“Tetraethoxymethane”的意思、由来-开放百科全书

Tetraethoxymethane is a chemical compound which is formally formed by complete ethylation of the hypothetical orthocarbonic acid C(OH)₄ (orthocarboxylic acid violates the Erlenmeyer rule and is unstable in free state).

History

Synthesis

The preparation of tetraethoxymethane from the highly toxic trichloronitromethane is known in the literature^[1]^[2]^[3]^[4] and achieves only yields of 46-49^[3] to 58%:^[4]

The obvious synthetic route from tetrachloromethane does not provide the desired product, as in the homologous tetramethoxymethane.^[5]

Starting from the less toxic trichloroacetonitrile (compared with trichloronitromethane), higher yields can be obtained (up to 85%).^[6] An alternative reaction, bypassing problematic reactants, is the reaction of dialkyltin dialkoxides with carbon disulfide at elevated temperature in an autoclave:^[7]

A more recent synthesis starts directly from sodium ethoxide, tin(IV)chloride, and carbon disulfide.^[8]

Properties

Tetraethoxymethane is water-clear, aromatic or fruity smelling,^[9] liquid of low-viscosity which is unstable against strong acids and strong bases.^[10]

Uses

Tetraethoxymethane can be used as a solvent and for the alkylation of CH-acidic compounds (e.g. phenols and carboxylic acids). In addition, it reacts with amines, enol ethers and sulfonamides,^[11] whereby spiro compounds can also be obtained. Spiro orthocarbonates (SOCs)^[12] are of some industrial interest, as they are used as additives for reducing shrinkage during the polymerization of epoxides (they are used as expanding monomers).^[13]

References

1. ^¹H. Bassett, Ueber das vierfach-basische kohlensaure Aethyl, Ann. 132, 54 (1864), {{DOI|10.1002/jlac.18641320106}}.
2. ^H. Tieckelmann, H.W. Post, The preparation of methyl, ethyl, propyl, and butyl orthocarbonates, J. Org. Chem., 13 (2), 265–267 (1948), {{DOI|10.1021/jo01160a014}}.
3. ^¹{{OrgSynth|Kurzcode=cv4p0457 |Autor=J.D. Roberts, R.E. McMahon |title=Ethyl Orthocarbonate |Jahrgang=1952 |Volume=32 |Seiten=68 |ColVol=4 |ColVolSeiten=457 |doi=10.15227/orgsyn.032.0068 }}
4. ^¹Europäische Patentschrift EP 0881212 B1, Production method of aminobenzene compound, Erfinder: H. Hashimoto et al., Anmelder: Takeda Chemical Industries, Ltd., veröffentlicht am 30. Oktober 2001.
5. ^R.H. De Wolfe, Carboxylic ortho acid derivatives: preparation and synthetic applications, Organic Chemistry, Vol. 14, Academic Press, Inc. New York – London, 1970, {{ISBN|978-0-12-214550-6}}.
6. ^US-Patent US 6825385, Process for the preparation of orthocarbonates, Erfinder: G. Fries, J. Kirchhoff, Anmelder: Degussa AG, erteilt am 30. November 2004.
7. ^S. Sakai et al., Reaction of Dialkyltin Dialkoxides with Carbon Disulfide at Higher Temperature. Preparation of Orthocarbonates, J. Org. Chem., 36 (9), 1176 (1971), {{DOI|10.1021/jo00808a002}}.
8. ^S. Sakai et al., A new method for preparation of tetraalkyl orthocarbonates from sodium alkoxides, tetrachlorostannane, and carbon disulfide, Synthesis 1984 (3), 233–234, {{DOI|10.1055/s-1984-30785}}.
9. ^J. H. Ruth, Odor Thresholds and Irritation Levels of Several Chemical Substances: A Review, Am. Ind. Hyg. Assoc. J. 47, A-142 – A-151, (1986).
10. ^{{Sigma-Aldrich|ALDRICH|163627|Datum=17. Oktober 2013}}
11. ^W. Kantlehner et al., Die präparative Chemie der O- und N-funktionellen Orthokohlensäure-Derivate, Synthesis, 1977, 73–90.
12. ^D.T. Vodak et al., One-Step Synthesis and Structure of an Oligo(spiro-orthocarbonate), J. Am. Chem., Soc., 124, 4942–4943 (2002), {{DOI|10.1021/ja17683i}}.
13. ^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}}.