Electrophilic addition of thioselenophosphinic acids to vinyl sulfides and selenides

Article abstract of DOI:10.1080/17415993.2015.1007142

The thioselenophosphinic acids, R₂P(Se)SH (R = Ph, Cy, aralkyl), prepared by acidification of the sodium salts or generated in situ by reaction of secondary phosphine sulfides with elemental selenium, add easily to diverse vinyl sulfides and vi

Full text of DOI:10.1080/17415993.2015.1007142

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Electrophilic addition of
thioselenophosphinic acids to vinyl
sulfides and selenides
Alexander V. Artem'eva, Ludmila A. Oparinaa, Oksana V.
Vysotskayaa, Nikita A. Kolyvanova, Nina K. Gusarovaa & Boris A.
Trofimova
a A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of
the Russian Academy of Sciences, Irkutsk, Russian Federation
Published online: 06 Feb 2015.
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To cite this article: Alexander V. Artem'ev, Ludmila A. Oparina, Oksana V. Vysotskaya,
Nikita A. Kolyvanov, Nina K. Gusarova & Boris A. Trofimov (2015): Electrophilic addition of
thioselenophosphinic acids to vinyl sulfides and selenides, Journal of Sulfur Chemistry, DOI:
10.1080/17415993.2015.1007142
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Journal of Sulfur Chemistry, 2015
http://dx.doi.org/10.1080/17415993.2015.1007142
Electrophilic addition of thioselenophosphinic acids to vinyl
sulfides and selenides
Alexander V. Artem’ev, Ludmila A. Oparina, Oksana V. Vysotskaya, Nikita A. Kolyvanov,
Nina K. Gusarova and Boris A. Trofimov∗
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk,
Russian Federation
(Received 20 October 2014; accepted 9 January 2015)
The thioselenophosphinic acids, R2P(Se)SH (R = Ph, Cy, aralkyl), prepared by acidification of the
sodium salts or generated in situ by reaction of secondary phosphine sulfides with elemental selenium, add
easily to diverse vinyl sulfides and vinyl selenides in a Markovnikov manner to give the corresponding S-
and Se-esters in a ∼ 60:40 molar ratio (83–96% total yield).
Keywords: vinyl sulfides; vinyl selenides; secondary phosphine sulfides; thioselenophosphinic acids;
addition
1. Introduction
The esters of dithio(diseleno)phosphinic and -phosphoric acids of general formula R2P(X)XRꢀ
(X = S, Se; R = OAlk, OAr, hydrocarbyl; Rꢀ = hydrocarbyl) attract growing attention as inifer-
ter agents for living radical polymerization,[1–4] biological active compounds [5,6] and building
blocks for organic synthesis.[7,8] From the viewpoint of atom economy and green chemistry,
one of the most efficient routes toward the above esters is the addition of dichalcogenophos-
phinic acids to alkenes. By now, the addition of O,Oꢀ-dialkyldithiophosphoric acids and, in a less
degree, dithiophosphinic acids to alkenes is the most developed. Thus, the electron-deficient sub-
strates add these acids in an anti-Markovnikov fashion,[9–15] whereas the electron-rich [16–18]
and unactivated [19–21] alkenes afford the Markovnikov-type adducts. The organophosphorus
diselenoacids, due to their instability,[22] are less studied in reactions with alkenes. It is known
*Corresponding author. Email: boris_trofimov@irioch.irk.ru
c
ꢁ 2015 Taylor & Francis

2
A.V. Artem’ev et al.
(a)
(b)
Scheme 1. The addition of thioselenophosphinic acids to alkenes: the known examples.
that the addition of R2P(Se)SeH acids, generated in situ from secondary phosphines and elemen-
tal selenium, to diverse electron-rich alkenes, for example, styrenes,[23] vinyl ethers,[24] vinyl
sulfides [25] and vinyl selenides,[26] provides the corresponding Markovnikov adducts in high
yields.
At the same time, the thioselenophosphinic acids, R2P(Se)SH, remain almost unexplored in
the addition reactions. To our knowledge, only several separate examples on the addition of
R2P(Se)SH species to C C bonds have been reported so far. Namely, the addition of Ph2P(Se)SH
acid to methyl vinyl ketone [27] selectively occurs in an anti-Markovnikov manner to furnish
the corresponding Se-ester (Scheme 1(a)). More recently,[28] we have shown that the addition of
thioselenophosphinic acids (in free form or in situ generated from secondary phosphine sulfides
and elemental selenium) to vinyl ethers bearing alkyl or aryl substituents proceeds according to
the Markovnikov rule to afford S- and Se-adducts in 73–95% total yield (Scheme 1(b)). Though
the ratio of these isomers depends on the nature of substituents both within vinyl ethers and
thioselenophosphinic acids, in the most cases, the S-esters were major products (from 57 to 80
mol% in the mixture of isomers). Meanwhile, the addition of R2P(Se)SH acids to vinyl ethers
containing bulk of sterically hindered groups, for example, 1-naphthyl and 2,6-dimethylphenyl,
provides S- and Se-adducts in nearly equal amounts.[28]
To examine the generality of this reaction and to elucidate the influence of substituents within
alkenes on its chemo- and regioselectivity, we have extended its scope over vinyl sulfides and
selenides, which are important and ever-growing family of functional alkenes.[29,30] Most sig-
nificantly, the vinyl sulfides and selenides, especially their simple alkyl and aryl representatives,
now are readily available via direct vinylation of thiols [31] or “elemental Se/organic halide”
systems,[32,33] correspondingly, with acetylene in the alkali media.
2. Results and discussion
We have shown that the diphenylthioselenophosphinic acid (1a), prepared by acidification of
its sodium salt with trifluoroacetic acid (1:1, 1,4-dioxane, r.t., 10 min), easily adds to vinyl sul-
fide 2a and vinyl selenide 2b in a Markovnikov manner to afford S- and Se-esters 3a,3b in a
ratio of ∼ 60:40 mol% (31P NMR data) (Scheme 2). The latter were isolated as mixtures of
both isomers in 94% and 84% total yield. Though our attempts to separate individual esters by
chromatographic methods (both column and TLC ones) were unsuccessful, their structures were

Journal of Sulfur Chemistry
3
Scheme 2. Addition of diphenylthioselenophosphinic acid (1a) to vinyl chalcogenides 2a,2b.
Table 1. Thioselenophosphinic esters 3c–3 g from secondary phosphine sulfides 4a–4d, vinyl chalcogenides 2b–2e
and elemental selenium.a
R1
Vinyl chalcogenide
S-/Se-esters
Molar ratio of S-/Se-estersb
Total yield (%)c
92
(2c)
Cy (4a, 1b)
3c
56:44
(4b, 1c)
(4b, 1c)
(2c)
(2d)
3d
3e
60:40
64:36
96
83
(2b)
(2e)
(4c, 1d)
(4d, 1e)
3f
59:41
58:42
87
87
3 g
aThe reaction conditions: secondary phosphine sulfide (0.5 mmol), vinyl chalcogenide (0.5 mmol), selenium (0.5 mmol), 1,4-dioxane (5
ml), 110°C, up to 1 h.
bDetermined by integration of signals in 31P NMR spectra.
cIsolated yield.
unambiguously established by the NMR (1H, 13C, 31P and 77Se) and FT-IR spectroscopy (vide
infra).
The generality of the above reaction (Scheme 2) is confirmed by the fact that the other thiose-
lenophosphinic acids 1b–1e, when generated in situ from secondary phosphine sulfides 4a–4d
and elemental selenium (110°C, 1,4-dioxande, up to 1 h), are added to various vinyl sulfides and
selenides 2b–2e (both alkyl- and aryl-substituted) in a similar manner to give the correspond-
ing S- and Se-esters 3c–3 g in 83–96% total yield with nearly the same ratio (ca. 60:40 mol%)
(Table 1). Notably, the order of reactants mixing does not affect the reaction course and the
product yields.
The data on Scheme 2 and Table 1 reveal that the structure of the substituents both in vinyl
chalcogenides (aryl, alkyl) and thioselenophosphinic acids (aryl, alkyl, aralkyl) has little effect
on the molar ratio of formed S- and Se-esters 3a–3 g (ca. 60:40, in all the cases). Moreover, this
ratio is almost independent (within the experimental error) of the nature of heteroatom within

4
A.V. Artem’ev et al.
vinyl chalcogenides (S or Se). Conversely, in the case of vinyl ethers,[28] the ratio of formed S-
and Se-esters (ranges from 50:50 to 80:20, respectively) is quite sensitive to the electronic and
steric properties of substituents within the both reactants.
1
The H, 13C, 31P and 77Se NMR shifts of the individual S- and Se-esters 3a–3 g are suffi-
ciently different; therefore, the structures of the latter were unambiguously established. Thus,
31P NMR spectra of S-esters show sharp singlet at 52.1–88.2 ppm flanked by 77Se satellites with
1
JP−Se coupling constant of 750–780 Hz, indicating the presence of P Se bond. The 77Se NMR
=
1
spectra of the S-esters reveal downfield doublet ( − 376) − ( − 190) ppm with the same JPSe
constant. The 31P NMR spectra of Se-esters show a sharp singlet at 50.8–88.6 ppm flanked by
77Se satellites (1JPSe = 346–378 Hz), while their 77Se NMR spectra contain a doublet (270–
427 ppm), having the characteristic one-bond 31P-77Se coupling of 351–376 Hz. The 1H and 13
C
NMR spectra of 3a–3 g reveal the expected peaks from the corresponding organic groups in their
typical regions.
=
In FT-IR spectra of the mixtures 3a–3 g, the stretching vibrations of the P–S and P Se bonds
within S-esters appear as middle bands at 542–601 and 494–523 cm−1, whereas the P–Se and
=
P S stretching within Se-esters 3a–3 g are manifested as weak bands at 416–455 and 656–698
cm−1
.
3. Conclusion
In summary, we have demonstrated for the first time that the thioselenophosphinic acids, when
free or in situ generated from secondary phosphine sulfide and elemental selenium, are easily
added to various vinyl sulfides and selenides in a Markovnikov manner to afford thioselenophos-
phinic S- and Se-esters in 83–96% total yield. In all the cases, the ratio of the S- and Se-esters
is close to 60:40, that is, it is weakly dependent on the structure of substituents both in vinyl
chalcogenides and thioselenophosphinic acids. The data obtained contribute to chemistry of both
thioselenophosphinic acids and vinyl chalcogenides.
4. Experimental
4.1. General
All reactions were performed under inert atmosphere (dry argon). 1,4-Dioxane was dried and
freshly distilled over sodium/benzophenone prior to use. Vinyl sulfides 2a,2c,2d,[31] vinyl
selenides 2b,2e [32,33] and sodium salt Ph2P(Se)SNa [34] were prepared according to published
methods. Secondary phosphine sulfides 4a–4d were prepared by oxidation of corresponding
phosphines with powdered sulfur (S8). Cy2PH was used as commercial (Aldrich), while the
1
other phosphines were synthesized from red phosphorus and styrenes.[35,36] The H, 13C, 31P
and 77Se NMR spectra were recorded using a Bruker AV-400 spectrometer at 400.13, 100.62,
161.98 and 76.31 MHz, respectively. The 1H NMR chemical shifts are expressed with respect to
residual protonated CDCl3 (7.27 ppm), which served as an internal standard. The 13C NMR shifts
are expressed with respect to the CDCl3 (77.0 ppm). Eighty-five percent H3PO4/D2O and Me2Se
were used as external standards for 31P and 77Se NMR, correspondingly. IR-FT spectra were
recorded on a Bruker Vertex 70 spectrometer. The C, H, S microanalyses were performed on a
Flash EA 1112 HNS-O/MAS analyzer, while the content of P was determined by the combustion
method.

Journal of Sulfur Chemistry
5
4.2. Addition of diphenylthioselenophosphinic acid to vinyl chalcogenides procedure
To a stirring solution of Ph2P(Se)SNa (0.160 g, 0.5 mmol) in 1,4-dioxane (5 ml), the 1,4-
dioxane solution of CF3COOH (0.5 ml, 1.0 mol/l, 0.5 mmol) was added. After 2–3 min, vinyl
chalcogenide 2a,2b (0.5 mmol) was added and the resulting mixture was stirred at r.t. for 10 min.
The solvent was removed in vacuo, hexane was added to the residue and the formed CF3COONa
was filtrated off. The filtrate was concentrated and purified by flash chromatography (0.5 cm of
basic Al2O3; hexane −ether, 9:1) to give S- and Se-esters 3a,3b.
4.2.1. [1-(Pentylsulfanyl)ethyl] diphenylthioselenophosphinate (S-3a/Se-3a = 60:40)
Yellow oil; yield: 0.201 g (94%). IR (neat, v, cm−1): 746 (P–C), 689 (P S), 565 (P–S), 521
=
=
(P Se), 422 (P–Se). Anal. Calcd for C19H25PS2Se: C, 53.38; H, 5.89; P, 7.25; S, 15.00. Found:
C, 53.43%; H, 5.75%; P, 7.11%; S, 14.89%.
4.2.1.1. S-[1-(Pentylsulfanyl)ethyl] diphenylthioselenophosphinate (S-3a) 1H NMR (400.13
3
MHz, CDCl3): δ = 0.91 (t, JHH = 7.0 Hz, 3 H, MeCH2), 1.31–1.33 [m, 4 H, Me(CH2)2],
3
1.56 (d, JHH = 7.0 Hz, 3 H, MeCH), 1.52–1.60 (m, 2 H, CH2), 2.54–2.62 and 2.69–2.77 (2
m, each 1 H, SCH2), 4.60–4.67 (m, 1 H, SCHS), 7.45–7.50 (m, 6 H, Hm,p in Ph), 7.75–7.85
and 7.86–8.02 (2 m, each 2 H, Ho in Ph). 13C NMR (100.62 MHz, CDCl3): δ = 13.21 (Me),
21.48 (CH2Me), 24.15 (MeCH), 28.33 (CH2Pr), 30.20 (CH2Et), 31.16 (SCH2), 51.00 (SCHS),
3
2
127.75 (d, JPC = 13.3 Hz, Cm in Ph), 130.82 and 131.41 (2 d, JPC = 11.2 and 11.6 Hz, Co
in Ph), 131.15 (d, 4JPC = 3.0 Hz, Cp in Ph) 132.93 and 133.17 (2 d, 1JPC = 72.4 and 75.8 Hz,
Ci in Ph). 31P NMR (161.98 MHz, CDCl3): δ = 52.11 (s, 1JP
= 779 Hz). 77Se NMR (76.31
=
Se
MHz, CDCl3): δ = –213 (d, 1JP
= 780 Hz).
=
Se
4.2.1.2. Se-[1-(Pentylsulfanyl)ethyl] diphenylthioselenophosphinate (Se-3a) 1H NMR
3
(400.13 MHz, CDCl3): δ = 0.91 (t, JHH = 7.0 Hz, 3 H, MeCH2), 1.31–1.33 [m, 4 H,
3
Me(CH2)2], 1.52–1.60 (m, 2 H, CH2), 1.76 (d, JHH = 7.0 Hz, 3 H, MeCH), 2.54–2.62 and
2.69–2.77 (2 m, each 1 H, SCH2), 4.60–4.67 (m, 1 H, SCHSe), 7.45–7.50 (m, 6 H, Hm,p in
Ph), 7.83–7.92 and 7.85–8.05 (2 m, each 2 H, Ho in Ph). 13C NMR (100.62 MHz, CDCl3):
δ = 13.21 (Me), 21.48 (CH2Me), 24.15 (MeCH), 28.33 (CH2Pr), 30.20 (CH2Et), 31.16 (SCH2),
51.00 (SCHS), 127.72 (d, 3JPC = 13.3 Hz, Cm in Ph), 130.50 and 130.89 (2 d, 2JPC = 11.6 and
4
1
11.2 Hz, Co in Ph), 131.07 (d, JPC = 3.0 Hz, Cp in Ph), 134.18 and 134.44 (2 d, JPC = 75.8
and 76.7 Hz, Ci in Ph). 31P NMR (161.98 MHz, CDCl3): δ = 50.80 (s, JPSe = 374 Hz). 77Se
1
NMR (76.31 MHz, CDCl3): δ = 425 (d, 1JPSe = 374 Hz).
4.2.2. [1-(Pentylselanyl)ethyl] diphenylthioselenophosphinate (S-3b/Se-3b = 62:38)
=
=
Yellow oil; yield: 0.199 g (84%). IR (film): 745 (P–C), 689 (P S), 560 (P–S), 520 (P Se), 420
(P–Se). Anal. Calcd for C19H25PSSe2: C, 48.11; H, 5.31; P, 6.53; S, 6.76. Found: C, 47.97%; H,
5.45%; P, 6.34%; S, 6.59%.
4.2.2.1. S-[1-(Pentylselanyl)ethyl] diphenylthioselenophosphinate (S-3b) 1H NMR (400.13
1
MHz, CDCl3): δ = H NMR (400.13 MHz, CDCl3): δ = 0.84 (t, 3JHH = 6.9 Hz, 3 H, MeCH2),
1.24–1.31 [m, 4 H, Me(CH2)2], 1.55 (d, 3JHH = 6.9 Hz, 3 H, MeCH), 1.57–1.67 (m, 2 H, CH2),
2.56–2.64 and 2.70–2.80 (2 m, each 1 H, SeCH2), 4.56–4.64 (m, 1 H, SCHSe), 7.36–7.43 (m,
6 H, Hm,p in Ph), 7.75–7.84 and 7.92–8.01 (2 m, each 2 H, Ho in Ph). 13C NMR (100.62 MHz,
CDCl3): δ = 14.57 (Me), 22.31 (CH2Me), 25.81 (MeCH), 26.20 (CH2Se), 30.16 (CH2Pr), 32.15

6
A.V. Artem’ev et al.
1
3
(CH2Et), 39.73 (d, JCSe = 3.8 Hz, SCHSe), 128.66 (d, JPC = 12.9 Hz, Cm in Ph), 131.63
2
4
and 132.36 (2 d, JPC = 11.2 Hz, Co in Ph), 131.96 (d, JPC = 2.8 Hz, Cp in Ph), 133.79 and
133.92 (2 d, 1JPC = 71.5 and 75.4 Hz, Ci in Ph). 31P NMR (161.98 MHz, CDCl3): δ = 54.90 (s,
1JP
= 774 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = –190 (d, JP
= 775 Hz), 329 (s,
1
=
=
Se
Se
SeCH2).
4.2.2.2. Se-[1-(Pentylselanyl)ethyl] diphenylthioselenophosphinate (Se-3b) 1H NMR
1
(400.13 MHz, CDCl3): δ = H NMR (400.13 MHz, CDCl3): δ = 0.83 (t, 3JHH = 6.9 Hz, 3 H,
3
MeCH2), 1.24–1.31 [m, 4 H, Me(CH2)2], 1.57–1.67 (m, 2 H, CH2), 1.78 (d, JHH = 6.9 Hz,
3 H, MeCH), 2.56–2.64 and 2.70–2.80 (2 m, each 1 H, SeCH2), 4.56–4.64 (m, 1 H, SeCHSe),
7.36–7.43 (m, 6 H, Hm,p in Ph), 7.75–7.84 and 7.92–8.01 (2 m, each 2 H, Ho in Ph). 13C NMR
(100.62 MHz, CDCl3): δ = 14.57 (Me), 22.30 (CH2Me), 26.53 (MeCH), 27.01 (CH2Se), 29.99
(CH2Pr), 32.15 (CH2Et), 35.83 (d, 1JCSe = 3.4 Hz, SeCHSe), 128.60 (d, 3JPC = 12.9 Hz, Cm in
2
4
Ph), 131.31 and 131.83 (2 d, JPC = 11.2 Hz, Co in Ph), 132.15 (d, JPC = 2.6 Hz, Cp in Ph),
134.98 and 135.21 (2 d, 1JPC = 75.0 and 76.7 Hz, Ci in Ph). 31P NMR (161.98 MHz, CDCl3):
1
1
δ = 53.30 (s, JP
= 378 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = 427 (d, JP
= 376
−
−
Se
Se
Hz), 329 (s, SeCH2).
4.3. General procedure for the synthesis of thioselenophosphinic esters 3c–3 g
The secondary phosphine sulfide 4a–4d (0.5 mmol) and powdered selenium (0.039 g, 0.5 mmol)
were added consecutively to a solution of vinyl chalcogenide 2b–2e (0.5 mmol) in 1,4-dioxane
(5 ml) at ambient temperature. The suspension was stirred at 110°C until the dissolution of sele-
nium residue (up to 1 h) to afford a yellow transparent solution. The solvent was removed under
reduced pressure (1 Torr, 50°C), and the residue was purified by flash chromatography (0.3–0.5
cm of basic Al2O3; CHCl3–hexane, 3:1) to give S- and Se-esters 3c–3 g.
4.3.1. 1-(Phenylsulfanyl)ethyl dicyclohexylthioselenophosphinate
(S-3c/Se-3c = 56:44)
Yellowish oil; yield: 0.205 g (92%). IR (neat, v, cm−1): 743 (P–C), 684 (P S), 542 (P–S), 494
=
=
(P Se), 455 (P–Se). Anal. Calcd for C20H31PS2Se: C, 53.92; H, 7.01; P, 6.95; S, 14.39. Found:
C, 54.04%; H, 7.10%; P, 6.72%; S, 14.48%.
4.3.1.1. S-[1-(Phenylsulfanyl)ethyl] dicyclohexylthioselenophosphinate (S-3c) 1H NMR
(400.13 MHz, CDCl3): δ = 1.06–1.26 (m, 10 H, Cy), 1.41–1.80 (m, 6 H, Cy), 1.71 (d,
3JHH = 6.8 Hz, 3 H, MeCH), 1.81–2.05 (m, 6 H, Cy), 4.67–4.71 (m, 1 H, SCHS), 7.52–7.57
(m, 2 H, PhS), 7.31–7.33 (m, 3 H, PhS). 13C NMR (100.62 MHz, CDCl3): δ = 25.59–26.25
(m, MeCH, C-2–6 in Cy), 40.65 and 41.79 (2 d, 1JPC = 38.7 Hz, PCH2), 54.22 (SCHS), 128.13
(Cp in PhS), 128.81 (Co in PhS), 133.49 (Ci in PhS), 133.92 (Cm in PhS). 31P NMR (161.98
MHz, CDCl3): δ = 88.27 (s, 1JP
= 753 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = –376 (d,
=
Se
1JP
= 750 Hz).
=
Se
4.3.1.2. Se-[1-(Phenylsulfanyl)ethyl] dicyclohexylthioselenophosphinate (Se-3c) 1H NMR
(400.13 MHz, CDCl3): δ = 1.06–1.26 (m, 10 H, Cy), 1.41–1.80 (m, 6 H, Cy), 1.89 (d,
3JHH = 6.8 Hz, 3 H, MeCH), 1.81–2.05 (m, 6 H, Cy), 4.67–4.71 (m, 1 H, SCHSe), 7.31–7.33
(m, 3 H, PhS), 7.52–7.57 (m, 2 H, PhS). 13C NMR (100.62 MHz, CDCl3): δ = 25.59–26.25
1
(m, MeCH, C-2–6 in Cy), 41.39 and 42.20 (2 d, JPC = 41.4 and 44.7 Hz, PCH2), 49.10
(SCHSe), 127.81 (Cp in PhS), 128.81 (Co in PhS), 133.06 (Cm in PhS), 134.35 (Ci in PhS). 31
P

Journal of Sulfur Chemistry
7
NMR (161.98 MHz, CDCl3): δ = 88.67 (s, 1JPSe = 351 Hz). 77Se NMR (76.31 MHz, CDCl3):
δ = 270 (d, 1JPSe = 360 Hz).
4.3.2. 1-(Phenylsulfanyl)ethyl bis(4-methoxyphenethyl)thioselenophosphinate
(S-3d/Se-3d = 60:40)
Yellowish oil; yield: 0.264 g (96%). IR (neat, v, cm−1): 740 (P–C), 692 (P S), 550 (P–S),
=
=
518(P Se), 421 (P–Se). Anal. Calcd for C26H31O2PS2Se: C, 56.82; H, 5.69; P, 5.64; S, 11.67.
Found: C, 56.73%; H, 5.47%; P, 5.42%; S, 11.93%.
4.3.2.1. S-[1-(Phenylsulfanyl)ethyl] bis(4-methoxyphenethyl)thioselenophosphinate (S-3d) 1H
3
NMR (400.13 MHz, CDCl3): δ = 1.73 (d, JHH = 6.9 Hz, 3 H, MeCH), 2.32–2.36 (m, 4 H,
CH2P), 2.60–2.94 (m, 4 H, CH2Ar), 3.76 (s, 6 H, OMe), 4.80–4.85 (m, 1 H, SCHS), 6.77–6.81
(m, 4 H, Ar), 7.06 (d, 3JHH = 8.4 Hz, 4 H, Ar), 7.24–7.31 (m, 3 H, Ho,p in PhS), 7.52–7.57 (m, 2
H, Hm in PhS). 13C NMR (100.62 MHz, CDCl3): δ = 25.11 (d, 3JPC = 2.8 Hz, MeCH), 28.72,
1
28.91 (CH2Ar), 38.21 and 39.66 (2 d, JPC = 41.4 and 39.1 Hz, PCH2), 53.90 (SCHS), 55.23
(OMe), 114.08 (C-2,6 in Ar), 128.28 (Cp in PhS), 128.96 (Co in PhS), 129.24 (C-3,5 in Ar),
132.06 (d, 3JPC = 17.1 Hz, C-1 in Ar), 133.24 (Ci in PhS), 133.50 (Cm in PhS), 158.29 (C-4 in
Ar). 31P NMR (161.98 MHz, CDCl3): δ = 64.89 (s, 1JP
= 768 Hz). 77Se NMR (76.31 MHz,
=
Se
CDCl3): δ = –275 (d, 1JP
= 759 Hz).
=
Se
4.3.2.2. Se-[1-(Phenylsulfanyl)ethyl] bis(4-methoxyphenethyl)thioselenophosphinate (Se-3d)
3
1H NMR (400.13 MHz, CDCl3): δ = 1.90 (d, JHH = 7.0 Hz, 3 H, MeCH), 2.32–2.36 (m, 4
H, CH2P), 2.60–2.94 (m, 4 H, CH2Ar), 3.76 (s, 6 H, OMe), 4.80–4.85 (m, 1 H, SCHSe), 6.77–
6.81 (m, 4 H, Ar), 6.98–7.01 (m, 4 H, Ar), 7.24–7.31 (m, 3 H, Ho,p in PhS), 7.52–7.57 (m, 2
H, Hm in PhS). 13C NMR (100.62 MHz, CDCl3): δ = 25.70 (d, 3JPC = 2.8 Hz, MeCH), 28.35,
28.47 (CH2Ar), 39.55 and 40.28 (2 d, 1JPC = 42.3 and 41.9 Hz, CH2P), 49.63 (SCHSe), 55.23
(OMe), 114.00 (C-2,6 in Ar), 128.07 (Cp in PhS), 128.96 (Co in PhS), 129.24 (C-3,5 in Ar),
132.12 (d, 3JPC = 16.0 Hz, C-1 in Ar), 132.91 (Cm in PhS), 134.15 (Ci in PhS), 158.23 (C-4 in
Ar). 31P NMR (161.98 MHz, CDCl3): δ = 65.09 (s, 1JPSe = 346 Hz). 77Se NMR (76.31 MHz,
CDCl3): δ = 350 (d, 1JPSe = 352 Hz).
4.3.3. [1-(Heptylsulfanyl)ethyl] bis(4-methoxyphenethyl)thioselenophosphinate
(S-3e/Se-3e = 64:36)
Yellowish oil; yield: 0.237 g (83%). IR (neat, v, cm−1): 733 (P–C), 684 (P S), 550 (P–S), 518
=
=
(P Se), 447 (P–Se). Anal. Calcd for C27H41O2PS2Se: C, 56.73; H, 7.23; P, 5.42; S, 11.22. Found:
C, 56.71%; H, 7.40%; P, 5.18%; S, 11.31%.
4.3.3.1. S-[1-(Heptylsulfanyl)ethyl] bis(4-methoxyphenethyl)thioselenophosphinate (S-3e) 1H
3
NMR (400.13 MHz, CDCl3): δ = 0.84 (t, JHH = 7.0 Hz, 3 H, MeCH2), 1.23–1.34 (m, 8 H,
CH2), 1.58–1.65 (m, 2 H, CH2), 1.72 (d, 3JHH = 6.9 Hz, 3 H, MeCH), 2.34–2.46 (m, 4 H, CH2P),
2.59–2.66 and 2.71–2.78 (2 m, each 1 H, SCH2), 2.84–2.93 (m, 4 H, CH2Ar), 3.74 (s, 6 H, MeO),
4.48–4.59 (m, 1 H, SCHS), 6.79 (d, 3JHH = 8.3 Hz, 4 H, H-3,5 in Ar), 7.06 (d, 3JHH = 8.3 Hz,
4 H, H-2,6 in Ar). 13C NMR (100.62 MHz, CDCl3): δ = 13.81 (Me), 22.34 (CH2Me), 25.68
3
(d, JPC = 2.6 Hz, MeCH), 28.64 (CH2Ar, CH2Am), 28.74 (CH2Bu), 29.21 (CH2Pr), 31.46
(CH2Et), 31.76 (CH2S), 38.60 and 39.26 (2 d, 1JPC = 39.9 and 39.5 Hz, CH2P), 51.53 (SCHS),
55.04 (MeO), 113.9 (C-3,5 in Ar), 129.02 (C-2,6 in Ar), 131.91 (d, 3JPC = 16.0 Hz, C-1 in Ar),

8
A.V. Artem’ev et al.
1
158.12 (C-4 in Ar). 31P NMR (161.98 MHz, CDCl3): δ = 62.70 (s, JP
= 765 Hz). 77Se
=
Se
NMR (76.31 MHz, CDCl3): δ = –273 (d, 1JP
= 757 Hz).
=
Se
4.3.3.2. Se-[1-(Heptylsulfanyl)ethyl] bis(4-methoxyphenethyl)thioselenophosphinate (Se-3e)
3
1H NMR (400.13 MHz, CDCl3): δ = 0.84 (t, JHH = 7.0 Hz, 3 H, MeCH2), 1.23–1.34 (m, 8
3
H, CH2), 1. 58–1.65 (m, 2 H, CH2), 1.89 (d, JHH = 6.9 Hz, 3 H, MeCH), 2.34–2.46 (m, 4 H,
CH2P), 2.71–2.78 and 2.59–2.66 (2 m, each 1 H, SCH2), 2.84–2.93 (m, 4 H, CH2Ar), 3.74 (s,
3
6 H, MeO), 4.48–4.59 (m, 1 H, SCHSe), 6.79 (d, JHH = 8.3 Hz, 4 H, H-3,5 in Ar), 7.06 (d,
3JHH = 8.3 Hz, 4 H, H-2,6 in Ar). 13C NMR (100.62 MHz, CDCl3): δ = 13.81 (Me), 22.34
(CH2Me), 26.31 (d, 3JPC = 2.6 Hz, MeCH), 28.35 (CH2Ar), 28.60 (CH2Am), 28.74 (CH2Bu),
28.98 (CH2Pr), 31.46 (CH2Et), 32.96 (CH2S), 39.75 and 40.11 (2 d, 1JPC = 41.5 and 40.7 Hz,
CH2P), 48.77 (SCHSe), 55.04 (MeO), 113.91 (C-3,5 in Ar), 129.0 (C-2,6 in Ar), 131.99 (d,
3JPC = 16.8 Hz, C-1 in Ar), 158.12 (C-4 in Ar). 31P NMR (161.98 MHz, CDCl3): δ = 63.19 (s,
1JPSe = 353 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = 347 (d, 1JPSe = 351 Hz).
4.3.4. [1-(Pentylselanyl)ethyl] bis(4-chlorophenethyl)thioselenophosphinate
(S-3f/Se-3f = 59:41)
Colorless oil; yield: 0.261 g (87%). IR (neat, v, cm−1): 733 (P–C), 656 (P S), 601 (P–S), 512
=
=
(P Se), 447 (P–Se). Anal. Calcd for C23H31Cl2PSSe2: C, 46.09; H, 5.21; P, 5.17; S, 5.35. Found:
C, 46.17%; H, 5.35%; P, 5.10%; S, 5.38%.
4.3.4.1. S-[1-(Pentylselanyl)ethyl] bis(4-chlorophenethyl)thioselenophosphinate (S-3f) 1H
3
NMR (400.13 MHz, CDCl31): δ = 0.87 (t, JHH = 7.0 Hz, 3 H, MeCH2). 1.30–1.36 (m, 4 H,
3
2CH2), 1.72–1.80 (m, 2 H, CH2), 1.83 (d, JHH = 7.0 Hz, 3 H, MeCH), 2.32–2.50 (m, 4 H,
CH2P), 2.67–2.74 and 2.78–2.83 (2 m, each 1 H, SeCH2), 2.85–3.00 (m, 4 H, CH2Ph), 4.52–
3
4.60 (m, 1 H, SCHSe), 7.10 (d, 4 H, JHH = 7.0 Hz, H-2,6 in Ar), 7.24–7.26 (m, 4 H, H-3,5
in Ar). 13C NMR (100.62 MHz, CDCl3): δ = 14.02 (Me), 22.26 (CH2Me), 26.14 (MeCH),
1
2
27.12 (d, JCSe = 58.9 Hz, CH2Se), 29.27 (d, JPC = 2.2 Hz, CH2Ar), 30.08 (CH2Pr), 32.21
1
3
(CH2Et), 38.22 and 39.24 (2 d, JPC = 40.8 and 40.0 Hz, CH2P), 39.85 (d, JPC = 3.5 Hz,
SCHSe), 128.89 (C-2,6 in Ar), 129.70 (C-3,5 in Ar), 132.48 (C-4 in Ar), 138.48 and 138.61
(2 d, JPC = 16.7 and 16.4 Hz, C-1 in Ar). 31P NMR (161.98 MHz, CDCl3): δ = 63.27 (s,
3
1JP
SeCH2).
= 762 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = –248 (d, JP
= 756 Hz), 330 (s,
1
=
=
Se
Se
4.3.4.2. Se-[1-(Pentylselanyl)ethyl] bis(4-chlorophenethyl)thioselenophosphinate (Se-3f) 1H
3
NMR (400.13 MHz, CDCl3): δ = 0.87 (t, JHH = 7.0 Hz, 3 H, MeCH2). 1.30–1.36 (m, 4 H,
3
2CH2), 1.72–1.80 (m, 2 H, CH2), 2.01 (d, JHH = 7.1 Hz, 3 H, MeCH), 2.32–2.50 (m, 4 H,
CH2P), 2.67–2.74 and 2.78–2.83 (2 m, each 1 H, SeCH2), 2.85–3.00 (m, 4 H, CH2Ph), 4.52–
3
4.60 (m, 1 H, SeCHSe), 7.10 (d, 4 H, JHH = 7.0 Hz, H-2,6 in Ar), 7.24–7.26 (m, 4 H, H-
3,5 in Ar). 13C NMR (100.62 MHz, CDCl3): δ = 14.02 (Me), 22.26 (CH2Me), 26.93 (MeCH),
1
2
27.12 (d, JCSe = 58.9 Hz, CH2Se), 28.83 (d, JPC = 2.2 Hz, CH2Ar), 29.92 (CH2Pr), 32.21
3
1
(CH2Et), 35.84 (d, JPC = 3.5 Hz, SeCHSe), 39.41 and 39.92 (2 d, JPC = 42.6 and 42.3 Hz,
CH2P), 128.89 (C-2,6 in Ar), 129.70 (C-3,5 in Ar), 132.53 (C-4 in Ar), 138.48 and 138.61 (2 d,
3JPC = 17.0 and 16.5 Hz, C1 in Ar). 31P NMR (161.98 MHz, CDCl3): δ = 62.80 (s, 1JPSe = 362
Hz). 77Se NMR (76.31 MHz, CDCl3): δ = 353 (d, 1JPSe = 361 Hz), 330 (s, SeCH2).

Journal of Sulfur Chemistry
9
4.3.5. [1-(Hexylselanyl)ethyl] diphenethylthioselenophosphinate (S-3 g/Se-3 g = 58:42)
Colorless oil; yield: 0.237 g (87%). IR (neat, v, cm−1): 748 (P–C), 698 (P S), 555 (P–S), 523
=
=
(P Se), 416 (P–Se). Anal. Calcd for C24H35PSSe2: C, 52.94; H, 6.48; P, 5.69; S, 5.89. Found:
C, 52.75%; H, 6.60%; P, 5.49%; S, 6.03%.
4.3.5.1. S-[1-(Hexylselanyl)ethyl] diphenethylthioselenophosphinate (S-3 g) 1H NMR
3
(400.13 MHz, CDCl3): δ = 0.90 (t, JHH = 7.0 Hz, 3 H, MeCH2). 1.31–1.43 (m, 6 H, CH2),
3
1.77–1.80 (m, 2 H, CH2), 2.07 (d, JHH = 6.6 Hz, 3 H, MeCH), 2.44–2.58 (m, 4 H, CH2P),
2.76–2.79 and 2.87–3.01 (2 m, each 1 H, SeCH2), 3.01–3.10 (m, 4 H, CH2Ph), 4.60–4.67 (m, 1
H, SCHSe), 7.23–7.32 (m, 10 H, Ph). 13C NMR (100.62 MHz, CDCl3): δ = 13.98 (Me), 22.48
(CH2Me), 26.10 (MeCH), 27.22 (d, 1JCSe = 59.2 Hz, CH2Se), 29.63 (CH2Pr), 29.71 and 29.79
3
1
(2 d, JPC = 3.5, CH2Ph), 30.29 (CH2Bu), 31.27 (CH2Et), 39.29 and 39.98 (2 d, JPC = 39.6
2
and 42.3 Hz, CH2P), 39.65 (d, JPC = 3.5 Hz, SCHSe), 126.49 (Cp in Ph), 128.24 (Co in Ph),
128.64 (Cm in Ph), 139.98 and 140.09 (2 d, 3JPC = 16.8 and 16.2 Hz, Ci in Ph). 31P NMR (161.98
MHz, CDCl3): δ = 62.96 (s, 1JP
= 759 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = –245 (d,
=
Se
1JP
= 757 Hz), 329 (s, SeCH2).
=
Se
4.3.5.2. Se-[1-(Hexylselanyl)ethyl] diphenethylthioselenophosphinate (Se-3 g) 1H NMR
3
(400.13 MHz, CDCl3): δ = 0.90 (t, JHH = 7.0 Hz, 3 H, MeCH2). 1.31–1.43 (m, 6 H, CH2),
3
1.77–1.80 (m, 2 H, CH2), 1.88 (d, JHH = 6.6 Hz, 3 H, MeCH), 2.44–2.58 (m, 4 H, CH2P),
2.76–2.79 and 2.87–3.01 (2 m, each 1 H, SeCH2), 3.01–3.10 (m, 4 H, CH2Ph), 4.60–4.67 (m, 1
H, SeCHSe), 7.23–7.32 (m, 10 H, Ph). 13C NMR (100.62 MHz, CDCl3): δ = 13.98 (Me), 22.48
(CH2Me), 27.08 (MeCH), 27.22 (d, 1JCSe = 59.2 Hz, CH2Se), 29.63 (CH2Pr), 29.71 and 29.79
(2 d, 3JPC = 3.5, CH2Ph), 30.12 (CH2Bu), 31.27 (CH2Et), 35.63 (d, 2JPC = 3.5 Hz, SeCHSe),
1
38.14 and 39.28 (2 d, JPC = 40.6 and 42.8 Hz, CH2P), 126.49 (Cp in Ph), 128.24 (Co in Ph),
128.64 (Cm in Ph), 140.11and 140.25 (2 d, 3JPC = 16.8 and 16.2 Hz, Ci in Ph). 31P NMR (161.98
1
MHz, CDCl3): δ = 62.90 (s, JPSe = 360 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = 353 (d,
1JPSe = 359 Hz), 329 (s, SeCH2).
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by the President of the Russian Federation (program for the support of leading scientific schools,
grant NSh-156.2014.3).
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