JPH0881429A - New imide compound and its production - Google Patents

Abstract

PURPOSE: To obtain a new imide compound, stable to visible light, capable of reversibly changing absorption characteristics only in an ultraviolet region and suitably utilizable as an optical recording material or a copying medium. CONSTITUTION: This new imide compound of formula I (Ar is a 6-11C aryl; R<1> is a 1-5C alkyl or a 6-11C aryl; R<2> to R<4> are each H, a 1-4C alkyl, a 2-4C alkoxycarbonyl or a 6-11C aryl and at least one of R<1> to R<4> is a 6-11C aryl), e.g. N-benzyl-N-benzoylcinnamamide. The compound of formula I is obtained by reacting either of an acid halide of formula II (X is a halogen) and an acid halide of formula III with a primary amine of formula IV.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel imide compound which is stable to visible light and reversibly changes its absorption characteristics only in the ultraviolet region, and which can be suitably used as an optical recording material or a copying medium. And a manufacturing method thereof.

[0002]

2. Description of the Related Art Generally, it is known that an organic compound that undergoes a photoreaction such as photoisomerization has a change in light absorption property. Compounds have been developed in which the absorption characteristics of light reversibly change with light of different wavelengths. Among them, photochromic compounds whose absorption characteristics in the visible light region change are well known, and spiropyrans, spirooxazines, azobenzenes, diarylethenes, fulgimides, etc.
Various studies have been conducted as recording materials for optical recording and copying media. However, these compounds are colored by changing to a structure with absorption in the visible light region by cyclization or isomerization with ultraviolet rays, and when irradiated with visible light, they return to the original compound without absorption in the visible light region. Since it is a type of compound that is decolorized by, there is a practical problem that the stability against visible light is essentially low.

On the other hand, there is also known a reaction in which absorption characteristics are reversibly changed only in the ultraviolet region without absorption in the visible light region, and trans-cis isomerization of stilbene, isomerization of benzene to benzvalene, α- Examples include isomerization of tropolone methyl ether to 1-methoxybicyclo [3.2.0] heptadien-2-one. However, since stilbene and benzene have unstable photoisomerization products, it is necessary to handle them at a low temperature, and α-tropolone methyl ether causes a large number of side reactions. Moreover, the photoreaction yield of the compound itself was low, and in any case, it was not practical as an optical recording material.

Further, these compounds whose light absorption properties are reversibly changed have a drawback in that the manufacturing method is complicated and many steps are required, so that the manufacturing cost is high.

[0005]

The object of the present invention is to solve the above-mentioned problems of the prior art, to reversibly change the absorption characteristics only in the ultraviolet region, to stabilize the photoreaction product, and It is an object of the present invention to provide a new type of compound which can be suitably used for a recording material such as an optical recording and a copying medium, and a method for producing the same, which has a relatively high photoreaction yield.

[0006]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that an imide compound having a specific structure is stable to visible light and has reversible absorption characteristics only in the ultraviolet region. The present invention has been completed by discovering that the above-mentioned various drawbacks of the prior art can be overcome.

That is, the gist of the first invention is the following general formula [1]:

[Chemical 5] (In the formula, Ar represents an aryl group having 6 to 11 carbon atoms, and R
¹ represents an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 11 carbon atoms, and R ² , R ³ and R ⁴ are independently selected hydrogen, an alkyl group having 1 to 4 carbon atoms, and a carbon number. 2-4 alkoxycarbonyl groups or 6-11 carbon atoms
And an aryl group of R ¹ , R ² , R ³ and R
^At least one of ⁴ represents an aryl group having 6 to 11 carbon atoms. ) And a second aspect of the present invention is the step of reacting one acid halide with a primary amine to form an amide, and further adding another acid halide to the amide. A method for producing an imide, which comprises a step of reacting

[Chemical 6] (In the formula, Ar has the same meaning as described above, and X represents halogen.) And an acid halide (A) represented by the general formula [3].

[Chemical 7] (In the formula, R ¹ has the same meaning as described above, and X represents halogen.) An acid halide (B) represented by the general formula [4]

Embedded image (Wherein R ² , R ³ and R ⁴ have the same meanings as described above), and in these raw materials, R ¹ , R ² , R ³ and R ⁴ At least one is an aryl group having 6 to 11 carbon atoms, which is a method for producing the novel imide compound.

First, the imide compound of the present invention will be described in more detail. In general formula [1], Ar has 6 to 6 carbon atoms.
Examples of the aryl group of 11 include a phenyl group, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and a tert-pentyl group at the o-, m- or p-position of a benzene nucleus. And an alkoxyl group such as an alkyl group, a methoxyl group, an ethoxyl group and an isopropoxyl group, or a substituted phenyl group substituted with a halogen such as fluorine, chlorine, bromine and iodine.

Examples of the alkyl group having 1 to 5 carbon atoms for R ¹ include methyl group, ethyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-pentyl group, Examples of the aryl group having 6 to 11 carbon atoms include a phenyl group, o-, m- of a benzene nucleus, or
Alkyl group such as methyl group, ethyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-pentyl group, etc. at the p-position, alkoxy group such as methoxyl group, ethoxyl group, isopropoxyl group or Substituted phenyl groups in which halogens such as fluorine, chlorine, bromine and iodine have been substituted are mentioned.

Further, the carbon number of R ² , R ³ and R ⁴ is 1
Examples of the alkyl group of ~ 4 include a methyl group, an ethyl group,
Isopropyl group, isobutyl group, sec-butyl group, tert-
Examples thereof include a methoxy group, an ethoxycarbonyl group, and an isopropoxycarbonyl group. Examples of the C 2-4 alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and an isopropoxycarbonyl group. Examples of the C 6-11 aryl group include phenyl. Group, alkyl group such as methyl group, ethyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-pentyl group, o-, m- or p-position of benzene nucleus, methoxyl group, ethoxyl Group, an alkoxyl group such as an isopropoxyl group, or a substituted phenyl group substituted with a halogen such as fluorine, chlorine, bromine and iodine.

The imide compound of the present invention having such a structure absorbs only in the ultraviolet region, and when it is irradiated with ultraviolet rays, it has the ethenyl group substituted with Ar and R ¹ , R ² , R ³ and R ⁴ among them. Cyclization occurs by reacting with the benzene nucleus of one aryl group having 6 to 11 carbon atoms. The yield of this photocyclization reaction is often high, and is generally about 50% or more.

The cyclized product as a reaction product has the following general formula [5] when R ¹ is an alkyl group having 1 to 5 carbon atoms.

[Chemical 9] (In the formula, Ar is an aryl group having 6 to 11 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² and R ³ are independently selected hydrogen, an alkyl group having 1 to 4 carbon atoms, Alkoxycarbonyl group having 2 to 4 carbon atoms or 6 to 11 carbon atoms
Represents an aryl group of, Y is hydrogen, halogen, carbon number 1 ~
5 shows a substituent selected from the alkyl groups of 5. ) Is a compound represented by.

When R ¹ is an aryl group having 6 to 11 carbon atoms, the following general formula [6]

[Chemical 10] (In the formula, Ar, R ² , R ³ and Y have the same meanings as described above, and R ⁴ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms or 6 to 11 carbon atoms.
Represents a substituent selected from the aryl groups of ) Is a compound represented by.

These photocyclized products are opened by heating to return to the original compounds. In addition, these photocyclized compounds have a wavelength of 240 nm compared to the imide compound represented by the general formula [1].
It absorbs almost no longer wavelength light. Furthermore, since the benzene ring and the ethenyl group involved in the cyclization reaction are spatially close to each other, side reactions are less likely to occur, and repeated reversible reactions can be endured. Therefore, by utilizing the characteristics as described above, it is possible to read with weak ultraviolet rays, and it can be expected to be used as a recording material capable of writing and erasing with strong ultraviolet rays and heat. For example, if the entire surface is previously exposed to ultraviolet rays, it can be used as a thermal paper. As specific applications, it can be expected to be used in various fields such as heat-sensitive or light-sensitive recording paper for recording confidential information, reusable heat-sensitive or light-sensitive recording paper, and optical element electronic materials such as optical switches.

Next, the method for producing the imide compound of the present invention will be described in detail. One of the raw materials, the acid halide (A), is represented by the general formula [2], and Ar is Ar of the general formula [1]. Specifically, for example, methyl group, ethyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group at the o-, m- or p-position of the benzene nucleus of cinnamic acid and cinnamic acid. Groups, alkyl groups such as n-pentyl group, isopentyl group, neopentyl group and tert-pentyl group, and chlorides and bromides of compounds substituted with halogen such as fluorine, chlorine, bromine and iodine. A preferred specific example of the acid halide (A) is cinnamic acid halide.

Examples of the acid halide (B) represented by the general formula [3] include chlorides or bromides of aliphatic carboxylic acids and aromatic carboxylic acids. Examples of the aliphatic carboxylic acid include acetic acid, Examples include propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and the like, and aromatic carboxylic acids include benzoic acid and various substituted benzoic acids. Preferred specific examples of the acid halide (B) include benzoic acid halide, methylbenzoic acid halide, halogenated benzoic acid halide and 2 to 4 carbon atoms.
Is a fatty acid halide of.

Examples of the primary amine represented by the general formula [4] include aliphatic amine, aromatic-substituted aliphatic amine and aliphatic amino acid ester. Examples of the aliphatic amine include ethylamine and propylamine. , Isopropylamine, butylamine, sec-butylamine, tert-
Butylamine, n-pentylamine, iso-pentylamine, tert-pentylamine, neopentylamine, 2-pentylamine, 3-pentylamine, 4-heptylamine, and the like, examples of aromatic substituted aliphatic amines include Benzylamine, 1-phenylethylamine, 1-phenylpropylamine, 1-methyl-1-phenylethylamine, 1-phenylbutylamine, 2-methyl-1-phenylpropylamine, 1-phenylpentylamine, 3-methyl-1
-Phenylbutylamine and o of these benzene nuclei
Methyl group, ethyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, n- at the-, m- or p-position
Pentyl group, isopentyl group, neopentyl group, tert-
Examples thereof include compounds in which an alkyl group such as a pentyl group and a halogen such as fluorine, chlorine, bromine and iodine are substituted. Examples of the aliphatic amino acid ester include alkyl esters of aliphatic amino acids such as glycine, alanine and valine, and examples of the alkyl group in the ester portion include a methyl group, an ethyl group and an isopropyl group. Preferred specific examples of the primary amine are benzylamine, 1-phenylethylamine, 1-methyl-1-phenylethylamine, 1
-Phenylpropylamine, diphenylmethylamine and glycine alkyl esters.

The production of the novel imide compound represented by the general formula [1] of the present invention is carried out by using the above-mentioned acid halide (A), acid halide (B) and primary amine. It is carried out by reacting at least one of R ¹ , R ² , R ³ and R ⁴ is an aryl group having 6 to 11 carbon atoms as a starting material. Specifically, first, a primary amine is reacted with (A) or (B) or one of the acid halides to form an amide,
The amide is reacted with the other acid halide. In this reaction, amines having no active protons such as triethylamine or organic bases such as nitrogen-containing heterocycles are usually made to coexist in order to supplement by-produced hydrogen halide. The reaction is carried out in the presence or absence of a solvent, preferably in the presence of a solvent. The solvent to be used is not particularly limited as long as it does not react with the above-mentioned acid halide or primary amine as a raw material, for example, benzene, toluene, xylene, hexane,
Examples thereof include hydrocarbon solvents such as heptane and cyclohexane, chlorine solvents such as methylene chloride and chloroform, ether solvents such as tetrahydrofuran, dioxane, and glyme. As the reaction conditions, the reaction temperature is 0 to 180.
C., preferably 10 to 150.degree. C., and the reaction time is 0.1 to 100 hours, preferably 0.5 to 50 hours.

[0019]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the contents of the present invention are not limited to these. Example 1 5.07 g (30 mmol) of cinnamic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml of triethylamine was dissolved.
(Equivalent ratio 1.1) and benzylamine (3.60 ml, equivalent ratio 1.1) were added, and the mixture was stirred at room temperature for 1 hour. 50 ml of water,
The extract was washed with 50 ml of saturated aqueous NaHCO ₃ solution and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain 4.79 g (20 mmol) of N-benzylcinnamic acid amide. The yield based on cinnamic acid chloride was 67%.

0.40 g of N-benzylcinnamic acid amide
(1.7 mmol) was dissolved in 20 ml of benzene, 0.28 ml of triethylamine (1.2 equivalent ratio) and 0.29 g of benzoic acid chloride (1.2 equivalent ratio) were added, and the mixture was heated with stirring for 24 hours to benzene. Was refluxed. Then, after washing with 20 ml of saturated aqueous NaHCO ₃ solution and 20 ml of 1N hydrochloric acid,
It was dried over magnesium sulfate and concentrated under reduced pressure. N-benzyl-N was purified by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier.
-0.37 g of benzoylcinnamic acid imide was obtained as colorless crystals. The yield based on N-benzylcinnamic acid amide is 64.
%, And the yield based on cinnamic acid chloride was 43%.

Melting point: 116 ° C.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 5.16 (s, 2H), 6.28 (d, J = 15.
0Hz, 1H), 7.08-7.66 (m, 15H),
7.53 (d, J = 15.0Hz, 1H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 49.2 (t), 121.6 (d), 127.
5 (d), 127.9 (d), 128.2 (d), 12
8.5 (d), 128.7 (d), 128.8 (d),
130.2 (d), 132.6 (d), 134.4
(S), 136.3 (s), 137.5 (s), 14
3.4 (d), 169.3 (s), 173.4 (s)

IR (KBr) cm ^-1 : 1695,165
5,1620,1350,1205,1190,114
0,705

Elemental analysis (C ₂₃ H ₁₉ NO ₂ ): Calculated value C = 80.91%; H = 5.61%; N = 4.
10% Found C = 80.93%; H = 5.53%; N = 4.
38%

Example 2 The N-benzylcinnamic acid amide synthesized in Example 1 was added to 0.4
0 g (1.7 mmol) was used and reacted in the same manner as in Example 1 except that 0.32 g of p-methylbenzoic acid chloride (equivalent ratio 1.2) was used in place of the benzoic acid chloride of Example 1, and N was reacted. 0.61 g of -benzyl-Np-methylbenzoylcinnamic acid imide was obtained as colorless crystals. The yield based on N-benzylcinnamic acid amide was 100%, and the yield based on cinnamic acid chloride was 67%.

Melting point: 114 ° C.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 2.33 (s, 3H), 5.14 (s, 2H),
6.29 (d, J = 15.4 Hz, 1H), 7.08-
7.44 (m, 12H), 7.54 (d, J = 15.4
Hz, 1H), 7.55 (d, J = 10.0Hz, 2
H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 21.6 (q), 49.2 (t), 121.7.
(D), 127.4 (d), 127.9 (d), 12
8.2 (d), 128.5 (d), 128.7 (d),
129.0 (d), 129.5 (d), 130.2
(D), 133.5 (s), 134.6 (s), 13
7.6 (s), 143.1 (d), 143.5 (s),
169.3 (s), 173.5 (s)

IR (KBr) cm ^-1 : 1695,165
5,1620, 1345, 1310, 1185, 113
5,980,760,700

Elemental analysis (C ₂₄ H ₂₁ NO ₂ ): Calculated value C = 81.10%; H = 5.96%; N = 3.
94% Found C = 81.04%; H = 5.89%; N = 4.
16%

Example 3 The N-benzylcinnamic acid amide synthesized in Example 1 was added to 0.4
0 g (1.7 mmol) was used and reacted in the same manner as in Example 1 except that 0.32 g (equivalent ratio 1.2) of m-methylbenzoic acid chloride was used in place of the benzoic acid chloride of Example 1, and N was used. 0.32 g of -benzyl-Nm-methylbenzoylcinnamic acid imide was obtained as colorless crystals. The yield based on N-benzylcinnamic acid amide was 53%, and the yield based on cinnamic acid chloride was 36%.

Melting point: 76-77 ° C.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 2.32 (s, 3H), 5.13 (s, 2H),
6.32 (d, J = 15.4 Hz, 1H), 7.12
(Dd, J = 2.0, 8.1 Hz, 2H), 7.20-
7.45 (m, 12H), 7.53 (d, J = 15.4
Hz, 1H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 21.2 (q), 49.1 (t), 121.7.
(D), 125.9 (d), 127.4 (d), 12
7.8 (d), 128.2 (d), 128.5 (d),
128.6 (d), 129.2 (d), 130.1
(D), 133.2 (d), 134.4 (s), 13
6.2 (s), 137.6 (s), 138.7 (s),
143.0 (d), 169.3 (s), 173.6
(S)

IR (KBr) cm ^-1 : 1695,165
5,1620,1345,1165

Elemental analysis (C ₂₄ H ₂₁ NO ₂ ): Calculated value C = 81.10%; H = 5.96%; N = 3.
94% Found C = 81.03%; H = 5.92%; N = 3.
90%

Example 4 The N-benzylcinnamic acid amide synthesized in Example 1 was added to 0.4
0 g (1.7 mmol) was used and reacted in the same manner as in Example 1 except that 0.32 g of o-methylbenzoic acid chloride (equivalent ratio 1.2) was used in place of the benzoic acid chloride of Example 1, and N was reacted. 0.29 g of -benzyl-N-o-methylbenzoylcinnamic acid imide was obtained as colorless crystals. The yield based on N-benzylcinnamic acid amide was 48%, and the yield based on cinnamic acid chloride was 32%.

Melting point: 94-95 ° C.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 2.32 (s, 3H), 5.09 (s, 2H),
6.48 (d, J = 15.1 Hz, 1H), 7.12-
7.38 (m, 14H), 7.54 (d, J = 15.1)
Hz, 1H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 19.3 (q), 48.4 (t), 121.0
(D), 125.9 (d), 127.4 (d), 12
7.6 (d), 127.9 (d), 128.3 (d),
128.4 (d), 128.6 (d), 130.1
(D), 130.9 (d), 131.2 (d), 13
4.4 (s), 136.3 (s), 137.4 (s),
143.4 (d), 169.3 (s), 173.2
(S)

IR (KBr) cm ^-1 : 1695,165
5,1620, 1345, 1310, 1190, 114
5,1045,975

Elemental analysis (C ₂₄ H ₂₁ NO ₂ ): Calculated value C = 81.10%; H = 5.96%; N = 3.
94% Found C = 80.97%; H = 5.78%; N = 3.
78%

Example 5 N-benzylcinnamic acid amide synthesized in Example 1 was added to 0.4
0 g (1.7 mmol) was used, and the reaction was carried out in the same manner as in Example 1 except that 0.46 g (equivalent ratio 1.2) of p-chlorobenzoic acid chloride was used instead of the benzoic acid chloride of Example 1, and N was reacted. 0.36 g of -benzyl-Np-chlorobenzoylcinnamic acid imide was obtained as colorless crystals. The yield based on N-benzylcinnamic acid amide was 56%, and the yield based on cinnamic acid chloride was 38%.

Melting point: 121-122 ° C.

¹ H-NMR (270 MHz, CDCl ₃ )
δ 5.14 (s, 2H), 6.33 (d, J = 15.2H
z, 1H), 7.18 (dd, J = 2.1, 8.4H
z, 2H), 7.25-7.41 (m, 10H), 7.
38 (d, J = 8.7 Hz, 2H), 7.56 (d, J
= 8.7 Hz, 2H), 7.58 (d, J = 15.2H
z, 1H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 49.1 (t), 121.0 (d), 127.
5 (d), 127.9 (d), 128.0 (d), 12
8.5 (d), 128.7 (d), 128.9 (d),
130.0 (d), 130.4 (d), 134.1
(S), 134.5 (s), 137.2 (s), 13
8.7 (s), 144.0 (d), 169.0 (s),
172.3 (s)

IR (KBr) cm ^-1 : 1700,165
0,1615,1335,1310,1185,113
5,975

Elemental analysis (C ₂₃ H ₁₈ NO ₂ Cl): Calculated C = 73.50%; H = 4.83%; N = 3.
73% Found C = 73.49%; H = 4.73%; N = 3.
70%

Example 6 The N-benzylcinnamic acid amide synthesized in Example 1 was added to 0.4
0 g (1.7 mmol) was used, and the reaction was carried out in the same manner as in Example 1 except that 0.46 g (equivalent ratio 1.2) of m-chlorobenzoic acid chloride was used in place of the benzoic acid chloride of Example 1, and N was reacted. 0.43 g of -benzyl-Nm-chlorobenzoylcinnamic acid imide was obtained as colorless crystals. The yield based on N-benzylcinnamic acid amide was 67%, and the yield based on cinnamic acid chloride was 45%.

Melting point: 101-102 ° C.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 5.13 (s, 2H), 6.36 (d, J = 15.
4 Hz, 1 H), 7.19 (dd, J = 1.8, 7.8)
Hz, 2H), 7.24-7.47 (m, 11H),
7.58 (d, J = 15.4 Hz, 1H), 7.63
(Dd, J = 1.8, 1.8 Hz, 1H),

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 49.1 (t), 121.1 (d), 126.
6 (d), 127.6 (d), 128.0 (d × 2),
128.6 (d), 128.8 (d), 130.0
(D), 130.5 (d), 132.3 (d), 13
4.2 (s), 134.9 (s), 137.2 (s),
137.9 (s), 144.2 (d), 169.2
(S), 172.0 (s)

IR (KBr) cm ^-1 : 1695,165
5,1620,1345,1190

Elemental analysis (C ₂₃ H ₁₈ NO ₂ Cl): Calculated value C = 73.50%; H = 4.83%; N = 3.
73% Found C = 73.69%; H = 4.71%; N = 3.
60%

Example 7 N- (1-phenylethyl) was prepared in the same manner as in Example 1 except that 3.96 g of 1-phenylethylamine (equivalent ratio 1.1) was used in place of the benzylamine of Example 1. 4.05 g of cinnamic acid amide was obtained. The yield was 57%. Next, 0.43 g (1.7 mmol) of the obtained N- (1-phenylethyl) cinnamic acid amide was reacted with 0.29 g (equivalent ratio 1.2) of benzoic acid chloride in the same manner as in Example 1, 0.59 g of N-benzoyl-N- (1-phenylethyl) cinnamic acid imide was obtained as a colorless liquid. N- (1
-Phenylethyl) cinnamic acid amide yield is 98%,
The yield based on cinnamic acid chloride was 56%.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 1.88 (d, J = 7.2 Hz, 3H), 6.06
(Q, J = 7.2 Hz, 1H), 6.11 (d, J = 1
5.5 Hz, 1 H), 7.01-7.70 (m, 16
H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 17.4 (q), 54.7 (d), 122.5
(D), 126.8 (d), 126.9 (d), 12
7.4 (d), 127.9 (d), 128.3 (d),
128.4 (d), 129.8 (d), 130.1
(D), 132.2 (d), 133.9 (s), 13
6.9 (s), 140.7 (s), 142.3 (d),
168.7 (s), 173.0 (s)

IR (neat) cm ^-1 : 1660, 16
25, 1380, 1340, 1305, 1275, 11
95,1070,765,700

High resolution mass spectrometry (FAB) (m / z)
(C ₂₄ H ₂₂ NO ₂ ) MH ⁺ : calculated value 356.1650, measured value 356.165.
7

Example 8 N was reacted in the same manner as in Example 7 except that 0.32 g of p-methylbenzoic acid chloride (equivalent ratio 1.2) was used in place of benzoic acid chloride in Example 7. 0.63 g of -p-methylbenzoyl-N- (1-phenylethyl) cinnamic acid imide was obtained as a colorless liquid. The yield based on N- (1-phenylethyl) cinnamic acid amide was 100%, and the yield based on cinnamic acid chloride was 57%.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 1.88 (d, J = 7.2 Hz, 3H), 2.32
(S, 3H), 6.04 (q, J = 7.2 Hz, 1
H), 6.11 (d, J = 15.7 Hz, 1H), 7.
06 (dd, J = 1.6, 7.9 Hz, 2H), 7.1
5-7.35 (m, 8H), 7.41 (d, J = 15.
7 Hz, 1 H), 7.50 (dd, J = 1.6, 7.9)
Hz, 2H), 7.57 (dm, J = 8.2Hz, 2
H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 17.7 (q), 21.4 (q), 55.0
(D), 122.6 (d), 127.0 (d), 12
7.2 (d), 127.6 (d), 128.1 (d),
128.5 (d), 129.0 (d), 129.3
(D), 129.9 (d), 134.3 (s), 14
0.9 (s), 142.3 (d), 143.5 (s),
168.8 (s), 173.3 (s)

IR (neat) cm ^-1 : 1964,16
58, 1620, 1450, 1374, 1338, 13
06,1272,1196,1176

High resolution mass spectrometry (FAB) (m / z)
(C ₂₅ H ₂₄ NO ₂ ) MH ⁺ : calculated value 370.1807, measured value 370.180
6

Example 9 Reaction was carried out in the same manner as in Example 7 except that 0.46 g of p-chlorobenzoic acid chloride (equivalent ratio 1.2) was used in place of benzoic acid chloride in Example 7, and N was reacted. 0.60 g of -p-chlorobenzoyl-N- (1-phenylethyl) cinnamic acid imide was obtained as a colorless liquid. The yield based on N- (1-phenylethyl) cinnamic acid amide was 91%, and the yield based on cinnamic acid chloride was 57%.

Melting point: 121-122 ° C.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 1.87 (d, J = 7.2 Hz, 3H), 6.03
(Q, J = 7.2 Hz, 1H), 6.12 (d, J = 1
5.7 Hz, 1 H), 7.10 (dd, J = 1.6,
7.9 Hz, 2H), 7.20-7.38 (m, 8
H), 7.39 (d, J = 15.7 Hz, 1H), 7.
48 (dd, J = 1.6, 7.9 Hz, 2H), 7.5
9 (dm, J = 8.6Hz, 2H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 17.6 (q), 54.9 (d), 122.1
(D), 127.0 (d), 127.6 (d), 12
8.1 (d), 128.5 (d), 128.8 (d),
130.0 (d), 130.1 (d), 133.9
(S), 135.3 (s), 138.6 (s), 14
0.6 (s), 143.1 (d), 168.7 (s),
172.0 (s)

IR (neat) cm ^-1 : 1696,16
52, 1620, 1340, 1192, 1172, 75
8

High resolution mass spectrometry (FAB) (m / z)
(C ₂₄ H ₂₁ NO ₂ Cl) MH ⁺ : Calculated value 390.1261, Measured value 390.127
0

Example 10 1-Methyl-1-instead of benzylamine of Example 1
N- (1-Methyl-1-phenylethyl) cinnamic acid amide was obtained in a yield of 41% in the same manner as in Example 1 except that phenylethylamine was used. The resulting N- (1-
Methyl-1-phenylethyl) cinnamic acid amide 0.45 g
(1.7 mmol) was reacted with 0.29 g of benzoic acid chloride (equivalent ratio 1.2) in the same manner as in Example 1 to give N-benzoyl-N- (1-methyl-1-phenylethyl) cinnamic acid. 0.46 g of imide was obtained as a colorless liquid. N-
The yield based on (1-methyl-1-phenylethyl) cinnamic acid amide was 73%, and the yield based on cinnamic acid chloride was 30%.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 1.87 (s, 6H), 6.19 (d, J = 15.
3Hz, 1H), 7.10-7.65 (m, 13H),
7.44 (d, J = 15.3 Hz, 1H), 8.03
(Ddd, J = 1.5, 3.1, 8.0 Hz, 2H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 29.3 (q), 62.9 (s), 121.5
(D), 125.0 (d), 126.4 (d), 12
7.7 (d), 128.2 (d), 128.5 (d),
129.0 (d), 129.8 (d), 130.1
(D), 133.8 (d), 134.4 (s), 13
6.6 (s), 142.7 (d), 147.2 (s),
166.2 (s), 174.8 (s)

IR (neat) cm ⁻¹ : 1700, 16
62, 1622, 1344, 1268, 1232, 11
58,784,764,698

High resolution mass spectrometry (FAB) (m / z)
(C ₂₅ H ₂₄ NO ₂ ) MH ⁺ : calculated value 370.1807, measured value 370.181
Three

Example 11 The same procedure as in Example 1 was repeated except that 1-phenylpropylamine was used instead of benzylamine in Example 1, and N-
(1-Phenylpropyl) cinnamic acid amide was obtained with a yield of 38%. Then obtained N- (1-phenylpropyl)
To 0.45 g (1.7 mmol) of cinnamic acid amide, 0.29 g of benzoic acid chloride (equivalent ratio 1.
2) was reacted to obtain 0.60 g of N-benzoyl-N- (1-phenylpropyl) cinnamic acid imide as a colorless liquid. N- (1-phenylpropyl) cinnamic acid amide based yield is 95%, cinnamic acid chloride based yield is 36%
Met.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 1.06 (t, J = 7.3 Hz, 3H), 2.31
(Ddq, J = 6.6, 13.8, 7.3 Hz, 1
H), 2.52 (ddq, J = 9.6, 13.8, 7.
3 Hz, 1 H), 5.82 (dd, J = 6.6, 9.6)
Hz, 1H), 6.06 (d, J = 15.5Hz, 1
H), 7.02 (ddd, J = 1.5, 1.5, 7.7)
Hz, 2H), 7.16-7.48 (m, 10H),
7.55 (ddd, J = 1.5, 1.5, 7.7 Hz,
2H), 7.63 (ddd, J = 2.3, 3.2, 8.
3Hz, 2H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 11.6 (q), 24.6 (t), 61.8
(D), 122.9 (d), 127.2 (d), 12
7.6 (d), 128.0 (d), 128.5 (d),
128.6 (d), 128.8 (d), 130.0
(D), 132.4 (d), 134.1 (s), 13
7.2 (s), 140.1 (s), 142.4 (d),
169.5 (s), 173.1 (s)

IR (neat) cm ^-1 : 1696,16
56, 1620, 1338, 1192, 1176, 78
8,760,698

High resolution mass spectrometry (FAB) (m / z)
(C ₂₅ H ₂₄ NO ₂ ) MH ⁺ : calculated value 370.1807, measured value 370.180
Four

Example 12 N- (diphenylmethyl) cinnamic acid amide was obtained in a yield of 87% in the same manner as in Example 1 except that diphenylmethylamine was used instead of benzylamine in Example 1. Next, 0.53 g (1.7 mmol) of the obtained N- (diphenylmethyl) cinnamic acid amide was reacted with 0.29 g of benzoic acid chloride (equivalent ratio 1.2) in the same manner as in Example 1 to give N- 0.67 g of benzoyl-N- (diphenylmethyl) cinnamic acid imide was obtained as colorless crystals. The yield based on N- (diphenylmethyl) cinnamic acid amide was 95%, and the yield based on cinnamic acid chloride was 83%.

Melting point: 129-131 ° C.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 6.15 (d, J = 15.4 Hz, 1H), 7.0
3 (dd, J = 1.4, 8.0 Hz, 2H), 7.17
−7.49 (m, 17H), 7.70 (ddd, J =
2.7, 4.4, 8.4 Hz, 2H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 63.8 (d), 122.6 (d), 127.
4 (d), 127.8 (d), 128.2 (d), 12
8.6 (d), 128.8 (d), 128.9 (d),
129.0 (d), 130.2 (d), 132.8
(D), 134.3 (s), 137.1 (s), 13
8.9 (s), 143.2 (d), 169.0 (s),
172.8 (s)

Example 13 N-acetyl-N was reacted in the same manner as in Example 7 except that 0.16 g of acetic acid chloride (equivalent ratio of 1.2) was used in place of benzoic acid chloride. -(1-
0.23 g of phenylethyl) cinnamic acid imide was obtained as colorless crystals. The yield based on N- (1-phenylethyl) cinnamic acid amide was 47%, and the yield based on cinnamic acid chloride was 27%.
%Met.

Melting point: 92 ° C.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 1.79 (d, J = 6.0 Hz, 3H), 2.39
(S, 3H), 5.98 (q, J = 6.0 Hz, 1
H), 6.67 (d, J = 15.5 Hz, 1H), 7.
32-7.41 (m, 10H), 7.62 (d, J = 1
5.5Hz, 1H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 17.7 (q), 26.2 (q), 52.2
(D), 121.2 (d), 126.0 (d), 12
6.8 (d), 127.9 (d), 128.3 (d),
128.5 (d), 130.1 (d), 134.0
(S), 140.8 (s), 144.1 (d), 16
9.9 (s), 173.0 (s)

IR (KBr) cm ^-1 : 1705,161
5,1380, 1330, 1315, 1235, 120
0,1005,765

Elemental analysis (C ₁₉ H ₁₉ NO ₂ ): Calculated value C = 77.79%; H = 6.53%; N = 4.
77% Found C = 77.61%; H = 6.45%; N = 4.
79%

Example 14 The procedure of Example 7 was repeated except that 0.19 g of propionic acid chloride (equivalent ratio of 1.2) was used instead of benzoic acid chloride, and N-propionyl- was reacted.
0.34 g of N- (1-phenylethyl) cinnamic acid imide was obtained as a colorless liquid. The yield based on N- (1-phenylethyl) cinnamic acid amide was 64%, and the yield based on cinnamic acid chloride was 36%.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 1.14 (t, J = 7.3 Hz, 3H) 1.78
(D, J = 7.0 Hz, 3H), 2.66 (dq, J =
7.3, 7.3 Hz, 1H), 2.67 (dq, J =
7.3, 7.3 Hz, 1H), 5.95 (q, J = 7.
0Hz, 1H), 6. 67 (d, J = 15.5 Hz,
1H), 7.32-7.42 (m, 10H), 7.61
(D, J = 15.5Hz, 1H)

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 9.7 (q), 18.1 (q), 32.1
(T), 52.6 (d), 121.6 (d), 126.
4 (d), 127.2 (d), 128.2 (d), 12
8. 6 (d), 128.9 (d), 130.4
(D), 134.5 (s), 141.2 (s), 14
4.3 (d), 170.3 (s), 177.7 (s)

IR (neat) cm ^-1 : 1868,16
18,1452,1378,1332,1178,10
74,764,700

High resolution mass spectrometry (FAB) (m / z)
(C ₂₀ H ₂₂ NO ₂ ) MH ⁺ : calculated value 308.1650, measured value 308.165.
9

Example 15 2.36 g (30 mmol) of acetic acid chloride was dissolved in 50 ml of dry ether, and 4.59 ml of triethylamine (equivalent ratio 1.1) and 6.04 g of diphenylmethylamine (equivalent ratio 1.1) were dissolved. In addition, the mixture was stirred at room temperature for 1 hour. Water 50
ml, saturated aqueous NaHCO ₃ solution (50 ml) and 1N hydrochloric acid, and the extract was dried over magnesium sulfate and concentrated under reduced pressure.
Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain 3.37 g (15 mmol) of N- (diphenylmethyl) acetic acid amide. The yield based on acetic acid chloride was 49%.

N- (diphenylmethyl) acetic acid amide
38 g (1.7 mmol) was dissolved in 20 ml of benzene, 0.26 ml of triethylamine (equivalent ratio 1.1) and 0.31 g of cinnamic acid chloride (equivalent ratio 1.1) were added, and the mixture was heated with stirring for 24 hours. The benzene was brought to reflux. Then, it was washed with 20 ml of saturated aqueous NaHCO ₃ solution, 20 ml of 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain 0.60 g of N-acetyl-N- (diphenylmethyl) cinnamic acid imide as a colorless liquid. The yield based on N- (diphenylmethyl) acetic acid amide was 99%, and the yield based on acetic acid chloride was 49%.

¹³ C-NMR (22.4 MHz, CDCl
₃ ) δ: 26.3 (q), 61.6 (d), 121.6
(D), 127.3 (d), 128.0 (d), 12
8.2 (d), 128.6 (d), 130.2 (d),
134.1 (s), 138.4 (s), 144.0
(D), 169.9 (s), 173.0 (s)

IR (neat) cm ^-1 : 1868,16
22, 1378, 1334, 1244, 1172, 78
4,760,700

High resolution mass spectrometry (FAB) (m / z)
(C ₂₄ H ₂₂ NO ₂ ) MH ⁺ : calculated value 356.1650, measured value 356.165.
Two

Example 16 1.01 g (6.0 mmol) of cinnamic acid chloride was dissolved in 20 ml of ether, 1.00 g (7.2 mmol) of glycine ethyl ester hydrochloride was added, and the mixture was stirred and suspended. 2.0 ml (14.4 mmol) of triethylamine was slowly added dropwise, and the mixture was stirred at room temperature for 14 hours. The reaction was stopped with 20 ml of water. Extract with 10 ml of ethyl acetate and add 1N hydrochloric acid 2
Wash with 0 ml and 20 ml of saturated aqueous sodium hydrogen carbonate solution,
After drying over magnesium sulfate, concentrating under reduced pressure, N-
(Ethoxycarbonylmethyl) cinnamic acid amide 1.151
g was obtained with a yield of 84%.

0.95 g (4.1 mmol) of the obtained N- (ethoxycarbonylmethyl) cinnamic acid amide was suspended in benzene (20 ml) to give 0.69 g of benzoic acid chloride.
(4.9 mmol), triethylamine 0.68 ml (4.9
mmol) was added and the mixture was heated to reflux. 10 ml of water was added, and the organic layer was washed with 1N hydrochloric acid and saturated aqueous sodium hydrogen carbonate solution,
After drying over magnesium sulfate and concentration under reduced pressure, 1.15 g of N-benzoyl-N- (ethoxycarbonylmethyl) cinnamic acid imide was obtained as a colorless liquid. The yield based on N- (ethoxycarbonylmethyl) cinnamic acid amide was 84%, and the yield based on cinnamic acid chloride was 57%.

¹ H-NMR (270 MHz, CDCl ₃ )
δ: 1.30 (t, J = 7.1 Hz, 3H), 4.25
(Q, J = 7.1 Hz, 2H), 4.70 (s, 2
H), 6.28 (d, J = 15.2 Hz, 1H), 7.
00-7.85 (m, 11H)

Reference Examples 1 to 5 0.1 mmol of each of the imide compounds obtained in Examples 1, 6, 12, 13, and 16 was dissolved in 5 ml of benzene together with an equivalent amount of benzyl, and this solution was placed in a Pyrex test tube. UV irradiation was performed for a predetermined time using a high-pressure mercury lamp at room temperature under an argon atmosphere. The solvent was removed under reduced pressure, and the product was isolated by purification by column chromatography using ethyl acetate-hexane as a developing solvent and silica gel as a support carrier. Imide compound as raw material, cyclized product, UV irradiation time, isolated yield, ¹ H-NM of photocyclized product
R and IR are shown in Table 1 and Table 2. The ultraviolet absorption spectra of the raw material imide and the cyclized product formed are shown in FIGS. 1 to 5, respectively.

When the cyclized product produced by the above-mentioned ultraviolet irradiation was heated to 70 ° C., the original imide compound was almost completely ring-opened in the time shown in the table.

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

INDUSTRIAL APPLICABILITY The novel imide compound of the present invention has almost no visible light absorption and thus is excellent in stability against visible light, has a high photoreaction yield due to ultraviolet rays and a high stability of a product of a photoreaction, and is reversible by heat. Since it has various characteristics such as smooth reaction, it is useful as a recording material. In addition, since the production method of the present invention uses inexpensive raw materials and has few production steps, the imide compound can be produced economically.

[Brief description of drawings]

FIG. 1 is an ultraviolet absorption spectrum of a raw material imide used in Reference Example 1 and an obtained cyclized product.

FIG. 2 is an ultraviolet absorption spectrum of a raw material imide used in Reference Example 2 and an obtained cyclized product.

FIG. 3 is an ultraviolet absorption spectrum of the raw material imide used in Reference Example 3 and the obtained cyclized product.

FIG. 4 is an ultraviolet absorption spectrum of a raw material imide used in Reference Example 4 and an obtained cyclized product.

5 is an ultraviolet absorption spectrum of the raw material imide used in Reference Example 5 and the obtained cyclized product. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Akimoto 2-14-3 Uchida, Sugito-cho, Kitakatsushika-gun, Saitama Prefecture

Claims (2)

[Claims] 1. The following general formula [1]: (In the formula, Ar represents an aryl group having 6 to 11 carbon atoms, and R
¹ represents an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 11 carbon atoms, and R ² , R ³ and R ⁴ are independently selected hydrogen, an alkyl group having 1 to 4 carbon atoms, and a carbon number. 2-4 alkoxycarbonyl groups or 6-11 carbon atoms
And an aryl group of R ¹ , R ² , R ³ and R
^At least one of ⁴ represents an aryl group having 6 to 11 carbon atoms. ) A new imide compound represented by: 2. A method for producing an imide, comprising a step of reacting one acid halide with a primary amine to form an amide, and a step of reacting the amide with another acid halide. As in the general formula [2] (Wherein Ar has the same meaning as in claim 1, X
Represents halogen. ) Acid halide (A)
And the general formula [3] (Wherein R ¹ has the same meaning as in claim 1 and X 1
Represents halogen. ) Acid halide (B)
And the general formula [4] (Wherein R ² , R ³ and R ⁴ have the same meanings as in claim 1), and
In these raw materials, at least one of R ¹ , R ² , R ³ and R ⁴ is an aryl group having 6 to 11 carbon atoms, The method for producing a novel imide compound according to claim 1.