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Research Article

Cite This: ACS Sustainable Chem. Eng. 2018, 6, 11380−11385 pubs.acs.org/journal/ascecg

Novel Route to Erucamide: Highly Selective Synthesis from

Acetonitrile at Room Temperature via a Photo-Fenton Process
Navpreet K. Sethi,*,† Hisayoshi Kobayashi,*,‡ Biling Wu,*,§ Renhong Li,*,§ and Jie Fan*,†

Key Lab of Applied Chemistry, Department of Chemistry, Zhejiang University, Hangzhou 310027, China

Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585,
Department of Materials Engineering, College of Material Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, China
S Supporting Information
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ABSTRACT: A new route to the synthesis of a fatty acid N-

derivative, erucamide, was discovered at room temperature
Downloaded via UNIV OF HULL on November 10, 2018 at 13:41:39 (UTC).

with extremely high selectivity from an off-the-shelf reagent,

acetonitrile, through a photo-Fenton process.

KEYWORDS: Erucamide, Room temperature, Acetonitrile, Photo-Fenton process, Highly selective

Fatty acid N-derivatives, i.e., fatty acid nitriles and fatty acid
The irradiation of MeCN and peroxide was carried out in the
amides, are considerably important molecules in the areas of absence and presence of silica support represented as series A
chemistry1−6 as well as biochemistry.7−10 These molecules are and B in Table SI (brief) and Table SII (descriptive). Each
present within living cells11−16 and bear renowned applications irradiation experiment had four sets of reactions with variable
in industry3,4,8−10,17−20 in addition to therapeutics.11,12,21−27 concentration of the reagents as shown in Table SI. The
irradiation for each sample was implemented by a UV lamp
The reported synthetic strategies include pyrolysis of
having a wavelength of 300 nm for a period of 2.5 h at room
biodegradable organic matter4,8,28−42 and ammoniolysis of temperature in the dark. The reactions were continued for
fatty acid precursors,18,43−47 involving extremely high temper- about 2 days (in the absence of radiation) under similar
atures up to 700 °C. However, there is a sole example that has conditions. All the above irradiated samples were extracted by
reported the use of low temperature instead (50 °C using fatty MeOH for a clear indication of the product(s) synthesized
ester).44 In the current work, an innovative method to from these mixtures. Benzonitrile was used as an internal
selectively synthesize a fatty acid N-derivative (erucamide) standard in all these reactions for quantification. Each extracted
has been reported at room temperature. The methodology mixture was analyzed by GC-MS analysis. A part of the total
illustrates the formation of higher homologues from a lower sample volume was expended for this experiment. The details
nitrile (MeCN) by means of C−CN activation followed by C− of the products formed in these irradiation reactions are
H activation initiated by peroxy free radicals. It has been described in Table SII in the Supporting Information.
The results indicated that the presence of silica and the
known that the MeCN molecule is capable of producing free quantity of reagents have significant effect on the formation of
•CN radicals, when irradiated by UV-light.48 However, from erucamide both qualitatively as well as quantitatively (Table
the best of our knowledge there is no report that indicates that SIII). Series A indicated that erucamide is formed as one of the
irradiation of the MeCN molecule could form higher analogues products. However, series B showed that relatively high yields
up to C22 chain length. In this report, we demonstrate the can be formed only when silica is present within the same
synthesis of higher analogues of MeCN by a free radical
mechanism initiated by peroxy free radicals further supported Received: March 20, 2018
by DFT calculations. The products formed were analyzed by Revised: July 29, 2018
GC-MS analysis qualitatively as well as quantitatively. Published: August 3, 2018

© 2018 American Chemical Society 11380 DOI: 10.1021/acssuschemeng.8b01177

ACS Sustainable Chem. Eng. 2018, 6, 11380−11385
ACS Sustainable Chemistry & Engineering Research Article

Figure 1. GC-MS chromatograms showing concentration of erucamide with respect to other products and internal standard in (A) absence of silica
and (B) presence of silica.

reaction. This difference associated with the presence of silica been clearly illustrated with the chromatograms shown in
was clearly confirmed by the increase of percentage yields Figure 1 both for series A and B in Figure 1A,B, respectively.
irrespective of the reagent quantities in series B (I−III). Reaction Mechanism. For elucidation of the reaction
However, the quantity of the reagents has a little influence on mechanism, DFT calculations were conducted. For each
the product yield in series B (except IV), but the selectivity is elementary step, the transition state (TS) was characterized.
majorly affected by them as shown by B-I−B-III. On the other Then, the intrinsic reaction coordinate (IRC) was evaluated in
hand, excessive peroxide tends to diminish the free radical both directions. From the end point of IRC, the usual
reaction as shown by IV. Above all, the best suited conditions optimization run was performed, indicating that the reactants
for this reaction is indicated by series B-III. The latter has and products were seamlessly connected via the TS.
11381 DOI: 10.1021/acssuschemeng.8b01177
ACS Sustainable Chem. Eng. 2018, 6, 11380−11385
ACS Sustainable Chemistry & Engineering Research Article

Figure 2. Structures as predicted by DFT calculations from steps A−D.

Figure 3. In situ C−H activation at the C13 position of the aliphatic nitriles.

According to our previously reported work,48 the hydroxyl the rest of the steps (B−D) are endothermic and are at close
(•OH) radicals formed by the photo-Fenton process react proximity to one another, that is, 43.3, 42.0, and 42.2 kcal
with CH3CN molecules producing •CH2CN radicals by means mol−1, respectively. The formation of the transition state,
of proton abstraction forming •CH2CN radicals, Step A. This however, requires relatively higher energy as described in Table
free radical species, •CH2CN, then react with other molecules SIV. However, the total energy of these reactions is negative
of CH3CN, to form a free •CN radical and a propionitrile indicating that the reactions are spontaneous (Table SIV). The
molecule, Step B. This molecule reacts further with other free structures elucidated from the calculated data are given as
radicals of •CH2CN and hence initiates a chain reaction shown Figure 2 for Steps A−D, respectively. However, IRC (reaction
in Figure 2. pathway) is only shown for Step C, Figure 2, for both reactants
The energy required for Step A, the proton abstraction step, as well as products. In this pathway, the •CH2CN radical
is exothermic (−23.4 kcal mol−1). However, the energies for approaches the central −CH2− carbon in the propionitrile
11382 DOI: 10.1021/acssuschemeng.8b01177
ACS Sustainable Chem. Eng. 2018, 6, 11380−11385
ACS Sustainable Chemistry & Engineering Research Article

molecule for •H abstraction. Once the butanenitrile molecule formed is greater, but at the same time the selectivity of the
is formed, the •CN free radical is released. Since the energy main product (erucamide) is compromised. The latter at 35 °C
difference for the three steps (B−D) is nearly the same, it is shown in Table SVI for erucamide.
indicates that the chain reaction does not require a very high
energy to continue this reaction, and room temperature is
apparently sufficient. The chain propagation of these reactions
This is a first report of highly selective synthesis of a long-
continues until a chain termination step is achieved. chained fatty acid N-derivative, erucamide, discovered via
It is discernible from Steps B−D that there were free •CN irradiation of acetonitrile at room temperature. The reactions
radicals left unreacted in these reactions. It is expected that free showed the potential of generation of higher analogues of
•CN radicals will abstract protons from the medium to form similar derivatives when suitable conditions are employed. The
HCN. Since the latter was never analyzed in any of the data, it range of experiments indicated the potential of the reactions
was expected to have neutralized in the form of CO2 and and their influential ability on selectivity and performance. The
H2O.49 In order to confirm this neutralization reaction, DFT calculations supported the suggested mechanism which is
another supporting experiment of CO2 determination was C−CN bond activation along with in situ C−H activation due
carried out separately, given in the Supporting Information, to peroxy free radicals. This long-chained analogue, erucamide,
Table SVII. has valuable therapeutic properties, and thus, the methodology
The chain propagation for aliphatic nitriles continues until a is useful for both pharmaceutical as well as synthetic laboratory
sufficient chain length (C22, erucamide) is achieved. There- operations.
after, the molecule undergoes C−H activation at the C13
position. There is no direct evidence of C−H activation in
aliphatic nitriles in higher analogues, but there are reported

S Supporting Information
examples that indicate the C−H activation at the terminal The Supporting Information is available free of charge on the
carbon,50 nonterminal carbon,50 and other positions in ACS Publications website at DOI: 10.1021/acssusche-
aliphatic nitriles.51,52 All the reported examples involve the meng.8b01177.
participation of metals. Since there is no metal involvement in
the current reactions, the •OH free radicals are the only Irradiation experiment tables with different products
activation source that are most probably responsible for the formed, selectivity tables with percentage yield, DFT
C−H activation in higher nitriles. There is precedent that C− energy table, experimental of irradiation reactions, NMR
H activation can be achieved by •OH free radicals in aliphatic spectroscopy data for erucamide, and CO2 determi-
aldehydes in the aliphatic region irrespective of the functional nation experiment with quantity by GC (PDF)
Therefore, the proposed mechanism as shown in Figure 3
involves free •OH radicals. These free radicals approach the
Corresponding Authors
C13 carbon for •H abstraction, leading to a free radical *E-mail: nksyork@gmail.com. (N.K.S.)
intermediate, which uses a neighboring •H radical to form a *E-mail: hisa@kit.ac.jp. (H.K.)
double bond thereby releasing a •H radical along with a H2O *E-mail: 960708631@qq.com. (B.W.)
molecule in the medium. The reason for the proton abstraction *E-mail: lirenhong@zstu.edu.cn. (R.L.)
at the C13 position is most probably the stability of the *E-mail: jfan@zju.edu.cn. (J.F.)
intermediate. ORCID
In series B, silica assists the process by increasing the surface
Navpreet K. Sethi: 0000-0003-0243-5940
area, availing the possibility of more coordination sites to the
adhered nitrile molecules, and hence influences the yields. Jie Fan: 0000-0002-8380-6338
Because of the presence of excessive water molecules in the Notes
The authors declare no competing financial interest.

medium, hydrolysis of the higher nitriles is very well-favored;
hence, formation of amides occurs.
Role of Silica. For the study of the role of silica in-depth in ACKNOWLEDGMENTS
such reactions, different experiments were carried out at silicas We would like to thank Dr. Yaqin Liu and Associate Prof.
with different mesh sizes [80−100 (i), 200−300 (ii), and 300− Jiankai Zou from Department of Chemistry Zhejiang
400 (iii)] and at three different temperatures (25, 30, and 35 University, Hangzhou, China, for performing NMR spectros-
°C) (Table SV). The range of temperature selection was not copy and GC-MS spectrometry data collection for our samples.
kept too high as it is a free radical reaction (discussed earlier).
The reaction conditions used were kept as per sample B-III
(standardized procedure). In samples at 25 °C, the long-
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11385 DOI: 10.1021/acssuschemeng.8b01177

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