A scalable production of anisonitrile through organoselenium-catalyzed dehydration of anisaldoxime under solventless conditions

Article abstract of DOI:10.1016/j.apcata.2017.05.007

An organoselenium-catalyzed dehydration reaction of anisaldoxime to produce the useful fine chemical anisonitrile was achieved under solventless conditions without using any dehydrant. Simple PhSe(O)OH could be employed as the recyclable and reusable catalyst without obvious deactivation, and the reaction generated no wastes at all. By an easily operable distillation process, the product could be isolated in high purity, as confirmed by NMR spectroscopic analysis. The reaction was scalable to at least kilogram-scale with excellent carbon mass balance at 99.3%, showing very great potential of the method in industrial-scale production. The mechanism of the reaction was also discussed based on the experimental findings.

Full text of DOI:10.1016/j.apcata.2017.05.007

Applied Catalysis A, General 541 (2017) 107–111
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Applied Catalysis A, General
journal homepage: www.elsevier.com/locate/apcata
Research Paper
A scalable production of anisonitrile through organoselenium-catalyzed
dehydration of anisaldoxime under solventless conditions
⁎
Xiaobi Jing, Tingting Wang, Yuanhua Ding, Lei Yu
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, China
A R T I C L E I N F O
A B S T R A C T
Keywords:
Anisonitrile
Organoselenium catalysis
Green chemistry
Dehydration
An organoselenium-catalyzed dehydration reaction of anisaldoxime to produce the useful fine chemical
anisonitrile was achieved under solventless conditions without using any dehydrant. Simple PhSe(O)OH could
be employed as the recyclable and reusable catalyst without obvious deactivation, and the reaction generated no
wastes at all. By an easily operable distillation process, the product could be isolated in high purity, as confirmed
by NMR spectroscopic analysis. The reaction was scalable to at least kilogram-scale with excellent carbon mass
balance at 99.3%, showing very great potential of the method in industrial-scale production. The mechanism of
the reaction was also discussed based on the experimental findings.
Fine chemical
1. Introduction
attention [24–45] for the applications in green synthesis. Compared
with conventionally employed transition-metal catalysts, organosele-
Anisonitrile is an important fine chemical that has been widely
nium catalysts are environment-safe because selenium is a metaboliz-
able element in organism [46]. Selenium is much cheaper than noble
metals [47]. Many of the organoselenium-catalyzed reactions were
performed with clean procedures [35–45] and the organoselenium
catalysts were so robust that could be recycled and reused for many
times without significant deactivation. We are interested in green
synthetic methods and have paid much attention on organoselenium
applied as the intermediate in perfume industry, pharmaceutical
industry and organic synthesis [1–3]. It was conventionally accessed
by aerobic oxidative reaction of (4-methoxyphenyl)methanol with
ammonium formate [4], palladium-assisted cyanation of 1-iodo-4-
methoxybenzene with tert-butyl isocyanide [5], oxidation of (4-meth-
oxyphenyl)methanamine [6], and so on. Although the above methods
provided comprehensive accesses to nitriles, from the viewpoint of
industrial application, the dehydration of anisaldoxime might be a more
practical method for the synthesis of anisonitrile owing to the easily
accessible and low cost starting materials as well as the high efficiency
of the process [7–15]. However, most of the reported aldoxime
dehydration reactions required organic solvent, metal or non-metal
chemical dehydrant or the environment-unfriendly transition-metal
catalyst, which inevitably generated large amount of solid wastes
catalysis, which afforded
a series of waste-free transformations
[36–43]. It has been found that catalyzed by PhSe(O)OH, the dehydra-
tion of aldoximes in MeCN solvent provided an efficient access to
nitriles [41,42]. Recently, as a part of our project to develop novel
antiseptics, we successfully applied this technology onto anisaldoxime
dehydration to produce the useful fine chemical anisonitrile through
very convenient and practical processes free of solvent. As anisaldoxime
was an electron-enriched substrate that facilitated the nucleophilic
attack onto the catalytic selenium species, the reaction generated
anisonitrile in excellent yield and a simple distillation afforded the
product with high purity, as confirmed by NMR spectroscopic analysis.
The residue could be directly reused as catalyst in the next round of
reaction without deactivation. The reaction was successfully magnified
to kilogram-scale to produce anisonitrile in 96.0% yield with excellent
carbon mass balance at 99.3%, showing very good reliability of the
method in industrial production. Herein, we wish to report our findings.
[
16–18]. Dehydration reactions of aldoximes in vapor phase are
methods with good atom economy, but require high energy consump-
tions [19,20]. These defects greatly retained their applications in
industrial production. Thus, developing alternative methods for prac-
tical production of anisonitrile is not only desirable but also timely in
the field.
On the other hand, organoselenium chemistry is a unique subject
with great application potential for the bioactivities of the related
compounds that have been widely employed in organic synthesis,
biochemistry, medicinal chemistry and even material science
[
21–23]. Recently, organoselenium catalysis began to draw much
⁎
Corresponding author.
E-mail address: yulei@yzu.edu.cn (L. Yu).
http://dx.doi.org/10.1016/j.apcata.2017.05.007
Received 15 February 2017; Received in revised form 8 May 2017; Accepted 9 May 2017
Available online 11 May 2017
0926-860X/ © 2017 Elsevier B.V. All rights reserved.

X. Jing et al.
Applied Catalysis A, General 541 (2017) 107–111
2. Experimental
2.1. General methods
Reagents were purchased from merchants with their purities more
than 98% and were directly used as received. Melting points were
measured by a WRS-2A digital instrument. IR spectrum of anisonitrile
1
13
was measured on a Bruker Tensor 27 Infrared spectrometer. H and
C
NMR spectra were recorded on a Bruker Avance 600 instrument
1
13
(
600 MHz for H and 150 MHz for
CDCl as the solvent and Me Si as the internal standard. Chemical
shifts for H NMR were referred to the internal Me Si (0 ppm) and J-
C NMR spectroscopy) using
3
4
1
4
values were shown in Hz. Mass spectrum of anisonitrile was measured
on a Shimadzu GCMS-QP2010 Ultra spectrometer (EI). Gas chromato-
graphy (GC) for the analysis of the reaction products employed a
capillary DB1701 column and a FID. The oven temperature was
programmed at 70–260 °C (heating rate = 30 °C/min). Elemental ana-
lysis was performed on an Elementar Vario EL cube instrument.
Fig. 2. The 1H NMR spectrum of the product 2 distilled from the reaction using the 5th
recycled catalyst.
2.2. General procedure for the dehydration of anisicaldoxime 1a to produce
anisonitrile 2a in 1 mmol-scale
To a reaction tube, 1 mmol of 1a, organoselenium catalyst and
solvent (for details please see Tables 1–3) were added. The tube was
heated at 65 °C in open air for 24 h. The mixture was then sent to GC
analysis by using 20 mg of biphenyl as the internal standard.
2.3. Procedure for the dehydration of anisicaldoxime 1a to prepare
anisonitrile 2a in 100 mmol-scale and the catalyst recycling
To a 50 mL round bottom flask, 15.1 g of 1a (100 mmol) and 0.95 g
of PhSe(O)OH (5 mmol) were added. The flask was then heated at 65 °C
in oil bath for 24 h and cooled to room temperature. A simplified
distillation device (vide infra, Fig. 1) was then equipped to isolate the
product 2a by distillation at 160–162 °C (oil bath temperature),
−
0.092 MPa. Only one fraction was collected as the product without
cutting and its purity was identified by NMR spectroscopic analysis
vide infra, Figs. 2 and 3). 0.85 g of 30 w/w% H was added into the
(
2 2
O
residue to reactivate the catalyst. A fresh portion of 15.1 g of 1a was
then added to restart the next round of reaction. Other nitriles 2b–g
could be prepared smoothly in 100 mmol-scale through similar
methods.
Fig. 3. The 13C NMR spectrum of the product 2 distilled from the reaction using the 5th
recycled catalyst.
that the carbon content in the residue was 26.86%, indicating that
45.2 g of carbon was contained in it. The carbon mass balance of the
reaction should be (609.8 + 45.2)/(635.6 + 23.9) = 99.3%.
2.4. Procedure for the kilogram-scale production of anisonitrile 2a
To a 5 L reaction kettle, 1 kg of 1a (6.61 mol, contained 635.6 g of
carbon) and 62.8 g (5 mol%, contained 23.9 g of carbon) of PhSe(O)OH
were added. The mixture was then heated at 65 °C for 24 h and cooled
to room temperature. Distillation under reduced pressure
2.5. Procedures for kinetics studies
10 mmol of 1a, 0.5 mmol of PhSe(O)OH and 5 mmol of anisole
(internal standard) were heated at 65 °C in open air. The reaction was
monitored by GC to get the yield of generated anisonitrile at different
reaction times. After 24 h, the liquid containing the product and the
internal standard was removed by distillation at 160 °C under reduced
(
157–160 °C/-0.099 MPa) led to 0.845 kg of 2a (96.0% yield, contained
609.8 g of carbon) and 168.3 g of residue. Elemental analysis indicated
2 2
pressure. 0.085 g of 30 w/w% H O was added into the residue to
reactivate the catalytic selenium species. After adding 10 mmol of 1a
and 5 mmol of anisole (internal standard) into the residue, the next
round of reaction was restarted. For experiments described in Fig. 4
(
vide infra), curves 5–6, the residue was directly reused as catalyst
without reactivating by H
2 2
O .
2.6. Characterization data of the products
2.6.1. Anisonitrile 2a
Solid, m.p. 56.2–57.0 °C (lit. 55–57 °C); IR (KBr): 2942, 2842, 2218,
−1
1
Fig. 1. (a) Photo of the simplified distillation device; (b) The device in application.
1606, 1510, 1460, 1305, 1259, 1176, 1023, 830 cm
;
H NMR
108

X. Jing et al.
Applied Catalysis A, General 541 (2017) 107–111
Fig. 4. Kinetics studies of the catalyst-recycled reactions.
(
400 MHz, CDCl
J = 8.4 Hz, 2H), 3.86 (s, 3H); C NMR (100 MHz, CDCl
62.9, 134.0, 119.2, 114.8, 103.9, 55.6; MS (EI, 70 eV): m/z (%) 134
3
, TMS, ppm): δ 7.60 (d, J = 8.4 Hz, 2H), 6.96 (d,
Table 1
Solvent screenings [a].
1
3
3
, ppm): δ
1
[
entry
solvent
2a/%[b]
3a/%[c]
+
+ 1] (9), 133 (100) [M+], 103 (60). Known compound [34].
M
1
2
3
4
5
6
7
8
9
MeCN
MeOH
EtOH
t-BuOH
DMF
DMSO
THF
1,4-dioxane
petroleum ether
H O
2
84.4
99.6
84.4
62.8
93.8
99.1
84.5
93.3
92.5
93.4
94.3
12.9
0
8.9
15.3
6.1
0
12.8
6.0
7.3
6.2
5.8
2
.6.2. Benzonitrile 2b
Oil; H NMR (600 MHz, CDCl
1
3
): δ 7.60–7.55 (m, 3H), 7.43 (t,
J = 8.4 Hz, 2H); Known compound [42].
2.6.3. 4-Methylbenzonitrile 2c
1
Oil; H NMR (600 MHz, CDCl
3
): δ 7.50 (d, J = 8.4 Hz, 2H), 7.25 (d,
J = 7.8 Hz, 2H), 2.40 (s, 3H); Known compound [42].
10
1
1
no solvent
2
.6.4. 4-Fluorobenzonitrile 2d
Oil; H NMR (600 MHz, CDCl
1
[
a] 1 mmol of 1a and 2 mL solvent were employed; [b] GC yields of 2a based on 1a; [c]
3
): δ 7.68−7.65 (m, 2H), 7.18–7.14
GC yields of 3a based on 1a.
(
m, 2H); Known compound [42].
.6.5. 4-Chlorobenzonitrile 2e
high yields in many polar or non-polar solvents (Table 1, entries 5–9).
The reaction in water could produce 2a in excellent yield as well
(
2
1
Solid, m.p. 93.6–94.2 °C (lit. 93–95 °C); H NMR (600 MHz, CDCl
3
):
Table 1, entry 10). More importantly, the reaction could be performed
δ 7.58–7.56 (m, 2H), 7.44–7.42 (m, 2H); Known compound [42].
without solvent to synthesize anisonitrile 2a in 94.3% yield (Table 1,
entry 11).
2
.6.6. Naphthalene-1-carbonitrile 2f
1
Oil; H NMR (600 MHz, CDCl
3
): δ 8.20 (d, J = 8.4 Hz, 1H), 8.04 (d,
J = 8.4 Hz, 1H), 7.90–7.86 (m, 2H), 7.67–7.65 (m, 1H), 7.61–7.58 (m,
3.2. Screenings of the catalysts
1
2
7
H), 7.49 (t, J = 7.8 Hz, 1H); Known compound [42].
As shown above, the PhSe(O)OH-catalyzed dehydration of anisal-
.6.7. Picolinonitrile 2 g
doxime 1a could produce anisonitrile 2a in excellent yields in most
solvents (Table 1). Considering the low cost, safe reaction conditions
and high production capacity for industrial application, the solvent-free
reaction should be the preferable protocol (Table 1, entry 11). Further
catalyst screenings were then performed (Table 2), but it was found that
the cheap and simple PhSe(O)OH should be the best catalyst among a
series of candidates (Table 2, entries 1 vs. 2–6). The electron-enriched
aryl selenious acid obviously had very poor catalytic activity for the
1
Oil; H NMR (600 MHz, CDCl
3
): δ 8.69 (d, J = 3.6 Hz, 1H),
.85–7.83 (m, 1H), 7.68 (d, J = 7.8 Hz, 1H), 7.53–7.51 (m, 1H);
Known compound [41].
3
. Results and Discussions
3
.1. Screenings of the solvents
The reaction was initially performed by heating anisaldoxime 1a
Table 2
with PhSe(O)OH (5 mol%) in MeCN solvent in open air at 65 °C. After
4 h, the mixture was cooled to room temperature (ca. 20 °C) and sent
Catalyst screenings [a].
2
entry
1
Se cat.
2a/%[b]
3a/%[c]
to GC analysis. The desired dehydration product 2a was found to be
produced in 84.4% GC yield, while the deoximation by-product 3a was
also detected (Table 1, entry 1). It was found that MeOH was a good
solvent for the transformation, affording 2a in almost quantitative yield
without generating 3a (Table 1, entry 2). Other alcohol solvents, such
as EtOH and t-BuOH, were not as good as MeOH, resulting in the
decreased product yield and the increased generation of the by-product
PhSe(O)OH
4-MeC H Se(O)OH
6 4
94.3
50.3
88.6
89.9
41.8
22.2
5.8
10.3
7.7
8.5
8.9
8.1
[d]
2
3
4
5
6
4-FC
3-FC
3-ClC Se(O)OH
6
H
H
4
Se(O)OH
Se(O)OH
6
4
[
[
d]
d]
6
H
4
3,5-(CF ) C H Se(O)OH
3 2 6 3
3
a (Table 1, entries 3–4 vs. 2). Through the organoselenium-catalyzed
[a] 1 mmol of 1a was employed; [b] GC yields of 2a based on 1a; [c] GC yields of 3a
based on 1a; [d] Reactions not completed.
dehydration reaction, anisaldoxime 1a could be converted into 2a in
109

X. Jing et al.
Applied Catalysis A, General 541 (2017) 107–111
Table 3
Table 5
Catalyst loading investigations [a].
Test of the generality of this protocol.
entry
catalyst loading/%[b]
2a/%[c]
3a/%[d]
entry
R
T1 (°C) [a]
T2 (°C) [b]
2: yield/% [c]
1
2
5
4
3
2
1
0.5
0.5
94.3
84.5
61.6
58.3
53.5
45.3
49.4
5.8
5.6
5.5
4.7
0
1
2
3
4
5
6
7
4-MeOC
Ph
6
H
5
65
65
65
85
75
65
65
160–162
60–62
65–68
110–113
70–73
163–165
72–74
2a: 91
2b: 84 (78)
2c: 74
2d: 73
2e: 66 (64)
2f: 82
[
[
[
[
[
e]
3
4
5
6
7
4-MeC
4-FC
4-ClC
1-C10
2-C
6
H
5
e]
6
H
5
e]
6
H
5
e]
0
3.8
H
7
e,f]
5
H
4
N
2 g: 69
[
a] 1 mmol of 1a was employed; [b] Catalyst loadings based on 1a; [c] GC yields of 2a
[a] Reaction temperature. [b] Reduced pressure distillation temperature. [c] Gross yields
of the isolated products outside the parentheses; nitrile yields after deduction of the
aldehydes from H NMR inside the parentheses.
based on 1a; [d] GC yields of 3a based on 1a; [e] Reactions not completed; [f] The
reaction time was extended to 48 h.
1
reaction, giving 2a in only 50.3% yield, while the by-product 3a was
generated in 10.3% yield and the reaction did not complete in 24 h, as
monitored by GC analysis (Table 2, entry 2). Electron-deficient 4-
reactions. As shown in Fig. 4, the reaction proceeded quickly and the
product yield reached 80% in the first 1 h reaction (curve 1). The
product yield slowly increased to 93% after 24 h. Using recycled
catalyst, the product yields were not reduced and underwent similar
procedures like the first round of reaction (Fig. 4, curves 2–4). It was
FC
ClC
the reaction (Table 2, entries 3–4 vs. 5–6).
H
6 4
Se(O)OH and 3-FC
H
6 4
Se(O)OH were good catalysts, but 3-
6
H
4
Se(O)OH and 3,5-(CF
3 2 6 3
) C H Se(O)OH were unfavourable for
2 2
notable that addition of catalytic amount of H O was the key for
catalyst recycling and reusing, otherwise the catalyst was deactivated,
resulting in the gradually decreased product yields in the 2nd and 3rd
rounds of reaction (Fig. 4, curves 5–6).
3.3. Catalyst loading investigations
More efforts were tried to reduce the catalyst loading of the reaction
(
Table 3). Unfortunately, the reduced catalyst loadings resulted in
3
.6. Substrate scope extension
decreased product yields (Table 3, entries 1 vs. 2–6). The reaction could
not complete within 24 h when less than 4 mol% of catalyst loadings
were employed (Table 3, entries 3-6). Extending the reaction time to
4
(
Generality of this protocol was also tested (Table 5). A series of
aldoximes 1 were treated under the optimized conditions and the
related products 2 were isolated through reduced pressure distillation
8 h could hardly improve the reaction with reduced catalyst loading
Table 3, entry 7). In summary, heating 1a with 5 mol% of PhSe(O)OH
with the simplified distillation device depicted in Fig. 1. The distilled
as catalyst but without solvent was finally screened out to be the
optimized reaction conditions.
products were directly sent to 1H NMR spectroscopic analysis to
confirm their purities (see supplementary information). Besides anisal-
doxime 1a (Table 5, entry 1), benzaldoxime 1b led to benzonitrile 2b in
7
benzaldehyde were also observed in its H NMR spectrum. Dehydration
of the electron-enriched substrate 4-methylbenzaldoxime 1c afforded
the pure product 4-methylbenzonitrile 2c in 74% yield (Table 5, entry
3
.4. Catalyst recycle & reuse in scaled-up reactions
8% yield (Table 5, entry 2), while traces of the deoximation product
1
A 100 mol-scale-magnified experiment under the optimized reaction
conditions were then performed and the product 2a could be distilled
under reduced pressure by using the simplified distillation device, as
shown in Fig. 1. The residue, which contained a series of low valent
3
). The electron-deficient aldoxime 1d and 1e were also tested, but
because of their high melting points, the reactions should be performed
at higher temperature, affording 2d and 2e in moderate yields (Table 5,
entries 4–5). By using this dehydration protocol, the bulky but electron-
enriched substrate 1-naphthaldehydoxime 1f could also produce the
related product 2f in good yield (Table 5, entry 6). It was notable that
the heterocycle-containing substrate 1 g was also preferable for the
reaction, giving 2 g in 69% yield (Table 5, entry 7).
2 2 2
organoselenium compounds such as (PhSe) , was re-oxidized by H O
to regenerate the catalytic PhSe(O)OH and then directly reused after
adding another portion of 1a. Table 4 shows that the catalyst could be
reused for at least 5 times without deactivation. The distilled product
2
a of the 5th round reaction was directly sent to NMR spectroscopic
1
analysis without any additional purification procedure. H NMR and
1
3
C NMR spectra both indicated that the purity of the product was very
high (Figs. 2 and 3), although fraction cutting was inoperable in the
experimental procedures by using the simplified distillation device
3.7. Reaction mechanism discussion
(
Fig. 1). Moreover, further scaled-up dehydration reaction of 1 kg of 1a
Based on the above experimental results as well as literatures [41], a
successfully produced 0.845 kg of 2a (in 96.0% yield) with carbon mass
balance at 99.3%, showing very good reliability of this method for
possible industrial applications in future.
plausible mechanism was given below. Nucleophilic addition of the pre-
catalyst PhSe(O)OH to anisaldoxime 1a initially generated the inter-
mediate 4 (Scheme 1, eqn. 1), which decomposed into the by-product
3
a and the organoselenium species 5 (Scheme 1, eqn. 2). Further
3
.5. Kinetics studies
decomposition of 5 afforded PhSeOH (Scheme 1, eqn. 3) [41], which
was the catalytic species in anisaldoxime dehydration (Scheme 1).
Dehydration of PhSeOH furnished the highly activated species PhSeO-
SePh (Scheme 1). Condensation of 1a with PhSeOSePh gave the
intermediate 6, which rearranged into the intermediate 7. The selen-
oxide syn-elimination of 7 led to the product 2a and regenerated the
catalytic species PhSeOH [48]. As PhSeOH species was highly activated
To get detailed information of the procedures, kinetics studies were
carried out by comparisons of the results of a series of 10 mmol-scale
Table 4
Catalyst recycle & reuse [a].
Recycle NO.
0 [b]
1
2
3
4
5
2 2 2
and might be reduced into the stable species (PhSe) , addition of H O
was necessary to reactivate the recycled catalyst before next round of
reaction (Fig. 4). Since nucleophilic attack of aldoximes to PhSeOSePh
was the key step during the processes, the electron-enriched anisaldox-
ime 1a as substrate led to higher nitrile yield than other simple or
2
2
weight/g
yield/% [c]
12.1
91.0
12.7
95.5
12.3
92.5
13.2
99.2
13.1
98.5
13.2
99.2
[
a]100 mmol reaction scale; [b] First use of the catalyst; [c] Isolated yields of 2.
110

X. Jing et al.
Applied Catalysis A, General 541 (2017) 107–111
online version, at http://dx.doi.org/10.1016/j.apcata.2017.05.007.
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Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
111