New N,S-Substituted Dienes from Mono(thio)substituted-2-nitrohalo-1,3-diene and Some Amines

Mono(thio)substituted nitrodiene compound 1 reacted with 2a–f and yielded 3a–f in methylene chloride. Compound 1 gave 7 by the reaction with 6. Compounds 5a–c were obtained by the reactions of 4a–c with 1. 3a also has been structurally characterized using single-crystal X-ray diffraction analyses.     

The Synthesis of Novel S-, S,S-, S,S,S-, and N,S-Substituted Nitrodienes from Polyhalonitrodienes and Thiols

Abstract

The novel S-, S,S-, and S,S,S-substituted nitrobutadienes were synthesized from the reactions of 2-nitrobutadiene compounds with some thiols. The new N,S-substituted nitrobutadienes were obtained from the reaction of the mono-thiosubstituted butadienes with morpholine, thiomorpholine, homopiperazine, and piperazine derivatives. The structures of new compounds were determined by spectroscopic techniques.

GRAPHICAL ABSTRACT      

Synthesis of Some Novel S- and N,S-Substituted Chlorobutadienes

Abstract

Mono(thio)substituted nitrodienes were synthesized by reactions of 2-nitro-pentachloro-1,3-butadiene with some thiols [(tert-butylbenzyl)thio- and 2,3,5,6-tetra-fluorophenylthio-] either directly or in ethanol in the presence of sodium hydroxide. N,S-Substituted 1,3-butadienes were obtained from the reaction of the mono(thio)substituted nitrodienes with morpholine and some piperazine derivatives in dichloromethane. Also mono- and di(thio)substituted perchlorobutadienes were synthesized from the reactions of hexachloro-1,3-butadiene with o-aminothiophenol in ethanol in the presence of sodium hydroxide. The structures of the new compounds were characterized by microanalysis and spectroscopic data.     

N,S-Substituted Dienes from Mono(arylthio)substituted- and S-, S,S-Substituted Dienes

Mono(thio)substituted dienes 1a-1b gave compounds 3a-c and 5d-g with piperazine and piperidine derivatives in dichloromethane. Compounds 8 , 9 , and 10 were obtained from the reactions of perchlorobutadiene ( 6 ) with 1,4-butanedithiol ( 7 ) in ethanol in the presence of sodium hydroxide. Compounds 12a-b , 13a-b were obtained from the reactions of perchlorobutadiene ( 6 ) with allylmercaptan (CH 2 =CH--CH 2 --SH) and mercaptoethanol (HO--CH 2 --CH 2 --SH).     

New N,S-Substituted Dienes from the Reactions of Some Aliphatic Mono(thio)substituted Nitrodienes with Aromatic Primary Amines and Cyclic Amines

Reaction of 2-nitropentachlorobutadiene with thiols and amines gave new N,S- and S,S-substituted nitrodiene compounds is discussed.     

Einige Neue N,S-Substituierte 2-Nitrodienverbindungen Aus Reaktionen Von Mono(p-fluorarylthio)substituierten Dienen Mit Aminen

2-Nitrodiene compound 1 was stirred with p-fluorothiophenol for a long time and compound 3 was obtained. Compound 1 gave bis(thio)substituted 2-nitrodiene compound 4 and tris(thio)substituted compound 5 with 2 moles of p-fluorothiophenol in the presence of NaOH in ethanol. The compounds 9a–g have been prepared from 8a–g and 3. Compound 7 was obtained from the reaction of mono(thio)substituted 2-nitrodiene with morpholine. Compound 3 gives 11a–d in the reaction with piperidines in CH₂Cl₂ (or ether). Compound 13a–b have been obtained from the reaction of compound 3 with primary amines 12a–b. Compound 3 gives 15 and 16 in the reaction with 2,5-dimethylpiperazine in CH₂Cl₂.

     

New N,S-Derivatives of Nitrodienes from Thioallyl-and Thiodibromopropyl Nitrodienes

Compound 3 and 5a, b were obtained from the reaction of 1,3,4,4-tetrachloro-1-thioallyl-2-nitro-1,3-butadiene (1) with thiomorpholine (2) and piperazine derivatives 4a, b in dichloromethane. The reaction of compound 1 and bromine gave compound 6. Compounds 8 and 10 were obtained from the reaction of 6 with 1-(diphenylmethyl)piperazine (7) and piperidine (9) in dichloromethane. The derivative 13 was synthesized from the reaction of 4-bromo-1,1,3,4-tetrachloro-2-nitro-1,3-butadiene (11) and allylmercaptane (12). Compounds 15 and 16a, b were obtained from the reaction of 1-allyl-4-bromo-1,3,4-trichloro-2-nitro-1,3-butadiene (13) with morpholine (14) and the piperazine derivatives 16a, b, in dichloromethane, respectively.     

NOVEL N,S-SUBSTITUTED DIENES BY THE REACTION OF 2-NITROTHIOSUBSTITUTED HALODIENES AND PRIMARY AMINES

Mono(thio)substituted 1a–c gave compounds 3a–c and 5a with o-toluidin (2) and m-toluidin (4) in ether. Compounds 9a–c and 11a, b were obtained from the reaction of compounds 1a–c with p-fluorophenylamine (8) and p-fluorobenzylamine (10). Compounds 7a and 15c were obtained from the reaction of 1a and 1c with p-phenylendiamine (6) and o-phenylendiamine (14). Compound 13c was synthesized from the reaction of compound 1c with benzidine (2).     

三烃基（Ph,Cy,Bu）锡芳硫（亚砜,砜）乙酸酯的合成及表征

合成了２２种三烃基（Ｐｈ，Ｃｙ，Ｂｕ）锡芳硫（亚砜，砚）乙酸酯，用元素分析、ＩＲ、ＨＮＭＲ、ＭＳ、ＸＰＳ等手段对其结构进行了表征，结果表明，三环己基锡芳硫（亚砜、砜）乙酸酯具有四配位锡原子的单体结构，三苯基（三丁基）锡芳硫（亚砜、砜）乙酸醌具有五配位原子的聚合结构，通过估算它们的正辛醇－水分配系数，预测其在环境中的吸附及生物富集能力。     

Thermal Investigation of the Compounds of the Copper(II) Mono(o-hydroxybenzoate) with Chelate Ligands

Heteroligand complexes of copper(II) were obtained as a result of the reaction of Cu(II) mono (o-hydroxybenzoate) (monohydrate) with 8-hydroxyquinoline (HOx), o-aminophenol (NH₂Ph) and 2,2′-dipyridyl (2,2′-dipy). The mixture of the mono compound with: Cu(II) di(o-aminobenzoate) or Cu(II) di(o-hydroxybenzaldoximate) were obtained by the reaction with o-aminobenzoic acid (H₂A) and o-hydroxybenzaldoxime (H₂Salox). The obtained compounds and their sinters were subjected to chemical, X-ray and thermal analyses. This revised version was published online in July 2006 with corrections to the Cover Date.     

N,N'-二(2-羟苄基)取代咪唑烷的合成、表征及抑菌活性

利用生物活性叠加原理,将"邻羟苯基"和"咪唑烷"分子片断有机结合,以水杨醛和乙二胺为起始原料,经缩合、NaBH4还原制得N,N'-二邻羟苄基乙二胺(2),进而与芳醛类化合物缩合关环,合成了8种N,N'-二(2-羟苄基)取代咪唑烷类化合物(3a～3h). 化合物的结构经1H NMR、IR、MS和元素分析等测试技术进行了表征. 结果表明,水杨醛与乙二胺的缩合反应,可专一性地生成对称双缩席夫碱化合物(1);芳醛上的取代基对缩合关环反应有显著影响,邻、对位吸电基可使芳醛的羰基活化,有利于缩合关环反应的进行,邻、对位供电基可使芳醛的羰基钝化,不利于缩合关环反应进行. 抑菌测试结果表明,质量分数为0.1%时,N,N'-二(2-羟苄基)取代咪唑烷化合物对不同菌株的抑菌活性具有明显的特异性,对白色念珠菌、大肠杆菌的抑菌率达100%.     

Supramolecular assemblies of two piperazine metal-organic bismuth(III) derivatives: a new precursor for the preparation of bismuth(III) oxide bromide nano-structures

Two BiBr₃ supramolecular complexes, [Bi(2-bpmp)Br_2.06Cl_0.94] (1) and [Bi(4-H₂bpmp)Br_4.29Cl_0.71]·H₂O (2) {2-bpmp = N,N′-bis(2-pyridylmethyl)piperazine and 4-bpmp = N,N′-bis(4-pyridylmethyl)piperazine}, were prepared by reaction of bismuth(III) chloride and potassium bromide with two nitrogen donor ligands under thermal gradient conditions using the branched tube method. Compounds 1 and 2 were structurally characterized by single-crystal X-ray diffraction. In monomeric 1, bismuth is coordinated by two pyridyl and piperazine nitrogens of 2-bpmp, and by three halides. Compound 2 is also monomeric but is bonded to only one pyridyl nitrogen. In both compounds, extensive hydrogen-bonding interactions lead to supramolecular networks; in 2, the hydrogen bonds are augmented by π–π stacking interactions. Thermal stabilities of both compounds were studied by thermal gravimetric and differential thermal analyses. Thermal decomposition of nanosized 1 and 2 in air produced BiOBr nanoparticles.     

二(桥-氯)-二[氯-(N,N,N''''-三苄基乙二胺)铜(Ⅱ)]的晶体结构

0 IntroductionThe copperdim er,bis(μ鄄hydroxo)鄄bis[chloro(N,N,N',N'鄄tetram ethylethylenediam ine) copper髤] chloride(Cu(OH )Cl·TM EDA),prepared from N,N,N',N'鄄tetram鄄ethylethylenediam ine (TM EDA) and CuCl, exhibitedexcellentcatalytic activity for t     

N,N＇-双(二苯膦甲基)哌嗪和钯配合物的合成及苄基氯的催化羰基化反应

含氮两亲膦体;N;N＇-双(二苯膦甲基)哌嗪和钯配合物的合成及苄基氯的催化羰基化反应     

New lead(II) complexes with N,S-ligands,including a lead pyrazolonate with unusual packing flexibility

The reaction of lead(II) acetate in methanol with thiosemicarbazones derived from β-keto esters and β-keto amides (HTSCs) afforded two lead(II) thiosemicarbazonates and numerous homoleptic ([PbL₂]) and/or heteroleptic ([Pb(OAc)L]) complexes containing deprotonated pyrazolones L⁻ formed by metal-induced cyclization of the starting HTSC ligands. All the complexes isolated were characterized by IR spectroscopy in the solid state and by ¹H and ¹³C NMR spectroscopy in DMSO solution; in addition, crystals containing [Pb(L⁶)₂] and [Pb(L⁷)₂] were examined by X-ray crystallography. [Pb(L⁶)₂] · 0.5H₂O · 0.3MeOH (HL⁶ = 4-ethyl-2,5-dihydro-3-methyl-5-oxo-1H-pyrazole-1-carbothiamide) showed three types of molecule with significant structural differences that appear to be determined by packing interactions. In all three molecules the Pb?Pb distances are very short [3.6096(8)–3.7562(8) Å], but density-functional-theoretic calculations at the B3LYP level do not support the existence of Pb–Pb bonds. In [Pb(L⁷)₂] (HL⁷ = N-ethyl-2,5-dihydro-3-methyl-5-oxo-1H-pyrazole-1-carbothiamide) all the molecules are of a single type, and they are linked in a three-dimensional network by weak intermolecular Pb?O bonds.     

New Effective Synthetic Method for Preparation of N,N-Dichlorocarbamates

A rapid, efficient, economical, and easy-to-scale method for the effective conversion of carbamates to corresponding N,N-dichlorocarbamates by using sodium hypochlorite in acidic medium has been described. N,N-Dichlorocarbamates were obtained in quantitative yield through a simple workup in reduced reaction time.

Synthesis and characterization of [chloro{2(1H)-pyridinethione-S}{tris(pyridin-2-ylthiolato)methyl-C,N,N′,N″]}nickel(II)], [Ni(TPTM)(SPyH)Cl]

The compound, [chloro{2(1H)-pyridinethione-S}{tris(pyridin-2-ylthiolato)methyl-C,N,N′,N″]}nickel(II)], [Ni(TPTM)(SPyH)Cl], was isolated from the reaction between NiCl₂ · 6H₂O and tris(pyridin-2-ylthiolato)methane in aqueous EtOH. X-ray crystallography at 120 K revealed an octahedral arrangement about Ni with a tetradentate tris(pyridin-2-ylthio)methyl-C,N,N,N ligand, a monodentate 2(1H)-pyridinethione-S ligand and a chloride. The 2(1H)-pyridinethione-S ligand was derived from tris(pyridin-2-ylthio)methane probably via an acid catalysed hydrolysis reaction. Intramolecular N–H–Cl and C–H–Cl interactions help to cement the molecular structure. Weak C–H–Cl and C–H–S hydrogen bonding interactions link molecules of [Ni(TPTM)(SPyH)Cl] into a 3D array. EPR and UV spectra, and Hartree–Fock theoretical calculations are reported.     

含氮两亲膦配体N，N‘—双（二苯膦甲基）哌嗪及钯配合物的合成和催化羰化反应

在温和的条件下,以季Lin盐（Ph2P(CH2OH)2]^ Cl^-与胺的曼尼希反应,高产率合成了含Ph2PCH2N=配位基团的两亲膦配体N,N'-双（二苯膦甲基）哌嗪。在正丁醇中于氮气保护下制备了Ph2P/Pd摩尔比为2：1和1：1的钯配合物。该钯配合物对氯苄的常压羰基化反应有很高的催化活性,苯乙酸的产率可达91%。