Alkylation of phenol by myrtenol

Article abstract of DOI:10.1007/s10600-011-9995-0

Alkylation of phenol by myrtenol in the presence of aluminum phenoxide and aluminum isopropoxide was studied in the temperature range 120-160°C. The reaction occurred with the formation of an array of alkylated phenols. Isomerization of the terpene substituent as a result of rearrangements of the bicyclic myrtenol structure was observed. The side reaction of myrtenol reduction occurred during the alkylation in the presence of aluminum isopropoxide. A significant number of compounds with two aromatic moieties was formed in the presence of aluminum phenoxide.

Full text of DOI:10.1007/s10600-011-9995-0

Chemistry of Natural Compounds, Vol. 47, No. 4, September, 2011 [Russian original No. 4, July-August, 2011]
ALKYLATION OF PHENOL BY MYRTENOL
*
A. A. Koroleva, I. Yu. Chukicheva,
I. V. Fedorova, and A. V. Kuchin
UDC 547.562.1+547.598+547.562.1ꢀ162+547.263ꢀ162
Alkylation of phenol by myrtenol in the presence of aluminum phenoxide and aluminum isopropoxide was
studied in the temperature range 120–160°C. The reaction occurred with the formation of an array of
alkylated phenols. Isomerization of the terpene substituent as a result of rearrangements of the bicyclic
myrtenol structure was observed. The side reaction of myrtenol reduction occurred during the alkylation in
the presence of aluminum isopropoxide. A significant number of compounds with two aromatic moieties was
formed in the presence of aluminum phenoxide.
Keywords: phenol, myrtenol, organoaluminum catalysts, alkylation.
Terpenophenols are known to exhibit a variety of biological activities [1–3]. The presence of isoprenyl substituents
modifies the role of the aromatic compounds, mainly by increasing their lipophilicity. This enhances the retention of the
prenylphenols in lipid cell membranes and the penetration through them [4]. The structure of the terpene substituent and the
terpenophenol in general can determine the type of activity. In this respect, studies elucidating the relationship between the
alkylation conditions and the resulting products are interesting. The goal of such investigations is to find the parameters that
facilitate the selective production of compounds with a given structure.
Herein the influence of two organoaluminum catalysts, aluminum phenoxide and aluminum isopropoxide, on the
products formed by alkylation of phenol (1) with myrtenol (2) (Scheme 1) is evaluated taking into account various thermal
regimes and reagent ratios. According to the literature [5–8], both catalysts are ortho-orienting.
Phenol, aluminum phenoxide, and aluminum diisopropoxide-phenoxide were alkylated by myrtenol at 120, 140, and
160°C. The catalysts were aluminum phenoxide (PhO) Al and aluminum isopropoxide (i-PrO) Al. (PhO) Al was produced
3
3
3
in situ by reacting phenol with metallicAl. (i-PrO) Al was transformed during the reaction into the mixed aluminum alkoxide-
3
phenoxide by reaction of equimolar amounts of phenol and (i-PrO) Al.
3
The alkylation with an equimolar ratio of aluminum alkoxides and myrtenol was carried out for 3 h with practically
complete conversion of myrtenol regardless of the nature of the organoaluminum component. The reaction with a catalytic
amount of the aluminum alkoxides occurred at temperatures of at least 160°C and continued for 8-15 h. The conversion of
myrtenol was 50–60%. The reaction products were a mixture of O- and C-alkylated phenols and myrtenol derivatives (numbering
of C atoms is given for convenience of reading spectra). These were monoalkylated phenols (3, 4); cyclic ethers (5, 8); a linear
ether (9); substituted phenols (10–16); dialkylated phenols 17 (chromone and o-substituted), 18 and 19 (ortho and o-substituted),
20 and 21 (ortho- and para-substituted); ortho-disubstituted phenol (22); myrtenol derivatives (22–27); and myrtenol derivatives
with two aromatic cores (28–33) (Scheme 1).
A variety of structures for the terpene substituent was noted in the alkylation products. The presence of a strained
cyclobutane moiety in the 2,6,6-trimethylcyclo[3.1.1]heptane skeleton of myrtenol was reflected in the chemical behavior of
this compound. The myrtenol structure can undergo Wagner–Meerwein rearrangement, the small ring of the bicyclic terpene
can open, and a Nametkin rearrangement can occur in the presence of electrophilic reagents, Bronsted and Lewis acids and as
a result of thermal treatment [9–11]. The presence of the double bond in the allyl position of myrtenol makes the hydroxyl
proton labile and explains the high reactivity of this terpene alcohol.
Institute of Chemistry, Komi Scientific Center, Ural Branch, Russian Academy of Sciences, 167982, Republic of
Komi, Syktyvkar, Russia, fax: (8212) 21 84 77, e-mail: chukicheva-iy@chemi.komisc.ru. Translated from Khimiya Prirodnykh
Soedinenii, No. 4, July–August, 2011, pp. 494–501. Original article submitted February 9, 2011.
©
556
0009-3130/11/4704-0556 2011 Springer Science+Business Media, Inc.

OH
10
OH
1
3
cat
6
3 - 33
+
7
5
1
2
8
1
9
8
8
3
5
9
10
1
7
1
1
5
3
7
3
5
3
6
7
5
O
6
9
1
3
5
8
O
7
11
9
10
O
12
O
3
5
12
O
5
6
12
O
8
O
1
10
12
3
1
7
12
12
6
11
7
10
11
10
10
11
9
13
11
11
11
10
4
5
6
7
9
15
7
8
3
5
OH
HO
12
7
9
OH
12
10
11
10
12
5
6
8
7
1
5
3
9
OH
3
1
5
1
1
14
11
8
11
11
HO
13
7
11
6
3
10
OH
10
3
3
8
12
5
1
10
7
OH
9
14
11
12
10
5'
7'
3'
6'
1'
7'
1'
3'
10
10'
12
OH
O
10
12
3
11
3
3
12
O
9'
1
7
10
11
6
6
5
12
11
6
13
11
8'
10'
5'
1
5
OH
3
5
1
1
7
7
6
7
17
15
16
18
1
5
10
5
7
6
OH
7
10
9
OH
3
5
5
12
12
6
11
11
O
1
8
3'
5'
6'
3
OH
11
1'
1
10
11
5'
12
3
7'
12
7
5
7
10
1
15
1'
10'
15
1'
6
3'
3'
8'
9'
10'
3
8'
3'
10'
6'
7'
10'
9'
5'
5'
7'
1'
19
20
21
22
12' OH
O
OH
5'
11'
7
6'
3
1
3'
7'
O
12
10
6
5
1
8
1'
O
7
10'
5
11
3
9
23
24
25
26
27
28
10
7
1
7
1
OH
7
12'
12'
11'
12
OH
O
11
12
12
7
1
11'
1
8
3
5
3
5
9
OH
10
11
11
3
11
12
O
10
8
5
8
11'
O
9
10
3
11
10
5
1
7
11'
11'
6
5
3
HO
HO
9
12
O
12'
12'
OH
8
9
10
29
30
31
33
32
Scheme 1
The use of organoaluminum catalysts for the alkylation has its own pecularities. Certain studies showed that the
reaction of terpenes with phenols involving such catalysts occurred in aluminum. It was assumed during the alkylation of
phenol by myrtenol that the terpene alcohol O atom first coordinated to the Al atom of the catalyst. Then, the terpene underwent
isomerization (in certain instances) and was bonded to phenol (Scheme 2).
557

TABLE 1. Alkylation of Phenol by Myrtenol in the Presence of (i-PrO) Al
3
Mass part of reaction products, %
phenol derivatives with
one terpene substituent
phenol derivatives with
two terpene substituents
Myrtenol conversion, %
ꢁ
T, Ñ
8
9
1
2
3
4
5
6
7
PhOH–myrtenol–( -PrO) Al, 1:1:1
i
3
120
140
160
96
98
95
11
–
–
12
2
–
9
39
15
–
–
–
–
–
–
20
7
–
9
–
15
37
61
24
33
17
37
PhOH–myrtenol–( -PrO) Al, 1:1:0.1
i
3
160*
60
–
–
–
2
–
25
36
______
1, ethers; 2, cyclic ethers; 3, ortho-substituted phenols; 4, para-substituted phenols; 5, O–C-substituted phenols (chromans);
6, O–C-substituted phenols; 7, C–C-substituted phenols; 8, myrtenol derivatives; 9, unidentified products.
*Reaction continued for 8 h; reaction did not go at 120 and 140ꢁC.
X
X
OH
OH
OH
+
+
9, 10, 15,
27, 33
6, 7
RO
RO
OR
(RO) Al
3
+
Al
X =
I
II
X
X
OH
OH
X
R = Ph- or i-Pr-
+
OH
+
5
3
+
+
4, 8, 11, 13,
14, 21, 28 - 32
III
V
IV
+
Scheme 2
Compounds 3–8, 11, 13, 14, 21, and 28-32 are examples of isomerization of the myrtenol substituent. One of the two
terpene substituents in 17 and 19 isomerized. Phenol derivatives 9, 10, 15, 27, and 33 had a myrtenyl substituent.
Tables 1 and 2 present the experimental results. Table 1 shows the products of phenol alkylation by myrtenol in the
presence of aluminum isopropoxide.
The influence of temperature and amount of catalyst on the product yields could be found by analyzing the data in
Table 1. In particular, the alkylation did not proceed selectively with equimolar amounts of (i-PrO) Al, phenol, and myrtenol
3
at 120°C. A difficultly separated product mixture was observed. The major fractions were O-substituted phenol derivatives
such as ether 9 and the mixture of chromans 4 and 5 in 11 and 12% yields, respectively. Furthermore, ortho-terpenophenol 14
and disubstituted terpenophenol 20 (9 and 7%, respectively) were formed under these same conditions in an approximately
equal amount. The formation of monoalkylated ortho-terpenophenols was significant (39%) at 140°C. The structure of the
terpene substituent in 11, 13, and 14 had the para-menthane structure. The reaction mixture contained a significant (20%)
amount of 19, a phenol derivative substituted at the O atom and the C atom in the ortho-position of the aromatic ring.
Practically the same (26%) amount of disubstituted terpenophenols was formed at 160°C. However, a greater variety
of structures was formed. These included 17, 18, and 22. The total content of monoalkylated terpenophenols 14 and 15 was
15% under these conditions. Carrying out the reaction with catalytic amounts of (i-PrO) Al gave disubstituted phenol derivatives
3
17 and 18 (overall yield 37%). Table 2 presents results for the alkylation of phenol by myrtenol in the presence of aluminum
phenoxide.
558

TABLE 2. Alkylation of Aluminum Phenoxide by Myrtenol
Myrtenol
Mass part of reaction products, %
ꢁ
T, Ñ
phenol derivatives with one terpene substituent
conversion, %
5
6
7
8
1
2
3
4
(PhO)3Al–myrtenol, 1:1
120
140
160
97
98
96
–
–
1
18
50
12
23
17
–
–
–
–
–
–
2
37
33
15
–
–
13
22
57
PhOH–myrtenol–(PhO)3Al, 1:1:0.1
160*
50
5
–
9
4
–
–
18
64
______
1, ethers; 2, chromans; 3, ortho-substituted phenols; 4, para-substituted phenols; 5, dialkylated phenols; 6, diphenols; 7,
myrtenol derivatives; 8, unidentified products.
*Reaction continued for 8 h; reaction did not go at 120 and 140ꢁC.
The alkylation of aluminum phenoxide by myrtenol at 120 and 140°C occurred with formation of chromans, ortho-
monosubstituted phenols, and diphenols. The chroman content increased from 18 to 50% upon increasing the temperature
from 120 to 140°C whereas that of ortho-monosubstituted phenols decreased from 23 to 17%. Diphenols were formed in
approximately equal amounts, 37 and 33%, respectively, under these temperature conditions. Increasing the temperature
further to 160°C produced a large amount of polymeric products and resins. Chromans (12%), diphenols (15%), and insignificant
amounts of ethers and disubstituted phenols (1 and 2%, respectively) were isolated under these conditions. Compound 6 was
formed regardless of the reaction temperature. Its maximum content (34% of total reaction products) was found at 140°C
whereas it was obtained in 11 and 10% at 120 and 160°C, respectively. Derivative 6 with a bornyl moiety was the dominant
chroman for the reaction at 160°C. The content of 3 was only 2%. Phenol derivatives with the chroman structure 7 were
obtained in 7% yield at 120°C; chroman 8, 16% at 140°C. Monoalkylated orto-substituted phenols included two basic structures.
Compound 12 was formed at 120°C (20% of total amount of reaction products); 16, at 140°C (17%).
A distinguishing feature of the alkylation of (PhO) Al by myrtenol was the presence in the reaction products of
3
compounds with two aromatic cores (28–33). Heating to 120°C gave mainly phenol derivative 29 (21.6%). Increasing the
temperature further did not enhance the selective formation of any product.
Phenol reacted with myrtenol in the presence of a catalytic amount of (PhO) Al at temperatures of at least 160°C for
3
8 h. The myrtenol conversion was 50%. The products included ether 9, 5%; ortho-substituted phenol 15, 9%; and para-
substituted phenol 10, 4%. Polymerization products were also present.
Myrtenol derivatives myrtanol (24), myrtenal (23), myrtenol ether (27), and ꢂ-pinene (25) and limonene (26) were
formed in addition to the alkylation products via the reaction of phenol with myrtenol in the presence of organoaluminum
catalysts (i-PrO) Al and (PhO) Al. The presence of myrtanol (24) in the reaction products was explained by a Meerwein–
3
3
Ponndorf–Verley reduction [12] that occurred in the presence of aluminum isopropoxide. Alkylation of phenol by myrtenol
using equimolar amounts of (i-PrO) Al at 140°C formed 15% myrtanol and at 160°C, 37% myrtanol of the total amount of
3
reaction products. Carrying out the reaction with a catalytic amount produced 19% myrtanol. Myranol was observed in the
products of the reaction occurring in the presence of (PhO) Al (160°C, reagent method, 13% of total amount of reaction
3
products). Myrtenal (23) was formed by the reaction with a catalytic amount of (i-PrO) Al (6%) and (PhO) Al (13%).
3
3
Another myrtenol derivative, ether 27, which was obtained in 5% yield as a result of intermolecular dehydration of the alcohols
[13], was identified in the products of phenol alkylation in the presence of (PhO) Al.
3
A comparison of the action of (PhO) Al and (i-PrO) Al found that both catalysts were primarily ortho-orienting. The
3
3
optimum temperature range for phenol alkylation by myrtenol was 120–140°C. Selective alkylation occurred with a reagent
amount of the organoaluminum compound. The main products in the presence of (i-PrO) Al were ortho-substituted phenols,
3
among which 11 dominated. The chroman fraction was large with 6 predominating in the presence of (PhO) Al.
3
Other features were evident for each of the alkoxides. First, diphenols were formed if (PhO) Al was used. Derivatives
3
28–31 had the chroman structure with a second aromatic ring bonded to the terpene. Terpenophenols similar to 32 [14] were
prepared by reacting an excess of phenol with unsaturated terpenes such as ꢃ-terpinene, 3-carene, sabinene, limonene, and
559

ꢂ-pinene on Amberlite ion-exchange resin. In this instance, two phenols in the para-position relative to the phenol hydroxyl
were added to the terpene. Ortho-substituted derivatives were formed in the presence of (PhO) Al.
3
Second, phenol was disubstituted by terpenes in the presence of (i-PrO) Al with compounds of structures 17–19
3
dominating. The reaction of myrtenol and phenol in the presence of (i-PrO) Al was accompanied by reduction of myrtenol to
3
myrtanol as a side reaction.
EXPERIMENTAL
IR spectra were recorded in thin layers and KBr pellets on a Shimadzu IR Prestige 21 IR-Fourier spectrometer; PMR
13
and C NMR spectra, in CDCl on a Bruker Avance 300 (operating frequency 300 and 75 MHz, respectively) using CHCl
3
3
13
resonances (ꢄ 7.26 ppm, ꢄ 76.90 ppm) as internal standards. Resonances were assigned using C NMR spectra recorded
H
C
in JMOD mode and 2D NMR spectroscopic methods. The purity of the starting materials was monitored and reaction products
were analyzed byGCon a Shimadzu GC-2010AF chromatograph using an HP-1 capillary column (60 m ꢅ 0.25 mm ꢅ 0.25 ꢆm;
100–240°C temperature regime; heating rate 6°C/min), a flame-ionization detector, and He carrier gas. The course of reactions
was monitored by TLC on Sorbfil plates. Compounds were detected using an alcohol solution of vanillin and heating to
100–150°C. Silica gel 60 (70–230 ꢆm) was used for column chromatography.
Alkylation of Aluminum Phenoxide by Myrtenol. A two-necked 100-mL flask equipped with a thermometer and
reflux condenser was charged with phenol (3.73 g, 39.6 mmol), heated to 160°C, treated in portions with Al (chips, 0.36 g,
13.2 mmol), and held at the temperature until the Al dissolved completely. The mixture was cooled to room temperature,
treated with myrtenol (2.0 g, 13.2 mmol), and held at the set temperature for 3 h. The course of the reaction was followed
using TLC (solvent system hexane:Et O, 9:1, detection by alcoholic vanillin/H SO ). When the reaction was finished the
2
2
4
mixture was transferred to a separatory funnel, treated with HCl solution (5 mL, 0.05 N), and extracted with Et O (2 ꢅ 15 mL).
2
The Et O extract was worked up with aqueous NaOH (5%, 2 ꢅ 5 mL), washed with H O and saturated NaCl solution, and
2
2
dried over anhydrous MgSO . The solvent was removed. The products were separated by adsorption column chromatography
4
over a column (30 ꢅ 0.8 cm) of Silica gel 60 (70–230 ꢆm) with elution by petroleum ether:Et O with increasing (from 0 to 4%)
2
fraction of Et O. The reagents were loaded simultaneously if (i-PrO) Al was used. The reaction mixture was worked up and
2
3
the reaction products were separated using the aforementioned methods.
Alkylation of Phenol by Myrtenol in the Presence of (PhO) Al or (i-PrO) Al. A two-necked 100-mL flask
3
3
equipped with a thermometer and reflux condenser was charged with phenol (0.56 g, 6.0 mmol), heated to 160°C, and treated
in small portions with aluminum chips (0.016 g, 0.6 mmol). After the Al was completely dissolved in the phenol, the solution
was cooled to 40°C and treated with myrtenol (1 g, 6 mmol). The reagents were loaded simultaneously if (i-PrO) Al (10% of
3
starting phenol) was used. The reaction was carried out maintaining the temperature at 160°C until myrtenol was fully
converted (GC and TLC monitoring). When the reaction was finished, the mixture was cooled, diluted with Et O, treated with
2
HCl solution (10%) to decompose the catalyst, and washed with saturated NaOH solution and water until neutral. The organic
layer was dried over anhydrous Na SO . The solvent was removed. The products were separated by adsorption column
2
4
chromatography over a column (30 ꢅ 0.8 cm) of SiO (100–200 mesh) with elution by petroleum ether:Et O with increasing
2
2
(from 0 to 4%) fraction of Et O.
2
2-tert-Butyl-3-ethyl-3-propylchroman (3) was prepared by alkylation using the reagent method in the presence of
(PhO) Al at 160°C (1.4% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 1.02 (3H, s, CH -9), 1.11 (3H, s, CH -8), 1.32 (2H, m, H-7), 1.53 (1H, m,
3
3
3
H-1), 1.74 (2H, m, H-6), 1.86 (2H, m, H-5), 3.15 (2H, s, H-10), 3.54 (1H, s, H-3), 6.82-7.16 (4H, m, H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 20.03 (C-9), 24.35 (C-6), 26.11 (C-8), 26.33 (C-5), 34.76 (C-7), 39.56
3
(C-10), 41.41 (C-2), 46.01 (C-4), 49.46 (C-1), 87.31 (C-3), 117.13 (C-13), 119.74 (C-15), 122.74 (C-11), 127.14 (C-14),
127.62 (C-16), 157.57 (C-12).
1-Isopropyl-2,4,4a,9-tetrahydro-3H-xanthene (4) was prepared by alkylation using the reagent method in the
presence of (i-PrO) Al at 120°C (7.4% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.99 (3H, d, J = 6.8, CH -10), 1.03 (3H, d, J = 6.8, CH -9), 1.51
3
3
3
(2H, m, H-5), 1.61 (2H, m, H-4), 3.00 (1H, m, H-8), 3.18 (2H, s, H-7), 4.46 (1H, m, H-3), 6.75-7.35 (4H, m, H-13-16).
560

13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 21.17 (C-10), 23.40 (C-4), 25.30 (C-6), 27.59 (C-8), 28.05 (C-7),
3
29.51 (C-4), 79.92 (C-3), 114.95 (C-13), 120.15 (C-15), 126.94 (C-11), 127.77 (C-14), 135.43 (C-2), 144.09 (C-1), 155.81
(C-12).
*
*
11-Isopropyl-12-methyl-8-oxatricyclo[7.3.1.0 2,7 ]trideca-2(7),3,5,11-tetraene (5) was prepared by alkylation using
the reagent method in the presence of (i-PrO) Al at 120°C (4.8% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.85 (3H, d, J = 6.8, CH -9), 0.90 (3H, d, J = 6.8, CH -10), 1.39
3
3
3
(2H, m, H-5), 1.50 (3H, s, CH -7), 2.44 (1H, m, H-8), 2.77 (2H, m, H-3), 3.00 (1H, m, H-6), 4.76 (1H, m, H-4), 6.92-7.22 (4H,
3
m, H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 15.14 (C-7), 20.60 (C-10), 20.60 (C-9), 27.03 (C-8), 29.20 (C-5),
3
34.99 (C-3), 39.77 (C-6), 82.59 (C-4), 114.76 (C-13), 119.76 (C-15), 127.18 (C-14), 128.89 (C-16), 132.02 (C-11), 134.34
(C-1), 136.57 (C-2), 153.00 (C-12).
3-tert-Butyl-2-ethyl-3-propylchroman (6) was prepared by alkylation using the reagent method in the presence of
(PhO) Al at 120°C (11.0% yield) and at 160°C (9.8% yield) and in the presence of (i-PrO) Al at 140°C (14.0% yield).
3
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.92 (3H, s, CH -8), 0.94 (3H, s, CH -9), 1.61 (2H, m, H-3), 1.76
3
3
3
(1H, m, H-4), 1.83 (2H, m, H-3), 2.11 (2H, m, H-5), 2.72 (2H, d, J = 14.3, H-10), 3.97 (1H, m, H-6), 6.77-7.10 (4H, m,
H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 19.77 (C-8), 20.47 (C-9), 24.20 (C-3), 25.67 (C-2), 33.95 (C-10),
3
38.48 (C-5), 44.76 (C-4), 45.11 (C-7), 46.89 (C-1), 81.11 (C-6), 116.63 (C-13), 120.13 (C-15), 122.01 (C-11), 126.75 (C-14),
129.39 (C-16), 156.80 (C-11).
3-tert-Butyl-3-methyl-2,4-diethylchroman (7) was prepared by alkylation using the reagent method in the presence
of (PhO) Al at 120°C (6.8% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.85 (3H, s, CH -10), 1.00 (3H, s, CH -9), 1.03 (3H, s, CH -8), 1.58 (2H,
3
3
3
3
m, H-3), 1.67 (1H, m, H-4), 2.46 (2H, m, H-5), 2.90 (1H, m, H-6), 4.57 (1H, m, H-2), 6.85–7.14 (4H, m, H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 12.28 (C-10), 18.75 (C-8), 19.57 (C-9), 36.05 (C-3), 38.93 (C-4),
3
39.51 (C-5), 41.96 (C-6), 42.78 (C-7), 49.11 (C-1), 80.25 (C-2), 116.39 (C-16), 119.91 (C-14), 126.75 (C-12), 127.24 (C-13),
129.99 (C-15), 153.57 (C-11).
1-Isopropyl-4-methyl-1,2,3,4-tetrahydrodibenzofuran (8) was prepared by alkylation using the reagent method in
the presence of (PhO) Al at 140°C (15.5% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.91 (3H, d, J = 6.64, CH -10), 0.94 (3H, d, J = 6.64, CH -9), 1.47
3
3
3
(3H, d, J = 6.92, CH -7), 1.69 (2H, m, H-6), 2.14 (2H, m, H-5), 2.39 (1H, m, H-8), 2.85 (1H, m, H-1), 3.10 (1H, m, H-4), 7.23–
3
7.61 (4H, m, H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 18.67 (C-7), 20.15 (C-10), 20.45 (C-9), 23.05 (C-5), 28.23 (C-1),
3
29.70 (C-8), 31.88 (C-4), 40.64 (C-6), 110.97 (C-13), 118.19 (C-3), 119.74 (C-16), 121.88 (C-15), 122.62 (C-14), 128.38
(C-11), 155.22 (C-2), 156.35 (C-12).
6,6-Dimethyl-2-phenoxymethylbicyclo[3.1.1]hept-2-ene (9) was prepared by alkylation using the catalytic method
in the presence of (PhO) Al at 160°C (5.3% yield) and the reagent method in the presence of (i-PrO) Al at 120°C (10.9%
3
3
yield).
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.92 (3H, s, CH -8), 1.37 (3H, s, CH -9), 1.27 (2H, m, H-7), 2.19 (1H, m,
3
3
3
H-5), 2.27 (1H, m, H-1), 2.47 (2H, m, H-4), 4.45 (2H, s, H-10), 5.67 (1H, m, H-3), 6.96-7.01 (3H, m, H-13-15), 7.30–7.35
(2H, m, H-12, 16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 21.10 (C-8), 26.24 (C-9), 31.32 (C-7), 31.58 (C-4), 38.13 (C-6), 40.95
3
(C-5), 43.33 (C-1), 70.63 (C-10), 114.93 (C-12, 16), 120.13 (C-3), 120.59 (C-14), 129.31 (C-13, 15), 144.07 (C-2), 159.04
(C-11).
4-(6,6-Dimethylbicyclo[3.1.1]hept-2-en-2-ylethyl)phenol (10) was prepared by alkylation using the catalytic method
in the presence of (PhO) Al at 160°C (4.0% yield), the reagent method in the presence of (i-PrO) Al at 140°C (5.0% yield),
3
3
and the catalytic method in the presence of (i-PrO) Al at 160°C (1.5% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.74 (3H, s, CH -9), 1.21 (3H, s, CH -8), 1.96 (2H, t, J = 2.8, H-4),
3
3
3
2.05 (1H, m, H-5), 2.30 (2H, m, H-7), 2.32 (1H, m, H-1), 3.20 (2H, s, H-10), 5.21 (1H, m, H-3), 6.61–7.03 (4H, m, H-12, 13,
15, 16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 20.01 (C-9), 26.24 (C-8), 31.37 (C-4), 31.82 (C-7), 38.23 (C-6), 40.71
3
(C-5), 42.61 (C-10), 45.44 (C-1), 114.93 (C-13, 15), 117.36 (C-3), 130.28 (C-12, 16), 134.01 (C-11), 147.05 (C-2), 155.50
(C-14).
561

2-[1-(4-Hydroxymethylcyclohexyl)-1-methylethyl]phenol (11) was prepared by alkylation using the reagent method
in the presence of (i-PrO) Al at 140°C (24.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.83 (2H, m, H-3), 0.87 (2H, m, H-5), 0.90 (2H, m, H-2), 0.92 (2H, m,
3
H-6), 1.28 (3H, s, CH -10), 1.30 (3H, s, CH -9), 1.69 (1H, m, H-1), 1.89 (1H, m, H-4), 3.23 (2H, m, H-7), 5.09 (1H, s,
3
3
CH OH), 6.76–7.25 (4H, m, H-13-16).
2
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 22.61 (C-10), 22.66 (C-9), 24.33 (C-2, 6), 25.88 (C-3, 5), 33.58
3
(C-1), 35.65 (C-8), 49.72 (C-4), 66.05 (C-7), 115.10 (C-13), 120.37 (C-15), 126.41 (C-14), 127.00 (C-16), 134.54 (C-11),
152.45 (C-12).
2-(2-Hydroxymethyl-6,6-dimethylbicyclo[3.1.1]hept-3-yl)phenol (12) was prepared by alkylation using the reagent
method in the presence of (PhO) Al at 120°C (19.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.90 (3H, s, CH -8), 1.25 (3H, s, CH -9), 1.95 (2H, m, H-7),
3
3
3
2.16 (2H, m, H-4), 2.33 (1H, m, H-2), 2.50 (1H, m, H-1), 2.54 (1H, m, H-5), 2.94 (1H, m, H-3), 3.49 (2H, d, J = 11.72, H-10),
6.83–7.16 (4H, m, H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 20.19 (C-8), 23.45 (C-7), 26.65 (C-9), 37.51 (C-3), 37.75 (C-5), 39.18
3
(C-6), 39.98 (C-2), 42.14 (C-1), 66.77 (C-10), 115.08 (C-13), 119.78 (C-15), 127.10 (C-16), 127.83 (C-14), 131.18 (C-11),
151.76 (C-12).
2-(4-Isopropenyl-1-methylcyclohex-3-enyl)phenol (13) was prepared by alkylation using the reagent method in
the presence of (i-PrO) Al at 140°C (7.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.83 (3H, m, CH -9), 0.88 (3H, m, CH -10), 1.53 (2H, m, H-6), 1.58 (2H,
3
3
3
m, H-5), 1.65 (1H, m, H-8), 1.68 (3H, s, CH -7), 1.99 (1H, m, H-4), 5.43 (1H, m, H-3), 5.48 (1H, m, H-2), 7.03–7.12 (4H, m,
3
H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 19.70 (C-9), 20.15 (C-10), 27.83 (C-5), 28.47 (C-7), 32.00 (C-8),
3
37.98 (C-6), 41.14 (C-4), 43.23 (C-1), 115.06 (C-13), 122.05 (C-15), 127.41 (C-16), 128.28 (C-14), 129.18 (C-2), 132.86
(C-11), 137.34 (C-3), 153.91 (C-12).
2-(4-Isopropenylcyclohex-1-enylmethyl)phenol (14) was prepared by alkylation using the reagent method in the
presence of (i-PrO) Al at 120°C (8.6% yield), at 140°C (2.0% yield), and at 160°C (6.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 1.53 (2H, m, H-5), 1.78 (3H, s, CH -7), 2.01 (1H, m, H-4), 2.20
3
3
(2H, m, H-6), 2.24 (2H, m, H-3), 3.39 (2H, s, H-10), 4.47 (2H, d, J = 1.5, H-9), 5.70 (1H, m, H-2), 6.84–7.22 (4H, m, H-13-
16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 21.09 (C-7), 27.63 (C-5), 28.53 (C-6), 29.20 (C-3), 37.74 (C-10),
3
40.72 (C-4), 108.84 (C-9), 115.08 (C-13), 117.22 (C-15), 122.21 (C-2), 124.86 (C-11), 127.18 (C-14), 130.12 (C-16), 136.57
(C-1), 149.64 (C-8), 153.97 (C-12).
2-(6,6-Dimethylbicyclo[3.1.1]hept-2-en-2-ylethyl)phenol (15) was prepared by alkylation using the catalytic method
in the presence of (PhO) Al at 160°C (9.3% yield) and the reagent method in the presence of (i-PrO) Al at 140°C (2.0% yield)
3
3
and at 160°C (9.0% yield).
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.85 (3H, s, CH -9), 1.21 (2H, m, H-7), 1.28 (3H, s, CH -8), 2.09
3
3
3
(2H, m, H-4), 2.14 (1H, m, H-5), 2.37 (1H, t, J = 5.6, H-1), 3.40 (2H, s, H-10), 5.47 (1H, t, J = 2.9, H-3), 6.84-7.20 (4H, m,
H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 20.82 (C-9), 26.25 (C-8), 31.32 (C-4), 31.49 (C-7), 38.01 (C-6), 39.03
3
(C-10), 40.63 (C-5), 45.37 (C-1), 116.02 (C-13), 118.68 (C-15), 120.56 (C-3), 126.54 (C-11), 127.98 (C-14), 131.01 (C-16),
147.05 (C-2), 155.07 (C-12).
2-(2,6,6-Trimethylbicyclo[3.1.1]hept-3-yl)phenol (16) was prepared by alkylation using the reagent method in the
presence of (PhO) Al at 120°C (4.3% yield) and at 140°C (17.3% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.88 (3H, s, CH -8), 0.91 (3H, m, CH -10), 1.21 (3H, s, CH -9), 1.76
3
3
3
3
(2H, m, H-7), 1.91 (2H, m, H-4), 2.14 (2H, m, H-2), 2.36 (1H, m, H-1), 2.51 (1H, m, H-5), 2.53 (1H, m, H-3), 6.77–7.12 (4H,
m, H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 19.82 (C-8), 21.66 (C-10), 23.28 (C-7), 24.25 (C-4), 26.77 (C-9),
3
31.59 (C-2), 35.07 (C-5), 36.22 (C-6), 41.04 (C-3), 49.21 (C-1), 115.18 (C-13), 120.05 (C-15), 126.77 (C-14), 130.74 (C-16),
132.48 (C-11), 152.75 (C-12).
4-(6,6-Dimethylbicyclo[3.1.1]hept-2-en-2-ylethyl)-9-isopropyl-8,9,10,10a-tetrahydro-6H-benzo[c]chromene (17)
was prepared by alkylation using the reagent method in the presence of (i-PrO) Al at 160°C (6.0% yield).
3
562

PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.84 (3H, s, CH -9), 1.33 (6H, s, CH -9ꢀ, 10ꢀ), 1.42 (3H, s, CH -8), 1.76
3
3
3
3
(2H, m, H-3ꢀ), 1.95 (1H, m, CH-8ꢀ), 2.08 (2H, m, H-5ꢀ), 2.18 (2H, m, H-4), 2.20 (1H, m, H-4ꢀ), 2.40 (2H, m, H-7), 2.42 (1H,
m, H-1), 2.52 (1H, m, H-5), 3.20 (2H, s, H-10), 3.32 (1H, m, H-6ꢀ), 4.51 (2H, s, H-7ꢀ), 5.26 (1H, m, H-3), 5.72 (1H, m, H-2ꢀ),
6.83–7.31 (3H, m, H-14-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 20.92 (C-10ꢀ), 20.94 (C-9ꢀ), 22.97 (C-9), 26.06 (C-8), 26.74 (C-3ꢀ),
3
26.93 (C-8ꢀ), 31.25 (C-5ꢀ), 31.39 (C-4), 36.96 (C-7), 37.85 (C-6), 38.05 (C-6ꢀ), 40.18 (C-4ꢀ), 43.16 (C-5), 44.77 (C-10), 51.23
(C-1), 70.47 (C-7ꢀ), 114.75 (C-13), 116.74 (C-15), 120.41 (C-2ꢀ), 120.73 (C-2), 122.24 (C-14), 126.54 (C-11), 128.64 (C-16),
143.90 (C-1ꢀ), 146.41 (C-2), 154.48 (C-12).
3-(2-((6,6-Dimethylbicyclo[3.1.1]hept-2-en-2-yl)methoxy)benzyl)-6,6-dimethylbicyclo[3.1.1]hept-2-ene (18) was
prepared by alkylation using the reagent method in the presence of (i-PrO) Al at 160°C (6.0% yield) and the catalytic method
3
in the presence of (i-PrO) Al at 160°C (12.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.82 (3H, s, CH -9), 0.83 (3H, s, CH -9ꢀ), 1.39 (3H, s, CH -8), 1.40 (3H,
3
3
3
3
s, CH -8ꢀ), 1.98 (2H, m, H-5, 5ꢀ), 2.10 (2H, m, H-4ꢀ), 2.13 (1H, m, H-1), 2.26 (2H, m, H-7ꢀ), 2.31 (1H, m, H-1ꢀ), 2.32 (2H, m,
3
H-4), 2.38 (2H, m, H-7), 3.88 (2H, s, H-10ꢀ), 4.48 (2H, s, H-10), 5.56 (1H, m, H-3ꢀ), 5.70 (1H, m, H-3), 6.81–7.37 (4H, m,
H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 20.89 (C-8, 8ꢀ), 26.57 (C-9), 26.63 (C-9ꢀ), 31.11 (C-7), 31.27 (C-4ꢀ),
3
31.59 (C-7ꢀ), 31.78 (C-4), 35.19 (C-6), 37.82 (C-6ꢀ), 40.30 (C-5), 41.11 (C-5ꢀ), 44.53 (C-10ꢀ), 51.30 (C-1ꢀ), 72.39 (C-10),
114.72 (C-16), 119.40 (C-3), 119.92 (C-14), 120.37 (C-3ꢀ), 127.59 (C-15), 129.10 (C-13), 130.52 (C-12), 145.45 (C-2ꢀ),
145.54 (C-2), 157.56 (C-11).
3-[2-(4-Isopropenylcyclohex-1-enylmethyl)phenoxy]-2,6,6-trimethylbicyclo[3.1.1]heptane (19) was prepared by
alkylation using the reagent method in the presence of (i-PrO) Al at 140°C (20.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.89 (3H, d, J = 9.3, CH -10), 0.93 (3H, s, CH -9), 1.33 (3H, s,
3
3
3
CH -8), 1.86 (3H, s, CH -10ꢀ), 1.87 (2H, m, H-5ꢀ), 1.92 (1H, m, H-1), 1.98 (1H, m, H-2), 2.00 (1H, m, H-4ꢀ), 2.02 (2H, m,
3
3
H-4), 2.04 (2H, m, H-7), 2.09 (2H, m, H-6ꢀ), 2.25 (2H, m, H-3ꢀ), 3.12 (2H, s, H-7ꢀ), 3.48 (1H, m, H-3), 4.85 (2H, s, H-9ꢀ), 5.19
(1H, m, H-2), 6.93–7.18 (4H, m, H-13-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 14.07 (C-10), 21.93 (C-10ꢀ), 22.28 (C-9), 27.65 (C-8), 28.05 (C-7),
3
28.68 (C-5ꢀ), 33.90 (C-6ꢀ), 36.15 (C-3ꢀ), 36.85 (C-4), 37.23 (C-7ꢀ), 39.21 (C-6), 39.63 (C-2), 42.09 (C-4ꢀ), 43.97 (C-5), 45.73
(C-1), 80.25 (C-3), 108.96 (C-9ꢀ), 109.51 (C-16), 119.85 (C-14), 120.14 (C-2ꢀ), 127.95 (C-15), 128.02 (C-13), 130.75 (C-12),
132.15 (C-1ꢀ), 150.32 (C-8ꢀ), 157.11 (C-11).
4-(6,6-Dimethylbicyclo[3.1.1]hept-2-en-2-ylethyl)-2-(2,6,6-trimethylbicyclo[3.1.1]hept-3-yl)phenol (20) was
prepared by alkylation using the reagent method in the presence of (i-PrO) Al at 120°C (8.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.79 (3H, s, CH -9ꢀ), 0.92 (3H, s, CH -9), 1.06 (3H, d, J = 7.3,
3
3
3
CH -10), 1.28 (3H, s, CH -8ꢀ), 1.31 (3H, s, CH -8), 1.75 (2H, m, H-4), 1.79 (2H, m, H-4ꢀ), 1.81 (1H, m, H-2), 2.01 (2H, m,
3
3
3
H-7ꢀ), 2.03 (1H, m, H-5ꢀ), 2.08 (1H, m, H-1ꢀ), 2.10 (1H, m, H-1), 2.27 (2H, m, H-7), 2.33 (1H, m, H-5), 2.37 (1H, m, H-3),
3.24 (2H, s, H-10ꢀ), 5.26 (1H, m, H-3ꢀ), 6.77-7.13 (3H, m, H-13, 14, 16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 19.84 (C-9), 20.29 (C-82), 21.61 (C-10), 26.25 (C-9ꢀ), 26.40 (C-8),
3
27.74 (C-7), 29.73 (C-4), 29.88 (C-4ꢀ), 31.38 (C-7ꢀ), 31.83 (C-2), 36.67 (C-6), 37.89 (C-6ꢀ), 40.73 (C-3), 41.09 (C-5), 41.34
(C-10ꢀ), 42.64 (C-5ꢀ), 45.46 (C-1), 46.21 (C-1ꢀ), 114.97 (C-13), 117.36 (C-3ꢀ), 129.87 (C-14), 130.27 (C-16), 131.42 (C-15),
131.67 (C-11), 147.72 (C-2ꢀ), 153.76 (C-12).
2,4-bis-[1-Methyl-1-(4-methylcyclohexyl)ethyl]phenol (21) was prepared by alkylation using the reagent method
in the presence of (PhO) Al at 160°C (2.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.88 (3H, m, CH -7), 0.90 (3H, m, CH -7ꢀ), 1.05 (3H, s, CH -9ꢀ), 1.08
3
3
3
3
(3H, s, CH -10ꢀ), 1.25 (2H, m, H-1, 1ꢀ), 1.27–1.30 (16H, m, H-2, 3, 5, 6, 2ꢀ, 3ꢀ, 5ꢀ, 6ꢀ), 1.39 (3H, s, CH -9), 1.42 (3H, s,
3
3
CH -10), 1.52–1.58 (2H, m, H-4, 4ꢀ), 7.19–7.62 (3H, m, H-13, 14, 16).
3
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 18.67 (C-7), 20.13 (C-7ꢀ), 23.05 (C-9, 10), 28.23 (C-9ꢀ, 10ꢀ), 29.72
3
(C-3, 3ꢀ, 5, 5ꢀ), 30.08 (C-2, 2ꢀ, 6, 6ꢀ), 31.95 (C-1, 1ꢀ), 37.12 (C-8ꢀ), 37.43 (C-8), 40.64 (C-4, 4ꢀ), 119.73 (C-13), 121.86 (C-16),
122.61 (C-14), 132.87 (C-11), 140.67 (C-15), 150.29 (C-12).
2-(6,6-Dimethylbicyclo[3.1.1]hept-2-en-2-ylethyl)-6-(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)phenol (22) was
prepared by alkylation using the reagent method in the presence of (i-PrO) Al at 160°C (9.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.79 (3H, s, CH -9), 0.85 (3H, s, CH -10ꢀ), 1.07 (3H, s, CH -9ꢀ), 1.09
3
3
3
3
(3H, s, CH -8ꢀ), 1.20 (3H, s, CH -8), 1.23 (2H, m, H-3ꢀ), 1.41 (2H, m, H-2ꢀ), 1.62 (2H, m, H-4), 1.66 (1H, m, H-4ꢀ), 1.78 (1H,
3
3
563

m, H-5), 2.07 (2H, m, H-5ꢀ), 2.20 (1H, m, H-1), 2.28 (2H, m, H-7), 3.41 (1H, m, H-6ꢀ), 3.90 (2H, s, H-10), 5.38 (1H, m, H-3),
6.62–7.15 (3H, m, H-14-16).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 11.40 (C-10ꢀ), 20.13 (C-9ꢀ), 21.08 (C-9), 22.60 (C-8ꢀ), 26.11 (C-8),
3
29.68 (C-3ꢀ), 31.12 (C-4), 31.33 (C-7), 31.79 (C-2ꢀ), 32.86 (C-5ꢀ), 37.64 (C-6), 40.99 (C-10), 42.25 (C-4ꢀ), 43.48 (C-5), 45.40
(C-1), 46.01 (C-1ꢀ), 49.34 (C-7ꢀ), 52.31 (C-6ꢀ), 115.32 (C-15), 120.43 (C-3), 125.83 (C-11), 129.35 (C-14), 129.56 (C-16),
130.14 (C-13), 147.14 (C-2), 155.85 (C-12).
The spectral properties of 23–26 agreed with those published earlier [15, 16].
2,2ꢀ-Oxy–bis-(methylene)-bis-(6,6-dimethylbicyclo[3.1.1]hept-2-ene) (27) was prepared by alkylation using the
catalytic method in the presence of (PhO) Al at 160°C (5.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.87 (6H, s, CH -8, 8ꢀ), 1.34 (6H, s, CH -9, 9ꢀ), 2.17 (2H, m, H-1, 1ꢀ),
3
3
3
2.19 (2H, m, H-5, 5ꢀ), 2.24 (4H, m, H-4, 4ꢀ), 2.41 (4H, m, H-7, 7ꢀ), 3.83 (4H, s, H-10, 10ꢀ), 5.26 (2H, m, H-3, 3ꢀ).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 21.08 (C-8, 8ꢀ), 29.98 (C-9, 9ꢀ), 31.46 (C-4, 4ꢀ), 31.54 (C-7, 7ꢀ), 38.00
3
(C-6, 6ꢀ), 39.85 (C-1, 1ꢀ), 43.47 (C-5, 5ꢀ), 72.57 (C-10, 10ꢀ), 119.41 (C-3, 3ꢀ), 145.63 (C-2, 2ꢀ).
*
*
2-(12-Isopropyl-8-oxatricyclo[7.3.1.0 2,7 ]trideca-2(7),3,5-trien-9-ylmethyl)phenol (28) was prepared by
alkylation using the reagent method in the presence of (PhO) Al at 140°C (1.4% yield) and at 160°C (2.3% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.97 (3H, d, J = 6.6, CH -9), 1.08 (3H, d, J = 6.6, CH -10), 1.26
3
3
3
(2H, m, H-5), 1.37 (1H, m, H-8), 1.62 (1H, m, H-4), 1.85 (2H, m, H-6), 2.32 (1H, m, H-3), 2.81 (2H, dd, J = 14.8, H-7), 3.06
(2H, m, H-2), 6.84–7.16 (8H, m, H-13-16, 13ꢀ-16ꢀ).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 19.51 (C-5), 19.70 (C-9), 21.20 (C-10), 26.23 (C-8), 28.15 (C-2),
3
33.89 (C-6), 34.13 (C-3), 44.43 (C-7), 48.97 (C-4), 79.99 (C-1), 114.92 (C-13), 117.43 (C-13ꢀ), 120.05 (C-15), 120.47
(C-15ꢀ), 123.08 (C-11ꢀ), 126.65 (C-11), 127.50 (C-16), 128.35 (C-14), 128.61 (C-14ꢀ), 132.51 (C-16ꢀ), 152.95 (C-12ꢀ), 154.75
(C-12).
*
*
2-(9-Isopropyl-8-oxatricyclo[7.3.1.0 2,7 ]trideca-2(7),3,5-trien-12-ylmethyl)phenol (29) was prepared by
alkylation using the reagent method in the presence of (PhO) Al at 120°C (21.6% yield), at 140°C (16.0% yield), and at 160°C
3
(0.6% yield).
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 1.11 (3H, d, J = 6.9, CH -9), 1.13 (3H, d, J = 6.9, CH -10), 1.61
3
3
3
(2H, m, H-5), 1.69 (2H, m, H-6), 1.82 (1H, m, H-8), 1.95 (1H, m, H-1), 2.24 (2H, m, H-3), 2.90 (2H, m, H-7), 3.03 (1H, m,
H-2), 6.83–7.19 (8H, m, H-13-16, 13ꢀ-16ꢀ).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 17.08 (C-9), 17.25 (C-10), 21.58 (C-3), 25.00 (C-5), 30.04 (C-6),
3
31.85 (C-7), 36.63 (C-8), 37.74 (C-2), 40.91 (C-1), 79.42 (C-4), 115.06 (C-13ꢀ), 115.24 (C-13), 118.88 (C-15ꢀ), 120.10
(C-15), 127.15 (C-14), 127.32 (C-14ꢀ), 127.79 (C-16ꢀ), 128.11 (C-11ꢀ), 128.29 (C-16), 130.39 (C-11), 154.24 (C-12ꢀ), 156.81
(C-12).
*
*
2-[2-(9-Methyl-8-oxatricyclo[7.3.1.0 2,7 ]trideca-2,4,6-trien-12-ylmethyl)propyl]phenol (30) was prepared by
alkylation using the reagent method in the presence of (PhO) Al at 140°C (16.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 1.04 (3H, m, CH -9), 1.33 (2H, m, H-3), 1.69 (3H, s, CH -7), 1.87 (2H,
3
3
3
m, H-2), 1.89 (1H, m, H-4), 2.12 (1H, m, H-8), 2.37 (2H, m, H-6), 2.88 (2H, m, H-10), 2.93 (1H, m, H-5), 6.80–7.19 (8H, m,
H-13-16, 13ꢀ-16ꢀ).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 17.02 (C-9), 21.52 (C-3), 24.53 (C-2), 29.95 (C-7), 30.96 (C-6), 31.81
3
(C-10), 36.62 (C-5), 37.70 (C-8), 40.84 (C-4), 79.27 (C-1), 114.91 (C-13), 115.05 (C-13ꢀ), 118.82 (C-15), 120.84 (C-15ꢀ),
126.63 (C-16ꢀ), 127.24 (C-14), 127.53 (C-11ꢀ), 127.74 (C-11), 127.98 (C-16), 130.96 (C-14ꢀ), 153.68 (C-12), 156.77 (C-12ꢀ).
*
*
2-[1-Methyl-1-(12-methyl-8-oxatricyclo[7.3.1.0 2,7 ]trideca-2(7),3,5,-trien-9-yl)ethyl]phenol (31) was prepared
by alkylation using the reagent method in the presence of (PhO) Al at 120°C (4.0% yield) and at 160°C (2.3% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.93 (3H, m, CH -7), 1.42 (3H, s, CH -10), 1.44 (3H, s, CH -9), 1.68
3
3
3
3
(2H, m, H-6), 1.76 (1H, m, H-1), 2.03 (2H, m, H-5), 2.92 (2H, m, H-3), 2.97 (1H, m, H-2), 6.7–7.19 (8H, m, H-13-16, 13ꢀ-16ꢀ).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 17.05 (C-7), 23.99 (C-9, 10), 24.04 (C-6), 24.45 (C-3), 33.37 (C-5),
3
36.00 (C-1), 37.90 (C-2), 42.71 (C-8), 87.05 (C-4), 115.79 (C-16), 116.62 (C-13ꢀ), 119.73 (C-15ꢀ), 120.91 (C-14), 126.74
(C-13), 126.86 (C-16ꢀ), 127.78 (C-12), 128.53 (C-15), 135.74 (C-11ꢀ), 154.01 (C-12ꢀ), 158.68 (C-11).
2-(2-(3-(2-Hydroxyphenyl)-4-methylcyclohexyl)propan-2-yl)phenol (32) was prepared by alkylation using the
reagent method in the presence of (PhO) Al at 120°C (10.7% yield).
3
564

PMR spectrum (300 MHz, CDCl , ꢄ, ppm): 0.93 (3H, m, CH -7), 1.19 (2H, m, H-6), 1.29 (3H, s, CH -10), 1.32 (3H,
3
3
3
s, CH -9), 1.39 (2H, m, H-5), 1.51 (1H, m, H-1), 1.60 (2H, m, H-3), 1.76 (1H, m, H-4), 2.93 (1H, m, H-2), 6.7–7.19 (8H, m,
3
H-13-16, 13ꢀ-16ꢀ).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 17.19 (C-7), 24.25 (C-10), 26.24 (C-9), 29.95 (C-5), 31.83 (C-6),
3
34.76 (C-1), 36.64 (C-3), 40.86 (C-8), 42.73 (C-4), 47.91 (C-2), 115.07 (C-13), 115.30 (C-13ꢀ), 120.03 (C-15), 120.43
(C-15ꢀ), 126.88 (C-14), 127.10 (C-14ꢀ), 127.73 (C-16), 128.57 (C-16ꢀ), 130.98 (C-11), 135.74 (C-11ꢀ), 153.83 (C-12), 154.01
(C-12ꢀ).
2-(6,6-Dimethyl-3-phenoxybicyclo[3.1.1]hept-2-ylmethyl)phenol (33) was prepared by alkylation using the reagent
method in the presence of (PhO) Al at 160°C (4.0% yield).
3
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.85 (3H, s, CH -9), 1.28 (3H, s, CH -8), 1.80 (2H, m, H-4), 1.82
3
3
3
(2H, m, H-7), 2.10 (1H, m, H-5), 2.18 (1H, m, H-2), 2.48 (1H, m, H-1), 2.93 (2H, dd, J = 3.8, 8.5, H-10), 4.71 (1H, m, H-3),
6.80–7.32 (9H, m, H-13-16, 12ꢀ-16ꢀ).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 20.05 (C-9), 26.83 (C-8), 27.77 (C-4), 29.96 (C-7), 36.26 (C-10),
3
36.46 (C-6), 41.07 (C-5), 45.89 (C-1), 82.58 (C-3), 115.22 (C-12, 12ꢀ), 115.47 (C-13), 120.08 (C-15), 120.88 (C-14ꢀ), 127.00
(C-11, 16), 127.45 (C-13ꢀ, 15ꢀ), 129.47 (C-16ꢀ), 152.19 (C-12), 159.07 (C-11ꢀ).
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