Sodium formate, reaction with acetyl chloride

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

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... 

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. ... 

Isotope labeling by derivative formation with deuterated reagents is useful for the preparation of analogs such as dg-acetonides, da-acetates, da-methyl ethers, dg-methyl esters, etc. The required reagents are either commercially available or can be easily prepared. (The preparation of da-methyl iodide is described in section IX-F. Various procedures are reported in the literature for the preparation of dg-acetone, da-diazometh-ane57.i63.i73 and da-acetyl chloride. ) These reactions can be carried out under the usual conditions and they need no further discussion. A convenient procedure has been reported for the da-methylation of sterically hindered or hydrogen bonded phenolic hydroxyl functions by using da-methyl iodide and sodium hydroxide in dimethyl sulfoxide solution. This procedure should be equally applicable to the preparation of estradiol da-methyl ether derivatives. 

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>. 

Azaferrocene (206) has been prepared by the reaction of sodium pyrrole, cyclopentadienylsodium, and ferrous chloride,157 or better by the reaction of potassium pyrrole with cyclopentadienyliron dicarbonyl iodide.158 It has been found159 that dioxane is a better solvent than benzene for this latter reaction. This reaction has also been applied to 2,4- and 2,5-dimethylpyrrole,158 3-acetyl-2-methyl-and 3-acetyl-2,4-dimethylpyrrole,160 and 2-methylpyrrole.159 The 2-methylazaferrocene from this latter pyrrole has been resolved with (—)6,6 -dinitrodiphenic acid.159 A compound (207) believed to be an intermediate in the formation of azaferrocenes has been isolated.161... 

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). 

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°). ... 

The treatment of compound 13s with sodium azide in dimethylformamide in presence of ammonium chloride allows ring opening of acetylated aziridine and formation of product 13t. The ring opening reaction is completely regiospecific giving azide 13t as the only product. 

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