CA2130272A1 - Photochromic naphthopyrans - Google Patents

Abstract

Described are novel reversible photochromic naphthopyran compounds substituted at the number eight carbon atom on the naphtho portion of the naphthopyran ring with, for example, a methoxy group.
Also described are organic host materials that contain or that are coated with such compounds. Articles such as ophthalmic lenses or other plastic transparencies that incorporate the novel naphthopyran compounds are also described.

Description

W O 93/1707t PCT/US93/00873 ,.....
Z~3027Z

PHOTOC~RC~.IC NAPHTHOPYRANS

DESCRIPTION OF T~E_I~VENTION

The pre~ent in~entlon relates to certain novel naphthopyrsn compounds. More particularly, this invention relates to novel photochromic naphthopyran compound6 with unexpected properties, and to composition6 and articles containing 6uch novel naphthopyran compounds. When exposed to light radiation involving ultraviolet (W ) 10 rays, 6uch as the ultraviolet radlation in 6unl~ght or the llght of a mercury lamp, many photochromic compounds exhlbit a rever61ble change in color. When the ultraviolet radiation is discontinued, the photochromic compound will return to its original color or colorless 6tate.
Variou6 classe6 of photochromic compounds have been synthesized and ~ugge6ted for use in applications in which a ~unlight-induced rever~ible color change or darkening i~ desired.
U.S. Patent 3,567,605 (Becker) de~cribes a ~eriefi of chromene derivatives, including certaln benzopyrans and naphthopyrans. These 20 compounds are described as derivatives of chromene and are reported to undergo a color change, e.g., from colorle6s to yellow-orange, on irradiation by ultxaviolet light at temperature6 below about -40C.
Irradistion of the compound6 with ~is~b~e light or upon raising the temperature to within the range of -10C. to 0C. i~ reported to 25 reverse the coloration to a colorless 6tate. U.S. patent 4,931,221 de8cribeC 8 series of spiropyrans in which two cyclopropyl groups are appended to the po~ition adjacent to the oxygen in the pyran ring.
U.S. patent 4,563,458 describes certain 2H chromenes as precursors of certain chroman-4-aldehyde6, which are reacted with certain amines to 30 prepare 4-aminomethylene-chromans and -chromenes that are used in medicaments.
European Patent Publication 246,114 and U.S. Patent 4,826,977 describe a serie6 of photochromic spiropyrans in which a spiro-adamantane group is appended to the pos tion adjacent to the 35 oxygen in the pyran ring. United States Patent 4,818,096 and European Patent Publication 250,193 de~cribe photoreactive plastic lenses that are coated or impregnated with the photochromic Z~30~

spiropyran6 of European Patent Publlcation 246,114 in combination with a photochromic benzopyran or naphthopyran having an aminophenyl 6ubstituent at the position adjacent to the oxygen in the pyran ring.
European Patent Publication 294,056 describe6 a proces6 for producing 5 a polyurethane plastic having photochromic properties. Rever~ible cleavage photochromic compounds disclosed therein include a naphthopyran derivative in which the pyran ring i8 substituted at the 3-p w ition of the pyran ring with di(p-methoxyphenyl) 6ubstituents.
Japanese Patent Publication HEI 2(1990)-69471 describe~ spiropyran 10 compound~ in which a norbornylidene group is su~6tituted at the position adjacent to the oxygen in the pyran ring.
Padwa et al in J. Org. Chem., Volume 40, No. 8, 1975, page 1142, describe~ the investigation of photochemical reactions of 2,2-dimethylbenzopyran and related compounds, identifies the 15 by-products and sugge6ts pathways to the ring-opened color ~ ~ntermediate6 and the final non-colored phenolics. The color forms ; examined by the authors are reported as being unstable at room temperature. The authors do not suggest ways in wh~ch the ~tability of the examined compounds might be improved, nor any modification that 20 might be made to the structure of the known pyran compoundc.
The present invention relates to novel naphthopyran compounds conta~ning certain substltuents at the number eight carbon atom on the naphtho portion of the naphthopyran. The ab60rption maxima of these compounds have been found to be unexpectedly h~gher than the 25 corresponding un~ubstituted compound~.

~T~ a ~S~RIPTION OF THE INVE~In~
In recent-years, photochromic plastic materials, particularly plastic materials for optlcal applications, have been the subject of 30 considerable attention. In particular, photochromic ophthalmic plastic lenses have been investigated because of the weight advantage they offer, vis-a-vis, glass len6e6. Moreover, photochromic transparencies for vehicles, such as cars and airplanes have been of interest because of the potential safety features that such 35 tran~parencies offer.
Ideal photochromic compounds for use in optical applications, such as conventional ophthalmic lenses, are those which possess (a) a W O 93~17071 PCT/US93/00873 ` Z13~Z~7Z

high quantum efficiency for coloring, (b) a relatively fast change in optical density over tlme, (c) a high optical density at 6aturation, (d) a low quantum y~eld for bleaching wlth visible light and 5e) a relatively fast thermal fade at ambient temperature but not 60 rapid a 5 thermal fade rate that the combination of visible light bleaching and thermal fade prevent coloring by the ultraviolet component of ~trong sunlight. The afore6aid propertie~ are desirably retained when the photochromic compound is applied to or incorporated within conventional rigid ~ynthetic plastic material~ customarily used for lO ophthalmic and plano lenses. A naphthopyran such a6 3,3-diphenyl-3H-naphtho[2,l-b]pyran, changes color on expo~ure to ultraviolet; b1~t, at room temperature and above, this compound changes optical density too 810wly, ha6 too low an optical den~ity at saturation, and bleache6 too rapidly for u6e in an ophthalmic len~.
In accordance with the present invention, there has been discovered certain novel reversible photochromic naphthopyran compounds with unexpected propertie~. The~e compounds are ~ub~tituted at the number eight carbon atom on the nsphtho portion of the naphthopyran, and exhibit a dramatic bathochromic shift of thelr 20 absorption maximum in both the ~i~ible spectrum of the activated form and the W spectrum of the unactivated form. The shift ln the W
spectrum has contributed to an increase in sensitivity as mea6ured by how fast the optical density of the compounds change with time, and to an increase in the compounds optical den~ity, as measuled by how dark 25 they become, v~avis, naphthopyrans substituted at the number five, seven or nine carbon atom of the naphtho portion of the naphthopyran.
In particular, 3,3-diaryl-3H-naphtho- ~2~l-b] pyran~ that are appropriately sub~tituted at the number e~ght carbon atom have a high quantum efficiency for coloring, good sensitivity and saturated 30 optical den&ity, and an acceptable bleach or fade rate. Such compound~ are particularly suitable ror u~e in ophthalmic applications.

W O 93~17071 PCT/US93/00873 ~., ~ ., Z130272 `
. ' ! . ,' . i , Naphthopyran compounds contemplated to be within the scope of the present invention may be represented by the following graphic formula I, RB ~ (I) In graphic formula I, R5 and Rg are each selected from the group consisting of hydrogen, Cl C4 alkoxy, e.g., methoxy, and Cl-C4 20 alkyl, e.g., methyl. R8 is 6elected from the group consi6ting of halogen, Cl-C5 acyloxy, benzoyloxy, methoxybenzoyloxy, di(Cl-C5) alkylamino and L0-, wberein L is a Cl-C12 alkyl, C6-C9 aryl(Cl-C3)alkyl, C5-C7 cyclo~lkyl, or Cl-C4 alkyl eubstituted C5-C7 cycloalkyl. The C6-C~ moiety of the C6-Cg aryl(Cl-C3~alkyl group 25 compri~es unsubstituted and alkyl-sub~tituted benzene groups9 i.e., ¦ mono-, di-, or tri-, alkyl substituted benzene. Preferably, R8 is chloro, bromo, Cl-C2 acyloxy, e.g., acetoxy, benzoyloxy, di(Cl-C2) ~ alkylamlno, and L0 wherein L i6 a Cl-C4 alkyl, C6-C7 aryl(Cl-C2)alkyl, ¦ C5-C6 cycloalkyl, or Cl-C2 alkyl substituted C5-C6 cycloalkyl.
I 30 In graphic formula I, B and B' are each selected from the groupconsisting of (i) the unsubstituted or substituted aryl group6 phenyl and naphthyl, (ii) the unsubstituted or substituted heterocyclic aromatic groups pyridyl, thienyl, benzothienyl, furyl and benzofuryl, and (iii) B and B' taken together form the adamantyl group, said aryl 35 and heterocyclic group substituents each being selected from Cl-C4 alkyl, Cl-C4 haloalkyl, Cl-C4 alkoxy, Cl-C4 alkoxy(Cl-C4)alkyl, W O 93tl7071 PCT/US93/00873 ; .
- 5 - ~3`~Zq%
di(Cl-C~)alkylamino and halogen, said halogen (halo) substituents being 6elected from fluorine, chlorine and bromine, prov~ded that at least one of ~ ~nd B' i~ a sub6tituted or ur.substituted phenyl gro-tp except when B and B' form the adamantyl group.
Preferably B and B' are each phenyl or sub~tituted phenyl, e.g., mono- or di-(Cl-C4)alkyl ~ub6tituted phenyl, such as methylphenyl; mono- or di-(Cl-C4)alkoxy ~ub6t~tuted phenyl, ~uch as methoxyphenyl; and halophenyl, such as chlorophenyl and fluorophenyl.
The phenyl 6ub6tituents may be located at the ortho, meta, and/or para lO position~. Typically, the substituted phenyl contain6 less than 3 6ub~tituents, i.e., zero (none), one or two 6ubstituent~. More particularly, B and B' are the 6ub6tituted phenyl groups repre~ented by the following graphic formulae I-A and I-B respectively, ~ ~ y~ ~ Z~) b (1 - ~) (1 - B) wherein Yl may be selected from the group con6i~ting of Cl-C5 alkyl, e.g., methyl, ethyl, propyl, butyl and pentyl, Cl-C5 alkoxy, e.g., methoxy, ethoxy, propoxy, butoxy and pentoxy, fluoro and chloro, preferably Cl-C3 alkyl, Cl-C3 alkoxy and fluoro; Zl may be selected ~0 from the group consisting of hydrogen and Yl, preferably hydrogen;
each Y2 and Z2 may be selected from the group consisting of Cl-C~
alkyl, Cl-C5 alkoxy, cyano, hydroxy, halogen, preferably chloro or fluoro, acrylyl, methacrylyl, acryloxy (Cl-C4) alkyl, and methacryloxy (Cl-C4) alkyl. Preferably, each Y2 and Z2 are ~elected from the group 35 consisting of Cl-C3 alkyl, Cl-C3 alkoxy and fluoro. In a particular embodiment, Y2 is Cl-C3 alkyl or Cl-C3 alkoxy, Z~ is Cl-C3 alkyl, or Cl-C3 alkoxy; and a and b are each integer6 of from 0 to 2; preferably ~ r ~ s, ~

a i8 0 or l, and b is 0, l or 2. The po6itionlng of ~he Y2 and Z2 subst~tuents is prefersbly in the 3,4 or 5 position6. When a or b i8 l, the preferred position i6 meta or para to the carbon atom attached to the pyran rin8. When a or b is 2, the positions are preferably at 5 the 3 and 4, 3 and 5, or 4 and 5 numbered carbon atoms.
Compounds represented by graphic formulae I may be prepared by various synthetic routes. For example, the reaction of 2,6-dihydroxynaphthalene with an appropriate reagent, e.g, dimethyl sulfate will yield the corresponding substituted hydroxynaphthalene 10 e.g., 6-methoxy-2-hydroxynaphthalene. The intermediate 6-substituted-2-hydroxynaphthalene may then be reacted further with the appropriate di6ubstituted, i.e., B,B'-sub6tituted, propargyl alcohol, e.g., l,l-diphenyl-2-propyn-l-ol, der acidic conditions to form compounds of graphic formula I. Becau~e of the limited 15 availability of 2,6-dihydroxynaphthalene, it is contemplated that other-sub~tituted dihydroxynapht~alene starting reagents, i.e, ~ 2,3-d1hydroxynaphthalcne-6-sulfonic acid sod~um salt and - 2,7-dihydroxynaphthalene-3-6-di~ulfonic acid disodium 6alts, which are more readily available in commercial quantities, may be used to 20 synthesize the compound6 of graphic fonmula I. The presence of an alkoxy group, e.g., methoxy, on the number 5 andlor 9 carbon atoms of - the resultinK naphthopyran compound does not affect the unexpected - photochromic properties observed for the naphthopyran compounds having the described substituent6 on the number 8 carbon atom. It is also 25 contemplated that other starting dihydroxy~aphthalene reagents which result in sub6tituent6 on the naphtho portion of the naphthopyran (in addltion to the desired 6ubstituent on the number 8 carbon atom) that do not affect the observed unexpected bathochromic sh~ft of the absorption maximum may be used to synthesize the naphthopyran 30 compounds of graphic formula I.
Compound6 represented by graphic formula I may be used in those applicaLion6 in which organic photochromic substances may be employed, such as for example in optical lense6, e.g., ophthalmic and plano lenses, face shields, goggles, visors, camera lenses, windows, 3S automotive windshields, aircraft and automotive tran6parencies, e.g., T-roofs, sidelights and backlights, plastic films and ~heets, textiles and coating6, e.g., in coating compositions such as paints.

" ` :.` ': ,, `:
2130;;~72 Naphthopyran6 represented by graphic formula I exhibit color change6 from colorles6 to color6 ranging from yellow to orange.
Of pPrt~cular current interest ~re the following naphthopyrans:
(1) 8-methoxy-3,3-diphenyl-3H-naphtho [2,1-b~pyran.
(2) 8-methoxy-3-(2-fluorophenyl)-3-(4-methoxyphenyl)-3H-naphtho[2,1-b] pyran.
(3) 8-methoxy-3-phenyl-3-(4-methylphenyl)-3H-naphtho[2,1-b]
pyran.

(4) 8-methoxy-3-phenyl-3-(4-trifluoromethylphenyl)-3H-naphtho[2,1-b~ pyran.

(5) 8-methoxy-3-(2-fluorophenyl)-3-(4-methylphenyl)-3H-naphtho[2,1-b3 pyran (6) 8-methoxy-3-(4-dimethylaminophenyl)-3-(phenyl)-3H-naphtho[2,1-b] pyran.

(7) 5,8-dimethoxy-3,3-diphenyl-3H-naphtho[2,1-b] pyr~n.

(8) 8-bromo-3-phenyl-3-(4-methylphenyl)-3H-naphtho~2,1 b]
pyran.

(9) 5,8,9-trimethoxy-3,3-diphenyl-3H-naphtho[2,1-b]pyran.
Naphthopyrans described herein may be dissolved i~ common organic solvents such a~ benzene, toluene, chloroform, ethyl acetate, methyl ethyl ketone, acetone, ethyl alcohol, methyl alcohol, acetonitrile, tetrahydrofuran dioxane, methyl ether of ethylene 25 glycol, dimethylformamide, d~methyl~ulfoxide, morpholine and ethylene glycol. They may al80 be dispersed ~n fluorocarbons and in liquid6 containin~ water and/or alcohol~.
The aforede6cribed naphthopyran compounds may also be dis601ved in solution6 prepared with tran~parent organic host 30 materials, e.g., transparent polymers (homopolymers or copolymers) or blends of 6uch transparent polymers and optionally a suitable organic solvent, e.g., transparent polymers dissolved in one or more of the aforede6cribed organic solvents. Examples of such solutions include a poly(vinyl acetate)-acetone solution, a nitrocellulose-acetonitrile 35 601ution, a poly(vinyl chloride)-methyl ethyl ketone solution, a poly(methylmethacrylate)-acetone solution, a cellulose W 0 93/17071 P ~ /US93/00873 acetate-dimethylformamide solution, a poly(vinyl pyrrolidone)-acetonitrile solution, a polystyrene-benzene 601ution and an ethyl cellulose-methylene chloride solution. The aforesaid photochromic solutions or compositions may be applied to a compatible ho~t 5 material, e.g., a transparent support, such as cellulose triacetate, polyethylene terephthalate or baryta paper and dried to obtain an article that will color on exposure to ultraviolet radiation and that will return to it~ original 6tate by removing the source of ultraviolet radiation.
The naphthopyran compound~ described herein (or composition6 containing them) may be applied to or incorporated also within a coating compo6ition applied to a compatible support; or applied to or incorporated within the article comprising the compatible host, e.g., a polymerized organic material such a~ a synthetic polymeric plastic 15 host material.
The naphthopyrans described hereinabove may be incorporated in 6ynthetic pla6tic material6 cu6tomarily used for pla6tic optical len~e6, both plano and ophthalmic, e.g., material6 such a6 methyl methacrylate, polycarbonate6 and polymerizates prepared from CR-39 20 diallyl glycol carbonate monomer.
On irradiation of the compounds of graphic formula I with ultraviolet light, the naphthopyran ring i~ believed to open rever~ibly at the carbon-oxygen bond between the number 3-carbon atom and the ring oxygen. The formation of the open form of the colorles6 25 compound i8 believed to be re~ponsible for the coloring ob6erved on exposure to ultraviolet light. The colored form of the photochromic compound6 of graphic formula I wlll fade to the colorles6 state at normal ambient temperature6 when not expo6ed to ultraviolet light.
Commercially available photoresctive inorganic gla6s 30 ophthalmic lenses contsining ~ilver halide psrticles darken to 8 gray or brown color in 6unlight. In order to duplicate thi~ color change in a plastic lens using the organic photochromic naphthopyrans of graphic formula I, it i8 contemplated that 6uch naphthopyrans be used in combination with other appropriate complementary organic 35 photochromic materials so that together they produce the de6ired near neutral gray or brown color shade when the plastic lens containing ':

~ 2~30Z7Z

g such photochromic materials are expofied to ultraviolet light. For example, a compound which color6 to yellow may be blended with a compound that colors to an appropr~ate purple to produce a brown shade. Similarly, a compound which is orange in it6 colored state 5 will produce a shade of gray when used in conjunction with an appropriate blue coloring compound. The afore6s~d described combination of photochromic material6 may be used alRo in applications other than ophthalmic lenses.
Sp~ro(indolino) pyrido benzoxazine photochromic compound~

10 de6cribed in U.S. Patent 4,637,6~8 and ~piro(indolino) naphthoxazines described in U.S. Patents 3,562,172, 3,578,602, 4,215,010 and 4,342,668 are reported to color to color~ ranging from purple to blue when activated, and these compounds may be used in admixture with or in conjunction with the yellow-orange novel naphthopyran photochromic 15 compounds described in thi~ applicatlon to obtain a near gray color when expo~ed to unfiltered 6unlight. In addition, certain spiro(indolino)benzoxazine6 described in U.S.Patent 4,816,5~4 color to shades of purple/blue when activated, and these compounds may be u6ed also in admixture with or in conjunction with the photochromic 2~ naphthopyran6 described in this application.
The aforesaid fir6t mentioned 6piro(indolino)-type compounds may be represented by the following graphic formula:

~/
30 ( Rl 1 ) d~ ~ ,( R~) o . ..
i, 213~0?.72 10 -In the above graphic formula II, Rl may be selected from the group con~i6ting of Cl-C8 slkyl, e.g., methyl, ethyl, n-propyl, isopropyl, butyl, etc., phenyl, phen(Cl-C4)alkyl, e.g., benzyl, naphth(Cl-C4)slkyl, e.g., l-naphthylmethyl, allyl, 5 acrylyl(C2-C6)alkyl, methacrylyl- (C2-C6)alkyl, carboxy(C2-C6-)alkyl, e.g., ~-carboxyethyl, y-carboxypropyl, ~-carboxybutyl, cyano(C2-C6)alkyl, e.g., ~-cyanoethyl, y-cyanopropyl, ~-cyanoisopropyl, and ~-cyanobutyl, Cl-C4 acyloxy(C2-C6)alkyl, i.e., [RcC(O)ORd-, wherein Rc is a Cl-C4 alkyl and Rd is a C2-C6 alkyl], 10 e.g., acetoxyethyl, acetoxypropyl, propionyloxyethyl, acetoxybutyl, and propionyloxypropyl, hydroxy(C2-C6)alkyl, e.g., hydroxyethyl, hydroxypropyl and hydroxybutyl, (C2H40)m CM3, wherein m i6 a number of from 1 to 6, and mono- and disubstituted phenyl, ~aid phenyl 6ub6tituents being 6elected from Cl-C4 alkyl and Cl-C5 15 alkoxy, e.g., methoxy, ethoxy, propoxy, butoxy and pentoxy.
Preferably, Rl i6 ~elected from the group con6i6ting of Cl-C4 alkyl, phenyl, benzyl, l-naphth(Cl-C2)alkyl, such a6 l-naphthylmethyl, boxy(C2 C4)alkyl? cyano(C2-C4)alkyl, Cl-C4 acyloxy(C2-C4)alkyl.
e.g., Cl-C4 acyloxyethyl, hydroxy(C2-C4)alkyl, and (C2H40)m CH3, 20 wherein m i6 a number of from 1 to 3, e.g., 2.
R2 and R3 of the above graphic formula II may each be ~elected from the group consisting of Cl-C5 alkyl, phenyl, mono- and disub~tituted phenyl, benzyl, or R2 and R3 may combine to form a cyclic ring selected from the group consi~ting of an alicyclic ring Z5 containing from 6 to 8 carbon atoms (including the spiro carbon atom), norbornyl and adamantyl. The afore~a~d phenyl ~ubstituents may be selected from Cl-C4 alkyl and Cl-C5 alkoxy rad~cals. More particularly, R2 and R3 are each selected from Cl-C~ alkyl, e.g., methyl, ethyl, propyl, butyl and pentyl~ and phenyl. When one of R2 30 or R3 is a tertiary alkyl radical, such a6 tertiary butyl or tertiary amyl, the other is preferably an alkyl radical otner than a tertiary alkyl radical.
Y in graphic formula II may be carbon or nitrogen. The number and type of non-hydrogen substituent groups represented by R4 35 will vary depending upon whether Y is carbon or nitrogen.
Generally, when Y is carbon each R4 ~ub~tituent may be ~elected from the group consi6ting of halogen, e.g., chloro, fluoro, or bromo, .~
. ` 2~302~Z

Cl-C5 alkyl, Cl-C5 alkoxy, e.g., methoxy, ethoxy, propoxy, butoxy and pentoxy, nitro, cyano, thiocyano, Cl-C4 monohaloalkyl, e.g., Cl-C4 monochloroalkyl, such as chloromethyl ar.d chloroethyl, Cl-C2 polyhaloalkyl, a6, for example, trihaloalkyl ~uch as trichloroalkyl 5 or tr~fluoroalkyl, e.g., trifluoromethyl and 2,2,2-trifluoroethyl, and monoalkylamino or dialkylamino wherein the alkyl moiety of the alkylam~no group contain6 from one to four carbon atom6, e.g., methylamino, ethylamino, propyl~mlno, dimethylamlno and diethylamino.
The letter "e" in graphic formula II i~ an integer of from 0 to 2, e.g., l, and denotes the number of non-hydrogen R4 sub~tituents. In particular, when "e" is l or 2 and Y i6 carbon, each R4 substituent may be selected from the group Cl-C2 alkyl, Cl-C2 alkoxy, chloro, fluoro, bromo, nitro, snd trifluoromethyl.
15 When "e" is 0 (zero), there are no R4 ~ub~tituents and all of the aromatic carbon atoms in the naphtho group have their full complement of hydrogen atoms for the aromatic group shown.
When Y i6 nitrogen, each R4 (non-hydrogen) sub~tituent may be selected from Cl-C5 alkyl, e.g., Cl-C2 alkyl, Cl C5 y, 20 Cl-C2 alkoxy, a~d halogen, e.g., chloro, fluoro or bromo.
Typically, "e" i~ 0 ~zero~ when Y is nitrogen and thu~ there are no R4 ~ubstituent6.
Each Rll in graphic formul II may be selected from Cl-C5 alkyl, halogen, Cl-C5 alkoxy, nitro, cyano, Cl-C4 monohaloalkyl, 25 Cl-C4 polyhaloalkyl, Cl-C8 alkoxycarbonyl, and Cl-C4 acyloxy, i.e., RcC(O)O-, wherein Rc i8 a Cl-C4 alkyl, e.g., methyl. The letter "d"
in graphic formula II represents an integer that may vary from 0 to 4, e.g.~ 0 to 2, 6uch a~ l or 2, and denote~ the number of non-hydrogen 6ubstituent~. When "d" i~ 0 (zero), there are no R
30 ~ub6tituent6 and all of the aromatic carbon atoms have their full complement of hydrogen atom6 for the indole group.

2130~
- i2 -More particularly, spiro(indolino) pyridobenzoxazines (when Y i~ nitrogen) may be represented by the following graphic formula:

10 ~R~' )~ ~ ~ ( III) R

In graphic formula III, Rl, R2 and R3 are the same as defined w~th respect to graphic formula II. Each R4' may be selected from Cl-C5 alkyl, e.g., Cl-C2 alkyl, Cl-C5 alkoxy, e.g., 20 Cl-C2 alkoxy and halogen, e.g., chloro, fluoro or bromo. The letter "e" may be 0 or l. Commonly, "e" i8 O, and thu6, there are no R4' sub~tituent6. When "e" is l, the R4 ~ubstituent may be located on any of the ava~lable carbon a~om of the pyrido molety of the pyrido benzoxazine portlon of the compound, i.e., at the 5', 6', 8' 9' or 2~ lO' position~, most usually at the 8'~`9' or lO' po~itions.
Each Rll' in graphic formula III may be selected from the group con~isting of Cl~C~ alkyl~ e.g., methyl, ethyl, propyl, butyl and pentyl, halogen, e.g., chloro and fluoro, Cl-C5 alkoxy, e.g., methoxy, ethoxy, propoxy, butoxy and pentoxy, nitro, cyano, Cl-C4 30 monohaloalkyl, e.g., chloromethyl, fluoromethyl, chloroethyl, chloropropyl, etc., Cl-C4 polyhaloalkyl, e.g., trihaloalkyl, Cl-C8 alkoxycarbonyl, and Cl-C4 acyloxy, i.e., RcC(O)O-, wherein Rc is a Cl-C4 alkyl, e.g., methyl. An example of an acyloxy group is acetoxy. While any halogen, i.e., chlorine, bromine, iodine and 35 fluorine may be u~ed in respect to the aforesaid halogen or , haloalkyl substituents, chlorine, fluorine and bromine, particularly . . ~..
0.~7;~

chlorine and fluorine, are preferred for the halogen 6ubstituent and fluor~ne ~B preferred for the polyhsloslkyl substltuent, e.g., trifluoromethyl, (CF3~. Preferably, Rll' i8 ~elected from the group consisting of Cl-C2 alkyl, chlorine, fluorine, Cl-C2 trihaloalkyl, 5 e.g., trihalomethyl such as trifluoromethyl and Cl-C5 alkoxy.
The letter "d" in graphic formuls III is an integer from 0 to 4, e.g., 0 to 2, such as l or 2. When "d" i~ 2 or more, each Rll' substituent may be the same or different and in either case, are selected from the aforedescribed group. The Rll' substituent(s) 10 may be located on any of the available carbon atoms of the benzene ring of the indolino portion of the compound, i.e., at the 4, 5, 6 or 7 positions.
It is possibl~ that photochromic organic substances of graphic formula III (and IV) may be a mixture of isomers due to the 15 alternative directional mechanism by which intramolecular condensation occurs during formation of the starting indole reactant (Fischer's base). Indolization of 3-substituted phenylhydrazones can give rise to a 4-sub6tituted indole, a 6-substituted indole, or mixture~ thereof. Thus, when "d" is 1, the photochromic substnnce 20 may be substituted at the 4 position on the indoline ring, at the 6 position of that ring or compri~e a mixture of such isomer6. When "d" is 2, the Rll' substituent~ may be preæent at any combination of the 4, 5, 6, or 7 carbon atoms of the indoline ring and may comprise an isomeric mixture of such compounds, e.g., a mixture of compounds 25 having substituents at the 4 and 5, 4 and 6, 5 and 6, 4 and 7, 5 and 7, and 6 and 7 position6 of the lndoline ring. Commonly, when "d"
is 2 the Rll' substltuents are located at the 4 and 5, or 5 and 6 po~itions. Al60 contemplated are materials containing mixtures of such isomers, e.g., materials compri~ing 4 (and 6) and 5-6ubstituted 30 spiro(~ndolino) pyrido ben20xazines.
Non-limiting examples of spiro(indolino) pyridobenzoxazines of graphic formula III are described in Table l. Such pyridobenzoxazines are those in which Rl, R2, R3, snd Rll' are as indicated in Table l, the letter "e" is 0 (zero), and the letter "d"
35 is 0, 1 or 2. A hyphen ~-) indicates the absence of a non-hydrogen substituent.

2~30272 - 14 Table 1 Compound/ Rl R2 - R3 Rlll R

2 CH3 CH3 CH3 4(6)-CH3 5-~H3 CH3 CH3 ~2H5 6 CH3 CH3 C2H5 5-CH3 4(6)-CH3 8 n-C4Hg CH3 C2H5 9 CH3 CH3 phenyl CH3 phenyl phenyl 11 C2H5 CH3 C2H5 4(6)-C~3 5-CH3 15 12 n-C4Hg CH3 C2H5 5-C~3 (4)6-CH3 13 CH3 CH3 C~3 S-CH3 (4)S-CH3 14 n~C3H7 CH3 C~3 5-CH3 15 , n~~3H7 CH3 CH3 5-OCH3 16 n C3H7 CH3 CH3 4(6)-C~3 5-~H3 Compound 2 ln Table 1 may be nAmed 1,3,3,4(and 6),5-pentamethyl-spiro-[indolino-2,3' [3~]pyrido [3,2-~] ~1,4~ benzoxazine~.
Similarly, compound 6 in Table 1 may be named 1,3,4(and 6),5-tetramethyl-3-ethylspiro- [indolino-2,3' ~3~3 pyrldo ~3,2-~]
25 [1,4] benzoxazine~O Other compounds in Table 1 may be slmilarly - named taking into account the different substituents. Moreover, compounds derived from the description of graphic formula III may be similarly named by substituting the substituents described with respect to Rl, R2, R3~ R4 snd Rll' for thoRe found in the 30 description and in Table 1. When the letter "e" i5 1 or more, the R4' substituent(s) are given a prime (') designation. For nomenclature purposes, numbering of the pyrido benzoxazine portion of the molecule is counter clockwise starting with the nitrogen atom of the oxazine ring as the number 1' position. Numbering of the 35 indolino portion of the molecule i~ counter clockwise starting with the nitrogen atom as the number 1 position.

. . ~ . .
''` 2~30~72, Spiro(indolino)naphthoxazines that may be used in the practice of the present process may be represented by the following graph~c formula:

R ~73 ~ R ' ' ) ~ ~ R ~ ~ ) wherein Rl, R2 and R3 are the same as that described w~th respect to graphic formula II.
Each R4" substituent in graphic formula IV may be selected from the group consisting of halogen, e.g., chloro, fluoro, or bromo, Cl-C5 alkyl, Cl-C5 alkoxy (e.g., methoxy, ethoxy, propoxy, butoxy and pentoxy), n~tro, cyano, thiocyano, Cl-C4 monohaloalkyl, e.g., Cl-C4 monochloroalkyl, ~uch as chloromethyl and chloroethyl, 25 Cl-C2 polyhaloalkyl, ae for example 9 trihaloalkyl, such a6 trichloroalkyl or trifluoroalkyl, e.g., trifluoromethyl and 2,2,2-tr~Lluoroethyl, ~nd monoalkylamino or dialkylamino, whereln the alkyl moiety of the alkylamino group contains from l to 4 carbon atoms, e~g., methylamino, ethylamino, propylamino, dimethylamino and 30 diethylamino. More particularly, the R4" sub~tituent may be selected from the group Cl-C2 alkyl, Cl-C2 alkoxy, chloro, fluoro, bromo, nitro and trifluoromethyl. The letter "e" in graphic formula IV is an integer from 0 to 2, e.g., l or 2, and denotes the number of non-hydrogen R4" substituents. When "e" is 0, there are no R4"
35 6ubstituent6 and all of the aromatic carbon atoms of the naphtho moiety of the molecule represented by formula IV have their full complement of hydrogen atoms for the naphtho group shown.

WO 93/17071 PC1'/US93/00873 AE in the ca~e with graphic formula III, when "e" i8 1, the R4'l substituent may be located on any of the available carbon atoms of the naphtho moiety nf the naphthoxazine portion of the molecule, i.e., at the 5', 6', 7' 8', 9' or 10' position~.
5 Preferably, the R4" sub~tituent is present on the 7', 8' or 9 !
carbon atoms. When "e" is 2, the R4" 6ubstituent~ may be same or different and in either case are selected from the above-described group. When "e" is 2, the R4" sub~tituents are commonly located at the 7' and 9', or 8' and 10' po~ition~. For nomenclature purpose~, 10 numbering of spiro(indolino) naphthoxazines is the same a6 that de~cribed with regard to the spiro(indolino) pyrido benzoxszines of graphic formula III. Rll" and the letter "d" in graphic formula IV
are the 6ame a6 that described with respect to Rll and d in graphic formula II.
Non-limiting examples of ~piro(indolino) naphthoxazines 6elected from the description of graphic formula IV are de~cribed in Table 2. Such 6piro(indolino) naphthoxazines sre tho6e in which Rl, R2, R3, R4" and R11" are as indicated in Table 2, the letter "d" is 0, 1 or 2 and the letter "e" i6 1. As in Table 1, a hyphen (-) 20 ~ndicates the absence of a non-hydrogen substituent. In Table 2, all of the R4" sub6tituent6 are at the 9' carbon position.

`2~31~Z~72 Table 2 Compound/ Rl R2 R3 R4~ Rll" Rll"
(9 --) 5 l CH3 CH3 CH3 OCH3 2 CH3 CH3 CH3 OCH3 5-CH3 (4)6-CH3 4 CH3 CH3 CH3 OCH3 5-Cl (4)6~CH3 6 CH3 CH3 C2H5 OCH3 5-CH3 ~4)6-CH3 8 n-C4Hg CH3 C2~5 OCH3 9 CH3 CH3 phenyl OCH3 CH3 phenyl phenyl OCH3 15 ll CH3p-C6H4OCH3 p-C6H4OCH3 OCH3 12 C2H5C~3 C2H5 OCH3 5-CH3 13 n-C4~9CH3 C2H5 ~CH3 5-CH3 Compound 2 ln Table 2 may be named 1,3,3,4(and 6),5-pentamethyl-20 9'-methoxy-spiro[indolino-2,3' 13~]-naphth 12,l-b] [1,43-oxazine].
S~milarly, compound 6 ln Table 2 may be named 1,3,4 (and 6),5-tetramethyl-3-ethyl-9'-methoxy~plro [indolino-2,3' [3H]-naphth [2,1-bl 11,4~-oxazine. Other compounds in Table 2 can be 6~milarly named taking into account the different ~ub~tituent~. Moreover, 25 compounds derived from the description of graphic formula IV may be s~milarly named.

Spiro(indolino) benzoxazines compounds de~cribed in U.S.
Patent 4,816,584 may be represented by the following graphic formula V.

(R13)d R R3 ~/o ~( R1;) h ( V) wherein Rl, R2, R3 and d are the same as described with re~pect to graphic formula II dnd R12 and R13 are each selected from the group 20 consistlng of Cl-C5 alkyl, e.g., Cl-C2 alkyl, Cl-C5 alkoxy, e.g., Cl-C2 alkoxy, preferably methoxy, and h i6 the integer 1 or 2.
When "h" i8 1, the Rl~ eubstituent may be loosted on any of the a~ailable carbon atoms of the benzene ring of the benzoxazine moiety, i.e.~ at the 5, 6, 7 or 8 position6. Prèferably, the R12 25 substituent i~ located at the number 5, 6, or 7 carbon atom. When "h" is 2, the R12 substituents may be the 6ame or different and in either case are selected from the above-described group. When "h"
is 2, the R12 substituents are de~irably located at the 5 and 7 or 6 and 8 position6.
Examples of spiro(indolino)benzoxazines within the scope of graphic formula V are listed in ~able 3. Compound 1 may be named:
7-methoxy-1',3',3',4' (and 6'), 5'-pentamethylspiro- [2~-1,4-ben-zoxazine-2,2'-indoline3. Compounds 2-6 may be similarly named as substituted 6piro(indolino) benzoxazines using the substituents 35 de~cribed in Table 3 for such compounds. Moreover, compounds derived from the description of graphic formula V may be similarly named. In naming the spiro(indoline)benzoxazines, the I~PAC rules ..2~72 of organic nomenclature have been used. The posltions of the indolino portion of the molecule have been numbered counterclockwise stsrting with the nitrQgen atom a6 the number one (1~ posit~on, and are ~dentified by a prime number, e.g., 3'. The po~itions of the 5 benzoxazine portion of the molecule have been numbered clockwise -starting with the oxygen atom as the number one (1) po6ition.

Table 3 SUBSTITUENT
lO Compound No. Rl R2 R3 Rl3 Rl3 ~12 R~2 1 Me Me Me 4(6)-Me 5-Me 7-OMe 2 Me Me Me 4(6)-Me 5-Me 7-O;e 5-~Me 3 Me Me Me 5-OMe - 7-OMe 5-OMe 4 Me Me Me 4(6)-Me S-Me 7-OMe 6-Qme Me Me Et - - 7-OMe 5-OMe 6 nBu Me Me - - 7-OMe 5-OMe 20 BçY:
Me - methyl nBu z n-butyl Et - ethyl OMe - methoxy The naphthopyran compounds of the present invention may be combined w~th or used in con~u~ction wlth photochromic amounts of a 6p~ro(indolino) pyrid~ benzoxazine, or spiro(indollno~ naphthoxazine compounds in amounts and in a rstio 6uch that an orgsnic host 30 material to wh~ch the mixture of compound6 is applied or in which they are incorporated exhibits a de6ired resultant color, e.g., a substantially neutral color such as shade6 of gray or brown, when activated with unfiltered sunlight~ i.e., a~ near a neutral color as pos6ible given the colors of the activated pyran and oxazine 35 photochromic compounds. The relative amounts of the aforesaid oxazine and pyran compound~ used will vary and depend in part upon the relative intensities of the color of the activated ~pecie~ of such compounds, and the ultimate color desired. Similarly, the ~ ;", ,~ Q~72 naphthopyran compound6 of the pre~ent lnvention may be combined with photochromic amount6 of spiro(indolino)benzoxazine compounds in amounts and in a r~tio such that an organic hoEt material to which the mixture of compound6 is applied or in which they are incorporated 5 exhibits a near-brown color. Generally, the mole ratio of the aforede~cribed spiro(indolino) oxazine compound(s) to the pyran compound(s) of the present invention wlll vary from about 1:3 to about 3:1, e.g., between about l:l and about 2:1.
In addition, it i6 contemplated that the naphthopyran lO compound6 of the present invention may be admixed with photochromic amounts of other naphthopyran compounds, such as those described in U.S. Patent 5,066,818, i.e., those compounds containing at least one ortho-sub~tituted phenyl ~ubstituent at the 3-position of the pyran ring, preferably a monoortho-substituted phenyl 6ubstituent.
15 Compounds described in U.S. Patent 5,066,818 that are not 6ub6tituted on the nap1.tho portion of the naphthopyran may be represented graph~cally by the following graphic formula, : : .

~5 ~ 2 - ~ ~rI) wherein Yl may be selected from the group consisting of Cl-C5 alXyl, Cl-C5 alkoxy, fluoro and chloro. Preferably Yl is selected from the group consisting of Cl-C3 alkyl, Cl-C3 alkoxy and fluoro. Zl may be 35 selectèd from the group consisting of hydrogen and Yl. Each Y2 and Z2 may be selected from the group consisting of Cl-C5 alkyl, Cl-C5 alkoxy, cyano, hydroxy, halogen, preferably chloro or fluoro, ;~g~27Z

scrylyl, methacrylyl, acryloxy (Cl-C4) alkyl, and methacryloxy (Cl-C4j alkyl. Preferably, each Y2 and Z2 are selected from the group consisting of Cl-C3 alkyl, Cl-C3 alkoxy and fluoro. The letter6 a snd b in graphic formula VI are each an integer selected 5 from the group con6isting of 0, 1 or 2. When a or b are 0 (zero), the phenyl groups have their appropriate complement of ring hydrogens.
In a particular embodiment described in U.S. Patent 5,066,818, Yl is Cl-C3 alkyl, Cl-C3 alkoxy and fluoro, Zl i6 10 hydrogen, Y2 is Cl-C3 alkoxy or hydrogen, Z2 is selected from the group consisting of Cl-C3 alkoxy, Cl-C3 alkyl and hydrogen, a i6 0 or 1 and b i~ 0, 1 or 2. While Y2 and Z2 substituents may be located at -any of the unsubstituted portions of their respective phenyl groups, they are preferably in the 3, 4 or 5 positions. When a or b is 1, 15 the ~ubgtituent ii preferably meta or para to the carbon atom attached to the pyran ring. When a or b is 2, the 6ubstituents preferably are located at the 3 and 4, 3 and 5 or 4 and 5 numbered carbon atom8. The mole ratio of the naphthopyrans of the pre6ent invention to those described in U.S. Patent 5,066,818, i.e., those 20 not substituted on the number 8 carbon atom, may vary from 1:3 to 3:1, e.g., between 1:1 and about 2:1.
Specific compounds described in U.S. Patent 5,066,818 include:
(1) 3(2-fluorophenyl)-3(4-methoxyphenylj~3H-naphtho[2,1-b]
pyran.
(2) 3(2-fluorophenyl)-3(3,4-dimethoxyphenyl)-3~-naphtho-[2,1-b] pyran.
(3) 3(2-methyl-4-methoxyphenyl)-3(4-methoxyphenyl)-3H-naphths[2,1-b] pyran.
(4) 3(2-methylphenyl)-3(4-methoxyphenyl)-3H-naphtho[2,1-b]
pyran.
(5) 3-phenyl-3(2,4-dimethoxyphenyl)-3H-naphtho[2,1-b] pyran.
(6) 3(4-methoxyphenyl)-3(2,4-dimethoxyphenyl)-3H-naphtho-t2,1-b] pyran.
(7) 3(2,6-difluorophenyl)-3,t4-methoxyphenyl)-3H-naphtho-[2,1-b]pyran.

2 i ~ o~ ~ 22 Photochromic compounds of the present invention, mixtures of such compounds with other photochromic compound~, or compositions containing same (hereinafter "photochromic substances") may be applied to or incorporated into a host material by various methods ` S described in the art. Such methods include dissolving or dispersingthe sub6tance within the host material, e.g., imbibition of the photochromic substance into the host material by immersion of the host material in a hot solutlon of the photochromic substance or by thermal transfer; providing the photochromic substance a6 8 separate 10 layer between adjacent layers of the host material, e.g., a~ a part of a polymer film; and applying the photochromic sub6tance as part of a coating placed on the surface of the host material. The term "imbibition" or "imbibe" is intended to mean and include permeation of the photochromic substance alone into the host material, solvent 15 assi6ted transfer absorption of the photochromic sub6tance into a porou6 polymer, vapor phase transfer, and other such transfer mechanisms.
Compatible (chemically and color-wi6e) tints, i.e., dyes, ~- may be applied to the host material to achieve a more aesthetic 20 reeult, for medical reasons, or for reasons of fashion. The particular dye selected will vary and depend on the aforesaid need and result to be achieved. In o~e embodiment, the dye may be selected to complement the color resulting from the activated -~ photochromic substance6; e.g., to achieve a more neutral color or 25 ab~orb a particular wavelength of incident llght. In another embodiment, the dye may be selected to provide a desired hue to the host matrix when the photochromic substances is in an unactivated state.
Adjuvant materials may al60 be incorporated into the host 30 matlerial with the photochromic substances prior to, 6imultaneously with or sub~equent to application or incorporation of the photochromic sub6tances in the ho6t material. For example, ultraviolet light absorbers may be admixed with photochromic substances before their application to the host material or such 35 absorbers may be 6uperposed, e.g., superimpo6ed, as a layer between the photochromic substance and the incident light. Further, W O 93~17071 PCT/US93/00873 21~

stabilizer6 may be admixed with the photochromic substance6 prior to their application to the host material to improve the light fatigue resistance of the photochromic substances. Stabilizerfi, such as hindered amine light stabilizers and singlet oxygen quencher~, e.g., 5 a nlckel lon complex with an organlc ligand, are contemplated-. They may be used alone or in combination. Such stabillzers are described in U.S. Patent 4,720,356. Finally, appropriate protective coating(s) may be applied to the surface of the host material. The6e may be abrasion resistant coatings and/or coatings that serve as oxygen 10 barriers. Such coatings are known in the art.
Singlet oxygen quenchers that may be used as stabilizers include complexes of nickel(2+), i.e., Ni2+, with an organic ligand, cobalt (III) tris-di-n-butyldithiocarbamate, cobalt (II~
diisopropyldithiocarbamate, and nlckel diisopropyldith~ophosphate.
15 Such singlet oxygen quenchers are used in stabilizing amounts.
Preferred are eomplexes of Ni2+ such as [2,2-thiobiE~4~ 1,3~3-tetramethylbutyl) phenolato] (butylamine) ]
nickel, which i sold under the tradename of CYASORB W 1084; nickel ~O-ethyl(3,5-di-tert-butyl-4-hydroxybenzyl)] phosphonate, which i~
20 sold under the tradename I~GASTAB 2002; nickel dibutyldithiocarbamate, which i8 sold under th~ tradename RYLEX NBC; bi~[2,2'-thiobis-4-(1,1,3,3-tetramethylbu~7 )phenolato] nickel, which is sold under the tradename W -C~E.~ ~M lO~, nickel di-lsopropyl dithiophosphate and other Ni2~ comple~e~ sold under the tradenames of W -CHEK AM 105, 25 W -CHEK 126, and W -C~EK AM 205.
Hindered amine light ~tabilizers that may be used include bi6(2~2,6D6-tetramethyl-4-piperidinyl) ~ebacate, which i~ sold under the tradename TINW IN 770; bis(l,2,2,6,6-pentamethyl- 4-piperidinyl) sebacate, which is sold under the tradename TIN W IN 765;
30 di(l,2,2,6,6-pentamethyl-4-piperidinyl)butyl (3',5'-ditertiary-butyl-4-hydroxybenzyl)malonate, whicn is sold under the tradename TIN W IN 144; poly[(6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl)-(6-[2,2,6,6-tetramethyl-4-piperi-dinyl]-amino-hexamethylene)], which is sold under the tradename 35 C~IMASSORB ~44; and poly~6-(morpholino)-s-triazine-2,4-diyl][16-(2,2,6,6-tetramethyl-4-piperdyl)amino] hexamethylene], which W O 93/1707t PCT/US93/00873 ;~130Z~Z ~ r ~ ~ !

is sold under the tradename CYASORB 3346. Other hindered amine li~ht stabilizers that may be used are those sold under the tradename TIN WIN 622, SPINW EX A-36 and HOSTAVIN TMN 20. Such stabllizers are used in stabilizing amounts.
S The foregoing singlet oxygen quencher~ and hindered amine light stabilizers may be used singly or in combination in amounts sufficient to enhance the light-fatigue resistance of the photochromic substance(s) deficribed herein. Between 0.01 and about 5 percent by weight of the foregoing stabilizer~ may be used (alone or in 10 combination) to improve the light fatigue resistance of the photochromic material~.
The polymer ho~t material will usually be transparent, but may be translucent or even opaque. The polymer protuct need only be transparent to that portion of the electromagnetic spectrum, which 15 activates the photochromic ~ubstance, i.e., that wavelength of ultraviolet (W ) light that produce6 the open form of the substance and that portion of the visible 8pectrum that include~ the absorption maximum wavelength of the ~ubstance in lts W activated form, i.e., the open form. Further, the resin color ~hould not be such that it 20 mask~ the color of the activated form of the photochromic sub6tance, i.e., 80 the change in color i8 readily apparent to the ob6erver.
Preferably, the host materlal article is a solid transparent or optically clear material, e.g~, material6 ~uitable for optical application~, ~uch as plano and ophthalmic lenses, windows, automotive 25 transparencies, e.g., windshield6, aircraft transparencie6, plastic sheeting, etc~ -Example~ of ho6t material~ which may be used with the photochromic ~ub~tances or compositions deRcribed herein include:
polymers, i.e., homopolymers and copol~mers, of polyol(allyl 30 car~onate) monomers, polymers, i.e., homopolymer6 and copolymer6, of polyfunctional acrylate monomers, polyacrylates, poly(alkylacrylates) such as poly(methyl methacrylate), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), 35 poly(vinylidene chloride), polyurethanes, polycarbonates, poly(ethylene terephthalate), polystyrene, copoly(styrene-methyl methacrylate) copoly(styrene-acrylonitrile), polyvinylbutyral and W O g3/1707~ PCT/US93/00873 2~3b~

polymers, i.e., homopolymers and copolymers, of diallylidene pentaerythritol, particularly copolymers with polyol (allyl carbonate) monomers, e.g., diethylene glycol bis(allyl carbonate~, and acrylate monomer6 .
Transparent copolymers and blend6 of transparent polymers are al~o suitable as host materials. Preferably, the host material is an optically clear polymerized organic material prepared from a polycarbonate resin, 6uch as the carbonate-linked thermoplastic resin derived from a bisphenol, such as bi~phenol A, and phosgene, which is 10 sold under the trademark, LEXAN, i.e., poly(4-phenoxy-4'-phenoxy-carbonyl-2,2-propane); a poly(methyl methacrylate), such as the material sold under the trademark, PLEXIGLAS; polymerizates of a polyol(allyl carbonate) monomer, especially diethylene glycol bis(allyl carbonate), which monomer i6 ~old under the trademark CR-39, 15 and polymerizate~ of copolymers of a polyol (allyl carbonate), e.g., diethylene glycol biR(allyl carbonate), wlth other copolymerizable monomeric materials, such a~ copolymers with vinyl acetate, e.g., copolymers of from 80-90 percent diethylene glycol bi&(allyl carbonate3 and 10-20 percent vinyl acetate, particularly 80-85 percent 20 of the bis(allyl carbonate) and 15-20 percent vinyl acetate, and copolymere with a polyurethane having terminal diacrylate functionality, as described in U.S. patent 4,360,653; cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and copolymerfi of styrene with methyl 25 methacrylate, vinyl acetate and acrylonitrile.
Polyol (allyl carbonate) monomers which may be polymerized to form a tran~parent ho~t material are the allyl carbonates of linear or branched aliphatlc or aromatic liquid polyols, e.~., aliphatic glycol bis(allyl carbonate) compounds, or alkylidene bisphenol bis(allyl 30 carbonate) compound~. These monomers can be described as unsaturated polycarbonates of polyols, e.g, glycols. The monomers can be prepared by procedures well known in the art, e.g., method~ de~cribed in U.S.
Patents 2,370,567 and 2,403,113.

W 0 93/17071 P ~ /US93/00&73 ;~0~
~ 26 -The sforedescribed polyol (allyl carbonate) monomerfi may be repre8ented by the graphic formula:

R' ~ 0 - C ~ ~ ~ 3 n (VII) wherein R is the radical der1ved from an un~aturated alcohol and i~
commonly an allyl or ~ubstituted allyl group, R' is the radical 10 derived from the polyol, and n i8 a whole number from 2 - 5, preferably 2. The allyl group (R) may be ~ubstituted at the 2 pocition with a halogen, mo~t notably chlorine or bromlne, or an alkyl group containing from 1 to 4 carbon atoms, generally a methyl or ethyl group. The R group may be represented furtber by the 15 graphic f ormula:

H2c = c - CH2 ~ tVII-A) wherein Ro 18 hydrogen, halogen, or a Cl-C4 alkyl group. Specific example~ of R include the group~: allyl, 2-chloroallyl~
2-bromoallyl, 2-fluoroallyl, 2-methylallyl, 2-ethylallyl, 2-i80propylallyl, 2-n-propylallyl, and 2-n-butylallyl. Most 25 commonly R i6 the allyl group, H2C = CH - CH2-.
R' i8 a polyvalent radical derive~ from the polyol, which can be an aliphatic or aromatic polyol that Contain6 ~ 3, 4 or 5 hydroxy group~ Typically, the polyol contain8 2 hydroxy group~, -i.e., a glycol or bi~phenol. The aliphatic polyol Can be line8r or 30 branched and co~taîn f rom 2 to 10 carbon atom~. Commonly, the aliphatic polyol i~ an alkylene glycol having from 2 to 4 carbon atom8 or a poly(C~-C4) alkylene glycol, i.e., ethylene glycol, propylene glycol, trlmethylene glycoi, tetramethylene glycol, or diethylene glycol, triethylene glycol, etc.

The aromatic polyol can be represented by the graphic formula:

OH OH

(R~p~ ~, _~ (VIII) wherein A i~ a bivslent radical deri~ed from an acyclic aliphatic hydrocarbon, e.g., an alkylene or alkylidene radical, having from 1 15 to 4 carbon atom6, e.g., methylene, ethylene, and dimethylmethylene (i60propylidene), Ra represents lower alkyl substituents of frcm 1 to 3 carbon atoms and halogen, e.g., chlorine and bromine, and p ~6 the integer 0, 1, 2, or 3. Preferably, the hydroxyl group i8 in the ortho or para position.
Specific example~ of the radical R' include: alkylene j groups containing from 2 to 10 carbon atoms such a6 ethylene, ¦ (-CH2-CH2-), trimethylene, methylethylene, tetramethylene, ethylethylene, pe~tamethylene, hexamethylene, 2-methylhexamethylene, octamethylene, and decamethylene; alkylene ether groups such a6 1 25 CH2 -CH2-~ -C~2C~2-0-CH2C~2-- -c~2-o-cH2~cH2-9 and ¦ -CH2CH2CH2-0-CH2CH2CH2-; alkylene polyether groups such a6 ¦ 2 2 2CH~ O CH2~H2-, and -CH2CH2CH2-0-CH2CH2CH2-0-CN2CH2CH2-;
alkylene carbcnate and alkylene ether csrbonate group~ such as W O 93/t7071 PCT/US93/00873 2~30, ~

2CH2 C0-0-CH2CH2- and -cH2cH2-o-cH2cH
0-C~2CH2-; and i60propylidene bis(para-phenyl), i.e., 10 ~ ~ } (IX) Most commonlY~ R' i~ -C~2cH2-~ -C~2cH2- CH2CH2 ' -CH2CH2--0-CH2CH2-O-cH2cH2- .
Specific non-limiting examples of polyol (allyl carbonate) 20 monomer6 include ethylene glycol bis(2-chloroallyl carbonate), ethylene glycol bis(allyl carbonate), diethylene glycol bi6(2-methallyl carbonatc), diethylene glycol bi6(allyl carbonate), triethylene glycol bis(allyl carbonate~, propylene glycol bi6 ( 2-e thylal lyl carbonate), 1,3-propanediol bi6(allyl carbonate), 25 1,3-butaned~ol bi6(allyl carbonate), 1,4-butanediol bis~2-bromoallyl carbonate), dipropylene glycol bi6(allyl carbonate), trimethylene glycol bis(2-ethylallyl carbonate), pentamethylene glycol bis(allyl carbonate), and isopropyl~dene bisphenol bis(allyl carbonate).
Industrially important polyol bis(allyl carbonate) monomers ! 30 which may be utilized to prepare a transparent ho6t material are:

O O
Il 11 CH2 = CH-CH2-0-C-O-CH2-CH2-0-CH2CH2-0-CH2CH2-0-C-O-CH2CH = CH2, (X) Triethylene Glycol bis(Allyl Carbonate) W O 93/17071 PCT/US93tO0873 :~" z~30Z7Z

O O
Il 11 CH2 ~ C~-CH2-O-C-O-cH2cH2-o-cH2cH2o-c-o-cH2-cH CH2~ a (XI ) Diethylene Glycol bis(Allyl Carbonate) O
ll ll CH2 = CH-CH2-o-C-o-CH2CH2-o-C-o-CH2-CH ~ c~2. (XI I ) Ethylene Glycol bi~(Allyl Carbonate) 15 Diethylene glycol bis(allyl carbonate) is preferred.
Becau~e of the proce~s by which the polyol(allyl carbonate) monomer i8 prepared, i.e., by pho6genation of the polyol (or allyl alcohol) and subsequent esterification by the allyl slcohol (or polyol), the monomer product can contain related monomer 8pecie8 in 20 which the moiety connecting the allyl carbonate groups contains one or more carbonate groups. These related monomer æpecie~ can be represented by the graphic formula:

O O
R-O-C-[O-Rb-O-c-]sO-R (XI I I ) wherein R i8 as defined above, Rb i6 a bivalent radical, e.g., alkylene or phenylene, derived from a diol, and 8 i~ a whole number 30 from 2 to 5. The related monomer specie~ of diethylene glycol bis(allyl carbonate) can be represented by the graphic formula, O O
3~ CH2 = CH-cH2-o-c[-o-c~2-cH2-o-cH2-cH2-o-c~s-o-cH2-cH = CH2 (X I V ) wherein s is a whole number from 2 to ~. The polyol (allyl carbonate) monomer can typically contain from 2 to 20 weight percent ~ ~ ~ . . .
k ~
2130Z72 . ~ i of the related monomer species and such relsted monomer 6pecies can be present as mixtures, i.e., mixtures of the species repre6ented by s bein~ equal to 2, 3, 4, e~c.
In addition, a partially polymerized form of the polyol 5 (allyl carbonate) monomer, i.e., prepolymer, can be u6ed. In that embodiment, the monomer i6 thickened by heating or partlally polymerized by using small, e.g., 0.5-1.5 parts of lnitiator per hundred parts of monomer (phm), to provide a non-gel containing, more vi6cous monomerlc material.
As used in the present de6cription and claims, the term polyol(allyl carbonate) monomer or like name6, e.g., diethylene glycol bis(allyl carbonate), are intended to mean and include the named monomer or prepolymer and any related monomer species contained therein.
Polyfunctional acrylate monomers that may be u~ed to prepare cynthet~c polymeric ho6t material6 are esterification products of an acrylic acid moiety selected from the group con6i6ting of acrylic ac~d and methacrylic acid, and a polyol, e.g., a tiol, a triol or tetracarb~nol. More particularly, the 20 polyfunctional acrylate monomer may be represented by the following graphic fonmula:

( c~2=c (Rt )-C ( o ) )~nR ( XV ) 25 wherein Rt is hydrogen or methyl, n i~ the number 2, 3, or 4, and R"
is the multlvalent radical, i.e., a bi~alent, trivalent or quadravalent radical, remsining after removal of the hydroxy groups from a polyol, having from 2 to 4 hydroxy groups, e.g., a diol, a triol or tetracarbinol respectively. More particularly, Rt is 30 hydrogen or methyl, and n is 2 or 3, more usually 2.
R" may be selected from the group consisting of alpha, omega C2-C8 glycols, cyclohexane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, C2-C5 triols and pentaerythritol. Examples of such polyols include 3S ethylene glycol, trimethylene glycol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, propylene glycol, trimethylol propane, glycerol and the like.

W O 93/17071 PCT/USg3/00873 -`` 21302~2 i r ;r Examples of polyfunctional acrylate monomers, ~uch as diacrylates and triacrylates, include: ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propane diol diacrylate, 1,3-propane diol diacrylate, 1,2-propane diol dimethacrylate, 5 1,3-propane diol dimethacrylate, 1,4-butane diol diacrylatej 1,3-butane diol dimethacrylate, 1,4-butane diol dimethacrylate, 1,5-pentane diol diacrylate, 2,5-dimethyl-1,6-hexane diol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylol 10 propane trimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, trimethylol propane triacrylate, glycerol triacrylate, glycerol trimethacrylate, pentaerythritol triacryla~e, pentaerythritol dimethacrylate, pentaerythritol 15 tetraacrylate, pentaerythritol tetramethacrylate and mixtures of soch acrylate monomer6.
A portion of the polyfunctional acrylate monomer may be replaced with a monofunctional copolymerizable monomer containing the vlnyl (C~2-CH-) grouping. Such compatible monomers include 20 monofunctional acrylic and methacrylic acid ester6, and vinyl ester6 of C2-C6 carboxylic acids, i.e., vinyl carboxylates. Preferably, the copolymerizable monomer i8 a non-aromatic, e.g., non-benzenoid, containing monomer. Monofunctional acrylic or methacrylic ester monomers may be graphically illustrated by the following formula, CH2=C(Rt)-C(o)-o-R~ ~ ~ (XVI ) wherein Rt i~ hydrogen or methyl, and R''' i8 selected from the group c~nsi6ting of Cl-C12, e.g., Cl-C8, alkyl, C5-C6 cycloalkyl, 30 glycidyl and hydroxyethyl. Preferably, R''' is a Cl-C4 alkyl, e.g., methyl or cyclohexyl.
Examples of monofunctional acrylic acid type monomers include, for example, the acrylic and methacrylic acid e6ters of al~anols such as methanol, ethanol, propanol, butanol, pentanol, 35 hexanol, heptanol and octanol, e.g., methyl acrylate, methyl ~ methacrylate, ethyl acrylate and ethyl methacrylate, cycloalkanols - such as cyclopentanol and cyclohexanol, glycidol (3-hydroxy ' W O 93/17071 PCT/US93~00873 ,. , propylene oxide, (d, l, dl)) and ethylene glycol. Examples of vinyl carboxylate~ include vinyl acetate, vinyl propionate, vinyl butyrate and vinyl valerate. In addition to and/or in place of the aforedescribed monofunctional copolymerizable monomer, 5 monofunctional allylic and difunctional allylic copolymerizable compatible monomers may al60 replace a portlon of the polyfunctional scrylate monomer. Monofunctional allylic monomers contemplated include allyl esters of C2-C6 carboxylic acids, Cl-C6 allyl ether6 and other copolymerizable allyl compounds. Preferably the lO monofunctional allylic monomer i6 a non-aromatic compound.
Difunctional allylic copolymerizable monomers contemplated herein are the polyol (allyl carbonates) monomer~ of graphic formula VI.
The amount of photochromic ~ubstance or composition containing same applied to or incorporated into a host material is 15 not critical provided that a sufficient amount is u~ed to produce a photochromic effect discernihle to the naked eye upon activation.
Generally guch amount can be de6cribed as a photochromic amount.
The particular amount used depends often upon the inten6ity of color desired upon irradiation thereof and upon the method used to 20 incorporate or apply the photochromic substance6. Typically, the more compound applied or incorporated, the greater i6 the color intenslty. Generally, the amount of each photochromic ~ubstance incorporated into or applied to the ho~t material may range from about O.Ol or 0.05 to about lO to 20 percent by weight. More 25 typically, the amount of photochromic substance(6) incorporated into or applied to the host material will range from about O.Ol to about 2 weight percent, more particularly, from about O.Ol to about l weight percent, e.g., from about O.l or 0.5 to about l weight percent, based on the weight of the host material.
The present invention is more particularly described in the following examples which are intended as lllustrative only, since numerous modifications and variations therein will be apparent to those 6killed in the art.

, ~ . .

~ 33 ~ 2~27~
~XAMPLE 1 A reaction flask wac charged with 200 milliliters (ml) of ~cetone, 13.8 gram6 (g) (0.1 mole) of powdered potnsslum carbonate and 16.0 g (0.1 mole) of 2,6-dihydroxynaphthalene. 12.6 g 5 (0.1 mole) of dimethylsulfate was added dropwi~e and the reaction mixture was stirred at room temperature for 72 hours under a nitrogen atmosphere. 200 ml of a 10% aqueous codium hydroxide solution was then added to the reaction flask. A whlte precipitate that formed, was removed by vacuum filtration. The ~q~eous filtrate 10 was acidified with hydrochloric acid to a pH of 3 and the squeous ~olution extracted three times - e~ch time with 100 ml of methylene chloride. The extracts were combined, dried over anhydrous magnesium sulfate for 10 minutes and the ~olvent removed under vacuum. The remaining ~olid was washed with hot water - yielding 15 3.0 g of a solid product, which was confirmed by NMR spectroRcopy to be 6-methoxy-2-hydroxynaphthalene.
1.1 g (0.006 mole) of the aforedescribed product, 6-methoxy-2-hydroxynaphthalene, wa~ added to a reaction flasX
containing 100 ml of benzenç and 1.3 g (0.006 mole) of 20 1~1-diphenyl-2-propyn-1-ol. A catalytic amount (approximately 20.0 milligrams) of p-toluene sulfonic acid was added, the resulting mixture stirred and placed under a nitrogen atmosphere. The react~on m~xture was heated gently at 50C. for 4 hour6, and then 200 ml of a 10% aqueous sodium hydroxide solution was added to the 25 reaction fla6k. After ~tirring for 15 minutes, the reaction mixture wa~ extracted twice - each time with 100 ml of methylene chloride.
The ~xtraet6 were combined, dried over anhydrous magnesium sulfate and the ~olvent removed under vacuum. The product (1.0 grams) melted at 173-175C. An NMR spectrum confirmed the product to be 30 8-methoxy-3,3-diphenyl-3H-naphtho [2,1-b]pyran.

A reaction flask was charged with 8.0 g of 2-fluoro-4'-methoxybenzophenone, (prepared by the Friedel-Crafts 35 reaction of 2-fluorobenzoylchloride with anisole) in 150 ml of tetrahydrofuran and 14.0 g (1.5 equivalents) of sodium acetylide.
The reaction mixture was stirred under a nitrogen atmosphere for 72 .. . .. .

hour6, cooled by pouring it into a 500 ml beaker containing ice water and extracted three times - each tlme with 100 ml of methylene chloride~ The extracts were combined, dried over anhydrous magneslum sulfate and the solvent removed by va~uum. The product 5 (7.0 g) wa6 a yellow oil. The structure wa6 confirmed by NMR to be 1-(2-fluorophenyl)-1-(4-methoxyphenyl)-2-propyn-1-ol .
2~4 g (0.008 mole) of the aforedescribed product, 1-(2-fluorophenyl)-1-(4-methoxyphenyl)-2-propyn-1-ol~ was added to a reaction fla6k containing 100 ml of benzene and 1.4 g (0.008 mole) 10 of 6-methoxy-2-hydroxynaphthalene. A catalytic amount of p-toluene sulfonic acid (approximately 20.0 milligrams) was added and the re~ulting mixture stirred and heated between 30-35C. under a nitrogen atmosphere for 3 hours. The reaction mixture was tran6ferred to a ~olution containing 20% aqueous sodium hydroxide 15 and extracted three times - each time with 100 ml of methylene chloride. The extracts were combined, dried over anhydrou6 magne~ium 6ulfate and the 60lvent removed under vacuum. The , resultant oil wa~ column chromatographed on 8il~ ca using 1:10 mixture of ethyl acetate:hexane as the elutant and crystallized by 20 cooling in diethyl ether. The product (0.5 g) melted at 120-123C.
An NMR spectrum confirmet the product to be 8-methoxy-3-(2-fluoro-` phenyl)-3-(4-methoxyphenyl)-3H-naphtho[2,1-b] pyran.
:
~XAMPLE 3 A reaction flask was charged wlth 5 g ( 0.025 mole) of 4-methylbenzophenone, (prepared by the Fr~edel-Craf tB reaction of benzoylchloride with toluene) in 200 ml of tetrahydrofuran and with 8.2 g (0.03 mole) of sodium acetyllde. The reaction mixture wa~
stirred under a nitrogen atmosphere for 8 hours, after which the 30 reaction mixture was quenched in ice water and extracted three times - each time with 100 ml of diethyl ether. The extracts were combined, dried over anhydrous magnesium sulfate, and the solvent removed under vacuum. The product ( 5.0 g ) was confirmed by NMR
spectroscopy to be l-phenyl-l- (4-methylphenyl)-2-propyn-1-ol.
3S 5.0 g (0.02 mole) of the aforedescribed product, l-phenyl-1-(4-methylphenyl)-2-propyn-1-ol, was added to a reaction fla~k containing 3.0 g (0.02 mole) of 6-methoxy-2-hydroxynaphthalene and 200 ml of benzene. The mixture was 6tirred under a nitrogen atmosphere, at 35C. for 4 hours. The solvent wa6 removed on a rotary evaporator and the re~ulting crude oil was washed with 200 ml of a 10% aqueous 60dium hydroxide solution. The aqueous pha6e wa6 5 extracted three time~ - each time with 100 ml of diethyl ether. The extract6 were combined and dried over anhydrou6 magnesium sulfate for 15 minutes. The 601vent was removed under vacuum snd the re~ulting oil was crystallized using an ether-hexane mixture. The product cry6tals (3.0 g) melted at 169 -171C. An NMR spectrum 10 confirmed the product to be 8-methoxy-3-phenyl-3-(4-methylphenyl)-3H-naphtho[2,1-b]pyran.

A reaction flask was charged with 5.0 g (0.02 mole) of 15 4-trifluoromethylbenzophenone, 200 ml of tetrahydrofuran and 6.7 g (0.024 mole) of sodium acetylide. The reaction mixture was stirred for 72 hours under a nitrogen atmosphere at room temperature and then wa6 poured into a 500 ml beaker containing ice water and stirred for an additional thirty minute6. The aqueous pha~e was 20 extracted three time6 - each time with lO0 ml of diethyl ether. The extracts were comb~ned and dried over anhydrous magnesium sulfate for 5 minutes. The solids were filtered ~nd the colvent removed under vacuum. The product (2.75 g) was a yellow oil. The structure was confirmed by NMR spectroscopy to be 1-phenyl-1-(4-trifluoro-25 methylphenyl)-2-propynl-1-ol.
2.75 g( OoOl mole~ of the aforede6cribed product, l-phenyl-1-(4-trifluoromethylphenyl)-2-propynl-1-ol, wa~ added to a reaction flask containing 1.9 g (0.01 mole) of 6-methoxy-2-hydroxy-naphthalene and 200 ml of benzene. A catalytic amount 30 (approximately 20.0 milligram6) of p-toluene 6ulfonic acid was added and the mixture was heated to 35C. with stirring under a nitrogen atmosphere for 10 hours. The reaction mixture was transferred to a 500 ml beaker containing a 10% aqueous sodium hydroxide solution and 6tirred for an additional thirty minute6. The organic layer was 35 separated and the aqueous layer extracted twice - each time with 100 ml of methylene chloride. The extracts were combined and dried over 2130Z7~ ; - 36 -anhydrou6 magnesium sulfate for lO minute~. After filtering off the 601id6, the solvent was removed under vacuum to yield 3.0 g of an oil. Thi~ oil waæ column chromatographed on ~ ce 6el using 20%
ethyl acetate-hexane a~ the elutant. The solvent was removed under 5 vacuum and the product was crystsllized from hexane. The product (0.5 g) melted at 155-157C. The structure wafi confirmed by NMR
spectro~copy to be 8-methoxy-3-phenyl-3-(4-trifluoromethylphenyl)-3H-naphtho[2,1-b]pyran.

A reaction fla~k wa~ charged with 5.5 g (0.023 mole) of 2-fluoro-4'-methylbenzophenone, (prepared by the Friedel-Craft6 reaction of 2-fluorobenzoylchloride with toluene) in 200 ml of tetrahydrofuran and with 7.5 g (0.023 mole) of sodium acetylide.
15 The reaction mixture was stirred for 24 hours, then quenched with ice water and st~rred for an additional thirty minutes. The organic phase was separated and the aqueous phase was extracted three time~
- each t~me with 100 ml of methylene chloride. The extracts were combined and washed w~th distilled water until clear. The extract6 20 were dried o~er anhydrous magne6ium 6ulfate, and the solvent removed under vacuum. The product (5.5 g) wa6 a yellow oil. MMR
~pectro6copy confirmed the product to be 1-(2-fluorophenyl~-1-(4-methylphenyl)-2-propyn-1-ol.
5.5 g ( 0.023 mole) of the aforede6cribed product, 25 1-(2-fluorophenyl)-1-(4-methylphenyl)-2-propyn-l-ol~ wa~ added to a reaction flask containing 4.0 ~ (0.023 mole) of 6-methoxy-2-hydroxy-naphthalene and 200 ml of benzene. A catalytic amount (approximately 2~.0 milligram~) of p-toluene ~ulfonic acid was added with stirring and the reaction was heated st 40C. under a nitrogen 30 atmosphere for 6 hour6. The reaction mixture wa~ tran6ferred to a beaker containlng 200 ml of a 10% aqueous sodium hydroxide solution and stirred for 15 minutes. The organic phase was separated and the aqueous phase wa6hed twice - each time with 100 ml of methylene chloride. The extracts were combined, dried over anhydrous 35 magnesium sulfate and the solvent removed under vacuum. The resultant oil was column chromatographed on silica gel using 20%
ethyl acetate - hexane as the elutant. The photochromic fractions W O 93/17071 PC~r/US93/00873 ,. ., .~
Z~30Z.~2 j; .

were collected and the solvent removed under vacuum. The product (2.0 g) melted at 157-160C. NMR spectroscopy confirmed the product to be 8-methoxy-3-(2-fluorophenyl)-3-(4-methylphenyl~-3H-naphtho[2,1-b~pyran.
EXAMPL~ 6 A reaction flask was charged with 5.0 g (0.02 mole) of 4-(dimethylamino) benzophenone, 200 ml of tetrahydro~uran and 9.3 g (0.03 moles) of 60dium acetylide. The reaction mixture wa6 ~tirred 10 for 24 hours under a nitrogen atmo~phere. 3.1 g (0.01 mole~ ) of addltional ~odium acetylide were added each time to the reaction mixture after elapsed time6 of 8 and 16 hours. The reaction mixture was stirred an additional 24 hours, then tran~fered to a beaker containing a mixture of distilled water and methylene chloride and 15 stirred for 10 minutes. The organic layer was separated and the aqueous layer was extracted twice - each time w~th lG0 ml of methylene chloride. The extracts were combined, dr~ed over anhydrous magnesium sulfate and the solvent removed under vacuum.
The product wa~ crystallized using ~ hexane/ether mixture. The 20 product (4.2 g) melted at 121-123C. NMR Epectroscopy confirmed the product to be l-(phenyl)-1-(4-dimethylaminophenyl)-2-propyn-1-ol.
2.0 g ( 0.008 moles) of the aforede~cribed product, l-(phenyl)-1-(4-d~methylaminophenyl)-2-propyn-1-ol, was added to a reaction flask con~aining 1.56 g (0.009 mole) of 6-methoxy-2-25 hydroxynaphthalene and 150 ml of benzene. 5~0 g of acidic aluminawae added and the reaction mixture stirr~d for one hour at room temperature under a nitrogen atmo6phere. The reaction mixture wa6 hsated on a ste~m b~th for an additional forty-flve minutes. The reaction mixture wa6 vacuum filtered to remove the alumina which wa~
30 washed with 200 ml of ethyl acetate. The ethyl acetate was washed with 250 ml of a 10% aqueous sodium hydroxide solution, dried over anhydrou~ magnesium sulfate and the solvent was removed under vacuum. The resultant product was crystallized in an ether/hexane mixture. The product (2.0 g ) melted at a temperature greater than 35 225C. The 6tructure was confirmed by NMR spectro6copy to be 8-methoxy-3-(4~dimethylaminophenyl)-3-(phenyl~-3H-naphtho[2,1-b3 pyran.

.
Z1302~2 E~AMPLE 7 A 500 ml round bottom reaction flask wa6 charged with 4.0 g (0.025 mole) of 2,6-dihydroxynaphthalene, 200 ml of methylene 5 chloride and 2.6 g (0.025 mole) of acetic anhydride. One equivalent of triethylamine was slowly added with stirring. After stirring for an additional one hour9 dilute hydrochloric acid (200 ml) was added and unreacted 2,6-dihydroxynaphthalene removed by vacuum filtration. The or~anic phase was separated and the aqueous phase 10 extracted three times, each time with 100 ml of methylene chlorlde.
The extracts were comblned, dried and solvent removed under vacuum.
The resulting crude oil wa6 a 50-50 mixture of 6-acetoxy-2-hydroxy-naphthalene and 2,6-diacetoxynaphthalene.
The crude oil (4.0 g) wa6 mixed with 200 ml of benzene and 15 2.08 ~ (0.01 mole) of 1,1-diphenyl-2-propyn-1-ol. A catalytic amount (about 20.0 milligrams) of p-toluene sulfonic acid wa~ added to the mixture with 6tirring. After 4 hour~, a 5 weight percent 60d;um hydroxide solution was added, the organic phase separated and the aqueou~ phase extracted three times, each t~me with lOO ml of ZO methylene chloride. The extracts were combined, dried and solvent removed under vacuum to yield a crude yellow oil. The crude oil wa column chromatographed on silica gel using chloroform as the elut~nt. The solve~t was removed from the combined photochromic fractions to y~eld a crystalline product ha~ing a melting point of 25 180-182C. and an assay of 97.7%. NMR ~pectroscopy confirmed the product to be 8-acetoxy-3,3-diphenyl-3H-naphtho[2,1-b~pyran.

EX~MPLE ~
In addition to the product~ cited in Example~ 1-6,the 30 ~ollowing compounds were prepared using methods of synthe6is similar to those stated in the Examples :
Compound A - 3,3-diphenyl-3H-naphtho[2,1-b]pyran, Compound B - 5-methoxy-3,3-diphenyl-3H-naphtho[2,1-b]pyran, Compound C - 7-methoxy-3,3-diphenyl-3H-naphtho[2,1~b]pyran, Compound D - 9-methoxy-3,3-diphenyl-3H-naphtho[2,1-b]pyran, Compound E - 3-(2-fluorophenyl)-3-(4-methoxyphenyl~-3H-naphtho-~2,1-b]pyran.

~.;,.

~L~
All of the compounds of Examples 1-~ were imbibed by thermal tran~fer into te6t samples of a homopolymer of diethylene 5 glycol bis(allyl carbonate) by the following procedure. Esch naphthopyran wa6 dls~olved in toluene solvent to form a 4% ~olution of the compound. A piece of No. 4 Whatman filter paper was saturated with the naphthopyran solution and allowed to air dry.
The dried filter paper was placed on one side of the polymer test 10 sample, which measured 1/8 inch (0.3 centimeter) x 2 inch (5.1 centimeters) x 2 inch (5.1 centimeter6). A piece of untreated filter paper was placed on the other ~ide of the polymer te6t sample and the resuIting sandwich placed between two plates of flat aluminum metal plates. The entire a~sembly was then placed in a 15 155C. oven for a time sufficient to thermally transfer the naphthopyran into the polymer test sample. Residence time~ in the oven were adjusted to imbibe comparable amount6 of the naphthopyran compounds, as measured by W absorbance.
The imbibed test sample6 were removed from the oven, washed 20 with aeetone, and tested for photochromic response rates on an optical bench. The 6amples were illuminated by a filtered 150 watt Xenon lamp fitted with a copper sulfate bath. An OXl filter with a half-power b~nd width of 320-380 nm wac u~ed in conjunction with quartz metallized neutral den~ity filters to provide a total W
25 irradiance level of 3.0 mW/cm2 as measured u&ing a calibra~ed radiometer at a posltion corresponding to the illuminated ~urface of the sample.
This W -irradiance level i8 equivalent to approximately O.8 ~un of a clear noon, July sunshine mea~ured at latitude 41 lO'N
30 using the calibrated radiometer. Control of exposure wa~
facilitated by means of ~ shutter placed at the exlt lens of the Xenon arc lamp housing. A second beam of light provided by a filtered tungsten lamp arranged to pass through the sample area exposed by the W source was used to monitor changes in transmission 35 of the 6ample over different wavelength ranges in the visible region W O 93/17071 PCT~US93/00873 Z~30272 of the spectrum. The intensity of the monitoring beam after passing throu~h the 6ample was measured by means of an IL-1500 radiometer equipped with a silicon detector head and matching filters.
The ~ OD/Min, which represents the 6ensitivity of the 5 photochromic compound's respon~e to W light, was measured using photopic filters on the silicon detector. The re~ponse of the filtered detector approximated the luminosity curve. The ~ OD was mea~ured over the fir6t five (5) seconds of W expo~ure, then expre66ed on a per minute basis. The saturation optical density 10 (OD) was taken under identlcal cond~tions a8 the ~ OD/Min, except W expo~ure wa6 continued for 20 minute~.
The l~mbda max ( W ) reported in Table 4 i~ the wavelength in the ultra~olet range clo~est to the ~isible spectrum. The lambda max (visible) i6 the wavelength in the visible spectrum at 15 which the maxLmum ab~orption of the activated (colored) form of the photochromic compound o~cur6. The shift in Lambda Max ( W ) also re~ults in an unexpected increase in Sensiti~ity and Saturation OD
(compare the data for Example 1 versu~ the un~ubstituted analog of Example 3A, a6 well a~ Example 2 versu6 Example 8E). Re~ults are 20 tabulated ~n Table 4.

EXAMPLE LAMBDA MAX LAMBDA MAX~OD/MIN ~OD~
COMPOUNPS (VISIBLE) ( W )SENSITIVITY SATURATIQN
1 473 376 1.25 0.73 2 480 376 1.21 1.46 3 472 377 0.98 0.53 4 467 376 0.94 0.67 473 375 1.12 1.47 6 543 376 ~
7 446 365 0.72 0.32 8A 430 359 0.87 0.36 8B 432 323 0.49 0.46 8C 432 365 0.92 0.39 8D 426 329 0.62 0.31 8E 456 359 0.98 l.OO

W O 93/17071 PCT/US~3/00873 30Z`7Z

The results of Table 4 show that Compounds 8B, 8C and 8D, which were re6pectively substituted with a methoxy substituent at the number five, seven and nine carbon atoms on the naphtho portion 5 of the naphthopyran compound, exhibited no significant increaRe in the measured parameter~ over the unsubstituted analogous Compound 8A. Compound 1, which was sub~tituted with a methoxy ~ubstituent at the number eight carbon atom on the naphtho portion of the naphthopyran compound, demonstrated a surprisingly unexpected 10 increase in all the mea~ured parameters compared to the results obtained for Compounds 8A, 8B ,8C and 8D. Further substitution on the diaryl moieties of Compound 1, i.e., the diphenyl moieties, yielded Compounds 2-6. These compounds al~o had higher mea~ured results than those obtained for Compounds 8A, 8B ,8C and 8D.
15 Compound 7, which had a substituent different than methoxy at the number 8 carbon atom on the naphtho portior of the naphthopyran compound also exhibited a bathochromic shift in the vi~ible spectrum, but not as large as that of compound 1.
Although the pre6ent invention ha6 been described with 20 reference to the specific details of particular embodiments thereof, i~ ~8 not intended that such detail6 be regarded as limitations upon the scope of the invention except as and to the extent that they are included in the accompanying claims.

Claims

CLAIMS:

1. A naphthopyran represented by the following graphic formula:
wherein R5 and R9 are each selected from the group consisting of hydrogen, C1-C4 alkoxy and C1-C4 alkyl, R8 is selected from the group consisting of halogen, C1-C5 acyloxy, benzoyloxy, methoxybenzoyloxy, di(C1-C5)alkylamino, and LO-, wherein L is a C1-C12 alkyl, C6-C9 aryl(C1-C3)alkyl, C5-C7 cycloalkyl, or C1-C4 alkyl substituted C5-C7 cycloalkyl, and B and B' are each selected from the group consisting of (i) the unsubstituted or substituted aryl groups phenyl and naphthyl, (ii) the unsubstituted or substituted heterocyclic aromatic groups pyridyl, thienyl, benzothienyl, furyl, and benzofuryl, and (iii) B and B' taken together form the adamantyl group, said aryl and heterocyclic group substituents each being selected from C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 alkoxy(C1-C4)alkyl, di(C1-C5)alkylamino, and halogen, said halogen and halo substituents being selected from the group consisting of fluorine, chlorine and bromine, provided that at least one of B and B' is a substituted or unsubstituted phenyl, except when B and B' form the adamantyl group.

PCT/?? 93/?????

3. The naphthopyran of claim 2 wherein L is C1-C4 alkyl, C6-C7 aryl(C1-C2) alkyl, C5-C6 cycloalkyl, or C1-C2 alkyl substituted C5-C6 cycloalkyl.

4. The naphthopyran of claim 2 wherein R8 is methoxy, chloro or bromo.

5. The naphthopyran of claim 4 wherein Y1 is C1-C3 alkyl, C1-C3 alkoxy or fluoro; Z1 is hydrogen; each Y2 and Z2 is selected from the group consisting of C1-C3 alkyl and C1-C3 alkoxy; a is 0 or 1; and b is an integer from 0 to 2.

6. The naphthopyrans of claim 5 wherein the position of each Y2 and Z2 is meta or para to the carbon atom attached to the pyran ring when a and b are 1.

7. A naphthopyran selected from the group consisting of:
(a) 8-methoxy-3,3,-diphenyl-3H-naphtho [2,1-b]pyran, (b) 8-methoxy-3-(2-fluorophenyl)-3-(4-methoxyphenyl)-3H-naphtho[2,1-b]pyran, (c) 8-methoxy-3-phenyl-3-(4-methyl-phenyl)-3H-naphtho[2, 1-b]pyran, (d) 8-methoxy-3-phenyl-3-(4-trifluoro-methyl)-3H-naphtho[2,1-b] pyran, (e) 8-methoxy-3-(2-fluorophenyl)-3-(4-methylphenyl)- 3H-naphtho[2,1-b]pyran, (f) 8-methoxy-3-(4-dimethylaminophenyl)-3-(phenyl)-3H-naphtho[2,1-b]pyran, and (g) 8-acetoxy-3,3-diphenyl-3H-naphtho[2,1-b]pyran.

8. A photochromic article comprising a polymerized organic host material and a photochromic amount of a naphthopyran compound represented by the following graphic formula:

wherein R5 and R9 are each selected from the group consisting of hydrogen, C1-C4 alkoxy and C1-C4 alkyl, R8 is selected from the group consisting of halogen, C1-C5 acyloxy, benzoyloxy, methoxybenzoyloxy, di(C1-C5)alkylamino, and LO-, wherein L is a C1-C12 alkyl, C6-C9 aryl(C1-C3)alkyl, C5-C7 cycloalkyl, or C1-C4 alkyl substituted C5-C7 cycloalkyl, and B and B' aro each selected from the group consisting of (i) the unsubstituted or substituted aryl groups phenyl and naphthyl, (ii) the unsubstituted or substltuted heterocyclic aromatic groups pyridyl, thienyl, benzothienyl, furyl, and benzofuryl, and (iii) B and B' taken together form the adamantyl group, said aryl and heterocyclic group substituents each being selected from C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 alkoxy(C1-C4)alkyl, di(C1-C5)alkylamino, and halogen, sald halogen and halo substituents being selected from the group consisting of fluorine, chlorine and bromine, provided that at least one of B and B' is a substituted or unsubstituted phenyl, except when B and B' form the adamantyl group.

9. The photochromic article of claim 8 wherein the organic host material is selected from the group consisting of polymers of polyol(allyl carbonate) monomer, polyacrylates, poly(alkylacrylates), polymers of polyfunctional acrylate monomers, cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), polycarbonates, polyurethanes, poly(ethylene terephthalate), polystyrene, copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral, and polymers of diallylidene pentaerythritol.

11. The photochromic article of claim 10 wherein R8 is C1-C4 alkoxy, chloro or bromo.

12. The photochromic article of claim 11 wherein R8 is methoxy.

13. The photochromic article of claim 11 wherein Y1 is C1-C3 alkyl, C1-C3 alkoxy or fluoro; Z1 is hydrogen; each Y2 and Z2 is selected from the group consisting of C1-C3 alkyl and C1-C3 alkoxy; a is 0 or 1; and b is an integer from 0 to 2.

14. The photochromic article of claim 13 wherein the position of each Y2 and Z2 is meta or para to the carbon atom attached to the pyran ring when a and b are 1.

15. The photochromic article of claim 13 wherein the organic host material is a solid transparent homopolymer or copolymer of diethylene glycol bis(allyl carbonate), the carbonate-linked resin derived from a bisphenol and phosgene, polymethylmethacrylate, a polyacrylate or polyvinylbutyral.

16. The photochromic article of claim 15 wherein the photochromic compound is present in an amount of from about 0.01 to 20 weight percent.

17. The photochromic article of claim 16 wherein the article is a lens.

18. The photochromic article of claim 13 wherein there is present in addition a photochromic amount of a further photochromic substance selected from the group consisting of spiro(indolino) naphthoxazines, spiro(indolino)pyrido benzoxazines, splro(indolino) benzoxazines, 3,3-diaryl substituted naphthopyrans free of substitution at the number 8 carbon atom on the naphtho portion of the naphthopyran, and mixtures of such photochromic substances.

19. The photochromic article of claim 18 wherein the mole ratio of the naphthopyran compound to the further photochromic substance is from about 1:3 to 3:1.

20. The photochromic article of claim 18 wherein the further photochromic substance is a spiro(indolino) pyrido benzoxazine, spiro(indolino) benzoxazine, 3,3-diaryl substituted naphthopyran free of substitution at the number 8 carbon atom on the naphtho portion of the naphthopyran, and mixtures of such photochromic substances.

21. The photochromic article of claim 20 wherein the article is a lens.

22. The photochromic article of claim 21 wherein each photochromic substance is present in amounts of from about 0.05 to about 10 weight percent.

23. A naphthopyran represented by the following graphic formula:

wherein R5 end R9 are each selected from the group consisting of hydrogen, C1-C4 alkoxy and C1-C4 alkyl, R8 is selected from the group consisting of halogen, C1-C5 acyloxy, benzoyloxy, methoxybenzoyloxy, di(C1-C5)alkylamino, and LO-, wherein L is a C1-C12 alkyl, C6-C9 aryl(C1-C3)alkyl, C5-C7 cycloalkyl, or C1-C4 alkyl substituted C5-C7 cycloalkyl, and B and B' are the phenyl groups represented respectively by the followlng graphic formulae:

wherein Y1 is selected from the group consisting of C1-C5 alkyl, C1-C5 alkoxy, fluoro and chloro, Z1 is selected from the group consisting of hydrogen and Y1, each Y2 and Y2 are selected from the group consisting of C1-C5 alkyl, C1-C5 alkoxy, cyano, hydroxy, halogen, acrylyl, methacrylyl, acryloxy (C1-C4) alkyl and methacryloxy (C1-C4) alkyl, and a and b are each integers of from 0 to 2.
24. A photochromic article comprising a polymerized organic host material and a photochromic amount of a naphthopyran represented by the following graphic formula:
wherein R5 and R9 are each selected from the group consisting of hydrogen, C1-C4 alkoxy and C1-C4 alkyl, R8 is selected from the group consisting of halogen, C1-C5 acyloxy, benzoyloxy, methoxybenzoyloxy, di(C1-C5)alkylamino, and LO-, wherein L is a C1-C12 alkyl, C6-C9 aryl(C1-C3)alkyl, C5-C7 cycloalkyl, or C1-C4 alkyl substituted C5-C7 cycloalkyl, and B and B' are the phenyl groups represented respectively by the following graphic formulae:

wherein Y1 is selected from the group consisting of C1-C5 alkyl, C1-C5 alkoxy, fluoro and chloro, Z1 is selected from the group consisting of hydrogen and Y1, each Y2 and Z2 are selected from the group consisting of C1-C5 alkyl, C1-C5 alkoxy, cyano, hydroxy, halogen, acrylyl, methacrylyl, acryloxy (C1-C4) alkyl and methacryloxy (C1-C4) alkyl, and a and b are each integers of from 0 to 2.
25. The photochromic article of claim 24 wherein the organic host material is selected from the group consisting of polymers of polyol(allyl carbonate) monomer, polyacrylates, poly(alkylacrylates), polymers of polyfunctional acrylate monomers, cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), polycarbonates, polyurethanes, poly(ethylene terephthalate), polystyrene, copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral, and polymers of diallylidene pentaerythritol.