1932
TUGAROVA et al.
spectra were consistent with the previously described
Optical density (λ595
)
[9].
I
I
III
IV
5-Butoxymethyl-5-chloromethyl-1,3-dioxane (VII).
Control
II
IV
To a mixture of 0.1 mol of 3,3-bischloromethyloxetane
and 0.1 mol of paraformaldehyde in 80 mL of 1,4-
dioxane was added dropwise 2 mL of conc. sulfuric
acid. The mixture was stirred at 90–100°C for 5 h.
After cooling a solution of Na2CO3 was added. Then
the solvent was evaporated, and the residue was
distilled in a vacuum to give 5,5-bischloromethyl-1,3-
dioxane in 70% yield, bp 120°C (12 mmHg) [10].
VI
VI
VIII
VII
VII
VIII
II
V
II
V
I
IIII
I
III
To a mixture of 0.012 mol of butanol, 0.012 mol of
NaOH, 0.03 g of catamine AB, and 15 mL of DMSO
was added 0.012 mol of 5-chloromethyl-1,3-dioxane
under vigorous stirring and heating (65–70°C). Then
the mixture was washed with water and extracted with
chloroform. The organic layer was dried with MgSO4
and concentrated. The residue was distilled in a
vacuum. Yield 80%, bp 144°C (12 mmHg) [10].
Concentration, %
Toxicity of compounds I–VIII with respect to the strain
A. Brasilense Sp245.
stirred under reflux using a Dean–Stark trap. After
cooling, the catalyst was filtered off. The filtrate was
washed with 5% NaHCO3 solution and water. The
organic layer was dried over MgSO4 and fractionated.
Physicochemical constants and parameters of the NMR
spectra of the obtained compounds were similar to
those described previously [12–14].
2-(Chloromethyl)-1,1-dichlorocyclopropane (VIII).
To a solution of 0.1 mol of 3-chloroprop-1-ene, 0.2 g
of triethylbenzylammonium chloride in 300 mL of
chloroform at vigorous stirring and heating at 40–45°C
was added dropwise 320 g of 50% aqueous solution of
NaOH within 2 h. Then the mixture was washed with
water, and the organic layer was dried over MgSO4.
After removing chloroform, the residue was distilled in
a vacuum. Yield 98%, bp 58°C (5 mmHg). Physico-
chemical constants and parameters of the NMR spectra
were consistent with the previously described [11].
4-Hydroxymethyl-1,3-dioxolane and 5-hydroxy-
1,3-dioxane (I). Yield 93%, mp 190–195°C. Accord-
ing to gas chromatography-mass spectrometry data,
glycerol formal I consist of an equimolar mixture of 5-
hydroxy-1,3-dioxane and 4-hydroxymethyl-1,3-dioxolane.
REFERENCES
5,5-Dimethyl-1,3-dioxane (II). Yield 77%, mp
125°C.
1. Bogomazova, A.A., Mikhailova, N.N., and Zlotskii, S.S.,
Sovremennaya
khimiya
tsiklicheskikh
atsetalei.
5-Ethyl-5-hydroxymethyl-1,3-dioxane (III). Yield
97%, bp 85°C (4 mmHg).
Poluchenie, reaktsii i svoistva (Modern Chemistry of
Cyclic Acetals. Preparation, Reactions, Properties),
Saarbrücken: LAPLAMBERT Academic Publishing
GmbH&Co, 2011.
4-Methyl-1,3-dioxane (IV). Yield 69%, bp 114°C.
2-Isopropyl-1,3-dioxolane (V). Yield 92%, bp 121°C.
2. Shavshukova, S.Yu., Shvetsov, S.V., and Zlotskii, S.S.,
Sovremennye promyshlennye gerbitsidy. Poluchenie i
primenenie (Modern Industrial Herbicides. Preparation
and Application), Ufa: OOO “Monografiya,” 2011.
3. Bogomazova, A.A., Shiriazdanova, A.R., Mikhailova, N.N.,
Kuznetsov, V.M., and Zlotskii, S.S., Bashk. Khim. Zh.,
2010, vol. 17, no. 3, p. 33.
4. Timofeeva, S.A., Giniyatullina, E.Kh., Kuznetsov, V.M.,
Udalova, E.A., Shavshukova, S.Yu., and Zlotskii, S.S.,
Bashk. Khim. Zh., 2011, vol. 18, no. 3, p. 71.
4-Chloromethyl-1,3-dioxolane (VI). A mixture of
2 mol of epichlorohydrin, 360 mL of water, and 1 mL
of sulfuric acid was vigorously stirred at 90–100°C for
2 h. Then to the mixture was added 1.8 mol of para-
formaldehyde, and heating was continued until the mix-
ture became transparent. After adding 10% Na2CO3
solution, the resulting mixture was distilled. Fraction
with bp 100–145°C was extracted with chloroform,
dried with MgSO4, and distilled. Yield 92%, bp 148°C.
Physicochemical constants and parameters of the NMR
5. Kamnev, A.A., Tugarova, A.V., Antonyuk, L.P.,
Tarantilis, P.A., Kulikov, L.A., Perfiliev, Yu.D.,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 10 2014