Синтез и ИК-спектроскопия N гидроксиимидов
Електронний архів E-archive DonNTU – (Electronic archive Donetsk National Technical University)
Переглянути архів Інформація| Поле | Співвідношення | |
| Title |
Синтез и ИК-спектроскопия N гидроксиимидов
SYNTHESIS AND IR SPECTROSCOPY OF N HYDROXYIMIDES |
|
| Creator |
Новикова, Е.В.
Компанец, М.А. Кущ, О.В. Редько, А.Н. Симонов, М.А. |
|
| Subject |
N гидроксифталимид
инфракрасная спектроскопия N-hydroxyphthalimide infrared spectroscopy |
|
| Description |
Reaction of ring-substituted phthalic anhydrides (nitro-, halogen-, carboxy-, methyl and methoxy) in pyridine with hydroxylamine hydrochloride under reflux gives the corresponding N hydroxyphthalimides. IR spectra of the synthetized N-hydroxyimides shows maxima in the region of the carbonyl group valence vibration. Split strong band at 1791.5 - 1733 cm-1 corresponds to the C=O of N hydroxyphthalimide. Substituents COOH, F, Cl, Br, I, NO2 increase the value of sym. υ(C=O), and CH3, CH3O decrease the value of sym. υ(C=O), compared with unsubstituted structure. The change in force constants of carbonyl and hydroxyl groups under the strong influence of electronic effects of substituents, transmitted through the conjugation system cause the shift of bands in the IR spectra.The magnitude of force constants depend primarily upon the bond order. Transfer of the electron density from oxygen under the influence of electron-withdraving groups to the C=O bond causes the increasing of force constant (the bond strenght increased) and shifting frequency of carbonyl bond to higher values. Decrease of the wavenumber of carbonyl band also is observed for NHTPI, the structure with four phenyl substituents and NHNI, containing fused aromatic rings. For NDHPI characteristic carbonyl band shifts towards higher values. For O-H group the frequency changes is not so impressive as for C=O group because of greated distance from substituents. The vibrational frequency shifts of the C=O at the introduction into the molecule different substituents (compared with unsubstituted structure) depends upon the σ-substituents correlation constants. Satisfactory correlation (r = 0,97) established for 4-substituted N-hydroxyimides, and approximate correlation (r = 0,91) established for 3-substituted NHPI. Effect of substituent in 4-position of benzene ring is more pronounced. IR spectra of N hydroxynaphthalimide, containing condensed aromatic moiety, shows the highest decrease in frequency of sym. and antisym. vibration of C=O. The result of obtaining spectral-structural correlations could be used for the prediction of N-hydroxyphthalimide spectral characteristics and identification of catalytic species in kinetic experiments. Синтезирован ряд N-гидроксиимидов - замещенные в бензольном кольце N гидроксифталимиды, N-гидроксинафталимид, содержащий конденсированный ароматический фрагмент и N,N дигидроксипиромеллитимид с двумя N-OH группами. Проведено отнесение экспериментально наблюдаемых полос поглощения в ИК-спектрах полученных соединений, показано влияние природы заместителей на спектральные характеристики N-гидроксиимидов. |
|
| Date |
2014-04-15T16:32:55Z
2014-04-15T16:32:55Z 2014 |
|
| Type |
Article
|
|
| Identifier |
УДК 54.057 + 547.575
http://ea.donntu.edu.ua/handle/123456789/26004 |
|
| Language |
other
|
|
| Publisher |
Наукові праці ДонНТУ. Серія: Хімія і хімічна технологія. - 2014. - Вип. 2(23). - С. 90-97
|
|