Mechanism of the hydrolysis of α-(<Emphasis Type="Italic">p</Emphasis>-nitrophenyl)cinnamonitrile derivatives

The rate constant hydrolysis of α-(p-nitrophenyl)cinnamonitrile(NCPN) and its derivatives have been determined at various pH, and the rate equation which can be applied over a wide pH range is obtained. On the basis of the rate equation, hydrolysis product, general base, and substituent effects, a plausible mechanism of hydrolysis has been proposed: At pH < 4.0, the hydrolysis was initiated by the addition of water to β-carbon of the carbon-carbon double bond. At pH > 8.5, the addition of hydroxide ion to the double bond was rate controlling. In the range of pH 4.0–8.5, these two reactions occurred competitively. Published in Russian in Kinetika i Kataliz, 2007, Vol. 48, No. 5, pp. 670–676. This article was submitted by the authors in English.     

Modification chimique de polyisoprenes et de polybutadienes de faible masse par addition de trichlorosilane

The addition of trichlorosilane to carbon-carbon double bonds of low molecular weight polyisoprenes and polybutadienes has been studied with hexachloroplatinic acid as catalyst. The reaction was carried out in benzene as solvent, at 110, under nitrogen pressure. The reaction rate decreases as the carbon-carbon double bond substitution increases. In most cases, addition of trichlorosilane is accompanied by cyclization reactions more or less important depending on the polymer structure, except for 1,2-polybutadiene. Trichlororosilyl groups have been modified to trimethyl and trimethoxy derivatives.     

An unexpectedly mild thermal Alder-ene-type cyclization of enallenes

A mild, thermal Alder-ene reaction of enallenes has been developed. The allenic double bond acts as the "ene" and generates a carbon-carbon bond to an unactivated olefinic "enophile" in DMF at 120 degrees C to give [n.3.0] bicyclic systems (n = 3-5) in good yields. Except for a minor [2 + 2] cycloaddition byproduct, the reaction proceeded with complete atom economy, as there is no requirement of a catalyst or additional reactants, and no waste products are formed in the process.     

二氧化锆微球表面键合磺化交联聚苯乙烯固相萃取填料的制备及应用

以聚合诱导胶体凝聚法(PICA)制备二氧化锆微球,用钛酸酯偶联剂对其进行表面改性,使其接枝上碳碳双键基团。在溶液体系中,该双键与单体苯乙烯和二乙烯苯在自由基引发下交联聚合,形成的聚合物包覆在二氧化锆微球表面。再通过磺化方法将磺酸基离子连接到苯环上,得到阳离子交换固相萃取填料。通过红外光谱、扫描电镜/X射线能谱等手段对其进行了表征。将装填得到的固相萃取柱与高效液相色谱联用,测定了水中的甲基磺草酮、阿特拉津和乙草胺。3种化合物的色谱峰面积与质量浓度呈良好的线性关系,相关系数(r²)均大于0.99;甲基磺草酮、阿特拉津和乙草胺的检出限分别为5.41、6.72和13.4 μg/L。结果表明,制得的聚合物包覆二氧化锆微球的粒径为6~8 μm,用该填料制成的固相萃取小柱对3种目标物的吸附率高。     

Reactions of 1-nitrocyclohexene with alicyclic amines

The interaction of 1-nitrocyclohexene with alicyclic amines can proceed via nucleophilic addition at the carbon-carbon double bond (morpholine, piperazine) to form aza-Michael products or as deprotonation (piperidine, azepane) to give ammonium salts, 2-cyclohexene-1-nitronates. The preferred reaction pathway is determined by the amine basicity.     

Pd(II)-bipyridine catalyzed conjugate addition of arylboronic acid to alpha,beta-unsaturated carbonyl compounds

[Reaction: see text]. A Pd(II)-catalyzed conjugate addition of arylboronic acid to alpha,beta-unsaturated ketones, aldehydes, esters, etc. in the presence of 2,2'-bipyridine was developed. A mechanism involving transmetalation, insertion of the carbon-carbon double bond into the C-Pd bond, and protonolysis of the resulting C-Pd bond is proposed. The reaction conditions are mild and the yield is high. The presence of 2,2'-bipyridine is crucial for the reaction to inhibit beta-hydride elimination.     

Rhodium-catalysed substitutive arylation of cis-allylic diols with arylboroxines

Substitutive arylation of cis-allylic diols occurs upon treatment with arylboroxines in the presence of a rhodium(I) catalyst; the reaction proceeds through the addition of an intermediate arylrhodium(I) species across the carbon-carbon double bond and subsequent beta-oxygen elimination.     

Molybdenum-catalyzed ring-closing metathesis of allenynes

A ring-closing metathesis reaction of allenynes occurred at room temperature in the presence of a molybdenum alkylidene complex to give ring-closed vinylallenes. The vinylallene skeletons were constructed by a metathesis-type reaction between the alkyne moiety and the proximal carbon-carbon double bond of the allene moiety. [reaction: see text]     

The Regioselectivity of (Dimethylvinylidene)carbene Directed by Aromatic Ring upon the Addition into Aryl Alkenes in the Presence of Other Olefins

Regioselective cycloaddition of (dimethylvinylidene)carbene (1) into aryl alkenes in the presence of other olefins is reported. The reaction is presumably controlled by the phenyl group, which forms an aromatic π-complex with the carbene C-3 orbital, followed by the selective addition of 1 to the closest phenyl-substituted double bond. Also, this selectivity is assumed to be attributed to delocalization of aromatic π electrons which increases the electron density of the conjugated carbon-carbon double bond, thus leading to the facile addition of vinylidenecarbene.     

Highly site, regio-, and stereoselective multicomponent reaction of benzimidazole carbenes, isothiocyanates, and allenoates

The novel three-component reaction of benzimidazole carbenes with isothiocyanates and allenoates proceeded efficiently in a highly site, regio-, and stereoselective manner to produce predominantly spiro[benzimidazoline-2,3′-tetrahydrothiophene] derivatives. The reaction was proposed to occur via a tandem nucleophilic addition of carbenes to isothiocyanates followed by an unusual [3+2] cycloaddition to the less activated carbon-carbon double bond of allenoates.     

两相体系中催化氢化丙烯腈制备丙腈

膦配体TPPTS(三-间磺酸钠-三苯基膦)的水溶性很好,有关其过渡金属配合物催化剂的应用与研究活跃。近年来,对丙烯腈C=C双键加氢的研究多集中在以钯为中心金属的多相催化体系上,已报道的有聚硅氧烷钯体系,膦酸锆负载钯体系,高分子负载钯．金属氧化物催化剂,SiO2负     

Ramberg-Backlund反应在构筑碳碳双键中的应用

碳碳双键是有机化学中最基本的官能团之一，在众多的构筑碳碳双键的方法中 Ramberg-Baecklund反应占有很重要的地位。该方法的关键步骤是α－卤代砜在碱 性条件下，发生1，3－消除反应，得到环状砜，然后重排失去SO2形成双键，这样 形成的双键位置确定，即具有良好的区域选择性，并且在不同的反应条件下可得到 不同构型的产物，因而在有机合成中有很好的应用前景，对Ramberg-Baecklund反 应进行了较为详细的综述，并对我国实验室所进行的反应条件的改进和优化以及目 前的研究进展作了总结。     

Palladium-catalyzed intramolecular cyanoboration of allenes leading to the regioselective synthesis of β-cyanoallylboranes

Inter- and intramolecular addition of the boron-cyanide bond of cyanoboranes across a carbon-carbon double bond of allenes proceeded in the presence of palladium catalysts, affording allylboranes that bear a cyano group at the β-position regioselectively.     

Palladium-catalyzed, stereoselective, cyclizative alkenylboration of carbon-carbon double bonds through activation of a boron-chlorine bond

Palladium-catalyzed alkenylboration of carbon-carbon double bonds has been achieved using the reaction of chloro(diisopropylamino)boryl ethers of homoallylic alcohols with alkenylzirconium reagents. The reaction may proceed through an initial oxidative addition of the B-Cl bond, intramolecular insertion of the C═C bond into the B-Pd bond, transmetalation from the alkenylzirconium reagent, and reductive elimination of the products. The cyclization proceeds with high diastereoselectivity for the formation of cis-3,5- or trans-3,4-disubstituted-1,2-oxaborolane products. Cross-coupling of the resultant products with aryl iodides proceeds with retention of configuration at the boron-bound secondary carbon atom.     

Deoximation of Oximes,Sodium Oximates,and O-Benzoyloximes with Copper (II) Chloride Dihydrate

Oximes, O-benzoyloximes and sodium salt of aldoximes and ketoximes were deoximated to their parent carbonyl compounds with copper (II) chloride dihydrate in acetonitrile as well as water. This method works well with both aldoximes and ketoximes without any risk of overoxidation in the former case. In addition, sensitive groups like ester, acetamido, isolated as well as conjugated carbon-carbon double bond and phenolic and ether linkages could survive the reaction conditions. The yields and reaction rates were increased in case of aromatic oximes when the reaction was carried out in aqueous acetonitrile. A novel deoximation procedure using sodium oximate which showed considerable rate enhancement over that of oximes, and tolerance to hydrolytically labile ester and amide groups is also described.     

Dynamic 1H NMR study around the carbon-carbon single bond and partial carbon-carbon double bond in the two particular phosphorus ylides and in an enaminoester

Herein, a series of separate dynamic (1)H NMR effects are reported at different temperatures within a particular enaminoester involving a phenanthridine. These effects are attributed to restricted rotation around the two single bonds such as carbon-carbon (H(a)-C-C-H(b)) and nitrogen-carbon (NCCOOCH(3)). Activation energies (E(a)) for these interconversion processes in their rotational isomers are equal to 20 and 20 ± 1 kJ mol(-1), respectively. In addition, three dynamic (1)H NMR effects are investigated at different temperatures for a particular phosphorus ylide involving a 2-indolinone around the carbon-carbon single bond (H-C-C-PPh(3)) within the two Z- and E-rotational isomers and partial carbon-carbon double bond (OCH(3)-C=C-PPh(3)). Activation energies (E(a)) for these interconversion processes in rotational isomers are equal to 53, 63 and 73 ± 1 kJ mol(-1) , respectively. This behavior was also observed for other phosphorus ylide containing 2-mercaptobenzoxazole around the carbon-carbon single bond and partial carbon-carbon double bond with their relevant activation energies containing 13, 10 and 75 ± 1 kJ mol(-1), respectively.     

Reaction of some amines with unsaturated N-acylbenzoxazolones

It is shown that the addition of aniline proceeds at the carbon-carbon double bond of N-acryloyl-, N-chloroacryloyl-, and N-methylacryloylbenzoxazolones. The basicity of the amine has a substantial effect on the course of the reaction with various amines. Transamidation of the acryloyl residue occurs with strongly basic amines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1044–1048, August, 1974.     

Stereoselective synthesis of trisubstituted alkenylboranes by palladium-catalysed reaction of alkynyltriarylborates with aryl halides

The palladium-catalysed reaction of alkynyltriarylborates with aryl halides afforded trisubstituted alkenylboranes, in which two different aryl groups were installed across the carbon-carbon double bond in a cis arrangement.     

Ramberg-Bäcklund反应在功能有机分子合成中的应用

碳碳双键广泛地存在于功能有机分子中, 其构筑在合成化学中具有极其重要的意义. Ramberg-Bäcklund反应是构筑碳碳双键的重要方法之一, 其关键步骤是砜在碱性条件下进行1,3-消除, 得到环状砜, 然后重排除去SO₂形成双键.该方法具有良好的立体选择性, 底物在不同的反应条件下得到不同构型的产物, 因而可以应用于合成许多功能有机分子, 具有很好的应用前景. 结合自己的研究工作对Ramberg-Bäcklund反应在功能有机分子合成中的应用进行了较为系统的总结, 也对Ramberg-Bäcklund反应的拓展进行了简要介绍.     

A comparative ab initio study of intramolecular proton transfer in model alpha-hydroxyalkoxides

A comparative ab initio study was performed on the intramolecular proton-transfer reaction that occurs in alpha-hydroxyethanoxy, alpha-hydroxyphenoxide, and alpha-hydroxyethenoxy anions. The intramolecular proton transfer occurs in a five-member atom arrangement, between two oxygen atoms separated by a carbon-carbon bond. The chosen systems serve as models for alpha-hydroxyalkoxide molecules where the carbon-carbon bond varies from a single bond (the glycolate anion or alpha-hydroxyethanoxide anion) to a part of an aromatic ring (the alpha-hydroxyphenoxide anion), and finally to a double bond (the alpha-hydroxyethenoxide anion). Particular attention was given to the evolution along the intrinsic reaction coordinate of such properties as energies, relevant structural parameters, Mulliken charges, dipole moments, and 1H-NMR chemical shifts to reveal the similarities and differences for the proton transfer in the model systems.