Thermal cyclization of (2-Ethynylphenyl)triazenes: facile synthesis of substituted cinnolines and isoindazoles

High-temperature intramolecular cyclization of N, N-dialkyl-N'-(4-substituted-2-ethynylphenyl)triazenes provides under neutral conditions both 6-substituted cinnolines and 5-substituted isoindazoles in moderate to excellent yields.     

The constant-volume-velocity nature of hearing aids: conclusions based on computer simulations

In the literature there are several references which imply that various parts of a hearing aid are sources of constant volume velocity. Reported herein are the findings of an investigation of the validity of such statements. A computer scheme, referenced elsewhere, for modeling in situ hearing aids was utilized to test the constant-volume-velocity hypothesis. In particular, capabilities of the receiver, ear hook, and earmold tip to deliver constant volume velocity were investigated via a computer. To facilitate such an investigation, a universal receiver/earmold model was created. This model was broken down into "source" and "load"at three locations: the receive output, output of the ear hook, and medial tip of the earmold. At each location comparisons were made between computed values of source and load impedance. The constant-volume-velocity hypothesis was assumed to be valid for those cases where source impedance was much, much greater than load impedance. Plots of such impedances show that, for the cases investigated, this rarely occurred, except over certain frequency bands. With the exception of in-the-ear hearing aids, these results appear to contradict inferences made in the literature about the constant-volume-velocity nature of hearing aids.     

Reactions of methylpyrylium,thiapyrylium, and flavylium salts with tetracyanoethylene

The reaction of 2- or 4-methyl-2,6-diphenylpyrylium perchlorate with tetracyanoethylene (TCNE) in pyridine gives 2- or 4-(2,3,3-tricyanopropylidene)-2,6-diphenylpyran in good yield. Similar results are obtained from 2- or 4-methyl-2,6-diphenylthiapyrylium and 4-methylflavylium perchlorates. In one case a stable charge-transfer salt is isolated from the reaction of a methylene base and TCNE. The reaction mechanism of dye formation is discussed.     

Synthèse du mèthyl-1 diformyl-2,3 pyrrole,de la méthyl-1 pyrrolo[2,3-d] pyridazine et de la méthyl-1 oxo-6 (6h)cycloheptatrieno[b] pyrrole

This communication describes the synthesis of l-methyl-2,3-diformylpyrrole. This new compound is used to prepare a new heterocycle, l-methylcyclohepta[b]pyrrol-6-one and thus allows a new synthesis of l-methylpyrrolo[2,3-d]pyridazine.     

Dimethyldihydropyrene-dehydrobenzoannulene hybrids: studies in aromaticity and photoisomerization

The synthesis and study of dehydrobenzoannulene (DBA)-dimethyldihydropyrene (DDP) hybrids as models for the investigation of aromaticity in weakly diatropic systems is reported. Three new monofused DBA-DDP hybrids have been synthesized, and their NMR spectra are discussed with regard to quantifying the aromaticity remaining in multibenzene-fused DBAs. Nucleus-independent chemical shifts, determined at a series of locations for each compound, bond lengths, and (1)H and (13)C NMR chemical shifts were calculated and used to probe the aromaticity of these hybrids. Systems where more than one annulene/DBA is fused to the DDP core have also been obtained, and their potential use in photoinduced isomerization applications is discussed.     

Dynamics of a poly(ethylene oxide) tracer in a poly(methyl methacrylate) matrix: remarkable decoupling of local and global motions

The tracer diffusion coefficient of unentangled poly(ethylene oxide) (PEO, M=1000 gmol) in a matrix of poly(methyl methacrylate) (PMMA, M=10 000 gmol) has been measured over a temperature range from 125 to 220 degrees C with forced Rayleigh scattering. The dynamic viscosities of blends of two different high molecular weight PEO tracers (M=440 000 and 900 000 gmol) in the same PMMA matrix were also measured at temperatures ranging from 160 to 220 degrees C; failure of time-temperature superposition was observed for these systems. The monomeric friction factors for the PEO tracers were extracted from the diffusion coefficients and the rheological relaxation times using the Rouse model. The friction factors determined by diffusion and rheology were in good agreement, even though the molecular weights of the tracers differed by about three orders of magnitude. The PEO monomeric friction factors were compared with literature data for PEO segmental relaxation times measured directly with NMR. The monomeric friction factors of the PEO tracer in the PMMA matrix were found to be from two to six orders of magnitude greater than anticipated based on direct measurements of segmental dynamics. Additionally, the PEO tracer terminal dynamics are a much stronger function of temperature than the corresponding PEO segmental dynamics. These results indicate that the fastest PEO Rouse mode, inferred from diffusion and rheology, is completely separated from the bond reorientation of PEO detected by NMR. This result is unlike other blend systems in which global and local motions have been compared.