Mn(III)-based reaction of alkenes with quinolinones. Formation of peroxyquinolinones and quinoline-related derivatives

The reactions of 1,1-disubstituted alkenes with 4-hydroxyquinolin-2(1H)-ones under both Mn(III)-catalyzed aerobic oxidation conditions at room temperature and Mn(III)-mediated oxidation conditions at reflux temperature are described. The Mn(III)-catalyzed aerobic oxidation afforded bis(hydroperoxyethyl)quinolinones and azatrioxa[4.4.3]propellanes, while the oxidation with Mn(OAc)₃·2H₂O produced furo[3,2-c]quinolin-4-one analogues. The existence of a substituent at the 3-position of the 4-hydroxyquinolin-2(1H)-ones prevented a double reaction with the alkenes, and (endoperoxy)quinolinones and/or (hydroperoxyethyl)quinolinones were obtained under the Mn(III)-catalyzed aerobic conditions, while furo[3,2-c]quinolinone hemiacetals and vinylquinolinones were selectively produced under the Mn(III)-mediated oxidation conditions depending on the reaction temperature and times. Cyclic assembly of quinolinone-related 1,3-dicarbonyl compounds such as dihydropyridinones, pyranones, and dimedone derivatives was also examined under elevated temperature conditions.     

Comment on application of statistical multi-step direct emission theory to a neutron-emitting reaction

The statistical multi-step direct emission theory formulated by Feshbach, Kerman and Koonin (FKK) was applied to the analysis of 14 MeV (n, n') scattering on ⁹³Nb and Ag. It is concluded that the FKK theory as it stands disagrees with experimental data, because of anomalously large multi-step cross sections due to the resonance-like behaviour of non-DWBA matrix elements which are entered in the calculation.     

Energy levels of92Nb from 92Zr(p,nγ)92Nb

The energy levels of⁹²Nb were studied by means of the⁹²Zr(p, nγ) reaction. The deexcitation γ-rays were observed with a high-resolution Ge(Li) detector in the proton energy range 3.00–4.80 MeV in steps of about 25 keV. Many new excited states of ⁹²Nb were populated by this reaction. Excitation energies up to 1.77 MeV were determined with high precision, and a level scheme of ⁹²Nb is proposed. From a Hauser-Feshbach analysis, the γ-decay scheme and other information, the spin-parities of many levels were assigned.     

Does truth-table of linear norm reduce the one-query tautologies to a random oracle?

In our former works, for a given concept of reduction, we study the following hypothesis: “For a random oracle A, with probability one, the degree of the one-query tautologies with respect to A is strictly higher than the degree of A.” In our former works (Suzuki in Kobe J. Math. 15, 91–102, 1998; in Inf. Comput. 176, 66–87, 2002; in Arch. Math. Logic 44, 751–762), the following three results are shown: The hypothesis for p-T (polynomial-time Turing) reduction is equivalent to the assertion that the probabilistic complexity class R is not equal to NP; The hypothesis for p-tt (polynomial-time truth-table) reduction implies that P is not NP; The hypothesis holds for each of the following: disjunctive reduction, conjunctive reduction, and p-btt (polynomial-time bounded-truth-table) reduction. In this paper, we show the following three results: (1) Let c be a positive real number. We consider a concept of truth-table reduction whose norm is at most c times size of input, where for a relativized propositional formula F, the size of F denotes the total number of occurrences of propositional variables, constants and propositional connectives. Then, our main result is that the hypothesis holds for such tt-reduction, provided that c is small enough. How small c can we take so that the above holds? It depends on our syntactic convention on one-query tautologies. In our setting, the statement holds for all c < 1. (2) The hypothesis holds for monotone truth-table reduction (also called positive reduction). (3) Dowd (in Inf. Comput. 96, 65–76, 1992) shows a polynomial upper bound for the minimum sizes of forcing conditions associated with a random oracle. We apply the above result (1), and get a linear lower bound for the sizes.     

A unique peroxide formation based on the Mn(III)-catalyzed aerobic oxidation

The autoxidation of a mixture of 1,1-diarylsubstituted alkenes 4 and 4-hydroxy-1H-quinolin-2-ones 5 in the presence of a catalytic amount of manganese(III) acetate dihydrate in air gave 3,3-bis(2-hydroperoxyethyl)-1H-quinoline-2,4-diones 6 in 31-91% yields together with [4.4.3]propellane-type cyclic peroxides 7 (10-34%). A similar aerobic oxidation of 3-substituted quinolinones 8 yielded cyclic peroxide derivatives 9 and/or 3-hydroperoxyethylated quinolinediones 10 depending on the substituent. The structures of the bis(hydroperoxide) 6 (R¹=Me, Ar=4-ClC₆H₄) and the [4.4.3]propellane 7 (R¹=Me, Ar=Ph) have been corroborated by X-ray crystallography.     

Development and applications of “Mössbauer cameras”

Two different types of “Mössbauer camera” are presented in this review article. The first one uses an imaging technique for γ-rays which are converted to visual light by a Photon-counting Image Acquisition System (PIAS) combined with a Fiber Optic plate with CsI (Tl) Scintillator (FOS), while the second one is a mapping technique for γ-rays which are first focused by a Multi Capillary X-ray lens (MCX), and subsequently electrons and γ-rays are detected as function of the sample position by a micro-channel plate (MCP) and a Si-PIN detector, respectively. A mapping image of a silicon solar cell is shown as an example obtained by the latter system. We also report on the present status in developing a new combined lens for the mapping using a MCX and a Fresnel Zone Plate (FZP) in order to realize a submicron-meter spatial resolution in a laboratory.     

Spin-parity assignments for the excited states of 91Nb from the 91Zr(p,nγ)91Nb reaction

The energy levels of ⁹¹Nb were studied by means of the (p, nγ) reaction. The de-excitation γ-rays were observed with a Ge(Li) detector in the proton energy range from 3.25 to 5.51 MeV in steps of about 30 keV. Resonances attributed to isobaric analog states in the compound system ⁹¹Nb were observed in the excitation functions of the de-excitation γ-rays. From an analysis of these analog resonances, a Hauser-Feshbach analysis and the γ-decay scheme, the spin-parities of the levels up to 2792.6 keV (22 levels) were assigned.     

Elastic scattering of 119 MeV 3He particles and energy and mass-number dependence of optical potential parameters

The elastic scattering of 119 MeV ³He particles by ¹²C, ²⁷Al, ^58,60,62,64Ni, ⁵⁹Co, ^90,92Zr and ⁸⁹Y has been investigated over a wide angular range in order to study the mass-number dependence of the optical potential and odd-even differences in the elastic scattering. The elastic scattering cross sections have been analyzed in terms of the optimal model. The data, except for ¹²C, ²⁷Al and ⁵⁹Co, were fitted with r_R = 1.21 fm, a_R = 0.76 fm and r_I = 1.17 fm, fixed at the average values. The following formulae were obtained for the three remaining parameters by combining with the energy dependence of the parameters (90–120 MeV) obtained previously:

$\text{V=111.4?0.173E+}\text{Z}\text{A}{}^{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{+14.9}\text{N?Z}\text{A}\text{(}\text{MeV}\text{)}$

$\text{W}{}_{\mathrm{<mtext>D</mtext>}}\text{=24.8?0.028E (}\text{MeV}\text{)}$

,

$\text{a}{}_{\mathrm{I}}\text{=0.754+0.78}\text{N?Z}\text{A}\text{(}\text{fm}\text{)}$

The depths of the valleys of the angular distribution in the case of ${}^{59}\text{Co}\text{(I =}\text{7}\text{2}\text{)}$ are considerably shallower than those for Ni isotopes, while the depths in the case of ${}^{89}\text{Y}\text{(I =}\text{1}\text{2}\text{)}$ are nearly the same as those for Zr isotopes. Thus it may be concluded that the odd-even differences are attributed to the scattering from the quadrupole moment of the odd-A nucleus (if $\text{I >}\text{1}\text{2}$).     

Differential negative resistance caused by inter-subband scattering in a 2-dimensional electron gas

Differential negative resistance has been observed in the range $\text{0.5～1.2 kV}\text{cm}$ at 77 K in a two-dimensional electron gas formed at a modulation-doped AlGaAs/GaAs heterojuction interface. This differential negative resistance is attributed to the sudden onset of inter-subband scattering when electrons achieve sufficient energy from the electric field.     

Incident energy dependence of preequilibrium (p,p′) spectra

Proton energy spectra from (p, xp) reactions on⁹⁸Mo and¹⁰⁶Pd have been measured at incident energies of 12, 14, and 16 MeV to investigate the incident energy dependence of preequilibrium (p, p′) process. The (p, xp) energy spectrum for⁶⁰Ni has also been measured at an incident energy of 18 MeV to confirm the mass number dependence. These spectra were compared with a calculation based on the exciton model in which the square of the average effective matrix element ¦M¦² was assumed to beKA ^?3 E ^?1 and isospin conservation was taken into account. The calculated spectra using a constantK-value (430 MeV³) were in good agreement with all the measured ones. The role of isospin conservation in preequilibrium process was discussed through the present analyses.