FULL PAPER

DOI: 10.1002/chem.200500291

A New Synthesis of (PhPSe2)2 (Woollins Reagent) and Its Use in the

Synthesis of Novel P–Se Heterocycles

Ian P. Gray, Pravat Bhattacharyya, Alexandra M. Z. Slawin, and J. Derek Woollins*[a]

Abstract: A new and improved method heterocycles, including a spirocyclic and methyl phenylpropiolate). Useful
for the preparation of (PhPSe2)2 (Wool- heterocycle exhibiting a four-mem- selenocarbonyl and thiocarbonyl com-
lins reagent (WR), 1) is reported. Re- bered P2SeC ring, were obtained from pounds were obtained from the reac-
action of dichlorophenylphosphine the reaction of WR with two reactive tion of both WR and Lawesson=s re-
with Na2Se, (prepared from the reac- substrates (diphenylcyclopropenone agent with diphenylcyclopropenone.
tion of elemental selenium and sodium All new compounds were characterised
in liquid ammonia) gives WR with ex- spectroscopically and three demonstra-
Keywords: heterocycles · phospho-
cellent purity, high yield and on a tive X-ray structures are reported.
rus · selenium · Woollins reagent ·
larger scale than was previously possi-
X-ray structure
ble. Four novel phosphorus–selenium

Introduction ject of a few reports. Baxter et al.,[6] Bhattacharyya et al.[7]

and Bethke et al.[8a] have reported the selenation reactions
The synthesis and wide variety of reactions of dithiadiphos- of WR in the synthesis of selenoketenyl complexes and a
phetane disulfides has been the subject of many reviews, ar- range of selenoamides and selenoaldehydes, and Knapp and
ticles and communications over many years.[1] In contrast, Darout very recently described its use for the selenation of
their selenium analogues, the diselenaphosphetane disele- carboxylic acids.[8b] We have also reported the use of WR in
nides, have received very little attention. Shore et al.[2] re- the preparation of novel phosphorus–selenium heterocycles
ported the synthesis of (tBuPSe2)2 from dichloro-tert-butyl- by the reaction with several organic substrates containing re-
phosphine and Li2Se2, and, although this compound was active unsaturated C=C double bonds, CC triple bonds and
studied crystallographically, its potential chemistry has been CN triple bonds.[9] A further range of novel phosphorus–
overlooked. Hahn and co-workers were also able to obtain selenium heterocycles were prepared by treating WR with
this compound and its methyl and phenyl analogues[3] from dibasic nucleophiles.[10]
the reaction of the silyl esters of the triselenophosphonic
acids and DMSO, although no detailed experimental proce-
dure or spectroscopic data was reported. Karaghiosoff and Results and Discussion
co-workers[4] and Woollins et al.[5] have reported a range of
diselenaphosphetane diselenides synthesised from the oxida- To date, no suitable general method for the synthesis of dis-
tion of the corresponding homocyclic pentamers (PR)5 (R = elenaphosphetane diselenides has been established. Here,
Me, Et, 4-Me2NC6H4, An and Ph) by 10 equivalents of ele- we describe a new method that gives WR with excellent
mental selenium, including WR (R = Ph). purity and high yield. Reactions were carried out with WR
In recent years, the chemistry of (PhPSe2)2 1 (which has and two reactive substrates to yield four new phosphorus–
become known as Woollins reagent, WR) has been the sub- selenium heterocycles and a useful selenocarbonyl com-
pound. As a direct comparison, the reaction between one of
these substrates, diphenylcyclopropenone, and Lawesson=s
[a] Dr. I. P. Gray, Dr. P. Bhattacharyya, Prof. A. M. Z. Slawin, reagent was performed and gave the analogous thiocarbonyl
Prof. J. D. Woollins compound in high yield.
School of Chemistry, University of St Andrews
St Andrews, Fife KY16 9ST (UK)
Fax: (+ 44) 1334-46-3384 Preparation of Woollins reagent from (PhP)5 : WR is usually
E-mail: jdw3@st-and.ac.uk prepared from the pentamer (PhP)5 by following the litera-

Chem. Eur. J. 2005, 11, 6221 – 6227 G 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 6221
ture procedure[5c] (Scheme 1). Although this method produ-
ces the desired product, as indicated by the results of micro-
analysis and IR spectra, it has limitations. The pentamer is a

Scheme 1.

highly unpleasant compound, is air-sensitive and has a lin-

gering stench. One other major limitation of this method is
that the pentamer can be readily prepared on a small scale
only (5–10 g), which makes it an unsuitable precursor for
large-scale synthesis.

Preparation of WR from PhPCl2 and Na2Se: We have em-

ployed a new method to synthesise WR, producing material Figure 1. The upper spectrum shows the actual powder diffraction pattern
of high purity in high yield. Elemental selenium was added obtained for 1; the lower spectrum shows the powder diffraction pattern
to sodium metal dissolved in liquid ammonia at 78 8C, and simulated from single crystal data of 1.
was allowed to reflux at 34 8C. Once the ammonia was re-
moved, Na2Se was obtained as an off-white solid. The am-
monia was replaced by toluene, PhPCl2 was added and the
mixture was heated to reflux. The reaction was filtered to
remove the precipitated NaCl byproduct from the yellow so-
lution. A second portion of selenium was added and reflux
was continued. WR was isolated as red crystals in very high
yield (86 %), which were identified by performing micro-
analysis, IR spectroscopy, mass spectrometry, powder dif-
fraction and 31P solid-state NMR spectroscopy. The IR and
solid-state 31P NMR[11] spectra are identical to those ob-
tained for WR by using the previous method, and also to lit-
erature values.
The powder diffraction pattern of the product of this reac-
tion was compared to a theoretical pattern calculated from
single crystal data, unambiguously showing it to be Woollins Scheme 2.
reagent (Figure 1). A low intensity peak, due to an unidenti-
fied impurity, was also observed with 2q at 498. A powder
diffraction pattern was also collected for a sample produced
by the pentamer method, and showed it to contain a signifi-
cant amount of red selenium.
The use of 31P NMR spectroscopy allows us to monitor
the course of the reaction (Scheme 2). After 18 h of the ini-
tial reflux, a 31P NMR spectrum was recorded (Figure 2),
which shows the presence of both 2 (d = 102.3, 101.1, 89.9,
82.9 ppm) and 3 (d = 119.0, 108.8, 106.2, 92.8, 90.1 ppm), the
chemical shifts and coupling constants in accordance with
known literature values.[4, 5] The spectrum also shows the
presence of the starting PhPCl2 (d = 161.5 ppm) and
PhP(Se)Cl2 (d = 58.3 ppm) (Figure 2). This suggests that the Figure 2. 31P-{1H} NMR spectrum obtained after 18 h of reflux of Na2Se
reactive heterocycles 2 and 3 are formed by the reaction of and PhPCl2 in toluene.

6222 www.chemeurj.org G 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2005, 11, 6221 – 6227
Synthesis of Novel P–Se Heterocycles
FULL PAPER
PhPCl2 with Na2Se, and upon further addition of selenium, copy showed that only phenyl protons are present. Unfortu-
they are converted to WR. nately, the low yield meant that a suitable 13C NMR spec-
This new method involves the use of the unpleasant di- trum could not be obtained.
chlorophenylphosphine and the potentially hazardous liquid Crystals suitable for X-ray analysis were grown by layer-
ammonia; however, it bypasses the handling of the pentam- ing of a dichloromethane solution with hexane, allowing us
er (PhP)5. In addition, it produces a product of high purity, to unambiguously identify the structure of 6 as a four-mem-
in higher yield and by a cleaner process, but the real advant- bered P2SeC ring fused at the carbon atom to a three-mem-
age of this method is that it can be conducted on a much bered cyclopropene ring (Figure 3). The structure shows
larger scale (~ 150 g).

Reaction of WR with diphenylcyclopropenone: WR and di-

phenylcyclopropenone 4 were stirred together at 100 8C in
dichloromethane (in a sealed tube) resulting in a very dark
red solution plus a small amount of black selenium
(Scheme 3). Column chromatography (silica gel, toluene)

Scheme 3.
Figure 3. The X-ray structure of 6. Selected bond lengths (O) and angles
(8) (esd=s in parentheses): P(1) Se(1) 2.089(3), P(1) Se(12) 2.265(2),
P(1) C(1) 1.826(10), P(1) C(13) 1.840(9), C(13) C(15) 1.507(12),
produced an orange fraction followed by a purple fraction. C(14) C(15) 1.290(12), P(1)-Se(12)-P(2) 78.83(9), P(1)-C(13)-P(2)
The orange fraction proved to be the expected selenation 102.0(4).
product, the selenocarbonyl compound 5. This was isolated
in moderate yield (27 %) as an orange, air-stable, solid. The
identity of 5 was confirmed by microanalysis, 1H, 13C and that the exocyclic selenium atoms exist in a trans conforma-
77
Se NMR spectroscopy, IR spectroscopy and mass spec- tion, consistent with all known four-membered phosphorus–
trometry. The values obtained matched literature data from selenium ring systems of this type. The C=C double bond of
previous studies of this selenocarbonyl species. This com- the cyclopropene ring remains unchanged. The P2SeC ring
pound is of interest in organometallic chemistry as it has adopts a planar conformation that has been shown to be fav-
been reported to undergo insertion reactions with metal car- oured by similar ring systems, WR,[9a] tBuP2Se4[2] and
bonyl compounds.[12] PhP(Se)(m-NPh)P(Se)Ph.[9a] The internal P-Se-P bond angle
The second, purple fraction proved to be a new and un- in 6 (78.83(9)8) is substantially smaller than in WR
usual phosphorus–selenium heterocycle 6. This was isolated (85.45(9)8) and is closer to the values found for
in low yield (5 %) as a purple solid and was found to de- Ph2P2Se3CMe2[13] (77.73(7)8) and PhP(Se)(m-NPh)P(Se)Ph[9a]
grade in the presence of air and moisture over approximate- (75.28(4)8), indicating that the reduction in angle size is due
ly two weeks. The 31P NMR spectrum of 6 shows a sharp sin- to the introduction of the smaller heteroatom (C or N).
glet at d = 66.1 ppm, accompanied by an unusual pattern of Only two other examples of P2SeC four-membered rings
selenium satellites. There appeared to be three sets of satel- have been discovered; Ph2P2SeCH2[13] and Ph2P2SeCMe2.[13]
lites associated with each phosphorus atom, with 31P,77Se These are consistent with the above structure, but no three-
couplings of 304, 693 and 938 Hz, respectively. Closer in- membered ring has been shown to fuse to such a system.
spection suggests that the pattern is actually a 1J(31P,77Se)
coupling of 304 Hz attributed to the P Se single bonds, and Reaction of Lawesson?s reagent with diphenylcyclopropen-
a 1J(31P,77Se) coupling of 816 Hz attributed to the P=Se one: As a direct comparison, the reaction between diphenyl-
double bonds, which is split by a 2J(31P,31P) coupling of cyclopropenone and Lawesson=s reagent (LR) was per-
124 Hz. This assignment is further substantiated by formed (Scheme 4) to give 7 as the only product (confirmed
77
Se NMR studies. The 77Se NMR spectrum displays two dis- by microanalysis, 1H and 13C NMR spectroscopy, IR spec-
tinct signals; a doublet at d = 34.1 ppm with a 1J(31P,77Se) troscopy and mass spectrometry).[11] Like its selenium ana-
coupling constant of 820 Hz and a triplet at d = 507 ppm logue, 7 has been reported to undergo similar insertion reac-
with a 1J(31P,77Se) coupling constant of 306 Hz, assigned as tions with metal carbonyl compounds.[11] Unlike the corre-
P=Se and P Se, respectively. Results of 1H NMR spectros- sponding reaction with Woollins reagent, there was no sign

Chem. Eur. J. 2005, 11, 6221 – 6227 G 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 6223
 J. D. Woollins et al.

Scheme 4.

of the formation of any phosphorus-containing heterocyclic

products. Although this reaction did not produce any novel
heterocycles, it clearly demonstrates a novel and simple
route to this useful thiocarbonyl compound.

Reaction of WR with methyl phenylpropiolate: WR and

methyl phenylpropiolate were heated to reflux in toluene,
resulting in a red solution. The use of column chromatogra- Figure 4. The X-ray structure of 8. Selected bond lengths [O] and angles
phy (silica gel, toluene) afforded four phosphorus-containing [8] (esd=s in parentheses): Se(1) P(2) 2.096(2), P(2) Se(3) 2.2387(19),
Se(3) Se(4) 2.3286(11), Se(4) C(5) 1.924(6), C(5) C(6) 1.323(9); Se(1)-
fractions, from which compounds 8–10 were obtained in 20–
P(2)-Se(3) 112.21(9), P(2)-Se(3)-Se(4) 94.78(5), C(5)-Se(4)-Se(3) 96.1(2),
26 % isolated yields (Scheme 5). Compounds 8–10 were C(5)-C(6)-P(2) 112.3(4), C(6)-C(5)-Se(4) 123.8(5).

10 is assigned as the cis isomer.

This assignment of these iso-
mers is also reinforced by the
13
C NMR data, which revealed
the expected differences in
chemical shift and 31P,13C cou-
pling constants. The 1H NMR
spectra show that in both mole-
cules there are two phenyl
groups and one methoxy group
present.
Scheme 5.
The X-ray structure of 8 con-
firms the formation of a five-
found to be solids that were moderately stable in air, de- membered C2PSe2 ring. The
grading over a period of several weeks with the obvious ex- ring is essentially planar with a mean deviation of 0.06 O;
pulsion of red selenium. They are soluble in chloroform, tet- however, this was not found to be the case for heterocycles
rahydrofuran and dichloromethane and insoluble in diethyl containing similar ring systems formed from the reaction of
ether and hexane. The mass spectra of these compounds all WR with dimethyl acetylenedicarboxylate (C2PSe2 and
contain molecular ion peaks at m/z 506, corresponding to C2PSe2) and bicyclo[2.2.1]hept-2-ene (C2PSe2), which have
PhPSe3(PhC=C CO2Me), which is supported by microanaly- envelope conformations.[9a–c] The Se(3) Se(4) bond length
ses. (2.3266(11) O) is comparable to the Se Se bond lengths
The 31P NMR spectra of 8 and 10 display sharp singlets at found in (PhPSe)2CH2Se2 (2.338(1) O)[9b] and PhP(Se)-
d = 76.0 and 71.4 ppm, respectively, and each signal is ac- Se2(C2{CO2Me}2) (2.359(2) O)[9c] , with the plane of the
companied by two sets of selenium satellites (789 and phenyl group attached to C(6) lying almost perpendicular to
366 Hz for 8, 798 and 343 Hz for 10), indicating that in each the central C2PSe2 ring (C(5)-C(6)-C(7)-C(12) torsion angle
compound there is a P Se single bond and a P=Se double of 80.9(10)8).
bond present. This is further substantiated by the 77Se NMR Despite the similarities in the molecular ions and micro-
spectrum, which displays three doublets, due to 31P,77Se cou- analyses of 9, and 8 and 10, the spectra of 9 display a some-
pling, and indicates the presence of a PhP(Se)-Se-Se chain, what different pattern to those of 8 and 10. The 31P spec-
a fragment present in the products obtained from the reac- trum of 9 again displays a sharp singlet (d = 85.7 ppm), but
tion of WR with dimethyl acetylenedicarboxylate, norborna- in this case, only one set of selenium satellites is observed,
diene and norbornene.[9a, b] The X-ray structure of 8 with a 31P,77Se coupling constant of 822 Hz. This would indi-
(Figure 4) was obtained unambiguously and shows that the cate the presence of a P=Se double bond and the absence of
PhP(Se)-Se-Se chain is attached across the C=C double any P Se single bonds, therefore, compound 9 must adopt a
bond in a five-membered ring. The structure also shows that different structural motif to that of 8 and 10. The 77Se NMR
in 8, the ester group is trans to the phosphorus atom, thus spectrum displays a doublet at d = 207 ppm with a 31P,77Se

6224 www.chemeurj.org G 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2005, 11, 6221 – 6227
Synthesis of Novel P–Se Heterocycles
FULL PAPER
coupling constant of 823 Hz, confirming the presence of a Experimental Section
P=Se bond. There are also two distinct singlets at d = 688
and 519 ppm, respectively. The 1H NMR spectrum shows General: Unless otherwise stated, experiments were performed under an
that the molecule contains two phenyl groups and one me- oxygen-free nitrogen atmosphere by using predried solvents and standard
Schlenk techniques. All reagents were purchased from Aldrich, Acros or
thoxy group, with a 1H,31P coupling constant of 15 Hz.
Lancaster and were used as received. IR spectra were recorded as KBr
The X-ray structure of 9 was obtained (Figure 5) and was, discs in the range 4000–350 cm 1 by using a Perkin–Elmer System 2000
as expected, very different from that of 8. The molecule pos- Fourier-transform spectrometer; 1H, 31P, 13C and 77Se NMR spectra were
sesses a planar C3Se2 ring, with exocyclic CPh and recorded by using a Jeol GSX Delta 270 FT NMR spectrometer. Solid-
PhP(Se)OMe substituents arranged in a cis geometry with state 31P NMR spectra were recorded by using an Infinityplus 500 MHz
solid-state NMR spectrometer. Microanalyses were performed by the
University of St. Andrews microanalysis service. Mass spectra were re-
corded by both the University of St. Andrews mass spectrometry service
and the Swansea mass spectrometry service.
Synthesis
Preparation of (PhP)5 : PhPCl2 (8.9 g, 50 mmol) and Mg turnings (1.2 g,
50 mmol) were stirred together in THF (50 cm3) for 4 h. Room tempera-
ture was maintained by some external cooling. Acetone (5 cm3) was
added and excess Mg was filtered off. Upon the addition of water (2 Q
30 cm3), an oily off-white precipitate formed. The mixture was stirred vig-
orously for 40 min. The product was collected by suction filtration and
dried in vacuo to give a white solid (1.41 g, 26 % yield).
Preparation of (PhPSe2)2 (1): From (PhP)5 : (PhP)5 (1.01 g, 1.87 mmol)
and selenium (1.49 g, 18.7 mmol) were refluxed with stirring in toluene
(30 cm3) for 5 h. The reaction mixture was allowed to cool to room tem-
perature. The product was collected by suction filtration, washed with
toluene (2 Q 15 cm3) and dried in vacuo to give a red solid (1.96 g, 78 %
yield); IR (KBr disc): ñ = 1433 (s), 1300 (mw), 1280 (w), 1155 (w), 1108
Figure 5. The X-ray structure of 9. Selected bond lengths [O] and angles
(w), 1078 (s), 994 (m), 917 (w), 841(w), 744 (m), 734 (s), 702 (m), 678 (s),
[8] (esd=s in parentheses). Se(1) P(1) 2.096(3), P(1) O(6) 1.591(7), C(2)
615 (m), 508 (s, br), 486 (s), 430 cm 1 (s); elemental analysis calcd (%)
Se(3) 1.948(10), Se(3) Se(4) 2.3082(16), Se(4) C(5) 1.895(10), O(6)
for C12H10P2Se4 : C 27.09, H 1.89; found: C 26.62, H 1.80; EIMS (positive
C(6) 1.469(13), C(2) O(2) 1.202(12); C(1)-P(1)-Se(1) 113.1(3), C(5)-
mode): m/z: 534 [M] + .
C(1)-P(1) 126.6(8), C(2)-C(1)-P(1) 112.9(7), C(2)-C(1)-P(1) 112.9(7),
O(2)-C(2)-C(1) 126.4(9), O(2)-C(2)-Se(3) 119.7(8), C(1)-C(2)-Se(3) Preparation of (PhPSe2)2 (1): From PhPCl2 : Na (1.2 g, 52.2 mmol) was
113.9(7), C(2)-Se(3)-Se(4) 92.4(3), C(5)-Se(4)-Se(3) 91.1(3), C(1)-C(5)- dissolved in liquid NH3 (50 cm3) at 78 8C. Se (2.061 g, 26.1 mmol) was
Se(4) 122.0(8)C(5)-C(1)-C(2) 120.3(9). added, resulting in a dark red mixture. After 15 min of stirring, the NH3
was allowed to evaporate and was replaced by toluene (50 cm3). An
excess of PhPCl2 (6.60 cm3) was added and refluxed for 64 h. The prog-
ress of the reaction was monitored by 31P NMR analysis. Se (3.435 g,
respect to one another. The structure shows that, in contrast 43 mmol) was added and the mixture was refluxed for 3.5 h. The product
to 8, the ester group of the starting material has not re- was collected by suction filtration, washed with toluene (2 Q 15 cm3) and
dried in vacuo to give a red solid (5.68 g, 82 % yield); 31P NMR (solid
mained unchanged, with the methoxy group having migrat- state): d = 18.7 ppm (s); IR (KBr disc): ñ = 1434 (s), 1302 (mw), 1280 (w),
ed to form a bond to the phosphorus atom. The data ob- 1154 (w), 1109 (w), 1077 (s), 994 (m), 917 (w), 744 (m), 734 (s), 704 (m),
tained from the 13C NMR spectrum of 9 is that expected for 679 (s), 614 (m), 508 (s, br), 486 (s), 432 cm 1 (s); elemental analysis
this structure. calcd (%) for C12H10P2Se4 : C 27.09, H 1.89; found: C 27.12, H 1.41;
In 8 and 9, the C Se (1.895(10), 1.948(10) O) and P Se EIMS (positive mode): m/z: 534 [M] + .

bond lengths (ca. 2.10 O for P=Se double bonds and 2.24 O This reaction can be performed on a scale 20 times greater than that de-
scribed above, and by taking suitable handling precautions. Attempts
for P Se single bonds) and the angles at internal selenium
were made to repeat this procedure using a) Li (0.362 g, 52.2 mmol) and
atoms (91.1(3) to 96.1(2)8) are consistent with those found b) (nBu4N)BH4 (13.421 g, 52.2 mmol) instead of Na, however, both at-
for similar ring systems. There are no notable intermolecular tempts proved unsuccessful.
contacts within either structure. Reaction of WR with diphenylcyclopropenone—synthesis of 5 and 6:
WR (1), (0.2 g, 37.3 mmol) and diphenylcyclopropenone (0.154 g,
74.6 mmol) were stirred in dichloromethane (3 cm3) at 100 8C in a sealed
tube for 5 min, producing a dark red solution plus a tiny amount of black
Conclusion solid (selenium). Column chromatography (silica gel, toluene) produced
an orange fraction and a subsequent purple fraction. These were dried in
We have described a new method for the preparation of vacuo and produced an orange solid, 5, and a purple solid, 6.
WR, which gives a product of excellent purity and high Compound 5 (0.054 g, 27 % yield, based on ketone); 1H NMR (CDCl3):
yield, and which can be applied to syntheses on a much d = 7.61–8.25 ppm (m, 10 H; Ph); 13C NMR (CDCl3): d = 173.1 (s, C = Se),
larger scale than that previously employed. Reactions were 159.9 (s, Ph C-1), 134.6 (s, p-Ph), 132.4 (s, m-Ph), 129.7 (o-Ph), 122.8 ppm
(s, C-Ph); 77Se NMR (CDCl3): d = 330.0 ppm (s); IR: (KBr disc): ñ = 3463
carried out with Woollins reagent and two reactive sub-
(s, br), 1780 (m), 1596 (m), 1360 (m), 1331 (s), 1310 (s), 1287 (s), 1171
strates (diphenylcyclopropenone and methyl phenylpropio- (m), 764 (s), 685 cm 1 (s); elemental analysis calcd (%) for C15H10Se: C
late) to yield four new isolable phosphorus–selenium hetero- 66.92, H 3.74; found: C 66.74, H 3.51; EIMS (positive mode): m/z: 270
cycles, including the novel spirocyclic compound 6. [M] + .

Chem. Eur. J. 2005, 11, 6221 – 6227 G 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 6225
 J. D. Woollins et al.

Compound 6 (0.012 g, 5 % yield, based on WR): Yellow crystals suitable 128.3 (s, C-Ph-m), 128.0 (d, 3J(31P,13C) 14.5 Hz, P-Ph-m), 127.2 (s, C-Ph-
for X-ray analysis were grown by layering a dichloromethane solution p), 52.3 ppm (d, 2J(31P,13C) 5.2 Hz, OCH3); 31P NMR (CDCl3): d =
with hexane; 1H NMR (CDCl3): d = 7.16–7.37 ppm (m, 20 H; Ph); 85.7 ppm (s, 1J(31P,77Se) = 821.7 Hz); 77Se NMR (CDCl3): d = 687.5 (s,
31
P NMR (CDCl3): d = 66.1 ppm (s, 1J(31P,77Se) = 304.2 Hz, 1J(31P,77Se) = C(=O)Se), 518.0 (s, C(Ph)Se), 207.0 ppm (d, 1J(31P,77Se) = 822.5 Hz, P =
815.5 Hz), 2J(31P,31P) = 124.4 Hz; 77Se NMR (CDCl3): d = 34.1 (d, 1J- Se); selected IR data (KBr): ñ = 1638 (s, C=O), 546 cm 1 (m, P=Se); ele-
(31P,77Se) = 820.2 Hz), 506.9 ppm (t, 1J(31P,77Se) = 306.1 Hz); IR (KBr disc): mental analysis calcd (%) for C16H13O2PSe3 : C 38.04, H 2.59; found: C
ñ = 3048 (s), 1445 (m), 1435 (s), 1305 (w), 1086 (s), 754 (s), 727 (m), 706 37.69, H 2.34; EIMS (positive mode): m/z: 506 [M] + .
(m), 685 (s), 541 cm 1 (s, P=Se); elemental analysis calcd (%) for Compound 10 (0.070 g, 25 % yield); 1H NMR (CDCl3): d = 8.18 (m, 2 H;
C27H20P2Se3 : C 50.41, H 3.13; found: C 50.11, H 3.04; EIMS (positive Ph), 7.48 (m, 8 H; Ph), 3.37 ppm (s, 3 H, CH3); 13C NMR (CDCl3): d =
mode): m/z: 643 [M] + . 165.7 (d, 2J(31P,13C) 10.4 Hz, C = C-Ph), 164.3 (d, 2J(31P,13C) 18.7 Hz, C =
Reaction of Lawesson?s reagent with diphenylcyclopropenone—synthesis O), 133.2 (d, 1J(31P,13C) 74.9 Hz, P-Ph C-1), 132.8 (d, 4J(31P,13C) 3.1 Hz, P-
of 7: LR (0.133 g, 37.3 mmol) and diphenylcyclopropenone (0.154 g, Ph-p), 131.5 (d, 3J(31P,13C) 13.5 Hz, P-Ph-m), 131.3 (s, C-Ph-p), 129.0 (s,
74.6 mmol) were refluxed in toluene (3 cm3) for 3 min, producing a C-Ph-o), 128.7 (d, 3J(31P,13C) 10.8 Hz, C-Ph C-1), 128.6 (d, 2J(31P,13C)
brown/orange solution. Column chromatography (silica gel, toluene) pro- 15.6 Hz, P-Ph-o), 128.5 (s, C-Ph-m), 126.5 (d, 1J(31P,13C) 71.6 Hz, P-C =
duced a yellow fraction. This was dried in vacuo to give a yellow solid C), 52.3 ppm (s, OCH3); 31P NMR (CDCl3): d = 71.4 ppm (s, 1J(31P,77Se) =
(0.121 g, 74 % yield); 1H NMR (CDCl3): d = 7.25–7.85 ppm (m, 10 H; Ph); 798.3 and 342.8 Hz); 77Se NMR (CDCl3): d = 532.0 (d, 2J(31P,77Se) =
13
C NMR (CDCl3): d = 178.5 (s, C = S), 153.8 (s, Ph C-1), 133.8 (s, p-Ph), 7.2 Hz, C-Se), 420.6 (d, 1J(31P,77Se) = 343.3 Hz, P-Se), 25.0 ppm (d, 1J-
132.1 (s, m-Ph), 129.6 (o-Ph), 122.9 ppm (s, C-Ph); IR (KBr disc): ñ = (31P,77Se) = 798.7 Hz, P = Se); selected IR data (KBr): ñ = 1707 (s, C=O),
3449 (s, br), 1780 (m), 1595 (m), 1352 (s), 1331 (s), 1314 (m), 1298 (m), 1233 (s, C O), 539 cm 1 (m, P=Se); elemental analysis calcd (%) for
1172 (m), 762 (s), 688 cm 1 (s); elemental analysis calcd (%) for C15H10S: C16H13O2PSe3 : C 38.04, H 2.59; found: C 39.01, H 2.44; EIMS (positive
C 81.04, H 4.53; found: C 80.72, H 4.26; EIMS (positive mode): m/z: 222 mode): m/z: 506 [M] + .
[M] + . X-ray crystallography: Table 1 list details of data collections and refine-
Reaction of WR (1) with methyl phenylpropiolate: A mixture of Wool- ments. Data for 6 and 8 were collected at 293 K, and for 9 at 125 K by
3
lins reagent (0.300 g, 0.56 mmol) and methyl phenylpropiolate (0.18 cm ) using a Bruker SMART (sealed tube) system. Intensities were corrected
in toluene (7 cm3) was heated at reflux for 21 h resulting in a red solu- for Lorentz-polarisation and for absorption. The structures were solved
tion. After cooling to room temperature, the solution was subjected to by direct methods. The positions of the hydrogen atoms were idealised.
column chromatography (silica gel, toluene) and afforded successively Refinements were obtained with full-matrix least-squares based on F2 by
yellow, orange (8), yellow (9) and orange (10) eluates. Compounds 8–10 using SHELXTL.[14, 15]
were precipitated as yellow (8 and 9)
or orange (10) solids following the ad-
dition of hexane to dichloromethane Table 1. Details of the X-ray data collections and refinements for 6, 8 and 9.
solutions. Compound 6 8 9
Compound 8 (0.073 g, 26 % yield):
formula C27H20P2Se3 C16H13O2PSe3 C16H13O2PSe3
Yellow crystals suitable for X-ray anal-
crystal colour, habit yellow, block yellow, block yellow, plate
ysis were grown by layering of a di-
crystal size [mm3] 0.2 Q 0.1 Q 0.05 0.15 Q 0.1 Q 0.1 0.16 Q 0.04 Q 0.02
chloromethane solution with hexane;
1 crystal system monoclinic monoclinic monoclinic
H NMR (CDCl3): d = 8.02 (m, 2 H;
space group C2/c P21/c P21/n
Ph), 7.44 (m, 3 H; Ph), 7.18 (m, 3 H;
a [O] 13.6894(8) 9.6996(10) 11.041(4)
Ph), 7.01 (m, 2 H; Ph), 3.61 ppm (s,
b [O] 11.0398(5) 9.4792(9) 7.068(3)
3 H; CH3); 13C NMR (CDCl3): d =
3 31 13
c [O] 33.605(2) 19.1924(19) 22.564(8)
178.6 (d, J( P, C) 9.3 Hz, C = O),
a [8] 90 90 90
162.9 (d, 2J(31P,13C) 26.0 Hz, C-C = O),
1 31 13
b [8] 90.496(2) 100.033(2) 101.306(7)
144.5 (d, J( P, C) 60.2 Hz, P-C(Ph) =
g [8] 90 90 90
C), 133.7 (d, 3J(31P,13C) 10.4 Hz, C-Ph-
3 31 13
V [O3] 5078.5(5) 1737.6(3) 1726.7(11)
o), 132.8 (d, J( P, C) 12.5 Hz, P-Ph-
Z 8 4 4
m), 131.1 (d, 1J(31P,13C) 70.6 Hz, P-Ph Mr 643.25 505.11 505.11
4 31 13
C-1), 129.7 (d, J( P, C) 5.2 Hz, C-Ph- 1 [g cm 3] 1.683 1.931 1.943
m), 129.6 (d, 4J(31P,13C) 5.2 Hz, P-Ph- m [mm 1
] 4.485 6.445 6.486
p), 128.9 (d, 2J(31P,13C) 29.1 Hz, C-Ph F(000) 2512 968 968
2 31 13
C-1), 128.5 (d, J( P, C) 14.5 Hz, P- measured reflns. 10 621 8260 7042
Ph-o), 127.8 (s, C-Ph-p), 53.3 ppm (s, independent reflns. (Rint) 3584(0.0301) 2368(0.0588) 2432(0.02508)
OCH3); 31P NMR (CDCl3): d = final R1, wR2 [I > 2s(I)] 0.0623(0.1445) 0.0461, 0.1074 0.0882, 0.2010
1 31 77
76.0 ppm (s, J( P, Se) = 789.2 and
365.9 Hz); 77Se NMR (CDCl3): d =
525.8 (d, 2J(31P,77Se) = 9.5 Hz, C-Se),
341.4 (d, 1J(31P,77Se) = 367.2 Hz, P-Se),
26.8 ppm (d, 1J(31P,77Se) = 796.3 Hz, P = Se); selected IR data (KBr): ñ =
1742 (s, C=O), 1224 (m, C O), 523 cm 1 (m, P=Se); elemental analysis [1] a) M. P. Cava, M. I. Levinson, Tetrahedron 1985, 41, 5061; b) R. A.
calcd (%) for C16H13O2PSe3 : C 38.04, H 2.59; found: C 38.47, H 2.30; Cherkasov, G. A. Kutyrev, A. N. Pudovik, Tetrahedron 1985, 41,
EIMS (positive mode): 506 [M] + . 2567; c) M. Jesberger, T. P. Davis, L. Barner, Synthesis 2003, 1929;
Compound 9 (0.056 g, 20 % yield): Yellow crystals suitable for X-ray d) B. S. Pedersen, S. Scheibye, N. H. Nilsson, S. O. Lawesson, Bull.
analysis were grown by layering of a chloroform solution with hexane; Soc. Chim. Belg. 1978, 87, 223; e) H. Hoffman, G. Schumacher, Tet-
1 rahedron Lett. 1967, 8, 2963; f) M. R. St. J. Foreman, A. M. Z.
H NMR (CDCl3): d = 7.90 (m, 2 H; Ph), 7.64 (m, 2 H; Ph), 7.48 (m, 6 H;
Ph), 3.28 ppm (d, 3 H; 3J(31P,1H) 15.0 Hz, CH3); 13C NMR (CDCl3): d = Slawin, J. D. Woollins, J. Chem. Soc. Dalton Trans. 1996, 3653;
194.6 (d, 2J(31P,13C) 17.6 Hz, C = O), 178.6 (d, 2J(31P,13C) 10.4 Hz, C = C- g) M. R. St. J. Foreman, A. M. Z. Slawin, J. D. Woollins, Heteroat.
Ph), 138.8 (d, 1J(31P,13C) 120.8 Hz, P-C = C), 136.5 (d, 3J(31P,13C) 3.1 Hz, Chem. 1999, 10, 651.
C-Ph C-1), 132.1 (d, 2J(31P,13C) 12.5 Hz, P-Ph-o), 130.4 (s, C-Ph-o), 130.0 [2] J. T. Shore, W. T. Pennington, M. C. Noble, A. W. Cordes, Phospho-
(d, 1J(31P,13C) 121.4 Hz, P-Ph C-1), 129.6 (d, 4J(31P,13C) 4.2 Hz, P-Ph-p), rus Sulfur Relat. Elem. 1988, 39, 153.

6226 www.chemeurj.org G 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2005, 11, 6221 – 6227
Synthesis of Novel P–Se Heterocycles
FULL PAPER
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Chem. Eur. J. 2005, 11, 6221 – 6227 G 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 6227