HETEROCYCLES

■ Profile and Scientific Contributions of Doctor Ken’ichi Takeda

Wataru Nagata*

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

■ Novel Base-modified Nucleosides

Herman P. M. Thiellier, Gerrit-Jan Koomen, and Upendra K. Pandit*

*Laboratory of Organic Chemistry, University of Amsterdam, Nieuwe Achtergracht 129,1018 WS Amsterdam, The Netherlands

Abstract

Addition of halocarbenes to uridine derivatives leads to the formation of C₅-C₆ adducts, which upon heating yield novel 1,3-diazepine nucleosides.

■ Propellanes. XXXV. Attempted Preparation of a [5]Prismane Derivative from Diels-Alder Adducts of Tetraenic Propellanes

Zmira Bernstein and David Ginsburg*

*Department of Chemistry, Israel Institute of Technology, Haifa 32000, Israel

Abstract

Thermolysis of a suitable azopropellane did not give a prismane derivative.

■ The Reaction of ω-Vinyl Primary Disulfide with Halogen

Hiroyuki Morita and Shigeru Oae*

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

Abstract

Several olefinic disulfides were prepared by ordinary methods and allowed to react with halogenating reagents. The products obtained in this reaction were two types of β-halothiacycloalkanes as one would expect, ie., α-halomethylthiacycloalkane and β-halothiacycloalkane, which are not readily prepared by usual procedures.

■ Photolysis of Alkenyl Disulfide

Hiroyuki Morita and Shigeru Oae*

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

Abstract

Several alkenyl disulfides were prepared and the products of the photolysis were determined. The main products in this reaction were not thiacycloalkanes but unexpected 3-thiacycloalkanylalkenyl sulfides.

■ Peshawarine, an Unusual Isoquinoline Alkaloid

Maurice Shamma,* Alan S. Rothenberg, Gamini S. Jayatilake, and S. Fazal Hussain

*Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, U.S.A.

Abstract

The alkaloid peshawarine (1), found in Hypecoum parviflorum, is a member of the new isoquinolinobenzopyran group of isoquinoline alkaloids. The analog 11 was synthesized from (±)-canadaline (6) derived from berberine.

■ A Total Synthesis of (±)-Fendleridine

Yasushi Honma, Takeshi Ohnuma, and Yoshio Ban*

*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan

Abstract

The oxidative cyclization of the aminoalcohol (7) with mercuric acetate gave (±)-fendleridine (1a). In this synthetic course, the reduction product of N-tosyl vinylogous amide (3) with lithium aluminum hydride was now further purified, and the former assignment of the structure (4) was revised to be 5, based upon the chemical and spectroscopic evidences.

■ Photosensitized Oxygenations of Tryptophan Derivatives: Evidence for Involvement of Singlet Oxygen

Isao Saito, Yoshiyuki Takahashi, Mitsuru Imuta, Seiichi Matsugo, Hiroyuki Kaguchi, and Teruo Matsuura*

*Department of Synthetic Chemistry, Faculty of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyou-ku, Kyoto 606-8501, Japan

Abstract

Photosensitized oxygenations and microwave dischargegenerated singlet-oxygen reactions of tryptophan derivatives were investigated.

■ Studies on the Synthesis of Bisindole Alkaloids. V. The Hydrazine Method

James P. Kutney,* Edwin Jahngen, and Tetsuya Okutani

*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5, Canada

Abstract

The hydrazine method, which involves the removal of the C_18’ ester group in a series of synthetic bisindole derivatives by means of anhydrous hydrazine, can be employed for the synthesis of a family of bisindole derivatives possessing natural stereochemistry at the important C_18’ position.

■ Totoal Synthesis of 11-Epicorynoline

Ichiya Ninomiya,* Okiko Yamamoto, and Takeaki Naito

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

Abstract

Treatment of the 11,12-dehydro derivatives (V and VI) of B/C-cis-benzo[c]phenanthridines with performic acid afforded all possible stereoisomers (IX, X, II,and XI) of the 11,12-dihydroxyamine, of which the 11β-isomers (IX and X) were successfully converted into 11-epicorynoline (III).

■ Photo-oxidation of 1-Methyl-3-oxido-5-phenylpyridinium

Julie Banerji, Nicholas Dennis, and Alan R. Katritzky*

*School of Chemical Sciences, University of East Anglia, Norwich, Northfolk NR4 7TJ, U.K.

Abstract

Dipolar peroxide intermediates of type III, IV are supported for the photo-oxidation of 3-oxidopyridiniums by the isolation of unsymmetrical dimer X.

■ Synthesis of Tetrahydro-5H-dibenz[b,d]azepin-6(7H)-one

Mohammed N. Samimi, Udo Kraatz, and Friedhelm Korte*

*Lehrstuhl für Makromolekulare Stoffe, Institut für Chemie , Technische Universität München, Lichtenbergstrasse 4, D-85747 Garching, Germany

Abstract

9,10-Dimethyl-7a,8,11,11a-tetrahydro-5H-dibenz[b,d]azepin-6(7H)-one is synthesized in six steps starting from o-nitrocinnamic acid.

■ Comstituents of Higher Fungi. Part VIII. Isolactarorufin, a Novel Tetracyclic Sesquiterpene Lactone from Lactarius Rufus

Wlodzimierz M. Daniewski,* Marian Kocór, and Svanté Thorén

*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland

Abstract

Lactarius rufus extracts yielded along with tricyclic lactarorufins a novel tetracyclic secquiterpene lactone with cyclopropane ring condensed with lsctone ring-isolactarorufin (1). Its structcre was established on the basis of chemical transfomations and full spectral analysis.

■ Preferential Removal of a Methylenedioxy Group from Optically Active Isoquinolines

Sidney Teiterl* and Jay P. O’Brien

*The Department of Chemistry Research, Hoffman-La Roghe Inc., Nutley, New Jersey 07110, U.S.A.

Abstract

The optically active dimethoxymethylenedioxy-substituted benzylisoquinoline (2a) and tetrahydroprotoberberine (3a) were O-demethylenated with boron trichloride followed by hydrogenolysis of the bistetrazoyl ether intermediate over Pd-C to afford, with retention of absolute configuration, (2d) and (3d), respctively. In contrast, hydrogenolysis of the dextrorotatory bistetrazoyl aporphine (4c) -a substrate that can readily dehydrogenate-gave the racemate of (4d).

■ A Simple Route to Indolizine-2-carboxylates. Cycloaddition Reactions of Pyridinium Arylsulphonylmethylides

Rudolph A. Abramovitch* and Suchet S. Mathur

*Department of Chemistry, University of Alabama, Box 870336, University, Tuscaloosa, Alabama 35478-0336, U.S.A.

Abstract

Pyridinium-p-toluenesulphonylmethylides react with maleic anhydride in the presence of alcohols to give indolizine-2-carboxylates in a process involving selective decarboxylation and aromatization, and with phenylcyanoacetylene to give 1-cyano-2-phenylindolizines.

■ Ring Expansion of 3-Substituted 1,2-Benzoisothiazole 1,1-Dioxides to 1,2-Benzothiazepine 1,1-Dioxides

Rudolph A. Abramovitch,* Kundalika M. More, Ichiro Shinkai, and Panayencheri C. Srinivasan

*Department of Chemistry, University of Alabama, Box 870336, University, Tuscaloosa, Alabama 35478-0336, U.S.A.

Abstract

3-Substituted 1,2-benzoisothiazole 1,1-dioxides undergo a [2+2] cycloaddition with 1-diethylaminopropyne followed by rinq expansion to give the very stable 5-substituted 3-diethylamino-4-methylbenzo-1,2-thiazepine 1,1-dioxides (2). These can, however, be cleaved with lithium aluminum hydride to O-styrylsulfonamides. The stability of the ring system 4 is discussed briefly.

■ Novel Synthesis of N-Alkylated Lactams

Edward Grochowski* and Teresa Boleslawska

*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland

Abstract

A novel synthesis of γ- and δ-lactams from hydroxy and olefinic nitriles was described. The mechanism of this double two steps alkylation is discussed.

■ Stereochemical and Hydrogenolysis Studies with Substituted Isoxazolidines

John Palmer, John L. Roberts, Peter S. Rutledge,* and Paul D. Woodgate

*Department of Chemistry, University of Auckland, Private Bag 92019, Auckland, New Zealand

Abstract

The use of ¹³C n.m.r. and ¹H - ¹³C decoupling to assign the chemical shifts to protons geminal to substituents at the 3,4 and 5 positions of a pair of stereoisomeric isoxazolidines allows determination of the ring stereochemistries. Catalytic hydrogenation of N-phenylisoxazolidines with a 5-methoxycarbonyl group leads readily to azolidin-2-ones, but C-N hydrogenolysis is not achieved if there is a dimethoxyphenyl substituent at the 3 position of the isoxazolidine.

■ The Condensation of Histamine with Carbonyl Compounds

Gerhard G. Hebermehl* and Wolfgang Ecsy

*Institut für Organische Chemie, Technische Hochschule Darmstadt, Petersenstrasse. 22 64287 Darmstadt, Germany

Abstract

Substances of the spinaceamine type, 4,5,6,7-tetrahydroimidazo[5,6-c]pyridines can be obtained, by a biogenetic type synthesis, from histamine and carbonyl compounds in a buffer solution at pH 7.2 with an optimum yield.

■ The Isomerization of Hydrogenated Adducts Obtained from 1,4-Phthalazinedione

Manuel Lora-Tamayo,* Pilar Navarro, Dolores Romero, and José Luis Soto

*President of the Centro Nacional de Química Orgánica, C. S. I. C., Juan de la Cierva 3 , E-28006 Madrid, Spain

Abstract

The hydrogenated adducts obtained from 1,4-phthalazinedione with 1-vinylcyclohexene I and 1-vinylcyclopentene III, are isomerized with concentrated sulfuric acid to give the spiro-compounds II and IV respectively by contraction of ring C.
This ring contraction also takes place in the hydrogenated adducts X, XII, XIV and XVI corresponding to 1,3-pentadiene, 2-methyl-1,3-pentadiene and 2,4-hexadiene derivatives and it does not occur in the hydrogenated adducts of isoprene and 2,3-dimethylbutadiene derivatives XVIII and XIX.
In all the cases we have studied, the isomerization takes place when of the two carbon atoms involved in the ring contraction, the adjacent to the nitrogen atom is substituted, being not necessary any substitution on the other carbon atom.
The mechanism of the reaction is discussed.

■ 1,3-Dipolar Cycloadditions of Carbonyl Ylides to Thiocarbonyl and Carbonyl Compounds

Rolf Huisgen* and Scarlett Sustmann

*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany

Abstract

α,β-Dicyanostilbene oxide at 120° undergoes electrocyclic ring opening to a carbonyl ylidc which can be trapped by cycloaddition to the CS double bond of O-methyl thiobenzoate, methyl dithiobenzoate and dimethyl trithiocarbonate to produce 1,3-oxathiolanes. The carbonyl ylide combines with diethyl mesoxalate to give a 1,3-dioxolane. The corresponding carbonyl ylide from α-cyanostilbene oxide affords a 1,3-dioxolane which suffers cycloreversion and renewed cycloadditon to give 2-phenyl-1,3-dioxolane-4,4,5,5-tetracarboxylic ester.

■ The Reactions of Carbonyl Ylides with Azodicarboxylic Esters

Helmut Hamberger, Rolf Huisgen,* Volker Markowski, and Scarlett Sustmann

*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany

Abstract

The carbonyl ylides, generated by thermal electrocyclic ring opening of 2,3-diaryl-2,3-dicyanooxiranes, combine with azodicarboxylic esters to give primary cycloadducts which eliminate aroyl cyanide and produce α-cyanoarylidenehydrazine-N^β,N^β-dicarboxylic esters. Whereas the dimethyl esters are thermostable, the diethyl esters undergo a fragrmentation to ethyl α-cyanoarylidenehydrazine-N^β-carboxylate besides ethylene and carbon dioxide.

■ Oxidative Transformation of Dihydrocoralyne to 6’-Acetylpapaveraldine

Jiro Imai and Yoshikazu Kondo*

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

Abstract

Dihydrocoralyne III, obtained by partial reduction of coralynium salts in 86% yield, was autoxidized in solution at pH 8 to phenolbetaine IV in quantitative yield. Treatment of IV with m-chloroperbenzoic acid gave 6’-acetylpapaveraldine in 65% yield. Irradiation of III in the presence of air gave V in quantitative yield. The oxidative cleavage of IV was satis- factorily explained via the oxaziridine intermediate.

■ A New Modification of Bischler-Napieralski Reaction for β-Arylethylisocynates and β-Arylethylurethans

Yoshisuke Tsuda,* Kimiaki Isobe, Jun Toda, and Jun’ichi Taga

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

Abstract

Two-step treatment of β-arylethylisocyanates (1) and -urethans (2) with POCl₃ followed by SnCl₄ gave the corresponding dihydroisocarbostyrils (6) in satisfactory yields; the method was conveniently applicable to the hindered isocyanates and urethans with complex structure.

■ Synthesis of Alkaloid, Zephyranthine

Masae Yamaki, Mayumi Murata, Shuzo Takagi, Yoshisuke Tsuda, Takehiro Sano, Jun-ichi Taga, Kimiaki Isobe, Hirokazu Tanaka, Hiroshi Irie,* and Shojiro Uyeo

*Faculty of Pharmaceutical Sciences, Kyoto University, 46-29 Yoshida-shimoadachi-machi, Sakyo-ku, Kyoto 606-8501, Japan

Abstract

Synthesis of zephyranthine, which is an alkaloid isolated from Zephyranthes candida Nerb. was described.

■ Synthesis of 1-Hydroxy-4,6-dimethoxy-8-methylxanthone

Tetsuzo Kato,* Nobuya Katagiri, and Jun Nakano

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

Abstract

1-Hydroxy-4,6-dimethoxy-8-methylxanthone (VII), namely an isomer of lichexanthone (IIIb) was synthesized from ethyl orsellinate, which is readily prepared from diketene and ethyl acetoacetate.

■ A Novel Reaction for Synthesis of Nitrogen Heterocyclic Compounds

Yuan L. Chow* and Somasekharen K. Pillay

*Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby B. C. V5A 1S6, Canada

Abstract

Where stereoelectronic requirements are satisfactorily met for an intramolecular nucleophilic attack of an electron rich center at a C-nitroso group, the C-nitroso compounds rearrange to form the cyclic hydroxylamines.

■ Phenol Oxidation of Isoquinoline Alkaloids with Cuprous Chloride and Oxygen in Pyridine as an Enzymatic Model. Biomimetic Total Synthesis of Corytuberine, Isoboldine, Pallidine, Orientalinone and Kreysiginone

Tetsuji Kametani,* Yoshinori Satoh, Makoto Takemura, Yohko Ohta, Masataka Ihara, and Keiichiro Fukumoto

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

Abstract

Phenol oxidation of (+)-reticuline (1) perchlorate with cuprous chloride and oxygen in pyridine gave (+)-corytuberine (2), (+)-isoboldine (3), and pallidine (4). Under the same reaction conditions, (±)-orientaline (5) perchlorate yielded (±)-orientalinone (6) and its epimer (7), while (±)-1,2,3,4-tetrahydro-7-hydroxy-1-(4-hydroxy-3-methoxyphenethyl)-6-methoxyisoquinoline (8) hydrochloride furnished (±)-kreysiginone (9) and the diastereoisomer (10). Oxidation with cupric chloride and potassium superoxide in pyridine gave rise to the similar results.

■ Synthesis and Structure Assignments of Diethyl cis- and trans-5-Ethyl-2-oxo-4-piperidinemalonate

Tozo Fujii,* Shigeyuki Yoshifuji, and Kyoko Ikeda

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

Abstract

The Michael addition of diethyl malonate to 1-acetyl-5-ethyl-5,6-dihydro-2(1H)-pyridone (III) produced an 85 : 15 mixture of the trans- (IVa) and the cis-isomer (IVb) of the title lactam diester. The configuration of both isomers has been established by chemical interrelation of them with substances of known stereochemistry.

■ The Reaction of Thiobenzoyl Isocyanates with N,N’-Diphenylsulfur Diimide

Otohiko Tsuge,* Satoshi Urano, and Shuntaro Mataka

*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan

Abstract

Thiobenzoyl isocyanates (1) reacted with N,N’-diphenylsulfur diimide (2) affording phenyl isocyanate (3), 2,5-diaryl-1,3,2,4-dithiadiazoline (4), 5-aryl-1,2,4-dithiazolin-3-one (5), and N-phenyl-N’-thiobenzoylurea (7), along with traces of 2,5-diaryl-1,2,4-thiadiazolin-3-one (6).