SYNTHESIS OF 1-ALKOXY-3-N-SUCCINIMIDO-2-PROPANOLS
2027
The starting 1-alkoxy-3-chloro-2-propanols IV IX
were prepared by reactions of epichlorohydrin with
aliphatic alcohols in the presence of ZnCl2 (yield 80
90%). It should be noted that alternative procedures
are also known [7, 8]. In particular, Floress Gallardo
and Pollard [7] reacted epichlorohydrin with aliphatic
alcohols in the presence of H2SO4; the yield of
the target products did not exceed 55%. With BF3
OEt2 used as acid catalyst [8], the yield of the target
products did not exceed 55%, either.
ine proton appears as a multiplet at about 3.71 ppm.
Two methylene groups of the succinimide ring give
a singlet at 4.8 5.7 ppm. In the 13C NMR spectrum,
the C=O signals are observed at 178 237 ppm.
EXPERIMENTAL
1
The H NMR spectra were measured on a Bruker
spectrometer operating at 300 MHz, and the IR spec-
tra, on a Specord 75-IR spectrophotometer (thin films).
The purity of the products and the reaction prog-
ress were monitored by TLC on Silufol UV-254 plates,
with isopropyl alcohol heptane (1 : 5) as eluent.
In both the studies cited, the yield of the target
product was relatively low, and one of the reactants
was taken in a large excess (threefold or sixfold ex-
cess of aliphatic alcohol, or sixfold excess of epi-
chlorohydrin). Furthermore, BF3 OEt2 used in [8]
is expensive and toxic.
1-Propoxy-3-chloro-2-propanol. A three-necked
flask was charged with 6 g of 1-propanol, 9.3 g of
epichlorohydrin, and 0.2 g of ZnCl2. The mixture was
heated at 90 95 C for 3 h, after which the product
was cooled and vacuum-distilled. Yield 13 g (85%),
bp 95 96 C (20 mm Hg), n2D0 1.4391. Published data
[7]: bp 97 98 C (20 mm Hg), n2D0 1.4378.
We tested as acid catalysts in the reactions of epi-
chlorohydrin with aliphatic alcohols both Brønsted
(H2SO4, HClO4) and aprotic Lewis acids (AlCl3,
SnCl4, ZnCl2). The best result was obtained with
ZnCl2. When the reaction was performed at the equi-
molar ratio of the alcohol and epichlorohydrin in the
presence of 1.2 wt % ZnCl2 (relative to the sum of
the reactants) at the boiling point of the alcohol for
2.5 3 h, the yield of 1-alkoxy-3-chloro-2-propanols
IV IX reached 80 90%. Thus, the procedure is im-
proved by eliminating the excess of one of the com-
ponents, using a cheaper catalyst, and making shorter
the reaction time.
Other 1-alkoxy-3-chloro-2-propanols IV IX were
prepared similarly; their constants agree with pub-
lished data [7, 8].
1-Propoxy-3-N-succinimido-2-propanol XII.
A three-necked flask equipped with a reflux condenser,
dropping funnel, thermometer, and stirrer was charged
with 50 ml of 2 propanol, after which 4.6 g of finely
divided sodium metal was added with vigorous stir-
ring. When the whole amount of sodium dissolved,
the mixture was cooled, 19.8 g of succinimide was
added, and the mixture was stirred on a water bath at
70 75 C for 1 h. After that, 1-propoxy-3-chloro-2-
propanol was added dropwise over a period of 20 min.
The resulting mixture was heated on a water bath at
90 C for 3 h and then cooled; the NaCl precipitate
was filtered off. The 2-propanol was distilled off in
a water-jet-pump vacuum, and the product was vacu-
um-distilled. Yield of the substituted succinimide 23 g
(53%), bp 168 C (20 mm Hg), n2D0 1.4847.
The reaction course and the accumulation of 1-al-
koxy-3-chloro-2-propanols were monitored by gas
liquid chromatography on a Tsvet-104 device (flame
ionization detector; 200 0.03-cm column packed
with 5% polyethylene glycol adipate on Porapak;
2
sample volume 0.1 l; PHe 0.8 kg cm ; paper feed
1
velocity 240 mm h ; column temperature 140 C;
vaporizer temperature 200 C).
The composition and structure of substituted suc-
cinimides X XV were confirmed by elemental anal-
ysis, IR and NMR (1H, 13C) spectroscopy, and TLC.
Found, %: C 55.39, H 8.13, N 6.52.
C10H17NO4.
Calculated, %: C 55.80, H 7.96, N 6.51.
The IR spectra of substituted succinimides X XV
contain bands at 3604 3598 (free OH groups), 3537
3532 (intramolecular hydrogen bond), and 1715
1
N-Substituted succinimides X XV were prepared
similarly.
1705 cm (C=O).
1
The highest-field signal in the H NMR spectra of
X XV is the triplet of the terminal methyl group (3H)
at 0.9 1.0 ppm. The OCH2 protons give a multiplet
at about 2.9 ppm. A broad singlet centered at 4.15
4.20 ppm belongs to the hydroxyl proton. The meth-
CONCLUSIONS
(1) The optimal conditions of the reaction of epi-
chlorohydrin with aliphatic alcohols in the presence of
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78 No. 12 2005
Gasanov
