Synthesis and NMR spectroscopic characterization of Si-substituted 1-silacyclobutene derivatives

Hydroboration of trialkyn-1-yl(organo)silanes with one equivalent and two equivalents of 9-borabicyclo[3.3.1]nonane, 9-BBN afford dialkyn-1-ylsilanes and alkyn-1-ylsilanes, respectively. The alkyn-1-ylsilane derivatives are stable at room temperature and can be store under dry argon for prolong period of time. These compounds are attractive materials for further rearrangements to afford novel 1-silacyclobutene derivatives bearing Si-alkenyl or Si-alkynyl functionalities. The hydroboration reaction is well controlled by the Si-R¹ function, i.e., the starting silanes with R¹ = Ph selectively afford hydroboration of one Si-C≡C bond with one equivalent of 9-BBN, leaving the other two functionalities untouched. Under mild reaction conditions (25°C), the starting silanes with R¹ = Me lead to mixture containing dialkyn-1-ylsilane, alkyn-1-ylsilane and their respective 1-silacyclobutene derivatives. All new compounds are sensitive towards air and moisture and were studied by multinuclear magnetic resonance spectroscopy (¹H, ¹³C, ¹¹B, ²⁹Si NMR) in solution.     

Ketene dithioacetal derivatives of 1-phenyl-3,5-dioxopyrazolidine. Synthesis and NMR characterization

1-Phenyl-3,5-dioxopyrazolidine 1 reacts with carbon disufide and alkyl halides in presence of excess of sodium acetate in dimethylformamide to afford the ketene dithioacetals 3a-h . The ¹³C chemical shift assignments of these compounds were made on the basis of two-dimensional nmr studies performed on the N-methylketene dithioacetal derivative 4.     

Synthesis of stable derivatives of cycloprop-2-ene carboxylic acid

Large-scale syntheses of 3-(cycloprop-2-en-1-oyl)oxazolidinones from acetylene and ethyl diazoacetate are described. Unlike other cyclopropenes that bear a single substitutent at C-3, these compounds are stable to long-term storage. Although the cyclopropene derivatives are unusually stable, they are reactive toward cyclic and acyclic dienes in stereoselective Diels-Alder reactions.     

Synthesis and characterization of bi(metallacycloprop-1-ene) complexes

In all previously reported metallacycloprop-1-ene or η²-vinyl complexes, the metal center bears only one vinyl moiety. We have now successfully synthesized and structurally characterized the first complexes bearing two η²-vinyl moieties or spiro bi(metallacycloprop-1-ene) complexes from reactions of alkynes with rhenium phosphine complexes. Computational studies indicate that the metallacycloprop-1-ene rings are aromatic and the complexes represent a rare σ-type spirometalla-aromatic system.

Well-defined metallacycloprop-1-ene complexes have only previously been isolated with a metal center bearing one vinyl moiety. We have successfully obtained the first examples of structurally characterized spiro bi(metallacycloprop-1-ene) complexes.     

Synthesis,structure and reactivity of amino-benzodifurane derivatives

The reactivity of amino groups of some dialkyl esters of 2,6-diamino-benzo[1,2-b:4,5-b′]difuran-3,7-dicarboxylic acid towards acylic reactants was investigated. The easy and chemoselective obtainment of the N,N′-acetyl- and N,N′-benzoyl-derivatives makes the diamino compounds suitable monomers to prepare polymers with tunable chemo-physical behavior. Two novel polyamides, potentially useful for applications in the field of organic electronics, were synthesized and their properties examined. Single crystal X-ray analysis was performed on some of the prepared compounds, thus obtaining information on the extent of electronic conjugation. The obtainment of an oxazinone derivative by cyclization reaction of an N,N′-benzoyl ester was also described.     

Synthesis, reactivity and biological activity of novel bisbenzofuran-2-yl-methanone derivatives

Preparation of bisbenzofuran-2-yl-methanone (1), the corresponding ketoxime 4, semicarbazone and thiosemicarbazone 3a and 3b, ether derivatives of the ketoximes 5a-j and the alcohol 2 are described. These substances have been prepared in excellent yields. All the synthesized compounds except 5i have been tested against five different microorganisms and some of them were found to be active against some of the species studied.     

Synthesis, characterization and ethylene reactivity of 2-diphenylphosphanylbenzamido nickel complexes

Addition of primary amines to N-[2-(diphenylphosphanyl)benzoyloxy]succinimide affords 2-diphenylphosphanylbenzamides, Ph2PC6H4C(O)NHR (R = C(CH3)3, 3; R = H, 4; R = CH2CH2CH3, 5; R = CH(CH3)2, 6). Addition of NiCl(eta3-CH2C6H5)(PMe3) to the deprotonated potassium salts of the amides and subsequent treatment of two equivalents of B(C6F5)3 to the resulting products furnishes eta3-benzyl zwitterionic nickel(II) complexes, [Ph2PC6H4C(O)NR-kappa2N,P]Ni(eta3-CH2C6H5) (R = C6H5, 9; R = C(CH3)3, 10; R = H, 11; R = CH2CH2CH3, 12; R = CH(CH3)2, 13). Solid structures of 9, 11, 13 and the intermediate eta1-benzyl nickel(II) complexes, [Ph2PC6H4C(O)NR-kappa2N,P]Ni(eta1-CH2C6H5)(PMe3) (R = C6H5, 7; R = C(CH3)3, 8) were determined by X-ray crystallography. When ethylene is added to the eta3-benzyl zwitterionic nickel(II) complexes, butene is obtained by the complexes 9-12 but complex 13 provides very high molecular-weight branched polyethylene (Mw, approximately 1300000) with excellent activity (up to 5200 kg mol-1 h-1 at 100 psi gauge).     

Synthesis and thermal behavior of cis- and trans-1-tert-butyl-4,5-dimethyl-2-phenyl-2-(trimethylsiloxy)-1-(trimethylsilyl)-1-silacyclohex-4-ene

The cothermolysis of benzoyl(tert-butyl)bis(trimethylsilyl)silane with 2,3-dimethylbutadiene in a sealed tube at 140 °C for 24 h afforded cis- and trans-1-tert-butyl-4,5-dimethyl-2-phenyl-2-(trimethylsiloxy)-1-(trimethylsilyl)-1-silacyclohex-4-ene (2 and 3) in a ratio of approximately 1:1 in 66% combined yield. When cis-silacyclohex-4-ene 2 was heated in a sealed tube at 250 °C for 24 h, dyotropic ring contraction took place to give 1-[(tert-butyl)(trimethylsiloxy)(trimethylsilyl)silyl]-3,4-dimethyl-1-phenylcyclopent-3-ene (4), but not trans-2-tert-butyl-4,5-dimethyl-2-phenyl-1-(trimethylsiloxy)-1-(trimethylsilyl)-1-silacyclohex-4-ene (6). The thermolysis of trans-silacyclohex-4-ene 3 under the same conditions, however, afforded two products, 1-silyl-1-phenylcyclopent-3-ene 4 and trans-1-tert-butyl-4,5-dimethyl-2-phenyl-1-(trimethylsiloxy)-2-(trimethylsilyl)-1-silacyclohex-4-ene (5). The theoretical calculations were carried out to characterize the transition states and other local minima, and to evaluate the activation energies for the dyotropic rearrangement of 2 to 4 and 6, and 3 to 4 and 5. The energy barriers between 2 and 4, between 3 and 4, and between 3 and 5 were evaluated to be 188, 191, 192 kJ mol⁻¹, respectively. The energy barrier between 2 and 6, however, was calculated to be 201 kJ mol⁻¹ or higher. These results are consistent with the experimental finding that the thermal isomerization of 2 affords only 4, but 3 produces both 4 and 5.     

Ozonides of perfluorooct-1-ene and perfluorooct-2-ene

Ozonides of higher perfluoroalkenes were prepared for the first time by ozonation of perfluorooct-1-and-2-enes in Freon-113. The structures of the resulting compounds were confirmed by¹³C NMR spectroscopy and GLC-mass spectrometry.     

Analogues of DIOP. Synthesis, reactivity, and NMR behaviour

The (4R,5R)-4,5-Bis(diphenylphosphinomethyl)-2-(-naphthoxy)-1,3,2-dioxaphospholane (1) and (4R,5R)-4,5-bis(diphenylphosphinomethyl)-2-dimethylamino-2-oxo-1,3,2-dioxaphospholane (2), analogues of the chiral bisphosphine ligand DIOP, have been synthesized. Both compounds have a second phosphorus functionality in the backbone of the chiral bisphosphine. That the reactivities of the various phosphorus atoms in 1 are different was shown for the reaction with BH₃. The complexation behaviour of 1 towards Rh^I was studied with the aid of ³¹P NMR spectroscope.     

Synthesis,stereodynamics, and reactivity of isonitrile derivatives of dodecacarbonyltetrairidium

The reaction of Ir₄₍CO)₁₂ with t-BuNC or MeNC in the presence of trimethylamine oxide in refluxing tetrahydrofuran provides the substituted iridium clusters Ir₄(CO)_12-x(RNC)_x] (χ  14; R  t-Bu, Me). The infrared and ¹³C NMR spectra of these molecules indicate that most of them adopt structures related to Ir₄(CO)₁₂, i.e., they have only terminal carbonyl ligands. The variable temperature ¹³C NMR spectra for Ir₄(CO)₁₁(t-BuNC) establish a carbonyl scrambling process which is the formal inverse of the C_3v→ T_d scrambling mechanism proposed for Rh₄(CO)₁₂. The kinetics of substitution of Ir₄(CO)₁₂ by t-BuNC have been studied. Each substitution step occurs by a ligand-dependent, overall second-order reaction at a rate much greater than for substitution by PPh₃. The observed differences between t-BuNC and PPh₃, can be rationalized on the basis of steric differences between the two ligands.     

Synthesis of 2-methylidene-1-silacyclohexanes from 2,6-dibromohex-1-ene and polyhalosilanes

Various 2-methylidene-1-silacyclohexanes were prepared by straightforward syntheses from readily available polychloro- or polyfluorosilanes, magnesium and 2,6-dibromohex-1-ene using Barbier-type conditions or a previously synthesized Grignard reagent. Good yields were obtained considering the low stability of the products in the reaction conditions.     

Synthesis,molecular structure and reactivity of new biferrocenylpropane derivatives

New biferrocenylpropane derivatives FcC(CH₃)₂Fc′-C≡C–R [Fc?=?C₅H₅FeC₅H₄; Fc′?=?C₅H₅FeC₅H₃, R?=?C₆H₅ (L ₁ ), Fc (L ₂ )] and their complexes [FcC(CH₃)₂Fc′-C≡C–R][Co₂(CO)₆] [R?=?C₆H₅ (1); R?=?Fc (2)] have been synthesized by the Castro-Stephens coupling reaction and the reactions of ligands L ₁ , L ₂ with Co₂(CO)₈. Compounds L ₁ , L ₂ , 1 and 2 were characterized by elemental analysis, IR, ¹H (¹³C) NMR and MS, and the molecular structures of ligands L ₁ , L ₂ were determined by X-ray single crystal analysis. The electrochemical properties of L ₁ , L ₂ , 1 and 2 demonstrate two or three resolved one-electron redox processes.     

Synthesis and characterization of bispyrrolidine derivatives of H2@C60: differentiation of isomers using 1H NMR spectroscopy of endohedral H2

Bisadduct isomers of a H(2)@C(60) derivative with nitroxide addends have been synthesized, isolated and characterized. The (1)H NMRs of endohedral H(2) of the major isomers show well-separated chemical shifts, which could be useful for structural assignment and identification of the purity of the C(60) bisadduct isomers.     

Synthesis,structure, and reactivity of germanium-containing derivatives of substituted diethanolamines

The reaction of dialkanolamines RN(CH₂CH₂O)(CHR’CHR’OH) (R = Me, Ph, PhCH₂; R’ = H, Ph) with tetraethoxygermane gives either 2,2-diethoxy-1,3,6,2-dioxazagermocanes RN(CH₂CH₂O)(CHR’CHR’O)Ge(OEt)₂ or 1,7,9,15-tetraoxa-4,12-diaza-8-germaspiro[7.7]pentadecanes [RN(CH₂CH₂O) (CHR’CHR’O)]₂Ge depending on the reactant ratio. The chemical behavior of the obtained compounds in substitution reactions at germanium was studied. The product structure was confirmed by elemental analysis data and ¹H, ¹³C, and ¹⁹F NMR spectroscopy. The cyclotrigermanoxane [MeN(CH₂CH₂O)₂GeO]₃ was studied by X-ray diffraction.     

2-氨基-6-三氟甲基嘧啶衍生物的合成及表征

近几年,含嘧啶结构单元的高效低毒农药层出不穷,如用作杀菌剂的嘧啶胺类、嘧啶腺类及嘧啶丙烯酸酯类,除草剂有嘧啶磺酰脲类、嘧啶水杨酸类、酰基(硫)脲类及三唑并嘧啶磺酰脲类。将含氟基团引入杂环结构是新药创制的一个发展方向,     

Synthesis and NMR spectroscopic assignment of chlorinated benzimidazole-2-thione derivatives

The benzimidazole-2-thione scaffold is present in many drugs encompassing various therapeutic areas. Due to the broad spectrum of bioactivities it also represents an important starting point in drug discovery campaigns, especially those based on fragment-based design. Despite simple structures the tautomerism and regioisomerism of substituted benzimidazole-2-thiones makes unambiguous structural analysis difficult. Tautomeric duplicates are present in commercial libraries resulting in two tautomers being sold as different products. To showcase an example of appropriate structural determination, we synthesized and characterized a set of benzimidazole-2-thiones with different positions of a chlorine atom on the ring. Using NOESY and ¹³C NMR spectroscopy, we determined that the thione tautomer predominates in the thione-thiol equilibrium. Furthermore, NOESY and HMBC experiments confirmed the position of the substituents on the benzimidazole-2-thione ring.