PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
9
3
1
5
3.31 (C20 & C21); P NMR (CDCl , 161.7 MHz) d: 22.06; Tetramethyl(((4-(4-fluorophenyl)thiazol-2-yl)amino)methy-
3
þ
ESI-MS m/z: 437 [M þ H] ; Anal. calcd for C H N O P S lene)bis(phosphonate) (5h)
15
22 2 7 2
ꢁ
C, 41.32; H, 5.12; N, 6.82; Found: C, 41.24; H, 5.09; N, 6.76. White solid; Yield: 92%; Mp: 126–129 C; IR (KBr) (ꢀmax,
ꢂ1
1
cm ): 3352(NH), 1213(P ¼ O), 818 (P-C
); HNMR
Aliphatic
(
CDCl , 400 MHz) d: 7.92–7.43 (4H, m, Ar-H), 7.32 (1H, s,
3
Tetraethyl(((4-(4-methoxyphenyl)thiazol-2-yl)amino)methy- Ar-H), 5.18 (1H, s, -NH), 3.64 (6H, d, J ¼ 10.6 Hz, P-
lene)bis(phosphonate) (5e)
OCH ), 3.51 (6H, d, J ¼ 10.4 Hz, P-OCH ), 2.54 (1H, d,
3
3
ꢁ
13
Pale Yellow solid; Yield: 90%; Mp: 123–125 C, IR (KBr) J ¼ 22 Hz, P-C-H); C(CDCl3 100 MHz) d: 164.45 (C11),
,
ꢂ1
(
ꢀmax, cm ): 3213 (NH), 1244 (P ¼ O), 830(P-CAliphatic); 162.91 (C2), 152.45 (C7), 131.43 (C6), 131.32 (C4), 130.26
1
HNMR (CDCl , 400 MHz) d: 7.74–7.72 (2H, m, Ar-H), (C5), 116.45 (C1), 116.32(C3), 105.21 (C9), 69.34 (C14),
3
31
6
.92–6.90 (1H, s, Ar-H), 6.60–6.54 (2H, m, Ar-H), 5.60 (1H, 53.34 (C17 & C22), 53.12 (C20 & C21); P NMR (CDCl3,
þ
s, -NH), 4.40–4.01 (H, m, -POCH CH ), 3.65 (3H, s, 161.7 MHz) d: 20.32; ESI-MS m/z: 425 [M þ H] ; Anal.
2
3
-
-
(
OCH ), 2.42 (1H, d, J ¼ 22 Hz, P-C-H), 1.46–0.88 (12H, t, calcd for C14
H19FN
2
O
6
P
2
S C, 39.62; H, 4.53; N, 6.60; Found:
3
1
3
POCH CH ); C(CDCl , 100 MHz) d: 166.35 (C11), 159.32 C, 39.58; H, 4.42; N, 6.56.
2
3
3
C2), 150.44 (C7), 127.69 (C4), 127.50 (C6), 113.92 (C1),
1
6
13.54 (C3), 100.24 (C9), 64.01 (C14), 63.75 (C23 & C25)
3.46, 63.31 (C27 & C29), 55.35 (C8), 16.57, 16.39 (C24 &
Tetraethyl(((4-(4-fluorophenyl)thiazol-2-yl)amino)methyle-
ne)bis(phosphonate) (5i)
31
C26), 16.30, 16.01 (C28 & C30);
P NMR (CDCl ,
ꢁ
3
Yellow solid; Yield: 94%; Mp: 125–128 C; IR (KBr) (ꢀmax,
þ
1
61.7 MHz) d: 23.06; ESI-MS m/z: 493 [M þ H] ; Anal.
ꢂ1
1
cm ): 3346 (NH), 1242(P ¼ O), 832 (P-C
); HNMR
Aliphatic
calcd for C H N O P S C, 46.35; H, 6.15; N, 5.69; Found:
1
9
30 2 7 2
(
CDCl , 400 MHz) d: 7.65–7.48 (4H, s, Ar-H), 7.32 (1H, s,
3
C, 45.23; H, 6.03; N, 5.62.
Ar-H), 5.42 (1H, s, -NH), 4.65–4.61 (8H, m, POCH CH ),
2
3
3
.42 (12H, t, P-OCH CH ), 2.1 (1H, d, J ¼ 28 Hz, P-C-H),
2
3
1
3
C(CDCl , 100 MHz) d: 163.43 (C11), 151.06 (C7), 131.45
3
Tetrabutyl(((4-(4-methoxyphenyl)thiazol-2-yl)amino)methy-
lene)bis(phosphonate) (5f)
(
1
6
C5), 130.34 (C1), 130.23 (C3), 127.45 (C4), 126.42 (C6),
21.32 (C2), 105.42 (C9), 69.84 (C14), 66.85 (C23 & C25),
2.81 (C27 & C29), 16.45 (C24 & C26), 16.34 (C28 & C30);
ꢁ
Pale Yellow solid; Yield: 85%; Mp: 140–144 C; IR (KBr) (ꢀmax,
ꢂ1
1
cm ): 3246 (NH), 1246 (P ¼ O), 838 (P-C
); HNMR 31
Aliphatic
PNMR (CDCl3 161.7 MHz) d: 21.65; ESI-MS m/z: 481
,
(
CDCl , 400 MHz) d: 7.79–7.76 (2H, m, Ar-H), 7.24 (1H, s, Ar-
þ
3
[
5
M þ H] ; Anal. calcd for C H FN O P S C, 45.32; H,
18
27
2 6 2
H), 6.94–6.69 (2H, m, Ar-H), 5.67 (1H, s, -NH), 4.48–4.20 (8H,
.64; N, 5.83; Found: C, 45.28; H, 5.62; N, 5.78.
m, -POCH CH CH CH ), 3.86 (3H, s, -OCH ), 2.42 (1H, d,
2
2
2
3
3
J ¼ 28 Hz, P-C-H), 1.89–1.72 (8H, m, -POCH CH CH CH ),
2
2
2
3
Tetramethyl(((4-(4-bromophenyl)thiazol-2-yl)amino)methy-
lene)bis(phosphonate) (5j)
1
.46–1.35 (8H, m, -POCH CH CH CH ), 0.88–0.70 (12H, m,
2 2 2 3
13
-
POCH CH CH CH ); C(CDCl , 100 MHz) d: 165.36 (C11),
2 2 2 3 3
ꢁ
Yellow solid; Yield: 88%; Mp: 136–139 C; IR (KBr) (ꢀmax,
1
1
60.30 (C2), 150.40 (C7), 127.94 (C6), 127.40 (4), 125.63 (C5),
14.52(C1), 114.34 (C3), 103.24 (C9), 72.52 (C14), 66.52 (C21,
ꢂ1
1
cm ): 3295 (NH), 1256 (P ¼ O), 817 (P-C
); HNMR
Aliphatic
(
CDCl , 400 MHz) d: 7.83–7.54 (4H, m, Ar-H), 7.27 (1H, s,
C25, C29 & C35), 57.36 (C8), 31.73 (C22, C26, C30 & C36),
3
31
Ar-H), 5.25 (1H, s, -NH), 3.56 (6H, d, J ¼ 9.8 Hz, P-OCH ),
3
1
8.46 (C23, C27, C31 & C37), 13.17 (C24, C28, C32 & C33); P
3
.43 (6H, d, J ¼ 9.6 Hz P-OCH ), 2.73 (1H, d, J ¼ 22 Hz, P-
13
3
NMR (CDCl , 161.7 MHz) d: 24.32; ESI-MS m/z: 605
3
þ
C-H); C(CDCl3 100 MHz) d: 165.32 (C11), 151.23 (C7),
,
[
4
M þ H] ; Anal. calcd for C H N O P S C, 53.23; H, 7.12; N,
2
7
46 2 7 2
1
32.32 (C1), 132.29 (C3), 132.26 (C5), 129.45 (C4), 124.54
.63; Found: C, 53.18; H, 7.06; N, 4.58.
(
C2), 69.45 (C14), 53.45 (C17 & C22), 53.29 (C20 & C21);
31
P NMR (CDCl3 161.7 MHz) d: 20.45; ESI-MS m/z: 486
,
þ
[
M þ H] ; Anal. calcd for C H BrN O P S C, 34.45; H,
Tetraphenyl(((4-(4-methoxyphenyl)thiazol-2-yl)amino)me-
14 19
2
6 2
3
.98; N, 5.77; Found: C, 34.37; H, 3.86; N, 5.73.
thylene)bis(phosphonate) (5g)
White liquid; Yield: 87%; IR (KBr) (ꢀ , cm ): 3324
ꢂ1
max
1
(
NH), 1216 (P ¼ O), 812 (P-CAliphatic
)
HNMR (CDCl3,
Tetraethyl(((4-(4-bromophenyl) thiazol-2-yl)amino)methy-
lene)bis(phosphonate) (5k)
4
00 MHz) d: 7.84–6.74 (25H, m, Ar-H), 5.40 (1H, s, -NH),
3
.82 (3H, s, P-OCH ) 2.41 (1H, d, J ¼ 24 Hz, P-C-H);
ꢁ
3
Yellow solid; Yield: 92%; Mp: 145–148 C; IR (KBr) (ꢀmax,
1
3
ꢂ1
1
C(CDCl 100 MHz) d: 164.32 (C11), 160.40 (C2), 150.40
3
,
cm ): 3325(NH), 1252(P ¼ O), 848 (P-C
); HNMR
Aliphatic
(C23, C24, C25 & C26), 150.05 (C7), 132.51 (C28, C33),
(
CDCl , 400 MHz) d: 7.80–7.52 (4H, s, Ar-H), 7.24 (1H, s,
3
1
1
31.93(C38 & C43), 131.87 (C30, C35), 131.81(C40, C45)
28.32 (C4 & C6), 125.21 (C5), 121.58 (C29, C34), 121.32
Ar-H), 5.32 (1H, s, -NH), 4.75–4.62 (8H, m, POCH CH ),
2
3
3
.45 (12H, m, P-OCH CH ), 2.19 (1H, d, J ¼ 32 Hz, P-C-H);
2
3
13
(C39 & C44), 121.24 (C27& C31), 120.56 (42 & 46), 120.16
C(CDCl , 100 MHz) d: 165.23 (C11), 150.06 (C7), 132.45
3
(
5
C32 & C36), 120.10 (C37 & C41), 107.94 (C9), 69.56 (14), (C5), 132.34 (C1), 132.23 (C3), 128.45 (C4), 128.42 (C6),
3
1
5.28 (C8); P NMR (CDCl3, 161.7 MHz) d: 26.01; ESI-MS 123.32 (C2), 107.45 (C9), 71.84 (C14), 61.85 (C23 & C25),
þ
m/z: 685 [M þ H] ; Anal. calcd for C H N O P S C, 61.81 (C27 & C29), 16.32 (C24 & C26), 16.28 (C28 & C30);
35
30 2 7 2
31
6
1.38; H, 4.48; N, 4.09; Found: C, 60.26; H, 4.32; N, 4.02.
PNMR (CDCl3, 161.7 MHz) d: 21.86; ESI-MS m/z: 542