Tetraarylester der μ-Imidodiphosphorsäure und ihre Thioderivate — Strukturuntersuchungen

Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by ¹H, ¹³C, and ³¹P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the ²J_{P? N? P} coupling constants were determined by ¹³C{¹H, ³¹P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.     

Stereochemistry of cyclic ether formation—II : Intramolecular cyclisation of secondary aliphatic alcohols to tetrahydrofuran-type ethers

The mechanism and stereochemistry of δ-C atom functionalisation in the reactions of secondary straight-chain aliphatic alcohols with lead tetraacetate, ceric ammonium nitrate, and heavy metal (Pb⁴⁺, Hg²⁺, Ag⁺) salts (AcO)^?1, O^2?, CO₃^2?-halogen (I₂, Br₂, Cl₂) combinations are discussed. By demonstrating the intermediacy of 5-bromo-2-hexanol, it was confirmed that the dark silver oxidebromine induced cyclisation of 2-hexanol (and alcohols in general) involves (as the other hypohalite reactions) intramolecular 1,5-hydrogen abstraction by alkoxy radicals and formation of δ-bromohydrins. A novel and simple procedure for obtaining tetrahydrofurans from alcohols by way of the hypochlorite reaction, using silver or mercuric salts and chlorine, is described.     

反-1,2-双[2'-(5'-苯基恶唑基)]乙烯的晶体结构

用X射线单晶衍射法测定了反-1,2-双[2'-(5'-苯基恶唑基)]乙烯(POEOP)的晶体结构,POEOP晶体属单斜晶系, 空间群为P2~1/C, a=0.8268(2), b=0.5977(2), c=1.6292(3)nm;β=100.55(2)°; v=0.7915nm~3; Z=2; d~x=1.319g/cm~3。POEOP分子具有中心对称性,它的两个苯环和两个恶唑环是彼此平行的, 但整个分子却稍有些扭曲成螺旋浆式构型。键长数据表明POEOP分子中苯环与恶唑环以及恶唑环与C'=C双键间均有很大程度共轭。     

A decomposition procedure for the determination of arsenic in marine samples

The use of wet and dry ashing procedures to decompose marine biological tissues and to degrade organoarsenic compounds to inorganic arsenic for analysis by zinc-column arsine generation and atomic-absorption spectrophotometry was investigated. Wet ashing with nitric, sulphuric and perchloric acids (10:2:3 v/v) released the largest percentage of arsenic from fish tissue and quantitatively degraded methylated and other organoarsenic compounds to inorganic arsenic. The arsenic concentrations found when standard reference materials were ashed with this acid mixture were in agreement with the certified values.     

POLYMER-SUPPORTED LEWIS ACID CATALYSTS. Ⅵ. POLYSTYRENE-BONDED STANNIC CHLORIDE CATALYST

A polystyrene-bonded stannic chloride catalyst was synthesized by the method of lithium polystyryl combined with stannic chloride. This catalyst is a polymeric organometallic compound containing 0.25 mmol Sn (Ⅳ)/g catalyst. The catalyst showed sufficient stability and catalytic activity in organic reaction such as esterification, acetalation and ketal formation, and it could be reused many times without losing its catalytic activity.     

酰亚胺及磺酰苯酰亚胺的氰甲基化新方法

二乙胺基乙腈分別与苯邻二酰亚胺、丁二酰亚胺或邻-磺酰苯酰亚胺反应后,可生成相应的N-氰甲基苯邻二酰亚胺、N-氰甲基丁二酰亚胺,N-氰甲基邻磺酰苯酰亚胺及O-氰甲基邻磺酰苯酰亚胺。酰亚胺或磺酰苯酰亚胺的氰甲基化反应活性,随氮负离子的稳定性及其酸性增强而增大。     

Rhodium (II) compounds with functionalized metalated phosphines as bridging ligands

The reaction of Rh₂(O₂CCH₃)₄ · 2CH₃OH with the phosphine P(4-BrC₆H₄)₂(C₆H₅), 2, results in the formation of the monometalated compound Rh₂(O₂CCH₃)₃[PC] · 2CH₃CO₂H (PC representing a metalated P(4-BrC₆H₄)₂(C₆H₅)). The reaction involves selective metalation of the phosphine at one Br-substituted ring (12:1 isomer ratio). The reaction of Rh₂(O₂CCH₃)₃[(4-BrC₆H₃)P(4-BrC₆H₄)(C₆H₅)] · 2CH₃CO₂H, 4, with one additional mol of triphenylphosphine yields a mixture of two main stereoisomers Rh₂(O₂CCH₃)₂[(4-BrC₆H₃)P(4-BrC₆H₄)(C₆H₅)] [(C₆H₄)P(C₆H₅)₂] · 2CH₃CO₂H, 5a and 5b, that were isolated as pure compounds. These two compounds were resolved in the corresponding M and P enantiomers as trifluoroacetate derivatives that show good enantioselectivities in catalytic transformation of α-diazocarbonyl compounds.     

含烯烃配体的过渡金属卡宾配合物的研究 XVIII: 异构化的螺环[4.4]-1,3-壬二烯(二羰基)[乙氧基(芳基)卡宾]铁配合物和螯合烯丙基铁配合物的合成和结构

螺环[4.4]-1,3-壬二烯三羰基铁(1)与芳基锂试剂, ArLi(Ar=C~6H~5, o-,p-CH~3C~6H~4, p-CH~3OC~6H~4, p-ClC~6H~4, p-C~6H~5C~6H~4)在乙醚中于低温下反应, 生成的酰羰基金属盐用Et~3OBF~4在水溶液中于0℃烷基化生成不稳定的异构化的螺环[4.4]-1,3-壬二烯(二羰基)[乙氧基(芳基)卡宾]铁配合物(2-7)。这些配合物与膦在石油醚中于低温下加成反应, 转变为稳定的膦加成物(8-12)。12的结构经单晶X射线结构分析进一步证实。     

New developments in the Pd-catalysed cyclisation-coupling reaction of alkene-containing carbonucleophiles with organic halides (and triflates). The first examples of asymmetric catalysis.

The results of our preliminary investigations directed toward asymmetric catalysis of the cyclocarbopalladation of alkenes bearing a proximate nucleophile with organic halides (or triflates) are disclosed. A series of bidentate phosphine ligands were evaluated in intramolecular versions of this reaction using (E)-2-[7-(2-bromophenyl)-hept-4-enyl]-malonic acid dimethyl ester (1) and (Z)-2-[7-(2-trifluoromethanesulfonyloxy-phenyl)-hept-4-enyl]-malonic acid dimethyl ester (9) as model substrates. The highest enantioselective induction was obtained with aryl triflate 9 which produced the corresponding cyclopentylindane as a single diastereomer in 54% chemical yield and 43% ee by using PdCl₂[S-(−)-TolBINAP] as chiral catalyst and K₂CO₃ as base.     

从炔烃衍生物出发的有机合成方法学

研究了过渡金属催化的炔烃衍生物的异构化反应.从α,β-炔酮、2-炔酸酯和2-炔酸酰胺可以生成相应的(E,E)-共轭双烯酮、双烯酸酯和双烯酸酰胺.首次从2-炔醇异构化为相应的2-烯酮或2-烯醛.这一反应具有简单、高产率和立体选择性的优点.假设反应烯经过连二烯中间体,然后再异构化成产物,这一反应提供了方便而有潜在应用价值的方法以制备天然产物合成时的重要中间体.