Title of Invention

IMPROVED SYNTHESIS OF ANSA-METALLOCENE AND THEIR PARENT LIGANDS IN HIGH YIELD

Abstract The Present invention provides a method of making compounds comprising linked cyclopentadienyl and fluorenyl groups, including substituted analogs thereof, which are precursors to a«s<2-metallocenes comprising bridged cyclopentadienyl and fluorenyl ligands. In one aspect, this invention provides a preparative method for (5-cyclopentadienyl)[5-(2,7-di-tert-butylfluorenyl)] hex-1-ene, and owsa-metallocenes comprising this ligand.
Full Text CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Patent Application Serial No. 10/876,948 entitled "Improved Synthesis of ^/iwr-Metallocenes and Their Parent Ligands in High Yield," which was filed on June 25,2004 and is incorporated by reference herein in its entirety.
TECHNICAL FIELD OF THE INVENTION
This invention relates to the fields of organic synthesis and organometallic synthesis, including synthetic methods for ansa-mctallocenes, and their parent ligands.
BACKGROUND OF THE INVENTION
Metallocene compounds constitute useful catalyst components for a variety of chemical transformations including olefin polymerizations, where metallqcenes are often used in combination with a variety of cocatalysts. It is generally accepted that the metallocene structure itself is intimately involved in determining the physical properties of the resulting polyolefin and hence its eventual usefulness in a variety of end-use applications such as in film, pipe and blow-molded articles. Therefore, there is a need to develop new methods to prepare metallocenes that allow an assortment of substituents to be incorporated
into the metallocene structure.
It is likewise of interest to develop new methods to prepare bridged or ansa-metallocene compounds, which comprise two r|5-cyclopentadienyl-type ligands linked by a chemical spacer. A variety of substituents can he incorporated into the ansa-metallocene structure, including substituents on the cyclopentadienyl-type ligands, on the bridging group, or both, each of which helps determine the.physical properties of polyolefins prepared using these compounds. To accomplish this task, it is also of interest to develop new preparative methods for the DESCRIPTION OF THE INVENTION
This invention encompasses methods for the synthesis of organic compounds comprising two cyclopentadienyl-type groups linked by a bridging group, which constitute useful ligaads in preparing ansa-metallocene complexes. These anse-metallocenes can be used subsequently as catalyst components in olefin polymerizations. In one aspect, the methods of this invention generajly afford higher yields of the desired product than were heretofore available. In one aspect, for example, the methods disclosed herein permit a range of substituents to be incorporated into the ligand and the ansa-metallocene, which in turn can affect and determine the physical properties of polyolefins prepared using these compounds.
In one aspect of this invention, a method is provided for the synthesis of compounds comprising linked cyclopentadienyl and fiuorenyl groups, inchlding substituted analogs thereof, which are precursors to anra-metalloeenes comprising bridged cyclopentadienyl and fiuorenyl iigands. However, this method is also applicable to ligands comprising linked cyclopentadienyl and indenyl groups, indenyl and fiuorenyl groups, two cyclopentadienyl groups, two indenyl groups, or two fluoreny} groups. This invention will be illustrated throughout by examples for the preparation of linked cyclopentadienyl and fiuorenyl groups and onjfl-metaJJocenes comprising bridged cyclopentadienyl and fluorenyl ligands. In this aspect, for example, this invention provides a new high-yield method for making the metallocene, (S-cyclopentadienylJtS^J-di-tert-butylfluorenylJJhex-l-ene zirconium dichloridc, as well as its parent ligand, (5-cyclopentadienyl)[5-(2,7-di-tert-butylfiuarenyl)]hex~l-enc. However, many variations' in the substitution patterns for this ligand and criura-metallocene are possible, as disclosed herein.
In one aspect, this invention provides a method for making a compound of the formula
(Figure Remove)
(I), and isomers thereof, comprising:
(Figure Remove)

a) contacting a compound of the fonnula ^^ (H) and an
dkyi lithium reagent in an ethereal solvent to form a first mixture, wherein compound II
s substantially deprotonated to form Li(II);
b) rapidly combining the first mixture with a fulvene compound of the formula
(Figure Remove)

(ffl) to form a second mixture, wherein either Li(II) or compound in is optionally a limiting reagent, and wherein the limiting reagent, if present, has substantially reacted; and
c) contacting the second mixture with a proton source to form a third mixture

(Figure Remove)
R1 R*
comprising ^-/ (I), and isomers thereof;

wherein R1 and R2 independently are hydrogen or an aliphatic or substituted aliphatic group having from I to 20 carbon atoms; and
wherein each R3 independently is hydrogen or an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms.
Typically, compound I is formed in at least 85% yield, at least 90% yield, or at least 95% yield.
For example, compounds of the formula I mat can be prepared using this invention
(Figure Remove)
include the compound of the fonnula
disclosed herein using the precursorswhich can be prepared as
(Figure Remove)

(II) and compound HI having the formula ^—'J , wherein R3 can be typically H,
t-butyl, i-propyl, n-propyl, ethyl, or methyl, and wherein n is an integer from 1 to 6.
la another aspect, this invention provides a method of making a compound of the formula
(Figure Remove)

R2
11 /
(I), and isomers thereof, comprising: a) providing a source of a fluorenyi anion having the formula




b) rapidly combining the source of the fluorenyi anion with a fulvene compound (Figure Remove)


of the formula ^—U (HI) to form a mixture, wherein either the source of the fluorenyi anion or compound HI is optionally a limiting reagent, and wherein the limiting reagent, if present, has substantially reacted; and
c) contacting the mixture with a proton source to form
(Figure Remove)
R R2
ii /
(I), and isomers thereof;
wherein R1 and R2 independently are hydrogen or an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms; and
wherein each R3 independently is hydrogen or an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms.
In this aspect, for example, the source of the fluorenyl anion having the fonnula

(Figure Remove)
•" can typically comprise lithium, sodium, potassium,
magnesium, calcium, or a combination thereof, in addition to comprising the fluorenyl anion. For example, the source of the fluorenyl anion having the fonnula

(Figure Remove)

can typically comprise a salt of the fluorenyl anion comprising lithium, sodium, potassium, magnesium, calcium, or a combination thereof.
The ethereal solvent used in this method, can be independently selected from a range of ethereal solvents, including, but not limited to, dimethyl ether, diethyl ether, diisopropyl ether, di-n-propyl ether, di-n-butyl ether, methyl t-butyl ether, diphenyl ether, THF, 1,2-dimethoxyethane, or any combination thereof.
hi another aspect of the invention, the rapid combination of the ethereal solution of the fluorenyl component Li(II) and the fulvene compound in, is typically carried out over a time period of less than 1 minute. This combination time for the fluorenyl and the fulvene compounds is different than the total contact time between these compounds, prior to proceeding to the subsequent step in the process. The combination time describes the elapsed time over which the addition of the fulvene to the ethereal solution of the fluorenyl, or alternatively, the addition of the ethereal solution of fluorene compound to the fulvene, is initiated and completed.
This method can further compriseisolating compound I. For example, the method of this invention can further comprise removing the volatile components from the third mixture to provide a residue comprising I, optionally triturating the residue with a solvent in which I is substantially insoluble and IH is soluble, and isolating I. Examples of solvents that are useful in this trituration include, but are not limited to, alcohols having up to 8 carbon atoms, examples of which include, but are not limited to methanol, ethanol, i-propanol, n-propanol, n-butanol, see-butanol, t-buianol, 1-hexanol, 2-hexanol, 3-hexanol, any mixture thereof, or any combination thereof.
In a further aspect of this invention, a method is provided for making an ansa-metallocene compound of the fonnula
(Figure Remove)

(IV), comprising:
(Figure Remove)

a) contacting a compound of the.formula X (JQ and a first
aLkyl lithium reagent in a first ethereal solvent to form a first mixture, wherein compound
II is substantially deprotonated to form Li(II);
b) rapidly combining the first mixture with a fulvene compound of the formula
(Figure Remove)

«—U (III) to form a second mixture, wherein the limiting reagent has substantially reacted;
c) contacting the second mixture with a proton source to form a third mixture
(Figure Remove)

comprising ^-/ (I), including isomers thereof, in at least 85% yield;
d) removing the volatile components from the third mixture to provide a residue
comprising I;
e) optionally triturating the residue with a solvent in which I is substantially
insoluble and m is soluble to provide I, followed by isolation of I;
I) contacting the I with from 2 to 2.5 molar equivalents of a second alkyl lithium reagent in a second ethereal solvent to form a fourth mixture, wherein the I is substantially deprotonated to form U2(I);
g) contacting the fourth mixture with M1)^ and an optional hydrocarbon cosolvent
(Figure Remove)

b) removing the volatile components from the fifth mixture to provide IV in at least 80% yield;
i) optionally washing the IV in a non-polar solvent;
j) optionally extracting the IV with a polar solvent followed by removing the volatiles from the polar solvent solution to provide TV; and
k) optionally crystallizing the IV -from an aromatic solvent; wherein:
R1 and R2 are independently selected from an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms, or hydrogen; and
R3, in each instance, is independently selected from an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms, or hydrogen;
M'isZrorHf;and
X is Cl, Br, or I.
It was found that yields of the metallocene were improved when the volatile components were removed from the fifth mixture to provide IV.
This method can also be used to prepare a zirconocene analog having the structure
(Figure Remove)

, according to the method disclosed herein, wherein compound I

has the formula " , compound H has the formula


(Figure Remove)
-R3
, and compound TO has the formula
wherein:
R3 is H, t-butyl, i-propyl, n-propyj, ethyl, or methyl; and
n is an integer from 1 to 6.
As disclosed herein for the parent ligand, in this aspect also, the rapid combination of a lluorenyl component Li(II) with a fulvene component IQ is typically carried out over a time period of less than 5 minutes, less than 3 minutes, less man 1 minute, or less than IS seconds. This combination time for the fluorenyl and the fulvene compounds is different than the total contact time between these compounds, prior to proceeding to the subsequent step in the process.
Also in this aspect, the first and second ethereal solvents used in the preparation of the metallocene can be independently selected from a range of ethereal solvents, including, but not limited to, dimethyl ether, diethyl ether, diisopropyl ether, di-n-prqpyt ether, di-n-butyl ether, methyl t-butyl ether, diphenyl ether, THF, 1,2-dimethoxyethane, or any combination thereof.
This method of preparing the metallocene, which comprises removing the volatile components from the third mixture to provide a residue comprising I, can also optionally comprise triturating the residue with a solvent in which I is substantially insoluble and HI is soluble to provide I, followed by isolation of I. Examples of solvents that are useful in this trituration include, but are not limited to, alcohols having up to 8 carbon atoms, examples of which include, but are not limited to methanol, ethanol, i-propanol, n-propanol, n-butanol, sec-butanol, t-butanol, 1-hexanol, 2-hexanol, 3-hexanol, any mixture thereof, or any combination thereof.

These and other aspects, features, embodiments, and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed features.
The following patent applications, filed contemporaneously with the present application, are incorporated by reference herein in their entireties: U,S. Patent Application No. 10/877,039; U.S. Patent Application No. 10/876,891; U.S. Patent Application No. 10/876,930; and U.S. Patent Application No. 10/877,021.
The following is a brief description of the Figures.
FIGURE 1 represents a 1H NMR spectrum in CDCI3 of the pentane washing step, after removal of the volatiles, for fee synthesis of (5-cyclopentadienyl)[5-(2,7-di-tert-butylfluorenyl)]hex-l-ene zirconium dichloride.
FIGURE 2 represents a H NMR spectrum in CDC13 of the OfoCli extract that followed after a pentane washing step, for the synthesis of (5-cyclopentadienyl)[5-(2,7-di-teri-butylfluorenyl)]hex-l-ene zirconium diehloride.
The present invention provides a method of making a variety of organic compounds comprising two cyclopentadienyl-type groups linked by a bridging group, which constitute useful Hgands in preparing oawi-metallocene complexes. The methods disclosed herein can be applied to the preparation of compounds comprising linked cyclopcntadienyi and fiuorenyl groups, linked cyclopentadienyl and indenyl groups, linked indenyl arid fiuorenyl groups, two linked cyclopentadienyl groups, two linked indenyl groups, two linked fiuorenyl groups. In each case, these compounds can serve as precursor Ugands to the corresponding ansa-metallocenes, which themselves can be used as catalyst components in olefin polymerizations, In one aspect, the methods of this invention generally afford higher yields of the desired product than were heretofore available.
Ligaad Synthesis. In one aspect, the present invention provides a method for making a compound of the formula
(Figure Remove)

(I), including isomers thereof, in at least 85% yield, comprising:
(Figure Remove)

a) contacting a compound of the formula ^*x (II) and an
alkyl lithium reagent in an ethereal solvent to form a first mixture, wherein compound II
is substantially deprotonated to form Li(fl);
b) rapidly combining the first mixture with a fulvene compound of the formula
R' R2
^—'•> (HI) to form a second mixture, wherein the limiting reagent has substantially reacted; and
c) contacting the second mixture with a proton source to form a third mixture

Rs
(Figure Remove)
R2
comprising v^jf (I), including isomers thereof;
wherein:
R! and R* are independently selected from an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms, or hydrogen; and
R3, in each instance, is independently selected from an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms, or hydrogen.
This method provides I in at least 85% yield, at least 90% yield, or at feast 95% yield.
In the formulas I, n, and m, R1 and R2 can be independently selected from an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms, or hydrogen; and R3, in each instance, is independently selected from an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms, or hydrogen. Examples of aliphatic groups, in each instance, include, but are not limited to, an alkyl group, a cycloalkyl group, an alkenyl group,
a cycloalkenyl group, an alkynyl group, an alkadienyl group, a cyclic group, and the like, and includes all substituted, unsubstituted, branched, and linear analogs or derivatives thereof, in each instance having from one to 20 carbon atoms. Thus, aliphatic groups include, but are not Limited to, hydrocarbyls such as paraffins and alkenyls. For example, aliphatic groups as used herein include methyl, ethyl, propyl, n-butyl, left-butyl* sec-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, and the like.
The term isomers thereof, when used to describe the compound of formula I, is generally used to indicate mat this method can provide enantiomers or diastereomere which, can arise depending upon the identity of R1, R2, and each R3 moiety, all of which are independently selected, and this method can also provide regioisomers resulting from where the bridging group bonds to the cyclopentadienyl ring. The regioisomers of I would likely arise as a result of the regiochemistry of protonating the anionic complex formed from the reaction of Li(B) with III.
In another aspect, this method for making the ligand I comprises contacting a compound of the formula II and aft alkyl lithium reagent in an ethereal solvent to form a first mixture, wherein compound II is substantially deprotonated to form Li(n). In this aspect, this deprotonation reaction can by typically carried out with an equimolar amount of II and an alkyl lithium reagent, or with a slight excess of either, but is typically carried out with from 1.1 to 1.2 molar equivalents of alkyl lithium reagent so mat compound II is substantially deprotonated to form U(H). In mis aspect, the alkyl lithium reagent that can be used is any alkyl lithium reagent mat allows! to be prepared in at least 85% yield, including, but not limited to MeLi, n-BuLi, t-BuLi, n-hexylLi, LiCHzSiMes, LiCHaPh, LiCHiCMej, or any combination thereof. Therefore, the n and the alkyl lithium reagent react to form Li(H) in at least 85% yield to be substantially deprotonated, however, typically, II and the alkyl lithium reagent react to form U(II) in at least 9.0% yield, at least 95% yield, or at least 98% yield. While other reagents may be used to deprotonate n, the lithium alkyls, including n-BuLi, work well in this synthetic method. Thus, in this aspect, the duration of the contact time between n and an alkyl lithium reagent is typically that time necessary to substantially deprotonate II, that is the time necessary to form Li(II) in at least 85% yield, at least 90% yield, at least 95% yield, or at least 98% yield
The ethereal solvent used in this method, can be independently selected from a range of ethereal solvents, including, but not limited to, dimethyl ether, diethyl ether, diisopropyl ether, di-n-propyl ether, di-n-butyl ether, methyl t-butyl ether, diphenyl ether, THF, 1,2-dimetboxyethane, or any combination thereof. In one aspect, the ethereal solvent can be diethyl ether, THF, or any combination thereof, and in another aspect, the ethereal solvent can comprise diethyl ether.
In another aspect of the invention, the rapid combination of a fluorenyl compound Li(H) with a fulvene compound in is typically carried out over a time period of less than 5 minutes, less man 4 minutes, less than 3 minutes, less than 1 minutes, less than 1 minute, less than 45 seconds, less than 30 seconds, or less than 15 seconds. In mis aspect, the rapid combination of Li(Bl) with HI can also be carried out over a time period of less than 1 minute, less than 50 seconds, less titan 40 seconds, less than 30 seconds, less than 20 seconds, or leas man 10 seconds. This combination time for the fluorenyl and the fulvene compounds is different than the total contact time between these compounds, prior to proceeding to the subsequent step in the process. The combination time describes the elapsed time over which Hie addition of the fulvene to the ethereal solution of me fluorenyl, or alternatively, the addition of the ethereal solution of fluorene compound to the fulvene, is initiated and completed.
While not intending to be bound by theory, one explanation of why the rapid combination of the fulvene and the ethereal solution of the lithium fluorenyl results in high yields is as follows. It is possible that an intermediate, mono-Uthiated species, namely Li(l), forms relatively quickly upon reacting Li(DE) with m. Again, while not intending to be bound by theory, it is also possible mat Li(H) could engage in a slower deprotonation reaction of Li(I) to form LizOO, along with fluorene. In mis situation, slow combination of in to Li(II) might be expected to allow rapidly-formed ti(I) to be present together in solution with unreacted Li(H) for a sufficient period of time for the Li(H) to deprotonate Li(I) to form l*i(I). This process would, in turn, be expected to lower the yield of Li(I) and its product I that would form upon quenching this reaction mixture with a proton source. In contrast, and again while not intending to be bound by theory, the rapid combination of IH and Li(II) might be expected to form Li(I) quioldy and deplete the Li(II) before it could engage in the slower reaction with Li(I) to the extent necessary to reduce the yield of I.
Still another aspect of this invention is the combination of the ethereal solution of Li(U) and HI, which is typically carried out using from a 1:1 molar ratio to a 1:1,5 molar ratio of Li(II):in. This preparative method works with an excess of either reagent, but also works well using a 1:1 molar ratio of these reagents. In the event there is an excess of one reagent over the other, the limiting reagent in mis reaction can be present in at least 50% the mole fraction of the non-limiting reagent, at least 75% the mole fraction of the non-limiting reagent, or at least 90% the mole fraction of the non-limiting reagent. Also in the aspect, in the combination of the ethereal solution of Li(II) and m, typically in is present in slight excess over Li(II).
In yet another aspect of the present invention, the concentration of the Li(Il) compound in the first mixture, prior to rapidly combining mis ethereal Li(II) solution with the fulvene compound HI, can be from 0.2 M (molar) to 2.0 M. This Li(II) concentration in the first mixture, prior to rapidly combining this mixture with in, can also be from 0.5 M to \ .8 M, from 0.7 M to 1.5 M, or from 1,0 M.to 1.2 M. Further, this Li(H) concentration in the first mixture, prior to rapidly combining thia mixture with m, can also be 0.5 M, 0.6 M, 0.7 M, 0.8 M, 0.9 M, 1.0 M, 1.1 M, 1.2 M, 1.3 M, 1.4 M, 1.5 M, 1.6 M, 1.7 M, 1.8 M, 1.9 M, or 2.0 M.
Because the method of making I provides mis compound in at least 85% yield, the preparative method, in the event mere is an excess of one reagent over the other in the combination of the ethereal solution of Li(H) and m, at least 85% of the limiting reagent reacts, at least 90% of the limiting reagent reacts, or at least 95% of the limiting reagent reacts. Thus, in this aspect, the duration of the contact time between Li(H) and EQ is typically that time necessary such that the limiting reagent has substantially reacted, that is the time necessary for at least 85% of the limiting reagent to be consumed, at least 90% of the limiting reagent be consumed, or at least 95% of the limiting reagent be consumed.
In another aspect, this invention encompasses contacting the second mixture, formed from rapidly combining the ethereal solution of Li(II) with HI, with a proton source to form a third mixture comprising I. The proton source for this step carl be any proton source that protonates the Li(II) with in contact product to provide I. In this aspect, the proton source can comprise water, an aqueous acid, an aqueous ammonium salt, or any combination thereof. The proton source can also be water, an aqueous acid, an aqueous ammonium salt, or any combination thereof. While not required, when the proton source comprises or is an
aqueous acid, the aqueous acid can be relatively dilute, for example, from 0.5 M to 4 M. Typically, the proton source comprises an aqueous ammonium salt
This method for making compound I can further comprise isolating compound I. Compound I can typically be isolated in at least 85% yield. For example, the method of this invention can further comprise removing the volatile components from the third mixture to provide a residue comprising I, optionally contacting or triturating the residue with a solvent in which I is substantially insoluble andTH is.solublc, and isolating I. Thus, by describing the trituration solvent as a solvent in which I is substantially insoluble and m is soluble, it is intended that this solvent would provide for the isolation of I in the yields disclosed herein.
Examples of solvents that are useful in this trituration include, but are not limited to, an alcohol, including, but not limited to an alcohol having up to 8 carbon atoms. Examples of trituration solvents that can be used in mis .aspect of the invention include, but are not limited to, methanol, ethanol, i-propanol, n-propanol, n-butanol, sec-butanol, t-butanol, 1-hexanol, 2-hexanol, 3-hexanol, any mixture thereof, or any combination thereof. Typically, the trituration solvent can comprise methanol, ethanol, any mixture thereof, or any combination thereof. In this aspect, removing the volatile components of the third mixture can be achieved by any method known to one of ordinary skill in the art, including, but not limited to, evaporation, evaporation under reduced pressure, evaporation under the flow of a gas such as nitrogen, and the like. Similarly, isolating I following the optional trituration of the residue obtained upon removing the volatile components from the third mixture can be carried out by any method known to one of ordinary skill in the art, including, but not limited to, decanting the trituration solvent from the solid I, filtering off solid I, and the like.
Yet another aspect of this invention is the temperature at which the various contact steps are initiated, and the temperature at which the various contact steps are allowed to proceed or run for their duration. These two temperatures can be different or they can be the same. In one aspect, the initiation temperature for a contact step is different than the run temperature. Thus, contacting II and an alkyl lithium reagent in an ethereal solvent to form a first mixture, can typically be initiated from room temperature to -100°C, from 0°C to -100°C, from -30°C to -95°C, or from -50°e to -9D°C, or from -70°C to -85 °C. In another aspect, contacting II and an alkyl lithium reagent in an ethereal solvent to form a first mixture, can typically be initiated at room temperature, at 0°C, at -20*C, at -40°C, or at -78°C. Once H and the alkyl lithium reagent have been contacted in an ethereal solvent to
form a first mixture at the contact temperature, the first mixture can be maintained at one or more run temperatures for the duration of the contact step. In this aspect, for example, the run temperature can be from room temperature to -lOO'G, from OaC to -100°C, from -30°C to -95°C, or from -50°C to -90°C, or from -70°C to -85°C. In another aspect, this run temperature can be at room temperature, at 0"C, at -20°C, at -40°C, or at -78°C.
In another aspect, rapidly combining the ethereal solution of Li(II) with a fulvene compound HI to form a second mixture, can typically be performed from room temperature to -100aC, from 0°C to -1QO°C, from -30SC to -95°C, or from -50°C to -90°C, or from -70°C to -85°C. The temperature at which this rapid combination occurs is the temperature at which the contact between Li(II) and in is initiated. Once initiated, the run temperature can be, for example, from room temperature to -100°Cj from 0°C to -100°C, from -30°C to -95°C, or from -50°C to -90°C, or from -70°C to -85°C. In another aspect, this ran temperature can be at-78°C.
Compounds of the formula I that can be prepared using this invention include, but are
(Figure Remove)


not limited to, a compound of flic formula

, which can be prepared




as disclosed herein by reacting the compound

(TI) with a

\ ff
compound having the formula *—" , wherein R3 can be typically H, t-butyl, i-
propyl, n-propyl, ethyl* or methyl, and wherein n is an integer from 1 to 6. In another aspect, R3 can be typically t-butyl, i-nropyl, n-propyl, ethyl, or methyl, and wherein n can be an integer from 1 to 6.
Another compound of the formula I that can be prepared using this invention includes, but is not limited to, (5-cyclopentadienyl)[5-(2,7-di-tert-butylfiuorenyl)]hex-l-ene.
Thus, this invention provides a method for making (5-cyclopcntadienyl)[5-(2,7-di-tert-butylfluorenyl)]hex-l-ene, comprising:
a) contacting 2,7-di-tert-butylfluorene and an alkyl lithium reagent in an ethereal
solvent to form a first mixture, wherein the 2,7-di-tert-butylfluorene is substantially
deprotonated to form Li(2,7-di-tert-butylfiuorenyl);
b) rapidly combiniag the ethereal solution of Li(2,7-di-tert-butylfluorenyl) with 6-
(Figure Remove)

methyl-6-(3-butenyl)fulvene, *—» , to form a second mixture, wherein the
limiting reagent has substantially reacted; and
c) contacting the second mixture with a proton source to form a third mixture comprising (5-cyclopentadienyl)[5-{2,7-di-tert-butylfluorenyl)]hcx-l-cne in at least 85% yield.
In another aspect of this invention, the method disclosed herein can further comprise isolating the (5-cyclopentadienyl)[5-(2,7Ta4-tert-butylfluorenyl)]hex-l-ene. This method can also further comprise removing the volatile .components from the mird mixture to provide a residue comprising (5-cyclopentadienyl)[5-(2,7-di-tert-butylfluprenyl)]hex-l-ene. In this aspect, mis invention can also further comprise removing the volatile components from the third mixture to provide a residue comprising (5-cyclopentadienyl)[5-(2,7-di-tert-butylfluorcnyl)]hex-l-ene, optionally triturating the residue with a solvent in which (5-cyclopentadienyl)[5-{2,7-di-tert-butylfluorenyl)]hex-l-ene is substantially insoluble and 6-memyl-6-(3-butenyl)rulvene is soluble, and isolating the (5-cyclopentadicnyl)[5-(2,7-di-tert-butylfluorenyl)]hex-l-ene. Also in this aspect, this invention can further comprise isolating (5-cyelopentadienyl)t5-(2>7-di-tert-butyliluorenyl)]hex-l-ene in at least 85% yield.
Scheme 1 illustrates one aspect of this invention for the synthesis of the parent ligand, in which typical conditions are exemplified. As shown in Scheme I, 1.1 to 1.2 molar equivalents of n-butyl lithium were added to 2;7-di-tert-butylfluarene (V) m diethyl ether at -78°G, men this mixture was allowed to warm to room temperature and was stirred for at least 12 hours. The reaction mixture was then cooled to -78°C and 1.4 molar equivalents 6-butenyl-6-methylrulvene (VI) were added to the reaction mixture as quickly as possible, typically in less man 1 minute. While not intending to be bound by theory, it is believed mat
this rapid addition helped to boost the yield of the parent ligand. This reaction mixture was then typically allowed to warm to room temperature, and was stirred for at least 12 hours.
Scheme 1

(Figure Remove)
The Li(Y) and VI reaction was then quenched using methods known in the an and the product was isolated as a crude white solid comprising VIL Further purification of the resulting parent ligand VII was then achieved through the use of a methanol wash, which afforded the parent ligand of a sufficiently high purity to he used in the subsequent metalloccne synthesis. Using an alcohol wash, typically a methanol wash, rather than recrystallization, also helped boost the yield of the product.
If shorter reaction times were used, if pentane/EteO solvent mixtures of varying ratios were used for purification through crystallization of the crude ligand, or both, a reduction in the overall yield of the desired product -was observed. The Examples provided herein disclose full details of the synthetic methods employed, and illustrate comparative preparations that provided the desired compound in lower yield.
yJasa-Metallocene Synthesis. In another aspect, the present invention provides a method for making a compound of the formula.
(Figure Remove)

(IV), comprising:

(Figure Remove)

a) contacting a compound of the formula ^ (TJQ and a first
alkyl lithium reagent in a first ethereal solvent to form a first mixture, wherein compound
11 is substantially deprotonated to form Li(II);
b) rapidly combining the first mixture with a fulvene compound of the formula
(Figure Remove)
v—!f (UI) to form a second mixture, wherein the limiting reagent has substantially reacted;
c) contacting the second mixture with a proton source to form a third mixture
(Figure Remove)
R3
R1-
R2
comprising tt—^ (I), including isomers thereof, in at least 85% yield;
d) removing the volatile components from the third mixture to provide a residue
comprising I;
e) optionally triturating the residue with a solvent in which I is substantially
insoluble and HI is soluble to provide I, followed by isolation of I;
f) contacting the I with from 2 to 2.5 molar equivalents of a second alkyl lithium
reagent in a second ethereal solvent to form a fourth mixture, wherein the I is
substantially deprotonated to form Liz(I);
g) contacting the fourth mixture with M'JQ and an optional hydrocarbon cosolvent
(Figure Remove)
R3
R1-
Rz
to form a fifth mixture comprising ^^ (IV);
h) removing the volatile components from the fifth mixture to provide IV in at least 80% yield;
i) optionally washing the IV in a non-polar solvent;
j) optionally extracting the IV with a polar solvent followed by removing the volatiles from the polar solvent solution to, provide IV; and
k) optionally crystallizing the IV from an aromatic solvent; wherein:
R1 and R2 are independently selected from an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms, or hydrogen; and
R3, in each instance, is independently selected from an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms, or hydrogen;
M'isZrorHf;and
XisCl,Br, or I. (Figure Remove)


La this aspect, compound I can have the formula ' , compound II

can have the formula ^ , and compound DDt can have the formula

; wherein:
R3 is H, t-butyl, i-prppyl, n-propyl, ethyl, or methyl, n is an integer from 1 to 6; M1 is Zr; and X is Cl.
Some of the preparative steps of this method encompass the preparation of the parent ligand that is used to prepare the ansa-metalloeene in subsequent steps. Therefore, the various aspects disclosed herein for the preparation of the parent ligand are also applicable to that portion of the arts-a-metallocene synthetic method that involved preparing the parent ligand, including but not limited to steps a, b, c, d and optional step e. Such aspects include, but are not limited to: contact time; solvents; combination time; initiation temperature; run temperature; alkyl lithium reagents; definitions of R1, R2, R3, substantial deprotonation.

substantial reaction, and limiting reagent; molar ratios; proton sources; yields; trituration solvents; method of isolation of I, and the like.
Also in this aspect, the first and the second alkyl lithium reagents are selected independently, that is independent of the selection of each other. Thus, the first alkyl lithium reagent that can be used is any alkyl lithium reagent mat allows I to be prepared in at least 85% yield, including, but not limited to MeLi, n-BuLi, t-BuLi, n-hexylLi, L4CH2SiMe3, LiCHjPh, LiCHjCMej, or any combination thereof. The second alkyl lithium reagent that can be used is any alkyl lithium reagent that allows I to be deprotonated to form Lii(I) in at least 85% yield, at least 90% yield, at least 95% yield, or at least 98% yield. Thus, the second alkyl lithium reagent that can be used is any alkyl lithium reagent that allows IV to be prepared in at least 85% yield, including, but not limited to MeLi, n-BuLi, t-BuLi, n-hexylLi, LiCHjSiMej, LiCHjPh, LiCH2CMe3, or any .combination thereof. While the first and the second alkyl lithium reagents are selected independently, n-BuLi is typically selected for the first alkyl lithium and the second alkyl lithium.
While not intending to be bound by theory, the contact time between I and the at least 2 molar equivalents of a second alkyl lithium reagent is thought to affect the ansa-metallocene produced by this method. Accordingly, in this aspect, the contact time between I and the second alkyl lithium reagent can be at least 0,5 hour, at leant 1 hour, at least 2 hours, at least 3 hours, at least 4 hours, at least 5 hours, at least 6 hours, at least 7 hours, at least 8 hours, at least 9 hours, at least 10 hours, at least 11 hours, at least 12 hours, at least 13 hours, at least 14 hours, at least 15 hours, at least 16 hours, at least 17 hours, or at least 18 hours. Also in this aspect, the contact time between I and the second alkyl lithium reagent can be from 1 hour to 48 hours, from 3 hours to 30 hours, from 6 hours to 24 hours, from 8 hours to 20 hours, or from 10 hours to 18 hours.
Similarly, the first and the second ethereal solvents are also selected independently, that is independent of the selection of each other. The first and second ethereal solvents used in this method, can be independently selected from a range of ethereal solvents, including, but not limited to, dimethyl ether, diethyl ether, diisopropyl ether, di-n-propyl ether, di-n-butyl ether, methyl t-butyl ether, diphenyl ether, THF, 1,2-dimethoxyethane, or any combination thereof. In one aspect, the first and second ethereal solvents can be independently selected from diethyl ether, THF, or any combination thereof, and in another aspect, the first and second ethereal solvents can independently comprise diethyl ether.

In another aspect of this invention, the optional hydrocarbon cosolvent can be a range of aliphatic and aromatic cosolvents, but can be typically an aliphatic eosolvent. In one aspect, the optional hydrocarbon cosolvent can be butane, pentane, cyclopentane, hexane, heptane, cyctohexane, methyl cyclopentane, octane, or any combination thereof. In this aspect, pentane can be a typical optional cosolvent.
The volatile components of die fifth mixture, like that of me third mixture, can be removed by any method known to one of ordinary skill in the art, including, but not limited to, evaporation, evaporation under reduced pressure, evaporation under the flow of a gas such as nitrogen, and the like.
Similarly, in still another aspect of rats invention, the optional non-polar solvent that can be used to wash IV can be a range of non-polar solvents, including aliphatic or aromatic non-polar solvents. In this aspect, for example, the optional non-polar solvent can be butane, pentane, cyclopentane, hexane, heptane, cyclohexane, methyl cyclopentane, octane, or any combination thereof. Pentane can be a typical non-polar solvent used in this optional washing step of mis invention.
While not intending to be bound by theory, it is believed mat the hydrocarbon, for example, pentane, wash functions primarily to improve the purity of the IV without sacrificing its yield, because the starting materials and by-products are soluble in solvents such as pentane, and IV is relatively insoluble (see Figures 1 and 2). If polar solvents such as ethereal solvents are used to wash die crude IV obtained after removing the reaction volatiles from die reaction mixture, die purity of IV is improved, but the yield of IV suffers because of its greater solubility in ethers as compared to pentane. Also while not intending to be bound by theory, it is believed that removing the reaction volatiles from the reaction mixture crude IV, rattier than decanting die reaction solvent, helps improve the overall yield of IV, because of the solubility of IV in ethereal solvents.
In yet another aspect of this invention, the polar solvent that can be used to extract IV can be a range of polar solvents, including aliphatic or aromatic polar solvents. In this aspect, for example, the optional polar solvent can be CHCIj, CHzQz, 1,2-dichlorethane, or any combination thereof. In mis aspect, dichloromethane (CHjCh) is a typical polar solvent.
In a further aspect, die optional aromatic solvent that can be used to crystallize IV, can be a range of aromatic solvents, including, bat not limited to, benzene, toluene, xylene,

mesitylene, ethyl benzene, anisole, aniline, pyridine, 4-pbenylpyridine, or any combination thereof, including any isoraer thereof.
Scheme 2 illustrates one aspect of this invention for the synthesis of the ansa-rnetalloceae VIII using the parent ligand VII .prepared according to this invention, in which typical conditions are exemplified. As shown in Scheme 2, the process for preparing Vin in high yield encompassed using an appropriate length of time for deprotonation of VII, as well as the use of proper extraction procedures. For example, increasing the time for the deprotonation reaction of the parent ligand Vn using n-butyl lithium from 6 hours to at least 12 hours prior to addition to zirconium tetrachloride, increased the yield of metallocene VUI. Removing the volatile components of the Lij(VH) and ZrCU reaction mixture, rather than simply concentrating the solution and crystallizing out the metallocene Vffl, afforded higher yields of VTQ Further, using pentane to wash the resulting residue or solid obtained from removing the reaction volatiles improved the purity of the desired product. Using a non-polar solvent such as pentane, rather than diethyl ether, to wash the resulting residue or solid obtained from removing the reaction volatiles improved the overall yield of the desired product.
Scheme 2


2n-BuLi,0°C,
Cl
2) Zr€l4, 0°C,
Et2O/pentane
3) strip to dryness,
pentane wash,
CHjClj extraction

vm

(Figure Remove)
While metallocene VIII was somewhat soluble in non-polar solvents such as pentane, it was more soluble in polar solvents such as CHjCb, which served as a suitable extraction solvent. Figure I provides the *H NMR spectrum in CDCla solvent of the pentane extract, that is, the pentane wash liquid, used in the workup of the (5-cyclopentadienyl)[5-(2,7-di-tcrt-butylfluorenyl)Jhex-l-ene zirconium dichloride synthesis. While some metallocene product can be observed in this spectrum, additional byproducts that were removed by this wash are also observed. Figure 2 provides the 'H'NMR spectrum in CDCb solvent of the CHaCfe extract, that followed after a pentane washing step, from the solid product obtained during

workup of the (5-cyclopentadienyl)[5-(2,7-di-tert-burylfluonmyl)]hex-l-ene zirconium dichloride synthesis. A high concentration of pore metallocene VHI is observed in this spectrum, illustrating the suitability of this method for preparing pure VDI, the suitability of pentane as a wash solvent to remove unwanted byproducts and unreacted starting material, and the suitability of CHjCk as an extraction and crystallization solvent The Examples provided herein disclose full details of the synthetic methods employed to provide the desired metallocene in high yield, and illustrate comparative preparations that provided the desired compound in lower yield.
In an additional aspect of this invention, the entire sequence of parent ligand synthesis and metallocene preparation could be performed in a "one-pot" process, and a representative procedure for this one-pot synthesis is provided in the Examples. Although the one-pot method allowed anwz-metallocene VHI to be prepared in sufficiently high purity for further use, including, but not limited to, its use in olefin polymerization catalysis, me overall yield of VUJ was observed to be comparatively tower than that overall yield of VIII when the synthesis was conducted by first isolating the parent ligand VII.
Yet another aspect of this invention is the preparation of a compound of the formula
(Figure Remove)
, wherein R1, R2, R3, M1, and X are defined herein, using any process to prepare metallocene compounds that is know to one of ordinary skill, using the parent ligand prepared according to this invention. Thus, numerous processes to prepare metallocene compounds have been reported, examples of which include U.S. Patent Numbers 4,939,217, 5,191,132, 5,210,352, 5,347,026, 5,399,636, 5,401,817, 5,420,320, 5,436,305, 5,451,649, 5,496,781, 5,498,581, 5,541,272, 5,554,795, 5,563,284, 5,565,592, 5,571,880, 5,594,078, 5,631,203, 5,631,335, 5,654,454, 5,668,230, 5,705,579, and 6,509,427 which describe such methods, each of which is incorporated by reference herein, in its entirety. Other processes to prepare metallocene compounds that can be employed in mis invention have been reported in references such as: Kfippl, A. Alt, H. G. J. Mol. Catal A. 2001,165, 23; Kajigaeshi, S.; Kadowaki, T.; Nishida, A.; Fujisaki, S. The Chemical Society of Japan, 1986, 59, 97; Alt, H. G.; Jung, M.; Kehr, G. J. Organomet. Chem. 1998, 562,153-181; and Alt, H.
G-; lung, M. J. Organomet. Chem, 1998, 568, 87-112; each of which is incorporated by reference herein, in its entirety. Further, additional processes to prepare metallocene compounds that can be employed in this invention have been reported in: Journal of Organometallic Chemistry. 1996, 522, 39-54, which is incorporated by reference herein, in its entirety. The following treatises also describe such methods: Wailes, P. C.; Coutts, R. S. P.; Weigold, H. in Organometallic Chemistry of Titanium, Zirconium, and Hafnium, Academic; New York, 1974.; Cardin, D, J.; Lappert, M. F.; and Ragton, C. L.; Chemistry of Organo-Zirconium and -Hafnium Compounds; Halstead Press; New York, 1986; each of which is incorporated by reference herein, in its entirety.
For any particular compound disclosed herein, any general structure presented also encompasses all conformation*! isomers, regioisomers, arid stereotsomers that may arise from a particular set of substituents. The general structure also encompasses all enantioraers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context requires.
EXAMPLES
The present invention is farther illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort may be had to various other aspects, features, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit of the present invention or die scope of the appended claims.
The following examples and comparative examples encompass new synthetic methods for both the anja-metallocene parent ligands and for metaliocenes prepared therefrom. Specifically, these examples demonstrate that product yields of an ansa-raetallocene parent ligand can be improved by proper conditions for combining the ligand precursors. This invention is specifically illustrated using the two reactants, 2,7-di-fert-butylfluorenyl lithium and 6-butenyl-6-metbylfulvene, and through the choice of the deprotonation method for the ligand precursor, selection of the reaction solvent, and selection of the reaction work-up conditions.
In addition, the following examples and comparative examples demonstrate that high product yields of an o/wa-metallocene can be obtained by selection of the deprotonation
conditions for the parent ligand, selection of the reaction solvent, and reaction work-up conditions, also as follows. Specifically, this aspect of die invention is illustrated in the preparation of the metallocenc (S-cyclopentedienyOtS-ClJ-di-tert-butylfluorenyOlhex-l-ene zirconium dichloride.
GENERAL DETAILS
The solvents used in the following Examples were dried and distilled under nitrogen using standard methods. The Nuclear Magnetic Resonance (NMR) spectra reported herein were obtained on a Varian Mercury Plus 300 NMR spectrometer operating at 300 MHz for 1H NMR (CDC13 solvent, referenced against die peak of residual CHC13 at 7.24 ppm).
The 6-butenyl-6-methylfulvehe was prepared according to the method used by Stone and Little (J. Org. Chem. 1984,49,1849).
EXAMPLE 1
Preparation of l~(methyl)-1^3-but0nyl)-l-tydapentadienyl)-l-(2,7-di-tert-
bvtylfluQrenyljmethane by the reaction af2,7-di-tert-butylfluorenyl lithium and 6-butenyl-6-methylfulvene
Preparation 1. A one-liter flask was charged with 2,7-di-ten-butylfluorene (50 g, 179.6 mrhol) and a stir bar, capped with a rubber septum, and placed under a nitrogen atmosphere. Oiethyl ether (about 200 mL) was added via a cannula, and the resulting mixture was cooled to -78°C in a dry-ice bath. This mixture was stored at this temperature as n-butyllithium (19.0 mL of 10 M in hexanes, 190 mmol) was added slowly via syringe. After the addition of n-butylUmium was complete, the reddish solution was slowly wanned to room temperature and stirred overnight (at least 12 hours). After this time, the reaction mixture was cooled to -78°C, and 6-butenyl-6-methylfulvene (40 mL) was added quickly (in less than 1 minute) at this temperature with stirring. On completion of the fulvone addition the mixture was removed from the dry ice bath and wanned to room temperature, and a GC aliquot taken after ca. 15 minutes following removal of the dry-ice bath. The GC analysis indicated 85.3% yield of the product had formed.
Stirring was continued for 7 hours, after which time the reaction mixture was quenched with a saturated NHUCl/IfcO solution (300 mL). The organic layer was extracted with diethyl ether, washed twice with HjO (500 raL), dried over anhydrous Na2SO the solid and the mixture stirred overnight to afford the product as a finely divided white solid. After filtration, washing with MeOH, and drying overnight, 76 g (89%) of the desired parent ligand l-(me%l)4^34>utenyl)-l Preparation 2. Following the same procedure as described in Preparation 1 above in a second preparation afforded 70 g (90%) of the desired compound.
EXAMPLE 2
Comparative preparation of 1-(methyl)-!-(3-butenyl)-l-(tychpentadienyl)-l-(2,7-di-tert-butylfluorenyl) methane — Method AI
Preparation 1. A one-liter flask was charged with 2,7-di-tert-butylfluorene (50 g, 179.6 mrnol) and a stir bar, capped with.a rubber septum, and placed under a nitrogen atmosphere. Diethyl ether (about 300 mL) was added via a carmula, and the resulting mixture was cooled to -78°C in a dry-ice bath. This mixture was stirred at this temperature as n-butyllithium (21.5 mL of 10 M in hexanes, 215 mmol) was added slowly via syringe. After the addition of n-butyllithium was complete, the reddish solution was slowly wanned to room temperature and stirred overnight (at least 12 hours), to provide an ether solution of 2,7-di-/ert-burylfluorenyl lithium.
Another one-liter flask fitted with an addition funnel was charged with 6-butenyl-6-methylfulvene (37 g, 253 mmol) and a stir bar, and cooled to 0°C under a nitrogen atmosphere. The ether solution of 2,7-di-jtert-butylfluorenyl lithium prepared as above was added in a dropwiae fashion to the fulvene at 0*C via the addition funnel over the course of approximately one hour. The resulting dark-colored reaction mixture was wanned to room temperature and stirred overnight (at least 12 hours) under a nitrogen atmosphere. The reaction mixture was then quenched with the slow addition of a saturated NHaCl/HjO solution (300 mL), the organic layer extracted wife etiier, washed twice with HjO (500 mL), dried over anhydrous Na2SO4, filtered, and the filtrate evaporated to dryness, The crude product obtained by this method was then dissolved in pentane and maintained at 0°C in a freezer, thereby affording the product as a white solid that was washed with cold pentane, dried under vacuum, and isolated and used without further purification (60.4 g, 79%). Further product could be isolated in smaller quantities through concentrating the mother liquors and combined washings and placing them back in freezer.
Preparation 2. Another comparative preparation of the parent ligand 1-(methyl)-!-(3-butenyl)-l-(cyclopentadienyl)-I-(2,7-di-tert-butylfluorenyl)-methane according to the same reaction, work-up, and crystallization conditions as disclosed in Method Al, afforded 34.7 g (45% yield) of the desired product as a white solid.
EXAMPLES
Comparative preparation of l~(methyl)-l-(3-butenyl)-^l-(cydopentadienyl)-l-(2,7-di-tert-butylflitorenyl)-methane - Method A2
An ether solution of 2,7-di-tert-butylfluorenyl lithium was prepared and added in a dropwise fashion over the course of approximately one hour to the neat 6-butenyl-6-methylfulvene (at 0°C) in the same manner as disclosed in Method Al. The resulting reaction mixture was then wanned to room temperature and stirred for 2 days under a nitrogen atmosphere. After this time, an additional 5 mL of 6-butenyl-6-tnethylfulvene and an additional 30 mL of the n-butyllithium solution were added to the reaction mixture at room temperature and this mixture was stirred overnight at room temperature.
The reaction mixture was then quenched with the slow addition of a saturated NHjCl/HiO solution (300 mL), the organic layer extracted with ether, washed twice with H2O (500 mL), dried over anhydrous NajSO^ filtered, and the filtrate evaporated to dryness. The crude product obtained by this method was dissolved in and crystallized from a pentane:EtiO solution (4:1 mixture by volume) at 0°C, thereby affording SO.l g (66%) of the product as a white solid.
EXAMPLE 4
Comparative preparation of 1-(methyl)-l-(S-butenyl)-l-(cydopentadienyl)-l-(2,7-di-tert-butylfluorenyl) methane - Method A3
A THF solution of 2,7-di-terf-butylfluorenyl lithium was prepared and added in a dropwise fashion over the course of Approximately one hour to the 6-butenyl-6-methylftiivene solution (at 0°C) in the same manner as disclosed in Method Al. The resulting dark-colored reaction mixture was then wanned to room temperature and stirred overnight (at least 12 hours) under a nitrogen atmosphere. This THF reaction mixture was then quenched with the slow addition of a saturated Nl^Cl/IfcO solution (30D mL), the organic layer extracted with diethyl ether, washed twice with Hj>O (500 mL), dried over anhydrous NajSO4, filtered, and the filtrate evaporated to dryness. The crude product
obtained by this method was then dissolved in and crystallized from pentane at 0°C, thereby affording a 76% yield of the product as a white solid.
EXAMPLES
Preparation of (5-cydapentadimyl)[5-(2,7^i-tert-butyyiuorenyl)Jhex-l-ene zirconium dichloride
The following preparations demonstrate that greater and more reproducible product yields of metallocene were improved under specific conditions, which included selecting a length of time for the deprotonation reaction of the parent Ugand with butyllithiutn, and removal of the reaction solvent (diethyl elher) prior to extraction of the product.
Preparation 1. A one-liter flask was charged with the parent ligand 1-(methyl)-1-(3-butenyl)-Hcyclopcntadienyl)-l-(2,7-di-tert-butylfluoTenyl)-mettiane (46.3 g, 109.0 mrnol) and a stir bar, capped with a rubber septum, and placed under a nitrogen atmosphere. Diethyl ether (about 500 mL) was added to the flask and the mixture stirred and cooled to 0°C in an ice bath. While stirring was continued, n-butyllithium (23 mL of 10 M hi hexanes, 230 mmol) was added slowly to the mixture via syringe. After the addition of n-butyllithium was complete, die reaction mixture was warmed to room temperature and stirred overnight (at least 12 hours) under a nitrogen atmosphere.
In a nitrogen-filled drybox, a one-liter flask was charged with ZrCU (25.4 g, 109.0 mmol) and a stir bar, capped with a rubber septum, brought out of the drybox, charged with 300 mL of pentane under nitrogen, and cooled in an ice hath to 0°C. The diethyl ether mixture of dilithiated parent ligand was added to (he ZrCU slurry via cannula over the course of thirty-minutes at 0*C, and the resulting orange slurry was warmed to room temperature and stirred overnight (at least 12 hours). The solvent was then removed under vacuum affording an orange solid. Pentane (about 200 mL) was added to the solid, the slurry centrifuged and the supernatant decanted. The remaining solid was men extracted with methylene chloride, centrifuged, and the supernatant decanted and evaporated to dryness to afford 55.0 g (86%) of the desired metallocene (5-eyclopentadienyl)[5-(2,7-di-tert-butylfluorenyl)]hex-l -ene zirconium dichloride that was used without further purification.
Preparation 2. Duplication of the procedure used in Preparation 1 on two separate instances allowed isolation of the metallocene (5-cvc1opentadienyl)[5-(2,7-di-tert-butylflttorenyl)]hex-l-ene zirconium dichloride in yields of 80% and 84% respectively.
EXAMPLE 6
Comparative Preparation of (5-cyclopeniadiefyl)[5-(2,7-di'tert-butylfluorenyl)]hex-l~ ene zirconium dichloride - Method Bl
A one-liter flask was charged with flic parent ligand 1 -(methyl)-!-(3-butenyl)-!-(cyclopentadienyl)-l-(2,7i In a nitrogen-filled drybox, a one-liter flask was charged with ZrCU (12.7 g, 54.5 mmol) and a stir bar, capped with a rubber septum, brought out of the drybox, charged with 500 mL of pentane under nitrogen, cooled in an ice bath to 0°C, and fitted with an addition funnel. The diethyl ether mixture of dilithiated parent ligand was added to the ZrCU slurry via the addition funnel over the course of one hour at 0°C, and the resulting orange slurry was warmed to room temperature and stirred overnight (at least 12 hours). The resulting slurry was then centrifuged and the supernatant decanted and evacuated to dryness to afford 16 g of solid. The residual solid was then extracted with anhydrous and oxygen-free methylene chloride, centnfuged, and the supernatant decanted and evaporated to dryness to afford 13.6 g (43 %) of the desired metallocene (5-cycldpentadienyl)[5-(2,7-di-tert-butylfluorenyl)]hex-l-ene zirconium dichloride mat was used without further purification.
EXAMPLE?
Comparative One-Pot Preparation of (5-cyclopentadienyl)[5-(2,7-di-tert-butylftuorenyl)]hex-l-ene zirconium dichloride - Method C
An aliquot of n-butyl lithium (9.3 mL, 2.5 M in hexanes, 23.3 mmol) was added dropwise to 2,7-di-t-butylfluorene (5.85 g, 21 mmol) dissolved in Et2O (40 mL) at 0°C. The resulting mixture was wanned to room temperature and stirred for an additional 3 hours, giving rise to a dark red solution (lithium 2,7-di-t-butylfiuorenyl, abbreviated t-BuFluLi). This solution was added dropwise to a solution of 6-butenyl-6-methylmlvene (3.4 g, 23.1 mmol) in 10 mL of £t2O at 0°C over a period of 30 minutes. The resulting mixture was stirred at room temperature overnight (at least 12 hours), giving rise to a dark red solution.
An additional amount of fulvene (0.9 g, 6.2 mmol) was then added to this solution at room temperature and the resulting mixture was stirred for an additional 4 hours to provide a dark red solution. A portion of n-butyl lithium (93 mL, 2.5 M in hexanes, 23.3 mmol} was added dropwise to this solution at 0°C, after which the resulting mixture was wanned to room temperature and stirred for an additional 3 hours to provide a dark red solution of the dilithiated parent iigand (dilithiated l-(methyl)-H3^utenyl)-I-(cyclefentadienyl)-l-(2,7-di-tert-butylfiuorenyl)-methane). This solution was then added dropwise to ZrCU (5.38 g, 23.1 mmol) suspended in EtjQ (50 mL) at Q'C over a period of 20 minutes. The resulting mixture was warmed to room temperature and stirred overnight, giving rise to an orange-brown slurry, The slurry was centriruged and the supernatant decanted and evaporated to dryness to give 10 g of a dark brown solid. The remaining solid was extracted with CHjCk (ca. 180 mL) and the extract evaporated to dryness to give the metallocene (5-cyclopentadienyl}[5-(2,7-di-tert-butylfluarenyI)]-hex-l-ene zirconium dichloride as an orange red solid (3.5 g, 28.5% yield) that could be used without further purification.
Although any methods, devices, and materials similar to or equivalent to those described herein can be used in the practice or testing of the invention, the typical methods, devices and materials are herein described.
All publications and patents mentioned herein are incorporated herein by reference in their entireties, for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention. The publications discussed above and throughout the text are provided solely for their disclosure prior to die tiling date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.
To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.



We Claim:
1. A method of making a compound of the formula
(Figure Remove)

(I), and isomers thereof, comprising:


a) contacting a compound of the formula (H) and an
alkyl lithium reagent in an ethereal solvent to form a first mixture, wherein compound II
is substantially deprotonated to form Li(D);
b) rapidly combining the first mixture with a fulvene compound of the formula
RV ^R2(Figure Remove)

(III) to form a second mixture, wherein either Li(II) or compound HI is optionally a limiting reagent, and wherein the limiting reagent, if present, has substantially reacted; and
c) contacting the second mixture with a proton source to form a third mixture
(Figure Remove)Rs
R1-
R2
comprising ^—f (I), and isomers thereof;
wherein R1 and R2 independently are hydrogen or an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms; and
wherein each R3 independently is hydrogen or an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms.
2. The method of Claim 1, wherein: (Figure Remove)
formula, and compound in has the formula v—'J
wherein:
R3 is H, t-butyl, i-propyl, n-propyl, ethyl, or methyl, and
n is an integer from 1 to 6.
3. The method of Claim 1, further comprising isolating I.
4. The method of Claim 1, further comprising removing the volatile components
from the third mixture to provide a residue comprising I.
5 The method of Claim 1, further comprising removing the volatile components from the third mixture to provide a residue comprising I, optionally triturating the residue with a solvent in which I is substantially insoluble and ffl is soluble, and isolating I.
6. The method of Claim 5, wherein I is isolated hi at least 85% yield
7. The method of Claim 5, wherein the- trituration solvent comprises an alcohol.
8. The method of Claim 5, wherein the trituration solvent comprises methanol,
ethanol, any mixture thereof, or any combination thereof.
9. The method of Claim 1, wherein the ethereal solvent comprises dimethyl ether,
diethyl ether, diisopropyl ether, di-n-propyl ether, di-n-butyl ether, methyl t-butyl ether,
diphenyl ether, THF, 1,2-dimethoxyethane, or any combination thereof.
10. The method of Claim 1, wherein the ethereal solvent comprises diethyl ether,
THF, or any combination thereof.
11. The method of Claim 1, wherein the ethereal solvent comprises diethyl ether.
12. The method of Claim 1, wherein the concentration of the Li(II) reagent in the first
mixture prior to rapidly combining the first mixture with ffl, is from 0,5 M to 1.8 M.
13. The method of Claim 1, wherein the concentration of the Li(II) reagent in the first
mixture prior to rapidly combining the first mixture with m, is from 0.7 M to 1.5 M.
14. The method of Claim 1, wherein the alkyl lithium reagent comprises MeLi, n-
BuU, t-BuLi, n-hexylLi, iJCHzSiMej, UGHjPh, LiCHjCMej, or any combination
thereof.
15. The method of Claim 1, wherein n and the alkyl lithium reagent react to form
Li(II) in at least 95% yield.
16. The method of Claim 1, wherein the first mixture is combined with HI over a time
period of less than 3 minutes.
17. The method of Claim I, wherein the first mixture is combined with III over a time
period of less than 1 minute.
18. The method of Claim 1, wherein the first mixture is combined with III over a time
period of less than 30 seconds.
19. The method of Claim 1, wherein the proton source comprises water, an aqueous
acid, an aqueous ammonium salt, or any combination thereof.
20. The method of Claim 1, wherein step a is initiated from 0°C to -100°C.
21. The method of Claim 1, wherein step a is initiated at -78°C.
22. The method of Claim 1, wherein step a is conducted from room temperature to -
78°C.
23. The method of Claim 1, wherein step b. is initiated from OeC to -100°C.
24. The method of Claim 1, wherein step b is initiated at -78°C.
25. The method of Claim 1, wherein step b is conducted from room temperature to -
78°C.
26. The method of Claim 1, wherein the limiting reagent of step b is present in at least
50% the mole fraction of the non-limiting reagent.
27. The method of Claim 1, wherein at least 90% of the limiting reagent of step b has
reacted.
28. The method of Claim 1, wherein at least 95% of the limiting reagent of step b has
reacted.
29. The method of Claim 1, wherein compound I is formed in at least 85% yield.
30. The method of Claim 1, wherein compound I is formed in at least 90% yield.
31. The method of Claim 1, wherein compound I is formed in at least 95% yield.
32. A method for making (5-cyclopentadienyl)[5-(2,7-di-tert-butyh1uorenyl)]hex-l-
cne, comprising:
a) contacting 2,7-di-tert-butylfluorene and an alkyl lithium reagent in an ethereal solvent to form a first mixture, wherein the 2,7-di-tert-butylfluorene is substantially deprotonated to form Li(2,7-di-tert-butylfluorenyl);
b) rapidly combining the ethereal solution of Li(2,7-di-tert-butylfluorenyl) with 6-(Figure Remove)

methyl-6-(3-butenyI)fulvene, *—" , to form a second mixture, wherein the
limiting reagent has substantially reacted; and
c) contacting the second mixture with a proton source to form a third mixture comprising (5-cyclopentadienyl)[5-(2,7-di-tert-butylfluorenyl)]hex-l-ene in at least 85% yield.
33. The method of Claim 32, further comprising isolating the (5-eyclopentadienyl)[5-
(2,7-di-tert-butylfluorenyl)]hex-1-ene.
34. The method of Claim 32, further comprising removing the volatile components
from the third mixture to provide a residue comprising (5-cyclopcntadienyl)[5-(2,7-di-
tert-buryifluorenyl)]hex-1 -ene.
35. The method of Claim 32, further comprising removing the volatile components
from the third mixture to provide a residue comprising (5-cyclopentadienyl)[5-(2,7-di-
tert-butylfluorenyl))hex-l-cne, optionally triturating the residue with a solvent in which
(5-cyclopentadienyl)[5-(2,7-di-tert-butylfluorenyl)]hex-l-ene is substantially insoluble
jnd e-methyl^Cg-butenyljfulvene is soluble, and isolating the (5rcyQtopentadienyl)[5-
(2,7-di-tert-butylfluorenyl)]hex-1-ene.
36. The method of Claim 32, wherein (5-cyclopentadienyl)[5-(2,7-di-tert-
butylfluorenyl)]hex-l-ene is isolated in at least 85% yield.

37. The method of Claim 32, wherein the trituration solvent is an alcohol.
38. The method of Claims 5 or 32, wherein the trituration solvent comprises methanol,
ethanol, i-propanol, n-propanol, n-butanol, sec-butanol, t-butanol, 1-hexanol, 2-hexanol,
3-hexanol, any mixture thereof, or any combination thereof.
39. The method of Claim 32, wherein the ethereal solvent comprises dimethyl ether,
diethyl ether, diisopropyl ether, di-n-propyl ether, di-n-butyl ether, methyl t-butyi ether,
diphenyl ether, THF, 1,2-dimethoxyelhaneJ, or any combination thereof.
40. The method of Claim 32, wherein the alkyl lithium reagent comprises MeLi, n-
BuLi, t-BuLi, n-hexylLi, LiCHjSiMej, UCH2Ph, LiCHjCMej, or any combination
thereof.
40. The method of Claim 32, wherein the ethereal solution of Li(2,7-di-tert-butylfluorenyl) is combined with 6-methyl-6-(3-butenyi)fulvene over a time period of less than 3 minutes.
42. The method of Claim 32, wherein the ethereal solution of Li(2,7-di-tert-
butylfluorenyl) is combined with 6-methyl-6-(3-butenyl)rulvene over a time period of less
than 1 minute.
43. The method of Claim 32, wherein the proton source comprises water, an aqueous
acid, an aqueous ammonium salt, or any combination thereof.
44. A method for making a compound of the formula

(IV), comprising:
(Figure Remove)
a) contacting a compound of the formula ^^ (EL) and a first
alkyl lithium reagent in a first ethereal solvent to form a first mixture, wherein compound II is substantially deprotonated to form Li(II);
b) rapidly combining the first mixture with a fulvene compound of the formula(Figure Remove)

«•—9 (TO) to form a second mixture, wherein the limiting reagent has substantially reacted;
c) contacting the second mixture with a proton source to form a third mixture

(Figure Remove)R1-
R2
comprising y—/ (I), including isomers thereof, in at least 85% yield;
d) removing the volatile components from the third mixture to provide a residue
comprising 1;
e) optionally triturating the residue with a solvent in which I is substantially
insoluble and HI is soluble to provide I, followed by isplation of 1;
f) contacting the I with from 2 to 2.5 molar equivalents of a second alkyl lithium
reagent in a second ethereal solvent to form a fourth mixture, wherein the I is
substantially deprotonated to form Li2(I);
g) contacting the fourth mixture with M'^Q and an optional hydrocarbon cosolvent
(Figure Remove)R1-
R*
to form a fifth mixture comprising ^^ (IV);
b) removing the volatile components from the fifth mixture to provide TV in at least 80% yield;
i) optionally washing the IV in a non-polar solvent;
j) optionally extracting the IV with a polar solvent followed by removing the volatiles from the polar solvent solution to provide IV; and
k) optionally crystallizing the IV from an aromatic solvent; wherein:
R1 and R2 are independently selected from an aliphatic or substituted aliphatic group having from 1 hi 20 carbon atoms, or hydrogen; and
R3, in each instance, is independently selected from an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms, or hydrogen; M'isZrorHf;and X is Cl, Br, or I.
45. The method of Claim 44, wherein:
(Figure Remove)

compound I has the formula

, compound H has the
(Figure Remove)


_ , and compound m has the formula
wherein:
R3 is H, t-butyl, i-propyl, n-propyl, ethyl, or methyl, n is an integer from 1 to 6; Ml is Zr; and
X is Cl.

46. The method of Claim 44, wherein the optional trituration solvent is an alcohol.
47. The method of Claim 44, wherein the first and second alkyl lithium reagents
independently comprise MeLi, n-BuLi, t-BuLi, n-hexylLi, LiCHjSiMej, LiCHjPh,
LiCH2CMe3, or any combination thereof.
48. The method of Claim 44, wherein the first and second ethereal solvents independently comprise dimethyl ether, dietbyl ether, diisopropyl ether, di-n-propyl ether, di-n-buryl ether, methyl t-butyl ether, diphenyl ether, THF, 1,2-dimethoxyethane, or any combination thereof.
49. The method of Claim 44, wherein the fourth mixture comprises Li3(I) in at least
90% yield.
50. The method of Claim 44, wherein the hydrocarbon cosolvent comprises butane,
pentane, cyclopentane, hexane, heptane, cyclohexane, methyl cyclopentane, octane, or
any combination thereof.
51. The method of Claim 44, wherein the non-polar solvent comprises butane,
pentane, cyclopentane, hexane, heptane, cyclohexane, methyl cyclopentane, octane, or
any combination thereof.
52. The method of Claim 44, wherein the polar solvent comprises CHC13, CH2C12,1,2-
dichlorethane, or any combination thereof
53. The method of Claim 44, wherein the aromatic solvent comprises benzene,
toluene, xylene, mesitylene, ethyl benzene, anisole, aniline, or any combination thereof.
54. The method of Claim 44, wherein D and the first alkyl lithium reagent react to
form Li(II) in at least 95% yield.
55. The method of Claim 44, wherein the first mixture is combined with TO. over a
time period of less than 3 minutes.
56. The method of Claim 44, wherein the first mixture is combined with m over a
time period of less than 1 minute.
57. The method of Claim 44, wherein the first mixture is combined with HI over a
time period of less than 30 seconds.
58. A method for isolating (5-cyclopentadienyl)[5-(2,7-di-tert*butylfluorenyl)]hex-l-
ene zirconium dichloride, comprising:
a) contacting 2,7-di-tert-butylfluorene and a first alkyl lithium reagent in a first
ethereal solvent to form a first mixture, wherein the 2,7-di-tert-butylfluorene is
substantially deprotonated to form U(2,7-di-tert-butylfluorenyl);
b) rapidly combining the first ethereal solution of Ij(2,7-di-tert-butylfluorenyl) (Figure Remove)

with 6-methyl-6-(3-butenyl)fulvene, *—!( t to form a second mixture, wherein
the limiting reagent has substantially reacted;
e) contacting the second mixture with a proton source to form a third mixture comprising (5-cyclopentadienyl)[5-(2,7-di-tert-butylfluorenyl)]hex-l-ene in at least 85% yield;
d) removing the volatile components from the third mixture to provide a residue
comprising (S-cyelopentadienylJtS^^-di-tert-burylfluorenyOlhex-l -one;
e) optionally triturating the residue with a solvent in which (5-
cyclopentadienyl)[5-(2,7-di-tert-butyLfluorcnyl)]hex-l-ene is substantially insoluble and
6-methyI-6-(3-butenyl)fulvene is soluble, and isolating the (5-cyclopentadienyl)[5-(2,7-
di-tert-butylfluorenyl)]hex-1 -one;
f) contacting the (5-cyclopentadienyl)[5-(2>7-di-tert-butylfluorenyI)3hex-l-ene
with from 2 to 2.5 molar equivalents of a second alkyl lithium reagent in a second
ethereal solvent to form a fourth mixture, wherein the (5-cyclopentadienyl)[5-(2,7-di-tert-
butylfluorenyl)]hex-l-ene is substantially deprotonated to form Li2(5-
cyclopentadienyl)[5-(2,7-di-tert-butylfiuorenyi)]hex-l-ene;
g) contacting the fourth mixture with 2rCU and an optional hydrocarbon cosolvent
to form a fifth mixture comprising (5-cyclopentadienyl)[5-(2,7-di-tert-
butylfluorenyl)]hex-l-ene zirconium dichloride;
h) removing the volatile components from the fifth mixture to provide (5-eycIopentadienyl)[5-(2,7-di-tert-butylfluorenyl)]hex-l-ene zirconium dichloride in at least 80% yield;
i) optionally washing the (5-cyelopentadienyl)[5-(2,7-di-tert-butylfluorenyl)]hex-1-ene zirconium dichloride in a non-polar solvent;
j) optionally extracting the (5-cyclopentadienyl)[5-{2,7-di-tert-butylfluorenyl)]hex-l-ene zirconium dichloride with a polar solvent followed by
removing the volatiles from the polar solvent solution to provide (5-cvclopentadienvl)[5-(2,7-di-tert-butvlfluorenyl)]hex-l-ene zirconium dichloride; and
k) optionally crystallizing the (5-cyclopentadienyl)[5-(2,7-di-tert-butylfluorenyl)]hex-l-ene zirconium diehloride from an aromatic solvent.
59. The method of Claim 58, wherein the first ethereal solution of Li(2,7-di-tert-
butylfluorenyl) is combined with 6-methyl-6-(3-butenyl)fulvene over a time period of less
than 3 minutes.
60. The method of Claim 58, wherein the ethereal solution of Li(2,7-di-tert-
butylfluorenyl) is combined with 6^memyl-6^butenyl)fulvene over a time period of less
than 1 minute.
61. The method of Claims 32 or 58, wherein the ethereal solution of Li(2,7-di-tert-
butyifluorenyl) is combined with 6-memyl-6-(3-butenyl)fulvene over a time period of less
than 30 seconds.
62. A method of making a compound of the formula
(Figure Remove)
(I), and isomers thereof, comprising: a) providing a source of a fluorenyl anion having the formula
(Figure Remove)
b) rapidly combining the source of the fluorenyl anion with a fulvene compound R1 R2
of the formula «—" (IH) to form a mixture, wherein either me source of the fluorenyl anion or compound HI is optionally a limiting reagent, and wherein the limiting reagent, if present, has substantially reacted; and

c) contacting the mixture with a proton source to form
(Figure Remove)
R
R2
n r
(I), and isomers thereof;
wherein R1 and R2 independently are hydrogen or an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms; and
wherein each R3 independently is hydrogen or an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms.
63. The method of Claim 62, wherein the source of a fluorenyl anion is a compound
comprising limium, sodium, potassium, magnesium, calcium, or a combination thereof.
64. A method of making a compound pf the formula
65. (Figure Remove)
R3 .
RZ I
(T), and isomers thereof, comprising:
a) providing a salt of a fluorenyl anion having the formula
(Figure Remove)



b) rapidly combining the source of the fluorenyl anion with a fulvene compound(Figure Remove)

of the formula ^—'J (in) to form a mature, wherein either the source of the fluorenyl anion or compound HI is optionally a limiting reagent, and wherein the limiting reagent, if present, has substantially reacted; and

c) contacting the mixture with a proton source to form
(Figure Remove)
R1-
R2
ii /
(I), and isomers thereof;
wherein R1 and R2 independently are hydrogen or an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms; and
wherein each R3 independently is hydrogen or an aliphatic or substituted aliphatic group having from 1 to 20 carbon atoms.
65. The method of Claim 64, wherein the salt of a fluorenyl aniou is a compound comprising lithium, sodium, potassium, magnesium, calcium, or a combination thereof.

Documents:

7786-delnp-2006-abstract.pdf

7786-delnp-2006-assignment.pdf

7786-delnp-2006-Claims-(17-10-2012).pdf

7786-delnp-2006-claims.pdf

7786-delnp-2006-Correspondence Others-(03-07-2012).pdf

7786-delnp-2006-Correspondence-others (26-05-2008).pdf

7786-delnp-2006-Correspondence-Others-(17-10-2012).pdf

7786-delnp-2006-correspondence-others.pdf

7786-delnp-2006-Description (Complete)-(17-10-2012).pdf

7786-delnp-2006-description (complete).pdf

7786-delnp-2006-drawings.pdf

7786-delnp-2006-form-1.pdf

7786-delnp-2006-form-13.pdf

7786-delnp-2006-Form-18 (26-05-2008).pdf

7786-delnp-2006-form-2.pdf

7786-delnp-2006-form-26.pdf

7786-delnp-2006-Form-3-(03-07-2012).pdf

7786-DELNP-2006-Form-3.pdf

7786-delnp-2006-form-5.pdf

7786-DELNP-2006-PCT-101.pdf

7786-delnp-2006-pct-220.pdf

7786-delnp-2006-pct-237.pdf

7786-delnp-2006-pct-304.pdf

7786-delnp-2006-pct-search report.pdf


Patent Number 258728
Indian Patent Application Number 7786/DELNP/2006
PG Journal Number 06/2014
Publication Date 07-Feb-2014
Grant Date 03-Feb-2014
Date of Filing 20-Dec-2006
Name of Patentee CHEVRON PHILLIPS CHEMICAL COMPANY, LP
Applicant Address 10001 SIX PINES DRIVE, THE WOODLANNDS, TEXAS 77380, U.S.A.
Inventors:
# Inventor's Name Inventor's Address
1 THORN, MATTHEW G. 4858 BRIDGE LANE, APT 5 MASON, OH 45040, U.S.A.
2 MARTIN, JOEL L. 636 SE KENWOOD DRIVE, BAERLESVILLE, OK 74006, U.S.A.
3 YANG, QING 2917 MONTROSE DRIVE, BARTLESVILLE, OK 74006, U.S.A.
4 MASINO, ALBERT, P. 2628 S. OSWEGO AVENUE, TULSA, OK 74137, U.S.A.
PCT International Classification Number C07F 17/00
PCT International Application Number PCT/US2005/022533
PCT International Filing date 2005-06-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/876,948 2004-06-25 U.S.A.