Free radical reaction of dialkyl phosphites and organic dichalcogenides: A new facile and convenient preparation of arylselenophosphates

Article abstract of DOI:10.1081/SCC-120022165

Azobisisobutyronitrile-initiated free radical reaction of dialkyl phosphites with diaryl diselenides afforded arylselenophosphates in high yields. Arylthiophosphates and aryltellurophosphates can also be synthesized by similar reaction of diaryl disulfide

Full text of DOI:10.1081/SCC-120022165

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Free Radical Reaction of Dialkyl Phosphites and
Organic Dichalcogenides: A New Facile and Convenient
Preparation of Arylselenophosphates
Qing Xu a b , Chun-Gen Liang a b & Xian Huang a b
a Department of Chemistry , Zhejiang University (Xixi Campus) , Hangzhou, P.R. China
b Laboratory of Organometallic Chemistry , Shanghai Institute of Organic Chemistry ,
Chinese Academy of Sciences , Shanghai, P.R. China
Published online: 19 Aug 2006.
To cite this article: Qing Xu , Chun-Gen Liang & Xian Huang (2003) Free Radical Reaction of Dialkyl Phosphites and
Organic Dichalcogenides: A New Facile and Convenient Preparation of Arylselenophosphates, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 33:16, 2777-2785, DOI: 10.1081/
SCC-120022165
To link to this article: http://dx.doi.org/10.1081/SCC-120022165
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 16, pp. 2777–2785, 2003
Free Radical Reaction of Dialkyl Phosphites and
Organic Dichalcogenides: A New Facile and
Convenient Preparation of Arylselenophosphates
Qing Xu,1,2 Chun-Gen Liang,1,2 and Xian Huang1,2,
*
1Department of Chemistry, Zhejiang University
(Xixi Campus), Hangzhou, P.R. China
2Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai, P.R. China
ABSTRACT
Azobisisobutyronitrile-initiated free radical reaction of dialkyl
phosphites with diaryl diselenides afforded arylselenophosphates in
high yields. Arylthiophosphates and aryltellurophosphates can also
be synthesized by similar reaction of diaryl disulfides and diaryl
ditellurides with dialkyl phosphites.
*Correspondence: Xian Huang, Department of Chemistry, Zhejiang University
(Xixi Campus), Hangzhou 310028, P.R. China; Laboratory of Organometallic
Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, Shanghai 200032, P.R. China.
2777
DOI: 10.1081/SCC-120022165
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
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2778
Xu,Liang,and Huang
Arylselenophosphates are useful intermediates in organic chemistry[1]
and biochemistry.[2] Recently, Han and coworkers reported the palla-
dium-catalyzed selenophosphorylation of terminal acetylenes[1a] using
arylselenophosphates. Besides, peroxides or azobisisobutyronitrile
(AIBN) initiated free radical chain reactions of alkenes with arylseleno-
phosphates[1b] and its sulfurderivatives,
[3]
in the presence of tributyltin
hydride, has also been reported by other groups. Due to its importance, a
variety of procedures have been achieved to prepare arylselenophos-
phates.[1a,4,5] However, these methods usually implicate toxic, uncommon
reagents, strict reaction conditions or poor yield.
It is well established that organic dichalcogenides are good free
radical acceptors toward carbon radicals[6] in the order of RSSR<
RSeSeR<RTeTeR.[7] On the otherhand, phosphonyl ardicals can be
generated from dialkyl phosphites in the presence of peroxides, azo
[8]
compounds, orultraviolet light.
However, direct synthesis of arylchal-
cogenophosphates from organic dichalcogenides and dialkyl phosphites
via free radical procedure is seldom discussed.[4b] Therefore, we investi-
gated the AIBN-initiated free radical reactions as shown in Sch. 1.
We began ourstudy by examining the reaction of diethyl phosphite
with diphenyl diselenide. Initially this reaction was carried out in
refluxing benzene (5 mL) in the presence of 10 mol% AIBN, O,O-diethyl
phenylselenophosphate (3d) was obtained in moderate yield (68%). Then
various reaction conditions were investigated. Solvents such as benzene,
tetrahydrofuran, dichloromethane, chloroform, hexane, cyclohexane,
and toluene can be used in the reaction and we found benzene was the
best. The optimized reaction temperature was about 60–65ꢀC.[9] Further-
more, higher concentration of the starting materials and increased
amount of AIBN favored the completion of the reaction, resulting in
shorter reaction time and higher yield. Thus, the expected arylseleno-
phosphates was obtained in high yield by simply heating the mixture of
diaryl diselenide (0.5 mmol), dialkyl phosphites (1.2 mmol), and 50 mol%
of AIBN (82 mg, 0.5 mmol) in benzene (1 mL) (Sch. 2, Table 1). Compared
with the reported preparation of arylselenophosphates,[1a,4,5] the present
method has the advantages of easily available starting materials, simple
operation, mild condition, and high yield.
AIBN
ArYYAr + HP(O) (OR)
ArYP(O) (OR)
2
2
Y = S, Se, Te
Scheme 1.

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Arylselenophosphates
2779
AIBN ( 50 mol%)
C H , 60~65 , 24h
ArSeP(O) (OR)
ArSeSeAr + HP(O) (OR)
2
2
°C
6
6
3
1
2
Scheme 2.
Table 1. Preparation of arylselenophosphates 3.
Yielda
(%)
Entry
Product
3a
3b
3c
3d
3e
3f
C6H5SeP(O)(OCH3)2
89
94
91
98
94
82
87
94
97
p-ClC6H4SeP(O)(OCH3)2
p-CH3C6H4SeP(O)(OCH3)2
C6H5SeP(O)(OC2H5)2
p-ClC6H4SeP(O)(OC2H5)2
C6H5SeP(O)[OCH(CH3)2]2
p-ClC6H4SeP(O)[OCH(CH3)2]2
C6H5SeP(O)(On-C4H9)2
p-ClC6H4SeP(O)(On-C4H9)2
3g
3h
3i
aIsolated yields based on diaryl diselenides.
Though obviously the above reaction was an AIBN-initiated free
radical reaction, we did other experiments to confirm its free radical
nature. When the mixture of diethyl phosphite and diphenyl diselenide
was heated at 60–65ꢀC in benzene (1 mL) in the absence of AIBN, the
reaction proceeded slowly and afforded 3d in 78% yield after4 days’
stirring, indicating the generation of phosphonyl radical was thermal-
induced, which has been reported recently by Hubert et al.[8f ]
Inhibition of the same reaction by hydroquinone (50 mol%) was also
observed, resulting in longer reaction time and lower yield of the product.
All these facts elucidated the reaction of dialkyl phosphites and diaryl
diselenides was free radical in character. Possible reaction pathway form-
ing the arylselenophosphates was proposed as shown in Sch. 3. The initial
step of the free radical reaction is the AIBN- or thermal-induced genera-
tion of phosphonyl radical. Then arylseleno group abstraction from
diaryl diselenide by phosphonyl radical afforded the product and an
equivalent of the arylselenyl radical respectively. The fomer-formed
arylselenyl radical might combine with phosphonyl radical to form
anothermolecularof the product.

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2780
Xu,Liang,and Huang
AIBN or Heat
(RO) (O)PH
(RO) (O)P
2
(1)
2
(RO) (O)P
+
(RO) (O)PSeAr + ArSe
ArSeSeAr
2
2
(2)
(3)
(RO) (O)P
+
ArSe
(RO) (O)PSeAr
2
2
Scheme 3.
Table 2. Preparation of arylthiophosphates
aryltellurophosphates 5.
4
and
Yieldb
(%)
Product
Timea
4a
4b
4c
5a
5b
5c
C6H5SP(O)(OCH3)2
12
8
57
41
25
16
15
19
C6H5SP(O)(OC2H5)2
C6H5SP(O)(On-C4H9)2
C6H5TeP(O)(OCH3)2
C6H5TeP(O)(OC2H5)2
p-CH3C6H4TeP(O)(OCH3)2
4
10
10
10
aReaction time is given in days forayrlthiophosphates and
hours for aryltellurophosphates.
bIsolated yields based on diaryl dichalcogenides.
This method was also applied to synthesize the arylthiophosphates[10]
and aryltellurophosphates.[11] In contrast to the formation of arylseleno-
phosphates, the reaction of diphenyl disulfide and dialkyl phosphites was
very slow (Table 2, Entries 4a–c), even negligible reaction occurred in
12 h in the absence of AIBN,[10c] which might be ascribed to the slow
abstraction rate of phenylthio group by phosphonyl radicals. Reaction of
diaryl ditellurides and dialkyl phosphites afforded aryltellurophosphates
in very low yield, most of the reactants remain un-reacted (Table 2, Entries
5a–c). Prolonged reaction time and increased amount of AIBN addition
was useless to improve the yield. Aryltellurophosphates are instable
compounds[11] and the isolated pure products decomposed in a few days.
In conclusion, AIBN-initiated free radical reaction of dialkyl
phosphites and diaryl diselenides provided a novel and convenient
route to prepare the versatile arylselenophosphates. Using this method
arylthiophosphates and the instable aryltellurophosphates can also be
synthesized.

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Arylselenophosphates
2781
EXPERIMENTAL
1H NMR spectra were recorded on a Bruker Avance 400 spectrom-
eterusing CDCl with TMS as the internal standard. Infrared spectra
3
were recorded on a Bruker Vector 22 spectrometer. EIMS were run on
a HP 5989B mass spectrometer and HRMS were recorded on a Kratos
Concept 1H Series Mass spectrometer. Elemental analyses were per-
formed on an EA-1110 instrument. AIBN was obtained commercially
and used without further purification. Diphenyl disulfide,[12] diaryl dis-
elenides,[13] diaryl ditellurides[14] and dialkyl phosphates[15] were prepared
according to literature procedure. All solvents were dried and freshly
distilled prior to use.
General Procedure for the Free Radical Reaction of
Organic Dichalcogenides and Dialkyl Phosphites
In a tubular reactor equipped with a condenser, the solution of
dichalcogenides (0.5 mmol), dialkyl phosphite (1.2 mmol), and AIBN
(82 mg, 50 mol%) in anhydrous benzene (1 mL) was stirred at
about 60–65ꢀC underN 2. In the case of diaryl diselenides, the red
mixture gradually turned to yellow or even colorless and was monito-
red by TLC. Then the mixture was subjected to preparative TLC on
silica gel to afford the arylselenophosphates (Hexane/EtOAc, 2/1 for
3a–e, 5/1 for 3f–i). In the case of diphenyl disulfide and diaryl ditel-
lurides, the reactions were not complete and were heated for the time
as indicated in Table 2. Then the mixture was subjected to pre-
parative TLC (Hexane/EtOAc, 2/1 for 4a, 4b, 5a–c, 5/1 for 4c).
Reactions under different conditions were operated in a similar
manner.
O,O-Dimethyl Se-phenyl phosphoroselenoate3a. Yellowoil, b.p.[5a]
0.005
91–92ꢀC. H NMR (400 MHz, CDCl3): ꢀ ¼ 7.66–7.63 (dd, J ¼ 6.56 Hz,
1
J ¼ 1.48 Hz, 2H), 7.36–7.31 (m, 3H), 3.81 and 3.78 (d, J ¼ 13.16 Hz, 6H).
MS (EI): m/z (rel. intensity) ¼ 266 (22, Mþ), 157 (10), 109 (100), 77 (19). IR
(film): ꢁmax ¼ 3060, 3000, 2952, 2859, 1578, 1477, 1440, 1255, 1181, 1019,
985, 826, 787, 762, 740 cmꢁ1
.
O,O-Dimethyl Se-p-chlorophenyl phosphoroselenoate 3b. Yellow oil.
1H NMR (400 MHz, CDCl3): ꢀ ¼ 7.59–7.55 (dd, J ¼ 8.52 Hz, J ¼ 1.88 Hz,
2H), 7.31–7.28 (d, J ¼ 8.60 Hz, 2H), 3.82 and 3.79 (d, J ¼ 13.20 Hz, 6H).
MS (EI): m/z (rel. intensity) ¼ 300 (20, Mþ), 191 (8), 111 (3), 109 (100), 79
(14). IR (film): ꢁmax ¼ 3083, 3060, 2954, 2870, 1475, 1388, 1254, 1185,

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2782
Xu,Liang,and Huang
1090, 1010, 818, 787, 759 cmꢁ1. Anal. calcd. forC 8H10ClO3PSe: C, 32.08;
H, 3.36. Found: C, 32.26; H, 3.41.
O,O-Dimethyl Se-p-tolyl phosphoroselenoate 3c. Yellow oil. 1H NMR
(400 MHz, CDCl3): ꢀ ¼ 7.53–7.49 (dd, J ¼ 8.18 Hz, J ¼ 1.94 Hz, 2H),
7.15–7.12 (d, J ¼ 8.24 Hz, 2H), 3.82 and 3.79 (d, J ¼ 13.16 Hz, 6H), 2.35
(s, 3H). MS (EI): m/z (rel. intensity) ¼ 280 (40, Mþ), 171 (13), 109 (100),
91 (44), 79 (20). IR (film): ꢁmax ¼ 3022, 2951, 2849, 1490, 1445, 1399,
1254, 1181, 1014, 823, 805, 782, 759 cmꢁ1
. Anal. calcd. for
C9H13O3PSe: C, 38.73; H, 4.69. Found: C, 38.58; H, 4.66.
O,O-Diethyl Se-phenyl phosphoroselenoate 3d. Yellow oil, b.p.[5a]
0.005
102ꢀC. 1H NMR (400 MHz, CDCl3): ꢀ ¼ 7.66–7.63 (m, 2H), 7.37–7.29 (m,
3H), 4.23–4.12 (m, 4H), 1.33–1.28 (t, J ¼ 7.08 Hz, 6H). MS (EI): m/z (rel.
intensity) ¼ 294 (76, Mþ), 157 (25), 137 (33), 109 (100), 77 (34). IR (film):
ꢁmax ¼ 3061, 2984, 2929, 2909, 2871, 1578, 1477, 1440, 1391, 1251, 1161,
1102, 1013, 972, 796, 741 cmꢁ1
.
O,O-Diethyl Se-p-chlorophenyl phosphoroselenoate 3e. Yellow oil,
b.p.[5c] 172–174ꢀC. 1H NMR (400 MHz, CDCl3): ꢀ ¼ 7.59–7.56 (dd,
1
J ¼ 8.56 Hz, J ¼ 1.84 Hz, 2H), 7.31–7.28 (d, J ¼ 6.48 Hz, 2H), 4.22–4.15
(m, 4H), 1.34–1.30 (t, J ¼ 7.07 Hz, 6H). MS (EI): m/z (rel. intensity) ¼ 328
(48, Mþ), 191 (13), 137 (36), 111 (3), 109 (100). IR (film): ꢁmax ¼ 3065,
2984, 2929, 2909, 2870, 1474, 1444, 1389, 1253, 1162, 1090, 1011, 973,
816, 796, 759 cmꢁ1
.
O,O-Di-iso-propyl Se-phenyl phosphoroselenoate 3f. Yellow oil,
b.p.[5a]
101ꢀC. 1H NMR (400 MHz, CDCl3): ꢀ ¼ 7.68–7.65 (dd,
0.005
J ¼ 7.84 Hz, J ¼ 1.44 Hz, 2H), 7.33–7.30 (m, 3H), 4.80–4.77 (m, 2H),
1.35–1.24 (dd, J ¼ 33.26 Hz, J ¼ 6.18 Hz, 12H). MS (EI): m/z (rel.
intensity) ¼ 322 (52, Mþ), 280 (27), 238 (100), 165 (2), 157 (48), 77 (57).
IR (film): ꢁmax ¼ 3059, 2980, 2935, 2879, 1579, 1478, 1440, 1386, 1375,
1251, 1179, 1143, 1103, 981, 885, 778, 741 cmꢁ1
.
O,O-Di-iso-propyl Se-p-chlorophenyl phosphoroselenoate 3g. Yellow
oil. 1H NMR (400 MHz, CDCl3): ꢀ ¼ 7.62–7.58 (dd, J ¼ 8.50 Hz,
J ¼ 1.74 Hz, 2H), 7.29–7.27 (d, J ¼ 8.50 Hz, 2H), 4.81–4.76 (m, 2H),
1.35–1.26 (dd, J ¼ 26.12 Hz, J ¼ 6.56 Hz, 12H). MS (EI): m/z (rel.
intensity) ¼ 356 (100, Mþ), 315 (30), 272 (38), 191 (19), 165 (3), 156
(19). IR (film): ꢁmax ¼ 3065, 2981, 2936, 2879, 1475, 1387, 1376, 1252,
1179, 1142, 1090, 977, 885, 816, 767, 729 cmꢁ1. Anal. calcd. for
C12H18ClO3PSe: C, 40.53; H, 5.10. Found: C, 40.61; H, 5.15.
O,O-Di-n-butyl Se-phenyl phosphoroselenoate 3h. Yellow oil, b.p.[5a]
124ꢀC. H NMR (400 MHz, CDCl3): ꢀ ¼ 7.66–7.62 (dd, J ¼ 8.26 Hz,
1
0.005
J ¼ 1.54 Hz, 2H), 7.33–7.26 (m, 3H), 4.14–4.07 (m, 4H), 1.65–1.60 (t, J ¼
7.48 Hz, 2H), 1.38–1.31 (q, J ¼ 7.49 Hz, 2H), 0.92–0.87 (t, J ¼ 7.38 Hz,
6H). MS (EI): m/z (rel. intensity) ¼ 351 (Mþ þ 1, 100), 350 (Mþ, 43),

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Arylselenophosphates
2783
349 (Mþ ꢁ 1, 50), 157 (18), 137 (29), 77 (19), 57 (53). IR (film):
ꢁmax ¼ 3056, 2961, 2939, 2876, 1579, 1476, 1431, 1374, 1253, 1148,
1111, 1074, 1017, 980, 889, 824, 787, 740 cmꢁ1
.
O,O-Di-n-butyl Se-p-chlorophenyl phosphoroselenoate 3i. Yellow oil.
1H NMR (400 MHz, CDCl3): ꢀ ¼ 7.59–7.56 (dd, J ¼ 8.50 Hz, J ¼ 1.78 Hz,
2H), 7.30–7.27 (d, J ¼ 8.40 Hz, 2H), 4.14–4.07 (m, 4H), 1.66–1.61 (t,
J ¼ 7.46 Hz, 2H), 1.39–1.32(q, J ¼ 7.51 Hz, 2H), 0.93–0.89 (t,
J ¼ 7.38 Hz). MS (EI): m/z (rel. intensity) ¼ 384 (11, Mþ), 192 (17), 137
(46), 57 (100). IR (film): ꢁmax ¼ 3056, 2961, 2944, 2874, 1474, 1435, 1388,
1254, 1148, 1090, 1065, 1010, 975, 815, 781, 730 cmꢁ1. Anal. calcd. for
C14H22ClO3PSe: C, 47.28; H, 6.23. Found: C, 47.46; H, 6.27.
O,O-Dimethyl S-phenyl phosphorothioate 4a. Yellow oil, b.p.[10d]
70–75ꢀC/0.05 torr. H NMR (400 MHz, CDCl3): ꢀ ¼ 7.58–7.55 (m, 2H),
1
7.38–7.35 (m, 3H), 3.84 and 3.81(d, J ¼ 12.64 Hz, 6H). MS (EI): m/z (rel.
intensity) ¼ 218 (54, Mþ), 109 (100), 77 (4). IR (film): ꢁmax ¼ 3060, 2998,
2954, 2851, 1577, 1474, 1442, 1260, 1182, 1023, 985, 830, 795 cmꢁ1
.
O,O-Diethyl S-phenyl phosphorothioate 4b. Yellow oil, b.p.[10d]
84–88ꢀC/0.02 torr H NMR (400 MHz, CDCl3): ꢀ ¼ 7.58–7.55 (m, 2H),
1
7.37–7.34 (m, 3H), 4.23–4.16 (m, 4H), 1.33–1.29 (t, J ¼ 7.06 Hz, 6H).
MS (EI): m/z (rel. intensity) ¼ 246 (45, Mþ), 137 (7), 109 (100), 77 (6).
IR (film): ꢁmax ¼ 3061, 2984, 2938, 2907, 2870, 1583, 1475, 1442, 1392,
1256, 1162, 1093, 1013, 963, 796, 749 cmꢁ1
.
O,O-Di-n-butyl S-phenyl phosphorothioate 4c. Yellow oil, b.p.[10c]
0.005
118–119ꢀC. H NMR (400 MHz, CDCl3): ꢀ ¼ 7.58–7.55 (dd, J ¼ 7.56 Hz,
J ¼ 2.04 Hz, 2H), 7.36–7.34 (m, 3H), 4.14–4.07 (m, 4H), 1.66–1.61 (t, J ¼
7.52 Hz, 2H), 1.38–1.32 (q, J ¼ 7.51 Hz, 2H), 0.92–0.88 (t, J ¼ 7.38 Hz,
6H). MS (EI): m/z (rel. intensity) ¼ 303 (16, Mþ þ 1), 302 (10, M), 247
(13), 246 (9), 193 (3), 191 (50), 190 (30), 110 (34), 109 (32), 83 (100), 77
(42), 57 (37). IR (film): ꢁmax ¼ 3056, 2962, 2935, 2875, 1574, 1466, 1442,
1
1381, 1257, 1193, 1157, 1111, 1064, 1018, 985, 898, 833, 795, 748 cmꢁ1
.
O,O-Dimethyl-Te-phenyl tellurophosphonate 5a. Yellow oil. 1H NMR
(400 MHz, CDCl3): ꢀ ¼ 7.85–7.83 (d, J ¼ 6.54 Hz, J ¼ 1.42 Hz, 2H),
7.38–7.36 (m, 1H), 7.28–7.24 (m, 2H), 3.74 and 3.70 (d, J ¼ 13.6 Hz,
6H). MS (EI): m/z (rel. intensity) ¼ 316 (32, Mþ), 207 (15), 109 (100),
77 (52). IR (film): ꢁmax ¼ 3060, 2994, 2948, 2844, 1573, 1481, 1436, 1242,
1179, 1015, 817, 778, 759, 741 cmꢁ1. HRMS: calcd. for(C H11O3PTe)þ:
8
315.9508. Found: 315.9531.
O,O-Diethyl Te-phenyl tellurophosphonate 5b. Yellow oil. H NMR
1
(400 MHz, CDCl3): ꢀ ¼ 7.87–7.85 (dd, J ¼ 6.73 Hz, J ¼ 1.28 Hz, 2H),
7.39–7.37 (m, 1H), 7.29–7.25 (m, 2H), 4.19–4.13 (m, 4H), 1.34–1.31 (t,
J ¼ 7.06 Hz, 6H). MS (EI): m/z (rel. intensity) ¼ 344 (20, Mþ), 205 (9), 137
(19), 109 (100), 77 (57). IR (film): ꢁmax ¼ 3055, 2984, 2926, 2852, 1574,

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2784
Xu,Liang,and Huang
1475, 1436, 1390, 1240, 1160, 1093, 1015, 966, 796, 736 cmꢁ1. HRMS:
calcd. for(C 10H15O3PTe)þ: 343.9821. Found: 343.9803.
1
O,O-Dimethyl Te-p-tolyl tellurophosphonate 5c. Yellow oil. H NMR
(400 MHz, CDCl3): ꢀ ¼ 7.73–7.71 (dd, J ¼ 8.02 Hz, J ¼ 1.62 Hz, 2H),
7.08–7.06 (d, J ¼ 7.84 Hz, 2H), 3.74 and 3.71 (d, J ¼ 13.72 Hz, 6H), 2.35
(s, 3H). MS (EI): m/z (rel. intensity) ¼ 330 (44, Mþ), 219 (18), 109 (96), 91
(100). IR (film): ꢁmax ¼ 3030, 2949, 2849, 1487, 1444, 1379, 1241, 1180,
1019, 814, 801, 783, 759 cmꢁ1. HRMS: calcd. for(C 9H13O3PTe)þ:
329.9664. Found: 329.9691.
ACKNOWLEDGMENT
This work supported by the Natural Science Foundation of Zhejiang
Province and also by the Doctoral Program Foundation of National
Education Ministry of China.
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Received in Japan November5, 2002

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