Synthesis of 2,3-acetylenic amines by aminomethylation of acetylenes with geminal diamines

Article abstract of DOI:10.1134/S1070428010010021

A general and effective procedure has been developed for the synthesis of symmetrical and unsym- metrical 2,3-acetylenic amines by aminomethylation of terminal mono- and diacetylenes with geminal diamines in the presence of transition metal salts and complexes.

Full text of DOI:10.1134/S1070428010010021

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 1, pp. 43–48. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.G. Shaibakova, I.G. Titova, G.A. Makhmudiyarov, A.G. Ibragimov, U.M. Dzhemilev, 2010, published in Zhurnal Organicheskoi
Khimii, 2010, Vol. 46, No. 1, pp. 44–48.
Synthesis of 2,3-Acetylenic Amines by Aminomethylation
of Acetylenes with Geminal Diamines
M. G. Shaibakova, I. G. Titova, G. A. Makhmudiyarov, A. G. Ibragimov, and U. M. Dzhemilev
Institute of Petroleum Chemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received October 24, 2008
Abstract—A general and effective procedure has been developed for the synthesis of symmetrical and unsym-
metrical 2,3-acetylenic amines by aminomethylation of terminal mono- and diacetylenes with geminal diamines
in the presence of transition metal salts and complexes.
DOI: 10.1134/S1070428010010021
Alk-2-yn-1-amines are widely used in the synthesis
of cyclic and acyclic heteroatom compounds [1–9].
A well known procedure for the synthesis of such
amines is based on Mannich aminomethylation of
terminal acetylenes [10] by the action of secondary
amines and aldehydes or geminal diamines in the pres-
ence of copper-containing catalysts [11–17]. Dipiperi-
dinomethane was shown to be inactive in aminometh-
ylation of terminal acetylenes [18]. We recently found
[19] that N,N,N′,N′-tetramethylmethanediamine fairly
readily reacts with terminal acetylenes to give the cor-
responding N,N-dimethylalk-2-yn-1-amines. The pro-
posed procedure [19] makes it possible to avoid the
use of toxic solvents (dioxane, dimethylformamide,
methylene chloride, acetonitrile, dimethyl sulfoxide,
etc.) and ensures considerably lower consumption of
the catalyst in addition to shorter reaction time.
2-yn-1-amines, in the present work we examined reac-
tions of geminal diamines with terminal acetylenes and
diacetylenes in the presence of catalysts which showed
the highest activity in the aminomethylation of acety-
lenes with N,N,N′,N′-tetramethylmethanediamine [19].
We presumed that, by analogy with N,N,N′,N′-tetra-
methylmethanediamine [19], higher geminal diamines
can also be used for aminomethylation of terminal
alkynes to obtain the corresponding acetylenic amines.
First of all, we have developed a preparative proce-
dure for the synthesis of initial geminal diamines Ia
and Ib via transamination of N,N,N′,N′-tetramethyl-
methanediamine with piperidine and morpholine
(80°C, 6 h) in the presence of 5–10 mol % of
Sm(NO3)2·6H2O or CuCl (Scheme 1). These catalysts
ensured the best yields of the target products (Table 1).
The structure of compounds Ia and Ib was confirmed
by spectral methods, including 15N NMR spectroscopy.
With a view to extend the scope of aminomethyla-
tion of terminal alkynes with diamines in the presence
of transition metal catalysts, as well as to develop
an efficient procedure for the synthesis of various alk-
Table 1. Transamination of N,N,N′,N′-tetramethylmethane-
diamine with piperidine and morpholine (molar ratio di-
amine–amine–catalyst 1:2:0.05, 80°C, 6 h, argon)
Scheme 1.
Catalyst
Initial amine
Yield of Ia or Ib, %
Me
Me
NH
N
N
2
+
Sm(NO3)2·6H2O
CuCl
Piperidine
Piperidine
Piperidine
Morpholine
Morpholine
Morpholine
85
77
38
89
80
34
X
Me
Me
Sm(NO3)2 ·6H2O
No catalyst
Sm(NO3)2·6H2O
CuCl
or CuCl
N
N
–2Me2NH
X
X
Ia, Ib
No catalyst
X = CH2 (a), O (b).
43

SHAIBAKOVA et al.
44
Scheme 2.
[Cu]
CH
N
N
N
+
R
R
X
X
X
NH
–
Ia, Ib
IIa–IIj
X
II, X = CH2, R = Pr (a), Bu (b), C5H11 (c), C6H13 (d), Ph (e); X = O, R = C6H13 (f), C5H11 (g), Bu (h), Pr (i), Ph (j).
Scheme 3.
2
7
8
1
[Cu]
1:1
9
N
CH
( )n
X
N
N
HC
CH
IIIa, IIIb
+
X
X
2
5
( )n
1
N
3
[Cu]
1:2
N
Ia, Ib
4 X
6
X
( )n
IVa–IVc
III, n = 4, X = CH2 (a), O (b); IV, n = 4, X = CH2 (a), O (b), n = 6, X = O (c).
Diamine Ia displayed in the 15N NMR spectrum
only one signal at δN 314.7 ppm due to its symmetric
structure.
the presence of CuCl or Sm(NO3)2·6H2O [molar ratio
I–alkyne–catalyst 1:1:0.05]. The reactions were car-
ried out by heating the reactants at 80°C over a period
of 6 h, and the products were the corresponding 1-[pi-
peridino(morpholino)methyl]-2-alkyl(phenyl)acety-
lenes IIa–IIe whose yields ranged from 60 to 85%,
depending on the initial diamine and acetylenic sub-
strate (Scheme 2, Table 2).
Symmetric diamines Ia and Ib were brought into
reactions with terminal alkynes (pent-1-yne, hex-1-
yne, hept-1-yne, oct-1-yne, and phenylacetylene) in
Table 2. Aminomethylation of terminal alkynes with di-
amines Ia and Ib in the presence of CuCl (molar ratio di-
amine I–alkyne–CuCl 1:1:0.05, 80°C, 6 h)
We also tried to perform aminomethylation of
terminal diacetylenes with diamines Ia and Ib under
analogous conditions [5 mol % of Sm(NO3)2·6H2O or
CuCl, 80°C, 6 h]. In the reaction of octa-1,7-diyne
with an equimolar amount of dipiperidinomethane (Ia)
we obtained >90% of 1-(nona-2,7-diyn-1-yl)piperidine
(IIIa) (Scheme 3). The downfield region of the 13C
NMR spectrum of IIIa contained four signals at
δC 68.48, 84.55, 74.70, and 84.00 ppm, indicating the
presence of four nonequivalent triple-bonded carbon
atoms. The absence of a signal at δC 82.89 ppm (typ-
ical of methylene carbon atom in the N–CH2–N frag-
ment of initial diamine Ia), downfield shift of signals
from acetylenic carbon atoms (C8, C9; ∆δC 2.0–
6.0 ppm), and the absence of a signal assignable to
Initial diamine no.
Acetylene
Oct-1-yne
Yield, %
Ia
Ia
Ia
Ia
Ib
Ib
Ib
Ib
Ia
Ia
Ia
Ib
Ib
Ib
68
60
Hept-1-yne
Hex-1-yne
Pent-1-yne
Oct-1-yne
61
64
42
Hept-1-yne
Hex-1-yne
Pent-1-yne
Oct-1-yne
51
48
73
a61a
a63a
97
a85a
a64a
98
1
acetylenic proton (δ 3.13 ppm) in the H NMR spec-
Pent-1-yne
Phenylacetylene
Oct-1-yne
trum indicated that aminomethylation of initial octa-
1,7-diyne involved only one terminal acetylenic group.
Two-dimensional heteronuclear HMBC experi-
ments revealed couplings between 7-H (δ 3.0 ppm), on
the one hand, and C8 and C9, on the other. In addition,
the 13C NMR spectrum of IIIa contained cross peaks
between C7 (δC 47.51 ppm) and C2/C6 in the piperidine
Hex-1-yne
Phenylacetylene
a
In the presence of Sm(NO3)2·6H2O as catalyst.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 1 2010

SYNTHESIS OF 2,3-ACETYLENIC AMINES BY AMINOMETHYLATION OF ACETYLENES
45
Scheme 4.
Me
Me
N
N
N
N
HC
CH
+
+
O
O
Me
Me
Ib
Sm(NO3)2 · 6H2O
or CuCl
N
N
Me
N
O
+
O
O
N
NH
Me
–Me2NH, –
V
IVb
O
Me
N
Me
N
+
Me
Me
IVd
ring, so that compound IIIa was assigned the structure
Thus transition metal-catalyzed aminomethylation
of monosubstituted diacetylene.
of terminal mono- and diacetylenes with geminal di-
amines opens a convenient and promising synthetic
route to 2,3-acetylenic amines.
Our results allowed us to expect successful amino-
methylation at both ≡CH groups in other terminal
diacetylenes with geminal diamines with formation of
symmetrical bis(aminomethyl) derivatives in which the
acetylenic fragments are linked through polymethylene
chains. As diacetylenic substrates we selected hepta-
1,6-diyne, octa-1,7-diyne, and deca-1,9-diyne. By re-
action of hepta-1,6-diyne with dipiperidinomethane at
a ratio of 1:2 [5 mol % of CuCl or Sm(NO3)2·6H2O,
80°C, 6 h] we obtained 1,9-dipiperidinonona-2,7-diyne
(IVa) in more than 70% yield. The 13C NMR spectrum
of IVa contained signals from magnetically equivalent
(in pairs) carbon atoms in the acetylenic fragments at
δC 84.42 (C9, C14) and 74.76 ppm (C8, C15). Likewise,
the reactions of dimorpholinomethane with octa-1,7-
diyne and deca-1,9-diyne gave 1,10-dimorpholino-
deca-2,8-diyne (IVb) and 1,12-dimorpholinododeca-
2,10-diyne (IVc) in 75 and 70% yield, respectively
(Scheme 3).
EXPERIMENTAL
The progress of reactions was monitored by TLC
on Silufol plates using the following solvent systems:
acetone–methanol (9:2 to 9:3), acetone–chloroform
(9:1), and acetone–ethanol (9:1). Commercially avail-
able acetylenic substrates and solvents of chemically
pure grade were used. The mass spectra were recorded
1
on a VG-TRIO mass spectrometer. The H and 13C
NMR spectra were measured on Jeol FX-90Q (90 and
22.5 MHz, respectively) and Bruker Avance 400 spec-
trometers (400.13 and 100.62 MHz, respectively)
using CDCl3 as solvent and tetramethylsilane as in-
ternal reference. The IR spectra were recorded in KBr
on a Specord 75IR instrument. The elemental composi-
tions were determined on a Carlo Erba 1106 analyzer.
The products were analyzed by GLC on a Khrom-5
chromatograph equipped with a flame-ionization
detector and a 2000×3-mm column; stationary phase
SE-30; oven temperature programming from 50 to
280°C at a rate of 8 deg/min); injector temperature
300°C, detector temperature 250°C.
With a view to obtain unsymmetrically substituted
diamino diacetylene, octa-1,7-diyne was subjected to
aminomethylation with a 1:1 mixture of N,N,N′,N′-
tetramethylmethanediamine and dimorpholinomethane
under the above conditions. The reaction gave a mix-
ture of unsymmetrical 1-dimethylamino-10-morpho-
linodeca-2,8-diyne (V, yield 31%) and two symmet-
rically substituted products, 1,10-dimorpholinodeca-
2,8-diyne (IVb) and 1,10-bis(dimethylamino)deca-2,8-
diyne (IVd), at a ratio of ~1:1:1 (Scheme 4). The frac-
tion of unsymmetrical product V may be increased to
60% by adding first an equimolar amount of bis(di-
methylamino)methane and then (after 3 h) an equi-
molar amount of dimorpholinomethane.
Geminal diamines Ia and Ib (general procedure).
A glass reactor equipped with a magnetic stirrer was
charged under argon with 10 mmol of piperidine or
morpholine, 20 mmol of N,N,N′,N′-tetramethylmeth-
anediamine, and 0.5 mmol of CuCl or Sm(NO3)2·
6 H2O, and the mixture was stirred for 6 h at 80°C.
Compounds Ia and Ib were isolated by vacuum dis-
tillation or column chromatography.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 1 2010

SHAIBAKOVA et al.
46
1,1′-Methylenedipiperidine (Ia). Yield 85%,
Found, %: C 78.28; H 11.61; N 7.00. C13H23N. Cal-
culated, %: C 80.82; H 11.92; N 7.26.
bp 98–100°C (8 mm), n2D5 = 1.4798. IR spectrum:
1
ν 1235 cm–1 (C–N–C). H NMR spectrum, δ, ppm:
1-(Non-2-yn-1-yl)piperidine (IId). Yield 68%,
bp 148–151°C (8 mm), nD25 = 1.5297. IR spectrum, ν,
cm–1: 2260 (C≡C), 1200 (C–N–C). 1H NMR spectrum,
δ, ppm: 0.84 t (3H, J = 7 Hz), 1.00–1.65 m (12H),
2.09 t (2H), 3.10 s (2H), 2.37 m (4H), 2.14 m (4H).
13C NMR spectrum, δC, ppm: 12.91, 18.65, 22.42,
24.42, 26.25, 27.80, 30.53, 47.20, 52.80, 75.05, 84.03.
Found, %: C 76.65; H 11.46; N 6.76. C14H25N. Calcu-
lated, %: C 81.16; H 12.08; N 6.76.
2.67 s (2H), 2.27 m (8H), 1.34 m (12H). 13C NMR
spectrum, δC, ppm: 24.74, 25.71, 52.74, 82.89.
15N NMR spectrum: δN 314.7 ppm. Found, %:
C 73.04; H 12.06; N 14.58. C11H22N2. Calculated, %:
C 73.08; H 12.28; N 14.64.
4,4′-Methylenedimorpoline (Ib). Yield 89%,
bp 111–113°C (8 mm), nD25 = 1.5314. IR spectrum, ν,
1
cm–1: 1220 (C–N–C), 1070 (C–O–C). H NMR spec-
trum, δ, ppm: 2.79 s (2H), 2.37 m (8H), 3.57 m (8H).
13C NMR spectrum, δC, ppm: 51.86, 66.84, 81.56.
Found, %: C 55.98; H 9.64; N 14.51. C9H18N2O2. Cal-
culated, %: C 58.06; H 9.67; N 15.07.
1-(3-Phenylprop-2-yn-1-yl)piperidine (IIe). Yield
97%, bp 124–125°C (2 mm), nD25 = 1.5611. IR spec-
1
trum, ν, cm–1: 2160 (C≡C), 1220 (C–N–C). H NMR
spectrum, δ, ppm: 2.10–2.65 m (4H), 3.29 s (2H),
13
3.10–3.74 m (4H), 7.04–7.34 m (5H). C NMR spec-
Aminomethylation of terminal mono- and di-
acetylenes (general procedure). A glass reactor
equipped with a magnetic stirrer was charged under
argon with 1–3 mmol of diamine Ia or Ib, 1 mmol of
the corresponding terminal acetylene or 0.5 mmol of
diacetylene, and 0.05 mmol of CuCl or Sm(NO3)2·
6H2O, and the mixture was stirred for 6 h at 80°C.
Compounds II–IV were isolated from the reaction
mixture by vacuum distillation or column chromatog-
raphy.
trum, δC, ppm: 24.82, 25.80, 43.21, 52.80, 84.10,
84.21, 123.33, 127.92, 128.31, 131.77. Found, %:
C 84.21; H 6.28; N 7.36. C14H17N. Calculated, %:
C 86.60; H 6.18; N 7.22.
4-(Non-2-yn-1-yl)morpholine (IIf). Yield 85%,
bp 150–153°C (8 mm), nD25 = 1.5308. IR spectrum, ν,
cm–1: 2250 (C≡C), 1120 (C–O–C), 1040 (C–N–C).
1H NMR spectrum, δ, ppm: 0.89 br.s (3H), 1.35 m
(4H), 2.16 m (2H), 3.26 s (2H), 2.45 m (4H), 3.62 m
(4H). 13C NMR spectrum, δC, ppm: 13.24, 18.09,
21.71, 30.69, 47.47, 52.12, 66.48, 74.07, 85.82. Found,
%: C 76.65; H 11.46; N 6.3. C13H23NO. Calculated, %:
C 75.73; H 9.70; N 7.77.
1-(Hex-2-yn-1-yl)piperidine (IIa). Yield 64%,
bp 108–111°C (8 mm), nD25 = 1.5293. IR spectrum, ν,
cm–1: 2250 (C≡C), 1240 (C–N–C). 1H NMR spectrum,
δ, ppm: 0.89 t (3H, J = 7 Hz), 1.21–1.54 m (4H), 2.21 t
(2H), 2.39 m (4H), 2.51 m (4H), 3.19 s (2H). 13C NMR
spectrum, δC, ppm: 12.91, 18.65, 22.42, 24.42, 26.25,
27.80, 30.53, 47.20, 52.80, 75.05, 84.03. Found, %:
C 78.28; H 11.61; N 7.00. C11H20N. Calculated, %:
C 79.52; H 12.05; N 8.43.
4-(Oct-2-yn-1-yl)morpholine (IIg). Yield 51%,
bp 140–143°C (8 mm), nD25 = 1.5282. IR spectrum, ν,
cm–1: 1125 (C–O–C), 1240 (C–N–C), 2245 (C≡C).
1H NMR spectrum, δ, ppm: 0.89 br.s (3H), 1.35 m
(4H), 2.16 m (2H), 2.45 m (4H), 3.26 s (2H), 3.62 m
(4H). 13C NMR spectrum, δC, ppm: 13.24, 18.09,
21.71, 30.69, 47.47, 52.12, 66.48, 74.07, 85.82. Found,
%: C 75.93; H 12.37; N 7.27. C12H21NO. Calculated,
%: C 75.36; H 10.14; N 6.76.
1-(Hept-2-yn-1-yl)piperidine (IIb). Yield 61%,
bp 125–127°C (8 mm), nD25 = 1.5314. IR spectrum, ν,
cm–1: 2235 (C≡C), 1280 (C–N–C). 1H NMR spectrum,
δ, ppm: 0.87 t (3H, J = 7 Hz), 1.09–1.77 m (6H), 2.09 t
(2H), 2.41 m (4H), 3.41 m (4H), 3.18 s (2H). 13C NMR
spectrum, δC, ppm: 13.27, 18.19, 21.74, 23.73, 25.52,
30.79, 47.92, 53.16, 74.75, 85.33. Found, %: C 77.20;
H 11.72; N 6.92. C12H23N. Calculated, %: C 79.33;
H 12.85; N 7.82.
4-(Hept-2-yn-1-yl)morpholine (IIh). Yield 64%,
bp 120–123°C (8 mm), nD25 = 1.5275. IR spectrum, ν,
cm–1: 1120 (C–O–C), 1270 (C–N–C), 2245 (C≡C).
1H NMR spectrum, δ, ppm: 0.89 br.s (3H), 1.35 m
(4H), 2.16 m (2H), 3.26 s (2H), 2.45 m (4H), 3.62 m
(4H). 13C NMR spectrum, δC, ppm: 13.24, 18.09,
21.71, 30.69, 47.47, 52.12, 66.48, 74.07, 85.82. Found,
%: C 72.93; H 10.56; N 7.70. C11H19NO. Calculated,
%: C 72.93; H 10.50; N 7.73.
1-(Oct-2-yn-1-yl)piperidine (IIc). Yield 60%,
bp 129–131°C (8 mm), nD25 = 1.5310. IR spectrum, ν,
cm–1: 2230 (C≡C), 1190 (C–N–C). 1H NMR spectrum,
δ, ppm: 0.87 t (3H, J = 7 Hz), 1.23–1.53 m (8H),
1.60 m (4H), 2.16 t (2H, J = 7 Hz), 2.47 m (4H).
13C NMR spectrum, δC, ppm: 12.91, 18.65, 22.42,
24.42, 26.25, 27.80, 30.53, 47.20, 52.80, 75.05, 84.03.
4-(Hex-2-yn-1-yl)morpholine (IIi). Yield 73%,
bp 129–130°C (8 mm), nD25 = 1.4905. IR spectrum, ν,
cm–1: 1120 (C–O–C), 1190 (C–N–C), 2250 (C≡C).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 1 2010

SYNTHESIS OF 2,3-ACETYLENIC AMINES BY AMINOMETHYLATION OF ACETYLENES
47
1H NMR spectrum, δ, ppm: 0.89 br.s (3H), 1.35 m
(4H), 2.16 m (2H), 2.45 m (4H), 3.26 s (2H), 3.62 m
(4H). 13C NMR spectrum, δC, ppm: 13.24, 18.09,
21.71, 30.69, 47.47, 52.12, 66.48, 74.07, 85.82. Found,
%: C 75.93; H 12.37; N 7.27. C10H17NO. Calculated,
%: C 71.43; H 10.71; N 8.34.
1,12-Dimorpholinododeca-2,10-diyne (IVc).
Yield 70%, mp 70–72°C. IR spectrum, ν, cm–1: 1120
1
(C–O–C), 2275 (C≡C). H NMR spectrum, δ, ppm:
1.39 m (8H), 2.16 m (4H), 2.51 m (8H), 3.20 br.s (4H),
3.71 m (8H). 13C NMR spectrum, δC, ppm: 18.37,
28.32, 28.64, 47.72, 52.38, 66.87, 74.59, 85.28. Found,
%: C 69.98; H 9.01; N 7.47. C20H32N2O2. Calculated,
%: C 72.20; H 9.65; N 8.42.
4-(3-Phenylprop-2-yn-1-yl)morpholine (IIj).
Yield 98%, bp 130–131°C (2 mm), nD25 = 1.5657. IR
spectrum, ν, cm–1: 1120 (C–O–C), 1180 (C–N–C),
N,N,N′,N′-Tetramethyldeca-2,8-diyne-1,10-di-
amine (IVd) [19]. Yield 20%, bp 91°C (3 mm). IR
1
2265 (C≡C). H NMR spectrum, δ, ppm: 2.10–2.65 m
1
spectrum: ν 1270 cm–1 (C–N). H NMR spectrum, δ,
(4H), 3.29 s (2H), 3.10–3.74 m (4H), 7.04–7.34 m
(5H). 13C NMR spectrum, δC, ppm: 51.70, 52.38,
66.48, 81.23, 82.41, 123.23, 127.86, 128.31, 131.77.
Found, %: C 78.35; H 9.12; N 8.64. C13H15NO. Cal-
culated, %: C 77.60; H 7.45; N 6.99.
ppm: 1.47 t (4H, J = 6.87 Hz), 2.19 s (12H), 2.2–2.5 m
(4H), 3.11 s (4H). 13C NMR spectrum, δC, ppm: 18.65,
27.89, 43.80, 48.12, 75.66, 84.71. Found, %: C 75.9;
H 11.30; N 11.92. C14H24N2. Calculated, %: C 76.36;
H 10.91; N 12.72.
1-(Nona-2,7-diyn-1-yl)piperidine (IIIa). Yield
90%, bp 129–131°C (10 mm), nD25 = 1.5294. IR spec-
trum, ν, cm–1: 1200 (C–N–C), 1160 (C–O–C), 2260
N,N-Dimethyl-10-morpholinodeca-2,8-diyn-1-
1
amine (V). Yield 58%, bp 181°C (8 mm). H NMR
1
(C≡C). H NMR spectrum, δ, ppm: 1.81 s (1H),
spectrum, δ, ppm: 1.23 m (4H), 1.41 s (4H), 2.02 m
(4H), 2.19 s (6H), 2.31 br.s (4H), 3.19 s (2H), 3.21 s
(2H). 13C NMR spectrum, δC, ppm: 18.96, 26.93,
43.69, 47.60, 48.40, 52.41, 66.88, 74.70, 75.12, 84.90,
85.12. Found, %: C 73.26; H 9.93; N 10.70.
C16H26N2O. Calculated, %: C 73.28; H 9.93; N 10.69.
2.02 br.s (4H), 1.41 m (4H), 3.01 br.s (2H) 2.30 m
13
(4H), 1.41 m (4H), 1.22 m (2H). C NMR spectrum,
δC, ppm: 17.43, 17.73, 24.96, 25.8, 27.20, 27.33,
47.20, 52.70, 68.50, 74.61, 82.20, 86.00. Found, %:
C 79.24; H 9.46; N 7.25. C14H21N. Calculated, %:
C 82.76; H 10.34; N 6.80.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 08-03-00789) and by the Council for Grants at the
President of the Russian Federation (project no. NSh-
2349.2008.3).
4-(Nona-2,7-diyn-1-yl)morpholine (IIIb). Yield
54%, bp 133–135°C (10 mm), nD25 = 1.5287. IR spec-
1
trum, ν, cm–1: 2260 (C≡C), 1040 (N–C–N). H NMR
spectrum, δ, ppm: 1.41 m (4H), 1.80 s (1H), 2.03 br.s
(4H), 2.27 m (4H), 3.18 br.s (2H), 3.70 m (4H).
13C NMR spectrum, δC, ppm: 17.34, 17.68, 27.11,
27.39, 47.90, 52.40, 66.88, 68.40, 74.70, 82.40, 85.79.
Found, %: C 75.25; H 9.00; N 5.98. C13H17NO. Cal-
culated, %: C 76.09; H 9.28; N 6.83.
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1,9-Dipiperidinonona-2,7-diyne (IVa). Yield 71%,
bp 196–199°C (5 mm), nD25 = 1.5191. IR spectrum, ν,
cm–1: 2260 (C≡C), 1290 (C–N–C). 1H NMR spectrum,
δ, ppm: 1.37 br.m (4H), 1.80–2.20 m (4H), 2.47 m
(8H), 2.93 s (4H), 6.61 m (8H). 13C NMR spectrum,
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1,10-Dimorpholinodeca-2,8-diyne (IVb). Yield
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1
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