Mechanism of reactions of P(III) amidoesters with carboxylic acid chlorides [4]

Full text of DOI:10.1023/B:RUGC.0000016008.08714.a5

Russian Journal of General Chemistry, Vol. 73, No. 9, 2003, pp. 1495 1496. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 9, 2003,
pp. 1581 1582.
Original Russian Text Copyright
2003 by Sal’keeva, Nurmagambetova, Kurmanaliev.
LETTERS
TO THE EDITOR
Mechanism of Reactions of P(III) Amidoesters
with Carboxylic Acid Chlorides
L. K. Sal’keeva, M. T. Nurmagambetova, and O. Sh. Kurmanaliev
Buketov Karaganda State University, Karaganda, Kazakhstan
Received June 24, 2002
One of us previously showed [1, 2] that tert-butyl
phosphoramidites react with acetyl chloride by
an Arbuzov reaction scheme to form phosphorochlo-
ridites and acetylphosphonates via a quasiphospho-
nium intermediate. 2-tert-Butoxy-3-phenyl-1,3,2-
oxazaphospholane (I) obtained by transamidation of
tert-butyl tetraethylphosphorodiamidite (II) with
2-(phenylamino)ethanol has not been studied in these
reactions.
We found that oxazaphospholane I, too, reacts with
carboxylic acid chlorides also by an Arbuzov reaction
scheme to give acetylphosphonamidate III and ben-
zoylphosphonamidate IV.
Ph
NHPh
OH
N
O
(
Et N) POBu-t +
POBu-t + 2Et NH
2
2
2
II
I
Ph
Ph
O O
O CH2
N
O
MeCOCl
N
MeCOCl, Et N
3
P C Me
P C OCOMe
Me C=CH ,
2
2
O
Et N HCl
3
HCl
III
V
I
Ph
Ph
NO2
O Ph
P C=N
O O
N
O
PhCOCl
Me C=CH ,
N
P C Ph + NH NH
NO2
NO2
2
2
2
O
HCl
NO2
IV
VI
5
2
-tert-Butoxy-3-phenyl-1,3,2-oxazaphospholane
2-( -Acetoxyvinyl)-3-phenyl-1,3,2 -oxaza-
2
0
(
I), oil, isolated by column chromatography on silica
gel, eluent 1:1 ethyl acetate benzene, n 1.5076. IR
spectrum, , cm : 1020 (P O C), 1080 (C O), 1320
phospholane 2-oxide (V), bp 110 112 (2 mm), n
.4853, d 1.1552. IR spectrum, , cm : 1230 (P=O),
620 (C=C), 1700 (C=O). H NMR spectrum, , ppm
D
2
4
0
1
2
0
1
1
(
D
1
1
3
3
1
J, Hz): 2.6 s (CH C=O), 6.3 d (H C=, J 4 Hz).
(
P N), 1450, 1470, 1580 (Ph). P NMR spectrum:
36.7 ppm.
3
2
PH
Found, %: C 53.57; H 5.28; N 5.43; P 11.46.
C H NO P. Calculated, %: C 53.24; H 5.24; N 5.24;
1
P
1
2
14
4
5
2
-Acetyl-3-phenyl-1,3,2 -oxazaphospholane
P 11.61.
2
0
20
2
1
(
-oxide (III), bp 98 100 C (3 mm), n 1.5270, d4
D
5
1
2
-Benzoyl-3-phenyl-1,3,2 -oxazaphospholane
-oxide (IV), oil, isolated by column chromatography
on silica gel, eluent 1:1 ethyl acetate benzene, nD
.3752. IR spectrum, , cm : 1220 (P=O), 1720
21.1 ppm. Found, %:
C=O). 31P NMR spectrum:
2
P
2
0
C 53.33, N 6.22; P 13.78.
1
070-3632/03/7309-1495$25.00 2003 MAIK Nauka/Interperiodica

1496
SAL’KEEVA et al.
1
1
(
.5288. IR spectrum, , cm : 1225 (P=O), 1710
measured on
(32.44 MHz) against external 85% phosphoric acid.
a
Bruker WP-80 spectrometer
C=O). 31P NMR spectrum:
27.7 ppm.
P
2
-[(2,4-Dinitrophenylhydrazono)(phenyl)me-
5
REFERENCES
thyl]-3-phenyl-1,3,2 -oxazaphospholane 2-oxide,
mp 135 C.
1
2
. Gazizov, T.Kh., Sal’keeva, L.K., Gafurov, E.K., and
Kazantsev, A.V., Zh. Obshch. Khim., 1988, vol. 58,
no. 5, p. 1155.
The IR spectra were recorded on a Specord IR-75
spectrometer in thin layer. The H NMR spectra were
obtained on a Varian T-60 spectrometer (60 MHz)
against internal TMS. The P NMR spectra were
1
. Sal’keeva, L.K., Usmanova, L.N., and Gazizov, T.Kh.,
Zh. Obshch. Khim., 1992, vol. 62, no. 2, p. 353.
3
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 9 2003