Dichlorination of olefins with diphenyl sulfoxide/oxalyl chloride

Article abstract of DOI:10.1080/00397911.2020.1774901

The combination of diphenyl sulfoxide and oxalyl chloride was used to accomplish the dichlorination of olefins, in which chlorodiphenylsulfonium salt generated in situ was proposed to be the real active species as a chloronium ion source.

Full text of DOI:10.1080/00397911.2020.1774901

Synthetic Communications
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Dichlorination of olefins with diphenyl sulfoxide/
oxalyl chloride
Rui Ding, Shuai Huang, Qiyi Wang, Yongguo Liu, Baoguo Sun & Hongyu Tian
To cite this article: Rui Ding, Shuai Huang, Qiyi Wang, Yongguo Liu, Baoguo Sun & Hongyu Tian
(2020): Dichlorination of olefins with diphenyl sulfoxide/oxalyl chloride, Synthetic Communications,
DOI: 10.1080/00397911.2020.1774901
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https://doi.org/10.1080/00397911.2020.1774901
Dichlorination of olefins with diphenyl sulfoxide/
oxalyl chloride
ꢀ
ꢀ
Rui Ding , Shuai Huang , Qiyi Wang, Yongguo Liu, Baoguo Sun, and Hongyu Tian
Beijing Advanced Innovation Center for Food Nutrition and Human Health, Beijing Key Laboratory of
Flavor Chemistry, Beijing Technology and Business University, Beijing, China
ABSTRACT
ARTICLE HISTORY
Received 3 December 2019
The combination of diphenyl sulfoxide and oxalyl chloride was used
to accomplish the dichlorination of olefins, in which chlorodiphenyl-
sulfonium salt generated in situ was proposed to be the real active
species as a chloronium ion source.
KEYWORDS
Chlorodiphenylsulfonium
salt; dichlorination; diphenyl
sulfoxide; Olefins;
GRAPHICAL ABSTRACT
oxalyl chloride
Introduction
Dichlorination of olefins is a very versatile tool for organic chemists since organochlor-
ines are a class of valuable intermediates and building blocks of many bioactive com-
pounds. The research interest in chlorination methods of olefins has been increasing
continuously in recent years and a lot of new developed chlorination reagents emerged
in the literature. In addition to the traditional reagent molecular chlorine, the relatively
early developed alternatives include selenium reagents,[1] (dichloroiodo)benzene,[2] vari-
ous Mn mediated combined reagents,[3] tetraethylammonium trichloride,[4] HCl/
H2O2,[5] and hexachloroethane.[6] During the last decade, more and more novel
reagents have been developed, such as Bu4NI/dichloroethane,[7] trichloroisocyanuric
acid,[8] NCS/Ph3P,[9] oxone/chloride,[10] SO2Cl2/Ph3PO,[11] bisacetoxyiodobenzene/pyri-
dine hydrochloride,[12] transition metal Pd or V based combined reagents,[13] and 1-
chloro-1,2-benziodoxol-3-(1H)-one.[14] Lin’s group reported two electrocatalytic
approaches to accomplish the dichlorination of alkenes recently.[15] Some of these
reagents were applied successfully to the total syntheses of chlorosulpholipid cytotox-
ins[16] or stereoselective dichlorination using catalysts with chiral ligands.[17] A variety
of available chlorination methods provide a convenient platform for the development of
organochlorines with important bioactivities.
CONTACT Hongyu Tian
tianhy@btbu.edu.cn
Beijing Advanced Innovation Center for Food Nutrition and Human
Health, Beijing Key Laboratory of Flavor Chemistry, Beijing Technology and Business University, Beijing 102488, China.
ꢀ
These authors contributed equally to this work.
Supplemental data for this article can be accessed on the publisher’s website.
ß 2020 Taylor & Francis Group, LLC

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R. DING ET AL.
Scheme 1. Dichlorination of alkenes with Ph2SO/(COCl)2.
A straightforward method of sulfenyllactonization of olefin acids has been developed
using the combination of dimethyl sulfoxide and oxalyl chloride in our previous work,
in which a series of lactones containing a methylthio group can be obtained.[18]
However, when diphenyl sulfoxide, in analogy with dimethyl sulfoxide, was combined
with oxalyl chloride to react with olefin acids, chlorolactones or dichlorocarboxylic acids
were produced instead of corresponding lactones with a phenylthio group.[19] The for-
mation of dichlorocarboxylic acids prompted us to investigate generality of Ph2SO/
(COCl)2 as chlorination reagent for alkenes. Herein, we report a new dichlorination
method for various double bonds by using Ph2SO/(COCl)2 (Scheme 1).
Results and discussion
Dichlorination of olefin acids with Ph2SO/(COCl)2
The results of several typical types of olefin acids are shown in Table 1 (entries 1–6,
Table 1). The first three substrates were examined in our previous work about chloro-
[19]
lactonization of olefin acids, which gave dichlorides mainly in the absence of K2CO3.
trans-3-Pentenoic acid 1 was treated with Ph2SO/(COCl)2 to afford anti-3,4-dichloro-
pentanoic acid 2 in 70% yield with small amount of chlorolactone 3 (28% yield) (entry
1, Table 1). 4-Pentenoic acid 4 gave the dichloride 5 and the chlorolactone 6 in a ratio
of about 1:1 (entry 2, Table 1). The reaction of 5-hexenoic acid 7 produced the dichlor-
ide 8 in 87% yield and the chlorolactone 9 in 11% yield (entry 3, Table 1). Fortunately,
the dichlorocarboxylic acids and chlorolactones were easy to separate by routine work-
up, such as adjusting pH values and extraction. In contrast, the addition of K2CO3
could avoid the production of dichlorides to give an a,b-unsaturated lactone (for trans-
3-pentenoic acid 1) or chlorolactones (for 4-pentenoic acid 4 and 5-hexenoic acid 7) as
we discussed in our previous work.[19] In all the reactions, a cyclic chloronium ion
intermediate was formed first, which was then attacked by a nucleophile, chloride ion
or carboxyl group. For these substrates, the acidic condition favored the attack of chlor-
ide ion against carboxyl group to give dichlorides mainly, whereas the reaction of carb-
oxyl group predominated under the basic condition. In addition to these three olefin
acids, three more unsaturated acids were investigated. 3-Cyclopenten-1-carboxylic acid
afforded the dichloride 11 in 85% yield without the chlorolactone by-product (entry 4,
Table 1). For two conjugated olefin acids 12 and 13, no dichloride was obtained with
most of the starting materials recovered (entries 5 and 6, Table 1). Moreover, two con-
jugated esters were also explored. No reaction occurred to dimethyl fumarate 14 (entry
7, Table 1). Allyl trans-3-butenoate 14 was converted to 2,3-dichloropropyl trans-3-
butenoate 15 in 80% yield (entry 8, Table 1), in which the double bond conjugated to
carbonyl group was unreactive.

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Table 1. Dichlorination of olefin acids with Ph2SO/(COCl)2.a
Entry
1
Substrate
Product
Yield (%)b
OH
72 (2)/ 28 (3)
O
O
1
4
OH
2
3
49 (5)/47 (6)
87 (8)/ 11 (9)
OH
O
7
Cl
Cl
COOH
10
4
5
6
85
COOH
11
Ph
OH
-
-
NRc
NRc
O
12
13
HO
O
7
8
-
NRc
80
aAll reactions were carried out in CH2Cl2 at ꢁ78 ꢂC to room temperature using alkene (1
equiv.), Ph2SO (1.2 equiv.) and (COCl)2 (1.2 equiv.).
bIsolated yield after column chromatographic purification.
cNR: no reaction.
Dichlorination of simple olefins
Dichlorination of a series of olefins was also carried out using Ph2SO/(COCl)2 under
the similar conditions (Table 2). Cyclohexene 17 was converted to trans-1,2-dichloro-
hexane 18 in 83% yield (entry 1, Table 2). The reaction of 1-decene 19 afforded 1,2-
dichlorodecane 20 in 92% yield (entry 2, Table 2). When allylbenzene 21 was treated
with Ph2SO/(COCl)2, a mixture of two isomers 22 and 23 with a ratio of 4: 1 was
obtained in 93% yield (entry 3, Table 2). The formation of the minor product 23 should
be due to the 1,2-shift of phenyl group of the intermediate during the reaction. Styrene
24 reacted with Ph2SO/(COCl)2 to give a mixture of the dichloride 25 and monochloro-
substituted styrene with a ratio of 3.3: 1 (entry 4, Table 2). The yield of the dichloride
25 was 71% after column chromatographic purification. Similarly, the reaction of 2-
vinylnaphthalene 26 produced the dichloride 27 in 73% yield, but also with a small
amount of monochloro-substituted 2-vinylnaphthalene (ca. 17% by GC) (entry 5, Table
2). The reactions of both cis- and trans-1-phenyl-1-propenes (28 and 32) generated a
mixture of anti- and syn-dichlorides (29 and 30) in 75% and 82% yields respectively
(entries 6 and 7, Table 2). cis-1-Phenyl-1-propene 28 gave a 2.5: 1 anti: syn ratio,
whereas reactant 32 with the trans-configuration gave a 4.3: 1 anti: syn ratio. As in the

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R. DING ET AL.
Table 2. Dichlorination of olefins with Ph2SO/(COCl)2.a
Entry
1
Substrate
Product
Yield (%)
83
2
92
3
4
5
93b,c
71
73
6
7
75b,d
82b,e
aIsolated yield.
bCombined isolated yield.
cThe ratio of two isomers was 4:1.
d2.5:1 anti:syn dichloride was obtained.
e4.3: 1 anti: syn dichloride was obtained.
case of styrene 24, a monochloro-substituted by-product (E)-1-phenyl-2-chloro-1-pro-
pene 31 was also produced in about 10% yield.
Dichlorination of olefins with other functional groups
A series of unsaturated alcohols were treated with Ph2SO/(COCl)2 to produce the corre-
sponding dichlorides with hydroxyl group intact (entries 1–5, Table 3). The reaction of
1-hexen-3-ol 33 with Ph2SO/(COCl)2 gave a mixture of anti- and syn-1,2-dichloro-3-
hexanols 34 and 35 with a ratio of 1: 2.2 in a combined yield of 85% (entry 1, Table 3).
trans-2-Hexen-1-ol 36 was converted to anti-2,3-dichloro-1-hexanol 37 in 89% yield
(entry 2, Table 3). The reactions of both trans- and cis-3-hexen-1-ols 38 and 40 pro-
duced the corresponding dichlorides, but with different relative configuration (entries 3
and 4, Table 3). trans-3-Hexen-1-ol 38 gave anti-3,4-dichloro-1-hexanol 39 in 93% yield
(entry 3, Table 3), whereas cis-3-hexen-1-ol 40 afforded syn-3,4-dichloro-1-hexanol 41
in 91% yield (entry 4, Table 3). 3-Cyclohexene-1-methanol 42 reacted with Ph2SO/
ꢀ
ꢀ
ꢀ
(COCl)2 to produce (1 R ,3S ,4S )-3,4-dichlorocyclohexylmethanol 43 in 90% yield
(entry 5, Table 3). Moreover, but-3-enyl mesylate 44 was also converted to the corre-
sponding dichloride ( )-45 in 90% yield with the mesyloxy group unchanged (entry 6,
Table 3).

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5
Table 3. Dichlorination of olefins containing hydroxyl or carbonyl groups with
Ph2SO/(COCl)2.
Entry
1
Substrate
Product
Yield (%)
85a,b
2
3
4
5
89
93
91
90
6
7
90
87
8
93
9
55 (51)
27 (52)
10
11
81
NRc
aCombined isolated yield.
b1:2.2 anti:syn dichloride was obtained.
cNR: no reaction.

6
R. DING ET AL.
Scheme 2. The mechanism of dichlorination of the double bonds with Ph2SO/(COCl)2.
In addition, four unsaturated carbonyl compounds were also investigated by treat-
ment with Ph2SO/(COCl)2. 5-Hexen-2-one 46 was transformed into 5,6-dichloro-2-hex-
anone ( )-47 in 87% yield (entry 7, Table 3). Likewise, the reaction of 10-undecenal 48
produced 10,11-dichloroundecanal ( )-49 in 93% yield (entry 8, Table 3). For these two
substrates 46 and 48, no a chlorination of carbonyl groups occurred under the investi-
gated conditions. When chalcone 50 reacted with Ph2SO/(COCl)2, a mixture of
anti-2,3-dichloro-1,3-diphenylpropan-1-one 51 and (Z)-2-chloro-1,3-diphenylprop-2-en-
1-one 52 was formed with a ratio of 2: 1, which were separated by column chromatog-
raphy in 55% and 27% yields respectively (entry 9, Table 3). For 4-methoxychalcone 53,
anti-2,3-dichloro-1-phenyl-3-p-methoxyphenylpropan-1-one 54 was obtained in 81%
yield also with a small amount of by-product monochloro-substituted 4-methoxychal-
cone (ca. 11% determined by GC) (entry 10, Table 3). In the case of a simple ketone,
butyrophenone 55, no a chlorinated product was observed when it was treated with
Ph2SO/(COCl)2 (entry 11, Table 3).
Proposed mechanism for dichlorination of double bonds
The mechanism of dichlorination of double bonds with Ph2SO/(COCl)2 was proposed to
be as follows (Scheme 2). First, Ph2SO reacted with (COCl)2 to generate the active inter-
mediate chlorodiphenylsulfonium salt, which acted as a source of chloronium ion. Then
the chlorodiphenylsulfonium salt underwent electrophilic addition to a double bond to
produce a cyclic chloronium ion. The chloride ion attacked the cyclic chloronium ion to
afford the corresponding dichloride. Several substrates were observed to give single isomers
stereoselectively, such as trans-3-pentenoic acid 1 (entry 1, Table 1), 3-cyclopentene-1-car-
boxylic acid 10 (entry 4, Table 1), cyclohexene 17 (entry 1, Table 2), trans-2-hexen-1-ol
36, trans- and cis-3-hexen-1-ols 38 and 40, and 3-cyclohexene-1-methanol 42, chalcone 50
and 4-methoxychalcone 53 (entries 2 ꢃ 5, 9 and 10, Table 3), which indicated the
involvement of cyclic chloronium ions as intermediates. It was a powerful evidence for the
presence of cyclic chloronium ions as intermediates that the reactions of trans- and cis-3-
hexen-1-ols 38 and 40 afforded the products with the relative configurations that can only
be predicted via this mechanism (entries 3 and 4, Table 3). Meanwhile, the fact that the

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7
Scheme 3. The effect of phenyl groups adjacent or attached to the double bonds on dichlorination.
double bonds of two conjugated olefin acids 12 and 13, dimethyl fumarate 14 (entries
5–7, Table 1), as well as the double bond conjugated to the carbonyl group of allyl trans-
2-butenoate 15 (entry 8, Table 1), didn’t react with Ph2SO/(COCl)2, indicated that this
dichlorination is an electrophilic addition to the double bond.
The reaction of allylbenzene 21 produced a mixture of two isomeric dichlorides 22
and 23 (entry 3, Table 2), which was different from that of 1-dencene 19 with a single
dichloride product. Obviously, the isomer 23 was a rearrangement product, which
should be attributed to the 1,2-shifting propensity of phenyl group in the cyclic chloro-
nium ion intermediate (Scheme 3). All the substrates with double bonds conjugated to
phenyl groups, including substrate 24, 26, 28, 32 (entries 4–7, Table 2), and two chal-
cones 50 and 53 (entries 9 and 10, Table 3), produced certain amounts of monochloro-
substituted products. Moreover, both cis- and trans-1-phenyl-1-propenes 28 and 32
gave anti- and syn-dichlorides 29 and 30 with poor stereoselectivity (entries 6 and 7,
Table 2). These results could be explained by the involvement of carbocations stabilized
by the conjugated phenyl groups. The carbocations were able to undertake fragmenta-
tion to produce momochloro substituted products (Scheme 3).
It is noteworthy that the substrates containing hydroxyl group gave the corresponding
dichlorides with hydroxyl group unchanged (entries 1–5, Table 3). Even relatively react-
ive hydroxyl groups attached to allyl groups didn’t participate the reaction, although it
was reported that allyl alcohols could be converted to the corresponding halides with
[20]
halodimethylsulfonium salts generated in situ from (CH3)2S/Br2
or (CH3)2S/NBS
(NCS).[21] Our results demonstrated that the combination of Ph2SO/(COCl)2 has excel-
lent chemoselectivity toward a double bond and hydroxyl group, which might be a
problem for some chlorination reagents, such as chlorine, or NCS/Ph3P.[9] It was found
that unsaturated alcohols were easy to be converted to the corresponding cyclic ethers
with a methylthio group with DMSO/(COCl)2 in our previous work.[22] However, no

8
R. DING ET AL.
cyclization product was obtained, which indicated that no intramolecular nucleophilic
attack of the hydroxyl group on the intermediate cyclic chloronium ion occurred.
Moreover, the presence of active mesyloxy group in the substrate can be tolerated in
the dichlorination (entry 6, Table 3).
In addition, for the substrates 46 and 48 containing a double bond and unconjugated
carbonyl group, the combination of Ph2SO/(COCl)2 also presented chemoselectivity
toward the double bond. No a chlorinated product was generated as a by-product
(entries 7 and 8, Table 3). Butyrophenone 55 was not able to be converted to the corre-
sponding a chlorinated product (entry 11, Table 3). These results demonstrated that
this method possesses unique chemoselectivity for a double bond against a carbonyl
group, which is also a common problem for some chlorination reagents.[4,8,13] It was a
little surprised that chalcone 50 and 4-methoxychalcone 53 also underwent dichlorina-
tion although the double bond here is conjugated with a carbonyl group (entries 9 and
10, Table 3), which seems to conflict with the results of those unsaturated acids and
esters (entries 5–8, Table 1). More substrates with a,b-unsaturated carbonyl groups may
need to be explored further.
It was interesting to find that combination of DMSO/(COCl)2 didn’t undergo
dichlorination of double bonds, which should imply that chlorodimethylsulfonium salt
is unable to act as an active chloronium ion source toward a double bond. The chloro-
dimethylsulfonium salt and chlorodiphenylsulfonium salt demonstrate different reactiv-
ity. On the other hand, we did find that both DMSO/(COBr)2 and Ph2SO/(COBr)2 can
act as a bromonium ion source to accomplish various bromination of double bonds, tri-
ple bonds, or carbonyl compounds in our previous work.[23] These results might give us
some insights about the reactivity of halodialkylsulfonium and halodiarylsulfonium salts.
Conclusion
In summary, the combination of Ph2SO/(COCl)2 has been demonstrated to be an effi-
cient reagent for dichlorination of olefins, which presents excellent chemoselectivity for
the double bonds of the substrates containing hydroxyl, mesyloxy or unconjugated car-
bonyl groups. It has several remarkable advantages, such as short reaction time, easy
availability of the reagents, and functionality tolerance. This method provides us an
attractive alternative for the chlorination of olefins.
Experimental
NMR spectra were obtained on a Bruker AV 300 spectrometer (1H NMR at 300 MHz,
13C NMR at 75 MHz) in CDCl3 using TMS as an internal standard. Chemical shifts (d)
were given in ppm and coupling constants (J) in Hz. HRMS data were obtained on a
Micromass GCT Mass Spectrometer or Bruker Solarix XR FTMS. TLC was performed
with precoated TLC plates, silica gel 60 F-254, layer thickness 0.25 mm. Flash chroma-
tography separations were performed on 100–200 mesh silica gel. Reagents and solvents
are commercial grade and were used as supplied. Substrates are commercially available
and were purchased from Innochem.

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9
General procedures for dichlorination of olefin acids using Ph2SO and (COCl)2
To a solution of oxalyl chloride (0.51 mL, 6.0 mmol, 1.2 equiv.) in CH2Cl2 (10 mL)
cooled at ꢁ78 ꢂC was added dropwise a solution of diphenyl sulfoxide (1.21 g, 6.0 mmol,
1.2 equiv.) in CH2Cl2 (10 mL) under the atmosphere of nitrogen. After 10 min, a solu-
tion of alkenoic acid (5 mmol, 1.0 equiv.) in CH2Cl2 (10 mL) was added. The mixture
was then allowed to warm up to room temperature and stirred for 1 h. The mixture was
carefully basified with saturated NaHCO3 (aq.) at 0 ꢂC. The aqueous layer was separated
and extracted with CH2Cl2 (3 ꢄ 20 mL). The aqueous layer was acidified with 2 M HCl
solution and extracted with CH2Cl2 (3 ꢄ 20 mL). The combined extracts were washed
with brine, dried (Na2SO4), filtered, and concentrated in vacuum to afford the corre-
sponding dichloro acids (2, 5, 8, 11).
Trans-3,4-dichlorocyclopentanecarboxylic acid (11)
1
White solid, 778 mg, 85% yield. H NMR (CDCl3, 300 MHz) d 4.43–4.40 (m, 1 H, H-C-
3 or H-C-4), 4.37–4.32 (m, 1 H, H-C-4 or H-C-3), 3.39–3.24 (m, 1 H, H-C-1), 2.92–2.76
(m, 2 H, H-C-2 and H-C-5), 2.48–2.28 (m, 2 H, H0-C-2 and H0-C-5). 13C NMR (CDCl3,
75 MHz) d 180.60 (COOH), 65.39, 64.17 (C-3 and C-4), 40.21 (C-1), 36.49, 36.39 (C-2
and C-5). HRMS (ESI), m/z [M ꢁ H]ꢁ calcd for C6H7Cl2O2: 180.9828; found: 180.9826.
General procedure for dichlorination of olefins or olefins with hydroxy or
carbonyl group using Ph2SO and (COCl)2
To a solution of oxalyl chloride (0.51 mL, 6.0 mmol, 1.2 equiv.) in CH2Cl2 (10 mL)
cooled at ꢁ78 ꢂC was added dropwise a solution of diphenyl sulfoxide (1.21 g, 6.0 mmol,
1.2 equiv.) in CH2Cl2 (10 mL) under the atmosphere of nitrogen. After 10 min, a solu-
tion of substrate (5 mmol, 1.0 equiv.) in CH2Cl2 (10 mL) was added. The mixture was
then allowed to warm up to the temperature and stirred until TLC showed the reaction
completed. Distilled water (30 mL) was added dropwise at 0 ꢂC. After stirring for
10 min, the organic layer was separated and successively washed with brine. The com-
bined organic extracts were dried (Na2SO4), filtered, and concentrated in vacuum. For
16, 34, 35, and 37, the residue was purified by flash chromatography (silica gel, petrol-
eum ether/ethyl acetate ¼ 30:1 for 16, and 10:1 for 34, 35 and 37). For 17, 19, 21, 24,
26, 28 and 32, the corresponding dichloroalkanes and the byproduct diphenyl sulfide
cannot be separated by chromatography due to the similar polarity. The problem can be
solved by oxidizing diphenyl sulfide to diphenyl sulfoxide to differentiate the polarity.
The residue was dissolved in CH3CN (20 mL), then aqueous 30% H2O2 (1.5 mL,
15 mmol, 3.0 equiv.) and TMSCl (0.96 mL, 7.5 mmol, 1.5 equiv.) were added. The mix-
ture was stirred at room temperature for 30 min. After the disappearance of diphenyl
sulfide, the reaction mixture was quenched by adding water (20 mL), extracted with
CH2Cl2 (3 ꢄ 20 mL), and the extract washed with brine, dried (Na2SO4), filtered, and
concentrated in vacuum. Purification by flash chromatography (silica gel, petroleum
ether/ethyl acetate ¼ 20:1) afforded the corresponding dichloroalkanes.

10
R. DING ET AL.
ꢀ
ꢀ
ꢀ
(1R ,3S ,4S )-3,4-dichlorocyclohexylmethanol (43)
Colorless oil, 823 mg, 90% yield. H NMR (CDCl3, 300 MHz) d 4.40 (m, 1 H, H-C-2),
1
4.34 (q, J ¼ 3.0 Hz, 1 H, H-C-1), 3.53 (d, J ¼ 5.7 Hz, 2 H, H-CH2OH), 2.35 (dddd,
J ¼ 15,3, 12.3, 4.2, 3.0 Hz, 1 H, H0-C-6), 2.00–2.14 (m, 2 H, H0-C-3 and H-C-4),
1.84–1.98 (m, 2 H, H-C-3 and H-C-6), 1.50–1.70 (m, 2 H, H-C-5), 1.45 (br, 1 H, OH).
13C NMR (CDCl3, 75 MHz) d 66.93 (C-CH2OH), 59.81 (C-1), 59.74 (C-2), 33.33 (C-4),
30.63 (C-3), 27.16 (C-6), 22.33 (C-5). HRMS (EI), m/z [M – H2O]þ calcd for C7H10Cl2:
164.0154; found: 164.0152.
1-Mesyloxy-3,4-dichlorobutane (45)
1
Colorless oil, 994 mg, 90% yield. H NMR (CDCl3, 300 MHz) d 4.41 (m, 2 H, H-C-1),
4.23 (m, 1 H, H-C-3), 3.82 (dd, J ¼ 11.7, 5.1 Hz, 1 H, H-C-4), 3.70 (dd, J ¼ 11.7, 6.9 Hz,
1 H, H0-C-4), 3.03 (s, 3 H, CH3 (MsO)), 2.48 (m, 1 H, H-C-2), 2.05 (1 H, H0-C-2). 13C
NMR (CDCl3, 75 MHz) d 66.10 (C-1), 56.46 (C-3), 47.96 (C-4), 37.25 (CH3 (MsO)),
34,53 (C-2). HRMS (ESI), m/z [M þ Na]þ calcd for C5H10Cl2NaO3S: 242.9620;
found: 242.9621.
5,6-Dichloro-2-hexanone (47)
1
Light yellow oil, 835 mg, 87% yield. H NMR (CDCl3, 300 MHz) d 4.12 (dddd, J ¼ 9.9,
7.2, 5.1, 3.0 Hz, 1 H, H-C-5), 3.78 (dd, J ¼ 11.4, 5.1 Hz, 1 H, H0-C-6), 3.66 (dd, J ¼ 11.4,
7.2 Hz, 1 H, H-C-6), 2.61–2.80 (m, 2 H, H-C-3), 2.30–2.42 (m, 1 H, H0-C-4), 2.19 (s,
3 H, H-C-1), 1.83–1.97 (m, 1 H, H-C-4). 13C NMR (CDCl3, 75 MHz) d 207.04 (C-2),
60.30 (C-5), 48.20 (C-6), 39.58 (C-3), 29.99 (C-1), 29.01 (C-4). HRMS (ESI), m/z
[M þ Na]þ calcd for C6H10Cl2NaO: 191.0001; found: 191.0005.
Funding
Financial support from the National Key Research and Development Program
[2016YFD0400801].
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[3] (a) Marko, I. E.; Richardson, P. F. Controlling the Reactivity of Permanganate Anion.
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