Synthesis of eight-, nine-, and ten-membered, nitrogen-containing quinone-fused heterocycles

Article abstract of DOI:10.1055/s-2006-958937

A series of allylamino-, diallylamino-, homoallylamino-and bishomoallylamino naphthoquinones were synthesized. Ruthenium-mediated ring-closing metathesis (RCM) efficiently converted these substrates into novel eight-, nine-, and ten-membered quinone-fused heterocycles. Hydro-derivatives of diazacine, diazonine, and diazecine were isolated and characterized. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2006-958937

PAPER
239
Synthesis of Eight-, Nine-, and Ten-Membered, Nitrogen-Containing Quinone-
Fused Heterocycles
Synthesis of
N
a
itrogen-Co
r
ntaining
i
Q
uinon
t
e-Fused
H
ete
Y
rocycles erushalmi, N. Gabriel Lemcoff,* Shmuel Bittner*
Department of Chemistry, Ben Gurion University of the Negev, Beer Sheva, 84105, Israel
Fax +972(8)6472943; E-mail: bittner@bgumail.bgu.ac.il
Received 16 July 2006; revised 6 October 2006
yielding the vinylogous amides: 2-alkyl (aryl) amino-3-
Abstract: A series of allylamino-, diallylamino-, homoallylamino-
and bishomoallylamino naphthoquinones were synthesized. Ruthe-
nium-mediated ring-closing metathesis (RCM) efficiently convert-
ed these substrates into novel eight-, nine-, and ten-membered
chloro-1,4-naphthoquinones.12 Indeed, allylamine and ho-
moallylamine both smoothly substituted one chlorine
atom of quinone 1, producing the monosubstituted deriv-
quinone-fused heterocycles. Hydro-derivatives of diazacine, diazo- atives 2a and 2b in high yields (Scheme 1). Such substitu-
nine, and diazecine were isolated and characterized.
tions induce electronic enrichment of the quinone system
and inhibits the replacement of the second chlorine atom.
To enable a second substitution to take place, therefore, an
electron-withdrawing effect must be imposed on the
quinonic ring. Among the several methods developed,13–16
we chose to apply N-acylation of the monoaminoqui-
nones. Reaction of 2 with acetic anhydride, in the pres-
ence of sulfuric acid, afforded the acylated derivatives 3
in good yields. The substitution of the second chlorine
atom thus became possible and the 2,3-diallylamino- (4a),
2-allylamino 3-homoallylamino- (4b), 3-allylamino
2-homoallylamino- (4c) and 2,3-bishomoallylamino (4d)
derivatives could be obtained.
Key words: naphthoquinone, ring-closing metathesis, cyclization,
heterocycles, diazacines, diazecines, diazonines
Quinones and their derivatives are important biological
compounds, which participate in most crucial bioprocess-
es in living cells. They are found in higher plants, fungi,
bacteria, and throughout the animal kingdom. Their
central role in biosynthetic processes involves electron
transport in cellular respiration (ubiquinones) and photo-
synthesis (plastoquinones). Numerous natural products,
such as rifamycins,2 damavaricins3 and streptovaricins,4
contain the aminonaphthoquinone moiety in their
structure1 and derivatives of these compounds have been
synthesized and used as antitrypanosomal,5 antimalarial,6
antitumor7 and antineoplastic8 agents. They have also
found use in color chemistry, hair dying,9 and as photosta-
bilizers.10
1
The H NMR spectra of 4 displayed signals arising from
four different aromatic protons between d = 8.1–7.6 ppm,
as expected for such non-symmetric systems. The internal
vinylic protons on the double bonds appear as multiplets
between d = 4.6–5.4 ppm, while the terminal vinylic pro-
tons are observed as multiplets between d = 4.9–5.3 ppm.
Splitting patterns correspond to typical allylic signals,
with the methylene protons a- to the NH group observed
separately between d = 3.5–5.5 ppm and the methylene
protons b- to the NH group appearing separately between
d = 2.0–2.7 ppm. The infrared spectra exhibited typical
strong quinonic carbonyl absorption between 1635 and
1680 cm–1 and the NH stretching vibration between 3237
and 3330 cm–1.
As several of the highly active antibiotics contain quino-
nes embedded in a macrocyclic structure and, in several
cases, the quinone is bridged to the cyclic part via an NH
group, it became of interest to prepare and study such
model compounds.
Our strategy was to first attach two aliphatic chains via
NH bridges to a quinonic compound and, subsequently, to
join these chains to form a medium-sized ring. The avail-
ability and functional group tolerance of second-genera-
tion Grubbs’ catalysts made it an attractive candidate for
the preparation of such macrocyclic systems via alkene
ring-closing metathesis.11 In this paper we describe our
initial studies on attaching allylamine and homoallyl-
amine to a naphthoquinone core and the formation of
novel naphthoquinone hydro-derivatives of diazacine, di-
azonine and diazecine.
Ring-closing olefin metathesis (RCM), was performed us-
ing the ‘second-generation’ Grubbs’ catalyst {ruthenium
[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-
dichloro(phenymethylene)
(tricyclohexylphosphine)}
(Scheme 2). The reaction was accomplished by heating
4a–d in dry toluene, with the catalyst (0.05 equiv), at 70–
75 °C for 3–5 hours under argon. The corresponding cy-
clic products 5 were isolated in 85–96% yield. Since nei-
ther dimers nor polymers were formed, even when
concentrated solutions were used, it seems that the effec-
tive molarity17 of the molecules highly favors cyclization
over polymerization.18
It is known that aliphatic as well as aryl amines of en-
hanced nucleophilicity react with 2,3-dichloro-1,4-naph-
thoquinone (1), substituting only one chlorine atom,
1
The H NMR spectra of the eight-, nine- and ten-mem-
bered rings 5a–d lack the terminal vinylic hydrogen sig-
nals, as anticipated. Signals arising from the double bond
SYNTHESIS 2007, No. 2, pp 0239–0242
Advanced online publication: 14.12.2006
DOI: 10.1055/s-2006-958937; Art ID: T10506SS
x
x
.
x
x
.2
0
0
7
© Georg Thieme Verlag Stuttgart · New York

240
S. Yerushalmi et al.
PAPER
O
O
Cl
Cl
Cl
(Ac)2O
H2SO4
EtOH
+ NH2(CH2)nCH=CH2
(CH2)nCH=CH2
N
H
O
O
2
1
O
O
H
Cl
N
NH2(CH2)mCH=CH2
(CH2)mCH=CH2
(CH2)nCH=CH2
(CH2)nCH=CH2
N
N
O
Ac
O
Ac
4
3
2a 2b 3a 3b 4a 4b 4c 4d
n
1
-
2
-
1
2
-
1
1
2
2
m
-
1
2
1
2
Scheme 1 Synthesis of unsaturated bis-aminonaphthoquinones
2-(2-Propenylamino)-3-chloronaphthalene-1,4-dione (2a)
To 2,3-dichloro-1,4-naphthoquinone (1; 1.00 g, 4.40 mmol), dis-
solved in EtOH (100 mL) was added, dropwise at r.t., allylamine
(0.670 mL, 8.80 mmol). The mixture was stirred for 6 h then half of
the solvent was evaporated under vacuum and the remaining solu-
tion was cooled to 0–5 °C. The precipitated orange material was fil-
tered off, washed with cold EtOH (2 × 20 mL) and recrystallized (n-
hexane–CH2Cl2, 3:1) to afford the pure product 2a.
O
O
H
N
H
N
( )m
(CH2)mCH=CH2
(CH2)nCH=CH2
catalyst
– C2H4
N
N
( )n
O
Ac
O
Ac
4
5
Yield: 1.03 g (95%); fine orange needles; mp 116–118 °C (Lit.19
111–112 °C).
IR (KBr): 3384, 1658, 1585, 1529, 1320, 951, 765 cm–1.
5a 5b 5c 5d
N
N
Cl
Ru
n
1
1
1
2
2
1
2
2
Cl
Ph
P(Cy)3
m
UV/Vis (CHCl3): lmax (log e) = 275 (3.43), 335 (3.10), 462 nm
(3.43).
Grubbs' second-generation catalyst
1H NMR (500 MHz, CDCl3): d = 8.12 (dd, J = 1.2, 7.7 Hz, 1 H),
8.01 (dd, J = 1.2, 7.7 Hz, 1 H), 7.70 (td, J = 7.7, 1.2 Hz, 1 H), 7.61
(td, J = 7.7, 1.2 Hz, 1 H), 6.01 (s, 1 H), 5.92–5.99 (m, 1 H), 5.22–
5.29 (m, 2 H), 4.46–4.48 (m, 2 H).
Scheme 2 Synthesis of nitrogen-containing quinone-fused hetero-
cycles
13C NMR (125 MHz, CDCl3): d = 180.3, 176.8, 134.9, 134.0, 132.5,
hydrogens appear between d = 5.2–5.8 ppm (J = 10–11
Hz). The asymmetric nature of these cyclic molecules is 132.5, 129.7, 126.8, 117.5, 115.9, 115.9, 102.9, 47.0.
indicated by the unique chemical shifts observed for each
of the hydrogens. 13C NMR and HR-MS, all concur with
the expected cyclic structures.
2-(3-Butenylamino)-3-chloronaphthalene-1,4-dione (2b)
3-Butenylamine hydrochloride (100 mg, 0.929 mmol) and NaHCO3
(78 mg, 0.929 mmol) were dissolved in a mixture of MeOH (30 mL)
In summary, we have demonstrated here the applicability
of ring-closing olefin metathesis for the preparation of the
synthetically useful quinone-fused hydro derivatives of
diazacine, diazonine and diazecine, under rather mild con-
ditions, in high yields. Further studies on the cross-
metathesis of substituted quinones are in progress in our
laboratory.
and H2O (10 mL). 2,3-Dichloro-1,4-naphthoquinone (211 mg,
0.929 mmol) was added and the mixture was stirred at r.t. for 24 h.
The solvents were evaporated in vacuo and the crude orange prod-
uct was purified by column chromatography (n-hexane–EtOAc,
7:3) and recrystallization (n-hexane–CH2Cl2, 3:1) to afford the pure
product 2b.
Yield: 189 mg (78%); orange needles; mp 98–100 °C.
IR (KBr): 3437, 1629, 1584, 1540, 1313, 747 cm–1.
UV/Vis (CHCl3): lmax (log e) = 274 (3.89), 337 (2.97), 447 nm
IR spectra were recorded on a Nicolet 5ZDX FT-IR spectrometer.
1H and 13C NMR spectra were recorded on Bruker WP 200 SY and
Bruker DMX 500 instruments. Mass spectra (CI in CH4) were ob-
tained on a Finnigan 4020 quadrupole spectrometer and LC-MS
(APCI, atmospheric pressure chemical ionization) was performed
using a Bruker esquire 3000plus (Bruker Daltonics, Germany). UV/
Vis spectra were measured using a Jasco V530 diode array spectro-
photometer. TLC was carried out on Merck 5554 pre-coated silica
gel 60 plates. Melting points were measured using a Thomas–
Hoover capillary apparatus and are uncorrected. All chemicals, sol-
vents and reagents were of commercial quality.
(2.75).
1H NMR (500 MHz, CDCl3): d = 8.13 (dd, J = 0.8, 7.7 Hz, 1 H),
8.01 (dd, J = 0.8, 7.7 Hz, 1 H), 7.71 (td, J = 7.7, 1.4 Hz, 1 H), 7.61
(td, J = 7.7, 1.4 Hz, 1 H), 6.09 (s, 1 H), 5.76–5.84 (m, 1 H), 5.16–
5.23 (m, 2 H), 3.93 (q, J = 6.7 Hz, 2 H), 2.42–2.46 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 180.4, 176.8, 134.9, 134.1, 132.4,
132.5, 129.7, 126.8, 118.4, 118.4, 115.4, 102.9, 43.7, 34.9.
Synthesis 2007, No. 2, 239–242 © Thieme Stuttgart · New York

PAPER
Synthesis of Nitrogen-Containing Quinone-Fused Heterocycles
241
Preparation of 4a–d; Typical Procedure
(m, 1 H), 3.98–4.10 (m, 3 H), 2.95–2.99 (m, 1 H), 2.45–2.53 (m,
1 H), 2.11–2.19 (m, 1 H), 1.95 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 182.2, 179.7, 172.1, 135.4, 135.3,
133.2, 132.6, 132.6, 132.4, 130.0, 126.9, 126.8, 126.7, 117.9, 116.3,
48.5, 45.6, 31.5, 22.4.
2-Chloro-3-(2-propenylamino)-1,4-naphthalenedione (2a; 651 mg,
2.63 mmol) was dissolved in freshly distilled Ac2O (0.800 mL)
cooled to 5 °C and stirred under argon. H2SO4 (20 mL) was added
and the reaction mixture was warmed to r.t. and stirred for 12 h. The
solvent was then evaporated to give a yellow oil, which was redis-
solved in EtOH (25 mL). Allylamine (0.380 mL, 5.00 mmol) was
added dropwise to the ethanolic solution and the mixture was stirred
at r.t. for 4 h. Ice water (20 mL) was added and stirring was contin-
ued for an additional 2 h. The precipitated product was filtered off,
washed with H2O (2 × 10 mL), cold EtOH (2 × 10 mL) and recrys-
tallized to give the pure product 4a.
MS (ESI): m/z = 362.9 [M + K]+, 347.0 [M + Na]+, 325.0 [M + H]+.
2-(3-Butenylamino)-3-(3-butenylacetamido)naphthalene-1,4-
dione (4d)
Yield: 53%; orange needles; mp 108–109 °C.
IR (KBr): 3449, 1679, 1577, 1552, 1332, 956 cm–1.
UV/Vis (CHCl3): lmax (log e) = 273 (3.42), 339 (2.42), 455 nm
2-(2-Propenylamino)-3-(2-propenylacetamido)naphthalene-
1,4-dione (4a)
Yield: 571 mg (70%); orange needles; mp 115–116 °C (n-hexane–
CH2Cl2, 3:2).
IR (KBr): 3451, 1678, 1586, 1551, 1324, 952 cm–1.
(2.43).
1H NMR (500 MHz, CDCl3): d = 8.11 (dd, J = 1.3, 7.7 Hz, 1 H),
8.04 (dd, J = 1.3, 7.7 Hz, 1 H), 7.74 (td, J = 7.6, 1.3 Hz, 1 H), 7.62
(td, J = 7.6, 1.3 Hz, 1 H), 6.08 (s, 1 H), 5.66–5.77 (m, 2 H), 5.18–
5.23 (m, 2 H), 4.91–5.01 (m, 2 H), 3.98–4.04 (m, 1 H), 3.44–3.51
(m, 1 H), 3.34–3.40 (m, 1 H), 2.91–2.96 (m, 1 H), 2.42–2.50 (m,
1 H), 2.36–2.42 (m, 2 H), 2.10–2.18 (m, 1 H), 1.94 (s, 3 H).
UV/Vis (CHCl3): lmax (log e) = 272 (3.43), 338 (2.45), 452 nm
(2.51).
1H NMR (500 MHz, CDCl3): d = 8.12 (dd, J = 1.4, 7.7 Hz, 1 H),
8.08 (dd, J = 1.4, 7.7 Hz, 1 H), 7.77 (td, J = 7.6, 1.2 Hz, 1 H), 7.66
(td, J = 7.6, 1.2 Hz, 1 H), 6.17 (s, 1 H), 5.84–5.95 (m, 2 H), 5.26–
5.30 (m, 2 H), 5.04–5.12 (m, 2 H), 4.44 (dd, J = 6.0, 14.0 Hz,1 H),
4.09–4.14 (m, 1 H), 4.00–4.06 (m, 1 H), 3.83 (dd, J = 7.6, 14.1 Hz,
1 H), 1.97 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 182.1, 179.6, 171.8, 135.3, 135.2,
132.8, 132.5, 132.5, 132.6, 130.0, 126.8, 126.6, 118.0, 116.3, 116.2,
51.5, 45.8, 22.4.
13C NMR (125 MHz, CDCl3): d = 182.2, 179.7, 172.0, 135.4, 135.3,
133.8, 132.5, 132.5, 132.2, 130.1, 126.8, 126.9, 119.1, 116.3, 116.3,
48.8, 42.2, 34.2, 31.6, 22.3.
MS (ESI): m/z = 377.1 [M + K]+, 361.1 [M + Na]+, 338.4 [M + H]+.
Preparation of 5a–d; General Procedure
Compound 4 (1.20 mmol) was dissolved in dry toluene (40 mL) and
Grubbs’ second-generation catalyst (19 mg, 0.05 equiv) was added.
The reaction mixture was stirred at 70–75 °C under argon and mon-
itored by TLC (n-hexane–EtOAc, 1:1). After 5 h the solvent was
evaporated and the crude product was purified on a silica gel col-
umn (n-hexane–EtOAc, 1:1).
MS (ESI): m/z = 349.0 [M + K]+, 333.1 [M + Na]+, 311.1 [M+H]+.
2-(2-Butenylamino)-3-(2-propenylacetamido)naphthalene-1,4-
dione (4b)
Purified by column chromatography (n-hexane–EtOAc, 1:1) and re-
crystallization (n-hexane–CH2Cl2, 4:1).
1-Acetyl-1,2,5,6-tetrahydronaphtho[2,3-b][1,4]diazocine-7,12-
dione (5a)
Yield: 96%; orange needles; mp 186–187 °C.
IR (KBr): 3402, 1639, 1579, 1529, 1316, 975 cm–1.
Yield: 49%; orange needles; mp 112–113 °C.
IR (KBr): 3449, 1674, 1567, 1555, 1331, 956 cm–1.
UV/Vis (CHCl3): lmax (log e) = 272 (3.34), 337 (2.45), 450 nm
(2.51).
UV/Vis (CHCl3): lmax(log e) = 273 (3.31), 335 (2.39), 445 nm
(2.25).
1H NMR (500 MHz, CDCl3): d = 8.09 (dd, J = 1.2, 7.8 Hz, 1 H),
8.04 (dd, J = 1.2, 7.6 Hz, 1 H), 7.86 (td, J = 7.6, 1.4 Hz, 1 H), 7.75
(td, J = 7.6, 1.4 Hz, 1 H), 6.44 (s, 1 H), 5.63–5.76 (m, 2 H), 5.52–
5.57 (m, 1 H), 4.39–4.45 (m, 1 H), 3.63–3.69 (m, 1 H), 3.57–3.61
(m, 1 H), 1.97 (s, 3 H).
13C NMR (125 MHz, acetone-d6): d = 184.0, 108.2, 172.9, 147.5,
136.9, 136.9, 134.9, 134.3, 133.5, 132.5, 127.9, 127.9, 125.3, 51.2,
39.9, 22.9.
1H NMR (500 MHz, CDCl3): d = 8.08 (dd, J = 1.2, 7.7 Hz, 1 H),
8.03 (dd, J = 1.2, 7.7 Hz, 1 H), 7.73 (td, J = 7.7, 1.2 Hz, 1 H), 7.62
(td, J = 7.7, 1.2 Hz, 1 H), 6.11 (s, 1 H), 5.81–5.89 (m, 1 H), 5.70–
5.79 (m, 1 H), 5.18–5.23 (m, 2 H), 5.01–5.09 (m, 2 H), 4.40 (dd,
J = 6.3, 14.0 Hz, 1 H), 3.84 (dd, J = 7.1, 14.4 Hz, 1 H), 3.50–3.57
(m, 1 H), 3.36–3.44 (m, 1 H), 2.37–2.41 (m, 2 H), 1.96 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 182.1, 181.2, 172.0, 135.3, 133.8,
132.8, 132.5, 132.5, 132.5, 130.0, 124.4, 126.8, 126.6, 119.1, 118.7,
51.8, 42.3, 34.1, 22.4.
MS (EI, 70 eV): m/z (%) = 240.093 (100), 283.109 (22) [M + H]+.
HRMS (CI in CH4): m/z [M + H]+ calcd for C16H15N2O3: 283.10827;
MS (ESI): m/z = 363.1 [M + K]+, 347.1 [M + Na]+, 325.1 [M + H]+.
found: 283.10949.
2-(3-Butenylacetamido)-3-(2-propenylamino)naphthalene-1,4-
dione (4c)
Yield: 57%; orange needles; mp 101–102 °C.
IR (KBr): 3448, 1677, 1571, 1556, 1330, 950 cm–1.
7-Acetyl-2,3,6,7-tetrahydro-1H-naphtho[2,3-b][1,4]diazonine-
8,13-dione (5b)
Yield: 82%; orange needles; mp 179–181 °C.
IR (KBr): 3437, 1641, 1559, 1527, 1311, 956, 765 cm–1.
UV/Vis (CHCl3): lmax(log e) = 279 (3.39), 334 (2.38), 447 nm
(2.29).
1H NMR (500 MHz, CDCl3): d = 8.14 (dd, J = 1.3, 7.7 Hz, 1 H),
8.09 (dd, J = 1.3, 7.7 Hz, 1 H), 7.78 (td, J = 7.3, 1.3 Hz, 1 H), 7.67
(td, J = 7.5, 1.3 Hz, 1 H), 6.20 (s, 1 H), 5.86–5.96 (m, 1 H), 5.69–
5.77 (m, 1 H), 5.24–5.29 (m, 2 H), 4.99–5.04 (m, 1 H), 4.94–4.96
UV/Vis (CHCl3): lmax (log e) = 273 (3.78), 333 (2.43), 458 nm
(2.37).
1H NMR (500 MHz, CDCl3): d = 8.14 (dd, J = 1.0, 7.6 Hz, 1 H),
8.06 (dd, J = 1.0, 7.6 Hz, 1 H), 7.77 (td, J = 7.4, 1.3 Hz, 1 H), 7.65
(td, J = 7.6, 1.3 Hz, 1 H), 6.45 (s, 1 H), 5.76–5.81 (m, 2 H), 4.75
(dd, J = 4.9, 14.1 Hz, 1 H), 3.48–3.90 (m, 3 H), 2.50–2.63 (m, 1 H),
2.45–2.54 (m, 1 H), 1.98 (s, 3 H).
Synthesis 2007, No. 2, 239–242 © Thieme Stuttgart · New York

242
S. Yerushalmi et al.
PAPER
13C NMR (50 MHz, CDCl3): d = 182.1, 180.5, 172.2, 144.3, 135.3,
134.9, 134.3, 132.5, 131.0, 129.3, 126.7, 126.6, 44.6, 41.9, 27.8,
22.3.
MS (EI, 70 eV): m/z (%) = 237.095 (100), 297.122 (28) [M + H]+.
HRMS (CI in CH4): m/z [M + H]+ calcd for C17H17N2O3: 297.12392;
References
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found: 297.12229.
1-Acetyl-2,3,6,7-tetrahydro-1H-naphtho[2,3-b][1,4]diazonine-
8,13-dione (5c)
Yield: 89%; orange needles; mp 184–185 °C.
IR (KBr): 3436, 1654, 1557, 1555, 1331, 951 cm–1.
UV/Vis (CHCl3): lmax (log e) = 275 (3.38), 329 (2.33), 448 nm
(2.37).
1H NMR (500 MHz, CDCl3): d = 8.11 (dd, J = 1.3, 7.7 Hz, 1 H), 8.6
(dd, J = 1.3, 7.7 Hz, 1 H), 7.75 (td, J = 7.5, 1.3 Hz, 1 H), 7.65 (td,
J = 7.5, 1.3 Hz, 1 H), 6.46 (s, 1 H), 5.92–5.97 (m, 1 H), 5.22–5.29
(m, 1 H), 4.46–4.49 (m, 2 H), 4.05–4.13 (m, 1 H), 2.74–2.84 (m,
2 H), 1.98–2.01 (m, 1 H), 1.97 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 182.3, 179.6, 171.5, 143.3, 135.2,
133.0, 132.6, 132.5, 130.3, 126.7, 126.6, 123.4, 120.6, 52.6, 42.0,
24.8, 21.6.
MS (ESI): m/z (%) = 337.9 [M + K]+, 319.0 [M + Na]+, 297.0 [M +
H]+.
HRMS (CI in CH4): m/z [M+] calcd for C17H16N2O3: 296.11609;
found: 296.11693.
1-Acetyl-1,2,3,6,7,8-hexahydronaphtho[2,3-b][1,4]diazecine-
9,14-dione (5d)
Yield: 88%; orange crystals; mp 186–188 °C.
IR (KBr): 3409, 1639, 1551, 1527, 1315, 765 cm–1.
(11) (a) Deiters, A.; Martin, S. F. Chem. Rev. 2004, 104, 2199.
(b) Grubbs, R. H. Handbook of Metathesis; Wiley & Sons:
London, 2003.
(12) Finley, K. T. In The Chemistry of Quinonoid Compounds,
Part II; Patai, S., Ed.; Wiley: London, 1974, 877.
(13) Vladimirtsev, I. F.; Postovskii, I. Y.; Trefilova, L. F. Zh.
Obshch. Khim. 1954, 24, 181.
UV/Vis (CHCl3): lmax (log e) = 274 (3.89), 337 (2.97), 447 nm
(2.75).
1H NMR (500 MHz, CDCl3): d = 8.11 (dd, J = 1.3, 7.7 Hz, 1 H),
8.09 (dd, J = 1.3, 7.7 Hz, 1 H), 7.75 (td, J = 7.5, 1.3 Hz, 1 H), 7.64
(td, J = 1.3, 7.7 Hz, 1 H), 6.50 (s, 1 H), 5.66–5.71 (m, 1 H), 5.45–
5.52 (m, 3 H), 5.25–5.29 (m, 1 H), 4.86–4.90 (m, 1 H), 2.97–3.04
(m, 1 H), 2.22–2.46 (m, 2 H), 2.19–2.13 (m, 1 H), 1.82 (s, 3 H).
13C NMR (50 MHz, CDCl3): d = 182.2, 175.4, 172.5, 135.2, 134.0,
132.5, 130.0, 129.7, 126.7, 126.6, 126.5, 125.0, 121.0, 35.9, 32.2,
29.5, 29.2, 22.7.
(14) Agarwal, N. L.; Ghosh, S.; Tripathi, A.; Atal, C. K. J.
Heterocycl. Chem. 1984, 21, 509.
(15) Fries, K.; Billig, K. Ber. Dtsch. Chem. Ges., B 1925, 58,
1128.
(16) Win, T.; Bittner, S. Tetrahedron Lett. 2005, 46, 3229.
(17) Cacciapaglia, R.; Di Stefano, S.; Mandolini, L. Acc. Chem.
Res. 2004, 37(2), 113.
(18) Kirby, A. J. Adv. Phys. Org. Chem. 1980, 17, 183.
(19) Johnson, M. G.; Kiyokawa, H.; Tani, S.; Koyama, J.;
Morris-Natschke, S. L.; Mauger, A.; Bowers-Daines, M. M.;
Lange, B. C.; Lee, K.-H. Bioorg. Med. Chem. 1997, 1469.
MS (EI, 70 eV): m/z (%) = 213.084 (100), 310.129 (36) [M+].
HRMS (CI in CH4): m/z [M+] calcd for C18H18N2O3: 310.13174;
found: 310.12959.
Acknowledgement:
This research was supported in part by Grant No.2004318 from the
United States–Israel Binational Science Foundation (BSF), Jerusa-
lem, Israel. We wish to thank Mrs. Ethel Solomon and Mrs. Aliza
Levkowitz for skillful technical help.
Synthesis 2007, No. 2, 239–242 © Thieme Stuttgart · New York