JPS6125745B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel quinoline-carboxylic acid lactone compounds represented by the general formulas () and (). [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. (Here, 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 substituent) Benzyl group; 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. Furthermore, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ do not necessarily represent the same type in A and B 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, polyfluoromethyl, etc.)] The quinoline-carboxylic acid lactone compounds represented by the above general formulas () and () were newly synthesized by the inventors, and as such are normally Virtually colorless or slightly colored crystals,
When it comes into contact with an electron acceptor such as activated clay or phenolic resin, 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 fire 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 into 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. A novel quinoline-carboxylic acid lactone compound represented by the general formula () or () is
Although it can be synthesized by various methods, the following two methods are typical. (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 of (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 aqueous ammonia, caustic soda, or sodium carbonate, extracted with an inert solvent such as those mentioned above, and concentrated to obtain the desired lactone compound. The quinoline-carboxylic acid lactone compounds represented by () and () are isomers and are usually obtained as a mixture of isomers by the above-mentioned method. 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, and according to the above method, they are usually obtained as a mixture of isomers, but by selecting reaction conditions, (-a) or (-b) can be obtained. 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. Novel quinolines represented by the general formulas () and () obtained by the above method.
Specific examples of carboxylic acid lactone compounds and color tones 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-
[3,4-b]-quinolin-5-one () and 2,2-bis(4-pyrrolidino-2-methoxyphenyl)-2-[H]-5-[H]-furan-
[4.3-b]-Quinoline-5-one (), (compound number 1) production method 1.8 g 3-pyrrolidinoanisole, 1 g quinoline-2,3-dicarboxylic anhydride and 20 ml
of acetic anhydride 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, 1.6 g (theoretical yield 59.3%) of 2,2-bis(4-pyrrolidino-2-methoxyphenyl)-2-[H]-5-[H]-furan-[3,4
-b]-quinolin-5-one () and 2.2
-Bis(4-pyrrolidino-2-methoxyphenyl)-2-[H]-5-[H]-furan-[4.3-
b]-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) -Production method of 2-carboxyquinoline () 10 g of quinoline-2,3-dicarboxylic anhydride, 19.4 g of 3-ethoxydiethylaniline,
14.7 g AlCl ₃ and 100 ml dichloroethane 20
After stirring at ℃ for 20 hours, drain into dilute hydrochloric acid. The dichloroethane layer is separated, washed with water, and then 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 dilute hydrochloric acid to remove the precipitate, washed with water and dried to give 2-(2-
Ethoxy-4-diethylaminobenzoyl)-3
-9.8 g of a mixture of carboxyquinoline () and 3-(2-ethoxy-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, mp150~152℃
It was hot. On the other hand, when the liquid is concentrated to dryness under reduced pressure,
6.1 g of 3-(2-ethoxy-4-diethylaminobenzoyl)-2-carboxyquinoline () are 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-[3,4-b]-quinolin-5-one () (compound number 45) 1 g of 2-(2-ethoxy-4-diethylaminobenzoyl)-3-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 50ml toluene and 25ml
After adding 25% ammonia water and heating under reflux for 1 hour, the toluene layer was separated, washed with hot water, and concentrated to yield 1.1 g (theoretical yield 72.5%) of 2-(2-ethoxy-4-diethylamino-phenyl)-2- (1-benzyl-2-
Methyl-indol-3-yl)-2-[H]-5
-[H]-furan-[3,4-b]-quinoline-5-
get on(); Pale yellow-green crystal, mp218~
It was 220℃. 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 78.48 6.15 6.99 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 (, XI, XII,) were obtained.

[Table] Example 4 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 3 yielded 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.

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[Table] Example 5 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 6 2-(2-methoxy-4-dibutylaminophenyl)-2-(1-butyl-2-methyl-indol-3-yl)-2-[H]-5-[H]-furan- [3,4-b]-quinolin-5-one (
) (Compound No. 51) production method 2 g of 2-(1-butyl-2-methyl-indol-3-yl)-carbonylquinoline-3-carboxylic acid (Example 5), 1.8 g of 3-dibutylaminoanisole and 20 ml of acetic anhydride at 50-60 g
React at ℃ for 2 hours. Next, 100 ml of 20% caustic soda aqueous solution was added, and after heating under reflux for 1 hour, the toluene layer was separated, washed with hot water, and concentrated to obtain 2.5 g (theoretical yield: 80.0%) of 2-(2-methoxy-4-dibutylaminophenyl). enyl)-2-(1-butyl-2-methyl-indol-3-yl)-2-[H]-5-[H]
-Furan-[3,4-b]-quinolin-5-one () is obtained. White crystals, mp 258-260°C. Based on the analysis results below, the molecular formula of this compound is
It _was confirmed that _it was _{C39H45N3O3 .} C H N Theoretical value 77.56 7.53 6.96 Actual value 77.44 7.46 6.79 In addition, the corresponding quinoline-carboxylic acid lactone compound (XII) was prepared by using 3-diethylaminophenethole instead of 3-dibutylaminoanisole used in the above reaction. Obtained.

[Table] Example 7 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 (XI) and 3-(1-ethyl-2-methyl-indole-3
16.2 g (theoretical yield 90.1%) 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 (XI). Yellow powder, mp208~
It was 209℃. On the other hand, when the liquid was concentrated to dryness under reduced pressure, 11 g of 3-(1-ethyl-2-methyl-indol-3-yl)-carbonylquinoline-2-
Obtain carboxylic acid (XI). light brown powder, m.
p. It was 125-130℃. Example 8 2-(2-ethoxy-4-diethylaminophenyl)-2-(1-ethyl-2-methyl-indol-3-yl)-2-[H]-5-[H]-furan-[ 3,4-b]-quinolin-5-one (
) (Compound No. 43) production method 1 g of 2-(1-ethyl-2-methyl-indol-3-yl)-carbonylquinoline-3-carboxylic acid (XI, Examples 5 and 7), 0.8 g of 3
-React diethylaminophenetol and 10 ml of acetic anhydride at 50-60°C for 2 hours. Then, the same treatment as in Example 3 yielded 1.3 g (theoretical yield 87.3
%) of 2-(2-ethoxy-4-diethylaminophenyl)-2-(1-ethyl-2-methyl-indol-3-yl)-2-[H]-5-[H]-furan-[ 3,4-b]-quinolin-5-one ()
get. Pale yellow-green powder, mp 280-281°C. Based on the analysis results below, the molecular formula of this compound is
It _was confirmed that _it was _{C34H35N3O3 .} C H N Theoretical value 76.51 6.62 7.87 Actual value 76.40 6.53 7.79 In addition, the following aniline derivative was used in place of 3-diethylaminophenethole used in the above reaction to prepare the corresponding quinoline-carboxylic acid lactone compound (,,,,, ,
,,XI,,XI,
XII...
) was obtained.

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[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
The alkylnaphthalene KMCR (trade name of Kureha Chemical) was dissolved as 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 to completely emulsify it, and 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 applying pressure locally by printing or writing on the upper and lower lobes adjusted as above, 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 lobule. 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 of 0 to 4. (Here, 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 substituent) Benzyl group: R ³ ,
R ⁴ , R ⁵ , and R ⁶ are hydrogen, halogen, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an alicyclic group that may have a substituent, and a substituent. Phenyl group, sometimes substituted benzyl group, alkoxycarbonyl group, sometimes substituted benzyloxy group or dialkylamino group: n ²
represents 4 or 5: n ³ and n ⁴ represent 2 or 3, respectively. In addition, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ do not necessarily represent the same group in groups A and B at the same time)] A lactone compound of quinoline-carboxylic acid.