Description
Title of Invention: INDUSTRIAL METHODS FOR PRODUCING
ARYLSULFUR PENTAFLUORIDES
Technical Field
[0001] The invention relates to industrial methods useful in the production of arylsulfur
pentafluorides.
Background Art
[0002] Arylsulfur pentafluoride compounds are used to introduce one or more sulfur
pentafluoride groups into various commercial organic molecules. In particular, arylsulfur
pentafluorides are useful (as product or intermediate) in the development of liquid crystals
(Eur. J. Org. Chem. 2005, pp. 3095-3100) and as bioactive chemicals such as fungicides,
herbicides, insecticides, paraciticides, anti-cancer drugs, enzyme inhibitors, antimalarial
agent, and other like materials [see, for example, J. Pestic. Sci., Vol. 32, pp. 255-259 (2007);
Chimia Vol. 58, pp. 138-142 (2004); ChemBioChem 2009, 10, pp. 79-83; Tetrahedron Lett.
Vol. 51 (2010), pp. 5137-5140; J. Med. Chem. 2011, Vol. 54, pp. 3935-3949; J. Med. Chem.
2011, Vol. 54, pp. 5540-5561; WO 99/47139; WO 2003/093228; WO 2006/108700 Al; US
2005/0197370; US 7,381,841 B2; US 2008/176865; US 7,446,225 B2; WO 2010/138588 A2;
WO 2011/44184].
[0003] Arylsulfur pentafluorides have been synthesized using one of the following
synthetic methods: (1) fluorination of diaryl disulfies or arylsulfur trifluoride with AgF2 [see
J . Am. Chem. Soc, Vol. 82 (1962), pp. 3064-3072, and J . Fluorine Chem. Vol. 112 (2001),
pp. 287-295]; (2) fluorination of bis(nitrophenyl) disulfides, nitrobenzenethiols, or
nitrophenylsulfur trifluorides with molecular fluorine (F2) [see Tetrahedron, Vol. 56 (2000),
pp. 3399-3408; Eur. J . Org. Chem., Vol. 2005, pp. 3095-3100; and USP 5,741,935]; (3)
fluorination of diaryl disulfides or arenethiols with F2, CF3OF, or CF (OF)2 in the presence or
absence of a fluoride source (see US Patent Publication No. 2004/0249209 Al); (4)
fluorination of diaryl disulfides with XeF2 [see J . Fluorine Chem., Vol. 101 (2000), pp. 279-
283]; (5) reaction of l,4-bis(acetoxy)-2-cyclohexene with SF5Br followed by
dehydrobromination or hydrolysis and then aromatization reactions [see J . Fluorine Chem.,
Vol. 125 (2004), pp. 549-552]; (6) reaction of 4,5-dichloro-l-cyclohexene with SF5C 1
followed by dehydrochlorination [see Organic Letters, Vol. 6 (2004), pp. 2417-2419 and PCT
WO 2004/011422 Al]; and (7) reaction of SF5C 1 with acetylene, followed by bromination,
dehydrobromination, and reduction with zinc, giving pentafluorosulfanylacetylene, which
was then reacted with butadiene, followed by an aromatization reaction at very high
temperature [see J. Org. Chem., Vol. 29 (1964), pp. 3567-3570].
[0004] Each of the above synthetic methods has one or more drawbacks making it either
impractical (time and/or yield), overly expensive, and/or overly dangerous to practice. For
example, synthetic methods (1) and (4) provide low yields and require expensive reaction
agents, e.g., AgF2 and XeF2. Methods (2) and (3) require the use of F2, CF3OF, or CF (OF)2,
each of which is a toxic, explosive, and/or corrosive gas, and products produced using these
methods are at a relatively low yield. Note that handling of these gasses is expensive from the
standpoint of production, storage and use. In addition, synthetic methods that require the use
of F2, CF3OF, and/or CF2(OF)2 are limited to the production of deactivated arylsulfur
pentafluorides, such as nitrophenylsulfur pentafluorides, due to their extreme reactivity,
which leads to side-reactions such as fluorination of the aromatic rings when not deactivated.
Methods (5) and (6) also require expensive reactants, e.g., SF5C1 or SF5Br, and have narrow
application because the starting cyclohexene derivatives have limited availability. Finally,
method (7) requires an expensive reactant, SF5C1, and this method includes numerous steps
to reach the arylsulfur pentafluorides (timely and low yield).
[0005] As discussed above, conventional synthetic methodologies for the production of
arylsulfur pentafluorides have proven difficult and are a concern within the art.
[0006] Recently, useful methods have been developed for solving the problems discussed
above (see WO 2008/118787 Al; WO2010/014665 Al; US 2010/0130790 Al; US
2011/0004022 Al; US 7,592,491 B2; US 7,820,864 B2; US 7,851,646 B2). One of the key
steps described in each of these methods is the reaction of an arylsulfur halotetrafluoride with
a fluoride source such as various fluorides compounds including elements found in groups 1,
2, 13-17 and transition elements of the Periodical Table. In particular, hydrogen fluoride is a
useful fluoride source for the industrial process because of its availability and low cost, and
in addition, its liquid nature having a boiling point 19 °C. The liquid nature of hydrogen
fluoride is suitable for large scale industrial processes because of its transportability, fluidity,
and recyclability compared to solids, such as the fluorides of transition elements. However,
methods using hydrogen fluoride still have several drawbacks, including: (1) as hydrogen
fluoride is severely toxic, the amount of hydrogen fluoride used for a reaction must be
minimized for safety and for the sake of the environment; (2) there is evolution of a large
amount of a gaseous, toxic, corrosive hydrogen halide such as HC1 (bp of HC1, -85 °C) from
the reaction of an arylsulfur halotetrafluoride and hydrogen fluoride; (3) in some cases, a low
yield or less purity of the product is obtained, because byproducts such as chlorinated
arylsulfur pentafluorides are formed by side-reactions. These drawbacks cause significant
cost problems in the industrial production of arylsulfur pentafluorides.
[0007] The present invention is directed toward finding more suitable methods to produce
arylsulfur pentafluorides in an industrial scale and overcoming one or more of the problems
discussed above.
Summary of Invention
[0008] Embodiments of the present invention provide a method suitable for the industrial
production of arylsulfur pentafluoride, as represented by formula (I):
arylsulfur halotetrafluoride having a formula (II), shown below, is reacted with anhydrous
hydrogen fluoride (HF) to form arylsulfur pentafluoride (formula I): a molar ratio of the
arylsulfur halotetrafluoride to the anhydrous hydrogen fluoride (the arylsulfur
halotetrafluoride/the anhydrous hydrogen fluoride) is in the range of about 1/10 to about
1/150.
[0009] Embodiments of the present invention also provide methods for producing arylsulfur
pentafluoride (formula I), in which arylsulfur halotetrafluoride is reacted with hydrogen
fluoride in the presence of an additive to form arylsulfur pentafluoride. The additive is
selected from a group consisting of fluoride salts having a formula, M+F (HF) , non-fluoride
salts having a formula, M+Y , and organic compounds having one or more unsaturated bonds
(in a molecule).
[0010] These and various other features as well as advantages which characterize
embodiments of the invention will be apparent from a reading of the following detailed
description and a review of the appended claims.
Description of Embodiments
[0011] Embodiments of the present invention provide industrially useful methods for
producing arylsulfur pentafluorides, as represented by formula (I). Prepared arylsulfur
pentafluorides can be used, for among other things, to introduce one or more sulfur
pentafluoride (SF5) groups into various target organic compounds. As noted in the
Background of the present disclosure, these target organic molecules, after introduction of the
one or more sulfur pentafluoride groups, are useful as medicines, agrochemicals or liquid
crystals. The methods of the invention provide an industrial, cost-effective method for
producing arylsulfur pentafluorides of high purity and in high yield. The target organic
compounds for purposes of the present disclosure typically include at least one target
substitution site for modification by an SF5.
[0012] Embodiments of the invention include a method which comprises reacting an
arylsulfur halotetrafluoride, represented by formula (II), with hydrogen fluoride to form the
arylsulfur pentafluoride having a formula (I), in which a molar ratio of an arylsulfur
halotetrafluoride/hydrogen fluoride is in the range of about 1/10 to about 1/150, preferably
about 1/15 to about 1/100, and furthermore, about 1/15 to about 1/50 (see for example
Scheme 1, Process I).
Scheme 1: Process I
Process I
[0013] With regard to the compounds of formulas (I) and (II): substituents R1, R2, R3, R4,
and R5 each is independently a hydrogen atom; a halogen atom that is a fluorine atom, a
chlorine atom, a bromine atom, or an iodine atom; a substituted or unsubstituted alkyl group
having from 1 to 18 carbon atoms, preferably from 1 to 10 carbon atoms; a substituted or
unsubstituted aryl group having from 6 to 30 carbon atoms, preferably from 6 to 15 carbon
atoms; a nitro group; a cyano group; a substituted or unsubstituted alkanesulfonyl group
having from 1 to 18 carbon atoms, preferably from 1 to 10 carbon atoms; a substituted or
unsubstituted arenesulfonyl group having from 6 to 30 carbon atoms, preferably from 6 to 15
carbon atoms; a substituted or unsubstituted alkoxy group having from 1 to 18 carbon atoms,
preferably from 1 to 10 carbon atoms; a substituted or unsubstituted aryloxy group having
from 6 to 30 carbon atoms, preferably from 6 to 15 carbon atoms; a substituted or
unsubstituted acyloxy group having from 1 to 18 carbon atom, preferably from 1 to 10 carbon
atoms; a substituted or unsubstituted alkanesulfonyloxy group having from 1 to 18 carbon
atom, preferably from 1 to 10 carbon atoms; a substituted or unsubstituted arenesulfonyloxy
group having from 6 to 30 carbon atoms, preferably from 6 to 15 carbon atoms; a substituted
or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms, preferably from 2 to 10
carbon atoms; a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon
atoms, preferably from 7 to 15 carbons; a substituted carbamoyl group having 2 to 18 carbon
atoms, preferably from 2 to 10 carbon atoms; a substituted amino group having 1 to 18
carbon atoms, preferably from 1 to 10 carbon atoms; or a SF5 group.
[0014] With regard to X, in a formula (II), X is a chlorine atom, a bromine atom, or an
iodine atom.
[0015] The term "alkyl" as used herein is linear, branched, or cyclic alkyl. The alkyl part of
alkanesulfonyl, alkoxy, alkanesulfonyloxy, or alkoxycarbonyl group as used herein is also
linear, branched, or cyclic alkyl part.
[0016] The term "substituted alkyl" as used herein means an alkyl moiety having one or
more substituents such as a halogen atom, a substituted or unsubstituted aryl group, and any
other group with or without a heteroatom(s) such as an oxygen atom(s), a nitrogen atom(s),
and/or a sulfur atom(s), which does not limit reactions of this invention.
[0017] The term "substituted aryl" as used herein means an aryl moiety having one or more
substituents such as a halogen atom, a substituted or unsubstituted alkyl group, and any other
group with or without a heteroatom(s) such as an oxygen atom(s), a nitrogen atom(s), and/or
a sulfur atom(s), which does not limit reactions of this invention.
[0018] The term "substituted alkanesulfonyl" as used herein means an alkanesulfonyl
moiety having one or more substituents such as a halogen atom, a substituted or unsubstituted
aryl group, and any other group with or without a heteroatom(s) such as an oxygen atom(s), a
nitrogen atom(s), and/or a sulfur atom(s), which does not limit reactions of this invention.
[0019] The term "substituted arenesulfonyl" as used herein means an arenesulfonyl moiety
having one or more substituents such as a halogen atom, a substituted or unsubstituted alkyl
group, and any other group with or without a heteroatom(s) such as an oxygen atom(s), a
nitrogen atom(s), and/or a sulfur atom(s), which does not limit reactions of this invention.
[0020] The term "substituted alkoxy" as used herein means an alkoxy moiety having one or
more substituents such as a halogen atom, a substituted or unsubstituted aryl group, and any
other group with or without a heteroatom(s) such as an oxygen atom(s), a nitrogen atom(s),
and/or a sulfur atom(s), which does not limit reactions of this invention.
[0021] The term "substituted aryloxy" as used herein means an aryloxy moiety having one
or more substituents such as a halogen atom, a substituted or unsubstituted alkyl group, and
any other group with or without a heteroatom(s) such as an oxygen atom(s), a nitrogen
atom(s), and/or a sulfur atom(s), which does not limit reactions of this invention.
[0022] The term "substituted acyloxy" as used herein means an acyloxy moiety having one
or more substituents such as a halogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted aryl group, and any other group with or without a heteroatom(s)
such as an oxygen atom(s), a nitrogen atom(s), and/or a sulfur atom(s), which does not limit
reactions of this invention.
[0023] The term "substituted alkanesulfonyloxy" as used herein means an
alkanesulfonyloxy moiety having one or more substituents such as a halogen atom, a
substituted or unsubstituted aryl group, and any other group with or without a heteroatom(s)
such as an oxygen atom(s), a nitrogen atom(s), and/or a sulfur atom(s), which does not limit
reactions of this invention.
[0024] The term "substituted arenesulfonyloxy" as used herein means an arenesulfonyloxy
moiety having one or more substituents such as a halogen atom, a substituted or unsubstituted
alkyl group, and any other group with or without a heteroatom(s) such as an oxygen atom(s),
a nitrogen atom(s), and/or a sulfur atom(s), which does not limit reactions of this invention.
[0025] The term "substituted alkoxycarbonyl" as used herein means an alkoxycarbonyl
moiety having one or more substituents such as a halogen atom, a substituted or unsubstituted
aryl group, and any other group with or without a heteroatom(s) such as an oxygen atom(s), a
nitrogen atom(s), and/or a sulfur atom(s), which does not limit reactions of this invention.
[0026] The term "substituted aryloxycarbonyl" as used herein means an aryloxycarbonyl
moiety having one or more substituents such as a halogen atom, a substituted or unsubstituted
alkyl group, and any other group with or without a heteroatom(s) such as an oxygen atom(s),
a nitrogen atom(s), and/or a sulfur atom(s), which does not limit reactions of this invention.
[0027] The term "substituted carbamoyl" as used herein means a carbamoyl moiety having
one or more substituents such as a substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, and any other group with or without a heteroatom(s) such as an
oxygen atom(s), a nitrogen atom(s), and/or a sulfur atom(s), which does not limit reactions of
this invention.
[0028] The term "substituted amino" as used herein means an amino moiety having one or
more substituents such as a substituted or unsubstituted acyl group, a substituted or
unsubstituted alkanesulfonyl group, a substituted or unsubstituted arenesulfonyl group and
any other group with or without a heteroatom(s) such as an oxygen atom(s), a nitrogen
atom(s), and/or a sulfur atom(s), which does not limit reactions of this invention.
[0029] Among the substitutents, R , R2, R , R4, and R5, as described above, a hydrogen
atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, a nitro group, a cyano group, a substituted or unsubstituted
alkanesulfonyl group, a substituted or unsubstituted arenesulfonyl group, a substituted or
unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or
unsubstituted acyloxy group, and a substituted or unsubstituted alkoxycarbonyl group are
preferable. A hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted aryl group, and a nitro group are more preferable because of their
relative availability based on the starting materials.
[0030] Note that according to the nomenclature of Chemical Abstract Index Name, and in
accordance with the present disclosure, for example, C H -SF5 is named sulfur,
pentafluorophenyl-; P-CI-Q5H4-SF5 is named sulfur, (4-chlorophenyl)pentafluoro-; and p-
CH3-C6H 4-SF5 is named sulfur, pentafluoro(4-methylphenyl)-. C H5-SF4C 1 is named sulfur,
chlorotetrafluorophenyl-; p-CH3-C6H4-SF4Cl is named sulfur, chlorotetrafluoro(4-
methylphenyl)-; and p-N0 2-C6H4-SF4Cl is named sulfur, chlorotetrafluoro(4-nitrophenyl)-.
[0031] Arylsulfur halotetrafluorides of formula (II) include isomers such as trans-isomers
and cis-isomers as shown below; arylsulfur halotetrafluoride is represented by ArSF4X:
trans-Isomer
cis-Isomer
Process I (Scheme 1)
[0032] Embodiments of Process I include reacting arylsulfur halotetrafluoride, having a
formula (II), with hydrogen fluoride to form an arylsulfur pentafluoride having a formula (I),
in which a molar ratio of arylsulfur halotetrafluoride/hydrogen fluoride is in the range of
about 1/10 to about 1/150, preferably about 1/15 to about 1/100, and more preferably about
1/15 to about 1/50. When the amount of hydrogen fluoride is less than 10 mol against 1 mol
of an arylsulfur halotetrafluoride, the product's yield is relatively low. When the amount of
hydrogen fluoride is more than 150 mol against 1 mol of an arylsulfur halotetrafluoride, it
leads to low effectiveness in production cost.
[0033] In some embodiments of the present invention the hydrogen fluoride is anhydrous or
hydrous hydrogen fluoride. One particular embodiment that utilizes anhydrous hydrogen
fluoride is shown in Process I. When hydrous hydrogen fluoride is used herein, the content
of water must be minimized, as water may produce arylsulfonyl fluoride or arylsulfonyl
chloride as byproducts, and hence the yields of the products are decreased and the separation
from the byproducts becomes an issue.
[0034] The substituent(s), R1, R2, R , R4, and R5, of the products represented by the formula
(I) may be different from the substituent(s), R , R2, R , R4, and R5, of the starting materials
represented by the formula (II). Thus, embodiments of this invention include transformation
of the R , R2, R3, R4, and R5 to different R1, R2, R3, R4, and R5 which may take place during
the reaction of the present invention or under the reaction conditions, as long as the -SF 4X
moiety is transformed to a -SF 5 group.
[0035] Illustrative arylsulfur halotetrafluorides, as represented by formula (II), of the
invention include, but are not limited to: phenylsulfur chlorotetrafluoride, each isomer (o-, m-,
or p-isomer) of fluorophenylsulfur chlorotetrafluoride, each isomer of difluorophenylsulfur
chlorotetrafluoride, each isomer of trifluorophenylsulfur chlorotetrafluoride, each isomer of
tetrafluorophenylsulfur chlorotetrafluoride, pentafluorophenylsulfur chlorotetrafluoride, each
isomer of chlorophenylsulfur chlorotetrafluoride, each isomer of dichlorophenylsulfur
chlorotetrafluoride, each isomer of trichlorophenylsulfur chlorotetrafluoride, each isomer of
bromophenylsulfur chlorotetrafluoride, each isomer of dibromophenylsulfur
chlorotetrafluoride, each isomer of iodophenylsulfur chlorotetrafluoride, each isomer of
chlorofluorophenylsulfur chlorotetrafluoride, each isomer of bromofluorophenylsulfur
chlorotetrafluoride, each isomer of bromochlorophenylsulfur chlorotetrafluoride, each isomer
of fluoroiodophenylsulfur chlorotetrafluoride, each isomer of methylphenylsulfur
chlorotetrafluoride, each isomer of chloro(methyl)phenylsulfur chlorotetrafluoride, each
isomer of dimethylphenylsulfur chlorotetrafluoride, each isomer of
bromo(methyl)phenylsulfur chlorotetrafluoride, each isomer of bromo(dimethyl)phenylsulfur
chlorotetrafluoride, each isomer of (trifluoromethyl)phenylsulfur chlorotetrafluoride, each
isomer of bis(trifluoromethyl)phenylsulfur chlorotetrafluoride, each isomer of biphenylsulfur
chlorotetrafluoride, each isomer of (methanesulfonyl)phenylsulfur chlorotetrafluoride, each
isomer of (benzenesulfonyl)phenylsulfur chorotetrafluoride, each isomer of
(trifluoromethoxy)phenylsulfur chlorotetrafluoride, each isomer of
(trifluoroethoxy)phenylsulfur chlorotetrafluoride, each isomer of
(tetrafluoroethoxy)phenylsulfur chlorotetrafluoride, each isomer of phenoxyphenylsulfur
chlorotetrafluoride, each isomer of bromophenoxyphenylsulfur chlorotetrafluoride, each
isomer of nitrophenoxyphenylsulfur chlorotetrafluoride, each isomer of nitrophenylsulfur
chlorotetrafluorides, each isomer of chloro(nitro)phenylsulfur chlorotetrafluoride, each
isomer of cyanophenylsulfur chlorotetrafluoride, each isomer of acetoxyphenylsulfur
chlorotetrafluoride, each isomer of (benzoyloxy)phenylsulfur chlorotetrafluoride, each isomer
of (methanesulfonyloxy)phenylsulfur chlorotetrafluoride,
(trifluoromethanesulfonyloxy)phenylsulfur chlorotetrafluoride, each isomer of
(benzenesulfonyloxy)phenylsulfur chlorotetrafluoride, each isomer of
(toluenesulfonyloxy)phenylsulfur chlorotetrafluoride, each isomer of
(methoxycarbonyl)phenylsulfur chlorotetrafluoride, each isomer of
(ethoxycarbonyl)phenylsulfur chlorotetrafluoride, each isomer of
(phenoxycarbonyl)phenylsulfur chlorotetrafluoride, each isomer of (N,Ndimethylcarbamoyl)
phenylsulfur chlorotetrafluoride, each isomer of (N,Ndiphenylcarbamoyl)
phenylsulfur chlorotetrafluoride, each isomer of
(acetylamino)phenylsulfur chlorotetrafluoride, each isomer of (N-acetyl-Nbenzylamino)
phenylsulfur chlorotetrafluoride, each isomer of
(pentafluorosulfanyl)phenylsulfur chlorotetrafluoride, and other like compounds. Each of the
above formula (II) compounds can be prepared according to reported methods (for example,
see WO 2008/118787 Al, incorporated herein by reference for all purposes).
[0036] Arylsulfur halotetrafluorides (Formula II) used for the present inventions can be
obtained by the reported reactions described above. For example, arylsulfur
chlorotetrafluorides (ArSF4X; X=C1) are typically prepared by reaction of a diaryl disulfide
(ArSSAr) or arylthiol (ArSH) with chlorine (Cl ) and metal fluoride such as potassium
fluoride in acetonitrile solvent as shown below (Eq 1) (see WO 2008/118787 Al).
ArSSAr or ArSH + Cl2 + KF ArSF4Cl + KCl (Eq 1)
in CH3CN
After the reaction, the reaction mixture is filtered to remove solid metal halide such as KC1
and excess of solid KF, and the filtrate is concentrated under reduced pressure to give a crude
product, which generally includes about 5-80 weight % of acetonitrile. In order to purify, the
crude product is distilled, preferably under reduced pressure, or the crude product is
recrystallized from a suitable solvent if the product is crystalline.
[0037] The distilled or crystallized products of arylsulfur halotetrafluorides (Formula II) are
used for the reactions of the present inventions. The crude products arylsulfur
halotetrafluorides (Formula II) mentioned above are also usable for the reactions of the
present inventions [see Example 6 (ArSF4Cl:CH3CN=71:29 weight ratio), Example 8
(ArSF4Cl:C¾CN=57:43 weight ratio), and Example 14 (ArSF4Cl:CH3CN=74:26 weight
ratio)]. Thus, the crude products usable for the present inventions may be the materials
obtained by the filtration process to remove the metal halide and an excess of metal fluoride
followed by the concentration process to remove the solvent before the final purification
process such as distillation or crystallization. Using the crude product leads to significant cost
reduction since the purification process, such as a distillation or crystallization, is eliminated.
[0038] From the viewpoint of cost and yield, embodiments of Process I are preferably
carried out without any other solvents. However, in the case of no or low solubility of the
arylsulfur halotetrafluoride and/or its product, arylsulfur pentafluoride, in hydrogen fluoride,
a solvent which dissolves the arylsulfur halotetrafluoride and/or its product may be added to
increase the reaction rate and yield. The preferable solvents will not substantially react with
the starting materials, the final products, and/or the hydrogen fluoride. Suitable solvents
include, but are not limited to, nitriles, ethers, nitro compounds, halocarbons, aromatics,
hydrocarbons, and so on, and mixtures thereof. Illustrative nitriles are acetonitrile,
propionitrile, benzonitrile, and other like. Illustrative ethers are diethyl ether, dipropyl ether,
dibutyl ether, dioxane, glyme, diglyme, triglyme, and other like. Illustrative nitro compounds
are nitromethane, nitroethane, nitrobenzene, and so on. Illustrative halocarbons are
dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane,
tetrachloroethane, trichlorotrifluoroethane, and other like. Illustrative aromatics are benzene,
chlorobenzene, toluene, benzotrifluoride, and other like. Illustrative hydrocarbons are linear,
branched, or cyclic pentane, hexane, heptane, octane, nonane, decane, and other like. Among
these solvents, acetonitrile is preferable because of the high yield of the products. The
amount of the solvent used can be chosen so as to promote the reaction or at least not
interfere with the reaction of the arylsulfur halotetrafluoride and hydrogen fluoride.
[0039] In order to obtain a good yield of product in Process I, the reaction temperature can
be selected in the range of about -80°C to about +250°C, and preferably about -60 °C to about
+200 °C. A suitable temperature can be varied depending on the electron density of the
benzene ring of arylsulfur halotetrafluoride, which is caused by the substituents (R^R 5) on
arylsulfur halotetrafluoride. The electron density is changed by the electron-donating or -
withdrawing effect of the substituents (R^R 5) . For example, an electron-donating group
increases the electron density, while an electron-withdrawing group decreases the density.
The reaction proceeds at relatively low temperature with the arylsulfur halotetrafluorides
having high electron density on the benzene ring, while the reactions are smooth at relatively
high temperature with arylsulfur halotetrafluorides having low electron density on the
benzene ring. Therefore, the reaction temperature may be chosen in order that the desired
reaction be completed preferably within a week and more preferably within a few days.
[0040] Embodiments of the invention also include a method which comprises reacting an
arylsulfur halotetrafluoride having a formula (II), with hydrogen fluoride in the presence of a
fluoride salt having a formula, M+F~(HF) , to form the arylsulfur pentafluoride having a
formula (I) (see Scheme 2, Process II).
Process II (Scheme 2)
Process II
()
[0041] For compounds of formulas (I) and (II), R1, R2, R3, R4, R5, and X are the same as
defined above.
[0042] In addition, arylsulfur halotetrafluorides (Formula II) for Process II are also the same
as described above in Process I.
[0043] Regarding M+F(HF) , M is a cationic moiety and n is 0 or a mixed number greater
than 0. Preferable M is a metal atom, an ammonium moiety, or a phosphonium moiety.
Preferable fluoride salts are exemplified, but are not limited to: alkali metal fluoride salts
such as LiF, NaF, KF, RbF, CsF, and their hydrogen fluoride salts such as LiF(HF)n-,
NaF(HF)n', KF(HF) ', RbF(HF) , CsF(HF) in which n' is a mixed number greater than 0;
alkali earth metal fluoride salts such as BeF2, BeFCl, MgF , MgFCl, CaF2, SrF , BaF2;
ammonium fluoride salts such as ammonium fluoride, methylammonium fluoride,
dimethylammonium fluoride, trimethylammonium fluoride, tetramethylammonium fluoride,
ethylammonium fluoride, diethylammonium fluoride, triethylammonium fluoride,
tetraethylammonium fluoride, tripropylammonium fluoride, tributylammonium fluoride,
tetrabutylammonium fluoride, benzyldimethylammonium fluoride, pyridinium fluoride,
methylpyridinium fluoride, dimethylpyridinium fluoride, trimethylpyridinium fluoride, and
other like materials, and their hydrogen fluoride salts such as NH4F(HF) n , CH3NH 3F(HF) ',
(CH3)2NH2F(HF) , (CH3)3NHF(HF)n , (CH3)4NF(HF) , (C H5)3NHF(HF) ,
(C2H )4NF(HF) , (C3H7)4NF(HF) ', (C4H )4NF(HF) ', pyridine HF(HF) -, and other like
materials, in which n' is a mixed number greater than 0; phosphonium fluoride salts such as
tetramethylphosphonium fluoride, tetraethylphosphonium fluoride, tetrapropylphosphonum
fluoride, tetrabutylphosphonium fluoride, tetraphenylphosphonium fluoride, and other like
materials, and their (HF)n' salts (n' is a mixed number greater than 0). Mixed number herein
refers to whole numbers and any fraction of a whole number, e.g., 0.1, 0.2, 0.25, 0.3, 0.4, 0.5,
0.75, 0.8, 0.9, 1, 1.1, 1.2, 1.25, 1.3, 1.5, 1.75, 2, 2.5, 3, 3.5, 4, 4.5, 5, and so on.
[0044] Among the examples of fluoride salts mentioned above, alkali metal fluoride salts
and their hydrogen fluoride salts are preferable, and among them, sodium fluoride and
potassium fluoride and their (HF)n salts are more preferable due to cost performance.
[0045] As M+F can react with hydrogen fluoride, M+F actually exists as M+F (HF)n' (n' is
a mixed number greater than 0) in hydrogen fluoride.
[0046] As a hydrogen halide, such as hydrogen chloride, is much more acidic than
hydrogen fluoride, hydrogen chloride can react with the fluoride salt having a formula, M+F
(HF) , according to the following reaction below, to form M+C1 which is a neutral salt.
M+F(HF)„ + HC1 M+C 1 + (n+1) HF
Thus, the fluoride salt can neutralize gaseous and very acidic hydrogen halide, forming a
neutral salt, M+X
[0047] Embodiments in accordance with Process II allow for the use of either anhydrous or
hydrous hydrogen fluoride. In typical cases the hydrogen fluoride is anhydrous hydrogen
fluoride. However, where some amount of water is present in the process reaction, it should
be minimized, as water may produce arylsulfonyl fluoride or arylsulfonyl chloride
byproducts. Minimizing the water content means that it is preferable less than about 5 wt
and more preferably less than about 3 wt of water content in the hydrogen fluoride.
[0048] The amount of hydrogen fluoride used in Process II is typically selected from the
range of about 1/10 to about 1/150 of a molar ratio of arylsulfur halotetrafluoride/hydrogen
fluoride. A more preferable range is about 1/15 to about 1/100, and furthermore one is about
1/15 to about 1/50. When the amount of hydrogen fluoride is less than 10 mol against 1 mol
of an arylsulfur halotetrafluoride, the product's yield is relatively low. When the amount of
hydrogen fluoride is more than 150 mol against 1 mol of an arylsulfur halotetrafluoride, it
leads to low effectiveness in production cost.
[0049] The amount of a fluoride salt, M+F(HF) n, as an additive used for reactions herein is
typically selected in the range of about 0.1 to about 5 mol, more preferably about 0.2 to about
3 mol, and furthermore preferably about 0.5 to about 2 mol against 1 mol of an arylsulfur
halotetrafluoride. When the fluoride salt is less than 0.1 mol, the effect of the additive is too
small. When it is more than 5 mol, the effect is limited.
[0050] From the viewpoint of cost and yields of the reactions, Process II is typically carried
out without any other solvents. However, where there is little or no solubility of the arylsulfur
halotetrafluoride and/or its product, arylsulfur pentafluoride, in hydrogen fluoride, a solvent,
which dissolves the arylsulfur halotetrafluoride and/or its product, may be added to increase
the reaction rate and yield. Suitable solvents for Process II are the same as for Process I
mentioned above.
[0051] The reaction temperature and time are the same as for Process I as mentioned above.
[0052] Embodiments of the invention also include a method which comprises reacting an
arylsulfur halotetrafluoride having a formula (II), with hydrogen fluoride in the presence of a
non-fluoride salt having a formula, M+Y [Y excludes F(HF) n], to form the arylsulfur
pentafluoride having a formula (I) (see Scheme 3, Process III).
Process III (Scheme 3)
Process III
[0053] Hydrogen fluoride and its amount used in Process III is the same as for Process II, as
mentioned above.
[0054] For compounds represented by formulas (I) and (II), R1, R2, R3, R4, R5, and X
represent the same meaning as defined previously.
[0055] Arylsulfur halotetrafluorides (Formula II) for use in Process III is the same as
described in Process I.
[0056] Regarding M+Y , M represents the same meaning as defined above, and Y is an
anionic moiety [except for F (HF) ] whose conjugated acid HY is less than HX in acidity (for
example, HC1).
- + H+ « HY
Y ; a conjugated base
HY; a conjugated acid
[0057] Typical M are the same as those described for Process II. Typical Y are exemplified,
but not limited to, sulfates such as OS0 3Na, OS0 3K, OS0 3Li, OS0 3NH4, OS0 3Mgi 2,
OS0 3Ca 2, and other like materials; benzenesulfonate (C6H5S0 3), methylbenzenesulfonate,
dimethylbenzenesulfonate, trimethylbenzenesulfonate, bromobenzenesulfonate,
chlorobenzenesulfonate, nitrobenzenesulfonate, vinylbenzenesulfonate, methanesulfonate,
ethanesulfonate, and other like compounds; carbonates such as OC0 2H, OC0 Na, OC0 2K,
OC0 Li, OC0 2NH and other like materials; carboxylates such as formate (HCOO), acetate
(CH3COO), propionate (C2H5COO), butanoate (C3H COO), benzoate (C6H5COO),
methylbenzoate (CH3C H4COO), dimethylbenzoate, trimethylbenzoate, (methoxy)benzoate,
nitrobenzoate, bromobenzoate, chlorobenzoate, cinnamate (C6H5CH=CHCOO), acrylate
(CH =CHCOO), 1-mefhylacrylate, 2-methylacrylate, 1-phenylacrylate, and other like
materials.
[0058] Typical M+Y are exemplified, but not limited to, NaOS0 3Na (Na S0 4), KOS0 3K
(K2S0 4), LiOS0 3Li (Li2S0 4), NH4OS0 3NH4 [(NH4)2S0 4], MgS0 4, CaS0 4, C6H5S0 3Na,
Q5H5SO3K, SC - , C H5S0 3HNEt3, sodium methylbenzenesulfonate, potassium
methylbenzenesulfonate, potassium dimethylbenzenesulfonate, potassium
trimethylbenzenesulfonate, potassium chlorobenzenesulfonate, potassium
nitrobenzenesulfonate, potassium vinylbenzenesulfonate, potassium methanesulfonate,
potassium ethanesulfonate, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium
bicarbonate, potassium carbonate, potassium bicarbonate, lithium formate, sodium formate,
potassium formate, lithium acetate, sodium acetate, potassium acetate, lithium benzoate,
sodium benzoate, potassium benzoate, sodium methylbenzoate, potassium methylbenzoate,
potassium dimethylbenzoate, potassium trimethylbenzoate, potassium (methoxy)benzoate,
potassium nitrobenzoate, potassium bromobenzoate, potassium chlorobenzoate, potassium
cinnamate, potassium propenoate (acrylate), potassium 2-methylpropenoate, potassium 2-
butenoate, and other like materials.
[0059] When halogenated arylsulfur pentafluorides are formed as byproducts in the
reactions of arylsulfur halotetrafluoride and hydrogen fluoride, M+Y is typically used, in
which the anionic moiety having at least one unsaturated bond in a moiety is selected among
Y mentioned above, such as benzenesulfonate (C6H5SO3), methylbenzenesulfonate,
dimethylbenzenesulfonate, trimethylbenzenesulfonate, bromobenzenesulfonate,
chlorobenzenesulfonate, nitrobenzenesulfonate, vinylbenzenesulfonate, benzoate (C H5COO),
methylbenzoate (CH3C H4COO), dimethylbenzoate, trimethylbenzoate, (methoxy)benzoate,
bromobenzenoate, chlorobenzoate, nitrobenzoate, cinnamate (C6H5CH=CHCOO),
propenoate (CH2=CHCOO), 2-methylpropenoate, 2-butenoate, and other like materials. The
Y having at least one unsaturated bond may significantly decrease the formation of the
byproducts, halogenated arylsulfur pentafluorides [see impurity (la) of Example 26 in Table
6].
[0060] The amount of a non-fluoride salt, M+Y , used for the reaction is typically selected
in the range of about 0.1 to about 5 mol, more typically about 0.2 to about 3 mol, and
furthermore typically about 0.5 to about 2 mol against 1 mol of an arylsulfur halotetrafluoride.
When the non-fluoride salt is less than 0.1 mol, the effect of the fluoride salt is too low, and
when it is more than 5 mol, the effect is limited.
[0061] As a hydrogen halide, such as hydrogen chloride (HQ), is more acidic than HY,
hydrogen chloride can react with the non-fluoride salt having a formula^ M+Y , according to
the following reaction below, to form M+C1 , which is a neutral salt.
M+Y- + HC1 M+Cr + HY
Thus, the non-fluoride salt can neutralize gaseous and very acidic hydrogen halide, forming a
neutral salt such as M+X
[0062] From the viewpoint of cost and yields, Process III embodiments are typically carried
out without any additional solvents. However, where there is little or no solubility of
arylsulfur halotetrafluoride and/or its product, arylsulfur pentafluoride, in hydrogen fluoride,
a solvent which dissolves the arylsulfur halotetrafluoride and/or its product may be added to
increase the reaction rate and yield. Where appropriate, suitable solvents for Process III are
the same as for Process I as mentioned above.
[0063] The reaction temperature and time for Process III are the same as for Process I, as
mentioned above.
[0064] Embodiments of the invention also include a method which comprises reacting an
arylsulfur halotetrafluoride having a formula (II), with hydrogen fluoride in the presence of
an organic compound having one or more unsaturated bonds in a molecule to form the
arylsulfur pentafluoride having a formula (I) (see Scheme 4, Process TV).
Process IV (Scheme 4)
Process IV
( ) (I)
[0065] Hydrogen fluoride and its amount used for Process IV is the same as for Process II
as mentioned above.
[0066] For compounds represented by formulas (I) and (II), R , R2, R , R4, R-, and X
represent the same meaning as defined above.
[0067] Arylsulfur halotetrafluorides (Formula II) usable for Process IV are the same as
described in Process I.
[0068] With regard to an organic compounds having one or more unsaturated bonds in a
molecule, the organic compound is typically selected from a group consisting of arenes,
alkenes, and alkynes. These organic compounds are exemplified, but not limited to, arenes
such as benzene, toluene, xylene, durene, fluorobenzene, chlorobenzene, bromobenzene,
phenol, anisole, cresole, naphthalene, anthracene, and other like materials; alkenes such as
ethylene, vinyl chloride, vinyl bromide, vinylidene chloride, 1,2-dichloroethylene,
trichloroethylene, tetrachloroethylene, propene, butene, pentene, hexene, heptene, octene, and
other like materials; alkynes such as acetylene, propyne, and other like materials. Among
these compounds, arenes are typical due to availability and yield of products.
[0069] When halogenated arylsulfur pentafluorides are formed as byproducts in the
reactions of arylsulfur halotetrafluoride and hydrogen fluoride, the Process IV using organic
compounds having one or more unsaturated bonds in a molecule are preferable because the
process significantly decreases the formation of the byproducts (halogenated arylsulfur
pentafluorides) [see impurity (la) of Examples 21-25 in Table 6].
[0070] The amount of an organic compound used for the reaction is preferably selected in
the range of about 0.01 mol to a large excess, against 1 mol of an arylsulfur halotetrafluoride.
This may include the case where an organic compound is used as a solvent or as one of
solvents for the reaction, if the organic compounds do not effect the desired reactions and are
easily removed from the reaction mixture after the reaction, for example, because of low
boiling point. The amount is more preferable in the range of about 0.05 mol to about 5 mol,
furthermore preferably about 0.05 mol to about 1 mol against 1 mol of an arylsulfur
halotetrafluoride. When it is less than 0.01 mol, the effect of the additive is too small.
[0071] From the viewpoint of cost and yields of the reactions, Process IV is preferably
carried out without any other solvents. However, in the case of little or no solubility of the
arylsulfur halotetrafluoride and/or its product, arylsulfur pentafluoride, in hydrogen fluoride,
a solvent which dissolves the arylsulfur halotetrafluoride and/or its product may be added to
increase the reaction rate and yield. Suitable solvents for Process IV are the same as for
Process I mentioned above.
[0072] The reaction temperature and time for Process IV are the same as for Process I
mentioned above.
[0073] Embodiments of the invention also include a method which comprises reacting an
arylsulfur halotetrafluoride having a formula (II), with hydrogen fluoride in the presence of
additives to form the arylsulfur pentafluoride, having a formula (I) [see Process V (Scheme
5)], in which at least two additives are selected from a group consisting of fluoride salts
having a formula, M+F~(HF) , non-fluoride salts having a formula, M+Y [Y excludes F
(HF) ], and organic compounds having one or more unsaturated bonds in a molecule.
Process V (Scheme 5)
Process V
( ) (I)
[0074] Hydrogen fluoride, and its amount used, for Process V is the same as for Process II,
mentioned above.
[0075] For compounds of formulas (I) and (II), R , R2, R3, R4, R5, and X represent the same
meaning as defined above.
[0076] Arylsulfur halotetrafluorides (Formula II) usable for Process V are the same as
described in Process I.
[0077] The fluoride salts, M+F(HF) , the non-fluoride salts, M+Y [Y excludes F (HF) ],
and the organic compound having one or more unsaturated bonds in a molecule, are the same
meaning as defined above.
[0078] The total amount of the additives for Process V can be selected in the range of about
0.05 mol to a large excess, more preferably about 0.1 mol to about 5 mol, and furthermore
preferably about 0.5 to about 3 mol against 1 mol of an arylsulfur halotetrafluoride. The ratio
between or among the additives may be chosen in order to get a better yield of the product.
When the total amount of additives is less than 0.05 mol, the effect of the additive is too
small.
[0079] From the viewpoint of cost and yields of the reactions, Process V is preferably
carried out without any other solvents. However, in the case of little or no solubility of the
arylsulfur halotetrafluoride and/or its product, arylsulfur pentafluoride, in hydrogen fluoride,
a solvent which dissolves the arylsulfur halotetrafluoride and/or its product may be added to
increase the reaction rate and yield. Suitable solvents for Process V are the same as for
Process I mentioned above.
[0080] The reaction temperature and time for Process V are the same as for Process I
mentioned above.
[0081] According to the present invention, the highly pure arylsulfur pentafluorides having
the formula (I) can be cost-effectively produced in commercial production. The advancement
is unexpected in light of conventional production methods both in light of costs and yield. It
represents a significant hurdle to overcome the industrial aspects of the present invention as
other conventional methods require high cost performance due to no fluidity of solid fluoride
sources, hard control on the exothermic solid-liquid phase reactions at elevated temperature,
fine purification processes necessary for products of less purity, and unsatisfactory safety and
environment sustainability.
[0082] The following examples will illustrate the present invention in more detail, but it
should be understood that the present invention is not deemed to be limited thereto.
Examples
Example 1. Synthesis of phenylsulfur pentafluoride by reaction of phenylsulfur
chlorotetrafluoride with anhydrous hydrogen fluoride
Pr ce I
[0083] While N gas was flowed through a 250 raL fluoropolymer (FEP) vessel set with a
condenser (made of fluoropolymer), the vessel was cooled in a bath of -11 °C. A coolant (-25
°C) was flowed through the condenser. The vessel cooled at -11 °C was charged with 72.3 g
(3.62 mol) of anhydrous hydrogen fluoride which was cooled at -20 °C. Into the vessel, 35.0
g (0.152 mol) of phenylsulfur chlorotetrafluoride (this purity was 96 wt% and the other 4
wt% was phenylsulfur trifluoride) was added over 90 min through a syringe using a syringe
pump. The molar ratio of phenylsulfur chlorotetrafluoride and hydrogen fluoride was 1/24.
After the addtion, the reaction mixture was stirred at -10 °C for 20 hours. After that, the
reaction mixture was warmed to 25 °C and hydrogen fluoride was removed at the temperature
under atmospheric pressure. The residue was mixed with 100 mL of 10% aqueous KOH and
extracted with dichloromethane. The organic layer was separated, dried over anhydrous
magnesium sulfate, and filtered. The filtrate was concentrated by distilling the solvent at 70
°C under atmospheric pressure. The resulting residue was distilled under reduced pressure
(bath temperature about 110 °C and 32 mmHg) to give 20.6 g (yield 66%) of phenylsulfur
pentafluoride. The purity of the product was determined to be 99.7 %by GC analysis. The
product was identified by spectral comparison with an authentic sample.
Examples 2-11. Synthesis of arylsulfur pentafluorides (I) by reaction of arylsulfur
halotetrafluorides (II) with anhydrous hydrogen fluoride
II I
[0084] Various arylsulfur pentafluorides (I) were synthesized by reaction of the
corresponding arylsulfur halotetrafluorides (II) with anhydrous hydrogen fluoride. Table 1
shows the results, the starting materials and anhydrous hydrogen fluoride used for the
reactions, and reaction conditions, together with those of Example 1. The procedure was
conducted in a similar way as in Example 1, except for Example 7, in which 15.0 g (46.1
mmol) of compound (II) was placed in the vessel and then mixted with liquid anhydrous
hydrogen fluoride cooled at -20 °C, because the compound (II) was solid. In Example 11, a
mixture of 33.6 g (93.1 mmol) of compound (II) and 3.0 g of dry acetonitrile was added into
the reaction vessel through a syringe.
[0085] The products were identified by spectral comparison with authentic samples except
for Example 11, in which, product, 4-bromo-3-fluorophenylsulfur pentafluoride, was
identified by spectral analysis. Physical and spectral data of 4-bromo-3-fluorophenylsulfur
pentafluoride are as follows; bp 74-79 °C/6 mmHg; 1H NMR (CDC13) 7.45 (dd, J=9.0 Hz,
1.7 Hz, 1H), 7.54 (dd, J=8.6 Hz, 2.4 Hz, 1H), 7.67 (t, J=7.9 Hz, 1H); 1 F NMR (CDC13) 
63.03 (d, J=154 Hz, 4F), 82.07 (quintet, J=154 Hz, IF), -102.98 (s, IF); 1 C NMR (CD3CN) 
113.2 (d, J=21 Hz), 114.9 (doublet-quintet, J=27 Hz, 5 Hz), 123.1 (m), 134.0 (s), 152.9
(doublet-quintet, J=7 Hz, 20 Hz), 158.2 (d, J=250 Hz); GC-Mass 302 (M+), 300 (M+) .
Table 1. Synthesis of arylsulfur pentafluorides (I) by reaction of arylsulfur halotetrafluorides
(II) with anhydrous hydrogen fluoride
Example 12. Synthesis of phenylsulfur pentafluoride by reaction of phenylsulfur
chlorotetrafluoride with anhydrous hydrogen fluoride in the presence of K+F -HF added as an
additive
Process II
[0086] A dried 125 mL fluoropolymer (FEP) vessel was flowed with N2 gas and charged
with 48.0 g (2.40 mmol) of liquid anhydrous hydrogen fluoride which was cooled at -20 °C.
The vessel was set with a condenser (made of fluoropolymer) and a thermometer, and cooled
in a bath of -20 °C. A coolant (-15 °C) was flowed through the condenser. Into the vessel, 8.6
g (0.11 mol) of KF-HF was added. While the mixture was warmed to +15 °C, 22.1 g (96.2
mmol) (purity 96 wt and the other was phenylsulfur trifluoride) of phenylsulfur
chlorotetrafluoride was added to the mixture over 1 hour through a syringe. The temperature
of the reaction mixture was 3.4 °C and 13.6 °C at the starting point and completing point of
the addition, respectively. After the addition, the reaction mixture was stirred at 15 °C for 18
h. After that, the reaction mixture was warmed to 25 °C and hydrogen fluoride was removed
under atmospheric pressure. The residue was neutralized with about 15% aqueous KOH and
extracted with dichloromethane. The organic layer was separated, dried over anhydrous
magnesium sulfate, and filtered. The filtrate was concentrated by distilling the solvent at 70
°C under atmospheric pressure. The resulting residue was distilled under reduced pressure to
give 14.4 g (yield 73%) of phenylsulfur pentafluoride (boiling point 57.5 °C/ 35 mmHg). The
purity of the product was determined to be 100 % by GC analysis. The product was identified
by spectral comparison with an authentic reference sample.
Examples 13-19. Synthesis of arylsulfur pentafluorides (I) by reaction of arylsulfur
halotetrafluorides (II) with anhydrous hydrogen fluoride in the presence of a fluoride salt,
M F (HF) , added as an additive
Process II
II M+F (HF)n I
[0087] Various arylsulfur pentafluorides (I) were synthesized by reaction of the
corresponding arylsulfur halotetrafluorides (II) with anhydrous hydrogen fluoride in the
presence of a fluoride salt of formula, M+F~(HF)n, added as an additive. The procedure was
conducted in a similar way as in Example 12. Table 2 shows the results, the starting materials,
anhydrous hydrogen fluoride, and fluoride salts used for the reactions, and reaction
conditions together with those of Example 12.
Table 2. Synthesis of arylsulfur pentafluorides (I) by reaction of arylsulfur halotetrafluorides
[0088] The products were identified by spectral comparison with reference samples, except
for Example 19, in which, the product, 3,4-difluorophenylsulfur pentafluoride, was identified
by spectral analysis. Physical and spectral data of 3,4-difluorophenylsulfur pentafluoride are
as follows: bp 75-76 °C/25 mmHg; 1H NMR (CDC13) 7.27 (m, 1H), 7.53-7.58 (m, 1H),
7.62-7.66 (m, 1H); F NMR (CDC13) -133.75 (d, J=26 Hz, IF), -130.93 (d, J=26 Hz, IF),
63.60 (d, J=147 Hz, 4F), 82.56 (quintet, J=147 Hz, IF); C NMR (CDC13) 116.6 (dt, J=22
Hz, 4 Hz), 117.4 (d, J=19 Hz), 123.0 (m), 49.2 (quintet, J=20 Hz), 149.3 (dd, J=254 Hz, 13
Hz), 152.0 (dd, J=257 Hz, 12 Hz); GC-Mass 240 (M+).
[0089] As mentioned above, the fluoride salt can neutralize hydrogen chloride which is
formed from the reaction. Furthermore, for examples, as seen from the comparison between
Examples 3 and 12 and between Examples 10 and 15 at the same reaction temperature, the
addition of a fluoride salt can make the yield and purity of the products higher than without
the additive because the additive can make the reactions mild and surpress the formation of
tar.
Example 20. Synthesis of arylsulfur pentafluoride (I) by reaction of arylsulfur
halotetrafluoride (II) with anhydrous hydrogen fluoride in the presence of a non-fluoride salt
Process III
a non-fluoride salt
II
[0090] Liquid anhydrous hydrogen fluoride (61 g, 3.05 mol) was put in a dried 125 mL
fluoropolymer vessel in the same way as in Example 12. The vessel was then set with a
condenser (made of fluoropolymer) and a thermometer, and cooled in a bath of -20 °C.
Sodium acetate (9.0 g, 0.11 mol) was added portion by portion into a stirred liquid of
hydrogen fluoride in the vessel. The mixture was homogenious. A coolant (-15 °C) was
flowed through the condenser and the bath temperature was raised to -10 °C. Phenylsulfur
chlorotetrafluoride (23.4 g, purity 95 wt , 0.101 mol) was added to the mixture over 30 min
through a syringe using a syringe pump. The temperature of the reaction mixture was -8 °C
and -6 °C at the starting point and completing point of the addition, respectively. The bath
temperature was then raised to +5 °C and the reaction mixture was stirred for 70 min at +5 °C.
The bath temperature was then raised to +10 °C and the reaction mixture was stirred for 50
min. The bath temperature was then raised to +15 °C and the reaction mixture was stirred for
20 h at +15 °C. After the reaction, the bath temperature was warmed to room temperature and
hydrogen fluoride was removed by evaporation at room temperature. The residue was slowly
poured into 400 g of 23% aqueous KOH solution, and the mixture was stirred for 30 min.
The lower organic layer was separated and the upper aqueous layer was extracted with
dichloromethane. The combined organic layer was washed with saturated aqueous NaCl
solution, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated
by distilling the solvent on an oil bath of 70 °C at atmospheric pressure. The resulting residue
was distilled by heating in an oil bath of 180 °C and more at atmospheric pressure, giving
11.5 g of phenylsulfur pentafluoride which was a fraction of 145-150 °C. The purity of the
product was determined to be 99.6% by GC analysis. The product was identified by spectral
comparison with a reference sample. Table 3 summarizes the reaction conditions and results.
Table 3. Synthesis of arylsulfur pentafluorides (I) by reaction of arylsulfur halotetrafluorides
(II) with hydrogen fluoride in the presence of a non-fluoride salt
Ex. (II) HF Mol ratio Non-fluoride Mol. ratio Conditions (I) Yield Purity
(II) :HF salt (II) : non-fluoride salt
20 Q-SF C, 61 g NaOCOCH3
(3.06 mol) 1 : 30 1 : 1.1 5°C -> 10°C, 2 h 11.5 g . %
9.0 g 15 °C, 20 h (56%)
purity; 95% (110 mmol)
23.4 g (101 mmol)
Example 21. Synthesis of arylsulfur pentafluoride (I) by reaction of arylsulfur
halotetrafluoride (II) with anhydrous hydrogen fluoride in the presence of an organic
compound
Process IV
an organic compound
II
[0091] Example 21 was conducted in a similar way as in Example 12 except that an organic
compound was added in place of a fluoride salt. Table 4 shows the starting material,
anhydrous hydrogen fluoride, and an aromatic compound as an additive used for the reaction,
reaction conditions, and results. The product was identified by comparison with a reference
sample.
Table 4. Synthesis of arylsulfur pentafluorides (I) by reaction of arylsulfur halotetrafluorides
(II) with hydrogen fluoride in the presence of an organic compound
Mol ratio Organic Mol. ratio
Ex. (") HF (II) : HF compound (II) : organic compound Conditions (I) Yield Purity
21 CH3- >- S C Benzene
48.6 g 1 : 30 1 : 0.37 15 °C
(2.4 mol) 2.7 mL
purity; 81% 79 h
(30 mmol)
10.1 g 90%
(57%)
23.4 g (80.8 mmol)
[0092] A byproduct, 3-chloro-4-methylphenylsulfur pentafluoride (la), formed in Example
21 is shown in Table 6. As a comparison (at the same reaction temperature), Example 10
without any additive is also shown in Table 6. The byproduct (la) was 1.0% in Example 21,
while byproduct (la) was 8.1% in Example 10. This clearly indicates that an organic
compound (benzene) as an additive greatly prevents the formation of byproduct (la) by
washing out the side reactions (chlorination of the product). This provides a surprising
advantage over other conventional synthesis reactions.
Examples 22~26. Synthesis of arylsulfur pentafluorides (I) by reaction of arylsulfur
halotetrafluorides (II) with anhydrous hydrogen fluoride in the presence of two or more
additives selected from a group consisting of fluoride salts, non-fluoride salts, and organic
compounds
II I
[0093] Various arylsulfur pentafluorides (I) were synthesized by reaction of the
corresponding arylsulfur halotetrafluorides (II) with anhydrous hydrogen fluoride in the
presence of two or more additives, which are selected from a group consisting of fluoride
salts, non-fluoride salts, and organic compounds having one or more unsaturated bonds in a
molecule. The reaction was conducted in a similar way as in Example 12 except that two or
more additives were added in place of a fluoride salt. Examples 22-25 were performed with a
fluoride salt and an organic compound as additives, and Example 26 was performed with a
fluoride salt and a non-fluoride salt as additives. The product was identified by comparison
with a reference sample.
[0094] Table 5 shows the results, the starting material, anhydrous hydrogen fluoride, and
additives used for the reactions, and reaction conditions. According to this method using two
or more additives, products of high purity were obtained in better relative yields. At the same
reaction temperature (+15°C), the purities of the products of Examples 22-26 (96-99%) are
much higher than those of Example 10 (90.9%) without any additive and Example 21 (90%)
with one additive (benzene).
Table 5. Synthesis of arylsulfur pentafluorides (I) by reaction of arylsulfur halotetrafluorides
(II) with hydrogen fluoride in the presence of at least two additives selected from a group
consisting of fluoride salts, non-fluoride salts, and organic compounds
Mo!. rtio Additives Mol. ratio
Ex. (II) HF Conditions y
(11):HF (11):(A):(B) (I) Yield Purit
(A) (B)
22 CH - - S C 46.2 g KF HF Benzene 15 °C
1 : 26 1 : 1.2 : 0.11
8.6 g 0.9 mL 15 h
purity; 90% (2.31 mol)
C ~ S 5 15.1 g 96%
(77%)
(0.11 mol) (10 mmol)
23.4 g (89.8 mmol)
15°C
23 C SF4CI 38.6 g 1 : 22 KF- HF Benzene
1 : 1.3 : 0.23 98.1%
(1.9 mol) 8.6 g 1.8 mL 2 1 h
purity; 86%
C ~ S 13.1 g
(70%)
23.4 g (85.8 mmol) (0.11 mol) (20 mmol)
- - S C I 24 45.8 g KF- HF Benzene 15 °C
1 : 24 1 : 1.2 : 0.27
(2.3 mol) 8.6 g 2.2 mL 19 h
C ~ - S 13.3 g 98%
(65%)
purity; 94.5% (0.11 mol) (25 mmol)
23.4 g (94.3 mmol)
enzene
25 CH — - SF C I KF- HF B
43.1 g 1 : 1.2 : 0.33 15 °C 1.3 g
8.6 g 2.7 mL 99%
17 h
purity; 92% (2.15 mol) 1 : 23 H - S 1
(56%)
(0.11 mol) (30 mmol)
23.4 g (91.8 mmol)
CH3
KF- HF .
26 CH - - S CI 56.9 g 1 : 36 6.4 g 15°C 12.6 g
(2.85 mol)
[ J 1 : 1.0 : 0.37 97.5%
(82 mmol) 17 h (73%)
purity; 79% S0 K
23.4 g (78.8 mmol)
6.0 g (29 mmol)
[0095] For a more detailed discussion, Table 6 shows the contents of impurity (la) and other
byproducts (IIIa~c) contained in the products obtained in Examples 10, 15, and 21-26. The
formation of impurity (la) decisively hurts the yields and purity of products (I). Other
byproduts (IIIa~c) do not hurt the reaction because they depend on the additives and hence
suitable reaction conditions or suitable additives can be selected for the reaction. Example 10
was conducted without any additives, Example 15 was conducted with KF-HF as one
additive, Example 21 was conducted with benzene as one additive, Examples 22-25 were
conducted with KF-HF and benzene as two additives, and Example 26 was conducted with
KF-HF and potassium p-methylbenzenesulfonate as two additives. The amount of impurity
(la) was 8.1% in Example 10, 1.9% in Example 15, 1.0% in Example 21, and 0.2% in
Examples 22, no formation in Examples 23-25, and 0.7% in Example 26. It is clear that
KF-HF or benzene as one additive significantly prevents the formation of the impurity (la),
and that the use of both KF-HF and benzene or potassium p-methylbenzenesulfonate as two
additives almost or completely eliminate the formation of the impurity (la). Thus, the
impurity is significantly decreased or completely not formed by these additives. Again, this
shows the utility of the present invention.
Table 6. Contents of impurity (la) and other byproducts (IIIa~c) contained in the products
obtained in Examples 10, 15, and 21 - 26
1) Contents were determined by GC analysis. no=no formation. n.d.=not detected.
[0096] While the invention has been particularly shown and described with reference to a
number of embodiments, it would be understood by those skilled in the art that changes in the
form and details may be made to the various embodiments disclosed herein without departing
from the spirit and scope of the invention and that the various embodiments disclosed herein
are not intended to act as limitations on the scope of the claims. All publications cited herein
are hereby incorporated by reference.
Claims
[Claim 1]
A method for preparing arylsulfur pentafluoride having a formula (I) as follows:
comprising reacting arylsulfur halotetrafluoride of formula (II) with anhydrous
hydrogen fluoride to form the arylsulfur pentafluoride:
wherein a mol ratio of the arylsulfur halotetrafluoride to anhydrous hydrogen
fluoride is in the range of about 1:10 to about 1:150;
in which: R , R2, R , R4, and R5 each is independently a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 30 carbon atoms, a nitro group, a cyano group, a
substituted or unsubstituted alkanesulfonyl group having 1 to 18 carbon atoms, a substituted
or unsubstituted arenesulfonyl group having 6 to 30 carbon atoms, a substituted or
unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted
aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted acyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted alkanesulfonyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted arenesulfonyloxy group
having from 6 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group
having 2 to 18 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7
to 30 carbon atoms, a substituted carbamoyl group having 2 to 18 carbon atoms, a substituted
amino group having 1 to 18 carbon atoms, or a SF5 group; and
X is a chlorine atom, bromine atom, or iodine atom.
[Claim 2]
The method of claim 1 wherein the mol ratio of the arylsulfur halotetrafluoride to
the hydrogen fluoride is in the range of about 1:15 to about 1:100.
[Claim 3]
The method of claim 1 wherein X is CI.
[Claim 4]
A method for preparing an arylsulfur pentafluoride having a formula (I) as follows:
the process comprising:
reacting an arylsulfur halotetrafluoride having a formula (II):
with hydrogen fluoride in the presence of a fluoride salt of formula, M+F(HF) n, to
form the arylsulfur pentafluoride; wherein the mol ratio of an arylsulfur halotetrafluoride to a
fluoride salt is in a range of about 1:0.1 to about 1:5 and the mol ratio of an arylsulfur
halotetrafluoride to hydrogen fluoride is in a range of about 1:10 to about 1:150;
in which: R1, R2, R , R4, and R5 each is independently a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 30 carbon atoms, a nitro group, a cyano group, a
substituted or unsubstituted alkanesulfonyl group having 1 to 18 carbon atoms, a substituted
or unsubstituted arenesulfonyl group having 6 to 30 carbon atoms, a substituted or
unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted
aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted acyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted alkanesulfonyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted arenesulfonyloxy group
having from 6 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group
having 2 to 18 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7
to 30 carbon atoms, a substituted carbamoyl group having 2 to 18 carbon atoms, a substituted
amino group having 1 to 18 carbon atoms, or a SF5 group;
X is a chlorine atom, bromine atom, or iodine atom;
M is a metal atom, an ammonium moiety, or a phosphonium moiety; and
n is 0 or a mixed number greater than 0.
[Claim 5]
The method of claim 4 wherein X is CI.
[Claim 6]
The method of claim 4 wherein the fluoride salt is an alkali metal fluoride which is
selected from the group consisting of LiF(HF)n, NaF(HF)n, KF(HF)n, RbF(HF) , and
CsF(HF) in which n is 0 or a mixed number which is greater than 0.
[Claim 7]
A method for preparing an arylsulfur pentafluoride having a formula (I) as follows:
the process comprising:
reacting an arylsulfur halotetrafluoride having a formula (II):
with hydrogen fluoride in the presence of a non-fluoride salt of formula, M+Y~, to
form the arylsulfur pentafluoride;
in which: R1, R2, R3, R4, and R5 each is independently a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 30 carbon atoms, a nitro group, a cyano group, a
substituted or unsubstituted alkanesulfonyl group having 1 to 18 carbon atoms, a substituted
or unsubstituted arenesulfonyl group having 6 to 30 carbon atoms, a substituted or
unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted
aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted acyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted alkanesulfonyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted arenesulfonyloxy group
having from 6 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group
having 2 to 18 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7
to 30 carbon atoms, a substituted carbamoyl group having 2 to 18 carbon atoms, a substituted
amino group having 1 to 18 carbon atoms, or a SF5 group;
X is a chlorine atom, bromine atom, or iodine atom;
M is a metal atom, an ammonium moiety, or a phosphonium moiety;
Y is an anion moiety whose conjugated acid, HY, is less than HX in acidity, and Y
excepts F(HF)n in which n is 0 or a mixed number greater than 0.
[Claim 8]
The method of claim 7 wherein X is CI.
[Claim 9]
The method of claim 7 wherein the mol ratio of arylsulfur halotetrafluoride to nonfluoride
salt is in a range of about 1:0.1 to about 1:5.
[Claim 10]
The method of claim 7 wherein the mol ratio of arylsulfur halotetrafluoride to
hydrogen fluoride is in the range of about 1:10 to about 1:150.
[Claim 11]
A method for preparing an arylsulfur pentafluoride having a formula (I) as follows:
the process comprising:
reacting an arylsulfur halotetrafluoride having a formula (II):
with hydrogen fluoride in the presence of an organic compound to form the
arylsulfur pentafluoride, in which the organic compound has one or more unsaturated bonds
in a molecule;
in which: R , R2, R3, R4, and R5 each is independently a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 30 carbon atoms, a nitro group, a cyano group, a
substituted or unsubstituted alkanesulfonyl group having 1 to 18 carbon atoms, a substituted
or unsubstituted arenesulfonyl group having 6 to 30 carbon atoms, a substituted or
unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted
aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted acyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted alkanesulfonyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted arenesulfonyloxy group
having from 6 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group
having 2 to 18 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7
to 30 carbon atoms, a substituted carbamoyl group having 2 to 18 carbon atoms, a substituted
amino group having 1 to 18 carbon atoms, or a SF5 group; and
X is a chlorine atom, bromine atom, or iodine atom.
[Claim 12]
The method of claim 11 wherein X is CI.
[Claim 13]
The method of claim 11 wherein the mol ratio of arylsulfur halotetrafluoride to
organic compound is in the range of about 1:0.05 to about 1:5.
[Claim 14]
A method for preparing an arylsulfur pentafluoride having a formula as follows:
the process comprising:
reacting an arylsulfur halotetrafluoride having a formula
with hydrogen fluoride in the presence of additives to form the arylsulfur
pentafluoride, in which at least two additives are selected from a group consisting of fluoride
salts of formula, M+ F(HF)n, non-fluoride salts of formula, M+Y , and organic compounds
that have one or more unsaturated bonds in a molecule;
in which: R1, R2, R3, R4, and R5 each is independently a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or
unsubstituted aryl group having 6 to 30 carbon atoms, a nitro group, a cyano group, a
substituted or unsubstituted alkanesulfonyl group having 1 to 18 carbon atoms, a substituted
or unsubstituted arenesulfonyl group having 6 to 30 carbon atoms, a substituted or
unsubstituted alkoxy group having 1 to 18 carbon atoms, a substituted or unsubstituted
aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted acyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted alkanesulfonyloxy group
having from 1 to 18 carbon atoms, a substituted or unsubstituted arenesulfonyloxy group
having from 6 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group
having 2 to 18 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group having 7
to 30 carbon atoms, a substituted carbamoyl group having 2 to 18 carbon atoms, a substituted
amino group having 1 to 18 carbon atoms, or a SF5 group;
X is a chlorine atom, bromine atom, or iodine atom;
M is a metal atom, an ammonium moiety, or a phosphonium moiety;
n is 0 or a mixed number greater than 0; and
Y is an anion moiety whose conjugated acid, HY, is less than HX in acidity, and Y
is not F(HF) .
[Claim 15]
The method of claim 14 wherein the mol ratio of the arylsulfur halotetrafluoride to
the total amount of the additives is in a range of about 1:0.1 to about 1:5.