties:
.
. ~ . .
.. . . .
. . ~
: :
3~
~48-
Particle size anal~sis }~y Tyler Stanclard Sleve
Throuqh 10 ,lesh, Wt. ~100
Through 20 Mesh, Wt. ~ S
s Free Moisture, ~it. % 10
Free and Combined Moisture, Wt.~ 15 (Max.)
(Loss at 1700F)
Bulk Density, 1~5./cu. ft. 43 0
Particle Density 1.3
Surface Area, N2 absor~ent 2~0-300
(Bet Method) M2/gm
.
50 g of alpha methyl styrene is added to the ~iltrol and
' the reaction mass is heated to 100C~ 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 150C 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 ~rith 12 g Primol ~ and 0.3 g Ionox ~ 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
134 145 1.8 53~5
6 134 146 lo 8 31.0
7 135 147 1 8 49.2
'
':
J.~ 3~ ~
-49~
Con'-t.
Vapor Liquid 'r1eight o~
Fraction Temp, Tem~. V,~c mm. Fraction (gm)
8 135 148 1.8 51.5
9 136 149 I.8 46.2
137 151 l.. ~ 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)
Figure 4 is the GLC profile for Fractions 9-12. Figure 5
is the infrared spectrum for Fractions 9-12. Figure 6 is
the NMR spectrum for Fractions 9-12. Figure 7 is the mass
spectrum for Fraetions 9-12. Figure 8 is a second GLC
profile for Fractions 9-12.
Exam~le IV (A)
Preparation of alpha pinene di.mer
: Reaction:
30 ~ 2
(possible strueture:
and many other isomers)
.
"
~L1~3~6
50 -
Into a two-liter reaction flask equipped with stirrer,
thermometer, a~dition funnel and reflux condenser, are
placedlO0 g of alpha pinene and 40 g of Filtrol 25
(a 10-20 mesh granular acid activated clay produced by
the Filtrol Corporation of 5959 ~est 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.)
(Loss at 1700F)
Bulk Density, lbs./cu. ft.43.0
Particle Density 1.3
Surface Area, N2 absorbent280-300
(Bet Method M /gm)
The reaction mass is heated to 150C with stirring and
an additional 900 g of alpha pinene is added thereto over
a period of two hours while maintaining the reaction mass
at 150C. The reaction mass is then continued -to be
stirred at 150C until GLC analysis of sampler shows that
the reaction is complete (whereby little or no alpha pinene
remains~.
The reaction mass is then cooled to 80C and filtered
using filter cell.
The filtrate is distilled at 3 mm Hg. vacuum using a 12--
Goodloe column and starting at a 9:1 reflux ratio and then
'. .,
going to 4:1, Just prior to distillation, 30 g OL- Pri~ol P
is added -to the material to be distilled. The distilla-
tion data are as follows:
Vapro Liquid Reflux Weight of
Fraction Tem~, Temn. Vac, mm. Ratio_ Fraction
1 35/75 72/11550/359:1/9:1 44,1
2 39 95 3,0 9:1 53.q
3 41 ' 103 3.0 9:1 46,0
4 41 165 3.0 4:1 68,7
31/128 152/1681,0/,8 4:1/4:1 38,0
6 133 175 0,8 4:1 43.0
7 133 179 0,8 4:1 51,1
8 133 - 180 0,8 4:1 49.4
9 133 181 0,8 4:1 44.5
133 185 0,8 4:1 49.5
11 133 187 0,8 4:1 47.5
12 136 193 0,8 4:1 42.7
13 140 204 0.8 4:1 44,5
Figure 9 is the GLC profile for the alpha pinene dimer
- (fractions 9-llL~ ~Conditions: 2% Car~owax Column,
. " . .
, ;. ",,, . 25' X ~" programmed at 80-220C at 10C per minute),
- 25 ~
Figure 11 is the NMR spectrum for the product of Example
IV (A~, Figure 12 is the IR spectrum for the product of
Example IV CA).
. , . - .
,.. : . .. : .' , : .
~ :.
:
-52- ~~
Example IV (~)
Dimers of Cam~hene
Into a two-li-ter reac-tion flask equipped ~ith stir,
thermometer, addition funnel and reflux condenser l~ith
Bidwell Trap are placed:
Hexahydropentamethylindane 336 g
Filtrol 25 (Properties set 32 g
forth in Example I (A))
with stirring the mixture is heated to 155C. Over a
period of 2.25 hours while maintaining the reaction mass
at 155C, 547 g of Camphene is added thereto. The reac-
tion mass is then stirred for 7~ hours at 115/158C and
progress of dimerization is monitored on GLC apparatus
(Conditions: 5% SE 30 column, 10' X ~", pr4grammed at
20 80-240C at 8C per minute). GLC analysis shows very
little change after 2 hours. The reaction mass is then
filtered. The filter cake is washed with 200 g of
hexahydropentamethylindane. The weight of filtrate is
1056 grams.
The resultant filtrate is distilled in the presence of
Primol ~ (30 g~ and Ionox ~ (1 g) through an 18" Vigreux
column equipped with reflux head~ The following distilla-
- tion data is ohtained:
: 30
..
: Fract. Vapor Pot Pressure Weight of GLC Analysis
,' Num. Temp. Temp. mm Hg. Fr. (g.) o~ Fraction
1-6 45-100 87-160 2.6631.9 Recovered hexa-
hydropenta-
methylindane
7 149 170 3.5 10.5 ¦ Intermediate
I Section
-53
Con't.
Fract. Vapor Pot Pressu Weigh-t of GLC Analt~siS
Numb. Tem~. TemP. mm. H~. Er, (c-.) of Eraction
150 1 170 1, 2.8 1~40.7 jPracticall~
~ pure Dimers
9-11 152-168 1176_230 2.5 '214.8 Dimers
l I
~ 12 215 275 1 2.5 1 22.9 1
. j ~
13-14 225-250 290-306l 2.5 162.7 Very I,ittle
_ Eluted on GLC
-Residue - 41.7
Trap - 18.0
Figure 10 sets forth the GLC pro~ile for fractions 9-11,
the camphene dimer ~Conditions: 5% SE 30 co,lumn, 10' X ~",
20 programmed at 80-240C at 8C per minute).
'
' - The structure of the hexahydropentamentylindane, used as
'' ' a solvent is as follows:
' ~
' ' l 1 ~--
X
' Example IV _(C)
~ :
, - 30 Preparation of d-Limonene Dimer
.~, . .
,~ ~ Into a 500 ml reaction flask equipped with thermometer, stirrer, condenser and addition funnel are placed 5 g
i Primol ~3 and 2 g Filtrol 25. The reaction mixture is
35 heated to 150C and 40 g of limonene is added dropwise
over a periocl of 80 minutes. The reaction mass is then
heated et 1-0C for 3 hours.
:
"
-54~ 3r~
Tlie reaction mass is then cooled, filtered and disti.l]ed.
The resultincJ product is the dimer of cl limonene, confirm-
ed by GLC, N~IR and I~ analyses,
The GLC proflle is set fo~th in Figure 13, The NMP
spectrum is set forth in ~igure 1~ The IR spectrum is
set forth in Eigure 15.
E~am~l'e V
Patchouli oil. C80 parts) obtained from the Seychelle
Islands is blended with 10 parts of the alpha methyl
styrene dimer produced according to any one of Examples
I, II or III and 10 parts of the alpha pinene oE
Example IV ~A), The alpha methyl styrene dimer - alpha
pinene dimer mixture is found to act as an e~tender for
the patchouli oil in that the characteristic odor effect
of the latteF is substantially not modified.
Exam~l~e VI
.
. The extended patchouli oil prepared according to Example V
is successfully incorporated into a compounded composition
' of the Chypre type ~y blending the following ingredients:
:,; ' . 25
.,. ~ .~ Parts
.'
Cinnamic Aldehyde
. Ethyl Methyl Phenyl Glycidate
~:~ 30 Methyl Nonyl Ace.taldeh'yde' 2
, :~' , 'Oakmoss CAbsolute). 20
'. ' Sandalwood Oil CEast Indianl 20
Yetiveryl Acetate 20
Ylang Oil No. 1 20
senzoin Resoin ~Sumatra) 30
Alpha Ionone ~100~) 30
-55~ 3~
Glove Stem Oil (Zanzi~ar)36
~ergamot Oil 4C
~vdroxycitronellal ~o
Iso Eugenol 40
Extended Patchouli Oil (Ex. V~ 40
Coumarin 50
Musk Ketone 50
Amyl Salicylate 60
Cedarwood Oil (American)60
Citronellol 60
Benzyl Acetate 80
Phenyl Ethyl Alcohol 150
Terpinyl Ace-tate 150
.' 1000
Example VII
A patchouli oil extender hase is prepared ~y ~lendlng
the following ingredients:
~ Parts
- Mixture of 10 parts of alpha 3S
- me*hyl s-tyrene dimer produced
-: - 25 according to any one of Examples
~ I~ II or III and 28 parts of
: d-limonene dimer produced
: according to Example IV Ccl
. : .
Galaxolide 27
Isolongifolene Oxidate 20
Omega-Hydroxymethyl Longifolene 10
Cedrol 3
Sandalwood Oil (East Indian~ 2
100
- 5 6 ~
This mixture t46 parts) is th~n ~len(1ed ~ith nat~ral
patchouli oil (Seychelles) (60 parts) -to provide a
satisfactory extendecl patchouli oil.
Exam~le VIII
The extended patchouli oil prepared in Example VII is
incorporated into a compounded perfumery composition
of the Fougere type containing the follo~Jing ingredients:
Parts
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 ~0
Amyl Salicylate 60
Methyl Ionone 70
. Cedarwood Oil cAmerican) 80
25. Clove Stem Oil (Zanzibar) 80
Vetivert Oil (Bourbon)80
: Extended Patchouli Oil130
Lavandin Oil 140
. 1000
. .
. . Example IX
;' . ' .
Patchouli oil C8s parts) obtained from the Seychelle
Islands is blended with the 10 parts by weight camphene
dimer produced according to Example IV (B~ and 5 parts
of the alpha methyl styrenè dimer of Example II. The
camphene dimer - alpha methyl styrene dimer mixture is
_57~ 3,~
~ found to act ~s an exten-,ler for the patchouli oil in
that the characteristic odor effect oE the latter is
substantially not modified,
E~ample X
- The extended patchouli oil prepared according -to Example IX is successfully incorporated Into a compounded compo-
sition of the Chypre type by blending the following ingre-
dients:
P~rts
Cinnamic Aldehyde
Ethyl ~ethyl Phenyl Glycidate
Methyl Nonyl Acetaldehyde 2
Oakmoss (A~solutel 20
Sandalwood Oil ~East Indian~ 20
~etiveryl Acetate 20
?o Ylang Oil No. 1 20
Benzoln Resoin (Sumat.ra). 30
' Alpha Ionone Cl OO % 13 o
-' ''' .: : ' Clove Stem Oil CZanzi~arl 36
.' '':,'~ - Bergamot Oil ~ 40
, 25 . Hydroxycitronellal 40
Iso Eugenol 40
' Extended Patchouli Oil ~Ex. rx~, 40
, Coumarin 50
Musk Ketone 5 a
30 ~ Amyl Salicylate 60
~ - . Cedarwood Oil (Americanl, 60
:-' Citronellol 60
Benzyl Acetate 80
Phenyl Ethyl Alcohol 150
Terpinyl Acetate 150
1000
-58-
'~f~3~v~
EIY~m~le XI
-
Patchouli oil (80 parts) obtained Erom the Se~cheile
Islands is blended with the alpha pinene dimer produced
S according to ~xample IV (~) (20 ~arts). The alpha
pinene dimer is found to act as an extender for the
patchouli oil in that the characteristic odor effect
of the latter is substantially not modified.
Example XII
The extended patchouli oil prepared according to
Example XI i9 successfully incorporated into a compounded
composition of the Chypre type by blendlng the following
ingredients:
, .
Parts
Cinnamic Aldehyde
Ethyl Methyl Phenyl Glycidate
Methyl Nonyl Acetaldehyde 2
Oakmoss (Absolute) 20
Sandalwood Oil (East Indian) 20
- , Vetiveryl Acetate 20
:`- Ylang Oil No. 1 20
Benzoin Resoin (Sumatra) 30
Alpha Ionone (100%) 30
Clove Stem Oil (Zanzibar) 36
Bergamot Oil 40
Hydroxycitronellal 40
Iso Eugenol 40
, Extended Patchouli Oil (Ex. II) 40
Coumarin 50
Musk Ketone 50
Amyl Salicylate 60
Cedarwood Oil (American) 60
Citronellol 60
Benzyl Acetate 80
Phenyl Ethyl Alcohol 150
Terpinyl Acetate ~ 150
1000
-59 ~ 3~E;
E~am~l.e ~
A patchouli oil extender base is prepared ~y ~lendiny
the following ingredients:
Parts
Alpha Pinene Dimer produced 38
according to Example IV ~A)
Guaioxide 27
Isolongifolene Oxidate 2n
15 Omega-hydroxymethyl.longifolene 10
.
Cedrol 3
.
Sandalwood Oil (East Indian) 2
100
This mixture (46 parts) is then blended with natural
- - . patchouli oil (Seychelles) (60 parts) to provide a
. . .
: satisfactory extended patchouli oil.
: 25
Example XIV.
,
The extended patchouli oil prepared in Example XIII is
incorporated into a compounded perfumery composition of
the Fougere type containing the following ingredients:
., . Parts
Balsam Peru 30
3~ Labdanum Resin 30
Oakmoss Absolute 30
: Sandalwood Oil (East Indian) 30
-60- ,~
Linalyl Acetate 4 n
Terpinyl Ac~tate 40
Geranium Oil (sourbon) 50
Musk Ambrette 50
Coumarin 60
Amyl Salicylate 60
Methyl Ionone 70
Cedarwood Oil (American) ~0
Clove Stem Oil (Zanzibar) ~0
Vetivert Oil (Bourbon) 80
Extended Patchouli Oil 130
Lavandin Oil 140
1 0 0 0
~ 15 Example XV
_ _ r_ _
Patchouli oil (85 parts) obtained from the Seychelle
Islands is blended with the camphene dimer produced
according to Example IV (B) (15 parts). The camphene
dimer is found to act as an extender for the patchouli
oil in that the characteristic odor eEfect oE the latter
-. is substantially not modified.
. ., .,, . - . . . .
~ . Example XVI
.. ;,. . . . .
~- The extended patchouli oil prepared according to Example XV
is successfully incorporated into a compounded composition
of the Chypre type by blending the following ingredients:
~' ' . . . .
~ Parts
. . ~ , .
~- :. Cinnamic Aldehyde
Ethyl Methyl Phenyl Glycidate
- Methyl Nonyl Acetaldehyde 2
OakmoSs (Absolute) 20
Sandalwood Oil (East Indian) 20
: Vetiveryl Acetate 20
- - -61~ 3~
Ylany Oil No. 1 20
Benzoin Resin (Sumatra) 30
Alpha Ionone (100%) 30
Clove Stem Oil (Zanzi~ar)36
Bergamot Oil 40
Hydroxycitronellal 40
Iso Eugenol 40
Extended Patchouli Oil (Ex~ YI) 40
Coumarin . 50
Musk Ketone 50
Amyl Salicylate 60
Cedarwood Oil cAmerican)60
Citronellol 60
Benzyl Acetate 80
Phenyl Ethyl Alcohol 150
Terpinyl Acetate 150
1000
Exam~le XVII
.
A patchouli oil extender base is prepared ~y ~lending
the following ingredients:
., ,: . .
~ Parts
,: : 25
: . Camphene D~ner produced according 38
to Example rY ~BL
- Guaioxide 27
. - ~ 30
. Isolongifolene Oxidate 20
. ,: . :- .: -
.
Omega-hydroxymethyl longifolene 10
: 35 ~ Cedrol 3
.
Sandalwood Oil (East Indian)2
100
,
-62~ r~
This mi~ture (46 pa~ts) is then blencled ~ith natura].
patchouli oil (Seychelles) (f,0 part.s) to provide a sa~is~
Eactory extended patchouli oil.
Exam~le XVIII
The extended patchouli oil prepared according to E~ample
XVIII is incorporated i.nto a compounded perfllmery compo-
sition of the Fougere type containing the follo~liny in-
gredients:
Parts
Balsam Peru 30
Labdanum Resin ~ 30
Oakmoss A~solute 30
Sandalwood Oil (East Indian~ 30
Linalyl Acetate 40
Terpinyl Acetate 40
Geranium Oil ~Bourbon) 50
Musk Ambrette 50
Coumarin 60
Amyl Salicylate 6 a
~-; Methyl ronone - 70
; 25 Cedarwood Oil (American) 80
Clove Stem Oil ~,anzi~arl 80
~eti~ert Oil (Bour~on~ 80
. .
Extended Patchouli Oil 130
La~andin Oil 1`40
~ 1000
Example XX
.
The extended patchouli oil prepared according to
; 35 Example XIX is successfully incorporated into a com-
pounded composition of the Chypre type ~y blending
the following ingredients:
-63~
P. arts
Cinnamic Aldehyde
Ethyl rlethyl Phenyl Gl~,rcidate
Methyl Nonyl Acetaldeh~de 2
Oakmoss (Absolute) 20
Sandal~ood Oil (East Indian~ 20
Vetiveryl Acetate 20
Ylang Oil No. 1 20
Benzoin Resin (Sumatra)30
Alpha Ionone (100%) 30
Clove Stem O.il (Zanzibar) 36
Beryamot Oil 40.
Hydroxycitronellal 40
Iso Eugenol , ................... 40
Extended Patchouli Oil (Ex. XI) 40
coumarin 50
! Musk Ketone 50
Amyl Salicylate 60
Cedarwood Oil (American)60
Citronellol 60
. 20 Benzyl Acetate 30
Phenyl Ethyl Alcohol 150
Terpinyl Acetate 150
1 0 0 0
,~ .- .
, 25 Example ~XI
i , . - , .
-~ A patchouli oil extender base is prepared by blending
` . ~ the following ingredients:
~, .,,,", . . .
. ~ 30 . Parts
d-Limonene Dimer produced 38
according to Example IV(C~
Guaioxide 27
Isolongifolene Oxidate 20
, . . . .
64~
mega-hydroxymethyl longifolene 10
Cedrol
Sandalwood Oil (East Indian) 2
100
S
This mixture (46 parts) is then blended with natural
patchouli oil (Seychelles) (60 parts) to provide a
satisfactory extended patchouli oil.
Example XXII
The extended patchouli oil prepared according to Example
XVII is incorporated into a compounded perfumery composi-
tion of the Fougere type containing the following ingre-
dients:
~ Parts
Balsam Peru 30
. 20 Labdanum Resin 30
.: Oakmoss Absolute . 30
. . Sandalwood Oil ~East Indian) 30
Linalyl Acetate 40
; Terpinyl Acetate 40
25 - Geranium Oil IBourbon~ 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
. Lavandin Oil 140
1000
3v~
E~am~le XXIII
__.
Pre~arati.on oE dimerlza-tion ~roclucts from ulCa~
tur~entine
Into a 500 ml reaction flask equi.~ed with ther~.or.e-er
stirrer, condenser and addition funnel are ~].aced 5 g
Primol R and 2 g of a 20~ phosphoric acid on silica
catalyst produced by the Chemtron Corporation. The
reaction mass is hea.ted to 150~ and 50 g of sulrate
turpentine is added drop~ise over a period of 2 hours
with stirring. The reaction mass is then heated for
another 2 hours at 150C.
The reaction mass is then cooled and filtered and the
resulting dimerization product is a mixture of compounds
containing unreacted terpene monomers. The unreacted
terpene monomers are distilled and again dimerized using
a borontriflouride etherate catalyst. The resulting
dimerization products are then combined and distilled
and used in the following examples.
: , ,: . . .
~ Ex-amp-le XXIV
: .- - ~: -- -
. 25 ~etiver Oil ~70 parts~. obtained from Haiti is blended with
; ~ : the dimerization product produced according to Example XXIII.
The thus formed dimerization product is found to act as
an extender for the vetiver oil in that the characteristic
. odor effect of the latter is substantially not modified.
-. ...~..~: ~ Example~XXV
' . . ' ,' '' ' ' '
- Sandalwood oil ~75 parts~ obtained from Indonesia is
- blended with the dimerization product produced according
to Example XXIII (25 parts~. The dimerization product
thus produced is found td act as an extender for the san-
dalwood oil and that the characteristic odor effect of the
a3~
latter is substantially not modified.
Example XXVI
Patchouli oil (80 parts) obtained ~rom the Seychelle
Islands is blended with the alpha methyl styrene dimer-
ization product produced accordi:ng to Example I, II or
III (20 parts). The alpha methyl styrene dimerization
product is ound to act as an extender for the patchouli
oil in that the characteristic odor ef~ect of the latter
is substantially not modified.
Example XXVII
The extended patchouli oil prepared according to Example
XXVI is successfully incorporated into ~ compounded compo-
sition of the Chypre type by blending the followi~lg in-
gredients:
Parts
Cinnamic Aldehyde
Ethyl Methyl Phenyl Glycidate
Methyl Nonyl Acetaldehyde 2
Oakmoss (Absolute) 20
Sandalwood Oil (East Indian) 20
Vetiveryl Acetate 20
Ylang Oil No. 1 20
Benzoin Resin (Sumatra) 30
Alpha Ionone (100%) 30
Clove Stem Oil (Zanzibar)36
Bergamot Oil 40
Hydroxycitronellal 40
Iso Eugenol 40
Extended Patchouli Oil (Ex. XXVI) 40
Coumarin 50
Musk Ketone 50
-67~
~myl Salicyl.ate hO
Cedarwood Oil (~rnerican)~,0
Citronellol 60
Benzyl Ace-tate ~0
Phenyl Ethyl Alcohol 150
Terpinyl Acetate 150
! looo
!
Example XXVIII
A patchouli oil extender ~ase is prepared ~y blendi.ng the
following ingredients:
Parts
Dimerization product of alpha 38
methyl styrene ~produced according
to Example I, II or III)
,
Galaxolide 27
~ Isolongifolene Oxidate 20
- . :Omega-Hydroxymethyl Longifolene 10
Cedrol 3
Sandalwood Oil ~East Indian)......... 2
! `: ; 25 lOO
~: .
This mixture (46 parts) is then blended with natural
' :~ patchouli oil ~Seychelles) (60 parts) to provide a
satisfactory extended patchouli oil~
Examp'le X~
The extended patchouli oil prepared in Example XXVIII
. is incorporated into a compounded perfumery composition
~: 35 of the Fougere type containing the following ingredients:
.
- .
-
-68~
Parts
Balsam Peru 30
Labdanum ~esin 30
Oakmoss Absolute 30
Sandalwood Oil (East Indian) 30
' Linalyl Acetate 40
:I Terpinyl Acetate 40
Geranium~Oil (Bourbon)50
Musk Ambrette : 50
Coumarin 60
Amyl Salicylate G0
Methyl Ionone 70
Cedarwood Oil (American) 80
CloVe Stem Oil ,(Zanzibar) 80
Vetivert Oil (Bourbon)80
Extended Patchouli Oil130
Lavandin Oil 140
1000
20.
. ~ ' - .
.. . ..
~ '' ' '' ` ."'" ' . ' ' .
.~ ' , . . . . .
~': ,. - , : ' . .
~ . . ,
.. .~-: : - .
~ .
.. . . . .
: -69-
* * * * *
The perfumed materials used in the present invention
in addi-tion to their use in augmenting or enhancing the
aroma of perfumed rnaterial.s, colognes and perfumed art-
icles will also have improved the deodorizing properties
,5 of such a consumable material when present in appropriate
quantities.
.
; .. ..
. ,~ .; i i , . ,
~f,,', '.`'`~ '',: , '
';''"' ~ ,,' '
;~ 25
, , '. ' ' '
,, ,i .
, :~ i; 30
, ~ - - .
:
:
, ' ' ~' ~
