Crystal and molecular structures of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones

An X-ray study of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones is reported. The bond lengths inside the H ring are equalized due to the classical N-H...O hydrogen bond between the carbonyl oxygen and the amino group. In the 4-(2′-hydroxyethyl)amino-pent-3-en-2-one crystal, due to the classical N-H...O bonds, infinite zigzag chains are formed along the 0b axis and arranged into a layered structure due to the weak C-H...O interactions. In (±)-4-(2′-hydroxypropyl)aminopent-3-en-2-one crystal, however, centrosymmetric dimers are formed, which are then linked by weak C-H...O intermolecular interactions to form a layered structure along the a0b plane.     

Eine Synthese des 3-(N′-Methyl-2′-piperidyl)-chinolizidins

Zusammenfassung Im Anschluß an kürzlich erschienene Arbeiten über Synthesen von 3-(N-Methyl-2-piperidyl)-chinolizidin, einer Verbindung von der gleichen Struktur wie sie dem Alkaloid Pusillin zukommen soll, wird über eine eigene Synthese zweier stereoisomerer Verbindungen dieser Konstitution berichtet.     

核苷2′或3′-(硫代)膦酸酯的合成

通过(硫代)亚磷酸二酯与酮核苷的羰基的加成反应合成了2′位或3′位(硫代)膦酰修饰的核苷,在这一加成反应中,只检测和分离到一种异构体.文中对该异构体的构型进行了讨论.     

Microwave promoted one-pot synthesis of 3-(2′-amino-3′-cyano-4′-arylpyrid-6′-yl)coumarins

A facile procedure for the synthesis of 3-(2′-amino-3′-cyano-4′-arylpyrid-6′-yl)coumarins are being reported starting from 3- acetylcoumarin,aromatic aldehydes and malononitrile.The reactions were carded out on microwave irradiation in good yield with short time and easy work-up.The structures of all the compounds have been confirmed on the basis of their analytical,IR,~1H NMR, and mass spectral data.     

Synthesis and Crystal Structure of 1′-Methyl-4′- (4-chlorophenyl)-1H-indole-3-spiro-2′-pyrrolidine- 3′-spiro-4'-(2'-phenyloxazole)-2,5'(3H,4'H)-dione

The title compound (C26H20ClN3O3) has been synthesized by 1,3-dipolar cycloaddition reaction from isatin, sarcosine and (Z)-4-(4-chlorobenzylidene)-2-phenyloxazol-5(4H)-one through a one-pot procedure, and its structure was confirmed by IR, 1H NMR, elemental analysis and single-crystal X-ray diffraction analysis. The crystal belongs to the triclinic system, space group P1, with a = 9.3903(19), b = 11.398(2), c = 12.603(3) , α = 83.495(3), β = 68.988(3), γ = 67.178(3)°, V = 1160.1(4) 3, Z = 2, Mr = 457.90, Dc = 1.311 g/cm3, μ = 0.198 mm-1, F(000) = 476, the final R = 0.0489 and wR = 0.1144 for 3109 observed reflections with I > 2σ(I).     

Transition metal(II) complexes of 1-(α-hydroxynaphthyl)-2-(3′-methyl-5′-mercapto-1′,2′,4′-triazole)-2-aza-ethane

Summary Binuclear metal complexes of the type [M(HMTE)-(H₂O)₂]₂, where HMTE=1-(-hydroxynaphthyl)-2-(3-methyl-5-mercapto-1,2,4-triazolc)2-aza-ethane and M-Cu^II, Co^II, Ni^II and Mn^II have been prepared and characterized. An octahedral geometry around the metals is proposed. The complexes have been screened as possible fungicides.     

Synthesis and Structure Determination of (2S, 2′S)-3-Phenyl-2-(pyrrolidin-2′-yl)- propionic Acid

Abstract

Aβ²,β³-homoproline derivative, (2S, 2′S)-3-phenyl-2-(pyrrolidin-2′-yl)propionic acid, was synthesized starting from l-proline. After preparation of the (4S, 4aS)-4-benzyl-4a,5,6,7-tetrahydro-pyrrolo-[1,2-c]pyrimidine-1,3-dione under a mild condition, the absolute configuration of target compound was assigned using 2D H-H COSY and H-H NOESY technologies.     

Investigations in the region of 2,3′-biquinoline. 3. Synthesis of 2′-alkyl(aryl)-1′,2′-dihydro-2,3′-biquinolines and 2′-alkyl(aryl)-2,3′-biquinolines

A method was developed for the synthesis of 2-alkyl(aryl)-1,2-dihydro-2,3-biquinolines, based on the addition of organolithium compounds to 2,3-biquinoline in the presence of tetramethylethylenediamine. Their oxidation with manganese dioxide led to 2-alkyl(aryl)-2,3-biquinolines.For Communication 2, see [1].Stavropol State University, Stavropol 355009, Russia. Russian Chemical-Technology University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 350–354, March, 1998.     

Synthesis and functionalization oftrans-2-(2′-aminocyclohexyloxy)-andtrans-2-(2′-azidocyclohexyloxy)acetic acid

Summary Synthesis of the hydrochloride oftrans-2-(2-aminocyclohexyloxy)acetic acid (4) fromtrans-2-(2-azidocyclohexyloxy)acetic acid (1) is described.4 was acylated at the amino group to give compounds5–8.1 was converted into acid chloride (9) and amides10–13.

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Synthese und Funktionalisierung dertrans-2-(2-Aminocyclohexyloxy)- undtrans-2-(2-Azidocyclohexyloxy)essigsäure

Zusammenfassung Die Synthese destrans-2-(2-Aminocyclohexyloxy)essigsäurehydrochlorids (4), ausgehend vontrans-2-(2-Azidocyclohexyloxy)essigsäure (1), wird beschrieben.4 wurde durch Acylierung der Aminogruppe in die Verbindungen5–8 übergeführt.1 wurde in das Säurechlorid9 und die Carbonsäureamide10–13 umgewandelt.

     

Stereoselective synthesis and absolute configuration of (1′R,3R,4R)-4-acetoxy-3-(2′,2′,2′-trifluoro-1′-hydroxyethyl)azetidin-2-one

The title compound 3, an intermediate in the synthesis of fluorocarbapenems, is obtained with high stereocontrol by the condensation of (R)-(+)-ethyl 4,4,4-trifluoro-3-hydroxybutanoate with N-trimethylsilyl cinnamylidenimine. X-Ray diffraction analysis of the condensation product and chemical correlations allowed the unambiguous determination of the absolute configuration.     

Theoretical study on the hydrolysis mechanism of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine

The hydrolysis mechanisms of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine (FA-3TC) in the gas phase and in aqueous solution were studied by use of the density functional theory B3LYP/6-31 G(d, p) method. Two possible reaction pathways in the title reaction were considered. In one pathway water attacks the C=N double bond first (path A) while in the other water attacks the C—N single bond first (path B). The calculated results indicate that the first step in both pathways is the rate-limiting process and path A is more favorable than path B in the gas phase. The effect of solvent water on the title reaction was assessed at the B3LYP/6-31 G(d, p) level of theory based on the po-larizable continuum model (CPCM). In water the first mechanism (path A) is also favored.     

Synthesis of 5-substituted-3-[(2′S,3′S)-3′-hydroxy-2′-hydroxymethyltetrahydrofuran-3′-yl]-1,2,4-oxadiazoles and their epimers

5-Phenyl-3-[(2′R,3′S)-3′-hydroxy-2′-dimethoxymethyltetrahydrofuran-3′-yl]-1,2,4-oxadiazole 10a and its epimer 11a, 5-methyl-3-[(2′R,3′S)-3′-hydroxy-2′-dimethoxymethyltetrahydrofuran-3′-yl]-1,2,4-oxadiazole 10b and its epimer 11b were synthesized from cyanohydrin benzoates 8a, 9a and cyanohydrin acetates 8b, 9b, respectively, by treatment with hydroxylamine in methanol via intramolecular transacylation and subsequent cyclization of the corresponding amidoximes. Hydrolysis and reduction of the dimethoxymethyl groups in the above compounds gave the desired compounds 12a, 13a, 12b and 13b.     

Comeplexes of 1-(2′-hydroxybenzyl)-2-(2′-hydroxyphenyl)-benzimidazole with U(VI) and Ce(IV)

Some new U(VI) and Ce(IV) complexes of 1-(2′-hydroxybenzyl)-2-(2′-hydroxyphenyl)-benzimidazole have been prepared and characterized by spectrg magnetic and conductance studies. IR spectral data suggests that the ligand in all the complexes is monodenate through the tertiary nitrogen and that the phenolic oxygen is free from coordination. Conductivity measurements indicate that the nitrate and acetate complexes of U(VI) are non-electrolytes, whereas the nitrate complex of Ce(IV) is a 1:1 electrolyte.     

Die indikatoreigenschaften des vicinalen m-Xylenolphthaleins (3′ ,5′ ,3′' ,5′'-Tetramethylphenolphthalein)

Ohne ZusammenfassungMit 1 Abbildung     

Transition metal complexes derived from 2-hydroxyimino-3-(2′-hydrazonopyridyl)-butane

Summary The complexes of Mn^II, Co^II, Ni^II, Cu^II, Zn^II, Cd^II, Hg^II, Co^III and UO ₂ ²⁺ ions with 2-hydroxyimino-3-(2-hydrazonopyridyl)-butane (HL) have been synthesised and characterized by elemental analyses, molar conductivities, magnetic measurements and spectral (i.r., visible, n.m.r.) studies. I.r. spectra show that HL behaves as a neutral or mononegative ligand and binds in a bidentate and/or tridentate manner. Also, HL behaves as oxidizing agent towards Co^II forming diamagnetic Co^III complexes depending on the preparative conditions. Different stereochemistries are proposed for Mn^II, Co^III, Co^II, Ni^II and Cu^II on the basis of spectral and magnetic studies.     

Synthesis of 3-chloro-N′-(2-hydroxy-6-pentadecylbenzylidene)benzothiophene-2-carbohydrazide

3-Chloro-N′-(2-hydroxy-6-pentadecylbenzylidene)benzothiophene-2-carbohydrazide has been synthesized by the reaction of 2-hydroxy-6-pentadecylbenzaldehyde with 3-chloro-1-benzothiophene-2-carboxylicacidhydrazide in the presence of glacial acetic acid in ethanol. The structure of this new compound was confirmed by elemental analysis, IR, ¹H NMR, ¹³C NMR and mass spectral analysis.     

Coordination Networks Self-assembled by Transition Metal Salts With 4,4′-oxydianiline (4,4′-oda). Syntheses and Structures of ∞ 1 [Ni(NCS) 2 (4,4′-oda) 2 ], ∞ 2 [Co(NCS) 2 (4,4′-oda) 2 ] and ∞ 2 [M(N 3 )(4,4′-oda) 2 ]NO 3 (M=Cd II or Co II )

Four infinite complexes X 1 [Ni(NCS) 2 (4,4'-oda) 2 ], X 2 [Co(NCS) 2 (4,4'-oda) 2 ] and X 2 [M(N 3 )(4,4'-oda) 2 ]NO 3 [M=Cd II ( 3 ) or Co II ( 4 )] were obtained by reactions 4,4'-oxydianiline (4,4'-oda) with Ni(SCN) 2 , Co(SCN) 2 , Cd(N 3 ) 2 and Co(N 3 ) 2 , respectively which have been structurally established by single-crystal X-ray diffraction. Complex 1 contains one-dimensional double-stranded chains comprising 24-membered Ni 2 (4,4'-oda) 2 macrocycles, each formed by two 4,4'-oda ligands and two octahedral Ni II centers. Complex 2 exhibits two-dimensional non-interpenetrating networks consisting of large 48-membered macrocycles each formed by four 4,4'-oda ligands and four octahedral Co II centers. The crystal structures of 3 and 4 are isomorphous and both contain one-dimensional double-stranded chains comprising 24-membered M 2 (4,4'-oda) 2 macrocycles, which are interlinked by w -1,3-azide groups to generate cationic two-dimensional sheets. These sheets are further connected by hydrogen bonds between the amine groups and nitrate ions to furnish three-dimensional networks. Crystal data: complex 1 crystallizes in the monoclinic space group P 2 1 / c with a =11.990(4) Å, b =9.413(4) Å, c =12.827(4) Å, g =116.32(2), V =1297.6(8) Å 3 and Z =2; complex 2 crystallizes in the orthorhombic space group Pbca with a =9.583(2) Å, b =12.738(3) Å, c =21.039(4) Å, V =2568.2(9) Å 3 and Z =4; complex 3 crystallizes in the monoclinic space group C 2/ c with a =23.036(5) Å, b =5.920(1) Å, c =17.800(4) Å, g = 92.67(3), V =2424.8(9) Å 3 and Z =4; complex 4 crystallizes in the monoclinic space group C 2/ c with a = 22.861(5) Å, b =5.812(1) Å, c =17.720(4) Å, g =93.00(3), V =2351.2(8) Å 3 and Z =4.     

Eu(DMBM)2(2,2′-bipy)NO3的合成与荧光光谱

本工作首次合成了Eu(DMBM)₂(2,2′-bipy)NO₃(DMBM=二对甲氧基苯甲酰甲烷,2,2′-bipy-2,2′-联吡啶)。通过元素分析、热谱、电导率、红外和拉曼光谱、质子核磁共振谱对所合成化合物进行了表征。在77K测定了固体配合物的激发光谱和发光光谱。光谱数据说明配合物含有两种Eu(Ⅲ)格位。配合物中三种配体在Eu(Ⅲ)周围的分布情况略有不同,显示出不同的晶体场效应。光谱数据表明,配合物中Eu(Ⅲ)格位属于非中心对称的点群C₁或C₃或C₂。