Simple and convenient method for the synthesis of aryltellurophosphates catalyzed by cesium hydroxide

Article abstract of DOI:10.1080/00397911.2013.879897

In the presence of a catalytic amount cesium hydroxide, the corresponding aryltellurophosphates can be obtained by the reactions of dialkyl phosphites with diaryl ditellurides in excellent yield at room temperature, using dimethylsulfoxide as solvent. The possible reaction mechanism was discussed. The method could provide a new and expedient path for the preparation of aryltellurophosphates. Copyright

Full text of DOI:10.1080/00397911.2013.879897

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Simple and Convenient Method for the
Synthesis of Aryltellurophosphates
Catalyzed by Cesium Hydroxide
Ling Xiao Wang a , Liu Su a , Jian Hua Li a , Ning Bo Li a , Zhi Hong
Peng a , Yuan Yuan Li a & Xin Hua Xu a
a College of Chemistry and Chemical Engineering , Hunan
University , Changsha , China
Accepted author version posted online: 16 Apr 2014.Published
online: 09 Jun 2014.
To cite this article: Ling Xiao Wang , Liu Su , Jian Hua Li , Ning Bo Li , Zhi Hong Peng , Yuan Yuan Li &
Xin Hua Xu (2014) Simple and Convenient Method for the Synthesis of Aryltellurophosphates Catalyzed
by Cesium Hydroxide, Synthetic Communications: An International Journal for Rapid Communication
of Synthetic Organic Chemistry, 44:14, 2088-2093, DOI: 10.1080/00397911.2013.879897
To link to this article: http://dx.doi.org/10.1080/00397911.2013.879897
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Synthetic Communications1, 44: 2088–2093, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2013.879897
SIMPLE AND CONVENIENT METHOD FOR THE
SYNTHESIS OF ARYLTELLUROPHOSPHATES
CATALYZED BY CESIUM HYDROXIDE
Ling Xiao Wang, Liu Su, Jian Hua Li, Ning Bo Li,
Zhi Hong Peng, Yuan Yuan Li, and Xin Hua Xu
College of Chemistry and Chemical Engineering, Hunan University,
Changsha, China
GRAPHICAL ABSTRACT
Abstract In the presence of a catalytic amount cesium hydroxide, the corresponding aryltel-
lurophosphates can be obtained by the reactions of dialkyl phosphites with diaryl ditellurides
in excellent yield at room temperature, using dimethylsulfoxide as solvent. The possible reac-
tion mechanism was discussed. The method could provide a new and expedient path for the
preparation of aryltellurophosphates.
Keywords Aryltellurophosphates; cesium hydroxide; diaryl ditellurides
INTRODUCTION
S-, Se-, and Te-aryl phosphorochalcogenoates (chalcogenophosphates) are
very useful synthetic intermediates for synthetic and biological studies.[1–10] General
methods for the preparation of phosphorochalcogenoates esters bearing thio and=or
seleno substituents have been well documented.[11–15] However, as congener element,
there are a few reports for the preparation of Te-aryl phosphorotelluroates; therefore
only little was known about their reactivities, although the phosphorotellurate esters
should provide a great interest on account of their reactivities. To our knowledge,
Huang reported the aryltellurophosphates were prepared by the free radical reaction
initiated by azobisisobutyronitrile (AIBN) or sodium azide (NaN3).[16–18] An alterna-
tive preparation of Te-aryl phosphorotelluroates in good yields that used 4-methox-
yphenyltellurium trichloride and dialkyl or trialkyl phosphites was reported by
Hayashi et al.[19] The first method was in poor yield because the aryltelluropho-
sphates are instable compounds[20] and may decompose under such conditions,
Received October 19, 2013.
Address correspondence to Xin Hua Xu or Zhi Hong Peng, College of Chemistry and Chemical
Engineering, Hunan University, Changsha 410082, China. E-mail: xhx1581@hnu.edu.cn; pzh7251@
yahoo.com
2088

SYNTHESIS OF ARYLTELLUROPHOSPHATES
2089
Scheme 1. Synthesis of aryltellurophosphates.
whereas the second method needed extremely labile reagents ArTeCl3 and thus
needed to be performed under strict reaction conditions. Recently, Gao and cowor-
kers reported the reaction of diaryl ditellurides with dialkyl phosphites
[(RO)2P(O)H] catalyzed by CuI in the presence of organic base.[3] Though this
method is an atom-economical reaction and has excellent yields, it needs a stoichio-
metric amount of organic base. Considering the growing utility of organotellurium
compounds in organic synthesis, the development of a general, efficient, and econ-
omical method for the preparation of aryltellurophosphates is still highly desirable.
Cesium hydroxide, which performs as a super inorganic base, can react with
weakly acid substances to give a strongly nucleophilic anion.[21–23] The diaryl ditel-
lurides are not only nucleophiles but also electrophiles. The P-H bond in dialkyl
phosphites [(RO)2P(O)H] is a polar bond. It exhibits weak acid, which should react
with cesium hydroxide to form strongly nucleophilic (RO)2P-(O)Csþ. Therefore, we
assume that cesium hydroxide could catalyze the reaction of diaryl ditellurides with
dialkyl phosphates. In this article, we report the results (Scheme 1).
RESULTS AND DISCUSSION
We first tested the reaction of diethyl phosphite (DEP) and diphenyl ditellur-
ide, and the experiment showed that the yield was only 58% using commercial tetra-
hydrofuran (THF) as solvent in the presence of 20 mol% cesium hydroxide at room
temperature under an air atmosphere for 7 h. To determine the best experimental
conditions, we studied the effect of other solvents on the reaction. The results are
summarized in Table 1, and it can be seen that the reactions can hardly occur in
dichloromethane or toluene even when extending the reaction time (Table 1, entries
1–6). When dimethylformamide (DMF) was used as solvent, the reactions afforded
compound 3b in the yield of 76% for 7 h (Table 1, entry 10). The greatest yield was
obtained in dimethylsulfoxide (DMSO; Table 1, entry 12, 92%). This surprising
result together with the lack of reactivity in other solvents suggests that DMSO
might act not only as the solvent but also as an oxidant in the reaction.[24,25] Also,
we investigated the loading of catalyst and found that the optimal dosage of cesium
hydroxide was 20 mol% (Table 1, entries 12–14).
To assess the catalytic ability of cesium hydroxide to catalyze Te-P bond
formation, we evaluated several alkali metal hydroxides including lithium hydroxide,
sodium hydroxide, potassium hydroxide, and rubidium hydroxide (Table 2). The
results showed that cesium hydroxide had enough ability to catalyze Te-P bond
formation in the same conditions.
With the optimal condition in hand, the reactions of various diaryl ditellurides
and dialkyl phosphites were investigated, and the results are given in Table 3. The
reactions worked well for a variety of diaryl ditellurides and dialkyl phosphites.
Different dialkyl phosphites (such as dimethyl, diethyl, di-i-Pr, di-n-Bu) showed

2090
L. X. WANG ET AL.
Table 1. Preparation of compound 3b under various conditionsa
Entry
Solvent
Catalyst (mol%)
Time (h)
Yield (%)
1
2
CH2Cl2
CH2Cl2
Toluene
Toluene
EtOH
20
20
20
20
20
20
20
20
20
20
20
20
15
25
3
7
3
7
3
7
3
7
3
7
3
7
7
7
Trace
10
3
Trace
16
21
4
5
6
EtOH
THF
44
39
7
8
THF
DMF
DMF
58
43
9
10
11
12
13
14
76
62
DMSO
DMSO
DMSO
DMSO
92
76
93
aDiethylphosphite: 2.0 mmol; diphenylditelluride: 1.0 mmol; CsOH: 0.2 mmol; temp: rt.
Table 2. Influence of various bases on the reaction for diethyl phosphite with diphenylditelluridea
Entry
1
2
3
4
5
Base
Yield(%)
LiOH
0
NaOH
22
KOH
29
RbOH
69
CsOH
92
aDiethylphosphite: 2.0 mmol; diphenylditelluride: 1.0 mmol; solvent: DMSO; temp: rt; time: 7 h; alkali
metal hydroxide: 0.2 mmol.
good reactivity with diphenyl ditelluride in high yields (Table 3, entries 1–4). Diaryl
ditellurides with electron-donating (methyl, methoxyl) and electron-withdrawing
(chloride) groups were also employed (Table 3, entries 5–14). Despite variation of
Table 3. Preparation of Te-aryl phosphorotelluroatesa
Entry
R
Ar
Productb
Yield (%)
1
2
Me
Et
C6H5
C6H5
C6H5
3a[16]
3b[16]
3c[3]
3d[17]
3e[17]
3f[17]
3 g[17]
3 h[16]
3i[3]
91
92
91
90
88
87
84
90
91
89
91
93
89
90
3
i-Pr
n-Bu
Me
Et
4
C6H5
5
p-ClC6H4
p-ClC6H4
p-ClC6H4
p-CH3C6H4
p-CH3C6H4
p-CH3C6H4
o-OCH3C6H4
o-OCH3C6H4
o-OCH3C6H4
o-OCH3C6H4
6
7
n-Bu
Me
Et
8
9
10
11
12
13
14
n-Bu
Me
Et
3j[3]
3k
3 l
i-Pr
n-Bu
3 m
3n
aDialkyl phosphates: 2.0 mmol; diarylditellurides: 1.0 mmol; solvent: DMSO; temp: rt; time: 7 h; CsOH:
0.2 mmol.
b3a–3j are known compounds from the literature and 3k–3n are new compounds.

SYNTHESIS OF ARYLTELLUROPHOSPHATES
2091
Scheme 2. Possible reaction mechanism for the synthesis of aryltellurophosphates.
reaction rate, the yields were good and the functional groups present in the phenyl
group of diaryl ditellurides did not affect the yields obviously. Thus, this method
could be widely used in the synthesis of a variety of aryltellurophosphates.
A possible reaction mechanism for the reaction of diaryl ditellurides and dia-
lkyl phosphites to aryltellurophosphates in the present of cesium hydroxide is
depicted in Scheme 2. Dialkyl phosphites reacted with cesium hydroxide to give
(RO)2Pꢀ(O)Csþ, which underwent nucleophilic attack on ArTeTeAr to give aryltel-
lurophosphates and ArTeꢀCsþ. The latter was oxidized in the presence of water to
form diaryl ditellurides and catalyst cesium hydroxide.[25]
In summary, we have developed a highly efficient and simple method for the
preparation of Te-aryl phosphorotelluroates. It has many merits such as mild
reaction condition, convenient manipulation, solvents without need to remove water,
a catalytic amount of cesium hydroxide, and good yields.
EXPERIMENTAL
In a round-bottomed flask, cesium hydroxide (0.2 mmol) was added to a sol-
ution of dialkyl phosphites (2.0 mmol) and diaryl ditellurides (1.0 mmol) in DMSO
(5.0 mL). The reaction mixture was stirred at room temperature under an air atmos-
phere for 7 h. The reaction was monitored by thin-layer chromatography (TLC)
analysis. Then water (15 mL) was added and the mixture was extracted with ethyl
acetate (15 mL ꢁ 3). The combined organic phase was washed with water
(20 mL ꢁ 2), dried over anhydrous Na2SO4, and concentrated under vacuum. The
crude product was purified by column chromatography on silica gel (petroleum
ether–ethyl acetate ¼ 5:1). Compound 3b:[16] yellow oil, 31P NMR (162 Hz, CDCl3)
d (ppm) ꢀ 0.88; 1H NMR (400 Hz, CDCl3) d (ppm) 7.82–7.78 (m, 2H, Ph),
7.36–7.29 (m, 1H, Ph), 7.25–7.20 (m, 2H, Ph), 4.18–4.04 (m, 4H, CH2), 1.31–1.26
(m, 6H, CH3); 13C NMR (100 Hz, CDCl3) d (ppm) 139.3, 129.9, 129.1, 108.7,
64.1, 16.6; MS (EI): m=z ¼ 344 (M þ 2)þ.
FUNDING
The authors thank the National Natural Science Foundation of China (Nos.
21172061, 21273068) and the NSF of Hunan Province (11JJ5009).

2092
L. X. WANG ET AL.
SUPPLEMENTAL MATERIAL
Compounds 3a–3j are known from the literature and 3k–3n are new com-
pounds. Full experimental detail, 1H NMR, 13C NMR 31P NMR, and mass spectral
(MS) data, and the copies of representative compounds 3c and new compounds
3k–3n spectra (1H NMR, 13C NMR, 31P NMR, IR, MS) can be accessed on the
publisher’s website.
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