Acetic anhydride
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| Acetic anhydride | |
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| IUPAC name |
acetic anhydride
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| Systematic name | ethanoic anhydride |
| Other names | Ethanoyl ethanoate Acetic acid anhydride Acetyl acetate Acetyl oxide Acetic oxide |
| Identifiers | |
| CAS number | 108-24-7  |
| PubChem | 7918 |
| EC number | 203-564-8 |
| RTECS number | AK1925000 |
| SMILES |
O=C(OC(=O)C)C
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| InChI |
1/C4H6O3/c1-3(5)7-4(2)6/h1-2H3
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| InChI key | WFDIJRYMOXRFFG-UHFFFAOYAH |
| ChemSpider ID | 7630 |
| Properties | |
| Molecular formula | C4H6O3 |
| Molar mass | 102.09 g/mol |
| Appearance | clear liquid |
| Density | 1.082 g/cm3, liquid |
| Melting point |
−73.1 °C |
| Boiling point |
139.8 °C |
| Solubility in water | 2.6 g/100 ml, see text |
| Refractive index (nD) | 1.3901 |
| Hazards | |
| MSDS | ICSC 0209 |
| EU Index | 607-008-00-9 |
| EU classification | Corrosive (C) |
| R-phrases | R10, R20/22, R34 |
| S-phrases | (S1/2), S26, S36/37/39, S45 |
| NFPA 704 |
 2
2
1
|
| Flash point | 49 °C |
| Autoignition temperature |
316 °C |
| Explosive limits | 2.7–10.3% |
| Related compounds | |
| Related acid anhydrides | Propionic anhydride |
| Related compounds | Acetic acid Acetyl chloride |
| (what is this?) (verify) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) |
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| Infobox references | |
Acetic anhydride, or ethanoic anhydride, is the chemical compound with the formula (CH3CO)2O. Commonly abbreviated Ac2O, it is the simplest acid anhydride and is a widely used reagent in organic synthesis. It is a colorless liquid that smells strongly of acetic acid, formed by its reaction with the moisture in the air.
Contents |
[edit] Production
Acetic anhydride is produced by carbonylation of methyl acetate:[1]
- CH3CO2CH3 + CO → (CH3CO)2O
This process involves the conversion of methyl acetate to methyl iodide and an acetate salt. Carbonylation of the methyl iodide in turn affords acetyl iodide, which reacts with acetate salts or acetic acid to give the product. Rhodium and lithium iodides are employed as catalysts. Because acetic anhydride is not stable in water, the conversion is conducted under anhydrous conditions. In contrast, the Monsanto acetic acid process, which also involves a rhodium catalyzed carbonylation of methyl iodide, is at least partially aqueous.
To a decreasing extent, acetic anhydride is also prepared by the reaction of ketene with acetic acid at 45–55 °C and low pressure (0.05–0.2 bar).[2]
- H2C=C=O + CH3COOH → (CH3CO)2O (ΔH = −63 kJ/mol)
Ketene is generated by dehydrating acetic acid at 700–750 °C in the presence of triethyl phosphate as a catalyst or (in Switzerland and the CIS) by the thermolysis of acetone at 600–700 °C in the presence of carbon disulfide as a catalyst.[2]
- CH3COOH
H2C=C=O + H2O (ΔH = +147 kJ/mol) - CH3COCH3 → H2C=C=O + CH4
The route from acetic acid to acetic anhydride via ketene was developed by Wacker Chemie in 1922,[3] when the demand for acetic anhydride increased due to the production of cellulose acetate.
Due to its low cost, acetic anhydride is purchased, not prepared, for use in research laboratories.
[edit] Reactions
Acetic anhydride is a versatile reagent for acetylations, the introduction of acetyl groups to organic substrates.[4] In these conversions, acetic anhydride is viewed as a source of CH3CO+. Alcohols and amines are readily acetylated.[5] For example, the reaction of acetic anhydride with ethanol yields ethyl acetate:
- (CH3CO)2O + CH3CH2OH → CH3CO2CH2CH3 + CH3COOH
Often a base such as pyridine is added to function as catalyst. In specialized applications, Lewis acidic scandium salts have also proven effective catalysts.[6]
Aromatic rings are acetylated, usually in the presence of an acid catalyst. Illustrative is the conversion of benzene to acetophenone:
- (CH3CO)2O + C6H6 → CH3COC6H5 + CH3CO2H
Ferrocene may be acetylated too:[7]
- Cp2Fe + (CH3CO)2O → CpFe(C5H4COCH3)
[edit] Hydrolysis
Acetic anhydride dissolves in water to approximately 2.6% by weight.[8] Aqueous solutions have limited stability because, like most acid anhydrides, acetic anhydride hydrolyses to give acetic acid:[9]
- (CH3CO)2O + H2O → 2 CH3CO2H
[edit] Applications
As indicated by its organic chemistry, Ac2O is mainly used for acetylations leading to commercially significant materials. Its largest application is for the conversion of cellulose to cellulose acetate, which is a component of photographic film and other coated materials. Similarly it is used in the production of aspirin, acetylsalicylic acid, which is prepared by the acetylation of salicylic acid.[10] It is also used as a wood preservative via autoclave impregnation to make a longer lasting timber.
Because of its use for the synthesis of heroin by the diacetylation of morphine, acetic anhydride is listed as a U.S. DEA List II precursor, and restricted in many other countries.[11]
[edit] Safety
Acetic anhydride is an irritant and flammable. Because of its reactivity toward water, alcohol foam or carbon dioxide are preferred for fire suppression.[12] The vapour of acetic anhydride is harmful.[13]
[edit] References
- ^ Zoeller, J. R.; Agreda, V. H.; Cook, S. L.; Lafferty, N. L.; Polichnowski, S. W.; Pond, D. M. (1992), "Eastman Chemical Company Acetic Anhydride Process", Catal. Today 13: 73–91, doi:
- ^ a b Arpe, Hans-Jürgen (2007), Industrielle organische Chemie: Bedeutende vor- und Zwischenprodukte (6th ed.), Weinheim: Wiley-VCH, pp. 200–1, ISBN 3527315403, http://books.google.com/books?id=36kHHvzx6M8C&pg=PA200&lpg=PA200&dq=wacker+verfahren+essigs%C3%A4ureanhydrid&source=web&ots=n4is04tlMR&sig=NZFcsmFpA1p6p0PBp0zNzAWmFo4#PPA201,M1.
- ^ Milestones in the history of WACKER, Wacker Chemie AG, http://www.wacker.com/cms/en/wacker_group/wacker_facts/history/history.jsp, retrieved 2009-08-27.
- ^ "Acid Anhydrides", Understanding Chemistry, http://www.chemguide.co.uk/organicprops/anhydridemenu.html, retrieved 2006-03-25.
- ^ Shakhashiri, Bassam Z., "Acetic Acid & Acetic Anhydride", Science is Fun… (Department of Chemistry, University of Wisconsin), http://scifun.chem.wisc.edu/CHEMWEEK/AceticAcid/AceticAcid.html, retrieved 2006-03-25.
- ^ Macor, John; Sampognaro, Anthony J.; Verhoest, Patrick R.; Mack, Robert A. (2000), "(R)-(+)-2-Hydroxy-1,2,2-Triphenylethyl Acetate", Org. Synth. 77: 45, http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=V77P0045; Coll. Vol. 10: 464
- ^ Taber, Douglass F., Column chromatography: Preparation of Acetyl Ferrocene, Department of Chemistry and Biochemistry, University of Delaware, http://valhalla.chem.udel.edu/ferroc.html, retrieved 2009-08-27.
- ^ Acetic Anhydride: Frequently Asked Questions, British Petroleum, http://www.bp.com/liveassets/bp_internet/globalbp/STAGING/global_assets/downloads/pdfs/acetyls_aromatics_pta/AceticAnhydrideFAQ.pdf, retrieved 2006-05-03.
- ^ Acetic Anhydride: Material Safety Data Sheet (PDF), Celanese, http://www.celanese.com/msds/pdf/570-22027587.pdf, retrieved 2006-05-03.
- ^ Acetic anhydride, SIDS Initial Assessment Report, Geneva: United Nations Environment Programme, p. 5, http://www.inchem.org/documents/sids/sids/108247.pdf.
- ^ UN Intercepts Taliban's Heroin Chemical in Rare Afghan Victory, Bloomberg, http://www.bloomberg.com/apps/news?pid=20670001&refer=home&sid=aY1eg_RtBNNU, retrieved 2008-10-07.
- ^ "Data Sheets". International Occupational Safety and Health Information Centre. http://www.ilo.org/public/english/protection/safework/cis/products/icsc/dtasht/_icsc02/icsc0209.htm. Retrieved 2006-04-13.
- ^ "NIOSH". Pocket Guide to Chemical Hazards. http://www.cdc.gov/niosh/npg/npgd0003.html. Retrieved 2006-04-13.
