KR20010013430A - Substituted naphthopyrans - Google Patents

Abstract

The present invention relates to a novel reversible photochromic 2H-naphtho [1,2-b] pyran compound, for example the compound is a carbon atom at the naphtho-position of naphthopyran and 2 of the pyran ring. Has a specific substituent in the position. Certain substituents may also be present at carbon atoms 6, 7, 8, 9 or 10 in the naphtho-position of the naphthopyran. The present invention also relates to organic host materials containing or coated with the compound. The present invention also relates to articles such as ophthalmic lenses or other plastic transparent bodies incorporating the novel naphthopyran compounds or mixtures thereof with compensating photochromic compounds.

Description

Substituted naphthopyrans {SUBSTITUTED NAPHTHOPYRANS}

Many photochromic compounds change color reversibly when exposed to ultraviolet associated radiation, such as ultraviolet light in sunlight or mercury light. When ultraviolet irradiation is stopped, such photochromic compounds return to their original color or colorless state.

Various classes of photochromic compounds have been synthesized, and their use has been proposed where they are required to be induced by sunlight to change color reversibly or become dark colors. US Patent No. 3,567,605 to Becker describes various pyran derivatives, including certain benzopyrans and naphthopyrans. The compounds have been described as chromene derivatives and have been reported to change color, ie from colorless to orange, by ultraviolet radiation at about -30 ° C. Irradiation of visible light or raising the temperature above about 0 ° C. has been reported to return the color to a colorless state.

U.S. Pat.No. 5,066,818 discloses a variety of 3,3-diaryl-3H-naphtho [2,1-b] pyrans that are preferred for photochromic properties, i.e., high colorability and suitable fade. , Bleaching). In addition, the comparative example of the '818 patent reports that it takes too long to decolorize after the isomeric 2,2-diaryl-2H-naphtho [1,2-b] pyran is activated.

U. S. Patent No. 3,627, 690 describes photochromic 2,2-di-substituted-2H-naphtho [1,2-b] pyran compositions containing small amounts of base or acids of mild to moderate strength. It has been reported that when an acid or base is added to the naphthopyran composition, it can be used for eye protection such as sunglass by increasing the discoloration rate of the colored naphthopyran. The document also reported that in the absence of the above-mentioned additives the rate of decolorization of 2H-naphtho [1,2-b] pyrans leading to a complete recovery is from several hours to several days. U.S. Patent No. 4,818,096 discloses blue photochromic benzopyrans or naphthopyrans with nitrogen containing phenyl groups at the α-position to the oxygen of the pyran ring, including substituents at ortho or para-positions.

The present invention relates to a novel substituted 2H-naphtho [1,2-b] pyran compound, which was unexpectedly found to exhibit a high activation intensity and high color development as well as an appropriate decolorization rate. In particular, the use of specific substituents at position 5 of the naphtho residue of the naphthopyran compound increases the rate of decolorization without the addition of acids or bases. In addition, these compounds carry specific substituents at position 2 of the pyran ring. Certain substituents may also be present at carbon positions 6, 7, 8, 9 or 10 of the naphtho moiety of naphthopyran.

The present invention relates to certain novel naphthopyran compounds. More specifically, the present invention relates to novel photochoromic naphthopyran compounds and compositions and articles containing the naphthopyran compounds.

Recently, photochromic plastic materials, in particular optical plastic materials, have been of considerable interest. In particular, photochromic ophthalmic plastic lenses have been studied for their weight advantage over glass lenses. Moreover, photochromic transparents used in vehicles such as vehicles and airplanes are of interest due to the potential stability features they provide.

In accordance with the present invention, certain novel 2H-naphtho [1,2-b] pyran compounds can be prepared having a suitable decolorization rate, high activated intensity and high color development. These compounds may be described as naphthopyrans with specific substituents at position 2 of the pyran ring and position 5 carbon of the naphtho residue of the naphthopyran ring. Certain substituents may be present at carbon positions 6, 7, 8, 9 or 10 of the naphtho moiety of the naphthopyran ring. These compounds may be represented by the following structural formula (I).

In formula (I), R ₁ is a -C (O) W group where W is -OR ₄ or -N (R ₅ ) R ₆ , where R ₄ is hydrogen, allyl, C ₁ -C ₆ alkyl (eg methyl , Ethyl, propyl, butyl, pentyl and 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; R ₅ and R ₆ may each be selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono- or di-substituted phenyl. Phenyl substituents are C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy and halo substituents are chloro or fluoro.

Preferably, R ₁ is a -C (O) W group where W is -OR ₄ or -N (R ₅ ) R ₆ , wherein R ₄ is hydrogen, 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 ego; R ₅ and R ₆ may each be selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono- or di-substituted phenyl. Phenyl substituents are C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy and halo substituents are chloro or fluoro.

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

In formula (I), R ₂ and R ₃ are each hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₇ cycloalkyl, substituted or unsubstituted phenyl, -OR ₇ group, wherein R ₇ is hydrogen, 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, -CH (R ₈ ) X group, where X is -CN, -CF ₃ , halogen or -C (O) W, and R ₈ is hydrogen or C ₁ -C ₆ alkyl Or -C (O) Y, wherein Y is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, substituted or unsubstituted aryl group phenyl or naphthyl, phenoxy, C ₁ -C ₆ mono Or dialkyl substituted phenoxy, C ₁ -C ₆ mono- or dialkoxy substituted phenoxy, C ₁ -C ₆ alkylamino, phenylamino, C ₁ -C ₆ mono- or dialkyl substituted phenylamino, Or C ₁ -C ₆ mono- or dialkoxy substituted phenylamino), wherein each substituent of phenyl and naphthyl is selected from C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy and the halogen or halo substituent is chloro or Fluoro and n is an integer selected from 0, 1, 2 and 3.

Preferably, R ₂ and R ₃ are each hydrogen, C ₁ -C ₃ alkyl, C ₃ -C ₅ cycloalkyl, substituted or unsubstituted phenyl or -OR ₇ group, wherein R ₇ is hydrogen, C ₁ -C ₃ alkyl or —CH (R ₈ ) X group wherein X is —CN or —C (O) W and R ₈ is hydrogen or methyl; or —C (O) Y where Y is C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy), and the substituent of the phenyl is C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, n is an integer selected from 0 and 1. More preferably , R ₂ and R ₃ are each hydrogen, C ₁ -C ₃ alkyl, phenyl and -OR ₇ group, wherein R ₇ is hydrogen, C ₁ -C ₃ alkyl or -C (O) Y, wherein Y is C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy), n is an integer selected from 0 and 1. Most preferably, R ₂ and R ₃ are each hydrogen or C ₁ -C ₃ Alkyl In the definitions of R ₁ , R ₂ and R ₃ of formula I, unless otherwise stated, The worked letter has the same meaning.

In Formula I, B may be an unsubstituted, mono-, di- or tri-substituted aryl group phenyl and naphthyl, said aryl substituents being C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen, amino, C _1- C ₆ monoalkylamino, C ₁ -C ₆ dialkylamino, ie di- (C ₁ -C ₆ ) alkylamino, morpholino, piperidino, indolinyl, 1-imidazolidil, 2 Imidazolin-1-yl, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl and pyrrolidyl, wherein the halogen is fluoro or chloro. Preferably, B is unsubstituted, mono-, di- or tri-substituted phenyl, wherein the phenyl substituent is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, amino, C ₁ -C ₄ mono Alkylamino, C ₁ -C ₄ dialkylamino, morpholino, piperidino, indolinyl and pyrrolidyl, wherein the halogen is fluoro or chloro. More preferably, B is unsubstituted, mono- or di-substituted phenyl, wherein the phenyl substituent is C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, fluoro, C ₁ -C ₃ monoalkylamino, C ₁ -C ₃ dialkylamino, morpholino and piperidino. Most preferably, B is unsubstituted, mono- or di-substituted phenyl, wherein the phenyl substituent is C ₁ -C ₂ alkyl, C ₁ -C ₂ alkoxy, fluoro, C ₁ -C ₂ monoalkylamino, C ₁ -C ₂ dialkylamino, morpholino and piperidino.

B ′ of formula I is selected from the following groups (i) to (v):

(i) mono-substituted aryl groups phenyl and naphthyl, wherein the substituents of aryl 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 pyrrolidyl;

(ii) a group of formula (IAA)

Wherein U is hydrogen or C ₁ -C ₄ alkyl, V is unsubstituted, mono- and di-substituted phenyl, selected from the group consisting of naphthyl, phenyl, furanyl and thienyl, the substituent being C _1- C ₄ alkyl, C ₁ -C ₄ alkoxy, fluoro or chloro;

(iii) a group of formula IIB:

Wherein M is CH ₂ , O, S or NR ₁₄ where R ₁₄ is hydrogen, C ₁ -C ₆ alkyl, C ₅ -C ₇ cycloalkyl, phenyl, mono-substituted and di-substituted phenyl Is selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, chloro and fluoro), and R ₉ is C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, Chloro or fluoro and a is an integer selected from 0, 1, 2 and 3.

(iv) B and B 'together form an unsubstituted, mono- or di-substituted fluorene-9-ylidene, or a saturated C ₃ -C ₁₂ spiro-monocyclic hydrocarbon ring, for example cyclopropylidene , Cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptidene, cyclooctylidene, cyclononylidene, cyclodecylidene, cyclodecylidene, cyclododecylidene; Saturated C ₇ -C ₁₂ spiro-bicyclic hydrocarbon rings, eg bicyclo [3.2.1] octylidene, bicyclo [3.3.1] nonan-9-ylidene and bicyclo [4.3.2] Undecane; And saturated C ₇ -C ₁₂ spiro-tricyclic hydrocarbon rings, for example tricyclo [2.2.1.0 ^2,6 ] heptylidene and tricyclo [5.3.1.1 ^2,6 ] dodecylidene Except that tricyclo [3.3.1.1 ^3,7 ] ^decylidene , ie adamantylidene, 1,7,7-trimethyl bicyclo [2.2.1] heptidene, ie bonylidene and Bicyclo [2.2.1] heptylidene, ie nobornylidene, is excluded. Fluorene-9-ylidene substituents are selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, fluoro and chloro.

(v) B and B 'are each selected from the group defined in (d) (ii) and (d) (iii) above.

Preferably, B 'is

(i) mono-substituted phenyl, wherein the phenyl substituent is selected from amino, C ₁ -C ₄ monoalkylamino, C ₁ -C ₄ dialkylamino, morpholino, piperidino, indolinyl and pyrrolidyl );

(ii) a group represented by formula (IA), wherein U can be hydrogen, or methyl, and V is phenyl or mono-substituted phenyl (the wasteyl substituent is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, Fluoro, or chloro); And

(iii) a group represented by Formula IIB, wherein M is CH ₂ , O or NR ₁₄ , and R ₁₄ is hydrogen, C ₁ -C ₄ alkyl, phenyl and mono-substituted phenyl (the phenyl substituent is C _1- C ₄ alkyl, C ₁ -C ₄ alkoxy, chloro or fluorine), R ₉ is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, chloro or fluoro, a is 0, 1 and 2 Is selected from an integer of or

(iv) unsubstituted or mono-substituted fluorene-9-ylidene (the fluorene-9-ylidene substituent is a group consisting of C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, fluoro and chloro ), Or saturated C ₃ -C ₈ spiro-monocyclic hydrocarbon rings, saturated C ₇ -C ₁₀ spiro-bicyclic hydrocarbon rings, and saturated C ₇ -C ₁₀ spiro-tricyclic hydrocarbons And B and B 'which together form a member selected from the group consisting of rings.

More preferably, B 'is

(i) mono-substituted phenyl, wherein the phenyl substituent is selected from the group consisting of amino, C ₁ -C ₃ monoalkylamino, C ₁ -C ₃ dialkylamino, morpholino and piperidino;

(ii) a group represented by formula (IIB) wherein M is CH ₂ , O, or NR ₁₄ , R ₁₄ is selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl or phenyl; R ₉ is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and fluoro, and a is selected from 0, 1 and 2 integers); or

(iv) B and B 'which together form fluorene-9-ylidene or bicyclo [3.3.1] nonane-9-ylidene.

Most preferably, B 'is mono-substituted phenyl, 9-ethyl carbazolyl or 9-phenyl carbazolyl (the phenyl substituent is C ₁ -C ₂ monoalkylamino, C ₁ -C ₂ dialkylamino, morpho O or piperidino).

The compound represented by formula (I) can be prepared by the method described below. In Scheme A1, benzoyl derivatives of carbazole, dibenzothiophene or dibenzofuran are prepared according to the Frieded-Crafts method (see “Frieded-Crafts and Related Reactions”, George A. Olah, Interscience Publishers, 1964, vol. 3, Chapter XXX (Aromatic Ketone Synthesis); and "Regioselective Frieded-Crafts Acylation of 1,2,3,4-Tetrahydroquinoline and Related Nitrogen Heterocycles: Effect on NH Protective Groups and Ring Size", by Ishihara, Yugi et al., J. Chem. Soc., Perkin Trans. 1, pages 3401-3406 (1992); Heterocyclic Compound, Robert C. Elderfield, 1951, Vol. 2, Chapter 3 (Dibenzofuran) and Chapter 5 (Dibenzothiophene); The Chemistry of Heterocyclic Compounds, HD Hartough and SL Meisel, 1954, Vol. 7, Chapter IV (Dibenzothiophene and its Derivatives); Advances in Heterocyclic Chemistry, AR Katritzky and AJ Boulton, 1974, Vol. 16, Chapter V (Recent Advances in the Chemistry of Dibenzothiophenes And Heterocyclic Compounds, Robert C. Elderfield, 1952, Vol. 3, Chap ter 3 (The Chemistry of Carbazole).

In Scheme A1, the compounds represented by formulas (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 substituted benzoyl derivatives represented by formula (V), wherein R is a latent phenyl substituent To form.

Compounds represented by the formula (VB) are commercially available fluoro substitutions represented by the formula (VA) with primary or secondary amine compounds such as ethyl amine, morpholine, piperidine, etc., as shown in Scheme A2. Obtained or prepared by direct amination of benzophenone (see Barder, Henry et al., J. Org. Chem., Nucleophilic Displacements of Activated Fluorine in Aromatic Compound "Vol. 31., 2319-2321 (1991)). .

In Scheme A, the compounds represented by formula VA and amino compounds are dissolved in a solvent such as dimethyl sulfoxide (DMS) and refluxed to form amino substituted benzophenones represented by formula VB, wherein R is a latent phenyl substituent. Create

In Scheme B, ketones represented by Formula V, VB or, more generally, VC, are reacted with sodium acetylide in a suitable solvent such as anhydrous tetrahydrofuran (THF) to produce propargyl alcohol represented by Formula VI. Propargyl alcohols having the B 'group represented by the formula IIA can be prepared according to the methods disclosed in columns 2, 40-68 of US Pat. No. 5,274,132.

Naphthol represented by formula (XIIIA) may be prepared by Scheme C or D. In Scheme C, substituted or unsubstituted 1,4-dihydroxy-2-nattolic acid represented by Formula VII is methyl iodide in a suitable solvent such as anhydrous dimethylformamide (DMF) in the presence of ethyldiisopropyl amine. Reacts with an id (or ethyl iodide, propyl iodide, benzyl bromide, etc.) to produce methyl-1,4-dihydroxy-2-naphthoate represented by Formula VIII (or Formula XIIIA in Scheme E) do. This reaction is also described in J. of Org. Chem., Vol. 46 (17), 3477 (1981).

In Scheme D, substituted or unsubstituted acetophenone, benzophenone or benzaldehyde represented by Formula IX is reacted with dimethyl succinate (Formula X) in a suitable solvent such as toluene in the presence of a base such as sodium hydride or potassium t-butoxide To form an appropriately substituted monoester of a-arylidene succinic acid represented by formula (XI). Other ester substituents on the compounds represented by formula (XI) can be prepared by using other succinate esters, such as diethyl succinate. Compound XI is heated with acetic anhydride and anhydrous sodium acetate to produce an acetate derivative represented by formula (XII). Compound XII is reacted with anhydrous alcohols such as hydrochloric acid and anhydrous methanol to produce naphthol represented by Formula XIII (or Formula XIIIA in Scheme E). Scheme D is also described in Organic Reactions, Vol. VI, Chapter 1, 1-73, John Wiley & Sons, Inc., New York.

In Scheme E, propargyl alcohol represented by formula VI is coupled with naphthol represented by formula XIIIA to produce a compound represented by formula I.

As shown in Scheme F, the compound represented by Formula XIV (Formula I compound wherein R ₂ is hydroxy) can be converted into various other groups by reaction with an acylating agent or alkylating agent. For example, the compound represented by the formula (XIV) is reacted with methyl iodide (or other alkylating agent) in a suitable solvent such as anhydrous acetone in the presence of anhydrous potassium carbonate, wherein R ₂ is Oxy substituent). Alkylation reactions are also described in Organic Synthesis, Vol. 31, pages 90-93, John Wiley & Sons, Inc., New York. Alternatively, compound XIV is reacted with acetyl chloride (or other acylating agent) in a suitable solvent, such as methylene chloride in the presence of triethylamine (NEt ₃ ), represented by formula XVI, wherein R is an acetoxy (AcO) substituent. To form a compound. Acylation reactions are also described in Organic Synthesis, Vol. 32, pages 72-77, John Wiley & Sons, Inc., New York.

Compounds represented by formula (I) include optical lenses (e.g. ophthalmic and plano lenses for vision correction), shading surfaces, safety glasses, masking, camera lenses, windows, windshields of automobiles, transparent bodies of aircraft and automobiles (e.g. T-loops, metering and halo), plastic films and sheets, textiles and coatings (e.g. coating compositions such as paints), and verification marks on protective documents requiring identification or verification of identity (e.g. bills, passports and driver's licenses) Organic photochromic materials such as can be applied to the field can be used. Naphthopyran represented by the formula (I) shows a color change from colorless to orange to blue.

Examples of naphthopyrans that fall within the scope of the present invention are as follows:

(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.

Organic photochromic naphthopyrans of formula (I) can be used in admixture with other suitable compensating organic photochromic materials to form a medium gray or brown tint with these materials together when a plastic lens containing such photochromic materials is exposed to ultraviolet light. I think I make it. For example, a yellowish compound can be mixed with a suitable purpleish compound to produce a brown tint. Similarly, a compound that is orange in color development will produce a gray tint when used in combination with a suitable blue compound. The mixture of photochromic materials can also be used for applications other than spectacle lenses.

The novel naphthopyran compounds of the present invention, such as the compounds described above, can be used alone or as compensation photochromic compounds, i.e., organic photochromic compounds having at least one active absorption maximum in the range of about 400 to 700 nm, or It may be used in admixture with the containing material, and may be added, such as by dissolving or dispersing in the polymeric organic host material used to make the photochromic product with a suitable color when activated.

As a first group of compensating organic photochromic materials that can be used with the organic photochromic naphthopyrans of the present invention, within the visible range of greater than 570 nm, for example greater than about 570 nm and up to 700 nm There are compounds with an active absorption maximum in the visible range. These materials are typically blue, cyan or blue violet when exposed to ultraviolet light in a suitable solvent or substrate. Many of these compounds are described in published literature. For example, among these, spiro (indolin) naphthoxazine is described in US Pat. Nos. 3,562,172, 3,578,602, 4,215,010 and 4,342,668, and the 8 'and 9' positions of the naphthograph residues of the molecule. Spiro (indolin) naphthoxazine having a substituent on is described in US Pat. No. 5,405,958, Spiro (indolin) pyridobenzoxazine is described in US Pat. No. 4,637,698, and a spiro (benzindolin) pyridine Dobenzazine and spiro (benzindoline) naphthoxazine are described in US Pat. No. 4,931,219, spiro (benzindoline) naphthoppyran is described in Japanese Patent Publication No. 62/195383, and spiro (indole) Lin) benzoxazines are described in US Pat. No. 4,816,584, and spiro (indolin) benzopyrans, spiro (indolin) naphthopran and spiro (indolin) quinopyrans are described, for example, in US Pat. No. 4,880,667 It is, This is benzopyran and naphthopyrans having a substituent containing nitrogen in the 2-position of the ring are described in U.S. Patent No. 4,818,096. Spiro (indoline) pyrans are also described in Techniques in Chemistry, volume III, "Photochromism", Chapter 3, Glenn H. Brown, Editor, John Wiley and Sons, Inc., New York, 1971.

As the second group of compensating organic photochromic materials that can be used with the organic photochromic naphthopyrans of the present invention, there are compounds having at least one absorption maximum in the visible range of about 400 to 500 nm. These materials are typically yellow-orange when exposed to ultraviolet light in a suitable solvent or substrate. Such compounds include chromenes, ie benzopyrans and naphthopyrans. Many of these chromens are described in published literature, ie US Pat. Nos. 3,567,605, 4,826,977, and 5,066,818. Other examples of compensating benzopyrans and naphthopyrans that may be used with the naphthopyrans of the present invention are compounds having spiro adamantane groups in the alpha position relative to the oxygen atom of the pyran ring described in US Pat. No. 4,826,977, 1993 2H-naphtho- [1 having substituents at the 4 and 5 carbon atoms of the naphtho residues of naphthopyrans and the 2 positions of pyrans, the subject of pending US patent application Ser. No. 08 / 164,187, filed Dec. 9; , 2-b] -pyran compound, 3H-naphtho [2,1-b] pyran, having at least one ortho-substituted phenyl substituent at the 3 position of the pyran ring described in US Pat. No. 5,066,818, June 1993 3H- having a substituent on carbon atom 8 and a substituent on carbon atom 7 or 9, which is the subject of pending US patent application Ser. No. 08 / 080,246, filed on December 21, wherein these substituents are located at the naphtho residues of naphthopyrans. Naphtho [2,1-b] pyran unity Water, a phenyl substituent having a 5 or 6 membered heterocycle ring bonded to carbon atoms 3 and 4 of the (i) aryl substituent and (ii) the phenyl substituent at the 3 position of the pyran ring described in US Pat. No. 5,384,077, 1994 Diaryl-3H having a substituted or unsubstituted 5 or 6 membered heterocycle ring bonded to the g, i or l side of naphthopyran, the subject of pending US patent application Ser. No. 08 / 225,022, filed April 8, Naphtho [2,1-b] pyran compounds, naphthopyran compounds substituted with, for example, methoxy groups at the 8th carbon atom of the naphtho moiety of the naphthopyran ring of the subject of US Pat. No. 5,238,931, US Pat. Naphthopyran compounds described in US Pat. No. 5,274,132, such as 3-aryl-3-arylalkenyl naphthopyrans, and naphthos substituted with, for example, acetoxy groups on carbon number 5, the subject of US Pat. No. 5,244,602 [ 2,1-b] pyran is mentioned.

As a third group of compensating organic photochromic materials that can be used with the organic photochromic naphthopyrans of the present invention, absorption maximums within the visible range of about 400 to about 500 nm and visible of about 500 to about 700 nm There are compounds with another absorption maximum in the range. These materials typically have colors ranging from yellow to purple and yellow / brown to purple / grey when exposed to ultraviolet light in a suitable solvent or substrate. Examples of these compounds include substituted 2H-phenanthro [4,3-b] pyrans; At the 2-position of the substituted or unsubstituted heterocycle ring and pyran ring, such as substituted 3H-phenanthro [1,2-b] pyran and a benzothieno or benzofurano ring fused to the benz moiety of benzopyran The benzopyran compound like the compound which has a substituent is mentioned. The latter compounds are the subject of pending US patent application 08 / 286,039 and US patent 5,411,679, filed August 4, 1994.

The photochromic article of the present invention may comprise one photochromic compound or a mixture of photochromic compounds, depending on the purpose or need. Individual photochromic compounds or mixtures of photochromic compounds can be used to obtain an activated color such as medium gray or brown.

In addition, compounds of the present invention (hereinafter referred to as second group photochromic compounds) are organic photochromic materials belonging to the photochromic compounds of the first compensation group described herein, ie, compounds having a blue, cyan or blue violet color, Or other organic photochromic materials belonging to the second group of photochromic compounds. Each of the constituent compounds of the first or second group of photochromic compounds or mixtures of these compounds may be mixed with a third group of photochromic compounds described herein exhibiting a hue ranging from yellow to purple and tan to purple gray. Can be used in combination.

Each of the photochromic compounds described herein is substantially neutral in color, i.e., the color of the activated photochromic compound, when the photochromic compound or mixture thereof is activated or unfiltered daylight to the organic host material. As long as it is indicated, it can be used in an amount that brings about the desired color, such as almost intermediate color.

Medium gray represents spectra with relatively equal absorbance in the visible region ranging from 400 to 700 nm. Medium brown shows a spectrum in which the absorbance in the range of 400 to 550 nm is greater than the absorbance in the range of 550 to 700 nm. In addition to the lightness factor, another way of describing the quality of a color is the color coordinate, ie the hue. In the CIE system, color coordinates are obtained by finding the ratio of their sum of tristimulus values, for example x = X / (X + Y + Z) and y = Y / (X + Y + Z). The colors described by the CIE system can be represented by a hue diagram, a chart of color coordinates x and y (FW Billmeyer, Jr ,, and Max Saltzman, Principles of Color Technology, p. 47-52, Second Edition, John Wiley and Sons, NY (1981). As used herein, almost neutral colors have a color coordinate value of "x" and "y" for that color, with a luminous transmission of 40% due to exposure to solar radiation (Air Mass 1 or 2). After activation until x = 0.260 to 0.400, y = 0.280 to 0.400 (D65 roughness).

The amount of photochromic material or composition containing or applied to the host material is not limited so long as an amount sufficient to ensure that the photochromic effect upon activation is not visually identified. In general, such amounts can be described as photochromic amounts. The particular amount of use depends primarily on the desired color intensity upon its irradiation and the method used to mix or apply the photochromic material. Typically, the more photochromic materials applied or incorporated, the greater the color intensity below a certain limit.

The relative amount of use of the photochromic compound will vary in part depending on the relative color intensity of the activated form of the compound and the desired final color. Generally, the total amount or amount of photochromic material incorporated into the photochromic optical host material will range from about 0.05 to about 1.0, for example from 0.1 to about 0.45 mg per cm ² of the surface on which the photochromic material is incorporated or applied. Can be. When using a mixture of the above organic photochromic compensation groups, the weight ratio of such materials, namely (first: second), (second: third) and (naphthopyran of the present invention: other agents) Di-group compounds) will range from about 1: 3 to about 3: 1, for example from about 0.75: 1 to about 2: 1. The combination of the first, second and third organic photochromic compensation groups described may have a weight ratio in the range of about 1: 3: 1 to 3: 1: 3.

The photochromic materials of the present invention may be applied or incorporated into host materials such as polymeric organic host materials by various methods known in the art. Such methods include a method of dissolving or dispersing a photochromic material into a host material, such as casting the photochromic material in situ by adding the photochromic material to a monomeric host material prior to polymerization; Immersing the host material in a hot solution of the photochromic material or absorbing the photochromic material into the host material by heat transfer; Providing a photochromic material as a separation layer between adjacent layers of the host material, for example as a polymer film portion; And a method of applying the photochromic material as part of a coating located on the surface of the host material. The term "imbibition" or "absorb" refers to the penetration of only photochromic material into a host material, transfer of the photochromic material into a porous polymer with the aid of a solvent, gaseous delivery and other forms of such delivery. It means and includes the mechanism.

For medical or fashion reasons, compatible (chemically and colorally) colorants, ie dyes, may be applied to the host material for more aesthetic results. The particular dye chosen will depend on the above objectives and the results to be achieved. In one embodiment, the dye may be selected to compensate for the color derived from the activated photochromic material, for example to achieve a more intermediate color or to absorb a particular wavelength in incident light. In another embodiment, when the photochromic material is inactivated, a dye may be selected to provide the desired color to the host medium.

In addition to the photochromic material, an adjuvant may also be incorporated into the host material before, simultaneously or after the photochromic material is incorporated into the host material. For example, the ultraviolet absorber may be mixed with the photochromic material before it is applied to the host material, or may overlap, for example, as a layer between the photochromic material and incident light. In addition, a stabilizer may be mixed with the photochromic material prior to application of the photochromic material to the host material to improve the photoaging resistance of the photochromic material. Examples of stabilizers include hindered amine light stabilizers and singlet oxygen quenchers such as complexes of nickel ions with organic ligands. These may be used alone or in combination. These stabilizers are described in US Pat. No. 4,720,356. Finally, an appropriate protective film may be applied to the surface of the host material. These may be wear resistant coatings and / or coatings that act as oxygen barriers. Such coatings are known in the art.

The host material is usually transparent but may be translucent or even opaque. The host material is merely a portion of the electromagnetic spectral that activates the photochromic material, ie the wavelength of ultraviolet (UV) that produces the open form of the photochromic material, and photochromic in the UV activated form (ie, the open form). It only needs to be transparent to the portion of the visible spectrum that contains the maximum absorption wavelength of the material. Preferably, the host color should not be such that it covers the color of the activated form of the photochromic material, i.e., the color change is easily recognized by the viewer. More preferably, the host material product is suitable for optical applications such as solid transparent or optically transparent materials such as uneven and ophthalmic lenses, windows, automotive transparents (e.g. windshields), aircraft transparents, plastic sheets, polymer films and the like. Suitable material.

Examples of polymeric organic host materials that can be used with the photochromic materials or compositions disclosed herein include polyol (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers and alkoxylated polyhydric alcohols. Polymers of acrylate monomers (eg ethoxylated trimethylol propane triacrylate monomers), ie homopolymers and copolymers; Polymers of multifunctional (ie mono-, di-, tri-, tetra- or multifunctional) acrylate and / or methacrylate monomers, ie homopolymers and copolymers, polyacrylates, polymethacrylates, poly (C _1-12 alkyl methacrylate) (eg poly (methyl methacrylate)), polyoxy (alkylene methacrylate) (eg poly (ethylene glycol bismethacrylate)), poly (alkoxy Phenol methacrylate) (e.g. 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), polyurethane, thermoplastic polycarbonate, polyester, poly (ethylene terephthalate), polystyrene, poly Polymers of li (alpha methyl styrene), copoly (styrene-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinylbutyral, and diallylidene pentaerythritol, ie homopolymers and air Copolymers, in particular polyol (allyl carbonate) monomers such as diethylene glycol bis (allyl carbonate), and copolymers with 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 made from the following resins: thermoplastic polycarbonate resins, for example carbonate-linked, derived from bisphenol A and phosgene, sold under the trade name LEXAN Suzy; Polyesters such as the material sold under the trade name MYLAR; Poly (methyl methacrylate), for example a material sold under the trade name PLEXIGLAS; Other copolymerizable with polyol (allyl carbonate) monomers, especially polymers of diethylene glycol bis (allyl carbonate) sold under the trade name CR-39, and polyol (allyl carbonate) monomers such as diethylene glycol bis (allyl carbonate) Copolymers with monomer materials, for example copolymers with vinyl acetate (for example copolymers of 80-90% diethylene glycol bis (allyl carbonate) and 10-20% vinyl acetate, in particular 80-85% bis ( Allyl carbonate) and a copolymer of 15-20% vinyl acetate); Copolymers with polyurethanes having terminal diacrylate functionalities as described in US Pat. Nos. 4,360,653 and 4,994,208; And copolymers with aliphatic urethanes whose terminal portions contain allyl or acrylyl functional groups as described in US Pat. No. 5,200,483; Poly (vinyl acetate), polyvinylbutyral, polyurethane; A polymer of one of the group consisting of diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer and ethoxylated trimethylol propane triacrylate monomer; Cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene; And copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile. More particularly, the photochromic naphthopyrans of the present invention may be used in conjunction with optical organic resin monomers to produce optically clear polymers, i.e. materials suitable for optical applications, such as uneven and ophthalmic lenses, windows and transparent for automobiles. Can be. Such optically clear polymer may have a refractive index in the range of about 1.48 to about 1.75, for example about 1.495 to about 1.66.

The present invention is described in more detail in the following examples, which are merely illustrative, and those skilled in the art will be able to variously change and change the present invention.

Example 1

Step 1

4-fluorobenzophenone (25 g, 0.12 mole) and morpholine (15 g) were added to the reaction flask containing 100 mL of anhydrous dimethylsulfoxide, stirred and refluxed under argon atmosphere for 8 hours. Thereafter, the contents of the reaction flask mixture were added to 500 ml of ice-water mixture and stirred for 2 hours. The resulting solid product was filtered off, washed sequentially with water and hexane and then dried. The amount of isolated product was 30 g. Nuclear magnetic resonance (NMR) spectra confirmed that this product had a structure consistent with 4-morpholinobenzophenone and was used directly in the next step without further purification.

Step 2

4-morpholinobenzophenone (10 g, 0.037 mol) was dissolved in a reaction flask containing 50 ml of anhydrous dimethylformamide saturated with acetylene and stirred at room temperature. 18% by weight of a suspension of sodium acetylide in xylene / mineral oil (0.3 mol of sodium acetylide) was added to the reaction flask and the mixture was stirred. After stirring for 3 hours at room temperature under a nitrogen atmosphere, the contents of the reaction flask mixture were added to 250 ml of ice-water mixture and stirred for 1 hour. The resulting solid product was filtered off, washed sequentially with water and hexane and then dried. The amount of isolated product was 8 g. Nuclear Magnetic Resonance (NMR) spectra confirmed that this product had a structure consistent with 1- (4-morpholinophenyl) -1-phenyl-2-propyn-1-ol, and was then purified without further purification. It was used directly in the step.

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 the reaction flask containing 200 mL of toluene and stirred. A catalytic amount of p-toluene sulfonic acid (about 100 mg) was added and the mixture was stirred for 4 hours. Thereafter, the reaction mixture was poured into 10% by weight sodium hydroxide solution. The organic layer was separated, washed with water and dried over anhydrous sodium sulfate. 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 eluent. Photochromic fractions were collected and the eluate was removed in vacuo. The product was crystallized from hexanes. The recovered product had a melting point of 178-179 ° C. Nuclear magnetic resonance (NMR) spectra show that the product is 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran It has been shown to have a structure consistent with.

Example 2

2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran (2 g) prepared as in Example 1 ), Anhydrous potassium carbonate (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. Acetone was then removed in vacuo and each 25 ml of water and methylene chloride were added to the reaction mixture. The mixture was stirred for 30 minutes, the organic layer was separated, washed and dried. Residual solvent methylene chloride was removed under vacuum. The resulting oily concentrate was crystallized from a 1: 1 hexanes: diethyl ether mixture. The solid obtained was suction filtered, washed with hexanes and air dried. The product had a melting point of 175-176 ° C. Nuclear magnetic resonance (NMR) spectra show that the product is 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-methoxy-2H-naphtho [1,2-b] pyran It has been shown to have a structure consistent with.

Example 3

2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran (2 g) prepared as in Example 1 ) And triethylamine (2 g) were added to the 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 further stirred for 30 minutes. After that, the organic layer was separated, washed, and dried over anhydrous sodium sulfate. The solvent was evaporated to give an oily residue, which was crystallized from a 1: 1 hexanes: diethyl ether mixture. The solid was suction filtered, washed with hexanes and air dried. The product had a melting point of 143-145 ° C. Nuclear magnetic resonance (NMR) spectra show that this product is 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran It has been shown to have a structure consistent with.

Example 4

Step 1

N-ethylcarbazole (50 g, 0.25 mol) and benzoyl chloride (0.28 mol) were added to 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 reaction mixture. The reaction mixture was stirred for 1 hour and then poured into 5% by weight aqueous hydrochloric acid and ice mixture. The resulting mixture was stirred for 15 minutes and extracted with methylene chloride. The organic layer was separated, first washed with 10% by weight aqueous sodium hydroxide and then with distilled water. The organic layer was separated and dried over anhydrous sodium sulfate. Methylene chloride solvent was removed under vacuum. The resulting oily product was crystallized from hexanes. 35 g of the recovered product was filtered and air dried. Nuclear magnetic resonance (NMR) spectra showed that the desired product had a structure consistent with 2-benzoyl-9-ethylcarbazole.

Step 2

1- (9-ethylcarbazol-2-yl) -1 according to the procedure of step 2 of Example 1 except for using 2-benzoyl-9-ethylcarbazole in place of 4-morpholinobenzophenone -Phenyl-2-propyn-1-ol was prepared.

Step 3

1- (9-ethylcarbazol-2-yl) -1-phenyl-2-propyn-1- instead of 1- (4-morpholinophenyl) -1-phenyl-2-propyn-1-ol 2- (9-ethylcarbazol-2-yl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-, following the procedure of step 3 of Example 1, except that Naphtho [1,2-b] pyran was prepared.

Step 4

2- (9-ethylcarbazole- instead of 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran The procedure of Example 3 was followed except that 2-yl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran was used. The product was an oil. Nuclear magnetic resonance (NMR) spectra show that the product is 2- (9-ethylcarbazol-2-yl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b ] Has a structure consistent with piran.

Example 5

The procedure of Example 4 was followed except that N-phenylcarbazole was used in place of N-ethylcarbazole in Step 1. The product had a melting point of 188-189 ° C. Nuclear magnetic resonance (NMR) spectra show that the product is 2- (9-phenylcarbazol-2-yl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2- b] showed a structure consistent with pyran.

Example 6

Step 1

In step 2, 1- (4-dimethylaminophenyl) -1-phenyl-2-propyn-1-ol is prepared using 2,4-dimethylaminobenzophenone instead of 4-morpholinobenzophenone, which is 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naph according to the procedure of steps 2 and 3 of Example 1 except for use in step 3 To [1,2-b] pyran was prepared.

Step 2

2- (4-dimethylaminophenyl) instead of 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran The procedure of Example 3 was followed except that 2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran was used. The product had a melting point of 156 ° C. Nuclear magnetic resonance (NMR) spectra show that the product is a 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran. It has been shown to have a matching structure.

Example 7

Step 1

1- (4-dimethylaminophenyl) -1-phenyl-2-propyn-1-ol is used instead of 1- (4-morpholinophenyl) -1-phenyl-2-propyn-1-ol , Except that methyl-4-hydroxy-1-methyl-2-naphthoate is used instead of methyl-1,4-dihydroxy-2-naphthoate. Followed. The product had a melting point of 182-184 ° C. Nuclear magnetic resonance (NMR) spectra show that this product is consistent with 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-methyl-2H-naphtho [1,2-b] pyran It has been shown to have a structure.

Example 8

The procedure of Example 6 was followed except that 4,4'-bis (dimethylamino) benzophenone was used instead of 4-dimethylaminobenzophenone in Step 1. The product had a melting point of 222-224 ° C. Nuclear magnetic resonance (NMR) spectra show that this product is consistent with 2,2-bis (4-dimethylaminophenyl) -5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran It has been shown to have a structure.

Example 9

Part A

The test was carried out using the photochromic naphthopyrans of the examples incorporated or absorbed into the test square polymer by one of two different methods. In Method I, the photochromic naphthopyrans of the examples are incorporated into the polymer sample. The calculated amount of naphthopyran was calculated to produce a 1.5-fold ^10-3 molar solution. 4 parts ethoxylated bisphenol A dimethacrylate (BPA 2EO DMA), 1 part poly (ethyleneglycol) 600 dimethacrylate and 2 To a flask containing 50 g of a monomer mixture of 0.033% by weight of 2'-azobis (2-methyl propionitrile) (AIBN) was added. If necessary, naphthopyran was dissolved in the monomer mixture by stirring and mild heating. After a clear solution was obtained, it was poured into a flat sheet mold having an internal dimension of 2.2 mm x 6 inches (15.24 cm) x 6 inches (15.24 cm). Seal the mold and increase the temperature from 40 ° C. to 95 ° C. at 5 hour intervals under horizontal airflow, maintain the temperature at 95 ° C. for 3 hours and then lower to 60 ° C. for at least 2 hours before the end of the curing cycle. Placed in a programmable oven. After opening the mold, the polymer sheet was cut into 2 inch (5.1 cm) test square pieces using a diamond blade saw.

In Method II, photochromic naphthopyrans were absorbed into test square polymers prepared from diethylene glycol bis (allyl carbonate) compositions. The test square piece had dimensions of 1/8 inch (0.3 cm) x 2 inches (5.1 cm) x 2 inches (5.1 cm). In the absorption process, photochromic naphthopyrans were dissolved in a 1: 9 mixture of ethyl cellulose: toluene to form a 10% by weight solution. The solution was then spin coated onto test square pieces and dried. Samples were heated at 135-155 ° C. in a hot-air oven for a time sufficient to heat transfer the test square pieces. The residence time of the test square pieces in the oven was adjusted to absorb a significant amount of naphthopyran compound. This is to show significant UV absorption at λ _max of the compound near UV. After cooling, the ethyl cellulose / toluene resin film was removed from the test square pieces by washing with acetone.

Part B

Photochromic Test Square pieces were tested for photochromic response on an optical bench. Prior to testing on the optical bench, the photochromic test square piece is exposed to 365 nm ultraviolet light for 15 minutes to activate the photochromic compound and then placed in a 76 ° C. oven for 15 minutes to bleach or inactivate the photochromic compound. The test square pieces were cooled to room temperature and exposed to fluorescent room lamps for at least 2 hours and then covered for at least 2 hours before testing on an optical bench maintained at 75 ° F. (23.9 ° C.). A 150 W Xenon arc light on the bench, a remote shutter, a copper sulfate bath that acts as a heat sink for the arc light, and a Schott WG-320 nm cut-off filter to remove short wavelength radiation; A sample holder into which the medium density filter and the square piece to be tested was inserted was installed. The aimed ray from tungsten or the like was passed through the square piece at a small angle perpendicular to the square piece. After passing through the square pieces, light from tungsten or the like was passed through an optical filter attached to the detector. The optical filter passes the wavelength so that the detector resembles the response of the human eye. The output signal from the detector was processed by a radiometer.

The optical density change (ΔOD) was measured by inserting the test square piece in the bleached state into the sample stage, adjusting the transmission ratio to 100%, and opening the shutter from the xenon lamp to emit ultraviolet light to bleach the test square piece in the bleached state. Change to the activated (ie blacked) state, measure the permeation amount in the activated state, and the equation ΔOD = log (100 /% Ta), where% Ta is the permeation rate in the activated state, 10 standard), and the change in optical density was calculated and measured.

ΔOD / min, which represents the sensitivity of the photochromic compound to UV light, was measured over the initial 5 seconds of UV exposure and then expressed on a per minute basis. Saturated optical density (OD) was measured under the same conditions as ΔOD / min, except that UV exposure continued for 20 minutes for the examples of Table 1. Λ _max reported in Table 1 is the wavelength in the visible spectrum where 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 the time interval for absorption of the activated form of naphthopyrans in the test square, reaching half of the maximum absorption at room temperature (75 ° F., 23.9 ° C.) after removal of the active light source. Seconds). The results for the compounds of the examples are shown in Table 1.

Example Compound λ _max (visible light) ΔOD / min ΔOD @ saturation Bleaching (T 1/2) One 511 0.64 1.36 193 2 541 0.29 0.95 292 3 545 0.24 0.31 88 4 ^* 528 0.67 0.46 270 5 520 0.31 0.88 70 6 591 0.27 0.30 70 7 584 0.20 0.51 200 8 618 0.16 0.07 19 * Test square pieces were prepared by Method II. All others are prepared by Method I.

The results in Table 1 show that a range of values for bleach rate, ΔOD and sensitivity at saturation depend on the properties of substituents R ₁ , R ₂ , R ₃ , and B and B ′ for Example Compounds 1-8 of the present invention. Shows that it is obtained.

Although the present invention has been described in connection with the detailed description of specific embodiments, such details are not to be considered as limiting the scope of the invention except as included in the appended claims.

Claims (20)

Naphthopyran compound of Formula I: Formula I Where (a) R ₁ is a -C (O) W group where W is -OR ₄ or -N (R ₅ ) R ₆ , wherein R ₄ is hydrogen, 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 ) alkyl, or C ₁ -C ₆ haloalkyl ; R ₅ and R ₆ are each selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono- or di-substituted phenyl, wherein the phenyl substituent is C ₁ -C ₆ Alkyl and C ₁ -C ₆ alkoxy, said halo substituents being chloro or fluoro; (b) R ₂ and R ₃ are each hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₇ cycloalkyl, substituted or unsubstituted phenyl, or —OR ₇ group, wherein R ₇ is hydrogen, 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, -CH (R ₈ ) X group, wherein X is -CN, -CF ₃ , halogen or -C (O) W, and R ₈ is hydrogen or C ₁ -C ₆ alkyl ) Or -C (O) Y group wherein Y is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, substituted or unsubstituted aryl group phenyl or naphthyl, phenoxy, C ₁ -C ₆ mono- or dialkyl substituted phenoxy, C ₁ -C ₆ mono- or dialkoxy substituted phenoxy, C ₁ -C ₆ alkylamino, phenylamino, C ₁ -C ₆ mono- or dialkyl substituted phenyl Amino again C ₁ -C ₆ mono- or di-alkoxy substituted phenylamino a), and the substituent of each of said phenyl and naphthyl are selected from C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, said halogen or halo substituents Is chloro or fluoro and n is an integer selected from 0, 1, 2 and 3; (c) B is selected from the group consisting of unsubstituted, mono-, di- and tri-substituted aryl groups phenyl, and naphthyl, said aryl substituents being C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, Halogen, 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, wherein the halogen is fluoro or chloro; (d) B 'is (i) mono-substituted aryl groups phenyl and naphthyl (substituents for such aryl include 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); (ii) a group of formula (IAA) Chemical Formula IIA Wherein U is hydrogen or C ₁ -C ₄ alkyl, V is selected from unsubstituted, mono- and di-substituted members of the group consisting of naphthyl, phenyl, furanyl and thienyl, each of said substituents being C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, fluoro or chloro; And (iii) a group of formula IIB: Formula IIB Wherein M is CH ₂ , O, S or NR ₁₄ , wherein R ₁₄ consists of hydrogen, C ₁ -C ₆ alkyl, C ₅ -C ₇ cycloalkyl, phenyl, mono-substituted and di-substituted phenyl Selected from the group, the substituent of the phenyl is selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, chloro and fluoro), and R ₉ is C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy , Chloro or fluoro, a is an integer selected from 0, 1, 2 and 3) Is selected from the group consisting of; (e) B and B 'together form an unsubstituted, mono- or di-substituted fluorene-9-ylidene or are saturated C ₃ -C ₁₂ spiro-monocyclic hydrocarbons, saturated C ₇ -C ₁₂ spiro- Forms a member selected from the group consisting of acyclic hydrocarbons and saturated C ₇ -C ₁₂ spiro-tricyclic hydrocarbons, provided that the bicyclic and tricyclic hydrocarbons are adamantylidene, bonylidene and norbornyli Non-dene, said fluorene-9-ylidene substituent is selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, fluoro and chloro; (f) B and B 'are each selected from the group defined in (d) (ii) and (d) (iii) above. The method of claim 1, (a) R ₁ is a —C (O) W group where W is —OR ₄ or —N (R ₅ ) R ₆ , wherein R ₄ is hydrogen, 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 are each selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono- or di-substituted phenyl, wherein the phenyl substituent is C ₁ -C ₄ alkyl And C ₁ -C ₄ alkoxy, halo substituents are chloro or fluoro; (b) R ₂ and R ₃ are each hydrogen, C ₁ -C ₃ alkyl, C ₃ -C ₅ cycloalkyl, substituted or unsubstituted phenyl or -OR ₇ group, wherein R ₇ is hydrogen, C ₁ -C ₃ alkyl or —CH (R ₈ ) X group wherein X is —CN or —C (O) W and R ₈ is hydrogen or methyl; or —C (O) Y group, where Y is C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy), said phenyl substituent is C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, n is an integer selected from 0 and 1; (c) B is unsubstituted, mono-, di- or tri-substituted phenyl, said phenyl substituent being C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, amino, C ₁ -C ₄ monoalkyl Amino, C ₁ -C ₄ dialkylamino, morpholino, piperidino, indolinyl and pyrrolidyl, wherein the halogen is fluoro or chloro; (d) B ' (i) mono-substituted phenyl, wherein the phenyl substituent is a group consisting of amino, C ₁ -C ₄ monoalkylamino, C ₁ -C ₄ dialkylamino, morpholino, piperidino, indolinyl and pyrrolidyl Is selected from); (ii) a group of formula (IAA) Chemical Formula IIA (Wherein U is hydrogen or methyl, V is phenyl or mono-substituted phenyl and the wasteyl substituent is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, fluoro, or chloro); And (iii) a group of formula IIB: Formula IIB Wherein M is CH ₂ , O or NR ₁₄ , R ₁₄ is selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl, phenyl and mono-substituted phenyl, wherein the phenyl substituent is C ₁ -C ₄ Alkyl, C ₁ -C ₄ alkoxy, chloro or fluoro, R ₉ is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, chloro or fluoro, a is selected from integers of 0, 1 and 2 do) Is selected from the group consisting of; (e) B and B 'together form an unsubstituted, mono- or di-substituted fluorene-9-ylidene, or a saturated C ₃ -C ₈ spiro-monocyclic hydrocarbon ring, saturated C ₇ -C ₁₀ spiro A bicyclic hydrocarbon ring and a saturated C ₇ -C ₁₀ spiro-tricyclic hydrocarbon, wherein the fluorene-9-ylidene substituent is C ₁ -C ₃ alkyl, C ₁ -C ₃ selected from the group consisting of alkoxy, fluoro and chloro, What is naphthopy? The method of claim 2, (a) R ₁ is a —C (O) W group where W is —OR ₄ or —N (R ₅ ) R ₆ , wherein R ₄ is hydrogen, 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 hydrogen, C ₁ -C ₃ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and mono-substituted phenyl, wherein the phenyl substituents are C ₁ -C ₃ alkyl and C ₁ -C ₃ alkoxy is selected from the group consisting of halo substituents are fluoro; (b) R ₂ and R ₃ are each selected from the group consisting of hydrogen, C ₁ -C ₃ alkyl, phenyl and —OR ₇ group, wherein R ₇ is hydrogen, C ₁ -C ₃ alkyl or —C (O Y is a group wherein Y is C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, n is an integer selected from 0 and 1; (c) B is selected from the group consisting of unsubstituted, mono- and di-substituted phenyl, said phenyl substituent being C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, fluoro, amino, C ₁ -C ₃ monoalkylamino, C ₁ -C ₃ dialkylamino, morpholino and piperidino; (d) B ' (i) mono-substituted phenyl, wherein the phenyl substituent is selected from the group consisting of amino, C ₁ -C ₃ monoalkylamino, C ₁ -C ₃ dialkylamino, morpholino and piperidino; And (ii) a group of formula IIB: Formula IIB Wherein M is CH ₂ , O, or NR ₁₄ , R ₁₄ is hydrogen, C ₁ -C ₄ alkyl or phenyl, R ₉ is C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and fluoro Is selected from an integer consisting of 0, 1 and 2) Is selected from the group consisting of; (e) B and B 'together form fluorene-9-ylidene or bicyclo [3.3.1] nonan-9-ylidene, What is naphthopy? The method of claim 3, wherein R ₁ is a —C (O) W group where W is —OR ₄ or —N (R ₅ ) R ₆ , wherein R ₄ is hydrogen or C ₁ -C ₃ alkyl, and R ₅ and R ₆ are each hydrogen , C ₁ -C ₃ alkyl or phenyl; R ₂ and R ₃ are each hydrogen or C ₁ -C ₃ alkyl; B is unsubstituted, mono- or di-substituted phenyl, said phenyl substituent being C ₁ -C ₂ alkyl, C ₁ -C ₂ alkoxy, fluoro, C ₁ -C ₂ monoalkylamino, C ₁ -C ₂ Dialkylamino, morpholino or piperidino; B 'is mono-substituted phenyl, 9-ethyl carbazolyl or 9-phenyl carbazolyl, said phenyl substituent being C ₁ -C ₂ monoalkylamino, C ₁ -C ₂ dialkylamino, morpholino or piperidi old man, What is naphthopy? The method of claim 1, (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 Naphthopyran 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. The method of claim 6, Polymeric organic host materials include polyacrylates, polymethacrylates, poly (C _1-12 alkylmethacrylates), polyoxy (alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetates, 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 (alpha methylstyrene), copoly (styrene-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinylbutyral, and polyol (allyl carbonate) monomers, multiple Functional acrylate monomers, multifunctional methacrylate monomers, diethylene glycol dimethacrylate A photochromic product selected from the group consisting of polymers of the group consisting of monomers, diisopropenyl benzene monomers, alkoxylated polyhydric alcohol acrylate monomers and diallylidene pentaerythritol monomers. A photochromic article comprising a polymeric organic host material and a photochromic amount of the naphthopyran compound of claim 2. The method of claim 8, Polymeric organic host materials include polyacrylates, polymethacrylates, poly (C _1-12 alkylmethacrylates), polyoxy (alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetates, 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 (alpha methylstyrene), copoly (styrene-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinylbutyral, and polyol (allyl carbonate) monomers, multiple Functional acrylate monomers, multifunctional methacrylate monomers, diethylene glycol dimethacrylate A photochromic product selected from the group consisting of polymers of the group consisting of monomers, diisopropenyl benzene monomers, alkoxylated polyhydric alcohol acrylate monomers and diallylidene pentaerythritol monomers. The method of claim 9, Polymeric organic host materials include poly (methyl methacrylate), poly (ethyleneglycol bismethacrylate), poly (ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonates, poly (vinyl acetate), polyvinylbuty Ral, polyurethane, and polymers of members of the group consisting of diethylene glycol bis (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers A photochromic product, which is a transparent solid homopolymer or copolymer selected from the group. The method of claim 10, The photochromic compound is present in an amount of about 0.05 to 1.0 mg per cm ^{2 of the} surface of the organic host material to which the photochromic material is incorporated or applied. The method of claim 11, Photochromic product that is a lens. Claim | item photochromic amount of the naphthopyran compound of Claim 3; And poly (methyl methacrylate), poly (ethylene glycol bismethacrylate), poly (ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly (vinyl acetate), polyvinylbutyral, polyurethane, And a polymeric organic host material selected from the group consisting of diethylene glycol bis (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers. Discolorable products. Naphthopyran compound photochromic amount of claim 4; And poly (methyl methacrylate), poly (ethylene glycol bismethacrylate), poly (ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly (vinyl acetate), polyvinylbutyral, polyurethane, And a polymeric organic host material selected from the group consisting of diethylene glycol bis (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers. Discolorable products. Transparent solid polymeric host materials; And (b) the photochromic amount of each of at least one naphthopyran compound of claim 1 and (b) at least one other organic photochromic compound having at least one active absorption maximum in the range of about 400 to 700 nm. Photochromic products containing. The method of claim 15, Polymeric organic host materials include polyacrylates, polymethacrylates, poly (C _1-12 alkylmethacrylates), polyoxy (alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetates, 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 (alpha methylstyrene), copoly (styrene-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinylbutyral, and polyol (allyl carbonate) monomers, multiple Functional acrylate monomers, multifunctional methacrylate monomers, diethylene glycol dimethacrylate A photochromic product selected from the group consisting of polymers of the group consisting of monomers, diisopropenyl benzene monomers, alkoxylated polyhydric alcohol acrylate monomers and diallylidene pentaerythritol monomers. The method of claim 15, The organic photochromic compound (b) comprises (a) an organic photochromic material having at least one absorption maximum in the visible range of 400 to at least 500 nm; (b) an organic photochromic material having one absorption maximum in the visible range of about 400 to 500 nm and one absorption maximum in the visible range of 500 to 700 nm; (c) an organic photochromic material having one activation absorption maximum in the visible range greater than 570 nm; And (d) a mixture of said organic photochromic materials. The method of claim 17, The photochromic product, wherein the organic photochromic compound (b) is an organic photochromic material having one activation absorption maximum in the visible range of greater than 570 nm. The method of claim 16, Polymeric organic host materials include poly (methyl methacrylate), poly (ethyleneglycol bismethacrylate), poly (ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonates, poly (vinyl acetate), polyvinylbuty Ral, polyurethane, and polymers of members of the group consisting of diethylene glycol bis (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers A photochromic product, which is a transparent homopolymer or copolymer of a solid selected from the group. The method of claim 17, The organic photochromic compound (b) is spiro (indolin) naphthoxazine, spiro (indolin) pyridobenzoxazine, spiro (benzindolin) pyridobenzoxazine, spiro (benzindolin) naphthoxazine, spiro (Benz indoline) naphthopyrans, spiro (indolin) benzoxazine, spiro (indolin) benzopyran, spiro (indolin) naphthopyran, spiro (indolin) quinopyran, spiro (indolin) pyran, 3H Naphtho [2,1-b] pyran, 2H-phenanthro [4,3-b] pyran, 3H-phenanthro [1,2-b] pyran, a benzopyran compound and a mixture of said photochromic materials A photochromic product, selected from the group consisting of: