Claims
- 1. A process for the preparation of a fluoran compound of the formula ##STR13## wherein R, R.sub.1, R.sub.2 and R.sub.4 are each independently hydrogen, halogen, lower alkyl or lower alkoxy,
- R.sub.3 is hydrogen, halogen, lower alkyl, lower alkoxy or --NX.sub.3 X.sub.4, or (R.sub.1 and R.sub.2) or (R.sub.3 and R.sub.4), each pair together with the carbon atoms to which they are attached, form a fused benzene nucleus,
- X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are each independently hydrogen, alkyl containing not more than 12 carbon atoms which is unsubstituted or substituted by cyano, halogen, hydroxy, tetrahydrofuryl or lower alkoxy, or are cycloalkyl, aryl or aralkyl or (X.sub.1 and X.sub.2) or (X.sub.3 and X.sub.4) are each independently together with the nitrogen to which they are attached a 5- or 6-membered heterocyclic ring, and
- the ring A is unsubstituted by halogen, nitro, lower alkyl, lower alkylthio, lower alkoxy, lower alkoxycarbonyl, amino, mono-lower alkylamino, di-lower alkylamino or lower alkyl carbonylamino,
- which process comprises
- (1) reacting a ketonic acid of the formula ##STR14## with a substituted phenol derivative of the formula ##STR15## wherein Z is hydrogen, lower alkyl, formyl or lower alkanoyl and A, R, R.sub.1, R.sub.2, R.sub.3, R.sub.4, X.sub.1 and X.sub.2 have the given meanings, in concentrated or fuming sulfuric acid or in a mixture thereof at 0.degree. to 120.degree. C.,
- (2) adding the reaction product to an aqueous liquor containing a non-polar organic solvent and a base at a temperature of 50.degree. to 90.degree. C.,
- (3) separating the organic phase and
- (4) removing the organic solvent to obtain the fluoran of the formula (1).
- 2. A process according to claim 1, wherein Z is hydrogen, methyl, ethyl, formyl or acetyl.
- 3. A process according to claim 1, wherein Z is hydrogen or methyl.
- 4. A process according to claim 1, wherein each of R, R.sub.1, R.sub.2 and R.sub.4 independently is hydrogen, methyl, lower alkoxy, bromo or chloro.
- 5. A process according to claim 1, wherein R.sub.3 is halogen, lower alkyl or --NX.sub.3 X.sub.4.
- 6. A process according to claim 1, wherein X.sub.1 and X.sub.2 are lower alkyl, cyano-lower alkyl, cyclohexyl, phenyl, tolyl or benzyl, or --NX.sub.1 X.sub.2 is pyrrolidino or N--C.sub.1 -C.sub.5 -alkyl-N-tetrahydrofurfurylamino.
- 7. A process according to claim 1, wherein X.sub.3 and X.sub.4 are hydrogen, C.sub.1 -C.sub.8 -alkyl, cyclohexyl, phenyl, benzyl, or phenyl or benzyl each substituted by halogen, methyl, methoxy, carbomethoxy or trifluoromethyl.
- 8. A process according to claim 1, wherein the ring A is unsubstituted or substituted by halogen.
- 9. A process according to claim 1, wherein each of R, R.sub.1, R.sub.2 and R.sub.4 independently is hydrogen, chlorine or methyl, each of X.sub.1 and X.sub.2 independently is C.sub.1 -C.sub.8 -alkyl, cyclohexyl, tolyl or benzyl, or --NX.sub.1 X.sub.2 is pyrrolidino or piperidino, R.sub.3 is --NX.sub.3 X.sub.4, X.sub.3 is C.sub.1 -C.sub.8 -alkyl, phenyl, chlorophenyl, trifluoromethylphenyl, tolyl, xylyl or benzyl, X.sub.4 is hydrogen, lower alkyl or benzyl and the ring A is unsubstituted.
- 10. A process according to claim 1, wherein R, R.sub.1 and R.sub.4 are hydrogen, R.sub.2 is hydrogen or methyl, R.sub.3 is --NX.sub.3 X.sub.4, each X.sub.1 and X.sub.2 is lower alkyl or cyclohexyl, or --NX.sub.1 X.sub.2 is pyrrolidino, X.sub.3 is phenyl, tolyl, xylyl, chlorophenyl, trifluoromethylphenyl or benzyl and X.sub.4 is hydrogen, methyl or benzyl.
- 11. A process according to claim 1, wherein the reactant of formula (2) is 2-(4'-diethylamino-2'-hydroxybenzoyl)benzoic acid or 2-(4'-di-n-butylamino-2'-hydroxybenzoyl)-benzoic acid.
- 12. A process according to claim 1, wherein the reactant of formula (3) is 4-phenylamino-3-methyl-1-methoxybenzene, 4-(2',4'-dimethylphenylamino)-3-methyl-1-methoxybenzene, 4-n-octylamino-1-methoxybenzene, 4-dibenzylamino-1-methoxybenzene or 4-tert.butylphenol.
- 13. A process according to claim 1, wherein the reactants of formulae (2) and (3) are 2-(4'-diethylamino-2'-hydroxybenzoyl)benzoic acid and 4-phenylamino-3-methyl-1-methoxybenzene, 4-(2',4'-dimethylphenylamino)-3-methyl-1-methoxybenzene or 4-n-octylamino-1-methoxybenzene.
- 14. A process according to claim 1, wherein the reactants of formulae (2) and (3) are 2-(4'-diethylamino-2'-hydroxybenzoyl)benzoic acid and 4-dibenzylamino-1-methoxybenzene.
- 15. A process according to claim 1, wherein the reactants of formulae (2) and (3) are 2-(4'-di-n-butylamino-2'-hydroxybenzoyl)benzoic acid and 4-phenylamino-3-methyl-1-methoxybenzene.
- 16. A process according to claim 1, wherein the reactants of formulae (2) and (3) are 2-(4'-diethylamino-2'-hydroxybenzoyl)benzoic acid and 4-tert.butylphenol.
- 17. A process according to claim 1, wherein the non-polar organic solvent is toluene or xylene.
- 18. A process according to claim 1, wherein the addition step (2) of the reaction product is carried out at a temperature of 75.degree. to 90.degree. C.
- 19. A process according to claim 1, wherein the base is sodium hydroxide.
- 20. A process according to claim 1, which comprises condensing the ketonic acid of the formula (2) and the phenol derivative of formula (3) in a mixture of concentrated or fuming sulphuric acid at 10.degree. to 40.degree. C., adding the reaction product to an aqueous-organic medium containing toluene or xylene and a base and having a temperature of 70.degree. to 85.degree. C., and subsequently treating with a base at 70.degree. to 85.degree. C., and finally separating the toluene or xylene phase and isolating the fluoran of formula (1) by removing the solvent.
- 21. A process according to claim 15 wherein the compound of formula (1) melts at 180.degree.-182.degree. C.
Priority Claims (1)
Number |
Date |
Country |
Kind |
8913415 |
Jun 1989 |
GBX |
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Parent Case Info
This application is a continuation, of application Ser. No. 536,815, filed Jun. 11, 1990, abandoned.
US Referenced Citations (11)
Foreign Referenced Citations (8)
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Continuations (1)
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Number |
Date |
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Parent |
536815 |
Jun 1990 |
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