Cyclohexanol derivatives and fragrance compositions containing the same

Fragrant cyclohexanol derivatives are produced by condensing 2-ethylidene-5-norbornene with a phenol compound, in the presence of a Friedel-Crafts catalyst; and hydrogenating the condensation product in the presence of a metal catalyst. The compounds so produced have a green-floral odor and are advantageously used in soaps, detergents, shampoos, hair rinse, cosmetics, colognes and perfumes.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to cyclohexanol derivatives and fragrance 
compositions containing the same. 
2. Description of the Prior Art 
It is known that hydrogenated catecholcamphene adducts obtained by the 
hydrogenation of an adduct of camphene with catechol have a sandal odor. 
(Japan Patent Application Laid-Open No. 106,853/1977 and No. 
118,507/1982). It is also known that condensation of 
2-ethylidene-5-norbornene ("EBH") with phenol in the presence of a cation 
exchange resin gives a 1:1 condensation product. (Chemical Abstracts, Vol. 
84, 30579x (1974); Neft. Gaz, page 128 (1974)). 
While fragrant substances are known which have a green-floral type odor, 
many of the fragrance materials belonging to the green-floral odor type 
have an aldehyde group as a functional group. (Perfumer and Florist, 5 
(6), 1 (1980) and ibid., 6 (1), 1 (1981)). Unfortunately, the aldehyde 
group is known to be easily oxidizable and notoriously susceptible to 
attack by acids and alkalis. Hence, fragrant substances bearing an 
aldehyde group tend to be chemically labile or unstable. 
Additionally, many of the fragrant substances having a green-floral type 
odor have a relatively simple chemical structure and, hence, a low 
molecular weight, which results in the non-persistence of the odor. Hence, 
a need continues to exist for a fragrant substance or fragrance 
composition which has a green-floral type odor and which is chemically 
stable. Moreover, a need also continues to exist for such compositions or 
substances whose green-floral type odor is persistent. 
SUMMARY OF THE INVENTION 
Accordingly, it is an object of the present invention to provide a 
fragrance composition having a green-floral type odor which is chemically 
stable and not easily oxidizable or susceptible to attack by acids or 
alkalis. 
Moreover, it is also an object of the present invention to provide a 
fragrance composition having a green-floral type odor which is compatibile 
with, and can be incorporated with, soaps, detergents, shampoos, hair 
rinses and various types of comestics, cologne and perfume. 
According to the present invention, the foregoing and other objects are 
attained by providing a fragrant mixture comprising of least one 
cyclohexanol derivative having the formula:

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
According to the present invention, cyclohexanol derivatives are now 
available which can be used advantageously in the preparation of fragrance 
compositions. In particular, the cyclohexanol derivatives of the present 
invention are prepared by condensing 2-ethylidene-5-norbornene ("EBH") 
having the formula (I): 
##STR2## 
with a phenol compound of the formula (II): 
##STR3## 
wherein R is a hydrogen atom or a hydroxyl or lower alkoxy group, in the 
presence of a Friedel-Crafts catalyst; and hydrogenating the EBH-phenol 
compound adduct. 
When the EBH-phenol compound adducts are hydrogenated, the cyclohexanol 
derivatives of the present invention are produced. These derivatives have 
a green-floral type odor. 
In the production of the cyclohexanol derivatives according to the 
invention, EBH is first condensed with a phenol in the presence of a 
Friedel-Crafts catalyst. Examples of the phenol compounds to be used are 
phenol (in formula (II), R=H), catechol (R=OH), and guaiacol, guethol 
(o-ethoxyphenol) and the like (R=lower alkoxy having 1 to 4 carbon atoms). 
As the Friedel-Crafts catalyst, there may be used those acid cataylsts 
which are in general use, such as cation exchange resins, boron 
trifluoride, boron trifluoride etherate, boron trifluoride-acetic acid, 
boron trifluoride-phosphoric acid, boron trifluoride-methanol, celite, 
acid clay, sulfuric acid, aluminum trichloride, zinc chloride, stannic 
chloride and ferric chloride (G. A Olah: Friedel-Crafts Chemistry, 1973). 
The reaction is carried out by adding EBH dropwise to a solution of the 
phenol compound and Friedel-Crafts catalyst in an adequate solvent. The 
Friedel-Crafts catalyst is used in an amount of about 0.01 to 40 percent 
by weight based on the phenol compound. The molar ratio between the phenol 
and EBH is about 1:1 to 20:1, preferably about 1.5:1 to 10:1. 
As the solvent, a halogenated hydrocarbon, such as methylene chloride, 
chloroform or carbon tetrachloride, is preferred. While the reaction 
temperature depends on the catalyst species used, the reaction is 
generally carried out at about -10.degree. C. to 250.degree. C. For 
instance, when boron trifluoride-acetic acid is used, temperatures of 
about -10.degree. C. to 180.degree. C., especially room temperature to 
160.degree. C., are preferred, whereas when sulfuric acid, celite or acid 
clay is used, temperatures of about 50.degree. C. to 250.degree. C. are 
preferred. The reaction time also depends on the catalyst species used. 
Generally, the reaction is complete in 1 to 10 hours. 
The thus-obtained main product is considered, based on the .sup.1 -NMR data 
obtained, to be composed mainly of the following two compounds (III) and 
(IV): 
##STR4## 
wherein R is defined above. 
However, the condensation reaction between EBH and anisole as depicted 
below under "Alternative Synthesis 1" revealed that the EBH-phenol 
compound adduct is a compound of formula (III) (cf. Referential Example 
1). 
##STR5## 
The fact that various spectral data for the compounds (V) and (VI) obtained 
in the above confirmation reaction were in agreement with those for the 
compounds (VII) and (IX) obtained by an alternative method (Alternative 
Synthesis 2) proved that the structure of compounds (V) and (VI) are shown 
above (cf. Referential Examples 2-5). 
##STR6## 
The EBH-phenol compound adduct is then hydrogenated. It is necessary to 
perform this hydrogenation under such conditions that (1) hydrogenation of 
the aromatic ring, (2) elimination of other substituents than one phenolic 
hydroxyl group and (3) cleavage of the cyclopropane ring can take place. 
Such hydrogenation is effected by using a metal catalyst such as Raney 
nickel, nickel-on-diatomaceous earth, Raney cobalt, platinum, rhodium, 
ruthenium, ruthenium-on-active carbon or palladium. There is no particular 
limit to the amount of the catalyst. Preferably, however, the catalyst is 
used in the amount of about 0.1 to 20 percent by weight based on the 
above-mentioned EBH-phenol compound adduct. For instance, good results can 
be obtained by using about 1-20 percent by weight of Raney nickel or about 
0.1-5 percent by weight of ruthenium-on-activated carbon, each based on 
said adduct. The hydrogenation is carried out generally at a hydrogen 
pressure between about 1 atm. pressure and about 200 kg/cm.sup.2, 
preferably at about 10-150 Kg/cm.sup.2, more preferably at about 50-100 
Kg/cm.sup.2, and at a temperature of about 100.degree. C. to 300.degree. 
C., preferably about 130.degree.-230.degree. C. At temperatures below 
100.degree. C., the rate of reaction becomes slow, whereas, at 
temperatures exceeding 300.degree. C., the formation or hydrocarbons and 
other byproducts unfavorably increases. 
This hydrogenation reaction can be carried out either in the presence or in 
the absence of a solvent. However, the use of a lower alcohol such as 
methanol, ethanol or isopropyl alcohol, or a saturated hydrocarbon such as 
hexane or cyclohexane, for instance, is preferred. When a nickel catalyst 
is used, an alkaline substance or a neutral or acidic inorganic 
dehydrating agent may be added. 
The cyclohexanol derivatives obtainable in the above manner have the 
following physical characteristics: 
Appearance: Colorless viscous liquid; 
Boiling point: 95.degree.-125.degree. C./0.1 mmHg; 
Elemental analysis: C 78-82%; H 8-12%; O 7-14%. 
With respect to the molecular structure of the formed cyclohexanol 
derivative, compounds having the following three structures are formed 
depending on the mode of cleavage of the cyclopropane ring in the above 
hydrogenation reaction: 
##STR7## 
Moreover, with respect to the compounds having the formulas (X) to (XII), 
there are a number of possible isomers depending on the configuration of 
the cyclohexyl group and the configuration of the ethyl group. The use of 
gas chromatography with a capillary column has confirmed that the 
cyclohexanol derivative according to the present invention is a mixture of 
various isomers. 
The cyclohexanol derivative product according to the present invention has 
a green-floral type odor and has the following advantageous features: 
(1) Generally, many of the fragrance materials belonging to the 
green-floral odor type have an aldehyde group as the functional group 
(Perfumer and Florist, 5 (6), 1 (1980) and ibid., 6 (1), 1 (1981)) and the 
aldehyde group is easily oxidizable and susceptible to acids and alkalis, 
and therefore an instability problem is encountered. On the other hand, 
the compound according to the present invention is an alcohol free from 
such instability. 
(2) Many of the materials having a green-floral type odor have relatively 
simple chemical structures and are low in molecular weight, so that their 
odor is not persistent. On the other hand, the compounds according to the 
present invention contain 15 carbon atoms and have rather complicated ring 
structures, so that their odor remains persistent for a very long time. 
For instance, the odor is retainable for more than one month on filter 
paper. 
Accordingly, the cyclohexanol derivatives according to the present 
invention can be incorporated, in the form of a fragrance composition, 
into various products, such as soap, detergent, shampoo, hair rinse, 
various types of cosmetics, cologne and perfume. 
The present invention will be further illustrated by certain examples and 
references which are provided for purposes of illustration only and are 
not intended to limit the present invention. 
EXAMPLE 1 
(i) A solution composed of 372 g (3.0 moles) of guaiacol and 15 g of boron 
trifluoride-acetic acid was heated to 50.degree. C. while stirring. 
Thereto was added dropwise 120 g (1 mole) of EBH over 2.5 hours, while 
cooling in an adequate manner so as to prevent the temperature from rising 
with the progress of the exothermic reaction and to maintain the reaction 
temperature at 50.degree. C. After completion of the dropwise addition, 
stirring was continued at the same temperature for one additional hour. 
Thereafter, the reaction mixture was cooled to room temperature, followed 
by addition of 36 g of 15% aqueous sodium hydroxide. The aqueous layer was 
removed, and the organic layer was distilled under reduced pressure, 
whereby the unreacted starting guaiacol was first distilled off. Continued 
distillation under reduced pressure gave a product. 
Boiling point: 155.degree.-170.degree. C./0.1 mmHg; 
Yield: 34.7 g(14.2%). 
Gas chromatography-mass spectrometry of the product using Carbowax 20M (50 
m capillary column) gave a parent peak at m/e=244, indicating that the 
product was a 1:1 adduct of guaiacol with EBH. 
.sup.1 H-NMR (CDCl.sub.3, TMS internal standard, .delta.): 6.5 (complicated 
multiplet, aromatic ring hydrogens, 3H), 5.3 (phenol --OH), 3.7 (3H, 
--OCH.sub.3), 3.3-1.8 (complicated multiplet, 13H); 
IR (liquid film, cm.sup.-1): 3550, 3450, 3050, 2960, 2875, 1590, 1515, 
1490, 1465, 1380, 1350, 1320, 1270, 1200, 1130, 1100, 1080, 1060, 1040, 
960, 870, 850, 820, 795, 780, 760, 735. 
(ii) A 100-ml autoclave was charged with 20 g of the condensation product 
obtained in (i), 10 g of isopropyl alcohol and 2 g of Raney nickel, and 
hydrogenation was conducted at a reaction temperature of 
170.degree.-180.degree. C. and a hydrogen pressure of 50 Kg/cm.sup.2 
(gauge) with stirring for 3.5 hours. The product was rectified to give 
12.4 g (68%) of a viscous fraction boiling at 105.degree.-120.degree. 
C./0.35 mmHg. This fraction had a strong odor of the green-floral type. 
Gas chromatography-mass spectrometry of the product using Carbowax 20M (50 
m capillary column) revealed that 67.4% of the product was accounted for 
by cyclohexanol derivatives. The results of analyses are shown below: 
##STR8## 
Unhydrogenated material m/e=244 (20.3%) Others (12.3%) 
.sup.1 H-NMR (CDCl.sub.3, TMS internal standard, .delta.): FIG. 1 6.5 
(unhydrogenated aromatic ring), 3.7 (--OCH.sub.3) (unreacted methoxy 
group), 3.3-0.2 (complicated multiplet); 
IR (liquid film, cm.sup.-1): FIG. 2 3350, 2940, 2860, 1590, 1490, 1460, 
1380, 1270, 1100, 1050, 970, 780, 730, 
EXAMPLE 2 
(i) A solution composed of 744 g (6 moles) of guaiacol and 0.26 g of 
concentrated sulfuric acid was heated to 150.degree. C. while stirring. 
Thereto was added dropwise 240 g (2 moles) of EBH over 2.5 hours. After 
completion of the dropwise addition, the temperature was raised to 
200.degree. C. and stirring was continued at that temperature for 6 hours. 
Thereafter, the reaction mixture was cooled to room temperature, and 1.42 
g of 15% sodium hydroxide was added. After removal of the aqueous layer, 
the organic layer was distilled under reduced pressure, whereby the 
unreacted starting guaiacol was first distilled off. Continued 
distillation gave a product. 
Boiling point: 130.degree.-152.degree. C./0.1 mmHg, 
Yield: 152.9 g (62.7%) 
Gas chromatography-mass spectrometry of the product using a capillary 
column confirmed that the product contained the same compounds as those 
contained in the product of Example 1-(i), although two products differed 
in content of each constituent. 
EXAMPLE 3 
A 100-ml autoclave was charged with 20 g of the guaiacol-EBH adduct 
obtained in Example 1-(i), 10 g of ethanol and 1 g of 5% 
ruthenium-on-activated carbon, and hydrogenation was conducted at a 
reaction temperature of 150.degree. C. and a hydrogen pressure of 100 
Kg/cm.sup.2 while stirring for 4 hours. Rectification of the product gave 
12.9 g (71% yield) of a viscous fraction boiling at 99.degree.-115.degree. 
C./0.15 mmHg. This fraction had a strong odor of the same green-floral 
type as the fraction obtained in Example 1-(ii) and its physical 
characteristics data were almost the same as those for the fraction 
obtained in Example 1. 
EXAMPLE 4 
Rosy fragrance composition: 
______________________________________ 
Geraniol 130 (g) 
Citronellol 70 
Phenylethyl alcohol 593 
Nerol 50 
Geranium oil 20 
Palmorosa oil 20 
Benzyl acetate 20 
Hydroxycitronellal 40 
Linalool 25 
Octanol 1 
Octanal 1 
Geranyl acetate 10 
Phenylethyl acetate 10 
Citronellyl acetate 10 
1,000 
______________________________________ 
To 1,000 g of the above fragrance composition was added 50 g of the 
cyclohexanol derivative obtained in Example 1-(ii) to give a novel, fresh 
and rosy, retainable fragrance composition. 
EXAMPLE 5 
Fragrance composition for shampoo: 
______________________________________ 
Linalool 50 (g) 
Jasmine absolute oil 20 
Phenylethyl alcohol 150 
Rhodinol 150 
Rose absolute oil 10 
Hydroxycitronellal 300 
Indole 2 
4-(4-Hydroxy-4-methylpentyl)- 
78 
3-cyclohexene-1-carboxaldehyde 
.alpha.-Hexylcinnamic aldehyde 
150 
Cyclamen aldehyde 40 
Sandalwood oil 50 
1,000 
______________________________________ 
To 1,000 g of the above fragrance composition was added 50 g of the 
cyclohexanol derivative obtained in Example 1-(ii) to give a novel, fresh 
and retainable fragrance composition having a lily-of-the-valley-like 
odor. 
EXAMPLE 6 
Fragrance composition for soap: 
______________________________________ 
Citronellol 100 
Dimethylphenylethylcarbinol 
100 
Geraniol 100 
.alpha.-Hyxylcinnamic aldehyde 
150 
Hydroxycitronellal 200 
Phenylethyl alcoohol 250 
1,3,4,6,7,8-Hexahydro-4,6,6, 
20 
7,8,8-hexamethylcyclopenta- 
.gamma.-2-benzopyran 
p-tert-Butylcyclohexyl acetate 
50 
Acetylcedrene 30 
1,000 
______________________________________ 
To 1,000 g of the above fragrance composition was added 50 g of the 
cyclohexanol derivative obtained in Example 1-(ii), whereby a novel, fresh 
fragrance composition very well retainable on the skin was obtained. 
Referential Example 1 
Condensation product from EBH and anisole: 
Using 486 g (4.50 moles) of anisole, 180 g (1.50 moles) of EBH and 19 g of 
boron trifluoride-acetic acid, the procedure of Example 1-(i) was 
followed. Distillation gave a product. 
Boiling point: 130.degree.-160.degree. C./0.4 mmHg; 
Yield: 101 g (29.5%); 
GC-MS (Carbowax-20M, 50 m capillary column): 
m/e=228. 
The retention time data obtained by GC using a capillary column (Thermon 
600TK, 50 m) indicated that the product contained compounds (V) and (VI) 
as main products in proportions of 29.6% and 37.0%, respectively. These 
compounds were isolated by gas chromatography (Silicone SE-30, 2 m) and 
subjected to .sup.13 C-NMR spectrometry. The NMR data obtained for said 
compounds were in agreement with those for separately synthesized 
authentic samples (Referential Examples 3 and 4) of the main products 
(VII) and (IX), respectively. Gas chromatography-mass spectrometry using a 
capillary column revealed that the above condensation product contained 
isomers of the separately synthesized authentic samples (VII) and (IX), 
namely isomers differing in configuration of the aromatic ring, in a total 
amount of 7.7%. 
##STR9## 
Referential Example 2 
1-Ethyl-3-bromonortricyclene(1-ethyl-3-bromotricyclo[2,2,1,0.sup.2,6 
]heptane): 
To 120 g (1.0 mole) of EBH was added 172 g (1.0 mole) of 47% hydrobromic 
acid. The mixture was stirred vigorously at room temperature for 24 hours 
and, thereafter, extracted with 300 ml of ether and further with two 
100-ml portions of ether. The combined extract was washed with a 50-ml 
portions of saturated aqueous sodium chloride, and dried over magnesium 
sulfate. Unreacted EBH (282 g) was recovered by distillation under reduced 
pressure. Continued distillation gave a product. This product was composed 
of two isomers differing in configuration of bromine (72% and 28%). 
Boiling point: 88.0.degree.-90.0.degree. C./1.5 mmHg; 
Yield: 127.6 g (83% based on the reacted EBH). 
.sup.1 H-NMR (CDCl.sub.3, TMS internal standard, .delta.): 4.0 (1H, CH-Br), 
2.2-1.2 (complicated multiplet, 9H), 0.9 (3H, --CH.sub.3). 
IR (liquid film, cm.sup.-1): 3060, 2960, 2875, 1460, 1220, 895 800, 730. 
.sup.13 C-NMR (CDCl.sub.3, .delta.): 
For the major one (72%) of the two compounds produced (which presumably has 
the following configuration): 
##STR10## 
For the minor one (28%) of the two compounds produced (which presumably has 
the following configuration): 
Two peaks were unidentifiable as they overlapped with the peaks of the 
major product. 
##STR11## 
To confirm that the thus-obtained bromide has the carbon skeleton shown 
above, the bromide was subjected to debromination. That is, 10.1 g (50 
millimoles) of the above bromide, 20 ml of THF, 11.1 g (150 millimoles) of 
tert-butanol and 1.39 g (200 millimoles) of metallic lithium were added to 
a flask in that order at room temperature, followed by stirring for 30 
minutes. The mixture was further refluxed for an hour. After the reaction, 
10 ml of methanol was added for decomposing the excess lithium. The 
resulting mixture was poured into 100 ml of water and extracted with three 
100-ml portions of n-pentane. The extract was dried over anhydrous 
magnesium sulfate. The subsequent distillation gave a product. 
Boiling point: 138.degree.-140.degree. C., 
Yield: 4.53 g (74.3%), 
Purity (gas chromatography): 93.8% 
The .sup.13 C-NMR data for this product were in agreement with the 
literature data for 1-ethylnortricyclene [A. A. Bobyleva et al., Zh. Org. 
Khim., 13, 2085 (1977)]. 
.sup.13 C-NMR (CDC l.sub.3, .delta.c (intensity, multiplicity): 12.4(1,q), 
16.1(1.5,d), 23.1(1,t), 24.4(0,3,s), 31.8(1,d), 34.2(2,t), 36.4(1,t). 
Literature data: 
##STR12## 
12.4(C.sub.9), 16.3(C.sub.2 C.sub.6), 23.3(C.sub.8) 24.5(C.sub.1), 
32.0(C.sub.4), 34.3(C.sub.3 C.sub.5), 36.6(C.sub.7). 
Referential Example 3 
1-Ethyl-3-orthomethoxyphenylnortricyclene (VII): 
To a Grignard reagent prepared in a nitrogen atmosphere from 4.86 g (0.2 
mole) of magnesium turnings and an equivalent amount (37.4 g) of 
O-bromoanisole in ether (100 ml), there was added dropwise at room 
temperature a solution of 40.2 g (0.2 mole) of 
1-ethyl-3-bromonortricyclene (synthesized in Reference Example 2) in 
benzene (200 ml). Then, the ether was distilled off carefully under 
ordinary pressure. Thereafter, the benezene was refluxed for an hour. The 
reaction mixture was cooled with ice, 50 ml of 5% aqueous HCl was added 
dropwise, and the product was extracted with three 100-ml portions of 
ether. The extract was washed with one 50-ml portion of saturated aqueous 
sodium hydrogen carbonate and three 50-ml portions of saturated aqueous 
sodium chloride, and dried over magnesium sulfate. The product was 
distilled under reduced pressure and purified and isolated by column 
chromatography (Wakogel C-200). The product was a mixture of two compounds 
(exo and endo isomers with respect to position 3) and their contents were 
84% and 16%, respectively. The following physical constants are for the 
mixture as it is: 
Boiling point: 98.0.degree.-100.0.degree. C./0.02 mmHg; 
Yield: 19.1 g (40.9%); 
.sup.1 H-NMR (CDC l.sub.3, TMS internal standard, .alpha.): 7.3-6.6 
(complicated multiplet, 4H, aromatic ring hydrogens), 3.7 (3H, 
--OCH.sub.3), 3.1 (1H, Ar-CH); 2.1-1.2 (complicated multiplet, 12H). 
IR (liquid film, cm.sup.-1): 3050, 2960, 2930, 2860, 1600, 1580 1490, 1460, 
1440, 1240, 1110, 1050 1030, 875, 865, 785, 745, 720 .sup.13 C-NMR 
(CDCl.sub.3, .delta.c). 
.sup.13 C-NMR data for the major product (84% content): 157.3(s), 131.0(s), 
128.4(d), 126.8(d), 119.8(d), 109.5(d), 54.9(q), 44.8(d) 38.2(t), 36.0(d), 
30.1(t), 25.4(s), 23.3(t), 19.6(d) 16.8(d), 12.2(q). 
Referential Example 4 
1-Ethyl-3-paramethoxyphenylnortricyclene (IX): 
Using 2.43 g (0.1 mole) of magnesium turnings, an equivalent amount (18.7 
g) of p-bromoanisole and 20.1 g of 1-ethyl-3-bromonortricyclene, the 
procedure of Reference Example 3 was followed to give 
1-ethyl-3-paramethoxyphenylnortricyclene. The product was a mixture of two 
compounds (exo and endo isomers with respect to position 3: 78% and 22%). 
The following data were obtained using the mixture as it was: 
Boiling point: 103.0.degree.-105.0.degree. C./0.01 mmHg; 
Yield: 7.73 g (33.9%); 
.sup.1 H-NMR (CDCl.sub.3, TMS internal standard, .delta.); 7.2-6.6 (AA'BB' 
system, 4H, Ar--H), 3.1 (3H, --OCH.sub.3), 2.8 (1H, Ar-CH), 1.8-0.8 
(complicated multiplet, 9H); 
IR (liquid film, cm.sup.-1): 3050, 2960, 2940, 2875, 1625, 1585 1515, 1465, 
1250, 1180, 1105, 1040, 880, 860, 830, 795, 780, 755. 
.sup.13 C-NMR (CDCl.sub.3, .delta.c). 
.sup.13 C-NMR data for the major product (78% content): 157.7(s), 135.0(s), 
128.6(d), 113.2(d), 55.2(q) 49.4(d), 38.3(d), 37.8(t), 29.8(t), 26.0(s), 
23.2(t), 20.0(d), 16.4(d), 12.2(q). 
Referential Example 5 
1-Ethyl-3-metamethoxyphenylnortricyclene (VIII): 
Using 2.43 g (0.1 mole) of Mg turnings, an equivalent amount (18.7 g) of 
m-bromoanisole and 20.1 g of 1-ethyl-3-bromonortricyclene, the procedure 
of Referential Example 3 was followed to give 
1-ethyl-3-metamethoxyphenylnortricyclene. 
.sup.13 C-NMR (CDCl.sub.3, .delta.c): 159.3(s), 144.5(s) 128.7(d), 
120.2(d), 113.7(d), 113.2(d), 110.8(q), 54.9(d), 50.3(d), 38.3(d), 
30.0(t), 26.0(s), 23.2(t), 19.8(d), 16.5(d), 12.2(q). 
Having now fully described this invention, it will be apparent to one of 
ordinary skill in the art that many changes and modifications can be made 
thereto without departing from the spirit or scope of the invention as set 
forth herein.