Diphospho-myo-inositol phosphates (PP-InsP5 and bis-PP-InsP4) were isolated from Dictyostelium in order to clarify the precise positional isomerism by two-dimensional 1H/31P-NMR analysis. The diphosphorylated inositol phosphates are 4-PP-Ins(1,2,3,5,6)P5 and 4,5-bis-PP-Ins(1,2,3,6)P4 or their corresponding enantiomers. The vicinal arrangement of the diphospho groups with its steric and electrostatic constraints possibly qualifies bis-PP-InsP4 as a metabolite with high phosphate-group-transfer potential in phosphotransferase reactions.

Mesoionic 5-alkyl-4,6-dioxo-l,3-diphenyl-2-(3-vinylbenzylthio)-l,3-diazine (6) was prepared by condensation of alkylmalonic acid (5) with 1,3-diphenyl-2-(3-vinylbenzyl)isothiourea (4) by use of dicyclohexylcarbodiimide (DCC). Homopolymerization of 6 led to new polystyrene derivatives (7) with mesoionic 4,6-diox0-1,3-diazines as pendant groups. UV irradiation of 7 yielded polystyrene derivatives with bis(8-lactam) moieties as pendant groups (8). The change of some physical properties during the irradiation is discussed. 5-Heptyl-4,6-dioxo-l,3-diphenyl-2-(3-methylbenzylthio)-l,3-diazine (11) and 4-heptyl-l-(3-methylbenzylthio)-3,5-dioxo-2,6-diphenyl-2,6-diazabicyclo[2.2.0]hexane (12) as low-molecular-weight model compounds were synthesized for structural analysis.

Nach dem Schema der [3 + 21-Cycloaddition reagieren die 1,3-Dithiolylium-4-olate lc, d, f mit in situ bereitetem Formaldehyd zu den neuen 2-0xa-6,7-dithiabicyclo[2.2.1]heptanon-Derivaten 2a -c. Weiterhin vereinigt sich 1 a mit der CN-Doppelbindung des 3-Phenyl-2 H-2-azirincarbonsaure-ethylesters bei 100°C regio-und stereospezifisch zum em-Addukt 3 (92%), und die entsprechende Umsetzung von 1 a mit der NN-Doppelbindung des 4-Phenyl-l,2,4-triazolin-3,5-dions liefert 90% Tricyclus 4. Die analogen Reaktionen von 1 a -c, e mit Azodicarbonsauredimethylester fiihren zu den Cycloaddukten 5 a --d (91 -62%). Spektroskopische Daten und einige Abbaureaktionen bestatigen die Adduktstrukturen.

Darstellung der mesomeren HeteropentalenBetaine 4 und 7Die Synthese des Thieno[3,4-c]thiophens 4 ist zwar bereits bekannt 6,7), jedoch wird hier bezuglich der Darstellung der Vorstufe 3 eine abweichende, optimierte Vorschrift angegeben. Durch Umsetzung des gut zuganglichen 1,3-Dithiolylium-4-0lats~~~' 1 mit Dibenzoylethin (2) ist die Vorstufe 3 in 93proz. Ausbeute bequem erhaltlich. Die uberfiihrung von 3 in 4 mit Phosphor(V)-sulfid in siedendem Pyridin gelingt problemlos rnit 80-90% Ausbeute nach Lit. 'I.In ahnlicher Weise setzt man das nach einem optimierten The mesomeric heteropentalene betaines of type 4,7, and 18 display an unusual reaction behavior against the azodicarboxylic esters 8a-c. Surprisingly, 4 reacts with 8a,b to produce 17a,b, whereas the reaction of 4 with 8c leads to 11 and the novel azomethine imine 15. Also the reaction of 18 with 8a-c gives in two cases 20 or 25 beside the azomethine imine 19. Furthermore, 7 reacts with 8a to form 26, whereas the reaction of 7 with 8c surprisingly yields 29. Spectroscopic data as well as the results of

The syntheses of some novel furan-containing monomers, N-[w-(furfurylcarbamoyl)aIkyl]methacrylamide (2) and N-furfurylmethacrylamide (3), and their corresponding polymers are described. Time-conversion measurements of their Diels-Alder reactions with dimethyl butynedioate by means of 'H NMR spectroscopy showed a deviation from pseudo-first-order kinetics. The influence of spacer length on the reaction velocity is explained by steric hindrance and neighboring group effects. No deviations from pseudo-first-order kinetics were observed during the Diels-Alder reaction of the low-molecular-weight model compounds N-[w-(furfurylcarbamoyl)alkyI]isobutyramide (8) and N-furfurylisobutylamide (9) under the same reaction conditions. MS (70 eV): m/z238 (M+), 210 (MC -CO), 142 (M+ -C4H30-CH,-NH-), 96 (Mf -CH-CO-NB-, J = 5,4 Hz, 1 H), 840 (t; --NH-CHz-C4H30, J = 5,