Investigation on the se-acylation with N-acylbenzotriazoles

Article abstract of DOI:10.1080/10426507.2010.540605

The acylation of Se-nucleophiles with N-acylbenzotriazoles was investigated. Samarium phenylselenolate and benzylselenolate (RSeSmI ₂) reacted with N-aroyl and N-alkanoylbenzotriazoles smoothly and afforded the corresponding selenol esters in g

Full text of DOI:10.1080/10426507.2010.540605

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Phosphorus, Sulfur, and Silicon and the
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Investigation on the Se-Acylation with N-
Acylbenzotriazoles
Junyan Jiang a , Wencun Wang a , Xiaoxia Wang a , Xiangming Zhu a
Zhifang Li b
a College of Chemistry and Life Sciences , Zhejiang Normal
University , Jinhua, P.R. China
&
b Key Laboratory of Organosilicon Chemistry and Material
Technology , Ministry of Educations, Hangzhou Normal University ,
Hangzhou, P.R. China
Published online: 14 Oct 2011.
To cite this article: Junyan Jiang , Wencun Wang , Xiaoxia Wang , Xiangming Zhu & Zhifang Li (2011)
Investigation on the Se-Acylation with N-Acylbenzotriazoles, Phosphorus, Sulfur, and Silicon and the
Related Elements, 186:10, 2047-2054, DOI: 10.1080/10426507.2010.540605
To link to this article: http://dx.doi.org/10.1080/10426507.2010.540605
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Phosphorus, Sulfur, and Silicon, 186:2047–2054, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.540605
INVESTIGATION ON THE Se-ACYLATION WITH
N-ACYLBENZOTRIAZOLES
Junyan Jiang,1 Wencun Wang,1 Xiaoxia Wang,1
Xiangming Zhu,1 and Zhifang Li2
1College of Chemistry and Life Sciences, Zhejiang Normal University,
Jinhua, P.R. China
2Key Laboratory of Organosilicon Chemistry and Material Technology,
Ministry of Educations, Hangzhou Normal University, Hangzhou, P.R. China
GRAPHICAL ABSTRACT
Abstract The acylation of Se-nucleophiles with N-acylbenzotriazoles was investigated.
Samarium phenylselenolate and benzylselenolate (RSeSmI2) reacted with N-aroyl and
N-alkanoylbenzotriazoles smoothly and afforded the corresponding selenol esters in good
yields. Treatment of the RSeSmI2 with α,β-unsaturated N-acylbenzotriazoles afforded the
anticipated α,β-unsaturated selenol esters in moderate yields, due mainly to the side reaction
of conjugate addition.
Keywords N-Acylbenzotriazole; samarium(II) iodide; diselenides; Se-acylation; selenol esters
INTRODUCTION
N-Acylbenzotriazoles have found wide applications in organic synthesis. Being
less sensitive toward moisture, milder in reactivity, and more readily to crystallize, N-
acylbenzotriazoles often offer great advantages over the corresponding acid chlorides.
Received 1 October 2010; accepted 12 November 2010.
The authors are thankful to the National Natural Science Foundation of China (No. 20802070) for financial
support.
Address correspondence to Xiaoxia Wang, College of Chemistry and Life Sciences, Zhejiang Normal
University, Jinhua 321004, P.R. China. E-mail: wangxiaoxia@zjnu.edu.cn
2047

2048
J. JIANG ET AL.
They can acylate the N-, C-, O-, and S-nucleophiles smoothly under mild conditions
with satisfactory yield.1 Usually, racemization does not occur during the reaction2–4 and
good chemoselectivity could be obtained readily.5,6 However, despite their general use and
remarkable advantages in organic synthesis, the acylation of N-acylbenzotriazoles with
Se-nucleophiles has not been reported.
Selenol esters are useful intermediates in organic synthesis7,8 and a variety of meth-
ods have been developed for the preparation of them. These include: (a) acylation of
acyl halides with selenols,9 selenium anions generated in situ from diselenides,10a–c,10f–i
or phenyl tributylstannyl selenide (PhSeSnBu3);10d,e (b) reaction of carboxylic acids11 or
their triethylammonium salts12 with phenylselenocyanate or benzeneselenenyl chloride in
the presence of tributylphosphine; (c) ring opening of isopropylidene malonate derivatives
by samarium aryl selenolate;13 (d) reaction of acylzirconene chlorides with ArSeBr or di-
aryldiselenides;14 (e) reaction of aldehydes and diisobutylaluminum selenoate (iBu2AlSeR)
under Tishchenko-type conditions;15a and (f) free-radical Se-acylation of the diselenides
with In and acyl halides.15b However, although some of these synthetic approaches could
afford good, even excellent, yields of the selenol esters, they either utilized acyl halides,
which were moisture-sensitive and sometimes difficult to prepare and purify, or were lim-
ited to a narrow substrate scope. Sometimes, rarely available reagents, tedious procedures,
and/or harsh conditions were employed. Therefore, alternative methods for the preparation
of selenol esters were still required.
In continuation of our ongoing study on the nucleophilicity of heteroatom nucle-
ophiles toward N-acylbenzotriazoles, herein we employed samarium selenolates (RSeSmI2)
as the Se-nucleophile and the potential of the Se-acylation for the preparation of selenol
esters were explored.
RESULTS AND DISCUSSION
Samarium selenolates (RSeSmI2) were generated by the reductive cleav-
age of RSeSeR with SmI2.16a First, dibenzyldiselenide was subjected to the
SmI2–tetrahydrofuran (THF) solution. One hour later, the resulting mixture was
treated by N-benzoylbenzotriazole. The usual work-up afforded the desired selenol esters,
but the yield was rather unsatisfactory (Table 1, Entries 1 and 2).
Addition of hexamethylphosphoramide (HMPA), which was reported to enhance the
reactivity of SmI2 and facilitate the solubility of the selenolates,16a,b was attempted in the
reductive cleavage process and improvement in the yields of the selenoesters was observed
(Table 1, Entries 1 and 2). Especially the reaction of BnSeSmI2 and N-acylbenzotriazole
2c in the presence of HMPA afforded the expected product in 70% yield and thus made
the reaction synthetically valuable (Table 1, Entry 3). Fortunately, the acylation with N-
aroylbenzotriazoles of samarium phenylselenolate (PhSeSmI2) generated from diphenyldis-
elenide afforded more satisfactory yields (Table 1, Entries 4–13), tolerating both electron-
donating and electron-withdrawing substituents on the aryl. N-Alkanoyl benzotriazole
worked equally well (Table 1, Entries 14–16). It should be noted that the acylation be-
tween the samarium selenolate and N-acylbenzotriazole was very fast and the reaction was
quenched immediately after the addition of the N-acylbenzotriazole (in 3 min). In fact, pro-
longing the reaction time would lead to regeneration of the starting N-acylbenzotriazoles.
It may suggest that the leaving benzotriazolyl could reattack the selenol ester carbonyl and
make the reaction reversible (Table 1, Entry 4).

Se-ACYLATION WITH N-ACYLBENZOTRIAZOLES
2049
Table 1 Se-acylation with N-aroyl and N-alkanoylbenzotriazoles
O
O
R2
2
SmI2/HMPA
THF
Se
R1
Bt
N
N
R1
R1
Se
R2
N
Se
Bt=
1
3
Entry
R1
R2
Product
Yield%a
1
2
3
4
5
6
7
8
9
Bn
Bn
Bn
Ph
Ph
Ph
Ph
Ph
Ph
Ph-2a
3a
3b
3c
3d
3e
3f
3g
3h
3i
33 (28b)
42 (8b)
70
p-MeO(C6H4)-2b
p-Cl(C6H4)-2c
Ph-2a
p-Cl(C6H4)-2c
p-MeO(C6H4)-2b
o-Cl(C6H4)-2d
p-NO2(C6H4)-2e
78 (48c)
83
71
80
61
68
2f
O
2f
10
11
12
13
Ph
Ph
Ph
Ph
o-CH3(C6H4)-2g
p-CH3(C6H4)-2h
m-CH3(C6H4)-2i
2j
3j
3k
3l
52
78
86
83
3m
2j
14
15
16
Ph
Ph
Ph
CH3CH2-2k
3n
3o
3p
66
60
66
CH3(CH2)4CH2-2l
(CH3)2CH-2m
aIsolated yields based on N-acylbenzotriazoles. bIn the absence of HMPA. cThe acylation proceeded for more
than 15 min.
Compared with the acyl halides method,16a the acylation of the samarium selenolates
with N-acylbenzotriazoles was more efficient and the use of excess acylating reagent was
unnecessary. The reason may be that acyl halides could also induce the ring opening of
THF in the presence of the resulting Sm(III) salt,17 while N-acylbenzotriazoles would not.
We then extended the substrates to a,b-unsaturated N-acylbenzotriazoles. Thus, cin-
namoyl benzotriazole 4a was added to the samarium selenolate. After usual work-up, the
residue was purified by flash column chromatography on silica gel to give a solid, but 1H
NMR spectrum showed that the solid was crude 5a contaminated with a byproduct resulting
from Michael addition as indicated by the three characteristic dd peaks: δ 3.32 (dd, J =
6.4 Hz, J = 16.0 Hz, 1H), 3.51 (dd, J = 9.2 Hz, J = 16.0 Hz, 1H), and 4.77 (dd, J = 6.4 Hz,
J = 9.2 Hz, 1H) (see supporting information). The byproduct could not be isolated because
of its similar polarity to 5a, but pure 5a could be obtained by further recrystallization.
Both the 1H-NMR spectra of pure 5a and crude 5a (containing the byproduct) indicated the
absence of benzotriazolyl group. The liquid chromatography-mass spectrometry (LC-MS)
spectra of crude 5a showed two characteristic peaks: 311 and 467 (m/z). The LC-MS com-
bined with the 1H NMR spectra suggested that the byproduct should be compound 6a (467
was ascribed to the molecular ion peak of 6a [M (444)+Na] and 311 was ascribed to that
of 5a [M (287)+Na+H]; see supporting information). The ratio of 5a and 6a was 1:0.4 as
determined by 1H NMR analysis (Table 2, Entry 1).

2050
J. JIANG ET AL.
Table 2 The reaction between samarium phenylselenolate and unsaturated N-acylbenzotriazoles 4
O
Se
R
Bt
O
R
4
SmI2/HMPA
THF
PhSeSePh
+
R
O
Se
Se
5
6
Entry
R
Product
Temperature (◦C)
Time (h)
Ratioa
Yield%b
1
2
3
4
5
6
7
Ph-4a
Ph-4a
Ph-4a
p-Cl(C6H4)- 4b
p-Cl(C6H4)- 4b
p-MeO(C6H4)- 4c
5a:6a
5a:6a
5a:6a
5b:6b
5b:6b
5c
20
60
70
60
60
60
60
0.5
0.5
0.5
0.5
5
1:0.42
1:0.07
1:0.19
1:0.27
1:0.07
1:0
–
43
55
39
39
72
49
0.5
0.5
4d
5d
1:0
O
4d
8
9
p-CH3 (C6H4)-4e
Ph-4a
5e:6e
5a:6a
60
60
5
1
1:0.14
1:0.6c
64
40 (24d)
aDetermined by 1H-NMR. bIsolated yields of product 5. cFour equivalents of PhSeSmI2 were used. dPMR yield
of 6a.
Subsequent optimization of the conditions found that performing the acylation step
◦
at 60 C could improve the yield of 5a (Table 2, Entry 2). Increasing the temperature
could give better yield of 5a, but at the same time resulted in poorer selectivity (Table 2,
Entry 3). It was also found that prolonging the time could improve the selectivity for the
unsaturated selenol esters; thus, 5b/6b and 5e/6e were obtained in a ratio of 1:0.07 and
1:0.14 (Table 2, Entries 5 and 8). Again, the isolation of pure 6b and 6e failed, and only
pure 5b and 5e were obtained by further recrystallization. Under the optimized conditions,
it was gratifying to find that substrates 4c and 4d underwent clean Se-acylation, providing
the corresponding selenol esters 5c and 5d in 72% and 49% yield, respectively (Table 2,
Entries 6 and 7). In addition, we tried to use excess PhSeSmI2 in hope of getting byproduct
6 as the main or sole product. Thus, four equivalents of PhSeSmI2 and one equivalent of
cinnamoyl benzotriazole 4a were used as the substrates. However, the reaction resulted in
a mixture of 5a and 6a in a molar ratio of 1:0.6 (Table 2, Entry 9).
It may be interesting to compare the reactivity of samarium selenolate and samarium
thiolate. Samarium thiolate attacked preferably on the carbonyl of a,b-unsaturated N-
acylbenzotriazoles and afforded a,b-unsaturated thioesters exclusively,18 while the softer
samarium selenolate could also attack the electron-deficient olefin carbon, which combined
with the Se-acylation and finally afforded the b-phenylselanyl selenol ester 6.
CONCLUSION
The Se-acylation ability of N-acylbenzotriazoles has been demonstrated. With samar-
ium selenolate as the Se-nucleophile, N-aroyl and N-alkanoylbenzotriazoles underwent
the acylation smoothly and afforded the selenol esters in moderate to good yields. The

Se-ACYLATION WITH N-ACYLBENZOTRIAZOLES
2051
Se-acylation with α,β-unsaturated N-acylbenzotriazoles could also be achieved with high
regioselectivity.
EXPERIMENTAL
THF was distilled from sodium benzophenone immediately prior to use. All reactions
were conducted under a nitrogen atmosphere. Melting points are uncorrected. 1H (400 MHz)
and 13C (100 MHz) NMR spectra were recorded on a Bruker AV400 NMR instrument in
CDCl3 [with tetramethylsilane (TMS) as internal standard]. Chemical shifts (δ) are reported
in ppm and coupling constant J is given in Hz. IR spectra were recorded using KBr disks with
a NEXUS 670 FTIR spectrometer. Elemental analyses were performed on a Vario-ELIII
instrument. MS spectrum was analyzed on a Varian 500-MS equipped with an electrospray
ionization source and ion trap analyzer in the positive ionization mode, with data acquisition
using the Varian MS Workstation (Varian, America). LC-MS was carried on Agilent 1100
LC/MSD SL.
General Procedure for the Preparation of Selenol Esters 3a–n and 5a–e
General Procedure for the Preparation of Selenol Esters 3a–n. To a so-
lution of SmI2 (1.3 mmol) in dry THF (10 mL) under a nitrogen atmosphere was added
HMPA (0.6 mL) and diselenide (0.6 mmol) in anhydrous THF (2 mL) by syringe. After
the mixture was stirred at room temperature for 1 h, N-acylbenzotriazole 2 (1.0 mmol)
in anhydrous THF (2 mL) was added at room temperature. When the purple color of the
mixture faded (after 3 min), hydrochloric acid (0.1 N, 3 mL) was added immediately to
quench the reaction followed by extraction with EtOAc (20 mL × 3). The organic layer
was washed successively with Na2S2O3 (aq), Na2CO3 (aq), and brine, and dried over anhy-
drous Na2SO4. The solvent was removed under reduced pressure to give a residue, which
was purified by flash column chromatography on silica gel (petroleum ether/ethyl acetate
80:1–50:1) to give the corresponding selenol ester.
General Procedure for the Preparation of Selenol Esters 5a–e. To the
solution of SmI2 (1.3 mmol) in dry THF (10 mL) under nitrogen atmosphere was added
HMPA (0.6 mL) and diselenide (0.6 mmol) in anhydrous THF (2 mL) by syringe. After
the mixture was stirred at room temperature for 1 h, the temperature was raised to 60 ◦C.
N-Acylbenzotriazole 4 (1.0 mmol) in anhydrous THF (4 mL) was then added and stirring
was continued for the time indicated in Table 2. Hydrochloric acid (0.1 N, 3 mL) was added
followed by extraction with EtOAc (20 mL × 3). The organic layer was washed successively
with Na2S2O3 (aq), Na2CO3 (aq), and brine, and dried over anhydrous Na2SO4. The solvent
was removed under reduced pressure to give a residue, which was purified by flash column
chromatography on silica gel (petroleum ether/ethyl acetate 80:1–50:1) to give a mixture
of 5 and 6 as solid. Crystallization in THF afforded pure 5.
Benzenecarboselenoic acid Se-benzyl ester 3a.15b Yellow oil; IR (neat): υ (cm-1)
1670; 1H NMR δ 4.36 (s, 2H), 7.23–7.32 (m, 3H), 7.38 (d, J = 7.6 Hz, 2H), 7.46 (t,
J = 8.0 Hz, 2H), 7.48–7.52 (m, 1H); 7.90 (d, J = 8.0 Hz, 2H).
Benzenecarboselenoic acid, 4-methoxy-Se-benzyl ester 3b. Light brown solid; mp
◦
◦
1
40 C–41 C; IR (KBr): υ (cm−1) 1659; H NMR δ 3.87 (s, 3H), 4.33 (s, 2H), 6.92 (d,
J = 8.0 Hz, 2H), 7.20–7.38 (m, 5H), 7.88 (d, J = 7.6 Hz, 2H); 13C NMR δ 28.9, 55.6,
114.0, 126.9, 128.6, 129.0, 129.6, 132.3, 139.6, 164.1, 193.2; MS m/z (Jrel.,%): 307 (100)
[M+H]+. Anal. Calcd. for C15H14O2Se: C, 59.02; H, 4.62. Found: C, 59.53; H, 4.61.

2052
J. JIANG ET AL.
Benzenecarboselenoic acid, 4-chloro-Se-benzyl ester 3c.19 Colorless solid; mp 68
◦C–69 ◦C (lit. mp 70–71 ◦C); IR (KBr): υ (cm−1) 1671; 1H NMR δ 4.36 (s, 2H), 7.21–7.36
(m, 5H), 7.43 (d, J = 8.4 Hz, 2H), 7.84 (d, J = 8.4 Hz, 2H).
Benzenecarboselenoic acid Se-phenyl ester 3d.15b Yellow solid; mp 37 ◦C–38 ◦C
(lit. mp 37 ◦C–38 ◦C); IR (neat): υ (cm−1) 1678; 1H NMR δ 7.31–7.39 (m, 5H), 7.49–7.51
(m, 3H), 7.83 (d, J = 7.6 Hz, 2H).
Benzenecarboselenoic acid, 4-chloro-Se-phenyl ester 3e. Beige solid; mp 84 ◦C–85
◦C (lit.11 mp 83.5 ◦C–84.5 ◦C); IR (KBr): υ (cm−1) 1690; 1H NMR δ 7.42–7.52 (m, 5H),
7.58 (d, J = 6.4 Hz, 2H), 7.87 (d, J = 8.0 Hz, 2H).
Benzenecarboselenoic acid, 4-methoxy-Se-phenyl ester 3f.11 White solid; mp 76
◦C–78 ◦C (lit. mp 62–63 ◦C); IR (KBr): υ (cm−1) 1683; 1H NMR δ 3.88 (s, 3H), 6.96 (d,
J = 8.0 Hz, 2H), 7.41–7.42 (m, 3H), 7.58–7.60 (m, 2H), 7.91 (d, J = 7.6 Hz, 2H); 13C
NMR δ 55.6, 114.1, 126.0, 128.9, 129.3, 129.7, 131.3, 136.4, 164.2, 191.4.
Benzenecarboselenoic acid, 2-chloro-Se-phenyl ester 3g.15b Light brown solid; mp
◦
◦
◦
1
57 C–58 C (lit. mp 59 C); IR (KBr): υ (cm−1) 1701; H NMR δ 7.37–7.45 (m, 6H),
7.60–7.62 (m, 2H), 7.73 (d, J = 1.2 Hz, 1H).
Benzenecarboselenoic acid, 4-nitro-Se-phenyl ester 3h.15b Yellow solid; mp 127
◦C–128 ◦C (lit. mp 136 ◦C–138 ◦C); IR (KBr): υ (cm−1) 1676; 1H NMR δ 7.45–7.48 (m,
3H), 7.64 (d, J = 6.4 Hz, 2H), 8.09 (d, J = 8.8 Hz, 2H), 8.35 (d, J = 8.8 Hz, 2H).
Furan-2-carboselenoic acid Se-phenyl ester 3i.10c Pale yellow solid; mp 60 ◦C–61
◦C; IR (KBr): υ (cm−1) 1679; 1H NMR δ 6.59–6.61 (m, 1H), 7.22–7.23 (m, 1H), 7.42–7.43
(m, 3H), 7.58–7.60 (m, 2H), 7.65–7.66 (m, 1H).
Benzenecarboselenoic acid, 2-methyl-Se-phenyl ester 3j. Light brown solid; mp
46 C–47 C; IR (KBr): υ (cm−1) 1699; H NMR δ 2.48 (s, 3H), 7.26–7.35 (m, 2H),
7.43–7.46 (m, 4H), 7.60–7.62 (m, 2H), 7.91 (d, J = 7.6 Hz, 1H); 13C NMR δ 20.9, 126.1,
127.0, 128.9, 129.0, 129.4, 131.9, 132.3, 136.1, 136.6, 138.3, 195.5; MS m/z (Jrel.,%): 277
(100) [M+H]+. Anal. Calcd. for C14H12OSe: C, 61.10; H, 4.40. Found: C, 60.97; H, 4.36.
Benzenecarboselenoic acid, 4-methyl-Se-phenyl ester 3k.10d White solid; mp 97
◦
◦
1
◦
1
◦C–98 C; IR (KBr): υ (cm−1) 1689; H NMR δ 2.43 (s, 3H), 7.29 (d, J = 8.0 Hz, 2H),
7.42–7.44 (m, 3H), 7.59–7.61 (m, 2H), 7.84 (d, J = 8.0 Hz, 2H); 13C NMR δ 21.8, 126.0,
127.5, 129.0, 129.4, 129.6, 136.0, 136.4, 144.9, 192.8.
Benzenecarboselenoic acid, 3-methyl-Se-phenyl ester 3l. Light brown solid; mp 47
◦C–48 ◦C; IR (KBr): υ (cm−1) 1680; 1H NMR δ 2.44 (s, 3H), 7.38–7.44 (m, 5H), 7.59–7.61
(m, 2H), 7.73–7.75 (m, 2H); 13C NMR δ 21.4, 124.6, 125.9, 127.8, 128.8, 129.1, 129.4,
134.7, 136.4, 138.6, 138.9, 193.5; MS m/z (Jrel.,%): 277 (100) [M+H]+. Anal. Calcd. for
C14H12OSe: C, 61.10; H, 4.40. Found: C, 61.17; H, 4.43.
Naphthalene-1-carboselenoic acid Se-phenyl ester 3m.10d Light brown solid; mp
◦
1
68–69 C; IR (KBr): υ (cm−1) 1696; H NMR δ 7.47–7.60 (m, 6H), 7.67–7.69 (m, 2H),
7.90 (d, J = 7.6 Hz, 1H), 8.06 (d, J = 8.4 Hz, 1H), 8.20 (d, J = 7.2 Hz, 1H), 8.56 (d, J =
8.4 Hz, 1H); 13C NMR δ 124.6, 125.3, 126.9, 127.3, 127.3, 128.4, 128. 4, 128.4, 129.1,
129.5, 133.6, 133.9, 136.2, 136.3, 195.4.
Propaneselenoic acid Se-phenyl ester 3n.20 Yellow oil; IR (neat): υ (cm−1) 1721;
1H NMR δ 1.22 (t, J = 7.6 Hz, 3H), 2.74 (q, J = 7.6 Hz, 2H), 7.38–7.40 (m, 3H), 7.52–7.54
(m, 2H).
Heptaneselenoic acid Se-phenyl ester 3o.8a Yellow oil; IR (neat): υ (cm−1) 1724;
1H NMR δ 0.88 (t, J = 6.8 Hz, 3H), 1.24–1.37 (m, 6H), 1.67–1.70 (m, 2H), 2.69 (t, J =
7.6 Hz, 2H), 7.36–7.38 (m, 3H), 7.49–7.51 (m, 2H).

Se-ACYLATION WITH N-ACYLBENZOTRIAZOLES
2053
2-methylpropaneselenoic acid Se-phenyl ester 3p.10d Yellow oil; IR (neat): υ
1
(cm−1) 1720; H NMR δ 1.25 (t, J = 7.2 Hz, 6H), 2.86–2.93 (m, 1H), 7.36–7.37 (m,
3H), 7.48–7.51 (m, 2H).
(E)-2-propeneselenoic acid, 3-phenyl-Se-phenyl ester 5a.14b Yellow solid; mp 82
◦C–83 ◦C (lit. mp 80 ◦C–81 ◦C); IR (KBr): υ (cm−1) 1685, 1607; 1H NMR δ 6.78 (d, J =
16.0 Hz, 1H), 7.41–7.43 (m, 6H), 7.56–7.60 (m, 5H).
(E)-2-propeneselenoic acid, 3-(4-chlorophenyl)-Se-phenyl ester 5b.14b Yellow
solid; mp 103 ◦C–104 ◦C (lit. mp 99–100 ◦C); IR (KBr): υ (cm−1) 1674, 1602; 1H NMR δ
6.74 (d, J = 15.6 Hz, 1H), 7.37–7.59 (m, 10H).
(E)-2-propeneselenoic acid, 3-(4-methoxyphenyl)-Se-phenyl ester 5c. Yellow
solid; mp 83 ◦C–84 ◦C; IR (KBr): υ (cm−1) 1690, 1592; 1H NMR δ 3.86 (s, 3H), 6.65 (d,
J = 16.0 Hz, 1H), 6.92 (d, J = 8.8 Hz, 2H), 7.40–7.43 (m, 3H), 7.51–7.60 (m, 5H); 13C
NMR δ 55.5, 114.6, 123.9, 126.5, 128.9, 129.4, 130.5, 136.0, 141.1, 162.0, 190.5; MS m/z
(Jrel.,%): 307 (100) [M+H]+. Anal. Calcd. for C16H14O2Se: C, 60.58; H, 4.45. Found: C,
60.41; H, 4.41.
(E)-2-propeneselenoic acid, 3-(furan-2-yl)-Se-phenyl ester 5d. Brown solid; mp
56 ◦C–57 ◦C; IR (KBr): υ (cm−1) 1666, 1607; 1H NMR δ 6.51 (d, J = 2.0 Hz, 1H), 6.67
(d, J = 15.2 Hz, 1H), 6.74 (d, J = 3.2Hz, 1H); 7.34 (d, J = 15.2 Hz, 1H), 7.40–7.42 (m,
3H), 7.54–7.59 (m, 3H); 13C NMR δ 112.9, 117.2, 123.6, 126.4, 126.7, 129.0, 129.4, 135.9,
145.5, 150.5, 190.7; MS m/z (Jrel.,%): 279 (100) [M+H]+. Anal. Calcd. for C13H10O2Se:
C, 56.33; H, 3.64. Found: C, 56.18; H, 3.64.
(E)-2-propeneselenoic acid, 3-(4-methylphenyl)-Se-phenyl ester 5e. Yellow solid;
◦
◦
1
mp 86 C–87 C; IR (KBr): υ (cm−1) 1697, 1608; H NMR δ 2.39 (s, 3H), 6.74 (d, J =
16.0 Hz, 1H), 7.22 (d, J = 8.0 Hz, 2H), 7.41–7.47 (m, 5H), 7.58–7.62 (m, 3H); 13C NMR
δ 21.7, 125.3, 126.4, 128.7, 129.0, 129.4, 129.9, 131.2, 136.0, 141.3, 141.6, 191.1; MS m/z
(Jrel.,%): 303 (100) [M+H]+. Anal. Calcd. for C16H14OSe: C, 63.79; H, 4.68. Found: C,
63.87; H, 4.67.
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