258 Inorganic Chemistry, Vol. 50, No. 1, 2011
Kumar et al.
Preparation of [(CH2dCHCH2O)2PN]3 (2). The reaction of
allyl alcohol (3.13 mL, 46.02 mmol), NaH (2.00 g, 46.02 mmol),
and N3P3Cl6 (2.00 g, 5.75 mmol) was carried out and worked up
in a manner similar to that of compound 1, with stirring at room
temperature for 24 h followed by refluxing for 8 h. Compound 2
came out as a yellowish viscous liquid while using a 3% ethyl
acetate/hexane mixture as the eluent. Yield: 2.10 g (78%). IR (ν,
cm-1): 3085 s, 2935 s, 2879 s, 2734 w, 2879 s, 2073 w, 1954 m,
1875 m, 1648 s, 1457 s, 1419 s, 13661 m, 1228 vs, 1160 m, 1028 vs.
1H NMR (CDCl3, ppm): δ 5.88-6.00 (m, 6H, dCH-), 5.34 [d
(J = 17 Hz), 6H, trans -CHdCH2], 5.19 [d (J = 10.5 Hz), 6H,
cis -CHdCH2], 4.46 (s, 12H, -CH2-). 13C{1H} NMR: δ
132.86 [dCH-], 116.82 [CH2d], 66.18 [-CH2-]. 31P{1H}
NMR: δ 17.85 [s, P(OCH2CHdCH2)2]. MS (ES) [m/e (species)]:
478.10 [M þ 1]þ.
4H, -CH2- (toward SdO)], 4.40 [s, 4H, -CH2- (toward Ph)].
13C{1H} NMR: δ 146.55, 131.46, 128.58, 125.09 [PhC], 132.21
[dCH-], 118.00 and 118.27 [CH2d], 67.54 [-CH2-]. 31P{1H}
NMR: δ 11.37 [s, P(OCH2CHdCH2)2]. MS (ES) [m/e (species)]:
458.08 [M þ 1]þ.
Preparation of (NS(O)Ph)[NP(OCH2CHdCHCH2O)]2 (8).
The reaction of 4 (0.80 g, 1.74 mmol) and the Grubbs first-
generation catalyst (0.14 g, 0.014 mmol, 10 mol %) was carried out
and worked up in a manner similar to that of compound 5, with
refluxing for 8 h. The dispirocyclic compound 8 came out as a white
crystalline solid while using a 20% ethyl acetate/hexane mixture as
the eluent. Yield: 0.40 g (60%). Mp: 123-125 °C. IR (ν,cm-1): 2926
m, 2356 w, 1731 w, 1634 w, 1453 s, 1253 vs, 1181 vs, 1077 s, 1039 vs,
1
1001 vs. H NMR (CDCl3, ppm): δ 7.90-7.93 (m, 2H, C6H5),
7.41-7.50 (m, 3H, C6H5), 5.74 (s, 4H, dCH), 4.54-4.93 (m,
8H, -CH2-). 13C{1H} NMR: δ 146.52, 131.37, 128.61, 125.06
[PhC], 127.04 and 126.31 [-CHd], 63.63 and 63.90 [-CH2-].
31P{1H} NMR: δ 17.12 [s, spiro P]. MS (ES) [m/e (species)]: 402.04
[M þ 1]þ. Anal. Calcd for C20H22N3O4P3: C, 41.90; H, 4.27; N,
10.47. Found: C, 42.30; H, 4.84; N, 10.02.
Preparation of N3P3(OCH2CHdCHCH2O)3 (6). The reaction
of 2 (0.65 g, 1.46 mmol) and the Grubbs first-generation catalyst
(0.24 g, 0.29 mmol, 20 mol %) was carried out and worked up in a
manner similar to that of compound 5 with refluxing for 12 h.
Trispirocyclic compound 6 came out as a white crystalline solid
while using a 45% ethyl acetate/hexane mixture as the eluent. Yield:
0.35 g (65%). Mp (dec): 135-138 °C. IR (ν, cm-1): 3036 w, 2958 m,
2925 m, 2877 m, 2360 w, 2104 w, 1734 m, 1628 m, 1461 s, 1244 vs,
Preparation of (NPPh2)[NP(OCH2CH2CHdCH2)2]2 (9). The
reaction of homoallyl alcohol (1.49 mL, 17.40 mmol), NaH
(0.76 g, 17.40 mmol), and N3P3Cl4Ph2 (1.50 g, 3.48 mmol) was
carried out and worked up in a manner similar to that of
compound 1, with stirring at room temperature for 24 h.
Compound 9 came out as a yellowish viscous liquid while using
a 2% ethyl acetate/hexane mixture as the eluent. Yield: 1.40 g
(70%). IR (ν, cm-1): 3075 s, 2954 s, 2895 s, 1908 w, 1834 w, 1641
s, 1593 w, 1474 s, 1436 s, 1384 m, 1207 vs, 1122 vs, 1026 vs. 1H
NMR (CDCl3, ppm): δ 7.80-7.87 (m, 4H, C6H5), 7.34-7.46 (m,
6H, C6H5), 5.66-5.80 (m, 4H, dCH-), 4.98-5.05 (m, 8H,
dCH2], 3.85-3.97 (m, 8H, -OCH2-), 2.36 [q (J = 6.9 Hz),
8H, -CH2-]. 13C{1H} NMR: δ 136.97, 130.88, 130.49, 128.08
[PhC ], 134.08 [dCH-], 116.88 [dCH2], 64.82 [-OCH2-], 34.57
[-CH2]. 31P{1H} NMR: δ 20.87 [t (J = 33.65 Hz), P(C6H5)2],
15.54 [d (J = 33.65 Hz), P(OCH2CH2CHdCH2)2]. MS (ES) [m/
e (species)]: 574.21 [M þ 1]þ.
1
1047 vs, 1007 s. H NMR (CDCl3, ppm): δ 5.74 (s, 6H, dCH),
4.71-4.73 (m, 12H, -CH2-). 13C{1H} NMR: δ 127.00 [-CHd],
63.14 [-CH2-]. 31P{1H} NMR: δ 22.99 [s, spiro P]. MS (ES) [m/e
(species)]: 394.02 [M þ 1]þ. Anal. Calcd for C12H18N3O6P3: C,
36.65; H, 4.61; N, 10.69. Found: C, 37.10; H, 4.65; N, 10.41.
Preparation of [(CH2dCHCH2O)2PN]4 (3). The reaction of
allyl alcohol (1.46 mL, 21.57 mmol), NaH (0.94 g, 21.57 mmol),
and N4P4Cl8 (1.00 g, 2.15 mmol) was carried out and worked up
in a manner similar to that of compound 1, stirring at room
temperature for 24 h followed by refluxing for 6 h. Compound 3
came out as a yellowish viscous liquid while using a 2% ethyl
acetate/hexane mixture as the eluent. Yield: 1.00 g (73%). IR (ν,
cm-1): 3084 m, 2934 m, 2879 m, 2362 w, 1868 w, 1647 m, 1456 m,
1325 s, 1102 s, 1030 vs. 1H NMR (CDCl3, ppm): δ 5.87-6.00 (m,
6H, dCH-), 5.31 [d (J = 17 Hz), 8H, trans -CHdCH2], 5.16 [d
(J = 10.2 Hz), 8H, cis -CHdCH2], 4.47 (s, 16H, -CH2-).
13C{1H} NMR: δ 133.77 [dCH-], 116.72 [dCH2], 66.84
[-CH2-]. 31P{1H} NMR: δ 0.41 [s, P(OCH2CHdCH2)2]. MS
(ES) [m/e (species)]: 637.17 [M þ 1]þ.
Preparation of (NS(O)Ph)[NP(OCH2CH2CHdCH2)2]2 (10).
The reaction of homoallyl alcohol (1.52 mL, 17.80 mmol), NaH
(0.85g, 17.80mmol), andS-phenylthionylphosphazene (NS(O)Ph)-
(NPCl2)2 (1.10 g, 2.96 mmol) was carried out and worked up in a
manner similar to that of compound 1, with stirring at room
temperature for 24 h. Compound 10 came out as a yellow viscous
liquid while using a 3% ethyl acetate/hexane mixture as the eluent.
Yield: 0.85 g (56%). IR (ν, cm-1): 3076 m, 2960 s, 2925 s, 2856 m,
1731 w, 1641 m, 1471 m, 1439 m, 1234 vs, 1180 vs, 1024 vs. 1HNMR
(CDCl3, ppm): δ 7.91-7.95 (m, 2H, C6H5), 7.40-7.51 (m, 3H,
C6H5), 5.72-5.88 [m, 2H, dCH- (toward SdO)], 5.60-5.72 [m,
2H, dCH- (toward Ph)], 5.01-5.18 (m, 8H, CH2d), 4.02-4.16
[m, 4H, -OCH2- (toward SdO) ], 3.87-3.94 [m, 4H, -OCH2-
(toward Ph)], 2.48 [q (J = 6.6 Hz), 4H, -CH2- (toward SdO)],
2.33 [q (J = 6.6 Hz), 4H, -CH2- (toward Ph)]. 13C{1H} NMR: δ
146.45, 131.36, 128.53, 125.09 [PhC], 133.44 and 133.32 [dCH-],
117.50 and 117.61 [dCH2], 66.07 and 66.11 [-OCH2-], 34.28
[-CH2]. 31P{1H} NMR: δ 10.93 [s, P(OCH2CH2CHdCH2)2].
MS (ES) [m/e (species)]: 514.16 [M þ 1]þ.
Preparation of N4P4(OCH2CHdCHCH2O)4 (7). The reaction
of 3 (0.50 g, 0.78 mmol) and the Grubbs first-generation catalyst
(0.16 g, 0.19 mmol, 25 mol %) was carried out and worked up in a
manner similar to that of compound 5 with refluxing carried out for
14 h. Tetraspirocyclic compound 7 came out as a white crystalline
solid while using a 55% ethyl acetate/hexane mixture as the eluent.
Yield: 0.30 g (73%). Mp: 165-168 °C. IR (ν, cm-1): 3036 m, 2922 s,
2866 s, 1947 w, 1731 m, 1454 m, 1323 s, 1259 vs, 1220 w, 1042 vs. 1H
NMR (CDCl3, ppm): δ5.69 (s, 8H, dCH), 4.62 (m, 16H, -CH2-).
13C{1H} NMR: δ 127.42 [-CHd], 63.32 [-CH2-]. 31P{1H}
NMR: δ 7.16 [s, spiro P]. MS (ES) [m/e (species)]: 525.08
[M þ 1]þ. Anal. Calcd for C16H24N4O8P4: C, 36.65; H, 4.61; N,
10.69. Found: C, 36.82; H, 4.53; N, 10.65.
Preparation of [PhS(O)N][(CH2dCHCH2O)2PN]2 (4). The reac-
tion of allyl alcohol (1.01 mL, 14.80 mmol), NaH (0.65 g, 14.80
mmol), and S-phenylthionylphosphazene (NS(O)Ph)(NPCl2)2
(1.10 g, 2.96 mmol) was carried out and worked up in a manner
similar to that of compound 1, with stirring at room temperature for
24 h. Compound 4 came out as a yellow viscous liquid, while using a
8% ethyl acetate/hexane mixture as the eluent. Yield: 1.10 g (89%).
IR (ν, cm-1): 3083 m, 2930 s, 2357 m, 2108 w, 1887 w, 1741 w, 1647
Reaction of Compound 9 with 10 mol % of the Grubbs First-
Generation Catalyst. The reaction of 9 (0.50 g, 0.87 mmol) and
the Grubbs first-generation catalyst (71 mg, 0.08 mmol, 10 mol
%) was carried out and worked up in a manner similar to that of
compound 5, with refluxing for 10 h. The diansa compound
NPPh2[NP(OCH2CH2CHdCHCH2CH2O)]2 (11) came out as a
white crystalline solid while using a 5% ethyl acetate/hexane
mixture as the eluent. Yield: 0.11 g (24%). IR (ν, cm-1): 3046 m,
2956 s, 2901 s, 1730 m, 1596 w, 1436 s, 1222 vs, 1124 s, 1070 vs,
1038 vs, 1003 vs. 1H NMR (CDCl3, ppm): δ 7.86-7.93 (m, 4H,
C6H5), 7.44 (m, 6H, C6H5), 5.34-5.38 (s, 4H, dCH), 4.04-4.06
(m, 8H, -OCH2-), 2.25 (s, 4H, -CH2-), 2.14 (s, 4H, -CH2-).
13C{1H} NMR: δ 137.05, 130.94, 130.65, 128.14 [PhC ], 129.85
1
m, 1454 m, 1367 w, 1234 vs, 1178 s, 1100 vs, 1026 vs. H NMR
(CDCl3, ppm): δ 7.91-7.95 (m, 2H, C6H5), 7.41-7.48 (m, 3H,
C6H5), 5.87-6.00 [m, 2H, dCH- (toward SdO)], 5.68-5.85 [m,
2H, dCH- (towardPh)],5.39[d(J=17Hz),2H,transCH2dCH-
(toward SdO)], 5.25 [d (J = 9.6 Hz), 2H, cis CH2dCH-
(toward SdO)], 4.87-5.26 [m, 4H, CH2d (toward Ph)], 4.57 [s,