Investigation of the reaction of 2-bromo-1-naphthol with arylacetonitriles and LiTMP: Facile synthesis of 3-arylmethyl1-hydroxynaphthalene-2-carbonitriles

Article abstract of DOI:10.1039/b003935g

2-Bromo-1-naphthol reacts with arylacetonitriles and 3-thienylacetonitrile in the presence of LiTMP to give the rearranged 3-benzyl-1-hydroxynaphthalene-2-carbonitriles and 11-amino-5H-anthra[2,3-b]thiophen-10-one, respectively. The reactions proceed via a tandem addition-rearrangement pathway involving a non-synchronous [2 + 2] cycloaddition of an N-lithiated ketenimine and 2,3-didehydronaphthalene 1-oxide. An explanation of the orientation to and reactivity of the aforementioned aryne is presented in terms of chelation between the OLi group and the attacking nitrile nucleophile. Support for the intermediacy of 2,3-didehydronaphthalene 1-oxide was accomplished by obtaining 3-amino-1-naphthols from the reaction of 2-bromonaphthol and the appropriate lithium amide. Alternate non-aryne mechanisms were addressed, but were rejected based on experimental results. The Royal Society of Chemistry 2000.

Full text of DOI:10.1039/b003935g

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Investigation of the reaction of 2-bromo-1-naphthol with
arylacetonitriles and LiTMP: facile synthesis of 3-arylmethyl-
1-hydroxynaphthalene-2-carbonitriles
1
Sagun Tandel, Anlai Wang, Hongming Zhang, Pervaiz Yousuf and Edward R. Biehl*
Department of Chemistry, Southern Methodist University, Dallas, TX 752753, USA.
E-mail: ebiehl@post.smu.edu
Received (in Cambridge, UK) 16th May 2000, Accepted 26th July 2000
Published on the Web 4th September 2000
2-Bromo-1-naphthol reacts with arylacetonitriles and 3-thienylacetonitrile in the presence of LiTMP to give
the rearranged 3-benzyl-1-hydroxynaphthalene-2-carbonitriles and 11-amino-5H-anthra[2,3-b]thiophen-10-one,
respectively. The reactions proceed via a tandem addition–rearrangement pathway involving a non-synchronous
[2 ϩ 2] cycloaddition of an N-lithiated ketenimine and 2,3-didehydronaphthalene 1-oxide. An explanation of the
orientation to and reactivity of the aforementioned aryne is presented in terms of chelation between the OLi
group and the attacking nitrile nucleophile. Support for the intermediacy of 2,3-didehydronaphthalene 1-oxide
was accomplished by obtaining 3-amino-1-naphthols from the reaction of 2-bromonaphthol and the appropriate
lithium amide. Alternate non-aryne mechanisms were addressed, but were rejected based on experimental results.
through an earlier transition state than that for nitrile anion
Introduction
addition to 3,6-dimethylbenzyne. In such a transition state,
the bonding between the nitrile anion and the 2,3-
didehydronaphthalene would be weaker than that between the
nitrile and 3,6-dimethylbenzyne. Therefore the former transi-
tion state would be expected to collapse to give the usual aryne–
nitrile anion adduct9 rather than undergo a [2 ϩ 2] process.
The OLi group has been shown to promote the key [2 ϩ 2]
cycloaddition pathway in reactions involving 2,3-didehydro-
phenoxide. To see if the OLi group could also influence reac-
tions involving 2,3-didehydronaphthlene 1-oxide in a similar
way, a study of the reaction of 2-bromo-1-naphthol with
certain arylacetonitriles in the presence of lithium amide bases
was initiated. If this were to be the case, then the 2 ϩ 2 cyclo-
addition–aryne reaction would provide a ready access to
novel 3-arylmethyl-1-hydroxynaphthlene-2-carbonitriles using
readily available starting materials.
Potassium and sodium amides in liquid ammonia generate
didehydrophenoxides from halophenols reluctantly.1 However,
we2 have shown that lithium 2,2,6,6-tetramethylpiperidide
(LiTMP) can readily convert 2-bromophenol to 2,3-didehydro-
phenoxide. This aryne can be trapped by lithiated arylaceto-
nitriles to give 2-arylmethyl-6-hydroxybenzenecarbonitriles,
after proton quench. The benzonitrile products are most likely
formed via a tandem addition–rearrangement pathway (vide
infra).3 The key step in the process involves a [2 ϩ 2] non-
synchronous cycloaddition in which the C1 and C2 carbons of
a nitrile derived N-lithiated ketenimine [ArC H᎐C ᎐N–Li] add
᎐
᎐
1
2
regioselectively to the respective C2 and C3 positions of 2,3-
didehydrophenoxide to form a N-lithiated benzocyclobutan-
imine intermediate. The observed regioselectivity indicates that
the bonding in the transition state between the C3 of the aryne
and C2 of the ketenimine is further along in its formation than
that between C2 of the aryne and C1 of the ketenimine. In such
a transition state, a partial negative charge is developed at C2
of the aryne, whereas in the transition state for the opposition
mode of cycloaddition the partial negative charge is developed
at C3 of the aryne. Accordingly, the partial negative charge at
C2 in the former transition state would be stabilized to a greater
extent than that at C3 in the latter due to its closer proximity to
the electron-withdrawing OLi group at C1, and this favors the
observed products.4 These arguments are supported by density
functional theory (DFT) calculations.5,6
Our orientation–reactivity studies of the OLi group have
been extended to include the 2,3-didehydronaphthalene 1-oxide
intermediate. Previously, it was shown that 1,4-dimethoxy-2,3-
didehydronaphthalene reacts with arylacetonitrile anions to
give only simple addition products via the usual aryne pathway.7
On the other hand, 3,6-dimethylbenzyne reacts with aryl-
acetonitrile anions to give rearranged nitriles exclusively.
Semi-empirical AM1 calculations showed that 2,3-didehydro-
naphthalene was less stable by 0.72 kcal molϪ1 than benzyne
itself due to the difficulty of 2,3-didehydronaphthalene to
accommodate a shorter dehydro-bond at C2–C3.8 Because of
the increase in energy, nitrile anion addition to 1,4-dimethoxy-
2,3-didehydronaphthalene is, therefore, expected to proceed
Results and discussion
2-Bromo-1-naphthol 1 was chosen as the 2,3-didehydronaph-
thalene 1-oxide precursor, due to its ease of preparation.10
Compound 1 reacted with a variety of arylacetonitriles (2a–e)
and 3-thienylacetonitrile (2f) in presence of LiTMP in THF at
room temperature to give the corresponding 3-arylmethyl-1-
hydroxynaphthalene-2-carbonitriles 3a–e (eqn. (1)) in yields
ranging from 44 to 85%. However, the reaction of 1 with 3-
thienylacetonitrile 2f afforded 11-amino-5H-anthra[2,3-b]-
thiophen-10-one 4 in 44% yield (see eqn. (2)).
The reactions were carried out by first adding LiTMP to a
solution of 1 followed by the addition of nitriles 2a–f. The
order of the addition is the reverse of that generally used
in aryne reactions. GC monitoring of the reaction mixtures
indicated that the reaction did not commence until the addition
of 2a–f. During the addition of 2a–f, the solution immediately
developed a red color, which gradually deepened over the
course of the reaction. We have found throughout our extensive
studies of aryne reactions over the past forty years that, without
exception, such color changes are indicative of products formed
from a base-mediated aryne reaction.11 The red color in these
reaction solutions is thought to be due to the formation of
DOI: 10.1039/b003935g
J. Chem. Soc., Perkin Trans. 1, 2000, 3149–3153
This journal is © The Royal Society of Chemistry 2000
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Table 1 Physical properties of 3-arylmethyl-1-hydroxynaphthalene-2-
carbonitriles 3a–e, 11-amino-5H-anthra[2,3-b]thiophen-10-one 4, and
amines 15 and 16
Found (%) (Required)
Compound
(Formula)
Yield
(%)
Mp/ЊCa
C
H
N
3a
85
59
59
48
42
57
45
15
Viscous liquid
Viscous liquid
215–216
78.9
(78.4)
75.4
(75.3)
85.4
(85.3)
83.4
(83.5)
69.4
(69.7)
72.5
(72.4)
79.8
(79.7)
79.4
(79.3)
5.2
(5.3)
5.3
(5.5)
4.9
(4.8)
5.4
(5.5)
3.8
(3.7)
4.3
(4.2)
9.4
(9.3)
7.6
(7.5)
4.8
(4.7)
5.5
(5.4)
4.5
(4.4)
5.3
(5.1)
4.3
(4.2)
5.2b
(5.3)
5.1
(5.2)
6.3
C19H15NO2
3b
C18H13NO
3c
C22H15NO
3d
C19H15NO
3e
C19H12NOF3
4
C14H13NOS
15
C18H25NO
16
C15H17NO
Fig. 1 ORTEP diagram of compound 4.
Viscous liquid
138–140
the 11-amino-10-keto tautomer, which is presumably stabilized
by intramolecular H-bonding between the 11-amino and
10-carbonyl group.
160 (decomp.)
Viscous liquid
Viscous liquid
The products 3a–e and 4 are most likely formed via a tandem
addition–rearrangement pathway3 as shown in Scheme 1. In
this reaction sequence, reactant 1 reacts with LiTMP to give the
lithiated 2-bromonaphthalene 1-oxide 5. The nitriles 2a–f are
then added and react with LiTMP to give N-lithiated keten-
imines 8a–f via the lithiated arylacetonitriles 6a–f. In the
presence of LiTMP and 8a–f, 5 is converted to 2,3-didehydro-
naphthalene 1-oxide 7. The ketenimines 8a–f then add regio-
selectively to 7 to produce lithiated benzocyclobutanimines
9a–f, which in turn fragment to α-lithiated benzylbenzonitriles
10a–e and thienylmethylbenzonitrile 10f. With the exception of
10f, the naphthalene-2-carbonitriles 10a–e are converted to 3a–e
during acidic aqueous work up. In the exceptional case, the
thienyl derivative 10f cyclizes by a Stork type mechanism to the
tetracyclic compound 11, which can be converted to 4 via the
dilithiated intermediate 12. The lithiated derivative of 3-thien-
ylacetonitrile 2h has been found to react with 2,3-didehydro-
benzyl oxide in a similar fashion to give 9-aminonaphtho[2,3-b]-
thiophen-8-ylmethanol.15
The fact that 7, unlike 1,4-dimethyl-2,3-didehydronaph-
thalene, proceeds via a [2 ϩ 2] cycloaddition pathway rather
than the usual aryne addition pathway is most likely the result
of a favorable interaction between the lithium of the OLi group
in 7 and the nitrogen atom of the cyano group of the attacking
nucleophile 8a–f. Such an interaction, shown in Fig. 2, presum-
ably overcomes the inherent instability of the 2,3-didehydro-
naphthalene ring by bringing the bonding loci sufficiently close
in the transition state for the 2 ϩ 2 cycloaddition step.
(6.2)
a All solid products were recrystallized from 80% hexane–20% ethyl
acetate. b S 12.2% (12.1)
resonance delocalized α-lithiated derivatives of 3a–f. The fact
that nitriles 6a–f must be present for aryne generation to occur
is consistent with previous studies involving the generation of
other arynes possessing charged substituents.11,2 It has been
suggested12 that nitriles accelerate the rate of aryne generation
by increasing the strength of the base involved in the rate
determining hydrogen abstraction step of the aryne reaction.9
When the usual procedure was used, the yields of 3a–e and 4
were markedly lower due to significant amounts of dimeric and
polymeric side products. The use of the less expensive LDA as
an aryne generating base was explored as an alternate to the
considerably more expensive LiTMP. However, nitriles 3a–e
were formed in lower yields in these reactions due to the form-
ation of high molecular weight tars and the reduction of 1 to
1-naphthol by LDA.13
The identity of the structures of 3a–e and 4 was determined
1
by H NMR, 13C NMR, and FTIR spectroscopy. The spectral
data are presented in the Experimental section and the melting
points and elemental analyses are shown in Table 1. Single-
crystal X-ray diffractometry further aided in the identification
of the structure of 4. An ORTEP14 drawing of 4 is shown in
Fig. 1. NMR spectroscopy confirmed that 4 exists exclusively as
Since benzynes are reluctantly formed from the reaction of
alkali metals and halophenols, it could be argued that benzyne
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Scheme 1
not detect benzonitrile 3a, but rather revealed the presence of
starting materials 1 (62%) and 2a (98%) as well as 1-naphthol
(38%). In fact, 5 did not react with phenylacetonitrile 2a, whose
cyano group is even more electrophilic than that of 6a. Thus,
this alternate mechanism is unlikely. Haloarenes occasionally
react with certain nucleophiles under aryne-forming conditions
by a SRN116 pathway. However, this mechanism can also be
discarded since it would predict, incorrectly, a direct displace-
ment of the 2-bromo group by the α-carbon of 6.
Although these negative results add credence to the inter-
mediacy of 7 in these reactions, we were able to obtain
additional support by treating 1 with lithium di-n-butylamide
and lithium piperidide in the absence of arylnitrile for 2 days.
As shown in eqn. (3), these amides reacted with 1 to give 3-di-n-
Fig. 2 Possible transition state involving cycloaddition of lithiated
ketenimine 8 to aryne 7.
formation from 2-halo-1-naphthol should be even more
difficult given the increased C2–C3 bond length of the naph-
thalene system. Thus, it was prudent that other non-aryne
pathways for the formation of nitriles 3a–f be addressed. A
possible alternate non-benzyne mechanism, shown in Scheme 2,
(3)
butylamino-1-naphthol 15 and 3-(piperidin-1-yl)-1-naphthol
16 in 45% and 15%, respectively. The fact that cine substituted
products (i.e. substitution at the carbon adjacent to the
debromo carbon) were obtained in these reactions argues
strongly for the intermediacy of 7.4 Under these conditions,
LiTMP did not react with 1 and LDA reduced 1 to 1-naphthol
(38% yield).
Scheme 2
In conclusion, a facile, one-step preparation of 3-benzyl-1-
hydroxynaphthalene-2-carbonitriles
3a–e,
11-amino-5H-
suggests that the lithiated benzocyclobutanimines 9 could be
formed by an initial attack of the cyano group of the α-lithiated
arylacetonitrile 6 on C-2 of the naphthalene-1 oxide 5 by the
cyano group of the (enolate type mechanism) affording adduct
13. Cyclization of 13 (Michael type addition) and loss of HBr
from the resulting adduct 14 would then give 9.
anthra[2,3-b]thiophen-10-one 4 and 3-amino-1-naphthols 15
and 16 via 2,3-didehydronaphthalene 1-oxide 7 has been
described. Preparations of these 1,2,3-trisubstitued naph-
thalenes by conventional non-arynic methodology would be
difficult.
To test the validity of this alternative pathway, 2-bromo-
naphthalene 1-oxide 5 was treated with α-lithiophenylaceto-
nitrile 6b under conditions similar to those used in the
LiTMP-mediated reactions of 1, but with the absence of
LiTMP. GC-MS analysis of the reaction mixture, however, did
Experimental
General data
Melting points were taken on a Mel-Temp II capillary
J. Chem. Soc., Perkin Trans. 1, 2000, 3149–3153
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apparatus and are uncorrected with respect to stem correction.
IR spectra were recorded on a Nicolet Magna-IRTM 550 FTIR
(d, J = 8.4 Hz, 1 H); δC(400 MHz; CDCl3) 40.7, 94.0, 117.2,
121.0, 123.5, 124.0, 124.1, 126.2, 126.5, 126.7, 127.9, 129.5,
130.4, 133.0, 136.5, 136.9, 140.1, 160.1.
1
spectrometer, and the H and 13C NMR spectra were recorded
on a 400 MHz Bruker AVANCE DRX-400 multi-nuclear
NMR spectrometer; chemical shifts were referenced to TMS as
internal standard. Elemental analyses were obtained from
SMU Analytical Laboratories. 1-Naphthol, arylacetonitriles,
2,2,6,6-dimethylpiperidine, diisopropylamine, and n-BuLi were
purchased from Aldrich Chemical Company. Diisopropylamine
and 2,2,6,6-dimethylpiperidine were refluxed over and distilled
from calcium hydride. Tetrahydrofuran (THF) was distilled
from Na–benzophenone immediately prior to use. The glass-
ware was heated at 125 ЊC in an oven overnight prior to use.
All benzyne reactions were done under an atmosphere of dry
O2-free N2 via balloon.
11-Amino-5H-anthra[2,3-b]thiophen-10-one 4. δH(400 MHz;
CDCl3) 4.43 (s, 2 H), 7.21 (br, 2 H), 7.29 (s, 1 H), 7.31 (d, J = 6
Hz, 1 H), 7.45 (t, J = 8 Hz, 1 H), 7.56 (d, J = 8.8 Hz, 1 H), 7.61
(d, J = 5.2 Hz, 1 H), 8.33 (d, J = 7.6 Hz, 1 H); δC(400 MHz;
CDCl3) 33.8, 110.4, 111.8, 124.7, 125.2, 127.0, 127.3, 128.1,
129.6, 132.5, 133.5, 138.2, 140.2, 143.9, 147.4, 187.6.
General procedure for the reaction of 1 with lithium amides
In a flame-dried flask flushed with nitrogen, the lithium amide
(10 mmol) was prepared by adding n-BuLi (10 mmol, 2.5 M in
hexane) to a solution of the appropriate amine (10 mmol) in
THF (50 mL) at rt. The appropriate aryne precursor (2 mmol)
was then added and the resulting mixture stirred for 48 h. At
this point the reactions were worked up in the same manner
described above for the reaction involving arylacetonitriles. The
spectral properties of 15 and 16 are given below.
General procedure for the reaction of 1 with arylacetonitriles
In a flame-dried flask flushed with nitrogen, fresh LiTMP or
LDA (10 mmol) was prepared by adding n-BuLi (10 mmol, 2.5
M in hexane) to a solution of 2,2,6,6-tetramethylpiperidine
(1.8 g, 10 mmol) or diisopropylamine (1.0 g, 10 mmol) in THF
(50 mL) at rt. After stirring for 10 min, 2-bromo-1-naphthol
(0.45 g, 2 mmol) was added slowly and the stirring continued
for 10 min. The appropriate nitrile (2 mmol) was then added,
and the resulting solution immediately developed a dark red
color. After stirring overnight, the reaction mixture was
quenched with saturated NH4Cl solution (30 mL), and then
extracted with methylene chloride. The combined extracts were
washed with dilute HCl, dried (Na2SO4), and concentrated
(rotary evaporator) to give a crude oily material. Chrom-
atography of this material on silica gel (hexane–ethyl acetate,
9:1) gave the pure product 3a–e, and 4. The yields, mp and
elemental analyses for these compounds are presented in
Table 1 and the spectral data are given below.
3-Di-n-butylamino-1-naphthol 15. δH(400 MHz; CDCl3) 0.96
(t, J = 7.6 Hz, 6 H), 1.33–1.39 (m, 4 H), 1.63–1.68 (m, 4 H), 3.45
(t, J = 8.0 Hz, 4 H), 5.8 (s, 1 H), 7.24 (s, 1 H), 7.57–7.59 (m,
1 H), 7.65–7.67 (m, 1 H), 7.93–7.96 (m, 1 H), 8.01 (d, J = 1.2
Hz, 1 H), 8.23 (d, J = 1.2 Hz, 1 H); δC(400 MHz; CDCl3) 14.2,
20.6, 30.0, 53.2, 106.4, 125.6, 126.8, 132.2, 133.3, 134.1, 134.2,
151.6, 183.1, 183.3.
3-(Piperidin-1-yl)-1-naphthol 16. δH(400 MHz; CDCl3) 0.96
(t, J = 7.6 Hz, 6 H), 1.33–1.39 (m, 4 H), 1.63–1.68 (m, 4 H), 3.45
(t, J = 8.0 Hz, 4 H), 5.8 (s, 1 H), 7.24 (s, 1 H), 7.57–7.59 (m,
1 H), 7.65–7.67 (m, 1 H), 7.93–7.96 (m, 1 H), 8.01 (d, J = 1.2
Hz, 1 H), 8.23 (d, J = 1.2 Hz, 1 H).
1-Hydroxy-3-(4-methoxyphenylmethyl)naphthalene-2-carbo-
nitrile 3a. νmax/cmϪ1 2220 (aromatic CN), 3423 (phenolic
OH); δH(400 MHz; CDCl3) 3.81 (s, 3 H), 4.18 (s, 2 H), 6.89
(dd J = 6.4 Hz, 1.6 Hz, 3 H), 7.23 (d, J = 8.4 Hz, 2 H), 7.53
(t, J = 8.2 Hz, 1 H), 7.62 (t, J = 8.2 Hz, 1 H), 7.74 (d, J = 8.4 Hz,
1 H), 8.24 (d, J = 8.4 Hz, 1 H).
X-Ray analysis of 11-amino-5H-anthra[2,3-b]thiophen-10-one 4
X-ray analysis of crystals of 4 (C16H11NOS, M 265.32) was
carried out on a Brucker AXS P4 diffractometer at 228 K. The
crystal was orthorhombic, space group PZ1Z1Z1 with unit
cell a = 7.131(1), b = 12.598(2), c = 13.699(2) Å, β = 90.00Њ,
V = 1230.9(3) Å, Z = 4, Dx = 1.432 g cmϪ3, µ = 0.252 mmϪ1
.
Mo-Kα radiation (λ = 0.71073 Å), 903 reflections measured,
863 unique, 2409 with F ≥ 2σ(F) gave R1 = 0.032 in a full matrix
least squares refinement17 with 173 parameters. CCDC refer-
ence number 207/461. See http://www.rsc.org/suppdata/p1/b0/
b003935g/ for crystallographic files in .cif format.
1-Hydroxy-3-(phenylmethyl)naphthalene-2-carbonitrile
3b.
νmax/cmϪ1 2216 (aromatic CN), 3389 (phenolic OH); δH(400
MHz; CDCl3) 4.25 (s 2 H), 7.22 (s, 1 H), 7.33–7.28 (m, 5 H),
7.54 (d, J = 8.2 Hz, 1 H), 7.62 (t, J = 8.2 Hz, 1 H), 7.74 (d,
J = 8.2 Hz), 8.25 (d, J = 8.4 Hz, 1 H).
Acknowledgements
This work was supported, in part, by grants from the Welch
Foundation, Houston, TX, and the Petroleum Research
Corporation, administered by the American Chemical Society.
1-Hydroxy-3-(1-naphthylmethyl)naphthalene-2-carbonitrile
3c. νmax/cmϪ1 2220 (aromatic CN), 3390 (phenolic OH); δH(400
MHz; CDCl3) 4.71 (s, 1 H), 6.90 (s, 1 H), 7.36 (d, J = 8.2 Hz,
1H), 7.54–7.48 (m, 5 H), 7.61 (d, J = 8 Hz, 1 H), 7.91–7.95 (m, 3
H), 8.25 (d, J = 8.2 Hz, 1 H); δC(400 MHz; CDCl3) 37.7, 95.8,
117.5, 120.2, 123.3, 123.8, 124.4, 125.9, 125.9, 126.0, 126.1,
126.5, 127.9, 129.0, 129.4, 132.4, 134.2, 135.1, 136.2, 138.1.
References
1 G. B. R. deGraff, H. J. d. Hertog and W. C. Melger, Tetrahedron
Lett., 1965, 14, 963.
2 S. Tandel, H. Zhang, N. Quadra, G. P. Ford and E. R. Biehl,
J. Chem. Soc., 2000, 587.
3 P. D. Pansegrau, W. F. Rieker and A. I. Meyers, J. Am. Chem. Soc.,
1988, 110, 7148.
4 J. D. Roberts, C. W. Vaughan, L. A. Carlsmith and D. Semenov,
J. Am. Chem. Soc., 1956, 78, 611.
1-Hydroxy-3-(3-methylphenylmethyl)naphthalene-2-carbo-
nitrile 3d. νmax/cmϪ1 2225 (aromatic CN), 3410 (phenolic
OH); δH(400 MHz; CDCl3) 2.35 (s, 3 H), 4.21(s, 2 H), 7.09–7.10
(m, 2 H), 7.23 (d, J = 7.6 Hz, 2 H), 7.55 (d, J = 8 Hz, 2 H), 7.62
(t, J = 8 Hz, 1 H), 7.74 (d, J = 8 Hz, 1 H), 8.26 (d, J = 8.4 Hz, 1
H); δC(400 MHz; CDCl3) 21.8, 40.6, 94.5, 116.79, 116.8, 121.3,
122.7, 123.1, 126.5, 127.9, 127.8, 128.0 130.1, 130.3, 136.5,
138.1, 138.7, 138.9, 158.6.
5 W. J. Hehre, L. Radom, P. v. R. Schleyer and L. A. Pople, Ab Initio
Molecular Orbital Theory, John Wiley & Sons, New York, USA,
1997.
6 P. Perdew and L. Lou, A Guide to Density Functional Calculations
in Spartan, Wavefunction, Inc, 18401 Von Karman, #370, Irvine,
CA 97215, USA, 1997.
7 E. R. Biehl, S. P. Khanapure, M. Hansen, M. Dutt and D. Swartling,
Synthesis, 1994, 957.
1-Hydroxy-3-(3-trifluromethylphenylmethyl)naphthalene-2-
carbonitrile 3e. νmax/cmϪ1 2215 (aromatic CN), 3415 (phenolic
OH); δH(400 MHz; CDCl3) 4.25 (s, 2 H), 7.13 (s, 1 H), 7.41–7.53
(m, 5H), 7.60 (t, J = 8 Hz, 1 H), 7.70 (d, J = 8 Hz, 1 H), 8.28
3152
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View Article Online
8 G. P. Ford and E. R. Biehl, Tetrahedron Lett., 1995, 36, 3663.
9 J. D. Roberts, D. Semenow, H. E. Simmons and J. L. A. Carlsmith,
J. Am. Chem. Soc., 1956, 78, 601.
10 D. E. Pearson, R. D. Wysong and C. V. Breder, J. Org. Chem., 1967,
32, 2358.
11 A. Wang, J. A. Maguire and E. Biehl, J. Org. Chem., 1998, 63, 2451.
12 E. R. Biehl, K. C. Hsu and E. Nieh, J. Org. Chem., 1970, 35, 2454.
13 E. R. Biehl, S. M. Smith, S. Lapis and P. C. Reeves, J. Org. Chem.,
1972, 37, 3529.
14 C. K. Johnson, ORTEP, Report ORNL-3794, Oak Ridge National
Laboratory, Oak Ridge, Tennessee, 1965.
15 A. Wang and E. Biehl, J. Chem. Soc., Perkin Trans. 1, 1998, 1461.
16 J. F. Bunnett, Acc. Chem. Res., 1978, 11, 413.
17 G. M. Sheldrick, in SHELX-plus, V. 5/601, Madison, WI, 1994.
J. Chem. Soc., Perkin Trans. 1, 2000, 3149–3153
3153