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J = 7.4 Hz, 8 H), 7.19 (m, 8 H), 17.93 (br. s, 1 H) ppm. 13C NMR
(100 MHz, [D6]DMSO): δ = 60.5, 61.9, 121.5, 125.3 (q, JC,B = 2.8 Hz),
135.6 (q, JC,B = 1.1 Hz), 163.4 (q, JC,B = 49.5 Hz) ppm. VT 1H NMR
(400 MHz, [D6]DMSO, 80 °C): δ = 3.48–3.56 (m, 4 H), 3.61 (td, J =
yield (5.339 g). M.p. 141.2 °C (dec.). IR: νmax = 3328 (w), 3056 (w),
˜
2999 (w), 1579 (w), 1478 (m), 1425 (w), 944 (w), 845 (w), 735 (vs),
705 (vs), 614 (s), 603 (s) cm–1 1H NMR (400 MHz, [D6]DMSO): δ =
.
3.43 (s, 9 H), 6.80 (t, J = 7.2 Hz, 4 H), 6.93 (t, J = 7.4 Hz, 8 H), 7.19
11.6, 3.7 Hz, 4 H), 3.85–3.93 (m, 4 H), 4.03 (ddd, J = 13.4, 10.9, 2.6 Hz, (dddt, J = 6.7, 4.0, 2.6, 1.3 Hz, 8 H), 12.21 (s, 1 H) ppm. 13C NMR
4 H), 4.29 (s, 4 H), 6.80 (t, J = 7.2 Hz, 4 H), 6.93 (t, J = 7.4 Hz, 8 H),
(100 MHz, [D6]DMSO): δ = 57.5, 121.5, 125.3 (q, JC,B = 2.8 Hz), 135.5
(q, JC,B = 1.4 Hz), 163.4 (q, JC,B = 49.5 Hz) ppm. C27H30BN2O (395.35):
7.22 (m, 8 H) ppm. VT 13C NMR (100 MHz, [D6]DMSO, 80 °C): δ =
60.2, 61.8, 62.5, 121.0, 124.7 (q, JC,B = 2.8 Hz), 135.2 (q, JC,B = 1.2 Hz), calcd. C 82.03, H 7.65, N 3.54; found C 81.78, H 7.68, N 3.50.
163.2 (q, JC,B = 49.5 Hz) ppm. C34H41BN2O4 (552.52): calcd. C 73.91,
N,N-Diisopropylethylamine N-Oxide–TPB (1:1) (22): According to
H 7.48, N 5.07; found C 73.95, H 7.48, N 5.15.
Method B (16.1 mmol), 22 was isolated as a white solid in 73 %
N,N,N′,N′-Tetramethylenediamine Bis(N-oxide)–TPB (17): Accord-
ing to Method A (8.0 mmol), 16 was isolated as a white solid in 88 %
yield (3.321 g) over two steps. Alternatively, according to Method B
(8.0 mmol), 16 was isolated as a white solid in 98 % yield (3.668 g)
yield (5.465 g) over two steps. M.p. 182.4 °C (dec.). IR: νmax = 3565
˜
(m), 3512 (m), 3051 (m), 2997 (w), 1476 (m), 1426 (m), 1385 (m),
747 (m), 731 (vs), 704 (vs), 602 (s) cm–1 1H NMR (400 MHz,
.
[D6]DMSO): δ = 1.28 (t, J = 7.3 Hz, 3 H), 1.36 (d, J = 6.4 Hz, 6 H),
1.37 (d, J = 6.4 Hz, 6 H), 3.61 (q, J = 7.3 Hz, 2 H), 4.07 (sept, J =
6.6 Hz, 2 H), 6.79 (t, J = 7.2 Hz, 4 H), 6.92 (t, J = 7.4 Hz, 8 H), 7.17
(m, 8 H), 11.05 (s, 1 H) ppm. 13C NMR (100 MHz, [D6]DMSO): δ =
9.7, 16.4, 16.9, 54.3, 65.9, 121.5, 125.3 (q, JC,B = 2.8 Hz), 135.6 (q,
JC,B = 1.4 Hz), 163.4 (q, JC,B = 49.5 Hz) ppm. C32H40BNO (465.49):
calcd. C 82.57, H 8.66, N 3.01; found C 82.74, H 8.62, N 3.01.
over two steps. M.p. 165.5 °C (dec.). IR: νmax = 3052 (w), 2984 (w),
˜
1578 (w), 1474 (m), 1439 (m), 1424 (m), 923 (m), 847 (m), 733 (vs),
706 (vs), 611 (s) cm–1. 1H NMR (400 MHz, [D6]DMSO): δ = 3.32 (s, 12
H), 4.20 (br. s, 4 H), 6.80 (t, J = 7.2 Hz, 4 H), 6.93 (t, J = 7.4 Hz, 8 H),
7.18 (m, 8 H), 18.06 (br. s, 1 H) ppm. 13C NMR (100 MHz, [D6]DMSO):
63.2, 121.5, 125.3 (q, JC,B = 2.8 Hz), 135.5 (q, JC,B = 1.1 Hz), 163.4 (q,
JC,B = 49.5 Hz) ppm. VT 1H NMR (400 MHz, [D6]DMSO, 80 °C): δ =
3.34 (s, 12 H), 4.19 (s, 4 H), 6.80 (t, J = 7.2 Hz, 4 H), 6.93 (t, J = 7.4 Hz,
8 H), 7.18 (m, 8 H) ppm. VT 13C NMR (100 MHz, [D6]DMSO, 80 °C):
δ = 56.7, 63.1, 121.0, 124.7 (q, JC,B = 2.8 Hz), 135.2 (q, JC,B = 1.3 Hz),
163.2 (q, JC,B = 49.5 Hz) ppm. C30H37BN2O2 (468.45): calcd. C 76.92,
H 7.98, N 5.98; found C 76.68, H 8.03, N 5.97.
Diazabicyclo[2.2.2]octane N-Oxide–TPB (1:1) (23): According to
Method B (16.9 mmol), 23 was isolated as a white solid in 97 %
yield (7.399 g) over two steps. M.p. 132.0 °C (dec.). IR: νmax = 3286
˜
(w), 3054 (w), 2986 (w), 1579 (w), 1478 (m), 1425 (m), 1053 (m), 743
1
(s), 707 (vs), 613 (m), 602 (vs) cm–1. H NMR (400 MHz, [D6]DMSO):
δ = 3.12–3.16 (m, 6 H), 3.48–3.51 (m, 6 H), 6.80 (t, J = 7.2 Hz, 4 H),
6.94 (t, J = 7.4 Hz, 8 H), 7.19 (m, 8 H), 12.35 (s, 1 H) ppm. 13C NMR
(100 MHz, [D6]DMSO): δ = 46.8, 57.7, 121.5, 125.3 (q, JC,B = 2.8 Hz),
135.5 (q, JC,B = 1.1 Hz), 163.3 (q, JC,B = 49.3 Hz) ppm. C30H33BNO
(448.42): calcd. C 80.36, H 7.42, N 6.25; found C 80.10, H 7.42, N
6.28.
N-Methylpiperidine N-Oxide–TPB (3:2) (18): According to
Method C (16.5 mmol), 18 was isolated as a white solid in 26 %
yield (1.428 g) over two steps. M.p. 121.7 °C (dec.). IR: νmax = 3514
˜
(w), 3054 (w), 2984 (w), 1578 (w), 1478 (m), 1443 (m), 1424 (m), 963
(m), 930 (m), 732 (vs), 703 (vs), 610 (vs) cm–1 1H NMR (400 MHz,
.
[D6]DMSO): δ = 1.30–1.42 (m, 3 H), 1.58–1.70 (m, 9 H), 1.86–1.97 (m,
6 H), 3.26 (s, 9 H), 3.34–3.46 (m, 12 H), 6.80 (t, J = 7.2 Hz, 8 H), 6.93
(t, J = 7.4 Hz, 16 H), 7.18 (m, 16 H) ppm. 13C NMR (100 MHz,
[D6]DMSO): δ = 20.2, 20.3, 57.0, 64.8, 121.5, 125.3 (q, JC,B = 2.8 Hz),
N-Methylmorpholine N-Oxide–TPB (1:1) (24): According to
Method B (16.3 mmol), 24 was isolated as a white solid in 96 %
yield (6.811 g). M.p. 116.6 °C (dec.). IR: νmax = 3573 (w), 3512 (w),
˜
3057 (w), 2875 (w), 1477 (m), 1425 (m), 1118 (m), 744 (s), 734 (s),
135.5 (q, JC,B
= 1.1 Hz), 163.3 (q, JC,B = 49.3 Hz) ppm.
1
707 (vs), 604 (s) cm–1. H NMR (400 MHz, [D6]DMSO): δ = 3.48 (s, 3
C66H81B2N3O3+H2O (1004.03): calcd. C 78.95, H 8.33, N 4.19; found
C 78.83, H 8.32, N 4.21.
H), 3.54 (d, J = 13.1 Hz, 2 H), 3.74 (dt, J = 14.2, 7.3 Hz, 22 H), 3.92
(dd, J = 7.3, 1.6 Hz, 4 H), 6.80 (t, J = 7.2 Hz, 8 H), 6.93 (t, J = 7.3 Hz,
8 H), 7.19 (dtd, J = 5.5, 2.6, 1.5 Hz, 8 H), 12.35 (br. s, 1 H) ppm. 13C
NMR (100 MHz, [D6]DMSO): δ = 56.6, 60.5, 63.3, 121.5, 125.3 (q,
JC,B = 2.8 Hz), 135.5 (q, JC,B = 1.1 Hz), 163.3 (q, JC,B = 49.5 Hz) ppm.
C29H32BNO2+0.5H2O (446.40): calcd. C 78.03, H 7.45, N 3.14; found
C 78.04, H 7.53, N 3.16.
N-Methylpyrrolidine N-Oxide–TPB (3:2) (19): According to
Method C (17.3 mmol), 19 was isolated as a white solid in 24 %
yield (1.310 g) over two steps. M.p. 127.8 °C (dec.). IR: νmax = 3552
˜
(w), 3048 (w), 2984 (w), 1578 (w), 1478 (m), 1449 (m), 1428 (m),
1033 (m), 734 (vs), 705 (vs), 610 (s) cm–1 1H NMR (400 MHz,
.
[D6]DMSO): δ = 1.98–2.20 (m, 12 H), 3.35 (s, 9 H), 3.61–3.52 (m, 12
H), 6.79 (t, J = 7.2 Hz, 8 H), 6.93 (t, J = 7.4 Hz, 16 H), 7.18 (m, 16 H)
ppm. 13C NMR (100 MHz, [D6]DMSO): δ = 21.5, 53.7, 67.7, 121.5,
N-Methylpiperidine N-Oxide–TPB (1:1) (25): According to
Method B (16.5 mmol), 25 was isolated as a white solid in 81 %
125.3 (q, JC,B = 2.8 Hz), 135.6 (q, JC,B = 1.1 Hz), 163.4 (q, JC,B
=
yield (5.785 g) over two steps. M.p. 144.0 °C (dec.). IR: νmax = 3584
˜
49.5 Hz) ppm. C63H75B2N3O3 (943.60): calcd. C 80.16, H 8.01, N 4.42;
found C 80.09, H 7.99, N 4.42.
(w), 3520 (w), 3054 (w), 2985 (w), 1578 (w), 1478 (m), 1426 (m), 743
(s), 732 (s), 705 (vs), 604 (s) cm–1. 1H NMR (400 MHz, [D6]DMSO): δ =
1.39 (dtt, J = 13.5, 11.5, 4.1 Hz, 1 H); 1.64 (dp, J = 12.9, 4.1 Hz, 1 H),
1.74 (dt, J = 14.4, 3.9 Hz, 2 H), 1.88 (ddtd, J = 15.2, 11.3, 8.1, 7.4,
4.0 Hz, 2 H), 3.27 (dt, J = 11.8, 3.6 Hz, 4 H), 3.38 (s, 3 H), 3.55 (dd,
J = 7.7, 3.8 Hz, 4 H), 6.80 (t, J = 7.2 Hz, 4 H), 6.93 (t, J = 7.4 Hz, 8
H), 7.19 (m, 8 H), 11.89 (s, 1 H) ppm. 13C NMR (100 MHz, [D6]DMSO):
δ = 20.0, 20.1, 56.4, 64.5, 121.5, 125.3 (q, JC,B = 2.8 Hz), 135.5 (q,
JC,B = 1.4 Hz), 163.3 (q, JC,B = 49.3 Hz) ppm. C30H34BNO (435.42):
calcd. C 82.75, H 7.87, N 3.22; found C 82.69, H 7.85, N 3.21.
Triethylamine N-Oxide–TPB (1:1) (20): According to Method B
(15.8 mmol), 20 was isolated as a white solid in 48 % yield (3.213 g)
over two steps. M.p. 168.4 °C (dec.). IR: νmax = 3348 (m), 3054 (w),
˜
2986 (w), 1581 (w), 1479 (m), 1427 (m), 1152 (m), 747 (s), 734 (s),
708 (vs), 605 (s) cm–1 1H NMR (400 MHz, [D6]DMSO): δ = 1.32 (t,
.
J = 7.2 Hz, 9 H), 3.48 (q, J = 7.2 Hz, 6 H), 6.83 (t, J = 7.2 Hz, 4 H),
6.97 (t, J = 7.4 Hz, 8 H), 7.23 (m, 8 H), 11.51 (s, 1 H) ppm. 13C NMR
(100 MHz, [D6]DMSO): δ = 7.6, 57.9, 121.5, 125.3 (q, JC,B = 2.8 Hz),
135.6 (q, JC,B = 1.4 Hz), 163.4 (q, JC,B = 49.5 Hz) ppm. C30H36BNO
(437.43): calcd. C 82.37, H 8.30, N 3.20; found C 82.33, H 8.37, N
3.18.
N-Methylpyrrolidine N-Oxide–TPB (1:1) (26): According to
Method B (15.8 mmol), 26 was isolated as a white solid in 82 %
yield (5.433 g) over two steps. M.p. 115.3 °C (dec.). IR: νmax = 3566
˜
Trimethylamine N-Oxide–TPB (1:1) (21):[15] According to
Method B (16.2 mmol), 21 was isolated as a white solid in 83 %
(w), 3052 (w), 2985 (w), 1627 (w), 1587 (w), 1478 (m), 1447 (m), 735
(s), 709 (vs), 610 (vs) cm–1. 1H NMR (400 MHz, [D6]DMSO): δ = 2.00–
Eur. J. Org. Chem. 0000, 0–0
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