Fluoroaluminate A1F4 compounds

Details Fluoroaluminate A1F4 compounds Fluoroaluminate A1F4 compounds

1999-07-02

2001-01-23

Zitomer, Fred (Department: 1713)

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

Organic compounds

Unsubstituted hydrocarbyl chain between the ring and the -c-...

C546S009000, C548S402000, 57, C549S003000, C549S206000, C556S186000

Reexamination Certificate

active

06177563

ABSTRACT:

The present invention relates to fluoroaluminate compounds and methods for their preparation.
Many compounds of the general formula M
+
AlF
4
−
are known wherein the fluoroaluminate Al ion is six-coordinate and wherein M
+
is a cation, for example, wherein M is potassium, thallium, rubidium, or NH
4
. Usually, such compounds are insoluble in nonaqueous media and have extended corner-shared fluoro-bridged network structures in the solid state.
Tetrahedrally coordinated AlF
4
−
compounds have been proposed to exist in a hot melt form or in vapor phase, but upon cooling reassemble into six-coordinate forms. “Tetramethylammonium-fluoroaluminates, -gallates and indates”, by P. Bukovec and J. Siftar,
Monatsh. Chem.
1975, 106, 483-490, describes the “probable” synthesis of the material N(CH
3
)
4
AlF
4
via dissolution of AlF
3
in aqueous HF in the presence of tetramethylammonium fluoride. The material first isolated is N(CH
3
)
4
AlF
4
H
2
O which may be dehydrated at 120° C. to give a material of the noted stoichiometry. Evidence for the anhydrous tetrafluoroaluminate as containing a tetrahedral AlF
4
−
anion is based on the simplicity of the IR spectrum.
“Fluoroaluminates of some organic base cations” by A. K. Sengupta and K. Sen.,
Indian J. Chem.,
1979, 17A, 107-108, describes a series of preparations of fluoroaluminate salts of organic cations prepared by dissolution of aluminum hydroxide in aqueous HF in the presence of the organic cation or base. In this case a series of compounds are prepared and their chemical analyses and thermal decomposition behavior reported. The authors claim that the products of thermal decomposition of their compounds are “a mixture of aluminum fluoride and oxide”. The fact that oxide is present in the final materials indicates that the materials they have prepared are in all cases mixed fluoro/aquo/hydroxo aluminate species much like the N(CH
3
)
4
AlF
4
H
2
O material above.
The aqueous synthetic procedures taught in the above references are not likely to work well for many other compounds. An anhydrous process for preparation of fluoroaluminate compounds is desirable due to its versatility. Additionally, it is desirable to have compounds wherein the four-coordinate form of the AlF
4
−
is retained. Such materials provide low temperature routes to new phases of AlF
3
, AlF
3
being a well-documented catalyst for numerous fluorocarbon transformations of industrial importance. Additionally, the solubility of such AlF
4
−
species in non-aqueous (organic) solvents provides a simple route for deposition onto high surface area supports for eventual conversion to well dispersed AlF
3
catalyst phases. The present invention provides such four-coordinate compounds, their precursors, and anhydrous processes for their preparation.
SUMMARY OF THE INVENTION
The present invention comprises a compound of the formula I, M
+n
(AlF
4
−
)
n
wherein M
+n
is an organic cation or polycation other than NMe
4
+
, NEt
4
+
, N(n−Bu)
4
+
, guanidinium H
+
or PyridineH
+
, and n is an integer from 1 to 3.
In particular the present invention comprises compounds of the above formula wherein M is selected from the group consisting of N(R
2
)
4
, P(R
2
)
4
, AS(R
2
)
4
, HN(R
2
)
3
, H
2
N(R
2
)
2
, H
3
N(R
2
), (R
2
)
3
P═N═P(R
2
)
3
, S[N(R
2
)
2
]
3
,
R is hydrogen, C
1
-C
10
linear or branched alkyl or aryl;
R
2
is C
1
-C
10
linear or branched alkyl or aryl;
n is 1; and
k is 1 to 10;
provided that M
+n
is other than NMe
4
+
, NEt
4
+
, N(n−Bu)
4
+
, guanidinium (H
2
N═C(NH
2
)
2
)
+
and pyridinium (C
5
H
6
N)
+
.
The present invention further comprises compounds of formula I, M
+n
(AlF
4
−
)
n
wherein M
+n
is of the form ZH
+
, n is 1, and Z is a base capable of accepting n protons.
The present invention further comprises anhydrous PyH
+
AlF
4
−
wherein Py is pyridine and which when thermolyzed forms pure AlF
3
.
The present invention further comprises a polymer having a repeating unit of the formula (X) or formula (XI).
wherein
m is 0 or an integer equal to or greater than 1;
n is an integer greater than 1;
Q is NR, O, or S; and
R is H or C
1
-C
6
alkyl.
The present invention further comprises processes for the preparation of compounds of formula M
+n
(AlF
4
−
)
n
wherein M
+n
and n are defined above. One such process comprises reacting Al(R)
3
with M
+n
(HF)
q
F
n
−
wherein M is an organic cation or polycation; n is an integer from 1 to 3; q is an integer of at least 1; and each R is independently C
1
-C
12
alkyl, C
1
-C
12
alkoxy, C
1
-C
12
enolate, aryl, or C
1
-C
12
alkamide.
A second process for the preparation of M
+n
(AlF
4
−
)
n
wherein n is an integer from 1 to 3, M is an organic cation of formula ZH
n
+n
and Z is a base capable of accepting n protons, comprises reacting Al(R)
3
wherein each R is independently C
1
-C
12
alkyl, C
1
-C
12
alkoxy, C
1
-C
12
enolate, aryl, or C
1
-C
12
alkamide with a solution of HF and Z.
A third process for the preparation of M
+n
(AlF
4
−
)
n
wherein M
+n
is an organic cation or polycation, and n is an integer from 1 to 3 comprises reacting ZH
m
+m
(AlF
4
−
)
m
with Y, wherein Z is a base capable of accepting m protons wherein m is an integer from 1 to 3, and Y is a proton-accepting base or a phosphorus ylid of formula R
1
R
2
R
3
P═CR
4
R
5
wherein R
1
, R
2
and R
3
are each independently linear, branched or cyclic C
1
-C
10
alkyl or substituted C
1
-C
10
alkyl, C
1
-C
10
alkoxy, aryl, aryloxy, heterocyclic, substituted heterocyclic, or together two or more of R
1
, R
2
or R
3
may form a ring of 3 to 10 atoms; R
4
and R
5
are each independently hydrogen, linear, branched or cyclic C
1
-C
10
alkyl or substituted alkyl, C
1
-C
10
alkoxy, aryl, aryloxy, heterocyclic, substituted heterocyclic or R
4
and R
5
together may form a ring of 3 to 10 atoms.
A fourth process for the preparation of M
+n
(AlF
4
−
)
n
wherein M
+n
is an organic cation or polycation, and n is an integer from 1 to 3 comprises reacting ZH
m
+m
(AlF
4
−
)
m
, wherein Z is a base capable of accepting m protons wherein m is an integer from 1 to 3, with M
+n
(X
−
)
n
wherein M is an organic cation or polycation other than H
+
and X is a stronger base than Z.
A fifth process for the preparation of M
+n
(AlF
4
−
)
n
wherein M
+n
is an organic cation or polycation, and n is an integer from 1 to 3 comprises reacting ZH
m
+m
(AlF
4
−
)
m
, wherein Z is a base capable of accepting m protons wherein m is an integer from 1 to 3, with M
+n
(X
−
)
n
wherein M
+n
is an organic cation or polycation other than H
+
and X
−
is an anion which forms a compound ZH
m
+m
(X
−
)
m
easily separable from the M
+n
(AlF
4
−
)
n
product.


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