KR101418829B1 - Catalyst for producing 1,3-diphenyl-2-butene derivatives - Google Patents

Abstract

The present invention relates to a catalyst for preparing 1,3-diphenyl-2-butene type compound represented by the following formula 1. The catalyst has a selective C-C bond forming specificity, and illustrates high transformation ratio to a target compound with high selectivity. Thus, the catalyst of the present invention can be favorably used in a process for preparing 1,3-diphenyl-2-butene type compound.

Description

Catalyst for producing 1,3-diphenyl-2-butene derivatives Catalyst for producing 1,3-diphenyl-

The present invention relates to a catalyst for the production of a 1,3-diphenyl-2-butene compound represented by the following general formula (1), more specifically to a catalyst for the production of a 1,3- And a catalyst for the production of 1,3-diphenyl-2-butene compounds having an efficiency.

 [Chemical Formula 1]

Oligomers of olefins are used in various applications. In particular, dimers (dimers) of low molecular weight olefins (e.g., propylene, n-butene, isobutene, pentene) . Thus, simple and effective processing methods for the dimerization and oligomerization of olefins have been studied in order to prepare dimers of olefins (dimers). Particularly, a dimerization reaction process using a catalyst system has been intensively studied. The catalytic system is a very important research field in the chemical industry due to the significance of the development of a new CC bond formation reaction as well as the industrial importance of the process for producing an- It is considered to be a part.

For example, some metal complexes such as Ziegler-Natta type Ti catalysts and Ni catalysts have been developed and usefully used in the ethylene dimerization process. In addition, for the various organic reactions, the development of various single CC bond formation reactions has been extensively studied using the above and mechanically similar catalysts. For example, co-dimerization and hetero-dimerized Pd catalysts of various Ni, Co and ethylene or styrene have been developed and such new catalyst systems have been used to produce commercial nonsteroidal anti-inflammatory agents (NSAIDs) such as ibuprofen In the selective CC bond formation process.

In addition, up to now, most of the acid catalysts have been used for the oligomerization reaction involving the dimerization of olefins. Examples of the acid catalysts include sulfuric acid, hydrogen fluoride, phosphoric acid, aluminum chloride and boron fluoride or amorphous or crystalline aluminosilicates, Solid acid such as an ion exchange resin, a mixed oxide, and an acid with a carrier can be used as an example, and a solid phosphoric acid catalyst is widely used.

For example, Japanese Patent Publication (A) No. 8-29251 discloses a propylene oligomerization method using a solid phosphoric acid catalyst produced at a calcination temperature of 100 ° C or higher, and Japanese Patent Publication No. 7-59301 discloses an amorphous mixture of phosphoric acid and a siliceous raw material (250 ° C to 450 ° C) and a catalyst having a water vapor concentration of 3 mol% to 50 mol% (a catalyst composed of silicon orthophosphate and silicon pyrophosphate) is used to oligomerize propylene.

However, since the above catalysts do not primarily aim at dimerization of olefins, production of by-products can not be avoided, and thus there is an inadequate problem in the process for the selective dimerization reaction of olefins.

Therefore, for the selective dimerization reaction of olefins, it is necessary to develop a catalyst having simple and selective dimerization reaction characteristics and exhibiting high catalytic activity.

Under the above background, the present inventors have been studying a catalyst for an effective dimerization reaction of olefins, particularly styrene, in which a cationic (meth) acrylate compound synthesized by mixing a phosphine compound and a metal triflate (metal OTf) Palladium-based catalyst exhibits excellent selectivity and shows a conversion rate of 90% or more with a single 1,3-diphenyl-2-butene compound. Thus, the present invention has been completed.

An object of the present invention is to provide a palladium-based catalyst having high efficiency and excellent selectivity for producing 1,3-diphenyl-2-butene compound through a simpler method.

In order to solve the above problems, the present invention provides a catalyst for the production of a 1,3-diphenyl-2-butene compound represented by the following general formula (1).

 [Chemical Formula 1]

Wherein, X is OTf, BF ₄ or OCl _4, R is phenyl substituted by unsubstituted or C _{1 -4} alkyl Beach.

Preferably, X is OTf and R is phenyl.

The catalyst for preparing the 1,3-diphenyl-2-butene compound of the present invention can be synthesized by the method shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

As shown in Reaction Scheme 1, the catalyst for preparing a dimer of the present invention is obtained by synthesizing an intermediate represented by Formula 4 by reacting a [(Allyl) PdCl] ₂ compound represented by Formula 3 with a ligand material (PR ₃ ) , And a counter anion (X) with an intermediate represented by the above formula (4). In the above Reaction Scheme 1, R and X are as described above.

Preferably, the ligand material PR ₃ may be triphenylphosphine or tri (o-tolyl) phosphine, and the counter anion X may be AgOTf, AgBF ₄ or AgOCl be _four days.

The 1,3-diphenyl-2-butene compound is preferably synthesized through a dimerization reaction of a compound represented by the following general formula (2).

(2)

Wherein, R ₁ is hydrogen or C _{1 -4} alkyl, R ₂ is hydrogen, halogen, C _{1 -4} alkoxy, or C _{1 -4} alkyl.

Preferred examples of the compound represented by the formula (2) are as follows.

1) styrene,

2) 4-fluorostyrene,

3) 4-bromostyrene,

4) 4-acetoxystyrene,

5) 4-methylstyrene,

6)? -Methylstyrene,

7) 4- t butylstyrene,

8) 4-Trifluoromethylstyrene,

9) 2-fluorostyrene,

10) 3-bromostyrene, and

11) 4-chlorostyrene.

The present invention also relates to a process for preparing 1,3-diphenyl-2-butene compounds represented by the following general formula (3) by reacting a compound represented by the following general formula (2) Diphenyl-2-butene compound.

(2)

(3)

Wherein R ₁ and R ₂ are as defined above.

According to one embodiment of the present invention, it has been found that, as a result of the dimerization reaction of various compounds represented by Formula 2 using the catalyst represented by Formula 1, Respectively. This means that the catalyst of the present invention not only has excellent reaction selectivity but also has high catalytic activity properties.

The catalyst for the production of 1,3-diphenyl-2-butene compound according to the present invention has selective C-C bond formation properties and thus has an effect of exhibiting a high conversion ratio to a target compound with excellent selectivity.

Accordingly, the catalyst of the present invention can be usefully used in a process for producing a 1,3-diphenyl-2-butene compound.

Hereinafter, the present invention will be described in more detail with reference to the following examples and experimental examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example  1 to 4: Preparation of Palladium-Based Catalyst for Dimerization Reaction

0.0050 mmol of [(allyl) PdCl ₂ ], 0.011 mmol of the ligand material and 0.011 mmol of the counter anion material were dissolved in 3 ml of dichloromethane (CH ₂ Cl ₂ ) to obtain a palladium-hydride catalyst for the dimerization reaction And used directly in the dimerization reaction experiment. Table 1 below shows the materials used in detail.

division Starting material Ligand Counter anion Example 1 [(allyl) PdCl _2] 트리henylphosphine AgOTf Example 2 tri (o-tolyl) phosphine Example 3 트리henylphosphine AgBF4 Example 4 AgOCl4

Experimental Example : Dimerization reaction

In order to confirm the dimerization reaction characteristics of the catalysts prepared in Examples 1 to 4, a dimerization reaction experiment of various styrenes was carried out using the catalyst. As a result of the dimerization reaction, the catalysts of Examples 1 to 4 exhibited excellent conversion and separation yields, but the catalyst of Example 1 exhibited the highest efficiency.

Therefore, experiments for dimerization reaction of the catalyst of Example 1 showing the highest activity in Experimental Examples 1) to 11) were shown.

At this time, 1.0 mol% of catalyst and 0.1 mmol of styrene were used in the reaction. The compound obtained through the dimerization reaction was characterized by GC / MS and NMR.

1) Dimethylation of styrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and styrene was injected one by one while stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The conversion rate was 96% and the separation yield was 94%.

¹ H NMR 隆 (300 MHz, CDCl ₃ ): 7.457.24 (m, 10H), 6.486.47 (m, 2H), 3.74-3.70 (m, 1H), 1.56-1.33 );

^{13 CNMR δ (75 MHz, CDCl} 3): 145.8, 137.8, 135.4, 128.7, 127.5, 126.4, 42.8, 21.4;

LRMS (EI): 208 (m ^< ⁺ & gt ^; ).

2) Dimerization reaction of 4-fluorostyrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and 4-fluorostyrene was added dropwise with stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The conversion was> 99% and the separation yield was 98%.

^{1 H NMR δ (300 MHz,} CDCl 3): 7.32-7.18 (m, 4H), 7.02-6.94 (m, 4H), 6.37 -6.20 (m, 2H), 3.65- 3.56 (m, 1H), 1.44- 1.42 (d, J = 6 Hz, 3 H);

^{13 C} NMR (75 MHz, CDCl ₃ ): 163.8, 163.2, 160.6, 160.0, 141.3, 133.7, 129.0, 128.6, 127.9, 127.7, 127.6, 127.5, 115.5, 115.2, 115.1, 41.8, 21.5;

LRMS (EI): 244 (M ^< ⁺ & gt ^; ).

3) Dimerization reaction of 4-bromostyrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and 4-bromostyrene was added dropwise with stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The conversion rate was> 99% and the separation yield was 99%.

^{1 H NMR δ (300 MHz,} CDCl 3): 7.46-7.10 (m, 8H), 6.32-6.31 (d, J = 3Hz, 2H), 3.62-3.55 (m, 1H), 1.44-1.42 (d, J = 6 Hz, 3H);

^{13 CNMR δ (75 MHz, CDCl} 3): 1144.3, 136.3, 135.4, 131.6, 129.1, 127.9, 127.8, 120.9, 120.1, 42.1, 21.1;

LRMS (EI): 366 (M ^< ⁺ & gt ^; ).

4) Dimerization of 4-acetoxystyrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and 4-acetoxystyrene was added dropwise with stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The conversion rate was 95% and the separation yield was 90%.

^{1 H NMR δ (300 MHz,} CDCl 3): 7.37-7.24 (m, 4H), 7.0-6.99 (m, 4H), 6.42-6.26 (m, 2H), 3.68-3.58 (m, 1H), 1.45- 1.43 (d, J = 6 Hz, 3 H);

¹³ CNMR 隆 (75 MHz, CDCl ₃ ): 169.6, 169.5, 149.7, 149.0, 143.0, 135.3, 128.1, 127.8, 127.2, 126.9, 121.8, 121.5, 121.4, 42.1, 21.2;

LRMS (EI): 324 (m ⁺ ).

5) Dimerization reaction of 4-methylenestyrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and 4-methylenestyrene was added dropwise with stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The conversion rate was> 99% and the separation yield was 99%.

^{1 H NMR δ (300 MHz,} CDCl 3): 7.25-7.04 (m, 8H), 6.40-6.23 (m, 2H), 3.63-3.54 (m, 1H), 1.45-1.42 (d, J = 6Hz, 3H );

^{13 C} NMR (75 MHz, CDCl ₃ ): 142.8, 136.6, 134.9, 129.9, 129.1, 128.4, 127.9, 127.4, 126.7, 126.5, 125.4, 42.2, 21.6;

LRMS (EI): 236 (M ^< ⁺ & gt ^; ).

6) Dimerization of α-methylstyrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and alpha -methylstyrene was added dropwise while stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The dimer of? -methylstyrene was produced in a ratio of 1: 0.8 (NMR ratio based on the hydrogen peak of the alkene) of the compound represented by the formula (a) and the compound represented by the formula (b) The conversion rate was> 99%.

[Chemical Formula 4]

^{1 HNMR δ (300 MHz, CDCl} 3): 7.51-7.31 (m, 10H), 6.28 (s, olefinic H of a, 1H), 5.29 (s, olefinic H of b, 1H), 4.93 (s, olefinic H of b, 1H), 2.98 ( s, CH 2 of b, 2H), 1.71 (s, CH 3 of b, 3H), 1.66 (s, (CH 3) 2 of b, 6H), 1.37 (s, ( _{CH 3) 2 of a, 6H} );

^{13 C} NMR (75 MHz, CDCl ₃ ): 151.6, 150.6, 149.5, 149.1, 146.8, 145.0, 142.5, 141.0, 138.9, 137.8, 136.4, 128.3, 128.2, 127.9, 126.6, 126.3, 126.0, 125.9, 117.0, 49.7 , 40.3, 40.2, 39.3, 38.8, 38.1, 31.2, 29.6, 29.1, 17.3;

LRMS (EI): 236 (M ^< ⁺ & gt ^; ).

7) Dimerization of 4-t butylstyrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and 4- t butylstyrene was added dropwise with stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The conversion and separation yields were 97%.

^{1 H NMR δ (300 MHz,} CDCl 3): 7.47-7.32 (m, 8H), 6.58-6.48 (m, 2H), 3.78-3.69 (m, 1H), 1.59-1.56 (d, J = 6Hz, 3H ), 1.44 (s, 18H);

^{13 C} NMR (75 MHz, CDCl ₃ ): 150.1, 149.0, 142.8, 135.0, 134.8, 128.2, 127.1, 126.0, 125.5, 125.4, 42.1, 34.6, 31.7, 22.8, 21.3, 14.3;

LRMS (EI): 320 (m ⁺ ).

8) Dimerization reaction of 4-trifluoromethylstyrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and 4-trifluoromethylstyrene was added dropwise with stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The conversion was 90% and the separation yield was 85%.

^{1 H NMR δ (300 MHz,} CDCl 3): 7.64-7.40 (m, 8H), 6.50-6.49 (m, 2H), 3.81-3.72 (m, 1H), 1.55-1.53 (d, J = 6Hz, 3H );

^{13 C} NMR (75 MHz, CDCl ₃ ): 149.3, 140.9, 136.9, 130.0, 129.1, 128.7, 127.8, 126.5, 126.2, 125.7, 122.6, 119.0, 42.7, 21.0;

LRMS (EI): 344 (m ⁺ ).

9) Dimerization reaction of 2-fluorostyrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and 2-fluorostyrene was added dropwise with stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The conversion was 60% and the separation yield was 58%.

^{1 HNMR δ (300 MHz, CDCl} 3): 7.43-6.99 (m, 8H), 6.64-6.43 (m, 2H), 4.04-3.94 (m, 1H), 1.48-1.46 (d, J = 6Hz, 3H) ;

¹³ CNMR 隆 (75 MHz, CDCl ₃ ): 162.3, 161.9, 136.2, 132.4, 128.5, 127.9, 127.3, 125.2, 124.3, 124.1, 121.6, 115.9, 115.5, 36.2, 20.2;

LRMS (EI): 244 (M ^< ⁺ & gt ^; ).

10) Dimerization of 3-bromostyrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and 3-bromostyrene was added dropwise with stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The conversion rate was 93% and the separation yield was 95%.

¹ H NMR 隆 (300 MHz, CDCl ₃ ): 7.58-7.20 (m, 8H), 6.39-6.38 (m, 2H), 3.70-3.61 );

^{13 C} NMR (75 MHz, CDCl ₃ ): 147.6, 139.5, 135.9, 130.4, 130.2, 130.1, 129.6, 129.1, 127.9, 126.1, 125.0, 124.9, 122.8, 122.8, 42.4, 21.0;

LRMS (EI): 364 (M ^< ⁺ & gt ^; ).

11) Dimerization of 4-chlorostyrene

The catalyst of Example 1 was placed in a three-necked flask under a nitrogen atmosphere, and 4-chlorostyrene was added dropwise with stirring. Thereafter, the mixture was stirred for 12 hours, the catalyst was removed with a short pad silica, and the solvent was evaporated to obtain the product. The conversion was 92% and the separation yield was 90%.

¹ H NMR? (300 MHz, CDCl ₃ ): 7.28-7.14 (m, 8H), 6.35-6.23 (m, 2H), 3.62-3.53 );

^{13 CNMR δ (75 MHz, CDCl} 3): 143.8, 135.9, 135.4, 132.8, 132.1, 128.8, 128.7, 127.9, 127.5, 42.0, 21.2;

LRMS (EI): 276 (m ⁺ ).

As shown in Experimental Examples 1) to 11) above, the dimerization reaction was carried out using 0.1 mmol of the styrene derivative and 1.0 mol% of the catalyst of Example 1, and as a result, an excellent conversion ratio of 90% or more was obtained. Further, as a result of NMR analysis of the obtained compound, all of them were pure dimer compound which does not require separation and purification.

Particularly, the dimerization reaction experiment was carried out using only 0.025 mol% (styrene / palladium) of the catalyst of Example 1, and as a result, 9.4 g of pure E -1,3-diphenyl- (94%) of the title compound.

Claims (6)

A catalyst for producing a 1,3-diphenyl-2-butene compound represented by the following formula (1)
[Chemical Formula 1]

In this formula,
X is OTf, BF ₄ or OCl ₄ ,
R is the specific volume unsubstituted or C _{1 -4} alkyl substituted phenyl.
The method according to claim 1,
X is OTf,
Wherein R is phenyl.
2. The catalyst according to claim 1, wherein the 1,3-diphenyl-2-butene compound is synthesized through a dimerization reaction of a compound represented by the following formula (2)
(2)

In this formula,
R ₁ is hydrogen or C _{1 -4} alkyl,
R ₂ is hydrogen, halogen, C _{1 -4} alkoxy, or C _{1 -4} alkyl.
4. The compound according to claim 3, wherein the compound represented by formula (2)
1) styrene,
2) 4-fluorostyrene,
3) 4-bromostyrene,
4) 4-acetoxystyrene,
5) 4-methylstyrene,
6) 1-methylstyrene,
7) 4-t butylstyrene,
8) 4-Trifluoromethylstyrene,
9) 2-fluorostyrene,
10) 3-bromostyrene, and
11) 4-Chlorostyrene
Wherein the catalyst is at least one selected from the group consisting of:
Reacting a compound represented by the following formula (2) with a catalyst according to claim 1 or 2 to prepare a 1,3-diphenyl-2-butene compound represented by the following formula (3)
Preparation method of 1,3-diphenyl-2-butenes compound:
(2)

(3)

In this formula,
R ₁ is hydrogen or C _{1 -4} alkyl,
R ₂ is hydrogen, halogen, C _{1 -4} alkoxy, or C _{1 -4} alkyl.
6. The compound according to claim 5, wherein the compound represented by Formula (2)
1) styrene,
2) 4-fluorostyrene,
3) 4-bromostyrene,
4) 4-acetoxystyrene,
5) 4-methylstyrene,
6) 1-methylstyrene,
7) 4-t butylstyrene,
8) 4-Trifluoromethylstyrene,
9) 2-fluorostyrene,
10) 3-bromostyrene, and
11) 4-Chlorostyrene
≪ / RTI > and at least one member selected from the group consisting of polyvinylidene fluoride (PVDF)