_
´
J. Zabinski et al. / Journal of Molecular Structure 923 (2009) 132–140
134
bis(2-chloroethyl)amine hydrochloride (1.78 g; 10 mmol) by the
procedure analogous to that for 1a. M.p. 111–112 °C; 1H NMR
(400.13 MHz, DMSO-d6): d = 2.06 (s, 3H, 12-CH3), 3.40 (t, J = 6.6 Hz,
4H, 9-CH2, 90-CH2), 3.68 (t, J = 6.6 Hz, 4H, 8-CH2, 80-CH2), 7.77 (br s,
4H, 200-H, 300-H, 500-H, 600-H), 10.35 (s, 1H, NH) ppm; 13C NMR
(100.62 MHz, DMSO-d6): d = 24.16 (C-12), 42.26 (C-9, C-90), 50.21
(C-8, C-80), 118.81 (C-300, C-500), 128.31 (C-200, C-600), 131.71 (C-100),
143.54 (C-400), 169.10 (C-11); IR (KBr disc, cmꢀ1): 3302–3260 (m,
H 5.72, N 11.45, S 5.57%; 1H NMR (199.97 MHz, DMSO-d6):
d = 2.38 (s, 3H, 10-CH3), 3.69 (br s, 4H, 9-CH2, 90-CH2), 4.28 (br s,
4H, 8-CH2, 80-CH2), 7.05 (m, 4H, 2-H, 20-H, 6-H, 60-H), 7.40 (m,
2H, 300-H, 500-H), 7.77 (m, 2H, 200-H, 600-H), 7.94 (m, 4H, 3-H, 30-H,
5-H, 50-H), 9.22 (br s, 4H, NH2), 9.45 (br s, 4H, NH2) ppm; 13C
NMR (50.28 MHz, DMSO-d6): d = 20.88 (C-10), 47.75 (C-9, C-90),
66.75 (C-8, C-80), 114.57 (C-2, C-6, C-20, C-60), 119.48 (C-4, C-40),
126.91 (C-200, C-600), 129.78 (C-300, C-500), 130.16 (C-3, C-5, C-30, C-
50), 135.78 (C-100), 143.33 (C-400), 162.27 (C-7, C-70), 164.56 (C-1,
C-10) ppm; IR (KBr disc, cmꢀ1): 3526 (m) mN–H as; 3400–3200 (s,
br)
m
N–H as; 3190 (m)
m
N–H sym; 3059 (m)
CH2; 1593,1497 (s) C=C; 1543 (s) dN–H; 1454 (m) dC–H al
SO2 as; 1157 (s) SO2 sym; 826 (m) cH–C
mC–H ar; 2975–2855 (w, br)
mCH3 and
m
m
;
1338 (s)
m
m
.
br)
m
N–H sym, 3055 (s)
m
C–H ar; 2882 (w)
mCH2; 1670 (s) m=NH; 1608,
1489 (s)
1150 (s,)
m
m
C=C; 1570 (w) dN–H; 1319 (s) mSO2 as; 1269 (s) mC–O
SO2 sym; 1022 (s) mC–O sym; 841 (s) cH–C.
;
as
2.1.3. N,N-Bis[2-(4-cyanophenoxy)ethyl]-4-toluenesulfonamide (1c)
N,N-Bis(2-chloroethyl)-4-toluenesulfonamide 1a (0.89 g;
3 mmol), 4-hydroxybenzonitrile (0.71 g; 6 mmol), anhydrous
K2CO3 (1.38 g; 10 mmol), and N-methyl-2-pyrrolidone (10 ml)
were intensively stirred and heated at about 130 °C for 12 h. After
this time the reaction mixture was poured into ice water (50 ml) to
form an oil, which solidified after a few hours. The crystals were
collected by filtration, washed with water and dried. Recrystalliza-
tion from ethanol gave 0.55 g (40%) of colorless crystals of 1c. M.p.
133–137 °C; C25H23N3O4S (461.5): calcd. C 65.06, H 5.02, N 9.10, S
2.1.6. N,N-Bis[2-(4-cyanophenoxy)ethyl]-4-(acetylamino)-
benzenesulfonamide (2c)
A 0.76 g (50%) of white powder of 2c, hardly soluble in most
commonly used solvents was obtained from 1.02 g N,N-bis(2-
chloroethyl)-4-(acetylamino)benzenesulfonamide 1b (3 mmol)
and 0.72 g 4-hydroxybenzonitrile (6 mmol) by the procedure
described for 1c. The crude product was purified by refluxing with
acetone (10 ml). M.p. 215–216 °C; C26H24N4O5S (504.8): calcd. C
61.89, H 4.79, N 11.10, S 6.35%; found C 61.68, H 4.70, N 10.98, S
6.27%; 1H NMR (400.13 MHz, DMSO-d6): d = 2.09 (s, 3H, 12-CH3),
3.60 (br s, 4H, 9-CH2, 90-CH2), 4.21 (br s, 4H, 8-CH2, 80-CH2), 6.99
(m, 4H, 2-H, 6-H, 20-H, 60-H), 7.71 (m, 4H, 3-H, 5-H, 30-H, 50-H),
7.72 (m, 2H, 200-H, 600-H), 7.77 (m, 2H, 300-H, 500-H), 10.31 (s, 1H,
NH) ppm; 13C NMR (100.62 MHz, DMSO-d6): d = 24.12 (C-12),
47.74 (C-9, C-90), 66.76 (C-8, C-80), 103.07 (C-4, C-40), 115.43
(C-2, C-6, C-20, C-60), 118.69 (C-300, C-500), 119.03 (C-7, C-70),
128.15 (C-200, C-600), 132.22 (C-100), 134.11 (C-3, C-5, C-30, C-50),
143.27 (C-400), 161.42 (C-1, C-10), 168.99 (C-11) ppm; IR (KBr disc,
6.95%; found
C 64.58, H 5.04, N 8.81, S
6.97%; 1H NMR
(199.97 MHz, CDCl3): d = 2.41 (s, 3H, 10-CH3), 3.68 (t, J = 5.6 Hz,
4H, 9-CH2, 90-CH2), 4.24 (t, J = 5.6 Hz, 4H, 8-CH2, 80-CH2), 6.86 (m,
4H, 2-H, 20-H, 6-H, 60-H), 7.29 (m, 2H, 300-H, 500-H), 7.55 (m, 4H,
3-H, 30-H, 5-H, 50-H), 7.72 (m, 2H, 200-H, 600-H) ppm; 13C NMR
(50.28 MHz, CDCl3): d = 21.41 (C-10), 48.96 (C-9, C-90), 67.35 (C-
8, C-80), 104.43 (C-4, C-40), 114.99 (C-2, C-6, C-20, C-60), 118.84
(C-7, C-70), 127.00 (C-200, C-600), 129.82 (C-300, C-500), 133.95 (C-3,
C-5, C-30, C-50), 135.85 (C-100), 143.91 (C-400), 161.29 (C-1, C-10)
ppm; IR (KBr disc, cmꢀ1): 3100–3050 (w, br)
m
C–H ar; 2951–2928
CꢁN; 1605, 1574,
SO2 as; 1258 (s)
C–O sym; 837 (s) cH–C
(m, br)
m
CH3; 2885–2880 (w)
C=C; 1465–1450 (m) dC–H al; 1308 (s)
SO2 sym; 1011 (s)
m
CH2; 2226 (m)
m
m
cmꢀ1): 3337 (s)
2930 (m, br) CH3 and
(s) dN–H; 1458 (s) dC–H al; 1323 (s)
SO2 sym; 1018 (s)
m
N–H as; 3290 (m)
m
N–H sym; 3101 (m)
m
SO2 as; 1242 (s) m
m
C–H ar; 2951–
CꢁN; 1585, 1497 (s) C=C; 1535
C–O as; 1153 (s)
1512 (s)
m
m
m
m
CH2; 2222 (s)
m
C–O as; 1153 (s)
m
m
.
m
m
m
C–O sym; 833 (s) cH–C
.
2.1.4. N,N-Bis{2-[4-(ethoxyiminoyl)phenoxy]ethyl}-4-toluenesulfonamide
dihydrochloride (1d)
2.1.7. N,N-Bis[2-(4-amidinophenoxy)ethyl]-4-(acetylamino)-
benzenesulfonamide dihydrochloride (2)
Compound 2 was prepared by the method described for 1 from
N,N-bis{2-[4-(ethoxyiminoyl)phenoxy]ethyl}-4-(acetylamino)ben-
zenesulfonamide dihydrochloride 2d (obtained from N,N-bis[2-(4-
Dry ethanol (40 ml) was saturated with anhydrous HCl at
0–5 °C. To this solution N,N-bis[2-(4-cyanophenoxy)ethyl]-
4-toluenesulfonamide 1c (1.84 g; 4 mmol) was added, and the con-
tents were stirred in a sealed vessel for 24 h at room temperature.
Then the reaction mixture was diluted with dry diethyl ether
(100 ml) until colorless crystals were formed. The crystals were
quickly filtered off, and dried under reduced pressure over
anhydrous CaCl2.
cyanophenoxy)ethyl]-4-(acetylamino)benzenesulfonamide
2c
(1.40 g; 2.78 mmol) by the procedure given for 1d). The resulting
colorless precipitate 2 was filtered and dried to furnish 1.14 g
(64%) of fine white crystals. M.p. 274–276 °C (dec); C26H30N6O5S ꢂ
2HCl ꢂ 1½H2O (638.6): calcd. C 48.90, H 5.52, N 13.16, S 5.02%;
found C 49.16, H 5.40, N 13.18, S 4.84%; 1H NMR (400.13 MHz,
DMSO-d6): d = 2.10 (s, 3H, 12-CH3), 3.63 (br s, 4H, 9-CH2, 90-CH2),
4.25 (br s, 4H, 8-CH2, 80-CH2), 7.04 (m, 4H, 2-H, 20-H, 6-H, 60-H),
7.79 (br s, 4H, 200-H, 300-H, 500-H, 600-H), 7.85 (m, 4H, 3-H, 30-H, 5-
H, 50-H), 9.10 (br s, 4H, NH2), 9.31 (br s, 4H, NH2), 10.64 (s, 1H,
NH) ppm; 13C NMR (100.62 MHz, DMSO-d6): d = 24.02 (C-12),
47.82 (C-9, C- 90), 66.84 (C-8, C-80), 114.72 (C-2, C-6, C-20, C-60),
118.75 (C-300, C-500), 119.46 (C-40), 119.52 (C-4), 128.08 (C-200, C-
600), 130.20 (C-3, C-5, C-30, C-50), 143.20 (C-400), 162.40 (C-7, C-70),
164.42 (C-10), 164.49 (C-1), 169.16 (C-11) ppm; IR (KBr disc,
2.1.5. N,N-Bis[2-(4-amidinophenoxy)ethyl]-4-toluenesulfonamide
dihydrochloride (1)
Dry ethanol (40 ml) was saturated with anhydrous NH3 at 0–
5 °C. To the prepared solution all amount of N,N-bis{2-[4-(ethoxy-
iminoyl)phenoxy]ethyl}-4-toluenesulfonamide dihydrochloride 1d
obtained from 1c was added, and the whole was stirred in a sealed
vessel for 24 h at room temperature. Ethanol was evaporated un-
der reduced pressure almost to dryness. The residue was placed
in a solution of NaOH (1.0 g) in water (40 ml) and stirred for
15 min. The free base, which was formed as a fine white precipitate
was filtered, washed thoroughly with water, and dried under vac-
uum over anhydrous CaCl2. The dry colorless powder was then
mixed with anhydrous ethanol (10 ml), acidified with an excess
of ethanolic HCl, and refluxed to obtain a homogeneous solution.
After cooling, dry diethyl ether (30 ml) was slowly added with stir-
ring. After a few minutes the colorless crystals were filtered,
washed with dry diethyl ether, and dried to give 1.83 g (84%) of
the pure product 1. M.p. 228–232 °C; C25H29N5O4S ꢂ 2HCl ꢂ H2O
(586.5): calcd. C 51.19, H 5.67, N 11.94, S 5.47%; found C 51.04,
cmꢀ1): 3400–3200 (s, br)
2885 (m, br) mC–H al; 1666 (s)
1520 (s) dN–H; 1466–1550 (s) dC–H al; 1335 (s) mSO2 as; 1273 (s)
C–O as; 1142 (s) SO2 sym; 1022 (s) C–O sym; 845 (w) cH–C
mN–H; 3113–3063 (s, br) mC–H ar; 2930–
m
=NH; 1612, 1585 (s) C=C; 1540–
m
m
m
m
.
2.1.8. N,N-Bis[2-(4-cyano-2,6-dimethoxyphenoxy-)ethyl]-4-toluene-
sulfonamide (3c)
Compound 3c was obtained from N,N-bis(2-chloroethyl)-4-
toluenesulfonamide 1a (1.48 g; 5 mmol) and 4-hydroxy-3,5-