Synthesis and Crystal Structure of N-Acryloylcytisine and N-( -Morpholinopropionyl)cytisine

Ibraev, M. K.; Турдыбеков, Д. М.; Фазылов, С. Д.; Турдыбеков, К. М.; Газалиев, А. М.; Zhivotova, T. S.

doi:10.1023/b:rujo.0000043720.17713.bd

Cited by 9 publications

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“…However, the bulky cinnamoyl group in 6, which was bonded to N12, was planar (within ±0.083 °A ) and there was no stereochemical hindrance to destroy the conjugation (mesomeric effect). Neighboring C14=O14 and C15=C16 double bonds were mutually cis oriented, as was observed in 7 [3]. …”

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confidence: 66%

“…The C14=O14 carbonyl was also situated parallel to the plane of C11, N12, C13, and C14 in N-crotonylcytisine (7), N-betamorpholinepropionylcytisine [3], and in other cytisine derivatives [4]. This shows that formation of the conjugated system is favored.…”

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confidence: 78%

“…On the other hand, the chiral 3,7-diazobicyclo[3.3.1]nonane skeleton is interesting for studying structural features of substituted cytisines [3][4][5][6]. Until now, a large number of cytisine derivatives with various groups on the N atom have been synthesized [7][8][9][10][11][12], including acryloyl groups [13], thiazoles, benzthiazoles [11], and 1,2,4-thiadiazole groups [12].…”

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confidence: 99%

“…The reaction with acetic anhydride occurred with an excess of it. Acylation by the acid chlorides occurred in anhydrous toluene under reflux: R = -ÑH 3 (2); -Ñ 6 H 5 (3); -Ñ 6 H 4 -Br-o (4); -C 6 H 4 -NO 2 -n (5); -CH=CH-C 6 H 5 (6); -CH=CH-CH 3 (7) Acylation of 1 by acid chlorides was carried out without a HCl acceptor. Atom N12 of ring C played this role.…”

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Structural features of N-acylcytisines

et al. 2009

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747.945+547.79+548.737 G. Genzhemuratova, M. G. Levkovich, and Kh. M. ShakhidoyatovN-Acyl cytisine derivatives were synthesized by acylation with acetic anhydride; benzoyl and o-bromo-and p-nitrobenzoyl chlorides; and crotonyl and cinnamoyl chlorides. The structures of the synthesized compounds were studied using IR, PMR, and x-ray structure analysis (XSA). PMR spectra of the N-acylcytisines in solution typically had two rotational isomers around the N12-CO bond. Conformational analysis was performed using XSA for the position of the acyl group relative to the cytisine core. Bond lengths and angles of the acyl groups involved in the conjugation were analyzed.The broad spectrum of biological activity of cytisine (1) and its derivatives [1, 2] makes them a promising class for practical application. On the other hand, the chiral 3,7-diazobicyclo[3.3.1]nonane skeleton is interesting for studying structural features of substituted cytisines [3][4][5][6]. Until now, a large number of cytisine derivatives with various groups on the N atom have been synthesized [7][8][9][10][11][12], including acryloyl groups [13], thiazoles, benzthiazoles [11], and 1,2,4-thiadiazole groups [12]. In continuation of our research on transformations of 1 [11,12] and in order to find biologically active compounds in this series, we synthesized acyl derivatives via acylation of 1 with acetic anhydride and acid chlorides. The acylating agents were acetic anhydride; benzoyl-and o-bromo-and p-nitrobenzoyl chlorides; and crotonyl and cinnamoyl chlorides. The reaction with acetic anhydride occurred with an excess of it. Acylation by the acid chlorides occurred in anhydrous toluene under reflux: R = -ÑH 3 (2); -Ñ 6 H 5 (3); -Ñ 6 H 4 -Br-o (4); -C 6 H 4 -NO 2 -n (5); -CH=CH-C 6 H 5 (6); -CH=CH-CH 3 (7) Acylation of 1 by acid chlorides was carried out without a HCl acceptor. Atom N12 of ring C played this role. Structures of 2-7 were confirmed by IR and PMR spectra and by an x-ray structure analysis (XSA) for N-o-bromobenzoylcytisine (4), N-p-nitrobenzoylcytisine (5), and N-crotonylcytisine (6).IR spectra contained absorption bands at 1643-1653 cm -1 (ν CO ) and 1634-1647 (ν CO ). The physicochemical properties of 2, 3, and 7 agreed with those published. PMR spectra of the N-acylcytisines in solution characteristically showed several rotational isomers around the N12-CO and CO-R bonds. They could produce spectra of several conformers or simply give very broad spectral lines because the barriers to rotation were small. In several instances resonances could not be unambiguously assigned.

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confidence: 66%

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confidence: 78%

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Structural features of N-acylcytisines

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“…Taking into account experimental uncertainty, the bond lengths and angles in the cytisine moiety deviate insignificantly from the literature values published for cytisine and its derivatives [11][12][13][14]. The cytisine moiety adopts the chair-chair conformation with an equatorial substituent on N-12.…”

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confidence: 73%