Preparation and reactivity of chalcogenyl phosphonates and phosphane oxides

Article abstract of DOI:10.1002/ejoc.200700388

The preparation of new bis[(diphenylphosphinoyl)methyl] sulfides, selenides, and tellurides is described by the reaction of (diphenylphosphinoyl) methyl p-toluenesulfonate with sodium chalcogenides. The title compounds are subjected to Horner-Wittig-type

Full text of DOI:10.1002/ejoc.200700388

FULL PAPER
DOI: 10.1002/ejoc.200700388
Preparation and Reactivity of Chalcogenyl Phosphonates and Phosphane
Oxides
Claudio C. Silveira,*[a] Francieli Rinaldi,[a] and Rafael C. Guadagnin[a]
Keywords: Horner–Wittig reaction / Chalcogens / Phosphane oxides / Selenium / Tellurium
The preparation of new bis[(diphenylphosphinoyl)methyl]
sulfides, selenides, and tellurides is described by the reaction
of (diphenylphosphinoyl)methyl p-toluenesulfonate with so-
dium chalcogenides. The title compounds are subjected to
Horner–Wittig-type reactions with aldehydes and ketones to
give symmetrical divinylic sulfides, selenides, and tellurides
with preferential (E) stereochemistry. Unsymmetrical divi-
nylic sulfides can be prepared by the use of an appropriate
carbonyl compound.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
ferred.[5d] The synthesis of divinylic selenides by the Wittig–
Horner reaction was recently studied and described by the
reaction of the corresponding selenium bis(phosphonate)
with aromatic aldehydes.[5d] In the case of vinylic tellurides,
the most useful methods are Pd-catalyzed homocoupling[10]
and cross-coupling reactions,[11] NiII-catalyzed cross-coup-
ling reactions with alkynes[12a] and metal acetylides,[12b] and
carbonylation in the presence of PdII salts leading to carb-
oxylic acids.[13,14] Vinyl tellurides are especially useful in
transmetalation reactions. Their treatment with lithium,[15]
Li/Ce,[15a] Li/Zn,[16] Zn,[17,18] sodium,[19] calcium,[19] or
Grignard reagents,[20] followed by the capture of the vinyl
metals with electrophiles, occurs with retention of the
carbon–carbon bond geometry. In addition, higher order
vinylcuprates [vinylCu(R)CNLi2] can be accessed upon
transmetalation of vinyl tellurides with higher order cyano-
cuprates, and they can undergo 1,4-addition to enones,[21]
epoxides,[21a,22] and bromoalkynes.[23] Substitution of the
tellurium moieties by methyl or alkyl groups is achieved
upon treatment with Me2CuLi,[15d] with Grignard rea-
gents,[24] magnesium higher order cuprates,[25] and alkyl-
and alkynylzinc reagents.[26]
A straightforward method for the preparation of sym-
metrical divinyl tellurides is based on the hydrotelluration
of acetylenes with the system Te/NaBH4/EtOH/THF/
NaOH (aqueous).[27] This method, however, produces pre-
dominantly (Z) adducts, but it is efficient only with acetyl-
enes conjugated to aryl groups, C=C bonds, or other elec-
tron-withdrawing groups. In contrast, alkyl acetylenes are
fairly unreactive. Another method recently described for the
preparation of symmetrical divinyl tellurides employs aryl-
tellurophosphoranes derived from bis(triphenylmethylphos-
phonium) halotellurates.[5b]
Introduction
Organochalcogenium compounds have recently attained
remarkable development as synthetic reagents and interme-
diates; they are not only the subject of many review arti-
cles[1] but books as well.[2] Among the many classes of or-
ganochalcogenium compounds, vinylic chalcogenides exhi-
bit a peculiar role.[3] Several methods for the synthesis of
vinylic chalcogenides are known and the Wittig or Horner–
Wittig reactions are among the most useful ones.[4] We[5]
and others[6] recently reported convenient methods for the
synthesis of vinylic selenides, vinylic tellurides, and also vi-
nylic sulfides by Wittig or Horner–Wittig reactions.
From the many applications of vinyl selenides and vinyl
sulfides, the nickel-catalyzed coupling reaction with Grig-
nard reagents to give the corresponding cross-coupled
products has been described.[7] A chemoselective coupling
reaction was described by the reaction of (E)- and (Z)-
(phenylthio)ethenyl methyl selenides with Grignard rea-
gents, catalyzed by NiII species, in which only the selenium
organyl was removed. Stereospecific carbon–selenium bond
cleavage can be achieved by choosing the appropriate Ni
catalyst.[8] The coupling of vinylic selenides with trimethyl-
silylmagnesium chloride by NiCl2(Ph3P)2 or PdCl2(Ph3P)2
catalysis has also been applied to the synthesis of allylsi-
lanes.[9] However, in all these methods, when the coupling
reaction is performed, one of the two organic moieties
linked to the chalcogen atom, which is usually a phenyl or
a methyl group, is lost. To address this problem, we envi-
sioned that by using divinylic selenides in these coupling
reactions, both organyls linked to selenium could be trans-
[a] Departamento de Química, Universidade Federal de Santa
Maria,
In light of the above comments it is of interest to develop
practical stereoselective synthetic methods for symmetrical
and unsymmetrical divinylic chalcogenides with the aim to
Caixa Postal 5001 Campus, 97105-900 Santa Maria, RS, Brazil
Fax: +55-55-3220-8754
E-mail: silveira@quimica.ufsm.br
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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C. C. Silveira, F. Rinaldi, R. C. Guadagnin
FULL PAPER
use them in the construction of olefins with defined stereo-
chemistries and to attain easy access to vinyl–metal species.
Particularly interesting is the possibility that both organyls
linked to the chalcogenium atom in divinylic chalcogenides
could be used.
Results and Discussion
Scheme 2.
Here we describe our results obtained in the convenient
preparation of (tosylmethyl)diphenylphosphane oxide
2[28,29] from 1, and its conversion into bis(methyldiphenyl-
phosphane oxide) sulfide 3a, selenide 3b, and telluride 3c
by reaction with Na2Y (Y = S, Se, Te) in DMF (Scheme 1).
In all examples, a high preference for the (E/E) isomers
could be detected by 1H and 13C NMR spectroscopy, which
is in accordance with these one-step Horner–Wittig reac-
tions of phosphane oxides, usually (E) selective.[33] For ex-
ample, in the synthesis of vinyl sulfides[34] or vinyl fluo-
rides,[31] the diastereomeric ratio was 3:1 or lower. Pure (E)
or (Z) alkenes would be accessible by the two-step Horner–
Wittig strategy.[33] We were also able to obtain the pure (E)
isomer by successive washings with petroleum ether.
An interesting mixed phosphorus sulfide can be prepared
by a convenient choice of adequate starting materials. Thus,
phosphonoxide 13[35] can be prepared from CH3COSH by
treatment with NaH followed by reaction with tosylate 2.
Basic hydrolysis of 13 in MeOH and reaction with iodo-
methyl (diethyl)phosphonate in CH3CN furnishes 14
(Scheme 3). Preliminary studies on the reactivity of 14 with
NaH and cyclic ketones showed a small preference for the
mono Horner–Wittig reaction to occur at the diphenyl-
phosphane oxide side (ca. 3:1). In the next step, reaction of
the intermediate with aromatic aldehydes furnishes unsym-
metrical divinylic sulfides in a reaction closely related to the
one described in Scheme 2 to give compound 6.
Scheme 1.
Compound 1 was prepared by the reaction of diphenyl-
phosphane[30] with Na or Li, in THF, followed by the ad-
dition of p-formaldehyde at –40 °C. After the reaction was
complete, H2O2 (30% vol) was slowly added, at 0 °C to give
1 in 81% isolated yield. Next, treatment of hydroxylmethyl-
diphenylphosphane oxide 1 with base (Et3N) and TsCl in
CH2Cl2 at 0 °C furnished the corresponding tosylate 2 in
96% isolated yield. This interesting tosylate was prepared
previously in THF[31] and in pyridine.[32] To our purposes,
tosylate 2 can be conveniently converted to sulfide 3a, sele-
nide 3b, or telluride 3c by treatment with sodium chalcogen-
olates in DMF. Compounds 3a–c are very interesting spe-
cies, as they combine three active sites for metal binding,
which are the chalcogen atom and the two diphenylphos-
phoryl groups. We disclose here their use in Horner–Wittig-
type reactions, which could furnish the corresponding di-
vinylic chalcogenides according to Scheme 2. Thus, treat-
ment of 3a with an excess amount of base (NaH) and
3 equiv. of benzaldehyde furnished the corresponding bis-
(styryl) sulfide in 85% yield. We performed some reactions
with KH as the base, but no improvements in the yield or
stereoselectivity of the reaction was observed. We next ob-
Scheme 3.
Conclusions
We described a convenient method for the preparation of
served that in the reaction of 3a with ketones, which are bis[(diphenylphosphinoyl)methyl] sulfide, selenide, and tel-
less reactive in Wittig-type reactions, one can selectively luride by the reaction of (diphenylphosphinoyl)methyl p-
perform the reaction at one side of the substrate and vinylic toluenesulfonate with sodium sulfide, selenide, and tellur-
sulfide 5 can be prepared. Sulfide 5 can be isolated and ide, respectively. The bis[(diphenylphosphinoyl)methyl]
purified and subsequently reacted with a different carbonyl chalcogenides were subjected to Horner–Wittig reactions
compound, such as p-anisaldehyde to give 6, which allows with arenecarbaldehydes and NaH as base to give symmet-
easy entry to unsymmetrical divinylic sulfides (Scheme 2). rical divinylic sulfides, selenides, and tellurides, with prefer-
Similar reactions can be performed with selenide 3b and ential (E) stereochemistry. Unsymmetrical divinylic sulfides
telluride 3c to give symmetrical selenide 7 and telluride 10 can be prepared by the reaction with ketones followed by
and unsymmetrical selenide 9 and telluride 12, respectively. arenecarbaldehydes.
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Eur. J. Org. Chem. 2007, 4935–4939

Chalcogenyl Phosphonates and Phosphane Oxides
(6 mmol; prepared as below) in small portions.[36] The reaction
mixture was stirred for 1 h at 0 °C, then another 4 h at room temp.
After this, water (50 mL) was added, and the mixture was extracted
with ethyl acetate (4ϫ50 mL). The combined organic layers were
washed with water (2ϫ100 mL) and brine (100 mL). The organic
layer was dried (MgSO4), and the solvent was removed under re-
duced pressure. The residue was recrystallized (CH2Cl2/Et2O, 1:9).
Yield: 79%. M.p. 171–174 °C. 1H NMR (200 MHz, CDCl3): δ =
3.47 (d, JP,H = 5.73 Hz, 4 H), 7.27–7.56 (m, 12 H), 7.70–7.80 (m, 8
Experimental Section
(Diphenylphosphinoyl)methanol (1): Diphenylphosphane[30] (5.59 g,
30 mmol) was added to a flask containing Na metal (0.80 g,
35 mmol; cut into small pieces) in THF (60 mL) under an atmo-
sphere of argon, at 0 °C, and the reaction became reddish. Stirring
was maintained for an additional 20 min and then at room temp.
for 24 h. The reaction was then cooled to –40 °C and paraformal-
dehyde (0.99 g) was added. The temperature was slowly raised to
room temp. and stirred for another 24 h. Then, H2O (30 mL) was
added slowly, and the reaction was stirred for another 20 min and
neutralized to pH 7 with HCl (3 ). The organic phase was sepa-
rated, H2O2 (30% vol, ca 6 mL) was added dropwise at 0 °C. The
reaction was followed by TLC and after 2 h H2O was added. The
solution was extracted with ethyl acetate (2ϫ60 mL), and the com-
bined organic layers were washed with brine and dried (MgSO4).
After filtration, the solvents were removed under reduced pressure,
and the residue was purified by recrystallization (ethyl acetate/hex-
anes, 1:9). Yield: 83%. M.p. 136–137 °C. 1H NMR (400 MHz,
CDCl3): δ = 4.40 (s, 2 H), 5.82 (s, 1 H), 7.42–7.50 (m, 6 H), 7.72–
7.77 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 60.93 (d,
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 19.35 (d, JP,C
=
69.90 Hz), 128.36 (d, JP,C = 12.00 Hz), 130.80 (d, JP,C = 9.89 Hz),
131.73 (d, JP,C = 2.82 Hz), 132.07 (d, JP,C = 101.0 Hz) ppm. IR
(KBr): ν = 1193 (P=O), 1332, 1438, 2905 cm–1. MS: m/z (%) = 510
˜
(2) [M]+, 292 (34), 216 (18), 215 (100), 201 (30), 183 (19), 91 (54),
77 (45), 65 (10), 51 (28), 47 (35). HRMS (ESI): calcd. for
C26H24NaO2P2Se [M + Na]+ 533.0314; found 533.0309.
Preparation of Na2Se: Se (474 mg, 6 mmol) was added to a solution
of THF (15 mL), Na (32 mg, 14 mmol), and naphthalene (256 mg,
2 mmol) under an atmosphere of argon. The mixture was heated
at reflux for 3 h, and after the color of the solution turned yellow,
DMF (15 mL) was added. THF was removed with a Dean–Stark
apparatus by heating under a flow of argon, and the solution was
then ready to use.
JP,C = 84.06 Hz), 128.43 (d, JP,C = 11.30 Hz), 130.45 (d, JP,C
96.07 Hz), 131.21 (d, JP,C = 9.18 Hz), 131.90 (d, JP,C = 2.82 Hz)
ppm.
=
(Diphenylphosphinoyl)methyl p-Toluenesulfonate (2): To a solution
of (diphenylphosphinoyl) methanol 1 (4.64 g, 20 mmol) in CH2Cl2
(50 mL), under an atmosphere of argon, was added triethylamine
(2.12 g, 21 mmol) dropwise at 0 °C. The reaction mixture was
stirred 30 min at room temp., cooled to 0 °C, and p-tosyl chloride
(4.34 g, 21 mmol) was added. The reaction was kept at 0 °C for
30 min and then 4 h at room temp. Water (50 mL) was added, and
the mixture was extracted with CH2Cl2 (3ϫ30 mL). The organic
layer was dried (MgSO4), and the solvent was removed under re-
duced pressure. The solid residue was recrystallized (CH2Cl2/Et2O,
1:9) to afford colorless crystals. Yield: 96%. M.p. 124–125 °C
(ref.[31] 124–125 °C). 1H NMR (400 MHz, CDCl3): δ = 2.42 (s, 3
H), 4.62 (d, JP,H = 7.03 Hz, 2 H), 7.26 (d, J = 7.78 Hz, 2 H), 7.48–
7.62 (m, 8 H), 7.70–7.74 (m, 4 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 21.49, 64.60 (d, JP,C = 82.05 Hz), 127.95, 128.63 (d,
JP,C = 13.04 Hz), 128.84 (d, JP,C = 103.84 Hz), 129.83, 130.93,
131.28 (d, JP,C = 9.97 Hz), 132.66 (d, JP,C = 3.07 Hz), 145.39 ppm.
Bis[(diphenylphosphinoyl)methyl] Telluride (3c): To a solution of tos-
ylmethyldiphenylphosphane oxide 2 (3.86 g, 10 mmol) in dry DMF
(20 mL), under an atmosphere of argon at 0 °C was added Na2Te
(6 mmol, prepared from Te and NaH in DMF)[2a] in small portions.
The reaction mixture was stirred for 4 h at 50 °C and then water
(50 mL) was added. The mixture was filtered through Celite, ex-
tracted with ethyl acetate (4ϫ50 mL), and the combined organic
layers were washed with water (2ϫ100 mL) and brine (100 mL).
The organic layer was dried (MgSO4), and the solvent was removed
under reduced pressure. The solid residue was recrystallized
(CH2Cl2/Et2O, 1:9). Yield: 71%. M.p. 159–162 °C. 1H NMR
(400 MHz, CDCl3): δ = 3.46 (d, JP,H = 6.51 Hz), 7.41–7.52 (m, 12
H), 7.70–7.77 (m, 8 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
–1.23 (d, JP,C = 68.24 Hz), 128.47 (d, JP,C = 12.27 Hz), 130.97 (d,
JP,C = 9.97 Hz), 131.72 (d, JP,C = 3.07 Hz), 132.84 (d, JP,C
=
101.21 Hz) ppm. IR (KBr): ν = 1181 (P=O), 1437 cm–1. MS: m/z
˜
(%) = 558 (2) [M – 2]+, 353 (65), 229 (39), 227 (25), 215 (60), 201
(86), 183 (28), 91 (29), 77 (100), 51 (66), 47 (44). HRMS (ESI):
calcd. for C26H24NaO2P2Te [M + Na]+ 583.0211; found. 583.0219.
Bis[(diphenylphosphinoyl)methyl] Sulfide (3a): To a solution of tos-
ylmethyldiphenylphosphane oxide 2 (3.86 g, 10 mmol) in dry DMF
(30 mL), under an atmosphere of argon at 0 °C, was added an ex-
cess amount of Na2S (0.780 g, 10 mmol) in small portions. The
reaction mixture was heated at 60 °C for 90 min and then water
(50 mL) was added, and the mixture was extracted with ethyl ace-
tate (4ϫ50 mL). The combined organic layers were washed with
water (2ϫ100 mL) and brine (100 mL). The organic layer was
dried (MgSO4), and the solvent was removed under reduced pres-
sure. The solid residue was recrystallized (CH2Cl2/Et2O, 1:9) to give
General Procedure for the Preparation of Divinyl Chalcogenides 4,
7, and 10: NaH (dry 95%; 51 mg, 2 mmol) was added to a solution
of chalcogeno bis(phosphane oxide) (0.5 mmol) in THF (10 mL)
at room temp. After 20 min, the appropriate carbonyl compound
(1.5 mmol) was added, and the mixture was stirred for 3 h. A solu-
tion of saturated aqueous NH4Cl was then added, and the mixture
was extracted with ethyl acetate (20 mL). The organic layer was
dried (MgSO4), filtered, and removed under reduced pressure. The
residue was purified by column chromatography (hexanes).
1
3a. Yield: 81%. M.p. 149–152 °C. H NMR (400 MHz, CDCl3): δ
= 3.59 (d, JP,H = 6.19 Hz, 4 H), 7.41–7.53 (m, 12 H), 7.70–7.79
(m, 8 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 29.77 (d, JP,C
=
Bis(styryl) Sulfide (4): Yield: 85%. M.p. 40–42 °C. (E/Z), 7.2:1.
69.40 Hz), 128.53 (d, JP,C = 11.60 Hz), 131.01 (d, JP,C = 9.70 Hz),
131.39 (d, JP,C = 100.05 Hz), 131.98 (d, JP,C = 1.50 Hz) ppm. IR
1
Mixture of (E/Z) isomers: H NMR (400 MHz, CDCl3): δ = 6.46
(d, J = 10.8 Hz, 1 H), 6.59 (d, J = 10.8 Hz, 1 H), 6.67 (d, J =
(KBr): ν = 1180 (P=O), 1367, 1436, 2896 cm–1. MS: m/z (%) = 462
˜
1
15.6 Hz, 1 H), 6.82 (d, J = 15.6 Hz, 1 H) ppm. (E/E) Isomer: H
(6) [M]+, 217 (21), 216 (22), 215 (100), 201 (28), 183 (15), 125 (11),
91 (51), 77 (37), 51 (21), 47 (31). C26H24O2P2S (462.48): calcd. C
67.21, H 5.51; found C 67.52, H 5.23.
NMR (400 MHz, CDCl3): δ = 6.68 (d, J = 15.6 Hz, 2 H), 6.85 (d,
J = 15.6 Hz, 2 H), 7.20–7.39 (m, 10 H, arom) ppm. 13C NMR
(100 MHz, CDCl3): δ = 121.86, 125.90, 127.48, 128.64, 130.60,
Bis[(diphenylphosphinoyl)methyl] Selenide (3b): To a solution of tos-
ylmethyldiphenylphosphane oxide 2 (3.86 g, 10 mmol) in dry DMF
(20 mL), under an atmosphere of argon at 0 °C, was added Na2Se
136.43 ppm. IR (KBr): ν = 942, 1444, 1567, 1595 cm–1. GC–MS:
˜
m/z (%) = 238 (100) [M]+, 134 (32), 129 (33), 128 (40), 121 (77),
116 (56), 115 (85), 91 (74), 77 (85), 65 (32), 51 (69), 45 (33).
Eur. J. Org. Chem. 2007, 4935–4939
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4937

C. C. Silveira, F. Rinaldi, R. C. Guadagnin
FULL PAPER
Bis(4-chlorostyryl) Selenide (7): Yield 70%. M.p. 121–123 °C.
(E/Z), 7.7:1. Mixture of (E/Z) isomers: 1H NMR (400 MHz,
CDCl3): δ = 6.79 (d, J = 10.3 Hz, 1 H), 6.96 (d, J = 10.3 Hz, 1 H),
7.09 (d, J = 15.81 Hz, 1 H) ppm. (E/E) Isomer: 1H NMR
(400 MHz, CDCl3): δ = 6.82 (d, J = 15.8 Hz, 2 H), 7.12 (d, J =
15.8 Hz, 2 H), 7.25–7.34 (m, 10 H, arom) ppm. 13C NMR
(100 MHz, CDCl3): δ = 118.36, 127.12, 128.81, 133.33, 133.45,
(KBr): ν = 1255, 1462, 1568, 1606 cm–1. GC–MS: m/z (%) = 317
˜
(190) [M + 1]+, 316 (81) [M]+, 217 (25), 195 (77), 147 (25), 134
(82), 122 (19), 121 (100), 97 (30), 91 (19), 57 (60), 44 (27), 43 (35),
41 (37). C20H28OS (316.51): calcd. C 75.90, H 8.92; found C 75.84,
H 8.99.
(4-tert-Butylcyclohexylidene)methyl (4-Methylstyryl) Selenide (9):
Yield: 79%. (Z/E), 1:16. (E) Isomer: 1H NMR (200 MHz, CDCl3):
δ = 0.85 (s, 9 H), 1.01–1.22 (m, 3 H), 1.86–1.88 (m, 3 H), 2.09–2.16
(m, 1 H), 2.30 (s, 3 H), 2.44–2.48 (m, 1 H), 2.72–2.77 (m, 1 H),
6.01 (s, 1 H), 6.68 (d, J = 15.74 Hz, 1 H), 6.96 (d, J = 15.74 Hz, 1
H), 7.08 (d, J = 7.99 Hz, 2 H), 7.18 (d, J = 7.99 Hz, 2 H) ppm. (E)
Isomer: 13C NMR (100 MHz, CDCl3): δ = 21.13, 27.56, 27.98,
28.88, 32.32, 32.38, 37.01, 47.85, 107.10, 110.31, 118.31, 125.56,
135.26 ppm. IR (KBr): ν = 1100, 1174, 1400, 1488, 1586 cm–1. GC–
˜
MS: m/z (%) = 354 (24) [M]+, 274 (37), 239 (57), 204 (75), 182 (28),
125 (31), 101 (100), 75 (64), 51 (32).
Bis(styryl) Telluride (10): Yield: 78%. M.p. 50–52 °C. (E/Z), 6:1.
1
Mixture of (E/Z) isomers: H NMR (400 MHz, CDCl3): δ = 7.11
(d, J = 10.5 Hz, 1 H), 7.14 (d, J = 16.82 Hz, 1 H), 7.46 (d, J =
1
16.82 Hz, 1 H), 7.51 (d, J = 10.5 Hz, 1 H) ppm. (E/E) Isomer: H 129.24, 131.60, 136.78, 148.08 ppm. GC–MS: m/z (%) = 348 (12)
NMR (400 MHz, CDCl3): δ = 7.16 (d, J = 16.56 Hz, 2 H), 7.50 (d,
[M]+, 346 (6), 267 (7), 197 (8), 142 (10), 131 (16), 115 (19), 105
J = 16.56 Hz, 2 H), 7.22–7.39 (m, 10 H, arom) ppm. 13C NMR (35), 79 (32), 57 (100), 41 (68). C20H28Se (347.38): calcd. C 69.15,
(100 MHz, CDCl3): δ = 99.89, 126.02, 127.81, 128.53, 138.01,
H 8.12. found C 69.30, H 8.21.
143.07 ppm. IR (KBr): ν = 958, 1153, 1431, 1486, 1583, 1764,
˜
(4-tert-Butylcyclohexylidene)methyl (4-Methylstyryl) Telluride (12):
Yield: 74%. (Z/E), 1:15. (E) Isomer: 1H NMR (400 MHz, CDCl3):
δ = 0.86 (s, 9 H), 1.01–1.22 (m, 3 H), 1.83–1.90 (m, 3 H), 1.95–2.02
(m, 1 H), 2.20–2.27 (m, 1 H), 2.32 (s, 3 H), 2.50–2.56 (m, 2 H),
6.24 (s, 1 H), 6.97 (d, J = 16.59 Hz, 1 H), 7.10 (d, J = 7.99 Hz, 2
H), 7.20 (d, J = 7.99 Hz, 2 H), 7.28 (d, J = 16.59 Hz, 1 H) ppm.
(E) Isomer: 13C NMR (100 MHz, CDCl3): δ = 21.16, 27.60, 28.30,
29.07, 32.35, 36.26, 38.21, 47.76, 91.46, 99.30, 125.71, 129.18,
135.73, 137.21, 140.59, 153.82 ppm. GC–MS: m/z (%) = 398 (9)
[M]+, 396 (8), 268 (21), 115 (37), 105 (42), 91 (43), 79 (35), 57 (100),
41 (86). C20H28Te (396.02): calcd. C 60.65, H 7.13; found C 60.65,
H 6.87.
1972 cm–1. GC–MS: m/z (%) = 336 (11) [M]+, 210 (100), 209 (17),
195 (21), 179 (13), 167 (27), 165 (14), 90 (21), 89 (30), 77 (44).
(4-tert-Butylcyclohexylidene)methyl (Diphenylphosphinoyl)methyl
Sulfide (5): NaH (dry 95%; 51 mg, 2 mmol) was added to a solu-
tion of chalcogeno bis(phosphane oxide) 3a (462 mg, 1 mmol) in
THF (10 mL) at room temp. After 20 min, tert-butylcyclohexanone
(170 mg, 1.1 mmol) was added. The reaction was stirred for 6 h at
65 °C (oil bath temperature), and a solution of saturated aqueous
NH4Cl was added. The mixture was then extracted with ethyl ace-
tate (30 mL). The organic layer was dried (MgSO4), filtered, and
removed under reduced pressure. The residue was purified by col-
umn chromatography (CH2Cl2/hexanes/ethyl acetate, 1:5:4) to give
S-(Diphenylphosphinoyl)methyl Ethanethioate (13): Thioacetic S-
acid (761 mg, 10 mmol) in THF (40 mL) was added drop wise to
a solution of NaH (dry 95%; 328 mg, 13 mmol) in THF (20 mL)
at 0 °C. The reaction was stirred at room temp. for 30 min, and a
solution of tosylate 2 (3.86 g, 10 mmol) in THF (40 mL) was slowly
added at 0 °C. The reaction was stirred at room temp. for 30 min
and water was added, and the mixture was extracted with ethyl
acetate. The organic layer was washed with water, dried (MgSO4),
and filtered, and the solvent was removed under reduced pressure.
The residue was purified by column chromatography (hexanes/ethyl
acetate, 6:4). Yield 76%. 1H NMR (200 MHz, CDCl3): δ = 2.24 (s,
3 H), 3.78 (d, JP,H = 8.387 Hz, 2 H), 7.46–7.54 (m, 6 H), 7.73–7.82
1
5. Yield 65%. M.p. 177–179 °C. H NMR (200 MHz, CDCl3): δ =
0.82 (s, 9 H), 0.86–1.16 (m, 3 H), 1.53–1.97 (m, 4 H), 2.13–2.20 (m,
1 H), 2.68–2.75 (m, 1 H), 3.39 (d, JP,H = 8.25 Hz, 2 H), 5.55 (s, 1 H),
7.42–7.59 (m, 6 H), 7.75–7.85 (m, 4 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 27.47, 27.55, 28.47, 29.82, 32.30, 32.46 (d, JP,C
=
69.40 Hz), 35.94, 47.76, 113.58 (d, JP,C = 2.83 Hz), 128.43 (d, JP,C
= 11.30 Hz), 128.46 (d, JP,C = 12.01 Hz), 131.22 (d, JP,C = 9.20 Hz),
131.29 (d, JP,C = 9.20 Hz), 131.78 (d, JP,C = 103.30 Hz), 131.56 (d,
JP,C = 103.30 Hz), 131.96 (d, JP,C = 2.83 Hz), 144.34 ppm. IR
(KBr): ν = 1192 (P=O), 1436, 1618 (C=C) cm–1. MS: m/z (%) =
˜
398 (1) [M]+, 249 (8), 248 (10), 216 (48), 215 (100), 91 (10), 57 (12),
41 (15). C24H31OPS (398.54): calcd. C 71.78, H 7.63; found C
72.33, H 7.84.
(m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 26.93 (d, JP,C
70.64 Hz), 29.71, 128.35 (d, JP,C = 12.01 Hz), 130.72 (d, JP,C
=
=
General Procedure for the Preparation of Unsymmetrical Divinyl
Chalcogenides 6, 9, and 12: NaH (dry 95%; 25 mg, 1 mmol) was
added to a solution of chalcogeno phosphane oxide 5, 8, or 11
(0.5 mmol) in THF (15 mL) at room temp. After 20 min, the appro-
priate aldehyde (0.75 mmol) was added. The reaction was stirred
for 3 h at room temp., saturated aqueous NH4Cl was added, and
the mixture was extracted with ethyl acetate (20 mL). The organic
layer was dried (MgSO4) and filtered, and the solvent was removed
under reduced pressure. The residue was purified by column
chromatography (hexanes).
9.18 Hz), 130.83 (d, JP,C = 103.14 Hz), 132.01 (d, JP,C = 2.83 Hz),
192.65 ppm. IR (KBr): ν = 1126, 1192, 1439, 1704 cm–1.
˜
Diethyl [(Diphenylphosphinoyl)methylthio]methylphosphonate (14):
NaOH (3 , 10 mL) was added to a solution of thiophosphane
oxide (13; 2.90 g, 10 mmol) and methanol (10 mL). The mixture
was stirred at room temp. for 30 min. The temperature was reduced
to 0 °C, and iodomethyl phosphonate (2.78 g, 10 mmol) in CH3CN
(20 mL) was added. The reaction was stirred overnight at room
temp., water was added, and the mixture was extracted with ethyl
acetate. The organic layer was washed with ammonium chloride,
dried (MgSO4), and filtered, and the solvent was removed under
(4-tert-Butylcyclohexylidene)methyl (4-Methoxystyryl) Sulfide (6):
Yield: 78%. M.p. 67–69 °C. (Z/E), 1:12. (E) Isomer: 1H NMR
(200 MHz, CDCl3): δ = 0.86 (s, 9 H), 1.00–1.27 (m, 3 H), 1.75– 1:9). Yield: 72%. M.p. 96–98 °C. H NMR (200 MHz, CDCl3): δ
vacuo. The residue was purified by recrystallization (CH2Cl2/Et2O,
1
1.92 (m, 3 H), 2.05–2.18 (m, 1 H), 2.36–2.46 (m, 1 H), 2.79–2.89
(m, 1 H), 3.79 (s, 3 H), 5.80 (s, 1 H), 6.43 (d, J = 15.34 Hz, 1 H),
6.59 (d, J = 15.34 Hz, 1 H), 6.83 (d, J = 8.89 Hz, 2 H), 6.59 (d, J
= 8.89 Hz, 2 H) ppm. (E) Isomer: 13C NMR (100 MHz, CDCl3):
δ = 27.54, 27.87, 28.86, 30.30, 32.40, 36.37, 47.90, 55.17, 111.05,
= 1.30 (t, J = 7.1 Hz, 6 H), 2.94 (d, JP,H = 12.0 Hz, 2 H), 3.62 (d,
JP,H = 7.0 Hz, 2 H), 4.13 (qui, J = 7.3 Hz, 4 H), 7.27–7.55 (m, 6
H), 7.74–7.84 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
16.32 (d, JP,C = 6.13 Hz), 25.32 (d, JP,C = 148.6 Hz), 29.62 (d, JP,C
= 70.54 Hz), 62.63 (d, JP,C = 6.90 Hz), 128.56 (d, JP,C = 11.5 Hz),
113.97, 121.76, 126.61, 126.66, 129.93, 146.10, 158.62 ppm. IR 131.04 (d, JP,C = 9.97 Hz), 131.82 (d, JP,C = 100.45 Hz), 132.02 (d,
4938
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2007, 4935–4939

Chalcogenyl Phosphonates and Phosphane Oxides
S. K. Kang, S. W. Lee, M. S. Kim, H. S. Kwon, Synth. Com-
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216 (41), 215 (100), 201 (13), 141 (14), 125 (14), 77 (19), 47 (21).
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Received: May 2, 2007
Published Online: August 3, 2007
Eur. J. Org. Chem. 2007, 4935–4939
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4939