Reaction of P(IV) mono-and dichlorides with alkyldiphenylmethyl or triphenylmethyl ethers

Full text of DOI:10.1134/S0012500808010060

ISSN 0012-5008, Doklady Chemistry, 2008, Vol. 418, Part 1, pp. 17–18. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © M.B. Gazizov, Sh.N. Ibragimov, D.B. Bagautdinova, R.F. Karimova, O.D. Khairullina, O.G. Sinyashin, 2008, published in Doklady Akademii Nauk,
2
008, Vol. 418, No. 3, pp. 339–340.
CHEMISTRY
Reaction of P(IV) Mono- and Dichlorides
with Alkyldiphenylmethyl or Triphenylmethyl Ethers
M. B. Gazizov, Sh. N. Ibragimov, D. B. Bagautdinova, R. F. Karimova,
O. D. Khairullina, and Academician O. G. Sinyashin
Received July 12, 2007
DOI: 10.1134/S0012500808010060
Orthocarboxylates are known to be used for the
In this work, we have found a new reaction of com-
dechloroalkoxylation of P(IV) mono- and dichlorides I pounds I and II with alkyldiphenylmethyl or triphenyl-
and II [1]. However, no information is available on the methyl ethers (III):
application of ethers for this purpose.
1
2
2
1
2
2
R P(O)Cl + Ph H3 – nCOR
R P(O)OR + I + Ph H3 – nCCl
n
2 n
IV
I
III
V
1
2
1
2
2
R P(O)OP(O)R + R Cl + V
VI
1
2
2
1
I, R = Ph (a), Et (b); III, n = 2, R = Me (a), Et (b), n = 3, R = Me (c); V, n = 2 (a), n = 3 (b); VI, R = Ph (a), Et (b).
3
MeP(O)Cl + 3IIIb
[MeP(O)O] + 3Va + 3EtCl.
2
3
II
VII
At the first stage of the reaction of compounds I and of the resonance signal of the methyne proton at δ
III, the chlorine atom at P(IV) is substituted by an 5.5 ppm and the presence of the signal of the methyne
1
alkoxy group to form compound IV: the H NMR spec- proton in compound Va at δ 6.17 ppm with an initial
trum of a reaction mixture of Ib and IIIc 10 h after their intensity equal to that of the signal at 5.5 ppm. The
mixing shows a resonance signal at δ 3.75 ppm (d, completion of the reaction was determined from the
3
POMe, J = 11 Hz), while that of a mixture of com- disappearance of the doublet and quintet signals of pro-
êç
pounds Ib and IIIb exhibits a signal at δ 3.8 ppm (quin, tons of the POMe and POEt fragments, respectively.
3
3
êéëç ëç , J = J = 7 Hz).
2
3
êç
çç
To terminate the process, the reaction mixture was
heated to 150°C, whereas, in the case of dichloride II,
the temperature was raised to 180°C. The formation of
cyclic trimerVII was completed only under such severe
conditions.
However, the reaction between compounds I and III
occurs rapidly only on heating to 120–150°ë. Taking
into account that compounds I and IVb at this tem-
perature react to form P(IV) acid anhydrides, com-
pound VI [2], or cyclic trimeric anhydride VII in the
Thus, the nucleophilic substitution of the chlorine
case of P(IV) dichloride Ib [2, 3], the reactions of com- atom at P(IV) by an alkoxy group takes place at the first
pounds I with III and II with III were carried out in stage of the reaction of P(IV) chlorides I and II with
2
: 1 and 1 : 1 ratios, respectively. Indeed, the above ethers III. The resulting esters of P(IV) acids react with
reactions were completed to give compounds VI and initial compound I or II and, depending on the number
VII, which were isolated in a pure state.
of chlorine atoms in the latter, the reaction leads to the
formation of acyclic anhydride VI or cyclic trimeric
anhydride VII.
The completion of the first stage of displacement for
ethers IIIa and IIIb was judged from the disappearance
EXPERIMENTAL
1
Kazan State Technological University, ul. Karla Marksa 68,
Kazan, 420015 Tatarstan, Russia
The ç NMR spectra were recorded on a Tesla BS-
567A spectrometer operating at 100 MHz. Proton
1
7

1
8
GAZIZOV et al.
31
chemical shifts were referenced to TMS. The P NMR 9.9 mmol (38%) of a product with bp 120–125°ë
spectra were recorded on a CXP-100 spectrometer (12 mmHg), which consisted of 88% chloride Va and
1
operating at 36.5 MHz with 85% ç êé as the external 12% anhydride VIb according to H NMR.
3
4
reference.
Similarly, the reaction of 10.5 mmol of acid chloride
Reaction of diphenylchlorophosphinate Ia with
Ib and 5.3 mmol of ether IVb resulted in 3.5 mmol
(
diphenylmethyl)methyl ether IIIa. A mixture of
(
67%) of anhydride VIb contaminated with a small
1
3.2 mmol of compound Ia and 6.6 mmol of ether IIIa
amount of chloride Vb and 3.9 mmol (74%) of com-
pound Vb, mp 110–111°C (from hexane) (lit. [5]: mp
was heated in a sealed ampoule under a dry nitrogen
atmosphere at 150°C for 23 h, the pressure being
exhausted periodically. Anhydrous ether (20 mL) was
added to the cold reaction mixture and the mix was
carefully stirred. Crystalline diphenylphosphinic anhy-
dride VIa, precipitated after 10 min, was filtered off,
washed three times with anhydrous ether, and dried in
vacuum to give 5.3 mmol (80%) of compound VIa, mp
1
12°C).
Reaction of methyldichlorophosphonate II with
diphenylmethyl)ethyl ether IIIb. A mixture of
1.3 mmol of methyldichlorophosphonate and
1.3 mmol of (diphenylmethyl)ethyl ether was heated
in a sealed ampoule under a dry nitrogen atmosphere
for 35 h at 150°C and additionally for 9 h at 180°C, the
pressure being exhausted periodically. The distillation
of the liquid part gave 21.6 mmol (71%) of chloride Va,
(
3
3
3
1
1
40–141°C. P NMR (δ, ppm): 25.
For C H O P anal. calcd. (%): P, 14.81.
2
4
20
3 2
2
D
0
Found (%): P, 14.2.
The distillation of the ether extract afforded
.8 mmol (74%) of diphenylchloromethane Va, bp
bp 156°C (10 mmHg), n = 1.5970. The solid residue
in the ampoule was washed three times with anhydrous
ether and recrystallized from chloroform to give
4
1
2
0
15–116°C (0.2 mmHg), nD = 1.5970 (lit. [4]: bp 8.6 mmol (82%) of cyclic trimer VII, mp 110–111°C
1
2
0
(lit. [3]: mp 111–113°C). H NMR (CDCl , δ, ppm):
.43 (d, J = 17 Hz, PMe); ê NMR (δ, ppm): 16.
1
3
1
59°C (12 mmHg), nD = 1.5959). H NMR (CDCl , δ,
3
2
31
1
PH
ppm): 6.17 (s, 1H, CHCl), 7.2–7.6 (m, 10H, 2 Ph).
Similarly, the reaction of 11.4 mmol of compound
Ia and 5.7 mmol of ether IIIb resulted in 4.3 mmol
REFERENCES
(
76%) of anhydride VIa and 4.4 mmol (78%) of chlo-
ride Va.
Reaction of diethylchlorophosphinate Ib with
diphenylmethyl)ethyl ether IIIb. A mixture of
1.6 mmol of compound Ib and 25.8 mmol of ether
1
. Kirby, A.J. and Warren, S.G., The Organic Chemistry of
Phosphorus, Amsterdam: Elsevier, 1967. Translated
under the title Organicheskaya khimiya fosfora, Mos-
cow: Mir, 1971.
. Gazizov, M.B., Kachalova, T.N., Karimova, R.F., Khai-
rullin, R.A., and Sinyashin, O.G., Zh. Org. Khim., 1997,
vol. 67, no. 12, pp. 2055–2056.
. Gazizov, M.B., Kachalova, T.N., Pudovik, M.A., Sady-
kova, A.I., Gazizov, K.M., and Musin, R.Z., Zh. Org.
Khim., 2001, vol. 71, no. 3, pp. 523–524.
. Gazizov, M.B., Ibragimov, Sh.N., Khamidullina, O.D.,
Karimova, R.F., Pudovik, M.A., Sadykova, R.R., and
Sinyashin, O.G., Dokl. Chem., 2004, vol. 395, part 1,
pp. 47–49 [Dokl. Akad. Nauk, 2004, vol. 395, no. 3,
pp. 363–365].
(
5
2
IIIb was heated at 150°C for 24 h and 10 mL of hexane
was added. The bottom layer was treated six times with
hexane, followed by the double distillation of the resi-
due in vacuum to give 16.8 mmol (65%) of a product
with bp 131–132°C (0.2 mmHg) consisting of 95.5%
diethylphosphinic anhydride VIb and 5% diphenyl-
3
4
1
chloromethane Va according to ç NMR. VIb:
1
3
3
1
3
H NMR (CDCl , δ, ppm): 1.13 (dq, 6H, J = 20 Hz,
3
PH
2
JHç = 7.2 Hz, êëç ëç ), 1.66 (dq, 4H, J = 14 Hz,
2
3
PH
31
JHç = 7.2 Hz, êëç ëç ); ê NMR (δ, ppm): 57. Va:
2
3
5
. Gazizov, M.B., Khairullina, O.D., Ibragimov, Sh.N.,
Karimova, R.F., Chirkova, I.N., and Sinyashin, O.G.,
Dokl. Chem., 2006, vol. 409, part 2, pp. 133–134 [Dokl.
Akad. Nauk, 2006, vol. 409, no. 4, pp. 491–492].
H NMR (ëDCl , δ, ppm): 6.17 (s, 1H, CHCl), 7.2–7.6
3
(
m, 10H, 2 Ph). The hexane extracts were concentrated
and the residue was distilled in vacuum to give
DOKLADY CHEMISTRY Vol. 418 Part 1 2008