Preparation of 2,3-epoxycycloalkanones from bicyclo[n.1.0]Alkan-1-ols

Article abstract of DOI:10.1081/SCC-100000523

Copper- or iron-catalyzed oxidative rearrangement of bicyclo[n.1.0]alkan-1-ols yields 3-hydroperoxycycloalkanones and/or bicyclic peroxyhemiketals, which are transformed into 2,3-epoxycycloalkanones by treatment with a base.

Full text of DOI:10.1081/SCC-100000523

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PREPARATION OF 2,3-EPOXYCYCLOALKANONES FROM
BICYCLO[n.1.0]ALKAN-1-OLS
Jean-Pierre Barnier a , Vèronique Morisson a & Luis Blanco b
a Laboratoire des Carbocycles (Associ è au CNRS), Institut de Chimie Molèculaire
d'Orsay , Universitè de Paris-Sud , Bât. 420, Orsay, 91405, France
b Laboratoire des Carbocycles (Associ è au CNRS), Institut de Chimie Molèculaire
d'Orsay , Universitè de Paris-Sud , Bât. 420, Orsay, 91405, France
Published online: 09 Nov 2006.
To cite this article: Jean-Pierre Barnier , Vèronique Morisson & Luis Blanco (2001) PREPARATION OF 2,3-
EPOXYCYCLOALKANONES FROM BICYCLO[n.1.0]ALKAN-1-OLS, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 31:3, 349-357, DOI: 10.1081/SCC-100000523
To link to this article: http://dx.doi.org/10.1081/SCC-100000523
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SYNTHETIC COMMUNICATIONS, 31(3), 349–357 (2001)
PREPARATION OF
2,3-EPOXYCYCLOALKANONES
FROM BICYCLO[n.1.0]ALKAN-1-OLS
Jean-Pierre Barnier, Ve´ronique Morisson,
and Luis Blanco∗
Laboratoire des Carbocycles (Associe´ au CNRS), Institut de
Chimie Mole´culaire d’Orsay, Baˆt. 420, Universite´ de
Paris-Sud, 91405 Orsay, France
ABSTRACT
Copper- or iron-catalyzed oxidative rearrangement of bicy-
clo[n.1.0]alkan-1-ols yields 3-hydroperoxycycloalkanones and/or
bicyclic peroxyhemiketals, which are transformed into 2,3-epoxy-
cycloalkanones by treatment with a base.
Addition of hydrogen peroxide to α,β-ethylenic ketones in basic medium is
one of the most common methods to prepare 2,3-epoxyketones (1). Evidence has
been presented indicating that the reaction occurred by addition of HOO− to the
β-carbon atom, then the enolate could cyclize by ejection of an hydroxide ion (2).
In the usual conditions, reversal of hydroperoxide anion addition may compete
with closure to epoxyketone. In a few cases, the hydroperoxide resulting from
protonation by solvent of the intermediate enolate was isolated (3–5), and submis-
sion of this hydroperoxyketone to alkaline conditions could result in epoxyketone
formation (5). A reported by-product in the reaction of alkaline hydrogenperoxide
∗Corresponding author.
349
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

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350
BARNIER, MORISSON, AND BLANCO
with mesityl oxide (3) was identified as a cyclic peroxyhemiketal (4).
R1
R2
R4
O
R1
OH
R1
R2
R4
R3
HOO−
R4
R3
HOO
O
O
R3
O
Solvent
R2
R1
R2
R4
R3
HOO
O
B
Oxidative rearrangement of bicyclo[n.1.0]alkan-1-ols in the presence of oxy-
gen allows the preparation of 3-hydroperoxycycloalkanones and/or bicyclic per-
oxyhemiketals (6–9).
This paper deals with the synthesis of 2,3-epoxycycloalkanones from
bicyclo[n.1.0]alkan-1-ols via these peroxidated compounds.
RESULTS AND DISCUSSION
Using a conventionnal sequence (10) (see Sch. 1), bicyclo[n.1.0]alkan-
–
1-ols 4a–e were prepared by O Si bond cleavage in acidic methanol of the corre-
sponding trimethylsilylethers 3a–e (11,12). The bicycloalkanic compounds 3a–
e were obtained by cyclopropanation with CH2I2/Et2Zn (13) of 2-substituted
1-trimethylsilyloxycycloalkenes 2a–e, which were selectively synthetized (14)
from 2-substituted cycloalkanones 1a–e.
Treatment of illuminated etheral solutions of the bicycloalkanols 4a–e with
oxygen, in the presence of chromatographic silica gel and of a catalytic amount
Me3SiO
(CH2)n
Me3SiO
HO
O
R
R
R
R
a
c
b
(CH2)n
(CH2)n
(CH2)n
1a-e
2a-e
3a-e
4a-e
a
n = 1, R = CH3
n = 1, R = C4H9
n = 1, R = C6H13
n = 1, R = CH2Ph
n = 2, R = CH3
b
c
a - ClSiMe3, NaI, Pyridine, MeCN
b - CH2I2, Et2Zn, Hexane, air
c - MeOH, ClSiMe3 (2%)
d
e
Scheme 1.

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2,3-EPOXYCYCLOALKANONES
351
O
O
O
(CH2)n
R
HO
O
O
Et2O, O2, hν
R
+
+
H
and/or
HO
(CH2)n
(CH2)n
R
silica gel, Fe(acac)3
R
(CH2)n
O
H
O
4a-e
6a-e
7a-e
O
(CH2)n
5a-e
R
Scheme 2.
of ferric acetylacetonate (2 mol%), allowed the synthesis of the peroxidated com-
pounds 5a–e, which were isolated by silica gel column chromatography
(see Sch. 2 and Table 1, Method A) (9). Various amounts of the correspond-
ing 3-hydroxycycloalkanone 6 and of a cycloalk-2-enone 7 were also isolated.
Cycloalkenones 7 might not be intermediates in the formation of compounds 5,
because 5b was not detected when butylcyclohexenone 7b was treated using the
ferric-catalyzed conditions for the oxidative rearrangement of bicycloalkanols.
When methanol was present, messy reaction mixtures were obtained and
yields of the peroxidated compounds 5 were lowered. So methanol should be
carefully removed after deprotection of the silylated compounds 3.
Interestingly, the synthesis of the peroxidated compounds 5 from bicy-
cloalkanols 4 can be run in ethanol using cupric acetylacetonate. This oxida-
tive rearrangement of bicyclo[n.1.0]alkan-1-ols occurred also in the presence of
manganese(III) acetylacetonate, but the reaction was less selective. Treatment of
Table 1. Preparation of Peroxidated Compounds 5 by Oxidative Rearrangement of
Bicylo[n.1.0]alkan-1-ols 4
Peroxidated Compound 5
Bicycloalkanol 4
Method Aa
Method Bb
R
n
Reaction time (h) Yield (%) Reaction time (h) Yield (%)
a
b
c
d
e
CH3
1
1
1
1
2
3
3
3
3
36
35
55
68
50
54
5
3.5
54
84
C4H9
C6H13
CH2Ph
CH3
5
6
78
80
aEt2O, O2,hν, silica gel, Fe(acac)3.
bEtOH, O2, hν, Cu(acac)2.

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352
BARNIER, MORISSON, AND BLANCO
HO
O
O
Me3SiO
O
1) EtOH, ClSiMe3 (2%)
2) EtOH, Cu(acac)2 (4%), O2, hν
R
and/or
(CH2)n
R
(CH2)n
R
(CH2)n
O
O
H
3
5
Scheme 3.
bicyclo[n.1.0]alkan-1-ols with oxygen in the presence of vanadyl acetylaceto-
nate gave mainly cycloalkan-1,3-diones and/or 3-hydroxycycloalkanones (15).
The preparation of a bicycloalkanol 4 from the corresponding silylated compound
3 was carried out in ethanol by addition of CISiMe3 (2 mol%). Then, a one-pot
oxidative step was started in the presence of oxygen and light after addition of
4 mol% of cupric acetylacetonate to the reaction mixture in order to avoid an
acidic medium during this step (vide infra; see Sch. 3 and Table 1, Method B).
When cupric acetylacetonate or light (or both) was omitted, reaction time
was longer and the yield of the peroxidated compound decreased. For example,
complete transformation of the butylbicyclohexanol 4b was observed after 3.5 h
(yield of 5b: 84%) in the presence of oxygen, cupric acetylacetonate, and electric
bulb light. In the absence of light, the reaction time was about 24 h (yield of
5b: 57%). In the absence of light and cupric salt, complete transformation of 4b
occurred after 48 h, and the main product was the bicyclic peroxyketal 8 (in these
conditions, the oxidative rearrangement was run in the presence of HCl liberated
by the reaction of ClSiMe3 with EtOH). The round-bottomed flask was pre-treated
with an aqueous solution of tetrasodium ethylenediamine tetraacetate (2 h) in order
to ensure the absence of polyvalent ionic cations (mainly Fe3+) on the glass surface.
Me3SiO
HO
C2H5O
O
EtOH
EtOH (HCl)
O2
C4H9
C4H9
O
ClSiMe3 (2%)
C4H9
20°C, 0.5 h
3b
4b
59%
8
A 3-hydroperoxycycloalkanone structure could be attributed to the cyclo-
hexanic compounds 5a–d because they gave a very strong positive test on acidic
starch-potassium iodide paper and their IR spectra show a carbonyl stretching band
at 1715 cm−1. But it is probable that an equilibrium (8) between the hydroperox-
ycyclohexanone and a bicyclic peroxyhemiketal occurs (at least in chloroform),
because 13C NMR spectra of the compounds 5a–d show two sets of signals: one
=
wasassignedtoahydroperoxycyclohexanone(C Oat∼210ppm;C3 at∼85 ppm)

ORDER
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2,3-EPOXYCYCLOALKANONES
353
and the other could be assigned to the peroxyhemiketal (C1 at ∼107 ppm; C5 at
∼88 ppm). Signals at 119.9 and 87.9 ppm, respectively assigned to the C1 and C5
carbon atoms, are present in the 13C NMR spectrum of peroxyketal 8.
HO
O
O
O
R
R
O O
H
5a–d
13C NMR spectrum of the cycloheptanic compound 5e shows only one set
of signals (seven lines) that could be assigned to a peroxyhemiketal structure (C1
at 109.4 ppm; C6 at 85.9 ppm and no carbonyl signal).
Inthesynthesisoftheperoxidatedcompounds5, yieldsoftheferric-catalyzed
reactions were fairly good, but the cupric-catalyzed reactions gave generally higher
yields and, interestingly, in the case of 5e, the reaction rate was faster. The lower
yields of the compound 5a were due mainly to its volatility.
Treatment of the peroxidated compounds 5a–e with one equivalent of a
2 M NaOH aqueous solution in ether allowed fast and efficient syntheses of 2,3-
epoxycycloalkanones 9a–e, which were isolated by silica gel column chromatog-
raphy with good yields (see Sch. 4).
Spectroscopic properties of 9a and 9b were identical to those reported in the
1
literature (16–18), and the H-NMR spectra of compounds 9c–e show a charac-
teristic singulet at ∼3.1 ppm attributed to C2 H.
–
Preparation of the epoxycycloalkanones 9 from peroxidated compounds 5
could also be run using DBU, but the reaction rate was slower (e.g., complete
transformation of 5d needs 3 h at 20◦C with 1 equivalent of reactant; with NaOH
the reaction was over in 20 min). With NEt3 the reaction occurred but was too
slow to be synthetically useful (e.g., about 10% conversion of 5d was noticed
after 5 h at 20◦C with 1 equivalent of reactant). Epoxycycloalkanone 9b was also
HO
O
O
O
NaOH
O
and/or
H
Et2O − H2O
20°C
O
(CH2)n
R
(CH2)n
(CH2)n
R
R
O
O
77−85%
5a-e
9a-e
Scheme 4.

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354
BARNIER, MORISSON, AND BLANCO
isolated when the corresponding peroxidated compound 5b was chromatographed
on Florisilꢀ.
In summary, this work shows a new way to prepare 2,3-epoxycycloalkanones
starting from bicyclo[n.1.0]alkan-1-ols, which could be a complementary method
to the usual epoxydation of cycloalk-2-enones.
EXPERIMENTAL
For general methods and preparation of 1-trimethylsilyloxybicyclo[n.1.0]
alkanes 3, see a previous report (10).
Preparation of Peroxydated Compounds 5 (General Procedures)
Method A: To a solution of 1 mmol of 1-trimethylsilyloxybicycloalkane
3 in 3 mL of methanol, maintained under argon, were added 50 µL of a 0.4 M
solutionofClSiMe3 inmethanol(0.02mmol). After15minat20◦C, thesolventwas
evaporated under reduced pressure. The crude bicycloalkanol 4 was taken off with
12 mL of dry diethyl ether and 14 mg of Fe(acac)3 (0.04 mmol), and 1.2 g of 70–
230 mesh silica gel were added. The reaction mixture, maintained under oxygen,
was stirred at 30 cm of a 100-W domestic light bulb and the temperature was kept
at 20◦C by blowing an air stream on the reaction flask. After the indicated time (see
Table 1), the silica gel was separated by filtration and extracted with diethyl ether.
After evaporation of the solvent under reduced pressure, the peroxidated product 5
was separated by silica gel column chromatography (pentane/diethyl ether 80:20).
Method B: To a solution of 1 mmol of 1-trimethylsilyloxybicycloalkane 3
in 3 mL of ethanol, maintained under argon, were added 50 µL of a 0.4 M solution
of ClSiMe3 in ethanol (0.02 mmol). After 15 min at 20◦C, 10.5 mg of Cu(acac)2
(0.04 mmol) were added. The reaction mixture, maintained under oxygen, was
stirred at 30 cm of a 100-W domestic light bulb and the temperature was kept
at 20◦C by blowing an air stream on the reaction flask. After the indicated time
(see Table 1), the reaction mixture was diluted with diethyl ether and washed with
water. The organic phase was dried over Na2SO4 and, after evaporation of the
solvent under reduced pressure, the peroxidated product 5 was separated by silica
gel column chromatography (pentane/diethyl ether 80:20).
3-Hydroperoxy-3-methylcyclohexanone/5-methyl-6,7-dioxabicyclo[3.2.
1]octan-1-ol 5a. Method A, from 138 mg of methylbicyclohexane 3a: 38 mg,
35%. Method B, from 184 mg of methylbicyclohexane 3a: 77.6 mg, 54%. 13C
NMR (50 MHz, CDCl3) δ (hydroperoxyketone): 20.8, 24.1, 33.2, 40.2, 49.8,
84.8, 211.4; (peroxyhemiketal): 19.1, 22.1, 34.9, 35.9, 52.0, 86.2, 107.7; (hy-
droperoxide/peroxyhemiketal ∼4:1); 1H NMR (250 MHz, CDCl3) δ 1.33 (s, CH3

ORDER
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2,3-EPOXYCYCLOALKANONES
355
peroxyhemiketal) and 1.35 (s, CH3 hydroperoxide) (3H); 1.38–2.45 (m) and 2.39
(d, J = 14 Hz) (7.2H), 2.75 (dt, J = 14 and 1 Hz, 0.8H), 3.30–3.70 (m, 0.2H,
OH), 8.00–8.40 (m, 0.8H, OOH); Anal. calcd for C7H12O3:C, 58.32; H, 8.39; O,
33.29. Found: C, 57.98; H, 8.42; O, 33.54.
3-Butyl-3-hydroperoxycyclohexanone/5-butyl-6,7-dioxabicyclo-[3.2.1]
octan-1-ol 5b. Method A, from 85 mg of butylbicyclohexane 3b: 38.5 mg, 55%.
Method B, from 113 mg of butylbicyclohexane 3b: 78.3 mg, 84%. 13C NMR
(50 MHz, CDCl3) δ (hydroperoxyketone): 13.9, 20.7, 22.9, 25.1, 31.2, 36.6, 40.5,
48.2, 86.9, 211.9; (peroxyhemiketal): 13.8, 19.0, 22.9, 26.5, 34.1, 35.2, 35.8,
50.2, 88.6, 107.6; (hydroperoxide/peroxyhemiketal ∼1.2:1); 1H NMR (200 MHz,
CDCl3) δ 0.80–0.97 (m, 3H), 1.17–1.40 (m, 4H), 1.40–2.50 (m) and 2.36 (d,
J = 14.5 Hz) (9.5H), 2.68 (db, J = 14.5 Hz, 0.5H), 4.20–4.70 (m, 0.5H), OH),
8.60–9.20 (m, 0.5H, OOH); IR (neat) (cm−1): 3380 (broad), 2970, 2940, 2890,
1715, 1460; Anal. calcd for C10H18O3: C, 64.49; H, 9.74; O, 25.77. Found: C,
64.21; H, 9.72; O, 25.98.
3-Hexyl-3-hydroperoxycyclohexanone/5-hexyl-6,7-dioxabicyclo[3.2.1]
octan-1-ol 5c. Method A, from 82 mg of hexylbicyclohexane 3c: 47 mg, 68%.
13C NMR (50 MHz, CDCl3) δ 14.1, 19.1, 20.9, 22.5, 22.6, 23.0, 24.4, 29.6, 31.3,
31.6, 31.7, 34.3, 35.4, 36.2, 36.8, 40.6, 48.4, 50.8, 87.2 (hydroperoxide), 88.6 (per-
oxyhemiketal), 107.4 (peroxyhemiketal), 210.5 (hydroperoxide); (hydroperoxide/
peroxyhemiketal ∼1.2:1); 1H NMR (250 MHz, CDCl3) δ 0.80–1.02 (m, 3H), 1.15–
1.40 (m, 8H), 1.40–2.53 (m) and 2.39 (d, J = 14.5 Hz) (9.5H), 2.68 (d, J = 14.5
Hz, 0.5H), 2.70–2.90 (m, 0.5H, OH), 7.30–7.50 (m, 0.5H, OOH); IR (neat) (cm−1):
3390 (broad), 2970, 2940, 2870, 1715, 1465.
3-Benzyl-3-hydroperoxycyclohexanone/5-benzyl-6,7-dioxabicyclo[3.2.
1]octan-1-ol 5d. White solid, Method A, from 179 mg of benzylbicyclohexane
3d: 75 mg, 50%. Method B, from 130 mg of benzylbicyclohexane 3d: 86 mg, 78%.
13C NMR (50 MHz, CDCl3) δ (hydroperoxyketone): 20.7, 31.0, 40.4, 43.0, 47.9,
87.3, 126.6, 128.2, 130.5, 136.2, 211.2; (peroxyhemiketal): 19.0, 34.4, 35.2, 42.4,
50.4, 88.4, 107.4, 126.5, 128.2, 130.0, 135.9; (hydroperoxide/peroxyhemiketal
∼2:1); 1H NMR (200 MHz, CDCl3) δ 1.40–2.50 (m) and 2.39 (d, J = 14.3 Hz)
(7.4H), 2.70 (dt, J = 14.3 and 1.0 Hz, 0.6H), 2.84 (d, J = 13.9 Hz) with 2.95 (d,
J = 13.9 HZ) (AB system) and 2.95 (d, J = 13.9 Hz) with 3.08 (d, J = 13.9 Hz)
(AB system) (2H), 3.40–4.00 (m, 0.4H, OH); 7.03–7.45 (m, 5H), 8.35–8.95 (m,
0.6H, OOH); Anal. calcd for C13H16O3: C, 70.89; H, 7.32; O, 21.79. Found: C,
70.60; H, 7.31; O, 21.56.
6-Methyl-7,8-dioxabicyclo[4.2.1]nonan-1-ol 5e. Method A, from
14.5 mg of methylbicycloheptane 3e: 8.8 mg, 54%. Method B, from 198 mg of

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BARNIER, MORISSON, AND BLANCO
methylbicycloheptane 3e: 126.4 mg, 80%. 13C NMR (62.9 MHz, CDCl3) δ 23.4,
1
23.5, 35.8, 40.8, 53.3, 85.9, 109.4; H NMR (200 MHz, CDCl3) δ 1.33 (s, 3H),
1.36–2.16 (8H), 2.42 (dd, J = 12.7 and 1.3 Hz, 1H), 2.82 (d, J = 12.7 Hz, 1H),
3.05–3.13 (m, 1H, OH); IR (CDCl3) (cm−1): 3550, 3490 (broad), 2960, 2895,
2825, 1680 (broad), 1455, 1430; Anal. calcd for C8H14O3: C, 60.74; H, 8.92; O,
30.34. Found: C, 60.88; H, 8.79; O, 30.27.
Preparation of 2,3-Epoxycycloalkanones 9 (General Procedure)
In a round-bottom flask was stirred at room temperature a solution of perox-
idated compound 5 (1 mmol) in 3 mL of diethyl ether with 0.5 mL of a 2 M NaOH
aqueous solution (1 mmol). After 1 h, 3 mL of water were added and the organic
phase was separated. The aqueous phase was extracted with diethyl ether and the
combined organic phases were dried over Na2SO4. After solvent evaporation, the
crude epoxide was purified by silica gel column chromatography (pentane/diethyl
ether 80:20).
2,3-Epoxy-3-methylcyclohexanone 9a. From 30 mg of methyl substi-
1
tuted peroxycompound 5a: 20 mg, 77%. For the H- and 13C-NMR spectra of
3-methyl-2,3-epoxycyclohexanone, see, respectively, (16,17).
3-Butyl-2,3-epoxycyclohexanone 9b. From 44 mg of butyl substituted
peroxycompound 5b: 34 mg, 85%. For the 1H- and 13C-NMR spectra of 3-butyl-
2,3-epoxycyclohexanone, see (18).
2,3-Epoxy-3-hexylcyclohexanone 9c. From 45 mg of hexyl substituted
peroxycompound 5c: 32 mg, 82%. IR (neat) 2960, 2840, 1720, 1440 cm−1 13C
;
NMR (62.9 MHz, CDCl3) δ 14.0, 17.3, 22.4, 24.5, 26.3, 29.1, 31.6, 35.88, 35.93,
61.1, 65.4, 207.0; 1H NMR (250 MHz,CDCl3) δ 0.88 (tb, J = 6.5 Hz, 3H), 1.15–
1.49 (m, 8H), 1.52–1.78 (m, 3H), 1.79–2.19 (m, 4H), 2.46–2.60 (m, 1H), 3.08 (s,
1H); EI-MS (m/z) 196 (M+, 8), 168 (2), 126 (5), 125 (6), 111 (8), 97 (67), 96
(13), 95 (11), 85 (5), 55 (100); Anal. calcd for C12H20O2: C, 73.43; H, 10.27; O,
16.30. Found: C, 73.41; H, 10.34; O, 16.41.
3-Benzyl-2,3-epoxycyclohexanone 9d. From 34.8 mg of benzyl substi-
tuted peroxycompound 5d: 25 mg, 78%. IR (CCl4) 3080, 3040, 2940, 2880, 1715,
1500, 1435, 1390, 1365, 1350, 1325, 1250, 1120 cm−1 13C NMR (50 MHz,
;
CDCl3) δ 17.2, 26.3, 35.9, 42.2, 60.5, 65.2, 127.0, 128.5, 129.5, 135.4, 206.6; 1H
NMR (200 MHz, CDCl3) δ 1.55–1.73 (m, 1H), 1.73–2.18 (m, 4H), 2.44–2.60 (m,
1H), 3.00 (s, 2H), 3.12 (s, 1H), 7.08–7.44 (m, 5H); EI-MS (m/z) 202 (M+, 55),

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357
174 (21), 173 (82), 145 (15), 129 (47), 117 (19), 115 (23), 111 (7), 91 (100), 77
(12), 65 (21); Anal. calcd for C13H14O2: C, 77.20; H, 6.98; O, 15.82. Found: C,
76.82; H, 6.88; O, 16.04.
2,3-Epoxy-3-methylcycloheptanone 9e. From 57.6 mg of methylperox-
yhemiketal 5e: 45 mg, 78%. IR (neat) 2935, 2860, 1702, 1500, 1440, 1430, 1408,
1265, 1208, 1077, 1035, 918, 832, 810 cm−1 13C NMR (62.9 MHz, CDCl3) δ 23.5,
;
24.5, 25.1, 33.8, 40.7, 61.3, 65.9, 210.4; 1H NMR (250 MHz, CDCl3) δ 1.10–1.20
(m, 1H), 1.42 (s, 3H), 1.62–1.95 (m, 4H), 2.12–2.23 (m, 1H), 2.23–2.35 (m, 1H),
2.71 (ddd, J = 14.2, 11.1 and 4.2 Hz, 1H), 3.25 (s, 1H); EI-MS (m/z) 140 (M+,
4), 112 (5), 111 (8), 98 (46), 97 (51), 96 (13), 84 (14), 83 (21), 82 (11), 70 (13),
69 (22), 68 (18), 67 (16), 56 (12), 55 (54), 54 (45), 53 (14), 52 (11), 43 (72), 42
(100); Anal. calcd for C8H12O2: C, 68.55; H, 8.63; O, 22.83. Found: C, 68.25; H,
8.85; O, 22.29.
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Received in the UK January 13, 2000

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