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العنوان
Hydrazinecarbothioamides in the synthesis of biologically active heterocyclic compounds /
المؤلف
Ali, Maysa Mahsoun Abdelrhman.
هيئة الاعداد
باحث / مايسة محسون عبد الرحمن على
مشرف / علاء الدين عبد الحفيظ حسن
مشرف / أشرف عبد المنعم على
مشرف / نصر كامل محمد
مشرف / كمال محمد على الشايب
الموضوع
Chemistry, Organic.
تاريخ النشر
2020.
عدد الصفحات
268 p. :
اللغة
الإنجليزية
الدرجة
الدكتوراه
التخصص
Organic Chemistry
تاريخ الإجازة
1/1/2020
مكان الإجازة
جامعة المنيا - كلية الهندسه - الكيمياء
الفهرس
Only 14 pages are availabe for public view

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from 329

Abstract

1. First part:-
To a stirred solution of CNIND, in dry (tetrahydrofuran) THF, a solution of substituted alkenylidene hydrazinecarbothioamides were added. The reaction mixture was stirred for 3 hrs then allowed to stand for 52-72 hrs at room temperature with admission of air to give furo-imidazo[3.3.3]propellane derivatives in (71-84 %).
2. Second part:-
The reaction mixture of N-substituted alkenylidene hydrazinecarbothioamides and the electron poor (TCNE) in anhydrous THF at room temperature without using any catalyst affords (Z)-4-amino-3-(substituted amino)-2-(substituted imino)-2,3-dihydrothiazole-5-carbonitriles and (Z)-(4-amino-5-cyano-3-substituted thiazol-2(3H)-ylidene)carbonohydrazonoyl dicyanides in 50-60 % and 25-43 % yield, respectively.
3. Third part:-
A mixture of N-substituted hydrazinecarbothioamides and 2-(bis(methylthio)methylene)malononitrile were heated in dry ethanol for 50 oC containing 0.5 mL of triethylamine afforded various heterocyclic rings such as 5-amino-4-cyano-3-(methylthio)-N-phenyl-1H-pyrazole-1-carbothioamide in 65 % yield, 5-amino-3-(methylthio)-1H-pyrazole-4-carbonitrile in 20%, 4-substituted-3-(substituted amino)-1H-1,2,4-triazole-5(4H)-thione (20% and 65 %) and 4-cyano-2-(2,2-dicyano-1,1-bis(methylthio)ethyl)-N-ethyl-5-imino-3-(methylthio)-2,5-dihydro-1H-pyrazole-1-carbothioamide in 80 % yield. Refluxing of thiosemicarbazides with ethyl 2-cyano-3,3-bis(methylthio)acrylate in dry ethanol containing 0.5 mL of triethylamine afforded (Z)-ethyl 2-cyano-2-(5-(substituted amino)-1,3,4-thiadiazol-2(3H)-ylidene)acetates, ethyl 5-amino-3-(methylthio)-1-(substituted carbamothioyl)-1H-pyrazole-4-carboxylates and ethyl 5-amino-3-(methylthio)-1H-pyrazole-4-carboxylate in good yields.
4. Fourth part:-
A mixture of DMAD and (Z)-N-unsubstituted/substituted-2-(2-oxoacenaphthylen-1-(2H)-ylidene)hydrazinecarbothioamisdes, was refluxed in absolute ethanol for 20-30 min to afford (Z)-methyl 2-((Z)-3-unsubstituted-/substituted-4-oxo-2-((E)-(2-oxoacenaphthylen-1-(2H)-ylidene)hydrazono)thiazolidin-5-ylidene)acetates in 70-76% yields. Surprisingly, only in the case of allyl derivative, an unexpected compound, (1R,4S)-tetramethyl 5-((1R,2R,3R)-2-(((Z,E)-N-allyl-N’-(2-oxoacenaphthylen-1(2H)-ylidene)carbamohydrazonoyl)thio)-1,2,3-tris(methoxy-carbonyl)cyclopropyl)-4-methoxy-7-oxabicyclo[2.2.1]-hepta-2,5-diene-1,2,3,6-tetracarboxylate was obtained in 10% yield. In addition, the reaction of 4-acetyl[2.2]paracyclophanylidenehydrazine-carbothioamides with DMAD and DEAD gave 1,3-thiazolidinones bearing a paracyclophanyl moiety; by adaptation of the previously mentioned procedure.