TITLE OF INVENTION: PROCESS FOR PRODUCING DIAMINE PRECURSOR COMPOUND
TECHNICAL FIELD
The present invention relates to a process for simply and efficiently producing, from an inexpensive starting material, a nitro compound being a precursor for a specific diamine compound which is a starting material for producing a polyimide to be used for e.g. a liquid crystal aligning agent.
BACKGOUNDART
By virtue of their characteristics such as high mechanical strength, heat resistance, insulating properties and solvent resistance, polyimides are widely used as protective materials for liquid display elements or semiconductors, insulating materials or electronic materials for e.g. color filters. Particularly, recently, polyimides are widely used also as liquid crystal aligning agents to form liquid crystal alignment films to control the alignment state of liquid crystal in liquid crystal display elements to be used for e.g. liquid crystal televisions or liquid crystal displays.
A liquid crystal alignment film is formed by carrying out so-called rubbing treatment wherein a surface of a polyimide film obtainable by applying and baking a liquid crystal aligning agent solution containing a soluble polyimide or a polyimide precursor such as a polyamide acid (polyamic acid) on an electrode substrate made of e.g. glass, is rubbed in one direction with a cloth of e.g. cotton, nylon or polyester.
Rubbing treatment is required to obtain the essential properties of the liquid crystal alignment film. However, it has been found that such rubbing treatment brings about various problems such as flaws on the surface of the liquid crystal alignment film, formation of dust, in-plane non-uniformity in alignment treatment due to an influence of a mechanical force or static electricity, etc. Especially, recently it has been required more than ever to cope with such problems brought about by rubbing treatment, in view of the demands for higher performance, higher refinement and larger size of liquid crystal display elements.

On the other hand, various methods for obtaining liquid crystal alignment films have been proposed in order to suppress formation of flaws or peeling of films in the rubbing treatment of polyimide type liquid crystal alignment films. For example, methods of using a liquid crystal aligning agent prepared by adding a cross-linking
i agent such as a compound having an epoxy group or a compound having an epoxy group and a reactive group other than an epoxy group, to a polyamide acid and/or a polyimide, have been proposed (Patent Documents 1 and 2).
The present applicants have previously proposed a polyimide type liquid crystal aligning agent using a specific diamine compound as a polyimide which is scarcely
) susceptible to scratching even in such rubbing treatment (Patent Document 3). This liquid crystal aligning agent is one which employs a diamine compound protected by a t-butoxycarbonyl group detachable by heating and which contains a polyamide acid and/or a polyimide obtainable by reacting such a diamine compound with a tetracarboxylic dianhydride. In the case of this liquid crystal aligning agent, in the firing
i step in its production, the t-butoxycarbonyl group is detached by heating to form a highly reactive aliphatic amine, and such an aliphatic amine serves as a cross-linking point to strengthen the surface of the film, whereby it is possible to present a liquid crystal alignment film which is scarcely susceptible to scratching even by rubbing treatment. In the production of a polyamide acid and/or a polyimide as disclosed in the above
) Patent Document 3, a diamine compound represented by the following formula 21 is used as the diamine compound having a tert-butoxycarbonyl group (tertiary butoxycarbonyl group, hereinafter referred to also as a Boc group). The starting material for this diamine compound is expensive and not-readily available propargylamine (HC=CCH2NH2), as shown below. Further, in the purification of a nitro
i compound being a precursor compound for a diamine compound, column operation is required which is not practically suitable for carrying out an industrial production.
&■■_■ R.ILJ

Patent Document 1: JP-A-9-146100 Patent Document 2: JP-A-2007-11221 Patent Document 3: WO2010/050523
DISCLOSURE OF INVENTION TECHNICAL PROBLEM
It is an object of the present invention to provide a novel process for simply and efficiently producing, from an inexpensive starting material, a nitro compound being a precursor for a diamine compound having a tert-butoxycarbonyl group (Boc group) as a starting material for a polyamide acid and/or a polyimide to be used for e.g. a liquid crystal aligning agent.
Further, the present invention is to provide also a process for producing a diamine compound having a tert-butoxycarbonyl group from a nitro compound being a precursor compound for the diamine compound.
SOLUTION TO PROBLEM
As a result of an extensive research to accomplish the above object, the present invention has arrived at a novel production process having the following construction. As described below, such a production process provides novel compounds in the process steps. 1. A process which comprises:
reacting a compound represented by the formula 1 (wherein R1 is -CH2COOR or -CH2Ph(-Z)m (Z is a substituent on the phenyl group (Ph), and m is from 0 to 5) and R is a lower alkyl group or an alkali metal atom) with di-tert-butyl dicarbonate ((Boc)20) in accordance with the following reaction formula (1) to produce a compound represented by the formula 2,
reacting the compound represented by the formula 2 thus obtained, with a compound represented by the formula H-A-CH2-X (wherein A is -C=C- or -CH=CH-, and X is a leaving substituent) in the presence of a base in accordance with the following reaction formula (2) to produce a compound represented by the formula 3, and
then, subjecting the compound represented by the formula 3 thus obtained, to a coupling reaction with a compound represented by the formula 4 (wherein Y is a leaving

2. The process according to the above 1, wherein the compound represented by the formula 1 is glycine tert-butyl ester or its salt, or benzylamine or its salt.
3. The process according to the above 1 or 2, wherein the coupling reaction is carried out in the presence of a metal complex, a ligand and a base.
4. The process according to any one of the above 1 to 3, wherein the coupling reaction is carried out in the presence of a palladium complex containing a tertiary phosphine or a tertiary phosphite as the ligand.
5. The process according to any one of the above 1 to 4, wherein Y in the compound represented by the formula 4 is Br, I or a trifluoromethanesulfonic acid ester group.
6. The process according to any one of the above 1 to 5, wherein X in the compound represented by H-A-CH2-X is a halogen or a sulfonic acid ester group.
7. The process according to the above 1, wherein the compound represented by H-A-CH2-X is a propargyl halide or an allyl halide.
8. A process which comprises reducing the compound represented by the formula 5 obtained by the process as defined in any one of the above 1 to 7, in accordance with the following reaction formula (4) to produce a diamine compound represented by the formula 6 (wherein R2 is a hydrogen atom or-CH2COOR, and R is a lower alkyl group):

ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a novel process for simply and efficiently producing, from an inexpensive starting material, a nitro compound being a precursor compound for a diamine compound having a tert-butoxycarbonyl group as a starting material for a polyamide acid and/or a polyimide to be used for e.g. a liquid crystal aligning agent.
Further, the present invention provides a process for producing a diamine compound having a tert-butoxycarbonyl group from the nitro compound thus produced as a precursor compound for the diamine compound.
Still further, the present invention provides the following novel compounds:
DESCRIPTION OF EMBODIMENTS
Now, the present invention will be described in further detail. A. Production of compound represented by the following formula 2 by using, as

starting material, compound represented by the following formula 1
Using the compound represented by the formula 1, the compound represented by the formula 2 is produced by reacting it with (Boc)20 (di-tert-butyl dicarbonate) in accordance with the reaction formula (1).
In the formula 1, R1 is -CH2COOR or -CH2Ph(-Z)m (Z is a substituent on the phenyl group (Ph), and m is from 0 to 5) and R is a lower alkyl group or an alkali metal atom, and Ph is a phenyl group.
Here, the lower alkyl group is a C-i-6 alkyl group, preferably a C-M alkyl group, particularly preferably -CH2C02-tert-Bu (tert-butyl group). The alkali metal is preferably lithium, sodium or potassium, particularly preferably sodium or potassium.
Z is a substituent on the phenyl group, and it is a fluorine atom, a nitro group, a carboxyl group, an ester group, a cyano group or a C-M 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 the formula 1 is glycine-tert-butyl ester or its salt when R1 is -CH2C02-tert-Bu, or benzylarnine or its salt when R1 is -CH2Ph. Such glycine-tert-butyl ester or its salt, or benzylarnine or its salt, is readily available and inexpensive, as is different from e.g. propargylamine (HC=CCH2NH2).
t (Boc)20 Hti*x
H2N-R1 ► "N (1)
Boc
1 2
The reaction to obtain the compound represented by the above formula 2 is carried out preferably in the presence of a base. As the base, it is possible to use, for example, 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; an amine such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline orcollidine; or sodium hydride, potassium hydride, sodium tert-butoxide or potassium tert-butoxide.
In a case where a free amine is used as the compound represented by the formula 1, the reaction proceeds even if no base is present, but in a case where a base is to be used, it is preferred to use an amine in consideration of the operation efficiency

for post treatment after the reaction.
As a solvent for the reaction, any solvent may be used so long as it is stable and inert under the reaction conditions and does not hinder the desired reaction. For example, it is possible to use an aprotic polar organic solvent such as dimethylformamide, dimethyl sulfoxide, dimethyl acetate or N-methylpyrrolidone; an ether such as diethyl ether, isopropyl ether, THF (tetrahydrofuran), TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether) or dioxane; an aliphatic hydrocarbon such as pentane, hexane, heptane or petroleum ether; an aromatic hydrocarbon such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene ortetralin; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride or dichloroethane; a lower fatty acid ester such as methyl acetate, ethyl acetate, butyl acetate or methyl propionate; or a nitrile such as acetonitrile, propionitrile or butyronitrile.
These solvents may suitably be selected in consideration of the reaction efficiency, and one of them may be used alone, or two or more of them may be used as mixed. Such a solvent may be used as a solvent containing no water by employing a suitable dehydrating agent or a drying agent.
As the reaction temperature, it is possible to select preferably a temperature range of from -100°C to the boiling point temperature of the solvent used for the reaction, but it is 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 by the above reaction formula (1), may be purified by distillation, recrystallization or column chromatography by e.g. silica gel, but may be used as it is, without purification, for the next step.
A preferred example of the compound represented by the formula 2 to be thus produced, is Boc-NHCH2COOtert-Bu or Boc-NHCH2Ph(-Z)m (wherein 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-M alkoxycarbonyl group, and m is from 0 to 5). B. Production of compound represented by the following formula 3 from compound represented by the following formula 2
From the compound represented by the formula 2 obtained by the above reaction formula (1), a compound represented by the formula 3 is produced in accordance with

the following reaction formula (2) by reacting it with H-A-CH2-X (wherein A is -C=C- or -CH=CH-, and X is a substituent having detachability) in the presence of a base.
The above H-A-CH2-X is a propargyl-forming agent when A is -C=C-, or an allyl-forming agent when A is -CH=CH-. X is a substituent having detachability and may, for example, be a halogen such as F, CI, Br or I; a sulfonic acid ester group such as a p-toluenesulfonic acid ester group (-OSO2C6H4-P-CH3), a methanesulfonic acid ester group (-OSO2CH3) or a trifluoromethanesulfonic acid ester group (-OSO2CF3); an organic acid ester group such as acetic acid ester group (-OCOCH3) or a benzoic acid ester group (-OCOPh); or a carbonic acid ester group represented by a methoxycarbonyloxy group (-OCO2CH3), an ethoxycarbonyloxy group (-OCO2CH2CH3), i-propyloxycarbonyloxy group (-OC02CH(CH3)2) or a phenoxycarbonyloxy group (-OC02Ph). Among them, a halogen or a sulfonic acid ester group is preferred from the viewpoint of the reactivity.
As the base to be used for the reaction, it is possible to use, for example, 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; a base such as sodium tert-butoxide, potassium tert-butoxide, sodium hydride or potassium hydride; or an amine such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline orcollidine. Among them, sodium tert-butoxide, potassium tert-butoxide, sodium hydride or potassium hydride is, for example, preferred.
As a solvent for the reaction, any solvent may be used so long as it is stable and inert under the reaction conditions and does not hinder the desired reaction. For example, it is possible to use an aprotic polar organic solvent such as dimethylformamide, dimethyl sulfoxide, dimethyl acetate or N-methylpyrrolidone; an ether such as diethyl ether, isopropyl ether, THF, TBME, CPME or dioxane; an aliphatic hydrocarbon such as pentane, hexane, heptane or petroleum ether; an aromatic

hydrocarbon such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene or tetralin; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride or dichloroethane; a lower fatty acid ester such as methyl acetate, ethyl acetate, butyl acetate or methyl propionate; or a nitrile such as acetonitrile, propionitrile or butyronitrile.
These solvents may suitably be selected in consideration of the reaction efficiency, and one of them may be used alone, or two or more of them may be used as mixed. Further, in some cases, such a solvent may be used as a solvent containing no water by employing a suitable dehydrating agent or a drying agent.
Further, in order to let the above reaction proceed more efficiently, it is possible to add an iodide such as tetra-n-butyl ammonium iodide, sodium iodide or potassium iodide.
As the reaction temperature, it is possible to select preferably a temperature range of from -100°C to the boiling point temperature of the solvent used for the reaction, but it is 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 by the above reaction formula (2), may be purified by distillation, recrystallization or column chromatography by e.g. silica gel, but may be used as it is, without purification, for the next step.
A preferred example of the compound represented by the formula 3 to be thus produced, is Boc-N(CH2OCH)CH2COOt-Bu, Boc- N(CH2OCH)CH2Ph(-Z)m, Boc-N(CH2CH=CH2)CH2COOt-Bu or Boc- N(CH2CH=CH2)CH2Ph(-Z)m. Here, 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 C1-4 alkoxycarbonyl group, and m is from 0 to 5.
Among compounds represented by the formula 3, the following ester compound is a novel compound before the present application.
*^N^C02f-Bu Boc
C. Production of compound represented by the following formula 5 from compound represented by the following formula 3
From the compound represented by the formula 3 obtained by the above reaction formula (2), a compound represented by the formula 5 is produced by subjecting it to a

coupling reaction such as Sonogashira coupling or Heck reaction with a compound represented by the formula 4 in the presence of a metal complex, a ligand and a base.
ill me uumpuuiiu lepieseiueu uy me luimuia t, i ibd suusuiueiu naviny detachability, which may, for example, be a halogen such as F, CI, Br or I; or a sulfonic acid ester group such as a p-toluenesulfonic acid ester group (-OSO2C6H4-P-CH3), a methanesulfonic acid ester group (-OSO2CH3) or a trifluoromethanesulfonic acid ester group (-OSO2CF3). Among them, Br, I or a trifluoromethanesulfonic acid ester group is preferred from the viewpoint of the reactivity.
In this reaction, using a suitable metal complex and ligand, a metal complex catalyst is formed and used. Usually, as the metal complex, a palladium complex or a nickel complex is used, and depending upon the reaction, a copper catalyst is preferably permitted to be present as a promoter.
As the metal complex, ones having various structures may be employed, but it is preferred to use a so-called low-valent palladium complex or nickel complex, and particularly preferred is a zero-valent metal complex catalyst having a tertiary phosphine or tertiary phosphite as a ligand. Further, it is possible to use a suitable precursor which may readily be converted to a zero-valent metal complex catalyst in the reaction system. Still further, it is possible to mix a metal complex not containing a tertiary phosphine or tertiary phosphite as a ligand, with a tertiary phosphine or tertiary phosphite as a ligand, to form a low-valent metal complex catalyst having a tertiary phosphine or tertiary phosphite as a ligand.
The tertiary phosphine or tertiary phosphite may, for example, be triphenyl phosphine, tri-o-tolyl phosphine, diphenylmethyl phosphine, phenyldimethyl phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1 '-bis(diphenylphosphino)ferrocene, trimethyl phosphite, triethyl phosphite or triphenyl phosphite. A metal complex catalyst containing two or more such ligands as mixed, may also suitably be used.
As the metal complex catalyst, it is also preferred to use a palladium complex not

containing a tertiary phosphine or tertiary phosphite, and a metal complex containing a tertiary phosphine or tertiary phosphite, in combination. In such a case, the above-mentioned ligand may further be combined. The palladium complex not containing a tertiary phosphine or tertiary phosphite may, for example, be bis(benzylideneacetone) palladium, tris(benzylideneacetone) dipalladium, bis(acetonitrile) dichloropalladium, bis(benzonitrile) dichloropalladium, palladium acetate, palladium chloride or palladium/activated carbon. The palladium complex containing a tertiary phosphine or tertiary phosphite as a ligand may, for example, be (ethylene)bis(triphenylphosphine) palladium, tetrakis(triphenylphosphine) palladium or bis(triphenylphosphine) dichloropalladium.
The amount of such a palladium complex may be a so-called catalytic amount and is preferably at most 20 mol%, particularly preferably at most 10 mol%, to the compound represented by the formula 4. The copper catalyst to be used as a promoter at the same time, is preferably a monovalent one, and may, for example, be copper(l) chloride, copper(l) bromide, copper(l) iodide orcopper(l) acetate.
As the base, it is possible to use, for example, 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; an amine such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, collidine, pyrrolidine, piperidine, morpholine or N-methylmorpholine; or sodium acetate, potassium acetate or lithium acetate.
In the case of a terminal acetylene compound wherein A in the compound represented by the formula 3 as the starting material is -C=C-, such a compound may preliminarily be converted to a metal acetylide (LnM-C=C- wherein M is a metal, L is a ligand, and n is an integer other than 0) by using, as a base, organic lithium, organic magnesium or organic zinc, so that such a metal acetylide may be used for the reaction. M may, for example, be Li, Mg, Zn, Sn or B. L may, for example, be F, CI, Br, I, OH or C-i-6 alkoxy.
As a solvent for the reaction, any solvent may be used so long as it is stable and

inert under the reaction conditions and does not hinder the desired reaction. As the solvent, it is possible to use, for example, water, an alcohol, an amine, an aprotic polar organic solvent (such as DMF (dimethylformamide), DMSO (dimethyl sulfoxide), DMAc (dimethyl acetamide) or NMP (N-methylpyrrolidone)); an ether (such as Et20, i-Pr20, TBME, CPME, THF or dioxane); an aliphatic hydrocarbon (such as pentane, hexane, heptane or petroleum ether); an aromatic hydrocarbon (such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene or tetralin); a halogenated hydrocarbon (such as chloroform, dichloromethane, carbon tetrachloride or dichloroethane); a lower fatty acid ester (such as methyl acetate, ethyl acetate, butyl acetate or methyl propionate); or a nitrile (such as acetonitrile, propionitrile or butyronitrile). These solvents may suitably be selected in consideration of the reaction efficiency, and one of them may be used alone, or two or more of them may be used as mixed. Further, in some cases, such a solvent may be used as a solvent containing no water by employing a suitable dehydrating agent or a drying agent.
As the reaction temperature, it is possible to select preferably a temperature range of from -100°C to the boiling point temperature of the solvent used for the reaction, but it is 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 by the above reaction formula (3), is preferably purified by distillation, recrystallization or column chromatography by e.g. silica gel. Here, the recrystallization is preferably carried out at a temperature as low as possible.
Among compounds represented by the formula 5 thus produced, the following three compounds are novel compounds before the present application.
D. Production of diamine represented by the following formula 6 from compound represented by the following formula 5

formula (3), a diamine represented by the formula 6 is produced in accordance with the above reaction formula (4) as a nitro group on its benzene ring and an unsaturated bond in its side chain, and further, depending upon its structure, a benzyl group, are reduced. In the compound represented by the formula 6, R2 is a hydrogen atom when R1 in the compound represented by the formula 5 is a benzyl group, and when R1 is CH2COOR, R2 is also CH2COOR. Here, R is a lower alkyl group, and with respect to the lower alkyl group in this case, the same description as in the case of R1 applies.
The method for reducing the compound represented by the formula 5 may, for example, be a hydrogenation reaction which utilizes e.g. palladium/activated carbon or platinum/activated carbon as a catalyst, a reduction reaction which is carried out in the presence of Fe, Sn, Zn or a salt thereof and a proton, a reduction reaction which uses formic acid as the hydrogen source, or a reaction which uses hydrazine as the hydrogen source. Further, such reactions may be carried out in combination.
Among the above-exemplified reduction reactions, it is preferred to use the hydrogenation reaction from the viewpoint of the structure of the compound and the reactivity for the reduction reaction wherein the substrate is represented by the formula 5.
The catalyst to be used may, for example, be a metal catalyst supported on activated carbon which is available as a commercial product, such as palladium/activated carbon, platinum/activated carbon or rhodium/activated carbon. It may not necessarily be a metal catalyst supported on activated carbon, i.e. it may, for example, be palladium hydroxide, platinum oxide or Raney nickel. Good results are obtainable even by using palladium/activated carbon which is commonly widely employed.
As a solvent for the reaction, any solvent may be used so long as it is stable and inert under the reaction conditions and does not hinder the desired reaction. For example, it is possible to use an aprotic polar organic solvent such as

dimethylformamide, dimethyl sulfoxide, dimethyl acetate or N-methylpyrrolidone; an ether such as diethyl ether, isopropyl ether, THF, TBME, CPME or dioxane; an aliphatic hydrocarbon such as pentane, hexane, heptane or petroleum ether; an aromatic hydrocarbon such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene or tetralin; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride or dichloroethane; a lower fatty acid ester such as methyl acetate, ethyl acetate, butyl acetate or methyl propionate; or a nitrile such as acetonitrile, propionitrile or butyronitrile.
These solvents may suitably be selected in consideration of the reaction efficiency, and one of them may be used alone, or two or more of them may be used as mixed. Further, in some cases, such a solvent may be used as a solvent containing no water by employing a suitable dehydrating agent or a drying agent.
In order to let the above reduction reaction proceed more efficiently, the reaction may be carried out in the presence of activated carbon. The amount of activated carbon to be used in such a case is not particularly limited, but is preferably from 1 to 20 wt%, more preferably from 1 to 10 wt%, to the compound represented by the formula 5.
Further, in order to let the reaction proceed more efficiently, the reaction may be carried out under an elevated pressure. In such a case, in order to avoid reduction of the benzene nucleus, the reaction is carried out preferably within a pressure range of at most about 20 atmospheres (kgf), more preferably within a range of at most 10 atmospheres.
As the reaction temperature, it is possible to select preferably a temperature range of from -100°C to the boiling point temperature of the solvent used for the reaction, but it is 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 by the above reaction formula (4), is preferably purified by distillation, recrystallization or column chromatography by e.g. silica gel.
A preferred example of the compound represented by the formula 6 thus produced, is a compound wherein R2 is a hydrogen atom or CH2COOt-Bu.

Now, the present invention will be described in further detail with reference to Examples, but it should be understand that the present invention is by no means restricted by these Examples. Here, the analyzing device and conditions employed in Examples are as follows. 1H-NMRand13C-NMR
Device: Varian NMR System 400 NB (400MHz)
Solvents for measurement: CDCI3, DMSO-d6
Reference substances: Tetramethylsilane (TMS) (value 5 by 1H of TMS being 0.0 ppm)
CDCI3 (value 5 by 13C of CDCI3 being 77.0 ppm) EXAMPLE 1 (Example of the reaction formula (1))
HC|.H2N<-C02,-BU (B°C)2°'Et3N> "N^W-Bu
Toluene Boc
9 10
A suspension of glycine tert-butyl ester hydrochloride 9 (10.0 g, 59.7 mmol) in
toluene (46.2 ml_) was held at 60°C, and triethylamine (6.51 g, 64.3 mmol) was added
thereto, followed by stirring for 0.5 hour. Then, a solution of di-tert-butyl dicarbonate (10.0 g, 45.9 mmol) in toluene (11.6 ml_) was dropwise added to the reaction mixture, followed by a reaction for 6 hours.
Then, water (30 ml_) was added thereto, and then, the organic layer was separated. Thereafter, the solvent was distilled off from the organic layer, followed by recrystallization from n-hexane to obtain N-Boc-glycine-tert-butyl ester 10 (10.6 g, 45.9 mmol, yield: 100%). The structure of the product was confirmed by 1H-NMR analysis.
1 H-NMR (CDCI3): 5 4.98 (b-s, 1H, NH), 3.79 (d, 2H, J=5.6 Hz, NCH2C02-tert-Bu),
1.52-1.40 (m, 18H, (tert-Bu) x2).
EXAMPLE 2 (Example of the reaction formula (1))
HC|.H2N<-C02,-BU (B°C)2°'Et3N> «N^C02,-Bu
Toluene Boc
9 10
A suspension of glycine tert-butyl ester hydrochloride 9 (1.258 Kg, 7.505 mol) in
toluene (10 L) was held at 10°C, and triethylamine (0.9113 Kg, 9.006 mol) was added
thereto, followed by stirring for 1 hour. Then, di-tert-butyl dicarbonate (1.474 Kg, 6.754 mol) was dropwise added to the reaction mixture, followed by a reaction for 3 hours.

11 lei i, wdiei \o \-) wds ciuueu IU leiiini idle n le leciunui i, wi leieupui i n le uiycii MU
layer was separated. Thereafter, the solvent was distilled off from the organic layer to obtain the desired N-Boc-glycine-tert-butyl ester 10 (1.551 Kg, 6.706 mol, yield: 99%). The obtained N-Boc-glycine-tert-butyl ester 10 was confirmed by 1H-NMR analysis, whereby the result completely agreed with 1H-NMR of N-Boc-glycine-tert-butyl ester obtained in the above Example 1. EXAMPLE 3 (Example of the reaction formula (2))
HN^C02f-Bu HC=CCH2Br, f-BuOK, /i-Bu4NI^ ^^N^cO,f-Bu
Boc Toluene/THF Boc
10 11
A suspension of potassium tert-butoxide (80.05 g, 0.7134 mol) in THF (550 ml_) was dropwise added at room temperature to a solution of N-Boc-glycine tert-butyl ester 10 (150.0 g, 0.6485 mol) in toluene (550 ml_), whereupon the mixture was stirred for 10 minutes at room temperature. Then, the obtained reaction mixture was cooled with ice, and tetra-n-butylammonium iodide (7.186 g, 0.01946 mol) and a solution of propargyl bromide (84.86 g, 0.7134 mol) in toluene (200 ml_) were added in this order to the reaction mixture.
The obtained reaction mixture was stirred for 3 hours at room temperature, and then, a 8 wt% ammonium chloride aqueous solution (500 ml_) was added to terminate the reaction, whereupon 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, yield: 88%).
The structure of the terminal acetylene compound 11 as the product, was confirmed by 1HNMR analysis.
1 H-NMR (CDCI3): 5 4.20-4.10 (m, 2H, HC=CCH2N), 4.00-3.90 (m, 2H, NCH2 C02 -tert -Bu), 2.23 (t, 1H, J=2.6 Hz, HCEC), 1.50-1.40 (m, 18H, (tert-Bu) x2). EXAMPLE 4 (Example of the reaction formula (2))
HN C02f-Bu HC=CCH2Br, NaH^ ^^N C02f-Bu
Boc DMF Boc
10 11
A suspension of sodium hydride (55 wt% mineral oil dispersion, 0.8490 g, 19.46 mmol, before its use, it washed with 10 mL of hexane to remove the mineral oil) in DMF (6 mL) was cooled with ice, and to this solution, a solution of N-Boc-glycine tert-butyl ester 10 (3.000 g, 12.97 mmol) in DMF (12 mL) was slowly dropwise added.

The obtained reaction mixture was stirred for 1 hour at room temperature, and then, at the same temperature, a solution of propargyl bromide (1.697 g, 14.27 mmol) in DMF (12 ml_) was added to the reaction mixture. The reaction mixture was maintained at room temperature and reacted for 18 hours, whereupon water (60 ml_) was added under cooling with ice to terminate the reaction. Then, hexane (50 ml_) was added, followed by liquid separation to separate the organic layer, and the aqueous layer was extracted twice with hexane (50 ml_). The obtained organic layers were put together and washed with a saturated sodium chloride aqueous solution (50 ml_), and the organic layer was separated and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and from the obtained organic layer, the solvent was distilled off to obtain the desired compound 11 (2.605 g, 9.672 mmol, yield: 75%).
The structure of the obtained compound was confirmed by 1HNMR analysis, whereby the result completely agreed with 1HNMR of the compound 11 obtained by using t-BuOK in the above Example 3.
FYAMPI F F> CFY3mnlP nf thp raariinn fnrmi 1I3 (9.W
At room temperature, diethylamine (37.13 g, 0.5077 mol) and a solution of terminal acetylene 11 (152.9 g, 0.5680 mol) in THF (370 ml_) were added in this order to a suspension of 2-iodo-4-nitroaniline 12 (111.7 g, 0.4231 mol), bis(triphenylphosphine)palladium dichloride (2.970 g, 0.004231 mol) and copper(l) iodide (1.611 g, 0.008461 mol) in THF (500 ml_). Then, this reaction mixture was
heated to 40°C and stirred for 24 hours. In order to terminate the reaction, the reaction
mixture was poured into water (3,850 ml_), whereby the desired product was crystallized, but stirring was continued for 3 hours.
From the obtained reaction mixture, the desired product was collected by filtration and dried to obtain a crude product. The obtained crude product was recrystallized by using toluene to obtain the desired nitro compound 13 (144.6 g, 0.3566 mol, yield: 84%). The structure of the nitro compound 13 was confirmed by 1HNMR analysis.
1 H-NMR (CDCI3): 5 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, NH2), 4.45-4.32 (m. 2H, CECCH2N), 4.04-3.88 (m, 2H, NCH2C02tert-Bu), 1.55-1.40 (m, 18H, (tert-Bu) x2).
i~~ xx A n A i-^ ■ i— ^\ i i— i rii i" r i /^* \ At room temperature, diethylamine (10.4 g, 142 mmol) and a solution of terminal acetylene 11 (11.5 g, 42.6 mmol) in toluene (28.9 mL) were added in this order to a suspension of 2-iodo-4-nitroaniline 12 (7.50 g, 28.4 mmol),
bis(triphenylphosphine)palladium dichloride (99.6 g, 0.142 mmol) and copper(l) iodide (54.1 g, 0.284 mmol) in ethyl acetate (49.9 mL). Then, this reaction mixture was
heated to 50°C and stirred for 6 hours.
To the obtained reaction mixture, activated carbon (0.750 g) was added, and at
50°C, the activated carbon and the reaction residue were removed by filtration. To the
filtrate, water (22.5 mL) was added, and the organic layer was separated. Then, the solvent in the organic layer was distilled off under reduced pressure, and to the obtained crude product, toluene (46.2 mL) and activated carbon (1.15 g) were added. At a
temperature not exceeding 80°C, the activated carbon was removed by filtration, and
from the filtrate, the desired product was recrystallized to obtain the nitro compound 13 (10.3 g, 25.2 mmol, yield: 89%). The structure of the nitro compound 13 was confirmed by 1HNMR analysis, whereby the result completely agreed with 1HNMR of the nitro compound 13 obtained in the above Example 5. EXAMPLE 7 (Example of the reaction formula (3))
NH2 NH2 ^^„x\„« x „
At room temperature, diethylamine (11.1 g, 152 mmol) and a solution of terminal acetylene 11 (12.3 g, 45.6 mmol) in toluene (34.2 mL) were added in this order to a suspension of 2-iodo-4-nitroaniline 12 (8.03 g, 30.4 mmol), bis(triphenylphosphine)palladium dichloride (213 mg, 0.304 mmol) and copper(l) iodide

(116 g, 0.608 mmol) in toluene (10.3 ml_). Then, this reaction mixture was heated to
40°C and stirred for 1 hour.
To the obtained reaction mixture, ethyl acetate (53.4 ml_) and activated carbon
(0.803 g) were added, and at 50°C, the activated carbon and the reaction residue were
removed by filtration. To the filtrate, water (24.1 ml_) was added, and the organic layer was separated. Then, the solvent in the organic layer was distilled off under reduced pressure, and to the obtained crude product, toluene (35.6 ml_) and activated carbon
(1.23 g) were added. At 100°C, the activated carbon was removed by filtration, and
from the filtrate, the desired product was recrystallized to obtain the nitro compound 13 (10.2 g, 25.2 mmol, yield: 83%). The structure of the nitro compound 13 was confirmed by 1HNMR analysis, whereby the result completely agreed with 1HNMR of the nitro compound 13 obtained in the above Example 5. EXAMPLE 8 (Example of the reaction formula (3))
At room temperature, di(n-butyl)amine (2.93 g, 22.7 mmol) and a solution of terminal acetylene 11 (7.65 g, 28.4 mmol) in toluene (21.2 ml_) were added in this order to a suspension of 2-iodo-4-nitroaniline 12 (5.00 g, 18.9 mmol), bis(triphenylphosphine)palladium dichloride (133 mg, 0.189 mmol) and copper(l) iodide (72.0 g, 0.378 mmol) in toluene (7.6 ml_). Then, this reaction mixture was heated to
40°C and stirred for 27 hours.
To the obtained reaction mixture, ethyl acetate (33.3 ml_) and activated carbon
(0.500 g) were added, and at 50°C, the activated carbon and the reaction residue were
removed by filtration. To the filtrate, water (15.0 ml_) was added, and the organic layer was separated. Then, the solvent in the organic layer was distilled off under reduced pressure, and to the obtained crude product, toluene (20.8 ml_) and activated carbon
(0.766 g) were added. At 100°C, the activated carbon was removed by filtration, and
from the filtrate, the desired product was recrystallized to obtain the nitro compound 13

(5.48 g, 13.5 mmol, yield: 72%). The structure of the nitro compound 13 was confirmed by 1HNMR analysis, whereby the result completely agreed with 1HNMR of the nitro compound 13 obtained in the above Example 5. EXAMPLE 9 (Example of the reaction formulae (1) to (3))
A suspension of glycine tert-butyl ester hydrochloride 9 (10.02 g, 59.77 mmol) in
toluene (46.2 ml_) was held at 20°C, and triethylamine (6.680 g, 66.01 mmol) was added
thereto, followed by stirring for 1 hour. Then, a solution of di-tert-butyl dicarbonate (10.01 g, 45.86 mmol) in toluene (11.6 ml_) was dropwise added to the reaction mixture, followed by a reaction for 5 hours. After confirming completion of the reaction, water (40 ml_) was added thereto, and then, the organic layer was separated. Thereafter, the solvent was partly distilled off to obtain a toluene solution (43.47 g) containing the desired N-Boc-glycine-tert-butyl ester 10.
Then, a suspension of potassium tert-butoxide (5.490 g, 48.93 mol) in tetrahydrofuran (26.7 ml_) was dropwise added at room temperature to the toluene solution of N-Boc-glycine tert-butyl ester 10 obtained as described above, whereupon the mixture was stirred for 10 minutes at room temperature. This reaction mixture was cooled with ice, and tetra-n-butylammonium iodide (0.4864 g, 13.17 mmol) and a solution of propargyl bromide (5.820 g, 48.95 mmol) in toluene (10.0 ml) were added in this order to the reaction mixture. The reaction mixture was stirred for 3 hours at room temperature, and then, a 13 wt% ammonium chloride aqueous solution (23.7 ml_) was added to terminate the reaction, whereupon the organic layer was separated. Thereafter, the solvent was partly distilled off from the organic layer to obtain a toluene solution containing the desired terminal acetylene compound 11 (32.71 g).
At room temperature, diethylamine (9.47 g, 129 mmol) and the toluene solution of terminal acetylene 11 obtained as described above, were added in this order to a

suspension of 2-iodo-4-nitroaniline 12 (6.84 g, 25.9 mmol),
bis(triphenylphosphine)palladium dichloride (90.0 mg, 0.130 mmol) and copper(l) iodide (49.3 mg, 0.25.9 mmol) in ethyl acetate (45.5 ml_). Then, this reaction mixture was
heated to 50°C and stirred for 6 hour. To this reaction mixture, activated carbon (0.68
g) was added, and at 50°C, the activated carbon and the reaction residue were removed
by filtration. To the filtrate, water (20.5 ml_) was added, and the organic layer was separated. The solvent in the organic layer was distilled off under reduced pressure, and to the obtained crude product, toluene (42.5 ml_) and activated carbon (1.05 g)
were added. At a temperature not exceeding 80°C, the activated carbon was removed
by filtration, and from the filtrate, the desired product was recrystallized to obtain the nitro compound 13 (7.86 g, 19.4 mmol, yield: 75%). The structure of the nitro compound 13 was confirmed by 1HNMR analysis, whereby the result completely agreed with 1HNMR of the nitro compound 13 obtained in the above Example 5. EXAMPLE 10 (Example of the reaction formula (4))
5% palladium/activated carbon (14.40 g) was added to a suspension of the nitro compound 13 (144.0 g, 0.3552 mol) in toluene (1.500 L). This reaction mixture was
placed in a hydrogen atmosphere and then reacted at 50°C for 48 hours. After
completion of the reaction, the catalyst in the reaction mixture was removed by filtration, and from the obtained filtrate, the solvent was distilled off to obtain a crude product.
The obtained crude product was dissolved in THF (0.7400 L), and activated carbon (13.09 g) was added, followed by stirring at room temperature for 1 hour. Thereafter, the activated carbon was removed by filtration, and from the filtrate, the solvent was distilled off to obtain a purified product of diamine 14 (129.8 g, 0.3420 mol, yield: 96%). The structure of the diamine 14 was confirmed by 1HNMR.
1 H-NMR (DMSO-d6): 5 6.54-6.42 (m, 3H, Ar-H), 3.51-3.45 (m, 2H, NCH2C02tert-Bu), 3.38-3.30 (m, 2H, CH2 CH2 N), 2.51 -2.44 (m, 2H, ArCH2), 1.84-1.76 (m, 2H,
HH.r.H.r.H^ 1 4R-1 AA (m 1RH ftprt-Riil x91

Activated carbon (0.2006 g) and 5% palladium/activated carbon (0.2000 g) were added to a suspension of the nitro compound 13 (2.002 g, 4.938 mmol) in toluene (18.5 ml_). This reaction mixture was placed in a hydrogen atmosphere under 0.5 MPa and
then reacted at 50°C for 10 minutes. After completion of the reaction, the activated
carbon and the catalyst in the reaction mixture were removed by filtration, and from the obtained filtrate, the solvent was distilled off to obtain diamine 14 (1.790 g, 4.717 mol, yield: 97%). The structure of the obtained diamine 14 was confirmed by 1HNMR analysis, whereby the result completely agreed with 1HNMR of the diamine compound 14 obtained in the above Example 10. EXAMPLE 12 (Example of the reaction formula (2))
HN^C02*-Bu H2C=CHCH2Br, f-BuOK, /f-Bu4NI^ <^^^CO^-Bu
Boc Toluene Boc
10 15
ml_) was dropwise added at room temperature to a suspension of potassium tert-butoxide (31.53 g, 281.0 mmol) in toluene (100 ml_), followed by stirring for 30 minutes. Then, tetra-n-butylammonium iodide (7.985 g, 21.62 mmol) and a solution of allyl bromide (28.77 g, 237.8 mmol) in toluene (200 ml_) were added in this order to the reaction mixture.
The obtained reaction mixture was stirred for 2 hours at room temperature, and then, water (300 ml_) was added to terminate the reaction, and toluene (100 ml_) and water (200 ml_) were further added for liquid separation. The separated aqueous layer was extracted with toluene (200 ml_), and the organic layers were put together and washed with a saturated sodium chloride aqueous solution (200 ml_). The organic layer was separated and then dried over magnesium sulfate. Thereafter, the magnesium sulfate was collected by filtration and then, the solvent in the obtained organic layer was distilled off to obtain the desired product 15 (57.62 g, 212.3 mmol, yield: 98%). The structure of the desired product 15 was confirmed by 1HNMR.

23 1 H-NMR (CDCI3): 5 5.84-5.73 (m, 1H, -CH=CH2), 5.20-5.08 (m, 2H, -CH=CH2), 3.95-3.71 (m, 4H, -NCH2C02tert-Bu and -NCH2CH=), 1.55-1.38 (m, 18H, (tert-Bu) x2). EXAMPLE 13 (Example of the reaction formula (3))
MI room temperature, suuiurn acetate i^z.uio y, z^t.o/ rnrnui; anu palladium acetate (0.02758 g, 0.1228 mmol) were added to a mixed solution of a 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_), followed by a reaction at 110°C for 3 hours
(Heck reaction).
The obtained reaction mixture was filtrated by means of Celite, and ethyl acetate (60 ml_) and water (60 ml_) were added to the obtained filtrate for liquid separation. The separated aqueous layer was extracted further with ethyl acetate (60 ml_), and the organic layers were put together and washed with water (60 ml_). Thereafter, the organic layer was separated. Then, the solvent in 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, yield: 62%). The structure of the nitro compound 16 was confirmed by 1HNMR analysis.
1 H-NMR (CDCI3): 5 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-CH2-), 4.72-4.60 (m, 2H, NH2), 4.12-4.02 (m, 2H, C=CHCH2N), 3.94-3.88 (m, 2H, NCH2C02tert-Bu ), 1.55-1.39 (m, 18H, (tert-Bu) x2). EXAMPLE 14 (Example of the reaction formula (4))
5% palladium/activated carbon (0.3767 g) was added to a suspension of the nitro compound 16 (3.767 g, 9.245 mol) in toluene (37 ml_). This reaction mixture was
placed in a hydrogen atmosphere and then reacted at 50°C for 7 hours. After

completion of the reaction, the catalyst in the reaction mixture was removed by filtration by means of Celite, and from the obtained filtrate, the solvent was distilled off to obtain a crude product.
The obtained crude product was dissolved in THF (36 ml_), and activated carbon (0.35 g) was added, followed by stirring at room temperature for 30 minutes. Then, the activated carbon was removed by filtration, and from the filtrate, the solvent was distilled off to obtain a purified product of diamine 14 (3.477 g, 9.162 mmol, yield: 99%). The structure of the obtained diamine 14 was confirmed by 1HNMR analysis, whereby the result completely agreed with 1HNMR of the diamine 14 obtained in the above Example 10. EXAMPLE 15 (Example of the reaction formula (1))
K^ Toluene Boc K^
17 18
To a solution of benzylamine 17 (107.0 g, 0.9986 mol) in toluene (780 ml_), di-tert-butyl dicarbonate (217.9 g, 0.9986 mol) was dropwise added at room temperature, followed by a reaction for 1 hour. Thereafter, water (300 ml_) was added thereto to terminate the reaction, and then, toluene (60 ml_) was further added, whereupon the organic layer was separated, and the solvent was distilled off to obtain a crude product of the desired product.
Then, the obtained crude product was subjected to recrystallization from hexane to obtain the desired N-Boc-benzylamine 18 (183.0 g, 0.8829 mol, yield: 88%). The structure of the compound 18 was confirmed by 1H-NMR analysis.
1 H-NMR (CDCI3): 5 7.35-7.23 (m, 5H, -Ph), 4.88 (b-s, 1H, NH), 4.31 (d, 2H, J=5.6 Hz, NCH2Ph), 1.46 (s, 9H, tert-Bu). EXAMPLE 16 (Example of the reaction formula (2))
HN^Nj^j HC=CCH2Br, f-BuOK, /i-Bu4NI jf^n^^
Boc \^y Toluene Boc
18 19
A solution of N-Boc-benzylamine 18 (20.60 g, 99.39 mmol) in toluene (40 mL) was dropwise added at room temperature to a suspension of potassium tert-butoxide
(14.50g, 129.2 mmol) in toluene (80 mL), whereupon the mixture was heated to 60°C
and stirred for 2 hours. Then, the reaction mixture was cooled in an ice bath, and

tetra-n-butylammonium iodide (1.836 g, 4.969 mmol) and a solution of propargyl bromide (13.01 g, 109.3 mmol) in toluene (80 ml_) were added in this order to the reaction mixture.
Then, the mixture was stirred for 4 hours at room temperature, whereupon water (100 ml_) was added to terminate the reaction. Thereafter, the organic layer and the aqueous layer were separated. The aqueous layer was further extracted with ethyl acetate (50 ml_) and separated, and the organic layers were put together and washed with a saturated sodium chloride aqueous solution (30 ml_). Thereafter, the organic layer was separated, and the solvent was distilled off to obtain the desired product 19 (22.86 g, 93.18 mmol, yield: 94%). The structure of the desired product 19 was confirmed by 1HNMR analysis.
1 H-NMR (CDCI3): 5 7.35-7.23 (m, 5H, -Ph), 4.56 (s, 2H, CH2), 4.10-3.82 (b-m, 2H, CH2), 2.21 (b-s, 1H, H-C=C), 1.58-1.39 (b-m, 9H, tert-Bu). EXAMPLE 17 (Example of the reaction formula (3))
at room temperature, aietnyiamine (u.^atsj g, o.tsi3 mmoij ana a solution OT terminal acetylene compound 19 (2.089 g, 8.516 mol) in THF (2 ml_) were added in this order to a suspension of 2-iodo-4-nitroaniline 12 (1.499 g, 5.678 mmol), bis(triphenylphosphine)palladium dichloride (0.03985 g, 0.05678 mmol) and copper(l)
iodide (0.02163 g, 0.1135 mmol) in THF (7 ml_). Then, the mixture was heated to 40°C
and stirred for 6 hours.
To the obtained reaction mixture, water (10 ml_) and ethyl acetate (10 ml_) were added to terminate the reaction. Then, the reaction mixture was subjected to filtration by means of Celite. From the obtained filtrate, the organic layer was separated, and the solvent was distilled off to obtain a crude product. Then, the crude product was recrystallized by using toluene and hexane to obtain the desired product 20 (1.807 g, 4.737 mmol, yield: 83%). The structure of the product 20 was confirmed by 1HNMR analysis.
1 H-NMR (CDCb): 5 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, NCH2Ph), 6.63 (d, 1H, J=9.2 Hz, Ar-H), 5.10-4.67 (b-m, 2H, NH2), 4.59 (s, 2H, CH2), 4.25 (b-s, 2H, CH2), 1.51 (s, 9H, tert-Bu).
INDUSTRIAL APPLICABILITY
According to the present invention, it is possible to simply and efficiently produce, from an inexpensive starting material, a diamine compound which is useful as a starting material for a liquid crystal aligning agent. Further, the production process of the present invention is industrially useful, since it is thereby possible to carry out production in a large scale.
The entire disclosure of Japanese Patent Application No. 2010-182555 filed on August 17, 2010 including specification, claims and summary is incorporated herein by reference in its entirety.

1. An ester compound represented by the following formula:
2. A nitro compound represented by any one of the following formulae: