NL1003016C2 - Substituted pentadiene compound. - Google Patents

Description

- ι - SUBSTITUTED PENTADIENE COMPOUND 5

The invention relates to a substituted pentadiene compound (pd compound) according to the formula R2 H R2 R2 R2 R2 R2 \ or 15 Λ Λ AA ”h R2 R1 R1 R2 R2 R1 R1 R2 in which 20 R1-2 are substituents and at least one R2 substituent has the form RDR'a, where D is a heteroatom of group 15 or 16 of the Periodic Table of Elements, R 'is a substituent on the heteroatom, R is a linking group,

In the following, pentadiene will be abbreviated as 'pd'. The same abbreviation will be used for a pentadienyl group if it is clear from the context whether pentadiene itself or its anion is meant.

Unsubstituted pentadiene compounds are known. These compounds are described, inter alia, by Ernst (Chem. Rev. 1988, 88, 1255-1291). These compounds can be used as a ligand in a metallocene catalyst.

Surprisingly, it has now been found that excellent catalysts can be obtained when the pd compounds of the invention are used as a ligand in a transition metal complex.

100301e - 2 -

The pd compounds of the invention have been found to be able to stabilize highly reactive intermediates such as organometallic hydrides, borohydrides, alkyls and cations. For example, if a mono-pd-substituted metal complex is obtained from metals in a valence state lower than the highest possible, in which the pd-containing ligand is mono-anionic, then it exerts a strong stabilizing effect without the active sites of the complex, so that the complexes have excellent catalytic activity. The skilled person cannot infer from the said publication that the compounds according to the invention have such a specific action. Corresponding complexes in which the pd compound is not substituted in the manner indicated appear to be unstable or, if otherwise stabilized, to have poorer catalytic properties than the substituted pd compound complexes of the invention.

Organometallic complexes of the pd compounds of the invention have further been found to be suitable as stable and volatile precursors for use in Metal Chemical Vapor Deposition.

A substituted pd compound is understood to be a pentadiene substituted by at least one group of the form RDR 'n.

The R1 groups can be the same as the R2 groups defined below. The Rx groups can also be linked to form a ring. Preferably, the R1 groups are linked to a dimethylmethylene group.

The R2 groups can each be separately hydrogen or a hydrocarbon radical of 1-20 carbon atoms (such as alkyl, aryl, arylalkyl, etc.). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl.

1003016 - 3 -

Two adjacent R2 hydrocarbon radicals may also be linked together in a ring system. This can even occur twice, so that when two Rx groups also form a ring, the pd-5 compound eventually contains 3 rings. Such a group can also contain one or more R2 groups as substituents. R2 may also be a substituent containing, in addition to or instead of carbon and / or hydrogen, one or more hetero atoms from group 14-16 of the Periodic Table of the Elements. For example, a substituent can be an N, O, and or Si-containing group. One R2 may also be a cyclopentadienyl or pd group.

The R group forms the connection between the pd 15 and the DR'n group. The length of the shortest connection between the pd and D, hereinafter referred to as the main chain of R, is critical in that it determines the accessibility of the metal in the metal complex by the DR group to thereby achieve the desired intramolecular coordination. to get. Too short a length of the R group (or bridge) can prevent the donor from coordinating properly due to ring tension. The R group may be a hydrocarbon group of 1-20 carbon atoms (such as alkylidene, arylidene, arylalkylidene, etc.). Examples of such groups are methylene, ethylene, propylene, butylene, phenylene, with or without a substituted side chain. Preferably, the R group has the following structure: 30 (-ER42-) p with p = 1-4 and E is an element of group 14 of the Periodic Table. The R4 groups are as defined for R2.

Thus, the main chain of the R group may contain, in addition to carbon, silicon or germanium. Examples of such R groups are: 10 o 3 ö 1 ξ - 4 -:. .

dialkylsilylene, dialkylgermylene, tetraalkyldisilylene or tetraalkylsilaethylene (-SiR '2CR'2-). The alkyl groups in such a group preferably have 1-4 C atoms and are more preferably a methyl or ethyl group.

The DR '' group consists of a heteroatom D selected from group 15 or 16 of the Periodic Table of Elements and one or more substituent (s) R 'linked to D'. The number of R 'groups (n) is linked to the nature of the heteroatom D, and in that n = 2 if D is from group 15 and n = 1 if D is from group 16. Preferably, the heteroatom D is selected from the group of nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S); More preferably, the heteroatom is nitrogen (N). The R 'groups can be the same or different and can be selected from the same groups as defined for R2 with the exception of hydrogen. Preferably the R 'group is an alkyl, more preferably an n-20 alkyl group with 1-20 C atoms. More preferably, the R 'group is an n-alkyl of 1-10 C atoms. Another possibility is that two R 'groups in the DR' 'group are linked together to form an annular structure (so that the DR' 'group may be a pyrrolidinyl group).

25 The DR group can coordinate bonding with a metal.

The DR 'group can also be an aryl group, for example phenyl, tolyl, xylyl, mesitylyl, cumyl, tetramethylphenyl, pentamethylphenyl. When using a pd substituted with an aryl group as described above as a ligand on a metal, the coordination of this group on the metal can vary from ή1 to ή6.

The substituted pd compounds of the invention, when used as the sole pd-35 containing ligand in a metal complex in which the metal is not in the highest valence state, are found to yield compounds of good stability and good catalytic activity. The invention therefore also relates to this application.

Incidentally, these compounds can also be used with good results as ligands to metals, which are in their highest valency state. In this case, too, active catalysts are obtained, which in many cases give better results in a specific application than the known pd-containing ligands.

Metals that are catalytically active when one of their ligands is a compound of the invention are the metals of groups 4-12 of the Periodic Table and rare earths. Particularly suitable for the polymerization of olefins are such metal complexes in which the metal is selected from the group consisting of Ti, Zr, Hf, V, Co, Pd and Cr.

The invention therefore also relates to the metal complexes thus composed and their use as catalysts, in particular for the polymerization of olefins, both of linear and branched and cyclic olefins and whether or not conjugated dienes and mixtures thereof. Here, complexes of metals from groups 4 and 5 of the Periodic Table of Elements are preferably used as a catalyst component for polymerizing olefins; complexes of metals from groups 6 and 7 of the Periodic Table of the Elements also for metathesis and ring-opening metathesis polymerisations and complexes of metals from groups 8-10 of the Periodic Table of the Elements for olefin copolymerizations with polar comonomers, hydrogenations and carbonylations.

The order in which the substituents are attached to the pd is free.

A group of the form RDR'n can be applied to one of the free places on the pd-compound already substituted at one or more positions, for example according to the following synthetic route.

1 0 0 3 0 1 S

- 6 -

In a first step of this route, a substituted pd compound is deprotonated by reaction with a base, sodium or potassium.

Depending on the acid strength of the proton to be abstracted, organolithium compounds (RsLi) or organomagnesium compounds (RsMgX) can be used as base, wherein R5 is an alkyl, aryl or aralkyl group and X is a halide, for example n-butyl lithium or Ι -ΙΟ propyl magnesium chloride. Potassium hydride, sodium hydride, tertiary amines (such as pyridine and triethylamine), inorganic bases, for example NaOH and KOH, and alcoholates of Li, K and Na can also be used as the base. Mixtures of the above compounds are also applicable. Strong bases are preferably used, such as the mixture of n-butyl lithium and potassium t-butoxide.

This reaction can be performed in a polar dispersant such as an ether.

Examples of suitable ethers are tetrahydrofuran (THF) or dibutyl ether. Non-polar solvents, such as, for example, toluene, can also be used.

Then, during a second step of the synthesis route, the pentadienyl anion formed reacts with a compound of the formula (DR 'BRY) or (XR-Sul), wherein D, R, R's are n as defined above and Y is a halogen atom (X) or is a sulfonyl group (Sul).

As the halogen atom X, chlorine, bromine and iodine can be mentioned. Preferably, the halogen atom X is a chlorine or bromine atom.

The sulfonyl group has the form -SO 2 R 6, wherein R 5 is a hydrocarbon radical of 1-20 carbon atoms (such as alkyl, aryl, aralkyl, etc.). Examples of such hydrocarbon radicals are butane, pentane, hexane, benzene, naphthalene. R6 may also contain, in addition to or instead of carbon and / or hydrogen, one or more 1003016-7 heteroatoms from group 14-17 of the Periodic Table of the Elements, such as N, O or F.

Examples of sulfonyl groups are: phenylmethanesulfonyl, benzenesulfonyl, 1-5 butanesulfonyl, 2,5-dichlorobenzenesulfonyl, 5-dimethylamino-1-naphthalenesulfonyl, pentafluorobenzenesulfonyl, p-toluenesulfonyl, trichloromethanesulfonyl, trifluoromethyl-2,4anesulfonyl-sulfanesyl-sulfonyl 6-trimethylbenzenesulfonyl, 2-mesitylene sulfonyl, methanesulfonyl, 4-methoxybenzenesulfonyl, 1-naphthalenesulfonyl, 2-naphthalenesulfonyl, ethanesulfonyl, 4-fluorobenzenesulfonyl and 1-hexadecan sulfonyl.

Preferably the sulfonyl group is p-toluenesulfonyl or trifluoromethanesulfonyl.

When D is a nitrogen atom and Y is a sulfonyl group, the compound of the formula (DR'n-RY) is formed in situ by reaction of an amino alcohol compound (Rr2NR-OH) with successively a base (as defined above), potassium o £ sodium and a sulfonyl halide (Sul-X).

Also the second reaction step can be performed in a polar dispersant, as described for the first step.

The temperature at which the reactions are carried out is between -60 and 80 ° C. Reactions with X-R-Sul and with DR 'a-R-Y, in which Y is Br or I are usually carried out at a temperature between -20 and 20 ° C. Reactions with DR '- R-Y, where Y is Cl, are usually carried out at a higher temperature (10 to 80 ° C). The upper limit for the temperature at which the reactions are carried out is partly determined by the boiling point of the solvent.

After the reaction with a compound of the formula (X-R-Sul), a further reaction with LiDRof 1003016 - 8 - HDR 'is carried out to replace ora X with a DR' functionality. For this purpose, optionally in the same dispersing agent as mentioned above, a reaction is carried out at 20 to 80 ° C.

The synthesis of metal complexes with the above-described specific pd compounds as a ligand can take place according to the methods known per se. The use of these pd compounds does not require modifications of these known methods.

The polymerization of α-olefins, for example ethylene, propylene, butene, hexene, octene and mixtures thereof and with should be carried out in the presence of the metal complexes with the cyclopentadienyl compounds of the invention as a ligand. Particularly suitable for this are the complexes of transition metals, not in their highest valency state, in which just one of the cyclopentadienyl compounds according to the invention is present as a ligand and in which the metal is cationic during the polymerization. These polymerizations can be carried out in the known manner and the use of the metal complexes as a catalyst component does not necessitate any substantial adaptation of these processes. The known polymerizations are carried out in suspension, solution, emulsion, gas phase or as bulk polymerization. As the co-catalyst, an organometallic compound is usually used, the metal 30 being selected from Group 1, 2, 12 or 13 of the Periodic Table of the Elements. For example, mention may be made of trialkylaluminum, alkylaluminum halides, alkylaluminoxanes (such as methylaluminoxanes), tr is (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate or mixtures thereof. The polymerizations are carried out at temperatures between -50 ° C and + 350 ° C, more in particular between 25 and 250 ° C. The pressures used are between generally between atmospheric pressure and 250 MPa for bulk polymerizations, more particularly between 50 and 250 Mpa, for the other polymerization processes between 0.5 and 25 MPa. As dispersants and solvents, for example, hydrocarbons can be used as pentane, heptane and mixtures thereof. Aromatic, optionally perfluorinated hydrocarbons are also eligible. The monomer to be used in the polymerization can also be used as a dispersion or solvent.

The invention will be elucidated on the basis of the following examples without, however, being limited thereto.

15

Experimental part:

Reactions were monitored over time using gas chromatography (GC type: Hewlett Packard 5890 Series II, equipped with autosampler type HP6890 Series 20 Injector, integrator type HP3396A and HP Crosslinked Methyl Silicon Gum (25mx0.32mmxl, 05 // m) column with one of the following temperature programs: 50 ° C (5min.) rate: 7.5 ° C / min. 250 ° C (29 minutes) or 150 ° C (5min.) rate: 7.5 ° C / min. 250 ° C (29 minutes).

25 The products were characterized by GC-MS (type Fisons MD800, equipped with a guadrupole mass detector, autoinjector Fisons AS800 and CPSil8 column (30mx0.25mmxl * / m, low bleed) with one of the following temperature programs: 50 ° C (5min .) 30 rate: 7.5 ° C / min.250 ° C (29 minutes) or 150 ° C (5min.) Rate: 7.5 ° C / min.250 ° C (29 minutes)) and NMR Bruker ACP200 (1H = 200MHz .; 13C = 50 MHz) or Bruker ARX400 (xH = 400MHz.j 13C = 100MHz).

Complexes were characterized with Kratos MS80 mass spectrometer or Finnigan Mat 4610.

t0 0 3 0 1: - 10 -

Example I

Example Ia: Preparation of 6,6-dimethyl-1,3-cyclohexadiene

200 mL of dry diethyl ether was added to 50.7 g of dimedone (0.36 mol) and cooled to 0 ° C. Then, a suspension of lithium aluminum hydride (12.8 g; 0.337 mol) in dry diethyl ether was added to the resulting suspension. The ice bath was then removed and stirred at room temperature for 2 hours, after which a further slurry of 7.5 g of lithium aluminum hydride in diethyl ether was added. Then refluxed for 2 hours. After stirring at room temperature for 18 hours, the reaction mixture was gilled with successively, 20 mL of water, 20 mL of 15 NaOH (15%) and 60 mL of water. The resulting precipitate was filtered off and washed with 4 x 50 mL diethyl ether. The filtrate was dried over magnesium sulfate. The desiccant was filtered off and the filtrate evaporated on a rotary evaporator. 32.0 g of yellow liquid residue remained. This crude diol was placed in a distillation setup and 10 mL of H 2 SO 4 was added. Then stirred vigorously and heated for 2 hours to 130 2 C. The fraction that came over at 83 - 85 ° C was collected. This fraction, consisting of a clear colorless top and a gray cloudy bottom layer, was diluted with 150 mL diethyl ether and extracted successively with 100 mL Na 2 CO 3 (10%) and 2x 100 mL water. The diethyl ether layer was then dried over magnesium sulfate. After filtering off the desiccant, the filtrate was evaporated on a rotary evaporator, at 45 ° C and at atmospheric pressure. A colorless clear liquid residue was left which was distilled under vacuum at room temperature. A colorless clear liquid was collected in a cold trap.

Yield: 11.4 g of crude 6,6-dimethyl-1,3-cyclohexadiene 1003016 - 11 -1 H-NMR (CDCl3): 5.6 5.6 (m, CH, 4H); 2.05 (d, CH2, 2H); 0.90 (s, CH3, 6H) GC and GCMS: tr = 9.326; 60%; M = 108: 6,6-dimethyl-5 1,3-cyclohexadiene tr = 10,168; 12%; M = 110: 3,3-dimethyl-1-cyclohexene tr = 10,385; 19%? Ά = 110: 6,6-dimethyl-3-cyclohexene 10

Example Ib: Preparation of 3- (dimethylaminoethyl) -6,6-dimethyl-1,4-cyclohexadiene 6.9 g of potassium tertiary butoxide (62 mmol) was dissolved in 100 mL of dry diethyl ether and cooled to -15 70 ° C . Then 6.5 g of crude 6,6-dimethyl-1,3-cyclohexadiene was added. 37.0 mL BuLi in hexane, 1.6 M (59 mmol) was added to this reaction mixture. After the reaction mixture reached room temperature, it had become a yellow suspension. Then, at -70 ', 8.3 g of 2- (dimethylamino) ethyl chloride-HCl (58 mmol), which was first made HCl-free, using BuLi, added dropwise to the "anion mixture". Stirred at room temperature for 18 hours, after which the mixture was a dark beige suspension. After this, the mixture was cooled to 0 ° C, quenched with methanol and filtered over a pleated filter and washed with diethyl ether The filtrate was evaporated and petroleum ether was added to the dark brown liquid residue, stirred and filtered through a P4 glass filter. fraction passing at 59-60 ° C was collected The product was a colorless clear liquid.

Yield: 2.5 g of 3- (dimethylaminoethyl) -6,6-dimethyl-1,4-cyclohexadiene 100301a 5-12 -1 H NMR (CDCl3): δ = 5.47 (s, CH, 4H); 2.65 (t, CH, 1H); 2.30-2.10 (t, CH2, 2H) and (s, CH3, 6H); 1.50 (m, CH2, 2H); 0.95 (s, CH3, 6H).

Example Ic: Preparation 3- (dimethylaminoethyl) -6,6-dimethylcyclohexadienyl titanium dichloride 0.31 g of potassium tertiary butoxide (2.8 mmol) was dissolved in 10 mL of dry THF and then cooled to -70 ° C. Then 0.5 g (2.79 mmol) of 3- (dimethylaminoethyl) -6,6-dimethyl-1,3-cyclohexadiene was added. 1.75 mL of n-BuLi in hexane (1.6 M, 2.8 mmol) was added to this reaction mixture. After the reaction mixture reached room temperature, stirring was continued for an hour. Then, at -70 * 1.03 g of solid TiCl3 * 3THF was added and stirred at room temperature for 18 hours. The THF was removed and 10 mL of petroleum ether was added. After stirring for some time, this too was removed under reduced pressure. After good drying, 1.0 g of a green-brown solid containing 3- (dimethylaminoethyl) -6,6-dimethylcyclohexadienyltitanium dichloride remained, which was detected by direct inlet MS.

1003016

Claims (6)

1. Substituted pentadiene compound according to the formula R2 H R2 'V ^ Sr' R! R2> <^ VR2 10 or Λ / \ Λ h "H R2 R1 R1 R2 R2 R1 R1 R2 15 where, R1'2 are substituents and at least one R2 substituent has the form RDR'n, where D is a heteroatom of group Is 15 or 16 of the Periodic Table of the Elements, R 'is a substituent on the heteroatom, R is a linking group. A compound according to claim 1, characterized in that two Back groups together form a dimethylmethylene group. 3. A process for the synthesis of a dienyl compound according to any one of claims 1-2 by deprotonating a dienyl compound by reaction with a base, sodium or potassium and then reacting the anion formed with a compound of the formula (DR'n- RY), where R is a linking group, R 'is a substituent, D is an electron donating heteroatom from group 15 or 16 of the Periodic Table of Elements, 35. the number of R' groups bound to D and Y is a halogen atom (X ) or is a sulfonyl group (Sul). 10 0 3 0 H - 14 - A process for the synthesis of a dienyl compound according to any one of claims 1-2 by deprotonating a dienyl compound by reaction with a base, sodium or potassium and then reacting the anion formed with a compound of the formula (XR-Sul) wherein R is a linking group, X is a halogen atom and Sul is a sulfonyl group, after which a reaction is carried out with LiDR or HDR, wherein D is an electron donating heteroatom of group 15 or 16 of the Periodic Table of Elements, R 'is a substituent and 15. is the number of D-linked R 'groups. Use of a dienyl compound according to any one of claims 1-2 as a ligand in a metal complex. The use of a metal complex according to claim 20 for the polymerization of an olefin. 1003016 COOPERATION TREATY (PCT) REPORT ON INTERNATIONAL TYPE OF IDENTIFIKATJE OF OE NATIONAL APPLICATION Characteristic of the applicant ot van Oe jointly 8675NL Dutch application no. Indaneigsdaiim 1003016. 3 May 1996 Invited priority claim Applicant (Name) DSM NV Deun van nel request for an investigation of miematonaai type By oe bisante for Iniemaaonaai Onoerzoek (ISA) a «just request veffM research vennemaaonaal« pe Desiring nr SN 27503 NL I. CLASSIFICATION OF THE SUBJECT (with Bepessmg of various dassMcaras. Specify all cassifietete symbols) VOigene oe biatnatonea aessilxara (IPC) Int. Cl. 6: C 07 C 211/25, C 08 F 10/00, B 01 J 31/22, C 07 F 17/00 II. FIELDS OF TECHNIQUE EXAMINED _____ Minimum Documentation Examined___ Classification System Classatatrasymoolen Int. Cl. 6 C 07 C, C 07 F, C 08 F, B 01 J Undoubtedly other documents than oe mnmum documenara insofar as such documents contain the prayers examined qn III. HH NO RESEARCH FOR CERTAIN CONCLUSIONS (comments on supplement sheet) IV. '_; LACK OF UNIT OF INVENTION (Notes to Supplementary Ladder) I sorm PCT / lSA / 20llaiC6 1994 n