Aminomethylation of acetylene alcohols and their esters with gem-diamines catalyzed by complexes of d-transition and rare-earth metals

Article abstract of DOI:10.1134/S1070428011020023

An efficient synthetic procedure was developed for preparation of oxygen-containing propargylamines with high yields and selectivity by aminomethylation of propargyl alcohols and their esters with gem-diamines catalyzed by complexes and salts of d-transit

Full text of DOI:10.1134/S1070428011020023

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 2, pp. 161167. Pleiades Publishing, Ltd., 2011.
Original Russian Text  M.G. Shaibakova, I.G. Titova, A.G. Ibragimov, U.M. Dzhemilev, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47,
No. 2, pp. 173179.
Aminomethylation of Acetylene Alcohols and Their Esters
with gem-Diamines Catalyzed by Complexes
of d-Transition and Rare-Earth Metals
M. G. Shaibakova, I. G. Titova, A. G. Ibragimov, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, 450075 Russia
e-mail: ink@anrb.ru
Received May 25, 2009
Abstract—An efficient synthetic procedure was developed for preparation of oxygen-containing propargylamines
with high yields and selectivity by aminomethylation of propargyl alcohols and their esters with gem-diamines
catalyzed by complexes and salts of d-transition metals and lanthanides.
DOI: 10.1134/S1070428011020023
The interest to oxygen-containing propargylamines is
due to the possibility of their application as pharmaceuticals
exhibiting analgesic, antiarrhithmic, and spasmolytic action
and a havong low toxicity [1], and also as initial monomers
for the synthesis of hetero- and polycyclic compounds [2].
development of a one-pot synthesis of practically important
acyclic oxygen-containing propargylamines we examined
the aminomethylation of propargyl alcohols and their esters
with bisamine I and with symmetric higher gem-diamines
using as catalysts the salts and complexes of Cu, Mn, Ti,
Zr, Nb, Co, Fe, Sm, V, which formerly well catalyzed the
aminomethylation of the terminal acetylenes.
The known methods [3–6] of the preparation of oxy-
gen-containing propargylamines by the classic Mannich
reaction posses some limitations concerning their low
selectivity of these processes and the long reaction time
up to 115 h [5], and also the difficulties in the isolation
of the target heteroatomic acetylenes.
By the example of the reaction of 3-methylpent-1-yn-
3-ol (IIc) with N,N,N’,N’- tetramethylmethanediamine
(I) we investigated the effect of the metal nature and of
its ligand surrounding, of the solvent structure, and the
reaction conditions on the yield and the composition of
the aminomethylation products.
We recently reported on the mild aminomethylation in
high yields of terminal mono- and α, ω-diacetylenes us-
ing N,N,N’N’-tetramethylmethanediamine (I) and higher
gem-diamines in the presence of complexes and salts of
d-transition metals and lanthanides into the corresponding
propargylamines [7].
The studies showed that in the presence of CuCl
catalyst [at the molar ratio 3-methylpent-1-yn-3-ol–
bisamine I–CuCl 1 : 3 : 0.05] under argon within 6 h
6-(dimethylamino)-3-methylhex-4-yn-3-ol (IIIc) formed
in 92% yield (Scheme 1). On replacing CuCl with CuCl2
In extension of this research and also aiming at the
Scheme 1.
HO X
IIa_IId
N
+
IIIa_IIId
Catalyst
+
HO X
X OH
HO X
_(CH3)2NH
IVa_IVd
N
N
I
X = CH2 (a), CH2CH2 (b), CH3CH2C(CH3) (c), 1,1-cyclo-C6H10 (d).
161

SHAIBAKOVA et al.
162
under the above conditions (solven hexane, 63°C) com-
pound IIIc formed in 81% yield. The use as solvents of
C2H5OH, DMSO, and toluene resulted in a reduced yield
of compound IIIc. In some runs alongside the target
propargylamine IIIc formed also ~10% of 3,8-dimethyl-
deca-4,6-diyn-3,8-diol (IVc) resulting from the oxidative
coupling of initial compound IIc (Table 1).
and ethyl groups. Under the chosen conditions the amino-
methylation occurred exclusively at the active C–H bond
of the initial acetylene and did not involve the hydroxy
group as proved the presence of the hydroxy group signal
in the 1H NMR spectrum at 2.22 ppm and the correspond-
ing absorption band in the IR spectrum at 3620 cm–1.
In the developed optimum conditions (Table 1) the
aminomethylation of substituted propargyl alcohols
with bisamine I provides a possibility to obtain the cor-
responding propargylamines in fairly good yields. For
instance, the reaction of but-3-yn-1-ol (IIb) with bisamine
I under the action of the catalyst CuCl [(I)–(IIb)–CuCl
3 : 1 : 0.05, 80°C, 6 h] gave 4-(dimethylamino)pent-3-
yn-1-ol (IIIb) in 87% yield. In the aminomethylation
of propargyl alcohol (IIa) with diamine I catalyzed by
Sm(NO3)3·6H2O or Cp2TiCl2 4-(dimethylamino)but-2-
yn-1-ol (IIIa) was obtained in 59–65% yield. The ami-
nomethylation of 1-ethynylcyclohexanol with bisamine
I in the presence of the catalyst Sm(NO3)3·6H2O led to
the formation of 1-[3-(dimethylamino)prop-1-yn-1-yl]
cyclohexanol (IIId) in 91% yield.
The high catalytic activity and selectivity in the
aminomethylation of compound IIc with bisamine I
was observed in the presence of catalysts VO(acac)2 and
Sm(NO3)3·6H2O without solvent or in toluene solution.
At the use of these catalysts at the molar ratio (IIc)–(I)–
catalyst 1 : 3 : 0.05 in the toluene solution we obtained
compound IIIc in 78% yield, and without solvent, in
89% yield. The use of hexane as solvent resulted in the
reduction of the yield of compound IIIc to 35%.
In the 13C NMR spectrum of compound IIIa the
resonance signals of the acetylene sp-hybridized carbon
atoms were observed at 77.17 and 89.75 ppm. The carbon
atoms of the dimethylamino group gave rise to signals
at 43.89 ppm. In the 1H NMR spectrum the ethyl group
appeared as a triplet and quartet at 0.96 and 1.61 ppm
respectively. In the HMBC spectrum the cross peaks
corresponded to the coupling between the carbon atom
at the hydroxy group and the carbon atoms of the methyl
We further tried to carry out the aminomethylation
of acetylene alcohols with symmetric gem-diamines. To
this end we elaborated a preparative synthesis of gem-
diamines by catalytic transamination of bisamine I with
Table 1. The effect of the nature of catalyst and solvent on the yield of 6-(dimethylamino)-3-methylhex-4-yn-3-ol (IIIc)a
Catalyst
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
Cu(acac)2
CuBr
CuI
Solvent
–
Yield, %
92
Catalyst
CuI
Solvent
Yield, %
DMSO
23b
–
toluene
hexane
C2H5OH
DMSO
–
15
26c
ZrCl4
–
NbCl5
–
2
8
CoCl2
–
2
53d
87
Co(acac) 2
SnCl2
–
6
–
–
toluene
hexane
C2H5OH
DMSO
–
48
81e
MnCl2
–
15
80
72
35
89
78
46
2
Sm(NO3)3·6H2O
Sm(NO3)3·6H2O
Sm(NO3)3·6H2O
VO(acac) 2
VO(acac) 2
VO(acac) 2
Fe(acac)3
Cp2TiCl2
Cp2ZrCl2
–
5
toluene
76
hexane
42
–
–
14
toluene
–
17
hexane
CuI
toluene
hexane
C2H5OH
32
–
–
–
CuI
46
–
CuI
11
3
a Reaction conditions: molar ratio (I)–(IIc)–catalyst 3 : 1 : 0.05, 80°C, 6 h. Yield of compound IVc: b 31%, c 10%, d 20%, e10%.
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AMINOMETHYLATION OF ACETYLENE ALCOHOLS AND THEIR ESTERS
163
Table 3. Effect of catalyst nature on the yield of oxygen-
containing propargylamines in the reaction between propargyl
esters and N,N,N',N'-tetramethylmethanediamine (I)a
Table 2. Effect of the structure of gem-diamines and propar-
gyl alcohols on the yield of target propargylaminesa
Diamine no.
Alcohol no.
Yield, %
Catalyst
Acetylene ester
Yield, %
V
VI
V
IIa
IIa
IIb
VIIa, 59
VIIIa, 60
VIIb, 92
Sm(NO3)3·6H2O
CuCl
IXa
IXa
IXb
IXb
IXc
IXc
Xa, 55
Xa, 65
Xb, 55
Xb, 62
Xc, 70
Xc, 98
Sm(NO3)3·6H2O
CuCl
VI
V
IIb
IIc
IIc
IId
IId
VIIIb, 60
VIIc, 62
VIIIc, 48
VIId, 37
VIIId, 52
Sm(NO3)3·6H2O
VI
V
CuCl
a Molar ratio bisamine I–propargyl ester–catalyst 3 : 1 : 0.05, 80°C,
6 h.
VI
a Molar ratio acetylene alcohol–gem-diamine–catalyst 1 : 1 : 0.05,
we studied the reaction of propargyl acetate (IXa) with
N,N,N',N'-tetramethylmethanediamine in the presence of
complex catalysts under the above described conditions
(2-propynyl acetate–bisamine–catalyst, 1 : 3 : 0.05, 6 h,
80°C) giving 4-(dimethylamino)but-2-yn-1-yl acetate
(Xa) in 65% yield (Table 3).
80°C, 6 h.
secondary amines of various structures [8]. It turned out
that the synthesized gem-diamines in the presence of the
catalysts Sm(NO3)3·6H2O or CuCl under the above de-
veloped conditions (Table 1) enter the amino-methylation
reaction with acetylene alcohols affording the correspond-
ing propargylamines (Table 2).
The aminomethylation of 2-propynyl propionate
(IXb) and 2-propynyl 3-methylbutanoate (IXc) under the
above described conditions catalyzed by Sm(NO3)3·6H2O
and CuCl led to the formation of 4-(dimethylamino)
but-2-yn-1-yl propionate (Xb) and 4-(dimethylamino)
but-2-yn-1-yl 3-methylbutanoate (Xc) in 65 and 98%
yields respectively (Scheme 3, Table 3).
Under the action of 5 mol% of CuCl 1,1'-methylene-
dipiperidine (V) and 4,4'-methylenedimorpholine (VI)
reacted with acetylene alcohols like propargyl alcohol
(IIa), but-3-yn-1-ol (IIb), 3-methylpent-1-yn-3-ol (IIc),
1-ethynylcyclohexanol (IId) providing the corresponding
propargylamines VIIa–VIId, VIIIa–VIIId in 37–92%
yields (Scheme 2, Table 2).
Scheme 3.
To compare the activity of acetylene alcohols and
their esters in the aminomethylation with gem-diamines
R
O
_
O
N
IXa IXc
Catalyst
Scheme 2.
R
O
+
O
Xa_Xc
N
N
N
N
I
Y
Y
V, VI
R = CH3 (a), C2H5 (b), CH2CH(CH3)2 (c).
+
HO X
Esters IXa–IXc like acetylene alcohols IIa–IId react
with the higher symmetric gem-diamines V, VI to provide
the corresponding oxygen-containing propargylamines
XI, XII (Scheme 4).
IIa_IId
Y
N
Catalyst
The structure of compound XIc was proved by 1D
HO X
1
and 2D H and 13C NMR spectroscopy with the use of
_
VIIa_VIId, VIIIa_VIIId
HN
X
the results of homonuclear COSY and heteronuclear cor-
relation experiments HSQC and HMBC.
Y = CH2 (V, VII), O (VI, VIII); X = CH2 (a), CH2CH2
(b), CH3CH2C(CH3) (c), 1,1-cyclo-C6H10 (d).
In the upfield part of the COSY spectrum is clearly
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SHAIBAKOVA et al.
164
Scheme 4.
Table 4. Effect of catalyst nature and structure of initial gem-
diamines on the yield of propargylaminesa
R
O
O
gem-
Diamine
Acetylene
Catalyst
Yield, %
_
ester
IXa
IXb
IXc
IXa
IXb
IXc
IXa IXc
+
Sm(NO3)3·6H2O
Sm(NO3)3·6H2O
CuCl
V
V
XIa, 57
XIb, 66
XIc, 54
XIIa, 33
XIIb, 54
XIIc, 48
N
N
Y
Y
V
V, VI
Sm(NO3)3·6H2O
CuCl
VI
VI
VI
Y
CuCl
Catalyst
N
a
R
O
Molar ratio gem-diamine–propargyl ester–catalyst 1 : 1 : 0.05, 80°C,
_
HN
X
O
6 h.
XIa_XIc, XIIa_XIIc
and lanthanides opens a convenient and promising way
to the synthesis of propargylamines with hydroxy and
alkoxycarbonyl substituents.
Y = CH2 (V, XI), O (VI, XII); R = CH3 (a), C2H5 (b),
CH2CH(CH3)2 (c).
EXPERIMENTAL
seen the system of the isobutyl group: δ(CH3) 0.96, δ(H)
2.12, δ(CH2) 2.22 ppm. The piperidine fragment of mol-
ecule XIc consists of three interrelated multiplet proton
signals (δ 2.48, 1.61, 1.42 ppm). The methylene groups
δ(CH2) 3.28, δ(CH2) 4.70 ppm contain a pronounced
correlation peak in the COSY experiment indicating the
presence of long-range proton couplings through five
bonds, practically unseen in the 1D spectra.
The reaction progress was monitored by TLC on Silu-
fol plates with eluents acetone–CH3OH, 9 : 2–3, acetone-
CHCl3, 9 : 1, acetone–C2H5OH, 9 : 1. The propargyl alco-
hols and propargyl esters of carboxylic acids used in the
study were commercial products, and the used solvents
were of chemically pure grade. 1H and 13C NMR spectra
were registered on spectrometers Jeol FX-90Q [22.5
(13C), 90 MHz (1H)], Bruker Avance 400 [100.62 (13C),
400.13 MHz (1H)], solvent CDCl3, internal reference
TMS. IR spectra were recorded on a spectrophotometer
Specord 75 IR in KBr. The elemental composition of
compounds was determined on an analyzer Karlo Erba-
1106. The products were analyzed on a chromatograph
Chrom-5, flame-ionization detector, stationary phase
SE-30, columna 2000×3 mm, ramp from 50 to 280°C,
heating rate 8 deg/min, vaporizer temperature 300°C,
detector at 250°C.
In the 1D spectrum of compound XIc 11 nonequiva-
lent signals are observed, among which three carbon
signals in the strong field have a double intensity due to
coinciding pairs of signals of the gem-dimethyl group
δ(CH3) at 22.11 ppm and α- and β-carbon atoms of the
piperidine ring δ(Cα) 53.02, δ(Cβ) 25.63 ppm. The down-
field signal corresponds to the carboxy group [δ(CO)
171.87 ppm] and the C≡C bond (81.92, 78.81 ppm).
The unambiguous assignment of the signals in the 13C
NMR spectra were performed with the help of HSQC and
HMBC experiments. The long-range couplings through
three bonds were observed in the HMBC experiment
through an oxygen atom HC10/C11 and through a nitrogen
atom HC7/C2,6 thus unambiguously proving the assumed
structure of compound XIc.
Aminomethylation of propargyl alcohols and their
esters. General procedure. Under an argon atmosphere
a mixture of 1–3 mmol of an appropriate gem-diamine,
1 mmol of acetylene alcohol or acetylene ester, and
0.05 mmol of catalyst was stirred for 6 h at 80°C. The
reaction mixture was separated from the catalyst, the
reaction product was isolated by vacuum distillation.
The aminomethylation of propargyl esters with the
bisamine based on piperidine (V) led to higher yields
than at the application of the analogous derivative of
morpholine (VI) (Table 4).
Thus the aminomethylation of acetylene alcohols and
propargyl esters of carboxylic acids with gem-diamines
catalyzed by salts and complexes of transition metals
4-(Dimethylamino)but-2-yn-1-ol (IIIa). Yield 65%,
bp 60–62°C (8 mm Hg), [n]D22 1.4658. 1H NMR spectrum,
δ, ppm: 2.15 s (6H, 2CH3), 2.32 s (OH), 3.05 s (2H,
CH2), 4.24 s (2H, CH2). 13C NMR spectrum, δ, ppm:
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AMINOMETHYLATION OF ACETYLENE ALCOHOLS AND THEIR ESTERS
165
43.72, 47.69, 50.13, 79.18, 84.49. Found, %: C 66.06;
H 10.96; N 10.51. C7H13NO. Calculated, %: C 66.14;
H 10.24; N 11.02.
3-Methyl-6-piperidinohex-4-yn-3-ol (VIIc). Yield
62%, bp 126–128°C (8 mm Hg). IR spectrum, ν, cm–1:
3620 (COH), 1030 (NC). H NMR spectrum, δ, ppm:
1
0.98 t (3H, CH3, J 7.4 Hz), 1.40 s (3H, CH3), 1.50–1.56 m
(2H, CH2), 1.57 q (2H, J 7.3 Hz), 1.63–1.68 m (4H,
2CH2), 2.41 br.s (OH), 2.38–2.42 m (4H, 2CH2), 3.21 s
(2H, CH2). 13C NMR spectrum, δ, ppm: 9.14, 23.80,
25.60, 29.41, 36.58, 47.69, 53.15, 68.32, 79.15, 89.07.
Found, %: C 70.57; H 12.62; N 8.77. C12H21NO. Calcu-
lated, %: C 70.17; H 12.28; N 8.19.
5-(Dimethylamino)pent-3-yn-2-ol (IIIb). Yield 87%,
bp 65–67°C (7 mm Hg), [n]D24 1.5815. 1H NMR spectrum,
δ, ppm: 1.97 s (6H, 2CH3), 2.24 br.s (OH), 2.31 t (2H,
CH2, J 6 Hz), 3.17 s (2H, CH2), 3.33 t (2H, CH2, J 6 Hz).
13C NMR spectrum, δ, ppm: 22.26, 44.70, 47.11, 60.10,
75.66, 81.82. Mass spectrum, m/z (Irel, %): [M]+ 127
(79.4), 126 (100), 108 (33.53), 96 (38.3), 94 (42.35),
82 (91.3), 81 (24.7), 58 (31.7), 53 (44.11), 44 (54.7), 42
(92.9). Found, %: C 62.96; H 9.90; N 12.24. C6H11NO.
Calculated, %: C 63.72; H 9.73; N 12.39.
1-(3-Piperidino-1-prop-1-yn-1-yl)cyclohexanol
(VIId). Yield 55%, bp 147–149°C (7 mm Hg). 1H NMR
spectrum, δ, ppm: 1.08–1.16 m (2H, CH2), 1.18–1.30 m
(2H, CH2), 1.38–1.45 m (4H, 2CH2), 1.43–1.56 m (4H,
2CH2), 2.08–2.20 m (4H, 2CH2), 2.74 br.s (OH), 3.00 s
(2H, CH2), 3.90–4.00 m (4H, 2CH2). 13C NMR spec-
trum, δ, ppm: 22.65, 23.44, 24.96, 39.66, 47.14, 52.50,
67.52, 77.67, 89.49. Found, %: C 76.56; H 10.10; N 6.13.
C14H23NO. Calculated, %: C 76.02; H 10.41; N 6.33.
6-(Dimethylamino)-3-methylhex-4-yn-3-ol (IIIc).
Yield 92%, bp 46–48°C (1 mm Hg), [n]D24 1.4830. IR
spectrum, ν, cm–1: 3620 (COH), 2265 (C≡C). 1H NMR
spectrum, δ, ppm: 0.97 t (3H, CH3, J 7.4 Hz), 1.40 s (3H,
CH3), 1.61 q (2H, CH2, J 7.4 Hz), 2.20 s (6H, 2CH3),
2.22 br.s (OH), 3.18 s (2H, CH2). 13C NMR spectrum,
δ, ppm: 9.19, 29.50, 36.71, 43.89, 47.79, 68.03, 77.22,
89.74. Found, %: C 70.06; H 9.64; N 9.34. C9H17NO.
Calculated, %: C 69.69; H 10.96; N 9.05.
4-Morpholino-4-but-2-yn-1-ol (VIIIa). Yield 50%,
bp 128–131°C (7 mm Hg), nD20 1.6655. IR spectrum, ν,
1
cm–1: 3640 (COH), 1220 (NC), 1100 (COC). H NMR
spectrum, δ, ppm: 2.27 br.s (OH), 2.32–2.38 m (4H,
2CH2), 3.38 s (2H, CH2), 3.35–3.44 m (4H, 2CH2),
4.50 s (2H, CH2). 13C NMR spectrum, δ, ppm: 46.65,
51.58, 51.62, 65.95, 79.46, 81.13. Found, %: C 61.29;
H 8.68; N 9.93; C8H13NO2. Calculated, %: C 61.93;
H 8.39; N 9.03.
1-[3-(Dimethylamino)prop-1-yn-1-yl]-cyclohex-
anol (IIId). Yield 91%, mp 72–74°C. IR spectrum, ν,
cm–1: 3635 (COH), 2265 (C≡C). 1H NMR spectrum, δ,
ppm: 1.49–1.53 m (6H, 3CH2), 2.18 s (2H, CH2), 2.20 s
(6H, 2CH3), 2.79 br.s (OH), 4.00–4.04 m (4H, 2CH2).
13C NMR spectrum, δ, ppm: 23.30, 25.16, 40.11, 43.75,
47.76, 68.08, 78.17, 88.06. Found, %: C 72.22; H 10.43;
N 8.44. C11H19NO. Calculated, %: C 72.93; H 10.50;
N 7.73.
5-Morpholinopent-3-yn-1-ol (VIIIb). Yield 60%,
bp 131–134°C (7 mm Hg). IR spectrum, ν, cm–1: 3644
(COH), 1030 (NC), 1100 (COC). 1H NMR spectrum, δ,
ppm: 2.04 s (OH), 2.00–2.10 m (4H, CH2), 2.17 t (2H,
CH2, J 6.6 Hz), 3.25–3.36 m (4H, 2CH2), 3.33 s (2H,
CH2), 3.70 t (2H, CH2, J 7.2 Hz). 13C NMR spectrum,
δ, ppm: 22.39, 47.29, 52.45, 60.24, 66.86, 75.06, 82.58,
82.21. Found, %: C 63.7; H 8.79; N 8.05. C10H17NO.
Calculated, %: C 63.91; H 8.88; N 8.28.
4-Piperidino-but-2-yn-1-ol (VIIa). Yield 60%, bp
110–147°C (7 mm Hg). IR spectrum, ν, cm–1: 3640
1
(COH), 1040 (NC). H NMR spectrum, δ, ppm: 1.30–
1.39 m (2H, CH2), 1.47–1.58 m (4H, 2CH2), 2.47 br.s (4H,
2CH2), 2.47 br.s (OH), 3.19 s (2H, CH2), 4.17 s (2H, CH2).
13C NMR spectrum, δ, ppm: 23.57, 25.29, 47.55, 54.08,
54.87, 79.75, 81.05. Found, %: C 70.29; H 9.68; N 9.93.
C9H15NO. Calculated, %: C 70.59; H 9.80; N 9.15.
3-Methyl-6-morpholinohex-4-yn-3-ol (VIIIc). Yield
48%, bp 135–137°C (8 mm Hg), nD20 1.6672. IR spectrum,
ν, cm–1: 3620 (COH), 1120 (COC), 1030(NC). 1H NMR
spectrum, δ, ppm: 0.94 t (3H, CH3, J 7.4 Hz), 1.36 s (3H,
CH3), 1.59 q (2H, CH2, J 7.4 Hz), 2.30–2.36 m (4H,
2CH2), 2.58 br.s (OH), 3.22 s (2H, CH2), 3.30–3.39 m
(4H, 2CH2). 13C NMR spectrum, δ, ppm: 8.87, 29.14,
36.34, 46.89, 51.71, 66.15, 66.47, 76.39, 89.84. Found,
%: C 67.56; H 9.94; N 7.37. C11H19NO2. Calculated, %:
C 67.01; H 9.64; N 7.11.
5-Piperidino-1-pent-3-yn-1-ol (VIIb). Yield 92%,
bp 109–111°C (7 mm Hg), [n]D20 1.6600. IR spectrum,
ν, cm–1: 3640 (COH), 1100 (NC). 1H NMR spectrum, δ,
ppm: 1.05–1.18 m (2H, CH2), 1.27–1.43 m (4H, 2CH2),
1.95 br.s (OH), 2.11–2.24 m (4H, 2CH2), 2.34 br.s (2H,
CH2), 3.09 s (2H, CH2). 13C NMR spectrum, δ, ppm:
14.88, 23.48, 25.15, 47.45, 52.80, 60.40, 75.47, 82.21.
Found, %: C 71.70; H 10.79; N 8.05. C10H17NO. Calcu-
lated, %: C 71.86; H 10.18; N 8.38.
1-(3-Morpholinoprop-1-yn-1-yl)cyclohexanol
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SHAIBAKOVA et al.
166
(VIIId). Yield 59%, bp 158–161°C (7 mm Hg), nD20
1.6420. H NMR spectrum, δ, ppm: 1.25–1.35 m (6H,
1H NMR spectrum, δ, ppm: 1.15 t (3H, CH3, J 7.4 Hz),
1.43 m (2H, CH2), 1.60–1.63 m (4H, 2CH2), 2.38 q (2H,
CH2, J 7.6 Hz), 2.43–2.58 m (2H, CH2), 3.29 s (2H, CH2),
4.71 s (2H, CH2). 13C NMR spectrum, δ, ppm: 8.76,
23.34, 25.54, 27.13, 47.68, 50.10, 52.10, 78.71, 82.15,
173.35. Found, %: C 68.29; H 8.91; N 6.23. C12H19NO2.
Calculated, %: C 68.90; H 9.09; N 6.70.
1
3CH2), 1.40–1.48 m (4H, 2CH2), 1.70–1.81 m (4H,
2CH2), 2.45–2.55 m (4H, 2CH2), 3.22 s (2H, CH2),
3.37 br.s (OH), 3.60–3.70 m (4H). 13C, δ, ppm: 23.08,
24.97, 39.70, 46.92, 51.69, 66.15, 67.71, 77.28, 89.92.
Found, %: C 69.26; H 7.2; N 6.27; C13H21NO2. Calcu-
lated, %: C 69.95; H 9.42; N 6.28.
4-Piperidinobut-2-yn-1-yl 3-methylbutanoate
(XIc). Yield 54%, bp 156–158°C (7 mm Hg), nD21 1.4672.
IR spectrum, ν, cm–1: 1270 (NC), 1190 (RCO2), 1120
4-(Dimethylamino)but-2-yn-1-yl acetate (Xa). Yield
65%, bp 69–70°C (7 mm Hg), nD21 1.6803. IR spectrum,
ν, cm–1: 1210 (NC), 1190 (RCO2), 1110 (COC). 1H NMR
spectrum, δ, ppm: 2.09 s (3H, CH3), 2.90 s (6H, 2CH3),
3.28 s (2H, 2CH3), 4.71 s (2H, CH2). 13C NMR spec-
trum, δ, ppm: 20.66, 43.99, 47.91, 52.32, 79.00, 81.89,
170.16, 77.28, 89.92. Found, %: C 61.90; H 8.84; N 7.84.
C8H13NO2. Calculated, %: C 61.93; H 8.39; N 9.03.
1
(COC). H NMR spectrum, δ, ppm: 0.96 d (6H, 2CH3,
J 7 Hz), 1.35–1.46 m (2H, CH2), 1.56–1.68 m (2H, CH2),
2.06–2.19 m (CH), 2.17–2.25 m (2H, CH2), 2.41–2.55 m
(2H, CH2), 3.28 s (2H, CH2), 4.70 s (2H, CH2). 13C NMR
spectrum, δ, ppm: 22.11, 23.65, 25.46, 25.63, 42.80,
47.56, 51.86, 53.02, 78.81, 81.92, 171.87. Found, %:
C 70.35; H 9.35; N 5.62. C14H23NO2. Calculated, %:
C 70.89; H 9.70; N 5.91.
4-(Dimethylamino)but-2-ynyl propionate (Xb).
Yield 62%, bp 91–93°C (7 mm Hg), nD21 1.5285. IR spec-
trum, ν, cm–1: 1190 (RCO2), 1180 (COC), 1030, (NC).
1H NMR spectrum, δ, ppm: 1.12 t (3H, CH3, J 7.6 Hz),
2.29 s (6H, 2CH3), 2.35 q (2H, CH2, J 7.6 Hz), 3.25 s (2H,
CH2), 4.70 s (2H, CH2). 13C NMR spectrum, δ, ppm: 8.64,
28.62, 44.29, 47.37, 54.05, 79.29, 81.05, 173.24. Found,
%: C 63.98; H 8.46; N 8.34. C9H15NO2. Calculated, %:
C 63.91; H 8.88; N 8.28.
4-Morpholin-4-ylbut-2-yn-1-ylacetate (XIIa).
21
Yield 33%, bp 150–154°C (7 mm Hg), nD 1.6330.
IR spectrum, ν, cm–1: 1230 (NC), 1190 (RCO2), 1190
1
(COC). H NMR spectrum, δ, ppm: 2.02 s (3H, CH3),
2.39–2.50 m (4H, 2CH2), 3.31 s (2H, CH2), 3.61–3.71 m
(4H, 2CH2), 4.62 s (2H, CH2). 13C NMR spectrum, δ,
ppm: 20.30, 46.44, 46.93, 51.98, 66.55, 81.11, 82.98,
169.96. Found, %: C 59.26; H 7.89; N 6.60. C10H15NO3.
Calculated, %: C 60.91; H 7.61; N 7.11.
4-(Dimethylamino)but-2-yn-1-yl 3-methylbutano-
ate (Xc). Yield 98%, bp 99–101°C (7 mm Hg), nD21
1.5270. IR spectrum, ν, cm–1: 1230 (NC), 1180 (RCO2),
4-Morpholinobut-2-yn-1-yl propionate (XIIb).
Yield 54%, bp 145–148°C (7 mm Hg), nD21 1.6385. IR
spectrum, ν, cm–1: 1190 (RCO2), 1150 (COC), 1100 (NC).
1H NMR spectrum, δ, ppm: 2.56 t (3H, CH3, J 7.6 Hz),
2.27–2.39 m (4H, 2CH2), 1.16 q (2H, CH2, J 6.8 Hz),
3.33 s (2H, CH2), 3.45–3.57 m (4H, 2CH2), 4.72 s (2H,
CH2). 13C NMR spectrum, δ, ppm: 8.67, 26.96, 47.07,
51.83, 52.00, 66.43, 79.30, 81.18, 173.12. Found, %:
C 62.15; H 7.82; N 6.02. C11H17NO3. Calculated, %:
C 62.56; H 8.06; N 6.64.
1
1130 (COC). H NMR spectrum, δ, ppm: 0.93 c (6H,
2CH3), 1.80–1.89 m (CH), 1.97 d (2H, CH2, J 6.8 Hz),
2.04 d (6H, 2CH3), 3.04 d (2H, CH2, J 6 Hz), 4.47 s (2H,
CH2). 13C NMR spectrum, δ, ppm: 20.66, 43.99, 47.91,
52.32, 79.00, 81.89, 170.16, 77.28, 89.92. Found, %:
C 67.29; H 9.23; N 6.71. C11H19NO2. Calculated, %:
C 67.01; H 9.64; N 7.11.
4-Piperidino-1-but-2-yn-1-yl acetate (XIa). Yield
57%, bp 128–130°C (7 mm Hg), nD21 1.4705. IR spectrum,
ν, cm–1: 1210 (NC), 1190 (COC), 1180 (RCO2). 1H NMR
spectrum, δ, ppm: 1.39–1.45 m (2H, CH2), 1.53–1.64 m
(4H, 2CH2), 2.08 s (3H, CH3), 2.40–2.51 m (4H, 2CH2),
3.28 s (2H, CH2), 4.70 s (2H, CH2). 13C NMR spectrum,
δ, ppm: 20.36, 23.41, 24.55, 47.16, 52.70, 78.89, 82.76,
169.74. Found, %: C 67.68; H 8.74; N 7.13. C11H17NO2.
Calculated, %: C 67.69; H 8.72; N 7.18.
4-Morpholinobut-2-yn-1-yl 3-methylbutanoate
(XIIc). Yield 48%, bp 147–150°C (7 mm Hg), nD21 1.4751.
IR spectrum, ν, cm–1: 1220 (NC), 1190 (RCO2), 1020
(COC). 1H NMR spectrum, δ, ppm: 1.05 d (6H, 2CH3),
1.99–2.10 m (CH), 2.15–2.25 m (4H, 2CH2), 2.29 d (2H,
CH2, J 3.4 Hz), 3.24 s (2H, CH2), 3.59–3.64 m (4H,
2CH2), 4.72 s (2H, CH2). 13C NMR spectrum, δ, ppm:
21.75, 25.10, 47.18, 51.83, 52.66, 66.86, 79.39, 81.00,
173.43. Found, %: C 65.05; H 8.39; N 6.88. C13H21NO3.
Calculated, %: C 65.27; H 8.79; N 5.86.
4-Piperidino-1-but-2-yn-1-yl propionate (XIb).
Yield 66%, bp 149–151°C (8 mm Hg), nD21 1.5259. IR
spectrum, ν, cm–1: 1180 (RCO2), 1150 (COC), 1060 (NC).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

AMINOMETHYLATION OF ACETYLENE ALCOHOLS AND THEIR ESTERS
167
Scriven, E.F.V., Oxford: Pergamon, Press, 1996, vol. 5,
p. 245.
ACKNOWLEDGMENT
The study was carried out under the financial sup-
port of the Russian Foundation for Basic Research
(grant no. 08-03-00789) and of the Council for grants
of the President of the Russian Federation (grant NSh-
2349.2008.3).
3. Chukhadzhyan, E.O., Gevorkyan, A.R., Chukhadzhyan,
El.O., and Shakhatuni, K.G., Zh. Org. Khim., 2000, vol. 36,
p. 1304.
4. Praliev, K.D., Kabdraisova, A.Zh., and Fomicheva, E.E.,
Abstracts of Papers, III Mezhdunar. nauchn. konf. “Sovre-
mennye tendentsii razvitiya nauki v tsentral’noi Azii” (3rd
Int. Sci. Conf. on Contemporary Trends of Development on
Science and in Central Asia), Almaty, 2007, p. 293.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011