References and Notes
1
Metzner P.
Synthesis
1992,
1185
2 Herbert Haller LJ, and Barthel WF. inventors; US 2,358,925.
3 Leresque CL. inventors; US 2,560,296.
4 . inventors; Jpn. Kokai Tokyo 81 12 315.
5a
Jagodzinski TS.
Chem. Rev.
2003,
103:
197
5b
Lawesson SO.
Perregaard J.
Scheibye S.
Meyer
HJ.
Thompson I.
Bull. Soc. Chim. Belg.
1977,
679
5c
Caddick S.
SyntheticPages [Online]
2001,
66 ; http://www.syntheticpages.org/pages/66
6a
Kindler K.
Justus Liebigs Ann. Chem.
1923,
431:
187
6b
Zbruyev OI.
Stiasni N.
Kapper CO.
J. Comb. Chem.
2003,
5:
145
7
Brillion D.
Synth.
Commun.
1992,
1397
8
Albert A.
Ber.
Dtsch. Chem. Ges.
1915,
48:
470
9a
Gauthier JY.
Lebel H.
Phosphorus,
Sulfur Silicon Relat. Elem.
1994,
325
9b
Ikeda K.
Sato K.
Nishino R.
Aoyama S.
Suzuki T.
Sato M.
Bioorg.
Med. Chem.
2008,
16:
6783
10
Taylor EC.
Zoltewicz JA.
J. Am. Chem. Soc.
1960,
82:
2656
11
Liboska R.
Zyka D.
Bobek M.
Synthesis
2002,
1649
12a
Yousif NM.
Tetrahedron
1989,
45:
4599
12b
Pudovik AN.
Cherkasov RA.
Zimin MG.
Zabirov NG.
Bull. Acad.
Sci. USSR Div. Chem. Sci. (Engl. Transl.)
1979,
28:
805
13
Benner SA.
Tetrahedron
Lett.
1981,
22:
1851
14a
Shiao MJ.
Lai LL.
Ku WS.
Lin PY.
Hwu JR.
J. Org. Chem.
1993,
58:
4742
14b
Lin PY.
Ku WS.
Shiao MJ.
Synthesis
1992,
1219
15
Boys ML.
Downs VL.
Synth. Commun.
2006,
295
16
Manaka A.
Sato M.
Synth. Commun.
2005,
761
17
Brillon D.
Synth.
Commun.
1992,
1397
18
Rapaport E.
Cass MW.
White EH.
J.
Am. Chem. Soc.
1972,
94:
3153
19a
Moghaddam FM.
Hojabri L.
Dohendou M.
Synth. Commun.
2003,
4279
19b
Bagley MC.
Chapaneri K.
Glover C.
Merritt EA.
Synlett
2004,
2615
20
General Procedure
for the Synthesis of Thioamide
To a mixture of aryl
nitrile (1 equiv) and CaH2 (1 equiv) was taken in a two-necked
50 mL round-bottomed flask, and the content was cooled to 0 ˚C
and added thioacetic acid (1.5 equiv). After stirring for 15 min
the reaction mixture was heated in an oil bath at 80 ˚C
for the given period of time (Table
[¹]
).
After the completion of the reaction, the contents were cooled to
r.t., 50% aq EtOAc (2 × 10 mL)
was added and stirred for some time till the layers separated. Extraction was
done once again with EtOAc, and the combined organic layer was filtered
through Celite pad, and concentrated under reduced pressure to get
the crude product. It was then purified by crystallization using
PE and EtOAc (9:1). All the novel products were characterized by
NMR and MS analysis.
4-Bromo-2-chlorobenzenecarbothioamide
(2b)
¹H NMR (400 MHz, DMSO-d
6): δ = 7.31
(d, 1 H), 7.50 (q, 1 H), 7.75 (s, 1 H), 9.73 (br s, 1 H), 10.23
(br s, 1 H) ppm. ¹³C NMR (100 MHz,
DMSO-d
6): δ = 126.5,
129.1, 129.7, 133.3, 136.6, 141.3, 188.5 ppm. Anal. Calcd (%)
for C7H5BrClNS: C, 33.56; H, 2.01; N, 5.59.
Found: C, 33.54; H, 2.22; N, 5.55. MS: m/z = 251.0 [M+].
4-Chloro-3-nitrobenzenecarbothioamide (2d)
¹H
NMR (400 MHz, DMSO-d
6): δ = 7.8
(d, 1 H), 8.1 (d, 1 H), 8.5 (s, 1 H), 9.8 (br s, 1 H), 10.2 (br
s, 1 H) ppm.
¹³C NMR (100
MHz, DMSO-d
6): δ = 124.7,
128.0, 131.8, 132.4, 139.6, 147.2, 196.5 ppm. Anal. Calcd (%)
for C7H5ClN2O2S: C,
33.81; H, 2.33; N, 12.93. Found: C, 33.76; H, 2.38; N, 12.96. MS: m/z = 214.9 [M+].
2-(3,4-Dichlorophenyl)ethanethioamide (2f)
¹H
NMR (400 MHz, DMSO-d
6): δ = 3.8
(s, 2 H), 7.2 (d, 1 H), 7.5 (s, 1 H), 7.6 (d, 1 H), 9.4 (s, 1 H),
9.5 (s, 1 H) ppm. ¹³C NMR (100 MHz,
DMSO-d
6): δ = 50.5,
129.6, 129.8, 130.6, 131.1, 131.2, 138.8, 204.9 ppm. Anal. Calcd
(%) for C8H7Cl2NS: C,
43.65, H, 3.21, N, 6.36. Found: C, 43.76, H, 3.28, N, 6.34; MS: m/z = 219.9 [M+].
3-(4-Iodophenyl)propanethioamide (2g)
¹H
NMR (400 MHz, DMSO-d
6): δ = 3.7
(s, 2 H), 7.1 (d, 2 H), 7.6 (d, 2 H), 9.3 (br s, 1 H), 9.4 (br s,
1 H) ppm. ¹³C NMR: (100 MHz, DMSO-d
6): δ = 50.7,
93.0, 131.6, 137.3, 137.6, 205.4 ppm. Anal. Calcd (%) for
C8H8INS: C, 34.67; H, 2.91; N, 5.05. Found:
C, 34.65; H, 2.98; N, 5.11. MS:
m/z = 277.8 [M+].
2-[4-(Trifluoromethoxy)phenyl]ethanethioamide
(2i)
¹H NMR (400 MHz, DMSO-d
6): δ = 3.8
(s, 2 H), 7.2 (d, 2 H), 7.4 (d, 2 H), 9.4 (br s, 1 H), 9.5 (br s,
1 H) ppm. ¹³C NMR (100 MHz, DMSO-d
6): δ = 50.5,
116.7, 131.0, 131.3, 136.8, 137.3, 147.6, 147.7, 205.4 ppm. Anal.
Calcd (%) for C9H8F3NOS:
C, 45.95; H, 3.43; N, 5.95. Found: C, 45.98; H, 3.48; N, 5.98. MS: m/z = 235.8 [M+].
Propanethioamide (2t)
¹H
NMR (400 MHz, DMSO-d
6): δ = 1.2
(t, 3 H) 2.6 (q, 2 H), 7.2 (s, 1 H), 8.0 (s, 1 H) ppm. ¹³C
NMR (100 MHz, DMSO-d
6): δ = 15.0,
42.1, 208.6 ppm. Anal. Calcd (%) for C3H7NS: C,
40.41; H, 7.91; N, 15.71. Found: C, 40.45; H, 7.98; N, 15.78. GC-MS: m/z = 89.1 [M+].
2,2-Dimethylpropanethioamide (2v)
¹H
NMR (400 MHz, DMSO-d
6): δ = 1.3
(s, 9 H) 7.0 (br s, 1 H), 7.7 (br s, 1 H) ppm. ¹³C
NMR: (100 MHz, DMSO-d
6): δ = 32.5,
48.8, 221.8 ppm. Anal. Calcd (%) for C5H11NS:
C, 51.23; H, 9.46; N, 11.95. Found: C, 51.31; H, 9.48; N, 11.98. MS: m/z = 118.0 [M+].
21
Sivakumar M.
Senthilkumar P.
Pandit AB.
Synth. Commun.
2001,
2583
22a
Liboska R.
Zyka D.
Bobek M.
Synthesis
2002,
1649
22b
Oliver JE.
DeMilo AB.
Cohen CF.
Shortino
TJ.
Robbins WE.
J. Agric. Food Chem.
1976,
24:
1065
22c
Takikawa Y.
Shimada K.
Sato K.
Sato S.
Takizawa S.
Bull. Chem.
Soc. Jpn.
1985,
58:
995
22d
Abdel-Lateef MF.-A.
Eckstein Z.
Bull.
Acad. Pol. Sci., Ser. Sci. Chim.
1971,
19:
705
22e
Miwatashi S.
Arikawa Y.
Naruo K.
Igaki K.
Watanabe Y.
Kimura H.
Kawamoto T.
Ohkawa S.
Chem. Pharm. Bull.
2005,
53:
410
22f
Lin
PY.
Ku WS.
Shiao MJ.
Synthesis
1992,
1219
22g
Matsuda K.
Yanagisawa I.
Isomura Y.
Mase T.
Shibanuma T.
Synth.
Commun.
1997,
2393
22h
Sakai
TT.
Rama KN.
Bioorg.
Med. Chem.
1999,
7:
1559
22i
Chihiro M.
Nagamoto H.
Takemura I.
Kitano K.
Komatsu H.
Sekiguchi K.
Tabusa F.
Mori T.
Tominaga M.
Yabuuchi Y.
J. Med. Chem.
1995,
38:
353
22j
Kindler VK.
Justus Liebigs Ann. Chem.
1927,
452:
107
22k
Erlenmeyer H.
Junod J.
Guex W.
Erne M.
Helv. Chim. Acta
1948,
31:
1342
22l
Lehr H.
Guex W.
Erlenmeyer H.
Helv.
Chim. Acta
1944,
27:
970
22m
Edward JT.
Derdall GD.
Wong SC.
Can. J. Chem.
1977,
55:
2331