1
44
GHARIBYAN et al.
Based on the foregoing, we can assume that the
added dropwise to 1 ml of D O. The resulting
2
hydroalumination proceeds through the formation of
the same cyclic organometallic complex on the
reduction of both α-acetylenic alcohols and isopropenyl-
acetylene and diacetylene β-alcohols [1–3]. This is
evidenced by the fact that the triple bond in the tetra-
hydropyranyloxy derivative V is not reduced under the
reaction conditions.
precipitate was filtered off and washed with diethyl
ether. The filtrate was treated with ammonium chloride
solution, dried over magnesium sulfate, and con-
1
centrated. Yield 0.3 g (58.8%). Н NMR spectrum
(СDCl ), d , ppm (J, Hz): 3.47–3.70 m (5Н,
3
Н
ОСН СН ОН), 4.19 d (2Н, =СНСН О, J 7.0), 4.93 d
2
2
2
3
3
(1Н, DHC=, J 12.2), 4.99 d (1Н, DHC=, J
16.4),
cis
trans
5
.68–5.81 m (1Н, =CHCH O).
2
Thus, the hydroalumination of 2-(2-propyne-1-
yloxy)ethanol I is regiospecific: the hydride ion attacks
the carbon atom of the C≡C bond nearest to the ether
group. The splitting of the intermediate organometallic
complex by the deuterium oxide and iodine is not
stereoselective. This can be explained by the fact that
in contrast to the triple bond forming eight-membered
cyclic organometallic complex formed at the
hydroalumination of the diacetylene β-alcohols, in the
case of ethylene glycol monopropargyl ether I the
organometallic complex is more labile, and as a
consequence the electrophilic substitution does not
proceed stereoselectively.
2-[(3-Iodo-2-propen-1-yl)oxy]ethanol (IV). To a
suspension of 3.3 g (86 mmol) of lithium aluminum
hydride in 40 ml of anhydrous dioxane was added
dropwise 4.3 g (43 mmol) of 2-(2-propyn-1-yloxy)
ethanol I in 10 ml of anhydrous dioxane at –5°C. The
reaction mixture was refluxed with stirring for 6 h.
After cooling to 0°C, to the reaction mixture was
added 7.6 g (86 mmol) of ethyl acetate. The reaction
mixture was kept at 0°C for 1 h. Then to the mixture
was added by portions 8.21 g (86 mmol) of powdered
iodine for 0.5 h. The stirring was continued at 0°C for
1 h. After treating with the saturated sodium
thiosulfate solution the precipitate was filtered off, and
the organic layer was extracted with ether. The extract
was washed with sodium thiosulfate solution, brine,
and dried over magnesium sulfate. After the solvent
removal, the product was purified by column chro-
matography (hexane–diethyl ether, 8:1). Yield 4.5 g
(46.1%), R 0.52 (hexane–diethyl ether, 2:1). IR
spectrum, ν, cm : 930, 970, 1640, 3070 (CH=CHI),
1110 (C–O–C), 3300–3500 (OH). Н NMR spectrum
(СDCl ), d , ppm (J, Hz): 2.46 br. s (1Н, ОН), 3.27 t
(2Н, ОСН СН ОН, J 7.0), 3.51–3.55 m (4Н,
ОСН СН ОН), 4.20 d (2Н, =CHCH O, J 7.0), 6.32 d
(1Н, CHI, J
The starting monopropargyl ether of ethylene
glycol I was synthesized by a known method [4].
2
-(Allyloxy)ethanol (II). To a suspension of 1.5 g
40 mmol) of lithium aluminum hydride in 20 ml of
anhydrous dioxane was added dropwise 2.0 g
20 mmol) of 2-(2-propyn-1-yloxy)ethanol I in 5 ml of
(
(
f
–
1
anhydrous dioxane at –5°C. The reaction mixture was
refluxed with stirring for 6 h, cooled to 0°C, and
treated with 1.5 ml of water, 1.5 ml of 15% sodium
hydroxide solution, and 4.5 ml of water. The pre-
cipitate was filtered off. The filtrate was extracted with
diethyl ether and dried over magnesium sulfate. After
the solvent removal, the residue was distilled in a
1
3
Н
2
2
2
2
2
3
3
16.6), 6.37 d (1Н, CHI, J 11.9),
trans
cis
6.42–6.56 m (1Н, trans-IHC=CH), 6.62–6.92 m (1Н,
cis-IHC=CH). Found, %: С 26.45; Н 4.06; I 55.54.
С Н IО . Calculated, %: С 26.34; Н 3.98; I 55.65.
о
vacuum. Yield 1.57 g (78.0%), bp 85–87 С (2 mm Hg).
–
1
IR spectrum, ν, cm : 930, 970, 1645, 3070 (СН=CH ),
1
2
5
9
2
1
100 (C–O–C), 3300–3500 (OH). Н NMR spectrum
2
-[2-(2-Propynyl-1-oxy)ethoxy]tetrahydro-2H-
(
DMSO-d ), d , ppm (J, Hz): 2.65 br. s (1Н, ОН),
6
Н
pyran (V). To a mixture of 2.0 g (20 mmol) of 2-(2-
propyn-1-yloxy) ethanol I and 4.2 g (50 mmol) of
dihydropyran was added 20 mg of p-toluenesulfonic
acid. The mixture was stirred for 4 days at room tem-
perature, treated with a saturated potassium carbonate
solution, extracted with diethyl ether, and dried over
potassium carbonate. After the solvent removal, the
residue (3.5 g) was purified by column chromato-
graphy (hexane–diethyl ether, 10:1). Yield 2.2 g
3
=
5
.36–3.58 m (4Н, ОСН СН ОН), 3.93 m (2Н,
2
2
A
1
3
2
СНСН О), 5.18 d. d (1Н, Н , J 11.3, J 1.6),
2
cis
gem
1
B
3
2
.27 d. d (1Н, Н , J
16.5, J 1.6), 5.82–5.95 m
trans gem
2
(
1Н, Н ). Found, %: С 59.32; Н 10.09. С Н О .
5 10 2
Calculated, %: С 58.80; Н 9.87.
2
-[2-Propen-1-yloxy]ethanol-d (III). To a suspen-
1
sion of 0.4 g (10 mmol) of lithium aluminum hydride
in 5 ml of anhydrous dioxane was added dropwise
0
ml of anhydrous dioxane at –5°C. The reaction mixture
was refluxed with stirring for 6 h, cooled to 0°C and
.5 g (5 mmol) of 2-(2-propyn-1-yloxy)ethanol I in 1
(59.8%), R 0.41 (hexane–diethyl ether, 2:1). IR spec-
f
–
1
trum, ν, cm : 1040, 1080, 1100, 1130, 1200, 1370,
1
1445 (С–О–С), 2220 (С≡С). Н NMR spectrum
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 1 2013