Sodium formate, reaction with acetyl

Sodium amalgam, 50, 50, 51 Sodium azide, 50,107 Sodium formate, reaction with acetyl chloride, 50, 1 Sommelet reaction, 50, 71 Styrene, reaction with carbethoxy-carbene, 50,94... 

Dinitro-2-hydroxythiophene and 3-nitro-5-acetyl-2-hydroxythio-phene have been obtained from nitrochlorothiophenes through reaction with sodium formate in methanol. These compounds were colorless crystalline substances which decomposed with evolution of nitrogen oxides and formation of a dark resin even at —20°C. They gave, however, stable, colored, sodium salts, with ionization constants of the... 

Acetyl chloride, reaction with sodium formate, 50, 1 with propylene, aluminum chloride, and quinoline to give trans-3-pentene-2-one,... 

Yet a further increase in potency is observed when the para-isobutyl group is replaced by a benzene ring. One published synthesis for that compound is quite analogous to the malonate route to the parent drug. The acetyl biphenyl (50-1) is thus converted to the corresponding arylacetic acid by reaction with sulfur and morpholine, followed by hydrolysis of the first-obtained thiomorpholide. This is then esterified and converted to malonate anion (50-2) with sodium ethoxide and ethyl formate. The anion is quenched with methyl iodide hydrolysis of the esters followed by decarboxylation yields the NSAID flubiprofen (50-3) [51]. 

The condensation of 2-nitrobenzenesulfonyl chlorides with 3-amino-2-chloropyridine in the presence of pyridine at 60 °C gave the corresponding sulfonamides, which were reacted with sodium hydride and iodomethane to give the N-methylated products. Catalytic hydrogenation of the N-methylated compounds followed by acetylation, treatment with sodium hydride in DMF, and reaction with arylalkyl chlorides or methanesulfonates resulted in the formation of novel benzo[/]pyrido[]3,2-r-][l,2,5]thiadiazepines <2005JME7363>. 

A dry 2-1. three-necked round-bottomed flask equipped with a stirrer, a thermometer, a reflux condenser with calcium chloride tube, and a dropping funnel is charged with 300 g. (4.41 moles) of sodium formate (Note 1) and 250 ml. of anhydrous ether (Note 2). To this stirred mixture is added 294 g. (266 ml., 3.75 moles) of acetyl chloride (Note 3) as rapidly as possible, while the temperature is maintained at 23-27° (Note 4). After the addition is complete, the mixture is stirred for 5.5 hours at 23-27° to ensure complete reaction. The mixture is then filtered with suction, the solid residue is rinsed with 100 ml. of ether, and the washings are added to the original filtrate (Note 5). The ether is removed by distillation at reduced pressure, and the residue is distilled to yield 212 g. (64%) of colorless acetic formic anhydride, b.p. 27-28° (10 mm.), 38-38.5° (39 mm.) ii20d 1.388 (Note 6). 

Acetic formic anhydride has been prepared by the reaction of formic acid with acetic anhydride2 3 and ketene,4,5 and of acetyl chloride with sodium formate.6 The present procedure is essentially that of Muramatsu.6 It is simpler than others previously described and gives better yields. It is easily adapted to the preparation of large quantities, usually with an increase in yield. Acetic formic anhydride is a useful intermediate for the formyl-ation of amines,3,7 amino acids,8,9 and alcohols,2,10 for the synthesis of aldehydes from Grignard reagents,11 and for the preparation of formyl fluoride.12... 

The compound appears as large yellow crystals, m.p. 111°. With sodium hydroxide in alcohol an intense violet coloration is produced. With formaldehyde and sodium hydroxide in aqueous solution S7NCH2OH (m.p. 110.5°) is formed. With acetyl chloride in chloroform in the presence of pyridine reaction occurs at 0° with the formation of yellow needles of S7NCOCH3 (m.p. 104.4°). ... 

Peptides are also acetylated with the mixed anhydride of acetic acid and formic acid. The latter is made by the reaction of acetyl chloride with sodium formate in yields of 80-90%. 77 Mixed formic anhydrides with several carboxylic acids are obtainable with a copolymer of 4-vinylpyridine 1-oxide as catalyst. The reactions are carried out in acetonitrile with equimolar amounts of acid chloride and sodium formate. In most cases the mixed anhydride is the major product (Table 9). 7 The reactions are thought to proceed according to equation (39). 

Japanese chemists prepare the reagent either by the reaction of acetyl chloride with sodium formate or of formic acid with ketene. The reagent formylates amino acids in formic acid as solvent. The N-formyl group is useful as a blocking group in peptide synthesis. It is surprisingly resistant to basic hydrolysis but readily sol-volyzed in dilute acid. ... 

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