Thiophen estimation

Pyrrole has a planar, pentagonal (C2 ) stmcture and is aromatic in that it has a sextet of electrons. It is isoelectronic with the cyclopentadienyl anion. The TT-electrons are delocalized throughout the ring system, thus pyrrole is best characterized as a resonance hybrid, with contributing stmctures (1 5). These stmctures explain its lack of basicity (which is less than that of pyridine), its unexpectedly high acidity, and its pronounced aromatic character. The resonance energy which has been estimated at about 100 kj/mol (23.9 kcal/mol) is intermediate between that of furan and thiophene, or about two-thirds that of benzene (5). 

In summary, all estimates of resonance energies indicate a decrease in aromaticity in the sequence benzene > thiophene > pyrrole > furan. Similar sequences are also found for the benzo[6] and dibenzo analogues. A somewhat different sequence is found for the benzo[c] fused heterocycles with isoindole > benzo[c]thiophene > benzo[c]furan. As would be anticipated, the resonance energies for the benzo[c] heterocycles are substantially lower than those for their benzo[6] isomers. 

Mercury(II) acetate tends to mercurate all the free nuclear positions in pyrrole, furan and thiophene to give derivatives of type (74). The acetoxymercuration of thiophene has been estimated to proceed ca. 10 times faster than that of benzene. Mercuration of rings with deactivating substituents such as ethoxycarbonyl and nitro is still possible with this reagent, as shown by the formation of compounds (75) and (76). Mercury(II) chloride is a milder mercurating agent, as illustrated by the chloromercuration of thiophene to give either the 2- or 2,5-disubstituted product (Scheme 25). 

It is estimated that thiophene reacts with phenyl radicals approximately three times as fast as benzene. Intramolecular radical attack on furan and thiophene rings occurs when oxime derivatives of type (112) are treated with persulfate (8UCS(Pt)984). It has been found that intramolecular homolytic alkylation occurs with equal facility at the 2- and 3-positions of the thiophene nucleus whereas intermolecular homolytic substitution occurs mainly at position 2. 

Example 7 Estimate the Vapor Pressure of Thiophene at 500 K.. . . Example 8 Estimate the Vapor Pressure of Acetaldehyde at 0 C. . . Ideal Gas Thermal Properties. 

The SH, SCHs, and weakly directing halogens cause small shifts, which to a large extent are determined by magnetic anisotropy effects, especially in the case of the halogens. Attempts have been made to estimate these effects for the other thiophenes. Except for orthohydrogens, these effects are usually very small. 

The thermodynamic properties of thiophene,2-methylthiophene, ° and 3-methylthiophene have been computed from careful measurements of the heat capacity of the solid, liquid, and vapor states, the heat of fusion, the heat of vaporization, and the heat of combustion. From the heat of combustion of thiophene and from thermochemical bond energies, the resonance energy of thiophene has been re-estimated to be only 20 kcal/mole. 

Only within the past few years have serious attempts been made to estimate quantitatively the differences in reactivity between thiophene and benzene and between the 2- and 3-position of thiophene. Careful investigation on the acid-induced exchange of deuterium and tritium have shown that the ratios of the exchange rates in the 2- and 3-positions are 1045 61 for deuterium and 911 60 for tritium in 57% by weight aqueous sulfuric acid at 24.6°C. A kinetic isotope effect in the isotopic exchange has been found to be k-r/kr, = 0.51 0.03 in the 2-position and kr/kjy — 0.59 0.04 in the... 

Thiophene (C4H4S) is representative of the organic sulfur compounds that are hydrogenated in the commercial hyditodesulfurization of petroleum naphtha. Estimate both the combined and effective diflfusivities for thiophene in hydrogen at 660 °K and 3.04 MPa in a catalyst with a BET surface area of 168 m2/g, a porosity of 0.40, and an apparent pellet density of 1.40 g/cm3. A narrow pore sized distribution... 

Structures and nomenclature for the most important five-membered monocycles with one or more heteroatoms are depicted in Scheme 1. The aromaticity scale in five-membered heterocycles has been long debated.97-101 The decreasing order of aromaticity based on various criteria is (DRE values in kcal/ mol) benzene (22.6) > thiophene (6.5) > selenophene > pyrrole (5.3) > tellurophene > fur an (4.3). Pyrrole and furan have comparable ring strains (Scheme 38). The aromaticity of furan is still controversial 100 the NMR shielding by ring current estimated it at about 60% of the aromaticity of benzene, and other methods reviewed earlier102 estimated it at less than 20%. 

Bipolar Molecular Glasses. Recently, bipolar molecular glasses have been described that allow both injection of holes and electrons (Fig. 3.30). 2- 4-[bis(4-methylphenyl)amino]phenyl -5-(dimesitylboryl)thiophene (PhAMB-lT, 68) and 2- 4-[bis(9,9-dimethylfluorenyl)amino]phenyl -5-(dimesitylboryl)thiophene (F1AMB-1T, 69) show oxidation potentials of 0.62 and 0.58 V, and reduction potentials of —2.13 and —2.01 V vs. Ag/0.01 Ag+, respectively [145]. Oxidation as well as reduction leads to stable radical ions. With the conversion rules given above, the HOMO and LUMO levels can be estimated to be approximately at —5.3 and —2.8 eV. In comparison, for the bipolar compound 70, consisting of triarylamine and oxadiazole moieties, the values are —5.5 and — 2.7eV [129]. However, in this case no data on the stability of the radical ions are available. 

Methyl cation affinities of benzene and some substituted benzenes have been calculated. These follow a simple additivity rule and the value for benzene shows good agreement with the experimental estimate. Conclusive evidence is presented that these values are linearly related to the corresponding proton affinities. The competition between deuteriation and alkylation in the reaction of radiolytically formed perdeuterio ethyl cations with iV-methylpyrrole and with thiophene has been studied. Deuteriation, the Brpnsted acid pathway, predominates and intramolecular selectivities have been determined for each reaction. ... 

Unavailable because experimental methods for estimation of this parameter for substituted thiophenes are lacking in the documented literature... 

Let us now direct our attention to the P=C bond in phosphaalkene ion-radicals. The literature contains data on two such anion-radicals in which a furan and a thiophene ring are bound to the carbon atom, and the 2,4,6-tri(tert-butyl)phenyl group is bound to the phosphorus atom. According to the ESR spectra of anion-radicals, an unpaired electron is delocalized on a n orbital built from the five-membered ring (furanyl or thienyl) and the P=C bond. The participation of the phosphaalkene moiety in this MO was estimated at about 60% and some moderate (but sufficient) transmission of the spin density occurs through the P=C bridge (Jouaiti et al. 1997). Scheme 1.6 depicts the structures under discussion. 

Chromatographic separation clarified the peculiarities of acetonyl-thiothiophene cyclization in the presence of duminum chloride. " Gas-liquid chromatography also allowed quantitative estimates of the relative reactivities of thiophene and the isomeric thienothiophenes 1 and... 

Aromatic substitution reactions are often complicated and multistep processes. A correlation, however, in many cases can be found between the charged attacking species and the electron density distribution in the molecule attacked during electrophilic and nucleoph c substitution. No such correlation is expected in radical substitution where the attacking particles are neutral, rather a correlation between the reactivities of separate bonds and a free valency index of the bond order. This allows the prediction of the most reactive bonds. Such an approach has been used by researchers who applied quantum calculations to estimate the reactivities of the isomeric thienothiophenes and to compare them with thiophene or naphthalene. " Until recently quantum methods for studying reactivities of aromatics and heteroaromatics were developed mainly in the r-electron approximation (see, for example, Streitwieser and Zahradnik ). The M orbitals of a sulfur atom were shown not to contribute substantially to calculations of dipole moments, polarographic reduction potentials, spin-density distribution, ... 

Semiempirical methods of calculation with consideration of all valence electrons have been used only recently but already have given results on the reactivities of some aromatic and heteroaromatic com-pounds. " Thus, to analyze the reactivities of thiophene and the isomeric thienothiophenes 1-3 to electrophilic substitution, the semiempirical SCF LCAO MO method CNDO/2 was used, taking into account all valence electrons.The 3s, 3p, and 3d orbitals have been taken into account for the sulfur atom. Tlie reactivities were estimated from the difference between bond energies of the initial and the protonated molecule (in a complex). ... 

The reactivities of isomeric thienothiophenes calculated in n -electron approximation by the PPP method, and those calculated considering all valence electrons, show reasonable agreement. It should be noted, however, that the choice of parameters in PPP calculations is somewhat arbitrary, especially for heavy atoms (e.g., sulfur). This may lead to a discrepancy between theoretical (in 7r-electron approximation) and experimental estimation of reactivities. For example, Clark applied the semiempirical method PPP SCF MO to calculate the reactivities of different positions in thienothiophenes 1—3, thiophene, and naphthalene from the localization energy values and found the following order of decreasing reactivity for electrophilic substitution thieno[3,4-b]-thiophene (3) > thieno[2,3-Z>]thiophene (I) > thieno [3,2-b]thiophene... 

Reported relative rates ( hs/ hp,) are quite varied. As shown in Fig. 11, this ratio has been estimated to be from 1.5 (55) to as little as 0.13 (25) for some multiaromatic thiophene derivatives. Phenylnaphthalene was also reported to have a very different preference for the position of naphthalene ring hydrogenation in independent studies as compared to being an intermediate in the reaction matrix (56, 57). 

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