Aminochlorination of Alkenes with CFBSA

Article abstract of DOI:10.1002/ejoc.201600709

A novel catalyst-free aminochlorination of alkenes was developed by the direct addition of alkenes to N-chloro-N-fluorobenzenesulfonamide (CFBSA). The reaction produces 2-chloro-3-fluoramino and 3-chloro-2-fluoroamino adducts in 1,2-dichloroethane under reflux and dichloromethane at room temperature, respectively, in a regioselective manner. The electronic and steric effects of the fluorine atom of CFBSA have proven to be crucial for the reactivity and regioselectivity. A variety of transformations have been achieved to form 2-chloroenamines, chloroamines, aziridines and N-phenylbenzenesulfonamides under different conditions. Notably, the N–F bond in the adducts formed could be a useful handle for further transformations to useful compounds in organic synthesis.

Full text of DOI:10.1002/ejoc.201600709

DOI: 10.1002/ejoc.201600709
Full Paper
Aminochlorination
Aminochlorination of Alkenes with CFBSA
Xiao-Qiu Pu,[a] Hai-Yong Zhao,[a] Ze-Hai Lu,[a] Xiao-Peng He,[a] and Xian-Jin Yang*[a,b]
Abstract: A novel catalyst-free aminochlorination of alkenes be crucial for the reactivity and regioselectivity. A variety of
was developed by the direct addition of alkenes to N-chloro-N- transformations have been achieved to form 2-chloroenamines,
fluorobenzenesulfonamide (CFBSA). The reaction produces 2- chloroamines, aziridines and N-phenylbenzenesulfonamides un-
chloro-3-fluoramino and 3-chloro-2-fluoroamino adducts in 1,2- der different conditions. Notably, the N–F bond in the adducts
dichloroethane under reflux and dichloromethane at room tem- formed could be a useful handle for further transformations to
perature, respectively, in a regioselective manner. The electronic useful compounds in organic synthesis.
and steric effects of the fluorine atom of CFBSA have proven to
Introduction
the past few years, a variety of reagents have been employed
for the aminohalogenation, including NCS,[5] NBS,[6] NIS,[7]
NFSI,[8] chloramine-T,[9] bromamine-T,[10] and TsNCl2,[11] How-
ever, catalysts are often required for these reactions[12] [Fig-
ure 2, (1)].
Haloamines are versatile building blocks extensively used in
modern chemical syntheses (Figure 1).[1] It was reported that
bromoamination was utilized in the synthesis of natural product
allosadmin,[2] fluoroamination was applied in the synthesis of
GABA-AT inactivator,[3] and enamines can be conveniently syn-
thesized by the elimination of a hydrohalide from haloamines.
The difunctionalization of alkenes with aminohalogenating rea-
gents is a typical reaction to achieve aminohalogenation.[4] In
Figure 2. Synthesis of chloramine compounds.
As a good case, in 2014, Muñiz reported an acid-promoted
aminochlorination[13] [Figure 2, (2)]. This result encouraged us
to explore more efficient aminohalogenation methods.
N-Chloro-N-fluorobenzenesulfonamide (CFBSA, 1) is a react-
ive chlorinating reagent first explored in our laboratory.[14] As a
new chlorinating reagent, it is more reactive than chloramine-
B and more stable for storage than TsNCl2. Its high electrophilic
chlorination reactivity stems from the strong electron-with-
drawing behaviour of the fluorine atom and the phenylsulfonyl
group on the nitrogen atom. Herein, we report a catalyst-free
aminochlorination of alkenes with CFBSA [Figure 2, (3)]. Unlike
conventional Aminochlorination processes, the reaction devel-
oped here requires no activating additives and may provide
multifunctionalized vicinal N-fluoroamino and chloro adducts.
Also, the N–F bond in these adducts would probably lead to
the development of new chemical reactions.
Figure 1. Diverse applications of aminohalogenations.
[a] Key Laboratory for Advanced Materials & Institute of Fine Chemicals,
East China University of Science and Technology,
130 Meilong Road, Shanghai, China
E-mail: yxj@ecust.edu.cn
www.ecust.edu.cn
[b] Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Science,
345 Lingling Road, Shanghai 200032, China
E-mail: yxj@ecust.edu.cn
www.ecust.edu.cn
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under http://dx.doi.org/10.1002/ejoc.201600709.
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Results and Discussion
Table 1. Optimization of the reaction conditions.
We began with the use of styrene (2a) as a model substrate. To
our delight, without any catalyst a single product 3a was ob-
tained in 1,2-dichloroethane (DCE) at 85 °C in 96 % yield
(Entry 1 in Table 1). Other solvents including toluene, DCM (di-
chloromethene), hexane, dioxane, CH3CN and THF were also
used. In ethyl acetate a trace amount of product 3a was de-
tected (Entry 6 in Table 1). The proportion of 2a/1 was found
to influence both the reaction rate and yield (Entries 1, 9–14 in
Table 1). Entry 11 (Table 1) shows the best conditions for the
synthesis of 2-chloro-3-fluoramino adducts. Interestingly, when
DCE was used as solvent at room temperature, 3a was sepa-
rated in 25 % yield with partial starting material retained. How-
ever, with DCM as solvent the regioisomeric product 4a was
obtained in 50 % yield as a single product (Entry 16 in Table 1,
conditions B in the following experiments). When using CH3CN,
CHCl3, or THF as solvents, a mixture of 3a/4a was obtained
(Entries 17–19 in Table 1). Thus, the optimized conditions for
the regioselective formation of adduct 3 are conditions A:
1 equiv. of alkene 2, 1.2 equiv. of CFBSA, DCE as solvent, 85 °C;
and for the regioselective generation of adduct 4, conditions B
are chosen: 1 equiv. of alkene 2, 1.2 equiv. of CFBSA, DCM as
solvent, room temperature (less than 30 °C).
Entry
Solvent
Temp.
2a/1
Time
[h]
Product
(yield [%])[c]
1
2[a]
3[a]
4
DCE
DCM
85 °C
85 °C
85 °C
85 °C
85 °C
85 °C
85 °C
85 °C
85 °C
85 °C
85 °C
85 °C
85 °C
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:1
1:1.1
1:1.2
1:1.3
1:1.4
1:2
1:2
1:2
1:2
1:2
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
8
3
3
1
0.5
12
0.5
12
12
12
12
3a (96)
3a (89)
3a (94)
3a (78)
3a (95)
3a (trace)
3a (75)
3a (91)
3a (79)
3a (86)
3a (96)
3a (96)
3a (96)
3a (25)
3a (83)
4a (50)
hexane
dioxane
toluene
ethyl acetate
THF
CH3CN
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCM
CH3CN
CHCl3
THF
5
6[a]
7[a]
8
9
10
11
12
13
14
15[b]
16
17
18
19
room temp.
room temp.
room temp.
room temp.
room temp.
room temp.
4a (5), 3a (38)
4a (27), 3a (7)
4a (13), 3a (28)
1:2
Then, the scope of styrenes was tested under optimal reac-
tion conditions. As shown in Table 2, all styrenes regioselect-
ively provided products 3a–3h in good yields under condi-
[a] The reaction proceeded in a pressure glass tube. [b] 10 mol-% AgOAc was
added as catalyst in the reaction. [c] Isolated yields.
Table 2. Scope of substrates: aminochlorination for styrenes.
[a] Reaction conditions: 2 (1.0 mmol), CFBSA (250 mg, 1.2 mmol) and DCE (5.0 mL) at 85 °C. [b] Reaction conditions: 2 (1.0 mmol), CFBSA (250 mg, 1.2 mmol)
and DCM (5.0 mL) at room temp. (room temp. means < 30 °C). [c] Reaction conditions: 2 (1.0 mmol), CFBSA (250 mg, 1.2 mmol), N-fluoro-4-chlorobenzene-
sulfonamide (1.0 mmol) and DCM (5.0 mL) at room temp. [d] Reaction conditions: 2 (1.0 mmol), CFBSA (250 mg, 1.2 mmol), N-fluoro-4-fluoro-benzenesulfon-
amide (1.0 mmol) and DCE (5.0 mL) at room temp.
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Table 3. Scope of substrates: aminochlorination of other alkenes.
[a] Reaction condition A: 2 (1.0 mmol), CFBSA (250 mg, 1.2 mmol) and DCE (5.0 mL) at 85 °C. [b] Reaction conditions B: 2 (1.0 mmol), CFBSA (250 mg,
1.2 mmol) and DCM (5.0 mL) at room temp. [c] Two stereoisomers of 3s with a ratio of 5:1 (determined by the peak area ratio in the 1H NMR spectrum).
tions A. Of para-substituted styrenes, 4-bromostyrene produced
a low yield of 3f. With chlorine as substituent, ortho- and meta-
substituted substrates produced higher yields of 3g and 3h,
respectively, than that of 3d with a para-chloro substituent. Un-
der conditions B, electron-rich styrenes afforded products 4a–
4e in moderate yields. However, minimal products were pro-
duced for styrenes with electron-withdrawing substituents
(NO2, F and Cl). Nevertheless, the addition of N-fluoro-4-chloro-
benzenesulfonamide or N-fluoro-4-fluoro-benzenesulfonamide
to the above reactions enhanced the yield of adducts 4g and
4h.
The scope of alkenes was also tested (Table 3). Under condi-
tions A, 3-phenyl-1-propylene and 4-phenyl-1-butylene were
Figure 3. Single-crystal X-ray diffraction of 3c and 4e.
tolerated in this reaction with the formation of 3i, 3j, 3k, 3l,
rich 1-(4-methoxyphenyl)-1-propylene and 3-(4-methoxyphen-
yl)-1-propylene, respectively.
In order to clarify the structures of 3 and 4, we determined
the single-crystal structures of 3c and 4e (Figure 3).
Although the exact mechanism still requires further investi-
3m in 78–85 % yields. For chain alkenes 4-bromo-1-butylene, 1-
cyclohenylethylene and 3-chloro-2-methyl-1-propylene, 3n, 3o
and 3p were smoothly afforded as single isomers in 75–82 %
yields. An α,ꢀ-unsaturated aliphatic ester specifically yielded 3q
in 85 % yield; we note that this is the first report for an amino-
chlorination of α,ꢀ-unsaturated aliphatic esters. Cyclohexene gation, we suggest the following reaction process (Scheme 1).
and ethyl 3-cyclopentene-1-carboxylate provided 3r and 3s in In our reaction, product 4 was regioselectively formed in di-
1
75 % and 81 % yield, respectively. In the H NMR spectrum of chloromethane (DCM) at room temperature. In DCM, styrene
product 3s, two different configurations with a ratio of 5:1 were attacks C-l of CFBSA at room temperature to generate chlorin-
observed. Under conditons B, while no reaction was observed ium ion 5. Subsequently, the PhSO2NF– anion could selectively
for the majority of the above substrates, adducts 4i and 4j were attack C-1 to give 4. The regioselectivity could be determined
regioselectively produced in 90 % and 78 % yield for electron- by the following two factors: (1) the stability of the PhSO2NF–
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anion could largely increase in comparison that of PhSO2NNa– bond when 3a was treated with K2CO3 in refluxing methanol.
or PhSO2NH– in Chloroamine B, or PhSO2NCl– in PhSO2NCl2; (2) Surprisingly, compound 10 was produced when 4d was stirred
C-1+ is a much more stable cation than C-2+ in 5 for its conjuga- with a small amount of water at room temperature for 2 d. The
1
tion with the benzene ring. The high eletrophilic chlorination presence of aldehyde in the reaction mixture (detected by H
reactivity[14] and the good aminochlorination reactivity to p- and 13C NMR spectroscopy) probably suggests that 2-chloro-
methoxystyrene (Table 2, 4b) could corroborate this proposed acetaldehyde was generated along with the formation of com-
route. However, compound 3 was rapidly formed instead of pound 10; the reaction mechanism is not clear at present, how-
compound 4 at high temperature. Thus, a different mechanism ever (Scheme 2). Although the above conversions occurred eas-
including the initial nucleophilic attack of styrene onto the ni- ily under basic conditions, it is interesting to note that these
trogen atom and a subsequent or concerted nucleophilic attack adducts are much more stable under neutral or acidic circum-
of the chlorine anion onto the carbenium or aziridium species is stances. Thus, these adducts could be precursors of enamines
proposed. In this process, the increase of the N–Cl bond length and aziridines for medicinal chemistry, or as agents for con-
resulting from the increased temperature facilitates the depar- trolled release of fluorine under basic conditions.
ture of the chloride anion. An additional proof for this process
was supplied by a similar reaction with AgOAc as catalyst (En-
Conclusions
try 15 in Table 1).
We have described a catalyst-free aminochlorination of alkenes
with CFBSA. Different from previous methods, no activated ad-
ditives were required in the chloroamination process, and spe-
cial fluoroamino adducts were obtained. Pure 2-chloro-3-fluoro-
amino adducts 3 were afforded in high yields under reflux in
DCE. The regioisomeric adducts 4 were selectively formed when
the reaction was carried out at room temperature with DCM as
solvent. The reaction gave good reactivities and regioselectivi-
ties for most terminal alkenes used with both aromatic and
aliphatic substituents. The electronic and steric effects of the
fluorine atom in CFBSA are crucial for the good reactivity and
regioselectivity. In addition, the N-fluoroamino chlorinated ad-
ducts 3 can be further converted into 2-chloroenamines, chlo-
roamines and aziridines. Interestingly, 4d could also be trans-
formed into N-phenylphenylsulfonamide 10. These conversions
endow the adducts with potential applications as precursors in
chemical synthesis.
Scheme 1. Possible mechanism for the addition of styrenes to CFBSA.
We also envisioned that the conversion of the N–F bond in
adducts 3 or 4 would endow this reaction with additional val-
ues. As shown in Scheme 2, several conversions proceeded
smoothly. 2-Chloroenamines are valuable synthetic intermedi-
ates.[15] Usual elimination of chloroamine compounds can only
supply enamines, and 2-chloroenamines must be prepared
by aminochlorination of alkynes under catalysis.[16] Herein, 2-
chloroenamine 7 was generated in 70 % yield by elimination of
HF from 3a in the presence of Et3N. When 3a was treated with
2 equiv. of NaOH, aziridine 8 was produced in high yield. Com-
pound 9 was afforded by a conversion of the N–F into an N–H
Experimental Section
1. General Information: All starting chemicals were commercially
available and used without further purification. Fluorinating reagent
Selectfluor and chlorinating reagent CFBSA were purchased from
Shanghai Science Bio-pharmaceutical Co. Ltd. Substrates were pur-
chased from Energy Chemical Co. Ltd. and Damas-beta Co. Ltd.
Flash column chromatography was performed using silica gel (300–
400 mesh). 1H NMR spectra were recorded with a Bruker spectrome-
ter at 400 MHz. 19F NMR spectra were recorded with a Bruker spec-
trometer at 376 MHz. 13C NMR spectra were recorded with a Bruker
spectrometer at 100 MHz. Chemical shifts (δ values) are reported in
ppm downfield from the signal of internal tetramethylsilane (TMS).
J values are reported in Hz. IR spectra (film) were recorded with a
Nicolet 6700 spectrophotometer in the range of 400–4000 cm–1
.
HRMS (EI) spectra were recorded with a Waters GCT Premier mass
spectrometer with electron impact mode. CCDC 1465265 (for 3c),
and 1465267 (for 4e) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre.
2. Experimental Details
Scheme 2. Conversion of compounds 3a and 4d. Reaction conditions:
(a) acetonitrile (10 mL), 3a (1.0 mmol), Et3N (1.0 mmol), room temp.; (b) DCE
(10 mL), 3a (1.0 mmol), NaOH (2.0 mmol), reflux; (c) methanol (10 mL), 3a
(1.0 mmol), K2CO3 (1.0 mmol) room temp.
Preparation of N-Chloro-N-fluorobenzenesulfonamide (CFBSA):
In a 250 mL round-bottomed flask equipped with a large magnetic
stir bar, Chloramine-B (5.35 g, 0.025 mol, 1.0 equiv.) and Selectfluor
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(13.50 g, 0.038 mol, 1.5 equiv.) were dissolved in water (100 mL) at
(s, 3 H), 3.63–3.91 (m, 2 H), 5.07 (t, J = 7.2 Hz, 1 H), 7.19 (d, J =
room temperature. The reaction mixture was stirred at room tem- 8.0 Hz, 2 H), 7.25–7.28 (m, 2 H), 7.61 (t, J = 7.6 Hz, 2 H), 7.75 (t, J =
perature overnight (12 h). The mixture was extracted with dichloro-
methane (3 × 30 mL), and the organic layer was dried with sodium
7.6 Hz, 1 H), 7.94 (d, J = 7.6 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 21.33, 57.58, 60.23 (dd, J = 11.6 Hz), 127.39, 129.61,
sulfate. The solvent was removed under reduced pressure, and the 129.74, 130.03, 132.04, 134.89, 135.37, 139.32 ppm. 19F NMR
crude product (yellow liquid) was further purified by flash column
chromatography.
(376 MHz, CDCl3): δ = –46.24 (s, 1 F) ppm. IR (KBr): ν = 3004, 2925,
˜
2860, 1589, 1463, 1428, 1373, 1176, 1109 cm–1. HRMS-EI: calcd. for
C
15H15ClFNO2S 327.0496, found for C15H14ClNO2S [M+
– HF]
General Procedure for the Preparation of N-Fluorobenzene-
sulfonamides 3 (3a as an Example): Styrene 2a (104 mg,
1.0 mmol), CFBSA (250 mg, 1.2 mmol) and 1,2-dichloroethane
(5.0 mL) were added into a tube. The mixture was stirred at 85 °C
for 3 h. The reaction mixture was concentrated under reduced pres-
sure. The product was isolated by flash chromatography (silica gel;
petroleum ether/EtOAc = 20:1) to give 3a (300 mg, 96 %) as a white
solid.
307.0434.
N-{2-[4-(tert-Butyl)phenyl]-2-chloroethyl}-N-fluorobenzene-
sulfonamide (3c): White solid; m.p. 84.7–85.2 °C. 1H NMR (400 MHz,
CDCl3): δ = 1.32 (s, 9 H), 3.65–3.93 (m, 2 H), 5.07–5.11 (m, 1 H), 7.32
(d, J = 8.4 Hz, 2 H), 7.40 (d, J = 8.4 Hz, 2 H), 7.61–7.65 (m, 2 H),
7.74–7.78 (m, 1 H), 7.94–7.96 (dm, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 31.32, 34.76, 57.50, 60.23 (d, J = 11.6 Hz), 126.00, 127.15,
129.59, 129.99, 131.93, 134.73, 135.36, 152.40 ppm. 19F NMR
General Procedure for the Preparation of 4 (4a as an Example):
Styrene 2a (104 mg, 1.0 mmol), CFBSA (250 mg) and DCM (5 mL)
were added into a tube. Then the mixture was stirred at room temp.
for 12 h. The reaction mixture was concentrated under reduced
pressure. The product was isolated by flash chromatography (silica
gel; petroleum ether/EtOAc = 20:1) to give 4a (157 mg, 50 %) as a
colorless liquid.
(376 MHz, CDCl3): δ = 46.49 (s, 1 F) ppm. IR (KBr): ν = 3073, 3033,
˜
3039, 2957, 2903, 2867, 1584, 1450, 1416, 1371, 1186, 1176, 1091,
1027 cm–1. HRMS-EI: calcd. for C18H21ClFNO2S 369.0966, found for
C18H20ClNO2S [M+ – HF] 349.0904.
N-[2-Chloro-2-(4-chlorophenyl)ethyl]-N-fluorobenzenesulfon-
amide (3d): White solid; m.p. 100.9–101.1 °C. 1H NMR (400 MHz,
CDCl3): δ = 3.66–3.88 (m, 2 H), 5.06 (t, J = 7.2 Hz, 1 H), 7.32–7.38
(m, 4 H), 7.63 (t, J = 8.0 Hz, 2 H), 7.77 (t, J = 7.6 Hz, 1 H), 7.93 (d,
J = 7.6 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 56.72, 59.97 (d,
J = 11.7 Hz), 128.96, 129.29, 129.66, 130.04, 131.97, 135.32, 135.48,
136.34 ppm. 19F NMR (376 MHz, CDCl3): δ = –46.82 (s, 1 F) ppm. IR
Procedure for the Preparation of 7: Compound 3a (1.0 mmol),
Et3N (1.0 mmol) and acetonitrile (10 mL) were added into round-
bottomed flask (25 mL). Then the mixture was stirred at room temp.
for 3 h. The reaction mixture was concentrated under reduced pres-
sure. The product was isolated by flash chromatography (silica gel;
petroleum ether/EtOAc = 20:1) to give 7 (70 %) as a white solid.
(KBr): ν = 3098, 3073, 2922, 2854, 1598, 1494, 1449, 1365, 1174,
˜
1091 cm–1. HRMS-EI: calcd. for C14H12Cl2FNO2S 346.9950, found for
C14H11Cl2NO2S [M+ – HF] 326.9890.
Procedure for the Preparation of 8: Compound 3a (1.0 mmol),
NaOH (2.0 mmol) and DCE (10 mL) were added into round-bot-
tomed flask (25 mL). Then the mixture was stirred under reflux for
2 h. The reaction mixture was concentrated under reduced pressure.
The product was isolated by flash chromatography (silica gel; petro-
leum ether/EtOAc = 20:1) to give 8 (95 %) as a white solid.
N-[2-Chloro-2-(4-fluorophenyl)ethyl]-N-fluorobenzenesulfon-
amide (3e): White solid; m.p. 88.9–89.4 °C. 1H NMR (400 MHz,
CDCl3): δ = 3.67–3.88 (m, 2 H), 5.08 (t, J = 7.2 Hz, 1 H), 7.04–7.10
(m, 2 H), 7.36–7.40 (m, 2 H), 7.63 (t, J = 8.0 Hz, 2 H), 7.62–7.65 (m,
2 H), 7.77 (t, J = 7.6 Hz, 1 H), 7.94 (d, J = 7.6 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 56.78, 60.17 (d, J = 11.4 Hz), 116.05 (d, J =
21.3 Hz), 129.41, (d, J = 9.5 Hz), 129.64, 129.99, 131.88, 133.69,
133.70, 135.46, 163.02 (d, J = 247.2 Hz) ppm. 19F NMR (376 MHz,
Procedure for the Preparation of 9: Compound 3a (1.0 mmol),
K2CO3 (1.0 mmol) and methanol (10 mL) were added into round-
bottomed flask (25 mL). Then the mixture was stirred at room temp.
for 3 h. The reaction mixture was concentrated under reduced pres-
sure. The product was isolated by flash chromatography (silica gel;
petroleum ether/EtOAc = 20:1) to give 9 (97 %) as a white solid.
CDCl3): δ = –46.97, –111.93 ppm. IR (KBr): ν = 3079, 2926, 2862,
˜
1604, 1509, 1512, 1393, 1211, 1098 cm–1. HRMS-EI: calcd. for
C14H12ClF2NO2S 331.0245, found for C14H11ClFNO2S [M+ – HF]
311.0182.
3. Analytical Data for the Products
N-Chloro-N-fluorobenzenesulfonamide (CFBSA): Yellow liquid;
1
Rf = 0.55 (10 % ethyl acetate/petroleum ether). H NMR (400 MHz,
N-[2-(4-Bromophenyl)-2-chloroethyl]-N-fluorobenzenesulfon-
amide (3f): White solid; m.p. 113.2–113.5 °C. 1H NMR (400 MHz,
CDCl3): δ = 3.66–3.87 (m, 2 H), 5.04 (t, J = 7.2 Hz, 1 H), 7.26–7.29
(m, 2 H), 7.50–7.54 (m, 2 H), 7.63 (t, J = 8.0 Hz, 2 H), 7.77 (t, J =
7.6 Hz, 1 H), 7.93 (d, J = 7.2 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 57.77, 59.95 (d, J = 11.1 Hz), 123.38, 129.33, 129.68,
130.02, 131.87, 132.24, 135.50, 136.85 ppm. 19F NMR (376 MHz,
CDCl3): δ = 8.07 (d, J = 7.8 Hz, 2 H), 7.86 (t, J = 7.5 Hz, 1 H), 7.69 (t,
J = 7.9 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 136.78, 131.66,
129.70, 128.74 ppm. 19F NMR (376 MHz, CDCl3): δ = 17.72 (s, 1 F)
ppm. IR (neat): ν = 3071, 1582, 1450, 1390, 1190, 1085, 753, 682,
˜
683, 615, 559 cm–1. HRMS-EI: calcd. for C6H5ClFNO2S 208.9714,
found 208.9716.
CDCl3): δ = –45.78 (s, 1 F) ppm. IR (KBr): ν = 3099, 3071, 2921, 2852,
˜
N-(2-Chloro-2-phenylethyl)-N-fluorobenzenesulfonamide (3a):
White solid; m.p. 84.1–84.4 °C. H NMR (400 MHz, CDCl3): δ = 3.70–
3.89 (m, 2 H), 5.09 (t, J = 7.6 Hz, 1 H), 7.35–7.40 (m, 5 H), 7.62 (t, J =
8.0 Hz, 2 H), 7.76 (t, J = 7.6 Hz, 1 H), 7.94 (d, J = 7.27 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 57.58, 60.21 (d, J = 16.1 Hz), 123.70,
127.48, 129.06, 129.31, 129.62, 130.02, 135.40, 137.77 ppm. 19F NMR
1638, 1492, 1448, 1365, 1175 cm– 1 . HRMS-EI: calcd. for
C14H12BrClFNO2S 390.9445, found for C14H11BrClNO2S [M+ – HF]
370.9395.
1
N-[2-Chloro-2-(2-chlorophenyl)ethyl]-N-fluorobenzenesulfon-
amide (3g): White solid; m.p. 72.9–73.3 °C. 1H NMR (400 MHz,
CDCl3): δ = 3.77 (d, J = 7.2 Hz, 1 H), 3.86 (d, J = 7.2 Hz, 1 H), 5.66
(t, J = 6.8 Hz, 1 H), 7.26–7.38 (m, 3 H), 7.58–7.64 (m, 3 H), 7.54 (t,
J = 7.6 Hz, 1 H), 7.95 (d, J = 7.6 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 53.65, 59.00 (d, J = 11.7 Hz), 127.73, 128.98, 129.62,
130.00, 130.02, 132.01, 133.26, 135.15, 135.43 ppm. 19F NMR
(376 MHz, CDCl3): δ = –46.16 (s, 1 F) ppm. IR (KBr): ν = 3091, 3066,
˜
2933, 1652, 1582, 1496, 1449, 1384, 1186 cm–1. HRMS-EI: calcd. for
C
14H13ClFNO2S: 313.0340, found for C14H12O2ClNS [M+ – HF]
293.0276.
N-[2-Chloro-2-(p-tolyl)ethyl]-N-fluorobenzenesulfonamide (3b):
White solid; m.p. 108.3–108.6 °C. 1H NMR (400 MHz, CDCl3): δ = 2.35
(376 MHz, CDCl3): δ = –45.16 (s, 1 F) ppm. IR (KBr): ν = 3097, 2954,
˜
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Full Paper
2925, 2856, 1582, 1477, 1448, 1378, 1186, 1088 cm–1. HRMS-EI: (300 MHz, CDCl3): δ = 1.32 (s, 9 H), 2.08–1.95 (m, 1 H), 2.35–2.24 (m,
calcd. for C14H12Cl2FNO2S 346.9950, found C14H11Cl2NO2S [M+ – HF] 1 H), 2.79–2.69 (m, 1 H), 2.96–2.87 (m, 1 H), 3.46 (d, J = 6.6 Hz, 1 H),
326.9890.
3.59 (d, J = 6.3 Hz, 1 H), 4.11–4.07 (m, 1 H), 7.14 (d, J = 8.1 Hz, 2 H),
7.33 (d, J = 9.6 Hz, 2 H), 7.64 (t, J = 7.8 Hz, 2 H), 7.78 (t, J = 7.5 Hz,
1 H), 7.96 (d, J = 7.5 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
31.50, 34.51, 37.15, 56.48, 59.25, 59.41, 125.57, 128.28, 129.61,
130.04, 131.84, 135.40, 137.27, 149.21 ppm. 19F NMR (136 MHz,
N-[2-Chloro-2-(3-chlorophenyl)ethyl]-N-fluorobenzenesulfon-
amide (3h): White solid; m.p. 73.4–74.2 °C. 1H NMR (400 MHz,
CDCl3): δ = 3.57–3.81 (m, 1 H), 4.96 (t, J = 7.2 Hz, 1 H), 7.18–7.27
(m, 3 H), 7.32 (s, 1 H), 7.55 (t, J = 7.6 Hz, 2 H), 7.69 (t, J = 7.6 Hz, 1
H), 7.86 (t, J = 8.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
56.69, 60.08 (d, J = 11.5 Hz), 125.73, 127.80, 129.50, 129.66, 130.03,
130.35, 135.49, 139.74 ppm. 19F NMR (376 MHz, CDCl3): δ = –45.75
CDCl3): δ = –44.30 (s, 1 F) ppm. IR (KBr): ν = 3070, 3023, 2991, 2869,
˜
1585, 1510, 1448, 1372, 1310, 1182, 1090 cm–1. HRMS-EI: calcd. for
C20H25ClFNO2S 397.1278, found for C20H24ClNO2S [M+ – HF]
377.1208.
(s, 1 F) ppm. IR (KBr): ν = 3065, 2961, 2926, 2870, 1600, 1519, 1479,
˜
1377, 1186, 1086 cm–1. HRMS-EI: calcd. for C14H12Cl2FNO2S
346.9950, found C14H11Cl2NO2S [M+ – HF] 326.9889.
N-(5-Bromo-2-chloropentyl)-N-fluorobenzenesulfonamide (3n):
1
Gray solid; m.p. 50.1–50.4 °C. H NMR (400 MHz, CDCl3): δ = 2.16–
2.25 (m, 1 H), 2.45–2.54 (m, 1 H), 3.50–3.62 (m, 4 H), 4.30–4.37 (m,
1 H), 7.66 (t, J = 8.0 Hz, 2 H), 7.79 (t, J = 7.6 Hz, 1 H), 7.97 (d, J =
7.6 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 29.04, 38.18, 54.97,
58.90 (d, J = 12.7 Hz), 129.68, 130.05, 131.81, 135.53 ppm. 19F NMR
N-(2-Chloro-3-phenylpropyl)-N-fluorobenzenesulfonamide (3i):
Colorless liquid. 1H NMR (400 MHz, CDCl3): δ = 3.03 (dd, J = 8.0, J =
14.4 Hz, 1 H), 3.32 (dd, J = 4.4, 14.4 Hz, 2 H), 3.51–3.67 (m, 2 H),
4.28–4.35 (m, 1 H), 7.23–7.34 (m, 5 H), 7.63 (t, J = 8.0 Hz, 2 H), 7.70
(t, J = 7.6 Hz, 1 H), 7.95 (d, J = 7.6 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 41.51, 57.22, 58.64 (d, J = 11.7 Hz), 127.30, 128.63,
129.62, 129.81, 130.07, 131.84, 135.43, 136.20 ppm. 19F NMR
(376 MHz, CDCl3): δ = –43.14 (s, 1 F) ppm. IR (KBr): ν = 3093, 3060,
˜
2977, 2964, 2919, 2853, 2818, 1448, 1367, 1254, 1185 cm–1. HRMS-
EI: calcd. for C10H12BrClFNO2S 342.9443, found for C10H12BrClFNO2S
342.9442.
(376 MHz, CDCl3): δ = –44.12 (s, 1 F) ppm. IR (KBr): ν = 3061, 3021,
˜
2966, 2875, 1603, 1584, 1497, 1450, 1380, 1185, 1098 cm–1. HRMS-
EI: calcd. for C15H15Cl2FNO2S 327.496, found for C15H14Cl2NO2S [M+
– HF] 307.0434.
N-(2-Chloro-2-cyclohexylethyl)-N-fluorobenzenesulfonamide
1
(3o): White solid; m.p. 88.9–89.4 °C. H NMR (400 MHz, CDCl3): δ =
1.20–1.40 (m, 5 H), 1.63–1.86 (m, 6 H), 3.41–3.70 (m, 2 H), 4.03–4.08
(m, 1 H), 7.64 (t, J = 8.0 Hz, 2 H), 7.75–7.80 (m, 1 H), 7.99 (d, J =
7.2 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 25.71, 26.05, 26.07,
26.24, 30.28, 40.69, 56.97 (d, J = 11.8 Hz), 62.31, 129.50, 129.94,
131.90, 135.25 ppm. 19F NMR (376 MHz, CDCl3): δ = –45.76 (s, 1 F)
N-(3-Chloro-5-phenylpentyl)-N-fluorobenzenesulfonamide (3j):
Grayish solid; m.p. 60.5–61.0 °C. 1H NMR (400 MHz, CDCl3): δ = 1.99–
2.08 (m, 1 H), 2.25–2.35 (m, 1 H), 2.74–2.81 (m, 1 H), 2.92–2.99 (m,
1 H), 3.48 (d, J = 6.8 Hz, 1 H), 3.57 (d, J = 6.8 Hz, 1 H), 4.05–4.11 (m,
1 H), 7.22 (t, J = 7.6 Hz, 3 H), 7.31 (t, J = 8.0 Hz, 2 H), 7.64 (t, J =
8.0 Hz, 2 H), 7.78 (t, J = 7.6 Hz, 1 H), 7.96 (d, J = 7.6 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 32.01, 37.12, 56.38, 59.33 (d, J =
11.5 Hz), 126.39, 128.61, 128.67, 129.60, 130.01, 131.80, 135.40,
140.36 ppm. 19F NMR (376 MHz, CDCl3): δ = –43.86 (s, 1 F) ppm. IR
ppm. IR (KBr): ν = 3071, 2988, 2930, 2855, 1637, 1583, 1448, 1379,
˜
1185 cm–1. HRMS-EI: calcd. for C14H19ClFNO2S 319.0809 found for
C
14H19ClFNO2S [M+ – HF] 299.0749.
N-(2,4-Dichloro-2-methylbutyl)-N-fluorobenzenesulfonamide
(3p): Yellow liquid. 1H NMR (400 MHz, CDCl3): δ = 1.73 (s, 3 H), 3.52–
3.86 (m, 4 H), 7.67 (t, J = 4.4 Hz, 2 H), 7.78 (t, J = 7.6 Hz, 1 H), 7.80
(d, J = 7.3 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 26.70, 51.17,
(KBr): ν = 3071, 3024, 2960, 2872, 1603, 1584, 1450, 1380, 1185,
˜
1089 cm–1. HRMS-EI: calcd. for C16H17Cl2FNO2S 341.0653, found
341.0652.
60.39 (d, J = 11.2 Hz), 67.21, 129.10, 130.00, 132.21, 135.49 ppm. 19
F
N-[2-Chloro-4-(4-chlorophenyl)butyl]-N-fluorobenzenesulfon-
amide (3k): Colorless liquid. 1H NMR (300 MHz, CDCl3): δ = 1.95–
2.04 (m, 1 H), 2.20–2.30 (m, 1 H), 2.67–2.77 (m, 1 H), 2.85–2.94 (m,
1 H), 3.42 (d, J = 6.6 Hz, 1 H), 3.55 (d, J = 6.3 Hz, 1 H), 4.01–4.03 (m,
1 H), 7.11 (d, J = 8.1 Hz, 2 H), 7.24 (d, J = 7.8 Hz, 2 H), 7.62 (t, J =
7.8 Hz, 2 H), 7.76 (t, J = 7.5 Hz, 1 H), 7.93 (d, J = 7.8 Hz, 2 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 31.29, 36.83, 56.11, 59.29 (d, J =
NMR (376 MHz, CDCl3): δ = –36.78 (s, 1 F) ppm. IR (KBr): ν = 3061,
˜
2980, 2935, 2860, 1569, 1450, 1355, 1268, 1180 cm–1. HRMS-EI:
calcd. for C10H12Cl2FNO2S 298.9950, found for C10H11Cl2NO2S [M+
HF] 278.9869.
–
Ethyl 2-Chloro-3-(N-fluorophenylsulfonamido)-2-methyl-
propanoate (3q): Colorless liquid. 1H NMR (400 MHz, CDCl3): δ =
11.7 Hz), 128.70, 129.60, 129.95, 131.50, 132.02, 135.44, 138.75 ppm. 1.24 (t, J = 7.2 Hz, 3 H), 1.80 (s, 3 H), 3.59 (dd, J = 10.2, J = 7.2 Hz)
19F NMR (136 MHz, CDCl3): δ = –44.36 (s, 1 F) ppm. IR (KBr): ν = 3166,
3.47 (dd, J = 9.2, J = 12.8 Hz, 1 H), 4.17–4.24 (m, 2 H), 7.61 (t, J =
8.0 Hz, 2 H), 7.75 (t, J = 7.6 Hz, 1 H), 7.92 (d, J = 8.0 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 13.80, 25.37, 61.36 (d, J = 11 Hz),
˜
3067, 2955, 2927, 2866, 1584, 1492, 1381, 1185, 1091, 1061 cm–1
.
HRMS-EI: calcd. for C16H16Cl2FNO2S 375.0263, found for
C16H15Cl2NO2S [M+ – HF] 355.0212.
62.75, 126.39, 63.93, 129.60, 129.82, 131.85, 135.45, 168.77 ppm. 19
F
NMR (376 MHz, CDCl3): δ = –38.84 (s, 1 F) ppm. IR (KBr): ν = 3041,
˜
N-[4-(4-Bromophenyl)-2-chlorobutyl]-N-fluorobenzenesulfon-
amide (3l): White solid; m.p. 73.2–73.8 °C. 1H NMR (300 MHz,
CDCl3): δ = 2.05–1.93 (m, 1 H), 2.32–2.21 (m, 1 H), 2.72–2.74 (m, 1
H), 2.85–2.89 (m, 1 H), 3.43 (d, J = 6.3 Hz, 1 H), 3.58–3.56 (m, 1 H),
4.04–4.02 (m, 1 H), 7.07 (d, J = 8.0 Hz, 2 H), 7.39 (d, J = 8.1 Hz, 2 H),
7.64 (t, J = 7.8 Hz, 2 H), 7.77 (t, J = 7.5 Hz, 1 H), 7.94 (d, J = 7.5 Hz,
2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 31.38, 36.79, 56.11, 59.25
(d, J = 11.6 Hz), 120.13, 129.61, 129.97, 130.37, 131.61, 131.68,
135.44, 139.28 ppm. 19F NMR (176 MHz, CDCl3): δ = 43.82 (s, 1 F)
2980, 2935, 2864, 1745, 1585, 1449, 1381, 1312, 1242, 1186 cm–1
HRMS-EI: calcd. for C12H15ClFNO4S 323.0394, found 323.0392.
.
N-(2-Chlorocyclohexyl)-N-fluorobenzenesulfonamide (3r): Color-
1
less liquid. H NMR (400 MHz, CDCl3): δ = 1.25–1.33 (m, 1 H), 1.48–
1.51 (m, 1 H), 1.70–1.84 (m, 4 H), 2.01–2.10 (m, 2 H), 3.83–3.90 (m,
1 H), 4.59 (s, 1 H), 7.60 (t, J = 7.6 Hz, 2 H), 7.73 (t, J = 7.6 Hz, 1 H),
7.98 (d, J = 7.6 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 18.87,
22.83 (d, J = 10.08 Hz), 24.49 (d, J = 2.7 Hz), 33.36, 60.07 (d, J =
2.9 Hz), 64.75 (d, J = 11.5 Hz), 129.44, 129.64, 134.29, 129.64, 134.29,
135.03 ppm. 19F NMR (367 MHz, CDCl3): δ = 62.14 (s, 1 F) ppm.
ppm. IR (KBr): ν = 3069, 3024, 2955, 2925, 2863, 1585, 1448, 1381,
˜
1185, 1091, 1016 cm–1. HRMS-EI: calcd. for C16H16BrClFNO2S
418.9757, found for C16H15BrClNO2S [M+ – HF] 398.9688.
IR (KBr): ν = 3074, 2976, 2940, 2862, 1582, 1449, 1368, 1310,
˜
N-{4-[4-(tert-Butyl)phenyl]-2-chlorobutyl}-N-fluorobenzene-
1162 cm–1. HRMS-EI: calcd. for C12H15ClFNO2S 291.0496, found
sulfonamide (3m): White solid; m.p. 67.5–67.9 °C. 1H NMR 291.0495.
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Ethyl 3-chloro-4-(N-fluorophenylsulfonamido)cyclopentane-
carboxylate (3s): Colorless liquid. 1H NMR (400 MH, CDCl3): δ =
1.24 (t, J = 7.2 Hz, 3 H), 2.16–2.41 (m, 4 H), 2.93 (t, J = 7.6 Hz, 1 H),
134.50, 152.36 ppm. 19F NMR (376 MHz, CDCl3): δ = –74.14 (s, 1 F)
ppm. IR (KBr): ν = 3108, 3070, 3039, 2964, 2869, 1582, 1449, 1366,
˜
1176, 1109, 1086, 1025 cm–1. HRMS-EI: calcd. for C18H21ClFNO2S
4.10–4.17 (m, 2 H), 4.27–4.43 (m, 2 H), 7.59–7.63 (m, 2 H) 7.75 (t, J = 369.0966, found for C18H20ClNO2S 369.0973.
8.0 Hz, 1 H), 7.98 (d, J = 7.6 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 11.24, 28.44 (dd, J = 10.0 Hz), 38.11, 40.96, 70.90 (d, J =
11.4 Hz), 129.55, 129.78, 133.70, 133.75, 135.29, 173.62 ppm. 19F
NMR (367 MHz, CDCl3): δ = –63.71 (s, 1 F), –65.76 (s, 1 F) ppm.
N-[2-Chloro-1-(4-fluorophenyl)ethyl]-N-fluoro-4-nitrobenzene-
sulfonamide (4f): White solid; m.p. 130.4–130.9 °C. 1H NMR
(400 MHz, CDCl3): δ = 3.87 (dd, J = 7.2, J = 11.6 Hz,1 H), 4.15 (dd,
J = 7.2, J = 11.6 Hz, 1 H), 5.22 (dt, J = 7.2, J = 38.0 Hz, 1 H), 7.00–
7.04 (m, 2 H), 7.30–7.34 (m, 2 H), 8.00–8.03 (m, 2 H), 8.31–8.34 (m,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 43.09, 67.26 (d, J =
11.7 Hz), 116.03 (d, J = 21.6 Hz), 124.31, 128.70, 130.84, 131.06 (d,
J = 10.1 Hz), 140.44, 156.78 (d, J = 97.6 Hz) ppm. 19F NMR (376 MHz,
IR (KBr): ν = 30291, 2984, 2945, 2862, 1740, 1495, 1403, 1372,
˜
1230 cm–1. HRMS-EI: calcd. for C14H17ClFNO4S 349.0551, found
349.0549.
N-(2-Chloro-1-phenylethyl)-N-fluorobenzenesulfonamide (4a):
Colorless liquid. 1H NMR (400 MHz, CDCl3): δ = 3.88 (dd, J = 7.6, J =
CDCl3): δ = –110.48 (s, 1 F), –72.85 (s, 1 F) ppm. IR (KBr): ν = 3100,
˜
11.6 Hz, 1 H), 4.13 (dd, J = 7.6, J = 11.6 Hz, 1 H), 5.11 (dt, J = 7.2, 3037, 3011, 2964, 2926, 2867, 1605, 1528, 1510, 1383, 1349, 1227,
J = 37.2 Hz, 2 H), 7.13–7.22 (m, 5 H), 7.32 (t, J = 8.0 Hz, 2 H), 7.48 1182 cm–1. HRMS-EI: calcd. for C14H11ClF2N2O4S 376.0096, found
(t, J = 7.2 Hz, 1 H), 7.69 (d, J = 8.0 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 42.45 (d, J = 6.0 Hz), 67.06 (d, J = 11.4 Hz), 127.64,
128.03, 128.04, 128.09, 128.39, 132.15 (d, J = 4.3 Hz), 133.34,
133.68 ppm. 19F NMR (367 MHz, CDCl3): δ = –71.64 (s, 1 F) ppm. IR
376.0100.
4-Chloro-N-[2-chloro-1-(4-fluorophenyl)ethyl]-N-fluoro-
1
benzenesulfonamide (4g): White solid; m.p. 59.5–60.5 °C. H NMR
(400 MHz, CDCl3): δ = 3.86 (dd, J = 7.6, J = 11.2 Hz, 1 H), 4.13 (dd,
J = 7.4, J = 11.6 Hz, 1 H), 5.13 (dt, J = 4.6, J = 38.0 Hz, 1 H), 7.01 (td,
J = 8.4 Hz, 2 H), 7.30 (t, J = 8.4 Hz), 7.46 (d, J = 8.4 Hz, 2 H), 7.74 (d,
J = 8.4 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 43.39 (d, J =
5.6 Hz), 67.26 (d, J = 11.5 Hz), 115.87 (d, J = 21.5 Hz), 129.60, 130.88,
130.99 (d, J = 1.8 Hz), 141.91, 163.89 (d, J = 248.1 Hz) ppm. 19F NMR
(KBr): ν = 3004, 3072, 2965, 1584, 1499, 1445, 1389, 1189 cm–1
HRMS-EI: calcd. for C14H13ClFNO2S 313.0340, found 313.0342.
.
˜
N-[2-Chloro-1-(p-tolyl)ethyl]-N-fluorobenzenesulfonamide (4b):
Colorless liquid. 1H NMR (400 MHz, CDCl3): δ = 2.33 (s, 3 H), 3.88
(dd, J = 7.6, J = 11.2 Hz, 1 H), 4.15 (dd, J = 11.6, J = 7.2 Hz, 1 H),
5.10 (dt, J = 37.2, J = 7.6 Hz, 1 H), 7.10 (d, J = 7.6 Hz, 2 H), 7.20 (d,
J = 8.0 Hz, 2 H), 7.46 (t, J = 7.6 Hz, 2 H), 7.63 (t, J = 7.6 Hz, 1 H),
(367 MHz, CDCl3): δ = –111.18, –71.80 ppm. IR (KBr): ν = 3263, 3100,
˜
2966, 2905, 1605, 1513, 1403, 1241, 1151 cm–1. HRMS-EI: calcd. for
7.81 (d, J = 8.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.25, C14H11Cl2F2NO2S 364.9856, found 364.9853.
43.49 (d, J = 5.9 Hz), 67.82 (d, J = 12.5 Hz), 128.99, 129.00, 129.08,
N-[2-Chloro-1-(4-methoxyphenyl)ethyl]-N,4-difluorobenzene-
129.32, 129.49, 130.23 (d, J = 4.5 Hz), 134.50, 134.59 (d, J = 6.3 Hz),
sulfonamide (4h): White solid; m.p. 72.5–73.4 °C. 1H NMR (400 MHz,
CDCl3): δ = 3.79 (s, 3 H), 3.86 (dd, J = 7.2, J = 11.2 Hz, 1 H), 4.13
(dd, J = 7.2, J = 11.2 Hz, 1 H), 5.09 (dt, J = 7.2, J = 39.20 Hz, 1 H),
6.78–6.82 (m, 2 H), 7.08–7.14 (m, 2 H), 7.19 (d, J = 8.4 Hz, 2 H), 7.76–
6.82 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 43.66 (d, J =
5.1 Hz), 55.39, 67.80 (d, J = 11.5 Hz), 114.07, 116.48 (d, J = 22.7 Hz),
124.96 (d, J = 4.8 Hz), 130.43 (d, J = 1.7 Hz), 130.72 (d, J = 3.1 Hz),
139.40 ppm. 19F NMR (367 MHz, CDCl3): δ = –71.61 (s, 1 F) ppm.
IR (KBr): ν = 3098, 3073, 2945, 2854, 1586, 1462, 1372, 1172,
˜
1107 cm–1. HRMS-EI: calcd. for C15H15ClFNO2S 327.0496, found
327.0495.
N-[2-Chloro-1-(o-tolyl)ethyl]-N-fluorobenzenesulfonamide (4c):
Colorless liquid. 1H NMR (400 MHz, CDCl3): δ = 2.07 (s, 3 H), 4.0–
4.15 (m, 2 H), 7.34–7.38 (m, 3 H), 7.48–7.52 (m, 4 H), 7.83 (d, J = 132.46 (d, J = 9.8 Hz), 160.48, 166.35 (d, J = 256.6 Hz) ppm. 19F NMR
8.0 Hz, 2 H), 7.65 (t, J = 7.6 Hz, 1 H), 7.81 (d, J = 8.0 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 20.12 (d, J = 5.4 Hz), 50.43 (d, J =
7.4 Hz), 72.33 (d, J = 12.5 Hz), 127.04, 128.27, 128.65, 129.02, 134.40,
134.50, 136.59, 137.68 ppm. 19F NMR (367 MHz, CDCl3): δ = –63.32
(367 MHz, CDCl3): δ = –101.51, –72.75 ppm. IR (KBr): ν = 3106, 3069,
˜
2965, 2933, 2862, 1611, 1512, 1364, 1262, 1176, 1158, 1028 cm–1
HRMS-EI: calcd. for C15H14ClFNO3S 361.0351, found 361.0355.
.
N-[2-Chloro-1-(4-methoxyphenyl)propyl]-N-fluorobenzene-
sulfonamide (4i): White solid; m.p. 70.5–71.6 °C. 1H NMR (300 MHz,
CDCl3): δ = 1.74 (d, J = 6.3 Hz, 3 H), 3.77 (s, 3 H), 4.52–4.43 (m, 1
H), 4.84 (dd, J = 8.7, 8.7 Hz, 1 H), 6.72 (d, J = 8.7 Hz, 2 H), 7.16 (d,
J = 8.4 Hz, 2 H), 7.38 (t, J = 7.8 Hz, 2 H), 7.57 (t, J = 7.5 Hz, 1 H),
7.68 (t, J = 7.8 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 22.95,
55.28, 57.06, 72.01 (d, J = 11.2 Hz), 113.57, 124.66 (d, J = 5.6 Hz),
128.93, 129.39, 131.06 (d, J = 2.0 Hz), 134.32, 134.64, 160.06 ppm.
(s, 1 F) ppm. IR (KBr): ν = 3066, 3031, 3003, 2922, 2851, 1584, 1497,
˜
1448, 1363, 1174, 1088 cm–1. HRMS-EI: calcd. for C15H15ClFNO2S
327.0496, found 327.0495.
N-[2-Chloro-1-(4-methoxyphenyl)ethyl]-N-fluorobenzenesulfon-
amide (4d): White solid; m.p. 71.1–72.3 °C. 1H NMR (400 MHz,
CDCl3): δ = 3.79 (s, 3 H), 3.83–3.88 (m, 1 H), 4.10–4.15 (m, 1 H), 5.08
(dt, J = 7.2, 39.2 Hz, 1 H), 6.79–6.82 (m, 2 H), 7.21 (d, J = 8.4 Hz, 2
H), 7.44–7.48 (m, 2 H), 7.62 (t, J = 7.6 Hz, 1 H), 7.80 (d, J = 7.6 Hz, 2 19F NMR (136 MHz, CDCl3): δ = –74.36 (s, 1 F) ppm. IR (KBr): ν =
˜
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 43.70 (d, J = 5.4 Hz), 55.56,
67.67 (d, J = 11.6 Hz), 114.07, 125.19 (d, J = 4.7 Hz), 129.12, 129.51,
3073, 2989, 2973, 2936, 2837, 1608, 1584, 1513, 1400, 1250, 1172,
1029 cm–1. HRMS-EI: calcd. for C16H17ClFNO3S 357.0602, found
130.41, 134.62, 134.76, 160.36 ppm. 19F NMR (367 MHz, CDCl3): δ = 357.0605.
–72.10 (s, 1 F) ppm. IR (KBr): ν = 3056, 2952, 2860, 1653, 1638, 1616,
˜
N-[1-Chloro-3-(4-methoxyphenyl)propan-2-yl]-N-fluoro-
1448, 1377, 1357 cm–1. HRMS-EI: calcd. for C15H15ClFNO3S 343.0445,
found 343.0446.
benzenesulfonamide (4j): Yellow liquid. 1H NMR (400 MHz, CDCl3):
δ = 3.06–3.20 (m, 2 H), 3.65–3.74 (m, 2 H), 3.81 (s, 3 H), 4.31–4.45
(m,1 H), 6.86 (d, J = 8.0 Hz, 2 H), 7.15 (d, J = 8.0 Hz, 2 H), 7.6 (t, J =
7.6 Hz, 2 H), 7.73 (t, J = 7.6 Hz, 1 H), 7.96 (d, J = 8.0 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 39.53, 54.32, 56.44, 56.48 (d, J =
11.6 Hz), 112.97, 127.07, 128.59, 129.03, 129.86, 130.76, 134.42,
157.81 ppm. 19F NMR (367 MHz, CDCl3): δ = –72.10 (s, 1 F) ppm. IR
N-{1-[4-(tert-Butyl)phenyl]-2-chloroethyl}-N-fluorobenzene-
sulfonamide (4e): White solid; m.p. 85.1–85.7 °C. 1H NMR (400 MHz,
CDCl3): δ = 1.28 (s, 9 H), 3.85 (dd, J = 7.2, J = 11.2 Hz,1 H), 4.14 (dd,
J = 7.2, J = 11.2 Hz, 1 H), 5.12 (dt, J = 7.2, J = 39.2 Hz, 1 H), 7.17 (d,
J = 8.0 Hz, 2 H), 7.25 (d, J = 7.6 Hz, 2 H), 7.40 (t, J = 8.0 Hz, 2 H),7.56
(t, J = 7.6 Hz, 1 H), 7.76 (d, J = 7.6 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 31.36, 34.72, 43.64, 68.09, 125.63, 128.51, 129.51, 130.00,
(KBr): ν = 3056, 2965, 2926, 2839, 1601, 1581, 1493, 1448, 1072
˜
cm–1. HRMS-EI: calcd. for C16H17ClFNO3S 357.0602, found 357.0608.
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(Z)-N-(2-Chloro-2-phenylvinyl)benzenesulfonamide (7): White
solid; m.p. 78.0–79.6 °C. 1H NMR (400 MHz, CDCl3): δ = 6.95–7.01
(m, 2 H), 7.29–7.36 (m, 3 H), 7.45 (d, J = 7.6 Hz, 2 H), 7.55 (t, J =
8.0 Hz, 2 H), 7.62 (t, J = 7.6 Hz, 1 H), 7.90 (t, J = 8.0 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 116.09, 119.76, 125.67, 126.80,
128.48, 128.72, 129.61, 133.53, 135.10, 139.92 ppm. IR (KBr): ν =
˜
3274, 3075, 3032, 2922, 2850, 1652, 1593, 1448, 14401, 1347, 1165,
1092 cm–1. HRMS-EI: calcd. for C14H12ClNO2S 293.2771, found
293.0279.
1
2-Phenyl-1-(phenylsulfonyl) aziridine (8):[17] White solid. H NMR
(400 MHz, CDCl3): δ = 2.42 (d, J = 4.4 Hz, 1 H), 3.03 (d, J = 7.2 Hz,
1 H), 3.82 (t, J = 7.2 Hz, 1 H), 7.21–7.22 (m, 2 H), 7.29–7.55 (m, 3 H),
7.54 (t, J = 7.6 Hz, 1 H), 7.64 (t, J = 7.6 Hz, 1 H), 8.0 (d, J = 7.6 Hz, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 36.15, 41.28, 126.69, 128.02,
128.50, 128.72, 129.27, 133.80, 135.80, 138.16 ppm.
N-(2-Chloro-2-phenylethyl)benzenesulfonamide (9): White solid.
1H NMR (400 MHz, CDCl3): δ = 3.33–3.47 (m, 2 H), 4.79 (dd, J = 6.0,
7.6 Hz, 1 H), 4.93 (t, J = 6.0 Hz, 1 H), 7.18–7.22 (m, 2 H), 7.24–7.27
(m, 3 H), 7.43–7.48 (m, 2 H), 7.51–7.55 (m, 1 H), 7.76–7.79 (d, J =
7.6 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 50.44, 61.74,
127.05, 127.30, 129.01, 129.20, 129.38 ppm.
N-(4-Methoxyphenyl)benzenesulfonamide (10): White solid. 1H
NMR (400 MHz, CDCl3): δ = 3.76 (s, 3 H), 6.38 (s, 1 H), 6.77 (d, J =
8.0 Hz, 2 H), 6.96 (d, J = 8.4 Hz), 7.43 (t, J = 7.6 Hz, 2 H), 7.54 (t, J =
7.6 Hz, 1 H), 7.69 (d, J = 7.6 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 55.54, 114.56, 125.72, 127.41, 128.82, 129.06, 132.99,
139.03, 158.16 ppm.
Supporting Information (see footnote on the first page of this
article): Experimental procedures, new compounds' characterization
and crystal structure data.
Note: The authors declare no competing financial interests.
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Acknowledgments
We are grateful to the National Natural Science Foundation of
China (NSFC) (grant number 21372077) for financial support
and Dr. Xiao-Peng He for his revision for the manuscript.
Keywords: Alkenes · Aminochlorination · Sulfonamides ·
Chlorine
[1] J. E. G. Kemp, in: Comprehensive Organic Synthesis (Eds.: B. M. Trost, I.
Fleming), Pergamon, Oxford, 1991, vol. 7, p. 469.
Received: June 10, 2016
Published Online: ■
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Aminochlorination
Alkenes were aminochlorinated in
high yields and good regioselectivity
by the direct, catalyst-free addition of
alkenes to CFBSA (N-chloro-N-fluoro-
benzenesulfonamide).
X.-Q. Pu, H.-Y. Zhao, Z.-H. Lu, X.-P. He,
X.-J. Yang* ............................................ 1–9
Aminochlorination of Alkenes with
CFBSA
DOI: 10.1002/ejoc.201600709
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