Acetyl hypochlorite

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Acetyl hypochlorite
Chlorine acetate.png
Names
Systematic IUPAC name
Chloro acetate
Other names
  • Chlorine acetate
  • Chlorine(I) acetate
  • Chloro methylformate
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • Key: ZFDLFHQAGYPRBY-UHFFFAOYSA-N
  • InChI=1S/C2H3ClO2/c1-2(4)5-3/h1H3
  • CC(=O)OCl
Properties
C2ClH3O2
Molar mass 94.50 g/mol
AppearanceColorless liquid
Melting point 100 °C (212 °F; 373 K) (decomposes)
Reacts
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Acetyl hypochlorite, also known as chlorine acetate, is a chemical compound with the formula CH3COOCl. It is a photosensitive colorless liquid that is a short lived intermediate in the Hunsdiecker reaction. [1]

Contents

Preparation, properties, and structure

Acetyl hypochlorite is reported to be produced by the reaction of acetic anhydride and dichlorine monoxide at very low temperatures: [2]

Cl2O + (CH3CO)2O → 2CH3COOCl

The liquid can be distilled at reduced pressure, however it cannot be heated, as it violently decomposes at 100 °C to acetic anhydride, oxygen, and chlorine gas, and reacts with water and alcohols. This is a problem in the Hunsdiecker reaction, as it results in a lower yield from the decomposition of this compound if using water or an alcohol as a solvent, so the reaction uses the nonpolar carbon tetrachloride instead. The compound must be stored under 0 °C in the dark, as it slowly decomposes in the presence of light or above 0 °C into methyl chloride and carbon dioxide. [1] [2]

This compound reacts with various metals such as zinc and mercury to produce their respective chlorides and acetates. [2]

In modern uses, the compound is usually prepared in situ , by the reaction of mercury acetate or acetic acid and chlorine or hypochlorous acid, usually in a solvent such as carbon tetrachloride. [3] [1] The compound is in equilibrium with a mixture of acetic acid and hypochlorous acid. [4]

The carbonyl oxygen and the hypochlorite ion were shown to be on the same side. The O-Cl bond was shown to be 1.70 Å, and the molecular geometry around the central carbon was trigonal planar. [3]

Uses

This compound is used for the chlorination of various compounds, especially aromatic compounds, such as the chlorination of methyl acetamide, and has been proven to be a better chlorinating agent than molecular chlorine and hypochlorous acid. [4] However, this reaction is an unwanted side reaction in the Hunsdiecker reaction involving aromatic carboxylates. [1]

Hunsdiecker Reaction Mechanism.png

The Hunsdieker reaction is a mechanism to convert salts of carboxylic acids(usually salts of silver) into organic halides which uses aryl hypohalites, such as acetyl hypochlorite(produced in situ by the reaction of silver acetate and chlorine). In the mechanism of this reaction, 2 is the aryl hypohalite intermediate. However, the chlorine analog of the Hunsdiecker reaction is not efficient compared to the bromine and iodine and is not used very much compared to them due to the inconvenience of using a gaseous reagent. [5] [1]

An important use of this compound is the conversion of alkenes into vicinal diols, such as butene into 1,2-butanediol, where acetyl hypochlorite appears at an intermediate; the iodine version of this reaction is known as the Prévost reaction. [1]

Related Research Articles

<span class="mw-page-title-main">Chlorine</span> Chemical element, symbol Cl and atomic number 17

Chlorine is a chemical element; it has symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is a yellow-green gas at room temperature. It is an extremely reactive element and a strong oxidising agent: among the elements, it has the highest electron affinity and the third-highest electronegativity on the revised Pauling scale, behind only oxygen and fluorine.

<span class="mw-page-title-main">Carboxylic acid</span> Organic compound containing a –C(=O)OH group

In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group attached to an R-group. The general formula of a carboxylic acid is often written as R−COOH or R−CO2H, sometimes as R−C(O)OH with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic acids occur widely. Important examples include the amino acids and fatty acids. Deprotonation of a carboxylic acid gives a carboxylate anion.

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

In chemistry, an ester is a compound 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">Haloalkane</span> Group of chemical compounds derived from alkanes containing one or more halogens

The haloalkanes are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes that contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

<span class="mw-page-title-main">Sodium hypochlorite</span> Chemical compound (known in solution as bleach)

Sodium hypochlorite is an alkaline inorganic chemical compound with the formula NaOCl. It is commonly known in a dilute aqueous solution as bleach or chlorine bleach. It is the sodium salt of hypochlorous acid, consisting of sodium cations and hypochlorite anions.

In organic chemistry, an acyl chloride is an organic compound with the functional group −C(=O)Cl. Their formula is usually written R−COCl, where R is a side chain. They are reactive derivatives of carboxylic acids. A specific example of an acyl chloride is acetyl chloride, CH3COCl. Acyl chlorides are the most important subset of acyl halides.

In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens. Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

In organic chemistry, an aryl halide is an aromatic compound in which one or more hydrogen atoms, directly bonded to an aromatic ring are replaced by a halide. The haloarene are different from haloalkanes because they exhibit many differences in methods of preparation and properties. The most important members are the aryl chlorides, but the class of compounds is so broad that there are many derivatives and applications.

<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">Hypochlorite</span> Ion

In chemistry, hypochlorite, or chloroxide is an anion with the chemical formula ClO. It combines with a number of cations to form hypochlorite salts. Common examples include sodium hypochlorite and calcium hypochlorite. The Cl-O distance in ClO is 1.69 Å.

<span class="mw-page-title-main">Acetic anhydride</span> Organic compound with formula (CH₃CO)₂O

Acetic anhydride, or ethanoic anhydride, is the chemical compound with the formula (CH3CO)2O. Commonly abbreviated Ac2O, it is the simplest isolable anhydride of a carboxylic acid and is widely used as a reagent in organic synthesis. It is a colorless liquid that smells strongly of acetic acid, which is formed by its reaction with moisture in the air.

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

Dichlorine monoxide is an inorganic compound with the molecular formula Cl2O. It was first synthesised in 1834 by Antoine Jérôme Balard, who along with Gay-Lussac also determined its composition. In older literature it is often referred to as chlorine monoxide, which can be a source of confusion as that name now refers to the ClO radical.

The Hunsdiecker reaction is a name reaction in organic chemistry whereby silver salts of carboxylic acids react with a halogen to produce an organic halide. It is an example of both a decarboxylation and a halogenation reaction as the product has one fewer carbon atoms than the starting material and a halogen atom is introduced its place. A catalytic approach has been developed.

In chemistry, aminolysis (/am·i·nol·y·sis/) is any chemical reaction in which a molecule is lysed by reacting with ammonia or an amine. The case where the reaction involves ammonia may be more specifically referred to as ammonolysis.

Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.

Iodine compounds are compounds containing the element iodine. Iodine can form compounds using multiple oxidation states. Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while chlorine gas will halogenate carbon monoxide, nitric oxide, and sulfur dioxide, iodine will not do so. Furthermore, iodination of metals tends to result in lower oxidation states than chlorination or bromination; for example, rhenium metal reacts with chlorine to form rhenium hexachloride, but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide. By the same token, however, since iodine has the lowest ionisation energy among the halogens and is the most easily oxidised of them, it has a more significant cationic chemistry and its higher oxidation states are rather more stable than those of bromine and chlorine, for example in iodine heptafluoride.

Acetyl iodide is an organoiodine compound with the formula CH3COI. It is a colourless liquid. It is formally derived from acetic acid. Although far rarer in the laboratory than the related acetyl bromide and acetyl chloride, acetyl iodide is produced, transiently at least, on a far larger scale than any other acid halide. Specifically, it is generated by the carbonylation of methyl iodide in the Cativa and Monsanto processes, which are the main industrial processes that generate acetic acid. It is also an intermediate in the production of acetic anhydride from methyl acetate.

<span class="mw-page-title-main">Ethenone</span> Organic compound with the formula H2C=C=O

In organic chemistry, ethenone is the formal name for ketene, an organic compound with formula C2H2O or H2C=C=O. It is the simplest member of the ketene class. It is an important reagent for acetylations.

<span class="mw-page-title-main">Haloform reaction</span> Chemical reaction involving repeated halogenation of an acetyl group (–COCH3)

In chemistry, the haloform reaction is a chemical reaction in which a haloform is produced by the exhaustive halogenation of an acetyl group, in the presence of a base. The reaction can be used to transform acetyl groups into carboxyl groups or to produce chloroform, bromoform, or iodoform. Note that fluoroform can't be prepared in this way.

<span class="mw-page-title-main">Acetic acid</span> Colorless and faint organic acid found in vinegar

Acetic acid, systematically named ethanoic acid, is an acidic, colourless liquid and organic compound with the chemical formula CH3COOH. Vinegar is at least 4% acetic acid by volume, making acetic acid the main component of vinegar apart from water. It has been used, as a component of vinegar, throughout history from at least the third century BC.

References

  1. 1 2 3 4 5 6 "13". Acyl Halides. John Wiley & Sons Ltd. 1972. pp. 458–478. doi:10.1002/9780470771273.ch13. ISBN   9780470771273 . Retrieved 24 October 2022.
  2. 1 2 3 P. Schutzenberger (1861). "Substitution des corps electronegatifs (chlore, brome, iode, cyanogene, soufre, etc.) aux metaux dans les sels oxygenes: production d'une nouvelle classe de sels dans lesquels les corps electro-negatifs replacent l'hydrogene basique". Comptes Rendus (in French). 52: 135.
  3. 1 2 J. C. Evans; G. Y-S. Lo; Y-L. Chang (1965). "The vibrational spectra of acetyl hypochlorite". Spectrochimica Acta. 21 (5): 973–979. Bibcode:1965AcSpe..21..973E. doi:10.1016/0371-1951(65)80165-5.
  4. 1 2 M. Wayman; E. W. C. W. Thomm (1969). "N-Chlorination of secondary amides. I. Kinetics of N-chlorination of N-methyl acetamide". Canadian Journal of Chemistry. 47 (14): 2561–2567. doi: 10.1139/v69-423 .
  5. Robert G. Johnson; Robert K. Ingham (1956). "The Degradation Of Carboxylic Acid Salts By Means Of Halogen - The Hunsdiecker Reaction". Chemical Reviews . 56 (2): 219–269. doi:10.1021/cr50008a002.