KR102425716B1 - Myrcene derived compound and method for preparing the same - Google Patents

Abstract

The present invention relates to a myrcene derivative compound, which can be applied as a raw material for a modified polymerization initiator, and a method for preparing the same. Accordingly, the myrcene derivative compound represented by Formula 1 includes various functional groups, and thus can be used as a raw material for a polymerization initiator to form a modified polymerization initiator into which various functional groups are introduced.

Description

Myrcene derived compound and method for preparing the same

The present invention relates to a myrcene derivative compound, which can be applied as a raw material for a modified polymerization initiator, and a method for preparing the same.

In response to the recent demand for low fuel consumption for automobiles, a conjugated diene-based polymer having low rolling resistance, excellent abrasion resistance and tensile properties, and adjustment stability typified by wet road resistance is required as a rubber material for tires.

In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and rebound elasticity of 50°C to 80°C, tan δ, Goodrich heat, etc. are used as evaluation indicators of the vulcanized rubber. That is, a rubber material having a large rebound elasticity at the above temperature or a small tan δ Goodrich heat generation is preferable.

As a rubber material having a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known, but these have a problem of low resistance to wet road surfaces. Accordingly, recently, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. . Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the content of vinyl structure and styrene content defining rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. that it can be adjusted. Therefore, it is easy to change the structure of the finally manufactured SBR or BR, and it is possible to reduce the movement of the chain ends by bonding or modifying the chain ends, and to increase the binding force with fillers such as silica or carbon black. It is widely used as a rubber material for

When this solution-polymerized SBR is used as a rubber material for a tire, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be increased to control the required physical properties of the tire such as running resistance and braking force, and the glass transition temperature can be lowered. By properly adjusting it, fuel consumption can be reduced. The solution polymerization SBR is prepared by using an anionic polymerization initiator, and is used by bonding or modifying the chain ends of the formed polymer using various modifiers. For example, U.S. Patent No. 4,397,994 discloses a technique in which an active anion at the chain end of a polymer obtained by polymerization of styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, is combined using a binder such as a tin compound. did.

On the other hand, the solution polymerization SSBR is prepared using an anionic polymerization initiator, and an organic lithium compound is mainly used as the anionic polymerization initiator. The organolithium compound is used as it is or modified with a functional group-containing compound capable of imparting a functional group to the polymer chain. For example, there is a method of preparing and using a modified polymerization initiator having a styrene-based structural unit, a conjugated diene-based structural unit, or an arylamine structural unit by reacting a styrene-based compound, a conjugated diene-based compound, or an arylamine compound with an organolithium compound. , there is a limitation in industrial use due to poor economic feasibility, and in particular, in obtaining a modified polymerization initiator using a conjugated diene-based compound, it is difficult to manufacture the functional group because it is not easy to bind to the conjugated diene-based unit.

For example, JP03748277 describes an anionic polymerization initiator prepared by reacting an organolithium compound with an adduct in which nitrogen of a cyclic secondary amine is bonded to a conjugated diene carbon, but when prepared by the above reaction, a cyclic secondary amine remains Therefore, it may act as a scavenger in the reaction, and thus the yield of the anionic polymerization initiator may be reduced. Therefore, the process of filtration and purification after the reaction is essentially required. Therefore, there is a need for the development of a modified polymerization initiator with good economic feasibility and good industrial applicability.

US 4397994 A JP 03748277 B2

The present invention has been devised to solve the problems of the prior art, and it is used in a polymerization reaction to easily initiate the reaction, and is a novel novel that can be applied as a raw material for a modified polymerization initiator that can provide a functional group to the polymer. An object of the present invention is to provide a myrcene derivative compound having a structure and a method for preparing the same.

In order to solve the above problems, the present invention provides a myrcene derivative compound represented by the following formula (1):

[Formula 1]

In Formula 1,

A is -NR _a R _b , -OR _c , or -SR _d ,

Wherein R _a to R _d are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, unsubstituted or substituted with a substituent containing one or more heteroatoms selected from N, O, S, Si and F atoms , an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, or an aryl group having 2 to 30 carbon atoms, wherein R _a and R _b are connected to each other and replaced with an alkyl group having 1 to 30 carbon atoms or unsubstituted C 5 It may form an aliphatic ring group of to 20 carbon atoms, an aromatic ring group having 5 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms.

In addition, the present invention comprises the steps of preparing a compound represented by the following formula (3) by reacting a compound represented by the following formula (2) with an alkylsulfonyl chloride-based compound in the presence of an organic solvent (step 1); There is provided a method for preparing a myrcene derivative compound represented by the following formula (1), comprising reacting a compound represented by the formula (3) with a compound represented by the following formula (4) (step 2):

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 1]

In Formula 1, Formula 3 and Formula 4,

A is -NR _a R _b , -OR _c , or -SR _d ,

Wherein R _a to R _d are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, unsubstituted or substituted with a substituent containing one or more heteroatoms selected from N, O, S, Si and F atoms , an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, or an aryl group having 2 to 30 carbon atoms, wherein R _a and R _b are connected to each other and substituted or unsubstituted with an alkyl group having 1 to 30 carbon atoms. It may form an aliphatic ring group of to 20, an aromatic ring group of 5 to 20 carbon atoms, or a heterocyclic group of 3 to 20 carbon atoms,

M is a living group.

In addition, the present invention comprises the steps of preparing a compound represented by the following formula 5 by reacting a compound represented by the following formula 4-1 with an alkylsulfonyl chloride-based compound in the presence of an organic solvent (step a); and a step (step b) of reacting the compound represented by Formula 5 with the compound represented by Formula 2 below:

[Formula 2]

[Formula 4]

[Formula 5]

[Formula 1]

In Formula 1, Formula 4 and Formula 5,

A is -OR _c ,

Wherein R _c is an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, unsubstituted or substituted with a substituent containing one or more heteroatoms selected from N, O, S, Si and F atoms an alkynyl group, a cycloalkyl group having 2 to 30 carbon atoms, or an aryl group having 2 to 30 carbon atoms;

M is a living group.

Since the myrcene derivative compound represented by Formula 1 according to the present invention contains various functional groups, it can be used as a raw material for a polymerization initiator to form a modified polymerization initiator into which various functional groups are introduced.

In addition, the method for preparing the myrcene derivative compound according to the present invention prepares a compound represented by Formula 3 in which a living group, such as a methanesulfonate group (MsO ^- , CH ₃ SO ₃ ^- ), is introduced into the myrcene molecular structure, , by reacting a compound containing a functional group, such as a compound represented by Formula 4, therein, various functional groups can be easily introduced, and a myrcene derivative compound can be prepared in high yield.

In addition, the method for preparing the myrcene derivative compound according to another embodiment of the present invention prepares a compound represented by Formula 5 in which a living group, such as a mesyl group, is introduced into a functional group-containing compound, and the compound represented by Formula 2 By reacting with a myrcene derivative compound having a functional group introduced therein can be prepared in high yield.

The following drawings attached to the present specification illustrate specific embodiments of the present invention, and serve to further understand the technical spirit of the present invention together with the above-described content of the present invention, so the present invention is limited to the matters described in those drawings should not be construed as limited.
1 shows the results of H-NMR analysis of the myrcene derivative compound represented by Formula 1-5 prepared in Example 1 according to an embodiment of the present invention.
2 shows the results of H-NMR analysis of the myrcene derivative compound represented by Formula 1-7 prepared in Example 2 according to an embodiment of the present invention.
3 shows the results of H-NMR analysis of the myrcene derivative compound represented by Formula 1-6 prepared in Example 3 according to an embodiment of the present invention.
4 shows the results of H-NMR analysis of the myrcene derivative compound represented by Formula 1-8 prepared in Example 4 according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. Based on the principle that it can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

The term 'substitution' used in the present invention may mean that a functional group, atomic group, or hydrogen of a compound is substituted with a specific substituent, and when a functional group, atomic group, or hydrogen of a compound is substituted with a specific substituent, a functional group, atomic group, Alternatively, one or two or more plural substituents may be present depending on the number of hydrogens present in the compound, and when plural substituents are present, each substituent may be the same as or different from each other.

The term 'alkyl group' used in the present invention may mean a monovalent aliphatic saturated hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, sec-butyl) , tert-butyl (tert-butyl) and neopentyl (neo-pentyl) may include all of the branched alkyl group.

The term 'alkylene group' used in the present invention may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

The term 'alkenyl group' used in the present invention may refer to an alkyl group including one or two or more double bonds.

The term 'alkynyl group' used in the present invention may mean an alkyl group including one or two or more triple bonds.

The term 'cycloalkyl group' used in the present invention may mean including all cyclic saturated hydrocarbons or cyclic unsaturated hydrocarbons including one or two or more unsaturated bonds.

The term 'aryl group' used in the present invention may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded ( It may mean including all polycyclic aromatic hydrocarbons).

The terms 'derived unit' and 'derived functional group' used in the present invention may indicate a component, structure, or substance itself derived from a certain substance.

The present invention provides a myrcene derivative compound that can be applied as a raw material for preparing a modified polymerization initiator.

The myrcene derivative compound according to an embodiment of the present invention is a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

A is -NR _a R _b , -OR _c , or -SR _d ,

Wherein R _a to R _d are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, unsubstituted or substituted with a substituent containing one or more heteroatoms selected from N, O, S, Si and F atoms , an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, or an aryl group having 2 to 30 carbon atoms, wherein R _a and R _b are connected to each other and substituted or unsubstituted with an alkyl group having 1 to 30 carbon atoms. It may form an aliphatic ring group of to 20 carbon atoms, an aromatic ring group having 5 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms.

Specifically, in Formula 1, A is -NR _a R _b , -OR _c , or -SR _d , wherein R _a to R _d are each independently from N, O, S, Si and F atoms. It may be unsubstituted or substituted with a substituent containing one or more selected heteroatoms, and when unsubstituted, R _a to R _d are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and carbon number may be an alkynyl group having 2 to 20 carbon atoms, _{a cycloalkyl} group having 3 to 20 carbon atoms, or an aryl group having 3 to 20 carbon atoms. It may be a heteroalkenyl group having 2 to 20 carbon atoms, a heteroalkynyl group having 2 to 20 carbon atoms, a heterocycloalkyl group having 2 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms.

In addition, in -NR _a R _b , R _a and R _b are connected to each other and substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, an aliphatic ring group having 5 to 10 carbon atoms, an aromatic ring group having 5 to 10 carbon atoms, or 3 carbon atoms to 10 may form a heterocyclic group, wherein at least one of the carbon atoms forming the ring is substituted with a heteroatom, wherein the heteroatom is one selected from N, O, S, Si and F atoms It may be more than

More specifically, in Formula 1, A may be selected from the substituents represented by the following Formulas 1a to 1c.

[Formula 1a]

[Formula 1b]

[Formula 1c]

In Formulas 1a to 1c,

R ₁ , R ₂ , R ₅ , R ₇ and R ₈ are each independently an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, which is unsubstituted or substituted with a substituent including one or more heteroatoms selected from N, O and S atoms. A 10 alkenyl group, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 2 to 10 carbon atoms, or an aryl group having 2 to 10 carbon atoms, or R ₁ and R ₂ and R ₇ and R ₈ are each bonded to each other and have 5 to carbon atoms It forms an aliphatic ring group of 20 or an aromatic ring group of 5 to 20 carbon atoms,

R ₃ , R ₄ and R ₆ are each independently substituted with a substituent containing a heteroatom selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms, or N and O atoms; It is an unsubstituted alkylene group having 1 to 10 carbon atoms,

X and Z are each independently selected from N, O, and S atoms, and when X is O or S, R ₈ does not exist, and when Z is O or S, R ₅ does not exist.

Specifically, in Formulas 1a to 1c, R ₁ , R ₂ , R ₅ , R ₇ and R ₈ are each independently selected from N, O and S atoms substituted or unsubstituted with a substituent including at least one heteroatom. an alkyl group having 1 to 10 carbon atoms, or R ₁ and R ₂ and R ₇ and R ₈ are each bonded to each other to form an aliphatic ring group having 5 to 10 carbon atoms or an aromatic ring group having 5 to 10 carbon atoms, R ₃ , R ₄ and R ₆ are each independently an alkylene group having 1 to 10 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, R ₅ is an alkyl group having 1 to 10 carbon atoms, and X and Z are each independently N, O and S atom, R ₈ may not be present when X is O or S, and R ₅ may not be present when Z is O or S.

More specifically, in Formula 1, A may be a substituent represented by the following Formulas a to k.

[Formula a]

[Formula b]

[Formula c]

[Formula d]

[Formula e]

[Formula f]

[Formula g]

[Formula h]

[Formula i]

[Formula j]

[Formula k]

More specifically, the myrcene derivative compound represented by Formula 1 may be a compound represented by Formulas 1-1 to 1-11 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

In addition, the present invention provides a method for preparing the myrcene derivative compound that can be applied as a raw material for preparing a modified polymerization initiator.

The method for preparing the myrcene derivative compound represented by Formula 1 according to an embodiment of the present invention may be performed by one or more of the following two methods, Method 1 and Method 2, depending on the substituent A in Formula 1 above.

Specifically, in the method for preparing the myrcene derivative (Method 1) according to an embodiment of the present invention, the compound represented by the following Chemical Formula 2 and an alkylsulfonyl chloride-based compound are reacted with the following Chemical Formula 3 in the presence of an organic solvent. preparing the indicated compound (step 1); and reacting the compound represented by Formula 3 with the compound represented by Formula 4 below (step 2).

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 1]

In Chemical Formulas 1, 3, and 4, A is as defined above, and M is a living group.

Step 1 is a step for preparing a compound represented by Formula 3 in which a reactive site is introduced into the β-myrcene molecular structure, wherein the compound represented by Formula 2 and an alkylsulfonyl chloride-based compound are reacted in the presence of an organic solvent. It may be done by

Meanwhile, in the present invention, the compound represented by Formula 2 is a compound derived from β-myrcene, specifically, a primary reaction between β-myrcene and selenium dioxide, sequential addition of a reducing agent and an acid, and a secondary reaction It may be manufactured by

Illustratively, the compound represented by Formula 2 may be prepared through a reaction as shown in Scheme 1 below.

[Scheme 1]

As shown in Scheme 1, β-myrcene is a myrcene compound into which an alcohol group is introduced and a myrcene compound into which an aldehyde group is introduced through an allylic oxidation reaction (primary reaction) by selenium dioxide (SeO ₂ ). Herein, a reducing agent (eg, NaBH ₄ ) is added and reacted (secondary reaction), and after completion of the reaction, protonation (proton addition) is performed to prepare a myrcene compound in which all of the product is introduced with an alcohol group represented by formula (2). In addition, in the first reaction, t-butylhydroperoxide may be added together with selenium dioxide, and in this case, selenium hydroxide produced by reduction by the reaction (Se(OH) ₂ ) and It can act to oxidize it back to selenium dioxide by reacting. Through this oxidation reaction, the product can be induced in the form of E-isomer.

Here, the β-myrcene may have a compound structure represented by the following formula (6) among various myrcene isomers.

[Formula 6]

In the first reaction, β-myrcene and selenium dioxide may be reacted in a molar ratio of 1:0.01 to 1:1, and when t-butylhydroperoxide is added, t-butylhydroperoxide is selenium dioxide It may be added in a molar ratio of 0.5 to 5 to 1 mole. In addition, the first reaction may be performed in the presence of an organic solvent, and may be performed at a temperature of 0° C. to 60° C. for 1 hour to 72 hours.

In addition, the secondary reaction is performed by adding a reducing agent to the reaction product generated through the primary reaction, and the secondary reaction may be performed in the presence of an organic solvent, at a temperature of -20 °C to 30 °C. It may be carried out for 10 minutes to 24 hours. In addition, after the secondary reaction, an acid (eg, H ₃ O ⁺ ) may be added to perform protonation treatment.

In addition, in the present invention, the compound represented by Formula 2 in Step 1 and the alkylsulfonyl chloride-based compound may be reacted in a molar ratio of 1:0.5 to 5.

In addition, the alkylsulfonyl chloride-based compound may be a material that reacts with the compound represented by Formula 2 to provide a living group corresponding to M in Formula 3, wherein M in Formula 3 is a methanesulfonate group (CH ₃ SO ₃ ^- ) or an alkylsulfonate group such as a methylbenzenesulfonate group (C ₇ H ₇ SO ₃ ^- ).

In addition, the alkylsulfonyl chloride-based compound is not particularly limited as long as it is a compound capable of providing the living group, for example, methanesulfonyl chloride, p-toluenesulfonyl chloride, 2- It may be propanesulfonyl chloride (2-propanesulfonyl chloride), trichloromethanesulfonyl chloride (trichloromethanesulfonyl chloride), cyclohexanesulfonyl chloride (cyclohexanesulfonyl chloride) or cyclopentanesulfonyl chloride (cyclopentanesulfonyl chloride).

In addition, the reaction of step 1 may be performed in the presence of a basic compound, wherein the basic compound is diethylamine, triethylamine, diisopropylamine, triisopropylamine (triisopropylamine), potassium carbonate (porassium carbonate), calcium carbonate (calcium carbonate), sodium carbonate (sodium carbonate), sodium hydroxide (sodium hydroxide) and potassium hydroxide (potassium hydroxide) It may be at least one selected from the group consisting of. If, when the reaction of step 1 is performed in the presence of a basic compound, the basic compound may be used in a molar ratio of 0.1 to 3.0 to 1 mole of the compound represented by Formula 2.

In addition, the reaction of step 1 may be performed at a temperature of -20 °C to 30 °C for 10 minutes to 24 hours. If the reaction of step 1 is performed under the above temperature conditions, the compound represented by Formula 3 can be easily prepared in a shorter time.

Step 2 is a step of preparing a myrcene derivative compound represented by Formula 1 into which a functional group derived from the compound represented by Formula 4 is introduced, and may be performed by reacting the compound represented by Formula 3 with the compound represented by Formula 4 have. In this case, the compound represented by Formula 3 and the compound represented by Formula 4 may be reacted in a molar ratio of 1:0.1 to 1:20, and specifically, the reaction in step 2 is a compound represented by Formula 3 It may be carried out by using the compound represented by Formula 4 in a molar ratio of 0.1 to 10 relative to 1 mole.

In addition, in the present invention, the reaction of step 2 may be performed in the presence of a basic compound, and in this case, the basic compound may be used in a molar ratio of 0.1 to 3.0 relative to 1 mole of the compound represented by Formula 3 . Meanwhile, the basic compound may be as defined above. In addition, the reaction of step 2 may be performed at a temperature of 0 °C to 50 °C for 10 minutes to 24 hours.

In addition, the myrcene derivative compound represented by Formula 1 according to an embodiment of the present invention is prepared by a manufacturing method (Method 2) different from the above-mentioned manufacturing method (Method 1) according to the substituent A in Chemical Formula 1 as described above. can do.

Accordingly, another embodiment of the present invention provides another method (Method 2) for preparing the myrcene derivative compound represented by Formula 1 above.

Specifically, in the preparation method (Method 2) according to another embodiment of the present invention, a compound represented by the following Chemical Formula 5 is reacted with a compound represented by the following Chemical Formula 4 with an alkylsulfonyl chloride-based compound in the presence of an organic solvent. preparing a (step a); and reacting the compound represented by Formula 5 with the compound represented by Formula 2 below (step b).

[Formula 2]

[Formula 4]

[Formula 5]

[Formula 1]

In the method for preparing the myrcene derivative compound according to Method 2, A in Formulas 1, 4, and 5 is -OR _c , wherein R _c is selected from N, O, S, Si and F atoms. An alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, or a cycloalkyl group having 2 to 30 carbon atoms, unsubstituted or substituted by a substituent containing one or more heteroatoms an aryl group, and M is a living group.

Specifically, R _c and M are as defined above.

In addition, the compound represented by Formula 2 may be prepared by the method as defined above.

In step a, the compound represented by Formula 4 and the alkylsulfonyl chloride-based compound may be reacted in a molar ratio of 1:0.5 to 5, wherein the alkylsulfonylchloride-based compound is as defined above.

In addition, the reaction of step a may be performed in the presence of a basic compound, wherein the basic compound is as defined above. In addition, when the reaction of step a is performed in the presence of a basic compound, the basic compound may be used in a molar ratio of 0.1 to 3.0 relative to 1 mole of the compound represented by Formula 4.

In addition, the reaction of step a may be performed at a temperature of -20 °C to 30 °C for 10 minutes to 24 hours. If the reaction of step a is performed under the above temperature conditions, the compound represented by Formula 5 can be easily prepared in a shorter time.

In step b, a myrcene derivative compound represented by Formula 1 into which a functional group derived from the compound represented by Formula 5 is introduced (here, in the myrcene derivative compound represented by Formula 1, A is -OR _c in Formula 1) As a preparation step, it may be carried out by reacting the compound represented by the formula (5) with the compound represented by the formula (2). In this case, the compound represented by Formula 5 and the compound represented by Formula 2 may be reacted in a molar ratio of 0.1:1 to 20:1, and specifically, the reaction in step b is the compound represented by Formula 2 It may be carried out by using the compound represented by Formula 5 in a molar ratio of 0.1 to 10 to 1 mole.

In addition, in the present invention, the reaction of step b may be performed in the presence of a basic compound, wherein the basic compound is as defined above. In addition, when the reaction of step b is performed in the presence of a basic compound, the basic compound may be used in a molar ratio of 0.1 to 3.0 relative to 1 mole of the compound represented by Formula 5. In addition, the reaction of step 2 may be performed at a temperature of 0 °C to 50 °C for 10 minutes to 24 hours.

In general, as a method for preparing a myrcene derivative compound in which a functional group is introduced from myrcene, a halogenated myrcene compound having a reactive site is prepared by introducing a halogen element into the myrcene molecular structure, and a functional group-containing compound is reacted thereto. do. However, when a functional group is introduced into the myrcene molecular structure by reacting the halogenated myrcene compound with a functional group-containing compound, there is a problem in that an excessive amount of the functional group-containing compound is required and the functional group that can be introduced is limited to an amine group.

However, the production method according to an embodiment of the present invention prepares a compound represented by Formula 3 in which a living group (eg, a methanesulfonate group) is introduced into the myrcene molecular structure, and the same as the compound represented by Formula 4 here. By reacting the functional group-containing compound, various functional groups can be introduced, and functional groups can be easily introduced without excessive use of the functional group-containing compound. In addition, by preparing a compound represented by Formula 5 in which a living group (eg, a methanesulfonate group) is introduced into a functional group-containing compound, and reacting it with a compound represented by Formula 2, a myrcene derivative into which a functional group is introduced in a higher yield compounds can be prepared.

On the other hand, the organic solvent used in the preparation method according to an embodiment of the present invention is, for example, pentane, hexane, toluene, dimethylformamide, dimethylacetamide, n-butanol, butyl acetate, chloroform, 1,2-dichloroethane, dichloromethane, dimethyl sulfoxide, diocene, ethanol, ethyl acetate, diethyl ether, methyl-t-butyl ether, methyl ethyl ketone, n-propanol, iso-propanol, tetrahydrofuran, trichloroethylene or xylene .

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

production example

18.3 mmol of selenium dioxide and 73.4 mmol of t-butylhydroperoxide were added to 44 g of methylene chloride and stirred at 20° C. for 30 minutes to prepare a diluted solution. Then, the diluted solution was added to 5 g (36.7 mmol) of β-myrcene and reacted at 20° C. for 48 hours. After the reaction was completed, methylene chloride was removed with a rotary evaporator, diluted with diethylether, and washed twice or more with 10 wt% sodium hydroxide solution. Then, it was washed once more with Brine, and diethyl ether was removed with a rotary evaporator. After adding 72 g of methanol and cooling to 0°C, 36.7 mmol of NaBH ₄ was added thereto, the temperature was raised to 20°C, and the reaction was stirred for 1 hour. Thereafter, saturated ammonium chloride solution was added, water and diethyl ether were added, the layers were separated, filtered, and diethyl ether was removed using a rotary evaporator, and methylene chloride was added thereto for extraction. Here, the moisture is removed using magnesium sulfate, and the methylene chloride is again removed and purified using a rotary evaporator to (E)-2-methyl-6-methyleneocta-2,7-diene-, which is a compound represented by the following Chemical Formula 2 1-ol ((E)-2-methyl-6-methyleneocta-2,7-dien-1-ol) was prepared (yield 82%).

[Formula 2]

Example

Example 1

1) Preparation of a compound represented by Formula 3-1

After dissolving 39.4 mmol of (E)-2-methyl-6-methyleneocta-2,7-dien-1-ol and 43.4 mmol of triethylamine in 120 g of methylene chloride, the compound represented by Formula 2 prepared in Preparation Example , cooled to 0 °C. Here, 47.3 mmol of methanesulfonyl chloride was added thereto, and then the temperature was raised to 20° C. and reacted with stirring for 3 hours. After completion of the reaction, methylene chloride was added to dilute it, washed with 1N HCl solution, washed again with saturated sodium bicarbonate (NaHCO ₃ ) solution, neutralized, washed again with Brine, and then water was removed with magnesium sulfate. Thereafter, the methylene chloride is removed with a rotary evaporator, and (E)-2-methyl-6-methyleneocta-2,7-dien-1-yl methanesulfonate ((E)- 2-methyl-6-methyleneocta-2,7-dien-1-yl methanesulfonate) 8.0 g (yield 89%) was prepared.

[Formula 3-1]

In Formula 3-1, Ms represents a mesyl group.

2) Preparation of a compound represented by Formula 1-5

34.7 mmol of (E)-2-methyl-6-methyleneocta-2,7-dien-1-yl methanesulfonate, which is a compound represented by Formula 3 prepared in 1) above, was dissolved in 150 g of dimethylformamide, Here, 52.1 mmol of K ₂ CO ₃ and 0.75 g (7.49 mmol) of 1-methylpiperazine were sequentially added thereto and reacted at room temperature (about 25° C.) for 12 hours. Thereafter, 6.2 g of a myrcene derivative compound represented by the following Chemical Formula 1-5 was prepared by purification.

[Formula 1-5]

It was confirmed that the prepared myrcene derivative compound represented by Formula 1-5 was synthesized through GC/MS and H-NMR analysis. As a result of MS analysis, m/z=234 g/mol, and β-myrcene as a starting material was 136 g/mol. Also, H-NMR results are shown in FIG. 1 .

At this time, the GC/MS analysis uses ZB-5MS (0.25 mm (ID) × 30 ml, 0.25 μm d.f. capillary) as a column, and the gas flow rate (column (He)) is 1 ml/min, an oven The temperature was increased from 50° C. to 320° C. at 10° C./min for 3 minutes after 3 minutes and maintained for 15 minutes, and the injector temperature was adjusted to 250° C., split ratio 1/20, and the injection amount was measured by adjusting 0.2 μl.

In addition, H-NMR was measured with a 500 MHz Agilent DD1.

Example 2: Preparation of a compound represented by Formula 1-7

76.4 mmol of sodium hydride (NaH, 60 wt% in mineral oil) was dissolved in 105 g of dimethylformamide, and this was cooled to 0°C. Here, 52 g (38.2 mmol) of 7.5 wt% N,N-dimethylaminopropanol (N,N-dimethylaminopropanol, in dimethylformamide) was added, and the reaction was stirred at 0° C. for 1 hour. Thereafter, 34.7 mmol of 2-methyl-6-methyleneocta-1,7-dien-3-yl methanesulfonate, a compound represented by Formula 3, was added, and the temperature was raised to 20° C. to react for 12 hours. In this case, the compound represented by Formula 3 was prepared in the same manner as in 1) of Example 1. Thereafter, 5.2 g of a myrcene derivative compound represented by the following Chemical Formula 1-7 was prepared by purification.

[Formula 1-7]

It was confirmed that the prepared myrcene derivative compound represented by Chemical Formula 1-7 was synthesized through GC/MS and H-NMR analysis.

As a result of MS analysis, m/z=237 g/mol, and β-myrcene as a starting material was 136 g/mol. Also, H-NMR results are shown in FIG. 2 .

The GC/MS and H-NMR analysis were performed in the same manner as in Example 1.

Example 3: Preparation of a compound represented by Formula 1-6

34.7 mmol of 2-methyl-6-methyleneocta-1,7-dien-3-yl methanesulfonate, a compound represented by Formula 3, was dissolved in 150 g of dimethylformamide, and 52.1 mmol of K ₂ CO ₃ and mother 104.2 mmol of morphohline was sequentially added, and the reaction was stirred at room temperature (about 25° C.) for 12 hours. In this case, the compound represented by Formula 3 was prepared in the same manner as in 1) of Example 1. Thereafter, 5.1 g of a myrcene derivative compound represented by the following Chemical Formula 1-6 was prepared by purification.

[Formula 1-6]

It was confirmed that the prepared myrcene derivative compound represented by Formula 1-6 was synthesized through GC/MS and H-NMR analysis.

As a result of MS analysis, m/z=221 g/mol, and β-myrcene as a starting material was 136 g/mol. Also, H-NMR results are shown in FIG. 3 .

The GC/MS and H-NMR analysis were performed in the same manner as in Example 1.

Example 4: Preparation of a compound represented by Formula 1-8

In Example 3, except that 104.2 mmol of 3,3'-iminobis(N,N-dimethylpropylamine) (3,3'-iminobis(N,N-dimethylpropylamine)) was used instead of morpholine 5.1 g of a myrcene derivative compound represented by the following Chemical Formula 1-8 was prepared by performing the same reaction as in 3 .

[Formula 1-8]

It was confirmed that the prepared myrcene derivative compound represented by Formula 1-8 was synthesized through GC/MS and H-NMR analysis.

As a result of MS analysis, m/z=321 g/mol, and β-myrcene as a starting material was 136 g/mol. In addition, H-NMR results are shown in FIG. 4 .

The GC/MS and H-NMR analysis were performed in the same manner as in Example 1.

Example 5: Preparation of a compound represented by Formula 1-9

In Example 2, instead of 7.5 wt% N,N-dimethylaminopropanol, 7.5 wt% 1-[bis(3-(dimethylamino)propyl)amino]-2-propanol (1-[bis(3- (dimethylamino)propyl)amino]-2-propanol) 193 g (38.2 mmol, in dimethylformamide) was carried out in the same manner as in Example 2, except that the myrcene derivative compound represented by the following formula 1-9 8.6 g were prepared.

[Formula 1-9]

It was confirmed that the prepared myrcene derivative compound represented by Formula 1-9 was synthesized through GC/MS analysis. As a result of MS analysis, m/z=379 g/mol, and β-myrcene as a starting material was 136 g/mol.

Example 6: Preparation of a compound represented by Formula 1-1

In Example 3, 4.4 g of a myrcene derivative compound represented by Formula 1-1 was prepared in the same manner as in Example 3 except that 104.2 mmol of diethylamine was used instead of morpholine.

[Formula 1-1]

It was confirmed that the prepared myrcene derivative compound represented by Formula 1-1 was synthesized through GC/MS analysis, and as a result of MS analysis, m/z=179 g/mol. Meanwhile, β-myrcene as a starting material was 136 g/mol, and the GC/MS analysis was performed in the same manner as in Example 1.

Example 7: Preparation of a compound represented by Formula 1-2

In Example 3, 3.9 g of a myrcene derivative compound represented by the following Chemical Formula 1-2 was prepared in the same manner as in Example 3, except that 104.2 mmol of pyrrolidine was used instead of morpholine.

[Formula 1-2]

It was confirmed that the prepared myrcene derivative compound represented by Chemical Formula 1-1 was synthesized through GC/MS analysis, and as a result of MS analysis, m/z=205 g/mol. Meanwhile, β-myrcene as a starting material was 136 g/mol, and the GC/MS analysis was performed in the same manner as in Example 1.

Example 8: Preparation of a compound represented by Formula 1-3

In Example 3, 4.7 g of a myrcene derivative compound represented by the following Chemical Formula 1-3 was prepared in the same manner as in Example 3, except that 104.2 mmol of piperidine was used instead of morpholine.

[Formula 1-3]

It was confirmed that the prepared myrcene derivative compound represented by Chemical Formula 1-1 was synthesized through GC/MS analysis, and as a result of MS analysis, m/z=219 g/mol. Meanwhile, β-myrcene as a starting material was 136 g/mol, and the GC/MS analysis was performed in the same manner as in Example 1.

Example 9: Preparation of a compound represented by Formula 1-4

In Example 3, 4.8 g of a myrcene derivative compound represented by Formula 1-4 was prepared in the same manner as in Example 3, except that 104.2 mmol of azepane was used instead of morpholine.

[Formula 1-4]

It was confirmed that the prepared myrcene derivative compound represented by Formula 1-4 was synthesized through GC/MS analysis, and as a result of MS analysis, m/z=233 g/mol. Meanwhile, β-myrcene as a starting material was 136 g/mol, and the GC/MS analysis was performed in the same manner as in Example 1.

Example 10: Preparation of a compound represented by Formula 1-10

In Example 2, 7.5 wt% 2-((2-(dimethylamino)ethyl)(methyl)amino)ethan-1-ol (2-((2) -(dimethylamino)ethyl)(methyl)amino)ethan-1-ol) 75 g (38.2 mmol, in dimethylformamide) was carried out in the same manner as in Example 2, and represented by the following Chemical Formula 1-10 7.1 g of a myrcene derivative compound was prepared.

[Formula 1-10]

It was confirmed that the prepared myrcene derivative compound represented by Chemical Formula 1-10 was synthesized through GC/MS analysis. As a result of MS analysis, m/z=280 g/mol, and β-myrcene as a starting material was 136 g/mol.

Example 11: Preparation of a compound represented by Formula 1-11

In Example 2, instead of 7.5 wt% N,N-dimethylaminopropanol, 7.5 wt% 2-((2-(diethylamino)ethoxy)ethan-1-ol (2-((2-(diethylamino) )ethoxy)ethan-1-ol) 68 g (38.2 mmol, in dimethylformamide) was carried out in the same manner as in Example 2, except that 6.5 g of the myrcene derivative compound represented by the following Chemical Formula 1-9 was obtained. prepared.

[Formula 1-11]

It was confirmed that the prepared myrcene derivative compound represented by Formula 1-9 was synthesized through GC/MS analysis. As a result of MS analysis, m/z=267 g/mol, and β-myrcene as a starting material was 136 g/mol.

Example 12: Preparation of a compound represented by Formula 1-7

1) Preparation of a compound represented by Formula 5-1

39.4 mmol of N,N-dimethylaminopropanol and 43.4 mmol of triethylamine were dissolved in 120 g of methylene chloride, and the mixture was cooled to 0°C. After adding 47.3 mmol of methylsulfonyl chloride to this, the temperature was raised to 20° C. and the reaction was stirred for 3 hours. After completion of the reaction, methylene chloride was added to dilute it, washed with 1N HCl solution, washed again with saturated sodium bicarbonate (NaHCO ₃ ) solution, neutralized, washed again with Brine, and then water was removed with magnesium sulfate. Thereafter, methylene chloride was removed with a rotary evaporator, and 5.3 g of a compound represented by the following Chemical Formula 5-1 was prepared.

[Formula 5-1]

In Formula 5-1, Ms represents a mesyl group.

It was confirmed that the prepared compound represented by Chemical Formula 5-1 was synthesized through GC/MS analysis, and as a result of MS analysis, m/z=181 g/mol. Meanwhile, the starting material, N,N-dimethylaminopropanol, is 137 g/mol.

2) Preparation of a compound represented by Formula 1-7

34.7 mmol of (E)-2-methyl-6-methyleneocta-2,7-dien-1-ol, which is a compound represented by Formula 2 prepared in Preparation Example, was dissolved in 150 g of dimethylformamide, and therein, K ₂ CO ₃ 52.1 mmol and 52.1 mmol of the compound represented by Formula 5-1 prepared in 1) were sequentially added, and reacted with stirring at room temperature (about 25° C.) for 12 hours. After purification, 5.5 g of a myrcene derivative compound represented by Formula 1-7 was prepared.

[Formula 1-7]

It was confirmed that the prepared myrcene derivative compound represented by Chemical Formula 1-7 was synthesized through GC/MS analysis, and as a result of MS analysis, m/z=237 g/mol. On the other hand, the starting material, β-myrcene, was 136 g/mol, and the previous material, the compound represented by Chemical Formula 5-1, was 181 g/mol. At this time, the GC/MS analysis was performed in the same manner as in Example 1.

Claims (16)

Myrcene derivative compound represented by the following formula (1):
[Formula 1]

In Formula 1,
A is the following formula b, formula 1a, formula 1b or formula 1c,
[Formula b]

[Formula 1a]

[Formula 1b]

[Formula 1c]

In Formulas 1a to 1c,
R ₁ , R ₂ and R ₅ are each independently an alkyl group having 1 to 10 carbon atoms, or R ₁ and R ₂ are bonded to each other to form an aliphatic ring group having 5 to 10 carbon atoms,
R ₇ and R ₈ are each independently an alkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted with a substituent including at least one heteroatom selected from N and O atoms,
R ₃ , R ₄ and R ₆ are each independently an alkylene group having 1 to 10 carbon atoms that is unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms,
X and Z are each independently selected from N and O atoms, and when X is O, R ₈ does not exist, and when Z is O, R ₅ does not exist.
delete delete The method according to claim 1,
The myrcene derivative compound represented by Formula 1 is a myrcene derivative compound represented by the following Formulas 1-1 to 1-11:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

1) preparing a compound represented by the following formula (3) by reacting a compound represented by the following formula (2) with an alkylsulfonyl chloride-based compound in the presence of an organic solvent;
2) A method for producing a myrcene derivative compound represented by the following formula (1) according to claim 1, comprising reacting a compound represented by the formula (3) with a compound represented by the following formula (4):
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 1]

In Formula 1, Formula 3 and Formula 4,
A is the following formula b, formula 1a, formula 1b or formula 1c,
[Formula b]

[Formula 1a]

[Formula 1b]

[Formula 1c]

In Formulas 1a to 1c,
R ₁ , R ₂ and R ₅ are each independently an alkyl group having 1 to 10 carbon atoms, or R ₁ and R ₂ are bonded to each other to form an aliphatic ring group having 5 to 10 carbon atoms,
R ₇ and R ₈ are each independently an alkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted with a substituent containing one or more heteroatoms selected from N and O atoms,
R ₃ , R ₄ and R ₆ are each independently an alkylene group having 1 to 10 carbon atoms that is unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms,
X and Z are each independently one selected from N and O atoms, and when X is O, R ₈ is not present, and when Z is O, R ₅ is not present,
M is a methanesulfonate group.
6. The method of claim 5,
A method for preparing a myrcene derivative compound wherein the compound represented by Formula 2 and the alkylsulfonyl chloride-based compound are reacted in a molar ratio of 1:0.5 to 5 in step 1).
6. The method of claim 5,
The method for preparing a myrcene derivative compound, wherein the reaction of step 1) is carried out at a temperature of -20°C to 30°C for 10 minutes to 24 hours.
6. The method of claim 5,
A method for producing a myrcene derivative compound, wherein the compound represented by Formula 3 and the compound represented by Formula 4 are reacted in a molar ratio of 1:0.1 to 20 in step 1).
6. The method of claim 5,
The method for preparing a myrcene derivative compound wherein the reaction of step 2) is carried out at a temperature of 0° C. to 50° C. for 10 minutes to 24 hours.
6. The method of claim 5,
The method for producing a myrcene derivative compound, wherein the reaction of step 1) and step 2) is performed in the presence of a basic compound, respectively.
a) preparing a compound represented by the following formula (5) by reacting a compound represented by the following formula (4) with an alkylsulfonyl chloride-based compound in the presence of an organic solvent;
b) A method for producing a myrcene derivative compound represented by the following formula (1) according to claim 1, comprising reacting a compound represented by the formula (5) with a compound represented by the following formula (2):
[Formula 2]

[Formula 4]

[Formula 5]

[Formula 1]

In Formula 1, Formula 2, Formula 4 and Formula 5,
A is a substituent represented by the following formula 1c,
[Formula 1c]

In Formula 1c,
R ₇ and R ₈ are each independently an alkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted with a substituent including at least one heteroatom selected from N and O atoms,
R ₆ is an alkylene group having 1 to 10 carbon atoms that is unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms,
X is one selected from N and O atoms, and when X is O, R ₈ is not present, and when Z is O, R ₅ is not present,
M is a methanesulfonate group.
12. The method of claim 11,
A method for producing a myrcene derivative compound, wherein the compound represented by Formula 4 and the alkylsulfonyl chloride-based compound are reacted in a molar ratio of 1:0.5 to 5 in step a).
12. The method of claim 11,
The method for preparing a myrcene derivative compound wherein the reaction of step a) is carried out at a temperature of -20°C to 30°C for 10 minutes to 24 hours.
12. The method of claim 11,
A method for producing a myrcene derivative compound, wherein the compound represented by Formula 5 and the compound represented by Formula 2 are reacted in a molar ratio of 0.1 to 20:1 in step b).
12. The method of claim 11,
The method for preparing a myrcene derivative compound wherein the reaction of step b) is performed at a temperature of 0° C. to 50° C. for 10 minutes to 24 hours.
12. The method of claim 11,
The reaction of step a) and step b) is a method for producing a myrcene derivative compound, each of which is carried out in the presence of a basic compound.

Images