ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 7, p. 1175.
Original Russian Text A.A. Gevorkyan, A.S. Arakelyan, A.A. Movsisyan, Zh.L. Dzhandzulyan, K.A. Petrosyan, 2006, published in Zhurnal Obshchei
Khimii, 2006, Vol. 76, No. 7, p. 1223.
Pleiades Publishing, Inc., 2006.
LETTERS
TO THE EDITOR
Improved Procedure of Acetylene Aminomethylation
A. A. Gevorkyan, A. S. Arakelyan, A. A. Movsisyan,
Zh. L. Dzhandzulyan, and K. A. Petrosyan
Institute of Organic Chemistry, National Academy of Sciences of Armenia,
ul. Z. Sarkavagi 167A, Erevan, 375091 Armenia
e-mail: agevork@sci.am
Received December 30, 2005
DOI: 10.1134/S1070363206070310
Propragylic amines are the reagents widely applied
in organic synthesis. They become much more signi-
ficant after discovery of the cyclization of quarternary
ammonium salts obtained from them affording various
polycyclic compounds [1]. Among the methods for
preparation of propargyl amines one of the most
useful is the Mannich aminomethylation of 1-alkynes.
As a rule, this reaction is conducted using dioxane or
alcohol as solvents to achieve yield about 50 70%
[2 7]. The main disadvantage of this method is long
reaction duration and use of organic solvents. To
obtain products in a high yield, sometimes the reac-
tion mixture should be heated for 8 to 60 h [2 7].
80% [4]; 1-diethylamino-4-benzyloxy-2-propyne,
bp 170 172 C (11 mm Hg), yield 69%; 1-piperidino-
3-phenyl-2-propyne, bp 160 165 C (11 mm Hg),
yield 72.4% [6]; 1-morpholino-3-phenyl-2-propyne,
bp 165 168 C (11 mm Hg), yield 75.6% [6]. Struc-
ture of each amine was confirmed additionally by the
1
data of H NMR spectroscopy.
Under these conditions propargyl alcohol formed
polymeric substance, as we reported earlier [5], and
dimethylethynylcarbinol returned unchanged [3]. The
reasons for such failure are under study.
REFERENCES
We found that aminomethylation of acyetylenes
can be considerably accelerated (the reaction duration
is 4-6 h only) when the reaction is conducted not
alongside the common procedure (in a solvent, e.g.,
15 30 ml of dioxane per 0.1 mol of acetylenic com-
pound [2 7]), but without any solvent, by reaction
of acetylenic compound with small excess of para-
ormaldehyde and secondary amine (1.1 to 1.3 mol per
1 mole of acetylenic compound) in the presence of a
few drops of suspension formed from oversaturated
solution of cuprous chloride in DMF (1 g of the salt
in 3.5 ml of the solvent). This reagent mixture upon
heating in the temperature range 95 to 105 C for
4 6 h the yields aminomethylation repeatedly from
70 to 80%.
1. Babayan, A.T., Vnutrimolekulyarnye peregruppirovki
solei chetyrekhzameshchennogo ammoniya (Intramo-
lecular Rearrangements of the Salts of Tetrasubstututed
Ammonium), Erevan: Izdatel’stvo Akademii Nauk
Armyanskoi SSR, 1976, pp. 159 348.
2. Mannich, C. and Chang, Fu Tsong, Ber., 1933,
vol. 66B, p. 418; C.A., 1933, p. 2940.
3. Jones, E.R.H., Marszak, I., and Bader, H., J. Chem.
Soc., 1947, no. 9, p. 1578.
4. Coffman, D.D., J. Am. Chem. Soc., 1935, vol. 57,
no. 10, p. 1978.
5. Chukhadzhyan, E.O., Gevorkyan, A.R., Chukhad-
zhyan, E.O., and Shakhatuni, K.G., Zh. Org. Khim.,
2000, vol. 36, no. 9, p. 1304.
R C CH + CH2=O + HNR2
CuCl
69 80%
6. Chukhadzhyan, E.O., Doctorate (Chem.) Dissertation,
R C CCH2NR2 .
Erevan, 1985.
By this procedure we synthesized the following
series of acetylenic amines: 1-diethylamino-3-phe-
nyl-2-propyne, bp 133 135 C (11 mm Hg) yield 70
7. Osyan, A.M., Karapetyan, V.E., Grigoryan, V.V., Ba-
bayan, A.T., and Kocharyan, S.T., Khim. Zh. Armenii,
1997, vol. 40, no. 3 4, p. 157.
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