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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
  • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
  • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
  • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
  • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods

Definitions

• the present invention relates to a method for producing an aromatic compound.
• Aromatic compounds are used in various applications, for example, as liquid crystal materials, organic electroluminescence materials, medical and agricultural chemical intermediates, and the like. Aromatic compounds used in the above applications are produced, for example, by forming carbon-carbon bonds and carbon-heteroatom bonds by a coupling reaction.
• a catalyst is used in the coupling reaction to form a carbon-carbon bond and a carbon-heteroatom bond.
• a catalyst for the coupling reaction for example, a method of using a palladium source such as palladium chloride or palladium acetate together with a phosphine-based ligand such as triphenylphosphine and a method of using a palladium complex coordinated with an organic phosphine compound are known. Has been done. In recent years, for the purpose of reducing input energy by reducing the reaction temperature, reducing costs, etc., it has been studied to construct a highly active catalyst system while substituting an expensive ligand source.
• Patent Document 1 reports that a palladium complex catalyst in which a phosphine ligand and an allyl ligand are coordinated has high activity for carbon-carbon and carbon-nitrogen coupling reactions. For example, it is disclosed that it is used for the Suzuki-Miyaura coupling reaction at room temperature.
• Patent Document 2 reports that a palladium complex catalyst having a phosphine ligand and a paradacycle ligand acts as a highly active catalyst for a coupling reaction, and Buchwald using aryl chloride as a substrate. -Buchwald-Hartwig reaction etc. are described.
• the palladium catalysts disclosed in Patent Documents 1 and 2 have complicated synthetic routes and low industrial utility. Specifically, the synthesis of the palladium complex of Patent Document 1 requires a two-step synthesis consisting of a step of producing an allylpalladium dimer from palladium chloride and a step of reacting it with a phosphine ligand. .. The synthesis of the palladium complex of Patent Document 2 requires a two-step synthesis consisting of a step of reacting palladium acetate with o-diphenylamine and a step of reacting it with a phosphine ligand. As described above, there is a problem that it is difficult to industrially utilize the cross-coupling reaction in the production of aromatic compounds due to the complexity of catalyst preparation.
• An object of the present invention is to provide a method capable of producing an aromatic compound in high yield by utilizing a cross-coupling reaction.
• the present invention is as follows. [1] A method for producing an aromatic compound by a cross-coupling reaction between a nucleophile and an electrophile. A step of reacting the nucleophile with the electrophile to obtain the aromatic compound using Pd (OAc) 2 (PCy 3 ) 2 as a catalyst is included. Production method. [2] The cross-coupling reaction is a carbon-carbon coupling reaction. The manufacturing method according to [1]. [3] Each of the nucleophile and the electrophile is a compound having at least one aromatic ring. The manufacturing method according to [2].
• the nucleophile is a compound having at least one aromatic ring, and has at least one group selected from the group consisting of a boronic acid group and a boronic acid ester group on the at least one aromatic ring.
• the electrophile is a compound having at least one aromatic ring, and has at least one group selected from the group consisting of a halogen atom and a triflate group on the at least one aromatic ring.
• the electrophile is a compound having at least one aromatic ring.
• the nucleophile is a compound having at least one amino group.
• the electrophile is a compound having at least one aromatic ring, and has at least one group selected from the group consisting of a halogen atom and a triflate group on the at least one aromatic ring.
• the electrophile is a compound having at least one aromatic ring and has at least one chlorine atom on the at least one aromatic ring.
• an aromatic compound can be obtained in good yield by applying a cross-coupling reaction.
• the production method of the present embodiment is a method for producing an aromatic compound by a cross-coupling reaction between a nucleophile and an electrophile.
• the production method of the present embodiment includes a step of reacting the nucleophile with the electrophile to obtain the aromatic compound using Pd (OAc) 2 (PCy 3 ) 2 as a catalyst.
• the electrophile in this embodiment refers to a chemical species that receives electrons in a cross-coupling reaction system.
• the nucleophile in this embodiment refers to a chemical species that forms a bond to an atom having a low electron density in a cross-coupling reaction system.
• the cross-coupling reaction in the present embodiment refers to a reaction that binds two types of organic reaction substrates, that is, an electrophile and a nucleophile.
• the aromatic compound in the present embodiment is a product obtained by a cross-coupling reaction between a nucleophile and an electrophile, and is a compound having at least one aromatic ring.
• various aromatic compounds are produced in high yield by reacting two kinds of organic reaction substrates acting as electrophiles and nucleophiles with Pd (OAc) 2 (PCy 3 ) 2.
• Pd (OAc) 2 (PCy 3 ) 2 can be manufactured at.
• the catalyst Pd (OAc) 2 (PCy 3 ) 2 used in the present embodiment can be easily synthesized and can be easily applied to the production of aromatic compounds using a cross-coupling reaction. Since Pd (OAc) 2 (PCy 3 ) 2 is stable at room temperature (20 ⁇ 15 ° C.) and in the atmosphere and easy to handle, the manufacturing method using the catalyst is highly industrially usable.
• Pd (OAc) 2 (PCy 3 ) 2 used in the production method of the present embodiment, for example, a commercially available catalyst Pd (OAc) 2 (PCy 3) 2 manufactured by N.E. You may use it.
• Pd (OAc) 2 (PCy 3 ) 2 is prepared, for example, by mixing palladium acetate (Pd 3 (OAc) 6 ) and tricyclohexylphosphine (PCy 3 ) in the presence or absence of a solvent. Can be done.
• the cross-coupling reaction in the present embodiment is preferably a carbon-carbon coupling that newly forms a carbon-carbon bond or a carbon-nitrogen coupling reaction that newly forms a carbon-nitrogen bond.
• the carbon-carbon coupling reaction include a Suzuki-Miyaura coupling reaction, a Mizorogi-Heck reaction, and a Sonogashira coupling reaction. Among these, the Suzuki-Miyaura coupling reaction is preferable. Further, the carbon-nitrogen coupling reaction is preferably a Buchwald-Hartwig reaction.
• the electrophile in this embodiment is preferably a compound having at least one aromatic ring.
• the nucleophile in this embodiment may also be a compound having at least one aromatic ring.
• the aromatic ring contained in the electrophile and the nucleophile in the present embodiment may contain a heteroatom. That is, the aromatic ring in this embodiment also includes a complex aromatic ring.
• the reaction point in the electrophile is the carbon atom of the aromatic ring.
• the nucleophile is also preferably a compound having at least one aromatic ring. At this time, the reaction point in the nucleophile is the carbon atom of the aromatic ring.
• the nucleophile is not particularly limited as long as it is a compound containing at least one NH bond. At this time, the reaction point in the nucleophile is the nitrogen atom in the compound.
• reaction point refers to an atom in which a new covalent bond is formed by the reaction. Since the cross-coupling reaction is a reaction between reaction points existing in each of the electrophile and the nucleophile, the structure around the reaction points is arbitrary.
• the aromatic ring contained in the electrophoretic agent and the nucleophilic agent in the present embodiment is not particularly limited, and is, for example, a benzene ring, a biphenyl ring, a naphthalene ring, m-terphenyl, o-terphenyl, and p-ter.
• Examples thereof include a terphenyl ring such as phenyl, an acenaphthylene ring, a fluorene ring, a phenanthrene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a naphthacene ring, a perylene ring, and a pentacene ring.
• a terphenyl ring such as phenyl, an acenaphthylene ring, a fluorene ring, a phenanthrene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a naphthacene ring, a perylene ring, and a pentacene ring.
• the aromatic ring contained in the electrophoretic agent and the nucleating agent in the present embodiment is not particularly limited, and is, for example, a pyrrole ring, an oxazole ring, an isooxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, and an oxal ring.
• Examples include a heteroaromatic ring.
• the aromatic ring in this embodiment may have a substituent.
• the substituent is not particularly limited, for example, hydroxy group, a halogen atom, an alkyl group of C1 ⁇ C6, an alkenyl group of C2 ⁇ C6, an alkynyl group of C2 ⁇ C6, organic group represented by -OR 6, Examples thereof include an amino group represented by -N (R') (R ").
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• R 6 include an alkyl group of C1 to C6, an alkenyl group of C2 to C6, an alkynyl group of C2 to C6, and the like.
• R'and R independently include a hydrogen atom, an alkyl group of C1 to C6, an alkenyl group of C2 to C6, an alkynyl group of C2 to C6, an aromatic ring group, and the like.
• the aromatic ring group include an exemplary group similar to that of the aromatic ring contained in the electrophilic agent and the nucleophilic agent. Further, the aromatic ring group has the same substituent as described above. You may.
• the alkyl group of C1 to C6 means, for example, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent, and specifically, , Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned.
• the alkenyl group of C2 to C6 means, for example, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms which may have a substituent, and specifically, , Vinyl group, allyl group, vinyl group, allyl group, metalryl group, 1-buten-1-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 1-buten-3-yl
• the groups can be mentioned.
• the alkynyl group of C2 to C6 means, for example, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, and specifically, 2 -Propyne-1-yl group, 2-butyne-1-yl group, 3-butyne-1-yl group and the like can be mentioned.
• the nucleophilic agent is a compound having at least one aromatic ring, and a boronic acid group and boron on the at least one aromatic ring. It preferably has at least one group selected from acid ester groups. Further, the electrophile preferably has at least one aromatic ring, and preferably has at least one group selected from a halogen atom and a triflate group on the at least one aromatic ring. When the nucleophile has two or more aromatic rings and two or more boronic acid groups and / or boronic acid ester groups, the boronic acid groups and / or boronic acid ester groups are on the same aromatic ring.
• the electrophile has two or more aromatic rings and two or more halogen atoms and / or triflate groups
• the halogen atoms and / or triflate groups are substituted on the same aromatic ring. It may be substituted on a different aromatic ring.
• the carbon-carbon cross-coupling reaction in this embodiment is preferably represented by the following scheme.
• Formula (I) represents an electrophile
• formula (II) represents a nucleophile
• formula (III) represents a product aromatic compound.
• E1 and Nu each independently represent a unit having at least one aromatic ring.
• X is substituted on the carbon atom of the aromatic ring contained in E1 and represents at least one group selected from a halogen atom and a triflate group. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and the like.
• B ( RX ) ( RY ) is substituted on the carbon atom of the aromatic ring contained in Nu.
• R X and R Y each independently hydroxy group, an alkoxy group, R X and R Y may form a ring together.
• RX ) ( RY ) is not particularly limited as long as it is an organic boron group generally applicable to the Suzuki-Miyaura coupling reaction, and specifically, boronic acid (-(OH) 2 ) and boronic acid ester. (-(OR) 2 ), pinacol boron, etc. can be mentioned.
• boronic acid -(OH) 2
• boronic acid ester -(OR) 2
• pinacol boron, etc. can be mentioned.
• electrophile of the formula (IV) an aryl halide and an aromatic triflate are preferable, and an aryl chloride and an aryl bromide are more preferable.
• nucleophile of the formula (V) arylboronic acid and arylboronic acid ester are preferable.
• an aromatic compound having a biphenyl skeleton can be produced by a carbon-carbon cross-coupling reaction.
• the nucleophile is preferably a compound having at least one amino group.
• the electrophile preferably has at least one aromatic ring, and preferably has at least one group selected from a halogen atom and a triflate group on the at least one aromatic ring.
• the electrophile has two or more aromatic rings and two or more halogen atoms and / or triflate groups, the halogen atoms and / or triflate groups may be substituted on the same aromatic ring. , May be substituted on different aromatic rings.
• the carbon-nitrogen cross-coupling reaction in this embodiment is preferably represented by the following scheme.
• Formula (IV) represents an electrophile
• formula (V) represents a nucleophile
• formula (VI) represents a product aromatic compound.
• E2 represents a unit having at least one aromatic ring.
• X is substituted on the carbon of the aromatic ring contained in E2 and represents at least one group selected from a halogen atom and a triflate group.
• the halogen atom include a chlorine atom, a bromine atom, an iodine atom and the like.
• R X 'and R Y' are each independently, represent a hydrogen atom or any organic group.
• the optional organic group R X 'and R Y' for example, an alkyl group of C1 ⁇ C6, an alkenyl group of C2 ⁇ C6, an alkynyl group of C2 ⁇ C6, and aromatic ring group, and the like.
• examples of the aromatic ring group include an exemplary group similar to the aromatic ring contained in the electrophile and the nucleophile.
• the organic aromatic ring group the substituent described above, i.e., hydroxy group, a halogen atom, an alkyl group of C1 ⁇ C6, an alkenyl group of C2 ⁇ C6, an alkynyl group of C2 ⁇ C6, represented by -OR 6 It may be substituted with an oxy group, an amino group represented by -N (R') (R "), or the like.
• an aryl halide and an aromatic triflate are preferable, and an aryl chloride and an aryl bromide are more preferable.
• nucleophile of the formula (V) a primary amine and a secondary amine are preferable.
• an aromatic amine can be produced by a carbon-nitrogen cross-coupling reaction, for example, as shown by the following chemical reaction formula.
• the carbon-carbon cross-coupling reaction in the present embodiment includes reaction conditions such as Suzuki-Miyaura coupling reaction, Mizorogi-Heck reaction, and Sonogashira coupling reaction, preferably Suzuki-Miyaura coupling reaction. Can be applied.
• reaction conditions of the Buchwald-Hartwig reaction can be applied.
• the cross-coupling reaction in this embodiment is preferably carried out in the presence of a base.
• the base is not particularly limited, and examples thereof include potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium methoxyde, potassium phosphate, and the like.
• the amount of Pd (OAc) 2 (PCy 3 ) 2 used is not particularly limited, and is usually in the range of 0.001 mol% or more and 50 mol% or less with respect to the amount of the nucleophile or electrophile, preferably 0. The range is 0.01 mol% or more and 10 mol% or less.
• the reaction in this embodiment may be carried out in a solvent.
• the solvent is appropriately selected depending on the reaction temperature, the reaction substrate and the like.
• the solvent is not particularly limited as long as it can dissolve the substrate, and examples thereof include toluene, xylene, tetrahydrofuran, ethanol, acetonitrile, water and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.
• the reaction temperature may be appropriately selected depending on the solvent used, and is usually in the range of room temperature to 120 ° C.
• the room temperature here means 25 ⁇ 5 ° C.
• the reaction proceeds by using Pd (OAc) 2 (PCy 3 ) 2 even if the reaction temperature is set low, and the target product is obtained in good yield.
• Aromatic compounds can be obtained.
• the reaction temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and even more preferably room temperature.
• the obtained reaction solution may be concentrated as necessary, and then the residue may be directly combined with the next reaction to carry out the reaction, and appropriate post-treatment is carried out. Later, it may be obtained as an aromatic compound.
• Specific methods of post-treatment include extraction treatment and / or known purification such as crystallization, recrystallization, and chromatography.
• Catalyst preparation 1 Production of bis (acetato) bis (tricyclohexylphosphine) palladium (II) (Pd (OAc) 2 (PCy 3 ) 2 ) 80 g (360 mmol) of palladium acetate was dissolved in 700 mL of dichloromethane and insoluble by filtration. The component was removed. The obtained solution was transferred to a 2 L flask, the inside of the flask was sufficiently replaced with nitrogen, and 1 kg (720 mmol) of a 21.6% tricyclohexylphosphine toluene solution was added to obtain a mixture. The mixture was stirred overnight and then the solvent was removed on a rotary evaporator.
• Table 1 shows the yields of Example 1 and Comparative Examples 1 to 6.
• Table 2 shows the yields of Example 2 and Comparative Examples 7 to 10.
• the method for producing an aromatic compound of the present invention can obtain a product in a higher yield than the conventional production method. Therefore, the present invention is effective in the production of electronic component materials such as liquid crystal materials and organic electroluminescence materials, and the production of pharmaceutical intermediates, and contributes to the development of various industries.

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