JPS6343398B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel quinoline-carboxylic acid lactone compound represented by the general formula (). [In the formula, A and B are the same or different groups as shown below;
X is a halogen or a nitro group; and n' is an integer from 0 to 4.

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[Formula] (where R ¹ and R ² are hydrogen, an alkyl group that may have a substituent, an alicyclic group that may have a substituent, a phenyl group that may have a substituent,
or a benzyl group that may have a substituent; R ³ ,
R ⁴ , R ⁵ and R ⁶ are hydrogen, halogen, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alicyclic group which may have a substituent, and a substituent. A certain phenyl group,
Benzyl group, alkoxycarbonyl group, which may have a substituent, benzyloxy group or dialkylamino group, which may have a substituent; n ² is 4
or 5; n ³ and n ⁴ represent 2 or 3, respectively. Moreover, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are groups A, B
They do not necessarily indicate the same type of thing at the same time. The substituents that can be substituted on each group of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include alkyl, halogen,
cyan, alkoxy, alkylamino or polyfluoromethyl, etc.)] Quinoline represented by the above general formula ()
Lactone compounds of carboxylic acids are isomers of the following formula: It is a compound newly synthesized by the inventors together with a lactone compound of quinoline-carboxylic acid represented by the formula, which itself is usually a substantially colorless or slightly colored crystal, but it can be used with electron-accepting materials such as activated clay or phenolic resin. When it comes into contact with the body, the lactone ring in the compound opens and develops a green, blue, purple-blue, or red color. Therefore, it is very useful as a color-forming compound, particularly as a raw material for the production of recording materials such as pressure-sensitive recording paper, heat-sensitive recording paper, current-carrying heat-sensitive recording paper, hectograph transfer paper, and Xerox-type copying toner. It is well known that lactone compounds are used as color-forming compounds in recording materials, and various lactone compounds are known, but they do not meet all the properties required for color-forming compounds, such as coloring speed, coloring density, light resistance after coloring, and A lactone compound with excellent water resistance has not yet been invented. The lactone compound of the present application is most characterized by having a quinoline nucleus, and provides a color-forming compound that has a fast color development rate, a high color density, and is excellent in light resistance and water resistance. That is, lactone compounds having a benzene nucleus instead of a quinoline nucleus, such as crystal violet lactone (a), have excellent color development speed and color density, but are inferior in light resistance and water resistance. In addition, lactone compounds having a pyridine nucleus, such as lactone compounds (b,
Although c) is excellent in coloring speed, coloring density, and light fastness, its biggest drawback is that it is extremely poor in water resistance, and has not been put to practical use. In contrast, the lactone compound having a quinoline nucleus of the present invention newly synthesized by the present inventors solves all of these drawbacks, namely, it has a fast color development speed, a high color density, excellent light resistance, and water resistance. It is an extremely excellent color-forming compound with excellent properties. The novel quinoline-carboxylic acid lactone compound represented by the general formula () can be synthesized by the following two methods, including typical synthetic methods. (i) When A and B have the same structure (i.e. A=B): 1 mole of quinoline-2,3-dicarboxylic acid anhydride () or 1 mole of quinoline-2,3-dicarboxylic acid ()' and 2 moles (A-H) (usually preferably used in slight excess) are dehydrated. The reaction is carried out in a condensing agent, or with a dehydrating condensing agent in the presence of a Lewis acid catalyst in an inert solvent or without a solvent. As the dehydration condensation agent, lower fatty acid anhydrides such as acetic anhydride or propionic anhydride and inorganic acids such as phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, sulfuric acid, phosphoric acid or polyphosphoric acid are used. AlCl ₃ as a Lewis acid catalyst,
ZnCl ₂ , SnCl ₄ or FeCl ₃ etc. are used. Chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, trichlene, benzene, toluene, xylene, and the like are used as inert solvents. After the reaction, it is neutralized with a base such as ammonia water, caustic soda aqueous solution or sodium carbonate aqueous solution, extracted with an inert solvent such as those mentioned above, and concentrated to obtain the desired lactone compound. The lactone compound of quinoline-carboxylic acid, which is the target compound of the present application, and the compound ()' obtained together with the compound ()', which is represented by ()', has an isomer relationship with the compound ()', and is usually an isomer by the above method. obtained as a mixture of A mixture of isomers can be easily separated into its individual components by column chromatography, etc., but when used as a color-forming compound in recording materials, it should not be used as a mixture of isomers because the hues of the isomers are similar to each other. There is no inconvenience. (ii) If the structures of A and B are not the same: 1 mol of quinoline-2,3-dicarboxylic anhydride () and 1 mol of (A-H) or (B-
(-a) and (or) (-a)' and (-b) and (or )(-b)' ketoacid is obtained. When reacting without solvent, usually (A-H) or (B
-H) is preferably used in excess. As the Lewis acid and inert solvent, the same ones as in the case (i) above are used. Keto acids (-a) and (-a)' and (
-b) and (-b)' have an isomer relationship,
According to the above method, it is usually obtained as a mixture of isomers, but by selecting the reaction conditions (
-a) or (-b) is the main product,
Alternatively, it is possible to use (-a)' or (-b)' as the main product. Keto acid isomers can be easily separated into their respective components by recrystallization or fractional precipitation using PH, but there is no problem in using the isomer mixture for the next reaction. Then (-a) and (or) (-
a)', or (-b) and (or) (-
b) React 1 mol of the keto acid of ' with 1 mol of (B-H) or 1 mol of (A-H) in a dehydrating condensation agent. After the reaction, a lactone compound of quinoline-carboxylic acid is obtained by processing in the same manner as in the case (i) above. It is obvious that this method can be applied even when A and B have the same structure. Specific examples and color tones of the novel quinoline-carboxylic acid lactone compounds obtained by the above method are shown in Table 1. Note that the color tone is the color tone after color development of a toluene solution of the compound on silica gel.

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[Table] Next, examples of syntheses of representative compounds shown in Table 1 will be given. Example 1 2,2-bis(4-pyrrolidino-2-methoxyphenyl)-2-[H]-5-[H]-furan-
[4,3-b]-quinolin-5-one () and 2,2-bis(4-pyrrolidino-2-methoxyphenyl)-2-[H]-5-[H]-furan-
Method for producing [3,4-b]-quinolin-5-one (), (compound number 1). 1.8 g of 3-pyrrolidinoanisole, 1 g of quinoline-2,3-carboxylic anhydride and 20 ml of acetic anhydride are reacted at 50-60° C. for 1 hour. then
Add 100 ml of toluene and 50 ml of 25% ammonia water, heat under reflux for 1 hour, and separate the toluene layer.
After washing with hot water and concentrating, 1.6g (theoretical yield 59.3%) of 2,
2-bis(4-pyrrolidino-2-methoxyphenyl)-2-[H]-5-[H]-furan-[4,3-
b]-quinolin-5-one () and 2,2-
Bis(4-pyrrolidino-2-methoxyphenyl)
-2-[H]-5-[H]-furan-[3,4-b]-
A mixture of quinolin-5-one () is obtained. Pale green crystals, mp 196-198°C. From the analysis results below, the molecular formula of this compound is
It was confirmed that _{it was C33H33N3O4 .} C H N Theoretical value 73.98 6.22 7.85 Actual value 73.93 6.21 7.82 Example 2 2-(2-ethoxy-4-diethylaminobenzoyl)-3-carboxyquinoline () and 3-(2-ethoxy-4-diethylaminobenzoyl)-2 -Production method of carboxyquinoline () 10 g quinoline-2,3-carboxylic anhydride,
19.4g of 3-ethoxydiethylaniline, 14.7g
of AlCl ₃ and 100 ml dichloroethane at 20 °C
After stirring for 20 hours, drain into dilute hydrochloric acid. The dichloroethane layer is separated, washed with water, and the dichloroethane is distilled off under reduced pressure. After dissolving the residue in a dilute caustic soda aqueous solution, excess 3-ethoxydiethylaniline was extracted and removed with toluene. Next, the aqueous layer was adjusted to pH 3 with diluted hydrochloric acid to remove the precipitate, washed with water and dried to obtain 2-(2-ethoxy-4-diethylaminobenzoyl)-3-carboxyquinoline () and 3-(2-ethoxy-
9.8 g of a mixture of (4-diethylaminobenzoyl)-2-carboxyquinoline (theoretical yield 49.8
%). 9.8 g of this mixture was heated under reflux for 30 minutes with 10 ml of dichloroethane, cooled, and the insoluble matter was removed and dried to obtain 3.2 g of 2-(2-ethoxy-4-diethylaminobenzoyl)-3-carboxyquinoline (). Pale yellow powder, mp 150-152°C. On the other hand, when the liquid was concentrated to dryness under reduced pressure, it became 6.1g.
3-(2-ethoxy-4-diethylaminobenzoyl)-2-carboxyquinoline () is obtained.
Pale yellow powder, mp 112-115°C. Example 3 2-(2-ethoxy-4-diethylamino-phenyl)-2-(1-benzyl-2-methyl-indol-3-yl)-2-[H]-5-[H]-
Process for producing furan-[4,3-b]-quinolin-5-one () (compound number 45) 1 g of 3-(2-ethoxy-4-diethylaminobenzoyl)-2-carboxyquinoline (,
Example 2), 0.8 g of 1-benzyl-2-methylindole and 10 ml of acetic anhydride are reacted at 50-60°C for 2 hours. Then, the same treatment as in Example 1 was performed to obtain 1.2 g (theoretical yield 79.1%) of 2-(2-ethoxy-4-diethylaminophenyl)-2-(1-benzyl-2-methyl-indol-3-yl. )-2
-[H]-5-[H]-furan-[4,3-b]-quinolin-5-one () is obtained. pale yellow crystals,
It was mp214-215℃. From the analysis results below, the molecular formula of this compound is
It _was confirmed that _it was _{C39H37N3O3 .} C H N Theoretical value 78.62 6.27 7.05 Actual value 78.50 6.10 7.02 In addition, the following indoles were used in place of the 1-benzyl-2-methyl-indole used in the above reaction to prepare the corresponding quinoline-carboxylic acid lactone compound (, ,) was obtained. Furthermore, the corresponding quinoline-carboxylic acid lactone compound (
L) was obtained.

[Table] Example 4 2-(1-butyl-2-methyl-indole-
Process for producing 3-yl)-carbonylquinoline-3-carboxylic acid () 10 g of quinoline-2,3-dicarboxylic anhydride and 23.5 g of 1-butyl-2-methyl-indole are reacted at 85-90° C. for 3 hours. Then 100ml
After adding and dissolving 5% caustic soda aqueous solution, excess 1
-Butyl-2-methyl-indole was extracted and removed with toluene, and the aqueous layer was adjusted to pH 3 with dilute hydrochloric acid and the precipitate was dried. This was heated under reflux for 30 minutes with 20ml of acetonitrile, then cooled and dried to remove insoluble matter, yielding 15.9g.
(Theoretical yield: 82.0%) of 2-(1-butyl-2-methyl-indol-3-yl)-carbonylquinoline-3-carboxylic acid () is obtained. Light brown powder, mp 172-174°C. 1-Butyl-2-methyl- used in the above reaction
2-(1-ethyl-2-methyl-indol-3-yl)-carbonylquinoline-3-carboxylic acid (2) is obtained by using 1-ethyl-2-methyl-indole in place of indole. Theoretical yield
85.4%, yellow powder, mp 208-209°C. Example 5 2-(1-ethyl-2-methyl-indole-
Process for producing 3-yl)-carbonylquinoline-3-carboxylic acid () and 3-(1-ethyl-2-methyl-indol-3-yl)-carbonylquinoline-2-carboxylic acid (XI) 10 g of quinoline-2,3-dicarboxylic anhydride, 16 g of 1-ethyl-2-methyl-indole, 14.7 g of AlCl ₃ and 100 ml of trichlene at 20
After stirring for 20 hours at °C, drain into dilute hydrochloric acid. The trichlene layer is separated, washed with water, and then the trichlene is distilled off under reduced pressure. After dissolving the residue in a dilute caustic soda aqueous solution, excess 1-ethyl-2-methyl-indole was extracted and removed with toluene. Next, the aqueous layer was adjusted to pH 3 with diluted hydrochloric acid to remove the precipitate, washed with water and dried to give 2-(1-
ethyl-2-methyl-indol-3-yl)-
Carbonylquinoline-3-carboxylic acid () and 3-(1-ethyl-2-methyl-indole-3
16.2 g (90.1% of theoretical yield) of a mixture of -yl)-carbonylquinoline-3-carboxylic acid (XI) are obtained. Add 16.2 g of this mixture to 20 ml of acetonitrile and 30 g of this mixture.
After heating under reflux for several minutes, the mixture is cooled to remove insoluble matter and dried to obtain 5 g of 2-(1-ethyl-2-methyl-indol-3-yl)-carbonylquinoline-3-carboxylic acid (2). yellow powder, mp208~209
It was warm at ℃. On the other hand, when the liquid is concentrated to dryness under reduced pressure,
11 g of 3-(1-ethyl-2-methyl-indol-3-yl)-carbonylquinoline-2-carboxylic acid (XI) are obtained. Light brown powder, mp125~
It was 130℃. Example 6 2-(2-methoxy-4-dibutylaminophenyl)-2-(1-ethyl-2-methyl-indol-3-yl)-2-[H]-5-[H]-furan- [4,3-b]-quinolin-5-one (
) (compound number 50) production method 2 g of 3-(1-ethyl-2-methyl-indol-3-yl)-carbonylquinoline-2-carboxylic acid (XI, Example 5), 2 g of 3-dibutylaminoanisole and 20 ml of acetic anhydride at 50 to
React at 60°C for 2 hours. Then, by carrying out the same treatment as in Example 1, 2.5 g (theoretical yield 77.8%) of 2-(2
-methoxy-4-dibutylaminophenyl)-2
-(1-ethyl-2-methylindol-3-yl)-2-[H]-5-[H]-furan-[4,3-
b]-quinolin-5-one () is obtained.
Pale yellow crystals, mp 168-170°C. Based on the analysis results below, the molecular formula of this compound is
It _was confirmed that _it was _{C37H41N3O3 .} C H N Theoretical value 77.17 7.19 7.30 Actual value 77.05 7.10 7.18 In addition, the corresponding quinoline-carboxylic acid lactone compound () was obtained by using 3-butoxydibutylaniline in place of 3-dibutylaminoanisole used in the above reaction. .

[Table] Next, a method for producing pressure-sensitive recording paper, which is one example of the use of the compound of the present invention, is shown. Reference example 1 12g of 0.3g of compound number 1 lactone compound
Alkylnaphthalene KMCR (Kureha Chemical product name)
was dissolved in a solvent and emulsified at 50°C with a solution containing 3.25 g of gum arabic in 25 ml of water. next
Add a solution of 3.25 g of gelatin in 25 ml of water and emulsify it completely, then add acetic acid to adjust the pH to 4. At this time, a gelatin-gum arabic liquid film is formed around the oil droplets containing the lactone compound. After adding 50ml of water, adjust the pH to 4. To cure the film, 1 ml of 37% formalin aqueous solution was added, and then 10% caustic soda aqueous solution was added to adjust the pH to 9-10 and gradually return to room temperature. The suspension thus obtained is applied to the lower surface of the upper leaves and dried. Meanwhile, an electron acceptor such as phenolic resin is applied to the upper surface of the lower leaf. By combining the upper and lower leaves prepared as described above and applying local pressure using a print or brush, the capsule in the pressurized area ruptures and the lactone compound inside the capsule becomes an electron acceptor on the upper surface of the lower leaf. When it is adsorbed to the paper, it develops a green color and achieves the purpose of recording.

Claims (1)

[Claims] 1 General formula () [In the formula, A and B are the same or different groups as shown below;
X is a halogen or a nitro group; and n' is an integer from 0 to 4. [Formula] [Formula] [Formula] [Formula] (where R ¹ and R ² are hydrogen, an alkyl group that may have a substituent, an alicyclic group that may have a substituent; A certain phenyl group,
or a benzyl group that may have a substituent; R ³ ,
R ⁴ , R ⁵ and R ⁶ are hydrogen, halogen, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alicyclic group which may have a substituent, and a substituent. A certain phenyl group,
Benzyl group, alkoxycarbonyl group, which may have a substituent, benzyloxy group or dialkylamino group, which may have a substituent; n ² is 4
or 5; n ³ and n ⁴ represent 2 or 3, respectively. Moreover, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are groups A, B
They do not necessarily indicate the same type of thing at the same time. )] A lactone compound of quinoline-carboxylic acid represented by