Pyridinium chlorochromate

Pyridinium chlorochromate
Names
	IUPAC name Pyridinium chlorochromate
	Other names PCC; Corey-Suggs reagent
Identifiers
CAS Number	26299-14-9 ;
3D model (JSmol)	Interactive image;
ChEBI	CHEBI:176795;
ChemSpider	10608386 ;
ECHA InfoCard	100.043.253
EC Number	247-595-5;
PubChem CID	129695875;
UNII	DTV5HU1N27 ;
CompTox Dashboard (EPA)	DTXSID40893953 ;
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Properties
Chemical formula	C5H6ClCrNO3
Molar mass	215.56 g/mol
Appearance	yellow-orange solid
Melting point	205 °C (401 °F; 478 K)
Solubility in other solvents	soluble in acetone, acetonitrile, THF
Hazards
Main hazards	Suspected carcinogen and environmental pollutant
Safety data sheet	external SDS
GHS pictograms
GHS Signal word	Danger
GHS hazard statements	H350, H272, H317, H410
GHS precautionary statements	P201, P280, P273, P221, P308+313, P302+352
NFPA 704 (fire diamond)	2 1 2 OX
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	(what is ?)
	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. 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[]

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] and potassium chlorochromate.

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[]

Oxidation of alcohols[]

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. The reagent is more selective than the related Jones reagent, so there is little chance of over-oxidation to form carboxylic acids as long as water is not present in the reaction mixture. 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, the triterpene lupeol was oxidized to :^[9]

Babler oxidation[]

With tertiary alcohols, the chromate ester formed from PCC can isomerize via a [3,3]-sigmatropic reaction and following oxidation yield an enone, in a reaction known as the Babler oxidation:

This type of oxidative transposition reaction has been synthetically utilized, e.g. for the synthesis of morphine.^[10]

Using other common oxidants in the place of PCC usually leads to dehydration, because such alcohols cannot be oxidized directly.

Other reactions[]

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[]

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[]

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

References[]

^ Jump up to: ^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. ISBN 978-0471936237.
^ "Safety Data Sheet". Acros Organics. 2015. Retrieved 2016-06-10.
^ Lowe, Derek. "The Old Stuff". In The Pipeline. Science. Retrieved 2015-11-21.
^ 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.
^ 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.
^ Paquette, L. A.; Earle, M. J.; Smith, G. F. (1996). "(4R)-(+)-tert-Butyldimethylsiloxy-2-cyclopenten-1-one". Organic Syntheses. 73: 36.CS1 maint: multiple names: authors list (link); Collective Volume, 9, p. 132
^ 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". Organic Syntheses. 80: 1.CS1 maint: multiple names: authors list (link)
^ White, J. D.; Grether, U. M.; Lee, C.-S. (2005). "(R)-(+)-3,4-Dimethylcyclohex-2-en-1-one". Organic Syntheses. 82: 108.CS1 maint: multiple names: authors list (link); Collective Volume, 11, p. 100
^ 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.
^ Killoran, Patrick M.; Rossington, Steven B.; Wilkinson, James A.; Hadfield, John A. (2016). "Expanding the scope of the Babler–Dauben oxidation: 1,3-oxidative transposition of secondary allylic alcohols". Tetrahedron Letters. 57 (35): 3954–3957. doi:10.1016/j.tetlet.2016.07.076.

External links[]

[eEROS-1] Jump up to: ^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. ISBN 978-0471936237.

[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.

[corey-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". Organic Syntheses. 73: 36.CS1 maint: multiple names: authors list (link); Collective Volume, 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". Organic Syntheses. 80: 1.CS1 maint: multiple names: authors list (link)

[8] White, J. D.; Grether, U. M.; Lee, C.-S. (2005). "(R)-(+)-3,4-Dimethylcyclohex-2-en-1-one". Organic Syntheses. 82: 108.CS1 maint: multiple names: authors list (link); Collective Volume, 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.

[10] Killoran, Patrick M.; Rossington, Steven B.; Wilkinson, James A.; Hadfield, John A. (2016). "Expanding the scope of the Babler–Dauben oxidation: 1,3-oxidative transposition of secondary allylic alcohols". Tetrahedron Letters. 57 (35): 3954–3957. doi:10.1016/j.tetlet.2016.07.076.

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