Asymmetric synthesis of 4-formyl-1-(ω-haloalkyl)-β-lactams and their transformation to functionalized piperazines and 1,4-diazepanes

Chiral piperazine and 1,4-diazepane annulated β-lactams, prepared from the corresponding (3R,4S)-4-imidoyl-1-(ω-haloalkyl)azetidin-2-ones through reduction with sodium borohydride in ethanol, were transformed into novel methyl (R)-alkoxy-[(S)-piperazin-2-yl]acetates and methyl (R)-alkoxy-[(S)-1,4-diazepan-2-yl]acetates upon treatment with hydrogen chloride in methanol. On the other hand, bromination of (3R,4R)-1-allyl-4-formyl-β-lactams and (3R,4S)-1-allyl-4-imidoyl-β-lactams in dichloromethane, followed by sodium borohydride reduction of the resulting dibrominated azetidin-2-ones in ethanol, did not afford the envisaged bicyclic β-lactams but unexpectedly furnished (3R,4S)-1-(2-bromo-2-propenyl)azetidin-2-ones instead.     

链状[NH3CH2CH2NH3]AgAsS4的溶剂热合成及表征

利用溶剂热方法合成了链状[NH3CH2CH2NH3]AgAsS4,通过单晶X射线衍射技术对其进行了晶体结构分析,该化合物晶体属单斜晶系,空间群C2/c,晶胞参数a=1.35805(8)nm,b=0.65331(3)nm,c=2.27711(9)nm,β=106.42(3)°,Z=8.化合物具有有趣的梯子状双链结构,该阴离子链由AsS4与AgS3共用顶点交替连接而成,有机阳离子在阴离子链之间存在较强的N—H…S氢键.DSC和Tg分析结果表明化合物在200℃以下是稳定的.     

加速溶剂萃取/气相色谱-三重四极杆串联质谱法测定纺织品中24种多环芳烃

建立了加速溶剂萃取/气相色谱-三重四极杆串联质谱(ASE/GC-MS/MS)同时测定纺织品中24种多环芳烃(PAHs)的方法。样品经丙酮加速溶剂萃取,旋蒸浓缩后采用DB-35色谱柱程序升温分离,选择多反应监测模式(MRM)采集,外标法定量。结果表明,在一定浓度范围内多环芳烃的峰面积与质量浓度呈良好的线性关系,相关系数(r~2)均大于0.994,方法检出限为0.000 3~0.03 mg/kg,方法定量下限为0.001~0.10 mg/kg,加标回收率为80.3%~103%,相对标准偏差(RSD)为1.3%~9.2%。该方法灵敏、准确可靠,能满足纺织品中24种多环芳烃的测试要求。     

Catalytic Gas‐Phase Production of Lactide from Renewable Alkyl Lactates

A new route to lactide, which is a key building block of the bioplastic polylactic acid, is proposed involving a continuous catalytic gas‐phase transesterification of renewable alkyl lactates in a scalable fixed‐bed setup. Supported TiO₂/SiO₂ catalysts are highly selective to lactide, with only minimal lactide racemization. The solvent‐free process allows for easy product separation and recycling of unconverted alkyl lactates and recyclable lactyl intermediates. The catalytic activity of TiO₂/SiO₂ catalysts was strongly correlated to their optical properties by DR UV/Vis spectroscopy. Catalysts with high band‐gap energy of the supported TiO₂ phase, indicative of a high surface spreading of isolated Ti centers, show the highest turnover frequency per Ti site.     

Direct Access to Aryl Bis(trifluoromethyl)carbinols from Aryl Bromides or Fluorosulfates: Palladium‐Catalyzed Carbonylation

A palladium‐catalyzed carbonylative approach for the direct conversion of (hetero)aryl bromides into their α,α‐bis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane. In addition, aryl fluorosulfates proved highly compatible with these reaction conditions. The method is tolerant of a diverse set of functional groups, and it is adaptable to late‐stage carbon‐isotope labeling.     

Electrical,optical, and structural characterization of p‐type N‐doped SnO thin films prepared by thermal oxidation of sputtered SnNx thin films

We present a study of electrical and optical properties of nitrogen‐doped tin oxide thin films deposited on glass by the DC Magnetron Sputtering method. The deposition conditions to obtain p‐type thin films were a relative partial pressure between 7% and 11% (N₂ and/or O₂), a total working pressure of 1.8 mTorr and a plasma power of 30 W. The deposited thin films were oxidized after annealing at 250°C for 30 minutes. X‐ray diffraction results showed that the as‐deposited thin films exhibit a Sn tetragonal structure, and after annealing, they showed SnO tetragonal structure. X‐ray photoelectron spectroscopy results showed the presence of nitrogen in the samples before and after annealing. The measured physical parameters of the thin films were optical band gap between 1.92 and 2.68 eV, resistivity between 0.52 and 5.46 Ωcm, a concentration of p‐type carriers between 10¹⁸ and 10¹⁹ cm^?3, and a Hall mobility between 0.1 and 1.94 cm²V^?1s^?1. These thin films were used to fabricate p‐type thin film transistors.     

Gas-phase behaviour of negative ions produced from thiazidic diuretics under electrospray conditions

A systematic mass spectrometric study of 10 thiazidic diuretics and related compounds was undertaken by mass spectrometry (MS) with electrospray ionization in the negative ion mode. Collisional dissociation 'in-source' (CID-MS) and in a low-pressure collision cell (CID-MS/MS) were compared in both excitation regions. Spectra obtained by CID-MS and by CID-MS/MS were matched. Using the two methods, loss of HCl and consecutive dissociations from 2HCl losses were exhibited from compounds such as methyclothiazide and trichlormethiazide but not from other thiazidic diuretics that contain chlorine substituents in the aromatic moiety. However, deprotonated dichlorphenamide gave rise to loss of HCl by CID-MS and CID-MS/MS. For other diuretics such as hydroflumethiazide and hydrochlorothiazide, the loss of HCN and [HCN + SO(2)] was relevant. Reaction mechanisms were checked by means of deuterium-hydrogen exchange, which showed that deprotonation took place regioselectively on the heterocyclic moiety. The cleavage pathways require molecular isomerization forming ion-dipole complexes prior to decompositions, allowing long-distance proton transfer for neutral elimination. Identifications of the most specific fragmentations presented in this paper were applied to the screening and unambiguous identification of diuretics for horse doping control.     

Poly(4‐vinylpyridine) as the host ligand of metal‐containing chromophores for second‐order nonlinear optical active materials

Two formulas of grafted polymers with metal‐containing chromophores, potentially suitable for second‐order nonlinear optics applications, are described. Two chromophores were obtained from a tridentate ligand coordinated to Cu(II) or Pd(II) ions. The organometallic chromophore fragments were grafted to poly(4‐vinylpyridine) by the pyridinic nitrogen of the host polymer. Some qualities displayed by the new metallated polymers are remarkable: (1) a high value of the first hyperpolarizability coefficient of the chromophores, (2) a high content of the grafted chromophore in the polymers (up to 60 wt %), (3) a considerable increase in the glass‐transition temperatures (up to 240 °C), (4) good thermal stability in air (ca. 280 °C), and (5) good optical transparency of the films. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2987–2993, 2002     

Retroracemization using new forms of Belokon's original ligand: ­intermediate NiII complexes of N‐({2‐[N‐(S)‐alkylprolylamino]phenyl}phenylmethylene)‐(S)‐phenylalanine (alkyl is 2‐picolyl, 3‐picolyl or ethyl)

In the title compounds, [N‐(phenyl{2‐[N‐(S)‐(2‐picolyl)­prolyl­amino]­phenyl}methyl­ene)‐(S)‐phenyl­alaninato]­nickel(II), [Ni(C₃₃H₃₀N₄O₃)], (I), [N‐(phenyl{2‐[N‐(S)‐(3‐picolyl)­prolyl­amino]­phenyl}methyl­ene)‐(S)‐phenyl­alaninato]­nickel(II) hemihydrate, [Ni(C₃₃H₃₀N₄O₃)]·0.5H₂O, (II), and [N‐({2‐[N‐(S)‐ethyl­prolyl­amino]­phenyl}phenyl­methyl­ene)‐(S)‐phenyl­ala­nin­ato]­nickel(II), [Ni(C₂₉H₂₉N₃O₃)], (III), the Ni^II centres have approximate square‐planar coordination geometries from N₃O donor sets. The picolyl N atoms in (I) and (II) are too remote from the metal centres to interact significantly, but the metal coordination geometries experience tetrahedral distortion and/or displacement of the metal centre from the N₃O plane. These are linked to conformational differences between the ligands of the symmetry‐independent complexes (Z′ = 2), which in turn are related to molecular packing. In (III), where a less sterically demanding ethyl group replaces the picolyl substituents, there are none of the distortions or displacements seen in (I) and (II).