Gas phase reactions of Cl2O with X−(D2O)n=0–4 (X = O,OD, O2, DO2, and O3)

The reactions of Cl₂O with the cluster ions X⁻(D₂O)_n=0–4 (X = O, OD, O₂, DO₂, and O₃) were studied in a He buffer gas at temperatures within the range 171–298 K and pressures of 0.27–0.51 Torr, using a flow-tube apparatus. All ions were found to react with Cl₂O at rates slower than predicted by the collision rate and the charge center was transferred from X⁻ to Cl⁻ or ClO⁻. The primary product ions Cl⁻(DOCl) and ClO⁻(DOCl) were observed to react further to produce the ions Cl₃O⁻ and Cl₃O₂⁻. The rate constants for the observed reactions are reported and the role that thermodynamics plays in determining possible reaction channels is discussed.     

Synthesis of novel O,O"-dialkyl α-aminoalkylphosphonothioates

O,O"-Dialkyl -amino(cyclohexyl)phosphonothioates were synthesized by the reactions of O,O"-dialkyl phosphonothioites with [2-(N-cyclohexylideneamino)ethyl] vinyl ether.     

Oxomolybdenum(VI) complexes with glycine bisphenol [O,N,O,O′] ligand: synthesis and catalytic studies

The oxomolybdenum(VI) complex [MoOCl(L)] with a tetradentate glycine bisphenol ligand (H₃L) was prepared by reaction of [MoO₂Cl₂(DMSO)₂] with a ligand precursor in hot toluene. The product was isolated in moderate yield as separable cis and trans isomers along with the third minor component, [MoO₂(HL)]. The solid-state structure of trans-[MoOCl(L)] was determined by X-ray diffraction. The ligand has tetradentate coordination through three oxygens and one nitrogen, which is located trans to the terminal oxo whereas the sixth coordination site is occupied by a chloride. Both cis and trans isomers of [MoOCl(L)] are active catalysts for epoxidation of cis-cyclooctene and sulfoxidation of tolyl methyl sulfide. The cis isomer gave higher activity in epoxidation and sulfoxidation reactions at room temperature than the trans isomer but they performed identically at 50?°C.     

O,O′,O′′,O′′′-四芳基双二硫代磷酰亚胺的合成

合成了 6种 O,O′,O′′,O′′′-四芳基双二硫代磷酰亚胺的合成类化合物 ,产物经元素分析、IR,1 H NMR和 MS表征。     

Four-membered ring cyclic ketene –O,O–, –O,S–, –O,N–, –S,S–, –S,N–, and –N,N–acetals and their corresponding cations: a computational study

A systematic computational study of four-membered cyclic ketene –O,O–, –O,S–, –O,N–, –S,N– and –N,N-acetals as well as their protonated analogs have been performed at the second order M?ller Plesset level with a polarized triple zeta basis set. The main purpose of this study was to make predictions about the nucleophilicity of these systems and the variations in nucleophilicity with the hetero atoms. Our calculations suggest that all six target molecules are good nucleophiles, and that the N,N analog is the strongest and the S,S analog the weakest nucleophile. Our results include molecular geometries, bond lengths, proton affinities, vibrational frequencies, and calculated charges.     

Synthesis,spectral characterization,and evaluation of antimicrobial activity of O,O′-alkanediyl S-(N-phthalimidomethyl) dithiophosphates and zinc bis(O,O′-alkanediyl) dithiophosphates

The synthesis of novel dithiophosphate derivatives has been achieved. Two O,O′-alkanediyl S-(N-phthalimidomethyl) dithiophosphates and two Zinc bis(O,O′-alkanediyl) dithiophosphates are synthesized by an easy and facile chemical synthetic route. Zinc bis[O,O′-(2-methylpentane-2,4-diyl) dithiophosphate] L¹, Zinc bis[O,O′-(2-ethylhexane-1,3-diyl) dithiophosphate] L², O,O′-(2-methylpentane-2,4-diyl) S-(N-phthalimidomethyl) dithiophosphate L³ and O,O′-(2-ethylhexane-1,3-diyl) S-(N-phthalimidomethyl) dithiophosphate L⁴ are synthesized from the respective ammonium salts. Compounds L¹, L², L³, and L⁴ are characterized by (CHN) elemental analysis, ESI mass, FT-IR, ¹H, ¹³C, and ³¹P NMR techniques. The crystal structure of ammonium O,O′-(2-methylpentane-2,4-diyl) dithiophosphate is discussed. L¹, L², L³, and L⁴ were evaluated for antimicrobial activity. It was found that the phthalimide derivatives L³ and L⁴ showed much better antifungal potential against some species of fungus. The Zinc dithiophosphates L¹ and L² showed good antibacterial activity against Bacillus cereus and Escherichia coli.     

O,O,S-三甲基硫赶磷酸酯在甲胺磷中毒检验中的应用

利用气相色诤质谱(GC-MS)分析了甲胺磷中毒者的检材(血，胃内容物)，均检出了O，O，S-三甲基硫赶磷酸酯，确未检出过甲胺磷。研究了这一现象的原因和确定了O，O，S-三甲基硫赶磷酸酯(O，O，S-TMTP)可作为甲胺磷中毒的佐证物。     

Y2O3, La2O3, Sm2O3对氧化铝瓷烧结及力学性能的影响

研究了3种稀土氧化物对氧化铝陶瓷烧结性能和力学性能的影响.结果表明 含Y2O3,La2O3,Sm2O3的添加剂促进了氧化铝瓷的烧结,提高了氧化铝瓷的力学性能.Y2O3和Sm2O3掺量为0.50%,La2O3掺量为0.75%时氧化铝瓷在1600或1620 ℃保温2 h烧结,相对密度达98.9%以上,强度超过439 MPa,断裂韧性达5.15 MPa·m1/2以上.微观结构分析表明,Y2O3,La2O3,Sm2O3抑止氧化铝晶粒生长,细化晶粒,使晶粒尺寸较均匀形成致密化结构.     

O,O′-二烷基硫代磷酸锌添加剂质量改进

O,O'-二烷基硫代磷酸锌(我厂产品代号 T202,又名6411)添加剂是一种抗氧、抗腐蚀添加剂。它是用五硫化二磷与醇在70—100℃反应生成二烷基硫代磷酸(以下简称硫磷酸),再与氧化锌在65—75℃皂化,经脱水过滤而得的产品,为了便于过滤及储运,成品中含25—30%的稀释矿油。主要反应是:p_2S_5+4ROH→2(RO)_2PSSH+H_2S↑2(RO)_2PSSH+ZnO→[(RO)_2PSS]_2Zn+H_2O多年来由于原料变化大、工艺条件不稳定,使用不确当等原因,用户反映:在使用中有臭味,热稳定差;特别是生产过程中产生的废渣等又臭又毒,长期以来没有找到合适的处理方法,严重地污染了环境。为了解决上述问题,我们采取了以下措施:改善产品热稳定性脱除臭味1.提高热稳定性原 T202添加剂是采用仲醇为原料,成品抗磨性     

O,O—二烷基氢膦酸酯的某些反应研究进展

本文介绍Ｏ，Ｏ－二烷基氢膦酸酯中发生在σ＾４λ＾５Ｐ－Ｈ或σ＾３λ＾３Ｐ－ＯＨ键上的几类重要反应如烷基化反应、加成反应、Ａｔｈｅｒｔｏｎ－Ｔｏｄｄ反应等，以及这些反应在有机合成中的应用，并对某些新颖反应机理作初步探讨。     

Rotational isomerism of O,O′-dialkyl esters of phosphorodithioic acid

Compounds (RO)₂ P(:S)SH, RPrⁱ, Buⁿ, and Octⁿ, exhibit rotational isomerism about PO and PS bonds. Temperature-dependence studies of band intensities indicate values of ΔH for the equilibria between isomers to be 2.5 kJ mol⁻¹, RPrⁱ; 3.0 kJ mol⁻¹, RBuⁿ; and ∼4.5 kJ mol⁻¹, ROctⁿ.     

Preparation and characterization of organogermanium O,O′-dimethyl and diethyl-dithiophosphates

Organogermanium derivatives of dithiophosphoric acid of general formula R₄−_nGe[SP(S)(OR′)₂]_n, where n = 1–3, R, = Me, Ph and R′ = Me, Et, have been prepared and characterized by means of ¹H, ¹³C NMR and vibrational spectroscopy and mass spectrometry. The spectroscopic results indicate that the dithiophosphate groups are monodenate and that an approximate tetrahedral geometry about the germanium atom is maintained. This is in part confirmed by a preliminary X-ray crystallographic determination of PhGe[SP(S)(OMe)₂]₃, whose crystals are orthorhombic, space group Pn2₂₁a, a 13.674(4), b 14.566(3), c 13.154(3) Å, V 26201(1) ų and Z = 4 from 1225 observed reflections [1 > 2σI].     

Bestimmung Von Molybdän Nach Extraction Mit O,O,S - Triäthyldithiophosphat

Abstract

The interaction of molybdenum(V) with potassium thiocyanate in a medium of O,O,S-triethyldithiophosphate [(C₂H₅O)₂P(S)SC₂H₅] and ethanol at a ratio 4:1 has been studied.

The stability constant of the molybdenum(V) thiocyanate complex was determined to be 7.6 × 10² with a molar ratio Mo(v) : SCN of 1:1. A new method based on the formation of the molybdenum-thiocyanate complex in the organic phase has been developed for the determination of molybdenum in steel.     

C, O, S, N-苷的高效立体选择合成

研究了正氟乙酸糖苷和三甲基硅烷基糖苷醚作为糖苷给予体。在路易士酸存在时应用1-O-三氟乙酰基-2,3,4,6-四-O-苄基-α-D-吡喃葡萄糖和芳香醚合成C-芳基-D-吡喃葡萄糖苷的方法。在十分温和的条件下以81-99%的得率获得β-异构体, 这一方法被扩展到O, S, N-苷的合成。     

Theoretical Study on the Structures and Stability of Isomers and Complex of[Si,C,O,O] Sytem

A detailed singlet potential energy surface(PES) of [Si,C,O,O] system including a van der Waals (vdW) comples SiO……CO2,eight isomers,and twelve transiton states is investigated by MP2 and QCISD(T) (single-point)methods.At the final QCISD(T)/6-311 G(2df)//MP2/6-311G(d) level with zero-point energy included,the complex SiO……CO is found to be thermodynamically and kinetically the most stable species.Although eight ismoers are located as local energy minima,they are rather unstable toward isomerization to the dissociation fragments or comples.For the reaction of silocon atoms with carbon dioxide,two competitive reaction channels are found,and the primary pathway,which leads to the products of SiO and CO fragments,is the direct oxygen-abstraction process from carbon dioxide by silicon atom with a41.16 kJ/mol reaction barrier height.Our predications are in good agreement with previous experimental and theoretical studies.     

Theoretical Study on the Structures and Stability of Isomers and Complex of [Si, C, O, O] System

Introduction[Si,C ,O ,O]systemhasattractedmuchattentioninthefieldsofchemistryandmaterials1 3becauseofthefollow ingseveralcauses .First,theinterestisthepotentialimpor tanceininterstellarspace .Heretofore ,SiC ,SiOandCOhavebeendetectedwithintheinterstellarmediumformanyyears,butno [Si,C ,O ,O]isomerswereobservedinthenebulae .FormanySi containingsystemshavebeenstudiedexperimentallyandtheoretically ,4 8andinviewofthepossibleexistenceofthe [Si,C ,O ,O]radicalininterstellarspace ,weselectthe…