1
036
AKOPYAN, KHACHATRYAN
residue was recrystallized from acetone ethyl acetate
:1 (see table).
-Chloromethyl-1,4-dioxan-2-one (XV). Com-
pound XIII was chlorinated according to the proce-
dure described in [7]. Yield 12.34 g (82%), mp 54
C 52.64; H 5.26. C H O . Calculated, %: C 52.63;
5 6 3
H 5.26.
1
6
3-Methyl-6-methylene-1,4-dioxan-2-one (XVIII)
was synthesized as described above for compound
XVII. Yield 8.3 g (65%), bp 103 105 C (4 mm),
2
0
20
5
5 C (from chloroform petroleum ether, 1:1). IR
n
= 1.4236, d4 = 1.0686; MR = 30.54. IR spec-
D D
1
1
1
spectrum, , cm : 1113 1107 (COC), 1782 (C O),
trum, , cm : 1655 (C CH ), 1780 (C O). H NMR
spectrum, , ppm: 4.5 s (C CH , J = 2.8 Hz).
2
1
2
8
42 (C Cl). H NMR spectrum, , ppm: 4.3 d
2
2
(CH Cl; J = 7.2 Hz). Found, %: C 39.89; H 4.63;
Found, %: C 52.27; H 6.27. C H O . Calculated, %:
2
6
8
3
Cl 23.59. C H ClO . Calculated, %: C 39.87; H 4.65;
C 56.25; H 6.25.
5
7
3
Cl 23.62.
6
-Chloromethyl-3-methyl-1,4-dioxan-2-one
REFERENCES
(
XVI). 6-Hydroxymethyl-3-methyl-1,4-dioxan-2-one
1
.
Akopyan, S.M., Sbornic nauchnykh trudov Khimiya i
khimicheskaya tekhnologiya (Collection of Scientific
Papers Chemistry and Chemical Technology ),
Erevan: Erevan. Gos. Univ., 1989, no. 5, p. 76.
(XIV) was treated with thionyl chloride in pyridine,
following the procedure described in [7]. Yield 9.91 g
2
0
20
(87%), bp 89 91 C (2 mm), nD = 1.5099, d4
=
1
.3785; MR = 35.71; calculated: 35.87. IR spectrum,
D
1
,
cm : 1111 1108 (COC), 1780 (C O), 835
2. Akopyan, S.M., Pirumyan, G.P., and Avetisyan, T.V.,
1
Uch. Zap. Erevan. Gos. Univ., 2000, no. 2, p. 130.
(
C Cl). H NMR spectrum, , ppm: 4.5 d (CH Cl,
2
2
J = 7.3 Hz). Found, %: C 43.75; H 5.45; Cl 21.52.
C H ClO . Calculated, %: C 43.77; H 5.47; Cl 21.58.
3. Akopyan, S.M., Zh. Prikl. Khim. Arm., 1999, no. 2,
p. 82.
6
9
3
6
-Methylene-1,4-dioxan-2-one (XVII). A solution
of 0.066 mol of potassium hydrogen carbonate in
0 ml of water and 10 ml of dimethylformamide was
4. Akopyan, S.M., Tatevosyan, A.M., and Zali-
nyan, M.G., Arm. Khim. Zh., 1986, no. 12, p. 751.
2
5. Akopyan, M.S., Akopyan, S.M., and Pirumyan, G.P.,
added to 0.03 mol of compound XVI, and the mixture
was heated for 20 22 h under reflux with stirring. The
mixture was cooled and filtered, and the precipitate
was washed on a filter with petroleum ether. The
filtrate was combined with the washings, petroleum
ether was distilled off, and the residue was distilled
under reduced pressure. Yield 7.0 g (62%), bp 90
Inform. Tekhnol. Upravl. (Erevan), 2000, no. 1, p. 68.
6
.
Weygand Hilgetag Organisch-chemische Experi-
mentierkunst, Hilgetag, G. and Martini, A., Eds.,
Leipzig: Johann Ambrosius Barth, 1964, 3rd ed.
Translated under the title Metody eksperimenta
v organicheskoi khimii, Moscow: Khimiya, 1968,
pp. 272, 772.
2
0
20
9
2
1
2 C (4 mm), n = 1.4210, d = 1.1120; MR =
7. Organikum. Organisch-chemisches Grundpraktikum,
Berlin: Wissenschaften, 1976, 15th ed. Translated
under the title Organikum. Praktikum po organiche-
skoi khimii, Moscow: Mir, 1979, vol. 2, p. 103.
D
4
D
1
5.99. IR spectrum, , cm : 1652 m (C CH ),
2
1
112 1108 (COC), 1780 (C O). H NMR spectrum,
ppm: 4.6 s (C CH , J = 2.7 Hz). Found, %:
2
,
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 7 2003