Organic compounds -- part of the class 532-570 series – Organic compounds – Silicon containing
Reexamination Certificate
2002-11-06
2003-11-04
Barts, Samuel (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Silicon containing
C556S452000, C556S453000, C556S454000
Reexamination Certificate
active
06642403
ABSTRACT:
BACKGROUND OF THE INVENTION
Silylation is a process whereby a silyl group, typically a trimethylsilyl group, is introduced into a molecule, usually in substitution for an active hydrogen. Silylation is often part of a synthetic or analytic strategy in which a protic hydrogen of the type found in alcohols or amines is replaced in order to proceed in a synthetic step in which the hydrogen would otherwise interfere, or in order to make the molecule more volatile or more soluble in an organic solvent.
A goal of synthetic chemists is not only to synthesize new compounds, but also to be able to purify the new materials. Purification first involves the separation of the desired product from the reaction mixture and from various byproducts, which can be accomplished by methods such as evaporation, filtration and extraction. Ideally, only the desired product is soluble in a particular phase, and thus can be easily extracted. Typical phases used in separation are gas, liquid (organic and aqueous), and solid. A less common phase, the fluorous liquid phase, is becoming increasingly more utilized in synthetic chemistry as a means of separation, and it is this phase which relates to the present invention.
The fluorous phase is a phase comprising highly fluorinated solvents and compounds that dissolve in them. Perfluorocarbon and some very highly fluorinated liquids are nonpolar and nontoxic, and are immiscible with many common organic solvents and water. Because organic and inorganic compounds have little or no tendency to dissolve in the fluorous phase, it is very useful for extracting fluorous compounds.
For this reason, there has recently been considerable interest in “fluorous phase synthesis.” In fluorous synthesis, a fluorous phase label is attached to a substrate such that the labeled substrate and resulting products will be separable into the fluorous phase using a separation technique such as fluorous-organic liquid-liquid extraction. The substrate is then subjected to one or more reactions before the fluorous label is removed, yielding the desired small molecule. (D. P. Curran.
Angew. Chem. Int'l Ed.,
37, pp. 1174-1196 (1998), which is incorporated herein by reference.)
Fluorous synthesis is attractive for several reasons. First, the tagged molecule containing the fluorous label can be separated from untagged molecules using straightforward liquid-liquid or solid-phase extraction methods. Second, perfluoroalkyl chains are quite stable under organic reaction conditions, and thus tagged molecules containing fluorous labels can be exposed to a range of reaction conditions. Additionally, because fluorous labels can be attached and detached at the same site, the labels can be easily recycled. Finally, the substrates utilized in fluorous synthesis are soluble and thus can be identified and analyzed by analytical techniques which are typically utilized for the analysis of small molecules.
However, despite such advantages, there remains a need in the art for silylation reagents which would be suitable for fluorous phase synthesis for silylation reactions by rendering the silylated compounds soluble in fluorocarbon solvents. Such silylation reagents should have the same requirements in a reactivity sense to those used in conventional syntheses, however, there is also a need for an additional solubility in fluorous phases.
SUMMARY OF THE INVENTION
This invention relates to a series of fluoroalkylsilane compounds designated by the Formula I, wherein R
1
and R
2
are independently selected from the group consisting of hydrogen and lower alkyl groups of from about 1 to 5 carbon atoms; R
3
is R
1
R
5
wherein R
5
is any branched or straight chain perfluoroalkyl of from about 1 to 25 carbon atoms; R
4
is R
1
R
6
wherein R
6
is any branched or straight chain perfluroalkyl of from about 5 to 25 carbon atoms; R is selected from the group consisting of linear and branched alkyl groups; and X is a hydrolyzable group or atom.
This invention also relates to a process for producing the compound of Formula (I), comprising reacting an alkyldialkoxysilane with a perfluoroalkyl-substituted silane to produce a perfluoroalkyl-substituted dialkylsiloxyalkylsilane intermediate; and reacting the intermediate with halogen.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to a series of fluoroalkylsiloxysilanes which behave as silylation reagents and also enhance the solubility of the silylated products in fluorocarbon solvents for preferred uses in fluorous phase synthesis. Generally, and preferably, the fluoroalkylsiloxysilanes according to the present invention are compounds designated by
formula I:
In Formula I, R
1
and R
2
are independently selected from hydrogen or lower alkyl groups of from about 1 to 5 carbon atoms and are both preferably CH
3
. R
3
is R
1
R
5
where R
5
is any branched or straight chain perfluoroalkyl preferably of from about 1 to 25 carbon atoms and most preferably of from about 1 to 5 carbon atoms. R
4
is R
1
R
6
where R
6
is any branched or straight chain perfluoroalkyl preferably of from about 5 to 25 carbon atoms and preferably from about 5 to 10 carbon atoms. As noted above, each R
1
or R
2
group on Si or in R
3
or R
4
may be the same or different within the compound. It is preferred that the total number of fluorine atoms in R
3
and R
4
is at least about fourteen. R is generally any linear or branched alkyl group, preferably a lower alkyl of from about 1 to 6 carbon atoms, more preferably an alkyl group of about 1 to 3 carbon atoms, and most preferably a methyl group. X is a hydrolyzable group or atom, preferably a halogen, such as chlorine or bromine, or a dimethylamino group, and most preferably chlorine.
For example, a preferred silylation reagent according to the present invention is a compound according to formula I in which R=methyl; X=chlorine; and (R
1
)
2
═(R
2
)
2
═(CH
3
)
2
; R
3
═R
4
═(CH
2
)
2
(CF
2
)
5
CF
3
. Such a compound is represented by formula II.
Compounds according to formula I behave as silylation reagents due to the presence of a hydrolyzable Si—X bond. Additionally, the presence of at least about fourteen fluorine atoms makes the compounds generally soluble in the fluorous phase. As a result, the silylated product may be more easily extracted into the fluorous phase and thus isolated from the reaction mixture.
This invention also relates to a two-step process for producing the fluoroalkylsiloxysilanes represented by formula I. In general, the first step involves the reaction of an alkyldialkoxysilane, such as preferably methyldiethoxysilane, with an excess of a fluoroalkyl-substituted silane, thereby substituting the alkoxy, preferably ethoxy, groups for fluoroalkylsiloxy substituents. In the second step, a silyl-hydride is converted to the desired hydrolyzable group by, as preferred non-limiting examples, chlorination or bromination.
This reaction sequence thus provides for the ability to synthesize a variety of fluoroalkylsiloxysilane compounds according to the present invention because the fluoroalkyl and hydrolyzable substituents are introduced to the silane in different steps.
As an example, the process to produce preferred compound II is illustrated. In the first step, equation III, methyldiethoxysilane is reacted with an excess of tridecafluorooctyldimethylchlorosilane to produce the intermediate product, bis(tridecafluorooctyldimethylsiloxy)methylsilane, as well as bis(tridecafluorooctyl)tetramethyldisiloxane as a byproduct.
In the second step, illustrated by equation IV, the intermediate in equation (III) is reacted with chlorine gas to yield the desired silane of compound (II) and HCl as a byproduct.
The invention will be further illustrated in accordance with the following non-limiting example:
REFERENCES:
D.P Curran.Angew Chem Int'l Ed., 37, pp. 1174-1196 (1998).
Arkles Barry C.
Larson Gerald L.
Pan Youlin
Akin Gump Strauss Hauer & Feld L.L.P.
Barts Samuel
Gelest Inc.
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