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H. Yu et al.
PAPER
Substituted Taurines 5 and 6; General Procedure
1H NMR (300 MHz, D2O, HDO): d = 2.07 (s, 3 H, CH3), 3.35–3.46
(m, 3 H, CH, CH2), 4.08 (dd, J = 7.2, 10.5 Hz, 1 H, CHH), 4.31 (dd,
J = 3.6, 10.5 Hz, 1 H, CHH), 6.76 (d, J = 8.7 Hz, 2 H, ArH), 7.01
(d, J = 8.7 Hz, 2 H, ArH).
13C NMR (75.5 MHz, HCO2H): d = 155.9, 132.0, 130.7, 115.2,
66.0, 56.6, 38.9, 20.1.
To a stirred soln of NH3 (11.2 mmol) in MeOH (11.2 mL) was add-
ed AgNO3 (0.21 g, 1.23 mmol). After completely dissolved, a soln
of thiirane 2 (1.12 mmol) in MeOH (1 mL) was added dropwise at
r.t. over a period of 0.5 h. After stirring for a further 3 h, the solvent
was removed to afford yellow solid 3 or 4, which was suspended in
CH2Cl2 (20 mL). After addition of Na2S·9 H2O (1.75 g, 7.29 mmol),
to the suspended soln was added dropwise concd HCl (3.74 mL,
44.8 mmol) through a pressure-equilibrium addition funnel capped
with a balloon to keep that the mixture was stirred under the atmo-
sphere of H2S for 6 h. The soln was adjusted to basic with 2 M
NaOH, the mixture was filtered, and the AgS precipitates were
washed with CH2Cl2. The washings and filtrate were combined and
separated. The aqueous phase was extracted with CH2Cl2 (3 × 5
mL). The combined organic phases were washed with H2O (10 mL)
and brine (10 mL) and dried (MgSO4). After removal of the solvent
under reduced pressure, the residue was diluted with HCO2H (2
mL) and used directly in the next step without purification.
MS (ESI): m/z = 246 [M + H]+.
HRMS: m/z [M + H] calcd for C10H16NO4S: 246.0800; found:
246.0798.
1-Amino-3-(dibenzylamino)propane-2-sulfonic Acid (5f)
Colorless crystals; overall yield: 59% (from thiirane 2f); mp 190–
192 °C.
IR: 3431 (br, NH, OH), 2438 (Bn2NH+CH2), 1243 (SO2), 1214
cm–1 (SO2).
1H NMR (300 MHz, D2O, HDO): d = 2.99 (m, 2 H, CH2), 3.36 (m,
2 H, CH2), 3.42 (m, 1 H, CH), 4.14 (m, 2 H, 2 CHH), 4.46 (m, 2 H,
2 CHH), 7.20–7.20 (m, 10 H, ArH).
13C NMR (75.5 MHz, HCO2H): d = 131.3, 131.1, 130.2, 129.1,
59.1, 51.8, 51.6, 38.3.
To a performic acid soln, prepared by mixing and stirring 30% H2O2
(0.76 mL, 6.72 mmol) and 88% HCO2H (6.72 mL) at r.t. for 1 h,
cooled in an ice bath, was added dropwise the above prepared soln
at 0 °C over a period of 10 min. The resulting mixture was stirred
and allowed to warm to r.t. for 1.5 d. After removal of solvent, the
residue was crystallized (MeOH) to give colorless crystals of sub-
stituted taurines.
MS (ESI): m/z = 335 [M + H]+.
HRMS: m/z [M + H] calcd for C17H23N2O3S: 335.1423; found:
335.1418.
1-Aminohexane-2-sulfonic Acid (5a)
Colorless crystals; overall yield: 50% (from thiirane 2a); mp 339–
340 °C (dec.).
IR: 3420 (br, OH, NH), 1221 (SO2), 1150 cm–1 (SO2).
1H NMR (300 MHz, D2O, HDO): d = 3.25 (dd, J = 3.0, 13.8 Hz, 1
H, CHHN), 3.15 (dd, J = 9.0, 13.8 Hz, 1 H, CHHN), 2.95 (m, 1 H,
CHS), 1.79 (m, 1 H, CHH), 1.48–1.18 (m, 5 H, CH2CH2; 1 H,
CHH), 0.78 (t, J = 7.2 Hz, 3 H, CH3).
2-Amino-2-phenylethanesulfonic Acid (6g)
Colorless crystals; overall yield: 47% (from thiirane 2g); mp 314–
315 °C (Lit.9 314–315 °C).
13C NMR (75.5 MHz, D2O, HCO2H): d = 134.6, 130.3, 129.7,
127.3, 53.2, 52.9.
2-Amino-2-(4-methylphenyl)ethanesulfonic Acid (6h)
Colorless crystals; overall yield: 44% (from thiirane 2h); mp 290–
291 °C (dec.) (Lit.21 347 °C).
13C NMR (75.5 MHz, D2O, HCO2H): d = 57.5, 39.8, 28.6, 27.8,
22.4, 13.7.
MS (ESI): m/z = 182 [M + H]+.
1H NMR (300 MHz, D2O, HDO): d = 2.14 (s, 3 H, CH3), 3.25 (dd,
J = 4.8, 14.4 Hz, 1 H, NCH2), 3.40 (dd, J = 9.0, 14.4 Hz, 1 H,
NCH2), 4.57 (dd, J = 4.8, 9.0 Hz, 1 H, CH), 7.12 (d, J = 8.6 Hz, 2
H, ArH), 7.15 (d, J = 8.6 Hz, 2 H, ArH).
HRMS: m/z [M + H] calcd for C6H16NO3S: 182.0851; found:
182.0847.
13C NMR (75.5 MHz, HCO2H): d = 140.9, 132.1, 130.6, 127.6,
53.6, 52.7, 20.8.
1-Aminooctane-2-sulfonic Acid (5b)
Colorless crystals; overall yield: 43% (from thiirane 2b); mp 345–
MS (ESI): m/z = 216 [M + H]+.
346 °C (Lit.16 >360 °C).
HRMS: m/z [M + H] calcd for C9H14NO3S: 216.0674; found:
216.0662.
13C NMR (75.5 MHz, DMSO-d6): d = 55.6, 39.5, 31.1, 28.6, 27.9,
26.2, 22.1, 14.0.
2-Amino-2-phenylpropanesulfonic Acid (6i)
Colorless crystals; overall yield: 68% (from thiirane 2i); mp 236–
238 °C (Lit.10f 236–238 °C).
13C NMR (75.5 MHz, D2O, DMSO): d = 147.4, 130.4, 128.9, 127.1,
1-Amino-3-(benzyloxy)propane-2-sulfonic Acid (5c)
Colorless crystals; overall yield: 49% (from thiirane 2c); mp 269–
270 °C (Lit.16 227–229 °C).
13C NMR (75.5 MHz, D2O, HCO2H): d = 130.6, 130.28, 130.27,
64.4, 55.7, 31.1.
129.8, 59.7, 57.8, 51.8.
2-Amino-2-phenylbutanesulfonic Acid (6j)
Colorless crystals; overall yield: 44% (from thiirane 2j); mp 253–
255 °C (Lit.10f 253–255 °C).
13C NMR (75.5 MHz, D2O, DMSO): d = 139.0, 131.5, 131.0, 127.5,
1-Amino-3-phenoxypropane-2-sulfonic Acid (5d)
Colorless crystals; overall yield: 63% (from thiirane 2d); mp 329–
331 °C (Lit.16 307–309 °C).
13C NMR (75.5 MHz, D2O, HCO2H): d = 157.7, 129.9, 122.0,
63.3, 59.3, 34.3, 9.1.
114.8, 65.1, 56.4, 39.2.
2-Amino-2,2-diphenylethanesulfonic Acid (6k)
Colorless crystals; overall yield: 11% (from thiirane 2j); mp 239–
242 °C (dec.) [Lit.10f 239–242.5 °C (dec.)].
13C NMR (75.5 MHz, D2O, DMSO): d = 147.1, 130.4, 129.3, 128.4,
1-Amino-3-(4-methylphenoxy)propane-2-sulfonic Acid (5e)
Colorless crystals; overall yield: 47% (from thiirane 2e); mp 323–
325 °C.
IR: 3375 (br, NH, OH), 1247 (SO2), 1198 cm–1 (SO2).
62.2, 61.8.
Synthesis 2009, No. 13, 2205–2209 © Thieme Stuttgart · New York