A facile synthesis of 2,4,8,10-tetrahalo-6,12-diaryldibenzo[b,f][1,5]diazocines

3,5-Dihalo-2-aminobenzophenones 2 on prolonged reflux in dry pyridine gave 2,4,8,10-tetrahalo-6,12- diaryldibenzo[b,f][1,5]diazocines 3 in high yields. Attempted condensation of 2 with glycine ester hydrochloride under identical reaction conditions failed to afford 1,4-benzodiazepines.     

Distinct difference of chemical behaviors between 5H,7H-dibenzo[b,g][1,5]dithiocin 12-oxide and thiazocine S-oxide

5H, 7H-Diobenzo [b,g] [1,5] dithiocin 12-oxide (2) rearranged into 6-oxide (3) in the presence of CF₃CO₂H. The corresponding thiazocine S-oxide (5) was only protonated at the amino group under the same conditions. Furthermore, methylation of 2 afforded S-methylated product (7) in contrast to O-methylated product in 5.     

11-Substituted polyfluorodibenz[b,f][1,4]oxazepines

Tetrafluorodibenz[b,f][1,4]oxazepin-11-(10H)-ones have been synthesized and converted to 11-chloro and 11-piperidino substituted polyfluorodibenz[b,f][1,4]oxazepines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 539–542, April, 1989.     

A new synthesis of dibenzo[b,g][1,5]naphthyridine-6,12(5H,1H)dione (epindolidione)

A new convenient synthesis of dibenzo[b,g][1,5]naphthyridine-6,12(5H,11H)dione starting from N-phenylglycine ethyl ester is described. Ester condensation of N-phenylglycine ethyl ester with diethyl oxalate followed by reaction with aniline under acid catalysis gave a mixture of diethyl dianilinomaleate and diethyl dianilinofumarate in 54% yield. Upon heating this mixture in a high-boiling inert solvent, 3-anilino-2-ethoxycarbonyl-4-quinolone was obtained in 72% yield. Final ring closure of the quinolone derivative using polyphosphoric acid gave the epindolidione.     

A rapid and efficient access to diaryldibenzo[b,f][1,5]diazocines

2-Benzoylbenzoyl azides undergo facile cyclization under acidic conditions to give substituted dibenzo[b,f][1,5]-diazocines in good yields. This approach shortens the synthetic steps toward these compounds as compared with conventional methods. The mechanism of the diazocine synthesis is assumed to proceed by an unprecedented intermolecular [2 + 2] cyclization.     

Eight-membered heterocycles. 12H-dibenzo[d,g][1,3,2]dioxaphosphocin and 12H-dibenzo[d,g][1,3,2]dioxaborocin derivatives

The synthesis of phosphonite and thiophosphite derivatives of the 12H-dibenzo[d,g][1,3,2]dioxaphosphocin ring system is described. The 'H nmr shows evidence for long-range coupling of the C-12 methine proton to phosphorus. The ¹H nmr of the 12H-dibenzo[d,g][1,3,2]dioxaborocin ring system is compared to that of the phosphorus analog. The nmr spectral data suggest that the phosphorus and boron containing ring systems have similar ring conformations.     

Novel polycyclic heterocycles. IX. Dibenz[b,f] [1,4]oxazocin-11 (12H)one, 6,11-dihydro-12H-dibenz[b,f] [1,4]oxazocine,and their derivatives

Dibenz[b,f][1,4]oxazocin-11 (12H)one, 14 , was synthesized by the dicyclohexylcarbodiimide induced cyclization of α-(o-aminophenoxy)-o-toluic acid ( 13 ). Reduction of 14 by lithium aluminum hydride gave 6,11-dihydro-12H-dibenz[b,f][1,4]oxazocine ( 16 ). Both 14 and 16 were converted to a series of 12-alkylated and -acylated derivatives. The pmr spectra of some of these compounds are discussed.     

新型非对称二苯并[b,f][1,5]二氮杂环辛四烯的合成

以两种不同取代的2-氨基二苯甲酮为原料,氯苯为溶剂,BF3-Et2O为脱水剂,通过分子间脱水一步环化缩合制备非对称二苯并[b,f][1,5]二氮杂环辛四烯衍生物。运用HPLC监控反应过程,优化合成工艺,得到最佳反应条件为:等物质的量的两种不同取代2-氨基二苯甲酮和BF3-Et2O,在氯苯中回流反应12 h。化合物4a^4c为新化合物,其结构经1H NMR,13C NMR和MS(ESI)表征。     

Synthesis of 4,5-dihydropyrrolo[1,2,3-e,f][1,5]benzodiazepin-6(7H)-ones

A number (seven compounds) of 4,5-dihydropyrrolo[1,2,3-e, f][1,5]benzodiazepin-6(7H)-ones were obtained by condensation of 7-aminoindoles with -halopropionic acid derivatives with subsequent cyclization of the resulting 7-(-halopropionylamino)indoles by heating in the presence of bases in dimethylformamide. The compositions and structures of the intermediates and final products were confirmed by the results of elementary analysis and data from the IR, UV, and mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 505–507, April, 1981.     

Novel polycyclic heterocycles. VIII. 6,11-dihydro-12H-dibenzo[b,f] [1,4]thiazocines and their derivatives

6,11-Dihydro-12H-dibenzo[b,f][1,4]thiazocine, 4 , and its 2-chloro, 7 , and 2-(trifluoromethyl)-, 1 , derivatives, were prepared by the reaction of an o-aminobenzenethiol and α,α-dibromo-o-xylene. Acylation and alkylation at position-12 gave a series of ω-haloacyl-, ω-amino-acyl, and ω-aminoalkyl derivatives of these heterocycles. The conformations, proton magnetic resonance spectra, and x-ray crystallographic studies of these compounds are discussed.     

Synthesis of some benzo[b][1,8] and [1,5]naphthyridines

A series of carboxylic acid derivatives of the title compounds have been prepared as precursors of potential anti-tumor compounds, by annulation of 2-methylcyclohexanone to the appropriate aminopyridinecarboxaldehyde followed by aromatization and oxidation of the methyl group.     

二苯并[b,f][1,5]二氮杂芳辛四烯衍生物的合成及拆分

以邻氨基二苯甲酮为原料,经自身缩合环化合成了3种二苯并[1,5]二氮杂芳辛四烯衍生物(1a~1c);以邻苯二甲酸酐和溴苯为原料经傅-克反应制得中间体2-(4-溴苯甲酰溴)苯甲酸(M1);M1经叠氮化后自缩合制得6,12-二(4-溴苯基)二苯并[b,f][1,5]二氮杂环辛四烯(1d);以邻氨基苯甲酸甲酯为原料,经自身缩合环化制得中间体二苯并[b,f][1,5]二氮杂环辛四烯-6,12(5H,11H)-二酮(M2);M2经氯化合成6,12-二氯二苯并[b,f][1,5]二氮杂环辛四烯(1e),化合物1a~1e的结构经~1H NMR,~(13)C NMR和ESI-MS表征,其中化合物1c为新化合物。利用超临界色谱(SFC)技术对化合物1a~1e实现了手性拆分,获得5对具有高旋光度的光学活性异构体(ee99%)。