2-Alkyl-3-chloro(bromo)tetrahydrofurans

The reaction ofRS(SR)-2,3-dibromo- and 2,3-dichlorotetrahydrofurans with ethylmagnesium bromide in ether was investigated. It was shown that the main reaction products are 2-ethyl-3-bromotetrahydrofuran (27%) and 3-bromo-2-(2-ethyl-3-tetrahydrofuryl)tetrahydrofuran (65%) in the first case and 2-ethyl-3-chlorotetrahydrofuran (33%) and 3-chloro-2-(3-chloro-2-tetrahydrofuryl)tetrahydrofuran (65%) in the second.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. I. M. Gubkin Moscow Institute of Petroleum and Gas, 111917 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1430–1434, June, 1992.     

13C and1H NMR study of 3-R-substitutedtrans-2-oxadecalins and 1-R-substitutedcis- andtrans-2-oxahydrindans

Previously synthesized 3-substitutedcis- andtrans-2-oxadecalins and 1-substitutedcis- andtrans-2-oxahydrindans were studied by ¹³ C and ¹ H NMR. The structure and configuration of these compounds were established.A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 861–865, April, 1992.     

Enantioselective syntheses of no-carrier-added (n.c.a.) (s)-4-chloro-2-[f] fluorophenylalanine and (s)-(α-methyl) -4-chloro-2-[f]fluorophenylalanine

(S)-4-Chloro-2-fluorophenylalanine and (S)-(α-methy)-4-chloro-2-fluorophenylalanine were synthesized and labeled with no carrier added (n.c.a.) fluorine-18 through a radiochemical synthesis relying on the highly enantioselective reaction between 4-chloro-2-[¹⁸F]fluorobenzyl iodide and the lithium enolate of (2S)-1-(tert-butyloxycarbonyl)-2-(tert-butyl)-3-methyl-1,3-imidazolidine-4-one for (S)-4-chloro-2-[¹⁸F]fluorophenylalanine and (2S,5S)-1-(tert-butyloxycarbonyl)-2-(tert-butyl)-3,5-dimethyl-1,3-imidazolidine-4-one for (S)-(α-methyl) -4-chloro-2-[¹⁸F] fluorophenylalanine. Quantities of about 20–25 mCi were obtained at the end of sy nthesi s, ready for injection after hydrolysis and high performance liquid chromatography (HPLC) purification, with a radiochemical yield of 17%–20% corrected to the end of bombardment after a total synthesis time of 90–105 min from [¹⁸F] fluoride. The enantiomeric excesses were shown to be 97% or more for both molecules without chiral separation and the radiochemical and chemical purities were 98% or better.     

新型手性N-烷基-3-蒎胺类化合物的合成及其抑菌活性的研究

以(1S,5S)-(－)-α-蒎烯为原料合成了系列新型(1S,2S,3S,5R)-N-烷基-3-蒎胺类化合物. (－)-α-蒎烯经硼氢化氧化、重铬酸吡啶盐(PDC)氧化得到(1S,2S,5R)-(－)-3-蒎酮; 在BF3•(C2H5)2O催化下(1S,2S,5R)-(－)-3-蒎酮与伯胺化合物反应生成Schiff碱, 再经KBH4或NaBH4还原得到(1S,2S,3S,5R)-N-烷基-3-蒎胺类化合物. 采用FT-IR, 1H NMR, 13C NMR和GC-MS等分析手段对合成所得(1S,2S,5R)-N-烷基-3-蒎烷亚胺和(1S,2S,3S,5R)-N-烷基-3-蒎胺类化合物的结构进行了表征. 考察了(1S,2S,3S,5R)-N-烷基-3-蒎胺类化合物对大肠杆菌(E. coli)、金黄色葡萄球菌(S. aureus)、枯草芽胞杆菌(B. subtilis)、荧光假单胞菌(P. fluorescens)、白色念珠菌(C. albicans)、黑曲霉(A. niger)和米根霉(R. oryzae)等细菌和真菌的抑菌和杀菌活性. 结果表明(1S,2S,3S,5R)-N-正庚基-3-蒎胺对真菌和细菌均表现出良好的杀菌和抑菌活性.     

Asymmetric synthesis of heteroorganic analogs of natural products. 6. (S)-α-amino-ω-phosphonocarboxylic acids

Alkylation, by -haloalkylphosphonates, of the Ni(II) complex of the Schiff base formed from glycine and (S)-2-N-(N¹-benzylprolyl)-o-aminobenzophenone has been used for the asymmetric synthesis of (S)-2-amino-4-phosphonobutyric and (S)-2-amino-5-phosphonovaleric acids.Institute of Bioorganic Chemistry and Oil Chemistry, Ukrainian Academy of Sciences, 250800 Kiev. A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 397–402, February, 1992.     

Simple synthesis of substituted 3-oxabicyclo[3.1.0]hexan-2-ones and their rearrangement in the presence of lithium iodide

2-Alkenylidenemalonic ester monoepoxides react with organolithium and organomagnesium compounds to give 1-ethoxycarbonyl-4-alkyl-6-alkenyl(alkyl, aryl, alkynyl)-3-oxabicyclo[3.1.0]hexan-2-ones in high yields. The latter, when an alkenyl fragment is present, undergo rearrangement in the presence of LiI to substituted 1-ethoxycarbonyl-3-oxabicyclo[3.3.0]-6-octen-2-ones or 3-(1,3-butadienyl)-4-butanolides.Institute of Chemistry, Bashkir Science Center, Ural Branch, Russian Academy of Sciences, Ufa 450054. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 946–954, April, 1992.     

Reaction of benzothiazol-2-one with 4-hydroxy-4-methyl-2-pentynonitrile

Reaction between the title compounds gave the unexpected 3-[5,5-dimethyl-2,5-dihydrofur-4-yl-2-(3-isopropanol-2-propenonitrile)imino]benzothiazol-2-one, as a result of the addition of two cyanoacetylene molecules.Irkutsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk 664033. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 1003–1005, April, 1992.     

Investigation of neoascorbigen

The synthesis of N-methoxyascorbigen (neoascorbigen) — a natural substance from plants of the Cruciferae family — and also N-ethoxyascorbigen is described. In an acidic media under drastic conditions N-alkoxyascorbigens undergo transformations with the release of ascorbic acid and the formation of oligomers of 1-alkoxy-3-methyleneindolenine or with opening of the lactone ring, decarboxylation, and dehydration and the formation of 2-hydroxy-3-(1-alkoxy-3-indolyl)-4-hydroxymethylcyclopent-2-enone. Amides of neoascorbigen, 3-O-methylglycoside of N-ethoxyascorbigen, and the product of the reduction of N-ethoxyascorbigen by sodium borohydride were obtained for the first time.Scientific-Research Institute of the Search for New Antibiotics, Russian Academy of Medical Sciences, Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 178–186, February, 2000.     

Synthesis of 4-R-3-(4-R1-5-R2-1,2,3-triazol-1-YL)furazans. 1. Azidofurazans in 1,3-dipolar cycloaddition reactions with substituted acetylenes

The 1,3-dipolar cycloaddition of azidofurazans to substituted acetylenes has been studied and substituted 3-(1,2,3-triazol-l-yl)furazans have been synthesized.N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913, Russia; e-mail: mnn@cacr.ioc.ac.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 100–110, January, 2000.     

Synthesis of （S）-2-（3-Arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）ethoxy]phenyl}propanoic Acids

The synthesis of （S）-2-（3-arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）etho- xy]phenyl}propanoic acids is described. Their structures were confirmed by ^1H-NMR.     

Improved method for the preparation of 3-aryl- and 3-styrylimidazo[1,5-a]pyridines

A new convenient method is proposed for the preparation of 3-aryl- and 2-styrylimidazo[1,5-a]pyridines involving the cyclocondensation of 2-(acylaminobenzyl)pyridines in acetic anhydride with adding of p-toluenesulfonic acid.Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 252660 Kiev; e-mail: olga@elan-ua.net. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 640–642, May, 2000.     

Complexes of cobalt(2+) chloride with hydrochlorides of N-(1,2,4-triazol-5-yl)- and N-(tetrazol-5-yl)benzamidines

We have synthesized complex compounds of Co(2+) chloride with hydrochlorides of N-(1,2,4-triazol-5-yl)benzamidine and N-(tetrazol-5-yl)benzamidine. According to magnetochemistry and electron spectroscopy data, the ligands are coordinated in a bidentate fashion with the N atom of the amidine group and the N atom of the heterocycle with formation of the tetrahedral chromophore CoN₂Cl₂.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2311–2315, October, 1992.     

(S)-(4-溴-2-甲苯)(3-甲基吗啉)甲酮的合成

以(S)-2-氨基丙醇和氯乙酰氯为起始原料,经酰化和环合反应制得(S)-5-甲基吗啉-3-酮（4）; 4经还原制得(S)-3-甲基吗啉(5); 5与4-溴-2-甲基苯甲酸酰化缩合合成了(S)-(4-溴2-甲基苯基)(3-甲基吗啉)-甲酮,总收率57%,其结构经¹H NMR 和 ¹³C NMR确证。     

Spectrophotometic Determination Of Tin In Steels With2-(5-Nltro-2-Pyridylazo)-5-[N-n-Propyl-N-(3-Sulfopropyl)Amino]phenol

ABSTRACT

A highly sensitive azo dye, 2-(5-nitro-2-pyridylazo)-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol (Nitro-PAPS), is used as a colorimetric reagent for the determination of tin(IV) content. Nitro-PAPS reacts with tin(IV) to form a water-soluble complex in 1.0 M acetic acid. Full color development is attained within 5 minutes, and maintains constant absorbance for at least 24 hours. The apparent molar absorptivity is 7.7 x 10⁴ dm³ mol^?1 cm^?1 at a maximum wavelength of 580 ran. Beer's law is obeyed for tin(IV) in the range of 0-1.2 μg ml^?1. The proposed method is successfully applied to the determination of trace amounts of tin in steels.     

(CH3)2SBr2 – einige Reaktionen und Strukturen

(CH₃)₂SBr₂ – Reactions and Structures (CH₃)₂SBr₂ ( 1 ) is a donor acceptor complex (8-S-3 + 10-Br-2) which reacts with (CH₃)₂S(?O)NSi(CH₃)₃ to yield [(CH₃)₂S(O)?N? S(CH₃)₂]⁺Br^? ( 2 ). With SbBr₃ (CH₃)₂SBr⁺SbBr₄^? ( 3 ) can be isolated. 1 crystallizes monoclinic in the space group P2₁/c with a = 733.8, b = 734.2, c = 1132.7 pm, β = 92.8° and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 967.2, b = 793.3, c = 1168.3 pm and Z = 4. The SBr and BrBr force constants of 1 are compared with those of S₂Br₂, 3 and Br₂ resp. The nmr and mass spectra of 1 and 2 are communicated.     

Synthesis of (1,2,3-triazol-1-yl)furazans. 2. Reaction of azidofurazans with morpholinonitroethene

We have studied the 1,3-dipolar cycloaddition of azidofurazans to morpholinonitroethene and prepared 1,2,3-triazoles with furazan ring in position 1 and NO₂ group at position 4.For Communication 1 see [1].N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913; e-mail: mnm@carc.ioc.ac.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 406–408, March, 2000.     

Sulfur-containing spirocyclic compounds based on 3-methyl-(amino)-1-phenylpyrazol-5-ones

3-Methyl(amino)-1-phenylpyrazol-5-ones react with N-chlorosulfenylphthalimide to give 4-phthalimidothiopyrazoles which decompose to form 3-methyl(amino)-1-phenylpyrazol-5-one-4-thiones. They were identified as their spirocyclic adducts with dienes. Oxidation of the latter with m-chloroperbenzoic acid gives spirocyclic sulfoxides and sulfones.Institute of Organic Chemistry, Ukraine Academy of Sciences, Kiev 253660. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 187–192, February, 2000.     

Synthesis of 3-thienyl-substituted isothiazolines-2 and 1,2,4-thiadiazoles based on nitrile sulfides of the thiophene series

The reaction of substituted - and -thienylcarboxamides with chlorocarbonylsulfenyl chloride gave 5-thienylsubstituted 1,3,4-oxathiazol-2-ones. Decarboxylation of the latter by heating in o-dichlorobenzene generated in situ - and -thienylnitrile sulfides, which in the presence of dipolarophiles [dimethyl fumarate, N-phenylmaleinimide, chloro(trichloro)acetonitrile] give the corresponding 3-thienyl-substituted ²-isothiazolines and 5-chloromethyl(trichloromethyl)-1,2,4-thiadiazoles.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1892–1897, August, 1992.     

Heterocyclization of 1,1-dicyano-2-(trifluoromethyl)ethylenes with 1,3,3-trimethyl-3,4-dihydroisoquinoline and its derivatives

1,3,3-Trimethyl-3,4-dihydroisoquinolines react with 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene to give 4-amino-6,6-dimethyl-2,2-bis(trifluoromethyl)-3-cyano-6,7-dihydro-2H-benzo[a]quinolizines. The reaction of 3,3-dimethyl-1-cyanomethylidene-1,2,3,4-tetrahydroisoquinoline and the methyl ester of 3,3-dicyano-2-(trifluoromethyl)acrylic acid leads to 5,5-dimethyl-3-oxo-2-(trifluoromethyl)-2-(dicyanomethyl)-2,3,5,6-tetrahydropyrrolo[2,1-a]isoquinoline.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1888–1892, August, 1992.     

Reactions of 2-(4,5-dihydro-3-furyl)-1,3-diphenyl-1,3-diaza-2λ<Superscript>3</Superscript>-phospholidine and 4,5-dihydro-3-furylphosphonous diamides with nitrile imines

Reactions of 2-(4,5-dihydro-3-furyl)-1,3-diphenyl-1,3-diaza-2λ³-phospholidine (1) with nitrile imines are multistep processes involving cleavage of one P-N bond of the diazaphospholidine ring to form substituted 5-(2-chloroethyl)-4-(N,N′-diphenylethylenediamino)-1,4-dihydro-1,2,4λ⁵-diazaphosphorines 4 as final products. Analogs of phospholidine 1, namely, 4,5-dihydro-3-furylphosphonous dipiperidide and dimorpholide, react with C,N-diphenylnitrile imine with retention of both P-N bonds to give 5-(2-hydroxyethyl)-1,2,4-diazaphosphorinium chlorides. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1590–1593, July, 2005.