2306
L. Hintermann, K. Suzuki
PRACTICAL SYNTHETIC PROCEDURES
Diethyl 2,5-Dichloro-3,6-dihydroxyterephthalate (4b)
(3) Succinylsuccinate (or: succinylosuccinate) is a trivial name
for esters of 2,5-dioxocyclohexane-1,4-dicarboxylic acid
(or, in the more stable enol form: 1,4-dihydroxycyclohexa-
1,4-diene dicarboxylic acids), obtained by the condensation
of two molecules of succinic esters, compare: Nielsen, A. T.;
Carpenter, W. R. Org. Synth. Coll. Vol. V; John Wiley &
Sons: London, 1973, 288.
(4) With Br2: (a) Herrmann, F. Justus Liebigs Ann. Chem. 1882,
211, 306. (b) Bagrov, F. V.; Bagrov, D. F. Russ. J. Org.
Chem. 1994, 30, 637. With MnO2: (c) Padias, A. B.; Hall,
H. K. J. Org. Chem. 1985, 50, 5417. (d) Itami, K.;
Palmgren, A.; Thorarensen, A.; Bäckvall, J.-E. J. Org.
Chem. 1998, 63, 6466.
To a slurry of 3b (321.5 mg, 1 mmol) in CH2Cl2 (5 mL) and AcOH
(1 drop), a soln of Na2S2O4 (86% content; 256 mg, 1.26 mmol) in
H2O (3 mL) was added and the two-phase mixture was stirred at r.t.
for 2 h. t-BuOMe (20 mL) and H2O were added and the organic
phase was washed with sat. NaCl (2 ×). The soln was dried
(MgSO4), filtered, and evaporated to give a white solid from the yel-
low soln. Chromatography (silica gel, EtOAc–hexanes, 1:5 to 1:2)
gave 4b (306 mg, 95%) as mixed yellow and white (polymorphic)
crystals; mp 123.7–124.0 °C (corr.) (Lit.5 123 °C). Note: Addition
of MeOH or THF will speed up this biphasic reaction.
1H NMR: d = 1.45 (t, J = 7.2 Hz, 6 H), 4.50 (q, J = 7.2 Hz, 4 H),
9.34 (s, 2 H).
13C NMR: d = 14.0, 63.1, 119.2, 119.6, 148.3, 167.0.
(5) Hantzsch, A.; Zeckendorf, A. Ber. Dtsch. Chem. Ges. 1887,
20, 1308.
(6) (a) Liebermann, H.; Lewin, G.; Gruhn, A.; Gottesmann, E.;
Lisser, D.; Schonda, K. Justus Liebigs Ann. Chem. 1934,
513, 156. (b) Neidlein, R.; Throm, S. Arch. Pharm.
(Weinheim, Ger.) 1980, 313, 572.
(7) (a) von der Crone, J.; Pugin, A. US 3,130,195, 1964.
(b) Jaffe, E. E. US 3,124,582, 1964. Compare: (c) Imai, M.;
Ikuta, H.; Akahori, H.; Hasegawa, K.; Asano, M.;
Tsujimoto, M. JP 57185237, 1982. (d) Altiparmakian, R.
Helv. Chim. Acta 1978, 61, 1146.
(8) Hantzsch, A. Ber. Dtsch. Chem. Ges. 1915, 48, 797.
(9) (a) Curtin, D. Y.; Byrn, S. R. J. Am. Chem. Soc. 1969, 91,
1865. (b) Curtin, D. Y.; Byrn, S. R. J. Am. Chem. Soc. 1969,
91, 6102. (c) Swiatkiewicz, J.; Prasad, P. N. J. Am. Chem.
Soc. 1982, 104, 6913. (d) Strohmeier, M.; Orendt, A. M.;
Alderman, D. W.; Grant, D. M. J. Am. Chem. Soc. 2001, 123,
1713.
(10) (a) Byrn, S. R.; Curtin, D. Y.; Paul, I. C. J. Am. Chem. Soc.
1972, 94, 890. (b) Yang, Q.-C.; Richardson, M. F.; Dunitz,
J. D. J. Am. Chem. Soc. 1985, 107, 5535. (c) Yang, Q.-C.;
Richardson, M. F.; Dunitz, J. D. Acta Crystallogr., Sect. B.
1989, 45, 312. (d) Richardson, M. F.; Yang, Q.-C.;
Novotny-Bregger, E.; Dunitz, J. D. Acta Crystallogr., Sect.
B 1990, 46, 653.
(11) (a) Yatsenko, A. V. J. Mol. Model. 2003, 9, 207.
(b) Swerts, B.; Van Droogenbroeck, J.; Peeters, A.; Van
Alsenoy, C. J. Phys. Chem. A 2002, 106, 4245. (c) Peeters,
A.; Lenstra, A. T. H.; Van Doren, V. E.; Van Alsenoy, C.
THEOCHEM 2001, 546, 25. (d) Peeters, A.; Lenstra, A. T.
H.; Van Doren, V. E.; Van Alsenoy, C. THEOCHEM 2001,
546, 17. (e) Ceolin, R.; Toscani, S.; Agafonov, V.; Dugue, J.
J. Solid State Chem. 1992, 98, 366.
(12) (a) Asano, M.; Hasegawa, K.; Akahori, H.; Tsujimoto, M.
EP 55,847, 1982. (b) Morishima, S.; Wariishi, K.; Shibata,
M.; Ishida, T. EP 820,057, 1998.
(13) Thermal transesterification of b-oxo esters (in the absence of
a catalyst) is an old reaction: (a) Peters, T. Justus Liebigs
Ann. Chem. 1890, 257, 353. (b) Cohn, P. Monatsh. Chem.
1900, 21, 200. (c) Bader, A. R.; Cummings, L. O.; Vogel, H.
A. J. Am. Chem. Soc. 1951, 73, 4195. (d) Witzeman, J. S.
Tetrahedron Lett. 1990, 31, 1401.
Dibenzyl 2,5-Dichloro-3,6-dihydroxyterephthalate (4c)
A soln of 3c (418.5 mg, 0.94 mmol) in CH2Cl2 (10 mL) and a soln
of Na2S2O4 (86%; 250 mg, 1.08 mmol) in H2O (5 mL) were vigor-
ously stirred while MeOH (10 mL) was slowly added, causing a col-
or change from yellow to greenish yellow. After 10 min, the organic
solvents (CH2Cl2, MeOH) were removed (by rotatory evaporation)
and the resulting suspension was filtered. The yellow solid was
washed with H2O and dried in air to give 4c (379.6 mg, 90%) as yel-
low crystalline leaflets; mp 113–114 °C.
1H NMR: d = 5.47 (s, 4 H), 7.34–7.51 (m, 10 H), 9.21 (s, 2 H).
13C NMR: d = 68.6, 119.4, 119.8, 128.8, 129.0, 129.0, 134.6, 148.6,
167.2.
Bis[(1R)-menthyl] 2,5-Dichloro-3,6-dihydroxyterephthalate
(4d)
To a soln of 3d (177.5 mg, 0.33 mmol) in THF (5 mL), a soln of
Na2S2O4 (90 mg, ca. 0.5 mmol) in H2O (2 mL) was added dropwise.
AcOH (2 drops) was added and the biphasic mixture was vigorously
stirred for 10 min. The mixture was diluted with t-BuOMe (15 mL)
and the organic phase was washed with aq NaCl (3 ×), dried
(Na2SO4), and evaporated. The residue was purified by chromatog-
raphy (silica gel, EtOAc–hexanes, 1:5). The collected product frac-
tions were crystallized (hexanes, –20 °C) to give 4d (173.9 mg,
98%) as a yellow solid; mp 130.2–130.6 °C (corr.). Note: Crystalli-
zation of 4d from EtOH at 0 °C gave colorless crystals of a solvate
[4d·2 EtOH].17
1H NMR: d = 0.81 (d, J = 6.9 Hz, 6 H), 0.91 (d, J = 7.0 Hz, 6 H),
0.86–1.00 (m, 2 H), 0.96 (d, J = 6.6 Hz, 6 H), 1.05–1.26 (m, 4 H),
1.50–1.62 (m, 4 H), 1.69–1.80 (m, 4 H), 2.01 (sept d, J = 7.0, 2.6
Hz, 2 H), 2.16–2.24 (m, 2 H), 5.07 (td, J = 10.9, 4.4 Hz, 2 H), 9.28
(s, 2 H).
13C NMR: d = 15.7, 20.4, 21.7, 22.9, 25.8, 31.3, 33.8, 40.3, 46.8,
77.9, 119.5, 119.8, 148.5, 167.0.
Acknowledgment
We thank the Japan Society for the Promotion of Science for a post-
doctoral fellowship to L.H.
(14) Sinnreich, J.; Batzer, H. Helv. Chim. Acta 1979, 62, 1682.
(15) (a) Taber, D. F.; Amedio, J. C.; Patel, Y. K. J. Org. Chem.
1985, 50, 3618. (b) Christoffers, J.; Önal, N. Eur. J. Org.
Chem. 2000, 1633.
References
(16) Grandmougin, E. J. Prakt. Chem. 1907, 76, 124.
(17) This pseudo-polymorphism is analogous to that described
for the bromo analogue of 4b, for which X-ray crystal
structures of both the solvent-free substance and a solvate
are reported: Näther, C.; Nagel, N.; Bock, H.; Seitz, W.;
Havlas, Z. Acta Crystallogr., Sect. B. 1996, 52, 697.
(1) Current address: L. Hintermann, Institute of Organic
Chemistry, RWTH, Aachen, Germany.
(2) (a) Modern Arene Chemistry; Astruc, D., Ed.; Wiley-VCH:
Weinheim, 2002. (b) Hintermann, L. Nachr. Chem. 2005,
53, 776.
Synthesis 2008, No. 14, 2303–2306 © Thieme Stuttgart · New York