Regular Issue

Vol. 19, No. 7, 1982

22 data found. 1 - 22 listed
Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1191 - 1195
Published online:
DOI: 10.3987/R-1982-07-1191
Saturated Heterocycles. Part 31. Synthesis and Conformational Studies of 2-Oxo- and 2-Thiotetrahydro-1,3-oxazines with Condensed Skeletons

Géza Stájer, Angela E. Szabó, Ferenc Fülöp, Gábor Bernáth, and Pál Sohár

*Institute of Pharmaceutical Chemistry, Albert Szent-Györgyi Medical University, H-6701 Szeged, Eötvös u.6., Hungary


Stereoisomeric 2-oxo- and 2-thio-4,5- (and 5,6)-tetramethylenetetrahydro-1,3-oxazines (2 and 4) have been synthesized. 1H nmr spectra afford evidence that in the cese of the cis isomers of derivatives 2, prepared from 2-(aminomethyl)cyclohexanols, the O-inside conformer predominates, independently of the N-substituent (R = H, CH3); in derivatives 4, made from 2-(hydroxymethyl)cyclohexylamines, the N-inside conformer predominates if R = H, while the N-outside conformer does so when R = CH3.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1197 - 1202
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DOI: 10.3987/R-1982-07-1197
Cycloaddition Reactions of 1-Ethoxycarbonyl-1H-azepine and 1-Ethoxycarbonyl-1H-1,2-diazepine with 3,4,5,6-Tetrachloro-1,2-benzoquinone

Katsuhiro Saito, Shigenori Iida, and Toshio Mukai

*Faculty of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan


The reaction of 1-ethoxycarbonyl-1H-azepine (1) with 3,4,5,6-tetrachloro-1,2-benzoquinone at room temperature afforded a [6+4] type cycloadduct 3 as a major product in addition to two [4+2] type cycloadducts 4 and 5. Upon heating, 3 rearranged to 5 in a fairly good yield. In the same reaction with 1-ethoxycarbonyl-1H-1,2-diazepine (2), a [4+2] type cycloadduct 6 was formed. The low electron density at the 2 and 7 positions of 1 is considered to be one reason for the formation of the [6+4] type cycloadduct 3.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1203 - 1206
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DOI: 10.3987/R-1982-07-1203
A New 4,5-Dioxoaporphine and Other Constituents of Aristrochia indica

Basudeb Achari, Sarmistha Chakrabarty, Soumitra Bandyopadyay, and Satyesh C. Pakrashi

*Indian Institute of Chemical Biology, Calcutta-700 032, India


A new 4,5-dioxoaporphine, deduced to be 2-hydroxy-1-methoxy-4H-dibenzo[de,q]quinoline-4,5(6H)-dione (4a) from spectroscopic evidences, cepharadione A (4c), aristololactam AII (2b) and β-sitosterol-β-D-glucoside have been encountered in the roots of Aristolochia indica Linn.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1207 - 1210
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DOI: 10.3987/R-1982-07-1207
6-β-[Bistrifluoromethanesulfonyl]amidopenicillanic Acid. A Novel β-Lactamase Inhibitor

Peter S. F. Mézes, Richard W. Friesen, Thamaiah Viswanatha, and Gary I. Dmitrienko

*Guelph-Waterloo Centre for Graduate Work in Chemistry, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada


Benzyl 6-β-[bistrifluoromethanesulfonyl]amidopenicillanate, 4, was prepared by reaction of benzyl 6-β-aminopenicillanate, 3, with two equivalents of trifluoromethane sulfonic anhydride. In the presence of aqueous base 4 undergoes detriflation to yield 7 and in the presence of basic methanol 4 yields the α-methoxymonotriflamide 6. The free acid 5 obtained by hydrogenolysis of 4 has β-lactamase inhibitory properties.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1211 - 1214
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DOI: 10.3987/R-1982-07-1211
The Preparation of α,β-Unsaturated Ketones by the Grignard Reaction with β-(N-Alkyl-N-acylamino)enones

Choji Kashima and Yasuhiro Yamamoto

*Department of Chemistry, University of Tsukubaa, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan


The Grignard reaction of β-(N-alkyl-N-acylamino)enones afforded regioselectively α,β-unsaturated β-(N-alkyl-N-acylamino)alcohols, which were converted into α,β-unsaturated ketones by hydrolysis accompanying dehydration. The resulting α,β-unsaturated ketones were regioisomeric with α,β-unsaturated ketones derived from β-(N,N-dialkylamino)enones by the Grignard reaction.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1215 - 1217
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DOI: 10.3987/R-1982-07-1215
Configuration of Some Alkaloids by a Chiral NMR Shifts Reagent

Krzysztof Jankowski, Julius Isaraeli, Julien B. Chiasson, and Andrzej Rabczenko

*Department of Chemistry and Biochemistry, Université de Moncton, Moncton, New Brunswick, E1A 3E9, Canada


The optically active lanthanide shift reagents was used to quickly solve the problem of configuration of some alkaloids. The S isomers give smaller induced shift than R isomers when the complex is formed with europium d-camphorate.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1219 - 1222
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DOI: 10.3987/R-1982-07-1219
New Alkaloids, Leucotamine and O-Methylleucotamine, from Leucojum asetivum L

Shigeru Kobayashi, Kazuyoshi Yuasa, Kimihito Sato, Yasuhiro Imakura, and Tetsuro Shingu

*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan


The structures of leucotamine and O-methylleucotamine isolated from the leaves of Leucojum asetivum L., have been determined as 3 and 4, respectively, on the basis of spectral and chemical evidence.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1223 - 1225
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DOI: 10.3987/R-1982-07-1223
A Synthesis of Withasomnine from 4-Phenylpyrazole

Seiichi Takano, Yoko Imamura, and Kunio Ogasawara

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


Withasomnine(5), a pyrazole alkaloid isolated from Withania somnifera Dun.(Solanaceae), has been synthesized from 4-phenylpyrazole(1), a compound with potential symmetry.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1227 - 1231
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DOI: 10.3987/R-1982-07-1227
Acridone Alkaloids V. New Fulo- and Pyranoacridone Alkaloids from Glycosmis citrifolia (Willd.) Lindl

Tian-Shung Wu, Hiroshi Furukawa, and Kuo-Shih Hsu

*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan


Two new furoacridone alkaloids, furofoline-I(1) and -II(2), and a new linear pyranoacridone alkaloid, pyranofoline(3) were isolated from the root and stem bark of Glycosmis citrifolia (Willd.) Lindl., and their structures were elucidated.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1233 - 1236
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DOI: 10.3987/R-1982-07-1233
Revised Structure of Physoperuvine, an Alkaloid of Physalis peruviana Roots

Anil B. Ray, Yoshiteru Oshima, Hiroshi Hikino, and Chizuko Kabuto

*Chemistry Department, Faculty of Science, Banaras Hindu University, Varanasi-221 005, India


The previously reported physoperuvine, an alkaloid isolated from the roots of Physalis peruviana, has been found to be a hydrochloride and its structure has been settled as 3 by X-ray analysis. The forms of existence of physoperuvine, a free base, and its hydrochloride have been studied, revealing that while the salt remains exclusively in the amino-alcohol form (3), the free base is an equilibrium mixture of the amino-alcohol (1) and the amino-ketone (2), the equilibrium being shifted toward the former.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1237 - 1241
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DOI: 10.3987/R-1982-07-1237
Correlation od Singlet-Triplet Transitions of π-Electron Heterocycles with the HMO NV1 Energies

Cyril Párkányi

*Department of Chemistry, The University of Texas at El Paso, El Paso, Texaz 79968-0513, U.S.A.


The wavenumbers of the O-O bands in the phosphorescence spectra of pyridine-like heterocycles and/or the corresponding bands in their S→T absorption spectra are linearly correlated with the HMO N→V1 transition energies, i. e., the transition energies from the highest occupied π-molecular orbital to the lowest unoccupied π-molecular orbital. A similar relationship has been established in the case of thiophene-like heterocycles.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1243 - 1245
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DOI: 10.3987/R-1982-07-1243
Iodo- and Phenylselenocarbamete Cyclizations: New Versatile Methods for Functionalization of Olefinic Bonds

Seiichi Takano and Susumu Hatakeyama

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


Efficient methods for conversion of the unsaturated benzyl carbamates (6-9) into the cyclic carbamates (11-14) have been developed.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1247 - 1252
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DOI: 10.3987/R-1982-07-1247
Stereoselective Syntheses of (±)-18-Deoxypalustrine and (±)-18-Deoxy-13-epipalustrine

Masashi Ogawa, Junko Nakajima, and Mitsutaka Natsume

*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan


Total syntheses of the title compounds (4 and 5) were achieved in a regio- and stereoselective fashion via 13, 15, 17, 18, 22, and 34, starting from the compound (8) obtained by the SnCl2 effected reaction of an endo-peroxide derived from 7. Treatment of an amino-aldehyde derivative such as 23 in a basic condition furnished the preferential conversion of 2,6-cis-dialkylpiperidines into 2,6-trans derivatives through retro Michael intermediates.

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Communication | Regular issue | Vol 19, No. 7, 1982, pp. 1253 - 1256
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DOI: 10.3987/R-1982-07-1253
Synthesis of 7-Hydrazinocephalosporins

Daijiro Hagiwara, Kozo Sawada, and Masashi Hashimoto

*Central research Laboratories, Fujisawa Pharmaceutical Co. Ltd., 2-1-6 Kashima, Yodogawa-ku, osaka 532, Japan


Hydrazonation of 7-oxocephems 2a,b, followed by borane reduction of the resulting E and Z hydrazono compounds 3a,b and 4a,b, provided the key intermediates 5a,b, which were acylated to 6a,b, and then deprotected to yield the 7-hydrazinocephalosporin derivatives 7a,b.

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Report | Regular issue | Vol 19, No. 7, 1982, pp. 1257 - 1262
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DOI: 10.3987/R-1982-07-1257
Study of Orienration of the Nitrogen Lone-pair Electrons in 2-Methyl-3-oxo-2-azabicyclo[2.2.2]oct-7-ene Derivatives

Hiroshi Tomisawa, Hiroshi Hongo, Julien B. Chiasson, and Christopher K. Jakowski

*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan


The 13C NMR spectra of 5 or 6-cyano- and carboxy-2-methyl-3-oxo-2-azabicyclo[2.2.2]oct-7-ens have been studied in the presence of Ni(acac)2. The calculated contact shifts have been compared to experimental ones. According to NMR evidence the nitrogen lone-pair electrons are preferentially anti relative to the double band - showing some n-π nonbonded interaction. The simulation of the shift reagent experiment program, SIMULATION, written in APL, is used in this calculation.

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Report | Regular issue | Vol 19, No. 7, 1982, pp. 1263 - 1268
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DOI: 10.3987/R-1982-07-1263
Reaction of Ethyl β-Alkylaminocrotonates in the Presence of Organic Acid

Masatoshi Yamato, Koichi Sato, Kuniko Hashigaki, and Mayumi Ninomiya

*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan


Condensation of ethyl β-alkylaminocrotonates, obtained from ethyl acetoacetate and amines, in the presence of 3-mercaptopropionic acid gave 1,6-naphthyridine-2,5-dione derivatives. The structures of these compounds were determined on the basis of several informations of chemical reactivities and spectral data.

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Report | Regular issue | Vol 19, No. 7, 1982, pp. 1269 - 1275
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DOI: 10.3987/R-1982-07-1269
Selective Cleavage of Unsymmetrical 2,2-Spiro-1,3-dioxolanes. II. Cleavage of Ketal Ring of 5’-Bromo-6’,7’-dihydro-4-isopropylaminomethyl-1’-p-toluenesulfonyl-spiro[1,3-dioxolane-2,4’-(5H’)-indole and Its Analogs

Makiko Sakai

*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan


The bromodioxolane and its analogs (1-5) were treated with organic base (DBU, DBN, or morpholine), acid (p-toluenesulfonic acid or Lewis acid), or Lewis acid/tertiary amine, and yielded 4-alkoxyindoles (6-17). Reaction of 1 with organic base gave two isomeric 4-alkoxyindoles, 6 (tosylpindolol, a secondary alcohol) and 11 (a primary alcohol), while tri-n-octylamine with stannic chloride afforded 6 (74 %) without producing 11.

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Report | Regular issue | Vol 19, No. 7, 1982, pp. 1277 - 1280
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DOI: 10.3987/R-1982-07-1277
Selective Cleavage of Unsymmetrical 2,2-Spiro-1,3-dioxolanes. III. Cleavage of 4-Isopropylaminomethyl-1,3-dioxolanes Linked with Benzene, Thiophene, Furan, or Isoxazole on the C(2)-Spiro Atom

Makiko Sakai

*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan


The dioxolanes (1-3 and 7-11) were treated with stannic chloride and tertiary amine (triethylamine or tri-n-octylamine) and gave aromatic ethers 12-14. enol-ethers 4-6, and a bromoenol-ether 15, respectively.

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Report | Regular issue | Vol 19, No. 7, 1982, pp. 1281 - 1284
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DOI: 10.3987/R-1982-07-1281
Formation of the Idolizidine Ring System by an Unusual Base-Induced Cyclization

Joan Bosch and Josep Bonjoch

*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain


The formation of the indolizidine ring system by base-induced cyclization of ethyl 1-benzoyl-2-piperidinepropionate derivative is described.

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Report | Regular issue | Vol 19, No. 7, 1982, pp. 1285 - 1290
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DOI: 10.3987/R-1982-07-1285
Synthesis of (±)-8-Aza-11-deoxy-10-oxaprostaglandin E1

Noboru Kubodera, Hiroyuki Nagano, Michiro Takagi, and Isao Matsunaga

*Chugai Pharmaceutical Company, Ltd., 135, 1-Chome Komakado, Gotemba City, shizuoka 412-8513, Japan


Synthesis of new oxazolidine prostanoids, racemic 8-aza-11-deoxy-10-oxaprostaglandin E1(10), starting from DL-serine(1) is described.

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Report | Regular issue | Vol 19, No. 7, 1982, pp. 1291 - 1294
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DOI: 10.3987/R-1982-07-1291
Thermal Rearrangement of Cyclohexanone Oxime O-Benzyl Ether

Junko Koyama, Teruyo Sugita, Yukio Suzuta, and Hiroshi Irie

*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, kobe, Hyogo 658, Japan


Thermal rearrangement of cyclohexanone oxime O-benzyl ether under air gave 1,2,3,4,7,8,9,10-octahydro-6-phenylphenanthridine in 35% isolated yield, which yielded 6-phenylphenanthridine by dehydrogenation reaction with palladium carbon. The structure of the latter was confirmed by direct comparison with the authentic sample. The mechanism for the reaction was briefly discussed.

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Review | Regular issue | Vol 19, No. 7, 1982, pp. 1295 - 1318
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DOI: 10.3987/R-1982-07-1295
Biosynthesis of Isoflavonoid and Related Phytoalexins

Muhammad Afzal and Galib Al-Oriquat

*Institute of Organic Chemictry, C. S. I. C., Juan de la Cierva, 3, 28006 Madrid, Spain


Biosynthesis of isoflavonoid phytoalexins and related compounds is reviewed.

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22 data found. 1 - 22 listed