تحضير ايمايدات حلقية ثنائية وبعض مشتقاتها الكبريتية ودراسة خواصها الطيفية والتركيبية , عمليا ونظريا باستخدام نظرية دالية الكثافة == IR, NMR, MS Spectra and Structure of Some prepared Bicyclic Imides and Their Thione Derivatives; Experimental and Density Functional Theory studies
Author name:
عادل امعلا ضمد ال ازيرج
Supervisor name:
ناجي علي عبود
General topic:
Chemistry
Specific topic:
Chemistry
Degree:
Doctorate
University:
University Of Basrah - College Of Education For Pure Sciences
Language:
English
University location:
Basrah
First pages:
25T1591 - p.pdf
Abstract:
The present work involved four parts : First step concerned with the preparation some N, N’ - alkyl (aryl) bismaleimic acidsvia reaction of twice molar amounts of maleic anhydride and hydrazine for compound(A1), and different alkyl and aryl - diamines for compounds A2 - A7. The reaction wascarried out via nucleophilic attack of amino group in maleic anhydride. The structureof the compound (2Z,2Z’) - 4,4’ - (ethane - 1,2 - diylbis (azanediyl)) bis (4 - oxobut - 2 - enoicacid) (A2) was also unambiguously confirmed by X - ray single crystal structureanalysis. The white crystal crystallizes in the monoclinic system, space group C2/cwith the cell dimensions a =7.108(3), b=7.370(2), c= 20.859(6) Å, β = 91.260(4)oand Volume = 1092.65(6) Å3.Molecule is stabilized by an intramolecular O—H…O hydrogen bond. In thecrystal, molecules are connected through intermolecular N—H…O hydrogen bonds.Intermolecular and intramolecular hydrogen bonds coexist to stabilize the structure.The geometry calculated of compounds A1 - A7 was optimized using a Densityfunctional theory DFT with B3LYP hybrid functional and 6 - 311G (d, p) basis set, andis in good agreement with the structure obtained by the X - ray single crystal structureof compound A2. Also the fundamental vibrational frequencies of vibrational bandswere evaluated.The second part of this study was the treatment of N,N - alkyl and (aryl)bismaleimic acid (A1 - A7) with suitable dehydrating agents lead to dehydration andcyclization producing the corresponding N,N - alkyl and (aryl) bismaleimide (AD1 - AD7).The structure of the compound 1,1’ - (sulfonylbis(4,1 - phenylene)) bis (1H - pyrrole - 2,5 - dithione) (AD7) was also unambiguously confirmed by X - ray single crystalstructure analysis. The colorless crystal crystallizes in the monoclinic system, spaceAbstractix0200040000CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2phenyl4,4' - sulfonyldianilinedirect Aliphatic AromaticWavenumber cm¯¹Types of RCH str.CH2 - N strC=O strC - Ngroup P21/c with the cell dimension a =11.698(3), b=15.002(3), c= 20.053(6)Å andβ = 98.818(2)o Volume = 3478.07(13) Å3.FT - IR spectra show the position of the absorption bands vary with the type andlength of the link spacer (R) between the two maleimide rings on the compoundsAD1 - AD7.The absorption frequency of vinyl group increases with increasing methylene aliphatic chain spacer link between two maleimides ring, the correlation between some absorption bands and the type (direct link or aliphatic or aromatic) and length of aliphatic chain link spacer (R) between the two maleimide rings in the studied compounds AD1 - AD7 shown in the chart below.In the third part, a series of new bisthimalemide derivatives were prepared by thionation the compounds AD3, AD6 and AD7 with Lawesson’s reagent LR. Subsequent reaction of bismaleimimides AD3, AD6 and AD7 with Lawesson’s reagent afforded dithio derivatives.
