2306
Russian Chemical Bulletin, International Edition, Vol. 51, No. 12, pp. 2306—2307, December, 2002
Letters to the Editor
The first example of heterolytic fragmentation
of organic nitrates of a heterofunctional series
ꢀ
A. M. Korolev, L. T. Eremenko, L. V. Meshikhina
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
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42432 Chernogolovka, Moskovskaya obl., Russian Federation.
Fax: +7 (096) 515 5588. Eꢀmail: elt@icp.ac.ru
The reaction of pentaerythritol mononitrate (1a) with
A comparison of the reactivities of monosubsituted
pentaerythritol derivatives 1a,b showed that transformaꢀ
tions of mononitrate 1a require more drastic conditions.
The yields of heterocyclic glycol 2 in both cases are the
same (∼ 70%), the yields of unsaturated glycol 3 in reacꢀ
tions of 1a and 1b are 8.5 and 17%, respectively. OꢀNitꢀ
ration of glycol 3 obtained from 1a gave the known
2ꢀmethylidenepropaneꢀ1,3ꢀdiol dinitrate(4).5
a base yields an intramolecular nucleophilic substitution
product, viz., 3,3ꢀbis(hydroxymethyl)oxetane (2) (heteroꢀ
cyclization, pathway a) (this is a new method of its synꢀ
thesis). An unknown reaction for organic nitrates of a
heterofunctional series also takes place, viz., heterolytic
1
fragmentation (Grob's fragmentation, pathway b), leadꢀ
ing to 2ꢀmethylidenepropaneꢀ1,3ꢀdiol (3):
Mononitrate 1a (m.p. 78—79 °С) and bromide 1b (m.p.
6
,7
7
5—76 °С) were obtained according to the known procedures.
,3ꢀBis(hydroxymethyl)oxetane (2) and 2ꢀmethylideneproꢀ
3
paneꢀ1,3ꢀdiol (3). A. A solution of KOH (6.5 g, 115 mmol) in dry
EtOH (95 mL) was added to a stirred solution of compound 1a
(
18.1 g, 100 mmol) in dry EtOH (80 mL). The reaction mixture
was refluxed for 2 h, cooled, and KNO was filtered off. The
3
filtrate was concentrated, and the residue was distilled in vacuo
to give compound 3, yield 0.75 g (8.5%), b.p. 80—82 °С (1 Torr),
nD 1.4755 (Ref. 8: 93—95 °С (2 Torr),3 nD 1.4758 ) and
2
0
20
compound 2, yield 8.15 g (69%), b.p. 132—134 °С (1 Torr)
(
Ref. 2: b.p. 128 °С (0.4 Torr)).
1
: X = ONO (a), Br (b)
2
B. Compounds 2 and 3, identical to those described above,
3
were obtained according to the known procedure in yields 70
and 17%, respectively.
First, heterocyclic glycol 2 has been synthesized
from bromide 1b, whereupon the fragmentation prodꢀ
uct of 3 has not been observed, this has been obtained
later.3
2
ꢀMethylideneꢀ1,3ꢀpropaneꢀ1,3ꢀdiol dinitrate (4) was obꢀ
2
tained upon nitration of compound 3 (from 1a) according to the
known procedure, b.p. 64—65 °С (1 Torr), n
,4
5
20
1.4636 (Ref. 5:
D
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2141—2142, December, 2002.
066ꢀ5285/02/5112ꢀ2306 $27.00 © 2002 Plenum Publishing Corporation
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