Structural and mechanistic study of monoalkyl diazenes. Synthesis, characterization, and reactivity of 1,6-didehydro[10]annulene

Methodology for the preparation of allenes from propargylic hydrazine precursors under mild conditions is described. Oxidation of the propargylic hydrazines, which can be readily prepared from propargylic alcohols, with either of two azo oxidants, diethyl azodicarboxylate (DEAD) or 4-methyl 1,2-triazoline-3,5-dione (MTAD), effects conversion to the allenes, presumably via sigmatropic rearrangement of a monoalkyl diazene intermediate. This rearrangement is demonstrated to proceed with essentially complete stereospecificity. The application of this methodology to the preparation of other allenes, including two that are notable for their reactivity and thermal instability, is also described.

The structural and mechanistic study of a monoalkyl diazene intermediate in the oxidative transformation of propargylic hydrazines to allenes is described. The use of long-range heteronuclear NMR coupling constants for assigning monoalkyl diazene stereochemistry (E vs Z) is also discussed. Evidence is presented that all known monoalkyl diazenes are the E isomers, and the erroneous assignment of stereochemistry in the previous report of the preparation of (Z)-phenyldiazene is discussed.

The synthesis, characterization, and reactivity of 1,6-didehydro[10]annulene are described. This molecule has been recognized as an interesting synthetic target for over 40 years and represents the intersection of two sets of extensively studied molecules: nonbenzenoid aromatic compounds and molecules containing sterically compressed π-systems.The formation of 1,5-dehydronaphthalene from 1 ,6-didehydro[10]annulene is believed to be the prototype for cycloaromatizations that produce 1,4-dehydroaromatic species with the radical centers disposed anti about the newly formed single bond. The aromaticity of this annulene and the facility of its cycloaromatization are also analyzed.

Observations of 1-6 MeV Jovian electrons at 1 AU and a study of their propagation

The 1-6 MeV electron flux at 1 AU has been measured for the time period October 1972 to December 1977 by the Caltech Electron/Isotope Spectrometers on the IMP-7 and IMP-8 satellites. The non-solar interplanetary electron flux reported here covered parts of five synodic periods. The 88 Jovian increases identified in these five synodic periods were classified by their time profiles. The fall time profiles were consistent with an exponential fall with τ ≈ 4-9 days. The rise time profiles displayed a systematic variation over the synodic period. Exponential rise time profiles with τ ≈ 1-3 days tended to occur in the time period before nominal connection, diffusive profiles predicted by the convection-diffusion model around nominal connection, and abrupt profiles after nominal connection.

The times of enhancements in the magnetic field, │B│, at 1 AU showed a better correlation than corotating interaction regions (CIR's) with Jovian increases and other changes in the electron flux at 1 AU, suggesting that │B│ enhancements indicate the times that barriers to electron propagation pass Earth. Time sequences of the increases and decreases in the electron flux at 1 AU were qualitatively modeled by using the times that CIR's passed Jupiter and the times that │B│ enhancements passed Earth.

The electron data observed at 1 AU were modeled by using a convection-diffusion model of Jovian electron propagation. The synodic envelope formed by the maxima of the Jovian increases was modeled by the envelope formed by the predicted intensities at a time less than that needed to reach equilibrium. Even though the envelope shape calculated in this way was similar to the observed envelope, the required diffusion coefficients were not consistent with a diffusive process.

Three Jovian electron increases at 1 AU for the 1974 synodic period were fit with rise time profiles calculated from the convection-diffusion model. For the fits without an ambient electron background flux, the values for the diffusion coefficients that were consistent with the data were k_x = 1.0 - 2.5 x 10²¹ cm²/sec and k_y = 1.6 - 2.0 x 10²² cm²/sec. For the fits that included the ambient electron background flux, the values for the diffusion coefficients that were consistent with the data were k_x = 0.4 - 1.0 x 10²¹ cm²/sec and k_y = 0.8 - 1.3 x 10²² cm²/sec.