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Solid-phase syntheses of 1,3,5-tri-substituted and 1,3,4,5-tetra-substituted 1,4-diazepin-2-ones 15-18 have been accomplished by employing inexpensive commercially available alpha- and beta-amino acids on Wang resin. Reductive amination of the imine formed by condensation of Wang aldehyde resin respectively with beta-alaninate 2 and beta-homophenylalaninate 3, followed by aminoacylation with a set of alpha-N-Boc amino acids (Phe epsilon-( Z)-Lys, and Leu) gave tertiary amide resins 7 and 8. Exposure of resins 7 and 8 to an excess of vinyl magnesium bromide in the presence of copper cyanide gave the corresponding gamma,delta-unsaturated ketone resins 9 and 10 by way of a cascade addition. Diazepinones were made by Boc deprotection and intramolecular reductive amination. To diversify the heterocycle, N-alkylation was performed using a series of alkyl halides. Alternatively, diazepinones 15e-g were obtained from treatment of methyl beta-alaninate resins 4 and 20 under similar copper-catalyzed cascade conditions to afford the gamma,delta-unsaturated ketone 21, which was acylated using alpha-N-Fmoc-amino acids (Phe, Trp, gamma-(t-Bu)-Glu). Formation of diazepinones 15 followed a similar protocol, after Fmoc removal with piperidine. Cleavage of the heterocycles with TFA/TES 95:5 gave the N1-p-hydroxybenzyl diazepinones 15-18 in overall isolated yields from 6 to 24% after purification in purities ranging from 81 to 100% according to LCMS analysis. 相似文献
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Six 1,3,5-trisubstituted 1,4-diazepin-2-ones were synthesized by a sequence featuring the cascade addition of vinyl Grignard to N-[Boc-aminoacyl]-N-alkyl-beta-amino esters, followed by Boc group removal and annulation by a reductive amination. Relative to the parent sequence employing N-Boc-aminoacyl beta-amino esters to make 3,5-disubstituted heterocycle, the additional N-alkyl substituent caused a noticeable acceleration and gave relatively higher yield in the 1,4-diazepin-2-one annulation. 相似文献
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The electroeducation of 1-methyl-5-o-chlorphenyl-7-ethyl-1,2-dihydro-3H-thieno[2,3-e],[1,4]-diazepin-2-one (Clotiazepam) is investigated by different polarographic techniques. The electrochemical reactioninvolves a 2-electron exchange in both acidic and alkaline media. The reduction process is irreversible and the current is diffusion-controlled. With differential pulse polarography, the linear response range is 6.5 × 10-7— 1.10 × 10?5 M, with a relative standard deviationof 1.2% at the 2.6 × 10?6 M level. The method is applied to the determinationof Clotiazepam in tablets after simple dissolution in 0.1 M sulphuric acid. 相似文献
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Attanasi OA De Crescentini L Favi G Mantellini F Nicolini S 《The Journal of organic chemistry》2011,76(20):8320-8328
A novel and simple one-pot synthesis of 3-substituted 2,5,6,7-tetrahydro-1H-1,4-diazepin-2-ones from 1,2-diaza-1,3-dienes (DDs) and N-unsubstituted aliphatic 1,3-diamines is described. Here we also report a procedure to selectively obtain alkyl 5H-1,4-benzodiazepine-3-carboxylates from the DDs and 2-aminobenzylamine. Both processes occur by means of sequential 1,4-conjugated addition followed by regioselective 7-exo cyclization. The behavior of N-methyl- and N,N'-dimethyl-1,3-diaminopropanes toward the DDs furnished pyrazol-3-ones and bis-α-aminohydrazones, respectively. 相似文献
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Nicolas Wlodarczyk 《Tetrahedron letters》2007,48(14):2583-2586
A new efficient access to 1,4-diazepane derivatives is described via a microwave assisted synthesis of 7-substituted-1,4-diazepin-5-ones, which proceeds rapidly in good yields. Catalytic reduction gave 1,4-diazepan-5-ones and 1,4-diazepanes whereas a ring opening was observed by hydride reduction when a phenyl group occupies the N-benzylic position. 相似文献
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A novel method for N-methylation of the cyclic amide in the 1,4-benzodiazepine ring system is presented. Methods traditionally used involve treatment of the 1,4-benzodiazepinone anion with an alkyl halide. It has been demonstrated that these derivatives can be methylated on the amide nitrogen atom by use of dimethyl-formamide dimethyl acetal which acts as both reagent and solvent for the reaction. 相似文献
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Prof. Dr. Otto Hromatka Dieter Binder Gottfried Pixner 《Monatshefte für Chemie / Chemical Monthly》1975,106(5):1103-1109
The preparation of 7-chloro-1,3-dihydro-5-phenyl-thieno-[3,2-e]-1,4-diazepin-2-one (8 a) and 7-chloro-5-(2-chlorophenyl)-1,3-dihydro-thieno[3,2-e]1,4-diazepin-2-one (8 b) as well as the methylation in position 1 are described. 相似文献
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Zusammenfassung Bei der Nitrierung von 7-Chlor-5-phenyl-1H-thieno[2,3-e]1,4-diazepin-2(3H)-on (1) wurde ein Produkt erhalten, dessen Struktur durch chemische Beweisführung bestimmt wurde.
The nitration of 7-chlor-5-phenyl-1H-thieno[2,3-e]1,4-diazepin-2(3H)-one
The said compound (1) yielded a product whose structure was determined by chemical methods.相似文献
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The preparation of 7-methoxycarbonyl-5-phenyl-1H-thieno[2,3-e]1,4-diazepin-2(3H)-one (8) and its 1-methyl-derivative (10) is described. Hydrolysation of these two products yielded neither of the two possible acids3 respectively13. 相似文献
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V. unji A. Lisini A. Sega T. Kova
F. Kajfe B. Ru
i 《Journal of heterocyclic chemistry》1979,16(4):757-761
7-Chloro-5-phenyl-d5-3(S)-methyldihydro-1,4-benzodiazepin-2-one ( 1a ) was synthesized and its conformation in solution determined using a computer assisted LIS-NMR method. It was found, with Fr(fod)-d27 as a shift reagent, that a lanthanide coordinates to a carbonyl oxygen at a 2.02 Å distance (bond angle 158.07°, torsional angle 39.53°), while the substrate 1a adopts an expected quasi-boat conformation with a C(3)-methyl group exposed in a quasi-equatorial position. 相似文献
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Fenster E Rayabarapu DK Zhang M Mukherjee S Hill D Neuenswander B Schoenen F Hanson PR Aubé J 《Journal of combinatorial chemistry》2008,10(2):230-234
The parallel synthesis of gamma-turn-inspired peptidomimetic libraries has been demonstrated through two approaches toward the preparation of 1,4-diazepin-5-ones. In the first approach, 1,4-diazepin-5-ones scaffolds were prepared on gram scale and subsequently diversified to produce libraries. In a second approach, libraries of 1,4-diazepin-5-ones were produced directly through a three-component strategy that maximizes the diversity obtained in a single step. 相似文献