H. Heaney et al.
FULL PAPER
(FAB): m/z = 1405 [M]+. Second eluting diastereomer (P,S,S)-13aЈ:
3.43 (m, 8 H), 3.70 (q, J = 6.8 Hz, 4 H), 3.88 (2×br. d, 8 H), 4.43
(t, J = 7.2 Hz, 4 H), 4.53 (d, J = 10.0 Hz, 4 H), 4.90 (d, J = 10.0 Hz,
Pale yellow foam (2.70 g, 32%). [α]2D5 = +7.0 (c = 0.70, CHCl3). 1H
NMR (400 MHz, CDCl3): δ = 0.87 (br. t, 12 H), 1.30 (m, 24 H), 4 H), 6.77 (s, 4 H), 7.12–7.27 (m, 20 H) ppm. 13C NMR (100 MHz,
1.38 (d, J = 6.4 Hz, 12 H), 1.75–1.80 (m, 4 H), 1.90–1.95 (m, 4 H), CDCl3, 50 °C): δ = 14.2, 14.4, 19.5, 21.4, 23.0, 28.1, 32.5, 32.7,
3.33 (s, 12 H), 3.70 (q, J = 6.4 Hz, 4 H), 3.88 (d, J = 16.8 Hz, 4
H), 3.97 (d, J = 17.2 Hz, 4 H), 4.44 (t, J = 7.6 Hz, 4 H), 4.55 (d, J
36.1, 36.4, 46.1, 58.1, 72.6, 79.6, 113.0, 125.1, 127.3, 127.9, 128.1,
128.6, 128.9, 144.8, 150.6, 153.6 ppm. LRMS (FAB): m/z = 1573
= 10.0 Hz, 4 H), 4.98 (d, J = 10.0 Hz, 4 H), 6.80 (s, 4 H), 7.18– [M]+. C104H140N4O8 (1574.25): calcd. C 79.35, H 8.96, N 3.56;
7.30 (m, 20 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.2, 21.4, found C 79.45, H 9.02, N 3.53.
22.7, 27.8, 32.2, 35.4, 36.1, 45.3, 57.4, 60.2, 79.2, 112.2, 124.5,
Representative Procedure for the Reaction of Bis(aminol) Ethers with
Tetraalkoxyresorcinarenes Under Microwave-Assisted Conditions
127.1, 127.4, 127.9, 128.4, 128.5, 144.4, 150.3, 154.0 ppm. LRMS
(FAB): m/z = 1405 [M]+.
Tetrabenzoxazine 11a: Tetramethoxyresorcinarene 9a (0.50 g,
Tetrabenzoxazines (M,S,R)-13b/(P,S,S)-13bЈ: Prepared according to
0.6 mmol) was suspended in N,N-bis(methoxymethyl)-N-benzyla-
the representative procedure from tetrapentyl-tetraisopropyloxyre-
mine (0.93 g, 4.8 mmol) in a CEM microwave tube. The suspension
sorcinarene 9c (2.0 g, 2.1 mmol). The residue was placed on a col-
was heated under microwave irradiation at 150 °C for 10 min (with-
umn of silica gel and eluted with ethyl acetate/hexane (1:4) to afford
out cooling). The obtained orange oil was placed on a column of
silica gel and eluted with light petroleum/ethyl acetate (5:1) to af-
(M,S,R)-13b/(P,S,S)-13bЈ. First eluting diastereomer (M,S,R)-13b:
Yellow foam (1.20 g, 35%). [α]2D5 –116.0 (c = 0.32, CHCl3). IR
ford 11a (0.66 g, 82%).
(CH Cl ): ν = 3054, 2986, 2305, 1421, 1265, 896, 749, 705 cm–1. 1H
˜
2
2
Tetrabenzoxazines (M,S,R)-13a and (P,S,S)-13aЈ: Prepared accord-
ing to the representative procedure from tetrapentyl-tetrameth-
oxyresorcinarene 9a (0.46 g, 0.6 mmol) and N,N-bis(methoxyme-
thyl)-N-[(S)-(–)-(α-methylbenzyl)]amine (0.83 g, 4.5 mmol). The
suspension was heated under microwave irradiation at 150 °C for
10 min (without cooling). The obtained orange oil was placed on
a column of silica gel and eluted with light petroleum/ethyl acetate
(5:1) to afford (M,S,R)-13a (0.29 g, 38%) and (P,S,S)-13aЈ (0.27 g,
36%) as pale yellow foams.
NMR (400 MHz, CDCl3, 50 °C): δ = 0.77 (d, J = 4.0 Hz, 12 H),
0.85 (t, J = 6.2 Hz, 12 H), 0.98–1.10 (m, 12 H), 1.15–1.34 (m, 24
H), 1.39 (d, J = 6.4 Hz, 12 H), 1.69–1.77 (m, 4 H), 1.93–2.03 (m,
4 H), 3.83 (q, J = 6.4 Hz, 4 H), 3.86 (d, J = 16.8 Hz, 4 H), 4.14 (d,
J = 16.8 Hz, 4 H), 4.12 (m, 4 H), 4.31 (t, J = 7.2 Hz, 4 H), 4.53
(d, J = 9.8 Hz, 4 H), 4.59 (d, J = 9.8 Hz, 4 H), 6.82 (s, 4 H), 7.22–
7.34 (m, 20 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.2, 21.6,
21.9, 22.6, 22.7, 28.1, 32.1, 36.0, 36.7, 45.5, 57.0, 73.7, 79.5, 113.0,
125.3, 127.2, 127.5, 128.4, 129.1, 144.2, 149.8, 151.84 ppm. LRMS
(FAB): m/z = 1518 [M]+. Second eluting diastereomer (P,S,S)-13bЈ:
Yellow foam (1.10 g, 32%).[α]2D5 = +3.0 (c = 0.36, CHCl3). IR
Tetrabenzoxazines (M,S,R)-13b: and (P,S,S)-13bЈ: Prepared accord-
ing to the representative procedure from tetrapentyl-tetraisopro-
pyloxyresorcinarene 9c (0.10 g, 0.1 mmol). The suspension was
heated under microwave irradiation at 140 °C for 3×10 min. The
obtained orange oil was placed on a column of silica gel and eluted
with hexane/ethyl acetate (6:1) to afford (M,S,R)-13b (0.063 g,
39%) and (P,S,S)-13bЈ (0.064 g, 39%) as pale yellow foams.
(CH Cl ): ν = 2968, 2926, 2857, 1461, 1110, 942, 700 cm–1. 1H
˜
2
2
NMR (400 MHz, CDCl3, 50 °C): δ = 0.82–0.94 (m, 24 H), 1.03 (d,
J = 5.2 Hz, 12 H), 1.18–1.32 (m, 24 H), 1.41 (d, J = 6.4 Hz, 12 H),
1.67–1.76 (m, 4 H), 1.92–2.04 (m, 4 H), 3.72–3.92 (m, 12 H), 4.10
(m, 4 H), 4.34, (t, J = 7.2 Hz, 4 H), 4.52 (d, J = 10.0 Hz, 4 H),
4.93 (d, J = 10.0 Hz, 4 H), 6.86 (s, 4 H), 7.18–7.34 (m, 20 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 14.2, 21.2, 22.3, 22.6, 22.7, 27.9,
32.1, 36.3, 36.5, 46.7, 57.9, 74.0, 78.8, 113.3, 125.7, 127.0, 127.4,
128.3, 144.5, 150.2, 152.1 ppm. LRMS (FAB): m/z = 1518 [M]+.
Tetrabenzoxazines (M,S,R)-14a and (P,S,S)-14aЈ: Prepared accord-
ing to the representative procedure from tetraundecyl-tetrameth-
oxyresorcinarene 9d (0.50 g, 0.43 mmol). The suspension was
heated under microwave irradiation at 150 °C for 2×10 min. The
obtained orange oil was placed on a column of silica gel and eluted
with light petroleum/ethyl acetate (5:1) to afford (M,S,R)-14a and
(P,S,S)-14aЈ. First eluting diastereomer (M,S,R)-14a: Pale yellow
Tetrabenzoxazines (M,S,R)-13c/(P,S,S)-13cЈ: Prepared according to
the representative procedure from tetrapentyl-tetra-n-butyloxyre-
sorcinarene 9i (1.00 g, 1.0 mmol). The residue was placed on a col-
umn of silica gel and eluted with ethyl acetate/light petroleum (1:7)
to afford (M,S,R)-13c/(P,S,S)-13cЈ. First eluting diastereomer
(M,S,R)-13c: Pale yellow foam (0.50 g, 31%). [α]2D5 –105.0 (c =
oil (0.25 g, 33%). [α]2D5 –95.2 (c = 0.84, CHCl ). IR (CHCl ): ν =
˜
3
3
3060, 2922, 2852, 2359, 1589, 1467, 1321, 1229, 1098, 944,
754 cm–1. 1H NMR (400 MHz, CDCl3): δ = 0.80 (t, J = 6.4 Hz, 12
H), 1.17–1.27 (m, 72 H), 1.31 (d, J = 6.4 Hz, 12 H), 1.55–1.82 (m,
8 H), 3.18 (s, 12 H), 3.72 (q, J = 6.4 Hz, 4 H), 3.76 (d, J = 16.8 Hz,
4 H), 4.08 (d, J = 16.8 Hz, 4 H), 4.34 (t, J = 7.6 Hz, 4 H), 4.53 (d,
0.23, CHCl ). IR (CH Cl ): ν = 3053, 2958, 2305, 1466, 1421, 1265,
˜
3
2
2
896, 747 cm–1. H NMR (400 MHz, CDCl3, 50 °C): δ = 0.93 (t, J
1
= 7.2 Hz, 12 H), 0.97 (t, J = 6.4 Hz, 12 H), 1.41 (m, 32 H), 1.46
(d, J = 6.8 Hz, 12 H), 1.56–1.65 (m, 8 H), 1.86–1.92 (m, 4 H), 1.97– J = 10.0 Hz, 4 H), 4.63 (d, J = 10.0 Hz, 4 H), 6.65 (s, 4 H), 7.08–
2.02 (m, 4 H), 3.50–3.41 (m, 4 H), 3.47–3.52 (m, 4 H), 3.89–3.95
7.29 (m, 20 H) ppm. 13C NMR (100 MHz. CDCl3): δ = 14.1, 20.1,
(m, 8 H), 4.26 (d, J = 16.8 Hz, 4 H), 4.54 (t, J = 7.2 Hz, 4 H), 4.69 21.3, 22.7, 28.3, 29.4, 29.8, 29.8, 30.0, 30.1, 32.0, 35.4, 35.8, 57.3,
(d, J = 10.0 Hz, 4 H), 4.73 (d, J = 10.0 Hz, 4 H), 6.85 (s, 4 H),
7.31–7.39 (m, 20 H) ppm. 13C NMR (100 MHz, CDCl3, 50 °C): δ
= 14.3, 14.4, 19.6, 21.6, 23.0, 28.2, 32.5, 32.9, 36.2, 36.3, 45.2, 57.9,
72.7, 80.1, 112.9, 125.3, 127.5, 127.9, 127.9, 128.7, 129.0, 144.8,
150.5, 153.3 ppm. HRMS (FAB): calcd. for C104H140N4O8 [M]+
1573.0671; found 1573.0708. C104H140N4O8 (1574.25): calcd. C
79.35, H 8.96, N 3.56; found C 79.27, H 9.03, N 3.62. Second elut-
ing diastereomer (P,S,S)-13cЈ: Pale yellow foam (0.50 g, 31%).
60.1, 70.0, 112.2, 124.6, 127.3, 127.5, 127.8, 128.4, 128.8, 144.1,
144.4, 150.1, 153.6 ppm. HRMS (FAB): calcd. for C116H164O8N4
[M + H]+ 1742.2627; found 1742.2627. Second eluting diastereomer
(P,S,S)-14aЈ: Pale yellow oil (0.24 g, 31%). [α]2D5 –15.4 (c = 0.63,
CHCl ). IR (CHCl ): ν = 3059, 2922, 2851, 2346, 1589, 1467, 1322,
˜
3
3
1
1230, 1095, 946, 751 cm–1. H NMR (400 MHz, CDCl3): δ = 0.87
(t, J = 7.2 Hz, 12 H), 1.24–1.30 (m, 72 H), 1.38 (d, J = 6.4 Hz, 12
H), 1.76–1.94 (m, 8 H), 3.33 (s, 12 H), 3.69 (q, J = 6.4 Hz, 4 H),
3.88 (d, J = 16.8 Hz, 4 H), 3.96 (d, J = 16.8 Hz, 4 H), 4.43 (t, J =
[α]2D5 = +21.0 (c = 0.51, CHCl ). IR (CH Cl ): ν = 3053, 2959, 2305,
˜
3
2
2
1590, 1465, 1421, 1265, 896, 748 cm–1. 1H NMR (400 MHz, 7.2 Hz, 4 H), 4.55 (d, J = 10.0 Hz, 4 H), 4.99 (d, J = 10.0 Hz, 4
CDCl3, 50 °C): δ = 0.77 (t, J = 7.2 Hz, 12 H), 0.86 (br. t, 12 H), H), 6.80 (s, 4 H), 7.16–7.34 (m, 20 H) ppm. 13C NMR (100 MHz.
1.15–1.24 (m, 8 H), 1.30 (m, 24 H), 1.39 (d, J = 6.4 Hz, 12 H), CDCl3): δ = 14.1, 21.4, 22.7, 28.2, 29.4, 29.75, 29.83, 29.9, 30.1,
1.41–1.48 (m, 8 H), 1.74–1.79 (m, 4 H), 1.88–1.93 (m, 4 H), 3.32–
32.0, 35.4, 36.1, 45.4, 57.4, 60.2, 79.2, 112.3, 124.5, 127.2, 127.4,
5130
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Eur. J. Org. Chem. 2006, 5117–5134