Unexpected distinction in reactivity of pentafluorobenzenesulfonyl halides toward organolithiums and organomagnesium halides

Article abstract of DOI:10.1515/znb-2017-0092

C₆F₅SO₂Cl reacts with organolithiums and organomagnesium halides RM (R = Me, Bu, Ph; M = Li, MgX) to give mainly C₆F₅H and C₆F₅Cl. C₆F₅SO₂Br and

Full text of DOI:10.1515/znb-2017-0092

Z. Naturforsch. 2017; 72(10)b: 731–737
Vadim V. Bardin* and Alexander M. Maksimov
Unexpected distinction in reactivity of
pentafluorobenzenesulfonyl halides toward
organolithiums and organomagnesium halides
https://doi.org/10.1515/znb-2017-0092
fluoride and phenyllithium, although with the less basic
PhMgBr, only the substitution of fluorine atom occurs [10]
(Scheme 1, routes c and d). At low temperatures, sulfones
were obtained in high yield [5] (Scheme 1, route e).
Reactions of arenesulfonyl chlorides with alkyl- and
arylmagnesium bromide give mainly the correspond-
ing sulfones, but the processes are often complicated by
partial reduction of ArSO2Cl to ArSO2H; formation of sul-
foxides, sulfides, biaryls and alkyl or aryl chlorides; and
so on. It should be noted that these data are very old and
the compositions of products were not analyzed com-
pletely [11–13]. In all these cases, aryl moieties in ArSO2X
were phenyl, tolyl, xylyl or naphthyl, whereas the effect of
Received May 29, 2017; accepted July 20, 2017
Abstract: C6F5SO2Cl reacts with organolithiums and orga-
nomagnesium halides RM (Rꢀ=ꢀMe, Bu, Ph; Mꢀ=ꢀLi, MgX) to
give mainly C6F5H and C6F5Cl. C6F5SO2Br and PhMgBr form
C6F5H and (C6F5S)2. This is in contrast to known transforma-
tions of them which yield exclusively C6F5SO2Nu under the
action of O- and N-nucleophiles. Alternatively, C6F5SO2F is
converted to C6F5SO2R and 4-BuC6F4SO2F or 2-PhC6F4SO2Ph
under the same conditions. When Rꢀ=ꢀMe, minor amounts
of (C6F5SO2)2CH2 and 4-C6F5SO2CH2C6F4SO2F form in addi-
tion to C6F5SO2CH3.
Keywords: C-nucleophiles; organolithium; organomagne- electron-withdrawing substituent(s) in aryl moiety on the
sium halides; pentafluorobenzenesulfonyl halides.
reaction pathways was not investigated.
In search of the convenient synthetic routes to
(arylsulfonyl)polyfluoroarenes and (alkylsulfonyl)poly-
fluoroarenes, we explored the interaction of C6F5SO2X
with some organometallic compounds. Our expecta-
tions were based on the facts of the easy substitution
of chlorine atom in C6F5SO2Cl by O- and N-nucleophiles
and formation of organyl pentafluorobenzenesulfonates
[14–25] and pentafluorobenzenesulfonamides [22, 26–
30], respectively. Pentafluorobenzenesulfonyl fluoride
was the less promising reactant: the strong electron-
withdrawing effect of five fluorine atoms and SO2F group
caused the substitution of fluorine atom at C-4 carbon
atom, while fluorine atom bonded to sulfur remained
intact. For example, C6F5SO2F reacts with piperidine
in ether to yield 4-piperidinotetrafluorobenzenesulfo-
nyl fluoride [31]. The related substitution occurs with
other N-nucleophiles such as aniline [32] and hexam-
ethyldisilazane [33]. The latter forms 4-aminotetrafluor-
obenzenesulfonyl fluoride and NH(4-C6F4SO2F)2. The
interaction of sodium thiosulfate and C6F5SO2F in DMF
led to S(4-C6F4SO2F)2 [34].
1 Introduction
The nucleophilic substitution of halogen atoms X in
RSO2X is one of the typical reactions of this class of orga-
nosulfur derivatives [1, 2]. While O- and N-nucleophiles
convert RSO2X to the corresponding sulfonates and
sulfonamides, organolithiums and organomagnesium
halides (C-nucleophiles) give two types of products. The
reaction of aryllithium or arylmagnesium halides with
arenesulfonyl fluorides leads to the formation of diaryl-
sulfones [3–5] (Scheme 1, route a). When the nucleophile
is AlkM, aryl(alkyl)sulfones are the minor admixture
and major products are 1,1-bis(arylsulfonyl)alkanes [6–9]
(Scheme 1, route b). Similar reactions occur between
methanesulfonyl fluoride or phenylmethanesulfonyl
*Corresponding author: Vadim V. Bardin, N. N. Vorozhtsov
Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian
Academy of Sciences, 9 Lavrentiev Ave., 630090 Novosibirsk,
Russia, e-mail: bardin@nioch.nsc.ru
Alexander M. Maksimov: N. N. Vorozhtsov Novosibirsk Institute of
Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
630090 Novosibirsk, Russia
In fact, pentafluorobenzenesulfonyl halides displayed
the unpredictable reactivity toward these C-nucleophiles.
Herein we present results of reactions of C6F5SO2X (Xꢀ=ꢀF,
Cl, Br) with some organolithiums and organomagnesium
halides.
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ꢀV.V. Bardin and A.M. Maksimov: Reactivity of pentafluorobenzenesulfonyl halides
ether, 20-35 oC
ArSO2F + Ar'M
ArSO2Ar'
(a)
(b)
(c)
(d)
(e)
ether, 20-35 oC
ether, 18-20 oC
ether, 18-20 oC
(ArSO2)2CHR
ArSO2CH2R +
ArSO2F + RCH2M
PhCH2SO2F + PhLi
PhCH2SO2F + PhMgBr
PhCH2SO2CH(Ph)SO2Ph
PhCH2SO2Ph
THF, -78 oC
ArSO2F + RCH2M
M = Li, MgBr
ArSO2CH2R
Scheme 1:ꢀTypical reactions of organosulfonyl fluorides with C-nucleophiles.
1. ether, 25 oC
2. 5% HCl
2 Results and discussion
To avoid or minimize secondary processes, all reactions
were performed in excess of C6F5SO2X.
C6F5H + C6F5Cl + C6F5I
C6F5SO2Cl + 0.8 MeLi (+ LiI)
1
2
5
6
Scheme 3:ꢀReaction of C6F5SO2Cl with MeLi in the presence of LiI.
We found that the reaction of pentafluorobenze-
nesulfonyl chloride (1) with selected C-nucleophiles is
completely different from the reaction with by O- and pentafluorobenzene. Unexpectedly, a significant amount
N-nucleophiles, and C6F5SO2R was not formed. Thus, of decafluorodiphenyldisulfide was also formed (ratio of 2
pentafluorobenzene (2) was the only polyfluoroaromatic to 4ꢀ=ꢀ4:1), while 3 and C6F5SO2Ph were absent (Scheme 5).
product derived from 1 and PhMgBr in ether. Similarly, a
In contrast to C6F5SO2Cl and C6F5SO2Br, pentafluor-
mixture of pentafluorobenzene, bromopentafluoroben- obenzenesulfonyl fluoride (10) was converted to C6F5SO2R
zene (3) (ratio 27:1) and decafluorodiphenyldisulfide (4) using organolithiums or organomagnesium halides
(trace) was obtained from 1 and BuMgBr (Scheme 2) (here although this process is accompanied by parallel reac-
and below only polyfluoroaromatic products are pre- tions. For instance, the addition of PhMgBr to 10 in ether
sented on schemes).
at 25°C and subsequent hydrolysis gave (phenylsulfonyl)
The slow addition of MeLi (contained LiI) in ether to 1 pentafluorobenzene (11) and, presumably, a few 1-phenyl-
and subsequent hydrolysis gave 2, chloropentafluoroben- sulfonyl-2-phenyltetrafluorobenzene (12) (ratio 8:1). Under
zene (5) and iodopentafluorobenzene (6) in the ratio of the same conditions, the reaction of 10 with BuMgCl gave
5:1:2 (19F NMR). The expected C6F5SO2CH3 was not detected two main products, (butylsulfonyl)pentafluorobenzene
(Scheme 3).
(13) and 4-butyltetrafluorobenzenesulfonyl fluoride (14)
Products 2 and 5 (2:1) were produced from 1 and BuLi. (ratio 1:1) (Scheme 6).
In addition, minor amounts of butylpentafluoroben-
The action of MeLi on 10 also caused the substitu-
zene (7) and 1-(1-ethoxyethyl)pentafluorobenzene (8) tion of fluorine bonded to sulfur by a methyl group and
were detected by 19F NMR and GS-MC analysis, whereas the formation of (methylsulfonyl)pentafluorobenzene
C6F5SO2Bu was not found (Scheme 4).
(15). Unlike the above processes, the main by-products are
When pentafluorobenzenesulfonyl bromide (9) was bis(pentafluorophenylsulfonyl)methane (16) and 4-(pen-
combined with PhMgBr in ether, the major product was tafluorophenylsulfonylmethyl)tetrafluorobenzenesulfonyl
1. ether, 25 oC
C6F5H
C6F5SO2Cl + 0.7 PhMgBr
1
2. 5% HCl
2
1. ether, 25 oC
C6F5H + C6F5Br + C6F5SSC6F5 (trace)
C6F5SO2Cl + 0.6 BuMgBr
4
2
1
2. 5% HCl
3
Scheme 2:ꢀReaction of C6F5SO2Cl with organomagnesium bromides.
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1. ether, hexane, 25 oC
2. 5% HCl
C6F5SO2Cl + 0.7 BuLi
C6F5H + C6F5Cl + C6F5Bu + C6F5CH(CH3)OC2H5
1
2
5
7
8
Scheme 4:ꢀReaction of C6F5SO2Cl with BuLi.
1. ether, 25 oC
nucleophilic RMgBr. Probably, the first process proceeds
via the addition of RLi and subsequent homolytic dis-
sociation of S–Cl and then C–S bonds. The abstraction
of hydrogen atom by pentafluorophenyl radical from
solvent gives C6F5H, and recombination with chlorine
atom results in C6F5Cl (Scheme 8, route a). Alternatively,
the redox process can be a source of pentafluorophenyl
radical from C6F5SO2X (Xꢀ=ꢀCl, Br) and RMgBr (Scheme 8,
route b).
The other remarkable peculiarity is the formation of
C6F5I from C6F5SO2Cl and MeLi that contains LiI (Scheme 3)
and the absence of C6F5I in the reaction of C6F5SO2F
(Scheme 7). It should be noted that the closely related
replacement of the SO2Cl group by hydrogen and iodine
atoms was observed in the reaction of 1 with NaI in MeCN
at room temperature [35] (Scheme 9).
C6F5H + C6F5SSC6F5
C6F5SO2Br + 0.7 PhMgBr
2. 5% HCl
2
4
9
Scheme 5:ꢀReaction of C6F5SO2Br with phenylmagnesium bromide.
1. ether, 25 o
2. 5% HCl
C
C6F5SO2F + 0.7 PhMgBr
C6F5SO2Ph + 2-PhC6F4SO2Ph
11 12
10
1. ether, 25 oC
2. 5% HCl
C6F5SO2Bu + 4-BuC6F4SO2F
13 14
C6F5SO2F + 0.7 BuMgCl
10
Scheme 6:ꢀReaction of C6F5SO2F with organomagnesium halides.
fluoride (17). They were formed because of the hydrogen
abstraction from 15 by MeLi (Lewis base) and subsequent
attack of 10 at the sulfur atom and carbon atom C-4,
respectively, by the carboanion C6F5SO2CH2− (molar ratio of
15:16:17ꢀ=ꢀ5:6:1) (Scheme 7).
Following the author of [35], we concluded that the
formation of C6F5I in our case also proceeded via a similar
redox mechanism.
Comparing the reactivity of C6F5SO2F with C6F5SO2Cl
and C6F5SO2Br reveals the following distinctions. Under
the action of RMgX, pentafluorobenzenesulfonyl fluo-
ride underwent the substitution of fluorine atom bonded
to sulfur as well as of fluorine bonded to carbon atom
of pentafluorophenyl moiety. The other C-nucleophile,
C6F5SO2CH2−, generated by hydride abstraction from the
methyl group of 15 by methyllithium reacted with 10 in a
similar manner. In contrast, reactions of pentafluoroben-
zenesulfonyl chloride (bromide) led to the other type of
products. Taking into account the easy substitution of
chlorine in C6F5SO2Cl with O- and N-nucleophiles, this
reaction route was quite unexpected.
The investigation of reaction mechanisms was out of
the framework of this paper, but we would like to make
some suggestions. The analysis of products indicated
the radical nature of processes. Thus, the reaction of
C6F5SO2Cl with highly nucleophilic RLi always leads to
C6F5H and C6F5Cl (Schemes 3 and 4). The latter product
O
R
route 1:
+
C6F5SO2Cl + RLi
C6F5
C6F5
S
Cl
OLi
RSOOLi
+
S-H
C6F5
C6F5H
C6F5Cl
C6F5
+
Cl
route 2:
C6F5SO2Cl + RMgBr
+ R + +MgBr
C6F5SO2Cl
SO2Cl
C6F5SO2Cl
S-H
C6F5
C6F5H
+
C6F5
BrMg
+
BrMgOS(O)Cl
SO2Cl
Scheme 8:ꢀProposed routes of decomposition of C6F5SO2X (Xꢁ=ꢁCl,
as well as C6F5Br was not found in reactions with the less Br) under the action of C-nucleophiles.
1. ether, 25 oC
C6F5SO2F + 0.8 MeLi
C6F5SO2Me + (C6F5SO2)2CH2 + 4-C6F5SO2CH2C6F4SO2F
15 168 17
10
2. 5% HCl
Scheme 7:ꢀReaction of C6F5SO2F with MeLi.
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ꢀV.V. Bardin and A.M. Maksimov: Reactivity of pentafluorobenzenesulfonyl halides
CH3CN
C6F5SO2Br [39, 40] were prepared by the reported proce-
dures. The known compounds 13 [36], 15 [21], 2 [12], 3, 5,
6 [41], 4 [42], 8 [43] and 16 [44] were identified by 19F NMR
spectroscopy and GC-MS data. The preparation of 14 will
be reported in a forthcoming publication. The constitu-
tion of 12 (minor component) was deduced from the 1H, 19F
NMR spectra and GC-MS data of its mixture with 13. Yields
of products were determined by 19F NMR spectroscopy
using C6H5F as a quantitative internal reference. For reli-
able identification, compound 7 was prepared separately
by the modified procedure given in [45].
Experiment:
C6F5SO2Cl + NaI
C6F5I + C6F5H (1 : 1)
20 o
C
Proposed
mechanism:
C6F5SO2Cl + I
C6F5SO2Cl
C6F5SO2Cl
+ I
+ SO2 + Cl
C6F5
C6F5I
C6F5H
C6F5
C6F5
+
I
S-H
Scheme 9:ꢀExperimental data and the proposed route of formation
of C6F5I from C6F5SO2Cl and NaI in acetonitrile [35].
3 Conclusions
4.1 Preparation of butylpentafluorobenzene 7
1. Under the action of organolithiums or organomagne-
sium halides, pentafluorobenzenesulfonyl chloride
(bromide) mainly forms C6F5H, whereas the substitu-
tion of chlorine (bromine) with the organyl rest does
not occur. This distinguishes them from ArSO2Cl with
the less electron-withdrawing aryl moieties (phenyl,
tolyl, xylyl or naphthyl) which mainly form the cor-
responding diarylsulfones.
A solution of 2.4 m butyllithium in hexanes (5 mL,
12 mmol) was added dropwise to a cold (0–3°C) solu-
tion of C6F6 (5.2 g, 29 mmol) in ether (30 mL) within 1 h.
The reaction solution was stirred at 20–25°C for 1 h and
poured into 5% HCl. The organic phase was washed with
brine and dried with MgSO4. Volatiles were removed
under reduced pressure and the residue was distilled to
give 7 (1.45 g, 55%), b.p. 170–172°C (lit. [46]: b.p. 54–55°C/
2 Torr, 174–175°C/760 Torr).
2. In contrast to C6F5SO2X (Xꢀ=ꢀCl, Br), C6F5SO2F under-
goes only the nucleophilic substitution of fluorine in
the pentafluorophenyl substituent as well as at the
sulfur atom.
4.1.1 Butylpentafluorobenzene 7
3. Increased electron-accepting character of the aryl
moiety in arenesulfonyl halide facilitates redox reac- 1H NMR (CCl4): δꢀ=ꢀ2.71 (t, 3J(H1,H2)ꢀ=ꢀ7.5 Hz, 2H, H1),
tions, and decreases the substitution of chlorine 1.58 (tt, J(H2,H1)ꢀ=ꢀ7.5 Hz, J(H2,H3)ꢀ=ꢀ7.5 Hz, 2H, H2), 1.39
3
3
(bromine). On the other hand, C6F5SO2F reacts as its (tq, J(H3,H2)ꢀ=ꢀ7.5 Hz, J(H3,H4)ꢀ=ꢀ7.2 Hz, 2H, H3), 0.97 (t,
3
3
non-fluorinated analog (Scheme 1), although the par- 3J(H4,H3)ꢀ=ꢀ7.2 Hz, 3H, H4). – F NMR (CCl4): δꢀ=ꢀ−145.7 (m,
19
3
allel reaction at the C6F5 group also occurs.
2F, F2,6), −159.1 (t, J(F4,F3,5)ꢀ=ꢀ20 Hz, 1F, F4), −164.0 (m, 2F,
F3,5) [lit. [46]: 19F NMR ([D6]acetone): δꢀ=ꢀ−145.4 (2F), −158.2
(1F), −169.6 (2F)].
4 Experimental section
The NMR spectra were recorded on a Bruker Avance 300
(1H at 300.13 MHz, 19F at 282.40 MHz) spectrometer. The
4.2 Reaction of C6F5SO Cl with
phenylmagnesium2bromide
chemical shifts were referenced to TMS (1H), CCl3F [19F, A two-necked flask equipped with a magnetic stir bar,
with C6F6 as secondary reference (δꢀ=ꢀ−162.9 ppm)]. A Hewl- rubber septum and reflux condenser topped with an
ett-Packard 1800A (with HP-5MS column) instrument was adapter for inlet/outlet argon and connected with a
used for gas chromatography-mass spectrometry (GC-MS) bubbler was flushed with dry argon and charged with
analysis. BuLi (2.4 m solution in hexanes) (Sigma-Aldrich) C6F5SO2Cl (803 mg, 3.01 mmol) in ether (5 mL). A solution of
was used as supplied. Solutions of C4H9MgCl, C4H9MgBr 0.68 m PhMgBr in ether (3 mL, 2.04 mmol) was added with
and C6H5MgBr in ether were prepared from chlorobutane, a syringe within 15 min. The reaction mixture was stirred
bromobutane and bromobenzene and Mg, respectively. for 1 h and quenched with 5% HCl (2 mL). The organic
CH3Li was prepared from methyl iodide and lithium. Ether phase was decanted and dried with MgSO4. The solution
was distilled over LiAlH4 and stored over sodium. (Phenyl- contained C6F5SO2Cl (1.78 mmol) and C6F5H (1.06 mmol).
sulfonyl)pentafluorobenzene [36], and pentafluoroben- In addition, C6H6, C6H5Cl, and C6H5C6H5 (3:12:1) were found
zenesulfonyl halides C6F5SO2F [37], C6F5SO2Cl [38] and (GC-MS).
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MgSO4. The solution contained C6F5SO2Br (0.31mmol),
C6F5H (0.53 mmol) and (C6F5S)2 (0.13 mmol) (19F NMR). In
addition, C6H6, C6H5Br and C6H5C6H5 (6:8:1) were found
4.3 Reaction of C6F SO Cl with
butylmagnesiu5m b2romide
A solution of 0.32 m BuMgBr in ether (2.6 mL, 0.84 mmol) (GC-MS).
was added within 40 min with a syringe to a stirred solu-
It should be noted that C6F5SO2Br decomposes under
tion of C6F5SO2Cl (319 mg, 1.20 mmol) in ether (3 mL). the conditions of the GC-MS analysis. Thus, The GC-MS
The reaction mixture was left overnight and quenched analysis of a mixture of C6F5SO2Br and C6F5CF3 (quanti-
with 5% HCl (2 mL). The organic phase was decanted tative internal reference; molar ratio of 1:1.3; 19F NMR)
and dried with MgSO4. The solution contained C6F5SO2Cl showed the presence of C6F5Br, C6F5H and C6F5CF3 (molar
(0.16 mmol), C6F5H (0.81 mmol), C6F5Br (0.03 mmol) and ratio of 0.5:0.5:1.3), while C6F5SO2Br was not found.
traces of C6F5SSC6F5 (19F NMR). In addition, BuCl, BuBr and
C8H18 were found (GC-MS).
4.7 Reaction of C6F5SO F with
phenylmagnesium2bromide
4.4 Reaction of C6F5SO2Cl with methyllithium
A solution of 0.68 m PhMgBr in ether (1 mL, 0.68 mmol)
A solution of 0.92 m methyllithium in ether (1.1 mL, was added within 10 min to C6F5SO2F (266 mg, 1.06 mmol)
1.01 mmol) was added dropwise within 25 min with in ether (5 mL). The reaction mixture was stirred for 1 h
a syringe to a stirred solution of C6F5SO2Cl (311 mg, and washed with 5% HCl (2 mL). The organic phase was
1.16 mmol) in ether (3 mL) to give a brown suspension. decanted and dried with MgSO4.
It was stirred for 1 h and quenched with 5% HCl (1 mL).
The solution contained C6F5SO2F (0.69 mmol),
The brown organic phase was decanted and dried with C6F5SO2Ph (0.24 mmol) and 2-PhC6F4SO2Ph (0.03 mmol)
19
MgSO4. According to the F NMR spectrum, the solution (19F NMR). The solution was evaporated in vacuo and the
contained C6F5Cl (0.13 mmol), C6F5H (0.60 mmol) and C6F5I residue (a mixture of 11 and 12) was dissolved in CCl4.
(0.26 mmol).
4.7.1 (Phenylsulfonyl)pentafluorobenzene 11 (mixture
4.5 Reaction of C6F5SO2Cl with butyllithium
with 12)
3
A solution of 2.4 mbutyllithium (1 mL, 2.4 mmol) was added 1H NMR (CCl4): δꢀ=ꢀ8.00 (d J(H2,H3)ꢀ=ꢀ8.0 Hz, 2H, H2,6), 7.65
3
3
dropwise within 30 min with a syringe to a stirred solu- (t J(H4,H3,5)ꢀ=ꢀ7.5 Hz, 1H, H4), 7.57 (t J(H3,H2,4)ꢀ=ꢀ7.6 Hz, 2H,
tion of C6F5SO2Cl (854 mg, 3.2 mmol) in ether (3 mL) to give H3,5). – 19F NMR (CCl4): δꢀ=ꢀ−136.7 (m, 2F,F2,6), −146.4 (tt,
a white suspension. It was stirred overnight and treated 3J(F4,F3,5)ꢀ=ꢀ21 Hz, J(F4,F2,6)ꢀ=ꢀ7 Hz, 1F, F4), −159.9 (m, 2F,
4
with 5% HCl (3 mL). The organic phase was decanted, F3,5). – 19F NMR (ether): δꢀ=ꢀ−135.9 (m, 2F, F2,6), −145.9 (tt,
washed with brine and dried with MgSO4. According to 3J(F4,F3,5)ꢀ=ꢀ21 Hz, 4J(F4,F2,6)ꢀ=ꢀ7 Hz, 1F, F4), −159.6 (m, 2F, F3,5).
the 19F NMR spectrum, the solution contained C6F5SO2Cl – GC-MS: m/zꢀ=ꢀ308.
(0.45 mmol), C6F5Cl (0.78 mmol), C6F5H (1.57 mmol), C6F5Bu
and C6F5CH(CH3)OC2H5 (traces). In addition, BuCl and
BuSO2Cl (1:2) were detected by GC-MS.
4.7.2 1-Phenylsulfonyl-2-phenyltetrafluorobenzene 12
(mixture with 11)
4.6 Reaction of C6F5SO Br with
phenylmagnesium2bromide
1H NMR (CCl4): δꢀ=ꢀ8.00 (d 3J(H2,H3)ꢀ=ꢀ8.0 Hz, 2H, H2,6), 7.64 (t
3J(H4,H3,5)ꢀ=ꢀ7.6 Hz, 1H, H4), 7.59 (t 3J(H3,H2,4)ꢀ=ꢀ6.9 Hz, 2H, H3,5)
(SO2C6H5), 7.6–7.4 (5H, C6H5). – 19F NMR (CCl4): δꢀ=ꢀ−132.5 (ddd,
A solution of 0.68 m PhMgBr in ether (1 mL, 0.68 mmol) 3J(F6,F5)ꢀ=ꢀ22 Hz, 4J(F6,F4)ꢀ=ꢀ11 Hz, 5J(F6,F3)ꢀ=ꢀ11 Hz, 1F, F6), −135.9
was added within 15 min with a syringe to a stirred solu- (ddd, 3J(F3,F4)ꢀ=ꢀ23 Hz, 4J(F3,F5)ꢀ=ꢀ3 Hz, 5J(F3,F6)ꢀ=ꢀ11 Hz, 1F, F3),
tion of C6F5SO2Br (318 mg, 1.02 mmol) in ether (5 mL). Ini- −148.1 (ddd, 3J(F4,F3)ꢀ=ꢀ20 Hz, 3J(F4,F5)ꢀ=ꢀ23 Hz, 5J(F4,F6)ꢀ=ꢀ11 Hz,
tially, the colorless solution became yellow and turbid, 1F,F4), −154.5 (ddd, 3J(F5,F4)ꢀ=ꢀ20 Hz, 4J(F5,F6)ꢀ=ꢀ23 Hz,
but within several minutes it became transparent again. 5J(F5,F3)ꢀ=ꢀ3 Hz, 1F,F5). – 19F NMR (ether): δꢀ=ꢀ−131.5 (ddd,
After 1 h, the yellow solution was poured into 5% HCl 3J(F6,F5)ꢀ=ꢀ22Hz, 4J(F6,F4)ꢀ=ꢀ11Hz, 5J(F6,F3)ꢀ=ꢀ11Hz, 1F, F6), −135.0
(2 mL). The organic phase was decanted and dried with (ddd, 3J(F3,F4)ꢀ=ꢀ23 Hz, 4J(F3,F5)ꢀ=ꢀ3 Hz, 5J(F3,F6)ꢀ=ꢀ11 Hz, 1F, F3),
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ꢀꢀꢀꢁ
736ꢀ ꢀV.V. Bardin and A.M. Maksimov: Reactivity of pentafluorobenzenesulfonyl halides
−147.9 (ddd, 3J(F4,F3)ꢀ=ꢀ20 Hz, 3J(F4,F5)ꢀ=ꢀ23 Hz, 5J(F4,F6)ꢀ=ꢀ11 Hz, (0.42 mmol), (C6F5SO2)2CH2 (0.50 mmol) and, presumably,
1F, F4), −154.2 (ddd, 3J(F5,F4)ꢀ=ꢀ20 Hz, 4J(F5,F6)ꢀ=ꢀ23 Hz, 4-C6F5SO2CH2C6F4SO2F (0.08 mmol) (19F NMR).
5J(F5,F3)ꢀ=ꢀ3 Hz, 1F, F5). – GC-MS: m/zꢀ=ꢀ366.
4.9.1 (Methylsulfonyl)pentafluorobenzene 15
4.8 Reaction of C6F SO2F with
butylmagnesiu5m chloride
1H NMR (acetone): δꢀ=ꢀ3.33 (s, 3H, CH3). – 19F NMR
3
(ether): δꢀ=ꢀ−137.2 (m, 2F, F2,6), −146.3 (tt, J(F4,F3,5)ꢀ=ꢀ21 Hz,
A solution of 0.37 m BuMgCl in ether (2 mL, 0.74 mmol) 4J(F4,F2,6)ꢀ=ꢀ7 Hz, 1F, F4), −160.0 (m, 2F, F3,5) (lit. [21]: 1H NMR
19
was added to a stirred solution of C6F5SO2F (257 mg, (DMSO): δꢀ=ꢀ3.51 (s, 3H, CH3); F NMR (DMSO): δꢀ=ꢀ−137.56
1.0 mmol) in ether (3 mL). The suspension formed was (2F), −145.51 (1F), −159.4 (2F)).
stirred for 1 h, treated with 5% HCl (1 mL). The organic
phase was decanted and dried with MgSO4. The solution
contained C6F5SO2F (0.75 mmol), C6F5SO2Bu (0.06 mmol) 4.9.2 Bis(pentafluorophenylsulfonyl)methane 16
and 4-BuC6F4SO2F (0.07 mmol) (19F NMR). The solution
1
was evaporated under reduced pressure and the residue 1H NMR (acetone): δꢀ=ꢀ5.70 (s, 2H, CH2) (lit. [44]: H NMR
(a mixture of 13 and 14) was dissolved in CCl4.
(CDCl3): δꢀ=ꢀ6.08 (s)). – 19F NMR (acetone): δꢀ=ꢀ−134.5 (m,
4F, F2,6), −142.4 (tt, J(F4,F3,5)ꢀ=ꢀ20 Hz, J(F4,F2,6)ꢀ=ꢀ9 Hz, 2F,
3
4
F4), −159.4 (m, 4F, F3,5).
4.8.1 (Butylsulfonyl)pentafluorobenzene 13 (mixture
with 14)
4.9.3 4-(Pentafluorophenylsulfonylmethyl)-
tetrafluorobenzenesulfonyl fluoride 17
1H NMR (CCl4): δꢀ=ꢀ3.24 (t, 3J(H1,H2)ꢀ=ꢀ7 Hz, 2H, SCH2), 1.7–1.6
(m, 4H, 2CH2), 1.05 (t, 3J(H4,H3)ꢀ=ꢀ7 Hz, 3H, CH3). – 19F NMR
3
(CCl4): δꢀ=ꢀ−136.9 (m, 2F,F2,6), −145.3 (tt, J(F4,F3,5)ꢀ=ꢀ20 Hz, 1H NMR (acetone): δꢀ=ꢀ5.20 (s, 2H, CH2). – 19F NMR (acetone):
4J(F4,F2,6)ꢀ=ꢀ7 Hz, 1F, F4), −159.3 (m, 2F, F3,5). – 19F NMR δꢀ=ꢀ74.0 (t, 4J(SO2F,F2,6)ꢀ=ꢀ13 Hz, 1F, SO2F), −133.9 (m, 2F, F2,6),
(ether): δꢀ=ꢀ−136.0 (m, 2F, F2,6), −145.8 (tt, 3J(F4,F3,5)ꢀ=ꢀ21 Hz, −135.5 (m, 2F, F3,5) (C6F4SO2F), −135.4 (m, 2F, F2,6), −143.0 (tt,
4J(F4,F2,6)ꢀ=ꢀ7 Hz, 1F, F4), −159.5 (m, 2F, F3,5). – GC-MS: 3J(F4,F3,5)ꢀ=ꢀ21 Hz, 4J(F4,F2,6)ꢀ=ꢀ8 Hz, 1F, F4), −159.4 (m, 2F, F3,5)
m/zꢀ=ꢀ288.
(C6F5SO2CH2).
Acknowledgments: The work was supported by FASO
Russia on the project 0302-2016-0001. The authors would
like to acknowledge the Multi-Access Chemical Service
Center SB RAS for spectral and analytical measurements.
4.8.2 4-Butyltetrafluorobenzenesulfonyl fluoride 14
(mixture with 13)
1H NMR (CCl4): δꢀ=ꢀ2.93 (t, 3J(H1,H2)ꢀ=ꢀ7 Hz, 2H, CH2), 1.4–1.5
(m, 4H, 2CH2), 1.05 (t, 3J(H4,H3)ꢀ=ꢀ7 Hz, 3H, CH3). – 19F NMR
(CCl4): δꢀ=ꢀ72.3 (t, 4J(SO2F,F2,6)ꢀ=ꢀ15 Hz, 1F, SO2F), −136.1 (m,
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4.9 Reaction of C6F5SO2F with methyllithium
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The solution contained C6F5SO2F (1.03 mmol), C6F5SO2CH3
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V.V. Bardin and A.M. Maksimov: Reactivity of pentafluorobenzenesulfonyl halidesꢂ
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