Organic compounds -- part of the class 532-570 series – Organic compounds – Halogen containing
Patent
1998-09-22
2000-06-13
Killos, Paul J.
Organic compounds -- part of the class 532-570 series
Organic compounds
Halogen containing
570183, C07C 2200, C07C 2500
Patent
active
060751711
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
This invention relates to 2-substituted 7-haloindenes useful in coupling reactions to produce a wide variety of metallocene olefin polymerization catalyst intermediates and to metallocene catalysts derived from such intermediates.
BACKGROUND OF THE INVENTION
Metallocenes which comprise indene systems are well known .alpha.-olefin polymerization catalysts. Substitution patterns in such indene systems significantly influence poly-.alpha.-olefin properties, including tacticity and molecular weight.
Spaleck, et al., Organometallics (1994) 13:954-963 describes bridged zirconocene catalysts including indene systems illustrated by Compound 4 of "Scheme 1" (p. 955) which yield highly isotactic polypropylene when used with methylaluminoxane as a cocatalyst. As shown by "Scheme 2", Compound 10, Spaleck's synthesis requires an expensive 2-(bromomethyl) biphenyl starting material.
This invention provides a more cost effective synthesis of metallocene catalysts which comprise indene systems.
SUMMARY OF THE INVENTION
One aspect of this invention provides novel 2-substituted, 7-haloindenes of Formula I: ##STR1## in which R.sub.1 is any straight or branched chain alkyl group having 1 to 10 carbon atoms, and X is a halogen, i.e., fluorine, chlorine, bromine or iodine. A preferred embodiment of this aspect of the invention is 2-methyl-7-chloroindene.
Another aspect of the invention includes coupling of Formula I indenes with a Grignard reagent having the formula ArMgX to produce the novel compounds of Formula II: ##STR2## in which Ar may be any aryl group preferably a phenyl, or a napthyl. Formula II compounds in which Ar is a phenyl, e.g., Spaleck's compounds 13a and 13b, or a naphthyl group are useful for the synthesis of the zirconocene olefin polymerization catalysts of Spaleck's "Scheme 1". See Spaleck compounds 7a, 7b, 7c, 8 and 9.
The invention accordingly comprises the novel Formula I and II compounds per se, procedures for the synthesis thereof, procedures for the conversion of Formula II compounds to catalyst intermediates, including Spaleck's compounds 13a and 13b, for the production of metallocene catalysts from such intermediates and for the use of such catalysts to polymerize, e.g., an .alpha.-olefin.
DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a scheme for the synthesis of the Formula I compound, 2-methyl-7-chloroindene.
FIG. 2 is a NMR spectrum of 2-methyl-7-chloroindene produced by the FIG. 2 scheme as shown by Example 1.
FIG. 3 illustrates a scheme for the synthesis of the Formula I compound, 2-ethyl-7-chloroindene.
FIG. 4 illustrates a scheme for Grignard reagent coupling a Formula I compound to provide a Formula II compound.
DETAILED DESCRIPTION OF THE INVENTION PREPARATION OF FORMULA I COMPOUNDS
Either of two methods, as shown by Examples 1 and 2 and FIGS. 1 and 3, may be used to prepare Formula I compounds.
THE EXAMPLE 1 METHOD
The starting material for the Example 1 method is a malonic acid diester having the Formula III: ##STR3## in which R.sub.1 (which is the same R.sub.1 as in the Formula I and II compounds), R.sub.2 and R.sub.3 are the same or optionally different straight or branched chain alkyl groups having 1 to 10 carbon atoms. Alkyl groups specifically useful in this aspect of the invention include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, decyl and isodecyl groups. A preferred diester is methyl diethyl malonate in which R is methyl and R.sub.2 and R.sub.3 are ethyl.
The malonic acid diester of Formula III is reacted with an alkali metal hydride ZH, in which Z is lithium, sodium or potassium, to provide an intermediate compound in which the "H" of the Formula III diester is replaced by Z+, e.g., Na+. This reaction is appropriately carried out by adding a 40% to 60% dispersion of an alkali metal hydride in mineral oil to a non-interfering solvent such as tetrahydrofuran (THF) in a reaction vessel positioned in an ice bath. The malonic diester is added slow
REFERENCES:
patent: 5789634 (1998-08-01), Sullivan et al.
Barnes Hamlin H.
Sullivan Jeffrey M.
Boulder Scientific Company
Irons Edward S.
Killos Paul J.
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