US3769302A - Aliphatic amino-substituted flourans - Google Patents

Aliphatic amino-substituted flourans Download PDF

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US3769302A
US3769302A US00792324A US3769302DA US3769302A US 3769302 A US3769302 A US 3769302A US 00792324 A US00792324 A US 00792324A US 3769302D A US3769302D A US 3769302DA US 3769302 A US3769302 A US 3769302A
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chromogenic
diethylaminofluoran
sheet
solution
benzene
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T Hoover
A Wright
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Appvion LLC
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Assigned to APPLETON PAPERS INC. reassignment APPLETON PAPERS INC. MERGER (SEE DOCUMENT FOR DETAILS). FILED 12/1781, EFFECTIVE DATE: 01/02/82 STATE OF INCORP. DE Assignors: GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS), TUVACHE, INC.
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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
    • C09B11/10—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
    • 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

Definitions

  • R and R represent hydrogen radicals and alkyl radicals; and R represents ester, acyl, alkylene and phenyl radicals; said materials assuming a colored form upon reactive contact with a Lewis acid molecule.
  • Examples include 2- carbo-tert-butoxy methylamino] -6'-diethylaminofiuoran;
  • This invention pertains to chromogenic compounds for use in pressure sensitive record material and to an improved mark-forming manifold system incorporating these novel chromogenic compounds. More specifically, this invention pertains to aliphatic-amino-substituted dialkylamino fluorans which have the form of substantially colorless, i.e. white, or slightly colored solids, or approach being colorless when in liquid solution, but which may be converted to dark-colored forms upon reactive contact with appropriate acidic material.
  • This invention further, and in the most preferred embodiment, relates to such chromogenic compounds which, when placed in reactive contact with a Lewis acid material, yield neutral colored, i.e., gray to black, reaction products.
  • neutral-colored reaction products find particular use in pressure-sensitive, mark-forming recording systems by virtue of their having improved stability on exposure to light and improved reproduction capabilities when copied by Xerographic or diazo processes.
  • the chromogenic compounds of the present invention are aliphaticamino-substituted fiuorans.
  • marking in desired areas on support webs or sheets may be accomplished by effecting localized reactive contact between the chromogenic material and the acidic material on or in such a web or sheet, such material being brought thereto by transfer, or originally there, in situthe desired reactive contact forming dark-colored materials in the intended image areas.
  • Pressure-sensitive, mark-forming systems of the prior art include that disclosed in application for Letters Patent No. 392,404, filed Aug. 27, 1964, in the names of Robert E. Miller and Paul S. Phillips, Jr., now abandoned.
  • the above-mentioned patent application provides a marking system of disposing on and/or within sheet support material, mutually reactant but unreacted mark-forming components (at least one component of which is a polymeric material) and a liquid solvent in which each of the markforming components is solublesaid liquid solvent being present in such form that it is maintained isolated by a pressure-rupturable barrier from at least one of the markforrmng components until an application of pressure causes a breach or rupture of the barrier in the area delineated by the pressure pattern.
  • the mark-forming components thereby are brought into reactive contact, producing a distinctive mark.
  • It is a further object of this invention to provide a new and improved mark-forming system which comprises disposing, within a web or upon the surface of a web or sheetsupport-material, unreacted chromogenic material in a location suitable for subsequent reactive contact with an acidic material to produce dark-colored reaction products, thus providing means for making marks of desirable color intensity and hue.
  • R and R represent hydrogen radicals and alkyl radicals having less than five carbon atoms
  • R represents hydrogen, phenyl and alkyl radicals
  • a new composition of matter which comprises a dark-colored product of chemical reaction having a resonant chemical structure and produced by contact of a color-activating material with one of the above-mentioned chromogenic compounds.
  • the color-developing or activating material is an acidic substance useful for converting the chromogenic compounds to colored forms.
  • the method of marking of this invention i.e., the method of developing a dark-colored material from substantially colorless or slightly colored chromogenic compounds, comprises providing a chromogenic compound selected from among the above-mentioned compounds and bringing such chromogenic compound into reactive contact with an acidic color-activating substance, in areas where marking is desired, to produce a dark-colored form of the chromogenic compound by the action thereon of said acidic substance.
  • Acidic materials employed in this invention can be any compound within the definition of a Lewis acid, i.e., any electron acceptor.
  • acidic organic polymers such as phenolic polymers are employed as the acidic material.
  • the novel chromogenic materials exhibit the advantage of improved color stability when they are reacted with such phenolic polymers.
  • Solution formation of solid particles of the polymeric material in a solvent system with the substantially colorless chromogenic compounds permits penetration of the dark-colored reaction product into a porous support sheet, e.g., paper, so that the colored form of the chromogenic material is absorbed into the body of the sheet and is not merely on the surface of the sheet.
  • the absorption feature provides protection against erasure of recorded data by attrition of the surface of a record sheet made in accordance with the present invention.
  • Preferred chromogenic materials of this invention are those which yield, as the dark-colored reaction product with above-described Lewis acids, a neutral, i.e., gray to black substance.
  • a neutral i.e., gray to black substance.
  • Such preferred chromogenic materials are eligible to be used in the preferred pressure sensitive record units and mark-forming units of this invention. It is understood that colors with respect to hue, saturation, and lightness are customarily identified in a largely subjective manner. Neutral colors, i.e., shades which range from gray to black and which are substantially lacking in hue and saturation are also customarily identified in a subjective manner. An observer of the products resulting from reaction between preferred ones of the novel chromogenic materials of this invention and specified Lewisacid reactive materials is immediately aware that such reaction products are substantially neutral in hue.
  • FIG. 1 is a diagrammatic representation of a two-sheet unit manifold, in perspective.
  • the bottom surface of the overlying sheet is supplied on the surface or near the surface with a multiplicity of minute pressure-rupturable microcapsules containing a solution of the novel, substantially colorless, chromogenic component.
  • An acidic component such as an acid clay or a phenolic polymeric material lies within the lower web or undersheet or upon the upper surface of the lower web or undersheet.
  • a colored mark is made by the use of a stylus, a type character, or other pressure-exerting means applied to the twosheet unit manifold.
  • FIG. 2 is a sectional view of the two-sheet unit manifold of FIG. 1. The elements are not to scale and are so-shown in order to more effectively depict their interrelation.
  • the released solution is transferred from the overlying or base-sheet to the receiving surface of the underlying sheet in conformance with the pressure pattern of the writing operation.
  • the drawing shows that the top of the underlying sheet is coated or impregnated with a material reactant with the chromogenic material, e.g., an acid clay or an acidic phenolic polymer material; and that capsules are present on the overlying or base-sheet which capsules contain a liquid solution of chromogenic material.
  • the record material e.g., an acid clay or an acidic phenolic polymer material
  • the capsules can contain the polymeric phenolic material in liquid solution and the receiving surface of the underlying sheet can be supplied with the chromogenic material.
  • the improvement in the system resides in the chromogenic material, which chromogenic material is the novel substance of the instant invention.
  • the chromogenic material located within or upon the sheet; it is possible to incorporate the chromogenic material in a solid, crystalline state in a binder material so that the chromogenic material may be transferred from the overlying sheet, upon the application of pressure, to deposit some of the chromogenic material on the receiving surface of the undersheet, which receiving surface carries a color-activating polymeric material.
  • the chromogenic substance is dissolved in an appropriate solvent and minute droplets of the solution of the chromogenic material are encapsulated in minute, rupturable, capsules.
  • the polymeric mark-forming components should have a common solubility with the novel chromogenic material in at least one liquid solvent when the acid-reacting material is a phenolic or other acidic organic polymer. It is also noted that in a single system several chromogenic materials may be used with the same or different polymeric materials. Several polymeric materials can be reactively contacted with a single chromogenic compound or with a mixture of chromogenic compounds.
  • the solvent can be maintained in physical isolation in minute droplets until such time as it is released by application of pressure. This may be accomplished by several known techniques, but, preferably, isolation is maintained by encapsulation of individual droplets of the solvent in a microcapsule according to the procedures described, for example, in US. Pats. Nos. 2,712,507, issued July 5, 1955, on the application of Barrett K. Green; 2,730,457 issued Jan. 10, 1956, on the application of Barrett K. Green and Lowell Schleicher; 2,800,457 issued July 23, 1957, on the application of Barrett K. Green and Lowell Schleicher; 2,800,458 issued July 23, 1957, on the application of Barrett K. Green, reissued as Re. Pat. No. 24,899 on Nov.
  • the microscopic capsules when disposed within or upon a supporting web as a multiplicity in contiguous juxtaposition, are rupturable by pressure, such as normal marking pressure found, for example, in writing or typing operations.
  • the material or materials chosen as the wall material for the droplet-containing microcapsules in addition to being pressure rupturable, must be inert or unreactive with respect to the intended contents of the capsules and the other mark-forming components so that the capsule wall material will remain intact under normal storage conditions until such time as it is released by an application of marking pressure.
  • Preferred examples of eligible capsule wall materials include gelatin, gum arabic and many others thoroughly described in the aforementioned patents.
  • the capsule size should not exceed about 50 microns in diameter.
  • the capsules should be smaller than about microns in diameter.
  • the acidic organic polymeric material useful for developing the color of novel chromogenic compounds in this invention include phenolic polymers, phenol acetylene polymers, maleic acid-rosin resins, partially or wholly hydrolyzed styrene-maleic anhydride copolymers and ethylene-maleic anhydride copolymers, carboxy polymethylene and wholly or partially hydrolyzed vinylmethylether-maleic anhydride copolymer and mixtures thereof.
  • phenolic polymers found useful include alkyl-phenol acetylene resins, which are soluble in common organic solvents and possess permanent fusibility in the absence of being treated by cross-linking materials.
  • Another specific group of useful phenolic polymers are members of the type commonly referred to as novolacs (a type of phenol-formaldehyde polymeric material) which are characterized by solubility in common organic solvents and which are, in the absence of cross-linking agents, permanently fusible.
  • Resol resins if they are still soluble, may be used, though they are subject to change in properties upon aging.
  • phenolic polymer material found useful in practicing this invention is characterized by the presence of hydroxyl groups and by the absence of groups such as methylol,
  • a laboratory method useful in the selection of suitable phenolic resins is the determination of the infra red absorption pattern. It has been found that phenolic resins which undergo absorption in the 32003500 cmr region (which is indicative of hydroxyl groups) on the resin molecules and which do not absorb in the l6001700 cm. region are eligible. This latter absorption region is indicative of desensitization of hydroxyl groups which desensitization renders such groups unavailable for reaction with the chromogenic materials.
  • the acidic material used as a mark-forming component in the present invention is one of the aforementioned organic polymers
  • the liquid solvent chosen must be capable of dissolving it.
  • the solvent may be volatile or nonvolatile, and a singleor multiple-component solvent may be used which is wholly or partially volatile.
  • volatile solvents useful in practicing the present invention include toluene, petroleum distillate, perchloroethylene, and xylene.
  • non-volatile solvents include high-boiling-point petroleum fractions and chlorinated biphenyls.
  • the solvent chosen should be capable of dissolving at least about 0.3 percent, by weight, of the chromogenic material, and at least about 3 to 5 percent, by weight, of the acidic polymeric material to ield an effective reaction.
  • the solvent should be capable of dissolving an excess of the polymeric material, so as to provide every opportunity for utilization of the chromogenic material and, thus, to assure maximum coloration at the reaction site.
  • a further criterion for selection of the solvent is that the solvent must not interfere with the mark-forming reaction.
  • the presence of the solvent may be found to interfere with the mark-forming reaction or diminish the intensity of the mark, in which instances the solvent chosen should be sufliciently volatile to assure its removal from the reaction site soon after having brought the mark-forming components into reactive contact so that the mark-forming reaction can proceed.
  • mark-forming reaction requires that an intimate mixture of the components be brought about through solution of said components, one or more of the markforming components can be dissolved in solvent droplets isolated by encapsulation, the only requirement being that at least one of the components essential to the markforming reaction be maintained isolated until the markforming reaction is desired.
  • the mark-forming components are so chosen as to produce a mark upon application of pressure to a coated system of sheets at room temperature (20 to 25 degrees centigrade).
  • the present invention also includes a system wherein the solvent component is not liquid at temperatures near room temperature but is liquid and in condition for forming solutions only at elevated temperatures.
  • the support sheet member on which components of the system are disposed may comprise a single or a dual sheet assembly.
  • the record material is referred to as a self-contained or autogenous system.
  • the record material is referred to as a transfer system.
  • a transfer system may also be referred to as a two-fold system, in that at least two sheets are required and each sheet includes a component, or components, essential to the mark-forming reaction.
  • microcapsules are employed, they can be present in the sheet support material either disposed therethroughout or as a coating thereon, or both.
  • the capsules can be applied to the sheet material as a dispersion in the liquid vehicle in which they were manufactured, or, if desired, they can be separated from the vehicle and thereafter dispersed in a solution of the acidreacting polymeric component (for instance, 30 grams of water and 53 grams of a one percent, by weight aqueous solution of polyvinylmethylether-maleic anhydride) to form a sheet-coating composition in which, because of the inertness of the solution and the capsules, both components retain their identity and physical integrity.
  • a solution of the acidreacting polymeric component for instance, 30 grams of water and 53 grams of a one percent, by weight aqueous solution of polyvinylmethylether-maleic anhydride
  • a further alternative is to disperse one or more mark-forming components, and the chromogenic-material-containing microcapsules in a liquid medium not a solvent for either the mark-forming component or the microcapsules, with the result that all components of the mark-forming system may be disposed on or within the support sheet in the one operation.
  • the several components may be applied individually.
  • the capsules can also be coated onto a sheet as a dispersion in a solution of polymeric material which is not necessarily reactive with the capsule-contained solution of chromogenic materials.
  • the respective amounts of the several components can be varied according to the nature of the materials and the architecture of the record material unit desired or re quired. Suitable lower amounts include, in the case of the chromogenic material, about 0.005 to 0.075 pound per ream (a ream in this application meaning five hundred (500) sheets of 25"): 38" paper, totalling 3,300 square feet); in the case of the solvent, about 1 to 3 pounds per ream; and in the case of the polymer, about 0.5 pound per ream. In all instances, the upper limit is primarily a matter of economic consideration.
  • the slurry of capsules can be applied to a wet web of paper, for example, as it exists on the screen of a Fourdrinier paper machine, so as to penetrate the paper web a distance depending on the freeness of the pulp and the water content of the web at the point of application.
  • the capsules can be placed directly in or on a paper or support sheet. Not only capsule structures, but continuous films which contain a multitude of microscopic, unencapsulated, droplets for local release in an area subjected to pressure can be utilized. (See, for example, US. Pat. No. 2,299,694, which issued Oct. 20, 1942, on the application of Barrett K. Green.)
  • a solution thereof in an evaporable solvent can be introduced into an amount of water and the resulting mixture can be agitated while the evaporable solvent is blown off by an air blast.
  • This operation leaves an aqueous colloidal dispersion slurry of the polymeric material, which may be applied to finished paper so as to leave a surface residue, or the slurry may be applied to a wet web of paper or at the size-press station of a paper making machine.
  • the water-insoluble polymer can be ground to a desired or required particle size in a ball mill with water, preferably with a dispersing agent, such as a small quantity of sodium silicate.
  • a binder material of hdyrophilic properties is ground with the polymeric material, the binder itself may act as a dispersant.
  • an amount of binder material of up to 40 percent, by weight, of, the amount of polymeric material can be added to the ball-milled slurry of materials such binder materials being of the paper coating binder class, including, for example, gum arabic, casein, hydroxyethylcellulose, and latexes (such as styrenebutadiene copolymer).
  • oil absorbents in the form of fullers earth may be combined with the polymeric material particles to assist in retaining, in situ, the liquid droplets of chromogenic material solution to be transferred to it in data-representing configuration, for the purpose of preventing bleeding of the print.
  • Another method for applying the chromogenic or polymeric material individually to a single sheet of paper is by immersing a sheet of paper in 1-10 percent, by weight, solution of the material in an evaporable solvent.
  • this operation must be conducted individually for each reactant, because if the other reactant material were present, contact of the reactants would result in a premature coloration over the sheet area.
  • a dried sheet with one component can then be coated with a solution of another component, the solvent of which is a non-solvent to the already-supplied component.
  • the polymeric material can also be dissolved in ink composition vehicles to form a printing ink of colorless character, and, thus, may be used to spot-print a proposed record-sheet-unit sensitized for recording, in a reaction produced color in those spot-printed areas, by application of a solution of the chromogenic material.
  • a printing ink may be made of up to 75 percent, by weight, of the phenolic polymeric material in a petroleum-based solventthe ink being built to a viscosity suitable for printing purposes.
  • the relative amounts of reactive, mark-forming, components to be used in practice of this invention are those most convenient and economical amounts consistent with adequate, desired or required visibility of the recorded data.
  • the resolution of the recorded data is dependent on, among other things, particle or capsule size, distribution and amount of particles or capsules, liquid solvent migration, chemical reaction efliciency, and other factors, all of which can be optimized empirically by one skilled in the art. Such factors do not determine the principle of the present invention, which invention, in part, relates to means for enabling the bringing into solution contact by marking pressure, two normally solid, chemically reactive, components dissolved in a common liquid solvent component held isolated as liquid droplets.
  • the isolated liquid droplets are preferably in marking-pressure-rupturable capsules having polymeric-film walls, or are isolated, as a discontinuous phase, in a continuous marking-pressure-rupturable film.
  • the acidic markforming material reacts with the novel chromogenic material to effect distinctive color formation or color change.
  • the novel chromogenic material may be desirable to include other materials to supplement the polymer reactants.
  • kaolin can be added to improve the transfer of the liquid and/or the dissolved materials between the sheets.
  • other materials such as bentom'te, attapulgite, talc, feldspar, halloysite, magnesium trisilieate, silica gel, pyrophyllite, zinc sulfate, calcium sulfate, calcium citrate, calcium phosphate, calcium fluoride, barium sulfate and tannic acid can be included.
  • compositions useful for coating mark-forming materials into supporting sheets can be employed in compositions useful for coating mark-forming materials into supporting sheets.
  • An example of the compositions which can be coated onto the receiving surface of an underlying sheet of a multi-sheet to react with a capsule coating on the underside of an overlying sheet is as follows.
  • Coating composition Percent by weight Phenolic polymer mixture 17 Paper coating kaolin (white) 57 Calcium carbonate 12 Styrene butadiene latex 4 Ethylated starch 8 Gum arabic 2 Having disclosed, generally, the novel chromogenic materials of this invention and preferred methods for utilizing the novel chromogenic materials, in combination with other materials, as reactive components in markforming record material; examples will now be disclosed wherein preparation of several of the novel chromogenic materials is described.
  • EXAMPLE A Preparation of 2 carboxy 4 diethylamino-Z-hydroxybenzophenone, an intermediate useful in preparing the novel compounds of this invention
  • EXAMPLE B Preparation of 2-amino-6'-diethylaminofluoran, an intermediate useful in preparing the novel compounds of this invention
  • An agitating mixture of 31.3 grams of 2'-carboxy- 10 4-diethylamino-Z-hydroxybenzophenone (the product of Example A, above), 16.7 grams of p-hydroxyacetanilide, and milliliters of concentrated sulfuric acid (1.84 specific gravity) is heated at a temperature of about 100 degrees centigrade for about 45 minutes under a nitrogen atmosphere.
  • Therresulting red solution is heated at a temperature of about -135 degrees centigrade for an additional 3 hours and is then cooled by means of external cooling and addition, to the reaction mixture, of 200 grams of ice.
  • the pH of the reaction mixture is adjusted to 9.5 by slow addition of about 200 milliliters of 50 percent, by weight, aqueous sodium hydroxide solution and then the solution is warmed to about 70 degrees centigrade and agitated for about 15 minutes with 700 milliliters of benzene.
  • the benzene phase is removed and treated with sodium sulfate desiccant and an activated carbon adsorbent and the benzene phase is then concentrated to about 200 milliliters by evaporation.
  • the concentrated benzene solution is chilled to about 10 degrees centigrade and cream-colored crystals are removed from the solution by filtration.
  • the melting point of the material is about 212-213 degrees centigrade.
  • a first portion of red-colored benzene eluant was discarded.
  • Next-eluted, colorless, benzene solution was collected until the eluant no longer colored a paper coated with a mixture of kaolin and phenolic resin.
  • the collected eluant was concentrated to about 50 milliliters by evaporation and about 50 milliliters of n-hexane was added to crystallize the reaction product as nearly colorless crystals having a melting point of 161-162 degrees centigrade.
  • a benzene solution of the reaction product imparted a neutral or gray to black color to paper coated with a mixture of kaolin and phenolic resin.
  • the pH of the reaction mixture was adjusted to 10.5 by slow addition of about 136 milliliters of 50 percent, by weight, aqueous sodium hydroxide solution.
  • Solid reaction product which precipitated from solution with the raise in pH was separated by filtration and washed with 5-100 milliliter volumes of water. The remaining solid was washed with 4-100 milliliter volumes of hot benzene and the benzene and the benzene wash solution was treated with sodium sulfate desiccant and an activated carbon adsorbent before being concentrated, by evaporation, to about 125 milliliters. About milliliters of hexane was added to the concentrated solution and 12.5 grams of reaction product was crystallized (melting point, 144-148 degrees centigrade).
  • the product was further purified by being recrystallized from benzene.
  • the purified product had a melting point of 147- 149 degrees centigrade and a benzene solution of it imparted a green color to paper coated with a mixture of kaolin and phenolic resin. Results of elemental analysis of the product was as follows (in weight percent):
  • EXAMPLE 3 Preparation of 2'- [N- (carbethoxymethyl) -N-methylamino]-6'-diethylaminofluoran An agitating mixture of 8.0 grams of 6-diethylamino- 2' methylaminofluoran (as prepared in Example C, above), 2.52 grams of sodium bicarbonate, 0.83 gram of potassium iodide, 5.01 grams of ethylbromoacetate and 100 milliliters of 95 percent, by volume, ethanol were refluxed together for about two hours. The reaction mixture was cooled and filtered and ethanol was removed from the filtrate by evaporation under reduced pressure.
  • EXAMPLE 4 Preparation of -6'-diethylamino-2'-(N-phenacyl) aminofluoran
  • the agitating mixture was maintained at 55 degrees centigrade for an additional one hour.
  • reaction mixture was filtered and the insoluble material was washed with 30 milliliters of benzene to dissolve the reaction product.
  • Benzene was evaporated from the resulting solution under reduced pressure and the residue exhibited a melting point of 192- 195 degrees centigrade.
  • the residue was recrystallized from a mixture of 5 milliliters of benzene and 0.3 milliliter of hexane and the purified reaction product exhibited a melting point of 201-202 degrees centigrade.
  • a benzene solution of the reaction product imparted a green color to paper coated with a mixture of kaolin and phenolic resin. Results of elemental analysis of the product was as follows (in weight percent):
  • EXAMPLE 5 Preparation of 6-diethylamino-2'-[N(N',N-dimethylcarbamoylmethyl) amino] fluoran An agitating mixture of 10.90 grams of 2'-amino-6- diethylaminofluoran (Example B, above), 3.78 grams of N,N-dimethylchloroacetamide, 2.58 grams of sodium bicarbonate, 1.00 gram of potassium iodide and 100 milliliters of percent, by volume, ethanol was refluxed for about three hours. The reaction mixture was cooled to about 5 degrees centigrade and filtered to remove solid inorganic residues and the desired reaction product.
  • the solid material was slurried with three-SO-milliliter-volumes of hot benzene to leach out the reaction product.
  • the benzene from those volumes was evaporated to yield 2.27 grams of a crude reaction product having a melting point of 129-131 degrees centigrade. Recrystallization from 50 milliliters of benzene yielded 1.78 grams of purified reaction product having a melting point of 132-134 degrees centigrade.
  • a benzene solution of the reaction product imparted a green color to paper coated with a mixture of kaolin and phenolic resin.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Color Printing (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US00792324A 1969-01-21 1969-01-21 Aliphatic amino-substituted flourans Expired - Lifetime US3769302A (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US79243569A 1969-01-21 1969-01-21
US79240169A 1969-01-21 1969-01-21
US79232569A 1969-01-21 1969-01-21
US79227969A 1969-01-21 1969-01-21
US79232469A 1969-01-21 1969-01-21
US79227769A 1969-01-21 1969-01-21
US10560071A 1971-01-11 1971-01-11

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US00792324A Expired - Lifetime US3769302A (en) 1969-01-21 1969-01-21 Aliphatic amino-substituted flourans
US792325*A Expired - Lifetime US3637757A (en) 1969-01-21 1969-01-21 Diethylamino fluorans
US792279*A Expired - Lifetime US3624107A (en) 1969-01-21 1969-01-21 Nitro- and amino-substituted fluorans
US792435*A Expired - Lifetime US3627787A (en) 1969-01-21 1969-01-21 Amids- and sulfonamido-substituted fluorans
US792277*A Expired - Lifetime US3641011A (en) 1969-01-21 1969-01-21 5- and 6-dialkylaminobenzylidene-aminofluorans
US00105600A Expired - Lifetime US3713863A (en) 1969-01-21 1971-01-11 Mark-forming record materials and process

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US792325*A Expired - Lifetime US3637757A (en) 1969-01-21 1969-01-21 Diethylamino fluorans
US792279*A Expired - Lifetime US3624107A (en) 1969-01-21 1969-01-21 Nitro- and amino-substituted fluorans
US792435*A Expired - Lifetime US3627787A (en) 1969-01-21 1969-01-21 Amids- and sulfonamido-substituted fluorans
US792277*A Expired - Lifetime US3641011A (en) 1969-01-21 1969-01-21 5- and 6-dialkylaminobenzylidene-aminofluorans
US00105600A Expired - Lifetime US3713863A (en) 1969-01-21 1971-01-11 Mark-forming record materials and process

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US (6) US3769302A (fr)
BE (1) BE744705A (fr)
CH (1) CH567077A5 (fr)
FR (1) FR2028785A1 (fr)
GB (1) GB1269601A (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
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US3900215A (en) * 1972-01-24 1975-08-19 Fuji Photo Film Co Ltd Record sheet
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Cited By (9)

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Publication number Priority date Publication date Assignee Title
US3900215A (en) * 1972-01-24 1975-08-19 Fuji Photo Film Co Ltd Record sheet
US3919450A (en) * 1972-06-24 1975-11-11 Oji Paper Co Color developing high impact polystyrene sheet and method of developing color images inside the same
US4524373A (en) * 1982-02-24 1985-06-18 Kanzaki Paper Manufacturing Co., Ltd. Fluoran derivatives as new compounds, process for preparing the same and recording system utilizing the same as colorless chromogenic material
US5250708A (en) * 1991-08-13 1993-10-05 Milliken Research Corporation Poly(oxyalkylene) substituted aminophenol intermediate and xanthene colorant
US5331097A (en) * 1991-08-13 1994-07-19 Milliken Research Corporation Poly(oxyalkylene) substituted xanthene colorant and method for making the same
US5395948A (en) * 1992-03-17 1995-03-07 Ciba-Geigy Corporation Fluoran color formers
US20090099372A1 (en) * 2007-02-06 2009-04-16 Xerox Corporation Colorant Compounds
US7910754B2 (en) 2007-02-06 2011-03-22 Xerox Corporation Colorant compounds
CN106349091A (zh) * 2016-08-30 2017-01-25 沈阳化工大学 一种熔融态合成2‑（4‑二乙氨基‑2‑羟基苯甲酰基）苯甲酸的方法

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DE2001864B2 (de) 1977-05-26
US3713863A (en) 1973-01-30
US3637757A (en) 1972-01-25
CH567077A5 (fr) 1975-09-30
BE744705A (fr) 1970-07-01
US3624107A (en) 1971-11-30
US3641011A (en) 1972-02-08
GB1269601A (en) 1972-04-06
FR2028785A1 (fr) 1970-10-16
US3627787A (en) 1971-12-14
DE2065643B2 (de) 1977-03-31
DE2065643A1 (de) 1974-11-14
DE2001864A1 (de) 1970-07-30

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