Synthesis and properties of pentane amino derivatives

Article abstract of DOI:10.1134/S1070363210120091

Synthesis of pentane amino derivatives by the reaction of the corresponding amines with 1-bromopentanes of n-and iso-structure by environmentally safe methods in water medium was carried out. The structure of the compounds obtained was confirmed by elemental analysis, IR, ¹H and ¹³C NMR spectroscopy. The products synthesized were tested as reagents for the suppression of growth of the sulfate-reducing bacteria and as the anticorrosive substances. It was found that they are effective bactericides for the sulfate-reducing bacteria and exhibit high anticorrosive properties. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070363210120091

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 12, pp. 2455–2459. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.G. Talybov, E.G. Mamedbeili, V.M. Abbasov, K.A. Kochetkov, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80,
No. 12, pp. 1993–1997.
Synthesis and Properties of Pentane Amino Derivatives
A. G. Talybova, E. G. Mamedbeilia, V. M. Abbasova, and K. A. Kochetkovb
a Institute of Petrochemical Processes, Azerbaijan National Academy of Sciences,
ul. Hojaly 30, Baku, 1025 Azerbaijan
e-mail: eldar_mamedbeyli@mail.ru
b Nesmeyanov Institute of the Organoelemental Compounds, Russian Academy of Sciences, Moscow, Russia
Received January 12, 2010
Abstract―Synthesis of pentane amino derivatives by the reaction of the corresponding amines with 1-
bromopentanes of n- and iso-structure by environmentally safe methods in water medium was carried out. The
structure of the compounds obtained was confirmed by elemental analysis, IR, 1H and 13C NMR spectroscopy.
The products synthesized were tested as reagents for the suppression of growth of the sulfate-reducing bacteria
and as the anticorrosive substances. It was found that they are effective bactericides for the sulfate-reducing
bacteria and exhibit high anticorrosive properties.
DOI: 10.1134/S1070363210120091
The amino group containing compounds are widely
used as starting substances for the preparation of many
valuable organic and inorganic products [1]. Sub-
stituted diamines are used in the synthesis of aza-
crown ethers [2], specialty polymers [3], stable car-
bynes [4], silylenes [5], and some other stable ions.
They are used also for the preparation of complexes
with metals like magnesium, copper, silver, palladium(II),
and platinum(II). The latter complexes are studied as
model compounds bound with DNA and exhibiting
antitumor properties [6].
mentally safe processes, the so-called “green” chemistry,
which proceeds in water medium is desirable. Using
water provides some advantages like the simplicity of
the performance and high efficiency in many organic
reactions with the participation of water-soluble sub-
strates, reagents, and renewable materials without the
additional treatment [9]. Nowadays special attention of
researchers is attracted to the synthesis of alkylamines
using the environmentally safe methods, among them
the reactions in the water medium. In connection with
that the synthesis of new representatives of the above-
mentioned amines on the basis of the available raw
materials and improved procedures is quite actual.
The organic synthesis in water medium is
especially valuable because no toxic organic solvents,
in particular, chlorinated hydrocarbons, contaminating
the environment are used. The modern approach to
development of engineering, chemistry, and chemical
technology requires creating new environmentally safe
and resource-saving chemical processes. Significant
progress was achieved in performing chemical
processes in the medium of “green” solvents such as
ionic liquids or water [8]. As known, ionic liquids are
stable, practically nonvolatile, and non-combustible
substances. As compared to the other solvents they
well dissolve many substances, among them the
organometallic compounds. They can be regenerated
and used again. That is why nowadays ionic liquids are
often used as catalysts and solvents in chemical
processes. Besides, the development of environ-
In the work presented the results of synthesis of
new representatives of alkylamines in water medium
and investigation of their properties are reported. We
carried out reactions of various amines Ia–Id with the
bromine-substituted pentanes IIa, IIb leading to N-
alkylamines IIIa–IIIj (see the scheme).
The synthesis of the target products IIIa–IIIj was
performed in water medium at 50–90°C over 6–9 h.
Yield of the amines obtained were 74–85%. The
synthesis of alkylamines IIIc, IIId, IIIh, IIIi was
carried out at 50°C over 8 h at 5:1 amine–pentyl bromide
molar ratio. Monoethanolamine Ia and morpholine Ie
react with pentyl bromides at 60°C, and the reaction
time increases to 9 h. Optimal molar ratio in this case
2455

2456
TALYBOV et al.
RR1NH + R2Br
RR1NR2
IIа, IIb
Iа−Ie
IIIа−IIIj
RR1N = HO(CH2)2NH (Iа, IIIа, IIIе), PhCH2 NH (Ib, IIIb, IIIg), N(C2H5)2 (Iа, IIIc, IIIh),
N
(Id, IIId, IIIi),
2
N
O
(Ie, IIIe, IIIj); R = pentyl (IIа, IIIа−IIIe), iso-pentyl (Ibб, IIIе−IIIj).
13
is also 5:1. The reaction of benzylamine Ib with pentyl
bromides IIa, IIb proceeds at still higher temperature
(90°C) and the same reagent ratio.
1H and C NMR spectra of the compounds IIIa–IIIj
synthesized also confirm their structures.
The compounds synthesized IIIc, IIId, IIIi, IIIj
were tested as reagents for suppression of growth of
the sulfate-reducing bacteria. The evaluation of the
antibacterial action of reagents was carried out
according to the procedure [10] on a sample of bacteria
isolated from the formation waters of the Neft
Dashlary deposit. The amount of sulfate-reducing
bacteria in the medium under study was 10–6–10–4 cell/ml.
Testing results of the biocide activity of the com-
pounds synthesized are presented in Table 1.
Starting amines Ia–Ie are well or partially soluble
in water, and the formation of the corresponding
hydroxides [RR'NH2]+OH– is possible. Another
possible process is polyalkylation of amines Ia–Ie with
the pentyl bromides IIa, IIb leading to the quaternary
ammonium salts [RR'(C5H11)2N]+Br–. Ammonium
hydroxides and quaternary ammonium salts formed are
well soluble in water and play the role of phase-
transfer catalysts in the reaction of starting amines Ia–
Ie with the bromides IIa, IIb.
Bactericide properties of the compounds syn-
thesized in relation to the sulfate-reducing bacteria are
presented as compared with the German product
Dodigen-414 used in industry. As seen from Table 1
compounds IIIc, IIId, IIIi, IIIj exhibit higher degree
of suppression of growth of the sulfate-reducing
bacteria at different concentration as compared to the
reference substance. Compound IIIc shows the highest
effect in the concentration 25 mg l–1. At the decrease in
concentration to 20 mg l–1 the effectiveness of the
tested substances sharply decreases. Hence, com-
pounds IIIc, IIId, IIIi, IIIj may be recommended as
the bactericides for complex protection of the
machinery of oil wells from corrosion.
The purity of the compounds obtained and the
compositions of reaction mixtures were controlled by
GLC. The structure of the compounds obtained was
1
established by the IR and H and 13C NMR spec-
troscopy, and their composition, by the elemental
analysis. In the IR spectra of compounds Ia, IIIa, IIIf
the absorption bands at 3475 and 3440 cm–1
characteristic of the hydroxy group were observed [8].
In the other substances this band was absent. In the IR
spectra of the products IIIa–IIIj the absorption bands
at 1230–1220 cm–1 characteristic of the C–N bond
vibrations are present. The absorption bands observed
at 2920–2900 and 2860–2830 cm–1 are characteristic
of the C–H bonds in CH3 and CH2 groups respectively.
Table 1. Degree of suppression of growth of sulfate-reducing bacteria with the amines IIIc, IIId, IIIi, IIIj
Degree of suppression of sulfate-reducing bacteria, %
at the concentration of reagents, mg l–1
Compound
10
50
20
75
25
30
35
40
N-Pentyldiethylamine (IIIc)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
N-Pentylpiperidine (IIId)
45
60
N-(3-Metylbutyl)piperidine (IIIi)
N-(3-Methylbutyl)morpholine (IIIj)
Dodigen-414 (Germany), reference
50
70
47
63
15.0
35.0
80.0
80.0
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SYNTHESIS AND PROPERTIES OF PENTANE AMINO DERIVATIVES
Table 2. Effect of N-alkylamines on the corrosion rate of the St3 steel
Mineralized water + H2S/hydrocarbons = 9:1
degree of
Concentration,
mg l–1
Compound
steel corrosion rate,
g m–2 h–1
deceleration rate of corrosion without
protection of steel,
coefficient, γ
the inhibitor, g m–2 h–1
Z, %
N-pentyldiethylamine (IIId)
10
25
50
0.87
0.29
0.24
0.13
42.0
80.6
84.0
91.3
1.72
5.17
6.25
11.5
1.5
1.5
1.5
1.5
100
N-(3-Methylbutyl)piperidine (IIIi)
10
25
50
0.89
0.30
0.25
0.11
40.6
80.8
83.3
92.6
1.68
5.0
6.0
1.5
1.5
1.5
1.5
100
13.6
1-Methyl-3-ethyl-5-N-
piperidinobenzene (reference)
250
500
0.91
0.63
57
70
–
–
2.12
2.12
Compounds IIId, IIIi were tested also as prepara-
tions against the steel corrosion. The corrosion rate
was evaluated gravimetrically from the loss of mass of
the samples. The effectiveness of the compounds syn-
thesized was determined on the basis of the de-
celeration coefficients γ and the protection degree Z
for the St3 steel [11]. Results of testing the
anticorrosive properties of compounds IIId, IIIi are
listed in Table 2.
8MD chromatograph equipped with a 2000×3 mm glass
column (10% Apiezon on Chromosorb G), carrier gas
helium (40 ml min–1), detector katharometer, column
temperature 150°C, evaporator temperature 200°C.
N-Pentylamines, general procedure. To a solution
of 5–6 mmol of amines Ia–Ie in 5–7 ml of water
1 mmol of 1-bromopentane IIa, IIb was added. The
resulting mixture was stirred at the given temperature
(50–60°C) for 6–9 h. After that it was saturated with
10 g of dry NaOH. Organic layer was separated and
water layer was extracted with ether. Organic phases
were joined and dried over Na2CO3. After removing
the solvent the residue was distilled in a vacuum.
Anticorrosive properties of compounds under study
were evaluated against the practically used 1-methyl-3-
ethyl-5-(N-piperidino)benzene. As seen from Table 2,
compounds IIId, IIIi show higher anticorrosive
properties as compared to the reference substance.
N-Pentylethanolamine IIIa. This compound was
prepared from 9.15 g of monoethanolamine and 5.3 g
of 1-bromopentane. Yield 2.98 g (76%), bp 83–85°C
(2 mm Hg), nD20 1.4382, d420 0.8712. IR spectrum, ν,
cm–1: 3475 (OH), 3400 (NH), 2920 (CH3), 2820 (CH2),
Hence, in the course of this study new repre-
sentatives of the pentane amino derivatives were
synthesized by the environmentally safe method. The
compounds obtained exhibit sufficiently high
antibacterial and anticorrosive properties.
1
1225 (C–N). H NMR spectrum (D2O), δ, ppm: 0.87 t
(3H, CH3), 1.25 m (4H, CH2), 1.45 m (2H, CH2), 2.5 t
and 2.65 t (4H, CH2), 3.05 t (1H, NH), 3.6 t (2H,
CH2N), 4.75 br.s (1H, OH). 13C NMR spectrum (D2O),
δC, ppm: 13.8 (CH3), 22.4 (CH2), 29.0 (CH2), 29.5
(CH2), 49.1 (NHC), 50.7 (CNH), 60.0 (C–OH).
Electron impact mass spectrum, m/z (Irel, %): 131 [M+]
(37), 100 (100), 74 (100), 56 (100). Found, %: C
65.02; H 13.01; N 10.73. C7H17NO. Calculated, %: C
64.12; H 12.97; N 10.68.
EXPERIMENTAL
IR spectra were registered on an UR-20
spectrometer in the range 4000–400 cm–1. H and C
NMR spectra were taken on a Bruker-300 (300 MHz)
NMR spectrometer in CDCl3 and D2O. Chemical shifts
are presented against TMS. Mass spectra were
obtained on a VG707E instrument (ionizing electrons
energy 70 eV). The chromatographic analysis of
reaction mixtures and the evaluation of purity of the
compounds synthesized were carried out on a LKhM-
1
13
N-Pentylbenzylamine IIIb. This compound was
prepared from 10.7 g of benzylamine Ib and 3 g of 1-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 12 2010

2458
TALYBOV et al.
bromopentane IIa. Yield 2.97 g (86%), bp 112–112°C
(6 mm Hg), nD20 1.5073, d420 0.9088. IR spectrum, ν,
3.84 g (74%), bp 77–78°C (2 mm Hg), nD20 1.431, d420
0.8772. IR spectrum, ν, cm–1: 3440 (OH), 2910 (CH3),
1
1
cm–1: 2910 (CH3), 2850 (CH2), 1220 (CN). H NMR
2860 (CH2), 1225 (CN). H NMR spectrum (D2O), δ,
spectrum (CDCl3), δ, ppm: 0.95 t (3H, CH3), 1.35 q
(2H, CH2), 1.45–1.6 m (7H, NH, CH2), 2.63 t (2H,
NCH2), 3.8 s (2H, PhCH2), 7.15–7.4 (5H, Harom). 13C
NMR spectrum, (CDCl3), δC, ppm: 14 (CH3), 22
(CH2), 29 (CH2), 30 (CH2), 49 (NHCH2), 54.25
(CH2Ph), 126.82, 128.12, 128.37, 128.89 (Carom).
Found, %: C 81.51; H 10.61; N 7.99. C12H19N.
Calculated, %: C 81.37; H 10.73; N 7.90.
ppm: 0.9 d (6H, CH3), 1.3 m (2H, CH2), 1.5 m (1H,
CH), 1.3–1.6 m (4H, CH2), 2.4–2.65 m (2H, NCH2),
3.5 t (2H, NH2), 4.7 t (CH2OH). 13C NMR spectrum
(D2O), δC, ppm: 22.47 (CH3), 22.55 (CH3), 26.04
(CH), 38.22 (CH2), 50.95 (CH2N), 59.94 (CH2OH).
Found, %: C 64.09; H 13.04; N 11.65. C7H17NO.
Calculated, %: C 64.12; H 12.97, N 12.68.
N-(3-Methylbutyl)benzylamine IIIg. This com-
pound was prepared from 16 g of benzylamine Ib and
4.53 g of 1-bromo-2-methylbutane IIb. Yield 4.53 g
(82%), bp 78–79°C (2 mm Hg), nD20 1.4891, d420
0.8972. IR spectrum, ν, cm–1: 2920 (CH3), 2840 (CH2),
1225 (C–N). 1H NMR spectrum (CDCl3), δ, ppm: 0.95
d (6H, CH3), 1.4 q (2H, CH2), 1.7 sep (1H, CH), 2.7 t
(2H, N–CH2), 3.38 s (2H, Ph–CH2), 7.2–7.5 m (5H,
N-Pentyldiethylamine IIIc. This compound was
prepared from 36.6 g of diethylamine Ic and 15.1 g of
1-bromopentane IIa. Yield 11 g (77%), bp 41–42°C
(20 mm Hg), nD20 1.4109, d420 0.7779. IR spectrum, ν,
1
cm–1: 2910 (CH3), 2840 (CH2), 1230 (CN). H NMR
spectrum (D2O), δ, ppm: 0.9–1.2 d.d (9H, CH3), 1.4–
1.6 m (6H, CH2), 2.45 t (2H, NCH2), 2.6 q (4H,
CH2N). 13C NMR spectrum (D2O), δC, ppm: 12 (CH3),
14 (CH2), 22 (CH2), 27 (CH2), 39 (CH2), 48 (CH2N),
56 (NCH2). Found, %: C 75.82; H 14.51; N 9.50.
C9H21N. Calculated, %: C 75.54; H 14.67, N 9.78.
H
arom). 13C NMR spectrum (CDCl3), δC, ppm: 17.7
(CH3), 22.6 (CH2), 22.7 (CH3), 39.27 (CH), 47.7 (N–
CH2), 54.25 (PhCH2), 126.82, 128.12, 128.37, 128.89
(Carom). Found, %: C 81.62; H 10.59; N 7.81. C12H19N.
Calculated, %: C 81.37; H 10.73; N 7.90.
N-Pentylpiperiine IIId. This compound was pre-
pared from 17 g of piperidine Id and 6.0 g of 1-
bromopentane IIa. Yield 4.79 g (78%), bp. 65°C
(2 mm Hg), nD20 1.4221, d420 0.8419. IR spectrum, ν,
N-(3-Methylbutyl)diethylamine IIIh. This com-
pound was prepared from 36.6 g of diethylamine Ic
and 15.1 g of 1-bromo-3-methylbutane IIb. Yield 8.57 g
(60%), bp 139°C, nD20 1.4109, d420 0.7779. IR spectrum,
1
cm–1: 2900 (CH3), 2.830 (CH2), 1.230 (CN). H NMR
spectrum (D2O), δ, ppm: 1.04 t (3H, CH3), 1.3–1.7 m
(12H, CH2), 2.3 t (2H, NCH2), 2.4 s (4H, CH2piper). 13C
NMR spectrum (D2O), δC, ppm: 14.4 (CH3), 22.8
(CH2), 24.9 (CH3), 26.0 (CH2), 26.9 (CH2piper), 30.0
(CH2piper), 54.8 (CH2Npiper), 59.3 (NCH2aliph). Found,
%: C 77.82; H 13.62, N 9.13. C10H21N. Calculated, %:
C 77.42; H 13.55, N 9.03.
1
ν, cm–1: 2940 (CH3), 2860 (CH2), 1227 (C–N). H
NMR spectrum (D2O), δ, ppm: 1.07 d (6H, CH3), 1.15
t (6H, CH3), 1.47 q (2H, CH2), 1.79 sec (1H, CH), 2.5
q and 2.65 t (6H, CH2N). 13C NMR spectrum (D2O),
δC, ppm: 14 (CH3), 17 (CH3), 23 (CH3), 26 (CH3), 27
(CH2), 36 (CH), 46 (CH2N), 47 (CH2N), 51 (NCH2).
Found, %: C 75.63; H 14.48; N 9.62. C9H21N.
Calculated, %: C 75.54; H 14.67; N 9.78.
N-Pentylmorpholine IIIe. This compound was
prepared from 13 g of morpholine Ie and 4.53 g of 1-
bromopentane IIa. Yield 5 g (62%), bp 60°C
(2 mm Hg), nD20 1.4111, d420 0.8957. IR spectrum, ν,
N-(3-Methylbutyl)piperidine IIIi. This compound
was prepared from 25.5 g of piperidine Id and 9 g of
1-bromo-3-methylbutane IIb. Yield 13.8 g (81%), bp
60°C (2 mm Hg), nD20 1.4378, d420 0.8392. IR spectrum,
1
cm–1: 2910 (CH3), 2850 (CH2), 1230 (C–N). H NMR
spectrum (D2O), δ, ppm: 1.05 t (3H, CH3), 1.45–1.65
m (6H, CH2), 2.4 t (2H, NCH2), 2.5 m (4H, CH2N),
3.65–3.75 m (4H, OCH2). 13C NMR spectrum (D2O),
δC, ppm: 14 (CH3), 23 (CH2), 26 (CH2), 30 (CH2), 46
(NCH2), 54 (CH2N), 59 (CH2Nmorph), 66 (OCH2morph).
Found, %: C 68.75, H 12.97, N 8.92. C9H19NO.
Calculated, %: C 68.81, H 12.09, N 8.91.
1
ν, cm–1: 2920 (CH3), 2860 (CH2), 1230 (C–N). H
NMR spectrum (D2O), δ, ppm: 1 d (6H, CH3), 1.45 sep
(1H, CH), 1.5-1.8 m (6H, CH2pip, CH2aliph), 2.34 t (2H,
NCH2), 2.4 m (4H, CH2Npip).
13C NMR spectrum (D2O), δC, ppm: 11.8 (CH3),
18.0 (CH3), 25.5 (CH2), 24.5 (CH), 26 (CH2), 27
(CH2pip), 35 (CH), 54.4 (CH2Npip), 55.5 (CH2Npip), 57.7
(NCH2aliph). Found, %: C 77.73, H 13.45, N 9.10.
C10H21N. Calculated, %: C 77.42, H 13.55, N 9.03.
N-(3-Methylbutyl)ethanolamine IIIf. This com-
pound was prepared from 12.2 g of monoethanolamine
Ia and 6.1 g of 1-bromo-3-methylbutane IIb. Yield
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SYNTHESIS AND PROPERTIES OF PENTANE AMINO DERIVATIVES
4. Denk, M.K., Hatono, K., and Lough, A., Eur. J. Inorg.
Chem., 2003, no. 1, p. 224.
5. Lehman, J.F., Urguhart, S.G., Ennis, L.E., Hitchcock, A.P.,
Hatano, K., Gupta, S., and Denk, M.K., Organo-
metallics, 1999, vol. 18, no. 10, p. 1862.
6. Di Masi, N.G., Intini, F.P., Pacifico, C., Maresca, L.,
and Natile, G., Inorg. Chem. Acta, 2000, vol. 310, no. 1,
p. 27.
7. Chao-Jun, Li, Chem. Rev., 2005, vol. 105, no. 9, p. 3095.
8. Fernandez-Rodriguez, M.A., Shen, Q., and Hartwig, Z.F.,
J. Am. Chem. Soc., 2006, vol. 128, no. 10. p. 2180.
9. Mironov, V.A. and Yanovskii, S.A., Spektroskopiya v
organicheskoi khimii (Spectroscopy in Organic Chem-
istry), Moscow: Khimiya, 1985.
N-(3-Methylbutyl)morpholine IIIj. This com-
pound was prepared from 17.4 g of morpholine Id and
6 g of 1-bromo-3-methylbutane IIb. Yield 4.22 g
(71%), bp 70°C (10 mm Hg), nD20 1.4381, d420 0.8935.
IR spectrum, ν, cm–1: 2900 (CH3), 2850 (CH2), 1230
1
(C–N). H NMR spectrum (D2O), δ, ppm: 1.05 d (6H,
CH3), 1.5 q (2H, CH2), 1.8 sep (1H, CH), 2.4 t and 2.5
t (6H, CH2Naliph, CH2Nmoprph), 3.17 t (4H, OCH2morph).
13C NMR spectrum (D2O), δC, ppm: 12 (CH3), 17.7
(CH3), 23.3 (CH), 26.6 (CH2), 35.5 (NCH2), 53
(NCH2morph), 54 (NCH2morph), 57 (CH2Omorph), 67
(CH2Omorph). Found, %: C 69.01, H 12.34; N 9.02.
C9H19NO. Calculated, %: C 68.81; H 12.09, N 8.91.
10. Metodika kontrolya mikrobiologicheskoi zarazhennosti
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