KR20210108582A - Method of manufacturing cyclic hydrocarbon compound - Google Patents

Abstract

The present specification relates to a method for manufacturing a cyclic hydrocarbon compound. The method for manufacturing a cyclic hydrocarbon compound comprises a first step of preparing a reaction solution comprising a phenylene diester compound represented by chemical formula 1 and a solvent; a second step of heating the reaction solution; and a third step of dropping an acid represented by chemical formula 2 into the heated reaction solution. According to the present invention, yield and purity of the cyclic hydrocarbon compound can be improved.

Description

Method of producing a hydrocarbon ring compound {METHOD OF MANUFACTURING CYCLIC HYDROCARBON COMPOUND}

The present specification relates to a method for preparing a hydrocarbon ring compound.

Recently, as markets such as watches, laptops, mobile phones, TVs and monitors have exploded, the demand for light-weight and low-power-consumption displays is rapidly increasing every year. Liquid crystal display devices (LCDs) have been widely applied to such products because they are light in weight, exhibit thin display characteristics, and consume less power.

It is necessary to develop a hydrocarbon ring compound suitable as a liquid crystal compound used in a liquid crystal display device. In addition, a method capable of synthesizing such a hydrocarbon ring compound more easily and in high yield is also required.

The present specification is intended to provide a method for preparing a hydrocarbon ring compound.

The present specification relates to a first step of preparing a reaction solution comprising a phenylene diester compound represented by the following Chemical Formula 1 and a solvent;

a second step of heating the reaction solution above a reaction initiation temperature; and

It provides a method for producing a hydrocarbon ring compound comprising a third step of dropping an acid represented by the following formula (2) to the reaction solution heated above the reaction initiation temperature.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

E is a monovalent organic group,

X1 is a divalent organic group,

X2 is an alkylene group having 1 to 30 carbon atoms,

L1 is a halogen group,

R1 is hydrogen; heavy hydrogen; an alkyl group; or an alkoxy group,

R2 to R4 are each independently hydrogen; heavy hydrogen; or an alkyl group having 1 to 5 carbon atoms,

r1 is an integer from 1 to 4,

When r1 is 2 or more, a plurality of R1s are the same as or different from each other.

The method for preparing a hydrocarbon ring compound according to some embodiments of the present specification has an advantage in that there are few side reactions.

The compound prepared according to the method for preparing a hydrocarbon ring compound according to some embodiments of the present specification has an advantage of high purity.

The compound prepared according to the method for preparing a hydrocarbon ring compound according to some embodiments of the present specification has the advantage of high yield.

1 is a TLC (thin layer chromatography) measurement result of Experimental Example 1.
2 is a result of measuring the NMR of the obtained product of Experimental Example 2.

Hereinafter, the present specification will be described in detail.

The present specification relates to a first step of preparing a reaction solution comprising a phenylene diester compound represented by Formula 1 and a solvent;

a second step of heating the reaction solution above a reaction initiation temperature; and

It provides a method for producing a hydrocarbon ring compound comprising a third step of dropping the acid represented by the formula (2) to the reaction solution heated above the reaction initiation temperature.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, and when two or more are substituted , two or more substituents may be the same as or different from each other.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like.

In the present specification, the alkylene group is a divalent alkyl group, and descriptions of the alkyl group may be cited except for the divalent group.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. may be It is not limited.

The method for preparing a hydrocarbon ring compound of the present specification includes a first step of preparing a reaction solution containing a phenylene diester compound represented by Formula 1 and a solvent.

In an exemplary embodiment of the present specification, L1 is a halogen group.

In an exemplary embodiment of the present specification, L1 is a fluorine group, a chlorine group, a bromine group, or an iodine group.

In an exemplary embodiment of the present specification, L1 is a bromine group.

In an exemplary embodiment of the present specification, E is a monovalent organic group, and X1 is a divalent organic group.

In an exemplary embodiment of the present specification, X1 is a divalent organic group having a trans structure.

In an exemplary embodiment of the present specification, X1 includes a divalent aliphatic hydrocarbon ring having 4 to 10 carbon atoms having a trans structure.

In an exemplary embodiment of the present specification, X1 is represented by the following formula (4).

[Formula 4]

In Formula 4,

Ring A is a divalent aliphatic hydrocarbon ring,

X3 is NR' or O,

R' is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkynyl group.

In an exemplary embodiment of the present specification, X1 is represented by the following Chemical Formula 4-1.

[Formula 4-1]

In Formula 4-1,

a and b are integers from 0 to 7,

a+b is 2 to 8,

X3 is NR' or O,

R' is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkynyl group.

In an exemplary embodiment of the present specification, X3 is O.

In an exemplary embodiment of the present specification, X3 is NH.

In an exemplary embodiment of the present specification, X1 is represented by the following Chemical Formula 4-2.

[Formula 4-2]

In an exemplary embodiment of the present specification, E is represented by the following formula (5).

[Formula 5]

In Formula 5,

X4 is an ethynylene group,

R2 is hydrogen, a halogen group, a substituted or unsubstituted alkyl group, an aldehyde group, or a substituted or unsubstituted alkoxy group,

c is 0 or 1, r2 is an integer from 1 to 4,

E1 is a substituent represented by the following formula (6),

[Formula 6]

In Formula 6, X5 is a direct bond; O; C(=O)NH; NH; or NR3, R3 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkynyl group, L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group, l is an integer from 1 to 3, Z is a substituted or unsubstituted ethylenically unsaturated group, and when r2 and l are each 2 or more, the structures in parentheses are the same as or different from each other. do.

는 결합위치를 표시한 것이다.As used herein, * or

indicates the bonding position.

In an exemplary embodiment of the present specification, c is 1, and X4 is an ethynylene group.

In an exemplary embodiment of the present specification, R2 is hydrogen.

In one embodiment of the present specification, X5 is a direct bond.

In an exemplary embodiment of the present specification, X5 is O.

In an exemplary embodiment of the present specification, X5 is C(=O)NH.

In an exemplary embodiment of the present specification, X5 is NH.

In an exemplary embodiment of the present specification, X5 is NR3, and R3 is a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, l is an integer of 1 to 3, L is a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene group.

In an exemplary embodiment of the present specification, l is 1, and L is an alkylene group having 3 to 30 carbon atoms.

In an exemplary embodiment of the present specification, l is 1, and L is a cycloalkylene group having 3 to 30 carbon atoms.

In an exemplary embodiment of the present specification, Z may be a substituted or unsubstituted ethylenically unsaturated group. Here, the ethylenically unsaturated group includes an ethylene group and refers to a substituent capable of further polymerization or crosslinking reaction, and specifically, may be a vinyl group, an acrylate group, an epoxy group, and the like, preferably an acrylate group.

In an exemplary embodiment of the present specification, Z may be a substituted or unsubstituted acrylate group.

In an exemplary embodiment of the present specification, Z is represented by the following formula (7).

[Formula 7]

In Formula 7, R3 is hydrogen or a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, R3 is hydrogen.

In an exemplary embodiment of the present specification, X2 is an alkylene group having 1 to 30 carbon atoms.

In an exemplary embodiment of the present specification, X2 is an alkylene group having 3 to 30 carbon atoms.

In an exemplary embodiment of the present specification, X2 is an alkylene group having 3 to 20 carbon atoms.

In an exemplary embodiment of the present specification, X2 is an alkylene group having 5 to 20 carbon atoms.

In an exemplary embodiment of the present specification, X2 is an alkylene group having 5 to 15 carbon atoms.

In an exemplary embodiment of the present specification, R1 is hydrogen; heavy hydrogen; an alkyl group; or an alkoxy group.

In an exemplary embodiment of the present specification, R1 is hydrogen; heavy hydrogen; or an alkyl group.

In an exemplary embodiment of the present specification, R1 is hydrogen; heavy hydrogen; or an alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R1 is hydrogen; heavy hydrogen; or an alkyl group having 1 to 5 carbon atoms.

In an exemplary embodiment of the present specification, R1 is hydrogen; heavy hydrogen; or a methyl group.

In an exemplary embodiment of the present specification, R1 is hydrogen; or deuterium.

In an exemplary embodiment of the present specification, R1 is hydrogen.

In the exemplary embodiment of the present specification, the reaction solution may include all compositions necessary for the reaction, except for the acid represented by Formula 2 to be dropped in the third step.

In an exemplary embodiment of the present specification, the reaction solution may further include other additives, and specifically may further include a base.

The base may be K ₂ CO ₃ .

In the exemplary embodiment of the present specification, the type of the solvent is not particularly limited and a solvent used in the art may be employed. For example, the solvent may be dimethylformamide.

In the reaction solution, when the mole of the compound represented by Formula 1 is 1, the molar ratio of the base is 2 to 3, preferably 2.5.

The content of the reaction solvent is not particularly limited to an amount sufficient to dissolve the reactants. Based on the total weight of the reaction solution, the content of the solvent may be 80 wt% to 85 wt%.

The method for producing a hydrocarbon ring compound of the present specification includes a second step of heating the reaction solution above the reaction initiation temperature.

In an exemplary embodiment of the present specification, the reaction initiation temperature means a temperature at which the reaction of the compound represented by Formula 1 and the acid represented by Formula 2 is initiated.

In an exemplary embodiment of the present specification, the reaction initiation temperature is 80°C.

The method for producing a hydrocarbon ring compound of the present specification includes a third step of dropping the acid represented by Formula 2 to the reaction solution heated above the reaction initiation temperature.

In an exemplary embodiment of the present specification, the rate of dropping the acid represented by Formula 2 may be 0.05 mL/min or more and 0.1 mL/min or less based on 1 g of the substance represented by Formula 1.

When the acid represented by Formula 2 is added to the reaction solution and heated, impurities derived from the breakdown of the structure of the reactant by the acid such as quinone diacrylate are generated, thereby lowering the purity of the product.

In the method for producing a hydrocarbon ring compound of the present specification, in order to reduce impurities represented by quinone diacrylate generated by side reactions or suppress side reactions, the acid represented by Formula 2 is mixed with the phenylene diester represented by Formula 1 Without heating together with the compound, the reaction solution except for the acid represented by Formula 2 was first heated above the reaction initiation temperature, and then the acid represented by Formula 2 was slowly added.

The compound prepared according to the method for preparing a hydrocarbon ring compound of the present specification has no or less by-products such as quinone diacrylate produced by a side reaction and has high purity.

In an exemplary embodiment of the present specification, R2 to R4 are each independently hydrogen; heavy hydrogen; or an alkyl group having 1 to 5 carbon atoms.

In an exemplary embodiment of the present specification, R2 to R4 are each independently hydrogen; heavy hydrogen; or a methyl group.

In an exemplary embodiment of the present specification, R2 to R4 are each independently hydrogen; or deuterium.

In an exemplary embodiment of the present specification, R2 to R4 are hydrogen.

In an exemplary embodiment of the present specification, when the mole of the compound represented by Formula 1 is 1, the molar ratio of the total amount of the acid represented by Formula 2 is 2 to 3, preferably 2.5. .

The method for producing a hydrocarbon ring compound of the present specification may further include a fourth step of stirring for less than 5 hours from the time of dropping the acid represented by Formula 2 in the third step.

In an exemplary embodiment of the present specification, the fourth step may be stirred for less than 5 hours, less than 4 hours, or less than 3 hours from the time of dropping the acid represented by Formula 2 above.

The method for preparing a hydrocarbon ring compound of the present specification may further include a fifth step of obtaining the resulting compound represented by the following Chemical Formula 3 after the fourth step.

[Formula 3]

In Formula 3, E, R1, r1, X1, and X2 are as defined in Formula 1, and R2 to R4 are defined as in Formula 2 above.

The purity of the compound represented by Formula 3 obtained through the fifth step may be 80% or more, 85% or more, or 90% or more.

Here, the purity can be obtained by comparing the integral value of the sp2 peak of the product and the sp2 peak of the side reactant in 1H NMR analysis.

The compound prepared by the method for preparing a hydrocarbon ring compound of the present specification may be a liquid crystal compound.

The present specification provides a liquid crystal display device comprising a compound prepared by the above-described method for producing a hydrocarbon ring compound.

For the structure and description of the liquid crystal display device, structures and descriptions known in the art may be employed.

Hereinafter, the present specification will be described in more detail through examples. However, the following examples are only for illustrating the present specification, and not for limiting the present specification.

[Example 1]

compound 1-1 1 eq. And K ₂ CO ₃ 2.5 eq. was put in DMF (dimethylformamide) of 4 times the mass of the reactant to prepare a reaction solution. After heating to 80° C., 2.5 eq. of acrylic acid was added dropwise at 0.1 mL/min based on 1 g of material and stirred for 3 hours.

[Example 2]

compound 1-1 1 eq. And K ₂ CO ₃ 2.5 eq. was put in DMF (dimethylformamide) of 4 times the mass of the reactant to prepare a reaction solution. After heating to 80° C., 2.5 eq. of acrylic acid was added dropwise at 0.1 mL/min based on 1 g of material and stirred for 5 hours.

[Comparative Example 1]

compound 1-1 1 eq., K ₂ CO ₃ 2.5 eq. And 2.5eq. of acrylic acid was added to DMF (dimethylformamide) having 4 times the mass of the reactant to prepare a reaction solution. It was heated to 80° C. and stirred for 3 hours.

[Experimental Example 1]

After completion of the reaction of Example 1 and Comparative Example 1, each reaction solution was aliquoted and subjected to TLC analysis. The results are shown in FIG. 1, and the TLC phase reaction purity is 80% in the Example and 40% in the Comparative Example.

The purity of the reaction in the TLC phase was calculated by processing the TLC photograph using the Image J program. Specifically, the values of the intensity and area of TLC spots were plotted in a graph with the above program, and then the area values of each spot were calculated. Thereafter, the purity was determined by calculating the proportion of the peak of the target product.

[Experimental Example 2]

After completion of the reaction of Examples 1 and 2, each reaction solution was dropped into water to precipitate and centrifuge to obtain a precipitate. After obtaining the MC layer by MC/water extraction, the product was dried and residual impurities were washed away with methanol to obtain each product.

The results of measuring NMR for each obtained product are shown in FIG. 2 .

2, it can be seen that in Example 1, quinone diacrylate was hardly generated as a side reaction, and in Example 2, it was confirmed that quinone diacrylate was generated.

At this time, in Example 1, a yield of 53% and a purity of 90% Compound 1 was obtained, and in Example 2, a yield of 37% and a purity of 63% Compound 1 was obtained.

Here, the purity was obtained by comparing the integral value of the sp2 peak of the product and the sp2 peak of the side reactant in 1H NMR analysis.

Through this, when acrylic acid is added dropwise after heating the reactants except for acrylic acid as in Examples 1 and 2, it can be confirmed that the purity is high because there is little or no quinone diacrylate produced as a side reaction.

In addition, even if acrylic acid is added dropwise after heating the reactants except for acrylic acid, when the reaction time is longer than 5 hours as in Example 2, the quinone diacrylate generated as a side reaction increases, so that the purity and yield are lower than in Example 1. could confirm that

Claims (6)

A first step of preparing a reaction solution comprising a phenylene diester compound represented by the following Chemical Formula 1 and a solvent;
a second step of heating the reaction solution above a reaction initiation temperature; and
A method for producing a hydrocarbon ring compound comprising a third step of dropping an acid represented by the following formula (2) to the reaction solution heated above the reaction initiation temperature:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
E is a monovalent organic group,
X1 is a divalent organic group,
X2 is an alkylene group having 1 to 30 carbon atoms,
L1 is a halogen group,
R1 is hydrogen; heavy hydrogen; an alkyl group; or an alkoxy group,
R2 to R4 are each independently hydrogen; heavy hydrogen; or an alkyl group having 1 to 5 carbon atoms,
r1 is an integer from 1 to 4,
When r1 is 2 or more, a plurality of R1s are the same as or different from each other. The method according to claim 1, further comprising a fourth step of stirring for less than 5 hours from the time of dropping the acid represented by the formula (2) in the third step. The method according to claim 1, wherein R2 to R4 are hydrogen. The method according to claim 1, wherein L1 is a bromine group. The method for producing a hydrocarbon ring compound according to claim 2, further comprising a fifth step of obtaining a compound represented by the following formula (3) after the fourth step:
[Formula 3]

In Formula 3, E, R1, r1, X1, and X2 are as defined in Formula 1, and R2 to R4 are defined as in Formula 2 above. The method of claim 5, wherein the purity of the compound represented by Formula 3 obtained through the fifth step is 80% or more.

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