Dinitratocerium(IV) Chromate Dihydrate1

[Ce(NO3)2]CrO4.2H2O

[92989-80-5]  · CeCrH4N2O12  · Dinitratocerium(IV) Chromate Dihydrate  · (MW 416.18)

(mild oxidizing reagent for the transformation of several functional groups in dry benzene2)

Alternate Name: DCCD.

Solubility: sol DMF, DMSO; moderately sol H2O; insol MeCN, EtOH, PhH.

Form Supplied in: orange-red solid; readily available.

Preparative Method: to a hot solution of Potassium Dichromate (0.1 mol) a solution of Cerium(IV) Ammonium Nitrate (0.1 mol) is added. After cooling, the precipitate is washed with H2O and acetone and dried in the air (79%).2

Handling, Storage, and Precautions: stable >220 °C, and at rt for months. Chromium is a cancer suspect agent and inhalation of this reagent should be avoided.

Oxidations.

Oxidations with this reagent proceed heterogeneously in dry benzene at reflux. Evaporation of the solvent followed by chromatography gives pure product(s). Drawbacks encountered with CeIV oxidations1,3 are not observed when using DCCD.2

The reagent effects the oxidation of benzylic alcohols to the corresponding aldehydes in high yield (eq 1).2 Deactivated benzyl and allylic alcohols are not easily oxidized. Oxidation of arylethylene glycols is accompanied by carbon-carbon bond cleavage and produces the degraded aldehydes in high yields (eq 2).2 a-Hydroxy carboxylic acids are similarly converted to aldehydes efficiently (eq 3).2

Primary benzylamines are easily transformed to the corresponding aldehydes in quantitative yields (eq 4).2 Disulfides are produced in good yields by the oxidation of thiols (eq 5).2 The reagent oxidizes hydroquinones to quinones in high yields (eq 6).2 Benzoins are not oxidized efficiently.

A brief comparison between DCCD, Cerium(IV) Ammonium Nitrate (CAN),1a,3,4 Barium Manganate (BM),5 and Bis(pyridine)silver(I) Permanganate (BPSP)6 is given in Table 1.


1. (a) Ho, T. L. In Organic Synthesis by Oxidation with Metal Compounds; Mijs, W. J.; de Jonge, C. R. H. I., Eds.; Plenum: New York, 1986; p 569. (b) Molander, G. A. CRV 1992, 92, 29.
2. Firouzabadi, H.; Iranpoor, N.; Kiaeezadeh, F.; Toofan, J. SC 1984, 14, 973.
3. Ho, T. L. S 1973, 347.
4. Trahanovsky, K.; Young, L. B.; Brown, G. L. JOC 1967, 32, 3865.
5. Firouzabadi, H.; Mostafavipour, Z. BCJ 1983, 56, 914.
6. Firouzabadi, H.; Vessal, B.; Naderi, M. TL 1982, 23, 1847.

Habib Firouzabadi

Shiraz University, Iran



Copyright 1995-2000 by John Wiley & Sons, Ltd. All rights reserved.