Reaction of acyl halides and P(III) chlorides with alkyl diphenyl(or triphenyl)methyl ethers [2]

Full text of DOI:10.1134/S107036320702020X

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 2, pp. 309 311.
Original Russian Text M.B. Gazizov, O.D. Khairullina, Sh.N. Ibragimov, R.F. Karimova, D.B. Bagautdinova, O.G. Sinyashin, 2007, published in
Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 2, pp. 337 338.
Pleiades Publishing, Ltd., 2007.
LETTERS
TO THE EDITOR
Reaction of Acyl Halides and P(III) Chlorides
with Alkyl Diphenyl(or Triphenyl)methyl Ethers
M. B. Gazizova, O. D. Khairullinaa, Sh. N. Ibragimova,
R. F. Karimovaa, D. B. Bagautdinovaa, and O. G. Sinyashinb
a Kazan State Technological University,
ul. K.Marksa 68, Kazan, Tatarstan, 420015 Russia
e-mail: mukattisg@mail.ru
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received September 20, 2006
DOI: 10.1134/S107036320702020X
It is known that ortho esters of carboxylic acids
and acetals are used for dehaloalkoxylation of acyl
halides I and P(III) chlorides [1 4]. However, the use
of ethers for this purpose has never been reported.
methyl ethers III, which proceeds regioselectively:
The halogen atom is substituted exclusively by an
alkoxy group. The alternative reaction pathway in-
volving the diphenyl(or triphenyl)methoxy group is
not realized, and we failed to detect alkyl halides
R2Hal even in trace amounts.
In our work we discovered a new reaction of com-
pounds I and II with alkyl diphenyl(or triphenyl)-
R1COHlg + PhnH3 nCOR2
R1COOR2 + PhnH3 nCHlg,
I
III
IV
V
I, R1 = Me, Hlg = Cl (a), Br (b); R1 = Ph, Hlg = Cl (c); III, n = 2, R2 = Me (a), Et (b); n = 3, R2 = Me (c), Et (d); IV,
R1 = Me, R2 = Me (a), Et (b); R1 = Ph, R2 = Me (c), Et (d); V, n = 2, Hlg = Cl (a), Br (b); n = 3, Hlg = Cl (c), Br (d).
X2PCl + III
X2POR2 + V,
II
VI
O
O
O
II, X = Cl (a), X2 =
(b); VI, R2 = Et, X = Cl (a), X2 =
(b).
O
To assess the relative activity of the reagents and
their transformation degree, we studied this reaction
derivative Ib is more active than its chloro analogs Ia
and Ic; acetyl chloride and phosphorus trichloride are
found more reactive than benzoyl chloride and o-phe-
nylene phosphorochloridite, respectively, and tri-
phenyl derivatives IIIc and IIId are less active than
diphenyl derivatives IIIa and IIIb, probably, by steric
reasons.
1
by means of dynamic H NMR spectroscopy, taking
1H NMR spectra every 5 min and tracing the intensity
of the signals at , ppm (assignment, comp. no.):
6.31 s (CH, Vb), 6.17 s (CH, Va), 3.2 s (OMe, IIIa),
3.0 s (OMe, IIIc), 3.5 q (OCH2, IIIb), 3.05 q (OCH2,
IIId), 3.8 s (OMe, IVc), 4.05 q (OCH2, IVb), 4.2 q
(OCH2, IVd). It was found that the reactivity of com-
pounds I, II, and III depends on their nature. Bromo
Reaction of acyl halides I with alkyl diphenyl(or
triphenyl)methyl ethers. A mixture of equal quanti-
309

310
GAZIZOV et al.
n2D0 1.5959 [5]}. H NMR spectrum, , ppm: 6.17 s
1
ties of compound I and III was kept at room tem-
perature for 18 h or heated in a sealed ampule at 70 C
for 13 h; with less active acyl halides, the mixture was
additionally heated at 100 C for 10 h. Ether IV was
collected under high vacuum in a liquid nitrogen trap
and then distilled. Halides V were isolated by recrys-
tallization from hexane or by high-vacuum distillation.
(1H, CHCl), 7.2 7.6 m (10H, Ph).
Reaction of P(III) chlorides II with alkyl di-
phenyl(or triphenyl)methyl ethers. a. A mixture of
1.2 g of IIb and 2 g of IIId was heated at 70 C for
5 h and distilled with a Vigreux column to obtain
1.05 g (83%) of ethyl o-phenylene phosphite (VIb),
bp 87 88 C (15 mm Hg), nD20 1.5091 {published data:
bp 86 C (11 mm Hg), nD20 1.5085 [6]}. H NMR spec-
trum, , ppm: 1.11 t (3H, Me, JHH 7.5 Hz), 3.6 quin-
a. A mixture of 1.65 g of Ib and 3 g of IIIc was
kept at 25 C for 18 h to form 0.98 g (83%) of com-
pound IVb, bp 77 C, n2D0 1.3725 (published data: bp
1
3
77 C, n2D0 1.3723 [5]). H NMR spectrum, , ppm:
1
3
3
tet (2H, OCH2, JHH = JPH = 7.5 Hz), 7.25 s (4H,
C6H4O2). The residue was crystallized from hexane to
isolate 1.54 g (80%) of Vc, mp 111 112 C.
3
1.15 t (3H, Me, JHH 7.5 Hz), 1.9 s (3H, COMe),
3
4.05 q (2H, OCH2, JHH 7.5 Hz). Yield of Vb 2.6 g
(80%), bp 96 98 C (0.06 mm Hg), n2D0 1.6200; mp
45 C {pulished data: bp 172 C (11 mm Hg), mp 45 C
[5]}. H NMR spectrum, , ppm: 6.31 s (1H, CHBr),
7.1 7.6 m (10H, Ph).
b. A mixture of 6.43 g of IIa and 3.36 g of IIId
was kept at 25 C for 30 days and then distilled with a
Vigreux column to obtain 1.3 g (78%) of ethyl phos-
phorodichloridite (VIa), bp 55 58 C (150 mm Hg),
n2D0 1.4662 {published data: bp 55 60 C (150 mm Hg),
1
b. A mixture of 1.34 g of Ib and 3 g of IIIc was
heated at 70 C for 13 h to obtain 0.65 g (81%) of
compound IVa, bp 57 C, n2D0 1.3642 {published data:
n2D0 1.4660 [7]}. H NMR spectrum, , ppm: 1.26 t
1
1
(3H, Me, 3JHH 7.5 Hz), 4.25 quintet (2H, OCH2, 3JHH
=
3JPH = 7.5 Hz). The residue was crystallized from
hexane to isolate 2.6 g (80%) of Vc, mp 112 113 C.
bp 57 C, n2D0 1.3619 [2]}, H NMR spectrum, , ppm:
1.9 s (3H, COMe), 3.8 s (3H, OMe), and 3.39 g
(97%) of halide Vd, mp 152 153 C (published mp
1
152 C [5]), H NMR spectrum, , ppm: 7.02 7.5 m
c. A mixture of 7.75 g of IIa and 3 g of IIIb was
kept at 25 C for 30 days and then distilled with a
Vigreux column to obtain 1.68 g (81%) of VIa, bp
55 59 C (150 mm Hg), nD20 1.4661, and 2.39 g (84%)
of Va, bp 155 C (10 mm Hg), n2D0 1.6000.
(15H, Ph).
c. A mixture of 1.36 g of Ia and 5 g of IIId was
heated at 70 C for 13 h to obtain 1.25 g (82%) of IVb,
bp 77 C, n2D0 1.3722 and 4.68 g (97%) of Vc, mp
112 113 C {published data: bp 230 235 C (20 mm
1
The H NMR spectra were recorded on a Bruker
1
Hg), mp 112 C [5]}. H NMR spectrum, , ppm: 7.1
WP-80 and Tesla BS-567A spectrometers operating at
80 and 100 MHz, respectively. The chemical shifts
were measured for CDCl3 solutions against TMS.
7.5 m (15H, Ph).
d. A mixture of 0.85 g of Ib and 2.08 g of IIId
was heated at 70 C for 13 h to prepare 0.45 g (74%)
of IVb, bp 77 C, n2D0 1.3755 and 1.81 g (81%) of Vd,
mp 151 152 C.
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 03-03-
32547).
e. A mixture of 0.97 g of Ic and 2 g of IIId was
heated at 70 C for 25 h and then at 100 C for 10 h to
obtain 0.81 g (78%) of IVd, bp 91 92 C (15 mm Hg),
n2D0 1.5055 {published data: bp 106 C (25 mm Hg),
REFERENCES
1
n2D0 1.5052 [5]}. H NMR spectrum, , ppm: 1.2 t (3H,
1. Mezheretskii, V.V., Olekhnovich, E.P., Luk’ya-
nov, S.M., and Dorofeenko, G.N., Orto-efiry v organi-
cheskom sinteze (Ortho Ethers in Organic Synthesis),
Rostov-on-Don: Rostov. Gos. Univ., 1976.
2. Barton, D. and Ollis, W.D., Comprehensive Organic
Chemistry, Oxford: Pergamon, 1979, vol. 2. Translated
under the title Obshchaya organicheskaya khimiya,
Moscow: Khimiya, 1983.
3
3
Me, JHH 7.5 Hz), 4.2 q (2H, OCH2, JHH 7.5 Hz),
7 m (5H, Ph) and 1.64 g (86%) of IVc, bp 161 C
(0.14 mm Hg), mp 112 C.
f. A mixture of 1.31 g of Ic and 1.85 g of IIIa was
heated at 70 C for 25 h and at 100 C for 10 h to give
0.91 g (72%) of IVc, bp 199 200 C, n2D0 1.5172
{published data: bp 199.5 C, n2D0 1.5170 [5]}. H
1
NMR spectrum, , ppm: 3.8 s (3H, OMe), 7 m (5H,
Ph) and 1.5 g (80%) of Va, bp 155 C (10 mm Hg),
n2D0 1.5945 {published data: bp 159 C (12 mm Hg),
3. Yanovskaya, A.A., Yufit, S.S., and Kucherov, V.F.,
Khimiya atsetalei (Chemistry of Acetals), Moscow:
Nauka, 1975.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 2 2007

REACTION OF ACYL HALIDES AND P(III) CHLORIDES
311
4. Gazizov, M.B., and Khairullin, R.A., Itogi nauki Tekh.,
Ser. Org. Khim., 1990, vol. 15.
6. Arbuzov, A.E., Izbrannye trudy (Selected Works),
Moscow: Akad. Nauk SSSR, 1952.
5. Svoistva organicheskikh soedinenii. Spravochnik
(Properties of Organic Compounds. Handbook), Po-
tekhin, A.A., Ed., Leningrad: Khimiya, 1984.
7. Kormachev, V.V., and Fedoseev, M.S., Preparativnaya
khimiya fosfora (Preparative Chemistry of Phosphorus),
Perm: Ural. Otd. Ross. Akad. Nauk, 1992.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 2 2007