碳酸二苄酯的合成及光谱研究

以苯甲醇为原料,用氧化羰化法合成碳酸二苄酯,反应条件为100℃、2.4MPa、CuCl浓度为0.20mol/L、NMI浓度为0.40 mol/L、反应3 h.结果表明,苯甲醇的转化率为25.6%,碳酸二苄酯的选择性大于99.9%.用萃取重结晶的方法进行了分离提纯,得到了纯度为99.7%的碳酸二苄酯白色结晶,其熔点为27.2～29.1℃.用红外光谱,紫外光谱,核磁共振H谱以及质谱对碳酸二苄酯的分子结构进行了分析.

Synthesis of Diphenyl Carbonate over the Magnetic Catalysts Pd/La_(1-x)Pb_xMnO_3 (x=0.2-0.7)

The magnetic perovskite-supported palladium catalysts Pd/Lal_xPbxMnO3 （x = 0.2-0.7） were prepared and used for the oxidative carbonylation of phenol to diphenyl carbonate. The synthesized catalysts were characterized by the X-ray diffraction （XRD）, surface area measurement BET, vibration sample magnetometer （VSM） and tem- perature-programmed reduction （TPR）. The experimental results demonstrated that the magnetic Pd/La1-xPbxMnO3 （x = 0.4-0.5） obtain relative better catalytic activity. It can be explained by higher concentration of oxygen vacan- cies, larger amount and better mobility of lattice oxygen of their support. Furthermore, these samples possess suffi- cient saturated magnetization. Thus, Pd/La1-xPbxMnO3 （x = 0.4-0.5） may be suitable for operation in the magneti- cally stabilized bed reactor.

Linear-regioselective hydromethoxycarbonylation of styrene using Ru-clusters/CeO2 catalyst

Hydroalkoxycarbonylation of olefins has been considered to be one of the most attractive methods to synthesize esters. Controlling the regioselectivities of linear esters(L) and branched esters(B) is a challenging project for researchers working in this reaction. Although most of the attention has been paid to control the regioselectivity through ligand design in homogeneous catalytic systems, study in the area is still limited. Herein, Ru-clusters/CeO2 is employed as a heterogeneous catalyst for the hydromethoxycarbonylation of styrene without any additives. After optimization of the reaction conditions, the conversion of styrene is > 99% with 83% and 12% regioselectivity of linear and branched ester, respectively. By using different supports(CeO2(nanoparticle), CeO2-rod, and CeO2-cube), three catalysts including Ru-clusters/CeO2, Ru/CeO2-rod, and Ru/CeO2-cube are prepared and applied in the reaction. Structural characterizations demonstrate that the L/B ratio is related to the Ru size of supported Ru catalysts. Further Raman characterization and NH3-TPD demonstrate that the metal-support interaction and the concentration of oxygen vacancy of the catalyst have a great influence on the Ru size. The mechanism and kinetic analysis for this reaction are also investigated in this work.

Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (V) Screening Catalysts and Optimizing Synthesis Conditions

Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was Lao.szPbo.asMnOa and the average diameter could be about 25.4nm. The optimuna conditions for synthesis of DPC with Pd/LasPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catalyst/phenol mass ratio l to 50, pressure 4.5MPa, volume concentration of O2 25%, reaction temperature 60℃ and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the batch operation.

Cobalt carbonyl ionic liquids based on the 1,1,3,3-tetra-alkylguanidine cation:Novel, highly efficient, and reusable catalysts for the carbonylation of epoxides

A series of novel cobalt carbonyl ionic liquids based on1,1,3,3‐tetra‐alkyl‐guanidine,such as[1,1‐dimethyl‐3,3‐diethylguanidinium][Co(CO)4](3a),[1,1‐dimethyl‐3,3‐dibutylguanidinium][Co(CO)4](3b),[1,1‐dimethyl‐3,3‐tetramethyleneguanidinium][Co(CO)4](3c),and[1,1‐dimethyl‐3,3‐pentamethyleneguanidinium][Co(CO)4](3d),were synthesized in good yields and were also characterized using infrared spectroscopy,ultraviolet‐visible spectroscopy,1H nuclear magnetic resonance(NMR)spectroscopy,13C NMR spectroscopy,high‐resolution mass spectrometry,differential scanning calorimetry,and thermogravimetric analysis.The four compounds exhibited high thermal and chemical stability.In addition,the catalytic performance of these compounds was investigated in the carbonylation of epoxides,with3a exhibiting the best catalytic activity without the aid of a base as the additive.The catalyst could be reused at least six times without significant decreases of the selectivity or conversion rate.Moreover,the catalyst system exhibited good tolerance with terminal epoxides bearing alkyl,alkenyl,aryl,alkoxy,and chloromethyl functional groups.

Maillard Products Formed from Chicken Fat Oxidants and Amino Acids Act as a Flavor Enhancer in Comminuted Chicken Products

Lipid oxidation and degradation are generally recognized as unfavorable reactions in food processing. However, lipids can be utilized to produce meat-like flavorings through reaction with amino acids after degradation to carbonyls such as aldehydes and ketones. The fatty acids in chicken fat mainly comprise palmitic acid, oleic acid and linoleic acid. After being heated at 120 ~C for 3 h, the degraded carbonyls of chicken fat were reacted with cysteine, alanine, glycine and thiamine to form a chicken-like flavoring. The key aromatic components of the flavoring were identified by GC-MS. In the overall volatile profile, 22 kinds of compound were detected, among which 2-furanmethanol was formed by the Maillard reaction, 1-（2-furanyl）-ethanone by cyclization and 2,4,6-trimethyl-l,3,5-trithiane by the Strecker degradation of cysteine. Dihydro-2-methyl-3（2H）-furanone, dihydro-2-methyl- 3（2H）-thiophenone, 2-acetyl-lH-pyrroline and 4-methyl-5-thiazoleethanol were the degradation products of thiamine. The prepared chicken flavoring was added to comminuted chicken product （CCP）. GC-MS analysis and sensory evaluation showed that the flavor and odor of the CCP were greatly enhanced.

An efficient and facile synthesis of N-Cbz-β-aminoalkanesulfonamides

An efficient method for the synthesis of N-Cbz-β-aminoalkanesulfonamides was described.N-Cbz-β-aminoalkanesulfonamides were readily prepared in good yields from a variety of amino alcohols,including optically active ones,via N-Cbz protection with benzyl chloroformate,Mitsunobu esterification reaction with thiolacetic acid,N-chlorosuccinimide oxidation,and ammonolysis process.