US3833614A - Phthalides and naphthalides - Google Patents

Phthalides and naphthalides Download PDF

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US3833614A
US3833614A US00103865A US10386571A US3833614A US 3833614 A US3833614 A US 3833614A US 00103865 A US00103865 A US 00103865A US 10386571 A US10386571 A US 10386571A US 3833614 A US3833614 A US 3833614A
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hydrogen
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solution
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naphthol
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M Simon
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Polaroid Corp
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Polaroid Corp
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Priority to US00103864A priority Critical patent/US3833615A/en
Priority to US00103865A priority patent/US3833614A/en
Priority to US103392A priority patent/US3702245A/en
Priority to GB1798971A priority patent/GB1363864A/en
Priority to GB1799671A priority patent/GB1363866A/en
Priority to GB100874A priority patent/GB1363870A/en
Priority to GB1799471A priority patent/GB1363865A/en
Priority to GB58574A priority patent/GB1363869A/en
Priority to CH806471A priority patent/CH616008A5/de
Priority to BE768108A priority patent/BE768108R/fr
Priority to CA114,885A priority patent/CA973416A/en
Priority to CA114,884A priority patent/CA953731A/en
Priority to BE768107A priority patent/BE768107A/fr
Priority to AT488471A priority patent/AT322979B/de
Priority to DE2166141A priority patent/DE2166141C3/de
Priority to BE768109A priority patent/BE768109A/fr
Priority to DE19712127907 priority patent/DE2127907C3/de
Priority to MX15202371A priority patent/MX144572A/es
Priority to DE19712127925 priority patent/DE2127925C3/de
Priority to DE19712165998 priority patent/DE2165998A1/de
Priority to DE19712127818 priority patent/DE2127818A1/de
Priority to FR717120371A priority patent/FR2094078B1/fr
Priority to FR717120372A priority patent/FR2094079B1/fr
Priority to FR717120370A priority patent/FR2111648B2/fr
Priority to JP3925571A priority patent/JPS5437492B1/ja
Priority to CA114,883A priority patent/CA953730A/en
Priority to NLAANVRAGE7107765,A priority patent/NL169110C/xx
Priority to NLAANVRAGE7107767,A priority patent/NL168958C/xx
Priority to NLAANVRAGE7107766,A priority patent/NL169111C/xx
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/44—Integral units, i.e. the image-forming section not being separated from the image-receiving section
    • G03C8/48—Integral units, i.e. the image-forming section not being separated from the image-receiving section characterised by substances used for masking the image-forming section
    • 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
    • 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
    • C09B11/06—Hydroxy derivatives of triarylmethanes in which at least one OH group is bound to an aryl nucleus and their ethers or esters
    • C09B11/08—Phthaleins; Phenolphthaleins; Fluorescein
    • 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
    • C09B11/245—Phthaleins having both OH and amino substituent(s) on aryl ring
    • 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

Definitions

  • the present invention relates to novel chemical compounds, and more specifically, it relates to a new class of naphthol phthalein indicator dyes. in a particular aspect it relates to l-naphthol phthaleins useful as optical filter agents in photographic processes for protecting an exposed photosensitive material from post-exposure fogging during development in the presence of extraneous incident light.
  • U.S. Pat. No. 3,415,644 discloses a composite photosensitive structure, particularly adapted for use in reflection type photographic diffusion transfer color processes.
  • This structure comprises a plurality of essential layers including, in sequence, a dimensionally stable opaque layer; one or more silver halide emulsion layers having associated therewith dye image-providing material which is soluble and diffusible, in alkali, at a first pH, as a function of the point-to-point degree of its associated silver halide emulsions exposure to incident actinic radiation; a polymeric layer adapted to receive solubilized dye image-providing material diffusing thereto; a polymeric layer containing sufficient acidifying capacity to effect reduction of a processing composition from the first pH to a second pH at which the dye image-providing material is substantially nonditfusible; and a dimensionally stable transparent layer.
  • This structure may be exposed to incident actinic radiation and processed by interposing, intermediate the silver halide emulsion layer and the reception
  • the light reflecting agent (referred to in said patent as an opacifying agent) also performs an opacifying function, i.e., it is effective to mask the developed silver halide emulsions and also acts to protect the photoexposed emulsions from postexposure fogging by light passing through the transparent layer it the photoexposed film unit is removed from the camera before image formation is complete.
  • the composite photosensitive structure includes a rupturable container, retaining the alkaline processing composition having the first pH and light-reflecting agent, fixedly positioned extending transverse a leading edge of the composite structure in order to effect, upon application of compressive pressure to the container, discharge of the processing composition intermediate the opposed surfaces of the reception layer and the next adjacent silver halide emulsion.
  • the liquid processing composition distributed intermediate the reception layer and the silver halide emulsion permeates the silver halide emulsion layers of the composite photosensitive structure to initiate development of the latent images contained therein resultant from photoexposure.
  • dye image-providing material associated with each of the respective silver halide emulsion layers is individually immobilized as a function of the point-topoint degree of the respective silver halide emulsion layer photoexposure, resulting in imagewise distributions of mobile dye image-providing materials adapted to transfer, by diflusion, to the reception layer to provide the desired transfer dye image.
  • a sutficient portion of the ions of the alkaline processing composition transfers, by diffusion, to the polymeric neutralizing layer to effect reduction in the alkalinity of the composite film unit to the second pH at which dye image-providing material is substantially nondiffusible, and further dye image-providing material transfer is thereby substantially obviated.
  • the transfer dye image is viewed, as a reflection image, through the dimensionally stable transparent layer against the background provided by the reflecting agent, distributed as a component of the processing composition, mtermediate the reception layer and next adjacent silver halide emulsion layer.
  • the thus-formed stratum effectively mas ks residual dye image-providing material retained in association with the developed silver halide emulsion layer subsequent to processing.
  • an organic light-absorbing reagent such as a dye, which is present as a light-absorbing species at the first pH and which may be converted to a substantially non-light-absorbing species at the second pH is used in conjunction with the light-reflecting agent to protect the selectively exposed silver halide emulsions from post-exposure fogging when development of the photoexposed emulsions is conducted in the presence of extraneous incident actinic radiation impinging on the transparent layer of the film unit.
  • pH-sensitive dyes derived from certain hydroxy-substituted carbocyclic aryl compounds, viz., particular phenols and naphthols are disclosed as useful as optical filter agents for absorbing incident radiation actinic to selectively exposed photosensitive materials within a predetermined wavelength range in the longer wavelength region of the visible spectrum.
  • Certain of the novel dyes disclosed therein comprlse the subject matter of the present invention, namely, phthaleins containing two naphthol radicals at least one of which s substituted with a hydrogen-bonding group.
  • These indicator dyes find utility as optical filter agents in photographic processes employing alkaline processing solutions.
  • the invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products and compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • a novel class of phthalein indicator dyes derived from 1- naphthols which contain a p-hydroxynaphthyl radical possessing a hydrogen-bonding group substituted group substituted on a carbon atom adjacent to the p-hydroxy group, a second p-hydroxynaphthyl radical and a ringclosing moiety selected from a phthalide and naphthalide, which indicator dyes will be defined with greater particularity hereinafter.
  • the indicator dyes f the present invention like phthalein indicators in general such as phenol phthalein and l-naphtholphthalein, possess spectral absorption characteristics which are reversibly alterable in response to changes in environmental pH.
  • These dyes possess a highly colored form capable of absorbing visible radiation in alkaline media at a first pH value above their respective pKa and a substantially colorless form, i.e., a form which is substantially non-light-absorbing in the visible spectrum in less alkaline media at a second pH value below their respective pKa.
  • pKa is meant the pH at which about 50% of the dye is present in its light-absorbing form and about 50% is present in its non-light-absorbing form.
  • phthalein indicator dyes are commonly employed, for example, to measure changes in pH value as reflected by the change in color of the dye from one color to another or from colored to colorless or vice versa.
  • the indicator dyes of the present invention compared to conventional naphthol phthaleins possess a higher pKa which render them useful as optical filter agents in photographic processes performed under alkaline conditions, and certain of the indicator dyes provided herein are useful in photographic processes employing highly alkaline media.
  • the pKa of l-naphthol phthaleins may be increased by substituting one of the p-hydroxynaphthyl radicals with a hydrogen-bonding group on a carbon atom adjacent to the para hydroxy wherein one of R and R is a hydrogen-bonding group having a negative charge in basic solution and the other is hydrogen; B is a p-hydroxynaphthyl radical; and X represents the atoms necessary to complete a ring-closing moiety selected from a phthalide and a naphthalide.
  • R is a hydrogen-bonding group and R is hydrogen.
  • any hydrogen-bonding group may be used that is capable of raising the pKa.
  • the association of two atoms through hydrogen to form a hydrogen bond between or within molecules is well known.
  • hydrogen is attached to an electronegative atom, for example, 0 or N, the resultant bond is polarized. If directed toward another atom (M) with an unshared pair of electrons, the hydrogen acts as a bridge between the atoms (O-H M due to the electrostatic attraction to both atoms between which the hydrogen proton can be transferred.
  • an intramolecular hydrogen bond is formed between the p-hydroxy group and an adjacent hydrogenbonding group, i.e., a group containing a heteroatom possessing an active unshared pair of electrons, such as, O, N, S or halogen, e.g., R, which has a free electron pair or a negative charge in basic solution and which is capable of forming a 5-, 6- or 7-membered and preferably a 5- or 6-membered hydrogen-bonded ring with the p-hydroxy group.
  • the heteroatom in the hydrogenbonding group has attached to it a proton which is more acidic than the proton on the naphtholic OH and ionizes in basic solution to a negative charge.
  • Such groups include, for example, carboxy; hydroxy; o-hydroxyphenyl; bis trifluoromethyl carbinol; sulfonamido (NH-SOz-R wherein R may be alkyl, aryl, alkaryl); and sulfamoyl (SO NHR wherein R may be alkyl, aryl, alkaryl).
  • Suitable R and R substituents include branched or straight chain alkyl, e.g., methyl, ethyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl and eicosanyl; aryl, e.g., phenyl and naphthyl; and alkaryl, e.g., benzyl, phenethyl, phenylhexyl, p-octylphenyl and p-dodecylphenyl.
  • alkyl e.g., methyl, ethyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl
  • compounds containing a sulfamoyl or sulfonamido substituent afford the distinct advantage of allowing the immobilizing function to be combined with the hydrogen bonding function by selecting sulfonamido or sulfamoyl (SO -NHR') groups containing as R or R an immobilizing group, such as, hexadecyl or p-dodecylphenyl.
  • the compounds represented in the above formula may contain substituents other than those specified.
  • the naphthyl radicals may contain additional substituents and likewise, the ring-closing moiety may contain other substituents as may be desired.
  • R is hydrogen
  • R is a hydrogen-bonding group
  • the second p-hydroxynaphthyl radical also is substituted with a hydrogen-bonding group.
  • R and R the same or dilferent, each are hydrogen-bonding groups having a negative charge in basic solution and X has the same meaning as in Formula (I) above.
  • pKa of l-naphthol phthaleins including both phthalides and naphthalides may be increased by substituting only one of the p-hydroxy-naphthyl radicals with a hydrogen-bonding group in the 2- or 8-position, a further increase in pKa may be achieved by substituting both p-hydroxynaphthyl radicals with a hydrogen-bonding group. This elfect is especially apparent when the group is substituted in the 2-position.
  • Preferred hydrogen-bonding groups capable of ionizing in base to a negative charge are carboxy, sulfonamido and sulfamoyl.
  • the indicator dyes are represented in the above formulae may contain additional substituents as may be desired which do not interfere with the function of the dye for its selected ultimate use.
  • Typical substituents include branched or straight chain alkyl, such as methyl, ethyl, isopropyl, t-butyl, octyl, hexadecyl, and eicosanyl; aryl, such as, phenyl and naphthyl; alkaryl, such as, benzyl, phenethyl, phenylhexyl, and p-dodecylphenyl; alkoXy, such as, methoxy, ethoxy, butoxy, l-ethoxy-Z-(fi-ethoxyethoxy) and octadecyloxy; aryloxy, such as phenoxy, benzyloxy and naphthoxy; alkoxyalkyl, such as methoxyethyl
  • naphthol indicator dyes within the scope of the present invention are as follows:
  • Phthalein dyes including phthalides and naphthalides may be prepared by reacting the appropriate anhydride, acid or acid chloride, e.g., phthalic or naphthalic anhydride with the selected naphthol at elevated temperatures usually in the presence of a suitable catalyst, such as a Lewis acid catalyst.
  • a suitable catalyst such as a Lewis acid catalyst.
  • Another method of preparing these phthaleins comprises reacting the selected naphthol with phthalaldehydic or naphthalaldehydic acid in the presence of a mild acid catalyst, e.g. toluene p-sulfonic acid, to yield the corresponding (n)phthalidyl-substituted intermediate which is oxidized by treating with, for example, dichlorodicyanoquinone.
  • a mild acid catalyst e.g. toluene p-sulfonic acid
  • the oxidized intermediate is then reacted with another aromatic compound which may be a naphthol in the presence of an acid catalyst to yield the desired dye.
  • both symmetrical and unsymmetrical indicators may be prepared by selecting respectively, as the second aromatic compound, a naphthol that is the same or that is different from the starting naphthol initially reacted with aldehydic acid.
  • This method of preparing l-naphthol phthaleins and phthaleins derived from other selected aromatic compounds forms the subject matter of copending U.S. Patent Application Ser. No. 108,662 of Alan L. Borror filed Jan. 21, 1971.
  • Naphthol phthaleins also may be prepared by forming a (na)phthalidyl-substituted intermediate which is reacted in aqueous alkali with a naphthol, the same or difierent from the starting naphthol to form the leuco dye which is then oxidized to yield the indicator.
  • This method forms the subject matter of copending U.S. Patent Application Ser. No. 202,615 of Eva R. Karger and Paul T. MacGregor filed Nov. 26, 1971.
  • Another method of preparing naphthol phthaleins comprises the silver-catalyzed reaction of a 3-halo-3-(naphthyl) naphthalide-1,8 intermediate with a naphthol, the same or difi'erent from that comprising the 3-naphthyl substituent of the intermediate.
  • This method forms the subject matter of copending U.S. Patent Application Ser. No. 192,638 of Richard B. GreenWald filed Oct. 26, 1971, now U.S. Pat. No. 3,702,245.
  • Insoluble material (6.5 gms.) was removed by filtration, and the yellow-tan filtrate was evaporated to dryness to give pale yellow l-hydroxy-Z-naphthoyl chloride, m.p. 8788 C. Chilled anhydrous methanol ml.) was added quickly to the solid chloride in an exothermic reaction. The partial solution was heated about 5 minutes on the steam bath under a drying tube then allowed to cool. The suspension was chilled and the solid was collected to give 43 gms.
  • 3,3-Dichloronaphthalide (37.8 gms., 0.149 mole) was dissolved in 100 ml. of l,1,2,2-tetrachloroethane in a flame-dried 2 liter 3-neck round bottom flask fitted With an addition funnel, air condenser, mechanical stirrer and drying tube. The solution was chilled in an ice bath; the previously prepared complex solution was decanted into the addition funnel and added dropwise over 30-60 minutes to the well-stirred reaction mixture. A rich purple color developed immediately. The reaction mixture was stirred and allowed to come to room temperature overnight.
  • step (c) A solution of 1 equivalent of the naphthalide obtained in step (b) and 3 equivalents of l-naphthol was prepared in dry acetic acid (about 1 gm./l5- ml.). Boron trifluoride etherate (1 equivalent) was added, and the reaction mixture was heated to reflux for several hours.
  • dry acetic acid about 1 gm./l5- ml.
  • Boron trifluoride etherate (1 equivalent) was added, and the reaction mixture was heated to reflux for several hours.
  • step (c) A solution of 50 ml. of aqueous 10% sodium hydroxide was flushed with nitrogen for 2 hours. To the solution was added 2.3 gms. of the product of step (b) and 1.4 gms. of 2-n-propyl-sulfamoyl-l-naphthol as prepared in step (a). The resulting solution was heated at 60 C. overnight. The temperature was raised to 70 C. and heating was continued for about 48 hours. The reaction mixture was then cooled and the pH adjusted to approximately 1.0 with dilute hydrochloric acid. The white solids formed were collected and washed and taken up in benzene. The benzene solution was treated with charcoal, filtered and concentrated until solids began to precipitate. The precipitate was collected yielding 2.5 gms. of White solid (melting range 178-l80 C. dec.).
  • step (d) 710 mgs. of the product of step (c) were dissolved in about 30 ml. of dimethylformamide. To this was added 230 mgs. of 57% sodium hydride. The resulting solution was heated at 80 C. until the evolution of hydrogen had ceased. Then 470 mgs. of silver oxide was added, and the mixture was stirred overnight at room temperature. Heating was continued at 80 C. for 8 hours. The reaction mixture was filtered, and the filtrate poured into 30 ml. of water, acidified with dilute hydrochloric acid and the precipitate collected. The precipitate was taken up in benzene and chromatographed on silica gel. Elution with 10% ethyl acetate in benzene yielded about 100 mgs. of the title compound.
  • the amine-substituted intermediate obtained above was dissolved in dry pyridine (1 gm./ 10 ml.) in a flame-dried round-bottom flask fitted with a dropping funnel and chilled in an ice bath to about 5 C. Acetyl chloride (5 equivalents) was added dropwise. When addition was complete, the cooling bath was removed and the reaction mixture allowed to come to room temperature. The reaction mixture was poured into dilute hydrochloric acid. The solid that formed was collected, dissolved in methanol (1 gm./40 ml.) and filtered. Dilute alkali was added, and after stirring for about an hour, the precipitate was collected, washed and dried and recrystallized from ethyl acetate/hexane to yield the title compound.
  • the 3-chloro- 3 (3' carbomethoxy-4'-hydroxynaphthyl) naphthalide- 1,8 product was collected on a Biichner funnel and Washed with a small amount of dry hexane. Residual solvent was removed in a vacuum desiccator.
  • the 1 hydroxy-6-octadecyloxy-Z-naphthoic acid employed in step (b) above was prepared by adding sodium methoxide (67.4 gms., 1.35 mole) to a solution of 1,6
  • dihydroxy-naphthalene (100 gms., 0.625 mole) in 900 ml. of dry N,N-dimethyl-formamide saturated with dry carbon dioxide gas. A steady flow of carbon dioxide was maintained throughout the reaction. Approximately 125 ml. of dimethylformamide was distilled and the mixture was then refluxed for 15 minutes and an additional 125 ml. of solvent removed. The solution was cooled and the flow of carbon dioxide stopped. The reaction mixture was acidified with concentrated hydrochloric acid and then poured onto about 2000 gms. of ice. The precipitated dark solid was filtered and dried and then triturated with 1 liter of boiling benzene and filtered free of dark impurities. Recrystallization from water gave 1,6-dihydroxy- 2-naphthoic acid as a white solid (melting range 220- 221 C.).
  • the precipitate formed was collected and then dissolved in 12 ml. of aqueous sodium hydroxide and 36 ml. of ethanol. The solution was heated on a steam bath for minutes, cooled and made acidic with concentrated hydrochloric acid. The ethanol was evaporated and the solid material collected by filtration was taken up in ether. The ether solution was filtered, evaporated to dryness and triturated with petroleum ether.
  • EXAMPLE 8 Preparation of the compound of formula (8) A solution of '3-hydroxy-3-(3'-carbomethoxy-4'-hydroxynaphthyl) naphthalide-1,8 (528 mgs.), 2-hexadecyll-naphthol (480 mgs.), and boron trifluoride etherate (184 mgs.) in glacial acetic acid (12 cc.) was refluxed 3 hours. The solution was cooled and evaporated to half-volume. On standing a solid formed which was purified by recrystallization from ethanol.
  • EXAMPLE 9 Preparation of the compound of formula (3) 37.6 grams (0.2 mole) of 1-hydroxy-2-naphthoic acid and 20.3 grams (0.2 mole) of 3,3-dichlorophthalide were dissolved in ethyl ether by heating. The resulting solution was cooled and 23 ml. (0.2 mole) of stannic chloride was added dropwise. The mixture was stirred at room temperature for about 48 hours, after which the ethyl ether was removed by evaporation, leaving a green oil. Upon the addition of ethanol, the solution turned pink and a white solid precipitated out. The white solid was removed by filtration and sodium hydroxide was added to the filtrate until it became basic.
  • the base-insoluble material was filtered and the resulting filtrate acidified with acetic acid. A pink solid was obtained, filtered, and then dissolved in aqueous alkali. The base-insoluble material was filtered off and the filtrate was acidified with acetic acid to give a precipitate.
  • EXAMPLE 10 Preparation of the compound of formula (2) 10 g. (0.049 mole) of the methyl ester of 8-hydroxy-1- naphtholic acid, 2.3 ml. (0.016 mole) phthaloyl chloride and 5.8 ml. (0.05 mole) of stannic chloride were mixed with stirring at 110 C. and reacted for about two hours. The dark brown viscous reaction mixture was poured into ice water without cooling, and the resulting solid was reduced to small particles by grinding and then taken up in a mixture of water and chloroform. The chloroform layer was washed well with water and then dried for chromatography. The material was placed on a Florisilchloroform column.
  • the resulting indicator dyes are colored at a higher pH which renders them particularly useful as optical filter agents in photographic processes.
  • l-naphthol phthalein has a lower pKa of 7.0.
  • the compounds as represented in formulae (2) and (3) have a pKa of 8.5 and 12.5, respectively.
  • the compounds as represented in formulae (9), (7) and (12) have apKa of 9.8, 12.8 and 13.9. respectively.
  • (l-naphthol naphthalein was prepared in accordance with the method of Example 9 above by reacting l-naphthol with 3,3-dichloronaphthalide in the presence of stannic chloride.)
  • indicator dyes may be selected from the above-denoted class for use as optical filter agents in photographic processes, e.g., conventional tray processing and diffusion transfer processes where development of a photosensitive material is conducted in the presence of extraneous incident light.
  • the dyes described above have a highly colored, lightabsorbing form in alkaline media at a pH above their respective pKa and a substantially colorless form, i.e., a form which is substantially non-light-absorbing in the visible region in less alkaline media at a pH below their respective pKa.
  • an indicator dye or dyes may be selected from the aforementioned class of compounds which will be in a colored or lightabsorbing form at the particular pH employed during development and which may be converted to a substantially non-light-absorbing form subsequent to at least the initial stages of development to permit viewing of the final image.
  • the optical filter agent In photographic processes where the optical filter agent is retained in association with the final image formed, it may be readily converted to a form which does not interfere with viewing of the image and which does not detract from the brilliance, hues and other properties of the image.
  • the present invention provides indicator dyes that are particularly useful in diffusion transfer proecsses and especially in diffusion transfer photographic processes employing composite photosensitive elements such as those described in aforementioned US. Pat. 3,415,644.
  • a highly alkaline processing composition having a pH of 13-14 or higher is employed so that it is desirable to use an optical filter agent having a pKa of 11 or preferably 12 or higher that will provide protection from incident actinic radiation during the processing interval but subsequent to the initial stages of development may be rapidly converted to its colorless form to permit early viewing of the final image.
  • the indicator dyes used as the optical filter agents may be initially disposed in a layer of the composite film unit but preferably are initially disposed in the processing composition applied subsequent to selective photoexposure of the photosensitive structure.
  • the dyes selected When incorporated into the processing composition. it is desirable that the dyes selected exhibit good stability in highly alkaline media in addition to broad spectral absorpton in the visible spectrum and a high pKa.
  • the dyes employed as optical filter agents are preferably substantially non-ditfusible in the alkaline processing composition in order to achieve optimum efficiency as a radiation filter and to prevent ditfusion of filter agent into layers of the film unit where its presence mav be undesirable.
  • Indicator dyes which possess these preferred characteristics are those represented in Formula (II). These indicator dyes possess the desired unique combination of properties, namely. (1) efficient absorption of actinic radiation within the wavelen th range of about 550 nm. to 700 nm.. 2) a high pKa of 11 or more. (3) stability in highly alkaline media, and optionally, (4) non-diffusibility in aqueous alkali. As noted above, the photographic use of these dyes as optical filter agents in photographic processes is disclosed and claimed in copending US. Patent Application Ser. No. 103,392 filed concurrently herewith.
  • R and R the same or difierent, each are hydrogen-bonding groups selected from carboxy, hydroxy, o-hydroxyphenyl, sulfonamido and sulfamoyl, R is selected from hydrogen and alkoxy having 1 to 18 carbon atoms, and X represents the atoms necessary to complete a ring-closing moiety selected from phthalide and naphthalide, said ring-closing moiety being unsubstituted or substituted with a substituent selected from carboxy and alkoxy having 1 to 16 carbon atoms.
  • R and R each are selected from hydrogen, alkyl having 1 to 16 carbon atoms and a group containing a heteroatom possessing an active unshared pair of electrons selected from O, N and S, said heteroatom possessing a proton more acidic than the proton of the adjacent OH and ionizing to a negative charge in basic solution to form an intramolecular hydrogen bond with said OH, said group forming a 5-, 6- or 7-membered intramolecular hydrogen-bonded ring with said OH;
  • R and R each are selected from hydrogen, alkyl having 1 to 16 carbon atoms and a group containing a heteroatom possessing an active unshared pair of electrons selected from O, N and S, said heteroatom possessing a proton more acidic than the proton of the adjacent OH and ionizing to a negative charge in basic solution to form an intramolecular hydrogen bond with said OH, said group forming a 5-, 6- or 7-membered intramolecular hydrogen-bonded ring with said OH,
  • X represents the atoms necessary to complete a ringclosing moiety selected from phthalide and naphthalide, said ring-closing moiety being unsubstituted or substituted with a substituent selected from carboxy and alkoxy having 1 to 16 carbon atoms. 22.
  • R and R the same or difierent, each is a group containing a heteroatom possessing an active unshared pair of electrons selected from 0', N and S, said heteroatom possessing a proton more acidic than the proton of OH and ionizing to a negative charge in basic solution to form an intramolecular hydrogen bond with said OH, said group forming a 5-, 6- or 7-membered intramolecular hydrogen-bonded ring with said OH;
  • R is selected from hydrogen and alkoxy having 1 to 18 carbon atoms;
  • X represents the atoms necessary to complete a ring-closing moiety selected from phthalide and naphthalide, said ring-closing moiety being unsubstituted or substituted with a substituent selected from carboxy and alkoxy having 1 to 16 carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Indole Compounds (AREA)
  • Optical Filters (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US00103865A 1970-06-05 1971-01-04 Phthalides and naphthalides Expired - Lifetime US3833614A (en)

Priority Applications (29)

Application Number Priority Date Filing Date Title
US00103864A US3833615A (en) 1970-06-05 1971-01-04 Naphthalides and phthalides
US00103865A US3833614A (en) 1970-06-05 1971-01-04 Phthalides and naphthalides
US103392A US3702245A (en) 1970-06-05 1971-01-04 Photographic diffusion-transfer processes and elements utilizing ph-sensitive optical filter agents to prevent fogging by extraneous actinic radiation during development
GB1798971A GB1363864A (en) 1970-06-05 1971-05-28 Photographic products and development processes
GB1799671A GB1363866A (en) 1970-06-05 1971-05-28 Photographic products and development processes
GB100874A GB1363870A (en) 1970-06-05 1971-05-28 Indicator dyes
GB1799471A GB1363865A (en) 1970-06-05 1971-05-28 Photographic products and diffusion transfer processes
GB58574A GB1363869A (en) 1970-06-05 1971-05-28 Indole indicator dyes
CH806471A CH616008A5 (enrdf_load_stackoverflow) 1970-06-05 1971-06-03
CA114,883A CA953730A (en) 1970-06-05 1971-06-04 Naphthol phthalein indicator dyes
CA114,884A CA953731A (en) 1970-06-05 1971-06-04 Phenol phthalein indicator dyes
BE768107A BE768107A (fr) 1970-06-05 1971-06-04 Produits et procedes photographiques
AT488471A AT322979B (de) 1970-06-05 1971-06-04 Photographischer filmverband
DE2166141A DE2166141C3 (de) 1970-06-05 1971-06-04 Indikatorfarbstoffe
BE768108A BE768108R (fr) 1970-06-05 1971-06-04 Produits, compositions et procedes
DE19712127907 DE2127907C3 (de) 1970-06-05 1971-06-04 Photographisches Aufzeichnungsmaterial für das Diffusionsübertragungsverfahren
MX15202371A MX144572A (es) 1970-06-05 1971-06-04 Una unidad de pelicula fotografica
DE19712127925 DE2127925C3 (de) 1970-06-05 1971-06-04 21.01.71 USA 108277 Photographisches Aufzeichnungsmaterial für das Diffusionsübertragungsverfahren
DE19712165998 DE2165998A1 (de) 1970-06-05 1971-06-04 Indolfarbstoffe. Ausscheidung aus: 2127925
DE19712127818 DE2127818A1 (de) 1970-06-05 1971-06-04 Photographisches Aufzeichnungsmaterial fur das Diffusionsubertragungsfarbstoff verfahren
FR717120371A FR2094078B1 (enrdf_load_stackoverflow) 1970-06-05 1971-06-04
FR717120372A FR2094079B1 (enrdf_load_stackoverflow) 1970-06-05 1971-06-04
FR717120370A FR2111648B2 (enrdf_load_stackoverflow) 1970-06-05 1971-06-04
JP3925571A JPS5437492B1 (enrdf_load_stackoverflow) 1970-06-05 1971-06-04
CA114,885A CA973416A (en) 1970-06-05 1971-06-04 Photographic processes and products
BE768109A BE768109A (fr) 1970-06-05 1971-06-04 Produits et procedes photographiques
NLAANVRAGE7107765,A NL169110C (nl) 1970-06-05 1971-06-07 Werkwijze voor het ontwikkelen van een beeldsgewijs belicht lichtgevoelig element, fotografische filmeenheid geschikt voor het uitvoeren van die werkwijze; alsmede werkwijze voor het bereiden van een behandelingsvloeistof respectievelijk van een indicatorkleurstof geschikt voor het uitvoeren van respectievelijk voor gebruik bij de eerstgenoemde werkwijze.
NLAANVRAGE7107767,A NL168958C (nl) 1970-06-05 1971-06-07 Fotografische filmeenheid.
NLAANVRAGE7107766,A NL169111C (nl) 1970-06-05 1971-06-07 Werkwijze voor het ontwikkelen van een beeldsgewijs belicht lichtgevoelig element, fotografische filmeenheid geschikt voor het uitvoeren van die werkwijze; alsmede werkwijze voor het bereiden van een behandelingsvloeistof respectievelijk van een indicatorkleurstof geschikt voor het uitvoeren van respectievelijk voor gebruik bij de eerstgenoemde werkwijze.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US4378270A 1970-06-05 1970-06-05
US10339271A 1971-01-04 1971-01-04
US00103864A US3833615A (en) 1970-06-05 1971-01-04 Naphthalides and phthalides
US00103865A US3833614A (en) 1970-06-05 1971-01-04 Phthalides and naphthalides
US10826071A 1971-01-21 1971-01-21
US10827771A 1971-01-21 1971-01-21

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US00103865A Expired - Lifetime US3833614A (en) 1970-06-05 1971-01-04 Phthalides and naphthalides
US00103864A Expired - Lifetime US3833615A (en) 1970-06-05 1971-01-04 Naphthalides and phthalides
US103392A Expired - Lifetime US3702245A (en) 1970-06-05 1971-01-04 Photographic diffusion-transfer processes and elements utilizing ph-sensitive optical filter agents to prevent fogging by extraneous actinic radiation during development

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US00103864A Expired - Lifetime US3833615A (en) 1970-06-05 1971-01-04 Naphthalides and phthalides
US103392A Expired - Lifetime US3702245A (en) 1970-06-05 1971-01-04 Photographic diffusion-transfer processes and elements utilizing ph-sensitive optical filter agents to prevent fogging by extraneous actinic radiation during development

Country Status (9)

Country Link
US (3) US3833614A (enrdf_load_stackoverflow)
AT (1) AT322979B (enrdf_load_stackoverflow)
BE (3) BE768109A (enrdf_load_stackoverflow)
CA (3) CA953731A (enrdf_load_stackoverflow)
CH (1) CH616008A5 (enrdf_load_stackoverflow)
DE (3) DE2127818A1 (enrdf_load_stackoverflow)
FR (3) FR2094079B1 (enrdf_load_stackoverflow)
GB (4) GB1363866A (enrdf_load_stackoverflow)
NL (3) NL169110C (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976662A (en) * 1971-11-26 1976-08-24 Polaroid Corporation 1:1 Adducts of 1-naphthol and (Na)phthalaldehydic acid
US4035391A (en) * 1974-02-28 1977-07-12 Polaroid Corporation Phthalide and naphthalide derivatives

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816123A (en) * 1971-11-26 1974-06-11 Polaroid Corp Photographic processes and products employing 8-quinolinol phthaleins as optical filter agents
US4010168A (en) * 1971-12-02 1977-03-01 Polaroid Corporation Naphthalide indicator dyes
US3923519A (en) * 1972-01-03 1975-12-02 Polaroid Corp U.V. light absorbers in supports of integral diffusion transfer film units
US4025682A (en) * 1972-10-24 1977-05-24 Polaroid Corporation Photographic products
US4139381A (en) * 1977-09-23 1979-02-13 Polaroid Corporation Photographic products and processes employing pH sensitive filter dyes
AU523247B2 (en) * 1977-09-23 1982-07-22 Polaroid Corp. Sulfam(na)phthalein derivatives
AU522876B2 (en) * 1977-09-23 1982-07-01 Polaroid Corp. Sulfan (na) phthalein derivantives
US4456674A (en) * 1982-11-01 1984-06-26 Polaroid Corporation Color transfer photographic processes and products
US4496651A (en) * 1983-07-25 1985-01-29 Polaroid Corporation Color transfer photographic processes and products
US4615966A (en) * 1985-07-03 1986-10-07 Polaroid Corporation Color transfer photographic processes and products with indole phthalein filter dyes
US4891298A (en) * 1988-10-03 1990-01-02 Polaroid Corporation Photographic products and processes
US4886733A (en) * 1988-10-03 1989-12-12 Polaroid Corporation Photographic products and processes
US5384411A (en) * 1991-06-20 1995-01-24 Hewlett-Packard Company Immobilization of PH-sensitive dyes to solid supports
US5244771A (en) * 1991-08-20 1993-09-14 Polaroid Corporation Photographic products and processes
WO1993004403A1 (en) * 1991-08-20 1993-03-04 Polaroid Corporation Photographic products and processes
US5294375A (en) * 1991-08-20 1994-03-15 Polaroid Corporation Thermochromic materials
US6541177B1 (en) 2001-04-16 2003-04-01 Polaroid Corporatiion Diffusion transfer photographic film unit
WO2015137485A1 (ja) 2014-03-13 2015-09-17 三菱瓦斯化学株式会社 レジスト組成物及びレジストパターン形成方法
US10294183B2 (en) 2014-03-13 2019-05-21 Mitsubishi Gas Chemical Company, Inc. Compound, resin, material for forming underlayer film for lithography, underlayer film for lithography, pattern forming method, and method for purifying the compound or resin
KR102527656B1 (ko) 2015-03-30 2023-05-02 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 레지스트 기재, 레지스트 조성물 및 레지스트 패턴 형성방법
WO2016158457A1 (ja) 2015-03-30 2016-10-06 三菱瓦斯化学株式会社 化合物、樹脂、及びそれらの精製方法、リソグラフィー用の下層膜形成材料、下層膜形成用組成物、及び下層膜、並びに、レジストパターン形成方法、及び回路パターン形成方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3509174A (en) * 1967-01-30 1970-04-28 Ncr Co 3-(indol-3-yl)-phthalides
US3491111A (en) * 1967-01-30 1970-01-20 Ncr Co Indole- and carbazole-substituted phthalides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976662A (en) * 1971-11-26 1976-08-24 Polaroid Corporation 1:1 Adducts of 1-naphthol and (Na)phthalaldehydic acid
US4035391A (en) * 1974-02-28 1977-07-12 Polaroid Corporation Phthalide and naphthalide derivatives

Also Published As

Publication number Publication date
BE768109A (fr) 1971-12-06
NL169111B (nl) 1982-01-04
DE2127925B2 (de) 1976-09-09
DE2166141C3 (de) 1978-11-09
US3833615A (en) 1974-09-03
CA953731A (en) 1974-08-27
BE768108R (fr) 1971-12-06
DE2166141B2 (de) 1978-03-16
NL168958B (nl) 1981-12-16
DE2165998A1 (de) 1972-11-23
CH616008A5 (enrdf_load_stackoverflow) 1980-02-29
DE2127925A1 (de) 1972-02-24
FR2094079B1 (enrdf_load_stackoverflow) 1973-06-08
BE768107A (fr) 1971-12-06
DE2127907A1 (de) 1972-02-03
NL7107767A (enrdf_load_stackoverflow) 1971-12-07
FR2111648B2 (enrdf_load_stackoverflow) 1973-06-08
DE2127818A1 (de) 1971-12-16
GB1363870A (en) 1974-08-21
FR2094079A1 (enrdf_load_stackoverflow) 1972-02-04
DE2165998C2 (enrdf_load_stackoverflow) 1987-07-02
DE2166141A1 (de) 1973-04-12
FR2111648A2 (enrdf_load_stackoverflow) 1972-06-09
CA953730A (en) 1974-08-27
DE2127907B2 (de) 1976-05-13
NL169110B (nl) 1982-01-04
NL7107766A (enrdf_load_stackoverflow) 1971-12-07
GB1363864A (en) 1974-08-21
NL169110C (nl) 1982-06-01
AT322979B (de) 1975-06-25
GB1363866A (en) 1974-08-21
FR2094078A1 (enrdf_load_stackoverflow) 1972-02-04
CA973416A (en) 1975-08-26
FR2094078B1 (enrdf_load_stackoverflow) 1973-06-08
US3702245A (en) 1972-11-07
NL169111C (nl) 1982-06-01
NL168958C (nl) 1981-12-16
NL7107765A (enrdf_load_stackoverflow) 1971-12-07
GB1363865A (en) 1974-08-21

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