Author Topic: Sodium percarbonate and the Dakin reaction  (Read 1909 times)

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Sodium percarbonate and the Dakin reaction
« on: November 07, 2002, 07:55:00 PM »
This bee found a rather interesting reference today when reading a new chem book on reaction mechanisms. It involves the so-called Dakin-reaction.

Tetrahedron Letters 33(7) (1992) 865-866
Title: Sodium Percarbonate: A Convenient Reagent for the Dakin Reaction
Authors: G W Kabalka (*), N K Reddy, C Narayana
Departments of Chemistry and Radiology, The University of Tennesse, Knoxville, TN 37996-1600.

Abstract: Sodium percarbonate, a readily available, inexpensive and easy to handle reagent efficiently oxidizes hydroxylated benzaldehydes and hydroxylated acetophenones to hydroxyphenols.

Phenols and their derivatives are fundamentally important substrates used extensively in organic synthesis. In the Dakin reaction, hydroxylated benzaldehydes are converted to hydroxy-phenols through the replacement of formyl groups by a hydroxyl moiety using alkaline hydrogen peroxide (1). Other reagents have been employed to oxidize aromatic aldehydes to arylformates; these include peroxyacetic acid (2), peroxybenzoic acid (3), m-chloroperoxybenzoic acid (4) and organoperoxyselenic acid (5).
Sodium percarbonate (Na2CO3.1,5H2O2) is a very inexpensive large scale industrial chemical which is extensively used in the detergent industry as a bleaching agent (6). It has been used for the oxidation of sulfides (7), amines (7,8), organoboranes (9) as well as for the epoxidation of olefins (7) and hydrolysis of nitriles to amides (10). We now wish to report that sodium percarbonate oxidizes hydroxylated benzaldehydes and acetophenones to hydroxy phenols in good yields (Table).
In a typical procedure, a mixture of aromatic aldehyde (3.0 mmol) and sodium percarbonate (3.0 mmol) is dissolved in tetrahydrofuran (10.0 mL) and water (4.0 mL) and sonicated in an ultrasound bath under an argon atmosphere. The reaction is quenched with acetic acid (1.0 mL) and the solvent removed under vacuum. Methanol is added to the residue and the mixture filtered. The filtrate is concentrated under reduced pressure and chromatographed (silica gel; 30% ethyl acetate in hexanes).
Para-hydroxybenzaldehydes react more slowly than the corresponding ortho-hydroxybenzaldehydes. Meta-hydroxybenzaldehyde fails to undergo oxidation. 4-hydroxy-3-nitrobenzaldehyde also failed to react with Na2CO3.1,5H2O2 which may be due to intramolecular hydrogen bonding. In addition to aromatic aldehydes, we examined the conversion of hydroxylated acetophenones to hydroxyphenols. 2-hydroxyacetophenones (entries 11 and 13) were oxidized to catechols while 4-hydroxyacetophenones (entries 12 and 14) failed to undergo oxidation.

Table. Oxidation of hydroxylated benzaldehydes and acetophenones to hydroxyphenols

Entry  Substrated                         Time (h)  Product                Yield (%)
 01    salicylaldehyde                       5      catechol                  91
 02    4-hydroxybenzaldehyde                 8      hydroquinone              86
 03    3-hydroxybenzaldehyde                20      -----------------         --
 04    o-vanillin                            1      3-methoxycatechol         95
 05    2-hydroxy-4-methoxybenzaldehyde       2      4-methoxycatechol         83
 06    vanillin                              4      2-methoxyhydroquinone     93
 07    5-chloro-2-hydroxybenzaldehyde        5      4-chlorocatechol          92
 08    2-chloro-4-hydroxybenzaldehyde        7      2-chlorohydroquinone      62
 09    2-hydroxy-5-nitrobenzaldehyde         7      4-nitrocatechol           60
 10    4-hydroxy-3-nitrobenzaldehyde        20      -----------------         --
 11    2-hydroxyacetophenone (#)             8      catechol                  90
 12    4-hydroxyacetophenone                20      -----------------         --
 13    2-hydroxy-4-methoxyacetophenone       7      4-methoxycatechol         78 (*)
 14    3,5-dimethoxy-4-hydroxyacetophenone  20      -----------------         --
 # A mixture of THF-DMF-H2O (3:1:1) was used as a solvent for acetophenone reactions.
 * Based on 80% conversion of the starting material.

Acknowledgement: We thank the Department of Energy for support of this research.
Dedication: Dedicated to Professor Herbert C. Brown on the occasion of his 80th library.

1. Hassal CH. "Org Reaction"; Wiley, New York, 1957, vol 9, pp 73-106.
2. Boeseken J, Cohen WD, Kip CJ; Rec Trav Chim Pays-Bas 55 (1936) 815.
3. Ogata Y, Sawaki Y; J Org Chem 34 (1969) 3985.
4. Camps F, Coll J, Messeguer A, Pericas MA; Tetrahedron Lett 22 (1981) 3895.
5. Syper L; Synthesis (1989) 167.
6. Das TK; Mandavawalla AK, Dalta SK; Colourage 301 (1983) 25.
7. Ando T, Conk DG, Kimura T; Chem Lett (1986) 665.
8. Zajac WW, Walters TR, Woods JM; Synthesis (1988) 808.
9. Kabalka GW, Wadgaonkar PP, Shoup TM; Organometallics 9 (1990) 1316.
10. Kabalka GW, Deshpande SM, Wadganonkar PP, Chatla N; Syn Commun 20 (1990) 1445.

--- The End ---

Didn't find it in TFSE. Since the applied substances (sodium percarbonate) are not only extremely OTC but also relatively cheap, and since yields don't look that bad, SWiM thought by himself... "hell, let's share that one"  ;) .
Hint: think further, think methylating... This procudure might be an alternative to some Baeyer-Villiger oxidations.

EDIT: why do my posts using (pre)(/pre) always fuck up  :(

Ave Hive, synthetisandi te salutant!


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« Reply #1 on: November 08, 2002, 04:39:00 AM »
Information like this is why I read the Hive.  You just made my day man.  Once more the range of synthesis options provided to bees has been expanded.  Great find, I hope that someone tries this soon, and i'll definately be looking into it for the future ;)