3
3
4
CHar) 7.57 (dd, JHH ¼ 8.6 Hz and JHH ¼ 7.6 Hz,1 H,
3JHH ¼ 7.4 Hz and JHH ¼ 1.2 Hz,1 H,CH Dans),8.29 (d,
CHDans),7.78 (d, 3JHH ¼ 8.4 Hz, 2 H, CHar),7.89 (dd,
3JHH ¼ 8.6 Hz,1 H,CH Dans),8.55 (d, JHH ¼ 8.4 Hz,1 H,
3
3JHH ¼ 8.2 Hz and JHH ¼ 1.4 Hz,2 H,CH ar),8.26 (dd,
CHDans); 13C-NMR: (100.6 MHz,CDCl 3 , 5 ꢀC), d ¼ 10.9,21.0,
4
3JHH ¼ 7.3 Hz and JHH ¼ 1.1 Hz, 1 H, CHDans),8.38 (d,
45.3 [N(CH3)2],49.2,50.2,115.6,119.2,123.1,123.5 (2 CH
128.2,128.6 (2 CH ar),129.8,129.9,130.0,130.6,134.6,144.1
ar),
4
3JHH ¼ 8.9 Hz,1 H,CH Dans),8.53 (d, JHH ¼ 8.4 Hz,1 H,
3
CHDans); 13C-NMR: (100.6 MHz,CDCl 3 ,25 ꢀC) d ¼ 10.9,20.8,
45.3 [N(CH3)2],48.6 (SO 2NCH2Ar),50.3 (SO 2NCH2-Ar),
115.0,119.3,122.7,122.8,123.0,128.0,128.8,128.9,129.7,
(Car),147.2 (C ar),151.6; EI-MS:
m=z (%): calcd for
C22H26N3O4S 427.1566,found: 427.1573 (14,M +),171.1 (100,
[C10H6N(CH3)2+H]+).
129.8,129.9,130.3,130.9,134.9,139.3,151.6,151.8,152.4 (C
EI-MS: m=z (%): calcd for C28H30N4O2S 486.63; found: 486.2
ar);
N-(2,20-Bipyridin-5-ylmethyl)-5-dimethylaminonaphthalene-
N-propyl-1-sulfonamide (PD-BPY). 5-Dimethylaminonaphtha-
lene-N-propyl-1-sulfonamide (50 mg,0.17 mmol) and 200
mg of potassium carbonate were dissolved in 10 ml of dry
DMF. To this suspension a solution of 54 mg (0.22 mmol) of
5-bromomethyl-2,2-bipyridine in 40 ml of DMF was added
dropwise. The mixture was stirred at 25 ꢀC for 3 days under
argon atmosphere. After filtering the undissolved K2CO3 the
solvent was removed in vacuo and the residue was collected in
(85,M +),171.0 (100,[C 10H6N(CH3)2+H]+).
N-(2-Naphthalenemethyl)-5-dimethylaminonaphthalene-N-
propyl-1-sulfonamide (PD-NA). 5-Dimethylaminonaphthalene-
N-propyl-1-sulfonamide (102 mg,0.35 mmol) and 210 mg
of potassium carbonate were dissolved in 10 ml of dry DMF.
To this suspension a solution of 77 mg (0.35 mmol) of 2-
bromomethylnaphthalene in 20 ml of DMF was added drop-
wise. The mixture was stirred at 25ꢀC for 1 day under argon
atmosphere. After filtering the undissolved K2CO3 the solvent
was removed in vacuo and the residue was collected in
dichloromethane. After washing with water,aq. Na CO3 and
2
again with water the organic phase was dried with Na2SO4 .
After removal of the solvent under reduced pressure the resi-
due was chromatographed twice (SiO2 ,40–60 mm,dichloro-
methane–methanol 20 : 1 and SiO2 ,40–60 mm,petroleum
ether (40–60)–methanol–triethylamine 15 : 1 : 1) to yield 50.5
mg (64%) of a bright yellow solid. TLC (SiO2): Rf ¼ 0.20
(dichloromethane–methanol 20 : 1); 1H-NMR: (400 MHz,
dichloromethane. After washing with water,aq. Na CO3 and
2
again with water the organic phase was dried with Na2SO4 .
Further purification was achieved by column chromatography
(SiO2 ,40–60 mm,dichloromethane) yielding 130.1 mg (86%)
of a bright yellow solid. M.p.: 91–92ꢀC. TLC (SiO2): Rf ¼ 0.38
(dichloromethane); 1H-NMR: (400 MHz,CDCl 3 ,25 ꢀC),
3
CDCl3 ,25 ꢀC) d ¼ 0.67 (t, JHH ¼ 7.4 Hz,3 H,CH 3),1.42
3
3
3
(sext, JHH ¼ 7.6 Hz,2 H,CH 2CH2CH3),2.86 [s,6 H,
d ¼ 0.67 (t, JHH ¼ 7.38 Hz,3 H,CH 3),1.44 (sext, JHH ¼ 7.48
3
N(CH3)2],3.20 (t, JHH ¼ 7.9 Hz,2 H,C H2CH2CH3),4.51 (s,2
Hz,2 H,CH 2CH2CH3),2.90 [s,6 H,N(CH
3)2],3.23 (t,
3
3JHH ¼ 7.63 Hz,2 H,C
H2CH2CH3),4.63 (s,2 H,
3JHH ¼ 8.86 Hz and
H,NCH 2Bpy),7.18 (d, JHH ¼ 7.4 Hz,1 H,CH Dans),7.28
3
3
4
(ddd, JHH ¼ 7.5 Hz, JHH ¼ 4.8 Hz, JHH ¼ 1.1 Hz,1 H,
NCH2Naph),7.23 and 7.25 (d,
3JHH ¼ 7.63 Hz,je 1 H,CH
3
3
CHBpy),7.50 (dd, JHH ¼ 8.4 Hz and JHH ¼ 7.4 Hz,1 H,
and CHDans),7.44 (dd,
3
Naph
3JHH ¼ 6.15 and 3.20 Hz,2 H,CH Naph),7.51 (dd, JHH ¼ 8.61
3
3
CHDans),7.56 (dd, JHH ¼ 8.5 Hz and JHH ¼ 7.5 Hz,1 H,
3
4
3
CHDans),7.58 (dd, JHH ¼ 8.0 Hz and JHH ¼ 2.2 Hz,1 H,
Hz and JHH ¼ 7.14 Hz,1 H,CH Dans),7.51 (s,1 H,CH Naph),
3
4
3
3
CHBpy),7.78 (td, JHH ¼ 7.7 Hz and JHH ¼ 1.8 Hz,1 H,
CHBpy),8.22 (d, 3JHH ¼ 7.9 Hz,1 H,CH Bpy),8.24 (dd,
3JHH ¼ 7.4 Hz and 4JHH ¼ 1.2 Hz,1 H,CH Dans),8.31 (m,2 H,
7.60 (pt, JHH ¼ 8.24 Hz,1 H,CH Dans),7.63 (dd, JHH ¼ 6.03
4
3
Hz and JHH ¼ 3.81 Hz,1 H,CH Naph),7.69 (d, JHH ¼ 8.37
3
4
Hz,1 H,CH Naph),7.77 (dd, JHH ¼ 5.78 Hz and JHH ¼ 3.57
4
3
CHBpy and CHDans),8.43 (d, JHH ¼ 1.7 Hz,1 H,CH Bpy),8.52
Hz,1 H,CH Naph),8.29 (d, JHH ¼ 8.37 Hz,1 H,CH Dans),8.43
3
3
(d, 3JHH ¼ 8.61 Hz,1 H,CH Dans),8.56 (d, JHH ¼ 8.37 Hz,1 H,
3
(d, JHH ¼ 8.4 Hz,1 H,CH Dans),8.64 (dq, JHH ¼ 4.8 Hz and
4JHH ¼ 0.8 Hz,1 H,CH Bpy); 13C-NMR: (100.6 MHz,CDCl
25 ꢀC), d ¼ 11.0,21.0,45.3 [N(CH 3)2],48.0,48.6,115.2,119.2,
,
CHDans); 13C-NMR: (100.6 MHz,CDCl 3 ,25 ꢀC), d ¼ 11.1,
3
20.9,45.5 [N(CH 3)2],48.4,50.7,115.3,119.9,123.3,126.0
120.8 (CHBpy),121.0 (CH Bpy),123.1,123.8 (CH Bpy),128.2,
(CNaph),126.1 (C Naph),126.2 (C Naph),127.2 (C Naph),127.6
(CNaph),127.7 (C Naph),128.1,128.3 (C Naph),130.0,130.1,
130.2,130.3,132.8 (C Naph),133.2 (C Naph),133.7 (C Naph),
129.9,130.0,130.1,130.6,131.9 (CH Bpy),134.7,136.9 (CH Bpy),
137.0 (CHBpy),148.8 (CH Bpy),149. (C Bpy),151.8,155.6 (C Bpy),
155.7 (CBpy); EI-MS: m=z (%): calcd for C26H28N4O2S
460.1933; found: 460.1932 (27,M +),445.2 (20,[M À CH3]+),
135.3,151.7; EI-MS:
m/z (%): calcd for C26H28N2O2S
432.1871; found: 432.1873 (17,M +),198.1 (10),171.1 (100,
[C10H6N(CH3)2+H]+),141.1 (28).
431.2 (30,[M
À C2H5]+),267.1 (40),226.1 (65,
[M À C12H10NO2S]+),169.1 (33),101.1 (22),86.1 (100),50.1
(41).
N-(4-Nitrobenzyl)-5-dimethylaminonaphthalene-N-propyl-1-
sulfonamide (PD-NB). 5-Dimethylaminonaphthalene-N-propyl-
1-sulfonamide (100 mg,0.34 mmol) and 210 mg of potassium
carbonate were dissolved in 5 ml of dry DMF. To this suspen-
sion a solution of 81.3 mg (0.38 mmol) of 4-nitrobenzyl bromide
in 30 ml of DMF was added dropwise. The mixture was stirred
at 25 ꢀC for 15 h under argon atmosphere. After filtering the
undissolved K2CO3 the solvent was removed in vacuo and the
residue was collected in dichloromethane. After washing with
water,aq. Na 2CO3 and again with water the organic phase
was dried with Na2SO4 . Further purification was achieved by
column chromatography (SiO2 ,60–100 mm,dichloromethane)
yielding 65.5 mg (45%) of a green-yellow solid. TLC (SiO2):
[{N-(2,20-Bipyridin-5-ylmethyl)-5-dimethylaminonaphthalene-
N-propyl-1-sulfonamide}] bis(2,20-bipyridine)]ruthenium(II) bis-
(hexafluorophosphate) (PD-RU). A suspension of 56 mg
(0.12 mmol) of N-(2,20-bipyridin-5-ylmethyl)-5-dimethyl-
aminonaphthalene-N-propyl-1-sulfonamide and 60 mg of cis-
dichlorobis(2,20-bipyridine)ruthenium(II) dihydrate in 5 ml of
ethylene glycol and 1.5 ml of ethanol was heated under reflux
twice for 2 min in a microwave oven at 600 W. The completion
of complexation was controlled via TLC (acetonitrile–water–
methanol–potassium nitrate 40 : 10 : 10 : 1). After cooling the
now orange reaction mixture was treated with 20 ml of water
and 2.0 g of ammonium hexafluorophosphate. The volumi-
nous precipitate was filtered off and washed with water and
diethyl ether to yield 91.7 g (87%) of an intense orange solid,
melting at 183–185 ꢀC with decomposition. TLC (SiO2): Rf ¼
(acetonitrile–methanol–water–potassium nitrate 40 : 10 : 10 :
1); 1H-NMR: (250 MHz,CD 3CN,25 ꢀC) d ¼ 0.42 (t,
Rf ¼ 0.26 (dichloromethane); 1H-NMR: (400 MHz,CDCl
,
3
3
25 ꢀC), d ¼ 0.65 (t, JHH ¼ 7.4 Hz,3 H,CH 3),1.36 (sext,
3JHH ¼ 7.5 Hz,2 H,CH 2CH2CH3),2.89 [s,6 H,N(CH 3)2],3.19
(t, 3JHH ¼ 7.8 Hz, 2 H, CH2CH2CH3),4.56 (s,2 H,NC H2C6H5),
3
3
7.20 (d, JHH ¼ 7.4 Hz, 1 H, CHDans),7.34 (d, JHH ¼ 8.8 Hz,2
3
3
H,CH ar),7.50 (dd, JHH ¼ 8.4 Hz and JHH ¼ 7.4 Hz,1 H,
3
3
3
CHDans),7.56 (dd, JHH ¼ 8.6 Hz and JHH ¼ 7.6 Hz,1 H,
CHDans),8.05 (d, 3JHH ¼ 8.4 Hz, 2 H, CHar),8.22 (dd,
3JHH ¼ 7.3 Hz,3 H,CH 3),0.99 (psext, JHH ¼ 7.4 Hz,2 H,
3
CH2CH2CH3),2.85 [s,6 H,N(CH 3)2],2.98 (t, JHH ¼ 7.6 Hz,2
68
New J. Chem.,2002, 26,66–75