Acyl halide

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Acyl Halide

In

hydroxyl group (−OH) with a halide group (−X, where X is a halogen).[2]

If the acid is a

alkyl group, CO is the carbonyl group, and X represents the halide, such as chloride. Acyl chlorides are the most commonly encountered acyl halides, but acetyl iodide is the one produced (transiently) on the largest scale. Billions of kilograms are generated annually in the production of acetic acid.[4]

Preparation

Aliphatic acyl halides

On an industrial scale, the reaction of acetic anhydride with hydrogen chloride produces a mixture of acetyl chloride and acetic acid:[5]

(CH3CO)2O + HCl → CH3COCl + CH3CO2H

Common syntheses of acyl chlorides also entail the reaction of carboxylic acids with phosgene, thionyl chloride,[6] and phosphorus trichloride[7] Phosphorus pentabromide is used for acyl bromides, which are rarely of value.

Aromatic acyl chlorides

Benzoyl chloride is produced from benzotrichloride using either water or benzoic acid:[8]

C6H5CCl3 + H2O → C6H5COCl + 2 HCl
C6H5CCl3 + C6H5CO2H → 2 C6H5COCl + HCl

As with other acyl chlorides, it can be generated from the parent acid and other chlorinating agents phosphorus pentachloride or thionyl chloride.

Representative laboratory routes to

Friedel-Crafts acylation which uses formaldehyde as a reagent[citation needed], or by the direct chlorination of benzaldehyde derivatives.[10]

Acyl fluorides

Of commercial interest,

acyl fluorides.[11] Aromatic (as well as aliphatic) acyl fluorides are conveniently prepared directly from carboxylic acids, using stable, inexpensive commodity chemicals: PPh3, NBS and Et3N-3HF in a bench-top protocol.[12] Cyanuric fluoride
converts carboxylic acids to acyl fluorides.

Carboxylic acids react with sulfur tetrafluoride to give the acyl fluoride:[13]

SF4 + RCO2H → SOF2 + RC(O)F + HF

Acyl bromides and iodides

Acyl bromides and iodides are synthesized accordingly but are less common.[14]

Reactions

Acyl halides are rather reactive compounds often synthesized to be used as intermediates in the synthesis of other organic compounds. For example, an acyl halide can react with:

  • water, to form a carboxylic acid. This hydrolysis is the most heavily exploited reaction for acyl halides as it occurs in the industrial synthesis of acetic acid
    .

In the above reactions, HX (hydrogen halide or hydrohalic acid) is also formed. For example, if the acyl halide is an acyl chloride, HCl (hydrogen chloride or hydrochloric acid) is also formed.

Multiple functional groups

Adipoyl chloride

A molecule can have more than one acyl halide functional group. For example, "adipoyl dichloride", usually simply called adipoyl chloride, has two acyl chloride functional groups; see the structure at right. It is the dichloride (i.e., double chloride) of the 6-carbon dicarboxylic acid adipic acid. An important use of adipoyl chloride is polymerization with an organic di-amino compound to form a polyamide called nylon or polymerization with certain other organic compounds to form polyesters.

Phosgene (carbonyl dichloride, Cl–CO–Cl) is a very toxic gas that is the dichloride of carbonic acid (HO–CO–OH). Both chlorine atoms in phosgene can undergo reactions analogous to the preceding reactions of acyl halides. Phosgene is used a reactant in the production of polycarbonate polymers, among other industrial applications.

General hazards

Volatile acyl halides are

tosyl chloride) are irritants to the eyes, skin and mucous membranes
.

References

  1. doi:10.1351/goldbook.A00123
  2. doi:10.1351/goldbook.A00124
  3. ISBN 9780470771273
    .
  4. doi:10.1002/14356007.a01_045
  5. ISBN 3527306730
    .
  6. doi:10.15227/orgsyn.009.0032
    .
  7. ^
    doi:10.15227/orgsyn.012.0016
    .
  8. ISBN 3527306730
    .
  9. doi:10.15227/orgsyn.003.0075
    .
  10. doi:10.15227/orgsyn.009.0034
    .
  11. doi:10.1021/jo01060a600
    .
  12. S2CID 73481495
    .
  13. ISBN 978-0-471-26418-7
    .
  14. ISSN 0022-3263
    .
  15. PMID 20280752
    .

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