2
C. González-García et al. / Journal of Inorganic Biochemistry xxx (2016) xxx–xxx
comparison purpose, a similar investigation was performed on tin par-
ent compounds SnMe Cl , SnBu Cl , SnPh Cl and SnI
2.2.5. Diacetyl-2-(4-isopropyl-3-thiosemicarbazone)-3-(3-hydroxy-2-
1
2
2
2
2
2
2
4
.
naphthohydrazone), H
2
L
A
suspension of 2.17
g
(10.7 mmol) of 3-hydroxy-2-
naphthohydrazide in 10.00 mL of ethanol was added to a suspension
of 2.00 g (9.94 mmol) of HA PrTSC in 40 mL of the same solvent with
2
. Experimental
i
eight drops of conc. hydrochloric acid. The mixture was stirred for 4 h
and the cream precipitate was filtered off, washed with ethanol and vac-
uum dried (3.61 g, 95%). Found C: 59.02, H: 5.94, N: 18.03, S: 8.21.
2
.1. Measurements
Microanalyses were carried out using a LECO CHNS-932 Elemental
C
cm
19
H
23
1
N
5
O
2
S requires C: 59.20, H: 6.01, N: 18.17, S: 8.32. νmax(KBr)/
−
1
Analyzer. IR spectra in the 4000–400 cm
range were recorded as
−
3522 w (OH), 3359 m, 3342 m, 3178 m (NH), 1645 s (CO),
KBr pellets on a Jasco FT/IR-410 spectrophotometer. The ESI mass spec-
tra in positive mode were recorded on a Q-STAR PULSAR I instrument
using a hybrid analyzer QTOF (Quadrupole time-of-flight). Molar con-
ductivity was measured using a freshly prepared DMF or acetone solu-
tion (ca. 10
instrument. H, C and
trometer Bruker AVIII HD-300 MHz using DMSO-d
4
and TMS ( H and C) or SnMe (
MAS NMR spectra were recorded at 298 K in a Bruker AV400WB spec-
trometer equipped with a 4 mm MAS (magic-angle spinning) NMR
probe and obtained using a cross-polarization pulse sequence using
spinning rates of 10–14 KHz, pulse delays of 30 s, contact times of
1
628 m, 1523 s, 1496 s (thioamide II + amide II + CN), 813 w (CS).
+
+
ESI m/z 386.10 ([M] ).
2
.2.6. Diacetyl-2-(4-cyclohxyl-3-thiosemicarbazone)-3-(3-hydroxy-2-
−
3
M) at 25 °C with a Crison EC-Meter BASIC 30+
2
2
naphthohydrazone), H L
1
13
119
Sn NMR spectra were recorded on a spec-
or CDCl as solvent
Sn) as internal reference. Sn CP/
To a suspension of 3.21 g (13.6 mmol) of HAChTSC in 20 mL of eth-
anol with six drops of conc. hydrochloric acid was added a suspension of
6
3
1
13
119
119
2
1
.76 g (13.70 mmol) of 3-hydroxy-2-naphthohydrazide dissolved in
0 mL of ethanol. The mixture was stirred for 1 h and the cream solid
was filtered off, washed with ethanol and vacuum dried (5.61 g, 94%).
Found C: 62.18, H 6.37, N: 16.75, S: 7.42. C22 S requires C:
3444 sh (OH),
352 m, 3255 m (NH), 1672s (CO), 1627 m, 1528 s (thioamide
27 5 2
H N O
−
1
6
2.09, H: 6.40, N: 16.46, S: 7.53. νmax(KBr)/cm
8
ms and two-pulse phase-modulated high power proton decoupling.
3
Chemical shifts are reported relative to SnMe
secondary reference.
4
, using tin(IV) oxide as a
+
+
II + amide II + CN), 832 m (CS). ESI m/z 425.19 ([M] ).
2
.2.7. Diacetyl bis(3-hydroxy-2-naphthohydrazone), H
2
L3
2
.2. Synthesis of the compounds
To suspension of 2.00 (9.89 mmol) of 3-hydroxy-2-
a
g
naphthohydrazide in 30 mL of ethanol was added 0.40 mL
(4.95 mmol) of 2,3-butanedione and eight drops of conc. hydrochloric
acid. The mixture was stirred during 24 h and the cream solid was fil-
tered off, washed with ethanol and vacuum dried (2.06 g, 92%). Found
All the chemicals were purchased from standard commercial
sources and used as received.
C: 68.42, H 5.03, N: 11.98. C26
H
22
N
4
O
4
requires C: 68.71, H: 4.88, N:
i
2
.2.1. 4-Isopropyl-3-thiosemicarbazide, PrTSC
−
1
1
1.96. νmax(KBr)/cm
3411 w (OH), 3220 m (NH), 1649 s (CO),
Over a solution of 10.0 mL (93.7 mmol) of isopropylisothiocyanate in
0 mL of diethyl ether cooled in an ice bath, 4.5 mL (93.70 mmol) of
+
+
1631 m (amide II + CN). ESI m/z 454.16 ([M] ).
5
monohydrated hydrazine was added dropwise and the mixture was
2
.2.8. Diacetyl bis(4-cyclohexyl-3-thiosemicarbazone), H
2
L4
stirred for an hour. The white precipitated formed was filtered off,
0.25 mL (3.10 mmol) of 2,3-butanedione was added to a suspension
1
washed with diethyl ether and vacuum dried (11.78 g, 94%). H NMR
of 1.00 g (5.95 mmol) of ChTSC in 20 mL of ethanol with 10 drops of
conc. hydrochloric acid and the mixture was refluxed for 3 h. The
white precipitate was filtered off, washed with ethanol and vacuum
dried (1.00 g, 85%). Found C: 54.38, H 8.33, N: 21.09, S: 15.99.
3
i
(
DMSO-d
6
) δ 8.48 (1H, s, NH), 7.45 (1H, d, J = 8.6 Hz, NH- Pr), 4.40
2
3
(
2H, s, NH
3
), 4.35 (1H, m, CH), 1.11 (6H, d, J = 6.6 Hz, CH ).
2
.2.2. 4-Cyclohexyl-3-thiosemicarbazide, ChTSC
.71 mL (14.80 mmol) of monohydrated hydrazine was added
dropwise over solution of 2.00 (14.70 mmol) of
C
cm
18
H
32
1
N
6
S
2
requires C: 54.51, H: 8.13, N: 21.19, S: 16.17. νmax(KBr)/
−
0
3336 m, 3185 m (NH), 1525 s, 1490 s (thioamide II + CN),
+
+
a
g
867 m (CS). ESI m/z 396.21 ([M] ).
cyclohexylisothiocyanate dissolved in 50 mL of diethyl ether. The mix-
1
ture was stirred for an hour and the white solid formed was filtered
2.2.9. [SnMe
2
L ] 1
1
L1 and 22 mg
2
off, washed with diethyl ether and vacuum dried (2.31 g, 93%).
H
To a boiling suspension of 100 mg (0.26 mmol) of H
(0.52 mmol) of LiOH·H O in 8 mL of ethanol was added a solution of
57 mg (0.26 mmol) of SnMe Cl in 5 mL of the same solvent. The mix-
3
NMR (DMSO-d
6
) δ 7.35 (1H, d, J = 8.2 Hz, NH), 4.15 (1H, m, CH),
2
3
.86 (2H, br. s, NH ), 2.08–1.27 (10H, m, CH ).
2
2
2
2
ture was stirred for 5 min and the resulting orange solution was imme-
diately cooled in the fridge. After 3 h the orange precipitate formed was
filtered off, washed with cold ethanol and vacuum dried (110 mg, 80%).
i
2
.2.3. Diacetyl-2-(4-isopropyl-3-thiosemicarbazone), HA PrTSC
To a suspension of 1.00 g (7.52 mmol) of iPrTSC in 20 mL of water
Found C: 47.22, H: 4.93, N: 13.06, S: 5.90. SnC21
4
H
27
N
5
O
2
S requires C:
7.39, H: 5.11, N: 13.16, S: 6.02. νmax(KBr)/cm 3431 s (OH), 3266 m
NH), 1642 m (CO), 1530 m (thioamide II + amide II + CN), 821 w
with 10 drops conc. Hydrochloric acid was added 1.5 mL (17.6 mmol)
of 2,3-butanedione and the mixture was stirred for 1 h. The white
solid obtained was filtered off, washed with cold water and methanol
−
1
(
(
+
+
CS). ESI m/z 534.09 ([M + H] ).
1
and vacuum dried (1.39 g, 92%). H NMR (DMSO-d
6
) δ 10.56 (1H, s,
3
i
NH), 8.11 (1H, d, J = 8.4 Hz, NH- Pr), 4.48 (1H, m, CH), 2.40 (3H, s,
CH -CO), 1.95 (3H, s, CH -CN), 1.23 (6H, d, J = 6.6 Hz CH - Pr).
3 3 3
1
2
.2.10. [SnBu
2
L ] 2
i
This complex was obtained following the same procedure described
for the synthesis of 1 but adding 79 mg (0.26 mmol) of SnBu Cl (red,
2
2
2
.2.4. Diacetyl-2-(4-cyclohexyl-3-thiosemicarbazone), HAChTSC
The compound was obtained following the procedure described
141 mg, 88%). Slow evaporation of a solution in DMF yielded crystals
suitable for single crystal X-ray diffraction. Found C: 52.36, H: 6.28, N:
1
above but using 1.00 g (6.16 mmol) of ChTSC (1.31 g, 94%). H NMR
11.19, S: 5.12. SnC27
5.20. νmax(KBr)/cm
H
39
−1
N
5
O
2
S requires C: 52.58, H: 6.38, N: 11.36, S:
3
(
(
(
DMSO-d
1H, m, CH), 2.38 (3H, s, CH
10H, m, CH ).
6
) δ 10.59 (1H, s, NH), 8.1 (1H, d, J = 8.3 Hz, H-Ch), 4.15
3437 m (OH), 3266 m (NH), 1641 m (CO),
+
3
-CO), 1.95 (3H, s, CH -CN) 1.89–1.28
3
1536 s (thioamide II + amide II + CN), 808 w (CS). ESI m/z 618.19
+
2
([M + H] ).