Cycloaddition of Aroyl Isothiocyanate: A Novel Synthesis of Triazine, Oxazine, Pyrimidine, and Pyridine Derivatives

Article abstract of DOI:10.1002/jhet.3690

A simple and direct synthetic methodology for a novel series of azines and their annulated systems was performed. Heterocyclization of acyl isothiocyanate 2 with urea or malononitrile gave s-triazine 4 and 1,3-oxazine 7 derivatives, respectively. The reaction of heteroallene 1 with acetylacetone tolerated 2-thioxopyridine derivative 9. The latter compound underwent heterocyclization with urea, hydrazine hydrate, or phenyl hydrazine to give the annulated pyridines 10–12. Pyrimidinethione 14 was resulted from reaction of acylisothiocyanate with enamine 13. Condensation of compound 14 with hydrazine hydrate, phenyl hydrazine, urea, and 3-nitrobenzaldehyde in the presence of ethyl cyanoacetate or sodium hydroxide afforded 15–20, respectively.

Full text of DOI:10.1002/jhet.3690

Month 2019
Cycloaddition of Aroyl Isothiocyanate: A Novel Synthesis of Triazine,
Oxazine, Pyrimidine, and Pyridine Derivatives
a
a
c
Mohamed G. Assy, Hassan A. El-Sayed,
Nabil H. Ouf,a Ahmed Hamza,a,b and Hesham A. Morsy
*
*
aChemistry Department, Faculty of Science, Zagazig University, Zagazig 44519, Egypt
bDepartment of Chemistry, Faculty of Science, Al-furat Al-Awsat Technical University, Kufa, Iraq
cHigher Institution of Engineering & Modern Technology, Elmarg-Cairo, Egypt
*E-mail: hasanneg@gmail.com; heshselem@yahoo.com
Received March 17, 2019
DOI 10.1002/jhet.3690
Published online 00 Month 2019 in Wiley Online Library (wileyonlinelibrary.com).
A simple and direct synthetic methodology for a novel series of azines and their annulated systems
was performed. Heterocyclization of acyl isothiocyanate 2 with urea or malononitrile gave s-triazine 4 and
1,3-oxazine 7 derivatives, respectively. The reaction of heteroallene 1 with acetylacetone tolerated 2-
thioxopyridine derivative 9. The latter compound underwent heterocyclization with urea, hydrazine hydrate,
or phenyl hydrazine to give the annulated pyridines 10–12. Pyrimidinethione 14 was resulted from reaction
of acylisothiocyanate with enamine 13. Condensation of compound 14 with hydrazine hydrate, phenyl hy-
drazine, urea, and 3-nitrobenzaldehyde in the presence of ethyl cyanoacetate or sodium hydroxide afforded
15–20, respectively.
J. Heterocyclic Chem., 00, 00 (2019).
INTRODUCTION
anticorrosion agents [8]. The presence of triazines and
oxazines in agrochemical and pharmaceutical used
compounds is the main reason for their extensive study by
the chemists. For instance, there are many compounds
containing triazine core reported as antimalarial [9],
herbicidal [10], antimicrobial [11], anticancer [12].
Furthermore, acyl isothiocyanates are used as reaction
intermediates in construction of variety heterocycles
systems such as poly-functional triazines, pyridazines,
pyrimidines, pyridines, triazoles, thiazines, thiadiazoles,
pyrazoles, isothiazoles, and pyrans [13–15]. Recently, our
research area directed to design and synthesis of
biologically important heterocyclic systems from readily
available reagents [8,13,15]. Herein, we hope to use a
simple and rapid approach to synthesize a novel series of
The synthesis of nitrogen containing heterocyclic systems
attracted organic chemistry very much, due to their
enormous applications as drugs and agrochemicals. For
example, pyrimidine scaffolds (Fig. 1) are well-known
dihydrofolate reductases inhibitor [1] and are associated
with a wide area of pharmaceutical properties. Further,
pyrimidines and their fused systems have been reported as
antimicrobial [2], anti-inflammatory [3], antipyretic [4],
anti-HIV [5], antitumor agents [6], and antihypertensive [7].
Similarly, pyridine ring is an important six-membered
heterocycle core present in enormous applicable
compounds, such as insecticides, herbicides, dyes,
photoluminescences, electroluminescences, and metal steel
© 2019 Wiley Periodicals, Inc.

M. G. Assy, H. A. El-Sayed, N. H. Ouf, A. Hamza, and H. A. Morsy
Vol 000
derivative 4 (Scheme 1). The chemical structure of triazine
4 was supported by IR spectrum which leads to NH, C═O,
and C═S absorption bands at 3344, 3251, 1685, and
1234 cmÀ1, respectively. The 1H-NMR revealed the
presence of triazine in two tautomeric forms from the
downfield signals at 9.59, 9.36, and 11.65 ppm of NH
protons, in addition to aryl protons in the region 7.74–
7.51 ppm as two doublets and singlets. Malononitrile and
aroyl isothiocyanate derivative 2 underwent [4 + 2]
cycloaddition to produce oxazine derivative 7 presumably
via acyclic form 5 that underwent addition of enolic OH to
cyano function followed by partial hydrolysis of cyano
group (Scheme 1). The structure of target oxazine 7 was
shown from IR bands that contain NH, amide C═O, C═N,
Figure 1. Pyrimidine and pyridine scaffolds as antifolate agents. [Color
figure can be viewed at wileyonlinelibrary.com]
heterocyclic
systems
utilizing
2,4-dichlorobenzoyl
isothiocaynate as a simple synthetic precursor.
RESULTS AND DISCUSSION
and C═S at υ 3344, 3325, 3195, 1680, and 1233 cmÀ1
respectively. Its 1H-NMR displayed downfield signals at δ
,
Nucleophilic nitrogen of urea was added to heteroallen 2
carbon followed by cyclodehydration to furnish triazine
Scheme 1. Intermolecular ring closure of aroyl isothiocyanate into triazine 4 and oxazine 7.
Scheme 2. Synthetic route for annulated pyridines 10–12.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

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Cycloaddition of Aroyl Isothiocyanate
9.05 and 10.65 ppm for amino and imino protons,
respectively.
1H, and 13C-NMR data (cf. Experimental section).
Cyclocondesation of pyridine 9 with phenylhydrazine
afforded 1-phenylpyrazolo[3,4-b]pyridine 12 in 62%
yield (Scheme 2).
Acetylacetone and acyl isothiocyanate underwent
cyclocondensation of type [3 + 3] in the presence of
triethyl amine to provide pyridinethione derivative 9
(Scheme 2). The pyridine derivative 9 has absorption
bands at 3375, 1697, and 1234 cmÀ1 for N-H, C═O, and
C═S, respectively. Its 1H-NMR contained deshielded
signals at δ 7.92 and 13.69 ppm for OH and SH protons,
respectively. Upon reaction of pyridine 9 with urea, the
pyridopyrimidine 10 was produced as a result of
nucleophilic attack of urea to carbonyl and thiocarbonyl
functions (Scheme 2). 3-Acetylpyridine 9 was condensed
with hydrazine hydrate to form pyrazolopyridine
Enaminic carbon of enaminone derivative 13 underwent
nucleophilic attack to heteroallene 2 to furnish acetyl
pyrimidinethione derivative 15. The reaction started with
the formation of a non-isolable acyclic intermediate 14
that loss a molecule of H2O (Scheme 3). Its structure was
supported by IR and 1H-NMR spectra, where the IR
bands illustrate the presence of conjugated C═O and
1
C═S at 1701 and 1242 cmÀ1, respectively. The H-NMR
signals indicated the presence of two methyl groups as
individual singlets at δ 1.81 and 2.50 ppm, in addition to
aromatic protons as multiplet in range 7.39–7.68 ppm. Its
13C-NMR signals revealed 17 signals at δ 17.83, 30.85,
126.9, 127.5, 129.0, 130.0, 130.9, 132.2, 132.4, 132.5,
1
derivative 11. H-NMR data of compound 11 contain two
downfield signals at δ 12.99 ppm for NH proton. The
structure of compound 10 was confirmed from the IR,
Scheme 3. Synthesis of pyrimidine thione 15.
Scheme 4. Synthetic routes for pyrimidines 16–21.
Journal of Heterocyclic Chemistry
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M. G. Assy, H. A. El-Sayed, N. H. Ouf, A. Hamza, and H. A. Morsy
Vol 000
135.5, 136.6, 137.0, 144.1, 152.3, 193.5, and 201.1 ppm
for 2 SP3 and 15 SP2 carbons, respectively.
Fourier Transform infrared spectrometer. The 1H and
13C-NMR spectroscopy were determined with a JEOL-
JNM-LA 500 MHz spectrometer. The chemical shifts are
expressed on the δ (ppm) scale using tetramethylsilane as
the standard reference. Elemental analysis determined on
a PerkinElmer 240 (microanalysis), Microanalysis Center,
Cairo University, Cairo, Egypt. (E. Merck).
Pyrimidinethione 15 underwent heteroannulation via its
refluxing with hydrazine hydrate in ethanol for 3 h affording
pyrazolo[3,4-d]pyrimidine 16 in good yield (70%)
(Scheme 4). The IR of compound 16 confirm its formation
by the absence of C═O and C═S bands. Its 1H-NMR
confirmed the presence of two methyl groups as two
individual singlets at 2.44 and 2.50 ppm, in addition to the
aryl protons that are present at the predicted field. Its 13C-
NMR signals are exact with the chemical structure. Acetyl
4-(2,4-Dichlorophenyl)-6-thioxo-5,6-dihydro-1,3,5-triazin-
2(1H)-one (4).
A mixture of 2,4-dichlorobenzoyl
isothiocyanate (0.02 mol) with urea (0.022 mol) and
catalytic triethyl amine in dioxane was heated at refluxing
temperature for 4 h and cooled, and the obtained solid
was crystallized from ethanol, mp 188–190°C, yield
59%. IR (υ, cmÀ1): 3344, 3251 (2NH), 1685 (C═O),
1234 cmÀ1 (C═S). 1H-NMR (DMSO-d6/D2O, ppm): δ
7.51 (d, 1H, 3J = 8.32 Hz, Haryl), 7.59 (d, 1H,
3J = 8.32 Hz, Haryl), 7.74 (s, 1H, Haryl), 9.59 and 9.63,
11.65 (3 s, 3H, 3NH, D2O exchangeable). 13C-NMR
(DMSO-d6, ppm): δ 127.7, 129.5, 130.9, 131.6, 133.9,
136.1, 142.2, 166.8, 181.9 (SP2-C). Anal. Calcd for
C9H5Cl2N3OS (274.13): C, 39.43; H, 1.84; N, 15.33.
Found: C, 39.34; H, 1.89; N, 15.42.
pyrimidinethione
15
was
condensed
with
of
phenylhydrazine to form the hydrazone derivative 17
(Scheme 4). The IR bands of pyrimidine 17 leads to NH
and C═N at υ 3390, 3244, and 1620 cmÀ1, respectively.
1H-NMR contained two NH’s signals at δ 9.60 and
9.64 ppm in addition to aromatic multiplet and aliphatic
protons that present at the predicted field. Pyrimidine
derivative 16 was allowed to react with urea to furnish
pyrimido[4,5-d]pyrimidine of type 18 (Scheme 4). The
analytical of compound 18 are exact with its chemical
structure (cf. Experimental section). One-pot condensation
of acetyl derivative 15 with 3-nitrobenzaldehyde,
ammonium acetate, and ethyl cyanoacetate furnish pyridin-
5-yl-nicotinonitrile analogue 19 in moderate yield (40%)
(Scheme 4). The spectral data confirm the formation of
compound 19 by the presence of absorption bands at 3414,
2218, 1701, and 1242 cmÀ1 for NH, C≡N, C═O, and C═S
2-(2,4-Dichlorophenyl)-6-imino-4-thioxo-5,6-dihydro-4H-
1,3-oxazine-5-carboxamide (7).
A mixture of 2,4-
dichlorobenzoyl isothiocyanate (0.02 mol) with
malononitrile (0.02 mol) and catalytic triethyl amine in
dioxane was heated at refluxing temperature for 4 h and
cooled, and the obtained solid was crystallized from
ethanol, mp 210–212°C, yield 65%. IR (υ, cmÀ1): 3344,
3325, 3195 (NH, NH2), 1680 (C═O), 1608 (C═N), and
1
groups, respectively, in its IR bands. Its H-NMR revealed
new singlet and multiplet at δ 6.98 and 7.39–7.68 ppm for
pyridine and aryl protons, respectively. Its 13C-NMR is
exact with the chemical structure (cf. Experimental section).
Finall, actyl pyrimidine 15 underwent aldol condensation
with aromatic aldehydes (namely, benzaldehyde and 3-
nitrobenzaldehyde to form cinnamoylpyrimidine derivative
20 and 21(Scheme 4). Their 1H-NMR indicate the presence
aromatic and olefinic multiplet signals in addition to
aliphatic CH3 (cf. Experimental section).
1
1233 cmÀ1 (C═S). H-NMR (DMSO-d6, ppm): δ 2.99 (s,
3
1H, Hoxazine ring), 7.51 (d, 1H, J = 8.28 Hz, Haryl), 7.59
3
(d, 1H, J = 8.28 Hz, Haryl), 7.74 (s, 1H, Haryl), 9.05 (s,
2H, NH2), 10.65 (s, H, NH). 13C-NMR (DMSO-d6,
ppm): δ 48.00 (SP3-C), 127.7, 129.5, 131.0, 131.6, 133.9,
136.1, 142.3, 158.6, 166.8, 181.9 (SP2-C). Anal. Calcd
for C11H7Cl2N3O2S (316.16): C, 41.79; H, 2.23; N,
13.29. Found: C, 41.88; H, 2.17; N, 13.36.
1-(6-(2,4-Dichlorophenyl)-4-hydroxy-2-mercaptopyridin-3-
yl)ethanone (9).
A mixture of 2,4-dichlorobenzoyl
CONCLUSION
isothiocyanate (0.02 mol) with acetyl acetone (0.02 mol)
and catalytic piperidine in dioxane was heated at
refluxing temperature for 4 h and cooled, and the
obtained pyridine derivative was crystallized from acetic
acid, mp 310–312°C, yield 70%. IR (υ, cmÀ1): 3375,
(OH, NH), 1697 (C═O), and 1234 cmÀ1 (C═S). 1H-
NMR (DMSO-d6, ppm): δ 1.90 (s, 3H, Hacetyl), 7.51 (d,
1H, 1,3J = 8.28 Hz, Haryl), 7.59 (d, 1H, 1,3J = 8.28 Hz,
Haryl), 7.67 (s, 1H, Hpyridine), 7.74 (s, 1H, Haryl), 7.92 (s,
1H, OH), 13.47 (s, 1H, SH). 13C-NMR (DMSO-d6,
ppm): δ 28.50 (SP3-C), 127.6, 127.7, 127.9, 129.5, 129.7,
130.5, 132.8, 133.5, 134.7, 136.3, 137.0, 172.3 (SP2-C).
Anal. Calcd for C13H9Cl2NO2S (314.19): C, 49.70; H,
2.89; N, 4.46 Found: C, 49.58; H, 2.85; N, 4.53.
In summary, we described the utility of 2,4-
dichlorobenzoyl isothiocyanate as reactive intermediate to
a series of triazines, pyrimidines, and
pyridines and their annulated systems via cycloaddition
and intramolecular cyclization reactions.
synthesize
EXPERIMENTAL
All melting points are uncorrected and were measured
using an Electro-thermal IA 9100 apparatus. IR spectra
(KBr) were measured on a Nexus 670 FTIR Nicolet,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2019
Cycloaddition of Aroyl Isothiocyanate
7-(2,4-Dichlorophenyl)-5-hydroxy-4-methylpyrido[2,3-d]
pyrimidin-2(1H)-one (10).
132.5, 135.5, 136.5, 137.0, 144.1, 152.3, 193.5, 201.1
(SP2-C). Anal. Calcd for C19H14Cl2N2OS (389.30): C,
58.62; H, 3.62; N, 7.20. Found: C, 58.71; H, 3.58; N, 7.16.
To a susbended 3-acetyl
pyridine 9 (0.02 mol) in ethoxide solution (prepared from
0.23 g sodium metal in 20 mL of absolute ethanol), urea
(0.011 mol) was added, the reaction mixture was refluxed
for 6 h, ethanol was evaporated, and the residue was
suspended in 50 mL of water and neutralize with HCl to
give compound 10 that recrystallized from acetic acid,
mp 201–203°C, yield 68%. IR (υ, cmÀ1): 3444 (O-H),
3325 (N-H), 1693 (C═O), 1H-NMR (DMSO-d6/D2O,
ppm): δ 2.58 (s, 3H, Hmethyl), 7.43 (d, 1H, 1,3J = 8.40 Hz,
Haryl), 7.58 (d, 1H, 3J = 8.40 Hz, Haryl), 7.74 (s, 1H, Haryl),
8.12 (s, 1H, OH, D2O exchangeable), 12.57 (s, 1H, NH,
D2O exchangeable), 13C-NMR (DMSO-d6, ppm): δ 32.12
(SP3-C), 125.6, 126.0, 126.5, 127.0, 127.9, 130.5, 130.6,
132.8, 133.5, 137.0, 142.0, 148.8, 166.2 (SP2-C). Anal.
Calcd for C14H9Cl2N3O2 (322.15): C, 52.20; H, 2.82; N,
13.04. Found: C, 52.29; H, 2.85; N, 12.98.
6-(2,4-Dichlorophenyl)-3,4-dimethyl-5-phenyl-5H-pyrazolo
[3,4-d]pyrimidine (16). A mixture of pyrimidine thione 3
(0.02 mol) with hydrazine hydrate (0.02 mol) in ethanol
(20 mL) was heated at refluxing temperature for 3 h. The
resulted precipitate was filtered off and crystallized
ethanol, mp 292–294°C; yield 70%. IR (υ, cmÀ1): 1620
(C═N). 1H-NMR (DMSO-d6, ppm): δ 2.44 (s, 3H,
H
methyl), 2.50 (s, 3H, Hmethyl), 7.27–7.90 (m, 8H, Haryl).
13C-NMR (DMSO-d6, ppm): δ 29.06, 30.85 (SP3-C),
126.9, 127.4, 129.0, 130.1, 130.9, 132.2, 132.4, 132.5,
135.6, 136.6, 137.0, 144.0, 152.3, 158.0, 160.1 (SP2-C).
Anal. Calcd for C19H14Cl2N4 (369.25): C, 61.80; H, 3.82;
N, 15.17. Found: C, 61.89; H, 3.79; N, 15.22.
2-(2,4-Dichlorophenyl)-6-methyl-1-phenyl-4-(2-
phenylhydrazono)-5-(1-(2-phenylhydrazono)ethyl)-1,4-
dihydropyrimidine (17). A mixture of pyrimidine thione 3
6-(2,4-Dichlorophenyl)-3-methyl-1H-pyrazolo[3,4-b]
pyridin-4-ol (11).
Hydraine hydrate (0.015 mol) was
(0.02 mol) with phenyl hydrazine (0.02 mol) in ethanol
(20 mL) was heated at refluxing temperature for 4 h. The
resulted precipitate was filtered off and crystallized
ethanol, mp 168–170°C, yield 52%. IR (υ, cmÀ1): 3390,
3244 (2NH), 1620 (C═N). 1H-NMR (DMSO-d6/D2O,
ppm): δ 1.29 (s, 3H, Hmethyl), 2.50 (s, 3H, Hmethyl), 7.27–
7.90 (m, 18H, Haryl), 9.60, 9.64 (s, 2H, 2NH, D2O
exchangeable). Anal. Calcd for C31H26Cl2N6 (553.48): C,
67.27; H, 4.73; N, 15.18 Found: C, 67.35; H, 4.70; N, 15.23.
added to a solution of compound 9 in ethanol, the
resulted mixture was refluxed for 4 h, and after cooling,
the resulted solid was filtered off and crystallized from
acetic acid, mp 282–284°C, yield 75%. IR (υ, cmÀ1):
1
3450 (OH), 3152 (NH). H-NMR (DMSO-d6/D2O, ppm):
δ 2.58 (s, 3H, Hmethyl), 7.54–7.91 (m, 3H, Haryl), 8.16 (s,
1H, OH, D2O exchangeable), 12.89 (s, 1H, NH, D2O
exchangeable). 13C-NMR (DMSO-d6, ppm): δ 30.28
(SP3-C), 126.8, 127.5, 127.9, 128.1, 129.8, 130.4, 131.1,
131.9, 132.1, 132.7, 132.8, 133.0 (SP2-C). Anal. Calcd
for C13H9Cl2N3O (294.14): C, 53.08; H, 3.08; N, 14.29.
Found: C, 52.98; H, 3.05; N, 14.34.
7-(2,4-Dichlorophenyl)-4,5-dimethyl-6-phenylpyrimido
[4,5-d]pyrimidin-2(6H)-one (18). A mixture of pyrimidine
thione 3 (0.02 mol), urea (0.022 mol), and potassium
hydroxide (0.02 mol) in ethanol (20 mL) was heated at
refluxing temperature for 5 h. The resulted precipitate
was filtered off and crystallized ethanol, mp 180–182°C,
6-(2,4-Dichlorophenyl)-3-methyl-1-phenyl-1H-pyrazolo
[3,4-b]pyridin-4-ol (12).
Phenyl hydrazine (0.015 mol)
1
yield 63%. IR (υ, cmÀ1): 1701 (C═O), 1604 (C═N). H-
was added to a solution of compound 9 in ethanol, and
the resulted mixture was refluxed for 4 h, and after
cooling, the resulted solid was filtered off and crystallized
from acetic acid, mp 268–270°C, yield 62%. IR (υ,
cmÀ1): 3344 (OH). 1H-NMR (DMSO-d6/D2O, ppm): δ
2.57 (s, 3H, Hmethyl), 7.27–7.74 (m, 3H, Haryl), 8.59 (s,
1H, OH, D2O exchangeable). Anal. Calcd for
C19H13Cl2N3O (370.23): C, 61.64; H, 3.54; N, 11.35.
Found: C, 61.75; H, 3.50; N, 11.43.
NMR (DMSO-d6/D2O, ppm): δ 1.81 (s, 3H, Hmethyl),
2.58 (s, 3H, Hmethyl), 7.39–7.68 (m, 8H, Haryl). 13C-NMR
(DMSO-d6, ppm): δ 17.81, 30.83, (SP3-C), 126.9, 127.5,
129.01, 129.06, 130.0, 130.9, 132.2, 132.4, 135.5, 136.5,
136.9, 144.1, 148.0, 152.4, 158.0, 169.2 (SP2-C). Anal.
Calcd for C20H14Cl2N4O (397.26): C, 60.47; H, 3.55; N,
14.10. Found: C, 60.56; H, 3.52; N, 14.14.
6-(2-(2,4-Dichlorophenyl)-6-methyl-1-phenyl-4-thioxo-1,4-
dihydropyrimidin-5-yl)-4-(3-nitrophenyl)-2-oxo-1,2-
1-(2-(2,4-Dichlorophenyl)-6-methyl-1-phenyl-4-thioxo-1,4-
dihydropyrimidin-5-yl)ethanone (15). A mixture of 2,4-
dihydropyridine-3-carbonitrile (19).
A
mixture of
dichlorobenzoyl isothiocyanate (0.02 mol) with
4-(phenylamino)pent-3-en-2-one (13) (0.02 mol) and few
drops of piperidine in dioxane was refluxed for 6 h and
cooled, and the obtained solid was crystallized from
acetic acid, mp >300°C, yield 73%. IR (υ, cmÀ1): 1701
pyrimidine thione 3 (0.02 mol), 4-nitrobenzaldehyde
(0.02 mol), ethyl cyanoacetate (0.02 mol), and AcONH4
(0.16 mol) in acetic acid (20 mL) was refluxed for 10 h,
and the resulted solid was filtered off and crystallized form
acetic acid, mp 180–182°C, yield 40%. IR (υ, cmÀ1): 3414
1
1
(C═O), 1242 (C═S). H-NMR (DMSO-d6, ppm): δ 1.81
(NH), 2218 (C≡N), 1701 (C═O), 1242 (C═S). H-NMR
(s, 3H, Hacetyl), 2.58 (s, 3H, Hmethyl ring), 7.39–7.68 (m,
8H, Haryl). 13C-NMR (DMSO-d6, ppm): δ 17.83, 30.85
(SP3-C), 126.9, 127.5, 129.0, 130.0, 130.9, 132.2, 132.4,
(DMSO-d6/D2O, ppm): δ 2.58 (s, 3H, Hmethyl), 6.98 (s,
1H, Hpyridine), 7.39–7.68 (m, 12H, Haryl), 12.32 (s, 1H,
NH). 13C-NMR (DMSO-d6, ppm): δ 30.83, (SP3-C),
Journal of Heterocyclic Chemistry
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M. G. Assy, H. A. El-Sayed, N. H. Ouf, A. Hamza, and H. A. Morsy
Vol 000
REFERENCES AND NOTES
114.5, 125.5, 126.0, 126.6, 126.9, 127.5, 127.8, 128.2,
128.9, 129.0, 130.0, 130.9, 132.2, 132.4, 132.5, 135.5,
136.5, 137.0, 144.1, 148.2, 152.4, 154.0, 157.1, 158.1,
160.3, 169.8 (SP2-C). Anal. Calcd for C29H17Cl2N5O3S
(586.45): C, 59.39; H, 2.92; N, 11.94. Found: C, 59.28; H,
2.88; N, 11.89.
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dihydropyrimidin-5-yl)-3-phenylprop-2-en-1-one (20).
A
mixture of pyrimidine thione 3 (0.02 mol), benzaldehyde
(0.02 mol), and sodium hydroxide (0.02 mol) was stirred
at room temperature for overnight, and the formed solid
was filtered off and crystallized from acetic acid, mp
215–217°C, yield 71%. IR (υ, cmÀ1): 1701 (C═O), 1604
1
(C═N), 1242 (C═S). H-NMR (DMSO-d6, ppm): δ 2.58
(s, 3H, Hmethyl), 6.80–7.68 (m, 15H, Haryl and Holefin).
13C-NMR (DMSO-d6, ppm): δ 30.83, (SP3-C), 90.8,
112.5, 125.5, 126.0, 126.6, 126.9, 127.5, 129.0, 130.0,
130.9, 132.2, 132.4, 132.5, 135.5, 136.5, 136.9, 144.1,
154.2, 158.0, 169.0, 182.4 (SP2-C). Anal. Calcd for
C26H18Cl2N2OS (477.40): C, 65.41; H, 3.80; N, 5.87.
Found: C, 65.33; H, 3.77; N, 5.91.
1-(2-(2,4-Dichlorophenyl)-6-methyl-1-phenyl-4-thioxo-1,4-
dihydropyrimidin-5-yl)-3-(3-nitrophenyl)
prop-2-en-1-one
[15] El-Sayed, H. A.; Abdel Hamid, A. M.; Assy, M. G.; Faraj, T. S
Synth Commun 2018, 48, 786.
(21). A mixture of pyrimidine thione 3 (0.02 mol), 4-
nitrobenzaldehyde (0.02 mol), and sodium hydroxide
(0.02 mol) was stirred at room temperature for overnight,
and the formed solid was seperated and crystallized from
acetic acid, mp 215–217°C, yield 67%. IR (υ, cmÀ1):
1701 (C═O), 1604 (C═N), 1242 (C═S). 1H-NMR
(DMSO-d6, ppm): δ 2.50 (s, 3H, Hmethyl), 6.89–7.96 (m,
14H, Haryl and Holefin). 13C-NMR (DMSO-d6, ppm): δ
30.85, (SP3-C), 101.0, 116.5, 125.5, 126.0, 126.6, 126.9,
127.5, 129.0, 129.06, 130.0, 130.9, 132.2, 132.4, 132.5,
135.5, 136.5, 136.8, 137.0, 152.3, 154.2, 158.0, 169.0,
182.5 (SP2-C). Anal. Calcd for C26H17Cl2N3O3S
(522.40): C, 59.78; H, 3.28; N, 8.04. Found: C, 59.88; H,
3.32; N, 8.09.
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of the
article.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet