Synthesis and study of electrochemical behavior of new 4-ferrocenylbutylamine derivatives

Article abstract of DOI:10.24820/ark.5550190.p010.734

Ferrocene derivatives play important roles in the fields of biological, material and synthetic chemistries. Some 4-ferrocenylbutylamine derivatives were synthesized by the nucleophilic-substitution reactions of 4-bromobutylferrocene with various aliphatic

Full text of DOI:10.24820/ark.5550190.p010.734

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Arkivoc 2018, part vii, 0-0
Synthesis and study of electrochemical behavior of new 4-ferrocenylbutylamine
derivatives
Elmira Payami, Hassan Abbasi, Elaheh S. Yazdchi, Kazem D. Safa, and Reza Teimuri-Mofrad*
Department of Organic and Bio-Organic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
Email: teymouri@tabrizu.ac.ir
Received 08-29-2018
Accepted 11-17-2018
Published on line 12-02-2018
Abstract
Ferrocene derivatives play important roles in the fields of biological, material and synthetic chemistries. Some
4-ferrocenylbutylamine derivatives were synthesized by the nucleophilic-substitution reactions of 4-
bromobutylferrocene with various aliphatic and aromatic secondary amines, and their electrochemical
properties have been investigated. The electrochemical behavior of the synthesized compounds was studied
by cyclic voltammetry. The relationship between the peak currents and the square root of the scan rate
showed that the redox process is diffusion limited.
Keywords: 4-Ferrocenylalkylamine, SN2 reaction, ferrocene, cyclic voltammetry
DOI: https://doi.org/10.24820/ark.5550190.p010.734
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Introduction
Ferrocene or di (η5-cyclopentadienyl) iron (II) was accidentally discovered by Peter L. Pauson and Tom Kealy in
1951 when they attempted the reductive coupling of the Grignard reagent cyclopentadienyl magnesium
bromide in the presence of ferric chloride. The unique sandwich structure of ferrocene was first predicted by
infrared and nuclear magnetic resonance spectroscopies, and later confirmed by X-ray crystallography in
1954.1
Ferrocene derivatives play important roles in the fields of synthetic, material and biological chemistries.
Hence, chemists began to synthesize various ferrocene derivatives and investigated their applications in
various scientific fields.2 The ferrocenyl group plays an important role in electron-transfer reactions, which are
involved in many living systems, and in synthetic chemistry as multi-redox nano systems, especially, in
ferrocenyl polymers,3 dendrimers,4 nanoparticles,5 vectors,6 biosensors,7 biological-redox processes,8
molecular conductors and semiconductors,9 mixed-valence stabilizers,10 catalytic reactions,11 redox
recognition,12 as redox reagents,13 redox catalysts,14 electron-transfer catalysts,15 sensors,16 and green
catalysts.17 Ferrocenyl compounds possess many cytotoxic properties including antitumour effects,18
antimalarial19 and anti-cancer effect in human lung cancer cells.20 Many ferrocenyl derivatives display
interesting cytotoxic, antifungal and DNA-cleaving activities.21
The development of new methods for the formation of carbon–nitrogen bonds is an interesting challenge
in organic synthesis.22 A variety of powerful approaches have been devised, including venerable processes
such as reductive amination23 and Ullmann coupling,24 as well as the more recently developed Buchwald–
Hartwig reaction.25 Despite the utility of such processes, the discovery of novel methods for the formation of
carbon–nitrogen bonds remains an important objective.26,27 Perhaps the most classic reported approach in the
literature for carbon–nitrogen bond formation is the reaction of an amine with an alkyl halide,28,29
a
transformation that continues to play an important role in amine-derivatives synthesis.30 Because this process
generally follows a SN2 pathway, elevated reaction temperatures are typically employed for hindered primary
and secondary electrophiles that are inactivated.22 Due to the interesting electrochemical properties of the
ferrocene moiety, research and investigations of chemical and electrochemical properties of ferrocenyl
organic molecules are important. Cyclic voltammetry (CV) is a very useful electroanalytical technique for the
characterization of the electroactive species. This method provides valuable information regarding the
stabilities of the oxidation states and the rate of electron transfer between the electrode and the analyte.
Applications of cyclic voltammetry have been extended to almost every aspect of chemistry, e.g., the
investigation of biosynthetic reaction pathways, the examination of the ligand effect on the metal complex
potential, and enzymatic catalysis.31, 32
We report, herein, the synthesis and electrochemical properties of some 4-ferrocenylbutylamine
derivatives and obtain information about substituent effects on the electrochemical properties of the
ferrocene moiety using cyclic voltammetry.
Results and Discussion
Due to interesting electronic properties of ferrocene and its derivatives,33-37 we decided to synthesize a series
of novel 4-ferrocenylbutylamine derivatives. Initially, 4-chlorobutylferrocene (2) was synthesized from
ferrocene (1) as shown in Scheme 1.33 Subsequent reduction with NaBH4 solution in diglyme provided the
corresponding 4-chlorobutylferrocene (3).
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Scheme 1. Synthesis of 4-chlorobutylferrocene (3).
Compound 3 was subsequently treated with pyrrolidine in acetonitrile as solvent in reflux conditions. After
24 h, the reaction was not complete; the desired compound was obtained in only 20% yield (Table 1, Entry 6).
To increase the efficiency and improve the reaction conditions, the 4-bromobutylferrocene (4) was
synthesized (Scheme 2).
Scheme 2. Synthesis of 1-(4-butylferrocene)pyrrolidine (6a).
To optimize the reaction conditions for synthesis of 4-ferrocenylbutylamine derivatives, a variety of
solvents and bases were tested, as shown in Table 1. Among the various solvents and bases screened at 80 °C,
the best results were obtained when acetonitrile was used as a solvent and K2CO3 was employed as the base
(Table 1, Entries 2 and 9).
After optimization of the reaction conditions, to explore the scope and generality of the optimal method,
we investigated the synthesis of the corresponding 4-ferrocenylbutylamine derivatives (6a-h) via the N-
alkylation of compound 4 with a variety of aliphatic and aromatic amines (5a-h) (Scheme 3). Saturated
secondary amines such as dipropylamine, dibutylamine, pyrrolidine, morpholine, piperidine and N-methyl
piperazine show good reactivity in SN2 reactions with compound 4; morpholine showed the best reactivity
(Table 2, Entry 3). Aromatic amines undergo the same reaction with compound 4, and the results showed that
aromatic amines such as imidazole and pyrazole afforded the 4-ferrocenylbutylamines in good yield.
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Table 1. Optimization of nucleophilic substitution (SN2) reaction conditions for synthesis of 6a
Entry
1
2
3
4
5
6
7
8
X
Solvent
CH3CN
CH3CN
CH3CN
CH3CN
H2O
EtOH
Toluene
H2O
Base
Na2CO3
K2CO3
Et3N
NaHCO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Temp. (°C)
80
Yield (%)
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cl
43
74
37
29
40
35
38
5
80
80
80
80
reflux
80
80
80
reflux
80
9
10
11
CH3CN
EtOH
Toluene
20
15
10
Scheme 3. Synthesis of 4-ferrocenylbutylamine derivatives (6a-6h).
Subsequently, we synthesized the corresponding ferrocenyl-based ammonium salts from the morpholine
derivative (6c) by treating 6c with MeI to produce the ferrocenyl-based morpholinium iodide salt (6i) in very
good yield (Table 2, Entry 9).
Scheme 4. Synthesis of 4-(4-ferrocenylbutyl)-4-methyl morpholinium iodide (6i) from compound 6c.
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Table 2. Yields of compound (6a-i) under optimal conditionsa
Entry
Product
6a
Yield (%)b
1
2
3
4
5
6
7
8
9
74
82
87
71
73
57
69
78
91
6b
6c
6d
6e
6f
6g
6h
6i
a K2CO3, CH3CN, reflux
b Isolated yield
Cyclic voltammetry
To compare the influence of the substituents on the redox ability of Fe (II), electrochemical studies on the
synthesized ferrocene derivatives (6a-i) were carried out. Cyclic voltammetry (CV) experiments performed in
dry CH3CN/0.01 M LiClO4 solution exhibited quasi-reversible voltammetric behavior for the ferrocenyl group in
these compounds, with ∆Ep = Epa−Epc < 0.07 V at scan rates up to 0.15 V s-1 (Table 3). Cathodic and anodic
peak current ratios measured for the derivatives were in the range 1.07< ipc/ipa < 1.13, and Ep values were
independent of the scan rate.
Table 3. Selected potentials (V) and current (mA) data for 1.0 mM solutions of the 4-ferrocenylbutylamines
(6a-i) in CH3CN/0.1M LiClO4
Entry
Compound
∆Ep
Ipc /Ipa
1.13
1.08
1.11
1.07
1.12
1.08
1.07
1.12
1.10
1
2
3
4
5
6
7
8
9
6a
6b
6c
6d
6e
6f
6g
6h
6i
0.065
0.069
0.067
0.071
0.062
0.069
0.068
0.071
0.062
All of the newly synthesized compounds (6a-6i) exhibited only one pair of well-defined redox peaks in
CH3CN indicating the existence of only one kind of electroactive center in these compounds which correspond
to its ferrocenyl group. A series of voltammograms of the ferrocene compounds in CH3CN/0.100 M LiClO4, at
various scan rates, such as 50, 60, 70, 80, 90, 100, 120 and 150 mVs-1, were also recorded, as shown in Figure
1. It was found that both cathodic- and anodic-peak currents linearly increase with the increasing of scan rate.
The position of the cathodic peak slightly shifted towards the negative potential, and the anodic peak shifted a
little towards the positive direction with increase of scan rate. The plots of the anodic and cathodic currents
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versus the square root of scan rates (v1/2) show a linear relationship. This behavior suggests that the redox
process is diffusion limited (Figure 2).
Figure 1. CV curves of the 1-(4-ferrocenylbutyl)pyrrolidine (6a) in different scan rates.
Figure 2. Linear relationship between the A) cathodic peak current, B) anodic peak current and the square root
of the scan rates.
As indicated in Table 3, electrochemical parameters, such as the position of redox potentials and degree of
reversibility of the electrochemical behavior, are negligibly affected by the presence and type of the amine
functional groups attached to the central ferrocene rings. Therefore, it can be said that nature of the
appending groups does not significantly affect the electrochemical properties of the ferrocene rings.
Conclusions
In summary, we report the synthesis of some 4-ferrocenylbutylamine derivatives in good yields through the
substitution reactions of 4-bromobutylferrocene with various secondary aliphatic and aromatic amines. The
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electrochemical behavior of the synthesized compounds with the increase of scan rate was investigated.
Based on the results, the synthesized 4-ferrocenylbutylamine derivatives showed quasi-reversible single-
electron electroactivity. The relationship between the peak currents and the square root of the scan rate
showed that the electrode processes were diffusion controlled.
Experimental Section
General. Chemicals were either prepared in our laboratory or purchased from Merck, Sigma-Aldrich and
Yantai Suny Chem. International Co., Ltd. Commercial solid reagents were used without further purification.
Liquid reactants were distilled prior to use. Solvents were dried and distilled prior to use according to standard
laboratory practices; water was doubly distilled. THF and diglyme were dried by refluxing under argon over
sodium wire and distilled directly before use.
1
The H NMR and 13C NMR spectra were recorded at room temperature using a Bruker FT- 400 MHz and 100
MHz spectrometer, respectively. CDCl3 was used as solvent and internal standard, and chemical shifts are
presented with delta-values expressed in ppm referenced to CDCl3 peaks at 7.25 (1H NMR) and 78 ppm (13C
NMR), respectively. The FT-IR spectra were recorded on a Bruker-Tensor 270 spectrophotometer as KBr disks
or smears between salt plates. Elemental analyses were carried out with an Elementor Vario EL. III instrument.
Iron analysis was performed using an Analytikjene (novaa 400) Atomic Absorption Spectrophotometer. Cyclic
voltammetry measurements were performed on 1 mM solutions of ferrocene derivatives in dry CH3CN/0.1 M
LiClO4 using potentiostat/galvanostat Autolab (PGASTAT 30) equipped with a standard three-electrode cell. A
2-mm-diameter GC was used as the working electrode. A silver/silver chloride (Ag/AgCl) electrode and a
platinum electrode were used as the reference and counter electrodes, respectively. All potentials in this
study are reported with respect to the Ag/AgCl electrode.
Synthesis of 4-chlorobutylferrocene (3). The procedure for synthesis of 4-chlorobutylferrocene was carried
out according to the reported method.33
Synthesis of 4-bromobutylferrocene (4). The procedure for synthesis of 4-bromobutylferrocene was carried
out according to the reported method.34
General procedure for the synthesis of 4-ferrocenylbutylamine derivatives (6a-6h). 4-bromobutylferrocene
(4) (0.4g, 1.2 mmol), the appropriate amine derivatives (4.7 mmol) and potassium carbonate (0.63g, 5.94
mmol) were dissolved in acetonitrile (25 ml). The mixture was refluxed for 48 hours. After the completion of
the reaction, acetonitrile was evaporated under vacuum, and the cooled residue mixture was diluted with 25
ml of CH2Cl2 and washed with water (3×10 ml). The organic phase was dried over Na2SO4, filtered and the
solvent was removed under atmospheric pressure. The crude products were purified by preparative thin layer
chromatography on silica gel with EtOAc/MeOH (9:1) as eluent. Specific details are described for each of the
compounds.
1-(4-Ferrocenylbutyl)pyrrolidine (6a). From 0.4 g of 4-bromobutylferrocene, 0.25 g of light brown oil viscous
1
oil (6a) was obtained in 67% yield. FT-IR (KBr, cm-1): 3085, 2926, 2855, 1669, 1457, 1360, 1094, 1021, 488. H
NMR (400 MHz, CDCl3): δH 1.52-1.56 (4H, m, -CH2-), 1.84 (4H, m, -CH2-), 2.32-2.36 (2H, t, J 7 Hz CpCH2), 2.52-
2.54 (2H, m, NCH2), 2.64 (4H, br, NCH2), 4.02-4.04 (4H, d, J 6.2 Hz, Cp), 4.08 (5H, s, Cp). 13C NMR (100 MHz,
CDCl3): δC 22.3, 27.2, 28.0, 28.4, (-CH2-), 55.2, 53.0 (NCH2), 66.0, 67.0, 67.4 (Cp), 88.8 (Cipso Cp). Anal. Calc. for:
C18H25FeN (311.25): C, 69.46; H, 8.10; Fe, 17.94; N, 4.50. Found: C, 69.78; H, 7.99; Fe, 17.82; N, 4.41%.
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1-Methyl-4-(ferrocenylbutyl)piperazine (6b). From 0.4 g of 4-bromobutylferrocene, 0.35 g of light brown oil
viscous oil (6b) was obtained in 87% yield. FT-IR (KBr, max, cm-1): 3090, 2933, 2796, 1683, 1455, 1363, 1011,
486; 1H NMR (400 MHz, CDCl3): δH 1.48-1.50 (4H, m, -CH2-), 2.27 (2H, s, -CH3), 2.31-2.35 (4H, q, J 7 Hz, CpCH2),
13
2.44-2.49 (8H, br, NCH2) 4.01-4.02 (4H, d, J 1.35 Hz, Cp), 4.06 (5H, s, Cp). C NMR (100 MHz, CDCl3): δC 25.6,
27.9, 28.3, 57.3 (-CH2-), 44.8 (-CH3), 51.1, 53.8 (CH2N), 65.9, 66.9, 67.3 (Cp), 87.9 (Cipso Cp). Anal. Calc. for:
C19H28FeN2 (340.29): C, 67.06; H, 8.29; Fe, 16.41; N, 8.23. Found: C, 66.83; H, 8.34; Fe, 16.51; N, 8.32%.
1-(4-Ferrocenylbutyl)morpholine (6c). From 0.4 g of 4-bromobutylferrocene, 0.34 g of light brown oil viscous
1
oil (6c) was obtained in 87% yield. FT-IR (KBr, max, cm-1): 2923, 2854, 1665, 1469, 1362, 1057, 490; H NMR
(400 MHz, CDCl3): δH 1.49-1.53 (4H, m, -CH2-), 2.31-2.35 (4H, t, J 6.4 Hz, CpCH2), 2.43 (4H, br, NCH2) 3.70-3.72
(4H, m, OCH2), 4.02-4.04 (4H, d, J 4.96 Hz, Cp), 4.08 (5H, s, Cp); 13C NMR (100 MHz, CDCl3): δC 25.3, 27.8, 28.4 (-
CH2-), 57.8, 52.6 (NCH2), 65.1 (OCH2), 65.8, 66.9, 67.3 (Cp), 87.9 (Cipso Cp); Anal. Calc. for: C18H25FeNO (327.25):
C, 66.07; H, 7.70; Fe, 17.06; N, 4.28. Found: C, 65.92; H, 7.75; Fe, 17.11; N, 4.30%.
1-(4-Ferrocenylbutyl)piperidine (6d). From 0.4 g of 4-bromobutylferrocene, 0.27 g of light brown oil viscous
1
oil (6d) was obtained in 71% yield. FT-IR (KBr, cm-1): 2933, 2859, 1649, 1402, 1366, 1077, 486; H NMR (400
MHz, CDCl3): δH 1.50-1.51 (2H, m, -CH2-), 1.52-1.57 (4H, m, -CH2-), 1.57-1.62 (4H, m, -CH2-), 2.28-2.31 (4H, m,
13
CH2N, CpCH2), 2.38 (4H, br, CH2N), 4.00-4.03 (4H, d, J 1.6 Hz, Cp), 4.06 (5H, s, Cp); C NMR (100 MHz, CDCl3):
δC 23.0, 23.6, 24.6, 27.9, 28.3, (-CH2-), 50.9, 58.1 (NCH2), 65.8, 66.8, 67.2 (Cp), 87.9 (Cipso Cp); Anal. Calc. for:
C19H27FeN (325.28): C, 70.16; H, 8.37; Fe, 17.17; N, 4.31. Found: C, 69.89; H, 8.47; Fe, 17.27; N, 4.37%.
1-(4-Ferrocenylbutyl)imidazole (6e). From 0.4 g of 4-bromobutylferrocene, 0.27 g (73%) of light brown oil
1
viscous oil (6e) was obtained. FT-IR (KBr, cm-1): 2933, 2859, 1506, 1453, 1228, 1105, 1000, 650, 486; H NMR
(400 MHz, CDCl3): δH 1.42-1.50 (2H, m, -CH2-), 1.75-1.79 (2H, m, -CH2-), 2.32-2.36 (2H, t, J 7.5 Hz, CpCH2), 3.89-
3.92 (2H, t, J 6.5 Hz, NCH2), 4.01-4.03 (4H, d, J 9.66 Hz, Cp), 4.06 (5H, s, Cp), 6.98-7.14 (2H, m, Im), 7.49 (1H, s,
Im); 13C NMR (100 MHz, CDCl3): δC 27.0, 28.0, 29.7 (-CH2-), 45.9 (NCH2), 66.1, 66.9, 67.3 (Cp), 87.9 (Cipso Cp),
118.23, 128.78, 136.64 (C-Im); Anal. Calc. for: C17H20FeN2 (308.21): C, 66.25; H, 6.54; Fe, 18.12; N, 9.09. Found:
C, 65.98; H, 6.57; Fe, 18.27; N, 9.18%.
1-(4-Ferrocenylbutyl)pyrazole (6f). From 0.4 g of 4-bromobutylferrocene, 0.21 g (57%) of light brown oil
1
viscous oil (6f) was obtained. FT-IR (KBr, cm-1): 3094, 29.35, 2857, 1610, 1440, 1390, 1000, 486; H NMR (400
MHz): δH 1.44-1.52 (2H, m, -CH2-), 1.86-1.93 (2H, m, -CH2-), 2.32-2.36 (2H, t, J 7.6 Hz, CpCH2), 4.03-4.07 (9H, m,
Cp), 4.11-4.15 (2H, t, NCH2), 6.23, 7.36, 7.56 (3H, br, py). 13C NMR (100 MHz, CDCl3): δC 26.9, 27.9, 29.1, 50.8 (-
CH2-), 66.0, 66.9, 67.3 (Cp), 87.5 (Cipso Cp), 104.1, 127.7, 137.9 (C-py). Anal. Calc. for: C17H20FeN2 (308.21): C,
66.25; H, 6.54; Fe, 18.12; N, 9.09. Found: C, 66.79; H, 6.41; Fe, 17.89; N, 8.91%.
1-(4-Ferrocenylbutyl)dipropylamine (6g). From 0.4 g of 4-bromobutylferrocene, 0.28 g (69%) of light brown
1
oil viscous oil (6g) was obtained. FT-IR (KBr, cm-1): 2926, 2854, 1602, 1410, 1384, 1003; H NMR (400 MHz): δH
0.86-0.89 (3H, t, J 7.3 Hz, CH3), 1.40-1.50 (8H, m, -CH2-), 2.31-2.43 (8H, m, CpCH2, NCH2), 4.02-4.05 (4H, m, Cp),
4.09 (5H, s, Cp). 13C NMR (100 MHz, CDCl3): δC 10.9 (CH3), 19.1, 26.1, 28.0, 28.5 (-CH2-) 55.2, 53.0 (NCH2), 65.9,
66.9, 67.3 (Cp), 88.3 (Cipso Cp). Anal. Calc. for: C20H31FeN (341.32): C, 70.38; H, 9.16; Fe, 16.36; N, 4.10. Found:
C, 70.03; H, 9.29; Fe, 16.51; N, 4.17%.
1-(4-Ferrocenylbutyl)dibutylamine (6h). From 0.4 g of 4-bromobutylferrocene, 0.34 g (78%) of light brown oil
1
viscous oil (6h) was obtained. FT-IR (KBr, cm-1): 3092, 2948, 2863, 1729, 1460, 1372, 1004, 490; H NMR (400
MHz, CDCl3): δH 0.89-0.93 (6H, t, J 7.3 CH3), 1.25-1.34 (4H, m, -CH2-), 1.38-.144 (4H, m, -CH2-), 1.45-1.49 (4H, m,
-CH2-), 2.31-2.34 (2H, t, J 7.5 CpCH2), 2.38-2.41 (6H, m, NCH2), 4.02-4.03 (2H, m, Cp), 4.04-4.05 (2H, d, J 1.59
Hz, Cp), 4.09 (5H, s, Cp). 13C NMR (100 MHz, CDCl3): δC 13.1 (CH3), 19.7, 26.0, 28.0, 28.1, 28.4 (-CH2-), 52.8,
52.9 (NCH2), 65.9, 66.9, 67.3 (Cp), 88.2 (Cipso Cp). Anal. Calc. for: C22H35FeN (369.37): C, 71.54; H, 9.55; Fe,
15.12; N, 3.79. Found: C, 71.74; H, 9.47; Fe, 15.02; N, 3.77%.
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Synthesis of 4-(4-ferrocenylbutyl)-4-methyl morpholinium iodide (6i). 4-(4-ferrocenylbutyl)morpholine (6c)
(0.1 g, 0.31 mmol) and methyliodide (0.13g, 0.94 mmol) were dissolved in acetone (20 ml) and the mixture
was refluxed for 72 hours. After the completion of the reaction, the cooled mixture was diluted with ethyl
acetate and washed with water. The organic phase was dried over Na2SO4, filtered, and the solvent was
removed under atmospheric pressure. The crude product was purified by preparative thin layer
chromatography on silica gel with n-hexane/acetone (1:1) as eluent to give 0.09 g (91%) of a light brown
1
viscous oil (6i). FT-IR (KBr, cm-1): 2923, 2853, 1602, 1412, 1384, 1035, 487. H NMR (400 MHz, DMSO-d6): δH
1.47-1.54 (2H, m, -CH2-), 1.67-1.75 (2H, m, -CH2-), 2.33-2.37 (2H, t, J 7.6 Hz, CpCH2), 3.11 (3H, s, CH3), 3.138-
3.41 (4H, m, OCH2), 3.45-3.48 (2H, m, NCH2), 3.91 (4H, m, NCH2) 4.06-4.12 (9H, m, Cp). 13C NMR (100 MHz,
DMSO-d6): δC 20.7 (CH3), 27.1, 28.3, 46.0 (-CH2-), 58.9, 59.8 (NCH2), 63.5 (OCH2), 66.9, 67.7, 68.3 (Cp), 88.1
(Cipso Cp). Anal. Calc. for: C20H30FeIN (467.22): C, 51.42; H, 6.47; Fe, 11.95; I, 27.16; N, 3.00. Found: C, 50.99; H,
6.54; Fe, 12.12; I, 27.32; N, 3.03%.
Acknowledgements
The authors thank Research Affairs of the University of Tabriz for financial support.
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