Regioselectivity in aromatic Claisen rearrangements

Article abstract of DOI:10.1021/jo026385g

Theoretical calculations and the isomeric product composition for a series of eight meta-substituted allyl aryl ethers confirm the reliability of a new ¹H NMR methodology used to predict aromatic Claisen regioselectivity from ground-state confo

Full text of DOI:10.1021/jo026385g

Regioselectivity in Ar om a tic Cla isen Rea r r a n gem en ts
Fa´bio Cesar Gozzo, Sergio Antonio Fernandes, Denise Cristina Rodrigues,
Marcos Nogueira Eberlin,* and Anita J ocelyne Marsaioli*
Institute of Chemistry, State University of CampinassUNICAMP,
CP 6154, 13083-970 Campinas, SP, Brazil
anita@iqm.unicamp.br; eberlin@iqm.unicamp.br
Received September 2, 2002
Theoretical calculations and the isomeric product composition for a series of eight meta-substituted
1
allyl aryl ethers confirm the reliability of a new H NMR methodology used to predict aromatic
Claisen regioselectivity from ground-state conformational preference of the reactant allyloxy group.
Frontier HOMO-LUMO intramolecular orbital interactions, a classical approach in predicting
reactivity and selectivity for Claisen rearrangements of allyl vinyl ethers, is shown to fail to mimic
transition-state orbital interactions for aromatic Claisen rearrangements of meta-substituted allyl
aryl ethers. B3LYP/6-31G(d,p) calculations on reactants and transition states are shown, however,
to correctly predict the outcome of such aromatic Claisen rearrangements from either the preferential
reactant ground-state conformation (theoretical predictions that agree with the NMR measurements)
or the less energetic transition state, or both.
SCHEME 1
In tr od u ction
The recognition that the Claisen rearrangement is the
only known 3,3-sigmatropic shift enzyme-catalyzed reac-
tion (chorismate-perphenate rearrangement)1 has re-
awakened the interest for this pericyclic transformation
of allyl vinyl and allyl aryl ethers, and has further
promoted this classic and useful synthetic reaction to an
outstanding in vivo biosynthetic transformation.2 The
intramolecular cyclic nature of the Claisen rearrange-
ment is well established, and theoretical calculations
have indicated that this exothermic process occurs via a
nonsynchronized concerted pathway. There is, however,
considerable disagreement over the transition-state struc-
tures, which endangers product prediction and the
understanding of substituent and solvent effects. Par-
ticularly challenging has been to predict the regioselec-
tivity and transition-state structures for aromatic Claisen
rearrangements of meta-substituted allyl aryl ethers.4,5
Recent theoretical calculations on aromatic and ali-
phatic Claisen rearrangements were supported by a set
of experimental kinetic isotope effects.4 It was then
concluded that the nature of the electronic structure of
these transition states is between those calculated at the
B3LYP/6-31G* and MP2/6-31G* levels. The main draw-
back in comparing theoretical and experimental data on
Claisen rearrangements lies in the inaccuracy of experi-
mental results, which is often the case for kinetic isotope
effects of heavy atoms. This inaccuracy was well observed
in the above-mentioned study4 for which half of the
reported experimental data were found to be inaccurate
and then remeasured.
Probing transition-state structures through the regio-
selectivity of aromatic Claisen rearrangements should
provide therefore a reliable alternative since small dif-
ferences in transition-state structures lead to significant
product changes. It is therefore clear that our ability to
predict and explain the products of meta-substituted allyl
aryl ether deserves a more extensive theoretical inves-
tigation based on a reliable set of experimental data.
Toward this end, we have recently developed a new
methodology to predict aromatic Claisen regioselectivity
based on determining the ground-state conformational
preference of the reactant allyloxy moiety (A and B
conformers, Scheme 1) via a collection of 1H NMR data.6
From this study6 we verify that the reactant ground-
state conformation closely relates to the ratio of the
(1) Haslam, E. Shikimic Acid: Metabolism and Metabolites; Wiley:
New York, 1993; see also references therein.
(2) (a) Ziegler, F. E. Chem. Rev. 1988, 88, 1423. (b) Rhoads, S. J .;
Raulins, N. R. Org. React. 1975, 22, 1. (c) Bennett, G. B. Synthesis
1977, 589.
(3) (a) Aviyente, V.; Yoo, H. Y.; Houk, K. M. J . Org. Chem. 1997,
62, 6121. (b) Yamabe, S.; Okumoto, S.; Hayashi, T. J . Org. Chem. 1996,
61, 6218. (c) Ganem, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 936.
(d) Gajewski, J . J .; Conrad, N. D. J . Am. Chem. Soc. 1979, 101, 2748.
(4) Meyer, M. P.; DelMonte, A. J .; Singleton, D. A. J . Am. Chem.
Soc. 1999, 121, 10865.
(5) (a) Coates, R. M.; Rogers, B. D.; B. D.; Hobbs, S. J .; Peck, D. R.;
Curran, D. P. J . Am. Chem. Soc. 1987, 109, 1160. (b) Brandes, E.;
Gricco, P. A.; Gajewski, J . J . J . Org. Chem. 1989, 54, 515. (c) Gajewski,
J . J .; J urayj, J .; Kimbrough, D. R.; Gande, M. E.; Ganem, B.; Carpenter,
B. K. J . Am. Chem. Soc. 1987, 109, 1170.
(6) Rodrigues, D. C.; Fernandes, S. A.; Marsaioli, A. J . Magn. Reson.
Chem. 2000, 38, 970.
10.1021/jo026385g CCC: $25.00 © 2003 American Chemical Society
Published on Web 06/12/2003
J . Org. Chem. 2003, 68, 5493-5499
5493

Gozzo et al.
TABLE 1. NOE Differ en ces a n d Lon gitu d in a l
Rela xa tion s (T1) Used To Deter m in e Con for m a tion a l
P r efer en ces fr om 1H NMR Mea su r em en ts Usin g Eq 1 a n d
Th en To P r ed ict th e Ou tcom e of th e Ar om a tic Cla isen
Rea r r a n gem en t for th e Allyl Ar yl Eth er s, a n d th e
Obser ved Exp er im en ta l Rela tive Yield s of th e Tw o
Com p etitive P r od u ctsa
SCHEME 2
allyl
aryl
ether
total
product
ratio
yield %NOE(HA)b/ T1(HB)c/ population
(%)
%NOE(HB)
T1(HA)
ratio A:B
PA: PB
1
2
3
4
5
6
7
8
90
96
85
90
30
56
80
90
1.1
1.1
1.1
1
2.3
2.6
1.6
5.9
0.9
0.8
1.3
0.9
0.8
0.8
1
1.0:1.0
0.9:1.0
1.4:1.0
0.9:1.0
1.8:1.0
2.1:1.0
1.6:1.0
11:1.0
1.0:1.0
0.6:1.0
1.2:1.0
0.7:1.0
1.8:1.0
14:1.0
1.4:1.0
1.0:0
1.8
a
Errors associated with these measurements were found to be
less than <5%. b Determined at 500 MHz with an NMR spectrom-
eter from CDCl3 or C5D5N solutions. c Determined by a 180°sel
-
τ-90° pulse sequence for degassed samples.
competing Claisen rearrangement products. This inter-
esting relationship prompted us to reinvestigate the
system both theoretically and experimentally to verify
whether the preferential ground-state conformation of
aryl allyl ethers bears a correlation with the transition
state of lower energy, thus predicting the preferential
regiochemistry of aromatic Claisen rearrangements.
Herein we present additional experimental results on
a series of asymmetric meta-substituted allyl aryl ethers
TABLE 2. Electr on ic a n d Rela tive En er gies for th e
Con for m er s, Tr a n sition Sta tes, a n d In ter m ed ia tes for th e
Tw o Com p etitive Cla isen Rea r r a n gem en ts of th e Allyl
Ar yl Eth er s 1, 6, 8, a n d 4 As Ca lcu la ted by B3LYP DF T/
HF Hybr id F u n ction a ls a t th e 6-31G(d ,p ) Ba sis Set
allyl aryl
ether
electronic energy
(hartrees)
rel energy
(kcal/mol)
species
1
6
8
4
1A
-463.51630
-463.51634
-463.50108
-463.50277
-463.46264
-463.46256
-652.09238
-652.09162
-652.08396
-652.07250
-652.04184
-652.03507
-577.82567
-577.82332
-577.82253
-577.79018
-577.77651
-577.76021
-538.70239
-538.70312
-538.69282
-538.69460
-538.64637
-538.64672
0
0
1B
1IA
9.6
8.6
33.7
33.7
0
0.5
5.3
12.5
31.7
36.0
0
1.5
1.9
22.3
30.8
41.1
0.4
0
6.5
5.3
35.6
35.4
1
1IB
(1-8) via which the effectiveness of this new H NMR
1TSA
1TSB
6A
methodology has been further tested. Theoretical calcula-
tions on reactants, transition states, and intermediates
have also been performed to verify whether the prefer-
ential ground-state conformations would indeed correlate
with the thermodynamically or kinetically favored reac-
tion pathway for aromatic Claisen rearrangements.
Calculations have also been performed to test the ability
of frontier HOMO-LUMO orbital interactions to mimic
the transition state of aromatic Claisen rearrangements
of allyl aryl ethers, a classical approach used to predict
reactivity and selectivity for Claisen rearrangements of
allyl vinyl ethers.
6B
6IA
6IB
6TSA
6TSB
8A
8B
8IA
8IB
8TSA
8TSB
4A
4B
4IA
Resu lts a n d Discu ssion
4IB
P op u la tion of Con for m er s. Eight meta-substituted
allyl aryl ethers (1-8) were synthezised, and the ratios
of their two stable conformers (Table 1) determined at
equilibrium conditions by 1H NMR. The Kruse equation7
(eq 1) was applied to measure the population of conform-
4TSA
4TSB
values by the longitudinal relaxations (T1) and the
correlation times (τc) of these two hydrogens. The cor-
relation time ratio was considered close to 1 on the basis
of Kruse’s results for very similar molecules.7
η(HA) T1(HB) τc(HB)
population(A)
)
(1)
Regioselectivity. Table 1 also summarizes the ex-
perimental relative yields of the competitive products (P A
and P B) for the aromatic Claisen rearrangements of 1-8.
Note that when the population ratios of the two conform-
ers A and B (Scheme 1) are compared with the product
ratios (Scheme 2), a clear correlation between these two
ratios is noted: with no exception, the favored conformer
A or B leads to the major product P A or P B (Table 1).
For 1, for instance, NMR predicts that the populations
of conformers 1A and 1B are nearly equal (1:1), and
accordingly, the observed relative yields of 1P A and 1P B
population(B) η(HB) T1(HA) τc(HA)
ers A and B and then to predict the ratio of the two
competitive products. Kruse’s equation requires the
measurement of the NOE enhancements of both hydro-
gens ortho to the allyloxy residue (HA and HB) upon
excititation of the methylene group attached to the
oxygen of the allyloxy group, and correction of these
(7) Kruse, L. I.; DeBrosse, C. W.; Kruse, C. H. J . Am. Chem. Soc.
1985, 107, 5435.
5494 J . Org. Chem., Vol. 68, No. 14, 2003

Regioselectivity in Aromatic Claisen Rearrangements
F IGURE 1. B3LYP/6-31G(d,p) potential energy surface diagrams for the competitive aromatic Claisen rearrangements of (a) 1,
(b) 6, (c) 8, and (d) 4.
are nearly the same (1:1). For 8, NMR indicates that
conformer 8A greatly dominates over 8B, and indeed, 8P A
is observed as the exclusive product. For 2 and 4, NMR
indicates that conformers 2B and 4B are slightly favored,
and again, products 2P B and 4P B are formed preferen-
tially.
nearly the same energy; hence, 1 should show no con-
formational preference. But 6A and 8A are considerably
more stable than 6B (by 0.5 kcal/mol) and 8B (by 1.5 kcal/
mol), whereas the opposite is observed for 4; that is, 4B
is more stable than 4A by 0.4 kcal/mol. Therefore, the
theoretical predictions on the relative stabilities (hence
populations) of the two stable conformers A and B fully
agree with the NMR predictions (Table 1). Note also that
the increasing A:B ratios predicted by NMR with the
order 1 < 6 < 8 (Table 1) are also predicted by the
B3LYP/6-31G(d,p) calculations as they show, in the same
order, increasing energy differences between the corre-
sponding conformers A and B.
Tr a n sition -Sta te a n d In ter m ed ia te En er gies. Fig-
ure 1 shows potential energy surface diagrams for the
two competitive aromatic Claisen rearrengments of 1, 6,
8, and 4, whereas Figure 2 displays, as a representative
example, the optimized structure of 1TSA. In the dia-
grams of Figure 1, the energies of the reactant conform-
ers, transition states, and competitive intermediates to
final products are all compared. For 1 (Figure 1a), 1TSA
and 1TSB are both placed 33.7 kcal/mol above the
reactants, and are connected to either 1A or 1B via
intermediates 1IA and 1IB of close energies: +9.6 and
+8.6 kcal/mol above the reactants. Therefore, as pre-
dicted by NMR and as experimentally observed (Table
Th eor etica l Ca lcu la tion s. To verify whether the
favored conformer indeed correlates with the kinetically
or thermodynamically favored Claisen rearrangement,
calculations were performed using the B3LYP DFT/HF
hybrid functionals and 6-31G(d,p) basis set. For these
calculations, four representative allyl aryl ethers were
selected: 1, 6, 8, and 4 (Table 1). Ethers 1, 6, and 8 were
selected because of increasing preference for conformer
A, whereas conformer 4B is slightly predominant over
4; hence, they provide good test cases to test the accuracy
of the theoretical predictions. Table 2 summarizes the
electronic and relative energies calculated for conformers
A and B, for the transition states of both competitive
Claisen rearrangements (TSA and TSB), and for their
corresponding intermediates (IA and IB).
Rela tive En er gy of Con for m er s. For the four allyl
aryl ethers tested, conformers A and B (Scheme 1) are
found by the theoretical calculations as the only two local
minima, with an energy barrier of 1.3 kcal/mol separating
both conformers. Both 1A and 1B are found to display
J . Org. Chem, Vol. 68, No. 14, 2003 5495

Gozzo et al.
F IGURE 2. B3LYP/6-31G(d,p)-optimized geometry of the
transition state for the aromatic Claisen rearrangement of 1.
SCHEME 3
1), both 1P A and 1P B are nearly equally favored, both
kinetically and thermodynamically. For 6 and 8, however,
and again as predicted by NMR and observed experi-
mentally (Table 1), the 6P A and 8P A products formed via
intermediates 6IA (Figure 1b) and 8IA (Figure 1c) should
be favored since they are connected to the more stable
reactants 6A and 8A via the less energetic transition
states 6TSA (+31.7 kcal/mol) and 8TSA (+30.9 kcal/mol).
Therefore, aromatic Claisen rearrangements via inter-
mediates 6IA (+5.3 kcal/mol) and 8IA (+1.7 kcal/mol) are
both thermodynamically and kinetically favored. Note
that a greater difference in activation energy (TS ener-
gies) in favor of IA over IB is observed for 8 (-10.3 kcal/
mol) than for 6 (-4.3 kcal/mol), which also fully agrees
with the observed regioselectivity: a 14:1 mixture of 6P A/
6P B is formed, whereas 8P A is formed exclusively (Table
1).
For 4, the calculations (Figure 1d) also predict the
correct regioselectivity. The more stable conformer 4B
is connected to the thermodynamically favored interme-
diate 4IB (+5.3 kcal/mol) via the kinetically favored
Claisen rearrangement product, which proceeds via the
less energetic transition state 4TSB (+35.4 kcal/mol) to
form the predominant product 4P B (Table 1). Because all
the electronic energies were calculated at 0 K, whereas
the reactions were performed at 573 K (200 °C), a
quantitative relationship between the reaction product
ratios and the calculated transition-state energies is not
expected. Considering that the higher the temperature
the lower the selectivity, the reaction product ratio should
be smaller than the values calculated from the transition-
state energy difference.
F IGURE 3. Atomic orbitals forming frontier molecular orbit-
als in the simplest allyl vinyl ether (left) and in allyl aryl ethers
(as exemplified for 1, right), and their relative energies in
arbitrary off-scale units.
LUMO (allyl moiety) orbital interactions within the
resonating π-electron system.9
For aromatic Claisen rearrangements, however, the
replacement of a vinyl by an aryl group greatly increases
the number and complexity of the molecular π orbitals
of the allyl aryl ethers. Hence, simple frontier HOMO-
LUMO orbital interactions cannot be used to predict
reactivity (and regioselectivity) by mimicking the TS
orbital interactions for aromatic Claisen rearrangements.
Figure 3 clearly exemplifies this effect; note that for the
allyl vinyl ether (left) the LUMO has contributions from
the allyl group antibonding π orbital, but for the allyl
aryl ether 1 (right) the LUMO has only contributions
(coefficients) from the antibonding π orbitals of the aryl
group with no coefficients at all at the allyl group. As
π-orbital-containing substituents are added to the aryl
ring, the π stack becomes more complex, and any
resemblance to the allyl vinyl ether HOMO-LUMO
interactions disappears completely.
Con clu sion s
The regioselectivity of aromatic Claisen rearrange-
ments for meta-substituted allyl aryl ethers is correctly
predicted by NMR measurements or B3LYP/6-31G(d,p)
calculations, or both. NMR reveals the preferred confor-
mation of the reactants, which, with no exception, was
found to lead to the major isomeric product. B3LYP/6-
E lect r on ic Na t u r e of t h e Ar om a t ic Cla isen R e-
a r r a n gem en t. Orbital interaction and electronic struc-
ture analysis of the reactants and transition states for
aromatic Claisen rearrangements of allyl aryl ethers
reveals interesting aspects that greatly differ from those
of the classical Claisen rearrangement of allyl vinyl
ethers (Scheme 3). The transition state of the classical
Claisen rearrangement can be described as proceeding
through intramolecular HOMO (O-vinyl moiety) and
(8) Fleming, I. Frontier Orbitals and Organic Chemical Reactions;
J ohn Wiley & Sons: New York, 1994; p 98.
(9) (a) Hammond, G. S.; Hogle, D. H. J . Am. Chem. Soc. 1955, 77,
338. (b) Curtin, D. Y. Rec. Chem. Prog. 1954, 15, 111.
5496 J . Org. Chem., Vol. 68, No. 14, 2003

Regioselectivity in Aromatic Claisen Rearrangements
produced almost identical NOE difference spectra displaying
closely related ratios. The NOE enhancements at positions A
and B of the allyl aryl ether Claisen rearrangement products
were performed at 298 K on degassed samples prepared as
mentioned above.
GC, IR, a n d MS Mea su r em en ts. GC-MS analyses were
carried out using an instrument equipped with a fused-silica
capillary column (30 m × 0.25 mm i.d. × 0.25 µm film
thickness); the column temperatures were programmed from
373 to 563 K at 15 K min-1. Helium was used as the carrier
gas at a flux of 1 mL min-1. Electron ionization mass spectra
were acquired at 70 eV. The scanning speed was 0.84 scan s-1
from m/z 40 to m/z 550.
Com p u ta tion a l Meth od s. Structures of the species inves-
tigated were fully optimized by theoretical calculations with
no symmetry constraints using B3LYP DFT/HF hybrid func-
tionals and 6-31G(d,p) basis sets10 as implemented in Gaussian
98.11 Transition states were characterized by a single negative
vibrational frequency. The optimized geometries in Cartesian
coordinates of all the species investigated herein are available
as Supporting Information.
31G(d,p) calculations, which accurately describe the
energetics of the two competitive Claisen rearrange-
ments, predict correctly the major isomeric product by
providing reliable relative energies of competitive con-
formers, transition states, and intermediates. For all allyl
aryl ethers studied herein, the favored product has been
shown to arise from the more favored conformer A or B
via both the kinetically and thermodynamically favored
reaction pathway. The regioselectivity for the Claisen
rearrangement of meta-substituted allyl aryl ethers is
mainly influenced, as expected, by the electronic effects
of the meta substituent, which governs the relative
stability of conformers, transition states, and intermedi-
ate to final products.
Because product ratios can be correctly predicted from
the population ratios of conformers, it is concluded that
the electronic effect of the meta group affects the stability
of both conformers and transition states, thus creating
a somewhat fortuitous but close and useful relationship
between the energies of the ground state of the reactants
and transition states for aromatic Claisen rearrange-
ments. However, B3LYP/6-31G(d,p) calculations have
shown that, owing to the complex electronic structure of
the allyl aryl ethers, simple frontier HOMO-LUMO
intramolecular orbital interactions fail to mimic transi-
tion-state orbital interactions, and therefore, these in-
teractions cannot be used to predict the reactivity or
regioselectivity of the aromatic Claisen rearrangement.
Fortunately, however, either NMR data or theoretical
calculations on the preferred conformer or competitive
transition states, or both, have been demonstrated in this
study to be reliable for reactivity and regioselectivity
predictions of the outcome of aromatic Claisen rearrange-
ment of allyl aryl ethers.
P r ep a r a tion of Allyl Ar yl Eth er s 1-8. Gen er a l P r oce-
d u r e. Appropriate hydroxybenzene derivatives were dissolved
in dry acetone, and both anhydrous K2CO3 (2 equiv) and allyl
bromide (1.5 equiv) were added. The mixture was refluxed and
monitored by thin-layer chromatography (TLC). After comple-
tion of the reaction (∼8 h), the reaction mixture was filtered
and acetone was removed under vacuum. The residue was
purified by flash chromatography on silica gel to yield the
desired ally aryl ether in an average yield of 90%.
3-(Allyloxy)m eth ylben zen e (1): IR (film) (cm-1) 3031,
2923, 2867, 1602, 1585, 1490, 1457, 1423, 1290, 125.6969,
1159, 1033, 993, 925, 770, 690; 1H NMR (499.883 MHz, CDCl3)
3
4
4
δ ) 2.32 (s, 3H), 4.51 (ddd, J ) 5.4 Hz, J ) 1.5 Hz, J ) 1.0
Hz, 2H), 5.27 (ddt, 3J ) 10.5 Hz, 2J ) 1.5 Hz, 4J ) 1.0 Hz,
1H), 5.39 (ddt, 3J ) 17.3 Hz, 4J ) 1.5 Hz, 2J ) 1.5 Hz, 1H),
3
3
3
6.02 (ddt, J ) 17.3 Hz, J ) 10.5 Hz, J ) 5.4 Hz, 1H), 6.72
3
4
4
(dt, J ) 8.1 Hz, J ) 2.2 Hz, 1H), 6.74 (t, J ) 2.2 Hz, 1H),
3
4
3
6.76 (dt, J ) 8.1 Hz, J ) 2.2 Hz, 1H), 7.15 (t, J ) 8.1 Hz,
1H); 13C NMR (125.696 MHz) δ ) 20.32, 68.64, 111.55, 115.57,
117.49, 121.65, 129.16, 133.44, 139.45, 158.59; EI-MS m/z (rel
intens) 148 (100) (148.2038 calcd for C10H12O, M+), 133 (72),
105 (36), 91 (15), 77 (16), 41 (12).
Exp er im en ta l Meth od s
NMR Sp ectr a . These spectra were acquired at 499.883 or
300.069 MHz for 0.2 mol L-1 solutions in CDCl3 or d5-pyridine
using TMS as the internal reference. Broad-band decoupled
and DEPT (θ ) 135° and 90°) 13C NMR spectra were acquired
at 125.696 or 75.452 MHz. 2D NMR data (H,H correlation
spectroscopy, gradient COSY, and H,C correlation spectros-
copy, HSQC) were taken using pulse sequences applied to the
1H and 13C NMR signal assignments of all compounds. In the
degassed T1 and NOE relaxation experiments, the samples
were submitted four times to a cyclic operation involving rapid
vacuum and sonication at 263 K followed by introduction of
argon into the evacuated tube equipped with an appropriate
septum and a stainless steel syringe needle connected to a
vacuum pump via thick-walled silicone-rubber tubing. Argon
was introduced via a second stainless steel syringe needle.
1H T1 Mea su r em en ts. After a rapid approximation of the
longest 1H T1, accurate 1H T1 measurements were made at
298 K by applying a standard, 180°-τ-90°-D, sequence. The
delay for each sample was 5 times the approximate longest
T1. A minimum of 11 τ values were used, and exponential
processing was performed by the appropriate software. The
errors for the T1 measurements were near 2%. Typical data
acquisition parameters were spectral width 8000 Hz, acquisi-
tion time 2 s, relaxation delay 60 s, and 8 or 16 repetitions or
number of transients. Typical data processing parameters were
line broadening 1.0 Hz and FT size 65 K.
3-(Allyloxy)-6-ch lor om eth ylben zen e (2): IR (film) (cm-1
)
2923, 2863, 1649, 1597, 1577, 1482, 1410, 1381, 1309, 1242,
1171, 1033, 993, 927; 1H NMR (499.883 MHz, CDCl3) δ ) 2.32
3
4
(s, 3H), 4.48 (dt, J ) 5.4 Hz, J ) 1.2 Hz, 2H), 5.27 (1H, ddt,
3J ) 10.5 Hz, J ) 1.2 Hz, J ) 1.2 Hz, 1H), 5.39 (ddt, J )
4
2
3
17.2 Hz, 4J ) 1.2 Hz, 2J ) 1.2 Hz, 1H), 6.02 (ddt, 3J ) 17.2
3
3
3
4
Hz, J ) 10.5 Hz, J ) 5.4 Hz, 1H), 6.67 (dd, J ) 8.8 Hz, J
4
3
) 2.9 Hz, 1H), 6.73 (d, J ) 2.9 Hz, 1H), 7.20 (d, J ) 8.8 Hz);
13C NMR (125.696 MHz) δ ) 20.32, 68.96, 113.29, 117.30,
117.73, 125.696.93, 129.55, 133.05, 136.96, 157.10; EI-MS m/z
(rel intens) 182 (100) (182.6489 calcd for C10H11OCl, M+), 167
(14), 147 (68), 141 (50), 91 (8), 77 (29), 41 (12).
3-(Allyloxy)h yd r oxyben zen e (3): IR (film) (cm-1) 3400,
2872, 1598, 1492, 1461, 1424, 1283, 1172, 1148, 1027, 936, 836,
765, 686; H NMR (499.883 MHz, CDCl3) δ ) 4.48 (ddl, J )
1
3
(10) (a) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
(b) Becke, A. D. Phys. Rev. A 1988, 38, 3098.
(11) Frisch, M. J .; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J . R.; Zakrzewski, V. G.; Montgomery, J . A.,
J r.; Stratmann, R. E.; Burant, J . C.; Dapprich, S.; Millam, J . M.;
Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J .;
Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo,
C.; Clifford, S.; Ochterski, J .; Petersson, G. A.; Ayala, P. Y.; Cui, Q.;
Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.;
Foresman, J . B.; Cioslowski, J .; Ortiz, J . V.; Stefanov, B. B.; Liu, G.;
Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.;
Fox, D. J .; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.;
Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; J ohnson, B. G.; Chen,
W.; Wong, M. W.; Andres, J . L.; Head-Gordon, M.; Replogle, E. S.;
Pople, J . A. Gaussian 98; Gaussian, Inc.: Pittsburgh, PA, 1998.
Nu clear Over h au ser Effect (NOE) En h an cem en t Meas-
u r em en ts. NOE difference measurements were performed on
the same samples as used to determine 1H T1 values. The pulse
sequences CYCLENOE, available in the instrument, were
employed in different experiments for each sample and
J . Org. Chem, Vol. 68, No. 14, 2003 5497

Gozzo et al.
4
3
5.1 Hz, J ) 1.0 Hz, 2H), 5.27 (dl, J ) 10.5 Hz, 1H), 5.39 (dl,
169.26; EI-MS m/z (rel intens) 192 (34) (192.2128 calcd for
3J ) 17.3 Hz, 1H), 5.72 (s, OH, 1H), 6.02 (ddt, J ) 17.3 Hz,
C11H12O3, M+), 150 (100), 157 (10), 122 (6), 43 (4).
3
3J ) 10.5 Hz, J ) 5.1 Hz, 1H), 6.44 (t, J ) 1.0 Hz, 1H), 6.50
3
4
2-Allyl-3-h yd r oxym et h ylben zen e (1P A) a n d 4-a llyl-3-
h yd r oxym eth ylben zen e (1P B): mixture of 1P A and 1P B; IR
(film) (cm-1) 3429, 3078, 2925, 2855, 1708, 1637, 1586, 1508,
1468, 1420, 1272, 1177, 1156, 1111, 996, 956, 913, 816, 776,
747; 1H NMR (499.883 MHz, CDCl3) δ ) 2.28 (s, 3H), 2.29 (s,
3
4
3
4
(dt, J ) 8.4 Hz, J ) 1.0 Hz, 1H), 6.51 (dt, J ) 8.4 Hz, J )
1.0 Hz, 1H), 7.11 (t, 3J ) 8.4 Hz, 1H); 13C NMR (125.696 MHz)
δ ) 68.89, 102.37, 107.21, 108.08, 117.88, 130.16, 133.07,
156.66, 159.83; EI-MS m/z (rel intens) 150 (100) (150.1760
calcd for C9H10O2, M+), 135 (13), 110 (21), 95 (9), 77 (3), 41
(9).
3
3
4
3H), 3.37 (dl, J ) 6.1 Hz, 2H), 3.43 (ddd, J ) 5.8 Hz, J )
2
3
4
1.5 Hz, J ) 1.5 Hz, 2H), 5.02 (ddt, J ) 17.1 Hz, J ) 1.8 Hz,
2J ) 1.8 Hz, 1H), 5.06 (ddt, 3J ) 10.1 Hz, 4J ) 1.8 Hz, 2J ) 1.5
3-(Allyloxy)m eth oxyben zen e (4): IR (film) (cm-1) 3088,
2939, 2836, 1594, 1492, 1454, 1424, 1363, 1334, 1288, 1265,
1201, 1151, 1083, 1044, 992, 927, 836; 1H NMR (499.883 MHz,
C5H5N) δ ) 3.38 (s, 3H), 4.51 (ddd, J ) 5.4 Hz, J ) 1.5 Hz,
4J ) 1.2 Hz, 2H), 5.28 (ddt, 3J ) 10.5 Hz, 2J ) 1.5 Hz, 4J ) 1.2
Hz, 1H), 5.41 (ddt, 3J ) 17.2 Hz, 4J ) 1.5 Hz, 2J ) 1.5 Hz),
6.05 (ddt, J ) 17.2 Hz, J ) 10.5 Hz, J ) 5.4 Hz, 1H), 6.49
(t, J ) 2.2 Hz, 1H), 6.51 (dt, J ) 8.2 Hz, J ) 2.2 Hz, 1H),
6.52 (dt, J ) 8.2 Hz, J ) 2.2 Hz, 1H), 7.19 (t, J ) 8.2 Hz,
1H); 13C NMR (125.696 MHz) δ ) 55.20, 68.76, 101.16, 106.37,
106.80, 117.66, 129.82, 133.20, 159.79, 160.76; EI-MS m/z (rel
intens) 164 (100) (164.2028 calcd for C10H12O2, M+), 149 (18),
137 (45), 121 (20), 91 (27), 77 (46), 41 (15).
3-(Allyloxy)n itr oben zen e (5): IR (film) (cm-1) 3098, 2872,
1617, 1582, 1529, 1482, 1425, 1351, 1322, 1286, 1248, 1100,
1024, 994, 931, 861, 818, 729, 738, 672; 1H NMR (499.883 MHz,
Hz, 1H), 5.13 (ddt, 3J ) 9.9 Hz, J ) 1.8 Hz, J ) 1.5 Hz, 1H),
5.14 (ddt, 3J ) 17.1 Hz, 4J ) 1.8 Hz, 2J ) 1.5 Hz, 1H), 5.96
(ddt, 3J ) 17.1 Hz, 3J ) 9.9 Hz, 3J ) 5.8 Hz, 1H), 6.00 (ddt, 3J
4
2
3
4
3
3
) 17.1 Hz, J ) 10.1 Hz, J ) 6.1 Hz, 1H), 6.64 (sl, 1H), 6.66
3
3
3
(d, J ) 7.9 Hz, 1H), 6.70 (dl, J ) 7.6 Hz, 1H), 6.77 (d, J )
7.6 Hz, 1H), 7.00 (d, 3J ) 7.9 Hz, 1H), 7.01 (t, 3J ) 7.9 Hz,
1H); 13C NMR (125.696 MHz) δ ) 19.56, 20.98, 30.55, 34.79,
113.35, 115.37, 116.25, 116.50, 121.63, 122.08, 122.78, 123.83,
126.99, 130.20, 135.51, 136.66, 137.92, 138.16, 153.90, 153.97;
EI-MS m/z (rel intens) 148 (90) (148.2038 calcd for C10H12O,
M+), 133 (100), 105 (77), 91 (47), 77 (40), 51 (21), 41 (8).
3
3
3
4
3
4
3
4
3
2-Allyl-6-ch lor o-3-h ydr oxym eth ylben zen e (2P A): IR (film)
(cm-1) 3428, 3080, 2978, 2925, 2855, 1637, 1581, 1493, 1442,
1398, 1379, 1278, 1227, 1193, 1164, 1140, 1106, 1031, 998, 917,
807, 661, 620; 1H NMR (499.883 MHz, CDCl3) δ ) 2.28 (s, 3H),
3.33 (dl, 3J ) 6.2 Hz, 2H), 4.90 (s, OH, 1H), 5.14 (ddt, 3J )
16.9 Hz, 4J ) 1.8 Hz, 2J ) 1.8 Hz, 1H), 5.16 (ddt, 3J ) 10.1
3
4
CDCl3) δ ) 4.62 (dt, J ) 5.4 Hz, J ) 1.5 Hz, 2H), 5.35 (ddt,
3J ) 10.5 Hz, J ) 1.5 Hz, J ) 1.5 Hz, 1H), 5.45 (ddt, J )
17.3 Hz, 4J ) 1.5 Hz, 2J ) 1.5 Hz, 1H), 6.05 (ddt, 3J ) 17.3
Hz, 3J ) 10.5 Hz, 3J ) 5.4 Hz, 1H), 7.25 (dt, 3J ) 8.3 Hz, 4J )
2.2 Hz, 1H), 7.43 (t, 3J ) 8.3 Hz, 1H), 7.74 (t, 4J ) 2.2 Hz,
4
2
3
4
2
3
3
Hz, J ) 1.8 Hz, J ) 1.8 Hz, 1H), 5.94 (ddt, J ) 16.9 Hz, J
) 10.1 Hz, 3J ) 6.2 Hz, 1H), 6.61 (d, 3J ) 8.4 Hz, 1H), 7.11 (d,
3J ) 8.4 Hz, 1H); 13C NMR (75.452 MHz) δ ) 19.74, 34.51,
116.77, 118.05, 124.07, 125.696.56, 130.21, 135.60, 135.68,
152.30; EI-MS m/z (rel intens) 182 (100) (182.6489 calcd for
1H), 7.82 (dl, J ) 8.3 Hz, 1H); 13C NMR (125.696 MHz) δ )
3
69.33, 109.05, 115.88, 118.53, 121.89, 129.95, 132.12, 149.18,
159.09; EI-MS m/z (rel intens) 179 (2) (179.1741 calcd for
C9H9NO3, M+), 162 (2), 132 (2), 77 (3), 41 (100).
C
10H11OCl, M+), 167 (17), 147 (87), 132 (33), 91 (54), 77 (24),
51 (36), 41 (13).
4-Allyl-6-ch lor o-3-h ydr oxym eth ylben zen e (2P B): IR (film)
(cm-1) 3428, 3080, 2978, 2925, 2855, 1637, 1581, 1493, 1442,
1398, 1379, 1278, 1227, 1193, 1164, 1140, 1106, 1031, 998, 917,
807, 661, 620; 1H NMR (300.069 MHz, CDCl3) δ ) 2.32 (s, 3H),
4-(Allyloxy)-2-h yd r oxya cetop h en on e (6): IR (film) (cm-1
)
3433, 3088, 2928, 1634, 1584, 1506, 1426, 1372, 1332, 125.6963,
1195, 1135, 1068, 1004, 938, 796, 574; 1H NMR (499.883 MHz,
CDCl3) δ ) 2.55 (s, 3H), 4.56 (dt, 3J ) 5.1 Hz, 4J ) 1.6 Hz,
2H), 5.32 (dt, 3J ) 10.5 Hz, 4J ) 1.6 Hz, 1H), 5.42 (dt, 3J )
3
4
3.45 (dt, J ) 5.7 Hz, J ) 1.8 Hz, 2H), 4.90 (s, OH, 1H), 4.97
(ddt, 3J ) 17.2 Hz, 4J ) 1.8 Hz, 2J ) 1.8 Hz, 1H), 5.07 (ddt, 3J
) 10.3 Hz, J ) 1.8 Hz, J ) 1.8 Hz, 1H), 5.92 (ddt, J ) 17.2
4
3
3
17.3 Hz, J ) 1.6 Hz, 1H), 6.03 (ddt, J ) 17.3 Hz, J ) 10.5
4
2
3
3
4
3
Hz, J ) 5.1 Hz, 1H), 6.41 (d, J ) 2.4 Hz, 1H), 6.46 (dd, J )
3
3
4
3
Hz, J ) 10.3 Hz, J ) 5.7 Hz, 1H), 6.67 (s, 1H), 7.06 (s, 1H);
13C NMR (75.452 MHz) δ ) 16.49, 31.29, 114.07, 115.62,
124.28, 125.696.68, 127.51, 134.78, 135.15, 152.30; EI-MS m/z
(rel intens) 182 (100) (182.6489 calcd for C10H11OCl, M+), 167
(44), 147 (60), 132 (42), 115 (27), 91 (90), 77 (45), 51 (62), 41
(12).
8.8 Hz, J ) 2.4 Hz, 1H), 7.60 (d, J ) 8.8 Hz, 1H), 12.55 (s,
1H); 13C NMR (125.696 MHz) δ ) 26.15, 68.88, 101.58, 107.93,
113.90, 118.31, 132.10, 132.26, 164.95, 165.05, 202.53; EI-MS
m/z (rel intens) 192 (14) (192.2128 calcd for C11H12O3, M+), 177
(37), 149 (9), 137 (19), 77(11), 41 (100).
2-(Allyloxy)n a p h th a len e (7): IR (film) (cm-1) 3057, 2918,
1630, 1600, 1510, 1470, 1390, 125.6968, 1217, 1183, 1120,
1012, 919, 838, 810, 746, 473; 1H NMR (499.883 MHz, CDCl3)
δ ) 4.63 (dt, 3J ) 5.4 Hz, 4J ) 1.5 Hz, 2H), 5.31(ddt, 3J ) 10.5
2-Allyl-1,3-d ih yd r oxyben zen e (3P A): IR (film) (cm-1
3415, 2918, 1614, 1465, 1370, 1294, 1206, 1106, 1020, 995, 919,
)
1
3
782, 742; H NMR (300.069 MHz, CDCl3) δ ) 3.47 (ddt, J )
4
4
3
4
2
3
4
6.0 Hz, J ) 1.8 Hz, J ) 1.5 Hz, 2H), 5.13 (ddt, J ) 10.1 Hz,
Hz, J ) 1.5 Hz, J ) 1.5 Hz, 1H), 5.46 (ddt, J ) 17.2 Hz, J
2J ) 1.8 Hz, 4J ) 1.5 Hz, 1H), 5.15 (ddt, 3J ) 17.2 Hz, 4J ) 1.8
2
3
3
) 1.5 Hz, J ) 1.5 Hz, 1H), 6.11 (ddt, J ) 17.2 Hz, J ) 10.5
2
3
Hz, 3J ) 5.4 Hz, 1H), 7.13 (dl, 4J ) 2.7 Hz, 1H), 7.17 (dd, 3J )
Hz, J ) 1.8 Hz, 1H), 5.29 (s, 2OH, 2H), 6.01 (ddt, J ) 17.2
3
3
3
4
3
4
Hz, J ) 10.1 Hz, J ) 6.0 Hz, 1H), 6.41 (d, J ) 8.4 Hz, 2H),
8.9 Hz, J ) 2.7 Hz, 1H), 7.32 (td, J ) 7.6 Hz, J ) 1.0 Hz,
6.96 (t, J ) 8.4 Hz, 1H); 13C NMR (75.452 MHz) δ ) 27.46,
3
3
4
3
1H), 7.42 (td, J ) 7.6 Hz, J ) 1.2 Hz, 1H), 7.71 (dl, J ) 7.6
3
3
108.26, 112.01, 115.93, 127.63, 135.94, 155.02; EI-MS m/z (rel
intens) 150 (96) (150.1760 calcd for C9H10O2, M+), 132 (18),
123 (49), 107 (20), 91 (100), 77 (29), 51 (47).
Hz, 1H), 7.73 (d, J ) 8.9 Hz, 1H), 7.75.452 (dl, J ) 8.6 Hz,
1H); 13C NMR (125.696 MHz) δ ) 68.75.452, 106.97, 117.70,
118.93, 123.62, 126.31, 126.73, 127.61, 128.99, 129.38, 133.16,
134.48, 156.49; EI-MS m/z (rel intens) 184 (20) (184.2368 calcd
for C13H12O, M+), 169 (13), 143 (8), 128 (6), 115 (100), 89 (10),
63 (9), 41 (12).
4-Allyl-1,3-d ih yd r oxyben zen e (3P B): IR (film) (cm-1
)
3390, 2976, 2929, 2856, 1723, 1617, 1511, 1464, 1377, 1265,
1225, 1161, 1112, 975.452, 917, 839, 738, 703; 1H NMR
(499.883 MHz, CDCl3): δ ) 3.34 (dl, 3J ) 6.4 Hz, 2H), 5.12 (s,
3-(Allyloxy)a cetylben zen e (8): IR (film) (cm-1) 3088,
2928, 2872, 1766, 1707, 1488, 1424, 1370, 1313, 1285, 1262,
1210, 1166, 1139, 1019, 900, 867, 783, 688, 529; 1H NMR
(499.883 MHz, CDCl3) δ ) 2.27 (s, 3H), 4.51 (ddd, 3J ) 5.1
3
2
3
OH, 2H), 5.14 (dd, J ) 9.9 Hz, J ) 1.5 Hz, 1H), 5.15 (dd, J
2
3
3
) 17.4 Hz, J ) 1.5 Hz, 1H), 6.00 (ddt, J ) 17.4 Hz, J ) 9.9
3
3
4
Hz, J ) 6.4 Hz, 1H), 6.36 (sl, 1H); 6.37 (dd, J ) 7.6 Hz, J )
2.4 Hz, 1H), 6.94 (d, 3J ) 7.6 Hz, 1H); 13C NMR (125.696 MHz)
δ ) 34.56, 103.30, 107.74, 116.31, 117.35, 131.06, 136.76,
155.16, 155.47; EI-MS m/z (rel intens) 150 (100) (150.1760
calcd for C9H10O2, M+), 132 (41), 123 (26), 107 (43), 91 (85), 77
(31), 51 (25).
4
4
3
4
Hz, J ) 1.7 Hz, J ) 1.5 Hz, 2H), 5.28 (ddt, J ) 10.5 Hz, J
2
3
4
) 1.5 Hz, J ) 1.5 Hz, 1H), 5.40 (ddt, J ) 17.3 Hz, J ) 1.7
Hz, 2J ) 1.5 Hz, 1H), 6.03 (ddt, 3J ) 17.3 Hz, 3J ) 10.5 Hz, 3J
4
3
) 5.1 Hz, 1H), 6.66 (t, J ) 2.4 Hz, 1H), 6.68 (dt, J ) 8.2 Hz,
4J ) 2.4 Hz, 1H), 6.81(dt, J ) 8.2 Hz, J ) 2.4 Hz, 1H), 7.25
(t, 3J ) 8.2 Hz, 1H); 13C NMR (125.696 MHz) δ ) 21.02, 68.88,
108.40, 112.27, 113.87, 117.72, 129.73, 132.00, 151.54, 159.42,
3
4
2-Allyl-3-m eth oxyben zen e (4P A): IR (film) (cm-1) 3443,
3078, 2928, 2838, 1637, 1596, 1499, 1470, 1440, 1326, 1274,
5498 J . Org. Chem., Vol. 68, No. 14, 2003

Regioselectivity in Aromatic Claisen Rearrangements
1243, 1211, 1115, 1070, 997, 913, 777, 736, 634; 1H NMR
113.84, 116.00, 130.71, 135.45, 161.30, 162.72, 203.08; EI-MS
m/z (rel intens): 192 (32) (192.2128 calcd for C11H12O3, M+),
177 (73), 149 (34), 121 (5), 91(14), 77 (20), 65 (14), 43 (100).
(499.883 MHz, CDCl3) δ ) 3.46 (ddd, 3J ) 5.8 Hz, 4J ) 1.8
4
3
2
Hz, J ) 1.5 Hz, 2H), 3.80 (s, 3H), 5.07 (ddt, J ) 10.9 Hz, J
4
3
4
5-Allyl-2,4-dih ydr oxyacetoph en on e (6P B): IR (film) (cm-1
)
) 1.8 Hz, J ) 1.5 Hz, 1H), 5.10 (ddt, J ) 17.4 Hz, J ) 1.8
Hz, 2J ) 1.8 Hz, 1H), 5.98 (ddt, 3J ) 17.4 Hz, 3J ) 10.9 Hz, 3J
) 5.8 Hz), 6.48 (dl, 3J ) 7.5 Hz, 1H), 6.49 (dl, 3J ) 7.5 Hz,
1H), 7.07 (t, 3J ) 7.5 Hz, 1H); 13C NMR (125.696 MHz) δ )
27.32, 55.79, 103.32, 108.79, 113.61, 115.34, 127.51, 136.30,
155.14, 158.22; EI-MS m/z (rel intens) 164 (100) (164.2028
calcd for C10H12O2, M+), 149 (31), 135 (38), 121 (36), 107 (46),
91 (36), 77 (59), 65 (25), 51 (33), 43 (13).
3281, 2923, 1637, 1508, 1434, 1373, 1329, 1238, 1134, 1052,
1
956, 916, 796, 636, 562; H NMR (499.883 MHz, CDCl3) δ )
2.56 (s, 3H), 3.36 (dl, 3J ) 6.4 Hz, 2H), 5.16 (ddt, 3J ) 10.3
2
4
3
2
Hz, J ) 1.7 Hz, J ) 1.5 Hz, 1H), 5.18 (ddt, J ) 17.1 Hz, J
4
3
3
) 1.7 Hz, J ) 1.5 Hz, 1H), 6.00 (ddt, J ) 17.1 Hz, J ) 10.3
3
Hz, J ) 6.4 Hz, 1H), 7.26 (s, 1H), 7.46 (s,1H), 12.55 (s, 1H);
13C NMR (125.696 MHz) δ ) 26.29, 34.15, 103.70, 114.20,
116.82, 117.49, 132.80, 136.09, 161.21, 163.71, 202.65; EI-MS
m/z (rel intens): 192 (57) (192.2128 calcd for C11H12O3, M+),
177 (100), 165 (3), 149 (16), 121 (3), 103 (3), 91 (4), 77 (5), 43
(14).
4-Allyl-3-m eth oxyben zen e (4P B): IR (film) (cm-1) 3417,
3078, 3034, 2928, 2838, 1619, 1596, 1519, 1468, 1434, 1285,
1
1202, 1162, 1113, 1037, 997, 959, 915, 836, 780, 633, 574; H
NMR (499.883 MHz, CDCl3) δ ) 3.37 (dl, 3J ) 6.1 Hz, 2H),
3
2
4
Allyl-2-n a p h th ol (7P A): IR (film) (cm-1) 3415, 3074, 2980,
2925, 2656, 1628, 1599, 1515, 1467, 1438, 1395, 1355, 1264,
1144, 1062, 986, 969, 914, 810, 746, 547; 1H NMR (499.883
MHz, CDCl3) δ ) 3.85 (dl, 3J ) 5.9 Hz, 2H), 5.09 (ddl, 3J )
17.1 Hz, 2J ) 1.7 Hz, 1H), 5.12 (ddl, 3J ) 10.3 Hz, 2J ) 1.7
3.79 (s, 3H), 5.16 (ddt, J ) 9.6 Hz, J ) 1.8 Hz, J ) 1.5 Hz,
1H), 5.17 (ddt, 3J ) 17.6 Hz, 2J ) 1.8 Hz, 4J ) 1.5 Hz, 1H),
5.32 (s, OH, 1H), 6.02 (ddt, 3J ) 17.6 Hz, 3J ) 9.6 Hz, 3J ) 6.1
4
3
4
Hz, 1H), 6.46 (d, J ) 2.4 Hz, 1H), 6.48 (dd, J ) 8.2 Hz, J )
2.4 Hz, 1H), 7.02 (d, 3J ) 8.2 Hz, 1H); 13C NMR (125.696 MHz)
δ ) 34.43, 55.28, 102.00, 106.22, 116.14, 117.46, 130.81,
136.79, 154.97, 159.49; EI-MS m/z (rel intens) 164 (100)
(164.2028 calcd for C10H12O2, M+), 149 (20), 137 (67), 121 (27),
103 (49), 91 (38), 77 (70), 65 (30), 51 (43), 41 (22).
3
3
3
Hz, 1H), 6.10 (ddt, J ) 17.1 Hz, J ) 10.3 Hz, J ) 5.9 Hz,
3
3
4
1H), 7.11 (d, J ) 8,8 Hz, 1H), 7.36 (td, J ) 7.5 Hz, J ) 1.0
Hz 1H), 7.50 (t, 3J ) 7.5 Hz, 4J ) 1.0 Hz 1H), 7.68 (d, 3J ) 8.8
3
3
Hz, 1H), 7.80 (d, J ) 7.6 Hz, 1H), 7.93 (d, J ) 7.6 Hz, 1H);
13C NMR (125.696 MHz) δ ) 29.20, 115.84, 116.84, 117.87,
122.98, 123.11, 126.43, 128.25, 128.52, 129.35, 133.20, 135.76,
151.11; EI-MS m/z (rel intens) 184 (96) (184.2368 calcd for
2-Allyl-3-n itr oben zen e (5P A): IR (film) (cm-1) 3402, 2928,
2856, 1637, 1608, 1525, 1452, 1333, 1280, 1206, 1153, 1092,
1000, 960, 919, 839, 807, 736, 668, 587; 1H NMR (499.883 MHz,
3
3
C
13H12O, M+), 169 (100), 152 (11), 141 (29), 128 (21), 115 (27),
CDCl3) δ ) 3.61 (dl, J ) 6.1 Hz, 2H), 5.15 (ddl, J ) 16.2 Hz,
2J ) 1.5 Hz, 1H), 5.16 (ddl, 3J ) 11.0 Hz, 2J ) 1.5 Hz, 1H),
5.83 (s, OH, 1H), 6.01 (ddt, J ) 16.2 Hz, J ) 11.0 Hz, J )
102 (5), 91 (9), 76 (13), 63 (19), 51 (2), 43 (1).
3
3
3
2-Allyl-3-h yd r oxya cetylben zen e (8P A): IR (film) (cm-1
)
3
3
6.1 Hz, 1H), 7.07 (d, J ) 8.2 Hz, 1H), 7.23 (dd, J ) 8.2 Hz,
3J ) 7.9 Hz, 1H), 7.42 (d, 3J ) 7.9 Hz, 1H); 13C NMR (125.696
MHz) δ ) 29.97, 116.65, 116.87, 120.04, 120.50, 127.65, 134.35,
150.99, 155.35; EI-MS m/z (rel intens) 179 (8) (179.1741 calcd
for C9H9O3N, M+) 162 (44), 150 (42), 145 (47), 131 (33), 116
(16), 103 (40), 89 (17), 77 (100), 65 (31), 51 (69), 43 (18).
4-Allyl-3-n itr oben zen e (5P B): IR (film) (cm-1) 3458, 3088,
2923, 2851, 1640, 1597, 1511, 1427, 1349, 1262, 1117, 1082,
3436, 3083, 2923, 1737, 1638, 1607, 1514, 1465, 1430, 1371,
1233, 1151, 1108, 1022, 976, 913, 672, 600; 1H NMR (499.883
3
MHz, CDCl3) δ ) 2.28 (s, 3H), 3.35 (dl, J ) 6.4 Hz, 2H), 5.12
3
2
4
3
(ddt, J ) 9.8 Hz, J ) 1.8 z, J ) 1.5 Hz, 1H), 5.13 (ddt, J )
17.4 Hz, 2J ) 1.8 Hz, 4J ) 1.5 Hz, 1H), 5.96 (ddt, 3J ) 17.4
3
3
3
Hz, J ) 9.8 Hz, J ) 6.4 Hz, 1H), 6.64 (dl, J ) 8.2 Hz, 1H),
6.66 (dl, J ) 8.2 Hz, 1H), 7.08 (t, J ) 8.2 Hz, 1H); 13C NMR
(75.452 MHz) δ ) 21.10, 34.40, 109.28, 113.50, 116.48, 123.39,
130.60, 136.19, 149.87, 154.69, 169.95; EI-MS m/z (rel intens)
192 (2) (192.2128 calcd for C11H12O3, M+) 150 (35), 135 (12),
123 (19), 107 (11), 77 (24), 43 (100).
3
3
1
998, 953, 928, 880, 818, 741; H NMR (499.883 MHz, CDCl3)
δ ) 3.48 (dl, 3J ) 6.4 Hz, 2H), 5.18 (ddl, 3J ) 17.1 Hz, 4J ) 1.5
3
2
Hz, 1H), 5.20 (ddl, J ) 10.2 Hz, J ) 1.5 Hz, 1H), 5.99 (ddt,
3J ) 17.1 Hz, J ) 10.2 Hz, J ) 6.4 Hz, 1H), 7.27 (d, J ) 8.2
3
3
3
4-Allyl-3-h yd r oxya cetylben zen e (8P B): IR (film) (cm-1
)
4
3
4
Hz, 1H), 7.68 (d, J ) 2.1 Hz, 1H), 7.76 (dd, J ) 8.2 Hz, J )
2.1 Hz, 1H); 13C NMR (125.696 MHz) δ ) 34.69, 110.54, 115.89,
117.62, 130.68, 133.85, 134.61, 147.42, 154.40; EI-MS m/z (rel
intens) 179 (100) (179.1741 calcd for C9H9O3N, M+), 164 (12),
147 (3), 132 (13), 118 (14), 103 (33), 89 (6), 77 (49), 63 (13), 51
(26), 41 (6).
3436, 3083, 2923, 1737, 1638, 1607, 1514, 1465, 1430, 1371,
1233, 1151, 1108, 1022, 976, 913, 672, 600; 1H NMR (499.883
3
4
MHz, CDCl3) δ ) 2.30 (s, 3H), 3.32 (dt, J ) 6.4 Hz, J ) 1.5
Hz, 2H), 5.07 (ddt, 3J ) 10.1 Hz, 2J ) 1.8 Hz, 4J ) 1.5 Hz,
1H), 5.09 (ddt, 3J ) 17.1 Hz, 2J ) 1.8 Hz, 4J ) 1.5 Hz, 1H),
3
3
3
5.90 (ddt, J ) 17.1 Hz, J ) 10.1 Hz, J ) 6.4 Hz, 1H), 6.54
3-Allyl-2,4-dih ydr oxyacetoph en on e (6P A): IR (film) (cm-1
)
4
3
4
(d, J ) 2.4 Hz, 1H), 6.59 (dd, J ) 8.1 Hz, J ) 2.4 Hz, 1H),
3134, 2923, 1625, 1589, 1494, 1373, 1320, 1274, 1211, 1112,
7.01 (d, J ) 8.1 Hz, 1H); 13C NMR (75.452 MHz) δ ) 20.87,
3
1
1039, 1001, 924, 794, 611, 563, 444; H NMR (499.883 MHz,
28.46, 113.45, 114.62, 115.99, 118.45, 127.43, 135.30, 149.78,
155.28, 169.73; EI-MS m/z (rel intens) 192 (14) (192,2128 calcd
for C11H12O3, M+) 150 (56), 135 (40), 123 (10), 107 (23), 77 (19),
43 (100).
3
3
CDCl3) δ ) 2.57 (s, 3H), 3.48 (dl, J ) 6.1 Hz, 2H), 5.12 (dl, J
) 10.3 Hz, 1H), 5.16 (dl, 3J ) 17.1 Hz, 1H), 5.99 (ddt, 3J )
17.1 Hz, 3J ) 10.3 Hz, 3J ) 6.1 Hz, 1H), 6.24 (s, OH, 1H), 6.41
3
3
(d, J ) 8.8 Hz, 1H), 7.56 (d, J ) 8.8 Hz, 1H), 12.55 (s, OH,
1H); 13C NMR (125.696 MHz) δ ) 26.17, 26.61, 107.65, 112.62,
J O026385G
J . Org. Chem, Vol. 68, No. 14, 2003 5499