Synthesis and matrix isolated photolysis of 2,3-dimethylbicyclo [2.2.0]hexa-2,5-diene-1,4-dicarboxylic acid anhydride: a potential percursor to 2,3-dimethyl-1,4-dehydrobenzene

The synthesis of the first member of a new class of Dewar benzenes has been achieved. The synthesis of 2,3- dimethylbicyclo[2.2.0]hexa-2,5-diene-1, 4-dicarboxylic acid and its anhydride are described. Dibromomaleic anhydride and dichloroethylene were found to add efficiently in a photochemical [2+2] cycloaddition to produce 1,2-dibromo- 3,4-dichlorocyclobutane-1,2-dicarboxylic acid. Removal of the bromines with tin/copper couple yielded dichloro- cyclobutenes which added to 2-butyne under photochemical conditions to yield 5,6-dichloro-2,3-dimethylbicyclo [2.2.0] hex-2-ene dicarboxylic acids. One of the three possible isomers yielded a stable anhydride which could be dechlorinated using triphenyltin radicals generated by the photolysis of hexaphenylditin.

Photolysis of argon matrix isolated 2,3-dimethylbicyclo [2.2.0]hexa-2, 5-diene-1,4-dicarboxylic acid anhydride produced traces whose strongest bands in the infrared were at 3350 and 600 cm^(-1). This suggested the formation of terminal acetylenes. The spectra of argon matrix isolated E- and Z- 3,4-dimethylhexa-1,5-diyne-3-ene and cis-and trans-octa- 2,6-diyne-4-ene were compared with the spectrum of the photolysis products. Possibly all four diethynylethylenes were present in the anhydride photolysis products. Gas chromatograph-mass spectral analysis of the volatiles from the anhydride photolysis again suggested, but did not confirm, the presence of the diethynylethylenes.

Photosensitized CIS-TRANS isomerization of 2,3-diphenylbutene-2 investigation of anomalous sensitizers for substituted Stilbene isometrization

The behavior of the photosensitized cis-trans isomerization of 2,3-diphenylbutene-2 was studied as a function of sensitizer energy by previously established methods. In addition, certain sensitizers for which parameters other than energy transfer are operative in inducting isomerizations, were studied in more detail. Sensitization of various stilbenes and substituted stilbenes by triphenylene is discussed in terms of excited state complex formation with stilbene. Sensitization by quinones, halogen-containing aromatics and 1,2-diketones is discussed in terms of attack by photolytically produced free radicals, either by addition to and elimination from the double bond, or in the cases of 1,2-diphenylpropene and 2,3-diphenylbutene-2, by hydrogen abstraction from one of the methyl groups and reversible abstraction by the allylic radical to produce cis-trans isomerized substrate and the structurally isomerized products, 2,3-diphenylpropene and 2,3-diphenylbutene-1.

2,4-dimethylene-1,3-cyclobutanediyl and 2,4-dimethylenebicyclobutane. Synthesis, spectroscopy, and reactivity of a triplet biradical and its covalent isomer

The preparation and direct observation of triplet 2,4-dimethylene-1,3- cyclobutanediyl (1), the non-Kekule isomer of benzene, is described. The biradical was generated by photolysis of 5,6-dimethylene-2,3- diazabicyclo[2.1.1]hex-2-ene (2) (which was synthesized in several steps from benzvalene) under cryogenic, matrix-isolation conditions. Biradical 1 was characterized by EPR spectroscopy (‌‌‌‌‌│D/hc│ =0.0204 cm^(-1), │E/hc│ =0.0028 cm^(-1)) and found to have a triplet ground state. The Δm_s= 2 transition displays hyperfine splitting attributed to a 7.3-G coupling to the ring methine and a 5.9-G coupling to the exocyclic methylene protons. Several experiments, including application of the magnetophotoselection (mps) technique in the generation of biradical 1, have allowed a determination of the zero-field triplet sublevels as x = -0.0040, y = +0.0136, and z = -0.0096 cm^(-1), where x and y are respectively the long and short in-plane axes and z the out-of-plane axis of 1.

Triplet 1 is yellow-orange and displays highly structured absorption (λ_(max)= 506 nm) and fluorescence (λ_(max) = 510 nm) spectra, with vibronic spacings of 1520 and 620 cm^(-1) for absorption and 1570 and 620 cm^(-1) for emission. The spectra were unequivocally assigned to triplet 1 by the use of a novel technique that takes advantage of the biradical's photolability. The absorption є = 7200 M^(-1) cm^(-1) and f = 0.022, establishing that the transition is spin-allowed. Further use of the mps technique has demonstrated that the transition is x-polarized, and the excited state 1s therefore of B_(1g) symmetry, in accord with theoretical predictions.

Thermolysis or direct photolysis of diazene 2 in fluid solution produces 2,4- dimethylenebicyclo[l.l.0]butane (3), whose ^(l)H NMR spectrum (-80°C, CD_(2)Cl_(2)) consists of singlets at δ 4.22 and 3.18 in a 2:1 ratio. Compound 3 is thermally unstable and dimerizes with second-order kinetics between -80 and -25°C (∆H^(‡) = 6.8 kcal mol^(-1), (∆s^(‡) = -28 eu) by a mechanism involving direct combination of two molecules of 3 in the rate-determining step. This singlet-manifold reaction ultimately produces a mixture of two dimers, 3,8,9- trimethylenetricyclo[5.1.1.0^(2,5)]non-4-ene (75) and trans-3,10-dimethylenetricyclo[6.2.0.0^(2,5)]deca-4,8-diene (76t), with the former predominating. In contrast, triplet-sensitized photolysis of 2, which leads to triplet 1, provides, in addition to 75 and 76t, a substantial amount of trans-5,10- dimethylenetricyclo[6.2.0.0^(3,6)]deca-3,8-diene (77t) and small amounts of two unidentified dimers.

In addition, triplet biradical 1 ring-closes to 3 in rigid media both thermally (77-140 K) and photochemically. In solution 3 forms triplet 1 upon energy transfer from sensitizers having relatively low triplet energies. The implications of the thermal chemistry for the energy surfaces of the system are discussed.

Measurement of the galactic cosmic ray antiproton flux from 0.25 gev to 3.11 gev with the isotope matter antimatter experiment (imax)

The intensities and relative abundances of galactic cosmic ray protons and antiprotons have been measured with the Isotope Matter Antimatter Experiment (IMAX), a balloon-borne magnet spectrometer. The IMAX payload had a successful flight from Lynn Lake, Manitoba, Canada on July 16, 1992. Particles detected by IMAX were identified by mass and charge via the Cherenkov-Rigidity and TOP-Rigidity techniques, with measured rms mass resolution ≤0.2 amu for Z=1 particles.

Cosmic ray antiprotons are of interest because they can be produced by the interactions of high energy protons and heavier nuclei with the interstellar medium as well as by more exotic sources. Previous cosmic ray antiproton experiments have reported an excess of antiprotons over that expected solely from cosmic ray interactions.

Analysis of the flight data has yielded 124405 protons and 3 antiprotons in the energy range 0.19-0.97 GeV at the instrument, 140617 protons and 8 antiprotons in the energy range 0.97-2.58 GeV, and 22524 protons and 5 antiprotons in the energy range 2.58-3.08 GeV. These measurements are a statistical improvement over previous antiproton measurements, and they demonstrate improved separation of antiprotons from the more abundant fluxes of protons, electrons, and other cosmic ray species.

When these results are corrected for instrumental and atmospheric background and losses, the ratios at the top of the atmosphere are p/p=3.21(+3.49, -1.97)x10^(-5) in the energy range 0.25-1.00 GeV, p/p=5.38(+3.48, -2.45) x10^(-5) in the energy range 1.00-2.61 GeV, and p/p=2.05(+1.79, -1.15) x10^(-4) in the energy range 2.61-3.11 GeV. The corresponding antiproton intensities, also corrected to the top of the atmosphere, are 2.3(+2.5, -1.4) x10^(-2) (m^2 s sr GeV)^(-1), 2.1(+1.4, -1.0) x10^(-2) (m^2 s sr GeV)^(-1), and 4.3(+3.7, -2.4) x10^(-2) (m^2 s sr GeV)^(-1) for the same energy ranges.

The IMAX antiproton fluxes and antiproton/proton ratios are compared with recent Standard Leaky Box Model (SLBM) calculations of the cosmic ray antiproton abundance. According to this model, cosmic ray antiprotons are secondary cosmic rays arising solely from the interaction of high energy cosmic rays with the interstellar medium. The effects of solar modulation of protons and antiprotons are also calculated, showing that the antiproton/proton ratio can vary by as much as an order of magnitude over the solar cycle. When solar modulation is taken into account, the IMAX antiproton measurements are found to be consistent with the most recent calculations of the SLBM. No evidence is found in the IMAX data for excess antiprotons arising from the decay of galactic dark matter, which had been suggested as an interpretation of earlier measurements. Furthermore, the consistency of the current results with the SLBM calculations suggests that the mean antiproton lifetime is at least as large as the cosmic ray storage time in the galaxy (~10^7 yr, based on measurements of cosmic ray ^(10)Be). Recent measurements by two other experiments are consistent with this interpretation of the IMAX antiproton results.