7
0
S. Zhu et al. / Journal of Fluorine Chemistry 93 (1999) 69±71
NH), 1620 (s, C=O), 1230 (s, C±F). MS (m/e, %): 326 (M ,
(
m/e, %): 346/348 (M , 2.97/2.02), 216/263 (M -CF Cl, ),
2
233/235 (M -ClCF CO, 100.00/38.23), 218/220 (M -
ClCF CONH, 58.03/20.72), 104 (PhCHN , 70.28), 85/87
1.24), 298 (M -CO, 0.60), 185 (M -C H F CO , 66.19),
6
2
3 2
141 (C H F CO , 100.00), 113 (C H F , 8.07). Elemental
2
2
6
3
6 3
(
lyses for C H Cl F N O : Anal Calc. C 38.04, H 2.31, N
ClCF2 , 38.00/13.14), 77 (C H , 36.85). Elemental ana-
analyses for C H F N O : Anal Calc. C 55.21, H 3.07, N
15 10 4 2 2
6
5
8.59; Found: C 55.24, H 3.21, N 8.74%.
1
1
8
2 4 2 2
8
.07, F 21.93; Found: C 37.84, H 2.23, N 7.79, F 22.27%.
1
H NMR(DMSO-d ) ꢀ(ppm): 8.53 (d, 2H, NH,
6
3JHH 7.5 Hz), 7.05 (d, 4H, J 8.6 Hz), 5.30 (t, 1H,
3
HH
1
H NMR(DMSO-d ) ꢀ(ppm): 9.50 (broad, 2H, NH), 7.50
6
J
HH 7.5 Hz), 3.05 (s, 2H, CH
), 2.13 (s, 3H, CH3). IR
2
�
1
(
m, 2H), 7.20 (m, 3H), 7.20±6.75 (m, 6H), 5.75(s, CH). 19
F
(nmax, cm ): 3250 (s, NH), 1667 (s, C=O). MS (m/e, %):
NMR(CDCl ): � 115.8 (d, 4F, J
18 Hz). IR (nmax,
204 (M , 10.81), 203 (M -H, 21.96), 189 (M -CH
3
, 10.06),
H , 68.43), 59
4
3
H±F
�
1
cm ): 3320 (s, NH), 1640 (s, C=O), 1230 (s, C±F). MS
160 (M -H±CONH, 33.58), 91 (CH
C
6
3
(
2
1
m/e, %): 420 (M , 2.95), 261 (M -C H F CO, 100.00),
6
(CH
3
CO
2
, 100.00). Elemental analyses for C11
Anal Calc.: C 64.71, H 5.88, N 13.73; Found: C 64.80, H
H
12
N
2
O
2
:
3 2
46 (M -C H F CONH, 46.01), 141 (C H F CO , 90.18),
6
3
2
6 3 2
04 (C H CHN , 13.38). Elemental analyses for
6
5.63, N 13.75%.
5
C H F N O : Anal Calcd. C 62.69, H 3.48, N 6.97;
2
1 14 4 2 2
Found: C 62.54, H 3.47, N 6.79%.
3
. Results and discussion
This note describes a facile preparation of the title
compounds by catalysis of ¯uoroalkanesulfonic acids:
1
H NMR(DMSO-d ) ꢀ(ppm): 9.50 (broad, 2H, NH), 7.53
6
Cat:
2RfCONH2 RCHO ! RCHꢀNHCORf H2O
3
(
(
d, JHH 6 Hz, 2H), 7.13 (d. 2H), 7.15±6.55 (m, 6H), 5.80
2
2
CH2Cl2
1
9
1
3
s, CH), 3.60 (s, OCH ). F NMR (CDCl ): � 115.5 (d, 4F)
3
3
�
1
IR (nmax, cm ): 3322 (s, NH), 1638 (s, C=O), 1220 (s,
R : CF (1a), CF Cl(1b), 2,6-C H F (1c)
f
3
2
6 3 2
C±F), MS (m/e, %): 432 (M , 2.03), 291 (M -C H F CO,
0.44), 141 (C H F CO , 100.00), 134 (MeOC H CHN ,
6 3 2 6 5
6
3 2
R:C H (2a), 4-CH C H (2b), 4-MeOC H (2c), H(2d)
4
6
5
3
6
6 4
3
1
This reaction is carried out in CH Cl and in the presence
2
2
1.05). Elemental analyses for C H F N O : Anal Calcd.
C 61.11, H 3.70, N 6.48; Found: C 61.24, H 3.53, N 6.59%.
22 16 4 2 3
of a 5±10% mol ratio of R SO H relative to the amount of
f
3
RCHO.
The products are nearly insoluble in cold CH Cl and are
2
2
readily isolated by simple ®ltration of the reaction mixture.
After washing with toluene, the crude recrystallized product
from mixed hot solvent (CH CN/H O 4/1) gave ®ne
3
2
1
H NMR(DMSO-d ) ꢀ(ppm): 9.33 (broad, 2H, NH),
6
crystals. All products are high-melting solids. Their struc-
tures are fully characterized by spectroscopic methods and
microanalysis. The IR spectra of all products showed
19
7
.30±6.80 (m, 6H), 4.84 (t, CH ), 3.60 (s, OCH ).
2
F
3
�
1
NMR(CDCl ): � 115.6 (d, 4F). IR (ꢁmax, cm ): 3300 (s,
3
Table 1
Preparation of the bisamides 3 and 4
b
Yields (%)
Entry
Reactants 1 (or 4) 2
Catalyst
Solvents
Time (t/h)
Temperature (t/8C)
Products
m.p. (8C)
1
2
3
4
5
5
6
7
8
9
1a 2a
1b 2a
1c 2a
1a 2a
1a 2a
1c 2c
1c 2c
1c 2d
1c 2d
4a 2b
4a 2b
T
T
T
f
f
f
OH
CH
CH
CH
2
2
2
Cl
Cl
Cl
2
2
2
24
24
20
10
24
8
50
5
3aa
3ba
3ca
3aa
3aa
3cc
3cc
3cd
3cd
5
87
84
90
86
0
234
217
283
234
234
236
236
185
185
2708
265
OHC
OH
50
80
80
100
100
50
50
50
50
a
R
f
SO
TsOH
OH
TsOH
OH
TsOH
3
H
C
C
6
H
H
6
6
6
T
f
Me-C
Me-C
6
H
H
5
5
92
89
82
80
78
76
6
8
T
f
CH
CH
CH
CH
2
2
2
2
Cl
2
Cl
2
Cl
2
Cl
2
24
24
24
24
R
R
f
SO3H
SO
1
0
f
3
H
6
a. R
b. Isolated yields based on 1.
c. Literature reported m. p. is 2748C.
f 3 f 2 2 2 2 2 2
SO H: R HCF CF , ICF CF OCF CF .