Synthesis of Substituted u-Oxo-bis[tetra-phenyl porphyrinatoiron] Compounds from Free Base Porphyrins by a One-pot Method

A novel method for synthesis of substituted u-oxo-bis[tetraphenyl porphyrinatoiron] compotmds （[TRPPFe]20） based on the reaction among free base porphyrins （TRPPH2）, FeSO4·7H2O and H2O in one pot was proposed and investigated. Four kinds of [TRPPFe]2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe]2O, the reaction time between FeSO4-7H2O and TRPPH2, the molar ratio of FeSO4-7H2O/TRPPH2 as well as the volume ratio of H2O/DMF, were investigated. The [TRPPFe]2O yield of 93% 98% could be obtained under the following optimal conditions： the reaction time of FeSOn-7H2O with TRPPH2 was about 10 h, the molar ratio of FeSOn-7H2O/TRPPH2 about 5 ： 1, and the volume ratio of H2O/DMF exceeded 2 ： 1. Further research indicated that only TRPPFeCI were formed once FeSOn-7H2O was replaced by FeCl2-4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe]2O, suggesting that halogen ions should be avoided in this novel synthetic method.

A Convenient Method for the Synthesis of 1,3,2-Oxazaphospholidin-[3,2-a]-8-oxo-10-thio(or seleno)-[1,3,2]-benzodiazaphosphorines

A Convenient method for the synthesis of fused phosphorusheterocycle 1,3,2-oxazaphosphorin-[3.2-a]-8-oxo-10-thio(or seleno)-[1,3,2]-benzodiazaphosphorines was carried out in one pot by the reaction of Tris(diethylamino)phosphine with multifunctional compounds 2-(N-(beta or gamma-hydroxyl) alkylene) amino-benzamides 1. When PCL3 was used, only chlorinated product was obtained.

六硝基六氮杂异伍兹烷的一锅合成

使用一锅法以四乙酰基二苄基六氮杂异伍兹烷为原料 ,经亚硝解脱苄再硝解合成目标化合物 ,改进了六硝基六氮杂异伍兹烷 (HNIW)的制备方法 .利用该方法合成的HNIW,反应收率可达 82 %以上 ,纯度达 98% (HPLC归一化法 ) .分离并鉴定了四乙酰基二亚硝基六氮杂异伍兹烷、苯甲醛、苯甲酸等中间产物 .

微乳液法处理RDX的生产废酸

为除去直接硝解法合成RDX时生产废酸中的不稳定有机副产物,以正庚烷/正己烷为油相溶剂(O)、十二烷基苯磺酸钠(SDBS)/十二烷基硫酸钠(SDS)为表面活性剂(S)、正丁醇/正戊醇为助表面活性剂(C)与水(W)配制成微乳液,对直接硝解法合成RDX结晶但不氧化产生的废酸用微乳液进行萃取,对萃取后的废酸进行高效液相色谱分析,甲醛吸收液用NaOH溶液滴定,考察了不同微乳液配方、微乳液与废酸的体积比、萃取次数、微乳液循环使用等因素对废酸萃取效果的影响。结果表明,O、S、C和W质量比为13∶2∶8∶1时配制的微乳液萃取与循环使用效果最佳,微乳液与废酸体积比为5∶1时萃取一次可除去废酸中约95%的不稳定副产物,可在被萃取物加热分解后循环使用4次,萃取后的废酸在70℃保持稳定。

1-甲基咪唑硝酸盐辅助直接硝解法制备降感RDX

考察了离子盐1-甲基咪唑硝酸盐([mimH]NO3)辅助直接硝解乌洛托品(HA)制备黑索今(RDX)的结晶工艺条件。研究了搅拌速度、结晶温度、[mimH]NO3用量、滴水速度对RDX晶形的影响。用扫描电镜和撞击感度仪分析、表征了其晶形和感度。结果表明,最佳结晶工艺条件为:[mimH]NO3与HA的物质的量之比为0.015,水的滴加速度1滴/40 s,搅拌速度800 r·min-1,结晶过程温度10～70℃。该工艺条件下所得RDX粒度均匀,形状规整,呈八面体型。按GJB772A-1997-601.1方法,测得其爆炸概率为17%。

小分子法合成1,5-二乙酰基-3,7-二硝基-1,3,5,7,-四氮杂辛烷工艺研究

以甲醛、氨为起始原料,中间体不分离,经过缩合、乙酰化、硝解等反应得到1,5-二乙酰基-3,7-二硝基-1,3,5,7,-四氮杂辛烷(DADN),考察了甲醛与氨的配比、缩合时间、乙酰化时间、硝酸用量及硝硫混酸的配比、加料温度和硝解时间等因素对DADN收率的影响,确立了最佳工艺。结果表明,当甲醛与氨的摩尔比为1:1.5,缩合反应时间60min,乙酰化时间25min,硝硫混酸摩尔比1:3,加料温度18℃,硝解时间为25min,DADN产率为84.4%。

Adsorption of CO_(2) on MgAl layered double hydroxides: Effect of intercalated anion and alkaline etching time

The adsorption of CO_(2) on MgAl layered double hydroxides(MgAl-LDHs) based adsorbents has been an effective way to capture CO_(2),however the adsorption capacity was hampered due to the pore structure and the dispersibility of adsorption active sites.To address the problem,we investigate the effect of intercalated anion and alkaline etching time on the structure,morphology and CO_(2) uptake performances of MgAl-LDHs.MgAl-LDHs are synthesized by the onepot hydrothermal method,followed by alkaline etching of NaOH,and characterized by x-ray diffraction,N_(2) adsorption,scanning electron microscopy and Fourier transform infrared spectroscopy.The CO_(2) adsorption tests of the samples are performed on a thermogravimetric analyzer,and the adsorption data are fitted by the first-order,pseudo-second-order and Elovich models,respectively.The results demonstrate that among the three intercalated samples,MgAl(Cl) using chloride salts as precursors possesses the highest adsorption capacity of CO_(2),owing to high crystallinity and porous structure,while MgAl(Ac) employing acetate salts as precursors displays the lowest CO_(2) uptake because of poor crystallinity,disorderly stacked structure and unsatisfactory pore structure.With regard to alkaline etching,the surface of the treated MgAl(Cl) is partly corroded,thus the specific surface area and pore volume increase,which is conducive to the exposure of adsorption active sites.Correspondingly,the adsorption performance of the alkaline-etched adsorbents is significantly improved,and MgAl(Cl)-6 has the highest CO_(2) uptake.With the alkaline etching time further increasing,the CO_(2) adsorption capacity of MgAl(Cl)-9 sharply decreases,mainly due to the collapse of pore structure and the fragmentized sheet-structure.Hence,the CO_(2) adsorption performance is greatly influenced by alkaline etching time,and appropriate alkaline etching time can facilitate the contact between CO_(2) molecules and the adsorbent.

One-pot molten salt method for constructing CdS/C_(3)N_(4) nanojunctions with highly enhanced photocatalytic performance for hydrogen evolution reaction

The construction of heterojunction photocatalysts for efficiently utilizing solar energy has attracted considerable attention to solve the energy crisis and reduce environmental pollution.In this study,we use the energy released from an easily-occurred exothermic chemical reaction to serve as the drive force to trigger the formation of Cd S and C_(3)N_(4) nanocomposites which are successfully fabricated with cadmium nitrate and thiourea without addition of any solvents and protection of inert gas at initial temperature,a little higher than the melting point of thiourea.The as-prepared Cd S/C_(3)N_(4) materials exhibit high efficiency for photocatalytic hydrogen evolution reaction(HER)with the HER rate as high as 15,866μmol/(g·hr)under visible light irradiation(λ>420 nm),which is 89 and 9 times those of pristine C_(3)N_(4) and Cd S,respectively.Also,the apparent quantum efficiency(AQE)of Cd S/C_(3)N_(4)–1:2–200–2(Cd S/C_(3)N_(4)–1:2–200–2 means the ratio of Cd to S is 1:2 and the reaction temperature is set at 200℃ for two hours)reaches 3.25%atλ=420±15 nm.After irradiated for more than 24 hr,the HER efficiencies of Cd S/C_(3)N_(4) do not exhibit any attenuation.The DFT calculation suggests that the charge difference causes an internal electric field from C_(3)N_(4) pointing to Cd S,which can more effectively promote the transfer of photogenerated electrons from Cd S to C_(3)N_(4).Therefore,most HER should occur on C_(3)N_(4) surface where photogenerated electrons accumulate,which largely protects Cd S from photo-corrosion.

Synthesis of Novel 1-Alkyl-2-chloro(alkoxy)-1H-indole 3-Carbaldehyde Oximes and Oxime-ethers(esters) Derivatives

A convenient synthesis of 1-alkyl-2-chloro-1H-indole-3-carbaldehyde oximes（5a―5d） and 1-alkyl-2-phenoxy-1H-indole-3-carbaldehyde oximes（6a―6d） from 2-indolone was completed via the Vilsmeier-Haack reac-tion,with N-alkylation and oximation as the key steps.An improved one-pot method for the synthesis of 1-alkyl-2-alkoxy-1H-indole-3-carbaldehyde oximes（7a―7h） from 1-alkyl-2-chloro-1H-indole-3-carbaldehydes（3a―3d） was described.The Williamson reactions and esterification reactions were performed and the oxime-ethers and oxime-esters were synthesized,respectively.The new synthesized compounds（3a―11d） were characterized by 1H NMR,IR,MS,and elemental analysis.

新型高能化合物HNFX和TNFX的合成

简要介绍了新型高能化合物3,3,7,7–四(二氟氨基)八氢–1,5–二硝基–1,5–二氮杂环辛烷(HNFX)和3,3–双(二氟氨基)八氢–1,5,7,7–四硝基–1,5–二氮杂环辛烷(TNFX)的性质和合成背景。综述了HNFX和TNFX的合成方法和反应机理,重点介绍了用一锅硝解法合成HNFX的具体工艺方法,并指出了当前HNFX和TNFX合成路线的难点和工艺操作事项。

Facile synthesis of hydrochar-supported catalysts from glucose and its catalytic activity towards the production of functional amines

Since the utilization of abundant biomass to develop advanced materials has become an utmost priority in recent years,we developed two sustainable routes(i.e.,the impregnation method and the one-pot synthesis)to prepare the hydrochar-supported catalysts and tested its catalytic performance on the reductive amination.Several techniques,such as TEM,XRD and XPS,were adopted to characterize the structural and catalytic features of samples.Results indicated that the impregnation method favors the formation of outer-sphere surface complexes with porous structure as well as well-distributed metallic nanoparticles,while the one-pot synthesis tends to form the inner-sphere surface complexes with relatively smooth appearance and amorphous metals.This difference explains the better activity of catalysts prepared by the impregnation method which can selectively convert benzaldehyde to benzylamine with an excellent yield of 93.7%under the optimal reaction conditions;in contrast,the catalyst prepared by the one-pot synthesis only exhibits a low selectivity near to zero.Furthermore,the gram-scale test catalyzed by the same catalysts exhibits a similar yield of benzylamine in comparison to its smaller scale,which is comparable to the previously reported heterogeneous noble-based catalysts.More surprisingly,the prepared catalysts can be expediently recycled by a magnetic bar and remain the satisfying catalytic activity after reusing up to five times.In conclusion,these developed catalysts enable the synthesis of functional amines with excellent selectivity and carbon balance,proving cost-effective and sustainable access to the wide application of reductive amination.

Amorphous and Crystallizable Thermoplastic Polyureas Synthesized through a One-pot Non-isocyanate Route

A simple one-pot non-isocyanate route for synthesizing thermoplastic polyureas is presented. In situ urethanization was conducted from the ring-opening reaction of ethylene carbonate with poly(propylene glycol) bis(2-aminopropyl ether) and hexanediamine,m-xylylenediamine, or diethylene glycol bis(3-aminopropyl) ether at 100 °C for 6 h under normal pressure. Melt transurethane polycondensation was successively conducted at 170 °C under a reduced pressure of 399 Pa for different time periods. A series of nonisocyanate thermoplastic polyureas(NI-TPUreas) were prepared. The NI-TPUreas were characterized by gel permeation chromatography,FTIR, 1 H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray diffraction, atomic force microscopy,and tensile test. NI-TPUreas exhibited Mn of up to 1.67 × 104 g/mol, initial decomposition temperature over 290 °C, and tensile strength of up to 32 MPa. Several crystallizable NI-TPUreas exhibited Tm exceeding 98 °C. NI-TPUreas with good thermal and mechanical properties were prepared through a green and simple one-pot non-isocyanate route.

Stereoselectiveα-Glycosylation with GlcN_(3)Donors Enabled Collective Syntheses of Acinetobacter baumannii Capsular Polysaccharides K43,K47 and K88 Repeating Units

Collective syntheses of A.baumannii CPS K43,K47 and K88 repeating units have been accomplished via a newα-glycosylation method with GlcN_(3) as donors,which features:1)mild reaction conditions,2)good to high yields,3)excellent stereoselectivities.The synthetic route also highlights an orthogonal one-pot coupling strategy on the basis of glycosyl ortho-(1-phenylvinyl)benzoates for stereoselective constructions of both 1,2-trans and 1,2-cis glycosidic bonds,precluding the issues of aglycone transfer.

高温硝解EDTA容量法快速测定铅精粉中的铅

试样经NH4HF2助溶,HNO3-KClO3溶解后,在冒SO3白烟时(340℃),高温硝解残渣。在1mol/L的H2SO4介质中沉淀铅,生成PbSO4沉淀,过滤除去溶解于溶液的干扰元素,用pH=5.5～5.9的HAC-NAC缓冲溶液溶解PbSO4沉淀,以二甲酚橙作指示剂,EDTA容量法测定铅。本方法克服了国标方法测定流程长,多点测定(残渣、滤液、溶液中的铅),溶解矿样过程繁杂,费时费力等缺点。建立的方法可一次性测定铅量,经用铅精粉国家一级标准物质GBW07167验证,结果与标准值吻合,方法的精密度RSD%(n=11)在0.1%～0.3%之间,方法简便、快速。适合于钡含量低(<2%)的铅精粉中铅的测定。

Preparation of Peptide Selenoesters from Their Corresponding Acyl Hydrazides

Main observation and conclusion Selenoesters are useful substitutes for traditional thioesters in protein ligation chemistry due to their high reactivity in the trans-thio/selenoesterification reaction.However,existing synthetic routes to access peptide selenoester require a selenoesterification reaction between a selenide and a protected peptide with a free carboxylate at the C-terminus.

Selective Synthesis of 2-Aryl-l-benzylated-1 H-benzimidazoles

An efficient and simple procedure was developed for the green synthesis of various 2-aryl-l-ben- zylated-1H-benzimidazoles in high yields by condensation of o-phenylenediamine with aldehydes with P2O5/SiO2 as catalyst under solvent-free and ambient conditions.

One‑Pot Rational Deposition of Coaxial Double‑Layer MnO_(2)/Ni(OH)_(2) Nanosheets on Carbon Nanofibers for High‑Performance Supercapacitors

Constructing“nanoglue”between inorganic electroactive species and conductive carbon scaffolds is an effective strategy to improve their compatibility and binding interaction,holding a great promise for fabricating high-performance hybrid electrodes for supercapacitors.However,multistep reactions are usually required to obtain these multicomponent systems,thus giving rise to the complicated and time-consuming issues.Herein,we for the first time,demonstrate a green one-pot method to anchor coaxial double-layer MnO_(2)/Ni(OH)_(2)nanosheets on electrospun carbon nanofibers(CNFs)(denoted as MNC),where the intermediate MnO_(2)layer serves as the“nanoglue”to couple the vertically aligned Ni(OH)_(2)nanosheets and conductive CNFs.Benefiting from the unique chemical composition and hierarchical architecture,the resultant electrode delivers outstanding electrochemical performance,including an excellent specific capacitance(1133.3 F g^(-1)at 1 A g^(-1))and an ultrahigh rate capability(844.4 F g^(-1)at 20 A g^(-1)).Moreover,the asymmetric supercapacitor assembled by using the MNC as positive electrode and the CNF as negative electrode can achieve an optimal energy density of 35.1 Wh kg^(-1)and a maximum power density of 8000 W kg^(-1).The one-pot strategy that stabilizes electroactive metal hydroxides on conductive carbons using a MnO_(2)“nanoglue”to design advanced hybrid electrodes is expected to be broadly applicable not only to the supercapacitor technology but also to other electrochemical applications.

Post-functionalization of disubstituted polyacetylenes via click chemistry

We report a synthetic design and the experimental exploration of preparation of disubstituted polyacetylenes （PAs, P3） through 1,3-dipolar cycloaddition of azides with precursor PA bearing alkyne pendants. The precursor PA （P2） was derived by desilylation of the pristine PA with trimethylethynylsilane side chains （P1）. P1 was obtained by polymerization of a dual-alkyne containing monomer with one of the alkynes end-capping by trimethylsilane （M） under the promotion of WC16-Ph4Sn catalyst. Two synthetic routes, i.e. two-steps （from P1 to P3 via precursor P2） and one-pot （from P1 to P3 without separation and purification of P2） were tried and the results indicated that one-pot strategy is more facile and resultant P3-1 showed higher purity and higher molecular weight than the resultant of P3-2. By using the techniques such as GPC, FTIR and 1H NMR spectroscopy the polymerization behavior and the structures of the polymers were well characterized.

Facile Synthesis of N-Sulfonylcyclothioureas in Water

A sequential one-pot synthesis of N-sulfonylcyclothioureas from N-monosulfonyl diamines, CS2 and chloroace- tic acid at room temperature in water is described. In the absence of highly toxic thiophosgene and organic solvents, this method is environmentally benign. Simple reaction conditions, easy purification of the products, good yields and thioglycolic acid as the useful byproduct are also important attributes of this methodology. The plausible mechanism including tandem reactions is proposed.