Новый способ синтеза солей 1-N-алкоксиаминопиридиния
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Дата
2017
ORCID
DOI
10.20998/2413-4295.2017.07.30
Науковий ступінь
Рівень дисертації
Шифр та назва спеціальності
Рада захисту
Установа захисту
Науковий керівник
Члени комітету
Видавець
НТУ "ХПИ"
Анотація
Найдено, что взаимодействие метил-N-хлор-N-алкоксикарбаматов с 4-диметиламинопиридином
является общим способом синтеза хлоридов 1-N-алкоксиаминопиридиния. Предложен новый способ синтеза
хлоридов 1-N-алкоксиаминопиридиния аммонолизом хлоридов N-(1-пиридиний)-N-алкоксимочевин в спиртовом
растворе при комнатной температуре. Впервые получен фторид 1-N-метоксиамино-4-диметиламинопиридиния взаимодействием хлорида N-(1-4-диметиламинопиридиний)-N-метоксимочевины с KF в
ацетонитриле. Структура солей 1-N-алкоксиаминопиридиния доказана с помощью данных cпектров ЯМР 1Н, 13С и
масс-спектров.
It was found, that methyl N-alkoxy-N-chlorocarbamates interaction with 4-dimethylaminopyridine was overall manner of synthesis of 1-N-alkoxyaminopyridinium chlorides. New1-N-n-octyloxyamino-4-dimethylaminopyridinium and 1-Nbenzyloxyamino- 4-dimethylaminopyridinium chlorides have been synthesized by the methyl N-chloro-N-n-octyloxycarbamate and methyl N-benzyloxy-N-chlorocarbamate interaction with 4-dimethylaminopyridine in acetonitrile solution, respectively. The novel synthesis of 1-N-alkoxyaminopyridinium chlorides by reaction of N- -алкоксимочевин alkoxy-N-(1- pyridinium)ureas chlorides ammonolysis has been proposed. 1-N-Methoxyamino-4-dimethylaminopyridinium chloride and 1- N-n-butyloxyamino-4-dimethylaminopyridinium chloride have been synthesized by reaction of N-1-4-dimethylaminopyridinium- N-methoxyurea chloride and N-n-butyloxy-N-(1-4-dimethylaminopyridinium)urea chloride, respectively, with excess of ammonia in ethanol solution at room temperature during few minutes. Evidently, the carbamoyl proton elimination by ammonia causes further formation 1-N-alkoxy-4-dimethylaminopyridinium chlorides and HNCO. It is new example of decarbamoylation of N-alkoxy-N-(1-pyridinium)ureas salts. 1-N-Metoxyamino-4-dimethylaminopyridinium fluoride has been synthesized by N-1-(4-dimethylamino)pyridinium-N-methoxyurea chloride reaction with potassium fluoride in acetonitrile. Probably, in this reaction N-1-(4-dimethylamino)pyridinium-N-methoxyurea caution decarbamoylation occurs after the chloride anion exchange on fluoride anion. 1-N-Alkoxyaminopyridinium salts structures have been confirmed by data of NMR 1H spectra, NMR 13C spectra and mass-spectra.
It was found, that methyl N-alkoxy-N-chlorocarbamates interaction with 4-dimethylaminopyridine was overall manner of synthesis of 1-N-alkoxyaminopyridinium chlorides. New1-N-n-octyloxyamino-4-dimethylaminopyridinium and 1-Nbenzyloxyamino- 4-dimethylaminopyridinium chlorides have been synthesized by the methyl N-chloro-N-n-octyloxycarbamate and methyl N-benzyloxy-N-chlorocarbamate interaction with 4-dimethylaminopyridine in acetonitrile solution, respectively. The novel synthesis of 1-N-alkoxyaminopyridinium chlorides by reaction of N- -алкоксимочевин alkoxy-N-(1- pyridinium)ureas chlorides ammonolysis has been proposed. 1-N-Methoxyamino-4-dimethylaminopyridinium chloride and 1- N-n-butyloxyamino-4-dimethylaminopyridinium chloride have been synthesized by reaction of N-1-4-dimethylaminopyridinium- N-methoxyurea chloride and N-n-butyloxy-N-(1-4-dimethylaminopyridinium)urea chloride, respectively, with excess of ammonia in ethanol solution at room temperature during few minutes. Evidently, the carbamoyl proton elimination by ammonia causes further formation 1-N-alkoxy-4-dimethylaminopyridinium chlorides and HNCO. It is new example of decarbamoylation of N-alkoxy-N-(1-pyridinium)ureas salts. 1-N-Metoxyamino-4-dimethylaminopyridinium fluoride has been synthesized by N-1-(4-dimethylamino)pyridinium-N-methoxyurea chloride reaction with potassium fluoride in acetonitrile. Probably, in this reaction N-1-(4-dimethylamino)pyridinium-N-methoxyurea caution decarbamoylation occurs after the chloride anion exchange on fluoride anion. 1-N-Alkoxyaminopyridinium salts structures have been confirmed by data of NMR 1H spectra, NMR 13C spectra and mass-spectra.
Опис
Ключові слова
строение солей, хлориды N-(1-пиридиний)-N-алкоксимочевин, аммонолиз, N-хлор-N-алкоксикарбаматы, N-алкоксигидразины, декарбамоилирование, обмен аниона, 4-диметиламинопиридин, 1-N-alkoxyaminopyridinium, salts, N-alkoxy-N-(1-pyridinium)ureas chlorides, ammonolysis, N-alkoxy-Nchlorocarbamates, N-alkoxhydrazines, decarbamoylation, synthesis, anion exchange, 4-dimethylaminopyridine
Бібліографічний опис
Новый способ синтеза солей 1-N-алкоксиаминопиридиния / В. Г. Штамбург [и др.] // Вісник Нац. техн. ун-ту "ХПІ" : зб. наук. пр. Сер. : Нові рішення в сучасних технологіях = Bulletin of National Technical University "KhPI" : coll. works. Ser. : New solutions in modern technologies. – Харків : НТУ "ХПІ", 2017. – № 7 (1229). – С. 211-218.