WO1997006455A1 - Composes photochromes de naphtopyranes - Google Patents

Composes photochromes de naphtopyranes Download PDF

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Publication number
WO1997006455A1
WO1997006455A1 PCT/US1995/010047 US9510047W WO9706455A1 WO 1997006455 A1 WO1997006455 A1 WO 1997006455A1 US 9510047 W US9510047 W US 9510047W WO 9706455 A1 WO9706455 A1 WO 9706455A1
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WO
WIPO (PCT)
Prior art keywords
article
substituted
phenyl
group
naphthyl
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Application number
PCT/US1995/010047
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English (en)
Inventor
Frank J. Hughes
Original Assignee
Bmc Industries, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
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Priority to PCT/US1995/010047 priority Critical patent/WO1997006455A1/fr
Publication of WO1997006455A1 publication Critical patent/WO1997006455A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters

Definitions

  • the present invention generally relates to naphthopyran compounds. More specifically, the present invention relates to photochromic naphthopyran compounds and to articles made of photochromic compounds.
  • Photochromism generally concerns the ability of a compound to reversibly change color under different light conditions.
  • One particular type of photochromic phenomenon concerns the reversible change in color of a compound from an original color to a different color when the compound is exposed to a source of ultraviolet radiation, such as solar radiation or light radiated from a mercury lamp.
  • the photochromic compound fades to the original color within a period of time after the compound is isolated from the ultraviolet radiation, such as by placing the compound in a dark room.
  • photochromic compounds such as naphthopyrans
  • plastic ophthalmic lenses to effect color changes in the plastic lenses when the lenses are exposed to particular lighting conditions.
  • different photochromic compounds may be blended to create a color effect that is different from the respective color effects of the individual photochromic compounds.
  • a first photochromic compound that turns orange or red when activated by light and a second photochromic compound that turns blue when activated by light may be blended to form a photochromic mixture that produces a shade of gray when activated by light.
  • photochromic compounds have been reported which exhibit changes in color when exposed to ultraviolet light.
  • One particular class of photochromic compounds includes the 3, 3 -disubstituted naphthopyrans.
  • One specific group of 3.3-disubstituted naphthopyran of interest includes the 3H- naphtho[2,lb]pyrans.
  • the color response of the 3H-naphtho[2,lb]pyrans to ultraviolet light extends to purple, red, orange or yellow, depending upon the composition and structure of the particular 3H-naphtho[2,lb]pyrans.
  • a general expression of the 3H-naphtho[2,lb]pyrans is provided in graphical formula I:
  • the Becker patent describes chromenes and chromene derivatives which are photochromic at relatively low temperatures.
  • the patent also describes chromenes and chromene derivatives which are photochromic at room temperature, such as diphenyl-3H-naphtho[2,lb]pyran, where R, and R 2 of formula I are each unsubstituted phenyl groups.
  • Additional photochromic compounds are described in U.S. Patent No. 4,931,221 to Heller et al.
  • One type of photochromic compound described in Heller generally has the form of graphical formula I with R, and R 2 being cyclopropyl radicals and with any of various substituents included on the naphtho portion of the naphthopyran rings.
  • Heller reports a larger bathochromic shift in the visible spectrum of 3H-naphtho[2,lb]pyrans that include the cyclopropyl radicals as compared to 3H-naphtho[2,lb]pyrans that include alkyl groups or a spirocycloalkyl group in place of the cyclopropyl radicals.
  • Tanaka describes compounds in which R, and R 2 of graphical formula I are alkyl groups. Tanaka also describes compounds in which, together, R, and R 2 of graphical formula I are either a norbornylidene radical or a bicyclo[3,3,l]9-nonylidene radical. Tanaka reports several fade times and maximum absorption wavelengths associated with various 3H- naphtho[2,lb]pyrans that include either the alkyl radicals, the norbornylidene radical or the bicyclo[3,3,l]9-nonylidene radical as R, and R 2 .
  • U.S. Patent 5,238,981 to Knowles teaches a 3H- naphtho[2,lb]pyran compound in which R, and R 2 of graphical formula I are each selected from a group of organic radicals that includes phenyl and naphthyl.
  • the organic radicals placed at R, and R 2 are either substituted or unsubstituted.
  • Potential substituents of substituted organic radicals placed at R, and R 2 provided that one of the organic radicals placed at R, and R 2 is a phenyl group, include various non-aryl groups.
  • Various potential substitutions on the naphtho portion of the naphthopyrans ring are taught, including an 8-methoxy substitution.
  • Van Gemert describes 3H-naphtho[2,lb]pyrans in which R, and R 2 of graphical formula I are each phenyl, naphthyl, various heterocyclic groups, and certain non-aryl groups. Van Gemert also discusses substitution of various non-aryl substituents into any phenyl, naphthyl, heterocyclic, and non-aryl groups placed at R, and R 2 . Van Gemert also states that certain substitutions at the number 5 carbon on the naphtho ring causes a bathychromic shift of the absorption maximum of the 3H-naphtho[2,lb]pyrans.
  • Van Gemert describes certain 3H- naphtho[2,lb]pyrans in which R, of graphical formula I is a phenyl group, a naphthyl group, a furyl group, or a thienyl group and in which R 2 of graphical formula I is an arylalkenyl radical.
  • Van Gemert describes a bathychromic shift associated with the 3H-naphtho[2,lb]pyrans that include the arylalkenyl radical relative to certain other naphthopyrans disclosed in U.S. Patent No. 3,567,605.
  • Rq. R 10 . and R n are each selected from the group consisting essentially of hydrogen, a first stable organic radical, a heterocyclic group, halogen, a first nitrogen-substituted group, and a first nitrogen-substituted ring compound.
  • a and B are each selected from the group consisting essentially of hydrogen, substituted phenyl, and substituted naphthyl. provided that at least one of A or B is substituted phenyl or substituted naphthyl.
  • any substituent of any substituted phenyl or substituted naphthyl at A or B is selected from the group consisting essentially of hydrogen, a second stable organic radical, a heterocyclic group, halogen, a second nitrogen-substituted group, and a second nitrogen-substituted ring compound, provided that at least one substituent of at least one substituted phenyl or substituted naphthyl at either A or B is phenyl, naphthyl, or furyl.
  • the present invention further includes a photochromic article comprising a host material and a photochromic amount of a naphthopyran compound and additionally includes the following 3-(4- biphenylyl)-3-phenyl- 8-methoxy-3H-naphtho[2, l b]pyran, 3-(4- biphenylyl)-3-phenyl-3H-naphtho[2,lb]pyran, and 3,3-di(4-biphenylyl)-8- methoxy-3H-naphtho-[2, lb]pyran.
  • Novel naphthopyran compounds of the present invention may be represented by graphic fo ⁇ nula II as follows:
  • substituents may be placed on the pyran portion and the naphtho portion of the naphthopyran rings.
  • the positions represented in graphic formula II by R 4 , R 5 , R ⁇ , R 7 , R 8 , RQ, R 10 , and R n , respectively, may be filled with hydrogen; a stable organic radical, such as alkyl, alkoxy, unsubstituted or substituted phenyl, naphthyl, cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl, aroyloxy; a heterocyclic group; halogen; a nitrogen-substituted group, such as amino or nitro; or a nitrogen-substituted ring compound, such as morpholino, piperidino, or piperazino.
  • A is hydrogen, a substituted phenyl group, or a substituted naphthyl group
  • B is hydrogen, a substituted phenyl group, or a substituted naphthyl group, provided that at least one of A and B is substituted phenyl or substituted naphthyl.
  • the substituents of any phenyl or naphthyl group or groups at A or B are selected from the following: a stable organic radical, such as alkyl, alkoxy, unsubstituted or substituted phenyl, naphthyl, cycloalkyl. furyl. alkoyl.
  • the naphthopyran compounds represented by graphic formula II are derivatives of 3,3-aryl-disubstituted-aryl chromenes. These naphthopyran compounds exhibit a su ⁇ rising and highly desirable bathychromic shift of the maximum activated wavelength.
  • the bathychromic shift exhibited by the inventive naphthopyran compounds provide photochromic species which turn orange, reddish-orange or purple when activated by solar radiation or an ultraviolet radiation source.
  • Photochromic compounds with maximum activated wavelengths approaching 500 nanometers change from original states of color to deep shades of orange, reddish-orange or red when activated by ultraviolet light.
  • the colored forms of the activated photochromic compounds fade to the original, unactivated colored states at ambient temperatures when isolated from the ultraviolet light.
  • Photochromic compounds that turn deep shades of orange, reddish orange, or red when activated are hereinafter referred to as "intense photochromes" for purposes of this disclosure only.
  • inventive naphthopyrans represented by graphical equation II especially the intense photochromes, exhibit a deeper color and a larger bathochromic shift in the visible spectrum of the activated form as compared to existing naphthopyrans.
  • inventive naphthopyrans represented by graphical equation II especially the intense photochromes, approach a maximum activated wavelength of 500 nanometers; exhibit deep shades of orange, reddish orange, or purple; and include an acceptable fade characteristic.
  • the inventive intense photochromes may be blended with one or more other photochromic compounds of different maximum activation wavelengths from that of the inventive intense photochromes to make photochromic mixtures.
  • the other photochromic compounds turn colors other than orange, reddish orange and purple when activated with ultraviolet light.
  • one or more of the inventive intense photochromes is preferably blended with another photochromic compound which has a different maximum activation wavelength and which turns blue when activated with ultraviolet light to make the photochromic mixture. It has been discovered that photochromic mixtures that include the inventive intense photochromes and blue-turning photochromic compounds change to desirable shades of gray when activated by ultraviolet light, such as that present in sunlight.
  • the photochromic mixtures may be desirably applied to or incorporated within substrates, such as conventional synthetic plastic materials often used for optical elements.
  • Compounds of graphic formula II above may be prepared by reacting a suitable ketone precursor with lithium acetylide in a tetrahydrofuran solvent. The product of this reaction is then reacted with a suitably substituted 2-naphthol with a catalytic amount of p-toluenesulfonic acid. The resultant material is then purified by recrystallization, column chromatography, or a combination of recrystallization and column chromatography.
  • a preferred naphthopyran compound is 3-(4-biphenylyl)-3-phenyl-8-methoxy-3H-naphtho[2,lb]pyran that may be represented by graphic formula III below:
  • 3-(4-biphenylyl)-3-phenyl-8-methoxy-3H-naphtho[2, lb]pyran unexpectedly exhibits a maximum activated wavelength of absorption of about 484 nanometers, very near 500 nanometers, when irradiated with ultraviolet light. Additionally, when activated by ultraviolet light, the 3-(4- biphenylyl)-3-phenyl-8-methoxy-3H-naphtho[2,lb]pyran turns a deep shade of orange.
  • the 3 -(4-biphenylyl)-3 -phenyl-8- methoxy-3 H-naphtho [2, 1 bjpyran desirably blends with blue-turning photochromic compounds, such as a substituted spiroindolino naphthoxazine, to advantageously make one ofthe photochromic compound blends that changes to an intense shade of gray when activated by ultraviolet radiation.
  • blue-turning photochromic compounds such as a substituted spiroindolino naphthoxazine
  • Compounds represented by graphic formula II may be used in many applications of plastic substrates.
  • compounds represented by graphic formula II may be incorporated into a host material that is applied to or used to make an article.
  • compounds represented by graphic formula II may be incorporated with a host material to make a coating for a suitable substrate.
  • compositions, such as photochromic mixtures, that contain one or more of the photochromic compounds represented by graphic formula II may be incorporated into a host material that is applied to or used to make an article.
  • compounds represented by graphic formula II and compositions containing compounds represented by graphic formula II may be incorporated into a coating material that is applied to a host material.
  • a polymerized organic material such as a synthetic polymerized plastic, is one example of the host material.
  • the article include plastic optical elements, such as piano and ophthalmic lenses.
  • Non-exhaustive illustrations of suitable synthetic polymerized plastics include polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polyurethane, cellulose ester and bis-polyol (allyl carbonate) monomer-based polymer.
  • bis-polyol (allyl carbonate) monomer and similar phrases are intended to mean and include the named monomer or prepolymer and any related monomer series contained therein.
  • bis-polyol (allyl carbonate) monomers include ethylene glycol bis(allyl carbonate), diethylene glycol bis(2-methallyl carbonate), diethylene glycol bis(allyl carbonate), propylene glycol bis(2-ethylallyl carbonate), 1-3-propanediol bis(allyl carbonate), 1,3 -butanediol bis(allyl carbonate), 1 ,4-butanediol bis(2,bromoallyl carbonate), dipropylene glycol bis(allyl carbonate), trimethylene glycol bis(2-ethylallyl carbonate), pentamethylene glycol bis(allyl carbonate), and isopropylidene bisphenol bis(allyl carbonate).
  • the amount of a particular one of the compounds represented by graphic formula II, or a particular composition containing one ofthe compounds represented by graphic formula II, that is inco ⁇ orated into the host material or the coating material is defmed, for pu ⁇ oses of this disclosure, as the photochromic amount.
  • the photochromic amount is not critical, provided that a sufficient amount to produce a photochromic effect perceptible to the human eye is used.
  • the photochromic amount often depends on the desired intensity of the color on activation of the particular inventive naphthopyran and on the method of inco ⁇ oration or application of the particular inventive naphthopyran.
  • the photochromic amount inco ⁇ orated into or applied to the host material or inco ⁇ orated into the coating material ranges from about 0.01 to about 20 percent by weight, based on the weight of the host material or the weight of the coating material, as applicable.
  • Step 1 Five grams of 4-phenylbenzophenone were placed together with 5 grams of lithium acetylide in 250 milliliters of tetrahydrofuran and stirred for 72 hours. The resultant mixture was poured over ice and diluted with water to form an organic layer and an aqueous layer. The organic layer was separated from the aqueous layer and dried with anhydrous sodium sulfate. The dried organic layer was evaporated to obtain a solid material. The solid material was then triturated with acetone. Nuclear magnetic resonance (NMR) spectroscopy showed the resultant material to be relatively pure (4-biphenylyl)phenyl propargyl alcohol.
  • NMR Nuclear magnetic resonance
  • Step 1 Five grams of bis-(4-biphenyl)ketone were placed together with
  • the recrystallized product was shown to be relatively pure 3,3-di(4-biphenylyl)- 8-methoxy-3H-naphtho-[2,lb]pyran by nuclear magnetic resonance (NMR) spectroscopy.
  • Step 2 Two grams of the diphenyl propargyl alcohol were mixed with 1.71 grams of 6-methoxy-2-naphthol in 200 milliliters of benzene. Twenty milligrams of p-toluenesulfonic acid were then added and the mixture was stirred under reflux for 8 hours.
  • the resultant mixture was cooled and washed with 10% aqueous sodium hydroxide.
  • the organic solvent (benzene) was removed using a rotary evaporator.
  • the resulting material was dissolved in a solvent and the solvent solution was cooled to yield a recrystallized product.
  • the recrystallized product was shown to be relatively pure 3 ,3-diphenyl-8-methoxy-3H-naphtho-[2, 1 b]pyran by nuclear magnetic resonance NMR spectroscopy.
  • Example 1 The photochromic compounds formed in Example 1 (3-(4- biphenylyl)-3-phenyl-8-methoxy-3H-naphtho[2,lb]pyran), Example 2 (3-(4- biphenylyl)-3 -phenyl-3H-naphtho- [2, 1 b]pyran), Example 3 (3 ,3-di(4-biphenylyl)- 8-methoxy-3H-naphtho-[2,lb]pyran) and Comparative Example 1 (3,3-diphenyl-8-methoxy-3H-naphtho-[2,lb]pyran), along with the Comparative Example 2 purchased sample of 3,3-diphenyl-3H-naphtho-[2,lb]pyran, were each dissolved in chloroform in separate containers.
  • Each of the chloroform-dissolved photochromic compounds were then irradiated with ultraviolet light of maximum wavelength of 350 manometers and measured for maximum abso ⁇ tion wavelength, ⁇ max .
  • the fade time, T, /2 was then determined for each of the irradiated compounds.
  • the fade time for a particular chloroform-dissolved photochromic compound is defined as the time interval, at room temperature (72°F), for the absorbance of the activated form of the chloroform-dissolved photochromic compound to decrease to one half of the maximum absorbance, after the photochromic compound is isolated from the activating source of ultraviolet light.
  • the maximum abso ⁇ tion wavelength and fade time determined for each of the irradiated photochromic compound are presented in Table 1 : TABLE 1
  • the Table 1 values also illustrate that the 3-(4-biphenylyl)-3-phenyl-8-methoxy-3H-naphtho[2,lb]pyran of Example 1 and the 3,3-di(4-biphenylyl)-8-methoxy-3H-naphtho[2,lb]pyran of Example 3 each have longer wavelengths of activation than the 3,3-diphenyl-8-methoxy-3H- naphtho[2,lb]pyran of Comparative Example 1.
  • the longer maximum wavelengths of activation of the 3-(4-biphenylyl)-3-phenyl-8-methoxy-3H- naphtho[2,lb]pyran of Example 1, of the 3-(4-biphenylyl)-3-phenyl-3H- naphtho[2,lb]pyran of Example 2, and the 3,3-di(4-biphenylyl)-8-methoxy-3H- naphtho[2,lb]pyran of Example 3 are desirable characteristics for photochromic compounds.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Optical Filters (AREA)
  • Pyrane Compounds (AREA)

Abstract

L'invention porte sur un composé de naphtopyrane de formule (I), dans laquelle: R4, R5, R6, R7, R8, R9, R10 et R11 sont chacun sélectionnés dans un groupe consistant essentiellement en hydrogène, un premier radical organique stable, un groupe hétérocyclique, halogène, un premier groupe à substitution azote, un premier composé cyclique à substitution azote; A et B sont tous deux sélectionnés dans un groupe consistant essentiellement en hydrogène, phényle substitué et naphtyle substitué, sous réserve que l'un d'eux au moins soit phényle substitué ou naphtyle substitué; et que tout substituant de tout phényle substitué ou naphtyle substitué en A ou B soit sélectionné dans le groupe consistant essentiellement en hydrogène, un second radical organique stable, un groupe hétérocyclique, un halogène, un second groupe à substitution azote et un second composé cyclique à substitution azote, sous réserve qu'au moins un substituant de tout phényle substitué ou de tout naphtyle substitué en A ou B soit phényle, naphtyle ou furyle.
PCT/US1995/010047 1995-08-08 1995-08-08 Composes photochromes de naphtopyranes WO1997006455A1 (fr)

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PCT/US1995/010047 WO1997006455A1 (fr) 1995-08-08 1995-08-08 Composes photochromes de naphtopyranes

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010215578A (ja) * 2009-03-18 2010-09-30 Tokuyama Corp クロメン化合物の製造方法
US8518546B2 (en) 2003-07-01 2013-08-27 Transitions Optical, Inc. Photochromic compounds and compositions
US8545984B2 (en) 2003-07-01 2013-10-01 Transitions Optical, Inc. Photochromic compounds and compositions
US8698117B2 (en) 2003-07-01 2014-04-15 Transitions Optical, Inc. Indeno-fused ring compounds
US10000472B2 (en) 2003-07-01 2018-06-19 Transitions Optical, Inc. Photochromic compounds

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5066818A (en) * 1990-03-07 1991-11-19 Ppg Industries, Inc. Photochromic naphthopyran compounds
US5238981A (en) * 1992-02-24 1993-08-24 Transitions Optical, Inc. Photochromic naphthopyrans
US5244602A (en) * 1990-12-03 1993-09-14 Ppg Industries, Inc. Photochromic naphthopyrans

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5066818A (en) * 1990-03-07 1991-11-19 Ppg Industries, Inc. Photochromic naphthopyran compounds
US5244602A (en) * 1990-12-03 1993-09-14 Ppg Industries, Inc. Photochromic naphthopyrans
US5238981A (en) * 1992-02-24 1993-08-24 Transitions Optical, Inc. Photochromic naphthopyrans

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8518546B2 (en) 2003-07-01 2013-08-27 Transitions Optical, Inc. Photochromic compounds and compositions
US8545984B2 (en) 2003-07-01 2013-10-01 Transitions Optical, Inc. Photochromic compounds and compositions
US8698117B2 (en) 2003-07-01 2014-04-15 Transitions Optical, Inc. Indeno-fused ring compounds
US9309455B2 (en) 2003-07-01 2016-04-12 Transitions Optical, Inc. Indeno-fused ring compounds
US10000472B2 (en) 2003-07-01 2018-06-19 Transitions Optical, Inc. Photochromic compounds
US10005763B2 (en) 2003-07-01 2018-06-26 Transitions Optical, Inc. Photochromic compounds
US10501446B2 (en) 2003-07-01 2019-12-10 Transitions Optical, Inc. Photochromic compounds
US10532997B2 (en) 2003-07-01 2020-01-14 Transitions Optical, Inc. Photochromic compounds
US10532998B2 (en) 2003-07-01 2020-01-14 Transitions Optical, Inc. Photochromic compounds
JP2010215578A (ja) * 2009-03-18 2010-09-30 Tokuyama Corp クロメン化合物の製造方法

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