Synthesis and characterization of 3-[N-(2-methacroyloylethyl)-N,N-dimethylamino]propane sulfonate and its crystal structure

Article abstract of DOI:10.14233/ajchem.2015.18997

3-[N-(2-Methacroyloylethyl)-N,N-dimethylamino]propane sulfonate (DMAPS) was synthesized by the ring-opening reaction of 1,3- propanesultone, then electrophilic substitution with 2-(dimethylamino)ethyl methacrylate in the presence of acetone at 60 °C. 2-(Dimethylamino)ethyl methacrylate and a little polymerization inhibitor dissolved in acetone was added in three-necked flask, the mixture was heated to 60 °C. 1,3-Propanesultone was dissolved in acetone and then be added drop-wise into the flask over 8 h. The product was characterized by NMR and Mass spectrum. The crystal structure of 3-[N-(2-Methacroyloylethyl)-N,N-dimethylamino]propane sulfonate was investigated using X-ray diffraction and SHELXTL97 software and the result indicated that DMAPS crystallized in the orthorhombic system, space group P2₁/c with a = 14.6818(18), b = 7.1104(9), c = 14.9180(18) ?, V = 1548.5(3) ?³; Z = 4.

Full text of DOI:10.14233/ajchem.2015.18997

Asian Journal of Chemistry; Vol. 27, No. 10 (2015), 3818-3820
A
SIAN
J
OURNAL OF HEMISTRY
C
http://dx.doi.org/10.14233/ajchem.2015.18997
Synthesis and Characterization of 3-[N-(2-Methacroyloylethyl)-
N,N-dimethylamino]propane Sulfonate and its Crystal Structure
1,2
2
2,*
2
1,2
JIAN XIAO , XIU-QIN ZHANG , KAI WANG , QIANG CHEN and WEI-WEI XUE
1School of Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu Province, P.R. China
2High Technology Research Institute of Nanjing University, Changzhou 213162, Jiangsu Province, P.R. China
*Corresponding author: E-mail: wkcoool@163.com
Received: 8 January 2015;
Accepted: 27 February 2015;
Published online: 22 June 2015;
AJC-17354
3-[N-(2-Methacroyloylethyl)-N,N-dimethylamino]propane sulfonate (DMAPS) was synthesized by the ring-opening reaction of 1,3-
propanesultone, then electrophilic substitution with 2-(dimethylamino)ethyl methacrylate in the presence of acetone at 60 °C.
2-(Dimethylamino)ethyl methacrylate and a little polymerization inhibitor dissolved in acetone was added in three-necked flask, the
mixture was heated to 60 °C. 1,3-Propanesultone was dissolved in acetone and then be added drop-wise into the flask over 8 h. The
product was characterized by NMR and Mass spectrum. The crystal structure of 3-[N-(2-Methacroyloylethyl)-N,N-dimethylamino]propane
sulfonate was investigated using X-ray diffraction and SHELXTL97 software and the result indicated that DMAPS crystallized in the
orthorhombic system, space group P21/c with a = 14.6818(18), b = 7.1104(9), c = 14.9180(18) Å, V = 1548.5(3) Å3; Z = 4.
Keywords: 3-[N-(2-Methacroyloylethyl)-N,N-dimethylammonio]-propane sulfonate, Synthesis, Characterization, Crystal structure.
CH3
INTRODUCTION
N
CH3
O
The importance of zwitterionic compounds as biological
and ships aspects has been well established1. Some zwitterionic
compounds had been reported for the surfactant, medicines
and anticoagulant material, etc.2,3. For example, 2-methacry-
loyloxyethyl phosphorylcholine could be used for biomedical
materials4,5, 3-[(2-acrylamido)dimethylamino]propane sulfonate
is a useful monomer in the preparation of anticoagulant material6.
3-[N-(2-methacroyloylethyl)-N,N-dimethylamino]-
propane sulfonate (DMAPS, I), as one of zwitterionic compounds,
could be utilized for the synthesis of different chemicals that
have important application in the preparation of anticoagulant
polymeric films, such as P-AM-DMAPS7, etc. 2-(dimethyl-
amino)ethyl methacrylate (1) was synthesized by the method
of ester exchange with tetraphenyl titanate as a catalyst8, (I)
could be prepared from (1) with 1,3-propanesultone in the
presence of acetone at 50 °C for 20 h9. Herein, we report
DMAPS (1) was synthesized by methacryloyl chloride with
N,N-dimethyl ethanolamine in the presence of dichloromethane
at 0 °C for 12 h. (I) was prepared form the ring-opening reac-
tion of 1,3-propanesultone, then electrophilic substitution with
2-(dimethyl-amino)ethyl methacrylate (1) in the presence of
acetone at 60 °C for 8 h. Meanwhile, the crystal structure of
(I) also was investigated. The synthesis of DMAPS presented
as Scheme-I.
Et3N, 0 °C, 12 h
Cl
N
+
(
1)
HO
O
O
O
O
O
S
O
O
O
O-
N+
S
O
(I)
Scheme-I: Route for the synthesis of DMAPS
EXPERIMENTAL
N,N-Dimethyl ethanolamine and methacryloyl chloride
were supplied by Forever Reagent Co. Ltd. of Shanghai
(Shanghai, People’s Republic of China), their mass content
are 99 % determined by GC. 1,3-Propanesultone was supplied
by Aladdin Industrial Corporation (Shanghai, People’s
Republic of China), its mass content is 99.0 %. All other
chemicals were of reagent grade and used without purification
as received.

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

3820 Xiao et al.
Asian J. Chem.
TABLE-2
GEOMETRIC PARAMETERS FOR COMPOUND (I)
According to the data from X-ray crystallographic analysis,
compound (I) crystallized in a P21/c space group of the mono-
clinic system. The only H atom was positioned geometrically
and constrained to ride on C1 with C–H = 0.93 Å and Uiso(H)
=1.2Ueq(C). Hydrogen-bond geometry for compound (I) was
listed in Table-3. Unit cell parameters: a = 14.6818(18), b =
7.1104(9), c = 14.9180(18) Å, V = 1548.5(3) Å3; Z = 4.
Bond
C1–C2
C1–S1
Dist. (Å)
Bond
Dist. (Å)
1.523 (2)
1.7690(18)
0.9700
0.9700
1.525 (2)
0.9700
0.9700
1.521(2)
0.9700
0.9700
1.497(2)
0.9600
0.9600
0.9600
1.507(2)
0.9600
0.9600
0.9600
1.509 (2)
1.510 (3)
C6–H6A
C6–H6B
C7–O4
C7–H7A
C7–H7B
C8–O5
0.9700
0.9700
1.447(2)
0.9700
0.9700
1.198 (3)
1.345 (3)
1.491 (3)
1.368 (5)
1.446 (5)
0.9600
0.9600
0.9600
0.9300
0.9300
1.4589 (17)
1.4406 (16)
1.4380 (17)
0.8500
C1–H1A
C1–H1B
C2–C3
C2–H2A
C2–H2B
C3–N9
C3–H3A
C3–H3B
C4–N9
C4–H4A
C4–H4B
C4–H4C
C5–N9
C8–O4
C8–C9
TABLE-3
HYDROGEN-BOND GEOMETRY FOR COMPOUND (I)
C9–C11
C9–C10
C10–H10A
C10–H10B
C10–H10C
C11–H11A
C11–H11B
O1–S1
O2–S1
O3–S1
O6–H6D
O6–H6C
D–H
(Å)
H···A
(Å)
D···A
(Å)
D–H···A
(°)
D–H···A
O6–H6C···O1i
O6–H6C···O1ii
C1–H1B···O6iii
C3–H3A···O1iv
C3–H3B···O3v
C4–H4A···O4
C4–H4C···O3v
C5–H5A···O3v
C5–H5C···O2vi
C7–H7A···O3vii
C7–H7B···O2vi
C11–H11A···O2viii
0.85
0.85
0.97
0.97
0.97
0.96
0.96
0.96
0.96
0.97
0.97
0.93
2.36
2.39
2.44
2.55
2.55
2.46
2.41
2.50
2.39
2.55
2.59
2.42
2.816 (3)
2.902 (3)
3.383 (3)
3.476 (3)
3.392 (3)
2.958 (2)
3.272 (3)
3.342 (3)
3.308 (3)
3.472 (3)
3.546 (3)
3.309 (4)
114
119
163
159
145
112
149
146
160
159
170
159
C5–H5A
C5–H5B
C5–H5C
C6–N9
C6–C7
Angle
0.8499
Data (°)
Angle
Data (°)
C2–C1–S2
113.56 (13)
108.9
108.9
108.9
108.9
107.7
106.61 (14)
110.4
110.4
110.4
110.4
108.6
116.53 (14)
108.2
108.2
108.2
108.2
107.3
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
116.84 (15)
108.1
108.1
108.1
108.1
107.3
O4–C7–C6
108.62 (16)
110.0
110.0
110.0
110.0
C2–C1–H1A
S1–C1–H1A
C2–C1–H1B
S1–C1–H1B
H1A–C1–H1B
C1–C2–C3
C1–C2–H2A
C3–C2–H2A
C1–C2–H2B
C3–C2–H2B
H2A–C2–H2B
N9–C3–C2
N9–C3–H3A
C2–C3–H3A
N9–C3–H3B
C2–C3–H3B
H3A–C3–H3B
N9–C4–H4A
N9–C4–H4B
H4A–C4–H4B
N9–C4–H4C
H4A–C4–H4C
H4B–C4–H4C
N9–C5–H5A
N9–C5–H5B
H5A–C5–H5B
N9–C5–H5C
H5A–C5–H5C
H5B–C5–H5C
N9–C6–C7
N9–C6–H6A
C7–C6–H6A
N9–C6–H6B
C7–C6–H6B
H6A–C6–H6B
S1–C1–C2–C3
C1–C2–C3–N9
N9–C6–C7–O4
O5–C8–C9–Cl1
O4–C8–C9–Cl1
O4–C7–H7A
C6–C7–H7A
O4–C7–H7B
C6–C7–H7B
H7A–C7–H7B
O5–C8–O4
Symmetry code: (i) x,y,z+1; (ii) -x+1,-y,-z+1; (iii) -x+1, -y+1,-z+1;
(iv) -x+1,y+1/2,-z+1; (v) x, y+1, z; (vi) x, -y+1/2, z-1/2; (vii) x, -y-1/2,
z-1/2; (viii) -x, y+1/2, -z+1/2
108.3
122.3 (2)
124.5(2)
113.1 (3)
124.2 (3)
116.3 (3)
119.5 (3)
109.5
ACKNOWLEDGEMENTS
O5–C8–C9
O4–C8–C9
This work was financially supported by the Science and
Technology Research Project of Changzhou City-Technology
Support Program (Industry) (CE20140028). The authors also
gratefully acknowledged the support of Nanjing University and
Changzhou University in analysis.
C11–C9–Cl0
C11–C9–C8
C10–C9–C8
C9–C10–H10A
C9–C10–H10B
H10A–C10–H10B 109.5
C9–C10–H10C 109.5
H10A–C10–H10C 109.5
H10B–C10–H10C 109.5
109.5
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C9–C11–H11A
C9–C11–H11B
H11A–C11–H11B 120.0
120.0
120.0
C4–N9–C5
C4–N9–C6
C5–N9–C6
C4–N9–C3
C5–N9–C3
C6–N9–C3
C8–O4–C7
H6D–O6–H6C
O3–S1–O2
O3–S1–O1
O2–S1–O1
O3–S1–C1
O2–S1–C1
O1–S1–C1
109.26 (16)
111.73 (15)
110.40 (14)
110.04 (14)
105.70 (15)
109.54 (13)
115.31 (16)
108.1
113.00 (13)
111.94 (13)
112.11 (11)
107.28 (10)
107.06 (10)
104.86 (10)
-173.05 (13) C2–C3–N9–C4
-175.76 (15) C2–C3–N9–C5
76.9 (2)
-5.5 (4)
174.2 (2)
-59.8 (2)
-177.62 (16)
63.44 (19)
0.5 (3)
-179.25 (17)
167.92 (17)
-60.14 (18)
61.43 (17)
-179.31 (15)
C2–C3–N9–C6
O5–C8–O4–C7
C9–C8–O4–C7
C6–C7–O4–C8
C2–C1–S1–O3
C2–C1–S1–O2
C2–C1–S1–O1
O5–C8–C9–C10 174.2 (2)
O4–C8–C9–C10 -6.0 (3)
C7–C6–N9–C4
C7–C6–N9–C5
C7–C6–N9–C3
-62.3 (2)
59.5 (2)
175.54 (15)