Asian Journal of Chemistry; Vol. 27, No. 6 (2015), 2099-2101
A
SIAN
J
OURNAL OF HEMISTRY
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Synthesis and Crystal Structure of (5-Ethyl-2-methyl-2-phenyl-1,3-dioxan-5-yl)methanol
1,*
1
1,2
1
XIAN-YOU YUAN , XIN-YU ZHANG , GUANG-CHUAN OU , LIN YUAN1,2 and MIN ZHANG
1Department of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou, Hunan, P.R. China
2Key Laboratory of Functional Organometallic Materials of Hunan Province College, Hengyang Normal University, Hengyang, Hunan, P.R. China
*Corresponding author: Tel: +86 746 6381164, E-mail: yuanxianzhangmin@163.com
Received: 4 April 2014;
Accepted: 5 June 2014;
Published online: 17 March 2015;
AJC-16970
A new compound (5-ethyl-2-methyl-2-phenyl-1,3-dioxan-5-yl)methanol, obtained from the reaction of 2,2-bis(hydroxymethyl)butanol
with acetophenone, has been synthesized and characterized by IR and 1H NMR. Single crystal X-ray diffraction analyses indicated that
the title compound belongs to tetragonal system with space group I4(1)/a with a = 29.921(2) Å, b = 29.921(2) Å, c = 5.9627(9) Å. Mr
= 236.30, V = 5338.1(10) Å3, Dc = 1.176 g/cm3, Z = 16, µ = 0.081 mm-1, F(000) = 2048, R = 0.0595, wR = 0.1645. In the title compound,
the 1,3-dioxane ring adopts a chair conformation and the phenyl substituent occupies an equatorial site. In the crystal, adjacent four
molecules are connected by O-H···O hydrogen bonding interactions into a tetramer.
Keywords: 1,3-Dioxane, Acetophenone, Synthesis, Crystal structure.
Chemical Plant. 2,2-bis(Hydroxymethyl)butanol was the
product of Aladin. Crystal structure was determined on a
Bruker SmartApex II diffractometer. Elemental analyses were
performed by direct combustion with a PE2400 instrument.
The IR spectra were recorded in the 4000-400 cm-1 region
using KBr pellets and a Niconet AVATAR-360 spectrometer.
1H NMR spectra were recorded in a CDCl3 solution with a
BrukerAV-400 spectrometer. Melting point data were recorded
in a Buchi B545 spectrometer.
Synthesis of (5-ethyl-2-methyl-2-phenyl-1,3-dioxan-5-
yl)methanol: 2,2-bis(Hydroxymethyl) butanol (1.3400 g, 10
mmol) and acetophenone (1.3215 g, 11 mmol) were added
into 50 mL round-bottom flask provided with a stirrer and a
reflux condenser. Both a solution of N,N-dimethylformamide
(5 mL), cyclohexane (8 mL) and 1-acetyl-3-methylimidazole
hydrogen sulfate (0.1 g) were simultaneously added dropwise
to the flask and the reacting solution was kept at 378 K under
reflux for 4 h. After the reaction completion, the reaction
mixture was poured into separator funnel and separated. The
organic layer was washed with water (10 × 3 mL), dried with
MgSO4. Once more filtered and evaporated to dryness. Then
the white solid powder was obtained 1.3 g (yield: 53 %). The
melting point of purified product was 357.3-358.1 K. The
product was recrystallized from cyclohexane to afford
colourless crystals (Scheme-I). Anal. Calcd. for C14H20O3: C,
INTRODUCTION
Acetal compounds have many characters such as aroma1
and chemical stability2, which are used widely in fragrances
and food flavors3,4. Acetal compounds are stable in neutral
and alkaline conditions and will degradate and generate a
material of small molecules in acidic conditions. Polyfunc-
tional branched compounds are the new class of compounds
with a wide range of applications.The synthesis of these
compounds rich in raw materials and simple manufacturing
process, in the synthesis of fine chemicals and other industries
have shown important uses and has great potential for deve-
lopment5-7. Ionic liquids as a catalyst have especial advantages
in the synthesis of acetal compounds in 21st century green8.
To our knowledge the report of 2,2-dimethylolbutyric acetal
(ketone) was rare. Herein, in this paper, a novel compounds
(5-ethyl-2-methyl-2-phenyl-1,3-dioxan-5-yl)methanol was
synthesized by using 2,2 -bis(hydroxymethyl) butanol with
acetophenone as raw material, ionic liquid as catalyst, DMF
and cyclohexane as solvent and its structure has been charac-
terized.
EXPERIMENTAL
The ionic liquid of 1-acetyl-3-methylimidazole hydrogen
sulfate was prepared according to the literature method9. All
the starting materials and solvents were commercially available
and used without further purification. acetophenone and ethyl
acetate were obtained commercially from Tianjin Damao
71.19; H, 8.47 %. Found C, 71.10; H, 8.29 %. IR (KBr, νmax
,
cm-1): 3327, 2954, 2870, 1461, 1377, 1242, 1087, 1021, 878,
767, 703.