Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • 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
  • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
  • B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/10—Spiro-condensed systems
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Definitions

• each R represents either a hydrogen atom or a lower alkyl group having from one to five carbon atoms; wherein each R, represents either a hydrogen atom, a substituted or unsubstituted lower alkyl group having from one to five carbon atoms or a substituted or unsubstituted phenyl group; and wherein the pyrazolyl group is attached to the fluoran moiety of either the 6 position or the 7' position of the latter.
• These compounds are generally substantially colorless but capable of becoming highly colored when brought into reactive contact with many conventional Lewis acid materials. Accordingly, these compounds are highly useful as a component of pressure-sensitive copying papers.
• each R represents either a hydrogen atom or a lower alkyl group having from one to five carbon atoms; wherein each R, represents either a hydrogen atom, a substituted or unsubstituted lower alkyl group having from one to five carbon atoms or a substituted or unsubstituted phenyl group; and wherein the pyrazolyl group is attached to the fluoran moiety at either the 6 position or the 7 position of the latter.
• impact or pressure sensitive carbonless transfer papers have recently come into wide usage in the United States and throughout the world. Ordinarily, such papers are printed and collated into manifolded sets capsble of producing multiple copies. in this connection, pressure applied to the top sheet causes a corresponding mark on each of the other sheets of the set.
• the top sheet of paper upon which the impact or pressure is immediately applied, ordinarily has its back surface coated with microscopic capsules containing one of the reactive ingredients which produce a mark.
• a receiver sheet, placed in contact with such back face of the top sheet has its front surface coated with a material having a component reactive with the contents of the capsules so that when capsules are ruptured upon impact by stylus or machine key, the initially colorless or substantially colorless contents of the ruptured capsules react with a coreactant therefor on the receiver sheet and a mark forms on the receiver sheet corresponding to the mark impressed by the stylus or machine key.
• i'm act transfer papers are designated by the terms CB, F8 and CF, which stand respectively for "coated back", coated front and back" and coated front".
• the CB sheet is usually the top sheet and the one on which the impact impression is directly made;
• the CPD sheets are the intermediate sheets, each of which have a mark formed on the front surface thereof and each of which also transmits the 2 contents of ruptured capsules from its back surface to the front of the next succeeding sheet;
• the CF sheet is the last sheet and is only coated on its front surface to have an image formed thereon.
• the CF sheet is not normally coated on its back surface as no further transfer is desired.
• carbonless impact transfer paper and the type with which the compounds of the present invention are preferably utilized, is the type illustrated, for example, in Green (507) and Macaulay (308) wherein microscopic capsules containing a liquid fill comprising a solution of an initially colorless chemically reactive color forming dye precursor are coated on the back surface of the sheet, and a dry coating of a co-reactantchemical for the dye precursor is coated on the front surface of a receiving sheet.
• color precursors disclosed in the patents referred to above are capable of undergoing an acidbase type reaction with an acidic material.
• Other previously known color precursors are the spiro-dipyran compounds disclosed in the patent to Harbort, No. 3,293,060 with specific reference being made to the disclosure of the 060 patent extending from column ll, line 32 through column 12, line 21.
• the color precursors disclosed in the patents listed above are gener ally initially colorless and are capable of becoming highly colored when brought into contact with an acidic layer such as an acid-leached bentonite-type clay or an acid-reacting polymeric material, or the like.
• the color precursor materials disclosed above are dissolved in a solvent and the solution is encapsulated in accordance with the procedures and processes described and disclosed by Macaulay (308) and by Green (507) as mentioned above.
• Other processes for encapsulating color precursors are disclosed in U.S. Pat. No. 3,429,827 to Runs and U.S. Pat. No. 3,578,605 to Baxter. [n this connection, it should be mentioned that the exact nature of the capsule itself is not critical as long as the same is capable of containing the color precursor and can be ruptured by the application of pressure in accordance with conventional carbonless copying procedures.
• Solvents known to be useful in connection with dissolving color precursors include chlorinated biphenyls, vegetable oils (castor oil, coconut oil, cotton seed oil, etc.) esters (dibutyl adipate, dibutyl phthalate, butyl benzyl adipate, benzyl octyl adipate, tricresyl phosphate, trioctyl phosphate, etc.), petroleum derivatives (petroleum spirits, kerosene, mineral oils, etc.), aromatic solvents (benzene, toluene, etc.), silicone oils, or combinations of the foregoing. Particularly useful are the alkylated naphthalene solvents disclosed in U.S. Pat. No. 3,806,463 to Konishi et al.
• the-color precursors are conventionally contained in pressure rupturable microcapsules which are included in the back coatings of the sheets of carbonless copying manifolded sets.
• the acidic coatings are generally utilized as front coatings with the color precursor material in a solvent therefor being transferred from an adjacent back coating to the acidic layer front coating upon rupture of the capsules which contain the color precursor material.
• the present invention is directed to a family of normally substantially colorless chromogenic 3'-amino-6' or 7'-(pyrazol-l-yl) fluoran color precursor compounds having the following structural formula:
• each R represents either a hydrogen atom or a lower alkyl group having from one to five carbon atoms; wherein each R, represents either a hydrogen atom, a substituted or unsubstituted lower alkyl group having from one to five carbon atoms or a substituted or unsubstituted phenyl group; and wherein the pyrazolyl group is attached to the fluoran moiety at either the 6' position or the 7' position of the latter.
• a solid Lewis acid electron acceptor material such as the acid-leached bentonitetype clay disclosed in the application of Baxter, Ser.
• the fluoran compounds of the present invention may be prepared by reacting one mole of an appropriate o-(4-amino-2-hydroxybenzoyl)benzoic acid with one mole of an appropriately substituted l-(hydroxyphenyl)pyrazole compound in the presence of a condensing agent such as sulfuric acid, phosphorus pentoxide, polyphosphoric acid or zinc chloride and in accordance with the following formula:
• R and R are as defined above; wherein the of Hi (approximately 57% HI by weight) and the mixhydroxy group is attached to the phenyl group of the ture was refluxed for 12 to 16 hours.
• the reaction pyrazole compound at either the 3 position or 4 position thereof; and wherein in the product compound, the pyrazolyl group is attached to the fluoran moiety at either the 6' position or 7' position of the latter.
• substituted l-(hydroxyphenyl) pyrazole compound may be produced by treating a corresponding l-(methoxyphenyl)pyrazole compound with Hi and the l- (methoxyphenyl) pyrazole compound may be produced by reacting a methoxy phenyl hydrazine commixture was allowed to cool to room temperature and was then poured into 500 ml of ice water. A sufficient amount of ammonia was added to adjust the pH of the mixture to about 8.0, at which time a large quantity of a grey precipitate appeared. The precipitate was recovered utilizing a Buchner funnel, was washed with distilled water until the wash water was neutral and was air dried in an oven at 90 to ll0C. Approximately 30 gms of 3,5-dimethyl-l-(S-hydroxyphenyl) pyrazole pound with an appropriate diketone in accordance with eredthe following formula:
• EXAMPLE ll 40 gms of 3,5-dimethyl-l-(3-methoxy phenyl) pyrazole produced in accordance with Example I were added to 125 ml of a constant boiling aqueous solution CH5C
• EXAMPLE III 24.4 gms (0.l3 moles) of 3,5-dimethyl-I-(S-hydroxyphenyl) pyrazole produced in accordance with Example ii and 27.0 gms (0.095 moles) of o-(4-diethylamino-2-hydroxy benzoyl) benzoic acid were dissolved in 400 ml of concentrated [4,80] maintained at a temperature of 0 to 10C.
• the temperature of the mixture was raised to room temperature and the reaction was permitted to proceed for approximately 72 hrs.
• the reaction mixture was then poured into 1.500 ml of ice water and a sufficient amount of a 50% NaOH solution was added to make the overall mixture strongly alkaline (pH of l0-l2). During this period ice was added as required to maintain the temperature below room temperature.
• the precipitated solids were extracted with benzene (3 x 800 ml), treated with activated carbon (Darco) and filtered.
• solution A was allowed to cool to room temperature. (When a small quantity of solution A was applied to an acidic clay coating on a paper substrate, a vivid red color appeared.) Then, 3.26 gms of terephthaloyl chloride were added to 10.0 gms of R-300 solvent and this mixture was also warmed slightly on a hot plate until a clear solution (solution B) was .obtained. Solution B was then allowed to cool to room temperature. After solutions A and B were prepared, 100 gms of an aqueous solution containing 2.0 weight percent Elvanol' 50-42 (a commercial product of E. l.
• duPont de Nemours which is a polyvinyl alcohol with 87 to 89% hydrolysis and a viscosity of 35 to 45 cps in a 4% aqueous solution at 20C) were placed in a semi-micro Waring blender and then solutions A and B were mixed together at room temperature and the resultant solution was added to the Elvanol solution in the blender.
• the blender was activated and high shear agitation was continued for about two minutes until an emulsion having a dispersed phase particle size of about 2 to l microns was obtained.
• the aqueous solution containing the Elvanol polyvinyl alcohol formed the continuous phase and the solution containing the R-300 solvent, 3'-diethylamino 6'-(3,5-dimethylpyrazol-l-yl)fluoran and terephthaloyl chloride formed the dispersed phase.
• the emulsion was then transferred to a suitable container such as a beaker and was stirred with a variable speed mechanical stirrer at 300 to 500 rpm while an aqueous solution containing 1.86 gms of diethylentriamlne, L44 gms of sodium carbonate and ml of water was added.
• microcapsules pyryazol-l-yl)fluoran was then brought into contact with an acid-leached bentonite-type clay coating on the surface of another sheet of paper and when an impression was made on the reverse side of the sheet coated containing 3'-diethylamino-6'-(3,5-dimethylwith microcapsules, a corresponding red colored reproduction of such impression immediately appeared on the acid-leached bentonite-type clay coating.
• a chromogenic 3'-amino-(pyrazol-l-yl) fluoran compound having the following structural formula:

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Color Printing (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

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Applications Claiming Priority (2)

Related Child Applications (1)

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ID=27061977

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Citations (2)

Family Cites Families (8)

• 1974
  • 1974-11-21 US US525991A patent/US3929828A/en not_active Expired - Lifetime
• 1975
  • 1975-07-09 US US05/594,287 patent/US3979141A/en not_active Expired - Lifetime
  • 1975-10-03 GB GB4065175A patent/GB1473773A/en not_active Expired
  • 1975-11-10 DE DE19752550365 patent/DE2550365A1/de active Pending
  • 1975-11-13 JP JP50136745A patent/JPS5174024A/ja active Pending
  • 1975-11-13 AU AU86575/75A patent/AU8657575A/en not_active Expired
  • 1975-11-20 BE BE162034A patent/BE835767A/xx unknown
  • 1975-11-20 FR FR7535465A patent/FR2291979A1/fr active Granted
  • 1975-11-20 NL NL7513600A patent/NL7513600A/xx not_active Application Discontinuation
• 1976
  • 1976-12-10 JP JP14861576A patent/JPS52141716A/ja active Pending

Patent Citations (2)

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