SODIUM PERCARBONATE 1
of organic sulfides by anhydrous sodium percarbonate in glacial
Sodium Percarbonate1
acetic acid is a second-order reaction.5 Solvent-free, chemoselec-
tive oxidation of sulfides to sulfones is readily achievable using
O
SPC and Amberlyst as a solid support.6
Na
O O
H
O
Na
O
O
SPC
O
S
H (1)
R1 R2 aq CH3CN R1 S
R2
[15630-89-4] 2Na2CO3·3H2O2 (MW 157)
Na2CO3·3/2 H2O2
The deselenylation of Ä…-(phenylseleno)carbonyl compounds
Na2CO3·1.5 H2O2
to the corresponding Ä…,²-unsaturated carbonyl compounds has
InChI = 1/CH2O3.2Na.H2O2/c2-1(3)4;;;1-2/h(H2,2,3,4);;;1-2H/
been carried out in tetrahydrofuran using acetic anhydride and
q;2*+1;/p-2/fCO3.2Na.H2O2/q-2;2m;
a large excess of SPC (eq 2).7 The reaction is applicable to Ä…-
InChIKey = MFLMBWASGCAJGO-KNVCLVHBCD
phenylseleno-substituted ketones, aldehydes, esters, and lactones.
Quenching the reaction with aqueous iron(II) sulfate leads to a
Alternate Names: sodium percarbonate (SPC), sodium carbonate
straightforward recovery of the product.
peroxy hydrate, sodium carbonate perhydrate.
ć%
Solubility: relatively soluble in water at 20 C, 1 mol L-1 (pH
of 1% aqueous solution <"10.5), AcOH, THF, and other polar
O
organic solvents. O
Form Supplied in: free flowing white granular powder. R2
R2
SPC, Ac2O
R3 (2)
Physical Data: bulk density (gL-1), 0.95 1.08; active oxygen
R3
THF, rt
e"8.0%
R1
R1 SePh
Handling, Storage, and Precautions: SPC is very stable in dry
conditions but should be protected from moisture to avoid
decomposition. One of the advantages of using SPC is that it
Sulfonic acids can be safely prepared on a large scale by
is easier and safer to handle than concentrated H2O2; however,
oxidation of benzimidazole-2-thiones with aqueous SPC (eq 3).8
the solid is an irritant. Therefore, precautions should be taken
A convenient synthesis of diphenyldiselenide by oxidation of
to avoid inhalation of the powder and contact with skin. All
selenophenol with SPC in the presence of air has also been
operations using this reagent are best conducted in an efficient
reported.9
fume hood.
H
R1 R1
N N
Introduction. SPC is sodium carbonate sesquiperhydrate.
SPC/H2O
S SO2H
2Na2CO3·3H2O2 (SPC) contains hydrogen peroxide but is a
reflux
N N
conveniently handled solid. The structure of SPC has been deter- R2 R2
(3)
H H
mined: there are hydrogen bonds between carbonate ions and
hydrogen peroxide molecules.2,3 Aqueous solutions are alkaline
(pH 10 11) and relatively unstable. In solution, the dominant
chemistry of SPC is that of H2O2. Thus, SPC offers a conve-
Nitrogen. SPC has been used to oxidize aniline and p-chloro-
nient source of hydrogen peroxide, which is advantageous since
aniline to nitrobenzene and p-chloronitrobenzene, respectively, in
concentrated solutions of hydrogen peroxide are not readily avail-
good yields (eq 4).4 Primary amines are readily oxidized to the
able and are dangerous to handle. SPC also acts as a source of
corresponding C-nitroso compounds in good yields in a biphasic
H2O2 under anhydrous or near-anhydrous conditions, which is
system of ethyl acetate (or dichloromethane) and water contain-
an advantage in reactions involving peroxy acid formation from
ing sodium percarbonate, sodium bicarbonate, and N,N,N ,N -
acid chlorides, anhydrides, or imidazolides. A further advantage
tetraacetyl ethylenediamine (TAED).10 Preparation of optically
of the use of SPC for peracid formation from acid chlorides is that
active 2-4-hydroxyisooxazolines can also be achieved using
the sodium carbonate readily neutralizes the HCl liberated during
SPC (eq 5).11
the reaction, thus minimizing chlorohydrin formation when the
system is used for epoxidation.
NO2
NH2
Functional Group Oxidations.
SPC
(4)
Sulfur and Selenium. SPC is an effective agent for oxidizing
both sulfur and selenium. For example, ultrasound-assisted oxi-
R
R
dation of sulfides to the corresponding sulfones (eq 1) occurs in
R = H, Cl R = H, Cl
quantitative yield using SPC in aqueous acetonitrile.4 Oxidation
Avoid Skin Contact with All Reagents
2 SODIUM PERCARBONATE
OH
has been developed for the oxidation of highly electron-deficient
N
O2 O
pyridines to their corresponding N-oxides (eq 11).16
X = Br, Cl
O
S
B
R1 X
R
R
Re catalyst, SPC
SPC, THF, 0 °C + 
O
R +
R
+
R N R N O
MeCN, 50 °C
+
R R
N
N (10)
(5)
O

OH
OH
O2 O
SPC
S
HOOC
R1 R1
THF/H2O
Tf2O/Na2CO3Å"1.5H2O2
O N O N
(11)
+
solvent, 0 °C
Cl N Cl
Cl N Cl
O

R1 = Br
SPC has been found to be highly effective for the cleavage of
Alkanes. The use of SPC/trifluoromethanesulfonic acid has
tosylhydrazones to aldehydes and ketones (eq 6) in good yields.12 been reported for the oxidation of saturated hydrocarbons.
Oxygen is inserted into a C C bond in adamantane, affording a
NHTs
O
N high yield of 4-oxohomoadamantane (eq 12); under these con-
SPC
(6) ditions, no adamantane-1-ol was detected.17 The oxidation of
DMF/H2O
R R1
R R1 benzylic methylenes has been observed using SPC when promoted
by metal catalysis (eq 13).18
R1 = H, Me
R1 = H, Me
O
A mixture of SPC and silica gel in aqueous DMF has been
SPC
shown to be effective for Nef oxidations (eq 7).12 The role of the (12)
CF3SO3H
silica gel in this reaction is unknown but reactions were found to
 10 °C, 8 h
be faster in its presence. SPC, in warm aqueous acetone, affords
a practical method to prepare amides from a variety of nitriles
including aryl, pyridyl, arylalkyl, and aliphatic nitriles (eq 8).13
SPC
MeCN, 81 °C
O
NO2
SPC
Adogen 464
(7)
DMF/H2O
R R1
R R1 O
OH O
silica gel
SPC
(13)
+
(8) +
R CN R CONH2
acetone/H2O (3/2)
O
R = alkyl, aryl
R = alkyl, aryl
The oxidation of cycloalkyl primary amines to nitro compounds
Oxidation of Alkenes. The epoxidation of unactivated alkenes
has been achieved using SPC at room temperature; 1-amino-
(eq 14), as well as Ä…,²-unsaturated alcohols and Ä…,²-unsaturated
adamantane and 1,3,5,7-tetraaminoadamantane afforded the
ketones (eq 15), has been carried out using SPC in the presence
corresponding nitroadamantanes (eq 9) in high yields.14
of a small amount of water, which aids in the release of hydrogen
peroxide from the inorganic salt.19
X
X1
(9)
SPC, (AcO)2N(CH2)2N(OAc)2
R3 O R4
R3 R4
Y SPC
Y1
Y
Y1
NaHCO3, H2O/CH2Cl2
(14)
H2O/EtOH
Y O3, CH2Cl2
Y1
R1 R2 R1 R2
O O
X = NH2, Y=H
X1 = NO2, Y1 = H, 95%
X = Y = NH2
R6 R2
X1 = Y1 = NO2, 91% R6 R2
SPC
(15)
O
H2O/EtOH
SPC is an efficient and versatile reagent for the oxidation of
R5 R5
pyridines and tertiary amines in the presence of a rhenium-based
O O
catalyst (eq 10).15 Trifluoromethanesulfonic anhydride with SPC
A list of General Abbreviations appears on the front Endpapers
SODIUM PERCARBONATE 3
O OH
OH OH
Styrene, cylohexene, and cinnamyl alcohol are oxidized to the
corresponding epoxides in 73, 74, and 75% yields, respectively, by
SPC, aq HBr
(20)
SPC,4 and there are patents describing the use of percarbonate for
AcOH, 50 °C
the epoxidation of methylenecyclohexanes.20,21 Ultrasonication 84%
significantly increases the rates of a number of oxidation reac-
tions involving SPC; although for most applications, the use of
ultrasound is not required. In terms of olefin epoxidation, reac-
Baeyer Villiger Oxidation of Ketones. SPC has been shown
tions of a series of mono- and diolefins with percarbonate using
to be effective for the in situ generation of trifluoroperacetic acid in
a dichloromethane/acetic anhydride solvent system have been
buffered anhydrous systems for use in Baeyer Villiger reactions.
reported. Without ultrasound, 60 80% yields of epoxides were
Addition of trifluoroacetic anhydride to a suspension of SPC in
obtained after 18 24 h; with ultrasound, the reactions were com-
CH2Cl2 at ambient temperature in the presence of ketones gave
plete in 1 3 h. Yields of epoxides were slightly higher in the latter
good yields of esters (eq 21).28 This method has distinct advan-
case but, once again, care had to be taken to prevent the reactions
tages over classical trifluoroperoxyacetic acid (TFPAA) genera-
from proceeding too vigorously.22
tion from high strength (85 90%) H2O2, a reagent that must be
Epoxidation of enones using percarbonate and polyleucine
handled with great care. SPC is known to perform very well in
(PLL) in a series of mixed solvent systems was examined and
conversions of cyclic ketones to lactones (eq 22)29 with typical
it was shown that ether aqueous mixtures gave the highest ee
yields near 80%.
(enantiomeric excess). In particular, a water/1,2-dimethoxyethane
(DME) mixture gave a rapid conversion to the epoxide (>99%
yield) and high ee (eq 16).23 Organocatalysis (chiral pyrrolidine
O O
derivatives) provided asymmetric epoxidation of Ä…,²-unsaturated
SPC TFAA
O
aldehydes using sodium percarbonate (eq 17).24
CH2Cl2, 2 h, 84%
(21)
O
O
O
PLL SPC
(16)
DME H2O Ph Ph
Ph Ph
20 min, >99
96% ee
O
O
O
SPC
(22)
CF3CO2H
O
O
O
0 °C to rt, 98%
SPC or H2O2
R H
R H
CHCl3, rt
cat (10 mol %)
dr: 90:10, 98% ee
R = CO2Et
R = CO2Et
Dakin Reaction. SPC has been used successfully in the Dakin
reaction. Catechol can be prepared from both salicylaldehyde and
Ph
2-hydroxyacetophenone using SPC in aqueous THF (eq 23).30
cat =
(17)
Ph
Aromatic ortho-hydroxyaldehydes have also been utilized.
N
H
OTMS
Hydroquinone was obtained in 86% yield from 4-hydroxybenzal-
dehyde while meta-substituted and 4-hydroxyacetophenone failed
to undergo oxidation.
When SPC is mixed with acetic (or trifluoroacetic acid), pyra-
zole, alkene, and MTO (methyltrioxorhenium) in THF, it gives a
vibrant yellow color that is characteristic of the peroxo activated
O
MTO species. Stirring for 2 h, the TFA/SPC reaction results in
OH
complete conversion of the olefin to the epoxide (eq 18).25 R1 SPC
(23)
H2O/THF
R
OH
1 mol % MTO
R
rt OH
O
2.5 equiv SPC
R (18)
R1 = H, Me
R
R
2.5 equiv TFA
R
12 mol % pyrazole
Carbon carbon cleavage in catechols using H2O2 or SPC is
Alcohols, Aldehydes, Ketones, and Phenols. SPC, mixed with
catalyzed by iron sulfophthalocyanines, the products being malic
pyridinium dichromate and a phase-transfer catalyst in dichloro-
ć%
acids.31 Oxidative cleavage of Ä…-haloketones,32 as well as Ä…-
ethane at 80 C, provides a good oxidizing system for the oxidation
ketols and Ä…-diketones,33 to carboxylic acids by SPC in aque-
of allylic and benzylic alcohols (eq 19).26 Secondary alcohols are
ous acetone solutions is quite effective. For aromatic Ä…-diketones,
selectively and efficiently oxidized by SPC in the presence of a
ć%
catalytic amount of aqueous HBr in acetic acid at 50 C (eq 20).27 the presence of an electron-donating group in the para-position
slows down the oxidation process. The oxidation by SPC of
PDC (0.1 equiv) Ä…-diketones has also been carried out in anhydrous solvents (1,2-
R1 R1
Adogen 464 (0.2 equiv)
dichloroethane and acetonitrile). The reaction is more effective
OH O
(19)
Na2CO3Å"1.5 H2O2 (4 equiv)
R2 when performed in the presence of small amounts of pyruvate
R2
ClCH2CH2Cl, 80 °C
decarboxylase (PDC).34
Avoid Skin Contact with All Reagents
4 SODIUM PERCARBONATE
The cleavage of Ä…-diketones is also readily carried out using 3. Carrondo, M. A. A. F. de C. T.; Griffith, W. P.; Jones, D. P.; Skapski, A.
C., J. Chem. Soc., Dalton Trans. 1977, 2323.
SPC in aqueous acetone (eq 24).35
4. Ando, T.; Cork, D. G.; Kimura, T., Chem. Lett. 1986, 665.
5. Karunakaran, C.; Kamalam, R., React. Kinet. Catal. Lett. 2002, 76,
37.
O
SPC
CO2H
(24) 6. Gòmez, M. V.; Caballero, R.; VÄ…zquez, E.; Moreno, A.; Hoz, de la A.;
H2O/acetone
CO2H
Dìaz-Ortiz, A., Green Chem. 2007, 9, 331.
65 °C
O
7. Kabalka, G. W.; Reddy, N. K.; Narayana, C., Synth. Commun. 1993, 23,
543.
SPC in acetonitrile cleaves benzylic alcohols containing Ä…-
8. Hinkley, J. M.; Potcari, A. R.; Walker, J. A., II; Swayze, E. E.; Townsend,
substituted hydroxy, keto, acid, or ester groups to furnish ben-
L. B., Synth. Commun. 1998, 28, 1703.
zaldehyde and benzoic acid.36 A molybdenyl acetylacetonate
9. Liu, Y.; Yang, Q.; Cheng, W., Jingxi Huagong 1996, 13, 27.
assisted oxidation of Ä…-functionalized alcohols has also been
10. Zajac, W. W., Jr.; Walters, T. R.; Woods, J. M., Synthesis 1988,
reported (eq 25).37
808.
Na2CO3Å"1.5 H2O2 (4 equiv)
11. Liu, J.; Eddings, A.; Wallace, R. H., Tetrahedron Lett. 1997, 38,
OH
O O
O
MoO2(acac)2 (0.1 equiv)
6795.
+ +
Ph X Adogen 464 (0.2 equiv)
Ph X Ph OH 12. Narayana, C.; Reddy, N. K.; Kabalka, G. W., Synth. Commun. 1992, 22,
Ph H
MeCN
2587.
(25)
13. Kabalka, G. W.; Deshpande, S. M.; Wadgaonkar, P. P.; Narayana, C.,
X: COPh (a); CH(OH)Ph (b); CH2OH (c); CO2Me (d); CO2H(e)
Synth. Commun. 1990, 20, 1445.
14. Zajac, W. W., Jr; Walters, T. R.; Woods, J. M., J. Org. Chem. 1989, 54,
The peroxovanadium species generated from V2O5 and H2O,
2468.
liberated from a peroxy salt such as SPC, transforms alde-
15. Jain, S. L.; Joseph, J. K.; Sain, B., Synlett 2006, 2661.
hydes directly to esters in alcoholic media (eq 26).38 Nitroarene-
16. Zhu, X.; Kreutter, K. D.; Hu, H.; Player, M. R.; Gaul, M. D., Tetrahedron
catalyzed39 oxidations of aryl methyl ketones to benzoic acids
Lett. 2008, 49, 832.
using SPC have been carried out successfully.
17. Olah, G. A.; Wang, Q.; Krass, N.; Prakash, G. K. S., Rev. Roum. Chim.
O 1991, 39.
O
18. Muzart, J.; Aìt-Mohand, S., Tetrahedron Lett. 1995, 36, 5735.
+
OH
R1 V2O5 SPC
R H
(26)
R OR1 19. Rocha Gonsalves, A. M. d A.; Johnstone, R. A. W.; Pereira, M. M.;
HClO4
Shaw, J., J. Chem. Res. (S) 1991, 208; (M) 1991, 2101.
20. U. S. Pat. 5,157,131 (1992).
R = aryl, alkenyl; R1 = Me, CH2CH2OH
21. U. S. Pat. 5,175,373 (1992).
SPC efficiently oxidizes a variety of organoboranes (eq 27)40 22. Tao, F.-G.; Xu, L.-X.; Lu, Y.-Z.; Ma, S.-M.; Sun, C.-Z.; Xie, G.-Y., Acta
Chim. Sin. Engl. Ed. 1989, 463.
to their corresponding alcohols. Iodoarenes are also oxidized to
23. Allen, J. V.; Drauz, K. H.; Flood, R. W.; Roberts, S. M.; Skidmore, J.,
diacetoxyiodoarenes (eq 28)41 by sodium percarbonate in anhy-
Tetrahedron Lett. 1999, 40, 5417.
drous ternary solvent system, Ac2O/AcOH/CH2Cl2.
24. Suden, H.; Ibrahem, I.; Còrdova, A., Tetrahedron Lett. 2006, 47,
Na2CO3Å"1.5H2O2
99.
R3B 3 ROH
(27)
THF H2O
25. Vaino, A. R., J. Org. Chem. 2000, 65, 4210.
26. Muzart, J.; N Ait Ajjou, A.; Aìt-Mohand, S., Tetrahedron Lett. 1994, 35,
I
1989.
27. Jain, S. L.; Sharma, V. B.; Sain, B., Tetrahedron 2006, 62, 6841.
AcOH/Ac2O/CH2Cl2
.
+ 2 Na2CO3 3H2O2 + Ac2O
3
28. Kang, H.-J.; Jeong, H.-S., Bull. Korean Chem. Soc. 1996, 17, 5.
25 40 °C, 6.5 h, 18 84%
R
29. Olah, G. A.; Wang, Q.; Trivedi, N. J.; Prakash, G. K. S., Synthesis 1991,
I(OAc)2
739.
R = F, Cl, Me, OMe
(28)
30. Kabalka, G. W.; Reddy, N. K.; Narayana, C., Tetrahedron Lett. 1992, 33,
+ 6AcOH + 4 AcONa + 2CO2
865.
3
31. Sorokin, A.; Fraisse, L.; Rabion, A.; Meunier, B. J., Mol. Catal. A: Chem.
R
1997, 117, 103.
R = F, Cl, Me, OMe
32. Yang, D. T. C.; Cao, Y. H.; Kabalka, G. W., Synth. Commun. 1995, 25,
3695.
Related Reagents. Hydrogen Peroxide; Sodium Perborate
33. Yang, D. T. C.; Cao, Y. H.; Evans, T. T.; Kabalka, G. W., Synth. Commun.
(SPB); meta-Chloroperbenzoic Acid (MCPBA).
1996, 26, 4275.
34. Aìt-Mohand, S.; Muzart, J., Synth. Commun. 1995, 25, 2373.
35. Yang, D. T. C.; Evans, T. T.; Yamazaki, F.; Narayama, C.; Kabalka, G.
W., Synth. Commun. 1993, 23, 1183.
1. (a) Mckillop, A.; Sanderson, R. W., Tetrahedron 1995, 51, 6145.
36. Aìt-Mohand, S.; Levina, A.; Lunak, S.; Muzart, J., Inorg. Chem. Acta
(b) Muzart, J., Synthesis, 1995, 1325. (c) Mckillop, A.; Sanderson, W.
1995, 238, 183.
R., J. Chem. Soc., Perkin Trans. 1 2000, 471.
2. Adams, J. M.; Pritchard, R. G., Acta Crystallogr. Sect. B 1977, 33, 37. Riahi, A.; Maignien, S.; Aìt-Mohand, S.; Muzart, J., J. Mol. Catal. A:
3650. Chem. 1998, 135, 269.
A list of General Abbreviations appears on the front Endpapers
SODIUM PERCARBONATE 5
38. Gopinath, R.; Barkakaty, B., J. Org. Chem. 2003, 68, 2944. 41. Zielinska, A.; Skulski, L., Molecules 2002, 7, 806.
39. Bjłrsvik, H.-R.; Vedia Merinero, J. A.; Liguori, L., Tetrahedron Lett.
2004, 45, 8615.
George W. Kabalka & Marepally Srinivasa Reddy
40. Kabalka, G. W.; Wadgaonkar, P. P.; Shoup, T. M., Tetrahedron Lett. 1989,
University of Tennessee, Knoxville, TN, USA
30, 5103.
Avoid Skin Contact with All Reagents