Regular Issue

Vol. 38, No. 7, 1994

27 data found. 1 - 27 listed
Communication | Regular issue | Vol 38, No. 7, 1994, pp. 1449 - 1452
Published online:
DOI: 10.3987/COM-93-6665
Novel Efficient Synthesis and Structural Analysis of Furanose-Type Phosphono Sugars

Mitsuji Yamashita,* Akihiro Yabui, Tatsuo Oshikawa, Tadashi Hanaya, and Hiroshi Yamamoto

*Department of Applied Chemistry, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu 432-8561, Shizuoka, Japan


Reaction of 2-benzyloxymethyl-1-methoxy-3-phospholene 1-oxide with mCPBA afforded 3,4-epoxyphospholane derivatives, whose isomerized allylic alcohols were cis-dihydroxylated by osmium(VIII) oxide-catalyzed oxidation to give ribo-, arabino-, xylo-, and lyxo-furanose-type phosphono sugars. The nmr data suggest a twist conformation.

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Communication | Regular issue | Vol 38, No. 7, 1994, pp. 1453 - 1457
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DOI: 10.3987/COM-94-6715
Formation of a Strained Triazapentalenoindene Skeleton via the Rearrangement of 2,3-Dihydro-7-nitro-1H-Imidazo[2,1-a]phthalazin-4-ium-6-olate Effected by Dichloroacetic Anhydride

Mónika Fuxreiter, Antal Csámpai,* and János Császár

*Department of Organic Chemistry, Eötvös Loránd University Budapest, H-1518 Budapest 112, P.O.Box 32, Hungary


On treatment with dichloroacetic anhydride 2,3-dihydro-7-nitro-1H-imidazo[2,1-a]phthalazin-4-ium-6-olate (5) underwent a backbone rearrangement leading to isoindole derivative (12), which represents a new strained ring system with three condensed five-membered heterocycles. The structure of its stable 3-deacylated form, 3,3a,5a-triaza-1,1-dichloro-1,2,3,3a,4,5,6,6a-octahydro-7-nitropentaleno[3a,3-a]indene-2,6-dione (13) was evidenced by ir, ms, nmr, and X-ray methods.

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Communication | Regular issue | Vol 38, No. 7, 1994, pp. 1459 - 1464
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DOI: 10.3987/COM-94-6716
Addition of Thiols to Acetylene Substituted Indoles

Géza Galambos,* Pál Csókási, Csaba Szántay, Jr., Gábor Gzira, and Csaba Szántay*

*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, P.O.Box 17, Hungary


The preparation of synthetically useful thio enol ether substituted indoles is described.

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Communication | Regular issue | Vol 38, No. 7, 1994, pp. 1465 - 1469
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DOI: 10.3987/COM-94-6724
Two Distinct Dynamic Processes in Non-Planar Tetrabenzoporphyrin

Ru-Jen Cheng,* Yu-Ren Chen, and Chun-Chang Chen

*Department of Chemistry, National Chung-Hsing University, Taichung, 402, Taiwan, R.O.C.


Two distinct dynamic processes including N-H tautomerism and porphyrin ring inversion have been establised through variable-temperature 1H nmr spectroscopy and isotope effect analysis in meso-tetraphenyltetrabenzoporphyrin consistent with the non-planar nature of the macrocycle from previous structural result.

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Communication | Regular issue | Vol 38, No. 7, 1994, pp. 1471 - 1474
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DOI: 10.3987/COM-94-6728
Pseudothiacrown and Pseudothiolariat Ethers for Double Recognition Systems toward Copper (I) and Silver (I)

Tatsuya Nabeshima,* Ikuo Yosejima, and Yumihiko Yano

*Department of Chemistry, Faculty of Engineering, Gunma University, 1-5-1 Tenjin-cho, Kiryu 376-8515, Japan


Linear and branched polythioethers with bipyridine moieties at the termini bind Cu(I) to afford pseudothiacrown and pseudothiolariat ethers by conformational change of the polyether chain, and the pseudocrowns extract Ag(I) selectively.

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Communication | Regular issue | Vol 38, No. 7, 1994, pp. 1475 - 1478
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DOI: 10.3987/COM-94-6737
Diepoxymontin, a Novel Acetogenin from Annona montana

Yang-Chang Wu,* Fang-Rong Chang, Keh-Shaw Chen, Sz-Chi Liang, and Maw-Rong Lee

*Graduate Institute of Natural Products, Kaohsiung Medical College, 100 Shih Chuen 1st Rd., Kaohsiung 80708 Taiwan, R.O.C.


Tandem mass spectrometry has been used to elucidate the structure of diepoxide α,β- unsaturated -γ-lactonic acetogenin, diepoxymontin, which is the first example of acetogenin having an adjacent epoxides in place of tetrahydrofuran moiety.

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Communication | Regular issue | Vol 38, No. 7, 1994, pp. 1479 - 1482
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DOI: 10.3987/COM-94-6738
Syntheses of (±)-4-Amino-1,3,4,5-tetrahydrobenz[cd]indole-4-carboxylic Acid, (±)-4-N,N-Dipropylamino-4-hydroxymethyl- and (±)-4-Propyloxy-1,3,4,5-tetrahydrobenz[cd]indole

Masanori Somei,* Naokatsu Aoki, and Kyoko Nakagawa

*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan


Simple syntheses of the title compounds are reported starting from indole-3-carboxaldehyde.

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Communication | Regular issue | Vol 38, No. 7, 1994, pp. 1483 - 1486
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DOI: 10.3987/COM-94-6743
Highly Asymmetric Induction in the Diels-Alder Reaction of 3-Alkoxycarbonyl-substituted

Katsuo Ohkata, Tomotaka Kubo, Keiko Miyamoto, Makiko Ono, Junko Yamamoto, and Kin-ya Akiba*

*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan


The asymmetric Diels-Alder reactions of 3-alkoxycarbonyl-substituted chromones (1c) with 2,3-dimethyl- and 2-methyl-1,3-butadienes in the presence of ZnCl2 at ambient temperature afforded the adducts (3c and 4b) with high diastereofacial selectivity (>98%) in high yield.

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Communication | Regular issue | Vol 38, No. 7, 1994, pp. 1487 - 1490
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DOI: 10.3987/COM-94-6744
Regioselective Prenylation of Phenols by Palladium Catalyst: Syntheses of Prenylphenols and Chromans

Masao Tsukayama,* Makoto Kikuchi, and Yasuhiko Kawamura

*Department of Chemical Science and Technology, Faculty of Engineering, University of Tokushima, Minamijosanjima-cho, Tokushima 770-8506, Japan


The palladium-catalyzed coupling reaction of iodophenols (1) with 2-methyl-3-butyn-2-ol gave alkynylphenols (2). Catalytic hydrogenation of 2 over Raney nickel and the subsequent dehydration of the resultant alkylphenols (3) gave regioselectively the desired prenylphenols (4). Dehydration of alkylphenols (3f-h) gave chromans (7).

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Communication | Regular issue | Vol 38, No. 7, 1994, pp. 1491 - 1496
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DOI: 10.3987/COM-94-9754
Lewis Acid Promoted Tandem [4+2] Cycloaddition-Rearrangement Process — A Simple and Efficient Synthesis of Highly Functionalized Oxabicyclo[3.3.1]nonanes

Masahiro Toyota, Yoshihiro Wada, Youichi Nishikawa, Toshihiro Wada, and Keiichiro Fukumoto*

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


Catalytic Lewis acid promoted tandem [4+2]cycloaddition-rearrangement processes of the trienic esters (4), (8) and (9) are reported. The novel tandem reactions proceed under thermal (110 °C, aluminum catalyst) conditions and afford the highly functionalized oxabicycl[3.3.1]nonanes (5), (10) and (11), respectively.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1497 - 1506
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DOI: 10.3987/COM-93-6646
Novel Rearrangement of the Trioxane Ring System of the Antimalarial Arteether upon Treatment with Acid in an Aqueous Methanol Solvent System

John K. Baker* and Hsien Tao Chi

*Department of Medicinal Chemistry and the Research Institute of Pharmaceutical Sciences, School of Pharmacy, University of Mississippi, University, Mississippi 38677, U. S. A.


While arteether does not have a uv-chromophore, the treatment of arteether with a HCl, water, methanol system has been previously proposed as a method of generating a uv-chromophore upon which to base a quantitative analysis. The present study demonstrates that the originally proposed structure for the product was not correct and that the reaction is far more complex than originally proposed. It was found that the reaction yields 5 different α,β-unsaturated ketones (A-1, A-2, A-3, A-4, and A-5; whose structures are reported here for the first time) that have strong uv chromophores and 4 additional products (new compounds B-1 and B-2; previously reported α-artemether and β-artemether) that do not have any significant chromophores. The structure and stereochemistry of these novel reaction products were determined using thermospray hplc/ms, 1H-nmr, 13C-nmr, and two-dimensional nmr methods.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1507 - 1518
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DOI: 10.3987/COM-94-6675
Intramolecular Diels-Alder Reaction of Furans with Allenyl Ethers: High Effect of the Chain Length on the Structure and Reactivity of the Cycloadducts

Hsien-Jen Wu,* Shie-Hsiung Lin, and Chu-Chung Lin

*Department of Applied Chemistry, National Chiao Tung University, Hsinchu, 30050, Taiwan, R.O.C.


The structure and reactivity of the cycloadducts of the title reaction were found to be highly dependent on the chain length between the furan diene and the allenyl ether dienophile. Reaction of the propargyl ether (2) with t-BuOK in t-BuOH at 85 °C for 3 h gave a mixture of the cycloadducts (3) and (4) in 90% yield, which were transferred to the benzo derivatives (5), (6) and (7). Treatment of the propargyl ether (8) with t-BuOK in t-BuOH at 85 °C for 5 h gave the products (9) and (10) in a ratio of 8:1 in 65% yield, no detectable amount of the cycloadduct (8b) was obtained. Refluxing of the propargyl ether (13) with t-BuOK in t-BuOH at 85 °C for 4 h gave the allenyl ether (14). Heating 14 in DMSO at 150 °C for 12 h still did not give 15.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1519 - 1526
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DOI: 10.3987/COM-94-6702
Synthesis of 4H-Pyrrolo[2,1-c][1,4]benzothiazines and N-Methyl-1,3,4,5-tetrahydro-2H-3-benzazepin-2-ones

Huey-Min Wang, Meng-Chiao Lin, and Ling-Ching Chen*

*Graduate Institute of Pharmaceutical Sciences, Kaohsiung Medical College, 100 Shih Chen 1st Rd., Kaohsiung 80708, Taiwan, R.O.C.


Pummerer-type reaction was carried out with α-acyl sulfides and phenyliodine (III) bis(trifluoroacetate) instead of a-acyl sulfoxides to prepare 4H-pyrrolo[2,1-c][1,4]benzothiazines and N-methyl-1,3,4,5-tetrahydro-2H-3-benzazepin-2-ones.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1527 - 1532
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DOI: 10.3987/COM-94-9706
Compared Reactivity of 3-, 5-, 6-, and 8-Aminoimidazo[1,2-a]pyridines in Combes Reaction: Access to Imidazonaphthyridines and Dipyrido[1,2-a:3‘,2‘-d]imidazole

Yves Blache, Alain Gueiffier,* Olivier Chavignon, Henry Viols, Jean Claude Teulade, and Jean Pierre Chapat

*Laboratoire de Chimie Organique Pharmaceutique, URA-CNRS, Faculté de Pharamcie, Université Montpellier I, 15 Avenue Charles Flahault, 34060 Montpellier, France


The synthesis of imidazo[1,2-a][1,8]naphthyridines and dipyrido[1,2-a:3‘,2‘-d]imidazole by treatment of aminoimidazo[1,2-a]pyridines following the Combes procedure is described.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1533 - 1540
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DOI: 10.3987/COM-94-6714
Stereoselective Synthesis of (±)-5-(1-Benzyloxyethyl)-6-(2-tert-Butyldiphenyloxyethyl)-2-piperidinone: A Formal Total Synthesis of Thienamycin

Shinji Tanimori,* Toshio Niki, Mingqi He, and Mitsuru Nakayama

*Department of Agricultural Chemistry, College of Agriculture, University of Osaka Prefecture, Sakai, Osaka 593-8531, Japan


(±)-5-(1-Benzyloxyethyl)-6-(2-tert-butyldiphenyllsilyloxyethyl)-2-piperidinone (2), a synthetic intermediate for thienamycin (1), has been synthesized stereoselectively in nine steps from methyl 2-oxo-6-endo-methylbicyclo[3.1.0]hexane-1-carboxylate (3) using Lewis acid catalyzed homoconjugate addition of benzyl alcohol to 3 as a key step.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1541 - 1549
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DOI: 10.3987/COM-94-6717
Synthesis of Vinca Alkaloids and Related Compounds. Part LXIX. Synthesis of 15-Substituted Eburnane Derivatives

István Moldvai, Csaba Szántay Jr, and Csaba Szántay*

*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, P.O.Box 17, Hungary


Starting from 15α-chlorovincamine (1), 15β-hydroxy-14-epivincamine (2a) and its 14-O-alkyl derivatives (2b, 2c) have been prepared via 14,15β-epoxyvincamine (3). The latter compound was transformed into (+)-15-oxodihydroeburnamine (6). The structures of 2-3 were established via detailed nmr investigations.a

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1551 - 1571
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DOI: 10.3987/COM-94-6720
Synthesis and Biological Activities of New HMG-CoA Synthase Inhibitors: 2-Oxetanones with a Side Chain Containing Biphenyl, Terphenyl or Phenylpyridine

Hirokazu Hashizume,* Hajime Ito, Naoaki Kanaya, Hajime Nagashima, Hiroyuki Usui, Reiko Oshima, Munefumi Kanao, Hiroshi Tomoda, Toshiaki Sunazuka, Tohru Nagamitsu, Hidetoshi Kumagai, and Satoshi Omura

*Fuji Chemical Industries, Ltd., 530 Chokeiji, Takaoka, Toyama 933- 0951, Japan


A series of 1233A analogs containing biphenylyl, terphenylyl or phenylpyridyl groups in their side chain were synthesized and tested for the inhibitory activities against 3-hydroxy-3-methylglutaryl coenzyme A (HMG-CoA) synthase and inhibition for the cholesterol biosynthesis in the mouse liver. The compounds with an oxetane, cyclobutanone or g-butyrolactone ring as isosters of a 2-oxetanone ring were entirely inactive. Among synthetic analogs, anti-4-[3-[2-(5-isopropyl-2-pyridyl)ethyl]phenyl]ethyl]-3-hydroxymethyl-2-oxetanone (10b) was most active in vitro. The structure-activity relationships on the transformations of 2-oxetanone and its side chain were obtained.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1573 - 1580
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DOI: 10.3987/COM-94-6721
A Synthesis of 7-Substituted 1H-Pyrano[4,3-b]quinoline Derivatives

Yutaka Azuma,* Atsuko Sato, and Mieko Morone

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


The reaction of 4-chloro-3-ethynyl-6-methyl-2H-pyran-2-one (2) with aniline derivatives having a electron-donating group at the 3-position in EtOH gives 7-substituted 1H-pyrano[4,3-b]quinolin-1-one derivatives (3).

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1581 - 1588
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DOI: 10.3987/COM-94-6722
An Alternative Synthesis of 2-Benzyloxy-6-hydroxymethyl-3-isobutyl-5-methoxypyrazine 4-Oxide, a Key Intermediate for Synthesis of OPC-15161

Satoshi Hashizume, Atsunori Sano, and Masahisa Oka*

*Tokyo Research Laboratories, Wako Pure Chemical Ind., Ltd., 1633 Matoba, Kawagoe, Saitama 350-1101, Japan


2-Benzyloxy-6-hydroxymethyl-3-isobutyl-5-methoxypyrazine 4-oxide (5e), a key intermediate for synthesis of OPC-15161 (1a) having an inhibitory activity against superoxide anion generation, was prepared from 5-amino-2-benzyloxy-3-isobuyl-6-methoxycarbonylpyrazine 4-oxide (5b) by 3-step reaction.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1589 - 1594
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DOI: 10.3987/COM-94-6723
An Enantioselective Synthesis of (+)-Indolizidine 195B

Robert Bloch,* Cécile Brillet-Fernandez, Petra Kühn, and Gérard Mandville

*Laboratoire des Carbocycles, Associé au CNRS, Institut de Chimie Moleculaire d‘Orsay, Bat. 420, Université de Paris-Sud , 91405 Orsay Cedex, France


A versatile enantioselective synthesis of the dendrobatid alkaloid (+)-indolizidine 195B is described, starting from the readily available lactol (1).

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1595 - 1600
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DOI: 10.3987/COM-94-6727
Diels-Alder Reaction of 1,2,3-Triazine with Aldehyde Enamine

Junko Koyama,* Tamaki Ogura, and Kiyoshi Tagahara

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


The Diels-Alder reaction of 4-methyl-1,2,3-triazine with several aldehyde enamines was carried out to afford 2,5-disubstituted pyridines. As an application of this method, we accomplished the synthesis of alkaloid, fusaric acid.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1601 - 1607
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DOI: 10.3987/COM-94-6731
Intramolecular Nitrile Imine Cycloadditions to the Acetylenic Bond in the Synthesis of Pyrazolo[1,5-a][4,1]benzoxazepines and Pyrazolo[1,5-a][5,1]benzoxazocines

Gianluigi Broggini, Luisa Garanti, Giorgio Molteni, and Gaetano Zecchi*

*Dipartimento di Chimica Organicane Industriale , dell‘Universitè , Via Golgi 19, I-20133 Milano, Italy


The intramolecular nitrile imine cycloaddition methodology has been applied to the construction of the title heterocyclic systems. The efficiency of this synthetic approach is rather variable, being markedly dependent on the kind of substitution at the acetylenic bond.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1609 - 1618
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DOI: 10.3987/COM-94-6733
Hydroisoquinoline Ring Construction via the Diels-Alder Reaction of Arecolone-derived Enole Silyl Ethers

Jian Ma, Masako Nakagawa,* Yasuhiro Torisawa, and Tohru Hino

*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan


Diels-Alder reaction of the arecolone-derived siloxydienes (7, 14) was described. the hexahydroisoquinoline derivatives (21, 22, 23) were prepared from the reaction of 14 with methyl propiolate followed by Michael addition to the amido acrylates (18, 19, 20).

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1619 - 1625
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DOI: 10.3987/COM-94-6736
Protonation and Sulfonation of Gramine in Strong Sulfuric Acid

Tine M. Fatum, Uffe Anthoni, Carsten Christophersen,* and Per H. Nielsen

*Marine Chemistry Section, The H. C. Ørsted Institute, University of Copenhagen, Universitersparken 5, DK-2100 Copenhagen, Denmark


Gramine (3-dimethylaminomethylindole) when treated with concentrated sulfuric acid at room temperature, after protonation at the dimethylamino group and at position 3, was sulfonated at the aromatic positions. Initial sulfonation in either the 5- or 6-position was succeeded by introduction of a second sulfonic acid group giving a mixture of gramine-4,6-disulfonic acid, gramine-5,7-disulfonic acid and gramine-2,6- or gramine-2,5-disulfonic acid.

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1627 - 1639
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DOI: 10.3987/COM-94-6740
Ketene Addition on Thienoanellated Thiazines and Thiazepines with Subsequent Ring Enlargement Reaction to Thieno[2,3-b][1,4]thiazocines and Thieno[2,3-b][1,4]thiazonines

Thomas Erker

*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Straße 10, A-1090 Vienna, Austria


Reaction of alkylthiothieno[2,3-b][1,4]thiazine derivatives or alkylthiothieno[2,3-b][1,4]thiazepine derivatives (4, 5, 12, 16, and 24) with substituted acetyl chlorides in the presence of triethylamine led to azeto[1,2-d]thieno[2,3-d][1,4]thiazine derivatives and azeto[1,2-d]thieno[2,3-b][1,4]thiazepine derivatives. Some of them were ring opened by treatment with trifluoroacetic acid to give the thieno[2,3-b][1,4]thiazocine derivatives (27 - 30) and the thieno[2,3-b][1,4]thiazonine derivative (32), respectively. 6-Ethyl-1H-thieno[2,3-b][1,4]thiazine-2(3H)-thione (13), after reaction with α-chlorophenylacetyl chloride and triethylamine, afforded the thiazolo[2,3-b][1,4]thiazine derivative (34).

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Paper | Regular issue | Vol 38, No. 7, 1994, pp. 1641 - 1650
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DOI: 10.3987/COM-94-6741
Synthesis of N-Substituted Imidoethyl-3-aminomethyl-2,3-dihydro-1,4-dioxino[2,3-b]pyridines

Abdelhakim Benarab, Corinne Comoy, and Gérald Guillaumet*

*Laboratoire de Chimie Bioorganique et Analytique, URA-CNRS N° 499, Université d‘Orléans, BP 6759, Rue de Chartres, 45067 Orleans Cedex 2, France


The multistep synthesis of N-substituted imidoethyl-3-aminomethyl-2,3-dihydro-1,4-dioxino[2,3-b]pyridines using as a final step the Mitsunobu reaction between aliphatic alcohols and imides is described.

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Review | Regular issue | Vol 38, No. 7, 1994, pp. 1651 - 1664
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DOI: 10.3987/REV-93-SR21
Synthesis of Nitro Derivatives of Triazoles

Ou Yuxiang,* Chen Boren, Li Jiarong, Dong Shuan, Li Jianjun, and Jia Huiping

*Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China


This paper reviews the synthesis routes of nitro derivatives of triazoles with emphases on those used as energetic materials.

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27 data found. 1 - 27 listed