Preparation and catalytic applications of partially fluorinated binaphthol ligands

New partially fluorinated binaphthols were obtained using a copper-catalyzed oxidative coupling. The corresponding enantiomerically pure compounds were prepared by fractional crystallization of the corresponding bis(menthyl)carbamates. Nucleophilic aromatic substitution using oxygen- and carbon-based nucleophiles resulted in functionalized derivatives without concomitant racemization. The titanium(IV) complexes of these ligands are catalytically active in the asymmetric oxidation of sulfides.     

Synthesis,characterization and properties of methylaminocellulose

Homogeneously prepared tosylcelluloses (TC) with degrees of substitution (DS) of DS_Tos 0.1–1.8 were used as intermediates for the synthesis of methylaminocelluloses (MAC) by nucleophilic substitution with methylamine. TC with DS_Tos up to 1.1 were shown to be valuable intermediates for selective synthesis of MAC with DS_MA varying from 0.1 to approximately 1. No nucleophilic substitution was observed at higher DS_Tos. At the chosen reaction conditions (60 °C, 48 h) residual tosyl moieties remained unchanged and little hydrolysis took place. The samples obtained were characterized by means of elemental analysis, FTIR and ¹³C CP/MAS NMR spectroscopy. ¹³C CP/MAS NMR spectroscopy was found to be an efficient tool for quantification of DS_MA. Furthermore, the swelling behaviour in water was investigated and preliminary tests concerning the bilirubin adsorption capacity of MAC were carried out.     

Toward phenanthridin-2-ylidene: electrophilicity versus acidity in planar-constrained C-aryl iminium salts

A phenanthridinium salt was prepared in four steps, including an intramolecular CH-arylation and a hydride abstraction reaction. Treatment with sterically demanding bases does not lead to the corresponding carbene, but rather to addition products: the planar-constrained geometry significantly enhances the electrophilicity over the acidity of C-aryl iminium salts.     

The synthesis of N-substituted ureas II: Nucleophilic substitution of ureas at the carbonyl group

Summary N-Arylsubstituted ureas undergo exchange of the N-residue upon reaction with amines. Using kinetic measurements, investigation of product distribution, regioselectivity, catalysis, and substrate influences, it was shown that this reaction proceeds via a second order nucleophilic substitution at the urea carbonyl center. By means of semiempirical calculations using the MNDO method the alternative mechanism of fragmentation was investigated.

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Zur Synthese N-substituierter Harnstoffe II: Nucleophile Substitution von Harnstoffen an der Carbonylgruppe

Zusammenfassung N-Arylsubstituierte Harnstoffe erleiden bei der Reaktion mit Aminen einen Austausch des N-Restes. Durch kinetische Messungen, Untersuchung der Produktverteilung, Regioselektivität, Katalyse und des Einflusses des Edukts konnte abgeleitet werden, daß es sich hiebei um eine nucleophile Substitution zweiter Ordnung am Carbonylzentrum des Harnstoffs handelt. Durch semiempirische Rechnungen mit Hilfe der MNDO Methode wurde der alternative Reaktionsmechanismus einer Fragmentierung untersucht.

     

Efficient synthesis of 2- and 3-substituted-2,3-dihydro [1,4]dioxino[2,3-b]pyridine derivatives

A versatile new approach for the synthesis in three steps of 2-substituted-2,3-dihydro[1,4]dioxino[2,3-b]pyridines B via a Smiles rearrangement using easily available reagents is described. A study illustrating the influence of experimental conditions on the progress of the reaction is reported.     

Functionalization of saturated hydrocarbons. High temperature bromination of octahydropentalene. Part 19

The synthesis and thermal bromination of octahydropentalene was studied. The reaction afforded 1a,3a,4b,6b-tetrabromo-1,2,3,4,5,6-hexahydropentalene (14) with remarkable regio- and stereospecificity. The structure of the product was determined by ¹H and ¹³C NMR data and single X-ray structural analysis. The treatment of octahydropentalene with tenfold bromine gave the octabromopentalene derivative. The formation mechanism of the products is discussed.     

有机磷化合物的质谱研究(Ⅵ)——磷酰二胺酯类化合物的电子轰击质谱和化学电离质谱

本文报道了7种新的N-烷基-N′-乙氧羰基甲基-N′-芳磺酰基-O-乙基磷酰二胺酯化合物的电子轰击质谱(EIMS)和化学电离质谱(CIMS,甲烷为反应气)。结果表明,无论是EIMS,还是CIMS均存在较多的骨架重排离子峰;取代基对谱图有较大的影响;EIMS中P—N键的断裂为重要质谱特征,CIMS中MH~+准分子离子为重要特征离子,还存在分子离子反应的产物。     

侧基为苯胺四聚体的聚丙烯酰胺的合成和表征

以异溴丁酸羟乙酯为引发剂、溴化亚铜和2,2′-联吡啶为催化剂和配体,引发丙烯酸琥珀酰胺酯(NAS)进行原子转移自由基聚合,得到的聚丙烯酸琥珀酰胺酯(PNAS)的分子量可以通过配比和转化率预测.进一步与单端氨基苯胺四聚体(TA)在50℃下反应,得到的聚合物用1H-NMR和FT-IR的测试,结果表明,当TA/NAS的摩尔比为3∶1时,PNAS上的琥珀酰胺酯可以完全被取代,从而得到侧链为苯胺四聚体的导电高分子.聚合物的结构和分子量以及分布用核磁共振氢谱、FT-IR和GPC进行表征;电化学性质用循环伏安法进行了测试.     

A new and versatile Ugi/SNAr synthesis of fused 4,5-dihydrotetrazolo[1,5-a]quinoxalines

A combinatorial synthetic route yielding fused tetrazolo[1,5-a]quinoxalines is described. The use of 2-fluorophenylisocyanide in the Ugi-tetrazole reaction (tetrazole-U-4CR) followed by a nucleophilic aromatic substitution (S_NAr) affords the tricylic tetrazolo[1,5-a]quinoxaline moiety in good yields and with high diversity.     

Chlorodimethylaluminum-promoted nucleophilic addition of lithium pentamethylcyclopentadienide to aliphatic aldehydes and DDQ-mediated carbon-carbon bond cleavage of the adducts providing the parent aldehydes

Treatment of aliphatic aldehyde with lithium pentamethylcyclopentadienide in the presence of chlorodimethylaluminum provided the corresponding carbinol in excellent yield. The carbinol returns to the parent aldehyde and pentamethylcyclopentadiene by the action of a catalytic amount of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ).