NL1003009C2 - Synthesis of a substituted cp compound. - Google Patents

Description

- 1 -

SYNTHESIS OF ONE

5 SUBSTITUTED CP CONNECTION

The invention relates to a process for substituting a cyclopentadiene with at least one group of the form -RDR by deprotonating already substituted Cp-compound with at least another group by reacting with a base, sodium or potassium and then leaving the cyclopentadienyl anion formed react with a sulfonyl group-containing compound.

In the following, cyclopentadiene will be abbreviated as "Cp". The same abbreviation will be used for a cyclopentadienyl group if it is clear from the context whether cyclopentadiene itself or its anion is meant.

A method for such a synthesis is known from Szymoniak et al. (J. Org. Chem, 1990, 55, 1429-1432).

Described herein is a method for the synthesis of a tetramethylcyclopentadiene with a diphenylphosphine-containing substituent. The synthesis proceeds in the following way: The tetramethylcyclopentadienyl is deprotonated to the anion, this anion is reacted with 2-30 chloroethyltosylate and then, in a second reaction step, with lithium diphenylphosphide. The yield is 68%. Multiple isomers of the alkylated cyclopentadiene can be obtained in such alkylation reactions.

For example, Jutzi et al. (Synthesis 1993, 684) describe that such a synthesis route cannot lead to the 1,2,3,4,5-pentage-substituted cyclopentadiene, because only partial substitution of the tetramethylcyclopentadiene occurs. Jutzi isolates these geminal products with a yield of 65%.

Geminally substituted cyclopentadiene is a cyclopentadiene containing two substituents not equal to a hydrogen atom to the sp3 carbon of the cyclopentadiene ring.

The object of the invention is to provide a simple method for the synthesis of a substituted Cp compound of which at least 1 substituent has the form -RDR'n, with the conversion being as high as possible and with the least possible formation of geminal products.

The invention is characterized in that the sulfonyl group-containing compound is a compound of the formula (DR'n-R-Sul), wherein R is a linking group, R 'is a substituent, D is a heteroatom of group 15 or 16 of the Periodic 20 is the System of Elements, n is the number of D-linked R 'groups and Sul is a sulfonyl group.

It has now surprisingly been found that when the introduction of a substituent having the form -RDR'n is carried out in the above manner, it is possible to obtain non-geminally substituted Cps.

A further advantage of the synthesis method according to the invention is that, in contrast to the method performed by Szymoniak and Jutzi, for applying one or more substituents of the form -RDR to a substituted Cp compound, only one synthesis step has to be are carried out.

Another advantage of the synthesis method according to the invention is that yields greater than or equal to 95% are realized.

1003009 - 3 - ΓΙ-

During the process according to the invention only partial product is formed.

The geminal products are easily separated by converting the product from the above synthesis into a salt, by reaction with potassium, sodium or a base, after which this salt is washed with a dispersing agent, in which the salt of the non-geminal products does not dissolve.

The substituted Cp compound can be used as a ligand in a metal complex.

During the first step of the synthesis route, a Cp compound already substituted with at least one other group is deprotonated by reaction with a base, sodium or potassium.

As base can be used, for example, organolithium compounds (R3Li) or organomagnesium compounds (R3MgX) in which R3 = an alkyl, aryl or aralkyl group and X = halide, such as, for example, n-butyl lithium or i-20 propyl magnesium chloride.

Potassium hydride, sodium hydride, inorganic bases, such as NaOH and KOH, and alcoholates of Li, K and Na can also be used as the base.

Mixtures of the above compounds can also be used.

This reaction can be performed in a polar dispersant such as, for example, an ether. Examples of ethers are tetrahydrofuran (THF) or dibutyl ether. Non-polar solvents, such as, for example, toluene, can also be used.

Cp compounds are understood to mean Cp itself and Cp already substituted in at least one position, where two substituents can form a closed ring.

A substituted Cp compound contains at least 1 alkyl, alkenyl and / or aralkyl substituent.

The alkyl substituents can be either linear, branched or cyclic alkyl groups. Also, in the substituents, in addition to carbon and hydrogen, one or more heteroatoms from groups 14-17 of the Periodic Table may exist # e.g. 0, N, Si or 5 F. Examples of suitable substituents are methyl, ethyl, (iso) propyl, secondary butyl, pentyl, hexyl and octyl, (tertiary) butyl and higher homologues, cyclohexyl, benzyl. Combinations of these substituents on the Cp compound are also possible.

Substituted Cp compounds can be prepared by reacting a halide of the substituting compound in a mixture of the Cp compound and an aqueous solution of a base in the presence of a phase transfer catalyst. Almost equivalent amounts of the halogenated substituents can be used. An equivalent amount is understood to mean an amount in moles corresponding to the desired substitution rate, for example 2 moles per mole of Cp-20 compound if two-fold substitution with the respective substituent is intended.

Depending on the size and associated steric hindrance of the compounds to be substituted, up to three to six-fold substituted Cp compounds can be obtained. When reacting with tertiary halides, as a rule, only triply substituted Cp compounds can be obtained, with primary and secondary halides generally being able to be substituted with four and often even five or sixfold. Since a substituent of the form -RDR'n is introduced in a second step by means of the method according to the invention, a maximum of four substituents are introduced in this first step.

Substituents that can be applied by this method are, for example, alkyl groups, 1003009-5, both linear and branched and cyclic, alkenyl and aralkyl groups. In addition to carbon and hydrogen, one or more hetero atoms from groups 14-17 of the Periodic System may also be present, for example 0, N, 5 Si or F. Examples of suitable groups are methyl, ethyl, (iso) propyl, secondary butyl, pentyl, hexyl and octyl, (tertiary) butyl and higher homologues, cyclohexyl, benzyl.

The substituents are preferably used in the process in the form of their halides.

It is also possible with this method to obtain Cp compounds which are substituted with specific combinations of substituents without intermediate separation or purification. For example, a two-fold substitution can first be carried out using a certain alkyl halide and in the same reaction mixture a third substitution with another substituent by adding a second, different halide to the mixture after some time. This can be repeated so that it is also possible to manufacture Cp derivatives with three or more different substituents.

The substitution takes place in a mixture of the Cp compound and an aqueous solution of a base. The concentration of the base in the solution is between 20 and 80%. Hydroxides of an alkali metal, for example K or Na, are very suitable. The base is present in an amount of 5-60 moles per mole of Cp compound.

The substitution takes place in the presence of a phase transfer catalyst capable of transferring OH ions from the aqueous phase to the Cp and halide-containing organic phase, which react there with a cleavable H of the Cp compound. -atom. The phase transfer catalysts are used in an amount of 0.01-2 equivalents to the amount of Cp.

1003009 - 6 -

When performing the process, the components can be added to the reactor in various sequences.

After the reaction has ended, the aqueous phase and the Cp compound-containing organic phase are separated. The Cp compound is then recovered from the organic phase by fractional distillation.

Then, during a second step 10 of the synthesis route, the cyclopentadienyl anion formed reacts with a compound of the formula (DR '- - R-Sul), in which R is a linking group, R' is a substituent, D is an electron donating heteroatom of group 15 or is 16 of the Periodic Table of the Elements, n is the number of D-linked R 'groups and Sul is a sulfonyl group.

In the following, the respective parts in this connection will be discussed in more detail.

al The RDR group

The R group forms the link between the Cp 25 and the DR group. The length of the shortest connection between the Cp and D is critical in that it uses the Cp compound as a ligand in a metal complex to determine the accessibility of the metal by the DR group to thereby facilitate possible intramolecular coordination. to ease. Too short a length of the R group (or bridge) can prevent the donor from coordinating properly due to ring tension.

The R 'groups can each individually be a hydrocarbon radical of 1-20 carbon atoms (such as alkyl, aryl, arylalkyl, etc.). Examples of such hydrocarbon radicals are methyl, ethyl, 1003009-7 propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl.

R '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 5 of the Elements. For example, a substituent can be an N, O and / or Si-containing group. R 'should not be a cyclopentadienyl or derivative group.

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: 15 (—ER22-) p with p = 1-4 and E an atom from group 14 of the Periodic System. The R2 groups can each be H or a group as defined for R1.

The main chain of the R group can therefore contain, in addition to carbon, silicon or germanium.

Examples of such R groups are: dialkylsilylene, dialkylgermylene, tetraalkyldisilylene or tetraalkylsilaethylene (-SiR'jCR'j-). 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 30 of the Elements and one or more substituent (s) R 'bound to D'. The number of R 'groups (n) is linked to the nature of the heteroatom D, in that n = 2 if D is from group 15 and n = 1 if D is from group 16. With Heteroatom D is preferably selected from the group nitrogen (N), oxygen (0), phosphorus (P) or sulfur (S); more preferably, the heteroatom is nitrogen (N).

1003009 - 8 - r *

Also preferably the R 'group is an alkyl, more preferably an n-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 5 in the DR' 'group are linked together to form an annular structure (so that the DR' 'group may be a pyrrolidinyl group).

The DR group can coordinate bonding with a metal.

(B) the sulfone leaf soup

The sulfonyl group is in the form -SO 2 Re, where R 6 is a hydrocarbon radical of 1-20 carbon atoms (such as alkyl, aryl, aralkyl, etc.). Examples of such hydrocarbon radicals include butane, pentane, hexane, benzene, naphthalene. R6 may also contain, in addition to or instead of carbon and / or hydrogen, one or more heteroatoms from group 14-17 of the Periodic Table of the Elements, such as N, 0 or F.

Examples of sulfonyl groups are: phenylmethanesulfonyl, benzenesulfonyl, 1-butanesulfonyl, 2,5-dichlorobenzenesulfonyl, 5-dimethylamino-1-naphthalenesulfonyl, pentafluorobenzenesulfonyl, p-toluenesulfonyl, 25-chloromethanesulfonyl, trifluoromethane-2,4-trifluoromethanes 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.

The second reaction step can be performed in a polar dispersant such as, for example, an ether. Examples of ethers are THF or dibutyl ether. Non-polar solvents, such as, for example, toluene 1003009-9, can also be used.

The temperature at which the reaction is carried out is -60 to 80 ° C. The upper temperature limit is partly determined by the boiling point of the compound DR'n-5 R-Sul and the boiling point of the solvent.

When D is a nitrogen atom, the compound of the formula (DR'n-R-Sul) is formed in situ by reaction of an amino alcohol compound (R'2NR-OH) with successively a base (as defined above), potassium or sodium and a sulfonyl halide (Sul-X).

During the synthesis process according to the invention partly geminal products can be formed. A geminal substitution is a substitution in which the number of substituents increases by 1, but where the number of substituted carbon atoms does not increase. The amount of geminal products formed is low when the synthesis is carried out from a substituted Cp compound having 1 substituent and increases as the substituted Cp compound contains more substituents. In the presence of sterically large substituents on the substituted Cp compound, little or no geminal products are formed. Examples of sterically large substituents are secondary or tertiary alkyl substituents.

The amount of the mineral product that is formed is also low when the second step of the reaction is carried out under the influence of a Lewis base, the conjugated acid of which has a dissociation constant, pKa less than or equal to -2.5. The ρΚ, values are based on D.D. Perrin: Dissociation Constants of Organic Bases in Aqueous Solution, International Union of Pure and Applied Chemistry, Butterworths, London 1965. The 35 values were determined in aqueous H 2 SO 4 solution.

Ethers can be mentioned as an example of suitable Lewis bases.

1003009 - ίο -: - * '

When geminal products have been formed during the process of the invention, these products can be easily separated from the non-geminal products by converting the mixture of geminally and non-geminally substituted products into a salt, by reaction with potassium, sodium or a base, after which the salt is washed with a dispersing agent in which the salt of the non-geminal products does not dissolve or dissolves poorly.

The compounds as mentioned above can be used as base.

Suitable dispersing agents are non-polar dispersing agents, such as alkanes. Examples of suitable alkanes are: heptane and hexane.

The substituted Cp compounds of which at least 1 substituent has the form -RDR '' are very suitable for use as a ligand in a metal complex.

The metal complexes with the Cp compounds as a ligand are suitable as a catalyst component. These catalyst components, together with a cocatalyst, are used in the polymerization of olefins.

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

Examples 30 Experimental part:

Reactions were monitored over time using gas chromatography (GC type: Hewlett Packard 5890 Series II, equipped with autosampler type HP6890 Series Injector, integrator type HP3396A and HP Crossi inked 35 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.) 1003009 - 11 - rate: 7.5 ° C / min 250 ° C (29 minutes) The products were characterized by GC-MS (type Fisons MD800, equipped with a guadrupole mass detector, autoinjector Fisons AS800 and CPSil8 column 5 (30mx0.25mmxlym, low bleed) 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)) and NMR Bruker ACP200 (1H = 200MHz, 13C = 50MHz) or Bruker ARX400 (1H = 400MHz; 13C = 100MHz).

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

Example I

Preparation of 2- (N.N-dimethvlaminoethyl) toss plate in situ

In a three-necked round bottom flask equipped with magnetic stirrer and dropping funnel, a solution of n-butyl lithium in hexane (1 equivalent) was added under dry nitrogen to a solution of 2-dimethylaminoethanol 20 (1 equivalent) in dry THF at -10 * C (dosing time: 60 minutes). After adding all butyl lithium, the mixture was brought to room temperature and stirred for 2 hours. Then the mixture was cooled (-10 ° C) after which paratoluenesulfonyl chloride (1 equivalent) was added. It was then stirred at this temperature for 15 minutes before the solution was added to a cyclopentadienyl anion.

Similar tosylates can be prepared in an analogous manner. In some of the following examples, a tosylate is always coupled to alkylated Cp compounds. In addition to the desired substitution reaction, this coupling also involves geminal coupling. In almost all cases, the geminal isomers could be separated from the non-geminal isomers by converting the non-geminal isomers into their sparingly soluble potassium salt, loose; - 12 - followed by washing this salt with a solvent in which this salt does not or dissolves poorly.

Example II

Example Ha: Preparation of tri (2-propyl) cyclopentadiene

180 g of 50% NaOH (2.25 mol), 9.5 g of Aliquat 336 (23 mmol) and 15 g of (in a 200 ml double-walled reactor fitted with a baffles »cooler» overhead stirrer, thermometer and dropping funnel were added. 0.227 mol) of freshly cracked cyclopentadiene. The reaction mixture was stirred turbulently for a few minutes at a speed of 1385 rpm. Then 84 g of 2-propyl bromide (0.68 mol) was added. It was cooled with water. A few minutes after adding the 2-propyl bromide, the temperature rose about 10 10 C. The GC was shown to form 2-20 propylcyclopentadiene approximately 30 minutes after the addition of all 2-propyl bromide (monosubstituted). Then the reaction mixture was heated to 50 ° C. After 2 hours, stirring was stopped and phase separation was awaited.

The water layer was drained and 180 g (2.25 mol) of fresh 50% NaOH was added. Then it was stirred for an additional hour at 50 ° C. GC showed that at that time in the mixture of di-tri and tetra-substituted cyclopentadiene was between 90 and 95% tri (2-propyl) cyclopentadiene. The product was distilled at 1.3 mbar and 77-78 ° C. After distillation, 31.9 g of tri (2-propyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-MS, 13C and -NMR. 1 1003009

Example Ilb: Preparation of potassium (dimethvlaminoethyl) tri (2-propyl) cyclopentadienyl. In a dry 500 mL three-necked magnetic stirrer under a dry nitrogen atmosphere, a solution of 62.5 mL of n-butyl lithium (1.6 M in n-hexane; 100 mmol) added to a solution of 19.2 g (100 nunol) of triisopropylcyclopentadiene in 250 mL of THF 5 at -60 ° C. After warming up to room temperature (in about 1 hour), stirring was continued for 2 hours. After cooling to -60 ° C, a solution of in-situ prepared (dimethylaminoethyl) tosylate (105 mmol) (Example I) was added over 5 minutes. The reaction mixture was warmed to room temperature and stirred overnight. After addition of water, the product was extracted with petroleum ether (40-60 ° C). The combined organic layer was dried (Na2 SO4) and evaporated under reduced pressure. The conversion was higher than 95%. The geminal product isomers were removed by converting the non-geminal isomers into the sparingly soluble potassium (2-dimethylaminoethyl) triisopropylcyclopentadienyl and the potassium salt was washed with hexane. The overall yield of product (starting from triisopropyl cyclopentadiene) was about 55%.

Example IIc; Preparation of Bis (dimethvlaminoethyltri- (2-propyl) cvylopentadiene) In a dry 500 mL three-necked magnetic stirrer, a solution of 62.5 mL of n-butyl lithium (1.6 M in n-hexane; 100 mmol) was added to a solution under a dry nitrogen atmosphere of 19.2 g (100 mmol) of tri- (2-propyl) cyclopentadiene in 250 mL of 30 THF at -60 ° C. After warming to room temperature (in about 1 hour) stirring was continued for 2 hours After cooling to -60 ° C , a solution of in situ prepared (dimethylaminoethyl) tosylate (105 mmol) (Example I) was added over 5 minutes The reaction mixture was warmed to room temperature and then stirred overnight After adding water, the product was extracted with petroleum ether ( 40 - 60 ° C) The 1003009-14 combined organic layer was dried (Na2 SO4) and evaporated under reduced pressure, the conversion was higher than 95%, part of the product thus obtained (10.1 g; 38.2 mmol) was again alkylated under the same conditions with (dimethyla minoethyl) tosylate (39.0 mmol).

The bis (2-dimethylaminoethyl) tri- (2-propyl) cyclopentadiene was obtained in a 35% yield via column chromatography.

10

Example III

Example III: Preparation of di (cvlohexyl) cyclopentadiene

A 15 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% NaOH (7.5 mol) and cooled to 8 ° C. Then 20 g of Aliquat 336 (49 mmol) and 33 g (0.5 mol) of freshly cracked cyclopentadiene were added.

The reaction mixture was stirred turbulently for several minutes. Then 172 g of cyclohexyl bromide (1.05 mol) was added. It was cooled with water. After stirring at room temperature for 2 hours, the reaction mixture was heated to 70 ° C and stirred for another 6 hours. GC showed that at that time 79% di (cyclohexyl) cyclopentadiene was present. The product was distilled at 0.04 mbar and 110-120 ° C. After distillation, 73.6 g of di (cyclohexyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-MS, 13C and XH-NMR.

Example Illb: Preparation of (dimethylaminoethyl) dicclohexyl cyclopentadiene 35 In a 250 ml three-necked round bottom flask equipped with magnetic stirrer and dropping funnel, 1003009-15 of dicyclohexylcyclopentadiene (6.90 g; 30.0 g) was added under nitrogen atmosphere to a cooled (0 ° C) solution. mmol) in dry tetrahydrofuran (125 ml) added a solution of n-butyl lithium in hexane (18.7 ml; 1.6 mol / L; 30 mmol) dropwise. After stirring at room temperature for 24 hours, 30.0 mmol of in situ prepared 2- (dimethylaminoethyl) tosylate (Example I) was added. After stirring for 18 hours, the conversion was found to be 88% and water (100 ml) was carefully added dropwise to the reaction mixture, after which the tetrahydrofuran was distilled off. The crude product was extracted with ether and the combined organic phase was dried (sodium sulfate) and evaporated. The residue was purified on a silica gel column, resulting in 7.4 g

(Dimethylaminoethyl) dicyclohexylcyclopentadiene. Example IV

Example IVa; Preparation of di- and tri (2-pentyl) cyclopentadiene 20 A 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 900 g (11.25 mol) of clear 50% NaOH. Then, 31 g of Aliquat 336 (77 mmol) and 26.8 g (0.41 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes, then 155 g of 2-pentyl bromide (1.03 mol) was added over an hour. It was cooled with water. After stirring at room temperature for 3 hours, the reaction mixture was heated to 70 ° C, followed by stirring for another 2 hours. Stirring was stopped and phase separation was awaited. The water layer was drained and 900 g (11.25 mol) of fresh 50% NaOH were added. Stirring was then continued for 2 hours at 70 ° C. GC showed that at that time the mixture consisted of di- and tri (2-pentyl) cyclopentadiene (about 1: 1). The products were distilled at 2 1003009-16 mbar, 79-81 C C and 0.5 mbar, 102 C. C. After distillation, 28 g of di- and 40 g of tri (2-pentyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-5 MS, 13C and 1 H NMR.

Example IVb: Preparation of dimethylaminoethyl vidif2-pentyl) cyclopentadiene

In a 250 ml three-necked round bottom flask equipped with magnetic stirrer and dropping funnel, a nitrogen (0 ° C) solution of di-2-pentylcyclopentadiene (7.82 g; 38.0 mmol) in dry tetrahydrofuran (125 ml) was added under nitrogen atmosphere. a solution of n-butyl lithium in hexane (24.0 ml; 1.6 mol / L; 38 15 mmol) was added dropwise. After stirring at room temperature for 24 hours, 2- (dimethylaminoethyl) tosylate (38.0 mmol) prepared in situ (Example I) was added. After stirring for 18 hours, the conversion was found to be 92% and water (100 ml) was carefully added dropwise to the reaction mixture, after which the tetrahydrofuran was distilled off. The crude product was extracted with ether and the combined organic phase was dried (sodium sulfate) and evaporated. The residue was purified on a column with silica gel, resulting in 8.2 g of (dimethylaminoethyl) di (2-pentyl) cyclopentadiene.

Example IVci Preparation of (dimethvlaminoethyl-tri- (2-olentyl) cycloentadiene) The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-propyl) cyclopentadiene (Example 11b). The conversion was 90%. dimethylaminoethyl-tri- (2-pentyl-cyclopentadiene) was obtained by distillation in a yield of 54%. The (dimethylaminoethyl)-tri- (2-pentyl-cyclopentadiene) was obtained after preparative column purification on silica gel with successive 1003009-17 petroleum ether (40-60 ° C). ) and THF with an efficiency of 57%.

Example IVd; Preparation of (di-n-butvlaminoethyl) -5 tr i- (2-pentyl) cyclopentadiene

The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-propyl) cyclopentadiene (Example 11b) whereby the tosylate of N, N-di-n-butylaminoethanoic was prepared in situ. The conversion was 88%. The 2- (di-n-butylaminoethyl) -di- (2-pentyl) cyclopentadiene was obtained after preparative column purification on silica gel with petroleum ether (40-60 ° C) and THF successively, followed by distillation under reduced pressure with a yield of 51%.

Example V

Example Va: Preparation of di (2-propyl cyclopentadiene) In a 200 ml double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel, 180 g of clear 50% NaOH (2.25 mol), 9.5 g of Aliguat 336 (23 mmol) and 15 g (0.227 mol) of freshly cracked cyclopentadiene were combined The reaction mixture was stirred turbulently for a few minutes at a speed of 1385 rpm Then 56 g of 2-propyl bromide (0.46 mol) was added. was cooled with water A few minutes after addition of the 2-propyl bromide, the temperature rose about 10 ° C. Then it was stirred at 50 ° C for 6 hours. GC 30 showed that at that moment in the mixture of that tri (2 -propyl) cyclopentadiene 92% di (2-propyl) cyclopentadiene was present The product was distilled at 10 mbar and 70 ° C. After distillation, 25.35 g of di (2-propyl) cyclopentadiene was obtained.

The characterization was done by GC, GC-MS, 13C and -NMR.

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Example Ex: Preparation of (dimethvlaminoethylvidi (2-piodvi) cycloadadiene

The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-5 propyl) cyclopentadiene (Example Ilb). The conversion was 97%. The dimethylaminoethyldi (2-propyl) cyclopentadiene was obtained by distillation with a yield of 54%.

Example Vc: Preparation of (di-n-butyl-aminoethyl) di-2-propyl-cyclopentadiene

The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-propyl) cyclopentadiene (Example 11b) whereby the tosylate of N, N-di-n-butylaminoethanol was prepared in situ. The conversion was 94%. The non-geminal di-n-butylaminoethyldi (2-propyl) cyclopentadiene was obtained by distillation with a yield of 53%. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 100 300 9

Example VI

2

Example CLA: Preparation of di (2-butyl] cycloentadiene 3

A 4 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, 5 thermometer and dropping funnel was charged with 600 g of 6 clear 50% NaOH (7.5 mol) and cooled to 10 ° C. Then 30 g of Aliguat 336 (74 mmol) and 48.2 g (0.73 mol) of freshly cracked cyclopentadiene 9 were added. The reaction mixture was stirred turbulently for several minutes. Then 200 g of 2-butyl bromide 11 (1.46 mol) was added over half an hour. 12 was cooled with water. After stirring for 2 hours at room temperature 13, the reaction mixture was heated to 60 ° C, after which 14 was stirred for another 4 hours. The GC was shown to have more than 90% di (2- 16 butyl) cyclopentadiene present in the mixture at that time. The product was distilled at 20 mbar and 80-90 ° C. After distillation, 90.8 g of di (2-butylcyclopentadiene) were obtained.

- 19 -

The characterization was done by GC, GC-MS, 13C and XH-NMR.

Example VIb: Preparation of (dimethvlaminoethyl) di (2-5 butyl) cyclopentadiene

In a 250 ml three-necked round bottom flask fitted with a magnetic stirrer and dropping funnel, a cooled (0 ° C) solution of di- (2-butylcyclopentadiene (8.90 g; 50.0 mmole)) in dry tetrahydrofuran was added under nitrogen atmosphere. 150 ml) a solution of n-butyl lithium in hexane (31.2 ml; 1.6 mol / L; 50 mmol) added dropwise After stirring at room temperature for 24 hours, the 2- (dimethylaminoethyl) tosylate (50.0 mmol) (Example I) After stirring for 18 hours, the conversion was found to be 96% and water (100 ml) was carefully added dropwise to the reaction mixture, after which the tetrahydrofuran was distilled off, the crude product was extracted with ether and the combined organic phase was added to 20. dried (sodium sulfate) and evaporated The residue was purified on a column with silica gel, resulting in 8.5 g of (dimethylaminoethyl) di (2-butyl) cyclopentadiene. 1 2 3 4 5 6 7 8 9 10 11 100 3009

Example VII

2

Example Vila; Preparation of tri (2-3 butyl) cyclopentadiene 4

A 5 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, 6 thermometer and dropping funnel was charged with 400 g of 7 (5.0 mol) clear 50% NaOH (5 mol). Then 8 9.6 g of Aliquat 336 (24 mmol) and 15.2 g (0.23 mol) of fresh 9 cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for several minutes. Then 99.8 g of 2-butyl bromide (0.73 mol) was added over half an hour. It was cooled with water. After stirring at room temperature for half an hour, the reaction mixture was heated to 70 ° C and stirred for another three hours. Stirring was stopped and phase separation was awaited. The water layer was drained and 400 g (5.0 mol) of fresh 50% NaOH were added. Then 5 was stirred for another two hours at 70 ° C. GC showed that at that time more than 90% tri (2-butyl) cyclopentadiene was present in the mixture of di-tri- and tetra (2-butylcyclopentadiene) .The product was distilled at 1 mbar and 91 ° C. After distillation 40.9 g of tri (2-butyl) cyclopentadiene were obtained.

Characterization was done using GO, GC-MS, 13C and XH-NMR.

Example Vllb: Preparation of 15 (dimethvlaminoethyl) tri (2-butyl) cyclopentadiene

The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-propylcyclopentadiene) (Example 11b). The conversion was 92%. The product was obtained by distillation with a yield of 64%.

Example VIII

Example Villa: Preparation of di- and tri (3-pentyl) cyclopentadiene 25 A 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 430 g (5.4 mol) of clear 50% NaOH . Then 23 g of Aliquat 336 (57 mmol) and 27 g (0.41 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for several minutes, then 150 g of 3-pentyl bromide (1.0 mol) was added over an hour. It was cooled with water. After stirring at room temperature for 1 hour, the reaction mixture was heated to 70 ° C and stirred for another 3 hours. Stirring was stopped and phase separation was awaited. The water layer was drained and 540 g of 1003009-21 (6.70 mol) of fresh 50% NaOH was added. Stirring was then continued for 4 hours at 70 ° C. GC showed that at that time the mixture consisted of di- and tri (3-pentyl) cyclopentadiene (about 3: 2). The 5 products were distilled at 0.2 mbar, 51 C C and 0.2 mbar, 77-80 C. C. respectively. After distillation, 32 g of di- and 18 g of tri (3-pentyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-10 MS, 13C and -NMR.

Example VlIIb: Preparation of (dimethvlaminoethvl) di (3-pentvl) cycloadadiene

The reaction was carried out identically as for (dimethylaminoethyl) tri (2-propyl) cyclopentadiene (Example 11b). The conversion was 99%.

The (dimethylaminoethyl) di (3-pentyl) cyclopentadiene was obtained after preparative column purification on silica gel with 20 successively petroleum ether (40-60 ° C) and THF with an efficiency of 85%.

Example VIIIc: Preparation of (di-n-butyl-aminoethyl) di- (3-pentyl-cyclopentadiene) The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-propyl) cyclopentadiene (Example Ilb) with the tosylate of N N-di-n-butylaminoethanol was prepared in situ The conversion was 95% The product was obtained after successive column purification on silica gel with petroleum ether (40-60 ° C) and THF successively with a yield of 75%.

Example VlIId: Preparation of f2-dimethvlaminoethyl (-35-tri-f3-pentyl) cyclopentadiene

The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-1003009-22: propyl) cyclopentadiene (Example 1ib). The conversion was 94%. The (2-dimethylaminoethyl) -tri- (3-pentyl) cyclopentadiene was obtained after preparative column purification on silica gel with successively 5 petroleum ether (40-60 ° C) and THF with a yield of 61%.

Example IX

Example IXa: Preparation of dif2-10 propylclolohexylpropyl diadiene

150 g clear 50% NaOH (1.9 mol), 7 g Aliquat 336 (17.3 15 mmol) and 8.5 g (0.13 mol) were placed in a 200 ml double-walled reactor equipped with battles, cooler, overhead stirrer, thermometer and dropping funnel. freshly cracked cyclopentadiene combined. The reaction mixture was stirred turbulently for a few minutes at a speed of 1385 rpm. Then 31.5 g of 2-propyl bromide (0.26 mol) was added. It was cooled with water. The total dosing time was 1 hour. After adding the bromide, the reaction mixture was heated to 50 ° C. After 2 hours, stirring was stopped and separation was awaited.

The water layer was drained and 150 g (1.9 mol) of fresh 50% NaOH were added. Then 20.9 g (0.13 mol) of cyclohexyl bromide were added, followed by stirring at 70 ° C for an additional 3 hours. GC was used to show that 80% di (2-propylcyclohexylcyclopentadiene) was present in the mixture at that time. The product was distilled at 0.3 mbar and 80 ° C. After distillation, 17.8 g of di (2-propyl) cyclohexylcyclopentadiene was obtained.

The characterization was done by GC, GC-MS, 13C and 1 H NMR. 1 1003009

Example IXb: Preparation of cclohexyl (dimethvlaminoethyl) -di- (2-propylcycloadadiene - 23 - ι-ι »

In a pouring vessel, a solution of n-butyl lithium in hexane (25.0 mL; 1.6 mol / L) was added to a solution of cyclohexyldiisopropylcyclopentadiene (9.28 g; 40.0 mmol) in dry THF (150 mL) at room temperature. ; 40.0 mmol) was added dropwise. Then a solution of n-butyl lithium in hexane (25.0 mL; 1.6 mol / L; 40.0 mmol) in a cold (-78 ° C) solution of dimethylaminoethanol (3.56 g; 40.0 mmol) in THF (100 mL). After stirring for an hour and a half at room temperature, the mixture was again cooled to -78 ° C and the solid p-toluenesulfonyl chloride (8.10 g; 40.0 mmol) was added slowly. The mixture was brought to 0 ° C and stirred for 5 minutes, cooled again to -78 ° C, after which the mixture from the first pour was added all at once. After stirring at room temperature for 16 hours, the conversion was 100%. After column chromatography, 11.1 g of cyclohexyl (dimethylaminoethyl) -di- (2-propyl) cyclopentadiene were obtained.

20

Example X.

Example Xa: Preparation of tr (cclohexyl) cyclopentadiene

A 25 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% NaOH (7.5 mol) and cooled to 8 ° C. Then 20 g of Aliguat 336 (49 mmol) and 33 g (0.5 mol) of freshly cracked cyclopentadiene were added.

The reaction mixture was stirred turbulently for several minutes. Then 256 g cyclohexyl bromide (1.57 mol) was added. It was cooled with water. After stirring at room temperature for 1 hour, the reaction mixture was heated to 70 ° C and stirred for another 2 hours. After 2 hours, stirring was stopped and phase separation was awaited. The water layer was drained and 600 g (7.5 mol) of fresh 50% NaOH were added. Then 1003009-24 was stirred for another 4 hours at 70 ° C. GC showed that at that time 10% di- and 90% tri- (cyclohexyl) cyclopentadiene was present in the mixture. The product was distilled at 0.04 mbar and 130 ° C. After distillation, 87.4 g of tri (cyclohexyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-MS, 13C and 1H NMR.

Example Xb; Preparation of (dimethvlaminoethyl vtriccvlohexyl vclopentadiene)

The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri- (2-propyl) cyclopentadiene (Example Ilb). The conversion 15 was 91%. The product was obtained in a yield via silica gel preparative column purification with successively petroleum ether (40-60 ° C) and THF as eluent. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 100 300 9

Example XI

2

Example Xla: Preparation of 3-tetraphthylcyclopentadiene 4

A 5 1 L double-walled reactor equipped with a baffle, cooler, overhead stirrer, 6 thermometer and dropping funnel was charged with 1050 g of 7 clear 50% NaOH (13.1 mol) and cooled to 10 ° C. Then 32 g of Aliquat 336 (79 mmol) and 51 g (0.77 mol) of freshly cracked cyclopentadiene were added.

10

The reaction mixture was stirred vigorously for several minutes. Then 344 g of ethyl bromide (3.19 mol) 12 was gradually added over an hour. It was cooled with water. After stirring at room temperature for 1 hour, the reaction mixture was heated to 35 ° C, followed by a further stirring for 6 hours. Stirring was stopped and 16 was waited for phase separation. The water layer was drained and 1050 g (13.1 mol) of fresh 50% NaOH were added. Then another 5 hours at - 25 -.,. ..

stirred at room temperature. GC showed that at that time 15% tri-, 78% tetra- and 7% penta (ethyl cyclopentadiene) were present in the mixture. The product was distilled at 11 mbar and 91 ° C. After distillation 5, 74.8 g tetra (ethyl ) cyclopentadiene.

The characterization was done by GC, GC-MS, 13C and 1 H NMR.

Example Xlb: Preparation of 10-dimethlaminoethyl-tetraethyl-chloropentadiene

In a pouring vessel, a solution of n-butyl lithium in hexane (6.00 ml; 1.65 mol / L; 9,) was added to a solution of tetraethylcyclopentadiene (2.066 g; 11.6 mmol) in dry THF (20 ml) at room temperature. 90 mmol) 15 drops.

Then, in a second pouring vessel, a solution of n-butyl lithium in hexane (5.90 ml; 1.65 mol / L; 9.74 mmol) was added to a cold solution (-78 ° C) of 2-dimethylaminoethanol (0.867 g; 9.74 mmol) in THF (35 ml). After stirring at room temperature for two hours, the mixture was again cooled to -78 ° C and the solid p-toluenesulfonyl chloride (1.855 g; 9.74 mmol) was added slowly. The mixture was brought to 0 ° C and stirred for 5 minutes, after which the mixture from the first pouring vessel was added all at once. After 16 hours, the conversion was 100%.

After column chromatography, 2.6 g of (dimethylaminoethyl) tetraethylcyclopentadiene were obtained.

30

Example XII

Example Xlla: Preparation of tetra (octyl) cyclopentadiene

A 35 1.5 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 900 g of clear 50% NaOH (11.3 mol) and cooled to 1003009-26-10 ° C. Then 30 g of Aliquat 336 (74 mmol) and 48 g (0.72 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for several minutes. Then 577 g of octyl bromide 5 (2.99 mol) was added in an hour. It was cooled with water. After stirring at room temperature for 1 hour, the reaction mixture was heated to 35 ° C and stirred for another 6 hours. Stirring was stopped and ase separation was awaited. The water layer was tapped for 10 µl and 920 g (11.5 mol) of fresh 50% NaOH was added. Stirring was then continued for 5 hours at room temperature. The GC was shown to contain 10% tri-, 83% tetra- and 7% penta (octyl) cyclopentadiene at the time. The product was distilled under reduced pressure. After vacuum distillation, 226.6 g of tetra (octyl) cyclopentadiene were obtained.

The product was characterized by GC, GC-HS, 13C and 1 H NMR.

20

Example Xlb: Preparation of (dimethvlaminoethyl) tetra-n-octyl cyclopentadiene

In a pouring vessel, a solution of n-butyl lithium in hexane (24.8 ml; 1. 6 mol / L; 39.6 mmol) was added dropwise.

Then, in a second pouring vessel, a solution of n-butyl lithium in hexane (24.6 ml; 1.6, 30 mol / L; 39.6 mmol) was added to a cold solution (-78 ° C) of 2-dimethylaminoethanol (3, 53 g; 39.6 mmol) in THF (30 ml) was added dropwise. After stirring at room temperature for two hours, the mixture was again cooled to -78 ° C and the solid p-toluenesulfonyl chloride (7.54 g, 39.6 mmol) was added slowly. The mixture was brought to 0 ° C and stirred for 5 minutes, after which the mixture from the first pour was added all at once.

1003009 - 27 -

After 16 hours, the conversion was 87%. After column chromatography, 19.2 g of (dimethylaminoethyl) tetra-n-octylcyclopentadiene were obtained.

5

Example XIII

Example XlIIa: Preparation of tetra (propyl clover flea tadiene)

A 10 1 L double-walled reactor fitted with a baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 1000 g of clear 50% NaOH (12.5 mol) and cooled to 10 ° C. Then 30 g of Aliquat 336 (74 mmol) and 50 g (0.75 mol) of freshly cracked cyclopentadiene 15 were added. The reaction mixture was stirred turbulently for several minutes. Then 373 g of propyl bromide (3.03 mol) was added over an hour. It was cooled with water. After stirring at room temperature for 1 hour, the reaction mixture was heated to 35 ° C, followed by a further stirring for 6 hours. Stirring was stopped and phase separation was awaited. The water layer was drained and 990 g (12.4 mol) of fresh 50% NaOH was added. Stirring was then continued for 5 hours at room temperature. GC showed that at that time 14% tri-, 80% tetra- and 6% penta (propyl) cyclopentadiene was present in the mixture. The product was distilled under reduced pressure. After vacuum distillation, 103.1 g of tetra (propyl) cyclopentadiene were obtained.

The product was characterized by GC, GC-MS, 13C and 1 H NMR.

Example XlIIb: Preparation of (dimethylaminoethyl) tetra-n-propyl cyclopentadiene 35 In a 500 ml three-necked flask, a solution of tetra-n-propyl cyclopentadiene (35.0 g; 150 mmol) in dry THF (200 ml) was added at room temperature 1003009-28 - a solution of n-butyl lithium in hexane (93.8 ml; 1.6 mol / L; 150 mmol) was added dropwise.

Then, in a second pouring vessel, a solution of n-butyl lithium in hexane (93.8 ml; 1.6 mol / L; 150 mmol) was added to a cold solution (~ 78 ° C) of 2-dimethylaminoethanol (13.35 g (150 mmol) in THF (100 ml). After stirring at room temperature for two hours, the mixture was again cooled to -78 ° C and the solid p-toluenesulfonyl chloride (28.5 g, 150 mmol) was slowly added. The mixture was brought to -20 ° C and stirred for 5 minutes, after which the mixture from the first pour was added. After 16 hours, the conversion was 97%. After column chromatography, 39.6 g of (dimethylaminoethyl) tetra-n-15 propyl cyclopentadiene were obtained.

Example XIV

Preparation of (2-phenoxyethyl) -tetramethyl-cyclopentadiene In a 1 liter three-necked round bottom flask equipped with a dropping funnel, a solution of paratoluenesulfonyl chloride (141.5 g; 0.743 mol) and triethylamine (149.6 g; 1.48 mol) was added. in THF (400 ml) a solution of 2-phenoxyethanol (102.6 g; 0.744 mol) in THF (70 ml) was added (dosing time: 35 minutes). After 2 weeks of stirring (conversion: 88%), the suspension was filtered. The filtrate was evaporated, suspended in petroleum ether (40-60 ° C) and filtered again. The solid contained one equivalent of water (1 H-NMR) and was therefore dried in an excicator over 30 phosphorus pentoxide under reduced pressure for 13 days. The yield was 161.6 g, which still contained 9 mol% water.

To a 1 liter three neck round bottom flask equipped with mechanical overhead stirrer and dropping funnel, a solution of 35 tetramethylcyclopentadiene (12.2 g; 0.10 mol) mmol) in ether (500 ml) at 2 ° C over 35 minutes was added. butyl lithium (63 ml; 1.6 mol / L; 0.10 mol) 1003009-29. This mixture was stirred at room temperature overnight, after which the tosylate of 2-phenoxyethanol (29.5 g; 0.10 mol) was added over an hour. After stirring for two days, water (80 ml) was added to the reaction mixture. The organic phase was separated from the water layer, dried with sodium sulfate and evaporated. The residue was distilled under reduced pressure, resulting in 20.7 g of product.

In a 250 ml three-necked round bottom flask equipped with a magnetic stirrer, a solution of (2-phenoxyethyltetramethylcyclopentadiene in diethyl ether) was added with a solution of n-butyl lithium (10.8 ml; 1.6 mol / L; 15 17.3 mmol) under a nitrogen atmosphere. After stirring at room temperature for one hour, the lithium 5- (2-phenoxyethyl) - 1,2,3,4-tetramethylcyclopentadienyl was crystallized at -80 ° C, filtered immediately under nitrogen and then washed twice with petroleum ether. drying, 14.2 g of the lithium salt were obtained.

Example XV Preparation of (isopropoxyethyl) tetramethyl-cyclopentadiene.

In a 250 ml three-necked round bottom flask fitted with a dropping funnel, a solution of n-butyl lithium in hexane (35 ml; 1.6 mol / L; 56 mmol) was added to a solution of tetramethylcyclopentadiene (6.24 g; 51) under a nitrogen atmosphere. mmol) in diethyl ether. After stirring for 16 hours at room temperature, the tosylate of 2-isopropoxyethanol (14.01; 57 mmol) was added all at once. After stirring at room temperature for 16 hours, the reaction mixture was filtered and the precipitate was washed with diethyl ether. The combined organic layer was evaporated and the residue was distilled under reduced pressure resulting in 6.06 g of product.

1003009 - 30 -

In a three-necked round bottom flask, the crude product isopropoxyethyltetramethylcyclopentadiene was added dropwise to a cooled (0 ° C) suspension of potassium hydride (0.55g; 12.3mmol) in THF (100ml) under nitrogen atmosphere. After stirring at 0 ° C for half an hour, the mixture was slowly brought to room temperature (over four hours). After stirring overnight at room temperature, the solid was filtered under nitrogen and washed with petroleum ether (40-60 ° C) (twice with 100 ml) resulting in 3.22 g of potassium 5- (isopropoxyethyl) -1,2,3 .4-tetramethylcyclopentadienyl.

Example XVI

Preparation of (methoxyethyl tetramethyl-cyclopentadiene) A three-necked flask was charged with 12.4 g of 1,2,3,4-tetramethylcyclopentadiene (0.10 mol) dissolved in 350 ml of ether. The solution was cooled to 2 ° C and 63 ml of n- butyl lithium (1.6M in hexane, 0.10 mol) was added dropwise, followed by stirring at room temperature for 18 hours, followed by a solution of 23.5 g of 2-methoxyethyl tosylate (0.15 g) over a period of about 15 minutes. 10 mol) in 25 ml ether and then stirred at room temperature for 18 hours, then 50 ml water was added dropwise. Water and organic phase were separated. The water layer was extracted 2x with ether. The combined ether layers were dried over magnesium sulfate. magnesium sulfate was filtered off and the filtrate evaporated.

The residue (17.0 g) contained 1,2,3,4-tetramethyl-5 (2-methoxyethylcyclopentadiene). After gas chromatography analysis of the crude reaction mixture, the conversion of tosylate and tetramethylcyclopentadiene was found to be 100%.

35 1003009

Claims (2)

1. Conclusion 1.2 A method for substituting a cyclopentadiene with at least 1 group of the form -RDR 'by deprotonating cyclopentadiene already substituted with at least another group by reaction with a base, sodium or potassium and then the cyclopentadienyl anion formed Reacting with a sulfonyl group-containing compound, characterized in that the sulfonyl group-containing compound is a compound of the formula (DR 'nR-Sul), wherein R is a compound group, 15 R 'is a substituent, D is a heteroatom of group 15 or 16 of the Periodic Table of the Elements and Sul is a sulfonyl group. 2. Process according to claim 1, characterized in that the product obtained by the process according to claim 1 is converted into a salt by reaction with potassium, sodium or a base, after which this salt is washed with a dispersant, in which the salt of does not dissolve the non-ground products. 3. Cyclopentadiene containing at least 1 substituent of the form -RDR'n and at least 1 other substituent. Use of a substituted cyclopentadiene according to claim 3 as a ligand in a metal complex. The use of a metal complex according to claim 4 for the polymerization of an olefin. 10 0 3 GO δ COOPERATION TREATY (PCT) Sender: BODY FOR Γ_ | INTERNATIONAL At the | RESEARCH (ISA) PATENT COUNCIL Pa tl to 2 REQUEST FOR PAYMENT OF ADDITIONAL TAXES Ri-iswiik zh in accordance with PCT Article 17 (3) (a) and Rule 40.1 DATE OF TRANSMISSION of the International Investigation Authority Reference of the applicant or ^ authorized ^ * 8661EN _IDENTIFICATION OF THE DUTCH APPLICATION_ Dutch application no. Filing date 1003009 3 May 1996 Applicant (Name) DSM NV __VERZOEK_ This Netherlands Research Authority is of the opinion that the above Dutch application does not meet the requirement of unity of invention. The reasons why this is considered to be the case are stated below with reference to the claims, which relate to each individual invention: 2. Conclusion 3-5 See Annex for further explanation The International Research Authority intends to prepare a report on the International type novelty search on the parts of the application relating to the invention's first invention, ie the invention to which claims No. 1.2 ........... relate. The report will also cover other parts of the application only if a request for additional investigations is made within the time limit set below and the fees due are paid. PCT Article 17 (2) (b) in conjunction with Article 17 (2) (a) applies to conclusions no .................... An investigation is not feasible and therefore these conclusions are not involved in the investigation. THE PATENT COUNCIL IS GIVEN OPPORTUNITY WITHIN 45 DAYS FROM THE SHIPPING DATE STATED ABOVE ABOVE OR, IF APPLICABLE, MORE REQUESTS TO SUBMIT FURTHER INQUIRIES. THE AUTHORITY FOR INTERNATIONAL RESEARCH European Patent Office The competent official- Patentlaan 2, Rijswijk ZB \ J]. γ [ψ 'I m' Ö PnniT PCT / lSAyJöê mod 07-1979 * r 'COOPERATION CONVENTION (PCT) REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE IDENTIFICATION OF OE NATIONAL APPLICATION Characteristic of the applicant ol of o · gemacnegae 8661NL no Ne3n9eno 300 May 1996 Inaugurated priority applicant Applicant (Name) DSM NV Oaum from nai request for a research # * of niemaionaai type By oe msanee «ear in temet on aai Onoerzoek (ISA) to the request for a survey of mamaooraai type eegettend nr. SN 27496 EN L CLASSIFICATION OF THE SUBJECT (for sepaasmg of vorsaiülanoe dasaftcaees. Specify all dassrfwaoe symbols) 'according to oe mamaoonaw nassiftnaee (IPC) Int.Cl.6; C 07 C 211/25, C 07 C 209/68, C 07 C 41/30, C 07 C 43/162, C 07 G 17/00, C 08 F 10/00 II. FIELDS OF TECHNIQUE RESERVED Unsourced minimum documentation Classification system Assassination sym int. Cl. 6: C 07 C, C 07 F, C 08 F Onoeaocnte anoere ooeumenaoe to, inter alia, mnmum documenaae insofar as primordial documents etg. I y i NO EXAMINATION FOR CERTAIN CONCLUSIONS (comments on supplement olad) j IV.1 x 1 LACK OF UNIT OF INVENTION (comments on supplement olad) j ~ orro PCT / lSAvΓ0 * ifi * CS