SHORT PAPER
A Convenient Synthesis of 9,10-Bis(3-methylphenyl)anthracene on a Kilo-Lab Scale
199
temperature of the solution had reached 130 ± 5 °C, the voltage was
r.t. overnight. The white 4b was filtered on an 18.5 cm Büchner on
reduced to 2/3 maximum, and CuCl (650 g, 4.83 mol) was added
Whatman #54 paper, and the filtrate removed for recycling. The
product was washed with 95% EtOH (500 mL) and dried at 85 °C/
25 Torr for 16 h; yield: 227 g (63%); mp 220−222.5 °C. The product
was stored in an opaque container since it is slightly light-sensitive.
2
in about 50-g portions during about 20 min at 125 ± 5 °C. The reac-
tion was endothermic and HCl evolved with foaming. Gray CuCl
separated. More voltage was applied to the mantle to obtain a brisk
reflux for 1 h, then the voltage was lowered. When the suspension
had cooled to 125 ± 5 °C without stirring, it was filtered by decan-
tation on a porcelain Büchner funnel with 15-cm Whatman #54
paper, which was pre-warmed by pouring about 100 mL of hot
1
H NMR (CDCl /TMS): δ = 2.48 (s, 6 H, CH ), 7.24−7.37 [high-or-
3
3
der m, 10 H, H-2,3,5,8, and 2 î (H-2’,4’,6’)], 7.46−7.51 (over-
lapped dd, 2 H, 2 î H-5’), 7.68−7.74 (AA’BB’ system, 4 H, H-
1
,4,6,7).
3
-chlorotoluene on it under 100 Torr pressure. Another 400 mL of
UV (5.7 î 10-5 M in toluene): λ
= 339 nm (ε = 4200), 355
hot 3-chlorotoluene was used to rinse the CuCl in the flask and the
material on the funnel. The hot filtrate was transferred to a 6-L
beaker covered with a watch glass and aluminum foil, and allowed
to cool to r.t. Then it was placed in a −20 ± 10 °C freezer overnight.
The product was filtered on 18.5 cm Whatman #54 paper in a
porcelain Büchner. This first filtrate was removed for re-use or re-
max
(
9600), 373 (16000), 393 (15100).
Anal. calcd for C H (358.5): C, 93.81; H, 6.19. Found C, 93.75;
2
8
22
H, 6.40.
distillation. The yellow solid was washed with 95% EtOH (500 mL) Acknowledgement
and dried at 85 °C/25 Torr for 16 h; yield: 233−263 g (86−97%);
1
2
The work was sponsored by Packard Instrument B. V., Groningen,
The Netherlands; and permission to publish by Ing. Manfred Bösel
and Jan ter Wiel is most gratefully appreciated. The NMR spectrum
was determined and interpreted by Walter J. Boyko, Villanova Uni-
versity. The UV spectrum was determined by Farzad Kobarfard.
The manuscript was critically reviewed by Charles J. Kelley.
yellow needles; mp 210.5−212.5 °C (Lit. mp 210 °C). It is a de-
layed-action (4−6 h) lachrymator and should be handled in a fume
hood.
9
,10-Di-m-tolylanthracene (4b)
A 5-L 4-necked flask placed in a heating mantle was fitted with a
mechanical stirrer, a combination thermometer and gas inlet adapt-
er, a quadruple-surface condenser of 500 mm working length fitted
at the top with a gas outlet adapter leading to a fume hood inlet, and
a straight adapter of 200 mm length on top of which was a funnel
with an ST29/42 joint covered with a watch glass. Mg (73.0 g, 3.00
mol) was added, argon flow was started, and 40% of maximum volt-
age was applied to the mantle. The straight adapter and funnel were
replaced with a 1-L addition funnel. When the temperature of the
flask had reached 60 ± 10 °C, 100−200 mL of a solution of 3-bro-
motoluene (1b; 513 g, 354 mL, 3.00 mol) in THF (3 L) was added.
The Grignard reaction usually started with some violence. The rest
of the 3-bromotoluene in THF was added in a thin stream at a rate
to maintain rapid reflux, usually for 1 h. Some heat was needed to
maintain reflux toward the end, and reflux was then maintained by
heating for 2 h. The addition funnel was replaced with a straight
adapter and funnel. The mixture was allowed to cool to 60 ± 2 °C
References
(1) Berlman, I. B. Handbook of Fluorescence Spectra of Aromatic
Molecules, 2nd ed., Academic Press: New York, 1971.
(2) Morris, J. V.; Mahaney, M. A.; Huber, J. R. J. Phys. Chem.
1976, 80, 969.
(3) Hamal, S.; Hirayama, F. J. Phys. Chem. 1983, 87, 83.
(4) Ingold, C. K.; Marshall, P. G. J. Chem. Soc. 1926, 3080.
(5) Willemart, A. Bull. Soc. Chim. Fr. 1942, 9, 83.
(6) Étienne, A.; Arditti, G.; Chmelevsky, A. Bull. Soc. Chim. Fr.
1965, 669.
(7) Kelley, C. J.; Ghiorghis, A.; Kauffman, J. M. J. Chem. Res. (S)
1999, 80; (M), 401.
(8) Kauffman, J. M. Synthesis 1999, 918.
(9) Rehahn, R.; Schlüter, A-D., Feast, W. J. Synthesis 1988, 386.
(10) Heilbron, I. M.; Heaton, J. S. Org. Syn. Coll. Vol. I, 2nd ed.
1941, 207.
whereupon the catalyst NiCl •dppp (2.0 g) was added through the
2
straight adapter, cautiously at first. When any mild exotherm had
subsided within a few minutes, 9,10-dichloroanthracene (6; 247 g,
(11) Aryan, Z. S.; Wiles, L. A. J. Chem. Soc. 1962, 1725.
(12) Tanimoto, I.; Kushioka, K.; Kitagawa, T.; Maruyama, K. Bull.
Chem. Soc. Jpn 1979, 52, 3586.
(13) Jay, K.; Stieglitz, L. Chemosphere 1991, 22, 987.
(14) Wagner, G.; Herrmann, R.; Scherer, W. J. Organomet. Chem.
1996, 516, 225.
1
.00 mol) was added in portions as fast as the violent reaction al-
lowed: ª45 min. The black liquid was then allowed to cool to 50 ±
°C; then MeOH (50 mL) was added, very cautiously at first. An
5
exotherm to 60 °C was a good indicator that excess Grignard re-
agent was present, as desired. The hot liquid mixture was then
poured into MeOH (6 L) in a 12-L pail with mechanical stirring.
Crude 4b usually crystallized at once. After 10−30 min of stirring,
the pail was covered and kept at −2 °C overnight. The crude was fil-
tered on a 24 cm Büchner using polyethylene filter cloth,1 washed
(15) Minato, A.; Tamao, K.; Hayashi, T.; Suzuki, K.; Kumada, M.
Tetrahedron Lett. 1981, 22, 5319.
(16) Kauffman, J. M.; Bjorkman, C. O. J. Chem. Educ. 1976, 53,
33.
7
with 95% EtOH (500 mL), and slurried with H O (2 L) and 12 M
(17) A gift from National Filter Media, P. O. Box 156, 691 North
400 West, Salt Lake City, UT, 84110, USA; style 192 058 03.
(18) Custom-made by Tom Cachaza, The Glassblowers,
Turnersville, NJ, 08112, USA.
2
HCl (90 mL) for 10−30 min, filtered on the same cloth, washed with
minimum H O, and dried at 85 °C /25 Torr for 16 h. The dry 4b
2
(
ª252 g) was loaded onto a 10-cm-high column of alumina sand-
wiched between 1 cm layers of sand in a side-arm extractor of 6 cm
1
8
inside diameter and 60 cm working length. Continuous extraction
was carried out with heptane (3.5 L) in a tared 5-L flask overnight.
The extract was kept at −2 °C overnight. The heptane was decanted
and the flask with 4b was dried at 85 °C/25 Torr for 5 h. The yellow
Article Identifier:
1437-210X,E;2001,0,02,0197,0199,ftx,en;M00900SS.pdf
4
b was recrystallized from 10 mL/g of 2-ethoxyethanol, usually 2.2
L, with transfer of the hot clear solution to a 6-L beaker, and kept at
Synthesis 2001, No. 2, 197–199 ISSN 0039-7881 © Thieme Stuttgart · New York