Annelation of lactam rings to 2,3,4,4a-tetrahydro-1H-carbazole derivatives

In the reaction of 4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole and its 6-methyl- and 6-bromosubstituted derivatives with 2-chloroacetamide respectively by 9-carbamoylmethyl-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazolium chlorides are formed, which can be cyclized into 5,6,7,7a-tetrahydro-1H, 4H-imidazo[2,1-k]-carbazol-2(3H)-one derivatives. Reaction of 4a-methyl-2,3,4,4a-tetrahydro-1H-carbazole hydrochloride with acrylamide gives 8a-methyl-1,2,6,7,8,8a-hexahydro-5H-pyrimido[2,1-k]carbazol-3(4H)-one. 7a, 12-Dimethyl-3,4,4a,5,6,7,7a,12-octahydropyrido[3,2-j]carbazol-2(1H)-one was synthesized by the reaction of 4a,9-dimethyl-2,3,4,4a-tetrahydro-9H-carbazole with acrylamide. Department of Organic Chemistry, Kaunas University of Technology, Kaunas LT-3028, Lithuania; Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 645–648, May 1999.     

Stereochemistry of cyclic compounds. Communication 60. Synthesis of dicarboxylic acids of the decahydrofluorene series

Summary A method was developed for the preparation of cis-4,5,7,7a-tetrahydro-3a-methyl-3-vinylinden-6 (3aH)-one from cis-tetrahydro-7a-methyl-1,5 (4H)-indandione, and from this isomeric acids of the decahydrofluorene series were synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8 pp. 1456–1463, August, 1964     

Access to Wieland-Miescher ketone in an enantiomerically pure form by a kinetic resolution with yeast-mediated reduction

Both enantiomers of Wieland-Miescher ketone [3,4,8, 8a-tetrahydro-8a-methyl-1,6(2H,7H)-naphthalenedione], in a highly enantiomerically enriched form, became readily available by a newly developed kinetic resolution with yeast-mediated reduction. From a screening of yeast strains, Torulaspora delbrueckii IFO 10921 was selected. The collected cells of this strain, obtained by an incubation in a glucose medium, smoothly reduced only the isolated carbonyl group of the (S)-enantiomer, while the (R)-enantiomer remained intact. Starting from both enantiomers ( approximately 70% ee) prepared by an established proline-mediated asymmetric Robinson annulation, the reduction with T. delbrueckii gave the (R)-enantiomer (98% ee) and the corresponding alcohol (4aS,5S)-4,4a, 5,6,7,8-hexahydro-5-hydroxy-4a-methyl-2(3H)-naphthalenone (94% ee, 94% de) in preparative scale in nearly quantitative yields. An approach for the asymmetric synthesis of the Wieland-Miescher ketone was also successful. 2-Methyl-2-(3-oxobutyl)-1,3-cyclohexanedione, the prochiral precursor, was reduced with this strain to give a cyclic acetal form of (2S, 3S)-3-hydroxy-2-methyl-2-(3-oxobutyl)cyclohexanone, in a stereomerically pure form.     

Steroid analogs without ring B

Conclusions A new method was developed for the synthesis of trans-octahydro-6-p-methoxyphenyl-8a-methyl-1(2H)-naphthalenone (XI), an analog of D-homoestrone without ring B.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 855–859, April, 1967.     

(+)-(1S,7aS)-1-羟基-7a-甲基-茚满-4-烯-5-酮的合成及其烷基化反应研究

以2-甲基-2-(3-丁酮)环戊烷-1,3-二酮为原料,经环合和还原反应合成了手性(+)-(1S,7aS)-1-羟基-7a-甲基-茚满-4-烯-5-酮(3);3在其羟基未进行保护情况下与不同芳香侧链进行α,β-不饱和酮的α-位烷基化反应,制备了5个3的衍生物,其结构经1H NMR确证。     

3a, 4-二氢-苯并吡喃[4,3-c]吡唑-3(2H)-酮类衍生物的合成及其活性

设计合成了33种新型的3a, 4-二氢-苯并吡喃[4,3-c]吡唑-3(2H)-酮类化合物,其结构经MS,1H NMR和元素分析的确证。并对化合物7k的单晶进行了结构测定。初步生物活性测试表明标题化合物具有一定的杀虫杀菌活性。     

Two new norsesquiterpenes from Ligularia lapathifolia

Two new norsesquiterpenes were isolated from the extracts of the roots and rhizomes of Ligularia lapathifolia (Franch.) Hand.-Mazz. Their structures were identified as 2-acetyl-3a-methyl-5-(2-methyl-but-2-enoyloxy)-3a,4,5,6,7,7a-hexahydro-H-indene-4-carboxylic acid (1) and 2-acetyl-8a-methyl-2-(2-methyl-but-2-enoyloxy)-6-oxo-1,2,3,4,4a,5,6,8a-octahydro-naphthalene-1-carboxylic acid (2), respectively, on the basis of spectral data and for 1 by single-crystal X-ray analysis.     

高效大量合成AF-5的中间体:(4aR,7R)-1-丁基 -4a-甲基-7-(1-甲基-1-羟乙基)-2(1H)-八氢萘酮

化合物(4 aR,7R)-1-丁基-4 a-甲基-7-(1-甲基-1-羟乙基)-2(1H)-八氢萘酮是合成AF-5的重要中间体,传统方法是在强碱叔丁醇钾的作用下对化合物(4 aR,7R)-4 a-甲基-7-(1-甲基-1-羟乙基)-2(1H)-八氢萘酮进行烷基化反应而得到的.为了使操作更方便、安全,适合大量制备,并提高收率,作者探索了多种碱性条件,并选择氢氧化钾的叔丁醇溶液代替叔丁醇钾,最终使该步烷基化反应可以工业化.     

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 [1,3]benzoxazino[2,3-k-and [2,4]benzodiazepino[3,2-k]-carbazole derivatives

Alkylation of 4a-methyl-, 4a,6-dimethyl- and 6-bromo-4a-methyl-2,3,4,4a-tetrahydro-1H-carbazoles using 2-chloromethyl-4-nitrophenol gives [1,3]benzoxazino[2,3-k]carbazoles. Derivatives of [2,4]benzodiazepino[3,2-k]carbazole have been synthesized by alkylation of the indicated carbazolenines using 2-bromomethylbenzonitrile followed by hydrolysis of the nitrile group of the 9-(2-cyanobenzyl)-carbazolium salts obtained to amide.Kaunas Technological University, Kaunas, LT-3028, Lithuania Translated from Khimiya Geterotsiklichenskikh Soedinenii, No. 6, pp. 818–821, June, 1999.     

Natural (+)-carotol as a donor of chirality in the synthesis of enantiomerically pure hydroindene building blocks

3-Isopropyl-7a-methyl-1,2,3,6,7,7a-hexahydro-inden-5-one is a building block used in the reconstruction of the cyathane skeleton. In this article, a new and efficient method of the synthesis for (3R,7aR)-3-isopropyl-7a-methyl-1,2,3,6,7,7a-hexahydro-inden-5-one has been described.     

Photochemical Synthesis of 9-Methyl-tetracyclo[5.3.04,9.08,10]-decane-2,6-dione

Irradiation (λ > 340 nm) cis-8a-methyl-1,2,4a,7,8,8a-hexahydronaphthalene-2.7-dione ( 1 ) in benzene affords the title compound 2 via an intramolecular [2 + 2]-cycloaddition.     

Reaction of Tetracyanoethylene with 2-Substituted Cyclohexanones

Reactions of 2-methylcyclohexanone and menthone with tetracyanoethylene gave 2-(1,1,2,2-tetracyanoethyl)cyclohexanones which underwent quantitative transformation in the solid phase into 3,4-cyanosubstituted 2-aminopyrans in 2-3 days at room temperature. 2-Methyl-2-(1,1,2,2-tetracyanoethyl)cyclohexanone reacted with hydroiodic acid to afford 8a-hydroxy-2-iodo-4a-methyl-1,4,4a,5,6,7,8,8a-octahydroquinoline-3,4,4-tricarbonitrile. The reaction of 2,2'-methylenedi(cyclohexanone) with tetracyanoethylene resulted in formation of 7-imino-4,5-tetramethylene-2'-oxo-6-oxabicyclo[3.2.1]octane-2-spiro-1'-cyclohexane-1,8,8-tricarbonitrile.     

Synthesis of 3a,4,6,7,11b,12-hexahydro-3a-methyl-7-phenylbenzo[a]furo[2,3-g]quinolizines

By alkylation of stereoisomeric 7a-methyl-2-oxo-5-phenylfuro-[2,3-c]piperidines with phenacyl bromide and subsequent reduction of the keto group by sodium borohydride, amino alcohols were obtained; heating of these products in 70% sulfuric acid affords 3a,4,6,7,11b,12-hexahydro-3a-methyl-7-phenylbenzo[a]furo[2,3-g]quinolizines. It was found that the cis-quinolizidine, upon heating to 150°C in acetic acid, is isomerized to the trans-quinolizidine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1679–1682, December, 1993.     

Synthesis of new heterocycles through a cation-driven tandem ring-enlargement-annulation reaction

[reaction: see text] The thionium ion, generated through a cyclopropylcarbinyl-cyclobutyl ring expansion, is, for the first time, intramolecularly intercepted by activated aromatic rings to generate new versatile 2a-methyl-8b-(phenylsulfanyl-1,2a,3,8b-tetrahydro-2H-cyclobuta[c]chromenes.     

4a,6-Bis-(N-methlanilino)-7-hydroxy-2,3,8-trimethyl-4a,9a-dihydro-xanthen-1,4-dion: Ein thermolyseprodukt von 6-(N-methylanilino)-7a-methyl-3a,7a-dihydroindazol-4,7-dion

Summary 4a,6-Bis-(N-methylanilino)-7-hydroxy-2,3,8-trimethyl-4a,9a-dihydro-xanthene-dione (4) was obtained by thermolysis of 6-(N-methylanilino)-7a-methyl-3a,7a-dihydroindazol-4,7-dione (1) The structure was determined on basis of 1D- and 2D-NMR techniques.Herrn Prof. Dr. G. Zigeuner zum 70. Geburtstag gewidmet     

A new method for preparation of dihydrodinaphthopyranopyrans

The syntheses of 7a,15a-dlhydro-15a-methylnaphtho[2,l-b] naphtho [1',2':5,6] pyrano[3,2-e]pyran (II) and 7a,15a-dihydro-7a-methyl-15a-isopropyi naphtho [2,1-b] naphtho [1' ,2' : 5,6] pyrano [3,2-e] pyran (III) from 2-naphthol and corresponding dimethylol ketones in one step were described. Amberlyst-15® was used as catalyst.     

Synthesis of 1,3-disubstituted-2-amino-5-hydroxyindoles by reductive aromatization

Reductive aromatization and demethylation of 1,3-disubstituted-2-amino-5-oxo-7a-methyl-5,7a-dihydroindoles with zinc, pyridine and a trace of water yields 1,3-disubstituted-2-amino-5-hydroxyindoles. Simple derivatives of the 5-hydroxy substituent are described.     

Synthesis and spectroscopic characterizations of both 4b,5-dihydro-4b-methyl-11H-isoindolo[2,1-a]benzimidazol-11-ones and 2,3,3a,4-tetrahydro-3a-methyl-1H-pyrrolo[1,2-a]benzimidazol-1-ones

The complete assignment of the ¹H and ¹³C nmr spectra of some derivatives of both 4b,5-dihydro-4b-methyl-11H-isoindolo[2,1-a]benzimidazol-11-one I and 2,3,3a,4-tetrahydro-3a-methyl-1H-pyrrolo[1,2-a]-benzimidazol-1-one II was herein reported by the combined use of one and two-dimensional nmr techniques. Eight compounds, three of which are novel, 2a, 3, 6 , were thus prepared. Their uv and ir spectra were also obtained. In addition, the mass spectra of compounds 1, 2a, 2b, 3 and 6 are reported.     

6α-取代的(1S, 7aS)-(+)-1-叔丁氧基-7a-甲基-2, 3, 5, 6, 7, 7a-六氢茚-5- 酮的合成

用化学动力学控制的方法在化合物3的5-C上C=O与6-C发生烯醇化生成锂盐,然后可在6-C位分别引入甲基、烯丙基、苄基、溴以及羟基取代基。产物6、7、8、9a和11经鉴定,除9α外其他都是α和β构型的混合物,其中以α-构型取代物为主。