- Thermal rearrangements of tetrahydroimidazo[1,5-b]isoxazole-2,3-dicarboxylates. Synthesis of 3H-imidazol-1-ium ylides and their silver derivatives
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Isoxazolines 2 from the cycloaddition of imidazoline 3-oxides 1 with DMAD undergo rearrangement to 3,4-dihydro-2H-imidazol-1-ium-1-(1,2-bis-methoxycarbonyl-2-oxo-ethanides) 3, which spontaneously undergo elimination to give 3H-imidazol-1-ium-1-(1,2-bis-me
- Co?kun, Necdet,?etin, Meliha
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experimental part
p. 2053 - 2060
(2010/04/26)
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- FT-IR kinetic and product study of the OH radical and Cl-atom - Initiated oxidation of dibasic esters
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Using a relative kinetic technique, rate coefficients have been measured, at 296 ± 2 K and 740 Torr total pressure of synthetic air, for the gas-phase reaction of OH radicals with the dibasic esters dimethyl succinate [CH3OC(O)CH2CH2C(O)OCH3], dimethyl glutarate [CH3OC(O)CH2CH2C(O)OCH3], and dimethyl adipate [CH3OC(O)CH2CH2CH2CH2 C(O)OCH3]. The rate coefficients obtained were (in units of cm3 molecule-1 s-1): dimethyl succinate (1.89 ± 0.26) × 10-12; dimethyl glutarate (2.13 ± 0.28) × 10-12; and dimethyl adipate (3.64 ± 0.66) × 10-12. Rate coefficients have been also measured for the reaction of chlorine atoms with the three dibasic esters; the rate coefficients obtained were (in units of cm3 molecule-1 s-1): dimethyl succinate (6.79 ± 0.93) × 10-12; dimethyl glutarate (1.90 ± 0.33) × 10-11 and dimethyl adipate (6.08 ± 0.86) × 10-11. Dibasic esters are industrial solvents, and their increased use will lead to their possible release into the atmosphere, where they may contribute to the formation of photochemical air pollution in urban and regional areas. Consequently, the products formed from the oxidation of dimethyl succinate have been investigated in a 405-L Pyrex glass reactor using Cl-atom-initiated oxidation as a surrogate for the OH radical. The products observed using in situ Fourier transform infrared (FT-IR) absorption spectroscopy and their fractional molar yields were: succinic formic anhydride (0.341 ± 0.068), monomethyl succinate (0.447 ± 0.111), carbon monoxide (0.307 ± 0.061), dimethyl oxaloacetate (0.176 ± 0.044), and methoxy formylperoxynitrate (0.032-0.084). These products account for 82.4 ± 16.4% C of the total reaction products. Although there are large uncertainties in the quantification of monomethyl succinate and dimethyl oxaloacetate, the product study allows the elucidation of an oxidation mechanism for dimethyl succinate.
- Cavalli, Fabrizia,Barnes, Ian,Becker, Karl Heinz
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p. 431 - 439
(2007/10/03)
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- REACTION OF ETHYL 2-AMINO-4,6-O-BENZYLIDENE-2-DEOXY-D-GLUCONATE WITH ACETYLENIC ESTERS
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Ethyl 2-amino-4,6-O-benzylidene-2-deoxy-D-gluconate adds to acetylenic esters to give sugar enaminones.The following acetylene derivatives have been employed: methyl propiolate, ethyl phenylpropiolate, and dimethyl acetylenedicarboxylate (6).With compound 6, the reaction leads to a mixture of the expected enaminone and the isomeric oxazolidine derivative.The structures and configurations of the new compounds were studied by spectroscopic and chemical methods.
- Miquel, Luis M. Vazquez de,Blazquez, Jose A. Serrano,Barros, Fernando J. Garcia,Guillen, Manuel Gomez
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