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Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 2361–2367
4.1.2. 1-Benzyloxy-2-propanol
(CH); 73.23 (CH2–Ph); 71.03 (CH2–Ph); 17.25 (CH3).
13C NMR spectrum was earlier presented in [41]. Mass
spectrum (m=e): 256 [Mþ, 1]; 165 (36); 107 (18); 91 (100);
79 (6); 65 (13); 39 (2).
GC–MS and NMR spectra of benzyl glycidyl ether
[26], benzyl methyl ether [27], benzyl propyl ether [27],
and tetraethylene glycol benzyl vinyl ether [12] have
been reported previously.
1H NMR (CDCl3): d ¼ 7:30 ꢀ 7:35 (m, 5 H, Ph); 4.55
(s, 2 H, CH2); 3.97 (m, 1 H, CHðMÞ; JAM ¼ 3:0 Hz,
JBM ¼ 7:5 Hz, JMX ¼ 6:3 Hz); 3.42 (q, 1 H, CHðAÞ
JAB ¼ 8:5 Hz, JAM ¼ 3:0 Hz); 3.26 (q, 1 H, CHðBÞ
JAB ¼ 8:5 Hz, JBM ¼ 7:5 Hz); 1.12 (d, 3 H, CHðXÞ
;
;
;
4.4. General procedure
JMX ¼ 6:3 Hz). Mass spectrum (m=e): 165 [Mþ, 30]; 107
Preparation of Kꢀ, Kþ(15-crown-5)2 1 tetrahydrofu-
ran solution was performed at ambient temperature in an
apparatus presented in [12]. Potassium (about 1.5 g) was
distilled into a reactor under a high vacuum. Then, 0.2 M
15-crown-5 solution in tetrahydrofuran (10 mL) was
dropped on the metal mirror. After 25 min of ultrasonic
mixing a deep blue 0.1 M solution of 1 was obtained. The
solution was finally filtered through a glass frit.
The reaction was conducted in a 50 mL reactor
thermostatted at 25 °C. In one series of experiments 0.1
M solution of 1 (10 mL) was gradually introduced into
the reactor filled with 0.5 M of selected alcohol in tet-
rahydrofuran (10 mL) while mixing. In the other ex-
periments the blue potassium solution was titrated with
0.1 M alcohol solution until discoloration of the reac-
tion mixture. Benzyl bromide (10% excess in relation to
potassium ions) was used as the quenching agent to
transform non-volatile reaction products into the vola-
tile compounds. Then, water (2 mL) was added to the
reaction mixture obtained at the excess of 1. The basicity
of the water phase was found in the system with meth-
anol or propanol, which indicated the presence of po-
tassium hydroxide. The products obtained were
identified matching their mass spectra, retention times,
as well as NMR spectra.
(32); 91 (100); 79 (6); 77 (5); 65 (18); 51 (1).
4.2. Benzyl vinyl ether (23)
A mixture of 0.01 mol 2-bromoethylbenzyl ether, 0.01
mol 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and tet-
rahydrofuran (10 mL) was stirred intensely at 60 °C for
8 h. Subsequently cooled pentane (10 mL) was added
and the mixture was left at 0 °C overnight. The salt
precipitate was filtered and washed with 10 mL of tet-
rahydrofuran and pentane mixture (1:1). Volatile frac-
tions 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. Mass spectrum
(m=e): 134 [Mþ, 4]; 116 (7); 105 (11); 91 (100); 77 (7); 65
(30); 51 (9); 39 (11). 1H and 13C NMR spectra (in
CDCl3) have been already presented in [39,40].
4.3. 1,2-Dibenzyloxypropane (24)
A mixture of 0.1 mol 1,2-propanediol, 0.22 mol
benzyl chloride, 50% NaOH (60 mL), 0.007 mol tetra-
butylammonium hydrogensulfate, and benzene (60 mL)
was stirred intensely at 70–80 °C on a water bath for 3 h.
Subsequently cooled water (100 mL) and hexane (100
mL) was added. The layers were separated, the organic
layer washed three times with water (50 mL) and dried
with anhydrous MgSO4. After removal of hexane and
benzene the residue was distilled under reduced pressure.
1,2-Dibenzyloxypropane was finally obtained in 62%
yield (purity >97%; GC). B.p. ¼ 170–171 °C/2 mm Hg.
Acknowledgements
The authors are indebted to Dr. K. Skutil for the
analysis of gaseous compounds with the GC technique.
References
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1H NMR (CDCl3): d ¼ 7:25 ꢀ 7:37 (m, 10 H, Ph);
4.61 (s, 2 H, CH2); 4.55 (s, 2 H, CH2); 3.76 (m, 1 H,
CHM, JAM ¼ 6:0 Hz, JBM ¼ 4:8 Hz, JMX ¼ 6:3 Hz); 3.55
(q, 1 H, CHA, JAB ¼ 10:2 Hz, JAM ¼ 6:0 Hz); 3.45 (q, 1
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ꢀ