HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Regular Issue
Vol. 24, No. 4, 1986
Published online:
■ Brunonine, a New C20-Diterpenoid Alkaloid
Wei Deng and Wei Liang Sung*
*Institute of Materia Medica, Chinese Academy of MedicalSceince, Nan-wei Road, Beijing 100050, China
Abstract
The structure of brunonine (1), a new C20-diterpenoid alkaloid isolated from the whole plant of Delphinium brunonianum Royle, was established on the basis of spectroscopy and the result of X-ray crystallography. Brunonine (1) was shown to possess the atisine azomethines (4) skeleton, with an ethoxylgroup at C(19) position.
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■ Three New C19-Diterpenoid Alkaloids, Delbrunine, Delbruline and Delbrusine from Delphinium brunonianum Royle
Wei Deng and Wei Liang Sung*
*Institute of Materia Medica, Chinese Academy of MedicalSceince, Nan-wei Road, Beijing 100050, China
Abstract
The structure elucidations of delbrunine (1), delbruline (2) and delbrusine (3) isolated from Delphinium brunonianum Royle are presented.
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■ The Diterpenoid Alkaloids from Aconitum scaposum var. vaginatum
Qing Ping Jiang and Wei Liang Sung*
*Institute of Materia Medica, Chinese Academy of MedicalSceince, Nan-wei Road, Beijing 100050, China
Abstract
The structure determinations of vaginatine (1), vaginaline (2) and vaginadine (3), diterpenoid alkaloids from Aconitum scaposum var. vaginatum, are reported.
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■ Intramolecular Cycloaddition of Allenecarboxylate. An Effect of Orbital Overlap Requirement of the Ester Linkage
Mitsutaka Yoshida, Mari Hiromatsu, and Ken Kanematsu*
*Institute of Synthetic Organic Chemistry, Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
The intramolecular cyclizations of the allenecarboxylates have been examined and two types of the cycloadditions are observed. The periselectivity in these reactions was discussed on the basis of the effect of orbital overlap requirements of the ester linkage in the transition state.
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■ The Preparation of Aza-β-lactam, 1,3,4-Thiadiazine, β-Lactam, and 1,3,4-Thiadiazepine Derivatives by the Reaction of Thiosemicarbazidines with α- and β-Haloacyl Halides
Tadashi Okawara, Rie Kato, Tetsuo Yamasaki, Naohiko Yasuda, and Mitsuru Furukawa*
*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan
Abstract
The reaction of thiosemicarbazide (I) with α- and β-haloacyl halides provided aza-β-lactam (III), 1,3,4-thiadiazine (V) , β-lactam (X) , and 1,3,4-thiadiazepine (XI and XII) derivatives under two phase conditions.
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■ Reactions of Sulfonyl Substituted Furoxans with Olefins
Tomio Shimizu,* Yoshiyuki Hayashi, Masayuki Miki, and Kazuhiro Teramura
*Department of Color Chenistry and Technology, Faculty of Industrial Arts, Kyoto Institute of Technology, Matsugasaki-goshokaidoumati, Sakyo-ku, Kyoto 606-0962 Kyoto, Japan
Abstract
3,3’-Bi-2-isoxazolines were obtained from the reaction of bis(butylsulfonyl)furoxan with olefins in xylene-DMF (1 : 1) at the refluxing temperature. On the other hand, 3-(1-hydroxyimino)ethyl-2-isoxazolines were obtained from the reactions of 3-methyl-4-methylsulfonylfuroxan with olefins under similar conditions.
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■ 1,3-peri-Repulsion; a New Synthetic Control Factor for Methyl Epimers by Opening or Closing γ-Lactone and Its Fixation by Dithioacetal
Tetsuichi Shibata,* Tamiko Ohkura, Nobuko Shimizu, and Seiichi Inayama
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
The inversion of methyl adjacent to ketone from equatorial to axial was achieved by virture of 1,3-peri-repulsion of the hydroxyl group formed by opening γ-lacone in a series of tetrahydro-l-α-santonin and their derivatives, and was confirmed chemically by fixation of the adjacent ketone by ethylene dithioacetal without epimerization of the methyl group.
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■ Dithioacetal; as a Chiroptical Functional Group to Determine Absolute and Relative Configuration by CD and 1H NMR Spectra
Tetsuichi Shibata,* Tamiko Ohkura, and Seiichi Inayama
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
Ethylene dithioacetal (EDT) was first used as a chiroptical group to determine both absolute and relative configurations of asymmetric centers in α and β-positions in relation to EDT by the signs of the Cotton effect in CD and by an aromatic solvent-induced shift of 1H NMR, respectively, in a series of EDTs of 4,10-dimethyldecal-3-ones compared with those of steroid ketones.
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■ 2(S),5(S)-Bis(hydroxymethyl)-3(R),4(R)-dihydroxypyrrolidine. Obtention, Symmetry, and Liquid State Conformation
Marie-Thérèse Martin and Chiristphe Morin*
*Laboratoire de Chimie Appliquée aux Corps Organisés, Muséum National d’Histoire Naturelle, 63, rue de Buffpn, 75231 Paris Cedex 5, France
Abstract
A chiral polyhydroxylated pyrrolidine bearing a C2-axis of symmetry has been obtained. Full 1H nmr assignments could be made allowing determination of 34T as the liquid state conformation.
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■ Total Synthesis of Nuclea Alkaloid Naucleficine
Takeaki Naito, Etsuko Doi, Okiko Miyata, and Ichiya Ninomiya*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
The first total synthesis of naucleficine (1), an alkaloid of Nauclea officinalis, was achieved according to the route involving enamide photocyclization.
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■ Bridgehead Nitrogen Heterocycles. Synthesis of Methanoazepines Fused with Tetrazole, 1,2,4-Triazole and 1,2,4-Triazine
Shin-ichi Nagai, Naoki Kato, Taisei Ueda, Noriichi Oda, and Jinsaku Sakakibara*
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
Cyclohexa- (5a) and cycloheptatriazine (5b) were synthesized from the corresponding pyrazoles (3a-b). Hydrazinolysis of 2-ethoxy-3-azabicyclo[3.2.1]octan-2-ene (7c) gave 2-hydrazino-3-azabicyclo[3.2.1]octan-2-ene (7d) which readily underwent ring closure with nitrous acid, triethyl orthoformate and ethyl pyruvate to afford tetrazolo[1,5-a]azepine (8), 1,2,4-triazolo[4,3-a]azepine (9) and 1,2,4-triazino[4,3-a]azepine (10).
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■ Studies on the Chemical Transformation of Rotenoids. I. Ring Transformation of (-)-(6aS,12aS,2R)-Rotenone into Benzopyrano[3,4-c]pyrazoles
Shin-ichi Nagai, Teppei Akiyama, Taisei Ueda, Noriichi Oda, and Jinsaku Sakakibara*
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
Rotenone (1) underwent the ring transformation into 3-substituted 1-(2-methylethenyl-4-hydroxy-2,3-dihydrobenzofuran-5-yl)-7,8-dimethoxy-1,9b,2,3,3a,4-hexahydro-[1]benzopyrano[3,4-c]pyrazol-1-enes (4a-e) when treated with hydrazines in the strong basic medium. The stereochemistry of the products was established by 1H-NMR spectra confirming the cis B/C fusion.
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■ Photochemical Transformation of 2-Naphthyl-1,2-benzisothiazolinones
Nobumasa Kamigata,* Hirokazu Iizuka, and Michio Kobayashi
*Department of Chemistry, Faculty of Science, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan
Abstract
Photochemical reaction of 2-naphthyl-1,2-benzisothiazol-3(2H)-ones in benzene under argon gives ring-expansion isomer, benzonaphthothiazepinone, probably via homolytic cleavage of the S-N bond and intramolecular recombination of the biradical, followed by the hydrogen shift to regeneration of an aromatic ring.
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■ Acidic Transformation of Sesamolin, the Sesami-oil Constituent, into an Antioxidant Bisepoxylignan, Sesaminol
Yasuko Fukuda,* Minoru Isobe, Masayasu Nagata, Toshihiko Owaea, and Mitsuo Namiki
*Ichimura Gakuen Junior College, Uchikubo 61, Inuyama, Aichi 484- , Japan
Abstract
Intermolecular transformation of sesamolin(1) was proved to give sesaminol(2) during the industrial bleaching process of unroasted sesame seed oil. The mechanistic proof was demonstrated by a model experiment in organic solvents in the presence of acids and by a scrambling experiment under the model condition using m-cresol as a competitor.
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■ A Novel and Facile Synthesis of Pyrrolo[2,3-d]pyrimidines
Tsuneo Itoh,* Ikuko Fujii, Yasuo Tomii, Hisako Nishimura, Haruo Ogura, Yoshihisa Mizuno, Norio Kawahara, and Takako Shimamori
*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
A novel two-step procedure for preparation of pyrrolo[2,3-d]pyrimidines is reported.
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■ Novel Routes to Branchd-chain and Amino-sugars from Levoglucosenone, a Chiral Synthon Available from Cellulose. Structural Determination at Quaternary Carbon Atom by X-Ray Diffraction
Yvonne Gelas-Mialhe, Jacques Gelas,* Danielle Avenel, Rachid Brahmi, and Hélène Gillier-Pandraud
*Ecole National Supérieure de Chimie de Clermont-Ferrand, BP45, 63170 Aubière, France
Abstract
Structural modifications of levoglucosenone, a chiral bicyclic enone available from cellulose, afford a novel access to branched-chain and amino-sugars: methyl, hydroxymethyl and aminomethyl derivatives at position 2. Assignment of the absolute configuration at the quaternary carbon atom has been deduced from X-ray crystallographic data.
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■ Activated Nitriles in Heterocyclic Synthesis: A New Approach for the Synthesis of Pyran Derivatives
Nadia S. Ibrahim*
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
The reacrion of cinnamonitriles with acetylacetone and ethyl acetoacetate is reported. Several new polyfunctional pyrans could be prepared. Spectral data of the synthesised products is reported.
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■ Synthesis of 5-Fluoro-3-(2-tetrahydrofuryl)-6-vinyluracil. Design of a 5-FU-Derivative with Extended Conjugation
Gerrit-Jan Koomen, Hilka Wolschrijn, John B. M. van Rhijn, Martin J. Wanner, and Upendra K. Pandit*
*Organic Chemistry Department, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
Synthesis of a 6-vinyl-5-fluorouracil dervative is described.
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■ Praziquantel Analogues. I. New and Short Synthesis of 2-Acyl-4-oxo-1,2,3,4,6,7,12,12b-octahydropyrazino[1’,2’:1,2]pyrido[3,4-b]indoles
Nativitat Vallas, Víctor M. Segarra, and Joan Bosch*
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
A series of potential anthelmintic 2-acyl-4-oxo-1,2,3,4,6,7,12,12b-octahydropyrazino[1’,2’: 1,2]pyrido[3,4-b]indoles has been synthesized in high yield by Pictet-Spengler reaction between tryptamine and the appropriate N-acyl-N-(2,2-diethoxyethyl)glycine ethyl ester.
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■ Thio-Claisen Rearrangement of Cyclic S-Allylthioimidates
Hiroki Takahata, Yasunori Banba, Mayumi Mozumi, and TakaoYamazaki*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
Palladium(II)-catalyzed or non-catalyzed thio-Claisen rearrangement of cyclic S-allylthioimidates is described.
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■ Synthesis of the First Monosubstituted 1,2,4-Triazine Di-N-oxide. 13C NMR of 1,2,4-Triazine N-Oxides and Use of Hydrogen/Deuterium Isotope Shifts for the Assignments of Some Dihydro-1,2,4-triazine Tautomers
Misa V. Jovanovic*
*Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75275-0314, U.S.A.
Abstract
3-Amino-1,2,4-triazine 2,4-dioxide (4) was prepared by oxidation of 3-amino-1,2,4-triazine 2-oxide (3) with hydrogen peroxide in polyphosphoric acid, the first 1,2,4-triazine 2,4-dioxide ever reported. Same starting material gave ring contracted products as well as ring C-oxidation under a variety of reaction conditions employed in the attempted synthesis of the title compound (4). 13C nmr proved to be a method of choice for structural assignments of isomeric N-oxides. H/D isotope shifts unequivocally established the structures of compounds which could conceivably exist as several tautomers.
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■ Isoindolo[2,1-b]isoquinolinium Bromide Previously Described as Isoquinolylbenzoic Acid Bromide
Jürgen Dusemund* and Eckhard Kröger
*Institut fur Organische Chemie, Freien Universität Berlin, Takustrasse 3, D-14195 Berlin, Germany
Abstract
Treatment of 3 with bromine in chloroform affords the isoindolo[2,1-b]isoquinolinium salt 5a and not the 2-(3-isoquinolyl)-benzoyl bromide 4a. Compound 5a was also obtained from 4c and thionyl bromide. Reactions of 5a with alcohols and acetone led to 6a-c.
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■ Facile Synthesis of Styrylquinuclidines
Fiore J. Ricciardi* and Peter H. Doukas
*Department of Medical Chemistry, School of Pharmacy, Temple University, 3307 North Broad Street, Philadelphia, Pennsylvania 19140, U.S.A.
Abstract
3- and 2-Quinuclidinecarboxaldehydes, 3 and 12, were prepared by Wittig reaction and DIBAH reduction respectively. These aldehydes were used to prepare the corresponding 3- and 2-styrylquinuclidines. 4-7 and 13-16, via Wittig reactions.
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■ Base Catalysed Reaction of 2-Cyanomethyl-1,3-banzothiazole with Benzofuroxanes
Harsha Narayan Borah and Jagir Singh Sandhu*
*Division of Natural Products Chemistry, Regional Reseach Labratory (CSIR), Jorhat-6, Assam, India
Abstract
2-Cyanomethyl-1,3-benzothiazole (2) reacts with benzofuroxanes (1) to give quinoxaline N,N’-dioxides (3) in good yields.
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■ Synthesis and Properties of Some S-Derivatives of 1-Benzyl- and 1-(2-Pyridylmethyl)-5-substituted 2-Mercaptoimidasoles
Ricardo Bossio,* Stefano Marcaccini, and Roberto Pepino
*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e lolo Applicazioni, c/o Dipartimento di Chimica Organica "Ugo Schiff", Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
The synthesis of imidazol-2-ylthio derivatives IIa-d by reacting 1-benzyl and 1-(2-pyridylmethyl)-5-substituted 2-mercaptoimidazoles IIIa-d with chloroacetic acid is described. The interesting imidazol-2-ylthio derivatives Va,b,d and VI were obtained on heating IIa-d with acetic anhydride. The reaction between IIIa and 2-chloronicotinic acid chloride was also studied. The structures of all of the compounds were determined by ir and 1H-nmr spectroscopy. Compounds Vb and Vd were also obtained by unequivocal synthesis to support our interpretation.
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■ Novel Syntheses of Fused-imidazoles III. Simplified Construction of the Imidazo[2,1-b]thiazoline System
Ivan Lantos* and Michael McGuire
*Chemical Reserch and Development, Smith Kline and French Laboratories, Philadelphia, PA 19101, U.S.A.
Abstract
A simple, convenient synthesis of 5-aminoimidazo[2,1-b]thiazolines is described, based on the condensation of aminothiazoline with aryl carboxaldehydes in the presence of potassium cyanide.
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■ Synthesis of 3,7-Dihydro-4H-pyrrolo[2,3-d]pyrimidin-4-ones
Anker Jørgensen*
*Department of Chemistry, Odense University, Campusvej 55 DK-5230 Odense M., Denmark
Abstract
A series of 9 new 3-aryl-3,7-dihydro-2,5,6-trimethyl-7-phenylmethyl-4H-pyrrolo[2,3-d]pyrimidin-4-ones 2a-i were prepared in 44-66% yields by heating methyl 2-acetamido-4,5-dimethyl-1-phenylmethyl-1H-pyrrolo-3-carboxylate 1 in a mixture of phosphorus pentoxide, triethylamine hydrochloride and an appropriate aniline at 150°C for 25-45 min. Similar reactions of 1 with primary alkylamines can lead to formation of 7-phenylmethyl-2,5,6-trimethyl-pyrrolo[2,3-d][1,3]oxazin-4(7H)-one 3 and 3-alkyl-3,7-dihydro-2,5,6-trimethyl-7-phenylmethyl-4H-pyrrolo[2,3-d]pyrimidin-4-one 7.
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■ Stereospecific Synthesis of Optically Active 2-Phenylsulfonyl-3-(1-hydroxyethyl)-4-azetidinone: A Precursor of Thienamycin-type Carbapenems
Masao Shiozaki,* Tetsuo Hiraoka, Hiroaki Yanagisawa, Hiroshi Maruyama, Naoyuki Kishi, and Osamu Oda
*Chemical Research Laboratories and Analytical & Metabolic Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
Stereospecific synthesis of optically active (2R,3S)-2-phenylsulfonyl-3-(1R-hydroxyethyl)-4-azetidinone from L-threonine is described. This compound is one of the key compounds for the synthesis of the thienamycin-type carbapenems.
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■ Reactivity of Heterocyclic Ambident S···N Anions in SRN1 Substitution Reactions
Monique Meyer, André Samat, and Michel Chanon*
*U.A. 126 C.N.R.S., Laboratoire de Chimie Inorganique, Université d‘Aix-Marseille III, rue H. Poincaré, 13397 Marseille Cedex 13, France
Abstract
Ambident anions of 2-mercaptoazoles react, under photo-stimulation conditions, with α,p-dinitrocumene according to an SRN1 mechanism (short chain) leading to S-alkylated compounds in agreement with a kinetically controlled reaction. Regioselectivity is governed by nucleophilicity and not by the basicity of the heteroatom. The N-alkylation observed in the case of 2-mercaptoimidazole proceeds from a new photochemical rearrangement with homolytic cleavage of the C-S bond followed by the recombination of the α,p-dinitrocumyl radical with the ambident heterocyclic radicals.
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■ Synthesis of (5-Hydroxy-2-pyridyl)glycine. Oxazole Formation in the Bucherer-Bergs Reaction. Atudies on Amino Acids VI
Claus Herdeis* and Rolf Gebhard
*Institut für Pharmazie und Lebensmittelchemie, Universität München, Sophienstraße 10, D-80333 München, Germany
Abstract
(5-Hydroxy-2-pyridyl)glycine (1) has been prepared. Bucherer-Bergs reaction of (5-benzyloxy-2-pyridyl)carbaldehyde (6) furnished the oxazole 7b and not the hydantoin 9. Hydrolysis of the oxazole 7b gave the sodium salt of the hydantoic acid 11. After acidic workup the urea derivative 12 was obtained. This demonstrates that the oxazole 7b and not the former postulated isomer 5a is the product of 2-pyridylcarbaldehyde derivatives in the Bucherer-Bergs reaction.