Vol. 27, No. 10 (2015)
Synthesis of 3-[N-(2-Methacroyloylethyl)-N,N-dimethylamino]propane Sulfonate and its Crystal Structure 3819
TABLE-1
1H NMR spectrum was obtained with Bruker AV-300
spectrometer at 300.13 MHz and measured in D2O solution at
20 0.5 °C. The sample was dissolved in a 5 mm diameter
tube at a concentration of about 20 mg/mL. X-ray diffraction
was performed on a BrukerAPEXII CCD diffractometer. Mass
spectrum of (I) was analyzed using Trace DSQ GC/MS (Thermo
Electron Co., USA).
CRYSTALLOGRAPHIC DATA FOR COMPOUND (I)
Item
Data or description
Formula
C11H23NO6S
Formula weight
297.36
Temperature (K)
293 (2)
Wavelength (Å)
0.71073
Crystal system
Monoclinic
Synthesis of 3-[N-(2-methacroyloylethyl)-N,N-dimethyl-
amino]propane sulfonate: In a 100 mL three-necked flask,
N,N-dimethyl ethanolamine (20 mmol) and triethylamine (40
mmol) were dissolved by dichloromethane in an ice-water bath.
Methacryloyl chloride was dissolved in dichloromethane,
then it was added into the reaction vessel slowly. After 12 h, the
system was filtered. The organic layer was washed with water,
saturated sodium bicarbonate solution and saturated sodium
chloride solution successively. The organic layer was dried over
anhydrous sodium sulfate. The product purified by column
chromatography (petroleum ether:ethyl = 3:1). Compound (1)
was obtained in the form of a colourless liquid (Yield: 75 %).
To a 250 mL three-necked flask equipped with a magnetic
stirrer, condenser and dropping funnel, 0.11 mol of 2-(dimethyl-
amino)ethyl methacrylate (1) and a little hydroquinone
dissolved in 30 mL acetone was added and the mixture was
heated to 60 °C in a thermostated water bath. 0.1 mol of 1,3-
propanesultone was dissolved in 30 mL acetone was added and
then added drop-wise in to the flask over 8 h under magnetic
stirring, subsequently react at 60 °C for 2 h. The DMAPS was
precipitated from the reaction medium in the form of white
crystal, separated by filtration, vigorously washed with acetone.
After filtration, the fine compound (I) was obtained by
recrystallization of the filter residue using absolute ethanol as
solvent. Crystals of (I) that suitable for X-ray diffraction were
obtained by slow evaporation of 95 % ethanol solution of (I).
X-ray crystallography: A colourless block-like crystal
of compound (I) grown in 95 % ethanol with dimensions of
0.27 mm × 0.20 mm × 0.16 mm was used for structural determi-
nation. Diffraction data were collected on a Bruker APEXII
CCD diffractometer by using graphite monochromated MoKα
radiation (λ = 0.71073 Å). The structure was solved by direct
methods withSHELXS-97 and refined on the F2 by full-matrix
least-squares method with SHELXL-97. All non-hydrogen
atoms were refined anisotropically.
Space group
a (Å)
b (Å)
P21/c
14.6818(18)
b = 7.1104(9)
c = 14.9180(18)
1548.5(3)
c (Å)
Volume (Å3)
Z
4
Calculated density (g/cm3)
Absorption coefficient (mm-1)
F(000)
1.276
0.23
640
Crystal size (mm)
Theta range for data collection (°)
Reflections collected/unique
Completeness to θ = 25.39 (%)
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I>2σ(I)]
R indices (all data)
Largest diff. peak and hole (e. Å-3)
0.27 × 0.20 × 0.16
1.4 to 27.5
3495/2944 [R(int) = 0.108]
99.9
0.9407 and 0.9642
Full-matrix least-squares on F2
3495/15/175
1.05
R1 = 0.0548, wR2 = 0.1546
R1 = 0.0625, wR2 = 0.1639
0.63 and -0.48
Fig. 1. General appearance of compound I with the atoms represented by
thermal vibration ellipsoids of 50 % probability
RESULTS AND DISCUSSION
1
Identification of resonance in the spectra: In the H
NMR spectrum of DMAPS, the peaks at 6.03 ppm and 5.65
ppm were due to the proton of olefin double bond, 4.70 ppm
was assigned to the proton of D2O.The peaks at 4.51, 3.70,
3.50, 2.84 and 2.04 ppm were assigned to the H of CH2 group,
the peak at 3.09 and 1.80 ppm were assigned to the H of CH3
group. In the MS spectrum, the m/z 280 was assigned to
molecular ion peak (M+1).
The crystal configuration of DMAPS was confirmed by
X-ray structural analysis. Experimental details for X-ray data
collection were presented in Table-1 and the geometric para-
meters for compound (I) were listed in Table-2. Molecular
structure and packing plot of DMAPS were showed in Figs. 1
and 2, respectively.
Fig. 2. Packing diagram for compound I