A Two-Step Oxidative Cleavage of 1,2-Diol Fatty Esters into Acids or Nitriles by a Dehydrogenation–Oxidative Cleavage Sequence

Article abstract of DOI:10.1002/cssc.201801640

Dehydrogenative oxidation of vicinal alcohols catalyzed by a commercially 64 wt.% Ni/SiO₂ catalyst leads to the formation of α-hydroxyketone. This first step was developed without additional solvent according to two protocols: “under vacuum” or “with an olefin scavenger”. The synthesis of ketols was carried out with good conversions and selectivities. The recyclability of the supported nickel was also studied. Acyloin was then cleaved with oxidative reagent “formic acid/hydrogen peroxide”, which is cheap and can be used on a large scale for industrial oxidation processes. The global yield of this sequential system was up to 80 % to pelargonic acid and azelaic acid monomethyl ester without intermediate purification. By treating the acyloin intermediate with hydroxylamine, nitriles were obtained with a good selectivity.

Full text of DOI:10.1002/cssc.201801640

Accepted Article
Title: A two-step oxidative cleavage of 1,2 diol fatty esters into acids or
nitriles via a dehydrogenation-oxidative cleavage sequence
Authors: Boris Guicheret, Yann Bertholo, Philippe Blach, Yann Raoul,
Estelle Metay, and Marc Lemaire
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.201801640
Link to VoR: http://dx.doi.org/10.1002/cssc.201801640
A Journal of
www.chemsuschem.org

10.1002/cssc.201801640
ChemSusChem
FULL PAPER
A two-step oxidative cleavage of 1,2 diol fatty esters into acids or
nitriles via a dehydrogenation-oxidative cleavage sequence
Boris Guicheret,[a] Yann Bertholo,[a] Philippe Blach,[b] Yann Raoul,[b] Estelle Métay*,[a] Marc Lemaire[a]*
Dedication ((optional))
Abstract: The dehydrogenative oxidation of vicinal alcohols
catalysed by a commercially 64w%Ni/SiO2 catalyst leads to the
formation of α-hydroxyketone. This first step was developed without
additional solvent according to two protocols: “under vacuum” or “with
an olefin scavenger”. The synthesis of ketols was carried out with
good conversions and selectivities. The recyclability of the supported
nickel was also studied. Acyloin was then cleaved with oxidative
reagent “formic acid-hydrogen peroxide” mixture, cheap and used in
large scale for oxidation industrial process. The global yield of this
Figure 1. Classical pathways for the synthesis of azelaic and pelargonic acids.
sequential system was up to 80% to pelargonic acid and azelaic acid
mono methyl ester without intermediate purification. By treating the
acyloin intermediate with hydroxylamine, nitriles were obtained with a
good selectivity.
ACO).5 Currently, the use of toxic ozone and explosive
intermediate is in balance with the efficiency of the process in term
of productivity and atom economy. From a general point of view,
two main strategies can be considered to synthesize azelaic and
pelargonic acids from oleic acid (figure 1).3 Considering the direct
oxidative cleavage (route A) of the carbon-carbon double bond,
ozonolysis is probably the most efficient way to produce the
desired acids. Alternatives were developed, as for example the
Introduction
In recent years, attractive tools were developed to convert
biomass to consumer products. Among the abundant renewable
feedstock, oils are notably converted into fatty esters or acids
which are modified for lubricant, solvent or plasticizer
applications.1 Another part is dedicated to the production of
biodiesel from the methanolysis of vegetable oils.2 The portion of
biodiesel into diesel is ordered by the European directives which
are at the moment fixed at 7%. These part could be reduced with
keeping a similar production, thus the valorisation of these
derivatives constitutes a challenging research program. One
alternative may concern the modification of the C-C double bond
by an oxidative cleavage to acid building blocks.3 From oleic
derivatives, such transformation allows the formation of azelaic
(AA) and pelargonic acids (PA). The main oxidative
transformation of oleic acid (OA) to AA and PA is carried out by
ozonolysis.4 It was also noticed that treatment of the ozonide
intermediate with hydroxylamine hydrochloride provides a mixture
of acids and nitriles (nonanenitrile PN and 8-cyanooctanoic acid
7
use of stoichiometric oxidant (nitric acid6 or KMnO4 ) but these
reagents can damage the material by corrosion and generate a
large amount of salts. Catalysts, such as osmium tetroxide8 or
ruthenium tetroxide9 associated with sodium periodate were also
efficient for the acid formation. Other systems, further to the
studies of Ishii10 and Venturello11, were developed using
hydrogen peroxide associated with homogeneous metal as
rhenium,12 ruthenium,13 iron14 or ammonium/polyoxometalate.15
In the latter case, the polyperoxometalates used generally contain
tungstic acid as active metal oxide. These systems were able to
cleave a carbon-carbon double bond with an excess of hydrogen
peroxide (5 eq). The polyoxometalate-H2O2 olefin cleavage
mechanism supposes several intermediates including aldehydes
(perhydrolysis of epoxide) or alpha hydroxyketone and diketone
by successive oxidation of the diol.11 An efficient system
(polyoxometale-H2O2) leads to azelaic acid derivatives and
pelargonic acid with 80% yield. The weak point of these conditions
concerns the recycling of the catalytic system, but some recent
results seem promising.16 Two Heterogeneous catalyst systems
in the presence of hydrogen peroxide have also been reported
recently by Do, one with tungsten oxide nanoparticules and the
other one with molybdenum oxide.17 The indirect oxidative
cleavage (route B) was also studied. Kockritz has reported an
efficient Au/Al2O3-O2 system in basic conditions to cleave 9,10-
[a]
[b]
Dr. Boris Guicheret, Yann Bertholo, Dr. Estelle Métay, Prof. Marc
Lemaire
ICBMS-UMR 5246 – Université Lyon 1 – CNRS – INSA – ESCPE
Bâtiment Lederer – 69622 Villeurbanne Tel : 04 72 44 85 07
E-mail: estelle.metay@univ-lyon1.fr
Dr. Philippe Blach, Dr. Yann Raoul
Oleon, Avril Group
Rue les Rives de l'Oise, 60280 Compiègne
dihydroxystearic acid (DHSA) to PA and AA in 90% yield.18
company have related a homogeneous cobalt-air19 system able
A
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
to produce 80% yield of PA and AA from DHSA. Our group has
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801640
ChemSusChem
FULL PAPER
also reported the oxidation of DHSA by bleach without added
metal.20 A mechanistic study concerning the oxidative cleavage of
diols mentioned that α-hydroxyketone and diketone compounds
are key intermediates notably with a gold catalyst.21 Another
group recently employed a combination of Pt/C and V2O5 to
cleave cyclohexanediol and proposed also the corresponding
ketol as intermediate.22 However, the access of such compounds
was poorly described in the literature. One reference reports the
use of KMnO4 in dilute and pH controlled conditions which
modified directly OA to the desired acyloin function.23
Epoxystearate was also converted to ketol in DMSO in the
presence of catalytic BF3-Etherate.24 Recently, we have
developed a procedure for the dehydrogenation of diols into
acyloins using Ru/C.25 The access to α-hydroxyketone is
important as this motif could be converted into aldehydes by a
retro-acyloin reaction catalysed by a thiazolium catalyst.26
Table 1. Evaluation of nickel and copper catalysts.
Conv. of 1[b]
(%)
Sel. 1a[b]
(%)
Sel. 1b-1c
(%)
Entry
Catalyst
1
2
3
Sponge copper
Sponge nickel
64w%Ni/SiO2
45
84
80
77
-
95
99
10-7
12-7
[a] Reaction conditions: 100 mL Schlenk flask fitted with a condenser, 6
mmol of 1. [b] Determined by GC and H-NMR.
Then the catalyst was dried using isopropanol and vacuum. The
residual catalyst powder was weighted and the corresponding
mass of the starting material was introduced with the ratio 3: 1
respectively diol: catalyst. The reactor was heated to 175 °C
under argon then connected to vacuum at 10mbar. After four
hours reaction, 1 was partially converted into the desired KA with
a good selectivity using copper sponge (Table 1, entry 1).
Unfortunately, the appearance of the catalyst was modified at this
temperature as orange copper aggregates were observed in the
crude mixture. The nickel catalysts (Table 1, entry 2-3) have
displayed a higher efficiency compared to copper as both nickel
catalysts allowed to reach high conversions in 4 hours, 95% and
99% respectively for sponge nickel and nickel on silica. The
selectivity for 1a reached 80% and approximately 10% of diketone
were also identified. Similar results were obtained with both nickel
catalysts. The reaction time was then optimized with
64%wNi/SiO2. The first objective was to determine when the
diketone co-product was formed. Surprisingly, when the reaction
was stopped after 1 hour only 3% conversion was observed by
GC and after four hours reaction, the result was the same as
before (table 1, entry 3).
In this report, we describe a two-step procedure dealing first with
a dehydrogenation to prepare a ketol followed by an oxidation to
synthesise carboxylic acids from diols or a treatment with
hydroxylamine hydrochloride to obtain nonanenitrile PN and
methyl 8-cyanooctanoate MCO. We have demonstrated that
vicinal alcohols and more precisely 9,10-dihydrostearic acid mono
methyl ester could be selectively dehydrogenated to α-
hydroxyketone by Ru/C. Regarding the price of ruthenium, the
use of other metals was considered.
Figure 2. Consecutive oxidative cleavage of DHSE strategy.
Results and Discussion
To our knowledge, the transformation of diols to ketols catalysed
by a low price heterogeneous metal was only described for the
synthesis of dihydroxyketone (DHA) in gas phase.27 In addition,
the dehydrogenation of secondary and primary alcohols
respectively to ketones and aldehydes has known a large interest
from the last ten years. Cu/Al2O3,28 Ni/Al2O3,29 Ag/Al2O3,30 Raney
Nickel31 and La-Cu/MgAlO32 are efficient system to convert 2-
octanol to 2-octanone. To shift the equilibrium, styrene was added
in some cases, as a hydrogen scavenger.31
Table 2. Determination of the activation time of the catalyst.
Activation
time (min)b
Conv. of 1[c]
Sel. 1a[c]
(%)
Sel. 1b-1c[c]
Entry
(%)
%
1
2
3
4
No
10
15
30
3
98
96
97
96
-
31
86
93
1-0
1-1
1-1
For this study, the 9,10-dihydroxystearic acid mono-methyl ester
DHSE was used as a model benchmark to carry out the
dehydrogenation step. The mono-dehydrogenation of DHSE
using nickel catalyst was explored. At the beginning, nickel and
copper sponge were compared to 64w%Ni/SiO2. Experiments
were accomplished in 100 mL schlenk. As nickel and copper
sponge are in suspension in water, they were washed 8 times with
MilliQ water and the pH was adjusted to neutral.
[a] Reaction conditions: 100 mL Schlenk flask fitted with a condenser, 6
mmol of 1. [b] Activation: H2 balloon in a schlenk containing DHSE, catalyst
at 175°C. Reaction time = activation time+30 min under vacuum (10 mbar).
[c] Determined by GC and 1H-NMR.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801640
ChemSusChem
FULL PAPER
A larger quantity (10 mol%) leads to the same result but the time
was decreased to one hour. With larger quantities of nickel, the
selectivity stays high (96%) (Table 3, entry 4-5) and good
conversions were observed. The elimination of hydrogen under
vacuum is limited to high boiling point starting material, as a
consequence, we explored the introduction of an olefin as
hydrogen scavenger and carried out the transformation in a
closed reactor. 1-Decene in reason of its boiling point was
evaluated as hydrogen scavenger. The activation of the catalyst
under hydrogen was accomplished for 20 min before the
introduction of 1-decene. With a low quantity of hydrogen
scavenger (Table 4, entry 2), the conversion was not completed
but the reaction was selective (96%) for 1a. With sub-
stoichiometric quantity of decene 0.8-0.9-1 eq. (table 4, entry 3-4-
5), the conversions were similar for the third (70%). If more olefins
were added, no reaction was observed. 1H-NMR analysis
revealed the absence of terminal olefin in the crude. More
precisely, isomerisation of the double bond occurred in this case,
inhibiting the hydrogen scavenger as the reduction is more difficult.
1-decene was then introduced with a syringe pump for one hour
(table 4, entry 7). The conversion of DHSE was complete after 20
min, with 94% selectivity for ketol.
Table 3. Influence of the quantity of the catalyst.
Conv. of 1[c] Sel. 1a[c] Sel. 1b-1c[c]
Entry
64w%Ni/SiO2 mol%
(%)
(%)
%
Traces
Traces
Traces
2-1
1[b]
2[b]
3
4
5
2.5
5
10
20
35
33
77
74
87
93
94
95
92
96
97
1-1
[a] Reaction conditions: 100 mL Schlenk flask fitted with a condenser, 6
mmol of 1. Activation: H2 balloon in a schlenk containing DHSE, catalyst at
175°C. Reaction time = activation time+1h under vacuum (10 mbar). [b] 2h
under vacuum. [c] Determined by GC and 1H-NMR.
The catalyst activation occurs during the process. To clarify this
point, the reaction mixture was set up under hydrogen gas during
a fixed time. After this activation time, H2 was continuously
removed under vacuum and the crude stirred for 30 min at 175°C.
10 min was too short to reach high conversion (Table 2, entry 2).
In fact, 31% DHSE 1 was converted to ketol (96% sel.) and
diketone 1b (traces). No monoketone 1c was observed.
A longer activation time (Table 2, entry 3-4) allowed to obtain
more than 85% conversion with the same selectivity in favour of
the desired product 1a. Finally, the best result was obtained after
30 min under hydrogen, but the vacuum is necessary at this point
as only 10% of ketol were measured before pumping.
Figure 3. Dehydrogenation of 20g of DHSE using syringe pump 1-decene
introduction.
The required quantity of catalyst was then evaluated. With 2.5 and
5 mol% (Table 3, entries 1-2), the duration of the reaction was
longer giving respectively 33 and 77% conversion of DHSE with
94% selectivity for 1b.
The reaction was carried out from 20 g of starting material (figure
3) and allowed the production of 18.2g of ketol with 95% purity
after a fast distillation of decane. On 100 g scale, the preparation
of acyloin from DHSE was carried out in a steel autoclave to
produce 87g of KA with 90% purity yield after distillation of decane
and crystallisation in pentane. 4% diketone 1b, 2%
monoketone1c and 4% DHSE were also identified.
Table 4. Optimization of 1-decene equivalences.
The influence of the temperature rapidly demonstrated that 175°C
is a good compromise between conversion and selectivity. More
precisely, at 160°C a low conversion (20%) was observed. At
higher temperatures, 180 and 185°C, the conversion of 1 was
close to 80% and the selectivity for 1a 90%, but monoketone 1c
resulting of diol dehydration was also formed.
1-decene
eq.
Conv.of 1[b]
Sel. 1a[b]
(%)
88
96
94
94
92
81
94
Sel. 1b-1c[b]
%
Entries
(%)
34
59
71
70
70
33
99
5
1
2
3
4
5
6
7
8
No
0.5
0.8
0.9
1
1.1
1.1
1.2
6-3
1-0
3-0
3-0
3-1
6-3
1-1
20-20
40
[a] Reaction conditions: 100 mL Schlenk flask fitted with a condenser, 6
mmol of 1. Activation: H2 balloon in closed schlenk containing DHSE,
catalyst at 175°C. 1-Decene was added with a syringe pump. Reaction time
= activation time + 2 hours in closed schlenk. [b] Determined by GC and 1H-
NMR.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801640
ChemSusChem
FULL PAPER
Graph 1: Recycling of Nickel silica(Reaction conditions: 100 mL
Table 5. Dehydrogenation of varied vicinal alcohols
Schlenk flask fitted with a condenser, 6 mmol of 1. Cat. 190
mg. Activation (20min): H2 balloon in closed schlenk
containing DHSE, catalyst at 175°C. 1.1 eq. of 1-decene
introduced after activation time Reaction during 1 hour with a
syringe pump. Conv. and Sel. Determined by GC and 1H-NMR.)
Entry
Protocol
Conv
. (%)
Selectivity –
(isolated yield%)
a
b
4
4
c
1
-
100
80
60
40
20
0
20
16
12
8
90-
(80)
92-
A
B
93
97
1
2
(90)
88-
(57)
A
88
6
3
4
A
B
87
96
88
90-
(70)
6
3
3
Trac
es
0
3
run 1 run 2 run 3 run 4 run 5
Conv. DHSE 1 (%)
Diketone 1b (%)
Ketol 1a (%)
4
92-
(75)
Monoketone 1c (%)
A
B
82
10
2
2
The recyclability of nickel on silica was later studied. The previous
conditions developed, with the introduction of olefin with a syringe
pump, were repeated five times with the same catalyst. As nickel
catalyst are sensitive to air, between each recycling tests, the
catalyst was always kept with solvent, then dried in the schlenk
and activated under H2 before each run. The first run was stop
before 1 hour due to a heating system failure. The conversion of
DHSE was 87% and 85% yield of KA were measured (Graph 1,
run 1). From run 2 to 5, conversion of DHSE were higher than
97% in favour of 90% yields of ketol product. The formation of 1b
and 1c was below 5% yield after each recycling test.
5
6
-
-
-
A
B
25
28
60
64
-
-
20
18
7
8
A
99
99
A or B
1-2
[a] Reaction conditions: Method A: 100 mL Schlenk flask fitted with a
condenser, 6 mmol of diols. Activation (20 min): H2 balloon in closed schlenk
containing DHSE and catalyst at 175°C, Reaction time =activation time+1h
under vacuum (10 mbar vacuum strategy). Method B: diol 6 mmol, 1-decene
1.1 eq filled by syringe pump in one hour in closed schlenk (Olefin strategy).
Conversion and selectivity determined by GC and 1H-NMR. Isolated yield
after flash chromatography.
The retained conditions under a reduced pressure (protocol A) or
in the presence of a hydrogen scavenger (protocol B) were
applied on other substrates in order to evaluate the method. Diols
were dehydrogenated according to both protocols, the results are
detailed in the following table. Initially, diols from fatty acids were
introduced under these dehydrogenation conditions. The diol
diester 2 (Table 5, entry 2), 80% purity, was converted at 96% into
2a (90%) by heating under a reduced pressure (method A). The
protocol (B) using 1-decene allowed 90% conversion of
dihydroxyerucate 3 derived from erucic acid with 96% selectivity
for ketol function 3a (table 5, entry 3) in 70% isolated yield. The
similar polarity of the ketol 3a and the diketone 3b is responsible
of the difference between conversion and isolated yield. Di-
hydroxycycododecane 4 was also converted under the vacuum
protocol and 75% of 2-hydroxycyclododecanone 4a were isolated
(Table 5, entry 4). Unexpectedly, cyclohexanediol has shown a
different reactivity (entry 5 table 5). Dihydroxycyclohexane was
not converted selectively to ketol. A large amount of catechol was
also detected by 1H-NMR. 1,2-octane diol was also poorly
reactive and 15% of 1-hydroxy-2-octanone and 5% of 2-octanone
were measured by gas chromatography.
However the dehydrogenation of secondary alcohols under
vacuum in the presence of a nickel catalyst was very efficient
(table 5 entry 7). This result is in agreement with other study
dealing with the alcohol dehydrogenation with Raney nickel.
Nevertheless, Protocol A and B were not efficient to convert
primary alcohol, octanol into octanal (table 5 entry 8). Another
challenge was dedicated to the evaluation of the reactivity of
hydroxylated triglyceride (TGH).
The reaction conditions were modified by the introduction of
dodecane to decrease the viscosity of the medium. Although the
complexity of the H-NMR 75-80% conversion of vicinal alcohol
and 55-60% ketol TGHD function formation were determinated.
(H-NMR analysis available in supporting information)
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801640
ChemSusChem
FULL PAPER
Figure 4: Formation of ketol from hydroxylated triglyceride
Table 6. Effect of formic acid quantity[a]
Selectivity (%)[b]
Formic
acid eq.
Conv.[b]
(%)
KA
entry
PA
30
30
94
92
AAM-(AA)
30-(nd)
30-(nd)
82-(4)
With this efficient tool in hand, the next part of this study was
devoted to the cleavage of ketol into carboxylic acid. This
transformation can be accomplished with oxidant in stoichiometric
quantities generating a large amount of salts.33 From an atom
economy point of view, oxygen is the best oxidant. In several
studies, the use of vanadium catalyst is reported with good
selectivities for the cleavage to acids or ester.34 Vanadium
supported on heterogeneous acids (Nafion, argils) allowed the
recovery of the metal.35 Under an oxygen pressure, the cleavage
of ketol occurred without catalyst, but in this case, side-reactions
were in competition with the selective formation of acid.36
Vanadium lixiviation were also mentioned which explained a low
metal recovery and a low turnover number. Hydrogen peroxide
was used with methyltrioxorhenium to cleave ketols.37 H2O2-KOH
was efficient stoichiometric oxidant to react with complex
molecules.38
1[c]
2[c]
3
2.5
5
10
15
95
95
10
20
4[d]
82
[a] Reaction conditions: KA (2g, 6mmol), 30w%H2O2 (2.2g, 21 mmol, 3.5 eq.
introduced by syringe pump for 1 hour at 30°C), HCOOH (entry 1, 0.7g, 15
mmol, 2.5 eq.); (entry 2, 1.4g, 30 mmol, 5 eq.), (entry 3, 2.8g, 60 mmol, 10
eq.), (entry 4, 5.6g, 120 mmol, 20 eq.); reaction carried out in 25 mL three
necked flask. [b] Determined by external eicosan gas chromatography
calibration. [c] Two phases appear after complete addition of H2O2 [d] Conv.
and sel. determinate after 2 hours reaction time.
An apparition of two liquid phases during H2O2 dropwise addition
can explain this result. The same phenomenon was observed with
5 eq (table 6, entry 2). A larger quantity of formic acid (20 eq.) was
also efficient after a shorter reaction time (2 hours) since
conversion was similar to the reaction with 10 eq. after 4 hours
reaction. In order to understand the role of this excess of formic
acid, an additional experiment was accomplished with 5 eq. of
For this study, oxygen was not selected to perform the
cleavage but the efficiency of peracids was considered and more
precisely the association of hydrogen peroxide and formic acid.
Performic acid was commonly used for epoxide preparation in
large scale, but also as co-oxidant associated with transition
metal.12,39,40 The first reaction was accomplished using 10
equivalents of formic acid from 2 g of ketol and 3.5 equivalents of
H2O2 (Figure 5).
formic acid in the presence of
2
mol% of TBAHS
(tetrabutylammonium hydrogensulfate) which can act as a phase
transfer agent. In these conditions, the conversion after 4 hours
reached 75% with the selectivity in pelargonic and azelaic acid
derivatives at 95% and 94% respectively.
Figure 5. Oxidation of KA to acid in performic acid medium.
Ketols can also be transformed by the Beckmann fragmentation
of α-hydroxy oximes into nitrile and aldehyde.41,42 This
transformation proceed in the presence of hydroxylamine. In
addition in these conditions, aldehydes are converted into
nitriles.43 As a consequence, KA was mixed with 2.2 mol of
hydroxylamine hydrochloride per mol of KA in methanol allowing
the solubilisation of salts. These conditions were efficient since
47% of PN and 40% of MCO was obtained by GC. The methylated
PA and AAM were also detected in 4 and 2% respectively.
This oxidant treatment allowed 95% conversion of Ketol KA and
the formation of 90% of pelargonic acid was identified by GC with
an internal standard calibration. Only 78% of azelaic acid mono
methyl ester AAM were detected. The lower quantity of azelaic
derivative prompted us to change the extracted solvent
substituting ethyl acetate by MTBE (Methyl tert-butyl ether)
previously employed by Kockritz.21b This modification allowed us
to recover additional 4% of azelaic acid AA. In these conditions
the reaction medium has a monophasic appearance which could
be due to the ability of formic acid to solubilise fatty KA in water.
The possibility to decrease the quantity of formic acid was then
evaluated (Table 6). With 2.5 eq. of formic acid a low conversion
was noticed (Table 6, entry 1).
Scheme 1. Formation of nitrile from KA.
The nature of the hydroxylamine is essential for the cleavage into
nitrile since only the corresponding oxime of the KA is observed
when the reaction was carried out with an aqueous solution of
hydroxylamine. In order to observe the Beckmann fragmentation
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801640
ChemSusChem
FULL PAPER
[1]
[2]
[3]
C. Zhang, T. F. Garrison, S. A. Madbouly and M. R. Kessler, Prog. Polym.
Sci., 2017, 71, 91–14.
the presence of an acidic source is required as for example
trifluoromethanesulfonic acid.44
G. Baskar and R. Aiswarya, Renew. Sustain. Energy Rev., 2016, 57,
496–504.
A. E. Kerenkan, F. Béland and T.-O. Do, Catal. Sci. Technol., 2016, 6,
971–987; A. Köckritz and A. Martin, Eur. J. Lipid Sci. Technol., 2011, 113,
83–91.
Conclusions
[4]
R. G. Ackman, M. E. Retsoof, L. R. Gallay and F. A. Vandenheuvel, Can.
J. Chem., 1961, 39, 1956–1963; A. C. Brown, C. G. Goebel, H. F.
Oehlschlaeger, R; P. Rolfes. Method of making azelaic acid. Patent
US2813113. November 12, 1957.
In conclusion, we have developed a two-step procedure for the
oxidative cleavage of diols into carboxylic acids or nitriles. The
first step can be performed according to two strategies. Both
require the use of a heterogeneous nickel catalyst which could be
recycled. The first one supposes a connection with vacuum and
the second one needs an addition of a hydrogen scavenger, 1-
decene. These procedures were mainly applied to fatty acid
derivatives with success in order to obtain various
hydroxyketones. The reactivity of these chemicals was also
evaluated to reach carboxylic acids or nitriles in simple conditions.
[5]
[6]
G. Yu. Ishmuratov, M. P. Yakovleva, L. P. Botsman, Yu. V. Legostaeva,
I. S. Nazarov, and D. V. Baidimirov Russ. J. Org. Chem., 2015, 51, 610–
614.
E. K. Ellingboe. Nitric acid oxidation of oleic and other fatty acids. Patent
US2203680, june 11, 1940.
[7]
[8]
I. Garti and E. Avni, J. Am. Oil Chem. Soc., 1981, 58, 840–841.
B. R. Travis, R. S. Narayan and B. Borhan, J. Am. Chem. Soc., 2002,
124, 3824–3825.
[9]
S. Rup, F. Zimmermann, E. Meux, M. Schneider, M. Sindt and N. Oget,
Ultrason. Sonochem., 2009, 16, 266–272.
Experimental Section
[10] Y. Ishii, K. Yamawaki, T. Ura, H. Yamada, T. Yoshida and M. Ogawa, J.
Org. Chem., 1988, 53, 3587–3593.
[11] E. Antonelli, R. D’Aloisio, M. Gambaro, T. Fiorani and C. Venturello, J.
Org. Chem., 1998, 63, 7190–7206.
General procedure of dehydrogenation under vacuum: A schlenk,
100mL, equipped with condenser, and close with septum was purged 3
times with argon. DHSE, 2g, (6 mmol), 192 mg, 35 mol% of 64wt%Ni/SiO2
were introduced in the schlenk reactor. Atmosphere was purged by argon
then hydrogen. The reaction was heated to 175 °C under hydrogen
(balloon) during 15 min at 800 rpm (catalyst activation time). Schlenk tube
was connected to the pump and pressure was controlled at 10 mbar. After
1 hour, the reaction was cooled down to room temperature and argon was
introduced in the schlenk. The crude was diluted by 25 mL of ethyl acetate.
Catalyst was filtered through celite and ethyl acetate was concentrated.
The crude (1.90 g), was purified by silica column chromatography to afford
1.6 g (yield: 80%) of desired ketol compound (eluent: DCM/EtOAc =
100:0~98:2).
[12] M. Rüsch, G. Klaas, P. Bavaj and S. Warwel, Lipid Fett, 1995, 97, 359–
367.
[13] A. Behr, N. Tenhumberg and A. Wintzer, RSC Adv., 2012, 3, 172–180.
[14] P. Spannring, V. Yazerski, P. C. A. Bruijnincx, B. M. Weckhuysen and R.
J. M. KleinꢀGebbink, Chem. – Eur. J., 2013, 19, 15012–15018.
[15] A. Haimov, H. Cohen and R. Neumann, J. Am. Chem. Soc., 2004, 126,
11762–11763; A. Godard, P. D. Caro, S. Thiebaud-Roux, E. Vedrenne
and Z. Mouloungui, J. Am. Oil Chem. Soc., 2013, 90, 133–140; T. B.
Khlebnikova, Z. P. Pai, L. A. Fedoseeva and Y. V. Mattsat, React. Kinet.
Catal. Lett., 2009, 98, 9–17.
[16] L. C. de la Garza, K. D. O. Vigier, G. Chatel and A. Moores, Green Chem.,
2017, 19, 2855–2862.
[17] A. S. Ello, A. Enferadi‑Kerenkan, A. Trokourey, T.‑O. Do J. Am. Oil
Chem. Soc. 2017 94, 1451–1461; A. Enferadi-Kerenkan, A. Serge Ello,
T.-O. Do Ind. Eng. Chem. Res. 2017, 56, 10639−10647.
[19] A. Kulik, A. Janz, M.-M. Pohl, A. Martin and A. Köckritz, Eur. J. Lipid Sci.
Technol., 2012, 114, 1327–1332.
General procedure of dehydrogenation using 1-octene as hydrogen
scavenger: A schlenk, 100 mL, equipped with condenser, and close with
septum was purged 3 times with argon. DHSE, 2 g, (6 mmol), 192 mg, 35
mol% of 64wt%Ni/SiO2 were introduced in the schlenk reactor. Atmosphere
was purged again with argon and finally with hydrogen. The reaction was
heated to 175 °C under hydrogen (balloon) during 15 min at 800 rpm
(catalyst activation time). Thereafter, hydrogen atmosphere was replaced
by argon. 924 mg of 1-decene (99%), 1.1 eq., was introduced dropwise by
a syringe pump for 1 hour. After complete addition of 1-decene the reaction
was kept stirring for 15 min. The reaction was cooled, and argon was
introduced in the schlenk reactor. The crude was diluted by 25 mL of ethyl
acetate. Nickel catalyst was filtered through celite and organic layers were
concentrated. Decane is removed by fast distillation (60 °C: 0.5 mbar). The
crude product 1.98 g, containing more than 90% of desired ketol
compound was kept.
[19] A. Bieser, G. Borsotti, F. Digioia, A. Ferrari, A. Pirocco, Continuous
process of oxidative cleavage of vegetable oils. Patent WO2011/080296.
July 7, 2011.
[20] M. Lemaire, A. Favre-Reguillon, B. Paquit, S. Claude, Y. Raoul, Method
for preparation of carboxylic acids by oxidative cleavage of a vicinal diol.
Patent WO2011107721. September 9, 2011.
[21] a) A. Kulik, A. Martin, M.-M. Pohl, C. Fischer and A. Köckritz, Green
Chem., 2014, 16, 1799–1806; b) A. Kulik, A. Janz, M.-M. Pohl, A. Martin
and A. Köckritz Eur. J. Lipid Sci. Technol. 2012, 114, 1327–1332.
[22] N. Obara, S. Hirasawa, M. Tamura, Y. Nakagawa, K. Tomishige
ChemCatChem 2016, 8, 1732-1738.
[23] J. E. Coleman, C. Ricciuti and D. Swern, J. Am. Chem. Soc., 1956, 78,
5342–5345.
Acknowledgements
[24] E. Brousse and D. Lefort, C. R. Acad. Sci., 1965, 261 (groupe8), 1990–
1991.
[25] Duc Vu, B. Guicheret, N. Duguet, E. Métay and M. Lemaire, Green
Chem., 2017, 19, 3390–3399.
The authors thank the French National Agency for financial
support through a Ph.D. grant to B.G. (ANR-13-CDII-0001-
COUPOX).
[26] E. Deruer, N. Duguet and M. Lemaire, ChemSusChem, 2015, 8, 2481–
2486.
[27] G. M. Lari, C. Mondelli and J. Pérez-Ramırez, ACS Catal., 2015, 5,
́
Keywords: Dehydrogenation • diols • hydroxyketones • Nickel •
1453–1461.
[28] F. Zaccheria, N. Ravasio, R. Psaro and A. Fusi, Chem. Commun., 2005,
253–255.
Nitriles
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801640
ChemSusChem
FULL PAPER
[29] K. Shimizu, K. Kon, K. Shimura and S. S. M. A. Hakim, J. Catal., 2013,
300, 242–250.
J. Mol. Catal. Chem., 2004, 212, 171–182. M. Vennat, P. Herson, J.-M.
Brégeault and G. B. Shul’pin, Eur. J. Inorg. Chem., 2003, 908–917.
[36] E. Rozhko, K. Raabova, F. Macchia, A. Malmusi, P. Righi, P. Accorinti,
S. Alini, P. Babini, G. Cerrato, M. Manzoli and F. Cavani, ChemCatChem,
2013, 5, 1998–2008.
[30] T. Mitsudome, Y. Mikami, H. Funai, T. Mizugaki, K. Jitsukawa and K.
Kaneda, Angew. Chem. Int. Ed Engl., 2008, 47, 138–141; K. Shimizu, K.
Sugino, K. Sawabe and A. Satsuma, Chem. – Eur. J., 2009, 15, 2341–
2351.
[37] S. L. Jain, V. B. Sharma and B. Sain, Synth. Commun., 2003, 33, 3875–
3878.
[31] M. E. Krafft and B. Zorc, J. Org. Chem., 1986, 51, 5482–5484.
[32] M. Zhang, Y. Zhao, Q. Liu, L. Yang, G. Fan and F. Li, Dalton Trans., 2016,
45, 1093–1102.
[38] K. C. Nicolaou, D. L. F. Gray and J. Tae, J. Am. Chem. Soc., 2004, 126,
613–627.
[33] P. W. Clutterbuck and F. Reuter, J. Chem. Soc. Resumed, 1935, 1467–
1469; R. Floresca, M. Kurihara, D. S. Watt and A. Demir, J. Org. Chem.,
1993, 58, 2196–2200; J. Yan, B. R. Travis and B. Borhan, J. Org. Chem.,
2004, 69, 9299–9302.
[39] A. Köckritz, M. Blumenstein and A. Martin, Eur. J. Lipid Sci. Technol.,
2010, 112, 58–63.
[40] D. Swern, Chem. Rev., 1949, 45, 1–68.
[41] D. Miljkovic, J. Petrovic, M. Stajic, M. Miljkovic J. Org. Chem. 1973, 38,
3585-3588.
[34] M. Kirihara, S. Takizawa and T. Momose, J. Chem. Soc. [Perkin 1], 1998,
7–8.
[42] R. E. Gawley, Organic Reactions, 1988, 35, 0-75.
[43] S. T. Chill, R. C. Mebane Synth. Commun., 2009, 39, 3601-3606.
[44] H. Fujioka, W. Miyazaki, T. Yamanaka, H. Yamamoto, Y. Kita,
Tetrahedron Lett. 1990, 31, 5951-5954.
[35] M. Dakkach, A. Atlamsani and S. Sebti, Comptes Rendus Chim., 2012,
15, 482–492; L. El Aakel, F. Launay, J.-M. Brégeault and A. Atlamsani,
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801640
ChemSusChem
FULL PAPER
Entry for the Table of Contents (Please choose one layout)
Layout 1:
FULL PAPER
Text for Table of Contents
Author(s), Corresponding Author(s)*
Page No. – Page No.
Title
((Insert TOC Graphic here: max.
width: 5.5 cm; max. height: 5.0 cm))
Layout 2:
FULL PAPER
Author(s), Corresponding Author(s)*
Page No. – Page No.
Title
Nitriles or carboxylic acids can be obtained from diols via an efficient two-step
sequence including a dehydrogenation.
This article is protected by copyright. All rights reserved.