Geminal systems. 16. Reactions of N-chloro-N-alkoxy-N-alkylamines with amines

Штамбург, В. Г.; Rudchenko, V. F.; Nasibov, Sh. S.; Червин, И. И.; Плешкова, А. П.; Kostyanovskii, R. G.

doi:10.1007/bf00963422

Cited by 7 publications

(8 citation statements)

References 7 publications

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“…The obtained white precipitate was filtered off, washed by benzene (5 ml), dried at 2 Torr, yielding N-ethoxy-N-(4-dimethylaminopyridin-1-ium-1-yl)urea chloride (2c) (28,0 mg, 81%), which was identified by its 1 Н NMR spectra. 1…”

Section: Decarbamoylation Of N-ethoxy-n-(4-dimethylaminopyridin-1ium-mentioning

confidence: 99%

“…[10][11][12][13] Our previous XRD studies confirmed that 4-dimethylamino substituted 1-alkoxyaminopyridinium salts (1-3 and 5) predominantly exist in their quinonoid form (B) 3,6-9 ( Figure 5). In pyridinium moiety the N-C(2), the N-C(6), the C(3)-C(4) and the C(4)-C(5) bonds are elongated and the C(2)-C(3) and the C(5)-C(6) bonds are shortened comparably to the same bonds in pyridine and at 4-position unsubstituted 1alkoxyaminopyridinium salts (1,2). In compounds 1-3 and 5 the C(4)-NMe2 bond is strongly shortened and is near to the length of a C=N double bond.…”

Section: Introductionmentioning

confidence: 95%

“…Five types of 1-alkoxyaminopyridinium salts are known: N-alkoxy-N-(pyridin-1-ium-1-yl)-N-tert-alkylamine salts (1), [1][2][3] N-alkoxy-N-(pyridin-1-ium-yl)urea salts (2), [3][4][5][6] Nalkoxy-N-(1-pyridinium)carbamate chlorides(3), 7 N-alkoxy-N-(pyridin-1-ium-1-yl)benzamide chlorides(4) 3 and unsubstituted 1-alkoxyamino-4-dimethylamino-pyridinium salts 5 8,9 (Figure 1). 1-Alkoxyamino-4-dimethylaminopyridinium salts 5 were synthesized by the reaction of methyl N-alkoxy-Nchlorocarbamates with 4-dimethylaminopyridine (DMAP).…”

Section: Introductionmentioning

confidence: 99%

“…The known types of 1-alkoxyaminopyridinium salts 1-were synthesized by the interaction of appropriate N-alkoxy-N-chloroamines and N-alkoxy-Nchloroamides with pyridines[1][2][3][4][5][6][7][8][9] (Figure 2).…”

mentioning

confidence: 99%

“…1 Н NMR (300 MHz, СD3OD) δ = 3.304 (6H, s, NMe2), 3.644 (3H, s, NOMe), 7.024 (2H, d, 3 J=8.1 Hz, C(3,5)H Py), 8.305 (2H, d, 3 J=8.1 Hz, C(2,6)H Py). MS (FAB) m/z 373 2M + •Cl -(1), 371 2M + •Cl -(4), 168 M + (100), 137 (41), 122 (22).b) The solution of N-methoxy-N-(4-dimethylaminopyridin-1-ium-1-yl)urea chloride (2b) (0.147 mmol, 36.2 mg) in dimethylsulfoxide (2 mL) was kept at 19 °C for 22 h, then DMSO was distilled off at 65-68 °C and 2 Torr, then the obtained residue was washed twice by benzene (10 mL and 3 mL),yielding N-methoxy-N-(4-dimethyl-aminopyridin-1ium-1-yl)urea chloride (1b) (34.0 mg, 92%) which was identified by its 1 Н NMR spectrum 1. Н NMR (300 MHz, СD3OD) δ =3.330 (6H, s, NMe2), 3.892 (3H, s, NOMe), 7.074 (2H, d, 3 J= 6.6 Hz, C(3,5)H Py), 8.292 (2H, d, 3 J= 6.6 Hz, C(2,6)H Py).…”

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confidence: 99%

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Decarbamoylation of N-Alkoxy-N-(4-Dimethylaminopyridin-1-Ium-1-Yl)ureas Chlorides in Dimethylsulfoxide as Route to 1-Alkoxyamino-4-Dimethylaminopyridinium Chlorides

Штамбург

Shtamburg

Anishchenko³

et al. 2018

ECB

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Section: Decarbamoylation Of N-ethoxy-n-(4-dimethylaminopyridin-1ium-mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Decarbamoylation of N-Alkoxy-N-(4-Dimethylaminopyridin-1-Ium-1-Yl)ureas Chlorides in Dimethylsulfoxide as Route to 1-Alkoxyamino-4-Dimethylaminopyridinium Chlorides

Штамбург

Shtamburg

Anishchenko³

et al. 2018

ECB

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The properties and structure of N-chloro-N-methoxy-4-nitrobenzamide

Штамбург¹,

Tsygankov²,

Шишкин³

et al. 2012

Mendeleev Communications

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Mendeleev Communications As it was shown by S. A. Glover et al., 2-10 N-X-N-alkoxycarboxamides [X = OC(O)R, OAlk, Cl] represent a new unusual family of amides, or anomeric amides. The presence of two strongly electronegative substituents with lone electron pairs (Lp) should effect the pyramidality of the amide nitrogen atom which should be sp 3 hybridized. 2,10 In the ON -X group of anomeric amides the N-X bond should be elongated and destabilized and N-OAlk bond should be shortened due to n O(Alk) ® s * N-X anomeric effect action. 2-9 The high IR n values of C=O group in most of such amides was recognized as the argument for their nitrogen pyramidality, 2,6 which was later confirmed by XRD studies. 9-15 However, XRD evidence for the case of N-chloro-N-alkoxybenzamides was lacking because of their lability. Herein, we have fulfilled XRD study of N-chloro-N-methoxy-4-nitrobenzamide which was synthesized by the chlorination of N-methoxy-4-nitrobenzamide (Scheme 1). ‡ In fact, the inves tiga

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Synthesis and structure of N-alkoxyhydrazines and N-alkoxy-N’,N’,N’-trialkylhydrazinium salts

Штамбург

Шишкин

Zubatyuk

et al. 2013

Mendeleev Communications

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Mendeleev Communications N-Alkoxyhydrazines represent an interesting example of ON -N geminal systems. 1-10 Usually, N-alkoxyhydrazines are very unstable due to n N ® s* N-O(Alk) orbital interaction within the N-OAlk bond. 11 Only one compound of this type 1 is known, 11 in which the donor capacity of nitrogen is decreased owing to its participation in aziridine cycle (Scheme 1). Tetramethoxyhydrazine 2 3 easily dissociates into two dimethoxyaminyl radicals on heating since its N-N bond is weakened by n O(Me) ® s* N-N anomeric effect. 3,4 The other N-alkoxy-N-alkylhydrazines are postulated as unstable primary intermediates in nucleophilic substitution at nitrogen atom in the reactions of N-chloro-N-alkoxy-N-tert-alkylamines with N-nucleo philes 9,11 and in the reactions of N-acyloxy-N-alkoxybenzamides with anilines. 12,13 However, N-alkoxyhydrazines with electron-withdrawing substituents at both nitrogen atoms, such as N,N'-dialkoxy-N,N'-bis-(alkoxycarbonyl)hydrazines 14 and N,N'-diacyl-N,N'-dialkoxyhydrazines 8,15,16 are relatively stable compounds. Among them, structure of N,N'-bis(4-chlorobenzoyl)-N,N'-diethoxyhydrazine 3 has been studied by XRD. 8 For the further XRD studies of N-alkoxyhydrazines structures we selected N,N'-bis(methoxycarbonyl)-N,N'-dimethoxyhydrazine 5 and N-methoxyhydrazine 7. Compound 5 is major product of methanolysis of methyl N-chloro-N-methoxycarbamate 4 in the presence of Et 3 N. 17 Compound 7 was synthesized by the reaction of compound 4 with potassium salt of N-acetylbenzenesulfonamide in MeCN (see Scheme 1). ‡ Synthesis and structure of N-alkoxyhydrazines and N-alkoxy-N',N',N'-trialkylhydrazinium salts †

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Geminal systems. 16. Reactions of N-chloro-N-alkoxy-N-alkylamines with amines

Cited by 7 publications

References 7 publications

Decarbamoylation of N-Alkoxy-N-(4-Dimethylaminopyridin-1-Ium-1-Yl)ureas Chlorides in Dimethylsulfoxide as Route to 1-Alkoxyamino-4-Dimethylaminopyridinium Chlorides

Decarbamoylation of N-Alkoxy-N-(4-Dimethylaminopyridin-1-Ium-1-Yl)ureas Chlorides in Dimethylsulfoxide as Route to 1-Alkoxyamino-4-Dimethylaminopyridinium Chlorides

The properties and structure of N-chloro-N-methoxy-4-nitrobenzamide

Synthesis and structure of N-alkoxyhydrazines and N-alkoxy-N’,N’,N’-trialkylhydrazinium salts

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