KR20160079655A - Method of manufacturing optically active benzothiophenes compound with high yield and high purity - Google Patents
Method of manufacturing optically active benzothiophenes compound with high yield and high purity Download PDFInfo
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- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
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Abstract
The present invention relates to a process for producing an optically active benzothiophene compound having a high yield and a high optical purity, and more particularly to a process for preparing an optically active benzothiophene compound by quenching at the end of the reaction for synthesizing an optically active benzothiophene compound, Optically active benzothiophene compound having a high yield and a high optical purity can be synthesized.
Description
The present invention relates to a process for producing an optically active benzothiophene compound having a high yield and a high optical purity, and more particularly to a process for preparing an optically active benzothiophene compound by quenching at the end of the reaction for synthesizing an optically active benzothiophene compound, Optically active benzothiophene compound having a high yield and a high optical purity can be synthesized.
The metallocene compound invented by the Kaminsky group in 1980, which is known as a catalyst for polyolefin polymerization, is composed of a combination of a main catalyst, which is a main component of a transition metal compound, and a cocatalyst, which is a main component of an organometallic compound (aluminum).
The metallocene compound has an excellent catalytic activity as compared with a Ziegler-Natta catalyst known as a conventional olefin polymerization catalyst, and can easily control the molecular weight distribution and stereoregularity of the polymer. When such a metallocene compound is used, it has a narrow molecular weight distribution (MWD = 2 to 3) and a comonomer having a homogeneous composition (uniform distribution of comonomer throughout the polymer main chain) and has excellent optical properties such as transparency There is an advantage that a polyolefin copolymer can be easily produced.
The metallocene compound is generally activated by using aluminoxane, borane, borate or other activator. For example, a
On the other hand, the metallocene compound can produce a polyolefin copolymer having various stereoregularity, copolymerization properties, molecular weight, crystallinity and the like depending on the structural modification of the ligand and the polymerization conditions. To solve this problem, studies have been made on ligands for metallocene catalysts.
Among the compounds used as ligands for metallocene catalysts, the benzothiophene compounds represented by the following formula (1) have two chiral centers and thus exist in the form of cis- and trans- .
[Chemical Formula 1]
At this time, since the cis-type compound exists in a solid state, the product can be easily produced and obtained, while the trans-type compound is present in a liquid state, so that the product remaining through the column after filtration must be recovered There is a hassle. Therefore, when a large amount of trans-form is produced during the synthesis reaction, there is a disadvantage that the yield is decreased due to a large loss in the step of obtaining the product.
SUMMARY OF THE INVENTION The present invention has been made to solve the above problem, and it is an object of the present invention to provide a process for preparing optically active benzothiophene compound by quenching at the end of reaction for synthesizing an optically active benzothiophene compound, To a method for synthesizing a base compound.
In order to achieve the above object, in the present invention,
(i) reacting (1-benzothiophene) with n-butyl lithium, CuCN and (2E) -2-methyl-2-butenoyl chloride sequentially to synthesize a compound represented by the following formula ;
(ii) reacting the compound of formula (2) in the presence of an acid catalyst to synthesize an isomer represented by the following formulas (3a) and (3b); And
(iii) quenching the isomer-containing reaction solution represented by the above general formulas (3a) and (3b).
(2)
[Chemical Formula 3]
(3b)
In this formula,
R 1 and R 2 are each hydrogen or an alkyl group having 1 to 10 carbon atoms.
The method of the present invention comprises the steps of: extracting using an organic solvent after quenching; Filtration to obtain a cis-type optically active benzothiophene-based compound; And drying the obtained cis-type optically active benzothiophene-based compound.
Further, in the present invention, the optically active benzothiophene compound synthesized by the above method is a compound wherein the optically active benzothiophene compound has the isomer mixture ratio of the compound represented by Formula 3a: the compound represented by Formula 3b is 51:49 To 99: 1. ≪ / RTI >
According to the method of the present invention, a cis-type optically active benzothiophene compound having a high yield and a high optical purity can be synthesized by a simple method of adding a quenching step at the end of the synthesis reaction.
1 is NMR data of a benzothiophene compound synthesized according to Example 1 of the present invention.
2 is NMR data of a benzothiophene compound synthesized according to Example 2 of the present invention.
3 is NMR data of a benzothiophene compound synthesized according to Example 3 of the present invention.
4 is NMR data of a benzothiophene compound synthesized according to Comparative Example 2 of the present invention.
5 is NMR data of a benzothiophene compound synthesized according to Comparative Example 3 of the present invention.
6 is NMR data of a benzothiophene compound synthesized according to Comparative Example 4 of the present invention.
7 is NMR data of a benzothiophene compound synthesized according to Comparative Example 5 of the present invention.
8 is NMR data of a benzothiophene compound synthesized according to Comparative Example 6 of the present invention.
9 is NMR data of a benzothiophene compound synthesized according to Comparative Example 7 of the present invention.
10 is NMR data of a benzothiophene compound synthesized according to Comparative Example 8 of the present invention.
Hereinafter, the present invention will be described in more detail.
The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.
In the case of benzothiophene compounds which are conventionally used as ligands for metallocene catalysts, isomers of cis- and trans-type compounds are present at the time of synthesis, since the cis-type compounds are present in a solid state While the trans-type compound is present in a liquid state, there is a disadvantage in that the yield is reduced due to a large loss in the step of obtaining the product.
Accordingly, the present invention provides a method for increasing the synthesis yield of a cis-type optically active benzothiophene compound in the synthesis of a benzothiophene-based compound.
Specifically, the present invention provides a method for synthesizing a cis-type optically active benzothiophene compound having a high yield and a high optical purity.
That is, in one embodiment of the present invention
(i) reacting (1-benzothiophene) with n-butyl lithium, CuCN and (2E) -2-methyl-2-butenoyl chloride sequentially to synthesize a compound represented by the following formula ;
(ii) reacting the compound of formula (2) in the presence of an acid catalyst to synthesize an isomer represented by the following formulas (3a) and (3b); And
(iii) quenching the isomer-containing reaction solution represented by the above general formulas (3a) and (3b).
(2)
[Chemical Formula 3]
(3b)
Wherein R 1 and R 2 are each hydrogen or an alkyl group having 1 to 10 carbon atoms.
The method of synthesizing the optically active benzothiophene compound of the present invention can be explained in detail with reference to the following reaction formula 1.
[Reaction Scheme 1]
(1-benzothiophene) and n-butyllithium, CuCN and (2E) -2-methyl-2-butenoyl chloride (or tigloyl chloride) represented by the
At this time, it is preferable that the compound of formula 4: butyllithium: CuCN: 2-methyl-2-butenoyl chloride is mixed in a ratio of 1: 1: 0.5: 1.
In addition, in the method of the present invention, after completion of the reaction, HCl is added as a reaction terminator, followed by extraction using a conventional organic solvent and drying to obtain the compound of Formula 2 as a product.
In the method of the present invention, the compound of formula (2) may be reacted at room temperature in the presence of an acid catalyst to synthesize the isomers represented by the above formulas (3a) and (3b).
At this time, the acid catalyst is added to cause a hydrolysis reaction or the like, and typical examples thereof include sulfuric acid, hydrochloric acid, phosphoric acid and the like.
In the process of the present invention, the molar ratio of the compound of Formula 2 to the acid catalyst may be in the range of 1: 5 to 10, specifically 1: 7.
If the molar ratio of the acid catalyst is more than 10 parts by weight, the reaction rate may increase and side reactions may occur. If the amount is less than 5 parts by weight, the reaction rate may decrease and the reaction may not proceed smoothly.
In the method of the present invention, an organic solvent such as chlorobenzene may be used as a reaction solvent. In this case, the molar ratio of the compound of Formula 2 to the reaction solvent may be in the range of 1: 1 to 3, specifically 1: 7 have.
If the molar ratio of the organic solvent is more than 3 mol, the reaction concentration may be lowered and the reaction rate may be decreased or the reaction may not be performed smoothly. If the molar ratio is less than 1 mol, the reactant concentration may increase and side reactions may occur have.
The reaction of the present invention can be carried out at room temperature for about 1 to 3 hours.
In addition, in the method of the present invention, after completion of the reaction, quenching may be performed on the isomer-containing reaction solution represented by the above formulas (3a) and (3b).
At this time, the quenching step may be performed by putting cooling water at 0 ° C into the reaction solution and rapidly cooling the reaction solution to -20 ° C. As a result, a part of the trans-type optically active benzothiophene compound represented by the general formula (3b) was converted into the cis-type optically active benzothiophene compound represented by the general formula (3a) Can be increased.
At this time, the weight ratio of the compound of Formula 2: cooling water may be in the range of 1:10 to 100, specifically 1:15 to 90. If the amount of the cooling water used is less than 10, the reaction efficiency in which a part of the trans-type optically active benzothiophene compound is converted into the cis-type optically active benzothiophene compound is decreased, and the cis-type optically active benzothiophene There is a disadvantage that the synthesis yield of the compound is lowered.
That is, in the method of the present invention, when the compound of Formula 2 is stirred in the presence of the acid catalyst, the cis-type optically active benzothiophene compound represented by Formula 3a and the trans- Benzothiophene compound can be synthesized at a ratio of about 50:50.
Subsequently, when the reaction solution is quenched by injecting a certain amount of cooling water into the reactor as in the method of the present invention, the enol form is advantageously obtained in the keto-enol form in the totomerization process, The isomer selectivity is lost, and the cis-type optically active benzothiophene compound is present in a proportion of 50% or more.
On the other hand, when the reactor containing the mixed solution is immersed in ice and the reaction solution is slowly cooled, the temperature lowering rate of the reaction solution is lowered, so that some cis-type optically active benzothiophene compounds react with trans- Based compound is low, and the synthesis yield of the cis-type optically active benzothiophene compound is finally low.
Therefore, in the method of the present invention, it is preferable that the quenching step is to terminate the reaction within one hour after the cooling water is introduced to prevent the reaction solution from being heated again.
In addition, the method of the present invention is characterized in that after the quenching step
Extracting and obtaining a cis-type optically active benzothiophene compound by using an organic solvent; And
And drying the obtained cis-type optically active benzothiophene-based compound.
In an embodiment of the present invention,
As the optically active benzothiophene compound synthesized by the method of the present invention,
The optically active benzothiophene compound may be prepared by reacting a compound represented by the general formula (3a): the isomer mixture ratio of the compound represented by the general formula (3b) in the range of 51:49 to 99: 1, specifically 51:49 to 70:30, 49 to 55:45. ≪ / RTI >
Further, in the present invention, a metallocene catalyst for preparing an olefin-based copolymer containing the benzothiophene compound produced by the above method can be prepared.
As described above, according to the method of the present invention, when synthesizing an optically active benzothiophene compound, the synthesis yield of a cis-type optically active benzothiophene compound is improved by a simple method of adding a quenching step at the time of reaction termination It is possible to synthesize optically active benzothiophene compounds of high yield and high optical purity.
Hereinafter, the present invention will be described in detail by way of examples with reference to the following examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.
Example
(Production Example 1)
1-benzothiophene of
After completion of the reaction, 3N HCl was added, and the organic layer was separated by transferring to a separate funnel. The HCl layer was extracted 3 times with CH 2 Cl 2 , and the combined extract was washed with saturated Na 2 CO 3 aqueous solution Lt; / RTI > Removal of the solvent by evaporator vacuum gave 2.47 g (76%) of the compound of formula (2).
1 H NMR (CDCl 3): δ 7.85-7.82 (m, 2H, 4,7- H in C 8 H 5 S), 7.75 (m, 1H, 3-H in C 8 H 5 S), 7.44-7.34 (m, 2H, 5,6- H in C 8 H 5 S) , 6.68 (m, 1H, MeCd C H Me), 1.99 (m, 3H, Me Cd CHMe), 1.92 (m, 3H, MeCd CH Me).
13 C NMR (CDCl 3): δ 191.5, 143.3, 142.4, 139.1, 138.9, 137.7, 130.3, 127.1, 125.9, 125.0, 122.9, 14.9, 12.9.
(Example 1)
286 mg (1.32 mmol) of the compound of Formula 2 in Preparation Example 1 was added to 2.5 mL of chlorobenzene, followed by addition of 2 mL of 98% H 2 SO 4 , and the mixture was reacted at room temperature for 2 hours. Then, 20.84 g of ice water at 0 ° C was added to the mixture, and the mixture was quenched with stirring for 30 minutes. After completion of the reaction, the reaction solution was transferred to a separate funnel, extracted three times with CH 2 Cl 2, and the organic layer was separated and neutralized with saturated aqueous Na 2 CO 3 solution. Water was removed using MgSO 4 and the solvent was removed by evaporator vacuum to give a beige solid (76.45%). As a result of NMR measurement on the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 53: 47 (see Fig. 1).
1 H NMR (CDCl 3): δ 2H, 6,7-H), 3.73 (m, 0.5H, 1-H), 3.19 (m, (d, J = 7.2 Hz, 1.5H, 1/2-Me), 1.39 (d, J = 7.5 Hz, 1.5H, 2- / 1 -Me), 1.36 (d, J = 7.2 Hz, 1.5H, 1- / 2-Me), 1.30 (d, J = 7.5 Hz, 1H, 1.5H, 2- / 1-Me).
13 C NMR (CDCl 3): δ 128.1, 127.4, 124.4, 124.6, 124.2, 124.0, 55.7, 50.2, 40.6, 35.1, 19.0, 16.3, 15.4, 11.2.
(Example 2)
The solid phase compound (76.45%) was obtained in the same manner as in Example 1, except that 10.42 g of ice water was added instead of 20.84 g of ice water in the quenching step. As a result of NMR measurement on the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 55:45 (see FIG. 2).
(Example 3)
A solid compound (76.45%) was obtained in the same manner as in Example 1, except that 5.21 g of ice water was added in place of 20.84 g of ice water in the quenching step. As a result of NMR measurement on the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 51:49 (see FIG. 3).
(Comparative Example 1)
(70%) was obtained in the same manner as in Example 1, except that water was not added in the quenching step and the solution was cooled to room temperature. As a result of NMR measurement on the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 32:68.
(Comparative Example 2)
(71%) was obtained in the same manner as in Example 1, except that 1.3 g of ice water was added instead of 20.84 g of ice water in the quenching step. As a result of NMR measurement on the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 12:88 (see FIG. 4).
(Comparative Example 3)
(71%) was obtained in the same manner as in Example 1, except that 2.6 g of ice water was added in place of 20.84 g of ice water in the quenching step. As a result of NMR measurement on the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 18:82 (see FIG. 5).
(Comparative Example 4)
(70%) was obtained in the same manner as in Example 1, except that 2.3 g of ice water was added in place of 20.84 g of ice water in the quenching step. As a result of NMR measurement on the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 30:70 (see FIG. 6).
(Comparative Example 5)
(70%) was obtained in the same manner as in Example 1, except that 2 g of ice water was added in place of 20.84 g of ice water in the quenching step. As a result of NMR measurement of the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 20:80 (see FIG. 7).
(Comparative Example 6)
(69%) was obtained in the same manner as in Example 1, except that 1.7 g of ice water was added instead of 20.84 g of ice water in the quenching step. As a result of NMR measurement on the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 17: 83 (see FIG. 8).
(Comparative Example 7)
(68%) was obtained in the same manner as in Example 1, except that 1 g of ice water was added instead of 20.84 g of ice water in the quenching step. As a result of NMR measurement on the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 18:82 (see FIG. 9).
(Comparative Example 8)
(68%) was obtained in the same manner as in Example 1, except that 0.65 g of ice water was added instead of 20.84 g of ice water in the quenching step. As a result of NMR measurement on the obtained compound, the mixing ratio of the compound of Formula 3a: Formula 3b was 26:74 (see FIG. 10).
As can be seen from Table 1, in the case of Examples 1 to 3 in which the cooling water was added at a ratio of 10 to 100 to the compound of Formula 2, the content of the cis isomer was high, , And in the case of Comparative Examples 1 to 8 charged at less than 10, the trans isomer content was high.
Claims (13)
(ii) reacting a compound of the following formula (2) in the presence of an acid catalyst to synthesize an isomer represented by the following formula (3a) and (3b); And
(iii) quenching the isomer-containing reaction solution represented by the following general formulas (3a) and (3b): < EMI ID =
(2)
[Chemical Formula 3]
(3b)
In this formula,
R 1 and R 2 are each hydrogen or an alkyl group having 1 to 10 carbon atoms.
(1-benzothiophene): butyllithium: CuCN: 2-methyl-2-butenoyl chloride are mixed in a ratio of 1: 1: 0.5: 1 equivalent in the step of synthesizing the compound of Formula 2 Wherein the optically active benzothiophene compound is a compound represented by the following formula (1).
Wherein the step of synthesizing the isomers represented by the above formulas (3a) and (3b) is carried out at room temperature for 1 to 3 hours.
Wherein the acid catalyst comprises sulfuric acid. ≪ RTI ID = 0.0 > 8. < / RTI >
Wherein the molar ratio of the compound of Formula 2 to the acid catalyst is 1: 5 to 10. < RTI ID = 0.0 > 11. < / RTI >
Wherein the quenching step is carried out by introducing cooling water at 0 ° C.
Wherein the weight ratio of the compound of Formula 2 to the cooling water is in the range of 1:10 to 100. < RTI ID = 0.0 > 11. < / RTI >
Wherein the weight ratio of the compound of Formula 2 to the cooling water is in the range of 1:15 to 90.
The method according to claim 1, wherein the reaction is terminated within 1 hour after the quenching step.
The method comprises: after the quenching step, extracting a cis-type optically active benzothiophene compound using an organic solvent; And
And drying the obtained cis-type optically active benzothiophene-based compound. The method for synthesizing an optically active benzothiophene-based compound according to claim 1,
Wherein the optically active benzothiophene compound is represented by the following formula (3a): the isomer mixture ratio of the compound represented by the following formula (3b) is 51:49 to 99: 1;
[Chemical Formula 3]
(3b)
In this formula,
R 1 and R 2 are each hydrogen or an alkyl group having 1 to 10 carbon atoms.
Wherein the isomer mixture ratio of the compound represented by Formula 3a: Formula 3b is 51:49 to 70:30.
Wherein the isomer mixture ratio of the compound represented by Formula 3a: Formula 3b is 51:49 to 55:45.
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| Alexey N, Ryabov, ET AL: "ZIRCONIUM COMPLEXES WITH CYCLOPENTADIENYL LIGANDS INVOLVING FUSED A THIOPHENE FRAGMENT", ORGANOMETALLICS, US, vol. 21, no. 14, 6 August 2002 (2002-08-06), pages 2842-2855 |
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