Halogenated 3-pyridylketones

The oxidation of 2,6-dichloro-3-benzylpyridines and bis(2,6-dichloro-3-pyridyl)methanes, respectively, was accomplished using chromic trioxide in a highly acidic medium. The synthesis of several phenyl-3-(2,6-dichloropyridyl)ketones and of bis(2,6-dichloro-3-pyridyl)ketone are reported.     

Photochemisches Verhalten von 1- und 2-alkylierten 1, 2-Dihydronaphthalinen bei tiefen Temperaturen

The irradiations of 1, 1-dimethyl- (8), 1, 1-di-(tri-deuteriomethyl)- (d₆– 8 ), 1, 1, 2, 2-tetramethyl- ( 9 ) and cis- and trans-1, 2-dimethyl-1, 2-dihydronaphthalenes (cis- and trans- 10 ) were investigated in 2, 2-dimethylbutane/pentane at ?100° using a mercury high-pressure lamp, and with mercury high- and low-pressure lamps at room temperature. The results were compared with one another, and those of the individual compounds are collected in schemes 2 and 4–7. The most important results are the following: 1. The 1, 2-dihydronaphthalenes undergo a conrotatory ring opening to the o-quinodimethanes on irradiation with high- or low-pressure lamps at room temperature or at ?100°. Thermal reactions ([1, 7a]H-shifts, electrocyclisations) are suppressed at ?100°. The o-quinodimethanes formed from 8 (scheme 2), 9 (scheme 5) or cis- 10 (scheme 6) undergo on irradiation with the high-pressure lamp, [1, 5]H-shifts or photochemical Diels-Alder reactions after renewed photochemical excitation, to yield the benzobicyclo[3.1.0]hex-2-ene derivatives. These Diels-Alder reactions do not proceed stereospecifically, and therefore are not orbital symmetry controlled reactions. 2. If the 1, 2-dihydronaphthalenes are irradiated at room temperature with either a high- or a low-pressure lamp, then the initially formed o-quinodimethanes undergo thermal [1, 7a]H-shifts, in preference to all other reactions, as long as this is sterically possible; the resulting products can undergo secondary photochemical transformations. Such o-quinodimethanes are formed on irradiation of 8, 9 and cis- 10 . From trans- 10 , an o-quinodimethane mixture is formed, of which one component (cis, cis- 22 ) undergoes thermal [1, 7a] H-shifts, while the other (trans, trans- 22 ) suffers a thermal disrotatory electrocyclisation to give cis- 10 . If a high-pressure lamp is used in the last experiment, then the competing photochemical Diels-Alder cyclisation to bicyclic compounds of the type 23 (scheme 7) can result in the trans, trans- 22 . As was shown by Salisbury [3], and confirmed by ourselves in other cases [2], photochemical Diels-Alder reactions or [1, 5]H-shifts in the o-quinodimethanes require light of wavelength ? 400 nm (high-pressure lamp). The present photochemical investigations amplify and confirm our earlier conclusions concerning the photochemistry of the 1, 2-dihydronaphthalenes [2].     

Methylthiomethylierung von Anilinen und Phenolen, 3. Mitt.: Darstellung von N-Aryl-S,S-dialkylsulfimiden

Zusammenfassung Aus Anilinen, die im aromatischen Ring mit CH₃, CH₃SCH₂, CH₃O, Cl, Br oder NO₂ substituiert sind, und Sulfoxiden wird in Anwesenheit von P₄O₁₀ und Triäthylamin eine Reihe von N-Aryl-S,S-dialkylsulfimiden erhalten. Diese Reihe umfaßt Verbindungen mit CH₃-, C₂H₅- und –(CH₂)₄-Gruppen am Schwefelatom. Das Sulfimid aus Mesidin lagert sich—formal analog zu einerSommelet—Hauser-Umlagerung—zum 2,4,6-Trimethyl-2-methylthiomethylcyclohexa-3,5-dien-1-imin um.

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Methylthiomethylation of anilines and phenols, III: Preparation of N-aryl-S,S-dialkylsulfimides

The synthesis of a number of N-aryl-S,S-dialkylsulfimides by reaction of anilines with sulfoxides in presence of P₄O₁₀ and triethylamine is given. This series includes compounds with CH₃-, CH₃SCH₂-, CH₃O-, Cl-, Br- and nitro-groups attached to the aromatic nucleus, resp., and with CH₃-, C₂H₅-or–(CH₂)₄-groups on the sulfur atom. The sulfimide obtained from mesidine is rearranged in formal analogy to aSommelet-Hauser rearrangement to 2.4.6-trimethyl-2-methylthio-methylcyclohexa-3.5-dien-1-imine.

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Als 1. Mitt. soll gelten:P. Claus, Mh. Chem.99, 1034 (1968).

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2. Mitt.:P. Claus undW. Vycudilik, Tetrahedron Letters1968, 3607.     

The critical probability for Voronoi percolation in the hyperbolic plane tends to 1/2

We consider percolation on the Voronoi tessellation generated by a homogeneous Poisson point process on the hyperbolic plane. We show that the critical probability for the existence of an infinite cluster tends to 1/2 as the intensity of the Poisson process tends to infinity. This confirms a conjecture of Benjamini and Schramm [5].     

Investigation of the40Ca(γ,N) reaction at 60 MeV

The values of the angle-integrated cross section for the decay to various low-lying states in³⁹K following the⁴⁰Ca(,) reaction at a mean photon energy of 60 MeV are reported on, together with the values of the reduced Legendre coefficientsa _i . The⁴⁰Ca(,gp) and⁴⁰Ca(,n) reactions yield the same angular cross-section values and these agree with the corresponding RPA-calculations.Senior Research Associate NFWO     

Ein Beitrag über Ba3Pt4HgO11: Das erste Erdkalimetall-Oxoplatinat(II,V)/Oxomercurat

A Contribution on Ba₃Pt₄HgO₁₁: The First Alkaline-Earth Oxoplatinate(II,V)/Oxomercurate Single crystals of Ba₃Pt₄HgO₁₁ were prepared by oxygen high pressure technique (4 200–3 600 bar) and investigated by X-ray methods. It crystallizes with hexagonal symmetry, space group D? P6 2c, a = 6.021, c = 17.374 Å, Z = 2. Ba₃Pt₄HgO₁₁ represents a new structure type, showing structural relationships to Ba₂Hg₃Pd₇O₁₄ and to the precious metal 6L-perovskites. The Hg²⁺ ions show dumb-bell like coordination, Pt²⁺ a square-planar surrounding and Pt⁵⁺ face shared double octahedra.