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M. Alajarꢀın et al. / Tetrahedron 63 (2007) 2078–2083
containing diethyl ether (15 ml) under nitrogen atmosphere
at room temperature over a period of 30 min with stirring.
The resulting mixture was then stirred for 3 h. The precipi-
tated pale yellow solid was filtered, washed with diethyl
ether (3ꢂ10 ml), and dried under vacuum.
4.4.1. Tri-l5-phosphazene 7a. Yield: 62%; mp (decomp.)
277–279 ꢀC (colorless prisms from chloroform/n-hexane);
1H NMR (300 MHz, CDCl3): d¼2.89 (d, J(H,H)¼12.0 Hz,
3H; CHAHBN), 3.48 (d, J(H,H)¼12.0 Hz, 3H; CHAHBN),
4.05 (pseudoquint, J(H,H),(H,P)¼7.5 Hz, 3H; CHAHBP),
4.26 (pseudot, J(H,H),(H,P)¼15.0 Hz, 3H; CHAHBP), 5.77
(t, J(H,H)¼8.0 Hz, 2H; Harom), 6.17 (d, J(H,H)¼8.0 Hz,
2H; Harom), 6.19 (t, J(H,H)¼6.0 Hz, 1H; Harom), 6.44–6.48
(m, 6H; Harom), 7.05–7.16 (m, 15H; Harom), 7.26–7.37 (m,
9H; Harom), 7.50–7.63 (m, 12H; Harom); 13C{1H} NMR
(75.4 MHz, CDCl3): d¼37.66 (ddd, 1J(C,P)¼46.4 Hz,
3J(C,P)¼8.8, 7.6 Hz; CH2P), 47.47 (q, 2J(C,P)¼4.6 Hz;
4.3.1. Triphosphazide 6a. Yield: 49%; mp>350 ꢀC (yellow
prisms from dichloromethane/diethyl ether); 1H NMR
(300 MHz, CDCl3): d¼3.49 (d, J(H,H)¼14.3 Hz, 3H;
CHAHBN), 3.86 (d, J(H,H)¼14.3 Hz, 3H; CHAHBN), 4.17
(pseudot, J(H,H),(H,P)¼14.8 Hz, 3H; CHAHBP), 4.22 (m,
3H; CHAHBP), 5.83 (t, J(H,H)¼6.9 Hz, 2H; Harom), 6.16 (t,
J(H,H)¼7.2 Hz, 1H; Harom), 6.66 (d, J(H,H)¼7.4 Hz, 2H;
Harom), 6.92–6.95 (m, 9H; Harom), 7.11–7.13 (m, 9H; Harom),
7.23–7.26 (m, 6H; Harom), 7.43 (t, J(H,H)¼9.0 Hz, 6H;
Harom), 7.53 (d, J(H,H)¼7.4 Hz, 3H; Harom), 7.66 (d,
J(H,H)¼9.2 Hz, 6H; Harom), 8.11 (br s, 3H; Harom);
13C{1H} NMR (75.4 MHz, CDCl3): d¼40.24 (m; CH2P),
3
CPh), 57.86 (CH2N), 118.48, 122.77 (d, J(C,P)¼12.8 Hz;
3
s-cis-CH]C–N]P), 125.46, 125.60 (d, J(C,P)¼27.8 Hz;
s-trans-CH]C–N]P), 126.12, 127.42, 128.14 (d, 4J(C,P)¼
4.1 Hz), 128.76 (d, 3J(C,P)¼10.4 Hz; mC–PhP), 130.91 (br
1
s; pC–PhP), 130.98 (d, J(C,P)¼91.0 Hz; iC–PhP), 131.52
(d, 2J(C,P)¼8.1 Hz; oC–PhP), 131.68 (br s; pC–PhP),
131.85 (d, 1J(C,P)¼87.2 Hz; iC–PhP), 131.92 (d,
2J(C,P)¼9.5 Hz; oC–PhP), 139.20 (q), 141.76 (q), 151.13
(q); 31P{1H} NMR (121.4 MHz, CDCl3): d¼4.32; IR
(Nujol): n¼1446 (CP), 1110 (NP) cmꢁ1; MS (FAB+): m/z
(%)¼1036 (18) [M++Na], 1014 (62) [M++1], 1013 (100)
[M+]; C67H59N4P3 (1013.13): calcd C 79.43, H 5.87, N
5.53; found C 79.30, H 5.92, N 5.66.
2
48.81 (q, J(C,P)¼3.9 Hz; PhC), 57.33 (CH2N), 118.80 (br
s), 119.20 (br s), 125.72, 126.26, 126.63, 128.24 (d,
3J(C,P)¼12.2 Hz; mC–PhP), 128.39, 128.49, 128.61 (d,
1J(C,P)¼81.3 Hz; iC–PhP), 128.67 (d, 3J(C,P)¼11.6 Hz;
mC–PhP), 130.89 (d, 1J(C,P)¼83.5 Hz; iC–PhP), 131.40 (d,
2J(C,P)¼9.3 Hz; oC–PhP), 131.45 (br s; pC–PhP), 131.57
(br s; pC–PhP), 132.87 (d, 2J(C,P)¼7.5 Hz; oC–PhP),
135.00 (q), 141.30 (q), 150.50 (q); 31P{1H} NMR
(121.4 MHz, CDCl3): d¼8.60 (br s, Dn1/2¼1105 Hz); IR (Nu-
jol): n¼1462 (CP), 1112 (NP) cmꢁ1; MS (FAB+): m/z (%)
1098 (19) [M++1], 700 (100); C67H59N10P3 (1097.17): calcd
C 73.34, H 5.42, N 12.77; found C 73.20, H 5.27, N 12.64.
4.4.2. Tri-l5-phosphazene 7b. Yield: 87%; mp (decomp.)
291–293 ꢀC (colorless prisms from dichloromethane/diethyl
ether); 1H NMR (300 MHz, CD2Cl2): d¼3.37 (d,
J(H,H)¼14.2 Hz, 3H; CHAHBN), 3.47 (d, J(H,H)¼14.2 Hz,
3H; CHAHBN), 4.01 (pseudoquint, J(H,H),(H,P)¼7.7 Hz,
3H; CHAHBP), 4.23 (pseudot, J(H,H),(H,P)¼15.1 Hz, 3H;
CHAHBP), 5.84 (t, J(H,H)¼8.4 Hz, 2H; Harom), 6.18 (d,
J(H,H)¼7.9 Hz, 2H; Harom), 6.26 (t, J(H,H)¼7.5 Hz, 1H;
Harom), 6.71 (t, J(H,H)¼2.6 Hz, 3H; Harom), 6.98 (dd,
J(H,H)¼8.7, 2.9 Hz, 3H; Harom), 7.15 (dt, J(H,H)¼7.3,
3.5 Hz, 6H; Harom), 7.24–7.29 (m, 12H; Harom), 7.37–7.45
(m, 9H; Harom), 7.59–7.66 (m, 6H; Harom); 13C{1H} NMR
(75.4 MHz, CD2Cl2): d¼39.03 (ddd, 1J(C,P)¼46.1 Hz,
3J(C,P)¼11.2, 4.1 Hz; CH2P), 47.95 (br s; PhC), 56.94
(CH2N), 111.40 (q), 123.35 (d, 3J(C,P)¼11.6 Hz; s-cis-
CH]C–N]P), 126.11, 126.66, 127.44 (d, 3J(C,P)¼
4.3.2. Triphosphazide 6b. Yield: 50%; mp 279–281 ꢀC
(yellow prisms from dichloromethane/diethyl ether); 1H
NMR (300 MHz, CD2Cl2): d¼3.76 (d, J(H,H)¼16.5 Hz,
3H; CHAHBN), 4.00 (d, J(H,H)¼16.5 Hz, 3H; CHAHBN),
4.16 (br d, J(H,H)¼12.3 Hz, 6H; CH2P), 5.84 (t,
J(H,H)¼7.6 Hz, 2H; Harom), 6.18 (t, J(H,H)¼7.6 Hz, 1H;
Harom), 6.69 (d, J(H,H)¼8.1 Hz, 2H; Harom), 6.93–6.97 (m,
6H; Harom), 7.14–7.31 (m, 18H; Harom), 7.45 (dd,
J(H,H)¼8.4, 1.7 Hz, 3H; Harom), 7.54 (d, J(H,H)¼8.4 Hz,
3H; Harom), 7.61–7.66 (m, 6H; Harom), 8.23 (br s, 3H; Harom);
13C{1H} NMR (75.4 MHz, CD2Cl2): d¼40.57 (m; CH2P),
49.32 (q, 2J(C,P)¼4.2 Hz; PhC), 58.52 (CH2N), 119.90 (br
s), 120.10 (q), 120.15 (br s), 126.76, 127.27, 127.78 (d,
1J(C,P)¼96.2 Hz; iC–PhP), 128.76 (d, 3J(C,P)¼11.6 Hz;
3
27.3 Hz), 127.55, 128.58 (d, J(C,P)¼12.8 Hz; mC–PhP),
129.18 (d, 3J(C,P)¼10.4 Hz; mC–PhP), 130.66 (d,
1J(C,P)¼65.5 Hz; iC–PhP), 131.36 (d, 2J(C,P)¼8.7 Hz;
oC–PhP), 131.48 (br s; pC–PhP), 131.67 (br s; pC–PhP),
132.04 (d, 2J(C,P)¼9.3 Hz; oC–PhP), 133.12 (d,
4J(C,P)¼2.9 Hz), 139.34 (q), 139.50 (q), 151.32 (q), the
resonance of one iC–PhP was not observed; 31P{1H} NMR
(121.4 MHz, CDCl3): d¼3.91; IR (Nujol): n¼1457 (CP),
1105 (NP) cmꢁ1; MS (FAB+): m/z (%)¼1250 (89) [M++4],
1248 (100) [M++2], 1246 (25) [M+]; C67H56Br3N4P3
(1249.82): calcd C 64.39, H 4.52, N 4.48; found C 64.27,
H 4.65, N 4.53.
3
mC–PhP), 128.84, 129.16 (d, J(C,P)¼12.2 Hz; mC–PhP),
129.81 (d, 1J(C,P)¼82.4 Hz; iC–PhP), 131.51 (d, 2J(C,P)¼
8.7 Hz; oC–PhP), 131.89 (br s; pC–PhP), 131.02 (br s;
pC–PhP), 133.09 (d, 2J(C,P)¼7.5 Hz; oC–PhP), 133.64,
134.59 (q), 139.85 (q), 149.91 (q); 31P{1H} NMR
(121.4 MHz, CD2Cl2): d¼7.50 (br s, Dn1/2¼639 Hz); IR
(Nujol): n¼1465 (CP), 1105 (NP) cmꢁ1; MS (FAB+): m/z
(%) 1334 (6) [M++4], 1332 (9) [M++2], 1330 (4) [M+],
700 (47), 154 (100); C67H56Br3N10P3 (1333.86): calcd C
60.33, H 4.23, N 10.50; found C 60.25, H 4.11, N 10.55.
4.4. General procedure for the preparation of
the tri-l5-phosphazenes 7
Acknowledgements
A solution of the corresponding triphosphazide 6 (1 mmol)
in CDCl3 (10 ml) was heated at 60 ꢀC in an oil bath for
24 h. After cooling, the solvent was removed under reduced
pressure and the crude product was crystallized.
This work was supported by the MEC and FEDER (Project
ꢀ
ꢀ
CTQ2005-02323/BQU) and Fundacion Seneca-CARM
(Project 00458/PI/04). J.B. also thanks the MEC for a fellow-
ship.