Ciba-geigy Corporation

Ciba-geigy Ag

Giba-geigy Corporation

Robert Garner

Jean C Petitpierre

Jean-Claude Petitpierre

John Barry Henshall

Michael J Whitehead

Max Dunnenberger

Davor Bedekovic

Jerry L Pool

Brian J Williams

A process for the preparation of a fluoran compound of the formula ##STR1## wherein R, R.sub.1, R.sub.2 and R.sub.4 are each independently hydrogen, halogen, lower alkyl or lower alkoxy,

Process for the manufacture of fluoran compounds

Anhydride compounds of the formula ##STR1## wherein A is an optionally substituted amino-phenyl or optionally substituted 3-indolyl radical, Hal represents halogen, Z represents hydrogen, alkyl of 1 to 4 carbon atoms or an optionally substituted phenyl radical and n is 1 to 4; these anhydrides are particularly useful as starting materials for the manufacture of halogenated 3-aryl-3-indolyl-phthalides or fluoran derivatives.

(N-Substituted benzoyl)halobenzoic acid anhydrides

Phthalide compounds of the formula ##STR1## wherein A and B, independently of the other, represent a monovalent radical of the formula ##STR2## wherein X.sub.1 represents an amino group of the formula ##STR3## X.sub.2 represents halogen or an amino group of the formula ##STR4## W is hydrogen or halogen, R.sub.1 and T.sub.1 each represents alkyl of at most 12 carbon atoms which is unsubstituted or substituted by halogen, hydroxyl, cyano, lower alkoxy or lower alkylcarbonyloxy, cycloalkyl, phenyl, benzyl or phenyl or benzyl which are substituted by halogen, nitro, lower alkyl or lower alkoxy, R.sub.2 and T.sub.2 each represents hydrogen, alkyl of at most 12 carbon atoms, which is unsubstituted or substituted by halogen, hydroxyl cyano, lower alkoxy or lower alkyl-carbonyloxy; cycloalkyl, benzyl or benzyl which is substituted by halogen, nitro, lower alkyl or lower alkoxy, and T.sub.2 may also represent acyl having 1 to 8 carbon atoms or each pair of substituents R.sub.1 and R.sub.2 or T.sub.1 and T.sub.2 together with the nitrogen atom to which they are attached independently represents a 5- or 6-membered, heterocyclic radical, R.sub.3 represents hydrogen, halogen, lower alkyl, lower alkoxy or lower alkyl-carbonyloxy, Y, Y.sub.1 and Y.sub.2 each represents hydrogen, alkyl which has at most 12 carbon atoms and is unsubstituted or substituted by halogen, hydroxyl, lower alkoxy or cyano, or benzyl which is unsubstituted or substituted by halogen, nitro, lower alkyl or lower alkoxy, Z represents hydrogen, lower alkyl or phenyl, and wherein the benzene ring D is not further substituted or additionally contains halogen and the rings E and G independently of the other, are unsubstituted or substituted by halogen, nitro, lower alkyl or lower alkoxy, with the proviso that at least one of W and X.sub.2 is halogen; these compounds are particularly useful as color formers in pressure-sensitive or heat-sensitive recording materials.

Pyrrolidino and piperidino benz ring substituted phthalides

Fluoran compounds of the formula ##STR1## wherein one of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represents n-alkyl having 6 to 12 carbon atoms and the other R's, independently of each other, represent hydrogen, alkyl having 1 to 12 carbon atoms, alkoxyalkyl having 2 to 8 carbon atoms or benzyl optionally substituted in the ring by nitro, halogen or alkyl having 1 to 6 carbon atoms. The fluoran compounds are particularly useful as color formers which give intense dark green color when they are brought into contact with an electron-accepting co-reactant.

Fluoran compounds

A 3-indolyl-3-bis-aminophenyl-phthalide compound of the formula ##STR1## wherein R.sub.1 represents alkyl which has at most 12 carbon atoms and is unsubstituted or substituted by halogen, hydroxyl, cyano or lower alkoxy, cycloalkyl, or unsubstituted or substituted phenyl or benzyl wherein the substituents are halogen, nitro, lower alkyl or lower alkoxy,

3-Indolyl-3-bis-amino-phenyl-phthalide compounds

2(Indol-3'-oyl) 3,4,5,6-tetrahalo benzoic acid anhydrides

Phthalides of the formula ##STR1## wherein R.sub.1 and R.sub.2, independently of the other, represent hydrogen, alkyl with 1 to 12 carbon atoms, alkoxyalkyl with 2 to 8 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, benzyl or phenyl, X represents alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or acyloxy with 2 to 12 carbon atoms, Y represents alkyl with 2 to 12 carbon atoms, alkoxy with 3 to 12 carbon atoms or acyloxy with 2 to 12 carbon atoms, Z represents hydrogen, alkyl having 1 to 12 carbon atoms or phenyl, U represents alkyl having 3 to 12 carbon atoms, benzyl or cyanoethyl, or may also represent W when R.sub.1 and R.sub.2 both are benzyl, W represents hydrogen, methyl or ethyl and n is 1 or 2, the benzene rings A and B may be substituted by an amino group optionally substituted by alkyl with 1 to 6 carbon atoms and the benzene ring B may also be substituted by nitro or halogen. The phthalides are particularly useful as color formers which give intense blue colors when they are contacted with an electron-accepting co-reactant such as silton clay or a phenolic resin.

3-Indolyl-3-phenyl-phthalides

An azomethine compound of the general formula ##STR1## wherein A and B, independently of the other, represent naphthylene or phenylene which are unsubstituted or substituted by halogen, cyano, nitro, lower alkyl, lower alkoxy, benzyloxy or phenoxy,

Azomethine compounds

Bis-aminoarylethane compounds of the general formula ##STR1## wherein R.sub.1 and R.sub.2, which can be the same or different, represent hydrogen, alkyl of at most 12 carbon atoms which is unsubstituted or substituted by cyano or halogen, alkoxyalkyl of 2 to 8 carbon atoms, benzyl or phenyl,

Bis-aminoarylethane amide compounds

A process for the manufacture of color formers comprising reaction of 2 moles of an indole in the presence of a condensation agent with about 1 mole of an anhydride of the formula ##STR1## wherein A is the residue of a benzene or naphthalene or of a heterocyclic ring, the new color formers obtained by reacting 2 moles of an indole with a halogen- or nitro-substituted phthalic anhydride, or the anhydride of a vicinal naphthalene pyridine or quinoline dicarboxylic acid, the new 3,3-bis-(indol-3-yl)-phthalides substituted at the nitrogen atom with aralkyl or alkyl with 6 to 18 carbon atoms or alkenyl radicals with 3 to 18 carbon atoms or substituted alkyl or alkylene groups with 1 to 18 and 3 to 18 carbon atoms respectively and pressure sensitive recording paper containing at least one of the new color formers.

Process for the manufacture of color formers of indoles and anhydrides

Indolyl methylene leuco dyestuffs of the formula ##STR1## wherein X.sub.1 and X.sub.2 independently of the other, represent alkyl with 2 to 12 carbon atoms, alkenyl with at most 12 carbon atoms or phenylalkyl with 1 to 4 carbon atoms in the alkyl part, Y.sub.1 and Y.sub.2 independently of the other, represent hydrogen, alkyl with 1 to 12 carbon atoms or phenyl, Z represents alkyl with 1 to 12 carbon atoms, alkenyl with at most 12 carbon atoms, aryl, aralkyl or a heterocyclic residue and the rings A and B may be further substituted by cyano, nitro, halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or acyl with 1 to 8 carbon atoms, said methylene compounds are particularly useful as slow developing color formers in pressure-sensitive recording material and exhibit good light and air stability.

Indolyl methylene leuco dyestuffs

Nitro-phthalides of the formula ##STR1## in which E is a radical of the formula ##STR2## X and X' each represents alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or acyloxy with 2 to 12 carbon atoms, and X may also be hydrogen. Z represents hydrogen, alkyl having 1 to 12 carbon atoms or phenyl, Y represents hydrogen, alkyl having 1 to 12 carbon atoms, benzyl or cyanoethyl, R.sub.1, R.sub.2, R.sub.1 ' and R.sub.2 ', independently of the other, represents hydrogen, alkyl with 1 to 12 carbon atoms, alkoxyalkyl with 2 to 8 carbon atoms, cycloalkyl with 5 or 6 carbon atoms, benzyl or phenyl and the benzene ring B may be further substituted by halogen, nitro or an amino group optionally substituted by alkyl with 1 to 6 carbon atoms. The nitro-phthalides are particularly useful as color formers which give intense green, blue-green or blue colors when they are brought into contact with an electron-accepting co-reactant.

Growing community of inventors

Bury, United Kingdom

Robert Garner