Regular Issue

Vol. 23, No. 3, 1985

24 data found. 1 - 24 listed
Communication | Regular issue | Vol 23, No. 3, 1985, pp. 547 - 548
Published online:
DOI: 10.3987/R-1985-03-0547
High-pressure Synthesis of Cryptands with Aliphatic Bridging Units

Marek Pietraszkiewicz, Piotr Salanski, and Janusz Jurczak*

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


N,N’-Dimethyl diazacoronands react with α,ω-diiodoalkanes under high pressure (10 kbar) to give the bis-quaternary salts which are transformed into cryptands via demethylation with triphenylphosphine.

PDF (47KB)
Communication | Regular issue | Vol 23, No. 3, 1985, pp. 549 - 551
Published online:
DOI: 10.3987/R-1985-03-0549
An Aromatic Version of Claisen Rearrangements of Ester Silyl Enolates — A Facile Synthesis of 2,3-Disubstituted Furans

Hideo Nomoto, Eiki Shitara, Keiichiro Fukumoto,* and Tetsuji Kametani

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


The [3,3]sigmatropic rearrangement of furfuryl ester silyl enolates (4)~(6) was studied and found to proceed under very mild conditions to give the carboxylic acids (13)~(15) after acid treatment.

PDF (70KB)
Communication | Regular issue | Vol 23, No. 3, 1985, pp. 553 - 556
Published online:
DOI: 10.3987/R-1985-03-0553
Synthesis of Substituted Tetrahydrofurans and Tetrahydropyrans 1. Oxidative Cyclization of p-Methoxystyrene Derivatives with DDQ

Yuji Oikawa, Kiyoshi Horita, and Osamu Yonemitsu*

*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan


In the course of synthetic studies of polyether antibiotics, we tried to develop a new synthetic method of substituted tetrahydrofuran and tetrahydropyran rings. When p-methoxystyrene derivatives having a hydroxy group at a suitable position was treated with DDQ, an oxidative cyclization of E-olefins, not Z-olefins, occurred yielding substituted tetrahydrofurans and tetrahydropyrans, though in low yields.

PDF (116KB)
Communication | Regular issue | Vol 23, No. 3, 1985, pp. 557 - 562
Published online:
DOI: 10.3987/R-1985-03-0557
Studies on Indenopyridine Derivatives and Related Compounds. IV. Synthesis and Stereochemistry of Ethyl 9,9-Dimethyl-1,2,3,9a-tetrahydro-9H-indezo[2,1-b]pyridine-3-carboxylate and Its Derivatives

Ryuji Yoneda, Tatsuya Terada, Shinya Harusawa, and Takushi Kurihara*

*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan


The simplified analogs of lysergic acid, namely ; 4-diethylphosphoryl or 3-methyl derivatives (15a, 15b, and 22) of ethyl 1,9,9-trimethyl-1,2,3,9a-tetrahydro-9H-indeno[2,1-b]pyridine-3-carboxylate are synthesized. The structure and stereochemistry of these products as well as some intermediates are also discussed.

PDF (128KB)
Communication | Regular issue | Vol 23, No. 3, 1985, pp. 563 - 566
Published online:
DOI: 10.3987/R-1985-03-0563
A Novel Stereoselective Synthesis of Morphinan Skeleton

Tetsuji Kametani,* Yukio Suzuki, and Toshio Honda

*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan


A basic skeleton of morphinan alkaloids was stereoselectively synthesized by employing a thermolysis of a benzocyclobutene derivative.

PDF (72KB)
Communication | Regular issue | Vol 23, No. 3, 1985, pp. 567 - 569
Published online:
DOI: 10.3987/R-1985-03-0567
A Modified Synthesis of the (+)-8α-phenylsulfonyl-des-AB-cholestane via an Intramolecular Nucleophilic Attack to Epoxide — A Total Synthesis of Vitamine D3

Hideo Nomoto, Hiroshi Kurobe, Keiichiro Fukumoto,* and Tetsuji Kametani

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


An intramolecular alkylation of the phenylsulfonyl epoxide (6), which was readily obtained from the aldehyde (5), gave a separable mixture of the alcohols (7a) and (8a). The alcohol (8a) was then dehydrated via the corresponding mesylate (8b) to afford the olefin (9) which on hydrogenation furnished (+)-8α-phenylsulfonyl-des-AB-cholestane (1). Further this product was converted into vitamin D3 (4).

PDF (64KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 571 - 583
Published online:
DOI: 10.3987/R-1985-03-0571
The 5-Alkoxymethyl-, 5-Alkylthiomethyl-, and 5-Dialkylaminomethylisoxazoles

Ronald G. Micetich,* Chia C. Shaw, Tse W. Hall, Paul Spevak, Robert A. Fortier, Peter Wolfert, Brian C. Foster, and Buljit K. Bains

*Faculty of Pharmacy , University of Alberta, Edmonton, Alberta T6G, 2N8, Canada


A variety of methods were used for the preparation of the 5-alkoxymethyl-, 5-alkylthiomethyl-, and 5-dialkylaminomethylisoxazoles. A novel method for the separation of the isomeric mixture of 3-(5-)methoxymethyl-5-(3-)methylisoxazoles (obtained by reaction of 1-methoxypentane-1,3-dione with hydroxylamine), based on the difference in reactivity with n-butyllithium, is described. Methods for the preparation of 5-alkylthimethylisoxazoles from the 5-methylisoxazoles; and 5-alkoxymethylisoxazoles from the 5-hydroxymethylisoxazoles are also reported.

PDF (277KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 585 - 592
Published online:
DOI: 10.3987/R-1985-03-0585
Lithiation Reactions of 5-Alkoxymethyl-, 5-Alkylthiomethyl-, and 5-Dialkylaminomethylisoxazoles

Ronald G. Micetich,* Chia C. Shaw. Tse W. Hall, Paul Spevak, and Buljit K. Bains

*Faculty of Pharmacy , University of Alberta, Edmonton, Alberta T6G, 2N8, Canada


The 5-alkoxymethyl- and 5-alkylthiomethylisoxazoles undergo exclusive lateral lithiation at the C-5 methylene, the products reacting separately with methyl iodide, dimethyl disulfide, and carbon dioxide to give after work up the respective 5α-alkoxyethyl, 5α-alkylthioethyl , the mixed acetal, the thioacetal, the α-alkoxy acid and the α-thioalkoxy acid of the isoxazoles. This reaction can be repeated to give the mixed ortho ester, the thio ortho ester, the mixed α-ketal acid, and the mixed-thioketal acid. This method provides a very convenient route to these classes of compounds. The 5-dialkylaminomethylisoxazole is lithiated at the C-4 position.

PDF (182KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 593 - 602
Published online:
DOI: 10.3987/R-1985-03-0593
On the Synthesis of (±)-Mesembranone by the Dissolving Metal Reduction of 4-Aryl-4-aminoethylcyclohexenones. Isolation of N-Methyl-5-(3’,4’-dimethoxyphenyl)-2-azabiocyclo[3.3.1]nonan-8-one

Ignacio H. Sánchez,* María Larraza, Humbert J. Flores, Eduardo Díaz, and Krzysztof Jankowski

*Facultad de Química, Universidad Nacional Autónama de México, Circuito Exterior, Ciudad Universitaria, Coyoacán 04510, Mexico


The novel 2-azabicyclo[3.3.1]nonan-8-one derivative 4 has been isolated as byproduct in the synthesis of (±)-mesembranone (2) by the dissolving metal reduction of the 4-aryl-4-aminoethylcyclohexenone 1.

PDF (188KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 603 - 609
Published online:
DOI: 10.3987/R-1985-03-0603
Reaction of 4-Bromoalkyl-4-methoxy-2,5-oxazolidione with Alcohol or α-Amino Acid Ester and Transformation of the Products

Chung-gi Shin,* Naoyuki Takamatsu, Yoshiaki Sato, and Yasuchika Yonezawa

*Departmnet of Applied Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan


Reaction of N-carboxy α-dehydroamino acid anhydride with methanol in the presence of NBS gave 4-bromoalkyl-4-methoxy-2,5-oxazolidione, which was further treated with alcohol or α-amino acid ester to give extremely different two types of products, 2-oxazolinone and α-(oximino)acyl-α-amino acid derivatives respectively.

PDF (127KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 611 - 616
Published online:
DOI: 10.3987/R-1985-03-0611
The Synthesis and Aminolysis of Some 4-Chloro-2-(substituted) Thiopyrimidines

Derek T. Hurst* and Matthew Johnson

*School of Analytical and Biological Chemistry, Kingston Polytechnic, Kingston-on-Thames, KT1 2EE, U.K.


Some 2-methylthio,2-methylsulphinyl and 2-methylsulphonyl-4-chloropyrimidines have been prepared. In each case which was studied except one the chloride ion was that which was preferentially displaced by diethylamine. The pseudo first order rate constant for each reaction was determined the results showing that oxidation of the 2-methylthio group greatly enhances the rate of displacement of the 4-chloro group.

PDF (147KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 617 - 622
Published online:
DOI: 10.3987/R-1985-03-0617
Isolation and Structure of a New Alkaloid from the Roots of Rauwolfia Serpentina Benth

Salimuzzaman Siddiqui,* S. Salman Ahmad, S. Imtiaz Haider, and Bina Shaheen Siddiqui

*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan


A new dihydroindole alkaloid sandwicoline has been isolated from undried winter roots of Rauwolfia serpentina of Nepalies origin and its structure detemined as 21-monohydro-N-methylsandwicine through chemical and spectral studies.

PDF (136KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 623 - 632
Published online:
DOI: 10.3987/R-1985-03-0623
A Study of the Preparation and Reactions of the Unusually Labile 5-Methyl[1,2,4]oxadiazolo[2,3-c]quinazolin-2-one

Darshan Ranganathan,* Shakti Bamezai, and P. Veeraraghavan Ramachandran

*Department of Chemistry, Indian Institute of Technology, Kanpur 208016, India


A Π2s + Π2s + ω2s cycloaddition of 4-isocyanato-2-methyl quinazoline 3-oxide leads to the title compound, 5-methyl[1,2,4]oxadiazolo[2,3-c]quinazolin-2-one (1) . Surprisingly, the weakest bond in 1 is 4-5. Rupture of this bond takes place thermally as well as with P(OR)3 leading to the isomeric, 5-methyl[1,2,4]oxadiazolo[3,4-c]quinazolin-3-one (11). A detailed thermolytic study of 1 has given products arising from scission of the bonds 2-3, 3-4 and 4-5. The 3-4 bond is preferentially broken on photolysis of 1 in MeOH.

PDF (233KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 633 - 639
Published online:
DOI: 10.3987/R-1985-03-0633
Synthesis of α-Hydroxydimethylacetals from Nitrogen Heterocyclic Ketones Using Hypervalent Iodine Oxidation

Robert M. Moriarty,* Om Prakash, Cyriac T. Thachet, and Hikmat A. Musallam

*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.


The synthesis of various α-hydroxydimethylacetals (2a-2j) has been achieved by the oxidation of nitrogen containing heterocyclic ketones (1a-1j) using C6H5I(OAc)2-KOH-MeOH . The nmr and mass spectra of the acetals are discussed.

PDF (182KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 641 - 648
Published online:
DOI: 10.3987/R-1985-03-0641
Pyrazolo[5,1-c]-1,2,4-tiazoles from 1,2,4-Triazolium Salts and Substituted Acetonitriles

Pedro Molina,* Mateo Alajarín, and María-Jesús Vilaplana

*Departmento de Química Orgánica, Facultad de Ciencias, Universidad de Murcia, 30071 Murcia, Spain


3-Substituted 4-amino-1-methyl-5-methylthio-1,2,4-triazolium salts react with acetonitriles activated by another electron-delocalizing group to give enamines which undergo cyclization by action of hydrogen chloride to give pyrazolo[5,1-c]-1,2,4-triazole derivatives.

PDF (148KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 649 - 651
Published online:
DOI: 10.3987/R-1985-03-0649
Reactivity of Cyanodithioformate towards Primary Amiens

Carmen de Diego, Encarnación Gómez, and Carmen Avendaño*

*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain


The two electrophilic carbon atoms of methyl cyanodithioformate 1 are able to react with primary amines giving a variety of different products depending upon the nature of amines. The one step reaction with o-dinucleophiles giving condensed heterocompounds in moderate to good yields is of interest.

PDF (67KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 653 - 659
Published online:
DOI: 10.3987/R-1985-03-0653
A New Route to Hexahydropyrrolizines Derivatives via Nonstabilized Ylide Generated from N-Methylpyrrolidine N-Oxide

Jacqueline Chastanet and Georges Roussi*

*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France


N-Methylpyrrolidine N-oxide treated with lithium diisopropylamide in the presence of various olefins, leads to the corresponding hexahydropyrrolizines(6) via the ylide intermediate (5).

PDF (156KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 661 - 665
Published online:
DOI: 10.3987/R-1985-03-0661
Synthesis of (±)-Gaddain, a New Lignan from Jatropha gossypifolia Linn (Euphorbiaceae)

Julie Banerji* and Biswanath Das

*Chemistry Department, University College of Science, 92 Acharya Prafulla Chandra Road, Calcutta-700009, India


(±)-Gadain, a new lignan isolated from Jatropha gossypifolia, has been synthesised by the condensation of 3-(3,4-methylenedioxybenzyl)-butyrolactone with piperonal in the presence of sodium methoxide in methanol. The key intermediate lactone was prepared by the Stobbe condensation of piperonal with dimethyl succinate followed by hydrogenation to the butanoic acid derivative and the reduction of the potassium salt of butanoic acid with calcium borohydride.

PDF (123KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 667 - 670
Published online:
DOI: 10.3987/R-1985-03-0667
Cyclopentenone from Furan: An Unususal Marckwald Reaction

Giovanni Piancatelli* and Enzo Castagnino

*del C. N. R., c/o Istituto do Chimica Organica, Università degli Studi di Roma "La Sapienza", Piazzale Aldo Moro 2 - 00185 Roma, Italy


A “one pot” conversion of methyl furfurylidenepyruvate 5 directly to the cyclopentenone 8, by means of the Marckwald reaction, is described.

PDF (104KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 671 - 676
Published online:
DOI: 10.3987/R-1985-03-0671
Synthesis of Vinca Alkaloids and Related Compounds. XXIII. Transposition of Functionality on the Indolo-quinolixidine Seleton

Mária Incze, Ferenc Sóti, Zsuzsa Kardos-Bologh, Mária Kajtár-Peredy, and Csaba Szántay*

*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, Pusztaszeri ut 59-67, P.O.Box 17, Hungary


Bromination and subsequent reactions with nucleophiles of a substituted indolo[2,3-a]quinolizidine derivative yielded instead of the expected indolenine derivatives 7-substituted indolo[2,3-a]quinolizidines.

PDF (140KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 677 - 681
Published online:
DOI: 10.3987/R-1985-03-0677
New Synthesis of Functionalized β-Lactams from Azabutadiene Analogues and Ester Enolates

Mitsuo Komatsu, Shinji Yamamoto, Yoshiki Ohshiro,* and Toshio Agawa

*Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Toyonaka, Osaka 560-0043, Japan


Reaction of the 2-azabutadiene 1 with α-lithioesters 2a,b gave N-styryl-2-azetidinones 3a,b in high yields in contrast to the δ-lactam formation of 1-azadienes with 2. The azines 7a,b also reacted with the enolate 2a to result in β-lactam formation: N-alkylidenamino-2-azetidinones 8a,b and/or 1,1’-bi(2-azetidinone)s 9a,b were obtained in good yields.

PDF (110KB)
Report | Regular issue | Vol 23, No. 3, 1985, pp. 683 - 690
Published online:
DOI: 10.3987/R-1985-03-0683
4-Nitro- and 4-Cyanopyridazines

Antonius T. M. Marcelis and Henk C. van der Plas*

*Laboratory of Organic Chemistry, Agricultural University, De Dreijen 5, 6703 BC Wageningen, The Netherlands


3-Acyl-1,2,4,5-tetrazines react with 1-nitro-2-dimethylaminoethene and 1-cyano-2-morpholinoethene by an inverse electron demand Diels-Alder reaction to give, after elimination of nitrogen and the secondary amine, the corresponding 3-aryl-5-nitro- and 3-aryl-5-cyanopyridazines. Besides these compounds, 1-benzylidene-2-dialkylaminomethylenehydrazines were isolated. They are also obtained from reaction of the 3-aryl-1,2,4,5-tetrazines with secondary aliphatic amines. Tetrazines with two electron-withdrawing groups like 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine and 3,6-bis(piperidinocarbonyl)-1,2,4,5-tetrazine also react with the nitro- or cyanoenamine to give the corresponding 3,6-disubstituted 4-nitro- or 4-cyanopyridazines.

PDF (170KB)
Review | Regular issue | Vol 23, No. 3, 1985, pp. 691 - 729
Published online:
DOI: 10.3987/R-1985-03-0691
D-Ribonolactone in Organic Synthesis — A Review

Krishna L. Bhat, Shin-Yih Chen, and Madeleine M. Joullié*

*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.


The use of D-ribonolactone, on inexpensive, commercialiy available sugar, as a chiral template in organic synthesis is described. The versatility of this compound is illustrated with selected examples from the literature. The regio- and stereoselective functionalizaotion of D-ribonolactone and its use in the synthesis of precursors for many natural products demonstrate that D-ribonolactone is a valuable alternative to other sugars.

PDF (606KB)
Review | Regular issue | Vol 23, No. 3, 1985, pp. 731 - 740
Published online:
DOI: 10.3987/R-1985-03-0731
Ring Annelations via Reissert Compounds

Frank D. Popp* and Barrie C. Uff

*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.


Conversion of isoquinoline and related heterocycles to the corresponding Reissert compound provides a starting point for the annelation of an additional ring. This has proved an attractive route to a wide range of ring systems. The review discusses the versatility of such procedures which include cycloaddition of cyclic Reissert salts with alkynes, addition of Reissert compound conjugate bases to suitable Michael acceptors, intramolecular cyclisations of Reissert compounds derived from chloroalkyl-substituted acid chlorides, the reaction of conjugate bases of chloroformate derived Reissert compound analogs with suitable electrophiles including heterocumulenes, and other methods. Annelations are exemplified with a variety of heterocycles in addition to isoquinoline and quinoline, including phthalazine, phenanthridine and 3,4-dihydro-β-carboline.

PDF (193KB)
24 data found. 1 - 24 listed