MX2008008053A - Photochromic indeno-fused naphthopyrans - Google Patents

Abstract

Photochromic materials comprising indeno- fused naphthopyrans having substituents comprising a 4-fluorcVhenyl group and a 4-aminophenyl group bonded to the 3- position of the indeno- fused naphthopyran are disclosed. The photochromic materials may exhibit faster fade rates as compared to similar indeno-fiised naphthopyrans without a 4- fluorophenyl group and a 4-aminophenyl group bonded to the 3-position of the indeno-fiised naphthopyran. Substituted 2-propyn-l-ols utilized for the synthesis of the indeno-fused naphthopyrans disclosed herein are disclosed. Photochromic compositions and articles, such as optical elements, incorporating the photochromic materials disclosed herein are also disclosed.

Description

NAFTOPIRANOS FUNDIDOS DE INDENO, FOTOCROMICOS BACKGROUND Various, non-limiting embodiments of the present disclosure relate to photochromic materials comprising fused indene naphthopyrans, which have substituents including a 4-fluorophenyl group and a 4-aminophenyl group attached to the 3-position of the Naphthopyran, Photochromic materials, according to various, non-limiting embodiments of the present disclosure, may also exhibit faster fading regimes in comparison to similar fused indene naphthopyrans, without a 4-fluorophenyl group and a group of 4 -am? Nophenyl linked to position 3 of the naphthopyran. Other, non-limiting, embodiments of the present disclosure also refer to substituted 2-prop-n-1-oles for the synthesis of the molten naphthopyrans described herein. Still other, non-limiting modalities described herein refer to photochromic compositions and articles, such as optical elements, that incorporate the photochromic materials. Many conventional photochromic materials, such as, for example, photochromic naphthopyrans, may undergo a transformation from a first form or state to a second form or state, in response to the absorption of electromagnetic radiation. For example, many conventional, thermally reversible photochromic materials are capable of being transformed between a first "light" or "bleached" elementary state and a second "colored" activated state, in response to the absorption of certain wavelengths of electromagnetic radiation (or "actinic radiation"). As used herein, the term "actinic radiation" refers to electromagnetic radiation that is capable of causing a photochromic material to transform from a first state or form to a second state or shape. The photochromic material can then be reversed back to the clear elemental state in response to thermal energy, in the absence of actinic radiation. Articles and photochromic compositions, which contain one or more photochromic materials, for example, photochromic lenses for optical applications, generally exhibit the optical materials they contain. Thus, for example, optical lenses containing photochromic materials can be transformed from a clear state to a color state upon exposure to actinic radiation, such as certain wavelengths found in sunlight, and can then revert back to the state clear in the absence of such radiation in the absorption of thermal energy. When used in photochromic articles and compositions, conventional photochromic materials are typically incorporated into a host polymer matrix by an embedding, mixing and / or binding action. Alternatively, the photochromic material can be imbibed in a preformed article or coating. As used herein, the term "photochromic composition" refers to a photochromic material in combination with one or more other materials, which may or may not be photochromic materials. For many photochromic applications, it is generally convenient to have a photochromic material that can rapidly reverse from its colored activated state to the light elemental state form, while still maintaining acceptable characteristics, such as color density. For example, in photochromic optical applications, the optical lenses comprising the photochromic materials, are transformed from an optically clear state, to a colored state, as the user moves from a region of low actinic radiation, such as in an interior, to a region with high actinic radiation, such as direct sunlight. As the lenses become colored, less electromagnetic radiation from the visible and / or ultraviolet regions of the electromagnetic spectrum is transmitted through the lens to the user's eyes. In other words, more electromagnetic radiation is absorbed by the lens, in the colored state than in the optically clear state. When the user subsequently moves from the region of high actinic radiation, the photochromic materials in a user may be inferior to the optimum, during this time, due to the combined effect of the lower ambient light and the reduced transmission of the visible light through the the colored lenses.

Accordingly, for certain applications, it may be advantageous to develop photochromic materials that can transit more rapidly from the colored form to the clear form, as compared to conventional photochromic materials. As used herein, the term "decolorization regime" is a measure of the rate at which the photochromic material is transformed from the activated colored state to the unactivated clear state. The decolorization regime for a photochromic material can be measured, for example, by activating a photochromic material at saturation, ba or controlled conditions, in a given matrix, which measures the absorbance of the activated stable state (ie, optical density). saturated) and then determine the period of time it takes for the absorbance of the photochromic material to decrease by half the absorbance value of the activated stable state. As measured in this way, the decolorization regime is designated by T ^, in units of seconds. The absorption spectrum of a photochromic material in the activated state form will correspond to the color of the article containing the photochromic material, for example, the color of the lens used, when exposed to actinic radiation. As the specific wavelengths within the visible region of the electromagnetic radiation are absorbed by a photochromic material in the form of the activated state, the wavelengths within the visible region that are transmitted (ie not absorbed) correspond to] Color of the photochromic material in the open form. The absorption of the wavelengths of light around 500 nm to about 520 nm, in the visible region of about 500 nm to about 520 nm, in the visible region of the electromagnetic spectrum, results in a photochromic material exhibiting a "reddish" color, that is, it absorbs the visible radiation from the short wavelength or blue end of the visible spectrum and transmits the radiation from the longest wavelength or red end of the visible spectrum. Conversely, the absorption of wavelengths of light from around 580 nm to around 610 nm in the visible region of the electromagnetic spectrum, in a photochromic material, which exhibits a "bluer" color, ie absorbs visible radiation of the longest wavelength at the red end of the visible spectrum, and transmits the radiation from the shortest wavelength or blue end of the visible spectrum. Many current photochromic compounds have activated state absorption spectra that absorb visible light towards the blue end of the visible spectrum and exhibit a reddish color in the activated form. If the photochromic material has an activated state absorption spectrum, which is displaced batochromically, ie displaced to absorb light having a longer wavelength, the photochromic material will exhibit a stronger blue color than the current photochromic material. For certain applications, it may be desirable to have a photochromic material having an absorption spectrum of activated form, displaced batochromically, for actinic radiation and which, therefore, may exhibit a bluer color.

BRIEF COMPENDI Several non-limiting embodiments described here relate to photochromic materials comprising fused indene naphthopyrans having substituents comprising a 4-fluorophenyl group and a 4-ammophenyl group attached at the 3-position of the fused naphthopyran indeno. The photochromic materials, according to certain non-limiting modalities, may have faster fading regimes than a melted naphthopyran of indeno, photochromic, comparable, having no substituents, comprising a 4-fluorophenyl group and a 4-am group. Nophenyl attached to the 3-position of the indene naphthopyran. In a non-limiting embodiment, the photochromic material may comprise a naphthopyran fused indene, comprising a group B attached to its 3-position., and a group B 'attached to its position 3. The group B can be a substituted phenyl group, in which the substituent at the 4-position of the phenyl group 4 -substituted is NR1R2, where R1 and R2 are each, independently, hydrogen, Ci-Ce alkyl, C5-C7 cycloalkyl, phenyl, mono-substituted or di-substituted phenyl, wherein said phenyl substituents are C?-C6 alkyl or C?-C6 alkoxy, or R1 and R2 together with the nitrogen atom form a ring, which contains nitrogen, represented by the following graphic formula II: in which each Y is selected, independently, for each occurrence of -CH2-, -CH (R3) -, -C (R3) 2-, -CH (ar? lo) -, - C (ar? lo) 2- , and -C (R3) (aplo) -, and Z is -Y-, -S-, -S (0) -, -S0? - -NH-, -N (R3) -, or -N (ar ? lo) -, where each R3 is, independently 'C? -C6 alkyl, or hydroxy (C? -C6) alkyl, each aryl is, independently, femlo or naphthyl, m of an integer, 1, 2 or 3, and p is an integer 0, 1, 2 or 3 and when p is 0, Z is -Y-. Still other non-limiting embodiments of the present description refer to a photochromic material having the structure, as indicated in structure III: wherein R16, R17, R18, R19, and R20 represent groups as described herein in the following and indicated in the claims. Still other non-limiting embodiments of the present disclosure refer to a chemical compound having the structure as indicated in structure VI: VI in which R12 represents a group as described herein and stated in the claims. Still other non-limiting embodiments of the present disclosure relate to a method of obtaining a photochromic material, this method comprises reacting the compound of Figure VII, with a 7H-benzo [C] fluoren-5-ol to form a 3H, 13H -indeno- [2 ', 3': 3, 4] naphthol [1,2-b] pyran. Other non-limiting modalities refer to photochromic articles comprising a substrate and the photochromic material, according to any of the non-limiting modalities described herein.

BRIEF DESCRIPTION OF THE DRAWINGS The various non-limiting modalities, described here, can be better understood when read in conjunction with the following Figures. Figures 1-2 illustrate schematic diagrams of reaction schemes for obtaining intermediate products for the synthesis of photochromic materials, according to the various non-limiting modalities described herein. Figure 3 illustrates a schematic diagram of a reaction scheme for obtaining the photochromic materials according to several non-limiting modalities, described herein.

DETAILED DESCRIPTION As used in this specification and the appended claims, the articles "a" and "the" include plural references, unless otherwise stated and unambiguously limited. Additionally, for the purposes of this specification, unless otherwise stated, all numbers expressing ingredient quantities, reaction conditions and other properties or parameters used in the specification shall be understood as modified, in all cases , for the term of "approximately". Therefore, unless stated otherwise, it should be understood that the numerical parameters set forth in the following specification and appended claims are approximations. At least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, the numerical parameters must be read according to the number of significant reported digits and the application of ordinary rounding techniques. Also, while the numerical ranges and parameters that indicate the broad scope of the invention are approximations, as discussed above, the numerical values indicated in the Examples section are reported as precisely as possible. However, it should be understood that such numerical values inherently contain certain errors, which result from the measuring equipment and / or the measurement technique. The photochromic compounds and materials according to various non-limiting embodiments of the invention will now be discussed. As used herein, the term "photochromic" means that it has an absorption spectrum for at least the visible radiation, which varies in response to the absorption of at least the actinic radiation. As used herein, the term "actinic radiation" refers to electromagnetic radiation that is capable of causing a photochromic material to transform from a first form or state to a second form or state. further, as used herein, the term "photochromic material" means any substance that is adapted to have photochromic properties, i.e., is adapted to have an absorption spectrum for at least the visible radiation, which varies in response to the absorption of at least the actinic radiation. As used herein, the term "photochromic composition" refers to a photochromic material in combination with one or more other materials, which may or may not be photochromic materials. As used herein, the term "fused naphthopyran of indene" is defined as a photochromic compound having a ring skeleton comprising an indene [2 ', 3': 3,] nato [1,2 b] pyran, as shown below in (1). Ndeno fused naphthopyrans are examples of photochromic naphthopyrans. As used herein, the term "photochromic naphthopyrans" refers to naphthopyrans that are capable of transferring between a first "closed form" and a second "closed form", in response to the absorption of actinic radiation. As used herein, the term "closed form" corresponds to the elementary state of the melted naphthopyran of indene and the term "open form" corresponds to the form of the activated state of the molten naphthopyran of mdene. As used herein, the terms "position 3", "position 6", "position 11", etc. refer to the 3, 6 and 11 position, respectively, of the ring atoms of the indene naphthopyran skeleton, as illustrated by the positions numbered in structure (I) below. In addition, rings of the indented naphthopyran skeleton ring can be denoted by a letter form A to E. so that each ring can be referenced by its corresponding letter. Thus, for example, as used herein, the terms "ring C" or "ring of the molten naphthopyran of methion" correspond to the lower ring of the naphthyl structure of the naphthopyran fused indene, as denoted by the ring labeled " C "in structure (I) below. As used herein, the term "attached to a carbon of the C-ring" means the bond to a carbon in at least one of the 5-position, 6-position, 6-position, or 7-position, according to the numbering indicated in the structure (I) According to several non-limiting embodiments, described herein, groups B and B 'in the 3-position of the indene-fused naphthopyran are part of the naphthopyran skeleton of indene, photochromic, illustrated above in (I). Without the attempt to be limited by any particular theory, it is believed that groups B and B 'can help to establish the open form of the indene naphthopyran fused structure. According to several non-limiting modalities, described here. the groups B and / or B 'can be of any structure having at least one pi bond, capable of being conjugated with the pi system of the open form of the naphthopyran fused naphthopyran core structure, such as, in the various non-limiting embodiments of the present invention, a substituted phenyl substituent. According to various non-limiting embodiments of the present disclosure, groups B and B 'of the photochromic materials may each comprise a 4-substituted phenyl group, wherein the substituent at the position of each group of Phenyl 4-substituted groups B and B 'are noted below. Various non-limiting embodiments of the photochromic materials of the present disclosure will now be discussed in detail. According to certain non-limiting embodiments, the present disclosure provides a photochromic material comprising a naphthopyran fused indene, comprising a group B attached to the 3-position of the melted naphthyl of indene and a group B 'attached to the 3-position of the naphthopyran cast indene. The group B can be a 4-fluorophenyl group and the group B 'can be a substituted phenyl group, in which the substituent at the 4-position of the 4-substituted phenyl group is -NR -'- R2. According to several non-limiting embodiments, R1 and R2 can each be independently of the other, hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, phenyl, mono-substituted phenyl, or di-substituted phenyl, in which the substituents of phenyl can be C1-C6 alkyl or Ci-Cd alkoxy, or R1 and R2 can form together with the nitrogen atom a nitrogen-containing ring, represented by the following graphic formula II: in which each -Y- can be chosen, independently, in each occurrence, -CH2-, -CH (R ~ -C (RJ) -CH (ar? lo) -, - C (aplo) 2-, and -C (R3) (aryl) -, and Z is -Y-, -S-, -S (O) -, - S02-, -NH-, -N (R3) - or -N (ar? Lo) -, where each R3 is, independently, C? -C6 alkyl, or hydroxy (C? -C6) alkyl, each aplo may independently be phenyl or naphthyl,? m 'is an integer of 1, 2 or 3, and p' is an integer 0, 1, 2, or 3 and when? p 'is 0, Z is -Y- According to certain non-limiting modalities, photochromic materials may have a faster fading rate, as measured in a fragment of polymethacrylate, which a photochromic material comprising a molten naphthylpiran of mdene, wherein the molten naphthopyran of mdene lacks the group of 4-fluoropyran attached in its 3-position, and a phenyl substituted in the 3-position, in which the substituent in the position 4 of the phenyl 4 -substituted is -NR ^^ R2.As used throughout the present description, the term "regime of coloration ", represents a value of kinetic regime that can be expressed by measuring the value T ^ of the photochromic material. As used herein, the term "fading regime" is a measure of the regime in which the photochromic material is transformed from the activated colored state to the inactivated clear state. The decolorization regime for the photochromic material can be measured, for example, by activating a photochromic material at saturation, under controlled conditions in a given matrix, by measuring its activated steady state absorbency (ie, saturated optical density) and then determining the period of time it takes for the absorbance of the matera to the photochromic, to decrease half of the absorbance value of the activated stable state. As measured for this form, the decolorization regime is designated by T ^ with units of seconds. Thus when the decolorization regime is said to be more "fast" the photochromic compound changes from the activated state of color to the light elemental state at a faster rate. The fastest discoloration regime can be indicated, for example, by a decrease in the value of the measurement of ^ for the photochromic material. That is, as the fading regime becomes faster, the period of time for the absorbency to halve the initial activated absorbency value will become shorter. More detailed measurement procedures to determine the values of T ^ for the photochromic materials described herein are indicated in the following Examples. It will be appreciated by those skilled in the art that the decolorization regime of the photochromic material may be dependent on the medium in which the photochromic material is incorporated. As used, the term "incorporated", when used in relation to a photochromic material, is a medium element physically and / or chemically combined with it. In the present description all the photochromic performance data disclosed here, for example the decolorization regime (Ti,), the wavelength (? Max V1S) of maximum absorbency, the saturated optical density and the performance regime, are measured using a standard protocol involving the incorporation of the photochromic material into a fragment of the polymer test, comprising a meta-plate polymer, unless specifically noted otherwise. As used herein, the terms "maximum absorbance wavelength" "or"? mdX V1S "is the wavelength in the visible spectrum in which the maximum absorbance of the activated (colored) form of the photochromic material is.As used herein, the term" saturated optical density "(abbreviated" OD Sat ") is a measure of the absorbance of the stable state (ie, the optical density) of the activated photochromic material, under standard conditions, as defined in the Examples, as used herein, the term "performance regime" or "PR" is A measure of the performance of the photochromic material and is calculated by the equation: Performance Classification = ((DO Sa.) / T, x 10,000- Performance ratings typically have values from 1 to 100, with the highest values being generally preferred.

The photochromic performance test and the standard protocol for the formation of the polymer test fragment, which incorporates the photochromic materials of the various non-limiting embodiments of the present disclosure, are presented in greater detail in the present Examples section. One skilled in the art will recognize that, although the exact values for the decolorization regimes and other data of photochromic performance may vary, depending on the means of incorporation, the photochromic performance data described herein may be illustrative of the relative regimes and data values. that are expected for the photochromic material. when they are incorporated into other media. According to other non-limiting embodiments, the photochromic material comprises a molten naphthopyran of mdene, wherein group B can be a 4-fluorophenyl group, and group B 'can be a group of 4-morpholinophenyl, a 4-p? per? dmofenil, a 4- phenyl (substituted piperidino), a 4-p? rrol? d? nofenilo, a 4-fen? lo (pyrrolidino substituted) or a 4-p? peraz? nofenilo, where the substituent can be a (C1-C6) alkyl or hydroxy (C1-C6) alkyl. In certain non-limiting embodiments, the 4-phopranone group may be a 4-piperazophenyl (N'-substituted), in which the substitution in the nitrogen may be a substituent of (C1-C6) alkyl. with still other non-limiting embodiments, the B 'group may be a 4- (N, N-dialkylamino) phenyl, in which the alkyl groups may be the same or different and may be (C1-C6) alkyls, such as, example, methyl, ethyl, propyl, isopropyl and butyl.

At Ra = F, Rh = piperidino A2 Ra = F, b = morpholino A3 Ra = H, Rb = H A4 Ra = H, Rb = piperidino A5 Ra = H, Rb = morphoIino A6 Ra = F, Rb = 1-1 According to certain non-limiting embodiments, described herein, photochromic materials comprising a naphthopyran fused indene, having a group B, including a group of 4-fluorophenyl and a group B 'with a 4-aminophenyl group, as points and claims here, may have a decolorization regime as measured by a value T ^ i, which is faster than a comparable naphthopyran melt of indene, without the combined groups B and B ', as noted above. For example and with reference to Structure (A), compound Al, according to a specific non-limiting modality, the photochromic material, where group B is 4-fluorophenyl / Ra = F) and group B 'is 4- piperidinophenyl (R = pipepdmo) has a fading regime of? - 118 seconds. In contrast and with reference to Structure (A), compounds A3 and A4, two comparable photochromic materials, where group B is phenyl (Ra = H) and group B 'is either phenyl (Rb = H) or -p? per? dmofenilo (Rb = piperidmo), respectively, have a lower fading regime, values? of 723 seconds and 180 seconds, respectively. Further, with reference to Structure (A), compound A6, the comparable photochromic material, where group B is 4-fluorophenyl (Ra = F) and group B 'is phenyl (Rb = H), has a value T ^ s of the fading regime less than 542 seconds. Further, with reference to Structure (A), compound A2, according to another specific non-limiting embodiment, the photochromic material in which group B is a 4-fluorophenyl (Ra F) and group B 'is a 4-morphonophenyl (Rb = morpholmo) has a decolorization rate of? H 151 seconds. In contrast and with reference to the Structure (A), compounds A3 and A5, two comparable photochromic materials, where group B is phenyl (Ra = H) and the group B 'is either phenyl (Rn = H) or 4-morpholinophenyl (Rb = morpholino), respectively, they have T ^ values of fading regime of less than 723 seconds and 241 seconds, respectively, In addition, with reference to Structure (A), compound A6, comparable photochromic material, where group B is 4-fluorophenyl (Ra) = F) and group B 'is phenyl (Rb = H) have a value? of discoloration regime less than 542 seconds. Certain non-limiting embodiments of the photochromic materials may comprise, in addition to the groups B and B ', as described herein, a first group that removes electrons, attached to a carbon of the ring C of the fused naphthopyran of indene. According to certain non-limiting embodiments of the photochromic material, the first group that removes electrons can be attached to the 6-position of the ring C of the fused naphthopyran of indene. As used here, the terms "group" "groups" mean an arrangement of one or more atoms. As used herein, the term "group withdrawing electrons" can be defined as a group that removes electron density from a pi system, such as, for example, the pi system of the indene naphthopyran fused backbone. In addition, a "group that removes electrons", as used herein, can be defined as a group having a positive Hammett DE value, when the group is attached to a carbon that participates in an aromatic system, such as the aromatic pi system. of the naphthopyran nucleus fused of indene. As used herein, the term "Hammett Dp value" is a measure of the electronic influence, as an influence that donates or removes electrons, from a substituent attached to a carbon that participates in an aromatic pi system, which is transmitted to Through an aromatic pi electron system, the Hammett Dp value is a relative measure that compares the electronic influence of the substituent, in the para position, of a phenyl ring, to the electronic influence of a substituted hydrogen in the para position. Typically for aromatic substituents in general, a negative Hammett Dp value is indicative of a group or substituent having an electron donating influence on a pi electron system (ie, an electron donor group) and a Hammett Dp value. positive is indicative of a group or substituent that has an electron withdrawing influence on a pi electron system (ie, an electron withdrawing group).

Electron withdrawing groups, suitable for use in connection with various non-limiting embodiments of the photochromic material described herein, may have a Dp value of Hammett ranging from about 0.03 to about 0.75. Suitable electron withdrawing groups may comprise, for example (without limitation, halogens, such as fluorine Dp = 0.06), chlorine (Dp = 0.23) and bromine (Dp = 0.23); perfluoroalkyl (for example -CF3, (Dp = 0.54) or perfluoroalkoxy (for example, -OCF3, (Dp = 0.35), wherein the perfluoroalkyl portion of either perfluoroalkyl or perfluoroalkoxy, may comprise, for example, trifluoromethyl or other perfluoroalkyl portions, having the formula CnF2n + l, where? n 'is an integer from 1 to 10; cyano (| JP = 0.66); -OC (= 0) R4 (for example -OC (= 0) CH3, Dp = 0.31), -S02Z (for example, S02CH3, Dp = 0.68 or - (= 1) -, where X is hydrogen (-CHO), Dp = 0.22), C1-C5 alkyl (for example, - C (= 0) CH3, Dp = 0.50), -OR5 (Dp = 0.4) or -NR6R7) for example - C (= 0) NH2 (Dp = 0.36), in which each of R5, R6 and R7 are, independently, hydrogen C 1 -C 6 alkyl, C 5 -C 7 cycloalkyl, phenyl, substituted phenyl, disubstituted phenyl, alkylene glycol or polyalkylene glycol, wherein the phenyl substituents may be C 1 -C 6 alkyl or C 1 -C 6 alkoxy. removal of electrons, which have Hammett Dp values in the range of from 0.05 to approximately 0.75 are indicated in "Section 9 Physicochemical Relations" in the Lange's Handbook of Chemistry, Ed. 15, J.A. Dean, McGraw Hill editor 1999, pages 9.1-9.8. whose description is incorporated herein by reference. It will be appreciated by those skilled in the art that the "p" subscript, when used in relation to the Hammett D value, refers to a Hammett Dp value as measured when the group is located in the para position of a ring. phenyl of a model system, such as a model system of para-substituted benzoic acid. As used herein, the term "polyalkylene glycol" means a substituent having the general structure of - [O- (CaH2a)] bO ", where xa 'and? B' are each, independently, integers from 1 to 10, and R "can be H, alkyl, a reactive substituent, or a second photochromic material. Non-limiting examples of polyalkylene glycols can be found in U.S. Pat. No. 6,113,814, column 3, lines 30.64, the description of which is incorporated herein by reference. Non-limiting examples of the reactive substituents can be found in U.S. Patent Application Serial No. 11 / 102,280, paragraphs [0033] - [0040], the disclosure of which is incorporated herein by reference. According to other non-limiting embodiments, the photochromic materials of the present disclosure can further comprise a second electron withdrawing group, attached at the 11-position of the indene-fused naphthopyran. According to several non-limiting modalities, the second electron withdrawing group can be fluorine, chlorine, bromine, perfluoroalkyl, perfluoroalkoxy, cyano, -0C (= 0) R8, S02X, or -C (= 0) -X wherein X is hydrogen, C? -C6 alkyl, -OR9 or -NR10 R11, wherein R8, R9, R10, and R11, are each, independently, hydrogen, C1-C6 alkyl, C6-C7 cycloalkyl, phenyl, phenyl mono -substituted or di-substituted phenyl, wherein said phenyl substituents are C? -C6 alkyl or C? -C6 alkoxy. Further discussion of the photochromic material comprising a naphthopyran fused indene, a first electron withdrawing group and, in certain non-limiting modalities, a second group of electron withdrawals, as indicated above, can be found in the Non-Provisional Application of US, Serial No. 11 / 314,141, entitled, "Photochromic Materials Having Electron Removal Substituents," filed concurrently with the present, the disclosure of which is incorporated by reference in its entirety. According to certain non-limiting embodiments, the photochromic materials of the present disclosure may comprise a naphthopyran fused indene, in which the first electron withdrawing group, attached to its 6-position, may be a first group of fluorine, and the The second electron withdrawing group, united in its 11-position, can be a second group of fluorine. According to other non-limiting embodiments, the photochromic materials of the present description have the structure represented by the following formula (III): With reference to structure (III), it can be an integer ranging from 0 to 3 and? Q 'can be an integer ranging from 0 to 3. Each R16 and R17 can, for each occurrence, comprise, for example, hydrogen , fluorine, chlorine, bromine perfluoroalkyl, perfluoroalkoxy; cyano -0C (= 0) R21; -S02X; -C (= 0) -X, where X can be, for example, hydrogen, C? -C6 alkyl -OR22, or where R21, R22, R23, and R24 can each be, independently, hydrogen, Cx-C? Alkyl ,, C5-C7 cycloalkyl, phenyl, mono-substituted, or disubstituted phenyl, wherein the phenyl substituents may be C? -C6 alkyl or C? -C6 alkoxy; Ci-Cβ alkyl; C3-C7 cycloalkyl; substituted phenyl or -OR25, where R25 can be, for example, C C-C6 alkyl, phenyl (C? ~C3) alkyl, mono (C?-C6) substituted alkyl phenyl (Ci-C3) alkyl, mono (Ci) -Cβ) substituted alkoxy phenyl (C? -C3) alkyl, (Ci-Cβ) alkoxy (C2-C4) alkyl, C3-C7 cycloalkyl, or mono (C? -C4) substituted alkyl C3-C7 cycloalkyl, and said substituents of phenyl may be Ci-Ce alkyl or Ci-Cβ alkoxy; monosubstituted phenyl, said phenyl having a substituent located at the position for which the substituent is a dicarboxylic acid residue or its derivatives, a residue of diamine or its derivatives, a residue of diamine or its derivatives, an amino alcohol residue or its derivatives, a polyol or its derivatives, -CH2-, - (CH2) t-, or - [0- (CH2) t] k-? where? t 'is the integer 2, 3, 4, 5 or 6 and? k' is an integer from 1 to 50, the substituent being connected to a group of aplo in other photochromic material; or -N (R26) R27, wherein R26 and R27 can each be, independently, for example, hydrogen, Ci-Ce alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl benzot? en-2-? benzot? en-3-? lo, dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, C? -C8 alkylaryl, C3-C? 0 cycloalkyl, C4-C20 bicycloalkyl, C5- C2o tricycloalkyl or Ci - C2o alkoxyalkyl, wherein said aryl group is phenyl or naphthyl. Alternatively R26 and R27 join with the nitrogen atom, to form a C3-C2 hetero-bicycloalkyl or hetero-bicycloalkyl ring or a C4-C20 hetero-tricycloalkyl ring; a ring containing nitrogen, represented by the following graphic formula VAT: VAT in which each -Y-, can be, independently, for each occurrence, -CH2-, -CH (R -C (R28) 7- -CH (aplo) -, C (ar? Lo) 2-, or -C (R, 2? 80) (aryl) -, and Z can be -Y-, -O-, -S-, -S (O) -, -S02- , -NH-, -N (R28) -, or -N (aplo) -, where each R28 can be, independently, Cx-C? alkyl or hydroxy (C? C) alkyl, each aryl can independently be phenyl or naphthyl,? m 'is an integer 1, 2 or 3, and? p' is an integer 0, 1, 2, or 3 and when? p 'is 0, Z is -Y-; a group represented by one of the following graphic formulas IVB or IVC: IVB IVC wherein R, 3J0U, R, 3J1 and R, 32 can each be, independently, for example, hydrogen, C? -C6 alkyl, phenyl, or naphthyl or the groups R30 and R31 can together form a ring of 5 to 8 carbon atoms and each R29 can, independently, for each occurrence be C? -C6 alkyl, C? -C6 alkoxy, fluorine or chlorine and xg 'is an integer 0, 1, 2, or 3; or a C4-Ci8 unsubstituted, mono-, or di-substituted spirobicyclic amine, or an unsubstituted, mono-substituted or disubstituted spirotriccyl amine, wherein said substituents are, independently, aryl, C? -C6 alkyl, C? -C6 alkoxy, or phenyl (C? -C6) alkyl. In addition, a group R16 in the position 6 and a group R16 in the position 7, together can form a group represented by one of the formulas IVD and IVE: IVD IVE where T and T 'can each be, independently, oxygen or the group -NR26. where R26, R30 and R31 may be as noted above. In addition, with reference to structure (III),, R18 and R19 can each be, independently, for example, hydrogen, hydroxy, C? -C6 alkyl; C3-C7 cycloalkyl; aillo; substituted or replaced phenyl; substituted or replaced benzyl; chlorine; fluorine; the group -C (= 0), where it can be, for example, hydrogen, hydroxy, C? -C6 alkyl, Ci-C? alkoxy, unsubstituted, mono- or di-substituted groups, femlo or naphthyl, phenoxy, phenoxy substituted by mono-? -alcox (C 1 -C 6), amino, mono-alkylammo (C 1 -C 6), dialkylammo (C 1 -C 6), phenylamm, substituted phenyl or mono (C 1 -C 6) alkyl or phenylamino substituted by mono- or di-alkyl (C1-C6), -OR33, where R33 can be, for example, C] -C6 alkyl, phenol (C? -C3) alkyl, phenyl mono (Ci-C?) Alkyl substituted phenol (C? C3) alkyl, mono (Ci-Cβ) substituted alkoxy phenyl (Ci-C3) alkyl, C? -C6 alkoxy (C2-C4) alkyl, C3-C7 cycloalkyl, mono (C? -C4) substituted alkyl C3-C7 cycloalkyl , Ci-Cg chloroalkyl, C? -C6 fluoroalkyl, allyl, or the group -CH (R34) W, in which R34 can be hydrogen or C1-C3 alkyl and W can be CN, CF3, or COOR35, where R35 can be hydrogen or C1-C3 alkyl, or R33 may be the group C (= 0) ", where W" m can be, for example, hydrogen, C? -C6 alkyl, C? -C6 alkoxy, the groups phenyl or naphthyl, phenoxy, unsubstituted, mono- or di-substituted, unsubstituted aryl groups, mono- or di-substituted, phenyl or naphthyl, phenoxy, mono-, or di- (Ci-Cβ) substituted alkyl phenoxy, mono -o di- (C? -C6) substituted alkoxy phenoxy, amino, mono (C? -C6) alkylamino, di (Ci-C?) alkylamino, phenylamino, mono- or di- (Cx-C?) substituted alkyl phenylamino, or mono- or di- (C ~ Cg) phenylamino substituted alkoxy, wherein each phenyl, benzyl or aryl substituent group can be. independently, C -C6 alkyl or C? -Cg alkoxy; or a mono-substituted phenyl, said phenyl having a substituent located in the para position, wherein this substituent is: a dicarboxylic acid residue or its derivatives, a residue of diamine or its derivatives, an amino alcohol residue or its derivatives , a polyol residue or its derivatives, -CH2-, - (CH2) t- / or - [O- (CH2) t] ~, where? t 'is an integer 2, 3, 4, 5 or 6 and ? k 'is an integer from 1 to 50, the substituent being connected to an aryl group in another photochromic material. Alternatively, R18 and R19 together form an oxo group a spiro-carbocyclic group containing 3 to 6 carbon atoms, or a spiro-heterocarbocyclic group containing 3 to 6 carbon atoms or a spiro-heterocyclic group containing 3 to 6 atoms of carbon, or a spiro-heterocyclic group containing 1 or 2 oxygen atoms and of 3 to 6 carbon atoms, which includes the spiro-carbon atom, said spiro-carbocyclic or spiro-heterocyclic groups are tempered with 0, 1 or 2 benzene rings. Still referring to the structure (III); R20 can be -NR36R37, wherein R36 and R37 can each be, independently, eg, hydrogen, C -C6 alkyl, C5-C7 cycloalkyl, phenyl, phenyl, mono-substituted or di-substituted phenyl, wherein said phenyl substituents are C? -Ce alkyl or C? -Cg alkoxy. Alternatively, R36 and R37 may, together with the nitrogen atom, form a nitrogen-containing ring represented by the following graphic formula V: V in which each -Y'- can, independently be, for each occurrence: -CH2-, -CH (R 38. -C (R "-Cll (ar? Lo) -, C (aplo) 2-C (R JB, lanío 'and Z' can be -Y'-, -O-, -S (O) -, -S02-, -NH-, -N (R38) -, or -N (ar? Lo) -, where each R38 is, independently, C? -Ce alkyl, or hydroxy (Ci-? C6) alkyl, each aplo is independently phenyl or naphthyl, m 'is an integer 1, 2 or 3, and p' is an integer 0, 1, 2, or 3 and when p 'is 0, Z' is -Y '-.

According to certain non-limiting embodiments, when R20 is morpholino, R16 may not be a 4-substituted piperid, attached to the 7-position of the molten naphthopyran backbone. According to certain non-limiting embodiments, the photochromic material may comprise a structure according to structure (III), wherein R20 may comprise dialkyl ammo, morpholm, pipepdino, pipepdm, substituted pyrrolidm, substituted pyrrolidm, piperizine, or substituted piperizine. The substituent on the piperidino, pyrrolidino, or piperizino portions may comprise (C? -C6) alkyl or hydroxy (C? -C6) alkyl, such as, for example, hydroxymethyl The alkyl substituents of the dialkylamino, may be the same or different and they are C? -C6 alkyls. According to still other non-imitative modalities, the photochromic material can comprise a structure according to the structure (III), where R16 can be a fluorine group, located at the 6-position of the naphthopyran fused indene of the structure (III) and R17 may comprise a second fluorine group located at position 11 of the indene fused naphthopyran of structure (III). Non-limiting methods of obtaining the photochromic materials of various non-limiting embodiments of the present disclosure will now be discussed with reference to Figures 1 and 2. Various methods of synthesizing the 7H-benzo [C] fluoren-5-ol compounds, suitable for their use in the present description can be found, for example in the US Patent No. 6,295,785 in column 11, lines 5 to 18, line 35 and the examples; U.S. Patent No. 5,645,767 in column 5, lines 322 to column 8, line 32 and the examples. Application of U.S. Serial No. 11 / 102,280 (filed April 8, 2006), and U.S. Application. Serial No. 11 / 102,279 (filed April 8, 2005), paragraphs [0099] to [0106] and the examples, said descriptions are incorporated herein by reference. For example, Figure 1 illustrates a non-limiting reaction scheme to obtain the 7H-benzo [C] fluoren-5-o compounds, which may, in certain non-limiting embodiments, have substituents R 'and R ", such as, for example, a first and a second group that removes electrons The 7H-benzo [C] fluoren-5-ol compounds, substituted and replaced, can then be further reacted, as illustrated in Figure 4, with a 1- ( 4-aminophenyl) -1- (4-fluorophenyl) -2-propylene-ol (the general synthesis of which is shown in Figure 2), as described below, to form photochromic materials comprising 3H, 13H- mdeno [2 ', 3': 3, 4] naphtho [1,2-b] pyran (according to several non-limiting embodiments, described herein, further comprises, a group B in addition to its 3-position, and a group B 'attached to its position 3, in which group B and group B' may be as defined and claimed here, it will be appreciated that these reaction schemes are presented for the purposes of only and do not try to be limiting here. Additional examples of methods of obtaining the photochromic materials described herein are set forth in the Examples. 3í Referring now to Figure 1, benzophenone 1 which may be substituted, for example, with a first substituent R 'and / or a second substituent R ", is subjected to a Stobbe condensation, with dimethyl succinate, to give carboxylic acid 2, as a mixture of double-bond isomers (when R 'is not equal to R ", the mixture of isomers can be separated at this point or taken directly in subsequent reactions and then separated.) The carboxylic acid 2 is reacted with the acetic anhydride at elevated temperature to produce the substituted naphthalene 3, where R * is the acetate The ester of naphthol 4 is reacted with an excess of methyl magnesium bromide to give the diol 5 in an aqueous process The diol 5 is cyclized with a sulfonic acid, such as, for example, dodecylbenzene sulfonic acid (! DBSA ") to give 7H-benzo [C] fluoren-4-ol 6. Referring now to Figure 2, in which a non-limiting approach of 1- (4-aminophenyl) -1- (4 - fluorophenyl) -2-propin-1-ol is presented, the 4,4'-difluorobenzophenone (7) is reacted with a secondary amine HNR '' 'R' '' 'to give the 4-amino-4'- fluorobenzophenone 8, where R '' 'and R' '' 'may be the same as R36 and R37, respectively, as noted and claimed here. The acetylide anion, for example sodium acetylide in dimethylformamide saturated with acetylene, is added to the carbonyl of 4-amino- '-fluorobenzophenone 8 to give, in an aqueous preparation, 1- (-ammophenyl) -1 - (4-fluorophenyl) -2-propm-l-ol 0. Referring now to Figure 3, 7H-benzo [C] fluoren-5-ol 6 (a synthesis which is shown in Figure 1 can be reacted with 1- (-ammophenyl) -1- (4-fluorophenyl) -2-prop? nl-ol 9 (a synthesis which is shown in Figure 2). The condensation of 6 and 9 is catalyzed with an acid sulphonic, such as, for example, DBSA or methanesulfonic acid, and provides 3 H, 13 H -indeno [2 ', 3': 3,4] naphtho [1,2-b] pyran 10, according to various embodiments not limiting the present description, which comprises a group B attached to its position 3 and a group B 'attached to its position 3, in which the group B and the group B' can be as defined and claimed here. the matter recognize that various modifications in the material reagents and / or the reaction conditions can be made to the reaction schemes indicated in Figures 1-3, to provide the various non-limiting embodiments of the photochromic materials comprising the molten naphthopyrans of mdeno, substituted, as noted and claimed herein, and that such modifications are within the scope of the invention of the present disclosure. As discussed above, the synthesis of the photochromic materials of the present disclosure may include the reaction of a 7H-benzo [C] fluoren-5-ol 6 with a 1- (4-aminophen) -1- (4-fluorophenyl) -2-prop? Nl-ol 9. Likewise, the amino group of 1- (4-aminophenyl) -1- (4-fluorophenyl) -2-prop? Nl-ol 9 may be substituted , as noted here. According to certain non-limiting embodiments, the present disclosure provides a chemical compound, represented by structure (VI): SAW wherein the group can be a 4-fluorophenyl substituent and the B 'group represents a substituted 4-phenol substituent, wherein the R12 substituent can be -NR13R14. According to certain non-limiting embodiments, R13 and R14 can be combined with the nitrogen atom to form a ring containing nitrogen, represented by the following graphic formula II: II in which each -Y- can be chosen, independently, for each occurrence of -CH2-, -CH (R15) -, -C (R15) 2-, CH (aplo) -, -C (aplo) 2-, and -C (R15) (aplo) -, and Z is -Y-, -0-, -S-, -S (O) -, -S02-, -NH-, -N (R3) -, or - N (aryl) -, in which each R15 can be, independently, for example, C -C6 alkyl, or hydroxy (C? -Cg) alkyl, each aryl can independently be phenyl or naphthyl, m is an integer 1, 2 or 3, and p is an integer 0, 1, 2, or 3, with the proviso that when p is 0, Z will be -Y-. According to certain non-imitative modalities of the prop-1-ol of structure VI, R 12 may comprise the dialkylammo, morphol, pipelide, substituted piperid, pyrrolid, substituted pyrrolid or piperazinium or substituted piperazimo. The substituents on the pipepdino, pyrrole dmo, or piperazmo moieties, may comprise, for example, (C? -C6) alkyl or hydroxy (0? -Ce) alkyl. The alkyl substituents of the dialkylamino may be the same or different and are (Ci-Cβ) alkyl. In certain other non-limiting embodiments of the photochromic materials of the present disclosure, they may be represented by their chemical names, as determined, at least in part, by the IUPAC nomenclature system. The photochromic materials, considered by the present disclosure, include: (a) 3- (4-fluorophen? L) -3- (4-morphonophenyl) -13, 13-d? Met? L-3H, 13H-? Ndeno [ 2 ', 3': 3, 4] naphtho [1, 2-b] pyran; (b) 3- (4-fluorophenyl) -3- (4-morphonophenyl) -6,11-d? fluoro-13, 13-d? met? l-3H, 13H-mdeno [2 ', 3': 3 , 4] naphtho [1,2-b] pyran; (c) 3- (4-fluorophenyl) -3- (4-p? pepd? nofenil) -13, 13-d? met? l-3H, 13H-? ndeno [2 ', 3': 3, 4] naphtho [1, 2-b] pranus; (d) 3- (4-fluorophenyl) -3- (-p? per? d? n-phenyl) -6,11-d? fluoro-13, 13-d? met? l-3H, 13H-? ndeno [2 ', 3': 3,4] naphtho [1,2-b] pranus; (e) 3- (4-fluorophen? l) -3- (4- (2-methylpiperidino) phenyl) -13, 13-d? met? -3H, 13H-índeno [2 ', 3': 3, 4] naphtho [1, 2-b] pranus; (f) 3- (4-fluorophen? l) -3- (4- (2-methylpiperidyl) phenyl) -6,11-d? f luoro-13, 13-d? met? l-3 H, 13 H -indeno [2 ', 3': 3,4] naphtho [1,2-b] pranus; (g) 3- (4-fluorophen? l) -3- (4-p? pepz? nofen? l) -13, 13-d? met? l-3H, 13H-mdeno [2 ', 3': 3 , 4] naphtho [1, 2-b] pranus; (h) 3- (4-fluorophenyl) -3- (4-p-per-zomophenyl) -6,11-d? -fluoro-13, 13-d? met? l-3H, 13H-mdeno [2 ', 3 ': 3,4] naphtho [l, 2-b] pranus; (i) 3- (4-fluorophenyl) -3- (4-pyrrolidonephenyl) -13, 13-d? met? l-3H, 13H-? ndeno [2 ', 3': 3, 4] naphtho [1,2-b] pyran; (j) 3- (4-fluorophen?) -3- (4-pyrrolidone) -6, 11-d? fluoro-13, 13-d? met? l-3H, 13 H -indeno [2 ', 3': 3, 4] naphtho [1,2-b] pyran; (k) 3- (4-fluorophen? l) -3- (4- (N, N-diethylammo) phenyl) -13, 13-d? met? l-3H, 13H-mdeno [2 ', 3': 3,4] naphtho [1, 2-b] pranus; and (1) 3- (4-fluorophen? l) -3- (4- (N, N-diethylammo) phenyl) -6,11-d? fluoro-13, 13-d? met? l-3H, 13H - índeno [2 ', 3': 3,4] naphtho [l, 2-b] pranus.

The photochromic materials of the present disclosure, for example the photochromic materials comprising the photochromic materials of the present disclosure, for example photochromic materials including a fused naphthopyran indene attached in the 3-position, and a group B 'attached to its 3-position , wherein the group B is a 4-fluorophenyl group and the group B 'is a 4-substituted phenyl group, where the substituent which is at the 4-position of the phenyl group 4-sust? tu? is, is -NRXR2, as noted herein, can be used in applications where photochromic materials can be employed, such as optical elements, for example an ophthalmic element, an exhibit element, a window, a mirror, a cell element of active liquid crystal or a passive liquid crystal cell element. As used herein, the term "optical" belongs to or is associated with light and / or vision. As used herein, the term "ophthalmic" belongs or is associated with the eye and vision. As used herein, the "display" element means a representation that can be read by a machine, of information in words, numbers, symbols, designs or drawings. Non-limiting examples of display elements include screens, monitors and security elements, such as security markings. As used herein, the term "window" means an aperture adapted to allow the transmission of radiation therethrough. Non-limiting examples of windows include aircraft and automobile windshields, automotive and aircraft transparencies, for example, T-roofs, side lights and rear lights, filters, shutters and optical switches. As used herein, the term "mirror" means a surface that specularly reflects a large fraction of the incident light. As used herein, the term "liquid crystal cell" refers to a structure that contains a liquid crystal material that is capable of being ordered.A non-limiting example of a liquid crystal cell element is a liquid crystal display In certain non-limiting embodiments, the photochromic materials of the present disclosure may be used in an ophthalmic element, such as corrective lenses, which include single vision or multiple vision lenses, which may or may not be segmented, such as , but not limited to bifocal lenses, trifocal lenses and progressive lenses), corrective lenses, or magnifying lenses, a protective lens, a viewfinder, lenses for bulging eyes and a lens for an optical instrument, such as a camera or telescopic lenses. other non-limiting embodiments, the photochromic materials of the present disclosure, can be used in plastic films and sheets, textiles and coatings you.

Furthermore, it is considered that the photochromic materials, according to several non-limiting modalities, described herein, can each be used alone, in combination with other photochromic materials, according to several non-limiting modalities, described herein, or in combination with a complementary photochromic conventional material, appropriate. For example, photochromic materials, according to various non-limiting embodiments described herein, may be used in conjunction with conventional photochromic materials having maximum activated absorption within the range of about 400 to about 800 nanometers. In addition, the photochromic materials, according to several non-limiting embodiments, described herein, may be used in conjunction with the conventional complementary polimepable photochromic material or may be compatible, such as, for example, that described in U.S. Pat. Nos. 6,113,814 (in col 2, line 39 to col 8, line 51) and 6,555,028 (in col.2, line 65 to col.12, line 66) whose descriptions are specifically incorporated herein by reference. As discussed above, according to several non-limiting embodiments, described herein, the photochromic compositions may contain a mixture of photochromic materials. For example, although not limited to that, mixtures of photochromic materials can be used to obtain certain activated colors, such as almost neutral gray or almost neutral brown. See, for example, U.S. Pat. No. 5,645,787, col. 12, line 66 to col. 13, line 19, which describes the parameters that define the neutral gray and brown colors and whose description is incorporated here specifically as a reference.

Various non-limiting modalities, described herein, provide a photochromic composition comprising an organic material, said organic material being at least one polymeric material, an oligomeric material and a monomer material, and a photochromic material, according to any of the non-limiting modalities of those indicated above, incorporated in at least a portion of the organic material. According to various non-limiting embodiments described herein, the photochromic material can be incorporated in a portion of the organic material by at least one of the mixture and bonding of the photochromic material with the organic material or its precursor. As used herein, with reference to the incorporation of photochromic materials, in an organic material, the terms "mixing" and "mixing" mean that the photochromic material intermixes with at least a portion of the organic material, but does not bind to the organic material Also, as used herein with reference to the incorporation of photochromic materials into an organic material, the terms "joined" or "attached" mean that the photochromic material is linked to a portion of the organic material or its precursor As discussed above, the photochromic compositions, according to various non-limiting embodiments, described herein, may comprise an organic material chosen from a polymeric material, an oligomeric material and / or a monomeric material Examples of polymeric materials that can be used with set with several non-limiting modalities, described herein, include, without limitation, polymers of mon bis (allyl carbonate) dimers, diethylene glycol dimethacrylate monomers, ethoxylated bisphenol A dimethacrylate monomers, diisopropenyl benzene monomers; ethoxylated bisphenol A dimethacrylate monomers, ethylene glycol bismetacrylate monomers, poly (ethylene glycol) bismethyl monomers, ethoxylated phenol bismethyl methacrylate monomers, polyhydric alcohol acrylate monomers, such as trimethylol triacrylate monomers, alkoxylated propane, such as ethoxylated trimethylolpropane tpacrylate monomers, urethane acrylate monomers, vmylbenzene monomers and styrene. Other non-limiting examples of suitable polymeric materials include polyfunctional type polymers, for example mono-, di- or multi-functional acrylate and / or meta-platelet monomers, poly (C? -C? 2 alkyl) methacrylates such as poly (methyl methacrylate), poly (oxyalkylene) dimethacrylate, poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose acetate, cellulose acrylate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly ( vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride, polyurethanes, polythiourethanes, thermoplastic polycarbonates, polyesters, poly (ethylene terephthalate), polystyrene, poly (methylstyrene), copolymers of styrene and methyl methacrylate, copolymers of styrene and acrylonitrile, polyvinylbutyral and pentaerythritol polymers of diallylidene, particularly, copolymers with polyol monomers (carbonate of aillo, for example, diethylene glycol-bis (carbonate of allyl) o) and acrylic monomers, for example ethyl acetate, butyl acrylate. The copolymers of the aforementioned monomers, combinations and mixtures of the aforementioned polymers and copolymers with other polymers are also considered, for example, to form inter-penetrant network products. Also, according to several non-limiting modalities, in which the transparency of the photochromic composition is convenient, the organic material can be a transparent polymeric material. For example, according to several non-limiting embodiments, the polymeric material may be an optically clear polymer material, prepared from a thermoplastic polycarbonate resin, which is sold under the LEXAN® trademark., a polyester. such as the material sold under the trademark MYLAR®, a poly (methyl meta-plate), such as the material sold under the trademark of PLEXIGLÁS®, and polymers of a polyol monomer (carbonate of aillo), especially diethylene glycol. glycol-bis (carbonate of aillo), this monomer is sold under the trademark of CR-39®, and polyurea-polyurethane (polyurea-urethane) polymers, which are prepared, for example, by the reaction of an oligomer of polyurethane and a diamam curing agent, a composition for one of such polymers is sold under the trademark of TRIVEX® by PPG Industries, Inc. Other non-limiting examples of suitable polymeric materials include polymers of polyol copolymers ( carbonate of aillo), for example diethylene glycol bis (carbonate of aillo), with other copolymerizable monomeric materials, such as, but not limited to: copolymers with vinyl acetate, copolymers with a polyurethane ue has terminal functionality of diacrylate and copolymers with aliphatic urethanes, whose terminal portion contains functional groups of aillo or acnlilo. Still other suitable polymeric materials include, without limitation, polyvinyl acetate, polyvinyl acetate, polyurethane, polythiourethanes, selected diethylene glycol polymers, dimethacrylate monomers, diisopropenyl benzene monomers, ethoxylated bisphenol A dimethacrylate monomers, monomers of ethylene glycol bismethacrylate, ethoxylated phenol bismetacrylate monomers and ethoxylated trimethylolpropane tpacplate monomers, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and copolymers of styrene with methyl methacrylate , vmilo acetate and acrylonitrile. According to a non-limiting embodiment, the polymeric material may be of the optical reams sold by PPG Industries, Inc., under the designation CR, such as, for example, CR-307, CR-407 and CR-607.

According to a certain specific non-limiting embodiment, the organic material can be a polymeric material chosen from poly (carbonate) copolymers of ethylene and vmyl acetate, copolymers of ethylene and vinyl alcohol, copolymers of ethylene, vmyl acetate and vinyl alcohol (such such as those resulting from the partial saponification of copolymers of ethylene and vmilo acetate), cellulose acetate butyrate, poly (urethane), poly (acrylate, poi (methacrylate), epoxides, ammoplast functional polymers, poly (anhydride), poly (urethane-urea), functional polymers of N-alkoxymethyl (meth) acrylamide, poly (siloxane), pol? (silane, and combinations and mixtures thereof.) Various non-limiting embodiments described herein provide photochromic articles comprising a substrate and a photochromic material, according to any of the foregoing non-limiting embodiments, connected to or incorporated in a portion of the substrate. used here, the term "connected to 1, means associated with, or directly or indirectly through another material or structure. In a non-limiting embodiment, the photochromic articles of the present disclosure can be an optical element for example, but not limited to, an ophthalmic element, an exhibit element, a window, a mirror, an active liquid crystal cell element, and a passive liquid crystal cell element. In certain non-limiting modalities,. The photochromic article is an ophthalmic element, for example, but not limited to, corrective lenses, which include single vision, or multiple vision lenses, which may be either segmented or non-segmented (such as, but are not limited to). , bifocal lenses, trifocal lenses and progressive lenses), non-corrective lenses, magnification lenses, protective lenses, a viewfinder, protruding lenses, and lenses for an optical instrument. According to several non-limiting embodiments, described herein, in which the substrate of the photochromic article comprises a polymeric material, the photochromic material can be connected to at least a portion of the substrate, by the incorporation of the photochromic material into at least a portion of the material polimépco of the substrate, or at least a portion of the oligomeric or monomeric material from which the substrate is formed. For example, according to a non-limiting embodiment, the photochromic material can be incorporated into the polymeric material of the substrate by the on-site casting method. Additionally or alternatively, the photochromic material can be incorporated into at least a portion of the polymeric material of the substrate by embedding. The method of embedding and molding on the site, are discussed below. According to other non-limiting embodiments, the photochromic material may be connected to at least a portion of the substrate of the photochromic article as part of at least one partial coating, which is connected to at least a portion of a substrate. According to this non-limiting embodiment, the substrate can be a polymeric substrate or an inorganic substrate (such as, but not limited to, a glass substrate).

In addition, the photochromic material can be incorporated into at least a portion of the coating composition, prior to the application of this coating composition to the substrate, or alternatively, a coating composition can be applied to the substrate, at least partially, and in followed by the photochromic material can be embedded in at least a portion of the coating.

As used herein, the terms "set" and "set" include, without limitation, curing, polymerizing, entangling, retting and drying.

For example, in a non-limiting embodiment of 3 to the present disclosure, the photochromic article may comprise at least a partial coating of a polymeric material, connected to at least a portion of its surface. According to this non-limiting embodiment, the photochromic material can be mixed or bonded with at least a portion of the polymeric material of the at least partial coating. This at least partial coating, comprises a photochromic material which can be directly connected to the substrate, for example, by directly applying a coating composition, comprising a photochromic material to at least a portion of a surface of the substrate and at least partially hardening the coating composition. Additionally or alternatively, this at least partial coating, comprising a photochromic material. it can be connected to the substrate, for example, through one or more additional coatings. For example, and without limitation, according to several non-limiting embodiments, a coating composition can be applied to at least a portion of the surface of the substrate, at least partially harden, and then the coating composition comprising the photochromic material , it can be applied over the additional coating and cure, at least partially. Non-limiting methods of applying coating compositions to substrates are discussed in the following. Non-limiting examples of additional coatings and films that can be used in conjunction with the photochromic articles described herein include sizing or compatible coatings, protective coatings, including transition coatings, abrasion resistant coatings and other coatings that protect against abrasion. effects of the polymerization reaction chemicals and / or protect against deterioration, due to environmental conditions, such as humidity, heat, ultraviolet light, oxygen (eg UV light protective coatings and oxygen barrier coatings) coatings against the reflection, conventional photochromic coatings and polarization coatings and stretched polarization films, and their combinations. Non-limiting examples of sizing coatings or compatibilizers, which may be used in conjunction with various non-limiting embodiments, described herein, include coatings comprising coupling agents, at least partial hydrolysates of coupling agents, and mixtures thereof. As used herein, the "coupling agent" means a material having a group capable of reacting, binding and / or associating with a group on a surface. Coupling agents, according to several non-limiting modalities described herein, may include organometallics, such as silanes, titanates, zirconates, aluminates, zirconium aluminates, their hydrolysates and mixtures thereof. As used herein, the phrase "at least partial hydrolysates of the coupling agents" means that some or all of the hydrolysable groups in the coupling agent are hydrolyzed. Other non-limiting examples of size coatings that are suitable for use in conjunction with the various non-limiting embodiments disclosed herein include those size coatings described in U.S. Pat. 6,025,026 in column 3, line 3 to column 11, line 40, and U.S. 6,150,430, in column 2, line 39 to column 7, line 58, the descriptions of which are specifically incorporated herein by reference. As used herein, the term "transition coating" means a coating that aids in the creation of a property gradient between two coatings. For example, although not limited here, a transition coating can assist in creating a hardness gradient, between a relatively hard coating (such as an abrasion resistant coating) and a relatively smooth coating (such as a photochromic coating). Non-limiting examples of transition coatings include the acrylate-based thin films, cured by radiation, as described in US Patent Application, Publication 2002/0165686 in paragraphs [0079] - [0173], which is specifically incorporated herein as reference. As used herein, the term "abrasion resistant coating" refers to a protective polymeric material that exhibits an abrasion resistance that is greater than the standard reference material., for example a polymer obtained from monomer CR-39, available from PPG Industries, Inc., as tested in a method comparable to the ASTM F-735 Standard Test Method for Abrasion Resistance of Plastics and Transparent Coatings, Using the Method of Oscillating Sand Non-limiting examples of abrasion resistant coatings include abrasion resistant coatings, comprising organosilanes, organosiloxanes, abrasion resistant coatings based on inorganic materials, such as silica, titania and / or zirconia, and organic abrasion resistant coatings of the type that are curable by ultraviolet light.

Non-limiting examples of anti-reflection coatings include monolayer or multilayer coatings, metal oxides, metal fluorides or other such materials, which may be deposited on the articles described herein (or on self-supporting films that are apply to articles), for example, through the vacuum deposit, electronic deposit, etc. Non-limiting examples of conventional photochromic coatings include, but are limited to, coatings comprising conventional photochromic materials. Non-limiting examples of polarization coatings and polarized stretch films include, but are not limited to, coatings (such as those described in US Patent Application, Publication No. 2005/0151926) and stretched films comprising dichroic compounds that are known in art. As discussed herein, according to several non-limiting embodiments, an additional coating or film, at least partially, can be formed on the substrate before forming the coating, comprising the photochromic material, according to several non-limiting embodiments, here described, on the substrate. For example, according to certain non-limiting embodiments, a sizing coat or compatibilizer can be formed on the substrate, before applying the coating composition comprising the photochromic material. Additionally or alternatively, a further at least partial additional coating can be formed on the substrate, after forming the coating, which comprises the photochromic material, according to several non-limiting embodiments described herein, on the substrate, for example, as an overcoat. coating in the photochromic coating. For example, according to certain non-limiting embodiments, a transition coating may be formed on the coating, comprising the photochromic material and an abrasion-resistant coating may be formed on the transition coating. For example, in accordance with a non-limiting embodiment, a photochromic article is provided comprising a substrate (such as, but not limited to a flat-concave or planoconvex ophthalmic lens substrate), comprising an abrasion-resistant coating on the minus a portion of its surface, a sizing coat or compatibilizer on at least a portion of the abrasion resistant coating; a photochromic coating comprising a photochromic material, according to several non-limiting embodiments described herein, in at least a portion of the sizing coat or compatibilizer; a transition coating on at least a portion of the photochromic coating and an abrasion resistant coating on at least a portion of the transition coating. Furthermore, according to this non-limiting embodiment, the photochromic article may also comprise, for example, a coating against the reflection, which is connected to a surface of the substrate and / or a polarization coating or film, which is connected to a surface of the substrate. Non-limiting methods of obtaining photochromic compositions and photochromic articles, such as optical elements, according to several non-limiting modalities described herein, will now be discussed. A non-limiting embodiment provides a method of obtaining a photochromic composition, the method comprising incorporating a photochromic material into at least a portion of an organic material. Non-limiting methods of incorporating photochromic materials into an organic material include, for example, mixing the photochromic material in a solution or melt of a polymeric, oligomeric or monomeric material, and then curing, at least partially, the polymeric, oligomeric or monomeric material (with or without joining the photochromic material to the organic material) and embedding the photochromic material in the organic material (with or without binding of the photochromic material to the organic material). Another non-limiting modality provides a method of obtaining a photochromic article, which comprises connecting a photochromic material, according to several non-limiting modes, discussed above, to at least a portion of a substrate. For example, if the substrate comprises a polymeric material, this photochromic material may be connected to at least a portion of the substrate, by at least one method of in situ molding and by embedding. For example, in the site molding method, the photochromic material can be mixed with a polymer solution or a melt, or other oligomeric and / or monomeric solution or mixture, which are subsequently molded into a mold having a desired configuration and at least partially cure to form the substrate. Optionally, according to this non-limiting embodiment, the photochromic material can be attached to a portion of the polymeric material of the substrate, for example by copolymerization with its monomeric precursor. In the embedding method, the photochromic material can be diffused into the polymeric material of the substrate, after it is formed, for example, by immersing the substrate in a solution containing the photochromic material, with or without heating. Immediately, although not required, the photochromic material can be bonded with the polymeric material. Other non-limiting embodiments, described herein, provide a method of obtaining an optical element, comprising connecting a photochromic material to at least a portion of a substrate or at least one of the molding in a mold, coating and lamination. For example, according to a non-limiting embodiment, in which the substrate comprises a polymeric material, the photochromic material can be connected to when a portion of a substrate is formed by molding within a mold. According to this non-limiting embodiment, a coating composition comprising the photochromic material, which may be a liquid coating composition or a powder coating composition, is applied to the surface of a mold and cured, at least partially . Then, a solution of polymer or melt, or an oligomeric or monomeric solution or mixture is molded on the coating and cured, at least partially. After curing, the coated substrate is removed from the mold.

Non-limiting example of powder coatings, in which the photochromic materials, according to several non-limiting modalities described herein, can be used, are pointed out in U.S. Pat. No. 6,068,797 in column 7, line 50 to column 19, line 42, which is specifically incorporated herein by reference. According to yet another non-limiting embodiment, in which the substrate comprises a polymeric material or an inorganic material, such as glass, the photochromic material can be connected to at least a portion of a substrate by coating. Non-limiting examples of suitable coating methods include the rotary coating, spray coating (e.g., using a liquid or powder coating), curtain coating, roller coating, rotary and spray coating, over-molding and combinations thereof . For example, according to a non-limiting mode, the photochromic material can be connected to the substrate by over-molding. According to this embodiment it did not limit, a requirement composition, comprising the photochromic material (which may be a liquid coating composition, a powder coating composition, (as previously discussed) may be applied to a mold and then the substrate it can be placed inside the mold, so that the substrate contacts the coating, causing it to spread over at least a portion of the surface of the substrate, then the coating composition can be cured, at least partially, and the substrate The overmoulding can be done by placing the substrate in a mold, so that the open region is defined between the substrate and the mold, and then a coating composition comprising the substrate is injected. photochromic material within the open region, then the coating composition can be cured, at least partially, and its Coated substrate can be removed from the mold. Additionally or alternatively, a coating composition (with or without a photochromic material) can be applied to a substrate (for example, by any of the above methods), the coating composition can be cured, at least partially, and then a material Photochromic can be embedded (as previously discussed) in a coating composition. According to yet another non-limiting embodiment, in which the substrate comprises a polymeric material or an inorganic material, such as glass, the photochromic material can be connected to at least a portion of a substrate by lamination. According to this non-limiting embodiment, a film comprising the photochromic material can be adhered or otherwise connected to a portion of the substrate, with or without an adhesive and / or the application of heat and pressure. Then, if desired, a second substrate can be applied on the first substrate and the two substrates can be laminated together (ie, by the application of heat and pressure) to form an element, wherein the film comprising the photochromic material It stands between the two substrates. Methods for forming films comprising a photochromic material may include, for example, and without limitation, combining a photochromic material with a polymer solution or oligomeric solution or its mixture, molding or extruding a film thereof and, if required, curing, at less partially, the movie. Additionally or alternatively, a film (with or without a photochromic material) and imbibed with the photochromic material (as discussed above) can be formed. In addition, several non-limiting modalities, described herein, consider the use of various combinations of the above methods to form photochromic articles, in accordance with the various non-limiting modalities described herein. For example, and without limitation, according to a non-limiting modality, a photochromic material can be connected to the substrate by inoration into an organic material from which the substrate is formed (for example, using the molding method on the site and / or the embedment) and then a photochromic material (which can be the same or different from the aforementioned photochromic material) can be connected to a portion of the substrate using the mold molding, coating and / or rolling methods discussed above. Likewise, those skilled in the art will appreciate that the photochromic compositions and articles, acing to various non-imitative modalities described herein, may also comprise other additives, which aid in the process and / or performance of the composition or article.- non-limiting examples of such additives include photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers, (such as, but not limited to, ultraviolet light absorbers and light stabilizers, such as amine light stabilizers. obstructed (HALS) = heat stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not limited to, surfactants), free radical scavengers, adhesion promoters (such as hexanodiol diacrylate, and coupling agents) and combinations and their mixtures Acing to several non-limiting modalities, the materials The photochromes described herein may be used in amounts (or ratios) such as the organic material or substrate on which the photochromic materials are inorated or otherwise connected, exhibiting the desired optical properties. For example, the amount and types of photochromic materials may be selected so that the organic material or substrate may be clear or colorless, when the photochromic material is in the closed form (i.e., in the bleached or activated state) and may exhibiting a desired resultant color when the photochromic material is in the open form (ie, when activated by actinic radiation). The precise amount of the photochromic material to be used in the various photochromic compositions and articles, described herein, is not critical, as long as a sufficient amount is used to produce the desired effect. It should be appreciated that the particular amount of the photochromic material used may depend on a variety of factors, such as, but not limited to, the absorption characteristics of the photochromic material, the color and intensity of the color desired in the activation, and the method used to inorate or connect the photochromic material to the substrate. Although not limited thereto, acing to several non-limiting embodiments described herein, the amount of the photochromic material that is inorated into the organic material, may vary from 0.01 to 40 weight percent, based on the weight of the organic material. Various non-limiting modalities, described herein, will now be illustrated in the following non-limiting examples.

EXAMPLES In Part I of the Examples, the synthetic procedures used to obtain photochromic materials, according to certain non-limiting embodiments, described herein, are set forth in Examples 1-4. In Part II, the formation of methacrylate test fragments, which incorporate certain photochromic materials, as described herein, together with comparative photochromic materials, and test procedures to determine the rate of discoloration (T ^), the wavelength Maximum absorbency, and saturated optical density, are described.

PART I: SYNTHETIC PROCEDURES Example 1 Stage 1 Piperidine (23.4 grams (vg ')) was added, 4,4 '-difluorobenzophenone (60 g), tpetilamma (30.6 g) to a reaction flask, containing 100 milliliters (? Ml') of dimethylsulfoxide. The resulting mixture was heated to 105 ° C and stirred overnight under a nitrogen atmosphere. After 24 hours at 105 ° C, the reaction was cooled in 1400 ml of water, with vigorous stirring, to give a light tan solid precipitate. The solid was filtered, washed with water and dried in air to obtain 79.5 g of the desired product, 4-fluoro-4-p? Per? Dmobenzophenone. This material was used in the next step with further purification.

Step 2 The product from Step 1, 1,4-fluoro-4'-piperidmobenzophenone (78 g), was added to a reaction flask containing 500 ml of the N, N-dimethylformamide saturated with acetylene. The resulting mixture was stirred using a mechanical stirrer, at room temperature, under a nitrogen atmosphere. The sodium acetylide in xylenes / mineral oil (73.5 g of an 18 wt% solution) was added over thirty minutes to the reaction mixture while stirring. After stirring for one hour at room temperature, the reaction was cooled in 4 liters of water, with vigorous stirring, to give a solid yellow-brown precipitate. The solid was filtered, washed with water and dried in open air to obtain 85 g of the desired product, 1- (4-fluorophenyl) -1- (-piperidinophenyl) -2-propyn-1-ol. This material was used in Step 7, they are further purified.

Step 3 The potassium t-butoxide (68.8 g) was weighed into a reaction flask, equipped with a mechanical stirrer, placed under a nitrogen atmosphere and 700 ml of toluene was added, followed by the 4,4 '-difluorobenzophenone ( 100 g). The reaction mixture was mechanically stirred and heated to 70 ° C. A solution of dimethyl succinate (80 g) in 100 ml of toluene was added to the reaction mixture over a period of 60 minutes. The reaction mixture was heated at 70 ° C for 4 hours. After cooling to room temperature, the reaction mixture was poured into 500 ml of water and the toluene layer was discarded. The aqueous layer was extracted with diethyl ether (1 x 400 ml) to remove the neutral products and then the aqueous layer was acidified with concentrated HCl. An oily yellow-brown solid was obtained from the aqueous layer, and extracted with 3 x 300 ml of ethyl acetate. The organic layers were combined, washed with a saturated solution of NaCl (1 x 500 ml) and dried over anhydrous sodium sulfate. Removal of the solvent by rotary evaporation gave 122 g of the acid, 4-d? (4-fluorophenyl) -3-methoxycarbonyl-3-butenoic acid, as a brown oily solid. This material was not purified afterwards, but was used directly in the next step.

Step 4: The product of Step 3 (4,4-d (4-fluorophenyl)) 3-methoxycarbon-1-3-butenoic acid, 122 g) and acetic anhydride (250 ml) were added to a reaction flask. The reaction mixture was refluxed for 5 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and subsequently poured into 1200 ml of water. The resulting precipitate was collected by vacuum filtration and washed with cold water to provide 110 g of 1- (4-fluorophenyl) -2-methoxycarbonyl-4-acetoxy-5-fluoronaphthene. The product was used without further purification in the subsequent reaction.

Step 5 The 1- (4-fluorophenyl) -2-methox? Carbon? L-4-acetoxy? -6-fluoronaphthalene of Step 4 (110 g) and 400 ml of methanol were combined in a reaction flask. 5 ml of concentrated hydrochloric acid was added to the reaction flask and heated to reflux for 4 hrs under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and then to 0 ° C. White crystals of the desired product (1- (4-fluorophenyl) -2-methox? Carbon? L-4-hydroxyl-6-fluoronaphthalene, 65 g) were obtained and subsequently filtered and dried under vacuum. This material was not purified further, but was used directly in the next step.

Step 6: The product from Step 5 (1- (4-fluorophenyl) -2-methox? Carbon? L-4-h? Drox? -6-fluoronaphthalene, 39.4 g) was added to a reaction flask containing 300 ml. of tetrahydrofuran. The resulting mixture was cooled in an ice-water bath and stirred under a nitrogen atmosphere. 167 ml of a solution of methylmagnesium bromide (3M in diethyl ether) was added in drops over thirty minutes. The resulting yellow reaction mixture was warmed to room temperature and stirred overnight. The reaction mixture was emptied into 400 1 of water, and neutralized with the concentrate to the acidity, the mixture was extracted with three 300 ml portions of ether, and the organic portions were combined and washed with 1 liter of a solution of NaCl saturated. The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting brown oil (37.8 g) was transferred into a reaction vessel (equipped with a Dean-Stark trap) containing 300 ml of xylene, to which five drops of dodecylbenzenesulfonic acid were added. The reaction mixture was refluxed for 3 hours and cooled. The xylene was removed by rotary evaporation to provide 35 g of 3,9-difluoro-7,7-dimethyl-5-hydroxy-7-G-benzo [C] fluorene, as a light brown oil. This material was not purified and used directly in the next stage.

Step 7 The product of Step 6 (3,9-difluoro-7,7-dimethyl-5-hydroxy-7H-benzo [fluorene, 5.55 g) the product of Step 2 (1- (4-fluorophenyl) -1 - (4-piperidinophenyl) -2- propin-1-ol, 5.8 g), 8 drops of methanesulfonic acid and 250 ml of chloroform were combined in a reaction flask and stirred at reflux temperature under an atmosphere of nitrogen. After two hours, an additional 3.0 g of (1- (4-fluorophenyl) -1- (4-piperidinophenyl) -2-propin-1-ol, and 8 drops of dodecyl-benzenesulfonic acid were added to the mixture. This reaction mixture was heated at 5 ° C overnight and then cooled to room temperature.The reaction mixture was carefully washed with a mixture of 250 ml of a saturated solution of sodium bicarbonate and 250 ml of water The organic layer was separated, dried over sodium sulfate and concentrated by rotary evaporation.The residue was subjected to chromatography on a column of silica gel, using a mixture of hexane and ethyl acetate (95/5) as the The photochromic fractions were collected and concentrated by rotary evaporation to obtain a bluish white solid (8.0 g) The white-blue foam was then purified by precipitation with methanol to give 3.5 g of a greenish-white solid. that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4-piperidinophenyl) -6,11-difluoro-13, 13-dimethyl-3H, 13H-indene [2 '.3': 3, 4 [ - naphthol [1,2-b] pyran.

Example 2 Step 1 The product of Example 1, Step 3, in U. Patent 5,645,767 (l-phenyl-2-methoxycarbyl-4-acetoxynaphthalene, 50 g) was added to a reaction flask containing 500 ml of tetrahydrofuran. The resulting mixture was cooled in an ice-water bath and stirred under a nitrogen atmosphere. 703 ml of a solution of methyl magnesium chloride (1M in tetrahydrofuran) were added in drops over forty and five minutes. The resulting yellow reaction mixture was stirred at 0 ° C for 2 hours and slowly warmed to room temperature. The reaction mixture was poured into 2 liters of an ice / water mixture. Ethyl ether (1 liter) was added and the layers separated. The aqueous layer was extracted with 500 ml portions of ether and the organic portions were combined and washed with 1 liter of water. The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting oil was transferred into a reaction vessel (equipped with a Dean-Stark trap) containing 500 ml of toluene, to which ten drops of dodecylbenzenesulfonic acid were added. The reaction mixture was heated to reflux for 2 hours and cooled. The toluene was removed by rotary evaporation to provide 40.2 g of a light yellow solid. An NMR srum showed the product with a structure consistent with 7,7-d? Met? L-5-h? Drox? -7H-benzo [C] fluorene. this material was not further purified and used directly in the next step.

Step 2 The product of Step 1, 7,7-d? Met? L-5-hydrox? -7H-benzo [C] fluorene (6.0 g), the product of Example 1, step 2, step 1 - (4-fluorofeml) -1- (4-pipepdmophenyl) -2-propm-l-ol (7.1 g), seven drops of methanesulfonic acid and 250 ml of chloroform were combined in a reaction flask and shaken at reflux temperatures. After two hours, an additional 2.0 g of l- (4-fluorophenyl) -1- (4-p? Per? Dmofeml) -2-propm-1-ol and four drops of methanesulfonic acid were added to the mixture. reaction. This was followed by the addition of 1.0 g more of 1- (4-fluorophenyl) -1- (4-p? Pepdmofenil) -2-propm-l-ol and four drops of methanesulfonic acid after another two hours. The reaction mixture was refluxed for 6 hours and then cooled to room temperature. The reaction mixture was carefully washed with a mixture of 200 ml of a saturated solution of sodium bicarbonate and 200 ml of water. The organic layer was separated, dried over sulphate. of sodium and concentrated by marked evaporation. The residue was chromatographed on a column of silica gel, using a mixture of hexane and ethyl acetate 893/7) as the eluent. The photochromic fractions were collected and concentrated by rotary evaporation to obtain a bluish solid (11 g). the blue solid was further purified by crystallization from a 1.1 mixture of diethyl ether and hexane, to give 9.2 g of a white solid. An NMR spectrum showed that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4-piperidinophenyl) -13, 13-dimethyl-3H, 13H-índeno [2 ', 3'; 3, 4] naphtho- [1,2-b] -piran.

Example 3 The product of Example 1, Step 6 (3,9-difluoro-7,7-dimethyl-5-hydroxy-7H-benzo [fluorene, 5.0 g) (1- (4-fluorophenyl) -1- (4-piperidinophenyl) -2-propyn-l-ol, 5.3 g), 7 drops of methanesulfonic acid and 250 ml of chloroform were combined in a reaction flask and stirred at reflux temperature under a nitrogen atmosphere. After one hour, an additional 5.0 g of (1- (4-fluorophenyl) -1- (4-piperidinophenyl) -2-propyn-1-ol, was added to the reaction mixture and heating continued, after two hors, 2.0 g more than (1- (4-fluorophenyl) -1- (4-p? pepdmofenil) -2-prop? nl-ol, and 4 drops of methanesulfonic acid were added to the reaction mixture. The mixture was heated for another four hors, and then cooled to room temperature.The reaction mixture was carefully washed with a mixture of 125 ml of a saturated solution of sodium bicarbonate and 125 ml of water.The organic layer was separated, dried over sodium sulfate and concentrated by rotary evaporation.The residue was chromatographed on a column of silica gel, using a mixture of hexane, methylene chloride and ethyl acetate (60/35/5) as the diluent. The photochromic fractions were collected and concentrated by rotary evaporation to obtain a blue solid (4.0 g). zul was further purified by crystallization from a 1: 1 mixture of diethyl ether and hexane, to give 3.4 g of a white solid. An NMR spectrum showed that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4-morpholinophenyl) -6,11-d? Fluoro-13, 13-d? Met? L-3, 13H-? Ndeno [2 ', 3': 3, 4] naphthol [1,2-b] pyran.

EXAMPLE 4 The product of Example 2, Step 1, 7,7-d? Met? L-5-hydrox? -7H-benzo [] f luorene (4.0 g), the (1- (4) - L-fluorophenyl) - 1- (4-p? pepdmofenyl) -2-propylene-ol, 6.3 g), 8 drops of methanesulfonic acid and 200 ml of chloroform were combined in a reaction flask and it was stirred at reflux temperature under a nitrogen atmosphere. After one hour, an additional 4.6 g of (1- (4-fluorophenyl) -1- (4-piperidinophenyl) -2-propyn-1-ol was added to the reaction mixture and heating continued, after two hours, 5.0 g more of (l- (4-fluorophenyl) -1- (4-piperidinophenyl) -2-propyn-1-ol, and 4 drops of methanesulfonic acid were added to the reaction mixture. He heated for another four hors, and then cooled to room temperature. The reaction mixture was carefully washed with a mixture of 100 ml of a saturated solution of sodium bicarbonate and 100 ml of water. The organic layer was separated, dried over sodium sulfate and concentrated by rotary evaporation. The residue was subjected to chromatography on a column of silica gel, using a mixture of hexane, methylene chloride and ethyl acetate (60/37/3) as the diluent. The photochromic fractions were collected and concentrated by rotary evaporation to obtain a blue solid (4.0 g). The blue solid was further purified by crystallization from diethyl ether to provide 3.4 g of a white solid. An NMR spectrum showed that the product had a structure consistent with 3- (4-fluorophenyl) -3- (4-morpholinophenyl) -6,11-d? Fluoro-13, 13-d? Met? L-3, 13H-índeno [2 ', 3': 3, 4] naphthol [1,2-b] pyran.

PART II: TEST The photochromic performance of the photochromic materials of Examples 1-4 and Comparative Example C-1-CE6 were tested using the following optical bench setting. In addition, a fifth compound, according to certain non-limiting modalities of the present disclosure, the Example was tested. It will be appreciated by those skilled in the art that the photochromic materials of Example 5 and Comparative Examples 1-6 can be made in accordance with the teachings and examples described herein, with appropriate modifications, which will be readily apparent to those skilled in the art, of reading the present description. In addition, those skilled in the art will recognize that various modifications to the methods described, as well as to other methods, can be used in obtaining the photochromic materials of Examples 1-4, without deviating from the scope of the present disclosure, as noted. in the specification and the present claims.

Methacrylate Fragment Procedure A quantity of the photochromic material to be tested, calculated to provide a solution of 1.4 x 10 ~ 3M, was added to a flask containing 50 g of a monomer mixture of 4 parts bisphenol A dimethacrylate ethoxylated (BPA 2E0 DMA), 1 part poly (ethylene glycol) dimethacrylate 600 and 0.033 weight percent 2,2'-azobis (2-methyl-propionate) ("AIBN"). The photochromic material was dissolved in a stirred monomer mixture and moderately heated. After obtaining a clear solution, it was degassed under vacuum before pouring into a flat sheet mold having interior dimensions of 2.2 mm x 15.24 cm x 15.24 cm. The mold was sealed and placed in a programmable furnace of horizontal air flow this furnace is programmed to increase the temperature from 40 ° C to 95 ° C over an interval of 5 hours, maintained at the temperature of 95 ° C for 3 hours and then lower the temperature to 60 ° C for at least 2 hours. After opening the mold, the polymer sheet was cut using a diamond blade saw in 5.1 cm test squares. The test squares, which incorporate the photochromic materials prepared as described above, were tested for the photochromic response in an optical bench. Before testing on the optical bench, the squares 3 of photochromic test were exposed to ultraviolet light of 365 nm, for about 15 minutes, to cause the present photochromic materials to be transformed from the non-activated elemental state (or bleached to an activated state (colored) and then placed in an oven to 75 ° C for about 15 minutes, to allow the photochromic material to revert back to the non-activated state.The test squares were then cooled to room temperature, exposed to fluorescent light for at least 2 hrs and then maintained covered (ie, in a dark environment) for at least 2 hours, before testing at an optical bench maintained at 23 ° C. The bank was equipped with a 300-watt xenon arc lamp, a remotely controlled shutter , a Melles Griot KG2 filter that modifies the UV and IR wavelengths and acts as a heat absorber, in neutral density filters, and a sample retainer, placed inside a water bath at 23 ° C, in the which the square to be tested is inserted. A collimated beam of light from a tungsten lamp was passed through the square at a small angle (approximately 30 °) normal to the square. After passing through the square, the light from the tungsten lamp was directed to a collection sphere, where an Ocean Optics S2000 spectrometer was mixed and activated, where the spectrum of the measuring beam was collected and analyzed. ? ma? -v-s is the wavelength in the visible spectrum in which the maximum absorption of the activated (colored) form of the photochromic material in the square occurs. The wavelength? Max V1S was determined by testing the photochromic test squares on a Vanan Cary 4000 UV-Visible spectro-meter. The output signals of the detector were processed by a radiometer. The saturated optical density (Saturated OD) for each test square was determined by opening the xenon lamp shutter and measuring the transmittance after exposing the test fragment to UV radiation for 30 minutes. The ? max-V? S in the Saturated DO was calculated from the activated data, measured by the S2000 spectrometer in the optical bank. The Discoloration Regime was measured by the half-life of discoloration (ie, Ti,) is the time interval in seconds, for the absorbance of the activated form of the photochromic material in the test squares to reach half the absorbance value of the Saturated DO, at room temperature (23 ° C), after removing from the activated light source., The Performance Regime ("PR") was calculated from the Saturated DO and T by the equation: PR = ((Saturated DO) / T ^) x 10,000 The photochromic data of certain photochromic materials, according to the present description, are presented in Table 1. The photochromic data for comparative photochromic materials (ie, fused indeno, photochromic naphthopyrans, where the groups b and B ', are not combined). 4-fluorophenyl group and a 4-aminophenyl group, as noted herein), are presented in Table 2.

TABLE 1 - Photochromic Materials and Test Results TABLE 2 - Photochromatographic and Comparative Materials and Test Results D mas-vis OD Tl / 2 Ej Photochromic Material PR (nm) Sat (sec; 3, 3-d? F in? L-13, 13-d? Met? L- CE1 3H, 13H-mdeno [2 ', 3': 3, 4] naf to 532 1.50 723 21 [1, 2-b ] pyran 3-phenol-3- (4-p? Pepdmofenil) -6, 11-d? F luoro-13, 13-d? Met? L-CE2 616 0.73 94 3H, 13H-? Ndeno [2 ', 3 ': 3, 4] naphtho [l, 2-b] p? Rano 3-phenol-3- (4-p? Per? D? Nofenil) - 13, 13-d? Met? L-3H, 13H-CE3 599 1.04 180 50? Ndeno [2 ', 3': 3, 4] naphtho [l, 2- b] pyran It will be understood that the present disclosure illustrates aspects of the invention relevant to the clear understanding of the invention. Certain aspects of the invention will be apparent to those of ordinary skill in the art and, therefore, to facilitate a better understanding of the invention, are not presented in order to simplify the present disclosure. Although the invention has been described in relation to certain embodiments, the invention is not limited to the particular embodiments described, and attempts to cover the modifications that are within the spirit and scope of the invention, as defined by the appended claims.

Claims (20)

1. A photochromic material, which comprises: a naphthopyran fused indene, comprising a group B attached to its 3-position, and a group B 'attached to its 3-position, in which group B is a 4-fluorophenyl group and the Group B 'is a 4-substituted phenyl group, in which the substituent, at the 4-position of the 4-substituted phenyl group, is -NRXR2, where R1 and R2 are each, independently, hydrogen, C? -C6 alkyl , C5-C7 cycloalkyl, phenyl, mono-substituted or disubstituted phenyl, wherein said phenyl substituents are C? -C6 alkyl or C? -C6 alkoxy, or R1 and R2 together with the nitrogen atom form a ring, containing nitrogen, represented by the following graphic formula II: wherein each Y is selected, independently, for each occurrence of -CH2-, -CH (R3) -, -C (R3) 2-, -CH (ar? lo) -, -C (ar? lo) 2- , and -C (R3) (aplo) -, and Z is -Y-, -S-, -S (0) -, -S02- -NH-, -N (R3) -, or -N (ar? lo) -, wherein each R3 is independently C '-C6 alkyl, or hydroxy (C6C6) alkyl, each aryl is independently phenyl or naphthyl, m is an integer, 1, 2 or 3, and p is an integer 0, 1, 2, or 3 and when p is 0, Z is -Y-.

2. The photochromic material of claim 1, wherein this photochromic material has a faster decolorization rate than a comparable photochromic material, which includes a naphthopyran fused indene, wherein this naphthopyran fused from deno lacks a group of 4-fluoroenyl and a 4-substituted phenyl, in which the substituent in the 4-position is -NR-'R2, in its 3-position.

3. The photochromic material of claim 1, wherein the group B 'is one of 4- (N, N-dialkylamino) phenyl, 4-p? Pepdmphenyl, 4- (substituted p? P? E) phenyl-4-pyrrolidphenyl, 4- (substituted pyrrolidone) phenyl, 4- piperizmphenyl 4- (p? Pepzmo substituted) phenyl, wherein the substituents on the piperidm, pyrrolid or, or pipepzmo groups comprise (C? -Cg) alkyl or hydroxy (C? -C6) alkyls and the alkyl groups of the dialkyl ammon are (C? -Cg) alkyls identical or different.

4. The photochromic material of claim 1, further comprising a first group that removes electrons, attached to the 6-position of the indene naphthopyran.

5. The photochromic material of claim 4, wherein the first electron withdrawing group is bound to the 6 position of fused naphthopyran indene.

6. The photochromic material of claim 4, wherein the first group that removes electrons is fluorine, chlorine, bromine, perfluoroalkyl, perfluoroalloxy, cyano, OC (= 0) R4.-S0X or -C (= I) -X. X is hydrogen, C? -C6 alkyl, ?OR5 or -NR6R7, where R4, R5, R6 and R7 are each, independently, hydrogen, C? -C5 alkyl, C5-C7 cycloalkyl, phenyl, monosubstituted phenyl or disubstituted phenyl, wherein said phenyl substituents are C? -Cg alkyl or C? -C6 alkoxy.

7. The photochromic material of claim 4, further comprising a second electron withdrawing group, attached in the 11-position of the indene naphthopyran melt.

8. The photochromic material of claim 7, wherein the second group that removes electrons is fluorine, chlorine, bromine, perfluoroalkyl, perfuoroalkoxy, cyano, OC (= 0) R4, -S02X or -C (= 0) -X, X is hydrogen, C? -C6 alkyl / -OR5 or -NR10Rn, where R8, R9, R10 and R11 are each, independently, hydrogen, C? -Cg C5-C7 cycloalkyl, phenyl, monosubstituted phenyl or disubstituted phenyl, where said femlo substituents are C? -Cg alkyl or C? -Cg alkoxy.

9. The photochromic material of claim 1, further comprising a first fluorine substituent attached to the 6-position, of the indene-fused naphthopyran, and a second fluorine substituent in the 11-position of the indene-fused naphthopyran.

10. A photochromic material, which has the structure: (R11 in which: s is an integer that varies from 0 to 3, q is an integer that varies from 0 to 3, and each R16 and each R17, for each occurrence, comprises, hydrogen, fluorine, chlorine, bromine, perfluoroalkyl, pefluoroalkoxy , cyano, --OC (= 0) R4, -S02X or -C (= 0) -X, X is hydrogen, C? -C6 alkyl, _0R2"2 or -NR, 2 / 3JnR24, where R21, R22, R23 and R24 are each, independently, hydrogen, C-alkyl? -Cg C5-C7 cycloalkyl, phenyl, monosubstituted phenyl or disubstituted phenyl, wherein said phenyl substituents are C? -Cg alkyl or C? -C6 alkoxy, C? -Cg alkyl, C3-C7 cycloalkyl, substituted or unsubstituted phenyl, -OR25, wherein R25 is hydrogen, C? -C6 alkyl, phenyl (C? -C3) alkyl, phenyl (C-C3) alkyl substituted with mono (C? -C6) alkyl, mono (C? -C6) alkoxy substituted phenyl (C? ~ C3) alkyl, (C? -Cg) (C2-C4) alkoxy alkyl, C3-C7 cycloalkyl, or mono (C? -C4) substituted alkyl C3-C7 cycloalkyl, and said phenyl substituents may wherein C is -C6 alkyl or C6C6 alkoxy, monosubstituted phenyl, said phenyl having a substituent located at the position where the substituent is a dicarboxylic acid residue or its derivatives, a residue of diamine or its derivatives, a residue of diamine or its derivatives, a residue of amino alcohol or its derivatives, a polyol or its derivatives, -CH2-, - (CH2) t-, or - [0- (CH2) t] Y-, where? t 'is the integer 2, 3, 4 , 5 or 6 and? K 'is an integer from 1 to 50, the substituent being connected to an aryl group in another photochromic material; or -N (R26) R27, wherein R26 and R27 can each be, independently, for example, hydrogen, C? -C8 alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl benzothien-2-yl benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, C? -C8 alkylaryl, C3-C20 cycloalkyl, C-C20 bicycloalkyl, C5-C20 tricycloalkyl or Ci- C2o alkoxyalkyl, wherein said group of aryl is phenyl or naphthyl. Alternatively R26 and R27 join with the nitrogen atom, to form a C3-C20 hetero-bicycloalkyl hetero-bicycloalkyl ring or a C4-C20 hetero-tricycloalkyl ring; a ring containing nitrogen, represented by the following graphic formula IVA: VAT in which each -Y-, can be, independently, for each occurrence, -CH2 -CH (R 28. -C (R28) 2"-CH (aryl ) -, C (aryl) 2-, or -C (aryl) -, and Z can be -Y-, -O-, -S-, -S (O) -, -S02-, -NH-, - N (R28) -, or -N (aryl) -, where each R28 can be, independently, C-C6 alkyl or hydroxy (C? ~ Cg) alkyl, each aryl can be, independently, phenyl or naphthyl,? M ' is an integer 1, 2 or 3, and? p 'is an integer 0, 1, 2, or 3 and when? p' is 0, Z is -Y-, a group represented by one of the following graphic formulas IVB or IVC: IVB IVC wherein R 30 R, 3J1i and R, 32 can each be, independently, for example, hydrogen, C? -C6 alkyl, phenyl, or naphthyl or the groups R30 and R31 can together form a ring of 5 to 8 carbon atoms. carbon and each R29 can, independently, for each occurrence be C -Cg alkyl, C? -Cg alkoxy, fluorine or chlorine and? g 'is an integer 0, 1, 2, or 3; or a C4-C? e, substituted, mono-, or di-substituted spirobicyclic amine, or a substituted, mono-substituted or di-substituted spiro-cyclic amine, wherein said substituents are, independently, aryl, C? -Cg alkyl, C? -Cg alkoxy, or phenyl (C? -Cg) alkyl or. In addition, a group R16 in the position 6 and a group R16 in the position 7, together can form a group represented by one of the formulas IVD and IVE: IVD IVE where T and T 'can each be, independently, oxygen or the group -NR, where R, R and R can be as noted above; R18 and R19 can each be, independently, for example, hydrogen, hydroxy, C? -Cg alkyl; C3-C7 cycloalkyl; aillo; substituted or replaced phenyl; substituted or replaced benzyl; chlorine; fluorine; the group - C (= 0), where W can be, for example, hydrogen, hydroxy, C? -C6 alkyl, C? -C6 alkoxy, substituted, mono- or di-substituted aryl groups, phenyl or naphthyl, phenoxy , phenoxy substituted by mono- or di-alkoxy (C? -Cg), amino, mono-alkylamino (C? -C6), dialkylamino (C? -C6), phenylamino, phenylamino mono or di-alkyl (C? - Cg) substituted or phenylamino substituted by mono- or di-alkyl (C? -C6), -OR33, where R33 can be, for example, C? -C6 alkyl, phenyl (C? -C) alkyl, phenyl mono (Ci-Cg) substituted alkyl phenyl (C1-C3) alkyl, mono (C? -C6) ) substituted alkoxy phenyl (C? -C3) alkyl, C? -C6 alkoxy (C2 ~ C) alkyl, C3-C7 cycloalkyl, mono (C? -C4) substituted alkyl C3-C7 cycloalkyl, C? -Cg chloroalkyl, C -C6 fluoroalkyl, allyl, or the group -CH (R34) W, in which R34 can be hydrogen or C? -C3 alkyl and W can be CN, CF3, or COOR35, where R35 can be hydrogen or C? -C3 alkyl, or R33 may be the group -C (= 0) ", where" m can be, for example, hydrogen, C? -C6 alkyl, C? -C6 alkoxy, phenyl or naphthyl, phenoxy, unsubstituted, mono groups - or disubstituted, unsubstituted aryl groups, mono- or disubstituted, phenyl or naphthyl, phenoxy, mono-, or di- (C? -Cg) substituted alkyl phenoxy, mono- or di- (C? -C6) substituted alkoxy phenoxy , amino, mono (Ci-Cg) alkylamino, di (Cx-Cg) alkylamino, phenylamino, mono- or di- (C? -Cg) substituted alkyl phenylamino, or mono- or di- (C? C6) substituted phenylamino alkoxy, wherein each phenyl, benzyl or aryl substituent group can be. independently, C? -Cg alkyl or C? -Cg alkoxy; or a mono-substituted phenyl, said phenyl having a substituent located in the para position, in which this substituent is: a dicarboxylic acid residue or its derivatives, a residue of diamine or its derivatives, a residue of am o-alcohol or its derivatives, a polyol residue or its derivatives, -CH2-, - (CH2) t-, or - [0- (CH2) t] k-, where? t 'is an integer 2, 3, 4, 5 or 6 and? K 'is an integer from 1 to 50, the substituent being connected to an aryl group in another photochromic material. Alternatively, R18 and R19 together form an oxo group a spiro-carbocyclic group containing 3 to 6 carbon atoms, or a spiro-heterocarbocyclic group containing 3 to 6 carbon atoms or a spiro-heterocyclic group containing 3 to 6 atoms of carbon, or a spiro-heterocyclic group containing 1 or 2 oxygen atoms and of 3 to 6 carbon atoms, which includes the spiro-carbon atom, said spiro-carbocyclic or spiro-heterocyclic groups are tempered with 0.1. or 2 benzene rings, and R20 can be -NR36R37, wherein R36 and R37 can each be, independently, for example, hydrogen, C? -C6 alkyl, C5-C7 cycloalkyl, phenyl, phenyl, mono-substituted or phenyl di-substituted, wherein said phenyl substituents are C -C6 alkyl or C? -C6 alkoxy, R36 and R37 may, together with the nitrogen atom, form a nitrogen-containing ring represented by the following graphic formula V: V in which each -Y'- can, independently be, for each occurrence: -CH2-, -CH (RJB) -, -C (R38) 2 -CH (aryl) -, C (aryl) 2-, or -C (R38) (aryl) -, and Z 'can be -Y' -, - 0-, -S-, -S (0) -, -S02-, -NH- , -N (R38) -, or -N (aryl) -, wherein each R38 is, independently, C? -Cg alkyl, or hydroxy (C? ~ Cg) alkyl, each aryl is, independently, phenyl or naphthyl, 'is an integer 1, 2 or 3, and p' is an integer 0, 1, 2, or 3 and when p 'is 0, Z' is -Y'-; with the proviso that if R20 is morpholino, R16 is not 4-substituted piperidino in position 7 of structure III.

11. The photochromic material of claim 10, wherein R20 comprises the substituted dialkylamino, morpholino, piperidino, substituted piperidino, pyrrolidino, substituted pyrrolidino, piperazino or substituted piperazine, wherein the substituent on the piperidino, pyrrolidino or piperazino comprises the alkyl (C? - C6) or hydroxy (C? -Cg) -alkyl and the alkyl groups of the dialkylamino are the same or different in the alkyl group (C? -Cg).

12. The photochromic material of claim 10, wherein R16 is a group of fluorine in the 6-position and R17 is a fluorine group in the 11-position.

13. The photochromic material of claim 10, selected from: (a) 3- (4-fluorophenyl) -3- (4-morpholinophenyl) -13, 13-dimethyl-3H, 13H-indene [2 ', 3': 3, 4] naphth [1, 2-b] pyran; (b) 3- (4-fluorophenyl) -3- (4-morpholinophenyl) -6,11-difluoro-13, 13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho , 2-b] pyran; (c) 3- (4-fluorophenyl) -3- (4-piperidinophenyl) -13, 13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (d) 3- (4-fluorophenyl) -3- (-piperidinophenyl) -6,13-difluoro-13,13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1, 2-b] pyran; (e) 3- (4-fluorophenyl) -3- (4- (2-methylpiperidino) phenyl) -13, 13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1, 2-b] pyran; (f) 3- (4-fluorophenyl) -3- (4- (2-methylpiperidino) phenyl) -6,11-difluoro-13, 13-dimethyl-3H, 13H-indene [2 ', 3': 3, 4] naphtho [1,2-b] pyran; (g) 3- (4-fluorophenyl) -3- (4-piperizinophenyl) -13, 13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1,2-b] pyran; (h) 3- (4-fluorophenyl) -3- (4-piperizinophenyl) -6,1-difluoro-13, 13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [1 , 2-b] pyran; (i) 3- (4-fluorophenyl) -3- (4-pyrrolidinophenyl) -13, 13-dimethyl-3H, 13H-indene [2 ', 3': 3,] naphtho [1,2-b] pyran; (j) 3- (4-fluorophenyl) -3- (4-pyrrolidinophenyl) -6,11-difluoro-13, 13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [l , 2-b] pyran; (k) 3- (4-fluorophenyl) -3- (4- (N, N-diethylamino) phenyl) -13, 13-dimethyl-3H, 13H-indene [2 ', 3': 3,4] naphtho [ 1, 2-b] pyran; and (1) 3- (4-fluorophenyl) -3- (4- (N, N-diethylamino) phenyl) -6,11-difluoro-13, 13-dimethyl-3H, 13H-indene [2 ', 3' : 3,4] naphtho [l, 2-b] pyran.

14. A chemical compound, represented by the structure: SAW wherein R is -NR13R, wherein R and R are each, independently, hydrogen, C? -Cg alkyl, C5-C7 cycloalkyl, phenyl, monosubstituted phenyl or disubstituted phenyl, wherein the phenyl substituents are C? -Cg alkyl or C6-C6 alkoxy, or R13 and R14 can, together with the nitrogen atom, form a nitrogen-containing ring, represented by the following graphic formula II: in which each -Y- can be chosen, independently, for each occurrence of -CH2-, -CH (R15) -, -C (R15) 2-, CH (aryl) -, -C (aryl) 2-, and -C (R15) (aryl) -, and Z is -Y-, -O-, -S-, -S (O) -, -S02-, -NH-, -N (R3) -, or -N (aryl) -, in which each R15 can be, independently, for example, C? -Cg alkyl, or hydroxy (C? -C6) alkyl, each aplo can be, independently, phenyl or naphthyl, m is an integer 1, 2 or 3, and p is an integer 0, 1, 2 or 3, with the proviso that when p is 0, Z is -Y-.

15. The chemical compound of claim 14, wherein R12 comprises the dialkylammo, morfol or, pipepdmo, substituted pipepdmo, pyrrolidmo, substituted pyrrolidmo, piperazmo or pyrrolidmo or piperazm comprising alkyl (C6C6) or hydroxy (C6C6) alkyl, and the alkyl groups of the dialkylamide are the same or different alkyl (C? -C6).

16. A method for obtaining a photochromic material, which comprises: reacting the chemical compound of claim 14 with a 7H-benzo [C] fluoren-5-ol, to form a 3H, 13H-mdeno [2 ', 3': 3, 4] naphtho [1,2-b] pyran.

17. A photochromic article, which comprises: a substrate; and a photochromic material, according to claim 1, connected to at least a portion of the substrate. 10 <

18. The photochromic article of claim 17, wherein this photochromic article is an optical element, said optical element being at least one of an ophthalmic element, an exhibit element, a window, a mirror, an active liquid crystal cell element a passive liquid crystal cell element.

19. The photochromic article of claim 17, wherein the substrate comprises a polymeric material and the photochromic material is incorporated into at least a portion of a polymeric material by at least one of the mixture with at least a portion of the polymeric material and the embedded in the polymeric material. at least a portion of the polymeric material.

20. The photochromic article of claim 17, wherein the photochromic article comprises at least one partial coating connected to at least a portion of the substrate, said at least one partial coating comprising the photochromic material.