ESTERIFICATION REACTION OF ACETIC ACID WITH n-AMYL ALCOHOL OVER ZEOLITEBETA

在连续流动反应装置上研究了β沸石分子筛上正戊醇的酯化反应。经５００℃焙烧后的β分子筛对该反应有较好的催化作用。在β分子筛上，适宜的反应温度范围是１４０～１５０℃，较高的反应温度将降低催化剂的活性与选择性。随着乙酸／正戊醇摩尔比和ＬＨＳＶ的增加，酯的选择性增加。文中还讨论了离子交换度和焙烧温度对β分子筛表面性质和催化性能的影响。     

SYNTHESIS OF 1-(ACETYLSALICYLYL)-BENZOTRIAZOLE AND ITS REACTION WITH POLYVINYL ALCOHOL

l-(Acetylsalicylyl)-benzotriazole, a new active amide of acetylsalicylic acid has been synthesized either from acetylsalicylic acid and benzotriazole using DCCI as condensation agent or via acetylsalicylyl chloride and benzotriazole in the presence of triethylamine. The obtained active amide reacted readily with the hydroxyl group of PVA to produce the acetylsalicylyl ester of PVA.     

SYNTHESIS OF ACETIC ACID BY ISOMERIZATION OF METHYL FORMATE

A novel route for the isomerization of methyl formate to aceticacid was investigated by examining the nature of the metal catalysts,promot-ers and solvents under mild CO pressure.Both palladium and cobalt com-pounds in the N-methyl pyrrolidone solvent were highly efficient catalysts.     

SYNTHESIS OF ACETIC ACID BY CARBONYLATION OF METHANOL ON Ni(Ⅱ)CATALYSTS

The synthesis of acetic acid by carbonylation of methanol in the presence of Ni(Ⅱ)complexcatalysts at 200℃ under mild pressure was studied.The results showed that among the tested catalyststhe MCC-Ⅰ catalyst had the best performance for the reaction with a mathanol conversion of 98.2%and a carbonyl compound yield of 94.5%.The effects of the pKa values of ligands and the Debyevalues of solvents on the reaction were determined and a suggested mechanism involved in this reactionwas briefly discussed.     

SYNTHESIS AND MORPHOLOGICAL STRUCTURE OF POLY (PHENYLENE SULFIDE AMIDE)

Poly (phenylene sulfide amide) (PPSA) has been synthesized by using sulfur as Ssource which reacts with dichlorobenzamide (DCBA) and alkali in polar organic solvent atthe atmospheric pressure. The polymer structures were determined by elemental analysis,FT-IR and ~1H-NMR. It is shown that the yielded polymer has linear structure and itsstructure unit is -p-C_6H_4-CONH-p-C_6H_4-S-. The polymer morphology was studied byX-ray diffraction and polarized microscopy. The results show that PPSA is a crystallinepolymer and its spherulites are the aggregation of nontwisting lamella or micro-threadstructure. Under shearing force, these crystals are dispersed to form micro-fibrillarstructure. The decomposition kinetics of PPSA was also studied at different beating rates.The decomposition energy of PPSA is higher than that of PPS.     

SYNTHESIS AND CRTYSTAL STRUCTURE OF LUTETIUM (Ⅲ) COMPLEX WITH 1,3,5-BENZENETRICARBOXYLIC ACID

<正> LuC9H3O6(H2O)5·4H2O, Mr = 528. 3, monoclinic, C2/c, a = 14. 673(3), b=16.930(4), c= 14. 383(4)(?) , β=118.77(2)°, Z = 8, 7 = 3132(1) (?)3, Dc = 2. 24g/cm3, μ(MoKα) = 67.0cm-1, F(000) = 2064, R = 0. 052 for 4080 observed reflections. The Lutetium ion is eight-coordinated by three oxygen atoms, one from a 1, 3, 5,-benzenetricarboxylate ligands, two from another one, and five aqua ligands,forming a polymeric zigzag chain along the [101] direction. The Lu -O distances fall in the range of 2. 229 -2. 404(?).     

SYNTHESIS OF MESO-TETRA (4-METHOXYPHENYL-3-SULFONATE) PORPHINE AND SPECTROPHOTOMETRIC STUDY OF COLOUR REACTION WITH COPPER

In this paper meso-tetra (4-methoxyphenyl-3-sulpho) Porphine (TMPPS_4) was synthesized and its colour reaction with copper was studied. It was found to be a highly sensitive and highly selective reagent for the direct spectrophotometric determination of ultramicro amount of copper. The apparent molar absorptivity of the complex is 3.72×10~5L/mol·cm. Beer's law is obeyed for Cu(Ⅱ)of 0～1.4μg/10ml. The interference of 21 different ions and 6 kinds of salts were examined and found to be minimal. The complex formation of Cu(Ⅱ) with TMPPS_4 is generally slow at room temperature<<25℃>, but the reaction can be accelerated in the presence of NH_2OH·>HCl and completed within 5min. At PH 5.2 the Soret band of TMPPS_4 overlaps almost completetely with that of the complex. Therefore, the complex formation is taken to completion at this PH. Then the Soret band of TMPPS_4 shifted away from that of the complex by acidification.This simple and rapid method has been successfully applied to the direct determination of Cu in Al-alloys, industrial water, foods and human hair.     

SYNTHESIS OF THE COMPLEXES OF MACROPOROUS SULFONATED RESINS WITH FERRIC CHLORIDE ANDTHEIR CATALYTIC BEHAVIOR FOR ESTERIFICATION OF ACETIC ACID WITH BUTANOL

INTRODUCTIONOnthesulfonatedresinswereirnmobilizedBronstedacidsorLewisacidstobeabletofo～polymer--supporTedsuperacidswhichhavebeenattractedmuchattentionbysyntheticchemistsbecauseoftheirpotentialofapplicationinIndustry['J.Thepolymer--supportedsuperacldcatalystshavebothactivesitesofBronstedacidsandLewisacids.Insyntheticapplicationthesespedespossesstheadvantagesoftheeaseofseparationfromthereactionsystem,lowcorrosiontotheequipmentsandreusability.Sinceseventiestherearemanypapersthatreportedp…     

SYNTHESIS OF 3-BENZYL-GLYCERIC ACID:A KEY INTERMEDIATE OF A NOVEL CYCLIC ESTER MONOMER

A route was proposed to synthesize 3-benryl-glyceric acid (3-BGA) as an important intermediate for the synthesis ofa novel six-membered cyclic ester monomer - 3-benzyloxymethyl-1,4-dioxane-2,5-dione (3-BMG). According to this route,3-BGA was obtained from ring-opening reaction of benzyl alcohol with methyl glycidate, which was prepared from theepoxidation of methyl acrylate using sodium hypochlorite as the oxidant.     

NEW HETEROCYCLIC SYSTEM SYNTHESIS I REACTION OF DIHYDRO-1,5-BENZO-DIAZEPINES AND THIAZEPINES WITH (ETHOXYCARBONYL)CARBENES

Dihydro-1-benzoyl-1,5-benzodiazepines react with (ethoxycarbonyl)carbenes to give 4H-azirino-[1,2-a][1,5]-benzodiazepines and unexpected new tin9 system 1H-pyrrolo-[1,2-a][1,5]-benzodiazepines. Dihydro-1,5-benzothiazepines react with (ethoxycarbonyl)carbenes in cyclohexane to gire unexpected rin9 cleavage products ethyl (2E, 4E)-3-aryl-2-arylthiohexadienoates.     

SYNTHESIS, STRUCTURE AND PROPERTIES OF INTERPENETRATING SULFONIC ACID RESINS WITH HIGH CAPACITY

Two series of interpenetrating sulfonic acid resins (ISAR), 10×n and n×10, were prepared by means of the wet method, and the physicochemical, thermodynamic and kinetic properties of the ISAR were measured. The results show: 10×n resins exhibit better properties than n×10 ones, mainly in higher apparent degree of crosslinking and larger conformational entropy effect, among which, 10×1 resin exhibits the best thermodynamic and kinetic properties. In the DTA graphs of n×10 resins, there are two T_g and two T_(ox), but in those of 10×n, only one T_g and one T_(ox). This result well supports the conclusion that 10×n resins have much better interpenetrating structural aspects.     

SYNTHESIS OF TETRAMETHYL SALVIANOLIC ACID F AND TRIMETHYL PRZEWALSKINIC ACID A

ＳＹＮＴＨＥＳＩＳＯＦＴＥＴＲＡＭＥＴＨＹＬＳＡＬＶＩＡＮＯＬＩＣＡＣＩＤＦＡＮＤＴＲＩＭＥＴＨＹＬＰＲＺＥＷＡＬＳＫＩＮＩＣＡＣＩＤＡ￥ＣｈｕｎＢｏＡＩａｎｄＬｉａｎＮｉａｎｇＬｉ（ＩｎｓｔｉｔｕｔｅｏｆＭａｔｅｒｉａＭｅｄｉｃａＣｈｉｎｅｓｅＡｃ...     

SYNTHESIS OF α-AMINO-β-(4-IMIDAZOLYL)-ETHYLPHOSPHONIC ACID,THE PHOSPHONOISOSTERE OF HISTIDINE

A short synthesis starting from 4-imidazolylmethanol(2)was developedfor the phosphonoisostere of histidine,-amino-β-(4-imidazolyl)-ethylphosphosphonic acid,His(P)(1).The synthesis features Wittig-Hornerreaction of aldehyde(4)with diphosphonate(5)followed by selectivedetritylation with 50% formic acid.     

LEWIS ACID PROMOTFED ASYMMETRIC ENE－REACTION OF（－）－MENTHYL GLYOXYLATE WITH HOMOALLYL SILYL ETHER

ＬＥＷＩＳＡＣＩＤＰＲＯＭＯＴＦＥＤＡＳＹＭＭＥＴＲＩＣＥＮＥ－ＲＥＡＣＴＩＯＮＯＦ（－）－ＭＥＮＴＨＹＬＧＬＹＯＸＹＬＡＴＥＷＩＴＨＨＯＭＯＡＬＬＹＬＳＩＬＹＬＥＴＨＥＲＹｏｎｇＪｕｎＣＨＥＮ；ＤｏｎｇＷＡＮＧ；ＪｉＳｈｅｎＬＩ（Ｉｎｓｔｉｔｕｔｅ...     

SYNTHESIS AND PROPERTIES OF 1-(2-IMIDAZOLYLAO)2-NAPHTHOL-4-SULFONIC ACID

Synthesis of 1-(2-imidazolylazo)-2-naphthol-4-sulfonic acid is described including its physical and chemical properties and spectroscopic data. The reagent reacts with various transition metal ions to form water-soluble and colored chelates which can be decomposed by EDTA exoept cobalt chelate. Present method has good selectivity.     

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED POLY(ESTER-AMIDE)S BASED ON GALLIC ACID AND DL-2-AMINOBUTYRIC ACID

INTRODUCTIONHighly branched macromolecules including dendrimers and hyperbranched polymers are interesting materialswith unique molecular structures and potential applications[1-5]. The two types of polymers have many analogousphysical and chemical properties such as high solubility, low viscosity and abundance of terminal groups. Theformer attracts much attention of researchers due to its perfect monodisperse architecture, but its preparation isgenerally tedious because of various protect…     

KINETIC STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A NOVEL COPOLYMER-BOUND CIS-DICARBONYLRHODIUM COMPLEX

The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh) coordinated with the ethylene diacrylate (M') crosslinked copolymer of methyl acrylate (M) and 2-vinylpyddine (V)shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex. Polar solvents can accelerate the reaction. Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system. A mechanism similar to that of soluble rhodium catalyst was proposed.     

SYNTHESIS OF CHIRAL MIXED-LICAND COMPLEXES AND THEIR USE IN ASYMMETRIC SYNTHESIS OF CHRYSANTHEMIC ACID

Several chiral mixed-ligand complexes have been synthesized and theirefficiency as catalysts for the asymmetric synthesis of chrysanthemic acid tested.     

REACTION OF α-BENZENESULFONYLPHENYLACETIC ACID WITH ALKYL HALIDES. DECARBOXYLATIVE ALKYLATION VS. DECARBOXYLATIVE PROTONATION

The reaction of α-benzenesulfonylphenylacetic acid with some alkyl halides, using as base NaH in DMSO, leads to decarboxylative protonation to give benzylphenylsulfone. Decarboxylative alkylation occurs only when CO₂ is expelled by flushing with nitrogen. The mechanism of the decarboxylative protonation is investigated.     

SYNTHESIS AND STRUCTURE OF A NEW TYPE OF COORDINATION COMPOUND OF Tb（Ⅲ）WITH BENZOIC ACID

<正> The synthesis and crystal structure of a novel rare earth coordination compound are reported. [TbL3(HL)H2O]2 (HL=henzoic acid) Mr=1324. 81, triclinic, space group P1, a=9. 148(1), b=11. 4 60(2), c=13. 506(2) A ;a=112. 76(1), B=91.83(1),y=91. 99(1) ;Z=1 ;V=1303. 3(4)A3;Dc=1.69g.cm-3;F(000)= 656;u=28. 4cm-1(MoKa). The final R is 0. 024. Each rare-earth ion in the title complex is nine-coordinated by seven oxygen atoms from five benzoate groups, one benzoic acid, and one aqua molecule, forming a distorted monocapped square antiprism.