Über Darstellung und Reaktivität von 2,4-Diazabicyclo[3.3.1]nonan-3-onen

The 2-cyclohexenones1 a andd resp. react with urea in HCl/EtOH to give 1-hydroxy-4-methyl-7-phenyl- and 1-hydroxy-2,4-diazabicyclo[3.3.1]nonane-3-ones3a and3d resp., whereas the 2-cyclohexenones1b andc resp. transformed by urea to 1,7-dimethyl- and 1-methyl-4-ureido-2,4-diazabicyclo[3.3.1]nonan-3-ones9b andc resp. In the condensation of isophorone1e with urea a product C₁₃H₂₈N₈O₄ of indisdinct structure was formed, whereas the bicyclus3e could not be isolated.Reaction ofAcOAc with3a yielded the 5-methyl-3-oxo-7-phenyl-2,4-diazabicyclo[3.3.1]non-1-ylacetate (15); on heating of3a with acids decomposition to1a and urea took place. NoWagner-Meerwein-rearrangement was observed. The MS-spectra of3a andd are discussed; NMR- and IR-data are reported.No significant herbicidal, fungicidal or insecticidal activity was found in screening-tests on3a.

     

Zur kenntnis von [O2]+[Mn2F9]−

[O₂]⁺[Mn₂F₉]^? has been prepared for the first time by reaction of MnO₂ or MnF_x (x = 2,3,4) with a mixture of fluorine and oxygen (P_F2/O₂ ≈ 300–3500 atm., t ≈ 350–550°C) either as a dark red powder or as ruby red needles or plates. From single crystal studies the space group is C2/c - C⁶_2h (No. 15) with a = 17.55₂, b = 8.37₃, c = 9.10₁ Å, β = 102.3°, Z = B (at ?150°C). The crystal structure has been refined to R = 0.053 (1619 unique reflections). From the structure determination [O₂]+[Mn₂F₉] has ‘mänder’ like bands of double chains of [MnF₆] octahedra, which are stacked up in layers parallel to (100) with O₂⁺-cations (d_0?0 = 1.10₀ Å) located between the layers. ν_O2 is at 1838 cm^?1 and the magnetic moment μ_eff = 5.63 B.M. is as expected for a ‘spin only’ case without spin-spin interaction.     

Dihydrodiazepine aus valenzisomeren diazatricyclo[3.2.0.0.2,4]Heptanen1)

Cycloaddition of diazoalkanes to diazabicyclo[2.2.0]hexenes and subsequent extrusion of nitrogen afford diazatricyclo[3.2.0.0^2,4]heptanes that are easily valence isomerized to novel dihydrodiazepines.     

Mechanism of the thermal conversion of tetracyclo[3.3.0.02,4.0.3,6]oct-7-ene into dihydropentalenes

One of a number of possible mechanisms has been established for the title reaction.     

Zur kenntnis von [O2]22+[Ti7F30]2−

[O₂]²⁺₂[Ti₇F₃₀]^2? has been obtained by reaction of TiO₂ with a mixture of fluorine and oxygen (p_F2/O2 ≈ 300–3500 atm., t ≈ 300–450°C) either as colourless powder or in form of colourless, clear needles. From single crystal studies the spacegroup is P$\text{3}$ - C_3i¹ (No. 147) with a = 10.19₂, c = 6.50_o Å, Z = 1. The crystal structure has been refined to R = 0.086 [R_w = 0.058] (748 unique reflexions [F_o > 2σ(F_o)]). From the structure determination [O₂]²⁺₂[Ti₇F₃₀]^2? has isolated columns of partially distorted [TiF₆] octahedra (- column structure) which are connected only quite loosely by (disordered) O₂⁺ cations. ν_O2+ is at 1857 cm^?1, the magnetic moment μ_eff = 2.35 B.M. (295 K) is quite as expected for a ‘spin-only’ case.     

Some chemistry of 6,7-benzotricyclo[3.3.1.02,8]-nona-3,6-dien-9-one (benzobarbaralone)

Some reactions of benzobarbaralone 3 have been studied. Ring expansion occurs in reaction of 3 with diazomethane-lithium chloride to yield benzobullvalone 5 and the spirooxirane 6. The tosylhydrazone of 5 was converted to the fluxional benzobullvalene 9. Decarbonylation of 3 to benzocyclooactatetraene occurs upon irradiation. On reaction with Fe₂CO)₉, 3 gives a σ-π allyl tricarbonyliron complex, 11, with rearranged skeleton.     

Stereoelectronic effects on cyclobutyl participation. The 10-tetracyclo[5.2.1.02,6.O3,9]decyl cation

While the solvolysis of tosylate 5c proceeds very rapidly to generate 4 or its rapidly equilibrating classical alternative, the epimeric compound 6c proved to be unreactive; bond orientation effects are implicated.     

An INDO-LMO and 13C NMR spectroscopic study of the C-H bonds in tetracyclo[3.2.0.02,7.04,6]heptane (quadricyclane) and tricyclo[3.1.0.02,4]hexane

Using an INDO approximation to Von Niessen's charge density localization method, the percent s character of the C atom hybrid orbitals engaged in C-H bonds is computed for a series of open-chain and cyclic saturated and unsaturated hydrocarbons. A semi-empirical linear relationship is found between these quantities and the experimental nuclear spin-spin coupling constants J_CH (standard deviation 4·98 Hz). The experimental values of J_CH were measured for quadricyclane (1) and tricyclo[3.1.0.0^2,4]hexane (2) and were shown to be in fair agreement with the theoretical predictions. An analogous relationship is also established between the percent s character of the involved C atom hybrid orbital and the C-H bond distance, the standard deviation being 0·0040Å. This relation is used in order to predict the different C-H bond lengths in the vibrational ground state of 1 and 2, for which equal CH distances were assumed in the analysis of electron diffraction experiments. The results indicate that molecular geometries can be refined with the use of semi-empirical correlations of the above mentioned type.