Russian Journal of General Chemistry, Vol. 75, No. 8, 2005, pp. 1325 1326. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 8, 2005,
pp. 1396 1397.
Original Russian Text Copyright
2005 by Gazizov, Ibragimov, Khamidullina, Karimova, Pudovik, Sinyashin.
LETTERS
TO THE EDITOR
New Reaction of Organic Monohalides with Orthoformates
M. B. Gazizov*, Sh. N. Ibragimov*, O. D. Khamidullina*, R. F. Karimova*,
M. A. Pudovik**, and O. G. Sinyashin**
* Kazan State Technological University, Kazan, Tatarstan, Russia
** Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Kazan, Tatarstan, Russia
Received December 6, 2004
No information on reaction of organic halides with
orthoformic acid esters is available in the literature.
At the same, this reaction might give important un-
symmetrical ethers.
whereas the signal at 8.0 ppm compared in intensity
with those at 5.2 and 5.39 ppm.
Reaction of compounds Ia and IIa. A mixture of
3 g monochloride Ia and 1.26 g of ortho ester IIa was
heated at 150 C for 6 h and then distilled to obtain
2.45 g (83%) of methoxytriphenylmethane (IIIa), mp
We are the first to find that organic monohalides
possessing a high electrophilic reactivity, such as
chlorotriphenyl-, chlorodiphenyl-, and bromodiphenyl-
methanes (Ia Ic),in appropriate temperature condi-
tions react with orthoformates IIa IIc. Mixtures of
compounds I and II (molar ratio 1:1.1) were heated in
sealed ampules at 100 150 C to give unsymmetrical
ethers IIIa, IIIb IVa IVc containing several benzene
rings. Haloacetals Va Vc formed by the same reaction
decompose into alkyl formats VIa VIc and alkyl
halides [1].
1
81 83 C (from hexane). H NMR spectrum, , ppm:
7.5 7.02 m (15H, Ph), 3.0 s (3H, OMe).
Ethoxytriphenylmethane (IIIb), 2.85 (92%), was
obtained from 3 g of monochloride Ia and 1.76 g of
ortho ester IIb (150 C, 7 h), mp 84 C (from hexane).
1H NMR spectrum, , ppm: 7.4 7.0 m (15H, Ph),
3
3.4 q (2H, OCH2, 3JHH 7.5 Hz), 1.18 t (3H, Me, JHH
7.5 Hz).
PhnH3 nCHlg + HC(OR)3
PhnH3 nCOR + HC(OR)2Hlg,
Methoxydiphenylmethane (IVa), 2.76 g (71%),
was obtained from 4 g of monochloride Ib and 2.3 g
of ortho ester IIa (150 C, 6 h), bp 81 83 C (0.05
0.08 mm Hg), nD 0 1.5628. H NMR spectrum, ,
ppm: 7.58 7.22 m (10H, Ph), 5.2 s (1H, CH), 3.5 s
(3H, OMe).
Ia Ic IIa IIc IIIa, IIIb, IVa IVc Va Vc
Va Vc
HCOOR,
VIa VIc
1
RHlg
I, n = 3, Hlg = Cl (a); n = 2, Hlg = Cl (b), Br (c). II, R =
Me (a), Et (b), Bu (c). III, n = 3, R = Me (a), Et (b).
IV, n = 2, R = Me (a), Et (b), Bu (c). V, Hlg = Cl, R = Me
(a), Et (b); Hlg = Br, R = Et (c). VI, R = Me (a), Et (b),
Bu (c).
Ethoxytriphenylmethane (IVb). a. From 2.48 g
of monochloride Ib and 1.99 g of ortho ester IIb
(150 C, 7 h) we obtained 1.65 g (64%) of compound
IVb, bp 149 150 C (9 mm Hg), n2D0 1.5505. H NMR
1
Reaction progress was followed by means of dy-
1
spectrum, , ppm: 7.55 7.18 m (10H, Ph), 5.39 s (1H,
CH), 3.53 q (2H, OCH2, 3JHH 7.5 Hz), 1.2 t (3H, Me,
3JHH 7.5 Hz).
namic H NMR spectroscopy. As the reaction mixture
was heated, the intensity of the singlet signals at
6.17, 6.31, 4.85, and 5.0 ppm of compounds Ib, Ic,
IIa, and IIb decreased and that of the signals at 5.2
(s), 5.39 (s), 3.4 (s), 3.53 (q) ppm from the methine,
methoxyl, and methylene oxide protons of compounds
IVa and IVb, as well as at 3.0 (s), 3.4 (q), and 8.0
(s) ppm from the methoxyl, methylene oxide, and
methane protons of products IIIa, IIIb, and VIa VIc
increased. By the end of heating the signals at 4.85,
5.0 and 6.17, 6.31 ppm disappeared completely,
b. From 3 g of monobromide Ic and 1.98 g of
ortho ester IIb (150 C, 2 h) we isolated 1.43 g (56%)
of compound IVb, bp 150 151 C (9 mm Hg), nD20
1.5498.
Butoxydiphenylmethane (IVc), 4.13 g (89%), was
obtained from 3.9 g of monochloride Ib and 4.92 g of
1070-3632/05/7508-1325 2005 Pleiades Publishing, Inc.
Gazizov
