2
258 Lee et al.
Asian J. Chem.
MHz) and Varian Gemini (200 or 300 MHz) spectrometers.
Mass spectra were measured with HP 5890 GC/MASS (70
eV, EI). The organic solvents and chemicals were obtained
from commercial products and purified by the appropriate
methods before use. Except where noted, all starting materials
were purchased fromAldrich, Fluka, Fisher, Lancaster or TCI
Chemical Companies and used as received. Known compounds
prepared by modified procedures have been included in the
supplemental information.
(0.55 mL, 0.01 mol), paraformaldehyde (1.80 g, 0.02 mol)
and 6 M HCl (20 mL) was stirred for 0.5 h. Then the clear
solution was left standing for 3 days. In order to precipitate
solid, the clear solution in refrigerator was kept for 24 h. After
filtering precipitated solid, it was washed by hexane and
chloroform. A white solid product (0.32 g, yield 6.8 %) was
-1
then collected; m.p. 304-306 °C; IR (KBr, νmax, cm ): 3448
1
(OH), 2956, 1731 (C=O), 1655; H NMR (D
2
O, pH 10, 200
MHz) δ: 4.27 (s, 2H), 3.50 (d, J = 9.3 Hz, 8H), 2.42 (t, J = 6.9
13
Synthesis of 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-
diazadiphosphocine-1,5-diacetic acid (1a): A mixture of
glycine (0.75 g, 0.01 mol), hypophosphorous acid (0.55 mL,
Hz, 4H), 2.08 (m, 4H); C NMR (D O, pH 10, 50 MHz) δ:
2
173.0, 172.6, 170.4, 169.7, 52.3, 51.5, 48.9, 25.8.
Physical data of all the synthesized compounds 1a-c are
given in Table-1.
0
(
.01 mol), paraformaldehyde (1.80 g, 0.02 mol) and 6 M HCl
10 mL) was stirred for 0.5 h and then the clear solution was
left standing for 3 days. A white solid product (0.26 g, yield
%), was then collected by filteration, washed with a small
RESULTS AND DISCUSSION
8
amount of cold water, ethanol and dried in vacuo. Unreacted
starting materials remained in solution.: m.p. 273-275 °C; IR
As a part of research program related to the synthetic study
of pharmacologically interesting compounds and good chelating
agents for transition metal ions, we here report the synthesis
of an unusual medium signed ring heterocyclic ligand with
mixed aminophosphonic donating group. In order to synthesize
3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphos-
phocine-1,5-diacetic acid (1a), 2-[5-(1,2-dicarboxyethyl-3,7-
dihydroxy-3,7-dioxo-3[1,5,3,7]diazadiphosphocan-1-yl)-
succinic acid (1b) and 3,7-dihydroxy-3,7-dioxoperhydro-
1,5,3,7-diazadiphosphocine-1,5-di-(2-glutaric acid) (1c), we
executed the reaction of various amino acids (glycine, aspartic
-
1
1
(
KBr, νmax, cm ): 3445 (OH), 2999, 1718 (C=O), 1652; H
NMR (D O, pH 10, 200 MHz) δ: 3.87 (s, 4H), 3.50 (d, J = 9.3
2
13
Hz, 8H); C NMR (D
5.6; MS (MOLDI-TOF), m/z 331 (Anal. Calcd. for C, 26.24;
H, 5.50; N, 7.65; P, 16.92 found; C, 26.50; H, 5.53; N, 7.36; P,
2
O, pH 10, 50 MHz) δ: 178.5, 59.2,
5
1
6.71).
Synthesis of 2-[5-(1,2-dicarboxyethyl-3,7-dihydroxy-
,7-dioxo-3[1,5,3,7]diazadiphosphocan-1-yl)-succinic acid
3
(
1b):A mixture of L-aspartic acid (1.33 g, 0.01 mol), hypophos-
phorous acid (0.55 mL, 0.01 mol), paraformaldehyde (1.80 g,
.02 mol) and 6 M HCl (10 mL) was stirred for 0.5 h. And then
the clear solution was left standing for 3 days. Then mixture
was added ether, another separated with H O, dried in vacuo. A
white solid product (0.17 g, yield 7.8 %) was then collected;
acid, glutamic acid) with paraformaldehyde and H
The strongly acidic medium is required to promote the
second reaction of H PO and to avoid the side reactions of
3
PO
2
(Table-1).
0
3
2
the iminium ion such as the reduction by means of formalde-
hyde to N-methyl derivatives. The reaction was found to be
highly dependent on the experimental conditions employed.
High concentrations of the reactant, heat and very long reaction
times led to extensive formation of polymeric products; conver-
sely, low acidity (pH > 1) and low reactant concentrations gave
rise to complex mixtures.A clean reaction was effected dissol-
2
-1
m.p. 238-240 °C; IR (KBr, νmax, cm ): 3445 (OH), 2999, 1718
1
(
6
C=O), 1652; H NMR (D
2
O, pH 10, 200 MHz) δ: 4.24 (t, J =
13
.9 Hz, 2H), 3.48 (d, J = 9.2 Hz, 8H), 3.34 (m, 4H); C NMR
(D
2
O, pH 10, 50 MHz) δ: 174.1, 173.4, 52.1, 50.8, 48.5.
Synthesis of 3,7-dihydroxy-3,7-dioxoperhydro-1,3,5,7-
diazadiphosphocine-1,5-di-(2-glutaric acid) (1c):A mixture
of L-glutamic acid (1.47 g, 0.01 mol), hypophosphorous acid
ving glycine and H
3
PO
2
in 6 M HCl to obtain a 1 M solution
in both reagents and adding paraformaldehyde in slight excess
TABLE-1
PHYSICAL DATA OF PRODUCTS 1a-c
a
Entry
1
Product
OH
Compound
m.p. (°C)
273-274
Yield (%)
O
P
HOOCH C N
N CH COOH
1a
1b
1c
8.0
7.8
6.8
2
2
P
P
HO
O
O
OH
COOH
N CHCH COOH
2
3
HOOCH CHC N
150-152
304-305
2
2
HOOC
P
P
P
HO
O
O
OH
COOH
HOOC(H C) HC
N
N
O
CH(CH ) COOH
2
2
2 2
HOOC
HO