P. He, S.-Z. Zhu / Journal of Fluorine Chemistry 126 (2005) 825–830
829
0
0
0
0
0
0
4
.1.3. 2-(1,3-Dimethyl-indolinylidene)-(1 ,1 ,2 ,2 ,4 ,4 ,
0
(ppm): 7.55–7.16 (m, 4H, ArH), 6.57 (br, 1H, NH), 3.69 (s,
19
0
0
5
,5 -octafluoro-3 -oxa-pentyl)sulfonylimines 5c
White solid, m.p. 98–100 8C. FT-IR (nmax, cm ): 1563,
499, 1327, 1167, 1143, 952. H NMR d (ppm): 7.44–7.10
(m, 4H, ArH), 5.87 (t-t, J = 3.0, 52.5 Hz, 1H, HCF ), 4.42 (q,
J = 7.8 Hz, 1H, CH), 3.48 (s, 3H, NCH ), 1.68 (d,
3H, NCH ), 2.47 (s, 3H, 2-CH ). F NMR d (ppm): ꢀ73.97
3
3
ꢀ
1
(2F, s, ClCF ), ꢀ81.66 (t, J = 12 Hz, 2F, CF O), ꢀ120.97 (t,
2 2
2
2
1
1
J = 12 Hz, 2F, OCF ), ꢀ115.48 (m, 2F, CF S). MS m/z (ion,
f 2
+
+
%): 476/474 (M , 1.5/4), 159 (M ꢀR SO , 100). Anal.
14 11 8 2 3
2
calcd. for C H ClF N O S: C, 35.41; H, 2.32; N, 5.90;
found: C, 35.53; H, 2.34; N, 5.88.
3
1
9
J = 7.8 Hz, 3H, CHCH3). F NMR d (ppm): ꢀ80.93 (t,
J = 12 Hz, 2F, CF ), ꢀ88.80 (m, 2F, CF O), ꢀ117.11 (s, 2F,
2
2
0
0
0
0
0
0
0
0
0
OCF ), ꢀ137.63 (d, J = 53.4Hz, 2F, HCF ). MS m/z (ion,
4.2.3. 2-(1 ,1 ,2 ,2 ,4 ,4 ,5 ,5 -Octafluoro-3 -oxa-
pentyl)sulfonyl (1,2-dimethyl-1H-indol-3-yl)-
amide 6c
2
2
+
+
%
): 440 (M , 27), 159 (M ꢀR SO , 100), 144
f 2 14 12 8 2 3
f
2
+
(
M ꢀR SO NH, 37). Anal. calcd. for C H F N O S: C,
ꢀ
1
3
8.18; H, 2.73; N, 6.36; found: C, 38.49; H, 2.77; N, 6.35.
Carmine solid, m.p. 112–114 8C. FT-IR (n , cm ):
max
1
273, 2924, 2869, 1410, 1329, 1210, 1163, 857. H NMR d
3
4.1.4. 2-(1,3-Dimethyl-indolinylidene)-perfluoro-
butylsulfonylimines 5d
(ppm): 7.55–7.16 (m, 4H, ArH), 6.53 (br, 1H, NH) 5.78 (t-t,
J = 3.0, 49 Hz, 1H, HCF ), 3.70 (s, 3H, NCH ), 2.47 (s, 3H,
2
3
ꢀ
1
19
White solid, m.p. 111–113 8C. FT-IR (nmax, cm ): 1569,
499, 1328, 1165, 1138, 961. H NMR d (ppm): 7.45–7.11
2-CH3). F NMR d (ppm): ꢀ81.38 (t, J = 13Hz, 2F, OCF ),
2
1
1
ꢀ88.79 (m, 2F, CF O), ꢀ115.47 (m, 2F, SCF ), ꢀ137.60 (d,
2
2
+
J = 53Hz, 2F, HCF ). MS m/z (ion, %): 440 (M , 6), 159
(
NCH ), 1.69 (d, J = 7.5 Hz, 3H, CHCH ). F NMR d (ppm):
m, 4H, ArH), 4.44 (q, J = 7.6 Hz, 1H, CH), 3.48 (s, 3H,
1
2
9
+
(M ꢀR SO , 100). Anal. calcd. for C H F N O S: C,
3
3
f
2
14 12 8 2 3
ꢀ
80.98 (m, 3F, CF ), ꢀ113.53 (m, 2F, CF S), ꢀ120.97 (s,
38.18; H, 2.73; N, 6.36; found: C, 38.20; H, 2.85; N, 6.34.
3
2
2
F, CF ), ꢀ126.15 (m, 2F, CF CF ). MS m/z (ion, %): 442
f 2 f 2
2
3
2
+
+
+
(M , 30), 159 (M ꢀR SO , 100), 144 (M ꢀR SO NH, 44).
Anal. calcd. for C H F N O S: C, 38.01; H, 2.49; N, 6.33;
4.2.4. Perfluorobutylsulfonyl-(1,2-dimethyl-
1H-indol-3-yl) -amide 6d
1
4 11 9 2 2
ꢀ
1
found: C, 38.16; H, 2.61; N, 6.05.
Carmine solid, m.p. 92–94 8C. FT-IR (nmax, cm ): 3294,
962, 1409, 1352, 1226, 1192, 1143, 1033. H NMR d
1
2
(ppm): 7.52–7.16 (m, 4H, ArH), 6.65 (br, 1H, NH), 3.68 (s,
4
2
.2. Typical procedure for the preparation of
-fluoroalkanesulfonyl (1,2-dimethyl-1H-
1
9
3H, NCH ), 2.45 (s, 3H, 2-CH ). F NMR d (ppm): ꢀ81.12
3
3
indol-3-yl)-amide 6
(t, J = 9.3 Hz, 3F, CF ), ꢀ112.06 (t, J = 12 Hz, 2F, CF S),
2 2
3
2
ꢀ
121.26 (t, J = 3.4 Hz, 2F, CF ), ꢀ126.39 (m, 2F, CF ). MS
f 2
+
+
To a 10-mL round-bottom flask containing 1,2-dimethy-
lindoles 4 (1.0 equiv.) in 2 mL 1,4-dioxane was added
slowly fluoroalkanesulfonyl azides 1b (1.0 equiv.) at room
temperature within 2 min. Then the mixture was continu-
ously stirred at room temperature within 4 h until TLC
analysis shown the reaction finished. The solvent was
evaporated and the residue was chromatographed on a silica
column using petroleum ether:ethyl acetate (10:1) as eluant
to give pure product 6b as a carmine solid. To 6a and 6d, the
petroleum ether:ethyl ether (4:1) was selected.
m/z (ion, %): 442 (M , 4), 159 (M ꢀR SO , 100). HRMS
14 12 9 2 2
+
(MALDI) for C H F N O S [M H] calcd.: 443.04496;
+
found: 443.04703.
4.3. Typical procedure for the preparation of
N-unsubstituted-2-fluoroalkanesulfonimino-
3-diazo-indolines 8
To a 10-mL round-bottom flask containing simple indoles
7 (1.0 equiv.) in 2 mL anhydrous ethanol was added slowly
fluoroalkanesulfonyl azides 1a (2.0 equiv.) at room tem-
perature within 2 min. Then the mixture was continuously
stirred at r.t. within 5 min until TLC analysis shown the
reaction finished. The solvent was evaporated and the
residue was chromatographed on a silica column using
petroleum ether:ethyl acetate (4:1) as eluant to give pure
product 8a as a yellowish solid.
0
0
4
.2.1. 2-(5 -Iodo-3 -oxa-octafluoropentyl)sulfonyl-(1,
-dimethyl-1H-indol-3-yl)-amide 6a
2
ꢀ
1
Carmine solid, m.p. 100–102 8C. FT-IR (n , cm ):
max
1
266, 2963, 1413, 1333, 1262, 1153, 1093, 917. H NMR d
3
(
ppm): 7.54–7.16 (m, 4H, ArH), 6.53 (br, 1H, NH), 3.67 (s,
1
9
3
H, NCH ), 2.45 (s, 3H, 2-CH ). F NMR d (ppm): ꢀ65.29
3
3
(
t, J = 5.9 Hz, 2F, ICF ), ꢀ81.84 (t, J = 13 Hz, 2F, CF O),
2
2
0
0
ꢀ
85.87 (m, 2F, OCF ), ꢀ115.59 (s, 2F, CF S). MS m/z (ion,
4.3.1. 2-(5 -Iodo-3 -oxa-octafluoropentyl)-sulfonimino-3-
diazo-indolines 8a
2
2
+
+
%
C H F IN O S: C, 29.68; H, 1.94; N, 4.95; found: C,
): 566 (M , 1), 159 (M ꢀR SO , 100). Anal. calcd. for
f
2
ꢀ
1
Yellow solid, m.p. 122–124 8C. FT-IR (nmax, cm ):
+
3331, 2924, 2136 (s, C N N ), 1568 (s, C N), 1327,
1
4
11
8
2 3
ꢀ
2
9.29; H, 2.08; N, 4.71.
1
1
156, 913. H NMR d (ppm): 10.02 (br, 1H, NH), 7.41–7.27
19
0
0
4
.2.2. 2- (5 -Chloro-3 -oxa-octafluoropentyl) sulfonyl-
1,2-dimethyl-1H-indol-3-yl)-amide 6b
(m, 4H, ArH). F NMR d (ppm): ꢀ65.03 (s, 2F, ICF ),
2
(
ꢀ81.72 (s, 2F, CF O), ꢀ85.62 (m, 2F, OCF ), ꢀ116.88 (s,
2
2
ꢀ1
+
+
Carmine solid, m.p. 116–118 8C. FT-IR (n , cm ):
max
2F, CF S). MS m/z (ion, %): 564 (M , 22), 227 (IC F , 23),
2 2 4
1
265, 2925, 2858, 1411, 1345, 1211, 1148, 975. H NMR d
+
+
+
3
221 (M ꢀR , 47), 193 (M ꢀR –N , 20), 145 (M ꢀR SO N,
f
f
2
f
2