´
M. Alajarın et al. / Tetrahedron 62 (2006) 6190–6202
6199
(dd, J(H,H)¼7.5, 2.1 Hz, 6H, oH-PhP); 13C{1H} NMR
(75.4 MHz, CDCl3): d¼27.42 (CH3), 37.48 (m, CH2P),
iC-PhP), 131.66 (d, 4J(C,P)¼2.7 Hz, pC-PhP), 131.91
4
2
(d, J(C,P)¼2.1 Hz, pC-PhP), 131.96 (d, J(C,P)¼9.3 Hz,
2
4
39.05 (q, J(C,P)¼3.4 Hz, CH3C), 57.68 (CH2N), 118.56,
oC-PhP), 132.54 (d, J(C,P)¼4.1 Hz), 137.99 (q), 139.67
3
2
2
122.52 (d, J(C,P)¼12.6 Hz, s-cis-CH]C–N]P), 125.29
(q), 150.33 (d, J(C,P)¼1.4 Hz, q), 150.95 (d, J(C,P)¼
1.6 Hz, q), the resonance of one iC-PhP was not observed;
31P{1H} NMR (121.4 MHz, CDCl3): d¼0.29 (s, 2P), 0.39
(s, 1P); IR (Nujol): n¼1437 (CP), 1110 (NP) cmꢁ1; MS
(FAB+): m/z (%)¼1146 (10) [M++6], 1144 (29) [M++4],
1142 (38) [M++2], 1140 (21) [M+], 154 (100);
C62H54ClBr2N4P3 (1143.30): Calcd C 65.13, H 4.76, N
4.90; found C 65.01, H 4.65, N 4.77.
(d, 3J(C,P)¼28.7 Hz, s-trans-CH]C–N]P), 128.20,
128.37 (d, 3J(C,P)¼12.6 Hz, mC-PhP), 128.71 (d, 3J(C,P)¼
1
11.5 Hz, mC-PhP), 130.66 (d, J(C,P)¼85.1 Hz, iC-PhP),
4
2
131.21 (d, J(C,P)¼1.8 Hz, pC-PhP), 131.49 (d, J(C,P)¼
8.6 Hz, oC-PhP), 131.70 (d, 4J(C,P)¼1.1 Hz, pC-PhP),
2
1
132.12 (d, J(C,P)¼9.2 Hz, oC-PhP), 132.41 (d, J(C,P)¼
102.1 Hz, iC-PhP), 141.99 (q), 151.33 (q); 31P{1H} NMR
(121.4 MHz, CDCl3): d¼0.22; IR (Nujol): n¼1459 (CP),
1114 (NP) cmꢁ1; MS (FAB+): m/z (%)¼950 (100) [M+
ꢁ1]; C62H57N4P3 (951.06): Calcd C 78.30, H 6.04, N 5.89;
found C 78.15, H 5.89, N 5.75.
4.12.4. Tri-l5-phosphazenes 5d+5d0. Yield: 83%; 1H NMR
(300 MHz, CDCl3): d¼ꢁ0.74 [s, 6H, CH3 (d+d0)], 3.05–
3.70 [m, 36H, CHAHBP (d+d0)+CH2N (d+d0)], 3.80–4.04
[m, 12H, CHAHBP (d+d0)], 6.39–6.52 [m, 5H, Harom
(d+d0)], 6.93–7.04 [m, 5H, Harom (a+b)], 7.10–7.13 [m,
4H, Harom (d+d0)], 7.26–7.48 [m, 34H, Harom (a+b)], 7.80–
7.88 [m, 8H, Harom (d+d0)]; 13C{1H} NMR (75.4 MHz,
CDCl3): d¼27.48 [CH3 (d+d0)], 37.34–38.41 [m, CH2P
(d+d0)], 39.02 [q, 2J(C,P)¼3.5 Hz, CH3C (d+d0)], 53.26
[CH2N (d/d0)], 53.54 [CH2N (d/d0)], 56.81 [CH2N (d/d0)],
56.13 [CH2N (d/d0)], 57.88 [CH2N (d/d0)], 57.91 [CH2N
(d/d0)], 111.81 [q (d/d0)], 111.94 [q (d/d0)], 118.59 (d+d0),
122.21 [q (d/d0)], 122.25 [d, 3J(C,P)¼11.6 Hz, s-cis-
CH]C–N]P (d+d0)], 122.30 [q (d/d0)], 123.97 [d,
3J(C,P)¼12.7 Hz, s-cis-CH]C–N]P (d+d0)], 124.20 [d,
3J(C,P)¼12.2 Hz, s-cis-CH]C–N]P (d/d0)], 124.27
4.12.2. Tri-l5-phosphazene 5b. Yield: 74%; mp (decomp.)
1
316–318 ꢀC (colorless prisms from chloroform); H NMR
(300 MHz, CDCl3): d¼ꢁ0.69 (s, 3H, CH3), 3.23 (pseudo-
quint, J(H,H)(H,P)¼8.4 Hz, 3H, CHAHBP), 3.45 (d, J(H,H)¼
13.3 Hz, 3H, CHAHBN), 3.65 (d, J(H,H)¼13.3 Hz, 3H,
CHAHBN), 3.95 (pseudot, J(H,H)(H,P)¼14.5 Hz, 3H,
CHAHBP), 6.55–6.57 (m, 3H, Harom), 6.96 (dd, J(H,H)¼
8.6, 2.5 Hz, 6H, Harom), 7.25–7.42 (m, 24H, Harom), 7.81–
7.87 (m, 6H, Harom); 13C{1H} NMR (75.4 MHz, CDCl3):
d¼27.59 (CH3), 38.09 (m, CH2P), 39.10 (q, 2J(C,P)¼
3.2 Hz, CH3C), 56.46 (CH2N), 111.71 (q), 123.69 (d,
3J(C,P)¼12.2 Hz, s-cis-CH]C–N]P), 127.07 (d, 3J(C,P)¼
27.8 Hz, s-trans-CH]C–N]P), 128.50 (d, 3J(C,P)¼
3
[d, J(C,P)¼12.2 Hz, s-cis-CH]C–N]P (d/d0)], 125.41 [d,
3
12.8 Hz, mC-PhP), 128.87 (d, J(C,P)¼11.0 Hz, mC-PhP),
3J(C,P)¼28.4 Hz, s-trans-CH]C–N]P (d+d0)], 126.57
[d, 3J(C,P)¼29.0 Hz, s-trans-CH]C–N]P (d+d0)],
127.11 [d, 3J(C,P)¼28.4 Hz, s-trans-CH]C–N]P
(d+d0)], 128.35–132.60 (d+d0), 138.25 [q (d/d0)], 138.31 [q
(d/d0)], 139.95 [q (d/d0)], 139.99 [q (d/d0)], 141.57 [q
(d+d0)], 149.99 [q (d/d0)], 150.19 [q (d/d0)], 150.65 [q (d/
d0)], 150.83 [q (d/d0)], 151.35 [q (d+d0)]; 31P{1H} NMR
(121.4 MHz, CDCl3): d¼ꢁ0.11 (s, 1P), ꢁ0.05 (s, 1P), 0.84
(s, 1P), 0.88 (s, 1P), 1.04 (s, 1P), 1.16 (s, 1P); IR (Nujol):
1
2
130.23 (d, J(C,P)¼90.5 Hz, iC-PhP), 131.13 (d, J(C,P)¼
9.3 Hz, oC-PhP), 131.60 (br s, pC-PhP), 131.81 (br s, pC-
PhP), 131.91 (d, 1J(C,P)¼105.2 Hz, iC-PhP), 131.99
(d, 2J(C,P)¼9.3 Hz, oC-PhP), 132.60, 139.65 (q), 150.77 (q);
31P{1H} NMR (121.4 MHz, CDCl3): d¼0.49; IR (Nujol):
n¼1457 (CP), 1119 (NP) cmꢁ1; MS (FAB+): m/z (%)¼
1190 (48) [M++6], 1188 (84) [M++4], 1186 (60) [M++2],
1184 (15) [M+], 154 (100); C62H54Br3N4P3 (1187.75):
Calcd C 62.70, H 4.58, N 4.72; found C 62.58, H 4.44, N 4.57.
n¼1442 (CP), 1123 (NP) cmꢁ1
; MS (FAB+): m/z
(%)¼1066 (31) [M++4], 1064 (89) [M++2], 1062 (74)
[M+], 154 (100); C62H55ClBrN4P3 (1064.41): Calcd C
69.96, H 5.21, N 5.26; found C 69.82, H 5.08, N 5.12.
4.12.3. Tri-l5-phosphazene 5c. Yield: 79%; mp (decomp.)
1
325–326 ꢀC (colorless prisms from chloroform); H NMR
(300 MHz, CDCl3): d¼ꢁ0.73 (s, 3H, CH3), 3.23 (pseudo-
quint, J(H,H)(H,P)¼6.8 Hz, 3H, CHAHBP), 3.34 (d, J(H,H)¼
13.3 Hz, 2H, CHAHBN), 3.38 (d, J(H,H)¼13.1 Hz, 1H,
CHAHBN), 3.61 (d, J(H,H)¼13.3 Hz, 2H, CHAHBN), 3.65
(d, J(H,H)¼13.1 Hz, 1H, CHAHBN), 3.89 (pseudot,
J(H,H)(H,P)¼14.7 Hz, 3H, CHAHBP), 6.48–6.50 (m, 3H,
Harom), 6.96 (dd, J(H,H)(H,P)¼8.6, 2.7 Hz, 2H, Harom),
7.01 (dd, J(H,H)(H,P)¼8.6, 2.7 Hz, 1H, Harom), 7.13 (d,
J(H,H)¼8.7 Hz, 2H, Harom), 7.15 (d, J(H,H)¼8.7 Hz, 1H,
Harom), 7.27–7.49 (m, 24H, Harom), 7.78–7.89 (m, 6H,
Harom); 13C{1H} NMR (75.4 MHz, CDCl3): d¼27.50
(CH3), 37.91 (ddd, 1J(C,P)¼46.5 Hz, 3J(C,P)¼11.9,
4.12.5. Tri-l5-phosphazene 5e. Yield: 85%; mp 301–
1
303 ꢀC (colorless prisms from chloroform/n-hexane); H
NMR (300 MHz, CDCl3): d¼ꢁ0.69 (s, 3H, CH3), 2.50 (s,
9H, CH3-Ar), 2.87 (d, J(H,H)¼12.3 Hz, 3H, CHAHBN),
3.14 (pseudoquint, J(H,H)(H,P)¼6.8 Hz, 3H, CHAHBP),
3.58 (d, J(H,H)¼12.3 Hz, 3H, CHAHBN), 4.04 (pseudot,
J(H,H)(H,P)¼14.4 Hz, 3H, CHAHBP), 6.43 (d, J(H,H)¼
7.2 Hz, 3H, Harom), 6.48 (s, 3H, Harom), 7.05 (dd, J(H,H)¼
7.1, 2.7 Hz, 3H, Harom), 7.20–7.36 (m, 27H, Harom), 7.84–
7.89 (m, 3H, Harom); 13C{1H} NMR (75.4 MHz, CDCl3):
d¼19.56 (CH3-Ar), 28.26 (CH3C), 37.46 (m, CH2P), 38.86
2
2
3.9 Hz, 3 CH2P), 38.96 (q, J(C,P)¼3.9 Hz, CH3C), 53.59
(q, J(C,P)¼3.5 Hz, CH3C), 57.52 (CH2N), 118.16, 122.09
3
(2 CH2N), 56.19 (CH2N), 111.52 (2 q), 121.99 (q), 123.40
(d, 3J(C,P)¼12.3 Hz, s-cis-CH]C–N]P), 123.72 (d,
(d, J(C,P)¼12.2 Hz, s-cis-CH]C–N]P), 128.18, 128.40
(d, 3J(C,P)¼11.6 Hz, mC-PhP), 128.62 (br s, pC-PhP),
131.05 (d, 3J(C,P)¼8.7 Hz, mC-PhP), 131.33 (br s, pC-
PhP), 132.19 (d, 1J(C,P)¼81.8 Hz, iC-PhP), 132.21 (d,
2J(C,P)¼9.3 Hz, oC-PhP), 133.19 (dleft iC-PhP), 139.88
(q), 149.59 (q), the resonance of one oC-PhP and the quater-
nary atom s-trans-C]C–N]P was not observed; 31P{1H}
NMR (121.4 MHz, CDCl3): d¼ꢁ1.43; IR (Nujol): n¼1437
3J(C,P)¼12.3 Hz,
2
s-cis-CH]C–N]P), 126.62
(d, 3J(C,P)¼26.6 Hz, s-trans-CH]C–N]P), 127.16 (d,
3J(C,P)¼28.2 Hz, 2 s-trans-CH]C–N]P), 128.61 (d,
3J(C,P)¼13.4 Hz, mC-PhP), 128.86 (d, J(C,P)¼11.9 Hz,
3
mC-PhP), 129.43 (d, 4J(C,P)¼4.5 Hz), 131.08 (d,
2J(C,P)¼8.8 Hz, oC-PhP), 131.46 (d, 1J(C,P)¼81.2 Hz,