Pyridinium chlorochromate
| Template:Chembox header | Pyridinium chlorochromate | |
|---|---|
| Chemical structure of the Pyridinium Chlorochromate Ball-and-stick model of the pyridinium cation Ball-and-stick model of the chlorochromate anion | |
| Template:Chembox header | General | |
| Systematic name | Pyridinium Chlorochromate |
| Synonum | PCC |
| Molecular formula | C5H5NHClCrO3 |
| Molar mass | 215.56 g/mol |
| Appearance | orange crystalline powder |
| CAS number | 26299-14-9 |
| Template:Chembox header | Properties | |
| Melting point | 205 °C |
| Solubility | soluble in dichloromethane, benzene, diethyl ether, sol acetone, acetonitrile, THF |
| Template:Chembox header | Hazards | |
| MSDS | external MSDS sheet |
| Main hazard | oxidizing, toxic, flammable carcinogenic, irritant |
| NFPA 704 | Template:NFPA 704 |
| R/S statement | R: 49-8-43-50/53 S: 53-45-60-61 |
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Overview
Pyridinium chlorochromate, a reddish orange solid reagent, is used to oxidize primary alcohols to aldehydes and secondary alcohols to ketones. Pyridinium chlorochromate, or PCC, will not fully oxidize the alcohol to the carboxylic acid as does the Jones reagent. A disadvantage to using PCC is its toxicity. PCC was developed by Elias James Corey and William Suggs in 1975.
Pyridinium dichromate or PDC is a similar oxidizing agent with chemical formula (C5H5NH)2Cr2O7. In this compound chromium is present as the dichromate ion. PDC presents the advantage of being less acidic than PCC.
Preparation
The original preparation by Corey involves adding one equivalent of pyridine to a solution of one equivalent of chromium(VI) trioxide and concentrated hydrochloric acid:
- C5H5N + HCl + CrO3 → [C5H5NH][CrO3Cl]
Agarwal et al. presented an alternative synthesis that avoids the harmful side product chromyl chloride (CrO2Cl2). Chromium(VI) oxide pyridinium chloride:
- [C5H5NH+]Cl- + CrO3 → [C5H5NH][CrO3Cl]
Properties and uses
PCC is primarily used as an oxidant. In particular, it has proven to be highly effective in oxidizing primary and secondary alcohols to aldehydes and ketones, respectively. Rarely does over-oxidation occur (whether intentionally or accidentally) to form carboxylic acids. A typical PCC oxidation involves addition of the alcohol to a suspension of PCC in dichloromethane. A sample reaction would be:
- 2 C5H5NHCrO3Cl + 3 R2CHOH → 2 C5H5NHCl + "CrO1.5" + 3 R2C=O + 3 H2O
In practice the chromium byproduct deposits with pyridine as a sticky black tar, which can complicate matters. Addition of an inert adsorbent such as crushed molecular sieves or silica gel allows the sticky byproduct to adsorb to the surface, and makes workup easier.
PCC is also remarkable for its high selectivity. For example, when oxidizing tertiary allyl alcohols, unsaturated aldehydes are observed as the sole product. This reaction is known as the Babler oxidation. Otherwise such oxidations commonly afford dienes as by-products resulting from dehydration.
Another notable oxidative reaction of PCC is its efficient conversion of unsaturated alcohols or aldehydes to cyclohexenones. This particular pathway is known as oxidative cationic cyclization.
Controversy
PCC is controversial as it contains chromium(VI). More environmentally friendly oxidants listed above are therefore favored by green chemists. Other methods for oxidizing alcohols using less toxic reagents have been introduced:
- DMSO-based oxidations (Swern oxidation, Moffatt oxidation)
- hypervalent iodine based oxidation (such as the Dess-Martin periodinane)
References
- Agarwal, S, Tiwari, H. P., Sharma, J. P., 'Pyridinium Chlorochromate: an Improved Method for its Synthesis and use of Anhydrous acetic acid as catalyst for oxidation reactions', Tetrahedron (journal) 1990, 46, 4417-4420.
- Corey, E.J., and Suggs, W. 'Pyridinium Chlorochromate. An Efficient Reagent for Oxidation of Primary and Secondary Alcohols to Carbonyl Compounds', Tetrahedron Lett. 1975, 16, 2647-2650.
- Paquette, L. A.; Earle, M. J.; Smith, G. F. Organic Syntheses, Coll. Vol. 9, p.132 (1998); Vol. 73, p.36 (1996). (Article)
- Piancatelli, G. 'Pyridinium Chlorochromate', Encyclopedia of Reagents for Organic Synthesis 2001. (Article)
- Tu, Y.; Frohn, M.; Wang, Z.-X.; Shi, Y. Organic Syntheses, Vol. 80, p.1 (2003). (Article)
- White, J. D.; Grether, U. M.; Lee, C.-S. Organic Syntheses, Vol. 82, p.108 (2005). (Article)
External links
- IARC Monograph "Chromium and Chromium compounds"
- History of PCC
- Datasheet PDC
- National Pollutant Inventory - Chromium VI and compounds fact sheet