Synthesis ofN-(3-azido-2-nitroxypropyl)-,N-(2,3-diazidopropyl)-, andN-(2-azido-3-methoxypropyl)-N-alkylnitramines

N-(3-Azido-2-nitroxypropyl)-N-alkylnitramines andN-(2,3-diazidopropyl)-N-alkylnitramines were prepared by nitration and azidation ofN-alkyl-N-(2-hydroxy-3-chloropropyl)sulfamates andN-(3-azido-2-hydroxypropyl)-N-alkylsulfamates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 206–208, January, 1999.     

Quantum chemical study of the transformation of 2-(N-alkylamino)-3-(indol-1-yl)-and 2-(N-alkylamino)-3-(indol-3-yl)maleimides by protic acids: Tandem hydride transfer/cyclization mechanism

The geometric parameters, the charge distribution, and the energetics of N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)-and N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimides and their conjugated acids were studied by density functional theory calculations at the B3LYP/6-31G(d) level. The mechanism of the tandem hydride transfer/cyclization sequence, which occurs after protonation of N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)-and N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimides, was analyzed. The investigation of the potential energy surface for the tandem hydride transfer/cyclization of the iminium cation that formed upon protonation revealed that the hydride transfer followed by intramolecular cyclization at position 7 of the indole fragment in N-methyl-2-(N-ethylanilino)-3-(indol-1-yl)maleimide is the preferable process, unlike alternative intramolecular cyclization involving the cationic center at the C(2) atom of the indole fragment and the benzene ring of the N-ethylaniline fragment of the indoleninium cation in N-methyl-2-(N-ethylanilino)-3-(indol-3-yl)maleimide. A study of the key intermediates of the assumed reaction mechanism demonstrated that these intermediates are actually stationary points on the potential energy surface (minima and transition states). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2069–2073, December, 2006.     

Synthese und Reaktionsverhalten von 3-(Bis(alkylthio)methylen)-3H-isobenzofuran-1-on-und 2-(Bis(alkylthio)methylen)-3(2H)-benzofuranon-Derivaten

Summary 3(Bis(alkylthio)methylene)-3H-isobenzofuran-1-ones2a–e and 2-(bis(alkylthio)methylene)-3(2H)-benzofuranone derivatives4a–c are obtained by reaction of phthalides1a–d or 3(2H)-benzofuranone (coumaranone3), respectively, with carbon disulfide under basic conditions followed by alkylation. The reaction behaviour of the new compounds2 and4 is investigated. 2-((2-Dimethylthio-1-oxo)ethyl)benzoic acid N,N-dimethylamide (7a) and 2-((2-dimethylthio-1-oxo)ethyl)-benzoic acid 2-methylpiperidide (7b) are surprisingly formed instead of the methylthio substitution products by treatment of2a with the corresponding amine in the presence of aluminum chloride.

Herrn Professor Dr. Dr. h. c.Waldemar Adam zum 60. Geburtstag gewidmet     

Synthesis of 1-(9-butylcarbazol-3-yl)-5-oxopyrrolidine-3-carboxylic acid derivatives

A series of condensation products of 1-(9-butylcarbazol-3-yl)-5-oxopyrrolidine-3-carbohydrazide with 2-propanone, 2-butanone, 2,4-pentanedione, 2,5-hexanedione, ethyl 3-oxobutanoate, and aromatic aldehydes was obtained. Substituted oxadiazoles were synthesized from carbohydrazide or the corresponding hydrazone. Spectral properties of the synthesized compounds were examined. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1009–1017, July, 2008.     

Synthesis of N-nitrooxazolidines and N-nitrotetrahydro-1,3-oxazines from N-(2-hydroxyalkyl)- and N-(3-hydroxyalkyl)sulfamates

A method was developed for the preparation of functionally substituted N-nitrooxazolidines and N-nitrotetrahydro-1,3-oxazines by nitration of the products obtained in the reactions of N-(2-hydroxyalkyl)- and N-(3-hydroxyalkyl)sulfamates with formaldehyde.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

3-Cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines in the synthesis of substituted 3-(aminomethyl)pyridines

The reactions of substituted 3-cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines with lithium aluminum hydride in anhydrous diethyl ether afforded the corresponding 3-aminomethyl derivatives, which were used in the synthesis of the corresponding amides.     

A new synthesis ofE- andZ(-)(1R,3S)-2,2-dimethyl-3-(3,3,3-trifluoro-2-chloropropen-1-yl)cyclopropanecarboxylic acids from (+)-3-carene

A new synthesis ofE- andZ(-)(1R,3S)-2,2-dimethyl-3-(3,3,3-trifluoro-2-chloropropen1-yl)cyclopropanecarboxylic acids from (+)-3-carene in 21 % total yield was carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 517–518, March, 1995.     

Reaction of 2-(2-oxoethylidene)furan-3(2H)-ones with isopropylidenehydrazides of aromatic carboxylic acids: Synthesis of 3-hydroxy-3-(2-oxoethyl)-2,3-dihydropyridazin-4(1H)-ones

3-Hydroxy-3-(2-oxoethyl)-6-phenyl-2,3-dihydropyridazin-4(1H)-ones were obtained by the reaction of methyl 3-oxo-5-phenylfuran-2(3H)-ylideneacetate or 2-[2-(4-chlorophenyl)-2-oxoethylidene]-5-phenylfuran-3(2H)-one with benzoic or p-nitrobenzoic isopropylidenehydrazides. Equilibrium C₍₅₎H and C₍₅₎H₂ tautomeric forms were detected in solutions of the 4-chlorophenyl derivatives in DMSO-d₆. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1156–1158, August, 2007.     

Synthesis of 2-oxazolidinones from (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol

A series of isomeric 2-oxazolidinones has been synthesized from (1S, 2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 579–584, April, 2006.     

新型荧光试剂1-(8-喹啉)-3-(2-吡啶)-三氮烯的合成及其分析应用

将具有荧光特性的8-氨基喹啉和吡啶类试剂结合, 并引入杂环三氮烯结构, 合成了新型荧光试剂1-(8-喹啉)-3-(2-吡啶)-三氮烯(QPyT). 其结构经元素分析、红外光谱和核磁共振谱证实. 研究结果表明, 在碱性介质中, 该试剂在λex/λem=216 nm/343 nm处产生强荧光, 并且能被Pb(Ⅱ)猝灭. 据此建立了QPyT测定Pb(Ⅱ)的新型荧光分析法. 该方法的线性范围为1.6×10-7~1.2×10-5 mol /L, 检测限为9.0×10-8 mol/L. 将其应用于水中Pb(Ⅱ)的测定, 结果令人满意.     

Synthesis of novel 3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones

An efficient method for the synthesis of novel 3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones from various 2-dimethylaminomethylidenecyclohexane-1,3-diones, (1,3-thiazol-2-yl)acetonitriles, and dimethylformamide dimethyl acetal was developed. These transformations proceeded through intermediate 2-[2-(4-aryl-1,3-thiazol-2-yl)-2-cyanoethenyl]-3-oxocyclohex-1-en-1-olates. They were isolated as piperidinium salts and used in further heterocyclization reactions with aromatic amines, giving novel 1-aryl-3-(1,3-thiazol-2-yl)-7,8-dihydroquinoline-2,5(1H,6H)-diones. These compounds were also obtained by preparative three-step “one pot” synthesis under controlled microwave irradiation. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 412–417, February, 2008.     

Synthesis and Stereochemistry of (1S,3S,4S,7R11R)-3-(4-Nitrophenyl)-11-aza-2,6-dioxatricyclo[5,3,1,04,11]undecane

The reaction of (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol with glutaraldehyde has been studied. It has been established on the basis of AM1 and PM3 calculations and ¹H NMR spectra recorded in the presence of the shift reagent Eu(fod)₃ that (1S,3S,4S,7R,11R)-3-(4-nitrophenyl)-11-aza-2,6-dioxatricyclo[5,3,1,0^4,11]undecane is formed as the result of the reaction.     

1-(4-硝基苯)-3-(3-甲基吡啶)-三氮烯合成及其与铜的显色反应

报道了新显色剂 1-(4-硝基苯)-3-(3-甲基吡啶)-三氮烯(NPMPDT)的合成及其与铜的显色反应.在OP的存在下,pH 10.5的Na2B4O7-NaOH缓冲溶液中,该试剂能与铜发生显色反应,铜与NPMPDT形成摩尔比为2∶1型的黄色配合物,在460 nm处有一最大正吸收,在535 nm 处有一最大负吸收.以460 nm为参比波长,535 nm为测量波长进行双波长测定,其表观摩尔吸光系数ε＝2.18×105 L·mol-1·cm-1,铜的质量浓度在0～0.48 μg/mL 范围内符合比尔定律,用本法测定大米和面粉中微量的铜,结果满意.     

On the chemistry of pyrrole pigments,XCVII: Synthesis,stereochemistry, and solvatochromic effects of a 1-(dipyrrinon-9-yl)-3-(dipyrrinon-9-ylidene)-1-propene

Summary By condensing a dipyrrinon-9-yl-acrolein with a dipyrrinone unsubstituted in position 9, an unsymmetricb-vinylogous verdinoid pigment was prepared. The configuration of this molecule was elucidated by means of 2D¹H NMR experiments to be (4Z,10E,12Z,17Z) in solutions of chloroform and dimethylsulfoxide, and its conformation was derived to be 5syn,9syn,11anti,16syn. The pronounced solvatochromic effect of this molecule with a cyclic helical geometry could be explained by solvent induced conformational changes.

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Zur Chemie von Pyrrolpigmenten, 97. Mitt.: Synthese, Stereochemie und Solvatochromer Effekt eines 1-(Dipyrrinon-9-yl)-3-(dipyrrinon-9-yliden)-1-propens

Zusammenfassung Durch Kondensation eines Dipyrrinon-9-yl-acroleins mit einem in Position 9 unsubstituierten Dipyrrinon wurde ein unsymmetrischesb-vinyloges verdinoides Pigment dargestellt. Die Konfiguration dieses Moleküls wurde mit Hilfe von 2D-¹H-NMR-Experimenten in Lösungen von und Dimethylsulfoxid als (4Z,10E,12Z,17Z) abgeleitet; seine Konformation konnte zu 5syn,9syn,11anti,16syn festgelegt werden. Die ausgeprägte Solvatochromie dieses Moleküls mit cyclisch helikaler Geometrie konnte auf solvensinduzierte konformative Veränderungen zurückgeführt werden.

     

The Synthesis of 3-(2'-Hydroxybutyl) isobenzofuran-1 (3H)-one

l（3H】．Isobenzoturans（Dhthalldes】werereDortedtoexhibitawiderangeofbiologicalactivities．Forexample,3－n－butylphthallde（NB）exhibitsantlasthmatlc’,antlconvuls－ant“actlvltles．PenEandZhouhavestudiedonthemetabolismofNBPInrats‘．Theyfoundthat...     

1-(4-硝基苯基)-3-(2-吡嗪)-三氮烯的合成及与镉(Ⅱ)的显色反应

报道了显色剂1-(4-硝基苯基)-3-(2-吡嗪)-三氮烯化合物的合成及其与镉(Ⅱ)的显色反应。在非离子表面活性剂Triton X-100存在下,pH 10.5的Na2B4O7-NaOH的缓冲介质中,该试剂能与镉(Ⅱ)与发生显色反应,形成摩尔比为4∶1的黄棕色配合物,配合物在波长453 nm处有最大吸收峰,表观摩尔吸光系数ε为6.90×104L.mol-1.cm-1,镉(Ⅱ)质量浓度在0~0.56μg/mL范围内遵守比尔定律。用拟定方法测不同废水中的镉(Ⅱ)。     

Synthesis and Molecular Structure of 1-Acetyl-1-（4-iodophenyl）-3-cyclohexylurea

1INTRODUCTION N-acyl urea is an important class of compounds because of their various bioactivities,and they can be used as pesticides[1]and pharmaceuticals[2].On the other hand,many natural products bearing N-acylurea functionality also exhibit the inter…     

1-(8-喹啉)-3-(2-苯并噻唑)三氮烯的合成及其与铜(Ⅱ)的显色反应

合成了新的三氮烯试剂:1 (8 喹啉) 3 (2 苯并噻唑) 三氮烯(QBTT),并研究了该试剂与Cu2 的显色反应,建立了测定铜的灵敏度较高、选择性较好的光度分析新方法。在选定的实验条件下,Cu2 与QBTT在室温下迅速生成络合比为1∶1的紫色络合物,其最大吸收波长为590nm,表观摩尔吸光系数ε=7.48×104L·mol-1·cm-1,Cu2 的质量浓度在0～1.0μg/mL范围内符合比尔定律,该方法可用于测定食品中的微量铜。     

Synthesis and Alkylation of Piperidinium 4,5-trans-3-Cyano-6-hydroxy-4-(2-iodophenyl)-6-methyl-5-(2-methylphenyl)carbamoyl-1,4,5,6-tetrahydropyridine-2-thiolate. Molecular and Crystal Structure of 3-(2-Iodophenyl)-2-(4-phenyl-2-thiazolyl)acrylonitrile

The reaction of o-iodobenzaldehyde, cyanothioacetamide, and N-acetoacetyl-o-toluidine in the presence of piperidine gave piperidinium 4,5-trans-3-cyano-6-hydroxy-4-(2-iodophenyl)-6-methyl-5-(2-methylphenyl)carbamoyl-1,4,5,6-tetrahydropyridine-2-thiolate used in the synthesis of substituted 4,5-trans-2-alkylthiotetrahydropyridines and 2-(2-thiazolyl)acrylonitriles. The structure of 3-(2-iodophenyl)-2-(4-phenyl-2-thiazolyl)acrylonitrile was studied using X-ray diffraction structural analysis.