Synthesis of new substituted 2,3-dihydro-1,4-dioxin-2-ones and 1,4-dioxan-2-ones

Article abstract of DOI:10.1023/B:RUJO.0000003199.27202.93

3-Alkyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones reacted with acetyl chloride in the presence of zinc(II) chloride to give the corresponding 3-alkyl-5-acetyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones. Oxidation of the latter with hydrogen peroxide in formic acid, followed by treatment with magnesium bromide, afforded 3-alkyl-6-methyl-1,4-dioxane-2,5-diones. Successive chlorination and dechlorination of 6-hydroxymethy 1-1,4-dioxan-2-ones yielded 6-methylene-1,4-dioxan-2-ones.

Full text of DOI:10.1023/B:RUJO.0000003199.27202.93

Russian Journal of Organic Chemistry, Vol. 39, No. 7, 2003, pp. 1034 1036. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 7, 2003,
pp. 1097 1100.
Original Russian Text Copyright
2003 by Akopyan, Khachatryan.
Synthesis of New Substituted 2,3-Dihydro-1,4-dioxin-2-ones
and 1,4-Dioxan-2-ones
S. M. Akopyan and A. G. Khachatryan
Erevan State University, ul. A. Manukyana 1, Erevan, 375025 Armenia
Received September 27, 2002
Abstract 3-Alkyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones reacted with acetyl chloride in the presence of
zinc(II) chloride to give the corresponding 3-alkyl-5-acetyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones. Oxidation
of the latter with hydrogen peroxide in formic acid, followed by treatment with magnesium bromide, afforded
3
-alkyl-6-methyl-1,4-dioxane-2,5-diones. Successive chlorination and dechlorination of 6-hydroxymethyl-1,4-
dioxan-2-ones yielded 6-methylene-1,4-dioxan-2-ones.
We previously synthesized 2,5-substituted 2,3-di-
hydro-1,4-dioxins [1 3]. In continuation of our studies
on the preparation and properties of dihydro-1,4-di-
oxinones, we have synthesized 3-alkyl-5-acetyl-6-
methyl-2,3-dihydro-1,4-dioxin-2-ones by reaction of
phenylhydrazones (see table). Oxidation of the endo-
cyclic double bond in IV VI with hydrogen peroxide
in formic acid (performic acid) gave 3-alkyl-5,6-di-
hydroxy-1,4-dioxan-2-ones VII IX. The latter were
treated with an equimolar amount of magnesium
bromide to obtain 3-alkyl-6-methyl-1,4-dioxane-2,5-
diones X XII (Scheme 2).
3-alkyl-6-methyl-2,3-dihydro-1,4-dioxin-2-ones I III
with acetyl chloride in the presence of a catalytic
amount of zinc(II) chloride (Scheme 1).
Dioxanediones X XII are crystalline substances.
1
Their structure was proved by the IR and H NMR
Scheme 1.
spectra (see table). The IR spectra of X XII lack
characteristic absorption due to stretching vibrations
of the double bond but contain strong bands at 1110
1
1
108 and 1785 1780 cm , respectively.
The reaction of 3-alkyl-6-hydroxymethyl-1,4-di-
oxan-2-ones XIII and XIV [4] with thionyl chloride
in pyridine afforded 3-alkyl-6-chloromethyl-1,4-di-
oxan-2-ones XV and XVI. Treatment of the latter
with potassium hydrogen carbonate resulted in forma-
tion of 6-methylene derivatives XVII and XVIII
(Scheme 3). The use of alkali metal alkoxides as
I, IV, R = H; II, V, R = Me; III, VI, R = Et.
The structure of products IV VI was confirmed by
1
the IR and H NMR spectra, elemental analyses, and
their conversion into the corresponding 2,4-dinitro-
Scheme 3.
Scheme 2.
IV, VII, X, R = H; V, VIII, XI, R = Me; VI, IX, XII, R = Et.
XIII, XV, XVII, R = H; XIV, XVI, XVIII, R = Me.
1
070-4280/03/3907-1034$25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS OF NEW SUBSTITUTED 2,3-DIHYDRO-1,4-DIOXIN-2-ONES
-Dihydro-1,4-dioxin-2-ones IV VI and 1,4-dioxane-2,5-diones X XII
Found, % Calculated, %
1035
2
Comp. Yield,
IR spectrum, 1H NMR spectrum,
mp, C
Rf
Formula
no.
%
, cm 1
, ppm (J, Hz)
C
H
C
H
IV
61.3
59 61
0.41
53.87
5.21
C H O
53.85
5.13
1730 (C O)
5.6 d (3), J = 7.2
7.7 s (7), J = 11.8
8.2 s (8), J = 10.7
7
8
4
1660 (C C)
108 (COC)
1
V
58.0
63.1
63.7
65.0
62.5
56
0.42
0.40
0.41
0.41
0.44
56.53
58.74
46.27
49.88
53.10
5.93
6.60
4.63
5.53
6.29
C H O
56.47
58.69
46.15
50.00
53.16
5.88
6.52
4.61
5.55
6.33
1745 (C O)
4.4 q (3), J = 7.4
7.6 s (7), J = 13.0
8.1 s (8), J = 12.7
8
10
4
1
1
665 (C C)
110 (COC)
VI
X
72 73
70 71
89 90
74 76
C H O
1745 (C O)
4.5 m (3), J = 7.3
7.7 s (7), J = 12.3
8.0 s (8), J = 13.3
9
12
4
1
1
660 (C C)
112 (COC)
C H O
1780 (C O)
108 (COC)
4.7 d (3), J = 7.5
8.6 q (6), J = 10.1
5
6
4
1
8
.8 d (7), J = 8.4
XI
XII
C H O
1785 (C O)
112 (COC)
4.8 q (3), J = 7.6
8.6 q (6), J = 9.8
6
8
4
1
8
.7 d (7), J = 8.3
C H O
1780 (C O)
110 (COC)
8
10
4
1
dehydrohalogenating agents leads to opening of the
dioxane ring.
chromatograph equipped with a steel column, 2000
4 mm, which was packed with 5% of SE-30 on
Chromosorb PAW; carrier gas helium, flow rate
The structure of compounds XVII and XVIII was
1
6
0 ml/min; heat conductivity detector; oven tempera-
confirmed by the IR and H NMR spectra. The pres-
ture 453 473 K; as well as by TLC on Silufol UV-
ence of a double bond therein was proved by chemical
tests (reactions with bromine and potassium perman-
ganate). Successive hydrochlorination and dehydro-
chlorination of XVIII afforded 3,6-dimethyl-2,3-di-
hydro-1,4-dioxin-2-one which was described by us
previously [2].
2
4
54 plates (butanol acetic acid 50% aqueous acetone,
0:40:20; development with iodine vapor).
3-Alkyl-5-acetyl-6-methyl-2,3-dihydro-1,4-di-
oxin-2-ones IV VI were synthesized by the procedure
described in [6]. Their properties are given in table.
2
,4-Dinitrophenyl hydrazones: IV, mp 106 108 C.
1
,4-Dioxan-2-one is known to selectively absorb
Found, %: N 16.82. C H N O . Calculated, %:
N 16.66; V, mp 118 119 C. Found, %: 16.11.
C H N O . Calculated, %: N 16.00; VI, mp 133
1
%
carbon(II) oxide from exhaust gas [4]. We have found
that 3,6-substituted 1,4-dioxan-2-ones also selectively
absorb carbon(II) oxide from products of combustion
of carburant and diesel fuel [5]. Examination of the
ecological parameters of eight newly synthesized
compounds IV VI, IX XII, XVII, and XVIII is now
in progress.
13 12
4
6
14 14
4
6
44 C. Found, %: N 15.45. C H N O . Calculated,
15 16 4 6
: N 15.38.
3-Alkyl-6-methyl-1,4-dioxane-2,5-diones X XII.
3-Alkyl-5-acetyl-6-methyl-2,3-dihydro-1,4-dioxin-2-
ones IV VI were oxidized by the procedure described
in [6]. The resulting 3-alkyl-5,6-dihydroxy-6-methyl-
EXPERIMENTAL
1
,4-dioxan-2-ones (without isolation) were heated for
The IR spectra were recorded on a UR-20 instru-
ment (Carl Zeiss). The H NMR spectra were obtained
on a Varian-300 spectrometer using TMS as internal
reference. The purity of the initial compounds and
products was checked by GLC on an LKhM-72M
3 5 h in boiling toluene containing an equimolar
amount of magnesium bromide. The mixture was
cooled to room temperature and washed with cold
water. The organic layer was separated, washed over
anhydrous magnesium sulfate, and evaporated, and the
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 7 2003

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