Novel photochromic heterocyclic fused indenonaphthopyrans

The This invention relates to certain novel naphthopyran compounds. More specifically, the invention relates to novel photochromic heterocyclic fused Indenonapthopyran compounds and compositions and articles the such new indenonaphthopyran-compounds. If it contains electromagnetic radiation, the ultraviolet rays, such as for example, ultraviolet radiation in sunlight or the light a mercury vapor lamp, suspended, many showing photochromic Compounds exhibit a reversible change in color. When the ultraviolet radiation is discontinued, is such a photochromic compound to its original state Color or colorless return.

Various Classes of photochromic compounds have been synthesized and Use in applications proposed in which a sunlight induced reversible color change desired or blackout becomes. US Patent 3,567,605 (Becker) describes a series of pyran derivatives, include certain benzopyrans and Napthopyrane. These Compounds are described as derivatives of chromene and are is described as a color change, eg. as from colorless to yellow-orange due to irradiation by ultraviolet light subjected at temperatures below -30 ° C will. Irradiation of the compounds with visible light or increase the temperature to about 0 ° C brings the coloring - as reported - in a colorless state.

US Patent 5,066,818 describes various 3,3-diaryl-3H-naphtho [2,1-b] pyrans as the desired photochromic properties comprising, ie, high colorability and acceptable fade, for the treatment of eye diseases and other applications. As part of a comparative example in the '818 patent are also the isomers 2,2-diaryl-2H-naphtho [1,2-b] pyrans, which are reported that they unacceptably long periods need, to fade after activation disclosed.

US Patent 3,627,690 describes photochromic 2,2-di-substituted 2H-naphtho [1,2-b] pyran compounds, minor amounts of either a base or a weak to medium Acid. The addition of either an acid or a base to the naphthopyran - as described - increases the Fade rate of the colored Naphthopyrans what they sense in applications for eye protection, example for Sunglasses makes. It is there further reported that the fade rate of 2H-naphtho [1,2-b] pyrans without the above said additives from several hours to several days will take, to complete Back Education to get.

US Patent 4,818,096 discloses purple-/ blue colored photochromic benzo- or naphthopyrans which at the α-position the oxygen of the pyran ring a vinyl group having a Nitrogen containing substituent in the ortho- or para-position. WO 96/14596 describes novel photochromic naphthopyran indenofusionierte, wherein the 2,1-positions of the indeno group at the f side of the naphthopyran fused.

The present invention relates to new Indenonaphtho [1,2-b] pyran compounds, the substituted or unsubstituted heterocyclic have ring whose 2,3- or 3,2-positions with the d, h, i, n, o or p side of the indenonaphthopyran are fused, and certain substituents at the 3-position of the Pyran ring. It has been unexpectedly found that these Compounds a bathochromic shift of the wavelength in the show visible spectrum in which the maximum absorption of activated (colored) form of the photochromic compound, ie the λ_MaxValue (Vis), occurs, What then, in activated colors ranging from orange to blue / gray results.

Detailed Description of the Invention

in recently Time were photochromic plastic materials, particularly materials plastic for optical applications subject to appreciable attention. specifically photochromic lenses plastic were tested because they offer weight advantages Compared to lenses of glass. About that also were photochromic transparent materials for vehicles, such. as cars and airplanes, due to its potential safety features, the transparent materials such offer of interest.

In accordance with the present invention has now been discovered that certain new indeno [2,1-f] naphtho [1,2-b] pyrans having activated colors, ranging from orange to blue / gray, can be produced. These compounds be described as indenonaphthopyrans, the unsubstituted one, monosubstituted or di-substituted heterocyclic ring, whose 2,3- or 3,2-positions with the g-, h-, i, n, o or p-sides of indenonaphthopyran fused and specific substitution<?page 3?>ducks having at the 3-position of the pyran ring. Certain substituents can also to the Nos. 5, 6, 7 or 8 carbon atoms of the naphthopyran compound be present, if the heterocyclic ring to the n, o or p side of the is indenonaphthopyran fused; or to Figures 9, 10, 11 or 12 carbon atoms of the naphthopyran compound, if the heterocyclic fused ring at the g, h, or i side of the indenonaphthopyran becomes.

The above indenonaphthopyran connections can The following graphic formulas I and I 'in which the letters a through p the sides or surfaces of different molecular rings which include the compound represent, represents be and the numbers 1 through 13 identify the ring atoms of the Heterocyclic fused indenonaphthopyran. In the definition the substituents shown in formulas I and I ', like symbols have the same meaning, unless otherwise specified.

<img img-content="cf" img-format="tif" he="60" wi="128" file="00030001.tif" />

in graphic formulas I and I 'can A is an unsubstituted, monosubstituted or disubstituted or be heterocyclic ring selected from the group consisting of benzothieno, benzofurano and indolo, the 2,3 or 3,2 positions of the heterocyclic ring to the g, h, i, n, o or p side the indenonaphthopyran fused. Each of the above-described heterocyclic ring substituents can C₁-C₆Alkyl, C₅-C₇Cycloalkyl, C₁-C₆Alkoxy, bromine, be chlorine or fluorine. preferably is the heterocyclic ring A is unsubstituted or mono-substituted and the heterocyclic ring substituents are C₁-C₄Alkyl or C₁-C₄Alkoxy. Most preferably, the heterocyclic Ring A is unsubstituted or mono-substituted, the 2,3 or 3,2-position the heterocyclic ring is to the g or p side of the indenonaphthopyran fused and heterocyclic ring substituents are C₁-C₃Alkyl or C₁-C₃Alkoxy.

in of graphic formula I, R₁ Hydrogen, Hydroxy, bromo, be fluorine or chlorine, and R₂ can the group CH (V)₂ be, wherein V is -CN or -COOR₅ , and each R₅ provides Hydrogen, C₁-C₆alkyl, Phenyl- (C₁-C₃) Alkyl, mono- (C₁-C₆) -alkylsubsituiertes Phenyl- (C₁-C₃) Alkyl, mono- (C₁-C₆) Alkoxy-phenyl (C₁-C₃) Alkyl or the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl are, or R₂ may the -CH (R₆) Y , wherein R₆ Hydrogen, C₁-C₆Alkyl or the unsubstituted, mono- or disubstituted aryl groups phenyl or naphthyl, and Y -COOR₅, -COR₇ or -CH₂OR₁₁ , wherein R₇ Hydrogen, C₁-C₆Alkyl, the unsubstituted, mono- or disubstituted aryl groups phenyl or naphthyl, amino, mono-C₁-C₆alkylamino, Di- (C₁-C₆) Alkylamino, for example, Dimethylamino, methylpropylamino, etc., phenylamino, mono- or Di- (C₁-C₆) Alkyl-substituted Phenylamino, mono- or di- (C₁-C₆) alkoxy it phenylamino, diphenylamino, mono- or di- (C₁-C₆represents) alkyl substituted diphenylamino, that is, each phenyl has one or two C₁-C₆-Alkylsubsituenten On, mono- or di- (C₁-C₆) Alkoxy substituted diphenylamino, Morpholino or piperidino group; R₁₁ Hydrogen, -COR₅, C₁-C₆Alkyl, C₁-C₃Alkoxy- (C₁-C₆) Alkyl, phenyl (C₁-C₃) Alkyl, mono- (C₁-C₆) -alkylsubsituiertes Phenyl- (C₁-C₃) Alkyl, mono- (C₁-C₆) Alkoxy-substituted Phenyl- (C₁-C₃) alkyl or unsubstituted, mono- or di-substituted aryl groups phenyl or represents naphthyl, where all of the abovementioned aryl groups substituents C₁-C₆alkyl or C₁-C₆alkoxy are. Alternatively, R₁ and R₂ together the group = C (V)₂ or = C (R₆) W form, wherein W is -COOR₅ or -COR₇ is.

preferably is R₁ Is hydrogen, hydroxy, fluorine, or Is chloro and R₂ is the group -CH (V)₂Wherein V is -CN or equal -COOR₅ and each R₅ provides Hydrogen, C₁-C₄Alkyl, phenyl (C₁-C₂) Alkyl, mono- (C₁-C₄) -alkylsubsituiertes Phenyl- (C₁-C₂) Alkyl, mono- (C₁-C₄) -alkoxysubsituiertes Phenyl- (C₁-C₂) alkyl or unsubsituierten or mono-alkyl substituted phenyl or naphthyl or represents R₂ is the group &lt;?page 4?&gt;CH (R₆) Y, wherein R₆ Hydrogen, C₁-C₄alkyl or the unsubstituted or mono-substituted Aryl groups phenyl or naphthyl, and Y is -COOR₅. -COR₇ or -CH₂OR₁₁ , wherein R₇ Hydrogen, C₁-C₄Alkyl, the unsubstituted or mono-substituted Aryl groups phenyl or naphthyl, amino, mono (C₁-C₄) Alkylamino, di- (C₁-C₄) Alkylamino, phenylamino, mono- or di- (C₁-C₄) Alkyl-substituted Phenylamino, mono- or di- (C₁-C₄) Alkoxy substituted phenylamino, diphenylamino, mono- or di- (C₁-C₄) -alkylsubsituiertes Diphenylamino, mono- or di- (C₁-C₄) Alkoxy-substituted Diphenylamino, morpholino or piperidino; R₁₁ provides Hydrogen, -COR₅, C₁-C₄Alkyl, C₁-C₂Alkoxy- (C₁-C₄) Alkyl, phenyl (C₁-C₂) Alkyl, mono- (C₁-C₄) Alkyl substituted phenyl (C₁-C₂) Alkyl, mono- (C₁-C₄) Alkoxy-substituted Phenyl- (C₁-C₂) alkyl or the unsubstituted or mono-substituted alkyl groups Represents phenyl or naphthyl, where all of the above aryl group C₁-C₄alkyl or C₁-C₄Alkoxy.

more preferably is R₁ Is hydrogen, hydroxy or Is chloro and R₂ is the group -CH (V)₂Wherein V CN is equal to, or R₂ is the group -CH (R₆) Y, wherein R₆ hydrogen or C₁-C₄represents alkyl and Y is -COOR₅ or -CH₂OR₁₁ , wherein R₅ Is hydrogen or C₁-C₄alkyl , and R₁₁ Hydrogen, -COR₅ or C₁-C₄is alkyl. Alternative form R₁ and R₂ the group = C (V)₂ or = C (R₆) West from where W is -COOR₅ is.

in graphic formulas I and I ', R₃ and R₄ each C₁-C₆Alkyl, C₁-C₆Alkoxy, bromine, be chlorine or fluorine, and m and n are integers 0, 1, or second Preferably, R₁ and R₂ each C₁-C₄Alkyl, C₁-C₄Alkoxy, chloro or fluorine, and m and n are each integers 0 or 1. Most preferably, R₃ and R₄ each C₁-C₃Alkyl and C₁-C₃Alkoxy, and m and n are integers 0 or the first

B and B 'in graphic Formulas I and I 'may each selected be selected from the group consisting of: (I) the unsubstituted, mono-, di- and trisubsubstituierten aryl groups phenyl and naphthyl; (II) the unsubstituted, mono- and di-substituted aromatic heterocyclic Groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, Benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, Carbazolyl and fluorenyl, wherein each of said aryl and aromatic heterocyclic substituents in parts (I) and (II) selected is selected from the group consisting of hydroxy, aryl, mono (C₁-C₆) Alkoxyaryl, di (C₁-C₆) Alkoxyaryl, mono (C₁-C₆) Alkylaryl, di (C₁-C₆) Alkylaryl, Bromoaryl, Chloroaryl, Fluoroaryl, C₃-C₇-Cycloalkylaryl, C₃-C₇cycloalkyl, C₃-C₇cycloalkyloxy, C₃-C₇-Cycloalkyloxy- (C₁-C₆) Alkyl, C₃-C₇-Cycloalkyloxy- (C₁-C₆) Alkyl, C₃-C₇-Cycloalkyloxy- (C₁-C₆) Alkoxy, aryl (C₁-C₆) Alkyl, aryl (C₁-C₆) Alkoxy, aryloxy, aryloxy (C₁-C₆) Alkyl, aryloxy (C₁-C₆) Alkoxy, Mono- and di- (C₁-C₆) Alkylaryl (C₁-C₆) Alkyl, mono- and di- (C₁-C₆) -alkoxyaryl- (C₁-C₆) Alkyl, mono- and di- (C₁-C₆) Alkylaryl (C₁-C₆) Alkoxy, mono- and di- (C₁-C₆) -alkoxyaryl- (C₁-C₆) Alkoxy, amino, Mono (C₁-C₆) Alkylamino, Di- (C₁-C₆) Alkylamino, diarylamino, N- (C₁-C₆) -alkylpiperazino, N-Arylpiperazino, aziridino, indolino, piperidino, Arylpiperidino, Morpholino, thiomorpholino, tetrahydroquinolino, Tetrahydroisochinolino, Pyrryl, C₁-C₆alkyl, C₁-C₆-Bromoalkyl, C₁-C₆-Chloroalkyl, C₁-C₆-Fluoroalkyl, C₁-C₆Alkoxy, mono (C₁-C₆) Alkoxy (C₁-C₄) Alkyl, acryloxy, Methacryloxy, bromo, chloro and fluoro; (III) the groups represented by the following graphic formulas: <img img-content="cf" img-format="tif" he="25" wi="81" file="00060001.tif" />wherein E is carbon or may be oxygen and D is oxygen or substituted nitrogen may be, with the proviso that when D is substituted nitrogen , E is carbon, said nitrogen substituents are selected from the group consisting of hydrogen, C₁-C₆Alkyl and C₂-C₆acyl; each R₈ C₁-C₆Alkyl, C₁-C₆Alkoxy, hydroxy, Bromine, chlorine or fluorine; R₉ and R₁₀ Is hydrogen or C₁-C₆are alkyl; and p is an integer of 0, is 1 or 2; (IV) C₁-C₆alkyl, C₁-C₆-Bromoalkyl, C₁- C₆-Chloroalkyl, C₁-C₆-Fluoroalkyl, C₁-C₆Alkoxy- (C₁-C₆) Alkyl, C₃-C₆Cycloalkyl, mono- (C₁-C₆) Alkoxy (C₃-C₆) Cycloalkyl, mono- (C₁-C₆) Alkyl (C₃-C₆) -cycloalkyl, Bromo (C₃-C₆) Cycloalkyl, chloro (C₃-C₆) Cycloalkyl and fluoro (C₃-C₆) Cycloalkyl; and (v) the group represented by the following graphic formula: <img img-content="cf" img-format="tif" he="18" wi="17" file="00070001.tif" />wherein X in graphic Formula IIC hydrogen or C₁-C₄can be alkyl and Z in graphic selected formula IIC may be from the group of unsubstituted, mono- and disubstituted Members of Grup&lt;?page 5?&gt;pe consisting of naphthyl, phenyl, furanyl and Thienyl, wherein each of said groups substituents in this Part (V) C₁-C₄alkyl, C₁-C₄Alkoxy, bromine, Fluoro or chloro; or (VI) B and B ', taken together, fluoren-9-ylidene, mono- or di-fluoren-9-ylidene or a train Member selected from the group consisting of saturated C₃-C₁₂spiro-monocyclic Hydrocarbon rings, for example, cyclopropylidene, cyclobutylidene, Cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene, Cyclononyliden, cyclodecylidene, Cycloundecyliden and cyclododecylidene; saturated C₁-C₁₂-spirobicyclischen Hydrocarbon rings, such as [2.2.1] heptylidene, ie norbornylidene, 1,7,7-trimethylbicyclo [2.2.1] heptylidene, d. h. bornylidene, bicyclo [3.2.1] octylidene, bicyclo [3.3.1] nonan-9-ylidene and bicyclo [4.3.2] undecane, and saturated C₁-C₁₂spiro-tricyclic hydrocarbon rings, For example, tricyclo [2.2.1.0^2.6] heptylidene and tricyclo [3.3.1.1^3.7] Decylidene, ie Adamantylidene and tricyclo [5.3.1.1^2.6] Dodecyliden, wherein each is selected from said fluoren-9-ylidene substituents from the group consisting of C₁-C₄Alkyl, C₁-C₄Alkoxy, bromo, fluoro and chloro.

more preferably, B and B 'are each selected from the group consisting of: (I) phenyl, mono-substituted phenyl and di-substituted phenyl, preferably substituted in the meta and / or para-position; (II) the unsubstituted, mono- and di-substituted aromatic heterocyclic groups furanyl, benzofuran-2-yl, Thienyl, benzothien-2-yl, dibenzofuran-2-yl and dibenzothien-2-yl, each of said phenyl and aromatic heterocyclic Substituents in (I) and (II) is selected from the group consisting from hydroxy, aryl, aryloxy, aryl (C₁-C₃) Alkyl, amino, mono- (C₁-C₃) Alkylamino, di- (C₁-C₃) Alkylamino, N- (C₁-C₃) -alkylpiperazino, Indolino, piperidino, Morpholino, pyrryl, C₁-C₃alkyl, C₁-C₃chloroalkyl, C₁-C₃fluoroalkyl, C₁-C₃Alkoxy, mono (C₁-C₃) -akoxy- (C₁-C₃) Alkyl, fluoro and chloro; (III) the group represents by the graphic formulas IIA and IIB, wherein E is carbon and D is oxygen, R₈ C₁-C₃Alkyl or C₁-C₃is alkoxy, R₉ and R₁₀ are each hydrogen or C₁-C₄alkyl are; and p is the integer 0 or 1; (IV) C₁-C₄alkyl; and (v) the group represented by the graphic formula IIC wherein X is hydrogen or methyl and Z is phenyl or mono substituted phenyl, wherein said phenyl selected is selected from the group consisting of C₁-C₃Alkyl, C₁-C₃Alkoxy and fluoro; 'Taken or (VI) B and B together Fluoren-9-ylidene form, mono-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C₃-C₈spiro-monocyclic Hydrocarbon rings, saturated C₇-C₁₀spiro-bicyclic hydrocarbon rings and saturated C₇-C₁₀spiro-bicyclic Hydrocarbon rings, said fluoren-9-ylidene substituent selected is selected from the group consisting of C₁-C₃Alkyl, C₁-C₃Alkoxy, fluorine and chlorine.

At the Most preferably, B and B 'is selected from the group consisting of (i) phenyl, mono- and di-substituted phenyl; (II) the unsubstituted, mono- and di-substituted aromatic heterocyclic groups furanyl, benzofuran-2-yl, thienyl and benzothien-2-yl, wherein each of said phenyl and aromatic heterocyclic Substituents in (II) and (II) is selected from the group consisting from hydroxy, C₁-C₃alkyl, C₁-C₃Alkoxy, aryl, Indolino, fluoro and chloro; and (III) the group represented by graphic formula IIA, wherein E is carbon and D is oxygen , R₈ C₁-C₃Alkyl or C₁-C₃Alkoxy; R₉ and R₁₀ are each hydrogen or C₁-C₃alkyl are; and p is the integer 0 or 1; or (IV) B and B ', taken together, Fluoren-9-ylidene, adamantylidene, bornylidene, norbornylidene or bicyclo [3.3.1] nonane-9 form ylides.

compounds represents by graphic formulas I and I ', the substituents R₃ and R₄As previously described herein, have, can prepared by the reactions described in the following A to E will. compounds represented by graphic formula V or VA (as shown in Reactions A and B shown) by Friedel-Crafts methods as shown in reaction A shown, using an appropriately substituted or unsubstituted Benzoyl chloride of graphic formula IV with a commercially available substituted or unsubstituted heterocyclic compound of graphic Formula III prepared. See the publication Friedel-Crafts and Related Reactions, George A. Olah, Interscience Publishers, 1964, Vol. 3, Chapter XXXI (Aromatic Crafts Acylation of 1,2,3,4-tetrahydroquinoline and Related Nitrogen Heterocycles: Effect on NH Protective Groups and Ring Size "at Ishihara, Yugi et al., J. Chem. Soc., Perkin Trans. 1, 3401 pages until 3406., 1992

in Reaction A, the compounds represented by the graphic Formulas III (wherein X is oxygen, nitrogen or sulfur), and IV dissolved in a solvent, For example, in carbon disulfide or methylene chloride, and in the presence of a Lewis column, such as., aluminum chloride or tin tetrachloride, reacted to represents the corresponding substituted benzophenone form by graphic formula V.

&lt;?page 6?&gt;

REACTION A <img img-content="cf" img-format="tif" he="26" wi="130" file="00090001.tif" />

in Reaction B, the substituted or unsubstituted ketone represented, by graphic formula VA with Natriumazetylid in a suitable Solvent, such. As anhydridischem tetrahydrofuran (THF), is reacted, to the corresponding propargyl alcohol represented by graphic form formula VI. Propargyl alcohols which B or B 'groups comprise which differ from substituted and unsubstituted phenyl, can from commercially available Ketones or ketones prepared by the reaction of an acyl halide with a substituted or unsubstituted benzene, naphthalene or a heteroaromatic compound are produced. propargyl, having a B or B 'group exhibit and represents would by graphic formula IIC, can by the methods as described in US Patent 5,274,132, column 2, lines describes 40-68 manufactured.

REACTION B <img img-content="cf" img-format="tif" he="20" wi="91" file="00100001.tif" />

in Reaction C represents the substituted or unsubstituted ketone by graphic formula V with an ester of succinic acid, such as z. B. dimethyl represents, implemented by graphic formula VII. The addition of the reactants, a solvent such as toluene, which tert-butoxy or Sodium hydride contains, as the base, leads to half esters of the Stobbe condensation, represented by the graphical Formula VIII. The half ester (VIII) undergoes a cyclodehydration in the presence of acetic anhydride to the heterofusionierten Acetoxynaphthaline, represents form by graphic formulas IXA and IXB. The connection IXA and IXB may be separated by crystallization, in an aqueous alcoholic solution a base can be hydrolyzed, for example, sodium hydroxide, followed by treatment in an aqueous hydrochloric acid (H⁺) To the Carboxynaphthole represents form by graphic formulas XA or XB.

&lt;?page 7?&gt;

REACTION C <img img-content="cf" img-format="tif" he="163" wi="125" file="00110001.tif" />

in Reaction D are represented by the graphical Carboxynaphthole Formulas XA and XB are cyclized by heating, eg., From about 160 ° C to about 220 ° C in the presence of an acid, such. as phosphoric acid, represents a hydroxy-substituted fluorenone benzfusioniertes form by graphic formulas XIA and XIB. See the Article by FG ​​Baddar et al. in J. Chem. Soc., page 986 1958. An alternative method for synthesizing the compound represented is XIB by graphic formula of CF Koelsch in the Journal of Organic Chemistry, Volume 26, page 2590, 1961 described.

The represents coupling of compounds represented by graphic formulas XIA and XIB with propargyl by graphic formula VI in the presence of a catalytic Amount of an acid, for example, dodecylbenzenesulfonic (DBSA Dodecylbenzene sulfonic acid), results in the indeno-fused naphthopyran represented by graphic formulas IA and IB.

&lt;?page 8?&gt;

REACTION D <img img-content="cf" img-format="tif" he="195" wi="111" file="00130001.tif" />

in Reaction E, further methods for preparing compounds represents by graphic formula I ', a plurality of R₁- And R₂substituents has described. Starting with the compound represented with graphic formula I'C leads the Treatment with an α-Bromoester of graphic formula XII in the presence of tin dust is activated represents to the compound by graphic formula I'D. This reaction, which is called Reformatsky reaction, is by RL Shriner in Organic Reactions, Vol. 1, pages 1-37, 1942 gereviewt. represents Compound by graphic formula I'D may be further reacted with chlorinating reagents, for example with thionyl chloride derivatives represented, by graphic formula I'e produce. The compound represented graphic formula I'e can dehydrohalogenating are prepared by heating in the presence of a tertiary amine, for example collidine to α, β-unsaturated ester graphic formula I'F to obtain.

&lt;?page 9?&gt;

alternative may represent the connection by graphic formula I'C be condensed with a compound containing an active methylene represents contains by graphic formula XIII, in the presence an amine to the compound represented by graphic prepare formula I'g. This reaction, which is known as the Knoevenagel condensation, is, by G. Jones in Organic Reactions, Vol. 15, pages 204-599, 1967 gereviewt.

all the steps of the reaction E can also be carried out with a compound analogous to represents the connection by graphic formula I'C is, however, the A group having in the position as shown in the graphical Formula I represents.

REACTION e <img img-content="cf" img-format="tif" he="154" wi="131" file="00150001.tif" />

compounds represents by graphic formula I, I ', IA, IB, I'C, I'D, I'e, I'F and I'g can in those Applications are used, in which organic photochromic substances can be used, such. as for optical lenses, eg. as vision corrective lenses and Plano lenses, face shields, goggles, visors, camera lenses, Windows, car windshields, transparent materials in aircraft and cars, z. B. T-Roofs, side and rear lights, plastic films and coatings, textiles and coatings, eg, coating compositions such as z. B. sprays and verification marks on security documents, For example, documents such as banknotes, passports and drivers' licenses for which Authentication or verification of authenticity may be desired can. represents Heterocyclic merged indenonaphthopyrans by graphic formulas described above exhibit color changes from colorless to colors ranging from orange to blue / gray.

&lt;?page 10?&gt;

Examples by considering drawn indenonaphthopyran compounds within the scope of the invention conclude the following: <ul><li>(A) 3,3-Di (4-methoxyphenyl) -16- (ethoxycarbonyl) methyl-16-hydroxy-3,16-di [H] -benzofuro [2 ', 3': 3,4] naptho [1, 2-b] pyran;</li><li>(B) 3- (4-methoxyphenyl) -3- (4-morpholinophenyl) -16- (ethoxycarbonyl) methyl-16-hydroxy-3,16-di [H] -benzofuro [2 ', 3': 7,8 ] indeno [2 ', 3': 3,4] naphtho [1,2-b] pyran;</li><li>(C) 3-Phenyl-3- (4-methoxyphenyl) -16- (ethoxycarbonyl) methyl-16-hydroxy-3,16-di [H] -benzofuro [2 '', 3 '': 6 ', 7' ] indeno [3 ', 2': 4,3] naphtho [1,2-b] pyran; and</li><li>(D) 3-Phenyl-3- (4-morpholinophenyl) -16- (ethoxycarbonyl) methyl-16-hydroxy-3,16-di [H] -benzofuro [2 '', 3 '': 6 ', 7' ] ideno [3 ', 2': 4,3] naphtho [1,2-b] pyran.</li></ul>

it is considering been drawn that the organic photochromic Idenonaphthopyrane the present invention alone, in combination with other Idenonaphthopyranen of the present invention or in combination with one or more other appropriate complementary organic photochromic materials, ie, organic photochromic Compounds within at least one activated absorption maxima the range between about having 400 and 700 nanometers, or substances containing such, can be used and introduced, ie dissolved in a polymeric organic host material or can be dispersed, which is used to prepare photochromic articles and which color when activated, becomes an appropriate hue.

Except there, where it is indicated otherwise, all numbers expressing wavelengths, quantities understand of ingredients or reaction conditions used herein are, as modified in all instances by the term "about".

Examples complementary organic photochromic compounds include other indenonaphthopyrans, Chromenes and oxazines, for example, naphthopyrans which the 2,1-position having an indeno group fused to the f side of the naphtho-portion, and certain substituents at the 3-position of the pyran ring, substituted 2H-phenanthro [4,3-b] pyran and 3H-phenanthro [1,2-b] pyran compounds, benzopyran compounds, having substituents at the 2-position of the pyran ring including a dibenzofusionierte 5-membered heterocyclic compound and a substituted or unsubstituted heterocyclic ring, such. as a benzothieno or Benzufuranoring fused to the benzene portion of the benzopyran, Spino (benzindoline) napththopyrane, Spiro (indoline) benzopyrans, Spino (indoline) naphthopyrans, spiro (indoline) quinopyrans, Spiro (indoline) pyrans, Spino (indoline) napthoxazine, spiro (indoline) pyridobenzoxazines, Spino (benzindoline) pyridobenzoxazines, Spiro (benzindoline) naphthoxazines, spiro (indoline) benzoxazines, and mixture Such photochromic compounds. Many such photochromic Compounds are described in the general literature, for example in U.S. Patent No. 3,562,172.; 3,567,605; 3,578,602; 4,215,010; 4,342,668; 4,816,584; 4,818,096; 4,826,977; 4,880,667; 4,931,219; 5,066,818; 5,238,931; 5,274,132; 5,384,077; 5,405,958; 5,429,774; 5,466,398; 5,514,817; 5,552,090; 5,552,091; 5,565,146; 5,573,712; 5,578,252; WO 96 14596 and in Japanese Patent Publication 62/195383. Spiro (indoline) pyrans are also in the text, Techniques in Chemistry, Volume III, "Photochromism", Chapter 3, Glenn H. Brown, Editor, John Wiley and Sons, Inc., New York, 1971 is described.

Other photochromic substances contemplated are photochromic Metalldithizonate, for example, mercury, for example, are described in U.S. Patent 3,361,706, fulgides and fulgimides, such. as the 3-furyl and 3-thienyl and fulgimides which in US Pat. No. 4,931,220 at column 20, line 5 through column 21, Line 38 will be described.

The Revelations that the to such photochromic compounds in above are referenced patents, are in their entirety by reference locked in. The photochromic articles of the present inventions can a photochromic compound or a mixture of photochromic compounds included as needed.

Each the photochromic compounds described herein may in Amounts (or in a proportion) can be used, so that an organic Host material to which the photochromic compounds or Mixture of compounds is applied or in which they contain are, a desired resultant color, eg, a substantially neutral Color when activated with unfiltered sunlight, i. h. as near a neutral as possible, going from the colors of the activated photochromic &lt;?page 11?&gt;compounds out. Neutral gray and neutral brown colors are preferred.

A neutral gray color exhibits a spectrum that has a relatively uniform absorption in the visible range between 400 and 700 nanometers. A neutral brown color exhibits a spectrum in which the absorption in the range between 400 and 550 nanometers greater than moderate is in the 550-700 nanometer range. An alternative way of color to describe, with the help of their chromatographic coordinates, what quality the a color in addition to its luminance factor, ie, its chromaticity describe. In the CIE system, the chromaticity coordinates are obtained by that the ratios the tristimulus values ​​to their sum takes, for example, x = X / (X + Y + Z) and y = Y / (X + Y + Z). Color as described in the CIE system, can on a chromaticity are plotted, usually a Plott of chromaticity x and y. See pages 47 to 52 of Principles of Color Technology, at FW Bill Meyer, Jr., and Max Saltzman, Second Edition, John Wiley and Sons, NY (1981). As used herein, is an approximately neutral Color is one in which the chromaticity coordinate values ​​of "x" and "y" for the color within the following ranges (D65 Selbstleuchtner) are: x = 0.260 to 0.400, y = 0.280 to 0.400 as a result of activation 40% Lumineszenztransmission due to exposure to sunlight (Air mass 1 or 2).

The Amount of photochromic substance or composition selbige contains, applied to or incorporated into a host material is not critical tion under the Vorausset that a sufficient amount is used is to provide a photochromic effect discernible to the naked eye is, after activation to produce. Generally such amount can are called photochromic amount. The particular amount, which is used depends often requested by the intensity color upon irradiation thereof and upon the method from which is used to incorporate the photochromic substances or apply. Usually is the color intensity up to a certain limit is greater, the more photochromic substance applied or is introduced.

The relative amounts of the photochromic compounds used above will vary and depend in part upon the relative intensities of the color of the activated Species of such compounds from, and of the final desired Color. In general, the amount of total photochromic on a photochromic introduced optical host material or applied thereto Substance from 0.05 to 1.0, for example, from 0.1 to 0.45 milligrams per square centimeter of surface rich, to which the photochromic substance (the photochromic substances) is introduced or applied (be).

The photochromic substances of the present invention may be applied a host material, such. as a polymeric organic host material, be applied or introduced into selbiges by various methods are described in the prior art. Such methods conclude dissolve or dispersing the photochromic substance within the host material a, z. B. the pouring in place by adding the photochromic substance to the monomeric host material prior to polymerization; vacuuming of photochromic substances in the host material by immersion the host material in a hot solution the photochromic substance or by thermal transfer; providing the photochromic substance as a separate layer between adjacent Layers of the host material, for example as part of a Polymer film; and applying the photochromic substance as part Coatings or a film placed on the surface of Host material. The term "absorbing" or "imbibe" is intended penetration the photochromic substance alone into the host material, the a solvent supported Transfer of the photochromic substance into a porous polymer, vapor phase transfer, mean and include, and other such transfer mechanisms.

Compatible (Chemical and color type) inks, ie, dyes, may on the host material are applied in order to achieve a more aesthetic result, for medical reasons or for reasons of fashion. The special selected Dye will vary and or of the needs mentioned above the achieved result depend. In another embodiment, the dye may be selected be that he is the complement of the color off the activated photochromic substances obtained, for. example, a rather to achieve a neutral color or a specific wavelength of the incident light. In another embodiment, the dye selected are that it gives the host matrix a desired color when the photochromic Substances in a non-activated state.

The Host material is usually be transparent, but may be translucent or even opaque. The Host material need only be transparent in that the part of the electromagnetic spectrum, which the photochromic substances activated, ie the wavelength ultraviolet (UV) light that the free form of the substance produced or that portion of the visible light, the maximum of the Absorption wavelength &lt;?page 12?&gt;of the Substance in its UV activated form includes, ie, in the free form is concerned. Preferably, the host color should not be so, to the color of the activated form of the photochromic substance masked, ie, so that the change in the color is immediately apparent to the viewer. More preferably, provides the host material article is a solid transparent material or an optically clear material is, for example, a material suitable for optical applications, such. as plano lenses and spectacle lenses, windows, Auto-transparent materials, such. As windshields, aircraft transparencies materials, plastic coatings, Polymeric films, etc.

Examples of polymeric organic host materials which photochromic with the Substances or compositions, as described herein, may be used conclude A: polymers, ie, homopolymers and copolymers, of polyol (allyl carbonate) monomers, Diethylene glycol dimethacrylate monomers, Diisopropenylbenzenmonomeren, ethoxylated bisphenol A dimethacrylate, Ethylenglycolbismethacrylatmonomeren, Poly (ethlyenglycol) bismethacrylatmonomeren, ethoxylated phenol and alkoxylated polyhydric Alkoholacrylatmonomeren such. B. ethoxylated trimethylol propane triacrylate; Polyme re, ie homopolymers and copolymers, of polyfunctional, for example, mono-, di- or multi-functional acrylate and / or methacrylate monomers, poly (C₁-C₁₂alkyl methacrylates) such as. for example, poly (methyl methacrylate), poly (oxyalkylendimethacrylat), poly (alkoxylated Phenolmethacrylat), 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 (ethlyenterephthalat), Polystyrene, poly (alpha methylstyrene), copoly (styrolmethylmethacrylat), copoly (styrolacrylonitril), polyvinyl butyral; and polymers, ie, homopolymers and copolymers, monomers of diallylidene pentaerythritol, particularly copolymers with polyol (allyl carbonate), For example, diethylene glycol bis (allyl carbonate), and acrylate monomers.

Transparent Copolymers and blends of transparent polymers are also suitable as a host material. Preferably, the host material is produced an optically clear polymerized organic material contain from a thermoplastic polycarbonate resin, such. B. the carbonate-linked Resin, obtained from bisphenol A and phosgene, sold under the trademark LEXAN is sold; a polyester, such as, for. example, the material is sold under the trademark MYLAR; a poly (methyl methacrylate), such as. for example, the material sold under the trademark PLEXIGLAS becomes; Polymerizates of a polyol (allyl carbonate) monomer, especially Diethylene glycol bis (allyl carbonate) sold under the trademark CR-39 is sold and polymerizates of copolymers of a polyol (allyl carbonate), For example, diethylene glycol bis (allyl carbonate), with other copolymerizable monomeric materials such as. for example, copolymers with vinyl acetate, z., copolymers of 80 to 90% diethylene glycol bis (allyl carbonate) and 10 to 20% vinyl acetate, in particular 80 to 85% of the bis (allyl carbonate) and 15 to 20% vinyl acetate, and copolymers with a polyurethane, the terminal diacrylate comprises, as described in U.S. Patents 4,360,653 and 4,994,208; and copolymers with aliphatic urethanes, the terminal units which contain allyl or acrylyl functional groups, as described in U.S. Patent 5,200,483 describes; Poly (vinyl acetate), polyvinylbutyral, polyurethane, Polymers of members of the group consisting of diethylene glycol dimethacrylate monomers, Diisopropenyl benzene, ethoxylated bisphenol A dimethacrylate monomers, Ethylenglycolbismethacrylatmonomeren, poly (ethlyenglycol) bismethacrylatmonomeren, ethoxylated phenol and ethoxy lated trimethylol propane triacrylate; Cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, Polystyrene and copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile.

Especially consider drawn to the use of photochromic indenonaphthopyrans of the present invention together with optical organic resin monomers, which are used to produce optically clear polymerizates, ie, materials suitable for optical applications, such. as plano lenses and spectacle lenses, windows and transparent materials in automobiles. Such optically clear polymers can have a refractive index ranging from about 1.48 to 1.75, for example, from 1.495 to 1.66. are specifically contemplated optical Resins sold by PPG Industries, Inc. under the designation CR-307 and CR-407th

Although the present invention with reference to specific details of their particular embodiments has been described, it is not intended that such details as limitations for the scope of the invention be considered other than that and to the extent that they are included in the accompanying claims.