Regular Issue

Vol. 22, No. 6, 1984

23 data found. 1 - 23 listed
Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1303 - 1306
Published online:
DOI: 10.3987/R-1984-06-1303
Thermal Ring Expansion of 2-Vinylthiacycloalkane N-Imides by [2,3]-Sigmatropic Rearrangement

Haruki Sashida and Takashi Tsuchiya*

*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan


The thermolysis of the 2-vinylthiacyclo-pentane, -hexane, and -heptane N-(p-toluenesulfonyl)imides (7) resulted in the [2,3]-sigmatropic rearrangement to give the corresponding ring expansion products (8).

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Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1307 - 1313
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DOI: 10.3987/R-1984-06-1307
Crystal Structure Determination of the 2,6-Diphenyl-1,3,6,2-dioxazaphosphocane-p-monoborane Adduct. Evidence for the Lack of Transannular Interaction and Observation of a PhosphorusIV Atom Deformation towards Pseudopentacoordination

Rosalinda Contreras,* Apolonia Murillo, and Alain Klaébé

*Centro de Investigación y de Estudios Avanzados, Departmento de Química , I.P.N, Apartado 14-740, México, D.F., 07000, Mexico


The X-ray crystal structure of the title compound shows a crown conformation of the ring and a strong 1,3 diaxial interaction between the P-BH3 group and the two corresponding hydrogens. This interaction leads an approach between the phosphorus and nitrogen. As a result the structure of phosphorusIV changes towards a pseudopentacoordinated geometry. The intracyclic Lewis interaction between N and P atoms is discarded due to the observed planarity of intracyclic anilic nitrogen.

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Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1315 - 1318
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DOI: 10.3987/R-1984-06-1315
A Convenient Synthetic Method of 1-Acyl-2-aryl-3,3-dimethylindole Involving Isolable Diastereomeric Atropisomers

Takeo Kitamura,* Toshitaka Koga, Tanezo Taguchi, and Kazunobu Harano

*Daiichi College of Pharmaceutical Sciences, 22-1 Tamagawa-cho, Minami-ku, Fukuoka 815-0037


The synthesis of 1-acyl-2-aryl-3,3-dimethylindoline was improved by the reaction of 1-acyl-2-hydroxy-3,3-dimethylindoline with an arene in the presence of BF3·O(C2H5)2 in dioxane, and stable diastereomeric atropisomers were isolated as products when the arene was β-naphthol.

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Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1319 - 1322
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DOI: 10.3987/R-1984-06-1319
Reaction of α-Silyl Carbanion with Oxime Ethers

Takeo Konakahara,* Masayuki Matsuki, and Kenji Sato

*Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan


In the presence of LDA, 2-(trimethylsilylmethyl)pyridine reacts with p-substituted benzaldoxime methyl ethers to give stereoselectively trans-2-aryl-3-(2-pyridyl)aziridines and (Z)-1-amino-1-aryl-2-(2-pyridyl)ethenes. From the temperature-dependent 1H-nmr spectra of trans-2-phenyl-3-(2-pyridyl)aziridine, ΔF* was estimated to be about 14 kcal / mol at the coalescence temperature (Tc = 0 °C).

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Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1323 - 1326
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DOI: 10.3987/R-1984-06-1323
Mass Spectra of Hexahydroproaporphine Type Alkaloids

Sheng-Teh Lu* and Ian-Lih Tsai

*School of Pharmacy, Kaohsiung Medical College, 100 Shih Chuen 1st Rd., Kaohsiung 80708, Taiwan, R.O.C.


Mass spectra of litsericine (1), N-methyllitsericine (2), lauformine (3) and N-methyllauformine (4) belonging to the hexahydroproaporphine group were measured, and the main fragmentation pathways for these alkaloids were presumed from the examination of their mass shifts.

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Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1327 - 1330
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DOI: 10.3987/R-1984-06-1327
On the Configuration of the C5-Substituents of Lycopodium Alkaloids, 8-Deoxyserratinidine, Epidihydrofawcettidine, Serratinidine, and Dihydrofawcettidine

Takashi Harayama,* Tooru Taga, Kenji Oskai, and Kaoru Kuriyama

*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan


The configuration of the C5-substituents of 8-deoxyserratinidine, epidihydrofawcettidine, serratinidine, and dihydrofawcettidine was determined as formulas 2, 3, 4, and 5, respectively, by 1H-NMR, Brewster’s benzoate rule, and an X-ray analysis of 8-deoxyserratinidine.

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Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1331 - 1334
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DOI: 10.3987/R-1984-06-1331
Reductive Formation of Pyrimidinylmethylenephosphoranes by Reaction of Trichloromethylpyrimidines with Triphenylphosphine

Shoetsu Konno, Yumi Sato, Takao Sakamoto, Nobuya Katagiri, and Hiroshi Yamanaka*

*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan


The reaction of trichloromethylpyrimidines (1) with ca. 5 equivalent amounts of TPP gave pyrimidinylmethylenephosphoranes (9), whereas in the presence of 2 equivalent amounts of TPP, 1 was converted into the corresponding pyrimidinylchloromethylenephosphosphoranes (2). Condensation of 2 and 9 with aldehydes gave smoothly pyrimidine derivatives having an olefinic side chain. The pathway of the reduction to form the phosphoranes was discussed with experimental evidence.

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Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1335 - 1337
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DOI: 10.3987/R-1984-06-1335
Reactions of 3-Dicyanomethyl-1-ethylbenzotriazolium Ylide with Acetylenic Esters

Enrique Díez-Barra, José Elguero, and Carmen Pardo*

*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain


The titled compound (1) reacts with acetylenic esters (2) giving 1:1 adducts (4), via 1,3-dipolar cycloaddition. Concerning the regioselectivity of the reaction, experimental results are in agreement with theoretical calculations and correspond to an inverted polarization of the azomethineimine moiety with regard to most known examples.

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Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1339 - 1342
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DOI: 10.3987/R-1984-06-1339
Unexpected ’One-pot’ Formation of the Novel Macrocycle 1,8,15-Trithia[2.2.2](3,5)-1,3,4-thiadiazolinophane-4,11,18-trithione

Sebastiano Pappalardo,* Francesco Bottino, amd Corrado Tringali

*Dipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 8, I-95125 Catania, Italy


The titie compound (1) is obtained in 15% yield from the reaction of equimolar amounts of 2,5-dimercapto-1,3,4-thiadiazole (2), dibromomethane and potassium hydraxide in ethanol. A possible mechanism, involvmg the self-condensation of the extremely reactive intermediate 3-bromomethyl-5-mercapto-1,3,4-thiadiazoline-2-thione (12a) to macrocycle (1), is proposed.

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Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1343 - 1345
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DOI: 10.3987/R-1984-06-1343
Biotransformation of a Tetrahydroprotoberberine N-Metho Salt to a Spirobenzyisoquinoline Accompanying N-Methyl Group Transfer to O-Methyl Group by Callus Cultures of Corydalis Species

Kinuko Iwasa,* Akiko Tomii, Narao Takao, Toshimasa Ishida, and Masatoshi Inoue

*Kobe Pharmaceutical University, Motoyamakita, Higashinada, Kobe 658-8558, Japan


The Structure and stereochemistry of base C, a 13-hydroxytetrahydroprotoberberine metabolite in cell cultures, have been determined by X-ray analysis. Thereby the biotransformation of a tetrahydroprotoberberine N-metho salt to a spirobenzylisoquinoline , involving a migration of the N-methyl group to the O-methyl group was first demonstrated.

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Communication | Regular issue | Vol 22, No. 6, 1984, pp. 1347 - 1350
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DOI: 10.3987/R-1984-06-1347
Synthesis of Indole and Related Compounds from Halo-nitroaromatics

Takao Sakamoto, Yoshinori Kondo, and Hiroshi Yamanaka*

*Pharmaceutical Institute, Pharmaceutical Institute, Aobayama, Sendai 980-8578, Japan


5,7-Dimethyl-6-azaindole was synthesized by treatment of 3-amino-2,6-dimethyl-4-pyridineacetaldehyde diethyl acetal with hydrochloric acid in boiling ethanol. According to the similar manner, indole and ethyl 4-indolecarboxylate were obtained from the corresponding 2-aminophenylacetaldehyde derivatives in satisfactory yields. The starting materials were easily prepared by palladium-catalyzed cross-coupling reaction of o-halonitroaromatics with trimethylsilylacetylene followed by the reaction with sodium ethoxide and catalytic reduction of the o-nitro group.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1351 - 1357
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DOI: 10.3987/R-1984-06-1351
Claisen Rearrangement of Meta-substituted Aryl Propargyl Ethers in Poly(ehtylene glycol)

Usha Rao and Kalpattu Kuppuswami Balasubramanian*

*Department of Chemistry, Indian Institute of Technology, Madras, 600 036, India


The thermal rearrangement of meta-substituted aryl propargyl ethers was studied in poly(ethylene glycol)-200. The rearrangement was not regiospecific.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1359 - 1362
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DOI: 10.3987/R-1984-06-1359
A New Preparation of an Ochotensin-type Isoquinoline by Photolysis

Yoshiro Hirai, Hiroyuki Egawa, and Takao Yamazaki*

*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan


The photolysis of 1-benzoyl-3,4-dihydroisoquinoline hydrochlorides (3) and (4) gave spirobenzylisoquinolines (5) and (6).

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1363 - 1368
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DOI: 10.3987/R-1984-06-1363
The Influence of Alkyl Substituents on Internal Photodimerization of Pyrimidine-6-azapyrimidine Dinucleotide Analogues

Jadwiga Jankowska, Henryk Koroniak, and Krzysztof Golankiewicz*

*Facluty of Chemistry, Adam Mickiewicz University, ul. Grunwaldzka 6, 60-780 Poznán, Poland


The new internal photodimers of dinucleotide analogues in which 5-alkyl derivatives of uracil and 6-azauracil are connected with trimethylene chain have been obtained. The structure is discussed on the basis of spectroscopic data.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1369 - 1375
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DOI: 10.3987/R-1984-06-1369
Addition of Phthalimido Nitrene to Substituted Cyclopentadienes

Krishna Narasimhan* and Perumal Raja Kumar

*Department of Organic Chemistry, Guindy Campus, University of Madras, Chennai-600 025, India


The aziridines 3,3a and 3b obtained by the cycloaddition of phthalimidonitrene to cyclopentadiene derivatives 2, 2a and 2b undergoes facile ring expansion, when treated with sodium hydride to give substituted pyridine derivatives 4, 4a and 4b respectively. Hydrazinolysis of the aziridines gives the cyclopentadiene derivatives through the intermediacy of N-aminoaziridines 5,5a and 5b. Oxidation of the aziridines 3,3a with lead tetraacetate gives ths aziridine 6 and 6a.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1377 - 1382
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DOI: 10.3987/R-1984-06-1377
A Novel Photochemical Method for the Synthesis of Flavonols

T. Sudhakar Rao, Anil Kumar Singh, and Girish Kumar Trivedi*

*Department of Chemistry, Indian Institute of Technology, Powai, Bombay 400 076, India


Photolysis of the nitrochromenes followed by acidic hydrolysis of the photoproducts yields the corresponding flavonols in high yields.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1383 - 1385
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DOI: 10.3987/R-1984-06-1383
2-Aryl-oxazolo- and Thiazolopyridines. Synthesis via Cyclization of N-(2-Chloro-3-pyridinyl)arylamides and Thioamides

Axel Couture* and Pierre Grandclaudon

*Laboratoire de Chimie Organique Physique, Université des Sciences et Technologies de Lille, 59655 Villeneuve d’ Ascq Cedex, France


Chloropyridinylenamides can be easily converted into oxazalo- and thiazolo [5,4-b]pyridines by treatment with polyphosphoric acid and Lawesson reagent respectively.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1387 - 1390
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DOI: 10.3987/R-1984-06-1387
Epoxidation of 3-(3’-Butenyl)-4-hydroxycoumarins and Intramolecular 6-Exo Cyclization to 3,4-Dihydro-2-hydroxymethyl-2H,5H-pyrano[2,3-b][1]benzopyran-5-one

Pierfrancesco Bravo,* Giuseppe Resnati, Calimero Ticozzi, and Giancarlo Cavicchio

*CNR, Centro Studio Sostanze Organiche Naturali, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy


Several 3-(3’-butenyl)-4-hydroxycoumarins were synthetized and oxidized with m-chloroperbenzoic acid. 3,4-Dihydro-2-hydroxymethyl-2H,5H-pyranol[2,3-b][1]benzopyran-5-ones were obtained through an intramolecular 6-Exo cyclization of intermediate epoxide.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1391 - 1394
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DOI: 10.3987/R-1984-06-1391
A Convenient Synthesis of Novel 3-Amidino-2-oxo-1,2-dihydroquinoxaline

Yoshihisa Kurasawa,* Yoshihisa Okamoto, and Atsushi Takada

*School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108-8641, Japan


The reactions of 3-(5-oxo-1,2,4-oxadiazolin-3-yl)-2-oxo-1,2-dihydroquinoxaline (2) and 2-oxo-1,2-dihydroquinoxaline-3-amidoxime (3), derived from 3-cyano-2-oxo-1,2-dihydroquinoxaline (1), with FeSO4-HCl and Fe-HCl afforded Fe(II) complexes of 3-amidino-2-oxo-1,2-dihydroquinoxaline (4), whose treatment with NaOH gave the free ligand 4.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1395 - 1402
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DOI: 10.3987/R-1984-06-1395
Syntheses and Reactions of Pyridazine Derivatives XX. Studies on the Radical Methylation of the 1,2-Diazine System

Gottfried Heinisch* and Gerhard Lötsch

*Institut für Pharmazeutische Chemie, Universität Wien , Pharmaziezentrum, Althanstrasse, 14 A-1090 Wien, Austria


Protonated pyridazines (1,2,3) on reaction with methyl radical (generated by oxidative decarboxylation of acetic acid or by redox reaction of t-BuOOH/FeSO4·7H2O) are shown mainly to be attacked at positions β to the nitrogen atoms. However, formation of compounds 2,4,5,6,8,9 and 10 indicates lower degree of regioselectivity compared with homolytic benzylation or acylation of the 1,2-diazine system. Synthesis of ethyl 5-styryl-4-pyridazinecarboxylates (13,14) was achieved by homolytic methylation of ethyl 4-pyridazinecarboxylate (11) followed by condensation with aromatic carbaldehydes.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1403 - 1410
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DOI: 10.3987/R-1984-06-1403
Synthesis of Novel Carboxyl Porphyrins and Their Iron Complexes: 5,10,15,20-Tetra[α,α,α,α-o-(2,2-dimethyl-ω-carboxylalkanamido)phenyl]porphinato Iron Complexes

Yoh-ichi Matsushita, Etsuo Hasegawa, Kiyoshi Eshima, and Eishun Tsuchida*

*School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan


Novel porphyrin derivatives having 2,2-dimethyl-ω-carboxylalkyl chains as amphiphilic moieties and their iron complexes are synthesized. The typical compound is bromo-5,10,15,20-tetra[α,α,α,α-O-(2,2-dimethyl-12-carboxyldodecanamido)phenyl]porphinato iron(III). The lipophilic-liophilic balance can be controlled by changing the alkyl chain length.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1411 - 1415
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DOI: 10.3987/R-1984-06-1411
A Stereoselective Synthesis of 1,5-Disubstituted Thieno[3’,2’:3,4]piperidino[1,2-c]oxazolidin-3-ones through N-Oxaacyliminium Ion Cyclization

Shinzo Kano,* Yoko Yuasa, Tsutomu Yokomatsu, and Shiroshi Shibuya

*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan


A stereoselective synthesis of 1-phenyl- (5) and 5-methyl-1-phenylthieno[3’,2’:3,4]piperidino[1,2-c]oxazolidin-3-ones (8a,b) was achieved by reduction of the corresponding N-substituted 5-phenyloxazolidine-2,4-diones (4, 7a,b) with diisobutylaluminum hydride, followed by treatment of the reduction products with formic acid. Reduction of 8a,b with LiAlH4 afforded the corresponding 4-(α-hydroxybenzyl)-6-methylthieno[3,2-c]pyridines (10a,b), respectively.

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Report | Regular issue | Vol 22, No. 6, 1984, pp. 1417 - 1420
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DOI: 10.3987/R-1984-06-1417
Consecutive Menschutkin Reaction of Cyclic Amines with Dichloromethane under High Pressure: Synthesis of Methylenebisamines

Kiyoshi Matsumoto,* Shiro Hashimoto, Yukio Ikemi, and Shinichi Otani

*Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan


The reaction of heterocyclic amines such as pyrrolidine, piperidines, and morpholines with dichloromethane in methanol in the kiro bar region affording the corresponding methylenebisamines is described.

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23 data found. 1 - 23 listed