PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
ꢃ1
refluxed with drying pipe for 1 h. Then, the solvent was 13.95. IR (KBr) ꢀmax (cm ): 3440 (NH), 2965 (CH ), 1612
2
removed in vacuum and the resulting oil was purified by (Ar), 1261 (P ¼ O), 1201 (P–O–Ar), 754 (Ar–H). ESI MS
þ
þ
column chromatography on silica gel by using petroleum found m/z: 316.0 [M þ H] , 338.1 [M þ Na] , 653.1
þ
ether/ethyl acetate (v/v ¼ 1/1) as eluent to give the desired [2M þ Na] .
products 4a–n.
2
-Phenoxy-4H-spiro[benzo[e][1,4,2]oxazaphosphinine-
3,3-Dimethyl-2-phenoxy-3,4-
3,1’-cyclohexane] 2-oxide (4d)
dihydrobenzo[e][1,4,2]oxazaphosphinine 2-oxide (4a)
ꢀ
1
White solid, yield: 90%, m.p. 145–146 C. H NMR
ꢀ
1
Orange solid, yield 89%, m.p. 98–100 C.
H
NMR (400 MHz, CDCl ) d: 1.45–1.50 (m, 1H), 1.54–1.60 (m, 1H),
3
(
400 MHz, CDCl ) d: 1.51 (d, 3JP-H ¼ 16.0 Hz, 3H, –CCH ), 1.66–1.71 (m, 3H), 1.82–1.83 (m, 2H), 1.94–2.08 (m, 2H),
3
3
1
2
7
7
2
1
3
7
1
.63 (d, 3JP-H ¼ 16.8 Hz, 3H, –CCH ), 4.03 (d, 3J
¼
2.18–2.25 (m, 1H), 4.12 (d, 3JP-H ¼ 22.5 Hz, N–H),
6.81–6.85 (m, 2H), 6.97–7.02 (m, 2H), 7.15–7.19 (m, 3H),
3
P-H
3.50 Hz, 1H, N–H), 6.71–6.74 (m, 1H), 6.79 (t, J
.6 Hz, 1H), 6.93–6.97 (m, 2H), 7.12–7.17 (m, 3H), 7.30–7.34 (m, 2H). 13C NMR (100 MHz, CDCl ) d:
¼
H-H
3
.26–7.31 (m, 2H). 13C NMR (100 MHz, CDCl ) d: 23.1 (d, 19.7–20.3 (m), 24.97, 29.5–30.0 (m), 51.4 (d, JP-C
¼
3
JP-C ¼ 3.5 Hz), 23.6 (d, 2J
¼ 5.9 Hz), 49.1 (d, 1J
¼
144.4 Hz), 117.6, 119.1 (d, JP-C ¼ 8.7 Hz), 120.3 (d, J
¼
P-C
P-C
P-C
43.7 Hz), 117.4, 119.2 (d, 3J
¼ 6.8 Hz), 120.3, 120.5 (d, 1.3 Hz), 120.5 (d, JP-C ¼ 4.2 Hz), 124.6, 125.1, 129.7, 131.5
P-C
JP-C ¼ 4.2 Hz), 124.7, 125.2, 129.7, 132.0 (d, 3J
¼
¼
(d, JP-C ¼ 7.4 Hz), 140.7 (d, J
¼ 7.50 Hz), 150.2 (d, J
¼
P-C
P-C
P-C
31
.5 Hz), 140.4 (d, 2J
¼ 7.4 Hz), 150.2 (d, 2J
10.1 Hz). P NMR (162 MHz, CDCl ) d: 11.77. IR (KBr)
P-C
P-C
3
3
1
ꢃ1
0.1 Hz). P NMR (162 MHz, CDCl ) d: 13.57. IR (KBr) ꢀmax (cm ): 3439 (NH), 2935, 2857 (CH ), 1597 (Ar), 1253
3
2
ꢃ1
ꢀmax (cm ): 3439 (NH), 2978, 2928 (CH ), 1614 (Ar), 1264 (P ¼ O), 1192 (P–O–Ar), 748 (Ar–H). ESI MS found m/z:
3
þ
þ
þ
(
2
P ¼ O), 1199 (P–O–Ar), 736 (Ar–H). ESI MS found m/z: 330.0 [M þ H] , 352.1 [M þ Na] , 682.1 [2M þ Na] .
þ
þ
þ
90.1 [M þ H] , 312.1 [M þ Na] , 601.1 [2M þ Na] .
3
-Methyl-2-phenoxy-3-phenyl-3,4-
3-Ethyl-3-methyl-2-phenoxy-3,4-
dihydrobenzo[e][1,4,2]oxazaphosphinine 2-oxide (4e)
dihydrobenzo[e][1,4,2]oxazaphosphinine 2-oxide (4b)
ꢀ
1
White solid, yield: 87%, m.p. 161–162 C. H NMR
White solid, yield: 89%, m.p. 90–93 C. H NMR (400 MHz, (400 MHz, CDCl ) d: 1.93 (d, 3J
¼ 16.8 Hz, 3H, CH ),
ꢀ
1
3
P-H
3
CDCl ) d: 0.98–1.22 (m, 3H, CCH CH ), 1.51 (q, 3J
¼
4.42 (d, 3JP-H ¼ 20.2 Hz, 1H, N–H), 6.76 (t, J
¼7.84 Hz,
3
2
3
P-H
P-H
1
6.4 Hz, 3H, CCH ), 1.85–2.21 (m, 2H, CCH CH ), 3.91 (d, 1H), 6.82–6.90 (m, 2H), 7.00–7.04 (m, 1H), 7.12–7.16 (m,
3 2 3
3
JP-H ¼ 29.76 Hz, 1H, N–H), 6.74–6.78 (m, 1H), 6.79–6.85 3H), 7.26–7.34 (m, 5H), 7.64–7.67 (m, 2H). 13C NMR
¼ 4.1 Hz), 56.0 (d, J ¼
(m, 1H), 6.95–7.00 (m, 2H), 7.16–7.20 (m, 3H), 7.30–7.34 (t, (100 MHz, CDCl ) d: 25.3 (d, J
3
P-C
P-C
JP-H ¼ 7.72 Hz, 2H). 13C NMR (100 MHz, CDCl ) d: 6.2 (d, 141.3 Hz), 116.5, 119.5 (d, JP-C ¼ 6.7 Hz), 120.0, 120.6 (d, J
3
P-
JP-C ¼ 10.4 Hz), 7.9 (d, J
¼ 6.8 Hz), 19.0 (d, J
¼
¼ 4.2 Hz), 125.1, 125.3, 126.7 (d, J
¼ 4.8 Hz), 128.0 (d,
P-C
P-C
C
P-C
4
.1 Hz), 20.0 (d, J
¼ 5.7 Hz), 7.2 (d, J
¼ 6.2 Hz), 29.2
J
¼ 2.3 Hz), 128.6 (d, J
¼ 2.0 Hz), 129.7, 132.7 (d,
P-C
P-C
P-C
P-C
(
2
d, JP-C ¼ 2.4 Hz), 52.5 (m), 117.1, 117.5, 119.0 (d, J
¼
J ¼ 8.6 Hz), 139.4 (d, J
¼ 3.8 Hz), 140.1 (d, J
¼
P-C
P-C
P-C
31
.6 Hz), 119.1 (d, J
¼ 2.3 Hz), 120.0, 120.2, 120.6 (d, J
7.2 Hz), 150.2 (d, J
¼ 10.2 Hz). P NMR (162 MHz,
P-C
P-C
P-C
ꢃ1
¼
4.2 Hz), 124.7 (d, JP-C ¼ 4.6 Hz), 125.2 (d, J
¼ 4.3 Hz), CDCl ) d: 8.22. IR (KBr) ꢀ
(cm ): 3439 (NH), 2936
P-C
3
max
1
1
29.7, 131.9 (d, JP-C ¼ 7.6 Hz), 132.0 (d, J
¼ 7.3 Hz), (CH ), 1612 (Ar), 1263 (P ¼ O), 1192 (P–O–Ar), 751
P-C
3
þ
40.2 (d, JP-C ¼ 7.3 Hz), 140.5 (d, J
¼ 7.5 Hz), 150.1 (d, (Ar–H). ESI MS found m/z: 352.1 [M þ H] , 374.1
P-C
31
þ
þ
JP-C ¼ 7.6 Hz), 150.2 (d, J
¼ 7.6 Hz).
P NMR [M þ Na] , 725.2 [2M þ Na] .
P-C
ꢃ1
(162 MHz, CDCl ) d: 12.77, 12.44. IR (KBr) ꢀ
(cm ):
3
max
3
439 (NH), 2972, 2934 (CH , C H ), 1611 (Ar), 1262
3 2 5
3
-(4-Methoxyphenyl)-3-methyl-2-phenoxy-3,4-
(P ¼ O), 1197 (P–O–Ar), 744 (Ar–H). ESI MS found m/z:
þ
þ
þ
dihydrobenzo[e][1,4,2]oxazaphosphinine 2-oxide (4f)
3
04.1 [M þ H] , 326.1 [M þ Na] , 629.2 [2M þ Na] .
ꢀ
1
White solid, yield: 85%, m.p. 142–144 C. H NMR
(
3
6
400 MHz, CDCl ) d: 1.91 (d, 3J
¼ 16.8 Hz, 3H, –CCH ),
3
P-H
3
2
3
-Phenoxy-4H-spiro[benzo[e][1,4,2]oxazaphosphinine-
,1’-cyclopentane] 2-oxide (4c)
.75 (s, 3H, –OCH ), 4.45 (d, 3J
¼ 20.88 Hz, 1H, N–H),
3
P-H
.75–6.77 (m, 1H), 6.82–6.88 (m, 4H), 6.98–7.00 (m, 1H),
ꢀ
1
White solid, yield: 90%, m.p. 123–124 C. H NMR 7.11–7.16 (m, 3H), 7.25–7.29 (m, 2H), 7.54–7.57 (m, 2H).
(
400 MHz, CDCl ) d: 1.79–1.80 (m, 6H), 2.20–2.26 (m, 1H), 13C NMR (100 MHz, CDCl ) d: 25.2 (d, J
¼ 3.66 Hz),
3
3
P-C
2
6
1
.46–2.52 (m, 1H), 4.39 (s, 1H, N–H), 6.72–6.79 (m, 2H), 55.0 (d, JP-C ¼ 49.6 Hz), 56.2, 114.0 (d, J
¼ 2.0 Hz),
P-C
.89–6.95 (m, 2H), 7.10–7.17 (m, 3H), 7.24–7.28 (m, 2H). 116.5, 119.4, 119.4, 119.8, 120.6 (d, J
¼ 4.2 Hz), 125.0,
P-C
3C NMR(100 MHz, CDCl ) d: 24.2–24.6(m), 34.6, 35.1 (d, 125.2, 128.0 (d, JP-C ¼ 4.8 Hz), 129.7, 131.3 (d, J
¼
3
P-C
JP-C ¼ 9.1 Hz), 58.7 (d, J
¼147.3 Hz), 117.9, 119.2 (d, J
3.5 Hz), 132.9 (d, J ¼ 8.5 Hz), 140.0 (d, J
¼ 7.2 Hz), 115.2
31
P-C
P-C
P-C
¼
6.7 Hz), 120.2, 120.7 (d, J
¼ 4.1 Hz), 124.5, 125.2, (d, J ¼ 10.1 Hz), 159.2 (d, J
¼ 2.5 Hz).
P NMR
P-C
P-C
ꢃ1
1
1
29.6, 132.5 (d, JP-C ¼ 6.9 Hz), 140.9 (d, J
¼ 7.3 Hz), (162 MHz, CDCl ) d: 8.70. IR (KBr) ꢀ
(cm ): 3439
max
P-C
3
3
1
50.3 (d, JP-C ¼ 9.7 Hz). P NMR (162 MHz, CDCl ) d: (NH), 2935 (CH ), 1611 (Ar), 1261 (P ¼ O), 1195 (P–O–Ar),
3
3