1584
Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 1580–1585
4.2. Benzyl vinyl ether (11)
hexane and benzene on a rotatory evaporator the resi-
due was distilled under reduced pressure. Triethylene
glycol benzyl methyl ether has been finally obtained in
70% yield as a novel compound (purity > 97%; GC).
B.p. ¼ 191 °C/2 mm Hg.
A mixture of 0.01 mol 2-bromoethyl benzyl ether,
0.01 mol 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and
tetrahydrofuran (10 mL) was vigorously stirred at 60 °C
for 8 h. After cooling pentane (10 mL) was added and
the mixture was left overnight at 0 °C. The salt precip-
itate was filtered off and washed with 10 mL of tetra-
hydrofuran and pentane mixture (1:1). Volatile fractions
were removed by distillation and benzyl vinyl ether was
obtained in practically quantitative yield (purity > 99%;
GC). B.p. ¼ 50–51 °C/16 mm Hg. MS; m/z (%): 134
(Mþ, 4), 116 (7), 105 (11), 91 (100), 77 (7), 65 (30), 51 (9),
39 (11). MS data were also presented in [24], and 1H and
13C NMR (CDCl3) spectra in [25].
1
2
3
4
5
6
7
PhCH2-O-CH2CH2-O-CH2CH2-O-CH2CH2-O-CH3
1H NMR (CDCl3): 7.40–7.20 (m, 5H, Ph), 4.56 (s,
2H, CH2-1), 3.70–3.60 (m, 10H, CH2-2,3,4,5,6), 3.48–
3.56 (m, 2H, CH2-7), 3.36 (s, 3H, CH3). 13C NMR:
138.14 (C-1, Ph), 128.25 (Cmeta, Ph), 127.58 (Cortho, Ph),
127.47 (Cpara, Ph), 78.06 (CH2-1), 71.79 (CH2-7), 70.49
(CH2-2,3,4), 70.39 (CH2-5), 69.27 (CH2-6), 58.88 (CH3).
MS, m/z (%): 254 (Mþ, 2), 195 (2), 148 (14), 133 (14),
120 (6), 105 (12), 92 (100), 77 (10), 72 (7), 65 (24), 59
(92), 45 (25), 39 (7). HRMS (EI, 70 eV) calcd. for
C14H22O4 [Mþ] 254, 1518. Found 254, 1515.
4.3. Ethylene glycol benzyl butyl ether (13)
A mixture of 0.1 mol ethylene glycol monobutyl
ether, 0.11 mol benzyl chloride, 50% NaOH (60 mL),
0.005 mol tetrabutylammonium hydrogensulfate, and
benzene (50 mL) was vigorously stirred in 70–80 °C on a
water bath for 3 h. After cooling, water (100 mL) and
hexane (100 mL) were added. The layers were separated,
the organic layer has been washed with water (3 ꢁ 50
mL) and dried with anhydrous MgSO4. Having re-
moved hexane and benzene on a rotatory evaporator the
residue has been distilled under reduced pressure. Eth-
ylene glycol benzyl butyl ether was finally obtained in
88% yield as a novel compound (purity > 97%; GC).
B.p. ¼ 161–162 °C/2 mm Hg.
4.5. Diethylene glycol benzyl methyl ether (21)
A mixture of 0.1 mol diethylene glycol monomethyl
ether, 0.11 mol benzyl chloride, 50% NaOH (60 mL),
0.005 mol tetrabutylammonium hydrogensulfate, and
benzene (50 mL) was vigorously stirred at 70–80 °C on a
water bath for 3 h. After cooling, water (100 mL) and
hexane (100 mL) were added. The layers were separated,
the organic layer was washed with water (3 ꢁ 50 mL)
and dried with anhydrous MgSO4. Having removed
hexane and benzene on a rotatory evaporator the resi-
due was distilled under reduced pressure. Diethylene
glycol benzyl methyl ether was finally obtained in 80%
1
2
3
4
5
6
7
PhCH2-O-CH2CH2-O-CH2CH2CH2CH3
1H NMR (CDCl3): 7.40–7.20 (m, 5H, Ph), 4.57 (s,
2H, CH2-1), 3.60–3.62 (m, 4H, CH2-2,3), 3.47 (t, J ¼
6.7 Hz, 2H, CH2-4), 1.62–1.52 (m, 2H, CH2-5), 1.43–
1.30 (m, 2H, CH2-6), 0.92 (t, J ¼ 7.2 Hz, 3H, CH3). 13
C
NMR: 138.26 (C-1, Ph), 128.25 (Cmeta, Ph), 127.64
(Cortho, Ph), 127.46 (Cpara, Ph), 73.14 (CH2-1), 71.14
(CH2-4), 70.07 (CH2-3), 69.35 (CH2-2), 31.66 (CH2-5),
19.21 (CH2-6), 13.86 (CH3). MS, m/z (%): 208 (Mþ, 25),
151 (3), 134 (4), 117 (6), 107 (19), 91 (100), 73 (17), 55
(14), 57 (43), 41 (15). HRMS (EI, 70 eV) calcd. for
C13H20O2 [Mþ] 208, 1463. Found 208, 1464.
4.4. Triethylene glycol benzyl methyl ether (18)
A mixture of 0.1 mol ethylene glycol monobutyl
ether, 0.11 mol benzyl chloride, 50% NaOH (60 mL),
0.006 mol tetrabutylammonium hydrogensulfate, and
benzene (50 mL) was vigorously stirred at 70–80 °C on a
water bath for 3 h. After cooling, water (100 mL) and
hexane (100 mL) were added. The layers were separated,
the organic layer was washed with water (3 ꢁ 50 mL)
and dried with anhydrous MgSO4. Having removed
Fig. 1. 2D-NMR HETCOR (H, C) spectrum of diethylene glycol
benzyl methyl ether (21) – methylene region.