Page 29 of 73
The Journal of Organic Chemistry
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6H), 7.64‒7.70 (m, 4H); C NMR (126 MHz, CDCl
3
) δ 22.8, 25.5 (d, JP‒C = 37.2 Hz), 26.5,
2
1
8.2, 30.8 (d, JP‒C = 13.6 Hz), 32.4, 44.9, 128.7 (d, JP‒C = 10.0 Hz), 129.6 (d, JP‒C = 54.5 Hz),
3
1
b
31.0 (d, JP‒C = 2.7 Hz), 132.0 (d, JP‒C = 9.08 Hz); P NMR (202 MHz, CDCl
3
) δ 15.82. GC
t
R
= 13.13 min; GCꢀMS (EI, 70 eV) m/z = 318 (M‒BH ) (1.45), 284 (21), 283 (100), 269 (7),
3
2
55 (13), 245 (7), 241 (12), 235 (5), 234 (13), 233 (11), 222 (8), 220 (24), 213 (19), 200 (20),
99 (88), 187 (5), 186 (31), 185 (18), 184 (9), 183 (63), 157 (5), 152 (13), 133 (8), 124 (5),
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121 (24), 115 (6), 109 (25), 108 (75), 107 (25), 91 (30), 83 (5). HRMS (ESIꢀTOF) m/z:
+
[
M‒3H] Calcd for C19
H24BPCl 329.1389; Found 329.1391.
(4ꢀChlorobutyl)diꢀoꢀtolylphosphine sulfide (23a). This compound was prepared according
to General Procedure from methyldi(oꢀtolyl)phosphine sulfide 19 (0.207 g, 0.79 mmol),
n‒BuLi (0.75 ml, 1.6 M in hexanes, 1.19 mmol), and 1ꢀbromoꢀ3ꢀchloropropane (0.188 g, 1.19
o
mmol) as a white solid, yield: 0.185 g (69%); mp = 128.1‒129.4 C; R 0.39 (hexane/EtOAc,
f
1
8
:1); H NMR (500 MHz, CDCl
3
) δ 1.61‒1.72 (m, 2H), 1.88 (p, JH‒H = 6.94 Hz, 2H), 2.09 (s,
6H), 2.60‒2.67 (m, 2H), 3.50 (t, JH‒H = 6.62 Hz, 2H), 7.14‒7.20 (m, 2H), 7.34‒7.45 (m, 4H),
13
8.09‒8.16 (m, 2H); C NMR (126 MHz, CDCl ) δ 19.7, 21.3 (d, J = 5.4 Hz), 30.7 (d, JP‒C
3
P‒C
=
57.2 Hz), 33.3 (d, JP‒C = 16.3 Hz), 44.0, 126.2 (d, JP‒C = 11.8 Hz), 130.6 (d, JP‒C = 77.2 Hz),
131.7 (d, JP‒C = 2.7 Hz), 132.0 (d, JP‒C = 10.9 Hz), 132.4 (d, JP‒C = 11.8 Hz), 140.2 (d, JP‒C
=
3
1
d
9.1 Hz); P NMR (202 MHz, CDCl3) δ 40.12; GC t
R
= 21.89 min; GCꢀMS (EI, 70 eV) m/z
=
336 (M) (4), 301 (30), 269 (23), 247 (11), 246 (66), 245 (12), 231 (15), 213 (11), 212 (16),
211 (10), 197 (10), 196 (10), 179 (12), 165 (17), 154 (16), 153 (40), 152 (14), 133 (10), 123
+
(9), 122 (11), 121 (22), 92 (9), 91 (100); HRMS (ESIꢀTOF) m/z: [M+H] Calcd for
C
18
H22PSCl 337.0941; Found 337.0936.
(5ꢀChloropentyl)diꢀoꢀtolylphosphine sulfide (23b). This compound was prepared according
to General Procedure from methyldi(oꢀtolyl)phosphine sulfide 19 (0.214 g, 0.82 mmol),
n‒BuLi (0.77 ml, 1.6 M in hexanes, 1.23 mmol), and 1ꢀbromoꢀ4ꢀchlorobutane (0.211 g, 1.23
o
mmol) as a white solid, yield: 0.219 g (76%); mp = 130.2‒131.2 C; R 0.41 (hexane/EtOAc,
f
1
8:1); H NMR (500 MHz, CDCl
3
) δ 1.48‒1.58 (m, 2H), 1.71‒1.78 (m, 2H), 2.08 (s, 6H),
2.57‒2.65 (m, 2H), 3.48 (t, JH‒H = 6.62 Hz, 2H), 7.13‒7.18 (m, 2H), 7.34‒7.44 (m, 4H),
1
3
8
.10‒8.16 (m, 2H); C NMR (126 MHz, CDCl ) δ 21.3 (d, J = 4.5 Hz), 21.4 (d, JP‒C = 1.8
3
P‒C
Hz), 28.0 (d, JP‒C = 17.3 Hz), 31.3 (d, JP‒C = 57.2 Hz), 32.0, 44.7, 126.2 (d, JP‒C = 12.7 Hz),
130.7 (d, JP‒C = 77.2 Hz), 131.6 (d, JP‒C = 3.6 Hz), 132.0 (d, JP‒C = 10.0 Hz), 132.4 (d, JP‒C =
31
d
1
1.8 Hz), 140.2 (d, JP‒C = 8.2 Hz); P NMR (202 MHz, CDCl3) δ 40.12; GC t = 23.26 min;
R
GCꢀMS (EI, 70 eV) m/z = 350 (M) (4), 315 (20), 284 (10), 247 (13), 246 (80), 245 (10), 231
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