Pyridinium chlorochromate

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Pyridinium chlorochromate
Chemical structure of pyridinium chlorochromate
Ball-and-stick model of the pyridinium cation
Ball-and-stick model of the chlorochromate anion
Names
IUPAC name
Pyridinium chlorochromate
Other names
PCC
Identifiers
26299-14-9 N
ChemSpider 10608386 N
Jmol 3D model Interactive image
Properties
C5H6ClCrNO3
Molar mass 215.56 g/mol
Appearance yellow-orange solid[1]
Melting point 205 °C (401 °F; 478 K)
Solubility in other solvents soluble in acetone, acetonitrile, THF
Hazards
Main hazards Carcinogenicity, aquatic toxicity
Safety data sheet external SDS
GHS pictograms GHS-pictogram-rondflam.svgGHS-pictogram-silhouette.svgGHS-pictogram-exclam.svgGHS-pictogram-pollu.svg
H350, H272, H317, H410
P201, P280, P273, P221, P308+313, P302+352
R-phrases R49, R8, R43, R50/53
S-phrases S53, S45, S60, S61
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oil Health code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g., chloroform Reactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g., phosphorus Special hazard OX: Oxidizer. E.g., potassium perchlorateNFPA 704 four-colored diamond
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Pyridinium chlorochromate (PCC) is a yellow-orange salt with the formula [C5H5NH][CrO3Cl]. It is a reagent in organic synthesis used primarily for oxidation of alcohols to form carbonyls. A variety of related compounds are known with similar reactivity. Although no longer widely used, PCC offers the advantage of the selective oxidation of alcohols to aldehydes or ketones, whereas many other reagents are less selective.[1]

Structure and preparation[edit]

PCC consists of a pyridinium cation, [C5H5NH]+, and a tetrahedral chlorochromate anion, [CrO3Cl]. Related salts are also known, such as 1-butylpyridinium chlorochromate, [C5H5N(C4H9)][CrO3Cl].

PCC is commercially available. Discovered by accident,[3] the reagent was originally prepared via addition of pyridine into a cold solution of chromium trioxide in concentrated hydrochloric acid:[4]

C5H5N + HCl + CrO3 → [C5H5NH][CrO3Cl]

In one alternative method, formation of chromyl chloride (CrO2Cl2) fume during the making of the aforementioned solution was minimized by simply changing the order of addition: a cold solution of pyridine in concentrated hydrochloric acid was added to solid chromium trioxide under stirring.[5]

Uses[edit]

Oxidation of alcohols[edit]

PCC is used as an oxidant. In particular, it has proven to be highly effective in oxidizing primary and secondary alcohols to aldehydes and ketones, respectively. Unlike with the related Jones reagent, rarely does over-oxidation occur to form carboxylic acids, whether intentionally or accidentally. A typical PCC oxidation involves addition of an alcohol to a suspension of PCC in dichloromethane.[6][7][8] The general reaction is:

2 [C5H5NH][CrO3Cl] + 3 R2CHOH → 2 [C5H5NH]Cl + Cr2O3 + 3 R2C=O + 3 H2O

For example, triterpene lupeol was oxidized to lupenone:[9]

Example of PCC oxidation of secondary alcohol

Other reactions[edit]

With tertiary alcohols, the chromate ester formed from PCC can isomerize via a [3,3]-sigmatropic reaction, the Babler oxidation. Other common oxidants usually lead to dehydration because such alcohols cannot be oxidized directly.

PCC also converts suitable unsaturated alcohols and aldehydes to cyclohexenones. This pathway, an oxidative cationic cyclization, is illustrated by the conversion of (−)-citronellol to (−)-pulegone. PCC also effects allylic oxidations, for example, in conversion of dihydrofurans to furanones.[1]

Related reagents[edit]

Other more convenient or less toxic reagents for oxidizing alcohols include dimethyl sulfoxide, which is used in Swern and Pfitzner–Moffatt oxidations, and hypervalent iodine compounds, such as the Dess–Martin periodinane.

Safety[edit]

One disadvantage to the use of PCC is its toxicity, which it shares with other hexavalent chromium compounds.

See also[edit]

References[edit]

  1. ^ a b c Piancatelli, G.; Luzzio, F. A. (2007). "Pyridinium Chlorochromate". e-EROS Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002/9780470842898.rp288.pub2. 
  2. ^ "Safety Data Sheet". Acros Organics. 2015. Retrieved 2016-06-10. 
  3. ^ Lowe, Derek. "The Old Stuff". In The Pipeline. Science. Retrieved 2015-11-21. 
  4. ^ Corey, E. J.; Suggs, J. W. (1975). "Pyridinium Chlorochromate. An Efficient Reagent for Oxidation of Primary and Secondary Alcohols to Carbonyl Compounds". Tetrahedron Lett. 16 (31): 2647–2650. doi:10.1016/S0040-4039(00)75204-X. 
  5. ^ Agarwal, S.; Tiwari, H. P.; Sharma, J. P. (1990). "Pyridinium Chlorochromate: An Improved Method for Its Synthesis and Use of Anhydrous Acetic Acid as Catalyst for Oxidation Reactions". Tetrahedron. 46 (12): 4417–4420. doi:10.1016/S0040-4020(01)86776-4. 
  6. ^ Paquette, L. A.; Earle, M. J.; Smith, G. F. (1996). "(4R)-(+)-tert-Butyldimethylsiloxy-2-cyclopenten-1-one". Org. Synth. 73: 36.  ; Coll. Vol., 9, p. 132 
  7. ^ Tu, Y.; Frohn, M.; Wang, Z.-X.; Shi, Y. (2003). "Synthesis of 1,2:4,5-Di-O-isopropylidene-D-erythro-2,3-hexodiulo-2,6-pyranose. A Highly Enantioselective Ketone Catalyst for Epoxidation". Org. Synth. 80: 1. 
  8. ^ White, J. D.; Grether, U. M.; Lee, C.-S. (2005). "(R)-(+)-3,4-Dimethylcyclohex-2-en-1-one". Org. Synth. 82: 108.  ; Coll. Vol., 11, p. 100 
  9. ^ Lao, A.; Fujimoto, Y.; Tatsuno, T. (1984). "Studies on the Constituents of Artemisia argyi Lévl & Vant". Chem. Pharm. Bull. 32 (2): 723–727. doi:10.1248/cpb.32.723. Retrieved 2016-06-05. 

Further reading[edit]

  • Tojo, G.; Fernández, M. (2006). Tojo, G., ed. Oxidation of Alcohols to Aldehydes and Ketones: A Guide to Current Common Practice. Basic Reactions in Organic Synthesis. New York: Springer. ISBN 978-0-387-23607-0. 

External links[edit]