Chemistry:Acetyl chloride
| |||
| |||
| |||
| Names | |||
|---|---|---|---|
| Preferred IUPAC name
Acetyl chloride[2] | |||
| Systematic IUPAC name
Ethanoyl chloride | |||
| Other names
Acyl chloride
| |||
| Identifiers | |||
3D model (JSmol)
|
|||
| 605303 | |||
| ChEBI | |||
| ChemSpider | |||
| EC Number |
| ||
| 1611 | |||
PubChem CID
|
|||
| RTECS number |
| ||
| UNII | |||
| UN number | 1717 | ||
| |||
| |||
| Properties | |||
| CH 3COCl | |||
| Molar mass | 78.49 g/mol | ||
| Appearance | Colorless liquid | ||
| Density | 1.104 g/ml, liquid | ||
| Melting point | −112 °C (−170 °F; 161 K) | ||
| Boiling point | 52 °C (126 °F; 325 K) | ||
| Reacts with water | |||
| -38.9·10−6 cm3/mol | |||
| Structure | |||
| 2.45 D | |||
| Hazards | |||
| GHS pictograms |   
| ||
| GHS Signal word | Danger | ||
| H225, H302, H314, H335, H412 | |||
| P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P273, P280, P301+312, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P312, P321, P330, P363, P370+378, P403+233 | |||
| NFPA 704 (fire diamond) | |||
| Flash point | 4 °C (39 °F; 277 K) | ||
| 390 °C (734 °F; 663 K) | |||
| Explosive limits | 7.3–19% | ||
| Related compounds | |||
Related acyl chlorides
|
Propionyl chloride Butyryl chloride | ||
Related compounds
|
Acetic acid Acetic anhydride Acetyl bromide | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |||
 verify (what is   ?)
| |||
| Infobox references | |||
Acetyl chloride (CH
3COCl) is an acyl chloride derived from acetic acid (CH
3COOH). It belongs to the class of organic compounds called acid halides. It is a colorless, corrosive, volatile liquid. Its formula is commonly abbreviated to AcCl.
Synthesis
On an industrial scale, the reaction of acetic anhydride with hydrogen chloride produces a mixture of acetyl chloride and acetic acid:[3]
- [math]\ce{ (CH3CO)2O + HCl -> CH3COCl + CH3CO2H }[/math]
Laboratory routes
Acetyl chloride was first prepared in 1852 by French chemist Charles Gerhardt by treating potassium acetate with phosphoryl chloride.[4]
Acetyl chloride is produced in the laboratory by the reaction of acetic acid with chlorodehydrating agents such as phosphorus trichloride (PCl
3), phosphorus pentachloride (PCl
5), sulfuryl chloride (SO
2Cl
2), phosgene, or thionyl chloride (SOCl
2). However, these methods usually give acetyl chloride contaminated by phosphorus or sulfur impurities, which may interfere with the organic reactions.[5]
Other methods
When heated, a mixture of dichloroacetyl chloride and acetic acid gives acetyl chloride.[5] It can also be synthesized from the catalytic carbonylation of methyl chloride.[6] It also arises from the reaction of acetic acid, acetonitrile, and hydrogen chloride.[citation needed]
Occurrence
Acetyl chloride is not expected to exist in nature, because contact with water would hydrolyze it into acetic acid and hydrogen chloride. In fact, if handled in open air it releases white "smoke" resulting from hydrolysis due to the moisture in the air. The smoke is actually small droplets of hydrochloric acid and acetic acid formed by hydrolysis.
Uses
Acetyl chloride is used for acetylation reactions, i.e., the introduction of an acetyl group. Acetyl is an acyl group having the formula –C(=O)–CH
3). For further information on the types of chemical reactions compounds such as acetyl chloride can undergo, see acyl halide. Two major classes of acetylations include esterification and the Friedel-Crafts reaction.
Acetic acid esters and amide
Acetyl chloride is a reagent for the preparation of esters and amides of acetic acid, used in the derivatization of alcohols and amines. One class of acetylation reactions are esterification, for example the reaction with ethanol to produce ethyl acetate and hydrogen chloride:
- [math]\ce{ CH3COCl + HO-CH2-CH3 -> CH3-COO-CH2-CH3 + HCl }[/math]
Frequently such acylations are carried out in the presence of a base such as pyridine, triethylamine, or DMAP, which act as catalysts to help promote the reaction and as bases neutralize the resulting HCl. Such reactions will often proceed via ketene.
Friedel-Crafts acetylations
A second major class of acetylation reactions are the Friedel-Crafts reactions.[7]
See also
- Acetic acid
- Acetyl bromide
- Acetyl fluoride
- Acetyl iodide
References
- ↑ Merck Index, 11th Edition, 79.
- ↑ Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. pp. 796–797. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
- ↑ Cheung, Hosea; Tanke, Robin S.; Torrence, G. Paul (2000). "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a01_045.
- ↑ See:
- Gerhardt, Charles (1852) "Ueber wasserfreie organische Säuren" (On anhydrous organic acids), Annalen der Chemie und Pharmacie, 83 : 112–116.
- Gerhardt, Charles (1853) "Untersuchungen über die wasserfreien organischen Säuren" (Investigations into anhydrous organic acids), Annalen der Chemie und Pharmacie, 87 : 57–84 ; see especially pp. 68–71.
- ↑ 5.0 5.1 Leo A. Paquette (2005). "Acetyl chloride". Handbook of Reagents for Organic Synthesis, Activating Agents and Protective Groups. John Wiley & Sons. p. 16. ISBN 978-0-471-97927-2.
- ↑ Erpenbach, Heinz; Klaus Gehrmann & Winfried Lork et al., "Production of acetyl chloride", US patent 4352761, published 1982-10-05
- ↑ Charles Merritt, Jr and Charles E. Braun "9-Acetylanthracene" Org. Synth. 1950, 30, 2. doi:10.15227/orgsyn.030.0001
External links
Acetyl halides and salts of the acetate ion
| |||||||||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| AcOH | He | ||||||||||||||||||
| LiOAc | Be(OAc)2 BeAcOH |
B(OAc)3 | AcOAc ROAc |
NH4OAc | AcOOH | FAc | Ne | ||||||||||||
| NaOAc | Mg(OAc)2 | Al(OAc)3 ALSOL Al(OAc)2OH Al2SO4(OAc)4 |
Si | P | S | ClAc | Ar | ||||||||||||
| KOAc | Ca(OAc)2 | Sc(OAc)3 | Ti(OAc)4 | VO(OAc)3 | Cr(OAc)2 Cr(OAc)3 |
Mn(OAc)2 Mn(OAc)3 |
Fe(OAc)2 Fe(OAc)3 |
Co(OAc)2, Co(OAc)3 |
Ni(OAc)2 | Cu(OAc)2 | Zn(OAc)2 | Ga(OAc)3 | Ge | As(OAc)3 | Se | BrAc | Kr | ||
| RbOAc | Sr(OAc)2 | Y(OAc)3 | Zr(OAc)4 | Nb | Mo(OAc)2 | Tc | Ru(OAc)2 Ru(OAc)3 Ru(OAc)4 |
Rh2(OAc)4 | Pd(OAc)2 | AgOAc | Cd(OAc)2 | In | Sn(OAc)2 Sn(OAc)4 |
Sb(OAc)3 | Te | IAc | Xe | ||
| CsOAc | Ba(OAc)2 | Hf | Ta | W | Re | Os | Ir | Pt(OAc)2 | Au | Hg2(OAc)2, Hg(OAc)2 |
TlOAc Tl(OAc)3 |
Pb(OAc)2 Pb(OAc)4 |
Bi(OAc)3 | Po | At | Rn | |||
| Fr | Ra | Rf | Db | Sg | Bh | Hs | Mt | Ds | Rg | Cn | Nh | Fl | Mc | Lv | Ts | Og | |||
| ↓ | |||||||||||||||||||
| La(OAc)3 | Ce(OAc)x | Pr | Nd | Pm | Sm(OAc)3 | Eu(OAc)3 | Gd(OAc)3 | Tb | Dy(OAc)3 | Ho(OAc)3 | Er | Tm | Yb(OAc)3 | Lu(OAc)3 | |||||
| Ac | Th | Pa | UO2(OAc)2 | Np | Pu | Am | Cm | Bk | Cf | Es | Fm | Md | No | Lr | |||||
 |  |
