Tetraethoxymethane is a

chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...

which is formally formed by complete ethylation of the hypothetical

orthocarbonic acid Orthocarbonic acid, carbon hydroxide, or methanetetrol is the name given to a hypothetical compound with the chemical formula or . Its molecular structure consists of a single carbon atom bonded to four hydroxyl groups. It would be therefore a ...

C(OH)₄ (orthocarbonic acid violates the Erlenmeyer rule and is unstable in the free state).

History

Tetraethoxymethane was described the first time in 1864.H. Bassett, ''Ueber das vierfach-basische kohlensaure Aethyl'', Ann. 132, 54 (1864), .

Synthesis

The preparation of tetraethoxymethane from the highly toxic trichloronitromethane is known in the literatureEuropäische Patentschrift EP 0881212 B1
''Production method of aminobenzene compound''
Erfinder: H. Hashimoto et al., Anmelder: Takeda Chemical Industries, Ltd., veröffentlicht am 30. Oktober 2001. and achieves only yields of 46-49 to 58%: Tetraethyl ortho carbonic Acid Synthesis-A V

The obvious synthetic route from

tetrachloromethane Carbon tetrachloride, also known by many other names (such as carbon tet for short and tetrachloromethane, also IUPAC nomenclature of inorganic chemistry, recognised by the IUPAC), is a chemical compound with the chemical formula CCl4. It is a n ...

does not provide the desired product, as in the homologous

tetramethoxymethane Tetramethoxymethane is a chemical compound which is formally formed by complete methylation of the hypothetical orthocarbonic acid . Preparation The obvious synthetic route from the tetrahalomethanes does not yield the desired product, instead ...

.R.H. De Wolfe, ''Carboxylic ortho acid derivatives: preparation and synthetic applications'', Organic Chemistry, Vol. 14, Academic Press, Inc. New York – London, 1970, . Starting from the less toxic

trichloroacetonitrile Trichloroacetonitrile is an organic compound with the formula CCl3CN. It is a colourless liquid, although commercial samples often are brownish. It is used commercially as a precursor to the fungicide etridiazole. It is prepared by dehydration of ...

(compared with trichloronitromethane), higher yields can be obtained (up to 85%). An alternative reaction, bypassing problematic reactants, is the reaction of dialkyltin dialkoxides with

carbon disulfide Carbon disulfide (also spelled as carbon disulphide) is an inorganic compound with the chemical formula and structure . It is also considered as the anhydride of thiocarbonic acid. It is a colorless, flammable, neurotoxic liquid that is used as ...

at elevated temperature in an autoclave: Tetraethyl ortho carbonic Acid Synthesis-B V

Another route reacts thallous ethoxide with carbon disulfide in dry methylene dichloride.Shizuyoshi Sakai, Yoshitaka Kuroda, Yoshio Ishii (1972): "Preparation of orthocarbonates from thallous alkoxides and carbon disulfide". ''Journal of Organic Chemistry'', volume 37, issue 25, pages 4198–4200. A more recent synthesis starts directly from

sodium ethoxide Sodium ethoxide, also referred to as sodium ethanolate, is the Ionic compound, ionic, organic compound with the formula , , or NaOEt (Et = ethyl group, ethyl). It is a white solid, although impure samples appear yellow or brown. It dissolves in p ...

, tin(IV)chloride, and carbon disulfide.

Properties

Tetraethoxymethane is a water-clear, aromatic or fruity smelling, liquid of low-viscosity which is unstable against strong acids and strong bases.

Uses

Tetraethoxymethane can be used as a solvent and for the alkylation of CH-acidic compounds (e.g.

phenols In organic chemistry, phenols, sometimes called phenolics, are a class of chemical compounds consisting of one or more hydroxyl groups (− O H) bonded directly to an aromatic hydrocarbon group. The simplest is phenol, . Phenolic compounds ar ...

and

carboxylic acid In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an Substituent, R-group. The general formula of a carboxylic acid is often written as or , sometimes as with R referring to an organyl ...

s). In addition, it reacts with

amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...

enol ether In organic chemistry an enol ether is an alkene with an alkoxy substituent. The general structure is R2C=CR-OR where R = H, alkyl or aryl. A common subfamily of enol ethers are vinyl ethers, with the formula ROCH=CH2. Important enol ethers incl ...

s and

sulfonamide In organic chemistry, the sulfonamide functional group (also spelled sulphonamide) is an organosulfur group with the Chemical structure, structure . It consists of a sulfonyl group () connected to an amine group (). Relatively speaking this gro ...

s, whereby

spiro compound In organic chemistry, spiro compounds are Organic compound, compounds that have at least two Cyclic compound, molecular rings sharing one common atom. Simple spiro compounds are bicyclic (having just two rings). The presence of only one common at ...

s can also be obtained. Spiro orthocarbonates (SOCs) are of some industrial interest, as they are used as additives for reducing shrinkage during the polymerization of

epoxide In organic chemistry, an epoxide is a cyclic ether, where the ether forms a three-atom ring: two atoms of carbon and one atom of oxygen. This triangular structure has substantial ring strain, making epoxides highly reactive, more so than other ...

s (they are used as expanding monomers).R. Acosta Ortiz et al., ''Novel diol spiro orthocarbonates derived from glycerol as anti-shrinkage additives for the cationic photopolymerization of epoxy monomers'', Polymer International, 59(5), 680–685 (2010), {{doi, 10.1002/pi.2755.

References

Orthocarbonates Ethoxy compounds