CA1109398A - PERFUME WITH DIMERIZATION OF .alpha.-METHYL STYRENES AND STYRENES - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

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 a mixture of (A) a dimerization product of an alpha methyl styrene or a methyl or other C2-C4 lower alkyl homologue thereof or mixture of same and (B) one or more "dimerization"
(or "coupling") products of one or more terpenes which are monocyclic and have two carbon-carbon double bonds or which are bicyclic and have one carbon-carbon double bond or one or more hydrogenated derivatives thereof or mixtures of same.

Description

1. Field of the Invent.ion This invention relates to the discovery that certain o~or-less liquid hydrocarbons, specifically: (i) alpha meth sty~ene dimerization products, dimeri~ation products of methyl or other C2-C~ 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 monocyc.lic ter-pene containing two carbon-carbon double bonds and a bi,cy-clic terpene containing one carbon-carbon double bond or mixtures of same or hy2rogenation 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 the characteristic odor effect of such p~rfumery materials.

2, Description Oe the P.rior Art i . - _ Compounded perfumery compositions contain 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 contai.n high percentages of hydrocarbon constituents such as pat-.
chouli oil (an essential oil derived from Pogostemon Pa~-. 25 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, ' 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, ttempts have been m~de to simulate the odor of patchouli ' l! I
!l~i ., .

oil, sandalwood oil, and vetlver oil bv use of blends oE
svnthetic perfumery chemicals, t}-e creation oI .such oils having identical aromas with reference to the natural oils has not been achleved.
In United States Pa-tent 3,673,120 issued on June 27, 1972, 8-camphene carbinol was indicated to be useful as a per-fumery extender for patchouli oil in perfumery compositions when present i.n a concentration of from 1 to 200 parts by weight per 100 parts by weight of khe patchouli o~l. How-~ ever, 8-camphene carbinol has the disadvantage of signifi-cantly 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.
", I
In IJnited States Patent 2,422,145 issued on June 10, 1947, water-soluble hydroxy polyo~yethylene ethers of partial ' 20 higher fatty acld esters of low molecular weight polyhy-i~ droxylic compounds were found to form clear extended solu-¦ tions with essential oils which could be used as such or 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 of such ethers as mannitan monopalmitate hydroxy polyoxy- ;
, ethylene ether with about ~0 ^x-~ethylene units per mole with such solution being capable, upon dilution with wate~, of forming a clear, stable aqueous dispersion of essential oil and hydroxy polyoxyethylene ether. U.S. Patent 2,422,145, however, does not disclos~ the formation of solutions of essential oil in organic solvents which are immiscible with water. Furthermore, the ethers of U.S.
j35 Patent 2,422,145 significantly reduce the strength of the il perfumery material when used in conjunction with same.
"

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3q~

Cyclohexane dicarboxylic acid diesters hclving the structure:
O
C/~/
~ \

C ~
\OR,z where Rl and R2 are less than 13 carbon aliphatic or alieyelic hydrocarbon moieties are disclosed to be useful "perfume harmonizing agents" in Japanese Published Appli~
:15 eation at J 5213692,7 issued on November 15, 1977 to Asahi ', Denka Kogyo. However~ such materials as these eyclohexane diearboxylic acid diesters detraet from the strenght of ',` the perfume material with which it is'used.

¦'20 Pr~cesses for preparing alpha methyl styrene dimers and methyl homologues thereof are broadly diselosed in the ,~
," ,~",. prior art, for example: `.

".............. French Patent 1,317,412 assigned to Socony Mobil Oil Company dated February 8, 1963;
,.
¦ U.S. Patent 3,161,692 issued on Deeember 15, 1964 ¦ , assigned to' Soeony Mobil Oil Company;
.
.. ~30 Japanese Kokal 78-21149 (February 27,1978, based ::~ ! on application 76/94045 of August 9, 1976);
I ' 1, ,U.S.S.R~ Patent 191,511 issued on January 26, 1967;

~3S 'U.S. Patent 3,523,981 assigned to Olin eorporation, ¦¦ issued on August 11, 1975;

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Deutsche Offenlegullysschrift 2,101,089 issued on August 10 t 1972;

U.S. Paten-t 3,890,402 assi~ned to Phillips ~etroleum Company, issued on June 17, 1975;

Petropoulos and Fisher, J. Am. Chem. Soc. 30, 1938-41 ~1958); 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:

B O

, CH3 C~
¦ wherein R is independently hydrogen or methyl ky contact-l,~20 ing a compound of Formula I:
I ,1 .

(I) R ~ C = ~H2 I where mixture of compounds of Formula I, wherein ~ is hydrogen or methyl, with a sulfuric acid catalys~ at a , temperature of 100 to 225C which comprises employing a -¦ catalyst consisting essentially of about 0.05 up to about 13 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.
.
Jap~nese Kokai 78/21149 discloses the production of unsat- j 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. Also disclosed Il . . ' !1l .i ., .
1. 1 .

3~
~7--in the Japanese Kokai 78/21149 is the use of ~-entonite as a catalyst.

Nothing in the prior art teaches the use of alpha methy~ ¦
st~rene dimers, me-thyl homologues thereof or hydrogenated derivatives thereof as perfume diluents or as ~erfume extenders. Furthermore, nothing in -the prior art teac~es the use of hydrogenated derivatives of such alpha methyl styrene dimers or methyl homologues thereof~
In United States Patent 3,415,893 issued on December 10, 1968, synthetic pine oil`, a material well known to be use-- Eul in the perfumery arts was indicated to be synthesized in such a manner that alpha pinene and aqueous sulfuric ; 15 acid containing emulsifier were agitated under controlled l temperature conditions until the content of terpene alco~
i 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 distilled to 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 I of the reaction and that the by-product portion ls a use-I ful solvent. Nothing in U.S. Patent 3,145,8g3 discloses ; the usefulness of the diterpene - alpha methyl styrene i dimer mixtures of our invention and the advantages thereof as extenders in perfumery.
i , .
! Diterpenes and hydrogenated diterpenes resulting from the action of var~ous acids on monoterpenes have been studied by various investigators since the discovery over a century -1 35 ago of dipinene by Deville, Ann. Chim. Phys. ~2) 75, 66 ; ~ (1840) and Ann. Chim. 37, 192 (1840) who obtained dipinene from terpentine oil and sulfuric acid. These experiments ~, , . i 1. 1 of ~eville w~re reviewed as ~as the litc~turc of ~,vn~
tic dipinenes in gen~r~1, hv Dulou, C~limie et In~lu~trie, 27 (Special ~Tumber) 651 (lq32) ~herein compounds haviny the structures of dipinene, indicated to be:

~ and were sta-ted to be produced ~rom alpha pinene having the structure:
~. ~

''20 Di-alpha pinene was also produced by Kuwata, J. Faculty _ I Eng. Tokyo Imp. Uffiv. 18 117-24 (1929) by the action of ¦ Japanese acid clay on d-alpha-pinene. In a two-stage II reaction, Venable, J. Am. Chem. Soc. 45, 728-34 (1923) 1 treated alpha pinene with Fullers earth causing it first ¦25 to undergo a molecular rearrangement and then causing a subsequent polymerization to dipinene. 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-~ j closed to be produced in Japanese Ko]cai 73 92,355 of ; 3 November 30, 1973 wherein camphene is passed through a I strongly acidic cation exchanye resin at one atmosphere - ! and in vacuo at less than or equal to 130C to produce camphene dimers and trimers. Japanese Kokai 73 92,355 ~ (Patent Application No. 27686/72) contains the following ; claim:
' ' 1.

- . :
' :
:

9 ~ 3~i ~
I

"The process to manufacture oligomer.s o~ c~mphene by the pol~merizat.ion o~ camphene at less than 130C and under a-tmospheric or reduced pressure with the catalysts of ion e~change resin of ~5 strong acid type."

In addition, Japanese Kokai 73 92,355 also contains the ` following relevant disclosure:

10 "By this invention, the produced oligomers are removed ~rom the reactlon 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 15 tetramer or higher oligomers, and are colorless and odorless which are suitable for use in fragrances, . cosmetics and food additives."
i .
I The specific properties of the camphene dimers and their . 20 utility in the manner described herein as perfumery exten-ders and diluents are not disclosed in Japanese Kokai . i 73 92,355, however.

.~ ~ 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. ~bstracts 45:5880 (abstract of "The Essence of Dictamnus Hispanicus",;
; J. Sistare (InstO IAlonso Barba' Barcelona, Spain) Anales . .. : 130 Real Soc. Espan. Fis. Ey. Quim. 47 B, 171-4 (1951)).
~ ''' ' I`
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 competable with many many mineral oils and can be blended , ~ .
.

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lo~ 3 ~

~ith rubber -to nroduce soEt tackv com~os:itions. The hydrosenated pinene ~olyme.rs indlcated to he so produced in U.S. Patent 2,249,112 are produced according to the following reaction scheme:

~Z
ii~ ' , ~

'25 ~2 1, an~ statecl to have the structures:

~ - ~ and ¦

- The hydrogenated terpene polymers of 2,249,112 are not taught to be useful as perfume extenders and are not indicated to have the properties in conjunction with certain perfume essential oils as is disclosed and claimed in the instant application.

Perfume extenders have been broadly used as l'adultera~ts"
i in the art of perfumery. Thus, for example, in the text ! entitled "The Art of Perfumery and Method of Obtaining the Odors of Plants" authored by Piesse (Lindsay and Blakiston, Publishers, Philadelphia, 1856) turpentine and spike oil are indicated to be adulterants for lavender oil ¦ on page 255o In Poucher "Perfumes and Cosmetics"
,. , . 1, Van Nostrand Company 1923 terpene residues obtained during the manufacture of concentrated lemon oil-are indicated ~ to be adulterants for lemon oil. In Vol. l of "The Essen- ¦ tial Oils", Guenther, Krieger Publishing company 1975, Vol. l Terpinyl Acetate, and Turpentine Oil (containing d-alpha pinene) are indicated to be used as adulterants.
In Vol. 2 of "The Essential Oils" camphorene, a "diterpene'~
! is indicated to be widely applied as fixatives in the j sending of soaps. Alpha camphorene has the structure:
, , ,. ,:

H2C~C~
, i. H~ ~CH ~13 ~CH C~ 3 ~ ,C~2 112~ C
.

-12~ $~ 3~

U.S. Patent 3,50~,7G9 issued on r~larch 2~, 1970, ~u'~uhar~) j discloses a toilet preparation containing a storaye- ¦
stabilizing amount of a hydrocarbon which may ~e a mono-cyclic hydrogenated terpene polyrner of the formula (C10~
and/or a bi-c~clic hydrogenated terpene polvmer of the for-mula (C1oH17)n where n is a whole nu~ber of from 2 to 4 and a cosmetic base, such as a cold cream or a cleansing cream base. In column 2 of U.S. Patent 3,502,769 at line 15, it is indicated that the hyd:rogenated terpenes are produced from alicyclic ~erpene hydrocarbons. It is fur-ther indicated that, for example, mono-cyclic terpenes such as menthadienes (e.g., alpha-terpinene, gamma-ter-pinene, alpha-phellandrene, beta-phellandrene, terpinolene, limonene, etc.) and bi-cvclic terpenes such as the cam-phenes are first polymerized to form hydrocarbon comDounds , formula (C10~16)n~ wherein n is a posltive whole j number from 2 to 4. It is further specified that these polymers are either dimers, trimers, or tetramers, and that the resultant polymers are then completely hydrogenated 1 20 and in the case of the menthadienes, form mono-cyclic polymers ofthe formula ~CloHlg)n~ wherein n is a w~ole number of from 2 to 4, and in the case of the bi-cyclic j terpenes, it is indicated that there are formed ~i-cyclic , ~: ; ~ polymers of the formula (C10~17~n wherein n is a whole '' !
I 25 num~er 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:
j ~3 Cr~ ~ 3 C 3 C 13 ~ C~~'kC--Di-pentene Dimer Reduced Dimer t~J ~ 3 ~ C~ ~ 0 ~

C~CI~ ~U~ ~H~ H~C CH~, H ,~ CH3 ~ Di-pentene Dimer Reduced Dimer :, .

Although perfumes are shown to be usable in conjunction with the hydrogenated terpene polymer materials which are further 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 oE (i) such terpene dimerization products as dimerization products of camphene or of alpha-pinene or beta-pi.nene and (ii) alpha-methyl styrene dimerization products of our invention are useful in the manner described herein as perfumery extenders and diluents.

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Descript.ion of the clrawings:

Figu e 1 is the GLC profile for the produc-t produced according to Exam~le I, Eraction 19.
Figure 2 is the infrared spectrum for the produet produc-ed according to E~ample I, Fraction 19.

Figure 3 is the NMR spectrum or the product prod~ced according to Example I, Fraction 19.

Figure 4 is the GLC profile for the product produced according to Example I~, Fraction 3.

Figure 5 is the infrared spectrum for the product produc-I ed according to Example I, Fraction 3 as well as Example I . III.

I Figure 6 is the NMR spectrum for the product produced ! 20 aecording to Example I, Fraction 3 as well as the product produced according to Example III.
~ i .
I Figure 7 is the mass spectrum for the product produced according to Example I, Fraetion 3 as well as the product I
!25 produced according to Example III.
i . Figure 8 is the GLC profile for the product produced aeeording to Example III, Fraetions 9-12 wherein a . ~ Filtrol R eatalyst is used as the dimerizing agent.

; ~ ¦ Figure 9 is the GLC profile for the dimerization product . i of alpha-pinene produced according to Example IV(A)~
, ..
Figure 10 is the GLC profile for the dimerization produet of eamphene produeed according to Example IV(B).
!i , Figure 11 is the NMR spectrum for the product produced , according to Example IV(A).

Eigure 12 is the infrared spectrum for the product produc-ed according to Example IV(~).

Figure 13 is the GLC profile for the product produced according to Example IV(C), the dimerization product of limonene.

Fi~ur~ 14 is the NMR spectrum for the product produced according to Example IV(C), the dimer of limonene.

is the infrared spectrum for the product produc-ed according to Example IV~C~, the dimer of limonene.

.

Il 20 '' "':' , ~l , ;~ ~ 1 25 ~ ~ ,- ' .',', ` 1 I ~
.` ~ 130 ~ ' ' -,`
: . ' , .
. . . ' - '.

I
~
i -lfi~ 3 De~ tion of the Preferred Embod-ments Surprisingly, it has been found that either (i) in the alternative; or (ii) mixtures of (A): dimerization products 5- of (i) monocyclic terpenes containing two carbon-carbon double bonds, (ii) bicyclic terpenes containing one carbon-carbon double bond and (iii) a monocyclic terpene contain-. ing two carbon-carbon double bonds and a bicyclic terpene containing one carbon-carkon double bond or mixtures of - 10 same or hydrogenation products thereof or mi~tures of said hydrogenation products and said dimerization products and/or (B) alpha methyl st~rene climerization products, ;. dimerization products of methyl or other C2-C4 lot~er alkyl homologues thereof and hydrogenated derivatives thereof may be used as diluents or extenders of various perfumery materials without appreciable loss of the characteristic ~i odor effect of such perfumery materials.

Dimerlzation products (A) are produced by dirnerizing . 20 such compounds as camphene having the structure:

or alpha pinene ha~ing the structure:

~3 35 or d-lironene ~having the structure: ~ ~

.~,1 ' . ' , '.
~i .
.. . ..
' ' ' ' ', , . . . I
.
, ' .L~ 3w~
`~17 , or alpha-phellandrene having the structure:

10~b -- ~/
/\

or gamma-terpinene having the structure:

. 20 `

- . ~ or delta 3-carene having the structure:

3Q I i O De a ~hellAndrene ha ~y the str~ct e: ~ ¦

.

r~ fi1 or beta-terpinene having the structure:

. 5 or alpha-terpinene having the st:ructure:

- '10 ~
.., ~.

l15 or terpinolene havihg the structure:

~ ~ 1~20 .~ ~ . or beta pinene having the structure~
~ ~ ' 11125 ~ ~

. 3Q
. or by "dimerizing" mixtures of two or more of such com- ¦
~ ~ : . pounds, such as the mixture of C10 terpenes commonly known .. ~ as "sulfate ~urpentine" or hy "dimerizing" a C10 terpene and a dehydrogenated terpene ~e.g., cymene~ in the presence : 35 of acid catalysts, such as sulfuric acid and hydrofluroic :
¦ acid or in the presence of acid clay catalysts, such as . j Japanese Acid Clay or Fullers earth or cation-.. exchanc~e 11 .
~. .

. ' ~ .

3~3~ ~ ~

resin catalysts, The said "dimerization" products are compounds having such possible structures as:

: and the hydrogenation products thereof have such possible structures as:

15= ~ ( ~ ,20 Insofar as the dimer1zation 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 lO 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 of said reaction products.
' .
. ~ 30 Dimerization products (B) produced by dimerizinq alpha m hyl ~tyre7e h~- ir tl~c s~ruc-~re:

r ,1 .j I ~

. . . : ~ ::
. . . ~

or by dimer.izing a methyl or other C2-C4 lower alkyl homo-logue thereof having,,for exam~le, the struc-ture:

S /~

in the presence of Lewis Acid catalysts, Bronstedt acid catalysts such as ~lfuric acid or in the presence of acid clay catalysts such as Japanese Acid Clay or Fullers earln or cation exchange resin catalysts. The di~sri~a-' tion product'of alpha methyl styrene so u5eful have the ~15 structures ~ ~ R5 ~ / \

j ~5 !' "

wherein orle of R5 or R5 is methyl or other C2 C~ lower alkyl anr~ the other of R5 or R5 ls hydrogen or each OL
R5 and R5 are the same or r1ifferent C1-C4 lower alkyl, e.g., methyl. Hydrogenation products thereof have the structures:

1~ ~\0 ' .
.j !l5 I ' ' O
,j , I .

--~2--\C~` ~ 5 Cl~

: ! ' ~ / i ~ .

;30 /[~

5' ~ ~

~5 ;~ ., `:

-23- ~ ~f~

wherein one or both o~ R5 and ~.5 is methyl or other C2-C4 lower alkyl. Such hy~rogenation products can be represented bv the generic structures:

,' ",~' i ~ I ' R3 ~ J R3 : ; : . . ~ R4 ~:~ - 25 . ~ " ' .

.
. 30 wherein R3 and R~ are the same or different and represent . .- hydrogen or methyl or other C~-C4 lower alkyl; wherein the dashed lines and wavy line represent carbon-carbon single bonds or carbon-carbon doub].e 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 riny and where the line~

-24~

represen~s either a carbon-carbon single bond or no bond.

In the case of the hydrogenation product, when P~3 and/or R4 are lower alkyl, for example, methyl, the methyl groups mav be in a "cis" or "trans" rel~tionship to one another and with respect to ~he cyclohexyl moieties.

A signIficant property of the above-said mixtures of dimerization products and hydrogenated dimerization pro-ducts is that they have a broad range of solubi.lities for various types of perfumery materials including complete solubili.ty 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 sub-20 ject 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 ~ $ ~ ~-3 Patchouli Oil Cinnamon.itrile~
Geranonitrile Thus, it has been discovered that the dimers of our invention can be used as partial re~lacemen-ts ~or cer-tain essential oils and synthetic suhstitutes 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 synthe-tic perfume oils or natural perfume oils or mixtures of natural perfume oils and synthetic perfume oils with which there has been incorporated from 1~ about 1 up to about 30 parts of either (i) in the alterna-tive or (ii) a mixture of (A) an alpha methyl styrene or alpha methyl styrene methyl or othex C2-C4 lower alkyl - homologue dimerization product or hydrogenated derivative thereof or mixture of alpha methyl styrene or alpha methyl 2~ styrene methyl (or other C2-C4 lower alkyl) homologue dimerization product and one or more hydrogenated deriva-; tives thereof which have at least one of the following .- . structures:
., ;. .

. . . .

:

- 2 6 ~ 3 ~ ;:3 J ~

S C~
"``~'-1 .

C~ i 0~,/ i 15 ,\0` ~

\ ~

3 0 . ~ : /

, ~ 5 -C

lS R R

R5 ~/~

. R5 '. ~' ' , ', ' , ' ~ : '' ' "

R5 ~<

R;

-28~

wherein one or both of ~5 and R5 is methyl or other C2-C~ lower al~:yl, (These com~ounds being re~resented collectively by the generic structures:

~ ~ ~' ~

.

in the case of alpha methyl styrene dimerization products and dimerization products of methyl or other C2-C4 lower alkyl homolog.ues thereof and the structures~:
-. .
, ~ R~

--29-- :

R~ ~ R5 R5 15 wherein one of R5 and R5 is methyl or other C2-C4 lower alkyl and the other is hydrogen, or both R5 and R5 are methyl or other C2-C4 lower alkyl in the case of the hydrogenated derivatives thereof wherein the dashed lines and wavy lines represent carbon-carbon single bonds or 20 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 xing containing the dashed lines and the wavy 25 lines is a benzene ring; and wherein the line iilllllllllllllllllll - 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 - 30 . 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 terp~ne containing one carbon-carbon double bond or (iii) a reaction product of a monocyclic terpene containing two carbon-carbon double bonds and a bicyclic terpene contain-r!;3 ~ 3 v ~

ing one carbon-c~rbon douhle bond and~or hydrogcnatecl derivatives the~eof per lon parts of compounded singLe phase liquid perfumery composition. S~ecific e~mples 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 product.s of d-limonene;
Dimerization products of ga~ma terpinene;
Dimerization products of alpha phellandrene Dimerization products of ~3-carene;
Dimerization p~oducts of beta phellandrene;
~imerization products of terpinolene;
Mixed dimerization products of alpha phellandrene and ~3-carene wherein a mixture of the two is subjected to a dimerization reaction;
Mixed dimerization products of alpha phellandrene 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 ~3-carene;
Mixed dimerization products o f sulfate turpentine;
- Mixed dimerization products of terpinolene and gamma terpinene;
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-ery materials to which they are added.

P~3¢i'~

The above stated clirneri~ation products, hyclrogenatscl derivatives thereof and mi:~tures thereoE may ke pro-duced according to anv of the known methods in the prior art. Thus, a reaction scheme whereby a dirner-ization product (B) may be produced useful in our in-vention and wherek~ hydrogenatecl derivatives thereof also useful in our invention are produced and whereby mixtures of such hydrogenated derivatives and dimeriza-tion products are produced is exemplified below:

Reaction Scheme ~

~(possible structure;
and.many other ~ isomers) , ' \ ' - .

; \

~
. - - . .
'`' '- '.'" '' . ' ' ' . / \, ' ~- - , .
~possible structure; and many other isomers) .

. .

3~

The catalysts useful itl proclucing the climerization pro-ducts of ten carbon atom containing terpenes of our invention are Lewis acids such as borontrifluoride, alum-inum trichloride, sronstedt acids such as sulfuric ~ci~
and phosphoric acicl, 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 hexahvdro-1,1,2,3,3--pentamethyl-indane or in 10- the absence of solvents. The temperature o dimeriz~tion may vary from 20C up to 250C. A preferred catalyst system with preferred temperatures range are borontri-flouride etherate at 0-100C or Acid Clay at 80-175C.
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 ~eight ratio of 1:0.05 up to l:0.01.
"Turpentines" including "sulfate turpentine"1 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", 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 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 a~undant constituent in gum and sulfate turpentine, varying Erom 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 pinene is the most versatile chemically.
Gum turpentine contalns 5'~ to 3,~, of monocyclic p-menthadienes, commonly referred to as "~ipentene", the trivial name for dl-limonene, Table I - Com~osition of Southern Tur~entines (i) , . _ .

Com~onent Sulfate Gurn Wood ;
10Alpha Pinene 60-70 60-65 75-80 Beta Pinene 20-25 25-35 0-2 Camphene ~race 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 oxysenated 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 ,,,, , !~ occur in small amounts in sulfate turpentine. The ,~- 25 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~ 6~3 Species oE pine from which Turpentine is Chemical Composi~ion DeriVed of Turpentine (l) Pinus albicaulis A3-carene (35~) Engelmann (I~Thite- Other Terpenes (10~) bark pine) . A Sesquiterpene (7~O) A Diterpene (30gO) (2)- Pinus Aristata d].-andl-fi-Pinene (a6%) Engelmann ~Bristle- A m~ ricyclic Sesqui'er-cone pine) pene (4~) (3) Pinus attenuata Over 95~ d-~-Pinene Lemmon ~Knobcone No ~-Pinene or Ca~phene pine)

(4) Pinus balfouriana dl-and 1-4-Pinene (90~) 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%) . 25 Lambert (~ack dl-and l-~-Pinene (10%) .pine)~ :

.
- ~6) Pinus caribaea . l~-q-pinene ~61.5%) . ~ Morelet (Slash . l-~-Pinene (34%) pine) Tailings (4.5%) .
: ~ ~ - t7) Pinus clausa 1-4-Pinene (10~) :. (Engelmann) Vasey l-Camphene (10%) (Sand pine) l-f3-Pinene (75~) , , _ ~ ~!r~3~

(8) Pinlls contorta var. l~ hellanclrene Latifolia r.ngelmann ~Lodgepole pine) (9) Pinus coulteri n-Heptane (5%) (D. Don (Coulter l-~-Pinene (30-35~) pine) l-~LPhellandrene (35-45%) n-Undecane (10%) (10) Pinus echinata d-q-Pinene (85~) Miller tShortleaf 1-f-Pinene (ll~J
pine) Limonene (11) Pinus edulis ~-Pinene ~70-75~) Engelmann ,~Pinyon~ ~-Pinene (5%) Colorado pinyon ~-Cadiene (15-20%) pine) (12). Pinus flexilis dl- and 1-q-Pinene (80%) - 20 James ~Limber Albicaulene-A Monocyclic pinel Sesquiterpene (13%) Bicyclic Sesquiterpene - C7%) i,. -;,.-';', -. :
...... . . . . .
,, " .. ~ .
: i 25 ~131.Pinus gla~ra l-Limonene Walter CSpruce pine) , , .- . , : C14~ Pinus lam~ertiana . l-Q-Pinene (65%) .-: Douglas (Sugar 1-~-Pinene ~13%) ;~ 30 . ~ pine) Bicyclic Sesquiterpene : - of Cadalene Type (10%) - Lam~ertol ~Sesquiterpene . Alcohol C15H26O) (2%) -~6-(15) Pinus monoph~lla d-~-Pinene (859~) - Torrey and Fremont l-Limonene or Dipentcne (Sin~le~leaf pin~on) (4-5~) d-Cadinene (4-6%) (16) Pinus monticola d-~-Pinene (60%
Douglas (Western ~-Pinene (26~
white pine) n-Undecane (1-2%) Sesquiterpenes and perhaps Limonene (17) Pinus~muricata d-4-Pinene (9~-99~O) D. Don (Bishop Camphene (less than 190) pine) (18) Pinus palustris d-q-Pinene (65~) Miller (Longleaf l-p-Pinene (31.5%) pine) Tailings (3%) . 20 (19) Pinus ponderosa l-~B-Pinene (50%) Lawson (Ponderosa 1-~3-Carene (20%) pine) l-Limonene and Dipentene (25%) ; : d-Cadinene (3%) ~ Ponderene (less than 1%) .. . .
~20) Pinus ponderosa d-~-Pinene (60-70%) . ~ yar. scopulorum ~-Pinene (5%) : . Engelmann (Rocky Limonene t20 - 25%) - . 30 Mountain ponderosa pine) ~ . .
; (21) Pinus radiata dl-~-Pinene (75~O) D. Don (Monterey l-~-Pinene (22%) pl-e~

.

(22) Pinus resinosa ~(-Pinene ~i-t. (Red pine~) (Norway pine) (23) Pinus rigida var. Limonene serotina (Michan~
Loudon (Pond pine) (24) Pinus strobus dl~~.-Pinene (75%) Linnaeus (Eastern l~ -Pinene (15D6) white pine) Terpene ~lcohols and Ketones (4~) A Tricyclic Sesquiter-pene (0.3%) ' ~
(25) Pinus taeda d-q- Pinene (85~) Linnaeus tLoblolly l-d-Pinene (12~) pine) (26) Pinus torreyana l-Limonene (75%) - Parry (Torrey n-Decylaldehyde (10%) : : pine) n-Undecane (5%) . . . Longifolene (4%) Laurylaldehyde (0.2~) . 25 I Heptane and Nonane (less than 0.1% of each) -. (27) Pinus virginiana dl-~-Pinene (90%) MiIler ~Virginia l-~-Pinene (8%) . 30 - pine) (28) Pinus washoensis d-~3-Carene (chiefly, Mason and Stoc~well ~-Pinene, Dipentene, A
- Cyclic Sesquitexpene, ~, 35 1-Jg-Pinene-(i~3-Carene content is low) The dirnerization produc-ts "~" of our invention ancl hy-lro-yenated derivatives ma~ be procluced according to anv of the known methods in the prior art and according to one of the following reaction schemes:
s Reaction Scheme ~1:

~10 ~ ~+ ~

(minor: cis , ,, and trans i~omer mixt.) Reac'tion 'Schem'e ~2-' 20 2~ 0 .- . -" . ,.

, .,-: .30 Reaction Scheme #3 .. . . .
. ,-, ., - . .

35 ~ O

3~

Reacti.on ~cheme 1~4 ~ ;

~minor: cis and trans isomer mixt.) Reaction Scheme ~5:
. .

, ,:, .
,.:,, :

. Reaction Schem~ #6:
- -. . ~

N3C ` ~ ~C ~

.

.- ~ . .
,' . ' ' .f~3 Reaction Scheme "7:

~ R

' (Mixtures) (Minor: cis - and trans isomer mixt.) 15 Reaction Scheme #8:., .~ ~
' .

3 ~

., . - :
~ . 25 ~ ~ ~Mixtures) ' ~

Reaction Scheme #9:

30 ~ "

(Mixture) (Mixture~

Wherein R3 and I~ are the same or ~1ifferent and rc~present hydrogen or methyl or other C7-C~ lower al]~l and ~"h~rein ' the dashed lines, the wavv lines, and the line~ ¦and the line t t + are as defined above.
In this dimerization reaction, the catalysts that rnay be used are Lewis Acid such as borontriflouride-aluminum tri-chloride or Bronstedt Acids such as sulfuric acid or phos-phoric acid or such acids on car:riers such as alumina, sil-ica or cation exchange resin catalysts such as Amberlyst - 15, or acid clay catalysts such as Japanese 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 dimerization may be from about 20C up to about 250C with a pre~erred temperature range when using borontriflouride etherate of 0-100C or when using acid clays of from 80-' 200~C~ The pressure at which the reac'tion may be carried ~ out is conveniently atmospheric pressure but higher pressures or pressures lower than atmospheric may also ~ ' be used without ad~ersely 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 ;,' , 30 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 ~bout 80C up to about 150C at pressures of from about four atmospheres up to ahout thirty atmospheres.
The extended perfumery oils and chemicals of our invention may be used in compositions where the natural oils or .

chemic~ls would have been used, ~or e~mn].e, in comhina-tion with sandalwood oil, vetiver oil, oakmoss, ionone, labdanum, methyl ionone, patchouli oil and other s~lnthe-tic substitutes therefor.
The eXtended perEumery materials of our invention will find use as constituents of compounded perfumery composi-tions in which a number of perfumerv material.s of natural and/or synthetic origin ~ill be blended together to produce a particular desired odor effect. Such com~ositions may then be used in space sprays or can be blended in soap, detergent or deodorant compositons, including bath salts, shampoos, toilet waters, face creams, talcum powders, body lotions, sun cream preparations and shave lotions and creams. The perfu,m,ery compositions can also be uSed to perfume substrates such as fi~ers, fabrics and paper products.

The following,examples are given to illustrate emkodiments -of the lnvention as it is presently preferred to practice ' ., , it. 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 . claims..
:~ . . . . .
,:, ., ,25 .
~ :.", ~
:~ '' ' ' - : , , . ~ 30 ~ , ~: . .
, . , .

.

Examnle I

Pre~aration of alph~ methvl styrene cli~erization product .

Reaction: .

lo 2 ~J~ +~

~minor: cis and 15 , trans isomer mixt,) ~ Into a two-liter reaction flask equipped with thermometer, . reflux condenser, cooling ~ath., addition funnel, stirrer and gas ~u~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 is then . brought to 30C~ Over a period of two hours after the .~ sulfuric acid is added~ while ma;ntaining the temperature of the reaction mass at 20-33C~ 50~ g of alpha methyl ` 25 styrene`is added. After the addition of the alpha methyl styrene, the reaction mass ;`s 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 minutes . 30 and heated to 70C. The layers are sepa.rated and the -. . organic layer is washed neutral Cat 70C~ with a 5% sodium ~ :. hydroxide solution (two 250 ml volumes~ and a 5~ sodium .:~. ` chloride solution (three 2S0 ml volumes~, 650 g of crude product ïs recovered and distilled after adding to the mixture 15 g of Primol ~ and 0.2 g of ~onox ~ through a 12" ~igreaux column as follows:

` - -4~

Vapor Liguid ~leig~t oL
Fraction Temp. Temp. V~c, ~n.Frn~tion 1 69 101/135 760/760102.2 2 132 145 2,3 2.8 3 132 146 2.3 26,4 4 132 14~ 2.3 16.0 132/134 148/148 2.2/2.2 19.4 6 132 149 2.2 26.2 7 132 149 Z.2 21.6 8 132 142 2.2 25.~
9 132 150 2.2 2~.2 133 150 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 23.7 133 155 31.5 16 135 162 2.3 29.4 17 137 - 169 2.3 23.1 18 I39 176 2.3 12.5 - 19 142 202 -- 13.2 141 221 2,3 10.3 - 21 188 - 230 10.5 25 ~22 1~7 242 2~3 8.1 '; . .- . .. .
Figure 1 sets forth a GLC profile for Fraction 19~ This fraction is primarily the alpha methyl styrene dimer .
having the structure:

(cis and trans isomers) ., - ~ ' .

.

;

I Figure 2 ls the infr.lred spectrum ~or Fraction ].9. Figure I ~ 3 is the NMR spectrum fro Fr~ction 1'3. The mass spectrum ~ for Fraction 19 which is -the compound having the structure:
S .' 0 ~ (Ci5 and trans . isomers) 15 is as follows: -.

M/E Rel~t~ve Inte~~sity j 3g 235 ~1 274 ` : 51 18 . .
: ~ 77 19 - ~1 42 : ~ -'- ~. -; - 103 14 .: . 1 : 25 ~ 119 100 . 143 20 ` ~ ~36 206 ' ' ' .

The GLC profile for Fraction 3 which is primarily the . compound having the structure:
. ~ \~

~

;' ` ` ' .
.

.

-~6-is s~t forth in Figure 4. Figure 5 sets forth the infr~-red spectrum or Fraction 3. ~igure 6 sets forth the ~ IP.
spectrum for Fraction 3, Figures 4, 5 and 6 also represent, respectivel~, the GLC, IR and NMR spectrum for the product produced according to Example III, infra.

Example II

Preparation'of 'alpha methvl- stYr'ene d'imerization procluc Reacti'on:

2~J~

minor) (major: cis and trans isomer mixture) . ,, .,:
`' 25 Into a one-liter reaction flask equi ped with thermometer, ' ' addition funnel, heating~mantle, reflux-condenser, stir, -~ Y-adapter and distillation head ;s added 100 g of cyclo-hexane followed by 5 g of p-toluene sulfonic acid, The resulting mixture is heated to 50C and over a one hour period, 500 g of alpha methyl styrene is added to the -"' - ' reaction flask. ~he'reaction mass is'then heated to 100C
~' and maintained at that te~perature for a period of four hours. 529~3 g of crude product 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 following distillation data:

-~7-Fraction Vapor I,iquid ~ei~ht oE
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 34.0 142 16~ 2.4 49.6 6 144 170 2.4 100.4 7 164 195 2.4 58.5 a 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 12 214 225 2.2 18.1 13 210 250 2.2 41.6 ' ' ' .
Exam~le III

Preparation of alpha methyl styrene dimer -, -, . :
~ : ; Reaction~

2 ~ -~ ~

~ -30 ., ,., ,-.: .
C ' K, .~ . . ', `` Into a 1,000 ml reaction flask equipped with thermometer, addition funnel, heating mantle, reflux conclenser 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 -having the following properties~

. . ~

.
.
.. .

~ .3 Particle si.ze analysis by Tyler Stancl~rd Sieve Through 10 ~lesh, ~t. ~100 Throllgh 20 Mesh, Wt. ~ 5 Free Moisture, Wt. ~ . 10 Free and Combined ~50isture, Wt.~ 15. (Max.) (Loss at 1700F) Bulk Density, lbs./cu. ft. 43.0 Particle Density 1.3 Surface Area, N2 absorbent 280-300 (Bet Method) U2/gm 50 g of alpha methyl styrene is added to the Filtrol and the reaction mass is heated to 100C. ~nother 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 ho~rs. The reaction mass is then :..... .`. : filtered yielding 470 g of crude product which is then mixed with 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 ~i~uid Weight of Fraction . Temp. Temp. Vac, mm. Fraction ~gm) :: 30 1 38/88 135/140 2.5/2.5 1.2 2 .133 142 2.0 7.0 3 134 142 2.0 . 1~.0 ~: ~ 134 142 2.0 - 17.1 134 145 1.8 53.5 6 134 146 1.8 31.0 .
7 135 147 1~8 49.2 - .

;~ ' '.
, Con'-t.
Vapor ' ~iquid ',~Jeight of FractionTem~. TemP. Vac. mm. Fraction ( 8 135 148 1.8 51.5 9 136 149 1.8 46.2 137 151 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) Figure 4 is the GLC prof~le 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 Fractions 9-12. Figure 8 is a second GLC
profile for Fractions 9-12.

- Example IV (A) Preparation of alpha pinene dimer .~
70\
Reactlon-~- . - . - , , ~ 2 .. . .
. . ~ X
/ \
~ (possible structure:
and many other isomers) - ~\
-50~ 3~

Into a two-li-ter reaction flask equip~ed with stirrer, thermometer, addition funnel and reflux con~enser, are p ac~l:. 'CG 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 West Cen-tury Boulevard, Los ~ngeles, California 90045 having the follo~,7ins properties:

Particle Size Analysis by Tyler Standard Sieve Through 10 Mesh, Wt. ~ 100 Throuyh 20 Mesh, ~lt. ~ 5 Free Moisture, Wt. ~ 10 Free and Combined Moisture, Wt. 15 (Max ) (Loss at ~700F) Bulk Density, lbs./cu. ft. ~3.0 Particle Density 1.3 . .
Surface Area, N2 a~sor~ent 280-300 et Method M2/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 .. ..

J~ 3~

going to 4:1~ Just prior to distlllation, 30 g of Primol is added to -the ~aterial to be distilled. ~he distilla-tion data are as follows:

Vapro Liquid Ref 1UX Weight oE
Fraction Tem~. Tem~ Vac, mm, ~atio Fraction 1 35/75 72/115 50/35 9:1/9:1 ~4.1 2 39 95 3.0 9:1 53.q 10 3 41 103 3.0 9:1 46.0 4 ~1 165 3.0 4:1 68.7 31/128 152/168 1.0/.8 4~1/4:1 3~.0 6 133 175 0.~ 4:1 43.0 7 133 179 0.8 4:1 51~].
15 8 133 , .. 180 0.8 ~:1 49.g 9 133 1~1 0,8 4:1 44.5 133 185 0.8 4:1 ~9.5 11 133 187 0.8 4:1 47.5 12 136 193 0.8 4:1 42.7 2013 140 204 018 ~:1 44.5 : Figure 9 i8 the GLC profile for the alpha pinene dimer (fractions 9~ Conditions: 2% Car~owax Column, 25i 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 ~).
: ~ : 30 - , .: . -, ' ' ' .

ExAmple IV (B) Dimers of Camphene Into a two-liter reaction flask equipped with stir, thermometer, addition funnel and reflux condenser with 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 ~", prQgrammed at 80-240C at aoc 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.
; 25 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 obtained:
: 30 ",.,,,, A~ ~ Fract. Vapor Pot Pressure Weight of GLC Analysis Num. Temp. Temp. mm Hg. Fr. (g.) of Fraction 1-6- 45-10087-160 ~2.6631.9 Recovered hexa~
hydropenta-methylindane 7 149 7 ~ 10.5 Intermediate ~ Section 3~
Con't.

Fracl, Vapor Pot Pressu Weigh-t of GLC Anal~sis Numb. -Temp. Tem~. mm. Hg. Fr. (~.) of Praction lS0 1 170 1 2.8 ' ~0.7 I Practicall~
l ¦ ¦ Pure Dimers .. . , 9-11152-1681176-230 2.5 i 214.8 Pure Dimers 10 _ I - ,. ! ..
, 1~215 275 2.5 1~ 22.9 . . ~
13-14225-250 290-306l 2.5 1 62.7 Very Little l I ! Eluted on GLC
Residue - 41.7 Trap - 18.0 Figure 10 sets forth the GLC profile for fxactions 9-11, the camphene dimer (Conditions: 5% SE 30 column, 10' X ~", 20 programmed at 80-240C at 8C per minute).
.~ .
- The structure of the hexahydropentamentylindane, used as i a solvent is as follows:

`~ Example IV (C) ., - ~-:
Preparation of d-Limonene Dimer :~ ~ Into a 500 ml reaction flask equipped with thermometer, stirrer, condenser and addition funnel are placed 5 g Primol ~ and 2 g Filtrol 25. The reaction mixture is 35 heated to 150C and 40 g of limonene is added dropwise over a period of 80 minutes. The reaction mass is then heated at 150C for 3 hours.

-54- ~ 3~

The reaction mass is then cool.ed, ~iltered and distil].ed.
The resultin~ product is the climer of d-limonene, confirm-ed by GLC, N~IR and IR analyses~

The GLC profile is set forth in ~igure 13. The MMR
spectrum is set forth in Figure 1~ The IR spectrum is set forth in Figure 15.

Exam~le V
- Patchouli oil ~80 parts~ ohtained 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 of Example rv (A)~ The alpha methyl styrene dimer - alpha pinene dimer mixture is found to act as an extender for the patchouli oil in that the characteristic odor éffect of the latter is substantially not modified.

Exam~le~VI
,: , .~ . ` The extended patchouli oil prepared according to Example V ,' .,.'`.'-' is successfully incorporated into a compounded composition of the Chypre type ~y ~lending the following ingredients:
. . 25 Parts ' . ' Cinnamic Aldehyde .~ ; Ethyl Methyl Phenyl Glycidate ', - 30 ~ Methyl Nonyl Acetaldeh'yde' 2 -, Oakmoss (Absolute~. 20 .'.. : ,'.~ ' Sandalwood Oil OEast Indian¦ 20 - . Yetiveryl Acetate 20 Ylang Oil No~ 1 20 Benzoin Resoin (Sumatra~ 30 Alpha Ionone (100~ 30 'l~f~'3''~

Glove Stem Oil (Zanzibar)36 Bergamot Oil 4G
Hydroxycitronellal 40 Iso Eugenol 40 Extended Patchouli Oil (Ex,~ VJ 40 Coumarin 50 Musk Ketone 50 Amyl Salicylate 60 Cedarwood Oil (American)60 ; 10 Citronellol 60 Ben~yl Acetate 80 Phenyl Ethyl Alcohol 150 Terpinyl Acetate 150 : Exa~ple VII

A patchouli oil extender base is prepared ~y ~lending the following ingredients: -: 20 Parts - , - . .
., . . , . - .
- Mixture of 10 parts of~alpha `38 . ~.
; methyl styrene dimer produced ~- 25 according to any one of Examples I, Il or III and 28 parts of . d-limonene~dimer produced : according to Example lV ~C1 . Galaxolide 27 . j - .
Isolongifolene Oxidate 20 Omega-Hydroxymethyl Longi~olene 10 ` 35 Cedrol 3 .
Sandalwood Oil ~East IndianJ 2 , , . . . .

This mixture (46 parts) is then blen~e~ with na-tural patchouli oil ~Seychelles) (60 parts) -to provide a satisfactorv extended 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 t:he following ingredients:
Parts .
Balsam Peru 30 Labdanum Resin 30 Oakmoss Absolute -, 30 Sandalwood Oil (East Indian) 30 Linalyl Acetate ~0 Terpinyl ~cetate 40 Geranium pil (Bourbon~ 50 Musk Ambrette 50 : . Coumarin 60 Amyl Salicylate 60 . : ;Methyl Ionone ~ 70 . . Cedarwood Oil ~merican~ 80 25~ Clove Stem Oil ~Zanzibar~ 8d ~eti~ert Oil ~Bourbon~ .80 Extended Patchouli Oil 130 . Lavandin Oil 140 ~'~-. . ,,. . 1000 -;- ~ 30 .. . ... . .
: . Example IX
. ' '.. . .
.. . - : , ~
:~ : Patchouli oii C85 parts) obtained from the Seychelle : Islands is blended with the 10 parts by weight camphene dimer produced according to Example rv ~B) and 5 parts of the alpha methyl styrene dimer of Example II. The camphene dimer - alpha methyl styrene dimer mi~ture is ' : :
.

~ found to act as an e~tender ~or the patchouli oil in that ~he characteristic odor effect oE the latter is substantially not modified.

Exam~le X

The extended patchouli oil prepdred according to Example IX is successfully incorporated into a compounded compo-sition of the Chypre type by blending the following ingre-~ 10 dients:

, . .
Parts . . _ Cinnamic Aldehyde Ethyl Met~yl Phenyl Glycidate Methyl Nonyl Acetaldehyde 2 Oakmoss ~A~solute~ 20 Sandalwood Oil ~East Indianl 20 ~etiveryl Acetate 20 Ylang Oi.l No. 1 - 20 Benzoin Resoin ~Sumatra~. 30 .
Alpha Ionone U00%] 30.
CloYe Stem Oil CZanzi~arl. 36 ~ . Bergamot Oil 40 : :~ . 25 . ~ydroxycitronellal 40 ; Iso Eugenol 40 . . Extended Patchouli Oil ~Exq rx~. 40 : . Coumarin 50 Musk Ketone 50 ~ `30 Amyl Salicylate 60 :;': - ~ Cedarwood Oil (Americanl. 60 . Citronellol 6a : . Benzyl Acetate 80 Phenyl Ethyl Alcohol 150 Terpinyl Acetate 150 1000 ~
ll ,11 ' ' Exam~le XI
~ ,~

Patchouli oil '(80 parts) obtained from the Seychelle Islands is blended with the alpha pinene dimer produced according to ~xample IV (A) (20 parts), 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 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 Acetaldehyde2 . . 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 ;~ ; ;30 ~ 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 .

.

. .

~ .

3~3~
-59~

Exam~le ~III

A patchouli oi1 extenaer base is prepared ~y ~lending the following ingreclients:

Parts Alpha Pinene Dimer produced38 according to Example IV ~A) Guaioxide 27 Isolongifolene Oxidate 20 15 Omega-hydroxymethyl.longifolene 10 Cedrol 3 Sandalwood Oil (East Indian) This mixture (46 parts) is then blended with natural patchouli oil (Seychelles~ (60 parts) to provide a sati~fact~ry extended patchouli oil.

: ~ Example XIV

; The extended patchouli oil prepared in Example XIII is . incorporated into a compounded per~umery 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 .

.

3~

Linalyl Acetate 4n Terpinyl Acetate 40 Geranium Oil (Bourbon)50 Musk Ambret-te 50 Coumarin 60 Amyl Salicylate 60 Methyl Ionone 70 Cedarwood Oil (American) 80 Clove Stem Oil (Zanzibar) 80 Vetivert Oil (Bour~on)80 Extended Patchouli Oil130 Lavandin Oil 1~0 Example XV

Patchouli oil (85 parts) obtained from the Seychelle Islands is blended with the camphene dimer produced accordiny 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 effect of the latter ;` ; ~ is substantially not modified.
~ . ~ ~, j, .. . .. .
, . ~., .~ ~, - . .. . . .
;~;; "~ ~- Example XVI
:^ 2~
~ 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 ,.... .. . .
` ~ ~ Cinnamlc Aldehyde Ethyl Methyl Phenyl Glycidate Methyl Nonyl Acetaldehyde 2 Oak~osS (A~-solute? 20 Sandalwood Oil (East Indian) 20 Vetiveryl Acetate 20 93~

~61-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~ XI) ao Coumarin . 50 Musk Ketone ~ 50 Amyl Salicylate 60 Cedarwood Oil ~American) 60 Citronellol 60 Benzyl Acetate, 80 Phenyl Ethyl Al,coh,ol 150 Terpinyl Acetate 150 ExamDle'X~II
, . ' A patchouli oil extender base is prepared ~y ~lending ,,' ~ '' the follo~ing ingredients:
:"... .... . . . . ..
,",,,"~ ,,, P'arts ~' ,25 ' Camphene Dimer produced accordi'ng '38 ~:- ' to Example IY ~B~ ' Guaioxide ' 27 :: -, : 30 .`;:,,'",,`.'~ Isolongifolene Oxidate 20 ' ~ omega-hydroxymekhyl longifolene 10 :
Cedrol 3 Sandalwood Oil (East Indian) 2 .

3~

This mi~ture (46 parts) is then hlencled with natural patchouli oil (Seychelles) (f~0 parts~ to provide a s~tis factory extended patchouli oil, Exam~le XVIII

The extended patchouii oil prepared according to Example XVIII is incorporated into a cornpounded perfumery compo-sition of the Fougere type conta;ning the follo~ling in-gredients:

Parts Balsam Peru ' 30 Labdanum Resin . 30 Oakmoss Absolute 30 Sandalwood Oil ~East ~ndian~ 30 Linalyl Acetate 40 , Terpinyl,Acetate 40 Geranium Oil (Bourbo~50 ' '' ~, : Musk Ambrette 50 '' '' .' :'' 'Coumarin 60 ., ~, .. ,: . . .. . .
' Amyl Salicylate . 60 ' Methyl ronone ~ 70 Cedarwood Oil (Americanl80 Clove. Stem Oil.~anzibar) 80 . Yeti~ert Oil '(Bourbon~ 80 '. Extended Patchouli Oil 13~
'~ ,' , . - La~andin Oil . -~40 '' 30 ~ ' , 1000 ,,: . . :
.
, - . Examp'l'e'XX
, The extended patchouli oil pxepared according to Example XIX is successfully incorporated into a com-pounded composition of the Chypre type ~y blending the following ingredients:

3f~

Parts Cinnamic Aldehycle E-thyl ~ethyl Phenyl Glyci~.ate ~lethyl Nonyl Acetaldeh~de 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~ XI) 40 Coumarin 50 Musk Ketone 50 Amyl Salicylate 60 Cedarwood Oil (American~60 : ~ Citronellol 60 -20 . Benzyl Acetate 80 Phenyl Ethyl Alcohol 150 -- Terpinyl Acetate . : _ ,, , . 1 0 0 0 ~ 25 Example-XXI
.';', . , '' ~, . '~ - ' ~ .
- ~ A patchouli oil extender base is prepared ~y blending tho foLLowing ingrodients: Yarts ~ -~- d-Limonene Dimer produced 38 - ~ according to Example IV(C) .
Guaioxide 27 Isolongifolene Oxidate 20 - . .

, .
, .

3~

Omega-hydroxym~thyl lonyifolen~ 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.

10 Example XXII ~.

The extended patchouli oil prepared according -to Example XVII is incorporated into a compounded perfumery composi-tion of the Fougere type containlng the followin~ ingre-dients:
. ..

Parts Balsam Peru 30 Labdanum Resin 30 : ~ Oakmoss Absolute . 30 ; - Sandalwood Oil (East Indian) 30 ~; .. ' ;: Linalyl Acetate 40 Terpinyl Acetate 40 .~ .. , . - . .
: . 25 Geranium Oil (Bourbon) - 50 -- Musk Ambrette ~ 50 - coumarin 60 : - Amyl Salicylate 60 : Methyl Ionone 70 . : .',. 30 . Cedarwood Oil (American) -80 Clove Stem Oil (Zanzibar)80 - - Vetivert Oil (Bourbon) 80 Extended Patchouli Oil 130 Lavandin Oil 140 ~ ' .. .
':

E~amDle XXIII

Preparation of dimerlzation _oclucts from ~ulf t~
tur~entine Into a 500 ml reaction flask equiPDed ~ith thermom2ter, stirrer, condenser and addition funnel are placed 5 g Primol R and 2 g of a 20~ phosphoric acid on silica catalyst produced by the Chemtron Corporation. The reaction mass is heated to 150C and 50 g of sulfate turpentine is added dropwise over a period of 2 hou-s with stirring. The reac-tion mass ls then heated for another 2 hours at 150C.

The reaction mass i5 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 catalvst. The resultir.g ', ' 20 dimerization products are then com~ined and distilled - , and used in,the following examples.

"', ',~,;''' -Exam~le XXIV -~
. .
,. . - -. . -,,. - 25 Yetiver Oil (70 partsl 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 su~stantially not modified~
Example~-XX~ -': ' .
Sandalwood oil C75 partsl obtained from Indonesia is blended with the'dimerization product produced according '~ 35 to Example XXIII (25 ~arts). The dimerization product thus produced is found to act as an extender for the san-dalwood oil and that the characteristic odor effect of the latter is su~stantially not modified.

ExamPle XXVI
. .
Patchouli oil (80 parts) obtainecl from the Seychelle Islands is blended with the alpha methyl styren dimer-ization product produced according to Examle I, II or III (20 paxts). The alpha methyl styrene dimerization product is found to act as an extencler for the patchouli oil in that the characteristic oclor ef:Eect of the latter is substantially not modified.

Example XXVII

The exténded patchouli oil prepared according to Example XXVI is successfully incorporated into a compounded compo-Si~ .; 0~ Lhe Cnypre type by blending the following in-gredients:

Parts ~` ` - Cinnamic Aldehyde - Ethyl Methyl Phenyl ~lycidate Methyl Nonyl Acetaldehyde 2 ~ Oakmoss (Absolute) 20 Sandalwood Oil (East Indian)- 20 . .Vetiveryl Acetate 20 lang Oil No. 1 20 ~ - - Benzoin Resin ~Sumatra) 30 - - 30 Alpha Ionone (100%~ 30 . Clove Stem Oil (Zanzibar~36 - : Bergamot Oil 40 Hydroxycitronellal 40 .
Iso Eugenol - 40 . Extended Patchouli Oil (Ex. X~VI) 40 - Coumarin ~ 50 Musk Ketone 50 .

~7-Amyl Sa]ic~late 60 Cedarwood Oi.l (American) ~60 Citronellol 60 Benzyl Acetate ~0 Phenyl Ethyl Alcohol 150 Terpinyl Acetate 150 Example XXVIII
A patchouli oil extender base is prepared by blending the follo~ing 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 This mixture (46 parts~ is then blended with natural patchouli oil (Seychelles~ (60 partsl to provide a satisfactory extended patchouli oil~
.; 30 . - -~ i. Example XXIX -~
:, . ----The extended patchouli oil prepared in Examp:ie XXVIII
is incorporated into a compounded perfumery composition of the Fougere type containing the following ingredients:

3-~
-6~-Parts Balsam Peru 30 Labdanum Resin 30 : 5 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 Oil130 Lavandin Oil 140 ,, ' . ., ' . ~ .

. 25 .
, :' . . ' .. , . - .
. :. .,.; . " ' : . ' . .. 30 . . - , :
',' .' '' " ' ' - ' .

,: , ~ .

--69-- ! j * * * *
' The perEumed materials used in the present invention in acldition to their use .in auymentiny or enhancing the aroma of perfumed materials, colognes and perfumed art- .
icles will also have improved the deodorizing propexties

- 5 of such a consumable material when present in appropriate quantities.

' ' .

: ;20 .
., .
.. . ; , ::,' ! ;
.. . . .
~" ., 3 0 . : -- ~
, " , .. ' .
:, ~ - ' . 35

Claims (12)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A mixture of (A) a dimerization product of an alpha-methyl styrene or a methyl or other C2-C4 lower alkyl homologue thereof or mixture of same having one of the generic structures:

and or hydrogenated derivatives thereof or mixture of the foregoing wherein one of R5 and R5 is C1-C4 alkyl and the other of R5 and R5 is hydrogen or R5 and R5 are both C1-C4 alkyl; wherein the linerepresents 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 then the lineis no bond and when the line + + + +
is a carbon-carbon single bond then the line is a carbon-carbon single bond, said hydrogenated alpha methyl styrene dimerization product having at least one structure defined according to at least one of the generic structures selected from the group consisting of:

and wherein one of R5 and R5 is C1-C4 alkyl and the other is hydrogen or each of R5 and R5 is C1-C4 alkyl; wherein the dashed lines and the wavy line represent carbon-carbon single bonds or carbon-carbon double bonds with the pro-viso that when there is one double bond present in the ring having a wavy line and dashed lines, only the wavy line is a double bond and when there is more than one double bond present in the ring containing the dashed lines and the wavy line, 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 and (B) a reaction product selected from the group consisting of (I) one or more twenty carbon atoma contain-ing dimerization products of (i) one monocyclic terpene containing two carbon-carbon double bonds or (ii) two different monocyclic terpenes containing two carbon-car-carbon double bonds or (iii) one bicyclic terpene contain-in one carbon-carbon double bond or (iv) two different bicyclic terpenes, each containing one carbon-carbon double bond or (v) one monocyclic terpene containing two carbon-carbon double bonds and one bicyclic terpene con-taining one carbon-carbon double bond; (II) hydrogenation products of one or more twenty carbon atom containing said dimerization products of twenty atom-containing terpenes and one or more hydrogenation products of one or more twenty carbon atom containing said dimerization products of terpenes.

2. The mixture of Claim 1 wherein the reaction product (B) is a dimerization product selected from the group consisting of:

Dimerization products of alpha-pinene;
Dimerization products of beta-pinene;
Dimerization products of camphene;
Dimerization products of d-limonene, Dimerization products of turpentine;

Hydrogenated dimerization products of alpha-pinene;

Hydrogenated dimerization products of beta-pinene;

Hydrogenated dimerization products of camphene;

Hydrogenated dimerization products of d-limonene;

Hydrogenated dimerization products of turpentine;

Mixtures of said dimerization products; and Mixtures of said hydrogenated dimerization products.

3. The mixture of Claim 1 wherein the dimerization product (A) is an .alpha.-methyl styrene dimer having the structure:

4. The mixture of Claim 1 wherein the dimerization product (A) is a hydrogenated dimerization product having at least one structure selected from the group consisting of:

; ;

; ;

and

5. A single phase liquid compounded perfumery composition which comprises at least one natural perfumery oil, synthetic perfumery oil or synthetic perfumery chemical or a mixture of natural perfumery oils and synthetic perfumery oils or a mixture of natural perfumery oils and synthetic perfumery chemicals or a mixture of synthetic perfumery oils and synthetic perfumery chemicals with which there is intimately admixed from about 1 up to about 30 parts by weight of at least an odorless perfumery extender which is a mixture defined according to Claim 1, 2 or 4 per 100 parts by weight of said compounded single phase liquid perfumery composition.

6. A process for extending a perfumery product selected from the group consisting of natural perfumery oils, synthetic perfumery oils, synthetic perfumery chemicals, mixtures of natural perfumery oils and synthetic perfumery oils, mixtures of natural perfumery oils, synthetic perfumery oils and synthetic perfumery chemicals and mixtures of synthetic perfumery oils and synthetic perfumery chemicals without substantially altering the aroma thereof which comprises intimately admixing from about 1 up to about 30 parts by weight of a mixture of (A) one or more dimerization products selected from the group consisting of .alpha.-methyl styrene dimerization products and hydrogenated .alpha.-methyl styrene dimerization products, said .alpha.-methyl styrene dimerization products being defined by at least one generic structure selected from the group consisting of:

and wherein one of R5 and R5' is C1-C4 alkyl and the other of R5 and R5' is hydrogen or R5 and R5' are both C1-C4 alkyl;
wherein the line, represents 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 then the line is no bond and when the line + + + + + is a carbon-carbon single bond then the line is a carbon-carbon single bond, and said hydrogenated alpha methyl styrene dimerization product having at least one structure defined according to at least one of the generic structures selected from the group consisting of:

and wherein one of R5 and R5' is C1-C4 alkyl and the other is hydrogen or each of R5 and R5' is C1-C4 alkyl; wherein the dashed lines and the wavy line represent carbon-carbon single bonds or carbon-carbon double bonds with the proviso that when there is one double bond present in the ring having a wavy line and dashed lines, only the wavy line is a double bond and when there is more than one double bond present in the ring containing the dashed lines and the wavy line, 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 and (B) a reaction product selected from the group consisting of (I) dimerization products of (i) the same or different monocyclic ten carbon atom-containing terpenes containing two carbon-carbon double bonds, or (ii) the same or different bicyclic ten carbon atom-containing terpenes containing one carbon-carbon double bond, or (iii) a monocyclic terpene containing two carbon-carbon double bonds and a bicyclic terpene containing one carbon-carbon double bond and (II) hydrogenation products of said dimerization product, with from 70 up to 99 parts by weight of said perfumery product.

7. The process of Claim 6 wherein the reaction product is a dimerization product and the dimerization product is the dimerization product of camphene.

8. The process of Claim 6 or 7 wherein the dimerization product (A) is an .alpha.-methyl styrene dimerization product defined according to the structure:

9. The process of Claim 6 or 7 wherein the dimerization product (A) is a hydrogenated dimerization product of .alpha.-methyl styrene having a structure selected from the group consisting of:

; ;

; ;

and

10. The process of Claim 6 wherein the reaction product (B) is a dimerization product and the dimerization product is a dimerization product of .alpha.-pinene.

11. The process of Claim 6 wherein the reaction product (B) is a dimerization product and the dimerization product is a dimerization product of d-limonene.

12. The process of Claim 6 wherein the reaction product (B) is a dimerization product and the dimerization product is a dimerization product of turpentine.