Synthesis of 2′-Deoxyribofuranosides of 8-Aza-7-deazaguanine and Related Pyrazolo[3,4-d]pyrimidines

The N(1)- and N(2)-(2′-deoxyribofuranosides) 1 and 2 , respectively, of 8-aza-7-deazaguanine were prepared via phase-transfer glycosylation in the presence or absence of Bu₄NHSO₄ as catalyst of 6-amino-4-methoxy-lH-pyrazolo[3,4-d]pyrimidine ( 7c ) with 2-deoxy-3,5-di-O-(p-toluoyl)-α-D -erythro-pentofuranosyl chloride ( 10 ). On a similar route, but without catalyst and employing THF as organic phase, the 6-amino-4-chloronucleosides 11b and 12b were synthesized from 7a and converted into the N(1)-and N(2)-substituted 4-thioxo analogues 17a and 18a , respectively. The ratio of N(1)- to N(2)-glycosylation was 2:1 for 7c and 1:1 for 7a , viz. depending on the nucleobase structure. The rate of the H⁺-catalyzed N-glycosyl hydrolysis was strongly decreased for the N(2)-(β-D -2′-deoxyribofuranosides) as compared to the N(1)-compounds. However, the N(1)-nucleoside 1 , which is an isostere of 2′-deoxyguanosine, is sufficiently stable to be employed later in solid-phase oligonucleotide synthesis.     

Elektronenmangelverbindungen des Galliums Zur Kenntnis von Ca3Ga5

Electron Deficient Compounds of Gallium: Crystal Structure of Ca₃Ga₅ The stoichiometry of the formerly described compound Ca₂Ga₃ is corrected to Ca₃Ga₅. This compound crystallizes in the orthorhombic system, space group Cmcm (No. 63) with the lattice constants see ?Inhaltsübersicht”?. In the structure there is a Ga framework for which on the basis of the Gillespie/Nyholm conception and by calculating the bond numbers according to Pauling a characteristic electron concentration can be derived.     

13C-NMR-spektren stereoisomerer 1,4-dialkylspiro[4.5]decan-derivate

The ¹³C NMR spectra of a series of 7-substituted 1,4-dialkylspiro[4.5]decanes and of suitable reference compounds are assigned and the derived substituent effects upon the chemical shifts are discussed. In particular, consideration of γ and δ-effects allows the differentiation between 1,4-cis- and 1,4-trans-compounds. Furthermore, the (relative) configuration of the chiral spiroatom C-5 is determined.     

Massenspektrometrische Identifizierung von biogenen Aminen in Form ihrer 1-Dimethylamino-naphthalin-5-sulfonyl-Derivate

Zusammenfassung Von etwa 80 1-Dimethylamino-naphthalin-5-sulfonyl-(DANS-)Derivaten biogener Amine und verwandter Verbindungen mit unterschiedlichen strukturellen Elementen wurden die durch Elektronenstoß induzierten Fragmentierungen untersucht. Die Prinzipien dieser Fragmentierungen und die Brauchbarkeit der Massenspektrometrie bei niedrigem Auflösungsvermögen für die Identifizierung dünnschicht-chromatographisch getrennter DANS-Derivate biogener Amine aus Gewebsextrakten werden diskutiert.

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Mass spectrometric identification of biogenic amines as 1-dimethylamino-naphthalene-5-sulphonyl derivatives

The fragmentation by electron impact of approximately 80 1-dimethylamino-naphthalene-5-sulphonyl (DANS) derivatives of biogenic amines and related substances of different structural features has been studied. The principles of these fragmentations and the suitability of low resolution mass spectrometry for the identification of thin-layer chromatographically separated DANS-derivatives of biogenic amines from tissue extracts are discussed.

     

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