Heterogeneous catalytic synthesis and structure of 5,5a,10a,11-tetrahydro-10H-indeno[1,2-b]quinoline

Hydrogenation of 10H-indeno[1,2-b]quinoline in benzene in the presence of R₂S₇ gave 5,5a,10a,11-tetrahydro-10H-indeno[1,2-b]quinoline, the structure of which was established by mass-, IR, UV,¹³C, and¹H NMR spectra. Thecis fusion of the indan and tetrahydroquinoline fragments, the axial orientation of the proton at C(5a), and the equatorial orientation of the proton at C(10a) were confirmed by molecular mechanics calculations using the PC MODEL program.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1098–1101, June, 1994.     

Formylation of Furyl-substituted Imidazo[1,2-a]pyridine, Imidazo[1,2-a]pyrimidine and Imidazo[2,1-b]thiazole

Vilsmeier formylation of 2-(2-furyl)-substituted imidazo[1,2-a]pyridine and imidazo[1,2-a]pyrimidine, and also 6-(2-furyl)imidazo[2,1-b]thiazole with 1 mole of reagent occurs at the free position of the imidazole ring, while with an excess of the reagent it also occurs at the position 5 of the furyl group.     

Spatial Configuration of Derivatives of 5,5a,6,7-Tetrahydropyrido[1,2-a]benzimidazole and 6,7-Dihydro-5aH-pyrido[1,2-b]benzoxazole

The spatial configurations of 7,9-diphenyl-5a,6-tetramethylene-5,5a,6,7-tetrahydropyrido[1,2-a]benzimidazole and 7,9-diphenyl-5a,6-tetramethylene-2,5a,6,7-tetrahydropyrido[1,2-a]benzimidazol-2-one have been established by X-ray crystallography. Analogous configurations are proposed for a series of other derivatives of 5,5a,6,7-tetrahydropyrido[1,2-a]benzimidazoles and some derivatives of 6,7-dihydro-5aH-pyrido[1,2-b]benzoxazoles on the basis of ¹H NMR spectroscopic data and the results of quantum chemical calculations using the MNDO, AM1, and PM3 methods.     

微波辐射下一锅法合成2-氨基-6-溴-4-芳基-5H-茚并[1,2-b]吡啶-3-腈衍生物

以芳香醛、4-溴茚酮、丙二腈和醋酸铵为原料,分别用微波辐射和传统加热法,一步法合成7种未见文献报道的2-氨基-6-溴基-4-芳基-5H-茚并[1,2-b]吡啶-3-腈衍生物.对比两种方法,在常压下微波具有反应时间短、产率较高等特点.所有化合物均经IR,1HNMR和元素分析确定.     

Bromination of Substituted 5H-Imidazo[1,2-b]-1,2,4-triazepin-4-ones and -thiones

The reactions of substituted 5H-imidazo[1,2-b]-1,2,4-triazepin-4-ones and -thiones with bromine and N-bromosuccinimide have been studied. Derivatives of 3- and 8-bromo-, 3,8-dibromoimidazo[1,2-b]-1,2,4-triazepine and 5H-2-bromomethyl-3-methyl-7,8-diphenylimidazo[1,2-b]-1,2,4-triazepin-4-one are formed, depending on the degree of substitution, the nature of the brominating agent, and the reaction conditions.     

Condensed Isoquinolines. 17. Enamine Properties of Benzimidazo[1,2-b]isoquinolin-11(5H)-one in Alkylation Reactions

The alkylation of benzimidazo[1,2-b]isoquinolin-11(5H)-one has been studied. This occurs at N₍₅₎ or C₍₆₎ depending on the type of alkylating agent and the reaction conditions. It was shown that C₍₆₎ alkylation is effected in reactions with reactive alkyl halides. A repeat alkylation occurs preferentially at the same position. Interaction with o-xylylidene dibromide leads to spiro[benzimidazo[1,2-b]-isoquinolin-6,2'-indan]-11-one and 1,6-dihydro-11H-6a,11b-diazobenzo[b]benzo[5,6]cyclohepta[1,2,3-l,m]fluoren-11-one, which are derivatives of new heterocyclic systems.     

Photochromic dihetarylethenes. 6. Photochromic derivatives of thieno[3,2-b]thiophene

1,2-Bis{5-(2-benzothiazolyl)-2-methyl-6-trifluoromethylthieno[3,2-b]thiophen-3-yl}hexafluorocyclopentene possessing high fatigue resistance was synthesized for the first time. Its photochromic and fluorescence properties were studied. The structure of its cyclic form was established by X-ray diffraction analysis.     

Hetero-Diels-Alder reaction of some 1,3-diaza-1,3-butadienes with ketenes. Synthesis of functionalized pyrimido[1,2-b]-benzothiazoles and 1,3,4-thiadiazolo-[3,2-a]pyrimidines

Summary Reaction of 1,3-diaza-1,3-butadienes (1a–c) with various ketenes and chloroketenes results in the formation of substituted 4-oxo-pyrimido[2,1-b]benzothiazoles (4a–d) and 1,3,4-thiadiazolo[3,2-a]pyrimido-4-ones (4e,f). Reaction of 1,3-diaza-1,3-butadienes1d,e with ketenes and chloroketenes leads to the 2-morpholine-substituted compounds7 and15, respectively. All reactions proceedvia formation of [4+2] cycloadducts that eliminate methylthiol, methylsulfenyl chloride, or morpholine.

---

Hetero-Diels-Alder-Reaktion einiger 1,3-Diaza-1,3-butadiene mit Ketenen. Synthese funktionalisierter Pyrimido[1,2-b]benzothiazole und 1,3,4-Thiadiazolo[3,2-a]pyrimidine

Zusammenfassung Die Reaktion der 1,3-Diaza-1,3-butadiene1a–c mit verschiedenen Ketenen und Chlorketenen führt zu substituierten 4-Oxo-pyrimido[2,1-b]benzothiazolen (4a–d) und 1,3,4-Thiadiazolo[3,2-a]pyrimido-4-onen(4e,f). Die 1,3-Diaza-1,3-butadiene1d,e ergeben mit Ketenen und Chlorketenen die 2-Morpholin-substituierten Verbindungen7 und15. Alle Reaktionen verlaufen über [4+2]-Cycloaddukte, die Methylthiol, Methylsulfenylchlorid oder Morpholin eliminieren.

     

Synthesis and Properties of 6-Amino-7-hetaryl-5-R-5H-pyrrolo[2,3-b]pyrazine-2,3-dicarbonitriles

We have established that when 5-chloro-6-[cyano(2,3-dihydro-1-R-benzo[d]azol-2-yl)methyl]-2,3-pyrazinedicarbonitriles are reacted with nucleophilic reagents (aliphatic and aromatic amines, hydrogen sulfide), annelation of the five-membered ring occurs on the [b] face of the pyrazine with formation of 6-amino-7-hetaryl-5-R-5H-pyrrolo[2,3-b]pyrazine-2,3-dicarbonitriles and 6-amino-7-(1H-benzo[d]imidazol-2-yl)thieno[2,3-b]pyrazine-2,3-dicarbonitrile respectively. Further heating with excess of acylating reagent leads to formation of a novel heterocyclic system 1H-benzo[4,5]imidazo[1,2-c]pyrazino[2',3':4,5]pyrrolo[3,2-e]pyrimidine. Reaction of vicinal dinitriles with hydrazine hydrate leads to the novel system 1H-pyrrolo[2',3':5,6]pyrazino[2,3-d]pyridazine.     

Dipyrrolo[1,2-a;2',1'-c]pyrazines. 6. Electrophilic Substitution in a Series of Dipyrrolo[1,2-a;2',1'-c]pyrazine and 5,6-Dihydrodipyrrolo[1,2-a;2',1'-c]pyrazine Derivatives. Phosphorylation of Dipyrrolo[1,2-a;2',1'-c]pyrazines

We have studied the behavior of asymmetrically substituted dipyrrolo[1,2-a;2',1'-c]pyrazines and their 5,6-dihydro analogs under phosphorylation reaction conditions.     

Condensed Isoquinolines. 16. Enamine Properties of Benzo[4,5]imidazo[1,2-b]isoquinolin-11(5H)-one in Terms of Its Acylation Reactions

A study has shown that the acylation of benzo[4,5]imidazol[1,2-b]isoquinolin-11(5H)-one occurs at N₍₅₎ or at C₍₆₎ depending on the nature of the acylating reagent and the reaction conditions. It was found that principally C-acylation takes place in the absence of base. The reaction with -halo-substituted carboxylic acid chlorides leads to the formation of C-acylated products which are converted to derivatives of the novel heterocyclic system 7H-2a,6b-diazabenzo[b]cyclopenta[l,m]fluorene-1,7(2H)-dione in the presence of base.     

Pyrido[2,3-d]pyrimidines,II. One step synthesis of pyrido[2,3-d]pyrimidines and pyrimido[4,5-b]quinolines from 6-amino uracils

Summary Reduction of 6-azidouracils2 with hydrogen palladium or sodium dithionite afforded the corresponding 6-aminouracils5 which could also be obtained by reaction of2 with triphenylphosphanevia phosphazenes and subsequent hydrolysis (Staudinger reaction). The use of trimethylphosphite instead of phosphanes yields with2b the expected trimethoxyphosphazene3c, whereas2a reacts to the phosphonoaminopyrimidine4. The syntheses of 5-hydroxy pyrido[2,3-d]pryimidine-2,4,7-triones6, pyrido[2,3-d]pyrimidine-2,4,5-triones8, cyclopenta[e]pyrido[2,3-d]pyrimidin-2,4,5-triones7a,c, and tetrahydro-pyrimido[4,5-b]quinolin-2,4,5-triones7b,d by condensation of 6-aminouracils5 with malonates, ethylaceto/benzoylacetate, ethyl 2-oxocyclopentanecarboxylate and ethyl 2-oxocyclohexanecarboxylate, respectively, are described.

---

Pyrido[2,3-d]pyrimidine, 2. Mitt. Einstufige Synthese von Pyrido[2,3-d]pyrimidinen und Pyrimido[4,5-b]chinolinen aus 6-Aminouracilen

Zusammenfassung Reduktion der 6-Azidouracile2 mit Wasserstoff/Palladium oder Natriumdithionit ergibt die entsprechenden 6-Aminouracile5, die auch durch Reaktion von2 mit Triphenylphosphin und anschließende Hydrolyse erhalten werden können (Staudinger-Reaktion). Die Verwendung von Trimethylphosphit anstelle von von Trimethylphosphin ergibt mit2b das erwartete Trimethoxyphosphazin3c, während2a zum Phosphonoaminopyrimidin4 reagiert. Die Synthesen der 5-Hydroxy-pyrido[2,3-d]pyrimidin-2,4,7-trione6, der Pyrido[2,3-d]pyrimidin-2,4,5-trione8, der Cyclopenta[e]pyrido[2,3-d]pyrimidin-2,4,5-trione7a,c und der Tetrahydro-pyrimido[4,5-b]chinolin-2,4,5-trione7b,d durch Kondensation der 6-Aminouracile5 mit Malonat, Acetat, Ethyl-2-oxocyclopentancarboxylat und Ethylcyclohexancarboxylat werden beschrieben.

     

Synthesis and X-ray diffraction studies of 3-cyano-2-trifluoromethyl-4H-pyrido[1,2-a]pyrimidine derivatives

Reactions of 2-chloro-1-cyano-2-trifluoromethylethylenes with 2-aminopyridines were studied. According to the data of NMR spectroscopy and X-ray diffraction analysis, the first stage of the reaction involves alkenylation of the exocyclic nitrogen atom of 2-aminopyridines followed by formation of pyrido[1,2-a]pyrimidines. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1261–1264, July, 2000.     

Addition compounds of nucleophiles and 3-ethylthio-6-oxo-6H-1,2-dithiolo[4,3-c]1,2-dithiolium tetrafluoroborate. Synthesis of 3H,6H-1,2-dithiolo[4,3-c]1,2-dithiole-3-one-6-thione

Summary A smooth method of synthesizing 3H, 6H-1,2-dithiolo[4,3-c]1,2-dithiole-3,6-dithione (3), and also its partial desulfuration to yield 3H, 6H-1,2-dithiolo[4,3-c]1,2-dithiole-3-one-6-thione (4) is presented. The ethylation product5 of the monothione4 reacts with various nucleophilic reagents to form remarkably stable adducts. The adducts of5 with methanol,tert-butyl mercaptan, and with aniline could be isolated and characterized by their¹H-NMR spectra.

---

Anlagerungsverbindungen von Nukleophilen an 3-Ethylthio-6-oxo-6H-1,2-dithiolo[4,3-c]1,2-dithioliumtetrafluoroborat. Synthese von 3H,6H-1,2-Dithiolo[4,3-c]1,2-dithiol-3-on-6-thion

Zusammenfassung Eine glatte Synthese für 3H,6H-1,2-Dithiolo[4,3-c]1,2-dithiol-3,6-dithion (3) und für dessen partielle Entschwefelung zu 3H,6H-1,2-Dithiolo[4,3-c]1,2-dithiol-3-on-6-thion (4) wird angegeben. Das Ethylierungsprodukt5 des Monothions4 reagiert mit unterschiedlichen Nukleophilen zu bemerkenswert stabilen Addukten. Die Addukte mit Methanol,tert.-Butylmercaptan und mit Anilin wurden isoliert und durch ihr¹H-NMR-Spektrum charakterisiert.

     

Synthesis of 12-aryl-1-oxo-1,2,3,4,5,12-hexahydroindolo-[2,1-b]quinazoline-6-carbonitriles by recyclization of 11-aryl-1-oxo-2,3,4,5,10b,11-hexahydro-1H-indolo[2,3-b]quinoline-10b-carbonitriles

A general and convenient method for the synthesis of 12-aryl-1-oxo-1,2,3,4,5,12-hexahydroindolo[2,1-b]quinazoline-6-carbonitriles was proposed. The method is based on the recyclization of 11-aryl-1-oxo-2,3,4,5,10b,11-hexahydro-1H-indolo[2,3-b]quinoline-10b-carbonitriles. The structure of 12-(3-methoxyphenyl)-8-methyl-1-oxo-1,2,3,4,5,12-hexahydroindolo[2,1-b]quinazoline-6-carbonitrile was studied by X-ray diffraction analysis.     

Synthesis of 3-amino-4-methyl-6-trifluoromethylthieno[2,3-b]pyridine-2-carboxanilide and its crystal and molecular structure

4-Methoxy-1,1,1-trifluoropent-3-en-2-one reacts with cyanothioacetamide to give 3-cyano-4-methyl-6-trifluoromethylpyridine-2(1H)-thione, which was transformed into 3-amino-4-methyl-6-trifluoromethylthieno[2,3-b]pyridine-2-carboxanilide by the reaction with chloroacetanilide. The crystal and molecular structure of the amide obtained was studied by X-ray analysis. Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 4, pp. 701–703, April, 1998.     

Pyrrolocoumarins. 1. Synthesis and Spectroscopic Investigation of 7-Oxo- and 1,2,7-Trioxo-1,2-dihydropyrano-[3,2-e]indole and Their Derivatives

A preparative route is proposed for the synthesis of the novel heterocyclic systems 7-oxo- and 1,2,7-trioxo-1,2-dihydropyrano[3,2-e]indole using classical Fischer and Sandmeyer methods respectively. We have studied various conditions for cyclization of the starting coumarin 6-isonitrosoacetamide and the methyl or ethyl pyruvate 6-coumarinylhydrazones. The syn- and anti-form ratio of the latter and the structure of all of the synthesized compounds were determined using spectroscopic data analysis.Dedicated to the memory of a dear teacher, the prominent Russian science professor Nikolai Nikolaevich Suvorov. Founder of indole chemistry in Georgia. In love with, and a warm favourite of, Georgia.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 238–245, February, 2005.     

Investigation of Nitrogen- and Sulfur-containing Heterocycles. 53. Reactions of 5-Amino-6-mercaptopyrimidines with Derivatives of p-Chloronitrobenzene. Synthesis of a New Heterocyclic System - Pyrimido[4,5-b]-1,4-benzothiazepine

A series of pyrimidyl aryl sulfides was obtained from the reaction of 5-amino-6-mercaptopyrimidines with derivatives of p-chloronitrobenzene containing carbonyl functional groups. The properties of these sulfides and methods of their cyclization into derivatives of a new tricylic system, pyrimido[4,5-b]-1,4-benzothiazepine, were studied.     

Synthesis of 5H-thiazolo[3,2-a]pyrimidine derivatives from 6-methyl-2-thiouracil and 1-acyl-2-bromoacetylenes. X-ray structural study of 3-benzoyl-7-methyl-5H-thiazolo[3,2-a]pyrimidin-5-one

3-Acyl-7-methyl-5H-thiazolo[3,2-a]pyrimidin-5-ones were synthesized by the reaction of 1-acyl-2-bromoacetylenes with 6-methyl-2-thiouracil, carried out with heating in DMF, dioxane, or acetonitrile in the presence of triethylamine. The structure of 3-benzoyl-7-methyl-5H-thiazolo[3,2-a]pyrimidin-5-one was established by X-ray structural analysis.Deceased in 1995.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2306–2308, September, 1996.     

Synthesis of annelated derivatives of tetrafluoro-10<Emphasis Type="Italic">H</Emphasis>-imidazo[1,2-<Emphasis Type="Italic">b</Emphasis>][1,2]benzooxazin-10-one and 2-pentafluorophenylpyrazine 1,4-dioxide by condensation of alicyclic 2-hydroxyamino oximes with pentafluorophenylglyoxal

Reactions of alicyclic 2-hydroxyamino oximes with pentafluorophenylglyoxal afford mixtures of annelated derivatives of 2-pentafluorophenylpyrazine 1,4-dioxide and tetrafluoro- 10H-imidazo[1,2-b][1,2]benzooxazin-10-one. The structures of the latter were established by X-ray diffraction analysis.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1636–1639, August, 2004.