Synthesis of some [1,3]benzodioxoles via the reaction of o-quinones with phosphorus ylides

Article abstract of DOI:10.1080/10426500390220862

3,5-Di(tert-butyl)benzo-1,2-quinone 1c, phenanthrene-9,10-quinone 11, and 1,2-naphthoquinone 18 react with 1-phenylethylidene(triphenyl)phosphorane 2j, cyclopentylidene(triphenyl)phosphorane 2k, cyclohexylidene(triphenyl) phosphorane 21, and tetrahydro-2-furanyl-methylidene(triphenyl)phosphorane 8 to give the corresponding 2-substituted [1,3]benzodioxoles 5-7, 10, 12-14, 20-22 in low to high yields, instead of Wittig products, with exception of 11, 12-dihydro-10H-cyclopenta[b]phenanthro[9,10-d]furan 17. A possible explanation for these reaction sequences is discussed.

Full text of DOI:10.1080/10426500390220862

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Synthesis of Some [1,3]Benzodioxoles via the Reaction
of o-Quinones with Phosphorus Ylides
Daman R. Gautam a , Konstantinos E. Litinas a , Konstantina C. Fylaktakidou a & Demetrios
N. Nicolaides a
a Aristotle University of Thessaloniki , Thessaloniki, Greece
Published online: 23 Aug 2006.
To cite this article: Daman R. Gautam , Konstantinos E. Litinas , Konstantina C. Fylaktakidou & Demetrios N. Nicolaides
(2003) Synthesis of Some [1,3]Benzodioxoles via the Reaction of o-Quinones with Phosphorus Ylides, Phosphorus, Sulfur, and
Silicon and the Related Elements, 178:9, 1851-1864, DOI: 10.1080/10426500390220862
To link to this article: http://dx.doi.org/10.1080/10426500390220862
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Phosphorus, Sulfur, and Silicon, 178:1851–1864, 2003
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500390220862
SYNTHESIS OF SOME [1,3]BENZODIOXOLES
VIA THE REACTION OF o-QUINONES
WITH PHOSPHORUS YLIDES
Daman R. Gautam, Konstantinos E. Litinas,
Konstantina C. Fylaktakidou, and Demetrios N. Nicolaides
Aristotle University of Thessaloniki, Thessaloniki, Greece
(Received February 4, 2003)
3,5-Di(tert-butyl)benzo-1,2-quinone 1c, phenanthrene-9,10-quinone
11, and 1,2-naphthoquinone 18 react with 1-phenylethylidene(tri-
phenyl)phosphorane 2j, cyclopentylidene(triphenyl)phosphorane 2k,
cyclohexylidene(triphenyl)phosphorane 2l, and tetrahydro-2-furanyl-
methylidene(triphenyl)phosphorane 8 to give the corresponding 2-
substituted [1,3]benzodioxoles 5–7, 10, 12–14, 20–22 in low to high
yields, instead of Wittig products, with exception of 11,12-dihydro-10H-
cyclopenta[b]phenanthro[9,10-d]furan 17. A possible explanation for
these reaction sequences is discussed.
Keywords: [1,3]Benzodioxoles; o-quinones; phosphorus ylides
The reactions of o-quinones with phosphorus ylides can lead to the for-
mation of both expected and unexpected interesting compounds depend-
ing on the quinone and the ylide used.
Only a few double or bis-Wittig reactions of o-quinones with mono
and especially with bis-ylides have been reported.1−7 Usually the
reaction proceeds through an initial Wittig mono-olefination of the
quinone with formation of a reactive ortho-quinone methanide inter-
mediate, which is further transformed to benzofuran or benzopyran
derivatives.1,5,8−16
The formation of [1,3]benzodioxole derivatives, instead of Wittig re-
action products, also has been reported to proceed in reactions between
D. R. Gautam thanks the State Scholarships Foundation (IKY), Greece for financial
support and Tribhuvan University, Kathmandu, Nepal for granting him the Ph.D. study
leave.
Address correspondence to Demetrios N. Nicolaides, Laboratory of Organic Chem-
istry, Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki
54006, Greece.
1851

1852
D. R. Gautam et al.
certain o-quinones and phosphorus ylides. Bestmann and Lang8 re-
ported in 1969 that tetrachloro-o-benzoquinone 1a reacts with ben-
zylidene(triphenyl)phosphorane 2a to give 2-phenylmethylene-4,5,6,7-
tetrachloro-1,3-benzodioxole 3 (R1 R2 R3 R4 Cl, R5 H, R6 Ph) and
triphenylphosphine. The corresponding [1,3]benzodioxoles 3 also were
obtained from the reaction of the same o-quinone 1a with ylides 2b,17
2c,2 2d–f,18 and 2g,5 as well as from the reactions of 2d–f with quinone
1b.18 The formation of the corresponding 1,3-dioxoles in high yields
(82–90%), instead of Wittig products also was reported to proceed in
the reactions of 3,5-di(tert-butyl)benzo-1,2-quinone 1c with ylides 2d–f
(Scheme 1).19
Then we reported that the reactions of 4-methylchromene-2,7,8-
trione 1d with ylides 2b, 2h, 2i,20 as well as with ylides 2j–l21 afford the
corresponding fused 1,3-dioxolocoumarin derivatives 3 in 4–37% yields.
The reaction of 1d with ylide 2m gave, in addition to the corresponding
dioxole 3 (7%), the betaine 4 as the major product (28%) (Scheme 1).21
In connection with these studies we report now our results on the
reactions of ylides 2j, 2k, 2l, 8 with o-quinones 1c, 11, 18, which
lead to the formation of the title compounds in low to high yields
(10–90%).
SCHEME 1

Reaction of o-Quinones with Phosphorus Ylides
1853
RESULTS AND DISCUSSION
The reactions studied and the products obtained are depicted in
Schemes 2, 3, and 4.
We studied first the reaction of 3,5-di(tert-butyl)benzo-1,2-quinone
1c with 1-phenylethylidene(triphenyl)phosphorane 2j, prepared from
1-phenylethyl(triphenyl)phosphonium bromide, by using different
bases and experimental conditions. Treatment of a methylene chlo-
ride solution of 1c and the phosphonium salt under vigorous stir-
ring with aqueous lithium hydroxide solution (Method A), for 24 h
at room temperature (r.t.) and separation of the reaction mixture by
column chromatography gave 4,6-di(tert-butyl)-2-methyl-2-phenyl-1,3-
benzodioxole 5 in 90% yield. When a mixture of equimolar amounts of 1c
and the phosphonium salt in dioxane, which contained a small amount
of water, was treated with potassium carbonate under reflux (Method
B) for 20 h unreacted quinone 1c (19%) and product 5 (92%, based on
the quinone consumed) were obtained. We also tried the reaction at 0◦C
under N2 atmosphere, by treating a THF solution of equimolar amounts
of the above reactants with n-BuLi (Method C) for 18 h at r.t. Separation
of the reaction mixture by column chromatography gave unreacted 1c
(18%) along with compound 5 (83%, based on the quinone consumed)
(Scheme 2).
The reactions of quinone 1c with ylide 2k and ylide 2l, pre-
pared in situ from the corresponding phosphonium bromides,
SCHEME 2

1854
D. R. Gautam et al.
according to Method B afforded 4ꢁ,6ꢁ-di(tert-butyl)spirocyclopentane-
1,2ꢁ-benzodioxole and 4ꢁ,6ꢁ-di(tert-butyl)spirocyclohexane-1,2ꢁ-
6
benzodioxole 7 in 69% and 38% yield respectively.
When quinone 1c was treated with tetrahydro-2-furanylmethyl-
(triphenyl)phosphonium bromide, as described in Method B, for 45 h, it
gave (E)-4-[4,6-di(tert-butyl)benzo[d][1,3]dioxol-2-yl-3-buten-1-ol 10 in
27% yield along with 3,5-di(tert-butyl)-1,2-benzenediol (38%) and un-
reacted quinone 1c (25%). Obviously, tautomerization of the expected
ylide 8 initially formed to the ylide 9 via the opening of the tetrahydrofu-
ran ring; the reaction conditions22 and further reaction of the latter with
1c can account for the formation of the product 10 obtained (Scheme 2).
The reactions between phenanthrene-9,10-quinone 11 and ylides
2k, 2l, 8 were carried out according to Method B and gave
spirocyclopentane-1,2ꢁ-phenanthro[9,10-d][1,3]dioxole 12 (17%), spiro-
cyclohexane-1,2ꢁ-phenanthro[9,10-d][1,3]dioxole 13 (16%), and (Z ) 4-
(phenanthro[9,10-d][1,3]dioxol-2-yl)-3-buten-1-ol 14 (55%) respectively
(Scheme 3). From the reaction of 11 and 2k in addition to product 12,
11,12-dihydro-10H-cyclopenta[b]phenathro[9,10-d]furan 17 also was
obtained in 6% yield (obviously via an initial Wittig monoolefina-
tion of 11) followed by tautomerization-aromatization of the o-quinone
methanide 15 formed to the o-hydroxy derivative 16 and further
cyclization of the latter, as is suggested in Scheme 3.
SCHEME 3

Reaction of o-Quinones with Phosphorus Ylides
1855
SCHEME 4
The reaction of commercial 1,2-naphthoquinone 18 with the ylide
2j according to Method B resulted in a complicated mixture of prod-
ucts. Separation of the reaction mixture by column chromatography
gave from the faster moving band 2-methyl-2-phenyl-5-(2-methyl-2-
phenylnaphtho[1,2-d][1,3]dioxol-5-yl)-naphtho[1,2-d][1,3]dioxole 20 in
20% yield (Scheme 4). The structure suggested for this product agrees
well with the recorded analytical and spectral data, and especially with
the MS, 1H-NMR, and the 13C-NMR data, which reveal the symmetry of
the structure. The recorded 1H-NMR spectrum of the product in ques-
tion exhibited a two proton singlet at δ 7.12 ppm for the two symmetric
4-H, 4ꢁ-H of the two joined dioxolo-naphthalene systems, in good agree-
ment with the suggested 5,5ꢁ-linkage, for its two moieties.
The similar products 21 and 22 (Scheme 4) also were obtained in 32%
and 38% yield, respectively, from the reactions of the same quinone 18
with ylides 2k and 2l, under the same conditions, as it was established
from the analytical and spectral data of these products. Obviously prod-
ucts 20–22 are the 5,5ꢁ-dimers of the expected, but not isolated or de-
tected monomeric dioxoles 23a–c, respectively (Scheme 4), and were
formed via dimerization of them, or, more probably, compounds 20–22
were produced from the reaction of the known24 bis-quinone 19, formed

1856
D. R. Gautam et al.
by dimerization of quinone 18 and the ylides. Although in other reac-
tions of quinone 18 with some ylides, studied previously by us, only
products of the monomeric quinone 18 were obtained,4,10 the trans-
formation of 18 into the bis-quinone 19 by its treatment with ethyl
azidoformate also has been reported24 without comments.
When a dioxane solution of the quinone used in the above reactions
was treated under reflux with potassium carbonate and in the absence
of any of the above phosphonium salts, the starting quinone was quickly
converted to a tarry mass which remained at the bottom of the TLC
plate. Furthermore, when in a control experiment pure quinone 18,
obtained from a commercial sample by column chromatography, was
treated with ylide 2j under the conditions described above, compound
20 was again formed, as indicated by TLC examination of the reaction
mixture.
The analytical and spectral data (MS, IR, 1H-NMR, 13C-NMR) of all
1,3-dioxoles prepared agree well with the structures suggested for them
(see Experimental section).
From the experimental and the literature data presented in this arti-
cle we can notice that the formation of 1,3-dioxoles instead of an initial
Wittig olefination mainly was observed in the reactions of hindered
o-quinones 1a–c as well as in the reactions of the hindered phospho-
ranes 2d–f, 2j–l and that in the cases of reactions between the above
o-quinones and ylides the corresponding 1,3-dioxoles are formed almost
quantitatively. 1,3-Dioxoles also were formed, but in lower yield, from
the reactions of the less hindered quinones 1d, 11, 18 (19) with ylides
2j–l, 8 (9), as well as from the reactions between quinone 1a and ylides
2a–c, 2g–i.
It is obvious that the 1,3-dioxole formation is favored when the
o-quinone or the ylide used bear bulky substituents in the proximity of
their carbonyl carbon and their carbanionic carbon respectively. How-
ever, it must be noted that in contrast to above observations Wittig
olefination also has been observed to proceed between the quinones 1a,
6,13,14
1c and the ylides Ph3P COOR, Ph3P CHCOR, Ph3P CBr2
as
well as between the ylide 2e and quinone 11.1 Sidky and Boulos18 and
later Abdou19 suggested the following mechanistic reaction sequence
1 + 2 → 24 → 25 → 26 → 3 (Scheme 5) in order to explain the forma-
tion of 1,3-dioxoles 3 from the reactions between 1a–c and 2d–f.
According to their suggested mechanism, nucleophilic carbon attack
on the carbonyl carbon of quinone 1 by the phosphorane 2 yields the
betaine species 24, like in the first step of the normal Wittig reaction.
Subsequent anti elimination of triphenylphospine results in the for-
mation of the intermediate epoxide 25, which isomerizes to the stable

Reaction of o-Quinones with Phosphorus Ylides
1857
SCHEME 5
1,3-dioxole 3 through the dipolar form 26 or directly by an orbital sym-
metry allowed conversion.
We consider that an intermediate betaine conformer 24 suitable for
the anti elimination of triphenylphosphine is highly hindered—much
more hindered than the conformer 24ꢀ—which however is more suitable
for the continuation of the Wittig reaction sequence. This means that
the suggested19,22 original nucleophilic attack by the ylide to the car-
bonyl carbon of quinone seems to be not very possible. The formation
of an intermediate betaine 28 (Scheme 5), followed by ring closure—
triphenylphosphine elimination also could lead to the formation of 1,3-
dioxoles 3. Betaine 28 is less hindered and its intermediacy can also
explain the isolation of betaine 4 (Scheme 1) previously reported.21
Ohshiro et al.25 reported the formation of 1,3-dioxoles from the re-
action between nitroalkanes and o-quinones. They suggested that the
nitroalkane anion formally added to the cabonyl oxygen of the o-quinone
to give the intermediate 29 (Scheme 5), similar to 28, which by further
–
cyclization–elimination of NO2 affords 1,3-dioxoles. One of the possi-
ble mechanism of this abnormal addition is electron transfer from anion
to the quinone and subsequent radical coupling in the solvent cage.

1858
D. R. Gautam et al.
Although a similar mechanism can also be suggested for the forma-
tion of 1,3-dioxoles 3 via 28 from hindered o-quinones and phospho-
ranes, more evidence is necessary to explain their abnormal behavior
with certainty. Finally we note, that in contrast to the reaction of the
O-methyl monoxime of quinone 11 with ylides Ph3P CHCOR (R Ph,
OEt), which proceeded via an initial Wittig monoolefination of the
quinone carbonyl,26−28 the reactions of the O-methyl monoximes of hin-
dered quinones 1b, 1d with ylides Ph3P CHR (R Ar, COOEt, COOMe,
CH CRꢁ2) afforded the corresponding 2-R substituted benzoxazoles29,30
and the reactions with ylides Ph3P C(CH2R)COOEt (R = CH3, Ph,
H) gave 2H-[b][1,4]benzoxazine derivatives31 instead of any Wittig
product.
EXPERIMENTAL
M.p.s were determined on a Kofler hot-stage apparatus and are uncor-
rected. IR spectra were obtained with a Perkin-Elmer 1310 spectropho-
tometer as Nujol mulls except otherwise stated. NMR spectra were
1
recorded on a Bruker AM 300 (300 MHz, and 75 MHz for H and 13C,
respectively, using CDCl3 as solvent and TMS as an internal standard.
J values are reported in Hz. Mass spectra were determined on a VG-
250 spectrometer at 70 eV under Electron Impact (EI) conditions, or on
a Perkin Elmer API 100 Sciex Simple quadrupole under Electronspray
Ionization (ESI) conditions. High resolution mass spectra (HRMS) were
recorded on an Ionspec mass spectrometer under Matrix-Assisted Laser
Desorption-Ionization Fourier Transform Mass Spectrometer (MALDI-
FTMS) conditions with 2,5-dihydroxybenzoic acid (DHB) as the matrix.
Microanalyses were performed on a Perkin-Elmer 2400-II Element an-
alyzer. THF was refluxed over sodium and benzophenone and distilled,
when the mixture turned blue. Silica gel N◦60, Merck A.G. has been
used for column chromatographies.
Reaction of Quinone 1c with Ylide 2j
Method A (Phase Transfer Catalysis)
To a stirred solution of quinone 1c (0.66 g, 3 mmol) and 1-
phenylethyl(triphenyl)phosphonium bromide (1.341 g, 3 mmol) in
methylene chloride (45 ml) a freshly prepared 5N lithium hydroxide
solution (7.5 ml) was added at once and the two-phase reaction mixture
was further stirred at r.t. for 24 h. The organic phase was separated and
the aqueous layer was extracted with methylene chloride (3 × 45 ml).

Reaction of o-Quinones with Phosphorus Ylides
1859
The combined organic phases were dried over sodium sulfate, the sol-
vent was removed in a rotary evaporator, and the residue was subjected
to column chromatography, using hexane/ethyl acetate mixtures as
eluent.
Reactions of Quinones 1c, 11, 18 with Ylides 2j--l, 8
Method B (General Procedure)
To a stirred mixture of quinone 1c, 11, 18 (3 mmol), the corresponding
phosphonium salt (3 mmol) and potassium carbonate (3.6 mmol) in dry
dioxane (15 ml), water (98 mg) was added and the mixture was heated
under reflux for 4–72 h. After cooling at r.t. the precipitate was filtered
and washed with methylene chloride. The filtrates were combined, the
solvents were removed in a rotary evaporator, and the residue was sub-
jected to column chromatography. Mixtures of n-hexane with increasing
amounts of ethyl acetate or methylene chloride were used as eluents.
In addition to the reaction products, unreacted starting quinones were
eluted generally after the products described, unless otherwise stated.
Quinone 1c was recovered from the reactions with ylides: 2j (1c re-
covered 127 mg, 19%); 2k (150 mg, 23%); 2l (98 mg, 15%); 8 (170 mg,
26%). Quinone 11 was recovered from the reactions with ylides: 2j (11
recovered 134 mg, 21%); 2k (245 mg, 39%); 2l (313 mg, 50%); 8 (98 mg,
16%).
Reactions of Quinones 1c, 11 with Ylide 2j
Method C (General Procedure)
1-Phenylethyl(triphenyl)phosphonium bromide (0.66 g, 3.3 mmol)
was suspended in dry THF (50 ml) under dry N2. n-Butyllithium
(3.63 mmol) in hexane (2.27 ml) was added to the stirred mixture (at
r.t. in the case of 1c, at 0◦C in the case of 11) and stirring was continued
for 7 min. The red solution was then added to a solution of the quinone
1c, 11 (3 mmol) in dry THF (35 ml) at the same temperature, under N2.
The red color was discharged and the reaction mixture was stirred for
further 18–24 h. The solvent was removed in a rotary evaporator. The
residue was extracted with methylene chloride (3 × 100 ml) and dried
over sodium sulfate. The solvent was evaporated under reduced pres-
sure and the residue was subjected to column chromatography, using
mixtures of n-hexane with methylene chloride or with ethyl acetate as
eluents. In addition to the reaction products obtained, unreacted start-
ing quinone 1c (119 mg, 18%), 11 (289 mg, 46%) were recovered from
the reactions, eluted after the products obtained.

1860
D. R. Gautam et al.
4,6-Di(tert-butyl)-2-methyl-2-phenyl-1,3-benzodioxole 5
It was obtained from the reaction between 1c and 2j with Method A
(90%) or with Method B (20 h, 92%), or with Method C (18 h, 83%), m.p.
53–55◦C (hexane). Anal. Calcd. for C22H28O2, C 81.4, H 8.7. Found; C
81.8, H 8.8. IR cm−1 3025, 1592; NMR: 1H, δH 1.26 (s, 9H), 1.38 (s, 9H),
1.95 (s, 3H), 6.76 (s, 2H), 7.28–7.38 (m, 3H), 7.62 (d, 2H, J = 6.7); 13C,
δC 27.5, 29.6, 31.7, 34.1, 34.7, 104.1, 115.0, 115.9, 125.0, 128.2, 128.5,
131.4, 142.1, 142.2, 144.2, 147.0; EIMS: m/z 324 (M+, 65%), 309 (66),
267 (13), 247 (26), 207 (78), 191 (48), 147 (92), 105 (76), 91 (100), 77 (83).
4ꢀ,6ꢀ-Di(tert-butyl)spirocyclopentane-
1,2ꢀ-[1,3]benzodioxole 6
It was obtained from the reaction between 1c and 2k, prepared in
situ from cyclopentyl(triphenyl)phosphonium bromide with Method B
(21 h, 69%), m.p. 57–58◦C (ether/hexane). Anal. Calcd. for C19H28O2,
1
C 79.1, H 9.8. Found: C 79.3, H 10.1. IR cm−1 3050, 1590; NMR: H,
δH 1.27 (s, 9H), 1.34 (s, 9H), 1.78–1.92 (m, 4H), 2.07 (t, 4H, J = 6.5),
6.70 (s, 1H), 6.74 (s, 1H); 13C, δC 23.3, 29.4, 31.7, 34.0, 34.7, 37.1, 101.0,
103.7, 114.6, 126.1, 131.1, 143.7, 145.4, 147.3; EIMS: m/z 288 (M+, 7%),
273 (16), 192 (6), 179 (17), 106 (100), 104 (21), 77 (37), 57 (27).
4ꢀ,6ꢀ-Di(tert-butyl)spirocyclohexane-
1,2ꢀ-[1,3]benzodioxole 7
It was obtained from the reaction between 1c and 2l, prepared in situ
from cyclohexyl(triphenyl)phosphonium bromide with Method B (72 h,
38%), m.p. 64–65◦C (ether/hexane). Anal. Calcd. for C20H30O2, C 79.4,
1
H 10.0. Found: C 79.7, H 10.1. IR cm−1 3060, 1590; NMR: H, δH 1.28
(s, 9H), 1.35 (s, 9H), 1.42–1.59 (m, 2H), 1.68–1.81 (m, 4H), 1.83–1.99
(m, 4H), 6.70 (s, 1H), 6.73 (s, 1H); 13C, δC 23.3, 24.7, 29.4, 31.7, 34.0,
34.7, 35.2, 103.9, 114.5, 117.1, 131.2, 142.3, 143.6, 147.1; EIMS: m/z
303 (M++H, 18%), 302 (100, M+), 287 (90), 259 (30), 231 (4), 81 (13).
(E)4-[4,6-Di(tert-butyl)benzo[d][1,3]dioxol-2-yl]-
3-buten-1-ol 10
It was obtained from the reaction between 1c and 8, prepared in
situ from tetrahydro-2-furanylmethyl(triphenyl)phosphonium bromide
with Method B (45 h, 27%) (eluted after unreacted 1c), m.p. 59–61◦C
1
(hexane). IR cm−1 3300, 1665, 1590, 1480; NMR: H, δH 1.28 (s, 9H),
1.35 (s, 9H), 1.37 (brs, 1H), 2.42 (q, 2H, J = 6.4), 3.75 (t, 2H, J = 6.4),
5.85 (dd, 1H, J = 6.4, 15.3), 6.11 (dt, 1H, J = 6.4, 15.3), 6.34 (d, 1H,
J = 6.4), 6.72 (d, 1H, J = 1.7), 6.76 (d, 1H, J = 1.7); 13C, δC 29.5, 31.6,
34.0, 34.7, 35.3, 61.4, 104.0, 109.4, 115.2, 127.7, 131.5, 134.6, 142.6,
144.4, 147.3; EIMS: m/z 304 (M+, 100%), 273 (17), 259 (43), 243 (13),

Reaction of o-Quinones with Phosphorus Ylides
1861
233 (22), 217 (16), 207 (29), 191 (28), 175 (16), 145 (20), 131 (29), 115 (35),
105 (33); MALDIHRMS (DHB): m/z 304.2037 [M]+. C19H28O3 requires
m/z 304.2033.
Spirocyclopentane-1,2ꢀ-phenanthro[9,10-d][1,3]dioxole 12
It was obtained from the reaction between 11 and 2k, prepared in situ
from cyclopentyl(triphenyl)phosphonium bromide with Method B,
(19 h, eluted after 17, 17% yield), m.p. 116–118◦C (DCM/hexane). Anal.
Calcd. for C19H16O2, C 82.6, H 5.8. Found: C 82.6, H 5.7. IR cm−1 3050,
1600, 1510; NMR: 1H, δH 1.90–2.03 (m, 4H), 2.26 (t, 4H, J = 7.3), 7.48–
7.64 (m, 4H), 7.91 (d, 2H, J = 8.3), 8.64 (d, 2H, J = 8.3); 13C, δC 23.5,
37.6, 120.1, 121.5, 123.2, 124.2, 126.7, 126.9, 128.7, 137.3; EIMS: m/z
276 (M+, 100%), 247 (87), 210 (22), 194 (12), 191 (11), 181 (65), 163 (83),
152 (98).
Spirocyclohexane-1,2ꢀ-phenanthro[9,10-d][1,3]dioxole 13
It was obtained from the reaction between 11 and 2l, prepared in situ
from cyclohexyl(triphenyl)phosphonium bromide with Method B (67 h,
10%), m.p. 106–108◦C (ether/hexane) Anal. Calcd. for C20H18O2, C 82.7,
1
H 6.25. Found: C 82.4, H 6.2. IR cm−1 3050, 1600, 1515; NMR: H, δH
1.47–1.67 (m, 2H), 1.77–1.95 (m, 4H), 2.09 (t, 4H, J = 6.0), 7.50–7.63
(m, 4H), 7.93 (d, 2H, J = 8.4), 8.66 (d, 2H, J = 8.3); 13C, δC 23.3, 24.8,
35.3, 119.9, 120.1, 120.2, 123.2, 124.1, 126.6, 126.7, 137.2; EIMS: m/z
291 (M++H, 52%), 290 (73, M+), 248 (18), 247 (16), 210 (34), 209 (18),
182 (36), 181 (52), 180 (17), 164 (30), 152 (60), 82 (37), 81 (100).
(Z ) 4-(Phenanthro[9,10-d][1,3]dioxol-2-yl)-3-buten-1-ol 14
It was obtained from the reaction between 11 and 8, prepared in
situ from tetrahydro-2-furanylmethyl(triphenyl)phosphonium bromide
with Method B (72 h, 55%) (eluted after unreacted 11), m.p. 87–88◦C
(DCM/hexane). IR cm−1 (KBr) 4323, 3050, 1636, 1600; NMR: 1H, δH 1.22
(t, 1H, J = 7.1), 1.99–2.06 (m, 1H), 2.22–2.78 (m, 1H), 3.90–3.96 (m,
1H), 4.01–4.06 (m, 1H), 5.26 (ddt, 1H, J = 1.5, J = 3.7, J = 8.8), 5.90
1
2
3
(dd, 1H, J = 3.7, J = 9.9), 7.16 (dd, 1H, J = 1.5, J = 9.9), 7.52 (, 1H,
1
2
1
2
J = 8.1), 7.56–7.65 (m, 3H), 7.99 (d, 1H, J = 8.1), 8.26 (d, 1H, J = 7.7),
8.61 (d, 2H, J = 8.4); 13C, δC 36.9, 59.2, 101.3, 121.0, 121.9, 122.6, 123.0,
124.4, 126.7, 127.0, 134.7, 147.3; ESIMS: m/z 293 [MH]+; MALDIHRMS
(DHB): m/z 292.1090 [M]+. C19H16O3 requires m/z 292.1093.
11,12-Dihydro-10H-cyclopenta[b]phenanthro-
[9,10-d]furan 17
It was obtained from the reaction between 11 and 2k, prepared in situ
from cyclopentyl(triphenyl)phosphonium bromide with Method B (19 h,

1862
D. R. Gautam et al.
eluted before 12, 6%), m.p. 156–158◦C (methylene chloride/hexane).
Anal. Calcd. for C19H14O, C 88.3, H 5.5. Found: C 88.1, H 5.5. IR cm−1
3050, 1605; NMR: 1H, δH 2.62–2.79 (m, 2H), 2.99 (t, 2H, J = 6.1), 3.09
(t, 2H, J = 6.3), 7.53–7.72 (m, 4H), 8.08 (d, 1H, J = 8.0), 8.28 (d, 1H,
J = 8.0), 8.70 (dd, 2H, J = 2.3 and J = 7.3); 13C, δC 24.0, 25.0, 28.1,
106.3, 119.0, 120.0, 123.0, 123.2, 123.3, 124.6, 124.8, 124.9, 126.7, 126.9,
127.6, 127.9, 128.1, 153.2, 161.5; EIMS: m/z 258 (M+, 100%), 257 (33),
231 (60), 215 (38), 210 (58), 209 (19), 202 (58), 189 (15), 181 (58), 165
(22), 152 (52).
2-Methyl-2-phenyl-5-(2-methyl-2-phenylnaphtho-
[1,2-d][1,3]dioxol-5-yl)-naphtho[1,2-d][1,3]dioxole 20
It was obtained from the reaction between 18 and 2j, prepared in situ
from 1-phenylethyl(triphenyl)phosphonium bromide with Method B
(18 h, 20%), m.p. 209–211◦C (methylene chloride/hexane). IR cm−1
(methylene chloride) 3040, 1625, 1595, 1460, 1260, 1170; NMR: 1H, δH
2.15 (s, 3H), 7.04–7.20 (m, 2H), 7.29–7.44 (m, 5 H), 7.69–7.73 (m, 2H),
7.92 (d, 1H, J = 7.6); 13C, δC 27.2, 91.8, 113.0, 117.9, 119.9, 123.7, 125.0,
125.8, 127.2, 128.3, 128.9, 129.2, 131.9, 140.4, 141.6, 142.1; EIMS: m/z
522 (M+, 54%), 508 (8), 420 (44), 419 (21), 405 (7), 318 (50), 317 (22),
289 (21), 103 (100), 77 (75); MALDIHRMS (DHB): m/z 522.1835 [M]+.
C36H26O4 requires m/z 522.1826.
5ꢀ-(Spirocyclopentane-1,2ꢀ-naphtho[1,2-d][1,3]dioxol-
5ꢀ-yl)spirocyclopentane-1,2ꢀ-naphtho[1,2-d][1,3]dioxole 21
It was obtained from the reaction between 18 and 2k, prepared
in situ from cyclopentyl(triphenyl)phosphonium bromide with Me-
thod B (18 h, 32%), m.p. 239–242◦C (ethyl acetate/hexane). IR cm−1
(methylene chloride) 3040, 1630, 1600, 1260; NMR: 1H, δH 1.85–2.0 (m,
8H), 2.20–2.34 (m, 8H), 7.08 (t, 2H, J = 7.6), 7.12 (s, 2H), 7.30 (d, 2H,
J = 7.6), 7.38 (t, 2H, J = 7.6), 7.86 (d, 2H, J = 7.6); 13C, δC 23.4, 37.5,
112.7, 119.5, 119.8, 123.5, 125.6, 127.2, 128.5, 128.9, 131.5, 140.6, 142.2;
EIMS: m/z 450 (M+, 49%), 422 (20), 385 (7), 356 (10), 338 (11), 271 (15),
226 (59), 225 (22), 215 (28), 202 (15), 67 (100); MALDIHRMS (DHB):
m/z 450.1818 [M]+. C30H26O4 requires m/z 450.1825.
5ꢀ-(Spirocyclohexane-1,2ꢀ-naphtho[1,2-d][1,3]dioxol-5ꢀ-
yl)spirocyclohexane-1,2ꢀ-naphtho[1,2-d][1,3]dioxole 22
It was obtained from the reaction between 18 and 2l, prepared in
situ from cyclohexyl(triphenyl)phosphonium bromide with Method B
(18 h, 38%), m.p. 226–228◦C (ether/hexane). IR cm−1 (methylene chlo-
1
ride) 3040, 1625, 1595, 1140; NMR: H, δH 1.52–1.62 (m, 4H), 1,77–
1.86 (m, 8H), 2.04–2.11 (m, 8H), 7.08 (t, 2H, J = 7.6), 7.12 (s, 2H), 7.30

Reaction of o-Quinones with Phosphorus Ylides
1863
(d, 2H, J = 7.6), 7.38 (t, 2H, J = 7.6), 7.87 (d, 2H, J = 7.6); 13C, δC 23.6,
24.6, 35.9, 113.0, 119.7, 119.8, 123.3, 125.5, 127.2, 128.8, 128.9, 131.4,
140.5, 142.2; EIMS: m/z 478 (M+, 100%), 435 (8), 397 (8), 271 (9), 226
(7), 215 (11), 202 (6), 81 (98); MALDIHRMS (DHB): m/z 478.2143 [M]+.
C32H30O4 requires m/z 478.2139.
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