1

1 - Chromium based oxidation reagents

Chromium(VI) compounds are widely used and very powerful oxidation agents1 for several
functional groups.
Their most common application is
the selective oxidation of primary
and secondary alcohols to
aldehydes, ketones,2,3 or carboxylic
acids. Aldehydes derived from
primary alcohols can only be
isolated under certain reaction
conditions or by using specialized
oxidation reagents.
The mechanism of this reaction is known to proceed via chromyl-esters4 which are cleaved to their
products through base-catalysis.
During reaction chromium species of lower oxidation states (IV and V) are also involved5,6.
In aqueous solutions primary alcohols are usually oxidized to carboxylic acids7,8, while in the
absence of water the oxidation will stop at the aldehyde. The complete oxidation to the carboxylic
acid can also be avoided if the intermediately-formed aldehyde are removed from the reaction
mixture by distillation or other means7.
Common reagents for the selective
oxidation of alcohols to aldehydes
and ketones are pyridinium
chlorochromate, known as Corey’s
reagent9, and a mixture of
chromium(VI) oxide and pyridine10,11
in dichloromethane, known as
Collins reagent12.

1 S.V.Ley, A.Madin, Oxidation Adjacent to Oxygen of Alcohols by Chromium Reagents in

Comprehensive Organic Synthesis, Pergamon Press, Oxford, 1991.
2 F.A.Luzzio, Organic. Reactions 53 (1998) 1.
3 G.Piancatelli, A. Scettri, M. D’Auria, Synthesis (1982), 245.
4 F.Holloway, M.Cohen, F.H.Westheimer, J.Am,Chem.Soc 71 (1951) 65.
5 a) K.B.Wiberg, G.Szeimies, J.Am.Chem.Soc. 96 (1974) 1889 ; b) K.B.Wiberg, S.K. Mukherjee,
J.Am.Chem.Soc. 96 (1974) 1884.
6 M.Doyle, R.J.Swedo, J.Rocek, J.Am.Chem.Soc, 95 (1973) 8352.
7 D.G.Lee, U.A.Spitzer J.Org.Chem. 35 (1970) 3589.
8 G.R.Robertson, Organic Synthesis, Coll. Vol. 1 p 138.
9 E.J.Corey, J.W.Suggs Tetrahedron Lett. 31 (1975) 2647.
10 G.I.Poos, G.E.Arth, R.E.Beyler, L.H.Sarett J.Am.Chem.Soc. 75 (1953) 422.
11 R.Ratcliffe, R. Rodehorst J.Org.Chem. 35 (1970) 4000.
12 J.C.Collins, W.W.Hess, J.F.Frank, Tetrahedron Lett. 30 (1968) 3363.
1
 In addition to the oxidation of alcohols, several other reactions can use chromium (VI) compounds
such as:
• the oxidation and the oxidative cleavage13 of double bonds,
• the oxidation of allylic14 or benzylic compounds to aryl ketones15, benzoic acids16 and aromatic
aldehydes17
• the oxidation of polyaromatic hydrocarbons to quinones
• recovery of carboxyl compounds from their oxime derivatives18
• the mild and selective oxidative deprotection of trimethylsilyl-19 or THP-ethers20
• oxidation of aromatic thioethers to sulfoxides21 and sulfones
• synthesis of (dichloroiodo)arenes22.
In past years numerous similar reagents with special properties, such as ease of preparation,
selectivity, and stability have been developed. Solid supported reagents have also recently gained
interest20,23,24,25.

Acros Organics offers a complete range of chromium based oxidation reagents, presented on the
following pages with additional information and literature.
AMMONIUM DICHROMATE, 99% (20881) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
BENZYLTRIETHYLAMMONIUM CHLOROCHROMATE, 98% (32760) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2,2’-BIPYRIDINIUM CHLOROCHROMATE, 97% (21727) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
CHROMIUM(VI) OXIDE, 99.9% (21410) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
CHROMIUM(VI) OXIDE, 99+% (19661) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
CHROMOSULFURIC ACID (29551) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
CHROMYL CHLORIDE, 99+% (19046) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
IMIDAZOLIUM DICHROMATE, 98% (32762) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
POLY (4-VINYLPYRIDINIUM DICHROMATE), CROSS LINKED WITH 2% DVB; 2.2MMOL Cr/G RESIN (21782) 6
POTASSIUM CHLOROCHROMATE, 98% (32761) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
POTASSIUM CHROMATE, P.A. (20234) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -
POTASSIUM DICHROMATE, 4WT% SOLUTION IN WATER (38280) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
POTASSIUM DICHROMATE, 99.5% (19776) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
POTASSIUM DICHROMATE, P.A. (19659) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
POTASSIUM DICHROMATE, REAGENT ACS (CRYSTALS) (42411) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
PYRIDINIUM CHLOROCHROMATE, 98% (18367) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
PYRIDINIUM DICHROMATE, 98% (20088) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
PYRIDINIUM FLUOROCHROMATE (30248) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
SILICAGEL, FUNCTIONALIZED WITH 20% PYRIDINIUM DICHROMATE (37222) . . . . . . . . . . . . . . . . . . . . 6
SILICAGEL, FUNCTIONALIZED WITH PYRIDINIUM CHLOROCHROMATE (37124) . . . . . . . . . . . . . . . . . . . . 5
SILVER CHROMATE, 99% (21125) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -
SODIUM DICHROMATE DIHYDRATE, 99% (21924) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

13 C.E.Harris, L.Y.Lee, H.Dorr, B. Singaram, Tetrahedron Lett. 36 (1995) 2921.

14 Marshall, Ley, Laos, Riegel, J.Am.Chem.Soc 79 (1957) 6308; Suga, Sugimoto, Fujita,
Matsuura, Bull. Soc. Chim.Jap 39 (1966) 2546; Dauber, Lorber Fullerton J.Org.Chem. 34 19 J.Muzart, Synthesis (1993) 11.
(1969) 3587. 20 M.M.Hervari, D.Ajami, M.Ghassemzadeh, Synthesis, 3 (1999) 393.
15 a) J.W.Burnham,W.P.Duncan, E.J.Eisenbraun, G.W.Keen, M.C.Hamming, J.Org.Chem 39. 21 C. Karunakaran, V. Chidambaranathan Croatica Chemica Acta 74 (2001) 51.
(1974) 1416; b) R. Rangarajan, E.J.Eisenbraun, J.Org.Chem. 50 (1985) 2435. 22 N.Obeid, L.Skulski, Molecules 6 (2001) 869.
16 L.Friedman, D.L Fishel, H.Shechter, J.Org.Chem 30 (1965) 1453. 23 A.Kirschnigg, H.Monenschein, R.Wittenberg, Angew. Chem 2001 113, 670.
17 H.Maehr, J. M. Smallheer, J.Org.Chem 46 (1981) 1752. 24 M.Z.Kassaee, S.Z.Sayyed-Alangi, H.Sajjadi-Ghotbabadi, Molecules 9 (2004) 825.
18 J. Drabovicz, Synthesis (1980) 125. 25 N. Deirmenba, B.Özgün, Monatshefte für Chemie 135 (2004) 407.
2
CHROMOSULFURIC ACID (29551)
Chromosulfuric acid is a very powerful oxidation agent. It can be used for the cleaning of
glassware, because it destroys organic substances by oxidation, but has often been replaced by
less toxic alternatives.

CHROMYL CHLORIDE, 99+% (19046)

Chromyl chloride26 has been used in the Etard27-reaction, the oxidation of methylarenes to
benzaldehydes28. It has also been used in the oxidation of olefins29 to epoxides30,31,
chlorocarbonylcompounds32, chloroacetals33, and carbonylcompounds34.
A complex of chromyl chloride with pyridine is a
very powerful oxidation reagent for alcohols
compared to the Collins reagent35.

POTASSIUM DICHROMATE, 99.5% (19776)

POTASSIUM DICHROMATE, 4WT% SOLUTION IN WATER (38280)
POTASSIUM DICHROMATE, REAGENT ACS (CRYSTALS) (42411)
POTASSIUM DICHROMATE, P.A. (19659)
Potassium dichromate is a widely used strong oxidation reagent. It has been used for the
oxidation of alcohols and for the oxidative cleavage of oximes, trimethylsilyl- and THP ethers under
solvent free conditions36. A solution of potassium dichromate and sulfuric acid can be used for the
oxidative cleavage of enaminedouble bonds13, a method to de-homologize aldehydes.

26 F.A.Luzzio, W.J.Moore, J.Org.Chem 58 (1993) 512.
27 A.L.Etard, Compt. Rend. 90, 534 (1880).
28 W. H.Hartford, M.Darrin, Chem,Rev. 58, (1958) 1-61.
29 M.Torrent, L.Deng, T.Ziegler, Inorg. Chem. 37 (1998) 1307 ; M.Torrent, L.Deng, M.Duran, M.
Solà, T.Ziegler Can.J.Chem 77 (1999) 1476.
30 N.Miyaura, J.K.Kochi, J.Am.Chem.Soc.105 (1983) 2368 ; F.W.Bachelor, U.O. Cheriyan,
Can.J.Chem. 54 (1976) 3383 ; F.W.Bachelor, U.O. Cheriyan J.Chem.Soc.Chem.Comm. (1973)
195.
31 C.Limberg, R.Koppe, Inorg.Chem. 38 (1999) 2106.
32 K.B. Sharpless and A.Y. Teranishi, J.Org.Chem. 38, 185 (1973).
33 J.-E. Bäckvall, M.W.Young, K.B.Sharpless, Tetrahedron Lett. (1977) 3523 ; K.B. Sharpless, A.Y.
Teranishi, and J.-E. Bäckvall, J. Am. Chem. Soc., 99 (1977) 3120.
34 F.Freeman, P.J.Cameron, J.Org.Chem. 33 (1968) 3970; F.Freeman, R.H.DuBois, N.J. Yamachika
Tetrahedron 25 (1969) 3441, .Freeman, N.J. Yamachika J.Am.Chem.Soc. 94 (1972) 1214.
35 K.B.Sharpless, K.Akashi, J.Am.Chem.Soc. 97 (1975) 5927.
36 I.Mohammadpoor.Baltork, M.M. Sadeghi, A.-H. Adibi, Molecules 6 (2001) 900.
3
 IMIDAZOLIUM DICHROMATE, 98% (32762)
A selective and mild reagent for the selective
oxidation of allylic and benzylic alcohols to
carbonyl compounds37.
Oximes, hydrazones and semicarbazones are
converted to the corresponding carbonyl
compounds using imidazolium dichromate
adsorbed on alumina38.

POTASSIUM CHLOROCHROMATE, 98% (32761)

Reagent for the oxidation of allylic-, benzylic- and secondary alcohols to aldehydes and ketones.

BENZYLTRIETHYLAMMONIUM CHLOROCHROMATE, 98% (32760)

The mechanism and kinetics of the oxidation of formic and oxalic acids with benzyltriethyl
ammonium chlorochromate39 has been determined.

37 S.Kim, D.C. Lhim Bull.Soc.Chim.Jap. 59 (1986) 3297.

38 S Kanta De, Letters in Organic Chemistry, 2/1, (2005).
39 K. Chouhan, P. K Sharma Ind.J.Chem., 43A, (2004), 1434-1438.
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PYRIDINIUM CHLOROCHROMATE, 98% (18367)
SILICAGEL, FUNCTIONALIZED WITH PYRIDINIUM CHLOROCHROMATE (37124)
Pyridinium chlorochromate (Corey’s reagent), a air-
stable yellow solid, is the reagent of choice for
many types of oxidation reactions3,40.
This reagent oxidizes 1° and 2° alcohols selectively
to aldehydes and ketones.
Addition of other aromatic amines like
benzotriazole41 increases the selectivity of this
reagent towards allylic alcohols rather than non-
allylic alcohols. 1H-Benzotriazole, 98% . . . . . 18388
PCC can be used for the oxidative cleavage of
boranes and oximes18 to aldehydes and ketones. 1H-Benzotriazole, 99% . . . . . 10567
The oxidation of 5,6-Dihydropyranes with PCC
leads to α,β-unsaturated δ-Lactones42.
PCC can also be used for several other
oxidation reactions, which are summarized in
the following scheme:

A higher reactivity and an easier work-up can

be achieved using reagent adsorbed on
alumina43 and in the presence of molecular
sieves1.

40 R.A.Fernandez, Synlett 5 (2003) 741. 42 F.Bonadies, R.DiFabio, C. Bonini, J.Org.Chem. 49 (1984) 1647.
41 E.J.Parish, S.Chitrakorn, Synth.Comm. 15 (1985) 393. 43 Y.-S. Cheng, W.-L. Liu, S.-H. Chen, Synthesis (1980) 223.
5
 PYRIDINIUM DICHROMATE, 98% (20088)
SILICAGEL, FUNCTIONALIZED WITH 20% PYRIDINIUM DICHROMATE (37222)
POLY (4-VINYLPYRIDINIUM DICHROMATE), CROSS LINKED WITH 2% DVB;
2.2MMOL Cr/G RESIN (21782)
Pyridinium dichromate, or the Corey Schmitt44 reagent, is a stable orange solid used for the
selective oxidation of allylic alcohols to α,β-unsaturated aldehydes in the presence of other
primary or secondary alcohols.
Depending on the solvent, the reagent oxidizes non-allylic
primary alcohols to the aldehydes in dichloromethaneor to
the carboxylic acidsin dimethylformamide
Another application of PDC is in the aromatization of 1,4-
dihydropyridines45.

2,2'-BIPYRIDINIUM CHLOROCHROMATE, 97% (21727)

2,2'-Bipyridinium chlorochromate is a mild, air stable and non-hygroscopic oxidation reagent46. It is
somewhat weaker than pyridinium chlorochromate, and a higher excess of reagent (usually 2-4
fold) is necessary for complete reaction1. It is used mostly for the oxidation of alcohols to carbonyl
compounds but the reagent has also been used together with m-Chloroperbenzoic acid AO
25579 for the oxidative cleavage of cyclic
acetales47 and for the oxidation of sulfides to m-Chloroperbenzoic acid . . . 25579
sulfoxides and sulfones.

PYRIDINIUM FLUOROCHROMATE (30248)

Pyridinium fluorochromate is a stable solid and can be stored for prolonged periods. It oxidizes
primary alcohols to aldehydes and secondary
alcohols to ketones in high yield, and can be used
for the oxidation of polycyclic aromatic
compounds to chinones48. Pyridinium fluoro-
chromate has a comparable selectivity in oxidation
reactions to pyridinium chlorochromate, but has a
lower acidity. This makes pyridinium fluoro-
chromate more suitable where acid sensitive
alcohols have to be oxidized49. The tolerance of
PFC against tert-Butyldimethylsilyl protecting
groups allows the oxidation of a secondary alcohol
in the presence of a (protected) primary alcohol50.
The reagent also has allowed the direct oxidation of organoboranes to ketones in the synthesis of
24-Ketolanosteryl acetate51.
44 E.J. Corey, G. Schmidt, Tetrahedron Lett. (1979) 399-402.
45 K.-Y Ko, J Y. Park, Bull. Korean Chem. Soc. 16 (1995) 200-201.
46 F.S.Guziec, F.A.Luzzio, Synthesis (1980) 691.
47 F.A. Luzzio, R.A. Bobb, tetrahedron Lett. 38 (1997) 1733. 49 M.N. Bhattacharjee , M. K. Chaudhuri, S. Purkayastha, Tetrahedron 43 (1987) 5389.
48 M.N. Bhattacharjee , M. K. Chaudhuri, H.S.Dasgupta, N.Roy, D.T. Khathing, Synthesis (1982) 50 T. Nonaka, S. Kanemoto, K. Oshima, H. Nozaki, Bull. Soc. Chim. Jap. 57 (1984) 2019.
588. 51 E.J.Parish, H.Sun, S. Kizito, T.L.Boss Molecules 5 (2000) 114.
6
SODIUM DICHROMATE DIHYDRATE, 99% (21924)
Sodium dichromate in sulfuric acid or in acetic acid is a very powerful oxidation reagent and was
widely used before the development of milder and more selective alternatives1.
Sodium dichromate and sulfuric acid in dimethyl sulfoxide oxidizes primary and secondary alcohols
to the aldehydes and ketones52. An aqueous solution of sodium dichromate oxidizes alkyl arenes
to carboxylic acids16. It can also oxidize primary alcohols to the carboxylic acids via the aldehydes,
which can only be isolated under special reaction conditions7.

CHROMIUM(VI) OXIDE, 99.9% (21410)

CHROMIUM(VI) OXIDE, 99+% (19661)
Chromium(VI) oxide is widely used for the preparation of other oxidation reagents such as the
Jones and Collins reagents. Chromium(VI) oxide can be used for the oxidation of aromatic
hydrocarbons to chinones53. The mixture of chromic acid and sulfuric acid in acetone, the Jones
reagent54, is widely used for oxidations.
Secondary alkohols are oxidized to ketones
while primary alkohols are oxidized to
carboxylic acids. The oxidation of secondary
alcohols to ketones can be performed in the
presence of isolated double and triple bonds,
where they will not be attacked by the
reagent. An example for the use of Jones
reagent is the oxidation of Pregnenolone55.

The complex of chromium(VI) oxide with

pyridine12 in dichloromethane is called the
Collins reagent56. The complex is difficult
and dangerous to prepare57, very hygroscopic,
not very soluble in dichloromethane and
usually requires a six-fold excess to complete
the reaction. It does, though, oxidize primary alcohols selectively to the aldehydes and tolerates
many functional groups.
The complex of chromium(VI) oxide with 3,5-
dimethylpyrazole is very soluble in
dichloromethane and generally requires a smaller
excess of reagent (~2.5 fold).

52 Y. S. Rao, R.Filler J.Org.Chem 39 (1974) 3304.

53 Organikum, p. 439 , 21st issue, Autorenkollektiv, Wiley-VCh, Weinheim 2001. 56 J. C. Collins, W. W. Hess, Organic Syntheses, Coll. Vol. 6, p.644.
54 A.Bowers, T.G. Halsall, E.R.H.Jones, A.J.Lemin, J.Chem.Soc. (1953) 2548. 57 Special precautions and procedures must be followed when mixing chromium trioxide and
55 C.Djerassi, R.R.Engle, A.Bowers, J.Org.Chem. 21 (1956) 1547. pyridine since the mixture is flammable.
7
 Chromium(IV) oxide in different solvents has been used for the oxidation of secondary alcohols to
ketones and the oxidation of aromatic side chains to benzaldehydes or benzoic acids. Examples
include Chromium (VI) oxide in:
• acetic acid (Fieser reagent),
• pyridine (Sarett reagent58),
• aqueous pyridine (Cornforth reagent59),
• acetic anhydride and sulfuric acid (Thiele reagent)60
• diethylether in the presence of Celite61.

Chromium(VI) oxide has been used as a

3,5-Dimethylpyrazole, 98,5% . . 11637 catalytic oxidant with tert-butylhydroperoxide
as a co-oxidant62.
tert-Butylhydroperoxide,
70% in water . . . . . . . . . . . . . . . 18034

AMMONIUM DICHROMATE, 99% (20881)

Ammonium dichromate on silica has been used in solvent free conditions for the oxidation of
primary and secondary alcohols to aldehydes63.

58 N. Arumugam, P. C. Srinivasan, Synth.Comm. 33 (2003) 2313.

59 R.H. Cornforth, J.W. Cornforth, G. Popják, Tetrahedron 18 (1962) 1351. 61 S.J.Flatt, G.W.F. Fleet, B.J.Taylor, Synthesis (1979) 815.
60 J.Thiele, E.Winter, Liebigs.Ann.Chem. 311 (1900) 353; see also: T. Nishimura, Org.Synth.Coll 62 J.Muzart, Tetrahedron Lett. 28 (1987) 2133.
Vol IV, (1963) 713. 63 F.Shirini, M.A.Zolfigol, M.Khaleghi, Bull.Korean.Chem.Soc 24 (2003) 1021.
8