A one-pot synthesis of novel functionalized (E)-β-arylvinyl bromides from anti-2,3-dibromo-3-(4-carboxyphenyl)propanoic acid

Article abstract of DOI:10.1515/znb-2008-0710

A facile one-pot synthesis of functionalized (E)-β-arylvinyl bromides bearing various 4-alkoxy-carbonyl and 4-aryloxycarbonyl groups was achieved by debrominative decarboxylation of anti-2,3-dibromo-3-(4-carboxyphenyl)propanoic acid in the presence of AgOAc and subsequent esterification in the presence of dicyclohexyl carbodiimide and dimethylaminopyridine. This method gives (E)-β-arylvinyl bromides in high stereoselectivities and high yields, and tolerates aldehyde, ester, and nitro functional groups.

Full text of DOI:10.1515/znb-2008-0710

A One-pot Synthesis of Novel Functionalized (E)-β-Arylvinyl Bromides
from anti-2,3-Dibromo-3-(4-carboxyphenyl)propanoic Acid
Chunxiang Kuanga, Yubo Jianga, Qing Yangb, Wensheng Zhanga, and Yaolin Wenc
a Department of Chemistry, Tongji University, Siping Road 1239, Shanghai 200092, China
b School of Pharmacy, Fudan University, Yixueyuan Road 138, Shanghai 200032, China
c Unilever Research China, Tianzhou Road 99, Shanghai 200233, China
Reprint requests to Prof. C. Kuang. Fax: +86-21-6598-3191. E-mail: kuangcx@mail.tongji.edu.cn or
Dr. Q. Yang. Fax: +86-21-5423-7692. E-mail: yangqing68@fudan.edu.cn
Z. Naturforsch. 2008, 63b, 865 – 870; received February 16, 2008
A facile one-pot synthesis of functionalized (E)-β-arylvinyl bromides bearing various 4-alkoxy-
carbonyl and 4-aryloxycarbonyl groups was achieved by debrominative decarboxylation of anti-2,3-
dibromo-3-(4-carboxyphenyl)propanoic acid in the presence of AgOAc and subsequent esterification
in the presence of dicyclohexyl carbodiimide and dimethylaminopyridine. This method gives (E)-β-
arylvinyl bromides in high stereoselectivities and high yields, and tolerates aldehyde, ester, and nitro
functional groups.
Key words: (E)-β-Arylvinyl Bromides, Stereoselectivity, One-pot Synthesis, Esterification
Introduction
tion of (E)-β-arylvinyl bromides bearing various func-
tional groups.
(E)-β-Arylvinyl bromides are important building
blocks in organic synthesis, especially as intermedi-
ates for carbon-carbon and carbon-hetero atom bond
formation by transition metal-catalyzed coupling reac-
tions [1]. The coupling products from functionalized
(E)-β-arylvinyl bromides have found numerous appli-
cations in the preparation of pharmaceuticals, liquid
crystal and natural products [2]. Although there is a ne-
cessity to incorporate functional groups in (E)-β-aryl-
vinyl bromides in order to find novel functionalized
compounds, synthetic methods available are limited in
scope. Traditional methods for preparation of (E)-β-
arylvinyl bromides can be classified into three major
categories. The first method is the Hunsdiecker-type
bromodecarboxylation [3] and the decarboxylation of
cinnamic acid dibromides [2b]. The second method
is the conversion of 1,1-dibromoalkenes to the corre-
sponding (E)-β-arylvinyl bromides by a reduction us-
ing diethyl phosphonate [4], an organolithium reagent
[5], a Grignard reagent [6], or lithium aluminum hy-
On the other hand, to find more convenient and
efficient methods for the synthesis of functional-
ized (E)-β-arylvinyl bromides is our ongoing pro-
gram. One of us previously reported the stereose-
lective synthesis of (E)-β-arylvinyl bromides by mi-
crowave irradiation of the corresponding anti-3-aryl-
2,3-dibromopropanoic acids in AcOH in the presence
of AgOAc [9]. Herein, we report a one-pot synthesis
of novel functionalized (E)-β-arylvinyl bromides (4)
having various 4-alkoxycarbonyl and 4-aryloxycarb-
onyl groups including aldehyde, ester or nitro moieties
from anti-2,3-dibromo-3-(4-carboxyphenyl)propanoic
acid (1) (Scheme 1). To the best of our knowledge,
the one-pot synthesis of functionalized (E)-β-arylvinyl
bromides from anti-2,3-dibromo-3-(4-carboxyphenyl)
propanoic acid has not been reported.
Results and Discussion
The starting dibromide 1 was easily prepared in two
dride [7]. The third method involves the reaction of steps by Knoevenagel condensation of 4-formylbenz-
CHBr3 with aryl aldehyde mediated by CrCl2 lead- oic acid with malonic acid followed by bromination
ing to the formation of (E)-β-arylvinyl bromides [8]. of the (E)-4-(2-carboxyvinyl)benzoic acid. The first
Generally, the above methods are not tolerant to reac- step of the following one-pot reaction was carried out
tive groups such as the aldehyde group. Hence it is ex- under conventional thermal conditions and gave (E)-
tremely difficult to apply these methods in the prepara- 4-(2-bromovinyl)benzoic acid (2) in high yield with
c
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866
C. Kuang et al. · Novel Functionalized (E)-β-Arylvinyl Bromides
Fg-R = alkyl or aryl groups bearing a -CHO, -CO2R, -NO2 functional group
Compound Fg-R Compound Fg-R
4a
4b
4c
4d
4e
4f
C2H5
4g
4h
4i
5-isopropyl-2-methylphenyl
4-formylphenyl
4-(propoxycarbonyl)phenyl
4-nitrophenyl
naphthalen-2-yl
i-C3H7
n-C8H17
cyclohexyl
benzyl
4j
4k
4l
phenyl
naphthalen-1-1yl
Scheme 1. One-pot synthesis of functionalized (E)-β-arylvinyl bromides.
Scheme 2. Coupling of (E)-
4-(2-bromovinyl)benzoic acid
with the Wang resin.
high stereoselectivity. Compound 2 carrying a car- (E)-β-arylvinyl bromides. (E)-β-Arylvinyl bromides
boxyl group is a new synthon for the preparation of carrying a naphthyl group (4k – l) were also easily
various derivatives that are useful intermediates in or- prepared in excellent yields. Even if an electron-
ganic synthesis. In the second step, we chose DCC/ withdrawing group such as –CHO, –CO2R, –NO2 was
DMAP as coupling agent for the esterification of acid present in the molecule, the reaction proceeded stereo-
2 with alcohols or phenols 3.
selectively in high yields.
It would be very convenient for a one-pot reaction
to use the same solvent in two successive steps. As
we previously reported, HOAc was the solvent in the
preparation of (E)-β-arylvinylbromides by microwave
irradiation of anti-3-aryl-2,3-dibromopropanoic acids
in the presence of AgOAc, but HOAc can not be ap-
plied in the esterification step. Recently, we found that
the conversion of dibromide 1 to acid 2 could be car-
ried out in benzene. When benzene was applied as
solvent for the DCC/DMAP coupling esterification, it
gave a high yield compared to other solvents such as
DMF, CH2Cl2. Therefore, benzene was used as the
common solvent for the two successive steps.
Various (E)-β-arylvinyl bromides were prepared by
this one-pot method. The results are summarized in
Scheme 1.
Further, acid 2 could be attached to the benzyl alco-
hol of Wang resin using a DCC/DMAP coupling pro-
cedure at ambient temperature to afford ester 5 in high
yield (Scheme 2). The Wang resin-bound ester 5 carry-
ing an active bromovinyl group can be applied to com-
binatorial and solid phase organic synthesis, which are
efficient techniques for the production of combinato-
rial libraries and are extensively used by the pharma-
ceutical and agricultural industries. Further, ester 5 is
an excellent substrate for Stille, Suzuki or Heck reac-
tions [1].
Conclusion
In summary, we have developed a simple and effi-
cient one-pot synthetic method for the preparation of
Isolated yields varied from 85 % to 94 %, and the 4-alkoxycarbonyl- and 4-aryloxy carbonyl (E)-β-aryl-
1
E/Z ratio determined by H NMR spectroscopy was vinyl bromides bearing various functional groups in
over 98: 2. These results indicate that the present re- high stereoselectivities and high yields. A wide range
action is very useful for the synthesis of both 4-alk- of functional groups including aldehyde, ester, and ni-
oxycarbonyl- (4a – e) and 4-aryloxycarbonyl- (4f – l) tro groups were found to tolerate the DCC/DMAP
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C. Kuang et al. · Novel Functionalized (E)-β-Arylvinyl Bromides
867
esterification condition. These functionalized (E)-β- J = 8.4 Hz, 2H of Ph). – 13C NMR (75 MHz, [D6]DMSO):
δ = 111.34, 126.35 (2 × C), 129.72, 130.28, 136.04, 139.64,
140.77, 166.96. – MS (EI): m/z (%) = 228 (48) [M+2]+,
226 (47) [M]+, 211 (99), 209 (100), 102 (88). – HRMS:
m/z = 225.9628 (calcd. 225.9629 for C9H779BrO2, [M]+). –
C9H7BrO2 (227.05): calcd. C 47.61, H 3.11, Br 35.19; found
C 47.55, H 3.02, Br 35.17.
arylvinyl bromides are important synthetic targets and
widely used synthons for synthetic chemists.
Experimental Section
Melting points were recorded using a Yanagimoto mi-
cro melting point apparatus and are uncorrected. 1H and
13C NMR spectra were recorded using a Bruker AM-300
spectrometer at 300 MHz (1H) and at 75 MHz (13C) in
CDCl3 with SiMe4 as an internal standard. Mass spectra
were obtained by EI, MALDI, and ESI methods, and HRMS
was measured by the EI method. IR spectra were recorded
on a Shimadzu IR-408 spectrophotometer. Elemental analy-
ses were performed on a Flash EA1112 instrument. Organic
solvents used were dried by standard methods when nec-
essary. Commercially obtained reagents were used without
further purification. All reactions were monitored by TLC
with HuanghaiGF254 silica gel coated plates. Flash column
chromatography was carried out using 300 – 400 mesh silica
gel at medium pressure. (E)-4-(2-Carboxyvinyl)benzoic acid
was prepared according to a literature procedure [10].
One-pot synthesis of functionalized (E)-β-arylvinyl bromides
4; general procedure
A mixture of anti-2,3-dibromo-3-(4-carboxyphenyl)prop-
anoic acid (1, 1.0 mmol), AgOAc (1.2 mmol) and benzene
(15 mL) was heated to 70 ◦C and stirred for 2 h, then cooled
to r. t. ROH (3, 1.0 mmol) and DMAP (1.0 mmol) were added
and the reaction mixture stirred for 10 min. DCC (1.5 mmol)
was added and the reaction mixture stirred for 24 h at ambi-
ent temperature. Subsequently water (20 mL) was added to
the mixture, and the product was extracted with EtOAc. The
organic layer was washed with sodium bicarbonate solution
and water and then dried with anhydrous sodium sulfate. Af-
ter evaporation of the solvent, the crude product was puri-
fied by column chromatography on silica gel with EtOAc-
hexane to give 4-alkoxycarbonyl- and 4-aryloxycarbonyl-
(E)-β-arylvinyl bromides 4.
anti-2,3-Dibromo-3-(4-carboxyphenyl)propanoic acid (1)
1 was prepared according to the previously described
◦
procedure [11]. White solid, m. p. 288 – 289 C (HOAc). –
Ethyl (E)-4-(2-bromovinyl)benzoate (4a)
IR (KBr): ν = 1704 (C=O), 930, 746 cm−1. – 1H NMR
(300 MHz, [D6]DMSO): δ = 5.40 (d, J = 11.9 Hz, 1H,
Ar-CHBr-), 5.62 (d, J = 11.9 Hz, 1H, -CHBr-), 7.77 (d,
J = 7.4 Hz, 2H of Ph), 7.93 (d, J = 7.4 Hz, 2H of Ph). –
MS (EI): m/z (%) = 354 (23) [M+4]+, 352 (47) [M+2]+,
350 (24) [M]+, 271 (42), 148 (100). – HRMS: m/z =
351.8766 (calcd. 351.8768 for C10H879Br81BrO4, [M]+). –
C10H8Br2O4 (351.98): calcd. C 34.12, H 2.29, Br 45.40;
found C 34.18, H 2.23, Br 45.35.
Prepared from compound 1 and ethanol (3a), 224 mg
(88 %). Colorless oil. – IR (neat): ν = 1714 (C=O), 1276,
1
1103, 935, 746 cm−1. – H NMR (300 MHz, CDCl3): δ =
1.39 (t, J = 7.3 Hz, 3H, CH3-CH2-), 4.37 (q, J = 7.3 Hz, 2H,
-O-CH2-CH3), 6.91 (d, J = 14.2 Hz, 1H, Br-CH=CH-), 7.14
(d, J = 14.2 Hz, 1H, Ar-CH=CH-), 7.35 (d, J = 8.6 Hz, 2H
of Ph), 8.00 (d, J = 8.6 Hz, 2H of Ph). – 13C NMR (75 MHz,
CDCl3): δ = 14.27, 61.03, 109.27, 125.88, 129.96, 130.03,
136.33, 139.91, 166.11. – MS (EI): m/z (%) = 256 (48)
[M+2]+, 254 (47) [M]+, 228 (36), 226 (37), 211 (99), 209
(100), 102 (91). – HRMS: m/z = 253.9945 (calcd. 253.9942
for C11H1179BrO2, [M]+).
(E)-4-(2-Bromovinyl)benzoic acid (2)
A mixture of anti-2,3-dibromo-3-(4-carboxyphenyl)prop-
anoic acid (1, 1.0 mmol), AgOAc (1.2 mmol), and benzene
(15 mL) was heated to 70 ◦C, stirred for 2 h, and cooled to r. t.
Water and EtOAc were added to the reaction mixture, and the
organic layer was separated. The aqueous layer was extracted
Isopropyl (E)-4-(2-bromovinyl)benzoate (4b)
Prepared from compound 1 and propan-2-ol (3b), 248 mg
with EtOAc. The combined organic layers were washed with (92 %). Colorless oil. – IR (neat): ν = 1709 (C=O), 1271,
1
water and brine and dried over anhydrous magnesium sulfate. 1098, 930, 746 cm−1. – H NMR (300 MHz, CDCl3): δ =
Evaporation of the solvent gave the crude product, which 1.29 (d, J = 6.6 Hz, 6H, -CH3), 5.13 – 5.21 (m, 1H, -CH-
was subjected to column chromatography (silica gel, hex- CH3), 6.84 (d, J = 14.1 Hz, 1H, Br-CH=CH-), 7.06 (d,
ane / EtOAc = 10 / 3, Rf = 0.42) to afford (E)-4-(2-bromo- J = 14.1 Hz, 1H, Ar-CH=CH-), 7.28 (d, J = 8.1 Hz, 2H of
vinyl)benzoic acid 2 in 96 % yield. Colorless crystals, m. p. Ph), 7.92 (d, J = 8.1 Hz, 2H of Ph). – 13C NMR (75 MHz,
268 ◦C (hexane/EtOAc). – IR (KBr): ν =1716 (C=O), 1608, CDCl3): δ = 21.88, 66.44, 109.16, 125.81, 129.99, 130.37,
935 cm−1. – 1H NMR (300 MHz, [D6]DMSO): δ = 7.30 136.35, 139.80, 156.56. – MS (EI): m/z (%) = 270 (45)
(d, J = 13.8 Hz, 1H, Br-CH=CH-), 7.48 (d, J = 13.8 Hz, [M+2]+, 268 (46) [M]+, 228 (37), 226 (38), 211 (99), 209
1H, Ar-CH=CH-), 7.60 (d, J = 8.4 Hz, 2H of Ph), 7.90 (d, (100), 102 (88). – HRMS: m/z = 268.0096 (calcd. 268.0098
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C. Kuang et al. · Novel Functionalized (E)-β-Arylvinyl Bromides
for C12H1379BrO2, [M]+). – C12H13BrO2 (269.13): calcd. Phenyl (E)-4-(2-bromovinyl)benzoate (4f)
C 53.55, H 4.87, Br 29.69; found C 53.64, H 4.90, Br 29.74.
Prepared from compound 1 and ◦phenol (3f), 248 mg
(82 %). White solid, m. p. 112 – 113 C (hexane/EtOAc). –
IR (KBr): ν = 1729 (C=O), 1261, 1072, 940, 741 cm−1. –
1H NMR (300 MHz, CDCl3): δ = 6.99 (d, J = 14.1 Hz,
1H, Br-CH=CH-), 7.17 – 7.23 (m, 3H; 2H of Ph, 1H, Ar-
CH=CH-), 7.30 (d, J = 7.8 Hz, 1H of Ph), 7.42 – 7.47 (m,
4H, 4H of Ph), 8.17 (d, J = 8.1 Hz, 2H of Ph). – 13C NMR
(75 MHz, CDCl3): δ = 109.85, 121.60 (2 × C), 125.88
(3 × C), 126.08 (2 × C), 129.45 (2 × C), 130.67 (2 × C),
136.23, 140.66, 165.90. – MS (EI): m/z (%) = 304 (48)
[M+2]+, 302 (47) [M]+, 228 (36), 226 (35), 211 (99), 209
(100), 102 (89). – HRMS: m/z = 301.9945 (calcd. 301.9942
for C15H1179BrO2, [M]+). – C15H11BrO2 (303.15): calcd.
C 59.43, H 3.66, Br 26.36; found C 59.48, H 3.69, Br 26.40.
Octyl (E)-4-(2-bromovinyl)benzoate (4c)
Prepared from compound 1 and octan-1-ol (3c), 305 mg
(90 %). Colorless oil. – IR (neat): ν = 1714 (C=O), 1271,
1
1103, 935, 741 cm−1. – H NMR (300 MHz, CDCl3): δ =
0.88 (t, J = 7.4 Hz, 3H, CH3-CH2), 1.28 – 1.95 (m, 12H,
-CH2-), 4.31 (t, J = 6.6 Hz, 2H, -OCH2-CH2-), 6.92 (d, J =
14.3 Hz, 1H, Br-CH=CH-), 7.14 (d, J = 14.3 Hz, 1H, Ar-
CH=CH-), 7.36 (d, J = 8.2 Hz, 2H of Ph), 8.00 (d, J =
8.2 Hz, 2H of Ph). – 13C NMR (75 MHz, CDCl3): δ = 14.03,
22.58, 25.39, 29.13, 29.18, 31.72, 34.85, 65.18, 109.23,
125.85, 130.01, 130.08, 135.32, 139.89, 168.11. – MS (EI):
m/z (%) = 340 (45) [M+2]+, 338 (46) [M]+, 228 (36), 226
(35), 211 (99), 209 (100), 102 (89). – HRMS: m/z = 338.0880
(calcd. 338.0882 for C17H2379BrO2, [M]+). – C17H23BrO2
(339.27): calcd. C 60.18, H 6.83, Br 23.55; found C 60.24,
H 6.79, Br 23.58.
5-Isopropyl-2-methylphenyl (E)-4-(2-bromovinyl) benzoate
(4g)
Prepared from compound 1 and 5-isopropyl-2-methyl-
phenol (3g), 331 mg (92 %). Colorless oil. – IR (neat):
ν = 1729 (C=O), 1261, 1082, 935, 746 cm−1. – 1H NMR
(300 MHz, CDCl3): δ = 1.16 (d, J = 12.9 Hz, 6H, CH3-CH-),
2.27 (s, 3H, Ar-CH3), 2.91 – 3.01 (q, J = 6.2 Hz, 1H, -CH-
CH3), 6.86 – 7.01 (m, 3H, Br-CH=CH-, 2H of Ph), 7.09 –
7.19 (m, 2H, Ar-CH=CH-, 1H of Ph), 7.37 (d, J = 8.2 Hz, 2H
of Ph), 8.10 (d, J = 8.2 Hz, 2H of Ph). – 13C NMR (75 MHz,
CDCl3): δ = 20.82, 25.42, 27.25, 109.85, 122.78, 126.16,
126.46, 127.20, 129.06, 130.65, 136.24, 136.63, 137.09,
140.64, 148.04, 164.85. – MS (EI): m/z (%) = 360 (48)
[M+2]+, 358 (47) [M]+, 228 (36), 226 (35), 211 (99), 209
(100), 102 (89). – HRMS: m/z = 358.0569 (calcd. 358.0569
for C19H1979BrO2, [M]+). – C19H19BrO2 (359.26): calcd.
C 63.52, H 5.33, Br 22.24; found C 63.48, H 5.38, Br 22.38.
Cyclohexyl(E)-4-(2-bromovinyl)benzoate (4d)
Prepared from compound 1 and cyclohexanol (3d),
284 mg (92 %). White solid, m. p. 61 – 62 ◦C (hex-
ane/EtOAc). – IR (KBr): ν = 1714 (C=O), 1270, 1103, 935,
1
751 cm−1. – H NMR (300 MHz, CDCl3): δ = 1.10 – 1.86
(m, 10H, -CH2-), 4.92 – 4.98 (m, 1H, -OCH-), 6.84 (d, J =
14.2 Hz, 1H, Br-CH=CH-), 7.07 (d, J = 14.2 Hz, 1H, Ar-
CH=CH-), 7.28 (d, J = 8.2 Hz, 2H of Ph), 7.93 (d, J =
8.2 Hz, 2H of Ph). – 13C NMR (75 MHz, CDCl3): δ =
23.61, 24.64, 31.57, 73.14, 109.13, 125.82, 130.01, 130.49,
136.37, 139.78, 165.45. – MS (EI): m/z (%) = 310 (49)
[M+2]+, 308 (48) [M]+, 228 (39), 226 (38), 211 (99), 209
(100), 102 (90). – HRMS: m/z = 308.0410 (calcd. 308.0412
for C15H1779BrO2, [M]+). – C15H17BrO2 (309.20): calcd.
C 58.27, H 5.54, Br 25.84; found C 58.30, H 5.62, Br 25.80.
4-(Formylphenyl) (E)-4-(2-bromovinyl)benzoate (4h)
Benzyl (E)-4-(2-bromovinyl)benzoate (4e)
Prepared from compound 1 and 4-hydroxybenzaldehyde
◦
Prepared from compound 1 and phenylmethanol (3e), (3h), 308 mg (93 %). White solid, m. p. 163 – 164 C (hex-
285 mg (90 %). White solid, m. p. 50 – 52 ◦C (hex- ane/EtOAc). – IR (KBr): ν = 1741 (C=O), 1734 (C=O),
ane/EtOAc). – IR (KBr): ν = 1714 (C=O), 1261, 1082, 1271, 1072, 940, 741 cm−1. – 1H NMR (300 MHz, CDCl3):
940, 751 cm−1. – 1H NMR (300 MHz, CDCl3): δ = 5.28 δ = 7.01 (d, J = 14.2 Hz, 1H, Br-CH=CH-), 7.20 (d, J =
(s, 2H, -CH2-Ph), 6.83 (d, J = 14.1 Hz, 1H, Br-CH=CH-), 14.2 Hz, 1H, Ar-CH=CH-), 7.40 – 7.47 (m, 4H of Ph), 7.99
7.05 (d, J = 14.1 Hz, 1H, Ar-CH=CH-), 7.28 – 7.38 (m, (d, J = 8.4 Hz, 2H of Ph), 8.17 (d, J = 8.1Hz, 2H of
7H, 2H of Ph, 5H of Ph), 7.95 (d, J = 8.3 Hz, 2H of Ph), 10.04 (s, 1H, -CHO). – 13C NMR (75 MHz, CDCl3):
Ph). – 13C NMR (75 MHz, CDCl3): δ = 66.75, 109.45, δ = 110.27, 122.43, 126.20, 128.27, 130.78, 131.22, 134.06,
125.93, 128.16, 128.26, 128.57, 129.58, 130.21, 135.90, 136.10, 141.10, 155.54, 164.01, 190.82. – MS (EI): m/z
136.29, 140.14, 165.90. – MS (EI): m/z ( %) = 318 (48) (%) = 332 (90) [M+2]+, 330 (92) [M]+, 228 (36), 226 (35),
[M+2]+, 316 (47) [M]+, 228 (36), 226 (35), 211 (99), 209 211 (99), 209 (100), 102 (89). – HRMS: m/z = 329.9888
(100), 102 (89). – HRMS: m/z = 316.0099 (calcd. 316.0098 (calcd. for C16H1179BrO3, [M]+). – C16H11BrO3 (331.16):
for C16H1379BrO2, [M]+). – C16H13BrO2 (317.18): calcd. calcd. C 58.03, H 3.35, Br 24.13; found C 58.10, H 3.30,
C 60.59, H 4.13, Br 25.19; found C 60.62, H 4.20, Br 25.22. Br 24.19.
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C. Kuang et al. · Novel Functionalized (E)-β-Arylvinyl Bromides
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Propyl (E)-4-(4-(2-bromovinyl)benzoyloxy)benzoate (4i)
Prepared from compound 1 and propyl 4-hydroxybenz-
MS (EI): m/z ( %) = 354 (88) [M+2]+, 352 (90) [M]+, 228
(40), 226 (39), 211 (99), 209 (100), 102 (92). – HRMS: m/z =
352.0096 (calcd. 352.0098 for C19H1379BrO2, [M]+). –
C19H13BrO2 (353.21): calcd. C 64.61, H 3.71, Br 22.62;
found C 64.70, H 3.75, Br 22.58.
◦
oate (3i), 358 mg (92 %). White solid, m. p. 100 – 101 C
(hexane/EtOAc). – IR (KBr): ν = 1738 (C=O), 1719 (C=O),
1281, 1072, 940, 762 cm−1. – 1H NMR (300 MHz, CDCl3):
δ = 1.04 (t, J = 7.5 Hz, 3H, CH3-CH2-), 1.75 – 1.84 (m, 2H,
CH3-CH2-OCH2-), 4.30 (t, J = 6.6 Hz, 2H, -OCH2-), 7.00
(d, J = 14.2 Hz, 1H, Br-CH=CH-), 7.20 (d, J = 14.2 Hz,
1H, Ar-CH=CH-), 7.27 – 7.46 (m, 4H, 4H of Ph), 8.13 – 8.18
(m, 4H, 4H of Ph ). – 13C NMR (75 MHz, CDCl3): δ =
10.46, 22.06, 66.63, 110.15, 121.61, 126.15, 128.15, 128.49,
130.75, 131.13, 136.13, 140.93, 154.38, 164.12, 165.82. –
MS (EI): m/z (%) = 390 (90) [M+2]+, 388 (88) [M]+, 228
(40), 226 (38), 211 (99), 209 (100), 102 (85). – HRMS: m/z =
388.0313 (calcd. 388.0310 for C19H1779BrO4, [M]+). –
C19H17BrO4 (389.24): calcd. C 58.63, H 4.40, Br 20.53;
found C 58.58, H 4.47, Br 20.42.
Naphthalen-1-yl (E)-4-(2-bromovinyl)benzoate (4l)
Prepared from compound 1 and naphthalen-1-ol (3l),
300 mg (85 %). White solid, m. p.118 – 119 ◦C (hex-
ane/EtOAc). – IR (KBr): ν = 1729 (C=O), 1255, 1057, 940,
762 cm−1. – 1H NMR (300 MHz, CDCl3): δ = 7.02 (d, J =
14.4 Hz, 1H, Br-CH=CH-), 7.23 (d, J = 14.4 Hz, 1H, Ar-
CH=CH-), 7.37 (d, J = 7.8 Hz, 1H, Ar-H), 7.48 – 7.56 (m,
5H, Ar-H), 7.80 (d, 1H, J = 8.1 Hz), 7.91 (d, J = 8.7 Hz, 2H,
Ar-H), 8.30 (d, J = 8.1 Hz, 2H of Ph). – 13C NMR (75 MHz,
CDCl3): δ = 110.01, 118.17, 121.15, 125.42, 126.09, 126.24,
126.48, 126.89, 128.04, 128.84, 130.83, 134.67, 136.23,
140.88, 146.73, 164.69. – MS (EI): m/z (%) = 354 (48)
[M+2]+, 352 (49) [M]+, 228 (38), 226 (37), 211 (99), 209
(100), 102 (90). – HRMS: m/z = 352.0096 (calcd. 352.0098
for C19H1379BrO2, [M]+). – C19H13BrO2 (353.21): calcd.
C 64.61, H 3.71, Br 22.62; found C 64.71, H 3.74, Br 22.66.
4-(Nitrophenyl) (E)-4-(2-bromovinyl)benzoate (4j)
Prepared from compound 1 and 4-nitrophenol (3j),
327 mg (94 %). Yellow solid, m. p. 161 – 162 ◦C (hex-
ane/EtOAc). – IR (KBr): ν = 1729 (C=O), 1255, 1057, 940,
746 cm−1. – 1H NMR (300 MHz, CDCl3): δ = 7.02 (d, J = Preparation of (E)-4-(2-bromovinyl)benzoic acid linked to
14.2 Hz, 1H, Br-CH=CH-), 7.20 (d, J = 14.2 Hz, 1H, Ar- Wang resin (5)
CH=CH-), 7.40 – 7.48 (m, 4H, 4H of Ph), 8.16 (d, J = 8.8 Hz,
Wang resin (5 mmol, 1.0 mmol g−1) was swollen in a min-
2H of Ph), 8.34 (d, J = 8.8 Hz, 2H of Ph). – 13C NMR
imal amount of benzene, and (E)-4-(2-bromovinyl)benzoic
(75 MHz, CDCl3): δ = 110.49, 122.51, 125.22, 126.25,
acid (2, 15 mmol), DCC (15 mmol), DMAP (1 mmol) in
127.88, 130.84, 136.04, 141.32, 145.41, 155.58, 163.71. –
benzene (30 mL) were added sequentially to the resin. The
MS (EI): m/z (%) = 349 (46) [M+2]+, 347 (48) [M]+, 228
resulting mixture was reacted for 24 h. The resin was fil-
(36), 226 (35), 211 (99), 209 (100), 102 (89). – HRMS: m/z =
tered and washed consecutively with benzene, CH2Cl2 and
346.9795 (calcd. 346.9793 for C15H1079BrNO4, [M]+). –
MeOH. The resin was dried under reduced pressure for
C15H10BrNO4 (348.15): calcd. C 51.75, H 2.90, Br 22.95;
24 h. The loading of the resin was estimated by IR analysis
found C 51.78, H 2.96, Br 22.86.
(v(C=O) = 1734 cm−1). The coupling yield was determined
by cleaving 100 mg of the resin with a solution of 20 % TFA
in CH2Cl2 for 20 min at ambient temperature. The solvent
Naphthalen-2-yl (E)-4-(2-bromovinyl)benzoate (4k)
mixture was evaporated and the residue recrystallized to pro-
vide 2 in 91 % yield. Compound 2 was identical with authen-
tic samples.
Prepared from compound 1 and naphthalen-2-ol (3k),
325 mg (92 %). White solid, m. p. 147 – 148 ◦C (hex-
ane/EtOAc). – IR (KBr): ν = 1724 (C=O), 1528, 1348,
1276, 1067, 940, 746 cm−1. – 1H NMR (300 MHz, CDCl3):
δ = 6.93 (d, J = 13.6 Hz, 1H, Br-CH=CH-), 7.13 (d, J =
13.6 Hz, 1H, Ar-CH=CH-), 7.29 (d, J = 9.0 Hz, 1H, Ar-H),
7.38 – 7.47 (m, 4H, Ar-H), 7.62 (s, 1H, Ar-H), 7.75 – 7.89
(m, 3H, 3H of Ph), 8.14 (d, J = 8.1 Hz, 2H of Ph). –
13C NMR (75 MHz, CDCl3): δ = 109.90, 118.61, 121.10,
125.71, 126.12, 126.56, 127.63, 127.75, 129.01, 129.43,
130.72, 131.48, 133.76, 136.24, 140.73, 148.49, 165.90. –
Acknowledgements
The work was supported by the Natural Science Founda-
tion of Shanghai, China (No. 06ZR14085) and by the Scien-
tific Research Foundation for the Returned Overseas Chinese
Scholars, State Education Ministry. We would like to thank
the Instrumental Analysis Center, Tongji University, China,
for asstistance.
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