MXPA01002555A - Polyalkoxylated naphthopyrans - Google Patents

Abstract

Described are novel photochromic polyalkoxylated naphthopyran compounds, examples of which are certain 2H-naphtho[1,2-b]pyrans, 3H-naphtho[2,1-b]pyrans and indeno[2,1-f]naphtho[1,2-b]pyrans, each having at least one polyalkoxylated substituent of from 2 to 50 alkoxy units per substituent. Specific substituents may also be present on the naphtho, indeno and pyrano portions of the compounds. These compounds may be represented by graphic formulae (I), (II) or (III). Also described are various substrates, e.g., paper, glass, organic polymeric materials, etc., that contain or that are coated with such compounds. Optically clear articles such as ophthalmic lenses or other plastic transparencies that incorporate the novel naphthopyran compounds or combinations thereof with complementary photochromic compounds, e.g., certain other naphthopyrans, indenonaphthopyrans, benzopyrans, oxazine-type compounds, etc., are also described.

Description

POLYCOXYLATED NAFTOPIRANS DESCRIPTION OF THE INVENTION The present invention relates to certain novel naphthopyran compounds. More particularly, this invention relates to photochromic polyalkoxylated naphthopyran compounds and compositions and articles containing such novel photochromic compounds. When exposed to electromagnetic radiation containing ultraviolet rays, such as ultraviolet radiation in sunlight or light from a mercury lamp, many photochromic compounds show a reversible color change. When ultraviolet radiation is suspended, such a photochromic compound returns to its original color or its colorless state. Various classes of photochromic compounds have been synthesized and have been suggested for use in applications where a reversible color change induced by sunlight is desired. U.S. Patent No. 3,567,605 (Becker) discloses a series of pyran derivatives, including certain benzopyrans and naphthopyrans. U.S. Patent No. 5,658,500 (Kumar), WO 95/16215 (Kumar) and WO 97/21698 (Kumar) discloses reversible photochromic 2H-naphtho [2, lb] pyrano compounds having an acceptable fade rate in addition of a high activated intensity and a high coloring speed. WO 97/22895 (Kumar) describes 3 H -naphtho [2, 1-b] pyran compounds. Transparent photochromic articles made of a polymeric organic host material incorporated with these compounds have less residual color and higher luminous transmittance in the activated state as compared to the incorporated photochromic articles with the corresponding compounds. WO 97/20239 (Van Gemert) discloses 3 H-naph or [2, 1-b] pyran compounds having an improved solar response and a higher activation wavelength. U.S. Patent No. 5,458,814 discloses 2,2-di-substituted-5,6-substituted-2H-naph or [1, 2-b] pyran monochromic compounds primarily for use in lenses and other plastic transparencies. These compounds have an acceptable fade rate in addition to a high activated intensity and a high coloration rate. US Patent No. 5,585,042 discloses 3,3-di-substituted-8-substituted-3H-naphtho [2, 1-b] pyran compounds for similar uses. These compounds show an improved solar response, a longer activation wavelength compared to unsubstituted naphthopyrans and an acceptable bleached or fading rate. U.S. Patent No. 5,645,767 discloses photochromic indene [2, 1-f] apto [1, 2-b] pyrans having high activated intensity, an acceptable dyeing rate and a high dyeing rate. Although the 3H-naphtho [2, 1-b] pyrans, 2H-naphtho [1,2-b] pyrans and indeno [2, 1-f] naphtho [1, 2-b] pyrans of good intensity and reasonable fading are Currently available, it is desirable to improve the fade rate of the photochromic compound without changing its activated color. This can be done either to match the same properties of complementary photochromic compounds or to allow the use of such compounds in rigid plastic matrices, where the activation / fading kinetics of the photochromic compounds often decrease. In accordance with the present invention, novel photochromic compounds have been discovered; specifically certain 2H-naphtho [2, 1-b] pyrans, 3H-naphtho [1,2-b] pyrans and indeno [2, 1-f] naphtho [1,2-b] pyrans having at least one substituent polyalkoxylated The presence of the polyalkoxylated substituent results in an improved bleached or bleached rate compared to the naphthopyrans having a single alkoxy substituent. Of equal importance, the activated colors do not change with this substitution. Depending on the location of the polyalkoxylated substituent, some other substituents may also be present in the naphtho, pyran and indene portions of the compounds described above.

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, it has been found that the rate of destaining of certain 2H-naphtho [2, 1-b] pyrans, 3H-naphtho [1,2-b] pyrans and indeo [2, 1-f] naphtho [1, 2-b] photochromic pyrans can now be improved by including at least one polyalkoxylated substituent in such compounds. The polyalkoxylated substituent can have from 2 to 50 alkoxy units and can be located in the naphtho or indene portion or in the pyran portion of the naphthopyran. The naphthopyrans of the present invention may also have certain additional substituents. Specifically, the 2H-naph opyrans may have substituents at positions 5 and 6 and may have additional substituents at positions 7, 8, 9 and 10; 3H-naphthopyrans may have substituents at positions 8 and 9 and may have additional substituents at positions 5 and 6; and the naphthopyrans fused to indene may have certain substituents at positions 5, 6, 7, 8, 9, 10, 11, 12 or 13. The naphthopyrans described in the foregoing may be represented by graphic formulas I, II and III, respectively, in which the internal ring numbers 1 to 13 identify the numbering of the ring atoms of the naphthopyrans and the letters aan represent the sides of the naphthopyran rings. In the definition of substituents that are shown in the following graphic formulas I, II and III, similar symbols have the same meaning unless stated otherwise.

II III In graphic formulas I, II and III R1 (R2, R3, R4, Rs or R6 can be the group R represented by the formula: -A [(C2H40) x (C3H60) and (C4H80) z] D, in where -A is -C (0) 0, -CH20 or -O and D is alkyl of 1 to 3 carbon atoms, provided, however, that only one R group is present in the naphtho or indene portion of the Naphthopyran The group - (C2H40) x- represents poly (ethylene oxide) - (C3H60) y- represents poly (propylene oxide) and - (C4H80) z- represents poly (butylene oxide). When used in combination, the poly (ethylene oxide), poly (propylene oxide) and poly (butylene oxide) groups of R may be in a random or block order within the R portion. The letters x, y and z they are each a number between 0 and 50 and the sum of x, y and z is between 2 and 50. The sum of x, y and z can be any number within the range of 2 to 50, for example 2, 3, 4. ..50 This sum can also vary from any number or lower than any higher number within the range of 2 to 50, for example 6 to 50, 31 to 50. The numbers for x, y and z are average values and may be partial numbers, for example 9.5. Preferably, Rlf R2, R3, R4, R5 or R6 is the group R, wherein X and Y are each a number between 0 and 50, z and O and the sum of x and y is between 2 and 50, more preferably , x is a number between 2 and 50, e and yz are each 0. Alternatively, the substituents Ra, R2, R3, R4, R5 or R6 in the graphic formulas I, II and III may be a different group of R; with the proviso that one such substituent is the group R. Rj_ can be hydrogen, alkyl of 1 to 3 carbon atoms or the group, -C (0) W, W is -OR7, -N (R8) R9, piperidino or morpholino, wherein R7 is allyl, alkyl of 6 carbon atoms, phenyl, phenyl substituted with monoalkyl of 1 to 6 carbon atoms, phenyl substituted with monoalkoxy of 1 to 6 carbon atoms, phenylalkyl of 1 to 3 atoms of carbon, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkyl of 1 to 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkoxy of 1 to 6 carbon atoms, alkoxy (of 1 to 6 carbon atoms) ) alkyl of 2 to 4 carbon atoms or haloalkyl of 1 to 6 carbon atoms; R8 and R9 are each selected from the group consisting of alkyl of 1 to 6 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl and monosubstituted or disubstituted phenyl, the phenyl substituents are alkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms, and the halo substituent is chloro or fluoro. Preferably, Rx is the group -C (0) W, W is -OR7 or -N (Rβ) R9, wherein R7 is alkyl of 1 to 4 carbon atoms, phenyl, phenyl substituted with monoalkyl of 2 to 4 carbon atoms, carbon, phenyl substituted with monoalkoxy of 1 to 4 carbon atoms, phenylalkyl of 1 to 2 carbon atoms, phenylalkyl of 1 to 2 carbon atoms substituted with monoalkyl of 1 to 4 carbon atoms, phenylalkyl of 1 to 2 carbon atoms substituted with monoalkoxy of 1 to 4 carbon atoms, monoalkoxy (of 1 to 4 carbon atoms) alkyl of 2 to 3 carbon atoms or haloalkyl of 1 to 4 carbon atoms; R8 and R9 are each selected from the group consisting of alkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl and monosubstituted or disubstituted phenyl, phenyl substituents are alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, and the halo substituents are chloro or fluoro. More preferably, R1 is the group -C (0) W, W is -0R7, wherein R7 is alkyl of 1 to 3 carbon atoms. R2, each R3 and R4 may be selected from the group consisting of hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, phenyl, monosubstituted or disubstituted phenyl, and the groups -OR10, and -OC (0) R10, wherein R10 is alkyl of 1 to 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkyl of 1 to 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkoxy of 1 to 6 carbon atoms, alkoxy (of 1 to 6 carbon atoms) alkyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 7 carbon atoms or cycloalkyl of 3 to 7 carbon atoms carbon substituted with monoalkyl of 1 to 4 carbon atoms, n is selected from the integers 0, 1 and 2 and the phenyl substituents are the same as for Rx. Preferably, R2 each R3 and R4 are selected from the group consisting of hydrogen, alkyl of 1 to 3 carbon atoms, cycloalkyl of 3 to 5 carbon atoms, phenyl, monosubstituted or disubstituted phenyl and the group -OR10, wherein R10 is alkyl of 1 to 4 carbon atoms, phenylalkyl of 1 to 2 carbon atoms, phenylalkyl of 1 to 2 carbon atoms substituted with monoalkyl of 1 to 4 carbon atoms, phenylalkyl of 1 to 2 carbon atoms substituted with monoalkoxy of 1 to 4 carbon atoms, alkoxy (of 1 to 4 carbon atoms) alkyl of 2 to 4 carbon atoms, cycloalkyl of 5 to 7 carbon atoms or cycloalkyl of 5 to 7 carbon atoms substituted with monoalkyl of 1 to 3 atoms of carbon, and the phenyl substituents are alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms. More preferably, R2, each R3 and R4 are selected from the group consisting of hydrogen, alkyl of 1 to 3 carbon atoms, phenyl, monosubstituted or disubstituted phenyl and the group -OR10, wherein R10 is alkyl of 1 to 3 Carbon atoms and phenyl substituents are methyl or methoxy. Rs and R6 together can form an oxo group, a spiro-heterocyclic group containing 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, which can be represented by the expression (-0- (alkanediyl 2 to 5 carbon atoms) -0-), for example spiro-1,3-dioxolane-2, spiro-1,3-dioxane-2, etc., or R5 and R6 can each be hydrogen, hydroxy, 1 to 6 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, allyl, phenyl, monosubstituted phenyl, benzyl, monosubstituted benzyl, chloro, fluoro, the group -C (0) X, wherein X is hydroxy, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, phenyl, monosubstituted phenyl, amino, monoalkylamino of 1 to 6 carbon atoms or dialkylamino of 1 to 6 carbon atoms, for example dimethylamino, methylpropylamino, et cetera, or Rs and R6 may each be the group -OR ^, wherein RX1 is alkyl of 1 to 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms no, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkyl of 1 to 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkoxy of 1 to 6 carbon atoms, alkoxy (of 1 to 6 carbon atoms) alkyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, cycloalkyl of 3 to 7 carbon atoms substituted with monoalkyl of 1 to 4 carbon atoms, chloroalkyl of 1 to 6 carbon atoms, fluoroalkyl of 1 to 6 carbon atoms, allyl, the group -CH (R12) Y, wherein R12 is hydrogen or alkyl of 1 to 3 carbon atoms and Y is CN, CF3 or COOR13 and R13 is hydrogen or alkyl of 1 to 3 carbon atoms; carbon, or RX1 is the group -C (0) Z, wherein Z is hydrogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, unsubstituted, monosubstituted or disubstituted aryl groups, phenyl or naphthyl, phenoxy, phenoxy mono or disubstituted with alkyl of 1 to 6 carbon atoms, phenoxy substituted with mono or dialkoxy of 1 to 6 carbon atoms, phenoxy substituted with mono- or dialkoxy of 1 to 6 carbon atoms, amino, monoalkylamino of the 6 carbon atoms, dialkylamino of 1 to 6 carbon atoms, phenylamino, phenylamino substituted with mono- or dialkyl of 1 to 6 carbon atoms, or phenylamino substituted with mono- or dialkoxy of 1 to 6 carbon atoms, each one of the substituents of the phenyl, benzyl and aryl group described above is alkyl of 1 to 6 carbon atoms or alkoxy of 6 carbon atoms. More preferably, R5 and R6 are each selected from the group consisting of hydrogen, hydroxy, alkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, chloro, fluoro and the group -0R11 (in the that R1X is alkyl of 1 to 3 carbon atoms, phenylalkyl of 1 to 2 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkyl of 1 to 3 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkoxy from 1 to 3 carbon atoms, alkoxy (from 1 to 3 carbon atoms) alkyl from 2 to 4 carbon atoms, chloroalkyl from 1 to 3 carbon atoms, fluoroalkyl from 1 to 3 carbon atoms, the group -CH ( R12) Y, wherein R12 is hydrogen or alkyl of 1 to 2 carbon atoms and Y is CN or COOR13, R13 is hydrogen or alkyl of 1 to 2 carbon atoms, or R1X is the group, -C (0) Z, wherein Z is hydrogen, alkyl of 1 to 3 carbon atoms, alkoxy of 3 carbon atoms, phenyl, naphthyl, the monosubstituted aryl groups phenyl or naphthyl, phenoxy, phenoxy substituted with mono- or dialkyl of 1 to 3 carbon atoms, phenoxy substituted with mono- or dialkoxy of 1 to 3 carbon atoms, monoalkylamino of 1 to 3 carbon atoms, phenylamino, phenylamino substituted with mono- or di-alkyl of 1 to 3 carbon atoms or phenylamino substituted with mono- or dialkoxy of 1 to 3 carbon atoms, each of the substituents of the aryl group is alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms. More preferably, Rs and R6 are each hydrogen, hydroxy, alkyl of 1 to 4 carbon atoms or the group -ORn, wherein R1X is alkyl of 1 to 3 carbon atoms. B and B 'are each selected from the group consisting of: (a) phenyl monosubstituted with R represented by the following graphic formula IV: IV where the group. R is the same as previously described; (b) unsubstituted, monosubstituted, disubstituted and trisubstituted aryl groups, phenyl and naphthyl; (c) the unsubstituted, monosubstituted and disubstituted heteroaromatic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazolyl and fluorenyl, each of the aryl and heteroaromatic substituents in subparagraphs (b) and (c) is selected from the group consisting of hydroxy, aryl, ie, phenyl and naphthyl, monoalkoxyaryl of 1 to 6 carbon atoms, dialkoxyaryl of 1 to 6. carbon atoms, monoalkylaryl of 1 to 6 carbon atoms, dialkylaryl of 6 carbon atoms, chloroaryl, fluoroaryl, cycloalkylaryl of 3 to 7 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, cycloalkyloxy of 3 to 7 carbon atoms carbon, cycloalkyloxy (of 3 to 7 carbon atoms) alkyl of 1 to 6 carbon atoms, cycloalkyloxy (of 3 to 7 carbon atoms) alkoxy of 1 to 6 carbon atoms, arylalkyl of 1 to 6 carbon atoms, arylalkoxy from 1 to 6 carbon atoms, aryloxy, aryloxy alkyl of 1 to 6 carbon atoms, aryloxyalkoxy of 1 to 6 carbon atoms, mono- and dialkyl (of 1 to 6 carbon atoms) arylalkyl of 6 carbon atoms, mono- and di-alkoxy (from 1 to 6) carbon atoms) arylalkyl of 1 to 6 carbon atoms, mono- and di-alkyl (of 6 carbon atoms) arylalkoxy of 1 to 6 carbon atoms, mono- and di-alkoxy (of 1 to 6 carbon atoms) ) arylalkoxy of 1 to 6 carbon atoms, amino, monoalkylamino of 1 to 6 carbon atoms, dialkylamino of 1 to 6 carbon atoms, diarylamino, N-alkylpiperazino of 1 to 6 carbon atoms, N-arylpiperazino, aziridino, indolino , piperidino, arylpiperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 6 carbon atoms, fluoroalkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms , monoalkoxy (of 1 to 6 carbon atoms) alkyl of 1 to 4 carbon atoms, acryloxy, methacryloxy, bromine, chlorine and fluorine; (d) the groups represented by the following graphic formulas VA and VB: VA VB wherein E is -CH2- or oxygen and G is oxygen or substituted nitrogen, with the proviso that when G is substituted nitrogen, E is -CH2-, the nitrogen substituents are selected from the group consisting of hydrogen, alkyl of 1 to 6 carbon atoms and acyl of 2 to 6 carbon atoms; each R 14 is alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, hydroxy, chloro or fluoro; R15 and R16 are each hydrogen or alkyl of 1 to 6 carbon atoms; and q is the integer 0, 1 or 2; (e) alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 6 carbon atoms, fluoroalkyl of 1 to 6 carbon atoms, alkoxy (of 1 to 6 carbon atoms) alkyl of 1 to 4 carbon atoms; and (f) the group represented by the following graphic formula VC: C = C] M VC wherein L is hydrogen or alkyl of 1 to 4 carbon atoms and M is selected from the unsubstituted, monosubstituted and disubstituted members of the group consisting of naphthyl, phenyl, furanyl and thianyl, each of the substituents of the group being alkyl 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, fluoro or chloro. Preferably, B and B1 are each selected from the group consisting of: (a) phenyl monosubstituted with R; (b) phenyl, monosubstituted and disubstituted phenyl; (c) unsubstituted, monosubstituted and disubstituted heteroaromatic groups, furanyl, benzofuran-2-yl, thianyl, benzothien-2-yl, dibenzofuran-2-yl and dibenzothien-2-yl, each of the phenyl substituents and heteroaromatics in subsections (b) and (c) is selected from the group consisting of hydroxy, aryl, aryloxy, arylalkyl of 1 to 3 carbon atoms, amino, monoalkylamino of 1 to 3 carbon atoms, dialkylamino of 1 to 3 carbon atoms, N-alkylpiperazino of 1 to 3 carbon atoms, indolino, piperidino, morpholino, pyrryl, alkyl of 3 carbon atoms, chloroalkyl of 1 to 3 carbon atoms, fluoroalkyl of 1 to 3 carbon atoms, alkoxy of 1 to 3 carbon atoms, monoalkoxy (from 1 to 3 carbon atoms) alkyl of 1 to 3 carbon atoms, chlorine and fluoro; (d) the groups represented by the graphic formulas VA and VB, wherein E is -CH2- and G is oxygen, R14 is alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms; each of R15 and R16 are hydrogen or alkyl of 1 to 4 carbon atoms; and q is 0 or 1; (e) alkyl of 1 to 4 carbon atoms, - (f) the group represented by graphic formula VC wherein L is hydrogen or methyl and M is phenyl or monosubstituted phenyl and the phenyl substituent is alkyl of 1 to 3 carbon atoms. carbon, alkoxy of 1 to 3 carbon atoms or fluoro. More preferably, B and B 'are each selected from the group consisting of: (a) phenyl monosubstituted with R; (b) phenyl, monosubstituted and disubstituted phenyl preferably substituted at the meta or para positions, or both; (c) unsubstituted, monosubstituted and disubstituted heteroaromatic groups, furanyl, benzofuran-2-yl, thienyl and benzothien-2-yl, each of the phenyl and heteroaromatic substituents in subparagraphs (b) and (c) is selected from a group consisting of hydroxy, alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 3 carbon atoms, phenyl, indolino, fluoro and chloro; (d) the group represented by the graphic formulas VA wherein E is -CH2- and G is oxygen, R14 is alkyl of 1 to 3 carbon atoms, or alkoxy of 1 to 3 carbon atoms; R15 and R16 are each hydrogen or alkyl of 1 to 3 carbon atoms; and q is 0 or 1. The compounds represented by the graphic formulas I, II and III can be prepared by the following steps. In reaction A, a poly (ethylene glycol) methyl ether represented by general formula IV (where x is the same as for group R) or another different poly (alkylene glycol) methylether is reacted with toluenesulfonyl chloride represented by graphic formula VII in the presence of triethylamine (TEA) to produce the methoxy (polyethoxy) -p-toluenesulfonate represented by graphic formula VIII. Another process for producing the compound of the graphic formula VIII is described by Bradshaw, J.S. et al., "Synthesis of Macrocyclic Acetáis Containing Lipophilic Substituents", Tetrahedron, vol. 43, No. 19, pp 4271 to 4276, 1987, the disclosure of which is incorporated herein by reference.

REACTION TO VII VIII In Reaction B, the alkoxylated toluenesulfonate represented by the graphic formula VIII is reacted with a naphthopyran represented by the graphic formula IX in the presence of anhydrous potassium carbonate and heat to form the alkoxylated naphthopyran of the graphic formula IA. Alternatively, the halogenated alkoxylated alcohols can be used in place of the alkoxylated toluene sulfonate to alkylate the hydroxy functionality using the reaction conditions mentioned above. Alkylating reactions are further described in Organic Synthesis, Vol. 31, pages 90-93, John Wiley & Sons, Inc., New York, New York. The compound represented by graphic formula IX can be prepared by coupling a naphthol substituted with a propargyl alcohol. This process is described in U.S. Patent No. 5,458,814, column 5, line 10 to column 7, line 38. Propargyl alcohol can be prepared according to the methods described in U.S. Patent No. 5,645,767, column 5, line 8 to column 6, line 30. The patents mentioned above are incorporated herein by reference.

REACTION B VIII IX IA In reaction C, a substituted naphthoic acid, represented by graphic formula X, is reacted with a poly (ethylene glycol) methyl ether represented by general formula VI using concentrated sulfuric acid and heat to form the alkoxylated naphthol represented by graphic formula XI . In graphic formula X, R2 and R3 are as previously defined. The alkoxylated naphthol represented by graphic formula XI is coupled with the propargyl alcohol represented by graphic formula XII to form the alkoxylated naphthopyran represented by graphic formula IB.

REACTION C COOH COO - [C2H40) x] - CH3 IB In reaction D, the alkoxylated toluenesulfonate represented by graphic formula VII is reacted with a benzophenone substituted with hydroxy represented by graphic formula XIII to form the alkoxylated benzophenone represented by graphic formula XIV. The alkoxylated benzophenone is reacted with sodium acetylide in a suitable solvent, such as anhydrous tetrahydrofuran (THF), to form the corresponding propargyl alcohol represented by graphic formula XV. Propargyl alcohol (XV) is coupled with the substituted naphthol of the graphic formula XVI to form the alkoxylated naphthopyran represented by graphic formula IIA.

REACTION D HA In reaction E, the alkoxylated toluenesulfonate represented by graphic formula VIII is reacted with an acetophenone, benzophenone or benzaldehyde, substituted with hydroxy, represented by graphic formula XVII to form the corresponding alkoxylated acetophenone, benzophenone or benzaldehyde. The compound of graphic formula XVIII is reacted with an ester of succinic acid such as dimethyl succinate represented by graphic formula XIX. In addition to the reactants to a solvent, for example toluene, which contains potassium t-butoxide or sodium hydride as the base, provides the Stobbe condensation of the half ester represented by graphic formula XX. The half ester (XX) undergoes cyclodehydration in the presence of acetic anhydride to form the alkoxylated acetoxynaphthalene represented by graphic formula XXI. This product is reacted with hydrochloric acid (H +) and an anhydrous alcohol such as anhydrous methanol to form the corresponding naphthol represented by graphic formula XXII. Naphthol (XXII) is coupled with a propargyl alcohol represented by graphic formula XII to form the alkoxylated naphthopyran represented by graphic formula IC.

REACTION E vm xvp xvm Stobbe reaction IC In reaction F, the compound represented by graphic formula XXIII is reduced with lithium aluminum hydroxide (LAH) to produce the compound represented by graphic formula XXIV. The processes for preparing the compound of the graphic formula XXIII are described in U.S. Patent No. 5,645,767 to which reference is made above. A poly (ethylene glycol) methyl ether represented by the general formula VI (wherein x is the same as for the group R) is reacted with the compound of the graphic formula XXIV using an acid (H +) to form the naphthopyran fused with the alkoxylated indene of the graphic formula IIIA.

REACTION F XXIII XXIV IIIA The alkoxylated naphthopyran compounds represented by the graphic formulas I, IA, IB, IC, II HA, III and IIIA can be used in those applications in which organic photochromic substances such as optical lenses can be used, for example ophthalmic lenses to correct Vision and Flat Lenses, Face Covers, Goggles, Sight Glasses, Camera Lenses, Windows, Car Windshields, Aircraft and Car Transparencies, for example, T-roofs, Slate and Taillights, Movies plastics and foils, textiles and coatings, for example coating compositions. As used herein, coating compositions include polymeric coating compositions prepared from materials such as polyurethanes, epoxy resins and other resins used to produce synthetic polymers; paints, that is, a pigmented liquid or paste used for decoration, protection or identification of a substrate, and inks, that is, a pigmented liquid or paste used for writing and printing on substrates, which includes paper, glass, ceramic materials , wood, masonry, textiles, metals and polymeric organic materials. The coating compositions can be used to produce check marks on security documents, for example documents such as checks, passports and driver's licenses, for which authenticity authentication or verification may be desired.

Depending on the degree of alkoxylation, the photochromic compounds of the present invention can be soluble in water, ie, soluble in the amount of at least 1 gram per liter. The water solubility of any of the photochromic compounds of the present invention provides handling and processing advantages that are not obtained by photochromic and water soluble compounds. In particular, the use of hazardous organic solvents as carriers for photochromic compounds is avoided. The use of such solvents in the cleaning of excess photochromic material from the surface of polymeric substrates after an imbibition or transfer process is also avoided. The 2H-naphtho- [1, 2-b] pyrans represented by graphic formula I show color changes from colorless to colors ranging from yellow to red / purple. The 3H-naphtho [2, 1-b] pyrans represented by graphic formula II show color changes from colorless to colors ranging from yellow to orange and red. The indeno [2,1-f] naphtho [1,2-b] pyrans represented by the graphic formulas III show color changes from colorless to colors ranging from orange to blue / gray. Examples of the naphthopyrans contemplated within the scope of the invention are the following: (a) 2,2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6-methoxy (polyethoxy) (16EO) - [2H] -naphtho [ 1, 2-b] pyran; (b) 2,2-diphenyl-5- (2- (2-methoxyethoxy) ethoxycarbonyl) -6-phenyl- [2 H] -naphtho [1,2-b] pyran; (c) 2, 2-d i f e n i l -5- (2 - (2 - (2-methoxyethoxy) ethoxy) ethoxycarbonyl) -6-methyl- [2 H] -naphtho [1,2-b] pyran; (d) 2, 2-d i f e n i 1 -5- (2 - (2 - (2-methoxyethoxy) ethoxy) ethoxycarbonyl) -6-phenyl- [2 H] -naphtho [1,2-b] pyran; (e) 2-2-Diphenyl-5-carbomethoxy-9- (2- (2- (2-methoxyethoxy) ethoxy) propyloxy) - [2 H] -naphtho [1,2-b] pyran; (f) 3-f e n i l -3- (4 - (2 - (2 - (2-methoxyethoxy) ethoxy) ethoxy) phenyl) - [3 H] -naphtho [1,2-b] pyran; (g) 3,3-di (4-methoxyphenyl) -6,11, 13-trimethyl-13- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) -indeno [1,2-f] naphtho [ 1, 2-b] pyran; (h) 3-phenyl-3- (4- (2- (2- (2-methoxy-ethoxy) ethoxy) ethoxy) phenyl) -8-methoxy-9- (2- (2- (2-methoxyethoxy) ethoxy ) ethoxycarbonyl) - [3 H] -naphtho [2, 1-b] pyran; and (i) 3-phenyl-3- (4-morpholinophenyl) -6- (2- (2-methoxyethoxy) ethoxy) -11, 13 -dimethyl-13-hydroxy-indene [2, 1-f] naphthol [1,2-b] pyran. It is contemplated that the photochromic naphthopyrans of the present invention may be used alone, in combination with other naphthopyrans of the present invention or in combination with one or more appropriate complementary organic photochromic materials, ie organic photochromic compounds having at least an absorption maximum activated within the range of between approximately 400 and 700 nanometers (or substances containing them) and which exhibit color when activated at an appropriate tone. Examples of complementary organic photochromic compounds include other naphthopyrans and indene naptopyrans, chromosomes and oxazines, 2 H -phenanthr [4, 3-b] pyran and 3 H -phenanthr [1,2-b] pyran substituted compounds, benzopyran compounds having substituents at the 2-position of the pyran ring and mixtures of such photochromic compounds. Such photochromic compounds are described 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; 5,238,981 5,274,132; 5,384,077; 5,405,958; 5,429,774 5,458,814; 5,466,398; 5,514,817; 5,552,090; 5,552,091 5,565,147; 5,573,712; 5,578,252; 5,637,262; 5,645,767 5,656,206; 5,658,500; 5,658,501; 5, 674, 432 and 5, 698, 141. Spiro (indoline) pyrans are also described in the text, Techniques in Chemistry. Volume III, "Photochromism", chapter 3, Glenn H. Brown, Editor, John Wiley and Sons, Inc., New York, 1971. The complementary organic photochromic materials may also include polymerizable photochromic compounds such as those described in the Patents of the United States Nos. 4,719,296; 5,166,345; 5,236,958; 5,252,742; 5,359,035 and 5,488,119. Other complementary photochromic substances contemplated are metal dithiozoates, for example mercury dithiozoates which are described, for example, in US Pat. No. 3,361,706; and fulgides and fulgimides, for example the fulgimides and fulgimides of 3-furyl and 3-thienyl which are described in U.S. Patent No. 4,931,220 in column 20, line 5 to column 21, line 38. The descriptions in relation to such photochromic compounds in the aforementioned patents are hereby incorporated, in toto, as a reference. The photochromic articles of the present invention may contain a photochromic compound or a mixture of photochromic compounds, as desired. The photochromic compounds of the present invention can be associated with a polymeric organic host material or other substrate, by various means. They can be incorporated, i.e., dissolved or dispersed, in the host material or they can be incorporated in a coating applied to a substrate, for example a polymer coating applied to a surface of the polymeric organic host material. Unless otherwise indicated, all numbers expressing values, such as wavelengths, ingredient amounts or reaction conditions used herein must be understood to be modified, in all cases, by the term "approximately " Each of the photochromic substances described herein can be used in amounts (or in a ratio) such that an organic host material to which the photochromic compounds or the mixture of compounds are applied or in which they are incorporated, show a desired resultant color, for example, a substantially neutral color when activated by unfiltered sunlight, that is, as close as possible to a neutral color providing the colors of the activated photochromic compounds. Neutral gray and neutral brown colors are preferred. An additional discussion of the neutral colors and ways of describing such colors can be found in U.S. Patent No. 5,645,767, column 12, line 66 to column 13, line 19. The amount of the photochromic naphthopyrans that are going to applying or to be incorporated into a carrier or host material are not critical on the condition that a sufficient amount is used to produce a photochromic effect discernible to the naked eye when activated. Generally, such an amount can be described as a photochromic amount. The particular amount used often depends on the intensity of color desired before the irradiation thereof and the method used to incorporate or apply the photochromic compounds. Typically, the more photochromic compound is applied or incorporated, the greater the color intensity up to a certain limit. The relative amounts of the above photochromic compounds used will vary and will depend in part on the relative intensities of the color of the activated species of such compounds, and the desired final color. Generally, the amount of total photochromic compound incorporated or applied to a photochromic optical host material can vary from about 0.05 to about 1.0., for example, from 0.1 to approximately 0.45 milligrams per square centimeter of volume or surface, to which the photochromic compounds are incorporated or applied. The amount of photochromic material incorporated in the coating composition can vary from 0.1 to 40% by weight based on the weight of the liquid coating composition. The photochromic naphthopyrans of the present invention can be associated with the host material by various methods described in the art. See, for example, column 13, lines 40 to 58 of U.S. Patent No. 5,645,767. The aqueous or organic solutions of the photochromic compounds can be used to incorporate the photochromic compounds into a polymeric organic host material or other materials such as textiles and polymeric coating compositions. The polymeric coating compositions can be applied to the substrate using a coating process such as that described in U.S. Patent No. 3,971,872, the disclosure of which is incorporated herein by reference. The application of the polymeric coating can be by any of the methods used in the coating technology such as, for example, coating by spraying, coating by centrifugation, coating by dispersion, coating by curtain, coating by immersion, coating by casting or roller and methods used in the preparation of overlays, such as the method of type described in U.S. Patent No. 4,873,029, which is incorporated herein by reference. The selected application method also depends on the thickness of the cured coating. The coating has a thickness ranging from 1 to 50 micrometers and can be applied by conventional methods used in coating technology. Coatings thicker than 50 microns may require molding methods typically used for overlays. Neither the host material will usually be transparent, but it can be translucent or even opaque. The host material only needs to be permeable to that portion of the electromagnetic spectrum which activates the photochromic substance, that is, that wavelength of ultraviolet (UV) light that produces an open or colored form of the substance and that portion of the visible spectrum which includes the maximum wavelength of absorption of the substance in its form activated by UV radiation, that is, the open form. Preferably, the host color should not be such that it masks the color of the activated form of the photochromic compounds, i.e., so that a color change for the observer is readily apparent. Compatible inks can be applied to the host material as described in U.S. Patent No. 5,645,767 in column 13, line 59 to column 14, line 3. Examples of polymeric organic host materials which can be used with the photochromic compounds described herein include: polymers, ie homopolymers and copolymers of the bis (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethyl methacrylate monomers , poly (ethylene glycol) bismetacrylate monomers, ethoxylated phenol bismetacrylate monomers, alkoxylated polyhydric alcohol acrylate monomers such as ethoxylated trimethylol propane triacrylate monomers, acrylate and urethane monomers such as those described in U.S. Pat. 5,373,033, and vinylbenzene monomers such as or those described in U.S. Patent No. 5,465,074 and styrene; polymers, that is, homopolymers and copolymers of polyfunctional acrylate or methacrylate monomers, for example monofunctional, difunctional or multifunctional, poly (alkyl methacrylate of 1 to 12 carbon atoms), such as pol i (methyl methacrylate), poly (oxyalkylene) dimethacrylate, 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), polyurethanes, polythiourethanes, thermoplastic polycarbonates, polyesters, poly (ethylene terephthalate), polystyrene, poly (alpha methylstyrene), copoly (styrene-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinylbutyral and polymers, that is, diallylidene pentaerythritol homopolymers and copolymers, particularly copolymers with polyol monomers (allyl carbonate), for example diethylene glycol bis (allyl carbonate), and acrylate monomers, for example ethyl acrylate, butyl acrylate. Additional examples of polymeric organic host materials are described in U.S. Patent No. 5,753,146, column 8, line 62 to column 10, line 34, the disclosure of which is incorporated herein by reference.

Transparent copolymers and clear polymer combinations are also suitable as host materials. Preferably, the host material or substrate for the photochromic polymeric coating composition is an optically clear polymerized organic material that is prepared from a thermoplastic polycarbonate resin such as the carbonate bound resin derived from bisphenol A and phosgene, which is sold under the trademark LEXAN; a polyester, such as the material sold under the MYLAR trademark; a poly (methyl methacrylate), such as the material sold under the trademark PLEXIGLÁS; polymers of a polyol monomer (allyl carbonate) especially diethylene glycol bis (allyl carbonate), monomer which is sold under the trademark CR-39, and polymerized copolymers of a polyol (allyl carbonate), for example diethylene glycol bis (allyl carbonate) with other copolymerizable monomeric materials such as copolymers with vinyl acetate, for example copolymers of 80-90 percent of diethylene glycol bis (allyl carbonate) and 10-20 percent vinyl acetate, particularly 80-85 percent of bis (allyl carbonate) and 15-20 percent of vinyl acetate, and copolymers with a polyurethane having a terminal diacrylate functionality, as described in U.S. Patent Nos. 4,360,653 and 4,994,208; and copolymers with aliphatic urethanes, the terminal portion of which contains allyl or acrylyl functional groups, as described in U.S. Patent No. 5,200,483; poly (vinyl acetate), polyvinyl butyral, polyurethane, polythiourethanes, polymers of members of the group consisting of diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismethyl methacrylate monomers, poly (ethylene glycol), ethoxylated phenol bismetacrylate monomers and ethoxylated trimethylol propane triacrylate monomers; cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile. More particularly, the use of the photochromic naphthopyrans of the present invention is contemplated with organic organic resin monomers used to produce optically transparent coatings and polymerizations, ie, materials suitable for optical applications such as, for example, lenses, ie, lenses flat and ophthalmic. The optically clear polymerizations can have a refractive index which can vary from about 1.48 to about 1.75, for example, from about 1495 to about 1.66. Specifically contemplated are the polymer resins of optical resins measured by PPG Industries, Inc. under the designation CR-, for example CR-307 and CR-407. The present invention is described more particularly in the following examples which are intended to be illustrative only, since numerous modifications and variations will be apparent to those skilled in the art.

EXAMPLE 1 STAGE 1 Poly (ethylene glycol) methyl ether (35 grams, 0.1 mole) having an average molecular weight number of about 350 is added and an equivalent of 19 grams of toluenesulfonyl chloride is added to a reaction flask containing 150 ml of chloroform and a slight excess of 11 grams of triethylamine. The resulting mixture is heated to reflux temperature and maintained at that temperature overnight. After cooling to room temperature, the reaction mixture is added to a beaker containing an equal volume of water. The resulting organic layer is separated and the solvent, chloroform, is removed under vacuum to provide methoxy (polyethoxy) -p-toluenesulfonate having an average molecular weight of 504. This material is not purified but is used directly in the next step.

STAGE 2 The product of step 1 (5 grams, 0.01 mole) is added to a reaction flask containing 50 mL of acetone, one molar equivalent of 2,2-bis [4-methoxyphenyl] -5-methoxycarbonyl-6-hydroxyethyl ester. 2H-naphtho [1,2-b] pyran (4.4 grams, 0.01 mole) which is the compound of Example 1 of U.S. Patent 5,458,814, and 2 grams of powdered potassium carbonate. The resulting reaction mixture is heated to reflux and maintained at that temperature overnight. The solvent, acetone, is removed by vacuum and the resulting residue is dissolved in chloroform and subjected to chromatography using a column of silica gel. After the residual starting materials and by-products have been eluted using a chloroform eluent, the solvent is changed to a combination of 10% ethanol and 90% chloroform, by volume, and the desired product is recovered from the column. A nuclear magnetic resonance (NMR) spectrum shows the product recovered, approximately 2 grams of a red oil, which has a structure consistent with 2,2-bis [4-methoxyphenyl) -5-methoxycarbonyl-6-methoxy (polyethoxy) -2H-naphtho [1,2-b] pyran having an average of 16 ethoxy units.

EXAMPLE 2 STAGE 1 g of 1-phenyl-4-hydroxy-2-naphthoic acid, 50 g of (ethylene glycol) methyl ether and 1 g of concentrated sulfuric acid are added to a reaction flask. The resulting mixture is heated to almost reflux temperature (about 190 ° C) for about 90 minutes. The resulting mixture is cooled to room temperature. Water and chloroform (200 mL of each) are added to the mixture, and the organic layer is separated. The organic layer is washed twice with 200 mL of water, twice with 200 mL of dilute aqueous sodium carbonate, once again with 200 mL of water and finally with 200 mL of dilute aqueous hydrochloric acid. The solvent, chloroform, is removed by vacuum and the resulting residue (4 grams) is dried under a stream of air overnight and used directly in the next step.

STAGE 2 The product of step 1, 4 g of 1,1-diphenyl-2-propin-1-ol, 50 mL of toluene and the like are added to a reaction flask. 2 or 3 drops of dodecylbenzenesulfonic acid. The resulting mixture is heated to about 50 ° C for 4 hours, cooled to room temperature and dried in vacuo. The resulting residue is dissolved in an eluent of hexane, ethyl acetate (2: 1, in a base by volume) and subjected to chromatography using a column of silica gel. The photochromic fraction is collected and the solvent is removed in a rotary aspirator, which provides an oil that crystallizes when allowed to stand. The recovered product (3 grams) has a melting point of 134-135 ° C. A nuclear magnetic resonance (NMR) spectrum shows that the product has a structure consistent with 2,2-diphenyl-5- (2- (2-methoxyethoxy) ethoxycarbonyl-6-phenyl [2H] -naf or [1, 2- b] pyrano EXAMPLE 3 The procedure of example 2 is followed, except that l-methyl-4-hydroxy-2-naphthoic acid is used in place of l-phenyl-4-hydroxy-2-naphthoic acid and tri (ethylene glycol) methyl ether instead of di ( ethylene glycol) methyl ether. A nuclear magnetic resonance (NMR) spectrum shows that the product, recovered as an oil (2.5 grams), has a structure consistent with 2,2-diphenyl-5- (2- (2- (2-methoxyethoxy) ethoxy) ethoxycarbonyl) -6-methyl-2H-naphtho [1, 2b] pyran EXAMPLE 4 The procedure of Example 2 is followed, except that tri (ethylene glycol) methyl ether is used in place of di (ethylene glycol) methyl ether. A nuclear magnetic resonance (NMR) spectrum shows that the product, recovered as an oil (2.5 grams), has a structure consistent with 2,2-diphenyl-5- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy -carbonyl) -6-phenyl-2H-naphtho [2, 1-b] pyran.

COMPARATIVE EXAMPLE 1 CE 1 is 2, 2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6-methoxy-2H-naphtho [1,2-b] pyran. It can be prepared by following the procedure described for Example 2 in U.S. Patent No. 5,458,814.

COMPARATIVE EXAMPLE 2 CE 2 is 2,2-diphenyl-5-methoxycarbonyl-6-phenyl-2H-naphtho [1,2-b] pyran. It can be prepared by following the procedure described for Example 7 in U.S. Patent No. 5,458,814 using methyl 1-phenyl-4-hydroxy-2-naphthoate in place of methyl 1,4-dihydroxy-2-naphthoate .

COMPARATIVE EXAMPLE 3 CE 3 is 2, 2-diphenyl-5-methoxycarbonyl-6-methyl-2H-naphthyl, 2b] pyran. It can be prepared by following the procedure described for example 8 in the United States Patent No. 5,458,814. Using 1, 1-diphenyl-2-propin-1-ol in place of 1,1-bis (4-methoxyphenyl) -2-propin-1-ol.

EXAMPLE 5 PART A A test is carried out with the photochromic compounds described in Examples 1 to 4 and Comparative Examples 1 to 3, in the following manner. An amount of photochromic compound calculated to provide a 1.5 x 10"3 molal solution is added to a material containing 50 grams of a monomer combination of 4 parts of ethoxylated bisphenol A dimethacrylate (BPA 2EO DMA), 1 part poly ( ethylene glycol) dimethacrylate 600, and 0.033 weight percent of 2, 2'-azobis (2-methylpropionitrile) (AIBN) The photochromic compound is dissolved in the monomer combination by stirring and warming up gently, if necessary. a clear solution is obtained, poured into a flat sheet mold having the inner dimensions of 2.2 mm x 15.24 cm (6 inches) x 15.24 cm (6 inches) .The mold is sealed and placed in a horizontal air flow , in a programmable oven that is programmed to increase the temperature from 40 ° C to 95 ° C for a period of 5 hours, maintain the temperature at 95 ° C for 3 hours, decrease it to 60 ° C for a period of 2 hours and then keep it 60 ° C for 16 hours. After the mold is opened, the polymer sheet is cut using a diamond blade saw in 5.1 cm (two inch) test squares.

PART B The photochromic test squares prepared in part A are tested for photochromic response in an optical cabinet. Prior to testing in the optical cabinet, the photochromic test squares are conditioned, i.e., exposed to ultraviolet light of 365 nanometers for approximately 15 minutes to activate the photochromic compounds and then placed in an oven at 76 ° C for approximately 15 minutes to whiten or inactivate the photochromic compounds. The test panels are then cooled to room temperature, exposed to fluorescent ambient lighting for at least 2 hours and then kept covered for at least 2 hours before performing a test in an optical cabinet that is maintained at 22.2 ° C. (72 ° F). The cabinet is adjusted with a 250 watt Xenon arc lamp, a remote controlled shutter, a copper sulphate bath that acts as a thermal cover for the arc lamp, a Schott WG-320 nm cut filter. which removes short wavelength radiation; neutral density filter and a sample holder in which the square to be tested is inserted. The power output of the optical cabinet, ie the dosage of light to which a sample lens is exposed, is calibrated with a photochromic test chart used as a reference standard. This results in an energy power that varies from 0.15 to 0.20 milliwatts per square centimeter (mW / cm2). The power output is measured using a portable GRASEBY Optronics Model S-371 portable photometer (serial No. 21536) with a UV-A detector (serial No. 22411) or comparable equipment. The UV-A detector is placed in the sample holder and the light output is measured. Adjustments are made to the power output by increasing or decreasing the wattage of the lamp or by adding or removing neutral density filters in the light path. A collimated beam of light monitoring from a tungsten lamp is passed through a square at a small angle (approximately 30 °) normal to the square. After passing through the box, the light of the tungsten lamp is directed to a detector through a monochromator set of Spectral Energy Corp. GM-200 adjusted to a previously determined visible lambda of the photochromic compound being measured. The output signals of the detector are processed by a radiometer. The change in optical density (? OD) is determined by inserting a test box in the bleached state within the sample holder, adjusting to the transmittance scale at 100%, when opening the Xenon lamp shutter to provide radiation ultraviolet to change the test frame from the blanched state to an activated state (ie, darkened), by measuring the transmittance in the activated state and by calculating the change in optical density according to the formula: ?? D = log ( 100 /% Ta), where% TA is the percentage of transmittance in the activated state and the logarithm is in base 10. The optical properties of the photochromic compounds of the test tables are reported in table 1. The value? OD / Min, which represents the sensitivity of the response of photochromic compounds in UV light, is measured during the first five (5) seconds of UV exposure, and then expressed on a per-minute basis. The saturation optical density (? OD @ saturation) is taken under conditions identical to those of? OD / Min, except that UV exposure is continued for 15 minutes. The maximum lambda (Vis) is the wavelength in nanometers (nm) in the visible spectrum at which the maximum absorption of the activated form (with color) of the photochromic compound occurs in a test frame. The maximum wavelength lambda (Vis) is determined by testing the photochromic test frame polymers of part A in a UV-visible spectrophotometer Varian Cary 3. The lambda (?) Max (UV) value is the wavelength, in nanometers, in the ultraviolet interval closest to the visible spectrum in which the absorption of the photochromic compound takes place. This absorption is also determined with the same spectrophotometer. The whitening speed (T 1/2) is the time interval, in seconds, for absorbance of the activated form of the photochromic compound in the test panels to reach half of the highest absorbency at room temperature 22.2 ° C, ( 72 ° F) after removing the activating light source.

In table 1 the results of the compounds of the examples can be compared with the corresponding comparative examples as follows: example 1 with CE1, examples 2 and 4 with CE2, and example 3 with CE3. The corresponding comparative examples have the same structure as the example compounds, except for the polyalkoxylated substituent.

TABLE 1 Table 1 shows that a comparison of the results for the compounds of the examples with the results for the corresponding compounds of the comparative examples essentially indicate that there is no change in color (? Mx (visible)) and a significant increase in speed bleaching, that is, a decrease in T ^. Specifically, T% for example 1 is 24% less than that of CEi, the average of examples 2 and 4 is 28% less than CE2 and for example 3 it is 42% less than CE3. Since T is shortened, a? OD @ lower saturation is obtained for the compounds of the examples. Essentially there is no difference in activation wavelength (? Max (UV)) between the compounds of the example and the corresponding comparative examples and only the sensitivity results for example 1 were greater than 0.02 units lower than those of comparative example 1 correspondent . The present invention has been described with reference to the specific details of particular embodiments thereof. It is not intended that such details be considered as limitations to the scope of the invention except to the extent or to the extent that they are included in the appended claims.

Claims (19)

1. A naphthopyran compound represented by the following graphic formulas: wherein, (a) R1, R2, R3, R4, R5 or R6 are the group R represented by the formula: -A [(C2H40) x (C3H60) and (C4H80) z] D, where -A is - C (0) 0, -CH20 or -O, D is alkyl of 1 to 3 carbon atoms, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and 50, with the proviso that only one group R is present in the naphtho or indene portion of the naphthopyran and with the proviso that one of the substituents Rlf R2, R3 , R4, R5 or R6 if the group R and such substituents are not R, then (b) R1 is hydrogen, alkyl of 1 to 3 carbon atoms or the group -C (0) W, W is -0R7, or -N (R8) R9 piperidino or morpholino, wherein R7 is allyl, alkyl of 1 to 6 carbon atoms, phenyl, phenyl substituted with monoalkyl of 1 to 6 carbon atoms, phenyl substituted with monoalkoxy of 1 to 6 carbon atoms , phenylalkyl of 1 to 3 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkyl of 1 to 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkoxy of 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkoxy of 1 to 6 carbon atoms, alkoxy (of 1 to 6 carbon atoms) alkyl of 2 to 4 atoms carbon or alloalkyl of the 6 carbon atoms, R8 and R9 are each selected from the group consisting of alkyl of 1 to 6 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl, monosubstituted phenyl and disubstituted phenyl, the phenyl substituents are alkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms, and the halo substituent is chloro or fluoro; (c) R2, each R3 and R4 are selected from the group consisting of hydrogen, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, phenyl, monosubstituted phenyl, disubstituted phenyl and -OR10 groups and - OC (0) R10, wherein R10 is alkyl of 1 to 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms, phenylalkyl of the 3 carbon atoms substituted with monoalkyl of 1 to 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkoxy of 1 to 6 carbon atoms, alkoxy (of 1 to 6 carbon atoms) alkyl of 2 to 4 atoms of carbon, cycloalkyl of 3 to 7 carbon atoms or monoalkyl of 1 to 4 carbon atoms substituted with cycloalkyl of 3 to 7 carbon atoms, the phenyl substituents are alkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms and n is selected from the integers 0, 1 and 2; (d) R5 and R6 together form an oxo group, a spiroheterocyclic group having 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, or R5 and R6 are each hydrogen, hydroxy, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, allyl, phenyl, monosubstituted phenyl, benzyl, monosubstituted benzyl, chloro, fluoro, the group -C (0) X, wherein X is hydroxy, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, phenyl, monosubstituted phenyl, amino, monoalkylamino of 1 to 6 carbon atoms or dialkylamino of 1 to 6 carbon atoms, 0 R5 and R6 are each the group -OR11 # wherein RX1 is alkyl 1 to 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkyl of 1 to 6 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkoxy of 1 to 6 carbon atoms, alkoxy (of 1 to 6 carbon atoms) alkyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, cycloalkyl of 3 to 7 carbon atoms substituted with monoalkyl of 1 to 4 carbon atoms , chloroalkyl of 1 to 6 carbon atoms, fluoroalkyl of 1 to 6 carbon atoms, allyl, the group -CH (R12) Y, wherein R12 is hydrogen or alkyl of 1 to 3 carbon atoms and Y is CN, CF3 or COOR13, and R13 is hydrogen or alkyl of 1 to 3 carbon atoms, or Rxl is the group -C (0) Z, wherein Z is hydrogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, unsubstituted, monosubstituted or disubstituted aryl groups, phenyl or naphthyl, phenoxy substituted with mono- or dialkyl of 1 to 6 carbon atoms, phenoxy substituted by mono- or dialkoxy of 1 to 6 carbon atoms, amino, monoalkylamino of 1 to 6 carbon atoms, dialkylamino of 1 to 6 carbon atoms, phenylamino, phenylamino substituted by mono- or dialkyl of 1 to 6 carbon atoms or phenylamino substituted with mono- or dialkoxy of 1 to 6 carbon atoms, each of the substituents of the phenyl, benzyl and aryl group is alkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms carbon, -y (e) B and B 'are each selected from the group consisting of: (i) monosubstituted phenyl with R; (ii) unsubstituted, monosubstituted, disubstituted and trisubstituted aryl groups, phenyl and naphthyl; (iii) the unsubstituted, monosubstituted and disubstituted heteroaromatic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazolyl and fluorenyl, each of the aryl and heteroaromatic substituents in parts (e) (ii) and (iii) is selected from the group consisting of hydroxy, aryl, monoalkoxyaryl of 1 to 6 carbon atoms, dialkoxyaryl of 1 to 6 carbon atoms, monoalkylaryl of 1 to 6 carbon atoms, dialkylaryl of 1 to 6 carbon atoms, chloroaryl, fluoroaryl, cycloalkylaryl of 3 to 7 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, cycloalkoxy of 3 to 7 carbon atoms, cycloalkyloxy (from 3 to 7 carbon atoms) alkyl of 1 to 6 carbon atoms, cycloalkyloxy (of 3 to 7 carbon atoms) alkoxy of 1 to 6 carbon atoms, arylalkyl of 6 carbon atoms, arylalkoxy of 1 to 6 carbon atoms, aryloxy, aryloxyalkyl of the 6 atoms d carbon, aryloxyalkoxy of 1 to 6 carbon atoms, mono- and di-alkyl of 1 to 6 carbon atoms) arylalkyl of 1 to 6 carbon atoms, mono- and di-alkoxy (of 6 carbon atoms) arylalkyl from 1 to 6 carbon atoms, mono- and di-alkyl (of 1 to 6 carbon atoms) arylalkoxy of 1 to 6 carbon atoms, mono- and di-alkoxy (of 1 to 6 carbon atoms) arylalkoxy of 1 to 6 carbon atoms, amino, monoalkylamino of 1 to 6 carbon atoms, dialkylamino of 1 to 6 carbon atoms, diarylamino, N-alkyl (from 1 to 6 carbon atoms) piperazino, N-arylpiperazino, aziridino, indolino, piperidino, arylpiperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrho, alkyl of 1 to 6 carbon atoms, chloroqu 1 to 6 carbon atoms, fluoroalkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, monoalkoxy (of 1 to 6 carbon atoms) alkyl of 1 to 4 carbon atoms, acryloxy, methacryloxy, bromine, chlorine and fluorine; (iv) the groups represented by the following graphic formulas: wherein E is -CH2- or oxygen and G is oxygen or substituted nitrogen, with the proviso that when G is substituted nitrogen, E is -CH2-, the nitrogen substituents are selected from the group consisting of hydrogen, alkyl of 1 to 6 carbon atoms, and acyl of 2 to 6 carbon atoms; each R 14 is alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, hydroxy, chloro or fluoro; R15 and R16 are each hydrogen or alkyl of 1 to 6 carbon atoms; and q is the integer 0, 1 or 2; (v) alkyl of 1 to 6 carbon atoms, chloroalkyl of 1 to 6 carbon atoms, fluoroalkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms alkyl of 1 to 4 carbon atoms; and (vi) the group represented by the following graphic formulas: H C = C M wherein L is hydrogen or alkyl of 1 to 4 carbon atoms and M is selected from the unsubstituted, monosubstituted and disubstituted members of the group consisting of naphthyl, phenyl, furanyl and thienyl, each of such group substituents being alkyl 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, fluoro or chloro.

2. The naphthopyran according to claim 1, characterized in that: (a) Rlf R2, R3, R4 / R5 or R6 are the group R, x and y are each a number between 0 and 50, z is O and the sum of x and y is between 2 and 50, and with the proviso that one of the substituents R1 # R2, R3, R4, R5 or R6 is the group R and that such substituents which are not R, then (b) Rx is the group -C (0) W, W is -OR ,, or -N (R8) R9, wherein R7 is alkyl of 1 to 4 carbon atoms, phenyl, phenyl substituted with monoalkyl of 2 to 4 carbon atoms, phenyl substituted with monoalkoxy from 2 to 4 carbon atoms, phenylalkyl of 1 to 2 carbon atoms, phenylalkyl of 1 to 2 carbon atoms substituted with monoalkyl of 1 to 4 carbon atoms, phenylalkyl of 1 to 2 carbon atoms substituted with monoalkoxy of 1 to 4 carbon atoms, monoalkoxy (of 1 to 4 carbon atoms) alkyl of 2 to 3 carbon atoms or alloalkyl of 1 to 4 carbon atoms; R8 and R9 are each selected from the group consisting of alkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, phenyl, monosubstituted phenyl and disubstituted phenyl, the phenyl substituents are alkyl of 1 to 4 carbon atoms. carbon or alkoxy 1 to 4 carbon atoms, the halo substituents are chloro or fluoro; (c) R2, each R3 and R4 are selected from the group consisting of hydrogen, alkyl of 1 to 3 carbon atoms, cycloalkyl of 3 to 5 carbon atoms, phenyl, monosubstituted phenyl, disubstituted phenyl and the -OR10 group, wherein R10 is alkyl of 1 to 4 carbon atoms, phenylalkyl of 1 to 2 carbon atoms, phenylalkyl of 1 to 2 carbon atoms substituted with monoalkyl of 1 to 4 carbon atoms, phenylalkyl of 1 to 2 carbon atoms substituted with monoalkoxy of 1 to 4 carbon atoms, alkoxy (of 1 to 4 atoms) carbon) alkyl of 2 to 4 carbon atoms, cycloalkyl of 5 to 7 carbon atoms or cycloalkyl of 5 to 7 carbon atoms substituted with monoalkyl of 1 to 3 carbon atoms and the phenyl substituents are alkyl of 1 to 3 carbon or alkoxy atoms of 1 to 3 carbon atoms; (d) R5 and R6 are each selected from the group consisting of hydrogen, hydroxy, alkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, chloro, fluoro and the group -OR ^, wherein RX1 is alkyl of 1 to 3 carbon atoms, phenylalkyl of 1 to 2 carbon atoms, phenylalkyl of 3 carbon atoms substituted with monoalkyl of 3 carbon atoms, phenylalkyl of 1 to 3 carbon atoms substituted with monoalkoxy of 1 to 3 carbon atoms, alkoxy (from 1 to 3 carbon atoms) alkyl from 2 to 4 carbon atoms, chloroalkyl from 1 to 3 carbon atoms, fluoroalkyl from 1 to 3 carbon atoms, the group -CH (R12) Y , wherein R12 is hydrogen or alkyl of 1 to 2 carbon atoms and Y is CN or C00R13, and R13 is hydrogen or alkyl of 1 to 2 carbon atoms, 0 R1: L is the group -C (0) Z, wherein Z is hydrogen, alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 3 carbon atoms, phenyl, naphthyl, monosubstituted aryl groups, phenyl or naphthyl, phenoxy, phenoxy substituted with mono- or dialkyl of 1 to 3 carbon atoms, phenoxy substituted with mono- or dialkoxy of 1 to 3 carbon atoms, monoalkylamino of 1 to 3 carbon atoms, phenylamino, phenylamino substituted with mono- or dialkyl of 1 to 3 carbon atoms or phenylamino substituted with mono- or dialkoxy of 1 to 3 carbon atoms , and the aryl substituents are alkyl of 1 to 3 carbon atom or alkoxy of 3 carbon atom ala; (e) B and B1 are each selected from the group consisting of: (i) phenyl monosubstituted with R; (ii) phenyl, monosubstituted phenyl, and disubstituted; (iii) the unsubstituted, monosubstituted and disubstituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl, dibenzofuran-2-yl and dibenzothien-2-yl, each of the phenyl and heteroaromatic substituents in the (e) (ii) and (iii) is selected from the group consisting of hydroxy, aryl, aryloxy, arylalkyl of 1 to 3 carbon atoms, amino, monoalkylamino of 1 to 3 carbon atoms, dialkylamino of 1 to 3 atoms carbon, N-alkyl (1 to 3 carbon atoms) piperazino, indoline, piperidino, morpholino, pyrryl, alkyl of 1 to 3 carbon atoms, chloroalkyl of 1 to 3 carbon atoms, fluoroalkyl of 1 to 3 carbon atoms carbon, alkoxy of 1 to 3 carbon atoms, monoalkoxy (of 1 to 3 carbon atoms) alkyl of 1 to 3 carbon atoms, chloro and fluoro; (iv) the groups represented by the following graphic formulas: wherein -CH2- is carbon and G is oxygen, R14 is alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms; R1S and R16 are each hydrogen or alkyl of 1 to 4 carbon atoms, and q is 0 or 1; (v) alkyl of 1 to 4; (vi) the group represented by the following graphic formula: \ H L "NM wherein L is hydrogen or methyl and M is phenyl or monosubstituted phenyl, the phenyl substituents are alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 3 carbon atoms or fluoro.

3. The naphthopyran according to claim 2, characterized in that: (a) R1; R2, R3, R4, R5 or R6 is the group R, and x is a number between 2 and 50, y and z are each 0, and with the proviso that one of the substituents R17 R2, R3, R4, Rs or R6 is the group R and that such substituents which are not R, then (b) Rx is the group -C (0) W, W is the group -0R7, and R7 is alkyl of 1 to 3 carbon atoms; (c) R2, each R3 and R4 are selected from the group consisting of hydrogen, alkyl of 1 to 3 carbon atoms, phenyl, monosubstituted phenyl, disubstituted phenyl and the group, -OR10, wherein R10 is alkyl of 1 to 3 carbon atoms, and the phenyl substituents are methyl or methoxy; (d) R5 and R6 are each hydrogen, hydroxy, alkyl of 1 to 4 carbon atoms, or the group -OR1 ?; wherein Rn is alkyl of 1 to 3 carbon atoms; (e) B and B 'are each selected from the group consisting of: (i) phenyl monosubstituted with R; (ii) phenyl, monosubstituted phenyl, and disubstituted; (iii) the unsubstituted, monosubstituted and disubstituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl and benzothien-2-yl, each of the phenyl and heteroaromatic substituents in subparagraphs (e) (ii) and (iii) are selects from the group consisting of hydroxy, alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 3 carbon atoms, phenyl, indolino, fluoro and chloro; and (iv) the group represented by the following graphic formula: wherein E is -CH2- and G is oxygen, R14 is alkyl 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms; R? S and R? S are each hydrogen or alkyl of 1 to 3 carbon atoms; and q is 0 or l;

4. A naphthopyran compound, characterized in that it is selected from the group consisting of: (a) 2, 2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6-methoxy (polyethoxy) (16EO) -2H-napht [ 1, 2-b] pyran; (b) 2, 2-difinyl-5- (2- (2-methoxyethoxy) ethoxycarbonyl) -6-f-enyl-2H-napht [1,2-b] pyran; (c) 2, 2-d i f e n i l -5- (2 - (2 - (2-methoxyethoxy) ethoxy) ethoxycarbonyl) -6-methyl-2H-napht [1,2-b] pyran; (d) 2, 2-d i f e n i l -5- (2 - (2 - (2-ethoxyethoxy) ethoxy) ethoxycarbonyl) -6-f-enyl-2H-napht [1,2-b] pyran; (e) 2-2-Diphenyl-5-carbomethoxy-9- (2- (2- (2-methoxyethoxy) ethoxy) propyloxy) -2H-naphtho [1,2-b] pyran; (f) 3-f e n i l -3- (4 - (2 - (2 - (2-methoxyethoxy) ethoxy) ethoxy) phenyl) -3H-naphtho [1,2-b] pyran; (g) 3, 3-di (4-methoxyphenyl) -6, 11, 13-trimethyl-13- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) -indeno [2,1-f] naphtho [ 1, 2-b] pyran; (h) 2-phenyl-3 - (4 - (2 - (2 - (2-methoxyethoxy) ethoxy) and oxy) phenyl) -8-methoxy-9- (2- (2- (2-methoxyethoxy) ethyloxy) ethylcarbonyl) -3H-naphthol [2, 1-b] pyran; and (i) 3-f-enyl-3- (4-morpholinophenyl) -6- (2- (2-methoxyethoxy) ethoxy) -11, 13-dimethyl-13-hydroxy-indeno [2,1-f] naphtho [ 1, 2-b] pyrano.

5. A photochromic article, characterized in that it comprises, in combination, a polymeric organic host material and a photochromic amount of the naphthopyran compound according to claim 1.

6. The photochromic article according to claim 5, characterized in that the polymeric organic host material is selected from the group consisting of polyacrylates, polymethacrylates, alkyl polymethacrylates of 1 to 12 carbon atoms, polyoxy (alkylene methacrylate), poly (methacrylates of alkoxylated phenol), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), polycarbonate thermoplastics, polyesters, polyurethanes, polythiourethanes, poly (ethylene terephthalate), polystyrene, poly (alpha-methylstyrene), copoly (styrene-methyl methacrylate), copolymers (styrene-acrylonitrile), polyvinylbutyral and polymers of members of the group consisting of monomers of polyol (allyl carbonate), polyfunctional acrylate monomers, polyfunctional methacrylate monomers, dimethacrylate monomers diethylene glycol, diisopropenyl benzene monomers, alkoxylated polyhydric alcohol monomers and diallylidene pentaerythritol monomers.

7. The photochromic article according to claim 6, characterized in that the polymeric organic material is an omopolymer or copolymer of monomer or monomers selected from the group consisting of acrylates, methacrylates, methyl methacrylate, ethylene glycol bis methacrylate, bisphenol A dimethacrylate ethoxylated, vinyl acetate, vinyl butyral, urethane, thiourethane, bis (allyl carbonate) diethylene glycol, diethylene glycol dimethacrylate, diisopropenyl benzene and ethoxylated trimethylol propane triacrylate.

8. The photochromic article according to claim 5, characterized in that the photochromic compound is present in an amount of 0.05 to 1.0 milligrams per square centimeter of polymeric organic host material surface to which the photochromic substance or substances is incorporated or applied.

9. The photochromic article according to claim 5, characterized in that the polymeric organic host material is an optical element.

10. The photochromic article according to claim 9, characterized in that the optical element is a lens.

11. A photochromic article, characterized in that it comprises a polymeric organic host material selected from the group consisting of: poly (methyl methacrylate), poly (ethylene glycol bismethacrylate), poly (ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly (acetate) vinyl), polyvinyl butyral, polyurethane and polymers of members of the group consisting of bis (allyl carbonate) diethylene glycol monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismetacrylate monomers, diisopropenyl benzene monomers and triacrylate monomers of ethoxylated trimethylol propane, and a photochromic amount of the naphthopyran compound according to claim 3.

12. A photochromic article, characterized in that it comprises, in combination, a solid substrate and a photochromic amount of each of: (a) at least one naphthopyran compound according to claim 1, and (b) at least one other photochromic compound organic that has at least a maximum absorption activated within the range of between 400 and 700 nanometers.

13. A photochromic article, characterized in that it comprises a polymerization of an optical organic resin monomer and a photochromic amount of a naphthopyran compound according to claim 1.

14. The photochromic article according to claim 13, characterized in that the refractive index of the polymerized is 1.48 to 1.75.

15. The photochromic article according to claim 13, characterized in that the polymerized is an optical element.

16. The photochromic article according to claim 15, characterized in that the optical element is a lens.

17. A photochromic article, characterized in that it comprises, in combination, a solid substrate and on at least one surface thereof, a cured coating of a coating composition having a photochromic amount of the naphthopyran compound according to claim 1.

18. The photochromic article according to claim 17, characterized in that the coating composition is selected from the group consisting of a polymeric coating composition, paint and ink.

19. The photochromic article according to claim 17, characterized in that the substrate is selected from the group consisting of glass, masonry, textiles, ceramics, metals, wood, paper and polymeric organic materials.