Synthesis, characterization of new heterocyclic derivatives, and studying the possibility for their applications as surfactants, antimicrobial agents and corrosion inhibitors

Other Title(s)

تحضير و تشخيص مشتقات حلقية غير متجانسة جديدة و دراسة إمكانية تطبيقها كمنشطات للسطوح و مضادات مايكروبية و مثبطات للتآكل

Dissertant

al-Ubaydi, Kafa Khalaf Hammud Muhammad

Thesis advisor

al-Azzawi, Ahlam Maruf

Comitee Members

Hamad, Ahmad Shihab
Abd Allah, Husayn Ismail
al-Sadi, Khulud Abd Salih
Khalil, Muhammad Rifat Ahmad
al-Majidi, Suad Muhammad Husayn

University

University of Baghdad

Faculty

College of Science

Department

Chemistry Department

University Country

Iraq

Degree

Ph.D.

Degree Date

2013

English Abstract

The present work involved synthesis of new heterocyclic derivatives and studying the possibility for their application as surfactants, antimicrobial agents, or corrosion inhibitors.

Performing these targets includes the following parts: 1.

Part one involved synthesis of ethylene diamine tetraacetic acid (EDTA) dianhydride [1] followed by synthesis of its bisamic acids [2-6] and its ester [7] then conversion of these newly heterocyclic compounds to the corresponding sodium salts [8-13] as shown in Scheme (1).

2.

Part two involved synthesis of several new N-substituted-3,4,5,6-tetrachlorophthalimides via the following steps (Schemes (2) and (3)): a) Synthesis of substituted 2-amino benzothiazoles [14-17], 1-amino-quinoline-2(1H)-one [18], and 2-amino-5-mercapto-1,3,4-thiadiazole [19].

b) Synthesis of N-(substituted) -3,4,5,6-tetrachlorophthalamic acids [20-27] via the reaction of the prepared heterocyclic amines in step (a) with 3,4,5,6- tetrachlorophthalic anhydride then dehydrated them to the corresponding imides[28-35].

c) Conversion of the prepared amic acids to the corresponding sodium salts [36-43].

3.

Part three based on 3,4,5,6- tetrachlorophthalimide as a starting compound in synthesis of several new heterocyclic derivatives via performing the following steps (Scheme (4)): a) Synthesis of 3,4,5,6-tetrachlorophthalimide [44] by using two methods, conventional method ( using ammonia or urea with heating) and microwave irradiation method (using hydroxylamine hydrochloride or urea).

b) Synthesis of 3,4,5,6-tetrachlorophthalimide potassium salt [45] which converted to corresponding acetate [46] via treatment with ethyl chloroacetate by applying two methods.

78 c) Synthesis of 2-(N-(3,4,5,6-tetrachlorophthalimidyl)) acetohydrazide [47] via treatment of the prepared acetate [46] with hydrazine hydrate using conventional and microwave irradiation methods.

d) Introducing of the resulted acetohydrazide compound [47] in reactions with different reagents in different synthetic paths afforded the new compounds [48-56] as indicated in Scheme (4).

4.

Part four involved synthesis of several new pyromellitic anhydride derivatives as shown in Schemes ((5) and (6)) indicating in the following steps: a) Synthesis of pyromellitic diimide [57] via reaction of pyromellitic anhydride with urea via conventional and microwave irradiation methods then compound [57] converted to the corresponding potassium salt [58] which inturn converted to the target compound (ethyl-2-(N-(pyromellitic diimidyl)) acetate) [59] via reaction with ethyl chloroacetate.

b) Treatment of the resulted acetate [59] with hydrazine hydrate producing 2-(N-(pyromellitic diimidyl)) acetohydrazide [60] which introduced in different synthetic reactions producing the new compounds [61-67].

5.

Part five involved synthesis of new heterocyclic derivatives in which heterocycles linked to cyclic imides or amic acids following different synthetic strategies(schemes (7), (8), and (9)) as indicated in the following: a) Synthesis of ethylene diamine tetraacetic acid dianhydride derivatives [68-71] via reaction of EDTA dianhydride [1] with aniline producing bisamic acid [68] which subsequently dehydrated producing bisimide [69] then converted through chlorosulfonation to the corresponding sulfonyl chloride derivative [70] and this inturn was converted to sulfonamide derivative [71] via reaction of 79 [70] with 2-amino -6-nitrobenzothiazole.

b) Synthesis of N-(2-Acetamido-6- nitro –benzothiazole-2-yl) imides [73,74] had been done through preparation of 2-(2-chloroacetylamino) 6- nitro- benzothiazole[72] by reaction of 2-amino-6- nitro-benzothiazole with chloroacetyl chloride and this introduced in reactions with potassium salts of both 3,4,5,6- tetrachlorophthalimide and pyromellitic diimide producing compounds [73] and [74] respectively.

c) N-(substituted) pyromelliticbisamic acids [75,76] was synthesized by reaction of pyromellitic anhydride with of two different heterocyclic primary amino compounds (folic acid or cefotaxime).

All the prepared compounds containing both imide and heterocyclic moieties were characterized by recording their melting points and infrared (FTIR) spectra.

1HNMR and 13CNMR spectra for some of them were also recorded.

6.

Part six involves introducing of the newly synthesized compounds in different applications including: a) The screening of some of the synthesized compounds for both antibacterial and antifungal activities using cup-plate agar diffusion method showed a good inhibition zone against several microorganisms such as Staphylococcus aureus, Escherichia coli, Serratia marcescens, Bacillus subtilus, Actinobacter bowmanii, Proteus mirabilis, Klebsiella pneumonia, Pseudomonas aeruginosa, Crytococcus albidus, Candida utilis, Candida gulliermondii, Candida krusei, and Rhodorula mucilaginosa.

b) Characterization of surfactant physical properties through using several techniques such as acid–base titration, conductivity measurements, determination of the critical micellization 80 concentration (CMC) of dimer EDTA via UV-Vis spectroscopy, and dye solubilization method.

c) Thermal analysis for some of the synthesized compounds was done by subjected these heterocyclic compounds to thermal gravimetrical analysis (TGA) and differential scanning calorimetry (DSC) and the tested compounds showed good thermal stability.

d) To achieve one of the most important application goals of this work, several compounds had been subjected to corrosion tests through weight loss experiments and/ or potentiostatic tests with carbon steel presence under different acidic media.

Several numerical results had been obtained from Polarization behaviour studies of carbon steel such as Ecorr, icorr , P%, the Tafel slope, transfer coefficient, polarization resistance, thermodynamic values (ΔG, ΔH, and ΔS), and Kinetic of Corrosion (A, Ea, ΔS*, and ΔH*).

Also, the adsorption mechanism was studied by applying Temkin isotherm.

The obtained results showed, in general, a good inhibition of these compounds under study against the corrode media hydrochloric acid and/ or sulfuric acid (different concentrations).

Main Subjects

Chemistry

No. of Pages

288

Table of Contents

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Language

English

Data Type

Arab Theses

Record ID

BIM-600589