Peracid-mediated n-oxidation and rearrangement of dimethylphosphoramides: plausible model for oxidative bioactivation of the carcinogen hexamethylphosphoramide (HMPA)

Dimethylphosphoramides react with $\text{m}$-chloroperoxybenzoic acid (MCPBA) in anhydrous acetone to yield the previously unknown $\text{P}$-dimdethylamino-oxyphosphonous derivatives $\text{via}$$\text{N}$-oxidation and rearrangement. Further MCPBA oxidation yields formaldehyde and nitrosomethane, isolated as its $\text{trans}$-dimer. These reactions provide a possible biomimetic model for the metabolic activation of hexamethylphosphoramide as a mutagen and carcinogen.     

Arylation with aryllead triacetates produced in situ by mercury-lead exchange

Reaction of a diarylmercury with lead tetraacetate to give an aryllead triacetate has been found to be a rapid reaction. The in situ generation of aryllead triacetates is thus an attractive alternative to the use of the purified reagents in the various electrophilic arylation reactions of these compounds.     

Hydrozirconation/oxidation of internal olefins a simple synthesis of triacontanol

Hydrozirconation of internal olefins followed by oxidation with anhydrous t-butyl hydroperoxide generates primary alcohols in good yields and high purity.     

Photorearrangement of photocycloadducts from arenes and 1,3-cyclohexadiene

The 4π_s+π_s photoadduct from an arene and 1,3-cyclohexadiene may undergo a photochemical rearrangement to the 4π_s+π_s adduct.     

The anhydride structure of several previously reported stable areneselenenic acids1

The compounds previously reported² to be the stable areneselenenic acids, $\text{o}$-nitro-($\text{la}$ and $\text{+o}$-benzoylbenzeneselenenic acid ($\text{lb}$), are shown actually to be the corresponding selenenic anhydrides (ArSeOSeAr). Solutions of the selenenic acids (ArSeOH), however, can be easily generated from the anhydrides byacid-catalyzed hydrolysis.     

New Possible Applications of Heavy Main-Group Elements in Organic Synthesis

Aside from elements of the 2nd row, and one element of the 3rd row of the periodic system—Si, P, S, and Se, respectively, whose organoelement groups such as Me₃Si and Ph₃P^⊕ have proven useful in numerous organic syntheses—other elements of the 3rd as well as 4th and 5th row (Ge, As, Sn, Sb, Te, Pb, Bi) can also be used as components of synthetically useful organoelement groups, the elements As, Sn, and Pb, in particular, offering certain advntages over the others. Some of these organoelement groups are suitable equivalents for Li- or halogen-substituents attached to carbon; they stabilize carbanionic centers (minimum of this effect at the 3rd-row elements), and owing to their suitability as leaving groups in β-eliminations, also open up interesting synthetic possibilities. The thermally unduced syn- and silica-gel induced anti-elimination of Ph₃Sn, Ph₂Sb, Ph₃Pb, together with β-OH, are novel. With the newly synthesized compounds Ph_nEl—Ch₂—Li (El = Sn, Pb, As, Sb, Bi) and other α- and β-lithiated R_nEl- and Ph₂As(O)-reagents such organoelement groups can be introduced into organic compounds and exploited in organic and organoelement synthesis.     

Dimetallic Complexes with Bridging Seven-membered Cycloolefins. Synthesis,Multinuclear NMR.-Spectroscopic Properties and Structure

The synthesis of dimetallic olefin complexes of the type L¹M¹C₇H₇M²L² (M¹ = Fe, Co, Rh; M² = Rh, Ir, Pd; L¹ = CO, C₅H₅; L² = diene, allyl, P(OR)₃) is described. The fluxional structures were investigated by ¹³C-, ⁵⁷Fe- and ¹⁰³Rh-NMR.-spectroscopy, and a cisoid dimetallic coordination, including a (metal, metal)-bond, can be deduced for the C₇H₇-ring. ⁵⁷Fe- and ¹⁰³Rh-chemical shifts give indications for the charge distribution in the 34e-complexes. The homodimetallic complex (Cp)Rh(tropone)Rh(Cp) ( 13 , Cp = cyclopentadienyl) and the corresponding 2-methoxytropone complex 14 were synthesized in addition to the above mentioned complexes. A fluxional bis(1-3-η-allyl)-coordination of the two Rh-atoms was derived from the temperature-dependent ¹³C-NMR.-spectra. A spin simulation of the (Cp)-multiplets of 12 and 13 yields information about (Rh, Rh)-spin-coupling which amounts to ≈5 Hz at 30°.     

The Conformation of 1,6-Diaza-2,7-cyclodecadione in Solution

From ¹H- and ¹³C-NMR. data, a crown conformation with trans amide bonds is deduced for 1,6-diaza-2,7-cyclodecadione ( 1 ) in solution. Compound 1 was obtained by reaction of 2-pyrrolidone with POCl₃.     

Eu(O2C-C≡C-CO2): An EuII Containing Anhydrous Coordination Polymer with High Stability and Negative Thermal Expansion

Anhydrous Eu^II–acetylenedicarboxylate (EuADC; ADC²⁻ = ⁻O₂C-C≡C-CO₂⁻) was synthesized by reaction of EuBr₂ with K₂ADC or H₂ADC in degassed water under oxygen-free conditions. EuADC crystallizes in the SrADC type structure (I4₁/amd, Z=4) forming a 3D coordination polymer with a diamond-like arrangement of Eu²⁺ nodes (msw topology including the connecting ADC²⁻ linkers). Deep orange coloured EuADC is stable in air and starts decomposing upon heating in an argon atmosphere only at 440 °C. Measurements of the magnetic susceptibilities (μ_eff=7.76 μ_B) and ¹⁵¹Eu Mössbauer spectra (δ=−13.25 mm s⁻¹ at 78 K) confirm the existence of Eu²⁺ cations. Diffuse reflectance spectra indicate a direct optical band gap of E_g=2.64 eV (470 nm), which is in accordance with the orange colour of the material. Surprisingly, EuADC does not show any photoluminescence under irradiation with UV light of different wavelengths. Similar to SrADC, EuADC exhibits a negative thermal volume expansion below room temperature with a volume expansion coefficient α_V=−9.4(12)×10⁻⁶ K⁻¹.