Ethyl 2-formylphenyl

Formylphenyl ethyl tellurium was obtained by lithiation of 1,3-dimethyl-2-phenylimidazolidine, reaction of the lithiated product with diethyl ditellurium, and hydrolytic cleavage of the imidazolidine ring1. 

Macrocycle LXXXVIII was prepared (13) in an 8% yield from the reaction of the disodium salt of ethane-1,2-dithiol with di(2-bromo-ethyl)amine in ethanol at high dilution, and it was found to complex with Ni(II) and Co(II) ions when these were added as salts. A macrocycle containing the same donor atoms (LXXXIX) has been obtained in the form of complexes (87) by the template reactions of l,2-bis(2-aminophenylthio)ethane and 1,4-bis (2-formylphenyl)-1,4-dithiabutane with Ni(II) and Co(II) perchlorates. Iron, cobalt, nickel, and zinc as their M(II) perchlorates have been used as templates in the formation of XC (55, 133). 

In 1992, Molina et al. synthesized partial structures of lavendamycin using the aza-Wittig reaction as the main strategy (68) to form a /3-carboline at the 2-position of a quinoline (Scheme 23) (68). The reactions of the iminophosphorane 194, prepared from 3-formyl-l-methyl indole by treatment with ethyl azidoacetate and triphenylphosphine, with the 2-formyl-quinoline derivatives 195 in toluene at 160°C in a sealed tube gave the corresponding quinoline derivatives 196 and 197. Treatment of iminophosphorane 194 with pyruvaldehyde yielded the key j3-carboline intermediate 198, which was reacted alternatively with the 2-aminobenzaldehyde 199 and JV-(0-formylphenyl)triphenyliminophosphorane 200 to obtain the corresponding partial structures of lavendamycin, 201 and 202, respectively. 

R = H, D) were obtained from the 6-methyl-3-ester derivative and its 6,7,8-deuterio derivative 291 (R = Me, R = COOEt, R -R" = H, D). These derivatives were transformed into 293 (R = H, D) by heating in POCI3. Optically active 291 (R = Me, R = COOEt, R -R = H) afforded optically active 6,7-dihydro-477 294 (R = H), but optically inactive AH-pyrido[l, 2-a]pyrimidine 293 (R = Me, R = COOEt, R = H). Similarly ethyl 9-(A -phenyl-iV-methylamino)-6-methyl-4-oxo-6,7-dihydro-4/7-pyrido[l,2-a] pyrimidine-3-carboxylate gave 9-[iV-(4-formylphenyl)-A -methylamino]-7-dimethylaminomethylene-6-methyl-6,7-dihydro-4-oxo-4/f-pyrido[l,2-u]pyr-imidine-3-carboxylates in a mixture of POCI3 and DMF at lower (20-25 °C) and higher (95 100°C) temperatures, respectively. 9-(Ethoxycarbonyl-methyl)-4-oxo-6,7-dihydro-47/-pyrido[l,2-a]pyrimidine-3-carboxylate 158 (but not 9-ethoxycarbonylmethylene-6,7,8,9-tetrahydro derivative 157) was also transformed into ethyl 9-(ethoxycarbonylmethyl)-7-(l-chloroethyl)-4-oxo-477-pyrido[l, 2-a]pyrimidine-3-carboxylate (99T10221). 

First, a homemade pre-monomer , 4-formylphenyl methacrylate 3, was synthesized to introduce the aldehyde component for conducting the Biginelli reaction. The monomers 1 and 2 were then obtained through reacting the pre-monomers 3 with ethyl acetoacetate and either urea or thiourea, respectively. With the help of a catalytic amount of concentrated hydrochloride (HCl), the two monomers were successfully synthesized in refluxed ethanol at moderate yields by recrystaUization. 

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