Hydrogen Peroxide Oxygenation of Furan-2-carbaldehyde via an Easy, Green Method

Article abstract of DOI:10.1021/acs.jafc.8b06284

Derivatives of 2(5H)-furanone (γ-crotonolactone) are important intermediate synthetic products with a wide range of biological effects that have become widely used in the pharmaceutical industry, medicine, and veterinary medicine, in particular in the prevention and treatment of fish diseases. However, the environmental issue of obtaining these compounds while reducing the negative impact on the surrounding environment remains relevant. This article describes for the first time a method of γ-crotonolactone synthesis that is based on the concept of green chemistry. Synthesis is carried out under mild conditions using nontoxic reagents by furfural oxidation. For the first time, a mixture of hydrogen peroxide and acetic acid was used for the oxidation of furfural in a ratio of 1:0.05. A mixture of organic acids (succinic, maleic, fumaric, formic, and cinnamic acids), obtained as a byproduct in the synthesis of γ-crotonolactone, can be used as a highly effective, ecofriendly organic fertilizer or in a preparation with a stimulating effect.

Full text of DOI:10.1021/acs.jafc.8b06284

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Agricultural and Environmental Chemistry
Hydrogen Peroxide Oxygenation of Furan-2-
carbaldehyde by the Easy Method of Green Chemistry
Viktor Zvarych, Anna Nakonechna, Mykhailo Marchenko, Oleksii Khudyi,
Vira Lubenets, Lidiia Khuda, Olga Kushniryk, and Volodymyr Novikov
J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.8b06284 • Publication Date (Web): 27 Feb 2019
Downloaded from http://pubs.acs.org on March 1, 2019
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1
2
3
Hydrogen Peroxide Oxygenation of Furan-2-carbaldehyde by the Easy Method
of Green Chemistry
4 Viktor Zvarych†, Anna Nakonechna†, Mykhailo Marchenko‡, Oleksii Khudyi‡, Vira
5 Lubenets†, Lidiia Khuda‡, Olga Kushniryk‡ and Volodymyr Novikov†, *
6
7
† Department of Technology of Biologically Active Substances, Pharmacy &
8 Biotechnology, Lviv Polytechnic National University, S. Bandery Str. 12, Lviv,
9 Ukraine
10
‡ Department of Biochemistry and Biotechnology, Yuriy Fedkovych Chernivtsi
11 National University, Kotsyubynsky Str. 2, Chernivtsi, Ukraine
12
*
13
Corresponding author: Volodymyr Novikov, Lviv Polytechnic National
14 University, S. Bandery Str. 12, Lviv, Ukraine, Tel. +380-67-6743067, e-mail:
15 volodymyr.p.novikov@lpnu.ua
16
17 ABSTRACT
18
Derivatives of 2(5H)-furanone (γ-crotonolactone) are important intermediate
19 synthetic products with a wide range of biological effects that have become widely
20 used in the pharmaceutical industry, medicine and veterinary medicine, in particular
21 in the prevention and treatment of fish diseases. However, the environmental issue of
22 obtaining these compounds to reduce the negative impact on the surrounding
23 environment remains relevant. The article describes for the first time the method of γ-
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24 crotonolactone synthesis, which is based on the concept of green chemistry. Synthesis
25 is carried out under mild conditions using non-toxic reagents by furfural oxidation.
26 For the first time, a mixture of hydrogen peroxide and acetic acid for the oxidation of
27 furfural was used in the ratio 1:0.05.
28
A mixture of organic acids (succinic, maleic, fumaric, formic acid and cinnamic
29 acid), obtained as a by-product in the synthesis of γ-crotonolactone, can be used as a
30 highly effective, eco-friendly organic fertilizer or preparation with a stimulating
31 effect.
32
33 Keywords: furan-2-carbaldehyde, 2(5H)-furanone (γ-crotonolactone), green
34 chemisty, hydrogen peroxide, acetic acid.
35
36 INTRODUCTION
37
The use of compounds of the furan series, namely derivatives of 2(5H)-furanone
38 (γ-crotonolactone or 2-butenolide), in synthetic organic chemistry and in the national
39 economy is known for a long time.1,2 Compounds of this class are found in beer,
40 kvass, fermented foods and especially in contaminated feeds exposed to mold.3,4
41 They attract considerable attention as growth regulators of plants,5 substances that
42 inhibit the tumor growth in the organism, as they are inhibitors of cell
43 metamorphosis6 and promoters of the growth of industrial fish cultures.7 2(5H)-
44 Furanones are known as compounds with the antifungal and antibacterial activities.8-
10
45
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46
Under the influence of γ-crotonolactone, the content of thiol groups in the
47 intestinal mucosa is increased due to the increased biosynthetic processes in the gut
48 associated with increased secretion of specific enzymes. The experiments for the
49 determination of the total proteolytic activity of fish intestine, exposed to γ-
50 crotonolactone, demonstrate it very clearly. The total proteolytic activity
51 characterizing the number of enzymes in the intestinal mucosa has increased
52 significantly (by 24%) for the 2nd day and continued to remain at a high level for 3
53 days. At 30th day it grew up to 30%. It is noted that the proteolytic activity of the
54 intestine continues to remain high even after the end of γ-crotonolactone addition to
55 the feed. 2(5H)-Furanone has not a negative effect on the fish body, on the contrary,
56 this drug helps to suppress the growth of pathogenic microflora in the intestine.11,12
57
At the same time, formic, fumaric, maleic, succinic, and cinnamic acids as a
58 product of the furfural oxidation are used in almost all fields of the industrial and
59 food chemistry. Formic acid and its salts are used in the feed industry, textile dyeing
60 and finishing, food additives, grass silage, natural rubber, leather tanning, etc.13
61 Fumaric acid is nontoxic and versatility reagent, that used in the resin industry, green
62 chemistry as an eco-friendly catalyst, and in the food industry as a nutritional additive
63 and acidulant.14 Maleic acid is not so widespread like fumaric acid. Maleic acid is
64 used for the production of maleinate resins, copolymers, and generally as a chemical
65 precursor of fumaric acid and maleic anhydride.15 Moreover, cinnamic acid and its
66 derivatives are known as natural occurring products.16 They were found in all green
67 plants.17 Cinnamic acids are also used in medicinal chemistry as a perspective objects
68 with a different useful spectrum of activities.18
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69
Another promising direction for the use of 2(5H)-furanone is a fish breeding,
70 which is particularly widespread in Central and Eastern Europe, as well as in Asia.
71 Drugs based on 2(5H)-furanone inhibit the development of cyanobacteria, which
72 prevents fish death in the ponds. In particular, there is a positive result in the use of
73 drugs based on γ-crotonolactone and a mixture of the above-mentioned organic acids
74 in the cultivation of fish in natural reservoirs and in recirculating aquaculture
75 systems, which stimulate the development of a natural fodder base in fish-breeding
76 ponds.19 It allows the use of such drugs in the technologies of intensive cultivation of
77 live feeds, in particular, freshwater planktonic crustaceans, such as daphniids. These
78 organisms are widely used both in ornamental aquaculture and in the larviculture of
79 many commercial fish species.20
80
Therefore, the aim of this study was to improve the synthesis of 2(5H)-furanone
81 using non-toxic and environment-friendly hydrogen peroxide oxygenation in the
82 presence of the catalytic amount of acetic acid in water.
83
84 MATERIALS AND METHODS
85
Chemicals. All alalytical grade chemicals were obtained from Sigma-Aldrich
86 and were used without any further purification. Double distilled water was used in
87 this study.
88
89
General Experimental Details
All melting points were determined in open capillary tubes on a Boetius
90 apparatus and are uncorrected. The 1H NMR and 13C NMR spectra were recorded on
91 a Bruker Аvance DRX-500 spectrometer (500 MHz) in DMSO-d6; the chemical
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92 shifts were measured relative to tetramethylsilane. Mass spectra were recorded on an
93 Agilent 1100 Series G1956B LC/MSD SL LCMS system, using electrospray
94 ionization at atmospheric pressure (70 eV). UV spectra were recorded on a
95 “SPECORD M 40” spectrophotometer. IR spectra were recorded on a “SPECORD M
96 80” spectrophotometer in tablets with KBr. Elemental analysis was carried out on a
97 Perkin Elmer 2400 CHN analyzer. The separate determination was carried out using a
98 HPP4001 liquid chromatograph with two serially coupled glass columns (150 × 3.3
99 mm) packed with the Separon SC-X C-18 adsorbent (0.6% acetic acid as the mobile
100 phase, flow rate of 0.3 cm3/min). Monitoring of the reactions was performed by TLC
101 method on “Silufol UV 254” plates.
102
103
Oxidation of furfural
The oxidation reaction with hydrogen peroxide was carried out in a three-necked
104 round bottom glass flask equipped with reflux condenser and mechanical stirrer. The
105 flask was loaded under stirring with the furfural (13.0 mL, 0.160 mol) and water (50
106 mL), and the mixture of H2O2 37.5% (14.7 mL, 0.192 mol) with acetic acid (0.55 mL,
107 0.0096 mol) was slowly added. The reaction mixture was kept under constant stirring
108 for 24 h at a temperature below 60C.
109
After completion of the reaction, water was removed under reduced pressure.
110 The light yellow precipitate of organic acids was filtered off. 2(5H)-Furanone was
111 obtained from the filtrate by vacuum distillation at a 12 mm Hg. The yield of 2(5H)-
112 furanone – 71%.
o
113
2(5H)-Furanone (1): Colorless to slight light yellow liquid, bp. 85–88 C / 12
114 mm Hg. 1H NMR (500 MHz, CDCl3) δ 4.88 (dd, 4J = 2.2 Hz, 3J = 1.7 Hz, 2H, 5-H),
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115 6.10 (dt, 4J = 2.2 Hz, 3J = 5.8 Hz, 1H, 3-H), 7.58 (dt, 4J = 1.7 Hz, 3J = 5.8 Hz, lH, 4-
13
116 H). С NMR (125 MHz, CDCl3,) δ 71.9, 121.1, 152.2, 173.7. IR (KBr, cm-1): 1739,
117 1781 (C=O), 1053-1205 (–C–O–C–). Anal. Calcd. for C4H4O2: C, 57.14; H, 4.80.
118 Found: C, 57.10; H, 4.71. MS (EI) m/z 85.11 [M+H]+.
119
Calculated and found data of succinic, maleic, fumaric, formic and cinnamic
120 acids are confirmed by the literary data.
121
122 RESULTS AND DISCUSSION
123
Catalytic oxidation of furan-2-carbaldehyde (furfural) attracts the attention of
124 many researchers. This aldehyde is derived from vegetable wastes21–23 and is
125 available on the market of chemical reagents. The furfural molecule contains several
126 reaction centers, which implies a wide variety of syntheses. The projects on the
127 oxidation of furfural by molecular oxygen after photoinitiation24 and in conditions of
128 heterogeneous catalysis, including the use of compounds of transitional and noble
129 metals (Сu(OAc)2, Mn(OAc)2, Pd(OAc)2, AgOAc, FeSO4, RuCl3, NiCl2, V2O5,
130 Co(NO3)2, TiO2-ZrO2, Pb(OAc)2 are well known.25–34 It was also reported about the
131 oxidation of furfural with hydrogen peroxide in the presence of a photogenic iron
132 catalyst in the form of a complex [FeCp(C6H5R)]PF6 (R=H, Cl or CH3).35 However,
133 insufficient attention was paid to the homogeneous reactions of furfural with aqueous
134 hydrogen peroxide in the works mentioned above.
135
At the same time, it is known that in the process of furfural oxidation with
136 hydrogen peroxide (Scheme 1), depending on the reaction conditions and the catalyst
137 type, various reactive compounds are formed,36,37 which provide means for the
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138 implementation of various synthetic pathways based on the reactions of furfural with
139 aqueous H2O2 and catalysts.
140
All of the given above methods are multistage and include the use of hard-to-
141 reach and in some cases toxic materials, such as organic solvents (dichloroethane,
142 chloroform), complex salts of heavy and transition metals in the role of catalysts such
143 as Cu2+, Mn2+, Pd2+, Ag+, Ru3+, Ni2+, V5+, Co2+. These catalysts are expensive and
144 have a negative impact on the environment.
145
Therefore, in this work the method of -crotonolactone synthesis was based on
146 the concept of green chemistry, namely the oxidation of furfural was carried out in an
147 aqueous solution without the use of organic solvents, and for the first time an aqueous
148 solution of hydrogen peroxide was used in the role of an oxidizer with a small
149 amount of acetic acid as a promoter of reaction. Oxidation was carried out for 24
150 hours with vigorous stirring and at a temperature below 60C. The process was
151 controlled by UV spectroscopy (residual aldehyde) and TLC (acid formation). The
152 composition of the reaction products was determined by high-performance liquid
153 chromatography (HPLC) (using authentic samples). As a result, the target product γ-
154 crotonolactone (1) was obtained with a yield of ~ 71% and a crystalline precipitate of
155 by-products (2-6) mixture of light yellow color (Scheme 2).
156
Using HPLC it was determined that the crystalline precipitate contains mainly a
157 mixture of organic acids, namely succinic (2), maleic (3), fumaric (4), formic (5),
158 cinnamic (6). This mixture of organic acids can be used in agriculture as non-toxic
159 ecologically pure organic fertilizer.
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160
Thus, using the concept of green chemistry an important intermediate synthetic
161 product with a wide range of biological effects γ-crotonolactone was synthesized by
162 the oxidation of furfural under soft conditions and using non-toxic reagents. For the
163 oxidation of furfural, a mixture of hydrogen peroxide and acetic acid was used in the
164 ratio 1 : 0.05 for the first time. A mixture of organic acids in the role of a by-product,
165 that can be used in the national economy as a highly effective, environmentally
166 friendly organic fertilizer, was obtained.
167
168 Acknowledgments
169 The authors would like to express their gratitude to the Ministry of Education and
170 Science of Ukraine, Scientific Research Project (Project number: 0116U004138) for
171 financial support.
172 Notes
173 The authors declare no competing financial interest.
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286 Figure captions
287 Scheme 1. Oxidation mechanism of furan-2-carbaldehyde.
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288 Scheme 2. Oxidation of furan-2-carbaldehyde with H2O2 and acetic acid in water.
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Scheme 1. Oxidation mechanism of furan-2-carbaldehyde.
O
H+
H
H2O2
H2O
OH
OH
O
O
O
OH
O
O
O
O
H
O
O
1
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Scheme 2. Oxidation of furan-2-carbaldehyde with H2O2 and acetic acid in water.
O
HO
2
3
(5%)
OH
O
O O
(11%)
HO
HO
OH
H2O2, AcOH
H
O
O
O
+
H2O, 60oC, 24 h
O
O
O
4
5
(3%)
(9%)
1
(71%)
OH
OH
O
O
6
(1%)
OH
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TOC graphic
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Oxidation mechanism of furan-2-carbaldehyde
164x25mm (600 x 600 DPI)
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Oxidation of furan-2-carbaldehyde with H O and acetic acid in water
2
2
129x78mm (600 x 600 DPI)
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