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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

Volume 30, Number 1

Reza Moradivalikboni 1,* Zabialah Heidarnezhad2, Fatemeh Heidarnezhad2 , Yuldashboy Hozhiboev1 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

DOI : http://dx.doi.org/10.13005/ojc/300156

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Article Published : 03 Apr 2014
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ABSTRACT:

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.

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Moradivalikboni R,* Heidarnezhad Z, Heidarnezhad F, Hozhiboev Y and Rahmanov R. 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. Orient J Chem 2014;30(1).

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Moradivalikboni R,* Heidarnezhad Z, Heidarnezhad F, Hozhiboev Y and Rahmanov R. 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. Orient J Chem 2014;30(1). Available from: http://www.orientjchem.org/?p=2815

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 analogues have been described in the literature 5-6. 1,3,4-thiadiazoles provided a usefulmethod for the synthesis of thiadiazolopyrimidine 7. Pyrimidine derivatives have been found to be associated with diverse biological activities and numerous reportshave appeared in the literature 8-12. This highlighted their chemistry and use. The pyrimidine derivatives have remarkable pharmacological activity 13,14 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.The 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 derivatives withelectrophiles20,21.Derivatives of 1,3,4-thiadiazolo [3,2-alpyrimidine are potential biologically active substances,22-25 The introductionof ketene dithioacetal fragments into the moleculesmakes it possible to synthesize heterocyclic systemswith various functional groups26,27. We Preparated2-R5-oxo  5-H  6 -Carbomorpholin  7-phenyl  1,3,4-thiadiazolo-[3,2-a] pyrimidine in two stage. In step first we have synthesize2-R5-oxo5-H6-EthylCarboxilate7-phenyl 1,3,4-thiadiazolo[3,2,-a]pyrimidine(3)  with use2- R 5-amino  1,3,4- thiadiazole(1) andethyl 2- formyl 3- oxo 3- phenyl propanoate (2 )(Figure 1).

 

 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 Figure 1.synthesisderivatives of 2-R5-oxo 5-H 6-ethylcarboxylate7-phenyl 1,3,4-thiadiazolo [3,2- a]pyrimidine


Click here to View Figure

 

In another  stage  2-R5-Oxo5-H6-EthylCarboxilate7-phenyl 1,3,4-thiadiazolo-[3,2,-a]pyrimidinereacted with  morpholin(4) until  produced  2-R 5-oxo  5-H  6 –Carbomorpholin 7 -phenyl  1,3,4-thiadiazolo-[3,2-a] pyrimidine(5-9)(f2).

 

http://www.orientjchem.org/wp-content/uploads/2014/04/Vol30_No1_React_Reza_fig1.jpg Figure  2. synthes is of  2- R 5-oxo  5-H  6-Carbomorpholin7-phenyl -1,3,4-thiadiazolo [3,2-a] pyrimidine

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Result and Discussion

we tried synthesisof  2- R 5-oxo  5-H  6-Carbomorpholin 7-phenyl -1,3,4-thiadiazolo [3,2-a] pyrimidinewith 2-R  5-oxo  5-H  6-ethylcarboxylate  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 asmethanolandethanolalcoholhave  more use. The herbicidal activities of the target compounds were evaluatedagainst a variety of weeds by flat-utensil method according with the standard bioactivity test.Applicability of this procedures, that  we synthesis  a wide variety of  2-R  5-oxo  5-H  6-R–amide derivatives7-phenyl  1 ,3,4- thiadiazolo [3,2-a] pyrimidine  from 2-R 5-oxo 5-H 6- ethyl carboxylate7-phenyl 1,3,4-thiadiazolo [3,2- a]pyrimidine and morpholinin the presence of alcohol ethanol at 78 oC and obtained the desirable products in good to excellent yields (Table 1).

 

 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 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
Click here to View table

 

Experimental

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. For example,2-CH3  5-oxo  5-H  6-ethylcarboxylate  7-phenyl 1,3,4- thiadiazolo [3,2-a] pyrimidine (1 mmol-0.315gr),morpholin(1 mmol- 0.087gr)reacted to gether in alcoholethanol at 78 oC.Andtheproduct(  2-CH3  5-oxo  5-H  6-carbomorpholin  7-phenyl 1,3,4- thiadiazolo [3,2-a] pyrimidine )isobtainedin 85%yield. 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).

Conclusions

Compound 2- R 5-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 . 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 pyrimidinethiosemicarbazide,1,3,4-thiadiazole compounds.

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