1,3-双(氯硅烷基)丙烷与活泼金属作用的偶联环化产物的研究

1,3-双(烃基氯硅烷基)丙烷Cl_(3-m)R_mSi(CH_2)_3SiR’_nCl_(3-n)的合成及其与水、氨(胺)、硫化氢的反应已有较详尽的报道,但与活泼金属作用的偶联环化反应则涉及较少。我们分别以钾-钠合金、金属锂对1,3-双(二烃基氯硅烷基)丙烷进行偶联环化,合成了五个新的非对称1,1,2-三甲基-2-烃基-1,2-二硅杂环戊烷类化合物(1a～     

Dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II): an effective catalyst for cross-coupling reaction of a secondary alkyl grignard reagent with organic halides

Dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) was found to be an effective catalyst for the cross-coupling reaction of sec-butylmagnesium chloride with bromobenzene, β-bromostyrene, and 2-bromopropene to give the corresponding sec-butyl derivatives in exceedingly high yields.     

Synergistic extraction of europium and americium into nitrobenzene by using hydrogen dicarbollylcobaltate and 1,3-bis(diphenylphosphino)propane dioxide

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B^?) in the presence of 1,3-bis(diphenylphosphino)propane dioxide (DPPPrDO, L) has been investigated. The equilibrium data have been explained assuming that the species $ {\text{HL}}^{ + } ,\,{\text{HL}}_{2}^{ + } ,\,{\text{ML}}^{3 + } \,{\text{and}}\,{\text{ML}}_{3}^{3 + } $ HL + , HL 2 + , ML 3 + and ML 3 3 + (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the complex species in nitrobenzene saturated with water have been determined. It was found that the stability constants of the corresponding complexes $ {\text{EuL}}_{n}^{ 3+ } \,{\text{and}}\,{\text{AmL}}_{n}^{ 3+ } , $ EuL n 3 + and AmL n 3 + , where n = 1, 3 and L is DPPPrDO, in water-saturated nitrobenzene are comparable.     

The crystal and molecular structure of [BPh4]{Ru(NO)[1,3-bis(diphenylphosphine)propane]2}

Summary The crystal structure of [BPh₄][Ru(NO)(DPP)₂] [DPP = 1,3-bis(diphenyIphosphine)propane ] has been determined by Patterson and Fourier methods using diffractometer data. Crystals are monoclinic, space group P21 /c, with a = 19.546(3), b = 19.139(3), c = 17.796(3) Å and = 98.04(5)°; Dc = 1.29 for Z = 4. The structure has been refined to R = 7.2% by least squares methods. The environment around the ruthenium atom is trigonal bipyramidal with two axial phosphorus atoms and two more phosphorus atoms and the nitrogen atom of the nitrosyl group in the equatorial plane. The Ru-P bond distances are chemically equivalent with a mean value of 2.39 A, and the Ru-N bond length is 1.72(2) A.     

Polymer-supported palladium perfluorooctanesulfonate [Pd(OPf)2]: A recyclable and ligand-free palladium catalyst for copper-free Sonogashira coupling reaction in water under aerobic conditions

Amberlyst A-21, a kind of well-known and cheap polymeric material, was treated with palladium perfluorooctanesulfonate [Pd(OPf)₂] giving a reagent with a palladium loading of 1.94 (wt%). The polymer-supported fluorous palladium catalyzes the highly efficient Sonogashira coupling reaction in water. The reactions can be performed under copper- and ligand-free conditions in an air atmosphere. The palladium catalyst is easily separated and can be reused several times without a significant loss of catalytic activity.     

Chelation control in the [3+3] annulation reaction of alkoxy-substituted 1,1-diacylcyclopropanes with 1,3-bis(trimethylsilyloxy)-1,3-butadienes

Functionalized arenes were prepared by chelation-controlled ‘[3+3] cyclization/homo-Michael’ reactions of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with benzyloxy- or methoxy-substituted 1,1-diacylcyclopropanes.     

Synthesis of aromatic polyethers by Scholl reaction. VII. Oxidative polymerization of 2,2-bis[4-(1-naphthoxy)phenyl]propane and 2,2-bis [4-(1-naphthyl)phenyl]propane

The synthesis and the mechanism of oxidative polymerization of 2,2-bis[4-(1-naphthoxy)phenyl]propane ( 4 ) and 2,2-bis[4-(1-naphthyl)phenyl]propane ( 9 ) are presented. Both monomers polymerize by two different propagation steps. The first one represents a cation-radical dimerization of the naphthyl groups to dinaphthyl structure. H⁺[FeCl₄]^? generated from the first propagation step initiates a transalkylation reaction which provides structural units containing isopropylidenic groups inserted between phenyl and naphthyl, and between two naphthyl groups, respectively. Since the phenyl groups resulted from the second propagation reaction are unreactive in both the oxidative coupling and the transalkylation steps this polymerization reaction leads to polymers with low molecular weights containing phenyl chain ends.