A facile atom-economic synthesis of imidazoles with chalcogenophosphoryl substituents via free-radical addition of secondary phosphine chalcogenides to 1-vinylimidazoles

Article abstract of DOI:10.1055/s-0030-1260025

Secondary phosphine sulfides and selenides react with 1-vinylimidazoles under radical initiation conditions to give the corresponding anti-Markovnikov adducts in up to 98% yields. Georg Thieme Verlag Stuttgart - New York.

Full text of DOI:10.1055/s-0030-1260025

PAPER
1777
A Facile Atom-Economic Synthesis of Imidazoles with Chalcogenophosphoryl
Substituents via Free-Radical Addition of Secondary Phosphine
Chalcogenides to 1-Vinylimidazoles
S
ynthesis of Imida
i
zole
s
w
n
ith Chalcoge
a
nophosphoryl Su
K
bstituents . Gusarova, Svetlana F. Malysheva, Nataliya A. Belogorlova, Lidiya N. Parshina, Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, 664033 Irkutsk,
Russian Federation
Fax +7(3952)419346; E-mail: boris_trofimov@irioch.irk.ru
Received 13 February 2011; revised 31 March 2011
phosphine sulfides and phosphine selenides were higher
Abstract: Secondary phosphine sulfides and selenides react with 1-
than those of the corresponding phosphines. Hence, the
vinylimidazoles under radical initiation conditions to give the cor-
reactions with phosphine chalcogenides 1–5 (Table 1)
were complete within 1.5–4 hours; in contrast, the corre-
sponding secondary phosphines required reaction times of
2–7 hours.5 To evaluate the comparative reactivity of
these PH-adducts with vinylimidazoles under radical ad-
dition conditions, we studied the competitive reaction of
bis(2-phenylethyl)phosphine (10) and bis(2-phenyleth-
yl)phosphine sulfide (1) with 1-vinylimidazole (6). Thus,
a solution of compounds 1, 6 and 10 (molar ratio = 1:1:1)
in 1,4-dioxane was subjected to UV irradiation in a quartz
tube under an argon atmosphere. The relative rates of
conversion of PH-adducts 1 and 10, and formation of the
corresponding imidazolylphosphine 11 and imidazolyl-
phosphine sulfide 9a (Scheme 1) were monitored by 31P
NMR spectroscopy.
responding anti-Markovnikov adducts in up to 98% yields.
Key words: 1-vinylimidazoles, phosphine sulfides, phosphine se-
lenides, radical addition
The imidazole ring is found frequently in natural products
and biologically active compounds1 such as biotin, hista-
mine, the essential amino acid histidine, and the pilo-
carpine alkaloids. Imidazole-tailored ionic liquids1f,2 and
organic catalysts3 are other applications of imidazole de-
rivatives. Significant interest has focused on the synthesis
of functionalized imidazoles containing organophospho-
rus substituents that are used as polydentate ligands for
the design of effective metal–complex catalysts.4 Recent-
ly, we reported the synthesis of 1-substituted imidazoles
possessing phosphinyl moieties via radical addition of
secondary phosphines to 1-vinylimidazoles.5
N
N
N
R
R
R
R
S
H
UV
+
+
P
H
+
P
N
R
P
N
1,4-dioxane
N
R
Herein, we report a strategy for the simple and atom-eco-
nomic synthesis of novel families of functionalized imida-
zoles. To achieve this goal we have examined, for the first
time, the reaction of 1-vinylimidazoles with secondary
phosphine chalcogenides. These substrates were prepared
from red phosphorus, styrenes and elemental chalcogens.6
R
R
P
S
10
R = PhCH2CH2
1
6
11
9a
Scheme 1 Competitive reaction of secondary phosphine 10 and
phosphine sulfide 1 with 1-vinylimidazole (6)
Our experiments revealed that secondary phosphine sul-
fides 1 and 2 and phosphine selenides 3–5 reacted readily
with 1-vinylimidazole (6), 2-methyl-1-vinylimidazole (7)
and 1-vinylbenzimidazole (8) under UV irradiation, or in
the presence of 2,2¢-azobis(isobutyronitrile) (AIBN) at
65–70 °C to form regioselectively the corresponding anti-
Markovnikov adducts 9a–k in high yields (Table 1).
The data obtained proved that phosphine sulfide 1 was
more active in the reaction with 1-vinylimidazole (6) than
bis(2-phenylethyl)phosphine (10). In the first 30 minutes
of the reaction the concentration of the formed tertiary
phosphine sulfide 9a was almost 1.80 times higher than
that of tertiary phosphine 11. After 60 minutes, this ratio
increased to 2.10, and after 90 minutes to 2.75; the con-
centration of the initial phosphine sulfide 1 being dimin-
ished faster than that of secondary phosphine 10. The
higher reactivity of secondary phosphine sulfides and se-
lenides compared to secondary phosphines in free-radical
additions to the electron-rich double bond of vinyl ethers,
under radical initiation, has been reported previously.9
It is pertinent to mention that secondary phosphine oxides
do not react with vinylimidazoles 6–8 under the above
conditions.5 This fact correlates well with the low reactiv-
ity of secondary phosphine oxides in the presence of rad-
ical initiators7 due to the high P–H bond dissociation
energy in the phosphoryl moiety.8
Analysis of the results obtained (Table 1), as well as pub-
lished data,5 showed that the reactivities of secondary
To summarize, the reported free-radical addition of sec-
ondary phosphine sulfides and phosphine selenides to 1-
vinylimidazoles represents a simple and atom-economic
synthesis of a novel family of functionalized imidazoles
possessing chalcogenophosphoryl moieties. These com-
SYNTHESIS 2011, No. 11, pp 1777–1782
x
x.
x
x
.
2
0
1
1
Advanced online publication: 05.05.2011
DOI: 10.1055/s-0030-1260025; Art ID: Z19311SS
© Georg Thieme Verlag Stuttgart · New York

1778
N. K. Gusarova et al.
PAPER
pounds are promising candidates for drug design and as ered as a basic contribution to both imidazole and organo-
polydentate ligands for the preparation of effective metal– phosphorus chemistry.
complex catalysts. The reaction developed may be consid-
Table 1 Addition of Secondary Phosphine Chalcogenides 1–5 to Imidazoles 6–8a
R3
R3
R2
R2
X
N
N
R1
R1
X
H
R1
R1
UV or AIBN
1,4-dioxane
P
+
P
N
R4
N
R4
1–5
9a–k
6–8
Entry
PH-adduct
Imidazole
Product
Conditions Yield (%)b
S
N
N
P
N
UV, 2 h
AIBN, 4 h
98
93
H
1
2
S
P
N
6
1
1
9a
9b
S
N
N
P
N
H
UV, 2 h
96
S
P
N
7
S
N
P
H
3
UV, 2 h
91
94
N
S
P
N
N
8
6
1
9c
N
N
S
S
N
4
5
UV, 1.5 h
P
P
N
H
2
3
9d
Se
H
N
P
N
UV, 1.5 h
AIBN, 3 h
98
80
N
Se
P
N
6
7
9e
Se
H
N
P
6
UV, 2 h
95
N
Se
P
N
N
3
9f
Synthesis 2011, No. 11, 1777–1782 © Thieme Stuttgart · New York

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Synthesis of Imidazoles with Chalcogenophosphoryl Substituents
1779
Table 1 Addition of Secondary Phosphine Chalcogenides 1–5 to Imidazoles 6–8a (continued)
R3
R3
R2
R2
X
N
N
R1
R1
X
H
R1
R1
UV or AIBN
1,4-dioxane
P
+
P
N
R4
N
R4
1–5
9a–k
6–8
Entry
PH-adduct
Imidazole
Product
Conditions Yield (%)b
t-Bu
t-Bu
N
N
N
7
8
9
UV, 2 h
UV, 1.5 h
UV, 3 h
96
98
95
Se
Se
P
P
N
H
6
t-Bu
t-Bu
4
9g
t-Bu
t-Bu
N
N
N
Se
Se
P
P
N
H
7
t-Bu
t-Bu
4
9h
t-Bu
t-Bu
N
N
Se
P
t-Bu
Se
H
P
N
8
N
t-Bu
4
9i
N
N
N
Se
Se
10
11
UV, 1.5 h
95
90
P
P
N
H
6
5
9j
N
Se
UV, 2 h
P
P
N
Se
N
H
N
8
5
9k
a The ratio of PH-adduct–imidazole was 1:1. All experiments were carried out under an Ar atmosphere.
b Yield of isolated product.
All reactions were carried out under an Ar atmosphere. 1,4-Dioxane
was distilled and dried according to a standard procedure. Diphe-
nylphosphine and 1-vinylimidazole (6) were obtained from Aldrich
Chemical Co. Diphenylphosphine chalcogenides 2 and 5 were pre-
pared by oxidation of diphenylphosphine with elemental S or Se
powder in EtOH. 1-Vinylimidazole (6) was distilled under reduced
pressure prior to use. 2-Methyl-1-vinylimidazole (7) and 1-vinyl-
benzylimidazole (8) were synthesized using literature methods.10
AIBN was recrystallized from EtOH prior to use. UV irradiation ex-
periments were carried out using a 200 W mercury arc lamp. Melt-
ing points were recorded on a Stuart melting point apparatus and are
uncorrected. IR spectra were obtained using Bruker Vertex 70 in-
strumentation. 1H, 13C, 31P and 77Se NMR spectra were recorded at
400.13, 100.62, 161.98 and 76.31 MHz, respectively, as CDCl3 so-
lutions, on a Bruker DPX-400 spectrometer. Chemical shifts are re-
ported in d (ppm) relative to the residual non-deuterated (CHCl3)
Synthesis 2011, No. 11, 1777–1782 © Thieme Stuttgart · New York

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N. K. Gusarova et al.
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solvent signal (1H, 13C) as the internal standard, or H3PO4 (31P) and
Me2Se (77Se) as external standards. Elemental analyses were ob-
tained using a ThermoFinnigan CHN Flash EA1112 analyzer.
[2-(1H-Benzo[d]imidazol-1-yl)ethyl]diphenethylphosphine Sul-
fide (9c)
Colorless crystalline solid; yield (method A): 381 mg (91%); mp
50–51 °C (hexane).
Tertiary Phosphine Sulfides 9a–d and Phosphine Selenides
9e–k; General Procedure
IR (KBr): 3085, 3062, 3005, 2931, 2859, 1614, 1496, 1454, 1403,
1366, 1332, 1284, 1242, 1217, 1161, 1009, 946, 872, 864, 750, 699,
666, 612, 551, 496, 427 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 1.97–2.03 (m, 4 H, PCH2),
2.23–2.28 (m, 2 H, PCH2CH2N), 2.75–2.84 (m, 4 H, CH2Ph), 4.51–
4.59 (m, 2 H, CH2N), 7.03 and 7.05 (m, 2 H, H-5,6, imidazole),
7.14–7.32 (m, 10 H, Ph), 7.43, 7.79 and 8.09 (m, 3 H, H-4,7,2, im-
idazole).
13C NMR (100.62 MHz, CDCl3): d = 28.59 (CH2Ph), 30.01 (d,
1JP–C = 49.6 Hz, PCH2CH2N), 33.62 (d, 1JP–C = 52.4 Hz, CH2P),
39.38 (CH2N), 109.75 (C-7, imidazole), 120.54, 122.89 and 123.62
(C-4, 6, 5, imidazole), 126.80 (p-C, Ph), 128.31 (o-C, Ph), 128.83
(m-C, Ph), 133.05 (C-8, imidazole), 140.02 (d, 3JP–C = 12.0 Hz, i-C,
Ph), 143.25 and 143.36 (C-2,9, imidazole).
A soln of phosphine chalcogenide 1–5 (1.0 mmol) and imidazole 6–
8 (1.0 mmol) in 1,4-dioxane (0.5 mL) was irradiated (200 W Hg arc
lamp) in a quartz ampoule (method A), or heated at 65–70 °C in the
presence of AIBN (1% wt of the total mass of reactants) in a sealed
ampoule (method B) (reaction times are given in Table 1). The re-
action progress was monitored using 31P NMR spectroscopy; the
disappearance of the signal due to the starting phosphine chalco-
genides (20–24 ppm for sulfides 1–2 and 2–8 ppm for selenides 3–
5), and the appearance of a new resonance at 46–48 ppm and 30–36
ppm for the tertiary phosphine sulfides 9a–d and phosphine se-
lenides 9e–k, being indicative of completion. The mixture was dis-
solved in Et2O (3 mL), filtered through a layer of Al2O3 (activity
level II, 0.5 cm), and the filter-bed washed with a mixture of hex-
ane–Et2O (3 mL, 1:1). The solvents were removed by distillation
under reduced pressure to give phosphine chalcogenides 9a–k.
31P NMR (161.98 MHz, CDCl3): d = 47.57.
Anal. Calcd for C25H27N2PS: C, 71.74; H, 6.50; N, 6.69; P, 7.40; S,
7.66. Found: C, 71.69; H, 6.49; N, 6.65; P, 7.36; S 7.54.
[2-(1H-Imidazol-1-yl)ethyl]diphenethylphosphine Sulfide (9a)
Light-yellow oil; yield (method A): 361 mg (98%); yield (method
B): 343 mg (93%).
[2-(1H-Imidazol-1-yl)ethyl]diphenylphosphine Sulfide (9d)
Light-yellow oil; yield (method A): 294 mg (94%).
IR (film): 3086, 3062, 2933, 1603, 1497, 1454, 1403, 1359, 1288,
1230, 1181, 1108, 1078, 1030, 965, 947, 907, 818, 753, 699, 663,
622, 597, 551, 497 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 1.91–2.17 (m, 6 H, CH2P),
2.83–2.88 (m, 4 H, CH2Ph), 4.23–4.30 (m, 2 H, CH2N), 6.89 and
7.03 (s, 2 H, H-4,5, imidazole), 7.13–7.27 (m, 10 H, Ph), 7.60 (s,
1H, H-2, imidazole).
13C NMR (100.62 MHz, CDCl3): d = 28.45 (CH2Ph), 31.98 (d,
1JP–C = 47.8 Hz, PCH2CH2N), 33.30 (d, 1JP–C = 49.3 Hz, CH2P),
41.10 (CH2N), 118.82 (C-4, imidazole), 126.77 (p-C, Ph), 128.24
(o-C, Ph), 128.77 (m-C, Ph), 129.27 (C-5, imidazole), 137.08 (C-2,
imidazole), 139.97 (d, 3JP–C = 12.7 Hz, i-C, Ph).
IR (film): 3139, 3054, 2923, 2852, 1672, 1586, 1509, 1481, 1437,
1400, 1181, 1105, 1035, 1021, 997, 845, 747, 709, 694, 628, 611,
560, 509, 492 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 2.88–2.95 (m, 2 H, CH2P),
4.36–4.42 (m, 2 H, CH2N), 6.84 and 6.87 (s, 2 H, H-4,5, imidazole),
7.42–7.78 and 7.75–7.80 (m, 10 H, Ph), 7.87 (s, 1 H, H-2, imida-
zole).
13C NMR (100.62 MHz, CDCl3): d = 33.79 (d, 1JP–C = 53.8 Hz,
CH2P), 42.49 (CH2N), 120.00 (C-4, imidazole), 128.77 (d,2JP–C
=
12.5 Hz, o-C, Ph), 130.00 (C-5, imidazole), 130.80 (d,3JP–C = 11.3
Hz, m-C, Ph), 131.13 (d, 1JP–C = 87.4 Hz, i-C, Ph), 131.94 (p-C, Ph),
136.81 (C-2, imidazole).
31P NMR (161.98 MHz, CDCl3): d = 46.21.
31P NMR (161.98 MHz, CDCl3): d = 39.17.
Anal. Calcd for C21H25N2PS: C, 68.45; H, 6.84; N, 7.60; P, 8.41; S,
8.70. Found: C, 68.40; H, 6.89; N, 7.45; P, 8.13; S, 8.32.
Anal. Calcd for C17H17N2PS: C, 65.37; H, 5.49; N, 8.97; P, 9.92; S,
10.27. Found: C, 65.31; H, 5.48; N, 8.90; P, 9.90; S, 10.20.
[2-(2-Methyl-1H-imidazol-1-yl)ethyl]diphenethylphosphine
Sulfide (9b)
Colorless crystalline solid; yield (method A): 367 mg (96%); mp
128–130 °C (hexane).
[2-(1H-Imidazol-1-yl)ethyl]diphenethylphosphine Selenide (9e)
Light-yellow oil; yield (method A): 407 mg (98%); yield (method
B): 332 mg (80%).
IR (film): 3107, 3062, 3003, 2932, 1602, 1497, 1454, 1402, 1359,
1323, 1230, 1150, 1108, 1077, 1030, 965, 907, 818, 753, 699, 662,
621, 573, 495, 470, 454 cm–1.
IR (KBr): 3064, 3026, 2997, 2931, 2868, 1602, 1523, 1497, 1453,
1424, 1357, 1286, 1271, 1230, 1142, 1110, 1072, 1020, 967, 944,
915, 803, 775, 729, 699, 676, 603, 552, 496 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 2.02–2.23 (m, 6 H, CH2P),
2.82–2.91 (m, 4 H, CH2Ph), 4.27–4.31 (m, 2 H, CH2N), 6.90 and
7.03 (s, 2 H, H-4,5, imidazole), 7.14–7.30 (m, 10 H, Ph), 7.56 (s, 1
H, H-2, imidazole).
1H NMR (400.13 MHz, CDCl3): d = 2.01–2.10 (m, 6 H, PCH2),
2.40 (s, 3 H, Me), 2.87–2.89 (m, 4 H, CH2Ph), 4.16–4.23 (m, 2 H,
CH2N), 6.81 and 6.89 (s, 2 H, H-4,5, imidazole), 7.14–7.23 (m, 10
H, Ph).
13C NMR (100.62 MHz, CDCl3): d = 29.22 (CH2Ph), 31.30 (d,
1JP–C = 40.5 Hz, PCH2CH2N), 32.85 (d, 1JP–C = 41.7 Hz, CH2P),
41.98 (CH2N), 118.75 (C-4, imidazole), 126.77 (p-C, Ph), 128.23
(o-C, Ph), 128.78 (m-C, Ph), 129.64 (C-5, imidazole), 137.13 (C-2,
imidazole), 139.69 (d, 3JP–C = 13.1 Hz, i-C, Ph).
13C NMR (100.62 MHz, CDCl3): d = 12.84 (Me), 28.31 (CH2Ph),
1
31.35 (d, JP–C = 47.8 Hz, PCH2CH2N), 33.10 (d, 1JP–C = 48.2 Hz,
CH2P), 39.85 (CH2N), 118.96 (C-4, imidazole), 126.57 (p-C, Ph),
128.0 (o-C, Ph), 128.45 (C-5, imidazole), 128.60 (m-C, Ph), 139.76
(d, 3JP–C = 13.6 Hz, i-C, Ph), 144.06 (C-2, imidazole).
31P NMR (161.98 MHz, CDCl3): d = 35.28 (s + d satellites, 1JP–Se
=
31P NMR (161.98 MHz, CDCl3): d = 46.10.
710 Hz).
Anal. Calcd for C22H27N2PS: C, 69.08; H, 7.11; N, 7.32; P, 8.10; S,
8.38. Found: C, 69.04; H, 7.09; N, 7.45; P, 8.30; S, 8.35.
77Se NMR (76.31 MHz, CDCl3): d = –392.10 (d, 1JP–Se = 710 Hz).
Anal. Calcd for C21H25N2PSe: C, 60.72; H, 6.07; N, 6.74; P, 7.46;
Se, 19.01. Found: C, 60.60; H, 6.09; N, 6.45; P, 7.30; Se, 18.92.
Synthesis 2011, No. 11, 1777–1782 © Thieme Stuttgart · New York

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Synthesis of Imidazoles with Chalcogenophosphoryl Substituents
1781
[2-(1H-Benzo[d]imidazol-1-yl)ethyl]diphenethylphosphine
Selenide (9f)
31P NMR (161.98 MHz, CDCl3): d = 34.90 (s + d satellites, 1JP–Se
=
705 Hz).
Colorless crystalline solid; yield (method A): 442 mg (95%); mp
105–106 °C (hexane).
77Se NMR (76.31 MHz, CDCl3): d = –388.9 (d, 1JP–Se = 706 Hz).
Anal. Calcd for C30H43N2PSe: C, 66.53; H, 8.00; N, 5.17; P, 5.72;
Se, 14.58. Found: C, 66.47; H, 8.04; N, 5.15; P, 5.43; Se, 14.50.
IR (KBr): 3084, 3057, 2919, 2862, 1601, 1496, 1453, 1444, 1383,
1362, 1331, 1282, 1251, 1220, 1197, 1162, 1010, 956, 866, 842,
770, 761, 741, 699, 653, 626, 570, 452 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 2.04–2.10 (m, 4 H, PCH2),
2.27–2.34 (m, 2 H, PCH2CH2N), 2.72–2.82 (m, 4 H, CH2Ph), 4.49–
4.56 (m, 2 H, CH2N), 7.00 and 7.02 (s, 2 H, H-5,6, imidazole), 7.16–
7.27 (m, 10 H, Ph), 7.40, 7.77 and 8.00 (m, 3 H, H-4,7,2, imidazole).
[2-(1H-Benzo[d]imidazol-1-yl)ethyl]bis[4-(tert-butyl)pheneth-
yl]phosphine Selenide (9i)
Colorless crystalline solid; yield (method A): 549 mg (95%); mp
170–173 °C (hexane).
IR (KBr): 3093, 3054, 2962, 2865, 1615, 1493, 1461, 1363, 1283,
1268, 1247, 1199, 1163, 1142, 1108, 1009, 928, 865, 827, 811, 768,
745, 563, 430, 416 cm–1.
1
13C NMR (100.62 MHz, CDCl3): d = 29.14 (d, JP–C = 40.7 Hz,
1
PCH2CH2N), 29.16 (CH2Ph), 33.87 (d, JP–C = 41.4 Hz, CH2P),
40.09 (CH2N), 109.49 (C-7, imidazole), 120.54, 122.55 and 123.29
(C-4, 6, 5, imidazole), 126.66 (p-C, Ph), 128.17 (o-C, Ph), 128.71
(m-C, Ph), 132.87 (C-8, imidazole), 139.55 (d, 3JP–C = 13.2 Hz, i-C,
Ph), 143.05 and 143.62 (C-2, 9, imidazole).
1H NMR (400.13 MHz, CDCl3): d = 1.25 (s, 18 H, Me), 2.04–2.12
(m, 4 H, CH2P), 2.28–2.39 (m, 2 H, PCH2CH2N), 2.68–2.87 (m, 4
H, CH2Ph), 4.51–4.61 (m, 2 H, CH2N), 6.10–7.43 (m, 10 H, H-5,6,
imidazole, Ph), 7.44, 7.80 and 7.96 (m, 3 H, H-4,7,2, imidazole).
31P NMR (161.98 MHz, CDCl3): d = 35.59 (s + d satellites, 1JP–Se
715 Hz).
=
13C NMR (100.62 MHz, CDCl3): d = 28.36 (CH2Ph), 28.90 (d,
1JP–C = 41.9 Hz, PCH2CH2N), 30.90 (Me), 32.53 (d, 1JP–C = 41.9 Hz,
CH2P), 34.04 (CMe), 39.84 (CH2N), 109.08, 120.38 and 122.20 (C-
7, 6, 5, imidazole), 125.25 (o-C, Ph), 127.52 (m-C, Ph), 132.70 (C-
77Se NMR (76.31 MHz, CDCl3): d = –388.10 (d, 1JP–Se = 715 Hz).
Anal. Calcd for C25H27N2PSe: C, 64.51; H, 5.85; N, 6.02; P, 6.65;
Se, 16.96. Found: C, 64.50; H, 5.82; N, 6.00; P, 6.63; Se, 16.92.
3
8, imidazole), 136.11 (d, JP–C = 13.6 Hz, i-C, Ph), 142.62 and
143.58 (C-2, 9, imidazole), 149.35 (p-C, Ph).
[2-(1H-Imidazol-1-yl)ethyl]bis[4-(tert-butyl)phenethyl]phos-
phine Selenide (9g)
31P NMR (161.98 MHz, CDCl3): d = 35.42 (s + d satellites, 1JP–Se
=
709 Hz).
Light-yellow oil; yield (method A): 506 mg (96%).
77Se NMR (76.31 MHz, CDCl3): d = –391.8 (d, 1JP–Se = 709 Hz).
IR (film): 3095, 3055, 2963, 2867, 1709, 1509, 1463, 1444, 1404,
1394, 1364, 1269, 1219, 1140, 1108, 1079, 1019, 963, 817, 756,
663, 622, 564, 484 cm–1.
Anal. Calcd for C33H43N2PSe: C, 68.62; H, 7.50; N, 4.85; P, 5.36;
Se, 13.67. Found: C, 68.59; H, 7.49; N, 4.79; P, 5.31; Se, 13.58.
1H NMR (400.13 MHz, CDCl3): d = 1.26 (s, 18 H, Me), 2.07–2.25
(m, 6 H, CH2P), 2.80–2.86 (m, 4 H, CH2Ph), 4.25–4.32 (m, 2 H,
CH2N), 6.88 and 7.02 (s, 2 H, H-4,5, imidazole), 7.09 and 7.27 (m,
8 H, Ph), 7.57 (s, 1 H, H-2, imidazole).
[2-(1H-Imidazol-1-yl)ethyl]diphenylphosphine Selenide (9j)
Light-yellow oil; yield (method A): 340 mg (95%).
IR (film): 3110, 3053, 2923, 2851, 1607, 1587, 1574, 1507, 1481,
1436, 1395, 1359, 1309, 1290, 1231, 1101, 1026, 997, 907, 845,
747, 692, 662, 623, 559, 541, 514, 495 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 2.97–3.04 (m, 2 H, CH2P),
4.35–4.41 (m, 2 H, CH2N), 6.85 and 6.87 (s, 2 H, H-4,5, imidazole),
7.40–7.75 (m, 10 H, Ph), 7.94 (m, 1 H, H-2, imidazole).
13C NMR (100.62 MHz, CDCl3): d = 28.66 (CH2Ph), 31.14 (d,
1
1JP–C = 40.0 Hz, PCH2CH2N), 31.24 (Me), 32.63 (d, JP–C = 40.7
Hz, CH2P), 34.34 (CMe), 41.95 (CH2N), 118.76 (C-4, imidazole),
125.61 (o-C, Ph), 127.87 (m-C, Ph), 129.42 (C-5, imidazole),
3
136.54 (d, JP–C = 15.9 Hz, i-C, Ph), 137.03 (C-2, imidazole),
13C NMR (100.62 MHz, CDCl3): d = 33.87 (d, 1JP–C = 47.5 Hz,
149.61 (p-C, Ph).
3
CH2P), 42.45 (CH2N), 119.04 (C-4, imidazole), 128.90 (d, JP–C
=
31P NMR (161.98 MHz, CDCl3): d = 35.58 (s + d satellites, 1JP–Se
708 Hz).
=
12.5 Hz, o-C, Ph), 130.27 (d, 1JP–C = 79.6 Hz, i-C, Ph), 130.54 (C-
2
5, imidazole), 131.30 (d, JP–C = 10.7 Hz, m-C, Ph), 136.02 (d,
77Se NMR (76.31 MHz, CDCl3): d = –392.1 (d, 1JP–Se = 708 Hz).
4JP–C = 2.1 Hz, p-C, Ph), 136.64 (C-2, imidazole).
Anal. Calcd for C29H41N2PSe: C, 66.02; H, 7.83; N, 5.31; P, 5.87;
Se, 14.97. Found: C, 66.00; H, 7.80; N, 5.32; P, 5.56; Se 14.72.
31P NMR (161.98 MHz, CDCl3): d = 30.50 (s + d satellites, 1JP–Se
=
735 Hz).
77Se NMR (76.31 MHz, CDCl3): d = –357.1 (d, 1JP–Se = 735 Hz).
Bis[4-(tert-butyl)phenethyl][2-(2-methyl-1H-imidazol-1-yl)eth-
yl]phosphine Selenide (9h)
Colorless crystalline solid; yield (method A): 531 mg (98%); mp
95–96 °C (hexane).
Anal. Calcd for C17H17N2PSe: C, 56.83; H, 4.77; N, 7.80; P, 8.62;
Se, 21.98. Found: C, 56.79; H, 4.72; N, 7.79; P, 8.59; Se, 21.93.
[2-(1H-Benzo[d]imidazol-1-yl)ethyl]diphenylphosphine
Selenide (9k)
Light-yellow oil; yield (method A): 368 mg (90%).
IR (KBr): 3092, 3054, 2963, 2904, 2865, 1577, 1501, 1454, 1426,
1363, 1269, 1214, 1145, 1108, 1073, 1021, 1000, 977, 871, 854,
840, 773, 734, 677, 571, 560, 523, 482, 462 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 1.27 (s, 18 H, Me), 2.13–2.22
(m, 6 H, CH2P), 2.41 (s, 3 H, Me), 2.81–2.88 (m, 4 H, CH2Ar),
4.15–4.22 (m, 2 H, CH2N), 6.79 and 6.89 (s, 2 H, H-4,5, imidazole),
7.08 and 7.30 (m, 8 H, Ph).
IR (film): 3054, 2988, 2916, 1647, 1614, 1587, 1495, 1459, 1436,
1383, 1369, 1333, 1311, 1284, 1241, 1200, 1159, 1100, 997, 910,
843, 800, 741, 692, 534, 493, 427 cm–1.
1H NMR (400.13 MHz, CDCl3): d = 3.04–3.11 (m, 2 H, CH2P),
4.58–4.65 (m, 2 H, CH2N), 6.85 and 6.87 (s, 2 H, H-5,6, imidazole),
7.31–7.36 and 7.64–7.70 (m, 11 H, H-4, imidazole, Ph), 7.72 and
7.92 (s, 2 H, H-7,2, imidazole).
13C NMR (100.62 MHz, CDCl3): d = 32.23 (d, 1JP–C = 48.7 Hz,
CH2P), 40.14 (CH2N), 109.62 (C-7, imidazole), 120.13 (C-4, imida-
zole), 122.56 (C-6, imidazole), 123.24 (C-5, imidazole), 128.75 (d,
13C NMR (100.62 MHz, CDCl3): d = 13.06 (Me), 28.65 (CH2Ph),
30.46 (d, 1JP–C = 42.5 Hz, PCH2CH2N), 31.19 (Me), 32.68 (d,
1JP–C = 44.5 Hz, CH2P), 34.29 (CMe), 40.92 (CH2N), 118.88 (C-4,
imidazole), 125.53 (o-C, Ph), 127.27 (C-5, imidazole), 127.75 (m-
3
C, Ph), 136.44 (d, JP–C = 13.6 Hz, i-C, Ph), 144.17 (C-2, imida-
zole), 149.70 (p-C, Ph).
Synthesis 2011, No. 11, 1777–1782 © Thieme Stuttgart · New York

1782
N. K. Gusarova et al.
PAPER
Y.; Zakharov, L.; Golen, J. A.; Rheingold, A. L. J. Am.
2JP–C = 12.4 Hz, o-C, Ph), 130.27 (d, JP–C = 79.8 Hz, i-C, Ph),
131.21 (d, 3JP–C = 10.9 Hz, m-C, Ph), 131.94 (d, 4JP–C = 2.5 Hz, p-C,
Ph), 132.82, 142.73 and 142.92 (C-8, 2, 9, imidazole).
31P NMR (161.98 MHz, CDCl3): d = 30.69, (s + d satellites, 1JP–Se
738 Hz).
1
Chem. Soc. 2006, 128, 438. (e) Debono, N.; Canac, Y.;
Duhayon, C.; Chauvin, R. Eur. J. Inorg. Chem. 2008, 2991.
(f) Canac, Y.; Debono, N.; Vendier, L.; Chauvin, R. Inorg.
Chem. 2009, 48, 5562. (g) Schulz, T.; Torborg, C.;
Schäffner, B.; Huang, J.; Zapf, A.; Kadyrov, R.; Börner, A.;
Beller, M. Angew. Chem. Int. Ed. 2009, 48, 918; Angew.
Chem. 2009, 121, 936. (h) Field, L. D.; Messerle, B. A.;
Vuong, K. Q.; Turner, P. Dalton Trans. 2009, 3599.
(5) Trofimov, B. A.; Malysheva, S. F.; Parshina, L. N.;
Gusarova, N. K.; Belogorlova, N. A. Synlett 2011, 94.
(6) (a) Gusarova, N. K.; Bogdanova, M. V.; Ivanova, N. I.;
Chernysheva, N. A.; Sukhov, B. G.; Sinegovskaya, L. M.;
Kazheva, O. N.; Alexandrov, G. G.; D’yachenko, O. A.;
Trofimov, B. A. Synthesis 2005, 3103. (b) Sukhov, B. G.;
Gusarova, N. K.; Ivanova, N. I.; Bogdanova, M. V.;
Kazheva, O. N.; Alexandrov, G. G.; D’yachenko, O. A.;
Sinegovskaya, L. M.; Malysheva, S. F.; Trofimov, B. A.
J. Struct. Chem. 2005, 46, 1066. (c) Gusarova, N. K.;
Malysheva, S. F.; Kuimov, V. A.; Belogorlova, N. A.;
Mikhailenko, V. L.; Trofimov, B. A. Mendeleev Commun.
2008, 18, 260. (d) Trofimov, B. A.; Gusarova, N. K.
Mendeleev Commun. 2009, 19, 295. (e) Malysheva, S. F.;
Artem’ev, A. V.; Gusarova, N. K.; Timokhin, B. V.;
Tatarinova, A. A.; Trofimov, B. A. Russ. J. Gen. Chem.
2009, 79, 1617. (f) Gusarova, N. K.; Malysheva, S. F.;
Belogorlova, N. A.; Kazheva, O. N.; Chekhlov, A. N.;
Alexandrov, G. G.; D’yachenko, O. A.; Sinegovskaya, L.
M.; Trofimov, B. A. J. Struct. Chem. 2010, 51, 120.
(7) (a) Leca, D.; Fensterbank, L.; Lacôte, E.; Malakria, M.
Chem. Soc. Rev. 2005, 34, 858. (b) Coudray, L.;
=
77Se NMR (76.31 MHz, CDCl3): d = –357.1 (d, 1JP–Se = 738 Hz).
Anal. Calcd for C21H19N2PSe: C, 61.62; H, 4.68; N, 6.84; P, 7.57;
Se, 19.29. Found: C, 61.56; H, 4.66; N, 6.81; P, 7.53; Se, 19.21.
Acknowledgment
This work was carried out with financial support of leading scienti-
fic schools by the President of the Russian Foundation (grant NSH-
3230.2010.3).
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Synthesis 2011, No. 11, 1777–1782 © Thieme Stuttgart · New York