Preparation and reactions of [2,2-bis(carbethoxy)propyl]cyclopentadienyldicarbonyliron

Although

, (Fp  η-C₅H₅Fe(CO)₂) (I) is stable and characterizable, the lower homologue FpCH₂CH(CO₂CH₃)₂ (II) is not; this we attribute to a facile elimination reaction resulting from the relatively acidic β-hydrogen of II. Formation of I from Fp^? and XCH₂CE₂CH₃ (X  Br, Cl; E  CO₂CH₂CH₃) and cleavage of its FeC bonds (using H⁺, Br₂, Ce^IV and Hg^II) occur without major amounts of ester group migrations, even though ·CH₂CE₂CH₃ radicals are involved in some of these reactions.     

Synthesis and reactions of 2,2-[60]fullerenoalkanoyl chlorides

2,2-[60]Fullerenoalkanoyl chlorides (1a-d) were easily and securely prepared from the corresponding 2,2-[60]fullerenoalkanoic acids (2a-d) by the reaction with thionyl chloride in an unusual mixed solvent, CH2Cl2/dioxane. The characterization of 1a-d by 1H and 13C NMR, FT-IR, and MALDI-TOF-MASS was conducted for the first time. The 2,2-[60]fullerenoalkanoyl chlorides thus obtained were readily converted to the corresponding amides and esters in moderate to excellent yields by the condensation with amines and alcohols, respectively. Upon applying the condensation, [60]fullerene-biomolecule hybrids were easily prepared.     

Effect of carbinol group placement on complementary reactions of dipyrromethane+bipyrrole species leading to corrole and/or an octaphyrin

Complementary reactions of a dipyrromethanedicarbinol+2,2′-bipyrrole and a 2,2′-bipyrroledicarbinol+a dipyrromethane were investigated to determine the effect of carbinol group placement on the product distribution and on the broader reaction course. Analytical-scale reactions were performed for both reactions to explore the interplay of acid catalyst, acid concentration, and solvent on the yield of corrole and an octaphyrin. The two reaction routes were further compared under representative conditions by assessing acid-catalyzed decomposition of the dicarbinol species affording benzaldehyde (TLC and GC-MS) and by performing time course experiments monitoring macrocycle yield (UV-vis), presence of benzaldehyde (TLC), and oligomer composition (LD-MS). The complementary reactions were generally found to be quite different. Key to this work was the refinement of a method for the acylation of 2,2′-bipyrrole.     

1,3-diallyl-5-[ω-(diphenylphosphino)alkyl] isocyanurates in reactions of complex formation with palladium(ii) dichloride

The reactions of phosphine derivatives of diallyl isocyanurates with palladium(ii) dichloride lead to the formation of complexes, whose structure, composition, and stability depend on the length of the methylene chain between the isocyanurate and diphenylphosphine fragments in the ligand. 1,3-Diallyl-5-[5′-(diphenylphosphino)pentyl and 10′-(diphenyl-phosphino)decyl] isocyanurates with PdCl₂ form monomeric L₂PdCl₂ trans-complexes in which P atoms of the ligands participate in coordination with the metal. 1,3-Diallyl-5-[2′-(diphenylphosphino)ethyl] isocyanurate with PdCl₂ forms a dimeric (LPdCl₂)₂ complex, which decomposes in a solution to the monomer including solvent molecule into the coordination sphere of the metal. The reactions of 1,3-diallyl-5-[4′-(diphenylphosphino)butyl] isocyanurate and 1,3-diallyl-5-[6′-(diphenylphosphino)hexyl] isocyanurate with PdCl₂ give monomeric chelate LPdCl₂ complexes in which one of the allyl groups of the isocyanurate cycle participates in coordination with the central ion along with the phosphorus atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1859–1865, September, 1998.     

Extraction of DDT [1,1,1,-trichloro-2,2-bis(p-chlorophenyl)ethane] and its metabolites DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)-ethylene] and DDD [1,1-dichloro-2,2-bis(p-chlorophenyl)-ethane]) from aged contaminated soil

Pressurised liquid extraction (PLE) was used to extract DDT [1,1,1,-trichloro-2,2-bis(p-chlorophenyl)ethane] and its metabolites, DDD [1,1-dichloro-2,2-bis(p-chlorophenyl)ethane] and DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene] from an aged, contaminated soil. Using three sequential static phases, PLE removed an equivalent quantity of DDT and its metabolites as Soxhlet extraction, in less time and with less solvent. Recovery was almost quantitative, implying appropriate sample work-up and manipulation.     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2''-bpy)3]2[Co(2,2''-bpy)2Cl][Co(2,2''-bpy)2]H2-[SbW18O60]·4H2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9-, formulated [Co(2,2'-bpy)3]2[Co(2,2'-bpy)2Cl][Co(2,2'-bpy)2]H2[SbW18O60]·4H2O (2,2'-bpy= 2,2(-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2'-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9- encapsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoⅡ and low-spin CoⅡ ions coexist in the title compound. Magnetic properties indicate that the compound is antiferromagnetic.     

Radical reactions of tricyclo[4.1.0.02,7]heptane and 1-phenyltricyclo[4.1.0.02,7]heptane with trifluoromethyl (phenylethynyl) sulfone

Russian Journal of Organic Chemistry -     

Synthesis of 4-R-2,2-dimethyl-1,2-dihydrobenzo[f]isoquinolines and (2,2-dimethyl-1,2-dihydrobenzo[f]isoquinolylidene-4)acetic acid derivatives

4-R-2,2-dimethyl-1,2-dihydrobenzo[f]isoquinolines and (2,2-dimethyl-1,2-dihydrobenzo[f]isoquinolylidene-4)acetic acid derivatives have been prepared by Ritter reactions of substituted acetonitriles with 2-methyl-1-(1-naphthyl)propan-2-ol.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 375–376, March, 1992.     

A 2,2′-bis(benzimidazolium)-dibenzo[24]crown[8] rigid pseudorotaxane system

Pseudorotaxanes from the self-assembly of simple 2,2′-bis(benzimidazolium) dications and DB24C8 is a first of its kind when a protonated bis(benzimidazole) without a methylene spacer between the two benzimidazolium units (a very rigid axle without flexibility) thread DB24C8 as a result of H-bonding interactions. The formation of these pseudorotaxanes was first ascertained from ¹H NMR spectroscopy and later corroborated by HRMS, 2D NMR and finally supported by rigorous DFT calculations.     

2,2']Bi[naphtho[2,3-b]furanyl]: a versatile organic semiconductor with a furan-furan junction

[2,2']Bi[naphtho[2,3-b]furanyl] was synthesized, characterized, and examined as an organic semiconductor for thin-film OFETs, bilayer OPVs, and organic light-emitting transistors (OLETs). In the devices, the material acted as a p-type semiconductor, showing moderately high mobility in OFETs, good photo conversion efficiency in OPVs, and blue-green emission in OLETs.     

Magnetic circular dichroism and anomalous fluorescence spectra of [2,2] (2,6)azulenophanes

The electronic absorption spectra of syn-[2,2] (2,6) azulenophane (1) and anti-[2,2] (2,6)azulenophane (2) were investigated via magnetic circular dichroism spectra. The anomalous fluorescence spectra were also observed. From the assignment of the absorption spectra, it was concluded that molecules 1 and 2 emitted the fluorescence from the third excited singlet state.