4
4
G. Olive and A. Jacques
Tetraethyl( N-methyl-1-amino-1-phenylmethane-1,1-diyl)bisphos-
1
phonate 7 (colorless liquid, 6.00 g, 15%). H-NMR (300 MHz, CDCl3)
�
1.20 (6H, t, J = 6.9, 2 CH3CH2O), 1.29 (6H, t, J = 7.1, 2 CH3CH2O),
2
.48 (3H, s, CH3N), 4.11 (8H, m, 4 CH3CH2O), 7.35 (3H, m, Aromatics
13
ortho and para), 7.82 (2H, m, Aromatics meta). C-NMR (75 MHz,
CDCl3) � 15.8 (t, J = 3.2, 2 CH3CH2O), 15.9 (t, J = 3.2, 2 CH3CH2O),
3
2
0.6 (t, J = 9.1, CH3N), 62.9 (t, J = 3.8, 2 CH3CH2O), 63.0 (t, J = 3.2,
CH3CH2O), 67.4 (t, J = 136.8 CP2), 126.8 (t not resolved, Aromatics
para), 127.0 (t not resolved, Aromatics meta), 128.4 (t, J = 5.4, Aromat-
31
ics ortho), 131.8 (t, J = 3.8, quaternary aromatic). P-NMR (121 MHz,
CDCl3) � 20.5 Anal. Calcd for C16H29NO6P2: C, 48.86; H, 7.43; N, 3.56.
Found: C, 49.32; H, 7.03; N, 3.76. Rf (EtOH/CH2Cl2 0.5/9.5) = 0.60.
Tetraethyl(N-benzyl-1-aminoethan-1,1-diyl)bisphosphonate 12 (or-
1
ange liquid, 33.48 g, 88%). H-NMR (300 MHz, CDCl3) � 1.38 (12H,
m, 4 CH3CH2O), 1.67 (3H, t, JPH = 16.8 CH3CP2), 4.06 (2H, s, CH2N),
13
4
.38 (8H, m, 4 CH3CH2O), 7.36 (5H, m, Aromatics). C-NMR (75 MHz,
CDCl3) � 16.1 (t, J = 3.2, 4 CH3CH2O) and CH3CP2), 47.4 (t, J = 5.9,
CH2N), 57.4 (t, J = 142.7, CP2), 62.4 (t, J = 3.8, 2 CH3CH2O), 62.9 (t,
J = 3.2, 2 CH3CH2O), 126.3 (Aromatic para), 127.6 and 127.7 (Aromat-
ics ortho and meta), 139.8 (quaternary aromatic). 31P-NMR (121 MHz,
CDCl3) � 23.3 Anal. Calcd for C17H31NO6P2: C, 50.12; H, 7.67; N, 3.44.
Found: C, 49.88; H, 7.41; N, 3.04.
0
0
P,P-Diethyl-P ,P -diisopropyl(pyrrolidine-2,2-diyl)bisphosphonate
6 (colorless liquid, 9.85 g, 25%). 16 was purified by preparative
1
HPLC on a Kromasil column (10 �m, 8 int = 50 mm, L = 25 cm) with
�
1
CH3CN/H2O 60/40 as eluent. Rate: 50 ml�mn . 70 mg by injection. UV
detector at 204 nm. TR (Kromasil column 10 �m, CH3CN/H2O 60/40,
�
1
rate: 0.5 ml�mn , UV detector at 204 nm) = 7.57 mn.
1
H-NMR (300 MHz, CDCl3) � 1.35 (6H, t, J = 7.8, 2 CH3CH2O), 1.37
(
2
12H, d, J = 6.6, 2 (CH3)2CHO), 1.88 (2H, t, J = 6.7, CH2CH2CH2),
.30 (2H, m, CH2CP2), 3.07 (2H, t, J = 6.5, CH2N), 4.21 (4H, m, 2
13
CH3CH2O), 4.82 (2H, m, 2 (CH3)2CHO). C-NMR (75 MHz, CDCl3)
16.2 (t, J = 4.9, 2 CH3CH2O), 23.5 (t, J = 5.4, 2 (CH3)2CHO), 24.0
�
(
d, J = 3.2, (CH3)2CHO), 24.1 (d, J = 3.2, (CH3)2CHO), 25.8 (t, J = 3.2,
CH2CH2CH2), 30.2 (t, J = 2.7, CH2P2), 47.1 (t, J = 4.3, CH2N), 61.5 (t,
J = 152.9, CP2), 62.4 (d, J = 7.5, CH3CH2O), 62.9 (d, J = 7.5, CH3CH2O),
31
7
(
1.0 (d, J = 7.5, (CH3)2CHO), 71.6 (d, J = 7.5, (CH3)2CHO). P-NMR
162 MHz, CDCl3) � 22.7 (d, JPP = 59, P(OiPr)2, 24.9 (d, JPP = 58,
15
P(OEt)2. N-NMR (C6D6) � � 340.4 (t, JN--P = 9.3). Anal. Calcd for
C14H31NO6P2: C, 45.28; H, 8.41; N, 3.77. Found: C, 45; 21; H, 8.55;
N, 4.02.