1100
BAIBURTLI et al.
Y, %
(a)
Acetalization procedure. A mixture of 0.01 mol of
alcohol 10 or 11, 0.012 mol of ketone 8 or aldehyde 9,
1
2
0 wt % catalyst, and 30 mL of benzene was refluxed for
–4 h up to separation of the calculated amount of water.
After the reaction completion, the mixture was cooled,
dried, filtered, and evaporated. Products 12 and 13 were
isolated at reduced pressure.
The following products were obtained using this
procedure.
τ, min
Y, %
(b)
2
,2-Dimethyl-4-hydroxymethyl-1,3-dioxolane
2. The physicochemical parameters agree with the
published data [11].
-Isopropyl-1,3-dioxolane 13. The physicochemical
1
2
parameters agree with the published data.
Reaction of olefins 14 and 15 with para-
formaldehyde (general procedure). A mixture 0.1 mol
of of styrene 14 or α-methylstyrene 15 and 0.12 mol
of paraformaldehyde in 40 mL of 1,4-dioxane in the
presence of 10 wt % zeolite was stirred at the boiling
point of 1,4-dioxane (100°С) for 4 h. After the reaction
completion, the catalyst was filtered off, and the solvent
was distilled off. Products 16 and 17 were isolated by
distillation at reduced pressure.
τ, min
Fig. 3. Influence of the kind of the catalyst on the yield Y of
compounds (a) 16 and (b) 17. Conditions: olefin 14 or 15 to
paraformaldehyde molar ratio 0.8 : 2, 10 wt % catalyst relative
to olefin, 100°С, solvent 1,4-dioxane. Zeolite: (1) СBV-720
and (2) H-Beta.
The following products were obtained using this
procedure.
exo-2-(Butoxy)bicyclo[2.2.1]heptane 5. The physi-
cochemical parameters agree with the published data
10].
exo-2-(2-Methylpropoxy)bicyclo[2.2.1]heptane 6.
The following products were obtained using this
procedure.
4
-Phenyl-1,3-dioxane 16. Yield 70%, Т = 94°С
b
[
1
(
12 mmHg). Н NMR spectrum [CDCl , δ, ppm (J, Hz)]:
3
1.39–1.43 m (2H, CH ), 3.64–3.75 m (2Н, СН ), 4.03 t
2
2
1
Yield 90%, Т = 64°С (12 mmHg). Н NMR spectrum
(1H, CH, J 2.1), 5.02 d (2H, CH , J 4.8), 7.22–7.39 m
b
2
1
3
(
CDCl , δ, ppm): 0.89 m (3H, CH ), 0.99–1.06 m (2H,
(5Н, Ph–). C NMR spectrum (CDCl , δ , ppm): 33.76
3 С
3
3
CH ), 1.27–1.42 m (2H, CH ), 1.50–1.58 m (4H, CH ),
(CH ), 68.42 (CH ), 77.03 (СН), 96.49 (CH ), 120.82–
2
2
2
2 2 2
2
.18 s (1H, CH), 2.28 s (1Н, CH), 3.19–3.33 m (1H, CH),
142.82 (Ph–). Mass spectrum, m/e (I , %): 86 (50), 71
(20), 57 (100), 43 (29).
rel
13
3.19–3.33 m (2H, CH2). C NMR spectrum (CDCl3,
δ , ppm): 21.76 (CH ), 25.32 (CH ), 28.71 (CH ), 36.32
С
3
2
2
4-Methyl-4-phenyl-1,3-dioxane 17. Yield 80%,
(
7
CH ), 37.98 (CH), 40.21 (CH ), 43.59 (CH), 70.42 (CH),
1
2
2
Т = 121°С (12 mm Hg). Н NMR spectrum [CDCl ,
b
3
+
9.02 (СН). Mass spectrum, m/e (I , %): 154 М (2), 94
rel
δ, ppm (J, Hz)]: 1.32 s (3H, CH ), 1.60–1.68 m (2H,
3
(100), 79 (82), 66 (82), 67 (62), 41 (51), 43 (38), 95 (35),
CH ), 3.67–3.71 m (2Н, СН ), 5.02 d (2H, CH , J 4.6),
2
2
2
83 (24), 55 (20), 68 (17), 57 (16), 112 (12), 44 (11).
13
7
.20–7.45 m (5Н, Ph–). C NMR spectrum (CDCl , δ ,
3 С
exo-2-(Propoxy)bicyclo[2.2.1]heptane 7. Yield
ppm): 25.11 (CH ), 35.55 (CH ), 69.44 (CH ), 77.61
3 2 2
1
9
0%, Т = 73°С (12 mmHg). Н NMR spectrum (CDCl ,
(С), 93.77 (CH ), 120.62–138.67 (Ph–). Mass spectrum,
b
3
2
δ, ppm): 0.85 m (3H, CH ), 0.98–1.08 m (2H, CH ),
m/e (I , %): 163 (30), 132 (24), 117 (26), 105 (100), 91
3
2
rel
1
.22–1.43 m (2H, CH ), 1.52–1.57 m (6H, CH ), 2.18
(28), 77 (29).
2
2
s (1H, CH), 2.28 s (1Н, CH), 3.20–3.31 m, (1H, CH),
1
3
3
.13–3.32 m (2H, CH2). C NMR spectrum (CDCl3,
CONCLUSIONS
δ , ppm): 11.29 (CH ), 25.32 (CH ), 26.02 (CH ), 28.71
С
3
2
2
(
(
CH ), 36.32 (CH ), 37.98 (CH), 40.21 (CH ), 43.59
CBV-720 zeolite surpasses H-Beta zeolite and KU-2
cation-exchange resin in the catalytic performance in
2
2
2
CH), 70.42 (CH ), 79.02 (СН).
2
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 7 2017