SYNTHESIS OF NEW SUBSTITUTED 2,3-DIHYDRO-1,4-DIOXIN-2-ONES
709
6
-Chloromethyl-1,4-dioxan-2-one (XV). Com- C 52.64; H 5.26. C H O . Calculated, %: C 52.63;
5
6
3
pound XIII was treated with thionyl chloride accord-
ing to the procedure described in [7]. Yield 12.34 g
82%), mp 54 55 C (from chloroform petroleum
ether, 1:1). IR spectrum, , cm : 1113 1107 (COC);
782 (C O); 842 (C Cl). H NMR spectrum,
ppm: 4.3 d (CH Cl; J = 7.2 Hz). Found, %: C 39.89;
H 4.63; Cl 23.59. C H ClO . Calculated, %: C 39.87;
H 4.65; Cl 23.62.
H 5.26.
-Methyl-6-methylene-1,4-dioxan-2-one (XVIII)
was synthesized in a similar way. Yield 8.3 g (65%);
3
(
1
20
20
bp 103 105 C (4 mm); nD = 1.4236; d4 = 1.0686;
1
1
1
,
MRD = 30.54. IR spectrum, , cm : 1655 (C C);
2
1
1780 (C O). H NMR spectrum, , ppm: 4.5 s
2
2
(
CH ; J = 2.8 Hz). Found, %: C 52.27; H 6.27;
2
5
7
3
C H O . Calculated, %: C 56.25; H 6.25.
6
8
3
6
-Chloromethyl-3-methyl-1,4-dioxan-2-one
REFERENCES
(
XVI). 6-Hydroxymethyl-3-methyl-1,4-dioxan-2-one
(
XIV) was treated with thionyl chloride in pyridine
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.
as described in [6]. Yield 9.91 g (87%); bp 89 91 C
2 mm); n2 = 1.5099; d4 = 1.3785. MR = 35.71;
0
20
(
D D
1
calculated: 35.87. IR spectrum, , cm : 1111
1
spectrum, , ppm: 4.5 d (CH Cl; J = 7.3 Hz). Found,
%
%
1
108 (COC); 1780 (C O); 835 (C Cl). H NMR
2
3
4
5
6
.
.
.
.
.
Akopyan, S.M., Pirumyan, G.P., and Avetisyan, T.V.,
Uch. Zap. Erevan. Gos. Univ., 2000, no. 2, p. 130.
2
2
: C 43.75; H 5.45; Cl 21.52. C H ClO . Calculated,
6
9
3
Akopyan, S.M., Zh. Prikl. Khim. Arm., 1999, no. 2,
p. 82.
: C 43.77; H 5.47; Cl 21.58.
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
Akopyan, S.M., Tatevosyan, A.M., and Zali-
nyan, M.G., Arm. Khim. Zh., 1986, no. 12, p. 751.
2
Akopyan, M.S., Akopyan, S.M., and Pirumyan, G.P.,
Inform. Tekhnol. Upravl. (Erevan), 2000, no. 1, p. 68.
added to 0.03 mol of 6-halomethyl-1,4-dioxan-2-one.
The mixture was heated for 20 22 h under reflux
with stirring. It was then cooled, and the precipitated
salt was filtered off and washed with petroleum ether
on a filter. The filtrate was combined with the
washings, petroleum ether was distilled off, and the
residue was distilled in a vacuum. Yield 7.0 g (62%);
bp 90 92 C (4 mm); n = 1.4210; d = 1.1120.
MR = 25.99. IR spectrum, , cm : 1652 m (C C);
1
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
4
D
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.
1
D
1
112 1108 (COC); 1780 (C O). H NMR spectrum,
ppm: 4.6 s ( CH ; J = 2.7 Hz). Found, %:
2
2
,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 5 2003