Basf Aktiengesellschaft

Andreas Oberlinner

Hans Baumann

Udo Mayer

Andreas Guentner

Rainer Dyllick-Brenzinger

Klaus Grychtol

Friedrich-Wilhelm Raulfs

3-Aminophenylpentane-1,5-diones of the formula I ##STR1## where R.sup.1 and R.sup.2 are, independently of one another, hydrogen, C.sub.1 -C.sub.8 -alkyl, C.sub.4 -C.sub.8 -cycloalkyl, cyano-C.sub.2 -C.sub.4 -alkyl, hydroxy-C.sub.2 -C.sub.4 -alkyl, chloro-C.sub.2 -C.sub.4 -alkyl, phenyl-C.sub.1 -C.sub.2 -alkyl which can be substituted by chlorine, or phenyl which can be substituted by clorine or methyl, or R.sup.1 and R.sup.2 form, together with the nitrogen to which they are bonded, a heterocyclic radical which can contain further hetero atoms,

3-aminophenylpentane-1,5-diones

Benzopyrans of the formula ##STR1## where X is a radical ##STR2## and R.sup.1, R.sup.2, R.sup.3, R.sup.4 and the ring A have the meanings stated in the description, a process for their preparation, and their use in pressure-sensitive or heat-sensitive layers.

Benzopyrans for use in recording systems

Benzopyran derivatives of the formula ##STR1## where X is the radical ##STR2## and R.sup.1, R.sup.2, R.sup.3, R.sup.4 and also the ring A have defined meanings are used in pressure- or heat-sensitive layers.

Benzopyran derivatives

Basic rhodamine dyes suitable for use in recording fluids for the ink jet process and for coloring paper stock have the formula ##STR1## where L is C.sub.2 -C.sub.10 -alkylene,

Basic rhodamine dyes

Carbazole containing benzopyrans

Mixtures of dye precursors which contain (a) the lactone of 2-carboxy-4,4'-bisdimethylaminobenzhydrol (I) and (b) crystal violet lactone and/or one or more fluoran lactones of the formula ##STR1## where R.sup.1 is alkyl, R.sup.2 is alkyl, phenalkyl, unsubstituted or substituted phenyl or cycloalkyl, or ##STR2## is pyrrolidinyl, piperidinyl or morpholinyl, R.sup.3 is H or tert.-butyl, R.sup.4 is H or methyl, R.sup.5 is H, alkyl or phenalkyl and R.sup.6 is H, alkyl, phenalkyl, cycloalkyl or unsubstituted or substituted phenyl, or ##STR3## is pyrrolidinyl, piperidinyl or morpholinyl, possess improved lightfastness in pressure-sensitive recording systems.

Mixtures of dye precursors, and pressure-sensitive recording material

Novel compounds of the general formula I ##STR1## where A.sup..crclbar. is an anion, R is hydrogen or unsubstituted or substituted alkyl or cycloalkyl, R.sup.1 and R.sup.2 independently of one another are each hydrogen or unsubstituted or substituted alkyl or cycloalkyl, or one of the radicals may furthermore be aryl, or R.sup.1 and R.sup.2, together with the nitrogen atom, form a saturated heterocyclic structure, the radicals R.sup.3 independently of one another are each hydrogen or C.sub.1 -C.sub.4 -alkyl, R.sup.4 and R.sup.5 independently of one another are each unsubstituted or substituted alkyl or cycloalkyl, or one of the radicals may furthermore be hydrogen, aryl or hetaryl, R.sup.4 and R.sup.5, together with the nitrogen atom, form a saturated heterocyclic structure, n is 1, 2 or 3, X is hydrogen, chlorine, bromine, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or nitro and Y is hydrogen or chlorine, are particularly useful for dyeing paper stocks.

Rhodamine dyes

Dye-forming components of the general formula ##STR1## where A is the radical of a fused benzo ring or 2,1-naphthalene ring, and either radical may be substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, nitro, chlorine, bromine or C.sub.1 -C.sub.6 -alkoxycarbonyl, R.sup.1 is C.sub.1 -C.sub.16 -alkyl, C.sub.7 -C.sub.10 -phenylalkyl or phenyl which is unsubstituted or substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, chlorine or bromine, and R.sup.2 and R.sup.3 independently of one another are hydrogen, C.sub.1 -C.sub.12 -alkyl, C.sub.2 -C.sub.4 -alkyl, which is substituted by cyano, chlorine, methoxy or ethoxy, C.sub.5 -C.sub.7 -cycloalkyl, C.sub.7 -C.sub.10 -phenylalkyl or trimethylene which is unsubstituted or substituted by 1, 2 or 3 methyl groups and is bonded to the carbon in the 6- and/or 8-position of the benzo ring, or R.sup.2 is C.sub.1 -C.sub.4 -alkyl and R.sup.3 is phenyl which is unsubstituted or substituted by chlorine, bromine, C.sub.1 -C.sub.3 -alkyl, methoxy or ethoxy, or R.sup.2 is benzyl and R.sup.3 is .beta.-cyanoethyl, or ##STR2## is morpholinyl, pyrrolidinyl, N'--C.sub.1 -C.sub.4 -alkylpiperazinyl or isoindolinyl. In contact with paper coated with electron acceptors the compounds (I) give violet or blue to green colorations, while on uncoated paper virtually no color is developed. The compounds (I) may be used as dye-forming components for pressure-sensitive recording or copying materials.

Spirodibenzopyrans

Fluorans of the formula (I) ##STR1## where R.sup.1 is hydrogen or methyl, R.sup.2 is hydrogen or unsubstituted or substituted alkyl, R.sup.3 is hydrogen, unsubstituted or substituted alkyl, cycloalkyl or unsubstituted or substituted phenyl, or ##STR2## is a 5-membered or 6-membered saturated heterocyclic radical, R.sup.4 and R.sup.5 independently of one another are each hydrogen, alkyl, alkoxy or halogen, R.sup.6 is hydrogen, halogen, alkyl, alkoxy, phenylalkoxy, phenoxy, phenyl or unsubstituted or substituted amino, or is pyrrolidinyl, piperidinyl or morpholinyl, R.sup.7 is hydrogen, alkyl or halogen, R.sup.8 is C.sub.1 -C.sub.5 -alkyl, and the radicals R.sup.4 and R.sup.5 and/or R.sup.6 and R.sup.7 together may furthermore each be a --CH.dbd.CH--CH.dbd.CH-- bridge, and the fused-on benzo ring may be further substituted, are used for the preparation of pressure-sensitive and heat-sensitive recording materials.

Fluoran colorants for recording systems

Dye intermediates of the formula ##STR1## where R.sup.1 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, methoxy, ethoxy, chlorine or bromine, or phenylalkyl of 7 to 10 carbon atoms, R.sup.2 is hydrogen or R.sup.1 and R.sup.2 together are dimethylene, trimethylene or tetramethylene, which are unsubstituted or substituted by alkyl of 1 to 12 carbon atoms, R.sup.3 and R.sup.5 are hydrogen, alkyl of 1 to 12 carbon atoms, cyano-, chlorine-, methoxy- or ethoxy-substituted alkyl of 2 to 4 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenylalkyl of 7 to 10 carbon atoms or trimethylene which is unsubstituted or substituted by 1 to 3 methyl and is bonded to the carbon atom in the 6-position or 6'-position of the benzene ring, R.sup.4 and R.sup.6 are alkyl of 1 to 12 carbon atoms, cyano-, chlorine-, methoxy- or ethoxy-substituted alkyl of 2 to 4 carbon atoms, phenylalkyl of 7 to 10 carbon atoms, phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, chlorine or bromine, or trimethylene bonded to the carbon atom in the 8-position or 8'-position of the benzene ring, or one or both of the groups ##STR2## are a pyrrolidine, piperidine, morpholine, thiomorpholine, N'-alkylpiperazine (alkyl being of 1 to 4 carbon atoms) or isoindoline radical, and the substituents R.sup.3, R.sup.4, R.sup.5 and R may be identical or different and the rings A and A' may be substituted by alkyl of 1 to 3 carbon atoms. The dye intermediates give deep bluish-green to green colorations with electron-attracting substances and may be used for the manufacture of pressure-sensitive recording materials.

7,7'-Diamino derivatives of 2,2'-spirodibenzopyranes

Dye intermediates of the formula ##STR1## where R.sup.1 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, methoxy, ethoxy, chlorine or bromine, or phenylalkyl of 7 to 10 carbon atoms, R.sup.2 is hydrogen or R.sup.1 and R.sup.2 together are dimethylene, trimethylene or tetramethylene, which are unsubstituted or substituted by alkyl of 1 to 12 carbon atoms, R.sup.3 and R.sup.5 are hydrogen, alkyl of 1 to 12 carbon atoms, cyano-, chlorine-, methoxy- or ethoxy-substituted alkyl of 2 to 4 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenylalkyl of 7 to 10 carbon atoms or trimethylene which is unsubstituted or substituted by 1 to 3 methyl and is bonded to the carbon atom in the 6-position or 6'-position of the benzene ring, R.sup.4 and R.sup.6 are alkyl of 1 to 12 carbon atoms, cyano-, chlorine-, methoxy- or ethoxy-substituted alkyl of 2 to 4 carbon atoms, phenylalkyl of 7 to 10 carbon atoms, phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, chlorine or bromine, or trimethylene bonded to the carbon atom in the 8-position or 8'-position of the benzene ring, or one or both of the groups ##STR2## are a pyrrolidine, piperidine, morpholine, thiomorpholine, N'-alkylpiperazine (alkyl being of 1 to 4 carbon atoms) or iso-indoline radical, and the substituents R.sup.3, R.sup.4, R.sup.5 and R.sup.6 may be identical or different and the rings A and A' may be substituted by alkyl of 1 to 3 carbon atoms. The dye intermediates give deep bluish-green to green colorations with electron-attracting substances and may be used for the manufacture of pressure-sensitive recording materials.

Spirodipyrans of the formula ##STR1## where A is the radical of a fused benzene ring or 2,1-naphthalene ring, the rings being unsubstituted or substituted by alkyl, alkoxy, nitro, chlorine, bromine or carbalkoxy,

Spirodipyrans

A pressure-sensitive recording material which comprises a substrate bearing a dye-forming component and a binder. The dye-forming component is a spirodipyran of the formula ##STR1## where A is the radical of a fused benzene or naphthalene ring (which rings may or may not be substituted), R.sup.1 is alkyl of 1 to 16 carbon atoms, substituted or unsubstituted phenyl or phenalkyl of 7 to 10 carbon atoms, R.sup.2 is H or together with R.sup.1 is a trimethylene or tetramethylene bridge which is unsubstituted or substituted by from 1 to 3 alkyl, R.sup.3 is benzyl or .beta.-phenylethyl and R.sup.4 is benzyl, .beta.-phenylethyl or substituted or unsubstituted phenyl, or R.sup.3 is alkyl of 1 to 4 carbon atoms and R.sup.4 is substituted or unsubstituted phenyl or R.sup.3 is benzyl and R.sup.4 is .beta.-cyanoethyl. The recording materials give violet to bluish green colorations (copies) only on paper coated with an electron acceptor.

Pressure-sensitive recording material

An azo compound useful in copying processes of the formula ##STR1## where R.sup.1 is hydrogen or alkyl of 1 to 4 carbon atoms, R.sup.2 and R.sup.3 are each alkyl of 1 to 4 carbon atoms, or one of the radicals R.sup.1, R.sup.2 and R.sup.3 is unsubstituted phenyl or phenyl substituted by alkyl of 1 to 4 carbon atoms, methoxy or ethoxy, and A denotes ##STR2## where R.sup.4 and R.sup.5 are each hydrogen; alkyl of 1 to 8 carbon atoms which may be substituted by hydroxy, alkoxy, halogen or alkoxycarbonyl; cyanoethyl; alkylcarbonyl with 1 to 3 carbon atoms in the alkyl; cyclohexyl; phenalkyl of 7 to 10 carbon atoms; or substituted or unsubstituted phenyl, or R.sup.4 is N,N-dialkylaminoalkyl or N,N-bisphenalkylaminoalkyl, or the group ##STR3## is a 5-membered or 6-membered saturated heterocyclic ring which may contain an --O-- or --S-- group as ring member, Y is hydroxy, alkyl, alkoxy, chlorine, bromine or alkylcarbonylamino, n is 0, 1 or 2, R.sup.6 and R.sup.7 are each hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl or unsubstituted phenyl or phenyl substituted by alkyl or alkoxy, and Z is hydrogen, hydroxy, methoxy, ethoxy or a sulfonic acid group. The light absorption of the yellow to orange colored compounds (I) is displaced, upon protonation of the compounds, by 150 to 200 nm toward the longer wavelength range, i.e. the salts are violet to blue in color. The compounds (I) are suitable for the production of pressure-sensitive n.c.r. papers.

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Ludwigshafen, Germany

Andreas Oberlinner