1760
V. I. Maslennikova et al. / Tetrahedron 59 (2003) 1753–1761
74.28; H, 8.97; N, 2.44; P, 8.61. C33H46NO3P requires: C,
73.99; H, 8.66; N, 2.61; P, 5.78%]; dP (32.4 MHz, CDCl3)
CH2), 1.72 (s, 3H, Ar–CH3), 1.78 (s, 3H, Ar–CH3), 1.94 (s,
3
3H, Ar–CH3), 2.41 (t, JHH¼6.6 Hz, 2H, CH2), 3.00–3.15
3
147.2; dH (200 MHz, CDCl3) 1.15 (t, JHH¼7.3 Hz, 6H,
(m, br., 2H, N(CH2CH3)2), 3.30–3.45 (m, br., 2H,
N(CH2CH3)2), 3.98 (d, 1H, JHH¼16.0 Hz, Ar–CH2–Ar),
2
NCH2CH3), 1.43 (s, 9H, C(CH3)3), 1.51 (s, 9H, C(CH3)3),
2.24 (s, 3H, CH3), 2.31 (s, 3H, CH3), 3.32–3.41 (br.m,
2
4.16 (d, 1H, JHH¼16.0 Hz, Ar–CH2–Ar), 5.90 (s, 1H,
3
3JPH¼9.4 Hz, JPH¼9.0 Hz, 4H, NCH2CH3), 3.97 (d,
OH), 6.80 (s, 1H, Ar–H), 6.91 (s, 1H, Ar–H), 7.08 (s, 1H,
Ar–H), 7.20 (s, 1H, Ar–H); dC (75.48 MHz, CDCl3) 11.88,
12.54, 13.80 (d, 3JPC¼4.6 Hz, N(CH2CH3)2), 14.74, 19.65–
19.75, 20.84 (CH2), 21.06 (CH2), 22.63, 22.72, 23.54, 23.93,
24.45 (CH2), 24.82 (CH2), 27.99, 29.65 (C(CH3)3), 30.07,
30.97, 31.32 (C(CH3)3), 31.53 (CH2), 31.59, 31.68
2
2JHH¼15.4 Hz, 1H, Ar–CH2–Ar), 4.36 (d, JHH¼15.4 Hz,
1H, Ar–CH2–Ar), 5.75 (br.s, 1H, OH), 6.84 (s, 1H,
H-arom.), 6.89 (s, 1H, H-arom.), 6.95–7.05 (3H, C6H5),
7.08 (br.s, 2H, H-arom.), 7.23–7.29 (2H, C6H5).
4
3.1.14. Diethylamido-O-(2-[2-hydroxy-3-tert-butyl-5-
methyl-benzyl]-4-methyl-6-tert-butyl-phenyl)-O-toco-
pherylphosphite (16b). A solution of 13 (6.05 g, 10 mmol)
in toluene (20 mL) was added dropwise to a solution of 11a
(3.40 g, 10 mmol) in toluene (30 mL) and the mixture was
refluxed for 24 h. The liquids were removed in vacuo and
the residue was purified by column chromatography (bas.
Alox, n-hexane; Rf¼0.4). The title compound 16b (5.80 g,
66.5%) is a yellow oil; [Found: C, 76.79; H, 10.14; N, 2.01.
C56H90NO4P requires: C, 77.11; H, 10.40; N, 1.61]; dP
(121.5 MHz, CDCl3) 147.64; dH (300 MHz, CDCl3) 0.78 (t,
3JHH¼6.9 Hz, 12H, CH3 from tocopherol side-chain), 1.02
(C(CH3)3), 32.22 (d, JPC¼5.9 Hz, C(CH3)3), 32.76, 33.79
(Ar–CH2–Ar), 34.15 (C(CH3)3), 34.31 (C(CH3)3), 34.62
(C(CH3)3), 35.30 (C(CH3)3), 37.31–37.63 (CH2), 39.13 (d,
2JPC¼22.9 Hz, N(CH2CH3)2), 39.39 (CH2), 74.68 (tert.-C),
117.45, 121.96, 123.80, 125.03, 125.44, 126.16, 127.89,
128.32, 129.04, 132.22, 135.25, 141.14, 141.42, 141.65,
145.77, 147.45, 147.67, 150.86 (Ar–C); m/z 957 [MþHþ].
3.1.16. 2-Diethylamino-4,5;7,8-dibenzo-9,90-di-tert-
butyl-11,110-dimethyl-1,3,2-dioxaphosphocin (17a).7 (a)
A solution of 11a (115.6 mg, 0.34 mmol) and 4b (91.1 mg,
0.34 mmol) in acetonitrile (1 mL) was maintained at
80–908C for 10 h.
3
(t, JHH¼6.7 Hz, 6H, N(CH2CH3)2), 1.10–1.50 (m, br.,
21H, CH and CH2 from tocopherol side-chain, 3H, CH3),
1.26 (s, 9H, C(CH3)3), 1.37 (s, 9H, C(CH3)3), 1.60–1.70 (m,
br., 2H, CH2), 1.79 (s, 3H, Ar–CH3), 1.85 (s, 3H, Ar–CH3),
1.95 (s, 3H, Ar–CH3), 2.11 (s, 3H, Ar–CH3), 2.16 (s, 3H,
Ar–CH3), 2.42 (t, br., 2H, CH2), 3.00–3.15 (m, br., 2H,
N(CH2CH3)2), 3.30–3.45 (m, br., 2H, N(CH2CH3)2), 84 (d,
(b) A solution of 16a (107.0 mg, 0.2 mmol) in acetonitrile
(1 mL) was maintained at 85–958C for 8 h.
(c) A solution of 16b (1.00 g, 0.114 mmol) in xylene
(15 mL) was heated under reflux for 8 h.
2
2
1H, JHH¼15.6 Hz, Ar–CH2–Ar), 4.16 (d, 1H, JHH
¼
15.6 Hz, Ar–CH2–Ar), 6.04 (s, 1H, OH), 6.67 (s, 1H, Ar–
H), 6.73 (s, 1H, Ar–H), 6.86 (s, 1H, Ar–H), 6.96 (s, 1H,
Ar–H); dC (75.48 MHz, CDCl3) 11.88, 12.90, 13.80 (d,
3JPC¼4.6 Hz, N(CH2CH3)2), 14.64, 19.65, 20.81, 20.99
(CH2), 22.62, 22.72, 23.56 (Ar–CH3 from bisphenol), 23.93
(Ar–CH3 from bisphenol and toc-CH), 24.45 (CH2), 24.81
(CH2), 27.98, 29.59 (C(CH3)3), 31.25, 31.40 (CH2), 32.04
The solvent was removed by distillation. The residue was
recrystallized from benzene and dried in vacuo. The title
compound 17a (72 (a), 48.5 (b), and 32.2 (c) mg, 48, 55, and
64% respectively) is a white solid, mp. 136–1378C; [Found:
C, 73.13; H, 9.44; N, 3.41. C27H40NO2P requires: C 73.44 H
9.13 N 3.17%]; dP (121.50 MHz, CDCl3) 144.42; d
3
H
(300.13 MHz, CDCl3) 1.29 (t, JHH¼7.1 Hz, 6 H,
4
(d, JPC¼5.81 Hz, C(CH3)3), 32.76, 33.79 (Ar–CH2–Ar),
N(CH2CH3)2),1.40 (s, 18 H, C(CH3)3), 2.28 (s, 6 H, CH3),
3.30 (d, 2JHH¼12.4 Hz, 1 H, e-CH2), 3.43 (p, 3JHH¼7.1 Hz,
4 H, N(CH2CH3)2), 4.35 (dd, 2JHH¼12.4 Hz, 5JPH¼2.8 Hz,
1 H, a-CH2), 7.00 (s, 2 H, Ar–H), 7.09 (s, 2 H, Ar–H); (C
(75.48 MHz, CDCl3) 14.28 (d, 3JPC¼4.2 Hz, N(CH2CH3)2),
20.94 (CH3), 30.86 (d, JPC¼4.2 Hz, C(CH3)3), 34.61 (CH2),
34.62 (C(CH3)3), 35.30 (C(CH3)3), 37.31–37.61 (CH2),
39.11 (d, 2JPC¼23.1 Hz, N(CH2CH3)2), 39.39 (CH2), 74.63
(tert.-C), 117.4, 122.84, 125.84 (2 s), 126.98, 127.70,
127.83 (d, JPC¼3.2 Hz), 127.93, 128.44, 129.09, 132.73,
132.83, 135.93, 141.70 (d, JPC¼4.9 Hz), 141.92 (d,
2
2
JPC¼2.2 Hz), 147.49 (d, JPC¼4.5 Hz), 147.68, 151.16
34.68 (C(CH3)3), 38.76 (d, JPC¼21.3 Hz, N(CH2CH3)2),
(Ar–C); m/z 873 [MþHþ], 912 [MþKþ].
126.28, 128.37, 132.57, 136.30 (d, JPC¼3.2 Hz), 141.57 (d,
JPC¼3.4 Hz), 148.13 (d, JPC¼7.9 Hz, Caryl); m/z 443
[MþHþ], 370 [M2HNEt2þHþ].
3.1.15. Diethylamido-O-(2-[2-hydroxy-3,5-di-tert-butyl-
benzyl]-4,6-di-tert-butyl phenyl)-O-tocopherylphosphite
(16c). A solution of 13 (12.10 g, 20 mmol) in toluene
(20 mL) was added dropwise to a solution of 11b (8.50 g,
20 mmol) in toluene (70 mL) and the mixture was refluxed
for 24 h. The liquids were removed in vacuo and the
residue was purified by column chromatography (bas. Alox,
n-hexane). The title compound 16c (17.3 g, 90.4%) is a
colourless oil; [Found: C, 77.69; H, 10.66; N, 1.75.
C62H102NO4P requires: C, 77.86; H, 10.75; N, 1.46%]; dP
(121.5 MHz, CDCl3) 147.66; dH (300 MHz, CDCl3) 0.78 (t,
3JHH¼7.2 Hz, 12H, CH3 from tocopherol side-chain), 1.02
3.1.17. 2-Diethylamino-4,5;7,8-dibenzo-9,90,11,110-tetra-
tert-butyl-1,3,2-dioxaphosphocine (17b).7 Was obtained
from 16c (1.00 g, 0.1 mmol) analogous to 17a (c). The title
compound 17b (37.8 mg, 72%) is a white solid, mp 162–
1638C; [Found: C, 75.76; H, 10.27; N, 2.74. C33H52NO2P
required: C 75.39 H 9.97 N 2.66%]; dP (121.1 MHz, CDCl3)
3
143.93; dH (300.13 MHz, CDCl3) 1.29 (t, JHH¼7.1 Hz, 6
H, N(CH2CH3)2), 1.31 (s, 18 H, C(CH3)3), 1.42 (s, 18 H,
C(CH3)3), 3.39 (d, JHH¼12.4 Hz, 1 H, e-CH2), 3.43 (p,
2
3JHH¼7.1 Hz, 6 H, N(CH2CH3)2), 4.41 (dd, 2JHH¼12.4 Hz,
3
(t, JHH¼7.0 Hz, 6H, N(CH2CH3)2), 0.90–1.50 (m, br.,
5JPH¼2.9 Hz, 1 H, a-CH2), 7.24 (d, 4JHH¼2.3 Hz, 2 H, Ar–
4
21H, CH and CH2 from tocopherol side-chain, 3H, CH3),
1.11 (s, 9H, C(CH3)3), 1.19 (s, 9H, C(CH3)3), 1.27 (s, 9H,
C(CH3)3), 1.39 (s, 9H, C(CH3)3), 1.60–1.70 (m, br., 2H,
H), 7.30 (d, JHH¼2.3 Hz, 2 H, Ar–H); dC (75.48 MHz,
3
CDCl3) 14.40 (d, JPC¼4.3 Hz, N(CH2CH3)2), 30.97 (d,
JPC¼5.1 Hz, C(CH3)3), 31.52 (C(CH3)3), 34.40, 35.08