Chemistry of diazoacenaphthenones and diazoacenaphthenes

Abstract

Removal of the solvent left 8 mg (90%) of a mixture of anti-(CH3,C1)B (27%) and (CH3,Cl)(CH3,Cl)lactone (73%) as determined by NMR.Conversion of (CH3,CH3)(CH3,CH3)lactone to anti-(CH3,CH3)B. The lactone (28 mg, 0.15 mmol), initially a suspension, was stirred in sodium hydroxide (15 mL, 0.1 , 1.5 mmol) for 2 h, the light yellow solution was acidified (ca. pH 2.5), the solution was stirred for a few hours and then extracted with CHC13, the extract was dried (MgS04), and the solvent was removed to yield 26 mg (93%) of anit-(CH3,CH3)B (90%) and lactone (10%) as shown by NMR.A similar experiment with (CH3CH2,CH3)(CH3CH2,CH3) lactone yielded onti'-(CH3CH2,CH3)B (79%) and lactone (21%).Rate Measurements. Low Rates. Bimane in CH3CN (0.1 mL) was added to temperature-equilibrated buffer (3 mL) contained in a quartz cell. The absorption spectrum was measured with a Cary Model 17 spectrophotometer. For several syn-bimanes, fluorescence spectra were recorded with a Hitachi-Perkin-Elmer MPF 4.High Rates. The bimane solution was added to the buffer being stirred by a small Teflon-coated bar moved by a small motor mounted below the cell holder with the chart paper running and the wavelength fixed at the absorption maximum. Smooth curves were usually observed after 1-2 s (mixing time). Sodium phosphate (pH 7-8) and sodium carbonate (pH 9-10) buffers were used. The pH values were measured at 25 °C and corrected to 50 °C with temperature factors recorded in the literature.31

100 Years of the Wolff Rearrangement

“…[100] The photolysis of 2-diazo-1-indanone (108) in MeOH was found to afford both 2-methoxy-1-indanone (110, 50%) and methyl benzocyclobutene-1-carboxylate (109, 15%). [101] Photolysis of the diazo ketones 111, [102] 112, [103] and 113, [104] leads to OϪH insertion but does not induce ring contraction. Electronic effects (111), as well as ring strain of the predicted products (112,113), are thought to impede the Wolff rearrangement.…”

“…Exceptions to this rule occur if CϪH insertion is strongly favored or Wolff rearrangement is strongly disfavored. [103] and related species [106] insert readily into CϪH bonds of the solvent, rather than forming highly strained Wolff products. Owing to the low migratory aptitude of OR, CϪH insertion is often the only reaction of diazoesters 117, with X ϭ H, [107] SiMe 3 , [108] CO 2 R, [64,107,109] COCF 3 , [110] and CONR 2 .…”

“…Some carbonyl carbenes are trapped by nitriles with formation of 1,3-oxazoles, [116] as exemplified by 124. [116a] Not surprisingly, 111 [102a] and 112 [103] (Scheme 18) also react with alkynes to give furans, and with nitriles to give 1,3-oxazoles.…”

“…This route is particularly useful if the diketones can be obtained by oxidation of hydrocarbons such as acenaphthene and phenanthrene. [103] Diazo transfer to beyeran-16-one failed whereas SeO 2 -oxidation followed by BamfordϪStevens reaction afforded the desired diazo ketone. [432] As a rule, ring closure is not a practical approach to cyclic α-diazo ketones.…”

Novel quinoxaline derivatives containing arylaminated aceanthrylene for organic red-light emitting diodes

“…This compound was prepared from oxalyl chloride and anthracene by the reported procedure (mp ¼ 268 C) [31].…”