Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
  • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
  • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
• • 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

• These compounds in solution are substantially colorless but may be changed, at will, to a colored state, in which the 2'-1 bond is broken, by being subjected to light predominating in components from blue through ultraviolet wave-lengths, and reversed back, at will, in solution, to the substantially colorless state by such solutions being subjected to light predominating in components of wavelengths in the green through infra-red region of the spectrum.
• These compounds are useful in sensitizing record materials so as to exhibit data by colored and uncolored areas thereon, which data has been selectively recorded thereon, or erased therefrom, by the application of recording light or erasing light or heat.
• Solutions of the compounds are also useful as components of optical filters which darken on being subjected to ultra-violet or blue light, such filters being adapted for protecting the eyes from tissue-damaging light or from temporarily-induced blindness from excessive light, inasmuch as they respond immediately to the coloring light waves which accompany great excesses of visible light.
• novel compounds of this invention will, in the absence of exposure to shortwave-length change-provoking light, remain in the colorless state indefinitely, when in solution, either at or about normal room temperatures; and that said compounds when in the colored states, in solution, not only will quickly revert to the colorless form by the action of longer-wave-length change-provoking light, but will also, even in the dark, rapidly revert to said colorless state, by thermal activity, at or about normal room temperatures.
• the rate of reversion is temperature-dependent, the rate increasing with increasing temperature.
• the rate at which these compounds revert from the colored form to the colorless form is normally expressed as the half-life of the colored form of the compound and is a quantitative measure of the thermal stability of such compounds at or about room temperature.
• the average varying from about one minute to about ten minutes.
• a suitable method for determining the half-life of the colored form of the instant compounds is to determine, at a selected wave-length, the rate of decrease in absorbence of a solution of the compounds wlr'le kept in the dark, over a known time interval, and, by the use of wellknown rate formulas and a graph plot of the variables, to calculate the interval of time required for the absorbence to decrease from a maximum value to half this value.
• solution as used herein, is meant the homogeneous mixture of one or more of the claimed compounds with a solid or liquid substance.
• stable as used in this application, it is meant that the compounds of this invention have considerably less room temperature thermal stability than numerous related compounds from different classes of spiro-pyran compounds; for example, such as the compounds disclosed in the above-specified co-pending application.
• radicals which may be attached at any one of the 4, 5, 6, 7, 5', 6', 7, and 8 positions are the following: CH CH CH CH(CH the phenyl group C 21 (3P CN; COCH CO C H CO H; NR NHCH N(CH NHCOCH N(CH N0 S 3; 2 5; 2h 3; s s); OCOCH SCI-l SH; SCOCH SCN; SOCH SO CH SO NH S(CH F; Cl; Br; I; 10 CH CH CH and CO CH
• Any of the substituents or group of sterically compatible substituents may be selected for attachment at the specified positions, and such compounds may be subsequently pared by condensing the selectively substituted salicylaldehyde (to give substituents in the 6, 7', or 8' positions, as desired) with the selectively substituted 2-ethyl- 3-alkylbenzoxazole (to give substituents in the 4, 5, 6, or 7 positions, as desired.)
• the 3-alkyl group may be introduced
• some of the compounds most suitable for the uses and purposes described herein, wherein the compounds are reversibly colorable but have a low or reduced thermal stability in the colored form within the temperature range suitable for normal human activity may be represented by the general structural formula R R7 Rs Example I
• R R7 Rs Example I
• the preparation of 3,3'-dimethyl-6-nitro-spiro-(benzoxazole 2,2-[2'H,1-benzopyran] Thirty-one grams (0.28 mole) of o-aminophenol and 38 grams (0.28 mole) of propionic anhydride are placed in a 250-milliliter round-bottom flask and heated on a steam bath for two hours.
• the mixture is then heated to drive off the water and ammonia, and the residue is distilled at atmospheric pressure to yield 25 grams of a light-yellow oil with a boiling point of 214 to 217 degrees centigrade, which is 2-ethylbenzoxazole.
• the 2-ethylbenzoxazole thus prepared, is placed in a lOO-milliliter round-bottom flask, and 32 grams (0.17 mole) of methyl-p-toluene sulfonate is added.
• the mixture is heated at 140 to 155 degrees centigrade for two hours and allowed to cool to room temperature.
• the resultant light-yellow solid is Washed several times with acetone to yield the second intermediate, 2-ethylbenzoxazole methyl-p-toluene sulfonate.
• Example II Preparation of 3,3'-dirnethyl-8'-nitro-spiro-(benzoxazole-2,2-[2H(l-benzopyran]): Place (0.28 mole of oaminophenol and (0.28 mole) of propionic anhydride in a 250-milliliter round-bottom flask and heat on a steam bath for two hours. The mixture then is heated to drive off the water and ammonia, and the residue is distilled at atmospheric pressure to yield a light-yellow oil with a boiling point of 214 to 217 degrees centigrade, which is 2-ethylbenzoxazole.
• the 2-ethylbenzoxazole thus prepared, is placed in a -milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added. The mixture is heated at to degrees centigrade for two hours and allowed to cool to room temperature. The resultant light-yellow solid is washed several times with acetone to yield the second intermediate, 2-ethylbenzoxazole methyl-p-toluene sulfonate.
• Example III Preparation of 3,3-dimethyl-6'-chloro-8-nitro-spiro- (benzoxazole-2,2'-[2H,1'-benzopyran])z Place (0.28 mole) of o-aminophenol and (0.28 mole) of propionic anhydride in a 250-milliliter round-bottom flask and heat on a steam bath for two hours. The mixture is then heated to drive off the water and ammonia, and the residue is distilled at atmospheric pressure to yield a light-yellow oil with a boiling point of 214 to 217 degrees centigrade, which is Z-ethylbenzoxazole.
• the 2-ethylbenzoxazole thus prepared is placed in a l00-milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added.
• the mixture is heated at 140 to 155 degrees centigrade for two hours and allowed to cool to room temperature.
• the resultant light-yellow solid is washed several times with acetone to yield the second intermediate, 2-ethylbenzoxazole methyl-p-toluene sulfonate.
• Example IV Preparation of 3,3'-dimethyl-6'-methoxy-8-nitro-spiro- (benzoxaZole-2,2'-[2H,1'benzopyran]): Place (0.28 mole) of o-aminophenol and (0.28 mole) of propionic anhydride in a 250-milliliter round-bottom flask and heat on a steam bath for two hours. The mixture is then heated to drive off the water and ammonia, and the residue is distilled at atmospheric pressure to yield a light-yellow oil with a boiling point of 214 to 217 degrees centigrade, which is Z-ethylbenzoxazole.
• the 2-ethylbenzoxazole thus prepared is placed in a IOO-milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added.
• the mixture is heated at 140 to 155 degrees centigrade for two hours and allowed to cool to room temperature.
• the resultant light-yellow solid is washed several times with acetone to yield the second intermediate, 2-ethylbenzoxazole methyl-p-toluene sulfonate.
• Example V Preparation of 3,3'-dimethyl-6'-nitro-8'-methoxy-spiro- (benzoxazole-2,2'-[2'H,1'-benzopyran]): Place (0.28 mole) of o-aminophenol and (0.28 mole) of propionic anhydride in a 250-1nilliliter round-bottom flask and heat on a steam bath for two hours. The mixture then is heated to drive off the Water and ammonia, and the residue is distilled at atmospheric pressure to yield a light-yellow oil with a boiling point of 214 to 217 degrees centigrade, which is 2-ethylbenzoxazole.
• the Z-ethylbenzoxazole thus prepared is placed in a 100-milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added.
• the mixture is heated at 140 to 155 degrees centigrade for two hours and allowed to cool to room temperature.
• the resultant light-yellow solid is washed several times with acetone to yield the second intermediate, 2-ethylbenzoxazole methyl-p-toluene sulfonate.
• Example VI Preparation of 3,3'-dimethyl-5-chloro-6'-nitro-spiro- (benzoxazole-2,2-[2'H,1-benzopyran]): Place (0.28 mole) of 2-amino-4-chlorophenol and (0.28 mole) of propionic anhydride in a 250-milliliter round-bottom flask and heat on a steam bath for two hours. The mixture then is heated to drive oil the water and ammonia, and the residue is distilled at atmosphic pressure to yield a light-yellow oil with a boiling point of 240 to 247 degrees centrigrade, which is 5-chloro-2 ethylbenzoxazole.
• the 5chloro-2-ethylbenzoxazole thus pre-. pared, is placed in a l-milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added. The mixture is heated at 140 to 155 degrees centigrade for two hours and allowed to cool to room temperature. The resultant light-yellow solid is washed several times with acetone to yield the second intermediate, S-chloro-Z- ethylbenzoxazole methyl-p-toiuene sulfonate.
• Example VII Preparation of 3,3,5-t.rirnethyl-6'-nitro-spiro-(benzoxazole-2,2'-[2'H,1'-benzopyran]: Place (0.28 mole) of 2-amino-4-methylphenol and (0.28 mole) of propionic anhydride in a 250-milliliter round-bottom flask and heat on a steam bath for two hours. The mixture then is heated to drive off the water and ammonia, and the residue is distilled at atmospheric pressure to yield a light-yellow oil with a boiling point of 228 to 235 degree centigrade, which is 5-methyl-2ethylbenzoxazole.
• ethylbenzoxazole thus prepared is placed in a -milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added. The mixture is heated at to degrees centigrade for two hours and allowed to cool to room temperature. The resultant light-yellow solid is washed several times with acetone to yield the second intermediate, 5 methyl Z-ethylbenzoxazole methyl-ptoluene sulfonate.
• the 5-methyl-2-ethylbenzoxazole thus prepared is placed in a 100-milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added.
• the mixture is heated at 140 to 155 degrees centigrade for two hours and allowed to cool to room temperature.
• the resultant lightyellow solid is washed several times with acetone to yield the second intermediate, 5-methyl-2 -ethylbenzo-xazole methyl-p-toluene sulfonate.
• Example 1X Preparation of 3,3',5-trimethyl-6'-nitro 8'-methoxyspiro (benzoxazole-2,2'-[2H,1-benzopyran]): Place (0.28 mole) of 2-amino-4-methylphenol and (0.28 mole) of propionic anhydride in a 250-milliliter round-bottom flask and heat on a steam bath for two hours. The mixture then is heated to drive off the water and ammonia, and the residue is distilled at atmospheric pressure to yield a light-yellow oil with a boiling point of 228 to 235 degrees centigrade, which is 5-rnethyl-2-ethylbenzoxazole.
• the S-methyl-Z-ethylbenzoxazole thus prepared, is placed in a lOO-milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added. The mixture is heated at 140 to 155 degrees centigrade for two hours and allowed to cool to room temperature. The resultant light-yellow solid is washed several times with acetone to yield the second intermediate, S-methyl-Z-ethylbenzoxazole methyl-p-toluene sulfonate.
• Example X Preparation of 3,3,5,7atetramethyl-6 nitro-8'-methoxyspiro-(benzoxazole 2,2 [2H,1' benzopyran1) Place (0.28 mole) of 2-amino-4,6-dimethylphenol and (0.28 mole) of propionic anhydride in a -250-milliliter roundbottom flask and heat on a steam bath for two hours. The mixture then is heated to drive off the water and ammonia, and the residue is distilled at atmospheric pressure to yield a light-yellow oil, which is 5,7-dimethyl-2- ethylbenzoxazole.
• the compound thus prepared is placed in a 100-milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added.
• the mixture is heated at 140 to 155 degrees cent-igrade for two hours and allowed to cool to room temperature.
• the resultant light-yellow solid is washed several times with acetone to yield the second intermediate, 5,7-dimethyl-2-ethylbenzoxazole methyl-p-toluene sulfonate.
• Example XI Preparation of 3,3-dimethyl-5phenyl-6"nitro-spiro- (benzoxazole-2,2'-[2H,1 benzopyran1) Place (0.28 mole) of 2-amino-4-phenylphenol and (0.28 mole) of propionic anhydride in a 250-rnilliliter round-bottom flask and heat on a steam bath for two hours. The mixture is then heated to drive ofl the water and ammonia, and the residue is distilled at atmospheric pressure to yield a light-yellow oil with a boiling point of 150 to 165 degrees centigrade, which is 5-phenyl-2-ethylbenzoxazole.
• the compound thus prepared is placed in la 100-milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added.
• the mixture is heated at 140* to 155 degrees centigrade for two hours and allowed .to cool to room temperature.
• the resultant light-yellow solid is washed several times with acetone to yield the second intermediate, 5-phenyl-2-ethyl-benzoxazole methyl-p-toluene sulfonate.
• Example XII Preparation of 3,3-dimethyl-5-phenyl-6-nitro-8'-methoxy spiro (benzoxazole-2,2'-[2H,1'-benzopyran]): Place (0.28 mole) of 2-amino-4-phenylphenol and (0.28 mole) of propionic anhydride in a 250-milliliter roundbottom flask and heat on a steam bath for two hours. The mixture then is heated to drive oif the water and ammonia, and the residue is distilled at atmospheric pressure to yield a light-yellow oil with a boiling point of 150 to 165 degrees centigrade/l mm. Hg, which is 5- phenyl-Z-ethylbenzoxazole.
• the compound thus prepared is placed in a -milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added.
• the mixture is heated at to degrees centigrade for two hours and allowed to cool to room temperature.
• the resultant light-yellow solid is washed several times with acetone to yield the second intermediate, S-phenyl-Z-ethylbenzoxazole methyl-p-toluene sulfonate.
• Example XIII Preparation of 3-methyl-3-ethyl-6'-nitro-spiro-(benz- 0xazole-2,2'-[2H,1'-benzopyran])2 Place (0.28 mole) of o-aminophenol and (0.28 mole) of n-butyric anhydride in a 250-milliliter round-bottom flask and heat on a steam bath for two hours. The mixture then is heated to drive off the Water and ammonia, and the residue is distilled at atmospheric pressure to yield a light-yellow oil with a boiling point of 220 to 232 degrees centigrade, which is Z-(n-propyl)-benzoxazole.
• the compound thus prepared is placed in a 100-milliliter round-bottom flask, and (0.17 mole) of methyl-p-toluene sulfonate is added.
• the mixture is heated at 140 to 155 degrees centigrade for two hours and allowed to cool to room temperature.
• the resultant light-yellow solid is washed several times with acetone to yield the second intermediate, 2-(n-propyl)-benzoxazole methyl-p-toluene sulfonate.

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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)
• Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)

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Cited By (8)

• 0
  • NL NL123451D patent/NL123451C/xx active
  • NL NL253899D patent/NL253899A/xx unknown
• 1960
  • 1960-07-01 GB GB23083/60A patent/GB889186A/en not_active Expired
  • 1960-07-12 CH CH794960A patent/CH398598A/fr unknown
• 1962
  • 1962-02-15 US US173355A patent/US3149120A/en not_active Expired - Lifetime

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