Formate

Biochemistry

Formate is a common C-1 source in living systems. It is formed from many precursors including choline, serine, and sarcosine. It provides a C-1 source in the biosynthesis of some nucleic acids. Formate (or formic acid) is invoked as a leaving group in the demethylation of some sterols. These conversions are catalyzed by aromatase enzymes using O₂ as the oxidant. Specific conversions include testosterone to estradiol and androstenedione to estrone.

Formate is reversibly oxidized by the enzyme formate dehydrogenase from Desulfovibrio gigas:

HCO−2 → CO₂ + H⁺ + 2 e⁻.

Formate esters

Formate esters have the formula HCOOR (alternative way of writing formula ROC(O)H or RO₂CH). Many form spontaneously when alcohols dissolve in formic acid; contrariwise, they hydrolyze easily in base. Some formate esters arise by the addition of formic acid to alkenes.

An important formate ester is methyl formate, which is produced as an intermediate en route to formic acid. Methanol and carbon monoxide react in the presence of a strong base, such as sodium methoxide:

CH₃OH + CO → HCOOCH₃.

Hydrolysis of methyl formate gives formic acid and regenerates methanol:

HCOOCH₃ → HCOOH + CH₃OH.

In laboratory, formate esters can be used to produce pure carbon monoxide.

Reaction with phosphorus pentachloride does not chlorolyze the ester bond, instead forming an (unusual) dichloromethyl ether.

Formate esters often are fragrant or have distinctive odors. Compared to the more common acetate esters, formate esters are less commonly used commercially because they are less stable. Ethyl formate is found in some confectionaries.

Formate salts

Formate salts have the formula M(O₂CH)(H₂O)_x. Such salts are prone to decarboxylation. For example, hydrated nickel formate decarboxylates at about 200 °C with reduction of the Ni²⁺ to finely powdered nickel metal:

Ni(HCO₂)₂(H₂O)₂ → Ni + 2 CO₂ + 2 H₂O + H₂.

Such fine powders are useful as hydrogenation catalysts.

Examples

• ethyl formate, CH₃CH₂(HCOO)
• sodium formate, Na(HCOO)
• potassium formate, K(HCOO)
• caesium formate, Cs(HCOO); see Caesium: Petroleum exploration
• methyl formate, CH₃(HCOO)
• methyl chloroformate, CH₃OCOCl
• triethyl orthoformate
• trimethyl orthoformate, C₄H₁₀O₃
• phenyl formate HCOOC₆H₅
• amyl formate