KR100590721B1 - Hydroformylation catalysts and preparation method thereof, and hydroformilation method using thereof - Google Patents

Abstract

The present invention relates to a hydroformylation catalyst, a method for preparing the same, and a hydroformylation reaction method using the same, and more particularly, to provide an imidazolylidene-based metal compound represented by the following Chemical Formula 1.

[Formula 1]

The hydroformylation catalyst of the present invention does not contain halogen, has excellent activity, high iso-aldehyde selectivity, and easy synthesis, and is suitable for use in hydroformylation of olefinic compounds.

Hydroformylation, catalysts, imidazolylidene, ligands

Description

HYDROFORMYLATION CATALYSTS AND PREPARATION METHOD THEREOF, AND HYDROFORMILATION METHOD USING THEREOF}

[Industrial use]

The present invention relates to a hydroformylation catalyst, a method for preparing the same, and a method for hydroformylation using the same, and more particularly, a novel hydroformylation catalyst and a method for preparing the hydroformylation reaction of an olefin compound and It relates to a hydroformylation reaction method using the same.

[Private Technology]

Research on the oxo reaction has already been extensively carried out, with more than 400 US patents filed between 1972 and 1999, and is still ongoing. In particular, research on catalysts has mostly focused on the development of new ligands and their applications. In particular, commonly used phosphine and phosphite-based ligands are already in the saturation stage of research and development.

Hydroformylation reaction catalysts have also been extensively studied, and in many processes, acetylacetonato-dicarbonyldium (Rh (AcAc) (CO) ₂ ), acetylacetonatocarbonyltriphenylphosphindium (Rh (AcAc)). (CO) (TPP)) or hydridocarbonyltri (triphenylphosphine) rhodium (HRh (CO) (TPP) ₃ ) and the like are mainly used, and these catalysts are readily available commercially.

In the case of the oxo process based on propene, tetracarbonyl cobalt sodium (NaCo (CO) ₄ ) is available from BASF, and Hidodorido (carbonyl) tributylphosphine is manufactured from Shell. Cobalt (HCo (CO) ₃ PBu ₃ ), Hiddidodocarbonyltri (triphenylphosphine) rhodium (HRh (CO) (TPP) ₃ ) at Union Carbide (UCC), and Luhechemy-Long-Plan (Ruhrchemie-Rhone-Poulence) uses rhodium / TPPTS as a catalyst.

Recently, many studies have been actively conducted to develop new catalysts using platinum, platinum or palladium as a core metal of the hydroformylation catalyst. However, in terms of activity and normal / iso (N / I) selectivity for the hydroformylation reaction, the performance of the rhodium catalyst has not yet been observed.

Studies on the hydroformylation of rhodium catalysts coordinated with N-Heterocyclic Carbene (NHC) have already been reported in towels ( Angew. Chem. Int. Ed. 2002, 41 , 1290). -1309, Organometallics , 2000, 19 , 3459-361). However, in the case of these compounds, halogenated materials such as chlorine (Cl), which is known as an inhibitor of hydroformylation reaction, are coordinated with rhodium, which is a central metal. In addition, there are few examples applied to the hydroformylation reaction of these compound olefins.

The present invention is to solve the above problems, the object of the present invention is that the catalyst does not contain a halogen, has excellent activity, high selectivity for iso-aldehyde and easy synthesis, hydroformylation of olefin compound It is to provide a novel hydroformylation reaction catalyst suitable for use in the reaction and a preparation method thereof.

It is also an object of the present invention to provide a hydroformylation reaction method using the novel hydroformylation reaction catalyst.

The present invention provides an imidazolylidene-based metal compound represented by the following formula (1) in order to achieve the above object.

[Formula 1]

In Chemical Formula 1,

M is a transition metal,

R ¹ and R ² are each an alkyl group, a cyclo alkyl group, an alkoxy group, a phenyl group, or a phenyl group to which 1 to 5 substituents are attached, and the substituents are nitro (-NO ₂ ), fluoride (F), chloride (Cl), Bromide (Br), methyl, ethyl, propyl or butyl.

R ³ and R ⁴ each represent a hydrogen, a halogen, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group,

L ¹ , L ² and L ³ are each hydrogen, CO, or acetylacetonato,

x, y and z are each an integer from 0 to 4, except where x, y and z are all zeros.

The present invention also provides a catalyst for hydroformylation reaction containing the above imidazolilidene-based metal compound.

The present invention also relates to a) i) 1 equivalent of the compound represented by the following formula (2); And ii) reacting 2 equivalents of an amine represented by Chemical Formula 3, an amine represented by Chemical Formula 4, or a mixture thereof to synthesize a dimine compound; b) reducing the diimine compound and adding an acid to prepare a diamine salt; c) reacting the diamine salt with triethyl orthoformate to prepare a cyclized imidazole salt; d) adding the imidazole salt to an organic solvent and preparing a slurry by adding at least one substance selected from the group consisting of liquid ammonia, sodium salt, potassium salt, and lithium salt; And e) adding the prepared slurry to a solution in which the metal precursor is dissolved and heating the imidazole- ylidene-based metal compound represented by Chemical Formula 1.

[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 2 to 4,

R ¹ and R ² are each an alkyl group, a cyclo alkyl group, an alkoxy group, a phenyl group, or a phenyl group to which 1 to 5 substituents are attached, and the substituents are nitro (-NO ₂ ), fluoride (F), chloride (Cl), Bromide (Br), methyl, ethyl, propyl or butyl.

R ³ and R ⁴ are each hydrogen, halogen, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group.

The present invention also comprises the steps of: a) dissolving the compound represented by Chemical Formula 1 in a solvent to prepare a catalyst solution; b) preparing a ligand solution by dissolving a ligand compound represented by Formula 5 or a mixture of Formula 6 and Formula 7 in a solvent; And c) mixing the catalyst solution with the ligand solution, and then heating and pressurizing the mixture with a mixed gas of an olefin compound, carbon monoxide, and hydrogen, represented by the following Formula 8, to provide a hydroformylation reaction method. .

[Formula 5]

In Formula 5, R ⁵ , R ⁶ , and R ⁷ are each a C ₁ to C ₂₀ alkyl group, a cyclo alkyl group, an alkoxy group, a phenyl group, a phenyloxy group or a phenyloxy group having 1 to 5 substituents, respectively. , The substituent is nitro (-NO ₂ ), fluoride (F), chloride (Cl), bromide (Br), methyl, ethyl, propyl or butyl.

[Formula 6]

[Formula 7]

[Formula 8]

In Formula 8, R ⁸ and R ⁹ are each hydrogen and a C ₁ to C ₂₀ alkyl group, a phenyl group, or a phenyl group having 1 to 5 substituents, and the substituents are nitro (-NO ₂ ), fluoride ( F), chloride (Cl), bromide (Br), methyl, ethyl, propyl or butyl.

Hereinafter, the present invention will be described in more detail.

The catalyst for hydroformylation of the present invention is an imidazolyylidene-based metal compound represented by the following Chemical Formula 1 [(L ¹ ) _x (L ² ) _y (L ³ ) _z (1-R ¹ , 3-R ² , 4 -R ³ , 5-R ⁴ -imidazol-2-ylidene) Metal (I)].

[Formula 1]

In Chemical Formula 1,

M is a transition metal,

R ¹ and R ² are each an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, or a phenyl group to which 1 to 5 substituents are attached, and the substituents are nitro (-NO ₂ ), fluoride (F), chloride (Cl) , Bromide (Br), methyl, ethyl, propyl or butyl.

R ³ and R ⁴ each represent a hydrogen, a halogen, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group,

L ¹ , L ² and L ³ are each hydrogen, CO, or acetylacetonato,

x, y and z are each an integer from 0 to 4, except where x, y and z are all zeros.

Preferred examples of the imidazolylidene-based metal compound represented by Formula 1 include acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl Acetylacetonato Carbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium).

The present invention is to provide an imidazolyylidene-based metal compound of Formula 1, which is a novel substance in which imidazolyydene is coordinated without halogen, and is also applied to the hydroformylation reaction of an olefin-based compound.

In the imidazolyylidene-based metal compound of Formula 1, the central metal M is a transition metal, preferably cobalt (Co), rhodium (Rh) or iridium (Ir), and more preferably rhodium (Rh).

In addition, R ¹ and R ² are each an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, or a phenyl group having 1 to 5 substituents attached thereto, and preferably a C ₁ -C ₂₀ alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group. Or a phenyl group having 1 to 5 substituents, more preferably methyl, ethyl, propyl, t-butyl, cyclohexyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and 2- Methyl-6-isopropylphenyl. Further, the substituent attached to the phenyl group is nitro (-NO ₂ ), fluoride (F), chloride (Cl), bromide (Br), methyl, ethyl, propyl or butyl.

R ³ and R ⁴ are each hydrogen, halogen, alkyl group, cycloalkyl group, alkoxy group, or phenyl group, preferably hydrogen, halogen, or C ₁ to C ₂₀ alkyl group, cycloalkyl group, alkoxy group, or It is a phenyl group, More preferably, it is a hydrogen, a methyl group, an ethyl group, or a phenyl group.

In addition, L ¹ and L ² and L ³ are each hydrogen, CO, or acetylacetonato. In addition, in Formula 1, x, y and z are preferably 0 to 4, except that all of x, y and z are 0. Most preferred examples of L ¹ , L ² and L ³ are L ¹ is CO, L ² is acetylacetonato, x and y are both 1 and z is 0.

The catalyst for hydroformylation reaction of the present invention can be used for the hydroformylation reaction of the olefin compound represented by the following formula (8), preferably ethene, propene, 1-butene, 1-pentene, 1-hexene, styrene Or as a catalyst for hydroformylation of olefinic compounds such as 1-octene.

[Formula 8]

In Formula 8, R ⁸ and R ⁹ are each hydrogen and a C ₁ to C ₂₀ alkyl group, a phenyl group, or a phenyl group having 1 to 5 substituents, and the substituents are nitro (-NO ₂ ), fluoride ( F), chloride (Cl), bromide (Br), methyl, ethyl, propyl or butyl.

In the imidazolyylidene-based metal compound of the present invention, a diimine compound is prepared by reacting a compound represented by Chemical Formula 2 with an amine represented by Chemical Formula 3 or an amine represented by Chemical Formula 4 in an equivalent ratio of 1: 2. Preferred examples of the amine include methylamine, ethylamine, propylamine, t-butylamine, siglohexylamine, 2,4,6-trimethylaniline, 2,6-diisopyro Pianyline (2,6-diisopropylaniline), 2-isopyrophyll-6-methylaniline (2-isopropyl-6-methylaniline) and the like can be used.

[Formula 2]

In Formula 2, R ³ and R ⁴ are each hydrogen, halogen, alkyl group, cyclo alkyl group, alkoxy group, or phenyl group.

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,

R ¹ and R ² are each an alkyl group, a cyclo alkyl group, an alkoxy group, a phenyl group, or a phenyl group to which 1 to 5 substituents are attached, and the substituents are nitro (-NO ₂ ), fluoride (F), chloride (Cl), Bromide (Br), methyl, ethyl, propyl or butyl.

The prepared diimine compound is reduced to an imine group using lithium aluminum hydride (LiAlH ₄ ) and converted to a diamine salt form by adding an acid. At this time, a preferable example of the acid may be hydrochloric acid, sulfuric acid, nitric acid or bromic acid, and more preferably hydrochloric acid.

When the diamine salt prepared above is reacted with triethyl orthoformate at high temperature, a cyclized imidazole salt is produced. The imidazole is determined depending on the kind of amine added.

When the imidazole salt prepared above is added to the organic solvent, it is present in the form of a slurry without melting. At this time, preferred examples of the organic solvent may be tetrahydrofuran (THF), diethyl ether, benzene, toluene or N, N-dimethylformamide (DMF), and more preferably anhydrous. Tetrahydrofuran can be used.

When the prepared slurry is mixed with salts such as liquid ammonia, potassium salt, sodium salt or lithium salt, the additives in the solution gradually melt to form a mixture in the slurry. At this time, it is preferable to use t-butanol potassium salt (t-BuOK), methanol potassium salt (MeOK), or ethanol potassium salt (EtOK) as the potassium salt, and methanol sodium salt (MeONa) as the sodium salt. ) Or ethanol sodium salt (EtONa) is preferable, and n-butyllithium salt (n-BuLi) or t-butyllithium salt (t-BuLi) is preferably used as the lithium salt.

The mixed form of the slurry is added to the organic solvent in which the metal (M) precursor is dissolved and heated, thereby obtaining an imidazole lylidene-based metal compound represented by Chemical Formula 1. Preferred examples of the metal precursor include Rh (AcAc) (CO) ₂ , Rh (AcAc) (CO) (TPP), HRh (CO) (TPP) ₃ , to which no halogen elements (Cl, Br, I, etc.) are attached. Ir (AcAc) (CO) ₂ , HIr (CO) (TPP) ₃ and the like can be used. At this time, a preferable example of the organic solvent may be toluene, benzene, tetrahydrofuran (THF), diethyl ether, and the like, more preferably Anhydrous toluene can be used.

The obtained compound of formula 1 may be purified using a solvent such as hexane, methanol, ethanol, ether, chloroform, dichloromethane.

The catalyst for the hydroformylation reaction prepared by the above method is a synthetic gas (CO / H ₂ ) by adding a ligand compound represented by the following Chemical Formula 5 or Eicosyl Phobane (EP), which is a mixture of the following Chemical Formulas 6 and 7 By the hydroformylation reaction for the olefin in the presence of the form, it is in the form of producing an aldehyde having an increased carbon number by one.

[Formula 5]

In Formula 5, R ⁵ , R ⁶ , and R ⁷ are each a C ₁ to C ₂₀ alkyl group, a cyclo alkyl group, an alkoxy group, a phenyl group, a phenyloxy group, or a phenyl group or phenyloxy group having 1 to 5 substituents Wherein the substituent is nitro (-NO ₂ ), fluoride (F), chloride (Cl), bromide (Br), methyl, ethyl, propyl or butyl.

[Formula 6]

[Formula 7]

The hydroformylation process is shown in Scheme 1 below.

Scheme 1

For the hydroformylation reaction, first, the catalyst and ligand for the hydroformylation reaction are dissolved in a solvent such as benzene, toluene, ethanol, pentanol, octanol, texanol, butylaldehyde, or pentylaldehyde, and a catalyst / ligand mixture solution. To prepare. As examples of the ligand, preferably triphenylphosphine, tributylphosphine, triphenyl phosphite, cyclohexylphosphine, or icosyl phoban can be used.

A mixture gas of the olefin compound, carbon monoxide, and hydrogen represented by the following Chemical Formula 8 together with the catalyst / ligand mixture solution may be injected into the reactor, heated, and pressurized while stirring to proceed the hydroformylation reaction.

[Formula 8]

In Formula 8, R ⁸ and R ⁹ are each hydrogen and a C ₁ to C ₂₀ alkyl group, a phenyl group, or a phenyl group having 1 to 5 substituents, and the substituents are nitro (-NO ₂ ), fluoride ( F), chloride (Cl), bromide (Br), methyl, ethyl, propyl or butyl.

Preferred examples of the olefin compound may be ethene, propene, 1-butene, 1-pentene, 1-hexene, styrene, or 1-octene.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

Example 1 Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium {Acetylacetonato Carbonyl (1,3 -bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium}

Synthesis of acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium is shown in Scheme 2 below.

Scheme 2

1.Synthesis of glyoxal-bis- (2,4,6-trimethylphenyl) imine {Glyoxal-bis- (2,4,6-trimethylphenyl) imine} ( 1a )

To the round bottom flask, glyoxal (glyoxal, 40%, 5 g, 43.59 mmol) and 2,4,6-trimethylaniline (2,4,6-trimethylaniline, 13 mL, 89.53 mmol) were added, followed by 50 mL of methanol. Added. The reaction solution was refluxed overnight (about 15 hours) and then stored in the refrigerator. The yellow crystalline precipitate produced after the above process was filtered off, washed with a small amount of cold methanol and dried in vacuo. (Yield 79%).

The obtained precipitate ( 1a ) was analyzed by hydrogen atom nuclear magnetic resonance spectrum ( ¹ H NMR (CDCl ₃ )), and the main peak value was ¹ H NMR (CDCl ₃ ): δ 2.19 (s, 12H, Ar- CH ₃ (m)), 2.32 (m, 6H, Ar—CH ₃ (p)), 6.94 (s, 4H, Ar—H), 8.13 (s, 2H, N = CH—).

2.Synthesis of N-N'-bis- (2,4,6-trimethylphenylamino) ethanedichloride {N, N'-Bis- (2,4,6-trimethylphenylamino) ethane Dichloride} ( 2a )

The synthesized diimine compound 1a (5 g, 17.10 mmol) was dissolved in diethyl ether purified under a nitrogen atmosphere and stirred vigorously. The reaction solution was cooled to about 0 ° C., and lithium aluminum hydride (LiAlH ₄ , 1.8 g, 45.06 mmol) was added in small portions with vigorous stirring, followed by stirring at room temperature until the yellow color of the solution disappeared. Residual LiAlH ₄ was removed, the product was dissolved in dichloromethane, and excess ethyl acetate was added. While stirring the solution, a small amount of concentrated hydrochloric acid (conc. HCl) was added to form a precipitate, and the resulting precipitate was filtered off and dried in vacuo. (Yield 74%).

The obtained precipitate ( 2a ) was analyzed by hydrogen atom nuclear magnetic resonance spectrum ( ¹ H NMR (DMSO-d ₆ )), and the main peak value was ¹ H NMR (DMSO-d ₆ ): δ 2.62 (s, 6H, Ar-CH ₃ (p)), 2.81 (s, 12H, Ar-CH ₃ (o)), 3.93 (s, 4H, -NCH _2- ), 7.34 (s, 4H, Ar-H), 8.95 (s, 4H, -NH _2- ).

3. Synthesis of 1,3-bis- (2,4,6-trimethylphenyl) imidazoliniumchloride {1,3-Bis- (2,4,6-trimethylphenyl) imidazolinium Chloride} ( 3a )

Compound 2a (4.7 g, 12.72 mmol) and triethyl orthoformate (25 mL, 147.30 mmol) were added to a round bottom flask. After the distillation apparatus was installed, the produced ethanol was removed while heating to 120 ℃. The reaction solution was cooled to room temperature after heating until no more ethanol was produced. The resulting precipitate was filtered and dried, dissolved in a small amount of chloroform, and recrystallized in a freezer by adding hexane. The resulting colorless solid was filtered off and dried in vacuo. (Yield 98%).

The obtained precipitate ( 3a ) was analyzed by hydrogen atom nuclear magnetic resonance spectrum ( ¹ H NMR (CD ₂ Cl ₂ )), and the main peak value was ¹ H NMR (CD ₂ Cl ₂ ): δ 2.32 (s, 6H, Ar-CH ₃ (p)), 2.38 (s, 12H, Ar-CH ₃ (o)), 4.43 (s, 4H, -NCH _2- ), 7.004 (s, 4H, Ar-H), 9.93 (s, 1H, -im-H).

4. Synthesis of Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium ( 5a )

The slurry was prepared by adding compound 3a (0.3 g, 0.875 mmol) to a Schlenk flask and adding 20 mL of purified tetrahydrofuran (THF). A t-butanol potassium salt (t-BuOK) (1M, 1 mL, 1 mmol) solution was added dropwise (added dropwise) to the THF slurry prepared above, followed by stirring at room temperature for 30 minutes. As the reaction proceeded, the white precipitate slowly dissolved into a pale yellow solution. Compound 4a was subjected to the next reaction without separation and purification. The THF solution in which Compound 4a was dissolved was added dropwise with vigorous stirring at room temperature to a toluene solution in which acetylacetonato-dicarbonyldium (Rh (AcAc) (CO) ₂ ) (0.22 g, 0.853 mmol) was dissolved. The reaction solution was stirred at 80 ° C. for 1 hour. Over time, the reaction solution turned dark brown. After cooling the reaction solution to room temperature, the solvent was removed under reduced pressure. The precipitate ( 5a ) produced in the above process was washed several times with methanol under a nitrogen atmosphere and dried in vacuo (yield 74%).

Analysis of the obtained precipitate ( 5a ) was measured by hydrogen atomic nuclear resonance spectrum ( ¹ H-NMR (CD ₂ Cl ₂ )) and carbon atom nuclear magnetic resonance spectrum ( ¹³ C-NMR (CD ₂ Cl ₂ )). , Main peak values are ¹ H NMR (CD ₂ Cl ₂ ): δ 1.69 (d, 6H, AcAc-CH ₃ ), 2.23 (s, 6H, Ar-CH ₃ (p)), 2.28 (s, 12H, Ar -CH ₃ (o)), 3.85 (s, 4H, -NCH _2- ), 5.12 (s, 1H, AcAc-H), 6.89 (s, 4H, Ar-H), and ¹³ C NMR (CD ₂ Cl ₂ ): δ 18.45, 21.18, 26.55, 27.66, 51.25, 129.53, 136.92, 137.03, 138.13, 186.05 (d, CO, J _(Rh-CO) 182 Hz), 190.91 (d, NCN, J _(Rh-C) 82 Hz). In addition, ESI mass spectrometry was performed on the obtained precipitate to obtain m / z 536.9 (M) and 507.1 (M-CO-1) values.

Example 2 Acetylacetonatocarbonyl (1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium {Acetylacetonato Carbonyl (1,3 -bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium}

Synthesis of acetylacetonatocarbonyl (1,3-bis (2,6-diisopropylphenyl) -4,5-dihydro imidazole-2-ylidene) rhodium is shown in Scheme 3 below.

Scheme 3

1.Synthesis of Glyoxal-bis- (2,6-diisopropylphenyl) imine {Glyoxal-bis- (2,6-diisopropylphenyl) imine} ( 1b )

Glyoxal-bis- (2,6-diisopropyl) in the same manner as in Example 1. 1, except that 2,6-diisopropylaniline (2,6-diisopropylaniline, 18 mL, 87.80 mmol) was used. Phenyl) imine ( 1b ) was synthesized. (Yield 84%).

The obtained precipitate ( 1b ) was analyzed by hydrogen atom nuclear magnetic resonance spectrum ( ¹ H NMR (CDCl ₃ )), and the main peak value was ¹ H NMR (CDCl ₃ ): δ 1.24 (d, 24H, -CH (CH ₃ ) ₂ ), 2.97 (m, 4H, -CH (CH ₃ ) ₂ ), 7.21 (m, 6H, Ar-H), 8.14 (s, 2H, = CH-).

2.Synthesis of N, N'-bis- (2,6-diisopropylphenylamino) ethane dichloride {N, N'-Bis- (2,6-diisopropylphenylamino) ethane Dichloride} ( 2b )

N, N'-bis- (2,6-diisopropylphenylamino) ethane dichloride in the same manner as in Example 1 2. except that the synthesized diimine compound 1b (5g, 13.27 mmol) was used. ( 2b ) was synthesized (yield 94%).

The obtained precipitate ( 2b ) was analyzed by hydrogen atom nuclear magnetic resonance spectrum ( ¹ H NMR (DMSO-d ₆ )), and the main peak value was ¹ H NMR (DMSO-d ₆ ): δ ■ 2.16 (d , 24H, -CH (CH ₃ ) ₂ ), 3.35 (m, 4H, -CH (CH ₃ ) ₂ ), 3.47 (s, 4H, -NCH _2- ), 7.26 (s, 6H, Ar-H), 8.68 (bs, 4H, -NH _2- ).

3. Synthesis of 1,3-bis- (2,6-diisopropylphenyl) imidazolinium chloride {1,3-Bis- (2,6-diisopropylphenyl) imidazolinium Chloride} ( 3b )

1,3-bis- (2,6-diisopropylphenyl) imidazolinium chloride (in the same manner as in Example 1 except 3, except that Compound 2b (5.0 g, 11.02 mmol) was used. 3b ) was synthesized (yield 100%).

Analysis of the obtained precipitate ( 3b ) was measured by the hydrogen atom nuclear magnetic resonance spectrum ( ¹ H NMR (CD ₂ Cl ₂ )), the main peak value is ¹ H NMR (CD ₂ Cl ₂ ): δ 1.34 (dd, 24H, -CH (CH ₃ ) ₂ ), 2.99 (m, 4H, -CH (CH ₃ ) ₂ ), 4.52 (s, 4H, -NCH _2- ), 7.30-7.50 (m, 6H, Ar-H) , 10.22 (s, 1H, im-H).

4. Synthesis of acetylacetonatocarbonyl (1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium ( 5b )

The synthesized compound 3b (0.3 g, 0.701 mmol) was added to a Schlenk flask and 20 mL of purified THF was added to prepare a slurry. To the THF slurry prepared above, a solution of t-butanol potassium salt (t-BuOK) (1M, 0.9 mL, 0.9 mmol) was added dropwise (dropwise added), followed by stirring at room temperature for 30 minutes. As the reaction proceeded, the slurry solution slowly turned brown. This formed compound 4b . Compound 4b was applied to the next reaction as it was without separation and purification. The THF solution in which Compound 4b was dissolved was added dropwise to the toluene solution in which Rh (AcAc) (CO) ₂ (0.16 g, 0.620 mmol) was dissolved at room temperature. The reaction solution was stirred at 80 degrees for 1 hour. Over time, the reaction solution turned dark brown. After cooling the reaction solution to room temperature, the solvent was removed under reduced pressure. The resulting precipitate was extracted with nucleic acid filled with nitrogen and then stored in a freezer to form a precipitate ( 5b ). The resulting precipitate was filtered off and dried in vacuo (15% yield).

The obtained precipitate ( 5b ) was analyzed by hydrogen atom nuclear magnetic resonance spectrum ( ¹ H NMR (CDCl ₃ )), and the main peak value was ¹ H NMR (CDCl ₃ ): δ 1.22 (dd, 23H, -CH (CH ₃ ) ₂ ), 1.72 (d, 6H, acac-CH ₃ ), 3.32 (m, 4H, -CH (CH ₃ ) ₃ ), 3.92 (s, 4H, -NCH _2- ), 5.11 (s, 1H, acac-H), 7.15-7.32 (m, 6H, Ar-H).

[Examples 3 to 10] Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazole-2-ylidene) rhodium catalyst and TPP ligand Hydroformylation of Used Propene

1. Preparation of Catalyst Solution

0.523 g of acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazole-2-ylidene) rhodium synthesized in Example 1 and hexadecane 5 mL was dissolved in toluene to a total volume of 250 mL.

2. Preparation of Ligand Solution

(1) It was dissolved in toluene so that the concentration of triphenylphosphine (TPP) was 39.3 mM so that the total volume was 50 mL. Hereinafter, the prepared solution is called TPP solution (I).

(2) It was dissolved in toluene so that the concentration of triphenylphosphine (TPP) was 780.0 mM so that the total volume was 50 mL. Hereinafter, the prepared solution is called TPP solution (II).

3. Hydroformylation of Propene

The hydroformylation reaction of the present invention was carried out using a high throughput screen unit (HTS) manufactured by Auto Clave. The HTS is equipped with 10 small reactors capable of reacting under the same conditions at high pressure and each reactor has a volume of 20 mL.

In the reactor of the HTS, each reactor corresponding to Examples 3 to 10 was previously determined, and 5 mL of each of the prepared catalyst solutions was added thereto, and the TPP solution (I) prepared above was added to the reactors of Examples 3 to 6, respectively. 0.5, 1.5, 2.5, and 5 mL each were added, and 0.625, 1.25, 2.5, and 5 mL of TTP solution (II) were added to the reactors of Examples 7 to 10, respectively. Hydroformylation of propene was carried out with the molar ratio of ligand / catalyst in the reactor being 1, 3, 5, 10, 25, 50, 100, 200, respectively. At this time, toluene solvent was added if necessary so that the volume of each reaction solution was 10 mL.

The reaction was carried out in the presence of propene: CO: H ₂ = 1: 1: 1 mixed gas, the pressure in the reactor was 6 bar, the volume of each reaction solution was 10 mL. Each reaction proceeded at 100 ° C. for 2.5 hours.

The content of the catalyst and ligand charged in the reaction is described in detail in Table 1 below.

[Examples 11 to 18] Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazole-2-ylidene) rhodium catalyst and TPPI ligand Hydroformylation of Used Propene

1. Preparation of Catalyst Solution

Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium catalyst in the same manner as described in Examples 3 to 10 The solution was prepared.

2. Preparation of Ligand Solution

(1) Triphenylphosphite (TPPI) was dissolved in toluene so that the concentration was 39.3 mM, and the total volume was 50 mL. Hereinafter, the prepared solution is referred to as TPPI solution (I).

(2) Triphenyl phosphite (TPPI) was dissolved in toluene so that the concentration was 780.0 mM, and the total volume was 50 mL. Hereinafter, the prepared solution is referred to as TPPI solution (II).

3. Hydroformylation of Propene

Except for using the TPPI solution as a ligand solution, the hydroformylation reaction of propene was carried out in the same conditions as in Examples 3 to 10 in the content shown in Table 1 below.

[Examples 19 to 22] Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazole-2-ylidene) rhodium catalyst and EP ligand Hydroformylation of Used Propene

1. Preparation of catalyst solution

Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium catalyst in the same manner as described in Examples 3 to 10 The solution was prepared.

2. Preparation of Ligand Solution

It was dissolved in toluene so that the concentration of icosyl phoban was 39.3 mM so that the total volume was 50 mL. Hereinafter, the prepared solution is referred to as an EP solution.

3. Hydroformylation of Propene

The hydroformylation reaction of propene was carried out in the same conditions as in Examples 3 to 6 except that the EP solution was used as the ligand solution.

Comparative Example 1 Hydroformylation of Propene with Acetyl Acetonatocarbonyltriphenylphosphinedium (Rh (AcAc) (CO) (TPP)) Catalyst and TPP Ligand

1. Preparation of Ligand / Catalyst Solution

0.48 g of Rh (AcAc) (CO) (TPP), a catalyst for hydroformylation reaction, 25.58 g of triphenylphosphine (TPP), a ligand, and 5 mL of hexadecane were dissolved in toluene to give a total volume of 250 mL. . Hereinafter, the prepared solution is called a TPP / Rh (AcAc) (CO) (TPP) solution. The molar ratio of the ligand / catalyst was set to 100 as described in Table 1 below.

2. Hydroformylation of Propene

Hydroformylation of propene was performed in the same manner as in Examples 3 to 10, except that 10 mL of the ligand / catalyst solution was used.

Comparative Example 2 Hydroformylation of Propene with Acetyl Acetonatocarbonyltriphenylphosphindium (Rh (AcAc) (CO) (TPP)) Catalyst and TPPI Ligand

1. Preparation of Ligand / Catalyst Solution

0.48 g of Rh (AcAc) (CO) (TPP), a catalyst for hydroformylation reaction, 30.26 g of triphenylphosphite (TPPI), a ligand, and 5 mL of hexadecane were dissolved in toluene to give a total volume of 250 mL. . Hereinafter, the prepared solution is referred to as a TPPI / Rh (AcAc) (CO) (TPP) solution. The molar ratio of the ligand / catalyst was set to 100 as described in Table 1 below.

2. Hydroformylation of Propene

Hydroformylation of propene was carried out in the same manner as in Examples 11 to 18 except that 10 mL of the ligand / catalyst solution was used.

[Comparative Example 3] Hydroformylation of Propene with Acetyl Acetonatocarbonyltriphenylphosphinedium (Rh (AcAc) (CO) (TPP)) Catalyst and EP Ligand

1. Preparation of Ligand / Catalyst Solution

0.48 g of Rh (AcAc) (CO) (TPP), a catalyst for hydroformylation reaction, 2.06 g of ligand Aicosylfoban, and 5 mL of hexadecane were dissolved in toluene to give a total volume of 250 mL. Hereinafter, the prepared solution is referred to as EP / Rh (AcAc) (CO) (TPP) solution. The molar ratio of the ligand / catalyst was set to 5 as shown in Table 1 below.

2. Hydroformylation of Propene

Hydroformylation of propene was carried out in the same manner as in Examples 19 to 22, except that 10 mL of the ligand / catalyst solution was used.

TABLE 1

division Catalyst solution Ligand Solution (Dose) Ligand / Catalyst (mol / mol) Example 3 Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium catalyst solution (5 mL) TPP solution (I) (0.5 mL) One Example 4 TPP solution (I) (1.5 mL) 3 Example 5 TPP solution (I) (2.5 mL) 5 Example 6 TPP solution (I) (5 mL) 10 Example 7 TPP solution (II) (0.625 mL) 25 Example 8 TPP solution (II) (1.25 mL) 50 Example 9 TPP solution (II) (2.5 mL) 100 Example 10 TPP solution (II) (5 mL) 200 Comparative Example 1 TPP / Rh (AcAc) (CO) (TPP) Solution 100 Example 11 Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium catalyst solution (5 mL) TPPI Solution (I) (0.5 mL) One Example 12 TPPI Solution (I) (1.5 mL) 3 Example 13 TPPI Solution (I) (2.5 mL) 5 Example 14 TPPI Solution (I) (5 mL) 10 Example 15 TPPI Solution (II) (0.625 mL) 25 Example 16 TPPI Solution (II) (1.25 mL) 50 Example 17 TPPI Solution (II) (2.5 mL) 100 Example 18 TPPI Solution (II) (5 mL) 200 Comparative Example 2 TPPI / Rh (AcAc) (CO) (TPP) Solution 100 Example 19 Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene) rhodium catalyst solution (5 mL) EP solution (0.5 mL) One Example 20 EP solution (1.5 mL) 3 Example 21 EP solution (2.5 mL) 5 Example 22 EP solution (5 mL) 10 Comparative Example 3 EP / Rh (AcAc) (CO) (TPP) solution  5

In addition, the hydroformylation reaction products obtained in Examples 3 to 22 and Comparative Examples 1 to 3 were analyzed by gas chromatography (GC: Gas Chromatography) to generate butyl aldehyde, and catalytic activity and N / I. The values and the like are shown in Table 2 together.

In Table 2, N / I value is the amount of normal-butylaldehyde (n-Butyraldehyde) generated in the reaction divided by the amount of iso-butylaldehyde (i-Butyraldehyde), and the amount of BAL produced is a hydroformylation reaction. After completion of the analysis of the amount of butyl aldehyde produced by GC as a percentage value, the catalytic activity is the value divided by the concentration and time of the catalyst using the total amount of normal aldehyde and isoaldehyde produced in the reaction. In this case, the unit of catalytic activity is expressed as Kg _(BAL) / mol _(Rh) / h.

TABLE 2

division N / I value BAL production amount (%, GC) Catalytic Activity Kg _(BAL) / mol _(Rh) / h Example 3 1.3 4.65 10.23 Example 4 1.5 8.25 18.17 Example 5 1.6 9.32 20.52 Example 6 1.85 9.03 19.88 Example 7 2.25 7.88 20.33 Example 8 3.05 7.29 18.79 Example 9 4.65 6.13 15.81 Example 10 5.6 5.06 13.05 Comparative Example 1 4.6 7.56 16.64 Example 11 1.2 8.16 17.64 Example 12 1.4 11.56 24.99 Example 13 1.16 10.48 22.65 Example 14 2.15 8.96 19.37 Example 15 2.65 5.89 14.68 Example 16 2.85 3.82 9.52 Example 17 3.1 2.75 6.84 Example 18 3.2 2.01 4.99 Comparative Example 2  3.2 2.49 5.49 Example 19 1.05 8.77 21.63 Example 20 0.35 5.27 13.00 Example 21 0.8 6.68 16.47 Example 22 1.25 6.01 14.83 Comparative Example 3 1.3 5.59 12.31

Catalyst of Acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazole-2-ylidene) rhodium catalyst used in Examples 3 to 22 above Looking at the activity and N / I selectivity, as shown in Table 1 and Table 2, when TPP is applied as a ligand, the catalytic activity is Rh (AcAc) (CO) (TPP) / TTP at a TPP concentration of 100 equivalent or less It is higher and shows the best value at 5 equivalents. In addition, N / I selectivity gradually increases as the concentration of the TTP ligand increases, showing a value (4.60) that is almost equal to Rh (AcAc) (CO) (TPP) / TPP at 4.65 at 100 equivalents.

In addition, when the ligand is changed to TPPI, which is known to bind weakly to rhodium metal than TPP, as shown in Table 2, it is equivalent to 1.5 times higher than Rh (AcAc) (CO) (TPP) / TPP at low ligand concentration. It showed high catalytic activity. At this time, N / I selectivity increased rapidly with increasing ligand concentration, and showed almost the same value of about 3 from the condition that the ligand was 50 equivalent or more.

In addition, in the case of applying EP having a higher electron density of phosphine as a ligand as compared to TPP, as shown in Table 3, when the equivalent amount of EP was present, it showed the highest catalytic activity. N / I selectivity at this time showed a very high selectivity to iso-butylaldehyde with a value of about 1.

The hydroformylation catalyst of the present invention does not contain halogen, has excellent activity, high selectivity of iso-aldehyde and easy synthesis, and is suitable for use in hydroformylation of olefinic compounds.

Claims (15)

Imidazolylidene-based metal compound represented by the following formula (1): [Formula 1]

In Chemical Formula 1, M is a transition metal, R ¹ and R ² are each an alkyl group, a cyclo alkyl group, an alkoxy group, a phenyl group, or a phenyl group to which 1 to 5 substituents are attached, and the substituents are nitro (-NO ₂ ), fluoride (F), chloride (Cl), Bromide (Br), methyl, ethyl, propyl or butyl, R ³ and R ⁴ are each hydrogen, a halogen, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group, L ¹ , L ² and L ³ are each hydrogen, CO, or Acetylacetonato, x, y and z are each an integer of 0 to 4 (except where x, y and z are all zeros). The imidazolyylidene-based metal compound of claim 1, wherein R ¹ and R ² are 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, or 2-methyl-6-isopropylphenyl, respectively. The imidazolilidene-based metal compound of claim 1, wherein each of R ³ and R ⁴ is hydrogen, a methyl group, an ethyl group, or a phenyl group. The imidazolyylidene-based metal compound of claim 1, wherein M is cobalt (Co), rhodium (Rh), or iridium (Ir). According to claim 1, wherein the compound represented by Formula 1 is acetylacetonatocarbonyl (1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidene ) Imidazolidene metal compound which is rhodium or acetylacetonatocarbonyl (1, 3-bis (2, 6- diisopropylphenyl) -4, 5- dihydroimidazole- 2-ylidene) rhodium. The catalyst for hydroformylation reaction containing the imidazole- ylidene-type metal compound of any one of Claims 1-5. The catalyst for hydroformylation of claim 6, wherein the catalyst for hydroformylation is used for hydroformylation of an olefin compound represented by the following formula (8). [Formula 8]

In Formula 8, R ⁸ and R ⁹ are each hydrogen and a C ₁ to C ₂₀ alkyl group, a phenyl group, or a phenyl group having 1 to 5 substituents, and the substituents are nitro (-NO ₂ ), fluoride ( F), chloride (Cl), bromide (Br), methyl, ethyl, propyl or butyl. The hydroformylation reaction of claim 7, wherein the olefin compound is at least one compound selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, styrene, and 1-octene. catalyst. a) i) 1 equivalent of the compound represented by Formula 2; And   ii) reacting 2 equivalents of an amine represented by Formula 3, an amine represented by Formula 4, or a mixture thereof to synthesize a dimine compound; b) reducing the diimine compound and adding an acid to prepare a diamine salt; c) reacting the diamine salt with triethyl orthoformate to prepare a cyclized imidazole salt; d) adding the imidazole salt to an organic solvent and preparing a slurry by adding at least one substance selected from the group consisting of liquid ammonia, sodium salt, potassium salt, and lithium salt; And e) adding the prepared slurry to a solution in which the metal precursor is dissolved and heating Method for producing an imidazolyylidene-based metal compound represented by the formula (1) comprising: [Formula 1]

In Chemical Formula 1, M is a transition metal, R ¹ and R ² are each an alkyl group, a cyclo alkyl group, an alkoxy group, a phenyl group, or a phenyl group to which 1 to 5 substituents are attached, and the substituents are nitro (-NO ₂ ), fluoride (F), chloride (Cl), Bromide (Br), methyl, ethyl, propyl or butyl, R ³ and R ⁴ are each hydrogen, a halogen, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group, L ¹ , L ² and L ³ are each hydrogen, CO, or Acetylacetonato, x, y and z are each an integer from 0 to 4, except where x, y and z are all zero; [Formula 2]

In Formula 2, R ³ and R ⁴ are each hydrogen, a halogen, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group; [Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4, R ¹ and R ² are each an alkyl group, a cyclo alkyl group, an alkoxy group, a phenyl group, or a phenyl group to which 1 to 5 substituents are attached, and the substituents are nitro (-NO ₂ ), fluoride (F), chloride (Cl), Bromide (Br), methyl, ethyl, propyl or butyl. 10. The compound of claim 9, wherein R ¹ and R ² are each methyl, ethyl, propyl, t-butyl, cyclohexyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and 2-methyl- A method for producing an imidazolyylidene-based metal compound which is 6-isopropylphenyl. The method of claim 9, wherein R ³ and R ⁴ are each hydrogen, methyl, ethyl, or phenyl. The method according to claim 9, wherein M is cobalt (Co), rhodium (Rh), or iridium (Ir). a) dissolving the compound represented by Chemical Formula 1 in a solvent to prepare a catalyst solution; b) preparing a ligand solution by dissolving a ligand compound represented by Formula 5 or a mixture of Formula 6 and Formula 7 in a solvent; And c) mixing the catalyst solution with the ligand solution, and then heating and pressurizing the mixture with a mixed gas of an olefin compound, carbon monoxide, and hydrogen represented by the following formula (8): Hydroformylation reaction method comprising: [Formula 1]

In Chemical Formula 1, M is a transition metal, R ¹ and R ² are each an alkyl group, a cyclo alkyl group, an alkoxy group, a phenyl group, or a phenyl group to which 1 to 5 substituents are attached, and the substituents are nitro (-NO ₂ ), fluoride (F), chloride (Cl), Bromide (Br), methyl, ethyl, propyl or butyl, R ³ and R ⁴ are each hydrogen, a halogen, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group, L ¹ , L ² and L ³ are each hydrogen, CO, or Acetylacetonato, x, y and z are each an integer from 0 to 4, except where x, y and z are all zero; [Formula 5]

In Formula 5, R ⁵ , R ⁶ , and R ⁷ are each a C ₁ to C ₂₀ alkyl group, a cyclo alkyl group, an alkoxy group, a phenyl group, a phenyloxy group or a phenyloxy group having 1 to 5 substituents, respectively. , The substituent is nitro (-NO ₂ ), fluoride (F), chloride (Cl), bromide (Br), methyl, ethyl, propyl or butyl; [Formula 6]

[Formula 7]

[Formula 8]

In Formula 8, R ⁸ and R ⁹ are each hydrogen and a C ₁ to C ₂₀ alkyl group, a phenyl group, or a phenyl group having 1 to 5 substituents, and the substituents are nitro (-NO ₂ ), fluoride ( F), chloride (Cl), bromide (Br), methyl, ethyl, propyl or butyl. The method of claim 13, wherein the olefin compound is at least one compound selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, styrene, and 1-octene. . The method of hydroformylation of claim 13, wherein the ligand is at least one selected from the group consisting of triphenylphosphine, tributylphosphine, triphenyl phosphite, tricyclohexylphosphine, and icosylfoban.