A. Noack, H. Hartmann / Tetrahedron 58 -2002) 2137±2146
2143
Table 8. Spectral data of compound 15±17
0
Number
15a
R1
R2
R3/R3
n
CO +cm21
)
l
max +lg e) +nm)
1H NMR, d-values, in CDCl3
+ppm) +assignment)
13C NMR, d-values, in CDCl3
+ppm)
C2H4OC2H4
C2H4OC2H4
H
1577
414 +4.60)
411 +4.45)
3.26 +t, 8H, CH2), 3.82 +t, 8H,
CH2), 6.08 +d, 2H, CH), 7.59 +d, 165.4, 172.6
2H, CH)
50.0, 66.1, 104.6, 128.6, 133.5,
15b
C6H5
1592
3.04 +t, 8H, CH2), 3.74 +t, 8H,
52.7, 66.9, 127.1, 127.8, 128.4,
NCH2), 7.28 +t, 2H, CH), 7.40 129.3, 131.1, 136.0, 136.4,
+t, 4H, CH), 7.63 +d, 4H, CH), 161.4, 177.4
7.81 +s, 2H, CH)
15c
15d
C6H5
C6H5
C6H5
H
1589
1589
442 +4.57)
440 +4.07)
6.41 +d, 2H, CH), 7.14 +t, 4H,
CH), 7.24 +d, 8H, CH), 7.31 +t, 131.6, 133.0, 146.8, 160.9, 176.7
8H, CH), 7.57 +d, 2H, CH)
6.85±6.98 +m, 4H, CH), 7.04± 117.9, 122.8, 123.6, 127.3,
7.06 +m, 10H, CH), 7.13±7.18 127.7, 128.1, 129.0, 134.6,
+m, 12H, CH), 7.33 +d, 4H, CH), 135.6, 143.3, 146.6, 153.2, 177.3
7.91 +s, 2H, CH)
114.6, 124.9, 125.2, 129.7,
C6H5
C6H5
C6H5
15e
CH3
H
1560
433 +4.54)
3.39 +s, 6H, CH3), 6.22 +d, 2H, 41.8, 107.1, 123.4, 125.4, 127.0,
CH), 7.23 +t, 2H, CH), 7.36±
7.46 +m, 8H, CH), 7.65 +d, 2H,
CH)
129.5, 133.2, 146.8, 162.1, 174.3
15f
CH3
CH3
H
H
1560
1595
364 +3.83), 427 +4.50) 3.01 +s, 6H, CH3), 3.14 +s, 6H, 41.4, 102.7, 125.4, 133.4, 164.5,
CH3), 6.00 +d, 2H, CH), 7.64 +d, 173.6
2H, CH)
15g
C6H5
1-C10H7
396 +4.21)
445 +4.39)
6.27 +d, 2H, CH), 7.05±7.11 +m, 122.0, 123.4, 124.0, 125.8,
2H, CH), 7.24±7.28 +m, 6H, 126.2, 1236.5, 126.9, 127.1,
CH), 7.36±7.59 +m, 10H, CH), 128.7, 129.4, 129.5, 130.6,
7.84±7.95 +m, 6H, CH), 8.04 +d, 130.9, 132.8, 135.3, 142.3,
2H, CH) 147.0, 161.4, 176.6
6.48 +d, 2H, CH), 7.17±7.19 +m, 114.8, 121.8, 123.7, 124.7,
15h
C6H5
2-C10H7
H
1599
2H, CH), 7.27±7.37 +m, 10H, 125.2, 125.4, 126.5, 127.2,
CH), 7.41±7.44 +m, 4H, CH), 127.5, 129.4, 129.5, 131.0,
7.60 +d, 2H, CH), 7.67 +m, 4H, 132.8, 133.9, 144.0, 146.6,
CH), 7.78 +d, 4H, CH)
337 +3.91), 401 +4.51) 3.29 +t, 4H, CH2), 3.60 +t, 4H,
160.5, 176.6
48.4, 50.1, 65.7, 104.9, 133.5,
16a
16b
C2H4OC2H4
H
1572
1566
CH2), 3.80±3.86 +m, 8H, CH2), 134.2, 144.1, 145.6, 151.7,
6.11 +d, 1H, CH), 7.61 +d, 1H, 152.1, 175.9
CH), 7.90 +s, 1H, CH)
C2H4OC2H4
C6H5
398 +4.42)
425 +4.27)
3.02 +t, 4H, CH2), 3.61 +t, 4H,
48.5, 52.0, 65.9, 66.2, 126.5,
CH2), 3.72 +t, 4H, CH2), 3.80 +t, 127.2, 127.7, 128.1, 128.7,
4H, CH2), 7.25 +t, 1H, CH), 7.34 130.0, 135.2, 135.5, 145.5,
+t, 2H, CH), 7.58 +d, 2H, CH), 161.0, 174.1, 176.0
7.71 +s, 1H, CH), 7.98 +s, 1H,
CH)
6.38 +d, 1H, CH), 7.15 +m, 2H, 113.5, 125.1, 125.5, 126.3,
CH), 7.23±7.40 +m, 18H, CH), 127.0, 127.8, 128.3, 129.7,
16c
C6H5
C6H5
H
1523
7.52 +d, 1H, CH), 7.93 +s, 1H,
CH)
330 +3.96), 382 +4.43) 3.62 +t, 8H, CH2), 3.81 +t, 8H, 48.6, 65.9, 127.7, 144.8, 174.1,
129.8, 144.0, 144.2, 145.4,
146.4, 161.7, 173.3, 176.2
17a
17b
17c
C2H4OC2H4
C6H5
±
±
±
1579
1573
1581
CH2), 7.91 +s, 2H, CH)
3.54 +s, 6H, CH3), 7.27±7.44
174.9
40.5, 125.4, 127.7, 128.2, 130.1,
CH3
389 +4.14)
398 +4.57)
+m, 10H, CH), 7.90 +s, 2H, CH) 145.1, 145.9, 174.1, 175.7
7.26±7.30 +m, 4H, CH), 7.37± 126.2, 127.1, 129.5, 129.8,
7.43 +m, 16H, CH), 7.94 +s, 2H, 144.1, 145.6, 173.7, 175.5
CH)
C6H5
C6H5
17d
CH3
CH3
1546
384 +4.43)
3.23 +s, 12H, CH3), 7.92 +s, 2H, 40.5, 127.7, 145.8, 174.2, 175.2
CH)
stoichiometric ratio in a polar solvent, such as acetonitrile or
methanol, 1-acylmethylmercapto-substituted vinamidinium
salts of the structure 9 are formed as intermediates. These
salts, whose isolation was not encouraged, can be converted
in situ by addition of a suitable base, such as triethylamine
or sodium methoxide, and re¯uxinginto the 5-acyl-
substituted 2-aminothiophene derivatives 10. As demon-
strated with a series of differently substituted 3-amino-
thioacrylamides 7, especially with several N+1),N+1)-
diarylamino- and/or C+2)-aryl substituted derivatives, as
well as with a variety of haloketones 8, such as 1-aryl-2-
bromoethanones 8a and 8b, this heterocyclisation method
usually gives high yields of products of the structure 10
+see Table 1).
The reported method for preparing5-acyl-substituted
2-aminothiophenes 10 can be extended, as exempli®ed
recently,12 to the synthesis of 5-acyl-substituted
2-aminothiazoles 12 +see Table 2). In this case N,N-di-
substituted N0-+dialkylaminomethylidene)thioureas 11,
the aza analogues of the N,N0-persubstituted 3-amino-
thioacrylamides 7, have to be used as educts. These
compounds are easily available, e.g. from N,N-disubstituted
thioureas13 by reaction with formamide acetals or trialkyl