Field of the Invention
[0001.] The present invention relates to a process for industrial production of
fluorosulfuric acid aromatic-ring esters.
Background Art
[0002.] Fluorosulfuric acid aromatic-ring esters are useful as low-cost
substitutes for trifluoromethanesulfonic acid aromatic-ring esters (Non-Patent
Document 1). As typical production processes of fluorosulfuric acid aromatic-ring
esters, there are known a process for producing a fluorosulfuric acid aromatic-ring
ester by thermal decomposition of an arenediazonium fluorosulfate (Non-Patent
Document 2), a process for producing a fluorosulfuric acid aromatic-ring ester with
the use of sulfonylchloridefluoride (SO2C1F) (Non-Patent Document 3) and a
process for producing a fluorosulfuric acid aromatic-ring ester with the use of
fluorosulfuric acid anhydride (Non-Patent Document 4). There is also known, as a
technique relevant to the present invention, a process for producing a fluorosulfuric
acid aromatic-ring ester with the use of sulfuryl fluoride (SO2F2) (Patent Document
1).
Prior Art Documents
Patent Documents
[0003.] Patent Document 1: U.S. Patent No. 3,733,304
Non-Patent Documents
[0004.] Non-Patent Document 1: J. Org. Chem. (U.S.), 1994, vol. 59, p. 6683
Non-Patent Document 2: Ber. Dtsch. Chem. Ges. B (Germany), 1930,
vol. 63. p. 2653
Non-Patent Document 3: J. Org. Chem. (U.S.), 1961, vol. 26, p. 4164
Non-Patent Document 4: J. Org. Chem. (U.S.), 1991, vol. 56, p. 3493
Summary of the Invention
Problems to be solved by the Invention
[0005.] In the processes of Non-Patent Document 2 and 4, however, the raw
substrate material or reactant (i.e. arenediazonium fluorosulfate or fluorosulfuric
acid anhydride) is difficult to obtain on a large scale. In the process of Non-Patent

Document 3, the target compound cannot always be obtained with a high yield (the
yield of the target compound ranges from 45 to 85%). In the process of Patent
Document 1, the reaction conditions of high temperature and high pressure (120°C,
350 psi) or long reaction time (18 hours) are required for the reaction of the raw
substrate material with sulfuryl fluoride in the presence of pyridine.
[0006.] Under these circumstances, there has been a strong demand to develop
an industrial production process for producing a fluorosulfuric acid aromatic-ring
ester rapidly with a high yield under moderate reaction conditions by the use of a
raw substrate material and a reactant both of which are easily available on a large
scale.
[0007.] It is an object of the present invention to produce an industrial
production process of a fluorosulfuric acid aromatic-ring ester in which the above-
mentioned problems have been solved.
Means for Solving the Problems
[0008.] As a result of extensive researches, the present inventors have found that
it is possible to produce a fluorosulfuric acid aromatic-ring ester by reacting an
aromatic-ring hydroxyl compound with sulfuryl fluoride in the presence of a tertiary
amine except pyridine and methylpyridine. The present invention is based on such a
finding. In the present invention, the reaction can be completed when the reaction
temperature is 75°C or lower, when the pressure is 1.0 MPa or lower or when the
reaction time is 12 hours or less. It is preferable to adopt either one of these reaction
conditions, and is particularly preferable to combine any of these reaction
conditions, for industrial production of the fluorosulfuric acid aromatic-ring ester.
[0009.] Namely, the present invention includes a process for producing a
fluorosulfuric acid aromatic-ring ester as set forth in the following inventive aspects
l to 4.
[0010.] [Inventive Aspect 1 ]
A process for producing a fluorosulfuric acid aromatic-ring ester of the
general formula [2], comprising reaction of an aromatic-ring hydroxyl compound of

the general formula [1] with sulfuryl fluoride (SO2F2) in the presence of a tertiary
amine except pyridine and methylpyridine
Ar-OH [1]
where Ar represents an aromatic-ring group or a substituted aromatic-ring group
Ar—OSO2F
[2]
where A has the same meaning as in the general formula [1].
[0011.] [Inventive Aspect 2]
The process according to Inventive Aspect 1, wherein the reaction is
conducted at a reaction temperature of 75°C or lower.
[0012.] [Inventive Aspect 3]
The process according to Inventive Aspect 1 or 2, wherein the reaction is
conducted at a reaction pressure of 1.0 MPa or lower.
[0013.] [Inventive Aspect 4]
The process according to any one of Inventive Aspects 1 to 3, wherein
the reaction is conducted in a reaction time of 12 hours or less.
[0014.] The sulfuryl fluoride used in the production process according to the
present invention is widely adapted as a fumigant and is easily available on a large
scale. Further, the target compound can be obtained rapidly with a high yield under
moderate reaction conditions in the production process according to the present
invention. In Patent Document 1, not only pyridine but also triethylamine and
methylpyridine are recited as a tertiary amine. However, the tertiary amine actually
used in Examples of Patent Document 1 was only pyridine. The effects of the
present invention (the rapid, high-yield production of the target compound under the
moderate reaction conditions) are achieved only by the use of the tertiary amine
except pyridine and methylpyridine (see Comparative Examples 1 to 3) and are not
at all disclosed in Patent Document 1. In particular, there is no need to utilize high-
pressure gas production equipment as the reaction can be conducted at a pressure of

1.0 MPa or lower. Furthermore, the crude product can be obtained with a high
purity and thereby subjected to the subsequent reaction step such as coupling
reaction without purification operation e.g. fractional distillation, recrystallization
etc.
[0015.] As mentioned above, all of the prior art problems can be solved in the
production process according to the present invention. The production process
according to the present invention is thus particularly useful for production of the
fluorosulfuric acid aromatic-ring ester.
Detailed Description of Embodiments
[0016.] Hereinafter, the production method of the fluorosulfuric acid aromatic-
ring ester according to the present invention will be described below in detail. It is
understood that: the scope of the present invention is not limited to the following
embodiments; and various modifications and variations can be made to the
following embodiments without departing from the scope of the present invention.
All of the publications cited in the present specification, such as prior art documents
and patent documents e.g. published patents and patent applications, are herein
incorporated by reference.
[0017.] In the production process according to the present invention, a
fluorosulfuric acid aromatic-ring ester of the general formula [2] is produced by
reaction of an aromatic-ring hydroxyl compound of the general formula [1] with
sulfuryl fluoride (SO2F2) in the presence of a tertiary amine except pyridine and
methylpyridine.
[0018.] In the aromatic-ring hydroxyl compound of the general formula [1], Ar
represents an aromatic-ring group or substituted aromatic-ring group. The aromatic-
ring group is of 1 to 18 carbon atoms. Examples of the aromatic-ring group are:
aromatic hydrocarbon groups, such as phenyl, naphthyl and anthryl; and aromatic
heterocyclic groups each containing a heteroatom e.g. nitrogen, oxygen, sulfur etc.,
such as pyrrolyl (including nitrogen-protected form), pyridyl, furyl, thienyl, indolyl
(including nitrogen-protected form), quinolyl, benzofuryl and benzothienyl.

[0019.] Examples of the substituted aromatic-ring group are those obtained by
substitution of any number of and any combination of substituents onto any of
carbon or nitrogen atoms of the above aromatic-ring groups. As such substituents,
there can be used: halogen atoms such as fluorine, chlorine, bromine and iodine;
lower alkyl groups such as methyl, ethyl and propyl; lower unsaturated groups such
as vinyl, allyl and propargyl; lower haloalkyl groups such as fluoromethyl,
chloromethyl and bromomethyl; C(CF3)2OH (including hydroxyl-protected form);
lower alkoxy groups such as methoxy, ethoxy and propoxy; lower haloalkoxy
groups such as fluoromethoxy, chloromethoxy and bromomethoxy; formyloxy
group; lower acyloxy groups such as acetyloxy, propionyloxy and butylyloxy; cyano
group; lower alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl and
propoxycarbonyl; lower alkoxycarbonyl lower alkyl groups such as
methoxycarbonylmethyl, ethoxycarbonylethyl and propoxycarbonylpropyl;
aromatic-ring groups such as phenyl, naphthyl, anthryl, pyrrolyl (including nitrogen-
protected form), pyridyl, furyl, thienyl, indolyl (including nitrogen-protected form),
quinolyl, benzofuryl and benzothienyl; protected carboxyl groups; protected amino
groups; hydroxyl group; protected hydroxyl groups; and groups of the formula:
X-Ar'-OH.
[0020.] In the formula: X-Ar'-OH, X represents a C(CH3)2 group, C(CF3)2
group, oxygen atom, nitrogen atom (including nitrogen protected form), sulfur atom,
SO group or SO2 group; and A' represents a phenylene group or substituted
phenylene group. The position of the substituent on the phenylene group is either 2-
position, 3-position or 4-position relative to hydroxyl group. As the substituent of
the substituted phenylene group, there can be used the same ones as those of the
above substituted aromatic-ring group.
[0021.] The following are specific examples of the aromatic-ring group
substituted with X-Ar'-OH (the substituted aromatic-ring group).


[0022.] It is noted that, in the present specification, the term "lower" means that
the group to which the term is attached is a group of 1 to 6 carbon atoms having a
straight-chain structure, a branched structure or a cyclic structure (in the case of 3 or
more carbons). The aromatic-ring group as the substituent of the aromatic-ring
group may further be substituted with any of halogen atoms, lower alkyl groups,
lower unsaturated groups, lower haloalkyl groups, C(CF3)2OH (including hydroxyl-
protected form), lower alkoxy groups, lower haloalkoxy groups, formyloxy group,
lower acyloxy groups, cyano group, lower alkoxycarbonyl groups, lower
alkoxycarbonyl lower alkyl group, protected carboxyl groups, protected amino
groups, hydroxyl group; protected hydroxyl groups and groups of the formula:
X-Ar'-OH. Examples of the protecting groups for the pyrrolyl, indolyl, hydroxyl,
carboxyl and amino groups are those described in "Protective Groups in Organic
Synthesis", Third Edition, 1999, John Wiley & Sons, Inc. Among others, it is
preferable to use the aromatic-ring group or the aromatic-ring group substituted with
any substituent other than "hydroxyl group", "aromatic-ring group" and
"X-Ar'-OH group". Particularly preferred are the aromatic hydrocarbon group or
the aromatic hydrocarbon group substituted with any substituent other than
"hydroxyl group", "aromatic-ring group" and "X-Ar'-OH group" (substituted
aromatic hydrocarbon group). In the case of an aromatic hydroxyl group having a
plurality of hydroxyl groups, a plurality of fluorosulfonylation reactions may
proceed depending on the reaction conditions adopted.
[0023.] In the fluorosulfuric acid aromatic-ring ester of the general formula [2],
Ar has the same meaning as in the aromatic-ring hydroxyl compound of the general
formula [1].

[0024.] Examples of the tertiary amine (except pyridine and methylpyridine) are
triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, N-
methylpiperidine, 1 -ethylpiperidine, N,N-dicyclohexylmethylamine, N,N-
dicyclohexylethylamine, 4-dimethylaminopyridine, 1,5-diazabicyclo[4.3.0]nona-5-
ene and l,8-diazabicyclo[5.4.0]undec-7-ene. It is less preferable to use a strong
basic tertiary amine such as l,8-diazabicyclo[5.4.0]undec-7-ene because the use of
such a strong basic tertiary amine causes generation of a considerable amount of
diaryl sulfate as a by-product (see Example 3). For this reason, triethylamine,
diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, N-methylpiperidine, 1-
ethylpiperidine, N,N-dicyclohexylmethylamine and N,N-dicyclohexylethylamine
are preferred. Particularly preferred are triethylamine, diisopropylethylamine, tri-n-
propylamine, tri-n-butylamine, N-methylpiperidine and 1-ethylpiperidine. These
bases can be used solely or in any combination thereof. In the present specification,
the term "methylpyridine" refers to 2,6-lutidine, 2,4,6-collidine etc. (naturally
including all of methyl positional isomers).
[0025.] It suffices to use the tertiary amine (except pyridine and methylpyridine)
in an amount of 0.7 mol or more per 1 mol of the aromatic-ring hydroxyl compound
of the general formula [1]. The amount of the tertiary amine (except pyridine and
methylpyridine) used is preferably 0.8 to 20 mol, more preferably 0.9 to 10 mol, per
1 mol of the aromatic-ring hydroxyl compound of the general formula [1].
[0026.] It suffices to use the sulfuryl fluoride (SO2F2) in an amount of 0.7 mol or
more per 1 mol of the aromatic-ring hydroxyl compound of the general formula [1].
The amount of the sulfuryl fluoride used is preferably 0.8 to 10 mol, more preferably
0.9 to 5 mol, per 1 mol of the aromatic-ring hydroxyl compound of the general
formula [1].
[0027.] The reaction can be conducted in a reaction solvent. Examples of the
reaction solvent are: aliphatic hydrocarbon solvents such as n-hexane and n-heptane;
aromatic hydrocarbon solvents such as toluene and xylene; halogenated solvents
such as methylene chloride and 1,2-dichloroethane; ether solvents such as
tetrahydrofuran, tert-butyl methyl ether and 1,2-dimethoxyethane; ester solvents

such as ethyl acetate and n-butyl acetate; amide solvents such as N,N-
methylformamide, l-methyl-2-pyrrolidinone, N,N-dimethylacetoamide and 1,3-
dimethyl-2-imidazolydinone; acetonitrile; dimethyl sulfoxide; and water. Among
others, n-heptane, toluene, methylene chloride, tetrahydrofuran, 1,2-
dimethoxyethane, ethyl acetate, N,N-dimethylformamide, l,3-dimethyl-2-
imidazolydinone, acetonitrile, dimethyl sulfoxide and water are preferred.
Particularly preferred are toluene, methylene chloride, tetrahydrofurane, 1,2-
dimethoxyethane, ethyl acetate, N,N-dimethylformamide and acetonitrile. These
reaction solvents can be used solely or in any combination thereof.
[0028.] It suffices to use the reaction solvent in an amount of 0.01 L (liter) or
more per 1 mol of the aromatic-ring hydroxyl compound of the general formula [1].
The amount of the reaction solvent used is preferably 0.05 to 20 L, more preferably
0.1 to 10 L, per 1 mol of the aromatic-ring hydroxyl compound of the general
formula [1]. Alternatively, the reaction can be conducted in a neat condition without
the use of the reaction solvent (see Example 6).
[0029.] Further, it suffices that the reaction temperature is in the range of -80 to
+100°C. The reaction temperature is preferably in the range of-60 to +75°C, more
preferably -40 to +50°C.
[0030.] It suffices that the reaction pressure is in the range of 2.0 MPa to
atmospheric pressure. The reaction pressure is preferably 1.0 to 0.001 MPa, more
preferably 0.8 to 0.002 MPa.
[0031.] It suffices that the reaction temperature is 24 hours or less. The reaction
time is preferably 12 hours or less, more preferably 6 hours or less. As the reaction
time varies depending on the raw substrate material, reactant and reaction
conditions, it is preferable to determine the time at which there can be seen almost
no decrease of the raw substrate material as the end of the reaction while monitoring
the progress of the reaction by any analytical means such as gas chromatography,
liquid chromatography or nuclear magnetic resonance.
[0032.] The fluorosulfuric acid aromatic-ring ester of the general formula [2]
can be obtained by any ordinary post treatment operation for organic synthesis. The

resulting crude product can be purified to a high purity, as needed, by activated
carbon treatment, fractional distillation, recrystallization, column chromatography or
the like.
[0033.] The thus-obtained fluorosulfuric acid aromatic-ring ester can be used as
an electrophilic reagent for various coupling reactions by transition metal catalysts.
Typical examples of the coupling reaction are name reactions such as Kumada-
Tamao-Corriu coupling reaction, Migita-Kosugi-Stille coupling reaction, Suzuki-
Miyaura coupling reaction, Negishi coupling reaction and Hiyama coupling
reaction.
[0034.] It is feasible to use the fluorosulfuric acid aromatic-ring ester for any
reaction other than the coupling reaction. For example, the fluorosulfuric acid
aromatic-ring ester can be used as a substitute for pseudohalide reaction as discussed
in "Organic Synthesis Developed Using Transition Metal; Its Various Reaction
Modes & New Developments" (Jiro TUJI et al., Kagaku Dojin, 1997). The
fluorosulfuric acid aromatic-ring ester can also suitably be used for
alkoxycarbonylation reaction (see Non-Patent Document 1 (J. Org. Chem. (U.S.),
1994, vol. 59, p. 6683) etc.)
[0035.] In the production process according to the present invention, the reaction
completed solution contains a stoichiometric amount of fluoride (salt or complex of
the tertiary amine except pyridine and methylpyridine and hydrogen fluoride) as a
by-product. The desired reaction of the subsequent step may sometimes be
promoted due to the existence of such a fluoride. In this case, it is feasible to
intentionally omit the post treatment and continuously subject the reaction
completed solution to the subsequent reaction as one-pot reaction for favorable
reaction results. In the case where the reaction completed solution is separated into
two phases, it is feasible to recover the phase containing the fluorosulfuric acid
aromatic-ring ester and directly subject the recovered phase to the subsequent
desired reaction.

Examples
[0036.] The present invention will be described in more detail below with
reference to the following examples. It should be understood that the following
examples are illustrative and are not intended to limit the present invention thereto.
[0037.] [Example 1]
Into a 50-mL pressure-proof reaction vessel of stainless steel (SUS), 5.00
g (30.8 mmol, 1.00 eq) of an aromatic-ring hydroxyl compound of the following
formula, 15.0 mL (0.5 L/mol) of toluene and 4.70 g (46.4 mmol, 1.51 eq) of
triethylamine were charged.

Then, 4.70 g (46.1 mmol, 1.50 eq) of sulfuryl fluoride was gradually blown from a
cylinder into the reaction vessel. The resulting solution was stirred for 2 hours at
room temperature. The pressure inside the reaction vessel was 1.0 MPa or lower
throughout the material charging and reaction steps. It was confirmed by gas
chromatography analysis of the reaction completed solution that the conversion rate
of the reaction was 100%.
The reaction completed solution was diluted with 30 mL of toluene,
washed with 15 mL of water, washed with 10 mL of IN hydrochloric acid, washed
with 10 mL of saturated aqueous sodium hydrogencarbonate solution, and then,
further washed with 10 mL of saturated sodium chloride solution. The recovered
organic phase was concentrated under a reduced pressure and dried under a vacuum.
There was thus obtained 5.68 g of a fluorosulfuric acid aromatic-ring
ester of the following formula.


The yield of the target compound was 76%. The gas chromatographic purity of the
target compound was 97.0% (the content of the toluene as the reaction solvent was
2.7%) The 'H-NMR and 19F-NMR measurement results of the target compound
were indicated below.
1H-NMR (standard material: Me4Si, deuterated solvent: CDCb] 5 ppm: 7.57 (Ar-H,
1H), 7.63 (Ar-H, 1H), 7.66 (Ar-H, 1H), 7.72 (Ar-H, 1H).
19F-NMR (standard material: C6F6, deuterated solvent: CDCl3] δ ppm: 98.86 (s, 3F),
200.12 (s, 1F).
[0038.] [Example 2]
Into a 50-mL pressure-proof reaction vessel of stainless steel (SUS), 4.05
g (25.0 mmol, 1.00 eq) of an aromatic-ring hydroxyl compound of the following
formula, 25.0 mL (1 L/mol) of toluene and 6.95 g (37.5 mmol, 1.50 eq) of tri-n-
butylamine were charged.

Then, 3.83 g (37.5 mmol, 1.50 eq) of sulfuryl fluoride was gradually blown from a
cylinder into the reaction vessel. The resulting solution was stirred for 3 hours at
room temperature. The pressure inside the reaction vessel was 1.0 MPa or lower
throughout the material charging and reaction steps. It was confirmed by gas
chromatography analysis of the reaction completed solution that the conversion rate
of the reaction was 81%.

The reaction completed solution was diluted with 50 mL of toluene,
washed with 50 mL of IN hydrochloric acid, washed twice with 40 mL of 5%
aqueous sodium hydrogencarbonate solution, and then, further washed with 40 mL
of saturated sodium chloride solution. It was confirmed by 19F-NMR measurement
of the recovered organic phase that there existed a fiuorosulfuric acid aromatic-ring
ester of the following formula.

The 19F-NMR measurement results of the target compound were the same as those
of Example 1.
[0039.] [Example 3]
Into a 50-mL pressure-proof reaction vessel of stainless steel (SUS), 4.05
g (25.0 mmol, 1.00 eq) of an aromatic-ring hydroxyl compound of the following
formula, 25.0 mL (1 L/mol) of toluene and 5.71 g (37.5 mmol, 1.50 eq) of 1,8-
diazabicyclo[5.4.0]undec-7-ene were charged.

Then, 3.83 g (37.5 mmol, 1.50 eq) of sulfuryl fluoride was gradually blown from a
cylinder into the reaction vessel. The resulting solution was stirred for 3 hours at
room temperature. The pressure inside the reaction vessel was 1.0 MPa or lower
throughout the material charging and reaction steps. It was confirmed by gas
chromatography analysis of the reaction completed solution that the conversion rate
of the reaction was 100%.
The reaction completed solution was diluted with 50 mL of toluene,
washed with 50 mL of IN hydrochloric acid, washed with 50 mL of 5% aqueous

sodium hydrogencarbonate solution, and then, further washed with 20 mL of 10%
sodium chloride solution. The recovered organic phase was concentrated under a
reduced pressure and dried under a vacuum. There was thus obtained a
fluorosulfuric acid aromatic-ring ester of the following formula.

The 19F-NMR measurement results of the target compound were the same as those
of Example 1. It was further confirmed by 19F-NMR measurement (internal
standard material: a,a,a-trifluorotoluene) that the target compound was contained in
an amount of 1.83 g. The yield of the target compound was 30%. The gas
chromatographic purity of the target compound was 30.3%. There was contained
67.3% of a diaryl sulfate of the following formula.

[0040.] [Example 4]
Into a 50-mL pressure-proof reaction vessel of stainless steel (SUS), 3.80
g (25.0 mmol, 1.00 eq) of an aromatic-ring hydroxyl compound of the following
formula, 25.0 mL (1 L/mol) of toluene and 4.91 g (38.0 mmol, 1.52 eq) of
diisopropylethylamine were charged.

Then, 4.10 g (40.2 mmol, 1.61 eq) of sulfuryl fluoride was gradually blown from a
cylinder into the reaction vessel. The resulting solution was stirred for 4 hours at

room temperature. The pressure inside the reaction vessel was 1.0 MPa or lower
throughout the material charging and reaction steps. It was confirmed by gas
chromatography analysis of the reaction completed solution that the conversion rate
of the reaction was 100%.
There was thus obtained a fluorosulfuric acid aromatic-ring ester of the
following formula.

The selectivity of the target compound was 96.3%. The 1H-NMR and 19F-NMR
measurement results of the target compound were indicated below.
1H-NMR (standard material: Me4Si, deuterated solvent: CDC13] δ ppm: 7.43 (Ar-H,
2H), 8.17(Ar-H,2H).
19F-NMR (standard material: C6F6, deuterated solvent: CDCI3] δ ppm: 200.43 (s,
1F).
[0041.] [Example 5]
Into a 300-mL pressure-proof reaction vessel of stainless steel (SUS),
15.2 g (99.9 mmol, 1.00 eq) of an aromatic-ring hydroxyl compound of the
following formula, 100 mL (1 L/mol) of toluene and 15.2 g (150 mmol, 1.50 eq) of
triethylamine were charged.


Then, 15.3 g (150 mmol, 1.50 eq) of sulfuryl fluoride was gradually blown from a
cylinder into the reaction vessel. The resulting solution was stirred for 3 hours at
room temperature. The pressure inside the reaction vessel was 1.0 MPa or lower
throughout the material charging and reaction steps. It was confirmed by gas
chromatography analysis of the reaction completed solution that the conversion rate
of the reaction was 100%.
The reaction completed solution was diluted with 100 mL of toluene,
washed with 50 mL of IN hydrochloric acid, washed with 50 mL of saturated
aqueous sodium hydrogencarbonate solution, and then, further washed twice with 20
mL of saturated sodium chloride solution. The recovered organic phase was dried
with anhydrous sodium sulfate, concentrated under a reduced pressure and dried
under a vacuum.
There was thus obtained 23.1 g of a fluorosulfuric acid aromatic-ring
ester of the following formula.

The yield of the target compound was 99%. The gas chromatographic purity of the
target compound was 99.7%. The I9F-NMR measurement results of the target
compound were the same as those of Example 4.
[0042.] [Example 6]
Into a 50-mL pressure-proof reaction vessel of stainless steel (SUS), 10.8
g (99.9 mmol, 1.00 eq) of an aromatic-ring hydroxyl compound of the following
formula and 12.1 g (120 mmol, 1.20 eq) of triethylamine were charged.


Then, 12.2 g (120 mmol, 1.20 eq) of sulfuryl fluoride was gradually blown from a
cylinder into the reaction vessel. The resulting solution was stirred for 3 hours and
30 minutes at room temperature. The pressure inside the reaction vessel was 1.0
MPa or lower throughout the material charging and reaction steps. It was confirmed
by gas chromatography analysis of the reaction completed solution that the
conversion rate of the reaction was 100%.
The reaction completed solution was diluted with 60 mL of ethyl acetate
and washed with 40 mL of water. The recovered aqueous phase was extracted with
20 mL of ethyl acetate. The recovered organic phases were combined together. The
combined organic phase was washed with 15 mL of IN hydrochloric acid, 15 mL of
saturated aqueous sodium hydrogencarbonate solution, and then, further washed
with 15 mL of saturated sodium chloride solution. The washed organic phase was
dried with anhydrous sodium sulfate, concentrated under a reduced pressure and
dried under a vacuum.
There was thus obtained 16.9 g of a fluorosulfuric acid aromatic-ring
ester of the following formula.

The yield of the target compound was 89%. The gas chromatographic purity of the
target compound was 99.6% (the content of the 4-methylphenol as the raw substrate

material was 0.2%) The 1H-NMR and 19F-NMR measurement results of the target
compound were indicated below.
'H-NMR (standard material: Me4Si, deuterated solvent: CDC13] δ ppm: 2.39 (s, 3H),
7.21 (Ar-H, 2H), 7.26 (Ar-H, 2H).
19F-NMR (standard material: C6F6, deuterated solvent: CDCI3] δ ppm: 198.78 (s,
IF).
[0043.] [Example 7]
Into a 50-mL pressure-proof reaction vessel of stainless steel (SUS), 830
mg (4.99 mmol, 1.00 eq) of an aromatic-ring hydroxyl compound of the following
formula, 15.0 mL (3 L/mol) of 1,2-dimethoxyethane and 1.15 g (11.4 mmol, 2.28
eq) of triethylamine were charged.

Then, 510 mg (5.00 mmol, 1.00 eq) of sulfuryl fluoride was gradually blown from a
cylinder into the reaction vessel. The resulting solution was stirred for 10 hours at
room temperature. The pressure inside the reaction vessel was 1.0 MPa or lower
throughout the material charging and reaction steps.
It was confirmed by 1H-NMR measurement of the reaction completed
solution that the conversion rate of the reaction was 100%. It was further confirmed
by 1H-NMR and I9F-NMR measurements of the reaction completed solution that
there existed a fluorosulfuric acid aromatic-ring ester of the following formula as a
main product.


The 1H-NMR and 19F-NMR measurement results of the target compound were
indicated below.
1H-NMR (standard material: Me4Si, deuterated solvent: CDCl3]δ ppm: 3.67 (s, 2H),
3.72 (s, 3H), 7.31 (Ar-H, 2H), 7.40 (Ar-H, 2H).
19F-NMR (standard material: C6F6, deuterated solvent: CDCl3] δ ppm: 199.23 (s,
IF).
[0044.] [Comparative Example 1]
Into a 50-mL pressure-proof reaction vessel of stainless steel (SUS), 4.05
g (25.0 mmol, 1.00 eq) of an aromatic-ring hydroxyl compound of the following
formula, 25.0 mL (1 L/mol) of toluene and 2.97 g (37.5 mmol, 1.50 eq) of pyridine
were charged.

Then, 3.83 g (37.5 mmol, 1.50 eq) of sulfuryl fluoride was gradually blown from a
cylinder into the reaction vessel. The resulting solution was stirred for 2 hours and
30 minutes at room temperature.
It was confirmed by gas chromatography analysis of the reaction
completed solution that the conversion rate of the reaction was 0%. It was further
confirmed by 19F-NMR measurement of the reaction completed solution that there
did not exist a fluorosulfuric acid aromatic-ring ester of the following formula.

As a result, the desired reaction did not proceed with the use of pyridine.
It is assumed that the severe reaction conditions as disclosed in Patent Document 1

(U.S. Patent No. 3,733,304) are required in order for the desired reaction to proceed
with the use of pyridine.
[0045.] [Comparative Example 2]
Into a 50-mL pressure-proof reaction vessel of stainless steel (SUS), 4.05
g (25.0 mmol, 1.00 eq) of an aromatic-ring hydroxyl compound of the following
formula, 25.0 mL (1 L/mol) of toluene and 4.02 g (37.5 mmol, 1.50 eq) of 2,6-
lutidine were charged.

Then, 3.83 g (37.5 mmol, 1.50 eq) of sulfuryl fluoride was gradually blown from a
cylinder into the reaction vessel. The resulting solution was stirred for 2 hours and
30 minutes at room temperature.
It was confirmed by gas chromatography analysis of the reaction
completed solution that the conversion rate of the reaction was 0%. It was further
confirmed by 19F-NMR measurement of the reaction completed solution that there
did not exist a fluorosulfuric acid aromatic-ring ester of the following formula.

As a result, the desired reaction did not proceed with the use of 2,6-
lutidine. It is also assumed that the severe reaction conditions as disclosed in Patent
Document 1 (mentioned above) are required in order for the desired reaction to
proceed with the use of 2,6-lutidine.

[0046.] [Comparative Example 3]
Into a 50-mL pressure-proof reaction vessel of stainless steel (SUS), 3.80
g (25.0 mmol, 1.00 eq) of an aromatic-ring hydroxyl compound of the following
formula, 25.0 mL (1 L/mol) of toluene and 3.26 g (41.2 mmol, 1.65 eq) of pyridine
were charged.

Then, 4.20 g (41.2 mmol, 1.65 eq) of sulfuryl fluoride was gradually blown from a
cylinder into the reaction vessel. The resulting solution was stirred for 4 hours at
room temperature.
It was confirmed by gas chromatography analysis of the reaction
completed solution that the conversion rate of the reaction was 0%. It was further
confirmed by 19F-NMR measurement of the reaction completed solution that there
did not exist a fluorosulfuric acid aromatic-ring ester of the following formula.

Although the same reaction was conducted by changing the amount of
the pyridine to 1.53 eq and changing the amount of the sulfuryl fluoride to 1.49 eq,
the conversion rate of the reaction was 0%. The reaction results were reproducible.
As a result, the desired reaction did not proceed with the use of pyridine.
It is also assumed that the severe reaction conditions as disclosed in Patent
Document 1 (mentioned above) are required in order for the desired reaction to
proceed with the use of pyridine.

[0047.] As described above, the production process according to the present
invention enables rapid, high-yield production of the target fluorosulfuric acid
aromatic-ring ester under moderate reaction conditions with the use of the raw
substrate material and reactant that are easily available on a large scale.
Industrial Applicability
[0048.] The target compound of the present invention, that is, fluorosulfuric acid
aromatic-ring ester is suitable for use as intermediates for pharmaceutical and
agrichemical products.

WE CLAIM:
1. A process for producing a fluorosulfuric acid aromatic-ring ester of the
general formula [2], comprising reaction of an aromatic-ring hydroxyl compound of
the general formula [1] with sulfuryl fluoride (SO2F2) in the presence of a tertiary
amine except pyridine and methylpyridine
Ar-OH [1]
where Ar represents an aromatic-ring group or a substituted aromatic-ring group
Ar—OSOzF
[2]
where A has the same meaning as in the general formula [1].
2. The process as claimed in claim 1, wherein the reaction is conducted at a
reaction temperature of 75°C or lower.
3. The process as claimed in claim 1 or 2, wherein the reaction is conducted at a
reaction pressure of 1.0 MPa or lower.

4. The process as claimed in any one of claims 1 to 3, wherein the reaction is
conducted in a reaction time of 12 hours or less.