New reaction of diphenyldichloromethane with aprotic dechloroalkoxylating reagents

Full text of DOI:10.1023/B:DOCH.0000021274.72658.1e

Doklady Chemistry, Vol. 395, Part 1, 2004, pp. 47–49. Translated from Doklady Akademii Nauk, Vol. 395, No. 3, 2004, pp. 353–355.
Original Russian Text Copyright © 2004 by Gazizov, Ibragimov, Khamidullina, Karimova, Pudovik, Sadykova, Sinyashin.
CHEMISTRY
New Reaction of Diphenyldichloromethane
with Aprotic Dechloroalkoxylating Reagents
M. B. Gazizov, Sh. N. Ibragimov, O. D. Khamidullina,
R. F. Karimova, M. A. Pudovik, R. R. Sadykova,
and Corresponding Member of the RAS O. G. Sinyashin
Received December 11, 2003
Methyl esters of P(IV) acids I and orthocarboxyl-
ates II show dechloroalkoxylating reactivity with
respect to organic compounds containing di- and
trichloromethyl groups [1, 2]. However, no information
is available on the application of compounds I and II in
reactions with organic compounds containing a dichlo-
romethylene group. Therefore, we studied reactions of
diphenyldichloromethane III with compounds I and II.
1
2
R R P(O)(OMe) + Ph CCl
2
2
(I)
(III)
1
2
Ph C(OMe)Cl + R R P(O)Cl,
2
(IV)
(V)
IV
Ph C=O + MeCl,
2
(VI)
(VII)
1
2
1
2
(
I + V)
(R R P(O)OP(O)R R + VII),
In this work, we determined the structures of the
products and the general schemes of the reactions under
study.
(VIII)
1
(
3Ib + 3III)
([R P(O)O]
3
+ 6VII + 3VI),
Mixtures of compounds I and III taken in a 1 : 1 or
: 1 ratio and a mixture of compounds II and III taken
(IX)
2
1
2
in a 2 : 1 ratio were heated in sealed ampoules. The
structures of the reaction products were determined by
I, V, and VIII: R = R = Et (a);
1
2
1
31
H and P NMR.
R = Me, R = MeO (b);
The major products of the reaction of compounds Ia
1
IX: R = Me.
and III taken in a 2 : 1 ratio were found to be benzophe-
none VI, diethylphosphinic anhydrideVIII, and methyl
chloride VII. The reaction of Ib with III yielded the
cyclic methylphosphonic anhydride IX as the ultimate
phosphorus-containing product, although the formation
of the intermediate ester anhydride VIIIb was
The conditions and result of the reaction between
compounds II and III depend on the nature of R. When
R = Et, heating at 150°ë for 30 h is required for the
completion of the reaction, the major product being
benzophenone ketal XIa. For R = i-Bu, the time of
heating of the reaction mixture increases to 40 h, com-
pounds XIb and VI being formed in a 3 : 1 ratio. The
other reaction products are alkyl formate XIII and alkyl
chloride XII, which are obviously formed upon the
decomposition of α-chloroacetal X [4].
confirmed by P NMR. In particular, the 31P NMR
31
spectrum of the reaction mixture after heating at 100°C
for 19 h showed three signals with δ 25, 22, and
P
1
6 (weak) ppm. These signals correspond to the P(IV)
atoms in compounds Ib, VIIIb, and IX, respectively.
The formation of product VIII from compounds I and
V was described in [3]. Cyclic anhydride IX is
obviously a product of the successive interaction of
anhydride VIIIb with the starting reactants III and I
followed by the intramolecular cyclization of the inter-
mediate, containing three phosphorus atoms:
Me(MeO)P(O)OP(O)(Me)OP(O)(Cl)(Me).
(
HC(OR) + Ph CCl )
3 2 2
(III)
(II)
Ph C(OMe)Cl + HC(OR) Cl,
2
2
(IV)
(X)
IV + II
Ph C(OR) + X,
2 2
(XI)
IV
HC(OR) Cl
VI + RCl,
(
XII)
Kazan State Technological University, ul. Karla Marksa 68,
Kazan, 420015 Tatarstan, Russia
Arbuzov Institute of Organic and Physical Chemistry,
Kazan Scientific Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
HCOOR + XII,
2
(XIII)
II, XI, XII, and XIII: R = Et (a), i-Bu (b).
0
012-5008/04/0003-0047 © 2004 åÄIä “Nauka /Interperiodica”

4
8
GAZIZOV et al.
Diphenyldichloromethane is known to show high the supernatant, the signals with δ 25 and 22 ppm were
ê
1
electron-accepting properties [5]. Therefore, we absent; in the H NMR spectrum, the signals at 3.55 (d,
3
3
believe that compounds I and II in the reactions under
J
= 12 Hz) and 3.80 ppm (d, J = 12 Hz) corre-
PH PH
study are aprotic dechloroalkoxylating nucleophiles: sponding to the methoxy group protons in compounds Ib
the substitution of an alkoxy group for a chlorine atom and VIIIb were absent. The supernatant was poured
in compound III occurs at the first stage of the reaction. into a distillation flask, and the precipitate was washed
When methyl esters of P(IV) acids are used, the with CCl . The latter was removed in vacuum. The sub-
4
intermediate α-chloroester IV is stabilized by elimina- sequent distillation of the residue gave 2.44 g (80%) of
tion of methyl chloride to form ketone VI. An analo- benzophenone, bp 155°C (10 mm Hg), mp 49°C. The
gous decomposition of aromatic α-chloroesters was recrystallization of the precipitate from chloroform
1
described in [6]. In contrast to compounds I, orthocar- gave 0.66 g (51%) of anhydride IX, mp 111–113°C. H
2
boxylates II show dechloroalkoxylating ability with NMR (CDCl , δ, ppm): 1.43 (d, J = 17 Hz, P(O)Me);
3
PH
respect to the intermediate α-chloroester IV, which δê 16 ppm.
results in the formation of ketal XI. However, this reac-
tivity of orthoester II decreases as the radical R
becomes more complicated, and a part of the α-chlo-
roester transforms into benzophenone.
For ë ç é ê anal. calcd. (%): P, 39.71. Found
%): P, 39.86.
3
9
6 3
(
Thus, we found a new reaction of diphenyldichlo-
romethane III with esters of P(IV) acids I and orthocar-
boxylates II, which begins with the exchange of a chlo-
rine atom for an alkoxyl group; then, depending on the
nature of the dechloroalkoxylating reactant, the ratio of
the reactants, and the temperature, the reaction yields
benzophenone VI or its dialkyl ketal XI and dieth-
ylphosphinic or methylphosphonic anhydride (VIII
and IX, respectively).
Interaction of Compounds II and III
(
a) A mixture of 27.96 mmol of orthoester IIa and
1
3.98 mmol of compound III was heated in a sealed
1
ampoule at 150°ë for 30 h. The H NMR spectrum of
the reaction mixture did not show the singlet at
5
.05 ppm of the methine proton of compound IIa. The
distillation of the reaction mixture in vacuum gave 2.65 g
(
(
74%) of benzophenone diethyl ketal, bp 150–152°ë
10 mm Hg), mp 51–52°ë (lit.: bp 294–295°ë,
1
mp 51−52°ë [8]). H NMR (CDCl , δ, ppm): 1.2 (t, 6H,
3
3
3
JHH = 7.5 Hz, Me), 3.37 (q, 4H, J = 7.5 Hz, OCH2),
HH
EXPERIMENTAL
7
.0–7.8 (m, 10H, Ph).
b) A mixture of 35.5 mmol of orthoester IIc and
6.9 mmol of compound III was heated in a sealed
1
The H NMR spectra were recorded on Bruker WP-80
(
and Tesla BS-567A spectrometers operating at 80
and 100 MHz, respectively. Proton chemical shifts
1
ampoule at 150°ë for 40 h. Volatile products were
removed in vacuum into a trap with liquid nitrogen. The
distillation of the residue gave 3.4 g of a fraction with
bp 160–167°ë (10 mm Hg) containing benzophenone
3
1
are referenced to TMS. The P NMR spectra were
recorded on an RYa-2303 spectrometer at 21 MHz,
with 85% ç êé as the external reference.
3
4
1
and its diisobutyl ketal in a 1 : 3 ratio. H NMR of this
3
fraction (CDCl , δ, ppm): 1.0 (d, 12H, J = 6.75 Hz,
3
HH
Interaction of Compounds I and III
3
Me), 1.75–2.17 (m, 2H, CH), 3.1 (d, 4H, J
=
HH
6
7
.25 Hz, OCH ), 7.10–7.75 (m, 10H, ketal Ph), 7.42–
(
a) A mixture of 14.56 mmol of compound III and
2
.90 (m, benzophenone Ph). The distillation of the con-
2
9.12 mmol of O-methyl diethylphosphinate Ia was
1
densate from the trap gave 1.37 g of isobutyl chloride
heated at 120°ë for 10 h. In the H NMR spectrum of
15
XIIb, bp 68–69°ë (lit.: 68.9°C, nD 1.4010 [9]), and
2.18 g of product XIIIb, bp 96–97°ë (lit.: bp 98°ë [7]).
the reaction mixture, the resonance signal with δ
3
3
.57 ppm and J = 12 Hz corresponding to the
PH
methoxy group protons of compound Ia was absent.
The distillation of the reaction mixture gave 2.1 g
(
79%) of benzophenone, bp 155°ë (10 mm Hg),
ACKNOWLEDGMENTS
mp 49°ë (lit.: mp 49°ë [7]), and 1.2 g (36.4%) of the
2
5
This work was supported by the Russian Foundation
for Basic Research, project no. 03–03–32547.
anhydride VIIIa, bp 112°ë (0.05 mm Hg), n 1.4625.
D
1
3
3
3
H NMR (CDCl , δ, ppm): 1.13 (dt, 6H, J = 20 Hz,
3
PH
2
JHH = 7.2 Hz, PCH CH ), 1.66 (dq, 4H, J = 14 Hz,
2
3
PH
JHH = 7.2 Hz, PCH CH ); δ 60 ppm.
2
3
P
REFERENCES
(
b) A mixture of 16.7 mmol of O,O-dimethyl meth-
ylphosphonate and 16.7 mmol of compound III was
1. Gazizov, M.B., Kachalova, T.N., Karimova, R.F., and
Sinyashin, O.G., Dokl. Akad. Nauk, 1998, vol. 359,
no. 5, pp. 644–646 [Dokl. Chem. (Engl. Transl.),
vol. 359, nos. 4–6, pp.71–73].
3
1
heated in a sealed ampoule at 100°ë for 19 h. A P
NMR spectrum of the reaction mixture was recorded,
methyl chloride was removed, and the content of the
ampoule was heated again at 120°ë for 9 h. An abun-
2. Gazizov, M.B., Kachalova, T.N., Karimova, R.F., et al.,
Zh. Obshch. Khim., 1997, vol. 67, no. 12, pp. 2055–2056.
31
dant precipitate formed. In the P NMR spectrum of
DOKLADY CHEMISTRY Vol. 395 Part 1 2004

NEW REACTION OF DIPHENYLDICHLOROMETHANE
49
3
. Kosolapoff, G. and Watson, R., J. Am. Chem. Soc., 1951,
7. Spravochnik khimika. Osnovnye svoistva neorga-
nicheskikh i organicheskikh soedinenii (Handbook on
Chemistry: Main Properties of Inorganic and Organic
Compounds), Nikol’skii, B.P., Ed., Leningrad: Khimiya,
vol. 73, no. 9, pp. 4101–4102.
4
. Mezheritskii, V.V., Olekhnovich, E.P., Luk’yanov, S.M.,
and Dorofeenko, G.N., Ortoefiry v organicheskom sin-
teze (Orthoesters in Organic Synthesis), Rostov-on-Don:
Rostov. Univ., 1976.
. Weygand, C. and Hilgetag, G., Organisch-Chemische
Experimentierkunst (Experimental Methods in Organic
Chemistry), Leipzig: Johann Ambrosius Barth, 1964.
. Pokonova, Yu.V., Galoidefiry. Sposoby polucheniya,
svoistva, primenenie (Haloesters: Synthesis, Properties,
and Application), Moscow: Khimiya, 1966.
1
964, vol. 2.
8
. Dictionary of Organic Compounds, Heilbron, I. and
Bunbury, H.M., Eds. Translated under the title Slovar’
organicheskikh soedinenii, Moscow: Inostrannaya Lite-
ratura, 1949, vol. 1.
5
6
9. Perel’man, V.I., Kratkii spravochnik khimika (Chemist’s
Concise Handbook), Moscow: Goskhimizdat, 1963.
DOKLADY CHEMISTRY Vol. 395 Part 1 2004