Synthesis, characterization, and structures of α-substituted selenenyl-acetophenones

Article abstract of DOI:10.1080/10426507.2013.844144

A series of α-substituted selenenyl acetophenone derivatives of the types, [PhC(OCH₂CH₂O)CH₂Se]₂, [PhC(OCH₂CH₂O)CH₂SeR], (PhCOCH₂Se) ₂, and [PhCOCH₂

Full text of DOI:10.1080/10426507.2013.844144

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Phosphorus, Sulfur, and Silicon and the Related
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SYNTHESIS, CHARACTERIZATION AND STRUCTURES OF
α-SUBSTITUTED SELENENYL-ACETOPHENONES
Ananda S. Hodage a , Prasad P. Phadnis a , Amey Wadawale a , K. I. Priyadarsini b & Vimal K.
Jain a
a Chemistry Division, Bhabha Atomic Research Centre , Trombay , Mumbai , 400 085 , India
Phone: +91-22-2559-5095 Fax: +91-22-2559-5095
b Radiation and Photochemistry Division, Bhabha Atomic Research Centre , Trombay ,
Mumbai , 400 085 , India
Accepted author version posted online: 30 Sep 2013.
To cite this article: Phosphorus, Sulfur, and Silicon and the Related Elements (2013): SYNTHESIS, CHARACTERIZATION AND
STRUCTURES OF α-SUBSTITUTED SELENENYL-ACETOPHENONES, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2013.844144
To link to this article: http://dx.doi.org/10.1080/10426507.2013.844144
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SYNTHESIS, CHARACTERIZATION AND STRUCTURES OF
α-SUBSTITUTED SELENENYL-ACETOPHENONES
Ananda S. Hodage,a Prasad P. Phadnis,a Amey Wadawale,a K. I. Priyadarsini,*b and Vimal
K. Jain*a
aChemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India, Email:
jainvk@barc.gov.in, Fax: +91-22-2550-5151; Tel: +91-22-2559-5095
bRadiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai
400 085, India, Email: kindira@barc.ernet.in
Abstract
A series of α-substituted selenenyl acetophenone derivatives of the types, [PhC(OCH2CH2O)CH2Se]2,
[PhC(OCH2CH2O)CH2SeR], (PhCOCH2Se)2 and [PhCOCH2SeR] have been prepared. These compounds have been
characterized by elemental analyses, IR and NMR (1H, 13C, 77Se) spectroscopy. The compounds,
[PhC(OCH2CH2)CH2Se]2 and (PhCOCH2Se)2 have been structurally characterized by single crystal X-ray
diffraction analyses. The former shows intra-molecular Se---O interaction while the latter exhibits inter-molecular
non-bonding Se---O interaction.
Keywords Selenenyl acetophenone, selenium, NMR, X-ray structure, Se---O non-bonding
interaction
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INTRODUCTION
The chemistry of organoselenium compounds has witnessed a rapid growth in the last
two decades or so owing to their applications in the diverse area like organic synthesis, materials
science and biology.1-3 Metal selenolates have emerged as versatile precursors for the synthesis
of metal selenide nanocrystals and for deposition of thin films.4
Biological relevance of selenium has now been well recognized as an essential micro-
nutrient.5,6 In general selenium is primarily present in the form of selenocysteine in
selenoenzymes in biological systems.7 The physiological functions of several selenoenzymes
have now been identified. Among these selenoenzymes, glutathione peroxidase (GPx), an
antioxidant enzyme, has received an extensive attention. To mimic GPx like activity, different
families of organoselenium compounds have been designed and synthesized,8,9 e.g., ebselen act
as glutathione peroxidase (GPx) mimic, antioxidant, radioprotector and an anti-inflammatory
drug.10 The potent applications of ebselen prompted researchers to design and synthesize
organoselenium compounds incorporating intra-molecular non-bonding Se---N/O interactions (I-
III) (Scheme 1) which have shown promising GPx mimicking activity.11-19 In this context, α-
phenylselenenyl acetophenone (IV) exhibit GPx like activity both in-vitro and in-vivo,20-22
whereas diphenylselenide shows hardly any activity. We have recently reported GPx like activity
in alkyl mono- and di-selenides, {X(CH2)n}2Se and {X(CH2)nSe}2 (X = HO, NH2, HOOC; n = 2
or 3).23-26 Thus it was envisioned to design organoselenium compounds containing both
acetophenone and X(CH2)n fragments with the hope to develop potent GPx mimics. Accordingly
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we have synthesized a series of α-substituted selenenyl acetophenone derivatives and structurally
characterized two such derivatives. Results of this work are reported herein.
RESULTS AND DISCUSSION
Synthesis and spectroscopy
The reaction of 2-(bromomethyl)-2-phenyl-1,3-dioxolane ethylene with Na2Se2 (prepared
from elemental Se with hydrazine hydrate and NaOH in DMF as a solvent) gave a greenish
solution which, after work-up, afforded pale yellow crystals of diselenide
[PhC(OCH2CH2O)CH2Se]2 (1) in 74 % yield. Treatment of PhC(OCH2CH2O)CH2SeNa,
prepared by reductive cleavage of Se-Se bond in 1 with NaBH4 in methanol, with bromo
compounds gave unsymmetrical seleno ethers (2-9). The reactions with HO(CH2)nBr, however
afforded a mixture of both protected (6, 7) as well as deprotected (8, 9) compounds which could
be easily separated by column chromatography. Acid hydrolysis of 6 and 7 with dil. HCl readily
gave 8 and 9, respectively. Deprotection of carbonyl group in 1 with ceric ammonium nitrate
(CAN) yielded the corresponding keto compound (PhCOCH2Se)2 (10). Synthetic routes for these
compounds are depicted in Schemes 2 and 3. These compounds were purified by column
chromatography and were characterized by microanalyses, IR and NMR spectroscopy and mass
spectrometry.
The IR spectra of carbonyl compounds 8-11 displayed a strong absorption in the region
1
1654-1685 cm-1 attributable to υC=O stretchings. The H and 13C{1H} NMR spectra exhibited
expected resonances and peak multiplicities. The glycolic protons (OCH2CH2O) appeared as
multiplets in the regions 3.72-3.89 and 4.02-4.19 ppm. The SeCH2 protons appeared as a singlet
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in the region 2.99-4.93 ppm. The resonance in the cyano derivative (11) is highly deshielded (δ
4.93 ppm). Similarly in the 13C{1H} NMR spectrum a singlet is observed in the region 26.4-42.7
1
1
ppm with JSe-C couplings (65-83 Hz) for CH2Se. The JSe-C for the cyano derivative (11) is
significantly reduced (43 Hz), owing to the strong electron withdrawing nature of CN group. The
carbonyl resonance in 8-11 appeared in the region 193.2-195.5 ppm, with the cyano compound
being most shielded.
77
The Se{1H} NMR spectra displayed a single resonance in the region 80-372 ppm and
the shifts showed pronounced influence of the substituents. The resonances for diselenides are
most deshielded.27 Due to electron withdrawing C=O group in 10 the 77Se{1H} NMR resonance
appeared at lower field (δ 372 ppm) than that for 1 (δ 310 ppm). Similarly the 77Se{1H}
resonance for compounds containing carbonyl group (8 and 9) are deshielded as compared to the
corresponding glycolic derivatives (6 and 7). The resonances for monoselenides containing
aliphatic side chain with two carbon atoms are shielded (2 (91 ppm) and 6 (80 ppm)) than the
signals for the corresponding derivative containing three carbon atoms (3 (128 ppm) and 7 (123
ppm)).
Molecular structures
The molecular structures of [PhC(OCH2CH2O)CH2Se]2 (1) and [PhCOCH2Se]2 (10) have
been established unambiguously by single crystal X-ray diffraction analyses. ORTEP drawings
with numbering scheme are shown in Figures 1 and 2 while selected interatomic parameters are
given in Table 2. The Se-Se distances of ~ 2.31 Å are well in agreement with the values reported
in diorganodiselenides (2.29-2.39 Å).28-30 The Se-C distances (~ 1.96 Å) are as expected.31-34 The
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C-Se-Se-C torsion angles in 1 and 10 are 78.1 and 90.3, respectively. The C-Se-Se-C torsion
angles in diselenides, in general, vary between 70 and 100º.35 The five-membered “COOC2”
glycolic ring is puckered. There are weak secondary Se---O interactions in both the molecules. In
the case of 1 both the glycolic oxygen atoms (O1 and O2) are equidistant from Se1 (3.177 Å). In
the case of 10 the carbonyl oxygen atom of one of the carbonyl groups (O1) makes a short
contact with the Se2 of the neighboring molecule (3.221 Å) so as to form a dimer. The Se---O
separations in both the molecules are shorter than the sum of their van der Waals radii (3.42 Å)
[Insert Figure 1]
[Insert Figure 2]
CONCLUSIONS
The α-substituted selenenyl acetophenone derivatives with OH / NH2 functionalized
aliphatic chains on Se atom have been synthesized. There are weak intra- and inter-molecular Se-
--O interactions in 1 and 10, respectively.
EXPERIMENTAL
Materials and Methods
Elemental selenium (99.99 %), sodium borohydride, 2-bromoethylamine hydrobromide,
3-chloropropylamine hydrochloride, 2-bromoethanol, 3-bromopropanol, potassium selenocynide
(KSeCN), ceric ammonium nitrate (CAN), picolyl chloride hydrochloride were purchased from
commercial sources (Aldrich / Fluka). The starting compound for all the selenides, 2-
(bromomethyl)-2-phenyl-1,3-dioxolane i.e., PhC(OCH2CH2O)CH2Br36 was prepared by
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literature procedure (supplementary materials). All reactions were carried out under a nitrogen
atmosphere. Solvents were purified and distilled prior to use. The compounds were purified by
column chromatography on silica gel 60/ 120 mesh size. Melting points were determined in
capillary tubes and are uncorrected. Elemental analyses were carried out on Flash EA 1112
Series CHNS Analyzer. NMR spectra were recorded on a Bruker Avance-II 300 MHz
1
spectrometer operating at 300.13 (1H), 75.47 (13C{1H}) and 57.25 (77Se{1H}) MHz. H and
1
13C{1H} NMR chemical shifts were relative to internal chloroform peak (δ = 7.26 ppm for H
13
77
and δ = 77.0 for C{1H} NMR). The Se{1H} NMR chemical shifts were relative to external
diphenyl diselenide (Ph2Se2) in CDCl3 (δ 463.0 ppm relative to Me2Se (0 ppm)). The mass
spectra were recorded on a MS-500 Ion Trap (IT) Varian mass spectrometer at Sophisticated
Analytical Instrumentation Facility (SAIF), Indian Institute of Technology-Bombay, Mumbai.
1
Selected H, 13C and 77Se NMR spectra for 1, 2 and 10 are presented in the Supplemental
Materials (Figures S 1 – S 9)
Synthesis
Synthesis of [PhC(OCH2CH2O)CH2Se]2 (1). To a greenish brown solution of Na2Se2 in
DMF (200 mL) (prepared by stirring a mixture of Se (20 g, 253 mmol), crushed NaOH (10.1 g,
.
253 mmol) and N2H4 H2O (65 % v/v, 4.70 mL, 61.3 mmol) for 2 h) at 90 ºC, solution of
PhC(OCH2CH2O)CH2Br (61.8 g, 254 mmol) in DMF (100 mL) was added drop wise over a
o
period of 30 min and the reaction mixture was further stirred at ~ 100 C for 3 h. The reaction
was monitored by TLC. A clear yellow solution was cooled to room temperature and diluted
with water while the product was precipitated in the form of yellow crystals. It was filtered,
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washed several times with water and cold methanol and recrystallized from hot methanol to yield
o
yellow crystals of the title compound (45.9 g, 74 %). m.p.: 95-96 C. Anal. Calcd. for
1
C20H22O4Se2: C, 49.60; H, 4.58; Found: C, 49.74; H, 4.55 %. H NMR (CDCl3) δ: 3.53 (s, 2JSe-H
= 11 Hz, 2H, -SeCH2-), 3.78-3.83 (m, 2H, -OCH2CH2O-), 4.06-4.10 (m, 2H, -OCH2CH2O-),
13
7.28-7.36 (m, 3H, C6H5), 7.45-7.82 (m, 2H, C6H5); C{1H} NMR (CDCl3) δ: 42.7 (1JSe-C = 83
Hz, -SeCH2-), 65.1 (-OCH2CH2O-), 108.9 (-C(OCH2CH2O)-), 125.6, 128.0, 128.1, 141.1 (-Ph);
77Se{1H} NMR (CDCl3) δ: 310 ppm. MS (IT) m/z: 487 [M+1]+, 332 [M-2C6H5], 283 [M/2+K].
Synthesis of PhC(OCH2CH2O)CH2SeCH2CH2NH2 (2) Pale yellow oil (91 %). To a
suspension of 1 (1.2 g, 2.48 mmol) in ethanol, NaBH4 (209 mg, 5.5 mmol) was added in a flow
of nitrogen. The reaction mixture was stirred for 2 h to form a clear colorless solution. To this,
solid 2-bromo ethylamine hydrobromide (1.01 g, 4.93 mmol) was added with stirring which
continued for 3 h whereupon a white slurry formed. The reaction was monitored with TLC. The
solvent was evaporated on a rotavapor. The residue was dissolved in water and extracted with
ethyl acetate. The organic layer was dried over sodium sulfate, evaporated on rotavapor and the
residue was purified by column chromatography with ethyl acetate:hexane mixture (20:80) as
eluent to afford a thick yellow oil (1.29 g, 91 %). Anal. IR (υ cm-1): 3375, 2949, 2888, 1488,
1
1447, 1042, 980, 703. H NMR (CDCl3) δ: 1.62 (s, 2H, -NH2), 2.56 (t, J = 6.5 Hz, 2H, -
SeCH2CH2-), 2.80 (t, J = 6.5 Hz, 2H, -CH2NH2), 2.99 (s, 2JSe-H =11 Hz, 2H, -SeCH2-), 3.73-3.78
(m, 2H, -OCH2CH2O-), 4.03-4.08 (m, 2H, -OCH2CH2O-), 7.28-7.31 (m, 3H, C6H5), 7.42-7.45
13
(m, 2H, C6H5); C{1H} NMR (CDCl3) δ: 29.7 (1JSe-C = 61 Hz, -SeCH2CH2-), 33.8 (1JSe-C = 73
Hz, -CH2Se-), 41.4 (-CH2NH2), 65.0 (-OCH2CH2O-), 109.0 (-C(OCH2CH2O)-), 125.5, 127.8,
127.9, 141.4 (-Ph); 77Se{1H} NMR (CDCl3) δ: 91 ppm.
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Compounds 3-5 were synthesized in a similar mannar using the corresponding organic
halide.
PhC(OCH2CH2O)CH2SeCH2CH2CH2NH2 (3). Pale yellow oil (86 %). IR (υ cm-1):
2934, 2887, 1560, 1486, 1043, 704. 1H NMR (CDCl3) δ: 1.75 (qn, J = 6.8 Hz, 2H, -CH2CH2CH2-
), 2.02 (bs, 2H, -NH2), 2.55 (t, J = 7.1 Hz, 2H, -SeCH2CH2-), 2.74 (t, J = 6.1 Hz, -CH2NH2), 3.04
(s, 2H, -CH2Se-), 3.77-3.88 (m, 2H, -OCH2CH2O-), 4.06-4.17 (m, 2H, -OCH2CH2O-), 7.30-7.37
13
(m, 3H, -C6H5), 7.47-7.51 (m, 2H, -C6H5); C{1H} NMR (CDCl3) δ: 22.3 (1JSe-C = 59 Hz, -
SeCH2CH2-), 33.8 (-CH2CH2CH2-), 34.1 (1JSe-C = 68 Hz, -SeCH2-), 41.7 (-CH2NH2), 65.0 (-
77
OCH2CH2O-), 109.2 (-C(OCH2CH2O)-), 125.6, 127.9, 141.4 (-Ph); Se{1H} NMR (CDCl3) δ:
128 ppm.
PhC(OCH2CH2O)CH2SeCH2py (4). Pale yellow oil (75 %); IR (υ cm-1): 2944, 2886,
1
1590, 1566, 1473, 1434, 1028, 982, 766, 704. H NMR (CDCl3) δ: 3.06 (s, 2JSe-H = 11 Hz, 2H, -
2
CH2Se-), 3.79-3.83 (m, 2H, -OCH2CH2O-), 3.90 (s, JSe-H = 14 Hz, 2H, -CH2py), 4.09-4.14 (m,
2H, -OCH2CH2O-), 7.13 (t, J = 6.2 Hz, 1H, -py), 7.25-7.29 (m, 1H, -py), 7.31-7.36 (m, 3H, -
Ph), 7.47-7.50 (m, 2H, -Ph), 7.62 (td, J = 7.9, 1.8 Hz, 1H, -py), 8.50 (d, J = 4.8 Hz, 1H, -py);
13C{1H} NMR (CDCl3) δ: 29.3 (1JSe-C = 61 Hz, -SeCH2py), 33.5 (1JSe-C = 74 Hz, -CH2Se-), 64.8
(-OCH2CH2O-), 109.1 (-C(OCH2CH2O)-), 121.0, 122.6, 125.3, 127.7, 127.7, 136.0, 141.4,
148.8, 159.2 (-Ph + -py); 77Se{1H} NMR (CDCl3) δ: 219 ppm.
PhC(OCH2CH2O)CH2SeC6H4(o-NO2) (5). Yellow crystalline solid (86 %). m. p.: 88-90
oC. Anal. Calcd. for C16H16NO4Se: C, 52.61; H, 4.41%; Found: C, 52.63; H, 4.42% . IR (υ cm-1):
1
2986, 2889, 1588, 1565, 1505, 1328, 1039, 708. H NMR (CDCl3) δ: 3.48 (s, 2JSe-H = 11 Hz, 2H,
-CH2Se-), 3.84-3.89 (m, 2H, -OCH2CH2O-), 4.15-4.19 (m, 2H, -OCH2CH2O-), 7.28-7.33 (m, 1H,
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aromatic), 7.35-7.43 (m, 3H, aromatic), 7.45-7.51 (m, 1H, aromatic), 7.57-7.60 (m, 2H,
aromatic), 7.67 (dd, J = 8.1 Hz, 1H, aromatic), 8.25 (dd, J = 8.1 Hz, 1H, aromatic); 13C{1H}
NMR (CDCl3) δ: 37.5 (1JSe-C = 79 Hz, -CH2Se-), 65.4 (-OCH2CH2O-), 125.3, 128.4, 128.5, 141.6
(-Ph); 125.5, 126.0, 126.4, 128.8, 129.9, 133.4 (-C6H4NO2); 77Se{1H} NMR (CDCl3) δ: 328
ppm.
Synthesis of PhC(OCH2CH2O)CH2SeCH2CH2OH (6) and PhCOCH2SeCH2CH2OH
(8). To a suspension of 1 (2.0 g, 4.13 mmol) in ethanol, NaBH4 (350 mg, 9.21 mmol) was added
in a flow of nitrogen. The reaction mixture was stirred for 2 h to form a clear colorless solution.
To this 2-bromo ethanol (0.6 mL, 8.26 mmol) was added and the contents were stirred for 3 h
until a white slurry formed. The reaction was monitored by TLC. The solvent was removed on a
rotavapor, residue was dissolved in water and extracted with ethyl acetate. Organic layer was
dried over sodium sulfate, evaporated on rotavapor and the residue was purified by column
chromatography eluting with ethyl acetate and hexane to give two fractions (by TLC). The first
fraction after solvent evaporation gave 6 while the second one afforded 8.
PhC(OCH2CH2O)CH2SeCH2CH2OH (6). Pale yellow oil (710 mg, 30 %). IR (υ cm-1):
3328 (-OH), 2932, 2875, 1595, 1578, 1448, 1277, 1042, 709. 1H NMR (CDCl3) δ: 2.73 (t, J = 5.9
Hz, 2H, -SeCH2CH2OH), 3.03 (bs, 1H, -OH), 3.08 (s, 2JSe-H = 10.5 Hz, 2H, -CH2Se-), 3.76 (t, J =
5.6 Hz, 2H, -SeCH2CH2OH), 3.79-3.87 (m, 2H, -OCH2CH2O-), 4.10-4.15 (m, 2H, -OCH2CH2O-
), 7.28-7.36 (m, 3H, -C6H5), 7.44-7.48 (m, 3H, -C6H5); 13C{1H} NMR (CDCl3) δ: 29.4 (1JSe-C
=
64 Hz, -SeCH2CH2OH), 34.5 (1JSe-C = 73 Hz, -SeCH2-), 61.7 (-CH2OH), 65.2 (-OCH2CH2O-),
109.1 (-C(OCH2CH2O)-), 125.5, 128.1, 128.3, 141.3 (-Ph); 77Se{1H} NMR (CDCl3) δ: 80 ppm.
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PhCOCH2SeCH2CH2OH (8). Pale yellow oil (840 mg, 42 %); IR (υ cm-1): 3358 (-OH),
2926, 1685 (C=O), 1276, 710. 1H NMR (CDCl3) δ: 2.03 (bs, 1H, -OH), 2.87 (t, J = 5.9 Hz, 2H, -
SeCH2CH2-), 3.86 (t, J = 6.0 Hz, 4H, -CH2SeCH2-), 7.45-7.50 (m, 2H, -C6H5), 7.56-7.61 (m, 1H,
-C6H5), 7.96 (dd, J = 6.6, 1.5 Hz, 2H, -C6H5); 13C{1H} NMR (CDCl3) δ: 26.3 (1JSe-C = 65 Hz, -
SeCH2CH2-), 28.4 (1JSe-C = 65 Hz, -CH2Se-), 61.4 (-CH2OH), 128.5, 128.6, 134.7 (-Ph), 195.5
(C=O); 77Se{1H} NMR (CDCl3) δ: 171 ppm.
Compounds 7 and 9 were synthesized in a similar mannar using 3-bromo propanol.
PhC(OCH2CH2O)CH2SeCH2CH2CH2OH (7). Pale yellow oil (14 %), IR (υ cm-1):
1
3407 (-OH), 2934, 2874, 1595, 1578, 1447, 1276, 1009, 709. H NMR (CDCl3) δ: 1.78 (qn, J =
2
6.6 Hz, 2H, -CH2CH2CH2-), 2.55 (t, J = 7 Hz, 2H, -SeCH2CH2-), 3.00 (s, JSe-H = 11 Hz, 2H, -
CH2Se-), 3.07 (br, 1H, -OH), 3.58 (t, J = 6.2 Hz, 2H, -CH2OH), 3.72-3.77 (m, 2H, -OCH2CH2O-
), 4.02-4.07 (m, 2H, -OCH2CH2O-), 7.22-7.31 (m, 3H, -C6H5), 7.41-7.45 (m, 2H, -C6H5);
13C{1H} NMR (CDCl3) δ: 21.3 (1JSe-C = 59 Hz, -SeCH2CH2-), 32.4 (-CH2CH2CH2-), 33.9 (1JSe-C
= 73.3 Hz, -SeCH2-), 61.5 (-CH2OH), 64.8 (-OCH2CH2O-), 109.0 (-C(OCH2CH2O)-), 125.3,
127.8, 127.8, 141.2 (-Ph); 77Se{1H} NMR (CDCl3) δ: 123 ppm.
PhCOCH2SeCH2CH2CH2OH (9). Pale yellow oil (52 %); IR (υ cm-1): 3408 (-OH),
1
2933, 2874, 1666 (C=O), 1595, 1578, 1447, 1276, 1010, 709. H NMR (CDCl3) δ: 1.78 (qn, J =
6.5 Hz, 2H, -SeCH2CH2-), 2.17 (br, 1H, -OH), 2.76 (t, J = 7.1 Hz, 2H, -SeCH2-), 3.70 (t, J = 6.1
Hz, 2H, -CH2OH), 3.79 (s, 2H, -SeCH2-), 7.43-7.48 (m, 2H, C6H5), 7.54-7.60 (m, 1H, C6H5),
7.94-7.96 (m, 2H, C6H5); 13C{1H} NMR (CDCl3) δ: 21.7 (1JSe-C = 63 Hz, -SeCH2-), 26.4 (1JSe-C
= 65 Hz, -COCH2-), 32.3, 61.3 (each s -CH2CH2-), 128.4, 128.5, 133.1, 134.7 (-Ph), 195.3 (-
C=O); 77Se{1H} NMR (CDCl3) δ: 211 ppm.
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Synthesis of [PhCOCH2Se]2 (10). To a hot acetonitrile solution (10 mL) of 1 (60 mg,
0.12 mmol), an excess of ceric ammonium nitrate (CAN) (140 mg, 0.38 mmol), dissolved in
water (5 mL) was added slowly until the orange color of CAN persisted for a long time. The
reaction mixture was refluxed until a white precipitate was formed. The reaction was monitored
by TLC. The solvents were evaporated under vacuum and the residue was extracted with ethyl
acetate, organic layer was dried over sodium sulfate and concentrated on rotavapor to yield a
pale yellow solid which was further purified on column chromatography as yellow crystals (30
mg, 61 %). m.p.: 125-126 oC. Anal. Calcd. for C16H14O2Se2: C, 48.50; H, 3.56; Found: C, 48.30;
1
H, 3.49. IR (υ cm-1): 1654 (C=O), 1447, 1415, 1274, 1011, 704. H NMR (CDCl3) δ: 4.30 (s,
2JSe-H = 14.7 Hz, 2H, -SeCH2-), 7.45 (t, J = 7.7 Hz, 2H, C6H5), 7.57 (t, J = 7.4 Hz, 1H, C6H5),
7.92 (d, J = 7.8 Hz, 2H, C6H5); 13C{1H} NMR (CDCl3) δ: 34.0 (1JSe-C = 77 Hz, -CH2Se-), 128.6,
128.7, 133.5, 135.1 (-Ph), 195.3 (-C=O); 77Se{1H} NMR (CDCl3) δ: 372 ppm.
X-ray Crystallography
Single crystal X-ray data on [PhC(OCH2CH2)CH2Se]2 (1) and (PhCOCH2Se)2 (10) were
collected at room temperature (298 ± 2 K) on a Rigaku AFC 7S diffractometer using graphite
monochromated Mo-Kα (λ = 0.71069 Å) radiation so that θmax = 27.5o. The unit cell parameters
(Table 1) were determined from 25 reflections measured by a random search routine. The
intensity data were corrected for Lorenz, polarization and absorption effects with an empirical
procedure.38 The structures were solved by direct methods using SHELX-9739 and refined by
full-matrix least squares methods. The non-hydrogen atoms were refined anisotropically. The
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hydrogen atoms were fixed in their calculated positions. The molecular structures were drawn by
ORTEP.40 X-ray data and selected bond and angles are presented in Tables 1 and 2 respectively.
[Insert Table 1]
[Insert Table 2]
SUPPLEMENTARY DATA
Crystallographic data for the structural analyses have been deposited with the Cambridge
Crystallographic Data Centre, CCDC Nos. 937751 [PhC(OCH2CH2O)CH2Se]2 (1) and 937750
[PhCOCH2Se]2 (10). Copies of this information may be obtained free of charge from: The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: (int. code) +44 1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk].
SUPPORTING INFORMATION (see footnote on the first page of this article):
Synthesis and characterization of Ph(OCH2CH2O)CH2Br, NMR (1H, 13C{1H} and
77Se{1H}) and mass spectra of all organoselenium compounds and the cif files of the single
crystal X-ray diffraction analyses of compounds 1 and 10 are available.
ACKNOWLEDGEMENTS
One of the authors (ASH) is grateful to Board of Research in Nuclear Sciences (BRNS),
Department of Atomic Energy (DAE) for a Junior Research Fellowship awarded to him. We are
also grateful to BRNS for the research grant under the Prospective Research Fund (PRF) Scheme
(Grant No. BRNS/2007/38/5).
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Table 1 Crystallographic and structural refinement data for selenoacetophenone derivatives
[PhC(OCH2CH2O)CH2Se]2 (1) and[PhCOCH2Se]2 (10).
1
10
Empirical formula
Formula weight
Crystal system/ space group
a / Å
C20H22O4Se2
484.30
C16H14O2Se2
396.19
Monoclinic/ I 2/a
11.934 (3)
10.872 (2)
15.133 (6)
90.00
95.00 (3)
90.00
1955.3 (10)
4
Orthorhombic/ Pbca
8.705 (3)
17.760 (9)
19.517 (7)
90.00
90.00
90.00
3017 (2)
8
1.744
b / Å
c / Å
α / o
β / o
γ / o
V / (Å3)
Z
Dc (g/cm3)
1.645
µ(Mo-Kα) mm-1/ F (000)
Crystal size
3.804/ 968
0.25 x 0.15 x 0.10
Yellow/ Prismatic
298
4.899/ 1552
0.30 x 0.30 x 0.10
Colorless/ Block
298
Color / Shape
Temp (K)
Theta range of data collection
Reflections collected
Independent reflections
Data/ Restraints/ Parameters
Goodness-of-fit on F2
Final R indices [I>2(I)]
R indices (all data)
Largest difference peak/hole
2.54-27.50
2239
1199
2239/ 0/ 118
0.993
R1 = 0.0385
R1 = 0.1151
0.391, -0.396
2.52-27.48
3453
1184
3453/ 0/ 181
0.935
R1 = 0.0490
R1 = 0.2308
0.422, -0.586
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Table 2 Selected bond lengths (Å) and bond angles (°) for compound 1 and 10
[PhC(OCH2CH2O)CH2Se]2 (1)
[PhCOCH2Se]2 (10)
Se(1)-Se(1′)
Se(1)-C(1)
C(1)-C(2)
C(2)-O(1)
C(2)-O(2)
2.3152 (11)
Se(1)-Se(2)
Se(1)-C(1)
Se(2)-C(9)
C(2)-O(1)
C(10)-O(2)
2.3118 (12)
1.975 (6)
1.965 (6)
1.231 (6)
1.200 (6)
1.962 (4)
1.511 (5)
1.429 (4)
1.426 (4)
Se(1)-C(1)-C(2)
C(1)-Se(1)-Se(1′)
C(1)-C(2)-C(3)
C(1)-C(2)-O(1)
C(1)-C(2)-O(2)
113.0 (3)
100.45 (13)
110.3 (3)
110.8 (3)
108.6 (3)
Se(1)-C(1)-C(2)
C(1)-C(2)-O(1)
C(1)-C(2)-C(3)
C(1)-Se(1)-Se(2)
Se(1)-Se(2)-C(9)
Se(2)-C(9)-C(10)
C(9)-C(10)-O(2)
C(9)-C(10)-C(11)
110.9 (4)
119.3 (6)
120.6 (6)
101.12 (18)
101.27 (16)
110.2 (4)
120.5 (6)
119.6 (6)
C(1)-Se(1)-Se(1′)-C(1') 78.1
C(1)-Se(1)-Se(2)-C(9) 90.3 (3)
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Figure 1 Molecular crystal structure of [PhC(OCH2CH2O)CH2Se]2 (1). Thermal ellipsoids are
drawn with 30% probability. Inset shows intra-molecular Se---O non-bonding
interactions.
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Figure 2 Molecular crystal structure of [PhCOCH2Se]2 (10). Thermal ellipsoids are drawn with
30% probability. Inset shows inter-molecular Se---O non-bonding interactions.
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R
N
R'
N
N
Se
2
Se
2
R = H, Me, Et, Pr
R' = Me, Et, Pr
R, R' = Me or c-Hx
(II)
(I)
R
O
SePh
OR'
Se
2
(IV)
R / R' = H / H; Me / H;
Et / H; Et / Me
(III)
Scheme 1
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O
O O
Br
Br
HOCH2CH2OH
p-TSA/Toluene
1/2 Na2Se2 DMF
O
O O
O O
i) NaBH4 /
EtOH
ii) R-Br
Se
Se R
Se
2
CAN
Acetonitrile
2
1/2
1/2
(1)
(10)
R
-(CH2)2NH2
-(CH2)3NH2
-CH2py
(2)
(3)
(4)
i) NaBH4 / EtOH
ii) Br(CH2)nOH
-C6H4(o-NO2) (5)
O
O O
OH
n
Se
Se
OH
n
+
n
2
3
n
2
3
aq. HCl
Acetone
(8)
(9)
(6)
(7)
Scheme 2. Synthesis of Compounds 1-10
O
O
Br
SeCN
KSeCN
Acetonitrile
(11)
Scheme 3
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