Ferric chloride–catalyzed deoxygenative chlorination of carbonyl compounds: A comparison of chlorodimethylsilane and dichloromethylsilane system

Article abstract of DOI:10.1177/1747519820910959

Deoxygenative chlorination of carbonyl compounds using the HMe₂SiCl/FeCl₃/EtOAc and HMeSiCl₂/FeCl₃/EtOAc systems has been systemically investigated. The HMe₂SiCl-FeCl₃ system showed the advantages of good substrate applicability, mild reaction conditions, simple operation, low cost, and easy availability of raw materials. Also, it provided a simple and efficient synthesis route for carbonyl deoxychlorination via a one-pot method. Using the HMeSiCl₂/FeCl₃/EtOAc system, the β-methylchalcone derivative could be obtained in good yields in addition to obtaining the chlorinated compound. Finally, two plausible reaction routes were proposed to describe the formation of the chlorinated compound and the β-methylchalcone derivative.

Full text of DOI:10.1177/1747519820910959

910959CHL0010.1177/1747519820910959Journal of Chemical ResearchXing et al.
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Research Paper
Journal of Chemical Research
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Ferric chloride–catalyzed deoxygenative
chlorination of carbonyl compounds:
A comparison of chlorodimethylsilane
and dichloromethylsilane system
https://doi.org/10.1177/1747519820910959
DOI: 10.1177/1747519820910959
journals.sagepub.com/home/chl
Bing-Han Xing , Xuan-Xuan Zhao, Yu-Jun Qin,
Pu Zhang and Zhi-Xin Guo
Abstract
Deoxygenative chlorination of carbonyl compounds using the HMe2SiCl/FeCl3/EtOAc and HMeSiCl2/FeCl3/EtOAc
systems has been systemically investigated. The HMe2SiCl-FeCl3 system showed the advantages of good substrate
applicability, mild reaction conditions, simple operation, low cost, and easy availability of raw materials. Also, it provided
a simple and efficient synthesis route for carbonyl deoxychlorination via a one-pot method. Using the HMeSiCl2/FeCl3/
EtOAc system, the β-methylchalcone derivative could be obtained in good yields in addition to obtaining the chlorinated
compound. Finally, two plausible reaction routes were proposed to describe the formation of the chlorinated compound
and the β-methylchalcone derivative.
Keywords
carbonyl compound, chlorodimethylsilane, deoxygenative chlorination, dichloromethylsilane, ferric chloride
Date received: 7 October 2019; accepted: 10 January 2020
bearing both hydrogen and chlorine moieties instead of tri-
Introduction
ethylsilane (HSiEt3) and chlorotrimethylsilane (Me3SiCl) as
Reduction of carbonyl compounds to hydroxyl compounds
separate hydrogen and chlorine sources, respectively.
via catalytic hydrosilylation is an essential synthetic method
Obviously, such direct conversion of carbonyl compounds
that has been widely used in academia and industry.1–4 Since
Ojima et al.5 first discovered this reaction in 1972, an enor-
mous amount of work has been published. The published
Department of Chemistry, Renmin University of China, Beijing, P.R.
China
works have mainly focused on searching for meaningful
catalysts or activators that are cheap, easy-to-handle, toler-
ant, and chemo- and/or regioselective.6–12 However, several
research groups have focused on the direct conversion
of hydroxyl groups to chlorides during hydrosilylation
reactions.13–18 For example, Onishi et al.19 reported that the
effective In(OH)3-catalyzed deoxygenative halogenation of
carbonylcompoundsusingchlorodimethylsilane(HMe2SiCl)
Corresponding authors:
Pu Zhang, Department of Chemistry, Renmin University of China,
Beijing 100872, P.R. China.
Email: zhangpu@ruc.edu.cn
Zhi-Xin Guo, Department of Chemistry, Renmin University of China,
Beijing 100872, P.R. China.
Email: gzhixin@ruc.edu.cn

2
Journal of Chemical Research 00(0)
Table 1. Optimized reaction conditions.a
Entry
Silane (equiv.)
Catalyst (equiv.)
Solvent
Time (h)
Yieldb (%)
1
2
3
4
5
6
7
8
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.8)
HMe2SiCl (1.2)
HMe2SiCl (1.0)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
HMe2SiCl (1.5)
–
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
EtOAc
1,4-Dioxane
DME
MeCN
Et2O
Hexane
DMF
DCM
CHCl3
24.0
4.0
7.0
10.0
10.0
12.0
24.0
2.0
1.0
6.0
24.0
7.0
24.0
24.0
24.0
24.0
24.0
24.0
24.0
0
93
95
96
93
97
88
97
97
93
73
66
44
Trace
Trace
0
Fe(II) acetate (0.05)
Fe(ClO4)3·3H2O(0.05)
FeCl2 (0.05)
In(OH)3 (0.05)
Fe(acac)3 (0.05)
AlCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
FeCl3 (0.05)
9
10
11
12
13
14
15
16
17
18
19
0
0
0
DME: 1,2-dimethoxyethane; DMF: N,N-dimethylformamide; DCM: dichloromethane.
aAll reactions were carried out with 1 (10.0mmol) in solvent (20mL) at room temperature.
bYields were determined by 1H NMR.
The bold values in Table 1 are used to highlight that this is the optimal reaction condition.
into chlorides under mild conditions shows significant supe-
riority to the conventional multistep approach involving
separate reduction and chlorination under harsh conditions.
Subsequently, Li et al.20 realized a similar reaction using
dichloromethylsilane (HMeSiCl2) with FeCl3 as the catalyst.
In addition, the deoxygenative chlorination of aromatic car-
bonyl compounds has also been explored. Savela et al.21
reported that using Fe(III) oxo acetate as a catalyst, hydrosi-
lylation of benzylic carbonyl compounds followed by subse-
quent chlorination could be easily achieved with HSiEt3 (as
a hydrogen source) and Me3SiCl (as a chlorine source).
Savela and Leino22 also found that if less Me3SiCl was used
(e.g. 8mol%), symmetrical and nonsymmetrical ethers were
obtained.
Recently, we reported the K2CO3-activated hydrosilyla-
tion of aldehydes and ketones with inexpensive polymeth-
ylhydrosiloxane as a reductive reagent.23 In this work, we
expanded our strategy to the deoxygenative halogenation of
carbonyls using silicon reagents and inexpensive catalysts.
Herein, we present FeCl3-catalyzed deoxygenative chlo-
rination of carbonyl compounds using HMe2SiCl or
HMeSiCl2 as the hydride and chloride sources, respec-
tively, in an efficient and simple manner.
Ethyl acetate (EtOAc) was used as the solvent, and the deox-
ygenative chlorination could not be conducted without cata-
lyst (Table 1, entry 1). However, high conversion was
obtained when the reaction was carried out in the presence of
Lewis acids (Table 1, entries 2–8). Common Lewis acids,
such as Fe(C2H3O2)2, Fe(ClO4)3·3H2O, FeCl2, In(OH)3,
Fe(acac)3, AlCl3, and FeCl3, all exhibited excellent catalytic
activity. When FeCl3 was used, 97% yield of chloroethylben-
zene was obtained within 2h (Table 1, entry 8). Because
FeCl3 is one of the least expensive inorganic catalysts, other
catalysts were not investigated in subsequent studies. To fur-
ther optimize the reaction, the molar ratios of HMe2SiCl to
acetophenone varied (Table 1, entries 9–11). The results indi-
cate that yields of the corresponding chlorides decreased
with a decrease in the amount of HMe2SiCl (Table 1, entries
10 and 11). When diminishing the equivalent of HMe2SiCl to
1.0, the yield of the chloroethylbenzene was only 73% after
24h (Table 1, entry 11). Notably, the 1.8equiv. of HMe2SiCl
could not lead to the yield improvement, while the reaction
time could be reduced to 1h (Table 1, entry 9).
The influences of solvents on deoxygenative chlorina-
tion were also investigated (Table 1, entries 12–19). When
1,4-dioxane was used as the solvent, the desired compounds
were only obtained in 66% yield (Table 1, entry 12), while
1,2-dimethoxyethane (DME) led to an even lower yield of
44% (Table 1, entry 13). For other solvents, such as ace-
tonitrile (MeCN), ether (Et2O), hexane, and N,N-
dimethylformamide (DMF), the starting substrate was fully
recovered or only a trace amount of the desired compound
was obtained (Table 1, entries 14–17); this indicates that no
Results and discussion
HMe2SiCl as hydride and chloride sources
First, acetophenone was used as a standard substrate, and the
catalytic activity of various catalysts was studied (Table 1).

Xing et al.
3
Table 2. Substrate scope of different carbonyl compounds.a
Table 2. (Continued)
Entry
Substrate
Product
Yieldb (%)
19
20
3s
3t
4s
4t
100
89
Entry
Substrate
Product
Yieldb (%)
21
3u
4u
0
1
3a
3b
3c
3d
3e
3f
4a
4b
4c
4d
4e
4f
97
96
88
91
96
93
95
100
92
79
81
88
91
22
23
3v
4v
0
0
2
3w
4w
3
24
3x
4x
94
4
25
26
27
3y
4y
83
54
95
5
3z
4z
6
3aa
4aa
7
3g
3h
3i
4g
4h
4i
28
3ab
3ac
4ab
4ac
79
29
30
5
8
40d
9
31
3ad
4ad
0
aReaction condition: 3 (10.0mmol), HMe2SiCl (15.0mmol), and FeCl3
(0.05mmol) in EtOAc (20mL) at room temperature.
bThe values below the structures refer to NMR yields.
c30.0mmol of HMe2SiCl was used.
10
11
12
13
3j
4j
3k
3l
4k
4l
dReaction carried out at 77°C, 2-chloroheptane (4ac) was obtained in
40% yield.
deoxygenative chlorination occurred. When dichlorometh-
ane (DCM) and chloroform were used, some side products
were generated, and the desired compound was not detected
(Table 1, entries 18 and 19). Although it was reported that
the carbonyl substrates gave good yield of the chloro com-
pounds in chloroform using HMe2SiCl with In(OH)3 as
catalyst,19 using chloroform as solvent in our experiment,
we could only recover most of the starting material. Thus,
EtOAc is the preferred solvent for the deoxygenative chlo-
rination reaction, and this is probably because the good
solubility of FeCl3 in EtOAc and the involving of a solvent-
coordinated hexavalent silicate which acts as an active
hydride species.
3m
4m
14
15
3n
3o
4n
4o
95
81
16
17
18
3p
3q
3r
4pc
4q
4r
100
100
93
After the reaction conditions were optimized, various
ketones were tested as substrates for the deoxygenative chlo-
rination reaction (Table 2). Unsubstituted aromatic ketones gave
corresponding chlorides in high yields (Table 2, entries 1–3).
(Continued) While the aromatic ketones that had a deactivating substituent

4
Journal of Chemical Research 00(0)
(Table 2, entries 4–17) and those that had a weak-activating sub- deoxychlorinated in the HMeSiCl2/FeCl3/EtOAc system.
stituent (Table 2, entries 18–20) were converted to chlorides in Aliphatic ketones (Table 3, entries 7–9) failed to give the
good-to-excellent yields (79%–100%); the substituents suscep- desired products at room temperature, and almost all of the
tible to reduction such as MeSO2– (Table 2, entry 10), NO2– starting arenes were recovered. These results imply that
(Table 2, entries 11 and 12), NC– (Table 2, entry 13), HMeSiCl2 probably reacted in a very different role than
CH3OOC– (Table 2, entry 14), and HOOC– (Table 2, entry 15) HMe2SiCl in the deoxygenative chlorination reaction.
were not affected. For the acetophenones that had the same sub-
stituent at different positions, the yields were similar (Table 2,
entries 4 and 5; entries 6 and 7; entries 11 and 12). However,
Mechanism proposal
each aromatic ketone that had an activating substituent (Table 2, On the basis of the above results, two plausible reaction
entries 21–23) failed to give the desired chloride, and the routes were proposed to explain the formation of the
Clemmensen-type reduction product was obtained. These chlorinated compound and β-methylchalcone derivative
results agree well with Onishi’s report, in which chloroform was (Scheme 1). In 2002, Onishi et al.19 reported that deoxyh-
used as the solvent.19 For aromatic ketones that had an activat- alogenation of carbonyl compounds with HMe2SiCl was
ing substituent, the reaction conditions were further optimized catalyzed by In(OH)3 and gave the proposed mechanism.
to obtain the desired chloride.
We believe that the HMe2SiCl/FeCl3 and HMeSiCl2/FeCl3
At room temperature, the equivalent of the HMe2SiCl systems in our experiment each gave the chlorinated com-
was increased to 2 or 3, and no target chloride was obtained, pound in a similar way to that proposed by Onishi (Scheme
whereas the yield of the reduction product (alkyl benzene) 1, path A). However, when HMeSiCl2 is employed as both
increased. With subsequent heating to 77°C, the target the hydride and chloride sources, alcoholysis of HMeSiCl2
chloride was still not obtained. Polycyclic aromatic sub- should be considered. Alcoholysis of organochlorosilane
strates (Table 2, entries 24 and 25) also effectively pro- and alcohols is an important chemical characteristic of the
duced the desired chloride. Benzophenone (Table 2, entry Si–Cl bond.26 HMeSiCl2 is more electrophilic than
26) produced chloride in 54% yield along with diphenyl- HMe2SiCl because of one more chlorine atom bonded to
methane in 43% yield. When aliphatic ketones are used as silicon. When HMeSiCl2 is used, the enol form of ketones
the substrates, the yields of the products were medium to (nucleophile) can easily attack dichloromethylsilane to
high (Table 2, entries 27–29); sometimes higher tempera- give enol silyl ether (Scheme 1, path B). First, alcoholysis
ture was necessary to obtain a satisfactory yield (Table 2, of the enol form of ketones occurs and affords an enol silyl
entry 30). In this context, aromatic heterocyclic ketones, ether. Then, nucleophilic attack of enol silyl ether on
such as thiophene-2-ketone (Table 2, entry 31), could not another ketone under the activation of FeCl3 produces an
be converted to the corresponding chloride, although a intermediate chelate via loss of dichloromethylsilane.
trace amount of the Clemmensen-type reduction product Finally, the chelate collapses to produce the final β-
was obtained.
methylchalcone derivative via loss of FeCl3 and H2O.
HMeSiCl2 as hydride and chloride sources
Conclusion
Sheng et al.24 reported that FeCl3-catalysted deoxygenative
chlorination of acetophenone can also be performed using
HMeSiCl2 as hydride and chloride sources with DME as the
solvent. Following their report, we used p-chlorobenzophone
as the substrate in our experiment. Surprisingly, a β-
methylchalcone derivative was obtained as the major product
in addition to the desired chloride. Also, there existed a trace
amount of 4-chlorostyrene. Subsequently, EtOAc was used as
the solvent to further study this reaction and the results are
summarized in Table 3. Aromatic ketones that had a deactivat-
ing substituent (Table 3, entries 1 and 2) afforded β-
methylchalcone derivatives along with the chlorinated
compound. Aromatic ketones that had a weak-activating sub-
stituent (Table 3, entries 3 and 4) resulted in only β-
methylchalcone derivatives in 82% and 72% yields,
respectively, and no chloride was obtained. However, aromatic
ketones that had an activating substituent, such as methoxy
and hydroxy (Table 3, entries 5 and 6), failed to give β-
methylchalcone derivatives and chlorides. These results agree
In summary, we have achieved deoxygenative halogena-
tion of carbonyl compounds using the HMe2SiCl/FeCl3/
EtOAc system. This method is eco-friendly and shows
good tolerance. We also performed deoxygenative halo-
genation using the HMeSiCl2/FeCl3/EtOAc system, and
β-methylchalcone derivative was obtained in high yields
in addition to obtaining the target chlorinated compound.
The differences between the HMe2SiCl/FeCl3/EtOAc
and HMeSiCl2/FeCl3/EtOAc systems were investigated
and the corresponding mechanisms were proposed. We
propose that the chlorinated compound was given in a
similar way to the mechanism proposed by Onishi for
both the systems, while a possible route, involving the
alcoholysis of enol form of ketone followed by nucleo-
philic attack on another ketone, was proposed for the
formation of the β-methylchalcone derivative in the
HMeSiCl2/FeCl3/EtOAc system.
with results reported by Elmorsy et al.,25 who treated tetrachlo- Experimental
rosilane with aromatic ketones; the substituents that increased
the negativity of the acetyl group decreased the yield of β-
General information
methylchalcone derivatives.
Chemicals were purchased from commercial sources and
We also found that no allyl chloride could be detected, used without further purification unless otherwise stated.
implying that β-methylchalcone derivative could not be Deuterochloroform (CDCl3) and HMe2SiCl were purchased

Xing et al.
5
Table 3. Reaction under the HMeSiCl2/FeCl3/EtOAc system.a
Entry
Substrate
Chlorinated product
Yieldb (%)
Aldol condensation product
Yieldb (%)
1
2
3
4
5
6
7
4g
4k
4s
28
60
0
5g
5k
5s
70
37
82
72
0
4t
0
5t
4u
4v
4aa
0
5u
5v
5aa
0
0
0
0
8
9
4ab
4ac
0
0
5ab
5ac
0
0
aReaction condition: 3 (10.0mmol), HMeSiCl2 (15.0mmol), and FeCl3 (0.05mmol) in EtOAc (20mL) at room temperature.
bThe values below the structures refer to NMR yields.
from J&K Scientific Ltd. All of the other chemicals were 15.0mmol) was added. Subsequently, the reaction flask was
purchased from Beijing InnoChem Science & Technology equipped with a 90° glass joint with a balloon to protect the
Co., Ltd., Acros, and Alfa Aesar. Column chromatography mixture from moisture. The reaction mixture was stirred vig-
was performed using 100–200 mesh silica gel, which was orously at room temperature until the reaction was com-
purchased from Qingdao Haiyang Chemical Co., Ltd. pleted (as detected by thin-layer chromatography (TLC)).
Nuclear magnetic resonance (NMR) spectra were recorded The solution was washed with saturated NaHCO3 solution
on a Bruker 400MHz spectrometer (1H: 400MHz; 13C: (3×10mL) to remove FeCl3. The organic layer was dried
101MHz).
over anhydrous Na2SO4. The solvent was then removed
under vacuum, and the mixture was purified via column
chromatography to afford the product.
General procedure for the deoxygenative
chlorination of carbonyl compounds with
HMe2SiCl
General procedure for the deoxygenative
chlorination of carbonyl compounds with HMeSiCl2
A 50mL single-neck round-bottom flask was loaded with
carbonyl compound (10.0mmol), FeCl3 (0.0811g, 0.5mmol), A 50mL single-neck round-bottom flask was loaded
and EtOAc (20mL). The reaction mixture was stirred at with carbonyl compound (10.0mmol), FeCl3 (0.0811g,
room temperature for 1min, and then HMe2SiCl (1.4193g, 0.5mmol), and EtOAc (20mL). The reaction mixture was

6
Journal of Chemical Research 00(0)
Scheme 1. Possible routes for the formation of chlorinated compound and β-methylchalcone derivative.
stirred at room temperature for 1min, and then HMeSiCl2 (400MHz, CDCl3) δ 7.38–7.28 (m, 5H), 4.63 (d, J=8.4Hz,
(1.7255g, 15.0mmol) was added. Subsequently, the reac- 1H), 2.22–2.20 (m, 1H), 1.95–1.87 (m, 1H), 1.86–1.78 (m,
tion flask was equipped with a 90° glass joint with a bal- 1H), 1.70–1.67 (m, 2H), 1.48–1.45 (m, 1H), 1.33–1.23 (m,
loon to protect the mixture from moisture. The reaction 1H), 1.22–1.03 (m, 3H), 0.97–0.88 (m, 1H); 13C NMR
mixture was stirred vigorously at room temperature until (101MHz, CDCl3): δ 141.0, 128.4, 128.0, 127.6, 69.9,
the reaction was completed (as detected by TLC). The solu- 45.7, 30.5, 30.3, 26.2, 26.0, 25.9. HRMS (ESI) m/z calcd
tion was washed with saturated NaHCO3 solution for [C13H18Cl]+ (M+H)+: 209.1092; found: 209.1089.
(3×10mL) to remove FeCl3. The organic layer was dried
1-(1-Chloroethyl)-4-fluorobenzene (4d):21 Isolated by
over anhydrous Na2SO4. The solvent was then removed silica gel column chromatography (petroleum ether/ethyl
1
under vacuum, and the mixture was purified via column acetate 300:1) in 91% yield. Colorless liquid; H NMR
chromatography to afford the product.
(400MHz, CDCl3): δ 7.43–7.35 (m, 2H), 7.06–7.00 (m,
2H), 5.08 (q, J=6.8Hz, 1H), 1.83 (d, J=6.8Hz, 3H); 13C
NMR (101MHz, CDCl3): δ 162.4 (d, JC-F =248Hz), 138.7
(d, JC-F =3Hz), 128.3 (d, JC-F =8Hz), 115.5 (d, JC-F =22Hz),
Characterization of the products 4a-5t
(1-Chloroethyl)benzene (4a):19 Isolated by silica gel col- 58.0, 26.6. 19F NMR (565MHz, CDCl3) δ −113.68 (s, 1F).
umn chromatography (petroleum ether/ethyl acetate 200:1) HRMS (ESI) m/z calcd for [C8H9ClF]+ (M+H)+:
in 97% yield. Colorless liquid; 1H NMR (400MHz, 159.0371; found: 159.0375.
CDCl3): δ 7.34 (d, J=7.1Hz, 2H), 7.27 (t, J=7.3Hz, 2H),
1-(1-Chloroethyl)-3-fluorobenzene (4e):28 Isolated by
7.21 (t, J=7.1Hz, 1H), 5.01 (q, J=6.8Hz, 1H), 1.77 (d, silica gel column chromatography (petroleum ether/ethyl
1
J=6.8Hz, 3H);13C NMR (101MHz, CDCl3): δ 142.8, acetate 300:1) in 96% yield. Colorless liquid; H NMR
128.7, 128.3, 126.5, 58.8, 26.5. High-resolution mass spec- (400MHz, CDCl3): δ 7.24 (td, J=8.0, 5.9Hz, 1H), 7.08
trometry (HRMS) (electrospray ionization (ESI)) m/z calcd (ddd, J=9.8, 8.0, 4.9Hz, 2H), 6.95–6.89 (m, 1H), 4.98 (q,
for [C8H10Cl]+ (M+H)+: 141.0466; found: 141.0467.
J=6.8Hz, 1H), 1.76 (d, J=6.8Hz, 3H);13C NMR (101MHz,
(1-Chloropropyl)benzene (4b):27 Isolated by silica gel CDCl3): δ 130.2 (d, JC-F =8Hz), 122.2 (d, JC-F =2Hz), 115.2
column chromatography (petroleum ether/ethyl acetate (d, JC-F =21Hz), 113.6 (d, JC-F =23Hz), 57.7, 26.5. 19F
300:1) in 96% yield. Pale yellow liquid; 1H NMR (400MHz, NMR (565MHz, CDCl3) δ −112.46 (s, 1F). HRMS (ESI)
CDCl3) δ 7.40–7.27 (m, 5H), 4.78 (dd, J=7.6, 6.8Hz, 1H), m/z calcd for [C8H9ClF]+ (M+H)+: 159.0371; found:
2.20–2.01 (m, 2H), 0.99 (t, J=7.3Hz, 3H);13C NMR 159.0368.
(101MHz, CDCl3): δ 141.8, 128.6, 128.2, 127.0, 65.5,
1-Chloro-2-(1-chloroethyl)benzene (4f):21 Isolated by
33.2, 11.8. HRMS (ESI) m/z calcd for [C9H12Cl]+ silica gel column chromatography (petroleum ether/ethyl
(M+H)+: 155.0622; found: 155.0618.
acetate 300:1) in 93% yield. Colorless liquid; H NMR
1
(Chloro(cyclohexyl)methyl)benzene (4c):21 Isolated by (400MHz, CDCl3): δ 7.65 (dd, J=7.8, 1.5Hz, 1H), 7.37–
silica gel column chromatography (petroleum ether/ethyl 7.29 (m, 2H), 7.26–7.20 (m, 1H), 5.58 (q, J=6.8Hz, 1H),
1
acetate 300:1) in 88% yield. Colorless liquid; H NMR 1.83 (d, J=6.8Hz, 3H);13C NMR (101MHz, CDCl3): δ

Xing et al.
7
57.2, 26.3. HRMS (ESI) m/z calcd for [C9H9ClN]+
(M + H)+: 166.0418; found: 166.0410.
140.0, 132.4, 129.6, 129.3, 127.8, 127.4, 54.5, 25.7. HRMS
(ESI) m/z calcd for [C8H9Cl2]+ (M + H)+: 175.0076;
found: 175.0074.
Methyl 4-(1-chloroethyl)benzoate (4n):19 Isolated by
silica gel column chromatography (petroleum ether/ethyl
1-Chloro-4-(1-chloroethyl)benzene (4g):21 Isolated by
silica gel column chromatography (petroleum ether/ethyl
1
acetate 100:1) in 95% yield. Colorless liquid; H NMR
1
acetate 300:1) in 95% yield. Colorless liquid; H NMR
(400MHz, CDCl3): δ 8.03 (dd, J=8.4, 1.9Hz, 2H), 7.52–
7.46 (m, 2H), 5.15–5.06 (m, 1H), 3.91 (d, J=2.3Hz, 3H),
1.84 (dd, J=6.8, 2.6Hz, 3H);13C NMR (101MHz, CDCl3):
δ 166.6, 147.6, 130.0, 126.5, 57.8, 52.2, 26.4. HRMS (ESI)
m/z calcd for [C10H12ClO2]+ (M+H)+: 199.0520; found:
199.0524.
(400MHz, CDCl3): δ 7.38–7.29 (m, 4H), 5.05 (q, J=6.8Hz,
1H), 1.82 (d, J=6.8Hz, 3H);13C NMR (101MHz, CDCl3):
δ 141.3, 134.0, 128.8, 127.9, 57.8, 26.5. HRMS (ESI) m/z
calcd for [C8H9Cl2]+ (M+H)+: 175.0076; found: 175.0070.
1-Bromo-4-(1-chloroethyl)benzene (4h):21 Isolated by
silica gel column chromatography (petroleum ether/ethyl
4-(1-Chloroethyl)benzoic acid (4o):19 Isolated by silica
gel column chromatography (petroleum ether/ethyl acetate
10:1) in 81% yield. White solid; m.p. 201–203°C. 1H NMR
(400MHz, dimethyl sulfoxide (DMSO)): δ 13.03 (s, 1H),
7.95 (d, J=8.3Hz, 2H), 7.60 (d, J=8.3Hz, 2H), 5.42 (q,
J=6.8Hz, 1H), 1.79 (d, J=6.8Hz, 3H); 13C NMR
(101MHz, DMSO): δ 167.4, 147.7, 131.1, 130.1, 127.3,
58.6, 26.3. HRMS (ESI) m/z calcd for [C9H10ClO2]+
(M+H)+: 185.0364; found: 185.0362.
1,3-Bis(1-chloroethyl)benzene (4p): Isolated by silica
gel column chromatography (petroleum ether/ethyl acetate
150:1) in 100% yield. Colorless liquid; 1H NMR (400MHz,
CDCl3): δ 7.33 (d, J=36.3Hz, 4H), 5.02 (q, J=6.8Hz, 2H),
1.78 (d, J=6.8Hz, 6H);13C NMR (101MHz, CDCl3): δ
143.3, 129.0, 126.4, 124.8, 58.5, 26.6. HRMS (ESI) m/z
calcd for [C10H13Cl2]+ (M+H)+: 203.0389; found:
203.0390.
1
acetate 300:1) in 100% yield. Colorless liquid; H NMR
(400MHz, CDCl3): δ 7.39 (d, J=8.4Hz, 2H), 7.21 (d,
J=8.3Hz, 2H), 4.95 (q, J=6.8Hz, 1H), 1.73 (d, J=6.8Hz,
3H);13C NMR (101MHz, CDCl3): δ 141.9, 131.8, 128.3,
122.1, 57.8, 26.5. HRMS (ESI) m/z calcd for [C8H9BrCl]+
(M + H)+: 218.9571; found: 218.9576.
1-(1-Chloroethyl)-4-(trifluoromethyl)benzene(4i):21 Iso-
lated by silica gel column chromatography (petroleum
ether/ethyl acetate 300:1) in 92% yield. Colorless liquid; 1H
NMR (400MHz, CDCl3): δ 7.54 (d, J=8.2Hz, 2H), 7.45
(d, J=8.3Hz, 2H), 5.02 (q, J=6.8Hz, 1H), 1.77 (d,
J=6.8Hz, 3H);13C NMR (151MHz, CDCl3) δ 146.7, 130.5
(q, JC-F =33Hz), 127.0, 125.7 (q, JC-F =4Hz), 126.7–121.3
(q, JC-F =272Hz), 57.5, 26.4.19 F NMR (565MHz, CDCl3)
δ −62.66 (s, 3F). HRMS (ESI) m/z calcd for [C8H9ClF3]+
(M+H)+: 209.0339; found: 209.0341.
1-(1-Chloroethyl)-4-(methylsulfonyl)benzene
(4j):
1-Chloro-3-(1-chloropropyl)benzene (4q): Isolated by
silica gel column chromatography (petroleum ether/ethyl
Isolated by silica gel column chromatography (petroleum
ether/ethyl acetate 30:1) in 79% yield. Colorless liquid; 1H
NMR (400MHz, CDCl3): δ 7.95 (d, J=8.3Hz, 2H), 7.63
(d, J=8.4Hz, 2H), 5.13 (q, J=6.8Hz, 1H), 3.07 (s, 3H),
1.87 (d, J=6.8Hz, 3H);13C NMR (101MHz, CDCl3): δ
148.7, 140.2, 128.0, 127.7, 57.0, 44.5, 26.4. HRMS (ESI)
m/z calcd for [C9H12ClO2S]+ (M+H)+: 219.0241; found:
219.0244.
1
acetate 300:1) in 100% yield. Colorless liquid; H NMR
(400MHz, CDCl3) δ 7.30 (s, 1H), 7.22–7.15 (m, 3H), 4.65
(dd, J=7.8, 6.5Hz, 1H), 2.10–1.91 (m, 2H), 0.92 (t,
J=7.3Hz, 3H); 13C NMR (101MHz, CDCl3): δ 143.7,
134.4, 129.9, 128.4, 127.2, 125.2, 64.4, 33.2, 11.6. HRMS
(ESI) m/z calcd for [C9H11Cl2]+ (M+H)+: 189.0232;
found: 189.0233.
1-(1-Chloroethyl)-4-nitrobenzene (4k):29 Isolated by
silica gel column chromatography (petroleum ether/ethyl
acetate 60:1) in 81% yield. Yellow liquid; 1H NMR
(400MHz, CDCl3): δ 8.14 (d, J=8.8Hz, 2H), 7.52 (d,
J=8.7Hz, 2H), 5.06 (q, J=6.8Hz, 1H), 1.79 (d, J=6.8Hz,
3H);13C NMR (101MHz, CDCl3): δ 149.7, 147.6, 127.5,
123.9, 56.9, 26.4. HRMS (ESI) m/z calcd for [C8H9ClNO2]+
(M+H)+: 186.0316; found: 186.0310.
1-(1-Chloroethyl)-2-methylbenzene (4r):30 Isolated by
silica gel column chromatography (petroleum ether/ethyl
1
acetate 300:1) in 93% yield. Colorless liquid; H NMR
(400MHz, CDCl3): δ 7.53 (d, J=7.6Hz, 1H), 7.23 (dd,
J=15.3, 8.5Hz, 2H), 7.16 (d, J=6.9Hz, 1H), 5.35 (q,
J=6.8Hz, 1H), 2.41 (s, 3H), 1.86 (d, J=6.8Hz, 3H);13C
NMR (101MHz, CDCl3): δ 140.5, 135.3, 130.6, 128.2,
126.6, 125.7, 55.0, 25.2, 19.0. HRMS (ESI) m/z calcd for
[C9H12Cl]+ (M+H)+: 155.0622; found: 155.0628.
1-(1-Chloroethyl)-3-nitrobenzene (4l): Isolated by silica
gel column chromatography (petroleum ether/ethyl acetate
1-(1-Chloroethyl)-4-methylbenzene (4s):19 Isolated by
silica gel column chromatography (petroleum ether/ethyl
1
120:1) in 88% yield. Yellow liquid; H NMR (400MHz,
1
CDCl3): δ 8.31 (s, 1H), 8.18 (d, J=8.2Hz, 1H), 7.78 (d,
J=7.7Hz, 1H), 7.57 (t, J=8.0Hz, 1H), 5.17 (q, J=6.8Hz,
1H), 1.90 (d, J=6.8Hz, 3H);13C NMR (101MHz, CDCl3):
δ 148.4, 144.8, 132.8, 129.8, 123.2, 121.6, 56.9, 26.4.
HRMS (ESI) m/z calcd for [C8H9ClNO2]+ (M+H)+:
186.0316; found: 186.0314.
acetate 200:1) in 100% yield. Colorless liquid; H NMR
(400MHz, CDCl3): δ 7.29 (d, J=8.1Hz, 2H), 7.13 (d,
J=7.9Hz, 2H), 5.05 (q, J=6.8Hz, 1H), 2.32 (s, 3H), 1.81
(d, J=6.8Hz, 3H);13C NMR (101MHz, CDCl3): δ 139.9,
138.1, 129.3, 126.5, 58.8, 26.5, 21.2. HRMS (ESI) m/z
calcd for [C9H12Cl]+ (M+H)+: 155.0622; found: 155.0620.
4-(1-Chloroethyl)-1,1′-biphenyl (4t):21 Isolated by silica
gel column chromatography (petroleum ether/ethyl acetate
300:1) in 89% yield. White solid; m.p. 52–54°C. 1H NMR
(400MHz, CDCl3): δ 7.50 (d, J=8.3Hz, 4H), 7.44–7.33
(m, 4H), 7.28 (t, J=7.3Hz, 1H), 5.07 (q, J=6.8Hz, 1H),
1.82 (d, J=6.8Hz, 3H); 13C NMR (101MHz, CDCl3): δ
4-(1-Chloroethyl)benzonitrile (4m):19 Isolated by silica
gel column chromatography (petroleum ether/ethyl acetate
150:1) in 91% yield. Colorless liquid; 1H NMR (400MHz,
CDCl3): δ 6.44 (d, J=8.2Hz, 2H), 6.31 (d, J=8.3Hz, 2H),
3.86 (q, J=6.8Hz, 1H), 0.62 (d, J=6.8Hz, 3H);13C NMR
(101MHz, CDCl3): δ 147.7, 132.5, 127.3, 118.4, 112.0,

8
Journal of Chemical Research 00(0)
141.8, 141.3, 140.6, 128.8, 127.5, 127.4, 127.2, 127.0,
Chlorocyclohexane (4ab):34 Isolated by silica gel col-
58.6, 26.5. HRMS (ESI) m/z calcd for [C14H14Cl]+ umn chromatography (petroleum ether/ethyl acetate 300:1)
(M+H)+: 217.0779; found: 217.0779.
in 79% yield. Colorless liquid; 1H NMR (400MHz, CDCl3):
1-Ethyl-4-methoxybenzene (4u):31 Isolated by silica gel δ 4.08–3.95 (m, 1H), 2.08 (d, J=10.9Hz, 2H), 1.81 (d,
column chromatography (petroleum ether/ethyl acetate J=5.6Hz, 2H), 1.74–1.62 (m, 2H), 1.55 (d, J=5.7Hz, 1H),
1
5:1) in 69% yield. Colorless liquid; H NMR (400MHz, 1.43–1.28 (m, 3H); 13C NMR (101MHz, CDCl3): δ 60.3,
CDCl3) δ 7.13 (d, J=8.6Hz, 2H), 6.85 (d, J=8.6Hz, 2H), 36.7, 25.2, 24.9. HRMS (ESI) m/z calcd for [C6H12Cl]+
3.80 (s, 3H), 2.61 (q, J=7.6Hz, 2H), 1.23 (t, J=7.6Hz, (M+H)+: 119.0622; found: 119.0624.
3H).13C NMR (101MHz, CDCl3) δ 157.6, 136.4, 128.7,
2-Chloroheptane (4ac): Isolated by silica gel column
113.8, 55.3, 28.0, 15.9. HRMS (ESI) m/z calcd for chromatography (petroleum ether/ethyl acetate 200:1) in
[C9H13O]+ (M+H)+: 137.0961; found: 137.0959.
40% yield. Colorless liquid; 1H NMR (400MHz, CDCl3) δ
4-Ethylphenol (4v):32 Isolated by silica gel column chro- 4.12–3.96 (m, 1H), 1.70 (ddd, J=9.0, 8.4, 4.1Hz, 2H), 1.51
matography (petroleum ether/ethyl acetate 5:1) in 63% (d, J=6.5Hz, 4H), 1.42–1.22 (m, 5H), 0.90 (t, J=7.0Hz,
yield. Colorless liquid; 1H NMR (400MHz, CDCl3) δ 7.07 3H); 13C NMR (101MHz, CDCl3) δ 59.0, 40.4, 31.4, 26.4,
(d, J=8.5Hz, 2H), 6.76 (d, J=6.5Hz, 2H), 4.58 (s, 1H), 25.4, 22.6, 14.0. HRMS (ESI) m/z calcd for [C7H16Cl]+
2.58 (q, J=7.6Hz, 2H), 1.20 (t, J=7.6Hz, 3H); 13C NMR (M+H)+: 135.0935; found: 135.0931.
(101MHz, CDCl3) δ 153.3, 136.6, 128.9, 115.2, 28.0, 15.9.
HRMS (ESI) m/z calcd for [C8H11O]+ (M+H)+: 123.0804; chromatography (petroleum ether/ethyl acetate 300:1) in
found: 123.0806.
43% yield. Colorless liquid; 1H NMR (400MHz, CDCl3): δ
Diphenylmethane (4ad):35 Isolated by silica gel column
N-(4-ethylphenyl)acetamide (4w): Isolated by silica gel 7.16 (ddd, J=20.5, 14.0, 7.1Hz, 10H), 3.91 (d, J=13.6Hz,
column chromatography (petroleum ether/ethyl acetate 2H); 13C NMR (101MHz, CDCl3): δ 141.1, 129.0, 128.5,
200:1) in 67% yield. Colorless liquid; 1H NMR (400MHz, 126.1, 42.0. HRMS (ESI) m/z calcd for [C13H13]+ (M+H)+:
CDCl3) δ 7.39 (d, J=8.4Hz, 2H), 7.14 (d, J=8.4Hz, 2H), 169.1012; found: 169.1011.
2.61 (q, J=7.6Hz, 2H), 2.16 (s, 3H), 1.21 (t, J=7.6Hz,
1-(Heptan-2-yloxy)-2-methylheptane (4ae): Isolated by
3H).13C NMR (101MHz, CDCl3) δ 168.2, 140.4, 135.5, silica gel column chromatography (petroleum ether/ethyl
1
128.3, 120.1, 28.3, 24.6, 15.7. HRMS (ESI) m/z calcd for acetate 200:1) in 52% yield. Colorless liquid; H NMR
[C10H14NO]+ (M+H)+: 164.1070; found: 164.1070.
(400MHz, CDCl3) δ 3.46–3.33 (m, 2H), 1.51–1.23 (m,
2-(1-Chloroethyl)naphthalene (4x):21 Isolated by silica 16H), 1.09 (d, J=6.1Hz, 6H), 0.88 (t, J=6.9Hz, 6H);13C
gel column chromatography (petroleum ether/ethyl acetate NMR (101MHz, CDCl3) δ 73.0, 37.5, 32.0, 25.6, 22.7,
1
300:1) in 94% yield. White solid; m.p. 67°C. H NMR 20.5, 14.1. HRMS (ESI) m/z calcd for [C14H31O]+
(400MHz, CDCl3): δ 7.90–7.83 (m, 4H), 7.60 (dd, J=8.5, (M+H)+: 215.2369; found: 215.2371.
1.8Hz, 1H), 7.56–7.48 (m, 2H), 5.30 (q, J=6.8Hz, 1H),
1,3-Bis(4-chlorophenyl)but-2-en-1-one (5g):36 Isolated
1.97 (d, J=6.8Hz, 3H); 13C NMR (101MHz, CDCl3): δ by silica gel column chromatography (petroleum ether/
140.0, 133.1, 133.1, 128.6, 128.1, 127.7, 126.4, 126.4, ethyl acetate 150:1) in 70% yield. Yellow solid; m.p. 80°C.
125.2, 124.5, 59.0, 26.4. HRMS (ESI) m/z calcd for 1H NMR (400MHz, CDCl3): δ 7.93 (d, J=8.6Hz, 2H),
[C12H12Cl]+ (M+H)+: 191.0622; found: 191.0620.
7.50 (d, J=8.7Hz, 2H), 7.45 (d, J=10.9Hz, 2H), 7.39 (d,
9-Chloro-9H-fluorene (4y):21 Isolated by silica gel col- J=8.7Hz, 2H), 7.10 (s, 1H), 2.58 (s, 3H); 13C NMR
umn chromatography (petroleum ether/ethyl acetate 100:1) (101MHz, CDCl3): δ 190.2, 154.3, 140.9, 139.0, 137.4,
in 83% yield. White solid; m.p. 92°C. 1H NMR (400MHz, 135.3, 129.7, 128.9, 128.8, 127.8, 121.7, 18.8. HRMS (ESI)
CDCl3): δ 7.61–7.54 (m, 4H), 7.32 (dt, J=7.5, 3.8Hz, 2H), m/z calcd for [C16H13Cl2O]+ (M+H)+: 291.0338; found:
7.26 (td, J=7.4, 1.2Hz, 2H), 5.70 (s, 1H); 13C NMR 291.0339.
(101MHz, CDCl3): δ 143.8, 140.0, 129.4, 128.0, 125.8,
1,3-Bis(4-nitrophenyl)but-2-en-1-one (5k):25 Isolated by
120.1, 57.6. HRMS (ESI) m/z calcd for [C13H10Cl]+ silica gel column chromatography (petroleum ether/ethyl
(M+H)+: 201.0466; found: 201.0465.
acetate 20:1) in 37% yield. Yellow solid; m.p. 154°C. H
1
(Chloromethylene)dibenzene (4z):33 Isolated by silica NMR (400MHz, CDCl3) δ 8.35 (dd, J=17.9, 8.8Hz, 4H),
gel column chromatography (petroleum ether/ethyl acetate 8.16 (d, J=8.8Hz, 2H), 7.74 (d, J=8.8Hz, 2H), 7.19 (s,
300:1) in 54% yield. Yellow color liquid; 1H NMR 1H), 2.68 (s, 3H); 13C NMR (101MHz, CDCl3) δ 189.4,
(400MHz, CDCl3): δ 7.41 (ddd, J=18.3, 17.8, 5.2Hz, 154.9, 150.2, 148.6, 148.3, 143.4, 129.3, 127.5, 124.0,
10H), 6.20 (s, 1H); 13C NMR (101MHz, CDCl3): δ 141.1, 124.0, 123.4, 19.2. HRMS (ESI) m/z calcd for
128.6, 128.1, 127.8, 64.3. HRMS (ESI) m/z calcd for [C16H13N2O5]+ (M+H)+: 313.0819; found: 313.0819.
[C13H12Cl]+ (M+H)+: 203.0622; found: 203.0623.
1,3-Di-p-tolylbut-2-en-1-one (5s):25 Isolated by silica
(3-Chlorobutyl)benzene (4aa):19 Isolated by silica gel gel column chromatography (petroleum ether/ethyl acetate
1
column chromatography (petroleum ether/ethyl acetate 200:1) in 82% yield. Yellow solid; H NMR (400MHz,
300:1) in 95% yield. Colorless liquid; 1H NMR (400MHz, CDCl3) δ 7.90 (d, J=8.2Hz, 2H), 7.48 (d, J=8.2Hz, 2H),
CDCl3) δ 7.37 (t, J=7.6Hz, 2H), 7.28 (d, J=6.1Hz, 3H), 7.26 (d, J=8.7Hz, 2H), 7.22 (d, J=8.0Hz, 2H), 7.15 (s,
4.10–4.02 (m, 1H), 2.92–2.81 (m, 2H), 2.11–2.05 (m, 2H), 1H), 2.57 (s, 3H), 2.42 (s, 3H), 2.39 (s, 3H);13C NMR
1.60 (d, J=6.6Hz, 3H); 13C NMR (101MHz, CDCl3) δ (101MHz, CDCl3) δ 191.6, 154.5, 143.2, 139.9, 139.3,
141.1, 128.5, 128.5, 126.1, 57.9, 41.9, 32.9, 25.4. HRMS 137.0, 129.3, 129.2, 128.4, 126.4, 121.5, 21.7, 21.3, 18.8.
(ESI) m/z calcd for [C10H14Cl]+ (M+H)+: 169.0779; HRMS (ESI) m/z calcd for [C18H18O]+ (M+H)+:
found: 169.0777.
250.1358; found: 250.1355.

Xing et al.
1,3-Di([1,1′-biphenyl]-4-yl)but-2-en-1-one (5t):25 Isolated
9
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by silica gel column chromatography (petroleum ether/ethyl
acetate 200:1) in 72% yield. Yellow solid; 1H NMR
(400MHz, CDCl3) δ 8.12 (d, J=8.4Hz, 2H), 7.74 (d,
J=8.5Hz, 2H), 7.70 (d, J=2.5Hz, 4H), 7.68 (d, J=3.8Hz,
4H), 7.50 (t, J=6.6Hz, 4H), 7.43 (t, J=6.7Hz, 2H), 7.31 (s,
1H), 2.69 (s, 3H);13C NMR (101MHz, CDCl3) δ 191.3,
154.5, 145.3, 142.1, 141.6, 140.3, 140.1, 138.2, 128.9, 128.2,
127.7, 127.3, 127.1, 127.0, 121.9, 18.8. HRMS (ESI) m/z
calcd for (C28H23O)+ (M+H)+: 375.1743; found: 375.1743.
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Declaration of conflicting interests
The author(s) declared no potential conflicts of interest with
respect to the research, authorship, and/or publication of this paper.
19. Onishi Y, Ogawa D, Yasuda M, et al. J Am Chem Soc 2002;
124: 13690–13691.
Funding
The author(s) disclosed receipt of the following financial support
for the research, authorship, and/or publication of this paper: This
work was supported by the Fundamental Research Funds for the
Central Universities and the Research Funds of Renmin University
of China (Grant No. 15XNLQ04).
20. Li Z, Sheng C, Qiu H, et al. Org Prep Proced Int 2007; 39:
412–415.
21. Savela R, Warna J, Murzin DY, et al. Catal Sci Technol
2015; 5: 2406–2417.
22. Savela R and Leino R. Synthesis 2015; 47: 1749–1760.
23. Zhao XX, Zhang P and Guo ZX. Chemistryselect 2017; 2:
7670–7677.
24. Sheng CQ, Li ZF, Yang CJ, et al. Chinese J Org Chem 2008;
28: 515–520.
ORCID iD
Bing-Han Xing
https://orcid.org/0000-0001-7990-4579
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1997; 7: 232–233.
Supplemental material
26. Silicone Research Group in Chengguang Institute of Chemical
Engineering. Silicone Monomer and polymer. Beijing, China:
Chemical Industrial Press, 1986, p. 121.
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Supplemental material for this article is available online.
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