Potassium Alkalide-Lipophilic Crown Ether Complexes
DCH16C5. 1H NMR (500 MHz, CDCl3): δ 1.10-2.04 (m, 18H),
3.10-3.90 (m, 16H). 13C NMR (75 MHz, CDCl3): 21.6-22.6,
27.1-28.3, 30.9-31.4, 66.2, 67.7, 68.4, 70.6, 71.2, 75.9, 76.7,
77.8, 78.2. IR (neat): 1111 (CO) cm-1. MS: m/e 342 (M+).
SCHEME 5
tr a n s-2-[2-(Meth oxy)eth oxy]eth oxycycloh exa n ol (1).
Under nitrogen, a mixture of 2-[2-(methoxy)ethoxy]ethanol
(12.50 g, 100 mmol) and 95% NaH (0.26 g, 10 mmol, 0.1 equiv)
was heated at 80 °C until a homogeneous solution was
obtained. The temperature was raised to 110 °C, and cyclo-
hexene oxide (10.20 g, 103 mmol) was added. The mixture was
stirred at 110 °C for 4 h and cooled to room temperature.
Vacuum distillation (160-170 °C/0.4 Torr) gave 10.60 g (49%)
of 1. Anal. Calcd for C11H22O4: C, 60.52; H, 10.16. Found: C,
1
60.51; H, 10.44. H NMR (500 MHz, CDCl3): δ 1.14-1.31 (m,
4H), 1.67-1.73 (m, 2H), 1.98-2.04 (m, 2H), 3.04-3.09 (m, 1H),
3.39 (s, 1H), 3.40-3.46 (m, 1H), 3.49 (d, 1H, J ) 1.2 Hz), 3.54-
3.57 (m, 2H), 3.58-3.63 (m, 1H), 3.65-3.70 (m, 4H), 3.85-
3.89 (m, 1H). 13C NMR (126 MHz, CDCl3): δ 24.0, 24.4, 29.8,
32.2, 59.0, 68.5, 70.4, 70.7, 71.9, 73.9, 84.8. IR (neat): 3453
(OH); 1101, 1039 (CO) cm-1
.
tr a n s-2-(10-Meth oxy-1,4,7-tr ioxan on yl)cycloh exan ol (2).
By the same procedure, cyclohexene oxide and MeOCH2(CH2-
OCH2)3CH2OH were reacted to provide 2 in 52% yield after
vacuum distillation (180 °C/0.8 Torr). Anal. Calcd for
C
13H26O5: C, 59.52; H, 9.99. Found: C, 59.67; H, 10.29. 1H
NMR (500 MHz, CDCl3): δ 1.16-1.28 (m, 4H), 1.67-1.73 (m,
2H), 1.98-2.04 (m, 2H), 3.03-3.08 (m, 1H), 3.38 (s, 1H), 3.41,-
3.45 (m, 1H), 3.49 (d, 1H), J ) 1.5 Hz), 3.55-3.56 (m, 2H),
3.58-3.63 (m, 1H), 3.64-3.69 (m, 4H), 3.85-3.89 (m, 1H). 13
C
NMR (126 MHz): δ 24.0, 24.4, 29.9, 32.2, 59.0, 68.6, 70.48,
70.54, 70.8, 71.9, 73.9, 84.8. IR (neat): 3443 (OH); 1103, 1049
(CO) cm-1
.
tr a n s-2-(12-Hyd r oxy-1,4,7,10-tetr a oxa d od ecyl)-1-cyclo-
h exa n ol (3). By the same procedure, cyclohexene oxide and
tetraethylene glycol (3 equiv) gave 3 in 25% yield after vacuum
distillation (170 °C/0.4 Torr). Anal.Calcd for C14H28O6: C,
57.51; 9.65. Found: C, 57.35; H, 9.54. 1H NMR (500 MHz,
CDCl3): δ 1.13-1.26 (m, 4H), 1.65-1.68 (m, 2H), 1.98-2.00
(m, 2H), 3.03-3.07 (m, 1H), 3.43 (br s, 2H), 3.81-3.83 (m, 1H),
4.01 (d, 1H, J ) 1.3 Hz). 13C NMR (126 MHz, CDCl3): δ 24.0,
24.3, 29.7, 32.1, 61.51, 61.52, 68.4, 70.2, 70.36, 70.39, 70.5, 70.6,
Infrared spectra were measured with a Perkin-Elmer 1600 or
BIO-RAD FTS-40A FTIR spectophotometer.
THF (POCH) was purified by a reported method.8 Potassium
(Aldrich) was distilled under high vacuum. The crown ethers
were dried at 50 °C under high vacuum for several hours before
use. CH15C5, CH18C6, and cis-DCH18C6 were obtained from
Aldrich. DCH18C6 (a mixture of cis and trans isomers) was
purchased from Merck.
73.7, 84.6. IR (neat): 3416 (OH), 1096 (CO) cm-1
.
tr a n s-2-[[2-Met h oxy)et h oxy]et h oxy]-1-[(2-m et h oxy)-
eth oxy]cycloh exa n e (4). Under nitrogen, 1 (3.30 g, 15.0
mmol) and 95% NaH (0.43 g, 18 mmol) were refluxed for 0.5
h. A THF solution of MsOCH2CH2OMe (2.70 g, 18 mmol) was
added via syringe pump during a 1-h period, and the mixture
was refluxed overnight. After the mixture was cooled to room
temperature, Et2O was added, and the solution was washed
with brine, dried over MgSO4, and evaporated in vacuo. The
crude product was chromatographed on alumina with hex-
anes-EtOAc (10:1) as eluent to give 1.87 g (45%) of 4. Anal.
Calcd for C16H32O6: C, 60.84; H, 10.21. Found: C, 61.08, 10.24..
1H NMR (500 MHz, CDCl3): δ 1.13-1.32 (m, 4H), 1.62-1.67
(m, 2H), 1.96-2.00 (m, 2H), 3.17-3.24 (m, 2H), 3.37 (s, 3H),
3.38 (s, 3H), 3.48-3.57 (m, 4H), 3.63-3.67 (m, 4H), 3.71-3.79
(m, 4H). 13C NMR (126 MHz, CDCl3): δ 23.55, 23.59, 30.2,
30.3, 58.87, 58.92, 69.21, 69.29, 70.3, 70.9, 71.9, 72.4, 81.97,
82.01. IR (neat): 1106 (CO) cm-1. MS: m/e: 277 (M+).
The GC-MS and NMR spectra of tetraethylene glycol
dimethyl ether12 and pentamethylene glycol dimethyl ether27
are reported in the literature.
Complete GC-MS data for dicyclohexano-15-crown-5, di-
cylohexano-16-crown-5, 4, and 6-8 are available as Supporting
Information.
Dicycloh exa n o-15-cr ow n -5.1c A mixture of 8.26 g (2.61
mmol) of dibenzo-15-crown-5,1a 1.6 g of glacial acetic acid, and
0.75 g of 5% rhodium on alumina catalyst in 200 mL of
1-BuOH was reacted under hydrogen (700 psi) at 110 °C for 2
h in a Parr pressure reactor. The mixture was cooled to room
temperature, and the hydrogen pressure was released. While
being flushed with nitrogen, the reactor was opened and
another 0.75 g of catalyst was added. After hydrogenation for
2 h, a third catalyst addition was made in the same manner.
After another 2 h, the mixture was filtered through Celite and
the 1-BuOH was evaporated in vacuo. The residue was passed
through a short column of alumina with dichloromethane as
tr a n s-1,2-Bis[[2-(m e t h oxy)e t h oxy]e t h oxy]cycloh e x-
a n e (5). By the same procedure, 1 and MsOCH2(CH2OCH2)2-
CH2OMe were reacted to form the crude product. Vacuum
distillation (130-133 °C/0.4 Torr) gave a 50% yield of 5. Anal.
Calcd for C16H32O6: C, 59.97; H, 10.07. Found: 59.62; H, 10.11.
1H NMR (500 MHz, CDCl3): δ 1.15-1.19 (m, 2H), 1.21-1.26
(m, 2H), 1.63-1.64 (m, 2H), 1.95-1.97 (m, 2H), 3.17-3.22 (m,
2H), 3.37 (s, 6H), 3.51-3.55 (m, 4H), 3.60-3.67 (m, 8H). 3.73-
3.75 (m, 4H). 13C NMR (126 MHz, CDCl3): δ 23.6, 30.3, 59.0,
70.4, 71.0, 72.0, 81.9. IR (neat): 1106 (CO) cm-1. MS m/e (rel
intens): 321 (0.5, M+), 200 (4), 186 (6), 142 (16), 141 (22), 121
(13), 103 (50), 87 (12), 81 (34), 59 (100), 45 (76).
1
eluent to give 7.00 g (81%) of DCH15C5. H NMR (500 MHz,
CDCl3): δ 1.00-2.05 (m, 16H), 3.15-3.95 (m, 16H). 13C NMR
(75 MHz, CDCl3): δ 22.4, 27.4-27.9, 67.7, 68.5, 70.9, 77.2-
77.9. IR (neat): 1103 (CO) cm-1. MS: m/e 328 (M+).
Dicycloh exa n o-16-cr ow n -5.1c Hydrogenation of dibenzo-
16-crown-51a under similar conditions gave a 70% yield of
(27) Ouchi, M.; Inoue, Y.; Kanzaki, T.; Hakushi, T. Bull. Chem. Soc.
J pn. 1984, 57, 887.
J . Org. Chem, Vol. 67, No. 22, 2002 7811