Ethenetetracarbonitrile and heterocyclization of symmetrical dithiobiurea as well as thioureidoethylthiourea derivatives

Article abstract of DOI:10.1515/znb-2004-0807

N,N′-Disubstituted hydrazinecarbothioamides 6a-c and substituted thioureidoethylthioureas 12a-c react with ethenetetracarbonitrile (TCNE) in ethyl acetate or chlorobenzene to form the derivatives of pyrazole 7, 8; thiadiazole 10, 11 thiadiazepine 9, thiadiazepane 13, imidazolidine 14 and diazepine 15.

Full text of DOI:10.1515/znb-2004-0807

Ethenetetracarbonitrile and Heterocyclization of Symmetrical
Dithiobiurea as well as Thioureidoethylthiourea Derivatives
Alaa A. Hassan, Aboul-Fetouh E. Mourad, Kamal M. El-Shaieb, and Ashraf H. Abou-Zied
Chemistry Department, Faculty of Science, El-Minia University, El-Minia, A. R. Egypt
Reprint requests to Prof. Dr. A. A. Hassan. E-mail: alaahassan2001@yahoo.com
Z. Naturforsch. 59b, 910 – 916 (2004); received January 30, 2004
Dedicated to Professor Dietrich D o¨ pp on the occasion of his 65th birthday
N,N’-Disubstituted hydrazinecarbothioamides 6a – c and substituted thioureidoethylthioureas
2a – c react with ethenetetracarbonitrile (TCNE) in ethyl acetate or chlorobenzene to form the
1
derivatives of pyrazole 7, 8; thiadiazole 10, 11 thiadiazepine 9, thiadiazepane 13, imidazolidine 14
and diazepine 15.
Key words: Ethenetetracarbonitrile, Dithiobiurea, Thioureidoethylthiourea Derivatives,
Heterocyclization
Introduction
Ethenetetracarbonitrile (TCNE) is considered as
a highly electron-deficient and strongly electrophilic
reagent, due to the fact that the cyano group is a
powerful electron-withdrawing group and a poor dipo-
larophile [1 – 3]. As a consequence, TCNE shows high
reactivity towards many nucleophiles like alcohols,
amines and thiols [3] and easily forms molecular com-
plexes by intermolecular charge-transfer interactions
[1, 3 – 5]. Its affinity for electrons is high, as demon-
strated by the formation of stable radical anion as well Chart 1.
as dianion, through two reversible processes [6, 7].
ogous, namely N,N’-disubstituted hydrazinecarboth-
ioamides 6 a – c and thioureidoethylthiourea deriva-
tives 12a – c towards TCNE.
The recent literature is enriched with progressive find-
ings about the reactions of TCNE with thiocarbony-
lylides [8], thiophenone S-methylide [9], alkylidenecy-
clobutenes [10], N-arylbenzo[d,e]isoquinolines [11]
and N-aryldibenz[c,e]azepines [11] as well as N-aryl-
isoindolines [12].
Results and Discussion
Addition of two equivalents of TCNE to a solution
On the other hand, the interaction of thiosemicar- of 6c in ethyl acetate as a solvent at room tempera-
bazide and dithiocarbazate derivatives with TCNE and ture resulted in a green colouration of the solution,
benzo- as well as naphthoquinones as π-acceptors af- which later became dark brown. This behaviour may
forded various heterocyclic compounds via a single- be explained as due to the initial formation of unstable
electron transfer mechanism [13 – 17].
charge-transfer (CT) complexes, followed by chemical
Recently, we have demonstrated that 4-substituted reaction. Monitoring of the reaction by visible spec-
thiosemicarbazides 1 a – c reacted with TCNE in troscopy failed, since the reaction is fast and also,
ethyl acetate with admission of air to give products 2 – at lower concentrations no significant colour changes
5
[18].
were observed any more.
These results prompted us to continue our investi-
The concentration residue was subjected to vacuum
gations on the behaviour of other electron poorer anal- sublimation to remove any unreacted TCNE. Chro-
0
932–0776 / 04 / 0800–0910 $ 06.00 ꢀc 2004 Verlag der Zeitschrift f u¨ r Naturforschung, T u¨ bingen · http://znaturforsch.com
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A. A. Hassan et al. · Ethenetetracarbonitrile and Heterocyclization of Symmetrical Dithiobiurea
911
Fig. 1. Suggested hydrogen Bond formation in coumpund 7a.
the steric energy value of compound 7a is found to
be ∆E = 25.36 Kcal/mol based on the aforementioned
semi-empirical calculations using the MM2 level of
theory [19], whereas this value is diminished in case
of hydrogen bonding to become ∆E = 15.50 Kcal/mol.
The stability of compounds 7 in this form supports the
exclusion of any other expected isomeric forms. Fur-
thermore, compound 7a was also assigned on the basis
Chart 2.
matographic separation of the residue obtained after
sublimation gave numerous zones, from which prod-
ucts 7 – 11 could be isolated (Chart 2). Due to insuf-
ficient solubility of 6b, c in ethyl acetate, the reac-
tion was carried out in chlorobenzene at room tem-
perature. In the latter solvent, nearly quantitative con-
versions were achieved already after four days, but
yields 7, 9 – 11 tended to be moderate. The structure
of 7 – 9 were delineated from the spectroscopic prop-
erties as follows: The IR spectrum of 7a shows ab-
of intramolecular H bridge detected by IR (in dilute
1
CCl ) and H NMR (see the Experimental Section).
4
On the other hand, the formation of compound
8
supports our suggested structure (Chart 2). The
1
H NMR spectrum of 8 clearly shows the absence
of pyrazole-NH and the presence of exocyclic NH2
at 7.25 ppm as well as allyl-NH at 7.57 ppm.
sorption characteristic of NH and NH groups at 3410,
2
−
1
−1
3
370 cm , cyano groups at 2218 and 2210 cm , C=S
13
The C NMR shows signals at 141.12, 88.64 and
−
1
1
at 1360 cm . The H NMR spectrum of 7a clearly
shows the presence of three different broad signals
centered at 7.30, 9.67 and 11.40 ppm with the ratio
1
52.26 ppm due to pyrazole-C-3, C-4 and C-5, re-
13
spectively. Also, the C NMR of 8 clearly indi-
cates the presence of allyl group at 43.12, 114.63 and
134.32 ppm as well as C=S at 176.32 ppm. The mass
spectrum of compound 8 exhibited a molecular ion
peak at m/z 232 (43%).
2
:1:1 due to exocyclic NH , NH attached to phenyl,
2
1
3
as well as pyrazole-NH, respectively. In its C NMR
spectrum pyrazole-C-3, -C-4 and –C-5 resonate at δ =
4
6.36, 59.76 and 153.66 ppm, respectively. Further
For the formation of thiadiazepines 9, the IR spec-
peaks at 117.92, 119.25 ppm (CN) and 175.46 ppm
C=S), besides the aromatic carbons support the as-
signed structure. The elemental analysis of 7a sug-
gested a gross formula C H N S. This was confirmed
−1
trum of 9a shows characteristic bands at 3380 cm
(
−1
(
NH ), 2225 and 2215 cm for cyano groups, in ad-
2
dition to C=N as well as Ar-C=C groups at 1630 and
−1
1
1
3
9
7
1590 cm . The H NMR of 9a shows one broad sin-
by the mass spectrum, which exhibited a molecular ion
at 295 (100%). The analytical data of compound 7a
also matched another isomers which could be ruled out
on the basis of H-NMR, C NMR, and the fragment
ions in the mass spectrum of 7a at m/z 268, 202, 135,
glet at 7.41 ppm due to NH as well as the aromatic
2
13
protons. The C NMR of 9a shows signals at 33.12,
87.94, 150.33 and 161.74 ppm due to thiadiazepine-
1
13
C-5, -C-6, -C-7 and -C-2, respectively.
The presence of TCNE is very important and es-
sential to allow the formation of thiadiazoles 10 and
1
19, 104, 77 and 51. The structure of 7a fits best to all
the spectroscopic data (see Experimental Section).
11, because on addition of 6a – c to ethyl acetate or
Interestingly the molecular modeling (MM2) [19] chlorobenzene without TCNE for 96 hours, gave again
of 7a, as an example, supported the suggested struc- compounds 6a – c and did not follow the previous se-
tural feature of 7 as indicated in Chart 2. Since the quence of chemical reactions. The structures of thia-
bond distance between the hydrogen atom in NH and diazoles 10 and of thiadiazole-2-thiones 11 were con-
˚
the NH group is found to be 1.5 A, we can sug- firmed by comparison with authentic samples.
2
gest a hydrogen bond is formed between them. Con-
The weaker donor 12 was expected to react simi-
sequently, this hydrogen bond can offer the formation larly to TCNE with 6a – c. Treatment of 12a – c with
of another six membered ring (Fig. 1). Additionally, two equivalents of TCNE in tetrahydrofuran as sol-
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A. A. Hassan et al. · Ethenetetracarbonitrile and Heterocyclization of Symmetrical Dithiobiurea
C-2 methylene groups. The 13C DEPT NMR spectrum
showed negative signals at δ = 43.77 and 47.76 ppm,
confirming the presence of two different methylene
1
groups in diazepine ring. The H NMR showed also,
the presence of allyl group which appeared as three
multiplets centered at δ = 3.91−3.96, 5.04−5.15 and
5
.88 − 5.96 ppm due to allyl-CH N, allyl-CH = and
2
2
1
allyl-CH=, respectively. In addition the H NMR spec-
trum exhibited three broad singlets centered at 7.20,
7
.54 and 7.83 ppm due to exocyclic NH , allyl-NH
2
and diazepine-NH, respectively. The decoupled carbon
spectrum of 15c showed signals at δ = 178.81 ppm as-
signed to C=S; 33.11, 61.22 and 166.83 ppm due to
diazepine C-5, C-6 and C-7 respectively, in addition to
the allyl carbons. The structure of thiadiazepane 13 as
confirmed on the basis of spectroscopic data and com-
parison with authentic samples.
Chart 3.
vent at room temperature resulted in a green coloura-
tion of the solution, which later became dark brown.
The residue remaining after concentration was sub-
jected to preparative layer chromatography to give
7
(
3
-substituted imino-[1,3,6]thiadiazepines 13a– c in
63– 69%) yield. Refluxing the reaction mixture for
h and concentration the preparative runs followed by
Experimental Section
Mp’s were determined in open glass capillaries on Gallen-
chromatographic separation, products 14 and 15 could Kamp melting point apparatus and are uncorrected. The IR
be isolated.
spectra were recorded with a Shimadzu 408 or Bruker Vac-
tor 22 FT IR instruments, using potassium bromide pellets
The molecular formula of compounds 14a – c is sup-
ported by the mass spectra, which gave the predicted
molecular ion peaks, and were further confirmed by
elemental analysis. The IR spectrum of (for example)
1
13
or CCl . The 300 MHz H and 75 MHz C NMR spectra
4
were recorded on a Bruker WM 300 instrument, chemical
shifts are expressed as δ (ppm) with tetramethylsilane as in-
ternal references, s = singlet, t = triplet, m = multiplet, br =
1
4a shows a sharp absorption characteristic of cyano
1
3
broad; C-assignment have been made with the aid of DEPT
35/90 spectra. The mass spectra (70 eV, electron impact
−
1
groups at 2220 cm and several peaks at 1620 and
1
−
1
1
590 cm for skeletal vibration of aryl groups, as well
mode) were obtained with a Varian MAT 311 doubly focus-
ing instrument. Elemental analyses were determined at the
Microanalytical Center, Cairo University, Egypt. For prepa-
ration layer chromatography 48 cm wide and 20 cm tall glass
−
1
as another absorption at 1350 cm due to C=S. The
1
H NMR spectrum of 14a clearly shows the presence
of two equivalent methylene groups at δ = 3.70 ppm
and one broad singlet at 9.59 ppm due to phenyl- plates, covered with a 1 mm thick layer of slurry applied and
NH, in addition to the aromatic protons. The pres- air-dried silica gel Merck PF254, were used. Zones were de-
1
3
ence of methylene groups is also evident from the
C
tected by their colour or by quenching of indicator fluores-
DEPT NMR spectrum exhibiting negative signals at cence upon exposure to 254 nm light.
δ = 50.66 ppm. The decoupled carbon spectrum of 14a
showed another signal at δ = 181.33 ppm assigned to Starting materials
C=S, pointing out that the addition did not occur at the
N,N’-Disubstituted hydrazinecarbothioamides 6a – c and
sulphur atom.
substituted thioureidoethylthioureas 12a – c were prepared
according to published procedures [20 – 27], as were
N,N’-diphenylhydrazinecarbothioamide (6a) [20, 21], N,N’-
dibenzylhydrazinecarbothioamide (6b) [22], N,N’-diallyl-
hydrazinecarbothioamide (6c) [23, 24], 1-phenyl-3-[2-(3-
phenylthioureido)ethyl]thiourea (12a) [25], 1-benzyl-3-[2-
(3-benzylthioureido)ethyl]thiourea (12b) [26] and 1-allyl-
The elemental analysis of 15c suggested a gross
formula C H N S. This was confirmed by the mass
spectrum, which exhibited a molecular ion at m/z 287
12
13
7
(
16%). The IR spectrum showed strong bands at 2218
−
1
and 2210 cm
3
due to cyano groups, 3410, 3380,
−
1
−1
200 cm
(NH and NH) as well as 1350 cm
2
1
(C=S). The H NMR spectrum clearly indicates the
3
-[2-(3-allylthioureido)ethyl]thiourea (12c) [27]. Ethenete-
presence of two multiplets at δ = 3.37 − 3.44 and tracarbonitrile (TCNE, Merck) was purified by crystalliza-
◦
3
.56 − 3.62 ppm are assigned to diazepine-C-3 and tion from chlorobenzene and sublimed, m. p. 198 – 199 C.
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A. A. Hassan et al. · Ethenetetracarbonitrile and Heterocyclization of Symmetrical Dithiobiurea
913
Reaction of N,N’-disubstituted hydrazinecarbothioamides pyrazole-NH). – 13C NMR (75.47 MHz, DMSO-d ): δ =
6
6
a−c with TCNE
46.20 (pyrazole-C-3), 52.90 (CH Ph), 59.88 (pyrazole-C-4),
2
1
17.89, 119.12 (CN), 126.86, 127.12, 128.96, 139.12 (Ar-
A solution of 6a, b (2 mmol) in dry cholorobenzene 25 ml,
C), 152.18 (pyrazole-C-5), 176.10 (C=S). – MS (EI, 70 eV):
or in 15 ml of ethyl acetate in case of 6c was added drop-
wise with stirring at room temperature to TCNE (4.0 mmol)
in chlorobenzene (20 ml) or ethyl acetate (10 ml). The reac-
tion mixture colour changed gradually from green to brown.
The stirring was containued for 48 h (in presence of ethyl
+
m/z (%) = 309 (100) [M ], 282 (38), 214 (41), 149 (38),
1
33 (42), 118 (83), 77 (62). – C H N S (309.35): calcd.
14 11 7
C 54.36, H 3.58, N 31.69, S 10.37; found C 54.28, H 3.46,
N 31.77, S 10.29.
acetate, and 96 h in case of chlorobenzene) with admission 5-Amino-3,3,4-tricyano-2,3-dihydropyrazole-1-carbothioic
of air to complete the reaction. After concentration to dry- acid allylamide (7c)
◦
ness the residue was sublimed at 80 C under vacuum to re-
◦
M. p. 194 C. – IR (KBr): ν = 3415, 3360 (NH2,
move all unreacted TCNE. The residue was then separated
NH), 2965, 2860 (Ali-CH), 2225, 2210 (CN), 1565 (C=C),
355 (C=S) cm . – H NMR (300.13 MHz, DMSO-
by preparative layer chromatography (100 mg per plate) us-
−1
1
1
ing a suitable solvent mixture as eluent (cyclohexane/ethyl
acetate 3:1) to give numerous coloured zones, the five intense
of which were removed and extracted. The first and second
zones, which quenched all indicator fluorescence upon ex-
posure to 254 nm UV-light, contained the thiadiazole deriva-
tives 10a – c (9 – 12%) and 11a – c (8 – 10%). The third zone
characterized by its brown colour contained the thiadiazepine
a – c (28 – 31%) and finally the slowest migrating zones
which always characterized by reddish brown and orange
colour) contained the pyrazole derivsatives 8 (7%) and 7a –
c (28 – 31%). Extraction of the zones with acetone gave a
residue, which was rechromatographed and recrystallized to
separate the pure compounds.
d ): δ = 4.11 (m, 2H, allyl-CH N), 5.17 − 5.21 (m, 2H,
6
2
allyl-CH =), 5.88 − 5.95 (m, 1H, allyl-CH=), 7.22 (br, s,
2
2
H,NH ), 7.57 (br, s, allyl-NH), 11.33 (br, s, 1H, pyrazole-
2
1
3
NH). – C NMR (75.47 MHz, DMSO-d ): δ = 43.56
allyl-CH N), 46.31 (pyrazole-C-3), 59.72 (pyrazole-C-4),
15.08 (allyl-CH =), 118.12, 119.20 (CN), 134.83 (allyl-
2
CH=), 152.93 (pyrazole-C-5), 176.12 (C=S). – MS (EI,
0 eV): m/z (%) = 259 (86) [M ], 232 (36), 166 (51),
04 (88), 99 (34), 41 (100). – C H N S (259.29): calcd.
C 46.32, H 3.50, N 37.81, S 12.37; found C 46.48, H 3.41,
N 37.94, S 12.52.
6
(
2
1
9
(
+
7
1
1
0 9 7
5
-Amino-3,4-dicyanopyrazole-1-carbothioic acid allylamide
(8)
5
-Amino-3,3,4-tricyano-2,3-dihydropyrazole-1-carbothioic
◦
M. p. 167 C. – IR (KBr): ν = 3430, 3386 (NH , NH),
2
acid phenylamide (7a)
2
968, 2946 (Ali-CH), 2222 (CN), 1625 (C=N), 1565 (C=C),
1360 (C=S) cm . – H NMR (300.13 MHz, DMSO-
−1
1
◦
M. p. 225 C. – IR (KBr): ν = 3410, 3370 (NH , NH),
2
−1
d ): δ = 4.08 (m, 2H, allyl-CH N), 5.16 − 5.22 (m,
2
218, 2210 (CN), 1620, 1586 (Ar-C=C), 1360 (C=S) cm
,
6
2
−3
−1
2H, allyl-CH =), 5.88 − 5.91 (m, 1H, allyl-CH=), 7.25
ν (CCl , 10
M, d = 3 cm) 3396, 3352 cm
(broad
2
4
13
1
(br, s, 2H,NH ), 7.57 (br, s, 1H,allyl-NH). – C NMR
2
NH and NH assoc.). – H NMR (300.13 MHz, DMSO-d ):
2
6
(
DMSO-d ): δ = 43.12 (allyl-CH N), 88.64 (pyrazole-
C-4), 114.63 (allyl-CH =), 117.32, 118.93 (CN), 134.32
allyl-CH=), 141.12 (pyrazole-C-3), 152.26 (pyrazole-C-5),
176.32 (C=S). – MS (EI, 70 eV): m/z (%) = 232 (43) [M ],
66 (23), 138 (18), 104 (61), 99 (76), 41 (100). – C H N S
232.27): calcd. C 46.54, H 3.47, N 36.18, S 13.81; found
C 46.68, H 3.53, N 36.10, S 13.64.
δ = 7.34 − 7.65 (m, 5H, Ar-H), 7.30 (br, s, 2H,NH ), 9.67
6
2
2
(br, s, 1H, NH), 11.40 (br, s, 1H, pyrazole-NH) the latter
2
(
three signals fade upon treatment of the DMSO-d -solution
6
+
1
3
with D O. – C NMR (75.47 MHz, DMSO-d ): δ = 46.36
2
6
1
(
(pyrazole-C-3), 59.76 (pyrazole-C-4), 117.92, 119.25 (CN),
9 8
6
1
5
27.43, 128.86, 129.85, 139.42 (Ar-C), 153.66 (pyrazole-C-
), 175.46 (C=S). – MS (EI, 70 eV): m/z (%) = 295 (100)
+
[M ], 268 (33), 202 (46), 135 (48), 119 (37), 104 (94), 77
7
-Amino-2-phenylimino-2H-[1,3,4]thiadiazepine-5,5,6-
tricarbonitr ile (9a)
(72), 51 (48). – C H N S (295.32): calcd. C 52.87, H 3.07,
13
9 7
N 33.20, S 10.86; found C 52.94, H 2.89, N 33.04, S 10.98.
◦
M. p. 212 C. – IR (KBr): ν = 3380 (NH ), 2225,
215 (CN), 3068 (Ar-H), 1630 (C=N), 1590 (Ar-
C=C) cm . – H NMR (300.13 MHz, DMSO-d ): δ = 7.41
2
2
5
-Amino-3,3,4-tricyano-2,3-dihydropyrazole-1-carbothioic
−1
1
6
acid benzylamide (7b)
1
3
(
br, s, 2H,NH ), 7.53 − 7.70 (m, 5H, Ar-H). – C NMR
2
◦
M. p. 244 C. – IR (KBr): ν = 3422, 3360 (NH2, (75.47 MHz, DMSO-d ): δ = 33.12 (thiadiazepine-
6
NH), 2220, 2210 (CN), 1630, 1600 (Ar-C=C), 1354 (C=S) C-5), 87.94 (thiadiazepine-C-6), 116.22, 117.41 (CN),
cm . – H NMR (300.13 MHz, DMSO-d ): δ = 4.65 123.14, 127.23, 128.88 (Ar-CH), 143.92 (Ar-C=N), 150.33
−1
1
6
(
(
br, s, 2H, CH Ph), 7.24 (br, s, 2H, NH ), 7.28 − 7.68 (thiadiazepine-C-7), 161.74 (thiadiazepine-C-2). – MS (EI,
2
2
+
m, 5H, Ar-H), 9.61 (s, br, 1H, NH), 11.28 (br, 1H, 70 eV): m/z (%) = 293 (100) [M ], 267 (11), 227 (11),
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A. A. Hassan et al. · Ethenetetracarbonitrile and Heterocyclization of Symmetrical Dithiobiurea
2
5
01 (18), 196 (22), 135 (27), 119 (25), 104 (81), 77 (47), and stirred at room temperature for 48 h, during which time
1 (28). – C H N S (293.31): calcd. C 53.23, H 2.41, the original colour changed from yellow to green and finally
1
3
7 7
N 33.43, S 10.93; found C 53.37, H 2.53, N 33.29, S 11.12.
to brown. After concentration, the solid residue was treated
with a few ml of acetone and subjected to plc using cyclohex-
ane/ethyl acetate (3:1) as eluent to afford one zone contained
the thiadiazepane derivatives 13a – c.
7
-Amino-2-benzylimino-2H-[1,3,4]thiadiazepine-5,5,6-
tricarbonitrile (9b)
On the other hand, when the reaction mixture was refluxed
in THF for 3 h, followed by concentration and separation the
residue by tlc using cyclohexane/ethyl acetate (1:1), gave two
zones. The fastest migrating one (brown colour) contained
the diazepine derivatives 15 (35 – 42%), and the second zone
◦
M. p. 226 C. – IR (KBr): ν = 3395 (NH ), 2960 (Ali-
2
CH), 2222, 2215 (CN), 3080 (Ar-CH), 1625 (C=N),
580 (Ar-C=C) cm . – H NMR (300.13 MHz, DMSO-
d ): δ = 4.64 (br, s, 2H, CH Ph), 7.38 (br, s, 2H,NH ),
−1
1
1
6
7
2
2
13
.48 − 7.68 (m, 5H, Ar-H). – C NMR (75.47 MHz,
(orange colour) contained the imidazolidine derivatives 14
DMSO-d ): δ = 32.96 (thiadiazepine-C-5), 48.68 (CH Ph),
6
2
(41 – 47%).
8
1
1
3
1
8.14 (thiadiazepine-C-6), 115.92, 117.22 (CN), 125.21,
7-Phenylimino-[1,3,6]thiadiazepane-2-thione (13a)
28.56, 129.20, 137.74 (Ar-C), 150.76 (thiadiazepine-C-7),
(Lit. [26]).
62.10 (thiadiazepine-C-2). – MS (EI, 70 eV): m/z (%) =
+
07 (100) [M ], 180 (13), 241 (8), 210 (19), 149 (34), 7-Benzylimino-[1,3,6]thiadiazepane-2-thione (13b)
18 (83), 77 (35), 51 (22). – C H N S (307.33): calcd. (Lit. [26]).
14 9 7
C 54.71, H 2.95, N 31.90, S 10.43; found C 54.58, H 3.11,
N 32.11, S 10.31.
7
-Allylimino-[1,3,6]thiadiazepane-2-thione (13c)
(Lit. [26]).
7
-Amino-2-allylimino-2H-[1,3,4]thiadiazepine-5,5,6-
2,2-Dicyanoimidazolidine-1,3-dicarbothioic acid
tricarbonitrile (9c)
bis-phenylamide (14a)
◦
M. p. 291 C. – IR (KBr): ν 3360 (NH), 2976 (Ali-CH),
◦
M. p. 181 C. – IR (KBr): ν = 3375 (NH ), 2960,
2
−1
2
220 (CN), 1620, 1590 (Ar-C=C), 1350 (C=S) cm . –
2
1
870 (Ali-CH), 2225, 2210 (CN), 1628 (C=N),
565 (C=C) cm . – H NMR (300.13 MHz, DMSO-
1
−1
1
H NMR (300.13 MHz, DMSO-d ): δ = 3.70 (t, 4H,
6
2
2
CH ), 7.12 − 7.41 (m, 10H, Ar-H), 9.59 (br, s, 2H,
13
d ): δ = 4.12 (m, 2H, allyl-CH N), 5.15 − 5.17 (m, 2H,
2
6
2
NH). –
C NMR (75.47 MHz, DMSO-d ): δ =
6
allyl-CH =), 5.92 − 6.00 (m, 1H, allyl-CH=), 7.36 (br, s,
2
+
50.66 (imidazolidine-C-4, 5), 76.44 (imidazolidine-C-2),
2
1
(
H, NH ). – MS (EI, 70 eV): m/z (%) = 257 (100) [M ],
2
1
1
3
17.20 (CN), 123.65, 125.76, 128.84, 139.40 (Ar-C),
91 (34), 163 (22), 99 (73), 64 (21), 41 (89). – C H N S
257.28): calcd. C 46.68, H 2.74, N 38.11, S 12.46; found
C 46.55, H 2.83, N 38.24, S 12.31.
10 7 7
+
81.33 (C=S). – MS (EI, 70 eV): m/z (%) = 392 (6)[M ],
37 (8), 312 (14), 268 (24), 135 (100), 93 (34), 77 (88). –
C H N S (392.50): calcd. C 58.14, H 4.11, N 21.41,
1
16 6
9 2
N,N’-Diphenyl-[1,3,4]thiadiazole-2,5-diamine (10a)
S 16.34; found C 57.92, H 4.22, N 21.56, S 16.51.
(
Lit. [28, 29]).
2
,2-Dicyanoimidazolidine-1,3-dicarbothioic acid
N,N’-Dibenzyl-[1,3,4]thiadiazole-2,5-diamine (10b)
bis-benzylamide (14b)
(Lit. [22]).
◦
M. p. 318 C. – IR (KBr): ν = 3380 (NH), 2960, 2880
N,N’-Diallyl-[1,3,4]thiadiazole-2,5-diamine (10c)
−1
(
Ali-CH), 2218 (CN), 1585 (Ar-C=C), 1360 (C=S) cm . –
H NMR (300.13 MHz, DMSO-d ): δ = 3.66 (t, 4H, 2CH ),
(Lit. [26, 30]).
1
6
2
4
(
.64 (br, 4H, 2CH Ph), 7.10 − 7.34 (m, 10H, Ar-H), 9.52
2
5
-Phenylamino-3H-[1,3,4]thiadiazole-2-thione (11a)
13
br, s, 2H, 2NH). – C NMR (75.47 MHz, DMSO-d ):
6
(Lit. [27, 31]).
δ = 50.53 (imidazolidine-C-4, 5), 54.66 (CH Ph), 76.12
(imidazolidine-C-2), 117.00 (CN), 123.44, 124.89, 128.63,
2
5
-Benzylamino-3H-[1,3,4]thiadiazole-2-thione (11b)
(
Lit. [32]).
140.18 (Ar-C), 181.42 (C=S). – MS (EI, 70 eV): m/z (%) =
+
420 (11) [M ], 365 (6), 296 (22), 149 (100), 77 (74). –
5
-Allylamino-3H-[1,3,4]thiadiazole-2-thione (11c)
C H N S (420.56): calcd. C 59.97, H 4.79, N 19.98,
2
6
1 20 2
(Lit. [23, 26]).
S 15.25; found C 60.12, H 4.62, N 20.08, S 15.36.
Reaction of substituted thioureidoethylthioureas 12a − c 2,2-Dicyanoimidazolidine-1,3-dicarbothioic acid
with TCNE
bis-allylamide (14c)
◦
Solutions (2 mmol) of 12a – c in 30 ml of tetrahydro-
M. p. 233 C. – IR (KBr): ν 3380 (NH), 2966, 2880 (Ali-
−1
1
furan (THF) were treated with 512 mg (4 mmol) of TCNE CH), 2220 (CN), 1610 (C=C), 1356 (C=S) cm . – H NMR
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915
(
300.13 MHz, DMSO-d ): δ = 3.68 (t, 4H, 2CH2 ), 4.10 (br, s, 1H, NHCH Ph). – 13C NMR (75.47 MHz, DMSO-
6
2
(
5
m, 4H, allyl-CH N), 5.13 − 5.17 (m, 4H, allyl-CH =), d6): δ = 32.66 (diazepine-C-5), 43.74 (diazepine-C-3),
2
2
.93−6.03 (m, 2H, allyl-CH=), 7.49 (br, s, 2H, allyl-NH). – 47.11 (diazepine-C-2), 54.31 (CH Ph), 61.00 (diazepine-C-
2
+
MS (EI, 70 eV): m/z (%) = 320 (12) [M ], 221 (34), 122 6), 116.88, 118.30 (CN), 123.77, 125.62, 128.93, 140.11 (Ar-
(
(
66), 99 (100), 68 (100), 68 (11), 41 (54). – C H N S
320.44): calcd. C 48.73, H 5.03, N 26.23, S 20.01; found m/z (%) = 337 (14) [M ], 296 (11), 255 (8), 229 (28),
C), 166.35 (diazepine-C-7), 178.71 (C=S). – MS (EI, 70 eV):
13 2
16 6
+
C 48.60, H 4.91, N 26.38, S 19.88.
149 (82), 91 (32), 77 (100). – C H N S (337.40): calcd.
16 15
7
C 56.96, H 4.48, N 29.06, S 9.50; found C 57.14, H 4.39,
N 28.92, S 9.66.
7
-Amino-5,5,6-tricyano-2,3,4,5-tetrahydro[1,4]diazepine-1-
carbothioic acid phenylamide (15a)
7
-Amino-5,5,6-tricyano-2,3,4,5-tetrahydro[1,4]diazepine-1-
◦
M. p. 246 C. – IR (KBr): ν = 3410, 3356, 3290 (NH ,
2
carbothioic acid allylamide (15c)
NH), 2980 (Ali-CH), 2218, 2210 (CN), 1620 (Ar-C=C),
◦
−1
1
M. p. 202 C. – IR (KBr): ν 3410, 3380, 3200 (NH ,
1
360 (C=S) cm . – H NMR (300.13 MHz, DMSO-d ):
2
6
NH), 2988 (Ali-CH), 2218, 2210 (CN), 1610 (C=C),
1
δ = 3.56 (m, 2H, diazepine-C-3), 3.68 (m, 2H, diazepine-
−
350 (C=S) cm . – H NMR (300.13 MHz, DMSO-d ):
6
1
1
C-2), 7.18 (br, s, 2H, NH ), 7.23 − 7.64 (m, 5H, Ar-
2
δ = 3.37 − 3.44 (m, 2H, diazepine-C-3), 3.56 − 3.62 (m,
H), 7.91 (br, s, 1H, diazepine-NH), 9.68 (br, s, 1H,
1
3
2H, diazepine-C-2), 3.91−3.96 (m, 2H, allyl-CH N), 5.04−
NHPh). – C NMR (75.47 MHz, DMSO-d ): δ = 32.86
2
6
5
.15 (m, 2H, allyl-CH =), 5.88 − 5.96 (m, 1H, allyl-CH=),
(
diazepine-C-5), 43.82 (diazepine-C-3), 46.45 (diazepine-
2
C-2), 60.66 (diazepine-C-6), 115.92, 117.26 (CN), 123.88, 7.20 (br, s, 2H, NH2), 7.54 (br, s, 1H, allyl-NH), 7.83 (br,
1
3
1
1
2
25.36, 128.84, 139.46 (Ar-C), 166.17 (diazepine-C-7), s, 1H, diazepine-NH). – C NMR (75.47 MHz, DMSO-
78.55 (C=S). – MS (EI, 70 eV): m/z (%) = 323 (10) [M ], d6): δ = 33.11 (diazepine-C-5), 43.77 (diazepine-C-3), 47.76
82 (14), 241 (7), 135 (76), 77 (93), 65 (100). – C H N S (diazepine-C-2), 52.86 (allyl-CH2N), 61.22 (diazepine-C-6),
+
1
5
13 7
(
323.38): calcd. C 55.71, H 4.05, N 30.32, S 10.11; found 114.92 (allyl-CH2=), 117.32, 118.53, (CN), 135.12 (allyl-
C 55.54, H 3.94, N 30.41, S 10.11.
CH=), 166.83 (diazepine-C-7), 178.81 (C=S). – MS (EI,
+
70 eV): m/z (%) = 287 (16) [M ], 247 (12), 205 (10), 179
(
23), 99 (56), 56 (44), 41 (100). – C H N S (287.34):
7
-Amino-5,5,6-tricyano-2,3,4,5-tetrahydro[1,4]diazepine-1-
12 13 7
calcd. C 50.16, H 4.56, N 34.12, S 11.16; found C 50.31,
H 4.71, N 33.96, S 11.27.
carbothioic acid benzylamide (15b)
◦
M. p. 261 C. – IR (KBr): ν 3422, 3374, 3310 (NH , NH),
2
Acknowledgement
2
1
978, 2888 (Ali-CH), 2225, 2220 (CN), 1590 (Ar-C=C),
−1
1
355 (C=S) cm . – H NMR (300.13 MHz, DMSO-d ):
A. A. Hassan is indebted to the A. v. Humboldt-Founda-
6
δ = 3.51 (m, 2H, diazepine-C-3), 3.66 (m, 2H, diazepine-C- tion for the award of a fellowship from August 2003 to Sept.
2
7
), 4.63 (br, s, 2H, CH Ph), 7.22 (br, s, 2H, NH ), 7.25 − 2003 and also for the donation of the Shimadzu 408 IR spec-
2
2
.61 (m, 5H, Ar-H), 7.88 (br, s, 1H, diazepine-NH), 9.53 trophotometer.
[
[
[
[
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9
16
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