Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2000-10-31
2002-01-01
Vollano, Jean F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C568S003000, C568S004000
Reexamination Certificate
active
06335466
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to compounds comprising a fluorinated aminoborate anion. In particular, the present invention relates to compounds comprising a fluorinated polyhedral aminoborate anion.
BACKGROUND OF THE INVENTION
A compound containing a weakly coordinating anion (i.e., an anion that coordinates only weakly with a cation) is useful in a variety of applications including as an electrolyte and a catalyst. Investigations of reactive metal and nonmetal cations continue to spur the development of new weakly coordinating anions. See, for example, Bochmann,
Angew. Chem., Int. Ed. Engl
. 1992, 31 1181; Strauss,
Chem. Rev
. 1993, 93, 927, Strauss,
Chemtracts
-
Inorganic Chem
. 1994, 6,1; and Seppelt,
Angew. Chem., Int. Ed. Engl
. 1993, 32, 1025. One of the most important uses of weakly coordinating anions is to enhance the catalytic activity of metal cations. Two examples that have received considerable attention recently are metallocene-catalyzed olefin polymerization, and lithium-catalyzed Diels-Alder reactions and 1,4-conjugate addition reactions. See Turner, European Patent Appl. No. 277,004, 1988; Pellecchia et al.,
Makromol. Chem., Rapid Commun
. 1992, 13, 265; DuBay et al.,
J. Org. Chem
. 1994, 59, 6898; Saidi et al.,
Chem. Ber
. 1994, 127, 1761; Kobayashi et al.,
Chem. Lett
. 1995, 307; and Arai et al.,
Angew. Chem., Int. Ed. Engl
. 1996,15, 3776.
Useful anions must not only be weakly coordinating, they must also be stable with respect to oxidation and/or fragmentation in the presence of highly electrophilic cations. In addition, an ideal weakly coordinating anion should have a single negative charge dispersed over a large surface composed of relatively nonpolar bonds to weakly basic atoms such as hydrogen or the halogens.
A variety of monoanions have been prepared to meet one or more desirable characteristics described above, including fluorinated carborane monoanion as described in commonly assigned U.S. Pat. No. 6,130,357, issued Oct. 10, 2000, which is incorporated herein by reference in its entirety. However, to date no fluorinated amino derivatives of polyhedral borate compounds (i.e., compounds comprising a fluorinated aminoborate anion) have been made. It is believed that fluorinated aminoborates are particularly useful as the amine functional group can be fuirther derivatized by a variety of groups, thereby allowing potential use in much wider range of applications than other polyhedral borate compounds. In addition, most current weakly coordinating anions (e.g., polyhedral borate anions) are relatively expensive to produce.
Therefore, there is a need for a fluorinated aminoborate anion that is weakly coordinating, and is thermally and hydrolytically stable. There is also a need for a method for relatively inexpensively producing the same.
SUMMARY OF THE INVENTION
This invention provides a compound comprising fluorinated aminoborate monoanion of the formula:
where R
1
, R
2
, R
3
, a, b, and c are defined below. In Formula I, R
1
, R
2
, and R
3
are bonded to N, which in turn is bonded to boron, and each of H and F is bonded to a different boron atom. Each of R
1
, R
2
, and R
3
is independently selected from the group consisting of hydrogen, C
1
-C
20
alky, C
3
-C
10
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
aralkyl, haloalkyl, alkenyl, polymer, and silyl. Exemplary polymers include polystyrene, polyethylene, polyethylene glycol, polypropylene, polyacrylate, polyurethane, polycarbonate, polytetrafluoroethylene, and other polymeric resins that allow a compound of the present invention to be bound to the polymeinc support. Preferably, each of R
1
, R
2
, and R
3
is independently selected from the group consisting of hydrogen, methyl, ethyl, butyl, benzyl, hexyl, cyclohexylmethyl, octyl, and dodecyl. The variable a is an integer from 6 to 14, preferably 10 or 12, and more preferably 12. The variable b is an integer from 0 to 12, preferably 0. And the variable c is an integer from 12 to 13, preferably c is a−1 (i.e., when a is 10 or 12, c is preferably 9 or 11, respectively; and the sum of 1+b+c is a.
Since the fluorinated aminoborate monoanion of the present invention is weakly coordinating and is stable under a variety of conditions, it can be formulated into a variety of forms. For example, the compound of the present invention can be dissolved in a variety of solvents to provide solutions which comprise the fluorinated aminoborate monoanion of the present invention. Alternatively, the compound of the present invention can be heated to provide a molten salt or a liquid comprising the fluorinated aminoborate monoanion of the present invention. Or a gel comprising the fluorinated aminoborate monoanion of the present invention can be formulated by admixing the compound of the present invention with appropriate polymer or by admixing the compound of the present invention with the polymer's precursor prior to a polymerization reaction.
Another embodiment of the present invention is a method for producing a compound comprising fluorinated aminoborate monoanion of Formula I above. Thus, the method of the present invention replaces at least one of the non-fluorine substituent on the boron atom with fluorine.
The compound of the present invention provides a multiple advantages including stability in a variety of thermal or chemical conditions. The fluorinated aminoborate monoanion of Formula I of the present invention is a weakly coordinating monoanion. Thus, the fluorinated aminoborate monoanion of Formula I can be used in a variety of applications including as an activator for catalysts, and as an electrolyte in batteries. These and other advantages will be readily apparent to those skilled in the art, based on the disclosure contained herein.
DEFINITIONS
The term “hydrocarbyl” refers to a compound having at least one carbon atom. Such compounds include aryl, alkyl, alkenyl and alkynyl. Moreover, hydrocarbyl can be straight chain, branched, or cyclic. Hydrocarbyl can also be substituted with other non hydrogen or carbon atoms such as halide, oxygen, sulfur, nitrogen or phosphorus.
The term “alkyl” refers to aliphatic hydrocarbons, preferably having one to about twenty carbon atoms, which can be straight or branched chain groups. Alkyl groups optionally can be substituted with one or more substituents, such as a halogen, alkenyl, alkynyl, aryl, hydroxy, alkoxy, carboxy, oxo or cycloalkyl. There may be optionally inserted along the alkyl group one or more oxygen, sulflur or substituted or unsubstituted nitrogen atoms. Exemplary alkyl groups include methyl, ethyl, i-propyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, trichloromethyl, and pentafluoroethyl.
The term “aryl” refers to aromatic ring moieties, preferably having five to about twenty ring atoms, including carboaryls, such as mono- and bicyclic aromatic carbocyclic ring moieties; and heteroaryls, such as mono- and bicyclic aromatic heterocyclic ring moieties. Aryl groups can be substituted with one or more substituents, such as a halogen, alkenyl, alkyl, alkynyl, hydroxy, amino, thio, alkoxy or cycloalkyl. Exemplary aryls include pyrrole, thiophene, fuiran, imidazole, pyrazole, 1,2,4-triazole, pyridine, pyrazine, pyrimidine, pyridazine, thiazole, isothiazole, oxazole, isoxazole, s-triazine, benzene, indene, indoline, isoindene, benzofuran, dihydrobenzofuran, benzothiophene, indole, 1H-indazole, azulene, tetrahydroazulene, benzopyrazole, benzoxazole, benzoimidazole, benzothiazole, 1,3-benzodioxole, 1,4-benzodioxan, purine, naphthalene, tetralin, coumarin, chromone, chromene, 1,2-dihydrobenzothiopyran, tetrahydrobenzothiopyran, quinoline, isoquinoline, quinazoline, pyrido[3,4-b]-pyridine, and 1,4-benisoxazine.
The term “alkenyl” refers to aliphatic hydrocarbons, preferably of two to about twenty carbon atoms, having one or more double bonds between adjacent carbon atoms. Alkenyl groups can be straight or branched chain groups. Exemplary alkenyl groups include vinyl, 1,3-butadienyl, 2-propenyl
Ivanov Sergei V.
Strauss Steven H.
Colorado State University Research Foundation
Townsend and Townsend / and Crew LLP
Vollano Jean F.
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