N,N,N',N'-tetramethylmethanediamine, efficient reagent for thioles aminomethylation

Article abstract of DOI:10.1134/S1070428012020042

Effi cient method was developed for thiols aminomethylation using N,N,N',N'-tetra-methylmethanediamine in the presence of Sm and Fe salts. Aminosulfi des were obtained in high yields and selectivity. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012020042

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 2, pp. 175−179. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © R.R. Khairullina, B.F. Akmanov, T.V. Tyumkina, R.V. Kunakova, A.G. Ibragimov, 2012, published in Zhurnal Organicheskoi Khimii,
2012, Vol. 48, No. 2, pp. 189−193.
N,N,N′,N′-Tetramethylmethanediamine, Efficient Reagent
for Thioles Aminomethylation
R. R. Khairullinaa, B. F. Akmanovb, T. V. Tyumkinaa,
R. V. Kunakovab, and A. G. Ibragimova
aInstitute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, 450075 Russia
е-mail: ink@anrb.ru
bUfa State Academy of Economics and Service, Ufa, Russia
Received April 7, 2011
Abstract—Efficient method was developed for thiols aminomethylation using N,N,N′,N′-tetra-methylmethanediamine
in the presence of Sm and Fe salts. Aminosulfides were obtained in high yields and selectivity.
DOI: 10.1134/S1070428012020042
Organic compounds containing nitrogen and sulfur and DMF reduced the yield of aminosulfide Iа to 50%.
are used as efficient plant protecting substances[1–3], The yield is fairly sensitive to the nature of the anion
antioxidants, anticorrosion, antiscoring, and antiwear at the central atom of the catalyst: SmCl3·6H2O (98%),
additives to fuels and lubricants [4–10].
Sm(NO3)3·6H2O (60%), Sm(acac)3·H2O (43%).
Up to now one of the most known methods for the
Without catalyst under the mentioned conditions
synthesis of aminosulfides remains the classic Mannich aminosulfide Iа formed in the yield not exceeding
aminomethylation of thiols by secondary amines and 40%. In this reaction CoCl2, CuCl, CuCl2·2H2O, NiCl2,
aldehydes [11], but this procedure possesses certain
MnCl2·2H2O, PdCl2, ZnCl2 did not show any considerable
limitations. For instance, the thiols aminomethylation catalytic activity.
using formaldehyde and dimethylamine occurs with
relatively low yields [12] due to the application and dosing
of the water solutions of the initial reagents. We report here
on a new approach to aminomethylation of mono- and
dithiols applying an available and industrially produced
N,N,N′,N′-tetramethylmethanediamine that exhibits a high
reactivity in the catalyzed aminomethylation of terminal
acetylenes with the use of gem-diamines [13–15].
In the developed optimal conditions (5 mol%
SmCl3·6H2O, 60°С, 1.5 h, CHCl3) the aminomethylation
of butyl-, heptyl-, isopropyl-, tert-butyl-, phenyl-, benzyl-,
1,3-benzothiazol-2-yl-, 1,3-benzoxazol-2-ylthiols with
the help of the diamine (molar ratio thiol–diamine 10 :
12) resulted in corresponding aminosulfides Ib–Ii in
84–98% yields.
H3C
CH3
N
N
R SH +
H3C
CH3
By an example of the reaction of pentylmercaptan with
diamine it was established that among the tested catalysts
based on halides and complexes of Cu, Sm, Fe, Co, Mn,
Pd, V, Zr, Ti the highest activity exhibited SmCl3·6H2O
and FeCl3·6H2O. In the presence of SmCl3·6H2O (the ratio
[pentylmercaptan] : [diamine] : [Sm] 10 : 12 : 0.5, 60°С,
1.5 h, solvent) in the argon atmosphere N,N-dimethyl-
1-(pentylsulfanyl)methanamine (Iа) formed in 98%
yield, and in the presence of FeCl3·6H2O in analogous
conditions, in 95% yield. The use as solvents of benzene
[Sm]
CH3
CH3
R S
N
_(CH3)2NH
Iа_Ii
R = C5H11 (а), C4H9 (b), C7H15 (c), i-Pr (d), t-Bu (e), Ph (f),
Bn (g),
N
S
N
O
(h),
(i).
175

KHAIRULLINA et al.
176
The formation of compounds Ia–Ii is confirmed by
sulfides formed (mp 105–110°С) of low solubility in
the appearance in the 1Н and 13С NMR spectra of signals
at δН 3.67–3.93 and δС 59.94–69.01 ppm of the fragment
SCH2N. In the IR spectra the characteristic absorption
bands of the stretching vibrations of the C–S bond in the
region 646–647 cm–1 indicate the presence of the thio-
ether group [16]. The mass spectra of compounds Ia–Ic
contain the peaks of molecular ions, m/z 161 (Ia), 147
(Ib), 189 (Ic), and of fragment ions [M – (СН3)2NCH2
+ Н]+ 104 (Ia), 90 (Ib), 132 (Ic), [M – Н]+ 223.682 (Ih)
and 207.646 (Ii).
organic solvents.
For comparison of the rate of accumulation of com-
pound Ia in the catalyzed and noncatalyzed reaction the
aminomethylation of C5H11SH with the diamine was car-
ried out directly in the nmr tubes. It was found that after
mixing the initial reagents signals appeared in the 1H and
13C NMR spectra at δH 3.9, δС 64.12 ppm and δH 2.4, δС
38.51 ppm belonging respectively to aminosulfide Iа and
dimethylamine. The comparison of the intensity of the
corresponding signals in the NMR spectra showed that
the catalyst accelerated the formation of compound Ia
more than twice.
Aiming at the development of a selective proce-
dure of the synthesis of diaminodisulfides we explored
the aminomethylation of dithiols with N,N,N′,N′-
tetramethylmethanediamine. At the aminomethylation
of dithiols (1,2-ethane-, 1,3-propane-, 1,4-butane-,
3,6-dioxa-1,8-octanedithiol, 4,4′-oxydithiophenol) with
the diamine (the ratio [dithiol] : [diamine] : [Sm] = 10 :
22 : 0.5, 60°С, 1.5 h, solvent CHCl3) diaminodisulfides
IIа–IIe formed in 80– 94% yields.
Hence the thiols aminomethylation with the help of
N,N,N′,N′-tetramethylmethanediamine using as catalysts
.
.
SmCl3 6H2O and FeCl3 6H2O is an efficient procedure
of the synthesis of aminosulfides with high yields and
selectivity.
EXPERIMENTAL
H3C
H3C
CH3
CH3
HS
SH
The reaction progress was monitored by TLC on
Sorbfil plates, eluent hexane–ethyl acetate, 2 : 1. Initial
compounds used in the study were of the purity ≥99%.
The solvents were purified by standard procedures [16].
1Н and 13С NMR spectra were registered on a spectrom-
eter Bruker Avance-400 at operating frequencies 300.13
and 100.62 MHz, solvent CDCl3 (δС 77.10 ppm). IR spec-
tra were recorded on a spectrophotometer Bruker Vertex
70 v from mulls in mineral oil. Mass spectra of com-
pounds Iа–Ic were measured on an instrument Shimadzu
GCMS-QP2010Plus (capillary column SPB-5 30 m ×
0.25 mm, carrier gas helium, ramp from 40 to 300°C at a
rate 8 deg/min, vaporizer temperature 280°C, ion source
temperature 200°C, ionizing energy 70 eV). Mass spectra
of compounds Ie, If were obtained on a spectrometer
MALDI-TOF Autoflex III (Bruker, Germany), α-cyano-
4-hydroxycinnamic and 2,5-dihydrobenzoic acids were
used as matrices (the sample was prepared by the method
N
N
X
+
CH3
CH3
H3C
H3C
[Sm]
N
N
S
S
_(CH3)2NH
X
IIа_IIe
X = (CH2)n, n = 2 (а), 3 (b), 4 (c), (CH2)2O(CH2)2O(CH2)2 (d),
p-C6H4OC6H4-p (e).
In the Н and 13С NMR spectra of compounds IIа–
1
IIe the signals at δН 3.43 – 4.53 and δС 64.06–64.91
ppm correspond to the fragment SCH2N. The molecule
is symmetric, and all the signals are magnetically
equivalent. In the 2D-spectra HMBC of compound IIe
cross-peaks are observed corresponding to the coupling
of the atoms C5–Н9 and С9–Н11 (C11–Н9) (see the figure).
At the aminomethylation of 1,2-ethanedithiol with
the diamine in the absence of solvent a mixture of poly-
H
H
11
H
H
3
4
1
O
H3C
H
2
5
9
N
S
S
8
N
10
12
H3C
CH3
7
6
2D (HMBC) couplings 4,4′-oxybis[phenyl-1-sulfanyl-(N,N-dimethyl)methaneamine] (IIe).
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N,N,N′,N′-TETRAMETHYLMETHANEDIAMINE, EFFICIENT REAGENT
177
of “dried drop” in chloroform, 1 : 10). The elemental com-
position was determined on an analyzer Karlo Erba-1106,
melting points, on an instrument RNMK 80/2617, refrac-
tion indices, on a refractometer IRF 454 BM. Individual
substances were obtained by chromatography on silica
gel of KSK grade (50 – 160 μm).
С7Н15S]+. Found, %: С 63.32; Н 12.35; N 8.16; S 16.17.
С10H23NS. Calculated, %: С 63.43; Н 12.24; N 7.40; S
16.93. M 189.362.
1-(Isopropylsulfanyl)-N,N-dimethylmethanamine
(Id). Yield 95% (SmCl3·6H2O), 98% (FeCl3·6H2O), nD20
1.6489, Rf 0.27. IR spectrum, cm–1: 2972–2766, 1450,
1
Aminomethylation of mercaptans with N,N,N′,N′-
tetramethylmethanediamine. A mixture of 10 mmol
of an appropriate mercaptan, 12 mmol of N,N,N′,N′-
tetramethylmethanediamine, 0.5 mmol of catalyst
SmCl3·6H2O or FeCl3·6H2O was stirred for 1.5 h at
60°С. Then from the reaction mixture N,N-dimethyl-N-
[(alkylsulfanyl)methan]amines I were isolated by column
chromatography on SiO2.
1377, 1264, 1153, 1041, 816, 656. Н NMR spectrum,
δ, ppm: 1.26 d (6Н, СН3, J 6.7 Hz), 2.44 br.s (6Н, СН3),
2.91 m (1Н, СН, J 6.7 Hz), 3.71 br.s (2Н, СН2). 13С NMR
spectrum, δ, ppm: 24.04 s (C5,6), 35.78 s (C4), 42.87 s
(C7,8), 62.41 s (С2). Found, %: С 54.32; Н 11.05; N 10.06;
S 24.57. С6H15NS. Calculated, %: С 54.08; Н 11.35;
N 10.51; S 24.06.
1-(tert-(Butylsulfanyl)-N,N-dimethylmethanamine
(Ie). Yield 97% (SmCl3·6H2O), 95% (FeCl3·6H2O), nD20
1.6480, Rf 0.27. IR spectrum, cm–1: 2973–2766, 1458,
1363, 1258, 1153, 1046, 817, 664. 1Н NMR spectrum, δ,
ppm: 1.30 m (9Н, СН3), 2.25 m (6Н, СН3), 3.88 br.s (2Н,
СН2). 13С NMR spectrum, δ, ppm: 31.50 s (C5,6,7), 41.77 s
(C4), 43.08 s (C8,9), 59.94 s (С2). Found, %: С 57.32; Н
11.50; N 9.47; S 21.71. С7H17NS. Calculated, %: С 57.08;
Н 11.63; N 9.51; S 21.77.
N,N-Dimethyl-1-(pentylsulfanyl)methanamine
(Iа). Yield 98% (SmCl3·6H2O), 95% (FeCl3·6H2O),
nD20 1.4672, Rf 0.36. IR spectrum, cm–1: 2929–2771, 1688,
1453, 1253, 1151, 1042, 816, 646. 1Н NMR spectrum, δ,
ppm: 0.88 m (3Н, СН3), 1.32 m (4Н, СH2), 1.57 m (2Н,
СH2), 2.20 br.s (6Н, СH3), 2.55 t (2Н, СH2), 3.93 br.s (2Н,
СН2). 13С NMR spectrum, δ, ppm: 13.65 s (C8), 22.03 s
(C7), 30.07 s (C6), 30.83 s (C5), 33.27 s (C4), 42.45 s
(C9,9′), 64.27 s (С2). Mass spectrum, m/z: 161 [M]+, 104
[M – (CH3)2NCH2 + H]+, 58 [M – С5Н11S]+. Found, %:
С 58.32; Н 11.24; N 10.27; S 20.17. С8Н19NS. Calculated,
%: С 59.57; Н 11.87; N 8.68; S 19.88. M 161. 309.
N,N-Dimethyl-1-(phenylsulfanyl)methanamine
(If). Yield 88% (SmCl3·6H2O), 90% (FeCl3·6H2O),
nD20 1.6500, Rf 0.37. IR spectrum, cm–1: 3071, 2973–2786,
1681, 1583, 1477–1437, 1254, 1127, 1046, 959, 742,
1
1-(Butylsulfanyl)-N,N-dimethylmethanamine
(Ib). Yield 98% (SmCl3·6H2O), nD20 1.4737, Rf 0.35. IR
spectrum, cm–1: 2958–2780, 1667, 1453, 1257, 1151,
1042, 786, 646. 1Н NMR spectrum, δ, ppm: 0.69 m (3Н,
СН3), 1.16 m (2Н, СН2), 1.36 m (2Н, СН2), 1.99 br.s (6Н,
СН3), 2.36 m (2Н, СН2), 3.67 br.s (2Н, СН2). 13С NMR
spectrum, δ, ppm: 13.42 s (C7), 21.75 s (C6), 32.38 s (C5),
33.05 s (C4), 42.32 s (C8,8′), 64.32 s (С2). Mass spectrum,
m/z (Irel, %): 147 (100) [M]+, 90 [M – (CH3)2NCH2 + H]+,
58 [M – С4Н9S]+. Found, %: С 56.73; Н 11.44; N 9.60;
S 22.23. С7Н17NS. Calculated, %: С 57.08; Н 11.63;
N 9.51; S 21.77. M 147.283.
691, 622. Н NMR spectrum, δ, ppm: 2.34 br.s (6Н,
СН3), 4.50 br.s (2Н, СН2), 7.29 t (3Н, СH, J 7.2 Hz),
7.51 d (2Н, СH, J 7.2 Hz). 13С NMR spectrum, δ, ppm:
42.71 s (C10,11), 69.01 s (C2), 126.37 s (C7), 128.94 s
(C6,8), 131.75 s (C5,9), 138.17 s (C4). Mass spectrum,
m/z (Irel, %): 167 (20) [M]+, 91 (25) [M – Ph + H]+, 58
(100) [M – PhS + H]+. Found, %: С 64.52; Н 7.95; N
8.27; S 19.26. С9H13NS. Calculated, %: С 64.62; Н 7.83;
N 8.37; S 19.17. M 167.272.
1-(Benzylsulfanyl)-N,N-dimethylmethanamine
(Ig). Yield 84% (SmCl3·6H2O), 84% (FeCl3·6H2O),
nD20 1.5552, Rf 0.29. IR spectrum, cm–1: 3061–3028,
2970–2775, 1602, 1494–1452, 1311, 1263, 1135, 1043,
1-(Heptylsulfanyl)-N,N-dimethylmethanamine
(Ic). Yield 98% (SmCl3·6H2O), nD20 1.4677, Rf 0.36. IR
spectrum, cm–1: 2926–2780, 1667, 1452, 1258, 1140,
1
815, 701, 641. Н NMR spectrum, δ, ppm: 2.33 s (6Н,
СН3), 3.81 s (2Н, СН2), 3.88 br.s (2Н, СН2), 7.25 br.s
(2Н, СH), 7.36 br.s (3Н, СH). 13С NMR spectrum, δ,
ppm: 36.94 s (C4), 43.04 s (C11,12), 63.21 s (C2), 126.93
s (C8), 128.24 s (C7,9), 128.63 s (C6,10), 139.00 s (C5).
Mass spectrum, m/z (Irel, %): 181 (20) [M]+, 91 (28)
[M – Bn + H]+, 58 (100) [M – BnS + H]+. Found, %:
С 66.21; Н 8.33; N 7.77; S17.69. С10H15NS. Calculated,
%: С 66.25; Н 8.34; N 7.73; S 17.69. M 181.299.
1
1042, 816, 647. Н NMR spectrum, δ, ppm: 0.84 m
(3Н, СН3), 1.31 m (8Н, СН2), 1.58 m (2Н, СН2), 2.23
br.s (6Н, СН3), 2.52 m (2Н, СН2), 3.87 br.s (2Н, СН2).
13С NMR spectrum, δ, ppm: 14.01 s (C10), 22.56 s (C9),
28.84 s (C8), 28.87 s (C7), 30.10 s (C6), 31.70 s (C5),
33.77 s (C4), 42.77 s (C11,11′), 64.67 s (С2). Mass spectrum,
m/z: 189 [M]+, 132 [M – (CH3)2NCH2 + H]+, 58 [M –
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KHAIRULLINA et al.
178
32.11 br.s (C4,6), 42.57 s (C10,10′), 64.46 br.s (С2,8). Found,
%: С 47.93; Н 10.14; N 12.40; S 29.53. С9Н22N2S2.
Calculated, %: С 48.60; Н 9.97; N 12.60; S 28.83.
1-(1,3-Benzothiazol-2-ylsulfanyl)-N,N-dimethyl-
methanamine (Ih). Yield 96% (SmCl3·6H2O), mp 67–
70°С, Rf 0.37. IR spectrum, cm–1: 2923–2854, 1657–
1587, 1462, 1406, 1330, 1275, 1134, 1061, 971, 723, 616.
1Н NMR spectrum, δ, ppm: 2.45 br.s (6Н, СН3), 4.93 t
(2Н, СН2), 7.23–7.33 m (4Н, СH). 13С NMR spectrum,
δ, ppm: 43.29 s (C13,14), 68.88 s (C11), 110.13 s (C9),
110.87 s (C6), 124.27 s (C7), 124.87 s (C8), 132.44 d
(C5), 147.13 s (C4), 181.44 s (С2). Mass spectrum, m/z:
223.682 [M – Н]+. Found, %: С 53.32; Н 5.45; N 13.01;
S 28.22. С10H12N2S2. Calculated, %: С 53.54; Н 5.39;
N 12.49; S 28.59. M 224.348.
N1,N1,N8,N8-Tetramethyl-2,7-dithiaoctane-
1,8-diamine (IIc). Yield 85% (SmCl3·6H2O), 72%
(FeCl3·6H2O), nD20 1.4927, Rf 0.13. IR spectrum, cm–1:
2937–2769, 1686, 1451, 1313–1259, 1164, 1042, 905,
816, 643. 1Н NMR spectrum, δ, ppm: 1.27 m (4Н, СН2),
1.82 br.s (12Н, СН3), 2.20 m (4Н, СН2), 3.46 m (4Н,
СН2). 13С NMR spectrum, δ, ppm: 25.65 s (C5,6), 32.53 s
(C4,7), 42.37 s (C11,11′), 64.06 s (С2,9). Found, %: С 50.32;
Н 10.34; N 12.01; S 27.32. С10Н24N2S2. Calculated, %:
С 50.80; Н 10.23; N 11.85; S 27.12.
N1,N1,N12,N12-Tetramethyl-5,8-dioxa-2,11-
dithiadodecane-1,12-diamine (IId). Yield 81%
(SmCl3·6H2O), 77% (FeCl3·6H2O), nD20 1.5135, Rf 0.13.
IR spectrum, cm–1: 2937–2770, 1680, 1450, 1315–1260,
1164, 1040, 905, 816, 645. 1Н NMR spectrum, δ, ppm:
2.27 br.s (12Н, СН3), 2.72 t (4Н, СН2), 3.58 t (4Н, СН2),
3.59 t (4Н, СН2), 3.96 br.s (4Н, СН2). 13С NMR spec-
trum, δ, ppm: 32.64 s (C4,11), 42.80 s (C15,16,17,18), 65.13 s
(C2,13), 70.25 s (С5,10), 71.58 s (С7,8). Found, %: С 48.52;
Н 9.54; N 9.41; S 22.97. С12Н28N2O2S2. Calculated, %:
С 48.61; Н 9.52; N 9.45; S 21.63.
1-(1,3-Benzoxazol-2-ylsulfanyl)-N,N-dimeth-
ylmethanamine (Ii). Yield 96% (SmCl3·6H2O),
mp 90–93°С, Rf 0.23. IR spectrum, cm–1: 2925–2855,
1650–1581, 1462, 1377, 1258, 1127, 1031, 959, 719, 612.
1Н NMR spectrum, δ, ppm: 2.44 br.s (6Н, СН3), 5.05 t
(2Н, СН2), 7.26–7.46 m (4Н, СH). 13С NMR spectrum,
δ, ppm: 43.17 s (C13,14), 67.65 s (C11), 113.81 s (C9),
120.88 s (C6), 124.70 s (C7), 126.78 s (C8), 141.89 d
(C5), 162.97 s (C4), 191.09 s (С2). Mass spectrum, m/z:
207.646 [M – Н]+. Found, %: С 57.32; Н 5.95; N 13.47;
S 15.57. С10H12N2OS. Calculated, %: С 57.67; Н 5.81;
N 13.45; S 15.40. M 208.281.
Aminomethylation of dithiols with N,N,N′,N′-
tetramethylmethanediamine. In an argon atmo-
sphere a mixture of 5 ml of chloroform, 0.5 mmol
of catalyst SmCl3·6H2O, 22 mmol of N,N,N′,N′-
tetramethylmethanediamine, 10 mmol of an appropriate
dithiol was stirred for 1.5 h at 60°С. Then from the reac-
tion mixture the corresponding diaminodisulfides II were
isolated by column chromatography on SiO2.
4,4′-Oxybis[(N,N-dimethyl)phenyl-1-sulfanyl-
methanamine] (IIe). Yield 80%, nD20 1.5478, Rf 0.13.
IR spectrum, cm-1: 2972–2860, 1657, 1580, 1483, 1313–
1236, 1151, 1094, 905, 820, 724, 615. 1Н NMR spectrum,
δ, ppm: 2.33 m (12Н, СН3), 4.43 s (4Н, СН2), 6.91 d
(4Н, СН, J 7.2 Hz), 7.45 d (4Н, СН, J 7.2 Hz). 13С NMR
spectrum, δ, ppm: 36.76 s (C11,11′,12,12′), 42.37 s (C11,11′),
63.94 s (С9,9′), 113.51 d (С4,4′,6,6′), 126.60 d (С5,5′),
126.82 d (С3,3′,7,7′), 149.93 d (С2,2′). Found, %: С 61.32;
Н 7.24; N 8.01; S 18.97. С18Н24N2S2O. Calculated, %:
С 62.03; Н 6.94; N 8.04; S 18.40.
N1,N1,N6,N6-Tetramethyl-2,5-dithiahexane-
1,6-diamine (IIa). Yield 90% (SmCl3·6H2O), 87%
(FeCl3·6H2O), nD20 1.5032, Rf 0.10. IR spectrum, cm–1:
2937–2778, 1681, 1451, 1314–1256, 1151, 1043, 902,
1
Aminomethylation of thiols with N,N,N′,N′-
tetramethylmethanediamine in the nmr tube in the
spectrometer probe was carried out in a dynamic mode
in two tubes. In the first tube 9.6 × 10–4 mol (100 mg)
of C5H11SH, 9.8 × 10–4 mol (100 mg) of N,N,N′,N′-
tetramethylmethanediamine, and 4.8 × 10–5 mol of
SmCl3·6H2O in 0.25 ml CDCl3 was mixed and then
placed into the spectrometer probe for registering NMR
spectra under the conditions of continuous registering at
298.1K. In the second tube the reaction was carried out
in the absence of the catalyst under analogous conditions
and the amounts of initial reagents.
816, 638. Н NMR spectrum, δ, ppm: 2.22 br.s (12Н,
СН3), 2.70 t (4Н, СН2), 3.88 br.s (4Н, СН2). 13С, δ,
ppm: 32.76 br.s (C4,5), 42.77 s (C9,9′), 64.91 br.s (С2,7).
Found, %: С 46.23; Н 9.84; N 13.40; S 30.53. С8Н20N2S2.
Calculated, %: С 46.11; Н 9.67; N 13.44; S 30.78.
N1,N1,N7,N7-Tetramethyl-2,6-dithiaheptane-
1,7-diamine (IIb). Yield 86% (SmCl3·6H2O), 83%
(FeCl3·6H2O), nD20 1.4967, Rf 0.15. IR spectrum, cm–1:
2937–2778, 1682, 1451, 1316–1249, 1151, 1043, 900,
1
836, 641. Н NMR spectrum, δ, ppm: 1.80 m (2Н,
СН2), 2.23 br.s (12Н, СН3), 2.62 t (4Н, СН2), 3.88 br.s
(4Н, СН2). 13С NMR spectrum, δ, ppm: 29.35 s (C5),
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N,N,N′,N′-TETRAMETHYLMETHANEDIAMINE, EFFICIENT REAGENT
179
Neftekhimiya, 2009, vol. 49, p. 532.
ACKNOWLEDGMENTS
7. Alimardanov, Kh.M., Sadygov, O.A., Suleimanova, E.T.,
Dzhafarova, N.A., Abdullaeva, M.Ya., and Babaev, N.R.,
Zh. Prikl. Khim., 2009, vol. 82, p. 1159.
The study was performed under the financial support
of the Russian Foundation for Basic Research (grant
no. 08-03-00789).
8. Dzhafarov, I.A., Mamedbeili, E.G., Gasanov, V.S., and
Gasanov, Kh.I., Zh. Prikl. Khim., 2009, vol. 82, p. 696.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012