DE2634987C2 - - Google Patents

Description

The invention relates to the use of new furo quinoline compounds as color former components for in microcapsules encapsulated chromogenic solutions as well as for pressure sensitive and heat sensitive recording materials. In particular, the invention relates to the use of newer ones Lactone compounds of quinoline carboxylic acid, which are essentially are colorless solids and a liquid solution have an almost colorless state, but with a reaction contact a dark colored with an acidic substance Accept condition.

In such marking-forming systems, a Marking in desired areas on a carrier web or a sheet by inducing a local Reaction contact between the chromogenic substance and the acidic substance in or on the web or sheet material causes, the chromogenic substance by transfer to the web or sheet material is applied or in this is already included. Through the reaction contact within the intended marking area creates a dark color.

Known pressure sensitive markers Systems contain the color-forming components on and / or in one or more carrier sheets, the color-forming components from each other when exposed to pressure breaking walls are insulated. Are located  all color-forming components on a single Sheet, then this sheet is called "autogenous reactive Sheet ".

In contrast, are the color-forming Components on separate sheets, then that will Recording material as a "transfer sheet system" designated. Be multiple leaves in the way stacked on top of each other that the top of this Leaves a receiving surface and the bottom one Represents transfer area, then you get one Multiple carbon copy rate.

In the most commonly used embodiment becomes a solution of basic chromogenic Substances, for example phthalides, pyromellitides and Fluoranes enclosed in microscopic ones Capsules on the surface of a transfer sheet coated while the adjacent receiving sheet with a Lewis acid, i.e. H. with an electron acceptor, is coated. There are numerous Lewis acid-type reagents are known which are described in Combination with basic chromogenic substances be used. The most used are acidic clays, such as attapulgite, silton clay, Zeolite, bentonite, halloysite, kaolin and silicon dioxide. In recent times there have been acid reactions Polymers used, either alone or in Combination with acidic clays. Examples of such Polymers are phenolic polymers, such as phenol-formaldehyde and phenol-acetylene polymers, maleic acid rosins, partially or fully hydrolyzed styrene Maleic anhydride copolymers, carboxypolymethylene and partially or fully hydrolyzed vinyl methyl ether-maleic anhydride copolymers and  Mixtures of the same. A large number of such acidic Polymers and solvents for these and for the chromogenic Substances are described in DE-PS 12 75 550.

Color images based on lactone compounds are known from the prior art, such as. B. that as Bluebilder used crystal violet lactone. From the DE-OS 22 59 409 are lactone color formers with a furopyrrole or furopyridine scaffold known.

The object of the present invention is to create new ones To provide color formers for recording materials, which have good color fastness and look good too for the production of chromogenic encapsulated in microcapsules Solutions.

The task is determined by the use new furoquinoline compounds of the general formula (I) and / or (II) solved.

The new chromogenic compounds of formula (I) and (II) are for use in the pressure sensitive described above Recording materials suitable, but can also in heat-sensitive recording materials, in electrothermal recording papers as well as in hectographic Transfer sheets can be used. You own an excellent color development speed and the color markings created are waterproof and possess high color fastness when the markings leaves containing sunlight for an extended period of time get abandoned. They are also very suitable for the production of chromogenic encapsulated in microcapsules Solutions.

The object of the invention is thus the use a chromogenic furoquinoline compound with the general Formula (I) and / or (II) according to the claim.

The preparation of the compounds according to the invention, in which B is an indolyl group is as follows Reaction scheme shown. 1 mole of quinoline-2,3-dicarboxylic anhydride (III) and 1 mole of (A-H) or 1 mole of (B-H) are either in a solvent or without a solvent  heated, or with the help of a Lewis acid catalyst exposed to a Friedel-Crafts reaction Obtain keto acid (IV-a or IV-b). Then 1 mole the keto acid and 1 mole of (B-H) or (A-H) together in a drainage condensing agent Brought reaction. Suitable drainage condensation agents are lower fatty acid anhydrides, such as acetic anhydride and propionic anhydride; Phosphorus oxychloride; Phosphorus trichloride; and inorganic acids such as Sulfuric acid and polyphosphoric acid. Suitable Lewis Acid catalysts include AlCl₃, ZnCl₂, SnCl₄ or FeCl₃. Suitable inert solvents are u. a. Chloroform, carbon tetrachloride, dichloroethane, Trichloroethane, tetrachloroethane, trichlorethylene, benzene, Toluene and xylene.

Reaction scheme

The lactone compounds of quinoline carboxylic acid (I) and (II) are isomers and those after the above Compounds produced are described processes usually obtained as a mixture of isomers, however you also get the connection in some cases (I) or the compound (II) alone. This isomer Mixtures can be added to the corresponding ones in a relatively simple manner Components are separated, such as by column chromatography, since, however, the one in one Recording system generated colors of the isomers one another similar is the use of such isomer mixtures not disadvantageous.

The table shows the new lactone compounds Quinoline carboxylic acid, which the general formulas I and / or II correspond and by those described above Processes can be made. In the table is also specified the color, which is a solution of the corresponding color-forming connection on contact with Silicon dioxide adopts.

table

The following are specific examples of the synthesis of some of those listed in the table Connections described.

Example 1

Preparation of 2- (1-ethyl-2-methylindol-3-yl) - 2- (4-pyrrolidine-2-methoxyphenyl) -2- [H] -5- [H] -furan [3,4-b] -quinolin-5-one (1a) and 2- (1-ethyl-2-methyl indol-3-yl) -2- (4-pyrrolidin-2-methoxyphenyl) -2- [H] -5- [H] furan- [4,3-b] -quinolin-5-one (1b); (Compounds No. 101).

10.5 g of 1-ethyl-2-methylindole, 13.2 g of quinoline 2,3-dicarboxylic acid anhydride and 30 ml of xylene were left in React reflux with each other for five hours. Then were 70 ml of 25% ammonia water is added to the contents dissolve and the unreacted indole was through Extraction with a small amount of toluene removed. Acidification of the ammonia water solution gave 12.2 g (51.7% of the theoretical yield) of a crude Mixture of 2- (1-ethyl-2-methylindol-3-yl) carbonyl quinoline-3-carboxylic acid and 3- (1-ethyl-2-methylindole-3- yl) carbonylquinoline-2-carboxylic acid in the form of pale pink Crystals with a melting point of 196 to 198 ° C.

Next, 2 g of the keto acid, 1 g of 3-pyrrolidine anisole and 20 ml of acetic anhydride at a temperature of 50 to 60 ° C for three hours reacted and then 50 ml 25% ammonia water is added to the acetic anhydride to decompose. After extraction with 100 ml Toluene was obtained by concentration 2.3 g (79.3% the theoretical yield) of a mixture of 2- (1-ethyl-2-methylindol-3-yl) -2- (4-pyrrolidin-2- methoxyphenyl) -2- [H] -5- [H] furan [3,4-b] quinoline- 5-one and 2- (1-ethyl-2-methylindol-3-yl) -2- (4- pyrrolidine-2-methoxyphenyl) -2- [H] -5- [H] -furan [4,3-b] -quinolin-5-one in the form of pale yellow-green Crystals with a melting point of 252 to 253 ° C.

Elemental analysis:
Calculated (as C₃₃H₃₁N₃O₃)
C 76.56 (%), H 6.05 (%), N 8.12 (%),
Found
C 76.65 (%), H 6.05 (%), N 8.10 (%).

Example 2

Preparation of 2- (1-ethyl-2-methylindol-3-yl) - 2- (4-piperidine-2-methoxyphenyl) -2- [H] -5- [H] -furan [3,4-b] -quinolin-5-one (2a) and 2- (1-ethyl-2- methylindol-3-yl) -2- (4-piperidin-2-methoxyphenyl) - 2- [H] -5- [H] furan [4,3-b] quinolin-5-one (2b); (Compounds No. 102).

2 g of the keto acid of Example 1, 1.1 g of 3-piperidine anisole and 30 ml of acetic anhydride were at a temperature of 50 to 60 ° C. reacted for three hours and then 50 ml of 25% ammonia water and 100 ml of toluene added and on for one hour Reflux temperature warmed. By separating the Toluene layer and subsequent concentration was obtained 2.1 g (70.0% of the theoretical yield) of one Mixture of 2- (1-ethyl-2-methylindol-3-yl) -2- (4- piperidine-2-methoxyphenyl) -2- [H] -5- [H] -furan [3,4-b] -quinolin-5-one and 2- (1-ethyl-2-methylindole- 3-yl) -2- (4-piperidin-2-methoxyphenyl) -2- [H] -5- [H] - furan- [4,3-b] -quinolin-5-one in the form of yellow Crystals with a melting point of 212 to 214 ° C.

Elemental analysis:
Calculated (as C₃₄H₃₃N₃O₃)
C 76.80 (%), H 6.27 (%), N 7.90 (%),
Found
C 76.75 (%), H 6.25 (%), N 7.88 (%).

Example 3

Preparation of 2- (1-ethyl-2-methylindol-3-yl) - 2- (4-diethylamino-2-benzyloxyphenyl) -2- [H] -5- [H] furan [3,4-b] -quinolin-5-one (3a) and 2- (1-ethyl-2- methylindol-3-yl) -2- (4-diethylamino-2-benzyloxyphenyl) - 2- [H] -5- [H] furan [4,3-b] quinolin-5-one (3b); (Compounds No. 104).

2 g of the keto acid of Example 1, 1.4 g of 3-diethylamino-benzyloxybenzene and 20 ml Acetic anhydride were at a temperature of 50 to 60 ° C together for four hours Brought reaction. By the same treatment as it was described in Example 2, was then obtained 2.6 g (78.9% of theoretical yield) one Mixture of 2- (1-ethyl-2-methylindol-3-yl) -2- (4-diethylamino-2-benzyloxyphenyl) -2- [H] -5- [H] - furan- [3,4-b] -quinolin-5-one and 2- (1-ethyl-2-  methylindol-3-yl) -2- (4-diethylamino-2-benzyloxy phenyl) -2- [H] -5- [H] -furan- [4,3-b] -quinolin-5-one in the form of pale yellow crystals with a melting point from 183 to 184 ° C

Elemental analysis:
Calculated (as C₃₉H₃₇N₃O₃)
C 78.62 (%), H 6.27 (%), N 7.05 (%),
Found
C 78.69 (%), H 6.25 (%), N 7.00 (%).

Example 4

Preparation of 2- (1-ethyl-2-methylindol-3-yl) - 2- (4-morpholine-2-methoxyphenyl) -2- [H] -5- [H] -furan [3,4-b] -quinolin-5-one (4a) and 2- (1-ethyl-2- methylindol-3-yl) -2- (4-morpholin-2-methoxyphenyl) - 2- [H] -5- [H] furan [4,3-b] quinolin-5-one (4b); (Compounds No. 106).

2 g of the keto acid of Example 1, 1.1 g of 3-morpholine anisole and 20 ml of acetic anhydride were at a temperature of 50 to 60 ° C for reacted for two hours. The same treatment as described in Example 2 yielded 2.0 g (66.7% of theoretical yield) a mixture of 2- (1-ethyl-2-methylindol-3-yl) -2- (4-morpholine-2-methoxyphenyl) -2- [H] -5- [H] furan [3,4-b] -quinolin-5-one and 2- (1-ethyl-2-methylindole- 3-yl) -2- (4-morpholin-2-methoxyphenyl) -2- [H] -5- [H] - furan- [4,3-b] -quinolin-5-one in the form of pale yellow Crystals with a melting point of 243 to 244 ° C.

Elemental analysis:
Calculated (as C₃₃H₃₁N₃O₄)
C 74.26 (%), H 5.87 (%), N 7.88 (%),
Found
C 74.21 (%), H 5.89 (%), N 7.85 (%).

Example 5

Preparation of 2- (1-ethyl-2-methylindol-3-yl) - 2- (4-diethylamino-2-ethoxyphenyl) -2- [H] -5- [H] furan [3,4-b] -quinolin-5-one (5a) and 2- (1-ethyl-2- methylindol-3-yl) -2- (4-diethylamino-2-ethoxyphenyl) -2- [H] -5- [H] furan [4,3-b] quinolin-5-one (5b); (Compounds No. 116).

2 g of the keto acid of Example 1, 1.1 g of 4-diethylamino-2-ethoxybenzene and 20 ml Acetic anhydride was left at one temperature from 50 to 60 ° C for one hour react. By the same treatment as her described in Example 2, was obtained 2.4 g (80.0% of theoretical yield) one Mixture of 2- (1-ethyl-2-methylindol-3-yl) -2- (4-diethylamino-2-ethoxyphenyl) -2- [H] -5- [H] -furan [3,4-b] -quinolin-5-one and 2- (1-ethyl-2-methylindole- 3-yl) -2- (4-diethylamino-2-ethoxyphenyl) -2- [H] -5- [H] - furan- [4,3-b] -quinolin-5-one in the form of pale yellow Crystals with a melting point of 280 to 281 ° C.

Elemental analysis:
Calculated (as C₃₄H₃₅N₃O₃)
C 76.51 (%), H 6.62 (%), N 7.87 (%),
Found
C 76.47 (%), H 6.60 (%), N 7.88 (%).

The production of pressure sensitive Recording material using the invention chromogenic compounds can by means of known methods. Generally will one or more of the lactone compounds according to the general formulas (I) and / or (II) in one difficultly volatile solvent, for example in an alkyldiphenyl or an alkylnaphthalene, solved and the solution is by known methods enclosed in microcapsules. An aqueous capsule dispersion is then on a carrier sheet, for example on a sheet of paper, coated and then dried.  

The production of a heat sensitive Recording material can also by means of known methods. Generally speaking which are represented by the general formula (I) and / or Formula (II) represented lactone compound and Color developers, such as bisphenol A, each in an aqueous solution of a binder, such as polyvinyl alcohol, ground and then mixed. The mixture obtained is then on a carrier sheet, such as on a Paper sheet, coated and then dried. Is the heat-sensitive manufactured in this way Recording material with a heated pen or a thermal printhead locally heated, then the lactone compounds and melt the color developer in the heated areas and react with each other to form a certain colored marker.

Claims (1)

Use of a chromogenic furoquinoline compound with the general formula: wherein X is a halogen or a nitro group, n 1 an integer from 0 to 4, A one of the following substituents and B represents one of the substituents wherein R¹ and R² are hydrogen, an unsubstituted or substituted alkyl, phenyl or benzyl substituent, R³, R⁴, R⁵ and R⁶ are hydrogen, halogen, an unsubstituted or substituted alkyl, alkoxy, alicyclic, phenyl, benzyl or benzyloxy-substituent or a dialkylamino substituent, and n ² 4 or 5 and n ³ and n ⁴ 2 or 3, for encapsulated in microcapsules chromogenic solutions as well as for pressure-sensitive and heat-sensitive recording materials.