Sequential and regioselective Friedel-Crafts reactions of gem-dihalogenocyclopropanecarbonyl chlorides with benzenes for the synthesis of 4-aryl-1-naphthol derivatives

Article abstract of DOI:10.1039/a605030a

Novel, sequential and regioselective Friedel-Crafts type reactions of (E)-3-aryl-2,2-dihalogenocyclopropanecarbonyl chlorides 1 and 2,2-dichlorocyclopropanecarbonyl chlorides 3 with benzenes produce various 4-aryl-3-halogeno-1-naphthols 2 and 4-aryl-1-naphthols 4, respectively. One of the benzannulations involves the intramolecular cyclization of acid chlorides 1, followed by intermolecular coupling with substituted benzenes to give 4-aryl-3-halogeno-1-naphthols 2. As a demonstration of this annulation, 4-aryl-3-bromo-1-naphthols 2i and 2k are successfully converted into new analogues of 1-aryl-3-hydroxymethyl-4-methoxy-2-naphthoic acid lactones 13, a class of lignan lactones. The other benzannulation involves three series of reactions using acid chlorides 3a-c: (1) the intermolecular Friedel-Crafts acylation of 3 with one benzene molecule giving the intermediary 2,2-dichlorocyclopropyl(phenyl)-methanones 14a-c; (2) the intermolecular trapping of 14a-c with another benzene molecule accompanied by regioselective ring opening; and (3) the final intramolecular cyclization giving 4-phenyl-1-naphthols 4a-c. The use of p-xylene also gives the corresponding 4-(p-xylyl)-1-naphthol 4d. The reactions of alternatively prepared ketones 14 with benzenes gives a variety of 'unsymmetrically' substituted 4-aryl-1-naphthols 4c,e-k under identical conditions. However, the reaction using p-methoxyphenyl ketone analogues 14g does not produce 4-aryl-1-naphthols, but gives 5-aryl-2-(p-methoxyphenyl)-3-methylfurans 16. These annulations proceed straightforwardly (in a one-pot manner) and this variation is due to the highly regioselective cyclopropane ring-openings.

Full text of DOI:10.1039/a605030a

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Sequential and regioselective Friedel–Crafts reactions of gem-
dihalogenocyclopropanecarbonyl chlorides with benzenes for the
synthesis of 4-aryl-1-naphthol derivatives
Yoshinori Nishii and Yoo Tanabe*
School of Science, Kwansei Gakuin University, 1-1-155 Uegahara, Nishinomiya, Hyogo 662,
Japan
N ovel, sequential and regioselective Friedel–Crafts type reactions of (E)-3-aryl-2,2-dihalogenocyclo-
propanecarbonyl chlorides 1 and 2,2-dichlorocyclopropanecarbonyl chlorides 3 with benzenes produce
various 4-aryl-3-halogeno-1-naphthols 2 and 4-aryl-1-naphthols 4, respectively. One of the benzannu-
lations involves the intramolecular cyclization of acid chlorides 1, followed by intermolecular coupling
with substituted benzenes to give 4-aryl-3-halogeno-1-naphthols 2. As a demonstration of this annulation,
4-aryl-3-bromo-1-naphthols 2i and 2k are successfully converted into new analogues of 1-aryl-3-
hydroxymethyl-4-methoxy-2-naphthoic acid lactones 13, a class of lignan lactones. The other benzannu-
lation involves three series of reactions using acid chlorides 3a–c: (1) the intermolecular Friedel–Crafts
acylation of 3 with one benzene molecule giving the intermediary 2,2-dichlorocyclopropyl(phenyl)-
methanones 14a–c; (2) the intermolecular trapping of 14a–c with another benzene molecule accompanied
by regioselective ring opening; and (3) the final intramolecular cyclization giving 4-phenyl-1-naphthols
4a–c. The use of p-xylene also gives the corresponding 4-(p-xylyl)-1-naphthol 4d. The reactions of
alternatively prepared ketones 14 with benzenes gives a variety of ‘unsymmetrically’ substituted 4-aryl-1-
naphthols 4c,e–k under identical conditions. H owever, the reaction using p-methoxyphenyl ketone
analogues 14g does not produce 4-aryl-1-naphthols, but gives 5-aryl-2-(p-methoxyphenyl)-3-methylfurans
16. These annulations proceed straightforwardly (in a one-pot manner) and this variation is due to the
highly regioselective cyclopropane ring-openings.
The characteristic features of cyclopropa(e)nes has brought
about number of both unique and useful synthetic
cyclopropyl)methanols with acid catalysts for the synthesis of
a
α- and β-halogenonaphthalenes, wherein two distinct types of
highly regioselective acid-induced cyclopropane ring cleavages
are involved.11a,d These results prompted us to extend the more
straightforward benzannulation aiming at the synthesis of the
4-aryl-1-naphthols.
This paper describes full details of the two types of novel,
sequential and regioselective Friedel–Crafts (F–C) type benz-
annulations of gem-dihalogenocyclopropanecarbonyl chlorides
1 and 3 producing various 4-aryl-1-naphthols 2 and 4, respect-
ively (Scheme 1).11b Since 4-arylnaphthalene derivatives are
reactions.1a–c This synthetic methodology has been continu-
ously developed over the past two or three decades. The poten-
tiality of these methods is largely ascribed to the nature of
cyclopropa(e)nes, i.e. relief of the inherent ring strain providing
a variety of thermal, oxidative and reductive, and electrophilic
and nucleophilic ring-opening reactions. Cyclopropa(e)ne ring
expansions (annulation accompanying ring reconstructions)
occupy a significant position in worthwhile synthetic methods.1
Among them, benzannulation (construction of aromatic rings)
utilizing cyclopropene intermediates has recently attracted
attention in organic reactions,2 wherein several naphthol
analogues were produced by the reaction of carbene–metal
complexes with cyclopropenes through rearrangement.
Another notable benzannulation utilizing cyclobutene deriva-
tives is also documented.3 These benzannulations are con-
sidered to be worthwhile synthetic methods in view of both
their unique reaction mode and practicality in providing a var-
iety of substituted aromatics.
OH
R2
Y
R2
R1
X
R1
AlCl3
COCl
X
X
Y
1
2
Our attention has been focused on the chemistry of gem-
dihalogenocyclopropane derivatives, because they possess the
following noteworthy features: (a) ease of preparation by the
addition of dihalogenocarbenes to olefins;4 (b) as the only pre-
cursor for halogenocyclopropanes when subjected to reductive
dehalogenation using tributyltin hydride, metal hydrides and
other reagents;5 (c) useful intermediates for Nazarov-type
cyclopentannulation;6 (d) synthons of choice for cyclopropane
derivatives by inter- and intra-molecular stereocontrolled C᎐C
bond formation through both anionic7 and radical type
methods;8 (e) other useful transformations;9 and (f) constitu-
ents of useful biologically active compounds.10 As part of our
ongoing program for new and useful reactions and compounds
utilizing gem-dihalogenocyclopropanes,8,11 we have previously
reported a novel benzannulation using aryl(gem-dihalogeno-
OH
R1
R3
Y
2
R3
R1
Y
COCl
AlCl3
Cl Cl
(R3 = H, Me)
Y
3
4
Scheme 1
attracting much attention as the basic skeleton of several bio-
logically active lignan-type natural products and pharma-
ceuticals,12 these compounds and their isosteres have been one
J. Chem. Soc., Perkin Trans. 1, 1997
477

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synthetic target of significance.13 Taking this background into
account, we evaluated the application of 4-aryl-1-naphthols to
the synthesis of new types of lignan lactones.
prepared by an alternative method and is the postulated inter-
mediate in the case where the intermolecular F–C acylation
initially occurred, mainly afforded an isomeric naphthol 6
under identical conditions [eqn. (3)]. (3) The controlled reac-
tion of (E)-1a without benzene gave the tricyclic ketone 7 and
3,4-dichloro-1-naphthol 8 as major products [eqn. (4)]. (4) The
controlled reaction of (Z)-1a with or without benzene, on the
other hand, gave the tricyclic ketone 7 as a major product in
good yield [eqn. (5)]. (5) Treatment of 7 with or without ben-
zene under identical conditions resulted only in the recovery
of 7.
These results clearly indicate that during this sequential F–C
reaction, intramolecular cyclization of the key ketene inter-
mediate 9 precedes the intermolecular coupling with benzene
(Scheme 3). The heavy lines in these structures indicate the
backbones of the starting 2,2-dichloro-3-phenylcyclopropane
moiety. Three important points should be noted: (1) bond-a
cleavage proceeded with high regioselectivity to result in the
selective synthesis of 2a;11a,d (2) even 1.2 equiv. of benzene was
sufficient for it to play its role as the intermolecular trapping
agent; and (3) the E-configuration of acyl chloride 1a was
critical for this successful benzannulation. We have recently
reported a new furan synthesis using 1a and 5 equiv. of reactive
benzenes such as toluene or anisole.11c Accordingly, the reaction
pathway involving 1 forks into two alternative branches, i.e., 4-
aryl-1-naphthol formation and diarylfuran formation, depend-
ing on the relative molar amounts of the benzenes used.
Table 1 lists the results of the synthesis of various 4-aryl-
3-halogeno-1-naphthols 2 (Method A). As for the para-
substituent (R2) in 1, the MeO group led to a decreased product
yield compared with the H or Cl. Whilst the use of toluene,
chloro- bromo-benzenes as reactants gave the corresponding
regioisomeric mixtures of 4-aryl-3-halogeno-1-naphthols 2, 2,6-
dichlorotoluene and 1,4-dichlorobenzene gave the correspond-
ing single products 2f, g, k, m and o.
Results and discussion
One of the sequential F–C reactions involved the intra-
molecular cyclization of (E)-3-aryl-2,2-dihalogenocyclo-
propanecarbonyl chlorides 1, followed by intermolecular coup-
ling with substituted benzenes to give 4-aryl-3-halogeno-1-
naphthols 2. Initially, we allowed (E)-2,2-dichloro-1-methyl-3-
phenylcyclopropanecarbonyl chloride (E)-1a to react with ben-
zene in the presence of an acid such as AlCl3, Et2AlCl, TiCl4,
SnCl4, ZnCl2, BF3ؒOEt2 or CF3CO2H. After optimizing the
conditions, the use of 1.1 equiv. of benzene and 2.2 equiv. of
AlCl3 at room temperature gave 3-chloro-2-methyl-4-phenyl-1-
naphthol 2a in 52% yield [Scheme 2, eqn. (1)]. To clarify this
OH
i
(1)
Cl
COCl
Cl Cl
(E )-1a
2a
OH
ii
(2)
(E )-1a
Cl
D5
2b
The structures of the naphthols 2a and 2f were unambigu-
ously determined by 1H and 13C NMR spectroscopy,14 H-H and
C–H COSY results, a DEPT spectrum and elemental analysis.
The NOESY spectra of 2a, 2b and 2f [interaction between the
OH (5.32 ppm) and the Me (2.51–2.53 ppm)], and that of 2f
[interaction between OH (5.32 ppm) and 8-H (8.35 ppm)] also
supported the assignment of a 4-aryl-2-naphthol skeleton to
the compounds (see Fig. 1).
OH
iii
(3)
D4
D5
Cl
O
Cl Cl
5
6
Murphy and Wattanasin reported the Lewis acid-promoted
annulation of 2-arylcyclopropyl aryl ketones 10, which were
prepared by cyclopropanation of chalcones for the synthesis of
tetralones.15 The modes of both this ring-expansion using 10
and the benzannulation using aryl(2,2-dihalogeno-3-phenyl-
cyclopropyl)methanols 1111a,d are quite different from that of
the present reaction, because those two methods involve the
intramolecular F᎐C alkylation of the 3-position on the cyclo-
propane ring and no F᎐C intermolecular coupling (Scheme 4).
We next evaluated the utility of the 4-aryl-3-halogeno-1-
naphthols 2. Following our work utilizing 2, we used the bromo-
naphthols 2i and 2k to prepare the two lignan lactones 13a and
13b, respectively (Scheme 5). Lithiation at the bromine position
in 2i and 2k, followed by trapping with CO2, gave the corre-
sponding carboxylic acids, which were converted into the esters
12a and 12b by double methylation of the hydroxy and the
carboxy groups with an excess of MeI. The desired lignans 13a
and 13b were obtained by bromination of the vicinal methyl
groups, followed by treatment with 1  aqueous NaOH and
acidic work-up. This sequence made good use of the bromine in
the naphthalene for effective derivatization, compared with our
earlier method for synthesizing natural lignan lactones utilizing
the α-chloronaphthane intermediate,11a,d wherein an extra
dechlorination step was required.
OH
Cl
O
iii
(E )-1a
+
(4)
Cl
Cl
Cl
8
7
i or iii
COCl
(5)
(6)
7
Cl Cl
(Z )-1a
i or iii
7 (recovery)
7
Scheme 2 Reagents and conditions: i, benzene (1.2 equiv.), AlCl3 (2.2
equiv.), 1,2-dichloroethane, room temp.; ii, [2H6]benzene (1.2 equiv.),
AlCl3 (2.2 equiv.), 1,2-dichloroethane, room temp.; iii, AlCl3 (2.2
equiv.), 1.2-dichloroethane, room temp.
reaction mechanism, we carried out the following five experi-
ments [eqns. (2)–(6)]. (1) An identical reaction of (E)-1a using
C6D6 in place of benzene gave the 4-C6D5-substituted naph-
thol 2b [eqn. (2)]. (2) The C6D5-substituted ketone 5, which was
The other sequential F᎐C reaction for benzannulation using
2,2-dichlorocyclopropanecarbonyl chlorides 3 involved the
following reaction series: (1) the intermolecular F᎐C acylation
478
J. Chem. Soc., Perkin Trans. 1, 1997

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Table 1 Sequential Friedel–Crafts reaction of acyl chlorides 1 with benzenes (Method A)
OH
R2
R2
R1
X
Y
R1
AlCl3 (2.2 equiv.)
COCl
X
X
Y
1
2
Substrate
X
R1
R2
H
Y-Benzene
Product
Yield (%)
1a
Cl
Me
Benzene
2a
2b
2c
2d
2e
2f
2g
2h
2i
2j
2k
2l
2m
2n
2o
52
50
[2H6]Benzene
Toluene
4-Me
4-Cl
4-Br
2,4-Cl2, 3-Me
2-Cl, 5-Cl
4-Cl
56a
81b
64c
60d
47
Chlorobenzene
Bromobenzene
2,6-Dichlorotoluene
1,4-Dichlorobenzene
Chlorobenzene
Benzene
Chlorobenzene
1,4-Dichlorobenzene
Benzene
1b
1c
Cl
Br
H
Me
H
H
51e
47
4-Cl
2-Cl, 5-Cl
72 f
48
1d
1e
Cl
Cl
Me
Me
Cl
48
2,6-Dichlorotoluene
Benzene
2,6-Dichlorotoluene
2,4-Cl2, 3-Me
2,4-Cl3, 3-Me
44d
23
OMe
44d
a Containing ca. 10% of 2-Me or 3-Me isomer. b Containing ca. 35% of 2-Cl isomer. c Containing ca. 20% of 2-Br isomer. d Exclusively single isomer.
e Containing ca. 30% of 2-Cl isomer. f Containing ca. 40% of 2-Cl isomer.
–
AlCl3
OH
Cl
O
a
AlCl3
–HCl
H3O+
COCl
–
–AlCl4
Cl
Cl
O
Cl
Cl Cl
Cl Cl
AlCl3
Cl–
Cl
–H+
8
(E)-1a
O
–HCl
Cl
Cl
–
AlCl3
Cl
–Cl–
OH
O
O
9
–HCl
H3O+
–H+
O
Cl
Cl
Cl
Cl
Cl
fast
Cl Cl
7
2a
Scheme 3
of 2,2-dichlorocyclopropanecarbonyl chlorides 3a–c with one
benzene molecule to give the ketones 14a–c; (2) the inter-
molecular trapping of 14a–c with another benzene molecule
accompanied by cyclopropane ring-opening; and (3) the final
intramolecular cyclization to give 4-aryl-1-naphthols 4a–c
(Scheme 6). It is also noteworthy that these reactions spon-
taneously took place in a one-pot manner with regioselective
bond-b cleavage to give a selective synthesis of 4 (Table 2,
Method B). Accordingly, the regioselective ring-cleavage
position of a or b depends on the difference in substituents
(3-position) on the cyclopropane ring. When p-xylene was used
as the solvent, the desired reaction also proceeded to give 4d.
However, the reactions using monosubstituted benzenes such as
toluene and p-methoxybenzene proved to very sluggish.
annulation using the intermediary ketones 14c–f which were
prepared in an alternative way by the coupling of ArMgBr (1.0
equiv.) with the acyl chlorides 3 in 52–61% yields. As expected,
these ketones gave the corresponding 4-aryl-1-naphthols 4c,e–
k under identical conditions. This improved method provided
access to a variety of compounds 4 bearing ‘unsymmetrical’
substituents, by using variously substituted benzenes which
could be incorporated stepwise (Table 3, Method C). A repre-
sentative structure, that of 4-phenyl-1-naphthol 4c, was also
unambiguously determined (1H and 13C NMR, H᎐H and C–H
COSYs, and NOESY spectral evidence).
Finally, we describe a new furan synthesis using 2,2-di-
chloro-1-methylcyclopropyl(p-methoxyphenyl)methanone 14g
(Scheme 7). Treatment of the p-methoxyphenyl substituted
ketone 14g with benzene, toluene and chlorobenzene, respec-
To confirm this reaction mechanism, we examined the benz-
J. Chem. Soc., Perkin Trans. 1, 1997
479

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Table 2 Sequential Friedel–Crafts reactions of acyl chlorides 3 with
benzene or p-xylene (Method B)
NOESY
NOESY
H
OH
H
OH
OH
2
R1
R3
Y
R3
R1
Y
Cl
Cl
COCl
Cl
AlCl3 (2.2 equiv.)
Cl Cl
Y
3
Y
Cl
2a Y = H5
2b Y = D5
2f
4
Fig. 1
Substrate
R1
R3
Y-Benzene
Product
Yield (%)
3a
3b
3c
3c
H
H
Me
H
Benzene
Benzene
Benzene
p-Xylene
4a
4b
4c
4d
38
40
58a
44
intramolecular
OH
Me
Me
Me
R2
R2
R1
X
H
COCl
R1
a
3.0 Equiv. of AlCl3 were used.
intermolecular
X
X
Y
OH
OMe
Y
2
1
i, ii, iii
Br
Y1
CO2Me
Y1
Y1
Y1
O
M
O
Y
Y
2i Y1 = H
2k Y1 = Cl
12a Y1 = H
12b Y1 = Cl
10
iv, v, vi
OMe
R2
M
H
R1
O
R2
O
Y
X
Y
R1
O
Y1
X
X
11
Y1
13a Y1 = H
13b Y1 = Cl
Scheme 4
tively, in the presence of AlCl3, gave the corresponding 5-aryl-2-
(p-methoxyphenyl)-3-methylfurans 16 in moderate yields; none
of the expected 4-aryl-1-naphthols were produced. This
unexpected result may be explained as follows; the p-
methoxyphenyl group participates in stabilizing the intermedi-
ary benzyl cation 15 to such a degree that during the cyclo-
propane ring-opening, attack by the carbonyl oxygen at the 2-
position of the cyclopropane ring occurs. This is followed by
intermolecular trapping with benzenes as is described for the
aforementioned benzannulations. Such a speculative mechan-
ism could explain the reported furan formation when (E)-3-
aryl-2,2-dihalogenocyclopropanecarbonyl chlorides (E)-1
reacts with anisole (p-methoxybenzene).11c
Scheme 5 Reagents and conditions: i, BusLi (2.5 equiv.), THF, Ϫ60 ЊC;
ii, CO2; iii, K2CO3 (2.4 equiv.), MeI (2.4 equiv.), DMF, room temp.; iv,
NBS (1.1 equiv.), cat. AIBN, CCl4, reflux; v, 10% aq. NaOH–dioxane,
70 ЊC; vi, 4  aq. HCl, room temp.
cyclopropanes. Further work on the use of gem-dihalogeno- or
halogeno-cyclopropanes for new types of benzannulations is
now underway.
Experimental
Melting points were determined on a hot-stage microscope
apparatus (Yanagimoto) and are uncorrected. 1H NMR Spectra
were recorded on a JEOL EX-90 (90 MHz) and/or JEOL α (400
MHz) spectrometer in CDCl3 using TMS as internal standard.
13C NMR Spectra were recorded on a JEOL α (100 MHz) spec-
trometer in CDCl3 using TMS as internal standard. IR Spectra
were recorded on a JASCO FT/IR-8000 spectrophotometer.
Mass spectra and HRMS were recorded on JMS-AutoMass 50
KTR-3 and JMS-AX505H machines, respectively. Silica gel
column chromatography was performed on a Merck Art. 7734
and/or 9385.
gem-Dihalogenocyclopropanecarbonyl chlorides 1 and 3
used as substrates throughout this study were readily prepared
by a reported procedure (Scheme 8).
In conclusion, we have investigated two distinct types of
sequential F᎐C reactions for new benzannulations using gem-
dihalogenocyclopropanecarbonyl chlorides, in which various
types of 4-aryl-1-naphthols were prepared. These reactions
proceed in a more straightforward, one-pot manner, than
the related annulations and via significantly different mechan-
isms. The variation in these annulations is unequivocally due to
the high degree of site-selectivity in the ring-openings (bonds-a
and -b); this behaviour is characteristic of gem-dihalogeno-
(1R*,3S*)-2,2-Dichloro-1-methyl-3-phenylcyclopropane-
carbonyl chloride (E)-1a, (1R*,3S*)-2,2-dichloro-3-phenyl-
480
J. Chem. Soc., Perkin Trans. 1, 1997

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Table 3 Stepwise Friedel–Crafts reaction of the ketones 14 with benzenes (Method C)
OH
O
Z
Y
Y
Cl
AlCl3 (2.2 equiv.)
Cl
14c-f
Z
4c,e-k
Ketone
Y
Z-Benzene
Product
Yield (%)
14c
14c
14d
14d
14e
14e
14f
14f
H
Benzene
2,6-Dichlorotoluene
Benzene
2,6-Dichlorotoluene
Benzene
2,6-Dichlorotoluene
Benzene
4c
4e
4f
4g
4h
4i
38
2,4-Cl2, 3-Me
2,4-Cl2, 3-Me
2,4-Cl2, 3-Me
2,4-Cl2, 3-Me
48a
52
4-Cl
23a
32
4-Me
3-Me
23a
55b
43a,b
4j
4k
2,6-Dichlorotoluene
a
Exclusively single isomer. b Exclusively 7-methyl isomer.
R3
R1
colourless crystals, mp 142–144 ЊC (Found: C, 54.0; H, 4.0.
C11H10Cl2O2 requires C, 53.90; H, 4.11%); νmax(KBr)/cmϪ1 3600–
2400, 1714 and 1249; δH (90 MHz) 1.83 (3 H, s), 2.90 (1 H, s) and
7.30–7.60 (5 H, m). A mixture of the carboxylic acid (1.08 g, 4.4
mmol), thionyl chloride (0.63 g, 5.3 mmol) and a drop of DMF
in benzene (10 cm3) was refluxed for 16 h. The mixture was then
concentrated under reduced pressure and distilled by bulb-to-
bulb distillation [bp 130–145 ЊC (oven temp.)/0.2 mmHg] to
give the title product (Z)-1a (1.16 g, 95%) as colourless crystals,
mp 82 ЊC (decomp.); δH (90 MHz) 2.01 (3 H, s), 3.05 (1 H, s) and
7.25–7.65 (5 H, m); νmax(KBr)/cmϪ1 2984, 1807 and 1448.
COCl
Cl Cl
3a-c
AlCl3
AlCl2
AlCl2
AlCl3
O
O
O
R1
R1
R3
R3
Cl
R1
-HCl R3
-2HCl
(1R*,3S*)-3-(4-Chlorophenyl)-2,2-dichloro-1-methylcyclo-
propanecarbonyl chloride 1d
b
Cl
Cl
Cl
Following the procedure for preparing the acid chloride (Z)-
1a described above, using the alcohol 17d, (1R*,3S*)-3-
(4-chlorophenyl)-2,2-dichloro-1-methylcyclopropanecarboxylic
acid (87%) was obtained as colourless crystals, mp 153–154 ЊC
(Found: C, 47.0; H, 3.1. C11H9Cl3O2 requires C, 47.26; H,
3.25%); δH (400 MHz) 1.42 (3 H, s), 3.59 (1 H, s), 7.22 (2 H, d, J
8.1) and 7.36 (2 H, d, J 8.1); δC 14.4, 39.1, 39.2, 65.6, 128.8,
129.8, 131.4, 133.9 and 174.9; νmax(KBr)/cmϪ1 2993, 2880, 1705
and 1300. The acid was converted into the product 1d (76%) by
bulb-to-bulb distillation [bp 180–185 ЊC (oven temp.)/0.2
mmHg] as colourless crystals, mp 63–66 ЊC; δH (400 MHz), 1.52
(3 H, s), 3.58 (1 H, s), 7.20 (2 H, d, J 7.3) and 7.36 (2 H, d, J
7.3); νmax(KBr)/cmϪ1 2999, 1772 and 1493.
14a-c
H3O+
OH
R1
R3
4a-c
Scheme 6
(1R*,3S*)-2,2-Dichloro-3-(4-methoxyphenyl)-1-methylcyclo-
propanecarbonyl chloride 1e
cyclopropanecarbonyl chloride 1b and (1R*,3S*)-2,2-
dibromo-1-methyl-3-phenylcyclopropanecarbonyl chloride 1c
were prepared from the alcohols 17a, 17b and 17c, respectively,
by the reported method.11c
Following the procedure for preparing the acid chloride (Z)-1a
described above, using the alcohol 17e, (1R*,3S*)-2,2-dichloro-
3-(4-methoxyphenyl)-1-methylcyclopropanecarboxylic
acid
(98%) was obtained as colourless crystals, mp 151–152 ЊC
(Found: C, 52.0; H, 4.1. C12H12Cl2O3 requires C, 52.39; H,
4.40%); δH (90 MHz) 1.42 (3 H, s), 3.58 (1 H, s), 3.81 (3 H, s),
6.90 (2 H, d, J 8.7), 7.21 (2 H, d, J 8.7) and 8.50–9.70 (1 H, br,
OH); νmax(KBr)/cmϪ1 3459, 1705 and 1514. The acid was con-
verted into the product 1e (60%) by bulb-to-bulb distillation [bp
170–175 ЊC (oven temp.)/0.2 mmHg] as purple crystals, mp 68–
73 ЊC; δH (90 MHz) 1.55 (3 H, s), 3.59 (1 H, s), 3.82 (3 H, s), 6.91
(2 H, d, J 8.6) and 7.20 (2 H, d, J 8.6); νmax(KBr)/cmϪ1 1780,
1514 and 1250.
(1R*,3R*)-2,2-Dichloro-1-methyl-3-phenylcyclopropane-
carbonyl chloride (Z)-1a
Jones reagent (5 cm3) was added to a stirred solution of (1R*,
3R*)-2,2-dichloro-1-methyl-3-phenylcyclopropylmethanol11f
(1.20 g, 5.0 mmol) in acetone (10 cm3) at 0–5 ЊC, and the mix-
ture was stirred at room temp. for 24 h. Acetone was evaporated
from the mixture and water was added to the residue. The mix-
ture was then extracted with ethyl acetate (20 cm3 × 2) and the
combined extracts were washed with water and brine, dried
(Na2SO4) and concentrated to give (1R*,3R*)-2,2-dichloro-1-
methyl-3-phenylcyclopropanecarboxylic acid (1.20 g, 98%) as
3-Chloro-2-methyl-4-phenyl-1-naphthol 2a [eqn. (1)]
Method A: typical procedure. AlCl3 (147 mg, 1.1 mmol) was
J. Chem. Soc., Perkin Trans. 1, 1997
481

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–
AlCl3
AlCl3
O
O
O
AlCl3
OMe
O
+
Cl
Cl
OMe
Me
Me
Cl
Cl
Me
Cl
Cl
Cl
OMe
OMe
Cl
Me
14g
15
–2HCl
W
O
W
OMe
Me
16a W = H
16b W = Me
16c W = Cl
Scheme 7
3-Chloro-2-methyl-4-(pentadeuteriophenyl)-1-naphthol 2b
[eqn. (2)]
R2
R2
R1
i, ii, iii
OH
Following the procedure of Method A described above, with
[2H6]benzene in place of benzene, the product 2b (50%) was
obtained as colourless crystals, mp 85–88 ЊC; δH (400 MHz) 2.51
(3 H, s), 5.32 (1 H, br s, OH), 7.24–7.54 (3 H, m) and 8.12 (1 H,
d, J 7.4); νmax(Nujol)/cmϪ1 3532, 3492, 1578 and 1502.
OH
R1
X
X
17a
R
1 = Me, R2 = H, X = Cl
17b R1 = R2 = H, X = Cl
17c R1 = Me, R2 = H, X = Br
(1R*,3R*)-2,2-Dichloro-1-methyl-3-phenylcyclopropyl(penta-
deuteriophenyl)methanone 5. According to the reported proce-
dure11c using C6D5MgBr in place of PhMgBr, the product 5
(65%) was obtained as colourless oil; δH (90 MHz) 1.44 (3 H, s),
3.58 (1 H, s) and 7.27–7.48 (5 H, m); νmax(neat)/cmϪ1 1686, 1244
and 1157.
17d
17e
R
R
1 = Me, R2 = X = Cl
1 = Me, R2 = MeO, X = Cl
iv, v
R2
3-Chloro-2-methyl-4-phenyl-5,6,7,8-tetradeuterio-1-naphthol
6 [eqn. (3)]. AlCl3 (248 mg, 1.86 mmol) was slowly added
portion-by-portion to a stirred solution of (1R*,3S*)-2,2-
dichloro-1-methyl-3-phenylcyclopropyl(pentadeuteriophenyl)-
methanone (262 mg, 0.85 mmol) in 1,2-dichloroethane (4 cm3)
at 0–5 ЊC, and the mixture was stirred at room temp. for 10 h.
Work-up similar to that of Method A gave the product 6 (65
mg, 28%) together with 3-chloro-4-methyl-5-(pentadeuterio-
phenyl)-2-phenylfuran (93 mg, 40%).11c Compound 6: colourless
crystals, mp 110–112 ЊC; δH (400 MHz) 2.51 (3 H, s), 5.32 (1 H,
br s, OH), 7.20–7.35 (2 H, m) and 7.40–7.55 (3 H, m);
νmax(KBr)/cmϪ1 3532, 3492, 1558 and 1462. 3-Chloro-4-methyl-
5-(pentadeuteriophenyl)-2-phenylfuran: colourless crystals, mp
70–76 ЊC; δH (400 MHz) 2.29 (3 H, s), 7.28–7.35 (1 H, m), 7.42–
7.48 (2 H, m) and 8.01 (2 H, d, J 8.3); νmax(KBr)/cmϪ1 2926,
2276 and 1564.
COCl
R1
X
X
1a–e
i, ii, iii
OH
OH
Me
Me
Cl Cl
(Z)–1a
Scheme 8 Reagents: i, 3,4-dihydro-2H-pyran; ii, CHX3, 50% aq.
NaOH; iii, H+; iv, Jones oxidation; v, SOCl2, cat. DMF
Controlled reaction using acyl chloride (E)-1a in the absence
of benzene [eqn. (4)]. AlCl3 (293 mg, 2.2 mmol) was added
portion-by-portion to a stirred solution of the carbonyl chlor-
ide (E)-1a (263 mg, 1.00 mmol) in 1,2-dichloroethane (5 cm3)
at 0–5 ЊC, and the mixture was stirred at room temp. for
10 h. Following the work-up procedure of Method A, a
crude oil was obtained which was purified by silica gel column
chromatography (hexane–diethyl ether, 5:1) to afford 8,8-
dichloro-2-methylcyclopropa[b]indan-1-one 7 (48 mg, 21%)
and 3,4-dichloro-2-methyl-1-naphthol 8 (50 mg, 22%). Com-
pound 7: colourless crystals, mp 65–67 ЊC; δH (400 MHz) 1.72 (3
H, s), 3.20 (1 H, s), 7.40–7.45 (1 H, m), 7.54–7.62 (2 H, m) and
7.70 (1 H, d, J 7.7); δC 11.8, 42.1, 44.4, 75.9, 124.5, 126.4, 128.8,
134.5, 136.0, 148.6 and 198.1; νmax(KBr)/cmϪ1 1725, 1620 and
1303; m/z (EI) 226 (M+), 193 and 191 (M+ Ϫ Cl). Compound 8:
colourless crystals; mp 118–120 ЊC; δH (400 MHz) 2.50 (3 H, s),
5.27 (1 H, br s, OH), 7.50–7.62 (2 H, m), 8.10 (1 H, d, J 8.5) and
8.21 (1 H, d, J 8.5); δC 13.9, 116.6, 121.5, 122.0, 123.7, 124.7,
126.2, 127.5, 130.2, 131.7 and 148.1; νmax(KBr)/cmϪ1 3374, 1586
and 1263; m/z (EI) 226 (M+), 193 and 191 (M+ Ϫ Cl).
added portion-by-portion to a stirred solution of cyclopro-
panecarbonyl chloride (E)-1a (132 mg, 0.50 mmol) and benzene
(47 mg, 0.60 mmol) in 1,2-dichloroethane (2.5 cm3) at 0–5 ЊC,
and the mixture was stirred at room temp. for 10 h. 1  Aqueous
HCl solution (ca. 5 cm3) and diethyl ether (ca. 5 cm3) were added
to the cooled mixture, which was then stirred at room temp. for
several min. The separated organic phase was washed with
water and brine, dried (Na2SO4) and concentrated to give a
crude oil. This was purified by silica gel column chroma-
tography (hexane–diethyl ether, 8:1) to give the product 2a (70
mg, 52%) as colourless crystals, mp 85–88 ЊC (Found: C, 75.6;
H, 4.5. C17H13ClO requires C, 75.98; H, 4.88%); δH (400 MHz)
2.52 (3 H, s), 5.32 (1 H, br s, OH), 7.22–7.38 (4 H, m), 7.40–7.55
(4 H, m) and 8.14 (1 H, d, J 7.4); δC 13.5, 115.6, 121.0, 122.9,
125.1, 125.3, 126.7, 127.4, 127.9, 128.3, 128.6, 130.7, 130.9,
132.3, 133.5, 138.6 and 148.8; νmax(KBr)/cmϪ1 3532, 3484, 1576,
1520 and 1506. Molar amounts of AlCl3 were optimized as
follows: 1.1 equiv. [vs. (E)-1a, 43%; 3.3 equiv.; 52%]. Under the
identical conditions Et2AlCl, SnCl4, ZnCl2, BF3ؒOEt2 or CF3-
CO2H failed to react. The reaction with TiCl4 was very sluggish.
Controlled reaction using the acyl chloride (Z)-1a in the pres-
482
J. Chem. Soc., Perkin Trans. 1, 1997

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ence or absence of benzene [eqn. (5)]. Following the procedure
of the controlled reaction using (E)-1a described above,
reaction using the acyl chloride (Z)-1a gave the tricyclic product
7 (64% with benzene; 70% without benzene), wherein neither of
the naphthols 2a and 8 was detected.
2.59 (3 H, s), 5.39 (1 H, br s, OH), 7.17 (1 H, d, J 8.5), 7.25 (1 H,
s), 7.34–7.45 (2 H, m), 7.46–7.58 (2 H, m) and 8.16 (1 H, d, J
8.5); νmax(KBr)/cmϪ1 3565, 1572 and 762.
3,7-Dichloro-2-methyl-4-phenyl-1-naphthol 2l (Method A).
Orange crystals, mp 113–116 ЊC (Found: C, 67.0; H, 3.8.
C17H12Cl2O requires C, 67.35; H, 3.99%); δH (400 MHz) 2.52 (3
H, s), 5.40 (1 H, br s, OH), 7.20–7.40 (4 H, m), 7.45–7.55 (3 H,
m) and 8.17 (1 H, s); νmax(KBr)/cmϪ1 3492, 1660, 1586 and 1496.
3,7-Dichloro-4-(2,4-dichloro-3-methylphenyl)-2-methyl-1-
naphthol 2m (Method A). Light yellow crystals, mp 178–179 ЊC
(Found: C, 55.8; H, 3.3. C18H12Cl4O requires C, 55.99; H,
3.13%); δH (400 MHz) 2.53 (3 H, s), 2.60 (3 H, s), 5.20–5.40 (1 H,
br s, OH), 7.02 (1 H, d, J 8.3), 7.10 (1 H, d, J 9.0), 7.29 (1 H, d, J
9.0), 7.43 (1 H, J 8.3) and 8.18 (1 H, s); νmax(KBr)/cmϪ1 3564,
1580, 1496 and 1344.
3-Chloro-7-methoxy-2-methyl-4-phenyl-1-naphthol 2n
(Method A). Amorphous solid; δH (400 MHz) 2.54 (3 H, s), 3.96
(3 H, s), 5.38 (1 H, br s, OH), 7.02–7.05 (1 H, d, J 9.2), 7.23–
7.40 (3 H, m) and 7.45–7.55 (4 H, m); νmax(KBr)/cmϪ1 3447,
2361 and 1034; m/z (EI) 268.0754 (M+. C18H15ClO2 requires
298.0762).
Controlled reaction using the tricyclic ketone 7 in the presence
or absence of benzene [eqn. (6)]. Following the procedure of the
controlled reaction described above, a reaction using the tri-
cyclic product 7 was carried out. It resulted in quantitative
recovery of starting material both with and without benzene.
3-Chloro-2-methyl-4-(p-tolyl)-1-naphthol 2c (Method A). The
crude product which was roughly purified with silica gel column
chromatography contained ca. 10% of the o-tolyl or m-tolyl
regioisomer. This mixture was further purified chromato-
graphically to give the pure product 2c as colourless crystals, mp
138–143 ЊC; δH (90 MHz) 2.31 (3 H, s), 2.49 (3 H, s), 5.20 (1 H,
br s, OH), 7.00–7.70 (7 H, m) and 8.00 (1 H, d, J 7.4);
νmax(KBr)/cmϪ1 3573, 1597, 1196 and 704; m/z (EI) 282.0808
(M+. C18H15ClO requires 282.0813).
3-Chloro-4-(4-chlorophenyl)-2-methyl-1-naphthol 2d
(Method A). The product 2d containing ca. 35% of the
2-chlorophenyl regioisomer was obtained as an amorphous
solid; δH (90 MHz) 2.53 (3 H × 4/11, s, 2-Cl-compound), 2.55
(3 H × 7/11, s), 5.52 (1 H, br s, OH), 7.02–7.90 (7 H, m) and
8.17 (1 H, d, J 8.4); νmax(KBr)/cmϪ1 3564, 1574 and 760; m/z
(EI) 302.0224 (M+. C17H12Cl2O requires 302.0266).
3-Chloro-4-(4-bromophenyl)-2-methyl-1-naphthol 2e (Method
A). The product 2e containing ca. 20% of the 2-bromophenyl
regioisomer was obtained as an amorphous solid; δH (90 MHz)
2.52 (3 H × 1/5, s, 2-Br-compound), 2.54 (3 H × 4/5, s), 5.45
(1 H, br s, OH), 7.05–7.90 (7 H, m) and 8.08–8.30 (1 H, m);
νmax(KBr)/cmϪ1 3565 and 1573; m/z (EI) 345.9759 (M+.
C17H12BrClO requires 345.9761).
3-Chloro-4-(2,4-dichloro-3-methylphenyl)-2-methyl-1-naph-
thol 2f (Method A). Light brown crystals, mp 171–173 ЊC
(Found: C, 61.1; H, 3.8. C18H13Cl3O requires C, 61.48; H,
3.73%); δH (400 MHz) 2.53 (3 H, s), 2.58 (3 H, s), 5.32 (1 H, br s,
OH), 7.04 (1 H, d, J 8.3), 7.16 (1 H, d, J 8.5), 7.36 (1 H, dd, J
8.5, 7.7), 7.42 (1 H, d, J 8.3), 7.48 (1 H, dd, J 8.3, 7.7) and 8.35
(1 H, d, J 8.3); δC 149.3, 136.3, 136.1, 135.1, 134.8, 132.7, 131.5,
129.8, 128.1, 127.6, 126.8, 125.5, 125.4, 122.8, 121.3, 115.5, 18.1
and 13.4; νmax(KBr)/cmϪ1 3572, 3500, 1576, 1504 and 1368.
3-Chloro-4-(2,4-dichloro-3-methylphenyl)-7-methoxy-2-
methyl-1-naphthol 2o (Method A). Brown crystals, mp 170–
173 ЊC; δH (400 MHz) 2.52 (3 H, s), 2.58 (3 H, s), 5.60–5.75 (1 H,
br, OH), 7.00–7.10 (3 H, m), 7.40 (1 H, d, J 8.1) and 7.38 (1 H,
d, J 2.4); νmax(KBr)/cmϪ1 3552, 2932, 1624, 1508 and 1228; m/z
(EI) 379.0072 (M+ Ϫ H. C19H14Cl3O requires 379.0061).
2-Methyl-4-phenyl-1-naphthol 4c
Method B: typical procedure. AlCl3 (440 mg, 3.3 mmol) was
added portion-by-portion to a stirred solution of 2,2-dichloro-
1-methylcyclopropanecarbonyl chloride11d 3c (200 mg, 1.1
mmol) in benzene (5 cm3) at room temp., and the mixture was
stirred for 10 h. Work-up was similar to that described in
Method A gave a crude oil, purification of which by silica gel
column chromatography (hexane–diethyl ether, 8:1) gave the
product 4c (145 mg, 58%) and 2-methyl-3-phenyl-1-naphthol
(60 mg, 24%). Compound 4c: colourless crystals, mp 73–75 ЊC;
δH (400 MHz) 2.17 (3 H, s), 5.46 (1 H, br s, OH), 6.77 (1 H, s),
7.24–7.54 (8 H, m) and 8.15 (1 H, d, J 11.6); δC 20.8, 111.1,
121.3, 122.7, 124.1, 126.1, 126.3, 126.8, 128.3, 130.7, 131.2,
133.4, 134.1, 139.7 and 150.4; νmax(KBr)/cmϪ1 3389 and 1595;
m/z (EI) 234.1065 (M+. C17H14O requires 234.1045), 219, 202
and 189. 2-Methyl-3-phenyl-1-naphthol: yellow oil; δH (400
MHz) 2.28 (3 H, s), 5.33 (1 H, br s, OH), 7.30–7.55 (8 H, m),
7.76 (1 H, d, J 7.6) and 8.13 (1 H, d, J 7.6); m/z (EI) 234 (M+.
C17H14O requires 234), 219, 202 and 189. 1H NMR data for the
methyl ether of 2-methyl-3-phenyl-1-naphthol were identical
with reported values.2
4-Phenyl-1-naphthol 4a (Method B). Colourless crystals, mp
133–135 ЊC (lit.,16 137 ЊC); δH (90 MHz) 5.46 (1 H, br s, OH),
7.00–8.00 (10 H, m) and 8.02–8.30 (1 H, m).
2,3-Dimethyl-4-phenyl-1-naphthol 4b (Method B). Amorph-
ous solid; δH (90 MHz) 2.16 (3 H, s), 2.39 (3 H, s), 5.40 (1 H, br s,
OH), 7.00–7.80 (7 H, m) and 8.02–8.20 (1 H, m); νmax(neat)/
cmϪ1 3442 and 1699; m/z (EI) 248.1185 (M+. C18H16O requires
248.1202).
2,2-Dichloro-1-methylcyclopropyl(phenyl)methanone 14c. A
solution of 2,2-dichloro-1-methylcyclopropanecarbonyl chlor-
ide 3c (500 mg, 2.7 mmol) in THF (2 cm3) was added to a
Grignard reagent [generated from Mg (71 mg, 3.0 mmol) and
bromobenzene (466 mg, 3.0 mmol) in THF (4 cm3)] at 0–5 ЊC,
and the mixture was stirred at 0–5 ЊC for 30 min. The mixture
was allowed to warm to room temp. during a period of 30 min,
after which it was stirred for an additional 1 h at this tem-
perature. The mixture was poured into an ice and aqueous sat.
NH4Cl mixture, which was then extracted twice with diethyl
ether. The combined extracts were washed with water and brine,
dried (Na2SO4) and concentrated to give a crude oil. This was
purified by silica-gel column chromatography (hexane–diethyl
3-Chloro-4-(2,5-dichlorophenyl)-2-methyl-1-naphthol
2g
(Method A). Colourless crystals, mp 151–152 ЊC (Found: C,
60.1; H, 3.5. C17H11Cl3O requires C, 60.48; H, 3.28%); δH (400
MHz) 2.53 (3 H, s), 5.45–5.50 (1 H, br, OH), 7.18 (1 H, d, J 8.4),
7.28 (1 H, d, J 2.1), 7.36–7.44 (2 H, m), 7.46–7.52 (2 H, m) and
8.16 (1 H, J 8.5); νmax(KBr)/cmϪ1 3568, 1578, 1092 and 762.
3-Chloro-4-(4-chlorophenyl)-1-naphthol 2h (Method A). The
product 2h containing ca. 30% of the 2-chlorophenyl regio-
isomer was obtained as an amorphous solid; δH (90 MHz) 5.69
(1 H, br s, OH), 6.95 (1 H × 1/3, s, 2-Cl-compound), 6.98 (1
H × 2/3, s), 7.05–7.70 (7 H, m) and 8.10–8.40 (1 H, m);
νmax(KBr)/cmϪ1 3540, 3069, 2978, 1588, 1343 and 766; m/z (EI)
288.0118 (M+. C16H10Cl2O requires 288.0110).
3-Bromo-2-methyl-4-phenyl-1-naphthol 2i (Method A).
Amorphous solid (Found: C, 64.8; H, 3.8. C17H13BrO requires
C, 65.20; H, 4.18%); δH (90 MHz) 2.56 (3 H, s), 5.32 (1 H, br s,
OH), 7.20–7.60 (8 H, m) and 8.14 (1 H, d, J 7.4); νmax(KBr)/
cmϪ1 3567 and 1573.
3-Bromo-4-(4-chlorophenyl)-2-methyl-1-naphthol 2j (Method
A). The product 2j containing ca. 40% of the 2-chlorophenyl
regioisomer was obtained as an amorphous solid; δH (90 MHz)
2.58 (3 H × 2/5, s, 2-Cl-compound), 2.60 (3 H × 3/5, s), 5.40 (1
H, br s, OH), 7.10–7.90 (7 H, m) and 8.04–8.28 (1 H, m);
νmax(KBr)/cmϪ1 3568 and 1574; m/z (EI) 345.9759 (M+.
C17H12BrClO requires 345.9761).
3-Bromo-4-(2,5-dichlorophenyl)-2-methyl-1-naphthol
2k
(Method A). Yellow crystals, mp 148–151 ЊC (Found: C, 53.1;
H, 2.6. C17H11BrCl2O requires C, 53.44; H, 2.90%); δH (90 MHz)
J. Chem. Soc., Perkin Trans. 1, 1997
483

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ether, 50:1) to give the product 14c (401 mg, 65%) as a colour-
less oil (Found: C, 57.4; H, 4.2. C11H10Cl2O requires C, 57.67;
H, 4.40%); δH (90 MHz) 1.49 (1 H, d, J 6.3), 1.63 (3 H, s), 2.31 (1
H, d, J 6.3), 7.40–7.79 (3 H, m) and 7.79–7.88 (2 H, m);
νmax(neat)/cmϪ1 1688, 1453 and 1262.
2,2-Dichloro-1-methylcyclopropyl(4-chlorophenyl)methanone
14d. Following the procedure for preparing the ketone 14c
described above, but using bromochlorobenzene in the place of
bromobenzene, the product 14d (64%) was obtained as a colour-
less oil (Found: C, 49.9; H, 3.3. C11H9Cl3O requires C, 50.13; H,
3.44%); δH (90 MHz) 1.50 (1 H, d, J 6.4), 1.64 (3 H, s), 2.29 (1 H,
d, J 6.4), 7.52 (2 H, d, J 8.1) and 7.89 (2 H, d, J 8.1); νmax(neat)/
cmϪ1 1688, 1589 and 1262.
2,2-Dichloro-1-methylcyclopropyl(p-tolyl)methanone 14e. Fol-
lowing the procedure for preparing the ketone 14c described
above, but using p-bromotoluene in the place of bromobenzene,
the product 14e (52%) was obtained as a colourless oil (Found:
C, 59.0; H, 4.8. C12H12Cl2O requires C, 59.28; H, 4.97%); δH (90
MHz) 1.46 (1 H, d, J 6.3), 1.63 (3 H, s), 2.29 (1 H, d, J 6.3), 2.47
(3 H, s), 7.32 (2 H, d, J 8.1) and 7.88 (2 H, d, J 8.1); νmax(neat)/
cmϪ1 1684, 1607 and 1264.
2.2), 7.41 (1 H, d, J 8.1) and 8.39 (1 H, J 2.2); νmax(Nujol)/cmϪ1
3280, 1600 and 1390; m/z (EI) 350.0026 (M+. C18H13Cl3O
requires 350.0034).
2,6-Dimethyl-4-phenyl-1-naphthol 4h (Method C). Amorph-
ous solid; δH (400 MHz) 2.16 (3 H, s), 2.50 (3 H, s), 5.28 (1 H, br
s, OH), 6.75 (1 H, s), 7.18 (1 H, dd, J 8.5, 1.5), 7.21–7.31 (3 H,
m), 7.36–7.51 (3 H, m) and 7.95 (1 H, s); νmax(KBr)/cmϪ1 3540,
1580 and 1462; m/z (EI) 248.1199 (M+. C18H16O requires
248.1202).
2,6-Dimethyl-4-(2,4-dichloro-3-methylphenyl)-1-naphthol 4i
(Method C). Amorphous solid; δH (400 MHz) 2.10 (3 H, s), 2.52
(3 H, s), 2.61 (3 H, s), 5.39 (1 H, br s, OH), 6.75 (1 H, s), 6.90–
7.50 (4 H, m) and 7.95 (1 H, s); νmax(KBr)/cmϪ1 3422, 2361 and
1655; m/z (EI) 331.0662 (M + H+. C19H17Cl2O requires
331.0658).
2,7-Dimethyl-4-phenyl-1-naphthol 4j (Method C). Amorph-
ous solid; δH (400 MHz) 2.16 (3 H, s), 2.36 (3 H, s), 5.27 (1 H, br
s, OH), 6.72 (1 H, s), 7.11 (1 H, s), 7.21–7.26 (3 H, m), 7.37–7.51
(3 H, m) and 8.06 (1 H, d, J 8.5); νmax(KBr)/cmϪ1 3424, 2361
and 1717; m/z (EI) 248.1193 (M+. C18H16O requires 248.1202).
2,7-Dimethyl-4-(2,4-dichloro-3-methylphenyl)-1-naphthol 4k
(Method C). Amorphous solid; δH (400 MHz) 2.08 (3 H, s), 2.36
(3 H, s), 2.38 (1 H, br s, OH), 2.59 (3 H, s), 6.68 (1 H, s), 6.91 (1
H, s), 7.00 (1 H, d, J 8.3), 7.25 (1 H, d, J 8.5), 7.39 (1 H, d, J 8.3)
and 8.07 (1 H, d, J 8.5); νmax(KBr)/cmϪ1 3432, 1577 and 1455;
m/z (EI) 330.0592 (M+. C19H16Cl2O requires 330.0580).
2,2-Dichloro-1-methylcyclopropyl(m-tolyl)methanone
14f.
Following the procedure for preparing the ketone 14c described
above, but using m-bromotoluene in the place of bromo-
benzene, the product 14f (56%) was obtained as a colourless oil
(Found: C, 59.0; H, 4.7. C12H12Cl2O requires C, 59.28; H,
4.97%); δH (90 MHz) 1.48 (1 H, d, J 6.4), 1.65 (3 H, s), 2.30 (1 H,
d, J 6.4), 2.46 (3 H, s), 7.30–7.54 (2 H, m) and 7.66–7.90 (2 H,
m); νmax(neat)/cmϪ1 1686, 1314 and 1269.
Methyl 1-(2,5-dichlorophenyl)-4-methoxy-3-methylnaphthalene-
2-carboxylate 12b
2,2-Dichloro-1-methylcyclopropyl(4-methoxyphenyl)-
BusLi (1.0  cyclohexane solution; 0.65 cm3, 0.65 mmol) was
added to a stirred solution of 3-bromo-4-(2,5-dichlorophenyl)-
2-methyl-1-naphthol 2k (100 mg, 0.26 mmol) in THF (1 cm3) at
Ϫ60 ЊC, and the mixture was stirred for 1 h at the same temp.
Several blocks of solid CO2 (ca. 5 g) were added to the mixture,
which was then stirred for 2 h at the same temp. The mixture
was allowed to warm to room temp. during a period of 30 min
after which it was stirred for an additional 30 min. Ice–aqueous
1  HCl was added to the mixture, which was then extracted
twice with diethyl ether. The combined extracts were washed
with water and brine, dried (Na2SO4) and concentrated to give
the crude 1-(2,5-dichlorophenyl)-4-hydroxy-3-methylnaphthal-
ene-2-carboxylic acid (110 mg). K2CO3 (180 mg, 1.3 mmol) was
added to a stirred solution of the crude naphthoic acid (110 mg)
and MeI (185 mg, 1.3 mmol) in DMF (2 cm3) at room temp.
after which the mixture was stirred for 1.5 h. It was then poured
into ice–water and extracted twice with diethyl ether. The com-
bined extracts were washed with brine, dried (Na2SO4), concen-
trated and purified by silica gel column chromatography
(hexane–diethyl ether, 15:1) to give the product 12b (59 mg,
61%) as colourless crystals, mp 153–157 ЊC (Found: C, 63.7; H,
4.0. C20H16Cl2O3 requires C, 64.02; H, 4.30%); δH (400 MHz)
2.45 (3 H, s), 3.60 (3 H, s), 3.96 (3 H, s), 7.25–7.60 (6 H, m) and
8.05–8.27 (1 H, d, J 9.0); νmax(KBr)/cmϪ1 2363, 1730 and 1583.
Methyl 4-methoxy-3-methyl-1-phenylnaphthalene-2-carb-
oxylate 12a. Following the procedure for preparing the ester
12b described above, with 2i in the place of 2k, the product 12a
was obtained (65%) as colourless crystals, mp 113–116 ЊC
(Found: C, 78.3; H, 5.6. C20H18O3 requires C, 78.41; H, 5.92%);
δH (90 MHz) 2.45 (3 H, s), 3.50 (3 H, s), 3.96 (3 H, s), 7.20–7.70
(8 H, m) and 8.05–8.27 (1 H, m); νmax(KBr)/cmϪ1 2946, 1732
and 1223. Note: The yield was improved by optimization after
our communication.11b
methanone 14g. Following the procedure for preparing the
ketone 14c described above, but using p-bromoanisole in the
place of bromobenzene, the product 14g (60%) was obtained as
a colourless oil (Found: C, 55.3; H, 4.7. C12H12Cl2O2: C, 55.65;
H, 4.97%); δH (90 MHz) 1.45 (1 H, d, J 7.1), 1.65 (3 H, s), 2.24 (1
H, d, J 7.1), 3.91 (3 H, s), 7.01 (2 H, d, J 9.1) and 7.94 (2 H, d, J
9.1); νmax(neat)/cmϪ1 2936, 1678 and 1601.
Method C: typical procedure
AlCl3 (147 mg, 1.1 mmol) was added portion-by-portion to a
stirred solution of the ketone 14c (115 mg, 0.50 mmol) in ben-
zene (2.5 cm3) at 0–5 ЊC, and the mixture was stirred at room
temperature for 10 h. Work-up similar to that for Method A
gave the naphthol 4c (66 mg, 56%).
4-(2,5-Dimethylphenyl)-2,5,8-trimethyl-1-naphthol 4d
(Method C). Amorphous solid; δH (400 MHz) 1.84 (3 H, s), 1.95
(3 H, s), 1.96 (3 H, s), 2.34 (3 H, s), 2.98 (3 H, s), 5.23 (1 H, br s,
OH), 6.68 (1 H, s), 6.92 (1 H, s) and 7.00–7.20 (4 H, m);
νmax(neat)/cmϪ1 3526, 2967, 2932 and 1439; m/z (EI) 290.1679
(M+. C21H22O requires 290.1672).
2-Methyl-4-(2,4-dichloro-3-methylphenyl)-1-naphthol 4e
(Method C). Light yellow crystals, mp 126–127 ЊC; δH (400
MHz) 2.14 (3 H, s), 2.60 (3 H, s), 5.57 (1 H, br s, OH), 6.79 (1 H,
s), 7.04 (1 H, d, J 8.1), 7.20 (1 H, d, J 8.0), 7.34–7.44 (2 H, m),
7.41 (1 H, d, J 8.1) and 8.21 (1 H, d, J 8.3); δC 18.1, 20.3, 110.9,
121.6, 122.8, 124.3, 125.1, 126.7, 127.5, 128.2, 130.0, 133.3,
133.9, 134.2, 134.9, 136.2, 137.4 and 151.1; νmax(neat)/cmϪ1
3422, 2361 and 1655; m/z (EI) 316.0430 (M+. C18H14Cl2O
requires 316.0423).
6-Chloro-2-methyl-4-phenyl-1-naphthol 4f (Method C).
Amorphous solid; δH (400 MHz) 2.17 (3 H, s), 5.57 (1 H, br s,
OH), 6.76 (1 H, s), 7.10–7.50 (7 H, m) and 8.20 (1 H, d, J 8.4);
δC 20.8, 111.3, 121.4, 122.8, 124.2, 125.7, 126.5, 128.6, 129.8,
132.1, 132.8, 133.5, 133.9, 138.2 and 150.7; νmax(Nujol)/cmϪ1
3540, 1580 and 1462; m/z (EI) 268.0666 (M+. C17H13ClO
requires 268.0656).
1-(2,5-Dichlorophenyl)-3-(hydroxymethyl)-4-methoxy-2-
naphthoic acid lactone 13b
A mixture of the methyl ester 12b (40 mg, 107 µmol), N-
bromosuccinimide (21 mg, 118 µmol) and azoisobutyronitrile (1
mg, 6 µmol) in CCl4 (0.5 cm3) was heated under reflux for 2 h.
After this the mixture was allowed to cool to room temp., when
it was diluted with water (ca. 5 cm3) and extracted twice with
6-Chloro-4-(2,4-dichloro-3-methylphenyl)-2-methyl-1-
naphthol 4g (Method C). Amorphous solid; δH (400 MHz) 2.12
(3 H, s), 2.58 (3 H, s), 5.30–5.80 (1 H, br s, OH), 6.79 (1 H, s),
7.00 (1 H, d, J 8.1), 7.10 (1 H, d, J 9.0), 7.28 (1 H, dd, J 9.0, J
484
J. Chem. Soc., Perkin Trans. 1, 1997

View Article Online
diethyl ether. The combined extracts were washed with brine,
dried (Na2SO4) and concentrated to give the crude bromide (60
mg). 4  Aqueous NaOH (2 cm3) was slowly added to a stirred
solution of the crude bromide (60 mg) in dioxane (2 cm3) at
70 ЊC. After the mixture had been stirred at the same temp. for 2
h it was allowed to cool to room temp. and diluted with diethyl
ether (ca. 5 cm3) and 4  aqueous HCl (adjusted to pH 1). The
separated organic phase was washed with water and brine, dried
(Na2SO4) and concentrated to give a crude oil. This was puri-
fied by silica gel column chromatography (hexane–ethyl acetate,
4:1) to give the product 13b (36 mg, 95%) as colourless crystals,
mp 235–240 ЊC (Found: C, 63.15; H, 2.97. C19H12Cl2O3 requires
C, 63.53; H, 3.37%); δH (400 MHz) 4.21 (3 H, s), 5.64 (1 H, d,
Jgem 14.2), 5.69 (1 H, d, Jgem 14.2), 7.27 (1 H, d, J 3.0), 7.41–7.45
(1 H, m), 7.50 (1 H, d, J 8.8), 7.53–7.57 (2 H, m), 7.60–7.71 (1
H, m) and 8.36 (1 H, d, J 8.8); νmax(KBr)/cmϪ1 2365, 1750 and
1589.
1-Phenyl-3-(hydroxymethyl)-4-methoxy-2-naphthoic acid lac-
tone 13a. Following the procedure for preparing the ester 13b
described above, with 12a in the place of 12b, the product 13a
(98%) was obtained as colourless crystals, mp 181–184 ЊC
(Found: C, 78.4; H, 4.6. C19H14O3 requires C, 78.61; H, 4.86%);
δH (400 MHz) 4.19 (3 H, s), 5.31 (2 H, s), 7.33–7.40 (2 H, m),
7.45–7.54 (4 H, m), 7.60–7.71 (1 H, m), 7.75 (1 H, d, J 8.05) and
8.35 (1 H, d, J 8.31); νmax(KBr)/cmϪ1 2922, 1760 and 1361.
Note: The yield was improved by optimization after our
communication.11b
combined extracts were washed with water and brine, dried
(Na2SO4) and concentrated. MeOH (50 cm3) and a little
toluene-p-sulfonic acid were added to the residue and the mix-
ture was stored overnight. Saturated aqueous NaHCO3 was
added to the mixture which was then evaporated to give a resi-
due; this was extracted with diethyl ether. The extract was
washed with water and brine, dried (Na2SO4), and concen-
trated. Recrystallization of the residue from hexane–diethyl
ether (5:1) gave the product 17d (5.17 g, 63%) as colourless
crystals, mp 127–128 ЊC (Found: C, 49.6; H, 4.4. C11H11Cl3O
requires C, 49.75; H, 4.17%); δH (400 MHz) 1.28 (3 H, s), 2.65 (1
H), 3.86 (1 H, d, Jgem 11.7), 4.01 (1 H, d, Jgem 11.7), 7.18–7.23 (2
H, m) and 7.30–7.35 (2 H, m); δC 15.0, 36.4, 39.1, 69.0, 69.2,
128.6, 131.2, 131.6 and 133.4; νmax(KBr)/cmϪ1 3225, 1491 and
1042.
(1R*,3S*)-3-(4-Methoxyphenyl)-2,2-dichloro-1-methylcyclo-
propylmethanol 17e. Following the procedure for preparing the
alcohol 17d described above, with (E)-3-(4-methoxyphenyl)-2-
methylprop-2-en-1-ol, the product 17e (77%) was obtained as
colourless crystals, mp 93–94 ЊC (Found: C, 58.6; H, 5.4.
C12H14Cl2O requires C, 58.79; H, 5.76%); δH (400 MHz) 1.20 (3
H, s), 1.50–1.90 (1 H, s, OH), 2.56 (1 H, s), 3.74 (3 H, s), 3.78 (1
H, d, Jgem 11.7), 3.96 (1 H, d, Jgem 11.7), 6.72–6.95 (2 H, m) and
7.01–7.28 (2 H, m); νmax(KBr)/cmϪ1 3362, 1514 and 1246.
Acknowledgements
We thank Dr Yukihiko Hashimoto, Dr Minoru Hayashi and
Mr Atsushi Sudoh of Tokyo University for HRMS measure-
ments. This work was partially supported by a Grant-in-Aid for
Scientific Research from the Ministry of Education, Science
and Culture (Japan).
2-(4-Methoxyphenyl)-3-methyl-5-phenylfuran 16a
Furan synthesis: typical procedure. AlCl3 (138 mg, 1.03
mmol) was added portion-by-portion to a stirred solution of
the ketone 14g (123 mg, 0.47 mmol) in benzene (2.2 cm3) at
room temp. and the mixture was stirred for 20 h. Work-up
similar to that described in method A gave the product 16a (55
mg, 44%) as colourless crystals, mp 91–92 ЊC (Found: C, 81.5;
H, 5.9. C18H16O2 requires C, 81.79; H, 6.10%); δH (90 MHz) 2.28
(3 H, s), 3.86 (3 H, s), 6.60 (1 H, s), 6.97 (2 H, d, J 8.6) and 7.19–
7.82 (7 H, m); νmax(KBr)/cmϪ1 2365, 1607 and 1507.
2-(4-Methoxyphenyl)-3-methyl-5-(p-tolyl)furan 16b. Follow-
ing the procedure for preparing the furan 16a described above,
using toluene in the place of benzene the product 16b (65%) was
obtained as colourless crystals, mp 105–107 ЊC (Found: C, 80.2;
H, 6.3. C19H18O2 requires C, 81.99; H, 6.52%); δH (90 MHz) 2.28
(3 H, s), 2.36 (3 H, s), 3.82 (3 H, s), 6.51 (1 H, s), 6.96 (2 H, d, J
9.1), 7.18 (2 H, d, J 8.6), 7.60 (2 H, d, J 8.6) and 7.61 (2 H, d, J
9.1); νmax(KBr)/cmϪ1 2920, 1601 and 1510.
5-(4-Chlorophenyl)-2-(4-methoxyphenyl)-3-methylfuran 16c.
Following the procedure for preparing the furan 16a described
above, with chlorobenzene in the place of benzene, the product
16c (37%) was obtained as colourless crystals, mp 85–86 ЊC
(Found: C, 72.1; H, 4.9. C18H15ClO2 requires C, 72.36; H,
5.06%); δH (90 MHz) 2.28 (3 H, s), 3.84 (3 H, s), 6.57 (1 H, s),
6.99 (2 H, d, J 8.6), 7.33 (2 H, d, J 8.6), 7.62 (2 H, d, J 8.6) and
7.62 (2 H, d, J 8.6); νmax(KBr)/cmϪ1 2930, 1605 and 1507.
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