S-, S,S-, S,S,S- Und N,S-Substituierte Dienverbindungen Und Dibutadienylpiperazinverbindungen Von 2-Nitropentachlorbutadien

Nitrodiene compound 1 was stirred with allylthiol for a long time and compound 3 was obtained. Compound 1 gave bis(thio)substituted 2-nitrodiene compound 4 and tris(thio)substituted 2-nitrodiene compound 5 with 2 moles allylthiol in the presence of NaOH in ethanol. Mono(allylthio)substituted diene compound 3 gave dibutadienyl substituted piperazine compounds with piperazine 6 in CH 2 Cl 2 (or diethylether). Compound 3 gave compound 9 with compound 8 . Compounds 11a-e have been obtained from the reaction of compound 3 with compounds 10a-e . Nach langem Rühren von der Verbindung 1 mit Allylthiol entsteht die Verbindung 3 . Die Verbindung 1 liefert mit zwei Mol von Allylthiol in ethanolischer Natronlunge die bis(thio)substituierte 2-Nitrodienverbindung 4 und tris(thio)substituierte Dienverbindung 5 . Mono(allylthio)substituierte Dienverbindung 3 ergibt mit Piperazine in CH 2 Cl 2 (oder in Ether) die dibutadienylsubstituierte Piperazinverbindung 7 . Die Verbindung 3 liefert mit der Verbindung 8 die Verbindung 9 . Durch die Reaktion von der Verbindungen 10a-c wurden die Verbindungen 11a-e erhalten.     

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.     

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.     

New N,S-Substituted Nitrobutadienes from Mono(Arylthio)Substituted Nitrobutadienes

N,S-Substituted nitrobutadienes 3a–g were synthesized from the reaction of the thiosubstituted derivatives 1a–g with thiomorpholine 2. The N,S-substituted nitrobutadienes 5a–g were obtained from the reaction of the thiosubstituted butadienes 1a–g with N-diphenylmethyl piperazine 4. The structure of butadiene 3c was elucidated by single crystal X-ray diffraction.     

DIBUTADIENYL PIPERAZINE,DIBUTADIENYL HOMOPIPERAZINES AND BUTADIENYL-SUBSTITUTED PIPERIDINES FROM MONOSUBSTITUTED HALODIENES

Compounds 3a–k were obtained from the reactions of compounds 1a–k with homopiperazine (2) in CH ₂ Cl ₂ . Compounds 1a–b, 1d–f, and 1h–l gave compounds 5a–b, 5d–f, and 5h–l with 2-methylpiperazine (4) in dichloromethane. Compounds 7c and 9c were obtained from the reactions of compound 1c with 4-ethoxycarbonyl piperazine (6) and 4-piperidinol (8) in CH ₂ Cl ₂ . Compounds 1a and 1f gave compounds 11a and 11f with 4-methylpiperazine (10), and compound 13f was obtained from the reactions of compound 1f with 4-methylpiperidine (12) in CH ₂ Cl ₂ .     

SOME NEW S-, S,S- AND N,S-SUBSTITUTED 2-NITRODIENES AND BUTADIENYL-SUBSTITUTED PIPERAZINES

Nitrodiene 1 reacted with 2a, b and gave the novel compounds 3a, b, 4a, b, and 5a. Monosubstituted diene compound 3a gave the compounds 9a with morpholine, 11a with piperidine, and 13a with homopiperazine. Compound 3a gives the thioether compound 15 by the reaction with the dithiol (HS─(CH₂)₂─O─(CH₂)₂─SH) in ethanol containing sodium hydroxide.     

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.     

Zinkkomplexe des chelatisierenden N,S,S-Liganden N-(2-Mercaptoethyl)-2-mercaptoanilin

Zinc Complexes of the Chelating N,S,S Ligand N-(2-Mercaptoethyl)-2-mercaptoaniline The organic compound N-(2-mercaptoethyl)-2-mercaptoaniline (LH₂) which as a ligand offers two SH functions, which can be deprotonated, and one NH donor function was prepared by a new method. Its reaction with zinc salts yielded the 1:1 complex ZnL. The structure analysis identified the complex as a molecular tetramer with bridging thiolate groups, a tetrahedral ZnNS₃ coordination, and a step-like Zn₄S₄ ring as the central structural unit. Attempts to break up the tetramer by addition of coligands were successful only for 2,2′-bipyridine which produced the complex LZn · bipy.     

Alternativ-Liganden. XXV. Neue Chelatliganden des Typs Me2ESiMe2(CH2)2E′Me2 (E=P,As; E′=N,P, As)

Alternative Ligands. XXV. New Chelating Ligands of the Type Me₂ESiMe₂(CH₂)₂E′Me₂ (E=P, As; E′=N, P, As) Chelating ligands of the type Me₂EsiMe₂(CH₂)₂E′ Me₂, have been prepared by the following routes: Starting from Me₂Si(Vi)Cl, the compounds with E=N and E′ =N ( 1 ), P ( 2 ), As ( 3 ) are obtained in yields of 65 to 78% by aminolysis to yield Me₂NSiMe₂Vi, followed by the LiE′ Me₂ catalyzed addition of He′Me₂ to the vinyl group. The intermediates ClSiMe₂(CH₂)E′Me₂ [E′=N ( 4 ), P ( 5 ), As ( 6 )] are produced by the reactions of 1 to 3 with PhPCl₂. 5 and 6 can be prepared in a purer form by the photochemical addition of HPMe₂ and HAsMe₂, respectively, to the vinyl group of Me₂Si(Vo)Cl. 4 to 6 react with LiEMe₂, in situ prepared from n-BuLi and HEMe₂, to yield the ligands Me₂ESiMe₂(CH₂)₂E′Me₂ ( 7–12 ) (E=P, As; E′=N, P, As). The new compounds have been characterized by analytical and spectroscopic investigations (NMR, MS).     

Unusual Conformational Behavior of 3,7-Dihetera(N,N-;N,O-;N,S-) Bicyclo[3.3.1]Nonan-9-Ols Via Nmr Analysis

Abstract

Based upon the analysis of ¹H NMR data, along with molecular modeling, it was shown that the reduction of 3,7-dihetera(N,N-; N,O-; N,S-)bicyclo[3.3.1]nonan-9-ones by LiAlH₄ led to a mixture of two stereoisomeric secondary alcohols with different orientations of the hydroxyl groups in one of the ring systems. Diaza derivatives in deuterochloroform exist in predominant chair-boat conformations. However, the replacement of nitrogen in one of the heterocycles by oxygen or sulfur led to stereoisomers one of which existed in chair-boat conformation and another in a chair–chair conformation. In all cases the boat conformation is stabilized by formation of an intramolecular hydrogen bond (IMHB) between a lone electron pair of the nitrogen atom and a proton on the pseudo axial hydroxyl group of the other ring.     

Rhenium(V) Complexes of N,N′-Ethylenebis(2-mercaptopropanamide). Synthesis,Characterization, and X-ray Crystal Structures

The preparation of benzoyl-protectcd N,N′-ethylenebis(2-mercaptopropanamide) (H₄emp) and its ligand-exchange reaction with ReO₂(en)₂Cl are described. Three diastereomers, [syn-ReO(meso-emp)]; [anti-ReO(meso-emp)]-, and a pair of cnantiomers, [ReO(rac-emp)]-, were formed due to syn and anti orientation of the two methyl groups of the ligand relative to the ReO core. The diastereomers were separated by reverse phase C₁₈ semipreparative HPLC and isolated as salts of [Ph₄As][ReO-(emp)]. The structures of [Ph₄ As][ReO(meso-emp)] were determined by single-crystal X-ray analyses. [Ph₄As][syn-ReO(mesocmp)]H₂O crystallizes in triclinic space group Pl with a = 10.326(3) Å, b = 13.672(4) A, c = 14.023(5) Å, α = 61.20(2)°, β =74.74(3)°, γ= 75.68(2)° V = 1656.6(8) ų, Z = 2, Dc = 1.676 gmL^?1, F(000) = 824 and R = 0.0329 for 5877 unique reflections. For (he complex [Ph₄As][anti-ReO(meso-emp)], the crystal data are: monoclinic, space group P2₁/n, a = 9.128(2) Å, b = 24.284(7) Å, c = 14.112(4) Å, β = 93.41(2)° V = 3122.5(15) À³, Z = 4, Dc = 1.740 gmL^?1, F(000) = 1608 and R = 0.0361 for 5487 unique reflections. In both structures the rhenium atom is penta-coordinated and in an approximately square pyramidal environment.     

Regioselective Deprotection of 1,3-Dibenzyl-5-(N,N-dimethylamino)-6-phenylethyluracil

The deprotection of 1,3-dibenzyl-5-(N,N-dimethylamino)-6-phenyl-ethyluracil I was investigated.A practical,regioselective N3 deprotection of compound I was performed with excellent yield using cyclohexene as a hydrogen donor.     

ChemInform Abstract: Vibrational Spectrum and Gas-Phase Structure of Disulfur Dinitride (S2N2)

The first gas-phase high-resolution FTIR spectra of S₂N₂ (D_2h) is presented together with a high-level quantum mechanical and experimental study of its molecular ground-state and equilibrium structures.     

Extraction Von Molybdän(V) MIT O,O, S-Tripropyldithiophosphat Aus Salzsauren Lösungen

Abstract

The solvent extraction of molybdenum with o,o,s-tripropyldithiophosphate from hydrochloric acid has been studied. The extractable species is H₂[MoOCl₅] .2 (C₃H₇O)₂-P(S)SC₃H₇ and the thiophosphate can be used to separate molybdenum from Th, Zr, Ti⁴⁺, V⁵⁺, Nb, Ta, Cu²⁺, Fe²⁺, Co²⁺, Ni and Mn²⁺.     

Synthesis and Reaction Chemistry of Sb(ECH2CH2NMe2)3 (E = O,S)

The antimony aminoalkoxide and aminothiolates Sb(ECH₂CH₂NMe₂)₃ [E = O ( 1 ), S ( 2 )] were synthesized and their ability to form adducts with other metal moieties investigated. Compound 1 forms 1:1 adducts with NiI₂ ( 3 ) and M(acac)₂ [M = Cd ( 4 ), Ni ( 5 )], while 2 undergoes ligand exchange with AlMe₃ to afford Me₂AlSCH₂CH₂NMe₂ ( 6 ). The structures of 2 – 4 and 6 were determined. Compound 2 incorporates three S, N‐chelating ligands though the interaction with nitrogen is weaker than in analogous alkoxide complexes. Product 3 reveals one iodine has migrated from nickel to antimony, and all three alkoxide ligands bridge the two metals through μ₂‐O atoms. In contrast, in 4 , only one alkoxide links the antimony and cadmium. Compound 6 adopts the same structure, a chelating S,N ligand generating a tetrahedral center at aluminum, as known tBu₂AlSCH₂CH₂NR₂ species (R = Me, Et).     

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     

Crystal and molecular structure of N,N,N′,N′-tetra(2-nitrilethyl) ethane-1,2-diamine and N-(2-nitrilethyl)benzylamine hydrobromide

N,N,N′,N′-tetra(2-nitrilethyl) ethane-1,2-diamine and N-(2-nitrilethyl)benzylamine hydrobromide were prepared by the addition reaction of acrylonitrile with corresponding amines, and the two structures were determined by X-ray single crystal diffraction. The two compounds crystallize in monoclinic system, and almost no classical hydrogen bond exists in the two crystal structures.     

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     

Flow Injection Analysis of Benzoyl Peroxide Using N,N,N,N-Tetramethyl-p-phenylenediamine (TMPDA) and Surfactants

Abstract

The flow injection analysis of benzoyl peroxide using N,N,N,N-tetramethyl-p-phenylenediamine (TMPDA, also known as Wurster's reagent) and a solvent system including the surfactant sodium dodecyl sulfate (SDS) and cerium(IV) as a catalyst at pH 6.0 at 612 nm was investigated. The method was applied to the analysis of acne cream and flour. The study included a 26-metal-ion search for other possible methods of catalysis and a buffer study of SDS and cetyltrimethyl ammonium bromide (CTAB).