Synthesis of spiroheterocycles containing thiadiazole thiadiazine and triazine moieties from nitrilimines

Article abstract of DOI:10.1080/10426507.2010.546587

A series of 5-substituted 1-methyl-3-phenyl-4,5-dihydro-1,2,4-triazin-6- ones was prepared by the reaction of -amino acid methyl esters with appropriate nitrilimines and treated with phosphorus pentasulfide to afford 5-substituted 1-methyl-3-phenyl-4,5-di

Full text of DOI:10.1080/10426507.2010.546587

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Synthesis of Spiroheterocycles
Containing Thiadiazole Thiadiazine and
Triazine Moieties from Nitrilimines
Hany M. M. Dalloul a
a Department of Chemistry, Faculty of Applied Science , Al-Aqsa
University of Gaza , Gaza, Palestine
Published online: 24 Aug 2011.
To cite this article: Hany M. M. Dalloul (2011) Synthesis of Spiroheterocycles Containing Thiadiazole
Thiadiazine and Triazine Moieties from Nitrilimines, Phosphorus, Sulfur, and Silicon and the Related
Elements, 186:9, 1876-1884, DOI: 10.1080/10426507.2010.546587
To link to this article: http://dx.doi.org/10.1080/10426507.2010.546587
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Phosphorus, Sulfur, and Silicon, 186:1876–1884, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.546587
SYNTHESIS OF SPIROHETEROCYCLES CONTAINING
THIADIAZOLE THIADIAZINE AND TRIAZINE MOIETIES
FROM NITRILIMINES
Hany M. M. Dalloul
Department of Chemistry, Faculty of Applied Science, Al-Aqsa University of Gaza,
Gaza, Palestine
GRAPHICAL ABSTRACT
Me
R
Ph
N
Me
N
N N
X
-
+
Ph
O
+
HX
CO2Me
P2S5
Me
R
X=NH, S
Me
Me
N
-
+
N
N N
N N
Ph
N
Me
N
Ph
Ph
S
X
X
S
Ph
R
R
Abstract A series of 5-substituted 1-methyl-3-phenyl-4,5-dihydro-1,2,4-triazin-6-ones was
prepared by the reaction of α-amino acid methyl esters with appropriate nitrilimines and
treated with phosphorus pentasulfide to afford 5-substituted 1-methyl-3-phenyl-4,5-dihydro-
1,2,4-triazin-6-thiones. When 1,2,4-triazin-6-thiones were allowed to react with nitrilimine,
the novel 4,6-dimethyl-2,8-di-phenyl-10-substituted-1-thia-3,4,6,7,9-pentaazaspiro[4.5]dec-
2,7-dienes were obtained and confirmed by their elemental analyses and spectral data. Some
of the synthesized compounds were tested in vitro for their antimicrobial activity.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
Keywords Nitrilimine; cycloaddition; spiroheterocycles; 1; 2; 4-triazin-6-one; 1; 2; 4-triazin-
6-thione; 1; 3; 4-thiadiazole
INTRODUCTION
In recent years, attention has been increasing regarding the synthesis of spirohete-
rocyclic compounds that exhibit various biological activities,1–8 pharmaceutical,9,10 and
Received 21 September 2010; accepted 1 December 2010.
Address correspondence to Hany M. M. Dalloul, Department of Chemistry, Faculty of Applied Science,
Al-Aqsa University of Gaza, P. O. Box 4051, 76888 Gaza, Palestine. E-mail: hmdalloul60@yahoo.com
1876

SYNTHESIS OF SPIROHETEROCYCLES
1877
antitumor properties.11,12 The synthesis of different spiroheterocycles was reported using
nitrilimines and cycloalkanone hydrazones or oximes.13–17 Recently, we described a ver-
satile and efficient one-pot synthesis of octaazadispiro-heterocyclic compounds utilizing
1,4-cyclohexanedione methyl hydrazone and nitrilimines.18 Quite recently, the spirohetero-
cyclic systems containing a thiazolidinone moiety were prepared in our laboratory via reac-
tion of several nitrilimines with 2-phenylimino-1,3-thiazolidin-4-one.19 Furthermore, our
search of the literature revealed that various spiroheterocycles exhibiting a thiadiazole moi-
ety have been synthesized by the reaction of different heterocyclic thiones with hydrazonoyl
halides in the presence of a suitable base.20 As a part of our continuing interest in the con-
struction of spiroheterocyclic systems by means of the nitrilimine 1,3-dipolar cycloaddition
methodology,15–22 the present work describes the synthesis of some new spiro-4,6-dimethyl-
2,8-diphenyl-10-substituted-1-thia-3,4,6,7,9-pentaazaspiro[4.5]dec-2,7-dienes via reaction
of C-phenyl-N-methylnitrilimines with 4,5-dihydro-1,2,4-triazin-6-thiones.
RESULTS AND DISCUSSION
Preparations
The 5-substituted 1-methyl-3-phenyl-4,5-dihydro-1,2,4-triazin-6-ones 3a–f and 4-
methyl-2-phenyl-6H-1-thia-3,4-diazin-5-one 4 were synthesized in good yield by the cy-
clocondensation reaction of nitrilimines 2, generated in situ by base catalyzed elimination of
hydrogen bromide from C-phenyl-N-methyl-hydrazonoyl bromide 1, with one molar equiv-
alent of α-aminoester hydrochlorides and ethyl 2-mercaptoacetate at room temperature (see
Scheme 1). It is worth to be mentioned that the reaction of C-aroyl-N-arylhydrazonoyl
halides with α-mercaptoalkanoic acids23 or their ethyl ester24 gave 4-arylhydrazono-5-oxo-
3-thiahexanoic acids and ethyl 6-aryl-4-aroyl-3-thia-5,6-diaza-4-hexenoates, which under-
went thermal cyclization to thiadiazinone rings in the presence of dicyclohexylcarbodiimide
or lithium hydride. The formation of compound 4 is assumed to involve the formation of the
nucleophilic addition intermediate 3ꢁ, which can not be isolated nor observed by thin layer
chromatography (TLC). The later intermediate ultimately cyclized intermolecularly to the
corresponding 4-methyl-2-phenyl-6H-1-thia-3,4-diazin-5-one 4. This can be explained on
the basis of the high nucleophilicity of the nitrogen atom carrying the methyl group.
The structures of the products 3a–f and 4 were elucidated on the basis of analytical
and spectroscopical data. Physical properties, molecular ion peaks, and elemental analysis
are presented in the Experimental section. No investigations were carried out concerning
optical purity and activity of compounds 3a–f. The electron impact (EI) mass spectra of
these compounds displayed the correct molecular ions in accordance with the suggested
molecular formulas. A main fragmentation mode of the closely related substituted 4,5-
dihydro-1,2,4-triazin-6-ones was reported to involve hetero ring-scission at the dotted lines
as shown in Scheme 2, leading to fragment ion M-105 as a base peak.25 The base peak
for 3a was at 189, for 3b (alanine rest) at M-43, for 3c (phenyl glycine rest) at M-105,
for 3d (valine rest) at M-71, for 3e (phenyl alanine rest) at M-119, and for 3f (S-benzyl
cystiene rest) was at 165. The IR spectra of the compounds 3a–f exhibit a characteristic
absorption band of NH in the 3370–3340 cm−1 region and a lactam carbonyl group band
in the 1680–1670 cm−1 region. Their 1H and 13C NMR spectra displayed the characteristic
signals of the suggested structures. The NH protons of the 1,2,4-triazinone ring appeared
at 6.5–6.2 ppm and the signal of the lactam group recorded at about 162–160 ppm. The

1878
H. M. M. DALLOUL
Me
H
+
N
Ph
Ph
Ph
N
Br
H
Br
+
1
i
Me
N
N
NHMe
COOMe
CH2
3'
N
S
Me
N
P2S5
iii
Ph
N
Ph
O
C5H5N
S
2
4
ii
Me
Me
N
N
N
N
Ph
S
O
S
6
HN
R
2
_
CHCl3 /∆
3a f
Me
N
Me
P2S5
C5H5N
N
S
N
N
Ph
Me
N
Me
N
Me
N
S
Ph
N
N
HN
8
N
2
Ph
S
Ph
CHCl3 /∆
HN
S
Ph
R
R
_
_
5a f
7a f
i) Et3N,0 oC; ii) H2NCH(R)COOMe, r.t.; iii) HSCH2COOEt, r.t.
a: R = H; b: R = Me; c: R = Ph; d: CHMe2; e: R = CH2Ph; f: R = CH2SCH2Ph
Scheme 1
compound 4 gave satisfactory combustion analysis for the proposed structure which was
confirmed on the basis of its spectroscopic data and is given in the Experimental section.
The conversion of 1,2,4-triazinones into the corresponding thiones has been re-
ported.26 The treatment of compounds 3a–f and 4 with phosphorus pentasulfide in refluxing
.
.
+
+
Me
Me
.
N
N
N
+
N
N
+
HN CH Ph
Ph
X
Ph
X
M-105
m/z = 105
Ph
H
H
.
H
C9H8N2X
X= O m/z = 160
X= S m/z = 176
C16H15N3X
3c X= O [M+] 265
5c X= S [M+] 281
+
HN
C
Ph
Scheme 2

SYNTHESIS OF SPIROHETEROCYCLES
1879
xylene in the presence of pyridine afforded 5-substituted 1-methyl-3-phenyl-4,5-dihydro-
1,2,4-triazin-6-thiones 5a–f and 4-methyl-2-phenyl-6H-1-thia-3,4-diazin-5-thione 6, re-
spectively (see Scheme 1), in good yields (see the Experimental section). Both the analytical
and spectroscopic data (IR, 1H NMR, 13C NMR, and mass spectra) of the title compounds
were in full agreement with the proposed structures, and depicted in the Experimental sec-
tion. The mass spectra displayed the correct molecular ion peaks (M+) in accordance with
the suggested structures. The main fragmentation of substituted 4,5-dihydro-1,2,4-triazin-
6-thiones was similar to that occurring in compounds 3a–f. The base peak for 5a was at
205 and for 5b–f was at 176 (see Scheme 2). Their IR spectra indicated the appearance
of a new absorption band in the 1395–1380 cm−1 region due to the C S function, instead
of lactam group (1680–160 cm−1). The 13C NMR data illustrated that the carbonyl ring
signal at 162–160 ppm was replaced by thione carbon (C S) signal at 176–172 ppm.
Thiocarbonyl groups are generally reactive towards 1,3-dipolarophiles.27,28 The reaction of
1,2,4-triazin-6-thiones 5a–f with nitrilimine 2 in refluxing chloroform gave in each case a
single product that proved to be the respective 4,6-dimethyl-2,8-diphenyl-10-substituted-
1-thia-3,4,6,7,9-pentaazaspiro[4.5]dec-2,7-dienes 7a–f (see Scheme 1). Similar reaction
of nitrilimine 2 with 1-thia-3,4-diazin-5-thione 6 afforded 4,6-dimethyl-2,8-diphenyl-1,9-
dithia-3,4,6,7-tetraazaspiro[4.5]dec-2,7-diene 8 (see Scheme 1).
The structure of the spiro compounds 7a–f and 8 has been ascertained from their ana-
lytical and spectroscopic data, which is summarized in the Experimental section. Their mass
spectra displayed the correct molecular ion peaks (M+) in accordance with the suggested
structures. The IR spectra of the title compounds 7a–f and 8 showed the disappearance of
thione absorption band (1395–1380 cm−1). Their 13C NMR spectra revealed all the signals
of the proposed structures. Especially, the tetrahedral carbon (spirocarbon) was found to
resonate at about 95–100 ppm. This is similar to the reported values of spiro carbon flanked
by two nitrogen atoms in five-membered heterocycles,15–17,19,28 which provide strong ev-
idence in support of the structures 7a–f and 8. The signals with other functional groups
present all appeared in the expected regions.
Antimicrobial Activity
Ten of the newly synthesized compounds were screened in vitro for their antimicro-
bial activity against a variety of bacterial strains such as Escherichia coli, Staphylococcus
aureus, and Klebsiella spp. and fungi such as Aspergillus niger and Candida albicans, em-
ploying the nutrient agar disc diffusion method29 at 10 mg/mL concentration in dimethyl
formamide (DMF) by measuring the average diameter of the inhibition zone in mm (see
Table S1). The data reported in Table S1 represent the average of three experiments. The
results showed that all the tested compounds exhibited a marked degree of activity against
bacteria and fungi compared with well-known antibacterial and antifungal substances such
as tetracycline and fluconazole. According to the National Committee for Clinical Labora-
tory Standards (NCCLS, 2004), zones of inhibition for tetracycline and fluconazole < 14
mm were considered resistant, between 15 and 18 mm were considered weakly sensitive,
and >19 mm were considered sensitive. Also, the results showed the degree of inhibition
to vary with the tested compounds (see Table S1).
CONCLUSIONS
The reaction of C-phenyl-N-methylnitrilimines with α-aminoesters and α-
mercaptoacetate leads to the formation of 1,2,4-triazin-6-ones and 1,3,4-thiadiazin-5-one,

1880
H. M. M. DALLOUL
which can be converted to 1,2,4-triazin-6-thiones 5a–f and 1,3,4-thiadiazin-5-thione
6 via treatment with phosphorus pentasulfide. The nitrilimine cycloadded to the C S
double bond of compounds 5a–f and 6 to give spiroheterocyclic compounds 7a–f and 8,
which were completely characterized. Some of the title compounds proved to have potent
antibacterial and antifungal activity. The results confirm that the antimicrobial activity is
strongly dependent on the nature of the substituents.
EXPERIMENTAL
Melting points were determined on electrothermal melting points apparatus and are
uncorrected. The IR spectra were measured as KBr pellets using Shimadzu FT-IR 8101
1
PC infrared spectrophotometer. The H NMR and 13C NMR spectra were recorded on a
Bruker AM 300 MHz spectrometer at room temperature in dimethyl sulfoxide-d6 (DMSO-
d6) solution using tetramethylsilane (TMS) as internal reference. Chemical shifts were
recorded as δ values in ppm downfield from internal TMS. EI mass spectra were run on a
Shimadzu GCMS-QP1000 EX spectrometer at 70 eV. Elemental analyses were performed
at the Microanalytical Center of the Cairo University, Egypt. The hydrazonoyl bromide 130
and α-aminoester hydrochlorides31 were prepared following reported procedures. Benzene,
triethylamine ethyl 2-mercaptoacetate and phosphorus pentasulfide were purchased from
Avocado Research Chemicals, England, and used without further purification.
5-Substituted 1-Methyl-3-Phenyl-4,5-Dihydro-1,2,4-Triazin-6-ones 3a–f
To a stirred and cooled solution (−5 to 0 ◦C) of hydrazonoyl bromide 1 (10 mmol) in
tetrahydrofuran (100 mL) was added a solution of the appropriate α-aminoester hydrochlo-
rides (15 mmol) in methanol (40 mL). To the resulting reaction mixture, triethylamine
(50 mmol) was dropwise added. After addition was completed, stirring was continued for 2
h at 0 ◦C and then at room temperature for 10–12 h. The solvent was removed under reduced
pressure, and the residue was washed with water to get rid of the triethylammonium salt.
The resulting crude product was triturated with ethanol (10 mL), collected, and recrystal-
lized from aqueous ethanol to give the desired triazinones 3a–f in good yield. The prepared
compounds 3a–f together with their physical and spectral data are given in supplemental
materials.
4-Methyl-2-Phenyl-6H-1-Thia-3,4-Diazin-5-one 4
This reaction was carried out as described for the preparation of compounds 3a–f
using ethyl 2-mercaptoacetate in place of α-aminoester hydrochlorides and stirring contin-
ued for 48 h at room temperature. The compound 4 obtained as white solid; yield: 82%;
mp 136–138 ◦C; IR νmax/cm−1: 1676 (C O lactam), 1595 (C N), 1228 (C S); 1H NMR
(DMSO-d6) δ 7.20–7.42 (m, 5H, Ar H), 4.30 (s, 2H, CH2), 3.24 (s, 3H, CH3); 13C NMR
(DMSO-d6) δ 159.46 (C O lactam), 143.18 (C N), 140.92, 129.51, 128.71, 125.10 (Ar
C C), 42.62 (CH3), 26.18 (CH2); MS, m/z: 206 [M+]; Anal. Calcd. for C10H10N2OS
(Mr = 206.27): C, 58.23; H, 4.89; N, 13.58%; Found: C, 58.35; H, 5.00; N, 13.65%.
1,2,4-Triazin-6-Thiones 5a–f and 1-Thia-3,4-Diazin-5-Thione 6
Phosphorus pentasulfide (6.5 mmol) was added to a solution of compounds 3a–f or
4 (10 mmol) in xylene (30 mL) and pyridine (15 mL). After being heated under reflux
for 3–4 h and stirred at room temperature overnight. The yellow solution was evaporated

SYNTHESIS OF SPIROHETEROCYCLES
1881
to dryness, and the residue was dissolved in water and then extracted with ethyl acetate
(4 × 30 mL). The extract was washed with brine, dried, and evaporated under reduced
pressure. The◦residual solid was collected and recrystallized from ethyl acetate/petroleum
ether (40–60 C) affording the desired compounds 5a–f and 6. The prepared compounds
5a–f together with their physical and spectral data are given in supplemental materials.
4-Methyl-2-Phenyl-6H-1-Thia-3,4-Diazin-5-Thione 6
Yield: 82%; mp 136–138 ◦C; IR νmax/cm−1: 1608 (C N), 1395 (C S), 1212 (C S);
1H NMR (DMSO-d6) δ 7.20–7.47 (m, 5H, Ar H), 4.12 (s, 2H, CH2), 3.26 (s, 3H, CH3);
13C NMR DMSO-d6) δ 172.97 (C S), 143.40 (C N), 138.72, 129.01, 128.68, 115.63
(Ar C C), 42.62 (CH3), 26.18 (CH2); MS, m/z: 222 [M+]; Anal. Calcd. for C10H10N2S2
(Mr = 222.33): C, 54.02; H, 4.53; N, 12.60%; Found: C, 53.85; H, 4.65; N, 12.75%.
Spiro Compounds 7a–f and 8
To a solution of the hydrazonoyl bromide 1 (5 mmol) and compounds 5a–f or 6 (5
mmol) in chloroform (50 mL), triethylamine (5 mmol) was added at room temperature. The
reaction mixture was refluxed for 12–18 h and monitored by TLC. After completion of the
reaction, the solvent was removed in vacuum and the residue was washed with water and
then triturated with methanol. The solid obtained was filtered off and recrystallized from
acetic acid to give the corresponding spiro products 7a–f and 8, respectively. The prepared
compounds 7a–f together with their physical and spectral data are listed below.
4,6-Dimethyl-2,8-Diphenyl-1-Thia-3,4,6,7,9-Pentaazaspiro[4.5]Dec-2,7-Dienes
7a
◦
Yield (60%); mp 186–188 C (decomp.); IR νmax/cm−1: 3368 (NH), 1614, 1596
1
(C N), 1201 (C S); H NMR (DMSO-d6) δ 7.14–7.53 (m, 10H, Ar H), 6.70 (s, 1H,
NH), 4.27 (s, 2H, CH2), 3.45 (s, 3H, CH3), 3.24 (s, 3H, CH3); 13C NMR (DMSO-d6) δ
146.27, 143.20 (C N), 140.82, 137.86, 134.64, 129.56, 128.66, 125.09, 122.77, 115.31
(Ar C C), 94.89 (tetrahedral carbon), 43.08 (CH3), 42.81 (CH3); 26.32 (CH2); MS, m/z:
337 [M+]; Anal. Calcd. for C18H19N5S (Mr = 337.45): C, 64.07; H, 5.68; N, 20.75%;
Found: C, 63.85; H, 5.80; N, 20.65%.
2,8-Diphenyl-4,6,10-Trimethyl-1-Thia-3,4,6,7,9-Pentaazaspiro[4.5]Dec-2,
7-Dienes 7b
◦
Yield (63%); mp 174–176 C (decomp.); IR νmax/cm−1: 3366 (NH), 1610, 1598
1
(C N), 1203 (C S); H NMR (DMSO-d6) δ 7.15–7.44 (m, 10H, Ar H), 6.65 (s, 1H,
NH), 4.44 (q, 1H, J = 6.8 Hz, CH), 3.41 (s, 3H, NCH3), 3.22 (s, 3H, NCH3), 1.58 (d, 3H,
J = 6.8 Hz, CH3); 13C NMR (DMSO-d6) δ 146.52, 143.10 (C N), 140.89, 137.84, 135.34,
129.60, 128.68, 125.05, 123.24, 115.91 (Ar C C), 97.56 (tetrahedral carbon), 48.77 (CH);
43.03 (CH3), 42.67 (CH3), 19.20 (CH3); MS, m/z: 351 [M+]; Anal. Calcd. for C19H21N5S
(Mr = 351.48): C, 64.93; H, 6.02; N, 19.93%; Found: C, 64.75; H, 5.90; N, 20.05%.

1882
H. M. M. DALLOUL
4,6-Dimethyl-2,8,10-Triphenyl-1-Thia-3,4,6,7,9-Pentaazaspiro[4.5]Dec-2,
7-Dienes 7c
◦
Yield (61%); mp 167–169 C (decomp.); IR νmax/cm−1: 3362 (NH), 1612, 1598
1
(C N), 1202 (C S); H NMR (DMSO-d6) δ 7.26–7.76 (m, 15H, Ar H), 6.57 (s, 1H,
NH), 5.41 (s, 1H, CH), 3.43 (s, 3H, NCH3), 3.21 (s, 3H, CH3); 13C NMR (DMSO-d6) δ
146.74, 143.02 (C N), 140.78, 138.43, 137.91, 134.86, 129.40, 129.02, 128.72, 128.12,
127.65, 126.22, 124.23, 115.81 (Ar C C), 98.44 (tetrahedral carbon), 56.83 (CH); 43.10
(CH3), 42.74 (CH3); MS, m/z: 413 [M+]; Anal. Calcd. for C24H23N5S (Mr = 413.55): C,
69.71; H, 5.61; N, 16.93%; Found: C, 69.55; H, 5.50; N, 17.05%.
4,6-Dimethyl-2,8-Diphenyl-10-Isopropyl-1-Thia-3,4,6,7,9-Pentazaspiro
[4.5]Dec-2,7-Dienes 7d
◦
Yield (65%); mp 195–197 C (decomp.); IR νmax/cm−1: 3370 (NH), 1618, 1599
1
(C N), 1205 (C S); H NMR (DMSO-d6) δ 7.18–7.52 (m, 10H, Ar H), 6.54 (s, 1H,
NH), 4.28 (d, 1H, J = 6.0 Hz, CH), 3.42 (s, 3H, CH3), 3.23 (s, 3H, CH3), 2.56 (m, 1H,
CH), 1.09 (d, 6H, J = 6.8 Hz, 2CH3); 13C NMR (DMSO-d6) δ 146.83, 143.70 (C N),
140.46, 137.89, 134.65, 129.12, 128.13, 124.83, 122.7, 115.94 (Ar C C), 99.19 (tetrahedral
carbon), 58.91 (CH); 43.09 (CH3), 42.65 (CH3), 32.89 (CH), 18.14, 16.68 (2CH3); MS,
m/z: 379 [M+]; Anal. Calcd. for C21H25N5S (Mr = 379.53): C, 66.46; H, 6.64; N, 18.45%;
Found: C, 66.60; H, 6.50; N, 18.60%.
10-Benzyl-4,6-Dimethyl-2,8-Diphenyl-1-Thia-3,4,6,7,9-Pentaazaspiro
[4.5]Dec-2,7-Dienes 7e
◦
Yield (63%); mp 183–185 C (decomp.); IR νmax/cm−1: 3372 (NH), 1620, 1601
1
(C N), 1206 (C S); H NMR (DMSO-d6) δ 7.17–7.53 (m, 15H, Ar H), 6.62 (s, 1H,
NH), 4.46 (t, 1H, J = 6.0 Hz, CH), 3.41 (s, 3H, CH3), 3.15 (d, 2H, J = 8.4 Hz, CH2),
3.25 (s, 3H, CH3); 13C NMR (DMSO-d6) δ 146.76, 143.62 (C N), 140.27, 138.20, 137.36,
134.58, 131.27, 129.18, 129.02, 128.63, 127.72, 126.71, 125.38, 115.94 (Ar C C), 96.87
(tetrahedral carbon), 43.54 (CH2); 43.10 (CH3), 42.81 (CH3); MS, m/z: 427 [M+]; Anal.
Calcd. for C25H25N5S (Mr = 427.58): C, 70.23; H, 5.89; N, 16.38%; Found: C, 70.40; H,
6.01; N, 16.25%.
10-(S-Benzylmethyl)-4,6-Dimethyl-2,8-Diphenyl-1-Thia-3,4,6,7,9-Pentaa
zaspiro[4.5]Dec-2,7-Dienes 7f
◦
Yield (60%); mp 196–198 C (decomp.); IR νmax/cm−1: 3378 (NH), 1605 (C N),
1222, 1208 (C S); 1H NMR (DMSO-d6) δ 7.23–7.62 (m, 15H, Ar H), 6.64 (s, 1H, NH),
4.31 (t, 1H, J = 6.0 Hz, CH), 3.80 (s, 2H, SCH2), 3.44 (s, 3H, CH3), 3.26 (s, 3H, CH3),
2.83 (d, 2H, J = 6.2 Hz, CH2S); 13C NMR (DMSO-d6) δ 146.21, 143.18 (C N), 142.02,
138.18, 137.29, 134.75, 131.25, 129.21, 129.00, 128.67, 127.77, 126.65, 125.32, 115.79
(Ar C C), 97.75 (tetrahedral carbon), 52.96 (CH), 43.13 (CH3), 42.87 (CH3), 36.68 (CH2);
35.32 (CH2); MS, m/z: 473 [M+]; Anal. Calcd. for C26H27N5S2 (Mr = 473.67): C, 65.93;
H, 5.75; N, 14.79%; Found: C, 66.10; H, 5.60; N, 14.92%.

SYNTHESIS OF SPIROHETEROCYCLES
1883
4,6-Dimethyl-2,8-Diphenyl-1,9-Dithia-3,4,6,7-Tetraazaspiro[4.5]Dec-2,7-
Diene 8
Yield (60%); mp 186–188 ◦C; IR νmax/cm−1: 3368 (NH), 1624, 1616 (C N), 1221,
1205 (C S); 1H NMR (DMSO-d6) δ 7.14–7.53 (m, 10H, Ar H), 6.70 (s, 1H, NH), 4.27
(s, 2H, CH2), 3.45 (s, 3H, CH3), 3.24 (s, 3H, CH3); 13C NMR (DMSO-d6) δ 146.27, 143.20
(C N), 140.82, 137.86, 134.64, 129.56, 128.66, 125.09, 122.77, 115.31 (Ar C C), 94.89
(tetrahedral carbon), 43.08 (CH3), 42.81 (CH3); 26.32 (CH2); MS, m/z: 354 [M+]; Anal.
Calcd. for C18H18N4S2 (Mr = 354.50): C, 60.99; H, 5.12; N, 15.80%; Found: C, 61.10; H,
5.05; N, 15.87%.
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