Oxidation cascade with oxone: Cleavage of olefins to carboxylic acids

Article abstract of DOI:10.1016/j.tet.2014.01.042

A variety of olefins is shown to be cleaved oxidatively to the corresponding acids with oxone as the reagent. The simple methodology that works well for a range of alkenes, i.e., styrenes, nitrostyrenes, stilbenes, cinnamic acids, chalcones, etc., involves heating of the reactant with oxone in acetonitrile-water mixture (1:1, v/v) at reflux. The oxidation cascade involves initial dihydroxylation followed by oxidative cleavage and oxidation of the resultant aldehydes to acids.

Full text of DOI:10.1016/j.tet.2014.01.042

Accepted Manuscript
Oxidation Cascade with Oxone: Cleavage of Olefins to Carboxylic Acids
Keshaba Nanda Parida, Jarugu Narasimha Moorthy
PII:
S0040-4020(14)00084-2
10.1016/j.tet.2014.01.042
TET 25216
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 1 October 2013
Revised Date: 8 January 2014
Accepted Date: 20 January 2014
Please cite this article as: Parida KN, Moorthy JN, Oxidation Cascade with Oxone: Cleavage of Olefins
to Carboxylic Acids, Tetrahedron (2014), doi: 10.1016/j.tet.2014.01.042.
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ACCEPTED MANUSCRIPT
Oxidation Cascade with Oxone: Cleavage of Olefins to Carboxylic Acids
Keshaba Nanda Parida and Jarugu Narasimha Moorthy*
†
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, INDIA
Abstract
A variety of olefins is shown to be cleaved oxidatively to the corresponding acids with oxone as the
reagent. The simple methodology that works well for a range of alkenes, i.e., styrenes, nitrostyrenes,
stilbenes, cinnamic acids, chalcones, etc., involves heating of the reactant with oxone in acetonitrile-water
mixture (1:1, v/v) at reflux. The oxidation cascade involves initial dihydroxylation followed by oxidative
cleavage and oxidation of the resultant aldehydes to acids.
*
Corresponding author.
Tel. +91-512-2597438; fax: +91-512-2597436; e-mail address: moorthy@iitk.ac.in (J. N. Moorthy)
Graphic for TOC
Keywords: Oxidation, Ozonolysis, Oxone, Styrenes, Stilbenes, Cinnamic Acids, Chalcones and Diols.
1

ACCEPTED MANUSCRIPT
1
.
Introduction
Oxidative cleavage of olefins to the corresponding carbonyl compounds, i.e., aldehydes, ketones and
acids, is a transformation that is of paramount importance in organic synthesis, and has been investigated
immensely in organic synthesis. This reaction may be performed by a variety of reagents based on
1
transition metals such as Mn, Cr, Mo, Ru, Pd, Re, V, Ce, W, Co, In, Os, etc. However, the use of
organometallic or metal-based reagents is associated with a serious drawback involving the formation of
byproducts that are hazardous and detrimental to the environment. Development of new synthetic
methodologies that are green, cost effective and environmentally benign is thus an incessant pursuit. In
2
3
this regard, although the use of ozone and oxygen is advantageous for oxidative cleavage of olefins,
2
d
2e
ozone is explosive and the reactions must be performed in a special apparatus. Literature reveals a
number of metal-free procedures for the cleavage of olefins. For example, Brooks et al. showed that
4
styrene can be cleaved with H O . Incidentally, the strength of H O varies with time and its source,
2
2
2
2
which limit its usage. Ochiai and co-workers reported that alkenes can be cleaved oxidatively with ArI in
5a
5b
the presence of stoichiometric amounts of iodosobenzene or m-CPBA. Nicolaou and co-workers
introduced a one-pot procedure for the cleavage of olefins by phenyliodonium diacetate (PIDA) reagent,
6
which involves the intermediacy of diol intermediates. Vinod et al. showed that the oxidative cleavage of
olefins can be accomplished by p-iodobenzoic acid as a catalyst in the presence of oxone in acetonitrile-
0
7
water at 60 C; the active species responsible for the oxidation was shown to be [hydroxy(4-
carboxyphenyl)-iodonium]ion.
8
9
In continuation of our on-going investigations with IBX and oxone, we recently reported that benzylic
alcohols can be oxidized to the corresponding acids in a facile manner using oxone as the terminal
9
oxidant in acetonitrile-water (1:1) at reflux. Given that olefins are reported to undergo dihydroxylation
7,10
with oxone and that the hydroxyl groups are oxidized with oxone in acetonitrile-water (1:1, v/v) at
2

ACCEPTED MANUSCRIPT
9
reflux conditions as shown recently by us, we suspected that olefins should be cleaved oxidatively by
oxone without any additive. Notwithstanding the finding by Vinod et al. that no oxidative cleavage was
7
observed when styrene was heated in the presence of oxone at 60 °C in acetontrile-water, we investigated
the oxidative cleavage of olefins at the reflux conditions. To our delight, oxone was indeed found to be a
very good reagent for tandem dihydroxylation followed by oxidative cleavage. In view of its cheap
availability and environmentally-benign attributes, oxone is assuming increasing importance in a variety
11
of oxidative transformations as a reagent as well as a co-oxidant. Herein, we report that oxone can be
directly employed as a reagent to oxidatively cleave a variety of olefins to the corresponding acids in
1
moderate to excellent isolated yields; H NMR monitoring of the reactions as well as the isolation of the
12
diol intermediates in some cases attest to the occurrence of a domino/cascade oxidations with oxone.
2
.
Results and discussion
At the outset, the reaction of styrene in CH CN-H O (1:1, v/v) with oxone was examined at reflux
3
2
conditions. TLC analyses indicated gradual formation of the diol intermediate and benzoic acid. As oxone
13
is known to decompose in the acidic medium, 3.0 equiv of the reagent was introduced in increments to
drive the reaction to completion. At the end of 14 h, the reaction led to benzoic acid in 70% isolated yield.
Inspired by this result, a number of olefins were subjected to oxidation likewise. As shown in Table 1,
substituents such as bromo, cyano, nitro and carboxy at para position afforded the corresponding acids in
7
7-93% yields (entries 2-5). The products in similar yields were also isolated for substrates containing
substitutents at ortho position as well (entries 7 and 8). However, p-methylstyrene was found to yield p-
methylbenzoic acid in a relatively poor yield (entry 6); we have shown in our previous investigation that
alkylaromatics undergo side-chain oxidation with oxone. We attribute the poor isolated yield in this
instance to competitive oxidation of the methyl group leading to an intractable mixture of products.
Indeed, when the reaction was conducted for 24 h with 5 equiv. of oxone, it gave a mixture of products,
3

ACCEPTED MANUSCRIPT
which includes p-toluic acid (16%), terephthalic acid (27%) and p-formylbenzoic acid (3%); it should be
noted that benzaldehyde is an intermediate in the oxidation of toluene, as has been shown by us
9
previously. When the electron rich substrates such as o-methylstyrene and p-methoxystyrene were
reacted with oxone at reflux, formation of messy product mixtures was observed. o-Toluic acid and p-
methoxybenzoic acid were isolated in 8 and 17% yields, respectively (entries 9 and 10). However, when
these reactions were conducted only for 12 h by employing 3 equivalents of oxone, 1-o-tolylethane-1,2-
diol and 1-(p-methoxyphenyl)ethane-1,2-diol were obtained in 56 and 30% yields, respectively.
Divinylbenzene was found to yield terephthalic acid in an excellent isolated yield, albeit with 8
equivalents of oxone introduced incrementally (entry 11). While the oxidation of p-bromo-β-
methylstyrene yielded p-bromobenzoic acid in 74% yield, that of p-bromo-α,β-dimethylstyrene led to p-
bromoacetophenone in 72% isolated yield (entries 12 and 13). p-Bromocinnamyl alcohol and p-
bromocinnamyl bromide underwent oxidation with 4 equivalents of oxone to provide p-bromobenzoic
acid in 72 and 81% yields, respectively (entries 14 and 15). The reaction of cyclohexene with oxone
yielded adipic acid in 58% yield (entry 16), while its phenyl derivative led to the corresponding keto acid
in 63% yield together with benzoic acid in 13% yield (entry 17). The reaction of tridecene with 5
equivalents of oxone over a period of 24 h of reaction duration led to dodecanoic acid in 61% yield (entry
1
8). Clearly, the results in Table 1 underscore the potential of oxone as a reagent for oxidative cleavage of
olefins.
4

ACCEPTED MANUSCRIPT
a
3 2
TABLE 1. Results of Oxidative Cleavage of Styrene Using Oxone in CH CN-H O
Entry
Substrate
Equiv./
Time (h)
Product
Isolated
Yield (%)
b
1
2
3
4
5
6
7
8
9
X = H
= p-Br
= p-NO2
= p-CN
= p-CO
= p-Me
= o-Br
= o-NO
= o-Me
3/14
3/12
3/14
3/14
3/19
3/24
3/24
3/17
5/24
5/24
70
90
92
93
77
43
77
82
2
H
2
c
8
d
1
0
= p-MeO
17
1
1
8/21
4/13
4/10
91
74
1
1
2
3
e
72
1
4
4/14
72
1
1
5
6
4/14
3/11
81
58
e,f
4
/20
63
1
1
7
8
5/24
61
a
b
3 2
All reactions were carried out in CH CN-H O (1:1, v/v) mixture at reflux. Isolated yields unless mentioned
c
d
otherwise. Isolated from a messy product mixture. 1-(4-Methoxyphenyl)ethane-1,2-diol was isolated in 15%
yield. 2 Equiv of H
e
f
2
SO
4
was added. Benzoic acid was also isolated in 13% yield.
5

ACCEPTED MANUSCRIPT
Spurred by the results in Table 1, oxidative cleavage of diarylolefins, i.e., stilbenes, was examined. From
TLC monitoring studies of the reaction of parent stilbene with oxone, it was concluded that 5.0
equivalents of oxone is necessary for completion of the reaction. As shown in Table 2, a number of
stilbene derivatives containing substituent(s) at para position(s) were found to undergo oxidative cleavage
in respectable yields (entries 1-5 and 7). The reaction was found to be highly sluggish for the stilbene
substituted at the ortho position, e.g., 2,2’-dibromostilbene (entry 7) suggesting that sterics possibly
impede the reaction. In the case of 4-methoxystilbene, the oxidation was found to yield an intractable
mixture of products. At least three products, i.e., benzoic acid (35%), p-methoxybenzoic acid (8%) and 1-
(
4-methoxyphenyl)-2-phenylethane-1,2-dione (20%) were isolated (entry 6). We have earlier noted that
the oxidation of aromatics containing e-donating groups likewise leads to messy product mixtures due
presumably to operation of electron transfer chemistry; this indeed is the limitation with oxone when
9
employed as an oxidant.
a
Table 2. Results of Oxidative Cleavage of Stilbenes Using Oxone in CH CN-H O
3
2
Product(s)
Yield (%)
Substrate
b
Oxone
Entry
Equiv/Time
(
h)
+
1
2
3
4
5
6
7
8
X = H
X = p-Br
X = H
X = H
X = H
X = H
X = p-Br
X = o-Br
Y = H
Y = p-Br
Y = p-Br
Y = p-NO2
Y = p-CN
Y = p-OMe
Y = p-NO
Y = o-Br
5/24
5/22
5/15
5/22
5/15
4/14
5/18
6/24
50
83
73
80
79
35
80
12
78
81
82
c
8
2
81
d
12
a
b
All reactions were carried out in CH CN-H O (1:1, v/v) mixture at reflux. Isolated yields unless mentioned
3
2
c
otherwise. 1-(4-Methoxyphenyl)-2-phenylethane-1,2-dione was isolated in 20% yield together with other products,
see text. The starting material was recovered unreacted in 75% yield.
d
6

ACCEPTED MANUSCRIPT
In logical extension of these studies, the oxone-mediated oxidation of cinnamic acids, cinnamides,
cinnamonitriles, nitrostyrene and chalcones was also explored. In Table 3 are consolidated these results;
in some instances, more equivalents of oxone was found to be necessary to ensure that the reactions went
to completion. As can be seen, all cinnamic acids, with the exception of the parent one and the p-methoxy
derivative (entries 1 and 7), were found to yield the corresponding benzoic acids in very good yields
(
entries 2-6). Parent nitrostyrene as well as its p-bromo derivative led to the corresponding acids (entries 8
and 9). p-Bromocinnamamide, methyl p-bromocinnamate and p-bromocinnamonitrile yielded p-
bromobenzoic acid in 76-80% yields (entries 10-12). While the parent chalcone afforded benzoic acid in
4
9% isolated yield, its bromo-derivative yielded the corresponding p-bromobenzoic acid in 80% yield
(
entries 13 and 14); the reactions were found to be incomplete in both cases even after 24 h.
Table 3. Results of Oxidative Cleavage of Cinnamic Acids, Nitrostyrenes, Cinnamamides and Chalcones
a
Using Oxone in CH CN-H O
3
2
Entry
Substrate
Equiv/
Time (h)
Product
Isolated
Yield (%)
b
1
2
3
4
5
6
7
X = H
= p-CN
= o-CO
= m-NO2
= p-Br
= p-NO
= p-MeO
5/20
5/20
5/22
5/24
5/30
5/20
5/24
44
90
85
81
73
81
CO H
2
X
2
H
2
c
15
8
6/24
76
9
5/24
86
1
1
0
1
5/24
5/22
76
80
7

ACCEPTED MANUSCRIPT
1
1
1
2
3
4
4/18
6/24
6/24
76
49
80
d
e
a
b
c
All reactions were carried out in CH CN-H O (1:1, v/v) mixture at reflux. Isolated yield. Intractable reaction
3
2
d
e
mixture. The starting material was recovered in 26% yield. The starting material was recovered unreacted in 7% .
3
.
Mechanism of Oxidation
We believe that the initial double bond oxidation is a common step in the oxidation of all substrates for
14
which the results are collected in Tables 1-3. Oxone has been reported to convert olefins to epoxides,
which under the employed conditions of the reaction open up to give diols; it should be noted that the
solution of oxone in acetonitrile-water (1:1, v/v) is strongly acidic, and we have found that the pH of the
solutions of oxone in acetonitrile-water (1:1, v/v) mixture employed for oxidations described herein is
typically ∼ 3-4. Thus, the initially formed epoxides should be expected to open up in acetontrile-water to
give the corresponding diols. We have indeed isolated the diol intermediates in some cases, e.g., styrene
(
entry 1, Table 1), p-methylstyrene (entry 6, Table 1) and 1-phenylcyclohexene (entry 15, Table 1), when
the reactions were run for a short period. Indeed, the fact that the reaction of styrene with oxone in
CH CN-H O (1:1, v/v) leads to dihydroxy products has previously been shown by Vinod and co-
3
2
7
1
workers. Further, the formation of diol intermediates is clearly revealed in the H NMR monitoring of the
reactions for some cases, e.g., p-nitrocinnamic acid, stilbene and 4,4’-dibromostilbene, cf. Supplementary
Information. The oxidative cleavage of diols presumably occurs via formation of the cyclic hypervalent
sulfur intermediate with oxone and subsequent decomposition to the latter to aldehyde/s (Scheme 1). The
0
fact that only dihydroxylated products are observed at 60 C and that the reflux condition leads to
cleavage products suggests that the initial epoxidation followed by opening is much faster than
8

ACCEPTED MANUSCRIPT
equilibrium formation of the 6-membered cyclic hypervalent sulfur intermediate that collapses to the
carbonyl compounds, cf. Scheme 1. When the product is aldehyde, it subsequently undergoes rapid
oxidation with oxone; the latter, i.e., oxidation of the aldehyde to the corresponding acid, is a well-known
15
reaction. Clearly, a cascade of oxidations that include dihydroxylation, cleavage to the aldehydes
followed by further oxidation the latter to the corresponding acids occur in tandem.
Scheme 1. Mechanism of Oxidative Cleavage of Styrene.
4
.
Conclusions
We have found that the cheap and environmentally-benign oxone can be employed directly for oxidative
cleavage of a number of olefins that include dialkyl, diaryl and alkyl aryl olefins, cinnamic acids,
cinnamyl alcohols, cinnamamides and chalcones to the corresponding acids. The oxidations proceed via
initial dihydroxylation of olefins to the diols. Of course, the aldehydes that are produced undergo further
9

ACCEPTED MANUSCRIPT
oxidation with oxone to the corresponding carboxylic acids under the employed conditions of reaction.
The procedure that involves heating of the substrate in CH CN-H O (1:1, v/v) mixture with incremental
3
2
addition of oxone is simple, convenient and cost-effective for a cascade oxidation of olefins, i.e.,
dihydroxylation, oxidative cleavage and oxidation of aldehydes, and thus should constitute an invaluable
addition to the repertoire of transformations accomplished by oxone as a reagent.
5
. Experimental Section
5
.1. General
Solvents were distilled prior to use and double distilled water was used for all the reactions. All reactions
were carried out in an open atmosphere without any precaution. The products were isolated by column
chromatography with a silica gel of 100−200 ꢀm particle size. NMR spectra were recorded with 400 and
5
00 MHz spectrometers.
5
.2. General Procedure for the Oxidative Cleavage of Olefins. To a solution of the olefin (0.5-1.2
mmol) in 16 mL of acetonitrile-water (1:1) mixture at reflux was introduced oxone incrementally over
the entire duration of the reaction. Progress of the reaction in each case was monitored by TLC analysis.
After completion of the reaction as judged by TLC analysis, the reaction mixture was cooled to rt, and
the organic matter was extracted with ethyl acetate. The combined organic extract was dried over anhyd
Na SO and concentrated in vacuo. The residue was subjected to a short-pad silica gel column
2
4
1
chromatography to isolate pure product/s. All the products were characterized by their H NMR spectral
data.
9
1
5
5
.2.1. Benzoic Acid. Colorless solid; R (25% EtOAc/pet. ether) 0.37; H NMR (CDCl , 400 MHz) δ
f
3
7
.49 (t, J = 7.3, 2H), 7.62 (t, J = 7.8 Hz, 1H), 8.12 (d, J = 7.3 Hz, 2H).
9
1
.2.2. p-Bromobenzoic Acid. Colorless solid; R
f
(50% EtOAc/pet. ether) 0.48; H NMR (CDCl
3
, 500
MHz) δ 7.62 (d, J = 8.55 Hz, 2H), 7.96 (d, J = 8.55 Hz, 2H).
1
0

ACCEPTED MANUSCRIPT
9
1
5
5
f 3 3
.2.3. p-Nitrobenzoic Acid. Colorless solid; R (10% CH OH/EtOAc) 0.32; H NMR (CDCl , 400
MHz) δ 8.27 (d, J = 8.8 Hz, 2H), 8.33 (d, J = 8.8 Hz, 2H).
9
1
.2.4. o-Bromobenzoic Acid. Colorless solid; R (50% EtOAc/pet. ether) 0.49; H NMR (CDCl , 500
f
3
MHz) δ 7.38-7.43 (m, 2H), 7.72 (d, J = 8.2 Hz, 1H), 8.02 (dd, J = 7.3 Hz, J = 2.1 Hz, 1H).
1
2
9
5
5
5
5
5
5
.1.5. Adipic Acid. Colorless solid; R (10% MeOH/EtOAc) 0.24; mp 146-148 °C (lit. mp 147.5-149
f
1
°
C). H NMR (acetone-d , 500 MHz) δ 1.63-1.67 (m, 4H), 2.30-2.35 (m, 4H).
6
9
1
.2.6. o-Nitrobenzoic Acid. Colorless solid; R
f
(10% CH
3
OH/EtOAc) 0.31; H NMR (CDCl
3
, 400
MHz) δ 7.68-7.73 (m, 2H), 7.86–7.92 (m, 2H).
9
1
.2.7. p-Cyanobenzoic Acid. Colorless solid; R (50% EtOAc/pet. ether) 0.19; H NMR (DMSO-d ,
f
6
5
00 MHz) δ 7.98 (d, J = 8.6 Hz, 2H), 8.07 (d, J = 8.6 Hz, 2H).
9
1
.2.8. p-Bromoacetophenone. Colorless solid; R (10% EtOAc/pet. ether) 0.43; H NMR (CDCl , 500
f
3
MHz) δ 2.58 (s, 3H), 7.60 (d, J = 8. 5 Hz, 2H), 7.82 (d, J = 8.5 Hz, 2H).
9
1
.2.9. Terephthalic Acid. Colorless solid; R
f
(10% CH
3
6
OH/EtOAc) 0.2; H NMR (DMSO-d , 500
MHz) δ 8.03 (s, 4H), 12.7 (bs, 2H).
9
1
.2.10. 1-Phenylcyclohexane-1,2-diol. Colorless solid; R (50% EtOAc/pet. ether) 0.5; H NMR (400
f
MHz, CDCl ) δ 1.37-1.45 (m, 1H), 1.51-1.55 (m, 1H), 1.64-1.73 (m, 3H), 1.82-1.88 (m, 3H),
3
3
.96-3.99 (m, 1H), 7.26 (t, J = 7.7 Hz, 1H), 7.37 (t, J = 7.4 Hz, 2H), 7.50 (d, J = 8.8 Hz, 2H).
7
1
5
5
.2.11. 6-Phenyl-6-oxo-hexanoic Acid. Colorless solid; R (75% EtOAc/pet. ether) 0.4; H NMR (400
f
MHz, CDCl ) δ 1.74-1.81 (m, 4H), 2.42 (t, J = 6.9 Hz, 2H), 3.01 (t, J = 6.9 Hz, 2H), 7.45 (t, J =
3
7
.7 Hz, 1H), 7.54 (t, J = 7.4 Hz, 2H), 7.95 (d, J = 8.7 Hz, 2H).
16.
.2.12. 1-(4-Methoxyphenyl)-2-phenylethane-1,2-dione. Yellow solid; R (25% EtOAc/pet. ether)
f
1
0
7
.5; H NMR (400 MHz, CDCl ) δ 3.99 (s, 3H), 6.98 (d, J = 8.8 Hz, 2H), 7.5 (t, J = 7.5 Hz, 2H),
3
.64 (t, J = 7.5 Hz, 1H), 7.94-7.98 (m, 4H).
1
7
1
5
5
.2.13. p-Toluic Acid. Colorless solid; R
f 3
(25% EtOAc/pet. ether) 0.37; H NMR (CDCl , 400 MHz) δ
2
.44 (s, 3H), 7.4 (d, J = 8.1 Hz, 1H), 8.01 (d, J = 8.1 Hz, 2H).
17
1
.2.14. 4-Methoxybenzoic Acid. Colorless solid; R (50% EtOAc/pet. ether) 0.4; H NMR (500 MHz,
f
CDCl3) δ 3.88 (s, 2H), 6.95 (d, J = 9.0 Hz, 2H), 8.07 (d, J = 9.0 Hz, 2H).
1
1

ACCEPTED MANUSCRIPT
1
7
1
5
5
5
5
5
5
.1.15. m-Nitrobenzoic Acid. Colorless solid; R
f
(10% MeOH/EtOAc) 0.31; H NMR (400 MHz,
CDCl ) δ 7.74-7.7 (m, 1H), 8.5 (m, 2H), 8.96 (m, 1H).
3
18
1
.2.16. 1-Phenylethane-1,2-diol. Colorless solid; R (50% EtOAc/pet. ether) 0.45; H NMR (400 MHz,
f
CDCl ) δ 3.66-3.74 (m, 2H), 4.82-4.84 (dd, 1H), 7.31-7.37 (m, 5H).
3
18
1
.2.17. 1-(4-Tolyl)ethane-1,2-diol. Colorless solid; R
f
(50% EtOAc/pet. ether) 0.5; H NMR (400
MHz, CDCl ) δ 3.62-3.72 (m, 2H), 4.78 (m, 1H), 7.17-7.25 (m, 5H).
3
1
9
1
.2.18. Phthalic Acid. Colorless solid; R (25% MeOH/EtOAc) 0.2; H NMR (500 MHz,
f
CDCl
3 6
+DMSO-d ) δ 8.34 (b, 2H), 7.55-7.56 (m, 2H), 7.32-7.33 (m, 2H).
19
1
.2.19. Isophthalic Acid. Colorless solid; R (10% CH OH/EtOAc) 0.23; H NMR (DMSO-d , 500
f
3
6
MHz) δ 7.63 (t, J = 7.7 Hz, 1H), 8.16 (dd, J = 7.7 Hz, J = 1.6 Hz, 2H), 8.48 (s, 1H).
1
2
2
0
1
.2.20. Dodecanoic acid. Colorless solid; R (50% EtOAc/pet. ether) 0.5; H NMR (400 MHz,
f
CDCl ) δ 0.86 (t, J = 6.6 Hz, 3H), 1.2-1.31(m, 1H), 1.61(m, 2H), 2.33 (t, J = 7.5 Hz, 2H).
3
1
9
1
5
5
.2.21. o-Toluic acid. Colorless solid; R (25% EtOAc/pet. ether) 0.5; H NMR (400 MHz, CDCl ) δ
f
3
2
.66 (s, 3H), 7.26 (m, 2H), 7.45 (m, 1H), 8.06 (dd, J = 7.5 Hz, J = 1.8 Hz, 1H).
1
1
8
1
.2.22. 1-(p-Methoxyphenyl)ethane-1,2-diol. Colorless solid; R (50% EtOAc/pet. ether) 0.3; H
f
NMR (400 MHz, CDCl ) δ 3.59-3.68 (m, 2H), 3.78 (s, 3H), 4.74 (q, J = 3.6 Hz, 1H), 6.87 (d, J =
3
8
.7 Hz, 2H), 7.23 (d, J = 8.7 Hz, 2H).
1
8
1
5
5
.2.23. 1-o-Tolylethane-1,2-diol. Colorless solid; R
f
(50% EtOAc/pet. ether) 0.5; H NMR (400
MHz, CDCl ) δ 2.33 (s, 3H), 3.61-3.7 (m, 2H), 5.05 (m, 1H), 7.12 – 7.22 (m, 2H), 7.47 (2H, J =
3
7
.32 Hz, 2H). .
2
1
1
.2.24. p-Formylbenzoic acid. Colorless solid; R (EtOAc) 0.25; H NMR (DMSO-d , 500 MHz) δ
f
6
8
.02 (d, J = 8.6 Hz, 2H), 8.13 (d, J = 8.6 Hz, 2H), 10.1 (s, 1H).
1
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Acknowledgments. JNM is thankful to the Department of Science and Technology, India for generous
financial support. KNP gratefully acknowledges the senior research fellowship from CSIR, New Delhi.
1
13
Supplementary Data Available. H and C NMR spectral reproductions for the products of oxidations
1
and NMR spectral reproductions for monitoring of the oxidations of cinnamic acid, p-nitrocinnamic acid,
stilbene, 4,4’-dibromostilbene and chalcone.
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SUPPORTING INFORMATION
Oxidation Cascade with Oxone: Cleavage of Olefins to Carboxylic Acids
Keshaba Nanda Parida and Jarugu Narasimha Moorthy*
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, INDIA
moorthy@iitk.ac.in
Table of Contents
1
1
2
3
4
5
6
7
8
9
1
H NMR spectrum of benzoic acid in CDCl
3
S-3
1
1
1
1
1
1
1
1
1
H NMR spectrum of p-bromobenzoic acid in CDCl3
H NMR spectrum of p-nitrobenzoic acid in CDCl
S-4
3
S-5
H NMR spectrum of o-bromobenzoic acid in CDCl3
S-6
H NMR spectrum of hexane-1,6-dicarboxylic acid in acetone-d
6
S-7
H NMR spectrum of o-nitrobenzoic acid in CDCl
H NMR spectrum of p-cyanobenzoic acid in DMSO-d
H NMR spectrum of p-bromoacetophenone in CDCl
H NMR spectrum of benzene-1,4-dicarboxylic acid in DMSO-d
H NMR spectrum of 1-(4-methoxyphenyl)-2-phenylethane-1,2-dione in
3
S-8
6
S-9
3
S-10
S-11
S-12
6
0
CDCl
3
1
1
1
1
1
1
1
1
1
1
1
2
3
4
5
6
7
8
9
H NMR spectrum of 4-toluic acid in CDCl
3
S-13
S-14
S-15
S-16
S-17
S-18
S-19
S-20
S-21
1
1
1
1
1
1
1
1
H NMR spectrum of m-nitrobenzoic acid in CDCl
3
H NMR spectrum of 1-phenylethane-1,2-diol in CDCl
3
3
C NMR spectrum of 1-phenylethane-1,2-diol in CDCl
3
H NMR spectrum of 1-phenylcyclohexane-1,2-diol in CDCl
3
H NMR spectrum of 1-(4-tolyl)ethane-1,2-diol in CDCl
H NMR spectrum of 4-methoxy benzoic acid in CDCl3
3
3 6
H NMR spectrum of o-phthalic acid in CDCl +DMSO-d
H NMR spectrum of 6-phenyl-6-oxo-hexanoic acid in CDCl
H NMR spectrum of dodecanoic acid in CDCl3
3
1
1
1
1
1
1
2
2
2
2
2
2
0
1
2
3
4
5
S-22
H NMR spectrum of o-toluic acid in CDCl
H NMR spectrum of 1-(p-methoxyphenyl)ethane-1,2-diol in CDCl3
H NMR spectrum of 1-o-tolylethane-1,2-diol in CDCl
H NMR spectrum of p-formylbenzoic acid in DMSO-d
H NMR monitoring of oxidation of 4,4’-dibromostilbene in CD CN-D O
3
S-23
S-24
3
S-25
6
S-26 S1
S-27
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1
1
1
1
26
27
28
29
H NMR monitoring of oxidation of p-nitrocinnamic acid in CD
3
CN-D
2
O
S-28
S-29
S-30
S-31
H NMR monitoring of oxidation of cinnamic acid in CD
H NMR monitoring of oxidation of chalcone in CD CN-D
2
H NMR monitoring of oxidation of stilbene in CD CN-D O
3 2
CN-D O
3
2
O
3
S2

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1
FIGURE S1. H NMR spectrum of benzoic acid in CDCl .
3
S3

ACCEPTED MANUSCRIPT
Br
COOH
1
FIGURE S2. H NMR spectrum of p-bromobenzoic acid in CDCl
3
.
S4

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O N
COOH
2
1
3
FIGURE S3. H NMR spectrum of p-nitrobenzoic acid in CDCl .
S5

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Br
COOH
1
FIGURE S4. H NMR spectrum of o-bromobenzoic acid in CDCl .
3
S6

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COOH
HOOC
1
FIGURE S5. H NMR spectrum of hexane-1,6-dicarboxylic acid in acetone-d .
6
S7

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NO2
COOH
1
FIGURE S6. H NMR spectrum of o-nitrobenzoic acid in CDCl
3
.
S8

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NC
COOH
1
FIGURE S7. H NMR spectrum of p-cyanobenzoic acid in DMSO-d
6
.
S9

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1
3
FIGURE S8. H NMR spectrum of p-bromoacetophenone in CDCl .
S10

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COOH
COOH
1
6
FIGURE S9. H NMR spectrum of benzene-1,4-dicarboxylic acid in DMSO-d .
S11

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OMe
O
O
1
FIGURE S10. H NMR spectrum of 1-(4-methoxyphenyl)-2-phenylethane-1,2-dione in CDCl .
3
S12

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COOH
Me
1
FIGURE S11. H NMR spectrum of 4-toluic acid in CDCl
3
.
S13