Oxidation of aliphatic 2,2-dichloroalkanals by HNO3 in CH 2Cl2: An easy and eco-friendly route to the corresponding 2,2-dichloroalkanoic acids

Article abstract of DOI:10.1081/SCC-120030698

A simple, economically convenient, and eco-compatible procedure for the oxidation of 2,2-dichloroalkanals to the corresponding alkanoic acids has been set up, employing HNO₃ in CH₂O₂, in the presence of NaNO₂ as catalyst.

Full text of DOI:10.1081/SCC-120030698

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Oxidation of Aliphatic 2,2‐Dichloroalkanals by HNO3
in CH Cl : An Easy and Eco‐friendly Route to the
2
2
Corresponding 2,2‐Dichloroalkanoic Acids
a
b
a
a
Franco Bellesia , Laurent De Buyck , Franco Ghelfi , Ugo M. Pagnoni & Paolo
c
Strazzolini
a
Dipartimento di Chimica, Università degli Studi di Modena e Reggio Emilia, Modena,
Italia
b
Department of Organic Chemistry, Faculty of Agricultural and Applied Biological
Sciences, Ghent University, Ghent, Belgium
c
Dipartimento di Scienze e Tecnologie Chimiche, Università di Udine, via del Cotonificio
108, I‐33100, Udine, Italia
Version of record first published: 21 Aug 2006.
To cite this article: Franco Bellesia , Laurent De Buyck , Franco Ghelfi , Ugo M. Pagnoni & Paolo Strazzolini (2004):
Oxidation of Aliphatic 2,2‐Dichloroalkanals by HNO in CH Cl : An Easy and Eco‐friendly Route to the Corresponding
3
2
2
2,2‐Dichloroalkanoic Acids, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 34:8, 1473-1481
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w
SYNTHETIC COMMUNICATIONS
Vol. 34, No. 8, pp. 1473–1481, 2004
Oxidation of Aliphatic 2,2-Dichloroalkanals
by HNO in CH Cl : An Easy and
3
2
2
Eco-friendly Route to the Corresponding
,2-Dichloroalkanoic Acids
2
1
Franco Bellesia, Laurent De Buyck, Franco Ghelfi,
2
1
1
Ugo M. Pagnoni, and Paolo Strazzolini
3,
*
1
Dipartimento di Chimica, Universit a` degli Studi di Modena e Reggio
Emilia, Modena, Italia
2
Department of Organic Chemistry, Faculty of Agricultural and
Applied Biological Sciences, Ghent University,
Ghent, Belgium
Dipartimento di Scienze e Tecnologie Chimiche,
3
Universit a` di Udine, Udine, Italia
ABSTRACT
A simple, economically convenient, and eco-compatible procedure for
the oxidation of 2,2-dichloroalkanals to the corresponding alkanoic
*
Correspondence: Paolo Strazzolini, Dipartimento di Scienze e Tecnologie Chimiche,
Universit a` di Udine, via del Cotonificio 108, I-33100 Udine, Italia; Fax: þ39-0432-
5
58803; E-mail: strazzolini@dstc.uniud.it.
1
473
DOI: 10.1081/SCC-120030698
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

ORDER
REPRINTS
1
474
Bellesia et al.
3 2 2
acids has been set up, employing HNO in CH Cl , in the presence of
NaNO as catalyst.
2
Key Words: Alkanals; Alkanoic acids; Oxidations; Nitric acid; Radical
reactions.
INTRODUCTION
2
,2-Dichloroalkanoic acids and their derivatives are valuable and versatile
[1–8]
substrates in synthetic organic chemistry.
CCl COY, which provides these molecules with a number of interesting features,
The bifunctional arrangement
2
[9–13]
can be secured by “classical” connective approaches,
acetic or trichloroacetic acids derivatives and exploiting ionic
starting from dichloro-
[9,12]
[
10,11]
or radical
[13]
or even pericyclic routes; nevertheless, in the overwhelming majority of cases
these methods also insert a third functional group at the b-carbon on the ensuing
molecular skeleton. In comparison, the nonconnective strategy, more appropriate
for large scale production of 2,2-dichloroalkanoic acids and derivatives bearing
no additional function on the aliphatic chain, has received much less attention
[
5]
so far. The Viehe’s direct chlorination of amides with COCl /Cl , as well as
2
2
the oxidation–chlorination of 2-alkyl-4,5-dimethyl-1,3-dioxolanes with trichloro-
[14]
isocyanuric acid are viable syntheses, but the excessive complexity make these
protocols tedious and thus less attractive for a potential scale-up. Chlorination by
the classical Hell–Volhard–Zelinskii reaction is unsuitable for the preparation of
a,a-dihalocarboxylic acids, being only useful for the introduction of a single Cl
[15]
atom (see for example Ref. ).
Currently, the more convenient way to obtain 2,2-dichloroalkanoic acids
(2) involves the oxidation of 2,2-dichloroalkanals (1), starting materials
smoothly obtainable by direct chlorination of aldehydes or even one-pot
[
16–19]
chlorination–oxidation of alcohols.
ing acids has been performed with KMnO ,
Final oxidation to the correspond-
[16]
[16,17]
K Cr O ,
2
H O /
2 2
4
2
7
[18]
[
16,17]
.
and, more recently, with Cl /2-picoline HCl.
NaHCO3,
To date,
2
alkaline permanganate remains the reagent of choice for the oxidation step,
but the actual need to minimize the amounts of toxic wastes and by-products
from chemical processes makes urgent the development of alternative and
[20,21]
more environmentally compatible synthetic protocols.
RESULTS AND DISCUSSION
Nitric acid in CH Cl solution proves to be a very versatile and mild-
in-nature reagent, having recently found many useful synthetic applications
2
2

ORDER
REPRINTS
Oxidation of 2,2-Dichloroalkanals by HNO3
1475
[
21–26]
in organic chemistry;
smoothly performing the oxidation of aldehydes to the corresponding
on the other hand, the special ability of HNO in
3
[27–29]
carboxylic acids is well known.
possibility of using the HNO –CH Cl system for the oxidation of some
Therefore, we decided to consider the
3
2
2
2,2-dichloroalkanals (1) to the corresponding alkanoic acids (2), also taking
into account the safe, easy availability,
[30]
and low cost of the chemicals to
be employed, in addition to the advantages of operating in an organic solvent.
When 2,2-dichlorohexanal (1e) was treated with HNO (1 : 2 up to 1 : 3
3
molar ratio) in CH Cl at room temperature, no conversion was observed
2
2
1
even after prolonged reaction times ( H NMR analysis of the intact reaction
mixture after dilution with CDCl ), probably as a consequence of the presence
3
of two electron-withdrawing a-Cl atoms causing a marked inhibition of the
oxidation process. We strongly deemed that the observed inertness towards
HNO attack had to be correlated to an ineffective generation of NO , the latter
3
2
[
26]
being considered responsible of the oxidation under the present conditions.
The catalytic role of HNO as initial source of the active species NO in
2
2
[
27,31]
the HNO oxidation of aldehydes to acids is well documented. There-
fore, we reasoned that the drawback could be circumvented by simply adding
3
NaNO (1% mol per mol of substrate) to the reaction mixture. As expected, in
2
the presence of nitrite the oxidation took place and 1e was smoothly converted
into acid 2e within 8 d at room temperature. The method was extended to a
series of aliphatic 2,2-dichloroalkanals, affording the corresponding acids
generally in good yields (Sch. 1, Table 1).
The efficiency of the oxidation proved to be independent with respect to
the length of the aliphatic chain and only in the case of 2,2-dichloro-3-phenyl-
propanal (1i), the reaction gave poor yields (Table 1, entry 10) owing to com-
petitive ring nitration. The productivity of the method can be considerably
enhanced by heating: in fact, the oxidation of 2,2-dichlorooctanal (1f), at
608C under moderate pressure, was complete within 24 hr, affording the
corresponding acid 2f in yields comparable to those obtained at room tempera-
ture (Table 1, entries 6 and 7).
The mechanism of the reaction, also in accordance with previous
[
31,32]
reports,
HNO playing the role of a convenient source of the active species NO , as
appears to be definitively of radical nature (Sch. 2), with
3
2
such or in its protonated form, responsible of the oxidation.
Scheme 1.

ORDER
REPRINTS
1
476
Bellesia et al.
Table 1. Oxidation of 2,2-dichloroalkanals (1) to the corresponding alkanoic acids
(2) with HNO
3
in CH
2
Cl
2
(Sch. 1).
R
a
b
Entry Substrate (1)
Conversion (%)
Product (2) Yield (%)
1
2
3
4
5
6
7
8
9
0
a
b
c
d
e
f
CH
3
.99
.99
.99
a
b
c
d
e
f
66
78
87
72
80
92
92
88
93
2 5
C H
(CH ) CH
3
2
2
c
CH(CH
(CH CH
(CH ) CH
3
)
2
98
2
)
3
3
3
3
3
98
97
2
5
d
f
(CH ) CH
98
f
2
2
5
9
g
h
i
(CH
(CH
CH Ph
)
CH
97
98
98
g
h
i
2 3
)13CH
e
1
47
2
a
1
3
Determined by H NMR on intact reaction mixture, after suitable dilution with CDCl .
Acid2wasthesolereactionproduct. Unlessotherwisestated, theoxidationwas performed
in 8 d at room temperature.
b
Isolated product.
Longer reaction time (15 d) was required.
c
d
Reaction carried out in 24 hr at 608C.
Not isolated; the reaction mixture contained in addition some 51% of ring-nitrated
products.
e
In conclusion, the procedure described above may represent a
valuable alternative to the existing methods for the oxidation of aliphatic
a,a-dichloroalkanals to the corresponding alkanoicacidsin terms of simplicity,
economicity, and eco-compatibility, especially in the case of large scale
processes. Furthermore, the operation in CH Cl offers evident advantages on
2
2
[33,34]
respect to previous similar oxidations performed in aqueous environment.
Scheme 2.

ORDER
REPRINTS
Oxidation of 2,2-Dichloroalkanals by HNO3
EXPERIMENTAL
1477
Unless otherwise specified, reagents, solvents, and products were commer-
cially available. 2,2-Dichloroalkanals were prepared according to literature
[
17,19]
procedures.
Hydro Chemicals France (Nanterre, France) and kept at 48C in the dark to
avoid decomposition; the acid was freshly distilled and its titre, averaging ca.
Commercial 100% HNO (d ¼ 1.51) was purchased from
3
24M, alkalimetrically checked prior to use. Reported boiling points refer to
the central cut of small scale distillations and are uncorrected. Melting points
were obtained with a Mettler FP 61 automatic apparatus and are uncorrected.
IR spectra were recorded on a Nicolet FTIR Magna 550 spectrophotometer
1
13
using the KBr technique. H- and C NMR spectra were recorded in CDCl3
on a Bruker AC-200 spectrometer at 200 and 50MHz, respectively. GC ana-
TM
lyses were carried out using a 0.25mm i.d. ꢀ 30m SPB5 fused silica capil-
lary column (Supelchem, Milano, Italy). MS measurements were performed
with a Fisons TRIO-2000 apparatus, working in the positive-ion electron impact
mode (70 eV).
General Procedure for the Oxidation of 2,2-Dichloroalkanals
In a typical procedure, a solution of the selected dichloroalkanal
1, 50.0 mmol) in CH Cl (10 mL) was admixed with finely grinded NaNO
2 2 2
(
(
0.5 mmol), treated with a solution of HNO3 (d ¼ 1.51, 150.0 mmol) in
CH Cl (10 mL), and kept under stirring for 8 d at room temperature (or
2
2
24 hr at 608C under moderate pressure) in a well sealed flask. After that
time, the reaction mixture was diluted with CH Cl (30 mL), washed with
2
2
1
0% aqueous Na SO (2 ꢀ 30 mL), dried over anhydrous Na SO , filtered,
2
4
2
4
and the solvent evaporated off. The obtained acids 2 were isolated after
conventional distillation or crystallized when suitable (Table 1).
2
,2-Dichlorobutanoic acid (2b). Colorless liquid, b.p. 1248C/4000 Pa
[16] 1
(
106–1088C/1867 Pa).
H NMR (CDCl ) d (TMS): 1.22 (t, 3H, CH ),
3 3
1
.49 (q, 2H, CH ), 11.90 (br s, 1H, COOH). C NMR (CDCl ) d (TMS):
3
2
2
3
9
.40 (CH ), 38.35 (CH ), 84.92 (CCl ), 171.97 (COOH).
3
2
2
2
,2-Dichloropentanoic acid (2c). Colorless liquid, b.p. 1318C/4000 Pa
[17] 1
(
65–678C/10 Pa).
H NMR (CDCl ) d (TMS): 1.02 (t, 3H, CH ), 1.56–
3 3
1
.78 (m, 2H, CH ), 2.36–2.49 (m, 2H, CH ), 11.94 (br s, 1H, COOH).
2 2
1
3
C NMR (CDCl ) d (TMS): 13.33 (CH ), 18.55 (CH ), 46.83 (CH ), 83.93
2
3
3
2
(
CCl ), 172.01 (COOH).
2
2
,2-Dichloro-3-methylbutanoic acid (2d). Colorless liquid, b.p. 1258C/
[16] 1
4
000 Pa (109–1118C/1467 Pa).
H NMR (CDCl ) d (TMS): 1.18 (d, 6H,
3

ORDER
REPRINTS
1
478
Bellesia et al.
1
CH ), 2.75 (heptet, 1H, CH), 11.44 (br s, 1H, COOH). C NMR (CDCl3)
3
3
d (TMS): 17.57 (CH ), 40.38 (CH), 90.20 (CCl ), 172.02 (COOH).
3
2
2
,2-Dichlorohexanoic acid (2e). Colorless liquid, b.p. 141 8C/4000 Pa
[17] 1
(
66–678C/1 Pa).
H NMR (CDCl ) d (TMS): 0.96 (t, 3H, CH ), 1.32–
3 3
1
.52 (m, 2H, CH ), 1.53–1.70 (m, 2H, CH ), 2.39–2.51 (m, 2H, CH ),
2 2 2
1
1.84 (br s, 1H, COOH). C NMR (CDCl ) d (TMS): 13.71 (CH ), 22.02
3
1
3
3
(
CH ), 27.11 (CH ), 44.67 (CH ), 84.13 (CCl ), 171.97 (COOH).
2
2
2
2
2
,2-Dichlorooctanoic acid (2f). Pale yellow liquid, b.p. 1168C/133 Pa
[17] 1
(
93–968C/2 Pa).
H NMR (CDCl ) d (TMS): 0.90 (t, 3H, CH ), 1.24–
3 3
1
.48 (m, 6H, CH ), 1.52–1.72 (m, 2H, CH ), 2.37–2.50 (m, 2H, CH ),
2 2 2
1
3
1.97 (br s, 1H, COOH). C NMR (CDCl ) d (TMS): 13.94 (CH ), 22.44
1
3
3
(
CH ), 24.99 (CH ), 28.50 (CH ), 31.40 (CH ), 44.91 (CH ), 84.12 (CCl ),
2
2
2
2
2
2
172.01 (COOH).
2
,2-Dichlorododecanoic acid (2g). Pale yellow liquid, b.p. 1358C/4 Pa
[17] 1
(
135–1368C/4 Pa).
H NMR (CDCl ) d (TMS): 0.88 (t, 3H, CH ), 1.18–
3 3
1
.51 (m, 14H, CH ), 1.51–1.78 (m, 2H, CH ), 2.33–2.48 (m, 2H, CH ), 11.91
2 2 2
1
3
(
br s, 1H, COOH). C NMR (CDCl ) d (TMS): 14.22 (CH ), 22.84 (CH ),
3 3 2
25.61 (CH ), 29.31 (CH ), 29.52 (CH ), 29.57 (CH ), 29.66 (CH ), 29.74
2 2 2 2 2
(
CH ), 32.11 (CH ), 45.49 (CH ), 84.94 (CCl ), 171.03 (COOH).
2
2
2
2
2
,2-Dichlorohexadecanoic acid (2h). Pale yellow solid, m.p. 328C
[17] 1
(hexane) [(33–358C (hexane)].
CH ), 1.17–1.50 (m, 18H, CH ), 1.50–1.82 (m, 2H, CH ), 2.34–2.49
H NMR (CDCl ) d (TMS): 0.88 (t, 3H,
3
3
2
2
1
3
(
m, 2H, CH ), 9.92 (br s, 1H, COOH). C NMR (CDCl ) d (TMS): 14.10
2 3
(
CH ), 22.68 (CH ), 25.04 (CH ), 28.85 (CH ), 29.25 (CH ), 29.35 (CH ),
3 2 2 2 2 2
2
9.44 (CH ), 29.56 (CH ), 29.65 (4 ꢀ CH ), 31.91 (CH ), 44.93 (CH ),
2
2
2
2
2
2
8
4.29 (CCl ), 171.23 (COOH).
ACKNOWLEDGMENTS
We thank the Ministero della Universit a` e della Ricerca Scientifica e
Tecnologica (MURST) and the F.W.O.-Vlaanderen and BOF-RUG for
financial assistance.
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Oxidation of 2,2-Dichloroalkanals by HNO3
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3
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Received in Poland August 18, 2003

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