Formaldehyde In Methanol Research Articles

Synthesis of 1, 2, 4-Oxadiazoles, Quinazolines and 1, 4-Benzodiazepines from Isatoic Anhydride

The reaction of isatoic anhydride [1] with amines was carried out to synthesize several new heterocyclic compounds. The reaction of [1] with benzamidoxime gave N-hydroxyiminobenzyl-2-aminobenzamide [2].5-(o-Aminophenyl)-3-phenyl-1, 2, 4-oxadiazole [3] was obtained by the ring closure reaction of [2] with base or acid. The acetylation of [3] gave 5-(o-acetylaminopheny1)-3-pheny1-1, 2, 4- oxadiazole [4], which was also prepared directly by the reaction of [2] with acetic anhydride. The condensation of [2] with formaldehyde in methanol gave 2, 3-dihydro-3-hydroxyiminobenzyl4(1 H)-quinazolinone [5]. The reaction of [1] with N'-chlorobenzamidine and guanidine gave 2-phenyl-4(3 H)-quinazolinone [6] and 5 H-quinazolino[3, 2-a] quinazoline-5, 12(6 H)-dione [7], respectively. The reaction of [1] with aminoacetal gave o-amino-N-(2, 2-diethoxyethyl)-benzamide [8], which was converted into 3 H-1, 4-benzodiazepine-5(4 H)-one [9]. The reaction of [1] with glycine ethyl ester gave directly 3 H-1, 4-benzodiazepine-2, 5(1 H, 4 H)-dione [10]. And the reaction of [1] with carbonohydrazide and malononitrile gave 1-anthraniloylcarbonohydrazide [11] and 2-amino-3-cyano-4(1 H)-quinolone [12], respectively.

New nucleoside analogues. β- D-glucopyranosyl derivatives of tetrahydro-1,3-oxazine

5-Alkyl-3-(β- D-glucopyranosyl)-5-nitrotetrahydro-1,3-oxazines ( 1–3) were obtained by treating D-glucopyranosylamine with 2-alkyl-2-nitropropane-1,3-diols and formaldehyde in methanol—butyl alcohol solution. Compounds 1–3 are readily hydrolyzed to yield 5-alkyl-5-nitrotetrahydro-1,3-oxazines ( 4–6) and D-glucose. Compounds 4–6 react with tetra- O-acetyl-β- D-glucopyranosyl isothiocyanate to yield derivatives of thiourea, viz., 5-alkyl-5-nitro-3-(tetra- O-acetyl-β- D-glucopyranosylthiocarbamoyl)tetrahydro-1,3-oxazines.

Synthesis of methyl groups catalysed by vitamin B 12r in vitro.

THE use of Raney metal catalysts for the reductive methylation of amines with formaldehyde and hydrogen is well known1. We wish to report that this reaction is also catalysed by vitamin B12r in vitro, and thus is potentially of biochemical importance. For example, a 1 : 1 mixture of aniline and formaldehyde in methanol and water absorbs hydrogen at room temperature and 1 atm. of pressure if a solution of vitamin B12r is added. N-methylaniline is formed in significant yield (1). Bis-dimethylglyoximato cobalt (II) complexes such as Co(D2H2)·2H2O (‘Diaquocobaloxime (II)’)2 (D = dianion of dimethylglyoxime) which may be regarded as simple models of vitamin B12r were similarly found to be cataly-tically active. Aniline could also be substituted by N-methylaniline which was converted to N,N-dimethylaniline under analogous conditions. In order to isolate or detect intermediates of this reaction, the reductive alkylation of aniline was also carried out using stoichio-metric amounts of the react ants. When 0.4 moles of aniline and 0.25 moles of formaldehyde (in 40 per cent aqueous solution) were added to a suspension of 0.20 moles of Co(D2H2)·2H2O in 1 l. of methanol under 1 atm. of hydrogen, 0.1 mole of hydrogen was rapidly absorbed on stirring and the cobaloxime dissolved completely. On addition of 1 l. of water a crystalline complex precipitated in a yield of 94 per cent, which was dissolved in methanol and reprecipitated by adding water. After drying at 0.1 mm of mercury 25° C it analysed for C21H29N604CoH2O, corresponding to

Benzyloxyacetonitrile and methyl benzyloxyacetimidate

In addition to the previously reported benzyloxyacetonitrile, methyl benzyloxyacetimidate has been shown to be a major product in the reaction of benzyl chloride, formaldehyde, and sodium cyanide in methanol. Pyrolytic elimination of methanol from the acetimidate occurs readily to yield the acetonitrile.

Comparison of Sterilizing Properties of Formaldehyde-Methanol Solutions With Formaldehyde-Water Solutions

Sterilizing properties of formaldehyde in anhydrous methanol and formaldehyde in water were compared. Formaldehyde in methanol achieved sterilization in 24 hr. Formaldehyde in water was found to sterilize in shorter periods of time and to have a longer shelf life than formaldehyde in methanol.

Comparison of Sterilizing Properties of Formaldehyde-Methanol Solutions With Formaldehyde-Water Solutions

Sterilizing properties of formaldehyde in anhydrous methanol and formaldehyde in water were compared. Formaldehyde in methanol achieved sterilization in 24 hr. Formaldehyde in water was found to sterilize in shorter periods of time and to have a longer shelf life than formaldehyde in methanol.