Amino Thiols and/or Their Disulfides via Thiazolinium Salts
after 15 h, characterized in the presence of compound 8. 1H NMR
(500 MHz, D2O): δ = 1.64 (dq, J = 8.6, 13.2 Hz, 1 H), 1.86–2.01
crude yield after 6 h, characterized in the presence of compound 8.
1H NMR (500 MHz, D2O): δ = 2.82 (t, J = 6.9 Hz, 2 H, CH2S),
(m, 2 H), 2.10–2.19 (m, 1 H), 2.65 (dd, JAX = 8.4, JAB = 14.5 Hz, 3.25 (t, J = 6.9 Hz, 2 H, CH2N), 4.25 (s, 2 H, CH2Ph), 7.47 (s, 5 H,
1 H, CHHS), 2.87 (dd, JBX = 5.1, JAB = 14.5 Hz, 1 H, CHHS),
3.18–3.27 (m, 2 H, CH2N), 3.58–3.54 (m, 1 H, CHN) ppm. 13C
NMR (125 MHz, D2O): δ = 23.2, 25.0, 28.9, 45.3, 62.6 ppm.
HRMS: calcd. for C5H12NS 118.0690; found 118.0696.
C6H5) ppm. HRMS: calcd. for C9H14NS 168.0847; found 168.0844.
Bis[2-(benzylamino)ethyl] Disulfide Hydrochloride (6f): Prepared ac-
cording to the General Procedure B from amino thiol 5f; quantita-
tive crude yield after 15 h, isolated as a white powder (113 mg,
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Bis{[(S,S)-2-pyrrolidinyl]methyl} Disulfide Hydrochloride (6a): Pre-
pared according to the General Procedure B from amino thiol 5a;
quantitative crude yield after 72 h, isolated as a white powder in
(76 mg, 75%). [α]2D0 = +289.2 (c = 0.5, MeOH). 1H NMR
(400 MHz, D2O): δ = 1.67–1.74 (m, 2 H), 1.93–2.03 (m, 4 H), 2.17–
2.23 (m, 2 H), 2.85 (dd, JAX = 9.6, JAB = 14.4 Hz, 2 H, CHHS),
3.11 (dd, JBX = 4.4, JAB = 14.4 Hz, 2 H, CHHS), 3.23–3.29 (m, 4
H, CH2N), 3.89–3.97 (m, 2 H, CHN) ppm. 13C NMR (63 MHz,
D2O): δ = 23.6, 29.7, 37.5, 45.8, 59.3 ppm. HRMS: calcd. for
C10H21N2S2 233.1146; found 233.1154. C10H22Cl2N2S2 (305.33 +
0.4HCl): calcd. C 37.54, H 8.76, N 7.06, S 20.04; found C 37.42,
H 8.70, N 7.25, S 19.77.
85%). H NMR (500 MHz, D2O): δ = 2.89 (t, J = 7.3 Hz, 4 H, 2
CH2S), 3.33 (t, J = 7.3 Hz, 4 H, 2 CH2N), 4.20 (s, 2 H, 4 CH2Ph),
7.38–7.43 (m, 10 H, 2 C6H5) ppm. 13C NMR (100 MHz, D2O): δ
= 38.4, 44.8, 50.9, 129.3, 129.8, 129.9, 130.3 ppm. HRMS: calcd.
for C18H25N2S2 333.1459; found 333.1462. C18H26Cl2N2S2 (405.45
+ 1.6HCl): calcd. C 46.61, H 6.00, N 6.04; found C 46.47, H 5.88,
N 6.42.
(R)-2-(Methylamino)-2-phenylethanethiol Hydrochloride (5g): Pre-
pared according to the General Procedure A (i) from thiazolidine
4g; quantitative crude yield after 2 h, characterized in the presence
of compound 8. 1H NMR (400 MHz, D2O): δ = 2.55 (s, 3 H,
NCH3), 3.12–3.17 (m, 2 H, CH2S), 4.32 (t, J = 7.2 Hz, 1 H, CHN),
7.41–7.45 (m, 2 H, C6H5), 7.49–7.52 (m, 3 H, C6H5) ppm. 13C
NMR (100 MHz, D2O): δ = 25.9, 30.9, 65.0, 128.2, 129.5, 130.1,
132.5 ppm. HRMS: calcd. for C9H14NS 168.0847; found 168.0852.
2-(Methylamino)ethanethiol Hydrochloride (5b): Prepared accord-
ing to the General Procedure A (i) from thiazolidine 4b; quantita-
tive crude yield after 2 h, characterized in the presence of com-
1
pound 8. H NMR (500 MHz, D2O): δ = 2.69 (s, 3 H, CH3), 2.80
Bis[(R,R)-2-(methylamino)-2-phenylethyl] Disulfide Hydrochloride
(6g): Prepared according to the General Procedure B from amino
thiol 5g; quantitative crude yield after 72 h, isolated as a white
(t, J = 6.0 Hz, 2 H, CH2S), 3.19 (t, J = 6.0 Hz, 2 H, CH2N) ppm.
Bis[2-(methylamino)ethyl] Disulfide Hydrochloride (6b): Prepared
according to the General Procedure B from amino thiol 5b; quanti-
tative crude yield after 5 d, isolated as a white powder (76 mg,
powder (105 mg, 79%). [α]2D0 = +93.1 (c = 0.8, MeOH). H NMR
1
(400 MHz, D2O): δ = 2.55 (s, 6 H, 2 NCH3), 3.28 (dd, JAX = 8.2,
JAB = 14.3 Hz, 2 H, 2 CHHS), 3.39 (dd, JBX = 6.4, JAB = 14.3 Hz,
2 H, 2 CHHS), 4.46 (dd, JAX = 8.2, JBX = 6.4 Hz, 2 H, 2 CHN),
7.38–7.43 (m, 4 H, C6H5), 7.50–7.55 (m, 6 H, C6H5) ppm. 13C
NMR (100 MHz, D2O): δ = 30.8, 39.4, 62.1, 128.6, 129.6, 130.3,
132.0 ppm. HRMS: calcd. for C18H25N2S2 333.1459; found
333.1448. C18H26Cl2N2S2 (405.45 + 0.2HCl): calcd. C 52.37, H
6.40, N 6.79; found C 52.35, H 6.41, N 6.73.
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91%). H NMR (400 MHz, D2O): δ = 2.64 (s, 6 H, 2 NCH3), 2.92
(t, J = 6.5 Hz, 4 H, 2 SCH2), 3.32 (t, J = 6.5 Hz, 4 H, 2 NCH2)
ppm. 13C NMR (63 MHz, D2O): δ = 31.9, 32.8, 47.0 ppm. HRMS:
calcd. for C6H17N2S2 181.0833; found 181.0836. C6H18Cl2N2S2
(253.26 + 0.4HCl): calcd. C 26.91, H 6.92, N 10.46, S 23.94; found
C 27.12, H 7.13, N 10.26, S 23.69.
2-(Butylamino)ethanethiol Hydrochloride (5c): Prepared according
to the General Procedure A (i, ii) from thiazolidine 4c; quantitative
crude yield after 15 h, isolated as a white powder (51 mg, 91%). 1H
NMR (400 MHz, D2O): δ = 0.82 (t, J = 7.6 Hz, 3 H, CH3CH2),
1.28 (sext, J = 7.6 Hz, 2 H, CH3CH2), 1.52–1.60 (m, 2 H, CH2),
2.73 (t, J = 6.8 Hz, 2 H, CH2S), 2.96 (t, J = 7.6 Hz, 2 H, NCH2),
3.14 (t, J = 6.8 Hz, 2 H, CH2N) ppm. 13C NMR (100 MHz, D2O):
δ = 12.7, 19.1, 19.8, 27.3, 47.2, 49.6 ppm. HRMS: calcd. for
Bis[(S,S)-2-isopropyl-2-(methylamino)ethyl] Disulfide Hydrochloride
(6h): Prepared according to the General Procedure B from amino
thiol 5h; quantitative crude yield after 48 h, isolated as a light-
brown powder (92 mg, 83%). [α]2D0 = +247.1 (c = 0.35, MeOH). 1H
NMR (500 MHz, D2O): δ = 0.99 (d, J = 7.0 Hz, 6 H, 2 CHCH3),
1.04 (d, J = 7.0 Hz, 6 H, 2 CHCH3), 2.21–2.29 (m, 2 H, 2 CHCH3),
2.78 (s, 6 H, 2 NCH3), 2.98 (dd, JAX = 8.2, JAB = 15.0 Hz, 2 H, 2
CHHS), 3.16 (dd, JBX = 4.1, JAB = 15.0 Hz, 2 H, 2 CHHS), 3.40–
3.45 (m, 2 H, 2 CHN) ppm. 13C NMR (100 MHz, D2O): δ = 16.2,
17.8, 27.7, 31.2, 34.2, 63.2 ppm. HRMS: calcd. for C12H29N2S2
265.1772; found 265.1764. C12H30Cl2N2S2 (337.42 + 0.6HCl):
calcd. C 40.50, H 8.58, N 7.80; found C 39.92, H 8.48, N 8.29.
C6H16NS 134.1003; found 134.1009. C6H16ClNS (169.72
+
0.1HCl): calcd. C 41.57, H 9.36, N 8.08; found C 41.77, H 9.57, N
8.03.
2-(Allylamino)ethanethiol Hydrochloride (5d): Prepared according
to the General Procedure A (i, ii) from thiazolidine 4d; quantitative
crude yield after 15 h, isolated as a white powder (30 mg, 60%). 1H
NMR (400 MHz, D2O): δ = 2.88 (t, J = 7.3 Hz, 2 H, CH2S), 3.20
(t, J = 7.3 Hz, 2 H, CH2N), 3.60 (d, J = 6.9 Hz, 2 H, CHCH2N),
5.38–5.44 (m, 2 H, CH2=CH), 5.75–5.85 (m, 1 H, CH=CH2) ppm.
13C NMR (100 MHz, D2O): δ = 29.9, 46.3, 49.4, 124.0, 127.1 ppm.
HRMS: calcd. for C5H12NS 118.0690; found 118.0679.
Bis[(S,S)-2-(benzylamino)-2-isopropylethyl] Disulfide Hydrochloride
(6i): Prepared according to the General Procedure B from amino
thiol 5i; quantitative crude yield after 48 h, isolated as a white pow-
der (135 mg, 84%). [α]2D0 = +208.2 (c = 0.5, MeOH). 1H NMR
(500 MHz, D2O): δ = 0.93 (d, J = 7.5 Hz, 6 H, 2 CHCH3), 0.96 (d,
J = 7.5 Hz, 6 H, 2 CHCH3), 2.20–2.27 (m, 2 H, 2 CHCH3), 2.85
(dd, JAX = 8.2, JAB = 15.0 Hz, 2 H, 2 CHHS), 2.95 (dd, JBX = 4.1,
JAB = 15.0 Hz, 2 H, 2 CHHS), 3.26–3.30 (m, 2 H, 2 CHN), 4.32–
4.39 (m, 4 H, 2 CH2Ph), 7.50 (s, 10 H, 2 C6H5) ppm. 13C NMR
(100 MHz, D2O): δ = 16.1, 17.6, 27.9, 34.4, 49.6, 60.6, 129.5, 129.9,
130.1 ppm. HRMS: calcd. for C24H37N2S2 417.2398; found
417.2386. C24H38Cl2N2S2 (489.61 + 1.4HCl): calcd. C 53.32, H
7.35; found C 53.55, H 7.38.
2-[(2-Mercaptoethyl)amino]ethanoic Acid Hydrochloride (5e): Pre-
pared according to the General Procedure A (i, ii) from thiazolidine
4e; quantitative crude yield after 15 h, isolated as a light-brown
1
powder (40 mg, 71%). H NMR (400 MHz, D2O): δ = 2.98 (t, J =
6.8 Hz, 2 H, CH2S), 3.42 (t, J = 6.8 Hz, 2 H, CH2N), 3.79 (s, 2
H, CH2) ppm. 13C NMR (100 MHz, D2O): δ = 32.5, 46.2, 48.1,
169.6 ppm. C4H10ClNO2S (171.65 + 0.1HCl): calcd. C 27.41, H
5.81, N 7.99; found C 27.50, H 5.68, N 7.84.
2-(Benzylamino)ethanethiol Hydrochloride (5f): Prepared according
to the General Procedure A (i) from thiazolidine 4f; quantitative
(R,R)-N,NЈ-Dimethylcysteine Hydrochloride (6j): Prepared accord-
ing to the General Procedure B from amino thiol 5j; quantitative
Eur. J. Org. Chem. 2009, 4357–4364
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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