5
72
J. Dziemidowicz et al.
PAPER
1
3
C NMR (D O): d = 10.2 (CH CH CH ), 23.3 (CH CH CH ), 30.3
2
2
2
3
2
2
3
(
ArCH Ar), 51.8 (d, J = 4.6 Hz, POCH ), 77.1 (CH CH CH ),
2 C-P 3 2 2 3
1
26.3 (d, JC-P = 178.8 Hz, Ar), 132.1 (d, JC-P = 10.5 Hz, Ar), 134.6
S
(d, JC-P = 14.7 Hz, Ar), 158.2 (s, Ar).
31
CH3
Me
P
O
K
P NMR (D O): d = 18.12.
O
Si CH3
CH3
2
R
S
Me
2
–
LR–ESI–MS: m/z (%) = 521.2 (100) [M – 2 × K] .
CH3
Si
5
,11,17,23-Tetrakis(O-methylphosphono)-25,26,27,28-tetra-
S
P
CH3
kis(2-methoxyethoxy)calix[4]arene Tetrapotassium Salt (2b)
Yield: 84%; white solid; mp >300 °C.
O
R
CH3
OMe
IR (KBr): 3200–3700, 1600–1700, 1467, 1194, 1082, 1036, 789
cm .
S-Me
–1
1
H NMR (D O): d = 2.88 (d, J = 10.74 Hz, 12 H, POCH ), 3.29 (d,
2
3
J = 12.72 Hz, 4 H, ArCH Ar), 3.30 (s, 12 H, CH CH OCH ), 3.85
2
2
2
3
(
t, J = 4.88 Hz, 8 H, CH CH OCH ), 4.11 (t, J = 4.88 Hz, 8 H,
2 2 3
CH CH OCH ), 4.37 (d, J = 12.72 Hz, 4 H, ArCH Ar), 7.10 (d, J =
2
2
3
2
1
13
2.70 Hz, 8 H, Ar).
H3C
S
P
CH3
C NMR (D O): d = 30.3 (ArCH Ar), 51.9 (d, J = 4.6 Hz,
2
2
C-P
Si
O
O
S-Me
POCH3), 58.1 (CH CH OCH ), 72.1 (CH CH OCH ), 73.0
R
CH3
2 2 3 2 2 3
(
CH CH OCH ), 126.3 (d, J = 179.2 Hz, Ar), 131.9 (d, JC-P = 10.5
2 2 3 C-P
Me
Hz, Ar), 134.8 (d, JC-P = 14.7 Hz, Ar), 158.2 (s, Ar).
3
1
P NMR (D O): d = 18.10.
2
–
LR–ESI–MS: m/z (%) = 1145.2 (7) [M – K] , 553.2 (100) [M – 2 ×
2
–
3–
4–
K] , 355.8 (82) [M –3 × K] , 257.1 (50) [M – 4 × K] .
S
P
CH3
O
K
Me-S Si CH3
R
5,17-Bis(O-methylphosphono)-25,26,27,28-tetrapropoxy-
calix[4]arene Dipotassium Salt (2c)
O-Me
CH3
Yield: 98%; white solid; mp >300 °C.
Scheme 2
IR (KBr): 3200–3700, 1600–1700, 1461, 1196, 1082, 1044, 775
–
1
cm .
1
makes this method an attractive alternative to reported
aqueous basic hydrolysis procedures.
H NMR (CD OD): d = 0.93 (t, J = 7.33 Hz, 6 H, CH CH CH ),
3
2
2
3
1
.16 (t, J = 7.82 Hz, 6 H, CH CH CH ), 1.88–1.94 (m, 4 H,
2 2 3
CH CH CH ), 1.99–2.05 (m, 4 H, CH CH CH ), 3.21 (d, J = 13.42
2
2
3
2
2
3
Hz, 4 H, ArCH Ar), 3.53 (d, J = 11.23 Hz, 6 H, OCH ), 3.68 (t, J =
2
3
Diethyl benzylphosphonate (1e), triethyl phosphonoacetate (1k),
and diethyl (cyanomethyl)phosphonate (1m) are commercially
available. Compounds 1a–d, 1f, 1i, 1j, 1n, 1o, 1p, 1r
6.86 Hz, 4 H, CH CH CH ), 4.12 (t, J = 8.30 Hz, 4 H, CH CH CH ),
2 2 3 2 2 3
4.50 (d, J = 13.42 Hz, 4 H, ArCH Ar), 6.10–6.18 (m, 6 H, Ar), 7.58
2
1
0
11
12
13
14
15
16
17
(d, J = 12.21 Hz, 4 H, Ar).
were synthesized by the following described procedures. All sol-
vents were dried and distilled by standard procedure. Melting points
are uncorrected. NMR spectra were recorded on a Varian Gemini
1
3
C NMR (CD OD): d = 9.1, 10.3 (CH CH CH ), 23.1, 23.6
2 2 3 2 C-P
3
2
2
3
(
7
CH CH CH ), 30.7 (ArCH Ar), 50.8 (d, J = 5.0 Hz, POCH3),
6.6, 77.0 (CH CH CH ), 121.9 (s, Ar), 127.5 (d, J = 179.6 Hz,
2 2 3 C-P
5
00 MHz spectrometer. IR spectra were measured on a Bruker
Ar), 127.6 (s, Ar), 132.5 (d, JC-P = 9.6 Hz), 132.8, (s, Ar) 136.6 (d,
JC-P = 14.7 Hz), 155.2 (s, Ar), 160.0 (s, Ar).
31P NMR (CD
IFS66 spectrometer. ESI–MS spectra were recorded on a MARI-
NER PerSeptve Biosystem. The products were characterized by
comparison of their physical data with those of known samples or
by their spectral data.
OD): d = 17.70.
3
+
HR–ESI–MS: m/z [M + K] calcd for C H K O P : 895.1947;
4
2
52
3
10 2
found: 895.1923.
5
,11,17,23-Tetrakis(O-methylphosphono)-25,26,27,28-tetra-
propoxycalix[4]arene Tetrapotassium Salt (2a); General Proce-
dure
A mixture of 1a (4 mmol) and potassium trimethylsilanolate (1.1
equiv for each phosphonate group, Table 1) in anhyd solvent (25
mL, Table 1) was stirred at r.t. for 16h. Then solvent was evaporated
5
,17-Bis(O-methylphosphono)-25,26,27,28-tetrakis(2-methoxy-
ethoxy)calix[4]arene Dipotassium Salt (2d)
Yield: 98%; white solid; mp >300 °C.
IR (KBr): 3200–3700, 1600–1700, 1467, 1198, 1082, 1048, 782
cm .
–
1
and the residue was suspended in anhyd Et O (25 mL). After filtra-
2
1
tion, the solid product was washed with anhyd Et O (10mL), filtered
H NMR (D O): d = 3.21 (d, J = 13.19 Hz, 4 H, ArCH Ar), 3.23 (s,
2
2
2
and dried under vacuum. The corresponding potassium salt 2a was
obtained in 88% yield; mp >300 °C.
6 H, CH CH OCH ), 3.31 (d, J = 10.74 Hz, 6 H, POCH ), 3.32 (s,
2
2
3
3
6 H, CH CH OCH ), 3.68–3.72 (m, 4 H, CH CH OCH ), 3.82–3.86
2 2 3 2 2 3
(
m, 4 H, CH CH OCH ), 3.88 (t, J = 5.37 Hz, 4 H, CH CH OCH ),
IR (KBr): 3000–3700, 1600–1700, 1464, 1191, 1080, 1040, 777
cm .
2 2 3 2 2 3
–
1
4.26 (t, J = 5.37 Hz, 4 H, CH CH OCH ), 4.33 (d, J = 13.19 Hz, 4
H, ArCH Ar), 6.20–6.30 (m, 6 H, Ar), 7.37 (d, J = 12.70 Hz, 4 H,
Ar).
1
2 2 3
2
1
H NMR (D O): d = 0.86 (t, J = 7.14 Hz, 12 H, CH CH CH ), 1.85–
2
2
2
3
1
3
.93 (m, 8 H, CH CH CH ), 2.87 (d, J = 10.71 Hz, 12 H, OCH ),
2
2
3
3
3
C NMR (D O): d = 30.4 (ArCH Ar), 51.8 (d, J = 4.6 Hz,
.23 (d, J = 12.77 Hz, 4 H, ArCH Ar), 3.82 (t, J = 7.69 Hz, 8 H,
2
2
C-P
2
POCH ), 58.0, 58.1 (CH CH OCH ), 71.8, 72.3 (CH CH OCH ),
7
CH CH CH ), 4.40 (d, J = 12.77 Hz, 4 H, ArCH Ar), 7.08 (d, J =
3
2
2
3
2
2
3
2
2
3
2
2.5, 73.5 (CH CH OCH ), 123.1 (s, Ar), 125.8 (d, J = 179.2 Hz,
1
2.36 Hz, 8 H, Ar).
2 2 3 C-P
Synthesis 2005, No. 4, 569–574 © Thieme Stuttgart · New York