Notes
J . Org. Chem., Vol. 61, No. 11, 1996 3869
anhydrous MgSO4 and filtered, the solvent was removed in the
usual manner to afford, after vacuum drying, crude 10 (4.3 g).
The crude product was sufficiently pure by TLC to be used for
the subsequent step without further purification. For charac-
terization, 50 mg of the crude reaction product was purified by
p.l.c. using 30:70 ethyl acetate:hexane. Isolation of the major
band afforded colorless crystalline 10 (42 mg, 84%),13 mp 89-
90 °C; 13C NMR δ ) 22.7, 61.5, 62.2, 124.4, 124.8, 126.0, 127.1,
128.3, 126.6, 131.1, 133.1, 153.8, 166.6; MS m/ z (%) 388 (32),
352 (18), 339 (13), 337 (28), 325 (11), 323 (13), 321 (19), 309 (24)
265 (19), 252 (21); HRMS M+ 388.1667, calcd for C25H24O4
388.1673.
AgNO3 (0.025g, 0.15 mmol) in THF (5.0 mL). The mixture was
protected from light and stirred at room temperature for 24 h
under Ar. The grey precipitate was filtered and vacuum dried
to afford 12 (52 mg), mp 135-138 °C dec.): 1H NMR δ ) 1.61
(s, H2O), 1.85 (m, THF), 3.40 (br, 6H), 3.75 (m, THF), 4.03 (s,
8H), 4.10 (br s, 6H), 4.64 (br, 2H), 4.85 (s, 2H), 6.93 (br, 2H),
7.33-7.50 (m, 6H), 7.53-7.55 (m, 4H), 7.69 (m, 2H), 8.08-8.19
(m, 6H); +FAB MS (matrix: 3-nitrobenzyl alcohol); m/ z (%) 880
(M+).
Bis-(4-m eth oxy-3-(m er ca p tom eth y)ln a p h th yl)m eth a n e
(13). To a solution of 149 (540 mg, 1.06 mmol) in DMSO (25
mL) was added thiourea (200 mg, 2.65 mmol) under N2, and the
solution was stirred at room temperature for 5 h. The reaction
was quenched by pouring the solution into a cold aqueous 10%
solution of NaOH (100 mL), and the resulting solution was left
to stir at room temperature for 2 h. The mixture was neutralized
at 0 °C by the addition of aqueous 10% HCl. The precipitate
was filtered, washed repeatedly with water, and air dried to give
13 (391 mg, 88%), mp 134-135 °C: 1H NMR δ ) 1.76 (t, 2H),
3.82 (d, 4H), 4.02 (s, 6H), 4.75 (s, 2H), 7.02 (s, 2H), 7.57-7.44
(m, 4H), 7.98 (dd, J ) 8.1 Hz, 2H), 8.17 (dd, 8.1 Hz, 2H); 13C
NMR δ ) 23.1, 35.1, 62.7, 122.8, 124.4, 126.0, 126.2, 128.3, 129.1,
132.5, 132.5, 132.8, 152.0; MS m/ z (%) 420 (66), 387 (45), 183
(100); HRMS M+ 420.1240, calcd for C25H24O2S2 420.1216.
Bis-(m eth yl-2-m eth oxy-3-n a p h th oyl)m eth a n e (11). A so-
lution of 2-hydroxy-3-naphthoic acid (2.0 g, 10.6 mmol) and
paraformaldehyde (0.43 g, 14. 2 mmol HCOH) in 0.5% H2SO4-
glacial acetic acid (20 mL) was refluxed for 10 h. After the
solution was cooled to room temperature, a light yellow precipi-
tate formed which was filtered and washed twice with 5 mL
portions of a saturated NaCl solution. The product was dried
under vacuum to give 3.9 g (95%) of bis(2-hydroxy-3-naphthoyl)-
methane as a light yellow powder, mp >300 °C. This was used
directly in the following step. To a solution of 3.9 g of in CH2-
Cl2 (15 mL) were added water (30 mL), 0.5 mL of the phase-
transfer catalyst Adogen, and aqueous 10% NaOH (10 mL). To
the vigorously stirred mixture at room temperature were added
dimethyl sulfate (6.5 mL, 60 mmol) dropwise over a period of
15 min at room temperature. The mixture was stirred at room
temperature for an additional 10 h. After separation of the two
layers, the aqueous layer was extracted twice with 20 mL
portions of CH2Cl2. The solvent was removed on a rotary
evaporator, and the residue was mixed with 10 mL water and
diethyl ether (50 mL). The ether layer was separated and
washed twice with 10 mL portions of aqueous 2.0 M NH4OH in
order to remove the excess dimethyl sulfate. The ether layer
was washed twice with 60 mL portions of saturated NaCl and
then was dried over anhydrous MgSO4, filtered, and evaporated
on a rotary evaporator. After the solution was dried under
vacuum, the crude product was flash chromatographed using
40:60 ethyl acetate:hexane to give 11 (2.1 g 95%) as a cream-
colored solid, mp 113-115 °C (lit.13 mp 133 °C, methanol): 13C
NMR δ ) 22.6, 52.3, 62.7, 123.7, 124.7, 125.2, 128.3, 129.3, 129.8,
130.0, 132.3, 135.2, 153.6, 166.8; MS m/ z (%) 444 (100), 412 (81),
397 (76), 381 (8), 353 (56), 337 (43), 324 (50), 280 (20); HRMS
M+ 444.1578, calcd for C27H24O6 444.1573.
Dith ia d ih om oca lixn a p h th a len e (12). A solution consist-
ing of 9 (1.96 g, 3.83 mmol) and 13 (1.60 g, 3.82 mmol) was
prepared in benzene (200 mL). This solution was added drop-
wise, over a 15 h period, into a solution of ethanolic KOH (2.5 g
in 500 mL 95% ethanol) under N2. The mixture was stirred
vigorously during the addition and for an additional 24 h after
the addition was completed. A colorless precipitate formed
which was filtered by suction filtration, washed with water, and
air dried. The product was flash chromatographed (CH2Cl2:
petroleum ether 80:20) to give 12 (350 mg). The filtrate was
concentrated to 50 mL, and the colorless crystals which sepa-
rated were filtered and washed with aqueous 10% HCl, cold
water, ethanol and finally petroleum ether to give 12 (2.15 g)
whose melting point was identical to that of the first crop
obtained from the first filtration. The total yield of 12 was 2.50
g (85%), mp 173-175 °C: 1H NMR: δ ) 3.34 (s, 6H), 3.81 (s,
4H), 3.82 (s, 4H), 3.94 (s, 6H), 4.58 (s, 2H), 4.84 (s, 2H), 6.87 (s,
2H), 7.32-7.36 (m, 4H), 7.39-7.44 (m, 2H), 7.48-7.54 (m, 2H),
7.69-7.74 (m, 4H), 7.88 (d, J ) 8.1 Hz, 2H), 8.00-8.03 (m, 2H),
8.12 (dd, J ) 8.1 Hz, 2H); 13C NMR δ ) 23.9, 30.8, 32.0, 34.9,
61.6, 62.7, 122.9, 123.7, 124.3, 124.5, 125.8, 126.0, 126.1, 128.2,
128.4, 128.6, 128.8, 129.0, 130.8, 131.2, 132.2, 132.6, 153.1, 155.3;
MS m/ z (%) 707 (3), 692 (2), 601 (5), 587 (3), 570 (3), 555 (8),
537 (4) 524 (6), 387 (48); HRMS M+ 772.2658, calcd for
Dith ia d ih om oca lixn a p h th a len e (16). A solution consist-
ing of 13 (0.28 g, 0.67 mmol) and 14 (0.34 g, 0.67 mmol) was
prepared in benzene (40 mL). This solution was added dropwise,
over a 10 h period, into a solution of ethanolic KOH (0.23 g in
110 mL of 95% ethanol), under N2. The mixture was stirred
vigorously during the addition and for an additional 18 h after
the addition was completed. A colorless precipitate formed
which was filtered by suction filtration, washed successively with
aqueous 10% HCl, water, and ethanol, and, finally, air dried to
give 0.42 g of 16 (81%), mp 285-290 °C: 1H NMR δ ) 3.76 (s,
8H), 3.85 (s, 12H), 4.61 (br s, 4H), 6.70 (s, 4H), 7.41-7.51 (m,
8H), 7.92-7.96 (m, 4H), 8.09-8.11 (m, 4H); 13C NMR δ ) 31.30,
34.47, 62.70, 122.69, 122.74, 122.82, 123.99, 124.16, 125.47,
125.53, 125.58, 125.81, 125.91, 125.96, 125.91, 125.96, 126.10,
128.17, 128.22, 128.25, 129.24, 129.40, 131.81, 132.78; MS m/ z
(%) 772 (5), 731 (6), 679 (6), 601 (16), 529 (10), 387 (20), 386
(22); HRMS M+ 772.2695, calcd for C50H44O4S2 772.2681.
Silver Ion Com p lex 16a . To a solution of 16 (121 mg, 0.157
mmol) in 6.0 mL of THF was added AgNO3 (0.026 g, 0.15 mmol)
in THF (5.0 mL). The mixture was protected from light and
stirred at room temperature for 24 h under Ar. The grey
precipitate was filtered and vacuum dried to afford 16a (98 mg),
mp 220-224 °C dec; 1H NMR δ ) 1.58 (s, H2O), 1.85 (m, THF),
3.75 (m, THF), 3.98 (s, 12H), 4.25 (s, 8H), 4.72 (s, 4H), 7.15 (s,
4H), 7.52-7.60 (m, 4H), 8.17-8.09 (m, 4H); +FAB MS (matrix:
3-nitrobenzyl alcohol) m/ z (%) 880 (M+).
Ack n ow led gm en t. We are grateful to Mu’Tah Uni-
versity, J ordan for providing a scholarship to one of us
(M.A.) and to Memorial University for providing finan-
cial assistance to Z.L. We thank Dr. C. R. J ablonski
for the high-resolution NMR spectra and Dr. B. Gregory
and Ms. M. Baggs for the mass spectra. All FAB/MS
and some HRP/MS were obtained by Mr. D. Drummond,
Department of Chemistry, University of New Brun-
swick.
Su p p or t in g In for m a t ion Ava ila b le: 1H NMR and 13C
NMR spectral data for the following new compounds: 5, 6, 7,
8, 9, 12, 12a , 13, 16, 16a . Also included are signal assign-
ments wherever determined. An ORTEP diagram of the X-ray
structure of 5 is included (4 pages). This material is contained
in libraries on microfiche, immediately follows the article in
the microfilm version of the journal, and can be ordered from
the ACS; see any current masthead page for ordering
information.
C
50H44O4S2 772.2681.
Silver Ion Com p lex 12a . A solution of 12 (110 mg, 0.15
mmol) in 2.5 mL of THF was added dropwise to a solution of
(13) Failla, S.; Finocchiaro, P.; Belsky, V. K.; Zavodnik, V. E.;
Sobolev, A. N. J . Inclusion Phenom. Mol. Recognit. Chem. 1993, 15,
247.
J O9520654