A general method for the synthesis of Te-aryl phosphorotellurate triesters

Article abstract of DOI:10.1055/s-2004-822386

A general and practical method for the synthesis of Te-aryl phosphorotellurates is described. A series of Te-aryl phosphorotellurates could be synthesized in good to excellent yields by the reaction of dialkyl, diaryl and trialkyl phosphites with arenetel

Full text of DOI:10.1055/s-2004-822386

PAPER
1481
A General Method for the Synthesis of Te-Aryl Phosphorotellurate Triesters
S
ynthesis of Phosphor
o
i
tellura
n
te Triesters oru Hayashi,* Toshiyuki Miura, Keiji Matsuchika, Yutaka Watanabe*
Department of Applied Chemistry, Faculty of Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan
Fax +81(89)9279944; E-mail: hayashi@eng.ehime-u.ac.jp
Received 15 April 2004
Dedicated to Professor Teruaki Mukaiyama on the occasion of the celebration of his 77th birthday
alkyl(diaryl) phosphorotellurate in excellent yields
Abstract: A general and practical method for the synthesis of Te-
(Scheme 1, Table 1, entries 1–5). Trialkyl phosphites also
gave the phosphorotellurates in excellent yields via the
Arbuzov-type dealkylation in the presence of a small
aryl phosphorotellurates is described. A series of Te-aryl phospho-
rotellurates could be synthesized in good to excellent yields by the
reaction of dialkyl, diaryl and trialkyl phosphites with arenetellury-
nyl and arenetellurenyl halides. A phenylphosphonotelluroate and a amount of 2,6-lutidine instead of triethylamine (Table 1,
phosphorotelluramidate were also prepared by a similar procedure.
entries 7–10). Although most of trialkyl phosphites suc-
cessfully reacted without base to give the desired product
in good yields, the addition of 2,6-lutidine was found to be
effective to avoid deposition of elemental tellurium with
decomposition of the product during the reaction, which
sometimes occurred without base (Table 1, entry 6).
Key words: phosphorus, phosphorotellurates, tellurium
General methods for the synthesis of phosphate esters and
phosphorochalcogenoates esters bearing thio and/or sele-
no substituents have been well established, and many
kinds of such compounds have been prepared for both
synthetic and biological studies.1 In contrast, there are
only two examples of the heavier analogues, i.e. phospho-
rotellurate esters, as unstable compounds, reported so far.2
Both examples are the Te-alkyl esters, which were synthe-
sized by alkylation of sodium or triethylammonium salts
of phosphorotellurates. In spite of the growing utilities of
organotellurium compounds in organic synthesis,3 there is
no other way for the preparation of phosphorotellurate es-
ters and therefore only little was known about their reac-
tivities, although the phosphorotellurate esters should
provide a great interest on account of their reactivities.
Herein we wish to report a general, and practical method
for the preparation of Te-aryl phosphorotellurates by the
reaction of phosphites with arenetellurynyl or arenetel-
lurenyl halides. Syntheses of a phenylphosphonotellurate
and a phosphorotelluramidate by a similar procedure are
also described.
Scheme 1
The reactions using AnTeCl3 required two molar equiva-
lents of the phosphite. The fact shows that the Te(IV) re-
agent is first reduced to AnTeCl, and then this reactive
Te(II) species react with another mole of phosphite, re-
sulting in the formation of the phosphorotellurates. Based
Table 1 Synthesis of Phosphorotellurate 2 with Arenetellurynyl
Chloride and Di- or Trialkylphosphites
Entry
R
R1
Basea
Time
(h)
Prod- Yield
uct
2a
2b
2c
2d
2e
2f
(%)
86
83
95
95
76
77c
94
91
89
89
1
2
Et
H
Et3N
0.5
1.0
4.0
2.0
1.0
0.2
1.0
0.7
0.7
1.0
We have already reported tellurium tetrachloride-mediat-
ed oxidative phosphorylation of alcohols and thiols by tri-
alkyl phosphites.4,5 During the course of our mechanistic
study of this reaction using p-methoxybenzenetellurynyl
chloride instead of TeCl4, we found that Te-p-methoxy-
phenyl O,O¢-dialkyl phosphorotellurate was formed in
concomitant with the phosphorylation of the alcohol.
Then, the reaction condition was optimized for maximiz-
ing the yields of these rare phosphorotellurates.
n-Bu
Bn
H
Et3N
3
H
Et3N
4
Ph
H
Et3N
5
o-Xyb
Me
Me
Et
H
Et3N
6
Me
Me
Et
none
7
2,6-lutidine
2,6-lutidine
2,6-lutidine
2,6-lutidine
2f
In the presence of an excess triethylamine, p-methoxyben-
zenetellurynyl chloride (AnTeCl3)6 smoothly reacted with
2 equivalents of dialkyl or diaryl phosphite at room tem-
perature to afford the corresponding Te-aryl O,O¢-di-
8
2a
2b
2c
9
n-Bu
Bn
n-Bu
Bn
10
a Amount of base: Et3N (3.3–3.6 equiv); 2,6-lutidine (0.5 equiv).
b o-Xy represents o-xylylenediyl.
SYNTHESIS 2004, No. 9, pp 1481–1485
Advanced online publication: 26.05.2004
DOI: 10.1055/s-2004-822386; Art ID: C03004SS
© Georg Thieme Verlag Stuttgart · New York
x
x
.
x
x
.2
0
0
4
c Elemental tellurium was deposited due to decomposition.

1482
M. Hayashi et al.
PAPER
on the consideration, we chose Te(II) species instead of
AnTeCl3. Arenetellurenyl halides7a (ArTeX, X = Cl, I) are
Te(II) species of choice, which are easily prepared by the
oxidation of diaryl ditellurides with halogen sources such
as sulfuryl chloride or iodine. As expected, the reaction of
ArTeX with an equimolar amount of phosphites gave the
corresponding phosphorotellurates in good yields
(Scheme 2, Table 2). This procedure provides a quite gen-
eral and efficient route toward the phosphorotellurate tri-
esters owing to wide availability of various diorganyl
ditellurides by several methods.7b
Scheme 4
The phosphorotellurates and derivatives described here
are stable enough to handle in air, and could be purified by
a simple column chromatography on silica gel. They
could be stored in solution for weeks without detectable
decomposition. It is in contrast to the reported Te-alkyl
phosphorotellurates that are known as too unstable and
sensitive towards air and moisture.2 The Te-aryl phospho-
rotellurates gradually turned orange to form the corre-
sponding diaryl ditellurides and pyrophosphates when
they are kept neat. Noteworthy is that a cyclic phosphoro-
tellurate 2e, isolated in a crystalline form, is quite stable
even in solid state and did not decompose for months.
Although phosphoroselenoate esters can be prepared by
the reaction of phosphorochloridates with alkylselenide
salt,8 an investigation of tellurium version was not suc-
cessful at all probably due to instability of the product un-
der strong basic condition.
The structure of the phosphorotellurates was confirmed
by 1H, 13C, 31P, 125Te NMR and FABMS data. Character-
istic 125Te-satellite peaks were observed in 31P NMR spec-
tra with large coupling constants (1J31
Te = 1128–1552
Scheme 2
125
P–
Hz) that indicated the direct connection between the phos-
phorus and the tellurium atoms (Table 3). Similar large
coupling constants were reported for a Te-alkyl phospho-
rotellurate and phosphoroselenoates. 125Te NMR spectra
showed doublet peaks with the same coupling constants
observed in 31P NMR spectra. A characteristic isotopic
fingerprint around calculated molecular mass weights in
their FABMS spectra also supported the expected struc-
ture.
Table 2 Synthesis of 2 from Arenetellurenyl Halides
Entry
R
R1
ArTeXa Baseb
Time Prod- Yield
(h)
uct
(%)
83
80
88
92
88
95
1
2
3
4
5
6
Me
Me
AnTeCl 2,6-lutidine 2.0
2f
n-Bu n-Bu AnTeCl 2,6-lutidine 1.5
2b
2d
2g
2h
2i
Ph
Et
H
H
H
H
AnTeCl Et3Nc
1.0
2.0
1.0
1.0
Since only little is known about the reactivities of phos-
phorotellurates,9 further study of the phosphorotellurates
is now under investigation.
PhTeId
PhTeId
PhTeIe
Et3N
Et3N
Et3N
Ph
Bn
a AnTeCl was prepared in situ from An2Te2 and SO2Cl2. PhTeI was
prepared from Ph2Te2 and I2 and used in situ or after isolation.
b Amount of base: 2,6-lutidine (0.5 equiv); Et3N (1.2–1.4 equiv, ex-
cept entry 3).
Phosphorotellurates 2 from AnTeCl3; Te-p-Methoxyphenyl
O,O¢-Diethyl Phosphorotellurate (2a); Typical Procedure
(Scheme 1)
To a stirred suspension of p-methoxybenzenetellurynyl chloride
(37.3 mg, 0.11 mmol) in CH2Cl2 (1.0 mL) was added successively
diethyl phosphite (34.5 mg, 0.25 mmol) and Et3N (36.4 mg, 0.36
mmol) at r.t. under N2. After stirring the mixture at r.t. until the
phosphite had been almost consumed (monitored by TLC), H2O
was added in one portion. The mixture was extracted with EtOAc,
washed successively with aq 1 N HCl, aq sat. NaHCO3 and brine.
The organic extract was dried (MgSO4), evaporated to dryness, and
the residue was purified by column chromatography on silica gel
(EtOAc–n-hexane, 1:1) to afford 2a (34.9 mg, 86%) as a colorless
oil. When a trialkyl phosphite was used, 2,6-lutidine (ca. 0.5 equiv)
was applied as base instead of Et3N (Tables 1 and 3).
c Excess amount of Et3N (3.5 equiv) was used.
d Isolated PhTeI was used.
e PhTeI was prepared and used in situ.
In addition to the phosphorotellurates, Te-aryl phe-
nylphosphonotellurate and Te-aryl phosphorotellurami-
date are successfully prepared by the same procedure
from O,O¢-diethyl phenylphosphonite and O,O¢-dibenzyl
N,N-diisopropyl
phosphoramidite,
respectively
(Schemes 3 and 4). Contrary to the case of the phospho-
nite, O-ethyl diphenylphosphinite gave diaryl ditelluride
quantitatively instead of the phosphinotellurate ester.
Phosphorotellurates 2 from ArTeX; Te-p-Methoxyphenyl O,O¢-
Diphenyl Phosphorotellurate (2d); Typical Procedure (Scheme
2)
To a stirred solution of bis(p-methoxyphenyl) ditelluride (39.7 mg,
0.085 mmol) in CH2Cl2 (1.0 mL) was added SO2Cl2 (13.7 mg, 0.10
mmol) at r.t. to prepare p-methoxybenzenetellurenyl chloride in
situ. After the color of the reaction mixture turned orange to dark
red (ca. 1 h), diphenyl phosphite (47.5 mg, 0.20 mmol) was added
Scheme 3
Synthesis 2004, No. 9, 1481–1485 © Thieme Stuttgart · New York

PAPER
Synthesis of Phosphorotellurate Triesters
1483
Table 3 1H, 13C, 31P, 125Te NMR Data for Compound 2a–i, 3 and 4
Product 1H NMR (400 MHz, CDCl3)
13C{1H} NMR (100 MHz, CDCl3)
d, J (Hz)
31P{1H} NMR
(162 MHz, CDCl3) d (126 MHz, CDCl3) d
125Te{1H} NMR
d, J (Hz)
3
2a
2b
1.32 (t, 6 H, J = 7.2), 3.80 (s, 3 H),
4.05–4.21 (m, 4 H), 6.77–6.82 (m, 2
H), 7.72–7.76 (m, 2 H)
15.76 (d, JP-C = 7.3), 55.14, 63.31 (d,
–0.79 (with satellite 362.6 (d, 1JP-Te
=
2JP-C = 5.7), 97.68 (d, 2JP-C = 7.9), 115.63 doublet1JP-Te = 1370 1370 Hz)
(d, 3JP-C = 2.2), 141.80 (d, 4JP-C = 3.4),
160.46 (d, 5JP-C = 2.8)
Hz)
0.90 (t, 6 H, J = 7.4), 1.35 (sext, 4 H, 13.56, 18.73, 31.90 (d, 3JP-C = 7.2), 55.16, –0.71 (with satellite 362.5 (d, 1JP-Te
=
J = 7.4), 1.63 (quint, 4 H, J = 7.1),
67.04 (d, 2JP-C = 6.2), 97.67 (d, 2JP-C
=
doublet1JP-Te = 1364 1364 Hz)
Hz)
3.80 (s, 3 H), 3.98–4.11 (m, 4 H), 6.79 7.7), 115.59 (d, 3JP-C = 2.4), 141.82 (d,
(d, 2 H, J = 8.3), 7.74 (dd, 3JH-H = 8.4, JP-C = 3.7), 160.47 (d, 5JP-C = 2.4)
4
4JP-H = 1.2)
2
2c
2d
2e
3.76 (s, 3 H), 5.05 (dd, 2 H, J = 9.0,
11.8), 5.08 (d, 2 H, J = 8.6, 11.8),
55.12, 68.52 (d, JP-C = 6.0), 97.40 (d,
2JP-C = 8.0), 115.60 (d, 3JP-C = 2.2),
–1.53 (with satellite 396.7 (d, 1JP-Te
doublet1JP-Te = 1418 1418 Hz)
Hz)
=
=
=
=
6.69–6.71 (m, 2 H), 7.25–7.35 (m, 10 127.97, 128.38, 128.43, 135.32 (d, 3JP-C
=
4
H), 7.62–7.66 (m, 2 H)
7.8), 142.0 (d, JP-C = 3.5), 160.54 (d,
5JP-C = 2.4)
3.80 (s, 3 H), 6.73–6.75 (d, 2 H), 7.13– 55.14, 97.16 (d, 2JP-C = 8.0), 115.68 (d,
7.36 (m, 10 H), 7.55–7.58 (m, 2 H)
3JP-C = 2.0), 120.93, 120.97, 125.43 (d,
–9.98 (with satellite 445.9 (d, 1JP-Te
doublet1JP-Te = 1552 1552 Hz)
3JP-C = 2.0), 129.37, 129.71 (d, 3JP-C = 1.0), Hz)
142.51 (d, 4JP-C = 3.0), 150.17 (d, 2JP-C
8.0), 160.78 (d, 3JP-C = 2.0)
=
2
3.79 (s, 3 H), 5.15 (dd, 2 H, JH-H = 14.2, 55.19, 68.12 (d, JP-C = 8.0), 95.77 (d,
3.80 (with satellite
389.3 (d, 1JP-Te
JP-H = 17.0), 5.19 (dd, 2 H, JH-H = 14.2, JP-C = 7.4), 115.91 (d, 3JP-C = 2.3),
doublet1JP-Te = 1438 1438 Hz)
2
JP-H = 21.4), 6.79–6.82 (m, 2 H), 7.15– 128.29, 128.71, 134.51, 142.39 (d, 4JP-C
=
Hz)
7.20 (m, 2 H), 7.28–7.32 (m, 2 H),
7.82–7.85 (m, 2 H)
3.4), 160.83 (d, 5JP-C = 2.5)
2
2f
3.72 (d, 6 H, 3JP-H = 13.2), 3.80 (s, 3
H), 6.80 (d, 2 H, J = 8.4), 7.74 (dd,
J = 8.8, 4JP-H = 1.4)
53.55 (d, JP-C = 5.1), 55.15, 97.14 (d,
3.93 (with satellite
331.7 (d, 1JP-Te
2JP-C = 8.2), 115.74 (d, 3JP-C = 2.3), 141.91 doublet1JP-Te = 1405 1405 Hz)
(d, 4JP-C = 3.6), 160.58 (d, 5JP-C = 2.6)
Hz)
2g
1.31 (t, 6 H, 2JH-H = 7.2), 4.05–4.21
15.69 (3JP-C = 7.4), 63.41 (d, 2JP-C = 5.5),
–0.57 (with satellite 382.2 (1JP-Te = 1343
(m, 4 H), 7.25 (t, 2 H, J = 7.2), 7.36 (t, 108.77 (d, 2JP-C = 8.0), 128.82 (d, 5JP-C
=
doublet1JP-Te = 1343 Hz)
1 H, J = 6.0), 7.84 (d, 2 H, J = 8.0)
2.2), 129.59 (d, 3JP-C = 1.9), 139.83 (d,
4JP-C = 4.0)
Hz)
2h
2i
3
0.89 (t, 6 H, J = 7.6), 1.34 (sext, 4 H, 13.51, 18.68, 31.82 (d, 3JP-C = 7.2), 67.12 –0.40 (with satellite 381.0 (1JP-Te = 1339
J = 7.6), 1.63 (quint, 4 H, J = 7.6),
(d, 2JP-C = 6.2), 108.78 (d, 2JP-C = 7.9),
128.76 (d, 5JP-C = 2.2), 129.54 (d, 3JP-C
doublet1JP-Te = 1339 Hz)
4.00–4.12 (m, 4 H), 7.22–7.28 (m, 2
=
Hz)
H), 7.33–7.38 (m, 1 H), 7.82–7.84 (m, 1.8), 139.81 (d, 4JP-C = 4.0)
2 H)
5.04 (d, 1 H, J = 12.0), 5.07 (d, 1 H,
68.67 (d, 2JP-C = 6.0), 108.52 (d, 2JP-C
=
–1.24 (with satellite 413.3 (1JP-Te = 1390
doublet1JP-Te = 1390 Hz)
J = 11.6), 5.08 (d, 1 H, J = 12.0), 5.10 8.1), 128.03, 128.44, 128.46, 128.95 (d,
(d, 1 H, J = 11.6), 7.17 (t, 2 H, J = 7.6), JP-C = 2.4), 129.62 (d, 4JP-C = 2.0), 135.21 Hz)
3
7.23–7.37 (m, 11 H), 7.73–7.78 (m, 2 (d, 3JP-C = 7.9), 140.12 (d, 5JP-C = 4.0)
H)
3
1.40 (t, 3 H, J = 7.1), 3.77 (s, 3 H),
4.20–4.37 (m, 2 H), 6.66–6.68 (m, 2
H), 7.33–7.57 (m, 7 H)
15.94 (d, JP-C = 7.1), 55.10, 63.02 (d,
22.7 (with satellite
483.23 (d, 1JP-Te
=
2JP-C = 6.9), 99.04 (d, 2JP-C = 6.0), 115.38 doublet1JP-Te = 1129 1129 Hz)
(d, 3JP-C = 1.9), 127.98 (d, 2JP-C = 14.3),
130.45 (d, 3JP-C = 11.5), 132.18 (d, 4JP-C
Hz)
=
3.4), 135.23 (d, 1JP-C = 118.1), 142.31 (d,
4JP-C = 2.6), 160.40 (d, 5JP-C = 2.1)
4
1.10 (d, 6 H, J = 6.4), 1.19 (d, 6 H,
21.67, 22.98, 46.65 (d, 2JP-C = 5.8), 55.12, 2.92 (with satellite
464.2 (1JP-Te = 1148
J = 6.4), 3.51 (sept, 1 H, J = 6.8), 3.57 66.51 (d, 2JP-C = 6.9), 99.22 (d, 2JP-C = 6.9), doublet1JP-Te = 1148 Hz)
(sept, 1 H, J = 6.8), 3.78 (s, 3 H), 4.99 115.30 (d, 3JP-C = 2.0), 127.68, 128.02,
Hz)
(dd, 1 H, 3JP-H = 8.0, 2JH-H = 12.0),
128.40, 136.33 (d, 3JP-C4 = 8.0), 142.06 (d,
JP-C = 3.2), 160.17 (d, 5JP-C = 2.2)
5.79 (dd, 1 H, 3JP-H = 8.8, 2JH-H
=
12.0), 6.74 (d, 2 H, J = 8.7), 7.27–7.36
(m, 5 H), 7.78 (d, 2 H, J = 8.7)
Synthesis 2004, No. 9, 1481–1485 © Thieme Stuttgart · New York

1484
M. Hayashi et al.
PAPER
and the resulting mixture was stirred for 1 h at r.t. Then H2O was
added, and the mixture was extracted with EtOAc, washed succes-
sively with aq sat. NaHCO3, H2O and brine. The organic extracts
were dried (MgSO4), evaporated, and the residue was purified by
silica gel column chromatography (EtOAc–n-hexane, 1:4) to afford
2d (74.5 mg, 88%). PhTeI was prepared similarly from diphenyl di-
telluride and I2. Procedure for the preparation of 2 from the isolated
PhTeI was the same as that for AnTeCl3 except for the amount of
the phosphite used (Tables 2 and 3).
Te-Phenyl O,O¢-Diethyl Phosphorotellurate (2g)
Rf = 0.20 (EtOAc–n-hexane, 1:4).
IR (neat): 3066, 2981, 2900, 1562, 1473, 1389, 1238, 1161, 1014,
964 cm–1.
FABMS: m/z calcd for C10H15PO3Te: 344; found: a maximum at
345 with tellurium isotopic fingerprint ranged between 336 and
346; 336 (5), 337 (11), 338 (11), 339 (24), 340 (42), 341 (59), 342
(39), 343 (96), 344 (45), 345 (100), 346 (13).
Te-Phenyl O,O¢-Dibutyl Phosphorotellurate (2h)
Rf = 0.40 (EtOAc–n-hexane, 1:2).
Te-p-Methoxyphenyl O,O¢-Diethyl Phosphorotellurate (2a)
Rf = 0.45 (EtOAc–n-hexane, 1:2).
IR (neat): 3020, 1587, 1489, 1441, 1248, 1217, 1045, 908 cm–1.
IR (neat): 3055, 2958, 2873, 1574, 1466, 1381, 1242, 1149, 976,
833 cm–1.
FABMS: m/z calcd for C11H17PO4Te: 374; found: a maximum at
375 with tellurium isotopic fingerprint ranged between 366 and
376; 366 (8), 367 (12), 368 (14), 369 (29), 370 (55), 371 (56), 372
(63), 373 (92), 374 (71), 375 (100), 376 (15).
FABMS: m/z calcd for C14H23PO3Te: 400; found: a maximum at
401 with tellurium isotopic fingerprint ranged between 393 and
403; 393 (11), 394 (10), 395 (24), 396 (41), 397 (61), 398 (38), 399
(96), 400 (46), 401 (100), 402 (17), 403 (6).
Te-p-Methoxyphenyl O,O¢-Dibutyl Phosphorotellurate (2b)
Rf = 0.41 (EtOAc–n-Hexane, 1:2).
Te-Phenyl O,O¢-Dibenzyl Phosphorotellurate (2i)
Rf 0.30 (EtOAc–n-hexane, 1:4).
IR (neat): 3062, 2950, 2885, 1574, 1454, 1377, 1238, 987 cm–1.
IR (neat): 3005, 2964, 2875, 1587, 1489, 1286, 1248, 1213, 1178,
1045, 978 cm–1.
FABMS: m/z calcd. for C20H19PO3Te, 468; found: a maximum at
469 with tellurium isotopic fingerprint ranged between 460 and
471; 460 (10), 461 (19), 462 (20), 463 (32), 464 (51), 465 (65), 466
(48), 467 (94), 468 (58), 469 (100), 470 (29), 471 (17).
FABMS: m/z calcd for C15H25PO4Te: 430; found: a maximum at
431 with tellurium isotopic fingerprint ranged between 422 and
432; 422 (5), 423 (10), 424 (10), 425 (29), 426 (57), 427 (61), 428
(66), 429 (95), 430 (75), 431 (100), 432 (17).
Te-p-Methoxyphenyl O-Ethyl Phenylphosphonotellurate (3)
Rf = 0.19 (EtOAc–n-hexane, 1:2).
Te-p-Methoxyphenyl O,O¢-Dibenzyl Phosphorotellurate (2c)
Rf = 0.31 (EtOAc–n-hexane, 1:3).
IR (neat): 3059, 2981, 2835, 1585, 1566, 1489, 1458, 1439, 1389,
1288, 1250, 1219, 1176, 1111, 1022, 949, 822 cm–1.
IR (neat): 3031, 1736, 1585, 1566, 1489, 1458, 1377, 1288, 1250,
1176, 987 cm–1.
FABMS: m/z calcd for C15H17PO3Te, 406; found: a maximum at
407 with tellurium isotopic fingerprint ranged between 399 and
408; 399 (9), 400 (10), 401 (24), 402 (45), 403 (59), 404 (46), 405
(93), 406 (55), 407 (100), 408 (17).
FABMS: m/z calcd for C21H21PO4Te, 498; found: a maximum at
498 with tellurium isotopic fingerprint ranged between 490 and
500; 490 (7), 491 (11), 492 (17), 493 (31), 494 (66), 495 (57), 496
(87), 497 (87), 498 (100), 499 (95), 500 (22).
Te-p-Methoxyphenyl N,N-Diisopropyl O-Benzyl Phosphorotel-
luramidate (4)
Rf = 0.31 (EtOAc–n-hexane, 1:3).
Te-p-Methoxyphenyl O,O¢-Diphenyl Phosphorotellurate (2d)
Rf = 0.26 (EtOAc–n-hexane, 1:4).
FABMS: m/z calcd for C19H17PO4Te, 470; found: a maximum at
471 with tellurium isotopic fingerprint ranged between 462 and
473; 462 (14), 463 (20), 464 (26), 465 (37), 466 (31), 467 (67), 468
(71), 469 (96), 470 (84), 471 (100), 472 (29), 473 (10).
IR (neat): 3062, 2966, 2885, 1585, 1489, 1365, 1246, 1157, 995,
821 cm–1.
FABMS: m/z calcd for C20H28PNO3Te, 491; found: a maximum at
492 with tellurium isotopic fingerprint ranged between 484 and
493; 484 (12), 485 (15), 486 (27), 487 (49), 488 (65), 489 (54), 490
(97), 491 (62), 492 (100), 493 (26).
Te-p-Methoxyphenyl O,O¢-o-Xylylenediyl Phosphorotellurate
(2e)
Mp 129.0–130.0 °C (EtOAc–hexane, dec.); Rf = 0.27 (EtOAc–n-
hexane, 1:1).
Acknowledgment
IR (Nujol): 2927, 2854, 2719, 1716, 1581, 1458, 1377, 1265, 1173,
1002, 818 cm–1.
The authors thank Venture Business Laboratory of Ehime Univer-
sity for their financial support. We also thank the Center for Coope-
rative Research and Development, Ehime University for
measurement of mass spectra. This work was financially supported
by the Fujisawa Foundation and Saneyoshi Scholarship Foundation.
FABMS: m/z calcd for C15H15PO4Te: 420; found: a maximum at
421 with tellurium isotopic fingerprint ranged between 413 and
422; 413 (14), 414 (15), 415 (33), 416 (55), 417 (58), 418 (61), 419
(93), 420 (71), 421 (100), 422 (21).
Anal. Calcd for C15H15PO4Te: C, 43.12; H, 3.62; Found: C, 43.08;
H, 3.49.
References
(1) Hartley, F. R. In The Chemistry of Organophosphorus
Compounds, Vol. 4; Patai, S.; Rappoport, Z., Eds.; Wiley:
Chichester, 1996.
(2) (a) Clive, D. L. J.; Menchen, S. M. J. Chem. Soc., Chem.
Commun. 1977, 658. (b) Clive, D. L. J.; Menchen, S. M. J.
Org. Chem. 1980, 45, 2347. (c) Czyzewska-Chlebny, J.;
Michalska, M. J. Chem. Soc., Chem. Commun. 1985, 693.
Te-p-Methoxyphenyl O,O¢-Dimethyl Phosphorotellurate (2f)
Rf = 0.40 (EtOAc–CHCl3, 1:10).
IR (neat): 3020, 1587, 1489, 1288, 1248, 1217, 1178, 1020 cm–1.
FABMS: m/z calcd for C9H13PO4Te: 346; found: a maximum at 347
with tellurium isotopic fingerprint ranged between 339 and 348;
339 (10), 340 (14), 341 (26), 342 (54), 343 (58), 344 (56), 345 (95),
346 (61), 347 (100), 348 (11).
Synthesis 2004, No. 9, 1481–1485 © Thieme Stuttgart · New York

PAPER
(3) Petragnani, N. Tellurium in Organic Synthesis; Academic
Synthesis of Phosphorotellurate Triesters
1485
Klamann, D., Ed.; Thieme: Stuttgart, 1990, 238; and
Press: London, 1994.
references cited therein. (b) Irgolic, K. J. In
(4) Watanabe, Y.; Yamamoto, T.; Iwasaki, T.; Ozaki, S. Chem.
Lett. 1994, 1881.
(5) Watanabe, Y.; Inoue, S.; Yamamoto, T.; Ozaki, S. Synthesis
1995, 1243.
(6) Reichel, L.; Kirschbaum, E. Liebigs Ann. Chem. 1936, 523,
24.
(7) (a) Irgolic, K. J. In Organotellurium Compounds, Methoden
der Organischen Chemie (Houben-Weyl), Vol. E12b;
Organotellurium Compounds, Methoden der Organischen
Chemie (Houben-Weyl), Vol. E12b; Klamann, D., Ed.;
Thieme: Stuttgart, 1990, 256.
(8) Han, L.-B.; Choi, N.; Tanaka, M. J. Am. Chem. Soc. 1996,
118, 7000.
(9) Substitution of the alkyltelluro group by aerobic oxidation in
methanol has been reported, see Ref. 2c.
Synthesis 2004, No. 9, 1481–1485 © Thieme Stuttgart · New York