Formaldehyde, reaction with diethyl

Fluorenylamine, 40,5 Formaldehyde, reaction with diethyl malonate to form diethyl bis-(hydroxymethyl)malonate, 40,27 Formamide, condensation with 4,4-dimethoxy-2-butanone to give 4-methylpyrimidine, 43, 77 Formic acid, and hydrogen peroxide, with indcne, 41, 53... 

When the 3,7-diaza-l,9-nonanediamine-Cu(II) complex (n = 1) was treated with formaldehyde and nitroethane, the nitro-substituted macrocycle was the only product. Reduction of the nitro group by zinc in aqueous acid gave the amine-substituted macrocycle as shown above. Other peraza-crowns were obtained starting with other tetraamines (Comba et al., 1988a, 1988b Law-rance and O Leary, 1987). A similar reaction with diethyl malonate gave only a 2% yield of the corresponding macrocycle (Lawrance and O Leary, 1987). 

Reactions with Ammonia and Amines. Acetaldehyde readily adds ammonia to form acetaldehyde—ammonia. Diethyl amine [109-87-7] is obtained when acetaldehyde is added to a saturated aqueous or alcohoHc solution of ammonia and the mixture is heated to 50—75°C in the presence of a nickel catalyst and hydrogen at 1.2 MPa (12 atm). Pyridine [110-86-1] and pyridine derivatives are made from paraldehyde and aqueous ammonia in the presence of a catalyst at elevated temperatures (62) acetaldehyde may also be used but the yields of pyridine are generally lower than when paraldehyde is the starting material. The vapor-phase reaction of formaldehyde, acetaldehyde, and ammonia at 360°C over oxide catalyst was studied a 49% yield of pyridine and picolines was obtained using an activated siHca—alumina catalyst (63). Brown polymers result when acetaldehyde reacts with ammonia or amines at a pH of 6—7 and temperature of 3—25°C (64). Primary amines and acetaldehyde condense to give Schiff bases CH2CH=NR. The Schiff base reverts to the starting materials in the presence of acids. 

Diethyl malonate, reaction with formaldehyde to form diethyl bis-(hydroxy methyl) malonate, 40, 27... 

Dioxo-8a-methyl-l, 2,3,4,6,7,8,8a-octahydronaphthalene has been obtained through the reaction of 2-methyl-l,3-cyclohexane-dione with acetonedicarboxylic acid and formaldehyde,3 4-diethyl-amino-2-butanone methiodide,3 pyridine and 4-diethylamino-2-butanone,4 triethylamine and 4-diethylamino-2-butanone,5 and by cyclization of 2-methyl-2-(3-oxobutyl)-l,3-cyclohexanedione using either aluminum fer/-butoxide or piperidine phosphate as catalyst.6 7... 

In preparation for the eventual removal of the undesired oxygen function at C-10 of 313 via a Birch reduction, the phenol 313 was phosphorylated with diethyl phosphorochloridate in the presence of triethylamine to give 314, which underwent stereoselective reduction with sodium borohydride with concomitant N-deacylation to deliver the amino alcohol 315. N-Methylation of 315 by the Eschweiler-Clarke protocol using formaldehyde and formic acid followed by ammonolysis of the ester group and acetylation of the C-2 hydroxyl function afforded 316. Dehydration of the amide moiety in 316 with phosphorus oxychloride and subsequent reaction of the resulting amino nitrile 317 with LiAlH4 furnished 318, which underwent reduction with sodium in liquid ammonia to provide unnatural (+)-galanthamine. 

Oxidation of compounds of the types thus far discussed proceeds readily at room temperature. Certain compounds which show no substantial reaction with periodic acid at room temperature can be oxidized at elevated temperature.22- 23 26 Thus, at 100° in aqueous solution the acetone mole exile is split to produce acetic acid and formaldehyde diethyl ketone yields propionic acid and probably ethanol lactic acid gives acetaldehyde and carbon dioxide acetaldehyde is oxidized to formic acid and methanol, which is converted into formaldehyde and pyruvic acid yields acetic acid and carbon dioxide. 

Cycloaddition to pyrrolidines. The reaction of diethyl aminomalonate with formaldehyde can generate an azomethine ylid (a - b) which cycloadds to 1,2-dipolarophiles to form pyrrolidines. 

Reaction between diethyl piperidyl-1,2-carboxylate and hydrazine gives amino derivative 115 (71AP216), and the synthesis of other N-substituted derivatives with pesticidal properties is illustrated by the preparation of 118. The hydantoin (116) is treated with formaldehyde followed by hydrogen bromide to give 117, which reacts with 5-ammonium-0,0-dimethylphosphorothioate to give 118 (7IBRP1337269). 

In the case of 1,3-dicarbonyl compounds, the solvent frequently interferes with the coupling reaction. So with diethyl sodio malonate in ethanol [212b], methanol [212b], dimethylacetamide [212b], or HMPTA [216], besides the dimer and the trimer, the compounds LIXa-c are obtained. They are presumably formed by oxidation of the solvent to the aldehyde and its condensation with the active methylene compound. No dimer was detected in the oxidation of sodio acetoacetate in ethanol, with the major product being LX [217]. Anodic oxidation of cyclic 1,3-diketones in aqueous methanolic sodium hydroxide does not yield the dimer but product LXI, formed by condensation of the starting compound with formaldehyde [218]. 

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