New P-Se compounds from the reaction of 2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide with alkyl-diols

Article abstract of DOI:10.1016/j.tet.2008.04.017

Reaction of alkyl-diols [HO(CH₂)_nOH, n=2-6, 8 and 10] with 2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide [(PhP(μ-Se)Se)₂ Woollins' reagent, WR] in dry dichloromethane gave a series of bisdiselenophosphonic acids at room temperature. Treatment of the acids with butylamine in tetrahydrofuran afforded the corresponding ammonium salts 1-7 in excellent yields (91-97%). Esterification of the salts with methyl iodide led to Se,Se-dimethyl esters 8-14 in medium to excellent yields (50-86%). Alternatively, heating the toluene solution of alkyl-diols [HO(CH₂)_nOH, n=2-4] and WR at reflux, afforded 1,3,2-dioxaphosphorinane-2-phenyl-2-selenides 16, 18 and 20 in reasonable to good yield. Meanwhile, when 1,2-ethylene glycol was used, a heterocycle containing a selenium atom, 2,4-bisphenyl-2,4-diseleno-1,5-dioxa-3-seleno-2,4-diphosphetane 15 was formed. In the case of 1,3-propanediol or 1,4-butanediol, the heterocycles containing two neighbouring selenium atoms, 2,5-diphenyl-(1,6,3,4,2,5)-dioxadiselenadiphosphocane-2,5-disulfides 17 and 19 were obtained together with 18 and 20. Perhaps due to a steric effect, pinacol and WR in toluene at reflux gave 1,3,2-dioxaphosphorinane-2-selenide 21 as the only product. One representative X-ray crystal structure of an ammonium salt is described.

Full text of DOI:10.1016/j.tet.2008.04.017

Tetrahedron 64 (2008) 5442–5448
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
New P–Se compounds from the reaction of 2,4-bis(phenyl)-1,3-
diselenadiphosphetane-2,4-diselenide with alkyl-diols
*
Guoxiong Hua, Yang Li, Alexandra M.Z. Slawin, J. Derek Woollins
School of Chemistry, University of St Andrews, Fife KY16 9ST, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of alkyl-diols [HO(CH2)nOH, n¼2–6, 8 and 10] with 2,4-bis(phenyl)-1,3-diselenadiphosphetane-
Received 28 January 2008
Received in revised form 14 March 2008
Accepted 3 April 2008
2,4-diselenide [(PhP(m-Se)Se)2 Woollins’ reagent, WR] in dry dichloromethane gave a series of bis-
diselenophosphonic acids at room temperature. Treatment of the acids with butylamine in tetrahydrofuran
afforded the corresponding ammonium salts 1–7 in excellent yields (91–97%). Esterification of the salts
with methyl iodide led to Se,Se-dimethyl esters 8–14 in medium to excellent yields (50–86%). Alternatively,
heating the toluene solution of alkyl-diols [HO(CH2)nOH, n¼2–4] and WR at reflux, afforded 1,3,2-dioxa-
phosphorinane-2-phenyl-2-selenides 16, 18 and 20 in reasonable to good yield. Meanwhile, when
1,2-ethylene glycol was used, a heterocycle containing a selenium atom, 2,4-bisphenyl-2,4-diseleno-1,5-
dioxa-3-seleno-2,4-diphosphetane 15 was formed. In the case of 1,3-propanediol or 1,4-butanediol, the
heterocycles containing two neighbouring selenium atoms, 2,5-diphenyl-(1,6,3,4,2,5)-dioxadiselenadi-
phosphocane-2,5-disulfides 17 and 19 were obtained together with 18 and 20. Perhaps due to a steric effect,
pinacol and WR in toluene at reflux gave 1,3,2-dioxaphosphorinane-2-selenide 21 as the only product. One
representative X-ray crystal structure of an ammonium salt is described.
Available online 8 April 2008
Key words:
Woollins’ reagent
Alkyl-diols
Ammonium salts of bisdiselenophosphonic
acid
Se,Se-dimethyl ester
2,4-Bisphenyl-2,4-diseleno-1,5-dioxa-3-
seleno-2,4-diphosphetane
1,3,2-Dioxaphosphorinane-2-phenyl-2-
selenide
Ó 2008 Elsevier Ltd. All rights reserved.
1. Introduction
corresponding ammonium salts or used as tetradentate bisdithio-
phosphonate ligands with a wide range of metal ions.7 Lawesson’s
Lawesson’s reagent has been widely used for the transformation
of carbonyl functional groups into thiocarbonyls as well as for the
synthesis of sulfur-containing heterocyclic compounds since the
beginning of the last quarter of the 20th century.1,2 Its selenium
counterpart, 2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-dis-
reagent also reacts with dihydric alcohols at higher temperature
leading to the formation of cyclic trithiopyrophosphonate and 1,3-
dioxaphosphorinane.8 However, similar reactions have not been
tried yet for WR and complexation of phosphinodiselenoate and
phosphorodiselenoate ligands has only been reported sparsely
since 19649 whilst studies on the metal complexes of selenium
compounds have been concentrated on the field of metal cluster
chemistry.10,11 Here, we report a series of new species bearing the
P(Se)–Se or P]Se motif obtained by reaction of WR with alkyl-diols
at both room temperature and in refluxing toluene. The new am-
monium salts and methyl esters of the bisdiselenophosphonic
acids, and the cyclic selenium-containing compounds gained at
higher temperature provides a valuable addition to the phospho-
diselenoate family.
elenide [PhP(Se)(m-Se)]2, Woollins’ reagent (WR) is receiving in-
creasing attention due to its efficiency in selenation. For example,
WR has been used to prepare a wide range of selenium-containing
compounds, such as large P/Se molecular aggregates or metal
complexes by nucleophilic ring-opening reactions with alkali-
metal thiolates,3 selenoamides and selenoaldehydes by simple
oxygen/selenium exchange or reaction with ArCN followed by hy-
drolysis as well as a variety of P–Se heterocycles by simple one-step
selenation.4 Recently, we have reported the use of WR for the
syntheses of symmetrical and unsymmetrical (E)-olefins from ke-
tones or aldehydes and to deoxygenate sulfoxides to give sulfides
under relatively mild conditions.5,6
2. Results and discussion
Interaction of Lawesson’s reagent with aliphatic diols gives
bisdithiophosphonic acids, which can be converted into the
WR was prepared as described previously in high yield (>80%)4d
and further purified by Soxhlet extraction. Cleavage of the four-
membered P2Se2 ring in WR by 1 equiv of diol in dichloromethane
at room temperature afforded the bisdiselenophosphonic acids
[quantitatively as yellow oils], which were converted into the
* Corresponding author. Tel.: þ44 1334 463384.
E-mail address: jdw3@st-and.ac.uk (J. Derek Woollins).
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.04.017

G. Hua et al. / Tetrahedron 64 (2008) 5442–5448
5443
Se
P
2
Se
P
Se
P
Se
P
Se
P
Se
HO(CH2)nOH
BuNH2
Ph
O(CH )
2 n O
Ph
O(CH2)nO
2 H3NBu
Ph
Ph
Se P
Se
SeH
Se
Se
SeH
Woollins' reagent
1 - 7, n = 2 - 6, 8, 10
Scheme 1. Synthesis of amine salts of bisdiselenophosphonic acid 1–7.
with the 31P resonance moving slightly upfield as the (CH2)n chain
length increases. Each singlet is accompanied by selenium satellites
[range 657–678 Hz] indicating, as expected, a P–Se bond order of
approximately 1.5; 1 has the highest J value (average 18 Hz differ-
ence) possibly due to the close distance between two phosphorus
atoms within 1. The 77Se–{1H} NMR spectra display doublets [
d(Se)
73.23, 91.34, 84.06, 87.81, 88.27, 84.75 and 87.81 ppm, respectively].
The 1H and 13C NMR spectra of 1–7 were as expected confirming the
presence of the phenyl, O(CH2)nO and H3NBu moieties. Microanal-
ysis results and mass spectra are in good agreement with theoretical
values whilst IR spectra show bands at 560–543 and 522–501 cmꢀ1
corresponding tov(PSe)asym and v(PSe)sym absorptions, respectively.
All attempts to crystallise salts proved unsuccessful apart from
salt 1. Single crystals of 1 were obtained by diffusion of the
dichloromethane solution into hexane. The building block for 1 is
displayed in Figure 1.12 This compound exhibits a very interesting
structuralmotif. Itconsists of a [PhP(Se)(Se)OCH2CH2O(Se)(Se)PPh]2ꢀ
anion and two [BuNH3]þ cations, forming a wing-like structure
with the two bulky phenyl groups oriented on the same side of the
anion which has an approximate mirror plane bisecting the P–O–
C–C–O–P axis. The P–Se bond lengths [2.1366(12), 2.1350(12),
2.1280(11) and 2.1490(13) Å] in line with other symmetrical phos-
phenium salts (typical bond length of 2.13 Å)13 are intermediate be-
tween single [ca. 2.38 Å] and double [P]Se double bond ca. 2.08 Å].14
Replacement of the two H3NBu cations in the amine salts of
bisdiselenophosphonic acid 1–7 by 2 equiv of iodomethane gen-
erated bis(phenyl-diselenophosphonic acid Se,Se-dimethyl esters)
8–14 as yellow oils in high yields (Scheme 2), which are soluble in
normal solvents such as chloroform, dichloromethane and acetone
but are insoluble in strong polar solvents such as alcohols or
amines. Esters 8–14 are stable to air and moisture for months at
room temperature. As expected, the diesters 8–12 are mixtures of
diastereoisomers. However, for 13 and 14, only one major com-
pound was obtained. These results were confirmed by analysis of
1H, 13C, 31P and 77Se NMR spectra. Diester 8 consists of diastereomer
pairs in approximately equal amounts, while 9–12 are a mixture of
three diastereomers of random populations. All attempts to further
purify these mixtures were unsuccessful. Despite the presence of
two stereogenic centres in 13 and 14, no separate signals assignable
Figure 1. X-ray crystal structure of 1, selected bond lengths (Å) and angles (ꢁ): Se(1)–
P(1) 2.1366(12), Se(11)–P(11) 2.1280(11), P(1)–O(1) 1.630(3), P(11)–O(11) 1.619(2),
P(1)–C(1) 1.817(4), P(11)–C(11) 1.827(4), O(1)–C(7) 1.454(5), O(11)–C(17) 2.439(4),
Se(2)–P(1) 2.1350(12), Se(12)–P(11) 2.1490(13), Se(1)–P(1)–Se(2) 118.65(5), Se(11)–
P(11)–Se(12) 117.22(5), Se(2)–P(1)–O(1) 110.97(12), Se(12)–P(11)–O(11) 111.21(12),
Se(1)–P(1)–O(1) 102.65(11), Se(11)–P(11)–O(11) 103.08(10), P(1)–O(1)–C(7) 123.3(2),
P(11)–O(11)–C(17) 122.9(2).
Se
P
Se
P
Se
P
Se
P
CH3I
O(CH2)nO
Ph
Ph
O(CH2)n O
Ph
Ph
THF, RT
Se-
Se-
SeCH3
8 - 14, n = 2 - 6, 8, 10
Scheme 2. Synthesis of Se,Se-dialkyl esters 8–14.
SeCH3
corresponding amine salts (1–7) by further treatment with butyl-
amine at room temperature (Scheme 1).
Salts 1–7 were obtained in highyields as white solid or colourless
pastes, which were moderately stable in air, degrading over a period
of several weeks with the obvious signs of red elemental selenium
accompanying the evolution of a foul-smelling gas. All salts are
soluble in chloroform, dichloromethane, and tetrahydrofuran and
insoluble in diethyl ether and hexane. The 31P–{1H} NMR spectra of
to either diastereoisomeric forms were observed in their 1H, 13C, 31
and 77Se NMR spectra.
P
Interestingly, heating a toluene solution of WR with ethylene
glycol at reflux led to new ring systems, a seven-membered ring
triselenapyrophosphonate 15 and a five-membered ring 1,3-di-
oxaphosphorinane-2-selenide 16 (Scheme 3). Different ratios of
1–7 display sharp singlets in the range of
d
(P) 78.65–84.85 ppm,
Se
O
E
O
Se
Se
Se
O
O
P
Se
P
Alkyl-Diol
P
P
+
E
P
Se
Toluene, reflux
Se n
Se
16, E = (CH2)2
15, E = (CH2)2, n = 1
17, E = (CH2)3, n = 2
19, E = (CH2)4, n = 2
18, E = (CH2)3
20, E = (CH2)4
21, E = C(CH3)2C(CH3)2
Scheme 3. Synthesis of P–Se heterocycles 15–21.

5444
G. Hua et al. / Tetrahedron 64 (2008) 5442–5448
Table 1
University of St Andrews microanalysis service. Mass spectrometry
was performed by the EPSRC National Mass Spectrometry Service
Centre, Swansea (UK) and the University of St Andrews Mass Spec-
trometry Service. We compared observed isotopomer distributions
with calculated patterns to confirm assignments. X-ray crystal data
for compound 1 was collected at 93 K by using a Rigaku MM007
High brilliance RA generator/confocal optics and Mercury CCD
system. Intensities were corrected for Lorentz-polarisation and for
absorption. The structure was solved by direct methods. Hydrogen
atoms bound to carbon were idealised. Structural refinement was
obtained with full-matrix least-squares based on F2 using SHELXTL.
CCDC 681330 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge
Crystallographic Data centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax þ44 1223 336 033; e-mail: deposit@ccdc.cam.ac.uk.
Proportion of 15 and 16 when various ratios of starting materials were applied
Entry
WR (mmol)
Ethylene glycol (mmol)
Yield of 15 (%)
Yield of 16 (%)
1
2
3
4
1.0
1.0
1.0
1.0
0.5
1.0
1.5
5.0
31
72
74
73
69
28
26
27
starting materials resulted in the same products 15 and 16 but with
different proportions (Table 1). It is noted that using a large excess
of ethylene glycol (entry 4) did not change the proportion of
products 15 and 16.
However, under the same reaction conditions, 1,3-propanediol
or 1,4-butanediol reacts with WR to give cyclic tetraselenapyr-
ophosphonates 17, 19 containing diselenides [–Se–Se–] as part of
ring, and 1,3-dioxaphosphorinane-2-selenides 18, 20, respectively.
Surprisingly, only 1,3,2-dioxaphosphorinane-2-phenyl-2-selenide
21 was obtained as pale yellow solid by the reaction of pinacol with
WR in toluene in 69% yield (Scheme 3).
3.2. General procedure for synthesis of dibutylammonium
bisdiselenophosphonates
Compound 15 was isolated as yellow oil. The 31P–{1H} NMR
spectrum obtained in dichloromethane consists of a singlet at dP
75.02 ppm with two sets of 77Se satellites (vide infra), arising from
two distinct isotopomers with one 77Se atom in the exo- or endo-
position of the ring. For these two sets of systems A2X (Seendo) and
AA0X (Seexo) (A, A0¼31P, X¼77Se), iterative simulation allowed for
complete analysis of chemical shifts and coupling constants, e.g.,
2J(P,P) (14.1 Hz). The magnitudes of J(P,Se) are as expected. The
A mixture of diol (1.0 mmol) and WR (0.54 g, 1.0 mmol) in dry
dichloromethane (20 ml) was stirred at room temperature for 20 h.
The red suspension disappeared and a greenish yellow solution was
formed along with a trace precipitate of grey elemental selenium.
The resulting mixture was filtered. The filtrate was concentrated in
vacuo leading to a green paste. The residue was dissolved in tet-
rahydrofuran (50 ml) (yellow solution) and butylamine (0.5 ml)
was added dropwise. This resulted in the formation of a brown
suspension and then a grey or pale grey suspension after 4 h stir-
ring at room temperature. Compounds 1–7 were filtered off and
washed with dichloromethane and diethyl ether.
77Se–{1H} spectrum of 15 showed two signals:
a triplet at
dSe¼696.24 ppm with 1J(P,Seendo)¼396 Hz, a doublet of doublets at
dSe¼5.37 ppm with 1J(P,Seexo)¼851 Hz and 3J(P,Seexo)¼9.8 Hz. The
MS, 1H and 13C NMR spectra also confirmed the identity of 15. In the
13C NMR spectrum the endocyclic carbon gave a doublet at dC
1
135.4 ppm with J(P,C)¼104 Hz, 3J(P,C)¼12.5 Hz.
3.2.1. Dibutylammonium 1,2-dioxoethane-1,2-bis(phenyl-
diselenophosphonate) (1)
We have recently published the first synthesis and character-
isation of the compounds 17 and 19, as 9- and 10-membered het-
erocycles containing the O–P–Se–Se–P–O linkage,15 therefore the
two compounds will not be discussed here in detail. Compounds 16,
18, 20 and 21, which are homologues of 17 and 19 were isolated as
white pastes. All are soluble in polar solvents such as alcohols and
acetone but are insoluble in less polar solvents. They are quite stable
to air and moisture. The 31P–{1H} NMR spectra of 16, 18, 20 and 21
display sharp singlets [dP 111.60, 93.27, 93.09, 99.19 ppm, J(31P–77Se)
876–911 Hz] indicating the presence of a P]Se double bond in each
molecule as anticipated. The results were further substantiated by
the 77Se–{1H} NMR spectra, which showed doublets [dSe ꢀ203.95,
ꢀ247.17, ꢀ212.44 and ꢀ84.14 ppm] with matching 31P–{1H}–77Se–
{1H} coupling constants. The 1H and 13C NMR spectra of 16, 18, 20
and 21 confirm the presence of the phenyl and O(CH2)nO (n¼2, 3 and
4) or OC(CH3)2C(CH3)2O moieties and mass spectrometry showed
the parent ions (ESIþ or CIþ mode) as [MþNa]þ or [MþH]þ.
White solid (701 mg) in 95% yield. Mp 96 ꢁC. Found (calcd for
C
22H38N2O2P2Se4): C 35.35 (35.69), H 5.01 (5.17), N 3.50 (3.78). Se-
lected IR (KBr, cmꢀ1): 2958 (s),1467 (w),1434 (m),1048 (s), 973 (m),
934 (s), 745 (m), 692 (m), 560 (s), 522 (m). 1H NMR (CDCl3,
d), 8.05
(m, 6H, NHþ3 ), 8.02 (dd, 3J(P,H)¼13 Hz, 3J(P,H)¼8 Hz, 4H, ArH), 7.82
(m, 3J(P,H)¼13 Hz, 2H, ArH), 7.36 (d, 2H, ArH), 6.81 (d, 2H, ArH), 3.82
(dd, 3J(P,H)¼26 Hz, 3J(H,H)¼6 Hz, 4H, OCH2), 2.96 (t, 3J(H,H)¼7 Hz,
4H, NCH2), 1.64 (m, 3J(H,H)¼7 Hz, 4H, CH2), 1.29 (m, 3J(H,H)¼6 Hz,
4H, CH2), 0.84 (t, 3J(H,H)¼7 Hz, 6H, CH3) ppm. 13C NMR (CDCl3,
d),
140.8 (d, 1J(P,C)¼76 Hz), 130.9 (d, 4J(P,C)¼3.1 Hz), 130.2 (d,
2J(P,C)¼14.5 Hz), 127.9 (d, 3J(P,C)¼12.5 Hz), 63.0, 40.1, 30.5, 20.0,
13.7 ppm. 31P–{1H} NMR (CDCl3,
d
), 84.85 (s, 1J(P,Se)¼678 Hz) ppm.
77Se–{1H} NMR (CDCl3,
d
), 73.23 (d, 1J(P,Se)¼678 Hz) ppm. MS (ESꢀ,
m/z): 588 [MꢀC4H12NSe]þ, 329 [MꢀC14H28N2PSe2]þ. MS (EI, m/z):
742 [M]þ, 663 [MꢀSeH]þ.
3.2.2. Dibutylammonium 1,3-dioxopropane-1,3-bis(phenyl-
diselenophosphonate) (2)
3. Experimental section
3.1. General
Colourless paste (732 mg) in 97% yield. Found (calcd for
C23H40N2O2P2Se4): C 36.32 (36.62), H 4.91 (5.34), N 3.59 (3.71).
Selected IR (KBr, cmꢀ1): 2958 (s),1588 (m),1467 (m),1435 (m),1098
(m), 1040 (s), 949 (m), 748 (m), 693 (s), 543 (s), 501 (m). 1H NMR
Unless otherwise stated, all reactions were carried out under an
oxygen free nitrogen atmosphere using pre-dried solvents and
standard Schlenk techniques. Subsequent chromatographic and
work up procedures were performed in air. Solvents were dried,
purified, and stored according to common procedures. 1H (270 Hz),
13C (67.9 Hz), 31P–{1H} (109 Hz) and 77Se–{1H} (51.4 Hz referenced
to external Me2Se) NMR spectra were recorded at 25 ꢁC (unless
stated otherwise) on a JEOL GSX 270. IR spectra were recorded as
KBr pellets in the range of 4000–250 cmꢀ1 on a Perkin–Elmer 2000
FTIR/Raman spectrometer. Microanalysis was performed by the
(CDCl3,
d
), 8.11 (m, 6H, NHþ3 ), 7.82 (m, 3J(P,H)¼13 Hz, 3J(P,H)¼8 Hz,
4H, ArH), 7.37 (d, 3J(P,H)¼13 Hz, 2H, ArH), 7.22 (d, 2H, ArH), 7.17
(d, 2H, ArH), 3.98 (dd, 3J(P,H)¼26 Hz, 3J(H,H)¼6 Hz, 4H, OCH2), 3.01
(t, 3J(H,H)¼7 Hz, 4H, NCH2), 1.97 (m, 2H, CH2), 1.64 (m,
3J(H,H)¼7 Hz, 4H, CH2), 1.30 (m, 3J(H,H)¼6 Hz, 4H, CH2), 0.83 (t,
3J(H,H)¼7 Hz, 6H, CH3) ppm. 13C NMR (CDCl3,
d), 141.7 (d,
1J(P,C)¼82 Hz), 131.8 (d, 4J(P,C)¼3.1 Hz), 128.5 (d, 2J(P,C)¼14.5 Hz),
127.9 (d, 3J(P,C)¼12.5 Hz), 63.5, 40.2, 30.7, 29.8, 19.9, 13.7 ppm. 31P–
{1H} NMR (CDCl3,
d
), 81.14 (s, 1J(P,Se)¼660 Hz) ppm. 77Se–{1H} NMR
(CDCl3,
d
), 91.34 (d, 1J(P,Se)¼660 Hz) ppm. MS (ESꢀ, m/z): 602

G. Hua et al. / Tetrahedron 64 (2008) 5442–5448
5445
[MꢀC4H12NSe]þ, 343 [MꢀC14H28N2PSe2]þ. MS (EI, m/z): 756 [M]þ,
29.0, 25.7, 19.9, 13.8 ppm. 31P–{1H} NMR (CDCl3,
d), 78.93 (s,
677 [MꢀSeH]þ.
1J(P,Se)¼657 Hz) ppm. 77Se–{1H} NMR (CDCl3,
d), 84.75 (d,
1J(P,Se)¼658 Hz) ppm. MS (ESꢀ, m/z): 672 [MꢀC4H12NSe]þ, 413
[MꢀC14H28N2PSe2]þ. MS (EI, m/z): 826 [M]þ, 747 [MꢀSeH]þ.
3.2.3. Dibutylammonium 1,4-dioxobutane-1,4-bis(phenyl-
diselenophosphonate) (3)
Colourless paste (695 mg) in 91% yield. Found (calcd for
3.2.7. Dibutylammonium 1,10-dioxodecane-1,10-bis(phenyl-
diselenophosphonate) (7)
C
24H42N2O2P2Se4): C 37.05 (37.51), H 5.12 (5.51), N 3.30 (3.65). Se-
lected IR (KBr, cmꢀ1): 2958 (s), 2866 (w), 1590 (w), 1466 (m), 1436
(m), 1118 (m), 1095 (m), 1035 (s), 748 (m), 694 (m), 566 (s), 543 (s),
Colourless paste (805 mg) in 95% yield. Found (calcd for
C
30H54N2O2P2Se4): C 41.98 (42.26), H 6.21 (6.38), N 3.50 (3.29).
506 (m). 1H NMR (CDCl3,
d
), 8.13 (m, 6H, NHþ3 ), 7.82 (m,
Selected IR (KBr, cmꢀ1): 2930 (vs), 2855 (m), 1590 (w), 1465 (m),
1435 (m), 1095 (m), 1025 (m), 748 (m), 694 (s), 566 (s), 543 (s), 504
3J(P,H)¼13 Hz, 3J(P,H)¼8 Hz, 4H, ArH), 7.42 (d, 3J(P,H)¼13 Hz, 2H,
ArH), 7.21 (d, 2H, ArH), 7.15 (d, 2H, ArH), 3.87 (dd, 3J(P,H)¼26 Hz,
3J(H,H)¼6 Hz, 4H, OCH2), 2.88 (t, 3J(H,H)¼7 Hz, 4H, NCH2), 1.78
(m, 4H), 1.72 (m, 3J(H,H)¼7 Hz, 4H, CH2), 1.29 (m, 3J(H,H)¼6 Hz, 4H,
(m). 1H NMR (CDCl3, ), 8.13 (m, 6H, NHþ3 ), 7.83 (m, 4H, ArH), 7.44–
d
7.34 (m, 6H, ArH), 3.78 (dd, 4H, OCH2), 2.80 (t, 4H, NCH2), 1.58–1.47
(m, 8H, CH2), 1.34–1.18 (m, 16H, CH2), 0.86 (m, 6H, CH3) ppm. 13C
CH2), 0.82 (t, 3J(H,H)¼7 Hz, 6H, CH3) ppm. 13C NMR (CDCl3,
d), 142.0
NMR (CDCl3,
d
), 142.2 (d, 1J(P,C)¼82 Hz), 131.7 (d, 4J(P,C)¼3.1 Hz),
(d,1J(P,C)¼84 Hz),131.8 (d, 4J(P,C)¼3.1 Hz),130.1 (d, 2J(P,C)¼14.5 Hz),
127.9 (d, 3J(P,C)¼12.5 Hz), 66.0, 40.2, 30.5, 26.7, 19.9, 13.7 ppm.
130.1 (d, 2J(P,C)¼14.5 Hz), 127.7 (d, 3J(P,C)¼12.5 Hz), 66.3, 40.2,
31.2, 30.1, 29.3, 29.1, 25.8, 20.0, 13.7 ppm. 31P–{1H} NMR (CDCl3,
d),
31P–{1H} NMR (CDCl3,
d
), 81.12 (s, 1J(P,Se)¼662 Hz) ppm. 77Se–
78.65 (s, 1J(P,Se)¼657 Hz) ppm. 77Se–{1H} NMR (CDCl3,
d), 87.81 (d,
{1H} NMR (CDCl3,
d
), 84.06 (d, 1J(P,Se)¼668 Hz) ppm. MS (ESꢀ,
1J(P,Se)¼658 Hz) ppm. MS (ESꢀ, m/z): 700 [MꢀC4H12NSe]þ, 441
[MꢀC14H28N2PSe2]þ. MS (EI, m/z): 854 [M]þ, 775 [MꢀSeH]þ.
m/z): 616 [MꢀC4H12NSe]þ, 357 [MꢀC14H28N2PSe2]þ. MS (EI,
m/z): 770 [M]þ, 691 [MꢀSeH]þ.
3.3. General procedure for synthesis of bis(phenyl-
diselenophosphonic acid Se,Se-dimethyl ester)
3.2.4. Dibutylammonium 1,5-dioxopantane-1,5-bis(phenyl-
diselenophosphonate) (4)
Colourless paste (365 mg) in 93% yield. Found (calcd for
A tetrahydrofuran solution of dibutylammonium bisdiseleno-
phosphonate (2.0 mmol) was cooled to 0 ꢁC and CH3I (0.60 g
0.26 ml, 4.2 mmol) was added dropwise to give a milky grey sus-
pension. Continued stirring overnight at room temperature gave
a pale green suspension. The resulting solution was concentrated in
vacuo and the residue was dissolved in ethyl acetate and washed
with 2% Na2S2O4 aqueous solution, twice with water and brine, and
dried over MgSO4. Concentration in vacuo left the crude diester,
which was purified on a silica gel column with dichloromethane as
an eluent to give esters 8–14.
C
25H44N2O2P2Se4): C 37.97 (38.48), H 5.51 (5.67), N 3.43 (3.58).
Selected IR (KBr, cmꢀ1): 2958 (vs), 2872 (m), 1588 (m), 1467 (m),
1435 (m), 1099 (m), 974 (m), 748 (m), 693 (m), 565 (s), 542 (s), 504
(m). 1H NMR (CDCl3, ), 8.10 (m, 6H, NHþ3 ), 7.81 (m, 4H, ArH), 7.36 (d,
d
2H, ArH), 7.25 (d, 2H, ArH), 7.08 (d, 2H, ArH), 3.78 (dd, 4H, OCH2),
2.95 (t, 4H, NCH2), 1.65 (m, 4H, CH2), 1.47 (m, 2H, CH2), 1.30–1.21 (m,
8H, CH2), 0.82 (m, 6H, CH3) ppm. 13C NMR (CDCl3,
d), 141.7 (d,
1J(P,C)¼80 Hz), 131.8 (d, 4J(P,C)¼3.1 Hz), 130.1 (d, 2J(P,C)¼14.5 Hz),
127.9 (d, 3J(P,C)¼12.5 Hz), 66.4, 40.1, 29.7, 29.5, 22.6, 19.9, 13.7 ppm.
31P–{1H} NMR (CDCl3,
d
), 80.28 (s, 1J(P,Se)¼660 Hz) ppm. 77Se–{1H}
NMR (CDCl3,
d
), 87.81 (d, 1J(P,Se)¼658 Hz) ppm. MS (ESꢀ, m/z): 630
3.3.1. 1,2-Dioxoethane-1,2-bis(phenyl-diselenophosphonic acid
Se,Se-dimethyl ester) (8)
[MꢀC4H12NSe]þ, 371 [MꢀC14H28N2PSe2]þ. MS (EI, m/z): 784 [M]þ,
705 [MꢀSeH]þ.
Pale yellow oil (537 mg) in 86% yield. Found (calcd for
C
16H20O2P2Se4): C 30.55 (30.89), H 3.01 (3.24). Selected IR (KBr,
3.2.5. Dibutylammonium 1,6-dioxohexane-1,6-bis(phenyl-
diselenophosphonate) (5)
cmꢀ1): 3054 (w), 2927 (m), 1436 (m), 1268 (w), 1105 (s), 1064 (m),
1021 (s), 942 (s), 775 (m), 745 (s), 712 (m), 688 (s), 550 (vs, P]Se).
Colourless paste (370 mg) in 93% yield. Found (calcd for
C26H46N2O2P2Se4): C 39.01 (39.21), H 5.43 (5.82), N 3.32 (3.52).
Selected IR (KBr, cmꢀ1): 2933 (vs), 2871 (m), 1588 (m), 1464 (m),
1435 (m), 1099 (m), 991 (s), 748 (m), 694 (s), 566 (s), 543 (s), 504
1H NMR (CDCl3,
d
), 7.98 and 7.91 (2ꢂdd, 3J(P,H)¼13.1 Hz, 3J(H,H)¼
7.9 Hz, 4H, ArH), 7.49–7.48 (2ꢂm, 6H, ArH), 4.48 and 4.36 (2ꢂm,
4H, OCH2), 2.06 and 2.08 (2ꢂd, 3J(P,H)¼6.4 Hz, 6H, SeCH3) ppm. 13
C
NMR (CDCl3,
d
), 135.7 and 135.6 (2ꢂd, 1J(P,C)¼99 Hz), 132.4 and
(m). 1H NMR (CDCl3,
d
), 8.15 (m, 6H, NHþ3 ), 7.83 (m, 4H, ArH), 7.44–
132.3 (2ꢂd, 4J(P,C)¼2 Hz), 130.5 and 130.4 (2ꢂd, 3J(P,C)¼13 Hz),
128.6 (d, 2J(P,C)¼15 Hz), 64.7 and 64.6 (2ꢂd, 2J(P,C)¼10.5 Hz, OCH2),
11.1 and 11.2 (2ꢂd, 2J(P,C)¼3.1 Hz, SeCH3) ppm. 31P–{1H} NMR
7.35 (m, 6H, ArH), 3.74 (m, 4H, OCH2), 2.82 (t, 4H, NCH2), 1.84 (m,
4H, CH2), 1.59 (m, 4H, CH2), 1.35–1.22 (m, 8H, CH2), 0.82 (m,
6H, CH3) ppm. 13C NMR (CDCl3,
d
), 142.0 (d, 1J(P,C)¼81 Hz), 130.8 (d,
(CDCl3,
d), 83.74 and 83.69 (2ꢂs, J(P,Seendo)¼446 Hz, J(P,Seexo)¼
4J(P,C)¼3.1 Hz), 130.1 (d, 2J(P,C)¼14.5 Hz), 127.8 (d, 3J(P,C)¼12.5 Hz),
827 Hz) ppm. 77Se–{1H} NMR (CDCl3,
d), 250.34 and 260.31 (2ꢂd,
66.1, 40.3, 31.2, 29.9, 25.6, 19.9, 13.7 ppm. 31P–{1H} NMR (CDCl3,
d
),
J(P,Seendo)¼446 Hz), ꢀ100.25 and ꢀ103.3 (2ꢂd, J(P,Seexo)¼
827 Hz) ppm. MS (EI, m/z): 624 [M]þ, 451 [MꢀSeꢀSeCH3]þ, 205
[MꢀC10H12OPSe3]þ. MS (CIþ, m/z): 625 [MþH]þ.
79.33 (s, 1J(P,Se)¼657 Hz) ppm. 77Se–{1H} NMR (CDCl3,
d), 88.27 (d,
1J(P,Se)¼653 Hz) ppm. MS (ESꢀ, m/z): 644 [MꢀC4H12NSe]þ, 385
[MꢀC14H28N2PSe2]þ. MS (EI, m/z): 798 [M]þ, 719 [MꢀSeH]þ.
3.3.2. 1,3-Dioxoethane-1,2-bis(phenyl-diselenophosphonic acid
Se,Se-dimethyl ester) (9)
Pale yellow oil (444 mg) in 70% isolated yield. Found (calcd for
C17H22O2P2Se4): C 31.65 (32.10), H 3.71 (3.49). Selected IR (KBr,
cmꢀ1): 3053 (w), 2954 (m), 2919 (m), 1436 (m), 1269 (w), 1105 (s),
1034 (s), 960 (s), 747 (m), 713 (m), 689 (s), 551(vs, P]Se), 498(m).
3.2.6. Dibutylammonium 1,8-dioxooctane-1,8-bis(phenyl-
diselenophosphonate) (6)
Colourless paste (401 mg) in 97% yield. Found (calcd for
C
28H50N2O2P2Se4): C 41.22 (40.79), H 6.07 (6.11), N 3.51 (3.40).
Selected IR (KBr, cmꢀ1): 2931(vs), 2860 (s), 1591 (w), 1464 (m), 1435
(m), 1024 (s), 748 (m), 694 (s), 565 (s), 544 (s), 504 (m). 1H NMR
1H NMR (CD2Cl2,
d
), 8.03–7.88 (3ꢂm, 4H, ArH), 7.58–7.43 (3ꢂm, 6H,
(CDCl3,
d
), 8.13 (m, 6H, NHþ3 ), 7.83 (m, 4H, ArH), 7.33 (m, 6H, ArH),
ArH), 4.42 and 4.22 (3ꢂm, 4H, OCH2), 2.28–2.21 (3ꢂm, 2H, CH2),
3.77 (dd, 4H, OCH2), 2.71 (t, 4H, NCH2), 1.57–1.40 (m, 8H, CH2),
2.13, 2.08 and 2.03 (3ꢂd, 6H, SeCH3) ppm. 13C NMR (CD2Cl2,
d),
1.27–1.21 (m, 12H, CH2), 0.82 (m, 6H, CH3) ppm. 13C NMR (CDCl3,
d
),
136.9, 135.9, 135.2, 132.4 (d, 2J(P,C)¼3.1 Hz), 131.7, 130.8, 130.6,
130.4, 130.3, 128.7, 128.4, 128.3, 63.1, 63.0 and 62.8 (3ꢂd, OCH2),
33.6, 30.5 and 30.2 (CH2), 13.5, 11.2 and 11.1 (SeCH3) ppm. 31P–{1H}
142.3 (d, 1J(P,C)¼83 Hz), 131.7 (d, 4J(P,C)¼3.1 Hz), 130.2 (d,
2J(P,C)¼14.5 Hz), 127.7 (d, 3J(P,C)¼12.5 Hz), 66.1, 40.5, 32.4, 29.9,

5446
G. Hua et al. / Tetrahedron 64 (2008) 5442–5448
NMR (CD2Cl2,
d
), three diastereoisomers (2.0:2.5:1.0), 81.95, 81.37
oil in 31% yield. Found (calcd for C20H28O2P2Se4): C 35.11 (35.42), H
4.04 (4.16). Selected IR (KBr, cmꢀ1): 3050 (w), 2930 (m), 2860 (w),
1437 (m),1268 (w),1106 (m), 989 (s), 747 (m), 713 (m), 690 (m), 552
and 81.05 (3ꢂs, J(P,Seendo)¼441 Hz, J(P,Seexo)¼826 Hz) ppm. 77Se–
{1H} NMR (CD2Cl2,
d), three diastereoisomers, 257.81, 254.66 and
254.11 (3ꢂd, J(P,Seendo)¼439 Hz), ꢀ103.45, ꢀ104.39 and ꢀ104.86
(3ꢂd, J(P,Seexo)¼827 Hz) ppm. MS (EI, m/z): 638 [M]þ, 465
[MꢀSeꢀSeCH3]þ, 205 [MꢀC11H14OPSe3]þ. MS (CIþ, m/z): 639
[MþH]þ.
(vs, P]Se), 499 (m). 1H NMR (CD2Cl2,
d), a pair of diastereoisomers:
7.95–7.87 (2ꢂm, 4H, ArH), 7.52–7.41 (2ꢂm, 6H, ArH), 4.28–3.92
(2ꢂm, 2ꢂ4H, OCH2), 2.08 and 2.04 (2ꢂd, 6H, SeCH3), 1.79 and 1.75
(2ꢂm, 4H, CH2), 1.52 and 1.45 (2ꢂm, 4H, CH2) ppm. 13C NMR
(CD2Cl2,
d
), 136.3 and 135.5 (2ꢂd, 1J(P,C)¼99.7 Hz), 132.2 and 131.5
3.3.3. 1,4-Dioxoethane-1,2-bis(phenyl-diselenophosphonic acid
Se,Se-dimethyl ester) (10)
(2ꢂd, 4J(P,C)¼3.1 Hz), 130.6 and 130.3 (2ꢂd, 3J(P,C)¼11.4 Hz), 128.5
and 128.4 (2ꢂd, 2J(P,C)¼14.5 Hz), 66.6 and 65.4 (2ꢂd, 2J(P,C)¼
6.2 Hz, OCH2), 30.0 and 29.8 (CH2), 25.5 and 25.4 (CH2), 10.8 and
Pale yellow oil (400 mg) in 62% yield. Found (calcd for
C
18H24O2P2Se4): C 33.19 (33.25), H 4.01 (3.72). Selected IR (KBr,
10.7 (2ꢂd, 2J(P,C)¼4.2 Hz, SeCH3) ppm. 31P–{1H} NMR (CD2Cl2,
d),
cmꢀ1): 3054 (w), 2952 (w), 2926 (w), 1436 (m), 1269 (w), 1105 (s),
two diastereoisomers (1:1): 80.41 and 80.36 (s, J(P,Seendo)¼437 Hz,
945 (s), 747 (m), 712 (m), 689 (s), 550 (vs, P]Se), 499 (m). 1H NMR
J(P,Seexo)¼826 Hz) ppm. 77Se–{1H} NMR (CD2Cl2,
d), two
(CD2Cl2,
d
), 7.96–7.78 (3ꢂm, 4H, ArH), 7.56–7.40 (3ꢂm, 6H, ArH),
diastereoisomers: 153.72 and 253.51 (2ꢂd, J(P,Seendo)¼436 Hz),
ꢀ102.38 and ꢀ102.47 (2ꢂd, J(P,Seexo)¼825 Hz) ppm. MS (EI, m/z):
680 [M]þ, 507 [MꢀSeꢀSeCH3]þ, 205 [MꢀC14H20OPSe3]þ. MS (CIþ,
m/z): 681 [MþH]þ.
4.38–4.06 (3ꢂm, 4H, OCH2), 2.86–2.69 (3ꢂm, 4H, CH2), 2.09, 2.08
and 2.07 (3ꢂd, 6H, SeCH3) ppm. 13C NMR (CD2Cl2,
d), 136.9, 136.2,
135.4, 132.4, 132.3, 131.7, 131.6, 130.7, 130.6, 130.4, 130.2, 128.6,
128.5, 128.4, 128.3, 68.1, 66.1 and 64.9 (3ꢂd, 2J(P,C)¼6.2 Hz, OCH2),
26.8, 26.6, 26.4 (CH2), 13.5, 11.1 and 11.0 (SeCH3) ppm. 31P–{1H}
3.3.6. 1,8-Dioxoethane-1,2-bis(phenyl-diselenophosphonic acid
Se,Se-dimethyl ester) (13)
NMR (CD2Cl2, d), three diastereoisomers (1:1:0.5), 81.07, 81.03 and
80.84 (3ꢂs, J(P,Seendo)¼437 Hz, J(P,Seexo)¼824 Hz) ppm. 77Se–{1H}
Yellow oil (334 mg) in 50% yield. Found (calcd for C22H32O2P2Se4):
C 36.97 (37.41), H 4.39 (4.47). Selected IR (KBr, cmꢀ1): 3050 (w),
2928 (m), 2854 (w),1436 (m),1269 (w),1105 (s), 990 (s), 746 (m), 713
NMR (CD2Cl2, d), three diastereoisomers (1:1:0.5), 254.80, 254.71
and 254.52 (3ꢂd, J(P,Seendo)¼440 Hz), ꢀ103.03, ꢀ102.82 and
ꢀ102.61 (3ꢂd, J(P,Seexo)¼825 Hz) ppm. MS (EI, m/z): 652 [M]þ, 479
[MꢀSeꢀSeCH3]þ, 205 [MꢀC12H16OPSe3]þ. MS (CIþ, m/z): 653
[MþH]þ.
(m), 689 (m), 552 (vs, P]Se), 499 (m). 1H NMR (CD2Cl2,
d), 7.94–7.76
(m, 4H, ArH), 7.51 (m, 6H, ArH), 4.22–4.01 (m, 4H, OCH2), 2.06 (d,
6H, SeCH3), 1.74 (m, 4H, CH2), 1.39 (m, 4H, CH2), 1.25 (m, 4H,
CH2) ppm. 13C NMR (CD2Cl2,
d
), 136.3 (d, 1J(P,C)¼100.0 Hz), 132.3 (d,
3.3.4. 1,5-Dioxoethane-1,2-bis(phenyl-diselenophosphonic acid
Se,Se-dimethyl ester) (11)
4J(P,C)¼3.1 Hz), 130.3 (d, 3J(P,C)¼12.4 Hz), 128.5 (d, 2J(P,C)¼13.5 Hz),
66.8, 29.9, 25.8, 20.1, 10.8 (SeCH3) ppm. 31P–{1H} NMR (CD2Cl2,
d),
Pale yellow oil (445 mg) in 67% yield. Found (calcd for
81.17 (s, J(P,Seendo)¼439 Hz, J(P,Seexo)¼834 Hz) ppm. 77Se–{1H} NMR
C
19H26O2P2Se4): C 33.79 (34.30), H 4.09 (4.16). Selected IR (KBr,
(CD2Cl2,
d
), 253.41 (d, J(P,Seendo)¼434 Hz), ꢀ103.03 (d, J(P,Seexo)¼
cmꢀ1): 3056 (w), 2949 (m), 2872 (w), 1436 (m), 1269 (w), 1105 (s),
823 Hz) ppm. MS (EI, m/z): 708 [M]þ, 535 [MꢀSeꢀSeCH3]þ, 205
974 (s), 747 (m), 713 (m), 689 (m), 552 (vs, P]Se), 499 (m). 1H NMR
[MꢀC16H24OPSe3]þ. MS (CIþ, m/z): 709 [MþH]þ.
(CD2Cl2,
d
), 7.94–7.77 (3ꢂm, 4H, ArH), 7.51–7.45 (3ꢂm, 6H, ArH),
4.26–4.04 (3ꢂm, 4H, OCH2), 2.08, 2.06 and 2.05 (3ꢂd, 6H, SeCH3),
3.3.7. 1,10-Dioxoethane-1,2-bis(phenyl-diselenophosphonic acid
Se,Se-dimethyl ester) (14)
1.86–1.54 (3ꢂm, 4H, CH2), 1.41–1.17 (3ꢂm, 2H, CH2) ppm. 13C NMR
(CD2Cl2,
d), 137.0, 135.5, 134.2, 132.3, 132.2, 131.6, 131.5, 130.7, 130.6,
Yellowoil(392 mg)in53%yield. Found(calcdforC24H36O2P2Se4):
C 38.96 (39.25), H 5.01 (4.94). Selected IR (KBr, cmꢀ1): 3050 (w), 2925
(m), 2853 (w),1436 (m),1269 (w),1105 (s), 983 (s), 746 (m), 713 (m),
130.4, 130.2, 128.6, 128.5, 128.4, 128.3, 66.4, 66.3 and 65.2 (3ꢂd,
OCH2), 29.8, 29.5 and 29.4 (CH2), 22.4, 22.3 and 19.8 (CH2), 13.5,
10.9 and 10.8 (SeCH3) ppm. 31P–{1H} NMR (CD2Cl2,
d
), three di-
689 (s), 553 (vs, P]Se), 499 (m). 1H NMR (CD2Cl2,
d), 7.92 (m, 4H,
astereoisomers (1:1:0.5), 80.60, 80.56 and 80.49 (3ꢂs, J(P,Seendo)¼
ArH), 7.50 (m, 6H, ArH), 4.20 (m, 4H, OCH2), 2.08 (d, 6H, SeCH3), 1.76
439 Hz, J(P,Seexo)¼826 Hz) ppm. 77Se–{1H} NMR (CD2Cl2,
d), three
(m, 4H, CH2),1.53 (m, 4H, CH2),1.41–1.25 (m, 8H, CH2) ppm.13C NMR
diastereoisomers, 253.81, 253.66 and 253.65 (3ꢂd, J(P,Seendo)¼
439 Hz), ꢀ102.38, ꢀ102.52 and ꢀ102.71 (3ꢂd, J(P,Seexo)¼
825 Hz) ppm. MS (EI, m/z): 666 [M]þ, 493 [MꢀSeꢀSeCH3]þ, 205
[MꢀC13H18OPSe3]þ. MS (CIþ, m/z): 667 [MþH]þ.
(CD2Cl2,
d
), 136.3 (d, 1J(P,C)¼99.7 Hz), 132.3 (d, 4J(P,C)¼3.1 Hz), 130.3
(d, 3J(P,C)¼11.4 Hz), 128.5 (d, 2J(P,C)¼14.5 Hz), 66.8, 29.9, 25.9, 19.8,
13.5, 10.8 (SeCH3) ppm. 31P–{1H} NMR (CD2Cl2,
d), 80.04 (s, J(P,Seendo)¼
437 Hz, J(P,Seexo)¼824 Hz) ppm. 77Se–{1H} NMR (CD2Cl2,
d), 253.34 (d,
J(P,Seendo)¼436 Hz), ꢀ102.06 (d, J(P,Seexo)¼825 Hz) ppm. MS (EI, m/z):
736 [M]þ, 563 [MꢀSeꢀSeCH3]þ, 205 [MꢀC18H28OPSe3]þ. MS (CIþ, m/
z): 737 [MþH]þ.
3.3.5. 1,6-Dioxoethane-1,2-bis(phenyl-diselenophosphonic acid
Se,Se-dimethyl ester) (12)
Purification by silica gel (eluent by dichloromethane) gave two
fractions. Compound 12a: 160 mg of pale yellow oil in 24% yield.
Found (calcd for C20H28O2P2Se4): C 35.09 (35.42), H 3.91 (4.16).
Selected IR (KBr, cmꢀ1): 3050 (w), 2929 (m), 2855 (w), 1436 (m),
1268 (w), 1105 (m), 987 (s), 746 (m), 713 (m), 689 (m), 552 (vs,
3.3.8. 2,4-Bisphenyl-2,4-diseleno-1,5-dioxa-3-seleno-2,4-
diphosphetane (15) and 1,3,2-dioxaphosphorinane-2-phenyl-2-
selenide (16)
A mixture of ethylene glycol (0.06 g, 1.0 mmol) and WR (0.54 g,
1.0 mmol) in toluene (10 ml) was heated at reflux for 2 h. The red
suspension disappeared and a green mixture was formed. Upon
cooling to room temperature the mixture was purified by silica gel
(toluene as eluent) to give 370 mg of 15 as greenish yellow oil and
30 mg of 16 as green oil.
P]Se), 499 (m). 1H NMR (CD2Cl2,
d), 7.95–7.87 (m, 4H, ArH),
7.52–7.48 (m, 6H, ArH), 4.25–4.05 (m, 4H, OCH2), 2.06 (d, 6H,
SeCH3), 1.82–1.77 (m, 4H, CH2), 1.53–1.45 (m, 4H, CH2) ppm. 13C
NMR (CD2Cl2,
d
), 136.3 (d, 1J(P,C)¼99.7 Hz), 132.3 (d, 4J(P,C)¼3.1 Hz),
130.3 (d, 3J(P,C)¼12.5 Hz), 128.5 (d, 2J(P,C)¼14.5 Hz), 66.3 (d,
2J(P,C)¼6.2 Hz, OCH2), 29.8 (CH2), 25.5 (CH2), 10.8 (d, 2J(P,C)¼4.2 Hz,
SeCH3) ppm. 31P–{1H} NMR (CD2Cl2,
d
), 80.43 (s, J(P,Seendo)¼434 Hz,
3.3.8.1. Compound
(15). Yield
72%.
Found
(calcd
for
J(P,Seexo)¼824 Hz) ppm. 77Se–{1H} NMR (CD2Cl2,
d), 253.62 (d,
C14H14O2P2Se3): C 32.49 (32.77), H 2.80 (2.75). Selected IR (KBr,
J(P,Seendo)¼436 Hz), ꢀ102.38 (d, J(P,Seexo)¼825 Hz) ppm. MS (EI,
m/z): 680 [M]þ, 507 [MꢀSeꢀSeCH3]þ, 205 [MꢀC14H20OPSe3]þ. MS
(CIþ, m/z): 681 [MþH]þ. Compounds 12b,c: 207 mg of pale yellow
cmꢀ1): 3058 (w), 2933 (w), 1436 (s), 1103 (s), 1054 (s), 1024 (m), 930
(m), 744 (m), 713 (s), 685 (s), 542 (s), 493 (m), 421 (m). 1H NMR
(CD2Cl2, d), 8.21–8.12 (m, 4H, ArH), 7.55–7.53 (m, 6H, ArH), 4.35 (m,

G. Hua et al. / Tetrahedron 64 (2008) 5442–5448
5447
4H, OCH2). 13C NMR (CD2Cl2,
d
), 135.4 (d, 1J(P,C)¼104 Hz), 133.2,
3.3.10.1. Compound (19). Yield 13%. Mp 108 ꢁC. Found (calcd for
133.0, 131.4, 131.3, 131.2, 130.4 (d, 3J(P,C)¼12.5 Hz), 129.0, 128.6,
C16H18O2P2Se4): C 30.77 (30.99), H 3.01 (2.93). Selected IR (KBr,
128.5,128.4,128.3, 67.0 ppm. 31P–{1H} NMR (CD2Cl2, 25 ꢁC,
d
), 75.02
cmꢀ1): 3039 (w), 2944 (m), 2910 (w), 1435 (m), 1103 (m), 1079 (m),
991 (s), 917 (m), 744 (s), 712 (s), 686 (s), 540 (s), 485 (m), 425 (m).
(s, 1J(P,Seendo)¼397 Hz, 1J(P,Seexo)¼852 Hz, 2J(P,P)¼14.1 Hz) ppm.
77Se–{1H} NMR (CD2Cl2,
d
), 696.24 (t, 1J(P,Seendo)¼396 Hz), 5.37 (dd,
1H NMR (CD2Cl2,
d), 8.04 (m, 4H, ArH), 7.56 (m, 6H, ArH), 4.39
1J(P,Seexo)¼851 Hz, 3J(P,Seexo)¼9.8 Hz) ppm. MS (CIþ): m/z 515
(m, 3J(P,H)¼40 Hz, 3J(H,H)¼8.9 Hz, 4H, CH2), 2.04 (m, 3J(H,H)¼
[MþH]þ.
8.9 Hz, 4H, CH2) ppm. 13C NMR (CD2Cl2,
d
), 137.5 (d, 1J(P,C)¼98 Hz),
132.3 (d, 4J(P,C)¼3 Hz), 129.6 (d, 3J(P,C)¼13 Hz), 128.4 (d,
2J(P,C)¼15 Hz), 65.9 (2J(P,C)¼32 Hz, CH2), 25.1 (3J(P,C)¼8 Hz,
3.3.8.2. Compound (16). Yield 12%. Found (calcd for C8H9O2PSe): C
38.31 (38.89), H 3.61 (3.67). Selected IR (KBr, cmꢀ1): 2928 (w), 1437
(m), 1114 (s), 1021 (vs), 918 (s), 823 (m), 790 (m), 747 (m), 718 (m),
CH2) ppm. 31P–{1H} NMR (CD2Cl2,
d
), 68.28 (s, 1J(P,Seendo)¼460 Hz,
1J(P,Seexo)¼808 Hz, 3J(P,P)¼4.7 Hz) ppm. 77Se–{1H} NMR (CD2Cl2,
d),
689 (m), 633 (m), 527 (m). 1H NMR (CD2Cl2,
d), 7.89–7.80 (m, 2H,
474.21 (d, 1J(P,Seendo)¼463 Hz, 2J(P,Seendo)¼21.5 Hz), ꢀ80.17 (d,
1J(P,Seexo)¼806 Hz) ppm. Accurate mass measurement (EIMS):
621.7450, calculated mass for C16H18O2P2Se4: 621.7445.
ArH), 7.57–7.45 (m, 3H, ArH), 4.53 (m, 4H, OCH2). 13C NMR (CD2Cl2,
d
), 134.4 (d, 1J(P,C)¼101 Hz), 133.0, 130.8 (d, 3J(P,C)¼13.5 Hz), 128.5
(d, 3J(P,C)¼14.5 Hz), 67.3 ppm. P–{1H} NMR (CD2Cl2, 25 ꢁC,
d
d
),
),
31
111.60 (s, 1J(P,Seexo)¼911 Hz) ppm. 77Se–{1H} NMR (CD2Cl2,
3.3.10.2. Compound (20). Yield 86%. Found (calcd for C10H13O2PSe):
C 43.29 (43.65), H 4.28 (4.76). Selected IR (KBr, cmꢀ1): 3055 (w),
2950 (m), 2890 (m), 1467 (m), 1437 (m), 1118 (m), 1080 (m), 1003
(vs), 992 (vs), 940 (s), 905 (m), 852 (m), 775 (m), 744 (m), 715 (s),
ꢀ203.95 (d, 1J(P,Seexo)¼911 Hz) ppm. MS (CIþ): m/z 249 [MþH]þ.
3.3.9. 2,5-Diphenyl-(1,6,3,4,2,5)-dioxadiselenadiphosphocane-
2,5-diselenide (17) and 1,3,2-dioxaphosphorinane-2-phenyl-2-
selenide (18)
A mixture of 1,3-propanediol (0.08 g, 1.0 mmol) and WR (0.54 g,
1.0 mmol) in toluene (10 ml) was heated at reflux for 2 h. The red
suspension disappeared and a green mixture was formed. Upon
cooling to room temperature the mixture was purified by silica gel
(toluene as eluent) to give 160 mg of 17 as yellow powder and
134 mg of 18 as green solid.
691 (m), 579 (s), 532 (m). 1H NMR (CD2Cl2,
d), 7.91–7.85 (m, 2H,
ArH), 7.54–7.48(m, 3H, ArH), 4.21 (dd, J(H,H)¼7.9 Hz, 3J(P,H)¼
16.0 Hz, 4H, OCH2), 2.02 (d, J(H,H)¼7.9 Hz, 4J(P,H)¼2.7 Hz, 4H, CH2).
13C NMR (CD2Cl2,
d
), 136.4 (d, 1J(P,C)¼137 Hz), 132.3 (d,
4J(P,C)¼3.1 Hz), 130.4, 130.2, 128.4 (d, 3J(P,C)¼14.5 Hz), 68.1, 29.4.
31P–{1H} NMR (CD2Cl2,
d
), 93.09 (s, 1J(P,Seexo)¼878 Hz) ppm. 77Se–
{1H} NMR (CD2Cl2,
d
), ꢀ212.44 (d, 1J(P,Seexo)¼880 Hz). MS (ESIþ):
m/z 298 [MþNa]þ.
3.3.9.1. Compound (17). Yield 30%. Mp 162–163 ꢁC. Found (calcd for
3.3.11. 1,3,2-Dioxaphosphorinane-2-phenyl-2-selenides (21)
mixture of pinacol (0.11 g, 1.0 mmol) and WR (0.54 g,
C
15H16O2P2Se4): C 29.52 (29.73), H 2.54 (2.66). Selected IR (KBr,
A
cmꢀ1): 1433 (m), 1262 (m), 1103 (s), 987 (s), 804 (m), 740 (m), 684
1.0 mmol) in toluene (10 ml) was stirred for 18 h at room temper-
ature, the colour of the mixture remained unchanged. 31P NMR
spectroscopy of the mixture showed that no reaction had occurred.
The mixture was heated at reflux for 2 h, the red suspension dis-
appeared and a brown suspension was formed. Upon cooling to
room temperature the mixture was purified by silica gel (toluene as
eluent) to afford 210 mg of 21 as pale yellow solid in 69% yield. Mp
87 ꢁC. Found (calcd for C12H17O2PSe): C 47.19 (47.54), H 5.51 (5.65).
Selected IR (KBr, cmꢀ1): 2980 (w), 2923 (w), 1478 (w), 1435 (m),
1374 (m), 1137 (m), 1118 (m), 956 (m), 912 (s), 861 (m), 715 (m), 690
(m), 538 (s, P]Se). 1H NMR (CD2Cl2,
d), 8.00–7.56 (m, 10H, ArH),
4.66 (m, J¼12 Hz, 2H, CH2), 4.30 (t, J¼12 Hz, 4H, CH2) ppm. 13C NMR
(CD2Cl2,
d
), 135.1 (d, 1J(P,C)¼103 Hz), 133.2 (d, 4J(P,C)¼3 Hz), 130.7
(d, 3J(P,C)¼12 Hz), 128.6 (d, 2J(P,C)¼15 Hz), 62.4 (d, 2J(P,C)¼15 Hz,
CH2), 28.4 (t, 3J(P,C)¼10 Hz, CH2) ppm. 31P–{1H} NMR (CD2Cl2,
d),
67.21 ppm, singlet with 77Se satellites (1J(P,Seexo)¼812 Hz,
1J(P,Seendo)¼465 Hz, 3J(P,P)¼4.2 Hz), lines for 2J(P,Seendo
) were
hidden under intensive central line, prohibiting calculation of
its coupling constant. 77Se–{1H} NMR (CD2Cl2,
d), 441.17 (dd,
1J(P,Seendo)¼465 Hz, 2J(P,Seendo)¼21.5 Hz), ꢀ61.15 (dd, 1J(P,Seexo)¼
810 Hz) ppm. Accurate mass measurement (EI, m/z): 609.7284,
calculated mass for C15H16O2P2Se4: 609.7281.
(m), 625 (m), 535 (s, P]Se). 1H NMR (CD2Cl2,
ArH), 7.48–7.40 (m, 3H, ArH),1.58 (s, 6H, CH3),1.27 (s, 6H, CH3) ppm.
13C NMR (CD2Cl2,
), 139.4 (d, J(P,C)¼120 Hz), 131.8 (d,
J(P,C)¼14.5 Hz), 129.2, 129.0, 128.3 (d, J(P,C)¼3.1 Hz), 90.6, 24.8,
d), 7.82–7.73 (m, 2H,
d
3.3.9.2. Compound (18). Yield 51%. Found (calcd for C9H11O2PSe): C
41.05 (41.40), H 4.07 (4.25). Selected IR (KBr, cmꢀ1): 3053 (w), 2956
(w), 2886 (w), 1438 (s), 1119 (m), 1106 (m), 1031 (vs), 921 (m), 737
24.2 ppm. 31P–{1H} NMR (CD2Cl2,
d
), 99.19 (s, J(P,Seexo)¼885 Hz,
J(P,C)¼120 Hz) ppm. 77Se–{1H} NMR (CD2Cl2,
d
), ꢀ81.14 (d,
J(P,Seexo)¼885 Hz) ppm. MS (EI, m/z): 304 [M]þ, 224 [MꢀSe]þ, 220
[MꢀC(CH3)2C(CH3)2]þ.
(m), 687 (m), 538 (s), 471 (m). 1H NMR (CD2Cl2,
d), 8.00–7.92 (m,
2H, ArH), 7.59–7.47 (m, 3H, ArH), 4.78 (m, 4H, OCH2), 4.26 (m, 2H,
CH2). 13C NMR (CD2Cl2,
d
), 133.9 (d, 1J(P,C)¼102 Hz), 133.2, 132.2,
Acknowledgements
131.2 (d, 3J(P,C)¼13.5 Hz), 128.5 (d, 3J(P,C)¼14.5 Hz), 65.9, 27.6 ppm.
31P–{1H} NMR (CD2Cl2,
d
), 93.27 (s, 1J(P,Seexo)¼876 Hz) ppm. 77Se–
The authors are grateful to the Engineering and Physical Science
Research Council (EPSRC, UK) for financial support.
{1H} NMR (CD2Cl2,
d
), ꢀ247.17 (d, 1J(P,Seexo)¼877 Hz) ppm. MS
(CIþ): m/z 263 [MþH]þ.
References and notes
3.3.10. 2,5-Diphenyl-(1,6,3,4,2,5)-dioxadiselenadiphosphocane-2,5-
diselenide (19) and 1,3,2-dioxaphosphorinane-2-phenyl-2-selenide
(20)
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A solution of 1,4-butanediol (0.07 g, 1.0 mmol) and WR (0.54 g,
1.0 mmol) in toluene (10 ml) was heated at reflux for 2 h. The red
suspension disappeared and a pale green solution was formed.
Upon cooling to room temperature the mixture was passed through
a flash chromatography column (silica gel, eluting with toluene and
1:9 ethyl acetate/toluene) leading to 80 mg of 19 as pale yellow
solid (eluting with toluene only) and 240 mg of 20 as yellow oil
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3. (a) Gray, I. P.; Slawin, A. M. Z.; Woollins, J. D. Dalton Trans. 2005, 2188; (b)
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12. Crystal data for 1: C22H38N2O2P2Se4, M¼740.32, space group P-1, triclinic, a¼
9.6618(16), b¼10.3511(16), c¼15.943(2) Å,
a
¼75.636(9),
b
¼78.360(11),
g
¼
88.528(13)ꢁ, U¼1512.3(4) Å3, Z¼2,
m
¼4.978 mmꢀ1, 10,428 reflections collected,
0.0264 independent reflections (Rint). The final R was 0.0426 for I>2
s(I) and
wR(F2) was 0.0769 for all data.
13. Schmidpeter, A. Multiple Bonds and Low Coordination in Phosphorus Chemistry;
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2857