BRPI9702489B1 - naphthopyran compound - Google Patents

Abstract

"naphthopyran compound" comprising novel reversible photochromic compounds of 2h-naphtho [1,2-b] pyranes, examples of which are compounds having certain substituents on carbon atom number 5 of the naphthoopyran naphtho moiety and at position 2 of the pyran ring . certain substituents may also be present on the carbon atoms number 6, 7, 8, 9 or 10 of the naphthalopyran portion.

Description

Description of the Invention The present invention relates to certain novel naphthopyran derivatives. More particularly, this invention relates to novel photochromic naphthoopyran compounds and to compositions and articles containing such novel naphthoopyran compounds. When exposed to light radiation involving ultraviolet rays, such as ultraviolet radiation in sunlight or the light of a mercury lamp, many photochromic compounds exhibit a reversible color change. When ultraviolet radiation is discontinued, such photochromic compound will return to its original color or colorless state.

Several classes of photochromic compounds have been synthesized and suggested for use in applications where sunlight-induced reversible color exchange or darkening is desired. U.S. Patent 3,567,605 (Becker) describes a number of pyran derivatives, including certain benzopyran and naphthopyran. Such compounds are described as chromene derivatives and have been reported to experience a color change, e.g., from colorless to orange yellow under ultraviolet light irradiation at temperatures below -30 ° C. Irradiation of the compounds with visible light or under a temperature increase above about 0 ° C has been reported to reverse color to a colorless state.

U.S. Patent 5,066,818 describes various 3,3-diaryl-3H-naphtho [2,1-b] pyranes as having desirable photochromic properties, i.e. high colorability and acceptable fade, for ophthalmic and other applications.

Also disclosed as a comparative example in the '818 patent isomeric 2,2'-diaryl-2H- [1,2-b] pyranes, which are reported to require unacceptably long fade times upon activation.

U.S. Patent 3,627,690 describes 2,2-disubstituted 2 H-naphtho [1,2-b] pyran compositions containing minimal amounts of a weak to moderate strength base or acid. The addition of an acid or base to the naphthalopyran composition has been disclosed as a fade rate enhancer to colored naphthalanes, thereby making them useful in eye protection applications such as sunglasses. It is further reported that the fade rate of 2H-naphtho [1,2-b] pyran without the aforementioned additives ranges from several hours to many days until complete reversal. U.S. Patent 4,818,096 discloses a blue-colored benzo or naphthopyran having in the alpha position relative to the pyran ring a group having a nitrogen-containing substituent at the ortho or para positions.

The present invention relates to novel substituted 2 H-naphtho [1,2-b] pyran compounds which have surprisingly been found to have an acceptable fade rate in addition to a high activated intensity and a high coloration rate. In particular, the use of certain substituents at the 5-position of the naphtho portion of the naphthopyran compound increases the fade rate without the addition of acids or bases. Moreover, these compounds have certain substituents at the 2-position of the pyran ring. Certain substituents may also be present on the carbon atoms number 6, 7, 8, 9 or 10 of the naphthalopyran naphtho moiety.

DETAILED DESCRIPTION OF THE INVENTION In recent years, photochromic plastic materials, particularly plastic materials for optical applications, have received considerable attention. In particular, photochromic ophthalmic plastic lenses have been investigated due to the weight advantage they offer over glass lenses. In addition, photochromic transparencies for vehicles, such as cars and airplanes, have been of interest due to the potential safety features such transparencies offer.

In accordance with the present invention, it has now been found that certain novel 2H-naphtho [1,2-b] pyran compounds can be prepared having an acceptable fade rate, high activated intensity and a high coloration rate. Such compounds may be described as naphthopyran having certain substituents at the 2-position of the pyran ring and at carbon number 5 of the naphtho portion of the naphthopyran ring. Certain substituents may also be present at the atoms 6, 7, 8, 9 and 10 of the naphtho portion of the naphthopyran ring. Such compounds may be represented by the following formula: In formula I, Rχ may be the group -CH2X or -C (G) Y, X may be halogen, hydroxy, benzoyloxy, C1-6 alkoxy, acyloxy C 1 -C 6, amino, C 1 -C 6 dialkylamino-C6-6 alkylamino, di (C 1 -C 6) alkylamino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, trimethylsilyloxy, or -OCH ( Rn) Z; Y may be the group -OCH (Rn) Z or an unsubstituted, monosubstituted or disubstituted heterocyclic ring selected from the group consisting of 1-indolinyl, morpholino, piperidino, 1-pyrrolidyl, 1-imidazolidyl, 2-imidazolin -1-yl, pyrazolidyl, pyrazolinyl and 1-piperazinyl; Z being -CN, -CF 3, halogen, -C (O) R 4, or -COOR] -; R11 and R11 may be hydrogen or C1 -C6 alkyl; Rn may be hydrogen; heterocyclic ring substituents may be C1 -C6 alkyl or C1 -C6 alkoxy, and halogen may be chloro or fluoro.

Preferably, R3 is -CH2X or -C (O) Y group, where X is hydroxy, alkoxy or C1-C4 acyloxy, Y is -OCH (Rn) Z group, or an unsubstituted heterocyclic ring or monosubstituted selected from the group consisting of 1-indolinyl, morpholino, piperidino, and 1-pyrrolidyl, where Z is -CN, C (O) Rn, or -COORn, Rn and Rn are hydrogen or C3-C4 alkyl, Rn is hydrogen; and the heterocyclic ring substituents are C1-C4 alkyl or C1-C4 alkoxy.

More preferably, R4 is -CH2X or -C (O) Y group, where X is hydroxy, C4-C4 alkoxy, or C1-C4 acyloxy and Y is an unsubstituted or monosubstituted heterocyclic ring selected from R4. group consisting of 1-indolinyl, morpholino, and piperidino. More preferably, R 4 is hydroxymethyl, acetoxymethyl, morpholinocarbonyl, or piperidinocarbonyl.

R 2 and each R 3 in the formula I may be hydrogen, C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, unsubstituted phenyl, mono-, di- or tri-substituted, the ORg group, where R g may be hydrogen, (C 1 -C 6) alkyl, phenyl (C 3 -C 3) alkyl, monosubstituted phenyl (C 4 -C 3) alkyl, (C 2 -C 4) alkoxy, C 2 -C 4 cycloalkyl, cycloalkyl C3 -C7 mono (C4 -C4) alkyl-substituted, C4 -C5 haloalkyl allyl, the group -CH (R7> W, where W may be -CN, CF3, halogen, -C (O) R7, or -COOR7 - where R 7 may be hydrogen, C 1 -C 6 alkyl, or (C 2 -C 4) alkoxy (C 2 -C 4) alkyl, or R 6 may be the -C (O) T group, where T may be hydrogen, C 1 -C 6 alkyl C 1 -C 6 alkoxy, unsubstituted or monosubstituted aryl phenyl or naphthyl groups, phenoxy, mono- or di-substituted alkoxy phenoxy, mono- or di-C 1 -C 6 substituted alkyloxy, C 1-6 monoalkylamino C6, phenylamino, phenyl- or mono- or di-C1 -C6 -substituted alkylamino, mono- or di-C1-6-substituted alkylamino, each of said substituents of phen or naphthyl being C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogen, each of said halogen or halo substituents being chloro or fluoro, and n is selected from integers 0, 1, 2, and 3.

Preferably R 2 and each R 3 are hydrogen, C 1 -C 4 alkyl, unsubstituted, mono-, di- or tri-substituted phenyl, the -ORg group, where R g is C 4 -C 4 alkyl, or the CH group (R7) W, where W is -COOR7, and R7 is hydrogen or C1-C4 alkyl, phenyl substituents are C4-C4 alkyl, C1-C4 alkoxy or fluoro and n is selected from integers 0, 1, and 2 .

More preferably, R 2 and each R 3 are hydrogen, C 1 -C 2 alkyl, unsubstituted, mono-, di- or trisubstituted phenyl, the -ORg group where R g is O-alkyl O 2 -C 2 , or the group -CH (R 7> W, where W is -COOR 7, and R 7 is C 4 -C 2 alkyl, phenyl substituents are C 1 -C 2 alkyl, C 1 -C 2 alkoxy, or fluoro, and n is selected from integers 0, 1, and 2. More preferably, R2 and R3 are hydrogen, phenyl, methoxy, methyl or fluoro.

In graphic formula I, B and B "each may be selected from the group consisting of: (i) the unsubstituted, mono-, di- and tri-substituted aryl, phenyl and naphthyl groups; the unsubstituted aromatic heterocyclic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzothienyl, dibenzofuranyl, and carbazolyl, mono-, di-, or tri-substituted, the aryl and heterocyclic substituents being selected from the group consisting of hydroxy, amino, C1 -C6 monoalkylamino, C1 -C6 dialkylamino, morphino, piperidino, 1-indiinyl, pyrrolidyl, 1-imidazolyl, 2-imidazolin-1-yl, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 monoalkoxy (C 1 -C 4) alkyl , acryloxy, methacryloxy, and halogen, where the halogen or (halo) group may be fluoro or chloro, (iii) the groups represented by the following graphic formulas II A and II B: where D may be carbon or oxygen and E may be oxygen or substituted nitrogen, provided that when E is substituted nitrogen, D is carbon, said nitrogen substituent being selected from the group consisting of hydrogen, Cq-Cg alkyl and Cq-Cg acyl; each Rq may be C1 -C6 alkyl, C1 -C6 alkoxy, hydroxy or halogen, wherein the halogen may be chloro or fluoro; Rg and Rio may each be hydrogen or alkyl. Cq-Cg; and m may be the integer 0, 1 or 2; jiv) C C-Cg alkyl, haloalkyl, ,, -Cg, alkoxy Οχ-Cg alkyl Οχ-Ο ^, cycloalkyl C3-Gg, monoalkoxy (Οχ-Cg), cycloalkyl (€ 3-05), monoalkyl (Οχ-Cg) C 6 -C 8 cycloalkyl, and C 3 -C 6 halocycloalkyl, said halo groups being fluoro or chloro; and (v) the group represented by the following formula: wherein each U may be hydrogen or C 2 -C 4 alkyl, and V may be selected from the unsubstituted, mono-, di- or tri-substituted members of the group consisting of naphthyl, phenyl furanyl, and thienyl, where the substituents for each member of said group are C 2 -C 4 alkyl, C 1 -C 4 alkoxy, fluoro or chloro; or (vi) B and B 'taken together may form a fluoren-9-ylidene or. form a member selected from the group consisting of saturated spiro-mono-cyclic hydrocarbon rings, eg, cyclopropylidene, cyclobutylidene, cyclopentylidene, cycloheptylidene, cycloheptylidene, cyclononylidene, cyclodecylidene, cycloundecylidene, cycloundedicyclo-cyclo-23-cyclohexylated cyclohexylated , eg, bicyclo [2.2.1] heptylidene, ie, norbornylidene, 1,7,7-trimethyl bicyclo [2.2.1] heptylidene, ie, bornylidene, bicyclo [3.2.1] octylidene, bicyclo [3.3.1] nonan 9-ylidene, bicyclo [4.3.2] undecane, and saturated C7-C χ 2 spiro-tricyclic hydrocarbon rings, eg tricyclo [2.2.1.0 ^ * 6] heptylidene, tricyclo [5.3.1.1 ^ 76] dodecylidene and tricyclo [3.3.1.17] decylidene, i.e. adaraantylidene, where fluoren-9-ylidene substituents may be selected from the group consisting of C1 -C4 alkyl, C1 -C4 alkoxy, fluoro and chloro.

Preferably, B and B 'are each selected from the group consisting of: (i) unsubstituted, mono-, di- and tri-substituted phenyl; (ü) the unsubstituted heterocyclic aromatic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzo-thien-2-yl, benzothien-3-yl, dibenzothienyl, dibenzofuranyl and carbazolyl di- and tri-substituted, each of phenyl and heterocyclic substituents being selected from the group consisting of morpholino, piperidino, C1-C4 alkyl, C4-C4 alkoxy and halogen, the halogen group or (halo) being fluoro or chloro; (iii) the groups represented by the graphic formula II A, where D is carbon and E is oxygen; each R 6 is C 4 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy or halogen, the halogen being chlorine or fluoro; R 9 and R 14 is each hydrogen or C 4 -C 4 alkyl; and m is the integer 0, 1 or 2; (iv) C4 -C4 alkyl, C4 -C5 alkoxy (C4 -C4) alkyl and C6 -C6 cycloalkyl; and (v) the group represented by the formula II C, where U is hydrogen or methyl, and V is phenyl or monosubstituted phenyl, the phenyl substituent being C4-C4 alkyl, C4-C4 alkoxy or fluoro; or (vi) B and B 'taken together form an unsubstituted or monosubstituted fluoren-9-ylidene or a member selected from the group consisting of saturated C3 -C3 spiro-monocyclic hydrocarbon rings, C7-3 spiro-bicyclic hydrocarbon rings Saturated C40, and saturated C7 -C40 spiro-tricyclic hydrocarbon rings.

More preferably, B and B 'are each selected from the group consisting of: (i) unsubstituted, mono- and disubstituted phenyl; (ii) the heterocyclic aromatic groups pyridyl, benzofuran-2-yl, benzo-thien-2-yl, dibenzothienyl and dibenzofuranyl, each of the phenyl and heterocyclic substituents being selected from the group consisting of morpholine, piperidine, C1 -C2 alkyl C 1 -C 2 alkoxy; and (iii) the groups represented by the formula II A, where D is carbon and E is oxygen; each R 6 is C 1 -C 2 alkyl, C 1 -C 2 alkoxy or fluoro; R 6 and R 8 are each hydrogen or C 1 -C 2 alkyl; and m is the integer 0, 1 or 2; or (iv) B and B 'taken together form fluoren-9-ylidene, bornylidene, norbornylidene, bicyclo [3.3.1] nonan-9-ylidene or adamantylidene. More preferably, B and B 'are each phenyl, methoxy-substituted phenyl, morpholine-substituted phenyl, dibenzofuran-2-yl, or 2,3-dihydroben-zofuran-5-yl.

Compounds represented by graphic formula I may be prepared by the following steps. Benzophenones represented by the formulas V and VA are either purchased or prepared by Friedel-Crafts methods using a suitably substituted or unsubstituted benzoyl chloride of formula IV and a commercially available substituted or unsubstituted benzene compound of the formula. III. See Friedel-Crafts and Related Reactions, George A. Olah, Interscience Publishers, 1964, Vol. 3, Chapter XXXI (Aromatic Ketone Synthesis), and "Friedel-Crafts Regioselective Acylation of 1,2,3,4-Tetrahydroquinoline" and Nitrogen Heterocycles Correlates: Effect on NH Protecting Groups and Ring Size "by Ishihara, Yugi et al, J. Chem. Soc., Perkin Trans. 1, pages 3401 to 3406, 1992.

The compounds represented by graphic formulas III and IV are dissolved in a solvent, such as carbon disulfide or methylene chloride, and reacted in the presence of a Lewis acid, such as aluminum chloride or tin tetrachloride, to form the corresponding substituted benzophenone represented by the formula V (or VA in Reaction 3). Re Rf represent potential phenolic substituents. In Reaction B, substituted or unsubstituted ketone represented by the formula VA, in which B and B1 may represent groups other than substituted or unsubstituted phenol, is reacted with sodium acetylide in a suitable solvent, such as tetrahydrofuran (THF) anhydrous to form the corresponding propargyl alcohol represented by graphic formula VI. Propargyl alcohols having groups B or B 'other than substituted or unsubstituted phenol may be prepared from commercially available ketones or, for example, from ketones prepared by reacting an acyl halide with a benzene, naphthalene, or substituted or unsubstituted heteroaromatic compound. Propargyl alcohols having groups B or B 'represented by graphic formula II C may be prepared by the methods described in U.S. Patent 5,274,132, column 2, lines 40 to 68.

Naphthols represented by the graphic formulas VIII and XIII, used in the preparation of naphthopyran of formula I, may be prepared as described in Reactions C or D. In Reaction C, 1,4-dihydroxy-2-naphthoic acid represented by the formula Graph VII, is reacted with an alkyl halide, e.g., methyl iodide, in the presence of ethyldiisopropyl amine in a suitable solvent, such as anhydrous dimethylformamide (DMF), to form the corresponding methyl-1,4-dihydroxy Naphthoate, which is represented by graphic formula VIII. This reaction is further described in The Journal of Organic Chemistry, 46 (1), 1981, page 3477.

In Reaction D, a substituted or unsubstituted acetophenone, benzophenone, or benzazide represented by formula IX is reacted with dimethyl succinate (formula X) in the presence of a base such as sodium hydride or potassium t-butoxide. in a suitable solvent such as toluene or THE to form a suitable substituted monoester of an alpha-arylidene succinic acid represented by the formula XI. Compound XI is heated with acetic anhydride and anhydrous sodium acetate to form a corresponding acetate derivative represented by the formula XII. Compound XII is reacted with hydrochloric acid and an anhydrous alcohol such as anhydrous methanol to form a corresponding naphthol represented by the formula. Graphic XIII. Reaction D is further described in the text Orqanic Reactions, Vol. VI, Chapter 1, pages 1-73, John Wiley & Sons, Inc., New York.

In Reaction E, a propargyl alcohol represented by the formula VI is coupled with a naphthol represented by the formula VII (VIII further substituted with (R 3) n) to form 6-hydroxy naphthopyran represented by the formula XIV. The 6-hydroxy substituent of compounds represented by the formula XIV may be converted, for example, to a · 6-alkoxy group by reaction with an alkyl halide, eg, methyl iodide, ethyl iodide, benzyl bromide, etc. . to form compounds represented by the formula XV. Compounds represented by graphic formula XV may be reduced, for example with lithium aluminum hydride in an inert solvent such as THF to provide the 5-hydroxymethyl-substituted compounds represented by graphic formula XVI. The 5-hydroxymethyl substituent of compounds represented by formula XVI may be derived in a variety of ways. It can be converted to an alkoxymethyl by reacting compounds represented by the formula XVI with an alkyl halide, such as methyl iodide, n-propyl bromide, benzyl bromide, etc., in the presence of a base such as potassium carbonate to produce compounds represented by the graphic formula XVII. Alternatively the hydroxymethyl may be acylated with an acyl halide, e.g. acetyl chloride, benzoyl chloride, etc. to obtain compounds represented by the formula XVIII. In a third example, hydroxymethyl may be reacted with trimethylsilyl chloride, in the presence of a acceptor acid, e.g., triethyl amine, to produce trimethylsilyl ethers represented by compounds of formula XIX.

In Reaction F, a propargyl alcohol represented by the formula VI is coupled with a naphthol represented by the formula XIII to form 6-aryl, 6-alkyl or 6-hydrogen naphthoxy compounds represented by the formula XX. Compounds represented by graphic formula XX may be reduced, e.g., with lithium aluminum hydride (LAH) in an inert solvent such as THF to give 5-hydroxymethyl compounds represented by graphic formula XXI. The S-hydroxymethyl substituent of compound compounds represented by graphic formula XXI may be derived in a number of ways. They may be converted to a chloromethyl group by reacting compounds represented by graphic formula XXI with thionyl chloride to produce compounds represented by graphic formula XXII. The 5-chloromethyl of the compounds represented by the formula XXII may be further derived using reactions known in the art, such as by reacting it with a primary, secondary, or heterocyclic amine, eg propyl amine, diethyl amine, morpholine, etc. to give 5-aminomethyl compounds represented by formula XXIII.

Alternatively, the hydroxymethyl group of compounds represented by graphic formula XXI may be reacted with alkyl halide, e.g., methyl iodide, propyl iodide, benzyl bromide, etc., to obtain compounds represented by graphic formula XIV.

Compounds with a 5-substituted amide group are prepared by a series of reactions found in Reaction G. Naphthols represented by the formula XIII are hydrolyzed to carboxyaphthols represented by the formula XXV using potassium hydroxide dissolved in a mixture of water and alcohol. The free hydroxy substituent of compounds of formula XXV is protected by reaction with. acetyl chloride to give acetoxy-substituted compounds of formula XXVI. The carboxy substituent of compounds of formula XXVI is converted to an acid chloride by reaction with thionyl chloride to obtain compounds of formula XXVII. The acid chloride of compounds of formula XXVII is converted to an amide group by reaction with a primary, secondary or heterocyclic amine, e.g., propyl amine, diethyl amine, morpholine, piperidine, etc., to obtain compounds of formula XXVIII. The acetoxy substituent of compounds of formula XXVIII is deprotected by reaction with methanol in the presence of HCl to obtain naphthols of formula XXIX. Pyranes containing a 5-amide group represented by formula XXX are prepared by reacting a naphthol of formula XXIX with a propargyl alcohol of formula VI.

Compounds represented by graphic formula I may be used in those applications in which organic photochromic substances may be employed, such as optical lenses, p, er corrective vision ophthalmic lenses and flat lenses, bulkheads, diving goggles, visors, camera lenses. , automotive windshields, aircraft and automotive transparencies, eg, sunroofs, side and rear lights, plastic films and blankets, textiles and coatings, eg, coating compositions such as inks, and check marks on safety documents such as paper money, passports and driver's licenses where authentication or authenticity verification is desirable.

Naphtopyranes represented by the graphic formula I exhibit color changes from colorless to color ranging from yellow to red / purple.

Examples of naphthopyran contemplated within the scope of the invention are as follows: (a) 2,2-bis (4-methoxyphenyl) -5-hydroxymethyl-6-methyl-9-methoxy-2H-naphtho [1,2- b] pyran; (b) 2,2-bis (4-methoxyphenyl) -5-hydroxymethyl-6-phenyl-2H-naphtho [1,2-b] pyran; (c) 2,2-bis (4-methoxyphenyl) -5-acetoxymethyl-6-phenyl-2H-naphtho [1,2-b] pyran; (d) 2- (4-methoxyphenyl) -2- (2,3-dihydrobenzofuran-5-yl) -5-piperidinocarbonyl-6-methyl-9-methoxy-2H-naphtho [1,2-b] pyran; (e) 2,2-bis (4-methoxyphenyl) -5-hydroxymethyl-6-methoxy-2H-naphtho [1,2-b] pyran; (f) 2,2-diphenyl-5-methoxymethyl-6-methoxy-2H-naphtho [1,2-b] pyran; (g) 2,2-spiroadamantylene-5-acetoxymethyl-6-methoxy-2H-naphtho [1,2-b] pyran; (h) 2,2-bis (4-methoxyphenyl) -5-trimethylsilyloxymethyl-6-methoxy-2H-naphtho [1,2-b] pyran; (i) 2- (4-methoxyphenyl) -2-t-butyl-5-methoxymethyl-6-phenyl-9-methoxy-2H-naphtho [1,2-b] pyran; and (j) 2- (4-methoxyphenyl) -2- (2,3-dihydrobenzofuran-5-yl) -5-chloromethyl-6-methyl-9-methoxy-2H-naphtho [1,2-b] pyran.

It is contemplated that the organic photochromic naphthoopyran of formula I will be used in combination with other appropriate complementary organic photochromic materials to produce a nearly neutral shade of gray to brown together when the plastic lens containing such photochromic materials is exposed. the ultraviolet light. For example, a yellow-colored compound may be mixed with an appropriate purple-colored compound to produce a brown shade. Similarly, a compound that is orange in its colored state will produce a shade of gray when used in conjunction with a compound that stains with a suitable blue. The combination of photochromic materials described above can also be used in applications other than ophthalmic lenses.

The novel naphthopyran compounds of the present invention, such as those described above, may be used individually or in combination with complementary photochromic compounds, ie organic photochromic compounds having at least activated absorption maxima within the range of about 400 to 700 nanometers, or substances containing same, and may be incorporated, eg, dissolved or dispersed, in a polymeric organic host material used to prepare photochromic articles and which compounds or mixtures of compounds color when activated to an appropriate color.

A first group of complementary organic photochromic substances contemplated for use with the organic photochromic naphthopyran of the present invention are those having a maximum active absorption within the visible range greater than 570 nanometers, eg, between about 570 to 700 nanometers. . These materials typically exhibit a blue, bluish-green, or bluish-purple coloration when exposed to ultraviolet light in an appropriate solvent or matrix. Many of such compounds are described in the available literature. For example, among others, spiro (indoline) naphthoxazine have been described in U.S. Patent Nos. 3,562,172; 3,578,602; 4,215,010; and 4,342,668; spiro (indoline) naphthoxazines having certain substituents at the 8 'and 9' positions of the naphthoazine portion of the molecule are described in U.S. Patent 5,405,958; spiro (indoline) pyridobenzoxazine are described in U.S. Patent 4,637,698; spiro (benzindoline) pyrido-benzoxazine and spiro (benzindoline) naphthoxazine are described in U.S. Patent 4,931,219; spiro (benzido-lidine) naphthopyran are described in Japanese Patent Publication 62/195383; spiro (indoline) benzoxazines are described in U.S. Patent 4,816,584; spiro (indoline) benzopyran, spiro (indoline) naphthopyran, and spiro (indoline) quinopyran are described, for example, in U.S. 4,880,667; and benzopyran and naphthopyran having a nitrogen-containing substituent at the 2- position of the pyran ring are described in U.S. Patent 4,818,096. Spiro (indoline) pyranes 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.

A second group of complementary organic photochromic substances contemplated for use with the organic photochromic naphthoopyran of the present invention are those having at least a maximum absorption within the visible range of from about 400 to less than 500 nanometers. These materials typically exhibit a yellow-orange color when exposed to ultraviolet light in an appropriate solvent or matrix. Such compounds include certain chromos, i.e. benzopyran and naphthopyran. Many of such chromos are described in the available literature, e.g., U.S. Patent 3,567,605; 4,826,977; and 5,066,818. Other examples of complementary benzopyran and naphthopyran which may be used with the naphthopyran of the present invention include: those having a spiro adamantane group at the alpha position relative to the oxygen atom of the pyran ring, which are written in U.S. Patent 4,826,977; 2H-naphtho [1,2-b] pyran compounds having certain substituents on the number 5 and 6 carbon atoms of the naphthoopyran naphtho moiety and the 2-position of the pyran which are the subject of US Patent Application Serial No. 08 1664,187, filed December 9, 1993; 3 H-naphtho [2,1-b] pyran having at least one ortho-substituted phenyl substituent at the 3- position of the pyran ring which are described in U.S. Patent 5,066,818; 3 H-naphtho [2,1-b] pyran compounds having certain substituents on carbon atom number 8 and certain substituents on carbon atom number 7 or 9, all substituents being on the naphtho portion of naphthopyran, which are matter of the US Copending Patent Application Series No. 08 / 080,246, filed June 21, 1993; 3H-naphtho [2,1-b] pyran substituted at the 3-position of the pyran ring with (i) an aryl substituent and (ii) a phenyl substituent having a 5 or 6 membered heterocyclic ring fused to side g, i or 1 naphthopyran which is the subject of US Copending Patent Application No. 08 / 225,022, filed April 8, 1994; naphthopyran compounds substituted at the number 8 carbon atom of the naphtho portion of the naphthopyran ring with, for example, a methoxy group which are the subject of U.S. Patent 5,238,931; naphthopyran compounds. examples of which are 3-aryl arylalkenyl naphthopyran, which are described in U.S. Patent 5,274,132; and carbon-substituted naphtho [2,1-b] pyran number 5 with, for example, an acetoxy group, which are the subject of U.S. Patent 5,244,602.

A third group of complementary organic photochromic substances contemplated for use with the organic photochromic naphthoopyran of the present invention are those having a maximum absorption within the visible range of between about 400 and about 500 nanometers and another maximum absorption within the range. visible range from about 500 to about 700 nanometers. These materials typically exhibit color (s) ranging from yellow to purple and yellow / brown to purple / gray when exposed to ultraviolet light in an appropriate solvent or matrix. Examples of such compounds include certain substituted 2H-phenanthro [4,3-b] pyranes; 3H-phenantho [1,2-b] pyranes; and benzopyran compounds, such as those having substituents at the 2- position of the pyran ring and a substituted or unsubstituted heterocyclic ring, such as a benzothiene or benzofuran ring fused to the benzyl portion of the benzopyran. Such compounds to be described below are the subject of U.S. Copending Patent No. 08 / 286,039, filed August 4, 1994, and U.S. Patent 4,511,679.

Photochromic articles of the present invention may contain a photochromic compound or a mixture of photochromic compounds as desired or required. Individual photochromic compounds or mixtures of photochromic compounds can be used to achieve certain activated colors such as gray or neutral browns.

The compounds of the present invention (hereinafter also referred to and included as a second photochromic compound) may also be used in combination with organic photochromic substances of the first complementary group of photochromic compounds described herein, ie those that are color-stained. blue, bluish green, or bluish purple with other photochromic organic substances in the second group previously described. Members of the first or second group of photochromic compounds or mixtures of such compounds may be combined with or used in conjunction with a third group described herein that exhibit colors ranging from yellow to purple and from yellow / brown to purple / gray.

Each of the photochromic substances described herein may be used in amounts (or in a proportion) such that an organic host material to which photochromic compounds or mixtures of compounds is applied exhibits a desired resulting color, e.g., a substantially neutral color. when activated with unfiltered sunlight, ie as close to neutral as possible given the colors of the activated photochromic compounds.

A neutral gray color exhibits a spectrum that has a relatively equal absorption in the visible range between 400 and 700 nanometers. A neutral brown color exhibits a spectrum in which the absorption in the range of 400-550 nanometers is slightly higher than in the range of 550 to 700 nanometers. An alternative way of describing color is in terms of its chromaticity coordinates, which describe the qualities in addition to its luminance factor, i.e., its chromaticity. In the CIE system, the chromaticity coordinates are obtained by taking the ratios of tristimulus values against their sums, e.g., x = X / (X + Y + Z) & y = Y / (X + Y + Z). Color as described in the CIE system can be plotted on a chromaticity diagram, usually a plot of the x and y chromaticity coordinates. See pages 47-52 of Color Technology Principles, by FWBillmeyer, Jr., and Max Salzman, Second Edition. , John Wíley and Sons, NY (1981), As used herein, a near neutral color is one in which the color coordinate values of "x" and "y" for the color are within the following ranges (illuminating D65): x = 0,260 to 0,400, y = 0,280 to 0,400 following 40% activation of light transmission by exposure to solar radiation (Air Mass 1 or 2).

The amount of photochromic substance or composition containing same applied to or incorporated into a host material is not critical as long as an amount sufficient to produce a discernible photochromic effect to the naked eye upon activation is used. Generally such amount may be described as a photochromic amount. The particular amount used often depends on the desired color intensity under irradiation and the method used to incorporate or apply the photochromic substances. Typically, the more photochromic substance applied or incorporated, the greater the color intensity up to a certain limit.

The relative amounts used of the aforementioned photochromic compounds will vary and will depend in part on the relative color intensities of the activated species of such compounds, and the desired final color. Generally, the total amount of photochromic substance incorporated into or applied to the photochromic optical host material will range from about 0.05 to about 1.0, e.g., from 0.1 to about 0.45 milligrams per square centimeter. surface to which the photochromic substance (s) is incorporated. When mixtures of the complementary organic photochromic groups described above are used, the weight ratio of such materials, ie, (first to second), second to third), and (naphthopyran of the present invention to other second group compounds) will range from about 1: 3 to about 3: 1, eg between about 0.75: 1 and about 2: 1. The combination of the first, second and third organic photochromic complementary groups may have a weight ratio ranging from about 1: 3: 1 to 3: 1: 3.

The photochromic substances of the present invention may be applied to or incorporated into a polymeric host material by various methods described in the art. Such methods include dissolving or dispersing the photochromic substance in the host material, e.g., fusing it into position by adding the photochromic substance to the monomeric host material prior to polymerization; soaking the photochromic substance in the host material by immersing the host material in a warm photochromic solution or by heat transfer; providing the photochromic substance as a separate layer between adjacent layers of the host material, e.g., as a part of a polymeric film; and applying the photochromic substance as part of a coating arranged on the surface of the host material. The term "imbibition" or "imbibe" (sic) is intended to include and include the permeation of the photochromic substance individually into the host material, solvent assisted transfer of the photochromic substance into a porous polymer, vapor phase transfer, and other mechanisms of transfer.

Dyes, i.e., chemically and chromatically compatible dyes, may be applied to the host material to achieve a more aesthetic result, for medical reasons, or for fashion reasons. The particular dye selected will vary and depend on the aforementioned need and the result to be achieved. In one embodiment, the dye may be selected to complement the color resulting from activated photochromic substances, e.g., to achieve a more neutral color or to absorb a specific wavelength of incident light. In another embodiment, the dye may be selected to provide a certain color to the host matrix when the photochromic substances are in a non-activated state.

Adjuvant materials may also be incorporated into the host material with the photochromic substances prior to, simultaneously with or after the application or incorporation of the photochromic substances into the host material. For example, ultraviolet light absorbers may be mixed with photochromic substances prior to their application to the host material or such absorbers may be overlapped, e.g., overlapped, as a layer between the photochromic substance and the incident light. In addition, stabilizers may be mixed with photochromic substances prior to their application to the host material to improve the light fatigue resistance of photochromic substances. Stabilizers such as blocked amine light stabilizers and internal oxygen scavengers, e.g., a nickel ion complex with an organic ligand, are contemplated. They can be used individually or in combination. Such stabilizers are described in U.S. Patent 4,720,356. Finally, suitable protective coating (s) may be applied to the surface of the host material. These may be abrasion resistant coatings and / or coatings that serve as oxygen barriers. Such coatings are known in the art.

The host material will usually be transparent, but may be translucent or even opaque. The host material need only be transparent to that portion of the electromagnetic spectrum that activates the photochromic substance, ie, that wavelength of ultraviolet light (UV) that produces the open form of the substance and that portion of the visible spectrum that includes the maximum absorption length. of the substance in its UV-activated form, ie in its open form. Preferably, the host color should not be such as to mask the color of the activated form of the photochromic substance, i.e., such that the color change is readily apparent to the observer. More preferably, the host material article is a transparent or optically clear solid material, e.g., materials suitable for optical applications such as flat and ophthalmic lenses, windows, automotive transparencies, eg, windshields, aircraft transparencies, plastic laminates, polymeric films. , etc.

Examples of polymeric organic host materials which may be used as the photochromic substances or compositions described herein include: polymers, ie, homopolymers and copolymers, polyol (allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, and alkoxylated polyhydric alcohol acrylate monomers such as ethoxylated trimethylol propane triacrylate monomers; polymers, i.e. , homopolymers and copolymers of polyfunctional acrylate and / or methacrylate monomers, ie, mono-, di-, tri-, tetra- or multi-functional polyacrylates, polymethacrylates, poly (C C - \C C2) alkyl methacrylates) such as poly (methyl methacrylate), polyoxy (alkylene methacrylates) such as poly (ethylene glycol bis methacrylates), poly (alkoxylated methacrylates) such as poly (bisphenol A ethoxylated dimethacrylate), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), polyurethanes, thermoplastic polycarbonates, polyesters, poly (terephthalate) ethylene), polystyrene, poly (alpha methylstyrene), copoly (methyl styrene methacrylate), copoly (styrene-acrylonitrile), polyvinyl butyral and polymers, ie, homopolymers and copolymers of diallylidene pentae-ritritol, particularly copolymers with monomers of polyol (carbone) diethylene glycol bis (allyl carbonate), and acrylate monomers.

Transparent copolymers and transparent polymer blends are also suitable host materials. Preferably, the host material is an optically clear polymerized organic material prepared from a thermoplastic polycarbonate resin, such as a bisphenol A and phosgene-derived carbonate bonded resin, which is sold under the trade name LEXAN; a polyester, such as material sold under the trade name, MYLAR; a poly (methyl methacrylate), such as material sold under the trade name PLEXIGLAS; polymerized from a polyol (allyl carbonate) monomer, which monomer is sold under the trade name CR-39 and polymerized from a polyol (allyl carbonate) copolymers, e.g. diethylene glycol bis (allyl carbonate), with other copolymerizable monomeric materials such as vinyl acetate copolymers, eg, 80-90 percent diethylene glycol bis (allyl carbonate) and 10-20 percent vinyl acetate copolymers, particularly 80-85 percent bis ( allyl carbonate) and 15-20 percent vinyl acetate, and copolymers with a polyurethane having terminal diacrylate functionality, as described in US Patents 4,360,653 and 4,994,208; and aliphatic urethane copolymers, the terminal portion of which contain allyl or acrylyl functional groups, as described in U.S. Patent 5,200,483; poly (vinyl acetate), polyvinyl butyral, polyurethane, group member polymers consisting of diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, and ethoxylated trimethylol propane triacrylate monomers; cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and styrene copolymers with methyl methacrylate, vinyl acetate and acrylonitrile. More particularly, the use of photochromic naphthopyran of the present invention is contemplated with optical organic resin monomers used to produce optically clear polymers, ie materials suitable for optical applications, such as, for example, flat and ophthalmic lenses, windows, and transparencies. automotive Such optically clear polymerizers may have a refractive index which may range from about 1.48 to about 1.75, e.g., from about 1.495 to about 1.66.

The present invention will be more particularly described in the following examples which are intended to be illustrative only, since numerous modifications and variations thereof will become apparent to those skilled in the art.

Example 1 Step 1 [00047] 4,4'-Dimethoxybenzophenone (0.27 mol) was dissolved in a reaction flask containing 200 ml of anhydrous tetrahydrofuran saturated with acetylene and stirred at room temperature. An 18 weight percent suspension of xylene sodium acetylide / mineral oil (0.3 mol sodium acetylide) was added to the reaction flask and the mixture was stirred. After stirring for 16 hours at room temperature under an inert nitrogen atmosphere, the contents of the reaction vial mixture were added to a mixture of 5 weight percent aqueous hydrochloric acid and ice. The resulting mixture was extracted with diethyl ether. The organic layer was separated, washed, and dried over anhydrous sodium sulfate. The solvents, diethyl ether and tetrahydrofuran, were removed under vacuum to give an oily product containing 1,1-bis (4-methoxyphenyl) -2-propyn-1-ol, which was not further purified but used directly in the next step.

Step 2 [00048] 1,1-Bis (4-methoxyphenyl) -2-propyn-1-ol (about 0.025 mol) from Step 1 and methyl, 4-hydroxy-6-methoxy-1-methyl-2-naphthoate (5g, 0.022 mol) were added to a reaction flask containing 200 ml of toluene and stirred. A catalytic amount of p-toluenesulfonic acid (about 100 milligrams) was added, and the mixture was stirred for 4 hours. Subsequently, the reaction mixture was poured into a 10 weight percent sodium hydroxide solution. The organic layer was separated, washed with water, and dried over anhydrous sodium sulfate. The remaining solvent, toluene, was removed under vacuum. The resulting oil was purified using a silica gel column and a 1: 3 mixture of chloroform: hexane as eluent. The photochromic fractions were combined and the eluent was removed under vacuum. The resulting product was induced to crystallize from hexane. The recovered product had a melting point of 132-133 ° C. A nuclear magnetic resonance spectrum (WMR) showed that the product had a structure consistent with 2,2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6-methyl-9-methoxy-2H-naphtho [1,2-b ] pirane.

Step 3 [00049] 2,2-Bis (4-methoxyphenyl} -5-methoxycarbonyl-6-methyl-9-methoxy- [2H] -naphtho [1,2-b] pyran (1.7g, 0.0034moi) from step 2 was dissolved in a reaction flask containing 200 ml and stirred Lithium aluminum hydride (0.13 g, 0.0034 mol) was carefully added and the mixture was stirred for 2 hours at room temperature. It was added followed by the addition of a 5 weight percent aqueous solution of hydrochloric acid. The resulting mixture was extracted with two 100 ml portions of methylene chloride. The organic extracts were combined and dried over magnesium sulfate. The product was induced to crystallize with diethyl ether and the crystals were collected by suction filtration The recovered product, 1.0 g, had a melting point of 125-127 ° C. nuclear magnetic resonance imaging (NMR) showed that the product had a structure consistent with 2,2-bis (4-methoxyphenyl) -5 -hydroxyiraethyl-6-methyl-9-methoxy-β-naphtho [1,2-b] pyran.

Example 2 Step 1 Potassium t-butoxide (75 grams (g), 0.75 mol) was added to a reaction flask containing 200 milliliters (ml) of toluene. The resulting slurry was heated to reflux temperature under a nitrogen atmosphere while a mixture of benzophenone (91 g, 0.5 mol), dimethyl succinate (90 g, 0.62 mol) and toluene (40 g) was added over the period. a 30 minute period. After addition, the resulting pasty mixture was kept at reflux temperature for two hours and then cooled to room temperature. About 400 ml of water was added and the mixture was stirred for 30 minutes. The aqueous layer was separated, acidified with dilute hydrochloric acid, and extracted with 200 ml of toluene. The solvent was removed under vacuum to give a later solidified viscous oil containing the product 4,4-diphenyl-3-methoxycarbonyl-3-butenoic acid. This material was not further purified but was used directly in the next step.

Step 2 The product from step 1 was dissolved in a reaction flask containing 200 ml of toluene, Acetic anhydride (100g) and anhydrous sodium acetate <15g) were added to the reaction flask and the mixture was refluxed for 17 minutes. The resulting mixture was cooled to room temperature and the solvent was removed under vacuum. Methylene chloride (200 ml) was added to the reaction flask containing the resulting residue. Water (200 ml) was added to the reaction flask followed by the slow addition of solid sodium carbonate until the evolving carbon dioxide ceased. The methylene chloride layer was separated, washed with water, and the solvent removed under vacuum. to give a viscous oil containing 1-acetoxy-3-methoxycarbonyl-4-phenylnaphthalene.

Step 3 [00052] Methanol (400 mL) was added to the reaction flask containing 1-acetoxy-3-methoxycarbonyl-4-phenyl-naphthalene from Step 2. Concentrated hydrochloric acid (2 mL) was added to the reaction flask and The resulting mixture was heated to reflux temperature. After 4 hours, the mixture was cooled to room temperature, the solvent was removed under vacuum, and the resulting crystals were collected by suction filtration. The collected crystals were washed with methanol and dried with air. The recovered product, 100 g, had a melting point of 174-176 ° C. A nuclear magnetic resonance spectrum (NMR) showed that the product had a structure consistent with 4-phenyl-3-methoxycarbonyl-1-naphthol.

Step 4 [00053] 4-Phenyl-3-methoxycarbonyl-1-naphthol (2 g) from Step 3 and 1,1-bis (4-methoxyphenyl) -2-propin-1-ol (2 g) from Step 1 Example 1 were added to a reaction flask containing 100 ml of toluene and stirred. The resulting mixture was heated to 40 ° C and a catalytic amount (a few drops) of dodecyl benzene sulfonic acid was added, i.e., an amount sufficient to produce a deep red color in the mixture. After 3 hours of stirring at 40 ° C, the mixture was cooled and washed with water. The organic layer was separated, and the solvent, toluene, was removed under vacuum. The resulting oil was purified using a silica gel column and a 2: 1 mixture of hexane: ethyl acetate as eluent. The photochromic fractions were collected and the solvent was removed under vacuum. The resulting product (2.0 g) was crystallized from a hexane-ether mixture and collected by suction filtration as off-white crystals. The recovered product had a melting point of 16-169 ° C. Nuclear magnetic resonance spectrum (NMR) showed that the product had a structure consistent with 2,2-bis (4-methoxyphenyl) -5-methoxycarbonyl-6-phenyl-2 H-naphtho [1,2-b] pyran, Step 5 [00054] 2,2-Bis (4-methoxyphenyl) -5-methoxycarbonyl-6-phenyl-2H-naphtho [1,2-b] pyran (10.0 g, 0.02 mol) from Step 4 It was dissolved in a reaction flask containing 300 ml of tetrahydrofuran. Lithium aluminum hydride (1.2 g, 0.032 mol) was carefully added to the stirred solution and the mixture was heated at 40 ° C for 2-1 / 2 hours. After cooling to room temperature, 2-propanol was added followed by the addition of a 5 weight percent aqueous hydrochloric acid solution. The resulting mixture was extracted with three 1000 ml portions of diethyl ether. The organic extracts were combined and dried over magnesium sulfate. The solvent, diethyl ether, was removed under vacuum. The resulting residue was induced to crystallize from diethyl ether and the crystals were collected by suction filtration. Three grams of the desired product was recovered. A nuclear magnetic resonance (NMR) spectrum showed that the product has a structure consistent with 2.2-bis (4-methoxyphenyl) -5-hydroxymethyl-6-phenyl-2H-naphtho [1,2-b] pyran.

Example 3 [00055] 2,2-Bis (4-Methoxyphenyl} -5-hydroxymethyl-6-phenyl-2H-naphtho [1,2-b] pyran (2.0 g, 0.004 mol) from Step 4 of Example 2, was dissolved in a reaction flask containing 200 ml of methylene chloride and 1.2 equivalent of triethylamine. Acetyl chloride (0.37 g, 0.0048 mol) was added to the stirred mixture which was heated at reflux temperature for 4 hours. After cooling to room temperature, diethyl ether was added and triethylamine hydrochloride, a by-product, was removed by filtration. The resulting product was purified on a silica gel column using chloroform as eluent. Etochromic fractions were collected and the solvent removed under vacuum. The recovered product, 0.2 g, was induced to crystallize from diethyl ether. A nuclear magnetic resonance (NMR) spectrum showed that the product had a structure consistent with 2.2-bis (4-methoxyphenyl) -5-acetoxymethyl-6-phenyl-2H-naphtho [1,2-b] pyran.

Example 4 Step 1 [00056] 3-Methoxycarbonyl-4-methyl-7-methoxy-1-naphthol (12 g) was added to a reaction flask containing potassium hydroxide (25 g), water (250 ml) and ethanol ( 50 ml). The mixture was heated in a water bath for 6 hours, cooled to room temperature, and poured into an excess of dilute aqueous hydrochloric acid (approximately 5 weight percent). The resulting solid product was removed by suction filtration and dried to obtain 11 g of the desired product, 3-carboxy-4-methyl-7-methoxy-1-naphthal.

Step 2 [00057] 3-Carboxy-4-methyl-7-7-methoxy-1-naphthol (11 g) from Step 1 was added to a reaction flask containing · 100 ml methylene chloride, Triethylamine (10 g, 0%). 1 mol) was added with stirring. The resulting exothermic reaction mixture was cooled in an ice bath. Acetyl chloride (4 g, 0.05 mol) was added dropwise while maintaining the temperature at 5 ° C. The mixture was stirred for an additional 15 minutes at 5 ° C and then warmed to room temperature when it was stirred for an additional 15 minutes before being poured into excess dilute aqueous hydrochloric acid (at approximately 5 weight percent). The precipitated product was filtered off with suction of the biphasic mixture, washed with fresh methylene chloride, and dried to obtain 11 g of the desired product. An NMR spectrum showed the product to have a structure consistent with 1-acetoxy-3-carboxy-4-methyl-7-methoxine phthalene.

Step 3 1-Acetoxy-3-carboxy-4-methyl-7-methoxynaphthalene (11 g) from Step 2 was added to a reaction flask containing 20 ml of thionyl chloride and the mixture was heated in a Maria. After about 30 minutes, when the hydrochloric acid evolution was complete, excess thionyl chloride was removed on a rotary evaporator to obtain the acid chloride as a solid. The product, 1-acetoxy-3-chlorocarbonyl-4-methyl-7-methoxynaphthalene, was not further purified but was used directly in the next step.

Step 4 A half of the 1-acetoxy-3-chlorocarbonyl-4-methyl-7-methoxynaphthalene from Step 3 was added in small portions to a reaction flask containing a mixture of methylene chloride (50 ml), piperidine ( 4.25 g, 0.05 mol) and triethyl amine (5 g, 0.05 mol). After the addition was complete, an excess of dilute aqueous hydrochloric acid (approximately 5 weight percent) was added and the resulting solution was mixed. The organic layer was separated, washed successively with water, dilute aqueous sodium carbonate, and water. The solvent, methylene chloride, was removed under vacuum to obtain the product as an oil. An NMR spectrum showed the product to have a structure consistent with 1-acetoxy-3-piperidinocarbonyl-4-methyl-7-methoxynaphthalene.

Step 5 A mixture (200 ml) of methanol and concentrated hydrochloric acid (2 ml) was added to a reaction flask containing 1-acetoxy-3-piperidinocarbonyl-4-methyl-7-methoxynaphthalene from Step 4. The mixture The resulting reaction mixture was refluxed in a water bath for 2 hours. The mixture was then cooled to room temperature and poured into dilute aqueous hydrochloric acid. The resulting precipitate was suction filtered, washed with water, and dried to obtain 4.8 g of the desired product as brown crystals. An NMR spectrum showed the product to have a structure consistent with 3-piperidinocarbonyl-4-methyl-7-methoxy-1-naphthol.

Step 5 [00061] 3-Piperidinocarbonyl-4-methyl-7-methoxy-1-naphthol (2.5 g) from Step 5 and 1- (2,2-dihydroxybenzofur-5-yl) -1- (4- methoxyphenyl) -2-propyn-1-ol (2.5 g) was added to a reaction flask containing 100 ml of toluene and stirred. The stirred mixture was heated to 50 ° C and a few drops of dodecyl benzenesulfonic acid were added (an amount sufficient to produce a deep red color).

After two hours, the reaction mixture was cooled to room temperature and water was added. The organic layer was washed with water and the solvent was removed on a rotary evaporator. The resulting oil was purified using a silica gel column and a 1: 1 hexane: ethyl acetate mixture as eluent. The photochromic fractions were combined, concentrated and induced to crystallize from a small amount of a diethyl ether: hexane mixture. The desired product was recovered by suction filtration and dried to obtain 2.6 g of crystals having a melting point of 201-203 ° C. NMR spectrum showed that the product had a structure consistent with 2- (4-methoxyphenyl) -2- (2,3-dihydroxybenzofuran-5-yl) -5-piperidinocarbonyl-6-methyl-9-methoxy-2H -naphtho [1,2-b] pyran, Example 5 Part A

Tests were performed with the photochromic naphthopyran of the Examples incorporated into the polymeric samples by the following method. The amount of naphthopyran calculated to give a 1.5-fold 10-3 molal solution was added to a vial containing 50 grams of a monomer mixture with 4 parts ethoxylated bisphenol A dimethacrylate (ΒΡΑ 2E0 DMA), 1 part dimethacrylate poly (ethylene glycol) 600, and 0.033 weight percent 2,2'-azobis (2-methyl propionitrile) (AIBN). Naphthopyran was dissolved in a mixture of monomers with stirring and gentle heating if necessary. After a clear solution was obtained, it was poured onto a flat plate mold having internal dimensions of 2.2 mm x 6 inches (15.24 cm) x 6 inches (15.24 cm). The mold was sealed and placed in a programmable horizontal air flow oven to raise the temperature from 40 ° C to 95 ° C over a 5 hour interval, maintain the temperature at 95 ° C for 3 hours and then lower it to 60 ° C at least two hours before the end of the cure cycle. After the mold was opened, the polymer sheet was cut using a square diamond blade saw having 2 inches (5.1 centimeters).

Part B

[00064] The photochromic test squares prepared in Part A have been tested for photochromic response rates on an optical bench. Prior to optical bench testing, the photochromic test squares were exposed to 365 nanometer ultraviolet light for about 15 minutes to activate the photochromic compounds and then placed in a 76 ° C oven for about 15 minutes to target or deactivate them. photochromic compounds. The test squares were 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 testing on an optical bench held at 75 ° F (23.9 ° C). A 150 watt Xenon arc lamp, a remote controlled curtain, a copper sulphate bath acting as a heat shroud for the arc lamp, a Schott WG-320 cut filter that removes radiation from short waves; neutral density filter (s) and a sample retainer into which the square to be tested has been inserted. A collimated beam of light from a tungsten lamp was passed through the square at a small normal squared angle. After passing through the square, the light from the tungsten lamp was directed through a photopic filter attached to a detector. The photopic filter passes wavelengths such that the detector throws the response of the human eye. The output signals from the detector (s) were processed by a radiometer.

Optical density (@OD) changes were determined by inserting a targeted test square into the sample retainer, adjusting the transmittance scale to 100%, opening the xenon lamp curtain to provide ultraviolet radiation to change the square. test the target state to an activated (ie, darkened) state by measuring the transmittance in the activated state, and calculate the optical density change according to the formula AOD = log (100 /% Ta) where% Ta is the percent transmittance. in the activated state and the logarithm is in base 10.

AOD / Min, which represents the sensitivity of the photochromic compound's response to UV light, was measured over the first five (5) seconds of UV exposure, and then expressed on a per minute basis. Saturation optical density (OD) was determined under conditions identical to Δ OD / Min, except that UV exposure was continued for 20 minutes for the examples in Table 1. The max lambda reported in Table 1 is the wavelength in the visible spectrum in which the maximum absorption of the activated (colored) form of the photochromic compound occurs in a diethylene glycol bis (diallyl carbonate) composition. Targeting Rate (T 1/2) is the time interval in seconds for the absorbance of the activated form of naphthopyran in the test squares to achieve the highest absorbance at room temperature (7S ° F, 23.9 ° C) after removal of the activating light source. Results for the compounds of the Examples are tabulated in Table 1. Table 1 The results of Table 1 show that the targeting rate of 2 H-naphtho [1,2-b] pyran is dramatically affected by the nature of the 5-position substituent. For example, Compounds 1 to 3 have an acceptable bleaching, ie, bleaching rate, while Compound 4 fades more slowly. All Example Compounds have a high saturation OD, i.e., activated intensity, and a high staining rate, i.e., sensitivity.

Although the present invention has been described with respect to the specific details of particular embodiments thereof, it is not intended that such details be construed as limiting the scope of the invention except as and to the extent that they are included in the appended claims.

Claims (6)

Naphthopyran compound, characterized in that it is represented by the following graphic formula: where: (a) R1 is selected from the group consisting of -CH2X and -C (O) Y, where X is halogen, hydroxy, benzyloxy, C1-4 alkoxy C 1 -C 6 acyloxy C 6 -C 6 amino, C 1 -C 6 monoalkylamino, C 1 -C 6 dialkylamino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, trimethyl siloxy and Y is a heterocyclic ring selected from the group consisting of 1 -indolinyl, morpholine, piperidine, 1-pyrrolidyl, 1-imidazolidyl, 2-imidazolin-1-yl, pyrazolidyl, pyrazolinyl, and 1-piperazinyl; (b) R2 and each R3 are hydrogen, C1-C4 alkyl, C3-C7 cycloalkyl, phenyl, the -ORg group, where Rg is hydrogen, C1-Cg alkyl, phenyl (C4-C3) phenyl, (C4-C3) alkyl ) monosubstituted phenyl, C 1 -C 6 alkoxy C 2 -C 4 alkyl, C 3 -C 7 cycloalkyl, C 3 -C 7 cycloalkyl monosubstituted with C 4 -C 4 alkyl, C 1 -C 6 haloalkyl, and from 0, 1 and 2, and the substituents phenyl being C 1 -C 4 alkyl, C 4 -C 4 alkoxy or fluorine; and (c) B and B 'are each selected from the group consisting of: (i) unsubstituted and monosubstituted aryl, phenyl and naphthyl groups, with aryl substituents being selected from the group consisting of hydroxy, amino, C 1-4 alkylamino -Cg, C 1 -C 6 dialkylamino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, 1-imidazolidyl, 2-imidazolin-1-yl, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl, C 1 -C 6 alkyl, C 1 haloalkyl] C 1 -C 6 alkoxy, C 1 -C 6 monoalkoxy C 4 -C 4 alkyl and halogen, said halogen being fluorine or chlorine; (ii) the groups represented by the following graphic formulas: where D is a carbon atom and E is oxygen; each R 6 is C 1 -C 6 alkyl, C 1 -C 6 alkoxy, hydroxy, chloro or fluoro, R 6 and R 10 are each hydrogen or C 1 -C 6 alkyl; and m is the integer 0, 1 or 2; (iii) C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy C 1 -C 4 alkyloxy, C 1 -C 6 cycloalkyl monoalkoxy, C 1 -C 6 cycloalkyl monoalkyl, and halo C6 -C6 cycloalkyl, said halo groups being fluorine or chlorine; and (iv) the group represented by the following graphic formula: where U is hydrogen or C4-C4 alkyl, and V is selected from the group consisting of unsubstituted or mono- and disubstituted members of the group consisting of naphthyl, phenyl, furanyl, and thienyl, the substituents for each member of said group being C1-C4 alkyl, C1-C4 alkoxy, fluorine or chlorine; or (v) B and B 'taken together form an unsubstituted, mono-, or disubstituted fluoren-9-ylidene or a member selected from the group consisting of saturated C3 -C12 spiro-monocyclic hydrocarbon rings, spiro-bicyclic hydrocarbon rings Saturated C7 -C12, saturated C7 -C12 spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituents being selected from the group consisting of C2 -C4 alkyl, C1 -C4 alkoxy, fluorine and chlorine. A compound according to claim 1 wherein: (a) Rg is selected from the group consisting of -CH2X and -C (O) Y, where X is hydroxy, C1-C4 alkoxy, or C2-acyloxy C4, Y is a heterocyclic ring selected from the group consisting of 1-indolinyl, morpholino, piperidino, and 1-pyrrolidyl; (b) R 2 and each R 3 are hydrogen, C 1 -C 4 alkyl, phenyl, the -ORg group, where R g is C 4 -C 4 alkyl and n is selected from integers 0, 1 and 2; and (c) B and B 'are each selected from the group consisting of: (i) unsubstituted and monosubstituted phenyl, each of the phenyl substituents being selected from the group consisting of morpholino, piperidino, C1-C4 alkyl, C1-alkoxy -C 4, and halogen, said halogen or (halo) being fluorine or chlorine; (ii) the groups represented by the following graphic formula: where D is carbon and E is oxygen; each R 6 is C 4 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxy, or halogen, said halogen being chlorine or fluorine; R 9 and R 40 are each hydrogen or C 1 -C 4 alkyl; and m is the integer 0, 1 or 2; (iii) C4 -C4 alkyl, C1 -C4 alkoxy C4 -C4 alkyl, and C3 -C5 cycloalkyl; and (iv) the group represented by the following graphic formula: where U is hydrogen or methyl, and V is phenyl or monosubstituted phenyl, said phenyl substituent being C1-C4 alkyl, C1-C4 alkoxy, or fluorine; or (v) B and B 'taken together form an unsubstituted or monosubstituted fluoren-9-ylidene or a member selected from the group consisting of saturated C3-C8 spiro-monocyclic hydrocarbon rings, C7-C10 spiro-dicyclic hydrocarbon rings saturated and saturated C 7 -C 30 spiro-tricyclic hydrocarbon rings. A compound according to claim 2, characterized in that: (a) Rq is the group -CH2X, or -C (O) Y, where X is hydroxy, alkoxy or C2 -C4 acyloxy and Y is a heterocyclic ring selected from the group consisting of 1-indolinyl, morpholino and piperidino; (b) R 2 and each R 3 are hydrogen, C 1 -C 2 alkyl, phenyl, the group -ORg, where R 5 is C 3 -C 2 alkyl and n is selected from integers 0, 1 and 2; and (c) B and B 'are each phenyl; and <ii) the groups represented by the following cryptographic formula: where D is carbon and E is oxygen; each R 0 is C 3 -C 2 alkyl, C 1 -C 2 alkoxy or fluorine; R 6 and R 40 are each hydrogen or C 4 -C 2 alkyl; and m is the integer 0, 1, or 2; or (v) B and B 'taken together form fluoren-9-ylidene, bornylidene, norbornylidene, bicyclo [3.3.1] nonan-9-ylidene or adamantilidene. A compound according to claim 3 wherein R 1 is hydroxymethyl or acetoxymethyl, morpholinocarbonyl or piperidino carbonyl; R 2 and each R 3 are hydrogen, phenyl, methoxy or methyl; and B and B 'are each phenyl, methoxy substituted phenyl, phenyl substituted morpholine, or 2,3-dihydrobenzofuran-5-yl. 5 Naphthopyran compound, characterized in that it is selected from the group consisting of: (a) 2,2-bis (4-methoxyphenyl) -5-hydroxymethyl-6-methyl-9-methoxy-2H-naphtho [1,2-b ] pyran; (b) 2,2-bis (4-methoxyphenyl) -5-hydroxymethyl-6-phenyl-2H-naphtho [1,2-b] pyran; (c) 2,2-bis (4-methoxyphenyl) -5-acetoxymethyl-6-phenyl-2H-naphtho [1,2-b] pyran; (d) 2- (4-methoxyphenyl) -2- (2,3-dihydrobenzofuran-5-yl) -5-piperidinocarbonyl-6-methyl-9-methoxy-2H-naphtho [1,2-b] pyran; (e) 2,2-bis (4-methoxyphenyl) -5-hydroxymethyl-6-methoxy-2H-naphtho [1,2-b] pyran; (f) 2,2-diphenyl-5-methoxymethyl-6-methoxy-2H-naphtho [1,2-b] pyran; (g) 2,2-spiroadamantylidene-5-acetoxymethyl-6-methoxy-2H-naphtho [1,2-b] pyran; (h) 2,2-bis (4-methoxyphenyl) -5-trimethylsilyloxymethyl-6-methoxy-2H-naphtho [1,2-b] pyran; (i) 2- (4-methoxyphenyl) -2-t-butyl-5-methoxymethyl-6-phenyl-9-methoxy-2H-naphtho [1,2-b] pyran; (j) 2- (4-Methoxyphenyl) -2- (2,3-dihydrobenzofuran-5-yl) -5-chloromethyl-6-methyl-9-methoxy-2H-naphtho [1,2-b] pyran.