KR101648137B1 - Method of preparing ligand compound and transition metal compound - Google Patents

Abstract

The present invention relates to a novel compound and a process for preparing a transition metal compound containing the same. When the transition metal compound prepared by the above method is used as a catalyst for producing an olefin-based polymer, an olefin-based polymer having excellent physical properties can be produced.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for preparing a ligand compound and a transition metal compound,

The present invention relates to a novel ligand compound and a process for producing a transition metal compound containing the same.

Metallocene catalysts for olefin polymerization have been developed for a long time. The metallocene compound is generally activated by using aluminoxane, borane, borate or other activator. For example, a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. When the chloride group of such a metallocene compound is substituted with another ligand (for example, benzyl or trimethylsilylmethyl group (-CH ₂ SiMe ₃ )), there has been reported an example in which the catalytic activity is increased.

European Patent EP 1462464 discloses a polymerization example using a hafnium metallocene compound having a chloride, benzyl, trimethylsilylmethyl group. Also, it has been reported that the production energy of the activated species varies depending on the alkyl ligand bound to the center metal (J. Am. Chem. Soc. 2000, 122, 10358). Korean Patent No. 820542 discloses a catalyst for the polymerization of olefins having a quinoline ligand, and this patent relates to a catalyst having a living group containing silicon and germanium atoms other than the methyl group.

Dow has disclosed in the early 1990s [Me ₂ Si (Me ₄ C ₅ ) N t Bu] TiCl ₂ (Constrained-Geometry Catalyst, CGC) in U.S. Patent No. 5,064,802. In the copolymerization reaction of ethylene and alpha-olefin, CGC (1) high molecular weight polymers with high activity at high polymerization temperatures, and (2) 1-hexene (1-hexene) And 1-octene are also excellent in the copolymerization of alpha-olefins with large steric hindrance. In addition, various characteristics of CGC were gradually known during the polymerization reaction, and efforts to synthesize the derivative and use it as a polymerization catalyst have actively been made in academia and industry.

One approach is to synthesize and incorporate a variety of metal compounds into which various bridges and nitrogen substituents have been introduced instead of silicon bridges. Representative metal compounds that have been known up to now include phosphorus, ethylene or propylene, methylidene and methylene bridges instead of CGC-structured silicon bridges. However, when applied to ethylene polymerization or copolymerization of ethylene and alpha olefins, But did not show excellent results in terms of activity or copolymerization performance.

As another approach, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and some polymerization using the compounds was attempted.

However, among all these attempts, only a few catalysts have actually been applied to commercial plants.

In order to solve the above problems, the present invention provides a novel ligand compound and a method for producing a transition metal compound containing the same.

In order to accomplish the above object, the present invention provides a process for preparing a compound represented by the following general formula (1), which comprises reacting a compound represented by the following general formula (6) and a compound represented by the following general formula (7)

[Chemical Formula 1]

[Chemical Formula 6]

(7)

In the above formulas (1), (6) and (7)

m is an integer of 1 to 2,

R ₁ , R ₂ and R ₃ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group or a silyl group having 7 to 20 carbon atoms, and at least two of R ₁ , R ₂ or R ₃ are connected to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring Except when R ₂ is hydrogen;

R ₄ , R ₅ and R ₆ are the same or different and each independently represents hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An alkylamino group having from 1 to 20 carbon atoms or an arylamino group having from 6 to 20 carbon atoms, and at least two R ₄ , R ₅ or R ₆ may be connected to each other to form an aliphatic or aromatic ring.

The present invention also provides a process for preparing a transition metal compound represented by the following general formula (2), which comprises reacting a ligand compound represented by the following general formula (1) with a metal precursor.

[Chemical Formula 1]

 (2)

In the above formulas (1) and (2)

m is an integer of 1 to 2,

R ₁ , R ₂ and R ₃ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group or a silyl group having 7 to 20 carbon atoms, and at least two of R ₁ , R ₂ or R ₃ are connected to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring Except when R ₂ is hydrogen;

R ₄ , R ₅ and R ₆ are the same or different and each independently represents hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An alkylamino group having from 1 to 20 carbon atoms or an arylamino group having from 6 to 20 carbon atoms, and two or more of R ₄ , R ₅ or R ₆ may be connected to each other to form an aliphatic or aromatic ring;

M is a Group 4 transition metal;

K represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An amino group, an arylamino group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms;

n is an integer of 2 to 3;

According to the production method of the present invention, a novel ligand compound and a transition metal compound can be obtained with a simple method and a high yield.

The novel ligand compounds obtained by the process of the present invention and the transition metal compounds containing them can be usefully used as catalysts for the polymerization reaction in the production of olefinic polymers.

1 shows the NMR spectrum of the ligand compound of Example 1. Fig.
Fig. 2 shows the NMR spectrum of the ligand compound of Example 2. Fig.
3 shows the NMR spectrum of the ligand compound of Example 3. Fig.
4 shows the NMR spectrum of the ligand compound of Example 4. Fig.
5 shows the NMR spectrum of the ligand compound of Example 5. Fig.
6 shows the NMR spectrum of the ligand compound of Example 6. Fig.
7 shows the NMR spectrum of the ligand compound of Example 7. Fig.
8 shows the NMR spectrum of the ligand compound of Example 8. Fig.
9 shows the NMR spectrum of the ligand compound of Example 9. Fig.
10 shows the NMR spectrum of the ligand compound of Example 10. Fig.
11 shows the NMR spectrum of the ligand compound of Example 11. Fig.
12 shows the NMR spectrum of the ligand compound of Example 12. Fig.
13 shows the NMR spectrum of the ligand compound of Example 13. Fig.
14 shows the NMR spectrum of the ligand compound of Example 14. Fig.
15 shows the NMR spectrum of the transition metal compound of Example 15. Fig.
16 shows the NMR spectrum of the transition metal compound of Example 16. Fig.
17 shows the NMR spectrum of the transition metal compound of Example 17. Fig.
18 shows the NMR spectrum of the transition metal compound of Example 18. Fig.
19 shows the NMR spectrum of the transition metal compound of Example 19. Fig.
20 shows the NMR spectrum of the transition metal compound of Example 20. Fig.
21 shows the NMR spectrum of the transition metal compound of Example 21.
22 shows the NMR spectrum of the transition metal compound of Example 22. Fig.
23 shows the NMR spectrum of the transition metal compound of Example 23. Fig.
24 shows the NMR spectrum of the transition metal compound of Example 24. Fig.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, integers, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the present invention will be described in detail.

The method for preparing a ligand compound of the present invention represented by the following formula (1) comprises reacting a compound represented by the following formula (6) and a compound represented by the following formula (7).

[Chemical Formula 1]

[Chemical Formula 6]

(7)

In the above formulas (1), (6) and (7)

m is an integer of 1 to 2,

R ₁ , R ₂ and R ₃ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group or a silyl group having 7 to 20 carbon atoms, and at least two of R ₁ , R ₂ or R ₃ are connected to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring Except when R ₂ is hydrogen;

R ₄ , R ₅ and R ₆ are the same or different and each independently represents hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An alkylamino group having from 1 to 20 carbon atoms or an arylamino group having from 6 to 20 carbon atoms, and at least two R ₄ , R ₅ or R ₆ may be connected to each other to form an aliphatic or aromatic ring.

The compound represented by formula (I) prepared according to the above method may be a ligand compound capable of forming a chelate with a metal.

Each of the substituents defined above is described in detail as follows.

The alkyl group includes a linear or branched alkyl group.

The alkenyl group includes a linear or branched alkenyl group.

According to one embodiment of the present invention, the silyl group is selected from the group consisting of trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, Tris (trimethylsilyl) silyl, and the like, but the present invention is not limited to these examples.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like, no.

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group means an alkyl group substituted by the aryl group.

The halogen group means a fluorine group, a chlorine group, a bromine group or an iodine group.

The alkylamino group means an amino group substituted by the alkyl group, and includes, but is not limited to, dimethylamino group, diethylamino group, and the like.

The arylamino group means an amino group substituted by the aryl group, and includes, but is not limited to, a diphenylamino group and the like.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like, no.

The reaction between the compound represented by the formula (6) and the compound represented by the formula (7) is a nucleophilic addition reaction to the carbonyl group and can be carried out by stirring or refluxing.

The compound represented by the formula (6) can be prepared by condensing a compound represented by the following formula (4) with a compound represented by the following formula (5) in the presence of a Lewis acid and hydrolyzing the compound.

[Chemical Formula 4]

[Chemical Formula 5]

Wherein R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and m are as defined in the above formula (1).

At this time, the Lewis acid may include AlCl ₃ , BlCl ₃ and the like, but the present invention is not limited thereto.

According to an embodiment of the present invention, the ligand compound represented by Formula 1 may be represented by one of the following structural formulas, but is not limited thereto.

The compound represented by formula (I) prepared according to the above method may be a ligand compound capable of forming a chelate with a metal.

According to an embodiment of the present invention, when the compound represented by Formula 1 is a compound represented by Formula 1a, the ligand compound represented by Formula 1a may be synthesized by, for example, the following reaction scheme 1 The present invention is not limited thereto.

[Formula 1a]

[Reaction Scheme 1]

According to another aspect of the present invention, there is provided a process for preparing a transition metal compound represented by the following Chemical Formula 2, which comprises reacting a ligand compound represented by the following Chemical Formula 1 with a metal precursor.

[Chemical Formula 1]

 (2)

In the above formulas (1) and (2)

m is an integer of 1 to 2,

R ₁ , R ₂ and R ₃ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group or a silyl group having 7 to 20 carbon atoms, and at least two of R ₁ , R ₂ or R ₃ are connected to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring Except when R ₂ is hydrogen;

R ₄ , R ₅ and R ₆ are the same or different and each independently represents hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An alkylamino group having from 1 to 20 carbon atoms or an arylamino group having from 6 to 20 carbon atoms, and two or more of R ₄ , R ₅ or R ₆ may be connected to each other to form an aliphatic or aromatic ring;

M is a Group 4 transition metal;

K represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An amino group, an arylamino group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms;

n is an integer of 2 to 3;

According to one embodiment of the present invention, the transition metal of Group 4 corresponding to M may be Ti, Zr, or Hf, but is not limited thereto.

According to an embodiment of the present invention, the transition metal compound represented by Formula 2 may be represented by one of the following structural formulas, but is not limited thereto.

In the above structural formula, Me represents a methyl group and Bn represents a benzyl group.

According to an embodiment of the present invention, the step of reacting the ligand compound represented by Formula 1 with a metal precursor comprises reacting MX ₄ (where X is a halogen element) and an organolithium compound with the metal precursor, And then reacting the compound represented by the formula (8).

[Chemical Formula 1]

 (2)

[Chemical Formula 8]

 KMgX

In Formula 8,

X is a halogen element,

K represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, An arylamino group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms.

According to an embodiment of the present invention, the organolithium compound may be n-butyllithium, MX ₄ may be MCl ₄ , and the compound of Formula 8 may be methylmagnesium bromide.

According to another embodiment of the present invention, the metal precursor may be a compound represented by the following general formula (9).

[Chemical Formula 9]

MK _{n +1}

In the above formula (9)

M is a Group 4 transition metal;

K represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An amino group, an arylamino group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms;

n is an integer of 2 to 3;

For example, when the metal compound represented by the formula (2) is a compound represented by the following formula (2a), it may be synthesized by the following reaction scheme 2, but is not limited thereto.

(2a)

 [Reaction Scheme 2]

The transition metal compound obtained by the production method of the present invention can be used as a catalyst for the polymerization reaction in the production of the olefinic polymer.

More specifically, the transition metal compound obtained by the process of the present invention may be used alone or in combination with at least one of the promoter compounds represented by the following general formula (10), (11) or (12) Can be used as a catalyst for the polymerization reaction.

[Chemical formula 10]

- [Al (R < 7 >) - O] _n -

In Formula 10,

R7 may be the same or different from each other and are each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

n is an integer of 2 or more;

(11)

J (R < 7 >) ₃

In Formula 11,

R7 is as defined in Formula 10 above;

J is aluminum or boron;

[Chemical Formula 12]

[EH] ⁺ [ZA ₄ ] ^- or [E] ⁺ [ZA ₄ ] ^-

In Formula 12,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a Group 13 element;

A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .

Examples of the compound represented by Formula (10) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane. A more preferred compound is methylaluminoxane.

Examples of the compound represented by Formula 11 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by the formula (12) include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra (p- Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.

Preferably, alumoxane can be used, more preferably methylalumoxane (MAO), which is alkylalumoxane.

The catalyst composition comprises, as a first method, 1) contacting a transition metal compound represented by Formula 2 and a compound represented by Formula 10 or Formula 11 to obtain a mixture; And 2) adding the compound represented by Formula 12 to the mixture.

The catalyst composition may be prepared by a method of contacting the transition metal compound represented by Formula 2 and the compound represented by Formula 10 as a second method.

In the first method of the catalyst composition, the molar ratio of the transition metal compound represented by Formula 2 / the compound represented by Formula 10 or Formula 11 is preferably 1 / 5,000 to 1/2, Preferably from 1/1000 to 1/10, and most preferably from 1/500 to 1/20. When the molar ratio of the transition metal compound represented by the general formula (2) / the compound represented by the general formula (10) or the general formula (11) is more than 1/2, the amount of the alkylating agent is very small and the alkylation of the metal compound can not proceed completely If the molar ratio is less than 1 / 5,000, the alkylation of the metal compound is performed, but the alkylated metal compound can not be completely activated due to the side reaction between the excess alkylating agent and the activating agent. The molar ratio of the transition metal compound represented by Formula 2 to the compound represented by Formula 12 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1/5 Lt; / RTI > When the molar ratio of the transition metal compound represented by the general formula (2) / the compound represented by the general formula (12) is more than 1, the activation of the metal compound is not completely achieved due to the relatively small amount of the activator, If the molar ratio is less than 1/25, the activation of the metal compound is completely performed. However, there is a problem that the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low.

In the second method of the catalyst composition, the molar ratio of the transition metal compound represented by Formula 2 to the compound represented by Formula 10 is preferably 1 / 10,000 to 1/10, more preferably 1 / / 5,000 to 1/100, and most preferably 1/3000 to 1/500. When the molar ratio exceeds 1/10, the amount of the activating agent is relatively small, and the activation of the metal compound is not completely achieved. Thus, there is a problem in that the activity of the catalyst composition is poor. When the molar ratio is less than 1 / 10,000, Although the activation is completely performed, there is a problem that the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low.

In the preparation of the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane or the like, or an aromatic solvent such as benzene, toluene or the like may be used as a reaction solvent.

In addition, the catalyst composition may contain the transition metal compound and the cocatalyst compound in the form of being carried on a carrier.

The polymerization reaction for polymerizing the olefin monomer in the presence of the catalyst composition containing the transition metal compound can be carried out by a solution polymerization process, a slurry polymerization process using a single slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor, Or by gas phase processes. Further, homopolymerization with one olefin monomer or copolymerization with two or more kinds of monomers can be carried out.

The polymerization of the polyolefin may be carried out by reacting at a temperature of from about 25 ° C to about 500 ° C and from about 1 to about 100 kgf / cm ² . In particular, the polymerization of the polyolefin may be carried out at a temperature of from about 25 to about 500 캜, preferably from about 25 to 200 캜, more preferably from about 50 to 100 캜. The reaction pressure can also be carried out at from about 1 to about 100 kgf / cm ² , preferably from about 1 to about 50 kgf / cm ² , and more preferably from about 5 to about 40 kgf / cm ² .

Specific examples of the olefin-based monomer in the polyolefin produced according to the present invention include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-undecene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aidocene and the like, or a copolymer obtained by copolymerizing two or more of these.

The polyolefin may be a propylene polymer, but is not limited thereto.

Hereinafter, preferred embodiments of the present invention will be described to facilitate understanding of the present invention. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

<Examples>

&Lt; Synthesis of ligand compound >

Example 1

( E ) -N - ((1,2,3,4- Tetrahydro -2- phenylquinoline -8- yl ) ( phenyl ) 메틸렌 ) -2,6-diisopropylbenzenamine

Example  1-1

Phenyl (2- phenyl -1,2,3,4- tetrahydroquinoline -8- yl ) Preparation of methanone

A water-cooled condenser was connected to a 250 ml 2-neck round bottom flask, and 2-phenyl 1,2,3,4-tetrahydroquinoline (10 g, 48 mmol) was added and dissolved in 48 mL of toluene. After the solution was cooled to 0 ° C, BCl ₃ (53 mL, 53 mmol, 1 M solution in methylene chloride) was added and stirred. Benzonitrile (10 mL, 96 mmol) and AlCl ₃ (6.4 g, 48 mmol) were added and refluxed overnight at 110 ° C. Then, it was vacuum dried at 110 ° C to remove the solvent, cooled to room temperature, and then 100 mL of 4N HCl was added thereto, followed by stirring at 80 ° C for 1 hour.

After cooling to room temperature, the reaction product was dissolved in methylene chloride, and the organic layer was collected. The collected organic layer was transferred to a separatory funnel, and water was added thereto. The pH of the water layer was adjusted to 9-10 by adding 1N KOH. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated to give a crude product of the yellow solid. This was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto to recrystallize the precipitate. The precipitate was filtered to obtain phenyl (2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl) methanone as a yellow crystal. (Yield: 94%)

Example  1-2

( E ) -N - ((1,2,3,4- Tetrahydro -2- phenylquinoline -8- yl ) ( phenyl ) 메틸렌 ) -2,6-diisopropylbenzenamine

After the water-cooled condenser was connected to a 100 ml 2-neck round bottom flask (rbf), the phenyl (2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl) methanone (10 g, 48 mmol) was added and dissolved in 21 mL of purified toluene. 2,6-diisopropylaniline (2.9 mL, 32 mmol) was added thereto, and the mixture was stirred at room temperature for 10 minutes. Then, TiCl ₄ (6.4 mL, 6.4 mmol, 1 M solution in toluene) was added, stirred at room temperature for 1 hour, and then refluxed at 110 ° C for 1 day. After the reaction was completed, the mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized with an excess amount of methanol. ( E ) -N- ((1,2,3,4-Tetrahydro-2-phenylquinolin-8-yl) (phenyl) methylene) -2,6-diisopropylbenzenamine was obtained by filtration. (Yield: 88%)

The NMR spectrum of the ligand compound synthesized in Example 1 is shown in FIG.

Example  2

( E ) - N - ((1,2,3,4- tetrahydro -2- phenylquinoline -8-yl) (phenyl) methylene) benzenamine

A 2-neck round bottom flask was connected to a water-cooled condenser. 2 g (6.4 mmol) of phenyl (2-phenyl-1,2,3,4-tetrahydroquinolin- And dissolved by adding 21 mL of toluene. 2.9 mL (32 mmol, 5 eq.) Of aniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 4.8 mL (1 M solution in toluene, 4.8 mmol, 0.75 eq.) Of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. This was filtered to give 2.2 g (5.6 mmol, 88% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 2 is shown in FIG.

Example  3

( E ) - N - ((1,2,3,4- tetrahydro -2- phenylquinoline -8- yl ) ( phenyl ) 메틸렌 ) -2,6-dimethylbenzenamine

(2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl) methanone of Example 1-1 (6.4 mmol) was placed in a 100 ml 2-neck round bottom flask Soluble in 21 mL of purified toluene. 3.3 mL (32 mmol, 5 eq.) Of 2,6-dimethylaniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 equivalent) of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the reaction mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. Filtration gave 2.1 g (5.2 mmol, 81% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 3 is shown in FIG.

Example  4

( E ) - N - ((1,2,3,4- tetrahydro -2- (1- naphthyl ) quinolin -8-yl) (phenyl) methylene) -2,6-dimethyl-benzenamine

Example  4-1

(2-( Naphthalen -One- yl ) -1,2,3,4- tetrahydroquinoline -8- yl ) ( phenyl ) 메탄one Manufacturing

A water-cooled condenser was connected to a 250 mL 2-neck round bottom flask, and then 12 g (48 mmol) of 2- (naphthen-1-yl) -1,2,3,4-tetrahydroquinoline was added and dissolved in 48 mL of purified toluene. After cooling the solution to 0 ° C, 53 mL (1 M solution in methylene chloride, 53 mmol, 1 equivalent) of BCl ₃ was added and stirred. Benzonitrile was added to 10 mL (96 mmol, 2 eq) and _{AlCl 3 6.4 g (48 mmol,} 1 eq.) Was refluxed over night at 110 ℃. After the reaction was completed, the reaction mixture was vacuum-dried at 110 ° C to remove the solvent. After cooling to room temperature, 4 N HCl (100 mL) was added and the mixture was stirred at 80 ° C for 1 hour.

After cooling to room temperature, the reaction mixture was dissolved in methylene chloride, and the organic layer was collected. The collected organic layer was transferred to a separatory funnel, water was added, and 1 N KOH was added to adjust the pH of the water layer to 9-10. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated to give a yellow solid. The residue was dissolved in a small amount of methylene chloride, and recrystallized with an excess amount of methanol. The product was filtered to obtain 15.7 g (43 mmol, 90% yield) of a yellow solid.

Example  4-2

( E ) - N - ((1,2,3,4- tetrahydro -2- (1- naphthyl ) quinolin -8-yl) (phenyl) methylene) -2,6-dimethyl-benzenamine

(2-naphthalen-1-yl) -1,2,3,4-tetrahydroquinolin-8-yl) (phenyl) methanone of Example 4-1 2.3 g (6.4 mmol) was added and dissolved in 21 mL of purified toluene. 3.3 mL (32 mmol, 5 eq.) Of 2,6-dimethylaniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 equivalent) of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the reaction mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. This was filtered to give 2.5 g (5.4 mmol, 85% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 4 is shown in FIG.

Example  5

( E ) - N - ((1,2,3,4- tetrahydro -2- (1- naphthyl ) quinolin -8-yl) (phenyl) methylene) -2,6-diisopropyl-benzenamine

(2-naphthalen-1-yl) -1,2,3,4-tetrahydroquinolin-8-yl) (phenyl) methanone of Example 4-1 2.3 g (6.4 mmol) of the product are dissolved in 21 mL of purified toluene. 3.9 mL (32 mmol, 5 eq.) Of 2,6-diisopropylaniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 equivalent) of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the reaction mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. This was filtered to give 1.7 g (3.3 mmol, 51% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 5 is shown in FIG.

Example  6

( E ) - N - ( Phenyl (2- phenylindolin -7- yl ) methylene) benzenamine Manufacturing

Example  6-1

Phenyl (2- phenylindolin -7- yl ) Preparation of methanone

A water-cooled condenser was connected to a 250 mL 2-neck round-bottomed flask, and 9.4 g (48 mmol) of 2-phenylindoline was added thereto and dissolved by adding 48 mL of purified toluene. After cooling the solution to 0 ° C, 53 mL (1 M solution in methylene chloride, 53 mmol, 1 equivalent) of BCl ₃ was added and stirred. Benzonitrile was added to 10 mL (96 mmol, 2 eq) and _{AlCl 3 6.4 g (48 mmol,} 1 eq.) Was refluxed over night at 110 ℃. After the reaction was completed, the reaction mixture was vacuum-dried at 110 ° C to remove the solvent. After cooling to room temperature, 4 N HCl (100 mL) was added and the mixture was stirred at 80 ° C for 1 hour. After cooling to room temperature, the reaction mixture was dissolved in methylene chloride, and the organic layer was collected. The collected organic layer was transferred to a separatory funnel, water was added, and 1 N KOH was added to adjust the pH of the water layer to 9-10. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated to give a yellow solid. This was dissolved in a small amount of methylene chloride, and an excess amount of methanol was added to recrystallize the solution. The product was filtered to obtain 14 g (quantitative yield) of a yellow solid.

Example  6-2

( E ) - N - ( Phenyl (2- phenylindolin -7- yl ) methylene) benzenamine Manufacturing

1.9 g (6.4 mmol) of phenyl (2-phenylindolin-7-yl) methanone of Example 6-1 was dissolved in 21 mL of purified toluene and the solution was added to a 100 mL 2-neck round bottom flask. 2.9 mL (32 mmol, 5 eq.) Of aniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 4.8 mL (1 M solution in toluene, 4.8 mmol, 0.75 eq.) Of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. Filtration gave 2.1 g (5.6 mmol, 88% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 6 is shown in FIG.

Example  7

( E ) - N - ( Phenyl (2- phenylindolin -7- yl ) methylene) -2,6- dimethylbenzenamine Manufacturing

1.9 g (6.4 mmol) of phenyl (2-phenylindolin-7-yl) methanone of Example 6-1 was dissolved in 21 mL of purified toluene and the solution was added to a 100 mL 2-neck round bottom flask. 3.3 mL (32 mmol, 5 eq.) Of 2,6-dimethylaniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 equivalent) of TiCl ₄ solution was added, stirred at room temperature for 1 hour and then at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. This was filtered to give 2.0 g (5.1 mmol, 79% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 7 is shown in FIG.

Example  8

( E ) - N - ( phenyl (2- phenylindolin -7- yl ) methylene) -2,6-diisopropylbenzenamine

1.9 g (6.4 mmol) of phenyl (2-phenylindolin-7-yl) methanone of Example 6-1 was dissolved in 21 mL of purified toluene and the solution was added to a 100 mL 2-neck round bottom flask. 3.9 mL (32 mmol, 5 eq.) Of 2,6-diisopropylaniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 equivalent) of TiCl ₄ solution was added, stirred at room temperature for 1 hour and then at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. This was filtered to give 1.6 g (3.5 mmol, 55% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 8 is shown in FIG.

Example  9

( E ) - N - ( Phenyl ( indoline -7- yl ) methylene) benzenamine Manufacturing

Example  9-1

Indolin -7- yl ( phenyl ) Preparation of methanone

A 250 mL 2-neck round-bottomed flask was connected to a water-cooled condenser and then 5.7 g (48 mmol) of indoline was added and dissolved in 48 mL of purified toluene. After cooling the solution to 0 ° C, 53 mL (1 M solution in methylene chloride, 53 mmol, 1 equivalent) of BCl ₃ was added and stirred. 10 mL of benzonitrile (96 mmol, 2 eq.) And 6.4 g (48 mmol, 1 eq.) Of AlCl ₃ were added and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was vacuum-dried at 110 ° C to remove the solvent. After cooling to room temperature, 4 N HCl (100 mL) was added and the mixture was stirred at 80 ° C for 1 hour.

After cooling to room temperature, the reaction mixture was dissolved in methylene chloride, and the organic layer was collected. The collected organic layer was transferred to a separatory funnel, water was added, and 1 N KOH was added to adjust the pH of the water layer to 9-10. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated to give a yellow solid. This was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added to recrystallize the solution. The product was filtered to obtain 11 g (quantitative yield) of a yellow solid.

Example  9-2

( E ) - N - ( Phenyl ( indoline -7- yl ) methylene) benzenamine Manufacturing

100 mL 2-neck round bottom flask) was connected with a water-cooled condenser, and 1.4 g (6.4 mmol) of indolin-7-yl (phenyl) methanone of Example 9-1 was added thereto and dissolved in 21 mL of purified toluene. 2.9 mL (32 mmol, 5 eq.) Of aniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 4.8 mL (1 M solution in toluene, 4.8 mmol, 0.75 eq.) Of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the reaction mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. This was filtered to give 1.9 g (6.2 mmol, 97% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 9 is shown in Fig.

Example  10

( E ) - N - ( Phenyl ( indoline -7- yl ) methylene) -2,6- dimethylbenzenamine Manufacturing

100 mL 2-neck round bottom flask) was connected with a water-cooled condenser, and 1.4 g (6.4 mmol) of indolin-7-yl (phenyl) methanone of Example 9-1 was added thereto and dissolved in 21 mL of purified toluene. 3.3 mL (32 mmol, 5 eq.) Of 2,6-dimethylaniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 equivalent) of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the reaction mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. This was filtered to give 1.9 g (5.8 mmol, 91% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 10 is shown in FIG.

Example  11

( E ) - N - ( Phenyl (1,2,3,4- tetrahydroquinoline -7- yl ) methylene) benzenamine Manufacturing

Example  11-1

Phenyl (1,2,3,4- tetrahydroquinoline -8- yl ) Preparation of methanone

A water-cooled condenser was connected to a 250 mL 2-neck round bottom flask, and then 6.4 g (48 mmol) of 1,2,3,4-tetrahydroquinoline was added and dissolved in 48 mL of purified toluene. After cooling the solution to 0 ° C, 53 mL (1 M solution in methylene chloride, 53 mmol, 1 equivalent) of BCl ₃ was added and stirred. Benzonitrile was added to 10 mL (96 mmol, 2 eq) and _{AlCl 3 6.4 g (48 mmol,} 1 eq.) Was refluxed over night at 110 ℃. After the reaction was completed, the reaction mixture was vacuum-dried at 110 ° C to remove the solvent. After cooling to room temperature, 4 N HCl (100 mL) was added and the mixture was stirred at 80 ° C for 1 hour.

After cooling to room temperature, the reaction mixture was dissolved in methylene chloride, and the organic layer was collected. The collected organic layer was transferred to a separatory funnel, water was added, and 1 N KOH was added to adjust the pH of the water layer to 9-10. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated to give a yellow solid. This was dissolved in a small amount of methylene chloride. The excess was recrystallized by addition of methanol, which was then filtered to obtain 11.4 g (quantitative yield) of a yellow solid.

Example  11-2

( E ) - N - ( Phenyl (1,2,3,4- tetrahydroquinoline -7- yl ) methylene) benzenamine Manufacturing

After the water-cooled condenser was connected to a 100 mL 2-neck round bottom flask, 1.5 g (6.4 mmol) of phenyl (1,2,3,4-tetrahydroquinolin-8-yl) methanone of Example 11-1 was added, and 21 mL . 2.9 mL (32 mmol, 5 eq.) Of aniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 4.8 mL (1 M solution in toluene, 4.8 mmol, 0.75 eq.) Of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the reaction mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. This was filtered to give 1.9 g (6.1 mmol, 95% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 11 is shown in Fig.

Example  12

( E ) - N - ( Phenyl (1,2,3,4- tetrahydroquinoline -7- yl ) methylene) -2,6-dimethylbenzenamine

After the water-cooled condenser was connected to a 100 mL 2-neck round bottom flask, 1.5 g (6.4 mmol) of phenyl (1,2,3,4-tetrahydroquinolin-8-yl) methanone of Example 11-1 was added, and 21 mL . 3.3 mL (32 mmol, 5 eq.) Of 2,6-dimethylaniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 equivalent) of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the reaction mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. Filtration gave 2.1 g (6.1 mmol, 95% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 12 is shown in FIG.

Example  13

( E ) - N - ( phenyl (1,2,3,4- tetrahydroquinoline -7- yl ) methylene) -2,6-diisopropylbenzenamine

After the water-cooled condenser was connected to a 100 mL 2-neck round bottom flask, 1.5 g (6.4 mmol) of phenyl (1,2,3,4-tetrahydroquinolin-8-yl) methanone of Example 11-1 was added, and 21 mL . 3.9 mL (32 mmol, 5 eq.) Of 2,6-diisopropylaniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 equivalent) of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the reaction mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. This was filtered to give 1.7 g (4.2 mmol, 66% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 13 is shown in Fig.

Example  14

( E ) - N - (Phenyl (2- t - butyl -1,2,3,4- tetrahydroquinoline -7-yl) methylene) benzenamine

Example  14-1

(2- tert - Butyl -1,2,3,4- tetrahydroquinoline -8- yl ) ( phenyl ) 메탄one Manufacturing

250 mL 2-neck round-bottomed flask) was connected to a water-cooled condenser, and 9.1 g (48 mmol) of 2- tert- butyl-1,2,3,4-tetrahydroquinoline was added thereto and dissolved in 48 mL of purified toluene. After cooling the solution to 0 ° C, 53 mL (1 M solution in methylene chloride, 53 mmol, 1 equivalent) of BCl ₃ was added and stirred. Benzonitrile was added to 10 mL (96 mmol, 2 eq) and _{AlCl 3 6.4 g (48 mmol,} 1 eq.) Was refluxed over night at 110 ℃. After the reaction was completed, the reaction mixture was vacuum-dried at 110 ° C to remove the solvent. After cooling to room temperature, 4 N HCl (100 mL) was added and the mixture was stirred at 80 ° C for 1 hour.

After cooling to room temperature, the reaction mixture was dissolved in methylene chloride, and the organic layer was collected. The collected organic layer was transferred to a separatory funnel, water was added, and 1 N KOH was added to adjust the pH of the water layer to 9-10. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated to give a yellow solid. The residue was dissolved in a small amount of methylene chloride, and recrystallized with an excess amount of methanol. The product was filtered to obtain 9.3 g (31.7 mmol, 66% yield) of a yellow solid.

Example  14-2

( E ) - N - (Phenyl (2- t - butyl -1,2,3,4- tetrahydroquinoline -7-yl) methylene) benzenamine

100 mL 2-neck round bottom flask) was connected to a water cooled condenser 1.9 g (6.4 mmol) of (2- tert- butyl-1,2,3,4-tetrahydroquinolin-8-yl) phenyl methanone obtained in Example 14-1 was dissolved in 21 mL of purified toluene. 2.9 mL (32 mmol, 5 eq.) Of aniline was added thereto, followed by stirring at room temperature for 10 minutes. Then, 4.8 mL (1 M solution in toluene, 4.8 mmol, 0.75 eq.) Of TiCl ₄ solution was added, stirred at room temperature for 1 hour, and refluxed at 110 ° C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and 50 mL of diethyl ether was added thereto. After stirring sufficiently, the reaction mixture was filtered through a glass filter with a celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride, and an excessive amount of methanol was added thereto for recrystallization. This was filtered to give 1.6 g (4.4 mmol, 69% yield) of a yellow solid.

The NMR spectrum of the ligand compound synthesized in Example 14 is shown in Fig.

&Lt; Synthesis of transition metal compound >

Example  15

In a glove box, a 1-neck round-bottomed flask was charged with 2 mmol of the ligand compound of Example 1 and 10 mL of purified toluene to obtain a n-butyllithium solution (0.88 mL, 2.2 mmol m 2.5 M solution in n-hexane) was added and stirred at room temperature for 1 hour. HfCl ₄ (673 mg, 2.1 mmol) was added to the reaction solution, which was then connected to an air-cooled condenser and stirred at 100 ° C for 2 hours. After cooling to room temperature, methyl magnesium bromide solution (2 mL, 6 mmol of 3 M solution in diethyl ether) was added, followed by stirring at room temperature for 1 day. After completion of the reaction, the reaction mixture was vacuum-dried at 100 ° C, cooled to 50 ° C, and 20 ml of n-hexane was added thereto. This was filtered through a 4G glass filter and the filtrate was dried in vacuo to give a yellow solid.

The NMR spectrum of the transition metal compound synthesized in Example 15 is shown in FIG.

Example  16

745 mg (2.1 mmol, 1.05 equivalent) of the ligand compound (2 mmol) of Example 2 and Hf (NMe ₂ ) ₄ were added to a 1-neck round bottom flask in a glove box and 6 mL of purified toluene was added thereto. The condenser was connected and stirred at a constant temperature for a certain period of time. After completion of the reaction, the temperature was raised to 100 ° C and vacuum drying was conducted to obtain an orange solid in a quantitative yield.

The NMR spectrum of the transition metal compound synthesized in Example 16 is shown in Fig.

Example  17

Example 2 A transition metal compound was prepared in the same manner as in Example 16 except that the ligand compound of Example 6 was used in place of the ligand compound, and an orange solid was obtained in a quantitative yield.

The NMR spectrum of the transition metal compound synthesized in Example 17 is shown in Fig.

Example  18

To a 1-neck round bottom flask in a glove box was added 600 mg of the ligand compound (1 mmol) of Example 7 and Hf (CH ₂ Ph) ₄ (1.1 mmol, 1.1 eq.) And dissolved in 2.5 mL of purified n- hexane And the mixture was stirred at room temperature for 1 day. After completion of the reaction, the product was vacuum dried to obtain an orange solid in a quantitative yield.

The NMR spectrum of the transition metal compound synthesized in Example 18 is shown in Fig.

Implementation 19

A transition metal compound was prepared in the same manner as in Example 15 except that the ligand compound of Example 8 was used instead of the ligand compound of Example 1 to obtain an orange solid in a quantitative yield.

The NMR spectrum of the transition metal compound synthesized in Example 19 is shown in Fig.

Example  20

A transition metal compound was prepared in the same manner as in Example 16 except that the ligand compound of Example 9 was used instead of the ligand compound of Example 2 to obtain an orange solid in a quantitative yield.

The NMR spectrum of the transition metal compound synthesized in Example 20 is shown in FIG.

Example  21

A transition metal compound was prepared in the same manner as in Example 16 except that the ligand compound of Example 10 was used instead of the ligand compound of Example 2 to obtain an orange solid in a quantitative yield.

The NMR spectrum of the transition metal compound synthesized in Example 21 is shown in FIG.

Example  22

A transition metal compound was prepared in the same manner as in Example 16 except that the ligand compound of Example 11 was used instead of the ligand compound of Example 2 to obtain an orange solid in a quantitative yield.

The NMR spectrum of the transition metal compound synthesized in Example 22 is shown in Fig.

Example  23

A transition metal compound was prepared in the same manner as in Example 16 except that the ligand compound of Example 12 was used instead of the ligand compound of Example 2 to obtain an orange solid in a quantitative yield.

The NMR spectrum of the transition metal compound synthesized in Example 23 is shown in FIG.

Example  24

A transition metal compound was prepared in the same manner as in Example 15 except that the ligand compound of Example 13 was used instead of the ligand compound of Example 1 to obtain an orange solid in a quantitative yield.

The NMR spectrum of the transition metal compound synthesized in Example 24 is shown in Fig.

Comparative Example  One

Tribenzyl ( E ) - (8 - (((2- methylcyclohexyl ) imino ) methyl ) -3,4- dihydroquinoline -One( 2H ) - yl ) zirconium

Tribenzyl (E) - (8 - (((2-methylcyclohexyl) imino) methyl) -3,4-dihydroquinolin-1 (2H) -yl) zirconium compound was synthesized according to Example 4 of PCT / KR2010 / 004842.

Preparation of propylene homopolymer

Example  25

A toluene solvent (200 mL) was added to a 300 mL minicable reactor, and then the temperature of the reactor was preheated to 70 占 폚. 5 x 10 ^-3 M of dimethylanilinium tetrakis (penta-flow-phenyl) borate crude transition metal compound of Example 15-treated catalyst in 2mL of triisobutylaluminum compound (2x10 ^-3 M, 1mL) in order to Lt; / RTI &gt; Polymerization was initiated while continuously injecting propylene (5 bar). After the polymerization reaction was carried out for 10 minutes, the remaining gas was taken out and the polymer solution was poured into an excessive ethanol-containing beaker to induce precipitation. The obtained polymer was washed with ethanol and acetone two to three times, respectively, and dried in a vacuum oven at 80 캜 for 12 hours or more.

Example  26

An olefin polymer was prepared in the same manner as in Example 25 except that the transition metal compound of Example 16 was used.

Example  27

An olefin polymer was prepared in the same manner as in Example 25 except that the transition metal compound of Example 17 was used.

Example  28

An olefin polymer was prepared in the same manner as in Example 25 except that the transition metal compound of Example 18 was used.

Example  29

An olefin polymer was prepared in the same manner as in Example 25 except that the transition metal compound of Example 19 was used.

Example  30

An olefin polymer was prepared in the same manner as in Example 25 except that the transition metal compound of Example 20 was used.

Example  31

An olefin polymer was prepared in the same manner as in Example 25 except that the transition metal compound of Example 21 was used.

Example  32

An olefin polymer was prepared in the same manner as in Example 25 except that the transition metal compound of Example 22 was used.

Example  33

An olefin polymer was prepared in the same manner as in Example 25 except that the transition metal compound of Example 23 was used.

Example  34

An olefin polymer was prepared in the same manner as in Example 25 except that the transition metal compound of Example 24 was used.

Comparative Example  2

An olefin polymer was prepared in the same manner as in Example 25 except that the transition metal compound of Comparative Example 1 was used.

The melting point (Tm) of the polymer was measured using Q100 from TA. The measurements were obtained through a second melting step, which was ramped to 10 ° C per minute to eliminate the thermal history of the polymer.

The physical properties of the polymer obtained in Example 26 and Comparative Example 2 were measured in the same manner as described above, and the results are shown in Table 1 below.

Catalytic activity
(Unit: kg / mol hr) Melting point
(Unit: ℃) Example 26 900 129.5 Comparative Example 2 <5 -

Claims (8)

A process for preparing a ligand compound represented by the following formula (1), comprising reacting a compound represented by the following formula (6) with a compound represented by the following formula (7)
[Chemical Formula 1]

[Chemical Formula 6]

(7)

In the above formulas (1), (6) and (7)
m is an integer from 1 to 2;
R ₁ , R ₂ and R ₃ are the same or different and each independently hydrogen, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms;
R ₄ , R ₅ and R ₆ are the same or different and each independently hydrogen or an alkyl group having 1 to 20 carbon atoms.
The method for producing a ligand compound according to claim 1, wherein the compound represented by Formula 6 is prepared by condensing a compound represented by Formula 4 with a compound represented by Formula 5 in the presence of a Lewis acid to hydrolyze the compound:
[Chemical Formula 4]

[Chemical Formula 5]

Wherein R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and m are as defined in the above formula (1).
A process for producing a ligand compound according to claim 1, wherein the compound represented by the formula (1) is represented by one of the following formulas:

A process for preparing a transition metal compound represented by the following formula (2), comprising reacting a ligand compound represented by the following formula (1) with a metal precursor:
[Chemical Formula 1]

(2)

In the above formulas (1) and (2)
m is an integer from 1 to 2;
R ₁ , R ₂ and R ₃ are the same or different and each independently hydrogen, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms;
R ₄ , R ₅ and R ₆ are the same or different and each independently hydrogen or an alkyl group having 1 to 20 carbon atoms;
M is a Group 4 transition metal;
K represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, An arylamino group having 6 to 20 carbon atoms and an alkylidene group having 1 to 20 carbon atoms;
n is an integer of 2 to 3;
5. The method of claim 4, further comprising the steps of: reacting MX ₄ (where X is a halogen element) and an organic lithium compound with the metal precursor; And
A process for producing a transition metal compound represented by Formula 2, comprising reacting a compound represented by Formula 8:
[Chemical Formula 8]
KMgX
In Formula 8,
X is a halogen element;
K represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, An arylamino group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms.
5. The method for producing a transition metal compound according to claim 4, wherein the metal precursor is a compound represented by the following general formula (9)
[Chemical Formula 9]
MK _{n + 1}
In the above formula (9)
M is a Group 4 transition metal;
K represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, An arylamino group having 6 to 20 carbon atoms and an alkylidene group having 1 to 20 carbon atoms;
n is an integer of 2 to 3;
5. The method for producing a transition metal compound according to claim 4, wherein M is selected from the group consisting of Ti, Zr and Hf.
The method for producing a transition metal compound according to claim 4, wherein the transition metal compound represented by Formula 2 is represented by one of the following formulas:

Images