M. Alajarꢀın et al. / Tetrahedron 63 (2007) 4450–4458
4457
CDCl3, 25 ꢀC): d¼1.48 (br s, 1H; CH), 3.33 (br s, 6H;
CH2P), 3.69 (br s, 6H; CH2N), 6.47 (d, J(H,H)¼2.7 Hz,
3H; Harom), 6.84 (dd, J(H,H)¼8.7, 3.0 Hz, 3H; Harom),
CH]C–N]P), 126.88 (d, 3J(C,P)¼27.8 Hz; s-trans-
CH]C–N]P), 128.48 (d, 3J(C,P)¼12.8 Hz; mC-PhP),
3
128.82 (d, J(C,P)¼11.0 Hz; mC-PhP), 130.80 (dright; iC-
1
2
7.23–7.52 (m, 33H; Harom); H NMR (300 MHz, CDCl3,
PhP), 131.00 (d, J(C,P)¼8.7 Hz; oC-PhP), 131.25 (br s;
60 ꢀC): d¼1.30 (pseudoq, J(H,H),(H,P)¼8.4 Hz, 1H; CH),
3.32 (br s, 6H; CH2P), 3.70 (s, 6H; CH2N), 6.49 (d,
J(H,H)¼2.7 Hz, 3H; Harom), 6.82 (dd, J¼8.7, 3.0 Hz,
3H; Harom), 7.23–7.44 (m, 33H; Harom); 13C{1H} NMR
pC-PhP), 131.57 (br s; pC-PhP), 131.92 (d, 2J(C,P)¼9.3 Hz;
oC-PhP), 132.86, 138.97 (q), 150.98 (q), the resonance of one
iC-PhP was not observed; 31P{1H} NMR (121.4 MHz,
CDCl3): d¼0.63; IR (Nujol): n¼1440 (CP), 1119 (NP) cmꢁ1
;
2
(75.4 MHz, CDCl3, 60 ꢀC): d¼26.18 (q, J(C,P)¼2.5 Hz;
MS (FAB+): m/z(%)¼1202 (95) [M++4], 1200 (100) [M++2],
1198 (31) [M+]; C63H56Br3N4P3 (1201.78): calcd C 62.96, H
4.70, N 4.66; found C 62.85, H 4.64, N 4.60.
1
3
CH), 28.12 (dt, J(C,P)¼46.4 Hz, J(C,P)¼8.2 Hz; CH2P),
56.96 (CH2N), 111.74 (q), 124.73 (d, 3J(C,P)¼10.4 Hz;
3
s-cis-CH]C–N]P), 126.86 (d, J(C,P)¼27.8 Hz; s-trans-
CH]C–N]P), 128.74 (d, 3J(C,P)¼12.2 Hz; mC-PhP),
4.6.5. Tri-l5-phosphazene 7g. Yield: 7%; mp 258–260 ꢀC
(colourless prisms from dichloromethane/diethyl ether); 1H
NMR (300 MHz, CDCl3): d¼ꢁ0.41 [d, J(H,H)¼7.0 Hz,
3H; (CH3)A], ꢁ0.21 [d, J(H,H)¼6.8 Hz, 3H; (CH3)B], 0.96
(m, 1H; CH), 2.81 (d, J(H,H)¼12.4 Hz, 3H; CHAHBN),
3.34 (d, J(H,H)¼12.4 Hz, 3H; CHAHBN), 3.66 (pseudoquint,
J(H,H),(H,P)¼7.6 Hz, 3H; CHAHBP), 3.94 (pseudot,
J(H,H),(H,P)¼15.9 Hz, 3H; CHAHBP), 6.37 (d, J(H,H)¼
7.0 Hz, 3H; Harom), 6.40 (br s, 3H; Harom), 7.02 (dt, J(H,H)¼
7.2, 1.8 Hz, 3H; Harom), 7.12 (d, J(H,H)¼6.9 Hz, 3H; Harom),
7.34–7.39 (m, 15H; Harom), 7.46–7.56 (m, 9H; Harom), 7.98–
8.03 (m, 6H; Harom); 13C{1H} NMR (75.4 MHz, CDCl3):
d¼19.53 [(CH3)A], 20.11 [(CH3)B], 35.48 [(CH3)2CH],
36.75 (dd, 1J(C,P)¼45.8 Hz, 3J(C,P)¼12.2 Hz; CH2P),
50.12 [q, 2J(C,P)¼3.1 Hz; (CH3)2CHC], 57.42 (CH2N),
2
4
131.05 (d, J(C,P)¼9.3 Hz; oC-PhP), 131.50 (d, J(C,P)¼
4
2.3 Hz; pC-PhP), 132.68 (d, J(C,P)¼4.1 Hz), 140.07 (q),
150.99 (q), the resonance of the iC-PhP was not observed;
31P{1H} NMR (121.4 MHz, CDCl3): d¼2.68; IR (Nujol):
n¼1474 (CP), 1116 (NP) cmꢁ1; MS (FAB+): m/z (%)¼
1175 (45) [M++5], 1173 (89) [M++3], 1171 (100) [M++1];
C61H52Br3N4P3 (1173.73): calcd C 62.42, H 4.47, N 4.77;
found C 62.34, H 4.38, N 4.81.
4.6.3. Tri-l5-phosphazene 7e. Yield: 74%; mp 321–323 ꢀC
(yellow prisms from chloroform/diethyl ether); H NMR
1
(300 MHz, CDCl3): d¼ꢁ0.92 (pseudot, J(H,H)¼7.3 Hz,
3H; CH3), 0.18 (pseudoq, J(H,H)¼7.3 Hz, 1H; CH3CHAHB),
0.32 (pseudoq, J(H,H)¼7.3 Hz, 1H; CH3CHAHB), 2.86 (d,
J(H,H)¼12.3 Hz, 3H; CHAHBN), 3.41 (pseudoquint,
J(H,H),(H,P)¼8.1 Hz, 3H; CHAHBP), 3.45 (d, J(H,H)¼
12.3 Hz, 3H; CHAHBN), 3.97 (pseudot, J(H,H),(H,P)¼
15.2 Hz, 3H; CHAHBP), 6.36–6.38 (m, 3H; HAr), 6.47 (d,
J(H,H)¼6.8 Hz, 3H; Harom), 7.00–7.60 (m, 30H; Harom),
7.90–7.96 (m, 6H; Harom); 13C{1H} NMR (75.4 MHz,
CDCl3): d¼8.98 (CH3CH2), 33.48 (CH3CH2), 36.98 (m;
CH2P), 44.53 (q, 2J(C,P)¼3.5 Hz; CH3CH2C), 57.56
(CH2N), 118.40, 122.64 (d, 3J(C,P)¼12.7 Hz; s-cis-
CH]C–N]P), 125.41 (d, 3J(C,P)¼27.8 Hz; s-trans-
CH]C–N]P), 128.22 (d, 4J(C,P)¼4.0 Hz), 128.36 (d,
3
118.14, 122.75 (d, J(C,P)¼12.8 Hz; s-cis-CH]C–N]P),
125.49 (d, 3J(C,P)¼27.8 Hz; s-trans-CH]C–N]P),
3
128.21, 128.30 (d, J(C,P)¼13.3 Hz; mC-PhP), 128.71 (d,
3J(C,P)¼11.0 Hz; mC-PhP), 130.69 (br s; pC-PhP), 131.10
(d, 1J(C,P)¼90.7 Hz; iC-PhP), 131.28 (br s; pC-PhP),
2
2
131.63 (d, J(C,P)¼8.7 Hz; oC-PhP), 132.45 (d, J(C,P)¼
1
9.3 Hz; oC-PhP), 132.80 (d, J(C,P)¼105.1 Hz; iC-PhP),
141.63 (q), 151.33 (q); 31P{1H} NMR (121.4 MHz,
CDCl3): d¼3.50; IR (Nujol): n¼1459 (CP), 1109 (NP) cmꢁ1
;
MS (FAB+): m/z (%)¼979 (100) [M+]; C64H61N4P3 (979.12):
calcd C 78.51, H 6.28, N 5.72; found C 78.38, H 6.15, N 5.61.
3
3J(C,P)¼12.8 Hz; mC-PhP), 128.70 (d, J(C,P)¼11.0 Hz;
4
mC-PhP), 130.94 (d, J(C,P)¼1.2 Hz; pC-PhP), 131.41 (d,
4.6.6. Tri-l5-phosphazene 7h. Yield: 72%; mp (decomp.)
328–330 ꢀC (colourless prisms from chloroform/diethyl
ether); 1H NMR (300 MHz, CDCl3): d¼ꢁ0.31 [d,
J(H,H)¼7.1 Hz, 3H; (CH3)A], ꢁ0.06 [d, J(H,H)¼7.0 Hz,
3H; (CH3)B], 1.03 (m, 1H; CH), 3.17 (d, J(H,H)¼16.0 Hz,
3H; CHAHBN), 3.40 (d, J(H,H)¼16.0 Hz, 3H; CHAHBN),
3.75 (pseudoquint, J(H,H),(H,P)¼7.7 Hz, 3H; CHAHBP),
4.00 (pseudot, J(H,H),(H,P)¼16.3 Hz, 3H; CHAHBP), 6.83
(d, J(H,H)¼2.4 Hz, 3H; Harom), 6.97 (dd, J(H,H)¼8.7,
2.4 Hz, 3H; Harom), 7.12 (dt, J(H,H)¼7.6, 2.9 Hz, 6H;
Harom), 7.20 (dd, J(H,H)¼8.4, 1.8 Hz, 3H; Harom), 7.24–
7.33 (m, 9H; Harom), 7.38–7.41 (m, 9H; Harom), 7.98–8.04
(m, 6H; Harom); 13C{1H} NMR (75.4 MHz, CDCl3):
d¼19.66 [(CH3)A], 19.84 [(CH3)B], 35.58 [(CH3)2CH],
2
4J(C,P)¼1.0 Hz; pC-PhP), 131.61 (d, J(C,P)¼8.7 Hz; oC-
PhP), 131.86 (d, 1J(C,P)¼91.5 Hz; iC-PhP), 132.23 (d,
2J(C,P)¼9.3 Hz; oC-PhP), 132.51 (d, 1J(C,P)¼88.9 Hz; iC-
PhP), 141.80 (q), 151.24 (q); 31P{1H} NMR (121.4 MHz,
CDCl3): d¼2.17; IR (Nujol): n¼1451 (CP), 1117 (NP) cmꢁ1
;
MS (FAB+): m/z (%)¼988 (12) [M++Na], 966 (100) [M++1];
C63H59N4P3 (965.09): calcd C 78.40, H 6.16, N 5.81; found C
78.29, H 6.11, N 5.92.
4.6.4. Tri-l5-phosphazene 7f. Yield: 81%; mp (decomp.)
348–350 ꢀC (yellow prisms from dichloromethane/diethyl
1
ether); H NMR (300 MHz, CDCl3): d¼ꢁ0.79 (pseudot,
J(H,H)¼7.4 Hz, 3H; CH3), 0.30 (pseudoq, J(H,H)¼7.4 Hz,
1H; CH3CHAHB), 0.37 (pseudoq, J(H,H)¼7.4 Hz, 1H;
CH3CHAHB), 3.24 (d, J(H,H)¼14.4 Hz, 3H; CHAHBN),
3.45 (d, J(H,H)¼14.4 Hz, 3H; CHAHBN), 3.48 (m, 3H;
CHAHBP), 4.00 (pseudot, J(H,H),(H,P)¼15.3 Hz, 3H;
CHAHBP), 6.68 (d, J(H,H)¼2.4 Hz, 3H; Harom), 6.81 (dd,
J(H,H)¼8.7, 2.7 Hz, 3H; Harom), 7.17–7.39 (m, 27H; Harom),
7.89–7.95 (m, 6H; Harom); 13C{1H} NMR (75.4 MHz,
CDCl3): d¼9.12 (CH3CH2), 33.62 (CH3CH2), 37.23 (m;
CH2P), 44.75 (q, 2J(C,P)¼3.4 Hz; CH3CH2C), 56.95
(CH2N), 111.04 (q), 122.77 (d, 3J(C,P)¼11.6 Hz; s-cis-
2
37.73 (m; CH2P), 50.38 [q, J(C,P)¼3.3 Hz; (CH3)2CHC],
57.75 (CH2N), 110.17 (q), 121.51 (d, 3J(C,P)¼11.0 Hz;
3
s-cis-CH]C–N]P), 126.31 (d, J(C,P)¼27.2 Hz; s-trans-
CH]C–N]P), 128.36 (d, 3J(C,P)¼12.8 Hz; mC-PhP),
128.69 (d, 3J(C,P)¼10.4 Hz; mC-PhP), 130.63 (d,
2J(C,P)¼8.1 Hz; oC-PhP), 130.75 (br s; pC-PhP), 131.23,
131.47 (d, 1J(C,P)¼92.4 Hz; iC-PhP), 131.76 (d,
4
2J(C,P)¼9.3 Hz; oC-PhP), 133.30 (d, J(C,P)¼3.2 Hz; pC-
PhP), 133.81 (dleft; iC-PhP), 138.12 (q), 151.29 (q);
31P{1H} NMR (121.4 MHz, CDCl3): d¼0.88; IR (Nujol):