DE69737400T2 - SUBSTITUTED NAPHTHOPYRANEES - Google Patents

Description

BESCHEIBUNG THE INVENTION

The The present invention relates to certain novel naphthopyran compounds. In particular, this invention relates to novel photochromic naphthopyran compounds and to compositions and articles containing such novel naphthopyran compounds contain. Many photochromic compounds have a reversible color change when it contains light radiation containing ultraviolet rays, like the Ultraviolet radiation in sunlight or the light of a mercury lamp, get abandoned. When the ultraviolet radiation is stopped, takes such a photochromic compound back to its original Color or colorless condition.

It Different classes of photochromic compounds are synthesized and has been proposed for use in applications in which a sunlight-induced reversible color change or Darkening desired is. The US patent 3,567,605 (Becker) describes a series of pyran derivatives including certain Benzopyrans and naphthopyrans. These compounds are called derivatives described by Chromen, and it is reported that they have a color change, d. H. from colorless to yellow-orange when irradiated with ultraviolet light at temperatures below about -30 ° C. It is reported that the irradiation of the compounds with visible Light or after increasing the temperature is above about 0 ° C the coloring reversed to a colorless state.

The U.S. Patent 5,066,818 describes that various 3,3-diaryl-3H-naphtho [2,1-b] pyrans desirable photochromic properties, d. H. high dyeability and acceptable fading, for ophthalmic and have other applications. In this patent are also known as Comparative example, the isomeric 2,2-diaryl-2H-naphtho [1,2-b] pyrans which are reported to be unacceptably long Times to fade after activation require.

The U.S. Patent 3,627,690 describes photochromic 2,2-disubstituted 2H-Naphtho [1,2-b] pyran compositions containing small amounts of either a base or a weak to moderately strong acid. It is reported that the addition of either an acid or a base to the naphthopyran composition, the fade rate the dyed Increased naphthopyrans, making them for Eye protection applications, such as glasses for sunglasses, become usable. It is further reported in that fade speed of 2H-naphtho [1,2-b] pyrans without the aforementioned additives in the Range from a few hours to many days, to a complete reversal to reach. U.S. Patent 4,818,096 describes a blue-dyeing photochromic benzo- or naphthopyran, which is in the α-position to the oxygen of the pyran ring bears a phenyl group which a nitrogen-containing substituent in the ortho or para positions Has.

WHERE 95/16215 describes photochromic 2H-naphtho [1,2-b] pyrans having a 5-carboxyl or Amido substituent and with an acceptable fade rate, high activated intensity and a high dyeing rate, those in photochromic objects, as ophthalmic lenses, are usable.

The The present invention relates to novel substituted 2H-naphtho [1,2-b] pyran compounds of which has unexpectedly been found to be an acceptable one Fade speed in addition to a high activated intensity and high staining speed to have. In particular, increased the use of certain substituents at the 5-position of the Naphthoteils of naphthopyran compound the fade rate without the addition of acids or bases. additionally these compounds have certain substituents at the 2-position of the pyran ring. Certain substituents can also be attached to the carbon atoms No. 6, 7, 8, 9 or 10 of the naphtho portion of naphthopyran.

DETAILED DESCRIPTION OF THE INVENTION

In In recent years, photochromic plastic materials, in particular Plastic materials for optical Applications have become the subject of considerable attention. In particular, photochromic plastic lenses have been studied because of the weight advantage they offer over glass lenses. Furthermore are photochromic transparent objects for vehicles, such as automobiles and planes, have become of interest due to the potential Security features that provide such transparent items.

In accordance with the present invention, it has now been found that certain novel 2H-naphtho [1,2-b] pyran compounds can be prepared with an acceptable fade rate, high activated intensity, and a high coloration rate. These compounds can be described as being naphthopyrans having certain substituents at the 2-position of the pyran ring and at the carbon atom No. 5 of the naphtho portion of the naphthopyran ring. Certain substituents may also be present on the carbon atoms 6, 7, 8, 9 or 10 of the naphtho portion of the naphthopyran ring. These compounds can be represented by the following structural formula:

In structural formula I, R _{1 is} the group -C (O) W, W is -OR ₄ or -N (R ₅ ) R ₆ , wherein R _{4 is} hydrogen, allyl, C ₁ -C ₆ alkyl, e.g. 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; and 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 disubstituted phenyl. The phenyl substituents may be C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy, and the halo substituent may be chlorine or fluorine.

R ₁ is preferably the group -C (O) W, W is the group -OR ₄ or -N (R ₅ ) R ₆ , in which 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; and 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 disubstituted phenyl. The phenyl substituents may be selected from C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy, and the halo substituent may be chlorine or fluorine.

More preferably, R _{1 is} the group -C (O) W, 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, and wherein R ₅ and R ₆ each are selected from the group consisting of hydrogen, C ₁ -C ₃ alkyl, C ₅ -C ₇ cycloalkyl, phenyl and monosubstituted phenyl. The phenyl substituents may be selected from the group consisting of C ₁ -C ₃ alkyl and C ₁ -C ₃ alkoxy and the halo substituent is fluoro. Most preferably, R _{1 is} the group -C (O) W, 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 in each case hydrogen, C ₁ -C ₃ -alkyl or phenyl.

R ₂ and each R ₃ in the structural formula I may be hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₇ cycloalkyl, substituted or unsubstituted phenyl, the group -OR ₇ , 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 and the group -CH (R ₈ ) X, wherein X is -CN, -CF ₃ , halogen or -C (O) W and R _{8 is} hydrogen or C ₁ -C ₆ alkyl, or R _{7 is} the In which Y is hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, the substituted or unsubstituted aryl groups phenyl or naphthyl, phenoxy, C ₁ -C ₆ -mono- or -C-O-; dialkyl-substituted phenoxy, C ₁ -C ₆ -alkylamino, phenylamino, C ₁ -C ₆ -mono- or -dialkyl-substituted phenylamino or C ₁ -C ₆ -mono- or -dialkoxysubstituted phenylamino wherein each of the phenyl and naphthyl substituents is selected from C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy wherein halo or halo substituents are chloro or fluoro and n is selected from integers 0, 1, 2 or third

Preferably R ₂ and each R _{3 are} hydrogen, C ₁ -C ₃ alkyl, C ₃ -C ₅ cycloalkyl, substituted or unsubstituted phenyl or -OR ₇ , wherein R _{7 is} hydrogen, C ₁ -C ₃ alkyl or the group -CH (R ₈ ) X, wherein X is -CN or -C (O) W and R _{8 is} hydrogen or methyl, or R _{7 is} the group -C (O) Y wherein Y is C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, wherein the phenyl substituents are C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, and n is selected from integers 0 and 1. More preferably, R ₂ and R _{3 are} each selected from the group consisting of hydrogen, C ₁ -C ₃ -alkyl, phenyl and -OR ₇ , wherein R _{7 is} hydrogen or C ₁ -C ₃ -alkyl, or R ₇ is the group -C (O) Y, wherein YC C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy, and n is selected from integers 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 in Structural Formula I, like letters have the same meaning unless otherwise specified.

In the structural formula I, B may be the unsubstituted mono-, di- or tisubstituted aryl groups phenyl and naphthyl, where the aryl substituents may be selected from the group consisting of 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-imidazolidyl, 2-imidazolin-1-yl, 2-pyrazolidyl , Pyrazolinyl, 1-piperazinyl and pyrrolidyl, wherein the halogen is fluorine or chlorine. B is preferably an unsubstituted, monosubstituted or disubstituted phenyl, where the phenyl substituents are selected from the group consisting of C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, amino, C ₁ -C ₄ -monoalkylamino, C ₁ -C ₄ dialkylamino, morpholino, piperidino, indolinyl and pyrrolidyl, wherein the halogen is fluorine or chlorine. B is preferably an unsubstituted, mono- or disubstituted phenyl. where the phenyl substituents are selected from the group consisting of C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, amino, C ₁ -C ₄ -monoalkylamino, C ₁ -C ₄ -dialkylamino, morpholino, piperidino, Indolinyl and pyrrolidyl, wherein the halogen is fluorine or chlorine. B is more preferably an unsubstituted, mono- or disubstituted phenyl, where the phenyl substituents are selected from the group consisting of C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, fluorine, amino, C ₁ -C ₃ -monoalkylamino, C ₁ -C ₃ dialkylamino, morpholino and piperidino. Most preferably, B is an unsubstituted or disubstituted phenyl wherein the phenyl substituents are selected from the group consisting of C ₁ -C ₂ alkyl, C ₁ -C ₂ alkoxy, fluoro, C ₁ -C ₂ monoalkylamino, C ₁ -C _2- dialkylamino, morpholino and piperidino.

In the structural formula I, B 'can be selected from the group consisting of the monosubstituted aryl groups phenyl and naphthyl, where the aryl substituents can be selected from the group consisting of 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.

Preferably, B 'is selected from the group consisting of monosubstituted phenyl, wherein the phenyl substituents are selected from the group consisting of amino, C ₁ -C ₄ monoalkylamino, C ₁ -C ₄ dialkylamino, morpholino, piperidino, indolinyl and pyrrolidyl.

More preferably, B 'is selected from the group consisting of monosubstituted phenyl wherein the phenyl substituents are selected from the group consisting of amino, C ₁ -C ₃ monoalkylamino, C ₁ -C ₃ dialkylamino, morpholino and piperidino.

Most preferably, B 'is monosubstituted phenyl wherein the phenyl substituents are C ₁ -C ₂ monoalkylamino, C ₁ -C ₂ dialkylamino, morpholino or piperidino.

The represented by the structural formula I compounds may according to be prepared according to the method described below. In Reaction A1 becomes the benzoyl derivative of a carbazole, dibenzothiophene or Dibenzofurans produced by Friedel-Crafts method; see. the publications Friedel-Crafts and Related Reactions, George A. Olah, Interscience Publishers, 1964, Vol. 3, Chapter XXXI (Aromatic Ketone Synthesis) and "Regioselective Friedel-Crafts Acylation of 1,2,3,4-Tetrahydroquinolines 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 to 3406, 1992, Heterocyclic Compounds, Robert C. Elderfield, 1951, Vol. 2, Chapter 3 (Dibenzofuran) and Chapter 5 (dibenzothiophenes), The Chemistry of Heterocyclic Compounds, H.D. Hartough and S.L. Meisel, 1954, Vol. 7, Chapter IV (dibenzothiophene and its derivatives), Advances in Heterocyclic Chemistry, A.R. Katritzky and A.J. Boulton, 1974, Vol. 16, Chapter V (Recent Advances in the Chemistry of Dibenzothiophenes) and Heterocyclic Compounds, Robert C. Elderfield, 1952, Vol. 3, Chapter 3 (The Chemistry of Carbazole).

In Reaction A1, the compounds represented by Structural 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 to form the correspondingly substituted benzoyl derivative represented by Structural Formula V. R represents potential phenyl substituents. Reaction A1

By The structural formula VB reproduced compounds are either for sale or, as shown in Reaction A2, by direct amination a commercially available fluorine-substituted benzophenol represented by the structural formula VA, with a primary or secondary Amine compound, e.g. Ethylamine, morpholine piperidine, etc.; see. the publication "Nucleophilic Displacements of Acti vated Fluorine in Aromatic Compounds "by Bader, Henry et al., J. Org. Chem. 31, pages 2319-2321, 1966.

In Reaction A2, the compounds represented by Structural Formula VA and the amino compound are dissolved in a solvent such as dimethylsulfoxide (DMS) and refluxed to form the corresponding amino-substituted benzophenone represented by Structural Formula VB. R represents potential phenyl substituents. Reaction A2

In Reaction B, the ketone represented by Structural Formulas V, VB or more generally VC is reacted with sodium acetylide in a suitable solvent such as anhydrous tetrahydrofuran (THF) to form the corresponding propargyl alcohol represented by Structural Formula VI. Propargyl alcohols having B 'groups represented by Structural Formula IIA can be prepared by the methods described in U.S. Patent 5,274,132, column 2, lines 40-68. Reaction B

The naphthols represented by Structural Formula XIIIA can be prepared by Reaction C or D. In Reaction C, substituted or unsubstituted 1,4-dihydroxy-2-naphthoic acid represented by Structural Formula VII with methyl iodide (or ethyl iodide, propyl iodide, benzyl bromide, etc.) in the presence of ethyl diisopropylamine in a suitable solvent such as anhydrous dimethylformamide (DMF ) to form the corresponding methyl-1,4-dihydroxy-2-naphthoate represented by Structural Formula VIII (or XIIIA in Reaction E). This reaction is further described in J. of Org. Chem., Vol. 46 (17), page 3477, 1981. Reaction C

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

In Reaction E, the propargyl alcohol represented by Structural Formula VI is coupled with the naphthol represented by Structural Formula XIIIA to form compounds represented by Structural Formula I. Reaction E

As shown in Reaction F, compounds represented by Structural Formula XIV (compounds of Structural Formula I in which R _{2 is} a hydroxy group) can be converted to a variety of different groups by reaction with acylating or alkylating agents. So z. For example, the compound represented by Structural Formula XIV may be reacted with methyl iodide (or other alkylating agent) in the presence of anhydrous potassium carbonate in a suitable solvent such as anhydrous acetone to form compounds represented by Structural Formula XV in which R _{2 is} a methoxy substituent is. Alkylation reactions are further described in "Organic Synthesis", Vol. 31, pages 90 to 93, John Wiley & Sons, Inc., New York, NY. Alternatively, compound XIV can be reacted with acetyl chloride (or other acylating agent) in the presence of triethylamine (NEt ₃ ) in a suitable solvent such as methylene chloride to form the compounds represented by structural formula XVI in which R _{2 is} an acetoxy substituent (AcO ) Substituent. Acylation reactions are further described in "Organic Synthesis", Vol. 32, pages 72 to 77, John Wiley & Sons, Inc., New York, NY. Reaction F

The compounds represented by Structural Formula I can be used in those applications in which organic photochromic substances can be used, such as optical lenses, e.g. Ophthalmic vision correction lenses and plan lenses, face masks, goggles, cap screens, camera lenses, windows, automobile windshields, aircraft and automobile transparent articles, e.g. As T-roofs, sidelights and taillights, plastic films and films, textiles and coatings, eg. Coating compositions, such as paints, and confirmation marks on Si safety documents, eg As documents, such as banknotes, passports and driving licenses, for which an authentication or confirmation of authenticity may be desired. Naphtho pyrans represented by Structural Formula I exhibit color changes from colorless to colors ranging from orange to blue.

• (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-(4-Dimethylaminophenyl)-2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho[1,2-b]pyran,
• (e) 2-(4-Dimethylaminophenyl)-2-phenyl-5-methoxycarbonyl-6-methyl-2H-naphtho[1,2-b]pyran und
• (f) 2,2-Bis(4-dimethylaminophenyl)-5-methoxycarbonyl-6-acetoxy-2H-naphtho[1,2-b]pyran.

Examples of contemplated naphthopyrans within the scope of the invention are the following:

• (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- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran,
• (e) 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-methyl-2H-naphtho [1,2-b] pyran and
• (f) 2,2-bis (4-dimethylaminophenyl) -5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran.

It it is envisaged that the photochromic naphthopyrans of the structural formula I in combination with other suitable complementary organic Photochromic materials are used, so they together one form almost neutral gray or brown hue when the plastic lens, which contains such photochromic materials exposed to ultraviolet light becomes. So z. B. a compound that turns yellow, with a compound, which colors to a suitable purple color, are mixed to one to form brown shade. In similar The result is a compound that turns orange in its colored state is a gray tint when used in conjunction with a suitable blue coloring Connection is used. The combination described above Of photochromic materials can also be used in other applications used in ophthalmic lenses.

The novel naphthopyran compounds of the present invention such as those which are described hereinbefore may be alone or in combination with complementary photochromic compounds, d. H. organic photochromic compounds with at least one activated absorption maximum in the range between 400 and 700 nanometers, or with substances containing these Compounds contain, can be used and can be transformed into a polymeric organic Host material used to make photochromic articles becomes, and that colors, if it is activated to a suitable color, incorporated, for. B. resolved or dispersed.

A first group of complementary organic photochromic substances for use with the organic photochromic naphthopyrans of the present invention are contemplated are those with an activated absorption maximum in the visible range of greater than 570 nanometers, z. B. about greater than 570 to 700 nanometers. These materials typically have one blue, bluish-green or bluish-purple Color up when exposed to ultraviolet light in a suitable solvent or a suitable matrix. Many such Links are in the public domain accessible Literature described. So z. B. spiro (indoline) naphthoxazines inter alia in U.S. Patents 3,562,172, 3,578,602, 4,215,010 and 4,342,668; Spiro (indoline) naphthoxazine with certain substituents at the 8 'and 9' positions of the naphthoxazine moiety of the molecule are described in U.S. Patent 5,405,958; Spiro (indoline) pyridobenzoxazines are described in U.S. Patent 4,637,698; Spiro (benzindoline) pyridobenzoxazines and spiro (benzindoline) naphthoxazines are disclosed in U.S. Patent 4,931,219 described; Spiro (benzindoline) naphthopyrans are in Japanese Patent Publication 62/195383 described; Spiro (indoline) benzoxazines are disclosed in U.S. Patent 4,816,584 described; Spiro (indoline) benzopyrans, spiro (indoline) naphthopyrans and spiro (indoline) quinopyrans are e.g. In the US patent 4,880,667; and benzopyrans and naphthopyrans with one Nitrogen-containing substituent in the 2-position of the pyran ring are described in U.S. Patent 4,818,096. Spiro (indoline) pyrans are also in the text Techniques in Chemistry, Vol. III, "Photochromism", Chapter 3, Glenn H. Brown, ed., John Wiley and Sons, Inc., New York, 1971.

A second group of complementary organic photochromic substances for use with the organic photochromic naphthopyrans of the present invention are contemplated are those having at least one absorption maximum in the visible range of between about 400 and less than 500 nanometers. These materials typically have a yellow-orange color, if they are ultraviolet light in a suitable solvent or suitable Be exposed to the matrix.

Such compounds include certain chromenes, ie, benzopyrans and naphthopyrans. Numerous such chromenes are described in the publicly available literature, e.g. In U.S. Patents 3,567,605, 4,826,977 and 5,066,818. Other examples of complementary benzopyrans and naphthopyrans that can be used with the naphthopyrans of the present invention include those having a spiroadamantane group at the α-position to the oxygen atom of the pyran ring, which are described in U.S. Pat U.S. Patent 4,826,977; 2H-Naphtho [1,2-b] pyran compounds having certain substituents on the carbon atoms Nos. 5 and 6 of the naphtho portion of the naphthopyran and at the 2-position of the pyran which is the subject of co-pending U.S. patent application Ser. 08 / 164,187, filed December 9, 1993; 3H-naphtho [2,1-b] pyrans having at least one ortho-substituted phenyl substituent at the 3-position of the pyran ring described in U.S. Patent 5,066,818; 3H-naphtho [2,1-b] pyran compounds having certain substituents on the carbon atom number 8 and certain substituents on the carbon atom number 7 or 9, all substituents being on the naphtho portion of the naphthopyran which is the subject of the pending US patent application Ser. Patent Application Serial No. 08 / 080,246, filed June 21, 1993; 3H-naphtho [2,1-b] pyrans having at the 3-position of the pyran ring an (i) an aryl substituent; and (ii) a phenyl substituent having a 5- or 6-membered heterocyclic ring fused to the number 3 carbon atoms and 4 of the phenyl substituent are described in U.S. Patent 5,384,077; Diaryl-3H-naphtho [2,1-b] pyran compounds having a substituted or unsubstituted 5- or 6-membered heterocyclic ring fused to the g, i or l side of the naphthopyran which is the subject of copending U.S. Patent Application Serial No. 08 / 225,022, filed April 8, 1994; Naphthopyran compounds which are attached to the carbon atom no. 8 of the naphtho part of the naphthopyran ring with z. A methoxy group which are the subject of U.S. Patent 5,238,931; Naphthopyran compounds, examples of which are 3-aryl-3-arylalkenylnaphthopyrans described in U.S. Patent 5,274,132; and naphtho [2,1-b] pyrans attached to carbon atom # 5 with e.g. An acetoxy group which are the subject of U.S. Patent 5,244,602.

A third group of complementary organic photochromic substances for use with the organic photochromic naphthopyrans of the present invention are contemplated are those with an absorption maximum in the sichtba ren Range from between about 400 to about 500 nanometers and another Absorption maximum in the visible range of between 500 to 700 nanometers. These materials typically have a color or colors that range from yellow to purple and from yellow / brown to purple / gray when exposed to ultraviolet light in a suitable solvent or a suitable matrix. Examples of this Compounds include certain substituted 2H-phenanthro [4,3-b] pyrans, substituted 3H-phenanthro [1,2-b] pyrans and benzopyran compounds, such as those having substituents at the 2-position of the pyran ring and a substituted or unsubstituted heterocyclic ring, such as a benzothieno or benzofuran ring attached to the benzo part of the Benzofuran is condensed. Such compounds described later are the subject of the pending U.S. Patent Application No. 08 / 286,039, filed August 4, 1994, and U.S. Patent 5,411,679.

photochromic objects of the present invention a photochromic compound or a mixture of photochromic compounds, as desired or required, included. Single photochromic compounds or Mixtures of photochromic compounds can be used to specific activated colors, such as neutral gray tones or brown tones.

The Compounds of the present invention (hereinafter also referred to as referred to and included as a second group of photochromic compounds) can also in combination with the organic photochromic substances of the first complementary Group of photochromic compounds described herein, d. H. those that are blue, bluish-green or bluish-purple to dye, or with other organic photochromic substances in the above second group photochromic compounds are used. All Members of the first or second group of photochromic compounds or mixtures of such compounds may be described with the herein described third group of photochromic compounds, the colors in the field from yellow to purple and from yellow / brown to purple / gray, combined or used in conjunction with it.

each The photochromic substances described herein may be used in amounts (or in a ratio) like this be used that an organic host material on which the photochromic compounds or the mixture of compounds is applied or in which they are incorporated, a desirable resulting color, d. H. a substantially neutral one Color when activated with unfiltered sunlight, d. H. the colors of the activated photochromic compounds so close as neutral as possible Color is given.

A neutral gray color has a spectrum that has a relatively equal absorption in the visible range between 400 and 700 nanometers. A neutral brown color has a spectrum in which the absorption in the range of 400 to 550 nanometers is moderately greater than in the range of 550 to 700 nanometers. An alternative way to describe color is as its chromaticity coordinate expressing the qualities of a color in addition to its reflectance, ie its chromaticity. In the CIE system, the chromaticity coordinates are obtained by taking the ratios of the normal color values to their sum, e.g. X = X / (X + Y + Z) and y = Y / (X + Y + Z). Color described in the CIE system can be plotted on a chromaticity diagram, usually a plot of the chromaticity coordinates x and y; see. Page 47 to 52 of Principles of Color Technology, FW Billmeyer, Jr. and Max Saltzman, 2nd Edition, John Wiley and Sons, NY (1981). As used herein, an almost neutral color is a color in which the chromaticity coordinate values of "x" and "y" for the color are in the following ranges (D65 bulbs): x = 0.260 to 0.400, y = 0.280 to 0.400 following activation to 40 percent light transmittance when exposed to solar radiation (air mass 1 or 2).

The Amount of photochromic substance or composition containing them applied or incorporated into a host material is not critical, provided that a sufficient amount is used one with the bare one To give eye recognizable photochromic effect upon activation. in the Generally, such an amount may be described as a photochromic amount become. The particular amount used often depends on the desired color intensity after irradiation and from the installation or application of the photochromic substances used. typically, holds that the more photochromic substance applied or incorporated the bigger the color intensity is up to a certain limit.

The relative amounts of the above-mentioned photochromes used Connections vary and hang partially from the relative intensities of the color of the activated Species of such compounds and the desired final color. Usually can the amount of total photochromic substance in a photochromic incorporated or applied optical host material, in the range of about 0.05 to about 1.0, e.g. From 0.1 to about 0.45 milligrams per square centimeter of the surface to which the photochromic substance (s) is incorporated or applied or are. When mixtures of the aforementioned organic photochromes complementary Groups used, the weight ratio varies such Materials, d. H. (first to second), (second to third) and (naphthopyran the present invention to other compounds of the second group), from about 1: 3 to about 3: 1, e.g. Between about 0.75: 1 and about 2: 1. The combination of the first, second and third described organic photochromic complementary Groups can have a weight ratio which varies from about 1: 3: 1 to 3: 1: 3: 1.

The Photochromic substances of the present invention can be applied to a host material, such as a polymeric organic host material, by various methods described in the art applied or incorporated therein. Such methods include dissolving or dispersing the photochromic substance in the host material, z. B. casting in situ by adding the photochromic substance to the monomeric Host material before polymerization, imbibing photochromic Substance in the host material by immersing the host material in a hot solution the photochromic substance or by heat transfer, providing the photochromic substance as a separate layer between adjacent ones Layers of the host material, e.g. B. as part of a polymeric Films, and the application of the photochromic substance as part of a Coating on the surface the host material is applied. The term "imbibing" or "imbibing" is intended to be intrusive the photochromic substance alone in the host material, by solvent supported transmission the photochromic substance into a porous polymer, the vapor phase transfer and other such transmission mechanisms mean and include.

On the host material can compatible (chemical or color white) colorations d. H. Dyes, to achieve a more aesthetic result, for medical reasons or for fashion reasons, be applied. The respective selected dye varies and depends on the above need and the result to be achieved. In one embodiment the dye can be selected Be the color that comes from the activated photochromic substances results, to complement, z. B. to a more neutral color reach or a particular wavelength of incident light to absorb. In another embodiment, the dye can be selected around the host matrix a desired hue when the photochromic substances are not in one activated state.

In the host material can be incorporated with the photochromic substances before, simultaneously with or after the application or incorporation of the photochromic substances in the host material and auxiliary materials. So z. For example, ultraviolet light absorbers may be mixed with photochromic substances prior to their application to the host material, or such absorbers may be stacked on top of each other, e.g. As a layer between the photochromic substance and the incident light are superimposed. Further, stabilizers may be mixed with the photochromic substances prior to their application to the host material, to improve the light fatigue resistance of the photochromic substances. Stabilizers, such as hindered amine light stabilizers and singlet oxygen quenchers, e.g. For example, a nickel ion complex with an organic ligand are envisaged. They can be used alone or in combination. Such stabilizers are described in U.S. Patent 4,720,356. Finally, one or more suitable protective coatings may be applied to the surface of the host material. These may be abrasion resistant coatings and / or coatings that serve as oxygen barriers. Such coatings are known in the art.

The Host material becomes ordinary be transparent, but can be translucent and even opaque. The host material just for that part of the electromagnetic spectrum that is the photochromic Substance activated, d. H. that wavelength of ultraviolet light (UV light), which generates the open form of the substance, and those Be transparent to part of the visible spectrum, which is the wavelength of the Absorption maximum of the substance in its UV-activated form, d. H. the open form, includes. The host color should be preferred not be such that they match the color of the activated form of the photochromic Substance masked, d. H. that the color change is easily apparent to the observer is. More preferably, the host material is a solid transparent or optically clear material, such as materials used for optical Applications, such as plan and ophthalmic lenses, windows, transparent objects for automobiles, z. As windscreens, transparent objects for aircraft, plastic films, polymeric films, etc. are suitable.

Examples of the polymeric organic host materials that can be used with the photochromic substances or compositions described herein include polymers, ie, homopolymers and copolymers, of polyol (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenylbenzene monomers, and alkoxylated polyhydric alcohol acrylate monomers such as ethoxylated trimethylolpropane triacrylate monomers; Polymers, ie homopolymers and copolymers of polyfunctional, ie mono-, di-, tri-, tetra- or multifunctional acrylate and / or methacrylate monomers, polyacrylates, polymethacrylates, poly (C ₁ -C ₁₂ -alkyl methacrylates), such as poly ( methyl methacrylate), 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-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinyl butyral and polymers, ie homopolymers and copolymers of diallylidene pentaerythritol, especially copolymers with 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 a optically clear polymerized organic material of a thermoplastic polycarbonate resin such as bisphenol A and phosgene derived carbonate-crosslinked resin, which is under the LEXAN brand, a polyester such as the MYLAR brand distributed material, a poly (methyl methacrylate), as under material sold by the PLEXIGLAS brand, polymers of a polyol (allyl carbonate) monomer, in particular diethylene glycol bis (allyl carbonate), which monomer sold under the trademark CR-39, and polymers of copolymers a polyol (allyl carbonate), e.g. B. diethylene glycol bis (allyl carbonate), with other copolymerizable monomeric materials, such as copolymers with vinyl acetate, e.g. B. copolymers of 80 to 90 percent diethylene glycol bis (allyl carbonate) and 10 to 20 percent vinyl acetate, especially 80 to 85 percent of the Bis (allyl carbonate) and 15 to 20 percent vinyl acetate, and copolymers with a polyurethane with terminal diacrylate, as described in US Pat. Nos. 4,360,653 and 4,994,208, and copolymers with aliphatic urethanes whose allyl end portion or acrylyl-functional groups, as disclosed in US Pat 5,200,483, poly (vinyl acetate), polyvinyl butyral, polyurethane, Polymers of members of the group consisting of diethylene glycol dimethacrylate monomers, Diisopropenylbenzene monomers and ethoxylated trimethylolpropane triacrylate monomers, cellulose acetate, Cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and Copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile. In particular, the use of the photochromic naphthopyrans of the present invention with optical organic resin monomers in Consider, which are used to optically clear polymers to produce, d. H. Materials used for optical applications, such as z. For example Plano and ophthalmic lenses, windows and transparent articles for automobiles, are suitable. Such optically clear polymers can one Have refractive indices ranging from about 1.48 to about 1.75, z. B. from about 1.495 to about 1.66.

The The present invention will be more specifically described in the following examples which are merely illustrative There are numerous modifications and variations in it for the Those skilled in the art are apparent.

EXAMPLE 1

Step 1

4-fluorobenzophenone (25 g, 0.12 mol) and morpholine (15 g) were placed in a reaction flask introduced containing 100 ml of anhydrous dimethyl sulfoxide, touched and refluxed under argon atmosphere for 8 hours. After that, the content became of the reaction flask was added to 500 ml of an ice-water mixture and stirred for 2 hours. The resulting solid product was filtered, followed successively with water of hexane, washed and then dried in air. The yield of the isolated product was 30 g. A nuclear magnetic resonance spectrum (NMR spectrum) showed that the product had a structure consistent with 4-morpholinobenzophenone not cleaned up, but directly in the next step has been used.

step 2

4-morpholinobenzophenone (10 g, 0.037 mol) was dissolved in a reaction flask containing Contained 50 ml of anhydrous dimethylformamide saturated with acetylene, and stirred at room temperature. An 18% by weight suspension of sodium acetylide in xylene / mineral oil (0.3 mol Sodium acetylide) was added to the reaction flask and the mixture was stirred. After 3 hours stir at room temperature under a nitrogen atmosphere became the contents of the reaction flask to 250 ml of an ice-water mixture added and stirred for 1 hour. The resulting solid product was filtered, followed by water of hexane, washed and dried in air. The yield of isolated product was 8 g. A nuclear magnetic resonance spectrum (NMR spectrum) showed that the product had a structure that with 1- (4-morpholinophenyl) -1-phenyl-2-propyn-1-ol, not further purified, but used directly in the next step has been.

step 3

1- (4-morpholinophenyl) -1-phenyl-2-propyn-1-ol (about 0.025 mol) from Step 2 and methyl 1,4-dihydroxy-2-naphthoate (5 g, 0.022 mol) were placed in a reaction flask containing Contained 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. Thereafter, the reaction mixture became poured into a 10 wt .-% sodium hydroxide solution. The organic Layer was separated, washed with water and dried over anhydrous Dried sodium sulfate. The remaining solvent Toluene was removed under reduced pressure. The resulting oil was using a silica gel column and a 1: 3 mixture of chloroform: hexane purified as eluent. The photochromes Fractions were pooled and the eluent was concentrated under reduced pressure Pressure removed. The crystallization of the product obtained was induced from hexane. The recovered product had a melting point from 178 to 179 ° C. A nuclear magnetic resonance (NMR) spectrum showed that the product had a structure consistent with 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran.

EXAMPLE 2

2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran (2 g), prepared as described in Example 1, anhydrous potassium carbonate (2 g) and methyl iodide (2 g) were placed in a reaction flask, 40 ml of anhydrous acetone, stirred and under argon atmosphere under backflow heated. Thereafter, the acetone was removed under reduced pressure, and it 25 ml each of water and methylene chloride were added to the reaction mixture added. The mixture was stirred for 30 minutes, and the organic layer was separated, washed and dried. The remaining solvent Methylene chloride was removed under reduced pressure. The resulting oily concentrate was crystallized from a mixture of hexane diethyl ether of 1: 1. The resulting solid was suction filtered, washed with hexane and dried in the air. The product obtained had a melting point from 175 to 176 ° C. A nuclear magnetic resonance (NMR) spectrum showed that the product had a structure consistent with 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-methoxy-2H-naphtho [1,2-b] pyran.

EXAMPLE 3

2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran (2 g) prepared as described in Example 1 and triethylamine (2 g) introduced into a reaction flask, the Contained 50 ml of anhydrous methylene chloride, and stirred. Acetyl chloride (2 g) was added to the 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 a further half hour. Thereafter, the organic layer was separated, washed and dried over anhydrous sodium sulfate. Evaporation of the solvent gave an oily residue which was crystallized from a 1: 1 mixture of hexane: diethyl ether. The solid was suction filtered, washed with hexane and dried in air. The product obtained had a melting point of 143-145 ° C. A nuclear magnetic resonance spectrum (NMR spectrum) showed that the product had a structure with 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran agreed.

EXAMPLE 4

Step 1

The Procedure of steps 2 and 3 of example 1 was repeated with the exception that in step 2 4-dimethylaminobenzophenone instead of 4-morpholinobenzophenone was used to prepare 1- (4-dimethylaminophenyl) -1-phenyl-2-propyn-1-ol, used in step 3 to prepare 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran.

step 2

The The procedure of Example 3 was repeated except that 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran instead of 2- (4-morpholinophenyl) -2-phenyl-5-methoxycarbonyl-6-hydroxy-2H-naphtho [1,2-b] pyran has been used. The product obtained had a melting point from 156 ° C. A nuclear magnetic resonance (NMR) spectrum showed that the product had a structure consistent with 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran.

EXAMPLE 5

Step 1

The The procedure of Step 3 of Example 1 was repeated with Except that 1- (4-dimethylaminophenyl) -1-phenyl-2-propyn-1-ol instead of 1- (4-morpholinophenyl) -1-phenyl-2-propyn-1-ol and methyl 4-hydroxy-1-methyl-2-naphthoate instead of methyl-1,4-dihydroxy-2-naphthoate were used. The product obtained had a melting point from 182 to 184 ° C. A nuclear magnetic resonance spectrum (NMR spectrum) showed that the product had a Had structure consistent with 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-methyl-2H-naphtho [1,2-b] pyran.

EXAMPLE 6

The The procedure of Example 4 was repeated except that in step 1, 4,4'-bis (dimethylamino) benzophenone was used in place of 4-dimethylaminobenzophenone. The obtained Product had a melting point of 222 to 224 ° C. A nuclear magnetic resonance spectrum (NMR spectrum) showed that the product had a structure that with 2,2-bis (4-dimethylaminophenyl) -5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran.

EXAMPLE 9

Part A

A test was conducted on the photochromic naphthopyrans of the examples incorporated or imbibed in test square polymers by one or two different methods. In Method I, the photochromic naphthopyrans of the Examples were incorporated into the polymeric samples. The amount of naphthopyran calculated to be 1.5 times a 10 ^-3 molar solution was charged to a flask containing 50 g of a monomer mixture of 4 parts of ethoxylated bisphenol A dimethacrylate (BPA 2EO DMA). , 1 part of poly (ethylene glycol) -600-dimethacrylate and 0.033 wt% of 2,2'-azobis (2-methylpropionitrile) (AIBN). The naphthopyrans were dissolved in the monomer mixture by stirring and gently heating, if necessary. After a clear solution was obtained, it was poured into a flat foil mold having the internal dimensions of 2.2 mm x 6 inches (15.24 cm) x 6 inches (15.24 cm). The The mold was sealed and placed in a horizontal programmable airflow oven programmed to raise the temperature from 40 ° C to 95 ° C over a 5 hour interval, maintain the temperature at 95 ° C for 3 hours and then at least 2 Hours was lowered to 60 ° C before the end of the curing cycle. After the molds were opened, the polymer films were cut into 2 inch (5.1 cm) test squares using a diamond saw blade.

In Method II was the photochromic naphthopyran in Prüfquadratpolymerisate imbibed from a diethylene glycol bis (allyl carbonate) composition were made. The test squares reasonably 1/8 inch (0.3 cm) × 2 Inch (5.1 cm) × 2 Inch (5.1 cm). In the imbibing process, the photochromic Naphthopyran to form a 10% by weight solution in a 1: 9 mixture of ethyl cellulose: toluene dissolved. The solution was then spin-coated on the test squares and allowed to dry calmly. Samples were then placed in a convection oven at 135 to 155 ° C for a time heated, which was sufficient to the photochromic substance in the test squares thermally transfer. The residence time in the oven for the test squares was set that comparable amounts of the naphthopyran compounds are imbibed were. This was done to give a comparable UV absorbance at lambda max of the connection in the near UV. After cooling it was the ethyl cellulose / toluene resin film from the test squares removed by washing with acetone.

part B

The photochromic test squares were tested for photochromic response rates on an optical bench. In front The examination on the optical bench, the photochromic test squares became ultraviolet light for about 15 minutes exposed by 365 nanometers to the photochromic compounds too and then put in a 76 ° C oven for about 15 minutes, to bleach or inactivate the photochromic compounds. The test squares were then cooled to room temperature, at least 2 hours exposed to fluorescent room lighting and then at least 2 hours before the exam on an optical bench maintained at 75 ° F (23.9 ° C). The bench was powered by a 150 watt xenon arc lamp, a regulated one Remote lock, one as a heat sink for the Arc lamp serving copper sulfate bath, a bulkhead WG-320nm exclusion filter, which removes short wavelength radiation, one or more neutral density filters and a sample holder, in which the to be tested Square introduced has been. A bundled Beam of light from a tungsten lamp was made by the square at one small angle perpendicular to the square. After passing through the square became the light from the tungsten lamp through a fotopic Filter directed, which was connected to a detector. The fotopic Filter leaves wavelength in such a way that the detector is the response of the human Eye imitates. The output signals from the detector (s) were processed by a radiometer.

The change the optical density (Δ OD) was determined by introduction a test square in the bleached state into the sample holder, adjusting the permeability scale to 100%, open the shutter from the xenon lamp to ultraviolet radiation to change of the test square from the bleached state to an activated (i.e., darkened) Condition, measuring the permeability in the activated state and calculating the change the optical density according to the formula Δ OD = log (100 /% Ta), where% Ta is the percentage permeability in the activated state is, and the base-10 logarithm is.

The Δ OD / min representing the sensitivity of the photochromic compound to UV light response was measured over the first 5 seconds of UV exposure and then expressed on a per-minute basis. Saturation of optical density (OD) was determined under identical conditions as Δ OD / min except that the UV exposure was continued for 20 minutes for the examples in Table 1. The lambda max indicated in Table 1 is the wavelength in the visible spectrum at which the maximum absorption of the activated (colored) form of the photochromic compound occurs in a diethylene glycol bis (allyl carbonate) composition. The fade rate (T 1/2) is the time interval in seconds for the extinction of the activated form of naphthopyran in the test squares to be half of the highest absorbance at room temperature (75 ° F, 23.9 ° C) after removal of the activating source Light reaches. The results for the compounds of the examples are shown in Table 1. Table 1

All test squares were prepared by the method 1.

The results of Table 1 show that a range of values for the fading rate Δ OD at saturation and the sensitivity for the compounds of Examples 1 to 8 of the present invention are dependent on the nature of the substituents R ₁ , R ₂ , R ₃ and B and B 'are obtained.

Even though the present invention with reference to specific details of particular embodiments has been described, is not intended to be such Details as limitations the scope of the invention are considered, except insofar and to the extent that they are from the attached claims are included.

Claims (14)

Naphthopyran compound represented by the following graphic formula:

wherein (a) R _{1 is} the group -C (O) W, wherein 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 disubstituted phenyl, where these substituents of the phenyl are selected from C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy and said halogen substituent is chlorine or fluorine, (b) R ₂ and each R _{3 is} hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₇ cycloalkyl, substituted or unsubstituted phenyl, the group Are -OR ₇ , wherein R ₇ is hydrogen, C ₁ -C ₆ alkyl, phenyl (C ₁ -C ₃ ) alkyl, mono (C ₁ -C ₆ ) alkyl substituted P -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, the group -CH (R ₈ ) X, wherein X is -CN, -CF ₃ , Halogen or -C (O) W and R ₈ is hydrogen or C ₁ -C ₆ -alkyl, or R _{7 is} the Group -C (O) Y is wherein Y is hydrogen or C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, the substituted or unsubstituted aryl groups phenyl or naphthyl, phenoxy, C ₁ -C ₆ mono or dialkyl-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 of these substituents of the phenyl and naphthyl is selected from C C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy and these halogen or these halogen substituents are chlorine or fluorine and n is selected from the integers 0, 1, 2 or 3, and (c) B is selected from the group consisting of unsubstituted, mono-, di- and trisubstituted aryl groups phenyl and naphthyl, where these substituents of the aryl are selected from the group consisting of 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, said halogen being chloro or fluoro, (d) B 'is selected from the group consisting of monosubstituted aryl groups phenyl and naphthyl, said substituents of Aryls are selected from the group consisting of 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. Naphthopyran according to claim 1, wherein (a) R _{1 is} the group -C (O) W, where W is -OR ₄ or -N (R ₅ ) R ₆ , where 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 ) is 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 and wherein 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 disubstituted phenyl, wherein these substituents of the phenyl are selected from C C ₁ -C ₄ -alkyl and C ₁ -C ₄ -alkoxy and this halogen substituent is chlorine or fluorine, (b) R ₂ and each R ₃ is hydrogen, C ₁ -C ₃ -alkyl, C ₃ -C ₅ -cycloalkyl, substituted or unsubstituted phenyl or -OR ₇ , wherein R ₇ is hydrogen, C ₁ -C ₃ alkyl or the group CH (R ₈ ) X is wherein X is -CN or -C (O) W and R ₈ is hydrogen or methyl or R _{7 is} the group -C (O) Y wherein Y is C ₁ -C ₃ alkyl or C ₁ C ₃ alkoxy, wherein these substituents of the phenyl are C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy and n is selected from integers 0 and 1, and (c) B is selected from the group consisting of unsubstituted, mono- and disubstituted phenyl, where these substituents of the phenyl are selected from the group consisting of C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, amino, C ₁ -C ₄ -monoalkylamino, C ₁ -C ₄ dialkylamino, morpholino, piperidino, indolinyl and pyrrolidyl, wherein said halogen is fluoro or chloro; (d) B 'is selected from the group consisting of monosubstituted phenyl, wherein said substituents of the phenyl are selected from the group consisting from amino, C ₁ -C ₄ -monoalkylamino, C ₁ -C ₄ -dialkylamino, morpholino, piperidino, indolinyl and pyrrolidyl. Naphthopyran according to claim 2, wherein (a) R _{1 is} the group -C (O) W, where W is -OR ₄ or -N (R ₅ ) R ₆ , where 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 and wherein 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 monosubstituted phenyl, where these substituents of the phenyl are selected from C ₁ C ₃ alkyl and C ₁ -C ₃ alkoxy and this halogen substituent is fluorine, (b) R ₂ and R _{3 are} each selected from the group consisting of hydrogen, C ₁ -C ₃ alkyl, phenyl and -OR ₇ , wherein R ₇ is hydrogen or C ₁ -C ₃ alkyl or R _{7 is} the group -C (O) Y, wherein Y is C ₁ -C ₃ alkyl or C ₁ -C ₃ alkoxy and n is selected from the integers 0 and 1, and (c) B is selected from the group consisting of s unsubstituted, mono- and disubstituted phenyl, wherein these substituents of the phenyl are selected from the group consisting of C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, fluoro, amino, C ₁ -C ₃ -monoalkylamino, C C ₁ -C ₃ dialkylamino, morpholino and piperidino, (d) B 'is selected from the group consisting of monosubstituted phenyl, where these substituents of the phenyl are selected from the group consisting of amino, C ₁ -C ₃ monoalkylamino, C ₁ C ₃ dialkylamino, morpholino and piperidino. A naphthopyran according to claim 3, wherein R _{1 is} the group -C (O) W, wherein 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 are} each hydrogen, C ₁ -C ₃ alkyl or phenyl, R ₂ and R _{3 are} each hydrogen or C ₁ -C ₃ alkyl, and B is unsubstituted, monosubstituted or disubstituted phenyl, said substituents of Phenyls are C ₁ -C ₂ alkyl, C ₁ -C ₂ alkoxy, fluoro, amino, C ₁ -C ₂ monoalkylamino, C ₁ -C ₂ dialkylamino, morpholino or piperidino and B 'is a monosubstituted phenyl, wherein these substituents of the phenyl C ₁ -C ₂ monoalkylamino, C ₁ -C ₂ dialkylamino, morpholino or piperidino. Naphthopyran compound selected from the group consisting out: (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- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran, (E) 2- (4-dimethylaminophenyl) -2-phenyl-5-methoxycarbonyl-6-methyl-2H-naphtho [1,2-b] pyran and (f) 2-2-Bis (4-dimethylaminophenyl) -5-methoxycarbonyl-6-acetoxy-2H-naphtho [1,2-b] pyran. Photochromic article containing a polymeric organic host material and a photochromic amount of a naphthopyran compound according to one of the claims 1-5. The photochromic article of claim 6, wherein the photochromic compound is present in an amount of from 0.05 to 1.0 mg / cm ^{2 of} organic host material surface on which the photochromic substance (s) are incorporated or coated. Photochromic article containing in combination a solid transparent polymeric organic host material and a photochromic amount of each (a) at least one naphthopyran compound according to one of the claims 1-5 and (b) at least one other organic photochromic compound with at least one activated absorption maximum in the range between 400 and 700 nm. A photochromic article according to claim 8, wherein said organic photochromic compound (b) is selected from the group consisting out: (a) organic photochromic substances with at least an absorption maximum in the visible range between 400 and less than 500 nm, (b) organic photochromic substances with an absorption maximum in the visible range between 400 and 500 nm and an absorption maximum in the visible range between 500 and 700 nm and (c) organic photochromic substances with an activated absorption maximum in the visible range of more than 570 nm and (d) mixtures of these organic photochromes Substances. A photochromic article according to claim 9, wherein the organic photochromic compound (b) an organic photochromic Substance with an activated absorption maximum in the visible Range of more than 570 nm. A photochromic article according to claim 9, wherein the organic photochromic compound (b) is selected from the group consisting from spiro (indoline) naphthoxazines, spiro (indoline) pyridobenzoxazines, spiro (benzindoline) pyridobenzoxazines, Spiro (benzindoline) naphthoxazines, spiro (benzindoline) naphthopyrans, Spiro (indoline) benzoxazines, spiro (indoline) benzopyrans, spiro (indoline) naphthopyrans, Spiro (indoline) quinopyranes, spiro (indoline) pyrans, 3H-naphtho [2,1-b] pyrans, 2H-phenanthro [4,3-b] pyrans, 3H-phenanthro [1,2-b] pyrans, benzopyran compounds and mixtures of such photochromic substances. The photochromic article of any one of claims 6-11, wherein the polymeric organic host material is selected from the group consisting of 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 polycarbonates, polyesters, polyurethanes, poly (ethylene terephthalate), polystyrene, poly (α-methylstyrene), copoly (styrene methyl methacrylate), copoly (styrene acrylonitrile), polyvinyl butyral and polymers of the members of the group consisting of polyol (allyl carbonate) monomeric polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, diisopropenylbenzene monomers, alkoxylated polyhydric alcohol acrylate monomers, and diallylidenepentaerythritol monomers. A photochromic article according to claim 12, wherein the polymeric organic host material is a solid, transparent homopolymer or copolymer is selected from the group consisting of poly (methyl methacrylate), poly (ethylene glycol bismethacrylate), poly (ethoxylated bisphenol A dimethacrylate), thermoplastic Polycarbonate, poly (vinyl acetate), polyvinyl butyral, polyurethane and Polymers of members of the group consisting of diethylene glycol bis (allyl carbonate) monomers, Diethylene glycol dimethacrylate monomers, diisopropenylbenzene monomers and ethoxylated trimethylolpropane triacrylate monomers. A photochromic article according to any one of claims 6-13, wherein the article is a lens.