Ciba-geigy Corporation

Davor Bedekovic

Ian J Fletcher

Rox Phaff

Heinz Balli

Sigmund Gunzenhauser

Robert Garner

John Barry Henshall

Brian J Williams

Jerry L Pool

The present invention relates to chromogenic methylenepyrrolines and processes and intermediates for their preparation and to their use. The chromogenic methylenepyrroline compounds according to the invention have the formula (I) defined in claim 1. These colour formers are suitable in particular for thermographic recording processes and produce intensive red, violet, blue or brown colourations. They are distinguished by the fact that they do not require any conventional electron-withdrawing acid colour developer.

Chromogenic methylenepyrrolines

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

Chromogenic phthalides and azaphthalides of the formula ##STR1## in which V.sub.1 and V.sub.2 are each, independently of the other, hydrogen, halogen, lower alkyl, lower alkoxy, (lower)alkoxycarbonyl or --NR.sub.1 R.sub.2, at least one of the radicals V.sub.1 and V.sub.2 being lower alkoxy or --NR.sub.1 R.sub.2, A is an unsubstituted or halogen-, cyano-, nitro-, (lower alkyl)-, (lower alkoxy)-, (lower alkyl)thio-, (lower alkyl)amino- or di(lower) alkyl)amino-substituted benzene, naphthalene, pyridine, quinoline, pyrazine or quinozaline ring, B is a substituted phenyl radical of the formula ##STR2## or a 3-indolyl of the formula ##STR3## Q is ##STR4## --S-- or --O--, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each, independently of the others, hydrogen, unsubstituted or halogen-, hydroxy-, cyano- or (lower alkoxy)-substituted alkyl, cycloalkyl or unsubstituted or ringsubstituted phenalkyl or phenyl, or the substituent pairs (R.sub.1 and R.sub.2) and (R.sub.3 and R.sub.4) are each, independently of each other, together with the nitrogen atom joining them, a five- or six-membered, heterocyclic radical,

Chromogenic phthalides and azaphthalides

Chromogenic phthalides and azaphthalides of the formula ##STR1## in which V.sub.1 and V.sub.2 are each, independently of the other, hydrogen, halogen, lower alkyl, lower alkoxy, (lower alkoxy)carbonyl or --NR.sub.1 R.sub.2, at least one of the radicals V.sub.1 and V.sub.2 being lower alkoxy or --NR.sub.1 R.sub.2, A is an unsubstituted or halogen-, cyano-, nitro-, (lower alkyl)-, (lower alkoxy)-, (lower alkyl)thio-, (lower alkyl)amino- or di(lower alkyl)amino-substituted benzene, naphthalene, pyridine, quinoline, pyrazine or quinoxaline ring, B is a substituted phenyl radical of the formula ##STR2## or a 3-indolyl of the formula ##STR3## Q is ##STR4## --S-- or --O--, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each, independently of the others, hydrogen, unsubstituted or halogen-, hydroxy-, cyano- or (lower alkoxy)-substituted alkyl, cycloalkyl or unsubstituted or ringsubstituted phenalkyl or phenyl, or the substituent pairs (R.sub.1 and R.sub.2) and (R.sub.3 and R.sub.4) are each, independently of each other, together with the nitrogen atom joining them, a five- or six-membered, heterocyclic radical,

Chromogenic phthalides and azaphthalides of the formula ##STR1## in which V.sub.1 and V.sub.2 are each, independently of the other, hydrogen, halogen, lower alkyl, lower alkoxy, (lower alkoxy)carbonyl or --NR.sub.1 R.sub.2, at least one of the radicals V.sub.1 and V.sub.2 being lower alkoxy or --NR.sub.1 R.sub.2, A is an unsubstituted or halogen-, cyano-, nitro-, (lower alkyl)-, (lower alkoxy)-, (lower alkyl)thio-, (lower alkyl)amino- or di(lower alkyl)amino-substituted benzene, naphthalene, pyridine, quinoline, pyrazine or quinoxaline ring, B is a substituted phenyl radical of the formula ##STR2## or a 3-indolyl of the formula ##STR3## Q is ##STR4## --S-- or --O--, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each, independently of the others, hydrogen, unsubstituted or halogen-, hydroxy-, cyano- or (lower alkoxy)-substituted alkyl, cycloalkyl or unsubstituted or ringsubstituted phenalkyl or phenyl, or the substituent pairs (R.sub.1 and R.sub.2) and (R.sub.3 and R.sub.4) are each, independently of each other, together with the nitrogen atom joining them, a five- or six-membered, heterocyclic radical, Y.sub.1 is hydrogen, lower alkyl, cycloalkyl, phenalkyl or phenyl, Y.sub.2 is hydrogen, lower alkyl or phenyl, Z.sub.1 and Z.sub.2 are each, hydrogen, unsubstituted or halogen-, hydroxyl-, cyano- or (lower alkoxy)-substituted alkyl acyl or unsubstituted or substituted benzyl, X is hydrogen, halogen, lower alkyl, C.sub.1 -C.sub.12 -alkoxy, C.sub.1 -C.sub.12 -acyloxy, benzyl, phenyl, benzyloxy, phenyloxy, halogen-, cyano-, (lower alkyl)- or (lower alkoxy)-substituted benzyl or benzyloxy, or the group --NT.sub.1 T.sub.2, T.sub.1 and T.sub.2 are each, independently of the other, hydrogen, lower alkyl, cycloalkyl, unsubstituted or substituted benzyl or acyl and T.sub.1 is also unsubstituted or substituted phenyl, and the benzene nucleus D is unsubstituted or substituted. These phthalides and azaphthalides are suitable in particular for use as color formers in pressure- or heat-sensitive recording materials and produce green, greenish blue, greyish blue, blue or violet-blue colors.

The invention relates to chromogenic 3,3-bisindolyl-4-azaphthalides of the general formula ##STR1## wherein Y.sub.1 is hydrogen, C.sub.1 -C.sub.12 alkyl which is unsubstituted or substituted by halogen, hydroxyl, cyano or lower alkoxy, or is C.sub.1 -C.sub.12 acyl, benzyl or benzyl substituted halogen, nitro, lower alkyl or lower alkoxy,

Recording material containing chromogenic 3,3-bisindolyl-4-azaphthalides

Chromogenic azaphthalides of the formula ##STR1## wherein R.sub.1 and R.sub.2 independently of each other are hydrogen, C.sub.1 -C.sub.12 alkyl which is unsubstituted or substituted by halogen, hydroxyl, cyano or lower alkoxy, or are cycloalkyl, benzyl or phenyl, or benzyl or phenyl which are substituted by halogen, nitro, cyano, lower alkyl, lower alkoxy or lower alkoxycarbonyl; or R.sub.1 and R.sub.2 together with the nitrogen atom to which they are attached are a 5-membered or 6-membered heterocyclic radical and in particular pyrrolidinyl;

Chromogenic dihydrofuropyridinones

The invention relates to ring-substituted 4-azaphthalides of formula ##STR1## wherein Q is a substituted phenyl radical of the formula ##STR2## or a 3-indolyl radical of the formula ##STR3## Y.sub.1 and Y.sub.2 are hydrogen, unsubstituted or substituted alkyl, acyl, or unsubstituted or substituted benzyl,

Ring-substituted 4-azaphthalides

Chromogenic dihydrofuropyridinones of the general formula ##STR1## wherein R.sub.1 and R.sub.2 independently of each other are hydrogen, C.sub.1 -C.sub.12 alkyl which is unsubstituted or substituted by halogen, hydroxyl, cyano or lower alkoxy, or are cycloalkyl, benzyl or phenyl, or benzyl or phenyl which are substituted by halogen, nitro, lower alkyl or lower alkoxy; or R.sub.1 and R.sub.2 together with the nitrogen atom to which they are attached are pyrrolidinyl;

Chromogenic 3,3-bisindolyl-4-azaphthalides

The invention relates to chromogenic dihydroquinazolines of the general formula: ##STR1## wherein: the ring A is a monocyclic or polycyclic, unsubstituted or substituted heterocyclic radical which may contain further heteroatoms as ring members,

Chromogenic dihydroquinazolines

Preparation of chromogenic azaphthalides

The invention relates to chromenoazaindolizines of the general formula ##STR1## wherein each of Y, X.sub.1 and X.sub.2 independently of the other is hydrogen, halogen, lower alkyl, lower alkanoylamino or a group of the formula ##STR2## each of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 independently of the other is hydrogen, C.sub.1 -C.sub.12 alkyl which is unsubstituted or substituted by halogen, hydroxy, cyano or lower alkoxy, or is cycloalkyl, phenyl, benzyl, or phenyl or benzyl each substituted by halogen, nitro, lower alkyl or lower alkoxy, or

Chromenoazaindolizine compounds

The invention relates to chromogenic dihydroquinazolines of the general formula ##STR1## wherein the ring A is a monocyclic or polycyclic, unsubstituted or substituted heterocyclic radical which may contain further heteroatoms as ring members,

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Therwil, Switzerland

Davor Bedekovic