Formimidation

NH4)2Ce(N03)6, CH3CN, H2O, rt, 3 h, 84-95% yield. These conditions gave a j3-lactam formimide that was then hydrolyzed with NaHC03, Na2C03, H2O, rt, 2 h, 78-95% yield. " ... 

C2H4O2 107-31-3) see Felbamate Hosequinan Fluphenazine Methyprylon Pyrithyldione Retinol methyl formimidate hydrochloride (CjH ClNO 15755-09-6) see Imipenem methyl ( )-2-formyl-2-phenylacetate sodium salt (C H,NaO, 246180-40-5) see Felbamate iV-methylglycine... 

Egri et al. investigated the one-pot synthesis of N-(3-chlorophenyl)-aminomethylenemalonate (250), starting from equimolar amounts of 3-chloroaniline, diethyl malonate, and ethyl formimidate hydrochloride or ethyl orthoformate (73ACH217). The reaction involving ethyl formimidate hydrochloride was conducted in the presence of triethylamine at 120-130°C for 2 hr and then at 140°C for 80 hr. The ethanol formed in the reaction was continuously distilled off. N-(3-Chlorophenyl)aminomethyl-enemalonate (250) was obtained in 98-99% yields. 

In the case of ethyl formimidate hydrochloride, only a small amount of symmetrically substituted /V,N -diarylformamidine (248) could be detected. Because of the higher reactivity of the unsymmetrically substituted compound (247), a shorter reaction period could be applied. 

Egri et al. prepared A-(3,4-dialkoxyphenyl)aminomethylenemalonates (257) in over 90% yields in the reactions of 3,4-dialkoxyanilines, ethyl formimidate hydrochloride and diethyl malonate in the presence of trieth-ylamine (70MIP3). The reaction mixtures were gradually heated to 120°C for 2 hr and were then reacted at 140°C for 10 hr, while the ethanol formed was continuously distilled off. These phenylaminomethylenemalonates (257) were also prepared in over 93% yields in the reactions of 3,4-dialkox-yanilines, ethyl orthoformate, and diethyl malonate in the presence of catalytic amounts of water at 140°C for 60 hr. 

When a mixture of 3,4-methylenedioxyaniline, ethyl formimidate, and diethyl malonate was reacted at 110-I20°C for 6 hr, 30% of diethyl malonate and 19% of 3,4-methylenedioxyaniline were recovered. In addition, 18% of /V-(3,4-methylenedioxphenyl)aminomethylenemalonate (258), 11% of formamidine (259), and 7% of /V-(3,4-methylenedioxyphenyl)amino-methylenemalonamate (260) were isolated from the reaction mixture by means of column chromatography (74MI2). 

V-(6-Methyl-2-pyridyl)aminomethylenemalonate (306) was obtained in 86% yield in the reaction of a l l mixture of N-(6-methyl-2-pyridyl)-formimidate (305) and diethyl malonate at 150°C for l hr [74JAP(K)93370]. 

Amino-6-methylpyridine was reacted with ethyl orthoformate in the presence of acetic acid at 80-110°C for 1.5 hr to give formimidate (305),... 

Imipenem Imipenem, [5R-[5a,6a(R)]]-6-(l-hydroxyethyl)-3-[[2-[(iminomethyl)amino] ethyl]thio]-7-oxo-l-azabicyclo[3.2.0]hept-2-en-2-carboxyUc acid (32.1.3.1), is the only car-bapenem presently used in clinics. It is synthesized from thienamycin isolated from Streptomyces cattleya by reacting it with the methyl formimidate [179-182]. 

When R in the formimidate is —CH2CF3, 4,5-diamino-2,6-dicyano-pyrimidine forms. This occurs because —OCH2CF3 is a better leaving group than cyanide and is eliminated in the first step rather than cyanide. Cyanoformimidates are available from reaction of alcohols with cyanogen (75USP3883532). 

A useful method for the preparation of ortho esters was first reported by Pinner [12], who prepared simple and mixed ortho esters by the reaction of alkyl formimidate salts with an excess of alcohols at room temperature for example, see Eq. (10). With ethyl alcohol, the reaction was exothermic and... 

In the Reaction of Ketenes with N-(2-Pyridyl)formimidates and Schiff... 

Katagiri et al. investigated the reactions of ketenes with ethyl N-(2-pyridyl)formimidate and Schiff bases derived from 2-aminopyridines (83CPB2899, 83H597 84JHC407, 84MI3 85CPB2671). 

Acetyl-4//-pyrido[ 1,2-a]pyrimidin-4-one 186 was formed in the reaction of ethyl iV-(2-pyridyl)formimidate 187 (R = H) and ketene in acetone at ambient temperature for 2 days in 12% yield (83H597). It was assumed that diketene formed first from ketene, then it reacted with the formimidate 187 (R = H). When excess ketene gas was passed over formimidates 187 (R = H and Me) at 75°C for 0.5-1.5 hours without solvent, 4//-pyrido[ 1,2-a]pyrimidin-4-ones 188 and 7V-(2-pyridyl)formamides were obtained in 25-85% and 0-45% yields, respectively. From the 5-methyl derivative of the formimidate 187 (R = 5-Me) only pyridopyrimidinone 188 (R = 7-Me) was obtained. It was proposed that both products were formed by 1,4-... 

From the reaction mixture of dichloroketene, obtained from dichloro-acetyl chloride with triethylamine in situ, and N-(2-pyridyl)formimidates 187 in diethyl ether or in 1,2-dimethoxyethane, the following were isolated by column chromatography 3-chloro-2-ethoxy-4//-pyrido[ 1,2-a]-... 

In a similar way /V-(2-pyridyl)formimidates 187 (R = H, 3-Me) in methylene chloride were reacted with chloroketene 195, prepared from the appropriate carboxylic acid with trifluoroacetic anhydride followed by treatment of the mixed anhydride with triethylamine in situ, to give 3-ribofuranosyl-2-ethoxy-4//-pyrido[l,2-a]pyrimidin-4-ones 196 (R = H, 3-Me) and enamine 197 in 10—17% yields, respectively (84MI3 85CPB2671). 

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