CATALYTIC PROPERTIES OF CYCLODEXTRIN DIMERS
519
À3
6
H), 3.83–3.53 (m, 30H), 3.45–3.30 (m, overlaps with
2 Â 10 M. Each run was initiated by adding 60 ml of a
13
HOD). C NMR: ꢀ 102.3, 83.6, 81.9, 73.2, 72.7, 72.3,
stock solution of ester in CH CN to 3 ml of 0.1 M
3
7
0.7, 60.6, 60.2, 51.8, 49.4. Fast atom bombardment mass
phosphate buffer (pH 8.04) containing a suitable amount
of CD derivative, pre-equilibrated at 35 Æ 0.1°C in the
thermostated cell holder of a Shimadzu 265 FW
spectrophotometer. The ester cleavage was followed by
monitoring the first-order appearance of the p-nitrophe-
nolate ion at 400 nm. In the presence of CDs, all of the
substrates gave saturation-type kinetics. The Eadie–
spectrometry (FAB-MS) (methanol): m/z 1179 (M 1) .
Anal. Calcd for C H NO
Á
35 2
4H O: C, 42.27; H, 6.69; N,
.12. Found: C, 41.97; H, 6.40; N, 1.31%.
44
75
1
General procedure for preparation of 3a and 3b. To a
solution of 2 (250 mg, 0.2 mmol) in DMF (4 ml) were
added anhydrous Na CO3 (106 mg, 1.0 mmol) and
1a
Hofstee approach was used to provide the constants kc
2
bis(bromomethyl)benzene (26.4 mg, 0.1 mmol). The
mixture was stirred at room temperature for 24 h. The
solid in the reaction solution was filtered off and the
filtrate was precipitated by addition of acetone (30 ml).
The precipitates were collected by suction and dried at
and K as given in Table 1.
M
Acknowledgement
8
0°C to give a white crude product. This crude product
Financial support from the National Natural Science
Foundation of China (Nos 29632004 and 29772023) is
gratefully acknowledged.
was dissolved in water (2 ml) and applied to a column
(
40 Â 3 cm i.d.) of CM-Sephadex C-25 resin (NH4
form). The column was eluted with 0.05 M ammonium
hydrogencarbonate to afford the product as white
crystals.
REFERENCES
Compound 3a: yield 99 mg (38%), m.p. 298.4°C
1
(
decomp.). H NMR: ꢀ 7.24 (s, 4H), 6.08–5.74 (m, 28H),
1
. (a) Bender ML, Komiyama M. Cyclodextrin Chemistry. Springer:
New York, 1978; (b) Saenger W. Angew. Chem., Int. Ed. Engl.
4
.82 (s, 14H), 4.49–4.35 (m, 14H), 3.62 (br s, 56H), 3.34
1
980; 19: 344; (c) Szejtli J. Cyclodextrins and Their Inclusion
(
br s, overlaps with HOD), 2.84–2.42 (m, overlaps with
13
Complexes. Akad e´ miai Kiad o´ : Budapest, 1982; (d) Szejtli J.
Cyclodextrin Technology. Kluwer: Dordrecht, 1988; (e) Wenz G.
Angew. Chem., Int. Ed. Engl. 1994; 33: 803.
. Van Etten RL, Glowes GA, Sebastian JF, Bender ML. J. Am.
Chem. Soc. 1967; 89: 3253.
DMSO). C NMR: ꢀ 138.1, 128.7, 102.3, 84.2, 81.7,
3.3, 72.7, 72.3, 71.2, 60.2, 59.2, 55.8, 55.5. FAB-MS
7
2
[
DMSO–glycerol–m-nitrobenzyl alcohol (1:1:1)]: m/z
2
4
1
458 (M ). Anal. Calcd for C H N O
Á
70 2
8H O: C,
96
156
2
3. (a) Komiyama M, Bender ML. Bioorg. Chem. 1977; 6: 323; (b)
Bender ML, Pollock EJ, Neveu MC. J. Am. Chem. Soc. 1962; 84:
4.31; H, 6.67; N, 1.08. Found: C, 44.15; H, 6.40; N,
.12%.
5
95.
. Breslow R, Greenspoon N, Guo T, Zarzycki R. J. Am. Chem. Soc.
989; 111: 8296.
4
Compound 3b: yield 91.7 mg (35%), m.p. 294.6°C
1
1
(
decomp.). H NMR: ꢀ 7.20 (s, 4H), 5.96–5.74 (m, 28H),
5. (a) Schoellmann G, Shaw E. Biochemistry.1963; 2: 252; (b)
Bender ML, Clement GE, Kezdy FJ. J. Am. Chem. Soc. 1964; 86:
4
.82 (s, 14H), 4.60–4.38 (m, 14H), 3.59 (br s, 56H), 3.37
3
680; (c) Cramer F, Macksen G. Angew. Chem. 1966; 78: 64; (d)
(
br s, overlaps with HOD), 2.81–2.40 (m, overlaps with
Cramer F, Macksen G. Chem. Ber. 1970; 103: 2138; (e) Breslow
R. Acc. Chem. Res. 1991; 24: 317; (f) Breslow R. Pure Appl.
Chem. 1994; 66: 1573; (g) Breslow R. Acc. Chem. Res. 1995; 28:
13
DMSO). C NMR: ꢀ 139.6, 129.8, 128.2, 102.4, 84.4,
1.8, 73.4, 72.8, 72.4, 71.3, 60.3, 59.3, 56.1, 55.5. FAB-
8
1
46; (h) Breslow R, Dong SD. Chem. Rev. 1998; 98: 1997; (i)
MS [DMSO–glycerol–m-nitrobenzyl alcohol (1:1:1)]:
m/z 2458 (M ). Anal. Calcd for C H N O
C, 44.00; H, 6.69; N, 1.07. Found: C, 44.29; H, 6.51; N,
1
Takahashi K. Chem. Rev. 1998; 98: 2013.
Á
9H O:
6. (a) Tabushi T, Kuroda Y, Shimokawa K. J. Am. Chem. Soc. 1979;
96
156
2
70
2
1
1
01: 1614; (b) Harada A, Furue M, Nozakura SI. Polym. J. 1980;
2: 29; (c) Fujita K, Ejima S, Imoto T. J. Chem. Soc., Chem.
.10%.
Commun. 1984; 1277; (d) Fujita K, Ejima S, Imoto T. Chem. Lett.
1985; 11; (e) Coates JH, Easton GJ, Van Eyk SJ, Lincoln SF, May
BL, Whalland CB, Williams ML. J. Chem. Soc., Perkin Trans. 1
Compound 3c was prepared by a procedure similar to
that for 3a except for using DMSO and K CO instead of
DMF and Na CO . Yield 108 mg (40%), m.p. 290.4°C
2
3
1
990; 2619; (f) Breslow R, Chung S. J. Am. Chem. Soc. 1990; 112:
2
3
9659; (g) Breslow R, Zhang B. J. Am. Chem. Soc. 1992; 114: 5882;
(h) Breslow R, Zhang B. J. Am. Chem. Soc. 1993; 115: 9353; (i)
Deschenaux R, Greppi A, Ruch T, Kriemler H-P, Raschdorf F,
Ziessel R. Tetrahedron Lett. 1994; 35: 2165; (j) Akiike T, Nagano
Y, Yamamoto Y, Nagamura A, Ikeda H, Ueno A, Toda F. Chem.
Lett. 1194; 1089; (k) Wang Y, Ueno A, Toda F. Chem. Lett. 1994;
1
(
5
decomp.). H NMR: ꢀ 7.52 (s, 1H), 7.39 (s, 2H), 6.12–
.77 (m, 28H), 4.82 (br s, 21H), 4.53 (br s, 7H), 3.63 (br s,
overlaps with HOD), 2.88–2.49 (m, overlaps with
13
DMSO). C NMR: ꢀ 159.3, 137.3, 121.1, 102.3, 84.1,
1.6, 73.2, 72.7, 72.3, 71.5, 60.1, 59.4, 56.8, 55.9. FAB-
1
67; (l) Venema F, Baselier CM, Van Dienst E, Ruel BMM,
8
Feiters MC, Engberson JFJ, Reinhoudt DN, Nolte RJM. Tetra-
hedron Lett. 1994; 35: 1773; (m) Jiang T, Sukumaran DK, Soni S-
D, Lawrence DS. J. Org. Chem. 1994; 59: 5149; (n) Okabe Y,
Yamamura H, Obe K, Ohta K, Kawai M, Fujita K. J. Chem. Soc.,
Chem. Commun. 1995; 581; (o) Breslow R, Dong SD. Chem. Rev.
MS [DMSO–glycerol–m-nitrobenzyl alcohol (1:1:1)]:
m/z 2459 (M ). Anal. Calcd for C H N O
Á
14H O:
70 2
95
155
3
C, 42.08; H, 6.80; N, 1.55. Found: C, 42.34; H, 6.66; N,
.31%.
1
1
998; 98: 1997, and references cited therein.
7
8
. Vallee BL, Williams RJP. Chem. Ber. 1968; 4: 397.
. (a) Blyth CA, Knowles JR. J. Am. Chem. Soc. 1971; 93: 3017; (b)
Blyth CA, Knowles JR. J. Am. Chem. Soc. 1971; 93: 3021; (c)
Hershfield R, Bender ML. J. Am. Chem. Soc. 1972; 94: 1376; (d)
Bonora GM, Fornasier R, Scrimin P, Tonellato V. J. Chem. Soc.,
Kinetic study. Rate measurements were made for
À5
solutions of the esters at a concentration of 1 Â 10
M
using 6–10 different CD concentrations from 2 Â 10À4 to
Copyright 2001 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 2001; 14: 515–520