Bromodecarbonylation and bromodecarboxylation of electron-rich benzaldehydes and benzoic acids with oxone and sodium bromide

Article abstract of DOI:10.1081/SCC-120005997

Benzaldehydes and benzoic acids bearing ortho- and paraelectron donating substituents having unshared electron-pair have undergone bromodecarbonylation or bromodecarboxylation on treatment with sodium bromide in the presence of Oxone in aqueous methanol.

Full text of DOI:10.1081/SCC-120005997

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BROMODECARBONYLATION AND
BROMODECARBOXYLATION OF ELECTRON-RICH
BENZALDEHYDES AND BENZOIC ACIDS WITH OXONE®
AND SODIUM BROMIDE
Bon-Suk Koo a , Eun-Hoo Kim a & Kee-Jung Lee b
a Department of Industrial Chemistry, Hanyang University, Seoul, 133-791, Korea
b Department of Industrial Chemistry, Hanyang University, Seoul, 133-791, Korea
Version of record first published: 16 Aug 2006
To cite this article: Bon-Suk Koo, Eun-Hoo Kim & Kee-Jung Lee (2002): BROMODECARBONYLATION AND
BROMODECARBOXYLATION OF ELECTRON-RICH BENZALDEHYDES AND BENZOIC ACIDS WITH OXONE® AND SODIUM BROMIDE,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:15,
2275-2286
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 15, pp. 2275–2286, 2002
BROMODECARBONYLATION AND
BROMODECARBOXYLATION OF
ELECTRON-RICH BENZALDEHYDES
AND BENZOIC ACIDS WITH OXONEÕ
AND SODIUM BROMIDE
*
Bon-Suk Koo, Eun-Hoo Kim, and Kee-Jung Lee
Department of Industrial Chemistry,
Hanyang University, Seoul 133-791, Korea
ABSTRACT
Benzaldehydes and benzoic acids bearing ortho- and para-
electron donating substituents having unshared electron-pair
have undergone bromodecarbonylation or bromodecarboxy-
lation on treatment with sodium bromide in the presence of
OxoneÕ in aqueous methanol.
Key Words: Bromodercarbonylation; Bromodecarboxyla-
tion; Oxone; Sodium bromide; Electron-rich benzaldehydes;
Benzoic acids
Potassium hydrogen persulfate (KHSO5), which is commercially avail-
able as OxoneÕ, can be used for the oxidation of alkenes,[1] arenes,[2]
*Corresponding author. Fax: þ82-2-2298-4101; E-mail: leekj@hanyang.ac.kr
2275
DOI: 10.1081/SCC-120005997
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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2276
KOO, KIM, AND LEE
Scheme 1.
amines,[3] imines,[4] sulfides,[5] selenides,[6] a-amino acids,[7] acetals,[8] and the
carbonyl regeneration from thioacetals,[9] oximes[10] and nitroalkanes.[11]
Recent reports deal with the use of OxoneÕ and aqueous sodium halides
as a convenient halogenating reagent to achieve oxidation of a,b-enones[12]
and bromination of pyrimidines.[13] Also, the use of bromine in alcohol has
been used to convert aldehydes to esters as a convenient and inexpensive
technique,[14] as shown in Scheme 1.
Based on the versatility of OxoneÕ as an oxidant and on halogen
generation from sodium halide, and on the fact that these strongly acidic
solutions may provide some advantage for direct conversion of aldehydes
into esters, we decided to test OxoneÕ and sodium bromide on benzalde-
hydes in aqueous methanol. Our results are compiled in Table 1; yields were
determined after isolation. Methyl and ethyl esters were prepared in good to
excellent yields, but iso-propyl ester was not produced in any quantity
(Entries 1 and 2). However, an electron-rich aromatic, p-anisaldehyde,
underwent competitive attack on the ring, giving 3-bromo-p-anisaldehyde
3a (39%), methyl 3-bromo-p-anisate 3b (5%), and affording, unexpectedly,
bromodecarbonylation product, 2,4-dibromoanisole 3c (38%).[15] In the
case of using two equivalents of OxoneÕ, 3c was produced in excellent
yield (78%) along with 3b (11%) (Entry 3), as shown in Scheme 2.
Analogous bromodecarbonylation of o-anisaldehyde, using two
equivalents of OxoneÕ, afforded 2,4-dibromoanisole 3c (15%) and the
Scheme 2.

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BROMODECARBONYLATION AND BROMODECARBOXYLATION
2277
Table 1. Reaction of Benzaldehydes with OxoneÕ and Sodium Bromide
Entry
1b
Substrate
Time (h)
24
Product/No.
1a
% Yielda
(71)
2
3
4
4
2
(90)
39 (0)
3a
3b
5 (11)
38 (78)
3c
4
24
4a
72 (5)
0 (15)
4b
3c
0 (15)
5
24
5a
73 (49)
5b
5c
0 (10)
0 (14)
(continued )

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2278
KOO, KIM, AND LEE
Table 1. Continued
Entry
6
Substrate
Time (h)
4
Product/No.
% Yielda
27 (0)
6a
6b
37 (0)
14 (65)
(22)
6c
7
24
7a
7b
(37)
8
4
8
(95)
aYields were based on isolated products purified by column chromatography using
1 eq. of OxoneÕ. Parentheses values were obtained using 2 eq. of OxoneÕ.
bEthyl benzoate (1b) (65%) was obtained using EtOH instead of MeOH, but
iso-propyl benzoate was not produced in iso-PrOH.
ring bromination products, 5-bromo-o-anisaldehyde 4a (5%) and methyl
5-bromo-o-anisate 4b (15%) (Entry 4). However, m-anisaldehyde gave
only ring bromination aldehydes 5a (49%) and 5b (10%) along with a
demethylation product, 2,4,6-tribromo-3-hydroxybenzaldehyde 5c (14%),
using two equivalents of OxoneÕ (Entry 5). To further investigate the
generality of our protocol, various aldehydes were chosen. 4-Acetamido-
benzaldehyde afforded bromodecarbonylation products, 4-bromoacetanilide
6b (37%), 2,4-dibromoacetanilide 6c (14%) and a simple ring bromination
product, 3-bromo-4-acetamidobenzaldehyde 6a (27%). But 6c (65%) was
produced using two equivalents of OxoneÕ (Entry 6). Moreover, a salient
feature of these reactions is the possibility of introducing two different halo-

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BROMODECARBONYLATION AND BROMODECARBOXYLATION
2279
gens into the aromatic ring, selectively (Entry 7). But, in the case of 4-acet-
amido-3-chlorobenzaldehyde, methyl 4-acetamido-3-chlorobenzoate
(95%) was obtained, exclusively (Entry 8).
8
Electron-deficient aromatic aldehydes have been shown to undergo
oxidation with OxoneÕ to give acids. However, electron-rich aromatic
aldehydes such as p-anisaldehyde, are converted to the Dakin product,
p-methoxyphenol.[16] The major question that warranted further investiga-
tion in the present study is: ‘‘what triggers the elimination of the aldehyde
group?’’[17]
To elucidate the possible pathway for the formation of the bromode-
carbonylation product, we next subjected various substituted benzoic acids
to our reaction conditions (Table 2). For example, the reaction of electron-
rich aromatic p-anisic acid with OxoneÕ/NaBr/Na2CO3 in aqueous metha-
nol at r.t. afforded the bromodecarboxylation product 4-bromoanisole 9b
(58%) and the ring bromination product 3-bromo-p-anisic acid 9a (13%)
(Entry 1). Similarly, 4-acetamidobenzoic acid gave 4-bromoacetanilide 6b
(56%), 2,4-dibromoacetanilide 6c (7%) and 4-acetamido-3-bromobenzoic
acid 10a (23%), respectively (Entry 2). Using two equivalents of OxoneÕ,
we obtained 2,4-dibromoanisole 3c (91%) and 2,4-dibromoacetanilide
6c (65%) from p-anisic acid and 4-acetamidobenzoic acid, respectively
(Entries 1 and 2) as shown in Scheme 3.
This modified Hunsdiecker reaction[18] was further extended to the
analogous benzoic acids such as 3-chloro-p-anisic acid and 4-acetamido-3-
chlorobenzoic acid, which afforded the corresponding bromides 7b (72%)
and 11 (43%), respectively (Entries 3 and 4). This is another valuable
reaction that introduces two different halogens into the aromatic ring,
selectively.
Scheme 3.

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2280
KOO, KIM, AND LEE
Table 2. Reaction of Benzoic Acids with OxoneÕ and Sodium Bromide
Entry
1
Substrate
Time (h)
24
Product/No.
% Yielda
13 (0)
9a
9b
58 (0)
0 (91)
3c
2
24
10a
23 (0)
56 (0)
7 (65)
(72)
6b
6c
3
4
24
24
7b
11
(43)
5
24
12
65 (25)
30 (68)
3c
6
24
13
75 (75)
(continued)

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BROMODECARBONYLATION AND BROMODECARBOXYLATION
2281
Table 2. Continued
Entry
7
Substrate
Time (h)
24
Product/No.
% Yielda
(71)
14a
14b
(8)
b
b
b
8
9
24
24
24
10
aYields were based on isolated products purified by column chromatography using
1 eq. of OxoneÕ. Parentheses values were obtained using 2 eq. of OxoneÕ.
bNo reaction and starting acid was recovered.
To gain further insight, various independent experiments have
been conducted in the present study, the results of which are presented
below; (a) acids bearing ortho- and para-electron donating substituents
having unshared electron-pair are particularly reactive (Table 2, Entries
1–3 and 5) compared with those having electron withdrawing groups
(Table 2, Entries 9 and 10); (b) acids bearing meta-electron donating sub-
stituents give only ring bromination products (Table 2, Entry 6); (c)
electron-rich aromatics such as p-toluic acid give mainly ring bromination
products, 3-bromo-p-toluic acid 14a (71%) and bromodecarboxylation/
concurrent with the side chain bromination product,[1a] 4-bromobenzyl bro-
mide 14b (8%) (Table 2, Entry 7).
We have shown in the present study that facile bromodecarbonyla-
tion[19] and bromodecarboxylation[19] of benzaldehydes and benzoic
acids can be carried out using a mixture of OxoneÕ and NaBr, thus
further widening the scope of the Hunsdiecker reaction. The procedure
described here is safe, economical and environmentally sound compared
with other reported methods. In further studies, we hope to elaborate

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2282
KOO, KIM, AND LEE
the mechanism of reaction and provide examples of this modified
Hunsdiecker reaction on substrates other than benzaldehydes and
benzoic acids.
EXPERIMENTAL
Melting point data were determined in open capillaries with an
Electrothermal melting point apparatus and are uncorrected. The progress
of reactions was followed by TLC, using silica gel with a fluorescent indi-
cator coated on aluminium sheets. 1H NMR spectra were recorded at
300 MHz in CDCl3, using TMS as an internal standard. Elemental analyses
were performed using a Carlo Erba EA 1180 element analyzer.
General procedure for the reaction of benzaldehydes with OxoneÕ and
sodium bromide: To a stirred solutions of benzaldehydes (5 mmol) in aque-
ous methanol (70 mL, 1 : 1 by volume) was added NaBr (2.57 g, 25 mmol)
and OxoneÕ (3.07 g, 5 mmol or 6.14 g, 10 mmol). The reaction was continu-
ously monitored by thin-layer chromatography and stirred at r.t. for gen-
erally 4–24 h. The reaction mixture was quenched with aqueous sodium
thiosulfate and extracted with ether (3 ꢀ 50 mL). The combined organic
layers were washed with water, dried over anhydrous MgSO4, filtered,
and concentrated in vacuo. The residue was chromatographed on a
silica gel column and eluted with hexane-EtOAc 10 : 1, giving the products
(Table 1).
The spectral and analytical data of products are as follows:
1a: oil (Lit.[20] b.p. 198–199ꢁ). H NMR ꢀ 3.91 (s, 3H), 7.40–7.55 (m,
1
3H), 8.02–8.06 (m, 2H).
1b: oil (Lit.[20] b.p. 212ꢁ). H NMR ꢀ 1.39 (t, J ¼ 7.2 Hz, 3H), 4.38 (q,
1
J ¼ 7.2 Hz, 2H), 7.40–7.57 (m, 3H), 8.03–8.06 (m, 2H).
2: oil (Lit.[20] b.p. 103–104ꢁ/15 Torr). H NMR ꢀ 2.39 (s, 3H), 3.89 (s,
1
3H), 7.22 (d, J ¼ 8.0 Hz, 2H), 7.92 (d, J ¼ 8.0 Hz, 2H).
3a: m.p. 51–52ꢁ (Lit.[20] b.p. 51–54ꢁ). H NMR ꢀ 3.99 (s, 3H), 7.01 (d,
1
J ¼ 8.4 Hz, 1H), 7.81 (d, J ¼ 8.4 Hz, 1H), 8.07 (s, 1H), 9.84 (s, 1H).
3b: m.p. 98ꢁ (Lit.[21] 99–100ꢁ). H NMR ꢀ 3.94 (s, 3H), 4.00 (s, 3H),
1
6.96 (d, J ¼ 8.7 Hz, 1H), 8.02 (dd, J ¼ 8.7, 2.1 Hz, 1H), 8.27 (d, J ¼ 2.1 Hz, 1H).
3c: m.p. 61–62ꢁ (Lit.[22] 60–61ꢁ). H NMR ꢀ 3.87 (s, 3H), 6.77 (d,
1
J ¼ 8.8 Hz, 1H), 7.37 (dd, J ¼ 8.8, 2.3 Hz, 1H), 7.66 (d, J ¼ 2.3 Hz, 1H).
4a: m.p. 115–116ꢁ (Lit.[20] 116–119ꢁ). H NMR ꢀ 3.93 (s, 3H), 6.90
1
(d, J ¼ 8.9 Hz, 1H), 7.63 (dd, J ¼ 8.9, 2.6 Hz, 1H), 7.91 (d, J ¼ 2.6 Hz, 1H),
10.38 (s, 1H).
4b: oil (Lit.[23] m.p. 39–40ꢁ). 1H NMR ꢀ 3.89 (s, 6H), 6.87 (d,
J ¼ 8.9 Hz, 1H), 7.56 (dd, J ¼ 8.9, 2.6 Hz, 1H), 7.91(d, J ¼ 2.6 Hz, 1H).

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BROMODECARBONYLATION AND BROMODECARBOXYLATION
2283
5a: m.p. 105–108ꢁ (Lit.[24] 110ꢁ). H NMR ꢀ 3.94 (s, 3H), 7.40 (s, 1H),
1
7.84 (s, 1H), 10.26 (s, 1H).
5b: m.p. 129–130ꢁ. H NMR ꢀ 3.94 (s, 3H), 6.93 (d, J ¼ 8.7 Hz, 1H),
1
7.58 (d, J ¼ 8.7 Hz, 1H), 10.23 (s, 1H). Anal. calcd. for C8H6Br2O2: C, 32.69;
H, 2.06. Found: C, 32.41; H, 1.98.
5c: m.p. 118–119ꢁ (Lit.[25] 119ꢁ). H NMR ꢀ 6.38 (s, 1H), 7.85 (s, 1H),
1
10.17 (s, 1H).
6a: m.p. 112ꢁ. H NMR ꢀ 2.30 (s, 3H), 7.82 (d, J ¼ 8.6, 1.8 Hz, 1H),
1
7.88 (s, 1H), 8.08 (d, J ¼ 1.8 Hz, 1H), 8.63 (d, J ¼ 8.6 Hz, 1H), 9.88 (s, 1H).
Anal. calcd. for C9H8BrNO2: C, 44.66; H, 3.33; N, 5.79. Found: C, 44.39;
H, 3.03; N, 5.52.
6b: m.p. 168ꢁ (Lit.[26] 165–168ꢁ). H NMR ꢀ 2.04 (s, 3H), 7.47 (d,
1
J ¼ 8.9 Hz, 2H), 7.56 (d, J ¼ 8.9 Hz, 2H), 10.07 (s, 1H).
6c: m.p. 142–143ꢁ (Lit.[27] 144.7ꢁ). H NMR ꢀ 2.24 (s, 3H), 7.42 (dd,
1
J ¼ 8.9, 2.1 Hz, 1H), 7.57 (s, 1H), 7.68 (d, J ¼ 2.1 Hz, 1H), 8.26 (d,
J ¼ 8.9 Hz, 1H).
7a: m.p. 90–93ꢁ (Lit.[28] 94ꢁ). 1H NMR ꢀ 3.90 (s, 3H), 3.96 (s,
3H), 6.95 (d, J ¼ 8.6 Hz, 1H), 7.94 (dd, J ¼ 8.6, 2.1 Hz, 1H), 8.05
(d, J ¼ 2.1 Hz, 1H).
7b: m.p. 68–70ꢁ (Lit.[29] 70ꢁ). 1H NMR ꢀ 3.88 (s, 3H), 6.79 (d,
J ¼ 8.7 Hz, 1H), 7.32 (dd, J ¼ 8.7, 2.3 Hz, 1H), 7.49 (d, J ¼ 2.3 Hz, 1H).
8: m.p. 93–94ꢁ. 1H NMR ꢀ 3.90 (s, 3H), 3.96 (s, 3H), 6.95 (d,
J ¼ 8.6 Hz, 1H), 7.94 (dd, J ¼ 8.6, 2.1 Hz, 1H), 8.05 (d, J ¼ 2.1 Hz, 1H).
Anal. calcd. for C10H10ClNO3: C, 52.76; H, 4.43; N, 6.15. Found: C,
52.53; H, 4.18; N, 5.88.
General procedure for the reaction of benzoic acids with OxoneÕ and
sodium bromide: To a stirred suspension of benzoic acids (5 mmol) in aque-
ous methanol (70 mL, 1 : 1 by volume) was added Na2CO3 (0.53 g, 5 mmol),
NaBr (2.57 g, 25 mmol) and OxoneÕ (3.07 g, 5 mmol or 6.14 g, 10 mmol).
The reactions were continuously monitored by thin-layer chromatography
and stirred at r.t. for 24 h. The reaction mixture was quenched with aqueous
sodium thiosulfate and extracted with ether (3 ꢀ 50 mL). The organic layers
were washed with aqueous Na2CO3, water, dried and evaporated. The resi-
due was chromatographed on a silica gel column and eluted with hexane-
EtOAc 10 : 1 to give the aryl bromide. The combined aqueous layer was
acidified with a 10% HCl solution to pH 2 and extracted with EtOAc
(2 ꢀ 50 mL). The organic layers were washed with water, dried and evapo-
rated to afford the acid products.
The spectral and analytical data of products are as follows:
9a: m.p. 202–204ꢁ (Lit.[30] 201–206ꢁ). H NMR ꢀ 3.96 (s, 3H), 6.95 (d,
1
J ¼ 8.5 Hz, 1H), 8.00 (dd, J ¼ 8.5, 1.8 Hz, 1H), 8.22 (d, J ¼ 1.8 Hz, 1H), 9.22
(brs, 1H).

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2284
KOO, KIM, AND LEE
9b: oil (Lit.[22] b.p. 124ꢁ/40 Torr). H NMR ꢀ 3.76 (s, 3H), 6.77 (d,
1
J ¼ 8.9 Hz, 2H), 7.36 (d, J ¼ 8.9 Hz, 2H).
10a: m.p. 220–221ꢁ (Lit.[31] 226–229ꢁ). H NMR ꢀ 2.27 (s, 3H), 7.97
(dd, J ¼ 8.5, 1.8 Hz, 1H), 8.12 (s, 1H), 8.23 (d, J ¼ 1.8 Hz, 1H), 8.35 (d,
J ¼ 8.5 Hz, 1H).
1
11: m.p. 148–150ꢁ (Lit.[27] 151.4ꢁ). H NMR ꢀ 2.24 (s, 3H), 7.39 (dd,
1
J ¼ 8.9, 2.1 Hz, 1H), 7.52 (d, J ¼ 2.1 Hz, 1H), 7.57 (s, 1H), 8.29 (d,
J ¼ 8.9 Hz, 1H).
12: m.p. 119–120ꢁ (Lit.[23] 119ꢁ). H NMR ꢀ 4.07 (s, 3H), 6.97 (d,
1
J ¼ 8.9 Hz, 1H), 7.67 (dd, J ¼ 8.9, 2.4 Hz, 1H), 8.27 (d, J ¼ 2.4 Hz, 1H),
10.23 (brs, 1H).
13: m.p. 201–202ꢁ (Lit.[32] 198ꢁ). H NMR ꢀ 3.92 (s, 3H), 7.44 (s, 1H),
1
7.82 (s, 1H).
14a: m.p. 204–205ꢁ (Lit.[33] 204–205ꢁ). 1H NMR ꢀ 2.45 (s, 3H), 7.30 (d,
J ¼ 7.9 Hz, 1H), 7.88 (dd, J ¼ 7.9, 1.5 Hz, 1H), 8.20 (d, J ¼ 1.2 Hz, 1H).
14b: m.p. 60–61ꢁ (Lit.[34] 61ꢁ). 1H NMR ꢀ 4.43 (s, 2H), 7.26 (d,
J ¼ 8.5 Hz, 2H), 7.47 (d, J ¼ 8.3 Hz, 2H).
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Received in the UKNovember 11, 2000