Reaction of 4,4-dimethyl-1,3-dioxane with dinitriles

Article abstract of DOI:10.1023/A:1012302127645

The reaction of 4,4-dimethyl-1,3-dioxane with bis(2-cyano)diethyl ether or 1,2-di(β-cyanoethoxy)-ethane yields the corresponding bis[2-(4,4-dimethyl-5,6-dihydro-2-oxazinyl)]diethyl ether and 1,2-di{β-[2-(4,4-dimethyl-5,6-dihydro-2-oxazinyl)]ethoxy} ethane

Full text of DOI:10.1023/A:1012302127645

Russian Journal of General Chemistry, Vol. 71, No. 1, 2001, pp. 126 127. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 1, 2001,
pp. 137 139.
Original Russian Text Copyright
2001 by Kuznetsov, Mazepa, Brusilovskii, Krasnoshchekaya.
Reaction of 4,4-Dimethyl-1,3-dioxane with Dinitriles
V. V. Kuznetsov, A. V. Mazepa, Yu. E. Brusilovskii, and S. P. Krasnoshchekaya
Bogatskii Physicochemical Institute, Ukrainian National Academy of Sciences, Odessa, Ukraine
Ufa State Petroleum Technical University, Ufa, Bashkortostan, Russia
Received December 14, 1999
Abstract The reaction of 4,4-dimethyl-1,3-dioxane with bis(2-cyano)diethyl ether or 1,2-di( -cyanoethoxy)-
ethane yields the corresponding bis[2-(4,4-dimethyl-5,6-dihydro-2-oxazinyl)]diethyl ether and 1,2-di{ -
[2-(4,4-dimethyl-5,6-dihydro-2-oxazinyl)]ethoxy}ethane which are readily hydrolyzed under the action of
aqueous alkali to give 3-methyl-3-amino-1-butanol.
1
One of the reasonably simple routes to 5,6-dihydro-
1,3-oxazines, which are important precursors of 1,3-
amino alcohols and aldehyds [1, 2], is based on the
reaction of 1,3-dioxanes with acetonitrile [3 5]. As
the above transformation is a modification of the Rit-
ter reaction, it follows the principal relationships of
formation of a new C N bond involving the nitrile
group [6, 7], on the one hand, and of the majority of
heterolytic reactions of 1,3-dioxacycloalkanes [8], on
the other hand. In this connection, proceeding with
studies of reactions of 1,3-heterocycles with nitriles
[9], we examined in this work the reactions of 4,4-di-
methyl-1,3-dioxane (I), which can be readily prepared
by the Prins reaction, with bis(2-cyano)diethyl ether
(II) and 1,2-di( -cyanoethoxy)ethane (III). These re-
actions were not reported previously.
were confirmed by mass spectrometry and H NMR
spectroscopy (see table). The molecular ion peaks are
lacking in the mass spectra, but the characteristic
fragmentation ions are present.
The significantly lower, as compared to the reac-
tion between dioxane I and acetonitrile [3 5], yield of
compounds IV and V is probably due to some side
polymerization reactions involving dinitriles [6]. In-
deed, significant amount of bottoms (up to 60% of
the initial weight) remains after vacuum distillation.
The other cause is the hydrolytic instability of ox-
azines IV and V: noticeable amounts of 3-methyl-3-
amino-1-butanol VI were detected in the reaction
products by GLC.
The products of these reactions were the corre-
sponding bis[2-(4,4-dimethyl-5,6-dihydro-2-oxazinyl)]-
diethyl ether (IV) and 1,2-di{ -[2-(4,4-dimethyl-5,6-
dihydro-2-oxazinyl)]ethoxy}ethane (V).
On hydrolysis with aqueous alkali, compounds IV
and V with the yield of 70 74% give amino alcohol
VI identified by GLC using a reference sample [3, 10].
OH
NaOH
IV, V
NH2
H3C CH3
VI
The new reactions supplement the known chemical
transformations of 1,3-dioxanes [8], though they can-
not be recommended as a preparative route to 5,6-di-
hydro-1,3-oxazine derivatives because of the low yield
of the target compounds.
The maximal yield of derivatives IV and V was
10%. The IR spectra of these compounds contain a
1
strong band
at 1650 cm . In addition, the com-
positions andCs=tNructures of the obtained compounds
1070-3632/01/7101-0126$25.00 2001 MAIK Nauka/Interperiodica

REACTION OF 4,4-DIMETHYL-1,3-DIOXANE WITH DINITRILES
127
1H NMR spectra and first fragment ions in the mass spectra of compounds IV and V
Compound no.
, ppm (3J, Hz)
Assignmenta
m/z (Irel, %)
IV
1.09 s (6H)
(CH3)2 C4
195 (4) [M
156 (100) [M
141 (28) [M
C5H11NO]+
1.62 t (2H, J 6.0)
2.29 t (2H, J 6.5)
3.59 t (2H, J 6.5)
4.07 t (2H, J 6.0)
1.12 s (6H)
1.55 t (2H, J 6.0)
2.28 t (2H, J 6.3)
3.54 t (2H, J 6.3)
3.56 t (2H, J 6.3)
4.08 t (2H, J 6.0)
C5H2
C8H14NO]+
C8H14NO
CH2 C2
O CH2 acyclic
C4H2
CH3]+
V
(CH3)2 C4
C5H2
156 (40) [M
141 (10) [M
C10H18NO2]+
C10H18NO2
CH3]+
CH2 C2
O C CH2
O
O CH2 C C=N
C6H2
a
The inner atom numbering in the oxazine ring is given.
EXPERIMENTAL
scribed in [1]. The boiling point of the resulting
amino alcohol VI was in agreement with the pub-
lished data [3, 10].
The IR spectra were obtained on a Specord IR-75
1
spectrophotometer in thin films; the H NMR spectra
were recorded on a Tesla BS-497 spectrometer from
20% solutions in CDCl3, with TMS as internal ref-
erence. The mass spectra were measured on an MKh-
1321 instrument at the ionizing electron energy of
70 eV. The GLC analysis was carried out on a Tsvet-
126 chromatograph (flame-ionization detector, 3000
4-mm column, stationary phase 5% OV-17 on Chro-
maton N-Super, carrier gas argon).
REFERENCES
1. Smith, M.E. and Adkins, H., J. Am. Chem. Soc., 1938,
vol. 60, no. 2, pp. 407 409.
2. Meyers, A.I., Nabeya, A., Adickes, H.W., and Po-
litzer, I.R., J. Am. Chem. Soc., 1969, vol. 91, no. 3,
pp. 763 764; Meyers, A.I., Nabeya, A.I., Adi-
ckes, H.W., Politzer, I.R., Malone, G.R., Koveles-
ky, A.C., Nolen, R.L., and Portnoy, R.C., J. Org.
Chem., 1973, vol. 38, no. 1, pp. 36 56.
Derivatives of 4,4-dimethyl-5,6-dihydro-1,3-ox-
azines IV and V. To a mixture of 0.6 mol of dioxane
I and 0.25 mol of dinitrile II or III in 150 ml of
hexane, 0.3 mol of concentrated H2SO4 was slowly ad-
ded dropwise with stirring and cooling with ice-cold
water (attempted addition of 1,3-dioxane to a mixture
of dinitrile and sulfuric acid led to tarring). Then the
reaction mixture was stirred at room temperature for
24 h and diluted with 100 ml of water; hexane was
separated in a separating funnel, and the aqueous layer
was extracted with chloroform (2 50 ml). After
evaporation of the combined organic layers, we re-
covered 15 20 ml of the initial dioxane I. To the re-
maining aqueous phase, cooled with ice, solid LiOH
was added to attain pH 9 10. The separated oily re-
action product with a specific odor was extracted with
chloroform (4 50 ml) and dried over anhydrous
MgSO4; the solvent was removed on a rotary evap-
orator, and the residue was fractionated in a vacuum.
Oxazine IV, bp 135 140 C (3 mm Hg), and oxazine
V, bp 145 150 C (3 mm Hg), were obtained as
viscous light yellow liquids with a typical amine odor.
In both cases large amount of bottoms remained after
vacuum distillation.
3. Kalyuskii, A.R., Kuznetsov, V.V., Posashkova, S.E.,
and Gren’, A.I., Russian Inventor’s Certificate
no. 1705290, 1992, Byull. Izobret., 1992, no. 2.
4. Kuznetsov, V.V., Kalyuskii, A.R., and Gren’, A.I.,
Zh. Org. Khim., 1995, vol. 31, no. 11, pp. 1667 1670.
5. Gren, A.I. and Kuznetsov, V.V., Abstracts of Papers,
IXth European Symp. on Organic Chemistry, Warsaw,
1995, report PA 46.
6. Zil’berman, E.N., Reaktsii nitrilov (Reactions of
Nitriles), Moscow: Khimiya, 1972, pp. 251 288.
7. Gridnev, I.D. and Gridneva, N.A., Usp. Khim., 1995,
vol. 64, no. 11, pp. 1091 1105.
8. Rakhmankulov, D.L., Karakhanov, R.A., Zlotskii, S.S.,
Kantor, E.A., Imashev, U.B., and Syrkin, A.M., Tekh-
nologiya organicheskikh veshchestv (Technology of
Organic Compounds), vol. 5: Khimiya i tekhnologiya
1,3-dioksatsikloalkanov (Chemistry and Technology
of 1,3-Dioxacycloalkanes), Moscow: VINITI, 1979.
9. Kuznetsov, V.V., Abstracts of Papers, XII Mezhdu-
narodnaya konferentsiya po proizvodstvu i primene-
niyu khimicheskikh reaktivov i reagentov Reaktiv-
99 (XII Int. Conf. on the Production and Use of
Chemicals Reagent-99 ), Ufa, 1999, p. 62.
10. Kalyuskii, A.R. and Posashkova, S.E., Available from
VINITI, 1988, Moscow, no. 8456-V88, Ref. Zh. Khim.,
1989, 9Zh115.
Hydrolysis of oxazines IV and V was carried out
by treatment with 20% NaOH by the procedure de-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001