NaBO2-NaCl-Na2CO3, NaBO2- Na2CO3-NaMoO4, NaBO2- Na2CO3-NaWO4, and NaBO2-NaCl-Na2WO4 ternary systems

The phase diagrams of the NaBO₂-NaCl-Na₂CO₃, NaBO₂-Na₂CO₃-Na₂MoO₄, NaBO₂- Na₂CO₃-Na₂WO₄, and NaBO₂-NaCl-Na₂WO₄ ternary systems were studied by a calculation-experimental method and differential thermal analysis. The coordinates of ternary eutectics were determined: E ₁: 612°C, 16 mol % NaBO₂, 42 mol % NaCl, and 42 mol % Na₂CO₃; E ₂: 568°C, 12 mol % NaBO₂, 28 mol % Na₂CO₃, and 60 mol % Na₂MoO₄; E ₃: 575°C, 12 mol % NaBO₂, 32 mol % Na₂CO₃, and 56 mol % Na₂WO₄; E ₄: 628°C, 8 mol % NaBO₂, 20 mol % NaCl, and 72 mol % Na₂WO₄; and E ₅: 655°C, 9 mol % NaBO₂, 53 mol % NaCl, and 38 mol % Na₂WO₄.     

Zur Bestimmung von NaOH, Na2CO3 und NaHCO3 in Gemischen

Ohne Zusammenfassung     

Separation of C1-C5 aliphatic carboxylic acids on a highly sulfonated styrene-divinylbenzene copolymer resin column with a C6 aliphatic carboxylic acid solution as the mobile phase

Simultaneous separation of C₁-C₅ aliphatic carboxylic acids (formic, acetic, propionic, iso-butyric, butyric, iso-valeric and valeric acids) on a highly sulfonated styrene-divinylbenzene copolymer resin column (TSKgel SCX,  mm i.d.) was performed with C₆ aliphatic carboxylic acids (3-methyl-n-valeric, iso-caproic and caproic acids) solutions as the mobile phases. Using 0.05 mM sulfuric acid at pH 4.0 as the mobile phase, although good separation of these C₁-C₅ acids was achieved, peaks of the C₅ acids (iso-valeric and valeric acids) with large hydrophobicity tailed strongly. In contrast, using 1 mM C₆ acids at pH ca. 4.0 as the mobile phases, although vacant peaks corresponding to the C₆ acids in the mobile phase appeared, the peak shapes of the C₅ acids were improved greatly. Excellent simultaneous separation, symmetrical peaks and relatively high-sensitivity conductimetric detection for these C₁-C₅ acids were achieved on the TSKgel SCX column in 15 min with 1 mM iso-caproic acid at pH 4.0 as the mobile phase.     

Friedel-Crafts acylation of aromatic compounds with carboxylic acids in the presence of P2O5/SiO2 under heterogeneous conditions

A convenient and efficient procedure for the Friedel-Crafts acylation of aromatic compounds with carboxylic acids in the presence of P₂O₅/SiO₂ is described. Both aromatic and aliphatic carboxylic acids reacted easily to afford the corresponding aromatic ketones. The use of non-toxic and inexpensive materials, simple and clean work-up, short reaction times and good yields of the products are the advantages of this method.     

One-pot,direct synthesis of acyl azides from carboxylic acids using Ph2PCl/I2/NaN3 reagent system

A mild,efficient and simple method for the preparation of acyl azides from carboxylic acids using chlorodiphenylphosphine in the presence of molecular iodine and sodium azide is described.     

Thermal analysis of Na2CO3 · H2O crystals

Monohydrated sodium carbonate crystals have been grown by slow evaporation of its aqueous solution maintained at 40 ± 1°C. The thermal dehydration of this crystal has been studied by dynamic and isothermal TG measurements. It is observed from dynamic TG that the single molecule of water of crystallization is lost in two steps of 0.3 mole and 0.7 mole at temperatures 426 ± 5 and 454 ± 5 K, respectively. From isothermal and dynamic TG measurements, the kinetic parameters E and Z are calculated using different known forms of the function F(). It is observed that consistency of E and Z values in isothermal and dynamic TG measurements for the two dehydration steps gives the correct function F() = −[log(1-)]^0.5. The activation energies for this function for the two dehydration steps are ≈6 and ≈9 kcal mole⁻¹, respectively.     

High-temperature equilibria and critical phenomena in the Na2CO3-NaCl-H2O and Na2CO3-Na2WO4-H2O systems

Phase equilibria in the Na₂CO₃-NaCl-H₂O and Na₂CO₃-Na₂WO₄-H₂O ternary systems formed by type 1 salts (NaCl, Na₂WO₄) and a type 2 salt (Na₂CO₃) were experimentally studied at temperatures from 425 to 500°C and pressures from 30 to 160 MPa with the contents of type 1 salts from 10 to 30 wt %. Transition from supercritical homogeneous fluid equilibria of the Na₂CO₃-H₂O system to heterogeneous equilibria of the title ternary systems was studied in the presence or absence of liquid phase immiscibility in the type 1 subsystems.     

煤矸石催化气化耦合气化灰提铝过程中K2CO3和Na2CO3作用的对比研究

以煤矸石为研究对象，对比研究了Na₂CO₃与K₂CO₃对煤矸石催化气化反应性及催化气化灰中Al的溶出行为的影响。同时，采用X射线衍射分析（XRD）和热重分析（TGA）研究了不同催化剂及温度作用下矸石中矿物质的热转变过程。结果表明，与K₂CO₃相比，煤矸石中的高岭石更容易与Na₂CO₃反应生成钠霞石，而酸浸可实现钠霞石中铝和硅元素的有效分离。此外，Na₂CO₃作为催化剂时，所得气化灰经盐酸浸取后铝的浸出率可达到94.2%。而K₂CO₃作催化剂时，其铝的浸出率只有83.7%。因此，对矸石催化气化耦合气化灰的铝提取来说，Na₂CO₃催化剂具有更好的选择性。     

Novel solvent-free reaction of C60 with active methylene compounds in the presence of Na2CO3 under high-speed vibration milling

Inorganic base, Na₂CO₃, was utilized to replace organic base, DBU, in the Bingel reaction employing diethyl bromomalonate under the mechanochemical ‘high-speed vibration milling’ conditions to give the cyclopropanated C₆₀1 in high yield. In contrast, reactions of C₆₀ with diethyl malonate and ethyl acetoacetate in the presence of Na₂CO₃ under HSVM conditions afforded 1,4-bisadduct 2 and dihydrofuran-fused C₆₀ derivative 3, respectively.     

负载碳酸钠煤焦催化气化反应特性研究

基于热重分析仪开展负载碳酸钠神府烟煤/遵义无烟煤煤焦气化实验,并借助扫描电子显微镜和孔结构及比表面积分析仪表征焦样孔结构及表观结构变化,考察了反应温度(650-800℃)、气化剂(水蒸气、二氧化碳)及碳酸钠负载量(钠离子负载量2.2%、4.4%、6.6%,质量分数)对神府烟煤/遵义无烟煤焦样气化反应活性的影响。结果表明,碳酸钠有利于促进神府/遵义煤热解过程孔隙结构的发展。在二氧化碳气氛下,适宜催化剂负载量使神府烟煤反应活性提高,过多负载催化剂堵塞煤焦内部孔隙结构,使得气化反应活性降低,遵义无烟煤反应活性随负载量增加而提高,两者反应活性均随温度升高而提高。在水蒸气气氛下,神府烟煤/遵义无烟煤在一定条件下反应活性随催化剂负载量增大、温度升高而提高。碳酸钠的添加能够在保证气化反应性的前提下降低气化反应温度和活化能。     

Mechanochemical synthesis of primary amides from carboxylic acids using TCT/NH4SCN

A facile and effective approach toward the synthesis of primary amides from carboxylic acids has been developed. In the presence of 2,4,6-trichloro-1,3,5-triazine, a combination of ammonium thiocyanate and potassium carbonate led to the rapid conversion of carboxylic acids into the corresponding amides within five minutes grinding at room temperature. The use of ammonium thiocyanate as the amine source is unprecedented and exclusive formation of primary amides is observed only under the liquid-assisted grinding conditions.     

KCl-KBO2-K2CO3, K2MoO4-KBO2-K2CO3, and K2WO4-KBO2-K2CO3 ternary systems

phase diagrams of KCl-KBO₂-K₂CO₃, K₂MoO₄-KBO₂-K₂CO₃, and K₂WO₄-KBO₂-K₂CO₃ ternary systems were studied by a calculation-experimental method and differential thermal analysis (DTA). The coordinates of ternary eutectics were determined to be E ₁: 622°C, 8.5 mol % KBO₂, 56.5 mol % KCl, and 35 mol % K₂CO₃; E ₂: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂MoO₄; E ₃: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂WO₄. The specific heats of melting of the eutectics were determined.     

Synthesis of 2-arylpropionic acids by electrocarboxylation of benzylchlorides catalysed by PdCl2(PPh3)2

Electrochemical carboxylation of benzylchlorides catalysed by Pd(II) complex afforded 2-arylpropionic acids in good yields under atmospheric pressure of carbon dioxide at constant current of 10 mA cm⁻². Mechanistic and electrochemical studies revealed the cooperative role of reduced palladium species in the activation of carbon dioxide.     

The efficient one-pot synthesis of tetraalkyl substituted furans from symmetrical acetylenes,EtAlCl2, and carboxylic esters catalyzed by Cp2TiCl2

A new one-pot method for the synthesis of tetraalkyl substituted furans in 74–80% yields has been implemented via the reaction between symmetrical acetylenes, ethylaluminum dichloride, and carboxylic esters in the presence of metallic Mg as an acceptor of halide ions, catalyzed by bis(cyclopentadienyl)titanium dichloride. A mechanism for the reaction is proposed and discussed.     

TS-1/H2O2碱溶液中低温氧化愈创木酚制备马来酸（英）

可再生生物质资源的开发与利用能够缓解化石燃料产生的温室气体对环境的负面影响.在生物质燃料制备过程中联产高附加值化学品能大幅提高生物质炼制的经济性.愈创木酚是常见的木质纤维素快速热解产物.本文研究了低温液相氧化愈创木酚制备马来酸,并重点考察了催化剂添加量、pH值、反应时间和反应温度等反应条件的影响.研究发现,在钛硅沸石-过氧化氢碱溶液氧化反应体系中（80℃,pH=13.3）,20₃0mol%的愈创木酚可以选择性转化为马来酸.同时初步探讨了愈创木酚氧化开环转化为马来酸的反应机理.     

Syntheses, crystal structures, and properties of three new metal selenites Na2Co2(SeO3)3, Na2Co1.67Ni0.33(SeO3)3, and Na2Ni2(SeO3)3

Three new sodium cobalt (nickel) selenite compounds, namely, Na₂Co₂(SeO₃)₃, Na₂Co_1.67Ni_0.33(SeO₃)₃, and Na₂Ni₂(SeO₃)₃ have been hydro-/solvothermally synthesized in the mixed solvents of acetonitrile and water. Single-crystal X-ray diffraction analyses reveal that these isostructural compounds belong to the orthorhombic Cmcm space group and their structures feature three-dimensional open frameworks constructed by the two-dimensional layers of [MSeO₃] pillared by the [SeO₃]²⁻ groups. The two different types of Na⁺ ions reside in the intersecting two-dimensional channels parallel to the a- and c-axes, respectively. Their thermal properties have been investigated via TGA-DSC. The magnetic measurements indicate the existence of the antiferromagnetic interactions in these compounds.     

Application of zirconium-modified silica gel as a stationary phase in the ion-exclusion chromatography of carboxylic acids II. Separation of aliphatic carboxylic acids with pyromellitic acid as eluent and with suppressed conductimetric detection

The application of zirconium-modified silica gels (Zr-Silica) as stationary phases for ion-exclusion chromatography with conductimetric detection (IEC–CD) for C₁–C₈ aliphatic carboxylic acids (formic, acetic, propionic, butyric, valeric, caproic, heptanoic and caprylic acids) was carried out using pyromellitic acid as the eluent. Zr-Silicas were prepared by the reaction of the silanol group on the surface of silica gel with zirconium tetrabutoxide [Zr(OCH₂CH₂CH₂CH₃)₄] in ethanol solution. An ASRS-Ultra anion self-regenerating suppressor in the K⁺ form was used for the enhancement of conductimetric detector response of these aliphatic carboxylic acids. A Zr-Silica adsorbed on 10 mg zirconium g⁻¹ silica gel was the most suitable stationary phase in IEC–CD for the separation of these aliphatic carboxylic acids. Excellently simultaneous separation and highly sensitive detection for these aliphatic carboxylic acids were achieved in 25 min by IEC–CD with the Zr-Silica column (250×4.6 mm I.D.) and a 0.2 mM pyromellitic acid containing 0.15% heptanol as the eluent.     

Regioselective bromination of aromatic compounds with Br2/SO2Cl2 over microporous catalysts

A new selective brominating system Br₂/SO₂Cl₂/zeolite, has been discovered. Partially cation-exchanged Ca²⁺-Y zeolite efficiently catalyzes the selective para-bromination of neat chlorobenzene (CB) by Br₂/SO₂Cl₂ affording a CB conversion of ∼89% and a para-selectivity of ∼97%. During the bromination reaction, SO₂Cl₂ oxidizes HBr, prevents its accumulation within the zeolite pores and yields a more active brominating species. The Ca²⁺-Y catalyst was found to be stable under the bromination conditions, and can easily be regenerated by calcination. The Br₂/SO₂Cl₂/Ca²⁺-Y brominating system could be applicable to other activated aromatic compounds such as o-xylene, toluene and fluorobenzene.     

Structure and basic magnetic properties of the honeycomb lattice compounds Na2Co2TeO6 and Na3Co2SbO6

The synthesis, structure, and basic magnetic properties of Na₂Co₂TeO₆ and Na₃Co₂SbO₆ are reported. The crystal structures were determined by neutron powder diffraction. Na₂Co₂TeO₆ has a two-layer hexagonal structure (space group P6₃22) while Na₃Co₂SbO₆ has a single-layer monoclinic structure (space group C2/m). The Co, Te, and Sb ions are in octahedral coordination, and the edge sharing octahedra form planes interleaved by sodium ions. Both compounds have full ordering of the Co²⁺ and Te⁶⁺/Sb⁵⁺ ions in the ab plane such that the Co²⁺ ions form a honeycomb array. The stacking of the honeycomb arrays differ in the two compounds. Both Na₂Co₂TeO₆ and Na₃Co₂SbO₆ display magnetic ordering at low temperatures, with what appears to be a spin-flop transition found in Na₃Co₂SbO₆.     

A novel synthesis of (Z)-2-(1-trimethylgermyl-1-alkenyl)-1,3,2-dioxaborinanes and their conversion into carboxylic acids

A novel procedure for preparing heterocyclic compounds such as (Z)-2-(1-trimethylgermyl-1-alkenyl)-1,3,2-dioxaborinanes based on 1-trimethylgermyl-1-alkynes is described. 1-Trimethylgermyl-1-alkynes easily obtainable by deprotonation of 1-alkynes with n-butyllithium followed by treatment with trimethylgermanium chloride, are readily hydroborated in n-pentane in the presence of boron trichloride in hexane at 0 °C for 3 h. The resulting supernatant clear solution was separated from boron trichloride-methyl sulfide complex. It was then reacted with 1,3-propane diol at 0 °C for 0.5 h. The resulting representative (Z)-2-(1-trimethylgermyl-1-alkenyl)-1,3,2-dioxaborinanes were isolated in good yields (65-86%) and in high stereochemical purities (>98%) as evidenced by NMR spectral data. The carbon skeletons present in these intermediates were confirmed by alkaline hydrogen peroxide oxidation to the corresponding carboxylic acids.