DE2516383A1 - INDOLINOSPIROPYRANE COMPOUNDS - Google Patents

Description

The invention relates to new Indolinospiropyranverbindungenoti, which can be used as color forming agents.

Indolinospiropyran compounds are already known which have a benzene nucleus in the spiropyr component which is substituted with an alkyl group, alkoxy group, nitro group or a halogenntora. Such compounds are described, for example, in U.S. Patents 3,090,687, 3,212,898, 3,291,6öh, 3,293,055, 3,320,067 and 3,442,648. However, none of these publications describe the new indolinospiropyran compounds according to the invention.

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5098A3 / 0929

The compounds according to the invention are characterized in that they have a disubstituted amino group in the 7'-position of the spiropyran part and that they therefore react with electron acceptor substances such as Lewis acids, whereby various dyes with high color intensity and excellent lightfastness after color formation are obtained will. The storage stability of these new compounds in microcapsules of color formation is excellent. The indolinospiropyran compounds according to the invention are therefore of particular value as color formers for pressure-sensitive copier papers.

The invention therefore relates to indolinospiropyran compounds the general formula:

(R ₂ )

n-6

(D

wherein R ₁ denotes a substituted or unsubstituted alkyl group, the substituent being a hydroxy, carboxy, benzyl or phenyl group, Rp ^ ^{ur e} ^ ⁿ hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a cyano group , a nitro group, a phenoxy group or a phenyl group, R, and Rk, which can be the same or different, each represent substituted or unsubstituted alkyl groups, the substituent or substituents being a cyano

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509843/0929

group, a halogen atom, an alkoxy group, a benzyl group or a substituted or unsubstituted phenyl group, where the substituent is an alkyl group, R. is a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom and η is an integer from 0 to 2, wherein the alkyl groups and the alkyl portion of the substituted alkyl group, the alkoxy groups and the alkoxycarbonyl groups have 1 to h carbon atoms.

The above-mentioned indolinospiropyran parabens are the general ones Formula I can be prepared by adding an indoline compound of the general formula:

CH3 CH3 j

wherein R ₁ , R "and η have the meanings given, with a salxcylaldehyde derivative of the general formula:

CHO
OH p \ ' (HD

Ί \

wherein R ", R ^ and R ₁ - have the meanings given above.

509843/0929

The new color formers according to the invention are essential colorless or slightly colored powdery substances which are stable in the atmosphere, but which experienced color changes to pink, bluish-red or reddish-purple when heated. The color formers according to the invention are in natural or synthetic high molecular substances, many animal, vegetable or mineral Waxes, ethyl cellulose, polyvinyl acetate, rosin-modified Alkyd resins and the like, soluble or miscible, and they are in a wide variety of organic liquids such as alcohols, e.g. methanol, ethanol etc., cellosolve ethers, e.g. ethyl cellosolve etc. Carbons, e.g. benzene, toluene, dibenzylbenzene, Dibenzyltoluene, alkylnaphthylenes etc., halogenated hydrocarbons, e.g., chloroform, chlorobenzenes, etc., and trioctyl phosphate and the like, are soluble.

A solution of the color formers according to the invention in the above organic liquids develop a pink, bluish-red or reddish-purple color immediately, . after the solution on active clay substances such as acid clay, attapulgite, zeolite, bentouite and the like, solid organic acids such as succinic acid, maleic acid, tannic acid, benzoic acid or the like, or acidic polymers such as carboxy polyethylene, phenol aldehyde polymers, Styrene / maleic anhydride copolymers containing residual acidic groups and the like are adsorbed has been. The color formed on such solid materials generally has one high color density and excellent water resistance and lightfastness. Thus, the invention Color formers as marking color formers for recording materials, such as heat-sensitive copier papers, hectares

509843/0929

graphic printing papers, pressure sensitive copier papers and the like, are suitable.

Specific classes of the present invention are Indolinospiropyranverbindungen lgruppe a substituted ALK3 ^r those of the formula I, '.-' orin (a) R _1, in which the substituent is a hydroxy or carboxy group (for example Hydroxym ^ thyl, hydroxyethyl, carboxymethyl, carboxyethyl etc. ), a benzyl group or a phenyl group and R ₀ , R ", Ri, R" and η have the meanings given above, in which (b) R "is an alkyl group (eg methyl, ethyl, propyl, butyl), an alkoxy group (eg Methoxy, ethoxy etc.), an alkoxycarbonyl group (eg methoxycarbonyl etc.), a halogen atom (eg bromine, chlorine etc.), a cyano group, a nitro group, a phenoxy or phenyl group, and Rj, R ", Ri, R and η hnben the meanings given above, '- / orin (c) R "and Ri, which can be the same or different, substituted alkyl groups, where the substituent is a cyano group, a halogen atom or an alkoxy group (e.g. cyanomethyl, cyanoethyl, chloromethyl, chloroethyl, Methoxyethyl etc.) is a e benzyl group or a substituted or unsubstituted phenyl group, where the substituent is an alkyl group (for example p-tolyl) and R .., R ^, R _n . and η have the meanings given, and / or in which (d) when R ₁ - an alkyl group (e.g. methyl, ethyl etc.), an alkoxy group (e.g. methoxy, ethoxy etc.) or a halogen atom (e.g. chlorine, bromine etc.) and R-, R ", R", R. and η have the meanings given above, the alkyl groups and the alkyl part of the substituted alkyl groups, the alkoxy groups and the alkoxycarbonyl groups have 1 to h carbon atoms.

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509843/0929

Representative compounds according to the present invention are, for example: 1,3, ^ - trimethylindolino-T ¹ -diethylaminobenzospiropyran, 1-phenyl-3,3-dimethylindolino-7'-diethylaminobenzospiropyran, 1,3 »3-trimethylindolino-7'- dibenz3 ^r laminobenz ο spiropyran., 1, 3. 3-trimethyl-5-chloroindolino-7'-dicyanoethylaminobenzospiropyran, 1, 3 »3-trimethyl-5-chloroindolino-7 ^f -diethylaminobenzospiropyran, 1,3 * 3-trimethyl-5-methoxyindolino -7 ^f -dibenzylaminobenzospiropyran, 1-phenyl-3,3-dimethylindolino-7'-dibenzylatninobenzospiropyran, 1,3,3 »5-tetramethylindolino-7 ^l -dibutylatninobenz o spiropyran, i-hydroxyethyl-3 j 3-dimethylindolino- 7'-dimethylaminobenzospiropyran and 1-ethyl-3,3>5-trimethylindolino-5'-methoxy-7'-diethylaminobenzospiropyran.

Representative indoline compounds of the formula II which can be used as starting materials for the preparation of the indolitiospirop3tan compounds of the invention are, for example, the following compounds: 1,3,3-trimethyl-2-methyleneindoline, 1-ethyl-3,3-dimethyl-2- methylene indoline, 1-carboxymethyl-3> 3-dimethyl-2-methylene indoline, 1-ß-hydroxyethyl-3,3-dimethyl-2-methylene _indoline} 1-ß-xthoxycarbonylethyl-3> 3-dimethyl-2-methylene indoline, 1- Jf-cyanopropyl-3,3-dimethyl-2-methyleneindoline, 1-butyl-3,3-dimethyl-2-methyleneindoline, 1-benzyl-3 , 3-dimethyl-2-methyleneindoline, 1-p-nitrobenzene-3, 3-diethyl-2-methylene indoline, 1-phenyl-3,3-dimethyl-2-methylene indoline, 1,3,3,5-tetramethyl-2-methylene indoline, 1,3,3,7-tetramethyl-2-methylene indoline, 1,3,3, ^, 7-pentamethyl-2-methylene indoline, 1,3.3 »5,7-pentamethyl-2-methylene indoline, 1,3,3-trimethyl-5-methoxy-2-methylene indoline, 1,3, 3-trimethyl-7- ^ nethoxy-2-methylene indoline, 1,3,3-trimethyl-ί ^, 7-dimethoxy-2-methylene _{indoline ί}

, 1, 3> 3-

509843/0929

Trimethyl- ^ ^ -diäthoxy ^ -methyleneindoline, 1,3 j3-trimethyl-5-chloro-2-methyleneindoline, 1,3,3 ~ trimethyl-7-chloro-2-methylene indoline, 1, 3, 3-trimethyl-5-t> rom-2-methylen.indoline, 1 ^^ - trimethyl - ^ - dichloro ^ -methyleneindoline, 1,3,3-trimethyl ^ -cyano ^ -methyleneindoline, 1, 3,3-trimethyl-5-ethoxycarbonyl-2-methyleneindoline, 1, 3, 3-trimethyl-5-nitro-2-raethyleneindoline, 1, 3 ^ -trimethyl-S-benzyl - ^ - niethylenindoline, 1,3 »3-trimethyl-5-phenoxy-2-πlethyleneindoline, 1 ^^ - trimethyl-S-phenyl ^ -methyleneindoline, 1-ethyl-3, 3. 5-trimethyl-2-methylene indoline, 1-ethyl-3,3-dimethyl-5-methoxy-2-methyleneindoline, 1-p-Tolyl-3,3,5-trimethyl-2-methylene indoline and the same.

Representative examples of salicylaldehyde derivatives of the formula IXI ₁ which can be used for the invention are, for example, the compounds 5-aminosalicylaldehyde, 4-dimethylaminosalicylaldehyde, 4-diethylaminosalicylaldehyde, 4-dibutylaminosalicylaldehyde, 4-dimethylamino-5-methylsalicylaldehyde, 4- methylsalicylaldehyde, ^ -Diäthylatnino-e-methoxysalicyla ldehyde, ^ -Diethy lamino-3- ^ chlorosalicylaldehyde, ^ -N-methyl-N-ß-cyauoätiylaminosalicylaldehyd, ^ -N-ethyl-N-ß-chloroethylamino -N-ß-methoxyethylaminosalicylaldehyde, ^ -N, N-Diß-cyanoäthylaminosalicylaldehyd, ^ -N ^ -Di-ß-chloroethylaminosalicylaldehyde, ^ -N-ethyl-N-benzylaminosalicylaldehyde, 4-N, N-dibenzylaminosalicylic acid Di-p-chlorobenzylate ninosalicylaldehyde, UN, N-di-p-methylbenzylaminosalicylaldehyde, UN-methyl-N-phenylaminosalicylaldehyde, ^ -N-ethyl-N-phenylate ninosalicylaldehyde, 4-N-methyl-N-ptolylate ninosalicylaldehyde, and the like.

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5098 ^ 3/0929

The reaction between the indoline compound of the formula II and the salicylaldehyde derivative of the formula III can, if necessary, in the presence of a base, such as triethylamine, Pyridine, quinoline and the like, or an acid such as glacial acetic acid, can be carried out to cause the reaction accelerate, and also in the presence of a volatile inert organic solvents, e.g. methanol, ethanol, methyl cellosolve, ethyl cellosolve, chloroform, benzene, Toluene and the like to ensure smooth reaction, whereby the indolinospiropyran color formers of the general formula I according to the invention are of high purity and high yield can be obtained.

The reaction can be carried out using about 1 mole of indoline compound of Formula II and about 1 to about 2 moles of the salicylaldehyde derivative of Formula III in the above volatile inert organic solvents and if necessary in the presence of the bases or acids described above at temperatures from about 50 to about 130 C for periods of about 3 to about 12 hours will. After the reaction has ended, the reaction mixture is cooled to precipitate the product, and the crystals formed in this way are filtered off. The filter cake is then washed with ethanol and the like washed, ■ whereby the new indolinospiropyran color former of the formula I is obtained. Alternatively can the reaction mixture is distilled under reduced pressure in order to remove volatile inert organic solvent, and wash the residue with ethanol and the like, by means of which the color former of the formula I is obtained. If necessary, the received in this way Color formers are recrystallized.

5098A3 / 0929

The invention is illustrated in the examples. example 1

7.0 g of 1,3,3-trimethyl-2-methylene indoline and 7.8 g of 4-diethylaminosalicylaldehyde Kurds added to 50 ml of ethanol. The appliance was kept for 7 hours at a temperature of 80 to 82 C. allowed to react, cooled to room temperature beforehand became. The precipitated crystals were filtered off and washed with ethanol, yielding 11.5 g of "1,3» 3-trimethylindolino-7'-diethylaminobenzospxropyran obtained as pale pink-white crystals with a melting point of 178 to 179 ° C became. A benzene solution of the color former thus obtained developed after adsorption acidic clay a bluish-red color.

Example 2

^> 2 g of 1,3,3-trimethyl-5-chloro-2-methyleneindoline and 4.2 g of ^ -diethylaminosalicylaldehyde were added to 25 ml of ethanol. The mixture was for 7 hours at 80 to 82 C and allowed to react, the product was worked up as in Example 1 to obtain 6.2 g of 1,3,3-trimethyl-5-chlorindolino-7 ^r -diathylaminobenzospxropyran as am ßrosa-v; hite Crystals having a melting point of 172 to 174 ° C were obtained. A benzene solution of the color former thus obtained was adsorbed on acid clay and a bluish-red color developed.

Example 3

2.4 g of 1-phenyl-3,3-dimethyl-2-methyleneindoline and 2.1 g of 4-diethylaminosalicylaldehyde were added to 20 ml of ethanol

5098 ^ 3/0929

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give and there were O, O5 g of triethylamine added. That resulting mixture, 5 b- was reacted at 80 to 82 C. calmly. Ethanol was distilled off under reduced pressure and the residue was washed with a small amount of ethanol gev.-ascb.en and from ethanol-ligroin (volume ratio 3 ϊ urocrystallized. whereby 3 »3 g of 1-phenyl-3 * 3-dimetliylindolino-T'-diethylatninobenzospiropyran obtained as pale pink-white crystals with a melting point of 150 to 15 C. became. A toluene solution of the color former obtained in this way was adsorbed on acid clay and it a reddish-purple color developed.

Example l

2.6 g 1 ^^ - trimethyl-E-methylene indoline and 5.0 g 4-dibenzylaminosalicylaldehyde were added to 20 ml of ethanol and 0.1 g of triethylamine were added. The resulting Mixture was 5 h. implemented at 8O to 82 C and the product was worked up as in Example 1, whereby 5 »8 g 1,3 * 3-trimethylindolino-7'-dibenzylaminobenzospiropyran. as pale pink-white crystals with a melting point of 115 to 118 C were obtained. A benzene solution of the on this quietly obtained color former was adsorbed on acidic clay and a bluish-red color developed Coloring.

Example 5

3 »0 S 1 ^^ - trimethyl-.S-methoxy ^ -methyleneindoline and 5.0 g ^ -dibenzylaminosalicylaldehyde were added to 30 ml of methanol, and 0.1 g of pyridine was added. The resulting mixture was reacted for 12 hours at 60 to 63 C and the pro-

50984 3/0929

Product was worked up v / ie in Example 1, by 6.1 g 1,3 »3-trimethyl-5-methoxyindolino-7 '-dibenzylaminobenzospiropyran as pale pink crystals with a melting point of 121 to 125 ° C. A benzene solution of the color former obtained in this way was adsorbed on acid clay and a bluish-red color was formed the end.

Example 6

2.4 g of 1-phenyl-3,3-dimethyl-2-methyleneindoline and 3.7 g of 4-dibenzylaminosalicylaldehyde were added to 20 ml of ethanol and 0.1 g of triethylamine was added. The resulting mixture was reacted for 6 h at 80 to 82 ° C. and the product was worked up as in Example 3, yielding 4.3 g of 1-phenyl-3 »3-dimethylindolino-7'-dibenzylaminobenzospiropyran as pale pinkish-white crystals with a melting point from 124 to 127 C. A toluene solution of the color former obtained in this way was adsorbed on acid clay and a reddish purple coloration developed.

Example 7

1.9 g 1,3,5-tetramethyl-2-raethyleneindoline and 2.3 g 4-dibutylaminosalicylaldehyde Were added .zu 15 ml of methanol and treated with 0.05 g of triethylamine. The resulting The mixture was reacted for 10 h at 60 to 63 C and that Product was worked up as in Example 1, giving 2.9 g of 1,3,3-trimethyl-5-methylindolino-7'-dibutylaminobenzospiropyran were obtained as pale pink-white crystals with a melting point of 130 to 135 ° C. A ben-

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509843/0929

inch solution of the color former obtained in this way It was adsorbed on acidic clay and formed a bluish-red color Coloring off.

Example 8

2.0 g of 1-β-hydroxyethyl-3) 3-dimethyl-2-methyleneindoline. and 1.7 g of ^ -Dimethylarninosalicji-laldehyd were added to 20 ml of methanol and mixed with 0.1 g of triethylamine. The resulting mixture became 12 h. reacted at 60 to 6 ° C. and the product was worked up as in Example 1, whereby 2.6 g of 1-β-hydroxyethyl-3,3-dimethylindolino-7'-dimethylaminobenzospiropyran were obtained as pale pink crystals with a melting point of 155 to 162 ° C . A benzene solution of the color former obtained in this way was adsorbed on acidic clay and a bluish-red color developed.

Example 9

2 O ₅ g of 1-ethyl-3,3,5-trimethyl-2-methyleneindoline and 2.3 g ^ -Dimethylamine-6-niethoxysalicylaldehyd were added to 15 ml of methyl cellosolve and 0.1 g of pyridine. The mixture was reacted for 5 hours at 110 to 120 ° C. and the product was worked up as in Example 3, giving 2.9 g of 1-ethyl-3,3-dimethyl-5-methylindolino-7'-diethylate ninobenzospiropyran as light pink crystals with a melting point from 148 to 153 C. A benzene solution of the color former obtained in this way developed a bluish-red color after adsorption on acid clay.

509843/0929

Example 10

2.1 g of 1,3,3-trimethyl-5-chloro-2-methyleneindoline and 2.6 g of U-N, N-di-ß-cynnoethylaminosalicylaldehyde were added to 20 ml of ethanol and 0.1 g of triethylamine was added. The resulting mixture was reacted for 5 h at 80 to 82 ° C. and the product was worked up as in Example 1, giving 3.5 g of 1,3,3-trimettryl-5-chloroindolino-7 ^l -N, N-di-ßcyanoäthylaminobenzospiropyran as light pink crystals with a melting point of 133 to 144 ° C were obtained. A benzene solution of the color former thus obtained was adsorbed on acid clay and a bluish-red color developed.

Example 11

As in Example 1, with the exception that the 1, 3, 3-trimethyl 2-methylene indoline and 4-diethyl aminosalicylaldehyde were replaced by the indoline and salicylaldehyde shown in the following table, various indolinospiropyran compounds became obtained according to the table nls light pink crystals. Benzene solutions of the on this Color formers obtained in this way are adsorbed on acidic clay. The table shows the color shade developed in each case.

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Table I.

Itidolin

Snlicylaldehyde Color formers

developed Fnrbc

C = CH ₂

C = CH ₂

CH ₃

OCH ₃

C ₂ HuCiI

CHO

C ₂ H ^ OCH ₃ CH ₃ CH ₃

OCH ₃

C ₂ HuCA

bluish-red

bluish-red

C ₂ Hu0CH ₃

CHO

C ₂ H ₅ C ₂ H ₅

cn

bläuly ^ h-red

GO

CD CO

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C. O -P I. ν CJ ο τ * τ · ΐΐ - -D ¹ p ■ Ρ U 3 *

O -H r-i

• Ο

δ _Ν ? ¹ 5098 Λ / S.
Where
δ ORIGINAL β
• rf
O Q •O / \ ο β
H O
O
» υ ο - η 43/0929 INSPECTED

5516383

ο υ

Indoline

Salicylaldehyde color former

developed color

CH3 CH3

CHO

C «CH ₂

CH _{3 CH 3}

CHO

CHO

C ₂ H ₅

reddish purple irbon

reddish-pur-

purple

CO 00 CO

b 1 au 1 i c 11 -> r ο t

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O I. S / J2 CJ O O •H -Η ί— ■ 3 I-i C. Xl

U ο ΰ

509843/0929

Claims (15)

wherein H. is a substituted or unsubstituted alkyl group, the substituent being a hydroxy, carboxy, benzyl or phenyl group, Rp for a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a cyano group, a nitro group, a Phenoxy group or a phenyl group, R ~ and R ^, which can be the same or different, are in each case substituted or unsubstituted alkyl groups, the substituent or substituents being a cyano group, a halogen atom, an alkoxy group, a benzyl group or a substituted or unsubstituted phenyl group, where the substituent is an alkyl group, R_ is a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom and η is an integer from 0 to 2, where the alkyl groups and the alkyl part of the substituted alkyl group, the alkoxy groups and the alkoxycarbonyl groups 1 to h have carbon atoms. -19- 509843/0929 ■ Λ9 - 2. Compounds according to claim 1, characterized in that R _{1 is} a substituted alkyl group, the substituent being a hydroxy, carboxy, benzyl or phenyl group. 3. Compounds according to claim 1, characterized in that Rp is an alkyl group, alkoxy group, Alkoxycarbonyl group, a halogen atom, a cyano group, a nitro group, a phenoxy group or is a phenyl group. H. Compounds according to claim 1, characterized in that R "and R., which can be the same or different, substituted alkyl groups, the substituent being a cyano group, a halogen atom or an alkoxy group, benzyl groups or substituted or unsubstituted phenyl groups, the substituent being an alkyl group is mean. 5 · Compounds according to claim 1, characterized in that R "is an alkyl group Is an alkoxy group or a halogen atom. 6 .. 1, 3>3-trimethylindolino-7'-diethylaminobenzospiropyran. 7. 1-Phenyl-3 »3-dimethylindolino-7'-diethylaminobenzospiropyran. 8. 1,3 s3-trimethylindolino-7'-dibenzylaminobenzospiropyran. -20- 509843/0929 - · 20 9. 1.3 »3-trimethyl-5-chloroindolino-7'-dicyanoethylamxnobenzοspiropyran. 10. 1, 3,3-trimethyl ~ 5-cb.lorindolino-7 ^! -diethylaminobenzospiropyran. 11. 1,3,3-trimethyl-5-methoxyindolino-7'-dibenzylaminob enz ο s pir opyran. 12. 1-Phenyl-3 »3-dimethylindolino-7'-dibenzylaminobenzospiropyran. 13. 1> 3.3 j 5 ~ tetramethylindolino-7'-dibutylatninobenzospiropyran, ~ \ k. 1-hydroxyethyl-3 j 3-dimethylindolino ~ 7 '-dimethylatninobenzospiropyran. 15. 1-Ethyl-3,3,5-trimethylindolino-5'-methoxy-7'-diet hylaminobenzοspiropyran. 5098Λ3 / 0929