CA1109396A - Perfumes with terpene dimerization (2o carbons) product or hydrogenation product of the dimerization product - 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 either (i) in the alternative or (ii) 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/or (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

L3~93i~l~6 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 .

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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.
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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;
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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~

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:

.. . .

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"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 ., .

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--~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~
. .

, -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~

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.

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~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~
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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:

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 .

:

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 ~> ~> i R5 \ C) ~/~

. - ;: . R5 ., .:
.. .. .

~ > ~ ~ \

~, , , 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~ ~

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 ~

3~

S R5 ~,~ R5 R~ R5 S ~

' ~. ~. ' ~ ~, : 25 -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~:

', ' , "' ' ' , ~ .

~ ~ ////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.

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 ' 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 `

~ ' `
, ,,, .

.
.

, (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~

Reaction Scheme "7:

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 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 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 ,51 ' 18' '' 77 19 - ' ' ' . . 9 1 4 2 2 ~ 119 100 , . 143 20 ¦ ,~ 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 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 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 - 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 '~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 -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 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 ~ 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 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 , -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 ,~ .- .
, 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 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 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 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 , ~ - - .
:

:

, ' ' ~' ~

Claims (3)

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

1. A compounded single phase liquid perfumery cornposition which comprises a natural perfumer oil or a synthetic perfume oil or a synthetic perfumery chemical or a mixture of two or more natural perfume oils or a mixture of two or more synthetic perfume oils or a mixture of two or more perfume chemicals or a mixture of one or more natural perfume oils, synthetic perfume oils and perfume chemicals with which there is intimately admixed a reaction product selected from the group consisting of (A) one or more twenty carbon atom containing dimerization products of (i) one monocyclic terpene containing two carbon-carbon double bonds or (ii) two different monocyclic terpenes containing two carbon-carbon double bonds or (iii) one bicyclic terpene containing 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 containing one-carbon-carbon double bond; (B) hydrogenation products of one or more twenty carbon atom containing said dimerization products of terpenes and (C) mixtures of one or more twenty carbon atom containing said dimerization products of terpenes and one or more of said hydrogenation products of one or more twenty carbon atom containing dimerization products of terpenes; said reaction product being present in a concentration of from about 1 up to about 30 parts by weight per 100 parts by weight of said compounded single phase liquid perfumery composition.

2. The compounded single phase liquid perfumery composi-tion of Claim 1 wherein the reaction product 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 dimeriziation products of turpentine;
Mixtures of said dimerization products and mixtures of said hydrogenated dimerization products.

3. 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 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 reaction 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, with from 70 up to 99 parts by weight of said perfumery product.