Thiophenes orientation

Using these assumptions and conventions, Imoto and co-workers have correlated a number of series of reactions of thiophenes and furans. The reactions studied are the acid-base equilibria pK values) and the acid catalyzed methylations (thiophenes only) of thiophene-and furan-carboxylic acids and the alkaline hydrolyses of their ethyl esters the side-chain bromination of the a-acetylthiophenes, and the a-mercuration of thiophenes and the polarographic half-wave potentials of the methyl esters of thiophene- and furan-carboxylic acids and of nitrothiophenes. The pK values were determined and the ester hydrolyses studied for all three substitution orientations in the thiophene series. For the 4-R-2-Y and 5-R-2-Y series, the p-values do not appear significantly different and the data could probably be combined into a single series unfortunately, however, no limits of accuracy are reported for the p-values, and some of the raw data are not readily available so recalculation is not easily possible. For the 5-R-3-Y series the p-values deviate considerably from the other values however, whereas they are higher for the pK values, they are lower for the ester hydrolyses, and it is possible that the differences are neither systematic nor significant. 

Photolysis of 2,3-bis(trifluoromethyl)thiophene gave an isomer mixture of 2,3- and 3,4-bis(trifluoromethyl) thiophenes and Dewar thiophenes. The 2,5- analogue gave 2,4-bis(trifluoromethyl)thiophene via an intermediate that was not the Dewar thiophene. This indicated that provided they are orientated correctly, two trifluoromethyl groups are sufficient to isolate a Dewar thiophene (84TL1917). 

The studies of ammonia synthesis over Fe and Re and the hydrodesulfurization of thiophene over Mo, described above, illustrate the importance and success of our approach of studying catalysis over single crystal samples at high pressures. The use of surfaces having a variety of orientations allows the study of reactions that are surface structure sensitive 6Uid provides insight into the nature of the catalytic site. Here we have shown that the ammonia synthesis... 

Finally, a more MB-oriented patent concerns a gene which participates in desulfurizing enzyme expression inhibition [107], The production of the microorganism which highly expresses the desulfurizing enzyme, even when cultured in the presence of a sulfate as only one sulfur source was included. The application was focused towards the decomposition of thiophene compounds. 

Thin polymer films have been prepared by surface catalysis in ultrahigh vacuum and electrochemical deposition from solution. These two routes of synthesis result in poly(thiophene), poly(aniline) and poly(3,5-lutidine) films that have similar infrared spectra. These polymer films are highly orientationally ordered the rings are perpendicular to the surface in poly(thiophene) and poly(3,5-lutidine) films, and the phenyl rings are parallel to the surface in poly(aniline). 

In this paper we describe the preparation of thin polymer films by surface catalysis and anodic deposition. The results indicate that both synthesis routes produce orientationally ordered films that have similar infrared spectra. It is also shown that thin ordered films of poly(thiophene) have different electrochemical behavior than the fibrous films that are electrically conducting. 

Aromatic molecules can be polymerized catalytically on clean metal surfaces, or electrochemically to produce oriented polymer films. Initial adsorption of aromatic molecules occurs by electron donation from the aromatic molecule to the surface. This electron donation creates radical cations that can polymerize. Molecular orientation in the films depends on the stable bonding configuration of the radical cation. Thiophene, pyridines, and pyrrole all polymerize with the ring substantially perpendicular to the surface, whereas aniline polymerizes with the phenyl rings parallel to the surface. The catalytically... 

A complete analysis of the IR spectra of thienothiophenes 1 and 2 in the gaseous, liquid, and crystalline states was carried out by Kimel feld et a/. The following isotopically substituted compounds were also studied 2-deuterothieno[2,3-h]thiophene (l-2d), 2-deuterothieno[3,2-I)]-thiophene (2-2d), 2,5-dideuterothieno[2,3-h]thiophene (l-2,5-d2), and 2,5-dideuterothieno[3,2-h]thiophene (2-2,5-dj). The IR spectra of oriented polycrystalline films of all compounds were measured in polarized light, and Raman spectra of liquid thienothiophenes 1, l-2d, and 1-2,5-dj, of crystals of thienothiophenes 2 and 2-2,5-d2 and melts of thienothiophenes 2 and 2-2d were analyzed. The planar structure of point-group Cj, for thienothiophene 1 in the liquid and gaseous states was assumed. Then the thirty vibrations of compounds 1 and l-2,5-d2 can be divided into four symmetry classes Aj (11), Bj (10), A2 (4), and B2 (5) the vibrations of molecule (l-2d) (C, symmetry) are divided into two classes A (21) and A" (9). 

It has been described [192] that the orientation of 2-mercaptomethylthiophene molecules adsorbed on Au(lll) is almost vertical at the saturation coverage. At low coverage, in turn, the molecules form striped islands, within which the thiophene rings are tilted by 45 10° with respect to the surface normal. 

H-NMR spectra of the dihydrobenzo[c]thiophene 5-oxides 5 have been investigated in various solvents510. The a-proton resonates at lower frequency when it is cis to the sulfoxide oxygen compared to the trans orientation. 

LB films prepared from poly-thiophene-3-acetic acid stearylamine or sulfonated polyaniline stearylamine polyion complexes, transferred to substrates, and doped by SbCls Absorption and infrared spectra, X-ray diffraction, and conductivity measurements Lateral d.c. conductivities of doped films were moisture dependent and were as high as 2 S cm"molecular organization consisted of randomly oriented polymers lying as extended chains parallel between the substrates and sandwiched between layers of stearylamine molecules whose chains were interdigitated 772... 

It is assumed that the heterocyclic core structure is responsible for the appropriate orientation of the aromatic rings in space and finally for binding to the enzyme. A wide variety of heterocycles can serve as templates, i.e. pyrrole, thiazole, oxazole furane, furanone, imidazole, isoxazole, pyrimidine and thiophene, but at the moment pyrazole and cylopentenone seem to be the most appropriate for achieving COX-2 specificity. For optimal activity, one aromatic ring must be substituted with a methylsulfonyl or a sulfonamide substituent in the para position. Substitution at position 4 of one of the aromatic systems with a sulfonamide or a methylsulfonyl group is essential for COX inhibition. Replacement of the methylsulfonyl group by a sulfonamide group reduces COX-2 selectivity but improves oral bioavailability. 

Most work, however, has been done on systems with several substitution sites. Formylation of the thieno[2,3-6]pyrroles (389) and (390) showed that in the former case, formylation takes place predominantly (90%) at C-5, and 10% at C-4. An electron-attracting substituent at C-5, as in 390, orients substitution into the thiophene ring (95% at C-2).407... 

Electron donor 2-substituents orient substitution in furan, thiophene and selenophene into the 5-position. In pyrrole, although the ratio of a to (3 reactivity is much smaller than in the other five-membered rings, 5-substituted 2-alkylpyrroles still appear to be the major products. 

Thieno[2,3-6]thiophene (7), upon reaction with DMF-POCb, was readily formylated at C-2 to give the aldehyde (54). Less than 0.1% of the C-3 substituted product was detectable by GC when exactly one equivalent of POCl3 was used. The orientation of the substituent was confirmed by conversion to the known acid (55) by oxidation, and by reduction to the known 2-methyl derivative (56 Scheme 12) (76AHC(19)123). 

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