Amines or salts thereof and methods of preparing same

Details Amines or salts thereof and methods of preparing same Amines or salts thereof and methods of preparing same

1996-02-12

2001-05-22

Badio, Barbara P. (Department: 1616)

Organic compounds -- part of the class 532-570 series

Organic compounds

Sulfonate esters

Reexamination Certificate

active

06235921

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to amines or salts thereof, which are useful as catalyst and the like, and to methods of preparing the amines or the salts.
Of amines, for example, metal salts of sulfonylamines and hydrates of these salts are disclosed in Japanese Patent Unexamined Publication JP-A-Hei-7-246338. These compounds disclosed therein are usable as Lewis acid catalysts and represented by the following general formula of M[RfSO
2
—N—SO
2
Rf′]
n
or of M[RfSO
2
—N—SO
2
Rf′]
n
·mH
2
O wherein Rf and Rf′ each represent perfluoroalkyl groups having a carbon atom number from 1 to 8, M represents a positive ion selected from a special group disclosed therein, n represents an integer that is the same as the valence of M, and m represents a natural number from 0.5 to 20.
Argyropoulos et al. Journal of Applied Polymer Science, Vol. 26, 3073-3084 (1981) discloses, as another example of amines, bis(ethoxysulfonyl)amine, HN(C
2
H
5
OSO
2
)
2
, and polysulfonylamine.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a novel amine or its salt, which has a fluorocarbon sulfonic acid ester group, and a method of preparing the amine or its salt.
According to the present invention, there is provided a novel first compound which is one of a first amine and a first salt of the first amine. This first compound has a fluorocarbon sulfonic acid ester group, and is represented by the general formula (1) (thus hereinafter referred to as “the first compound (1)”, “the first amine (1)”, or “the first salt (1)”):
 M[Rf
1
OSO
2
NSO
2
ORf
2
]
n
  (1)
wherein Rf
1
and Rf
2
represent the same or different fluorine-containing monovalent organic groups each of which has a carbon atom number from 2 to 18, a straight-chain portion, a branched-chain portion and/or a ring chain portion, and an optional unsaturated bond and an optional oxygen atom; M represents a positive ion which has a first valence and is one selected from the group consisting of hydrogen ion, ammonium ion, quaternary ammonium ions, alkali metal ions, alkali earth metal ions, transition metal ions, rare earth element ions, aluminum ions, gallium ions, iridium ions, thallium ions, tin ions, lead ions, arsenic ions, antimony ions, and bismuth ions; and n represents an integer that is the same as the first valence.
According to the present invention, there is provided a first method of preparing the first compound (1). This first method comprises the step of:
(a) reacting bis(chlorosulfonyl)amine represented by the formula (2) (hereinafter referred to as “the bis(chlorosulfonyl)amine (2)”) with a fluoroalcohol represented by the general formula (3) (hereinafter referred to as “the fluoroalcohol (3)”), so as to prepare the first amine (1) wherein M represents a hydrogen ion, and n is 1,
HN(SO
2
Cl)2  (2)
Rf
3
OH  (3)
wherein Rf
3
represents the same or different groups which are identical with the Rf
1
and the Rf
2
.
According to the present invention, there is provided a novel second compound which is one of a second amine and a second salt of the second amine. This second compound has a fluorocarbon sulfonic acid ester group, and is represented by the general formula (4) (thus hereinafter referred to as “the second compound (4)”, “the second amine (4)”, or “the second salt (4)):
—[M[N—SO
2
ORf
4
OSO
2
]
n
]
m
—  (4)
wherein Rf
4
represents a fluorine-containing bivalent organic group which has a carbon atom number from 3 to 18, a straight-chain portion, a branched-chain portion and/or a ring chain portion, and an optional unsaturated bond and an optional oxygen atom; M represents a positive ion as defined above; n represents an integer as defined above, and m represents an integer from 1 to 1,000.
According to the present invention, there is provided a second method of preparing the second compound (4). The second method comprises the step of:
(b) reacting bis(chlorosulfonyl)amine (2) with a fluorodiol represented by the general formula (5) (hereinafter referred to as “the fluorodiol (5)”), so as to prepare the second amine (4) wherein M is a hydrogen ion, and n is 1,
HORf
5
OH  (5)
wherein Rf
5
represents a bivalent organic group which is identical with Rf
4
.
In the invention, the above-mentioned first method further optionally comprises, after the step (a), the step of: (c) reacting the first amine (1) with a third compound, so as to prepare the first salt (1), the third compound being one selected from the group consisting of ammonia, quaternary ammonium compounds, hydroxides of an element, oxides of the element, carbonates of the element, halides of the element, fluorides of the element, chlorides of the element, bromides of the element, iodides of the element, and acetates of the element, the element being one selected from the group consisting of alkali metals, alkali earth metals, transition metals, rare earth elements, aluminum, gallium, iridium, thallium, tin, lead, arsenic, antimony, and bismuth.
In the invention, the above-mentioned second method further optionally comprises, after the step (b), the step of: (d) reacting the second amine (4) with the above-mentioned third compound, so as to prepare the second salt (4).
Similar to the above-mentioned conventional metal salts of sulfonylamines and hydrates of these metal salts, the first and second compounds (1) and (4) according to the present invention have fluorine-containing amine ions. These amine ions are stabilized by a strong electron attractive force of the fluorine atoms. Thus, the ionic bond between the fluorine-containing amine ions and the positive ions becomes small. With this, the first and second compounds (1) and (4) have large dissociation constants. Therefore, these compounds (1) and (4) are fully expected to be usable as a catalyst and the like, in the synthesis of organic compounds.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A novel first compound (1) according to the present invention is represented by the general formula (1):
M[Rf
1
OSO
2
NSO
2
ORf
2
]
n
  (1)
wherein Rf
1
and Rf
2
represent the same or different fluorine-containing monovalent organic groups. Examples of these groups are fluorine-containing straight chain or branched chain alkyl and alkenyl groups each having a carbon atom number from 2 to 18, fluorine-containing cycloalkyl and cycloalkenyl groups each having a carbon atom number from 3 to 18, fluorine-containing aryl groups each having a carbon atom number from 6 to 18, and mixtures thereof. Preferable examples of Rf
1
and Rf
2
are fluoroalkyl groups represented by RfCH
2
— and (Rf)
2
CH— where Rf is a fluoroalkyl group having a carbon atom number from 1 to 8.
Preferable examples of the positive ion represented by M in the general formula (1) are hydrogen ion, ammonium ion, quaternary ammonium ions, alkali metal ions, alkali earth metal ions, transition metal ions, and rare earth element ions.
The first compound (1) has the following six exemplary structures.
The above-mentioned bis(chlorosulfonyl)amine (2) used for preparing the first amine (1) can be synthesized, for example, by a method disclosed in Inorganic Syntheses, Vol. VIII, 1966, pp. 105-107, using phosphorus(V) chloride, sulfonic acid amide, and chlorosulfonic acid.
Preferable examples of the above-mentioned fluoroalcohol (3) used for preparing the first amine (1) are RfCH
2
OH and (Rf)
2
CHOH where Rf represents a fluoroalkyl group having a carbon atom number from 1 to 8, such as 2,2,2-trifluoroethylalcohol (CF
3
CH
2
OH), 2,2,3,3,3-pentafluoropropanol (CF
3
CF
2
CH
2
OH), 1,1,1,3,3,3-hexafluoro-2-propanol ((CF
3
)
2
CHOH), and 2,2,3,3-tetrafluoropropanol (CF
2
HCF
2
CH
2
OH).
In the step (a) of the above-mentioned first method, bis(chlorosulfonyl)amine (2) is reacted with the fluoroalcohol (3), in a solvent or without using solvent, for preparing the first amine (1). In order to obtain a higher yield, it is preferable to react 1 part by mol of bis(chlorosulfonyl)amine (2) w

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