Synthesis, crystal structure, and spectral characteristics of N-(tert-Butyl)aminomethanesulfonic acid

Article abstract of DOI:10.1134/S1070363215100102

A new method of the synthesis of N-(tert-butyl)aminomethanesulfonic acid in the system SO₂-(CH₃)₃CNH₂-CH₂O-H₂O was developed. The target compound [(CH₃)₃C]NHCH₂SO₃H was characterized by means of X-ray diffraction analysis, IR spectroscopy, and mass spectrometry.

Full text of DOI:10.1134/S1070363215100102

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 10, pp. 2282–2284. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © R.E. Khoma, V.O. Gel’mbol’dt, A.A. Ennan, V.N. Baumer, A.N. Puzan, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85,
No. 10, pp. 1650–1652.
Synthesis, Crystal Structure, and Spectral Characteristics
of N-(tert-Butyl)aminomethanesulfonic Acid
a,b
c
a
d,e
d
R. E. Khoma , V. O. Gel’mbol’dt , A. A. Ennan , V. N. Baumer , and A. N. Puzan
a
Physicochemical Institute for Human and Environmental Protection,
Ministry of Education and Science of the National Academy of Sciences of Ukraine,
ul. Preobrazhenskaya 3, Odessa, 65082 Ukraine
e-mail: rek@onu.edu.ua
b
Mechnikov Odessa National University, Odessa, Ukraine
c
Odessa National Medical University, Odessa, Ukraine
d
Institute of Single Crystals of the National Academy of Sciences of Ukraine, Kharkov, Ukraine
e
Karazin Kharkiv National University, Kharkov, Ukraine
Received April 2, 2015
Abstract—A new method of the synthesis of N-(tert-butyl)aminomethanesulfonic acid in the system SO
CH CNH –CH O–H O was developed. The target compound [(CH С]NHCH SO H was characterized by
means of X-ray diffraction analysis, IR spectroscopy, and mass spectrometry.
2
–
(
3
)
3
2
2
2
3
)
3
2
3
Keywords: sulfur(IV) oxide, paraformaldehyde, primary alkylamine, condensation
DOI: 10.1134/S1070363215100102
Compounds of zwitterionic structure, in particular,
aminoalkanesulfonic acids, their derivatives and salts
yield. The composition and structure of the target
compound was confirmed by mass spectrometry,
elemental analysis, IR and NMR spectroscopy, and
X-ray diffraction analysis.
[1–4] are promising components of buffer solutions
1, 2] widely used in biological research for
[
monitoring the medium pH. Moreover, the compounds
are valuable as biologically active species exhibiting
various types of pharmacological activity [4, 5].
IR spectroscopy data of the compound indicated the
zwitterionic structure similarly as for the earlier
investigated analogs [6, 7].
Earlier we developed an original method of synthesis
of aminoalkanesulfonic acids N-derivatives by an
example of sulfur(IV) oxide reaction with a mixture of
monoethanolamine and formaldehyde in aqueous
solution that led to the formation of N-(hydroxyethyl)-
aminomethanesulfonic acid [6] (Scheme 1).
General view of the molecule of N-(tert-butyl)amino-
methanesulfonic acid is presented in Fig. 1; the values
of bond lengths and bond angles are listed in Table 1.
Scheme 1.
R
N
In extention of [6] we attempted the preparation of
one of the N-derivatives of aminoalkanesulfonic acid
with the use in the reaction of tert-butylamine. In the
present report we describe the synthesis of N-(tert-
butyl)aminomethanesulfonic acid and the study of its
structure.
H O
2
3mRNH + 3(CH O)
m
+ 3mH O
2
2
m
2
N
N
R
R
R
N
O
R
The synthesis was accomplished by the reaction of
sulfur(IV) oxide with aqueous solution of a mixture of
tert-butylamine and formaldehyde; N-(tert-butyl)amino-
methanesulfonic acid was obtained in quantitative
+
3SO + 3H O
3
N
S
2
2
N
N
H
OH
R
R
O
R = CH CH OH, t-Bu.
2
2
2
282

SYNTHESIS, CRYSTAL STRUCTURE, AND SPECTRAL CHARACTERISTICS
2283
Fig. 1. General view of the molecule of N-(tert-butyl)-
Fig. 2. Crystal packing and hydrogen bonds in the molecule
aminomethanesulfonic acid; thermal ellipsoids at the 50%
probability level.
of N-(tert-butyl)aminomethanesulfonic acid. Hydrogen
bonds are depicted by dashed lines.
In the crystal packing of the molecules hydrogen
bonds N–H···O exist between the ammonium group of
one molecule and the oxygen atom of the sulfo group
of the neighboring molecule that is bound with the first
one through a spiral axis. Such hydrogen bonds led to
the formation of infinite chains of molecules stretched
along the crystallographic axis [010] (Fig. 2). There
were no hydrogen bonds between the neighboring
chains, only shortened interactions С–H···O were
observed. Characteristics of the hydrogen bonds are
given in Table 2.
was confirmed by an example of the system SO2–
(CH ) CNH –CH O–H O.
3
3
2
2
2
EXPERIMENTAL
Commercially available sulfur(IV) oxide was used
after preliminary purification and drying according to
the described method [9]. tert-Butylamine and
paraformaldehyde of “pure” grade were commercially
available reagents and were used without additional
purification.
IR spectra were recorded on a Spectrum BX II FT-
IR System (Perkin-Elmer) spectrophotometer in the
range of 4000–350 cm from KBr pellets. Mass
Hence, a possibility of the direct synthesis of N-
derivatives of aminomethanesulfonic acid through the
condensation accompanied by oxidation S(IV)→S(VI)
–1
spectra were registered on a МХ-1321 instrument
(
direct input of the sample into the ion source, energy
of ionizing electrons 70 eV). Elemental analysis on
carbon, hydrogen, and nitrogen was done on a CNH-
Table 1. Bond lengths and bond angles in the structure of N-
(
tert-butyl)aminomethanesulfonic acid
Bond d, Å Angle ω, deg
S –O 1.421(3) O S O 113.98(18) N C S
Angle
ω, deg
Table 2. Characteristics of hydrogen bonds D–H···A in the
molecule of N-(tert-butyl)aminomethanesulfonic acid
1
2
2
1
3
1
5 1
111.4(2)
1
3
2
1
1
3
1
1
S –O 1.453(3) O S O 114.63(19) C C N 109.1(3)
Distance, Å
Angle
DHA,
deg
1
1
3
1
1
3
1
2
Coordinates
of atom А
S –O 1.459(3) O S O 111.14(16) C C C
113.0(3)
D–H···A
1
5
2
1
5
1
1
2
S –C 1.761(4) O S C 104.93(18) N C C 108.0(3)
1
5
3
1
5
3
1
4
N –C 1.488(5) O S C 106.29(18) C C C
111.0(4)
1
1A
1
N H ···O 0.82(3) 2.03(4) 2.829(4) 166(4) –x + 1/2,
y + 1/2,
1
1
1
1
5
1
1
4
N –C 1.521(5) O S C 104.87(18) N C C 105.3(3)
–
z + 1/2
1
3
5
1
1
2
1
4
C –C 1.513(5) C N C 117.3(3)
C C C
110.2(3)
1
1B
3
N H ···O 0.93(3) 1.93(3) 2.862(4) 175(3) –x + 1/2,
1
2
C –C 1.524(5)
y – 1/2,
–z + 1/2
1
4
C –C 1.532(5)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 10 2015

2
284
KHOMA et al.
analyzer; sulfur content was determined in Schoeniger
flask.
1435 sh, 1408 m, 1382 m, 1324 m, 1286 m, 1266 m;
1245 s, 1234 s (SО ), 1199 sh, 1164 s; 1062 s, 1012 m
2
(
5
(
SО ); 878 w, 852 w, 800 m, 741 m, 605 s; 549 m (S–О),
20 m, 505 sh, 472 m, 444 m, 418 w. Mass spectrum
2
X-Ray diffraction was performed on an Oxford
Diffraction diffractometer (MoK -radiation, graphite
α
EI), m/z (I , %): 91 (10), 85 (13), 70 (98), 64 (87)
rel
monochromator, CCD-detector Sapphire-3). The solu-
tion and refinement of the structure were accomplished
with the use of the complex of programs SHELX-97
+
+
[SO ] , 59 (50), 57 (100) [(CH ) C] , 48 (38), 41 (94),
2 3 3
3
2
8
8 (27), 30 (29). Found, %: С 35.20; H 8.31; N 8.50; S
0.05. C H NO S. Calculated, %: C 35.91; H 7.84; N
5
13
3
[
8]. Hydrogen atoms were found from the difference
.38; S 19.17. M 167.23.
synthesis; the hydrogen atoms of methyl and
methylene groups were refined according the rider
model. The hydrogen atoms involved into hydrogen
bonds were refined isotropically. The main crystallo-
graphic data and the results of the crystal refinement:
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2
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8
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–
1
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2
2
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+
+
362 m (N H), 1624 m [δ(N H )], 1487 m, 1455 m,
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 10 2015