Interaction of dichloromethane with germanium

Conclusions Methyltrichlorogermane, bis(trichlorogermyl)methane, and Ge-hexachloro-1,3,5-germacyclohexane are formed in good yield from dichloromethane and elementary germanium in a flow-type setup at 380°.Let us thank L. A. Leites for taking the IR and Raman spectra and A. N. Egorochkin for the NMR spectra.Translated from Izvestiya Akademii Nauk SSSR, Seria Khimicheskaya, No. 10, pp. 1887–1889, October, 1964     

Synthese von 2,7-Dioxa-isotwistan und 2,7-Dioxatwistan. Vorläufige Mitteilung

The syntheses of 2,7-dioxa-isotwistane ( 14 ), 2,7-dioxa-twistane ( 19 ), and some of their derivatives ( 6 – 13 and 15 – 18 ) are described. The twistane-skeleton was obtained by a molecular rearrangement starting from the iodo-iso-twistane compound 8 .     

Infrared study of anion-water interactions in dichloromethane

The binding energy and number of anion-water interactions were investigated by infrared spectroscopy in aqueous CH₂Cl₂ solutions containing salts and cryptands. In these solutions the frequency of the bound OH vibration and the H-bond energy both correlate linearly (Badger-Bauer rule) and are of the same order of magnitude as those in water-organic H-bond acceptor systems. The frequency shift of the OH vibration and the H-bond energy both show an anion dependence which increases in the order: $$ClO_4^ - {\text{ }}<< {\text{ NO}}_{\text{3}}^ - \lesssim I^ -< {\text{ SCN}}^ - {\text{ }}< {\text{ }}Cl^{ - {\text{ }}} \lesssim CO_3^2 {\text{ }} \lesssim F^ -$$ to 340 cm^?1 and 17.2 kJ-mol^?1 of H-bonds, respectively, when compared to H₂O-CH₂Cl₂ interactions. Anion-water H-bond energies agree with the results of computer simulations and heats of hydration. This indicates that an H-bond may be regarded as an interaction between an acid H-atom and a partial charge-whether the H-bond acceptor is formally charged or not (anion or organic base). The magnitude of water-anion interaction energies show a similar order as is found for water interactions.     

[4](2,7)troponophane

The title compound $\text{5}$ and its dehydro analog $\text{6}$ were synthesized from $\text{10}$ and $\text{9,}$ respectively, and their physical properties were examined. Tropone ring in these compounds are deeply bent to tub shapes and conjugation of the carbonyl group is greatly reduced.     

Synthesis of 2,7-disubstituted-4,5,9,10-tetraazapyrenes

2,7-Dimethyl-4,5,9,10-tetraazapyrene (VI) was synthesized by the catalytic hydrogenation of 4,4′-dimethyl-2,2′,6,6′-tetranitrobiphenyl (IIa) with W-2 Raney nickel in the presence of alkali. 4,4′-Dicarbomethoxy-2,2′,6,6′-tetranitrobiphenyl (IIc) under similar conditions in neutral medium gave 4,4′-dicarbomethoxy-2,2′,6,6′-tetraaminobiphenyl (IV) which on oxidation gave 2,7-dicarbomethoxy-4,5,9,10-tetraazapyrene (V). 2,7-Dimethyl-, 2,7-dimethoxy-, and 2,7-diacetamido-4,5,9,10-tetraazapyrene di-N-oxides (III a,b,c) were obtained by catalytic reduction of the corresponding 4,4′-disubstituted-2,2′,6,6′-tetranitrobiphenyls with W-7 Raney nickel in the presence of alkali. Compound VI on oxidation with hydrogen peroxide gave the di-N-oxide (IIIa).     

Photodimerization of 1H-azepine-2,7-dione

1H-Azepine-2,7-dione 2 afforded photodimer 8 by irradiation using a high or low pressure mercury lamp. Photodimer 8 had a unique structure which must have formed with the prototropy in one of the two molecules of compound 2 . Measurement of the fluorescence spectra of 2 indicated a spectrum of the excimer during the dimerization of 2 . Irradiation of the dimer of 2 at its wave-length of maximal absorption failed to cause it to change into a monomer of 2 .     

2,7-二甲氧基-3,6-二苯氧基萘的合成

以3,6-二溴-2,7-二羟基萘为起始原料,与硫酸二甲酯经甲醚化反应得3,6-二溴-2,7-二甲氧基萘(2);2与苯酚在碘化亚铜催化下经取代反应合成了新化合物——2,7-二甲氧基-3,6-二苯氧基萘,总收率82.5%,其结构经1H NMR,13C NMR,ESI-MS和元素分析表征。     

2.2](2,7)-Fluorenophanediene, [2.2.2](2,7)-fluorenophanetriene, and their fluorenide ions

The McMurry coupling of 2,7-diformylfluorene affords a dimer, anti-[2.2](2,7)-fluorenophanediene, and a trimer, [2.2.2](2,7)-fluorenophanetriene, as cyclic oligomers. X-Ray crystallography of the dimer establishes its strained, layered structure with anti-conformation. While the fluorenyl groups of the dimer do not show any sign of rotation in the variable temperature 1H NMR spectra up to 120 degrees C, those of the trimer are fast rotating even at -50 degrees C. Treatment of the dimer and trimer with KH in DMSO furnished the respective dianion and trianion that are stable at room temperature in the solutions. While the trianion shows substantial conjugation through the etheno bridges, the dianion shows little conjugation through the etheno bridges and almost no proton-deuterium exchange of the fluorenyl C9-H with the solvent DMSO-d6 probably due to stereospecific protonation-deprotonation associated with the tightly layered structure.