Electronic structure acetic anhydride

Resonance stabilization in the products is best illustrated by the reactant anhydrides (Figure 3.10b). The unpaired electrons of the bridging oxygen atoms in acetic anhydride (and phosphoric anhydride) cannot participate in resonance structures with both electrophilic centers at once. This competing resonance situation is relieved in the product acetate or phosphate molecules. 

The one-step reaction of H2prCl6] with MeC02Li under 02 in a mixed solvent of acetic acid and acetic anhydride yields the Ir11 binuclear complex [Ir2(/u-02CMe)2Cl2(C0)2].483 Crystal-structure determinations of [Ir2(/x-02CMe)2Cl2(C0)2L2], (295), where L = MeCN, DMSO, and py, are reported. The one-electron oxidation product for (295), L = py, is EPR active at 77 K the odd electron occupies the 6Ir Ir orbital. 

History. Braun and Tschemak [23] obtained phthalocyanine for the first time in 1907 as a byproduct of the preparation of o-cyanobenzamide from phthalimide and acetic anhydride. However, this discovery was of no special interest at the time. In 1927, de Diesbach and von der Weid prepared CuPc in 23 % yield by treating o-dibromobenzene with copper cyanide in pyridine [24], Instead of the colorless dinitriles, they obtained deep blue CuPc and observed the exceptional stability of their product to sulfuric acid, alkalis, and heat. The third observation of a phthalocyanine was made at Scottish Dyes, in 1929 [25], During the preparation of phthalimide from phthalic anhydride and ammonia in an enamel vessel, a greenish blue impurity appeared. Dunsworth and Drescher carried out a preliminary examination of the compound, which was analyzed as an iron complex. It was formed in a chipped region of the enamel with iron from the vessel. Further experiments yielded FePc, CuPc, and NiPc. It was soon realized that these products could be used as pigments or textile colorants. Linstead et al. at the University of London discovered the structure of phthalocyanines and developed improved synthetic methods for several metal phthalocyanines from 1929 to 1934 [1-11]. The important CuPc could not be protected by a patent, because it had been described earlier in the literature [23], Based on Linstead s work the structure of phthalocyanines was confirmed by several physicochemical measurements [26-32], Methods such as X-ray diffraction or electron microscopy verified the planarity of this macrocyclic system. Properties such as polymorphism, absorption spectra, magnetic and catalytic characteristics, oxidation and reduc-... 

Cava and Pollack s elegant synthesis of benzo[c]thiophene52 has been extended to the synthesis of, for example, naphtho[l,2-c]thio-phene (47),52 methyl benzo[c]thiophene-5-carboxylate,54 and 1,3-dimethyl- (48)55 and l,3,4,6-tetraphenylthieno[3,4-c]thiophene (49).56 The last compound is of particular interest because it is a remarkably stable (cf. compound 48 which only exists transiently) nonclassical thiophene containing ten n electrons for which the only uncharged resonance structure (49) contains a tetravalent sulfur atom. When the sulfoxide (50) is pyrolyzed over aluminum oxide, it gives the parent cyclic sulfide and 51 by disproportionation.57 However, when 50 is heated in acetic anhydride in the presence of iV-phenylmaleimide,... 

The mechanism of acid-catalyzed cleavage of glycosidic bonds could be perhaps better understood by studying the mechanism of acetolysis, since the acetolysis is performed in the absence of water (most often in acetic anhydride), and thus, the electronic effects that exist in each glycopyranoside structure will not be... 

Diacetyl sulfide exists in the gas phase primarily in a conformation with a planar heavy-atom skeleton, and with one C = O bond syn and one anti with respect to the further S-C bond. Analysis of the electron diffraction data indicated that there must be less than 10% of the syn, syn conformer, and calculations using MP2 and B3LYP methods with the 6-31-I-G basis set placed the syn, syn form between 4 and 10 kJ mol above the syn, anti form, while the anti, anti conformation was less stable by about 30 kJ mol . Vibrational spectra showed that more than 99% of the gas was one conformer, and the crystal structure also revealed planar molecules with the same conformation as the gaseous molecules. Diacetyl sulfide thus resembles most related compounds in its conformational preferences, although apparently it differs from acetic anhydride, which has been reported to consist of a mixture of non-planar conformers. Distances in the ra structure of diacetyl sulfide include C = O 119.8(2) and 119.6 pm (the second parameter, without a quoted uncertainty, was set to have a fixed difference from the first parameter, as computed by the MP2... 

---