Decarboxylative Tribromination for the Selective Synthesis of Tribromomethyl Ketone and Tribromovinyl Derivatives

Article abstract of DOI:10.1002/adsc.201800851

Tribromomethyl ketone and tribromovinyl derivatives were selectively prepared from the decarboxylative tribromination. The reaction between propiolic acid derivatives and dibromoisocyanuric acid (DBCA)/H₂O afforded predominantly a tribromomethyl ketone derivative in the presence of AgOAc (10 mol%). When the same reaction was conducted with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) instead of AgOAc, tribromovinyl derivatives were exclusively formed in good yields. It was found that ethynyl bromide is an intermediate. (Figure presented.).

Full text of DOI:10.1002/adsc.201800851

Title: Decarboxylative Tribromination for the Selective Synthesis of
Tribromomethyl Ketone and Tribromovinyl Derivatives
Authors: Aravindan Jayaraman, Eunjeong Cho, Jimin Kim, and
Sunwoo Lee
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800851
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10.1002/adsc.201800851
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.200((will be filled in by the editorial staff))
Decarboxylative Tribromination for the Selective Synthesis of
Tribromomethyl Ketone and Tribromovinyl Derivatives
Aravindan Jayaraman,a Eunjeong Cho,a Jimin Kim,a and Sunwoo Lee*,a
a Department of Chemistry, Chonnam National University, Gwangju 61186, Republic of Korea
Fax: (+82) 62-530-3389; e-mail: sunwoo@chonnam.ac.kr
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.200######.
When the same reaction was conducted with 2,2,6,6-
tetramethyl-1-piperidinyloxy (TEMPO) instead of
AgOAc, tribromovinyl derivatives were exclusively
formed in good yields. It was found that ethynyl
bromide is an intermediate.
Abstract. Tribromomethyl ketone and tribromovinyl
derivatives were selectively prepared from the
decarboxylative tribromination. The reaction between
propiolic acid derivatives and dibromoisocyanuric acid
(DBCA)/H2O
afforded
predominantly
a
Keywords:
Decarboxylation;
ketone;
bromine;
tribromomethyl ketone derivative in the presence of
AgOAc (10 mol%).
tribromomethyl
tribromovinyl;
dibromoisocyanuric acid; electrophilic addition
substrate scope because the selectivity is highly
dependent on the electronic effects of the alkyne
substituents.[8] Very recently, we reported the metal-
free decarboxylative chlorination of propiolic acid for
the synthesis of trichloromethyl ketones.[9] A variety
of trichloromethyl ketone derivatives were
successfully synthesized under mild reaction
conditions. This result provided insight into the
development of synthetic methods for the production
of tribrominated compounds such as tribromomethyl
ketone and tribromovinyl derivatives. We envisioned
that the use of dibromoisocyanuric acid (DBCA),
which is an analogue of trichloroisocyanuric acid
(TCCA), in the reaction of propiolic acids might
Introduction
The development of selective synthetic methods for
preparing a series of valuable compounds from a
single starting material has received significant
attention in the field of organic synthesis.[1] In
addition, much effort has been devoted to developing
one-pot multi-bond forming reactions due to their
advantages in the atom and step economy in the
overall synthesis.[2]
Bromine-containing compounds are important
building blocks in organic synthesis and are widely
used in pharmaceuticals, agrochemicals and materials
science.[3] However tribromomethyl ketone and
tribromovinyl derivatives have been infrequently
studied compared to other multi-halogenated
compounds even though they have been used
extensively as bioactive compounds,[4] because, to the
best of our knowledge, few general synthetic methods
for their synthesis are available. Tribromomethyl
ketone is formed as a minor product in the reaction of
methyl ketone and H2O2-HBr system or 1,3-dibromo-
5,5-dimethylhydantoin (DBH).[5] A tribromovinyl
derivative was synthesized when terminal alkyne was
allowed to react with the excess amount of alumina
supported CuBr2.[6] It is known that tribromovinyl
group can be prepared from the alkynyl tellurium and
silane.[7] Recently, the synthesis of tribromomethyl
ketone and tribromovinyl derivatives from the
reaction of alkynylsilane with oxone-KBr was
reported. However, it exhibited a very limited
provide
both
products
selectively.
Dibromoisocyanuric acid is well known to the
powerful reagent for the electrophilic bromination of
aromatic compounds.[10] However, it has never been
used for the synthesis of tribromomethyl ketone and
tribromovinyl derivatives. Herein, we report the
selective synthesis of tribromomethyl ketone and
tribromo vinyl groups from the reaction of DBCA and
propiolic acid derivatives.
Results and Discussion
Phenyl propiolic acid was chosen as a standard
substrate and reacted with DBCA in the presence of
H2O. The amount of H2O used was 16 equiv which
was the same amount as in the synthesis of
trichloromethyl ketone. A number of solvents were
first tested, as shown in Table 1. When the reaction
was conducted in CH3CN, 2a was formed as a major
1
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10.1002/adsc.201800851
Advanced Synthesis & Catalysis
product with minor amounts of 3a (entry 1). The corresponding tribromomethyl ketones 2g, 2h, and 2i
reaction in DMF showed similar results, but the with 65%, 67%, and 61% yields, respectively. In
selectivity decreased (entry 2). However, for the addition, 3-(2-cyanomethyl)phenyl propiolic acid (1j)
reactions in DMAc and DMSO, the major product afforded 2j in 58% yield. Phenyl propiolic acids with
was 3a (entries 3 and 4). The addition of Pd(OAc)2, halide groups such as bromide, chloride, and fluoride
Cu(OTf)2 and Ni(OAc)2 did not yield satisfactory were afforded in good yields. However, 2q was not
results (entries 5 - 7). Interestingly, the reactions with obtained
Ag2O and AgOAc afforded only 2a with 76% and difluorophenyl)propiolic
79% yields, respectively (entries 8 and 9). No trifluoromethyl)phenyl,
from
the
reaction
acid,
of
but
3-(3,5-
3-(4-
1,1’-biphenyl-4-yl,
formation of 3a was observed in these reaction naphthalene-2-yl, and thiophen-2-yl propiolic acids
mixtures. Surprisingly, when the reaction conducted were transformed into their corresponding 2,2,2-
in
the
presence
of
2,2,6,6-tetramethyl-1- tribromomethyl ketone derivatives (2r, 2s, 2t and 2u)
piperidinyloxy (TEMPO), 3a was exclusively formed in 41-48% yields. Phenyl propiolic acids with
(entry 10). From these results, the optimal conditions electronic withdrawing substituents such as esters,
for the synthesis of tribromomethyl ketone and ketones, and aldehyde groups afforded the desired
tribromovinyl groups were determined. When the products in moderate to low yields. For ketone and
reaction of propiolic acid and DBCA/H2O was aldehyde substituents, the desired products 2w and 2x
performed with AgOAc, the tribromomethyl ketone were not obtained from the reaction performed in
group was predominantly formed. When the same CH3CN, but in DMF the reaction proceeded.
reaction was performed in the presence of TEMPO However, the 4-cyano-substituted phenyl propiolic
instead of AgOAc, the tribromovinyl group was acid failed to yield 2y in either CH3CN or DMF.
exclusively formed.
Alkyl-substituted propiolic acids such as 2-octynoic,
2-hexynoic, 2-pentynoic and 2-butynoic acids
Table 1. Optimization of the reaction conditions for afforded the corresponding tribromomethyl ketone
the synthesis of 2a and 3a.[a]
derivatives 2z, 2za, 2zb, and 2zc with 39-45% yields.
Table 2. Synthesis of tribromomethyl ketone
derivatives[a]
Ent
ry
1
2
3
4
5
6
7
Yield (%)[b]
2a/3a
71/7
66/11
8/57
5/36
40 / 27
52 / 13
64 / 8
76 / -
Solvent
Additive
CH3CN
DMF
-
-
-
DMAc
DMSO
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
-
[c]
Pd(OAc)2
Cu(OTf)2
[c]
[c]
Ni(OAc)2
8
9
10
Ag2O[c]
AgOAc[c]
TEMPO[d]
79 / -
-/90
[a]Reaction conditions : 1a (0.3 mmol), DBCA (0.45
mmol) and H2O (4.8 mmol) were reacted in solvent
(1.5 mL) at 25 oC for 12h. [b]Determined by 1H and
13C NMR with an internal standard. [c]0.03 mmol
was used. [d]0.3 mmol was used.
To evaluate the selective synthesis of
tribromomethyl ketone, a variety of aryl and alkyl-
substituted propiolic acids were reacted with
DBCA/H2O in the presence of AgOAc and the results
are summarized in Table 2. As expected, the phenyl
propiolic acid was successfully converted to 2a with
79% yield. The yields ranged from 70 to 78% for the
[a]Reaction conditions : 1 (2.0 mmol), DBCA (3.0
mmol), AgOAc (0.2 mmol) and H2O (32.0 mmol)
o
formation
of
the
alkyl-substituted
2,2,2-
were reacted in CH3CN (8.0 mL) at 25 C for 12 h.
[b]No product was formed in ether CH3CN or DMF.
[c]DMF was used as a solvent.
tribromoacetophenones such as 2b, 2c, 2d, 2e, and 2f.
Alkoxy-substituted aryl propiolic acids afforded the
2
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10.1002/adsc.201800851
Advanced Synthesis & Catalysis
After successfully demonstrating the selective
synthesis of tribromomethyl ketones in Table 2, we
proceeded to evaluate the synthesis of tribromovinyl
groups using the same starting materials. All propiolic
acid derivatives were reacted with DBCA/H2O in the
presence of TEMPO. As shown in Table 3, in most
cases the desired products bearing tribromo vinyl
groups were successfully obtained with higher yields
than those with tribromomethyl ketone. Especially,
1,2,2-tribromovinyl benzene derivatives bearing
electron withdrawing groups, such as 3v, 3w, 3x and
3y, were obtained in 78%, 86%, 87%, and 88% yields,
respectively. However, we failed to obtain 3g, 3i, and
3u due to bromination of their aryl rings. In addition,
we failed to isolate 3zb and 3zc due to their volatility,
but they were detected in the GC MS analysis.
Scheme 1. Acyl substitution reactions
The intermediates of the reaction pathway were
investigated to develop a plausible mechanism. To
identify the intermediate, the initial reaction 5 min of
phenyl propiolic acid and DBCA was monitored by
1H and 13C NMR spectroscopy and the results are
summarized in Table 4. When the reaction was
conducted in the absence of H2O and TEMPO,
phenylethynyl bromide (4a) and 3a were found with
71% and 12% yields, respectively, but only trace
amount of 2a was obtained (entry 1). When the same
reaction was conducted in the presence of TEMPO,
the yield of 4a decreased to 60% but remained as the
major product (entry 2). The reaction with H2O
afforded 2a as a major product and 4a as a minor
product in the absence of TEMPO (entry 3). However,
4a was formed as a major product in the presence of
TEMPO (entry 4). Based on these results, we propose
that phenylethynyl bromide (4a) was an intermediate
in the formation of both 2a and 3a.[11]
Table 3. Synthesis of tribromovinyl derivatives[a]
Table 4. Studies on the intermediate in the synthesis
of 2a and 3a[a]
Yield (%)
2a
trace
ND
51
ND
H2O
(equiv)
0
0
16.0
16.0
TEMPO
(equiv)
0
1.0
0
Entry
4a
71
60
11
52
3a
12
20
trace
29
[a]Reaction conditions : 1 (2.0 mmol), DBCA (3.0
1
2
3
4
mmol), TEMPO (2.0 mmol) and H2O (32.0 mmol)
o
were reacted in CH3CN (8.0 mL) at 25 C for 12 h.
[b]Failed to isolate the pure product. [c]~30% yield of
the product was detected using 1H NMR.
1.0
[a]Reaction conditions : 1a (0.3 mmol) and DBCA
(0.3 mmol) were reacted in CD3CN (1.5 mL) at 25
13
oC for 5 minute. [b]Determined by 1H and C NMR
It was observed that 2,2,2,-tribromoacetophenone
was successfully transformed into the corresponding
ester and amide via acyl substitution reactions with
benzyl alcohol and amine as shown in Scheme 1.
with internal standard. ND = not detected.
Next, we studied the reaction of 4a as an
intermediate to identify the reaction pathway, as
shown in Table 5. The reaction with DBCA/H2O in
the absence of TEMPO afforded 2a as a major
product (entry 1), and the same reaction with AgOAc
produced only 2a in 90% yield (entry 2). When the
reaction was conducted with TEMPO, only 3a formed
When
2,2,2-tribromo-
and
2,2,2-
trichloroacetophenone were used in a competitive
acyl substitution reaction with benzyl alcohol and
benzyl amine, 2,2,2-tribromoacetophenone (2a)
showed slightly higher reactivity than 2,2,2-
trichloroacetophenone (7).
3
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10.1002/adsc.201800851
Advanced Synthesis & Catalysis
with 91% yield (entry 3). These results are consistent
with that the reaction of 1a. When 4a was reacted
Table 6. Studies regarding the role of TEMPO and
with Br2 instead of DBCA, only 3a was formed with AgOAc[a]
89% yield (entry 4), but the yield of 3a decreased to
68% when using Br2/H2O (entry 5). When the
reaction was performed with TEMPO, 3a was formed
with 40% yield (entry 6). These results suggest the
following: 1) DBCA/H2O might provide Br2 and
others; 2) Br2 is a key reagent for the formation of 3a,
but not for 2a; 3) the formation of Br2 does not occur
Chamber A
Chamber B
Yield (%)
through a radical pathway.
Entry
Additive
2a
0
0
0
0
3a
56
52
12
0
1
2
3
4
-
Table 5. Results of the reaction pathway studies[a]
TEMPO
AgOAc
AgOAc
[a]Reaction conditions : Chamber A = DBCA (2.0
mmol) and H2O (32.0 mmol) were reacted in
o
CH3CN (8.0 mL) at 45 C, Chamber B = 4a (1.0
mmol) was stirred in CH3CN (3.0 mL) at 25 oC.
Yield
(%)
3a
Entry
Reagents
Additive
2a
DBCA (1 equiv) / H2O (16
equiv)
DBCA (1 equiv )/ H2O (16
equiv)
DBCA (1 equiv) / H2O (16
equiv)
18
When isotopically labeled H2 O was used in the
1
2
3
-
89
2
0
reaction with 1a and DBCA, the desired product 2a
bearing oxygen-18 was identified using high-
resolution mass spectrometry (HRMS), with a
molecular-mass of m/z = 356.7981 which corresponds
AgOAc
TEMPO
90
0
91
4
5
6
Br2 (1 equiv)
-
-
0
0
0
89
68
40
to that of C8H5Br3 O (m/z calculated for [M+H]+:
18
Br2 (1 equiv) / H2O (16 equiv)
356.8011). This suggests that the reaction pathway for
tribromomethyl ketone is different from that of
trichloromethyl ketone.
Br2 (1 equiv) / H2O (16 equiv) TEMPO
[a]Reaction conditions : 4a (0.4 mmol) was used in
CH3CN (1.5 mL) at 25 oC for 12 h. [b]Determined by
1H and 13C NMR with internal standard.
To study the role of TEMPO and AgOAc in the
subsequent reaction step, two chambers were
prepared and connected, as shown in Table 6.
Chamber A contained DBCA and H2O reacted in
18
Scheme 2. Reaction with H2 O.
Based on the above-mentioned results, we
proposed a reaction pathway as shown in Scheme 3.
Phenylpropiolic acid was chosen as a representative
alkynoic acids. Phenylpropiolic acid reacts with
DBCA to form 2-carboxy-3-phenylbromiren-1-ium
(A) followed by decarboxylation to afford 4a as an
intermediate through an ionic mechanism. It has been
previously demonstrated that the reaction of DBCA
and H2O generates bromine and hypobromous acid.[12]
In the presence of AgOAc, only HOBr can participate
in path I. The reaction of 4a and hypobromous acid
provided intermediate B and, followed by the addition
of hydroxide, afforded intermediate C and further
o
CH3CN at 45 C and Chamber B contained 4a
o
dissolved in CH3CN at 25 C. We obtained 3a in
56% yield in Chamber B (entry 1). The yield of 3a
showed 52% when TEMPO was added to Chamber A
(entry 2). These results indicated that Br2 is likely
generated from the reaction of DBCA and H2O and is
vaporized to react with 4a to afford 3a without
forming radicals. When either 10 mol% or an equal
amount of AgOAc were added, the yields of products
were 12% and 0%, respectively (entries 3 and 4).
From these results, it can be concluded that AgOAc
deactivates or blocks the formation of Br2.
bromination yielded 2a.
HOBr has been
demonstrated to oxidize TEMPO.[13] In the presence
of TEMPO, path II is predominant because HOBr can
oxidize TEMPO, in contrast to path I. Bromine
predominantly reacts with 4a to form intermediate B
and followed by the addition of bromide to afford 3a.
4
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10.1002/adsc.201800851
Advanced Synthesis & Catalysis
Although path I was suggested as an ionic mechanism, Phenylpropiolic acid (292 mg, 2.0 mmol) afforded
we cannot rule out a radical mechanism.
2,2,2-tribromo-1-phenylethanone (2a) (564 mg, 1.58
mmol, 79% yield); colorless oil; H NMR (500 MHz,
1
CDCl3): δ 8.33 (d, J = 8.7 Hz, 2H), 7.61 (t, J = 7.5 Hz,
1H), 7.48 (t, J = 8.4 Hz, 2H); 13C{1H} NMR (126
MHz, CDCl3) δ 181.5, 133.9, 131.8, 128.2, 128.2,
42.0; FTIR (neat) ʋ 3053, 1696, 1214, 991, 803 cm-1;
HRMS (FD) m/z cacld. for C8H5Br3O [M]+: 353.7891,
found: 353.7892; Anal. calcd. for C8H5Br3O : C,
26.93; H, 1.41. Found : C, 26.74; H, 1.67.
2,2,2-Tribromo-1-(o-tolyl)ethanone (2b)[14]
:
3-(o-Tolyl)propiolic acid (320 mg, 2.0 mmol)
afforded 2,2,2-tribromo-1-(o-tolyl)ethanone (2b)
1
(556 mg, 1.5 mmol, 75% yield); colorless oil; H
NMR (500 MHz, CDCl3): δ 8.01 (d, J = 7.8 Hz, 1H),
7.41 (t, J = 7.6 Hz, 1H), 7.31 (d, J = 7.7 Hz, 1H), 7.24
(t, J = 7.6 Hz, 1H), 2.40 (s, 3H); C{1H} NMR (126
13
Scheme 3. Proposed reaction pathways.
MHz, CDCl3) δ 187.4, 137.9, 132.3, 131.8, 131.2,
128.3, 125.1, 43.7, 20.8; FTIR (neat) ʋ 3057, 1728,
1261, 967, 817 cm-1; HRMS (FD) m/z cacld. for
C9H7Br3O [M]+: 367.8047, found:.367.8047; Anal.
calcd. for C9H7Br3O : C, 29.15; H, 1.90. Found : C,
29.44; H, 1.73.
Conclusion
In summary, the selective synthesis of
tribromomethyl ketone and tribromovinyl derivatives
were developed using the reaction of propiolic acid
derivatives and DBCA/H2O. In the presence of
AgOAc (10 mol%), tribromomethyl ketone
derivatives were successfully obtained in good yields.
When the reaction was conducted in the presence of
TEMPO, tribromovinyl derivatives were exclusively
formed in good yields. Alkynyl bromide was
proposed to be formed as an intermediate through an
ionic pathway. The formation of tribromomethyl
ketone likely occur through the reaction with HOBr
and the tribromovinyl group is likely produced via
reaction with bromine.
2,2,2-Tribromo-1-(m-tolyl)ethanone (2c):
3-(m-Tolyl)propiolic acid (320 mg, 2.0 mmol)
afforded 2,2,2-tribromo-1-(m-tolyl)ethanone (2c) (571
mg, 1.54 mmol, 77% yield); colorless oil; 1H NMR
(500 MHz, CDCl3): δ 8.16 (d, J = 7.9 Hz, 1H), 8.09 (s,
1H), 7.42 (d, J = 7.6 Hz, 1H), 7.36 (t, J = 7.7 Hz, 1H),
2.44 (s, 3H); 13C{1H} NMR (126 MHz, CDCl3) δ
181.8, 138.2, 134.7, 132.2, 128.9, 128.3, 127.9, 42.2,
21.4; FTIR (neat) ʋ 2920, 1694, 1165, 997, 808 cm-1;
HRMS (FD) m/z cacld. for C9H7Br3O [M]+: 367.8047,
found: 367.8047; Anal. calcd. for C9H7Br3O : C,
29.15; H, 1.90. Found : C, 29.42; H, 1.82.
2,2,2-Tribromo-1-(p-tolyl)ethanone (2d)[8]:
3-(p-Tolyl)propiolic acid (320 mg, 2.0 mmol)
afforded 2,2,2-tribromo-1-(p-tolyl)ethanone (2d) (578
mg, 1.56 mmol, 78% yield); colorless oil; H NMR
(500 MHz, CDCl3): δ 8.24 (d, J = 8.4 Hz, 2H), 7.27 (d,
1
Experimental Section
General experimental procedure for the synthesis J = 8.0 Hz, 2H), 2.44 (s, 3H); 13C{1H} NMR (126
of tribromomethyl ketones:
MHz, CDCl3) δ 181.0, 145.2, 132.0, 128.9, 125.3,
To a 20-mL screw cap vial added aryl propiolic acid 42.4, 21.7; FTIR (neat) ʋ 3034, 1691, 1183, 993, 832
(2.0 mmol, 1.0 equiv), silver acetate (23 mg, 0.2 cm-1; HRMS (FD) m/z cacld. for C9H7Br3O [M]+:
mmol, 0.1 equiv) dibromoisocyanuric acid (861 mg, 367.8047, found: 367.8047; Anal. calcd. for
3.0 mmol, 1.5 equiv) and water (576 mg, 32.0 mmol, C9H7Br3O : C, 29.15; H, 1.90. Found : C, 29.33; H,
16.0 equiv) in acetonitrile (5.0 mL), closed tightly. 1.75.
The solution was stirred at 25 °C for 12 h. The
resulting mixture charged to the separating funnel 2,2,2-Tribromo-1-(2,4-dimethylphenyl)ethanone
added water, 10% sodium thiosulphate extracted with (2e):
EtOAc. The organic layer washed with water and 3-(2,4-Dimethylphenyl)propiolic acid (348 mg, 2.0
dried over anhydrous MgSO4. After removing the mmol)
afforded
2,2,2-tribromo-1-(2,4-
EtOAc under vacuum, the crude product was purified dimethylphenyl)ethanone (2e) (547 mg, 1.42 mmol,
by column chromatography on a silica gel column 71% yield); colorless oil; 1H NMR (500 MHz,
with n-hexane/ethyl acetate as eluent to obtain the CDCl3): δ 7.99 (d, J = 8.0 Hz, 1H), 7.13 (s, 1H), 7.04
desired product.
(d, J = 8.0 Hz, 1H), 2.39 (s, 3H), 2.38 (s, 3H);
13C{1H} NMR (126 MHz, CDCl3) δ 186.6, 142.1,
138.8, 132.2, 128.9, 128.6, 125.6, 44.2, 21.4, 20.9;
2,2,2-Tribromo-1-phenylethanone (2a)[8]:
5
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10.1002/adsc.201800851
Advanced Synthesis & Catalysis
FTIR (neat) ʋ 2976, 1698, 1217, 979, 824 cm-1; HRMS (FD) m/z cacld. for C9H5Br3O3 [M]+:
HRMS (FD) m/z cacld. for C10H9Br3O [M]+: 397.7789, found: 397.7788; Anal. calcd. for
381.8204, found: 381.8212; Anal. calcd. for C9H5Br3O3 : C, 26.97; H, 1.26. Found : C, 27.01; H,
C10H9Br3O : C, 31.21; H, 2.36. Found : C, 30.97; H, 1.19.
2.49.
2-(2-(2,2,2-Tribromoacetyl)phenyl)acetonitrile
2,2,2-Tribromo-1-(4-(tert-butyl)phenyl)ethanone
(2f)[14]
3-(4-(tert-Butyl)phenyl)propiolic acid (404 mg, 2.0 2.0
mmol) afforded
(2j):
:
3-(2-(Cyanomethyl)phenyl)propiolic acid (370 mg,
mmol)
afforded
2-(2-(2,2,2-
2,2,2-tribromo-1-(4-(tert- tribromoacetyl)phenyl)acetonitrile (2j) (459 mg, 1.16
1
butyl)phenyl)ethanone (2f) (578 mg, 1.4 mmol, 70% mmol, 58% yield); colorless oil; H NMR (500 MHz,
1
yield); colorless oil; H NMR (500 MHz, CDCl3): δ CDCl3): δ 8.36 (d, J = 7.9 Hz, 1H), 7.68 (d, J = 7.8
8.30 (d, J = 8.9 Hz, 2H), 7.49 (d, J = 8.9 Hz, 2H), Hz, 1H), 7.61 (t, J = 7.6 Hz, 1H), 7.44 (t, J = 7.7 Hz,
1.36 (s, 9H); 13C{1H} NMR (126 MHz, CDCl3) δ 1H), 3.93 (s, 2H); C{1H} NMR (126 MHz, CDCl3)
13
181.0, 158.1, 132.0, 125.2, 125.2, 42.5, 35.3, 31.0; δ 185.3, 133.0, 131.3, 130.4, 130.1, 127.6, 117.1, 41.5,
FTIR (neat) ʋ 2963, 1693, 1224, 991, 850 cm-1; 22.9; FTIR (neat) ʋ 3069, 2260, 1700, 1221, 792 cm-
HRMS (FD) m/z cacld. for C12H13Br3O [M]+: 1; HRMS (FD) m/z cacld. for C10H6Br3NO [M]+:
409.8517, found: 409.8517; Anal. calcd. for 392.8000, found: 392.8002. Anal. calcd. for
C12H13Br3O : C, 34.90; H, 3.17. Found : C, 35.22; H, C10H6Br3NO : C, 30.34; H, 1.53; N, 3.54. Found : C,
3.39.
30.75; H, 1.66; N, 3.27.
2,2,2-Tribromo-1-(2-methoxyphenyl)ethanone
2,2,2-Tribromo-1-(4-bromophenyl)ethanone
(2g):
(2k)[14]
:
3-(2-Methoxyphenyl)propiolic acid (352 mg, 2.0 3-(4-Bromophenyl)propiolic acid (450 mg, 2.0 mmol)
mmol)
afforded
2,2,2-tribromo-1-(2- afforded 2,2,2-tribromo-1-(4-bromophenyl)ethanone
1
methoxyphenyl)ethanone (2g) (503 mg, 1.3 mmol, (2k) (627 mg, 1.44 mmol, 72% yield); brown oil; H
65% yield); colorless oil; 1H NMR (500 MHz, NMR (500 MHz, CDCl3): δ 8.21 (d, J = 8.8 Hz, 2H),
CDCl3): δ 7.69 – 7.67 (m, 1H), 7.47 (ddd, J = 8.4, 7.5, 7.63 (d, J = 8.8 Hz, 2H); C{1H} NMR (126 MHz,
13
1.7 Hz, 1H), 7.02 – 6.97 (m, 2H), 3.87 (s, 3H); CDCl3) δ 180.7, 133.3, 131.7, 129.5, 127, 41.2; FTIR
13C{1H} NMR (126 MHz, CDCl3) δ 187.1, 156.9, (neat) ʋ 2664, 1696, 1580, 1213, 737 cm-1; HRMS
132.5, 129.3, 122.8, 120.1, 111.8, 55.7, 43.6; FTIR (FD) m/z cacld. for C8H4Br4O [M]+: 431.6996, found:
(neat) ʋ 2923, 1650, 1485, 879, 747 cm-1; HRMS 431.6996; Anal. calcd. for C8H4Br4O : C, 22.05; H,
(FD) m/z cacld. for C9H7Br3O2 [M]+: 383.7996, 0.93. Found : C, 22.17; H, 1.18.
found: 383.7996; Anal. calcd. for C9H7Br3O2 : C,
27.94; H, 1.82. Found : C, 28.05; H, 1.63.
2,2,2-Tribromo-1-(3-bromophenyl)ethanone (2l):
3-(3-Bromophenyl)propiolic acid (450 mg, 2.0 mmol)
afforded 2,2,2-tribromo-1-(3-bromophenyl)ethanone
2,2,2-Tribromo-1-(4-methoxyphenyl)ethanone
(2h)[8]:
(2l) (601 mg, 1.38 mmol, 69% yield); brown oil; H
1
3-(4-Methoxyphenyl)propiolic acid (352 mg, 2.0 NMR (500 MHz, CDCl3): δ 8.41 (s, 1H), 8.28 (d, J =
mmol)
afforded
2,2,2-tribromo-1-(4- 8.0 Hz, 1H), 7.73 (d, J = 8.0 Hz, 1H), 7.36 (t, J = 8.0
methoxyphenyl)ethanone (2h) (518 mg, 1.34 mmol, Hz, 1H); C{1H} NMR (126 MHz, CDCl3) δ 180.3,
67% yield); colorless oil; 1H NMR (500 MHz, 136.73, 134.4, 130.2, 130.8, 129.6, 122.3, 40.7; FTIR
CDCl3): δ 8.36 (d, J = 9.1 Hz, 2H), 6.94 (d, J = 9.1 (neat) ʋ 3066, 1691, 1206, 750, 672 cm-1; HRMS
Hz, 2H), 3.90 (s, 3H); 13C{1H} NMR (126 MHz, (FD) m/z cacld. for C8H4Br4O [M]+: 431.6996, found:
CDCl3) δ 180.0, 164.0, 134.6, 120.1, 113.5, 55.6, 431.6996; Anal. calcd. for C8H4Br4O: C, 22.05; H,
42.8; FTIR (neat) ʋ 2970, 1682, 1594, 1171, 843 cm- 0.93. Found : C, 22.24; H, 1.26.
13
1; HRMS (FD) m/z cacld. for C9H7Br3O2 [M]+:
383.7996, found: 383.7995; Anal. calcd. for 2,2,2-Tribromo-1-(4-chlorophenyl)ethanone
C9H7Br3O2 : C, 27.94, H 1.82. Found : C, 28.22; H, (2m)[14]
:
1.66.
3-(4-Chlorophenyl)propiolic acid (361 mg, 2.0 mmol)
afforded 2,2,2-tribromo-1-(4-chlorophenyl)ethanone
(2m) (548 mg, 1.4 mmol, 70% yield); colorless oil;
1H NMR (500 MHz, CDCl3): δ 8.29 (d, J = 8.9 Hz,
1-(Benzo[d][1,3]dioxol-5-yl)-2,2,2-
tribromoethanone (2i):
3-(Benzo[d][1,3]dioxol-5-yl)propiolic acid (380 mg, 2H), 7.45 (d, J = 8.9 Hz, 2H); 13C{1H} NMR (126
2.0 mmol) afforded 1-(benzo[d][1,3]dioxol-5-yl)- MHz, CDCl3) δ 180.4, 140.6, 133.2, 128.6, 126.5,
2,2,2-tribromoethanone (2i) (489 mg, 1.22 mmol, 41.2; FTIR (neat) ʋ 2879, 1697, 1585, 1214, 748 cm-
61% yield); colorless oil; 1H NMR (500 MHz, 1; HRMS (FD) m/z cacld. for C8H4Br3ClO [M]+:
CDCl3): δ 8.04 (dd, J = 8.4, 1.9 Hz, 1H), 7.79 (d, J = 387.7501, found: 387.7504; Anal. calcd. for
1.8 Hz, 1H), 6.87 (d, J = 8.5 Hz, 1H), 6.09 (s, 2H); C8H4Br3ClO: C, 24.56; H, 1.03. Found : C, 24.44; H,
13C{1H} NMR (126 MHz, CDCl3) δ 179.7, 152.5, 1.24.
147.5, 129.1, 121.6, 111.7, 107.8, 102.2, 42.2; FTIR
(neat) ʋ 2888, 1682, 1484, 1439, 1247 cm-1; 2,2,2-Tribromo-1-(3-chlorophenyl)ethanone (2n):
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800851
Advanced Synthesis & Catalysis
3-(3-Chlorophenyl)propiolic acid (361 mg, 2.0 mmol) 3-([1,1'-Biphenyl]-4-yl)propiolic acid (444 mg, 2.0
afforded 2,2,2-tribromo-1-(3-chlorophenyl)ethanone mmol)
afforded
1-([1,1'-biphenyl]-4-yl)-2,2,2-
(2n) (532 mg, 1.36 mmol, 68% yield); colorless oil; tribromoethanone (2s) (390 mg, 0.9 mmol, 45%
1H NMR (500 MHz, CDCl3): δ 8.28 (t, J = 1.9 Hz, yield); colorless oil; H NMR (500 MHz, CDCl3): δ
1
1H), 8.23 (ddd, J = 8.0, 1.8, 1.0 Hz, 1H), 7.58 (ddd, J 8.44 (d, J = 8.8 Hz, 2H), 7.70 (d, J = 8.8 Hz, 2H),
= 8.0, 2.1, 1.0 Hz, 1H), 7.43 (t, J = 8.0 Hz, 1H); 7.65 (d, J = 7.0 Hz, 2H), 7.50 (t, J = 7.4 Hz, 2H), 7.45
13
13C{1H} NMR (126 MHz, CDCl3) δ 180.5, 134.8, – 7.41 (m, 1H); C{1H} NMR (126 MHz, CDCl3) δ
133.9, 131.6, 130.0, 129.8, 129.5, 40.8; FTIR (neat) ʋ 181.1, 146.7, 139.3, 132.6, 129.1, 128.7, 127.3, 126.8,
3071, 1678, 1274, 1207, 750 cm-1; HRMS (FD) m/z 126.7, 42.2; FTIR (neat) ʋ 3031, 1690, 1599, 1191,
cacld. for C8H4Br3ClO [M]+: 387.7501, found: 690 cm-1; HRMS (FD) m/z cacld. for C14H9Br3O
387.7504; Anal. calcd. for C8H4Br3ClO : C, 24.56; H, [M]+: 429.8204, found: 429.8204; Anal. calcd. for
1.03. Found : C, 24.22; H, 0.87.
C14H9Br3O : C, 38.84; H, 2.10. Found : C, 38.99; H,
2.11.
2,2,2-Tribromo-1-(4-fluorophenyl)ethanone
2,2,2-Tribromo-1-(naphthalen-2-yl)ethanone (2t):
(2o)[14]
:
3-(Naphthalen-2-yl)propiolic acid (392 mg, 2.0
3-(4-Fluorophenyl)propiolic acid (328 mg, 2.0 mmol) mmol) afforded 2,2,2-tribromo-1-(naphthalen-2-
afforded 2,2,2-tribromo-1-(4-fluorophenyl)ethanone yl)ethanone (2t) (391 mg, 0.96 mmol, 48% yield);
1
(2o) (502 mg, 1.34 mmol, 67% yield); colorless oil; colorless oil; H NMR (500 MHz, CDCl3): δ 8.96 (s,
1H NMR (500 MHz, CDCl3): δ 8.39 (m, 2H), 7.15 (m, 1H), 8.31 (dd, J = 8.8, 1.8 Hz, 1H), 7.99 (d, J = 8.2
2H); 13C{1H} NMR (126 MHz, CDCl3) δ 180.0, 165.9 Hz, 1H), 7.90 (d, J = 8.5 Hz, 2H), 7.65 (t, J = 7.5 Hz,
(d, J = 258.1 Hz), 134.8 (d, J = 9.5 Hz), 124.3 (d, J = 1H), 7.58 (t, J = 7.5 Hz, 1H); 13C{1H} NMR (126
3.3 Hz), 115.6 (d, J = 22.0 Hz), 41.5; FTIR (neat) ʋ MHz, CDCl3) δ 181.5, 135.6, 134.2, 131.9, 129.9,
3079, 1682, 1506, 1231, 1155 cm-1; HRMS (FD) m/z 129.4, 127.9, 127.7, 127.1, 126.7, 125.4, 42.2; FTIR
cacld. for C8H4Br3FO [M]+: 371.7796, found: (neat) ʋ 2985, 1737, 1373, 1236, 1044 cm-1; HRMS
371.7799; Anal. calcd. for C8H4Br3FO : C, 25.63; H, (FD) m/z cacld. for C12H7Br3O [M]+: 403.8047,
1.08. Found : C, 25.41; H, 0.94.
found: 403.8051; Anal. calcd. for C12H7Br3O : C,
35.42; H, 1.73. Found : C, 35.55; H, 1.51.
2,2,2-Tribromo-1-(3-fluorophenyl)ethanone (2p):
3-(3-Fluorophenyl)propiolic acid (328 mg, 2.0 mmol) 2,2,2-Tribromo-1-(thiophen-2-yl)ethanone (2u)[14]
:
afforded 2,2,2-tribromo-1-(3-fluorophenyl)ethanone 3-(Thiophen-2-yl)propiolic acid (304 mg, 2.0 mmol)
(2p) (495 mg, 1.32 mmol, 66% yield); colorless oil; afforded
2,2,2-tribromo-1-(thiophen-2-yl)ethanone
1H NMR (500 MHz, CDCl3): δ 8.14 (ddd, J = 7.9, 1.7, (2u) (305 mg, 0.84 mmol, 42% yield); colorless oil;
1.0 Hz, 1H), 8.01 (ddd, J = 9.8, 2.4, 1.9 Hz, 1H), 1H NMR (500 MHz, CDCl3): δ 8.27 (d, J = 4.0 Hz,
13
7.49-7.45 (m, 1H), 7.32 (m, 1H); C{1H} NMR (126 1H), 7.74 (d, J = 5.0 Hz, 1H), 7.17 (t, J = 4.7 Hz, 1H);
MHz, CDCl3) δ 180.4 (d, J = 2.5 Hz), 161.9 (d, J = 13C{1H} NMR (126 MHz, CDCl3) δ 175.4, 137.4,
248.0 Hz), 130.2 (d, J = 7.0 Hz), 129.9 (d, J = 7.7 Hz), 136.5, 132.6, 128.1, 40.9; FTIR (neat) ʋ 3103, 1666,
127.6 (d, J = 3.2 Hz), 121.1 (d, J = 21.3 Hz), 118.7 (d, 1404, 1241, 723 cm-1; HRMS (FD) m/z cacld. for
J = 24.1 Hz), 40.9; FTIR (neat) ʋ 2987, 1733, 1264, C6H3Br3OS [M]+: 359.7455, found: 359.7457; Anal.
1045, 733 cm-1; HRMS (FD) m/z cacld. for calcd. for C6H3Br3OS : C, 19.86; H, 0.83. Found : C,
C8H4Br3FO [M]+: 371.7796, found: 371.7799; Anal. 20.04; H, 1.03.
calcd. for C8H4Br3FO : C, 25.63; H 1.08. Found : C,
25.77; H, 0.95.
Methyl 4-(2,2,2-tribromoacetyl)benzoate (2v):
3-(4-(Methoxycarbonyl)phenyl)propiolic acid (408
mg, 2.0 mmol) afforded methyl 4-(2,2,2-
tribromoacetyl)benzoate (2v) (473 mg, 1.14 mmol,
2,2,2-Tribromo-1-(4-
(trifluoromethyl)phenyl)ethanone (2r):
3-(4-(Trifluoromethyl)phenyl)propiolic acid (428 mg, 57% yield); colorless oil; 1H NMR (500 MHz,
2.0
mmol)
afforded
2,2,2-tribromo-1-(4- CDCl3): δ 8.38 (d, J = 8.8 Hz, 2H), 8.13 (d, J = 8.8
(trifluoromethyl)phenyl)ethanone (2r) (348 mg, 0.82 Hz, 2H), 3.97 (s, 3H); 13C{1H} NMR (126 MHz,
1
mmol, 41% yield); colorless oil; H NMR (500 MHz, CDCl3) δ 181.3, 165.8, 134.4, 132.2, 131.6, 129.3,
CDCl3): δ 8.44 (d, J = 8.2 Hz, 2H), 7.75 (d, J = 8.3 52.6, 40.9; FTIR (neat) ʋ 2952, 1724, 1702, 1278, 749
Hz, 2H); C{1H} NMR (126 MHz, CDCl3) δ 180.8, cm-1; HRMS (FD) m/z cacld. for C10H7Br3O3 [M]+:
13
134.9 (q, J = 33.1 Hz), 132.0, 131.7, 123.2 (q, J = 411.7945, found: 411.7945; Anal. calcd. for
273.5 Hz), 125.2 (q, J = 3.7 Hz), 40.5; FTIR (neat) ʋ C10H7Br3O3 : C, 28.95; H, 1.70. Found : C, 28.99; H,
3055, 1699, 1325, 1264, 733 cm-1; HRMS (FD) m/z 1.92.
cacld. for C9H4Br3F3O [M]+: 421.7764, found:
421.7766; Anal. calcd. for C9H4Br3F3O : C, 25.44; H, 1-(4-Acetylphenyl)-2,2,2-tribromoethanone (2w):
0.95. Found : C, 25.67; H, 1.15.
3-(4-Acetylphenyl)propiolic acid (376 mg, 2.0 mmol)
afforded 1-(4-acetylphenyl)-2,2,2-tribromoethanone
(2w) (295 mg, 0.74 mmol, 37% yield); colorless oil;
1H NMR (500 MHz, CDCl3): δ 8.40 (d, J = 8.9 Hz,
1-([1,1'-Biphenyl]-4-yl)-2,2,2-tribromoethanone
(2s)[8]:
2H), 8.03 (d, J = 8.9 Hz, 2H), 2.66 (s, 3H); C{1H}
13
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800851
Advanced Synthesis & Catalysis
NMR (126 MHz, CDCl3) δ 197.1, 181.3, 140.5, 132.3, 187.9, 45.9, 20.4; FTIR (neat) ʋ 2919, 1737, 1421,
131.9, 127.9, 40.9, 26.9; FTIR (neat) ʋ 2930, 1695, 1210, 821 cm-1;
HRMS (FD) m/z cacld. for
1687, 1273, 749 cm-1; HRMS (FD) m/z cacld. for C3H3Br3O [M]+: 291.7734, found: 291.7738; Anal.
C10H7Br3O2 [M]+: 395.7996, found: 395.7996; Anal. calcd. for C3H3Br3O : C, 12.22; H, 1.03. Found : C,
calcd. for C10H7Br3O2 : C, 30.11; H, 1.77. Found : C, 12.59; H, 0.97.
29.87; H, 1.49.
General experimental procedure for the synthesis
4-(2,2,2-Tribromoacetyl)benzaldehyde (2x):
of tribromovinyl derivatives:
3-(4-Formylphenyl)propiolic acid (348 mg, 2.0 To a 20-mL screw cap vial added aryl propiolic acid
mmol) afforded 4-(2,2,2-tribromoacetyl)benzaldehyde (2.0 mmol, 1.0 equiv), acetonitrile, water (576 mg,
(2x) (269 mg, 0.7 mmol, 35% yield); colorless oil; 1H 32.0 mmol, 16.0 equiv), TEMPO (2,2,6,6-
NMR (500 MHz, CDCl3): δ 10.13 (s, 1H), 8.46 (d, J = tetramethylpiperidin-1-yl)oxidanyl) (312.4 mg, 2.0
13
8.3 Hz, 2H), 7.99 (d, J = 8.7 Hz, 2H); C{1H} NMR mmol, 1.0 equiv) dibromoisocyanuric acid (861 mg,
(126 MHz, CDCl3) δ 191.1, 181.8, 139.2, 133.5, 3.0 mmol, 1.5 equiv). The solution was stirred at
132.2, 129.1, 40.6; FTIR (neat) ʋ 2986, 1721, 1707, 25 °C for 12 h. The resulting mixture charged to the
1241, 735 cm-1; HRMS (FD) m/z cacld. for separating funnel added water, 10% sodium
C9H5Br3O2 [M]+: 381.7840, found: 381.7840; Anal. thiosulphate extracted with EtOAc. The organic layer
calcd. for C9H5Br3O2 : C, 28.09; H, 1.31. Found : C, washed with water and dried over anhydrous MgSO4.
28.11; H, 1.42.
After removing the EtOAc under vacuum, the crude
product was purified by column chromatography on a
silica gel column with n-hexane/ethyl acetate as
1,1,1-Tribromoheptan-2-one (2z):
Oct-2-ynoic acid (280 mg, 2.0 mmol) afforded 1,1,1- eluent to obtain the desired product.
tribromoheptan-2-one (2z) (316 mg, 0.9 mmol, 45%
1
yield); colorless oil; H NMR (500 MHz, CDCl3): δ 1,2,2-Tribromovinyl)benzene (3a):
3.18 (t, J = 7.4 Hz, 2H), 7.19 (pentet, J = 7.9 Hz, 2H), Phenylpropiolic acid (292 mg, 2.0 mmol) afforded
1.36-1.40 (m, 4H), 0.92 (t, J = 7.1 Hz, 3H),; C{1H} (1,2,2-tribromovinyl)benzene (3a) (613 mg, 1.8 mmol,
13
NMR (126 MHz, CDCl3) δ 190.9, 46.8, 32.9, 31.0, 90% yield); colorless oil; 1H NMR (500 MHz,
25.4, 22.3, 13.9; FTIR (neat) ʋ 2957, 1736, 1121, CDCl3): δ 7.34-7.41 (m, 5H); 13C{1H} NMR (126
1059, 751, cm-1; HRMS (FD) m/z cacld. for MHz, CDCl3) δ 139.4, 129.3, 128.7, 128.5, 124.6,
C7H11Br3O [M]+: 347.8360, found: 347.8366; Anal. 89.8; FTIR (neat) ʋ 3056, 1491, 1442, 783, 694 cm-1;
calcd. for C7H11Br3O : C, 23.96; H, 3.16. Found : C, HRMS (FD) m/z cacld. for C8H5Br3 [M]+: 337.7941,
24.01; H, 3.28.
found: 337.7941; Anal. calcd. for C8H5Br3 : C, 28.19;
H, 1.48. Found : C, 28.43; H, 1.55.
1,1,1-Tribromopentan-2-one (2za):
1-Methyl-2-(1,2,2-tribromovinyl)benzene (3b)[7]:
Hex-2-ynoic acid (224 mg, 2.0 mmol) afforded 1,1,1- 3-(o-Tolyl)propiolic acid (320 mg, 2.0 mmol)
tribromopentan-2-one (2za) (271 mg, 0.84 mmol, afforded
1-methyl-2-(1,2,2-tribromovinyl)benzene
42% yield); colorless oil; 1H NMR (500 MHz, (3b) (603 mg, 1.7 mmol, 85% yield); colorless oil; 1H
CDCl3): δ 3.17 (t, J = 7.3 Hz, 2H), 1.82 (sextet, J = NMR (500 MHz, CDCl3): δ 7.31-7.28 (m, 1H), 7.24 (t,
7.4 Hz, 2H), 1.02 (t, J = 7.5 Hz, 3H); C{1H} NMR J = 5.8 Hz, 2H), 7.21-7.19 (m, 1H), 2.32 (s, 3H);
13
(126 MHz, CDCl3) δ 190.7, 46.8, 34.7, 19.2, 13.4; 13C{1H} NMR (126 MHz, CDCl3) δ 139.1, 135.6,
FTIR (neat) ʋ 2968, 1735, 1264, 1120, 729 cm-1; 130.6, 129.6, 128.2, 126.3, 124.4, 90.8, 19.2; FTIR
HRMS (FD) m/z cacld. for C5H7Br3O [M]+: 319.8047, (neat) ʋ 2921, 1596, 1454, 822, 759 cm-1; HRMS
found: 319.8055; Anal. calcd. for C5H7Br3O : C, (FD) m/z cacld. for C9H7Br3 [M]+: 351.8098, found:
18.60; H, 2.19. Found : C, 18.88; H, 2.00.
351.8098; Anal. calcd. for C9H7Br3 : C, 30.46; H, 1.99.
Found : C, 30.42; H, 2.22.
1,1,1-Tribromobutan-2-one (2zb):
Pent-2-ynoic acid (184 mg, 2.0 mmol) afforded 1,1,1- 1-Methyl-3-(1,2,2-tribromovinyl)benzene (3c):
tribromobutan-2-one (2zb) (253 mg, 0.82 mmol, 41% 3-(m-Tolyl)propiolic acid (320 mg, 2.0 mmol)
yield); brown oil; 1H NMR (500 MHz, CDCl3): δ 3.22 afforded
1-methyl-3-(1,2,2-tribromovinyl)benzene
13
(q, J = 7.3 Hz, 3H), 1.30 (t, J = 7.3 Hz, 2H); C{1H} (3c) (625 mg, 1.76 mmol, 88% yield); colorless oil;
NMR (126 MHz, CDCl3) δ 191.8, 46.1, 26.5, 10.2; 1H NMR (500 MHz, CDCl3): δ 7.29 (t, J = 7.6 Hz,
FTIR (neat) ʋ 2982, 1736, 1458, 1045, 735 cm-1; 1H), 7.23-7.18 (m, 3H), 2.39 (s, 3H); C{1H} NMR
13
HRMS (FD) m/z cacld. for C4H5Br3O [M]+: 305.7891, (126 MHz, CDCl3) δ 139.3, 138.6, 130.1, 129.1,
found: 305.7898; Anal. calcd. for C4H5Br3O : C, 128.3, 125.7, 124.7, 89.6, 21.3; FTIR (neat) ʋ 2919,
15.56; H, 1.63. Found : C, 15.67; H, 1.77.
1481, 1250, 752 701 cm-1; HRMS (FD) m/z cacld. for
C9H7Br3 [M]+: 351.8098, found: 351.8098; Anal.
calcd. for C9H7Br3 : C, 30.46; H, 1.99. Found : C,
1,1,1-Tribromopropan-2-one (2zc):
But-2-ynoic acid (168 mg, 2.0 mmol) afforded 1,1,1- 30.57; H, 2.14.
tribromopropan-2-one (2zc) (230 mg, 0.78 mmol,
1
39% yield); brown oil; H NMR (500 MHz, CDCl3): 1-Methyl-4-(1,2,2-tribromovinyl)benzene (3d):
δ 2.79 (s, 3H); 13C{1H} NMR (126 MHz, CDCl3) δ 3-(p-Tolyl)propiolic acid (320 mg, 2.0 mmol)
8
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800851
Advanced Synthesis & Catalysis
afforded
1-methyl-4-(1,2,2-tribromovinyl)benzene 129.1, 129.0, 128.9, 127.5, 121.8, 116.9, 93.2, 21.3;
(3d) (617 mg, 1.74 mmol, 87% yield); colorless oil; FTIR (neat) ʋ 3065, 2250, 1482, 1411, 733 cm-1;
1H NMR (500 MHz, CDCl3): δ 7.31 (d, J = 8.2 Hz, HRMS (FD) m/z cacld. for C10H6Br3N [M]+:
2H), 7.21 (d, J = 8.0 Hz, 2H), 2.39 (s, 3H); C{1H} 376.8050, found: 376.8048; Anal. calcd. for
13
NMR (126 MHz, CDCl3) δ 139.5, 136.6, 129.2, 128.7, C10H6Br3N : C, 31.62; H, 1.59; N, 3.69. Found : C,
124.9, 89.5, 21.5; FTIR (neat) ʋ 3027, 1504, 1263, 31.66; H, 1.68; N, 3.77.
907 735 cm-1; HRMS (FD) m/z cacld. for C9H7Br3
[M]+: 351.8098, found: 351.8098; Anal. calcd. for 1-Bromo-4-(1,2,2-tribromovinyl)benzene (3k):
C9H7Br3 : C, 30.46; H, 1.99. Found : C, 30.55; H, 2.08. 3-(4-Bromophenyl)propiolic acid (450 mg, 2.0 mmol)
afforded
(3k) (613 mg, 1.46 mmol, 73% yield); colorless oil;
3-(2,4-Dimethylphenyl)propiolic acid (348 mg, 2.0 1H NMR (500 MHz, CDCl3): δ 7.36 (d, J = 8.7 Hz,
mmol) afforded
2,4-dimethyl-1-(1,2,2- 2H), 7.11 (d, J = 8.7 Hz, 2H); 13C{1H} NMR (126
1-bromo-4-(1,2,2-tribromovinyl)benzene
2,4-Dimethyl-1-(1,2,2-tribromovinyl)benzene (3e):
tribromovinyl)benzene (3e) (612 mg, 1.66 mmol, MHz, CDCl3) δ 138.3, 131.8, 130.3, 123.6, 123.3,
83% yield); colorless oil; 1H NMR (500 MHz, 90.6; FTIR (neat) ʋ 2555, 1481, 1391, 1072, 792 cm-
CDCl3): δ 7.10 – 7.11 (m, 1H), 7.05 – 7.07 (m, 2H), 1; HRMS (FD) m/z cacld. for C8H4Br4 [M]+: 415.7047,
13
2.36 (s, 3H), 2.29 (s, 3H); C{1H} NMR (126 MHz, found: 415.7045; Anal. calcd. for C8H4Br4 : C, 22.89;
CDCl3) δ 139.7, 136.3, 135.4, 131.3, 128.1, 127.1, H, 0.96. Found : C, 22.99; H, 1.16.
124.7, 90.7, 21.4, 19.2; FTIR (neat) ʋ 2918, 1510,
1444, 814, 776 cm-1; HRMS (FD) m/z cacld. for 1-Bromo-3-(1,2,2-tribromovinyl)benzene (3l):
C10H9Br3 [M]+: 365.8254, found: 365.8254; Anal. 3-(3-Bromophenyl)propiolic acid (450 mg, 2.0 mmol)
calcd. for C10H9Br3 : C, 32.56; H, 2.46. Found : C, afforded 1-bromo-3-(1,2,2-tribromovinyl)benzene (3l)
1
32.55; H, 2.47.
(596 mg, 1.42 mmol, 71% yield); colorless oil; H
NMR (500 MHz, CDCl3): δ 7.55 (t, J = 2.0 Hz, 1H),
7.50 (ddd, J = 7.9, 2.0, 1.1 Hz, 1H), 7.33 (ddd, J = 7.8,
1.7, 1.1 Hz, 1H), 7.26 (t, J = 7.9 Hz, 1H); 13C{1H}
1-(tert-Butyl)-4-(1,2,2-tribromovinyl)benzene (3f):
3-(4-(tert-butyl)phenyl)propiolic acid (404 mg, 2.0 NMR (126 MHz, CDCl3) δ 141.2, 132.4, 131.6, 130.0,
mmol)
afforded
1-(tert-butyl)-4-(1,2,2- 127.4, 122.6, 122.2, 91.1; FTIR (neat) ʋ 2872, 1559,
tribromovinyl)benzene (3f) (643 mg, 1.62 mmol, 81% 1465, 1260, 749 cm-1; HRMS (FD) m/z cacld. for
yield); colorless oil; H NMR (500 MHz, CDCl3): δ C8H4Br4 [M]+: 415.7047, found: 415.7045. Anal.
1
7.39 (d, J = 8.7 Hz, 2H), 7.34 (d, J = 8.6 Hz, 2H), calcd. for C8H4Br4 : C, 22.89; H, 0.96. Found : C,
1.33 (s, 9H); 13C{1H} NMR (126 MHz, CDCl3) δ 22.95; H, 1.14.
152.6, 136.4, 128.5, 125.4, 125.0, 89.3, 34.9, 31.2;
FTIR (neat) ʋ 2961, 1604, 1470, 831, 703 cm-1; 1-Chloro-4-(1,2,2-tribromovinyl)benzene (3m):
HRMS (FD) m/z cacld. for C12H13Br3 [M]+: 393.8567, 3-(4-Chlorophenyl)propiolic acid (361 mg, 2.0 mmol)
found: 393.8571; Anal. calcd. for C12H13Br3 : C, afforded
36.31; H, 3.30. Found : C, 36.47; H, 3.16.
1-chloro-4-(1,2,2-tribromovinyl)benzene
(3m) (578 mg, 1.54 mmol, 77% yield); colorless oil;
1H NMR (500 MHz, CDCl3): δ 7.37 (d, J = 8.8 Hz,
2H), 7.34 (d, J = 9.1 Hz, 2H); 13C{1H} NMR (126
MHz, CDCl3) δ 137.8, 135.4, 130.2, 128.8, 123.3,
1-Methoxy-4-(1,2,2-tribromovinyl)benzene (3h):
3-(4-Methoxyphenyl)propiolic acid (352 mg, 2.0 90.6; FTIR (neat) ʋ 3089, 1484, 1095, 827, 795 cm-1;
mmol)
afforded
1-methoxy-4-(1,2,2- HRMS (FD) m/z cacld. for C8H4Br3Cl [M]+: 371.7552,
tribromovinyl)benzene (3h) (616 mg, 1.66 mmol, found: 371.7549; Anal. calcd. for C8H4Br3Cl : C,
83% yield); colorless oil; 1H NMR (500 MHz, 25.60; H, 1.07. Found : C, 25.66; H, 0.98.
CDCl3): δ 7.36 (d, J = 8.9 Hz, 2H), 6.90 (d, J = 8.9
Hz, 2H), 3.83 (s, 3H); 13C{1H} NMR (126 MHz, 1-Chloro-3-(1,2,2-tribromovinyl)benzene (3n):
CDCl3) δ 160.1, 131.6, 130.7, 124.9, 113.8, 89.2, 3-(3-Chlorophenyl)propiolic acid (361 mg, 2.0 mmol)
55.9; FTIR (neat) ʋ 2957, 1604, 1503, 1249, 1173 cm- afforded
1-chloro-3-(1,2,2-tribromovinyl)benzene
1; HRMS (FD) m/z cacld. for C9H7Br3O [M]+: (3n) (570 mg, 1.52 mmol, 76% yield); colorless oil;
367.8047, found: 367.80442; Anal. calcd. for 1H NMR (500 MHz, CDCl3): δ 7.39 (t, J = 1.8 Hz,
C9H7Br3O : C, 29.15; H, 1.90. Found : C, 29.41; H, 1H), 7.34 - 7.32 (m, 2H), 7.29 - 7.27 (m, 1H);
1.84.
13C{1H} NMR (126 MHz, CDCl3) δ 141.0, 134.3,
129.8, 129.5, 128.8, 126.9, 122.7, 91.0; FTIR (neat) ʋ
3063, 1564, 1467, 1210, 712, cm-1; HRMS (FD) m/z
2-(2-(1,2,2-Tribromovinyl)phenyl)acetonitrile (3j):
3-(2-(Cyanomethyl)phenyl)propiolic acid (370 mg, cacld. for C8H4Br3Cl [M]+: 371.7552, found:
2.0
mmol)
afforded
2-(2-(1,2,2- 371.7549; Anal. calcd. for C8H4Br3Cl : C, 25.60; H,
tribromovinyl)phenyl)acetonitrile (3j) (600 mg, 1.58 1.07. Found : C, 25.64; H, 1.00.
1
mmol, 79% yield); colorless oil; H NMR (500 MHz,
CDCl3): δ 7.57 (ddd, J = 7.7, 1.4, 0.6 Hz, 1H), 7.45 1-Fluoro-4-(1,2,2-tribromovinyl)benzene (3o):
(td, J = 7.6, 1.6 Hz, 1H), 7.40 (td, J = 7.5, 1.4 Hz, 1H), 3-(4-Fluorophenyl)propiolic acid (328 mg, 2.0 mmol)
7.28 (dd, J = 7.6, 1.4 Hz, 1H), 3.75 (d, J = 3.0 Hz, afforded
1-fluoro-4-(1,2,2-tribromovinyl)benzene
2H); 13C{1H} NMR (126 MHz, CDCl3) δ 138.5, 130.5, (3o) (567 mg, 1.58 mmol, 79% yield); colorless oil;
9
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800851
Advanced Synthesis & Catalysis
1H NMR (500 MHz, CDCl3): δ 7.41 - 7.37 (m, 2H), CDCl3) δ 140.8, 138.9, 138.6, 132.0, 129.3, 128.7,
7.10 - 7.05 (m, 2H); 13C{1H} NMR (126 MHz, 126.9, 124.1, 122.2, 90.0; FTIR (neat) ʋ 3028, 1477,
CDCl3) δ 162.8 (d, J = 250.6 Hz), 135.5 (d, J = 3.6 1276, 816, 744 cm-1; HRMS (FD) m/z cacld. for
Hz), 130.9 (d, J = 8.6 Hz), 123.6, 115.7 (d, J = 22.1 C14H9Br3 [M]+: 413.8254, found: 413.8254; Anal.
Hz), 90.5; FTIR (neat) ʋ 3068, 1585, 1476, 1257, 757 calcd. for C14H9Br3 : C, 40.33; H, 2.18. Found : C,
cm-1; HRMS (FD) m/z cacld. for C8H4Br3F [M]+: 39.99; H, 2.09.
355.7847, found: 355.7851; Anal. calcd. for
C8H4Br3F : C, 26.78; H, 1.12. Found : C, 26.88; H, 2-(1,2,2-Tribromovinyl)naphthalene (3t):
1.09.
3-(Naphthalen-2-yl)propiolic acid (392 mg, 2.0
mmol) afforded 2-(1,2,2-tribromovinyl)naphthalene
(3t) (563 mg, 1.44 mmol, 72% yield); colorless oil;
1-Fluoro-3-(1,2,2-tribromovinyl)benzene (3p):
3-(3-Fluorophenyl)propiolic acid (328 mg, 2.0 mmol) 1H NMR (500 MHz, CDCl3): 7.91 (s, 1H), 7.86 (d, J
afforded
1-fluoro-3-(1,2,2-tribromovinyl)benzene = 8.7 Hz, 3H), 7.53 (t, J = 6.4 Hz, 2H), 7.47 (d, J =
(3p) (560 mg, 1.56 mmol, 78% yield); colorless oil; 8.6 Hz, 1H); 13C{1H} NMR (126 MHz, CDCl3) δ
1H NMR (400 MHz, CDCl3): δ 7.36 (td, J = 8.0, 5.8 136.7, 133.3, 132.7, 128.6, 128.4, 128.4, 127.8, 127.3,
Hz, 1H), 7.19 (ddd, J = 7.7, 1.5, 1.0 Hz, 1H), 7.14 - 126.8, 125.7, 124.8, 90.1; FTIR (neat) ʋ 3056, 1503,
7.04 (m, 2H); 13C{1H} NMR (126 MHz, CDCl3) δ 1272, 814, 748 cm-1; HRMS (FD) m/z cacld. for
162.3 (d, J = 248.0 Hz), 141.3 (d, J = 8.2 Hz), 130.2 C12H7Br3 [M]+: 387.8098, found: 387.8098; Anal.
(d, J = 8.4 Hz), 124.6 (d, J = 3.2 Hz), 122.9 (d, J = 2.4 calcd. for C12H7Br3 : C, 36.87; H, 1.80. Found : C,
Hz), 116.5 (d, J = 21.0 Hz), 116.0 (d, J = 23.0 Hz), 36.88; H, 1.69.
90.9; FTIR (neat) ʋ 3058, 1585, 1433, 1267, 767 cm-
1; HRMS (FD) m/z cacld. for C8H4Br3F [M]+: Methyl 4-(1,2,2-tribromovinyl)benzoate (3v):
355.7847, found: 355.7851; Anal. calcd. for 3-(4-(Methoxycarbonyl)phenyl)propiolic acid (408
C8H4Br3F : C, 26.78; H, 1.12. Found : C, 26.88; H, mg, 2.0 mmol) afforded methyl 4-(1,2,2-
1.14.
tribromovinyl)benzoate (3v) (622 mg, 1.56 mmol,
78% yield); colorless oil; 1H NMR (500 MHz,
1,3-Difluoro-5-(1,2,2-tribromovinyl)benzene (3q):
CDCl3): 8.05 (d, J = 8.7 Hz, 2H), 7.47 (d, J = 8.7 Hz,
3-(3,5-Difluorophenyl)propiolic acid (364 mg, 2.0 2H), 3.92 (s, 3H); C{1H} NMR (126 MHz, CDCl3)
13
mmol)
afforded
1,3-difluoro-5-(1,2,2- δ 164.9, 142.3, 129.4, 128.4, 127.5, 121.8, 89.5, 51.0;
tribromovinyl)benzene (3q) (618 mg, 1.64 mmol, FTIR (neat) ʋ 2878, 1725, 1277, 748, 709 cm-1;
82% yield); colorless oil; 1H NMR (500 MHz, HRMS (FD) m/z cacld. for C10H7Br3O2 [M]+:
CDCl3): δ 6.96 – 6.91 (m, 2H), 6.83 (tt, J = 8.8, 2.3 395.7996, found: 395.7997; Anal. calcd. for
Hz, 1H); 13C{1H} NMR (126 MHz, CDCl3) δ 162.6 C10H7Br3O2 : C, 30.11; H, 1.77. Found : C, 29.92; H,
(dd, J = 250.5, 12.9 Hz), 142.0 (t, J = 10.3 Hz), 121.4 1.65.
(t, J = 2.9 Hz), 112.1 (dd, J = 20.3, 6.6 Hz), 105.0 (t, J
= 25.1 Hz), 91.8; FTIR (neat) ʋ 2928, 1594, 1321, 1-(4-(1,2,2-Tribromovinyl)phenyl)ethanone (3w):
1122, 725 cm-1; HRMS (FD) m/z cacld. for 3-(4-Acetylphenyl)propiolic acid (376 mg, 2.0 mmol)
C8H3Br3F2 [M]+: 373.7753, found: 373.7753; Anal. afforded 1-(4-(1,2,2-tribromovinyl)phenyl)ethanone
calcd. for C8H3Br3F2 : C, 25.50; H, 0.80. Found : C, (3w) (659 mg, 1.72 mmol, 86% yield); colorless oil;
25.51; H, 0.77.
1H NMR (500 MHz, CDCl3): 7.96 (d, J = 8.6 Hz, 2H),
13
7.49 (d, J = 8.6 Hz, 2H), 2.61 (s, 3H); C{1H} NMR
1-(1,2,2-Tribromovinyl)-4-
(trifluoromethyl)benzene (3r):
(126 MHz, CDCl3) δ 197.1, 143.7, 137.2, 129.0,
128.4, 123.0, 90.9, 26.7; FTIR (neat) ʋ 3003, 1682,
3-(4-(Trifluoromethyl)phenyl)propiolic acid (428 mg, 1601, 1261, 716 cm-1; HRMS (FD) m/z cacld. for
2.0 mmol) afforded 1-(1,2,2-tribromovinyl)-4- C10H7Br3O [M]+: 379.8047, found: 379.8047; Anal.
(trifluoromethyl)benzene (3r) (695 mg, 1.7 mmol, calcd. for C10H7Br3O : C, 31.37; H, 1.84. Found : C,
85% yield); colorless oil; 1H NMR (500 MHz, 31.58; H, 1.77.
CDCl3): 7.66 (d, J = 8.1 Hz, 2H), 7.52 (d, J = 8.1 Hz,
2H); 13C{1H} NMR (126 MHz, CDCl3) δ 142.9, 131.2 4-(1,2,2-Tribromovinyl)benzaldehyde (3x):
(q, J = 32.9 Hz), 129.2, 125.6 (q, J = 3.6 Hz), 122.6, 3-(4-Formylphenyl)propiolic acid (348 mg, 2.0
123.6 (q, J = 272.4 Hz), 91.3; FTIR (neat) ʋ 3058, mmol) afforded 4-(1,2,2-tribromovinyl)benzaldehyde
1322, 1168, 1130, 752 cm-1; HRMS (FD) m/z cacld. (3x) (642 mg, 1.74 mmol, 87% yield); colorless oil;
for C9H4Br3F3 [M]+: 405.7815, found: 405.7815; Anal. 1H NMR (500 MHz, CDCl3): 10.0 (s, 1H), 7.9 (d, J =
calcd. for C9H4Br3F3 : C, 26.44; H, 0.99. Found : C, 8.5 Hz, 2H), 7.6 (d, J = 8.2 Hz, 2H); C{1H} NMR
13
26.12; H, 1.11.
(126 MHz, CDCl3) δ 191.2, 145.0, 136.4, 129.8,
129.5, 122.7, 91.3; FTIR (neat) ʋ 3086, 1686, 1599,
1205, 776 cm-1; HRMS (FD) m/z cacld. for C9H5Br3O
4-(1,2,2-Tribromovinyl)-1,1'-biphenyl (3s):
3-([1,1'-Biphenyl]-4-yl)propiolic acid (444 mg, 2.0 [M]+: 365.7891, found: 365.7891; Anal. calcd. for
mmol) afforded 4-(1,2,2-tribromovinyl)-1,1'-biphenyl C9H5Br3O : C, 29.31; H, 1.37. Found : C, 19.68; H,
(3s) (575 mg, 1.38 mmol, 69% yield); colorless oil; 1.30.
1H NMR (500 MHz, CDCl3): 7.59 - 7.56 (m, 4H),
7.50 - 7.44 (m, 5H); 13C{1H} NMR (126 MHz, 4-(1,2,2-Tribromovinyl)benzonitrile (3y)[8]:
10
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800851
Advanced Synthesis & Catalysis
3-(4-Cyanophenyl)propiolic acid (342 mg, 2.0 mmol) cacld. for C14H12O2 [M]+: 212.0837, found: 212.0837;
afforded 4-(1,2,2-tribromovinyl)benzonitrile (3y) Anal. calcd. for C14H12O2 : C, 79.22; H, 5.70. Found :
1
(644 mg, 1.76 mmol, 88% yield); colorless oil; H C, 79.19; H, 5.69.
NMR (500 MHz, CDCl3): 7.69 (d, J = 8.6 Hz, 2H),
13
7.51 (d, J = 8.6 Hz, 2H); C{1H} NMR (126 MHz, N-Benzylbenzamide (6)[9]:
CDCl3) δ 143.7, 132.4, 129.6, 122.0, 118.1, 113.1, 2,2,2-Tribromo-1-phenylethanone (2a) (714 mg, 2.0
91.9; FTIR (neat) ʋ 3089, 2229, 1603, 1401, 744 cm- mmol) afforded N-benzylbenzamide (6) (388 mg,
1
1; HRMS (FD) m/z cacld. for C9H4Br3N [M]+: 1.84 mmol, 92% yield); colorless oil; H NMR (500
362.7894, found: 362.78865; Anal. calcd. for MHz, CDCl3): 7.79 (d, J = 7.1 Hz, 2H), 7.49 (t, J =
C9H4Br3N : C, 29.55; H, 1.10; N, 3.83. Found : C, 7.4 Hz, 1H), 7.41 (t, J = 7.6 Hz, 2H), 7.35 – 7.27 (m,
13
29.65; H, 1.33; N, 3.64.
5H), 6.63 (s, 1H), 4.63 (d, J = 5.7 Hz, 2H); C{1H}
NMR (126 MHz, CDCl3) δ 167.3, 138.2, 134.3, 131.5,
128.7, 128.5, 127.8, 127.5, 126.9, 44.0; FTIR (neat)
1,1,2-Tribromohept-1-ene (3z):
Oct-2-ynoic acid (280 mg, 2.0 mmol) afforded 1,1,2- 3311, 3060, 1637, 1538, 1308, 692 cm-1; HRMS (FD)
tribromohept-1-ene (3z) (375 mg, 1.12 mmol, 56% m/z cacld. for C14H14NO [M]+: 211.0997, found:
1
yield); H NMR (500 MHz, CDCl3): colorless oil; 211.0997. Anal. calcd. for C14H14NO : C, 79.59; H,
2.66 (t, J = 7.5 Hz, 2H), 1.62 (pent, J = 7.6 Hz, 2H), 6.20; N, 6.63. Found : C, 79.89; H, 6.10; N, 6.53.
1.36 – 1.30 (m, 4H), 0.91 (t, J = 7.0 Hz, 3H); 13C{1H}
NMR (126 MHz, CDCl3) δ 129.8, 86.8, 40.9, 30.6,
27.3, 22.4, 14.0; FTIR (neat) ʋ 2956, 1455, 1205, 813, Acknowledgements
728 cm-1; HRMS (FD) m/z cacld. for C7H11Br3 [M]+:
331.8411, found: 331.8418; Anal. calcd. for This research was supported by the National
C7H11Br3 : C, 25.11; H, 3.31. Found : C, 25.21; H, Research Foundation of Korea (NRF) grant funded
3.52.
by the Korea government (MSIP) (NRF-
2015R1A4A1041036, NRF-2017R1A2B2002929). The
spectral and HRMS data were obtained from the
Korea Basic Science Institute, Gwangju center and
1,1,2-Tribromopent-1-ene (3za):
Hex-2-ynoic acid (224 mg, 2.0 mmol) afforded 1,1,2- Daegu center.
tribromopent-1-ene (3za) (310 mg, 1.02 mmol, 51%
1
yield); H NMR (500 MHz, CDCl3): colorless oil;
2.66 (t, J = 7.4 Hz, 2H), 1.65 (sextet, J = 7.5 Hz, 2H), References
13
0.96 (t, J = 7.4 Hz, 3H); C{1H} NMR (126 MHz,
CDCl3) δ 129.6, 87.0, 42.6, 21.0, 13.0; FTIR (neat) ʋ
2963, 1459, 1325, 1116, 742 cm-1; HRMS (FD) m/z
cacld. for C5H7Br3 [M]+: 303.8098, found: 303.8108;
Anal. calcd. for C5H7Br3 : C, 19.57; H, 2.30. Found :
C, 19.67; H, 2.64.
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General experimental procedure for acyl
substitution reactions:
To a 20-mL screw cap vial added 2,2,2-tribromo-1-
phenylethanone (2a) (2 mmol, 1.0 equiv), amine or
alcohol (2 mmol, 1.0 equiv), Et3N (4 mmol, 2.0
equiv), in THF (5.0 mL). The solution was stirred at
50 °C for 6 h. The resulting mixture charged to the
separating funnel added water, extracted with EtOAc.
The organic layer washed with water and dried over
anhydrous MgSO4. After removing the EtOAc under
vacuum, the crude product was purified by column
chromatography on a silica gel column with n-
hexane/ethyl acetate as eluent to give the desired
product.
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Mahoney, Pestic. Sci. 1995, 44, 137.
Benzyl benzoate (5)[9]:
2,2,2-Tribromo-1-phenylethanone (2a) (714 mg, 2.0
mmol) afforded benzyl benzoate (5) (373 mg, 1.76
[5] a) A. O. Terent’ev, S. V. Khodvkin, I. B. Krylov,
Y. N. Ogibin, G. I. Nikishin, Synthesis, 2006,
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1
mmol, 88% yield); colorless oil; H NMR (500 MHz,
CDCl3): 8.13 (dd, J = 8.4, 1.3 Hz, 2H), 7.58 (t, J = 7.4
13
Hz, 1H), 7.50 – 7.35 (m, 7H), 5.41 (s, 1H); C{1H}
NMR (126 MHz, CDCl3) δ 166.3, 135.9, 132.9, 130.0,
129.6, 128.5, 128.3, 128.1, 128.1, 66.6; FTIR (neat)
3033, 1715, 1266, 1105, 707 cm-1; HRMS (FD) m/z
11
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10.1002/adsc.201800851
Advanced Synthesis & Catalysis
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12
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Advanced Synthesis & Catalysis
FULL PAPER
Decarboxylative Tribromination for the Selective
Synthesis of Tribromomethyl Ketone and
Tribromovinyl Derivatives
Adv. Synth. Catal. Year, Volume, Page – Page
Aravindan Jayaraman, Eunjeong Cho, Jimin Kim,
and Sunwoo Lee*
13
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