118
Q. Qi et al. / Journal of Fluorine Chemistry 133 (2012) 115–119
4.4. Characterization of 5-(perfluoropropan-2-yl)thiazol-2-amine
(thin film) 3450, 3281, 3135, 2939, 1630, 1537, 1509, 1312, 1218,
1095, 1041, 949, 913, 721 cmÀ1
.
Sodium dithionite (261 mg, 1.5 mmol) in one portion was
added to a mixture of 2-aminothiazole (100 mg, 1.0 mmol),
NaHCO3 (252 mg, 3.0 mmol) and (CF3)2CFI (443 mg, 1.5 mmol)
in 5.2 mL acetonitrile and 1.3 mL water at 5–10 8C under argon. The
mixture was stirred until complete conversion of starting material
as indicated by TLC analysis (within 30 min). Acetonitrile was
removed under reduced pressure (Caution: the temperature of the
water bath of the rotvap maintained below 15 8C. Otherwise,
higher temperature resulted in the decomposition of the product).
The mixture was extracted with diethyl ether (4.0 mL Â 1) and the
organic layers were dried over Na2SO4. The solvent was removed
under vacuum to give a white solid in 76% yield, 204 mg. The white
solid was pure as indicated by 1H NMR spectroscopy and Mass
Spectroscopy. Note: The title product was stable for months when
stored at -20 8C. 5-(perfluoropropan-2-yl)thiazol-2-amine: White
4.5.3. 5-(Perfluoropropan-2-yl)-4-phenylthiazol-2-amine (Table 2,
entry 8)
The general procedure conducted with sodium dithionite (2.0 g,
11.4 mmol), 2-aminothiazole (1.0 g, 5.7 mmol), NaHCO3 (960 mg,
11.4 mmol) and (CF3)2CFI (2.52 g, 8.6 mmol) in 20.0 mL DMF and
10.0 mL water gave 1.66 g (85%) of the product as a white solid.
Mp: 132–133 8C. 1H NMR (300 MHz, CDCl3/TMS)
d 7.37 (m, 5H),
5.70 (br, 2H). 19F NMR (282 MHz, CDCl3)
d
À76.10 (d, J = 10.4 Hz,
6F), À174.33 (m, 1F). 13C NMR (100 MHz, CDCl3)
d 168.4, 156.2,
135.0 (d, J = 2.2 Hz), 129.0 (d, J = 2.9 Hz), 128.6, 127.7, 120.3 (qd,
J = 285.1, 27.2 Hz, CF3), 102.0 (d, J = 22.6 Hz), 89.4–93.4 (m). MS
(ESI positive ion): 345.0 (M+1); HRMS (ESI) calcd for C12H8F7N2S+1
(M+H): 345.0291. Found: 345.0302. IR (thin film) 3461, 3279,
3097, 2970, 1631, 1527, 1298, 1206, 1159, 1068, 969, 934, 922,
solid, isolated yield: 76%. 1H NMR (300 MHz, CDCl3/TMS)
1H), 5.44 (br, 2H). 19F NMR (282 MHz, CDCl3)
d
7.33 (s,
777, 754, 723, 706, 663, 596 cmÀ1
.
d
À75.93 (d,
J = 9.3 Hz, 6F), À167.60 (m, 1F). MS (ESI positive ion): 269.0 (M+1);
HRMS (ESI) calcd for C6H4F7N2S+1 (M+H): 268.9978. Found:
268.9977.
4.6. Reductive defluorination of 4-methyl-5-(perfluoropropan-2-
yl)thiazol-2-amine
A solution of sodium dithionite (123 mg, 0.7 mmol) and 4-
4.5. Typical procedure of the reductive polyfluoroalkylation of
substituted 2-aminothiazoles
methyl-5-(perfluoropropan-2-yl)thiazol-2-amine
(100 mg,
0.4 mmol) in 1.2 mL acetonitrile and 1.2 mL water was heated
to 60 8C under argon. The mixture was stirred until complete
conversion of starting material as indicated by TLC analysis.
Acetonitrile was removed under reduced pressure and water
(5 mL) was added. The mixture was extracted with ethyl acetate
(4.0 mL Â 3) and the combined organic layers were dried over
Na2SO4. The solvent was removed under vacuum and the residue
was purified by column chromatography on silica gel (petroleum/
ethyl acetate) to give 55 mg (60%) of the product as a white solid. 5-
Sodium dithionite (2.0 mmol) was added in one portion to a
mixture of 2-aminothiazole (1.0 mmol), NaHCO3 (2.0 mmol) and
polyfluoroalky iodide (1.5 mmol) in 10.0 mL acetonitrile/water
(3:1/v:v) at 5–10 8C under Ar atmosphere. The mixture was stirred
until complete conversion of starting material as indicated by TLC
or 19F NMR analysis. Acetonitrile was removed under reduced
pressure and water (5 mL) was added. The mixture was extracted
with ethyl acetate (4.0 mL Â 3) and the combined organic layers
were dried over Na2SO4. The solvent was removed under vacuum
and the residue was purified by column chromatography on silica
gel (petroleum/ethyl acetate) to give the product.
(1,1,1,3,3,3-
hexafluoropropan-2-yl)-4-methylthiazol-2-amine.
5.61 (br, 2H),
Mp: 104–105 8C. 1H NMR (300 MHz, CDCl3/TMS)
d
4.30 (m, J = 7.8 Hz, 1H), 2.20 (s, 3H). 19F NMR (282 MHz, CDCl3)
d
À66.70 (d, J = 7.3 Hz, 6F). 13C NMR (100 MHz, CDCl3)
d 168.3, 151.3,
122.6 (q, J = 281.4 Hz), 102.9, 47.8 (septet, J = 31.0 Hz), 14.98. MS
(ESI positive ion): 265.0 (M+1); HRMS (ESI) calcd for C7H7F6N2S+1
(M+H): 265.0229. Found: 265.0227. IR (thin film) 3469, 3231,
3080, 2927, 1613, 1574, 1533, 1509, 1348, 1331, 1271, 1224, 1203,
4.5.1. 5-(1,1,1,3,3,3-Hexafluoropropan-2-yl)thiazol-2-amine (Table
2, entry 1)
The general procedure conducted with sodium dithionite
(348 mg, 2.0 mmol), 2-aminothiazole (100 mg, 1.0 mmol), NaHCO3
(168 mg, 2.0 mmol) and (CF3)2CFI (443 mg, 1.5 mmol) in 7.5 mL
acetonitrile and 2.5 mL water gave 194 mg (78%) of the product as
1171, 1091, 965, 897, 867, 734, 695, 622, 530, 449 cmÀ1
.
Acknowledgments
a white solid. Mp 67–68 8C. 1H NMR (300 MHz, CDCl3/TMS)
d 7.13
(s, 1H), 5.23 (br, 2H), 4.16–4.32 (Septet, J = 7.9 Hz, 1H). 19F NMR
The authors gratefully acknowledge the financial support from
Special Fund for Agro-scientific Research in the Public Interest
(201103007), the National Key Technologies R&D Program
(2011BAE06B05), National Basic Research Program of China
(2010CB126103), the Key Program of National Natural Science
Foundation of China (21032006) and SIOC startup fund for financial
support. We also thank Mr. Yanchuan Zhao for helpful discussion.
(282 MHz, CDCl3)
CDCl3)
J = 31.0 Hz, –CH–). MS (ESI positive ion): 250.9 (M+1); HRMS (ESI)
calcd for C6H5F6N2S+1 (M+H): 251.0078. Found: 251.0072. IR (thin
film) 3468, 3287, 3122, 2678, 1630, 1556, 1528, 1513, 1353, 1278,
d
À67.31 (d, J = 7.9 Hz, 1F). 13C NMR (100 MHz,
d
170.3, 142.3, 122.3 (q, J = 210.9 Hz, CF3), À109.7, 48.2 (t,
1233, 1188, 1149, 1095, 1050, 902, 863, 738, 692, 533 cmÀ1
.
4.5.2. (2-Amino-5-(perfluoropropan-2-yl)thiazol-4-yl)methanol
(Table 2, entry 7)
Appendix A. Supplementary data
The general procedure conducted with sodium dithionite
(134 mg, 0.8 mmol), 2-aminothiazole (50 mg, 0.4 mmol), NaHCO3
(65 mg, 0.8 mmol) and (CF3)2CFI (171 mg, 0.6 mmol) in 3.0 mL
acetonitrile and 1.0 mL water gave 90 mg (79%) of the product as a
Supplementary data associated with this article can be found, in
white solid. Mp: 110–111 8C. 1H NMR (300 MHz, DMSO-d6/TMS)
7.60 (s, 2H, –NH2), 5.08 (t, J = 6.0 Hz, 1 H, –OH), 4.29 (dd, J = 2.1,
d
References
5.7 Hz, 2H, –CH2–). 19F NMR (282 MHz, DMSO-d6)
d
À75.70 (d,
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d
169.8, 157.6, 120.6 (qd, J = 286.6, 28.5, Hz), 98.3 (d, J = 24.7 Hz),
(c) V.A. Ryabinina, A.N. Sinyakova, V.R. Soultraitb, A. Caumontb, V. Parissib, O.D.
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58.1 (d, J = 8.8 Hz). MS (ESI positive ion): 299.0 (M+1); HRMS (ESI)
calcd for C7H6F7N2O1S+1 (M+H): 299.0084. Found: 299.0089. IR