The yields of monoesters at a particular yield of diesters were
derived from plots of product yield vs. time, such as that shown
in Fig. 1.
Tetradecanedioic acid dibutyl ester.14,23 1H NMR δ 0.93 (t,
6H), 1.26–1.45 (m, 20H), 1.55–1.63 (m, 8H), 2.26–2.31 (t, 4H),
4.04–4.09 (t, 4H).
Butyl esters of maleic acid and fumaric acid are mentioned in
many reports.27 A number of papers referred to dipropyl ester
and diethyl ester of hexanedioic acid.14,15,28
An example of monoesterification of symmetrical dicarboxylic
acids for preparative purposes
Hexanedioic acid (0.73 g, 5.0 mmol) and Dowex 50WX2 (50–
100 mesh) (5.0 g) were stirred at 70 1 ЊC in a mixture of butyl
formate (25 cm3) and octane (25 cm3) and the mixture was
monitored by GLC. After 3 h the catalyst was removed by fil-
tration and the solution was evaporated. The residue was
chromatographed with hexane–EtOAc (4:1) on a silica gel
column to give hexanedioic acid monobutyl ester13 (0.82 g,
85%) and hexanedioic acid dibutyl ester14–16 (0.05 g, 3%). The
Drying of ion-exchange resin
Dowex 50WX2 (50–100 mesh) (1 g) was kept over P2O5 (30 g) in
a desiccator. The weight of the resin decreased to 26% in 1 day
and 25% in 7 days. The resin dried for 7 days was used in the
transesterification.
Esterification catalysed by the dried resin and water
1
monoester: Rf = 0.29 in hexane–EtOAc (4:1); H NMR (270
A mixture of hexanedioic acid (0.146 g, 1 mmol), the dried
Dowex 50WX2 (50–100 mesh) (0.2 g), pentadecane (GC
internal standard, 20 µl), water, and butyl formate–octane
(1:1 (v/v), 10 cm3) was stirred at 70 1 ЊC. Samples of the
supernatant organic layer were then removed periodically and
analysed by GLC.
MHz, CDCl3) δ 0.93 (t, 3H), 0.91–0.96 (t, 3H), 1.31–1.45 (m,
2H), 1.56–1.74 (m, 6H), 2.30–2.42 (m, 4H), 4.05–4.10 (t, 2H).
1
The diester: Rf = 0.58 in 20% EtOAc–hexane; H NMR δ 0.93
(t, 6H), 1.30–1.45 (m, 4H), 1.55–1.74 (m, 8H), 2.25–2.36 (m,
4H), 4.08 (t, 4H).
Pentanedioic acid monobutyl ester.17,18 1H NMR δ 0.93 (t,
3H), 1.31–1.45 (m, 2H), 1.56–1.64 (m, 2H), 1.90–2.01 (m, 2H),
2.37–2.46 (m, 4H), 4.08 (t, 2H).
Distribution of dicarboxylic acid and monoester in aqueous layer
Hexanedioic acid (0.073 g), hexanedioic acid monobutyl
ester (0.107 g), pentadecane (0.01 cm2), water (0.4 cm3), and
HCO2Bu–octane (5 cm3) were stirred for 10 min at 70 ЊC. The
organic layer and the water layer were injected into the GLC.
When the percentages of HCO2Bu in the organic layer were 20,
40 and 60%, the percentages of the diacid in the water layer
were 94, 86 and 62%. The percentages of the monoester in the
water layer were less than 1% in all the conditions examined.
Pentanedioic acid dibutyl ester.19,20 1H NMR δ 0.93 (t, 6H),
1.31–1.45 (m, 4H), 1.58–1.66 (m, 4H), 1.89–2.00 (m, 2H), 2.37
(t, 4H), 4.08 (t, 4H).
Hexanedioic acid monopropyl ester.21 1H NMR δ 0.94 (t, 3H),
1.58–1.74 (m, 6H), 2.29–2.42 (m, 4H), 4.03 (t, 2H).
Hexanedioic acid monoethyl ester.22 1H NMR δ 1.26 (t, 3H),
1.62–1.76 (m, 4H), 2.29–2.42 (tt, 4H), 4.07 (t, 2H).
References
1 H. Ogawa, Y. Ichimura, T. Chihara, S. Teratani and K. Taya, Bull.
Chem. Soc. Jpn., 1986, 59, 2481; H. Ogawa, T. Chihara and K. Taya,
J. Am. Chem. Soc., 1985, 107, 1365; T. Chihara, J. Chem. Soc., Chem.
Commun., 1980, 1215; H. Ogawa, N. Hiraga, T. Chihara, S. Teratani
and K. Taya, Bull Chem. Soc. Jpn., 1988, 61, 2383.
2 K. Matoba and T. Yamazaki, Chem. Pharm. Bull., 1983, 31, 2955;
B. Rigo, D. Fasseur, P. Cauliez and D. Couturier, Tetrahedron
Lett., 1989, 30, 3073 and references cited therein; H. Junek, E.
Ziegler, U. Herzog and H. Kroboth, Synthesis, 1976, 332; J. Cossy,
D. Belotti, V. Bellosta and D. Brocca, Tetrahedron Lett., 1994, 35,
6089.
3 H. J. Gais, in Enzyme Catalysis in Organic Synthesis, ed. K. Drauz
and H. Waldmann, VCH, Weinheim, 1995, Section B, ch. 1, p. 178.
See also G. W. Breton, J. Org. Chem., 1997, 62, 8952; L.-M. Zhu and
M. C. Tedford, Tetrahedron, 1990, 48, 6587; A. M. Klibanov, Acc.
Chem. Res., 1990, 23, 114; E. Ozaki, T. Uragaki, K. Sakasita and
A. Sakima, Chem. Lett., 1995, 539 and references cited therein.
4 J. Zerda, G. Barak and Y. Sasson, Tetrahedron, 1989, 29, 1533.
5 M. Minami and S. Kai, Jpn. Kokai Tokkyo Koho, JP04,182,452
(1992) (Chem. Abstr., 1993, 118, 124071y).
6 T. Nishiguchi, K. Kawamine and T. Ohstuka, J. Org. Chem., 1992,
57, 312; H. Ogawa, M. Amano and T. Chihara, Chem. Commun.,
1998, 495; G. W. Breton, J. Org. Chem., 1997, 62, 8952; H. Ogawa,
M. Amano, T. Chihara, S. Teratani and K. Taya, J. Chem. Soc.,
Chem. Commun., 1986, 1337; J. H. Babler and M. J. Coghlan,
Tetrahedron Lett., 1979, 22, 1971; C. C. Leznoff, Acc. Chem. Res.,
1989, 11, 327; J. Otera, N. Dan-Oh and H. Nozaki, J. Chem. Soc.,
Chem. Commun., 1991, 1742; S. Murahashi, Y. Oda and T. Naota,
Chem. Lett., 1992, 2237; P. C. Zhu, J. Lin and C. U. Pittman, Jr.,
J. Org. Chem., 1995, 60, 5729; W. F. Balley, L. M. J. Zarcone and
A. D. Rivera, J. Org. Chem., 1994, 60, 2532; L.-M. Zhu and
M. C. Tedford, Tetrahedron, 1990, 48, 6587.
1
Octanedioic acid monobutyl ester. H NMR δ 0.923 (t, 3H),
1.33–1.41 (m, 6H), 1.57–1.67 (m, 6H), 2.28–2.37 (tt, 4H), 4.07
(t, 2H); 13C NMR (CDCl3) δ 13.7, 19.1, 24.5, 24.7, 28.7, 28.7,
30.7, 33.8, 34.3, 64.2, 173.9, 179.1; IR (film, cmϪ1) 2959, 2936,
2871, 2671, 1736 (C᎐O), 1709 (C᎐O), 1464, 1416, 1244, 1179,
᎐
᎐
1136, 1092, 1021, 942, 738.
Octanedioic acid dibutyl ester.14,15,19,23,24 1H NMR δ 0.93 (t,
6H), 1.31–1.42 (m, 8H), 1.55–1.65 (m, 8H), 2.28 (t, 4H), 4.06
(t, 4H).
Decanedioic acid mono butyl ester.25 1H NMR δ 0.93 (t, 3H),
1.31–1.45 (m, 10H), 1.56–1.65 (m, 6H), 2.23–2.37 (tt, 4H), 4.07
(t, 2H).
1
trans-Cyclohexane-1,2-dicarboxylic acid monobutyl ester. H
NMR δ 0.92 (t, 3H), 1.24–1.43 (m, 6H), 1.56–1.61 (m, 2H),
1.79–1.81 (m, 2H), 2.06–2.18 (m, 2H), 2.57–2.64 (m, 2H), 4.06–
4.10 (t, 2H); 13C NMR (400 MHz, CDCl3) δ 13.6, 19.0, 25.2,
25.2, 28.8, 28.9, 30.6, 44.5, 44.6, 64.4, 175.0, 180.9.
cis-Cyclohexane-1,2-dicarboxylic acid monobutyl ester.17 1H
NMR δ 0.92 (t, 3H), 1.34–1.49 (m, 6H), 1.56–1.63 (m, 2H),
1.77–1.80 (m, 2H), 2.00–2.05 (m, 2H), 2.84–2.85 (m, 2H), 4.07–
4.11 (t, 2H); 13C NMR δ 13.6, 19.1, 23.6, 23.8, 26.0, 26.4, 30.5,
30.9, 42.5, 64.4, 173.6, 179.3.
trans-Cyclohexane-1,4-dicarboxylic acid monobutyl ester.26
1H NMR δ 0.93 (t, 3H), 1.33–1.59 (m, 6H), 1.60–1.64 (m, 2H),
2.06–2.10 (m, 4H), 2.27–2.33 (m, 2H), 4.06 (t, 2H); 13C NMR
δ 13.7, 19.1, 27.8, 27.9, 30.7, 30.9, 42.1, 42.5, 64.3, 96.1, 175.5,
180.5.
7 T. Nishiguchi, S. Fujisaki, Y. Ishii, Y. Yano and A. Nishida, J. Org.
Chem., 1994, 59, 1191.
8 T. Nishiguchi, S. Fujisaki, M. Kuroda, K. Kajisaki and M. Saitoh,
J. Org. Chem., 1998, 63, 8183.
9 T. W. Greene and P. G. M. Wuts, Protecting Groups in Organic
Synthesis, 2nd edn., Wiley, New York, 1991; P. J. Kocienski,
Protecting Groups, Georg Thieme Verlag, Stuttgart, 1994.
10 J. Otera, Chem. Rev., 1993, 93, 1449.
11 M. Saitoh, S. Fujisaki, Y. Ishii and T. Nishiguchi, Tetrahedron Lett.,
1996, 37, 6733.
1
Tetradecanedioic acid monobutyl ester. H NMR δ 0.93 (t,
3H), 1.16–1.45 (m, 18H), 1.55–1.78 (m, 6H), 2.26–2.38 (tt, 4H),
4.07 (t, 2H).
3026
J. Chem. Soc., Perkin Trans. 1, 1999, 3023–3027