A Convenient Synthesis of N-Functionalized Perfluoroalkanesulfonamides

This article describes the synthesis of new N-functionalized perfluoroalkanesulfonamides (5) with two sulfonamides functionalities. Perfluoroalkanesulfonyl fluoride underwent a reaction with 2-chloroethylamine hydrochloride or 3-bromopropylamine hydrobromide to give N-(2-chloroethyl or 3-bromopropyl) perfluoroalkanesulfonamides (1). Reaction of (1) with potassium thiocyanate gave N-(2-thiocyanatoethyl or 3-thiocyanatopropyl) perfluoroalkanesulfonamides (3). The sulfonyl chloride derivatives (4) were prepared by reaction of 3 with sulfuryl chloride. In the last step, 4 reacted with ammonia to give the bis sulfonamides derivatives (5). The structures of all new compounds prepared were determined by ¹H, ¹⁹F, and ¹³C NMR spectroscopies and by HR-MS.     

Synthesis and Characterization of Bimetallic Nickel and Cobalt Carbonyl Complexes Containing Stannyl Groups

The bimetallic NiSn₂ complex Ni(SnBu₃^t)₂(CO)_3, 1, was obtained from the reaction of Ni(COD)₂ and Bu₃^tSnH and CO. The reaction of Co₂(CO)₈ and Bu₃^tSnH afforded the bimetallic Co–Sn complex Co(SnBu₃^t)(CO)₄, 3. Compound 3 was also obtained from the reaction of Co₄(CO)₁₂ and Bu₃^tSnH but in a lower yield. Both compounds 1 and 3 were characterized by single crystal X-ray diffraction, and possess trigonal bipyramidal geometries around the transition metal centre with two and one stannyl ligands, respectively.     

Synthesis of Novel bis-Phosphonate Derivatives by Pudovik Reaction

Synthesis of novel bis-(3-methyl-5-nitro-2-oxo-2,3-dihydro-2λ ⁵benzo[1,3,2]oxazaphosphol-2yl)substituted aryl methanes was accomplished by Pudovik reaction. Addition of equimolar quantities of 2-methylamino-4-nitro phenol (1) and ethanol to PCl₃ afforded cyclic condensation product. On reaction with respective aldehydes followed by treatment with phosphorus(III) monochloride of 1, and on subsequent reaction at reflux temperature, this rearranged from P(III) to P(V) state. Their structures were determined by IR, ¹H NMR, ¹³C NMR, ³¹P NMR, and mass spectral data.     

2-Phenyl-1-boraadamantane complexes. Synthesis and intramolecular dynamics

The reaction of triallylborane with 3-phenylprop-1-yne at 135–140 °C followed by treatment of the reaction mixture with MeOH afforded 7-benzyl-3-methoxy-3-borabicyclo[3.3.1]non-6-ene (1) in 81% yield. Hydroboration of compound1 with a solution of BH₃ in THF yielded the tetrahydrofuran complex of 2-phenyl-1-boraadamantane (2). The reactions of trimethylamine or pyridine with compound2 afforded the trimethylamine (3) or pyridine (4) complexes of 2-phenyl-1-boraadamantane. respectively. Hindered rotation about the C(2)−Ph bond in adduct3 was observed by¹H and¹³C NMR spectroscopy. The activation energy of this process is 58.6 kJ mol⁻¹ (determined by 2D¹H−¹H EXSY spectroscopy).     

白藜芦醇类似物的合成

3,5-二甲氧基苄溴(4)与NaCN反应生成3,5-二甲氧基苄腈(5), 5经水解得到3,5-二甲氧基苯乙酸(6). 5与苯甲醛或取代苯甲醛发生Knoevenagel反应生成化合物2a～2d, 为Z式构型. 6与苯甲醛或取代苯甲醛发生Perkin反应得到化合物3a～3c, 为E式构型. 2a～2d和3a～3c均为白藜芦醇类似物. 给出了各步反应产物的IR, ¹H NMR, ¹³C NMR和MS数据, 讨论了影响反应的因素, 并给出了化合物2a～2d和3a～3c对乳腺癌细胞MCF-7、肺癌细胞H446、乳腺癌细胞231的体外生理活性和对正常肝细胞L02体外毒性的半致死浓度.     

Synthesis and Structures of Titanosiloxane Cage Compounds

Reaction of (triphenylmethyl)silanetriol (1) with cyclopentadienyltitanium trichloride (CpTiCl₃) in the presence of triethylamine as a HCl scavenger gave both compounds of a partial open-cage type {[Ph₃CSiO(OH)]₃(Ph₃CSiO_3/2)(CpTiO_3/2)₄} (2) and cube type (Ph₃CSiO_3/2CpTiO_3/2)₄ (3). The 1:1 reaction of 1 and CpTiCl₃ in toluene solvent at reflux temperature for 3 d afforded compounds 2 (22%) and 3 (36%). When 1 is reacted with a 1.5 fold excess of CpTiCl₃ under the same conditions, compound 3 was obtained in high yield (81%) along with 2 in trace quantities. Compounds 2 and 3 were fully characterized by the analyses of ¹H, ¹³C, ²⁹Si NMR, IR, and FAB MS data. The solid-state structure of 3 was determined by a single crystal X-ray diffraction study. Compound 3 had shown to have catalytic activity for the oxidation of alkenes such as 1-octene, cyclooctene, and norbornene with t-butyl hydrogen peroxide. The effect of solvent was observed in this epoxidation reaction. The order of reactivity were decreased as follows: CHCl₃ > hexane THF.     

4-溴-2-环戊烯砜酯化衍生物的合成

以3,4-二溴环戊砜(1)为原料, 在无水吡啶作用下发生消除反应, 得到反应中间体4-溴-2-环戊烯砜(2), 再分别与一系列取代苯甲酸盐3a～3c以及茜素黄GG (3d)发生酯化反应, 合成出4种新环戊烯砜衍生物4a～4d, 并用IR, ¹H NMR, MS, 元素分析等表征了它们的结构.     

Synthesis and spectroscopic studies of new organotin(IV) complexes with tridentate N- and O-donor Schiff bases

The Schiff bases H₂L¹ and H₂L² have been prepared by the reaction of 2-amino-4-chlorophenol with pyrrole-2-carbaldehyde and 2-hydroxy-1-naphtaldehyde, respectively, and HL³ from reaction of 2-(aminomethyl)pyridine with 2-hydroxy-1-naphtaldehyde. Organotin complexes [SnPh₂(L¹)] (1), [SnPh₂(L²)] (2), [SnMe₂(L²)] (3) and [SnPhCl₂(L³)] (4) were synthesized from reaction of SnPh₂Cl₂ and SnMe₂Cl₂ with these Schiff bases. The synthesized complexes have been investigated by elemental analysis and FT-IR, ¹H NMR and ¹¹⁹Sn NMR spectroscopy. In complexes the Schiff bases are completely deprotonated and coordinated to tin as tridentate ligands via phenolic oxygen, pyrrolic, and imine nitrogens in 1, two phenolic oxygens and imine nitrogen in 2 and 3, and phenolic oxygen, imine and pyridine nitrogens in 4. The coordination number of tin in 1, 2, and 3 is five and in 4 is six.     

Synthesis of Azetidin-2-Ones from Imines and Acids Using Trichloroacetonitrile-Triphenylphosphine Reagent

A one step synthesis of azetidin-2-ones (3a-j) has been described by the reaction of imines (1) with acids (2) in presence of trichloroacetonitrile, triphenylphosphine and triethylamine.     

Synthesis and spectral characterization of new benzimidazolium compounds containing sulfur

Abstract

N-heterocyclic carbene (compound b) was synthesized from reaction of 1-(3-phenylpropyl)-3-methylbenzimidazolium iodide (a) and a strong base in an argon atmosphere. Then, 1-(3-phenylpropyl)-3-methylbenzimidazolium-2-carbodithioate (c) was prepared with carbene and CS₂. Finally, a group of alkyl 1-(3-phenylpropyl)-3-methylbenzimidazolium-2-carbodithioate halides was synthesized with alkyl halides and compound c, occurring products 1-6. Structural characterization of compounds was performed ¹H, and ¹³C NMR, IR, and MS spectroscopy and elemental analysis.     

Synthesis and Investigation of 1,2,3,4-Thiatriazol-5-ylcarbamates

Methyl 1,2,3,4-thiatriazol-5-ylcarbamate (2a), ethyl 1,2,3,4-thiatriazol-5-ylcarbamate (2b), 2-butyl 1,2,3,4-thiatriazol-5-ylcarbamate (2c), allyl 1,2,3,4-thiatriazol-5-ylcarbamate (2d), and 3-(1,2,3,4-thiatriazol-5-yl)oxazolidin-2-one (2e) were synthesized with high yields by the reaction of the corresponding carbon(isothiocyanatidic) acid, alkyl esters, and sodium azide in aqueous solution. The compounds were characterized by ¹H, ¹³C, and ¹⁵N NMR, vibrational spectroscopy (IR), and single crystal X-ray diffraction. The thermal stability was investigated by differential scanning calorimetry.     

Synthesis of 4-isobutyl substituted thiophenes byGewald reaction

Summary TheGewald reaction of 4-methyl-2-pentanone with alkyl cyanoacetates was investigated. Alkyl 2-amino-4-isobutylthiophene-3-carboxylates (4) were formed, together withbis-(2-amino-3-alkoxycarbonyl-4-isobutyl-5-thienyl)-disulfides (5) and alkyl 2-amino-4-isobutyl-5-morpholinothiophene-3-carboxylates (6). The absence of any 4-methyl substituted aminothiophene in the product mixtures came up highly unexpected. The mechanism of the reaction is discussed with respect to previously reported suggestions.Dedicated to Professor Dr.Karl Gewald on the occasion of his 65^th birthday     

以手征性联萘为模板合成一种新的螺旋环芳分子

基于2,2'-二取代的联萘衍生物在手性构型上高度稳定的特点, 分别从光学活性的(R)-和(S)-2,2'-二乙炔基-1,1'-联萘结构模板出发, 通过Sonogashira 偶连反应导入苄基砜, 然后用二异丙基氨基锂(LDA)处理制得的联萘二砜成功地合成了一种新的螺旋环芳分子——对映异构体(R,P)-3和(S,M)-3. MS, IR, ¹H和¹³C NMR以及元素分析表征了这些化合物．镜象特征的圆二色(CD)谱和比旋光度[α]_D的测定结果清楚地反映了它们的对映异构关系．     

One-Pot Synthesis of Cage-Functionalized,Ketal-Containing Crown Ethers

Acid-catalyzed reaction of pentacyclo[5.4.0.0^2,6.0^3,10.0^5.9]undecane-8,11-dione (1) with penta(ethylene glycol) produced two cage-functionalized, ketal-containing crown ethers, i.e., 2 and 3, in low yield. The structure of 2 was established unequivocally by direct methods. Alkali metal picrate extraction data obtained for 2 and for a structurally related model compound, i.e., 18-crown-6,indicate that 2 is an inefficient alkali metal picrate extracting agent.     

稀土-异烟酰肼席夫碱配合物的设计、合成与结构

由异烟酰肼和2-吡啶甲醛合成了席夫碱配体HL,并和稀土离子合成组装得一系列稀土配合物。用X-射线单晶衍射对配合物的结构进行了测定。通过荧光测试发现La配合物有荧光,而Eu,Dy则使配体的荧光淬灭。     

Synthesis of Novel Chalcone Analogues of Ferrocene Biarenes

Abstract

The novel structures of organometallic compounds, 1-biaryl-3-ferrocenyl-2-propene-1-one (5) and 3-biaryl-1-ferrocenyl-2-propene-1-one (9) were synthesized for nonlinear optical chromophores by Suzuki cross-coupling reaction. Their structures were determined with elemental analyses, IR spectra, ¹H NMR spectra, and ¹³C NMR spectra.     

Synthesis of Carbonyl Compounds from Alcohols Using Electrochemically Generated Superoxide Ions in RTILs

Abstract

We show that the superoxide ion (O₂ ^??) generated electrochemically from oxygen dissolved in room-temperature ionic liquids (RTILs) reacts with primary and secondary alcohols to form the corresponding ketones and carboxylic acids, respectively. Specifically, we study the conversion of benzhydrol to benzophenone and benzyl alcohol to benzaldehyde/benzoic acid. The kinetics (e.g., rate, selectivity, and yield) for these reactions are also determined as functions of the variations in the structure of the ionic liquids. The RTILs used here are imidazolium-based cations where the functional groups on the imidazolium ring are modified. Specifically, 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF₆], 1-butyl-2,3-dimethylimidazolium hexafluorophosphate [bdmim][PF₆], and 1-hexyl-3-methylimidazolium hexafluorophosphate [hmim][PF₆] are used as the reaction medium. These results are compared to an ammonium-based RTIL (N-butyl-N-trimethylammonium bis(trifluoromethylsulfonyl)imide). The results show that the nucleophilic attack by the O₂ ^?? of both the RTIL and the alcohol, especially that of the H atom at the R2 position of the [bmim][PF₆] and [hmim][PF₆], greatly affects the yields. No RTIL degradation products were detected for the reactions in [bdmim][PF₆] and N-butyl-N-trimethylammonium bis(trifluoromethylsulfonyl)imide ionic liquids. For the benzyl alcohol oxidation reaction in the RTIL, N-butyl-N-trimethylammonium bis(trifluoromethylsulfonyl)imide, benzaldehyde formed did not undergo further oxidation to form benzoic acid, which may be due to the greater hydrophobicity of this RTIL. The competitive reaction kinetics between the alcohol and RTIL component must be considered in the selection of the RTIL solvent system.     

Synthesis and spectroscopic studies of methoxy-substituted phenylthienylnicotinamidines

Abstract

Five thienylnicotinamidine derivatives 5a–e were prepared from their corresponding nicotinonitriles 3a–e on treatment with lithium trimethylsilylamide [LiN(TMS)₂] followed by hydrolysis using ethanolic/HCl (gas). The nicotinonitriles 3a–e were prepared via Suzuki coupling reaction of bromothienyl derivative 1 with the appropriate phenylboronic acids 2a–e. The DFT calculation was used to optimize the geometric structure of the newly synthesized nicotinamidines. The comparison of DFT/B3LYP calculated spectral data (¹H-NMR and ¹³C-NMR) with the experimental data showed acceptable agreement. Mass fragmentation patterns of 3,4-dimethoxyphenyl, 3,5-dimethoxyphenyl, and 3,4,5-trimethoxyphenyl thienylnicotinamidine derivatives were investigated.     

Synthesis and structure of tetra- and triphenylbismuth arenesulfonates

Tetraphenylbismuth arenesulfonates were synthesized by the reaction of pentaphenylantimony of-bismuth with triphenylbismuth bis(arenesulfonates). Triphenylbismuth bis(arenesulfonates) were synthesized by the reaction of triphenylbismuth with arenesulfonic acids in the presence of hydrogen peroxide. The crystal structures of the tetraphenylbismuth 2,5-dimethylbenzenesulfonate crystal hydrate (1), tetraphenylbismuth 3-carboxy-4-hydroxybenzenesulfonate (2), and triphenylbismuth bis(2,5-dimethylbenzenesulfonate) (3) were determined by X-ray diffraction analysis. The Bi atom in1 has a tetrahedral coordination (bond angles vary from 106.6(6) to 111.9(10)^o). The Bi coordination observed in2 is intermediate between tetrahedral and trigonal-bipyramidal, and that in structure3 is trigonal-bipyramidal, with the oxygen atoms in the axial positions. The Bi−O bond lengths are 2.19(2) and 2.27(2) Å. In the crystal of2, the anions form an infinite hydrogen-bonded chain. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2350–2354, December, 1999.     

新型单膦配位羧酸银配合物的合成、表征及其热稳定性的研究(英)

0 IntroductionIn recent years, silver carboxylates have attractedmany interests, mostly because they are promisingcandidates in the growth of metal thin films via metal-organic chemical vapor deposition (MOCVD) tech-niques. These sliver compounds show low light sensi-tivity and relatively high thermal stability. Several ex-amples of bisphosphine ligands coordinated silver car-boxlylates have been reported[1￣4].Monophosphine coordinated silver complexes areexpected to have better volatility,…