JP2008273906A - Nitrated urethane compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new nitrated urethane compound generating a base in high sensitivity and a method for easily producing the compound. <P>SOLUTION: The nitrated urethane compound is expressed by formula (1) (in the formula, X is a single bond, O, S, NR<SB>10</SB>or CR<SB>11</SB>R<SB>12</SB>; R<SB>1</SB>and R<SB>2</SB>are each a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group a heterocyclic group or together form a monocyclic or polycyclic group; R<SB>3</SB>to R<SB>12</SB>each represents an atom, a group or a ring structure exemplified in the definition of R<SB>1</SB>and R<SB>2</SB>, an alkoxy group, an alkoxycarbonyl group, an amino group, an aminocarbonyl group, an acyloxy group, an aroyloxy group, a sulfide group, a nitro group, a sulfonyl group or a halogen atom). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel nitrated urethane compound useful as a photopolymerization initiator, a photobase generator, and the like, a production method thereof, a novel nitrated hydroxy compound useful as a raw material for the nitrated urethane compound, and a production method thereof.

In recent years, compounds that generate bases by being decomposed by radiation such as ultraviolet light have attracted attention, and are particularly used for photoresist applications.
For example, 2-nitrobenzylcarbamic acid esters are known as compounds that generate amines by ultraviolet irradiation (see Patent Document 1). This compound gives a positive photoresist by adding it to an acid curable polymer together with a thermal acid generator (see Non-Patent Document 1), or a negative photoresist by adding it to a carboxylic acid-containing polymer. Is known (see Non-Patent Document 2).

  As for these 2-nitrobenzylcarbamic acid esters, compounds in which various substituents are introduced into the nitrobenzyl group and compounds in which the structure of the amine compound generated by radiation irradiation is designed in various ways have been studied. (See Non-Patent Document 3, Non-Patent Document 4, Non-Patent Document 5, and Non-Patent Document 6).

However, since 2-nitrobenzylcarbamic acid esters that have been conventionally studied are not sufficiently sensitive to radiation, development of a highly sensitive and high-performance photobase generator has been desired.
Japanese Patent Laid-Open No. 10-77257 Journal of Photopolymer Science and Technology, 3 (3), 419-420 (1990) Gov. Rep. Announce Index, 93 (18), 1-11 (1993) Bulletin of the Chemical Society of Japan, 71, 2483-2507 (1998) Tetrahedron, 53 (12), 4247-4264 (1997) Tetrahedron Letters, 41, 6341-6346 (2000) Chem. Eur. Journal, 12, 6865-6879 (2006)

  An object of the present invention is to provide a novel nitrated urethane compound capable of generating a base with high sensitivity and a simple production method thereof as a compound that replaces 2-nitrobenzylcarbamic acid esters. Another object of the present invention is to provide a nitrated hydroxy compound useful as a raw material for the nitrated urethane compound and a simple production method thereof.

  The present inventors have conducted intensive studies in view of the above problems. As a result, a novel nitrated urethane compound capable of generating a base with high sensitivity and a method for producing the same have been found, and the present invention has been completed. Specific embodiments of the present invention are as follows.

  [1] A nitrated urethane compound represented by the following formula (1).

In formula (1), R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms that may have a substituent, or an alkenyl having 2 to 12 carbon atoms that may have a substituent. A cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent, Alternatively, R ₁ and R ₂ are each bonded to each other to represent a monocyclic or polycyclic ring that may have a substituent, and at least one of R ₁ and R ₂ is not hydrogen,
R _{3 to} R ₉ each independently have hydrogen, an alkyl group having 1 to 12 carbon atoms that may have a substituent, an alkenyl group having 2 to 12 carbon atoms that may have a substituent, or a substituent. A cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a substituent. It has a C1-C12 alkoxyl group, a C1-C12 alkoxycarbonyl group that may have a substituent, a C1-C12 acyl group that may have a substituent, and a substituent An optionally substituted amino group having 1 to 12 carbon atoms, an aminocarbonyl group having 1 to 12 carbon atoms which may have a substituent, an acyloxyl group having 1 to 12 carbon atoms which may have a substituent, and a substituent; C6-C12 alloyoxyl group which may have, C1-C12 which may have a substituent Rufido group, a nitro group, a sulfonyl group, or halogen, or is formed by combining with another adjacent group, a monocyclic or polycyclic and may have a substituent,
—X— represents a single bond, —O—, —S—, —NR ₁₀ — or —CR ₁₁ R ₁₂ — (R ₁₀ , R ₁₁ and R ₁₂ are as defined above for R _{3 to} R _9. .)

  [2] The nitrated urethane compound according to item [1] represented by any one of the following formulas (1-1) to (1-4).

  [3] A nitrated hydroxy compound represented by the following formula (2).

In formula (2), R _{3 to} R ₉ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms that may have a substituent, or an alkenyl having 2 to 12 carbon atoms that may have a substituent. Group, optionally substituted cycloalkyl group having 3 to 12 carbon atoms, optionally substituted aryl group having 6 to 12 carbon atoms, optionally substituted heterocyclic group, substituted An alkoxyl group having 1 to 12 carbon atoms which may have a group, an alkoxycarbonyl group having 1 to 12 carbon atoms which may have a substituent, and an acyl group having 1 to 12 carbon atoms which may have a substituent , An amino group having 1 to 12 carbon atoms which may have a substituent, an aminocarbonyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 12 carbon atoms which may have a substituent Carbon having 6 to 12 carbon atoms which may have an acyloxyl group and a substituent, and carbon which may have a substituent 1-12 sulfide group, a nitro group, a sulfonyl group, or halogen, or is formed by combining with another adjacent group, a monocyclic or polycyclic and may have a substituent,
—X— represents a single bond, —O—, —S—, —NR ₁₀ — or —CR ₁₁ R ₁₂ — (R ₁₀ , R ₁₁ and R ₁₂ are as defined above for R _{3 to} R _9. .)

  [4] A nitrated hydroxy compound represented by the following formula (2-1).

  [5] represented by the following formula (4), comprising a step of reacting the nitrated hydroxy compound represented by the formula (2) according to the item [3] with the isocyanate compound represented by the following formula (3). A method for producing a nitrated urethane compound.

In the above formulas (3) and (4), R ₂ is an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkenyl group having 2 to 12 carbon atoms, and a substituent. A cycloalkyl group having 3 to 12 carbon atoms which may have a group, an aryl group having 6 to 12 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent;
R ₃ to R ₉ and -X- represents an R ₃ to R ₉ and -X- and as defined in the formula (2).

  [6] The reaction of the nitrated hydroxy compound represented by the formula (2) according to the item [3] and the carbonyl compound represented by the following formula (5) in the presence or absence of a base. The manufacturing method of the nitrated urethane compound represented by Formula (1) of item [1] including the process of making the amine compound represented by following formula (6) react after making it react.

In formula (5), Z ₁ and Z ₂ each independently represent halogen, an alkoxyl group having 1 to 12 carbon atoms which may have a substituent, a phenoxy group which may have a substituent, or a substituent. The imidazolyl group which may have is shown.

In Formula (6), R ₁ and R ₂ have the same meaning as R ₁ and R _{2 in} Formula (1).
[7] The nitrated hydroxy compound represented by formula (2) according to item [3], and Z ₁ —CO
—NR ₁ R ₂ (Z ₁ is halogen, an optionally substituted alkoxyl group having 1 to 12 carbon atoms,
An optionally substituted phenoxy group or a substituent shown also imidazolyl group, R ₁ and R _2, R ₁ and R ₂ of formula (1) according to claim [1], Is equivalent to The method for producing a nitrated urethane compound represented by formula (1) according to item [1], comprising a step of reacting a compound represented by formula (1) in the presence of a base.

  [8] A process for producing a nitrohydroxy compound represented by formula (2) according to item [3], comprising a step of reducing a nitrated carbonyl compound represented by formula (7) below.

In formula (7), R < ₃ > -R < ₉ > and -X- show the same meaning as R < ₃ > -R < ₉ > and -X- in said formula (2).

  Since the nitrated urethane compound of the present invention can generate a base with higher sensitivity than conventional 2-nitrobenzylcarbamic acid esters, it is useful as a photobase generator for photoresist.

Hereinafter, the present invention will be described in detail.
The nitrated urethane compound of the present invention is represented by the following formula (1).

In formula (1), R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms that may have a substituent, or an alkenyl having 2 to 12 carbon atoms that may have a substituent. A cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent, Alternatively, R ₁ and R ₂ are each bonded to each other to represent a monocyclic or polycyclic ring which may have a substituent, and at least one of R ₁ and R ₂ is not hydrogen.

Specific examples of R ₁ and R ₂ include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group. Moreover, examples of the —NR ₁ R ₂ group constituted by R ₁ and R ₂ being bonded to each other to form a single ring include a piperidine group and a pyrrolidine group.

In formula (1), R < ₃ > -R < ₉ > is respectively independently hydrogen, a C1-C12 alkyl group which may have a substituent, and a C2-C12 alkenyl which may have a substituent. Group, optionally substituted cycloalkyl group having 3 to 12 carbon atoms, optionally substituted aryl group having 6 to 12 carbon atoms, optionally substituted heterocyclic group, substituted C1-C12 alkoxyl group which may have a group, C1-C12 acyl group which may have a substituent, C1-C12 alkoxycarbonyl group which may have a substituent , An amino group having 1 to 12 carbon atoms which may have a substituent, an aminocarbonyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 12 carbon atoms which may have a substituent Carbon having 6 to 12 carbon atoms which may have an acyloxyl group and a substituent, and carbon which may have a substituent 1-12 sulfide group, a nitro group, a sulfonyl group, or halogen, or is formed by combining with another adjacent group, a monocyclic or polycyclic and may have a substituent.

Specific examples of R _{3 to} R ₉ include hydrogen, methyl group, ethyl group, methoxy group, ethoxy group, nitro group, dimethylamino group, chlorine and bromine.
In the formula (1), —X— represents a single bond, —O—, —S—, —NR ₁₀ — or —CR ₁₁ R ₁₂ — (R ₁₀ , R ₁₁ and R ₁₂ are the above R _{3 to} R _This is the same as ₉ ).

  Specific examples of the nitrated urethane compound represented by the above formula (1) include the compounds shown below.

  The nitrated hydroxy compound of the present invention, which is useful as a raw material for the nitrated urethane compound, is represented by the following formula (2).

In formula (2), R _{3 to} R ₉ and —X— are as defined in formula (1).
Specific examples of the nitrated hydroxy compound represented by the above formula (2) include the compounds shown below.

  The first aspect of the method for producing a nitrated urethane compound of the present invention is as follows by reacting a nitrated hydroxy compound represented by the above formula (2) with an isocyanate compound represented by the following formula (3). This is a method for producing a nitrated urethane compound represented by the formula (4).

In the above formulas (3) and (4), R ₂ is an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkenyl group having 2 to 12 carbon atoms, and a substituent. A cycloalkyl group having 3 to 12 carbon atoms which may have a group, an aryl group having 6 to 12 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent; _{3 to} R ₉ and —X— are as defined in the above formula (1).

In this production method, the reaction method is not particularly limited as long as the nitrated hydroxy compound and the isocyanate compound can be reacted. However, a solvent may be used to increase the contact efficiency or control the reaction temperature. it can. The solvent can be used without any particular problem as long as it is a liquid that does not react with the nitrated urethane compound and the isocyanate compound and is stable under the reaction temperature conditions. Specific examples include toluene, dichloromethane, ethylene glycol dimethyl ether and dimethyl sulfoxide.

  Moreover, in the said manufacturing method, in order to speed up reaction rate, a catalyst and an additive can be used. The catalyst is not particularly limited as long as it is a catalyst used in a reaction of synthesizing a urethane compound by reacting a hydroxy group and an isocyanate group. Specific examples include dibutyltin dilaurate and triethylamine. As the additive, lithium hydride or sodium hydride can be used for the purpose of activating the hydroxy compound. That is, the hydroxy compound may be converted to an alkali metal alcoholate using such an additive and then reacted with an isocyanate compound.

  Moreover, the 2nd aspect of the manufacturing method of the nitrated urethane compound of this invention exists in the presence of a base, the nitrated hydroxy compound represented by the said Formula (2), and the carbonyl compound represented by following formula (5). Or reacting without or present, the method further comprises a step of reacting the amine compound represented by the following formula (6) with the nitrated urethane compound represented by the above formula (1). .

In formula (5), Z ₁ and Z ₂ each independently represent halogen, an alkoxyl group having 1 to 12 carbon atoms which may have a substituent, a phenoxy group which may have a substituent, or a substituent. The imidazolyl group which may have is shown. In formula (6), R ₁ and R ₂ are as defined in formula (1) above.

As the carbonyl compound represented by the above formula (5), any carbonyl compound capable of synthesizing a halogenated formate ester, carbonate ester or urethane compound by reacting with a hydroxy compound can be used without any problem. Specific examples include phosgene, diphosgene, triphosgene, phenyl chloroformate, 4-chlorophenyl formate, ethyl chloroformate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and N, N′-carbodiimidazole. It is done.

  Moreover, as an amine compound represented by the said Formula (6), if it is a primary amine or a secondary amine, it can use conveniently. Specific examples include dimethylamine, diethylamine, dioctylamine, n-butylamine, piperidine, piperazine, 2,6-dimethylpiperazine, hexamethylenediamine and xylylenediamine.

A third aspect of the manufacturing method of nitration urethane compounds of the present invention, the nitrated hydroxy compound represented by the above formula _{(2), Z 1 -CO-} NR 1 R 2 (Z 1 is the formula ( 5), and R ₁ and R ₂ are as defined in the above formula (1).), Which comprises reacting the compound represented by the above formula (1) in the presence of a base. It is a manufacturing method of the nitrated urethane compound represented by 1).

  The manufacturing method of the nitrated hydroxy compound represented by the above formula (2) includes a step of reducing the nitrated carbonyl compound represented by the following formula (7).

In the formula (7), R _{3 to} R ₉ and —X— are as defined in the above formula (1).
The reducing agent that can be used in this production method is not particularly limited as long as it is a reducing agent that can reduce a carbonyl group to a hydroxy group without reducing the nitro group. Preferred reducing agents include sodium borohydride, lithium borohydride, and sodium.
Examples include tri-sec-butylborohydride, lithium aluminum hydride, diisobutylaluminum hydride, and the like, and sodium borohydride is particularly preferable.

  The reaction conditions for reducing the nitrated carbonyl compound are not particularly limited, but a solvent can be used to increase the contact efficiency and control the reaction temperature. The solvent is not particularly limited as long as it is a solvent that is stable under reducing reaction conditions. Preferable specific examples include diethylene glycol dimethyl ether, methanol, ethanol, butanol and the like.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. Note that Synthesis Example 1 and Synthesis Example 2 are described in the prior art (Journal of
American Chemical Society (1949) (71) 3556).

<Synthesis Example 1>
A 300 mL three-necked flask equipped with a thermometer and a Dimroth condenser was charged with 2-chlorobenzoic acid (15.7 g), 3-nitrophenol (16.4 g), sodium carbonate (12.7 g) and diethylene glycol dimethyl ether (200 mL). The reactor was charged with nitrogen. The reaction mixture was heated to 170 ° C. in an oil bath, and a mixture of copper powder (1.3 g), cuprous chloride (0.2 g) and diethylene glycol dimethyl ether (20 mL) was charged into the reactor. Since a precipitate was deposited, 50 mL of diethylene glycol dimethyl ether was added and heated for 5 hours. After the reaction mixture was cooled to room temperature, the precipitate was filtered and washed with diethylene glycol dimethyl ether (50 mL) and diethyl ether (100 mL). The obtained wet solid was dissolved in water (200 mL), and the copper-colored precipitate that did not dissolve was filtered off. When the obtained aqueous solution was neutralized with 1N HCl and the pH was adjusted to 2, a white precipitate was deposited. When 300 mL of acetonitrile was added thereto, the reaction mixture became a uniform solution. Crystals were precipitated from the homogeneous solution by distilling off acetonitrile with an evaporator. The crystals were filtered and dried to obtain colorless crystals (1.7 g). The results of ¹ H-NMR measurement of the obtained colorless crystals are shown below.

13.0 ppm (1H, s, COOH), 7.9 ppm (2H, dd, benzene ring), 7.7 ppm (2H, m, benzene ring), 7.5 ppm (1H, s, benzene ring), 7.4 ppm (2H, m, benzene ring), 7.2 ppm (1H, d, benzene ring)
From the above results, it was confirmed that this colorless solid was 2- (3-nitrophenoxy) benzoic acid represented by the following chemical formula.

<Synthesis Example 2>
2- (3-nitrophenoxy) benzoic acid (1.7 g) obtained in Synthesis Example 1 and concentrated sulfuric acid (10 mL) were placed in a 50 mL eggplant flask equipped with a Dimroth condenser, and the inside of the reactor was purged with nitrogen. . The reaction mixture was heated to 100 ° C. in an oil bath and stirred for 30 minutes. After cooling to room temperature, the reaction mixture was poured into 500 mL of water, resulting in a white precipitate. The precipitate was filtered, washed with water, and dried to obtain 1.5 g of a white solid. This white solid was dissolved in a small amount of acetic acid and heated to 100 ° C. After dissolution, when cooled to room temperature, 0.7 g of off-white crystals were obtained. The result of ¹ H-NMR measurement of the obtained white crystals is shown below.

8.3 ppm (1H, d, benzene ring), 7.8 ppm (2H, m, benzene ring), 7.7 ppm (1H, d, benzene ring), 7.5 ppm (1H, d, benzene ring), 7. 4ppm (1H, dd, benzene ring), 7.3ppm (1H, d, benzene ring)
From the above results, it was confirmed that this crystal was 1-nitroxanthenone represented by the following chemical formula.

<Example 1>
A 50 mL two-necked flask equipped with a Dimroth condenser was charged with 1-nitroxanthenone (1.84 g) obtained in Synthesis Example 2, sodium borohydride (0.36 g), and diethylene glycol dimethyl ether (20 mL). The mixture was stirred at 45 ° C. for 6 hours under a nitrogen atmosphere. To the reaction mixture was added 30 mL of 10% aqueous potassium dihydrogen phosphate solution, and the mixture was extracted with ethyl acetate to obtain a tan solution. The ¹ H-NMR measurement result of the obtained tan solution is shown below.

7.7 ppm (1H, dd, benzene ring), 7.4 ppm (1H, dd, benzene ring), 7.3 ppm (2H, m, benzene ring), 7.2 ppm (1H, dd, benzene ring), 7. 1 ppm (1H, dd, benzene ring), 7.0 ppm (1H, d, benzene ring), 6.2 ppm (1H, s, CH—O), 3.7 ppm (1H, br, —OH)
From the above results, it was confirmed that this solution was a diethylene glycol dimethyl ether solution of 1-nitroxanthhydrol represented by the following chemical formula.

<Example 2>
In a 100 mL two-necked flask equipped with a Dimroth condenser, 1-nitroxanthhydrol solution of diethylene glycol dimethyl ether obtained in Example 1 (11.7 g, 12.8 wt%), cyclohexyl isocyanate (1.0 g) and Dibutyltin dilaurate (0.1 g) was added and heated at 60 ° C. for 2 hours to precipitate a solid. After cooling the reaction mixture, 100 mL of hexane was added and the solid was filtered. This solid was dissolved in ethyl acetate, the ethyl acetate solution from which insoluble matter was filtered was concentrated, and hexane was added to precipitate an off-white solid. The result of ¹ H-NMR measurement of the obtained off-white solid is shown below (see FIG. 1).

7.8 ppm (1H, d, benzene ring), 7.7 ppm (1H, d, benzene ring), 7.5 ppm (3H, m, benzene ring), 7.4 ppm (1H, dd, benzene ring), 7. 2ppm (2H, m, benzene ring), 4.4ppm (1H, d, CH-O), 3.5ppm (1H, m, N-CH), 1.0-2.0ppm (10H, m, -CH) _2- )
From the above results, it was confirmed that this off-white solid was O- (cyclohexylaminocarbonyl) -1-nitroxanthhydrol (NXU) represented by the following chemical formula.

<Preparation Example 1>
0.60 g (3 mmol) of oxydianiline (manufactured by Tokyo Chemical Industry) is dissolved in 7.7 g of dimethylacetamide, and 0.88 g (3 mmol) of 3,4-3 ′, 4′-biphenyltetracarboxylic anhydride (manufactured by Tokyo Chemical Industry) is dissolved. ) Was added and stirred for 3 hours to obtain a 10 wt% polyamic acid solution as a viscous liquid. This solution was diluted with dimethylacetamide to obtain a 5% by weight polyamic acid solution.

<Preparation Example 2>
4.3 g (20 mmol) of 2-nitroveratryl alcohol (manufactured by Tokyo Chemical Industry) and 3.0 g (24 mmol) of cyclohexyl isocyanate (manufactured by Tokyo Chemical Industry) were mixed with 10 mL of toluene, and the reaction mixture was heated at 100 ° C. for 7 hours. After allowing to cool, the deposited precipitate was filtered to obtain 6.7 g (99% yield) of 2-nitroveratryloxycarbonylcyclohexylamine (NVC) as pale yellow crystals.

<Evaluation>
As a polyimide film forming solution, (1) the polyamic acid solution obtained in Preparation Example 1 alone (no addition), (2) the polyamic acid solution obtained in Preparation Example 1, and the NVC obtained in Preparation Example 2 A mixed solution of a polyamic acid and a photobase generator mixed with a dimethylacetamide solution (concentration: 5% by weight) at a ratio of 9: 1 (weight ratio), and (3) a polyamic acid solution obtained in Preparation Example 1, A mixed solution of polyamic acid and photobase generator prepared by mixing 9: 1 (weight ratio) of the NXU dimethylacetamide solution (concentration: 5% by weight) obtained in Example 2 was used.

  These polyimide film-forming solutions were spin-cast on a stainless steel plate, dried in air at 100 ° C. for 5 minutes, and then irradiated with ultraviolet rays for 167 seconds with an ultrahigh pressure mercury lamp (12 mW). Subsequently, it heated at 160 degreeC and the imidation rate after 1 hour and 2 hours was measured in the reflection IR spectrum. The imidization rate was calculated | required from the following formula with reference to the literature (Polymers for Advanced Technologies, 2006, 17, 131-136).

In the above formula, “Sample A ₁₃₇₆ / A ₁₂₄₁ ” is observed by IR spectrum after heating to 160 ° C. for 1 hour and after 2 hours by irradiating the coating film formed using each polyimide film forming solution. the ratio of absorbance of the absorbance and 1241cm ^-1 of been 1376cm ^-1, "before heating a ₁₃₇₆ / a _1241" is before the ultraviolet irradiation of the coating film formed using each polyimide film forming solution I
The ratio of the absorbance at ₁₃₇₆ cm ^{−1 and} the absorbance at ₁₂₄₁ cm ⁻¹ observed in the R spectrum. “Polyimide A ₁₃₇₆ / A ₁₂₄₁ ” indicates that equimolar cyclohexylamine is added to the polyamic acid solution obtained in Preparation Example 1. A coating film formed in the same manner as above using the added solution (no photobase generator added) was observed in the IR spectrum after heating at 160 ° C. for 2 hours (after complete imidization) at 1376 cm. ^-1 is the ratio of the absorbance at 1241 cm ^-1 .

  The results of the imidization rate determined as described above are shown in Table 1 and FIG.

2 is a ¹ H-NMR spectrum of the nitrated urethane compound of the present invention obtained in Example 2. FIG. It is a graph which shows the evaluation result performed in the Example.

Claims (8)

A nitrated urethane compound represented by the following formula (1).

[In Formula (1), R < ₁ > and R < ₂ > are each independently hydrogen, a C1-C12 alkyl group which may have a substituent, and a C2-C12 which may have a substituent. An alkenyl group, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or an optionally substituted heterocyclic group Or a monocyclic or polycyclic ring which may have a substituent formed by bonding R ₁ and R ₂ to each other, wherein at least one of R ₁ and R ₂ is not hydrogen,
R _{3 to} R ₉ each independently have hydrogen, an alkyl group having 1 to 12 carbon atoms that may have a substituent, an alkenyl group having 2 to 12 carbon atoms that may have a substituent, or a substituent. A cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a substituent. A C1-C12 alkoxyl group, a C1-C12 alkoxycarbonyl group that may have a substituent, a C1-C12 acyl group that may have a substituent, and a substituent. An optionally substituted amino group having 1 to 12 carbon atoms, an aminocarbonyl group having 1 to 12 carbon atoms that may have a substituent, an acyloxyl group having 1 to 12 carbon atoms that may have a substituent, and a substituent C6-C12 alloyoxyl group which may have a C1-C1 which may have a substituent A sulfide group, a nitro group, a sulfonyl group, or halogen, or is formed by combining with another adjacent group, a monocyclic or polycyclic and may have a substituent,
—X— represents a single bond, —O—, —S—, —NR ₁₀ — or —CR ₁₁ R ₁₂ — (R ₁₀ , R ₁₁ and R ₁₂ are as defined above for R _{3 to} R _9. .) ] The nitrated urethane compound according to claim 1, which is represented by any one of the following formulas (1-1) to (1-4).

A nitrated hydroxy compound represented by the following formula (2).

[In Formula (2), R < ₃ > -R < ₉ > is respectively independently C1-C12 alkyl group which may have hydrogen and a substituent, and C2-C12 which may have a substituent. An alkenyl group, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, an optionally substituted heterocyclic group, C1-C12 alkoxyl group which may have a substituent, C1-C12 alkoxycarbonyl group which may have a substituent, C1-C12 which may have a substituent An acyl group, an amino group having 1 to 12 carbon atoms that may have a substituent, an aminocarbonyl group having 1 to 12 carbon atoms that may have a substituent, and 1 to carbon atoms that may have a substituent; 12 acyloxyl groups, optionally having 6-12 carbon atoms, optionally having a substituent A sulfide group, a nitro group having 1 to 12 carbon atoms, a sulfonyl group, or halogen, or is formed by combining with another adjacent group, a monocyclic or polycyclic and may have a substituent,
—X— represents a single bond, —O—, —S—, —NR ₁₀ — or —CR ₁₁ R ₁₂ — (R ₁₀ , R ₁₁ and R ₁₂ are as defined above for R _{3 to} R _9. .) ] A nitrated hydroxy compound represented by the following formula (2-1).

The nitration represented by following formula (4) including the process with which the nitrated hydroxy compound represented by Formula (2) of Claim 3 and the isocyanate compound represented by following formula (3) are made to react. A method for producing a urethane compound.

[In the above formulas (3) and (4), R ₂ is an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkenyl group having 2 to 12 carbon atoms, A cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent;
R ₃ to R ₉ and -X- represents an R ₃ to R ₉ and -X- and as defined in the formula (2). ] After reacting the nitrated hydroxy compound represented by the formula (2) according to claim 3 and the carbonyl compound represented by the following formula (5) in the presence or absence of a base, The manufacturing method of the nitrated urethane compound represented by Formula (1) of Claim 1 including the process of making the amine compound represented by following formula (6) react further.

[In Formula (5), Z < ₁ > and Z < ₂ > are respectively independently a halogen, the C1-C12 alkoxyl group which may have a substituent, the phenoxy group which may have a substituent, or a substituent. The imidazolyl group which may have is shown. ]

[In Formula (6), R ₁ and R ₂ have the same meanings as R ₁ and R _{2 in} Formula (1). ] And nitrated hydroxy compound represented by formula (2) according to claim _{3, Z 1 -CO-NR 1} R 2 (Z 1 is halogen, alkoxy having 1 to 12 carbon atoms which may have a substituent group, an optionally substituted phenoxy group or a substituent shown also imidazolyl group, R ₁ and R _2, R ₁ and R in the formula (1) according to claim 1, _{2. The} method for producing a nitrated urethane compound represented by the formula (1) according to claim 1, comprising a step of reacting a compound represented by ₂ ) in the presence of a base. The manufacturing method of the nitrohydroxy compound represented by Formula (2) of Claim 3 including the process of reduce | restoring the nitrated carbonyl compound represented by following formula (7).

Wherein (7), R ₃ to R ₉ and -X- represents an R ₃ to R ₉ and -X- and as defined in the formula (2). ]

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