Regioselective addition of dithiophosphinic acids to vinyl sulfides and selenides: An efficient route toward functional dithiophosphinates

Article abstract of DOI:10.1002/hc.21215

Earlier unknown S-[1-(organosulfanyl)ethyl]- and S-[1-(organoselenyl)ethyl] dithiophosphinates were synthesized in 85-97% yields by regioselective addition of dithiophosphinic acids to diverse vinyl sulfides and selenides under mild conditions (ambient te

Full text of DOI:10.1002/hc.21215

Heteroatom Chemistry
Volume 00, Number 00, 2014
R
egioselective Addition of Dithiophosphinic
Acids to Vinyl Sulfides and Selenides: An
Efficient Route Toward Functional
Dithiophosphinates
Ludmila A. Oparina, Alexander V. Artem’ev, Nikita A. Kolyvanov,
Oksana V. Vysotskaya, Nataliya A. Chernysheva,
Vladimir I. Smirnov, Tatyana N. Borodina, Nina K. Gusarova,
and Boris A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
664033, Irkutsk, Russian Federation
Received 20 May 2014; revised 0 xxxx 0000
“
click” characteristics. Among the latter are mild re-
ABSTRACT: Earlier unknown S-[1-(organosul-
fanyl)ethyl]- and S-[1-(organoselenyl)ethyl] dithio-
phosphinates were synthesized in 85–97% yields by
regioselective addition of dithiophosphinic acids to
diverse vinyl sulfides and selenides under mild con-
ditions (ambient temperature, Et2O, 3 h). ꢀC 2014 Wi-
ley Periodicals, Inc. Heteroatom Chem. 00:1–6, 2014;
View this article online at wileyonlinelibrary.com.
DOI 10.1002/hc.21215
action conditions (usually room temperature and at-
mospheric pressure), high regioselectivity, as well as
rapid and almost quantitative formation of target
products with a minimum of by-products (if any) [1].
Owing to these benefits, the thiol-ene reaction cur-
rently has a wide application in such diverse areas
as small molecule organic synthesis [1], biochem-
istry [2], and polymer and material science [3].
However, while this reaction has been broadly
investigated with diverse thiols (involving natural
ones) [1], the addition of compounds containing,
for example, P–S–H functionalities, in particular,
thiophosphinic and -phosphoric acids, across C=C
double bonds, has received significantly less at-
tention. In previous studies, the addition of O,O’-
dialkyldithiophosphoric acids to electron-deficient
alkenes proceeding in an anti-Markovnikov fash-
ion has been mainly investigated [4]. Unactivated
substrates (aliphatic alkenes, terpenes) react with
these acids to give the Markovnikov-type adducts
INTRODUCTION
Over the past decades, the addition of S–H species
to C=C double bonds attracts a great interest of
researchers as one of most efficient and atom-
economic route toward C–S bond formation [1]. This
reaction, referred now to as thiol-ene addition, has
numerous advantages over alternative methods for
the synthesis of organosulfur compounds due to its
[5], often along with products of carbocationic re-
arrangements [5, 6]. As for electron-rich alkenes,
to our knowledge, only Markovnikov addition of
Ph P(S)SH and (EtO) P(S)SH to aryl vinyl ethers [7]
and vinyl acetate [8] has been described without pro-
viding reliable proofs for a structure of the prepared
adducts.
Correspondence to: Boris A. Trofimov; e-mail: boris_
trofimov@irioch.irk.ru.
2
2
Contract grant sponsor: President of the Russian Federation
(
Program for the Support of Leading Scientific Schools). Contract
grant number: NSh-156.2014.3
2014 Wiley Periodicals, Inc.
ꢀC
1

2
Oparina et al.
was formed as a mixture of the two diastereomers
(
RR/RS or SS/SR) with the ratio of 1:1.
The obtained S-esters are white powders
4a,c,d,g) or oils (4b,e,f, 5), stable to possible sym-
(
metrization with formation of dithioacetals and acy-
lals, (RS)2CHMe and [R2P(S)S]2CHMe. The synthe-
SCHEME 1. Synthesis of the starting acids 2a–c.
1
13
31
sized compounds were characterized by H, C, P,
7
7
and Se NMR, IR, and X-ray diffraction (for 4a)
techniques.
To further extend the potential of addition of
phosphorus thioacids to alkenes as an efficient ap-
proach to functional S-esters, in this work we have
studied the reaction of dithiophosphinic acids with
vinyl sulfides and selenides. The latter are cho-
sen as ene-components due to (i) their availabil-
ity [9] and (ii) potential usefulness of the designed
products, i.e., earlier unknown dithiophosphinic S-
esters, which are expected to be prospective inifer-
ters [10], S/Se sources for fabrication of semicon-
ducting nanocrystals [11], as well as new generation
pesticides [12].
The single-crystal X-ray analysis of S-ester 4a re-
vealed that this compound crystallizes in a racemic
group P-1 with two molecules per unit cell (Fig. 1).
The phosphorus atom has a distorted tetrahedral co-
ordination, similar to other reported dithiophosphi-
˚
nate structures [17]. The P–S (2.0996 A) and P=S
˚
(
1.9494 A) bond lengths are consistent with the lit-
erature values [17]. The S(3)–P(1)–S(1)–C(15) chain
adopts a synclinal conformation with an angle of
o
3
3.68 .
CONCLUSION
To summarize, the efficient method for the synthe-
sis of hitherto unknown dithiophosphinates bearing
dithio- and thioselenoacetal moieties has been devel-
oped utilizing electrophilic addition of dithiophos-
phinic acids to vinyl sulfides and selenides as well
as divinyl sulfide. The reaction proceeds under mild
condition to provide Markovnikov adducts in high
yields. Having in mind that the numerous dithio-
phosph(in)ates are highly biological active [7, 12],
the obtained products represent prospective agro-
chemicals and drug precursors. The presence of the
several chalcogen atoms within compounds 4a–g
and 5 makes them promising ligands for the con-
struction of metal complexes. Also, they can be used
as iniferters for living polymerization and capping
agents for stabilization of nanoparticles.
RESULTS AND DISCUSSION
The starting dithiophosphinic acids were synthe-
sized by the one-pot procedure from secondary phos-
phines 1a–c, which now are readily accessible from
red phosphorus and styrenes [13]. The oxidation of
1a–c with elemental sulfur in the presence of alkali
(1:0.25:1.1 molar ratio, EtOH, room temperature, 20
min), followed by acidification of the formed sodium
dithiophosphinate with aqueous HCl produced the
pure acids 2a–c in high yields (Scheme 1).
The examination of the prepared acids 2a–c in
a reaction with diverse vinyl sulfides 3a–c and se-
lenides 3d,e (equimolar reactant ratio) has showed
that the addition to latter is carried out in diethyl
ether at ambient temperature for 3 h to afford
Markovnikov-type adducts 4a–g in 85–97% yield
EXPERIMENTAL
(Table 1). The reaction is strictly regioselective, be-
cause no by-products have been found in reaction
FTIR spectra were recorded on a Bruker Vertex 70
1
31
1
13
31
77
mixtures ( H and P NMR). This fact is explained by
relatively high S–H acidity of the acids 2a–c (e.g., pKa
of aqueous ethanolic solution of Et2PS2H is 2.8 [14])
and by the electron-rich nature of the C=C bond
within vinyl chalcogenides 3a–e [15] that favors their
easy hydrofunctionalization.
instrument. The H, C, P, and Se NMR spectra
were run on a Bruker AV-400 spectrometer (400.13,
100.61 161.98, and 76.31 MHz, respectively). 85%
H3PO4/H2O was employed as an external standard
3
1
1
13
for P NMR, HMDS was used for H and C NMR,
7
7
and Me2Se was the external standard for Se NMR.
Melting points (uncorrected) were measured on a
Kofler micro hot stage apparatus. The microanalyses
were performed on a Flash EA 1112 CHNS analyzer.
All steps of the experiment were carried out
in argon atmosphere. Vinyl sulfides [9a] and se-
lenides [9b,c] were prepared by published meth-
ods. Secondary phosphines 1a–c were synthesized
On example of available divinyl sulfide [16], it
was demonstrated that the divinyl chalcogenides
also participate in this reaction. Thus, when twofold
amount of acid 2c was used, the addition to divinyl
sulfide takes place on the both vinyl groups, leading
to expected diadduct 5 in 90% yield (Scheme 2). Ac-
1
13
31
cording to H, C, and P NMR data, this compound
Heteroatom Chemistry DOI 10.1002/hc

Regioselective Addition of Dithiophosphinic Acids to Vinyl Sulfides and Selenides
TABLE 1 Atom-Economic Synthesis of S-Esters 4a–ga
3
Entry
Acid
Vinyl Chalcogenide
Product
Yield (%)b
1
(3a)
4a
94
(
(
2a)
2a)
2
3
(3b)
(3c)
4b
4c
90
97
(
2b)
4
(3b)
4d
91
(
2c)
5
6
(3d)
(3e)
4e
4f
85
92
(
2a)
(
2b)
7
(3d)
4g
95
(
2c)
a
Reaction condition: acid 2a–c (1 mmol), vinyl chalcogenide 3a–e (1 mmol), diethyl ether, stirring under argon at room temperature for 3 h.
Isolated yield.
b
Heteroatom Chemistry DOI 10.1002/hc

4
Oparina et al.
3
(
o-C in Ph), 128.5 (m-C in Ph), 142.5 (d, JPC = 16.8
3
1
Hz, ipso-C in Ph). P NMR (161.98 MHz, acetone-
d6): δ = 69.10. Anal. Calcd for C16H19PS2: C, 62.71;
H, 6.25; S, 20.93. Found: C, 62.93; H, 6.37; S, 21.08.
SCHEME 2. Addition of acid 2c to divinyl sulfide.
Bis(4-methylphenethyl) Dithiophosphinic Acid
(
(
(
2b). White powder, yield 1130 mg (84%); mp 70°C
−1
hexane). IR (KBr), cm : 2537 (S–H), 732 (P–C), 610
1
P=S), 534, 480, 465 (P–S). H NMR (400.13 MHz,
CDCl3): δ = 2.35 (br s, 7H, Me, SH), 2.39–2.45 (m, 4H,
CH2P), 3.02–3.09 (m, 4H, CH2Ar), 7.12–7.14 (m, 8H,
1
3
Ar). C NMR (100.62 MHz, CDCl3): δ = 21.0 (Me),
1
2
8.7 (CH2Ar), 40.7 (d, JPC = 48.3 Hz, CH2P), 128.3
(
C-2,6 in Ar), 129.5 (C-3,5 in Ar), 136.3 (C-4 in Ar),
3
31
1
36.9 (d, JPC = 16.4 Hz, C-1 in Ar). P NMR (161.98
MHz, CDCl3): δ = 68.38. Anal. Calcd for C18H23PS2:
C, 64.64; H, 6.96; S, 19.17. Found: C, 64.80; H, 7.17;
S, 19.35.
Bis(4-chlorophenethyl)dithiophosphinic
2c). White powder, yield 1290 mg (86%); mp
Acid
FIGURE 1 X-ray structure of 4a (50% thermal ellipsoid
probability). Selected bond lengths (A) and angles (deg):
S(1)–P(1) 2.0996(6), S(1)–C(15) 1.8468(15), S(2)–C(15)
(
1
(
˚
−1
06°C (hexane). IR (KBr), cm : 2569 (S–H), 734
1
P–C), 612, 656 (P=S), 490, 481 (P–S). H NMR
1
.8095(15), S(2)–C(16) 1.8477(16), S(3)–P(1) 1.9494(6),
P(1)–C(6) 1.8147(15), P(1)–C(7) 1.8193(16), S(3)–P(1)–S(1)
14.96(3), S(2)–C(15)–S(1) 109.23(7).
(400.13 MHz, CDCl3): δ = 2.21 (br s, 1H, SH),
1
2.36–2.43 (m, 4H, CH P), 3.04–3.09 (m, 4H, CH Ar),
2
2
3
3
7
8
.16 (d, J = 8.4 Hz, 4H, H-2,6 in Ar), 7.29 (d, J =
13
.4 Hz, 4H, H-3,5 in Ar). C NMR (100.62 MHz,
from red phosphorus, styrene, 4-chlorostyrene, and
-methylstyrene, correspondingly, according to pro-
1
CDCl3): δ = 28.4 (CH2Ar), 40.4 (d, JPC = 49.1 Hz,
4
CH2P), 128.8 (C-2,6 in Ar), 129.6 (C-3,5 in Ar), 132.5
tocol [13a]. Divinyl sulfide was prepared as described
in [16]. Diethyl ether and THF were distilled over
metal sodium prior to use.
3
31
(
C-4 in Ar), 138.3 (d, JPC = 15.9 Hz, C-1 in Ar).
P
NMR (161.98 MHz, CDCl3): δ = 67.32. Anal. Calcd
for C16H17Cl2PS2: C, 51.20; H, 4.57; S, 17.09. Found:
C, 51.37; H, 4.73; S, 17.31.
Synthesis of Dithiophosphinic Acids (2a–c):
General Procedure
Synthesis of S-Esters (4a–g): General Procedure
To a mixture of secondary phosphine 1a–c (4 mmol)
and NaOH (176 mg, 4.4 mmol) in EtOH (20 mL),
powdered sulfur S8 (256 mg, 1 mmol) was added
and the suspension was stirred until the dissolution
of sulfur (ca. 20 min). The resulting solution was
diluted with water (30 mL), acidified with HCl (36%,
To a solution of vinyl chalcogenide 3a–e (1 mmol) in
diethyl ether (7 mL), acid 2a–c (1 mmol) was added
and the suspension was stirred at ambient temper-
ature for 3 h. The solvent was removed from the
resulting mixture, and the residue was purified by
flash chromatography (neutral alumina, CHCl3) to
give S-esters 4a–g.
1
mL), and extracted with chloroform (2 × 20 mL).
The extract was dried over Na2SO4, the solvent was
evaporated, and residue was dried in vacuo (1 Torr)
to give pure acid 2a–c.
S-1-(Tert-butylsulfanyl)ethyl
Diphenethyldithiophosphinate (4a)
Diphenethyldithiophosphinic Acid (2a). White
powder, yield 1070 mg (87%); mp 64°C (hexane).
Colorless solid, yield 397 mg (94%); mp 62°C (hex-
−1
ane). IR (KBr), cm : 752 (P–C), 633 (P=S), 558, 473
−1
1
IR (KBr), cm : 2513 (S–H), 745 (P–C), 625 (P=S),
(P–S). H NMR (400.13 MHz, CDCl3): δ = 1.47 (s,
1
3
5
2
(
(
(
84, 510 (P–S). H NMR (400.13 MHz, CDCl3): δ =
9H, t-Bu), 1.81 (d, JHH = 7.0 Hz, 3H, MeCH), 2.24
.37 (m, 4H, CH2P), 2.78 (br s, 1H, SH), 2.98–3.05
-2.34 (m, 4H, CH2P), 2.91–3.13 (m, 4H, CH2Ph), 4.75
m, 4H, CH2Ph), 7.14–7.22 (m, 10H, Ph). 13C NMR
100.62 MHz, acetone-d6): δ = 29.6 (CH2Ph), 42.9
(dq, JPH = 10.6 Hz, JHH = 7.0 Hz, 1H, SCHS), 7.20–
3
3
13
7.31 (m, 10H, Ph). C NMR (100.62 MHz, CDCl3): δ
= 28.4 (CH2Ph), 28.7 (d, JPC = 3.0 Hz, MeCH), 30.9
1
3
d, JPC = 49.6 Hz, CH2P), 125.9 (p-C in Ph), 128.4
Heteroatom Chemistry DOI 10.1002/hc

Regioselective Addition of Dithiophosphinic Acids to Vinyl Sulfides and Selenides
5
1
1
(
Me in t-Bu), 37.6 and 39.7 (2d, JPC = 48.7 and 47.0
743 (P–C), 663, 657 (P=S), 504, 487 (P–S). H NMR
2
3
Hz, respectively, CH2P), 45.4 (C in t-Bu), 46.4 (d, JPC
3.0 Hz, SCHS), 126.96, 126.02 (p-C in Ph), 127.71,
27.74 (o-C in Ph), 128.15, 128.18 (m-C in Ph), 139.7
(400.13 MHz, CDCl3): δ = 1.78 (t, JHH = 6.8 Hz,
=
3H, Me), 2.20–2.29 (m, 4H, CH2P), 2.64–3.05 (m, 4H,
3
3
1
CH2Ar), 4.88 (dq, JPH = 12.2 Hz, JHH = 6.8 Hz, 1H,
3
31
3
and 139.9 (2d, JPC = 16.5 Hz, ipso-C in Ph).
P
SCHS), 7.04 (d, JHH = 8.2 Hz, 2H, H-2,6 in Ar), 7.12
3
NMR (161.98 MHz, CDCl3): δ = 71.88. Anal. Calcd
(d, JHH = 8.2 Hz, 2H, H-3,5 in Ar), 7.25–7.36 (m, 7H,
3
for C22H31PS3: C, 62.52; H, 7.39; S, 22.76. Found: C,
H-2,3,5,6 in Ar, o-p-H in PhS), 7.58 (d, JHH = 7.2 Hz,
1
3
6
3.00; H, 7.57; S, 22.92.
2H, m-H in PhS). C NMR (100.62 MHz, CDCl3): δ
=
25.4 (MeCH), 28.2, 28.4 (CH2Ar), 38.0 and 39.2
2d, JPC = 49.3 and 47.9 Hz, respectively, CH2P),
1
(
S-1-(Phenylsulfanyl)ethyl Diphenethyldithiophos-
phinate (4b). Yellowish oil, yield 398 mg (90%). IR
51.9 (SCHS), 128.5 (p-C in PhS), 128.8, 128.9 (C-2,6
−
1
in Ar), 129.1 (o-C in PhS), 129.7 (C-3,5 in Ar), 132.3,
132.4 (C-4 in Ar), 133.2 (ipso-C in PhS), 133.7 (m-C
(
film), cm : 749 (P–C), 697 (P=S), 558, 475 (P–S).
1
3
H NMR (400.13 MHz, CDCl3): δ = 1.64 (d, JHH =
3
in PhS), 138.6 and 138.7 (2d, JPC = 16.4 and 16.8
7
2
=
.0 Hz, 3H, MeCH), 2.12–2.21 (m, 4H, CH2P), 2.58–
3
1
3
3
Hz, respectively, C-1 in Ar). P NMR (161.98 MHz,
.92 (m, 4H, CH2Ph), 4.78 (dq, JPH = 12.0 Hz, JHH
3
CDCl3): δ = 73.32. Anal. Calcd for C24H25Cl2PS3: C,
7.0 Hz, 1H, SCHS), 7.10 (d, JHH = 7.4 Hz, 2H,
56.35; H, 4.93; S, 18.81. Found: C, 56.92; H, 4.60; S,
o-H in PhS), 7.03–7.27 (m, 11H, Ph, p-H in PhS),
3
13
19.08.
7
(
(
.44 (d, JHH = 7.2 Hz, 2H, m-H in PhS). C NMR
100.62 MHz, CDCl3): δ = 25.1 (MeCH), 28.5, 28.7
1
CH2Ph), 38.0 and 39.2 (2d, JPC = 48.7 and 47.8
S-1-(Pentylselanyl)ethyl Diphenethyldithiophos-
phinate (4e). Yellowish oil, yield 411 mg (85%). IR
Hz, respectively, CH2P), 51.3 (SCHS), 126.1, 126.2
−1
(
1
p-C in Ph), 128.0 (o-C in Ph, p-C in PhS), 128.3,
28.4 (m-C in Ph), 128.7 (o-C in PhS), 133.1 (ipso-C
(
film), cm : 749 (P–C), 698 (P=S), 559, 495, 470
1
(
P–S). H NMR (400.13 MHz, CDCl3): δ = 0.91 (t,
3
3
in PhS), 133.2 (m-C in PhS), 139.9 and 140.0 (2d, JPC
JHH = 7.0 Hz, 3H, Me), 1.38 (m, 4H, CH2), 1.78
3
1
3
=
16.4 and 16.8, 5 Hz, respectively, ipso-C in Ph).
P
(
2
m, 2H, CH2), 1.90 (d, JHH = 7.0 Hz, 3H, MeCH),
NMR (161.98 MHz, CDCl3): δ = 74.01. Anal. Calcd
.33–2.46 (m, 4H, CH2P), 2.77 and 2.84 (m, each
for C24H27PS3: C, 65.12; H, 6.15; S, 21.73. Found: C,
1
H, CH2Se), 2.91–3.12 (m, 4H, CH2Ph), 4.68 (dq,
3
3
6
4.88; H, 5.95; S, 21.48.
JPH = 12.0 Hz, JHH = 7.0 Hz, 1H, SCHSe), 7.20–
1
3
7
.27 (m, 10H, Ph). C NMR (100.62 MHz, CDCl3):
δ = 14.0 (MeCH2), 22.3 (MeCH2), 26.1 (CH2Se), 27.1
MeCH), 29.1 (CH2Ph), 30.0 (CH2Pr), 32.2 (CH2Et),
S-1-(Isobutylsulfanyl)ethyl
bis(4-methyl
(
phenethyl) Dithiophosphinate (4c). White solid,
yield 436 mg (97%); mp 87°C (hexane). IR (KBr),
2
3
7.3 (d, JPC = 3.4 Hz, SCHSe), 38.6 and 39.4 (2d,
1
−
1
1
JPC = 48.0 and 47.4 Hz, respectively, CH2P), 126.5,
cm : 757 (P–C), 654 (P=S), 562, 485 (P–S). H
3
126.6 (p-C in Ph), 128.3 (m-C in Ph), 128.7 (o-C in
NMR (400.13 MHz, CDCl3): δ = 1.01, 1.02 (2d, JHH
3
3
Ph), 140.1 and 140.2 (2d, JPC = 16.4 Hz, ipso-C in
=
6.8 Hz, 6H, Me2CH), 1.78 (d, JHH = 6.9 Hz,
3
1
77
3
3
Ph). P NMR (161.98 MHz, CDCl3): δ = 74.37. Se
NMR (76.31 MHz, CDCl3): δ = 349.4. Anal. Calcd for
C23H33PS2Se: C, 57.13; H, 6.88; S, 13.26. Found: C,
3
H, MeCH), 1.89 (dq, JPH = 12.0 Hz, JHH = 6.9
Hz, 1H, Me2CH), 2.33 (s, 6H, MeAr), 2.27–2.42 (m,
2
4
1
H, CH2P), 2.53 and 2.74 (2dd, each 1H, JHH =
3
57.42; H, 6.60; S, 13.72.
2.6 Hz, JHH = 7.5 Hz, CH2S), 2.94–3.08 (m, 4H,
3
3
CH2Ar), 4.60 (dq, JPH = 11.0 Hz, JHH = 6.9 Hz,
1
H, SCHS), 7.06–7.13 (m, 8H, Ar). 13C NMR (100.62
S-1-(Hexylselanyl)ethyl Bis(4-methylphenethyl)
MHz, CDCl3): δ = 21.0 (Me), 21.9, 22.3 (MeAr), 26.1
Dithiophosphinate (4f). Yellowish oil, yield 483 mg
(
(
1
(
1
MeCH), 28.4 (Me2CH), 28.7 (CH2Ar), 39.0 and 39.6
−1
(
5
92%). IR (film), cm : 738, 714 (P–C), 654 (P=S),
1
2d, JPC = 48.0, CH2P), 41.0 (CH2S), 49.6 (SCHS),
1
28, 483 (P–S). H NMR (400.13 MHz, CDCl3): δ
28.2 (C-2,6 in Ar), 129.4 (C-3,5 in Ar), 136.1, 136.2
3
=
0.85 (t, JHH = 6.7 Hz, 3H, Me), 1.26–1.38 (m,
3
3
C-4 in Ar), 137.2 and 137.3 (2d, JPC = 16.8 and
6
H, CH2), 1.68–1.75 (m, 2H, CH2), 1.84 (d, JHH =
3
1
7.0 Hz, respectively, C-1 in Ar). P NMR (161.98
6.8 Hz, 3H, MeCH), 2.24–2.36 (m, 4H, CH2P), 2.29
MHz, CDCl3): δ = 73.34. Anal. Calcd for C24H35PS3:
C, 63.96; H, 7.83; S, 21.34. Found: C, 63.70; H, 8.10;
S, 21.17.
(s, 6H, MeAr), 2.67–3.00 (m, 6H, CH2Se, CH2Ar),
3
3
4
.64 (dq, JPH = 12.0 Hz, JHH = 6.7 Hz, 1H,
13
SCHSe), 7.02–7.08, (m, 8H, Ar). C NMR (100.62
MHz, CDCl3): δ = 14.1 (MeCH2), 21.1 (MeAr), 22.6
(MeCH2), 26.2 (MeCH), 27.1 (CH2Se), 28.8 (CH2Ar),
29.8 (CH2Pr), 30.4 (CH2Bu), 31.4 (CH2Et), 37.3
S-1-(Phenylsulfanyl)ethyl bis(4-chlorophenethyl)
phosphinodithioate (4d). White solid, yield 465 mg
−1
2
(
91%); mp 105°C (hexane). IR (KBr), cm : 755,
(d, JPC = 3.4 Hz, SCHSe), 37.82 and 39.70 (2d,
Heteroatom Chemistry DOI 10.1002/hc

6
Oparina et al.
1
JPC = 48.3 and 47.0 Hz, respectively, CH2P), 128.2
129.2 and 129.4 (C-3,5 in Ar), 131.9, 132.0, and 132.1
3
(C-2,6 in Ar), 129.52 (C-3,5 in Ar), 136.1,136.2 (C-4
(C-4 in Ar), 138.2 and 138.3 (2d, JPC = 16.4 and 15.9
3
31
in Ar), 137.2 and 137.4 (2d, JPC = 16.4 and 17.0
Hz, respectively, C-1 in Ar). P NMR (161.98 MHz,
3
1
Hz, respectively, C-1 in Ar). P NMR (161.98 MHz,
CDCl3): δ = 71.46 and 73.53 with the ratio of 1:1.
Anal. Calcd for C36H40Cl4P2S5: C, 51.67; H, 4.82; S,
19.16. Found: C, 51.98; H, 5.11; S, 19.42.
7
7
CDCl3): δ = 74.56. Se NMR (76.31 MHz, CDCl3): δ
=
349.1. Anal. Calcd for C26H39PS2Se: C, 59.41; H,
.48; S, 12.20. Found: C, 59.62; H, 7.60; S, 12.61.
7
Crystallography of 4a
The single crystals of 4a were obtained by slow
evaporation of its hexane solution at 6–8°C for
overnight. The suitable sample was analyzed on
S-1-(Pentylselanyl)ethyl Bis(4-chlorophenethyl)
phosphinodithioate (4g). White solid, yield 524 mg
−
1
(
(
95%); mp 57°C (hexane). IR (KBr), cm : 779, 740
1
a Bruker D8 Venture diffractometer with Mo
P–C), 658 (P=S), 514, 484 (P–S). H NMR (400.13
3
Kα (λ = 0.71073 A˚ ) using the φ and ω scans.
MHz, CDCl3): δ = 0.87 (t, JHH = 6.8 Hz, 3H, Me),
The structure was solved and refined by direct
methods, and non-hydrogen atoms were refined
anisotropically using SHELX [18]. The coordinates
of the hydrogen atoms were calculated from ge-
ometrical positions. CCDC 1000860 contains the
supplementary crystallographic data for this paper.
These data can be obtained free of charge via
www.ccdc.cam.ac.uk/data_request/cif.
1
1
4
.29–1.37 (m, 4H, CH2), 1.70–1.77 (m, 2H, CH2),
3
.85 (d, JHH = 6.9 Hz, 3H, MeCH), 2.23–2.37 (m,
H, CH2P), 2.68–3.05 (m, 6H, CH2Se, CH2Ar), 4.62
3
3
(
dq, JPH = 12.5 Hz, JHH = 6.8 Hz, 1H, SCHSe),
3
7
.09 (d, JHH = 7.8 Hz, 4H, H-2,6 in Ar), 7.26 (d,
3
13
JHH = 7.3 Hz, 4H, H-3,5 in Ar). C NMR (100.62
MHz, CDCl3): δ = 14.1 (MeCH2), 22.3 (MeCH2), 26.2
(
3
MeCH), 27.1 (CH2Se), 28.6 (CH2Ar), 30.1 (CH2Pr),
2
Crystal data 4a: C H PS (M = 422.62), tri-
2.3 (CH2Et), 37.4 (d, JPC = 3.0 Hz, SCHSe), 38.6
22 31
3
1
clinic, space group P-1, a = 5.8614(13) A˚ , b =
and 39.3 (2d, JPC = 48.7 and 47.9 Hz, respectively,
˚
˚
1
3.008(3) A, c = 15.547(3) A, α = 100.999(6), β =
CH2P), 128.9 (C-2,6 in Ar), 129.7 (C-3,5 in Ar),
3
3
94.431(6), γ = 94.877(6), V = 1154.1(4) A˚ , Z =
1
=
32.4, 132.5 (C-4 in Ar), 137.7 and 137.8 (2d, JPC
16.4 and 16.0 Hz, respectively, C-1 in Ar).
−1
3
1
2, T = 100.0 K, μ(Mo K ) = 0.395 mm , D
=
P
α
calc
3
7
7
1.216 g/cm , 5580 reflections measured (4.58 ࣘ 2θ ࣘ
NMR (161.98 MHz, CDCl3): δ = 73.88. Se NMR
6
0.32), 4763 unique (Rint = 0.0765, Rsigma = 0.0381),
which were used in all calculations. The final R1 was
.0340 [I > 2σ(I)], and wR2 was 0.0848 (all data).
(
76.31 MHz, CDCl3): δ = 351.3. Anal. Calcd for
C23H31Cl2PS2Se: C, 50.00; H, 5.66; S, 11.61. Found:
C, 50.46; H, 5.60; S, 12.02.
0
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