944
J Chem Crystallogr (2008) 38:943–947
(S)-2-(4-Methoxyphenoxy) Propane-1,2-Diol (1)
Experimental Section
Apparatus and Chemicals
This compound prepared as the method described [9] from
(S)-glycidol (3.7 g, 0.05 mol), 4-methoxyphenol (6.2 g,
0.05 mol) and piperidine hydrochloride (0.3 g, 2.5 mmol)
as a catalyst to give 8.51 g (86%), m.p. 80–82 ꢁC,
Melting points were determined with GALLENKAMP
Model apparatus with open capillaries. Infrared spectra
_
were recorded on a MIDAC-FTIR Model 1700 spectro-
[a]D20: + 7.5ꢁ (c = 7,CHCl3). H NMR d: 3.65–3.77(m,
1
7H), 3.93–3.94(m, 2H), 4.01(m, 1H), 6.76–6.83(m, 4H).
13C NMR d: 63.15, 64.16, 69.49, 71.50, 114.98, 121.62,
129.62, 158.54. Anal. Calcd. for C10H14O4: C, 60.60; H,
7.07, found: C, 60.45; H, 7.10%.
photometer. The Elemental analyses were obtained with
CARLO-ERBA Model 1108 apparatus. 1H NMR
(400 MHz) and 13C NMR (100 MHz) spectra were
recorded on BRUKER DPX-400 high performance digital
FT-NMR spectrometer, with tetramethysilane as the
internal standard solutions in deuteriochloroform. Optical
rotations were recorded using PERKIN ELMER Model
341 polarimeter. All chemicals were reagent grade unless
otherwise specified. THF dried over NaH and distilled
prior to use.
(S)-2-[(4-Methoxyphenoxy) Methyl]-15-Crown-5 (2)
This compound prepared as the method described [10]. To
a suspension of 0.984 g (32.8 mmol, 80% in mineral oil) of
NaH in 200 mL of the dry THF at 0 ꢁC was added a
solution of 1.30 g (6.56 mmol) of (S)-3-(4-methoxyphen-
oxy)-1,2-propanediol, in 250 mL of THF. The reaction
mixture was refluxed for 2 h. After cooling to 0 ꢁC a
solution of 3.29 g (6.56 mmol) of tetra (ethylene glycol)
di(4-toluenesulfonate) in 250 mL of THF was added
slowly. The suspension was refluxed for 48 h. The solvent
was evaporated and 100 mL of water was added to the
residue. The mixture was extracted with CH2Cl2
(4 9 20 mL) and the combined organic layers were
washed with 50 mL of water, dried on MgSO4 and solvent
was evaporated. The crude product was purified column
chromatography (eluent: EtOAc/hexane/triethylamine: 5/5/
1) to yield as a viscous oil 0.91 g. (39 %) of pure product.
Synthesis
Scheme 1: Reagent and conditions, i: Piperidine hydro-
chloride, 70–80 ꢁC, 4 h; ii: NaH, THF.
O
O
i
OH + MeO
OH
(1)
OMe
OH
HO
+
O
O
O
1
aD30: -14.5ꢁ (c = 7, CHCl3). H NMR (CDCl3) d: 3.64–
OH
HO
4.03 (m, 24 H); 6.81–6.88 (M, 4H). IR (m, cm-1): 3,043,
2,940, 2,874, 1,602, 1,509, 1,463, 1,233, 1,133, 1,041, 941,
829, 743. Anal. Calcd. for C18H28O7: C, 60.66; H, 7.92;
found: C, 60.45; H, 8.05%.
ii
O
O
O
O
O
O
NaClO4 Complexes of (2)
(2)
OMe
A solution of 156 mg (0.5 mmol) of host (2) in 5 mL of
ethyl acetate was added to 70 mg (0.5 mmol) of NaClO4.
H2O dissolved in 2.5 mL ethyl acetate. Slowly evaporation
of the solvent over several days at room temperature yielded
light white crystals of complex. M.p. 114–115 ꢁC. IR (KBr)
(cm-1): 3,015, 2,928, 2,884, 2,363, 2,338, 1,522, 1,471,
1,445, 1,355, 1,240, 1,111, 1,047, 964, 944, 841, 746.
Tetra (Ethylene Glycol) Di(4-Toluenesulfonate)
4-Toluenesulfonyl chloride (10.47 g, 55.00 mmol) in
small portions was added to tetra (ethylene glycol)
(4.45 g, 25.0 mmol) in 30 mL of distilled pyridine at
-10 ꢁC. The mixture was kept overnight at 4 ꢁC. Then,
the mixture was extracted with CH2Cl2 (3 9 50 mL). The
organic layer was extracted with 6 N HCl at 0 ꢁC. The
combined organic layers were washed with water
(2 9 25 mL) and saturated NaHCO3 solution and dried
with CaCl2 and the solvent was evaporated. Purification
by flash column chromatography (eluent: ethanol/CH2Cl2
(98/2) yielded 10.59 g (84%) of tetra (ethylene glycol)
di(4-toluenesulfonate).
X-Ray Diffraction Measurement
The intensities of Bragg reflections which are used for
structure solutions were collected by Enraf-Nonius CAD4
diffractometer in the x/2h scan mode using graphite mono-
˚
chromated CuKa radiation (k = 1.54184 A) at 298 K. The
cell constants were obtained by the least-squares analysis of
123