اسم المؤلف:
نور عبد المجيد ضياف الدوري
اسم المشرف:
صبحي عطية محمود الجبوري | مظهر يونس محمد المهيدي
المستخلص:
تتناول هذه الاطروحة تحضير المركبات الحلقية غير المتجانسة ذات الحلقة الخماسية مثل معوضات الثايادايازول و3,2,1 - ترايازولين والثايازولدين - 4 - اون والحلقة الرباعية مثل الازتدين - 2 - اون والحلقة الثلاثية الاوكسازردين, فضلا عن تحضير الحلقة السداسية البرمدين | The thesis deals with hetero cyclic compounds with five member rings like thiadiazole substituted 1,2,3 - triazoline and thiazoldine - 4 - one, four member ring like azetidine - 2 - one and three member rings oxazirdine. Synthesis including six member ring compounds like pyrimidin - 2,4,6 - trione in addition to synthesis seven member ring compound like oxazepine are synthesized. In the present work 4 - bromo aniline is used as precursor for the synthesis of the required compound; the 2 - aminobenzothiazole - 6 - bromo (K1) is synthesized from the reaction of 4 - bromo aniline with potassium thiocyanate in presence of bromine, the later (K1) was reacted with ethyl chloroformate to give ethylcarbamate (K2),which is used for the synthesis of urea derivatives (K3 - 8).through (K2) reaction with substituted aniline. Pyrmidin - 2,4,6 - trione (K9 - 14) is synthesized from the reaction of malonic acid with urea derivatives in acetyl chloride.Schiff bases (K15 - 20) are prepared through the condensation of 2 - aminobenzothiazole with substituted benzyldehid. Seven member ring are synthesized by cyclaziation of Schiff bases (K15 - 20) by using malic anhydride in absolute ethanol to give 2 - aryl - 3 - N - 6 - bromobenzothiazole - 5 - 7 - dione oxazepene (K21 - 26). four member ring is prepared from the reaction of Schiff bases(K15 - 20) with chloro acetyl chloride in 1,4 - Dioxane in the presence of tri ethyl amine to give azetidine - 2 - one(K27 - 32). Thiazoldine - 4 - one(K33 - 38) is synthesized from the reaction of Schiff bases(K15 - 20) with thioglycolic acid in the presence of Zinc chloride. The Oxazirdine(K74 - 79) is also prepared from the reaction of Schiff bases(K15 - 20) with 3 - chloro per benzoic acid in pyridine. 2 - (2 - chloroacetamide) - 6 - bromobenzothiazole(K39) is prepared from the reaction of 2 - aminobenzothiazole - 6 - bromo (K1) with chloro acetyl chloride. The compound (K39) is used in the preparation of substituted aryl amino acetyl - 2 - amino - 6 - bromobenzothiazole (K40 - 46) through its reaction with substituted amine. The thiazoldine - 4 - one - 2 - imine (K47) is also synthesized from the reaction of compound (K39) with potassium thiocyanate. The thiazoldine - 4 - one - 2 - imine (K47) is reacted with substituted benzeldehyd to give 2 - (5 - (aryldin) - 2 - imino - 4 - oxo - thiazoldin - 3 - yl) 6 - bromobenzothiazole (K48 - 53).The 2 - (6 - bromobenzothiazole - 2 - ylimino) thiozoldine - 4 - one(K95) is prepared from the reaction of 2 - acetylamino - 6 - bromobenzothiazole(K39) with ammonium isothiocyanate in ethanol 96%. The thiazoldine - 4 - one(K95) is used in the preparation of 2 - (6 - bromobenzothiazole - 2 - ylimino) - 5 - (sub.Methyl) thiozoldine - 4 - one(K96 - 100) through its reaction with various amine and formaldehyde.The aminobenzothiazole (K1) is also used for the preparation of thiosemicarbazide (K54) by its reaction with carbon disulphide. The substituted 1,3,4 - thiadiazole (K55 - 60) is synthesized from the reaction of thiosemicarbazide (K54) with various of carboxylic acids in the presence of phosphorous oxychloride. The aminobenzothiazole (K1) is used in the preparation of aryl ( benzothiazole - 2 - ayl ) dithiocarbamate (K61 - 65) through its reaction with carbon disulphide and arylhalid or alkylhalid in ethanol.The 2 - azido - 6 - bromobenzothiazole (K66) is prepared from the reaction of sodium azide with diazonuim salt ( prepared from the reaction of benzothiazole (K1) with sodium nitrate , hydrochloric acid ). 1,2,3 - triazoline (K67 - 71) are synthesized through the reaction of 2 - azidobenzothiazole (K66) with various olefin in ethanol. The treatment of aminobenzothiazole (K1) with phenyl isothiocyanate gives (6 - bromobenzothiazole - 2 - yl) - 3 - phenylthiourea (K72) which is converted to (6 - bromobenzothiazole - 2 - yl) - 3 - phenyl - 2 - thioxydihydropermidine - 4 - 6 - one (K73) through its reaction with malonic acid in dry. Benzene. The 2 - hydrazinobenzothiazole (K80) is prepared from the reaction of 2 - aminobenzothiazole (K1) with a mixture from hydrazine hydrate and hydrochloric acid in ethylene glycol. Pyrazoline compounds (87 - 92) are synthesized from the reaction of chalcons (K81 - 86) ( which are prepared from the condensation of substituted benzaldehyde with acetophenone in a base medium ) with hydrazino (K80). The hydrazino (K80) is used in the preparation of 2 - amino( - 6 - bromobenzothiazole)isoandole - 1,3 - diaone (K93) and 1 - (2 - amino - 6 - bromobenzothiazole)pyrroline - 2,5 - di - one (K94) through its reaction with phathalic anhydride and malic anhydride in ethanol. For furthur work, the preparation of Schiff bases (K101 - 110) carried out. from the condensation of substituted benzaldehyde with hydrazino (K80) in the presence of glacial acetic acid in ethanol. The 3 - ( - 6 - bromobenzothiazole - 2 - ylamino) - 2 - (sub.aryl) - 5,7 - di - one oxazipene (K111 - 120) are synthesized by cyclazition of Schiff bases (K101 - 110) by using malic anhydride in methanol. Schiff bases (K101 - 110) are also used in preparation of 1 - ( - 6 - bromobenzothiazole - 2 - ylamino) - 4 - (sub.aryl) - 3 - chloro - 2 - oxo - zetidine - 2 - one (K121 - 130) through its rection with chloro acetyl chloride in presence of tri ethyl amine in 1,4 - Dioxan. The 3 - (6 - bromobenzothioazol - 2 - ylamino) - 2 - (substituted aryl)thiozoldin - 4 - one (K130 - 140) is prepared from the reaction of thioglycolic acid with Schiff bases (K101 - 110) in presence of zinc chloride in dry. Benzene. In order to show the antibacterial activity of prepared compounds (k11,k23,k41,k56,k61,k62,k89,k97,k112,k118,k126,k137,k139) are evaluated against four types of common bacteria (Bacillus subtillis, Staphylococcus aureus, Eschershia coli, Klebsiella peneuomina). The result of biological study are compared with standered antibiotic (Ciprofloxacine & Gentamycin). The structure of the synthesized compound are confirmed by I.R, 1H - NMR & 13C - NMR spectra and Some chemical physical data.
