Structural studies of N(4)-substituted thiosemicarbazones prepared from 4-formylantipyrine and a thiourea derived from 4-aminoantipyrine

Article abstract of DOI:10.1023/A:1023218724180

Reaction of 4-formylantipyrine with N(4)-dimethylthiosemicarbazide and 3-piperidylthiosemicarbazide produces the N(4)-dimethylthiosemicarbazone (1), and the 3-piperidylthiosemicarbazone (2), respectively. Compound 1 is triclinic, space group P-1 with a =

Full text of DOI:10.1023/A:1023218724180

C
Journal of Chemical Crystallography, Vol. 33, No. 2, February 2003 ( 2003)
Structural studies of N(4)-substituted thiosemicarbazones
prepared from 4-formylantipyrine and a thiourea derived
from 4-aminoantipyrine
Ayman K. El-Sawaf,(1) Simo´n Herna´ndez-Ortega,(2) Jesu´s Valde´s-Mart´ınez,(2)
John K. Swearingen,(3) and Douglas X. West(4)
Received November 2, 2001
Reaction of 4-formylantipyrine with N(4)-dimethylthiosemicarbazide and 3-piperidyl-
thiosemicarbazide produces the N(4)-dimethylthiosemicarbazone (1), and the 3-piperidyl-
thiosemicarbazone (2), respectively. Compound 1 is triclinic, space group P-1 with
˚
˚
˚
a = 6.329(1) A, b = 11.699(1) A, c = 11.943(1) A, = 65.83(1) ,
= 80.83(1) ,
= 84.90(1) , and V = 796.1(1) A with Z = 2, for Dcalc = 1.324 g/cm3. Compound
3
˚
˚
˚
˚
˚
2 is triclinic, space group P-1 with a = 6.784(1) A, b = 10.485(2) A, c = 13.462(3) A,
3
= 102.05(2) , = 98.61(2) , = 101.32(2) , and V = 899.8(5) A with Z = 2, for
Dcalc = 1.319 g/cm3. Reaction of 4-aminoantipyrine with phenyl isothiocyanate produced
N-antipyrine-N0-phenylthiourea (3). Compound 3 is monoclinic, space group P21/n with
˚
˚
˚
a = 6.863(7) A, b = 15.361(3) A, c = 16.332(5) A, = 90.35(6) , and V = 1720.7(18)
with Z = 4, for Dcalc = 1.306 g/cm3. Compounds 1 and 2 have intermolecular
3
˚
A
hydrogen bonding between the carbonyl oxygen of the antipyrine moiety and the NH
hydrogen of the thiosemicarbazone moiety. In 3 the two unique molecules are held
together as a dimer by interactions of the two thiourea NH’s and the antipyrine moiety’s
oxygen.
KEY WORDS: Antipyrine; thiosemicarbazone; thiourea; hydrogen bonding; planarity.
Introduction
wide variety of potentially useful biolog-
ical properties,1 and thiosemicarbazones
Antipyrine
(2,3-dimethyl-1-phenyl-5-
and thioureas have demonstrated significant
antitumor activity.2 The activity of thiosemi-
carbazones has been shown to be signifi-
cantly affected by substitution at the moiety’s
N(4)-position.3 Although there have been
a number of studies on 2-formylpyridine
thiosemicarbazones,4,5 only recently have
the spectral properties of 4-formylantipyrine
thiosemicarbazones and their metal complexes
been reported.6–10 Here we report the crystal struc-
tures of the N(4)-dimethylthiosemicarbazone
(1) and 3-piperidylthiosemicarbazone (2) of
pyrazolone) and its derivatives possess a
(1) Department of Chemistry, El-Menoufia University, Shebin
El-Kom, Egypt.
(2) Instituto de Qu´ımica, Universidad Nacional Auto´noma de Me´xico,
Circuito Exterior, Cuidad Universitaria, Coyoaca´n, 04510 Me´xico,
D. F., Mexico.
(3) Department of Chemistry, Illinois State University, Normal,
Illinois.
(4) Department of Chemistry, University of Washington, Seattle,
Washington.
To whom correspondence should be addressed. E-mail: jvaldes@
servidor.unam.mx
105
C
1074-1542/03/0200-0105/0 2003 Plenum Publishing Corporation

106
El-Sawaf, Herna´ndez-Ortega, Valde´s-Mart´ınez, Swearingen, and West
Fourier synthesis, and refined on F2 by a full-
matrix least-squares procedure using anisotropic
displacement parameters with SHELX-97.13
Hydrogens attached to nitrogens were found on a
difference Fourier map and refined isotropically
while hydrogens attached to carbons were located
in their calculated positions, and refined using
a riding model. Scattering factors are from
the International Tables for Crystallography
(1974, Vol IV)14 for 1 and 2 and Wassmaire
and Kirfel15 for 3. The graphics used are
PLATON.16
4-formylantipyrine, as well as N-4-antipyrine-
N0-phenylthiourea (3).
Experimental
N(4)-dimethyl- and 3-piperidylthiosemi-
carbazide were prepared by the method de-
scribed by Scovill.11 The thiosemicarbazones
were prepared by refluxing a 1:1 molar mixture
of 4-formylantipyrine (Aldrich) and the desired
thiosemicarbazide in absolute ethanol with two
drops of concentrated H2SO4 added as reported
previously.6 Compound 3 (mp 206–207 C) was
prepared by mixing 4-aminoantipyrine (Aldrich)
and phenyl isothiocyanate (Aldrich) in 95%
ethanol with gentle warming. On slow evapora-
tion a beige solid separated and was isolated by
suction filtration.
The crystals were grown by slow evaporation
of ethanol solutions and mounted in random
orientation on glass fibers. Reflections for 1, 2,
and 3 were acquired with Siemens P4, Nicolet
P3/F, and Nonius MACH3 diffractometers,
respectively. Crystal stability was monitored us-
ing three standard reflections every 97 reflections.
The structures were solved by direct methods,12
missing atoms were found by difference
Results
The thiosemicarbazones 1 and 2, were pre-
pared by condensation of 4-formylantipyrine
and the desired thiosemicarbazide, Scheme 1(a).
The thiourea, 3, was synthesized from 4-
aminoantipyrine and phenyl isothiocyanate as
shown in Scheme 1(b).
Table 1 summarizes the crystal data, collec-
tion information, and refinement data for the three
antipyrine derivatives, and Table 2 lists the atomic
coordinates and equivalent isotropic displacement
coefficients. Selected bond distances and angles
are shown in Table 3, bond distances and angles
Scheme 1. Procedure for the synthesis of (a) the thiosemicarbazones 1 and 2 and (b) the thoiurea 3.

Antipyrine thiosemicarbazones and thiourea
107
Table 1. Crystallographic Data and Methods of Data Collection, Solution and Refinement for 1, 2, and 3
1
2
3
CCDC no.
Color; habit
CCDC 171822
Yellow; prism
C15H19N5OS
317.4
293(2)
0.40 0.12 0.10
Triclinic
P-1
CCDC 171823
Yellow; prism
C18H23N5OS
357.5
293(2)
0.40 0.24 0.08
Triclinic
CCDC 171821
Beige, prism
C18H18N4OS
338.42
Empirical formula
Formula weight
Temperature, K
Crystal size, mm
Crystal system
Space group
293(2)
0.30 0.26 0.14
Monoclinic
P21/n
P-1
Unit cell dimensions
˚
a, A
6.329(1)
11.699(1)
11.943(1)
65.83(1)
80.83(1)
84.90(1)
796.1(1)
2
6.784(1)
10.485(2)
13.462(3)
102.05(2)
98.61(2)
101.32(2)
899.8(5)
2
6.863(7)
15.361(3)
16.332(5)
90
90.35(6)
90
1720.7
4
1.306
˚
b, A
˚
c, A
, deg
, deg
, deg
Volume, A
3
˚
Z
Density (calculated), Mg/m3
Absorption coefficient mm
1.324
1.884
1.319
1.727
1
0.200
F (000)
Radiation, (A)
range for data collection, deg
Index ranges
336
380
712
˚
Cu K , 1.54178
1.5–55.0
0
11
12
Cu K , 1.54178
1.5–55.0
0
11
14
Mo K , 0.71073
2.49–24.66
0
0
h
6
h
7
h
k
8
18
k
l
11
12
k
l
10
14
19
l
19
Reflections collected
2146
1930, 0.0543
1630
Face-indexed numerical
0.7738/0.866
2496
2262, 0.0468
2065
9-scan
0.6291/0.8705
0.024(4)
3282
3022
1843, 0.0221
9-scan
0.8410/1.0000
0.0052(8)
Independent reflections, Rint
Observed reflections, F > 3.0 (F)
Absorption correction
Min./max. transmission
Extinction correction
Final R indices (observed data)
R indices (all data)
Goodness of fit
R = 0.0672, wR = 0.0971
R = 0.0454, wR = 0.0746
R = 0.0487, wR = 0.0771
1.53
R = 0.0557, wR = 0.1001
R = 0.1277, wR = 0.1390
1.174
R = 0.0796, wR = 0.1189
1.54
Data to parameter ratio
Largest diff. peak/hole
8.0:1
0.36/ 0.37
8.98:1
0.31/ 0.31
6.47:1
0.348/ 0.330
for 3 have been arranged so that they correspond
to the analogous bonds of 1 and 2. The molecular
geometries, thermal ellipsoids (30%), and num-
bering schemes are shown in Figs. 1–3.
In the crystal structure of 1, the sulfur atom
and the imine nitrogen (N3) are syn with respect
In the crystal structure of 2, the sulfur and the
---
imine nitrogen are anti with respect to C7 N4,
Fig. 2. The angle between the mean plane of
phenyl ring and the mean plane of the pyrazole
ring is ca. 63 , and the angle between the mean
planes of the thiosemicarbazone moiety and the
pyrazole ring is ca. 13 . Neighboring molecules
---
to C7 N4, as shown in Fig. 1. The phenyl ring
---
is essentially perpendicular and the mean plane
of the thiosemicarbazone moiety is almost copla-
nar with the pyrazole ring. Neighboring molecules
form dimers held together by two N H
O hy-
drogen bonds involving the thiosemicarbazone N4
˚
and O1 (N
O = 3.066(3) A).
---
form dimers held together by two N H
O hy-
drogen bonds involving the thiosemicarbazone N4
Two unique molecules are present in the
asymmetric unit of 3. The two unique molecules
˚
---
---
and O1 (N1 O1 = 2.971(4) A).
interact through N H
O hydrogen bonds,

108
El-Sawaf, Herna´ndez-Ortega, Valde´s-Mart´ınez, Swearingen, and West
Table 2. Atomic Coordinates (x104) and Equivalent Isotropic Dis-
Table 2. Continued
2
3
˚
placement Coefficients (A x10 ) for 1, 2, and 3
x
y
z
Ueq
x
y
z
Ueq
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30
C33
C34
C35
C36
C37
C38
C39
C40
C41
C42
C43
C44
C45
C46
C47
C48
C49
C50
N11
N12
N13
N14
N31
N32
N33
N34
O11
O31
S11
S31
4432(12)
2494(12)
1690(16)
2745(14)
4638(16)
5496(14)
1.1393(11)
8249(13)
9414(15)
9300(17)
8094(18)
6929(17)
6986(15)
11247(12)
2451(13)
1762(12)
147(12)
3342(13)
4938(13)
6071(15)
6572(16)
5957(17)
4873(19)
4329(14)
1985(12)
758(13)
903(15)
1145(18)
34(2)
2010(19)
2195(15)
1558(13)
10048(9)
8280(10)
6773(10)
5193(9)
0710(9)
947(10)
2852(11)
4356(12)
5127(7)
872(6)
1070(6)
1833(7)
2404(7)
2214(6)
1443(6)
3205(7)
4280(6)
4708(7)
5612(8)
6045(7)
5599(8)
4709(6)
1376(7)
1250(6)
2118(6)
2104(6)
3540(6)
4970(6)
5124(7)
5974(8)
6645(7)
6497(8)
5660(6)
1053(7)
160(6)
6468(5)
6638(5)
6362(7)
5889(6)
5706(6)
5999(5)
5666(6)
6411(6)
6960(7)
6975(9)
6453(9)
5933(8)
5895(7)
6361(6)
8475(5)
8485(5)
8724(5)
8618(5)
8399(6)
9067(6)
9254(7)
8798(7)
8113(9)
7900(7)
9576(6)
8687(5)
8336(6)
8243(6)
8498(7)
8843(7)
8930(6)
8807(6)
6302(5)
6353(4)
6902(4)
6791(4)
8884(4)
8777(4)
8175(4)
8152(5)
6768(3)
8218(4)
54637(15)
95939(16)
45(2)
54(2)
76(3)
65(3)
68(3)
60(2)
63(3)
47(2)
77(3)
102(4)
94(4)
84(3)
67(3)
65(3)
46(2)
44(2)
45(2)
50(2)
51(2).
72(3)
75(3)
73(3)
90(4)
69(3)
66(3)
48(2)
60(3)
75(3)
93(4)
78(3)
58(3)
1
S1
O1
N1
N2
N3
N4
N5
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
3460(2)
3354(6)
4912(7)
5333(6)
1003(6)
2906(6)
6053(7)
3574(8)
2190(7)
3084(8)
183(8)
4220(8)
6680(9)
7585(10)
2344(9)
6661(9)
6755(8)
8803(9)
10156(10)
9542(14)
7499(14)
6101(10)
2687(1)
789(3)
9622(1)
15467(3)
12973(3)
14196(3)
12069(3)
11986(3)
10860(3)
14424(4)
13274(4)
12430(4)
13103(4)
10876(4)
11928(5)
9745(5)
11084(4)
12392(5)
15094(4)
15459(4)
16320(6)
16800(6)
16453(5)
15601(5)
66(1)
64(2)
55(2)
53(2)
55(2)
52(2)
58(2)
50(2)
45(2)
48(2)
48(2)
46(2)
65(2)
74(3)
61(2)
64(2)
48(2)
68(3)
89(3)
95(3)
90(3)
68(2)
3364(4)
2434(4)
1715(4)
1076(4)
846(4)
1617(4)
1976(4)
3031(4)
1340(4)
1477(4)
240(5)
1165(6)
3777(5)
4147(5)
2740(4)
2278(6)
2587(7)
3343(7)
3799(6)
3493(5)
2
S1
O1
N1
N2
N3
N4
N5
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
1762(1)
63(3)
14(1)
1332(2)
3189(2)
2627(2)
1241(2)
411(2)
1171(2)
1855(2)
1853(2)
2653(3)
1110(2)
578(2)
1483(3)
2892(3)
3126(3)
2717(3)
1301(3)
2949(3)
3413(3)
3289(2)
2551(3)
3176(3)
4526(3)
5267(3)
4657(3)
6146(1)
11113(1)
11134(2)
11575(2)
8601(2)
7958(2)
6745(2)
10960(2)
10164(2)
10319(2)
9393(2)
6981(2)
5675(2)
5381(2)
6132(2)
7231(2)
7477(2)
9743(2)
11870(2)
12228(2)
13155(2)
13794(2)
13513(3)
12586(3)
11930(2)
59(1)
48(1)
45(1)
44(1)
41(1)
45(1)
49(1)
38(1)
38(1)
40(1)
41(1)
43(1)
57(1)
61(1)
68(1)
59(1)
49(1)
54(1)
54(1)
40(1)
49(1)
61(1)
63(1)
62(1)
54(1)
516(7)
1385(7)
1941(8)
1592(7)
717(6)
2830(7)
2909(5)
3343(5)
1191(5)
96(5)
1268(5)
738(5)
2828(5)
4124(5)
3005(4)
942(4)
3628(3)
2145(3)
3153(3)
2794(3)
4724(4)
1393(4)
2584(3)
3931(4)
2303(4)
3213(4)
5059(5)
5348(5)
7035(5)
6725(5)
6452(4)
5579(4)
5273(4)
1077(4)
874(4)
68(3)
492(19)
493(19)
473(19)
438(18)
487(18)
476(18)
494(19)
56(2)
477(15)
533(17)
643(8)
725(9)
4046(8)
7247(4)
2769(4)
400
3673(2)
157(5)
943(4)
759(4)
254(4)
involving N13 and N14 (N
˚
O = 2.883(9) and
2.934(9) A, respectively) and N33 and N34 (N
˚
O = 2.798(9) and 2.89(1) A, respectively) to form
3
a dimer, as shown in Fig. 3. There are no signifi-
cant differences in the bond distances and angles
of the two different molecules. The greatest dif-
ference between the two unique molecules of 3 is
C13
C14
C15
C16
6879(12)
7780(12)
9690(12)
6376(11)
2773(6)
1940(5)
2044(6)
501(6)
6606(5)
6643(5)
6433(5)
6409(5)
40(2)
40(2)
47(2)
47(2)

Antipyrine thiosemicarbazones and thiourea
109
˚
Table 3. Selected Bond Distances (A) and Angles ( ) for 1, 2, and 3
1
2
3
Bond
S1 C7
---
1.666(8) 1.656(9)a
---
---
1.689(4) 1.680(3) S11 C16
---
O1 C3
1.246(5) 1.243(3) O11 C13
1.283(9)
1.387(9)
1.37(1)
1.47(1)
1.37(1)
1.44(1)
1.267(9)
1.410(9)
1.37(1)
1.47(1)
1.39(1)
1.39(1)
---
---
1.419(4) 1.406(3) N11 N12
N1 N2
---
N1 C5
N1 C11(C14)
---
N2 C3
---
1.341(6) 1.357(4) N11 C15
---
---
1.446(7) 1.467(4) N11 C23
---
1.386(6) 1.385(4) N12 C13
---
---
N2 C12(C15)
1.427(6) 1.424(4) N12 C24
---
N3 N4
1.372(6) 1.379(3)
---
N3 C6
1.266(5) 1.282(3)
---
N4 C7
---
1.370(5) 1.370(4) N13 C16
1.36(1)
1.38(1)
1.40(1)
1.35(1)
1.37(1)
1.42(1)
---
---
N5 C7
1.321(6) 1.343(4) N14 C16
---
N5 C8
---
1.463(6) 1.471(4) N14 C17
---
N5 C9(C12)
---
1.449(3) 1.462(4)
1.499(6) 1.497(4) C15 C30
---
C5 C10(C13)
Angles
--- ---
1.49(1)
1.48(1)
---
---
---
---
N2 N1 C5
107.8(3) 107.0(2) N12 N11 C15
107.4(6)
116.6(7)
121.8(7)
109.1(7)
119.8(7)
127.5(7)
106.8(6)
116.8(7)
121.9(7)
108.6(7)
120.6(7)
126.3(8)
--- ---
N2 N1 C11(C14)
119.2(4) 115.6(2) N12 N11 C23
--- ---
--- ---
C5 N1 C11(C14)
128.3(4) 124.2(2) C15 N11 C23
--- ---
--- ---
N1 N2 C3
108.1(3) 109.1(2) N11 N12 C13
--- ---
--- ---
N1 N2 C12(C15)
118.9(4) 118.8(2) N11 N12 C24
--- ---
C3 N2 C12(C15)
---
---
126.2(4) 126.3(2) C13 N12 C24
--- ---
N4 N3 C6
117.7(3) 115.5(2)
--- ---
--- ---
C7 N5 C8
---
---
---
---
N3 N4 C7
118.5(3) 123.9(2) C14 N13 C16
123.9(7)
128.0(8)
124.2(7)
125.9(8)
123.8(4) 120.8(2) C16 N14 C17
--- ---
C7 N5 C9(C12)
121.5(4) 126.5(2)
--- ---
O1 C3 N2
---
---
---
---
123.1(4) 123.1(2) O11 C13 N12
123.1(8)
130.5(7)
106.4(7)
122.3(7)
107.6(7)
130.1(8)
109.1(7)
121.8(8)
123.4(7)
124.9(7)
111.7(7)
123.4(8)
130.2(8)
106.3(7)
122.9(7)
108.0(8)
128.4(8)
110.0(7)
120.2(7)
123.7(7)
125.3(7)
111.0(7)
--- ---
O1 C3 C4
130.8(4) 130.8(3) O11 C13 C14
--- ---
--- ---
N2 C3 C4
106.0(3) 106.0(2) N12 C13 C14
--- ---
--- ---
C3 C4 C5
107.7(4) 107.1(2) C13 C14 N13
--- ---
--- ---
C3 C4 C6
123.8(3) 122.4(2) C13 C14 C15
--- ---
--- ---
C5 C4 C6
128.5(4) 130.5(2) C15 C14 N13
--- ---
--- ---
N1 C5 C4
109.9(3) 110.4(2) N11 C15 C14
--- ---
--- ---
N3 C6 C4
121.1(4) 122.9(3) N11 C15 C30
--- ---
--- ---
S1 C7 N4
120.7(3) 115.9(2) S11 C16 N13
--- ---
--- ---
S1 C7 N5
--- ---
123.5(3) 124.0(2) S11 C16 N14
--- ---
N4 C7 N5
115.8(3) 120.1(2) N13 C16 N14
aThe number in this column is the analogous bond in the S31 molecule.
---
in their planarity. For example, the mean plane
of the phenyl ring in the S11 molecule has an
angle of 38.2(3) to the mean plane of the pyra-
zole ring, but is at an angle of 72.9(3) in the S31
molecule.
the N5 C7 bond is most different as might be
expected due to the different functional groups
---
---
attached to N5. The N5 C7 bond is consider-
ably shorter than the N4 C7 bond indicating
some restriction of rotation in the former. In 3
the bond distances in the pyrazole ring are sim-
ilar to those of the thiosemicarbazones, but the
Discussion
---
C13 O11 bond is marginally longer. In addi-
---
The bond distances of the thiosemicar-
bazone and pyrazolone moieties in the thiosemi-
carbazones 1 and 2 are similar; the distance of
tion, the thione bond, C16 S11, is marginally
shorter indicating less delocalization of elec-
tron density in 3. In contrast to bond distances,

110
El-Sawaf, Herna´ndez-Ortega, Valde´s-Mart´ınez, Swearingen, and West
Fig. 1. A view of the two unique molecules of 3 with the atomic numbering scheme, showing the
intermolecular hydrogen bonding interactions. Thermal ellipsoids are drawn at the 30% probability
level.
the bond angles of the thiosemicarbazone moi-
eties show significant differences. In particular,
shows a significant difference between the two
--- ---
thiosemicarbazones, C5 N1 C11, is also sign-
--- ---
--- ---
--- ---
--- ---
N3 N4 C7, S1 C7 N4, and N4 C7 N5
are different by more than 4 . These differ-
ences in bond angles result from the size re-
quirements of the piperidyl ring compared to
the methyl groups of 1. There are also signif-
icant differences for the two molecules in the
bond angles involving the N-methyl function of
ficantly different for 3 (i.e., C15 N11 C21 and
---
---
C35 N31 C41), other comparable angles are
similar.
Considering the angles between mean planes
of the phenyl ring, the thiosemicarbazone and the
pyrazole ring, the smaller thiosemicarbazone 1 is
the more planar. Compared to 1 and 2, 3 is con-
siderably less planar consistent with the more un-
saturated nature of the thiosemicarbazone moiety
compared to the thiourea moiety.
--- ---
the pyrazolone moiety; both N2 N1 C11(C14)
--- ---
and C5 N1 C11(C14) differ by about 4 . One
of the angles in the pyrazolone moiety that
Fig. 2. A view of 1 with the atomic numbering scheme. Thermal ellipsoids are drawn at the 30% probability
level.

Antipyrine thiosemicarbazones and thiourea
111
Fig. 3. A view of 2 with the atomic numbering scheme. Thermal ellipsoids are drawn at the 30% probability
level.
Inthiosemicarbazonesthehydrogenattached
to N4 is often involved in weak intramolecular hy-
drogen bonding [5,17–19]. However, in these two
thiosemicarbazones formation of a 7-membered
have been deposited with the Cambridge Crystal-
lographic Data Center as supplementary publica-
tion No. CCDC 171822 for 1, CCDC 171823 for
2, and CCDC 171821 for 3. Copies of available
material can be obtained, free of charge, on appli-
cation to the Director, CCDC, 12 Union Road,
Cambridge CB21EZ, UK (Fax: +44-(0) 1223-
336033 or e-mail: deposit@ccdc.cam.ac.uk).
--- --- --- --- --- ---
ring (i.e., N4 H4 O1 C3 C4 C6 N3) is
---
less favorable than intermolecular N4 H4
O1
hydrogen bonds.
We have presented the structural infor-
mation for two N(4)-substituted thiosemicar-
bazones prepared with 4-formylantipyrine and a
thiourea prepared from 4-aminoantipyrine. There-
fore, since biological testing of both thioureas20
and thiosemicarbazones21 is being carried out
in many laboratories, these compounds repre-
sent new series that can be tested and a struc-
ture/activity relationship can be determined.
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