Synthesen von Dibenzo[b,e][1,4]dioxin-2,3-chinonen,einschliesslich der Ecklonochinone A und B sowie der Isoecklonochinone A und B

Syntheses of Dibenzo[b,e][1,4]dioxin-2,3-quinones Including the Ecklonoquinones A and B and the Isoecklonoquinones A and B Oxidation of monomesyloxy-substituted pyrocatechols with MnO₂ in toluene using phase-transfer conditions leads in high yield to monomesyloxy-substituted dibenzo[b,e][1,4]dioxin-2,3-quinones with loss of one mesyloxy group. In this way, ecklonoquinone A ( 2 ), ecklonoquinone B ( 3 ), isoecklonoquinone A ( 43 ), and isoecklonoquinone B ( 44 ) were prepared. Their structures are based on X-ray analyses of ecklonoquinone-A leucoacetate ( 45 ) and the mesyloxy-substituted quinone 20 . The reddish-violet dibenzodioxin-diquinone 49 was prepared from an intermediate of the iso-series. The parent compound 1 has been synthesized in yields better than 50% from pyrocatechol and methyl 2,5-dioxo-2,5-dihydrobenzoate as oxidant and 2-methoxypyridin as catalyst. To rationalize the specific effect on the dimerisation step of the mesyloxy group, the intermediacy of 1,4-quinone monoacetals is proposed. This also applies to a proposed biogenetic scheme.     

Silicon in organic synthesis. 14. Five ring annulation processes based upon thermal rearrangement of (1-trimethylsilylcyclopropyl)ethylenes

Pyrolysis of (1-trimethylsilylcyclopropyl)ethylenes affords silyl substituted cyclopentenes in high yield. Subsequent reaction of these products with varied electrophiles forms the basis of a new and versatile five-ring annulation sequence.     

Salt crystallization as damage mechanism in porous building materials--a nuclear magnetic resonance study

Salts can damage building materials by chemical reactions or crystallization, which is a serious threat to cultural heritage. In order to develop better conservation techniques, more knowledge of the crystallization processes is needed. In a porous material, the size of a salt crystal is limited by the sizes of the pores. It has been predicted that as a consequence, the solubility of a salt increases with decreasing pore size. This increase seems to be related to an increase of the stress generated by a crystal on the pore wall. It has been suggested that the resulting stress could become high enough to induce failure. We have studied the crystallization of salts in porous materials with well-defined pore sizes. Samples were saturated at 40 degrees C with saturated Na2SO4 and Na2CO3 solutions. Next we have cooled the samples to 0 degrees C and waited for nucleation. After nucleation occurred, the solubility in the porous material was measured with nuclear magnetic resonance (NMR) as a function of the temperature. The measurements on Na2CO3 indeed show an increase in solubility with a decrease in pore size. For Na2SO4, we did not observe a pore size-dependent solubility. However, we have to remark that these results show a metastable crystal phase. The results can be used to calculate the actual pressure exerted by the crystals onto the pore wall.     

A stereoselective cyclization to carbafuranose derivatives starting from 1,4-bis-epoxides

[reactions: see text] A concise synthesis of highly functionalized cyclopentane derivatives via a Brook rearrangement mediated stereoselective linchpin cyclization reaction involving tert-butyldimethylsilyl-1,3-dithianyllithium and homochiral 1,4-bis-epoxides is described.     

Pectenotoxin-2 synthetic studies. 2. Construction and conjoining of ABC and DE Eastern hemisphere subtargets

[reaction: see text] Practical asymmetric synthesis of aldehyde 2 and tetrazolyl sulfone 3 has allowed for their coupling via Julia olefination to generate 32 as a single product. This substance possesses the entire carbon backbone of the A-E substructure of pectenotoxin-2.     

Study of Zgamma events and limits on anomalous ZZgamma and Zgammagamma couplings in pp collisions at square root s = 1.96 TeV

We present a measurement of the Zgamma production cross section and limits on anomalous ZZgamma and Zgammagamma couplings for form-factor scales of lambda = 750 and 1000 GeV. The measurement is based on 138 (152) candidates in the eegamma (mumugamma) final state using 320(290) pb(-1) of pp(-1) collisions at square root of s = 1.96 TeV. The 95% C.L. limits on real and imaginary parts of individual anomalous couplings are /h(10,30)Z/ < 0.23, /h(20,40)Z/ < 0.020, /h(10,30)gamma/ < 0.23, and /h(20,40)gamma/ < 0.019 for lambda = 1000 GeV.     

Measurement of the Lambda0b lifetime in the decay lambda0b--> J/psiLambda0 with the D0 detector

We present measurements of the Lambda(0)(b) lifetime in the exclusive decay channel Lambda(0)(b)--> J/psiLambda(0), with J/psi--> mu(+)mu(-) and Lambda(0)--> ppi(-), the B0 lifetime in the decay B0-->J/psiK(0)(S) with J/psi--> mu(+)mu(-) and K(0)(S)-->pi(+)pi(-), and the ratio of these lifetimes. The analysis is based on approximately 250 pb(-1) of data recorded with the D0 detector in pp collisions at sqrt[s] = 1.96 TeV. The Lambda(0)(b) lifetime is determined to be tau(Lambda(0)(b)) = 1.22(+0.22)(-0.18)(stat) +/- 0.04(syst) ps, the B0 lifetime tau(B0) = 1.40(+0.11)(-0.10)(stat) +/- 0.03(syst) ps, and the ratio tau(Lambda(0)(b))/tau(B0) = 0.87(+0.17)(-0.14)(stat) +/- 0.03(syst). In contrast with previous measurements using semileptonic decays, this is the first determination of the Lambda(0)(b) lifetime based on a fully reconstructed decay channel.     

Organic homojunction diodes with a high built-in potential: interpretation of the current-voltage characteristics by a generalized Einstein relation

We realize p- and n-type doping of the organic semiconductor zinc-phthalocyanine using a novel strong organic donor. This allows us to demonstrate the first stable and reproducible organic p-n homojunctions. The diodes show very high built-in potentials, attractive, e.g., for organic solar cells. However, the diode characteristics cannot be described by the standard Shockley theory of the p-n junction since the ideality factor strongly increases with decreasing temperature. We show that this behavior can be explained by deviations from the Einstein relation for disordered materials.