Tetraethoxymethane

Last updated
Tetraethoxymethane
Tetraethyl ortho carbonic Acid Formula V.1.svg
Names
Preferred IUPAC name
(Triethoxymethoxy)ethane
Other names
Tetraethyl orthocarbonate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.000.985 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 201-082-2
PubChem CID
UNII
  • InChI=1S/C9H20O4/c1-5-10-9(11-6-2,12-7-3)13-8-4/h5-8H2,1-4H3
    Key: CWLNAJYDRSIKJS-UHFFFAOYSA-N
  • CCOC(OCC)(OCC)OCC
Properties
C9H20O4
Molar mass 192.25 g·mol −1
Appearanceliquid
Density 0.919
Boiling point 159.5 °C (319.1 °F; 432.6 K)
Hazards
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-exclam.svg
H226, H315, H319, H335
Related compounds
Other cations
Tetraethoxysilane
Related compounds
Tetramethoxymethane
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

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

Contents

History

Tetraethoxymethane was described the first time in 1864. [1]

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]

Tetraethyl ortho carbonic Acid Synthesis-A V.1.svg

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]

Tetraethyl ortho carbonic Acid Synthesis-B V.1.svg

Another route reacts thallous ethoxide with carbon disulfide in dry methylene dichloride. [8]

A more recent synthesis starts directly from sodium ethoxide, tin(IV)chloride, and carbon disulfide. [9]

Properties

Tetraethoxymethane is a water-clear, aromatic or fruity smelling, [10] liquid of low-viscosity which is unstable against strong acids and strong bases. [11]

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, [12] whereby spiro compounds can also be obtained. Spiro orthocarbonates (SOCs) [13] 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). [14]

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a functional group derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Organolithium reagent</span> Chemical compounds containing C–Li bonds

In organometallic chemistry, organolithium reagents are chemical compounds that contain carbon–lithium (C–Li) bonds. These reagents are important in organic synthesis, and are frequently used to transfer the organic group or the lithium atom to the substrates in synthetic steps, through nucleophilic addition or simple deprotonation. Organolithium reagents are used in industry as an initiator for anionic polymerization, which leads to the production of various elastomers. They have also been applied in asymmetric synthesis in the pharmaceutical industry. Due to the large difference in electronegativity between the carbon atom and the lithium atom, the C−Li bond is highly ionic. Owing to the polar nature of the C−Li bond, organolithium reagents are good nucleophiles and strong bases. For laboratory organic synthesis, many organolithium reagents are commercially available in solution form. These reagents are highly reactive, and are sometimes pyrophoric.

<span class="mw-page-title-main">Imine</span> Organic compound or functional group containing a C=N bond

In organic chemistry, an imine is a functional group or organic compound containing a carbon–nitrogen double bond. The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bonds. Imines are common in synthetic and naturally occurring compounds and they participate in many reactions.

<span class="mw-page-title-main">Acyl halide</span> Oxoacid compound with an –OH group replaced by a halogen

In organic chemistry, an acyl halide is a chemical compound derived from an oxoacid by replacing a hydroxyl group with a halide group.

<span class="mw-page-title-main">Oxalyl chloride</span> Chemical compound

Oxalyl chloride is an organic chemical compound with the formula Cl−C(=O)−C(=O)−Cl. This colorless, sharp-smelling liquid, the diacyl chloride of oxalic acid, is a useful reagent in organic synthesis.

<i>N</i>,<i>N</i>-Dicyclohexylcarbodiimide Chemical compound

N,N′-Dicyclohexylcarbodiimide (DCC or DCCD) is an organic compound with the chemical formula (C6H11N)2C. It is a waxy white solid with a sweet odor. Its primary use is to couple amino acids during artificial peptide synthesis. The low melting point of this material allows it to be melted for easy handling. It is highly soluble in dichloromethane, tetrahydrofuran, acetonitrile and dimethylformamide, but insoluble in water.

<span class="mw-page-title-main">Xanthate</span> Salt that is a metal-thioate/O-esters of dithiocarbonate

A xanthate is a salt or ester of a xanthic acid. The formula of the salt of xanthic acid is [R−O−CS2]M+. Xanthate also refers to the anion [R−O−CS2]. The formula of a xanthic acid is R−O−C(=S)−S−H, such as ethyl xanthic acid, while the formula of an ester of a xanthic acid is R−O−C(=S)−S−R', where R and R' are organyl groups. The salts of xanthates are also called O-organyl dithioates. The esters of xanthic acid are also called O,S-diorganyl esters of dithiocarbonic acid. The name xanthate is derived from Ancient Greek ξανθός (xanthos) meaning 'yellowish' or 'golden', and indeed most xanthate salts are yellow. They were discovered and named in 1823 by Danish chemist William Christopher Zeise. These organosulfur compounds are important in two areas: the production of cellophane and related polymers from cellulose and for extraction of certain sulphide bearing ores. They are also versatile intermediates in organic synthesis.

<span class="mw-page-title-main">Carbodiimide</span> Class of organic compounds with general structure RN=C=NR

In organic chemistry, a carbodiimide is a functional group with the formula RN=C=NR. On Earth they are exclusively synthetic, but in interstellar space the parent compound HN=C=NH has been detected by its maser emissions.

<span class="mw-page-title-main">Orthocarbonic acid</span> Hypothetical compound with formula C(OH)4

Orthocarbonic acid, carbon hydroxide, methanetetrol is the name given to a hypothetical compound with the chemical formula H4CO4 or C(OH)4. Its molecular structure consists of a single carbon atom bonded to four hydroxyl groups. It would be therefore a fourfold alcohol. In theory it could lose four protons to give the hypothetical oxocarbon anion orthocarbonateCO4−4, and is therefore considered an oxoacid of carbon.

<span class="mw-page-title-main">Acryloyl chloride</span> Chemical compound

Acryloyl chloride, also known as 2-propenoyl chloride, acrylyl chloride, or acrylic acid chloride, is the organic compound with the formula CH2=CHCO(Cl). It is a colorless liquid, although aged samples appear yellow. It belongs to the acid chlorides group of compounds.

In organic chemistry, Madelung synthesis is a chemical reaction that produces indoles by the intramolecular cyclization of N-phenylamides using strong base at high temperature. The Madelung synthesis was reported in 1912 by Walter Madelung, when he observed that 2-phenylindole was synthesized using N-benzoyl-o-toluidine and two equivalents of sodium ethoxide in a heated, airless reaction. Common reaction conditions include use of sodium or potassium alkoxide as base in hexane or tetrahydrofuran solvents, at temperatures ranging between 200–400 °C. A hydrolysis step is also required in the synthesis. The Madelung synthesis is important because it is one of few known reactions that produce indoles from a base-catalyzed thermal cyclization of N-acyl-o-toluidines.

<span class="mw-page-title-main">Sodium ethoxide</span> Ionic compound made of a C2H5–O anion and a sodium cation

Sodium ethoxide, also referred to as sodium ethanolate, is the ionic, organic compound with the formula CH3CH2ONa, C2H5ONa, or NaOEt. It is a white solid, although impure samples appear yellow or brown. It dissolves in polar solvents such as ethanol. It is commonly used as a strong base.

<span class="mw-page-title-main">Carbonyldiimidazole</span> Chemical compound

1,1'-Carbonyldiimidazole (CDI) is an organic compound with the molecular formula (C3H3N2)2CO. It is a white crystalline solid. It is often used for the coupling of amino acids for peptide synthesis and as a reagent in organic synthesis.

Alcohol oxidation is a collection of oxidation reactions in organic chemistry that convert alcohols to aldehydes, ketones, carboxylic acids, and esters where the carbon carries a higher oxidation state. The reaction mainly applies to primary and secondary alcohols. Secondary alcohols form ketones, while primary alcohols form aldehydes or carboxylic acids.

<span class="mw-page-title-main">Titanium ethoxide</span> Chemical compound

Titanium ethoxide is a chemical compound with the formula Ti4(OCH2CH3)16. It is a commercially available colorless liquid that is soluble in organic solvents but hydrolyzes readily. Its structure is more complex than suggested by its empirical formula. Like other alkoxides of titanium(IV) and zirconium(IV), it finds used in organic synthesis and materials science.

The Buchner ring expansion is a two-step organic C-C bond forming reaction used to access 7-membered rings. The first step involves formation of a carbene from ethyl diazoacetate, which cyclopropanates an aromatic ring. The ring expansion occurs in the second step, with an electrocyclic reaction opening the cyclopropane ring to form the 7-membered ring.

<span class="mw-page-title-main">Tantalum(V) ethoxide</span> Chemical compound

Tantalum(V) ethoxide is a metalorganic compound with formula Ta2(OC2H5)10, often abbreviated as Ta2(OEt)10. It is a colorless solid that dissolves in some organic solvents but hydrolyzes readily. It is used to prepare films of tantalum(V) oxide.

<span class="mw-page-title-main">Etabonate</span> Class of chemical compounds

Etabonate or ethyl carbonate is the chemical group with formula –CO
3
–C
2
H
5
, or H
3
C–CH
2
–O–C(=O)–O
–. The names are also used for esters R–OCO
2
C
2
H
5
, for the anion [C
2
H
5
OCO
2
], and for salts of the latter.

Expanding monomers are monomers which increase in volume (expand) during polymerization. They can be added to monomer formulations to counteract the usual volume shrinking to manufacture products with higher quality and durability. Volume Shrinkage is in first line for the unmeltable thermosets a problem, since those are of fixed shape after polymerization completed.

<span class="mw-page-title-main">Tetramethoxymethane</span> Chemical compound

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

References

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  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 2 "Ethyl Orthocarbonate". Organic Syntheses . doi:10.15227/orgsyn.032.0068 .
  4. 1 2 Europäische 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. 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. doi : 10.1021/jo00798a056
  9. 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.
  10. 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).
  11. Sigma-Aldrich Co. , product no. {{{id}}} .
  12. W. Kantlehner et al., Die präparative Chemie der O- und N-funktionellen Orthokohlensäure-Derivate, Synthesis, 1977, 73–90.
  13. Vodak, David T.; Braun, Matthew; Iordanidis, Lykourgos; Plévert, Jacques; Stevens, Michael; Beck, Larry; Spence, John C. H.; O'Keeffe, Michael; Yaghi, Omar M. (2002-04-11). "One-Step Synthesis and Structure of an Oligo(spiro-orthocarbonate)". Journal of the American Chemical Society. 124 (18). American Chemical Society (ACS): 4942–4943. doi:10.1021/ja017683i. ISSN   0002-7863. PMID   11982342.
  14. 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.