Reaction of 4-substituted thiosemicarbazides with (2,4,7-trinitro-9H- fluoren-9-ylidene)propanedinitrile

Article abstract of DOI:10.1002/jhet.5570430406

4-Substituted thiosemicarbazides 4a-c reacted with (2,4,7-trinitro-9H- fluoren-9-ylidene)-propanedinitrile (2) in pyridine with admission of air to form spiro[fluorene-9,3'-(1,2,4-triazole)]derivatives 5a-c and (4-substituted thiosemicarbazono)propanedinitriles 6a-c in modest yields. 2,4,7-Trinitro-9- fluorenone (8) as well as one reduction product thereof and of 2, namely compounds 9 and 10, respectively are also found. A rationale for the conversions observed is presented.

Full text of DOI:10.1002/jhet.5570430406

Jul-Aug 2006
849
Reaction of 4-Substituted Thiosemicarbazides with (2,4,7-Trinitro-
9H-fluoren-9-ylidene)propanedinitrile
Alaa A. Hassan,a* Yusria R. Ibrahim,a Ahmed M. Shawkya and Dietrich Döppb
a Chemistry Department, Faculty of Science, El-Minia University, El-Minia, A. R. Egypt.
E.mail: alaahassan2001@yahoo.com
bOrganische Chemie, Universität Duisburg-Essen, D-47048 Duisburg, Germany.
Received August 1, 2005
NO2
NH2
H
CN
CN
H
R NH C
S
N NH2
+
+
R NH C
S
N N C
O2N
NO2 O2N
NO2
N
N
N
R
NC
CN
S
4-Substituted thiosemicarbazides 4a-c reacted with (2,4,7-trinitro-9H-fluoren-9-ylidene)-propane-
dinitrile (2) in pyridine with admission of air to form spiro[fluorene-9,3'-(1,2,4-triazole)]derivatives 5a-c
and (4-substituted thiosemicarbazono)propanedinitriles 6a-c in modest yields. 2,4,7-Trinitro-9-fluorenone
(8) as well as one reduction product thereof and of 2, namely compounds 9 and 10, respectively are also
found. A rationale for the conversions observed is presented.
J. Heterocyclic Chem., 43, 849 (2006).
Introduction.
afford the aforesaid heterocycles in excellent yields, even
under mild reaction conditions [8,9,15].
Thiosemicarbazides are easily cyclized by action of
bases, acids or oxidants therefore they are useful and
versatile building blocks for the preparation of various
heterocycles. For examples, oxidation of aldehyde
semicarbazone and thiosemicarbazone derivatives by
metal salts has been used for the synthesis of 1,2,4-
triazole, 1,3,4-oxadiazole and 1,3,4-thiadiazole deriv-
atives [1-6]. The heterocyclizations of 1,4-disubstituted
thiosemicarbazides - in basic or acidic media and under
various reaction conditions - were investigated [7-10].
Four-, five-, six- and seven-membered heterocyclic
compounds were prepared by reaction of thiosemi-
carbazide derivatives with a- and ꢀ-haloketones [11-14].
In addition, microwave (MW) heating of thiosemi-
carbazides has been employed for rapid synthesis of a
wide variety of heterocyclic compounds such as thiadia-
zole, triazole-3-thiol, thioxoimidazole and thiadiazepine
derivatives [15,16]. Also, the thermal cyclization of 1-
aryl/alkyl-2-alkylisothiobiureas afforded 1,2,4-triazolines
[17]. Irradiation of glyoxylic acid methylester thiosemi-
carbazones in methanol solution gave triazines [18]. On
the other hand, the interaction of thiosemicarbazides with
ethenetetracarbonitrile and benzo- as well as naphthoquin-
ones as ꢁ-acceptors afforded thiazole, thiazine, thiadia-
zole, thiadiazine, thiadiazepine, pyrazine and indazole
derivatives [19-25].
It had been reported earlier that (2,4,7-trinitro-9H-fluoren-
9-ylidene)propanedinitrile (2) and other 9-(dicyano-
methylene)nitrofluorene derivatives react with secondary
amines with subsequent substitution of cyano by amino
groups to afford trinitro-substituted-9-(aminomethylene)
-
fluorenes [26], while we have reported the complex
Scheme 1
NO2
NO2
H
Ar N
+
CH3
C
Ar N
1a-c
O2N
NO2
O2N
NO2
CN
NC
CN
Ar N
N
NH2
2
Ar
3a-c
1 , 3: a: Ar = p-CH3-C6H4 ; b: Ar = p-CH3O-C6H4 ; c: Ar = p-Cl-C6H4
reaction of N-arylisoindolines (being tertiary amines) with
2 [27]. Recently, it has been found that addition of N2 of
amidines 1a-c to one of the cyano groups of 2, followed
by intramolecular conjugate addition of the methylene-
active ꢀ-carbon atom of the acetamidine moiety to C-9 of
the fluorene gives spiro[fluorene-9,4'-(1',2',3',4'-tetra-
hydropyridine]-5'-carbonitriles 3a-c (Scheme 1) [28]. This
fascinating versatility in the chemistry of 2 is intriguing
and justifies further investigations of reactions of this
acceptor with suitable donors. In this paper we describe
the reaction of 4-substituted thiosemicarbazides 4a-c with
(2,4,7-trinitro-9H-fluoren-9-ylidene)propanedinitrile (2,
Since N2 of the thiosemicarbazide group is a softer
nucleophilic center than the harder and more powerful
terminal nitrogen N1, reagents susceptible to nucleophilic
attack by N1 may in a second step undergo cyclization to

850
A. A. Hassan, Y. R. Ibrahim, A. M. Shawky and D. Döpp
Vol 43
previously referred to as 9-dicyanomethylene-2,4,7-
trinitro-fluorene).
group. The a priori possible isomeric structures 7a-c were
ruled out on the basis of the lowest field signals in the 13
C
nmr spectra (5a: 181.8, 5b: 181.4 and 5c: 181.3 ppm)
which clearly support a C=S group and not an isothiourea
carbon as in 7.
Results and Discussion.
Pyridine solutions of 2 and 4-substituted thiosemi–car–
bazides 4a-c in a molar ratio of 2:1 were kept at 100 °C
for 3 hours with admission of air. Chromatographic
separ–ation of the residue after concentration gave
numerous colored zones, from which products 5a-c and
6a-c could be isolated. In addition, the known compounds
8 [29] and 9,10 [27] were found in small quantities in all
cases (Scheme 2). Structural assignments of products 5
and 6 are based on spectral data and on combustion
analyses.
NH2
O2N
NO2
N
N
S
NR
7a, R = Ph
7b, R = PhCH2
7c, R = allyl
Scheme 2
NH2
2
CN
H
H
R
NH
C
S
N
NH2
+
R
NH
C
S
N
N
C
+
O2N
NO2
CN
N
N
N
R
S
4
6a-c (23 - 25 %)
5a-c (21-24%)
NO2
NH2
+
O2N
NO2
O2N
NO2
X
O
8 (6 - 8%)
9, X = O (12 - 16%)
10, X = C(CN)2 (8 - 11%)
R
4 -6
a
b
c
Ph
PhCH2
allyl
Compounds 5a-c.
Compounds 6a-c.
The molecular ions in their EI- mass spectra confirm
the molecular masses and the gross compositions. Further,
the following common features of the fragmentation
patterns lend support to the assigned structures: Loss of
N2 giving intense (M+-28) ions, and loss of R-NCS giving
rise to the ion m/z = 297 common in the spectra of all
three compounds. The odd-electron fragments represent
the three isocyanates indicating that the charge during
fragmentation may remain both with the nitroarene body
or the isothiocyanate fragments. The ir spectra show
characteristic absorptions for the NH2 groups in the ranges
of 3417 to 3437 (NH2); and 1343-1354 as well as 996-
1020 cm-1 to strong vibrational coupling of C=S and C-N
entities. Two bands around 1530 and 1340 cm-1 have to be
assigned to the nitro groups.
The ir spectra (in KBr) showed conjugated CN groups
at 2220-2225 cm-1, NH absorptions at 3315-3344 and
3268-3280 cm-1, and bands characteristic of vibrational
coupling of C=S and C-N groups at 1355 and 998-1015
1
cm-1 The H nmr spectra clearly show two broad signals
(N2H and N4H) at 9.71 and 9.88 for 6a, 8.65 and 9.45 for
6b as well as 7.89 and 8.69 ppm for 6c. Signals around
118.3 (CN) , 157 (C=N) and 183.7 ppm (C=S) in the 13C
nmr spectra lend further support to the structures assigned
to 6a-c. The mass spectra of thiosemicarbazones 6 are, on
the other hand, better explained assuming a degradation
via a cyclic tautomer A (Scheme 3).
Such ring-chain tautomeric equilibria for aldehyde
thiosemicarbazones and their role in mass spectral
fragmentation have been discussed before [29-33]. Both
1,2,4-thiazolidine-3-thiones [29,30] (under neutral
conditions) and 1,3,4-thiazolidineimines [29,31] (in acidic
medium) may exist in equilibrium with the thiosemi-
1
The H nmr spectra show the presence of NH2 groups
by broad signals for 2H between ꢀ = 6.45 and 6.50 ppm
and for additionally 5c, the expected signals for the allyl

Jul-Aug 2006
Reaction of 4-Substituted Thiosemicarbazides
851
Scheme 3
Scheme 4
CN
CN
NC
R
NC
CN
R
CN
NC
N
NC
N
CN
NC
N
NH
C
N
C
NH
NH
R
R
R
NH
N
NH
NH
N
N
N
N
H
-32
C
S
S
S
6a-c
A
A
-N2
CN
carbazone. The photochemical cyclization of some
aldehyde-semicarbazones to triazolinethiones has also
been reported [18], and the differences in the mass
spectral fragmentation between thiosemicarbazones and
thiosemicarbazones of aldehydes and ketones has been
noted early by Djerassi [32] and coworkers who
interpreted the fragmentations of thiosemicarbazones to
occur from cyclic ions of 1,3,4-thiadiazolium
connectivity.
CN
CN
CN
R-NC2
R
N
R
N
-HCN
-HCN
or
H
C
CN
or
C
CN
CH
RN
CN
R = Ph: m/z 169
R = Bn: m/z 183
R = Allyl: m/z 133
RN
C
-14
CN
R = Ph: m/z 155
R = Bn: m/z 169
The EI mass spectra of 6a-c are characterized by
molecular ions of low intensity and the loss of 32 a. m. u.
(representing sulphur). The resulting fragment ions
undergo loss of 28 a. m. u. (most likely dinitrogen),
followed by loss of either mass 14 or (successively) two
units of 27 a. m. u. (probably 2 x HCN) suggesting
The latter compound could also be formed by
hydrolysis of 12 or 13 by moisture contained in the
solvent pyridine. The modest yields of products 5 and 6
have to be accepted, since they are in fact overall yields
obtained in multistep sequences.
tautomerization of 6a-c to 4-organyl-5-thioxo-3,3-
.
dicarbonitrile radical cation A + on electron impact prior
Conclusion.
to fragmentation (see Scheme 4).
The identity of reduction products 9 and 10 as well as
The reactions and products presented here provide
insight into the spontaneous reactions between the
electron donating 4-substituted thiosemicarbazides 1a-c
and a suitable electron acceptor, here 2. In a fairly
complex and multistep process two types of a 3-spiro-
annelated triazolethione 5 and a 1-dicyanomethylene
thiosemicarbazone 6 products, are formed from 1a-c
and 2. The latter has a dual functioning role as a
dehydrogenating agent and a source of the dicyano-
methylene units. The results reported here supplement
the rich chemistry of (2,4,7-trinitro-9H-fluoren-9-
ylidene)propanedinitrile (2).
2,4,7-trinitro-9-fluorenone (8) derived from
2 was
demonstrated by comparison with authentic samples [27].
Formation of the spiro compounds 5a-c and the
thiosemicarbazonopropanedinitriles 6a-c as well as
products 8-10 derived from 2 may be rationalized as
outlined in Scheme 5.
Starting material 2 is partially reduced to 10. Both the
starting thiosemicarbazide 4 and the intermediate dihydro
compound 13 could serve as reducing agents. Nucleophilic
attack of the terminal NH2 of 4a-c on C-9 of 10, similar to
the attack of 4a,b on the C=C bond of ethanetetracarbo-
nitrile [24] with elimination of malononitrile from adduct
11 gives rise to 12. Intramolecular attack of the terminal
R-NH group on C-9 of the fluorene skeleton of 12 leads to
the intermediates 13a-c which have to be dehydrogenated
(pobably by another molecule of 2 or air-oxygen) to give
the spiro products 5a-c. The alternative option, namely
nucleophilic attack by the thione sulphur atom on C-9 of
12, is not observed since a product of structure 7 instead
of 5a-c is not found. Alternatively to attacking C-9,
however, N1 of 4a-c can add to the dicyanomethylene
carbon of 2 (again in analogy with the reaction of 4a,b
with ethenetetracarbonitrile [24]).
EXPERIMENTAL
Melting points (uncorrected) were determined in open glass
capillaries on a Gallenkamp melting point apparatus. The ir
spectra were recorded from potassium bromide disks with a
Shimadzu 408 or Bruker Vector 22 FT-IR instrument. The 300
MHz 1H and 75 MHz 13C nmr spectra were observed on a
Bruker WM 300 instrument with tetramethylsilane as the
internal standard using dimethylsulfoxide-d6 as solvent, br =
broad. The 13C nmr signals were assigned on the basis of DEPT
135/90 spectra for 5c and 6c. The mass spectra (70 eV, electron
impact mode) were recorded on an AMD 604 instrument.
Elemental analyses were carried out at the Microanalytical
Center, Cairo University, Egypt. Preparative layer
chromatography was performed on air dried 1.0 mm thick layers
of slurry applied silica gel Merck PF254 on 48 cm wide and 20
cm high glass plates. Zones were detected by their color or by
Adduct 14 in turn may release 6a-c and 2,4,7-
trinitrofluorene (15) (Scheme 3). It is conceivable that
compound 10 instead of 2 undergoes such a sequence as
well. The fluorenes may then undergo multistep oxida-
tions with air-oxygen to yield the fluorenones 8 and 9.

852
A. A. Hassan, Y. R. Ibrahim, A. M. Shawky and D. Döpp
Vol 43
Scheme 5
NO2
NH2
reduction
O2N
NO2
O2N
NO2
NC
CN
CN
NC
CN
(NO2)2
NH2
(NO2)3
2 =
NC
10 =
CN
NC
(NO2)2
NH2
(NO2)2
NH2
10
4 a-c
-H2C(CN)2
NH
HN
NC
..
N
H
N
C
S
N R
C
S
N R
H
H
CN
11 a-c
12 a-c
(NO2)2
(NO2)2
NH2
R
NH2
R
N
N
N
HN
HN
N
-2H
S
S
13 a-c
5 a-c
NO2
(NO2)3
H
O2N
NO2
15
2
4 a-c
NC
CN
H
S
CN
HN
N
C
S
N R
H
R NH C
N
N
C
CN
6 a-c
14 a-c
quenching of indicator fluorescence upon exposure to 254 nm
light.
contained compounds 5a-c and 6a-c. The material confined to
the start was rechromatographed using cyclohexane/
ethylacetate (2:1) to give another two zones, the faster
migrating one of which contained orange coloured 4-amino-
2,7-dinitro-9-fluorenone (9) whereas the second zone (deep
blue) contained (4-amino-2,7-dinitro-9H-fluoren-9-ylidene)pro-
panedinitrile (10). Extraction of the zones with acetone gave a
residue, which was rechromatographed with the same eluent to
enhance separation. Recrystallization from suitable solvents
afforded compounds 5, 6, 8-10.
Starting Materials.
4-Phenylthiosemicarbazide (4a) [35,36], 4-benzylthiosemi-
carbazide (4b) [36,37] and 4-(2-propenyl)thiosemicarbazide (4c)
[37,38] were prepared according to literature procedures. (2,4,7-
Trinitro-9H-fluoren-9-ylidene)propanedinitrile (2) was prepared
from 2,4,7-trinitro-9-fluorenone and malononitrile according to
Mukherjee [39].
Reaction of 4-Substituted Thiosemicarbazides 4a-c with 2.
4-Amino-2,7-dinitro-4'-phenyl-4',5'-dihydrospiro[fluoren-9,3'-
(1,2,4-triazole)]-5'-thione (5a).
A
solution of substituted thiosemicarbazides 4a-c (1
This compound had mp 286-288º, pale reddish orange crystals
from acetonitrile, yield 91 mg (21 % ); ir: 3437, 3356 (NH2),
1600 (aryl), 1352, 1020 (C=S, C-N), 1528, 1340 (NO2) cm-1; 1H
nmr: ꢀ 6.48 (br, 2H, NH2), 7.29-7.46, 8.11-8.71 and 9.06-9.24
(all m, 10H, aryl H); 13C nmr : ꢀ 71.66 (C-9 = C-3´), 114.00,
121.6, 124.0, 124.5, 125.3, 128.8 and 129.2 (all aryl CH),
139.40 (phenyl C-1), 141.6 (C-8a), 142.36 (C-9a), 143.8 (C-4b),
145.6 (C-4), 147.8, 148.6 (C-7, C-2) and 181.8 (C=S); EI-MS
m/z: % 432 (M+, 11), 404 ([M - N2]+, 74), 297 ([M - PhNCS]+,
28), 205 ([297 - 2 NO2]+ , 36), 189 (18), 135 ([PhNCS]+, 62), 77
(Ph+, 100), 65 (42).
mmol) in 10 mL of dry pyridine was added dropwise to a
solution of 2 (2 mmol) in 15 mL of dry pyridine with
stirring. The mixture was heated gently without increasing
the temperature above 100 ºC for 3 hours. The solvent was
removed by concentration and the residue was washed
several times with ethanol to remove residual pyridine. The
residue was dissolved in acetone and separated by
preparative layer chromatography using cyclohexane/
ethylacetate (5:1) as eluent into numerous zones, three of
which were extracted.
The fastest migrating zone contained 2,4,7-trinitro-9-
fluorenone (8), the second and third zones which quenched all
indicator fluorescence upon exposure to 254 nm uv-light
Anal. Calcd. for C20H12N6O4S (432.41): C, 55.55; H, 2.80; N,
19.44; S, 7.42. Found: C, 55.69; H, 2.71; N, 19.29; S, 7.58.

Jul-Aug 2006
Reaction of 4-Substituted Thiosemicarbazides
853
4-Amino-4'-benzyl-2,7-dinitro-4',5'-dihydrospiro[fluoren-9,3'-
[4-(2-Propenyl)-thiosemicarbazono]propanedinitrile (6c).
(1,2,4-triazole)]-5'-thione (5b).
This compound had mp 163-165º, pale brown crystals from
ethanol, yield 48 mg (25 %); ir: 3344, 3270 (NH), 2220 (CN),
1625 (C=N), 1560 (NH def. and C-N str.), 1358, 1015 (C=S, C-
This compound had mp 272-273º, pale reddish orange
crystals from acetonitrile, yield 103 mg (23 %); ir: 3420,
3342 (NH2), 1595 (aryl), 1354, 996 (C=S, C-N), 1525 and
1
N); H nmr: ꢀ 4.10 - 4.12 (br, 2H, allyl CH2N), 5.03-5.14 (m,
1
1344 (NO2) cm-1; H nmr: ꢀ 4.35 (br, 2H, CH2Ph), 6.45 (br,
2H, allyl CH2=), 5.81-5.90 (m, 1H, allyl CH=), 7.89 (br, 1H,
NH), 8.69 (br, 1H, NH); 13C nmr: ꢀ 43.6 (allyl CH2N), 115.6
(allyl CH2=), 118.2 (CN), 135.1 (allyl CH=), 156.9 (C=N), 183.4
(C=S); EI-MS m/z: % 193 (M+, 6), 161 ([M - S]+, 4), 133 ([161 -
N2]+, 100), 106 ([133 - HCN]+, 78), 79 (41), 42 (63).
2H, NH2), 7.22-7.32, 8.16-8.68 and 9.10-9.22 (all m, 10H,
aryl H); 13C nmr: ꢀ 71.12 (C-9 = C-3ꢀ), 114.8, 122.1, 123.8,
126.4, 128.1, 128.3, 128.6, 129.1 (all aryl CH), 142.9 (C-
4b), 141.1 (C-8a), 141.8 (C-9a), 146.4 (C-4), 147.5 (C-7),
148.8 (C-2) and 181.4 (C=S); EI-MS m/z: % 446 (M+, 7),
418 ([M - N2]+, 69), 297 ([M - PhCH2NCS]+, 21), 205([297 -
Anal. Calcd. for C7H7N5S (193.23): C, 43.51; H, 3.65, N,
36.24; S, 16.59. Found: C, 43.68; H, 3.73; N, 36.12; S, 16.77.
+
2 NO2]+, 28), 189 (11), 149 ([PhCH2NCS]+, 83), 91 (PhCH2 ,
2,4,7-Trinitro-9-fluorenone (8).
100), 77 (Ph+, 43).
Anal. Calcd. for C21H14N6O4S (446.44): C, 56.50; H, 3.16; N,
18.82; S, 7.18. Found: C, 56.39; H, 3.33; N, 18.67; S, 7.05.
This compound had mp 173-175°C (Lit. [34], 175°C), (6 - 8 %).
4-Amino-2,7-dinitro-9-fluorenone (9).
4-Amino-2,7-dinitro-4'-(2-propenyl)-4',5'-dihydrospiro[fluoren-
9,3'-(1,2,4-triazole)]-5'-thione (5c).
This compound had mp 310-312°C (Lit. [27] 310-312°C),
(12 - 16 %).
This compound had mp 212-214°, pale reddish orange
crystals from ethanol, yield 95 mg ( 24 %); ir: 3417, 3338
(NH2), 1588 (aryl), 1348, 1010 (C=S, C-N), 1530 and 1338
(4-Amino-2,7-dinitro-9H-fluoren-9-ylidene)propanedinitrile (10).
This compound had mp 340-342°C (Lit. [27] 340-342°C),
(8 –11 %).
1
(NO2) cm-1; H nmr: ꢀ 4.23 (br, 2H, allyl CH2N), 5.24-5.36 (m,
2H, allyl CH2=), 6.05-6.15 (m, 1H, allyl CH=), 6.50 (br, s, 2H,
NH2), 8.05-8.64, 9.02-9.20 (two m, 5H, aryl H); 13C nmr: ꢀ
43.12 (allyl CH2-N), 71.08 (C9 = C3ꢀ), 115.42 (allyl CH2=),
121.6, 124.0, 128.8 and 129.2 (all aryl CH), 135.13 (allyl CH=),
141.3 (C-8a), 142.1 (C-9a), 143.6 (C-4b), 146.0 (C-4), 147.4,
148.3 (C-7, C-2) and 181.3 (C=S); EI-MS m/z: % 396 (M+, 11),
368 ([M - N2]+, 100), 297 ([M - Allyl-NCS]+, 12), 205 (14), 99
(81), 41 (98).
Acknowledgement.
A. A. Hassan is indebted to the A. v. Humboldt-Foundation
for the award of a fellowship from August 2003 to Sept. 2003
and also for the donation of the Shimadzu 408 IR
spectrophotometer. Financial support of this work by Fonds der
Chemischen Industrie is gratefully acknowledged.
Anal. Calcd. for C17H12N6O4S (396.38): C, 51.51; H, 3.05; N,
21.20; S, 8.09. Found: C, 51.34; H, 2.92; N, 21.36; S, 7.92.
REFERENCES AND NOTES
(4-Phenylthiosemicarbazono)propanedinitrile (6a).
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This compound had mp 218-220º, brown crystals from
ethanol), yield 57 mg (25 %); ir: 3315 and 3280 (NH), 2225
(CN), 1635 (C=N), 1570 (NH def. and C-N str.), 1358, 998
1
(C=S, C-N) cm-1; H nmr: ꢀ 7.14-7.17, 7.24-7.36, 7.49-7.58
(all m, 5H, phenyl H), 9.71 (br, 1H, NH), 9.88 (br, 1H, NH-
Ph); 13C nmr: ꢀ 118.3 (CN), 122.9, 125.6, 128.8 (phenyl CH),
141.2 (phenyl C-1), 157.8 (C=N), 183.7 (C=S); EI-MS m/z: %
229 (M+, 6), 197 ([M - S]+, 9), 169 ([197 - N2]+, 37), 155
([169 - 14]+, 100), 128 (67), 101 (22), 92 (76), 77 (81), 64
(18), 51 (44).
Anal. Calcd. for C10H7N5S (229.26): C, 52.39; H, 3.08; N,
30.55; S, 13.99. Found: C, 52.47; H, 2.96; N, 30.39; S, 14.14.
(4-Benzylthiosemicarbazono)propanedinitrile (6b).
This compound had mp 201-203º, brown crystals from
acetonitrile, yield 56 mg (23 %); ir: 3330 and 3268 (NH), 2222
(CN), 1628 (C=N), 1565 (NH def. and C-N str.), 1355, 1005
1
(C=S, C-N); H nmr: ꢀ 4.33 (br, 2H, CH2-Ph), 7.08-7.15, 7.46-
7.53 (all m, 5H, phenyl H), 8.65 (br, 1H, NH-CH2Ph), 9.45 (br,
1H, NH-C=S); 13C nmr: ꢀ 52.6 (CH2), 118.3 (CN), 123, 126.5,
128.3, (phenyl CH); 139.6 (phenyl C-1), 156.8 (C=N), 183.8
(C=S); EI-MS m/z: % 243 (M+, 3), 211 ([M - S]+, 6), 183 ([211 -
N2]+, 12), 169 ([183 - 14]+, 100), 142 ([169 - HCN]+, 77), 115
([142 - HCN]+, 22), 104 (61), 77 (••), 64 (16), 51 (56).
Anal. Calcd. for C11H9N5S (243.29): C, 54.30; H, 3.73; N,
28.79; S, 13.18. Found: C, 54.19; H, 3.88; N, 28.93; S, 13.29.
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