330
GRIGORYAN et al.
amounts of corresponding amines with methyl -chlo-
rovinyl ketone in absolute ether. Their elemental
analyses were consistent with calculation. The salts
were obtained as hygroscopic syrups, Rf 0.47 (I), 0.52
(II), and 0.45 (III). The IR spectra contained, along
In a similar way, from 14.8 g of salt III we ob-
tained 4.5 g (70%) of dimethyl(prop-2-yn-1-yl)amine,
bp 75 76 C (680 mm), n2D0 1.4186 [8], mp 147 148 C
(picrate); mixture with an authentic sample gave no
melting point depression. From the residual reaction
mixture, 6.6 g (41.5%) of triacetylbenzene, mp 159
160 C [4], was isolated. Its mixture with an authentic
sample gave no melting point depression.
1
with bands at 1620 and 1680 cm (C=C, C=O), the
following bands: 690, 775, 1450, 1580, 1600, and
1
2240 cm (I, monosubstituted benzene ring and di-
1
substituted acetylene); 2230 cm (II, disubstituted
The IR spectra were recorded on a Specord 75 IR
spectrometer in mineral oil. TLC was carried out on
the Silufol UV-254 plates, eluent n-butanol ethanol
water acetic acid (10:7:6:4 v/v), development in
iodine vapor. The melting points were measured on a
Boetius hot stage equipped with an RNMK-0.5
microscope.
acetylene); and 2190 cm 1 (III, terminal acetylene).
Aquoues-alkaline cleavage of salts I III. A solu-
tion of 2.64 g of compound I was kept at room tem-
perature for 24 h. No formation of amine and carbonyl
compound was observed. The reaction mixture was
treated with a double molar amount (1.15 g) of potas-
sium hydroxide, left to stand for a day at room tem-
perature, after which it was heated on a boiling water
bath for 4 h, extracted with ether, and dried over
magnesium sulfate. The ether was removed, and the
residue was distilled in a vacuum to obtain 1.45 g
(91.2%) of dimethyl(3-phenylprop-2-yn-1-yl)amine,
bp 106 107 C (1 mm Hg), n2D0 1.5465 [5], mp 117
118 C (picrate), mixture with an authentic sample
gave no melting point depression. Acetone 2,4-dinitro-
phenylhydrazone, 0.6 g (29%), was precipitated, mp
126 127 C [6]; its mixture with an authentic sample
gave no melting point depression. Acidification of the
residual reaction mixture and subsequent distillation
gave 27% (by titrimetry) of formic acid as a charac-
teristic white precipitate with a mercury dichloride
solution.
REFERENCES
1. Babayan, A.T., Indzhikyan, M.G., and Minasyan, R.B.,
Arm. Khim. Zh., 1970, vol. 23, no. 3, p. 234.
2. Minasyan, R.B., Indzhikyan, M.G., and Babayan, A.T.,
Arm. Khim. Zh., 1969, vol. 22, no. 1, p. 23.
3. Babayan, A.T., Indzhikyan, M.G., Minasyan, R.B., and
Kinoyan, F.S., Arm. Khim. Zh., 1970, vol. 23, no. 3,
p. 240.
4. Ovakimyan, M.Zh., Cand. Sci. (Chem) Dissertation,
Yerevan, 1970.
5. Babayan, A.T., Grigoryan, Zh.V., and Chobanyan, P.S.,
Zh. Org. Khim., 1971, vol. 17, no. 11, p. 2253.
6. Dictionary of Organic Compounds, Heilbron, J. and
Bunbury, H. M., Eds., London: Eyre and Spottswoode,
1946, vol. 3. Translated under the title Slovar’ organi-
cheskikh soedinenii, Moscow: Inostrannaya Literatura,
1949, vol. 2, p. 13.
7. Babayan, A.T. and Terzyan, A.T., Dokl. Akad. Nauk
Arm. SSR, 1948, vol. 9, no. 1, p. 105.
8. Davtyan, N.M., Martirosyan, G.T., and Babayan, A.T.,
Zh. Org. Khim., 1968, vol. 4, no. 4, p. 556.
In a similar way, from 6.1 g of salt II we obtained
1.5 g (51.7%) of 1-(dimethylamino)but-2-yne, bp 113
116 C (680 mm Hg), nD20 1.4970 [7], mp 120 121 C
(picrate), mixture with an authentic sample gave no
melting point depression, 2.14 g (30.2%) of acetone
2,4-dinitrophenylhydrazone, and 32.1% of formic acid.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 2 2008