An Efficient One-Step Method for the Conversion of β-(Dimethylamino)sty­renes into Arylacetonitriles

Abstract

A new simple and efficient one-step method for the preparation of arylacetonitriles by reaction of b-(dimethylamino)styrenes with hydroxylamine hydrochloride in formic acid solution is described.

Development of Green/Red-Absorbing Chromophores Based on a Coumarin Scaffold That Are Useful as Caging Groups

“…By comparison of the photophysical data ( Figure 4 and Table 2) of the three caged derivatives (25)(26)(27) with those of the corresponding model compounds (4, 6 and 7, respectively; see Figure 2 and Table 1), the same tendency was found: the absorption maxima shifted to increasingly longer wavelengths upon incorporation of one, two or three nitro substituents at the ortho and para positions of the phenyl ring conjugated at the 2-position of the coumarin moiety. However, replacement of the methyl group at position 4 by benzoyloxymethyl caused a slight blue-shift in the absorption maximum of the dinitro-(558 nm in 6 vs 551 nm in 26) and the trinitro-(607 nm in 7 vs 596 nm in 27) coumarin derivatives.…”

“…Ndiethylamino)coumarin (25) 154.5, 150.8, 145.2, 140.5, 139.8, 133.6, 129.8, 129.2, 128.7, 127.2, 124.8, 123.9, 119.4, 111.4, 109.4, 107.3, 97.1, 84.7, 62.3, 44.7, 12.5 9, 163.0, 154.1, 151.1, 147.6, 145.4, 142.8, 133.6, 131.9, 129.8, 129.1, 128.7, 126.7, 124.9, 120.9, 118.7, 109.8, 109.4, 107.1, 97.2, 79.4, 62.1, 45.0, 12. (2,4,6-trinitrophenyl)methylene) Ndiethylamino)coumarin (27) 154.0, 151.2, 149.9, 145.4, 144.2, 133.7, 129.9, 129.0, 128.7, 127.4, 125.1, 123.2, 115.9, 110.2, 108.3, 107.2, 97.0, 73.4, 61.9, 45.0, 12.4 methylene)coumarin (28). After evaporation under reduced pressure, the crude product was purified by column 7, 160.5, 152.9, 148.8, 144.8, 143.2, 138.1, 131.6, 127.9, 127.6, 126.8, 126.7, 125.2, 123.0, 122.0, 117.7, 107.5, 107.2, 104.9, 95.3, 82.4, 66.3, 42.8, 19.0, 10.6 in which the superscript "s" stands for standard samples, Abs is the absorbance at the excitation wavelength (λ Ex ), A is the integrated area of the corresponding emission spectrum, and n is the refractive index of the solvent used.…”

“…to give the desired coumarin derivative (25)(26)(27). Ndiethylamino)coumarin (25) 154.5, 150.8, 145.2, 140.5, 139.8, 133.6, 129.8, 129.2, 128.7, 127.2, 124.8, 123.9, 119.4, 111.4, 109.4, 107.3, 97.1, 84.7, 62.3, 44.7, 12.5 9, 163.0, 154.1, 151.1, 147.6, 145.4, 142.8, 133.6, 131.9, 129.8, 129.1, 128.7, 126.7, 124.9, 120.9, 118.7, 109.8, 109.4, 107.1, 97.2, 79.4, 62.1, 45.0, 12. (2,4,6-trinitrophenyl)methylene) Ndiethylamino)coumarin (27) 154.0, 151.2, 149.9, 145.4, 144.2, 133.7, 129.9, 129.0, 128.7, 127.4, 125.1, 123.2, 115.9, 110.2, 108.3, 107.2, 97.0, 73.4, 61.9, 45.0, 12.4 methylene)coumarin (28).…”

“…for 10 and 12; 0.82 mmol, 2 mol equiv. for 13) were dissolved in anhydrous ACN (20 mL) (25,26) or in a 1:1 mixture of anhydrous DCM/ACN (20 mL) (27) under an Ar atmosphere and protected from light.…”

Synthesis of 3-cyano-4,6-dinitrobenzo[d]isoxazole and its reactions with anionic nucleophiles

“…Recently, 14 we have developed a convenient and effi cient single step route to arylacetonitriles based on β (N,N dimethylamino)styrenes by treatment of starting enamines with NH 2 OH•HCl in formic acid. Other alde hyde derivatives such as imines and acetals can also be transformed into nitriles under the conditions found.…”