Reaction of 2-R 5-oxo 5-H 6-Ethylcarboxylate 7-phenyl-[1,3,4] thiadiazolo-[3,2-a]pyrimidine with morpholin and their properties

Article abstract of DOI:10.13005/ojc/300156

In this article presents Synthesis of 2-R5-oxo 5-H 6-Carbomorpholin 7-phenyl 1, 3, 4-thiadiazolc-[3, 2-a] pyrimidine through reaction of 2-R 5 - Oxo 5 - H 6-EthylCarboxilate 7 - phenyl-1, 3, 4-Thiadiazolo-[3, 2-a] pyrimidine with morpholin. in particular, for the new antibacterial drugs in these homologousseries of compounds, we have synthesized 2-R5-oxo 5-H 6-Carbomorpholin 7-phenyl 1, 3, 4-thiadiazolo-[3, 2-a] pyrimidine. The structures of the compounds obtained are set NMR, ¹³C, IR-spectroscopy.

Full text of DOI:10.13005/ojc/300156

ISSN: 0970-020 X
CODEN: OJCHEG
2014, Vol. 30, No. (1):
Pg. 391-394
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Reaction of 2-R 5-oxo 5-H 6- Ethylcarboxylate 7-phenyl-[1,3,4]
thiadiazolo-[3,2-a]pyrimidine with Morpholin
and their Properties
REZA MORADIVALIKBONI1*,ZABIALAH HEIDARNEZHAD2,
FATEMEH HEIDARNEZHAD2,YULDASHBOY HOZHIBOEV 1 and RAHMAN RAHMANOV1
1V.I.Nikitin Institute of Chemistry Academy of Sciences of the Republic of Tajikistan.
2Department of Chemistry,Andimeshk Branch, Islamic Azad University, Andimeshk , Iran.
*Corresponding author E-mail: rmoradi02@yahoo.com
http://dx.doi.org/10.13005/ojc/300156
(Received: October 27, 2013; Accepted: December 02, 2013)
ABSTRACT
In this article presents Synthesis of 2-R5-oxo 5-H 6 -Carbomorpholin 7-phenyl 1,3,4-
thiadiazolo-[3,2-a] pyrimidine through reaction of 2- R 5 - Oxo 5 - H 6- EthylCarboxilate 7 – phenyl
-1, 3,4 – Thiadiazolo-[3,2-a] pyrimidine with morpholin. in particular,for the new antibacterial drugs
in these homologousseries of compounds, we have synthesized 2-R5-oxo 5-H 6 -Carbomorpholin
7-phenyl 1,3,4-thiadiazolo-[3,2-a] pyrimidine .The structures of the compounds obtained are set
NMR, 13C, IR- spectroscopy.
Keywords: 2-R 5-oxo 5-H 6 -Carbomorpholin 7-phenyl 1,3,4-thiadiazolo-[3,2-a]
pyrimidine - 2- R 5-Oxo 5-H 6-EthylCarboxilate 7 – phenyl -1, 3,4 –Thiadiazolo-[3,2-a]
pyrimidine –Morpholin -Synthesis - The reaction.
INTRODUCTION
and numerous reportshave appeared in the
literature 8-12. This highlighted their chemistry and
The diverse and interesting biological
activity of thiadiazoleshas been reported 1-4It is
well known that these heterocyclesare valuable
building blocks. Many methods for preparationof
these heterocyclic ring systems and their fused
use. The pyrimidine derivatives have remarkable
13,14
pharmacological activity
and widely used in
the field of anti-microbial, antiviral, etc. Thiadiazole
derivatives were shown to possess many biological
activities including anti-inflammatory 15-16
.
analogues have been described in the literature 5-6
.
1,3,4-thiadiazoles provided a usefulmethod for the
synthesis of thiadiazolopyrimidine 7.
The introduction of a substituent at position
6 of the1,3,4-thiadiazolo [3,2-a] pyrimidine system
efficientlyenhances the physiological activity of
the molecule17-19. This replacement occurs in the
reactions of 1,3,4 -thiadiazolo [3,2-a] pyrimidine
Pyrimidine derivatives have been found
to be associated with diverse biological activities

392
MORADIVALIKBONI et al., Orient. J. Chem., Vol. 30(1), 391-394 (2014)
derivatives with electrophiles20,21.Derivatives of 1,3,4-
thiadiazolo [3,2-alpyrimidine are potential biologically
active substances,22-25. The introduction of ketene
RESULT AND DISCUSSION
We tried synthesisof 2- R 5-oxo 5-H
dithioacetal fragments into the molecules makes 6-Carbomorpholin 7-phenyl -1,3,4-thiadiazolo [3,2-a]
it possible to synthesize heterocyclic systemswith pyrimidinewith 2-R 5-oxo 5-H 6-ethylcarboxylate
various functional groups26,27
.
7-phenyl 1 ,3,4-thiadiazolo [3,2-a] pyrimidine and
morpholin in varioussolvent. But alcohols are the
best solvents to this reaction .The alcoholssuch
We Preparated2-R5-oxo 5-H
6
-Carbomorpholin 7-phenyl 1,3,4-thiadiazolo- asmethanolandethanolalcoholhave more use. The
[3,2-a] pyrimidine in two stage. In step first we have herbicidal activities of the target compounds were
synthesize2-R5-oxo5-H6-EthylCarboxilate7-phenyl evaluatedagainst a variety of weeds by flat-utensil
1,3,4-thiadiazolo[3,2,-a]pyrimidine(3) with use2- R method according with the standard bioactivity
5-amino 1,3,4- thiadiazole(1) andethyl 2- formyl 3- test.
oxo 3- phenyl propanoate (2 )(Fig. 1).
Applicability of this procedures, that we
In another stage 2-R5-Oxo5-H6- synthesis a wide variety of 2-R 5-oxo 5-H 6-R-
EthylCarboxilate7-phenyl 1,3,4-thiadiazolo-[3,2,-a] amide derivatives7-phenyl 1 ,3,4- thiadiazolo [3,2-a]
pyrimidinereacted with morpholin(4) until produced pyrimidine from 2-R 5-oxo 5-H 6- ethyl carboxylate7-
2-R 5-oxo 5-H 6 –Carbomorpholin 7 -phenyl 1,3,4- phenyl 1,3,4-thiadiazolo [3,2- a]pyrimidine and
thiadiazolo-[3,2-a] pyrimidine(5-9)(f2).
morpholinin the presence of alcohol ethanol at 78
Table 1.synthesisof 2- R 5-oxo 5-H 6-Carbomorpholin 7-phenyl -1,3,4-thiadiazolo [3,2-a]
pyrimidinefrom 2- R 5-oxo 5-H 6-ethylcarboxylate 7-phenyl 1 ,3,4- thiadiazolo [3,2-a] pyrimidine
and morpholina
Entry Thiadiazol
pyrimidine
R-amine
derivatives
Product
Time(h)
(%)
Yieldb
point
Melting
O
O
O
O
N
N
N
O
N
N
OEt
H
S
N
Ph
5
Morpholin
7
90
170-172
H
S
N
N
Ph
O
O
O
N
N
N
N
O
COOEt
Ph
N
H3
C
S
N
O
Ph
H3
C
S
6
7
8
Morpholin
Morpholin
Morpholin
6
5
5
85
90
92
175-176
178-180
182-183
O
O
O
N
N
N
N
O
N
N
OEt
Ph
S
N
Ph
Ph
S
Ph
O
O
N
O
O
N
N
N
O
N
N
OEt
PhH2
C
PhH2C
S
N
Ph
S
Ph
O
O
O
O
N
N
N
O
N
N
OEt
9
Morpholin
6
80
181-183
Br
S
N
Ph
Br
S
N
Ph
a Reactions were carried out with 2-R 5-oxo 5-H 6-ethylcarboxylate 7-phenyl 1 ,3,4- thiadiazolo-[3,2-a] pyrimidine
and Morphplin
b Yields refer to isolated pure products

MORADIVALIKBONI et al., Orient. J. Chem., Vol. 30(1), 391-394 (2014)
393
oC and obtained the desirable products in good to
excellent yields (Table 1).
[3,2-a] pyrimidine (1 mmol-0.315gr),morpholin(1
mmol- 0.087gr) reacted to gether in alcoholethanol
at 78 C. And the product (2-CH3 5-oxo 5-H
o
ExPERIMENTAL
6-carbomorpholin 7-phenyl 1,3,4- thiadiazolo [3,2-a]
pyrimidine ) isobtainedin 85%yield.
A mixture of 2-CH3 5-oxo 5-H
6-ethylcarboxylate 7-phenyl 1,3,4- thiadiazolo [3,2-a]
pyrimidine (1 mmol),amin derivatives(1 mmol) was
stirred magnetically at 78oC and the progress of the
reaction was monitored by thin-layer chromatography
(TLC). The reaction mixture was filtered.In all the
cases, the product obtained after the usual work up
gave satisfactory spectral data.
2-CH3 5-oxo 5-H 6-carbomorpholin
7-phenyl -1,3,4-thiadiazolo [3,2-a] pyrimidine:1H
NMR (400 MHz, CDCl3, δ ppm): 0.9(s,3H,CH3 ););
3.65 (t,2H,CH2);7.30-7.46 (5H, Ph); - 13C NMR (100
MHz, CDCl3, δ ppm): 24.2(CH3),45.5 (CH2),45.5
(CH2),66.2 (CH2), 66.2 (CH2), 118 (C), 126,4 (CH)
, 126,4 (CH) ,128(CH), 128.7(CH), 128.7(CH),
136.9(C), 154.7(C), 159 .8(C),162.1(C), 163
(C),168(C).
For example,2-CH3 5-oxo 5-H
6-ethylcarboxylate 7-phenyl 1,3,4- thiadiazolo
O
O
C
COOEt
COOEt
N
N
Dioxan
N
N
O
C
C
+
R
S
N
Ph
S
R
NH2
2
1
3
R:(H ,CH3, Ph- ,PhCH2- ,Br)
Fig. 1: Synthesis derivatives of 2-R5-oxo 5-H 6-ethylcarboxylate7-phenyl
1,3,4-thiadiazolo [3,2- a]pyrimidine
O
O
O
N
COOEt
N
N
N
N
N
O
C2H5OH
Solvent
+
Morpholin
4
R
S
N
Ph
R
S
Ph
5-9
R:H(5) ,CH3(6) , Ph(7) , PhCH2(8) ,Br(9)
Fig. 2: Synthesis of 2- R 5-oxo 5-H 6-Carbomorpholin7-phenyl -1,3,4-thiadiazolo [3,2-a] pyrimidine
CONCLUSIONS
The pyrimidine derivatives haveremarkable
pharmacological activity and widelyused in the field
of anti-microbial, antiviral. Such medicinal utilities of
the Pyrimidine derivatives prompted to synthesize
the new pyrimidine thiosemicarbazide,1,3,4-
thiadiazole compounds.
Compound2-R5-oxo 5-H 6-Carbomorpholin
7-phenyl -1,3,4-thiadiazolo [3,2-a] pyrimidine were
procedure in excellent yields from 2- R 5-oxo 5-H
6-ethylcarboxylate 7-phenyl 1,3,4- thiadiazolo [3,2-a]
pyrimidine and morpholinthat have a broadspectrum
of antimicrobial activity .

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