Convergent Synthesis of Dumbbell type Dendritic Materials
Bull. Korean Chem. Soc. 2011, Vol. 32, No. 11 3939
13
C
+
Found: 2664.2074 [M + Na]. PDI: 1.01
6.56 (m, 22H), 6.63 (d, J = 1.4 Hz, 8H), 7.50 (s, 2H);
NMR (75 MHz, CDCl3) δ 54.0, 55.3, 64.6, 69.7, 70.1, 70.5,
99.9, 101.7, 102.0, 105.2, 106.4, 107.2, 122.6, 136.8, 138.9,
139.1, 146.4, 160.1, 160.3, 161.0; MS (MALDI): Calcd for
7-G4. Rf 0.4 (EtOAc); A yellowish oil; 96% yield; IR
−1
1
2936, 2878, 1597, 1458, 1346, 1204, 1153, 1053 cm ; H
NMR (300 MHz, CDCl3) δ 3.60-3.64 (m, 48H), 3.76 (s,
96H), 4.63 (s, 4H), 4.91 (s, 8H), 4.95 (s, 48H), 5.38 (s, 4H),
6.39 (m, 16H), 6.47 (m, 4H), 6.55-6.56 (m, 46H), 6.63 (d, J
+
C136H156N6O37: 2465.0510. Found: 2488.8962 [M + Na].
PDI: 1.01.
13
= 1.4 Hz, 8H), 6.66 (d, J = 1.6 Hz, 16H), 7.49 (s, 2H); C
6-G4. Rf 0.4 (EtOAc); A yellowish oil; 97% yield; IR
−1
1
2940, 2878, 1597, 1450, 1319, 1204, 1150, 1049 cm ; H
NMR (500 MHz, CDCl3) δ 3.59 (s, 24H), 3.61-3.65 (m, 8H),
3.76 (s, 96H), 4.63 (s, 4H), 4.90 (s, 8H), 4.95 (s, 48H), 5.38
(s, 4H), 6.39 (m, 16H), 6.47 (m, 4H), 6.52 (m, 2H), 6.56 (m,
44H), 6.63 (m, 8H), 6.66 (d, J = 1.3 Hz, 8H), 7.49 (s, 2H);
NMR (75 MHz, CDCl3) δ 53.8, 55.1, 64.4, 69.5, 69.8, 70.3,
99.7, 101.4, 101,7, 105.0, 106.2, 107.0, 122.6, 136.8, 138.7,
138.96, 139.02, 145.3, 159.9, 160.1, 160.8; MS (MALDI):
+
Calcd for C272H300N6O73: 4817.9947. Found: 4840.9252 [M
+ Na]. PDI: 1.02.
13
C NMR (75 MHz, CDCl3) δ 53.9, 55.2, 64.6, 69.7, 70.0,
70.37, 70.44, 99.9, 101.6, 101.9, 105.2, 106.4, 107.2, 122.6,
136.9, 138.8, 139.09, 139.14, 145.6, 160.0, 160.3, 160.9;
MS (MALDI): Calcd for C264H284N6O69: 4641.8899. Found:
Acknowledgments. This research was supported by a
grant (M2009010025) from the Fundamental R&D Program
for Core Technology of Materials funded by the Ministry of
Knowledge Economy (MKE), Republic of Korea and Basic
Science Research Program through the National Research
Foundation of Korea (NRF) funded by the Ministry of
Education, Science and Technology (2009-0071322) and by
the nuclear R&D Program of the Ministry of Education,
Science, & Technology of Korea.
+
4664.6483 [M + Na]. PDI: 1.01.
General Procedure for the Preparation of Dendrimers
7-Gm from Azide-Dendrons 1-Dm and Dodeca(ethylene-
glycol)-di(alkynes) 4. A mixture of azido-dendrons 1-Dm
(0.22 mmol) and dodeca(ethyleneglycol)-di(alkynes) 4 (0.1
mmol) in DMF-H2O (4:1, 2 mL) in the presence of 10
mol % CuSO4·5H2O with 20 mol % sodium ascorbate was
o
stirred at 50 C for ~2 h. The reaction mixture was poured
References and Notes
into brine (20 mL) and the resulting solution was extracted
with EtOAc (20 mL × 3). The combined organic phase was
dried with sodium sulfate, concentrated, and purified by
column chromatography to afford the desired product 7-Gm.
7-G1. Rf 0.15 (EtOAc:MeOH = 5:1); A yellowish oil;
98% yield; IR 2870, 1597, 1458, 1350, 1204, 1153, 1099,
1. (a) Grimsdale, A. C.; Müllen, K. Angew. Chem. Int. Ed. 2005, 44,
5592. (b) Tomalia, D. A. Prog. Polym. Sci. 2005, 30, 294.
2. (a) Newkome, G. R.; Moorefield, C. N.; F. Vögtle, Dendrimers
and Dendrons: Concepts, Synthesis, Applications; Wiley-VCH:
Weinheim, 2001. (b) Fréchet, J. M. J.; Tomalia, D. A. Dendrimers
and Other Dendritic Polymers; John Wiely & Sons Ltd., 2002.
3. Gitsov, I.; Lambrych, K. R.; Remnant, V. A.; Pracitto, R. J. Polym.
Sci. Part A, Polym. Chem. 2000, 38, 2711.
−1 1
1053 cm ; H NMR (500 MHz, CDCl3) δ 3.60 (s, 40H),
3.61-3.65 (m, 8H), 3.73 (s, 12H), 4.63 (s, 4H), 5.40 (s, 4H),
4. Namazi, H.; Adeli, M. J. Polym. Sci. Part A, Polym. Chem. 2005,
43, 28.
13
6.38-6.39 (m, 6H), 7.50 (s, 2H); C NMR (75 MHz, CDCl3)
δ 54.1, 55.3, 64.6, 69.6, 70.39, 70.45, 100.3, 106.0, 122.5,
5. Gitsov, I.; Wooley, K. L.; Fréchet, J. M. J. Angew. Chem. Int. Ed.
Engl. 1992, 31, 1200.
+
136.6, 145.5, 161.2; MS (FAB): m/z 1009.19 [M + H];
6. Gitsov, I.; Fréchet, J. M. J. Macromolecules 1993, 26, 6536.
7. van Hest, J. C. M.; Baars, M. W. P.; Elissen-Román, C.; van
Genderen, M. H. P.; Meijer, E. W. Macromolecules 1995, 28,
6689.
HRMS (FAB) Calcd for C48H76N6O17: 1008.5267. Found:
+
1009.5347 [M + H]. PDI: 1.01
7-G2. Rf 0.25 (EtOAc:MeOH = 5:1); A yellowish oil;
97% yield; IR 2870, 1597, 1458, 1350, 1204, 1153, 1103,
8. van Hest, J. C. M.; Delnoye, D. A. P.; Baars, M. W. P. L.; Elissen-
Román, C.; van Genderen, M. H. P.; Meijer, E. W. Chem. Eur. J.
1996, 2, 1616.
−1
1
1053 cm ; H NMR (500 MHz, CDCl3) δ 3.61 (s, 40H),
3.62-3.66 (m, 8H), 3.78 (s, 24H), 4.65 (s, 4H), 4.91 (s, 8H),
5.40 (s, 4H), 6.39 (m, 4H), 6.47 (m, 4H), 6.52 (m, 8H), 6.55
9. Chapman, T. M.; Hillyer, G. L.; Mahan, E. J.; Shaffer, K. A. J. Am.
Chem. Soc. 1994, 116, 11195.
13
(m, 2H), 7.49 (s, 2H); C NMR (75 MHz, CDCl3) δ 54.0,
10. Ge, Z.; Luo, S.; Liu, S. J. Polym. Sci. Part A, Polym. Chem. 2006,
44, 1357. and references therein.
55.3, 64.6, 69.7, 70.0, 70.4, 70.5, 99.9, 102.0, 105.1, 107.2,
122.5, 136.7, 138.7, 145.5, 160.3, 160.9; MS (FAB): m/z
11. Gitsov, I. J. Polym Sci. Part A: Polym. Chem. 2008, 46, 5295.
12. (a) Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B.
Angew. Chem. Int. Ed. 2002, 41, 2596. (b) Tornøe, C. W.;
Christensen, C.; Meldal, M. J. Org. Chem. 2002, 67, 3057.
13. (a) Wu, P.; Feldman, A. K.; Nugent, A. K.; Hawker, C. J.; Scheel,
A.; Voit, B.; Pyun, J.; Fréchet, J. M. J.; Sharpless, K. B.; Fokin, V.
V. Angew. Chem. Int. Ed. 2004, 43, 3928. (b) Malkoch, M.;
Schleicher, K.; Drockenmuller, E.; Hawker, C. J.; Russell, T. P.;
Wu, P.; Fokin, V. V. Macromolecules 2005, 38, 3663. (c)
Joralemon, M. J.; O’Reilly, R. K.; Matson, J. B.; Nugent, A. K.;
Hawker, C. J.; Wooley, K. L. Macromolecules 2005, 38, 5436.
14. (a) Lee, J. W.; Kim, B. K. Bull. Korean Chem. Soc. 2005, 26, 658.
(b) Lee, J. W.; Kim, B. K.; Jin, S. H. Bull. Korean Chem. Soc.
2005, 26, 833. (c) Lee, J. W.; Kim, B. K.; Kim, J. H.; Shin, W. S.;
Jin, S. H. Bull. Korean Chem. Soc. 2005, 26, 1790. (d) Lee, J. W.;
+
1554.3 [M + H]; HRMS (FAB) Calcd for C80H108N6O25:
+
1552.7364. Found: 1553.7435 [M + H]. PDI: 1.01
7-G3. Rf 0.3 (EtOAc:MeOH = 10:1); A yellowish oil;
95% yield; IR 2936, 2874, 1597, 1458, 1346, 1204, 1153,
−1
1
1103, 1053 cm ; H NMR (300 MHz, CDCl3) δ 3.62 (s,
40H), 3.62-3.65 (m, 8H), 3.78 (s, 48H), 4.65 (s, 4H), 4.92 (s,
8H), 4.97 (s, 16H), 5.41 (s, 4H), 6.40 (t, J = 2.0 Hz, 8H),
6.46 (d, J = 1.8 Hz, 4H), 6.56-5.67 (m, 22H), 6.63 (d, J = 1.9
13
Hz, 8H), 7.50 (s, 2H); C NMR (75 MHz, CDCl3) δ 54.0,
55.3, 64.6, 69.7, 70.0, 70.5, 99.9, 101.6, 101.9, 105.2, 106.3,
107.1, 122.6, 136.8, 138.8, 139.0, 145.5, 160.0, 160.2,
160.9; MS (MALDI): Calcd for C144H172N6O41: 2641.1559.