Inorganic Chemistry
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1
(0.19 g, 0.45 mmol) in 18% yield. H NMR (500 MHz, CDCl3) δ
7.59 (d, J = 2.5 Hz, 1H, ArCH), 7.50 (d, J = 2.5 Hz, 1H, ArCH), 4.87
(s, 2H, ArCH2N), 3.83 (s, 3H, OCH3), 3.36 (s, 9H, NCH3), 1.39 (s,
9H, C(CH3)3), 1.32 (s, 9H, C(CH3)3). 13C NMR (151 MHz, CDCl3)
δ 157.7 (s, 1C, ArCO), 147.5 (s, 1C, ArC), 143.8 (s, 1C, ArC), 130.8
(s, 1C, ArC), 128.2 (s, 1C, ArCH), 120.8 (s, 1C, ArCH), 65.8 (s, 1C,
ArCH2N), 64.1 (s, 1C, OCH3), 53.4 (s, 3C, NCH3), 35.6 (s, 1C,
C(CH3)3), 34.9 (s, 1C, C(CH3)3), 31.5 (s, 3C, C(CH3)3), 31.3 (s,
3C, C(CH3)3). HRMS(ESI): calcd for C19H34NO+: 292.262 [M −
I]+, found 292.26. Anal. calcd (found) for C19H34NO+I−: C, 54.41
(53.95); H, 8.17 (8.54); N, 3.34 (2.81)%.
pound was obtained as white powder (0.28 g, 0.57 mmol) in 27%
yield. 1H NMR (500 MHz, CDCl3) δ 7.56 (d, J = 2.5 Hz, 1H, ArCH),
7.44 (dd, J = 7.9, 2.5 Hz, 1H, ArCH), 5.42 (t, J = 4.6 Hz, 1H, CH),
4.97 (s, 2H, ArCH2N), 4.11−3.90 (m, 4H, CH2), 3.77 (s, 3H,
OCH3), 3.73 (d, J = 4.7 Hz, 2H, NCH2), 3.25 (s, 6H, NCH3), 1.3 (s,
9H, C(CH3)3), 1.26 (s, 9H, C(CH3)3). 13C NMR (126 MHz, CDCl3)
δ 157.8 (s, 1C, ArCO), 147.3 (s, 1C, ArC), 143.6 (s, 1C, ArC), 131.1
(s, 1C, ArCH), 128.0 (s, 1C, ArCH), 120.6 (s, 1C, ArC), 98.1 (s, 1C,
CH), 65.6 (s, 1C, ArCH2N), 65.4 (s, 1C, OCH3), 64.4 (s, 2C, CH2),
64.1 (s, 1C, NCH2), 51.4 (s, 2C, NCH3), 35.4 (s, 1C, C(CH3)3), 34.7
(s, 1C, C(CH3)3), 31.5 (s, 3C, C(CH3)3), 31.1 (s, 3C, C(CH3)3).
+
HRMS(ESI): calcd for C22H38NO3 : 364.28 [M − I]+, found 364.28.
N,N-Dibenzyl-1-(3,5-di-tert-butyl-2-methoxyphenyl)-
methanamine [LBnO‑Me]. Synthesis of [LBnO‑Me] was performed by
using appropriate substrates as follows: compound [LBn-H] (1.00 g,
2.41 mmol), NaH (0.072 g, 3.00 mmol, 1.25 equiv), and MeI (0.23
mL, 3.61 mmol, 1.5 equiv). Compound was obtained as white
powder, yield: (0.84 g, 1.96 mmol, 82%). 1H NMR (500 MHz,
CDCl3) δ 7.72−7.69 (m, 1H, ArCH), 7.44−7.40 (m, 4H, ArCH),
7.30 (dd, J = 10.9, 4.3 Hz, 4H, ArCH), 7.23−7.18 (m, 3H, ArCH),
3.64−3.63 (s, 2H, ArCH2N), 3.63−3.62 (s, 3H, OCH3), 3.56 (s, 4H,
NCH2Ar), 1.39 (d, J = 1.8 Hz, 9H, C(CH3)3), 1.34 (t, J = 3.4 Hz, 9H,
C(CH3)3). 13C NMR (126 MHz, CDCl3) δ 156.3 (s, 1C, ArCO),
145.4 (s, 1C, ArC), 141.4 (s, 1C, ArC), 140.0 (s, 1C, ArC), 132.1 (s,
1C, ArC), 128.9 (s, 4C, ArCH), 128.3 (s, 4C, ArCH), 126.9 (s, 2C,
ArCH), 125.3 (s, 1C, ArCH), 122.6 (s, 1C, ArCH), 62.0 (s, 1C,
ArCH2N), 58.4 (s, 2C, NCH2Ar), 52.5 (s, 1C, OCH3), 35.4 (s, 1C,
C(CH3)3), 34.7 (s, 1C, C(CH3)3), 31.8 (s, 3C, C(CH3)3), 31.3 (s,
3C, C(CH3)3). HRMS(ESI): calcd for C30H39NO: 429.301 [M +
H]+, found 429.30. Anal. calcd (found) for C30H39NO: C, 83.87
(83.75); H, 9.15 (8.93); N, 3.26 (3.06)%.
N-(3,5-Di-tert-butyl-2-methoxybenzyl)-1-(pyridin-2-yl)-N-(pyri-
din-2-ylmethyl)methanamine [LPicO‑Me]. Synthesis of [LPicO‑Me] was
performed by using appropriate substrates as follows: compound
[LPic-H] (1.00 g, 2.40 mmol), NaH (0.072 g, 3.00 mmol, 1.25 equiv),
and MeI (0.22 mL, 3.60 mmol, 1.5 equiv). Product was obtained as
white powder, yield: (0.72 g, 1.67 mmol, 69%). 1H NMR (500 MHz,
CDCl3) δ 8.56−8.45 (m, 2H, ArCH), 7.68−7.57 (m, 5H, ArCH),
7.20 (d, J = 2.5 Hz, 1H, ArCH), 7.15−7.11 (m, 2H, ArCH), 3.82 (s,
4H, NCH2Ar), 3.79−3.75 (m, 2H, ArCH2N), 3.64 (s, 3H, OCH3),
1.37 (d, J = 4.4 Hz, 9H, C(CH3)3), 1.29 (d, J = 3.7 Hz, 9H,
C(CH3)3). 13C NMR (126 MHz, CDCl3) δ 160.2 (s, 1C, ArCO),
156.3 (s, 1C, ArC), 149.1 (s, 2C, ArCH), 145.5 (s, 1C, ArC), 141.7
(s, 2C, ArC), 136.5 (s, 4C, ArCH), 125.1 (s, 1C, ArCH), 122.9 (s,
1C, ArC), 122.9 (s, 1C, ArCH), 122.0 (s, 2C, ArCH), 62.0 (s, 1C,
OCH3), 60.5 (s, 2C, NCH2Ar), 53.3 (s, 1C, ArCH2N), 35.4 (s, 1C,
C(CH3)3), 34.7 (s, 1C, C(CH3)3), 31.8 (s, 3C, C(CH3)3), 31.3 (s,
3C, C(CH3)3). HRMS(ESI): calcd for C28H37N3O: 431.29 [M + H]+,
found 431.29. Anal. calcd (found) for C28H37N3O: C, 77.92 (77.71);
H, 8.64 (8.59); N, 9.74 (9.62)%.
+ −
Anal. calcd (found) for C22H38NO3 I : C, 53.77 (53.34); H, 7.79
(8.32); N, 2.85 (2.67)%.
1,4-Bis((cyclohexyl(methyl)amino)methyl)naphthalene-2,3-diol
[LNCy-H2]. To a solution of 2,3-dihydroxynaphthalene (0.613 g, 3.8
mmol) in methanol (20 mL), N-methylcyclohexylamine (1.0 mL, 7.7
mmol) was added. While the mixture was stirred on an ice bath, an
aqueos solution of formaldehyde (0.65 mL, 8.6 mmol) was slowly
added. After 15 min a crude product precipitated as a white solid. It
was collected by filtration, washed with cold methanol, recrystallized
from toluene, and dried in vacuo to give the main product (1.44 g, 3.5
1
mmol) as a white crystalline powder in 92% yield. H NMR (500
MHz, CDCl3) δ 11.69 (br s, 1H), 7.73 (dd, J = 6.4, 3.3 Hz, 2H,
ArCH), 7.25 (dd, J = 6.4, 3.2 Hz, 2H, ArCH), 4.26 (s, 4H, ArCH2N),
2.67 (tt, J = 11.4, 3.2 Hz, 2H, NCH), 2.37 (s, J = 7.0 Hz, 6H, NCH3),
1.99 (d, J = 11.2 Hz, 4H, CH2), 1.84 (d, J = 13.1 Hz, 4H, CH2), 1.66
(d, J = 12.7 Hz, 2H, CH2), 1.41 (qd, J = 12.2, 2.9 Hz, 4H, CH2), 1.27
(ddt, J = 25.5, 12.6, 3.3 Hz, 4H, CH2), 1.15 (tt, J = 12.6, 3.3 Hz, 2H,
CH2). 13C NMR (126 MHz, CDCl3) δ 149.1 (s, 2C, ArOH), 127.0
(s, 2C, ArC), 122.5 (s, 2C, ArCH), 121.4 (s, 2C, ArCH), 110.8 (s,
2C, ArC), 62.5 (s, 2C, NCH), 53.3 (s, 2C, ArCH2N), 37.0 (s, 2C,
CH3), 28.3 (s, 4C, CH2), 26.2 (s, 2C, CH2), 25.8 (s, 4C, CH2).
HRMS(ESI): calc for C26H38N2O2: 411.30 [M + H]+, found: 411.30.
Anal. calcd (found) for C26H38N2O2: C, 76.06 (75.69); H, 9.33
(10.46); N, 6.82 (6.68)%.
[LCy-Na]. In the glovebox, to the stirred solution of LCy-H (1.50 g,
4.50 mmol) in THF the NaH (0.11 g, 4.50 mmol, 1.00 equiv) was
added. The solution turned cloudy, and gas evolution was observed.
The mixture was stirred, until the solution was clear. Next the solution
was placed at −15 °C, until colorless crystalline product appeared,
which was filtered off and dried under vacuum to obtain LCy-Na (1.81
g, 94%). 1H NMR (500 MHz, C6D6) δ 7.51 (s, 2H, ArCH), 7.13 (d, J
= 1.9 Hz, 2H, ArCH), 3.70 (bs, 4H, ArCH2N), 3.49−3.36 (m, 8H,
CH2THF), 2.73 (s, 2H, NCH), 2.09 (s, 6H, NCH3), 1.70 (s, 18H,
C(CH3)3), 1.49 (s, 18H, C(CH3)3), 1.62−1.01 (m, 20H, CH2),
1.37−1.28 (m, 8H, CH2THF). 13C NMR (126 MHz, C6D6) δ 166.8 (s,
2C, ArCO), 155.8 (s, 2C, ArC), 140.4 (s, 2C, ArC), 136.2 (s, 2C,
ArC), 130.7 (s, 2C, ArCH), 124.3 (s, 2C, ArCH), 68.0 (s, 4H,
CH2THF), 62.0 (s, 2C, NCH3), 58.9 (s, 2C, ArCH2N), 58.5 (s, 2C,
CH), 35.7 (s, 2C, C(CH3)3), 34.0 (s, 2C, C(CH3)3), 32.6 (s, 6C,
C(CH3)3), 32.1 (s, 1C, CH2), 30.7 (s, 6C, C(CH3)3), 30.1 (s, 1C,
CH2), 26.7 (s, 4C, CH2), 26.4 (s, 4C, CH2), 25.7 (s, 4C, CH2THF).
Anal. calcd (found) for C52H86N2O4Na2: C, 73.54 (74.01); H, 10.21
(10.43); N, 3.26 (3.11)%.
N-((1,3-Dioxolan-2-yl)methyl)-1-(3,5-ditert-butyl-2-methoxy-
phenyl)-N-methylmethanamine [LOxO‑Me]. Synthesis of [LOx
]
O‑Me
was performed by using appropriate substrates as follows: compound
[LOx-H] (1.00 g, 2.98 mmol), NaH (0.089 g, 3.72 mmol, 1.25 equiv),
and MeI (0.28 mL, 4.47 mmol, 1.5 equiv). Product was obtained as
white powder, yield: (0.41 g, 1.17 mmol, 39%). 1H NMR (500 MHz,
C6D6) δ 7.70 (d, J = 2.6 Hz, 1H, ArCH), 7.36 (d, J = 2.6 Hz, 1H,
ArCH), 5.03 (t, J = 4.3 Hz, 1H, CH), 3.66 (s, 2H, ArCH2N), 3.45 (s,
3H, OCH3), 3.42−3.35 (m, 2H, CH2), 3.29−3.19 (m, 2H, CH2), 2.71
(d, J = 4.3 Hz, 2H, NCH2), 2.29 (s, 3H, NCH3), 1.41 (s, 9H,
C(CH3)3), 1.27 (s, 9H, C(CH3)3). 13C NMR (126 MHz, C6D6) δ
156.6 (s, 1C, ArCO), 145.3 (s, 1C, ArC), 141.4 (s, 1C, ArC), 131.9
(s, 1C, ArCH), 126.1 (s, 1C, ArCH), 122.5 (s, 1C, ArC), 104.2 (s,
1C, CH), 64.4 (s, 2C, CH2), 61.5 (s, 1C, ArCH2N), 60.4 (s, 1C,
OCH3), 57.5 (s, 1C, NCH2), 43.3 (s, 1C, NCH3), 35.3 (s, 1C,
C(CH3)3), 34.5 (s, 1C, C(CH3)3), 31.5 (s, 3C, C(CH3)3), 31.2 (s,
3C, C(CH3)3). HRMS(ESI): calcd for C21H35NO3: 349.26 [M + H]+,
found 349.26. Anal. calcd (found) for C21H35NO3: C, 72.17 (71.87);
H, 10.09 (9.89); N, 4.01 (3.85)%.
[LC12-Na]. Compound LC12-Na was synthesized by using 1.50 g
(3.59 mmol) of LC12-H and NaH (0.086 g, 3.59 mmol, 1.00 equiv).
L
C12-Na was obtained as colorless crystalline product (1.62 g, 89%).
1H NMR (500 MHz, C6D6) δ 7.52 (s, 2H, ArCH), 7.13 (s, 2H,
ArCH), 4.26−2.94 (bs, 4H, ArCH2N), 2.74−2.26 (m, 8H, CH2THF),
2.26−1.75 (bs, 4H, NCH2), 1.71 (s, 6H, NCH3, 4H, CH2), 1,72 (s,
18H, C(CH3)3), 1.50 (s, 18H, C(CH3)3), 1.35−1.16 (m, 44H, CH2,
CH2THF), 0.93 (t, J = 6.8 Hz, 6H, CH3). 13C NMR (126 MHz, C6D6)
δ 166.9 (s, 2C, ArCO), 155.4 (s, 2C, ArC), 140.6 (s, 2C, ArC), 136.0
(s, 2C, ArC), 129.1 (s, 2C, ArCH), 123.2 (s, 2C, ArCH), 67.9 (s, 4H,
CH2THF), 63.7 (s, 2C, ArCH2N), 62.6 (s, 2C, NCH2), 57.0 (s, 2C,
NCH3), 40.8 (s, 2C, CH2), 35.4 (s, 2C, C(CH3)3), 34.4 (s, 2C,
C(CH3)3), 32.4 (s, 2C, CH2), 32.0 (s, 6C, C(CH3)3), 30.6 (s, 6C,
C(CH3)3), 29.9 (m, 10C, CH2), 28.0 (s, 2C, CH2), 27.5 (s, 2C,
CH2), 27.3 (s, 2C, CH2), 25.7 (s, 4C, CH2THF), 23.2 (s, 2C, CH2),
N-((1,3-Dioxolan-2-yl)methyl)-1-(3,5-di-tert-butyl-2-methoxy-
phenyl)-N,N-dimethylmethanaminium iodide [LOxO,N‑Me]. Com-
C
Inorg. Chem. XXXX, XXX, XXX−XXX