Palladium-catalyzed annulation reaction of o-bromobenzaldehydes with carbonyl compounds to produce naphthol and/or naphthalene derivatives

Article abstract of DOI:10.1016/S0040-4020(00)00043-0

o-Bromobenzaldehydes undergo annulation with 1,3-diaryl-2-propanones in the presence of a palladium catalyst to give the corresponding 1,3-diaryl-2- naphthols in fair to good yields. From the reaction of the aldehydes with 2- substituted 2-alkenals are fo

Full text of DOI:10.1016/S0040-4020(00)00043-0

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 1315–1320
Palladium-Catalyzed Annulation Reaction of
o-Bromobenzaldehydes with Carbonyl Compounds to
Produce Naphthol and/or Naphthalene Derivatives
*
Yoshito Terao, Tetsuya Satoh, Masahiro Miura and Masakatsu Nomura
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
Received 13 December 1999; accepted 13 January 2000
Abstract—o-Bromobenzaldehydes undergo annulation with 1,3-diaryl-2-propanones in the presence of a palladium catalyst to give the
corresponding 1,3-diaryl-2-naphthols in fair to good yields. From the reaction of the aldehydes with 2-substituted 2-alkenals are formed 2,4-
disubstituted 1-naphthols and/or 1,3-disubstituted naphthalenes accompanied by decarbonylation. ᭧ 2000 Elsevier Science Ltd. All rights
reserved.
Introduction
benzaldehydes with 1,3-diaryl-2-propanones affords the
corresponding 1,3-diaryl-2-naphthols which are of interest
as bulky oxygen ligands.1
1–13
Furthermore, the bromo-
Palladium-catalyzed arylation reactions using aryl halides
and their synthetic equivalents such as aryl triflates are now
recognized to be of genuine synthetic utility for preparing
aldehydes have been observed to couple with 2-substituted
2-alkenals, interestingly accompanied by decarbonylation,
to give 2,4-disubstituted 1-naphthols and/or 1,3-disubsti-
tuted naphthalenes. These new findings are described
herein. While palladium-catalyzed reactions of o-halo-
1
–3
substituted aromatic compounds.
In particular, the
reaction with alkenes (the Mizoroki–Heck reaction) and
that with organometallic compounds, especially with
organoboronates (the Suzuki–Miyaura coupling), are often
employed. Meanwhile, the reaction of ortho-functionalized
halobenzenes with unsaturated compounds, including
alkenes, alkynes and dienes, i.e. palladium-catalyzed
annulation, has also proven to be a powerful tool to construct
1
4,15
benzaldehydes with alkynes,
allyl or homoallyl
16
17
alcohols,
arylboronic acids
and active methylene
18
compounds under carbon monoxide to give indenones or
indenols, indenes or dihydronaphthalenes, polycondensed
aromatic compounds and benzofuranones, respectively,
have been reported, the present method employing arylation
of carbonyl compounds appears to be useful as a new,
convenient route leading to naphthol and/or naphthalene
derivatives.
1
–4
various heterocyclic and carbocyclic compounds.
Recently, several groups including ours have independently
reported that aryl halides can efficiently react with ketones
on their a-position without stoichiometric metalation under
the conditions similar to those for the Mizoroki–Heck
5
–8
Results and Discussion
reaction.
We also demonstrated that the arylation of
a,b-unsaturated carbonyl compounds regioselectively
occurs on their g-position. It may be reasonable to consider
9
When o-bromobenzaldehyde (1a) (1 mmol) was treated
with 1,3-diphenyl-2-propanone (2a) (1 mmol) in the
that the arylation reaction of the carbonyl compounds can
be extended to the annulation forming certain ring
systems. Indeed we observed that when benzyl ketones
and a,b-unsaturated carbonyl compounds are treated with
o-dibromobenzenes, benzofuran derivatives and benzo-
cyclobutane or indene derivatives, respectively, are
presence of Pd(OAc) (0.05 mmol) and PPh (0.2 mmol)
2
3
together with K CO (2 mmol) as base in refluxing o-xylene
2
3
at a bath temperature of 160ЊC for 5 h, 1,3-diphenyl-2-
naphthol (3) was produced in a yield of 54% (Scheme 1
and entry 1 in Table 1). The yield of product 3 was increased
up to 72% by using 2 mmol of 2a (Entry 2). Use of a
1
0
formed. In a further study of the annulation of carbonyl
relatively more effective base, Cs CO , in place of K CO
compounds, we have found that the reaction of o-bromo-
2
3
2
3
did not improve the reaction efficiency (Entry 3). The
reaction in toluene at 120ЊC was very sluggish (Entry 4).
Keywords: annulation; arylation; carbonyl compounds; palladium and
compounds.
The treatment of 2-bromo-5-methoxy-, 2-bromo-4,5-
*
Corresponding author. Tel.: ϩ81-6-8797361; fax: ϩ81-6-8797362;
e-mail: miura@ap.chem.eng.osaka-u.ac.jp
dimethoxy-, 2-bromo-5,6-dimethoxybenzaldehydes, (1b),
0
040–4020/00/$ - see front matter ᭧ 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(00)00043-0

1
316
Y. Terao et al. / Tetrahedron 56 (2000) 1315–1320
Scheme 2.
Scheme 1.
Table 1. Reaction of o-bromobenzaldehydes 1 with 1,3-diaryl-2-propa-
nones (reaction conditions: (1 mmol), (2 mmol), Pd(OAc)
0.05 mmol), PPh (0.2 mmol), K
60ЊC (bath temperature))
2
1
2
2
3
(
1
3
2
CO
3
(2 mmol) in o-xylene (5 cm ) at
Scheme 3.
a
Entry
1
2
Time/h
Product, % yield
b
c
1
2
3
4
5
6
7
8
9
1a
1a
1a
1a
1b
1c
1d
1a
1a
1e
2a
2a
2a
2a
2a
2a
2a
2b
2c
2a
5
5
4
5
7
4
3
3
3, 54
c
3, 72 (59)
3, 64
3, 18
d
d,e
f
4, 57 (45)
5, 51 (43)
6, 90 (75)
7, 60 (44)
8, 48 (45)
9, 52 (44)
8
2.5
1
0
a
GLC yield based on amount of 1 used. Value in parentheses indicates
isolated yield.
b
c
2
a (1 mmol) was used.
In entries 1 and 2, 0.32 and 1.23 mmol of 2a were recovered, respec-
tively. Recoveries of 2 in other entries were not determined.
Cs CO was used in place of K CO . Molecular sieves 4A (300 mg)
2 3 2 3
d
was also added.
Reaction in toluene at 120ЊC.
Product 4 was isolated after acetylation.
e
f
(
1c) and (1d) in place of 1a with 2a using K CO in o-xylene
2 3
gave the expected 1,3-diaryl-2-naphthols 4–6 (Entries 5–7).
From the reactions of 1a with 1,3-(4-methylphenyl)- and
1
2
,3-(4-chlorophenyl)-2-propanones, 2b and 2c, in place of
a were also obtained naphthols 7 and 8 (Entries 8 and 9).
The reaction of 1-bromo-2-naphthaldehyde (1e) with 2a
afforded 2,4-diphenyl-3-phenanthrol (9) (Scheme 2, Entry
1
0). These results may demonstrate generality of the present
method as a route to 1,3-diaryl-2-naphthols.
It seems reasonable to consider that the reaction of 1 with 2
proceeds via palladium-catalyzed arylation to give inter-
mediate A followed by base-catalyzed condensation (path
Scheme 4.

Y. Terao et al. / Tetrahedron 56 (2000) 1315–1320
1317
Table 2. Reaction of o-bromobenzaldehyde (1a) with 2-ethyl-2-hexenal
reaction was carried out in a mixed solvent of toluene–
DMF (Entries 2 and 4). Decrease in the amount of 1a to
1 mmol reduced the yield of 11 (Entry 3). Interestingly, with
(
(
(
10a) (reaction conditions: 1a (2 mmol), 10a (1 mmol), Pd(OAc)
2
0.05 mmol), PPh
3
2 3
(0.1 mmol), Cs CO (2 mmol), in Toluene-DMF
3
5 cm ) at 120ЊC)
a reduced amount of Pd(OAc) (0.01 mmol), 12 was selec-
2
3
a
Entry
Toluene:DMF (cm )
Time/h
Yield (%)
tively produced (Entry 6). On the other hand, use of K CO3
2
in place of Cs CO resulted in the formation of a significant
2
3
1
1
12
0
amount of 2,2 -diformylbiphenyl, neither 11 nor 12 being
detected by GC-MS. This may be due to the fact that the
allylic hydrogen in 10a is less acidic than the benzylic
hydrogen in 2.
1
2
3
5:0
3:2
3:2
4:1
0:5
0:5
10
1
1
1
1
51
67 (57)
30
10
10
19
7
b
c
4
5
6
64
49
5
15
50 (50)
d
Table 3 summarizes results for reactions using o-bromo-
benzaldehydes 1a–d and 2-substituted (E)-2-alkenals
10a–e, (E)-2-octenal (10f) or isophorone (10g). The
reactions of 1b and 1c with 10a and of 1a with (E)-2-
methyl-2-pentenal (10b) and (E)-2-propyl-2-hexenal (10c)
6
a
GLC yield based on amount of 10a used. Value in parentheses indicates
isolated yield.
b
c
d
Product 11 was isolated after acetylation.
1
a (1 mmol) was used.
using 0.05 mmol of Pd(OAc) in 3:2 toluene–DMF mixture
Pd(OAc) (0.01 mmol) and PPh
2
3
(0.04 mmol) were used.
2
gave the expected 1-naphthols 13–16 as the predominant
products (Entries 1–4). In each case a minor amount of the
corresponding naphthalene derivative was detected by
GC-MS. In contrast to these reactions, treatment of 1d
with 10a gave 1,3-diethyl-5,6-dimethoxynaphthalene (17)
in a yield of 76%, no 1-naphthol derivative being detected
(Entry 5). The reactions of 1a with 2-phenyl-2-pentenal
(10d) and 5-methyl-2-phenyl-2-hexenal (10e) also produced
naphthalenes 18 and 19 as the sole detectable coupling
products (Entries 6 and 7). From the reactions of 1a with
10f and 10g in refluxing o-xylene were obtained 4-butyl-2-
naphthaldehyde (20) and 1,2,3,4-tetrahydro-3,3-dimethyl-
anthracen-1-one (21) (Schemes 5 and 6).
5
–8
a in Scheme 3). Alternatively, dehydrative condensation
to give intermediate B may occur before the arylation (path
b). In order to determine which path is favorable, the reac-
tion mixture of 1a and 2a at a reaction time of 2 h was
analyzed by GC-MS. Neither A nor B could be detected,
only 3 together with the starting materials being observed.
This may be due to the fact that the intramolecular cycliza-
tion from A and/or B is relatively fast. Thus, the precedence
of paths a and b is not definitive.
When 1a (2 mmol) was treated with (E)-2-ethyl-2-hexenal
10a) (1 mmol) in the presence of Pd(OAc) (0.05 mmol),
(
2
PPh (0.1 mmol) and Cs CO (2 mmol) in toluene at 120ЊC
for 10 h, 2,4-diethyl-1-naphthol (11) (51%) was produced as
the major product together with 1,3-diethylnaphthalene (12)
Possible reaction sequences from 1 and 10 to naphthols and
naphthalenes are illustrated in Scheme 7. Base-catalyzed
dehydrative condensation of 1 and 10 to give intermediate
3
2
3
(
10%) (Scheme 4 and entry 1 in Table 2). Analysis of the
C
followed by palladium-catalyzed decarbonylative
reaction mixture by GC also confirmed that 1a completely
disappeared and ca. 0.3 mmol of benzaldehyde was formed
as a sole detectable by-product. Note that both 11 and 12
lack a carbonyl group in either 1a or 10a. The reaction in
DMF was considerably faster than in toluene, while the
relative product yields were comparable (Entry 5). It was
observed that the yield of 11 was increased when the
cyclization involving cleavage of the aldehyde C–H
bond
this route may be excluded, since it is not consistent with the
structures of products 18 and 19. On the other hand, the
structures of 16 and 20 as well as 18 and 19 may imply
that the initial reaction in each coupling of 1 and 10 is
15,19–21
could produce naphthalenes (path c). However,
palladium-catalyzed g-arylation to give intermediate D
9
(path d). To form 1-naphthols and naphthalenes from D,
Table 3. Reaction of o-bromobenzaldehydes 1a–d with 2-alkenals 10a–f
or isophorone (10g) (reaction conditions: 1 (2 mmol), 10 (1 mmol),
decarbonylation from one of the formyl moieties should
occur followed by dehydrogenative oxidation or dehydra-
tion. Palladium(0) and/or (II) species in the reaction
Pd(OAc)
2
(0.05 mmol), PPh
3
(0.1 mmol), Cs
2
CO
3
(2 mmol) in Toluene
3
3
(3 cm )-DMF (2 cm ) at 120ЊC)
a
Entry
1
10
Time/h
Product, % yield
b
1
2
3
1b
1c
1a
1a
1d
1a
1a
1a
1a
10a
10a
10b
10c
10a
10d
10e
10f
1
4
2
1
3
2
2
2
2
13, 60 (55)
b
14, 65 (60)
15, 52 (49)
16, 43 (43)
c
b
4
5
6
7
17, 76 (67)
18, 66 (62)
19, 77 (57)
20, 46 (38)
21, 78 (66)
Scheme 5.
d
8
d,e
9
10g
a
GLC yield based on amount of 10 used. Value in parentheses indicates
isolated yield.
Isolated after acetylation.
b
c
Reaction using 1a (0.6 mmol), 10c (0.3 mmol), Pd(OAc)
0.015 mmol), PPh (0.03 mmol), Cs CO (0.6 mmol).
Reaction in refluxing o-xylene.
PPh (0.2 mmol) was used.
2
(
3
2
3
d
e
3
Scheme 6.

1
318
Y. Terao et al. / Tetrahedron 56 (2000) 1315–1320
acetylated by treatment with acetic anhydride (2 mmol) in
3
pyridine (5 cm ) at room temperature for 2 h before the
chromatographic purification.
Product data
2
5
1
1
5
7
,3-Diphenyl-2-naphthol (3). mp 69–71ЊC; H NMR d
.32 (s, 1H), 7.35–7.44 (m, 4H), 7.48–7.55 (m, 5H), 7.59–
.63 (m, 2H), 7.69–7.71 (m, 2H), 7.84–7.87 (m, 2H);
13
C
NMR d 121.80, 123.66, 124.62, 126.41, 127.61, 128.04,
1
1
28.37, 128.44, 128.82, 129.46, 129.57, 129.63, 130.34,
31.20, 132.88, 134.61, 137.85, 147.65; MS m/z 296
ϩ
(M ). Anal. Calcd for C H O: C, 89.16; H, 5.44. Found:
22
16
C, 89.06; H, 5.46.
1
4
3
,3-Diphenyl-6-methoxy-2-naphthyl acetate (acetate of
). mp 116–116.5ЊC; H NMR d 1.68 (s, 3H), 3.92 (s,
H), 7.05 (dd, 1H, Jˆ2.4, 9.2 Hz), 7.20 (d, 1H,
1
Jˆ2.4 Hz), 7.36–7.88 (m, 3H), 7.41–7.47 (m, 6H), 7.54–
13
7
1
1
1
.56 (m, 2H), 7.79 (s, 1H); C NMR d 20.23, 55.37, 106.00,
19.14, 127.46, 127.57, 127.66, 128.00, 128.14, 128.21,
28.27, 129.17, 130.24, 131.92, 133.17, 134.88, 135.59,
ϩ
38.09, 141.79, 157.68, 169.44; MS m/z 368 (M ). Anal.
Scheme 7.
Calcd for C H O : C, 81.50; H, 5.47. Found: C, 81.37; H,
25 20 3
5
.54.
1
5,19–21
medium could participate in the decarbonylation
and
2
2
oxidation, while the detailed mechanisms as well as the
reason why only naphthalenes are produced in the cases
using 1d, 10d and 10e are not clear at the present stage.
Naphthaldehyde 20 may be formed by nucleophilic cycliza-
tion in intermediate D to give E followed by dehydration.
The reaction using 1a and 10g may similarly take place.
1,3-Diphenyl-6,7-dimethoxy-2-naphthol (5). mp 164–
165ЊC; H NMR d 3.74 (s, 3H), 3.99 (s, 3H), 5.15 (s, 1H),
1
6.70 (s, 1H), 7.14 (s, 1H), 7.38 (t, 1H, Jˆ7.3, 7.8 Hz), 7.45–
7.52 (m, 5H), 7.59 (t, 2H, Jˆ7.3, 7.8 Hz), 7.65–7.68 (m,
13
3H); C NMR d 55.60, 55.86, 103.78, 106.70, 121.25,
124.18, 127.36, 127.93, 128.12, 128.31, 128.43, 128.58,
1
1
29.49, 129.52, 131.04, 135.07, 138.12, 146.54, 147.85,
ϩ
50.00; MS m/z 356 (M ). Anal. Calcd for C H O : C,
24
20
3
Experimental
80.88; H, 5.66. Found: C, 80.79; H, 5.68.
1
13
H and C NMR spectra were recorded at 400 or 600 MHz
1,3-Diphenyl-5,6-dimethoxy-2-naphthol (6). mp 149–
150ЊC; H NMR d 3.95 (s, 3H), 4.02 (s, 3H), 5.19 (s, 1H),
1
and 100 MHz or 150 MHz, respectively, for CDCl solu-
tions. MS analysis was made by EI. GLC analysis was
carried out using a Silicone OV-17 glass column (f
2
and 2-propyl-2-hexenal (10c) were prepared by the
methods reported previously. Other starting materials were
commercially available. The solvents employed were puri-
fied by standard methods before use. The structures of all
3
7.14 (d, 2H, Jˆ3.4 Hz), 7.38–7.52 (m, 6H), 7.56–7.60 (m,
13
2H), 7.68–7.71 (m, 2H), 8.13 (s, 1H); C NMR d 57.09,
61.23, 116.13, 120.88, 121.69, 123.04, 124.38, 127.60,
128.31, 128.42, 129.28, 129.38, 129.64, 130.80, 131.14,
134.77, 138.14, 143.42, 146.48, 146.73; MS m/z 356
2
3
23
.6 mm×1.5 m). 1,3-Diaryl-2-propanones 2b and 2c
2
4
ϩ
(M ). Anal. Calcd for C H O : C, 80.88; H, 5.66.
24
20
3
Found: C, 80.69; H, 5.62.
1
new products were unambiguously determined by H and
13
1
C NMR with the aid of NOESY, COSY and COLOC
1,3-Di(4-methylphenyl)-2-naphthol (7). Oil; H NMR d
experiments.
2.42 (s, 3H), 2.47 (s, 3H), 5.33 (s, 1H), 7.28–7.42 (m,
1
3
9
H), 7.56 (d, 2H, Jˆ8.3 Hz), 7.79–7.82 (m, 2H);
C
General procedure for the reaction of
NMR d 21.23, 21.34, 121.67, 123.51, 124.67, 126.18,
o-bromobenzaldehydes 1 with carbonyl compounds 2 or 10
127.96, 128.82, 129.17, 129.26, 129.40, 130.15, 130.25,
1
31.03, 131.46, 132.91, 134.94, 137.35, 138.08, 147.84;
HRMS m/z (M ) calcd for C H O 324.1514, found
3
ϩ
In a 100 cm two-necked flask was placed K CO or Cs CO
2
3
2
3
24 20
(
2 mmol) which was then dried at 150ЊC in vacuo for 2 h.
324.1505.
Then, Pd(OAc) (0.01–0.05 mmol), PPh (0.04–0.2 mmol),
2
3
1
(1–2 mmol), 2 or 10 (1–2 mmol), 1-methylnaphthalene
1,3-Di(4-chlorophenyl)-2-naphthol (8). mp 159.5–
3
1
(ca. 100 mg) as internal standard and a solvent (5 cm ) were
160.5ЊC; H NMR d 5.16 (s, 1H), 7.34–7.46 (m, 7H),
13
added. The resulting mixture was stirred under N at 120–
7.56–7.61 (m, 4H), 7.80–7.84 (m, 2H); C NMR d
120.71, 123.99, 124.35, 126.83, 128.15, 128.64, 128.79,
129.15, 129.81, 129.91, 130.82, 130.88, 132.62, 132.83,
133.77, 134.64, 136.09, 147.47; MS m/z 364, 366, 368
2
1
60ЊC (bath temperature) for 1–21 h. After cooling, the
reaction mixture was extracted with diethyl ether and
dried over sodium sulfate. Products were isolated by column
chromatography on silica gel using hexane or hexane–
diethyl ether as eluent. In some cases, naphthols were
ϩ
(M ). Anal. Calcd for C H OCl : C, 72.34; H, 3.86; Cl,
22
14
2
19.41, Found: C, 72.22; H, 4.01; Cl, 19.37.

Y. Terao et al. / Tetrahedron 56 (2000) 1315–1320
1319
1
2
,4-Diphenyl-3-phenanthrol (9). mp 126–127ЊC; H NMR
14.99, 20.69, 23.20, 25.66, 32.53, 121.56, 124.02, 125.33,
126.01, 126.69, 127.24, 130.21, 131.34, 138.23, 142.44,
d 5.37 (s, 1H), 7.03–7.07 (m, 1H), 7.37–7.42 (m, 3H),
ϩ
7
3
.46–7.50 (m, 4H), 7.55–7.66 (m, 4H) 7.70–7.73 (m,
169.61; HRMS m/z (M ) calcd for C H O 256.1463,
17
20
2
1
3
H), 7.79 (dd, 1H, Jˆ1.0, 7.8 Hz), 7.89 (s, 1H); C NMR
found 256.1459.
d 123.83, 124.93, 125.51, 125.92, 127.32, 127.39, 127.55,
1
1
1
1
9
27.76, 128.38, 128.58, 128.73, 128.98, 129.00, 129.53,
29.94, 130.60, 130.67, 130.67, 133.87, 137.69, 138.13,
49.37; MS m/z 346 (M ). Anal. Calcd for C H O: C,
1,3-Diethyl-5,6-dimethoxynaphthalene (17): Oil; H NMR
d 1.33 (t, 3H, Jˆ7.6 Hz), 1.37 (t, 3H, Jˆ7.6 Hz), 2.79 (q, 2H,
Jˆ7.6 Hz), 3.04 (q, 2H, Jˆ7.6 Hz), 3.98 (s, 3H), 3.99 (s, 3H),
7.09 (s, 1H), 7.23 (d, 1H, Jˆ9.2 Hz), 7.65 (d, 1H, Jˆ9.2 Hz),
ϩ
2
6
18
0.14; H, 5.24. Found: C, 89.88; H, 5.08.
13
7
.79 (s, 1H); C NMR d 15.10, 15.54, 26.06, 29.39, 56.80,
1
2
,4-Diethyl-1-naphthyl acetate (acetate of 11). Oil; H
61.03, 113.70, 117.09, 120.05, 124.51, 126.62, 129.80,
ϩ
NMR d 1.28 (t, 3H, Jˆ7.3, 7.8 Hz), 1.39 (t, 3H, Jˆ7.3,
140.18, 142.04, 143.04, 148.11; MS m/z 244 (M ). Anal.
7
2
7
2
1
.8 Hz), 2.49 (s, 3H), 2.67 (q, 2H, Jˆ7.3, 7.8 Hz), 3.09 (q,
H, Jˆ7.3, 7.8 Hz), 7.25 (s, 1H), 7.47–7.50 (m, 2H), 7.74–
Calcd for C H O : C, 78.65; H, 8.25. Found: C, 78.52; H,
16
20
2
8.24.
1
3
.76 (m, 1H), 8.01–8.03 (m, 1H); C NMR d 14.32, 14.98,
1
0.66, 23.49, 25.68, 121.50, 124.00, 125.33, 126.03, 126.06,
27.23, 131.30, 131.58, 138.44, 142.10, 169.60; MS m/z 242
M ). Anal. Calcd for C H O : C, 79.31; H, 7.49. Found:
1-Methyl-3-phenylnaphthalene (18). mp 68–69ЊC;
H
NMR d 2.76 (s, 3H), 7.37 (t, 1H, Jˆ7.3, 7.8 Hz), 7.46–
ϩ
(
7,53 (m, 4H), 7.60 (s, 1H), 7.72 (d, 2H, Jˆ8.3 Hz), 7.89–
1
6
18
2
13
C, 79.19; H, 7.44.
7.91 (m, 2H), 8.00–8.02 (m, 1H); C NMR d 19.53,
1
23.99, 124.24, 125.79, 125.99, 126.35, 127.25, 127.38,
2
6
1
2
,4-Diethylnaphthalene (12). Oil; H NMR d 1.32 (t, 3H,
128.79, 128.83, 131.83, 133.86, 134.83, 138.18, 141.22;
MS m/z 218 (M ). Anal. Calcd for C H : C, 93.54; H,
6.46. Found: C, 93.42; H, 6.51.
ϩ
Jˆ7.3 Hz), 1.38 (t, 3H, Jˆ7.3 Hz), 3.07 (q, 2H, Jˆ7.3 Hz),
17
14
3
.09 (q, 2H, Jˆ7.3 Hz), 7.21 (s, 1H), 7.41–7.44 (m, 2H),
7
.48 (s, 1H), 7.77–7.79 (m, 1H), 7.98–8.01 (m, 1H);
1
3
1
C NMR
d
15.10, 15.42, 25.90, 29.01, 123.55,
23.94, 124.82, 125.40, 126.20, 128.24, 130.25, 134.17,
1-Isopropyl-3-phenylnaphthalene (19). Oil; H NMR d
1.46 (d, 6H, Jˆ6.6 Hz), 3.78–3.84 (m, 1H), 7.36–7.40 (m,
1H), 7.47–7.54 (m, 4H), 7.68 (d, 1H, Jˆ1.8 Hz), 7.72 (dd,
1
1
40.15, 141.44.
2
H, Jˆ1.1, 7.3 Hz), 7.89–7.93 (m, 2H), 8.14 (d, 1H,
13
2
1
1
,4-Diethyl-7-methoxy-1-naphthyl acetate (acetate of
Jˆ1.8 Hz); C NMR d 23.60, 28.68, 121.64, 123.21,
124.22, 125.70, 125.73, 127.24, 127.47, 128.79, 129.21,
130.58, 134.22, 138.22, 141.63, 145.22; MS m/z 246
(M ). Anal. Calcd for C H : C, 92.64; H, 7.36. Found:
C, 92.56; H, 7.53.
1
3). mp 79–80ЊC; H NMR d 1.26 (t, 3H, Jˆ7.8 Hz),
.36 (t, 3H, Jˆ7.8 Hz), 2.47 (s, 3H), 2.64 (q, 2H,
ϩ
Jˆ7.8 Hz), 3.01 (q, 2H, Jˆ7.8 Hz), 3.90 (s, 3H), 7.00 (d,
19
18
1
7
2
1
H, Jˆ2.4 Hz), 7.09 (s, 1H), 7.13 (dd, 1H, Jˆ2.4, 9.3 Hz)
1
3
.91 (d, 1H, Jˆ9.3 Hz); C NMR d 14.29, 15.07, 20.67,
1
3.58, 25.75, 55.16, 100.28, 117.42, 123.79, 125.78, 126.76,
4-Butyl-2-naphthaldehyde (20). Oil; H NMR d 0.98
(t, 3H, Jˆ7.3 Hz), 1.44–1.50 (m, 2H), 1.72–1.80 (m, 2H),
3.11 (t, 3H, Jˆ7.8 Hz), 7.58 (t, 1H, Jˆ8.3 Hz), 7.67 (t,
1H, Jˆ8.3 Hz), 7.80 (s, 1H), 8.01 (t, 1H, Jˆ8.3 Hz), 8.09
28.44, 132.31, 138.42, 141.36, 157.84, 169.51; MS m/z 272
M ). Anal. Calcd for C H O : C, 74.97; H, 7.40. Found:
ϩ
(
1
7
20
3
C, 74.94; H, 7.34.
13
(
d, 1H, Jˆ8.3 Hz), 8.19 (s, 1H); C NMR d 13.95,
2
1
1
7
3
1
1
1
,4-Diethyl-6,7-dimethoxy-1-naphthyl acetate (acetate of
22.82, 32.62, 32.70, 122.08, 124.24, 126.54, 128.91,
130.41, 133.13, 133.35, 133.68, 135.23, 140.55, 192.55;
1
4). mp 107–108ЊC; H NMR d 1.25 (t, 3H, Jˆ7.3, 7.8 Hz),
ϩ
.38 (t, 3H, Jˆ7.3, 7.8 Hz), 2.47 (s, 3H), 2.62 (q, 2H, Jˆ7.3,
.8 Hz), 3.01 (q, 2H, Jˆ7.3, 7.8 Hz), 3.98 (s, 3H), 4.00 (s,
HRMS m/z(M ) calcd for C H O 212.1201, found
212.1206.
15
16
1
3
H), 6.98 (s, 1H), 7.11 (s, 1H), 7.24 (s, 1H); C NMR d
4.42, 14.55, 20.71, 23.46, 25.90, 55.67, 55.83, 100.37,
03.20, 122.83, 124.45, 126.94, 130.04, 136.73, 141.36,
1,2,3,4-Tetrahydro-3,3-dimethylanthracen-1-one (21).
mp 105–105.5ЊC; H NMR d 1.10 (s, 6H), 2.59 (s, 2H),
1
ϩ
49.04, 149.63, 169.52; MS m/z 302 (M ). Anal. Calcd
for C H O : C, 71.50; H, 7.33. Found: C, 71.42; H,
3.00 (s, 2H), 7.46 (t, 1H, Jˆ8.3 Hz), 7.55 (t, 1H,
Jˆ8.3 Hz), 7.66 (s, 1H), 7.79 (d, 1H, Jˆ8.3 Hz), 7.95 (d,
1
8
22
4
13
7
.26.
1H, Jˆ8.3 Hz), 8.60 (s, 1H); C NMR d 28.25, 33.52,
4
3.78, 52.92, 125.95, 127.02, 127.44, 128.35, 128.51,
2
7
1
2
,4-Dimethyl-1-naphthol (15). mp 77–78ЊC; H NMR
d 2.37 (s, 3H), 2.59 (s, 3H), 4.92 (s, 1H), 7.08 (s, 1H),
129.82, 129.97, 131.68, 136.13, 137.66, 198.86; MS m/z
ϩ
224 (M ). Anal. Calcd for C H O: C, 85.68; H, 7.19.
16
16
7
1
1
.45–7.50 (m, 2H) 7.89–7.91 (m, 1H), 8.14–8.16 (m,
H); C NMR d 15.52, 18.64, 115.70, 121.38, 124.15,
Found: C, 85.64; H, 7.21.
1
3
24.52, 124.98, 125.16, 126.12, 129.49, 132.11, 146.93;
ϩ
HRMS m/z (M ) calcd for C H O 172.0888, found
1
2
12
172.0883.
Acknowledgements
4
-Ethyl-2-propyl-1-naphthyl acetate (acetate of 16). Oil;
This work was partly supported by a Grant-in-aid for
Scientific Research from the Ministry of Education,
Science, Sports and Culture, Japan. We thank Ms Y. Miyaji
of the Instrumental Analysis Center, Osaka University, for
helpful assistance in obtaining NMR spectra.
1
H NMR d 0.98 (t, 3H, Jˆ7.3 Hz), 1.38 (t, 3H, Jˆ7.3 Hz),
1
3
7
.66–1.71 (m, 2H), 2.48 (s, 3H), 2.61 (t, 2H, Jˆ7.8 Hz),
.07 (q, 2H, Jˆ7.3 Hz), 7.21 (s, 1H), 7.46–7.50 (m, 2H),
1
3
.72–7.74 (m, 1H), 8.00–8.02 (m, 1H); C NMR d 14.17,

1
320
Y. Terao et al. / Tetrahedron 56 (2000) 1315–1320
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