efficient one-pot synthesis of 5-perfluoroalkylpyrazoles by … · 2015-06-25 · 1 efficient...
TRANSCRIPT
1
Efficient One-pot Synthesis of 5-Perfluoroalkylpyrazoles by
Cyclization of Hydrazone Dianions
Thang Ngoc Ngo,a Syeda Abida Ejaz,
b Tran Quang Hung,
a Tuan Thanh Dang,
a,d Jamshed Iqbal,
b Joanna
Lecka,e Jean Sévigny,
e Peter Langer
a,c*
a Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany. E-mail: peter.langer@uni-
rostock.de; Fax: +49 381 4986412; Tel: +49 381 4986410
b Centre for Advanced Drug Research, COMSATS Institute of Information Technology, Abbottabad, Pakistan
c Leibniz Institut für Katalyse an der Universität Rostock e. V. (LIKAT), Albert-Einstein-Str. 29a, 18059 Rostock, Germany.
d Organic Chemistry, Institute of Chemical and Engineering Sciences, 8 Biomedical Grove, 07-01 Neuros, Singapore 138665.
E-mail: [email protected]
e Department of Microbiology-Infectiology and Immunology, Faculty of Medicine, Centre de Recherche du CHU de Québec –
Université Laval, Québec, QC, G1V 4G2, Canada
NMR spectra
1,3-diphenyl-5-(trifluoromethyl)-1H-pyrazole (4a): ..................................................................................................3
3-(4-methoxyphenyl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4b):.....................................................................5
3-(3-methoxyphenyl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4c): .....................................................................7
3-(2-methoxyphenyl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4d):.....................................................................9
3-([1,1'-biphenyl]-4-yl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4e): ............................................................... 11
1-phenyl-3-(p-tolyl)-5-(trifluoromethyl)-1H-pyrazole (4f): .................................................................................... 12
3-(2-fluorophenyl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4g): ...................................................................... 14
3-(4-fluorophenyl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4h): ...................................................................... 17
3-(naphthalen-2-yl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4i):...................................................................... 19
1-phenyl-5-(trifluoromethyl)-3-(4-(trifluoromethyl)phenyl)-1H-pyrazole (4j): ..................................................... 21
5-(perfluoroethyl)-1,3-diphenyl-1H-pyrazole (4k): ................................................................................................ 23
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2015
2
3-(4-methoxyphenyl)-5-(perfluoroethyl)-1-phenyl-1H-pyrazole (4l): .................................................................... 25
3-(naphthalen-2-yl)-5-(perfluoroethyl)-1-phenyl-1H-pyrazole (4m): ..................................................................... 27
3-([1,1'-biphenyl]-4-yl)-5-(perfluoroethyl)-1-phenyl-1H-pyrazole (4n): ................................................................ 29
5-(perfluoropropyl)-1,3-diphenyl-1H-pyrazole (4o): .............................................................................................. 31
3-(4-methoxyphenyl)-5-(perfluoropropyl)-1-phenyl-1H-pyrazole (4p): ................................................................. 33
Ethyl 3-(4-methoxyphenyl)-5-(trifluoromethyl)-1H-pyrazole-1-carboxylate (4q): ................................................ 35
Ethyl 3-(2-fluorophenyl)-5-(trifluoromethyl)-1H-pyrazole-1-carboxylate (4r): ..................................................... 37
2-phenyl-3-(trifluoromethyl)-4,5,6,7,8,9,10,11,12,13-decahydro-2H-cyclododeca[c]pyrazole (4s): ..................... 39
2-phenyl-3-(trifluoromethyl)-4,5,6,7-tetrahydro-2H-indazole (4t): ........................................................................ 41
2-phenyl-3-(trifluoromethyl)-4,5-dihydro-2H-indazole (4u): ................................................................................. 43
2-phenyl-3-(trifluoromethyl)-4,5-dihydro-2H-benzo[g]indazole (4v): ................................................................... 45
5-(4-methoxyphenyl)-3-(trifluoromethyl)-1H-pyrazole (5a): ................................................................................ 47
5-(4-methoxyphenyl)-3-(perfluoroethyl)-1H-pyrazole (5b):................................................................................... 49
5-(4-methoxyphenyl)-3-(perfluoropropyl)-1H-pyrazole (5c): ................................................................................. 51
5-(naphthalen-2-yl)-3-(trifluoromethyl)-1H-pyrazole (5d): .................................................................................... 53
5-(naphthalen-2-yl)-3-(perfluoroethyl)-1H-pyrazole (5e): ...................................................................................... 55
3-(3,3,3,3,3,3,3-heptafluoro-3l8-prop-1-yn-1-yl)-5-(naphthalen-2-yl)-1H-pyrazole (5f): ...................................... 57
3-(trifluoromethyl)-5-(4-(trifluoromethyl)phenyl)-1H-pyrazole (5g): .................................................................... 59
5-(perfluoroethyl)-3-(4-(trifluoromethyl)phenyl)-1H-pyrazole (5h):...................................................................... 61
3-(3,3,3,3,3,3,3-heptafluoro-3l8-prop-1-yn-1-yl)-5-(4-(trifluoromethyl)phenyl)-1H-pyrazole (5i): ...................... 63
2-phenyl-3-(trifluoromethyl)-2H-indazole (6a): ..................................................................................................... 64
2-phenyl-3-(trifluoromethyl)-2H-benzo[g]indazole (6b): ....................................................................................... 66
3-(4-methoxyphenyl)-5-(trifluoromethyl)isoxazole (8a): ....................................................................................... 68
3-(naphthalen-2-yl)-5-(trifluoromethyl)isoxazole (8b): .......................................................................................... 70
3
1,3-diphenyl-5-(trifluoromethyl)-1H-pyrazole (4a):
4
5
3-(4-methoxyphenyl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4b):
6
7
3-(3-methoxyphenyl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4c):
8
9
3-(2-methoxyphenyl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4d):
10
11
3-([1,1'-biphenyl]-4-yl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4e):
12
1-phenyl-3-(p-tolyl)-5-(trifluoromethyl)-1H-pyrazole (4f):
13
14
3-(2-fluorophenyl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4g):
15
16
17
3-(4-fluorophenyl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4h):
18
19
3-(naphthalen-2-yl)-1-phenyl-5-(trifluoromethyl)-1H-pyrazole (4i):
20
21
1-phenyl-5-(trifluoromethyl)-3-(4-(trifluoromethyl)phenyl)-1H-pyrazole (4j):
22
23
5-(perfluoroethyl)-1,3-diphenyl-1H-pyrazole (4k):
24
25
3-(4-methoxyphenyl)-5-(perfluoroethyl)-1-phenyl-1H-pyrazole (4l):
26
27
3-(naphthalen-2-yl)-5-(perfluoroethyl)-1-phenyl-1H-pyrazole (4m):
28
29
3-([1,1'-biphenyl]-4-yl)-5-(perfluoroethyl)-1-phenyl-1H-pyrazole (4n):
30
31
5-(perfluoropropyl)-1,3-diphenyl-1H-pyrazole (4o):
32
33
3-(4-methoxyphenyl)-5-(perfluoropropyl)-1-phenyl-1H-pyrazole (4p):
34
35
Ethyl 3-(4-methoxyphenyl)-5-(trifluoromethyl)-1H-pyrazole-1-carboxylate (4q):
36
37
Ethyl 3-(2-fluorophenyl)-5-(trifluoromethyl)-1H-pyrazole-1-carboxylate (4r):
38
39
2-phenyl-3-(trifluoromethyl)-4,5,6,7,8,9,10,11,12,13-decahydro-2H-cyclododeca[c]pyrazole (4s):
40
41
2-phenyl-3-(trifluoromethyl)-4,5,6,7-tetrahydro-2H-indazole (4t):
42
43
2-phenyl-3-(trifluoromethyl)-4,5-dihydro-2H-indazole (4u):
44
45
2-phenyl-3-(trifluoromethyl)-4,5-dihydro-2H-benzo[g]indazole (4v):
46
47
5-(4-methoxyphenyl)-3-(trifluoromethyl)-1H-pyrazole (5a):
48
49
5-(4-methoxyphenyl)-3-(perfluoroethyl)-1H-pyrazole (5b):
50
51
5-(4-methoxyphenyl)-3-(perfluoropropyl)-1H-pyrazole (5c):
52
53
5-(naphthalen-2-yl)-3-(trifluoromethyl)-1H-pyrazole (5d):
54
55
5-(naphthalen-2-yl)-3-(perfluoroethyl)-1H-pyrazole (5e):
56
57
3-(3,3,3,3,3,3,3-heptafluoro-3l8-prop-1-yn-1-yl)-5-(naphthalen-2-yl)-1H-pyrazole (5f):
58
59
3-(trifluoromethyl)-5-(4-(trifluoromethyl)phenyl)-1H-pyrazole (5g):
60
61
5-(perfluoroethyl)-3-(4-(trifluoromethyl)phenyl)-1H-pyrazole (5h):
62
63
3-(3,3,3,3,3,3,3-heptafluoro-3l8-prop-1-yn-1-yl)-5-(4-(trifluoromethyl)phenyl)-1H-pyrazole (5i):
64
2-phenyl-3-(trifluoromethyl)-2H-indazole (6a):
65
66
2-phenyl-3-(trifluoromethyl)-2H-benzo[g]indazole (6b):
67
68
3-(4-methoxyphenyl)-5-(trifluoromethyl)isoxazole (8a):
69
70
3-(naphthalen-2-yl)-5-(trifluoromethyl)isoxazole (8b):
71