New aryl-substituted 1,4-dioxanes prepared from propargyl ethers of (bromomethyl)(phenylalkyl)methanols

Full text of DOI:10.1023/B:RUJO.0000010201.76096.8a

Russian Journal of Organic Chemistry, Vol. 39, No. 8, 2003, pp. 1206 1208. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 8, 2003,
pp. 1276 1278.
Original Russian Text Copyright
2003 by Talybov, Nurieva, Karaev.
SHORT
COMMUNICATIONS
New Aryl-substituted 1,4-Dioxanes Prepared from Propargyl
Ethers of (Bromomethyl)(phenylalkyl)methanols.
G. M. Talybov, U. G. Nurieva, and S. F. Karaev
Azerbaidzhan State Oil Academy, Baku, 370010, Azerbaidzhan
Received December 4, 2002
1,4-Dioxane and its derivatives (especially those
with unsaturated substituents) are promising initial
compounds for synthesis and efficient inhibitors of
acid corrosion of metals [1, 2].
tion of phenylalkene with propargyl alcohol and
N-bromosuccinimide.
1,4-Dioxanes IX XII are also formed at direct
reaction of Grignard reagent with ethers of (bromo-
methyl)(phenylalkyl)methanols VII, VIII in diglyme
circumventing the isolation of compounds I IV.
We formerly showed that the key stage in the
synthesis of such heterocycles consisted in the intra-
molecular elimination of hydrogen halide from com-
pounds containing in their structure a fragment of
( -haloethoxy)ethanol [3, 4].
The composition and structure of compounds
obtained were confirmed by elemental analysis, IR
1
and H NMR spectra.
Aiming at preparation of new aryl-1,4-dioxanes
we carried out a synthesis of the key ethers I IV. The
procedure was three-stage and included isolation of
the ethers as individual compounds followed by the
hydrogen halide elimination in an ethereal suspension
of potassium hydroxide, and by heterocyclization.
7-Benzyl-8-bromo-4-methyl-3-oxa-1-octyn-4-ol
(I). To a stirred Grignard reagent prepared from
5.95 g (0.05 mol) of propargyl bromide, 1.2 g
(0.05 mol) of magnesium in 80 ml of ethyl ether in
the presence of traces HgCl2 was added gradually at
cooling to 0 5 C 13.6 g (0.05 mol) of ketone VII.
The mixture was heated to 30 C for 3 4 h, then
cooled and treated with 10% HCl. The water layer
Propargyl ethers of (bromomethyl)(phenylalkyl)-
methanols V, VI were prepared by bromoalkoxyla-
R = H, n= 1 (I, II, V, VII, IX, X); R = CH3, n = 0 (III, IV, VI, VIII, XI, XII); R = CH2C CH (I, III, IX,
XI), C2H5 (II, IV, X, XII).
1070-4280/03/3908-1206$25.00 2003 MAIK Nauka/Interperiodica

ARYL-SUBSTITUTED 1,4-DIOXANES
1207
was extracted with diethyl ether, the extract was dried
on Na2SO4. On removing the solvent the vacuum
distillation of the residue provided 11.2 g (72%) of
alcohol I, bp 148 149 C (p, 1 mm Hg), d420 1.2231,
n2D0 1.5235, MRD 77.79, calc. 77.29. Found, %:
C 57.42; H 6.08; Br 25.29. C15H19BrO2. Calculated,
%: C 57.89; H 6.15; Br 25.68.
5-Benzyl-6-bromo-4-oxa-2-hexanone (VII). To a
stirred mixture heated to 60 C containing 0.65 g of
HgO, 1 ml of concn. H2SO4, and 23.5 ml of water
was gradually added at stirring 12.6 g (0.05 mol) of
compound V. The mixture was boiled for 6 h at 60
65 C, extracted with ethyl ether, the water layer was
saturated with NaCl and again extracted with ethyl
ether. The combined organic solutions were dried on
Na2SO4, the solvent was removed, and the residue
was subjected to vacuum distillation to obtain 7.7 g
(57%) of compound VII, bp 116 117 C (p,3 mm Hg),
Similarly were obtained compounds II IV.
6-Benzyl-7-bromo-3-methyl-5-oxaheptan-3-ol
(II). Yield 75%, bp 138 139 C (p, 1 mm Hg), d420
1.2245, n2D0 1.5240, MRD 75.27, calc. 74.77. Found,
%: C 55.35; H 6.95; Br 26.14. C14H21BrO2. Calcd.,
%: C 55.82; H 7.03; Br 26.53.
20
d4 1.3440, n2D0 1.5480, MRD 64.04, calc. 63.54.
1
IR spectrum, , cm : 675 (C Br), 1100 (C O C),
1725 (C=O), 1515, 1620, 3040, 3080, 3100 (C6H5).
Found, %: C 53.02; H 5.10; Br 29.05. C12H15BrO2.
Calculated, %: C 53.14; H 5.54; Br 29.52.
8-Bromo-4,7-dimethyl-7-phenyl-6-oxa-1-octyn-4-
ol (III) Yield 48%, bp 112 113 C (p, 1 mm Hg),
d420 1.2658, n2D0 1.5448, MRD 77.71, Calcd. 77.21.
Found, %: C 57.56; H 6.02; Br 25.45. C15H19BrO2.
Calculated, %: C 57.89; H 6.15; Br 25.68.
6-Bromo-5-methyl-5-phenyl-4-oxa-2-hexanone
(VIII) was similarly prepared in 57% yield, bp 88
90 C (p, 1 mm Hg), d240 1.3696, nD20 1.5632, MRD
64.32, calc. 63.92. Found, %: C 53.01; H 5.25; Br
29.17. C12H15BrO2. Calculated, %: C 53.15; H 5.58;
Br 29.47.
7-Bromo-3,6-dimethyl-6-phenyl-5-oxaheptan-3-
ol (IV) Yield 52%, bp 108 109 C (p, 1 mm Hg), d420
1.2650, n2D0 1.5442, MRD 75.19, Calcd. 74.69.
Found, %: C 55.53; H 7.00; Br 26.39. C14H21BrO2.
Calculated, %: C 55.82; H 7.03; Br 26.53.
5-Benzyl-2-methyl-2-propargyl-1,4-dioxane (IX).
(a) To a stirred suspension of 4.44 g KOH in 80 ml
of ethyl ether was added 9.33 g (0.03 mol) of alcohol
I, and the mixture was heated at reflux for 4 h. Then
it was treated with water, the ether layer was separat-
ed and dried on MgSO4. On removing the ether the
residue was distilled in a vacuum to furnish 5.5 g
(79%) of compoundIX, bp142 143 C (p, 1 mm Hg),
d240 1.0449, n2D0 1.5318, MRD 68.28, calc. 67.78.
5-Benzyl-6-bromo-4-oxa-1-hexyne (V). To an
equimolar mixture of 38 g (0.32 mol) of allylbenzene
and 18 g (0.32 mol) of propargyl alcohol cooled to
5 C was gradually added at stirring 26 g (0.32 mol)
of N-bromosuccinimide maintaining the temperature
of the reaction mixture below 0 C. The stirring was
continued for 3 h at room temperature, the formed
succinimide was removed by filtration, to the residue
was added a solution of 15 g of NaOH in 100 ml of
water, the product was extracted into ethyl ether, and
the extract was dried on CaCl2. On removing the
ether the residue was subjected to vacuum distillation
to afford 38.9 g (67%) of ether V, bp 106 107 C
(p, 1 mm Hg), d420 1.3091, nD20 1.5540, MRD 61.94,
1
IR spectrum, , cm : 1100 (C O C), 2100 and 3330
(C C-H), 1515, 1620, 3040, 3080, 3100 (C6H5).
1H NMR spectrum, , ppm: 2.1 t (1H, CH), 2.6 d
(2H, CH2C ), 3.00 m (2H, CH2), 3.20 3.75 m [4H,
(CH2O)2], 7.3 m (5H, C6H5). Found, %: C 78.11;
H 7.45. C15H18O2. Calculated, %: C 78.23; H 7.88.
(b) To a stirred Grignard reagent prepared from
5.9 g of propargyl bromide, 1.2 g of magnesium in
50 of anhydrous diglyme at cooling to 0 C was
gradually added 13.5 g (0.05 mol) of ether III. The
mixture was heated at stirring to 75 80 C for 4 h,
then cooled to room temperature, treated with water,
and the product was extracted into ethyl ether. The
extract was dried with Na2SO4. On removing the
solvent the vacuum distillation of the residue furnish-
ed 5.3 g (46%) of compound IX.
1
calc. 61.44. IR spectrum, , cm : 680 (C Br), 1100
(C O C), 2110 and 3310 (C CH), 1515, 1620, 3040,
3080, 3100 (C6H5). Found, %: C 56.43; H 5.02;
Br 31.42. C12H13BrO. Calculated, %: C 56.92;
H 5.14; Br 31.62.
6-Bromo-5-methyl-5-phenyl-4-oxa-1-hexyne (VI)
was similarly prepared in 74% yield, mp 76 C. IR
1
spectrum, , cm : 660 (C Br), 1100 (C O C), 2100
1
and 3300(C C H). HNMR spectrum, , ppm:1.65 s
Substituted dioxanes X XII were similarly obtain-
ed by procedure (a).
(3H, CH3), 2.45 t (1H, CH), 3.45 s (2H, CH2Br),
4.01 d (2H, OCH2C ), 7.45 m (5H, C6H5). Found,
%: C 56.25; H 5.05; Br 31.15. C12H13BrO. Calculat-
ed, %: C 56.94; H 5.18; Br 31.57.
5-Benzyl-2-methyl-2-ethyl-1,4-dioxane (X):
Yield 80%, bp 136 C (p,1 mm Hg), d240 1.0136, nD20
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 8 2003

1208
TALYBOV et al.
1
1.5170, MRD 65.76, calc. 65.26. IR spectrum,
,
pellets. H NMR spectra were registered on spectro-
1
cm : 1100 (C O C), 2100 and 3330 (C C H), 1515, meter Bruker SF-400 (400.134 MHz) from solutions
1640, 3080, 3100 (C6H5). H NMR spectrum, , ppm: in CDCl3, internal reference HMDS.
1
0.85 1.45 m (5H, CH3CH2), 3.00 m (2H, CH2),
3.20 3.75 m (4H, (CH2O)2), 7.35 m (5H, C6H5).
Found, %: C 76.05; H 9.02. C14H20O2. Calculated,
%: C 76.33; H 9.15.
REFERENCES
1. Karaev, S.F., Garaeva, Sh.V., and Mamedov, F.V.,
Khimiya geteroatomnykh propargil,nykh soedinenii
(Chemistry of Propargyl Compounds Containing
Heteroatoms), Moscow: Khimiya, 1993.
2. Karaev, S.F., Mekhtieva, V.Z., Agaev, N.M., and
Dzharchieva, S.S., Abstracts of Papers, Vserossiiskaya
nauchno-prakticheskoi konf. Razrabotka, proizvodstvo
i primenenie khimicheskikh reagentov dlya neftyanoi i
gazovoi promyshlennosti (Development, Production,
and Application of Chemical Reagents for Petro-
chemical Industry), Moscow, 2002.
3. Karaev, S.F., Talybov, G.M., and Khabib Rakhman,
Tukhi, Zh. Org. Khim., 1993, vol. 29, p. 421.
4. Nurieva, U.G., Talybov, G.M., and Karaev, S.F.,
Abstracts of Papers, Vth Bakinskaya Mezhdunarodn.
Mamedalievskaya Neftekhim. Konf (V Mamedaliev
Petrochemical Baku Conf.), 2002, Baku, p. 91.
2,5-Dimethyl-2-propargyl-5-phenyl-1,4-dioxane
(XI) Yield 70%, bp 118 119 C (p, 1 mm Hg), d420
1.0771, n2D0 1.5516, MRD 68.28, Ecalc 67.78.
Found, %: C 78.12; H 7.65. C15H18O2. Calculated,
%: C 78.23; H 7.88.
2, 5-Dimethyl-5-phenyl-2-ethyl-1, 4-dioxane
(XII): Yield 75%, bp 102 103 C (p 1 mm Hg), d420
1.0368, n2D0 1.5312, MRD 65.76, Ecalc 65.26.
Found, %: C 76.18; H 9.07. C14H20O2. Calculated,
%: C 76.33; H 9.15.
The organomagnesium synthesis in diglyme afford-
ed compounds X XII in 40 50% yield.
IR spectra were recorded on spectrophotometers
UR-20 and Specord 75 IR from thin films or KBr
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 8 2003