Self-assembled Transition Metal Coordination Frameworks of ...

Chapter2 V _ _ _ _, 7 _
with acetonitrile. The compound was recrystallized from ethanol solution and dried in
vacuo over P4010. Yield 46%. Elemental analysis: Found (calc.): C, 63.15 (63.35); I-1,
\ '7 / \ S
5.99 (5.67); N, 19.66 (19.70); S, 11.26 (11.28)%.
1. \~.~. @| . /~.\
//T‘-\_\ /-/Q\\‘ IS
! H2N..._
"
,.CH3
\
-
/
H o
\
" i‘
|
.1
I. ­
L\\i*"'/|]l‘N'%\‘T"/"O H '~“I:;~-\. /L + NH _____ + W HN\ \\ _/- H —_‘2('—" \._N-,/ V 5/ L / \N I H /l\ ,1 N - \N Uin
/..\\ >
I“ /7' _ _/N /./) H L%--_J/
t_\:;_,__ H30 Hy,
Scheme 2.4. Reaction scheme of thiosernicarbazone HL7.
2-Benzoylpyridine-N(4),N(-4)-(butane-1, 4-diyl) thiosemicarbazone (HL8)
To a solution of 1.000 g (5. 52 mmol) of 4-methyl-4-phenyl-3­
thiosemicarbazide in 5 ml of acetonitrile, 0.392 g (5. 52 mmol) of pyrrolidine and
1.021 g (5.52 mmol) of 2-benzoylpyridine were added and refluxed for 1‘/2 h. The
solution was chilled (overnight) and the crystals that separated were collected and
washed well with acetonitrile. The compound was recrystallized from ethanol solution
and dried in vacuo over P40“). Yield 40%, M.p. 186 °C. Elemental analysis: Found
(calc.): C, 65.74 (65.78); H, 5.69 (5.84); N, 17.96 (18.05); S, 10.67 (10.33)%.
The compound 4-methyl-4-phenyl-3-thiosemicarbazide for the synthesis of
HL7 and HL8 was prepared by the following two steps.
(1') Preparation of carboxymethyl N-methyl, N-phenyl dithiocarbamate
A mixture consisting of 12 ml (5.200 g, 0.20 mol) of carbon disulfide and
21.6 ml (21.200 g, 0.20 mol) of N-methylaniline was treated with a solution of sodium
hydroxide (8.400 g, 0.21 mol) in 250 ml distilled water. This was then stirred at room
temperature for 4 h to get a straw colored solution, after the complete disappearance
of organic layer, and treated with 23.200 g (0.20 mol) of sodium chloroacetate and
allowed to stand overnight (17 hours). The solution was acidified with 25 ml of conc.
42