YATLUK et al.
772
Scheme 5.
Ti(OBu)4
+
BuOH
H[Ti(OBu)5]
(OR)3
Ti
Bu
Bu
O
O
H
RO
RO
OBu
–BuOH
O
OTi(OBu)3
O
RO
H[Ti(OBu)5]
RO
(OR)3
Ti
Bu
Bu
O
O
OTi(OBu)3
–BuOH
H
O
OBu
RO
BuOH
Ti(OBu)3[C3H5(OR)(OBu)]
+
C3H5(OR)(OBu)(OH)
+
Ti(OBu)4
Thus reactions of 2,3-epoxypropyl ethers with
1-butanol in the presence of titanium alkoxides give
addition products both according and contrary to the
Krasuskii rule. The overall yield increases as the
temperature rises, and the selectivity approaches 90%.
Analysis of the selectivity observed under catalysis by
titanium butoxide, base, mineral acid, and Lewis acid
suggests that the coordination–acid mechanism of
catalysis is preferred.
hydrochloric acid (to remove titanium butoxide). The
organic phase was separated, dried over sodium
sulfate, and subjected to fractional distillation under
reduced pressure. The target fraction was analyzed by
GLC. The reaction at 200°C was carried out in a sealed
ampule.
REFERENCES
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Sci., Part A: Polym. Chem., 1965, vol. 3, p. 2955.
EXPERIMENTAL
1-Butanol, titanium butoxide, and butyl, allyl, and
phenyl 2,3-epoxypropyl ethers were purified by dis-
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synthesized as described in [9]. 2,3-Dibutoxy-1-pro-
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from 3-butoxy-1,2-propanediol which was obtained
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chromatograph equipped with a thermal conductivity
detector; 2-m×3-mm column was packed with
Chromaton AW-HMDS impregnated with 5% of 1,2,3-
tris(β-cyanoethoxy)propane; carrier gas helium. The
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tanol. Required amounts of the reactants (Tables 1, 2)
were added to 0.2 mol of 1-butanol. The mixture was
heated for 10 h, cooled, and washed with dilute
sulfuric acid (to remove benzyldimethylamine), a solu-
tion of sodium carbonate (to remove sulfuric acid and
boron trifluoride–ether complex), or dilute (1:1)
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004