4
'-(12-Bromododecanyloxy)[2,2';6',2"]terpyridine (2). As a result of the reaction of 2,6-bis(2-
pyridyl)-4-pyridone (0.34 g, 1.4 mmol), 1,12-dibromododecane (0.89 g, 2.8 mmol), and potassium carbonate
o
1
(
0.37 g, 2.8 mmol), compound 2 (0.28 g, 42%) was obtained as a white powder; mp 97-98 C. H NMR
spectrum, δ, ppm (J, Hz): 1.40 (14H, m, (CH ) ); 1.56 (2H, m, CH ); 1.88 (4H, m, (CH ) ); 3.37 (2H, t, J = 6.8,
2
7
2
2 2
CH Br); 4.26 (2H, t, J = 6.4, CH O); 7.29 (2H, dd, J = 4.7, J = 7.4, H-5, H-5" Py); 7.81 (2H, t, J = 7.8, H-4,
2
2
1
2
H-4" Py); 8.04 (2H, s, H-3', H-5' Py); 8.62 (2H, d, J = 7.5, H-3, H-3" Py); 8.66 (2H, d, J = 4.1, H-6, H-6" Py).
1
3
C NMR spectrum, δ, ppm: 167.0, 156.6, 156.2, 148.7, 136.1, 123.3, 121.0, 107.5, 67.8, 33.0, 32.8, 29.5, 29.4,
2
9.1, 28.8, 28.2, 26.1. Found, %: C 65.56; H 7.02; 8.31. C H BrN O. Calculated, %: C 65.32; H 6.85; N 8.47.
2
7
34
3
Preparation of Disulfides 3, 4 (General Method). Potassium thioacetate was added to a solution of
4
'-(bromoalkyloxy)[2,2';6',2"]terpyridine in methanol. The reaction mixture was boiled for 10-12 h. After
cooling, saturated ammonium chloride solution (20 ml) was added to the mixture, which was then extracted with
methylene chloride (3 x 20 ml). The organic fraction was dried over anhydrous sodium sulfate, and the solvent
removed in vacuum.
Bis[6'-1-([2,2';6',2"]terpyridyl)oxy]hexyl Disulfide (3). As a result of the reaction of compound 1
(
(
0.16 g, 0.39 mmol) in methanol (10 ml) with potassium thioacetate (0.13 g, 1.2 mmol) for 10 h, compound 3
1
0.12 g, 86%) was obtained as a pinkish oil. H NMR spectrum, δ, ppm (J, Hz): 1.55 (4H, m, (CH ) ); 1.72 (2H,
2
2
m, CH ); 1.87 (2H, m, CH ); 2.73 (2H, t, J = 7.3, CH S); 4.23 (2H, t, J = 6.3, CH O); 7.35 (2H, dd, J = 4.8,
2
2
2
2
1
J2 = 6.8, H-5, H-5" Py); 7.84 (2H, t, J = 7.7, H-4, H-4" Py); 8.02 (2H, s, H-3', H-5" Py); 8.62 (2H, d, J = 7.9,
H-3, H-3" Py); 8.69 (2H, d, J = 3.5, H-6, H-6" Py).
Bis[12'-1-([2,2';6',2"]terpyridyl)oxy]dodecanyl Disulfide (4). As a result of the reaction of compound
2
(0.25 g, 0.5 mmol) in methanol (15 ml) with potassium thioacetate (0.17 g, 1.5 mmol) for 12 h, compound 4
o
1
(
(
0.22 g, 93%) was obtained as a pink-colored powder; mp 83-84 C. H NMR spectrum, δ, ppm (J, Hz): 1.41
14H, m, (CH ) ); 1.58 (2H, m, CH ); 1.88 (4H, m, (CH ) ); 2.66 (2H, t, J = 7.3, CH S); 4.25 (2H, t, J = 6.3,
2
7
2
2 2
2
CH O); 7.31 (2H, t, J = 4.8, H-5, H-5" Py); 7.83 (2H, t, J = 7.7, H-4, H-4" Py); 8.02 (2H, s, H-3', H-5' Py); 8.62
2
1
3
(
2H, d, J = 8.1, H-3, H-3" Py); 8.68 (2H, d, J = 4.0, H-6, H-6" Py). C NMR spectrum, δ, ppm: 167.2, 156.8,
56.2, 148.9, 136.4, 123.5, 121.2, 107.4, 68.0, 39.1, 34.0, 29.5, 29.3, 29.1, 28.4, 26.0, 24.6. Found, %: C 72.49;
H 7.85; N 9.23; S 6.95. C H N O S . Calculated, %: C 75.32; H 7.59; N 9.38; S 7.14.
1
5
4
68
6
2 2
Synthesis of Nanoparticles Modified with Bis[12'-1-([2,2';6',2"]terpyridyl)oxy]dodecanyl Disulfide (4).
A mixture of a solution (15 ml) of HAuCl ·3H O (0.17 g, 0.43 mmol) in distilled water and a solution of
4
2
tetraoctylammonium bromide (0.26 g, 0.47 mmol) in toluene (10 ml) was stirred vigorously to transfer HAuCl4
into the organic phase, which changed color from bright-yellow to dark-brown. The aqueous layer was
separated, and disulfide 4 (0.035 g, 0.04 mmol) was added to the organic layer. A freshly prepared solution of
NaBH (0.18 g, 4.7 mmol) in distilled water (12 ml) was added dropwise with intense stirring. The reaction
4
mixture was stirred for 3 h, the organic layer separated, evaporated to half volume, mixed with ethanol (50 ml)
o
and maintained at -10 C for 4 h. The precipitated solid was filtered off and washed with ethanol. Modified
-
1
nanoparticles of gold (0.2 g) were obtained. IR spectrum, cm : 1662, 1581, 1562 (C=C(Ar), C=N(Ar)).
Interaction of Gold Nanoparticles Modified with Bis[12'-1-([2,2';6',2"]terpyridyl)oxy]dodecanyl
Disulfide (4), with Cu(MeCN) ClO . Cu(MeCN) ClO (10 mg) was added to a suspension of gold
4 4 4 4
nanoparticles (0.1 g) modified with ligand 4 in absolute MeCN (10 ml). The obtained mixture was stirred at
room temperature for 1 day. The solid was filtered off and washed with ethanol. A black powder (0.08 g) was
-
1
obtained. IR spectrum, , cm : 1656, 1606, 1565 (C=C(Ar), C=N(Ar)).
Oxidation of 2,4-Di-tert-butylphenol Catalyzed by Modified Nanoparticles. A stream of air was
passed through a solution of 2,4-di-tert-butylphenol (0.05 g, 0.2 mmol) in a mixture of MeCN–H O, 1:1, for 4 h
2
in the presence of nanoparticles (1 mg) modified with coordination compound of disulfide 4 and
Cu(MeCN) ClO at room temperature. The reaction mixture was rinsed with concentrated aqueous ammonia
4
4
solution (2 ml), and extracted with methylene chloride. The organic phase was dried over anhydrous sodium
1
082