EP0005251B1 - Procédé de préparation de sulfinates de 4,4'-diaminobenzhydrol et de ses produits de substitution, et papier-calque contenant ces produits - Google Patents

Procédé de préparation de sulfinates de 4,4'-diaminobenzhydrol et de ses produits de substitution, et papier-calque contenant ces produits Download PDF

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Publication number
EP0005251B1
EP0005251B1 EP79101293A EP79101293A EP0005251B1 EP 0005251 B1 EP0005251 B1 EP 0005251B1 EP 79101293 A EP79101293 A EP 79101293A EP 79101293 A EP79101293 A EP 79101293A EP 0005251 B1 EP0005251 B1 EP 0005251B1
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Prior art keywords
radical
optionally substituted
general formula
sulphinates
organic solvents
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EP79101293A
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German (de)
English (en)
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EP0005251A2 (fr
EP0005251A3 (en
Inventor
Roderich Dr. Raue
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Bayer AG
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Bayer AG
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    • 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

Definitions

  • the alkyl radicals mentioned in the formulas (I) and (11) are generally those having 1-6 C atoms.
  • the alkyl radicals mentioned under D can have up to 20 carbon atoms.
  • Particularly suitable substituents of the alkyl radicals are, for example, halogen, hydroxy, C 1 -C 4 alkoxy or cyano.
  • Aryl is preferably understood to mean phenyl or 1- or 2-naphthyl and aralkyl is benzyl and ⁇ -phenyl-C 1 -C 4 -alkyl.
  • the phenyl rings can be substituted, for example, by 1-4 radicals such as halogen, C 1 -C 4 alkyl, hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, carboxyl, amidocarbonyl, cyano, nitro, amidosulfonyl, C 1 -C 3 alkylcarbonylamino or benzoylamino.
  • Cycloalkyl is especially cyclopentyl and cyclohexyl, e.g. can be substituted by 1-4 radicals, in particular methyl.
  • heterocyclic rings which are formed by R 1 and R 2 or by R 3 and R 4 with the adjacent nitrogen atom are the piperidine, N-methylpiperazine and the morpholine ring.
  • heterocyclic rings which are formed by R 1 and / or R 2 being bound to the aromatic radical A or by R 3 and / or R 4 being bound to the aromatic radical B are julolidine, lilolidine, N- Methyltetrahydroquinoline and 1,2-dimethylindoline called.
  • a and B preferably represent a 1,4-phenylene or 1,4-naphthylene radical. These radicals can be substituted by 1-4 substituents such as C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen.
  • Halogen is understood to mean in particular fluorine, chlorine and bromine.
  • Suitable hetaryl residues D are e.g. the quinoline (5), quinoline (6) and indazole (7) residues.
  • the process according to the invention is very particularly suitable for the production of sulfinates of Michler's hydrol (4,4'-tetramethyldiaminobenzhydrol).
  • Suitable solvents are monohydric and polyhydric alcohols, and also their ethers, for example methanol, ethanol, propanol, methyl glycol, ethyl glycol, butyl glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol, methyl glycol acetate, ethylene glycol nitrile diacetate, ethylene glycol nitrile diacetate, and ethylene glycol nitrile diacetate, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, ethylene glycol nitrile acetic acid, acetylene glycol acetylene diacetate, acetylene glycol acetylene di
  • Suitable starting materials of the general formula are: 4,4'-diaminobenzhydro !, 4,4'-tetramethyldiaminobenzhydrol, 4,4'-tetraethyldiaminobenzhydrol, 4,4'-tetramethyldiamino-2,2'-dimethoxybenzhydrol, 4,4'-tetramethyldia- mino-2,2'-dimethylbenzhydrol, 4,4'-Bisbenzylmethylaminobenzhydrol, 4,4'-Bisbenzyläthylaminobenzhydrol, 4,4'-Bisdibenzylaminobenzhydrol, 4,4'-Bisphenylmethylaminobenzhydrol, 4,4 '-bis- phenyläthylaminobenzhydrol, 4,4' -Bisäthyloxäthylaminobenzhydrol, 4,4'-Tetrachloräthyldiaminobenzhydr
  • Suitable low-molecular organic mono- or dicarboxylic acids are formic acid, acetic acid, propionic acid, glycolic acid, methoxyacetic acid, ethoxyacetic acid, oxalic acid, maleic acid and succinic acid. Acetic acid is preferred among these carboxylic acids.
  • Suitable sulfinic acids of the formula 111 are, for example, methanesulfinic acid, ethanesulfinic acid, propanesulfinic acid, butanesulfinic acid, decanesulfinic acid, dodecanesulfinic acid, octadecansulfinic acid, benzylsulfinic acid, 4-methylbenzylsulfinic acid, 4-chlorobenzylsulfinic acid, cyclohexylsulfinsulfonic acid, 2-chlorobenzene acid, benzene , 2-methylbenzenesulfinic acid, 4-ethylbenzenesulfinic acid, 4-methoxybenzenesulfinic acid, 4-ethoxybenzenesulfinic acid and 4-acetylaminobenzenesulfinic acid.
  • 4-methylbenzenesulfinic acid is particularly preferred.
  • the reaction can be carried out at a temperature of 20-100 °
  • Suitable solvents are: methanol, isopropanol, ethylene glycol, methyl glycol, ethyl glycol, butyl glycol, methyl glycol acetate, ethylene glycol diacetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, dioxane, tetrahydrofuran and acetonitrile.
  • Lactic acid can be used instead of glycolic acid with the same good result.
  • Michler's hydrol 85 g of Michler's hydrol are dissolved in a mixture of 50 ml of formic acid and 200 ml of ethanol and 50.8 g of sodium p-toluenesulfinate are added. After 10 minutes the sulfinate of Michler's hydrol crystallizes out. The suspension is allowed to stir for 4 hours at room temperature, is filtered off with suction and the reaction product is washed in small portions with 400 ml of alcohol until the filtrate is light, then with 0.5 l of a 1% aqueous sodium sulfinate solution.
  • Suitable hydroles are: 4,4'-tetramethyldiamino-2,2'-dimethoxybenzhydrol, 4,4'-tetramethyl-diamino-2,2'-dimethylbenzhydrol, 4,4'-bisbenzylmethylaminobenzhydrol, 4,4'-bisbenzylethylaminobenzhydrol, 4,4'-Bisdibenzylaminobenzhydrol, 4,4'-Bisphenylmethylaminobenzhydrol, 4,4 '-Bisphenylvesthylaminobenzhydrol, 4,4' -bis- äthyloxäthylaminobenzhydrol, 4,4'-Bischloräthyl- äthylaminobenzhydrol, 4,4'-Bispiperidinobenzhydrol, 4,4 ' -Bismorpholinobenzhydrol, 4,4 ' -Bismorpholinobenzhydrol, 4,4 ' -Bis-

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Color Printing (AREA)

Claims (3)

1. Procédé pour la préparation de sulfinates de formule générale:
Figure imgb0018
dans laquelle A et B représentent indépendamment l'un de l'autre, un reste 1,4-arylène éventuellement substitué, et
Ri, R2, R3 et R4 représentent indépendamment les uns des autres l'hydrogène ou un reste alkyle, cy- cloalkyle, arylalkyle ou aryle éventuellement substitué, ou bien
R1 et R2 ou R3 et R4 forment ensemble avec l'atome d'azote voisin un noyau hétérocyclique, ou bien
un ou plusieurs des restes
R1, R2,R3 et R4 forment avec l'azote et un atome voisin du reste A ou B un noyau hétérocyclique et D représente un reste alkyle, aryle, arylalkyle, cy- cloalkyle ou hétéroaryle,
par réaction de 4,4'-diaminobenzhydrols de formule générale:
Figure imgb0019
et avec des composés de formule:
Figure imgb0020
leurs sels alcalins ou alcalino-terreux en conditions anhydres dans des acides mono- ou dicar- boxyliques et éventuellement d'autres solvants organiques, ce procédé étant caractérisé en ce que l'on précipite les sulfinates par dilution par des solvants organiques anhydres.
2. Procédé selon la revendication 1 pour la préparation de sulfinates de formule générale:
Figure imgb0021
dans laquelle
R5, Rs, R7 et R8 représente indépendamment les uns des autres l'hydrogène ou un reste alkyle en C1-C4 et
R9 et R10 représentent indépendamment l'un de l'autre l'hydrogène, le chlore ou le brome ou un reste méthyle, éthyle, méthoxy ou éthoxy, R représente un reste alkyle en C1-C18 éventuellement substitué par un halogène ou un groupe phényle éventuellement substitué par un halogène ou un groupe méthyle, éthyle, hydroxy, méthoxy, éthoxy, nitro, carboxy ou acétylamino, par réaction de 4,4'-diaminobenzhydrots de formule générale:
Figure imgb0022
avec des composés de formule:
Figure imgb0023
ou leurs sels de métaux alcalins en présence d'acides monocarboxyliques aliphatiques et éventuellement d'autres solvants organiques à l'abri de l'eau, caractérisé en ce que l'on précipite les sulfinates par dilution avec des solvants organiques anhydres.
3. Papiers de copie incolores caractérisés en ce qu'ils contiennent comme composés chromogènes des sulfinates qui ont été préparés par l'un des procédés selon les revendications 1 et 2.
EP79101293A 1978-05-10 1979-04-30 Procédé de préparation de sulfinates de 4,4'-diaminobenzhydrol et de ses produits de substitution, et papier-calque contenant ces produits Expired EP0005251B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19782820486 DE2820486A1 (de) 1978-05-10 1978-05-10 Verfahren zur herstellung von sulfinaten des 4,4'diaminobenzhydrols und seiner substitutionsprodukte
DE2820486 1978-05-10

Publications (3)

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EP0005251A2 EP0005251A2 (fr) 1979-11-14
EP0005251A3 EP0005251A3 (en) 1979-12-12
EP0005251B1 true EP0005251B1 (fr) 1981-01-07

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Country Status (3)

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EP (1) EP0005251B1 (fr)
JP (1) JPS54148762A (fr)
DE (2) DE2820486A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4348330A (en) * 1980-03-14 1982-09-07 Ciba-Geigy Corporation Process for the production of sulphinates of benzhydrol compounds
DE3337296A1 (de) * 1983-10-13 1985-04-25 Bayer Ag, 5090 Leverkusen Thermoreaktives aufzeichnungsmaterial, seine herstellung und die verwendung von sauermodifizierten polymerisaten als akzeptoren in diesem aufzeichnungsmaterial

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193404A (en) * 1959-03-19 1965-07-06 Davis Chester Associated dye salts and method of forming colored indicia therewith
DE2208611A1 (de) * 1972-02-24 1973-09-06 Basf Ag Verfahren zur herstellung von aryleckige klammer auf 4,4'-bis-(dialkylamino)benzhydryl eckige klammer auf -sulfonen

Also Published As

Publication number Publication date
DE2820486A1 (de) 1979-11-15
JPS54148762A (en) 1979-11-21
JPS5735911B2 (fr) 1982-07-31
EP0005251A2 (fr) 1979-11-14
EP0005251A3 (en) 1979-12-12
DE2960119D1 (en) 1981-02-26

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