Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups

Definitions

• the present invention relates to a novel method for easily and efficiently producing a nitro compound, which is a precursor of a specific diamine compound, which is a raw material for producing a polyimide used for a liquid crystal aligning agent, from an inexpensive raw material.
• Polyimides are widely used as electronic materials such as protective materials, insulating materials, and color filters in liquid crystal display elements and semiconductors because of their high mechanical strength, heat resistance, insulation, and solvent resistance.
• polyimide has been widely used as a liquid crystal alignment agent for forming a liquid crystal alignment film for controlling the alignment state of liquid crystals in liquid crystal display elements used for liquid crystal televisions, liquid crystal displays and the like.
• the liquid crystal alignment film is obtained by applying a polyimide precursor such as polyamic acid (polyamic acid) or a liquid crystal aligning agent solution containing soluble polyimide as a main component to an electrode substrate such as glass and baking the surface of the polyimide film obtained from cotton.
• This liquid crystal aligning agent includes a polyamic acid and / or a polyimide obtained by using a diamine compound protected with a t-butoxycarbonyl group which is eliminated by heating and reacting with a tetracarboxylic dianhydride.
• the t-butoxycarbonyl group is eliminated by heating during the baking process in the production thereof, and a highly reactive aliphatic amine is formed. It is possible to provide a liquid crystal alignment film that is strong and hardly scratched even by rubbing treatment.
• the diamine compound having a tert-butoxycarbonyl group (tertiary butoxycarbonyl group, hereinafter also referred to as Boc group) is represented by the following formula 21:
• Diamine compounds are used.
• the starting material for this diamine compound is propargylamine (HC ⁇ CCH 2 NH 2 ), which is expensive and poorly available, as shown below.
• purification of nitro compounds, which are precursor compounds of diamine compounds requires column operations that are unsuitable for industrial production.
• a nitro compound which is a precursor of a diamine compound having a tert-butoxycarbonyl group (Boc group), which is a raw material of polyamic acid and / or polyimide used for a liquid crystal aligning agent or the like, is easily obtained from an inexpensive raw material. And it aims at providing the novel method of manufacturing efficiently. Furthermore, the present invention also provides a method for producing a diamine compound having a tert-butoxycarbonyl group from a nitro compound which is a precursor compound of a diamine compound.
• this production method includes a novel compound in the process. 1.
• a compound represented by formula 1 (wherein R 1 is —CH 2 COOR or —CH 2 Ph (—Z) m (Z is a substituent of a phenyl group (Ph)) M is from 0 to 5), R is a lower alkyl group or an alkali metal atom, and Ph is a phenyl group.) Di-tert-butyl dicarbonate ((Boc) 2 O
• HA—CH 2 —X where A is —C ⁇ C— or —CH ⁇
• a precursor compound of a diamine compound having a tert-butoxycarbonyl group which is a raw material of polyamic acid and / or polyimide, which is used as a liquid crystal aligning agent, simply and efficiently, from an inexpensive starting material.
• Certain novel methods of producing nitro compounds are provided.
• the present invention also provides a method for producing a diamine compound having a tert-butoxycarbonyl group from a nitro compound as a precursor compound of the produced diamine compound. Furthermore, according to the present invention, the following novel compounds are provided.
• the compound represented by the formula 1 is used as a raw material, and this is reacted with (Boc) 2 O (di-tert-butyl dicarbonate).
• the compound represented by the formula 2 is produced according to the reaction formula (1).
• R 1 is —CH 2 COOR or —CH 2 Ph (—Z) m (Z is a substituent on the phenyl group (Ph), and m is 0 to 5).
• R is a lower alkyl group or an alkali metal atom
• Ph is a phenyl group.
• the lower alkyl group is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and in particular, —CH 2 CO 2 -tert-Bu (tert-butyl group) is preferable.
• the alkali metal lithium, sodium or potassium is preferable, and sodium or potassium is particularly preferable.
• Z is a substituent on the phenyl group, and is 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 0 to 5, preferably 0 to 2.
• the compound represented by the formula 1 is glycine-tert-butyl ester or a salt thereof when R 1 is —CH 2 CO 2 -tert-Bu, or benzylamine or a salt thereof when R 1 is —CH 2 Ph. It is.
• These glycine-tert-butyl esters or salts thereof, and benzylamine or salts thereof are easy to obtain and inexpensive, unlike propargylamine (HC ⁇ CCH 2 NH 2 ) and the like.
• Bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; trimethylamine, triethylamine, tripropylamine , Triisopropylamine, tributylamine, diisopropylethylamine, amines such as pyridine, quinoline, collidine; sodium hydride, potassium hydride, sodium tert-butoxy, potassium tert-butoxy and the like.
• reaction proceeds without the presence of a base.
• amines are considered in consideration of the operability of post-treatment of the reaction. Is preferred. Any reaction solvent can be used as long as it is stable under the reaction conditions, is inert, and does not interfere with the intended reaction.
• aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethyl acetate, N-methylpyrrolidone; diethyl ether, isopropyl ether, THF (tetrahydrofuran), TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether) , Ethers such as dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin; chloroform, dichloromethane, four Halogenated hydrocarbons such as carbon chloride and dichloroethane; lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propyl
• solvents can be appropriately selected in consideration of easiness of reaction and the like, and can be used alone or in combination of two or more.
• the said solvent can also be used as a solvent which does not contain water using a suitable dehydrating agent and a desiccant.
• the reaction temperature can be selected from a temperature range of preferably ⁇ 100 ° C. or higher to the boiling point of the reaction solvent used, more preferably ⁇ 50 to 150 ° C., particularly preferably 0 to 60 ° C. .
• the reaction time is 0.1 to 1000 hours, more preferably 0.5 to 50 hours.
• the compound represented by Formula 2 obtained by the above reaction formula (1) may be purified by distillation, recrystallization, or column chromatography such as silica gel, but may be used as it is in the next step without purification. Good.
• Preferred examples of the compound represented by the formula 2 thus prepared are Boc-NHCH 2 COOtert-Bu, or Boc-NHCH 2 Ph (-Z) m (where Z is a substituent on the phenyl group). And 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 0 to 5.).
• HA—CH 2 —X is a propargylating agent when A is —C ⁇ C—, and is an allylating agent when A is —CH ⁇ CH—.
• X is a substituent capable of leaving, for example, halogen such as F, Cl, Br, I; p-toluenesulfonate group (—OSO 2 C 6 H 4 -p-CH 3 ), methanesulfone Sulfonic acid ester groups such as acid ester group (—OSO 2 CH 3 ) and trifluoromethanesulfonic acid ester group (—OSO 2 CF 3 ); acetate ester group (—OCOCH 3 ), benzoic acid ester group (—OCOPh) and the like Organic acid ester group; methoxycarbonyloxy group (—OCO 2 CH 3 ), ethoxycarbonyloxy group (—OCO 2 CH 2 CH 3 ), i-propyloxycarbonyloxy group (—OCO 2 CH (CH 3
• Bases used in the reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; tert-butoxy Bases such as sodium, potassium tert-butoxy, sodium hydride and potassium hydride; amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline and collidine can be used. Of these, tert-butoxy sodium, tert-butoxy potassium, sodium hydride, potassium hydride and the like are preferable.
• reaction solvent can be used as long as it is stable under the reaction conditions, is inert, and does not interfere with the intended reaction.
• aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethyl acetate, N-methylpyrrolidone; ethers such as diethyl ether, isopropyl ether, THF, TBME, CPME, dioxane; pentane, hexane, heptane, petroleum Aliphatic hydrocarbons such as ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane; acetic acid Lower fatty acid esters such as methyl, ethyl acetate, butyl a
• solvents can be appropriately selected in consideration of easiness of reaction and the like, and can be used alone or in combination of two or more. Moreover, depending on the case, the said solvent can also be used as a solvent which does not contain water using a suitable dehydrating agent and a desiccant.
• iodides such as tetra-n-butylammonium iodide, sodium iodide, potassium iodide and the like can be added.
• the reaction temperature can be preferably selected from a temperature range from ⁇ 100 ° C. or higher to the boiling point of the reaction solvent used, more preferably ⁇ 50 to 150 ° C., particularly preferably ⁇ 20 to 100 ° C. is there.
• the reaction time is 0.1 to 1000 hours, more preferably 0.5 to 50 hours.
• the compound represented by Formula 3 obtained by the above reaction formula (2) may be purified by distillation, recrystallization, or column chromatography such as silica gel, but may be used as it is in the next step without purification. Good.
• Boc-N (CH 2 C ⁇ CH ) CH 2 COOt-Bu Boc-N (CH 2 C ⁇ CH) CH 2 Ph (-Z ) m
• Z is a substituent on the phenyl group, which is a fluorine atom, a nitro group, a carboxyl group, an ester group, a cyano group or a C 1-4 alkoxycarbonyl group
• m is 0-5.
• ester compounds are novel compounds before the present application.
• Y is a substituent capable of leaving, for example, a halogen of F, Cl, Br, I; p-toluenesulfonic acid ester group (—OSO 2 C 6 H 4 -p Sulfonic acid ester groups such as —CH 3 ), methanesulfonic acid ester groups (—OSO 2 CH 3 ), and trifluoromethanesulfonic acid ester groups (—OSO 2 CF 3 ) are used.
• p-toluenesulfonic acid ester group —OSO 2 C 6 H 4 -p Sulfonic acid ester groups such as —CH 3 ), methanesulfonic acid ester groups (—OSO 2 CH 3 ), and trifluoromethanesulfonic acid ester groups (—OSO 2 CF 3 ) are used.
• a metal complex catalyst is formed using an appropriate metal complex and a ligand.
• a palladium complex or a nickel complex is used as the metal complex, and depending on the reaction, it is preferable that a copper catalyst coexists as a co-catalyst.
• the metal complex catalyst those having various structures can be used, but it is preferable to use a so-called low-valent palladium complex or nickel complex, particularly zero having tertiary phosphine or tertiary phosphite as a ligand.
• a valent metal complex catalyst is preferred.
• an appropriate precursor that can be easily converted into a zero-valent metal complex catalyst in the reaction system can be used.
• a metal complex that does not contain tertiary phosphine or tertiary phosphite as a ligand and a tertiary phosphine or tertiary phosphite that is a ligand are mixed to produce tertiary phosphine or tertiary phosphite.
• a low-valent metal complex catalyst having phosphite as a ligand can also be produced.
• tertiary phosphine or tertiary phosphite which is a ligand examples include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1 , 3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc. Can be mentioned.
• a metal complex catalyst containing a mixture of two or more of these ligands is also preferably used.
• a palladium complex not containing tertiary phosphine or tertiary phosphite in combination with a metal complex containing tertiary phosphine or tertiary phosphite as the metal complex catalyst.
• the above ligands may be further combined.
• Examples of palladium complexes that do not contain tertiary phosphine or tertiary phosphite include bis (benzylideneacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzonitrile) dichloropalladium, palladium acetate, and chloride. Palladium, palladium-activated carbon and the like can be mentioned.
• Examples of the palladium complex containing tertiary phosphine or tertiary phosphite as a ligand include (ethylene) bis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and bis (triphenylphosphine) dichloropalladium. Can be mentioned.
• the amount of these palladium complexes used may be a so-called catalytic amount, preferably 20 mol% or less, particularly preferably 10 mol% or less, relative to the compound represented by Formula 4.
• the copper catalyst used as a co-catalyst is preferably monovalent, and examples thereof include copper (I) chloride, copper (I) bromide, copper (I) iodide, and copper (I) acetate.
• Bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; methylamine, dimethylamine, trimethylamine , Ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, collidine, pyrrolidine, piperidine Amines such as morpholine and N-methylmorpholine; sodium acetate, potassium acetate, lithium acetate and the like can be used.
• inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphat
• a metal acetylide (L n) is used in advance by using organic lithium, organic magnesium, organic zinc or the like as a base.
• M is a metal
• L is a ligand
• n is a non-zero integer.
• M examples include Li, Mg, Zn, Sn, and B.
• L examples include F, Cl, Br, I, OH, C 1-6 alkoxy and the like.
• reaction solvents include water, alcohols, amines, aprotic polar organic solvents (DMF (dimethylformamide), DMSO (dimethylsulfoxide), DMAc (dimethylacetamide), NMP (N-methylpyrrolidone), etc.), 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, Mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane
• DMF dimethylformamide
• DMSO dimethylsulfoxide
• DMAc dimethylacetamide
• solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used alone or in combination of two or more. Moreover, depending on the case, the said solvent can also be used as a solvent which does not contain water using a suitable dehydrating agent and a desiccant.
• the reaction temperature can be selected from a temperature range of preferably ⁇ 100 ° C. or higher to the boiling point of the reaction solvent used, more preferably ⁇ 50 to 200 ° C., particularly preferably 20 to 150 ° C. .
• the reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.
• the compound represented by the formula 5 obtained by the above reaction formula (3) is preferably purified by distillation, recrystallization, column chromatography such as silica gel, and the like. Note that recrystallization is preferably performed at as low a temperature as possible.
• the compounds represented by the formula 5 thus produced the following three compounds are novel compounds before the present application.
• the diamine represented by the formula 6 is produced.
• R 1 of the compound represented by Formula 5 is a benzyl group
• R 2 is a hydrogen atom
• R 1 is CH 2 COOR
• R 2 is also CH 2 COOR.
• R is a lower alkyl group, and the same description as in R 1 applies to the lower alkyl group in this case.
• a hydrogenation reaction using palladium-activated carbon or platinum-activated carbon as a catalyst or a reduction reaction performed in the presence of Fe, Sn, Zn, or a salt thereof and protons.
• a reduction reaction using formic acid as a hydrogen source and a reaction using hydrazine as a hydrogen source. These reactions can also be carried out in combination.
• the hydrogenation reaction is preferably used in consideration of the structure of the compound whose substrate is represented by Formula 5 and the reactivity of the reduction reaction.
• the catalyst to be used examples include commercially available activated carbon-supported metals such as palladium-activated carbon, platinum-activated carbon, and rhodium-activated carbon. Further, the catalyst may not necessarily be an activated carbon-supported metal catalyst such as palladium hydroxide, platinum oxide, or Raney nickel. Good results are also obtained with the use of palladium-activated carbon, which is generally used widely.
• reaction solvent can be used as long as it is stable under the reaction conditions, is inert, and does not interfere with the intended reaction.
• aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethyl acetate, N-methylpyrrolidone; ethers such as diethyl ether, isopropyl ether, THF, TBME, CPME, dioxane; pentane, hexane, heptane, petroleum ether
• Aliphatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin and other aromatic hydrocarbons, chloroform, dichloromethane, carbon tetrachloride, dichloroethane and other halogenated hydrocarbons; methyl acetate, acetic acid Lower fatty acid esters such as ethyl, butyl a
• solvents can be appropriately selected in consideration of easiness of reaction and the like, and can be used alone or in combination of two or more. Moreover, depending on the case, the said solvent can also be used as a solvent which does not contain water using a suitable dehydrating agent and a desiccant.
• the reaction can be carried out in the presence of activated carbon.
• the amount of activated carbon used in this case is not particularly limited, but is 1 to 20% by weight, more preferably 1 to 10% by weight with respect to the compound represented by Formula 5.
• the reaction can be carried out under pressure.
• the reaction in order to avoid the reduction of the benzene nucleus, the reaction is preferably carried out in a pressure range of about 20 atm (kgf), more preferably in a range up to 10 atm.
• the reaction temperature can be selected from a temperature range of preferably ⁇ 100 ° C.
• the reaction time is 0.1 to 1000 hours, more preferably 1 to 200 hours.
• the compound represented by the formula 6 obtained by the above reaction formula (4) is preferably purified by distillation, recrystallization or column chromatography such as silica gel.
• a preferred example of the compound represented by the formula 6 thus produced is a compound in which R 2 is a hydrogen atom or CH 2 COOt-Bu.
• N-Boc-glycine-tert-butyl ester 10 (1.551 Kg, 6.706 mol, 99% yield).
• the N-Boc-glycine -tert- butyl ester 10 obtained was confirmed by 1 H-NMR analysis, and 1 H-NMR of N-Boc-glycine -tert- butyl ester obtained in Example 1 above Matched perfectly.
• the resulting reaction mixture was stirred at room temperature for 3 hours, then 8 wt% aqueous ammonium chloride solution (500 mL) was added to stop the reaction, and the organic layer was separated. Thereafter, the solvent was distilled off from the organic layer to obtain the desired terminal acetylene compound 11 (153.4 g, 0.5695 mol, 88% yield).
• the structure of the terminal acetylene compound 11 as a product was confirmed by 1 H-NMR analysis.
• 2-Iodo-4-nitroaniline 12 (111.7 g, 0.4231 mol), bis (triphenylphosphine) palladium dichloride (2.970 g, 0.004231 mol) and copper iodide (I) (1.611 g, 0.008461 mol) in THF (500
• diethylamine 37.13 g, 0.5077 mol
• terminal acetylene 11 152.9 g, 0.5680 mol
• the reaction mixture was then heated to 40 ° C. and stirred for 24 hours.
• the reaction mixture was poured into water (3850 mL) to stop the reaction, the target product crystallized, but the mixture was further stirred for 3 hours.
• 2-iodo-4-nitroaniline 12 (7.50 g, 28.4 mmol), bis (triphenylphosphine) palladium dichloride (99.6 mg, 0.142 mmol) and copper (I) iodide (54.1 mg, 0.284 mmol) in ethyl acetate ( To a suspension of 49.9 mL), 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 in this order at room temperature. The reaction mixture was then heated to 50 ° C. and stirred for 6 hours.
• Activated carbon (0.750 g) was added to the resulting reaction mixture, and activated carbon and the reaction residue were removed by filtration at 50 ° C., and water (22.5 mL) was added to the filtrate to separate the organic phase. Next, the solvent of the organic phase was distilled off under reduced pressure. Toluene (46.2 mL) and activated carbon (1.15 g) were added to the resulting crude product, and the activated carbon was removed by filtration at a temperature not exceeding 80 ° C. The product was recrystallized to obtain nitro compound 13 (10.3 g, 25.2 mmol, 89% yield). When the structure of the nitro compound 13 was confirmed by 1 H-NMR analysis, it completely coincided with the 1 H-NMR of the nitro compound 13 obtained in Example 5 described above.
• 2-Iodo-4-nitroaniline 12 (8.03 g, 30.4 mmol), bis (triphenylphosphine) palladium dichloride (213 mg, 0.304 mmol) and copper (I) iodide (116 mg, 0.608 mmol) in toluene (10.3
• 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 in this order at room temperature. The reaction mixture was then heated to 40 ° C. and stirred for 1 hour.
• 2-Iodo-4-nitroaniline 12 (5.00 g, 18.9 mmol), bis (triphenylphosphine) palladium dichloride (133 mg, 0.189 mmol) and copper (I) iodide (72.0 mg, 0.378 mmol) in toluene (7.6
• di (n-butyl) amine (2.93 g, 22.7 mmol) and terminal acetylene 11 (7.65 g, 28.4 mmol) in toluene (21.2 mL) were added in this order at room temperature. The reaction mixture was then warmed to 40 ° C. and stirred for 27 hours.
• reaction mixture was ice-cooled, and 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 this order. added.
• the reaction mixture was stirred at room temperature for 3 hours, and then 13 wt% aqueous ammonium chloride solution (23.7 mL) was added to stop 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 containing the desired terminal acetylene compound 11 (32.71 g).
• Acetic acid of 2-iodo-4-nitroaniline 12 (6.84 g, 25.9 mmol), bis (triphenylphosphine) palladium dichloride (90.0 mg, 0.130 mmol) and copper (I) iodide (49.3 mg, 0.25.9 mmol)
• diethylamine 9.47 g, 129 mmol
• toluene solution of terminal acetylene 11 obtained above were added in this order at room temperature. The reaction mixture was then heated to 50 ° C. and stirred for 6 hours.
• Activated carbon (0.68 g) was added to the reaction mixture, activated carbon and the reaction residue were removed by filtration at 50 ° C., water (20.5 mL) was added to the filtrate, and the organic phase was separated. The solvent in the organic phase was distilled off under reduced pressure, toluene (42.5 mL) and activated carbon (1.05 g) were added to the resulting crude product, and the activated carbon was filtered off at a temperature not exceeding 80 ° C. Crystallization gave nitro 13 (7.86 g, 19.4 mmol, 75% yield). When the structure of the nitro compound 13 was confirmed by 1 H-NMR analysis, it completely coincided with the 1 H-NMR of the nitro compound 13 obtained in Example 5 described above.
• Activated carbon (0.2006 g) and 5% palladium-activated carbon (0.2000 g) were added to a suspension of nitro compound 13 (2.002 g, 4.938 mmol) in toluene (18.5 mL).
• the reaction mixture was brought to a hydrogen atmosphere of 0.5 MPa, and reacted at 50 ° C. for 10 minutes.
• activated carbon and catalyst in the reaction mixture were removed by filtration, and the solvent was distilled off from the obtained filtrate to obtain diamine 14 (1.790 g, 4.717 mol, 97% yield).
• the structure of the obtained diamine compound was confirmed by 1 H-NMR analysis, it completely coincided with 1 H-NMR of the diamine compound 14 obtained in Example 10 described above.
• the resulting reaction mixture was stirred at room temperature for 2 hours, water (300 mL) was added to stop the reaction, and toluene (100 mL) and water (200 mL) were further added to separate the layers.
• the separated aqueous layer was extracted with toluene (200 mL), the organic layers were combined, washed with saturated brine (200 mL), and the organic layer was separated and dried over magnesium sulfate. Thereafter, magnesium sulfate was filtered off, and then the solvent of the obtained organic layer was distilled off to obtain the target product 15 (57.62 g, 212.3 mmol, 98% yield).
• the structure of the target product 15 was confirmed by 1 H-NMR.
• Acetic acid is added to a mixed solution of terminal olefin compound 15 (5.000 g, 18.43 mmol) and 2-iodo-4-nitroaniline 12 (3.243 g, 12.28 mmol) in N, N-dimethylacetamide DMAc (41 mL) at room temperature.
• Sodium (2.015 g, 24.57 mmol) and palladium acetate (0.02758 g, 0.1228 mmol) were added and reacted at 110 ° C. for 3 hours (Heck reaction).
• the resulting reaction mixture was filtered using celite, and ethyl acetate (60 mL) and water (60 mL) were added to the resulting filtrate for liquid separation.
• the separated aqueous layer was further extracted with ethyl acetate (60 mL), the organic layers were combined, washed with water (60 mL), and then the organic layer was separated. Subsequently, the solvent of the organic layer was distilled off to obtain a crude product.
• the obtained crude product was recrystallized from toluene to obtain the desired nitro compound 16 (3.093 g, 7.591 mmol, 62% yield).
• the structure of nitro compound 16 was confirmed by 1 H-NMR analysis.
• Di-tert-butyl dicarbonate (217.9 g, 0.9986 mol) was added dropwise to a toluene (780 mL) solution of benzylamine 17 (107.0 g, 0.9986 mol) at room temperature, and reacted for 1 hour. Thereafter, water (300 mL) was added to stop the reaction, toluene (60 mL) was further added to separate the organic layer, and the solvent was distilled off to obtain a crude product of interest.
• reaction mixture was then cooled in an ice bath and 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) in that order. Added to the reaction mixture.
• 2-iodo-4-nitroaniline 12 (1.499 g, 5.678 mmol), bis (triphenylphosphine) palladium dichloride (0.03985 g, 0.05678 mmol) and copper (I) iodide (0.02163 g, 0.1135 mmol) in THF (7
• a solution of diethylamine (0.4983 g, 6.813 mmol) and terminal acetylene compound 19 2.089 g, 8.516 mmol
• THF 2-iodo-4-nitroaniline 12
• a diamine compound useful as a raw material for a liquid crystal aligning agent can be easily and effectively produced from an inexpensive raw material.
• the production method of the present invention can be produced on a large scale and is industrially useful.

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