2-((Di-n-butylphosphoryl)methoxy)-N,N-di-n-octylacetamide (4b)
2-(((Di-n-butylphosphoryl)methyl)amino)-N,N-di-n-
octylacetamide (7b)
By the same procedure as described for 4a, starting from 2b
(0.60 g, 3.1 mmol), NaH (60% in oil) (0.15 g, 3.5 mmol), KI
(0.52 g, 3.1 mmol), and 3 (0.98 g, 3.1 mmol) afforded 4b
It was synthesized by the same procedure as described for 7a,
starting from 6b (1.20 g, 2.1 mmol) and 5% Pd/C (300 mg) in
1
1
(1.07 g, 73% yield) as an oil. H NMR d: 0.81–1.01 (12H, m,
ethanol (50 mL) in quantitative yield. H NMR d: 0.85–0.95
CH3), 1.18–1.26 (20H, m, (CH2)5CH3), 1.34–1.62 (12H, m,
CH2CH2CH3, NCH2CH2), 1.64–1.80 (4H, m, PCH2CH2),
3.05, 3.22 (2H, t, J = 6.4 Hz, CH2N), 3.83 (2H, d, J = 6.4 Hz,
PCH2O), 4.17 (2H, s, COCH2O). 13C NMR d: 14.0, 22.7, 24.7,
27.0, 29.3, 31.8, 49.6, 69.0, 166.5. HRMS: m/z 474.4099 [M + H]+.
C27H57NO3P calculated 474.4076.
(12H, m, CH3), 1.20–1.28 (20H, m, (CH2)5CH3), 1.26–1.65
(12 H, m, NCH2CH2, (PCH2(CH2)2), 1.65–1.78 (4H, m,
PCH2), 3.00 (2H, d, J = 7.9 Hz, PCH2N), 3.04, 3.21 (2H, t,
J = 6.6 Hz, CONCH2), 3.54 (2H, s, COCH2N). 13C NMR d:
14.0, 22.7, 24.0, 24.4, 27.0, 29.3, 31.3, 49.0, 52.6, 164.0.
HRMS: m/z 473.4229 [M + H]+. C27H58N2O2P calculated
473.4236.
Di-n-butyl((benzyl(2-(di-n-octylamino)-2-oxoethyl)amino)methyl)-
Di-n-butyl((bis(2-(di-n-octylamino)-2-oxoethyl)amino)methyl)-
phosphonate (6a).
phosphonate (9)
A mixture of 5a (1.00 g, 3.0 mmol), 3 (1.11 g, 3.3 mmol), KI
(0.47 g, 3 mmol) and K2CO3 (1.32 g, 9.5 mmol) in acetonitrile
(50 mL) was refluxed for 48 h. The solvent was evaporated and
the residue was dissolved in dichloromethane (200 mL).
The resulting solution was washed with water (3 ꢃ 50 ml).
The organic layer was dried with anhydrous MgSO4 and
concentrated under reduced pressure, followed by purification
by chromatography (SiO2, ethyl acetate) to give 6a (1.28 g,
A mixture of 8 (0.80 g, 1.5 mmol), paraformaldehyde (0.05 g,
1.6 mmol), 1a (0.31 g, 1.6 mmol), p-toluenesulfonic acid
(0.10 g), and molecular sieves in toluene (35 mL) was refluxed
for 48 h. Subsequently, K2CO3 (0.50 g) was added and the
mixture was refluxed for 10 min. After cooling to room
temperature, the mixture was washed with water (1 ꢃ 20 mL),
dried with anhydrous MgSO4, and concentrated under reduced
pressure. The residue was purified by chromatography (SiO2,
1
62% yield) as an oil. H NMR d: 0.82–0.95 (12H, m, CH3),
1
ethyl acetate) to afford 9 (0.65 g, 60%) as an oil. H NMR d:
1.20–1.30 (20H, m, (CH2)5CH3), 1.39 (4H, sextet, J = 7.0 Hz,
CH2CH3), 1.42–1.46 (4H, m, NCH2CH2), 1.63 (4H, pentet,
J = 7.0 Hz, OCH2CH2), 3.05, 3.25 (2H, t, J = 6.5 Hz,
CONCH2), 3.21 (2H, d, J = 9.9 Hz, PCH2N), 3.53 (2H, s,
NCH2Ar), 3.92–4.07 (4H, m, POCH2), 3.81 (2H, s, C(O)CH2N),
0.82–0.94 (18H, m, CH3), 1.23–1.30 (40H, s, (CH2)5CH3), 1.38
(4H, sextet, J = 7.0 Hz, CH3CH2), 1.43–1.47 (8H, m,
NCH2CH2), 1.62 (4H, pentet, J = 7.0 Hz, OCH2CH2), 3.17,
3.23 (4H, t, J = 6.6 Hz, CONCH2), 3.31 (2H, d, J = 9.3 Hz,
PCH2N), 3.74 (4H, s, NCH2CO), 4.07 (4H, q, J = 7.0 Hz,
CH2OP), 13C NMR d: 14.0, 18.5, 22.7, 27.0, 29.3, 31.8, 49.3, 60.0,
7.21–7.39 (5H, m, ArH). MS: m/z 595.7 [M
+
H]+.
C34H64N2O4P calculated 595.5.
60.5, 66.9, 167.5. HRMS: m/z 786.6879 [M
+
H]+.
C45H93N3O5P calculated 786.6853.
2-(Benzyl((di-n-butylphosphoryl)methyl)amino)-
N,N-di-n-octylacetamide (6b)
Tetra-n-butyl((benzylazanediyl)bis(methylene))-
bis(phosphonate) (11)
Using the same procedure as described for 6a, starting from 5b
(0.89 g, 3.0 mmol), 3 (1.11 g, 3.3 mmol), KI (0.47 g, 3 mmol),
and K2CO3 (1.32 g, 9.5 mmol) gave 6b as an oil (1.42 g, 73%
yield). 1H NMR d: 0.82–0.95 (12H, m, CH3), 1.15–1.23 (20H, m,
(CH2)5CH3), 1.30–1.60 (12 H, m, NCH2CH2, PCH2(CH2)2),
1.60–1.74 (4H, m, PCH2), 3.05, 3.25 (2H, t, J = 6.5 Hz,
CONCH2), 3.06 (2H, d, J = 4.7 Hz, PCH2N), 3.60 (2H, s,
NCH2Ar), 3.94 (2H, s, C(O)CH2N), 7.25–7.51 (5H, m, ArH).
MS: m/z 563.4 [M + H]+. C34H64N2O2P calculated 563.5.
A mixture of benzylamine (10) (0.43 g, 4.0 mmol), para-
formaldehyde (0.24 g, 8.0 mmol), 1a (1.79 g, 8.0 mmol),
p-toluenesulfonic acid (0.11 g), and molecular sieves in toluene
(35 mL) was refluxed for 24 h. Subsequently, K2CO3 (0.50 g)
was added and the mixture was refluxed for 10 min. The
mixture was washed with water (1 ꢃ 20 mL), dried with anhydrous
MgSO4, and concentrated under reduced pressure. The residue was
purified by chromatography (SiO2, ethyl acetate) to give 11 (1.49 g,
72%) as an oil. 1H NMR d: 0.85–0.96 (12H, m, CH3),
1.37 (8H, sextet, J = 7.0 Hz, CH2CH3), 1.62 (8H, pentet,
J = 7.0 Hz, OCH2CH2), 3.16 (4H, d, J = 9.2 Hz, PCH2N),
3.94–4.09 (8H, m, POCH2), 4.02 (2H, s, ArCH2N), 7.22–7.40
(5H, m, ArH). MS: m/z 520.3 [M + H]+. C25H48NO6P2
calculated 520.3.
Di-n-butyl(((2-(di-n-octylamino)-2-oxoethyl)amino)methyl)-
phosphonate (7a)
A suspension of 6a (1.00 g, 1.7 mmol) and 5% Pd/C (300 mg)
in ethanol (50 mL) was stirred under a hydrogen atmosphere
overnight. The catalyst was filtered off and the ethanol was
removed under reduced pressure to give 7a as an oil in quanti-
tative yield. 1H NMR d: 0.90–0.95 (12H, m, CH3), 1.24–1.30
(20H, m, (CH2)5CH3), 1.39 (4H, sextet, J = 7.0 Hz, CH3CH2),
1.50–1.54 (4H, m, NCH2CH2), 1.66 (4H, pentet, J = 7.0 Hz,
POCH2CH2), 3.15, 3.30 (2H, t, J = 6.5 Hz, CONCH2), 3.03
(2H, d, J = 11.9 Hz, PCH2N), 3.52 (2H, s, COCH2N),
4.06–4.15 (4H, m, POCH2). 13C NMR d: 14.0, 18.5, 22.7,
24.0, 24.4, 27.0, 29.3, 31.8, 50.0, 66.9, 164.0. HRMS: m/z
505.4119 [M + H]+. C27H57N2O4P calculated 505.4134.
Tetra-n-butyl(azanediylbis(methylene))bis(phosphonate) (12)
A suspension of 11 (1.30 g, 2.5 mmol) and 10% Pd/C (300 mg)
in ethanol (50 mL) was stirred under a hydrogen atmosphere
(10 bar) at room temperature for 72 h. The catalyst was filtered
off and the solvent was removed under reduced pressure, to give
12 as an oil in quantitative yield. 1H NMR d: 0.82–0.97 (12H, m,
CH3), 1.37 (8H, sextet, J = 7.0 Hz, CH2CH3), 1.63 (8H, pentet,
J = 7.0 Hz, OCH2CH2), 3.11 (4H, d, J = 10.6 Hz, PCH2N),
c
2056 New J. Chem., 2012, 36, 2048–2059
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012