Y. Shinohara et al.
chemicals and solvents were of reagent grade and purchased reduced pressure. Water (15 ml) and toluene (10 ml) were added.
from commercial vendors.
The aqueous phase was separated, washed with toluene
(10 ml ꢀ 2) and evaporated under reduced pressure to give
L-[2H4]homocysteine thiolactone HCl L-4 (0.30 g, 92%). Crystal-
lization from isopropanol afforded an analytical sample. m.p.
DL-3-Aminotetradeutero-2-thiophenone hydrochloride
(DL-[2H4]homocysteine thiolactone HCl) (2)
1
176–1771C. [a]2D5121.3 (c 0.05, H2O). H NMR (400 MHz, 2H2O): d
A solution of DL-[2H4]methionine 1 (1.00 g, 6.57 mmol) in 57%
hydriodic acid (25 g) was heated under reflux for 9 h. After
cooling, the solution was evaporated under reduced pressure
and remaining hydriodic acid was removed by azeotroping with
methanol (10 ml ꢀ 2). The residue was dissolved in water (10 ml)
and was subjected to anion-exchange column chromatography
(Dowex 1 ꢀ 8, 50–100 mesh, Clꢁ-form). The column was eluted
with 200 ml of water. The waste and effluent were evaporated
under reduced pressure to give DL-[2H4]homocysteine thiolac-
tone HCl 2 as a pale yellow solid (0.94 g, 91%). Crystallization
from ethanol afforded an analytical sample. m.p. 193–1971C
(dec.). 1H NMR (600 MHz, 2H2O): d 4.22 (1H, s, 3-H) 13C NMR
(150 MHz, 2H2O): d 27.21 (quintet, JC-D = 22 Hz, 5-C), 28.18
(quintet, JC-D = 21 Hz, 4-C), 58.04 (s, 3-C), 205.92 (s, 2-C). HR-ESI-
4.26 (1H, s, 3-H). HR-ESI-MS m/z 122.0586 [M1H]1 (Calcd. for
2
C4H4 H4NOS: 122.0578). Anal. Calcd. for C4H42H4NOSCl, C 30.47,
H(2H) 5.11, N 8.88. Found C 30.72, H(2H) 5.15, N 8.75.
Compound D-3 (0.35 g, 1.30 mmol) was treated in the same
manner as above to give compound D-4 (0.16 g, 78%).
Crystallization from isopropanol afforded an analytical sample.
m.p. 177–1781C. [a]D25 ꢁ21.7 (c 0.05, H2O). 1H NMR (400 MHz,
2H2O): d 4.24 (1H, s, 3-H). HR-ESI-MS m/z 122.0571 [M1H]1
(Calcd. for C4H42H4NOS: 122.0578). Anal. Calcd. for C4H42H4NOSCl,
C 30.47, H(2H) 5.11, N 8.88. Found C 30.63, H(2H) 5.19, N 8.73.
Acknowledgement
This work was supported by a grant from the Promotion and
Mutual Aid Corporation for Private Schools of Japan.
MS m/z 122.0578 [M1H]1 (Calcd. for C4H4 H4NOS: 122.0578).
Anal. Calcd. for C4H42H4NOSCl, C 30.47, H(2H) 5.11, N 8.88. Found
C 30.54, H(2H) 5.13, N 8.69.
2
(3S,20S)-3-(20-Methoxy-20-phenyl-)acetamido-4,5-tetradeu-
tero-2-thiophenone (L-3) and (3R,20S)-3-(20-methoxy-20-
phenyl-)acetamido-4,5-tetradeutero-2-thiophenone (D-3)
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