Paper
Dalton Transactions
addition of aqueous sodium hydrogen carbonate, the product for 1 day to give colorless crystals of [Zn(8-MeOTQA)](ClO4)2
was extracted with dichloromethane, dried and evaporated to (17.5 mg, 0.029 mmol) in 98% yield.
give 6,8-dimethoxy-2-chloromethylquinoline (142 mg, 0.63 mmol)
in 100% yield.
1H NMR (CD3CN): δ 8.66 (d, J = 8.2 Hz, 3H), 7.70–7.79
(m, 9H), 7.47 (dd, J = 1.8, 7.3 Hz, 3H), 4.71 (d, J = 17.9 Hz, 3H),
1H NMR (CDCl3): δ 8.15 (d, J = 8.5 Hz, 1H), 7.65 (d, J = 4.32 (d, J = 17.9 Hz, 3H), 3.73 (s, 9H). 13C NMR (CD3CN):
8.5 Hz, 1H), 7.55 (dd, J = 1.5, 7.9 Hz, 1H), 7.48 (dd, J = 7.0, δ 159.1, 150.8, 142.8, 136.3, 130.2, 129.5, 123.6, 122.3, 112.7,
8.2 Hz, 1H), 7.39 (dd, J = 1.5, 7.0 Hz, 1H), 4.88 (s, 2H), 2.56 59.0, 57.3. Anal. Calcd for C33H30Cl2N4O11Zn ([Zn(8-MeOTQA)]-
(s, 3H). 13C NMR (CDCl3): δ 155.3, 144.0, 139.6, 137.2, (ClO4)2): H, 3.80; C, 49.86; N, 7.05. Found: H, 3.77; C, 49.61;
127.0, 126.8, 123.00, 122.97, 120.8, 47.3, 14.4. Anal. Calcd for N, 7.05.
C11H10.2ClNO0.1S (+0.1H2O): H, 4.56; C, 58.58; N, 6.21. Found:
H, 4.51; C, 58.34; N, 6.06.
[Cd(8-MeOTQA)](ClO4)2. A mixture of 8-MeOTQA (7.9 mg,
0.015 mmol) in CHCl3 (0.03 mL) and Cd(ClO4)2·6H2O (6.6 mg,
Tris(8-methylthio-2-quinolylmethyl)amine (8-MeSTQA, 7). 0.015 mmol) in methanol (0.5 mL) was stand at 4 °C for 1 day
1H NMR (CDCl3): δ 8.09 (d, J = 7.9 Hz, 3H), 7.93 (d, J = 8.2 Hz, to give colorless crystals of [Cd(8-MeOTQA)](ClO4)2 (8.6 mg,
3H), 7.51 (d, J = 7.3 Hz, 3H), 7.43 (dd, J = 7.6, 7.9 Hz, 3H), 7.35 0.013 mmol) in 89% yield.
(d, J = 6.7 Hz, 3H), 4.18 (s, 6H), 2.56 (s, 9H). 13C NMR (CDCl3):
1H NMR (CD3CN): δ 8.59 (d, J = 8.5 Hz, 3H), 7.66–7.78
δ 157.8, 144.6, 138.8, 136.0, 125.9, 125.5, 123.0, 122.39, 122.35, (m, 9H), 7.58 (dd, J = 1.5, 7.3 Hz, 3H), 4.45 (br., 6H), 4.10
25.6, 14.4. Anal. Calcd for C33H32N4OS3 (7·H2O): H, 5.40; (s, 9H). 13C NMR (CD3CN): δ 158.1–150.3, 141.9, 136.8,
C, 66.41; N, 9.39. Found: H, 5.07; C, 65.97; N, 8.97. ESI-MS m/z: 130.0, 129.1, 124.0, 122.9, 113.2, 60.1, 58.1. Anal. Calcd for
601.2 ([M + Na]+).
C33H30CdCl2N4O11 ([Cd(8-MeOTQA)](ClO4)2): H, 3.59; C, 47.08;
Bis(8-methoxy-2-quinolylmethyl)(2-pyridylmethyl)amine N, 6.65. Found: H, 3.61; C, 46.96; N, 6.62.
(8-MeOBQPA, 8). To an acetonitrile solution (30 mL) of
[Zn(8-MeOBQPA)(CH3OH)](ClO4)2. To a chloroform solution
8-methoxy-2-chloromethylquinoline (483 mg, 2.33 mmol) and (0.1 mL) of 8-MeOBQPA (4.5 mg, 0.010 mmol) was added
2-aminomethylpyridine (0.11 mL, 1.16 mmol) was added pot- Zn(ClO4)2·6H2O (3.7 mg, 0.010 mmol) in methanol (0.8 mL)
assium carbonate (643 mg, 4.65 mmol) and potassium iodide and the solution was stand at 4 °C to give [Zn(8-MeOBQPA)-
(772 mg, 4.65 mmol). The resulting reaction mixture was (CH3OH)](ClO4)2 as colorless crystals (5.3 mg, 0.0071 mmol) in
refluxed for 2 days. The resulting solution was cooled to room 71% yield.
temperature and the solvent was evaporated. The residue was
1H NMR (CD3CN): δ 8.86 (d, J = 5.2 Hz, 1H), 8.60 (d, J =
extracted with CHCl3–water, dried, evaporated and washed 8.5 Hz, 2H), 8.04 (ddd, J = 7.8, 7.8, 1.5 Hz, 1H), 7.72–7.70
with acetonitrile to give 8-MeOBQPA as white powder (368 mg, (m, 4H), 7.67–7.60 (m, 3H), 7.52 (d, J = 4.1 Hz, 1H), 7.42
0.82 mmol) in 71% yield.
(dd, J = 4.9, 4.3 Hz, 2H), 4.50 (d, J = 3.4 Hz, 4H), 4.25
1H NMR (CDCl3): δ 8.53 (d, J = 4.9 Hz, 1H), 8.12 (d, J = (s, 2H), 3.90 (s, 6H). 13C NMR (CD3CN): δ 157.5, 155.4,
8.5 Hz, 2H), 7.91 (d, J = 8.5 Hz, 2H), 7.65–7.64 (m, 2H), 151.3, 148.6, 141.8, 141.6, 136.1, 130.0, 129.0, 125.8,
7.44–7.34 (m, 4H), 7.13 (dd, J = 4.9, 8.5 Hz, 1H), 7.02 (dd, J = 125.1, 122.7, 121.4, 111.6, 57.7, 57.4, 56.7. Anal. Calcd for
0.6, 7.3 Hz, 2H), 4.17 (s, 4H), 4.07 (s, 6H), 3.94 (s, 2H). C28H28Cl2N4O11Zn ([Zn(8-MeOBQPA)(H2O)](ClO4)2): H, 3.85; C,
13C NMR (CDCl3): δ 159.2, 159.1, 154.8, 148.9, 139.2, 136.2, 45.89; N, 7.65. Found: H, 3.62; C, 46.20; N, 7.54.
136.1, 128.2, 126.0, 122.9, 121.8, 121.0, 119.2, 107.6, 61.1, 60.5,
[Cd(8-MeOBQPA)(CH3OH)](ClO4)2. To a chloroform solution
56.1. Anal. Calcd for C28H26N4O2 (8-MeOBQPA): H, 5.82; (0.1 mL) of 8-MeOBQPA (4.5 mg, 0.010 mmol) was added
C, 74.64; N, 12.44. Found: H, 5.76; C, 74.61; N, 12.57. ESI-MS Cd(ClO4)2·6H2O (4.2 mg, 0.010 mmol) in methanol (0.8 mL)
m/z: 473.2 ([M + Na]+).
and the solution was stand at 4 °C to give [Cd(8-MeOBQPA)-
[Zn(6-MeOTQA)(DMF)(ClO4)]ClO4. A mixture of 6-MeOTQA (CH3OH)](ClO4)2 as colorless crystals (6.2 mg, 0.0079 mmol) in
(5.3 mg, 0.010 mmol) in CHCl3 (0.20 mL) and Zn(ClO4)2·6H2O 79% yield.
(3.7 mg, 0.010 mmol) in methanol (1.0 mL) and DMF
1H NMR (CD3CN): δ 8.79 (d, J = 5.5 Hz, 1H), 8.56 (d, J =
(0.1 mL) was stand at 4 °C for 1 day to give colorless crystals of 8.5 Hz, 2H), 8.03 (dd, J = 6.7, 1.8 Hz, 1H), 7.74–7.58 (m, 7H),
[Zn(6-MeOTQA)(DMF)(ClO4)]ClO4 (5.0 mg, 0.0056 mmol) in 7.53–7.48 (m, 3H), 4.39 (s, 4H), 4.15 (s, 8H). 13C NMR (CD3CN):
56% yield.
δ 157.2, 155.5, 150.4, 149.5, 141.2, 136.3, 129.7, 128.7, 125.8,
1H NMR (CD3CN): δ 8.56 (d, J = 9.2 Hz, 3H), 8.30 (d, J = 123.3, 121.9, 111.8, 58.1, 57.8, 57.2. Anal. Calcd for
8.5 Hz, 3H), 7.85 (s, 1H), 7.55 (dd, J = 9.2, 2.4 Hz, 3H), 7.42 C28H28CdCl2N4O11 ([Cd(8-MeOBQPA)(H2O)](ClO4)2): H, 3.64;
(d, J = 8.5 Hz, 3H), 7.30 (d, J = 2.4 Hz, 3H), 4.75 (s, 6H), C, 43.37; N, 7.23. Found: H, 3.33; C, 43.62; N, 7.19.
3.88 (s, 9H), 3.05 (s, 3H), 2.90 (s, 3H). 13C NMR (CD3CN):
X-ray crystallography
δ 165.0, 159.1, 155.1, 140.9, 140.4, 131.0, 128.1, 122.3, 107.6,
63.6, 56.7, 47.6, 37.9, 33.1. Anal. Calcd for C36H39Cl2N5O13Zn Single crystals of 2, 8-MeOTQA·0.5CH2Cl2 (4·0.5CH2Cl2), [Zn-
([Zn(6-MeOTQA)(DMF)(ClO4)]ClO4·H2O): H, 4.44; C, 48.80; (6-MeOTQA)(DMF)(ClO4)]ClO4·0.5H2O, [Zn(8-MeOTQA)](ClO4)2,
N, 7.90. Found: H, 4.22; C, 49.00; N, 7.90.
[Zn(8-MeOBQPA)(CH3OH)](ClO4)2·0.5H2O,
[Cd(8-MeOTQA)]-
[Zn(8-MeOTQA)](ClO4)2. A mixture of 8-MeOTQA (15.3 mg, (ClO4)2 and [Cd(8-MeOBQPA)(CH3OH)](ClO4)2·CH3OH were
0.030 mmol) in CHCl3 (0.03 mL) and Zn(ClO4)2·6H2O covered by paratone-N oil and mounted on a glass fibre. All
(11.1 mg, 0.030 mmol) in methanol (15 mL) was stand at 4 °C data were collected at 153 K on Rigaku Mercury or Saturn CCD
Dalton Trans.
This journal is © The Royal Society of Chemistry 2015