TWI547467B - Preparation of diamine precursor compounds - Google Patents

Description

Method for producing diamine precursor compound

The present invention relates to a novel method for producing a raw material of a polyimine which is a liquid crystal alignment agent or the like from a low-cost raw material, and is particularly useful as a precursor of a specific diamine compound.

Polyimine is widely used as an electronic material such as a liquid crystal display element and a semiconductor protective material, an insulating material, a color filter, etc. because of its high mechanical strength, heat resistance, insulation, and solubility. In particular, polyimine is widely used as a liquid crystal alignment agent for forming a liquid crystal alignment film for controlling a liquid crystal alignment state among liquid crystal display elements such as liquid crystal televisions and liquid crystal displays.

The liquid crystal alignment film is obtained by applying a solution of a polyimine precursor such as polyacrylamide or a liquid crystal alignment agent solution of a soluble polyimine to an electrode substrate of glass or the like, and baking the obtained polyimine. The surface of the film is wiped in a single direction with a cloth such as cotton, nylon, or polyester, and is formed by a so-called brushing treatment.

The brushing treatment of the polyimide film is a step necessary for exhibiting the characteristics of the liquid crystal alignment film, but it is known that the brushing treatment occurs due to the influence of scratches, dust, mechanical force or static electricity on the surface of the liquid crystal alignment film. Various problems such as unevenness in the surface of the alignment process. In particular, recently, high performance, high definition, and large size of liquid crystal display elements have been demanded, and therefore, problems associated with the brushing process are required to be severely demanded.

On the other hand, in the brushing treatment of the polyimine-based liquid crystal alignment film, various proposals have been made for a method of producing a liquid crystal alignment film which suppresses occurrence of scratches and film peeling. For example, a liquid crystal alignment agent obtained by adding a compound having an epoxy group and a crosslinking agent such as a compound having an epoxy group and a reactive group other than an epoxy group using a polyaminic acid and/or a polyamidimine has been proposed. Method (refer to Patent Document 1 and Patent Document 2).

The present inventors have previously proposed a polyimine which is not easily damaged by the brushing treatment, and is a polyimine-based liquid crystal alignment agent using a specific diamine compound (refer to Patent Document 3). The liquid crystal alignment agent is a polyglycine and/or polyimine which is obtained by reacting a diamine compound which can be removed from the t-butoxycarbonyl group upon heating, and reacting it with a tetracarboxylic dianhydride. . The liquid crystal alignment agent can provide a crosslinking amine having a higher reactivity by removing the t-butoxycarbonyl group by heating to form a highly reactive aliphatic amine during the calcination step in the production process. The surface of the film becomes a strong liquid, and the liquid crystal alignment film is not easily damaged even by the brushing treatment.

In the process of producing polylysine and/or polyimine disclosed in the above Patent Document 3, a diamine compound having a tert-butoxycarbonyl group (a 3-butoxycarbonyl group, hereinafter also referred to as a Boc group) is used. A diamine compound represented by the following formula 21 is used. The starting material of the diamine compound is a propargylamine (HC≡CH ₂ NH ₂ ) which is expensive and difficult to obtain as described below. Further, the nitro compound of the precursor compound of the diamine compound needs to be subjected to a column operation which is not suitable for industrial production in the refining process.

[Chemical 1]

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 9-146100

Patent Document 2: JP-A-2007-11221

Patent Document 3: International Publication WO2010/050523 Report

An object of the present invention is to provide a tert-butoxycarbonyl group (Boc group) which is a raw material for polyamic acid and/or polyimine which is used for a liquid crystal alignment agent or the like in a simple and efficient manner from a low-cost raw material. A novel method of the nitro compound of the precursor of the diamine compound.

Further, the present invention provides a process for producing a diamine compound having a tert-butoxycarbonyl group from a nitro compound of a precursor compound of a diamine compound.

The present invention has been made in an effort to achieve the above object, and has invented the invention of a novel manufacturing method having the following gist. This manufacturing method, as will be described later, includes a novel compound in the process.

A method for producing a compound represented by Formula 1 according to the following reaction formula (1) (wherein R ¹ is -CH ₂ COOR, or -CH ₂ Ph(-Z) _m (Z is benzene) a substituent of the group (Ph), m is 0 to 5), R is a lower alkyl group or an alkali metal atom, and Ph is a phenyl group, and is reacted with di-tert-butyl dicarbonate ((Boc) ₂ O). The compound represented by Formula 2, followed by the following reaction formula (2), in the presence of a base, the resulting compound of the formula (2), and HA-CH ₂ -X (wherein, A is -C≡C - or -CH=CH-, X is a dissociative substituent) The compound represented by the reaction is reacted to produce a compound represented by Formula 3, and then the compound represented by Formula 3 and Formula 4 are obtained according to the following reaction formula (3) The compound represented by the formula (wherein Y is a dissociable substituent) is subjected to a coupling reaction to produce a diamine precursor compound represented by the formula (5).

[Chemical 2]

2. The method according to the above 1, wherein the compound represented by Formula 1 is tert-butyl glycinate or a salt thereof, or a benzylamine or a salt thereof.

3. The method according to the above 1 or 2, wherein the coupling reaction is carried out under a coexisting metal complex, a ligand, and a base.

4. The method according to any one of the above 1 to 3, wherein the coupling reaction is carried out under a palladium complex in which a ligand containing a tertiary phosphine or a tertiary phosphite is present.

5. The method according to any one of the above 1 to 4, wherein in the compound represented by the formula 4, Y is a bromine, iodine or trifluoromethanesulfonate group.

6. The method according to any one of the above 1 to 5, wherein, in the compound represented by HA-CH ₂ -X, X is a halogen or a sulfonate group.

7. The method according to the above 1, wherein the compound represented by HA-CH ₂ -X is a propargyl halide or an allyl halide.

8. A production method according to the following reaction formula (4), wherein the compound represented by the formula 5 obtained by the method according to any one of the above 1 to 7 is reduced to produce the formula 6 (wherein R ² A method of a diamine compound represented by a hydrogen atom or -CH ₂ COOR, and R is a lower alkyl group.

[Chemical 3]

9. An ester compound represented by the following formula.

[Chemical 4]

10. A nitro compound which is represented by any of the following formulas.

[Chemical 5]

The present invention can provide a precursor compound of a tert-butoxycarbonyl diamine compound which is a simple and efficient raw material for producing a liquid crystal alignment agent for a polyphthalic acid and/or a polyimide. A novel method of nitro compounds.

Further, the present invention provides a process for producing a diamine compound having a tert-butoxycarbonyl group from a nitro compound of a precursor compound of the obtained diamine compound.

Further, the present invention provides the following novel compounds.

[Chemical 6]

[Formation of the Invention]

The invention will be described in more detail below.

A. A compound represented by the following formula 2 is produced from a compound represented by the following formula 1 as a raw material

The compound represented by Formula 1 is used as a raw material, and by reacting it with (Boc) ₂ O (di-tert-butyl dicarbonate), the compound represented by Formula 2 is produced according to the reaction formula (1).

In Formula 1, R ¹ is -CH ₂ COOR, or -CH ₂ Ph(-Z) _m (Z is a substituent on phenyl (Ph), m is 0 to 5), and R is a lower alkyl group or an alkali metal Atom, Ph is a phenyl group.

The lower alkyl group means an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably -CH ₂ CO ₂ -tert-Bu (tert-butyl). The alkali metal is preferably lithium, sodium or potassium, and particularly preferably sodium or potassium.

Z is a substituent on the phenyl group, a fluorine atom, a nitro group, a carboxyl group, an ester group, a cyano group or a C _1-4 alkoxycarbonyl group, preferably a methoxy group or a nitro group.

m is from 0 to 5, preferably from 0 to 2.

The compound represented by Formula 1 is a glycine-tert-butyl ester or a salt thereof when R ¹ is -CH ₂ CO ₂ -tert-Bu, and is a benzylamine when R ¹ is -CH ₂ Ph or Its salt. Such glycine-tert-butyl ester or a salt thereof, and benzylamine or a salt thereof are different from propargylamine (HC≡CCH ₂ NH ₂ ) and the like, and are readily available and inexpensive.

[Chemistry 7]

The reaction of the compound represented by the above formula 2 is preferably carried out in the presence of a base. The base may be an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate or cesium carbonate; trimethylamine, triethylamine Amines such as amine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, trimethylpyridine, etc.; sodium hydride, potassium hydride, tert-butoxy Sodium base, tert-butoxy potassium, and the like.

When the compound represented by Formula 1 is a free amine, the reaction can be carried out even in the absence of a base. However, when a base is used, it is preferred to use an amine in order to consider the handleability after the reaction.

The reaction solvent can be used, and it has any stability under the reaction conditions, and it is inactive and does not hinder any of the solvents for the intended reaction. For example, an aprotic polar organic solvent such as dimethylformamide, dimethylhydrazine, dimethylacetate or N-methylpyrrolidone; diethyl ether, isopropyl ether or THF (tetrahydrofuran) can be used. ); an ether of TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether), dioxane, etc.; an aliphatic hydrocarbon such as pentane, hexane, heptane or petroleum ether; benzene, toluene, and Toluene, , aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, nitrobenzene, and tetralin; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; methyl acetate, ethyl acetate, and acetic acid a lower fatty acid ester such as butyl ester or methyl propionate; a nitrile such as acetonitrile, propionitrile or butyronitrile.

The solvent may be appropriately selected in consideration of the reaction, and may be used singly or in combination of two or more kinds. The above solvent may be a solvent which does not contain water using a suitable dehydrating agent or drying agent.

The reaction temperature is preferably selected from the range of from -100 ° C to the boiling temperature of the reaction solvent to be used, more preferably from -50 to 150 ° C, particularly preferably from 0 to 60 ° C. The reaction time is preferably from 0.1 to 1,000 hours, more preferably from 0.5 to 50 hours.

The compound represented by the formula 2 obtained in the above reaction formula (1) can be purified by distillation, recrystallization, column chromatography such as hydrazine gel or the like, or can be used as it is in the subsequent step without purification.

Preferred examples of the compound represented by Formula 2 thus produced are, for example, Boc-NHCH ₂ COOtert-Bu, or Boc-NHCH ₂ Ph(-Z) _m (wherein Z is a substituent on a phenyl group, a fluorine atom, Nitro, carboxyl, ester, cyano or C _1-4 alkoxycarbonyl, m is from 0 to 5).

B. A compound represented by the following formula 3 is produced from a compound represented by the following formula 2

The compound represented by the formula 2 obtained by the above reaction formula (1) is reacted with HA-CH ₂ -X in the presence of a base (wherein, A is -C≡C- or -CH=CH-, X is The substituent of the dissociation ability), the compound represented by Formula 3 is produced according to the following reaction formula (2).

[化8]

The above HA-CH ₂ -X is a propargylating agent when A is -C≡C-, and is an allylation agent when A is -CH=CH-. X is a substituent having dissociation ability, such as halogen of fluorine, chlorine, bromine, iodine or the like; p-tosylate group (-OSO ₂ C ₆ H ₄ -p-CH ₃ ), methanesulfonate group (- a sulfonate group such as OSO ₂ CH ₃ ) or a trifluoromethanesulfonate group (-OSO ₂ CF ₃ ); an organic group such as an acetate group (-OCOCH ₃ ) or a benzoate group (-OCOPh); Acid ester group; methoxy carbon methoxy group (-OCO ₂ CH ₃ ), ethoxy carbon methoxy group (-OCO ₂ CH ₂ CH ₃ ), i-propoxy carbon methoxy group (-OCO ₂ CH (CH ₃ ) ₂ ), a carbonate represented by a phenoxycarbon alkoxy group (-OCO ₂ Ph), and the like. Among them, from the viewpoint of reactivity, a halogen or a sulfonate group is preferred.

The base used in the reaction may be an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate or cesium carbonate; tert-butyl a base such as sodium oxyhydride, potassium tert-butoxide, sodium hydride or potassium hydride; trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropyl An amine such as ethylamine, pyridine, quinoline or trimethylpyridine. Among them, preferred are tert-butoxy sodium, tert-butoxy potassium, sodium hydride, potassium hydride and the like.

The reaction solvent can be used, and it has any stability under the reaction conditions, and any one of the solvents which are inactive and do not interfere with the intended reaction. For example, an aprotic polar organic solvent such as dimethylformamide, dimethylhydrazine, dimethylacetate or N-methylpyrrolidone; diethyl ether, isopropyl ether, THF, TBME can be used; , ethers such as CPME and dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; benzene, toluene, xylene, An aromatic hydrocarbon such as chlorobenzene, dichlorobenzene, nitrobenzene or tetralin; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride or dichloroethane; methyl acetate or ethyl acetate; a lower fatty acid ester such as butyl acetate or methyl propionate; a nitrile such as acetonitrile, propionitrile or butyronitrile.

The solvent may be appropriately selected in consideration of the reaction, and may be used singly or in combination of two or more kinds. Further, depending on the case, the solvent may be a solvent which does not contain water using a suitable dehydrating agent or drying agent.

Further, in order to carry out the above reaction more efficiently, an iodide such as tetra-n-butylammonium iodide, sodium iodide or potassium iodide may be added.

The reaction temperature is preferably selected from the range of from -100 ° C to the boiling temperature of the reaction solvent to be used, more preferably from -50 to 150 ° C, particularly preferably from -20 to 100 ° C. The reaction time is preferably from 0.1 to 1,000 hours, more preferably from 0.5 to 50 hours.

The compound represented by the formula 3 obtained in the above reaction formula (2) can be purified by distillation, recrystallization, column chromatography such as hydrazine gel or the like, or can be used as it is in the subsequent step without purification.

A preferred example of the compound represented by Formula 3 thus produced is Boc-N(CH ₂ C≡CH)CH ₂ COOt-Bu, Boc-N(CH ₂ C≡CH)CH ₂ Ph(-Z) _m Boc-N(CH ₂ CH=CH ₂ )CH ₂ COOt-Bu, or Boc-N(CH ₂ CH=CH ₂ )CH ₂ Ph(-Z) _m . In the formula, Z is a substituent on a phenyl group, a fluorine atom, a nitro group, a carboxyl group, an ester group, a cyano group or a C _1-4 alkoxycarbonyl group, and m is from 0 to 5.

Among the compounds represented by Formula 3, the following ester compounds are novel compounds prior to the present application.

[Chemistry 9]

C. A compound represented by the following formula 5 is produced from a compound represented by the following formula 3

The compound represented by the formula 3 obtained in the above reaction formula (2) is subjected to a coupling reaction such as a round reaction or a black gram reaction with a compound represented by the formula 4 by coexisting a metal complex, a ligand and a base. A compound represented by Formula 5 is produced.

[化10]

In the compound represented by Formula 4, Y is a substituent having a dissociation ability, for example, a halogen of fluorine, chlorine, bromine or iodine; and a p-tosylate group (-OSO ₂ C ₆ H ₄ -p-CH ₃ ) a sulfonate group such as a methanesulfonate group (-OSO ₂ CH ₃ ) or a trifluoromethanesulfonate group (-OSO ₂ CF ₃ ). Among them, the viewpoint of reactivity is preferably a bromine, iodine or trifluoromethanesulfonate group.

This reaction is carried out using a metal complex catalyst formed by a suitable metal complex and a ligand. In general, the metal complex is a palladium complex or a nickel complex, and the reaction is preferably a copper catalyst for coexisting the catalyst.

The metal complex catalyst may use various structures, preferably a so-called low-valent palladium complex or a nickel complex, particularly preferably a zero-order phosphine or a tertiary phosphite as a ligand. Valence metal complex catalyst. Further, an appropriate precursor which is easily converted to a zero-valent metal complex catalyst in the reaction system can be used. In addition, in the reaction system, a metal complex which does not contain a ligand of a tertiary phosphine or a tertiary phosphite, and a tertiary phosphine or a tertiary phosphite of a ligand can form a ligand of 3 Low valence metal complex catalyst for phosphine or tertiary phosphite.

Grade III phosphine or tertiary phosphite such as triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis(diphenyl) Ethylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)di Ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, and the like. Further, a metal complex catalyst obtained by mixing two or more kinds of these ligands is also suitable.

The metal complex catalyst is used in combination with a palladium complex which does not contain a tertiary phosphine or a tertiary phosphite, and a metal complex which contains a tertiary phosphine or a tertiary phosphite. At this time, the above ligands may be additionally combined. Palladium complexes without a grade 3 phosphine or a grade 3 phosphite such as bis(benzylideneacetone)palladium, tris(benzylideneacetone)dipalladium, bis(acetonitrile)dichloropalladium, bis(benzonitrile) Dichloropalladium, palladium acetate, palladium chloride, palladium-activated carbon, and the like. Further, a palladium complex compound having a 3-stage phosphine or a 3-grade phosphite as a ligand, such as (extended ethyl) bis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, bis(triphenyl) Phosphine) dichloropalladium and the like.

The amount of the palladium complex to be used, that is, the amount of the catalyst is preferably 20 mol% or less, and particularly preferably 10 mol% or less based on the compound represented by Formula 4. At the same time, the copper catalyst used as the catalyst is preferably a monovalent substance such as copper (I) chloride, copper (I) bromide, copper (I) iodide or copper (I) acetate.

A base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate or cesium carbonate; methylamine, Methylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triiso Propylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, trimethylpyridine, pyrrolidine, piperidine, morpholine, N-A An amine such as kimorpholine; sodium acetate, potassium acetate, lithium acetate, and the like.

When A of the compound represented by Formula 3 of the starting material is a terminal acetylene compound of -C≡C-, a metal acetylene compound (L _n MC≡C-, a formula can be formed by using an organic lithium, an organomagnesium, an organozinc or the like for a base. Where M is a metal, L is a ligand, and n is an integer not including 0), and the metal acetylene compound is used in the reaction. M, such as lithium, magnesium, zinc, tin, boron, and the like. L is fluorine, chlorine, bromine, iodine, OH, C _1-6 alkoxy or the like.

The reaction solvent can be used, and it has stability under the reaction conditions, and inactivity does not hinder any of the reaction. The reaction solvent may be water, an alcohol, an amine, an aprotic polar organic solvent (DMF (dimethylformamide), DMSO (dimethylammonium), DMAc (dimethylacetamide), NMP ( N-methylpyrrolidone), ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether) Etc., aromatic hydrocarbons (benzene, toluene, xylene, , chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, acetic acid) Ethyl ester, butyl acetate, methyl propionate, etc., nitrile (acetonitrile, propionitrile, butyronitrile, etc.). These solvents may be appropriately selected in consideration of the ease of reaction, and may be used singly or in combination of two or more kinds. Further, depending on the case, the solvent may be a solvent which does not contain water using a suitable dehydrating agent or drying agent.

The reaction temperature is preferably selected from the range of from -100 ° C to the boiling temperature of the reaction solvent to be used, more preferably from -50 to 200 ° C, particularly preferably from 20 to 150 ° C. The reaction time is preferably from 0.1 to 1,000 hours, more preferably from 0.5 to 100 hours.

The compound represented by the formula 5 obtained in the above reaction formula (3) is preferably purified by column chromatography such as distillation, recrystallization or hydrazine gel. Further, recrystallization is preferably carried out as low as possible.

Among the compounds represented by Formula 5 thus produced, the following three compounds are novel compounds prior to the present application.

[11]

D. A diamine represented by the following formula 6 is produced from a compound represented by the following formula 5

[化12]

The compound represented by the formula 5 obtained by the above reaction formula (3), by reducing the nitro group of the benzene ring, the unsaturated bond of the branched portion thereof, and the benzyl group resulting from the structure, according to the above reaction formula (4) A diamine represented by Formula 6 is produced. In the compound represented by Formula 6, when R ¹ of the compound represented by Formula 5 is a benzyl group, R ² is a hydrogen atom, and when R ¹ is CH ₂ COOR, R ² is also CH ₂ COOR. R is a lower alkyl group, and the lower alkyl group at this time is the same as that in the case of R ¹ .

The method for reducing the compound represented by the above formula 5 may be a hydrogenation reaction using a palladium-activated carbon or a platinum-activated carbon for a catalyst; a reduction reaction of coexisting iron, tin, zinc or a salt thereof and protons; a reduction reaction using formic acid as a hydrogen source; a reaction using hydrazine as a hydrogen source; Also, the reaction can be carried out in combination.

In the above-mentioned reduction reaction, it is preferred to use a hydrogenation reaction in consideration of the reactivity of the structure of the compound represented by Formula 5 of the substrate and the reduction reaction.

The catalyst to be used is an activated carbon-supporting metal which can be obtained from a commercially available product, for example, palladium-activated carbon, platinum-activated carbon, ruthenium-activated carbon or the like. Further, it may be a metal catalyst which is not necessarily an activated carbon-supporting type such as palladium hydroxide, platinum oxide or Raney nickel. Good results are obtained even with the use of palladium-activated carbon which is generally widely used.

The reaction solvent can be used, and it has stability under the reaction conditions, and it is inactive and does not interfere with any of the solvents. For example, an aprotic polar organic solvent such as dimethylformamide, dimethylhydrazine, dimethylacetate or N-methylpyrrolidone; diethyl ether, isopropyl ether, THF, TBME, or the like can be used. An ether of CPME or dioxane; an aliphatic hydrocarbon such as pentane, hexane, heptane or petroleum ether; benzene, toluene, xylene, , aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, nitrobenzene, and tetralin; halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; methyl acetate, ethyl acetate, and acetic acid a lower fatty acid ester such as butyl ester or methyl propionate; a nitrile such as acetonitrile, propionitrile or butyronitrile.

These solvents may be appropriately selected in consideration of the ease of reaction, and may be used singly or in combination of two or more kinds. Further, depending on the case, the solvent may be a solvent which does not contain water using a suitable dehydrating agent or drying agent.

In order to carry out the above reduction reaction more efficiently, the reaction can be carried out under coexisting carbon. The amount of activated carbon used at this time is not particularly limited, but is preferably from 1 to 20% by weight, more preferably from 1 to 10% by weight, based on the compound represented by Formula 5.

Further, in order to carry out the reaction more efficiently, the reaction can be carried out under pressure. In this case, in order to avoid reduction of the benzene nucleus, it is preferred to carry out the reaction in a pressure range of 20 atm. (kgf), more preferably in a range of up to 10 atm.

The reaction temperature is preferably selected from the range of from -100 ° C to the boiling temperature of the reaction solvent to be used, more preferably from -50 to 150 ° C, particularly preferably from 0 to 80 ° C. The reaction time is preferably from 0.1 to 1,000 hours, more preferably from 1 to 200 hours.

The compound represented by the formula 6 obtained in the above reaction formula (4) is preferably purified by column chromatography such as distillation, recrystallization or hydrazine gel.

The compound represented by Formula 6 thus produced is preferably a compound represented by R ² as a hydrogen atom or CH ₂ COOt-Bu.

The invention will be more specifically illustrated by the following examples, but without limiting the invention, Further, the analysis apparatus and analysis conditions employed in the examples are as follows.

¹ H-NMR and ¹³ C-NMR;

Device: Varian NMR System 400 NB (400MHz)

Determination of solvent: CDCl ₃ DMSO-d ₆

Reference material: tetramethyl decane (TMS) (the δ value of ¹ H of TMS is 0.0 ppm)

CDCl ₃ (the δ value of ¹³ C of CDCl ₃ is 77.0 ppm)

Example 1 (Example of Reaction Formula (1))

[Chemistry 13]

A suspension of tert-butyl ester of glycine acid 9 (10.0 g, 59.7 mmol) in toluene (46.2 mL) was maintained at 60 ° C, and triethylamine (6.51 g, 64.3 mmol) was added and stirred for 0.5 hour. Next, a solution of di-tert-butyl dicarbonate (10.0 g, 45.9 mmol) in toluene (11.6 mL) was added dropwise to the reaction mixture for 6 hours.

The organic layer was then separated by the addition of water (30 mL). Thereafter, the solvent was evaporated from the organic layer, and then recrystallized from n-hexane to give N-Boc-glycine-tert-butyl ester 10 (10.6 g, 45.9 mmol, 100% yield). The structure of the product was confirmed by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ 4.98 (bs, 1H, NH), 3.79 (d, 2H, J = 5.6 Hz, NCH ₂ CO ₂ -tert-Bu), 1.52-1.40 (m, 18H, (tert -Bu)×2).

Example 2 (Example of Reaction Formula (1))

[Chemistry 14]

A suspension of toluene (10 L) of glycine acid tert-butyl ester hydrochloride 9 (1.258 Kg, 7.505 mol) was maintained at 10 ° C, and triethylamine (0.9113 Kg, 9.060 mol) was added and stirred for 1 hour. Next, di-tert-butyl dicarbonate (1.474 Kg, 6.754 mol) was added dropwise to the reaction mixture for 3 hours.

After the reaction was stopped by adding water (5 L), the organic layer was separated. Thereafter, the solvent was distilled away from the organic layer to give the desired N-Boc-glycine-tert-butyl ester 10 (1.551 kg, 6.706 mol, 99% yield). Obtained by the ¹ H-NMR analysis confirmed N-Boc- glycine -tert- butyl ester 10, the results obtained from the above Example 1 N-Boc- glycine -tert- butyl ester of ¹ H- NMR was identical.

Example 3 (Example of Reaction Formula (2))

[化15]

Potassium tert-butoxylate (80.05 g, 0.7134 mol) in THF (550 mL) was suspended in a drop of N-Boc-glycolic acid tert-butyl ester 10 (150.0 g, 0.6485 mol) in toluene (550 mL) In the solution, the mixture was stirred at room temperature for 10 minutes. Next, the obtained reaction mixture was ice-cooled, and then a solution of tetra-n-butylammonium iodide (7.186 g, 0.01946 mol) and propargyl bromide (84.86 g, 0.7134 mol) in toluene (200 mL) was added to the reaction. In the mixture.

After the resulting reaction mixture was stirred at room temperature for 3 hours, the reaction was quenched by adding 8% by weight aqueous ammonium chloride (500 mL), and the organic layer was separated. Thereafter, the solvent was evaporated from the organic layer to give the desired acetylene compound 11 (153.4 g, 0.5695mol, 88% yield).

The structure of the acetylene compound 11 at the end of the product was confirmed by ¹ H-NMR analysis.

¹ H _- NMR (CDCl ₃ ): δ 4.20-4.10 (m, 2H, HC ≡ CCH ₂ N), 4.00-3.90 (m, 2H, NCH ₂ CO ₂ -tert-Bu), 2.23 (t, 1H, J) = 2.6 Hz, HC ≡ C), 1.50-1.40 (m, 18H, (tert-Bu) x 2).

Example 4 (Example of Reaction Formula (2))

[Chemistry 16]

Sodium hydride (55 wt% mineral oil dispersion, 0.8490 g, 19.46 mmol), washed with 10 mL of hexane to remove mineral oil) DMF (6 mL) suspension after ice cooling, slowly N-Boc-gan A solution of tert-butyl ester 10 (3.000 g, 12.97 mmol) in DMF (12 mL) was added dropwise.

After stirring the resulting reaction mixture for 1 hour at room temperature, a solution of propargyl bromide (1.697 g, 14.27 mmol) in DMF (12 mL) was added to the mixture. The reaction mixture was kept at room temperature, and after reacting for 18 hours, water (60 mL) was added under ice cooling to stop the reaction. Next, hexane (50 mL) was added, and the organic layer was separated, and the aqueous layer was extracted twice with hexane (50 mL). The obtained organic layer was concentrated, washed with brine (50 mL), and then evaporated. After magnesium sulfate was collected by filtration, the obtained organic layer was evaporated to ethylamine (yield)

The structure of the obtained compound was confirmed by ¹ H-NMR analysis, and the result was identical to the ¹ H-NMR of the compound 11 obtained by using t-BuOK in the above Example 3.

Example 5 (Example of Reaction Formula (3))

[化17]

A solution of diethylamine (37.13 g, 0.5077 mol) and terminal acetylene 11 (152.9 g, 0.5680 mol) in THF (370 mL) was added to 2-iodo-4-nitroaniline 12 (111.7 g, 0.4231). Mol), a suspension of bis(triphenylphosphine)palladium dichloride (2.970 g, 0.004231 mol) and copper (I) iodide (1.611 g, 0.008461 mol) in THF (500 mL). The temperature was then raised to 40 ° C and the reaction mixture was stirred for 24 hours. In order to stop the reaction, water (3850 mL) was poured into the reaction mixture to crystallize, and the mixture was stirred for 3 hours.

The object mixture was filtered from the obtained reaction mixture to give a dried material. The obtained crude product was recrystallized using toluene to give the desired nitro compound 13 (144.6 g, 0.3566 mol, 84% yield). The structure of the nitro compound 13 was confirmed by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ 8.16 (d, 1H, J = 2.4 Hz, Ar-H), 7.99 (dd, 1H, J = 9.2, 2.4 Hz, Ar-H), 6.62 (d, 1H, J=9.2 Hz, Ar-H), 5.15 (s, 2H, NH ₂ ), 4.45-4.32 (m. 2H, C≡CCH ₂ N), 4.04-3.88 (m, 2H, NCH ₂ CO ₂ tert-Bu ), 1.55-1.40 (m, 18H, (tert-Bu) × 2).

Example 6 (Example of Reaction Formula (3))

[化18]

A solution of diethylamine (10.4 g, 142 mmol) and terminal acetylene 11 (11.5 g, 42.6 mmol) in toluene (28.9 mL) was added to 2-iodo-4-nitroaniline 12 (7.50 g, 28.4). A suspension of ethyl (49.9 mL) of bis(triphenylphosphine)palladium dichloride (99.6 mg, 0.142 mmol) and copper (I) iodide (54.1 mg, 0.284 mmol). Next, the reaction mixture was heated to 50 ° C and stirred for 6 hours.

Activated carbon (0.750 g) was added to the obtained reaction mixture, and after the activated carbon and the reaction residue were filtered off at 50 ° C, water (22.5 mL) was added to the filtrate to separate the organic phase. Next, the solvent of the organic phase is distilled off under reduced pressure, and toluene (46.2 mL) and activated carbon (1.15 g) are added to the obtained crude product. The activated carbon is filtered off at a temperature not exceeding 80 ° C, and the target material is recrystallized from the filtrate. Nitro 13 (10.3 g, 25.2 mmol, 89% yield). The structure of the nitro compound 13 was confirmed by ¹ H-NMR analysis, and the result was identical to the ¹ H-NMR of the nitro compound 13 obtained in the above Example 5.

Example 7 (Example of Reaction Formula (3))

[Chemistry 19]

A solution of diethylamine (11.1 g, 152 mmol) and terminal acetylene 11 (12.3 g, 45.6 mmol) in toluene (34.2 mL) was added to 2-iodo-4-nitroaniline 12 (8.03 g, 30.4). A suspension of bis(triphenylphosphine)palladium dichloride (213 mg, 0.304 mmol) and copper (I) iodide (116 mg, 0.608 mmol) in toluene (10.3 mL). Next, the reaction mixture was heated to 40 ° C and stirred for 1 hour.

Ethyl acetate (53.4 mL) and activated carbon (0.803 g) were added to the obtained reaction mixture, and the activated carbon and the reaction residue were filtered off at 50 ° C, and then water (24.1 mL) was added to the filtrate, and the organic phase was separated. Next, the solvent of the organic phase was distilled off under reduced pressure, and toluene (35.6 mL) and activated carbon (1.23 g) were added to the obtained crude product. After the activated carbon was filtered off at 100 ° C, the target material was recrystallized from the filtrate to obtain a nitro compound. 13 (10.2 g, 25.2 mmol, 83% yield). The structure of the nitro compound 13 was confirmed by ¹ H-NMR analysis, and the result was identical to the ¹ H-NMR of the nitro compound 13 obtained in the above Example 5.

Example 8 (Example of Reaction Formula (3))

[Chemistry 20]

A solution of bis(n-butyl)amine (2.93 g, 22.7 mmol) and terminal acetylene 11 (7.65 g, 28.4 mmol) in toluene (21.2 mL) was added to 2-iodo-4-nitroaniline 12 at room temperature. (5.00 g, 18.9 mmol), a suspension of bis(triphenylphosphine)palladium dichloride (133 mg, 0.189 mmol) and copper (I) iodide (72.0 mg, 0.378 mmol) in toluene (7.6 mL). Next, the reaction mixture was heated to 40 ° C and stirred for 27 hours.

Ethyl acetate (33.3 mL) and activated carbon (0.500 g) were added to the obtained reaction mixture. After the activated carbon and the reaction residue were filtered off at 50 ° C, water (15.0 mL) was added to the filtrate, and the organic phase was separated. Next, the solvent of the organic phase was distilled off under reduced pressure, and toluene (20.8 mL) and activated carbon (0.766 g) were added to the obtained crude product. After the activated carbon was filtered off at 100 ° C, the desired product was recrystallized from the filtrate to obtain a nitro compound. 13 (5.48 g, 13.5 mmol, 72% yield). The structure of the nitro compound 13 was confirmed by ¹ H-NMR analysis, and the result was identical to the ¹ H-NMR of the nitro compound 13 obtained in the above Example 5.

Example 9 (Examples of Reaction Formulas (1 to 3))

[Chem. 21]

A suspension of tert-butyl ester of glycine acid (10.02 g, 59.77 mmol) in toluene (46.2 mL) was maintained at 20 ° C, and triethylamine (6.680 g, 66.01 mmol) was added and stirred for 1 hour. . Next, a solution of di-tert-butyl dicarbonate (10.01 g, 45.86 mmol) in toluene (11.6 mL) was added dropwise to the reaction mixture for 5 hours. After confirming the completion of the reaction, water (40 mL) was added, and the organic layer was separated. Thereafter, a part of the solvent was distilled off from the organic layer to obtain a toluene solution (43.47 g) containing the desired N-Boc-glycine-tert-butyl ester 10.

Next, tert-butoxy potassium (5.490 g, 48.93 mol) of tetrahydrofuran (26.7 mL) was suspended and dropped into the toluene solution of N-Boc-glycine-tert-butyl ester 10 obtained above. The mixture was stirred at room temperature for 10 minutes. After the reaction mixture was ice-cooled, a solution of tetra-n-butylammonium iodide (0.4864 g, 13.17 mmol) and propargyl bromide (5.820 g, 48.95 mmol) in toluene (10.0 mL) was added to the reaction mixture. In the liquid. After the reaction mixture was stirred at room temperature for 3 hours, a 13% by weight aqueous solution of ammonium chloride (23.7 mL) was added to terminate the reaction, and the organic layer was separated. Thereafter, a part of the solvent was distilled off from the organic layer to obtain a toluene solution (32.71 g) containing the desired terminal acetylene compound 11.

Diethylamine (9.47 g, 129 mmol and the above-mentioned toluene solution of the terminal acetylene 11 obtained above was added to 2-iodo-4-nitroaniline 12 (6.84 g, 25.9 mmol), bis(triphenylphosphine) at room temperature. a suspension of palladium dichloride (90.0 mg, 0.130 mmol) and copper (I) iodide (49.3 mg, 0.259 mmol) in ethyl acetate (45.5 mL). The reaction mixture was then warmed to 50 ° C. After 6 hours, activated carbon (0.68 g) was added to the reaction mixture, and the activated carbon and the reaction residue were filtered off at 50 ° C, then water (20.5 mL) was added to the filtrate, and the organic phase was separated. After the solvent, toluene (42.5 mL) and activated carbon (1.05 g) were added to the obtained crude product, and the activated carbon was filtered off at a temperature not exceeding 80 ° C, and the object was recrystallized from the filtrate to obtain a nitro group 13 ( 7.86 g, 19.4 mmol, 75% yield. The structure of the nitro compound 13 was confirmed by ¹ H-NMR analysis, and the result was identical to the ¹ H-NMR of the nitro compound 13 obtained in the above Example 5.

Example 10 (Example of Reaction Formula (4))

[化22]

5% palladium-activated carbon (14.40 g) was added to a suspension of nitro compound 13 (144.0 g, 0.3552 mol) in toluene (1.500 L). The reaction mixture was allowed to react in a hydrogen atmosphere at 50 ° C for 48 hours. After the completion of the reaction, the catalyst in the reaction mixture was filtered off, and the solvent was evaporated to give a crude material.

The obtained crude substance was dissolved in THF (0.7400 L), and activated carbon (13.09 g) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the activated carbon was filtered off, and the solvent was distilled off from the filtrate to obtain a purified product of diamine 14 (129.8 g, 0.3420 mol, 96% yield). The structure of the diamine 14 was confirmed by ¹ H-NMR.

¹ H-NMR (DMSO-d ₆ ): δ 6.54-6.42 (m, 3H, Ar-H), 3.51-3.45 (m, 2H, NCH ₂ CO ₂ tert-Bu), 3.38-3.30 (m, 2H, CH ₂ CH ₂ N), 2.51-2.44 (m, 2H, ArCH ₂ ), 1.84-1.76 (m, 2H, CH ₂ CH ₂ CH ₂ ), 1.48-1.44 (m, 18H, (tert-Bu) × 2 ).

Example 11 (Example of Reaction Formula (4))

[化23]

Activated carbon (0.2006 g), 5% palladium-activated carbon (0.2000 g) was added to a suspension of nitro compound 13 (2.002 g, 4.938 mmol) in toluene (18.5 mL). The reaction mixture was allowed to stand in a hydrogen atmosphere of 0.5 MPa, and then reacted at 50 ° C for 10 minutes. After the completion of the reaction, the activated carbon and the catalyst in the reaction mixture were filtered off, and the solvent was evaporated to give a diamine 14 (1.790 g, 4.771 mol, 97% yield). The structure of the obtained diamine compound was confirmed by ¹ H-NMR analysis, and the results were identical to the ¹ H-NMR of the diamine compound 14 obtained in the above Example 10.

Example 12 (Example of Reaction Formula (2))

[Chem. 24]

A solution of N-Boc-glycolic acid tert-butyl ester 10 (50.00 g, 216.2 mmol) in toluene (200 mL) was added dropwise to a solution of tert-butoxy potassium (31.53 g, 281.0 mmol) in toluene (100 mL) Stir in the suspension for 30 minutes. Next, a solution of tetra-n-butylammonium iodide (7.985 g, 21.62 mmol) and allyl bromide (28.77 g, 237.8 mmol) in toluene (200 mL) was added to the reaction mixture.

After the resulting reaction mixture was stirred at room temperature for 2 hr, water (300 mL) was added and the reaction was stopped, and then toluene (100 mL) and water (200 mL) were added. The separated aqueous layer was extracted with toluene (200 mL), and the organic layer was concentrated and washed with saturated brine (200 mL). Thereafter, magnesium sulfate was collected by filtration, and the obtained organic layer solution was evaporated to give the object 15 (57.62 g, 212.3 mmol, 98% yield). By ¹ H-NMR confirmed structure of the desired product 15.

¹ H-NMR (CDCl ₃ ): δ 5.84-5.73 (m, 1H, -CH=CH ₂ ), 5.20-5.08 (m, 2H, -CH=CH ₂ ), 3.95-3.71 (m, 4H, -NCH ₂ CO ₂ tert-Bu and -NCH ₂ CH=), 1.55-1.38 (m, 18H, (tert-Bu) × 2).

Example 13 (Example of Reaction Formula (3))

[化25]

Sodium acetate (2.015 g, 24.57 mmol) and cesium acetate (0.02758 g, 0.1228 mmol) were added to the terminal olefin compound 15 (5.000 g, 18.43 mmol) and 2-iodo-4-nitroaniline 12 (3.243 g, at room temperature, A mixed solution of 12.28 mmol) of N,N-dimethylacetamide DMAc (41 mL) was reacted at 110 ° C for 3 hours (black gram reaction).

After the obtained reaction mixture was filtered through celite, ethyl acetate (60 mL) and water (60 mL) were added to the obtained filtrate. After separating the separated aqueous layer with ethyl acetate (60 mL), the organic layer was concentrated and washed with water (60 mL), and then the organic layer was separated. Next, the solvent of the organic layer was distilled off to obtain a crude material. The obtained crude product was recrystallized from toluene to give the desired nitro compound 16 (3.093 g, 7.591 mmol, 62% yield). The structure of the nitro compound 16 was confirmed by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ 8.10 (d, 1H, J = 2.4 Hz, Ar-H), 7.96 (dd, 1H, J = 8.8, 2.4 Hz, Ar-H), 6.61 (d, 1H, J=8.8 Hz, Ar-H), 6.53 (d, 1H, J = 15.6 Hz, Ar-CH=C), 6.18 (dt, 1H, J = 15.6, 6.0 Hz, C=CH-CH ₂ -), 4.72-4.60 (m, 2H, NH ₂ ), 4.12-4.02 (m, 2H, C=CHCH ₂ N), 3.94-3.88 (m, 2H, NCH ₂ CO ₂ tert-Bu), 1.55-1.39 (m, 18H, (tert-Bu) × 2).

Example 14 (Example of Reaction Formula (4))

[Chem. 26]

5% palladium-activated carbon (0.3767 g) was added to a suspension of nitro compound 16 (3.767 g, 9.245 mmol) in toluene (37 mL). After the reaction mixture was made into a hydrogen atmosphere, the reaction was carried out at 50 ° C for 7 hours. After the completion of the reaction, the catalyst in the reaction mixture was filtered off using celite, and the solvent was evaporated to give a crude material.

The obtained crude substance was dissolved in THF (36 mL), then activated carbon (0.35 g) was added, and the mixture was stirred at room temperature for 30 minutes. Next, activated carbon was filtered off, and the solvent was distilled off from the filtrate to obtain a purified product of diamine compound 14 (3.477 g, 9.162 mmol, 99% yield). The structure of the obtained diamine compound was confirmed by ¹ H-NMR analysis, and the results were identical to the ¹ H-NMR of the diamine compound 14 obtained in the above Example 10.

Example 15 (Example of Reaction Formula (1))

[化27]

Di-tert-butyl dicarbonate (217.9 g, 0.9986 mol) was added dropwise to a solution of benzylamine 17 (107.0 g, 0.9986 mol) in toluene (780 mL) at room temperature for 1 hour. Next, water (300 mL) was added to stop the reaction, and then the organic layer was separated by adding toluene (60 mL), and the solvent was distilled off to obtain a crude material of the object.

The resulting crude material was recrystallized from hexane to afford the desired N-Boc-benzylamine 18 (183.0 g, 0.8829 mol, 88% yield). The structure of the compound 18 was confirmed by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ 7.35-7.23 (m, 5H, -Ph), 4.88 (bs, 1H, NH), 4.31 (d, 2H, J = 5.6 Hz, NCH ₂ Ph), 1.46 (s , 9H, tert-Bu).

Example 16 (Example of Reaction Formula (2))

[化28]

A solution of N-Boc-benzylamine 18 (20.60 g, 99.39 mmol) in toluene (40 mL) was added dropwise to a suspension of tert-butoxy potassium (14.50 g, 129.2 mmol) in toluene (80 mL). After stirring to 60 ° C, it was stirred for 2 hours. Next, the reaction mixture was cooled in an ice bath, and then a solution of tetra-n-butylammonium iodide (1.836 g, 4.969 mmol) and propargyl bromide (13.01 g, 109.3 mmol) in toluene (80 mL) was sequentially added. Add to the reaction mixture.

After stirring at room temperature for 4 hours, water (100 mL) was added to stop the reaction. The organic layer and the aqueous layer were separated, and the aqueous layer was extracted with ethyl acetate (50 mL), and the organic layer was concentrated, and then washed with saturated brine (30 mL). After distilling off the solvent, the title compound 19 (22.86 g, 93.18 mmol, 94% yield). The structure of the target 19 was confirmed by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ 7.35-7.23 (m, 5H, -Ph), 4.56 (s, 2H, CH ₂ ), 4.10-3.82 (bm, 2H, CH ₂ ), 2.21 (bs, 1H, HC≡C), 1.58-1.39 (bm, 9H, tert-Bu).

Example 17 (Example of Reaction Formula (3))

[化29]

A solution of the diethylamine (0.4983 g, 6.813 mmol) and the terminal acetylene compound 19 (2.089 g, 8.516 mmol) in THF (2 mL) was added to 2-iodo-4-nitroaniline 12 (1.499 g). 5.678 mmol), a suspension of bis(triphenylphosphine)palladium dichloride (0.03985 g, 0.05678 mmol) and copper iodide (I) (0.02163 g, 0.1135 mmol) in THF (7 mL). Thereafter, the temperature was raised to 40 ° C and stirred for 6 hours.

Water (10 mL) and ethyl acetate (10 mL) were added to the resulting reaction mixture to stop the reaction. Next, the reaction mixture was filtered through celite, and the organic layer was separated from the obtained filtrate. The crude material was then recrystallized from toluene and hexane to afford title 20 (1.807 g, 4.437 mmol, 83% yield). The structure of the target 20 was confirmed by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ 8.11 (d, 1H, J = 2.4 Hz, Ar-H), 8.00 (dd, 1H, J = 9.2, 2.4 Hz, Ar-H), 7.40-7.23 (m, 5H, NCH ₂ Ph), 6.63 (d, 1H, J = 9.2 Hz, Ar-H), 5.10-4.67 (bm, 2H, NH ₂ ), 4.59 (s, 2H, CH ₂ ), 4.25 (bs, 2H) , CH ₂ ), 1.51 (s, 9H, tert-Bu).

[Industry use possibility]

The present invention can easily and efficiently produce a diamine compound which is suitable as a raw material of a liquid crystal alignment agent from a low-cost raw material. Further, the production method of the present invention can be mass-produced and is suitable for industrial use.

The entire contents of the specification, the scope of the patent application, and the summary of the Japanese Patent Application No. 2010-182555, filed on Jan. 17, 2010, are hereby incorporated by reference.

Claims (10)

A method for producing a diamine precursor compound represented by Formula 5, which is a compound represented by Formula 1 according to the following reaction formula (1) (wherein R ¹ is -CH ₂ COOR, or -CH ₂ Ph (-Z) _m (Z is a substituent of phenyl (Ph), m is 0 to 5), R is a lower alkyl or alkali metal atom, and di-tert-butyl dicarbonate ((Boc) ₂ O After carrying out the reaction to produce the compound represented by Formula 2, the compound represented by Formula 2 obtained is obtained in the presence of a base according to the following reaction formula (2), and HA-CH ₂ -X (wherein A is - The compound represented by C≡C- or -CH=CH-, X is a dissociable substituent) is reacted to produce a compound represented by Formula 3, and secondly, the resulting Formula 3 is represented by the following Reaction Formula (3). a compound which is coupled with a compound represented by Formula 4 (wherein Y is a dissociable substituent) to produce a diamine precursor compound represented by Formula 5, The method of claim 1, wherein the compound represented by Formula 1 is tert-butyl glycinate or a salt thereof, or a benzylamine or a salt thereof. The method of claim 1 or 2, wherein the coupling reaction is carried out under a coexisting metal complex, a ligand, and a base. The method of claim 1 or 2, wherein the coupling reaction is carried out under a palladium complex which coexists with a ligand containing a tertiary phosphine or a tertiary phosphite. The method of claim 1 or 2, wherein in the compound represented by Formula 4, Y is a bromine, iodine or trifluoromethanesulfonate group. The application method 1 or 2 of the scope of the patent, wherein the compound represented by the HA-CH ₂ -X wherein X is the halogen, or sulfonate group. The method of claim 1, wherein the compound represented by HA-CH ₂ -X is a propargyl halide or an allyl halide. A method for producing a diamine compound of the formula 6, wherein the compound represented by the formula 5 obtained by the method of any one of claims 1 to 7 is reduced according to the following reaction formula (4), A diamine compound represented by the formula 6 (wherein R ² is a hydrogen atom or -CH ₂ COOR, and R is a lower alkyl group), An ester compound which is an ester compound represented by the following formula, A nitro compound which is a nitro compound represented by any of the following formulas,