584 Ma, Wang, and Zhang
EXPERIMENT
(0.068 g, 1 mmol), and Ph3SnCl (0.385 g, 1 mmol)
were added to the solution of benzene (20 mL), con-
tinuing the reaction for 12 h at 40◦C The solid was
recrystallized from ether, and yellow crystals were
formed. Yield: 77%. mp 158–162◦C. Anal. Found: C
61.63, H 3.55, N 8.31. Calcd. for C33H25FN4SSn: C
61.23, H 3.89, N 8.65%. IR (KBr, cm−1): ν(C N),
1614; ν(S C N), 1557; ν(C S), 967; ν(Sn S), 328.
1H NMR [(CD3)2SO, ppm] δ : 8.48 (s, 1H, CH N),
7.33–7.58 (m, 24H, Ar H). 13C NMR (CDCl3. ppm):
167.1 (C S Sn), 153.2 (CH N), 149.7 (Ph C N),
137.6, 137.1, 137.0, 136.7, 135.2, 135.1, 134.9, 134.8,
130.7, 130.5, 130.1, 129.4 (Ar C); 119Sn NMR (CDCl3,
ppm): 61.5
Materials and Measurements
All reagents were commercially available, and they
were used without further purification. The melting
points were obtained with X-4 digital micromelt-
ing point apparatus and were uncorrected. Infrared
spectra were recorded on a Nicolet-6700 spectropho-
tometer using KBr disks and sodium chloride optics.
1H and 119Sn NMR spectra were recorded on Varian
mercury plus 400 spectrometer operating at 400 and
149.2 MHz, respectively. The spectra were acquired
at 298 K. The chemical shifts were reported in ppm
with respect to the references and were stated rela-
tive to external tetramethylsilane (TMS) for 1H NMR,
and neat tetramethyltin for 119Sn NMR. Elemental
analyses (C,H,N) were performed with a PE-2400II
apparatus.
[(CH3)3Sn(C15H10FN4S)n 4. The procedure is
similar to that of complex 3. The Schiff base com-
pound 1 (0.298 g, 1 mmol), sodium ethoxide (0.068
g, 1 mmol), and Me3SnCl (0.199 g, 1 mmol) were
added to the solution of benzene (20 mL), contin-
uing the reaction for 12 h at 40◦C. The solid was
recrystallized from ether, and yellow crystals were
formed. Yield: 73%. mp 137–141◦C. Anal. Found: C
46.53, H 4.38, N 11.87. Calcd. for C18H19FN4SSn: C
46.88, H 4.15, N 12.15%. IR (KBr, cm−1): ν(C N),
1656; ν(S C N), 1549; ν(C S), 943; ν(Sn S), 354;
Syntheses of Schiff Base Compounds 1–2 and
Triorganotin Schiff Base Complexes 3–6
C15 H11FN4S 1. The reaction was carried out
under nitrogen atmosphere, with the use of
standard Schlenk technique, 4-amino-5-phenyl-4H-
1,2,4-trizole-3-thiol (1.153, 6 mmol) was added to
the solution of dry ethanol (30 mL) and then added
4-fluorobenzaldehyde (0.745 g, 6 mmol) to the solu-
tion, continuing the reaction for 6 h at refluxing, the
yellow precipitate was collected by filtration, washed
with ether petroleum, and dried at the nitrogen at-
mosphere. mp >200◦C. Yield: 89%. Anal. Found: C,
60.01; H, 3.41; N, 19.07. Calcd. for C15H11FN4S: C,
60.39; H, 3.72, N, 18.78%. IR (KBr, cm−1): ν(S H)
2718, ν(C N) 1667, ν(S C N) 1578, ν(C S) 988.
1H NMR (CDCl3. ppm): 8.57 (s, 1H, CH N), 7.69–
7.88 (m, 9H, Ar H), 2.41 (s, 1H, S H).
1
ν(Sn N) 442. H NMR [(CD3)2SO, ppm] δ : 8.36 (s,
1H, CH N), 7.32–7.83 (s, 9H, Ar H), 0.87 (9H, CH3,
2 J119
= 81.2 Hz). 13C NMR (CDCl3. ppm): 168.4
1
H
Sn,
(C S Sn), 154.9 (CH N), 148.1 (Ph C N), 136.2,
135.5, 135.0, 134.8, 130.9, 130.2, 129.3, 128.6 (Ar C),
14.1 (CH3) (1 J119
ppm): −116.7.
= 497 Hz). 119Sn NMR (CDCl3,
13
C
Sn,
(Ph3Sn)(C13H9N4S2) 5. The procedure is sim-
ilar to that of complex 3. The Schiff base com-
pound 2 (0.287 g, 1 mmol), sodium ethoxide (0.068
g, 1 mmol), and Ph3SnCl (0.385 g, 1 mmol) were
added to the solution of benzene (20 mL), contin-
uing the reaction for 12 h at 40◦C The solid was
recrystallized from ether, and yellow crystals were
formed. Yield: 81%. mp 155–157◦C. Anal. Found: C
58.29, H 3.50, N 9.12. Calcd. for C31H24N4S2Sn: C
58.60, H 3.81, N 8.82%. IR (KBr, cm−1): ν(C N),
1664; ν(S C N), 1552; ν(C S), 951; ν(Sn S), 343.
1H NMR [(CD3)2SO, ppm] δ : 8.44 (s, 1H, CH N),
7.01–7.76 (m, 20H, Ar H), 7.35 (d, JH,H = 3.6 Hz,
1H), 7.12 (dd, JH,H = 4.8 Hz, 1H), 7.37 (d, 1H), 13C
NMR (CDCl3. ppm): 161.8 (C S Sn), 152.4 (CH N),
140.1 (Ph C N), 136.2, 134.5, 132.1, 130.6, 129.7,
128.9, 128.6, 126.6 (Ar C), 122.1, 119.4, 117.5, 110.2
(thiophene ring-C). 119Sn NMR (CDCl3, ppm): 53.2.
C13 H10 N4S 2. The procedure was the same
2
as in the Schiff base compound 1. 4-Amino-5-
phenyl-4H-1,2,4-trizole-3-thiol (1.153, 6 mmol) and
thiophene-2-carboxadehyde (0.673 g, 6 mmol) added
to ethanol of 30 mL, refluxing for 6 h, the yellow
precipitate was collected by filtration, washed with
ether–petroleum, and dried at the nitrogen atmo-
sphere. mp >200◦C. Yield: 81%. Found: C, 54.20;
H, 3.81; N, 19.20. Calcd. for C13H10N4S2: C, 54.52;
H, 3.52, N, 19.56%. IR (KBr, cm−1): ν(S H) 2787,
ν(C N) 1689, ν(S C N) 1573, ν(C S) 970. 1H NMR
(CDCl3. ppm): 8.85 (s, 1H, CH N), 7.61–7.85 (m, 8H,
Ar H), 2.47 (s, 1H, S H).
(Ph3Sn)(C15H10FN4S) 3. The reaction was car-
ried out under nitrogen atmosphere. The Schiff base
compound 1 (0.298 g, 1 mmol), sodium ethoxide
(CH3)3Sn(C13H9N4S2) 6. The procedure is sim-
ilar to that of complex 3. The Schiff base compound
Heteroatom Chemistry DOI 10.1002/hc