GB2072163A - Triaryl Methane Compounds - Google Patents

Triaryl Methane Compounds Download PDF

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GB2072163A
GB2072163A GB8104047A GB8104047A GB2072163A GB 2072163 A GB2072163 A GB 2072163A GB 8104047 A GB8104047 A GB 8104047A GB 8104047 A GB8104047 A GB 8104047A GB 2072163 A GB2072163 A GB 2072163A
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formula
compound
alkyl
aryl
radical
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B41M5/1366—Organic colour formers, e.g. leuco dyes characterised solely by tri (aryl or hetaryl)methane derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
    • C07C273/1863—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety from urea
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C09B11/16—Preparation from diarylketones or diarylcarbinols, e.g. benzhydrol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for the production of a compound of formula <IMAGE> which comprises reacting a compound of formula <IMAGE> or a mixture of the compounds (2a) and (2b) with a compound ZH or a compound of formula <IMAGE> or <IMAGE> or a mixture of the compounds (2c) and (2d) with a compound YH, both reactions under acidic conditions, wherein X and Y are the same or different and each represents an aromatic carbocyclic radical having an unsubstituted or substituted amino group in the para position to the indicated bond, or a heterocyclic group, and Z represents an aryl radical of formula <IMAGE> wherein R1 and R2 independently of one another represent hydrogen, C1-C12- alkyl, C2-C8-alkoxyalkyl, cycloalkyl, aralkyl, aryl, or substituted alkyl, cycloalkyl, aralkyl or aryl, or R1 and R2 together with the nitrogen atom which links them represent a five- or six- membered, preferably saturated, heterocyclic radical and W represents hydroxy, alkoxy, aryloxy, amino or substituted amino, and the aromatic carbocyclic radical of formula (1a) or (1b) may be further substituted by one or more halogen, cyano, nitro, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, V represents oxygen, sulphur or imino and T1 and T2 independently represent hydrogen, C1-C12-alkyl, C2-C12- alkenyl, aryl, aralkyl, and T1 also amido or ureido, or T1 and T2 together with the nitrogen atom which links them represent a five- or six-membered heterocyclic radical.

Description

SPECIFICATION Process for the Production of Triaryl Methane Compounds The present invention relates to the production of triaryl methane compounds. More particularly it relates to the production of triaryl methane compounds containing a carbocyclic moiety which contains a carboxylic acid group which, on oxidation, forms a lactone ring, giving a comound which can be used as a colour former.
Accordingly, the invention provides a process for the production of a compound of formula
wherein X and Y may be the same or different and each represents an aromatic carbocyclic radical having an unsubstituted or substituted amino group in the para position to the indicated bond, or a heterocyclic group, and Z represents an aryl radical of formula
wherein R, and R2 independently of one another represent hydrogen, C1-C12-alkyl, C2-C8-alkoxyalkyl, cycloalky, aralkyl, aryl, or .substituted alkyl, cyclo-alkyl, aralkyl oraryl, or R, and Rttogether with the nitrogen atom which links then represent a five- or six-membered, preferably saturated, heterocyclic radical and W represents hydroxy, alkoxy, aryloxy, amino or substituted amino, and the aromatic carbocyclic radical of formula (ia) or (1 b) may be further substituted by one or more halogen, cyano, nitro, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.
The process of the present invention comprises reacting a compound of formula
or a mixture of the compounds (2a) and (2b) with a compound ZH or a compound of formula
or a mixture of the compounds (2c) and (2d) with a compound YH, both reactions under acidic conditions, wherein X, Y and Z have the given meanings and V represents oxygen, sulphur or imino and T, and T2 independently represent hydrogen, C1-C12-alkyl, C2-C12-alkenyl, aryl, aralkyl, and T, also amido or ureido, or T, and T2 together with the nitrogen atom which links them represent a five- or six-membered, preferably saturated, heterocyclic radical.
As an aromatic carbocyclic radical, X and Y may be an amino substituted phenyl radical of formula
wherein R3 and R4 independently represent the groups listed for R, and R2 above, or together represent methylene groups linked to form a heterocyclic ring which may optionally be interrupted by an oxygen, sulphur or nitrogen atom, and R5 and R,, independently, represent hydrogen, hydroxy, halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, C2-C8-alkoxyalkyl, cycloalkyl, aralkyl, aryloxy, arylamino, aryl or a carboxylic acid, carboxylic ester or carboxylic amide group.
As a heterocyclic radical X and Y may represent a mono- or polycyclic (preferably di- or tricyclic) radical containing a 5- or 6-membered heterocyclic ring containing oxygen, sulphur and/or nitrogen as a ring member such as a thienyl, furyl, pyrrolyl, pyrazolyl, pyrazolonyl, pyridyl, thiazinyl, oxazinyl, benzothiazinyl, indolyl, indazolyl, benzothiazolyl, benzotriazolyl, naphthotriazolyl, quinolinyl, carbazolyl, phenothiazinyl or phenoxazinyl radical. The mono- or polynuclear heterocyclic radicals may be substituted by one or more of the groups defined for R5 and Re above.
When X and Y are heterocyclic radical, this is preferably one of the formula
wherein Q, represents hydrogen, C1-C12-alkyl, C2-C12-alkenyl or benzyl and Q2 represents hydrogen, C1-C 12-alkyl, or aryl, e.g. phenyl, and R5 and R8 have the given meanings.
When each of the radicals R, to Re, T,, T2, Q1 and Q2 represent alkyl, they may be straight or branched chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, octyl or dodecyl.
When each of the radicals Rr to Re represent alkoxyalkyl, this may have 1 to 4 carbon atoms in each part, but preferably the alkoxyalkyl radical is P-methoxyethyl or xB-ethoxyethyl.
When O,, T, and T2 represent alkenyl, this may be for example alkyl, 2-methallyl, 2-ethylallyl, 2butenyl or octenyl. Examples of cycloalkyl in the meaning of the R radicals are cyclopentyl or, preferably, cyclohexyl.
An aryl radical represented by the R and T radicals can be diphenyl, naphthyl or, preferably, phenyl. As aralkyl the R and T radicals may be phenylethyl or, preferably, benzyl.
When R1, R2, R3 and R4 represent substituted alkyl, cycloalkyl, aralkyl or aryl, the substituent may be one or more halogen, hydroxy, cyano, alkyl and/or alkoxy groups, the alkyl or alkoxy substituents having 1 to 4 carbon atoms.
When the pair of substituents (R, and R2), (R3 and R4) and (T, and T2), together with the nitrogen atom to which said pair is attached, form a heterocyclic radical, this is for example pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino or piperazino.
The reaction to produce compounds of formula (1 ) from compounds of formula (2a) to (2d) is carried out under acidic conditions. Any non-oxidising strong inorganic or organic acid may be used, for example, hydrochloric, sulphuric, phosphoric, formic, acetic, mono, di- or trichloroacetic, benzenesulphonic, p-toluene sulphonic or oxalic acid. The acid may be anhydrous or aqueous.
The reaction may optionally be carried out in the presence of an alcoholic solvent, e.g. methanol or ethanol.
The reaction may be carried out at an elevated temperature, e.g. at a temperature from 20 to 1 00 C, preferably from 80 to 1 000C.
The compounds of formulae (2a) to (2d) may be made by various routes, starting from the basic urea derivative of formula
wherein R,, T2 and V have the given meanings.
This compound may be reacted under acidic conditions with one or two molar equivalents of an aldehyde which is XCHO, YCH0 or ZOHO and one or two molar equivalents of a compound XH, YH or ZH having an active hydrogen atom, wherein X, Y and Z have the given meanings. Sufficient acid shouid be used to protonate the amino groups in the radicals X and Y or X and Z in compounds of formulae (2a) to (2d) above.
This reaction may be carried out between ambient temperature and 1 000C, optionally in the presence of an organic solvent, such as an alcohol, e.g. methanol or isopropanol.
Suitable acids include hydrochloric, sulphuric, phosphoric, mono-, di- or trichloroacetic, benzenesulphonic or p-toluenesulphonic acid.
For example, p-dimethylaminobenzaldehyde of formula (4) may be reacted with urea and N,Ndimethylaniline in the presence of an acid to form 1 ,3-bis[(p-dimethylamino-diphenyl)methyl] urea of formula (5) according to the following scheme
Generally, a mixture of the compound of the formula (5) and of the compound of formula
is obtained. The weight ratio of the compound of formula (5) to the compound of formula (5a) in advantageously between 1:9 to 9:1, preferably between 1:2 to 2:1.
The resulting compound of formula (5) or the mixture of the compounds of formulae (5) and (5a) can then be reacted with m-dimethylaminobenzoic acid in the presence of an acid to give the leuco triarylmethane of formula
commonly known as Leuco Crystal Violet Lacton, which on oxidation produces the colour former Crystal Violet Lactone.
Instead of the above reaction sequence N,N-dimethylaniline in the first reaction can be replaced by m-dimethylaminobenzoic acid, and in the second reaction N,N-dimethylaniline could be used in place of the m-dimethylaminobenzoic acid.
As a third alternative, in the first reaction, the p-dimethylamino-benzaldehyde may be replaced by the aldehyde of formula
and in the second reaction, N,N-dimethylaniline could be used in place of the m-dimethylaminobenzoic acid. All three reaction schemes lead to the same product.
In each of the three schemes it is preferred to use an excess of the active hydrogen compound in the first stage and remove the excess by filtration or steam distillation before the second stage is carried out.
The benzaldehyde derivatives used in these.reaction schemes can be easily prepared by the socalled Vilsmeier-Haack synthesis (Ber. 1927, 60, 119). It is not always necessary to isolate the aldehyde before reacting it with urea and the active hydrogen compound.
Compounds of formula (2a) in which X and Y are aromatic carbocyclic radicals can also be prepared by reacting the urea compound of formula (3) under acidic conditions optionally in the presence of an organic solvent, such as an alcohol or ketone, e.g. methanol, isopropanol or acetone, with a benzhydrol of formula
where the benzene rings may be further substituted by one or more halogen, cyano, nitro, alkyl and/or alkoxy substituents having 1 to 4 carbon atoms, and in which R7, R8 R, and Rro each independently represent C1-C12-alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl, in which the alkoxy group has 2 to 8 carbon atoms, or substituted alkyl, cycloalkyl, aralkyl or aryl.
Sufficient benzhydrol may be used to produce the compound of formula (2a) directly or only enough to react with one NH2-group of the urea may be used. The resulting intermediate may then be reacted with more benzhydrol or with an aldehyde and active hydrogen compound as above to react with the other NH2 group on the urea.
Suitable acids include hydrochloric, sulphuric, phosphoric, formic, mono-, di-, trichloroacetic acid, benzenesulphonic, p-toluene sulphonic or oxalic acid. Mineral acids are preferred on cost grounds.
The resulting compound of formula (2a) is then reacted under acidic conditions with a compound ZH to produce the compound of formula (1).
Since the compounds of formulae (2a) to (2d) can readily be isolated in crystalline form from the reaction mixture, the resulting compounds of formula (1) and colour formers produced from them can be obtained in a very pure form. For example, 4,4'-bis (dimethylamino) benzhydrol (commonly known as Michler's Hydrol) which is used as starting material in the production of Crystal Violet Lactone can contain, when prepared by the oxidation route from 4,4'-bis (dimethylamino-diphenyl) methane, such impurities as the unchanged methane base, tetramethylbenzidine, the corresponding ketone (Michler's ketone! and a hydrol ether. One or more of these impurities are often found in the resulting Crystal Violet Lactone. These impurities, however, are not present when the compound of formula (2a) to (2d) is used and hence do not appear in the f;nal product.
An impurity that is formed concurrent with compounds of the formula (2a) to (2d) is Leuco Crystal Violet. As this may have a detrimental effect on the properties of Crystal Violet Lactone it is an advantage to remove this compound. This impurity can readily be removed by solvent extraction with a water immiscible solvent, e.g. an aromatic hydrocarbon such as toluene, either on the compounds of formula (2a) to (2d) themselves or on the aqueous alkaline solution of Leuco Crystal Violet Lactone prepared from compounds (2a) to (2d). If this treatment is carried out then the final Crystal Violet Lactone need not be recrystallised from an organic solvent (with subsequent loss in yield) to obtain it in the necessary state of purity for use as a colour former.
A further advantage of the process of the invention is that the products of formula (1) are obtained in higher yields than by conventional methods.
In the examples which follow, the percentages quoted relate to weight, unless otherwise indicated.
Example 1 32 g of 4-Dimethyíaminobenzaldehyde are dissolved in 95 ml of 28% hydrochloric acid, 6 g of urea are added at room temperature followed by 31.5 g of N,N-dimethylaniline. Afterwards the mixture is stirred at room temperature until the reaction has finished. The reaction mixture is then added dropwise with good agitation to excess iced water containing 100 ml of ammonia 30%. The excess N,N dimethylaniline is removed by steam distillation (keeping the distillation mass alkaline to Brilliant Yellow paper throughout by addition of sodium hydroxide solution as required). The aqueous distillation residue is cooled to room temperature. The afforded 1 ,3-bis(4',4"-dimethylamino-diphenyl-methyl) urea is filtered off, washed with methanol and water, and dried: yield 50 g.
The urea derivative from above is charged into 345 ml of sulphuric acid 10.5% wt/vol. 30 g of mdimethylaminobenzoic acid are added and the mixture is heated at 95-1 000C for 3 hours. The reaction mixture is then cooled to 50C by the addition of ice/water and the pH adjusted to around 5 with ammonia 30% (ca 45 ml). The mixture is stirred for 45 minutes then heated to 750C and maintained at 750C for 30 minutes. The resulting 2-(4,4'-bis-dimethylaminobenzhydryl)-5dimethylaminobenzoic acid (Leuco Crystal Violet Lactone) is filtered off and washed sulphate-free with hot water and dried: yield 58 g.
Example 2 185 g of phosphorus oxychloride are added with good agitation over 1-2 hours at or below 250C to 110 g of dry dimethylformamide and the complex is stirred for a further 15 minutes. Then 140 g of N,N-dimethylaniline are run in over 2 hours at or below 45 OC and the mixture is stirred for 30 minutes and then heated to 1000C and maintained at 1000C for 2 hours and cooled to 500C. 70 g of ice are added carefully, followed by 105 g of hydrochloric acid (36%) and 30 g of urea and the whole is stirred for 1 5 minutes. Afterwards 157,5 of N,N-dimethylaniline are run in and the mixture is stirred overnight at room temperature, then heated to 600C and maintained at 600C for 2 hours. 760 g of iced water are then added and the mixture is neutralised with aqueous sodium hydroxide. The resulting mixture of 1,3-bis(4',4g-dimethylaminodiphenyl-methyl) urea and 1-(4',4"-dimethylamino- diphenylmethyl) urea (1:1) is filtered off, washed with methanol and water and dried: yield 225 g. The resulting urea derivative mixture is converted into Leuco Crystal Violet Lactone by reaction with mdimethylamino benzoic acid as described in Example 1.
Example 3 10.8 g of 4,4'-bis(dimethylamino) benzhydrol, in the form of a technical quality aqueous paste, 1.2 g of urea and 0.7 g of sulphuric acid 98% are added to 100 ml of methanol and the mixture is stirred overnight at ambient temperature. The reaction mass is neutralised with dilute ammonia and the resulting mixture of 1 ,3-bis(4',4',-dimethylamino-diphenyl-methyl) urea and 1 -(4',4"- dimethylamino-diphenyl-methyl) urea is filtered off, washed with methanol, with water and dried, (yield: 11.4 g). The resulting urea derivative mixture is converted into Leuco Crystal Violet Lactone by reaction with M-dimethylaminobenzoic acid as described in Example 1.
Example 4 32 g of 4-dimethylamino-benzaldehyde and 6 g of urea are added to 95 ml hydrochloric acid 28%. The mixture is cooled to 15 C and stirred to dissolve. Afterwards 39 g of mdimethylaminobenzoic acid are added and the mixture is heated at 1000C until no further reaction occurs. 95 ml of water are added and the aqueous mixture is neutralised with sodium hydroxide. The mixture of 1 ,3-bis[4'-dimethylamino-phenyl-(4"-dimethylaminophenyl-2"-carboxylic acid) methyl] urea and 1-(4'-dimethylamino-phenyl-(4"-dimethylamino-phenyl-2"-carboxylic acid) methyl] urea (1:1) is filtered off and washed successively with water, methanol and water and dried: yield 7 g. The urea derivative mixture is then converted into Leuco Crystal Violet Lactone by reaction with 2.8 g of N,Ndimethylaniline by the procedure described in Example 1.
Example 5 Leuco Crystal Violet can be removed from Leuco Crystal Violet Lactone in the following manner.
Leuco Crystal Violet Lactone (20.4 g) obtained as described in Example 1 is added to 200 ml water and sodium hydroxide (3.0 g) added. The reaction mixture is stirred, heated to 800C., and maintained until dissolution occurs. This solution is extracted with toluene to remove Leuco Crystal Violet. The resulting aqueous solution of purified Leuco Crystal Violet Lactone can now be oxidised in the usual manner to give Crystal Violet Lactone.

Claims (9)

Claims
1. A process for the production of a compound of formula
which comprises reacting a compound of formula
or a mixture of the compounds (2a) and (2b) with a compound ZH or a compound of formula
or a mixture of the compounds (2c) and (2d) with a compound YH, both reactions under acidic conditions, wherein X and Y are the same or different and each represents an aromatic carbocyclic radical having an unsubstituted or substituted amino group in the para position to the indicated bond, or a heterocyclic group, and Z represents an aryl radical of formula
wherein R1 and R2 independently of one another represent hydrogen, C1-C12-alkyl, C2-C8-alkoxyalkyl, cycloalkyl, aralkyl, aryl, or substituted alkyl, cycloalkyl, aralkyl or aryl, or R, an R2 together with the nitrogen atom which links them represent a five or six-membered heterocyclic radical and W represents hydroxy, alkoxy, aryloxy, amino or substituted amino, and the aromatic carbocyclic radical of formula (1 a) or (1 b) may be further substituted by one or more halogen, cyano, nitro, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, V represents oxygen, sulphur or imino and T, and T2 independently represent hydrogen, C1-C12-alkyl, C2-C12-alkenyl, aryl, aralkyl, and T, also amido or ureido, or T, and T2 together with the nitrogen atom which links them represent a five- or six-membered heterocyclic radical.
2. A process according to claim 1, wherein a compound of formula (2a) or (2b) is reacted with a compound ZH, or a compound of formula (2c) or (2d) is reacted with a compound YH.
3. A process according to claim 1 or 2, wherein X and Y independently represent an amino substituted phenyl radical of formula
wherein R3 and R4 independently represent the groups listed for R, and R2 in claim 1, or together represent methylene groups linked to form a heterocyclic ring which may optionally be interrupted by an oxygen, sulphur or nitrogen atom, and R5 and R gf independently, represent hydrogen, hydroxy, halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, C2Cs-alkoxyalkyl, cycloalkyl, aralkyl, aryl, aryloxy, arylamino, or a carboxylic acid, carboxylic ester or carboxylic amide group.
4. A process according to claim 1 or 2, wherein X and Y independently represent an indolyl radical of the formula
wherein Q, represents hydrogen, C1-C12-alkyl, C2-C12-alkenyl or benzyl and Q2 represents hydrogen, C1-C12-alkyi, or aryl, and Rs and Rff have the meanings given in claim 3.
5. A process according to any one of claims 1 to 4 wherein the compounds of formula (2a) to (2d) and their mixtures are prepared by reacting a compound of the formula
wherein V, T, and T2 are as defined in claim 1, under acidic conditions with one or two molar equivalents of an aldehyde which is X--CHO, Y--CHO or Z--CHO and one or two molar equivalent of a compound XH, YH or ZH, wherein X, Y and Z are as defined in claim 1.
6. A process according to claim 5 wherein p-dimethylaminobenzaldehyde is reacted with urea and N,N-dimethylaniline in the presence of an acid to form N-[4,4'-dimethylamino-diphenyl-methyl] urea or N,N'-bis[4,4'-dimethylamino-diphenyl-methylj urea or a mixture of these urea derivatives.
7. A process according to any one of claims 1 to 6 wherein N-[4,4'-dimethylamino-diphenylmethyl] urea or N,N'-bis[4,4'-dimethylamino-diphenyl-methyl] urea or their mixture is reacted with mdimethylamino-benzoic acid in the presence of an acid to give 2-(4,4'-bis-dimethylamino-benzhydryl)5-dimethylamino benzoic acid.
8. A process according to claim 1, wherein a compound of formula (2a) is used, wherein X and Y are an aromatic carbocyclic radical having an unsubstituted or substituted amino group in the para position and wherein this compound of formula (2a) is produced by reacting a compound of formula (3), as defined in claim 5, under acidic conditions with a benzhydrol of formula
where the benzene rings may be further substituted by one or more halogen, cyano, nitro, alkyl and/or alkoxy substituents having 1 to 4 carbon atoms, and in which R7, R8, Rg and Ro each independently represent C1-C12-alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl, in which the alkoxy group has 2 to 8 carbon atoms, or substituted alkyl, cycloalkyl, aralkyl or aryl.
9. A process as claimed in claim 1, substantially as hereinbefore described with reference to any of the foregoing Examples.
GB8104047A 1980-02-14 1981-02-10 Triaryl methane compounds Expired GB2072163B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0057661A2 (en) * 1981-01-22 1982-08-11 Ciba-Geigy Ag Process for the production of leuco triaryl methane compounds
US4399291A (en) 1981-12-09 1983-08-16 Sterling Drug Inc. Process for the production of substituted aminophthalides
US4528136A (en) * 1981-12-09 1985-07-09 The Hilton-Davis Chemical Co. Process for preparing 2-[bis(aryl)methyl]benzoic acids

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0057661A2 (en) * 1981-01-22 1982-08-11 Ciba-Geigy Ag Process for the production of leuco triaryl methane compounds
EP0057661A3 (en) * 1981-01-22 1982-08-25 Ciba-Geigy Ag Process for the production of leuco triaryl methane compounds
US4399291A (en) 1981-12-09 1983-08-16 Sterling Drug Inc. Process for the production of substituted aminophthalides
US4528136A (en) * 1981-12-09 1985-07-09 The Hilton-Davis Chemical Co. Process for preparing 2-[bis(aryl)methyl]benzoic acids

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