Release of Tertiary Alcohols from Dendrimers and Stylomers
FULL PAPER
(m), 772 (s), 699 (s), 673 cmꢀ1 (m); MS (CI): m/z (%): 319 (13), 318 (68)
[M+NH4]+, 185 (3), 184 (10), 183 (100), 169 (3), 168 (31), 167 (6), 166
(54), 93 (5).
tacos-1-anoyl}benzoate (4b): Compound 4b was prepared as described
above with 40 (3.10 g, 10.41 mmol) and triethylamine (2.10 g,
20.80 mmol) in CH2Cl2 (80 mL) and 4a (0.80 g, 1.24 mmol) in CH2Cl2
(20 mL) at ꢀ788C followed by MPLC of 1.00 g of the crude compound
to give a translucent paste (0.51 g, 56%). 1H NMR (400 MHz, CDCl3):
d=7.67–7.59 (m, 7H), 7.44–7.33 (m, 14H), 7.33–7.27 (m, 7H), 7.27–7.19
(m, 21H), 7.18–7.13 (m, 14H), 3.46–3.26 (brm, 20H), 3.26–3.13 (brm,
18H), 3.13–3.04 (m, 20H), 2.39–2.21 (brm, 8H), 2.06–1.93 (m, 8H), 1.93–
1.78 (m, 6H), 1.47 ppm (s, 42H); 13C NMR (100.6 MHz, CDCl3): d=
170.67 (s), 171.50 (s), 166.24 (s), 166.17 (s), 136.83 (s), 136.68 (s), 131.67
(d), 130.99 (s), 130.62 (d), 129.93 (d), 129.84 (d), 128.09 (d), 127.56 (d),
126.69 (d), 84.16 (s), 50.92 (t), 49.55 (t), 46.60 (t), 36.63 (t), 25.78 (q),
23.85 (t), 18.42 (t), 18.26 ppm (t); IR (neat): n˜ =3284 (w, br), 3064 (w),
3030 (w), 2983 (w), 2938 (w), 1775 (w), 1705 (s), 1663 (s), 1597 (w), 1579
(w), 1540 (m, br), 1491 (w), 1470 (w), 1454 (w), 1444 (w), 1385 (w), 1369
(w), 1290 (s), 1258 (w), 1197 (s), 1164 (s), 1134 (s), 1115 (s), 1085 (m),
1044 (w), 1031 (w), 974 (w), 917 (w), 891 (w), 846 (m), 832 (w), 797 (m),
777 (m), 730 (m), 719 (m), 701 (s), 649 (w), 611 cmꢀ1 (w); MS (MM): m/z
(%): 2630 (20), 2629 (24), 2610 (19), 2609 (43), 2608 (77), 2607 (86)
[M+H]+, 2606 (40), 1315 (18), 1305 (57), 1304 (100), 1303 (53), 870 (31),
869 (36), 826 (19), 825 (22); HRMS: m/z calcd for C159H193N12O21
[M+H]+: 2606.4355; found: 2606.4499.
General procedure for the synthesis of 2-carbamoylbenzoates 2b–6b,
9b–11b, 38b and 41b: A solution of 40 and triethylamine in CH2Cl2 was
added dropwise to a cold solution (ꢀ78 or 08C) of the multiamine (2a–
6a, 9a–11a, 38a or propane-1,3-diamine) in CH2Cl2 while keeping the
temperature below 58C. The formation of the product can be monitored
by using HPLC on a Macherey–Nagel Nucleosil 100-7 C2 column (250ꢃ
4 mm i.d.) eluted at 1 mLminꢀ1 with a gradient of water/acetonitrile from
50:50 to 5:95, over 20 min (containing 0.1% of TFA). After stirring at
room temperature for 1–3 h, the reaction mixture was treated with an
aqueous solution of KHSO4 (5%, 40–100 mL). The aqueous phase was
extracted with CH2Cl2 (30–40 mL) and the organic phases were dried
(Na2SO4) and filtered. After addition of some crystals of KHSO4, the sol-
vent was evaporated under reduced pressure and the product was dried
under high vacuum (0.5 mbar). MPLC of the crude compound (RP-C4,
water/acetonitrile 7:3, both containing 0.1% of TFA) and addition of
some crystals of KHSO4 to the product fraction, concentration and
drying under high vacuum (0.2 mbar, 2 h) gave the target compound.
Tris(1,1-dimethyl-2-phenylethyl)-2,2’,2’’-[nitrilotris(3,1-propanediylimino-
carbonyl)]tribenzoate (2b): Compound 2b was prepared as described
above with 2a (0.50 g, 2.66 mmol) in CH2Cl2 (10 mL) and 40 (2.88 g,
9.59 mmol) and triethylamine (1.94 g, 19.16 mmol) in CH2Cl2 (50 mL) at
1,1-Dimethyl-2-phenylethyl 2-{6,10,14,18,22,26,30-heptakis[3-({2-[(1,1-di-
methyl-2-phenylethoxy)carbonyl]benzoyl}amino)propyl]-35-{2-[(1,1-di-
methyl-2-phenylethoxy)carbonyl]phenyl}-35-oxo-2,6,10,14,18,22,26,30,34-
nonaazapentatriacont-1-anoyl}benzoate (5b): Compound 5b was pre-
pared as described above with 40 (1.86 g, 6.18 mmol) and triethylamine
(1.25 g, 12.36 mmol) in CH2Cl2 (10 mL) and 5a (0.50 g, 0.57 mmol) in
CH2Cl2 (50 mL) at room temperature followed by MPLC of 1.00 g of the
crude compound (water/acetonitrile 1:1, both containing 0.1% of TFA)
to give a translucent paste (0.10 g, 11%) containing small amounts of im-
purities. 1H NMR (400 MHz, CDCl3): d=7.58–7.52 (m, 9H), 7.37–7.27
(m, 27H), 7.25–7.16 (m, 27H), 7.16–7.10 (m, 18H), 3.39–3.09 (m, 60H),
3.05 (s, 18H), 2.36–2.18 (brm, 12H), 2.02–1.80 (brm, 18H), 1.44 ppm (s,
54H); 13C NMR (100.6 MHz, CDCl3): d=170.71 (s), 170.67 (s), 170.65
(s), 166.65 (s), 166.62 (s), 166.52 (s), 136.98 (s), 136.93 (s), 136.90 (s),
131.43 (s), 131.37 (d), 131.34 (d), 130.64 (d), 129.70 (d), 129.52 (d), 128.05
(d), 128.02 (d), 127.55 (d), 126.61 (d), 84.61 (s), 84.09 (s), 84.04 (s), 84.00
(s), 51.27 (t), 50.93 (t), 50.77 (t), 49.67 (t), 49.41 (t), 46.57 (t), 46.52 (t),
36.64 (t), 25.72 (q), 25.70 (q), 25.68 (q), 25.61 (q), 23.63 (t), 18.60 (t),
18.48 ppm (t); IR (neat): n˜ =3287 (w, br), 3063 (w), 3029 (w), 2982 (w),
2938 (w), 2624 (w), 1979 (w), 1773 (w), 1706 (s), 1663 (s), 1597 (w), 1579
(w), 1535 (m, br), 1470 (w), 1454 (w), 1444 (w), 1385 (w), 1369 (w), 1290
(s), 1258 (w), 1196 (s), 1175 (s), 1115 (s), 1085 (m), 1045 (w), 1031 (w),
974 (w), 915 (w), 891 (w), 846 (m), 830 (m), 797 (w), 773 (w), 731 (m),
719 (m), 701 (s), 648 (w), 612 cmꢀ1 (w); MS (ESI): m/z (%): 1747 (15),
1698 (18) [M+2H]2+, 1672 (3), 1670 (3), 1623 (3), 1198 (7), 1172 (3),
1165 (46), 1146 (5), 1140 (4), 1132 (48), 1121 (4), 1115 (8), 1113 (11),
1088 (6), 1082 (7), 1071 (4), 1039 (3), 874 (16), 849 (100), 841 (7), 835
(15), 816 (31), 812 (15), 808 (3), 804 (3), 802 (5), 783 (13), 779 (8), 774
(3), 750 (5), 746 (3), 321 (3), 282 (3), 155 (3), 133 (7); HRMS: m/z calcd
for C207H254N16O27 [M+2H]2+: 1697.9466; found: 1698.4383.
1
08C to give a white solid (2.29 g, 84%). H NMR (400 MHz, CDCl3): d=
7.63–7.58 (m, 3H), 7.38–7.29 (m, 9H), 7.27–7.12 (m, 15H), 3.49–3.32
(brm, 12H), 3.09 (s, 6H), 2.14–2.04 (brs, 6H), 1.48 ppm (s, 18H);
13C NMR (100.6 MHz, CDCl3): d=170.84 (s), 166.19 (s), 137.11 (s),
136.89 (s), 131.49 (d), 131.17 (s), 130.63 (d), 129.74 (d), 129.67 (d), 128.06
(d), 127.50 (d), 126.62 (d), 83.84 (s), 50.45 (t), 46.53 (t), 36.75 (t), 25.84
(q), 25.57 (q), 23.75 ppm (t); IR (neat): n˜ =3299 (w, br), 3059 (w), 3027
(w), 2977 (w), 2939 (w), 2863 (w), 2650 (w), 2377 (w), 2366 (w), 2346 (w),
2277 (w), 2162 (w), 2051 (w), 1980 (w), 1708 (s), 1660 (m, br), 1527 (w),
1580 (w), 1535 (m, br), 1496 (w), 1480 (w), 1469 (w), 1454 (w), 1385 (w),
1369 (w), 1289 (s), 1258 (w), 1200 (m), 1175 (m), 1115 (s), 1085 (m), 1031
(w), 972 (w), 917 (w), 891 (w), 847 (m), 827 (w), 797 (w), 772 (w), 730
(s), 701 (s), 649 (w), 611 cmꢀ1 (w); MS (ESI): m/z (%): 1054 (7), 1053
(26), 1052 (72), 1051 (100) [M+Na]+, 1031 (8), 1030 (24), 1029 (33)
[M+H]+, 920 (5), 919 (9); HRMS: m/z calcd for C63H73N4O9 [M+H]+:
1029.5359; found: 1029.5243.
1,1-Dimethyl-2-phenylethyl 2-{6,10,14-tris[3-({2-[(1,1-dimethyl-2-phenyl-
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
benzoate (3b): Compound 3b was prepared as described above with 40
(2.16 g, 7.2 mmol) and triethylamine (1.45 g, 14.4 mmol) in CH2Cl2
(10 mL) and 3a (0.50 g, 1.20 mmol) in CH2Cl2 (40 mL) at room tempera-
ture to give a transparent paste (0.26 g, 12%). 1H NMR (400 MHz,
CDCl3): d=7.64–7.58 (m, 5H), 7.43–7.35 (m, 10H), 7.35–7.29 (m, 5H),
7.28–7.19 (m, 15H), 7.19–7.12 (m, 10H), 3.41–3.32 (m, 10H), 3.32–3.23
(m, 10H), 3.20–3.11 (m, 8H), 3.08 (s, 10H), 2.40–2.22 (m, 4H), 2.05–1.92
(m, 8H), 1.88–1.79 (m, 2H), 1.48 ppm (s, 30H); 13C NMR (100.6 MHz,
CDCl3): d=171.25 (s), 166.33 (s), 136.86 (s), 136.84 (s), 131.61 (d), 131.10
(s), 130.63 (d), 129.85 (d), 129.74 (d), 128.08 (d), 127.53 (d), 126.66 (d),
83.13 (s), 50.85 (t), 49.45 (t), 49.24 (t), 46.54 (t), 36.66 (t), 25.77 (q), 23.71
(q), 23.49 (t), 18.50 ppm (t); IR (neat): n˜ =3311 (w, br), 3063 (w), 3027
(w), 2983 (w), 2936 (w), 2863 (w), 2650 (w), 2345 (w), 2295 (w), 2254 (w),
2163 (w), 2050 (w), 1980 (w), 1778 (s), 1706 (m), 1647 (m, br), 1597 (w),
1580 (w), 1547 (m, br), 1496 (w), 1480 (w), 1469 (w), 1454 (w), 1442 (w),
1386 (w), 1371 (w), 1303 (m), 1288 (m), 1258 (w), 1201 (m), 1158 (s),
1141 (s), 1117 (s), 1086 (m), 1031 (w), 972 (w), 918 (w), 890 (w), 846 (m),
798 (w), 780 (w), 730 (m), 702 (s), 649 (w), 609 cmꢀ1 (w); MS (ESI): m/z
(%): 1818 (7) [M+H]+, 1017 (3), 929 (4), 920 (9), 919 (85), 910 (38), 909
(100), 908 (21), 843 (7), 777 (9), 711 (5), 645 (8), 579 (6), 386 (19), 133
(6); HRMS: m/z calcd for C111H133N8O15 [M+H]+: 1817.9857; found:
1817.9747.
1,1-Dimethyl-2-phenylethyl
2-{6,10,14,18,22,26,30,34,38-nonakis[3-({2-
[(1,1-dimethyl-2-phenylethoxy)carbonyl]benzoyl}amino)propyl]-43-{2-
[(1,1-dimethyl-2-phenylethoxy)carbonyl]phenyl}-43-oxo-
2,6,10,14,18,22,26,30,34,38,42-undecaazatriteracont-1-anoyl}benzoate
(6b): Compound 6b was prepared as described above with 40 (1.44 g,
4.79 mmol) and triethylamine (1.16 g, 11.5 mmol) in CH2Cl2 (10 mL) and
6a (0.50 g, 0.57 mmol) in CH2Cl2 (50 mL) at ꢀ208C followed by MPLC
of 0.90 g of the crude product to give a translucent paste (0.35 g, 23%).
1H NMR (400 MHz, CDCl3): d=7.62–7.52 (m, 11H), 7.41–7.28 (m, 33H),
7.25–7.18 (m, 33H), 7.18–7.11 (m, 22H), 3.42–2.98 (m, 76H), 3.08 (s,
22H), 2.36–2.18 (brm, 16H), 2.01–1.77 (brm, 22H), 1.51 (s, 4H),
1.47 ppm (s, 62H); 13C NMR (100.6 MHz, CDCl3): d=170.48 (s), 170.38
(s), 170.65 (s), 166.68 (s), 166.55 (s), 137.26 (s), 137.19 (s), 136.94 (s),
131.53 (s), 131.41 (d), 130.65 (d), 129.67 (d), 129.47 (d), 128.09 (d), 127.55
(d), 126.65 (d), 83.99 (s), 83.96 (s), 50.63 (t), 49.33 (t), 46.56 (t), 46.49 (t),
36.51 (t), 25.78 (q), 23.63 (t), 18.23 ppm (t); IR (neat): n˜ =3288 (w, br),
3063 (w), 3030 (w), 2984 (w), 2938 (w), 2652 (w, br), 1980 (w), 1774 (w),
1,1-Dimethyl-2-phenylethyl 2-{6,10,14,18,22-pentakis[3-({2-[(1,1-dimeth-
yl-2-phenylethoxy)carbonyl]benzoyl}amino)propyl]-27-{2-[(1,1-dimethyl-
2-phenylethoxy)carbonyl]phenyl}-27-oxo-2,6,10,14,18,22,26-heptaazahep-
Chem. Eur. J. 2009, 15, 2846 – 2860
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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