JP2010001297A - Substituted naphthopyrans - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new photo-coloring (photochromic) naphthopyran compound and a composition and an article containing the naphthopyran compound. <P>SOLUTION: A compound having a specific substituent for the carbon atom at the fifth position of the naphtho-part of naphthopyran and at the second position in the pyran ring of naphthopyran, such as 2-(4-morpholinophenyl)-2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho[1, 2-b]pyran and 2-(9-ethylcarbazole-2-yl)-2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho[1, 2-b]pyran is provided. An organic host material containing the compound or an organic host material coated with the compound, and in addition an article containing the new naphthopyran compound or a mixture of the new naphthopyran compound and a complementary photo-coloring compound (for example, spiro (indoline) type compound) such as an ophthalmic lens and other transparent plastic articles are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

DESCRIPTION OF THE INVENTION This invention relates to certain novel naphthopyran compounds. In particular, the present invention relates to a novel photochromic [photochromic] naphthopyran compound and compositions and articles containing the naphthopyran compound. Many photochromic compounds exhibit reversible discoloration when exposed to light containing ultraviolet light, such as ultraviolet light contained in sunlight. When UV irradiation is interrupted, this type of photochromic compound returns to its original color or colorless state.

  Various photochromic compounds have been synthesized, and as these uses, there have been proposed uses in which reversible discoloration or darkening induced by sunlight is desired. US Pat. No. 3,567,605 (Becker) (Patent Document 1) describes a series of pyran derivatives including specific benzopyrans and naphthopyran. These compounds are described as chromene derivatives, and the compounds are reported to change color (for example, change from colorless to yellow-orange) upon irradiation with ultraviolet light at a temperature lower than about −30 ° C. It has been reported that when these compounds are irradiated with visible light or when the irradiation temperature is higher than about 0 ° C., the color is reversibly changed to a colorless state.

  U.S. Pat. No. 5,066,818 has desirable photochromic properties, i.e. high colorability and acceptable decolorization desirable for applications in the field of ophthalmology and other fields. A variety of 3,3-diaryl-3H-naphtho [2,1-b] pyrans have been described. The 2,2-diaryl-2H-naphtho [1,2-b] pyran isomer described as a comparative example in the patent specification requires an unacceptably long time for decolorization after activation Has been reported.

  U.S. Pat. No. 3,627,690 (Patent Document 3) describes a photochromic 2,2-disubstituted-2H-naphtho containing a small amount of a base or a weak to moderately strong acid. 1,2-b] pyran compositions are described. It has been reported that this type of composition is useful in applications for protecting eyes such as sunglasses because the addition of acid or base to this naphthopyran composition enhances the decoloration rate of colored naphthopyran. ing. Furthermore, the patent specification reports that the decolorization rate of 2H-naphtho [1,2-b] pyran without the additive ranges from hours to days to reach full reversibility. ing. US Pat. No. 4,818,096 (Patent Document 4) describes a blue color having a phenyl group having a nitrogen-containing substituent at the α-position or ortho- or para-position to the oxygen atom of the pyran ring. A photochromic benzopyran or naphthopyran that changes color is disclosed.

US Pat. No. 3,567,605 US Pat. No. 5,066,818 US Pat. No. 3,627,690 U.S. Pat. No. 4,818,096

  The present invention aims to provide a photochromic plastic material, in particular a photochromic plastic material for optical applications.

  Certain novel 2H-naphtho [1,2-b] pyran compounds of formula (I).

  The present invention has the unexpected property of exhibiting an acceptable decoloring rate in addition to high activation strength and high coloration rate. It relates to novel substituted 2H-naphtho [1,2-b] pyran compounds. In particular, when a specific substituent is present at the 5-position of the naphtho moiety of the naphthopyran compound, the decoloring rate can be increased without adding an acid or a base. Certain substituents may be bonded to the 6-position, 7-position, 8-position, 9-position or 10-position carbon atom of the naphtho moiety of naphthopyran.

  According to the present invention, a photochromic plastic material, particularly a photochromic plastic material for optical applications can be provided. In accordance with the present invention, certain novel 2H-naphtho [1,2-b] pyran compounds are prepared that have an acceptable decolorization rate, high activation intensity, and high coloration rate.

  This invention has the unexpected property of exhibiting an acceptable decoloring rate in addition to high activation strength and high coloration rate. It relates to novel substituted 2H-naphtho [1,2-b] pyran compounds. In particular, when a specific substituent is present at the 5-position of the naphtho moiety of the naphthopyran compound, the decoloring rate can be increased without adding an acid or a base. Certain substituents may be bonded to the 6-position, 7-position, 8-position, 9-position or 10-position carbon atom of the naphtho moiety of naphthopyran.

DETAILED DESCRIPTION OF THE INVENTION Recently, photochromic plastic materials, particularly photochromic plastic materials for optical applications, have attracted attention. In particular, photochromic ophthalmic plastic lenses are being studied because they are lighter than glass lenses. Furthermore, transparency with photochromic properties in vehicles such as cars and aircraft is important because it has the potential safety features brought about by it.

  In accordance with the present invention, it has been found that certain novel 2H-naphtho [1,2-b] pyran compounds are prepared that have an acceptable decolorization rate, high activation intensity, and high coloration rate. Such compounds may be described as naphthopyrans having specific substituents at the 2-position of the pyran ring and the 5-position carbon atom of the naphtho moiety of the naphthopyran ring. The specific substituent may be bonded to the 6-position, 7-position, 8-position, 9-position or 10-position carbon atom of the naphthopyran ring. These compounds are represented by the following formula (I):

In the above formula (I), R ₁ represents —C (O) W, W represents —OR ₄ or —N (R ₅ ) R ₆ , and R ₄ represents a hydrogen atom, allyl, C ₁ -C ₆ alkyl. (Eg, methyl, ethyl, propyl, butyl, pentyl, hexyl), phenyl, mono (C ₁ -C ₆ ) alkyl, substituted phenyl, mono (C ₁ -C ₆ ) alkoxy-substituted phenyl, phenyl (C ₁ -C ₃ ) alkyl, mono (C ₁ -C ₆ ) alkyl substituted phenyl (C ₁ -C ₃ ) alkyl, mono (C ₁ -C ₆ ) alkoxy substituted phenyl (C ₁ -C ₃ ) alkyl, C ₁ -C ₆ alkoxy (C ₂ -C ₄ ) alkyl or C ₁ -C ₆ haloalkyl, each of R ₅ and R ₆ is a hydrogen atom, C ₁ -C ₆ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono- or di- A group selected from the group consisting of substituted phenyl Show. The phenyl group may be substituted by C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy, and the halo substituent may be a base atom or a fluorine atom.

Preferably, R ₁ represents —C (O) W, W represents —OR ₄ or —N (R ₅ ) R ₆ , and R ₄ represents a hydrogen atom, C ₁ -C ₄ alkyl, phenyl, mono (C _1- C ₄ ) alkyl-substituted phenyl, mono (C ₁ -C ₄ ) alkoxy-substituted phenyl, phenyl (C ₁ -C ₂ ) alkyl, mono (C ₁ -C ₄ ) alkyl-substituted phenyl (C ₁ -C ₂ ) alkyl , Mono (C ₁ -C ₄ ) alkoxy substituted phenyl (C ₁ -C ₂ ) alkyl, mono (C ₁ -C ₄ ) alkoxy (C ₂ -C ₃ ) alkyl or C ₁ -C ₄ haloalkyl, R ₅ And R ₆ each represents a group selected from the group consisting of a hydrogen atom, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono- or di-substituted phenyl. Phenyl substituent may be selected from C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, and halo substituent may be a chlorine atom or a fluorine atom.

More preferably, R ₁ represents —C (O) W, W represents —OR ₄ or —N (R ₅ ) R ₆ , and R ₄ represents a hydrogen atom, C ₁ -C ₃ alkyl, phenyl, mono ( C ₁ -C ₃ ) alkyl substituted phenyl, mono (C ₁ -C ₃ ) alkoxy substituted phenyl, mono (C ₁ -C ₃ ) alkoxy (C ₂ -C ₃ ) alkyl or C ₁ -C ₃ haloalkyl, R Each of ₅ and R ₆ represents a group selected from the group consisting of a hydrogen atom, C ₁ -C ₃ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono-substituted phenyl. The phenyl substituent may be selected from the group consisting of C ₁ -C ₃ alkyl and C ₁ -C ₃ alkoxy, and the halo substituent is a fluorine atom. Most preferably, R ₁ represents —C (O) W, W represents —OR ₄ or —N (R ₅ ) R ₆ , R ₄ represents a hydrogen atom or C ₁ -C ₃ alkyl, R ₅ And R ₆ each represents a hydrogen atom, C ₁ -C ₃ alkyl or phenyl.

Each of R ₂ and R ₃ in formula (I) represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₃ -C ₇ cycloalkyl, substituted or unsubstituted phenyl, —OR ₇ , R ₇ is a hydrogen atom, C ₁ -C ₆ alkyl, phenyl (C ₁ -C ₃₎ alkyl, mono (C ₁ -C ₆₎ alkyl substituted phenyl (C ₁ -C ₃₎ alkyl, mono (C ₁ -C ₆₎ alkoxy substituted phenyl (C ₁ -C ₃₎ alkyl, C ₁ -C ₆ alkoxy (C ₂ -C ₄₎ alkyl, C ₃ -C ₇ cycloalkyl, mono (C ₁ -C ₄₎ alkyl substituted C ₃ -C ₇ cycloalkyl, C ₁ - C ₆ haloalkyl, allyl or —CH (R ₈ ) X, X represents —CN, —CF ₃ , a halogen atom or —C (O) W, R ₈ represents a hydrogen atom or C ₁ -C ₆ alkyl. Show. Or R ₇ represents —C (O) Y, Y represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, substituted or unsubstituted aryl (phenyl or naphthyl), phenoxy, C ₁ -C ₆ mono- or di-alkyl substituted phenoxy, C ₁ -C ₆ mono- or di-alkoxy substituted phenoxy, C ₁ -C ₆ alkylamino, phenylamino, C ₁ -C ₆ mono- or di-alkyl substituted phenylamino or C ₁ -C ₆ mono- - or di - an alkoxy substituted phenylamino, each phenyl substituent and naphthyl substituent is selected from C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, halogen or halo substituents Is a chlorine atom or a fluorine atom, and n is a number selected from 0, 1, 2, and 3.

Preferably, each of R ₂ and R ₃ represents a hydrogen atom, C ₁ -C ₃ alkyl, C ₃ -C ₅ cycloalkyl, substituted or unsubstituted phenyl or —OR ₇ , R ₇ represents a hydrogen atom, C ₁ — C ₃ alkyl or —CH (R ₈ ) X is represented, X represents —CN or —C (O) W, and R ₈ represents a hydrogen atom or methyl. Or R ₇ represents —C (O) Y, Y represents C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, and the phenyl substituent represents C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy. N represents a number of 0 or 1.

More preferably, each of R ₂ and R ₃ represents a group selected from the group consisting of a hydrogen atom, C ₁ -C ₃ alkyl, phenyl and —OR ₇ , and R ₇ is a hydrogen atom or C ₁ -C _3. Represents alkyl or —C (O) Y, Y represents C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, and n represents the number 0 or 1. Most preferably, each of R ₂ and R ₃ represents a hydrogen atom or C ₁ -C ₃ alkyl. In the definitions of R ₁ , R ₂ and R ₃ in formula (I), the same letters have the same meaning unless otherwise specified.

B in formula (I) may be unsubstituted or may be mono-, di- or tri-substituted aryl groups (phenyl and naphthyl), where the aryl substituent is C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen atom, amino, C ₁ -C ₆ monoalkylamino, C ₁ -C ₆ dialkylamino, ie di (C ₁ -C ₆ ) alkylamino, morpholino, piperidino, indolinyl , 1-imidazolidyl, 2-imidazolin-1-yl, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl and pyrrolidyl, the halogen atom being a fluorine atom or a chlorine atom.

Preferably, B is unsubstituted or mono- - or di - substituted phenyl, the phenyl substituents are C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen atom, amino, C ₁ -C ₄ Selected from the group consisting of monoalkylamino, C ₁ -C ₄ dialkylamino, morpholino, piperidino, indolinyl and pyrrolidyl, the halogen atom being a fluorine atom or a chlorine atom.

More preferably, B is unsubstituted or mono- or di-substituted phenyl and the phenyl substituent is C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, fluorine atom, amino, C ₁ -C ₃ monoalkylamino, C ₁ -C ₃ dialkylamino is selected from the group consisting of morpholino and piperidino.

Most preferably, B is unsubstituted or mono- or di-substituted phenyl and the phenyl substituent is C ₁ -C ₂ alkyl, C ₁ -C ₂ alkoxy, fluorine atom, C ₁ -C ₂ mono alkylamino, C ₁ -C ₂ dialkylamino is selected from the group consisting of morpholino and piperidino.

  B 'in the formula (I) may be selected from the group consisting of the following (i) to (iii).

(I) Mono-substituted aryl groups (phenyl and naphthyl). Aryl substituent amino, C ₁ -C ₆ monoalkylamino, C ₁ -C ₆ dialkylamino, morpholino, piperidino, indolinyl, 1-imidazolidyl, 2-imidazolin-1-yl, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl And may be selected from the group consisting of pyrrolidyl.
(Ii) Group represented by (IIA):

Where U may be a hydrogen atom or C ₁ -C ₄ alkyl, V may be unsubstituted, or from the group consisting of mono- or di-substituted naphthyl, phenyl, furanyl and thienyl. It may be a selected group, and each substituent of the group is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, a fluorine atom or a base atom.

  (iii) Group represented by the following formula (IIB):

Wherein M may be CH ₂ , O, S or N—R ₁₄ , where R ₁₄ is a hydrogen atom, C ₁ -C ₆ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono- and di- May be selected from the group consisting of substituted phenyl, wherein the phenyl substituent is selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, chlorine and fluorine atoms, R ₉ is C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, a chlorine atom or a fluorine atom, a is shows a number selected from 0, 1, 2, and 3.

B and B ′ may together form an unsubstituted, mono-substituted or di-substituted fluorene-9-ylidene, or may form a ring selected from the following group: saturated C _3- C ₁₂ spiro-monocyclic hydrocarbon rings (eg, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, Cyclododecylidene, cycloundecylidene, cyclododecylidene), saturated C ₇ -C ₁₂ spiro-bicyclic hydrocarbon rings (eg bicyclo [3.2.1] octylidene, bicyclo [3.3.1] nonane) 9-ylidene, bicyclo [4.3.2] undecane) and saturated C ₇ -C ₁₂ spiro - tricyclic hydrocarbon ring (e.g., tricyclo [2.2. .0 ^2,6]) heptylidene, tricyclo [5.3.1.1 ^2,6] dodecylidene). However, the above-mentioned cyclic hydrocarbon ring includes tricyclo [3.3.1.1 ^3,7 ] decylidene (ie, adamantylidene), 1,7,7-trimethylbicyclo [2.2.1] heptylidene (ie, , Bornylidene) and bicyclo [2.2.1] heptylidene (ie, norbornylidene). Fluoren-9-ylidene substituents are C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, may be selected from the group consisting of fluorine atom and chlorine atom.

  Each of B and B 'may be selected from the groups defined in (ii) and (iii) above.

  Preferably, B 'is selected from the group consisting of the following (i) to (iii).

(I) Mono-substituted phenyl. Phenyl substituent is amino, C ₁ -C ₄ monoalkylamino, C ₁ -C ₄ dialkylamino, morpholino, piperidino, are selected from the group consisting of indolinyl and pyrrolidyl.

(Ii) A group represented by the formula (IIA). U may be a hydrogen atom or methyl, and V may be phenyl or mono-substituted phenyl. The phenyl substituent is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, a fluorine atom or a base atom.

(Iii) A group represented by the formula (IIB). M may be CH ₂ , O or N—R ₁₄ , R ₁₄ may be selected from the group consisting of a hydrogen atom, C ₁ -C ₄ alkyl, phenyl and mono-substituted phenyl, R 1 selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, chlorine atom and fluorine atom. May be C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, chlorine atom or fluorine atom, and a is selected from 0.1 and 2.

B and B ′ together may form an unsubstituted or mono-substituted fluorene-9-ylidene, or a saturated C ₃ -C ₈ spiro-monocyclic hydrocarbon ring, saturated C ₇ -C ₁₀ spiro- bicyclic hydrocarbon rings and saturated C ₇ -C ₁₀ spiro - tricyclic hydrocarbon ring may form a ring selected from the group consisting of substituents of the fluorene-9-ylidene C ₁ -C ₃ alkyl , C ₁ -C ₃ alkoxy, a fluorine atom and a chlorine atom.

  More preferably, B 'is selected from the group consisting of (i) and (ii) below.

(I) Mono-substituted phenyl. Phenyl substituent is amino, C ₁ -C ₃ monoalkylamino, C ₁ -C ₃ dialkylamino is selected from the group consisting of morpholino and piperidino.

(Ii) A group represented by the formula (IIB). M represents CH ₂ , O or N—R ₁₄ , R ₁₄ represents a hydrogen atom, C ₁ -C ₄ alkyl or phenyl, R ₉ represents C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and fluorine atom A is a number selected from 0, 1 and 2.

  Alternatively, B and B 'together may form fluorene-9-ylidene or bicyclo [3.3.1] nonane-9-ylidene.

Most preferably, B ′ represents mono-substituted phenyl, 9-ethylcarbazolyl or 9-phenylcarbazolyl, wherein the phenyl substituent is C ₁ -C ₂ monoalkylamino, C ₁ -C ₂ dialkylamino, morpholino Or piperidino.

The compounds represented by Formula I can be prepared by the methods described below. In reaction A1, benzoyl derivatives of carbazole, dibenzothiophene or dibenzofuran are prepared by the Friedel-Crafts method. Publications: Friedel-Crafts and related reactions , George A. Olah, Interscience Publishers, 1964, Volume 3, XXXI chapter (Aromatic Ketone Synthesis )), And "Regioselective Friedel-Crafts acylation of 1,2,3,4-tetrahydroquinoline and related nitrogen heterocycles: effects on NH protecting groups and ring size" (Ishihara, Yugi et al., Jay. Chem. Soc., Perkin Trans. 1, 3401-3406, 1992), heterocyclic compounds , Robert C. Elderfield, 1951, Volume 2, Chapter 3 (Dibenzofuran) and Chapter 5 (Dibenzothiophene); Chemistry of Heterocyclic Compounds, HDHartough and SL Meisel , 1954, Vol. 7, IV chapters (dibenzothiophene and its derivatives); Advances in heterocyclic chemistry, rays. R. ARKatritzky and AJBoulton, 1974, Volume 16, Chapter V (Recent Advances in Dibenzothiophene Chemistry); and Heterocycles , Robert Sea Elderfield, 1952, 3rd See Volume 3, Chapter 3 (Carbazole Chemistry).

  In reaction A1, the compounds of formula III and IV are dissolved in a solvent such as carbon disulfide or methylene chloride in the presence of a Lewis acid such as aluminum chloride and the corresponding substitution represented by formula V A benzoyl derivative is formed. R represents a potential phenyl substituent.

  As shown in Reaction A2, the compound represented by Formula VB can be directly converted to a commercially available fluoro-substituted benzophenone represented by Formula VA using a first or second amine compound such as ethylamine, morpholine, piperidine, or the like. Obtained or prepared by amination. Publication: "Nucleophilic substitution of activated fluorine in aromatic compounds" (Bader, Henry et al., J. Org. Chem., Vol. 31, 2319-2321) See page 1966.

  In reaction A2, when the compound represented by formula VA and the amino compound are dissolved in a solvent such as dimethyl sulfoxide (DMS) and refluxed, the corresponding amino-substituted benzophenone represented by formula VB is generated. R represents a potential phenyl substituent.

  In reaction B, the ketone of formula V, VB, or the more general formula VC is reacted with sodium acetylide in a suitable solvent such as anhydrous tetrahydrofuran (THF) to provide the corresponding formula VI. Propargyl alcohol is produced. Propargyl alcohols having a B 'group of formula IIA can be prepared by the method described in US Pat. No. 5,274,132, 2 rans, lines 40-68.

  Naphthol represented by Formula XIIIA is prepared by Reaction C or Reaction D. In Reaction C, substituted or unsubstituted 1,4-dihydroxy-2-naphthoic acid of formula VII is converted to methyl iodide in the presence of ethyl diisopropylamine in a suitable solvent such as anhydrous dimethylformamide (DMF). (Or ethyl iodide, propyl iodide, benzyl bromide, etc.) produces the corresponding methyl-1,4-dihydroxy-2-naphthoate of formula VIII (or formula XIIIA in reaction E). . The reaction is Jay of Org Chem. (J. of Org. Chem.), 46 (17), 3477, 1981.

In Reaction D, the substituted or unsubstituted acetophenone, benzophenone, or benzaldehyde of formula IX is dimethyl succinate in the presence of a base such as sodium hydroxide or potassium t-butoxide in a suitable solvent such as toluene. Reaction with (Formula X) produces the appropriate substituted monoester of arylidene succinic acid represented by Formula XI. Other ester substituents of the compounds of formula XI can be prepared by using different succinates such as diethyl succinate. Heating Compound XI with acetic anhydride and anhydrous sodium acetate produces the corresponding acetate derivative represented by Formula XII. Reaction of compound XII with anhydrous alcohol such as hydrochloric acid and anhydrous methanol produces the corresponding naphthol of formula XIII (or formula XIIIA in reaction E). Reaction D further includes Text Organic Reaction , Vol. VI, Chapter 1, pp. 1-73, John Willey and Sons, Inc. (John Wiley & Sons. Inc.), New York.

  In Reaction E, propargyl alcohol represented by Formula VI is combined with naphthol represented by Formula XIIIA to form a compound represented by Formula I.

As seen in Reaction F, the hydroxyl group of the compound represented by Formula XIV (the compound of Formula I where R ₂ is a hydroxyl group) can be replaced with various different groups by reaction with an acylating agent or alkylating agent. It is. For example, is reacted with methyl iodide (or other alkylating agent) in the presence of anhydrous potassium carbonate in a suitable solvent such as anhydrous acetone compound represented by the formula XIV R ₂ is a methoxy substituent A compound represented by Formula XV is produced. The alkylation reaction is further described in "Organic Synthesis", Vol. 31, pages 90-93, John Willey and Sons, Inc., New York, NY. Alternatively, when compound XIV is reacted with acetyl chloride (or other acylating agent) in the presence of triethylamine (NEt ₃ ) in a suitable solvent such as methylene chloride, R ₂ is acetoxy (AcO) substituted. The compound represented by the formula XVI is formed. The acylation reaction is further described in “Organic Synthesis”, 32, 72-77, John Willey and Sons, Inc., New York, NY.

  The compounds of formula I may be used in other applications where organic photochromic (photochromic) materials can be used. For example, ophthalmic lenses such as vision correction ophthalmic lenses and flat lenses, face protectors, goggles, shading plates, camera lenses, windows, automobile windshields, aircraft and automobile T-roofs, sidelights and backlights Secrets such as transparent materials, plastic films and sheets, textiles, and coatings such as coating compositions such as paint, such as banknotes, certificates such as passports or driver's licenses that require authenticity verification or verification A verification mark on the certificate. The naphthopyran represented by Formula I exhibits a color change from colorless to orange to blue range.

Examples of naphthopyran encompassed within the scope of the invention are described below:
(A) 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran;
(B) 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-methoxy-2H-naphtho [1,2-b] pyran;
(C) 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran;
(D) 2- (9-ethylcarbazol-2-yl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran;
(E) 2- (9-phenylcarbazol-2-yl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran;
(F) 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran;
(G) 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-methyl-2H-naphtho [1,2-b] pyran; and (h) 2,2-bis (4- Dimethylaminophenyl) -5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran.

  The organic photochromic naphthopyran of formula I is suitable for other suitable organic photochromic properties so that when a plastic lens containing the photochromic material is exposed to UV light, it provides darkening to a near neutral gray or brown color. It may be used with substances. For example, mixing a yellow compound with a suitable purple compound may result in darkening to brown. Similarly, a compound whose color state is orange produces a gray shade when used in combination with a suitable blue color compound. The combination of the photochromic materials can be used for applications other than ophthalmic lenses.

  The novel naphthopyran compounds of the invention described so far may be used alone or as complementary photochromic compounds, i.e. having at least one activated absorption maximum in the range of about 400 to 700 nanometers. You may use with the organic photochromic compound which has, or the substance containing this. In addition, the novel compound may be blended by being dissolved or dispersed in an organic host polymer material used for preparing a photochromic article that changes color to an appropriate color when activated. .

The first group of complementary organic photochromic materials used in conjunction with the organic photochromic naphthopyran of the present invention has an activated absorption maximum in the visible range of 570 nanometers or more, eg, between about 570 and 700 nanometers. It is what has. These materials typically exhibit a blue, blue-green or blue-violet color when exposed to ultraviolet light in a suitable solvent or matrix. Many such compounds are described in the published literature. For example, among others, spiro (indoline) naphthoxazines are described in US Pat. Nos. 3,562,172; 3,578,602; 4,215,010; and 4,342,668, where the molecular naphthoxazine Spiro (indoline) naphthoxazines having specific substituents on the 8 ′ and 9 ′ positions of the moiety are described in US Pat. No. 5,405,958 and spiro (indoline) pyridobenzoxazines are described in US Pat. No. 4,637,698. Spiro (benzindoline) pyridobenzoxazine and spiro (benzindoline) naphthoxazine are described in U.S. Pat. No. 4,931,219, spiro (benzindoline) naphthopyran is described in Japanese Patent Publication 62/195383, Spiro (indoline) benzzoxazine is described in US Pat. No. 4,816,584 and spiro Indoline) benzopyran, spiro (indoline) naphthopyran and spiro (indoline) quinopyran are described, for example, in US Pat. No. 4,880,667, and benzopyran and naphthopyran having a nitrogen-containing substituent at the 2-position of the pyran ring are described in US Pat. 096. Spiro (indoline) pyran is also a text, technology in chemistry , Volume III, “Phototampering”, Chapter 3, Glen H. Brown (Glenn H.Brown), Editor, John Willey and Sons, Inc. New York, 1971.

  A second group of complementary organic photochromic materials used in conjunction with the organic photochromic naphthopyrans of the present invention are those that have at least one absorption maximum in the visible range between about 400 and 500 nanometers. These materials typically exhibit a yellow-orange color when exposed to ultraviolet light in a suitable solvent or matrix. Such compounds include certain chromenes, ie benzopyran and naphthopyran. Many such chromenes are described in published literature, for example, US Pat. Nos. 3,567,605, 4,826,977 and 5,066,818. Other examples of complementary benzopyrans and naphthopyrans that can be used with the naphthopyran of the present invention have a spiroadamantane group in the α-position to the oxygen atom of the pyran ring (described in US Pat. No. 4,826,977). ); 2H-naphtho- [1,2-b] pyran compounds having specific substituents at the 5th and 6th carbon atoms of the naphthopyran naphtho moiety and the 2nd position of pyran (co-pending US patent application no. 08 / 164,187 (filed Dec. 9, 1993); 3H-naphtho [2,1-b] pyran (US) having at least one ortho-substituted phenyl substituent at the 3-position of the pyran ring Patent No. 5,066,818); having a specific substituent at the 8th carbon atom of the naphtho moiety of naphthopyran and a specific substituent at the 7th or 9th carbon atom 3H-naphtho [2,1-b] pyran compounds (subject to co-pending U.S. Patent Application No. 08 / 080,246 (filed June 21, 1993)); i) aryl substituents and (ii) 3H-naphtho [2,1-b substituted with phenyl substituents having 5- or 6-membered heterocycles fused at the third and fourth carbon atoms of the phenyl substituent Pyran is described in US Pat. No. 5,384,077; diaryl-3H-naphtho [2,1 having a substituted or unsubstituted 5- or 6-membered heterocycle fused to the g, i, or l side of naphthopyran -B] pyran compounds (subject to co-pending US patent application No. 08 / 225,022 (filed April 8, 1994)); the 8th carbon atom of the naphtho moiety of the naphthopyran ring is, for example, a methoxy group US Patent 5, Naphthopyran compounds covered by 38,931; naphthopyran compounds such as 3-aryl-3-arylalkenyl naphthopyrans (described in US Pat. No. 5,274,132); substituted at the fifth carbon atom, for example with an acetoxy group Naphtho [2,1-b] pyran (subject to US Pat. No. 5,244,602).

  A third group of complementary organic photochromic materials used in conjunction with the organic photochromic naphthopyran of the present invention has an absorption maximum in the visible range between about 400 to 500 nanometers and about 500 to 700 nanometers. Having other absorption maxima in the visible range between. These materials exhibit colors ranging from yellow to purple and from yellow / brown to purple / grey when exposed to ultraviolet light in a suitable solvent or matrix. Examples of these compounds include certain substituted 2H-phenanthro [4,3-b] pyrans, substituted 3H-phenanthro [1,2-b] pyrans and benzopyran benzs having substituents at the 2-position of the pyran ring. Included are benzopyran compounds such as benzopyran having a substituted or unsubstituted heterocycle such as a benzothieno or benzofurano ring fused to the moiety. The benzopyran compounds are the subject of co-pending US patent application No. 08 / 286,039 (filed Aug. 4, 1994) and US Pat. No. 5,411,679.

The photochromic article of the present invention may contain one photochromic compound or a mixture of photochromic compounds as required. Each photochromic compound or mixture of photochromic compounds may be used to obtain certain active colors such as light gray or brown.
The compounds of the present invention (which are hereinafter referred to as being included in the second group of photochromic compounds) are in the first group of complementary organic photochromic materials, i.e. blue, blue-green or blue-violet. You may use together with the photochromic substance which changes color, or may use together with the other organic photochromic substance in the above-mentioned 2nd group. A compound of either the first or second group of photochromic compounds, or a mixture of such compounds, wherein said third group exhibits a color ranging from yellow to purple, or yellow / brown to purple / gray. These photochromic compounds may be used in combination.

  Each of the photochromic materials described herein is substantially free when the organic host material to which the photochromic material or mixture of compounds is applied or formulated is activated with a desired synthetic color, such as direct sunlight. It may be used in such an amount (or ratio) that it exhibits an intermediate color, that is, the coloration of the activated photochromic compound results in a color development as close to the intermediate color as possible.

The light gray exhibits a spectrum with a relatively equal amount of absorption in the visible range between 400 and 700 nanometers. The light brown color exhibits a slightly larger spectrum in the 400-550 nanometer range than in the 550-700 nanometer range. Another way of describing color is to display by chromaticity coordinates, which display the quality of the color in addition to the luminance factor, ie its chromaticity. In the CIE system, chromaticity coordinates are obtained by taking the ratio of the tristimulus values to the total value, eg, x = X / (X + Y + Z) and y = Y / (X + Y + Z). The colors displayed in the CIE system are plotted on a chromaticity diagram, usually with chromaticity coordinates x and y. See Color Technology Principles 47-52 (FW Billmeyer, Jr., and Max Saltzman, Volume 2, John Willey and Sons, New York (1981). As used herein, the near-intermediate color is activated with a chromaticity coordinate value of “x” and “y” for the color [light transmittance up to 40% by sunlight irradiation (air quantity: 1 or 2). Is a value within the following range (D65 light source): x = 0.260 to 0.400, y = 0.280 to 0.400 If an amount sufficient to provide a modifying effect is used, the amount of photochromic material or composition containing the material applied or incorporated into the host material is not critical. Is the photochromic amount ( The specific amount used often depends on the color intensity desired by irradiation and the method used to formulate or apply the photochromic material. The more tautomeric substances are applied or blended, the more the color intensity increases to a certain limit value.

The relative amounts of the above photochromic compounds used will vary to some extent depending on the relative color strength of the activated species of these compounds and the final color required. In general, the total amount of photochromic material incorporated or applied to the photochromic optical host material is about 0.05 to 1.0 mg, preferably 0.1 to 0.45 mg per cm ^{2 of} the surface on which the photochromic material is incorporated or applied. is there. When using the above organic photochromic scavenging groups, the weight ratios are: (first to second), (second to third), and (other second The naphthopyran of the present invention for a group of groups varies from about 1: 3 to about 3: 1, preferably from about 0.75: 1 to about 2: 1. The combination of the first, second, and third organic photochromic supplement groups may vary in a weight ratio range of about 1: 3: 1 to 3: 1: 3.

  The photochromic material of the present invention may be applied to or incorporated into a host compound such as an organic host material polymer by a variety of methods described in the art. Examples of such a method include a method in which a photochromic substance is dissolved or dispersed in a host material, for example, a method in which a photochromic material is added to a host material in a monomer state before polymerization and cast in situ; Dipping in a hot solution of the photochromic material or absorbing into the host material by heat transfer; introducing the photochromic material as an isolated layer, eg, as a polymerized thin layer, between adjacent layers of the host material; It can also be enumerated that the photochromic material is applied as a coating on the surface of the host material. The term `` immersion '' or `` immersion '' means that only the photochromic material penetrates into the host material, the photochromic material migrates into the porous polymer with the aid of a solvent, the transition as a vapor phase, and so on Meaning and including other transition mechanisms.

  In order to obtain a more aesthetic effect, compatible colorants, for example dyes, may be applied to the host material for medical reasons or in fashion (in terms of chemical and color).

  The particular dye to be chosen will vary depending on the above reasons and the results obtained. In one embodiment, the dye can be selected to capture the color due to the activated photochromic material, for example, to produce a more neutral color or to absorb a specific incident wavelength. In another embodiment, the dye can be selected to provide a preferred hue for the host matrix when the photochromic material is in a non-activated state.

  Auxiliary material may be incorporated with the photochromic substance in the host material prior to, simultaneously with or subsequent to application or incorporation of the photochromic substance in the host material. For example, an ultraviolet absorber may be mixed with the photochromic material before application to the host material, or such an absorber may be overlaid as a layer, for example, between the photochromic material and the incident light. . Further, a stabilizer may be mixed with the photochromic substance prior to application to the host material in order to improve the light fatigue resistance of the photochromic substance. Stabilizers such as hindered amine light stabilizers and singlet oxygen quenchers such as complexes of nickel ions and organic ligands are contemplated. These may be used alone or in combination. These stabilizers are described in US Pat. No. 4,720,356. Finally, a suitable protective coating may be applied to the surface of the host material. The protective coating may be an abrasion resistant coating or a coating that acts as an oxygen barrier. Such coatings are well known in the art.

  The host material is usually transparent, but may be translucent or even opaque. The host material includes the relevant portion of the electromagnetic spectrum that activates the photochromic material, i.e., the wavelength of the ultraviolet light that gives rise to the open form of the material, and the absorption maximum wavelength of the material in the activated form, i. It suffices if it is transparent only to the relevant portion of visible light. Preferably, the host color should not mask the activated form of the photochromic material. Therefore, the color change must be easily seen by the observer. More preferably, the host material is a solid, transparent or optically transparent material such as planar and ophthalmic lenses, windows, automotive transparent parts such as windshield, aircraft transparent parts, plastic sheets, polymer films, etc. is there.

Examples of polymeric organic host materials that may be used with the photochromic materials and the compositions described herein include: polymers, ie, polyol (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, di- Homopolymers and copolymers of isopropenylbenzene monomers and alkoxylated polyhydric alcohol acrylate monomers such as ethoxylated trimethylolpropane triacrylate monomers; polymers, ie multifunctional, ie mono-, di- Poly (C ₁ -C ₁₂ alkyls) such as homopolymers and copolymers of tri-, tetra- or polyfunctional acrylate and / or methacrylate monomers, polyacrylates, polymethacrylates, poly (methyl methacrylate) Methacrylates), polyoxy (alkylene methacrylates) such as poly (ethylene glycol bismethacrylates), poly (alkoxylated phenol methacrylates) such as poly (ethoxylated bisphenol A dimethacrylate), cellulose acetate, cellulose triacetate, Cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), polyurethanes, thermoplastic polycarbonates, polyesters, poly (ethylene terephthalate) ), Polystyrene, poly (α-methylstyrene), copoly (styrene-methylmethacrylate), copoly (styrene-acrylonitrile), polyvinylidene Butyral; and polymers, i.e., copolymers of di homopolymers of arylidene pentaerythritol and copolymers, in particular polyol (allyl carbonate) monomers, e.g., diethylene glycol bis (allyl carbonate) and acrylate monomers.

Transparent copolymers and blends of transparent polymers are also suitable as host materials. Preferably, the host material is an optically transparent polymerized organic material, which is a thermal resin such as a resin having a carbonate bond obtained from bisphenol A and phosgene sold under the trade name “LEXAN”. Plastic polycarbonate resin; polyester marketed under the trade name “MYLAR”; poly (methyl ketacrylate) marketed under the trade name “PLEXIGLAS”; polyol (allyl carbonate) monomer, in particular Polymers of diethylene glycol bis (allyl carbonate) marketed under the trade name "CR-39", and polyols (allyl carbonate) co-polymers such as diethylene glycol bis (allyl carbonate) and other copolymerizable monomers Copolymers such as vinyl Copolymers with diacetate, for example diethylene glycol bis (allyl carbonate) 80-90% and vinyl acetate 10-20%, in particular bis (allyl carbonate) 80-85% vinyl acetate 15-20% copolymer, USA Copolymers with polyurethanes having diacrylate functional groups at the ends described in US Pat. No. 4,360,653 and US Pat. No. 4,994,208; and allyl ends thereof described in US Pat. No. 5,200,483 Or polymers of the group consisting of copolymers with aliphatic urethanes containing acrylyl functionality, polyvinyl butyral, polyurethane, diethylene glycol dimethacrylate monomers, diisopropenylbenzene monomers, and ethoxylated trimethylolpropane monomers; Tate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and styrene and methyl methacrylate, copolymers of vinyl acetate and acrylonitrile. More preferably, the photochromic naphthalopyran of the present invention is used to produce optically transparent polymers, i.e. materials suitable for optical applications such as planar and ophthalmic lenses, windows and automotive transparency. It may be used together with a monomer for optical organic resin. Thus, the optically transparent polymer may have a refractive index that may range from about 1.48 to 1.75, preferably from about 1.495 to 1.66.
The present invention is described in more detail in the following examples, which are given by way of example only, and it will be apparent to those skilled in the art that this includes many modifications and variations. Let's go.

Example 1
Step 1
4-Fluorobenzophenone (25 g, 0.12 mol) and morpholine (15 g) were added to a reaction flask containing 100 ml of anhydrous dimethyl sulfoxide, stirred and refluxed for 8 hours under an argon atmosphere. The mixture in the flask was then added to 500 ml of ice-water mixture and stirred for 2 hours. The resulting solid product was filtered, washed successively with water and then hexane and air dried. The yield of isolated product was 30 g. Analysis by nuclear magnetic resonance (NMR) spectrum indicated the presence of a product having a structure consistent with 4-morpholinobenzophenone. This was used directly in the next step without generation.

Step 2
4-morpholinobenzophenone (10 mg, 0.037 mol) was dissolved in a reaction flask containing 50 ml of anhydrous dimethylformamide saturated with acetylene and stirred at room temperature. A suspension of 18 wt% sodium acetylide dispersed in styrene / mineral oil (0.3 mol of sodium acetylide) was added to the reaction flask and the mixture was stirred. After stirring for 3 hours under a nitrogen atmosphere at room temperature, the mixture in the reaction flask was added to 250 ml of an ice-water mixture and stirred for 1 hour. The resulting solid product was filtered, washed with water then hexane and air dried. The yield of isolated product was 8 g. Analysis by nuclear magnetic resonance (NMR) spectrum indicated the presence of a product having a structure consistent with 1- (4-morpholinophenyl) -1-phenyl-2-propyn-1-ol. This was used directly in the next step without generation.

Step 3
1- (4-morpholinophenyl) -1-phenyl-2-propyn-1-ol (about 0.025 mol) obtained in Step 1 and methyl-1,4-dihydroxy-2-naphthoate (5 g, 0. 022 mol) was added to a reaction flask containing 200 ml of toluene and stirred. A catalytic amount of p-toluenesulfonic acid (about 100 mg) was added and the mixture was stirred for 4 hours. The reaction mixture was then poured into a 10% strength by weight sodium hydroxide solution. The organic layer was separated, washed with water and dried over anhydrous sodium sulfate. The residual solvent, toluene, was removed under vacuum. The resulting oil was purified using a silica gel column and a 1: 3 mixture of chloroform: hexane as the eluent. The photochromic fractions were combined and the eluent was removed in vacuo. The resulting product was crystallized from a hexane solution. The recovered product had a melting point of 178-179 ° C. As a result of analysis by nuclear magnetic resonance (NMR) spectrum, a structure consistent with 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran was obtained. The presence of product was indicated.

Example 2
2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran (2 g), anhydrous carbonic acid prepared as described in Example 1 Potassium (2 g) and methyl iodide (2 g) were added to a reaction flask containing 40 ml of anhydrous acetone, stirred and refluxed under an argon atmosphere. The acetone was then removed under vacuum and 25 ml each of water and methylene chloride were added to the reaction mixture. The mixture was stirred for 30 minutes and the organic phase was separated, washed and dried. Residual solvent methylene chloride was removed under vacuum. The resulting thick oil was crystallized from a 1: 1 hexane: diethyl ether mixture. The resulting solid was filtered off with suction, washed with hexane and air dried. The product obtained had a melting point of 175-176 ° C. As a result of analysis by nuclear magnetic resonance (NMR) spectrum, a structure consistent with 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-methoxy-2H-naphtho [1,2-b] pyran was obtained. The presence of product was indicated.

Example 3
2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran (2 g) and triethylamine (2 g) prepared as in Example 1 were It was added to a reaction flask containing 50 ml of anhydrous methylene chloride and stirred. Acetyl chloride (2 g) was added to the reaction flask and the reaction mixture was stirred for 1 hour. Distilled water (50 ml) was added to the reaction flask and the reaction mixture was stirred for another half hour. The organic phase was then separated, washed and dried over anhydrous sodium sulfate. Evaporation of the solvent gave an oily residue that crystallized from a 1: 1 hexane: diethyl ether mixture. The solid was filtered off with suction, washed with hexane and air dried. The product obtained had a melting point of 143-145 ° C. As a result of analysis by nuclear magnetic resonance (NMR) spectrum, a structure consistent with 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran was obtained. The presence of product was indicated.

Example 4
Step 1
N-ethylcarbazole (50 g, 0.25 mol) and benzoyl chloride (0.28 mol) were placed in a reaction flask containing 500 ml of anhydrous methylene chloride and stirred at room temperature. Anhydrous aluminum chloride (0.30 mol) was slowly added to the mixture. The reaction mixture was stirred for 1 hour and then poured into a mixture of 5% by weight aqueous hydrochloric acid and ice. The resulting mixture was stirred for 15 minutes and extracted with methylene chloride. The organic phase was separated and the organic phase was separated and washed first with a 10% by weight aqueous sodium hydroxide solution and then with distilled water. The organic phase was separated and dried over anhydrous magnesium sulfate. The methylene chloride solvent was removed in vacuo. The resulting oily product was crystallized from hexane. The recovered product (35 g) was filtered and air dried. Analysis by nuclear magnetic resonance (NMR) spectrum indicated the presence of the required product having a structure consistent with 2-benzoyl-9-ethylcarbazole.

Step 2
1- (9-Ethylcarbazol-2-yl) -1-phenyl-in the same manner as in Step 2 of Example 1 except that 2-benzoyl-9-ethylcarbazole was used instead of 4-morpholinobenzophenone. 2-Propin-1-ol was obtained.

Step 3
1- (9-ethylcarbazol-2-yl) -1-phenyl-2-propyn-1-ol was used instead of 1- (4-morpholinophenyl) -1-phenyl-2-propyn-1-ol 2- (9-ethylcarbazol-2-yl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] except in the same manner as in Step 3 of Example 1. I got Piran.

Step 4
2- (9-ethylcarbazol-2-yl) -2 instead of 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran The same procedure as in Example 3 was performed except that -phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran was used. The product obtained was oily. As a result of analysis by nuclear magnetic resonance (NMR) spectrum, 2- (9-ethylcarbazol-2-yl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran and The presence of the required product having a matching structure was indicated.

Example 5
The same method as in Example 4 was performed except that N-phenylcarbazole was used instead of N-ethylcarbazole in Step 1. The product obtained had a melting point of 188-189 ° C. As a result of analysis by nuclear magnetic resonance (NMR) spectrum, 2- (9-epenylcarbazol-2-yl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran The presence of the required product having a structure consistent with was shown.

Example 6
Step 1
To obtain 1- (4-dimethylaminophenyl) -1-phenyl-2-propyn-1-ol in step 2, and in step 3 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxy To obtain carbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran, steps 2 and 3 of Example 1 were used except that 2,4-dimethylaminobenzophenone was used instead of 4-morpholinobenzophenone. Repeated.

Step 2
Instead of 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran, 2- (4-dimethylaminophenyl) -2-phenyl- The same method as in Example 3 was performed using 5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran. The product obtained had a melting point of 156 ° C. As a result of analysis by nuclear magnetic resonance (NMR) spectrum, a structure consistent with 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran The presence of the required product having

Example 7
Step 1
Instead of 1- (4-morpholinophenyl) -1-phenyl-2-propyne-1-ol, 1- (4-dimethylaminophenyl) -1-phenyl-2-propyn-1-ol is used to obtain methyl-1 , 4-methyl-1-hydroxy-2-methyl-2-naphthoate was used instead of 4-dihydroxy-2-naphthoate. The product obtained had a melting point of 182-184 ° C. As a result of analysis by nuclear magnetic resonance (NMR) spectrum, a structure consistent with 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-methyl-2H-naphtho [1,2-b] pyran The presence of the required product having

Example 8
The same method as in Example 6 was carried out except that 4,4′-bis (dimethylamino) benzophenone was used in Step 1 instead of 4-dimethylaminobenzophenone.
The resulting product had a melting point of 222-224 ° C. Nuclear magnetic resonance (NMR)
The required product having a structure consistent with 2,2-bis (4-dimethylaminophenyl) -5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran as a result of spectral analysis The presence of was shown.

Example 9
Part A
Tests were conducted using one of two different methods for the example photochromic naphthopyrans incorporated or immersed in square test polymers. In Method I, the photochromic naphthopyran of the example was incorporated into the polymerization sample. A quantity of naphthopyran calculated to give a 1.5 × 10 ⁻³ molar solution is added to 50 g of a monomer mixture of 4 parts ethoxylated bisphenol A dimethacrylate (BPA2EO DMA), 1 part poly (ethylene glycol) 600 dimethacrylate. , And 0.033 wt% 2,2′-azobis (2-methylpropionitrile) (AIBN). The naphthopyran was dissolved in the monomer mixture by stirring with gentle heating if necessary. After a clear solution was obtained, it was poured into a flat sheet mold with internal dimensions of 2.2 mm × 6 inches (15.24 cm) × 6 inches (15.24 cm). Programmable to seal the mold and set it so that the horizontal air flow temperature rises from 40 ° C to 95 ° C over 5 hours, is held at 95 ° C for 3 hours and then drops to 60 ° C Placed in the dryer for at least 2 hours before the end of the cure cycle. After opening the mold, the polymer sheet was cut into 2 inch (5.1 cm) square test pieces using a diamond blade saw.
In Method II, photochromic naphthopyran was infiltrated into a square test polymer prepared from a diethylene glycol bis (allyl carbonate) composition. The dimensions of the test piece were 1/8 inch (0.3 cm) × 2 inch (5.1 cm) × 2 inch (5.1 cm). In the dipping process, photochromic naphthopyran was dissolved in a 1: 9 mixture of ethyl cellulose: toluene to prepare a 10 wt% solution. The solution was then spin coated on a square specimen and dried. The sample was then heated in a hot air dryer at 135-155 ° C. for a time sufficient for the photochromic to heat transfer into the square specimen. The time for holding the square specimen in the dryer was adjusted so that a significant amount of the naphthopyran compound penetrated. This is so that the ultraviolet absorption at λmax of the compound in the near ultraviolet becomes a considerable amount. After coating, the ethylcellulose / toluene resin film was washed with acetone and removed from the square test piece.

Part B
The photochromic response speed of the square photochromic specimen was tested on the optical device table. Prior to testing on the optical bench, the square photochromic specimen is exposed to 365 nm UV light for about 15 minutes to activate the photochromic compound, and then about 15 to bleach or deactivate the photochromic compound. Placed in dryer at 76 degrees per minute. The square specimen is then cooled to room temperature, exposed to light in the fluorescence chamber for at least 2 hours, and then covered for at least 2 hours prior to testing on an optical bench held at 75 ° F. (23.9 ° C.). I left it over. 150 watt xenon arc lamp on optical stage, remote control shutter, copper sulfate bath acting as a heat bath for arc lamp, Schott WG-320 nm cut-off filter to remove short wavelength radiation, medium density filter and rectangular specimen A sample holder was inserted for insertion. A light beam collected from the tungsten lamp was applied to the test piece at a small angle perpendicular to the test piece. The light from the tungsten lamp was applied to the specimen and then passed through a photopic filter attached to the detector. The Hotopic filter passes wavelengths where the detector resembles the human eye response. The output signal from the detector is processed by a radiometer.
The optical density (ΔOD) changes by inserting a bleached rectangular specimen into the sample holder, adjusting the transmittance scale to 100%, and changing the rectangular specimen from the bleached state to the activated (ie, darkened) state. Therefore, the shutter of the xenon lamp that emits ultraviolet rays is opened, the transmittance is measured in the activated state, and the change in optical density is calculated according to the equation ΔOD = log (100 /% Ta). Where% Ta is the percent transmittance in the activated state and the logarithm is 10 at the bottom.
ΔOD / Min, which represents the response sensitivity of the photochromic compound to UV, was measured over the first 5 seconds of exposure to UV and then expressed on a minute basis. The saturation optical density (OD) was taken under the same conditions as ΔOD / Min, except that UV exposure was continued for 20 minutes for the samples in Table 1. The λmax reported in Table 1 is the wavelength in the visible spectrum, where the maximum absorption of the activated (colored) form of the photochromic compound in the diethylene glycol bis (allyl carbonate) composition occurs. . The bleaching rate (T _1/2 ) is half of the maximum absorption at room temperature (75 ° F., 23.9 ° C.) after absorption of the activated form of naphthopyran in the square specimen, excluding the activation light source. Is the time in seconds. The results for the example compounds are shown in Table 1.

* Square test specimens were prepared by Method II.
Otherwise, prepared by Method I.

Table 1 shows that the range of values for bleaching rate, ΔOD at saturation and sensitivity depend on the nature of the substituents R ₁ , R ₂ , R ₃ , and B and B ′ for the compounds of Examples 1-8 of the present invention. It shows that.

  Although the present invention has been described with respect to particular embodiments, such details are not intended to limit the scope of the invention.

Claims (20)

Naphthopyran compounds represented by the following formula:

In the above formula, R ₁ , R ₂ , R ₃ , B, B ′ and n have the following significance.
(A) R ₁ represents —C (O) W, W represents —OR ₄ or —N (R ₅ ) R ₆ , and R ₄ represents a hydrogen atom, allyl, C ₁ -C ₆ alkyl, phenyl, mono (C ₁ -C ₆ ) alkyl-substituted phenyl, mono (C ₁ -C ₆ ) alkoxy-substituted phenyl, phenyl (C ₁ -C ₃ ) alkyl, mono (C ₁ -C ₆ ) alkyl substituted phenyl (C ₁ -C ₃₎ alkyl, mono _(C 1 -C ₆₎ alkoxy substituted phenyl _(C 1 -C _{3) alkyl,} C 1 -C ₆ alkoxy _(C 2 -C ₄₎ an alkyl or _C 1 -C ₆ haloalkyl, _{R 5} And each of R ₆ represents a group selected from the group consisting of a hydrogen atom, C ₁ -C ₆ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono- or di-substituted phenyl. The phenyl group substituent is selected from C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy, and the halo substituent is a chlorine atom or a fluorine atom.
(B) Each of R ₂ and R ₃ represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₃ -C ₇ cycloalkyl, substituted or unsubstituted phenyl, —OR ₇ , R ₇ represents a hydrogen atom, C ₁ — C ₆ alkyl, phenyl (C ₁ -C ₃ ) alkyl, mono (C ₁ -C ₆ ) alkyl substituted phenyl (C ₁ -C ₃ ) alkyl, mono (C ₁ -C ₆ ) alkoxy substituted phenyl (C ₁ -C _{3) alkyl,} C 1 -C ₆ alkoxy _(C 2 -C _{4) alkyl,} C 3 -C ₇ cycloalkyl, mono _(C 1 -C ₄₎ alkyl substituted _C 3 -C _{7 cycloalkyl,} C 1 -C ₆ H represents haloalkyl, allyl or —CH (R ₈ ) X, X represents —CN, —CF ₃ , a halogen atom or —C (O) W, and R ₈ represents a hydrogen atom or C ₁ -C ₆ alkyl. Alternatively, R ₇ represents —C (O) Y, and Y represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, substituted or unsubstituted aryl (phenyl or naphthyl), phenoxy, C ₁ -C ₆ mono- or di-alkyl substituted phenoxy, C ₁ -C ₆ mono- or di-alkoxy substituted phenoxy, C ₁ -C ₆ alkylamino, phenylamino, C ₁ -C ₆ mono- or di-alkyl substituted phenylamino or C ₁ -C ₆ mono- or di-alkoxy substituted phenylamino, wherein each of the phenyl and naphthyl substituents is selected from C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, a halogen atom or a halo substituent Is a chlorine atom or a fluorine atom, and n is a number selected from 0, 1, 2, and 3.
(C) B is an unsubstituted or mono-, di- or tri-substituted aryl group (phenyl and naphthyl), where the aryl substituent is C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen atom, _amino, C 1 -C _{6 monoalkylamino,} C 1 -C ₆ dialkylamino, morpholino, piperidino, indolinyl, 1-imidazolidyl, 2-imidazolin-1-yl, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl and pyrrolidyl The halogen atom is a fluorine atom or a chlorine atom.
(D) B ′ is selected from the group consisting of the following (i) to (iii).
(I) Mono-substituted aryl groups (phenyl and naphthyl). Aryl substituents are amino, C ₁ -C ₆ monoalkylamino, C ₁ -C ₆ dialkylamino, morpholino, piperidino, indolinyl, 1-imidazolidyl, 2-imidazolin-1-yl, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl And selected from the group consisting of pyrrolidyl.
(Ii) Group represented by the following formula:

Wherein U is a hydrogen atom or C ₁ -C ₄ alkyl, and V is an unsubstituted or mono- or di-substituted group selected from the group consisting of naphthyl, phenyl, furanyl and thienyl, each substituent of a _C 1 -C _{4 alkyl,} C 1 -C ₄ alkoxy, fluorine atom or chlorine atom.
(Iii) a group represented by the following formula:

Wherein M is CH ₂ , O, S or N—R ₁₄ , wherein R ₁₄ is from a hydrogen atom, C ₁ -C ₆ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono- and di-substituted phenyl. The phenyl substituent is selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, chlorine atom and fluorine atom, and R ₉ is C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, A chlorine atom or a fluorine atom, and a represents a number selected from 0, 1, 2, and 3.
(E) B and B ′ may together form an unsubstituted, mono-substituted or di-substituted fluorene-9-ylidene, or may form a ring selected from the following group: : saturated _C 3 _{-C 12} spiro - monocyclic hydrocarbon ring, saturated _C 7 _{-C 12} spiro - bicyclic hydrocarbon rings and saturated _C 7 _{-C 12} spiro - tricyclic hydrocarbon ring. However, the above-mentioned bicyclic and tricyclic hydrocarbon rings do not include adamantylidene, bornylidene and norbornylidene. Fluoren-9-ylidene substituents being selected from the group consisting of _C 1 -C _{4 alkyl,} C 1 -C ₄ alkoxy, fluorine atom and chlorine atom.
(F) Each of B and B ′ is selected from the groups defined in (d) (ii) and (d) (iii) above. The naphthopyran according to claim ₁ , wherein R ₁ , R ₂ , R ₃ , B and B 'have the following significance:
(A) _{R 1} represents a -C (O) W, W represents a -OR ₄ or _{-N (R 5) R 6,} R 4 is a hydrogen _atom, C 1 -C ₄ alkyl, phenyl, mono (C ₁ -C ₄₎ alkyl-substituted phenyl, mono _(C 1 -C ₄₎ alkoxy substituted phenyl, phenyl _(C 1 -C ₂₎ alkyl, mono _(C 1 -C ₄₎ alkyl substituted phenyl _(C 1 -C ₂₎ alkyl , Mono (C ₁ -C ₄ ) alkoxy substituted phenyl (C ₁ -C ₂ ) alkyl, mono (C ₁ -C ₄ ) alkoxy (C ₂ -C ₃ ) alkyl or C ₁ -C ₄ haloalkyl, R ₅ And each of R ₆ represents a group selected from the group consisting of a hydrogen atom, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono- or di-substituted phenyl.
The phenyl substituent is selected from C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, and the halo substituent is a chlorine atom or a fluorine atom.
(B) Each of R ₂ and R ₃ represents a hydrogen atom, C ₁ -C ₃ alkyl, C ₃ -C ₅ cycloalkyl, substituted or unsubstituted phenyl, or —OR ₇ , and R ₇ is a hydrogen atom, C ₁ —C ₃ alkyl or —CH (R ₈ ) X is represented, X represents —CN or —C (O) W, and R ₈ represents a hydrogen atom or methyl. Alternatively, R ₇ represents —C (O) Y, and Y represents C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy. The phenyl substituent represents C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, and n represents a number of 0 or 1.
(C) B is unsubstituted or mono- - or di - substituted phenyl, the phenyl substituents are _C 1 -C _{4 alkyl,} C 1 -C ₄ alkoxy, halogen atom, _amino, C 1 -C ₄ monoalkylamino, C ₁ -C ₄ dialkylamino, morpholino, piperidino, selected from the group consisting of indolinyl and pyrrolidyl, halogen atom is a fluorine atom or a chlorine atom.
(D) B ′ is selected from the group consisting of the following (i) to (iii).
(I) Mono-substituted phenyl. Phenyl substituent is _amino, C 1 -C _{4 monoalkylamino,} C 1 -C ₄ dialkylamino, morpholino, piperidino, are selected from the group consisting of indolinyl and pyrrolidyl.
(Ii) A group represented by the following formula:

In the formula, U may be a hydrogen atom or methyl, V is phenyl or mono-substituted phenyl, and the phenyl substituent is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, fluorine atom or base atom. is there.
(Iii) a group represented by the following formula:

Wherein M is CH ₂ , O or N—R ₁₄ , R ₁₄ is selected from the group consisting of a hydrogen atom, C ₁ -C ₄ alkyl, phenyl and mono-substituted phenyl, wherein the phenyl substituent is C ₁ — Selected from C ₄ alkyl, C ₁ -C ₄ alkoxy, chlorine atom and fluorine atom, R ₉ is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, chlorine atom or fluorine atom, and a is 0, 1 And 2.
(E) B and B ′ may together form an unsubstituted or mono-substituted fluorene-9-ylidene, or a saturated C ₃ -C ₈ spiro-monocyclic hydrocarbon ring, saturated C ₇ -C ₁₀ spiro - bicyclic hydrocarbon rings and saturated C ₇ -C ₁₀ spiro - may form a ring selected from the group consisting of tricyclic hydrocarbon ring, substituent of the fluoren-9-ylidene C ₁ - Selected from the group consisting of C ₃ alkyl, C ₁ -C ₃ alkoxy, fluorine atom and chlorine atom. (A) R ₁ is a —C (O) W group, W is —OR ₄ or —N (R ₅ ) R ₆ , and R ₄ is a hydrogen atom, C ₁ -C ₃ alkyl, phenyl, Mono (C ₁ -C ₃ ) alkyl-substituted phenyl, mono (C ₁ -C ₃ ) alkoxy-substituted phenyl, mono (C ₁ -C ₃ ) alkoxy (C ₂ -C ₃ ) alkyl or C ₁ -C ₃ haloalkyl. R ₅ and R ₆ are each selected from the group consisting of a hydrogen atom, C ₁ -C ₃ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono-substituted phenyl, wherein the phenyl substituent is C ₁ -C Selected from ₃ alkyl and C ₁ -C ₃ alkoxy, wherein the halo substituent is a fluorine atom;
(B) R ₂ and R ₃ are each selected from the group consisting of a hydrogen atom, C ₁ -C ₃ alkyl, phenyl, and —OR ₇ , and R ₇ is a hydrogen atom or C ₁ -C ₃ alkyl, or , R ₇ is a —C (O) Y group, Y is C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, n is selected from the integers 0 and 1,
(C) B is selected from the group consisting of unsubstituted phenyl, mono-substituted phenyl and di-substituted phenyl, the phenyl substituent being C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, fluorine atom, amino, C _1- C _{3 monoalkylamino,} C 1 -C ₃ dialkylamino, selected from the group consisting of morpholino and piperidino,
(D) B ′ is selected from the group consisting of (i) and (ii) below:
(I) monosubstituted phenyl (wherein the phenyl substituents are _amino, C 1 -C _{3 monoalkylamino,} C 1 -C ₃ dialkylamino, phenyl substituent selected from the group consisting of morpholino and piperidino),
(Ii) a group represented by the following chemical formula:

(Where M is CH ₂ , 0 or N—R ₁₄ , R ₁₄ is a hydrogen atom, C ₁ -C ₄ alkyl or phenyl, R ₉ is C ₁ -C ₄ alkyl, C ₁ -C ₄ is selected from the group consisting of alkoxy and fluorine atoms, a is selected from the integers 0, 1 and 2), or
(E) B and B ′ together form fluorene-9-ylidene or bicyclo [3.3.1] nonane-9-ylidene,
The naphthopyran according to claim 2. R ₁ is a —C (O) W group, W is —OR ₄ or —N (R ₅ ) R ₆ , R ₄ is a hydrogen atom or C ₁ -C ₃ alkyl, R ₅ and R ₆ are each A hydrogen atom, C ₁ -C ₃ alkyl or phenyl, R ₂ and R ₃ are each a hydrogen atom or C ₁ -C ₃ alkyl, B is unsubstituted phenyl, mono-substituted phenyl or di-substituted phenyl, The phenyl substituent is C ₁ -C ₂ alkyl, C ₁ -C ₂ alkoxy, fluorine atom, C ₁ -C ₂ monoalkylamino, C ₁ -C ₂ dialkylamino, morpholino or piperidino, and B ′ is mono-substituted phenyl a 9-ethyl carbazolyl or 9-phenylcarbazolyl, the phenyl substituent is _C 1 -C _{2 monoalkylamino,} C 1 -C ₂ dialkyl Mino, a morpholino or piperidino, naphthopyran of claim 3. (A) 2- (4-Morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran,
(B) 2- (4-Morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-methoxy-2H-naphtho [1,2-b] pyran,
(C) 2- (4-Morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran,
(D) 2- (9-ethylcarbazol-2-yl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran,
(E) 2- (9-phenylcarbazol-2-yl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran,
(F) 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran,
(G) 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-methyl-2H-naphtho [1,2-b] pyran, and (h) 2,2-bis (4- Dimethylaminophenyl) -5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran,
A naphthopyran compound selected from the group consisting of:   A photochromic article comprising a polymeric organic host material and a photochromic amount of the naphthopyran compound of claim 1. Polymeric organic host material is polyacrylates, polymethacrylates, poly (C ₁ -C ₁₂ alkyl methacrylates), polyoxy (alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose Acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), thermoplastic polycarbonate, polyester, polyurethane, poly (ethylene terephthalate), polystyrene, poly (alphamethylstyrene) , Copoly (styrene-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinyl butyral and polyol (allyl) From the group consisting of polymers of elements in the group consisting of (rubonate) monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, diisopropenylbenzene monomers, alkoxylated polyhydric alcohol acrylate monomers and diarylidenepentaerythritol monomers. The photochromic article of claim 6, which is selected.   A photochromic article comprising a polymer organic host material and a photochromic amount of the naphthopyran compound of claim 2. Polymeric organic host material is polyacrylates, polymethacrylates, poly (C ₁ -C ₁₂ alkyl methacrylates), polyoxy (alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose Acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), thermoplastic polycarbonate, polyester, polyurethane, poly (ethylene terephthalate), polystyrene, poly (alphamethylstyrene) , Copoly (styrene-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinyl butyral and polyol (allyl) (Lubonate) monomer, polyfunctional acrylate monomer, polyfunctional methacrylate monomer, diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer, alkoxylated polyhydric alcohol acrylate monomer and diarylidene pentaerythritol monomer 9. A photochromic article according to claim 8, selected from the group.   Polymer organic host materials include poly (methyl methacrylate), poly (ethylene glycol bismethacrylate), poly (ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly (vinyl acetate), polyvinyl butyral, polyurethane, and diethylene glycol bis 10. A transparent, transparent homopolymer or copolymer selected from the group of polymers of (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylolpropane triacrylate monomers. The photochromic article as described in 1.   11. The photochromic article of claim 10, wherein the photochromic compound is present in an amount of about 0.05 to 1.0 milligrams per square centimeter of the organic host material surface on which the photochromic material is mixed or applied.   The photochromic article according to claim 11, wherein the article is a lens.   4. A photochromic naphthopyran compound according to claim 3 as well as poly (methyl methacrylate), poly (ethylene glycol bismethacrylate), poly (ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly (vinyl acetate), polyvinyl butyral, A polymer organic host material selected from the group consisting of polyurethane and a polymer of elements in the group consisting of diethylene glycol bis (allyl carbonate) monomer, diethylene glycol dimethacrylate monomer, diisopropenylbenzene monomer and ethoxylated trimethylolpropane triacrylate monomer Containing photochromic article.   5. A photochromic naphthopyran compound according to claim 4 as well as poly (methyl methacrylate), poly (ethylene glycol bismethacrylate), poly (ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly (vinyl acetate), polyvinyl butyral, A polymer organic host material selected from the group consisting of polyurethane and a polymer of elements in the group consisting of diethylene glycol bis (allyl carbonate) monomer, diethylene glycol dimethacrylate monomer, diisopropenylbenzene monomer and ethoxylated trimethylolpropane triacrylate monomer Containing photochromic article.   A solid transparent polymeric organic host material and a photochromic amount of (a) at least one naphthopyran compound of claim 1 and (b) at least one activated absorption maximum in the range of about 400-700 nanometers. A photochromic article containing at least one other organic photochromic compound. Polymeric organic host material is polyacrylates, polymethacrylates, poly (C ₁ -C ₁₂ alkyl methacrylates), polyoxy (alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose Acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), thermoplastic polycarbonate, polyester, polyurethane, poly (ethylene terephthalate), polystyrene, poly (alphamethylstyrene) , Copoly (styrene-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinyl butyral and polyol (allyl) From the group consisting of polymers of elements in the group consisting of (rubonate) monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, diisopropenylbenzene monomers, alkoxylated polyhydric alcohol acrylate monomers and diarylidenepentaerythritol monomers. 16. A photochromic article according to claim 15, which is selected. The organic photochromic compound (b) is
(A) an organic photochromic material having at least one absorption maximum in the visible region between 400 and 500 nanometers or less;
(B) an organic photochromic material having an absorption maximum in the visible region between about 400 and 500 nanometers and an absorption maximum in the visible region between 500 and 700 nanometers;
16. The photochromic article of claim 15, selected from the group consisting of (c) an organic photochromic material having an activated absorption maximum in the visible region above 570 nanometers, and (d) a mixture of the organic photochromic materials.   18. The photochromic article according to claim 17, wherein the organic photochromic compound (b) is an organic photochromic material having an activated absorption maximum in the visible region exceeding 570 nanometers.   Polymer organic host materials include poly (methyl methacrylate), poly (ethylene glycol bismethacrylate), poly (ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly (vinyl acetate), polyvinyl butyral, polyurethane, and diethylene glycol bis (allyl) 17. A solid transparent homopolymer or copolymer selected from the group of polymers of carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenylbenzene monomers and ethoxylated trimethylolpropane triacrylate monomers. Polymer organic host material.   The organic photochromic compound (b) is spiro (indoline) naphthoxazine, spiro (indoline) -pyridobenzoxazine, spiro (benzindoline) -pyridobenzoxazine, spiro (benzindoline) -naphthoxazine, spiro (benzindoline). -Naphthopyran, spiro (indoline)-benzoxazine, spiro (indoline)-benzopyran, spiro (indoline)-naphthopyran, spiro (indoline)-quinopyran, spiro (indoline) pyran, 3H-naphtho [2,1-b] pyran, 2H 18. A photochromic article according to claim 17, selected from the group consisting of phenanthro [4,3-b] pyran, 3H-phenanthro [1,2-b] pyran, benzopyran compounds and mixtures of these photochromic substances.