US3714187A - Spiro(indoline-2,2'-2h'-chromene)photochromic compounds - Google Patents

Spiro(indoline-2,2'-2h'-chromene)photochromic compounds Download PDF

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Publication number
US3714187A
US3714187A US00020761A US3714187DA US3714187A US 3714187 A US3714187 A US 3714187A US 00020761 A US00020761 A US 00020761A US 3714187D A US3714187D A US 3714187DA US 3714187 A US3714187 A US 3714187A
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group
solution
compounds
alkyl group
photochromic
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US00020761A
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H Ono
C Osada
H Katsuyama
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • 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
    • C09B57/00—Other synthetic dyes of known constitution
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances

Definitions

  • ABSTRACT Photochromic compounds having the formula l U ⁇ IY/ ⁇ %// I 2 R1 R k/R3 wherein R is a member selected from the group consisting of an alkyl group, a substituted alkyl group, and an aralkyl group; wherein R and R each is a member selected from the group consisting of an alkyl group and a phenyl group; and, wherein R is a member selected from the group consisting of an alkyl group, a nitro group, a halogen atom, an aldehyde group, an alkoxyl group, a carboxyl group, and a carboxylic acid ester group; said alkyl group having from one to five carbon atoms are disclosed.
  • the compounds are useful in recording media where their ability to change color on activation with
  • Field of the Invention riched with ultraviolet rays or sunlight. That is to say,
  • such compounds have stable electronic configurations, in the absence of activation, with their own specific spectral characteristics (in many cases, the unactivated compound is colorless).
  • the compound when the compound is irradiated with light of a specific wave length, the 2 compound has a different absorption spectrum and is converted into a colored state. When the irradiation of the light is stopped, the compound reverts to the original state (usually a colorless state).
  • Photochromism is observed in inorganic compounds and organic compounds and further some compounds exhibit photochromism as liquids and other compounds exhibit it as solids.
  • photochromic compounds can further be utilized as ultra violet-absorbing glasses, curtains, display materials, and the like.
  • inorganic photochromic compounds have a high intensity and a repeating intensity to sunlight and ultraviolet rays, they have a disadvantage that the light response time thereof is long. Also, although conventional photochromic compounds have a short light response time and a high density, they have the disadvantages that the light fastness thereof is weak and hence the repeating intensity is low. That is to say, compounds which are endowed with both advantages of the inorganic photochromic compounds and the organic photochromic compounds are rare.
  • R represents an alkyl group, analkyl group substituted with a substituent such as a cyano group, a hydroxyl group, a carboxyl group or an ethyl carboxylate or an aralkyl group; wherein R and R represent an alkyl group or a phenyl group; and R represents an alkyl group, a nitro group, a halogen atom, an aldehyde group, an alkoxyl group, a carboxyl group, or a carboxylic acid ester.
  • Suitable alkyl groups have from one to five carbon atoms. 7
  • the compounds represented by the above general formula are colorless under ordinary conditions but when they are irradiated with ultraviolet light having wavelengths of from 2,000 to 4,000 A, they are colored from blue to blue-purple and when they are placed in the dark, they retain the colored state for 10, 20, 30 or more days.
  • the photochromic compounds of the present invention prepared as above are generally colorless or yellow compounds.
  • a solvent such as benzene, toluene, carbon bisulfide, chloroform, ethyl acetate, methyl ethyl ketone, acetone, methyl alcohol, ethyl alcohol, acetonitrile, tetrahydrofuran, dioxane, B- oxymethyl ethyl ether, (methyl cellosolve), morpholine and ethylene glycol to provide a colorless solution and when the solution is irradiated with ultraviolet light, the solution changes to a blue color.
  • a solvent at normal temperature, such as benzene, toluene, carbon bisulfide, chloroform, ethyl acetate, methyl ethyl ketone, acetone, methyl alcohol, ethyl alcohol, acetonitrile, tetrahydrofuran, dioxane, B- oxymethyl ethyl ether, (methyl cellosolve), morpho
  • the compound of the present invention is dissolved in an ethyl acetate solution of polyvinyl acetate, an acetone solution of polymethyl methacrylate, an acetone solution of polyethyl methacrylate, a dimethylformamide solution of cellulose acetate, or a benzene solution of polystyrene, and the resultant solution is applied to a support such as a baryta-coated paper, a synthetic resin sheet such as a cellulose acetate sheet or a polyethylene terephthalate sheet followed by drying to provide a photochromic sheet.
  • a support such as a baryta-coated paper, a synthetic resin sheet such as a cellulose acetate sheet or a polyethylene terephthalate sheet followed by drying to provide a photochromic sheet.
  • the photochromic sheet thus prepared When the photochromic sheet thus prepared is irradiated with ultraviolet light, the sheet is colored blue to blue-purple and when the sheet thus colored is heated or exposed to visible rays after the ultraviolet irradiation, the sheet becomes colorless again. This process can be repeated numerous times.
  • photochromic materials utilizing the above mentioned compounds of the present in vention are a photographic or printing photochromic material prepared by applying the aforesaid composition containing the photochromic compound of this invention to a high molecular weight compound film or a baryta-coated paper, an interior photochromic material prepared by applying the above-mentioned composition to a curtain or glass, a sun glass prepared by applying the composition to a lens or glass, and a photochromic material for use as a filter.
  • the accompanying drawing is a graph showing the change in the spectral characteristics of the compound having the following structure (lit in the graph the absorption spectrum 1 of the compound before irradiation with ultraviolet light and the absorption spectrum 2 thereof after the irradiation of ultraviolet rays are shown.
  • Toshiba SHL-100 was used as the light source and benzene was used as the solvent.
  • EXAMPLE 1 In ml. of ethyl alcohol were dissolved 0.7 g of 5 ,5 '-methylene-bis( 1,2,3 ,3-tetramethyl-indoleniumtosylate) and 0.4 g of 5-nitro-salicylaldehyde and the resultant solution was refluxed for 30 minutes.
  • the solution containing the reaction product was cooled to precipitate crystals, which were recovered by filtration and washed with ethyl alcohol.
  • the crystals were recrystallized from a mixed solvent of ethyl alcohol and acetone to provide 0.5 g. of the crystal of 5 ,5 '-methylene-bis[ 6'-nitro-l ,3 ,3-trimethylspiro-( indoline-2,2'-2H'-chromene)] having a melting point of to 122 C.
  • EXAMPLE 2 In 30 ml. of ethyl alcohol were dissolved 1.4 g. of 5,5-methylene-bis( l ,2,3,3-tetramethyl-indoleniumtosylate), 0.8 g. of 3-methoxy-5-nitro-salicylaldehyde, and 0.5 g. of triethylamine and the resultant solution was refluxed for 20 minutes.
  • the product solution was cooled to precipitate crystals, which were recovered by filtration and washed with ethyl alcohol. Then, the crystals were recrystallized from a mixture of ethyl alcohol and acetone to provide 1.1 g. of the faint green crystals of 5,5"- methylene-bis[6-nitro-8 '-methoxyl ,3 ,3-trimethylspiro-(indoline-2,2'-2H'-chromene)] having a melting point of to 162 C.
  • EXAMPLE 3 In 30 ml. of ethyl alcohol were dissolved 1.4 g of 5 ,5 -methylene-bis( 1,2,3 ,3-tetramethyl-indoleniumtosylate), 0.8 g. of 3-formyl-salicylaldehyde, and 0.5 g of triethylamine, and the resultant solution was refluxed for 20 minutes.
  • the product solution was cooled to precipitate crystals, which were recovered by filtration and washed with ethyl alcohol. Thereafter, the crystals were recrystallized from a mixture of ethyl alcohol and acetone to provide 0.9 g of the faint brown crystals of 5 ,5 -methylene-bis[8 -formyl-1 ,3 ,S-trimethylspiro- (indoline-2,2'-2I-I-chromene)] having a melting point of 159 to 162 C.
  • EXAMPLE 4 In 30 ml. of ethyl alcohol were dissolved 1.1 g. of 5 ,5 '-methylene-bis( l-B -hydroxyethyl-2,3 ,3-trimethylindolenium-bromide), 0.8 g. of 3-formyl-5-nitro-salicylaldehyde, and 0.4 g. of triethylamine and the solution prepared was refluxed for 20 minutes.
  • EXAMPLE 5 In 30 ml. of ethyl alcohol were dissolved 1.3 g. of 5,5-methylene-bis(l-B -carboxyethyl-2,3,3-trimethylindolenium-bromide), 0.8 g. of S-nitro-salicylaldehyde, and the solution thus prepared was refluxed for minutes.
  • the product solution was cooled to precipitate crystals, which were recovered by filtration, washed with ethyl alcohol, and recrystallized from a mixed solvent of ethyl alcohol and tetrahydrofuran to provide 0.9 g. of the faint brown crystals of 5,5"-methylenebis]6'-nitro' l -B-carboxyethyl -3 ,3-dimethylspiro( indoline-2,2-2H'-chromene)].
  • EXAMPLE 6 ln ethyl alcohol were dissolved l.3 g. of 5,5- methylene-bis( l-B-carboxyethyl-2,3,3-trimethyl-indolenium-bromide). 1.2 g. of 3,5-dibromo-salicylaldehyde, and 0.4 g. of triethylamine and the resultant solution was refluxed for 20 minutes.
  • the product solution was cooled to precipitate the crystals, which were recovered by filtration, washed with ethyl alcohol and then recrystallized from a mixed solvent of ethyl alcohol and acetone to provide 1.0 g. of the faint brown crystals of 5,5"-methylene-bis[6',8- dibromo-l-B-carboxyethyl-3,3-dimethylspiro(indoline- 2,2-2H-chromene)] having a melting point of 158 to 160 C.
  • EXAMPLE 7 A benzene solution, a toluene solution, and a tetrahydrofuran solution of the compound prepared in Example I were all colorless and when each of the solutions was irradiated with a mercury lamp, the solution was immediately colored blue and when the solution was placed in the dark, the color of the solution quickly became colorless.
  • EXAMPLE 9 A benzene solution of the compound prepared in Example 2 was colorless but when the solution was exposed to sunlight, it was colored blue and when the solution was placed in the dark, the solution became colorless. The coloring and discharging procedure could be repeated 10, 20, 30 times or more.
  • the light-sensitive paper prepared hadthe same properties as those of the light-sensitive film of Example 7, that is, when the light-sensitive paper was irradiated with ultraviolet light, the photochromic layer was immediately colored dark blue and when it was placed in the dark, the layer became colorless.
  • EXAMPLE l0 A tetrahydrofuran solution or a benzene solution of the compound prepared in Example 3 was colorless but when the solution was irradiated with ultraviolet light, the solution was immediately colored blue and when the irradiation was terminated, the solution quickly became colorless.
  • the compound of the present invention can be'applied to a support or cast together with a sensitizer and a plasticizer.
  • a photochromic compound having the formula wherein R is a member selected from the group consisting of an alkyl group of from one to five carbon group consisting of an alkyl group of from one to five carbon atoms, a nitro group, a halogen atom, formyl and methoxy.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Optical Filters (AREA)
US00020761A 1969-03-18 1970-03-18 Spiro(indoline-2,2'-2h'-chromene)photochromic compounds Expired - Lifetime US3714187A (en)

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JP44020657A JPS4945064B1 (enrdf_load_stackoverflow) 1969-03-18 1969-03-18

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US (1) US3714187A (enrdf_load_stackoverflow)
JP (1) JPS4945064B1 (enrdf_load_stackoverflow)
BE (1) BE747554A (enrdf_load_stackoverflow)
DE (1) DE2012687A1 (enrdf_load_stackoverflow)
FR (1) FR2039667A5 (enrdf_load_stackoverflow)
GB (1) GB1304042A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100068442A1 (en) * 2007-10-24 2010-03-18 Chin Kang Sha Trimethine Cyanine Compounds, Their Preparation and Their Use

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5111376U (enrdf_load_stackoverflow) * 1974-07-12 1976-01-27
JPS5133769U (enrdf_load_stackoverflow) * 1974-09-05 1976-03-12

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1394163A (fr) * 1964-02-18 1965-04-02 Saint Gobain Compositions photochromes notamment pour la fabrication de vitrages à transmission variable

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1394163A (fr) * 1964-02-18 1965-04-02 Saint Gobain Compositions photochromes notamment pour la fabrication de vitrages à transmission variable

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100068442A1 (en) * 2007-10-24 2010-03-18 Chin Kang Sha Trimethine Cyanine Compounds, Their Preparation and Their Use
US8168282B2 (en) * 2007-10-24 2012-05-01 Orgchem Technologies, Inc. Trimethine cyanine compounds, their preparation and their use

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GB1304042A (enrdf_load_stackoverflow) 1973-01-24
FR2039667A5 (enrdf_load_stackoverflow) 1971-01-15
JPS4945064B1 (enrdf_load_stackoverflow) 1974-12-02
BE747554A (fr) 1970-08-31
DE2012687A1 (de) 1970-09-24

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