Anodic oxidation of bis(organylchalcogeno)acetylenes

The electrochemical oxidation of bis(organylchalcogeno)acetylenes has been examined in organic solvents. With symmetrical ones, R---Z---CC---Z---R (1) (Z=S, Se), and with unsymmetrical ones, R¹---S---CC---Z---R² (2) (Z=Se), in macroscale electrolyses the α-diesters R¹---Z(S)---CO---CO---Z---R² were obtained as the main products. If Z=Te, from 1 and 2, reactions were more complex and the cleavage of the C---Te bond was always observed.     

微波促进二氯菊酸甲酯的水解新工艺研究

采用微波技术对二氯菊酸甲酯在NaOH溶液中水解为二氯菊酸工艺进行了研究。结果表明,微波促进下最佳水解条件为:反应温度90℃,功率100 W,反应时间10 m in,物质的量比n(二氯菊酸甲酯)∶n(C2H5OH)∶n(NaOH)=1∶4∶1.5,重结晶后收率高达99.6%。与传统条件相比,时间缩短30倍,收率提高24.6%,无水乙醇用量减少60%,NaOH用量减少17%。并用红外光谱和熔点对二氯菊酸进行表征。     

二氯菊酸甲酯的研制

从３－（２,２,２－三氯乙基）－２,２－二甲基环丙烷羧酸甲酯出发制备二氯菊酸甲酯。应用均匀设计选择反应优化条件,并对实验数据建立数学模型,同时对模型进行分析     

2,2-二甲基-5,5-二乙氧羰基-1,3-二氧六环的合成

以丙二酸二乙酯为原料,对2,2-二甲基-5,5-二乙氧羰基-1,3-二氧六环的合成进行了研究。     

Synthesis and chemical properties of Di(2-fluoro-2-polyfluoroalkyl- alkenyl)sulfides and 2,6-bis(polyfluoroalkyl)-1,4-oxathiine 4,4-dioxides

ABSTRACT

Di(1,1-dihydropolyfluoroalkyl)sulfides were synthesized by alkylation of sodium sulfide with tosylates or triflates of the corresponding 1,1-dihydropolyfluoroalkanoles. Dehydrofluorination of the obtained sulfides with strong organic bases such as alkylimino tris(dialkylamino) phosphoranes results in the formation of E-isomers of di(2-fluoro-2-polyfluoroalkyl alkenyl)sulfides. Oxidation of di(1,1-polyfluoroalkyl)sulfides by hydrogen peroxide in acetic acid affords di(1,1-polyfluoroalkyl)sulfones, dehydrofluorination of these compounds under the action of triethylamine allowed access to the E-isomers of di(2-fluoro-2-polyfluoroalkyl-alkenyl)sulfones. The obtained sulfones are convenient starting compounds for the synthesis of previously unknown fluorine-containing derivatives of monocyclic oxathiines.     

Simple and efficient method for the oxidation of sulfides to sulfones using hydrogen peroxide and a Mo(VI) based catalyst

A simple and efficient method for the oxidation of sulfides to sulfones at room temperature using ammonium heptamolybdate and 30% H₂O₂ is developed. The reactions provide excellent yields within short time, also sensitive functional groups such as allyl, vinyl, propargyl, alcohol, ketone, ester, pyridine and nitrile are found to be tolerated.     

1，2─双（二乙基膦基）乙烷的合成

以二乙基氯化膦为原料，经乙炔化及加氢两步合成了１，２－双（二乙基膦基）乙烷，产率超过文献值。用红外光谱和核磁共振波谱分别测定了结构。     

Comparison of tris(dimethylphenylsilyl)methyllithium and tris(trimethylsilyl)methyllithium reactions with carbon disulfide: a new route for the synthesis of some 1,1-bis(benzylthio)- and bis(allylthio)-2,2-bis(dimethylphenylsilyl)ethenes

A series of bis(benzylthio)- and bis(allylthio)-2,2-bis(dimethylphenylsilyl) ethenes has been obtained by the reaction of (PhMe₂Si)₃CLi and CS₂ with benzyl and allyl bromides. A plausible mechanism for the formation of these compounds has been proposed. The reactivity of (PhMe₂Si)₃CLi toward CS₂ has been compared with that of (Me₃Si)₃CLi. The reaction of (PhMe₂Si)₃CLi with CS₂ and 2-methyloxirane gave a cyclic thiocarbonate.     

N-甲基-2,2-二(4-苯氧基苯氧基)乙酰胺的合成

二氯乙酸甲酯与甲胺反应,制备了中间体N-甲基二氯乙酰胺。在无水碳酸钾存在下,以N,N-二甲基甲酰胺(DMF)为溶剂,中间体与4-苯氧基苯酚反应得到目的产物。着重考察了反应温度、反应时间、物料投料比对目的产物收率的影响,从而确定了产物的合成工艺条件为:反应温度85°C,反应时间4h,物料投料比n(N-甲基二氯乙酰胺)∶n(4-苯氧基苯酚)=1.0∶2.2。在此条件下,产物的收率达82%以上。经IR、MS、1H NMR确定为N-甲基-2,2-二(4-苯氧基苯氧基)乙酰胺。     

2,2-二(3-氨基-4-羟基苯基)六氟丙烷的合成

以2,2-二(4-羟基苯基)六氟丙烷为原料,分别经硝化和还原反应合成出2,2-二(3-氨基-4-羟基苯基)六氟丙烷。并在实验室小试成功后,进行工厂中试研究,以确定中试的各个工艺参数。结果表明,对于第1步硝化反应,以乙醇做溶剂,用量为n(乙醇)/n〔2,2-二(4-羟基苯基)六氟丙烷〕=4,n(稀硝酸)/n〔2,2-二(4-羟基苯基)六氟丙烷〕=2.15,反应温度为60℃,反应时间为6 h的条件下,合成2,2-二(3-硝基-4-羟基苯基)六氟丙烷的产率达到最高值96%。对于第2步还原反应,采用自制FeCl3/活性炭为催化剂,乙醇做溶剂,n(水合肼)/n〔2,2-二(3-硝基-4-羟基苯基)六氟丙烷〕=0.2,m(FeCl3/活性炭)/m〔2,2-二(3-硝基4-羟基苯基)六氟丙烷〕=0.05,反应温度为85℃,反应时间为10 h的条件下,合成2,2-二(3-氨基-4-羟基苯基)六氟丙烷的产率达到最高值92%。该工艺条件在工厂已进行了中试研究,确定了工业实验的各个工艺参数和工艺条件。     

2,2-二羟甲基丁酸合成工艺研究

以正丁醛、甲醛和双氧水为主要原料,经羟醛缩合、氧化反应制备2,2-二羟甲基丁酸,考察了缩合、氧化反应条件。结果表明,最佳缩合反应条件为:正丁醛∶甲醛∶双氧水=1∶2.4∶1.4(摩尔比),缩合反应温度35℃左右,缩合反应时间6 h;氧化反应条件为:温度80℃左右,反应时间6 h。反应液采用离子交换→真空浓缩→溶剂结晶→重结晶工艺处理,2,2-二羟甲基丁酸产品总收率大于40%。     

Synthesis and characterization of new soluble cardo poly(amide-imide)s derived from 2,2-bis[4-(4-trimellitimidophenoxy)phenyl]norbornane

A series of new soluble poly(amide-imide)s were prepared from the diimide-dicarboxylic acid, 2,2-bis[4-(4-trimellitimidophenoxy)phenyl]norbornane, and various diamines by the direct polycondensation in N-methyl-2-pyrrolidinone containing CaCl_2, using triphenyl phosphite and pyridine as condensing agents. All the polymers were obtained in quantitative yields with inherent viscosities of 1.01-1.42 dL g⁻¹. Gel permeation chromatography (GPC) of the polymers showed number-average and weight-average molecular weight up to 67,300 and 118,000, respectively. The poly(amide-imide)s were amorphous and were readily soluble in various solvents such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), pyridine, cyclohexanone and tetrahydrofuran. Tough and flexible films were obtained by casting their DMAc solution. The films had tensile strength of 89-110 MPa and a tensile modulus range of 1.8-2.2 GPa. The glass transition temperatures of the polymers were determined by DSC method and they were in the range of 265-295 °C. The polymers were fairly stable up to a temperature around or above 450 °C, and lose 10% weight in the range of 472-504 °C and 490-520 °C in nitrogen and air, respectively.     

动力学拆分制备（R）-3,5-双三氟甲基苯乙醇

通过动力学拆分方法,由3,5-双三氟甲基苯乙酮出发,经过 NaBH4还原,制备得到高纯度消旋化的(R,S)-3,5-双三氟甲基苯乙醇。经过筛选得到2种高效高选择性动力学拆分(R,S)-3,5-双三氟甲基苯乙醇的脂肪酶：Novozym 435和Rhizopus arrhizus。以Rhizopus arrhizus作为实验脂肪酶,考察了影响其动力学拆分的因素,包括溶剂、反应温度和底物浓度,获得最佳的反应条件为：正己烷作为溶剂,40℃下反应,底物浓度为100 mmol/L。在最佳的条件下,以乙酸乙烯酯作为酰基供体进行动力学拆分反应,经过后期的分离纯化,成功制备得到了e.e.值接近100%的(R)-3,5-双三氟甲基苯乙醇。     

1,1-二甲硫基-2-硝基乙烯的合成

研究了以硝基甲烷和二硫化碳为原料,合成1,1-二甲硫基-2-硝基乙烯。考察了反应温度、反应时间、甲基化试剂、溶剂、投料比等对于反应产物的影响,得到优化工艺条件为:反应温度35℃,反应时间3h。以硫酸二甲酯为甲基化试剂,常温下反应时间3 h,重结晶得1,1-二甲硫基-2-硝基乙烯,收率为84%,产物通过IR、1H-NMR鉴定。     

Synthesis of 2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine-1-oxide and its hydrazones

An efficient method for preparation of earlier unknown S-oxide of 2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine by oxidation of 2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine hydrochloride with hydrogen peroxide in H₂O or EtOH/H₂O followed by the reaction mixture neutralization with Na₂CO₃ has been described. Interaction of the S-oxide with acetaldehyde, butanal, benzaldehyde, 4-methoxybenzaldehyde and 4-pyridinecarboxaldehyde in EtOH, C₆H₆, in the mixture of acetonitrile and ethanol or ethanol and benzene affords the unknown hydrazones, N-organylmethylidene-2(E),6(E)-bis(chloromethylidene)-4-thiomorpholinamine-1-oxides.     

1,4-二(溴甲基)-2-氟苯的合成工艺改进

以对二甲苯为原料,经硝化、还原、重氮化、溴代4步反应得到标题化合物。其中溴代反应中,1,4-二甲基-2-氟苯在偶氮二异丁腈(AIBN)引发下与N-溴代丁二酰亚胺(NBS)发生自由基反应。总收率达到30%,其结构经1HNMR和GC/MS确证。     

2-(4’-羧基苯基)-1,2-苯并异硒唑-3(2H)-酮的放大合成

为了克服依布硒林亲水性差及气味太重的缺点,同时保留依布硒林抗氧化的特性,参照现有方法放大合成了羧基依布硒林(ebselen)衍生物2-(4’-羧基苯基)-1,2-苯并异硒唑-3(2H)-酮,并对该方法优化、改进,用质谱及红外光谱对目标产物进行了表征。通过对合成的产物进行急性经口毒性试验,发现其经口半数致死量(LD50,medium lethal dose)大于5.5g/Kg,按照急性毒性分级标准确定该依布硒林衍生物属实际无毒级。     

Hydrophosphorylation of vinyl sulfides with elemental phosphorus in the KOH/DMSO(H2O) system: synthesis of 2-alkyl(aryl)thioethylphosphinic acids

Elemental phosphorus (red or white) reacts with alkyl and aryl vinyl sulfides in the superbase system KOH/DMSO(H₂O) at 75–120°C for 2–3?h to afford 2-alkyl(aryl)thioethylphosphinic acids in a yield of up to 31%.     

反体二氯菊酸的立体选择合成

以贲亭酸甲酯为原料,经自由基加成、立体有择环化合成了富反式二氯菊酸甲酯,收率高达95%,反顺比为88∶12。还以顺反混合体 (trans/cis=60/40) 二氯菊酸酰氯为原料,立体选择性转化合成富反式二氯菊酸酯,对催化剂、反应时间、溶剂进行条件实验,以4-二甲氨基吡啶催化立体转化效果最好,收率95%,反顺比达93/7。     

Theoretical and practical investigations of copper ion selective electrode with polymeric membrane based on N,N′-(2,2-dimethylpropane-1,3-diyl)-bis(dihydroxyacetophenone)

A novel ion-selective poly(vinyl chloride) (PVC) membrane sensor for Cu²⁺ ions based on N,N′-(2,2-dimethylpropane-1,3-diyl)-bis(dihydroxyacetophenone) (NDHA) as a new ionophore was prepared and studied. The best performance was observed for the membrane composition, including 30:65:1:4 (wt%) = PVC:DBP:KTpClPB:NDHA. The electrode showed a good Nernstian slope of 30.0 ± 0.5 mV/decade in a wide linear range activity of 3.0 × 10⁻⁷ to 1.0 × 10⁻² mol dm⁻³ Cu(NO₃)₂ with limit of detection 2.5 × 10⁻⁷. Sensor exhibited a fast response time (t_95% < 10 s) and could be used for about 4 months in the pH range of 3.0–7.4. The proposed potentiometric sensor was found to work satisfactorily in partially non-aqueous media up to 30 (vol%) content of methanol, ethanol and acetone. Applications of this electrode for the determination of copper in real samples, and as an indicator electrode for potentiometric titration of Cu²⁺ ion using EDTA, were reported. In order to predict the extraction ability of NDHA for different metallic ions, the complexes [M(NDHA)] and [M(H₂O)₆] (where M = Cu²⁺, Co²⁺, Hg²⁺, Pb²⁺, Ag⁺, Mg²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Cd²⁺, K⁺ and Al³⁺) were investigated using ab initio theoretical calculations. The metal binding capability was evaluated using the binding energy. Results of our study could be useful for prediction of the extraction power of this Schiff base and could play a guiding role in planning experiments.