SYNTHESIS OF N-SILYLATED CYCLOPENTAPHENANTHRENE COMPOUNDS

Abstract: A method for the synthesis of certain N-silylated cyclopentaphenanthrene (Group IV metal) complexes is disclosed.

Description: -1- SYNTHESIS OF N-SILYLATED CYCLOPENTAPHENANTHRENE COMPOUNDS This application is a continuation of United States application Serial No. 09/018,534 filed 04 February 1998. This application is related to Gately application Serial No. 09/016,641 filed 30 January 1998 and entitled "Silylated and N-Silylated Compound Synthesis". FIELD OF INVENTION This invention relates to the synthesis of N-silylated cyclopentaphenanthrene (Group IV metal) complexes. BACKGROUND OF THE INVENTION It is known to react lithium salts of N-silylated metallocene ligands with a Group IV metal halide wherein a metallocene compound useful as an olefin polymerization catalyst may be produced. SUMM.ARY OF THE INVENTION This invention provides methodology useful to produce ligands from which N-silylated cyclopentaphenanthrene (Group IV metal) complexes useful as olefin polymerization catalysts may be synthesized. An example of the methodology of the invention may include : (1) conversion of phenanthrene to 2,3 dehydro-1- oxycyclopentaphenanthrene (Compound A) : -2- 0 COMPOUND A (2) conversion of 2,3 dehydro-1-oxycyclopenta- phenanthrene to IH cyclopentaphenanthrene (Compound B) : COMPOUND B (3) conversion of IH cyclopentaphenanthrene to produce Compound C : COMPOUND C -3- in which R is an alkyl group, preferably a t-butyl group; and (4) conversion of Compound C to Compound D: ( CH 3 ) 2 -Si NR COMPOUND D in which R is an alkyl group, preferably a t-butyl group, and M is a Group IV metal, e.g., zirconium, titanium or hafnium. Preferably this conversion is accomplished by reacting Compound C with a Group IV metal secondary amide complex and an excess of (CH 3 ) 3 SiCl or its equivalent. DETAILED DESCRIPTION OF THE INVENTION The steps or subcombination of steps which may comprise each aspect of the invention are sequentially described. -4- Production of Compound A: Methods are known for the synthesis of Compound A. See, e.g., Schneider, et al., Organometallica (1997) 16:3414-3420, specifically page 3416, Scheme 1 and Scheme 2 and the product 12 produced in Scheme 2. Production of 1 H Cyclopentaphenanthrene Compound B: Scheme 2 of Schneider, et al., also describes the conversion of Compound A to Compound B. This invention provides a different method for that conversion which includes (i) reacting Compound A at a temperature of -50°C to 120°C, preferably, but not necessarily, in a proportion of about 2 to 3 mols of hydrazide per mol of Compound A with tosyl hydrazide in a medium comprising an aromatic hydrocarbon solvent, preferably toluene, and 1 to 20 mol percent, preferably 10 mol percent of a one to five carbon atom fatty acid, preferable acetic acid wherein the corresponding tosyl hydrazone is produced. Benzene, xylene, or mesitylene may be used instead of toluene. See Equation 1 and Example I. Functionally equivalent hydrazide other than tosyl hydrazide, e.g., phenylhydrazide are known to those skilled in the art and may be used in this method. -5- CH CH * 3-©< ( ) >- ■ SOJNHNHJ CH 3 C0 2 2 23322 1 18866 400 58g 50g 0.250 mol 0.2688 mol EQUATION 1 EXAMPLE I As indicated by Equation 1, 0.250 mol of Compound A and 0.686 mol of tosylhydrazide are combined in a mixture containing 1 1. toluene and 13 ml acetic acid. This reaction mixture is heated and a small portion, i.e., less than 50%, of the reaction solvent is distilled over five hours . The residual reaction mixture is then cooled to room temperature and filtered. The filter cake was washed with 100 ml toluene followed by 100 ml hexanes and vacuum dried the product. Yield = 90g (90% X H NMR) . The hydrazone product of Equation 1 is converted to X H cyclopentaphenanthrene (Compound B) as indicated by Equation 2 : -6- = NNHTS (TS = tosyl ; / / o/ Q/ \0) + 2 ' 2 HN ( isopropyl^+2.2 BuLi Toluene ,. / y a^/ ^ F 400 101 1 . 6M 216 40 . Og 22 . 2g 137 . 5ml COMPOUND B Equation 2 EXAMPLE II 22.2 g of diisopropylamine was diluted with 200 ml THF under N 2 and cooled in an ice/water bath . 1.6M BuLi was added over 20 minutes. The mixture was stirred one-half hour after completion of the BuLi addition. The lithium diisopropyla ide (LDA) solution thus formed was added over five minutes to a suspension of 40 grams of the tosylhydrazone in 500 ml toluene. This mixture was stirred overnight. 10 ml H 2 0 was then added and the resulting mixture was then stirred thirty minutes. 120g celite was added. This mixture was stirred for ten minutes and then filtered. The filtrate was concentrated under vacuum to give 18.6g of a light brown solid (86%) dehydrocyclopenta- phenanthrene (Compound B) . Other aromatic hydrocarbon solvents, e.g., benzene, xylene, mesitylene may be used instead of toluene. Any -7- secondary amine having one to five carbon atom alkyl groups may be used instead of diisopropyl amine. Appropriate proportions of reactants are 1 mol of hydrazone per 2 to 3 mols of secondary amine and 2 to 3 mols of butyl lithium. One series of steps useful to convert 1 H cyclopentaphenanthrene (Compound B) to Compound C is illustrated by Equations 3, 3(a) and Example 3: Toluene Compound B + BuLi ! Reaction mixture containing Li Et 2 0 Salt of Compound B FW 816 1.6M 32. lg 92.9ml 0.1486mol 0.1486 EQUATION 3 Reaction mixture Reflux reaction containing Li Salt mixture containing of Compound B + CH 3 S0 3 Si (Me) NHR -> Compound C Neat Reflux Stir 223 345 33.2g 0.1486 EQUATION 3(a) in which R is as defined, preferably t-butyl. EXAMPLE III As illustrated by Example III, 1 H cyclopentaphenanthrene (Compound B) was combined with and mostly dissolved in 700 ml toluene; 16 ml diethyl ether was added -8- followed by N-butyl lithium; precipitation of the lithium salt of Compound B occurred within 15 minutes . The reaction mixture was stirred overnight at room temperature. In this reaction, ethyl ether, Et 2 0 may be replaced by any ether having the formula R^R 2 wherein R 1 and R 2 are identical or different one to five carbon atom alkyl groups . The ether is preferably used in an amount corresponding to 2 moles of ether per 1 to 2 moles of Compound B. As illustrated by Equation 3(a), CH 3 S0 3 Si (CH 3 ) 2 NH (t- butyl) was added neat to the Equation 3 reaction mixture. This mixture was refluxed overnight, cooled to room temperature and filtered. Toluene was removed under vacuum. Yield - 50 g brown solid which was >90% pure Compound C ( X H NMR) . Equimole proportions of Compound B and CH 3 S0 3 Si (Me) 2 NHR, wherein R is preferably t-butyl, are appropriate. As illustrated by Example III, the conversion of Compound B to Compound C may be accomplished in a single pot. Alternatively, the lithium salt may be separated and then converted to Compound C. One series of steps useful to convert Compound C to Compound D is illustrated by Equation 4 : -9- CH ( CH3 ) 2 S i NH (t-butyl) Metallocene Ligand Ti(NMe 2 ) 4 Heptanes Reflux (CH 3 ) 2 si N R F 345 224 108.6 (R = alkyl, 256g 166g 483ml preferably 0.742ml 0.742ml 4.4ml t-butyl) EQUATION 4 EXAMPLE IV 256g of Compound C was added to 5 liters of heptanes in which it mostly dissolved at 50°C. The solution was filtered to remove a small amount of insoluble material. The filtrate was heated to reflux under nitrogen. 158 ml of Ti(NMe 2 ) 4 was then added by syringe. The reaction mixture was refluxed for three hours, then cooled to room temperature. Chlorotrimethylsilane (400g) was added and refluxed four hours, cooled to room temperature and filtered. Filter cake was washed with 2 x 500 ml toluene, followed by 500 ml hexanes and dried under vacuum. 257g (75% yield) of Yellow solid was obtained.

Claims: -10- CLAIMS : 1. A method which comprises : (i) reacting 2 ,3-dihydro-cyclopentaphenanthrene (Compound A) with tosylhydrazide wherein a first reaction mixture containing the tosylhydrazone compound: NNHTS (TS = Tosyl) is produced; (ii) reacting said tosylhydrazone compound produced in step (i) with a secondary amine and a butyl lithium in a mixed toluene and tetrahydrofuran medium wherein a second reaction mixture containing 1-H cyclopentaphenanthrene (Compound B) is produced. 2. The claim 1 method further comprising step (iii) converting said 1-H cyclopentaphenanthrene Compound B produced in step (ii) to Compound C having the formula: -11- (CH 3 ) 2 SiNHR wherein R is an alkyl group. 3. The claim 2 method wherein R is t-butyl . 4. A method which comprises : (i) reacting 2,3 dehydro-1-oxycyclopentaphenanthrene with tosylhydrazide having the formula o Me o NHNH O -12- in a non-interfering solvent wherein a tosylhydrazone compound having the formula: 0 N NH S O CH-. 0 is produced; (ii) reacting the tosylhydrazone produced in step (i) with LiN(R) 2 wherein R is a one to six carbon atom alkyl group, in a non-interfering medium to produce 1 H cyclopentaphenanthrene having the formula: -13- (iii) reacting the X H cyclopentaphenanthrene product of step (ii) with butyl lithium and CH 3 S0 3 Si (CH 3 ) 2 (t-butyl) wherein an N-silylated compound having the formula: CH-, wherein R is an alkyl group; (iv) reacting said n-silylated compound produced in step (iii) with Ti(NME 2 ) 4 and (Me) 3 SiCl wherein a titanocene compound having the formula: -14- CH, is produced. 5. The claim 4 method wherein R is t-butyl . 6. A method which comprises (i) reacting cyclopentaphenanthrene with butyl lithium in a mixed toluene and ether solvent wherein a first reaction mixture containing lithiated cyclopentaphenanthrene in said solvent mixture is produced; and (ii) reacting CH 3 S0 3 Si (CH 3 ) 2 NHR with said lithiated cyclopentaphenanthrene contained in step (i) first reaction mixture wherein a second reaction mixture is produced and wherein said second reaction mixture contains the compound -15- ;CH 3 ) 2 SiNHR wherein R is an alkyl group. 7. The claim 6 method in which R is t-butyl . 8. The claim 7 method further comprising separating said compound (CH 3 ) 2 SiNHR from said second reaction mixture.

Inventors: ASKHAM FREDRIC, ASKHAM, FREDRIC
Applicants: ASKHAM FREDRIC, BOULDER SCIENT CO, ASKHAM, FREDRIC, BOULDER SCIENTIFIC COMPANY
Application year: 1999
Main classification: C07F17
IPC codes: B01J31, C07C1, C07C13, C07C15, C07C29, C07C35, C07C303, C07C309, C07F7, C07F17, C08F4, C08F10