Reactivity of Carboxamides toward Benzoyl Chloride in Acetonitrile

Catalytic action of carboxamides at benzoyl chloride hydrolysis in acetonitrile at 25°C occurs by nucleophilic mechanism. Its first stage consists in reversible interaction between amides and substrate. The rate constants of the direct reaction were determined which characterized the oxygen-nucleophilic reactivity of amides toward benzoyl chloride. The assumption was confirmed that bimolecular addition of benzoyl chloride to the carbonyl oxygen of amides occurred in cyclic transition states.     

Reactivity of Cage-Like Amines toward p-Toluenesulfonyl Chloride and Diphenyl Chlorophosphate in Acetonitrile

The nucleophilic reactivity of amines of the norbornane, norbornene, and adamantane series toward ptoluenesulfonyl chloride and diphenyl chlorophosphate in acetonitrile at 25°C is determined mainly by the steric factor. Parameters characterizing spatial accessibility of the reaction center in the amine molecule have been determined. Cage-like substituents show no appreciable effect on the amine reactivity, as compared to common alkyl groups.     

The Reactivity of Diphenyl Carbonyl Oxide in Reactions with Alcohols

The reactivities of ten alcohols in the reactions with diphenyl carbonyl oxide Ph₂COO is characterized by the ratio k ^OH ₃₃ /k ₃₁, where k ^OH ₃₃ and k ₃₁are the rate constants of Ph₂COO reactions with an alcohol and diphenyldiazomethane PH₂CN₂, respectively. The values of k ^OH ₃₃ /k ₃₁range between 0.6 × 10^–2for MeOH to 6.0 for iso-PrOH at 70°C in acetonitrile. The donation of electron density to the alcohol hydroxyl group favors the attack of Ph₂COO; that is, Ph₂COO reacts as an electrophile.     

Oxidation of Magnesium with Benzoyl Chloride in a Mixture of Tetrahydrofuran and Benzene

The kinetic features of magnesium oxidation with benzoyl chloride in a mixture of tetrahydrofuran and benzene were studied. A reaction mechanism was suggested, involving attack of the oxidant molecule adsorbed on the metal surface by a similar molecule from the bulk of the solution.     

三苯基膦中微量氯离子的分离

三苯基膦 [P(C6H5) 3]是一种有机化合物 ,当作为催化剂使用时 ,对其中杂质微量氯离子的含量有严格要求。在用电极法测定其微量氯离子时 ,将氯离子从样品中全部提取是分析结果准确的关键之一。本文讨论了用电极法测定三苯基膦中微量氯离子的分离方法[1] 。1　仪器与试剂p HS- 2型酸度计 (上海第二分析仪器厂 )CT- 1型磁力搅拌器 (北京医用离心机厂 )80 1双液接饱和甘汞电极 (江苏电分析仪器厂 )氯离子选择性电极 (长沙半导体材料厂 )氢氧化钠溶液 :1 0 0 g· L-1硝酸 :0 .2 mol· L-1氯离子储备液 :1 g·L-1硝酸钠溶液 :p H4.0 ,0 .5mol…     

LC Determination of Propylene Glycol in Human Plasma After Pre-Column Derivatization with Benzoyl Chloride

A simple high-performance liquid chromatographic method, using photodiode array detection was developed for the determination of propylene glycol in human plasma and in the fluid retreived after continuous veno-venous hemofiltration. The method entailed alkaline derivatization with benzoyl chloride and ethylene glycol as internal standard. The separation of the compounds, after extraction with pentane, was carried out on a Pursuit C8 column with UV-detection at 230 nm. Validation samples were analyzed with an accuracy between 95 and 105%, and intra- and inter-day coefficients of variation of less than 8%. The calibration curve was linear over a concentration range of 5–100 mg L⁻¹ with a detection limit of 1 mg L⁻¹. Blood plasma samples of several patients were analysed by using the prescribed method with propylene glycol concentrations varying from 5 to 98 mg L⁻¹. Compared to previously described LC methods, this method is ten times more sensitive and thus suitable for use in pharmacokinetic studies of propylene glycol.     

The Reaction of Benzoyl Substituted Heterocyclic Ketene Aminals with 4-Nitrobenzhydroximic Acid Chloride

Heterocyclic ketene aminals 1 or 2 reacted with 4-nitrobenzhydroximic acid chloride (3) to give the 3,5-diaryl-4-(2-imidazolinyl)-isoxazoles 4 or 3,5-diaryl-4-(2-tetrahydropyrimidinyl)-isoxazoles 5. The mechanism of their formation were also discussed.     

Reactivity Ratios of Diethyldiallylammonium Chloride with Acrylamide or Acrylic Acid

The compositions of copolymers of diethyldiallylammonium chloride (DEDAAC) with acrylamide (AM), acrylic acid (AA) or sodium acrylic acid (NaAA) at low conversion were determined by elemental analysis, and the reactivity ratios of monomers in copolymerization were obtained by Kelen-Tudos method. The results showed that the reactivity ratios rDE and rAM are 0.31 and 5.27 for DEDAAC with AM, rDE and rAA are 0.28 and 5.15 for DEDAAC with AA, and rDE and rNaAA are 0.40 and 3.97 for DEDAAC with NaAA, respectively. The copolymerizations for DEDAAC with AM, AA or NaAA are non-ideal copolymerization and the products are random copolymers.     

Nafion功能化介孔催化剂上苯甲醚/苯甲酰氯酰基化反应研究

苯甲醚/苯甲酰氯的酰基化产物4-甲氧基二苯甲酮是多种精细化工产品的重要中间体. 本工作主要介绍了Nafion负载型SBA-15, SBA-16及Me-SBA-15介孔超强酸催化剂的制备及其在苯甲醚/苯甲酰氯酰基化反应中的应用. 实验结果表明, 单位时间单位Nafion活性位上的苯甲酰氯转化数高于传统HBeta沸石和硫酸氧化锆, 且载量的增加能显著提高酰基化催化性能. 甲基修饰的Me-SBA-15介孔材料明显改善了催化剂表面的疏水性能, 有效减缓了多聚芳烃副产物的生成, 反应的转化率得到大幅提高. 相对一维孔道结构的介孔SBA-15而言, 三维笼状结构的SBA-16对反应物及产物分子具有更好的扩散性能, 该结构优势由酰基化反应的高初始活性得以充分体现. 在整个反应过程中, 该类催化剂对4-甲氧基二苯甲酮具有专一的选择性.     

Characterization Reaction of Benzoyl Methylene Triphenylphosphorane and Benzoyl Methylene Tri-n-buthylphosphorane with Rhodium (III) and Ruthenium (III) Chloride. A Multinuclear NMR Study

The reactions of title ylide (C 6 H 5 ) 3 PCHCOC 6 H 5 , (BPPY) and (n-C 4 H 9 ) 3 PCHCOC 6 H 5 , (BBuPY) with rhodium (III) and ruthenium (III) chloride in equimolar ratios using methanol as solvent have yielded crystals of [(BPPY-H) 3 Rh], ( 1 ), [(BPPY) 2 Ru(MeOH) 2 (H 2 O) 2 ]Cl 3 , ( 2 ), and [Ru(BBuPY)Cl 2 S 2 ]Cl (S = H 2 O or CH 3 OH), ( 3 ). The IR and 1 H, 13 C, 31 P NMR data of the products were obtained. Analytical and NMR data are consistent with the cyclometalated and octahedral structures for ( 1 ) and ( 2 ) respectively.     

二乙基二烯丙基氯化铵与丙烯酰胺、丙烯酸共聚竞聚率

二乙基二烯丙基氯化铵;丙烯酰胺;丙烯酸;共聚合;竞聚率     

Synthesis and Reactivity of Aliphatic and (Hetero) Aromatic N-Alkyl-N-(Diphenyloxophosphinyl) Methyl Carboxamides and Lactams

A variety of aliphatic, aromatic and heteroaromatic N-alkyl-N-(diphenyloxophosphinyl) methyl carboxamides and lactams have been prepared by preliminar chloromethylation of the appropriate secondary amides and subsequent treatment with ethyl diphenylphosphinite.     

Structure and Reactivity of Arsazocompounds in Comparison with Phosphorus Analogs

Abstract

A suitable effective method of arwocompounds 2 synthesis through the alkoxyarsoranes I has been suggested. In dependence on the nature of substituents R and R arsazocompounds (as their phosphorus analogs) may exist in monomeric (2) and dimeric (3) forms, that has been confirmed by X-ray analysis.     

Reactivity with Respect to Bases of 5-Hydroxy-7-oxo-6-azabicyclo[3.2.1]octane-1,2,2-tricarbonitriles

Russian Journal of Organic Chemistry -     

Synthesis of Sodium Diselenides and its Reaction with Benzoyl Chloride Under Phase Transfer Catalysis and Microwave Irradiation Conditions

A simple, fast and efficient procedure for the synthesis of dibenzoyl diselenides involves the reaction of selenium with sodium hydroxide under phase transfer catalysis and microwave irradiation conditions to give sodium diselenides, which reacts with benzoyl chloride at 0-3 °C and conventional conditions to afford the dibenzoyl diselenides. The effect of microwave irradiation power, reaction time, solvent and operational method on the reaction is investigated.     

Synthesis and Crystal Structure of 2 Benzoyl Pyridine Thiosemicarbazato Palladium(II) Chloride

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氯乙烯发生亲电加成反应的活性与取向

氯乙烯与氯化氢亲电加成反应的主要产物为1,1一二氯乙烷,符合Markovnikov规则。氯乙烯与HA型化合物的亲电加成都具有相似结果。     

Heterocyclization of 6-tert-Butyl-3-hydrazino-2,5-dihydro-1,2,4-triazin-5-one with Benzoyl Chloride and Formic Acid

Reaction of 6-tert-butyl-3-hydrazino-2,5-dihydro-1,2,4-triazin-5-one with excess benzoyl chloride or formic acid afforded 6-tert-butyl-[1,2,4]triazolo[4,3-b][1,2,4]triazin-7(8H)-ones.     

对酞内酰胺苯甲酰氯柱前衍生反应HPLC法检测痕量芳香胺

建立了一种快速、灵敏检测痕量芳香胺的新方法。对苯胺、邻甲苯胺和间甲苯胺与对酞内酰胺苯甲酰氯（简称ＰＩＢ－Ｃｌ）的衍生反应条件、衍生物色谱分离及定量检测条件等进行了研究。衍生试剂在有机溶剂中与３种芳香胺反应迅速，衍生物用乙腈＋水（４８＋５２）作流动相，在反相色谱系统中得到了良好的分离。３种芳香胺的检出限分别为：苯胺１．５ｐｍｏｌ，邻甲苯胺和间甲苯胺均为２．０ｐｍｏｌ。     

氯乙烯/N-取代马来酰亚胺共聚竞聚率及共聚物组成

研究了氯乙烯(VC)与多种N-取代马来酰亚胺的溶液共聚合,求得各对单体的竞聚率.结果表明,各种马来酰亚胺的竞聚率都远高于VC的竞聚率,即N-取代马来酰亚胺单体的活性均比VC单体活性高.计算得到N-取代马来酰亚胺Q和e值.由于苯环的共轭效应,N-苯基及N-取代苯基马来酰亚胺具有较大的Q值.各对单体的e值差别较大,表明有形成交替共聚物的倾向.此外,还考察了聚合过程中共聚物组成的变化,用递推法预测了这类体系共聚物瞬时和累积组成随转化率的变化.