RSC Advances
Paper
1
4
.2.2 4,4-Dimethyl-1-phenylpentane-1,3-dione (4). 4 was
L
5
. Yield: 83%. H NMR (400 MHz, CDCl
3
): d 12.29 (s, 2H),
1
13
synthesized with a similar procedure as for 2. H NMR 7.43–6.83 (m, 22H), 6.20 (d, J ¼ 7.7 Hz, 2H), 1.21 (s, 18H).
C
(
2
7
400 MHz, CDCl ): d 206.11 (C]O), 158.26 (Ar-NH–C),
3
): d 7.92 (s, 2H), 7.52 (s, 1H), 7.46 (d, J ¼ 6.2 Hz, NMR (101 MHz, CDCl
3
H), 6.33 (s, 1H), 1.28 (s, 9H). Anal. calcd for C13
6.44; H, 7.90%. Found: C, 76.85; H, 7.46%.
.2.3 Ligands L –L
H
16
O
2
: C, C, 139.83, 136.59, 134.33, 132.50, 132.19, 129.48, 129.19, 128.94,
128.44, 127.73, 127.54, 127.16, 125.01, 124.37 (Ar-C), 97.24,
42.53, 27.61. Anal. calcd for C H N O S : C, 75.83; H, 6.36; N,
4
1
6
44 44 2 2 2
ꢀ
1
L1. To a 100 ml 3-neck ask were added 0.6837 g of 2, 0.6791 g 4.02%. Found: C, 75.62; H, 6.53; N, 4.34%. IR (KBr, cm ): 3447,
of methylthio aniline, 40 ml of toluene, and 0.1 g of p-toluene 3059, 2964, 2865, 2360, 2342, 1616, 1571, 1558, 1497, 1475,
sulfonic acid (TsOH) as catalyst, and heated to reux for 24 h. The 1439, 1289, 1120, 1089, 1023, 792, 750.
1
mixture was then vacuum dried, and recrystallized with ethanol
L
6
. Yield: 81%. H NMR (400 MHz, CDCl
3
): d 12.22 (s, 1H),
1
to afford L
1
as a yellow solid with 78% yield. H NMR (400 MHz, 7.30 (d, J ¼ 11.2 Hz, 6H), 6.85 (d, J ¼ 47.5 Hz, 2H), 6.34 (s, 1H),
CDCl
3
): d 12.05 (s, 1H), 7.30 (s, 1H), 7.25 (s, 1H), 7.23 (d, J ¼ 5.66 (s, 1H), 2.95 (d, J ¼ 4.7 Hz, 2H), 1.75 (s, 2H), 1.26 (s, 9H),
1
3
5
.0 Hz, 1H), 7.21–7.13 (m, 1H), 7.00 (t, J ¼ 7.7 Hz, 1H), 6.79 (t, J ¼ 1.09 (d, J ¼ 8.5 Hz, 3H). C NMR (101 MHz, CDCl
.6 Hz, 1H), 6.19 (d, J ¼ 7.7 Hz, 1H), 5.45 (s, 1H), 2.51 (s, 3H), 1.24 (C]O), 159.32 (Ar-NH–C), 139.77, 136.51, 132.89, 130.15,
3
): d 205.91
7
(
1
3
d, J ¼ 21.4 Hz, 9H). C NMR (101 MHz, CDCl ): d 206.30 (C]O), 129.56, 129.41, 128.44, 128.35, 128.14, 125.88, 124.48, 123.90
3
1
1
58.87 (Ar-NH–C), 137.91, 136.55, 132.38, 129.14, 128.52, 127.94, (Ar-C), 97.37, 52.07, 35.31, 27.71, 22.58, 13.56. Anal. calcd for
26.51, 125.14, 124.75, 124.71 (Ar-C), 97.14, 42.56, 27.60, 15.53. 27NOS: C, 74.75; H, 7.70; N, 3.96%. Found: C, 74.39; H,
: C, 71.29; H, 7.04; N, 4.89%. Found: 7.57; N, 3.73%. IR (KBr, cm ): 3449, 2963, 1617, 1562, 1507,
22
C H
ꢀ
1
Anal. calcd for C34
C, 71.38; H, 6.92; N, 4.75%. IR (KBr, cm ): 3452, 3070, 2964, 1387, 1299, 1218, 1186, 1086, 802, 766.
608, 1501, 1475, 1441, 1325, 1219, 1122, 1087, 751.
40 2 2 2
H N O S
ꢀ
1
1
Ligands L
for L1.
2
–L
6
were synthesized with a similar procedure as
2
2
4
.3. Binuclear titanium complexes (Ti L
1
–Ti L
4
)
1
2
L . Yield: 80%. H NMR (400 MHz, CDCl ): d 12.06 (s, 2H),
2
4.3.1 Ti L
1
. 0.573 g (1 mmol) of ligand L
1
was added to
Cl . A solution
2
(15 ml) was added to
3
7
8
(
.31 (s, 1H), 7.30 (s, 2H), 7.24 (d, J ¼ 7.1 Hz, 2H), 7.19 (d, J ¼ a 100 ml Schlenk ask, dissolved in 15 ml of CH
.6 Hz, 1H), 6.95 (t, J ¼ 7.3 Hz, 2H), 6.81 (t, J ¼ 7.3 Hz, 2H), 6.20 of TiCl (0.28 ml, 2.6 mmol) in CH Cl
2
2
4
2
d, J ¼ 7.9 Hz, 2H), 2.93 (t, J ¼ 7.3 Hz, 4H), 1.81–1.67 (m, 4H), another 100 ml Schlenk ask. The ligand solution was then
1
3
ꢃ
1
.21 (s, 18H), 1.07 (t, J ¼ 7.4 Hz, 6H). C NMR (101 MHz, slowly added to the TiCl
4
solution at ꢀ78 C. Aer 5 hours, the
ꢃ
CDCl
3
): d 206.13 (C]O), 158.43 (Ar-NH–C), 139.19, 136.73, mixture was slowly warmed to RT, then heated to 35 C for 24 h
2
1
30.21, 129.50, 129.11, 126.74, 125.82, 125.54, 124.97, 124.31 under stirring. The solvent was vacuum dried to afford Ti L
1
as
(
Ar-C), 97.35, 42.56, 34.97, 27.61, 22.50, 13.62. Anal. calcd for a red brown solid. Pure product was obtained by diffusing n-
2
C H N O S : C, 72.57; H, 7.69; N, 4.45%. Found: C, 72.83; H, hexane into dichloromethane solution of Ti L
with 67% yield.
): d 7.50 (s, 1H), 7.34 (s, 1H), 7.14 (t, J ¼
589, 1571, 1533, 1497, 1474, 1451, 1325, 1286, 1123, 1088, 7.3 Hz, 1H), 6.95 (s, 2H), 6.21 (s, 1H), 5.94 (s, 1H), 3.15 (d, J ¼
3
8
48 2 2 2
1
ꢀ
1
1
7
1
7
.88; N, 4.16%. IR (KBr, cm ): 3446, 3063, 2959, 2868, 1615,
H NMR (400 MHz, CDCl
3
1
3
51.
28.7 Hz, 3H), 1.31 (s, 9H). C NMR (101 MHz, CDCl
): d 12.14 (s, 1H), (]C–O), 172.20 (Ar-N]C), 166.35, 151.34, 130.31, 130.02,
.39 (d, J ¼ 6.6 Hz, 1H), 7.29 (s, 1H), 7.25 (s, 1H), 6.90 (d, J ¼ 128.90, 128.08, 128.04, 125.46, 117.14, 111.60 (Ar-C), 92.59,
1.1 Hz, 2H), 6.22 (s, 1H), 5.45 (s, 1H), 3.48 (s, 1H), 1.38 (s, 5H), 39.53, 27.79, 14.11. Anal. calcd for C34 Ti : C,
.21 (s, 9H). C NMR (101 MHz, CDCl ): d 203.30 (C]O), 183.66 46.45; H, 4.36; N, 3.19%. Found: C, 46.82; H, 4.73; N, 3.31%. IR
3
): d 210.41
1
3 3
L . Yield: 68%. H NMR (400 MHz, CDCl
7
2
1
H38Cl
6
N
2
O
2
S
2
2
1
3
3
ꢀ1
(
Ar-NH–C), 150.68, 138.85, 137.37, 136.14, 131.15, 130.33, (KBr, cm ): 3070, 2962, 2931, 2875, 1706, 1609, 1558, 1458,
1
2
28.94, 125.87, 125.48, 117.36 (Ar-C), 92.40, 39.97, 36.12, 27.40, 1318, 1275, 1211, 1125, 1091, 765.
2
2
3.02. Anal. calcd for C38
H
48
N
2
O
2
S
2
: C, 72.57; H, 7.69; N, 4.45%.
Complexes Ti L
2
2
–Ti L
5
were prepared using the same
ꢀ1
1
Found: C, 72.29; H, 7.35; N, 4.68%. IR (KBr, cm ): 3451, 3061, procedure as for Ti L .
2
1
2
966, 1623, 1386, 1316, 1189, 1088, 569, 461.
4.3.2 Ti L
2
. Yield: 75%. H NMR (400 MHz, CDCl
3
): d 7.57
1
L
4
. Yield: 78%. H NMR (400 MHz, CDCl
3
): d 12.08 (d, J ¼ (d, J ¼ 7.0 Hz, 1H), 7.33 (d, J ¼ 6.7 Hz, 1H), 7.19 (dd, J ¼ 7.7,
2
2
2
1
9
0.4 Hz, 2H), 7.30 (d, J ¼ 4.1 Hz, 2H), 7.29 (s, 1H), 7.27–7.22 (m, 3.1 Hz, 1H), 7.13 (t, J ¼ 7.6 Hz, 1H), 6.99 (s, 1H), 6.24 (d, J ¼
H), 7.22–7.14 (m, 1H), 6.95 (t, J ¼ 7.7 Hz, 2H), 6.80 (t, J ¼ 7.5 Hz, 20.7 Hz, 1H), 6.01 (s, 1H), 3.52 (s, 2H), 2.10 (dd, J ¼ 14.8, 7.3 Hz,
1
3
H), 6.20 (d, J ¼ 8.2 Hz, 2H), 5.44 (s, 2H), 2.94 (t, J ¼ 7.4 Hz, 4H), 2H), 1.32 (s, 9H), 1.23 (t, J ¼ 7.3 Hz, 3H). C NMR (101 MHz,
.77–1.67 (m, 4H), 1.46 (dd, J ¼ 13.4, 6.5 Hz, 4H), 1.29 (dd, J ¼ CDCl
3
): d 204.32 (]C–O), 165.78 (Ar-N]C), 149.71, 141.36,
.8, 4.0 Hz, 16H), 1.21 (s, 18H), 0.89 (t, J ¼ 6.5 Hz, 6H). C NMR 139.37, 136.75, 129.63, 126.57, 125.01, 117.34, 115.96, 113.45,
): d 206.02 (C]O), 158.39 (Ar-NH–C), 139.26, 113.20, 111.53 (Ar-C), 98.55, 31.58, 27.55, 22.64, 14.10, 13.56.
36.78, 130.38, 129.56, 129.09, 128.47, 127.93, 125.53, 124.93, Anal. calcd for C38 Ti : C, 48.80; H, 4.96; N, 3.00%.
24.28 (Ar-C), 97.37, 42.54, 39.24, 33.16, 31.82, 29.19, 28.97, Found: C, 49.25; H, 4.64; N, 3.43%. IR (KBr, cm ): 2965, 1620,
8.70, 27.61, 22.65, 14.10. Anal. calcd for C48
: C, 1563, 1460, 1289, 1208, 1091, 838, 756.
4.95; H, 8.91; N, 3.64%. Found: C, 74.59; H, 8.62; N, 3.91%. IR
1
3
(
101 MHz, CDCl
3
1
1
2
7
H
46Cl
6
N
2
O
2
S
2
2
ꢀ1
68 2 2 2
H N O S
2
1
4.3.3 Ti L . Yield: 80%. H NMR (400 MHz, CDCl ) d 7.56
3 3
ꢀ1
(
KBr, cm ): 3448, 3061, 2926, 2858, 1608, 1564, 1466, 1315, (d, J ¼ 7.9 Hz, 2H), 7.15 (dd, J ¼ 35.8, 18.6 Hz, 3H), 6.40 (s, 1H),
1
3
1220, 1188, 1100, 788.
6.09 (s, 1H), 4.14 (s, 1H), 1.63 (s, 6H), 1.32 (s, 9H). C NMR
(101 MHz, CDCl
3
): d 199.20 (]C–O), 181.31 (Ar-N]C), 160.32,
6962 | RSC Adv., 2018, 8, 6954–6964
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