Tetrahydrocyclopenta[e]pyrido[3,2-b][1,4]diazepine and -cyclopenta[e]pyrido[2,3-b][1,4]diazepine derivatives

In pursuing the study on compounds obtained by condensation of N-monoalkylated aromatic and hetero-aromatic diamines with α- and β-ketoesters, 7,8,9,10-tetrahydrocyclopenta[e]pyrido[3,2-b][1,4]diazepin-6(5H)-ones 4a, 4b and 5,7,8,10-tetrahydrocyclopenta[e]pyrido[2,3,-b][l,4]diazepin-9H)-ones 5a, 5b were prepared starting from 2,3-diaminopyridine or 2,3-diamino-5-chloropyridine and ethyl 2-oxo-cyclopentanecarboxylate. Compounds 4a,b and 5a,b suffer thermally induced ring contraction to the imidazolone derivatives 8a,b and 7a,b respectively and are unsuitable for preparing diazepinone derivatives. Thus the methylated diazepinones 15, 17 and 18 , stable on heating, were prepared. Compound 17 was transformed into the clozapine analogue 22 , through the diazepinthione 20 and its S-methyl derivative 21 .     

Synthesis of novel,substituted 4H-imidazo[1,5-a][1,4]benzodiazepines

Synthetic approaches to novel, substituted 4H-imidazo[1,5-a][1,4]benzodiazepines are described. The compounds prepared are, in general, derivatives of known ring systems and structures were assigned on the basis of spectroscopic evidence.     

Facile synthesis of some novel pyrido[3',2':4,5]thieno[2,3-b][1,4]thiazine-8-carboxylic acids

Model tetrahydropyrido[3',2':4,5]thieno[2,3-b][1,4]thiazines 9a-c were synthesized via reductive lactamization, using sodium dithionite, of the respective 2-[(carboxyalkyl)thio]-3-nitro-4,7-dihydrothieno[2,3-b]pyridine-5-carboxylic acids 7a-c. The latter derivatives were made via interaction of 2-chloro-7-cyclopropyl-3-nitro-4,7-dihydrothieno[2,3-b]pyridine-5-carboxylic acid (6) with each of alpha-mercaptoacetic, alpha-mercaptopropionic, and alpha-mercaptosuccinic acids and triethylamine in aqueous acetone at room temperature. The structures of 7a-7c and 9a-9c are supported by microanalytical and spectral (IR, MS, NMR) data. Compounds 9a and 9c showed potent inhibitory activity against the IGROV1 (Ovarian Cancer) cell line.     

Synthesis of tricyclic 4-chloro-pyrimido[4,5-b][1,4]benzodiazepines

[reaction: see text] A novel methodology was developed for the efficient synthesis of 4-chloro-pyrimido[4,5-b][1,4]benzodiazepines. The key is the intramolecular Friedel-Crafts cyclization of 5-amino-4-(N-substituted)anilino-6-chloropyrimidine with either a carboxylic acid or its derivatives to construct the 4-chloro-pyrimido[4,5-b][1,4]benzodiazepine core. Subsequent nucleophilic substitution allows the introduction of one more diversity point in the target molecules. This strategy provides an efficient method to access a library of compounds based on privileged substructures that are of great interest in drug discovery.     

Synthesis of novel imidazo[1,2-a][3,1]benzothiazines 4, imidazo[1,2-a]-[1,2,4]benzotriazines 5, and 4H-imidazo[2,3-c]pyrido[2,3-e][1,4]oxazines 6

Starting from the readily available 2-aminobenzhydrols ( 7 ), 3-amino-1,2,4-benzotriazine ( 11 ) and 2-amino-3-pyridinol ( 12 ), novel derivatives of 5-phenyl-5H-imidazo[1,2-a][3,1]benzothiazine-2-carboxylic acid, ethyl ester ( 4 ), imidazo[2,1-c][1,2,4]benzotriazine-2-carboxylic acid, ethyl ester ( 5 ) and 4H-imidazo[2,3-c]pyrido-[2,3-e][1,4]oxazine ( 6 ) were prepared.     

The Synthesis of pyrimido[4,5-b][1,4]diazocines and pyrido[2,3-b][1,4]diazoeines

The reaction conditions for the preparation of 7H,8H-1,3-dimethyl-2,4,6,9-tetraoxopyrimidino[4,5-b][1,4]-diazocine ( 9 ), 1,3-dimethy 1–2,4,6,11-tetraoxobenzo[f]pyrimidino[4,5-b][1,4]diazocine ( 10 ), 7H,8H-1,3-dimethyl-2,4,6,10-tetraoxopyrimidino[4,5-b][1,4]diazonine ( 16 ), and 7H,8H-6,9-dioxopyridino[2,3-b][1,4]diazocine ( 19 ) were determined. The mechanism of the formation of these compounds was established. The scope of these reactions was found to be general for eight and nine ring formation from 2,3-diamino-N-heterocycles.     

First synthesis of 4H-furo[3,2-f]pyrrolo[1,2-a][1,4]diazepines

The synthetic pathway leading to 4-H-furo[3,2-f]pyrrolo[1,2-a][1,4]diazepines is described in five steps starting from 2-hydroxyketones via 2-amino-3-furonitriles.     

2′,5′-二氢-1′H-吡咯骈[3′,4′:1,2]][60]富勒烯衍生物的合成

以甘氨酸乙酯盐酸盐与取代的苯甲醛为原料,制得了一系列亚胺,然后用亚胺与C(60)反应,得到带有不同取代基的吡咯烷骈[60]富勒烯衍生物.经~1H NMR,~(13)C NMR,FT-IR,UV-vis以及TOF-SIMS等方法对所得化合物结构进行了表征,并进行了产物的生物活性测试.     

2',5'-二氢-1'H-吡咯骈[3',4':1,2][60]富勒烯衍生物的合成

以甘氨酸乙酯盐酸与取代的苯甲醛为原料,制得了一系列亚胺,然后用亚胺与C~6~0反应,得到带有不同取代基的吡咯烷骈[60]富勒烯衍生物.经^1HNMR,^1^3CNMR,FT-IR,UV-vis以及TOF-SMS等方法对所得化合物结构进行了表征,并进行了产物的生物活性测试。     

Synthesis of thiopyrano[4″,3″:4′,5′]pyrido[3′,2′:4,5]furo[3,2-d]pyrimidines

<正>Reactions of the 6-hydroxy-thiopyrano[3,4-c]pyridine-5-carbonitrile derivative 1 withα-halo-carbonyl compounds gave the ortho-substituted intermediates 2a-c which were converted into furo[2,3-b]thiopyrano[4,3-d]pyridines 3a-c by fusion of a furan moiety under basic conditions.Further cyclization of 3a-c led to a fusion of a pyrimidine ring,yielding the tetracyclic products 6,7 and 8.In addition,condensation of 6 with various aromatic aldehydes afforded the corresponding imines 9a,b.Mannich reaction of 7 gave products 10a,b.     

Synthesis of 1,4-benzodiazepino[4,5-d][1,4]benzoxazepines

The novel 1,4-benzodiazepino[4,5-d][1,4]benzoxazepine ring system has been constructed via preformed benzoxazepine intermediates. Several derivatives have been prepared as potential anxiolytic agents.     

The synthesis of 4H-imidazo[5,1-c][1,4]benzothiazine derivatives

A facile synthesis of the 4H-imidazo[5,1-c][1,4]benzothiazine ring system is described. The synthesis utilized the annulation of an imidazole ring onto a 2H-1,4-benzothiazin-3(4H)-one via the addition of the anion of ethyl isocyanoacetate. Methods for the functionalization of the 1-, 3-, 4-, and 5-positions of the ring system are presented.     

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.     

Synthesis of 5,6-dihydro-4H-pyrrolo[1,2-a]thieno[2,3-f][1,4]diazepines

The reduction of 1-[3-(thienyl-2-carbonitrile)]pyrrole, formed by condensation of 3-aminothiophene-2-carbonitrile with 2,5-dimethoxytetrahydrofuran, gave 1-[3-(thienyl-2-aminomethyl)]pyrrole. This compound was found to be a convenient intermediate for the preparation of 4-aryl-5,6-dihydro-4H-pyrrolo[1,2-a]thieno-[2,3-f][1,4]diazepines which was accomplished by two different synthetic routes.     

Synthesis of novel imidazo[1,2-a]pyrrolo[2,1-c][1,4]benzodiazepines and pyrimido[1,2-a]pyrrolo[2,1-c][1,4]benzodiazepines

Several 1 1-amino-5H-pyrrolo[2,1-c][1,4]benzodiazepines have been used as starting material to prepare a number of derivatives of 9H-imidazo[1,2-a]pyrrolo[2,1-c][1,4]benzodiazepines and 10H-pyrimido[1,2-a]pyrrolo[2,1-c][1,4]benzodiazepines. The imidazole nucleus was built by reaction of amidines with ethyl bromopyruvate or aminoacetaldehyde dimethylacetal. Several derivatives of imidazo[1,2-a]pyrrolo[2,1-c][1,4]benzodiazepine have been prepared by formylation of the pyrrole ring followed by formation of thioamides. Condensation of 11-amino-5H-pyrrolo[2,1-c][1,4]benzodiazepines with diethyl ethoxymethylenemalonate afforded intermediate diesters which were transformed into the corresponding 10H-pyrimido[1,2-a]pyrrolo[2,1-c]-benzodiazepines.     

Triphenylantimony(V) Catecholates Based on o-Quinones,Derivatives of Benzo[b][1,4]-Dioxines and Benzo[b][1,4]-Dioxepines

Russian Journal of Coordination Chemistry - New catecholate complexes of triphenylantimony(V), (Etgly-3,6-DBCat)SbPh3 (I), (Propgly-3,6-DBCat)SbPh3 (II), and (Cat-3,6-DBCat)SbPh3 (III), based on...