Synthese und reaktionen von 1-germcyclohexa-2,4-dienen und 1-germacyclohexa-2,4-dien-eisentricarbonylen

1,1-Diakyl(aryl)4-alkyl(aryl)-4-methoxy-1-germacyclohexa-2,5-dienes undergo ether cleavage with sodium in n-pentane or liquid ammonia. Hydrolysis of the resulting sodium salts yields the 1,1-dialkyl(aryl)-4-alkyl(aryl)-1-germacyclohexa-2,4-dienes. Reduction of 1-chloro-4-methoxy-1-germacyclohexa-2,5-dienes with LiAlH₄ can be directed to give the 1H-1-germacyclohexa-2,4-dienes with ether cleavage.The 1H-1-germacyclohexadienes are chlorinated by PCl₅ and brominated by N-bromosuccinimide to the 1-chloro- or 1-bromo-1-germacyclohexa-2,4-dienes, respectively. 1,1-Diethyl-4-phenyl-4-methoxy-1-germacyclohexa-2,5-diene reacts with PCl₃ with ether cleavage and formation of the 6-chloro-1-germacyclohexa-2,4-diene. Ether cleavage is also possible with BCl₃, the 1-phenyl-1-chloro-4R-4-methoxy-1-germacyclohexa-2,5-dienes are transformed into the 1-phenyl-1,6-dichloro-4R-1-germacyclohexa-2,4-dienes.The Fe(CO)₃ complexes of 1,1-dialkyl(aryl)-1-germacyclohexa-2,4-dienes were synthesized.     

1-Trimethylsilyl-, 1-Trimethylgermyl- und 1-Trimethylstannyl-3,4-dimethylphospholen

1-Trimethylsilyl-, 1-Trimethylgermyl-, and 1-Trimethylstannyl-3,4-dimethylphospholene 1-Lithium-3,4-dimethylphospholen reacts with Me₃SiCl and Me₃GeCl yielding 1-trimethylsilyl-3,4-dimethylphospholene ( 1 ) and 1-trimethylgermyl-3,4-dimethylphospholene ( 2 ) respectively. 2 and 1-trimethylstannyl-3,4-dimethylphospholene ( 3 ) are formed using the reaction of 1 with Me₃GeCl and Me₃SnCl respectively. The ¹H, ¹³C and ³¹PNMR-spectra as well as the mass spectra of the new compounds are discussed.     

Die Protonierung von 1-Formyl- und 1-Acetyl-azulenen

NMR. data show that protonation of 1-formyl-azulene yields essentially a one-to-one mixture of conjugate acids in which the hydroxyl group assumes the syn-planar or anti-planar configuration relative to the tropylium nucleus. The presence of a minute amount of protonation in position 3 is demonstrated by the rapid hydrogendeuterium exchange in this position. Steric interference in 1-formyl-azulenes with a methyl group in the peri position 8 favours the anti-planar configuration. As shown by one example, the conjugate acids of 1-acetyl-azulenes without substituents in positions 2 or 8 assume the anti-planar configuration. In 1-acetyl-azulenes carrying a methyl group in position 8, addition of a proton to the carbon centre 1 is the preferred route of protonation, as a consequence of the accompanying strain release.     

Acyl- und Alkylidenphosphane. XXXII [1, 2]. Di-cyclo-hexoyl- und Diadamant-1-oylphosphan — Keto-Enol-Tautomerie und Struktur

Acyl- and Alkylidenephosphines. XXXII. Di-cyclohexoyl- and Diadamant-1-oylphosphine – Keto-Enol Tautomerism and Structure Lithium dihydrogenphosphide · DME (¹) [12] and cyclo-hexoyl or adamant-1-oyl chloride react in a molar ratio of 3:2 to give lithium di-cyclo-hexoylphosphide · DME and the corresponding diadamant-1-oylphosphide.2THF (¹) resp. Treatment of these two compounds with 85% tetrafluoroboric acid. diethylether adduct yields di-cyclo-hexoyl- ( 1b ) and diadamant-1-oylphosphine ( 1c ). In nmr spectroscopic studies 1b over a range of 203 to 343 K, a strong temperature dependence of the keto-enol equilibrium is found; thermodynamic data characteristic for the formation of the enol tautomer (ΔH⁰ = ?4.3 kJ. mol^?1; ΔS⁰ = ?9.2 J. mol^?1. K (^?1) are compared of 1,3-diketones. The enol tautomer of diadamant-1-oylphosphine ( E-1c ) as obtained from a benzene solution in thin colourless plates, crystallizes in the monoclinic space group P2₁/c {a = 722.2(2); b = 1085.5(4); c = 2434.8(5) pm; ß = 96.43(2)° at –100 ± 3°C; Z = 4}. An X- ray structure analysis (R_w = 0.033) shows bond lengths and angles to be almost identical within the enolic system (P? C 179/180; C? O 130/129; C? C(adamant-1-yl) 152/153 pm; C? P? C 99°; P? C? O 124°/124°; P? C? C 120°/120°; C? C? O 116°/116°. The geometry of the very strong, but probably asymmetric O‥H‥O bridge is discussed (O? H 120/130, O‥O 245 pm).     

Papier-chromatographische Trennung und Bestimmung von 1-Aminoanthrachinon- und 1-Amino-4-bromanthrachinon-2-sulfons?ure

Ohne Zusammenfassung

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Separation and determination of 1-Aminoanthraquinone- and 1-Amino-4-bromoanthraquinone-2-sulphonic acid by paper chromatography

     

1-Amino-2-phthalimido-diazen-1-oxide: Bildung,Eigenschaften und Fragmentierungen in Imido- und Amino-nitrene

1-Amino-2-phthalimido-diazene-1-oxides: Formation, Properties and Fragmentation Reactions into Imido- and Amino-nitrenes¹) Oxidatively generated phthalimido-nitrene ( 1 ) reacts with the nitrosoamines 2a-d (see Scheme 1) to give the corresponding (Z)-1-amino-2-phthalimido-diazene-1-oxides 3a-d in good yields. With the O-nitroso compound 2e , no addition of the nitrene 1 took place. The constitution the adducts 3 (R = NR′₂) is deduced from their spectroscopic properties (UV., IR., ¹H-NMR. and MS.) as compared to those of (Z)-1-aryl- and (Z)-1-alkyl-2-phthalimido-diazene-1-oxides 3 (R = aryl and alkyl, resp.). The (Z)-configuration of 3 (R = NR′₂) follows from an X-ray analysis which is reported separately. Compounds 3 (R = NR′₂) are cleaved photolytically as well as by acid to the corresponding nitrosoamines 2 (R = NR′₂) and the nitrene 1 , which could be trapped by cyclohexene to give 40% of 7-phthalimido-7-azabicyclo [4.1.0]heptane ( 8 ) and by dimethylsulfoxide to yield 96% of S, S-dimethyl-N-phthalimido-sulfoximide ( 13 ). Nucleophilic attack leads to fragmentation of 3 (R = NR′₂) into derivatives of phthalic acid and degradation products of intermediate aminonitrenes 24 corresponding to the respective nitrosoamines 2 (R = NR′₂) with loss of oxygen. A general rationalization for the formation of 24 includes as a key step of N- to C-migration of the O-atom (see Scheme 6). The final fate of 24 is depending on the type of the nucleophile used. Thus, hydrazinolysis of 3b and of 3c generates besides N, N′-phthaloylhydrazine ( 15 ), morpholine ( 14 ) from 3b and 1, 3-dihydroisoindole ( 16 ) together with 6′-methylidene-1, 2, 3, 4-tetrahydronaphthalene-2-spiro-1′-cyclohexa-2′, 4′-diene ( 17 ) from 3c (see Scheme 5). Treatment of 3b and of 3c with sodium methylate leads in both reactions to monomethyl phthalate ( 33 ) and, with 3b , to 1, 2-dimorpholinodiazene ( 31 ) and, with 3c , to 17 (see Scheme 7). Finally, the reaction of 3b with diethylamine generates N, N-diethylphthalamic acid ( 36 ), morpholine ( 14 ), 1,1,4,4-tetraethyl-2-tetrazene( 34 ) and l,l-diethyl-4,4-(3-oxapentamethylene)-2-tetrazene ( 35 ) (see Scheme 8).