cm3) was stirred at 70 ЊC in a lightly stoppered flask for 4–8 h.
The resultant light yellow solution was cooled to room tem-
perature and diluted with ethanol (100 cm3). The resulting pre-
cipitate was collected by vacuum filtration, washed successively
with ethanol (100 cm3) and diethyl ether (50 cm3) and dried
under vacuum to give the crude product. This material was
dissolved in water (10 cm3) and loaded onto a column (4.5 × 4.5
cm) of Hϩ form BioRex 70, 100–200 mesh (Biorad). The col-
umn was washed with water (400 cm3) and β-CDX was eluted
with 1 mol dmϪ3 NH4OH. Fractions containing β-CDX were
combined and evaporated to dryness under vacuum. The resi-
due was dissolved in water and the solution evaporated under
reduced pressure to remove excess ammonia (this procedure
was repeated several times). The product was dried under vac-
uum over P2O5 to give β-CDX in yields of 25–60%. Specific
preparative descriptions and characterisation data of β-CD-
tren, previously prepared by other methods,10 and previously
unreported β-CDtacdo are provided below. Similarly detailed
preparative and characterisation data for the remaining
β-CDXs shown in Fig. 1 are provided as supplementary data.†
tacdoH2, tacdoH5); δH[D2O–HCl (1:1), pH ~8.5] 5.09 (s,
7H ϩ solvent, H1), 4.26 (t, J 9.0, 1H, H5A), 3.8–4.2 (m, 25H,
H3, H5, H6), 3.5–3.7 (m, 13H, H2, H4), 3.39 (t, J 9.0, 1H,
H4A), 2.5–3.2 (m, 14H, H6A, tacdoH1, tacdoH3, tacdoH4),
1.6–2.0 (m, 6H, tacdoH2, tacdoH5); δH[D2O–HCl (1:2), pH
~6.0] 5.07 (br s, 7H, H1), 4.25 (t, J 9.0, 1H, H5A), 3.8–4.1 (m,
25H, H3, H5, H6), 3.5–3.7 (m, 13H, H2, H4), 3.43 (t, J 9.0, 1H,
H4A), 2.7–3.3 (m, 14H, H6A, tacdoH1, tacdoH3, tacdoH4),
1.7–2.2 (m, 6H, tacdoH2, tacdoH5); δH(D2O–HCl, pH ~1)
5.0 (br s, 7H ϩ solvent, H1), 4.33 (br t, 1H, H5A), 3.7–4.0 (m,
25H, H3, H5, H6), 3.2–3.6 (m, 27H, H2, H4, H6A, tacdoH1,
tacdoH3, tacdoH4), 2.2 (br, 6H, tacdoH2, tacdoH5).
Acknowledgements
We are grateful for the award of an Australian Postgraduate
Award to S. D. K. and to the Australian Research Commission
for supporting this research and to Nihon Shokhuin Kako Co.
for a gift of β-cyclodextrin.
References
6A-{2-[Bis(2-aminoethyl)amino]ethylamino}-6A-deoxy-â-cyclo-
dextrin (â-CDtren)
1 W. Saenger, in Inclusion Compounds, eds. J. L. Atwood, J. E. D.
Davies and D. D. MacNicol, Academic Press, London, 1984, vol. II,
p. 231.
2 R. J. Clarke, J. H. Coates and S. F. Lincoln, Adv. Carbohydr. Chem.
Biochem., 1988, 46, 205.
A mixture of β-CDtos (2.048 g, 1.59 × 10Ϫ3 mol), tris(2-
aminoethyl)amine (0.74 g, 5.07 × 10Ϫ3 mol) and KI (0.024 g) in
NMP (5 cm3) was treated according to the general procedure to
give β-CDtren as a white powder (1.192 g, 59%). Rc 0.31;
Electrospray-MS m/z 1263 (Mϩ) [Found: C, 43.84; H, 7.58; N,
4.40. Calc. for β-CDtrenؒ3H2O (C48H92N4O34): C, 43.76; H, 7.04;
N, 4.25%]; δH(D2O–NaOH, pH ~14) 5.00 (br s, 7H ϩ solvent,
H1), 3.5–3.8 (m, 26H, H3, H5, H6), 3.1–3.4 (m, 13H, H2, H4),
3.02 (t, J 9.0, 1H, H4A), 2.85 (d, J 12.0, 1H, H6A), 2.2–2.7 (m,
13H, H6AЈ, trenH); δH(D2O, pH ~9) 5.05 (br s, 7H, H1), 3.8–4.0
(m, 26H, H3, H5, H6), 3.5–3.7 (m, 13H, H2, H4), 3.41 (t, J 9.0,
1H, H4A), 3.05 (d, J 11.4, 1H, H6A), 2.4–2.9 (m, 13H, H6AЈ,
trenH); δH(D2O–HCl, pH ~1) 5.00 (s, 7H, H1), 4.10 (t, J 9.0,
1H, H5A), 3.6–4.0 (m, 25H, H3, H5, H6), 3.4–3.6 (m, 14H, H2,
H4), 2.9–3.4 (m, 14H, H6A, trenH); δC(D2O–NaOH, pH ~14),
107.0, 106.6, 106.4, 105.2 (C1), 87.6 (C4A), 85.0, 84.8, 84.5, 83.9
(C4), 77.3, 76.4, 76.3, 75.2, 74.9 (C2, C3, C5), 70.9 (C5A), 63.0
(C6), 59.8 (trenC3,3Ј), (56.9), 55.1 (C6A), 50.5 (trenC2), 46.2
(trenC1), 41.0 (trenC4,4Ј); δC(D2O, pH ~9) 104.7, 104.3 (C1),
86.4 (C4A), 84.0, 83.6 (C4), 75.9 (C2), 74.9 (C3), 74.7 (C5), 73.3
(C5A), 63.1 (C6), 58.7 (trenC3,3Ј), 55.7 (trenC2), 52.0 (C6A), 48.7
(trenC1), 40.7 (trenC4,4Ј); δC(D2O–HCl, pH ~1) 104.5, 103.8
(C1), 85.8 (C4A), 84.2, 83.8, 83.4 (C4), 75.8, 75.5, 75.0, 74.8,
74.5 (C2, C3, C5), 70.2 (C5A), 63.6, 63.1 (C6), 52.8 (trenC3,3Ј),
51.5 (C6A), 51.3 (trenC2), 47.0 (trenC1), 38.6 (trenC4,4Ј).
3 C. J. Easton and S. F. Lincoln, Chem. Soc. Rev., 1996, 25, 163.
4 S. E. Brown, J. H. Coates, P. A. Duckworth, S. F. Lincoln, C. J.
Easton and B. L. May, J. Chem. Soc., Faraday Trans., 1993, 89, 1035.
5 R. Breslow, Pure Appl. Chem., 1994, 66, 1573.
6 R. Breslow, Acc. Chem. Res., 1995, 28, 146.
7 S. E. Brown, J. H. Coates, C. J. Easton, S. J. van Eyk, S. F. Lincoln,
B. L. May, M. A. Style, C. B. Whalland and M. L. Williams, J.
Chem. Soc., Chem. Commun., 1994, 47.
8 S. E. Brown, J. H. Coates, C. J. Easton and S. F. Lincoln, J. Chem.
Soc., Faraday Trans., 1994, 90, 739.
9 S. E. Brown, C. A. Haskard, C. J. Easton and S. F. Lincoln, J. Chem.
Soc., Faraday Trans., 1995, 91, 1013.
10 C. A. Haskard, C. J. Easton, B. L. May and S. F. Lincoln, Inorg.
Chem., 1996, 35, 1059.
11 Y. Matsui, T. Yokoi and K. Moshida, Chem. Lett., 1976, 1037.
12 I. Tabushi, N. Shimizu, T. Sugimoto, M. Shiozuka and K.
Yamamura, J. Am. Chem. Soc., 1977, 99, 7100.
13 E. U. Akkaya and A. W. Czarnik, J. Am. Chem. Soc., 1988, 110, 8553.
14 M. Komiyama and Y. Matsumoto, Chem. Lett., 1989, 719.
15 M. I. Rosenthal and A. W. Czarnik, J. Inclusion Phenom. Mol.
Recognit. Chem., 1991, 10, 119.
16 E. U. Akkaya and A. W. Czarnik, J. Phys. Org. Chem., 1992, 5, 540.
17 H.-J. Schneider and F. Xiao, J. Chem. Soc., Perkin Trans. 2, 1992, 387.
18 R. P. Bonomo, V. Cucinotta, F. D’Alessandro, G. Impellizzeri,
G. Maccarrone, E. Rizzarelli and G. Vecchio, J. Inclusion Phenom.
Mol. Recognit. Chem., 1993, 15, 167.
19 V. Cucinotta, F. D’Alessandro, G. Impellizzeri, G. Maccarrone,
E. Rizzarelli and G. Vecchio, J. Chem. Soc., Perkin Trans. 2, 1996,
1785.
20 Y. Matsui and A. Okimoto, Bull. Chem. Soc. Jpn., 1978, 51, 3030.
21 D. D. Perrin and W. L. F. Armarego, Purification of Laboratory
Chemicals, Pergamon, London, 3rd edn., 1988.
22 G. H. Searle and R. J. Geue, Aust. J. Chem., 1984, 37, 659.
23 M. Briellmann, S. Kaderli, C. J. Meyer and A. D. Zuberbühler, Helv.
Chim. Acta, 1987, 70, 680.
24 P. Gans, A. Sabatini and A. Vacca, J. Chem. Soc., Dalton Trans.,
1985, 1195.
25 H. B. Henbest and W. R. Jackson, J. Chem. Soc., 1962, 954.
26 J. A. Riddock and W. B. Burge, Techniques of Chemistry, Wiley, New
York, 1970, vol. 11.
27 F. Guillo, B. Hamelin, L. Jullien, J. Canceill, J.-M. Lehn, L. De
Robertis and H. Driguez, Bull. Soc. Chim. Fr., 1995, 132, 857.
28 R. M. Smith and A. E. Martell, Critical Stability Constants,
Plenum, New York, 1975, vol. 2.
29 L. J. Zompa, Inorg. Chem., 1978, 17, 2531.
30 R. D. Hancock, M. S. Shaikjee, S. M. Dobson and J. C. A. Boeyens,
Inorg. Chim. Acta, 1988, 154, 229.
6A-(1,5,9-Triazacyclododecan-1-yl)-6A-deoxy-â-cyclodextrin (â-
CDtacdo)
A mixture of 1,5,9-triazacyclododecaneؒ3HCl23 (1.451 g,
5.18 × 10Ϫ3 mol) and sodium hydroxide (0.625 g, 15.62 × 10Ϫ3
mol) in ethanol (30 cm3) was stirred at room temp. for 90 min.
The mixture was filtered and the collected solid was washed
with ethanol (10 cm3). The combined filtrates were evaporated
under reduced pressure to give the free amine as a yellow oil.
This was dissolved in NMP (5 cm3) and β-CDtos (2.081 g,
1.61 × 10Ϫ3 mol) and KI (0.030 g) were added to the solution.
The resultant mixture was treated according to the general pro-
cedure to give β-CDtacdo as a white powder (0.709 g, 34%). Rc
0.75; Electrospray-MS m/z 1288 (Mϩ) [Found: C, 45.28; H,
7.34; N, 3.15. Calc. for β-CDtacdoؒ4H2O (C51H97N3O38): C,
45.03; H, 7.18; N, 3.08%]; δH(D2O–NaOH, pH ~14) 4.9 (br s,
7H ϩ solvent, H1), 4.14 (t, J 6.0, 1H, H5A), 3.7–4.0 (m, 25H,
H3, H5, H6), 3.17 (t, J 6.0, 1H, H4A), 2.88 (d, J 15, 1H, H6A),
2.64 (m, 13H, H6AЈ, tacdoH1, tacdoH3, tacdoH4), 1.66 (m, 6H,
Paper 7/04467D
Received 25th June 1997
Accepted 26th June 1997
† Available as supplementary material (SUP 57281; 9 pp.) deposited
with the British Library. Details are available from the editorial office.
3160
J. Chem. Soc., Perkin Trans. 1, 1997