Transformations of 2-Ethyl-2-methyl-2,3-dihydro-1H-indole at the 3-Position

Russian Journal of Organic Chemistry - The oxidation of N-acetyl-2-ethyl-2-methyl-2,3-dihydro-1H-indole with pyridinium chlorochromate, CrO3 · 2 Py, or CrO3 gave...     

Synthesis of 2-ethyl-2-methyl-2,3-dihydro-1H-indole, a new insecticide exhibiting juvenile hormone activity

Catalytic hydroamination of isoprene gave N-(1,2-dimethylprop-2-en-1-yl)aniline in a preparative yield. By heating at 260°C the product was converted into 2-ethyl-2-methyl-2,3-dihydro-1H-indole, a new ecologically safe insecticide exhibiting a juvenile hormone activity. Its insecticide properties against Tenebrio Molitor L. chrysalises were estimated at 7.5 points according to the Schmialek 9-point scale.     

Synthesis of 1- and 2-Carbamoylalkyl-2,3-dihydro-1H-indole and 9-Carbamoylalkyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole Derivatives

Treatment of 1,2,3,9a-tetrahydro-9H-imidazo- and 1,2,3,4,10,10a-hexahydropyrimido[1,2-a]indol-2-one derivatives with formic acid gave 1-carbamoylalkyl-2,3,3-trimethyl-2,3-dihydro-1H-indoles. 9-Carbamoylmethyl- and 9-(2-carbamoylethyl)-4a-methyl-2,3,4,4a,9,9a-hexahydro-1H-carbazoles were prepared from 5,6,7,7a-tetrahydro-1H,4H-imidazo- and 1,2,6,7,8,8a-hexahydro-5H-pyrimido[2,1-k]carbazolones in a similar manner. Synthesis of 2-(2-carbamoylpropyl)-2,3,3-trimethyl-2,3-dihydro-1H-indole was carried out by reduction of 1,3-dihydrospiro[2H-indolo-2,2'-piperidine] derivative with Zn in acetic acid solution.     

Synthesis of 5-[2-(Phenoxy)ethyl] Derivatives of 6-Methyluracil, 6-Methyl-2-thioxo-2,3-dihydro-1H-pyrimidin-4-one,and 2-Imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one

A synthesis of novel derivatives of 6-methyluracil, 6-methyl-2-thioxo-, and 2-imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one containing a 2-(phenoxy)ethyl substituent at position 5 of the pyrimidine ring has been carried out. It was found that 5-[2-(phenoxy)ethyl] derivatives of 6-methyl-2-thioxo- and 2-imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one are obtained by the condensation of the corresponding ethyl 3-oxo-2-(2-phenoxyethyl)butanoates with thiourea or guanidine. 6-Methyl-5-[2-(phenoxy)ethyl]uracils can be prepared by treating 6-methyl-5-[2-(phenoxy)ethyl]-2-thioxo-2,3-dihydro-1H-pyrimidin-4-ones with an excess of aqueous monochloroacetic acid solution. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1213–1217, August, 2005.     

Synthesis of nitro-substituted 4-methyl-2,3-dihydro- and 2,3,4,5-tetrahydro-1H-1,5-benzo-2-diazepinones

The nitration of 4-methyl-2,3-dihydro-1H-1,5-benzo-2-diazepinone gives the 7 nitro derivative. The 8-nitro isomer was obtained from 4-nitro-1,2-phenylenediamine. The catalytic hydrogenation of the nitrobenzodiazepinones gives the 7- and 8-amino derivatives. The nitrobenzodiazepinones exist in the enol form in alkaline media.     

One-Pot Synthesis of 2-Aryl-4-methyl-3-nitro-2,3-dihydro-1,5-benzothiazepines

Russian Journal of Organic Chemistry -     

Synthesis of 5(and 6)-nitro-4-methyl-2,3-dihydro-1h-1,5-benzo-2-diazepinones

The reaction of 4-nitro-o-phenylenediamine (I) with acetoacetic ester at room temperature under acid catalysis gives ethyl 3-(2-amino-5-nitrophenylamino)crotonate (II), which is readily cyclized to 7-nitro-4-methyl-2,3-dihydro-1H-1,5-benzo-2-diazepinone (III) on heating with alkaline agents. The reaction of I with acetoacetic ester in refluxing xylene gives isomeric 8-nitro-4-methyl-2,5-dihydro-1H-1,5-benzo-2-diazepinone (IVa) or 8-nitro-4-methyl-2,3-dihydro-1H-1,5-benzo-2-diazepinone (IVb), which are readily interconverted. The synthesis of IV is complicated by the side formation of 5-nitro-2-methylbenzimidazole (V) and thermal rearrangement of IVa and IVb to 5-nitro-1-isopropenylbenzimidazolone (VI). 6-Nitro-1-isopropenylbenzimidazolone (VII) is similarly obtained on heating III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 696–699, May, 1972.     

Synthesis and structure of 1-methyl-2,3-dihydro-1,2,4-triazolium salts and their free bases

1-Methyl-2,3-dihydro-1,2,4-triazolium iodides can be obtained by reacting methylhydrazones with S-methylthioamide hydriodides, by condensing 2-methylamidrazone hydriodides with aldehydes and ketones, or by reacting methyl iodide with 1-alkylidene (or arylidene)benzamidrazones. In solutions these salts are capable of undergoing tautomerism to 1-alkylidene(or arylidene)-2-methylamidrazone hydriodides. The influence of the structural factors on the position of the tautomeric equilibrium has been studied. The free bases obtained by neutralization of the respective salts by an alkali metal hydroxide are heretofore undescribed 1-alkylidene(or arylidene)-2-methylhydrazidoimines or 4-triazolines, depending on their structure. Under the action of oxygen, these compounds are readily oxidized to substituted 1-methyl-1,2,4-triazoles with heating.Translated from Khimiya Geterotsiklicheskikh Soedineniii, No. 10, pp. 1415–1421, October, 1984.     

Chlorination of 4-methyl-8-methoxy-2,3-dihydro-1H,1,5-benzodiazepin-2-one

The results of the chlorination of 4-methyl-8-methoxy-2,3-dihydro-1H,1,5-benzodiazepin-2-ones are compared with the results of quantum-chemical calculations of 4-methyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones with various substituents in the benzene ring in the case of homolytic halogenation. The chlorination of 4-methyl-8-methoxy-2,3-dihydro-1H-1,5-benzodiazepin-2-one (I) with N-chlorosuccinimide leads to 3-chloro- and 3,3-dichloro-4-methyl-8-methoxy-2,3-dihydro-1H-1,5-benzodiazepin-2-ones, whereas chlorination with sulfuryl chloride leads to 4-chloromethyl and 3,3-dichloro-4-methyl derivatives. The IR, PMR, and mass spectra of the synthesized compounds are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1272–1274, September, 1981.     

Synthesis of 2,3-dioxo-2,3-dihydro-4-methyl-6-chloro-1H-pyrrolo[2,3-b]pyridine and its 1-α-L-arabinopyranoside

A new type of isatin analog-2,3-dioxo-2,3-dihydro-4-methyl-6-chloro-1H-pyrrolo[2,3-b]pyridine — was obtained by oxidation of 4-methyl-6-chloro-1H-pyrrolo(2,3-b]pyridine. Condensation of L-arabinose with 4-methyl-6-chloro-2,3-dihydropyrrolo[2,3-b]pyridine and subsequent acetylation and dehydrogenation gave 1-(2,3,4-tri-O-acetyl--L-arabinopyranosyl)-4-methyl-6-chloropyrrolo[2,3-b]pyridine, which served as the starting compound for the synthesis of 1--L-arabinopyranosyl-4-methyl-6-chloropyrrolo[2,3-b]pyridine. Oxidation of 1-(2,3,4-tri-O-acetyl-L-arabinopyranosyl)-4-methyl-6-chloropyrrolo[2,3-b]pyridine gave 1-(2,3.4-tri-O-acetyl--L-arabinopyranosyl)-2,3-dioxo-2,3-dihydro-4-methyl-6-chloropyrrolo [2,3-b]pyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1083–1086, August, 1977.     

3-Phenylazo-4-methyl-2,3-dihydro-1,5-benzodiazepin-2-ones

The corresponding azo derivatives, which exist primarily in the azo form, are formed in the reaction of 2,3-dihydro-1,5-benzodiazepin-2-ones with diazonium cations. The hydrazone form of these compounds is possible in solutions of acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1558–1560, November, 1978.     

Synthesis,Antibacterial Activity,and Cytotoxicity of Newly Synthesized N-Substituted 5,6-Dimethoxy-1H-indole Derivatives

Russian Journal of General Chemistry - A series of novel functionalized N-substituted 5, 6-dimethoxy-1H-indole derivatives is synthesized. All products are evaluated for antibacterial activity...     

吲哚啉螺苯并吡喃硝基衍生物的合成

吲哚啉螺苯并吡喃类化合物受光或热的作用后,颜色能够可逆地改变。这类光致变色感光剂可作为非银盐感光材料,近年来国内在这方面也进行了研究。我们用七个取代水杨醛与     

4-氟苯基-2,3-二氢-1,5-苯并[b]硫氮杂类化合物的合成、结构和抑真菌活性

合成了26个4-氟苯基取代的1,5-苯并硫氮杂类化合物2a~2z,其结构经核磁共振波谱、红外光谱和高分辨质谱确证.采用抑菌圈法测试了其对白色念珠菌和新生隐球菌的抑菌活性,结果表明,4-(2,3-二氟苯基)/(2,5-二氟苯基)/(3,4-二氟苯基)-2,3-二氢-1,5-苯并[b]硫氮杂(2a~2f)对新生隐球菌有较强的抑制作用,但杂2a~2z对白色念珠菌均无活性.进一步考察了高活性杂2a~2f对新生隐球菌的最小抑菌浓度(MIC,MIC80)和最小杀菌浓度(MFC),发现其MIC和MFC远低于对照药氟康唑.在此基础上,对杂2a~2f进行了初步构效关系研究,并合成了4个系列21个杂衍生物3a~3f,4a~4f,5a~5f和6a~6c.通过考察其对新生隐球菌的抑菌效果,证明了杂2a~2f分子中的硫原子、碳氮双键结构单元以及2位的甲氧/乙氧羰基是该类化合物抑真菌的必需基团.     

Synthesis of 5H-1, 2-dihydro-2, 5-dioxochromeno [2,3-b] pyridines

Some representative 5H-1,2-dihydro-2,5-dioxochromeno[2,3-b]pyridines have been prepared by condensation of 2-isocyanatochromone (obtained by Curtius rearrangement of the azide of chromone-2-carboxylic acid) with enamines, followed by cyclization.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 5, pp. 588–589, May, 1970.     

Synthesis and mass spectra of 2,3-dihydro-1H-1,5-benzodiazepine-2-thiones

2,3-Dihydro-1H-1,5-benzodiazepine-2-thiones and their N-methyl and S-methyl derivatives were synthesized. It was demonstrated by means of the IR, UV, PMR, and mass spectra that in solutions with different polarities 1,5-benzodiazepine-2-thiones exist primarily in the thione form; the thione and enamino-thiol forms are the most probable forms in the gas phase.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 396–400, March, 1990.     

Synthesis of 4-styryl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones

4-Styryl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones were synthesized and their structure was established by means of PMR spectra and mass spectroscopy.Dnepropetrovsk State University Named in Honor of 300th Anniversary of the Reunion of Ukraina and Russia, Dnepropetrovsk 320625. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1560–1562, November, 1987.     

Synthesis of 4-Pyridyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones

4-Pyridyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones were obtained by the condensation of ethyl nicotinoyl- or isonicotinoylacetates with o-phenylenediamine. Alkylation of the pyridylbenzodiazepinones with ethyl iodide under phase-transfer catalysis conditions occurred at the amide nitrogen of the heterocycle, whereas in nitromethane it occurred at the nitrogen of the pyridine substituent. Bromination with N-bromosuccinimide occurred at position 3 of the heterocycle. Pyridyldibenzodiazepinones underwent thermal rearrangement to derivatives of vinylbenzimidazole.