Acenaphthyle

C12H7N3O4 5-Niho-1,2-acenaphthyl-enedione dioxime Ebchaction-photometric Co, Cu, Fe 3... 

However, Kupletskaya and co-workers (100) have shown that the products of photodecomposition of CpFe(CO)2R (R = Ph, 1-naphthyl, 1-azulenyl, or acenaphthyl) in air-saturated solution were those expected from the trapping of Ar radicals by oxygen. These results could be construed as evidence for photoinduced Fe—Ar bond homolysis, but it is more likely that these products arise from a free radical reaction initiated by the oxygen present in solution. A similar free radical-initiated homolysis of an Fe—(tj -CsHs) bond has been postulated for CpFe(CO)2(V CsH5) 101). 

Figure 6. Efficiency of energy transfer from acenaphthyl chromophores to the 9-methylanthryl end-group in benzene/ether solvent mixtures.

Conclusion the ring expansion of arylcarbenes and arylnitrenes can involve discrete bicycloheptatriene intermediates though not necessarily so. Whether they do or not depends on the stabilities of these intermediates. Bicycloheptatriene instability is no obstacle to ring expansion. The ring expansion of acenaphthyl-carbene > may be cited as a further example. 

Significant shortcomings of such a technique for the preparation of 4,4 -keto-bis(naphthalic anhydride) are low yields of bis-acenaphthyls (4,4 -diacenaphthylmethane-15% 4,4 -diacenaphthyl ketone-5 %) and work with phosgene and carbon disulfide. 

This bisfnaphthalic anhydride) was prepared from acenaphthene derivative-4,4 -diacenaphthyl sulfone, which was synthesized by the interaction of acenaphthene with a mixture of dimethybulfate and sulfuric anhydride [94] or chlorosulfonic acid [95]. Sulfone-bis-(4,5-dicarboxynaphthyl l) dianhydride results from oxidation of bis-acenaphthyl with potassium permanganate in pyridine [94] ... 

Its isomer 2,2 -sulfone-bi naphthalic anhydride) resulted from sulfonation of acenaphthene with chlorosulfonic acid at 125-130 °C and subsequent oxidation of the obtained bis-(acenaphthyl)-sulfone with chromium anhydride [95] ... 

Another important group of bis(naphthalic anhydrides) - the so called bis(ketonaphthalic anhydrides) - was formed by the Fri lel-Crafts reaction between aromatic dicarboxylic acids dichlorides and two-fold molar amounts of acenaphthene and subsequent oxidation of tte obtained bis-acenaphthyls to bis(ketonaphthalic anhydrides) [111-115] according to heme 24. 

Oxidation of bis-acenaphthyls Interaction of bis-fo-phenyl-enediamine) with 4-(phenyl glyoxalyl) naphthalic anhydride... 

Acenaphthyl)imino]tributylphosphoranes, [(2-azulenyl)imino]-tributylphosphorane or [(3-indenyl)imino]tributylphosphoranes interact with substrates such as a,j9-unsaturated ketones or BrCH2C(0)Ph to give acenaphthopyridine, azulenopyridine or pyrrole derivatives. Aza-Wittig reactions of ortho(vinyl) substituted aryliminotriphenyl phosphoranes provide routes to arylquinolines or benzoxazines. 

When trans-cyclododecen-3-ol is subjected to CH2l2-Cu/Zn treatment the trans,anti-bicyclotridecane (66) is produced in a highly stereoselective manner. The Simmons-Smith cyclopropanation procedure has also been employed in a new synthesis of (+ )-caryophyllene and in the preparation of the parent cyclohepta[a]acenaphthyl-enyl cation. ... 

Annulated derivatives of cyclopentadienyl, such as indenyl and fluorenyP (Figure 3.15), as well as acenaphthyl-substituted cyclopentadienyl, and pentalenyl, are some of the most important cyclopentadienyl derivatives. They, and their derivatives with interarmular bridges, play a major role in controlling stereochemistry during the metal-catalyzed polymerization of olefins, as is described in Chapter 21. A number of permethylindenyl complexes have been reported.- ... 

Repo, T. Jany, G Hakala, K. Klinga, M. Polamo, M. Leskela, M. Rieger, B. Metallocene dichlorides bearing acenaphthyl substituted cyclopentadienyl rings Preparation and polymerization behavior. J. Organotnet. Chem. 1997, 549,177-186. 

FIGURE 18.8 Diimine nickel complexes used for CHD polymerization (An = acenaphthyl). 

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