Malononitrile-derivative anion salts, and their uses as...

Details Malononitrile-derivative anion salts, and their uses as... Malononitrile-derivative anion salts, and their uses as...

1998-11-19

2001-12-25

Higel, Floyd D. (Department: 1613)

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

Organic compounds

Phosphorus esters

C558S386000, C558S440000, C558S453000, C546S096000, C546S256000, C548S340100, C548S300100, C534S838000

Reexamination Certificate

active

06333425

ABSTRACT:

The present invention is concerned with ionic compounds derived from malononitrile in which the anionic charge is delocalized, and their uses.
It is known and particularly interesting to introduce ionic groups in organic molecules or polymers having various functions. Coulombic forces correspond, indeed, to the stronger interactions which are available at the molecular level, and the ionic groups modify in a very noted manner the molecules to which they are attached. Coloring materials which are made soluble in water by means of sulfonate or carboxylate functions may be mentioned.
However, the —CO
2
−
1/mM
m+
or —SO
3
−
1/mM
m+
groups of this type are not dissociated, and they cause no solubility in solvents except water or certain highly polar protic solvents such as light alcohols, which considerably restrict the scope of their use.
On the other hand, salts of the compounds [R
F
SO
2
—N—SO
2
R
F
]
−
1/mM
m+
in which R
F
is a perfluorinated group and M
m+
is a cation of valence m+ which are soluble and are dissociated in ordinary aprotic media or solvating polymers, are known. It is however considered that the existence of two perfluoroalkylsulfonyl groups (in particular the existence of fluorine atoms on the a atom of carbon of each sulfonyl group) which exert an important attracting power on the electrons of the anionic charge, is a necessary condition to obtain properties of solubility and dissociation. For example, the pK
a
of the acid H[CF
3
SO
2
—N—SO
2
CF
3
] is only 1.95, as compared to that of the non-fluorinated acid CH
3
SO
3
H (pK
a
=0.3) and is clearly inferior to that of the perfluorinated acid CF
3
SO
3
H (pK
a
<−9) because of the basic character of the central nitrogen atom.
Surprisingly, the inventors have found that the compounds containing ionic groups —C(CN)
2
−
have excellent properties of solubility and dissociation, even when they contain no highly electroattractive perfluorinated groups.
The present invention consequently aims at supplying a family of ionic compounds having a good solubility and a good dissociation, without requiring complex modifications of the starting molecule. The precursors of the molecules of the invention are for the most part industrial products and/or easily accessible. In addition, it should be noted that the absence, or at least the decrease of the perfluorinated fraction in the compounds of the invention, enables to reduce production costs of the compounds and consequently the cost of the resulting applications.
An object of the present invention is an ionic compound which is a derivative of malononitrile comprising an anionic part which is associated to at least one cationic part M
+m
in a sufficient number to provide for the electronic neutrality of the whole, characterized in that M is a hydroxonium, a nitrosonium NO
+
, an ammonium —NH
4
+
, a metallic cation having a valency m, an organic cation having a valency m or an organometallic cation having a valency m, and in that the ionic part corresponds to one of the formulae R
D
—Y—C(C≡N)
2
−
or Z—C(C≡N)
2
−
in which:
Z represents an electroattractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from:
j) —CN, —NO
2
, —SCN, —N
3
, FSO
2
—, —CF
3
, R′
F
CH
2
— (R′
F
being a perfluorinated radical, preferably CF
3
—), fluoroalkyloxy, fluoroalkylthioxy, fluoroalkenyloxy, fluoroalkenylthioxy radicals;
jj) radicals comprising one or more aromatic nuclei possibly containing at least one nitrogen, oxygen, sulfur or phosphorus atom, said nuclei possibly being condensed nuclei and/or said nuclei possibly carrying at least one substituent selected from halogens, —CN, —NO
2
, —SCN, —N
3
, CF
2
═CF—O—, radicals R
F
— and R
F
CH
2
— in which R
F
is a perfluoroalkyl alkyl having 1 to 12 carbon atoms, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophorous group and/or at least one anionic ionophorous group;
with the proviso that one substituent Z may be a monovalent radical, a multivalent radical, or part of a multivalent radical (including a dendrimer) carrying at least one group —C(C≡N)
2
, or a segment of a polymer;
Y represents a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group or a phosphonyl group and:
R
D
is a radical selected from:
a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic or heterocyclic radicals, including polycyclic radicals;
b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, hydroxy;
c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms such as nitrogen, oxygen, sulfur;
d) radicals comprising condensed aromatic cycles which possibly comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;
e) halogenated or perhalogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl radicals, said radicals possibly comprising functional ether, thioether, imine, amine, carboxyl, carbonyl or hydroxy groups;
f) radicals R
C
C(R′)(R″)—O— in which R
C
is an alkyl perfluorinated radical and R′ et R″ are independently from one another a hydrogen atom or a radical such as defined in a), b), c) or d) above [for example CF
3
CH
2
O—, (CF
3
)
3
CO—, (CF
3
)
2
CHO—, CF
3
CH(C
6
H
5
)O—, —CH
2
(CF
2
)
2
CH
2
—];
g) radicals (R
B
)
2
N—, in which the radicals R
B
which are identical or different are such as defined in a), b), c), d) and e) above, one of the R
B
may be a halogen atom, or the two radicals R
B
together form a divalent radical which constitutes a cycle with N;
h) polymer radicals;
i) radicals having one or more cationic ionophorous groups and/or one or more anionic ionophorous groups;
with the proviso that one substituent R
D
may be a monovalent radical, part of a multivalent radical carrying a plurality of —Y—C
−
(C≡N)
2
groups or a segment of a polymer;
with the proviso that when Y is a carbonyl and R
D
is a perfluoroalkyl radical having 1 to 3 carbon atoms, or when Z is —CN, M is different from an alkali metal.
According to an embodiment of the invention, the cation is a metallic cation selected from cations of alkali metals, cations of alkali-earth metals, cations of transition metals, cations of trivalent metals, cations of rare earths. By way of example, Na
+
, Li
+
, K
+
, Sm
3+
, La
3+
, Ho
3+
, Sc
3+
, Al
3+
, Y
3+
, Yb
3+
, Lu
3+
, Eu
3
may be mentioned.
The cation may also be an organometallic cation, such as a metallocenium. By way of example, the cations derived from ferrocene, titanocene, zirconocene, from an indenocenium or a metallocenium arene, cations of transition metals complexed with ligands of phosphine type possibly having a chirality, organometallic cations having one or more alkyl or aryl groups covalently fixed to an atom or a group of atoms, may be mentioned. Specific examples include methylzinc, phenylmercury, trialkyltin or trialkyllead, chloro[ethylene-bis(indenyl)] zirconium (IV) or tetrakis-(acetonitrile)palladium(II). The organo-metallic cation may be part of a polymer chain.
In a specific embodiment of the invention, the organic cation is an onium cation selected from the group consisting of R
3
O
+
(oxonium), NR
4
+
(ammonium), RC(NHR
2
)
2
+
(amidinium), C(NHR
2
)
3
+
(guanidinium), C
5
R
6
N
+
(pyridinium), C
3
R
5
N
2
+
(imidazolium), C
3
R
7
N
2
+
(imidazolinium), C
2
R
4
N
3
+
(triazolium), SR
3
+
(sulfonium), PR
4
+
(phosphonium), IR
2
+
(iodonium), (C
6
R
5
)
3
C
+
(carbonium) cations. In a given onium cation, the

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