HK1124590A - Photochromic indeno-fused naphthopyrans - Google Patents

Description

Photochromic indeno-fused naphthopyrans

Technical Field

The present invention relates to photochromic indeno-fused naphthopyrans.

Background

[0001] Various non-limiting embodiments of the present disclosure are directed to photochromic materials comprising indeno-fused naphthopyrans having substituents comprising a 4-fluorophenyl group and a 4-aminophenyl group bonded to the 3-position of the indeno-fused naphthopyran. In addition, photochromic materials according to various non-limiting embodiments of the present disclosure may exhibit faster fade rates as compared to similar indeno-fused naphthopyrans that do not contain a 4-fluorophenyl and 4-aminophenyl group bonded to the 3-position of the indeno-fused naphthopyran. Other non-limiting embodiments of the present disclosure also relate to substituted 2-propyn-1-ols for the synthesis of the indeno-fused naphthopyrans disclosed herein. Other non-limiting embodiments disclosed herein relate to photochromic compositions and articles, such as optical elements, that incorporate photochromic materials.

[0002] Many conventional photochromic materials, such as photochromic naphthopyrans, can transform from a first form or state to a second form or state in response to absorption of electromagnetic radiation. For example, many conventional thermally reversible photochromic materials are capable of switching between a first "clear" or "bleached" ground-state form and a second "colored" activated-state form in response to the absorption of certain wavelengths of electromagnetic radiation (or "actinic radiation"). The term "actinic radiation" as used herein, refers to electromagnetic radiation capable of causing a photochromic material to transform from a first form or state to a second form or state. The photochromic material can then revert to a clear ground state form in response to thermal energy in the absence of actinic radiation. Photochromic articles and compositions, such as eyewear photochromic lenses, containing one or more photochromic materials typically exhibit an optically clear state and a colored state corresponding to the photochromic material they contain. Thus, for example, a lens containing a photochromic material may transform from a clear state to a colored state when exposed to actinic radiation (e.g., certain wavelengths found in sunlight), and may revert back to the clear state upon absorption of thermal energy in the absence of such radiation.

[0003] When used in photochromic articles and compositions, conventional photochromic materials are typically incorporated into the matrix polymer matrix by one of infiltration, mixing, and/or bonding. Alternatively, the photochromic material may be impregnated into a preformed article or coating. The term "photochromic composition" as used herein refers to a photochromic material in combination with one or more other materials, which may or may not be photochromic materials.

[0004] For many photochromic applications, it is often desirable to have a photochromic material that can quickly revert from a colored, activated state form to a clear, ground state form, while still maintaining acceptable characteristics, such as color density. For example, in photochromic eyewear applications, an optical lens comprising a photochromic material transitions from an optically clear state to a colored state as the wearer moves from a region of low actinic radiation, such as indoors, to a region of high actinic radiation, such as into a direct sunlight exposure region. As the lens becomes colored, less electromagnetic radiation is transmitted through the lens from the visible and/or ultraviolet regions of the electromagnetic spectrum into the wearer's eye. In other words, the lens in the colored state absorbs more electromagnetic radiation than the lens in the optically clear state. When the wearer subsequently returns from the area of high actinic radiation to the area of low actinic radiation, the photochromic material in the eyewear reverts from the colored activated state form to the clear ground state form in response to thermal energy. If the transition from colored to clear takes several minutes or more, at this time the wearer's vision may be less than optimal due to the combined effect of lower ambient light illumination and reduced visible light transmission through the colored lenses.

[0005]Therefore, for some applications, it would be advantageous to develop photochromic materials that can more rapidly transition from a colored form to a clear form as compared to conventional photochromic materials. The term "fade rate" as used herein is a measure of the rate at which a photochromic material transitions from an activated colored state to an unactivated clear state. The fade rate of a photochromic material can be determined, for example, by activating the photochromic material to color saturation under controlled conditions in a given substrate, measuring its activated steady state absorbance (i.e., saturated optical density), and then measuring the length of time it takes for the absorbance of the photochromic material to decrease to one-half the activated steady state absorbance value. Measured according to this method, the fade rate is designated T_1/2The unit is seconds.

[0006] The absorption spectrum of the photochromic material in the activated state corresponds to the color of an article containing the photochromic material, such as an ophthalmic lens, when exposed to actinic radiation. Because a particular wavelength in the visible region of electromagnetic radiation is absorbed by the photochromic material in its activated state, the wavelength in the visible region that is transmitted (i.e., not absorbed) corresponds to the color of the photochromic material in its open form. Absorbing light wavelengths from about 500 nm to about 520 nm in the visible region of the electromagnetic spectrum results in a photochromic material that exhibits a "reddish" color, i.e., it absorbs visible radiation from the short wavelength or blue end of the visible spectrum and transmits radiation from the longer wavelength or red end of the visible spectrum. Conversely, absorption of light wavelengths from about 580 nanometers to about 610 nanometers in the visible region of the electromagnetic spectrum results in the photochromic material exhibiting a "bluer" color, i.e., it absorbs visible radiation from the longer wavelength or red end of the visible spectrum and transmits radiation from the shorter wavelength or blue end of the visible spectrum.

[0007] Many current photochromic compounds have an active state absorption spectrum that absorbs visible light in the blue end of the visible spectrum and exhibit a reddish color in the activated form. If the photochromic material has a red-shifted activated-state absorption spectrum, i.e., absorbs light having a longer wavelength, the photochromic material exhibits a more blue color than the current photochromic materials. For certain applications, it is desirable to have a photochromic material that has a red-shifted activated form of absorption spectrum for actinic radiation, and thus can exhibit a blue color.

Disclosure of Invention

[0008] Various non-limiting embodiments of the present disclosure relate to photochromic materials comprising an indeno-fused naphthopyran, wherein the indeno-fused naphthopyran has substituents comprising a 4-fluorophenyl group and a 4-aminophenyl group bonded to the 3-position of the indeno-fused naphthopyran. Photochromic materials according to certain non-limiting embodiments may have faster fade rates than similar photochromic indeno-fused naphthopyrans that do not have substituents comprising a 4-fluorophenyl group and a 4-aminophenyl group bonded to the 3-position of the indeno-fused naphthopyran.

[0009]In one non-limiting embodiment, the photochromic material can comprise an indeno-fused naphthopyran that includes a group B attached to the 3-position thereof and a group B' attached to the 3-position thereof. The group B may be a 4-fluorophenyl group and the group B' may be a 4-substituted phenyl group, wherein the substituent at the 4-position of the 4-substituted phenyl group is-NR¹R²Wherein R is¹And R²Each independently is hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl, or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆Alkoxy, or R¹And R²Together with the nitrogen atom to form a nitrogen-containing ring represented by the following structural formula II:

wherein each-Y-is independently at each occurrence selected from: -CH₂-，-CH(R³)-，-C(R³)₂-, -CH (aryl) -, -C (aryl)₂-, and-C (R)³) (aryl) -, Z is-Y-, -S-, -S (O) -, -SO₂-，-NH-，-N(R³) -, or-N (aryl) -, in which each R is³Independently is C₁-C₆Alkyl or hydroxy (C)₁-C₆) Alkyl, each aryl group is independently phenyl or naphthyl, m is the integer 1, 2 or 3, p is the integer 0, 1, 2 or 3, and when p is 0, Z is-Y-.

[0010] Still further non-limiting embodiments of the present disclosure relate to photochromic materials having the structure set forth in structure III:

wherein R is¹⁶、R¹⁷、R¹⁸、R¹⁹And R²⁰Denotes the groups described herein below and are set forth in the claims.

[0011] Still further non-limiting embodiments of the present disclosure relate to compounds having the structure set forth in structure VI:

wherein R is¹²Denotes groups described herein and set forth in the claims. A still further non-limiting embodiment of the present disclosure is directed to a method of preparing a photochromic material comprising reacting a compound of figure VI with 7H-benzo [ C ]]Reaction of the fluoren-5-ol to form a 3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]A pyran.

[0012] Other non-limiting embodiments relate to a photochromic article comprising a substrate and a photochromic material according to any one of the non-limiting embodiments disclosed herein.

Drawings

[0013] The various non-limiting embodiments disclosed herein can be better understood when explained in conjunction with the following figures.

[0014] FIGS. 1-2 illustrate schematic diagrams of reaction schemes for preparing intermediates used in the synthesis of photochromic materials according to various non-limiting embodiments disclosed herein.

[0015] FIG. 3 illustrates a schematic diagram of a reaction scheme for preparing photochromic materials according to various non-limiting embodiments disclosed herein.

Detailed Description

[0016] The articles "a," "an," and "the" as used in the specification and the appended claims include plural referents unless expressly and unequivocally limited to one referent.

[0017] Further, for the purposes of this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and other properties or parameters used in the specification are to be understood as being modified in all instances by the term "about". Accordingly, unless otherwise indicated, it is to be understood that the numerical parameters set forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0018] Further, notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations as discussed above, the numerical values set forth in the examples section are reported as precisely as possible. It should be understood, however, that such numerical values inherently contain certain deviations from the measurement devices and/or measurement techniques.

[0019] Photochromic compounds and materials according to various non-limiting embodiments of the present invention will now be discussed. The term "photochromic" as used herein means having an absorption spectrum at least for visible radiation (which changes in response to at least the absorption of actinic radiation). The term "actinic radiation" as used herein, refers to electromagnetic radiation capable of causing a photochromic material to transform from a first form or state to a second form or state. Further, the term "photochromic material" as used herein refers to any substance suitable to exhibit photochromic properties, i.e. suitable to have an absorption spectrum at least for visible radiation (which changes in response to at least the absorption of actinic radiation). The term "photochromic composition" as used herein refers to a photochromic material in combination with one or more other materials that may or may not be photochromic materials.

[0020] The term "indeno-fused naphthopyran" as used herein is defined as: has a structure comprising an indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran as shown in the following (I). Indeno-fused naphthopyrans are examples of photochromic naphthopyrans. The term "photochromic naphthopyran" as used herein refers to naphthopyrans that are capable of converting between a first "closed-form" and a second "open-form" in response to absorption of actinic radiation. The term "closed-form" as used herein corresponds to the ground-state form of the indeno-fused naphthopyran, and the term "open-form" corresponds to the activated-state form of the indeno-fused naphthopyran.

[0021] As used herein, the terms "3-position," "6-position," "11-position," and the like, refer to the 3-, 6-, and 11-positions, respectively, of the ring atoms of the indeno-fused naphthopyran skeleton, as exemplified by the numbered positions on structure (I) below. Further, the rings of the indeno-fused naphthopyran skeleton may be represented by letters from a to E, and thus each ring may be referred to by its corresponding letter. Thus, for example, the term "C ring" or "C ring of an indeno-fused naphthopyran" as used herein corresponds to the lower ring of the naphthyl substructure of the indeno-fused naphthopyran, as represented by the ring labeled "C" in structure (I) below. The term "carbon-bonded to the C ring" as used herein means bonded to at least one carbon at the 5-position, 6-position, 7-position or 8-position according to the numbering listed in structure (I).

[0022] According to various non-limiting embodiments disclosed herein, the groups B and B' at the 3-position of the indeno-fused naphthopyran are part of the photochromic indeno-fused naphthopyran skeleton illustrated in (I) above. Without being bound by any particular theory, it is believed that the B and B' groups can help stabilize the open form of the indeno-fused naphthopyran structure. According to various non-limiting embodiments disclosed herein, the groups B and/or B' can be any structure having at least one pi bond capable of conjugating with the open form of the pi system of the parent indeno-fused naphthopyran structure, e.g., a substituted phenyl substituent in various non-limiting embodiments of the present disclosure. According to various non-limiting embodiments of the present disclosure, the B and B 'groups of the photochromic material may each comprise a 4-substituted phenyl group, wherein the substituents in the 4-position of each 4-substituted phenyl group of the B and B' groups are as set forth herein below.

[0023]Various non-limiting embodiments of the photochromic materials of the present disclosure are now discussed in detail. According to certain non-limiting embodiments, the present disclosure provides photochromic materials comprising an indeno-fused naphthopyran comprising a group B attached to the 3-position of the indeno-fused naphthopyran and a group B' attached to the 3-position of the indeno-fused naphthopyran. The group B may be a 4-fluorophenyl group and the group B' may be a 4-substituted phenyl group, wherein the substituent in the 4-position of the 4-substituted phenyl group is-NR¹R². According to various non-limiting embodiments, R¹And R²May each independently be: hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein the phenyl substituent may be C₁-C₆Alkyl or C₁-C₆Alkoxy, or R¹And R²May be linked together with the nitrogen atom to form a nitrogen-containing ring represented by the following structural formula II:

wherein each-Y-in each occurrence can be independently selected from: -CH₂-，-CH(R³)-，-C(R³)₂-, -CH (aryl) -, -C (aryl)₂-, and-C (R)³) (aryl) -, Z is-Y-, -S-, -S (O) -, -SO₂-，-NH-，-N(R³) -, or-N (aryl) -, in which each R is³Independently is C₁-C₆Alkyl or hydroxy (C)₁-C₆) Alkyl, each aryl group may independently be phenyl or naphthyl, ` m ` is the integer 1, 2 or 3 `, ` p ` is the integer 0, 1, 2 or 3 and when ` p ` is 0, Z is-Y-.

[0024]According to certain non-limiting embodimentsThe photochromic material can have a faster fade rate when measured in a polymethacrylate chip than a similar photochromic material comprising an indeno-fused naphthopyran, wherein the indeno-fused naphthopyran does not contain a 4-fluorophenyl group attached to the 3-position thereof and a 4-substituted phenyl group at the 3-position thereof, wherein the substituent at the 4-position of the 4-substituted phenyl group is-NR¹R²。

[0025]The term "fade rate" as used throughout this disclosure means that the T of a photochromic material can be determined_1/2Values represent kinetic velocity values. The term "fade rate" as used herein is a measure of the rate at which a photochromic material transitions from an activated colored state to an unactivated clear state. The fade rate of a photochromic material can be determined, for example, by activating the photochromic material to color saturation under controlled conditions in a given substrate, determining its activated steady state absorbance (i.e., saturated optical density), and then determining the length of time it takes for the absorbance of the photochromic material to decrease to one-half the activated steady state absorbance value. The fading rate is measured in this way as T_1/2Expressed in units of seconds. Thus, when the fade rate is said to be "faster," the photochromic compound transitions from the colored activated-state to the clear ground-state at a faster rate. Faster fade rates can utilize the T of photochromic materials_1/2A decreasing value of the data is measured. That is, as the fade rate becomes faster, the length of time that the absorbance decreases to half the initial activation absorbance value will become shorter. Determination of T for photochromic materials disclosed herein_1/2More detailed methods of measuring values are listed in the examples below.

[0026]One skilled in the art will appreciate that the rate of fade of the photochromic material may depend on the medium in which the photochromic material is incorporated. As used herein, the term "incorporated" when used in reference to a photochromic material is a means of mediation that is physically and/or chemically bonded. In the present disclosure, all photochromic performance data disclosed herein, such as fade rate(T_1/2) Maximum absorbance wavelength (. lamda.)_max-vis) Saturated optical density and performance rating, were determined using standard procedures, including incorporation of photochromic materials into polymer test chips comprising methacrylate polymers, unless specifically noted otherwise. The term "wavelength of maximum absorbance" or "λ" as used herein_max-vis"is the wavelength of the visible spectrum at which the maximum absorbance of the activated (colored) form of the photochromic material occurs. The term "saturated optical density" (abbreviated "Sat'd OD") as used herein is a measure of the steady state absorbance (i.e., optical density) of an activated photochromic material under standard conditions as defined in the examples. The term "performance rating" or "PR" as used herein is a measure of the performance of the photochromic material and is calculated by the following formula:

performance rating ((Sat'd OD)/T)_1/2)x10,000。

The performance grade typically has a value from 1 to 100, with higher values generally being preferred.

[0027] Photochromic performance tests and standard procedures for forming polymer test chips (photochromic materials incorporating various non-limiting embodiments of the present disclosure) are disclosed in more detail in the examples section herein. One skilled in the art will recognize that while the exact values of fade rate and other photochromic performance data may vary depending on the media incorporated, the photochromic performance data disclosed herein may be exemplified by the relative speeds and data values for the photochromic materials contemplated when incorporated into other media.

[0028]According to other non-limiting embodiments, the photochromic material comprises an indeno-fused naphthopyran in which the B group can be 4-fluorophenyl, and the B' group can be 4-morpholinophenyl, 4-piperidinophenyl, 4- (substituted piperidino) phenyl, 4-pyrrolidinyl (pyrrolidino) phenyl, 4- (substituted pyrrolidinyl) phenyl, or 4-piperazinyl (piperazino) phenyl, wherein the substituent can be C₁-C₆Alkyl or hydroxy (C)₁-C₆) An alkyl group. In some non-limiting senseIn an exemplary embodiment, the 4-piperazinylphenyl can be a 4- (N' -substituted) piperazinylphenyl wherein the substituent on the nitrogen can be C₁-C₆An alkyl substituent. According to a further non-limiting embodiment, the B' group may be a 4- (N, N-dialkylamino) phenyl group, wherein the alkyl groups may be the same or different, and may be C₁-C₆Alkyl groups, such as methyl, ethyl, propyl, isopropyl and butyl.

Structure A

A1 R^a＝F，R^bPiperidino

A2 R^a＝F，R^bMorpholino

A3 R^a＝H，R^b＝H

A4 R^a＝H，R^bPiperidino

A5 R^a＝H，R^bMorpholino

A6 R^a＝F，R^b＝H

[0029]According to certain non-limiting embodiments disclosed herein, a photochromic material comprising an indeno-fused naphthopyran having a B group (comprising a 4-fluorophenyl group) and a B' group (comprising a 4-aminophenyl group), as set forth and claimed herein, is polymerized by T_1/2When evaluated, can have a faster fade rate than a similar indeno-fused naphthopyran that does not contain the combined B and B' groups listed above. For example, with respect to structure (A), Compound A1, according to a specific non-limiting embodiment, wherein the B group is 4-fluorophenyl (R)^aIs F) and the B' group is 4-piperidinophenyl (R)^bPiperidino) photochromic materials having T_1/2Fading rate of 118 seconds. On the contrary, pairIn structures (A), Compounds A3 and A4, where the B group is phenyl (R)^aH) and the radicals B' are each phenyl (R)^bH) or 4-piperidinophenyl (R)^bPiperidino) two similar photochromic materials having a T of 723 seconds and 180 seconds, respectively_1/2Slower fade rates of value. Further, for structure (A), compound A6, wherein the B group is 4-fluorophenyl (R)^aF) and the group B' is phenyl (R)^bH) has a T of 542 seconds_1/2Slower fade rates of value.

[0030]Further, with respect to structure (A), Compound A2, according to another specific non-limiting embodiment, wherein the B group is 4-fluorophenyl (R)^aIs F) and the group B' is 4-morpholinophenyl (R)^bMorpholino) having T_1/2Fading rate of 151 seconds. In contrast, with reference to structure (A), Compound A3 and A5, wherein the B group is phenyl (R)^aH) and the radicals B' are each phenyl (R)^bH or 4-morpholinophenyl (R)^bMorpholino) having a T of 723 seconds and 241 seconds, respectively_1/2Slower fade rates of value. Further, for structure (A), compound A6, wherein the B group is 4-fluorophenyl (R)^aF) and the group B' is phenyl (R)^bH) has a slow fade rate T of 542 seconds_1/2The value is obtained.

[0031] Certain non-limiting embodiments of the photochromic materials can include, in addition to the B and B' groups described herein, a first electron-withdrawing group bonded to a carbon of the C-ring of the indeno-fused naphthopyran. According to certain non-limiting embodiments of the photochromic material, the first electron-withdrawing group can be bonded to the 6-position of the C-ring of the indeno-fused naphthopyran.

[0032]The term "group" as used herein refers to an arrangement of one or more atoms. The term "electron withdrawing group" as used herein may be defined as: groups that attract electron density from a pi-system, such as the pi-system of an indeno-fused naphthopyran skeleton. Further, as used herein "An electron withdrawing group "can be defined as: having a positive Hammett sigma when the group is attached to a carbon of an aromatic pi-system participating in an aromatic pi-system, e.g., an indeno-fused naphthopyran nucleus_pThe group of values. The term "Hammett σ" as used herein_pThe value "is a measure of the electronic influence, either on the electron donating or on the electron withdrawing, of substituents attached to carbons participating in an aromatic pi-electron system (i.e. transported through a polarizable pi-electron system, such as an aromatic pi-electron system). Hammett sigma_pThe values are relative measurements obtained comparing the electronic effect of the para substituent of the phenyl ring with the electronic effect of the para substituted hydrogen. Typically, for aromatic substituents, a negative Hammett σ is common_pThe value indicates a group or substituent having an electron donating effect on a pi-electron system (i.e., electron donating group), positive Hammett sigma_pThe values represent groups or substituents that have an electron withdrawing effect on the pi electron system (i.e., electron withdrawing groups).

[0033]Electron withdrawing groups suitable for use in connection with the various non-limiting embodiments of the photochromic materials described herein may have a Hammett σ of from about 0.05 to about 0.75_pThe value is obtained. Suitable electron withdrawing groups may include, for example, but are not limited to: halogen, e.g. fluorine (. sigma.)_p0.06), chlorine (σ)_p0.23), and bromine (. sigma.)_p0.23); perfluoroalkyl (e.g., -CF)₃，σ_p0.54) or perfluoroalkoxy (e.g., -OCF)₃，σ_p0.35), wherein the perfluoroalkyl or perfluoroalkyl portion of perfluoroalkoxy can include, for example, trifluoromethyl or have the formula C_nF_2n+1Wherein 'n' is an integer from 1 to 10; cyano group (sigma)_p＝0.66)；-OC(＝O)R⁴(e.g., -OC (═ O) CH₃，σ_p＝0.31)；-SO₂X (e.g., -SO)₂CH₃，σ_p0.68); or-C (═ O) -X, where X is hydrogen (-CHO, σ)_p＝0.22)，C₁-C₆Alkyl (e.g., -C (═ O) CH₃，σ_p＝0.50)，-OR⁵(σ_p0.4) or-NR⁶R⁷(e.g., -C (═ O) NH₂，σ_p0.36), wherein R⁴、R⁵、R⁶And R⁷Each of which may be independently of the others hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, monosubstituted phenyl, di-substituted phenyl, alkylene glycol or polyalkylene glycol, wherein the phenyl substituent may be C₁-C₆Alkyl or C₁-C₆An alkoxy group. Further, Hammett σ in the range of about 0.05 to about 0.75_pSuitable electron-withdrawing substituents for values are listed in Lange's Handbook of Chemistry, "Section 9 physical Relationship", 15 th edition J.A.dean, eds., McGraw Hill, 1999, pp 9.1-9.8, the disclosure of which is incorporated herein by reference. It will be understood by those skilled in the art that when used in conjunction with a Hammett σ value, the subscript "p" refers to the Hammett σ value determined when the group is located at the para-position of the phenyl ring of a model system (e.g., a para-substituted benzoic acid model system)_pThe value is obtained.

[0034]The term "polyalkylene glycol" as used herein refers to a compound having the general structure- [ O- (C)_aH_2a)]_b-OR "wherein 'a' 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 suitable polyalkylene glycols can be found in U.S. patent No.6,113,814 at column 3, lines 30-64, the disclosure of which is incorporated herein by reference. Non-limiting examples of reactive substituents can be found in U.S. patent application Ser. No.11/102,280 [0033]-[0040]The disclosure of which is incorporated herein by reference, as found in the paragraphs.

[0035]According to further non-limiting embodiments, the photochromic materials of the present disclosure may further comprise a second electron-withdrawing group bonded to the 11-position of the indeno-fused naphthopyran. According to various non-limiting embodiments, the second electron-withdrawing group may be fluorine, chlorine, bromine, perfluoroalkyl, perfluoroalkoxy, cyano, -OC (═ O) R⁸、-SO₂X or-C (═ O) -X, X being hydrogen, C₁-C₆Alkyl, -OR⁹or-NR¹⁰R¹¹Wherein R is⁸、R⁹、R¹⁰And R¹¹Each independently is hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group.

[0036] Further discussion of photochromic materials comprising an indeno-fused naphthopyran, a first electron-withdrawing group, and in certain non-limiting embodiments, a second electron-withdrawing group as listed above, may be found in U.S. non-provisional application serial No.11/314,141, entitled "photochromic materials with electron-withdrawing substituents," filed concurrently herewith, the entire disclosure of which is incorporated herein by reference.

[0037] According to certain non-limiting embodiments, the photochromic materials of the present disclosure may comprise an indeno-fused naphthopyran in which the first electron-withdrawing group bonded to the 6-position thereof may be a first fluorine group and the second electron-withdrawing group bonded to the 11-position thereof may be a second fluorine group.

[0038] According to other non-limiting embodiments, the photochromic materials of the present disclosure have a structure represented by formula (III) below.

[0039]For structure (III),'s' may be an integer from 0 to 3, and 'q' may be an integer from 0 to 3. Each R¹⁶And each R¹⁷Each occurrence may include, for example: hydrogen; fluorine; chlorine; bromine; a perfluoroalkyl group; a perfluoroalkoxy group; a cyano group; -OC (═ O) R²¹；-SO₂X; -C (═ O) -X, where X may be, for example, hydrogen, C₁-C₆Alkyl, -OR²²or-NR²³R²⁴Wherein R is²¹、R²²、R²³And R²⁴May each independently be hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein the phenyl substituent may be C₁-C₆Alkyl or C₁-C₆An alkoxy group; c₁-C₆An alkyl group; c₃-C₇A cycloalkyl group; substituted or unsubstituted phenyl; -OR²⁵Wherein R is²⁵May be, for example, hydrogen, C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical (C)₁-C₆) Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl radicals, or mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl, the phenyl substituent may be C₁-C₆Alkyl or C₁-C₆An alkoxy group; a monosubstituted phenyl, said phenyl having a substituent at the para position, wherein the substituent is: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-，-(CH₂)_t-, or- [ O- (CH)₂)_t]_k-, where't' is an integer of 2, 3, 4, 5 or 6, 'k' is an integer from 1 to 50, and the substituent is attached to an aryl group on another photochromic material; or-N (R)²⁶)R²⁷Wherein R is²⁶And R²⁷May each independently be, for example, hydrogen, C₁-C₈Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, C₁-C₈Alkylaryl group, C₃-C₂₀Cycloalkyl radical, C₄-C₂₀Bicycloalkyl radical, C₅-C₂₀Tricycloalkyl or C₁-C₂₀Alkoxyalkyl, wherein the aryl is phenyl or naphthyl. Or, R²⁶And R²⁷May be linked together with a nitrogen atom to form C₃-C₂₀A heterobicycloalkyl ring or C₄-C₂₀A heterotricycloalkyl ring; a nitrogen-containing ring represented by the following structural formula IVA:

wherein each-Y-in each occurrence can independently be: -CH₂-，-CH(R²⁸)-，-C(R²⁸)₂-, -CH (aryl) -, -C (aryl)₂-, or-C (R)²⁸) (aryl) -, Z may be-Y-, -O-, -S-, -S (O) -, -SO₂-，-NH-，-N(R²⁸) -, or-N (aryl) -, in which each R is²⁸May independently be C₁-C₆Alkyl or hydroxy (C)₁-C₆) Alkyl, each aryl group may independently be phenyl or naphthyl,'m' is the integer 1, 2 or 3, 'p' is the integer 0, 1, 2 or 3, and when 'p' is 0, Z is-Y-; a group represented by one of the following structural formulae IVB or IVC:

wherein R is³⁰、R³¹And R³²May each independently be, for example, hydrogen, C₁-C₆Alkyl, phenyl, or naphthyl, or the radical R³⁰And R³¹May together form a ring of 5 to 8 carbon atoms, each R²⁹May independently at each occurrence be C₁-C₆Alkyl radical, C₁-C₆Alkoxy, fluoro or chloro, 'g' is an integer 0, 1, 2 or 3; or unsubstituted, mono-or di-substituted C₄-C₁₈Spirobicyclic amines, or unsubstituted, mono-and di-substituted C₄-C₁₈Spirotricyclic amine of whichThe substituents are independently aryl, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, or phenyl (C)₁-C₆) An alkyl group. Further, R in the 6-position¹⁶Radicals and R in the 7-position¹⁶The groups may together form a group represented by one of IVD and IVE:

wherein T and T' may each independently be oxygen or a group-NR²⁶-, wherein R²⁶、R³⁰And R³¹As listed above.

[0040]Further, for structure (III), R¹⁸And R¹⁹May each independently be, for example: hydrogen; a hydroxyl group; c₁-C₆An alkyl group; c₃-C₇A cycloalkyl group; an allyl group; substituted or unsubstituted phenyl; substituted or unsubstituted benzyl; chlorine; fluorine; a radical-C (═ O) W, where W may be, for example, hydrogen, hydroxy, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, unsubstituted, mono-or di-substituted aryl radicals phenyl or naphthyl, phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, amino, mono (C)₁-C₆) Alkylamino, di (C)₁-C₆) Alkylamino, phenylamino, mono-or di- (C)₁-C₆) Alkyl-substituted phenylamino, or mono-or di- (C)₁-C₆) Alkoxy-substituted phenylamino; -OR³³Wherein R is³³May for example be C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkane (I) and its preparation methodBase, C₃-C₇Cycloalkyl radicals, mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl radical, C₁-C₆Chloroalkyl, C₁-C₆Fluoroalkyl, allyl, or a radical-CH (R)³⁴) W', wherein R³⁴May be hydrogen or C₁-C₃Alkyl, W' may be CN, CF₃Or COOR³⁵Wherein R is³⁵May be hydrogen or C₁-C₃Alkyl, or R³³May be a group-C (═ O) W 'where W' may be, for example, hydrogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, unsubstituted, mono-or di-substituted aryl radicals phenyl or naphthyl, phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, amino, mono (C)₁-C₆) Alkylamino, di (C)₁-C₆) Alkylamino, phenylamino, mono-or di- (C)₁-C₆) Alkyl-substituted phenylamino, or mono-or di- (C)₁-C₆) Alkoxy-substituted phenylamino; wherein each of said phenyl, benzyl or aryl substituents may independently be C₁-C₆Alkyl or C₁-C₆An alkoxy group; or a mono-substituted phenyl, said phenyl having a substituent located at the para position, wherein the substituent is: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-，-(CH₂)_t-, or- [ O- (CH)₂)_t]_k-, where't' is an integer of 2, 3, 4, 5 or 6, 'k' is an integer from 1 to 50, and the substituent is attached to an aryl group on another photochromic material. Or, R¹⁸And R¹⁹Together may form an oxo group, a spiro-carbocyclic group comprising 3 to 6 carbon atoms, or a spiro-heterocyclic group comprising 1 to 2 oxygen atoms and 3 to 6 carbon atoms containing a spiro carbon atom, which spiro-carbocyclic and spiro-heterocyclic groups are annelated with 0, 1 or 2 phenyl rings.

[0041]Also with respect to structure (III), R²⁰May be-NR³⁶R³⁷Wherein R is³⁶And R³⁷May each independently be, for example, hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl, or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group. Or, R³⁶And R³⁷May be linked together with the nitrogen atom to form a nitrogen-containing ring represented by the following structural formula V:

wherein each-Y' -in each occurrence can independently be: -CH₂-，-CH(R³⁸)-，-C(R³⁸)₂-, -CH (aryl) -, -C (aryl)₂-, or-C (R)³⁸) (aryl) -, Z 'may be-Y' -, -O-, -S-, -S (O) -, -SO₂-，-NH-，-N(R³⁸) -, or-N (aryl) -, in which each R is³⁸Independently is C₁-C₆Alkyl or hydroxy (C)₁-C₆) Alkyl, each aryl group may independently be phenyl or naphthyl, m ' is the integer 1, 2 or 3, p ' is the integer 0, 1, 2 or 3, and when p ' is 0, Z ' is-Y ' -.

[0042]According to certain non-limiting embodiments, when R²⁰When it is morpholino, R¹⁶May not be a 4-substituted piperidino attached to the 7-position of the indeno-fused naphthopyran skeleton.

[0043]According to certain non-limiting embodiments, the photochromic material can include a structure according to structure (III), wherein R²⁰May include dialkylamino, morpholino, piperidino, substituted piperidino, pyrrolidinyl, substituted pyrrolidinyl, piperazinyl, or substituted piperazinyl. The substituent on the piperidino, pyrrolidinyl or piperazinyl moiety may include (C)₁-C₆) Alkyl or hydroxy (C)₁-C₆) Alkyl groups, for example, hydroxymethyl. The alkyl substituents of the dialkylamino groups may be the same or different and may be (C)₁-C₆) An alkyl group.

[0044]According to a further non-limiting embodiment, the photochromic material can include a structure according to structure (III), wherein R¹⁶Can be a fluorine group at the 6-position of the indeno-fused naphthopyran of structure (III), R¹⁷A second fluorine group at the 11-position of the indeno-fused naphthopyran of structure (III) can be included.

[0045] Non-limiting methods of making photochromic materials of various non-limiting embodiments of the present disclosure will now be discussed with reference to fig. 1 and 2. Various methods of synthesizing 7H-benzo [ C ] fluoren-5-ol compounds suitable for use in the present disclosure may be found, for example, in the following: U.S. patent No.6,296,785, column 11, line 6 to column 28, line 35, and examples; U.S. patent No.5,645,767, column 6, line 32 to column 8, line 32, and examples; U.S. application serial No.11/102,280 (2005-8/4), [0069] to [0072] paragraphs and examples; U.S. application Ser. No.11/102,279 (4/8/2005 application), [0099] to [0106] paragraphs and examples; the disclosure of which is incorporated herein by reference.

[0046] For example, FIG. 1 illustrates one non-limiting reaction scheme for preparing 7H-benzo [ C ] fluoren-5-ol compounds, which in certain non-limiting embodiments have substituents R 'and R', such as first and second electron-withdrawing groups. The substituted and unsubstituted 7H-benzo [ C ] fluoren-5-ol compounds can then be further reacted with 1- (4-aminophenyl) -1- (4-fluorophenyl) -2-propyn-1-ol (which is shown in the conventional synthesis of figure 2) as depicted in figure 3, to form a mixture comprising 3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-B ] pyran (according to various non-limiting embodiments disclosed herein), further comprising a group B attached to its 3-position and a group B 'attached to its 3-position, wherein the group B and the group B' may be as defined and claimed herein. It is to be understood that the reaction schemes are provided for illustrative purposes only and are not intended to be limiting herein. Other examples of methods of preparing photochromic materials according to various non-limiting embodiments disclosed herein are set forth in the examples.

[0047]Referring now to FIG. 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 provide carboxylic acid 2 as a mixture of double bond isomers (when R 'is different from R', the mixture of isomers may be separated, or used directly in a subsequent reaction, followed by separation). Reaction of carboxylic acid 2 with acetic anhydride at elevated temperature produces substituted naphthalene 3, wherein R^*Is an acetate. Hydrolyzing the acetate to yield naphthol 4 (R)^*H). The ester of naphthol 4 is reacted with excess methyl magnesium bromide and treated with water to give diol 5. Cyclization of diol 5 with a sulfonic acid such as dodecylbenzenesulfonic acid ("DBSA") affords 7H-benzo [ C ]]Fluoren-5-ol 6.

[0048]Referring now to FIG. 2, wherein a non-limiting process for 1- (4-aminophenyl) -1- (4-fluorophenyl) -2-propyn-1-ol is provided, 4, 4 ' -difluorobenzophenone (7) is reacted with a secondary amine HNR ' R ' to give 4-amino-4 ' -fluorobenzophenone 8, wherein R ' and R ' can be reacted with R ' respectively³⁶And R³⁷As set forth and claimed herein. The carbonyl addition of an acetylide anion, such as sodium acetylene in acetylene saturated dimethylformamide, to 4-amino-4' -fluorobenzophenone 8 affords 1- (4-aminophenyl) -1- (4-fluorophenyl) -2-propyn-1-ol 9 by treatment with water.

[0049] Referring now to FIG. 3, 7H-benzo [ C ] fluoren-5-ol 6 (the synthesis of which is shown in FIG. 1) can be reacted with 1- (4-aminophenyl) -1- (4-fluorophenyl) -2-propyn-1-ol 9 (the synthesis of which is shown in FIG. 2). Catalytic condensation of 6 and 9 with a sulfonic acid such as DBSA or methanesulfonic acid gives a 3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-B ] pyran 10, according to various non-limiting embodiments of the present disclosure, comprising a group B attached to the 3-position thereof and a group B 'attached to the 3-position thereof, wherein the group B and the group B' may be as defined and claimed herein. Those skilled in the art will recognize that various modifications can be made to the starting materials, reagents, and/or reaction conditions in the reaction schemes set forth in FIGS. 1-3 to provide various non-limiting embodiments of photochromic materials comprising substituted indeno-fused naphthopyrans as set forth and claimed herein, and such modifications are within the scope of the disclosed invention.

[0050] As discussed above, the synthesis of the photochromic materials of the present disclosure may include the reaction of substituted or unsubstituted 7H-benzo [ C ] fluoren-5-ol 6 with 1- (4-aminophenyl) -1- (4-fluorophenyl) -2-propyn-1-ol 9. Further, the amino group of 1- (4-aminophenyl) -1- (4-fluorophenyl) -2-propyn-1-ol 9 may be substituted as set forth herein. According to certain non-limiting embodiments, the present disclosure provides compounds represented by structure (VI):

wherein the group B may be a 4-fluorophenyl substituent and the group B' represents a 4-substituted phenyl substituent wherein the substituent R¹²May be-NR¹³R¹⁴. According to certain non-limiting embodiments, R¹³And R¹⁴May each independently be hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl, or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group. According to other non-limiting embodiments, R¹³And R¹⁴May be linked together with the nitrogen atom to form a nitrogen-containing ring represented by the following structural formula II:

wherein each-Y-in each occurrence can be independently selected from: -CH₂-，-CH(R¹⁵)-，-C(R¹⁵)₂-, -CH (aryl) -, -C (aryl)₂-, and-C (R)¹⁵) (aryl) -, Z is-Y-, -O-, -S-, -S (O) -, -SO₂-，-NH-，-N(R³) -, or-N (aryl) -, in which each R is¹⁵May independently be, for example, C₁-C₆Alkyl or hydroxy (C)₁-C₆) Alkyl, each aryl group can be independently phenyl or naphthyl, m is an integer of 1, 2 or 3, p is an integer of 0, 1, 2 or 3, with the proviso that when p is 0, Z is-Y.

[0051]According to certain non-limiting embodiments of 2-propyn-1-ol of structure VI, R¹²May include dialkylamino, morpholino, piperidino, substituted piperidino, pyrrolidinyl, substituted pyrrolidinyl, piperazinyl, or substituted piperazinyl. Substituents on the piperidino, pyrrolidinyl or piperazinyl moiety may include, for example, (C)₁-C₆) Alkyl or hydroxy (C)₁-C₆) An alkyl group. The alkyl substituents of the dialkylamino groups may be the same or different and may be (C)₁-C₆) An alkyl group.

[0052] Certain other non-limiting embodiments of the photochromic materials of the present disclosure can be represented by their chemical names as determined, at least in part, by the IUPAC nomenclature system. Photochromic materials contemplated by the present disclosure include:

(a)3- (4-fluorophenyl) -3- (4-morpholinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(b)3- (4-fluorophenyl) -3- (4-morpholinophenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(c)3- (4-fluorophenyl) -3- (4-piperidinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(d)3- (4-fluorophenyl) -3- (4-piperidinophenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(e)3- (4-fluorophenyl) -3- (4- (2-methylpiperidino) phenyl) -13, 13-dimethyl-3H, 13H-indeno [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-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(g)3- (4-fluorophenyl) -3- (4-piperazinylphenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(h)3- (4-fluorophenyl) -3- (4-piperazinylphenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(i)3- (4-fluorophenyl) -3- (4-pyrrolidinylphenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(j)3- (4-fluorophenyl) -3- (4-pyrrolidinylphenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(k)3- (4-fluorophenyl) -3- (4- (N, N-diethylamino) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran; and

(l)3- (4-fluorophenyl) -3- (4- (N, N-diethylamino) phenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

[0053]Photochromic materials of the present disclosure, for example, photochromic materials comprising an indeno-fused naphthopyran that comprises a group B attached to its 3-position and a group B 'attached to its 3-position, wherein the group B is 4-fluorophenyl and the group B' is 4-Substituted phenyl, wherein the substituent at the 4-position of the 4-substituted phenyl is-NR¹R²As listed herein. The term "optical" as used herein means related to or associated with light and/or vision. The term "ocular" as used herein means associated with or relating to the eye and/or vision. The term "display" as used herein refers to an informational representation of a visible or machine readable word, number, symbol, pattern, or chart. Non-limiting examples of display elements include phosphor screens, detectors, and security elements, such as security markings. The term "window" as used herein refers to an opening suitable for transmission of radiation therethrough. Non-limiting examples of windows include aircraft and automotive windshields, automotive and aircraft transparencies, such as T-tops, sidelights and taillights, filters, skylights, and optical switches. The term "mirror" as used herein refers to a surface that is capable of reflecting a substantial portion of incident light. The term "liquid crystal cell" as used herein refers to a structure containing a liquid crystal material capable of being aligned. One non-limiting example of a liquid crystal cell element is a liquid crystal display.

[0054] In certain non-limiting embodiments, the photochromic materials of the present disclosure can be used in ophthalmic elements, such as corrective lenses, including single or multi-vision lenses, which can be segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal, trifocal, and progressive lenses), non-corrective lenses, magnifying lenses, protective lenses, visors, goggles, and optics such as lenses for cameras or telescopes. In other non-limiting embodiments, the photochromic materials of the present disclosure can be used in plastic films and sheets, textiles, and coatings.

[0055] Further, various non-limiting embodiments according to the present disclosure can each be used alone, in combination with other photochromic materials according to various non-limiting embodiments of the present disclosure, or in combination with suitable complementary conventional photochromic materials. For example, photochromic materials according to various non-limiting embodiments disclosed herein can be used in combination with conventional photochromic materials having a maximum activation absorption in the range of about 400 to about 800 nanometers. Further, photochromic materials according to the various non-limiting embodiments disclosed herein can be used in combination with complementary conventional polymerizable or compatible photochromic materials, such as those disclosed in U.S. patent nos.6,113,814 (column 2, line 39 to column 8, line 41) and 6,555,028 (column 2, line 65 to column 12, line 56), the disclosures of which are expressly incorporated herein by reference.

[0056] As discussed above, the photochromic composition may contain a mixture of photochromic materials in accordance with the various non-limiting embodiments disclosed herein. For example, although not limiting herein, mixtures of photochromic materials can be used to obtain certain activated colors, such as near neutral gray or near neutral brown. See, for example, U.S. patent No.5,645,767, column 12, line 66 to column 13, line 19, which describes parameters defining neutral gray and brown colors, the disclosure of which is incorporated herein by reference.

[0057] Various non-limiting embodiments disclosed herein provide photochromic compositions comprising an organic material that is at least one of a polymeric material, an oligomeric material, and a monomeric species, and a photochromic material according to any one of the non-limiting embodiments listed above incorporated into at least a portion of the organic material. According to various non-limiting embodiments disclosed herein, the photochromic material may be incorporated into a portion of the organic material using at least one of mixing and bonding the photochromic material with the organic material or a precursor thereof. As used herein, the terms "mixed" and "blended" with respect to the incorporation of a photochromic material into an organic material means that the photochromic material is blended or doped with at least a portion of the organic material, rather than bonded to the organic material. Further, as used herein with respect to incorporating photochromic materials into organic materials, the term "bonded" or "bonded" means that the photochromic material is attached to a portion of the organic material or a precursor thereof.

[0058]As discussed above, the photochromic compositions according to the various non-limiting embodiments disclosed herein can comprise organic materialsThe organic material is selected from a polymeric material, an oligomeric material, and/or a monomeric species. Examples of polymeric materials that may be used in conjunction with the various non-limiting embodiments disclosed herein include, but are not limited to, polymers of the following: a bis (allyl carbonate) monomer; diethylene glycol dimethacrylate monomer; diisopropenyl benzene monomer; ethoxylated bisphenol a dimethacrylate monomer; ethylene glycol dimethacrylate monomer; poly (ethylene glycol) dimethacrylate monomer; ethoxylated phenol dimethacrylate monomer; alkoxylated polyol acrylate monomers, such as ethoxylated trimethylolpropane triacrylate monomers; a urethane acrylate monomer; a vinyl benzene monomer; and styrene. Other non-limiting examples of suitable polymeric materials include polymers of multifunctional, e.g., mono-, di-, or multifunctional acrylate and/or methacrylate monomers; poly (C)₁-C₁₂Alkyl methacrylates), such as poly (methyl methacrylate); poly (oxyalkylene) dimethacrylate; poly (alkoxylated phenol methacrylate); cellulose acetate; cellulose triacetate; cellulose acetate propionate; cellulose acetate butyrate; poly (vinyl acetate); poly (vinyl alcohol); poly (vinyl chloride); poly (vinylidene chloride); a polyurethane; polythiourethane; a thermoplastic polycarbonate; a polyester; poly (ethylene terephthalate); polystyrene; poly (alpha-methylstyrene); copolymers of styrene and methyl methacrylate; copolymers of styrene and acrylonitrile; polyvinyl butyral; and diallyl pentaerythritol, and in particular, copolymers with polyol (allyl carbonate) monomers, such as diethylene glycol bis (allyl carbonate), and acrylate monomers, such as ethyl acrylate, butyl acrylate. Also included are copolymers of the foregoing monomers, combinations and mixtures of the foregoing polymers and copolymers with other polymers, for example to form interpenetrating network products.

[0059]Further, according to various non-limiting embodiments, wherein the transparency of the photochromic composition is desired, the organic material can be a transparent polymeric material. For example, according to various non-limiting embodiments, the polymeric material can beOptically clear polymeric materials prepared from thermoplastic polycarbonate resins, for example resins obtained from bisphenol A and phosgene and sold under the trade name LEXAN(ii) a Polyesters, e.g. sold under the trade mark MYLARThe substance of (1); poly (methyl methacrylate), e.g. sold under the trade mark PLEXIGLASThe substance of (1); polymers of polyol (allyl carbonate) monomers, especially diethylene glycol di (allyl carbonate) monomers sold under the trade name CR-39(ii) a And polyurea-polyurethane (polyureaurethane) polymers prepared, for example, by reaction of a polyurethane oligomer and a diamine curing agent, the trade name TRIVEX for the composition of one such polymer being PPG Industries, Inc. Other non-limiting examples of polymeric materials include the following polymers: copolymers of polyols (allyl carbonates) such as diethylene glycol bis (allyl carbonate) with other co-polymerizable monomeric materials such as, but not limited to: copolymers with vinyl acetate, copolymers with polyurethanes having terminal diacrylate functional groups, and copolymers with aliphatic urethanes containing allyl or acryloyl functional groups at the terminal portion. Other suitable polymeric materials also include, but are not limited to: poly (vinyl acetate), polyvinyl butyral, polyurethane, polythiourethane selected from diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer, ethoxylated bisphenol A dimethacrylate monomer, ethylene glycol dimethacrylate monomer, poly (ethylene glycol) dimethacrylate monomerPolymers of monomers, ethoxylated phenol dimethacrylate and ethoxylated trimethylolpropane triacrylate monomers, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile according to one non-limiting embodiment, the polymeric material may be an optical resin sold under the CR-name by PPG Industries inc, such as CR-307, CR-407 and CR-607.

[0060] According to certain specific non-limiting embodiments, the organic material may be a polymeric material selected from the group consisting of poly (carbonates), copolymers of ethylene and vinyl acetate; copolymers of ethylene and vinyl alcohol; copolymers of ethylene, vinyl acetate and vinyl alcohol (e.g., those resulting from the partial saponification of copolymers of ethylene and vinyl acetate); cellulose acetate butyrate; poly (urethane); poly (acrylates); poly (methacrylates); epoxy resins; an aminoplast functional polymer; poly (anhydrides); poly (urea urethanes); an N-alkoxymethyl (meth) acrylamide functional polymer; poly (siloxane); poly (silanes); and combinations and mixtures thereof.

[0061] Various non-limiting embodiments disclosed herein provide photochromic articles comprising a substrate and a photochromic material according to any one of the non-limiting embodiments discussed above, the photochromic material being attached to or incorporated into a portion of the substrate. The term "linked" as used herein means directly or indirectly related through another substance or structure. In one non-limiting embodiment, the photochromic articles of the present disclosure may be optical elements such as, but not limited to, ophthalmic elements, display elements, windows, mirrors, active liquid crystal cell elements, and passive liquid crystal cell elements. In certain non-limiting embodiments, the photochromic article is an ophthalmic element, such as, but not limited to: corrective lenses, including single or multi-view lenses, which may be segmented or non-segmented multi-view lenses (such as, but not limited to, bifocal, trifocal, and progressive lenses), non-corrective lenses, magnifying lenses, protective lenses, visors, and optics.

[0062] According to various non-limiting embodiments disclosed herein, wherein the substrate of the photochromic article comprises a polymeric material, the photochromic material can be attached to at least a portion of the substrate by incorporating the photochromic material into at least a portion of the polymeric material of the substrate, or at least a portion of the oligomeric or monomeric species forming the substrate. For example, according to one non-limiting embodiment, the photochromic material can be incorporated into the polymeric material of the substrate by a cast-in-place process. Additionally, or alternatively, the photochromic material may be incorporated into at least a portion of the polymeric material of the substrate by infiltration. Infiltration and cast-in-place methods are discussed below.

[0063] According to other non-limiting embodiments, the photochromic material can be associated with at least a portion of the substrate of the photochromic article as part of an at least partial coating associated with at least a portion of the substrate. According to this non-limiting embodiment, the substrate may be a polymeric substrate or an inorganic substrate (such as, but not limited to, a glass substrate). Further, the photochromic material can be incorporated into at least a portion of the coating composition prior to applying the coating composition to the substrate, or the coating composition can be applied to the substrate, at least partially set, and thereafter the photochromic material can be incorporated into at least a portion of the coating. The terms "set" and "fixing" as used herein include, but are not limited to, curing, polymerizing, crosslinking, cooling, and drying.

[0064] For example, in one non-limiting embodiment of the present disclosure, the photochromic article may comprise an at least partial coating of a polymeric material, the polymeric material being attached to at least a portion of the surface thereof. According to this non-limiting embodiment, the photochromic material may be mixed and/or bonded with at least a portion of the polymeric material of the at least partial coating.

[0065] The at least partial coating comprising the photochromic material can be directly attached to the substrate, for example, by applying a coating composition comprising the photochromic material directly to at least a portion of the surface of the substrate and at least partially fixing the coating composition. Additionally, or alternatively, at least a partial coating comprising a photochromic material may be attached to the substrate, for example, by one or more additional coatings. For example and without limitation thereto, according to various non-limiting embodiments, an additional coating composition can be applied to at least a portion of the substrate surface and at least partially fixed, after which a coating composition comprising a photochromic material can be applied to the additional coating layer and at least partially fixed. Non-limiting methods of applying the coating composition to a substrate are discussed herein below.

[0066] Non-limiting examples of additional coatings that may be used in conjunction with the photochromic articles disclosed herein include: a primer or compatible coating; protective coatings, including transitional coatings, abrasion resistant coatings, and other coatings that prevent polymerization chemistry and/or degradation due to environmental conditions such as moisture, heat, ultraviolet light, oxygen (e.g., UV-barrier coatings and oxygen barrier-coatings); an anti-reflective coating; a conventional photochromic coating; and a polarizing coating and a polarizing stretched film; and combinations thereof.

[0067] Non-limiting examples of primers or compatible coatings that may be used in conjunction with the various non-limiting embodiments disclosed herein include: a coating comprising a coupling agent, at least a partial hydrolysate of a coupling agent and mixtures thereof. The term "coupling agent" as used herein refers to a substance having groups capable of reacting, binding and/or associating with groups on a surface. Coupling agents in accordance with various non-limiting embodiments disclosed herein may include organometallic compounds such as silanes, titanates, zirconates, zirconium aluminates, hydrolysates thereof, and mixtures thereof the phrase "at least partial hydrolysate of a coupling agent" as used herein refers to hydrolysis of some to all hydrolyzable groups on the coupling agent. Other non-limiting examples of primer coatings suitable for use in conjunction with the various non-limiting embodiments disclosed herein include those described in the following: U.S. patent 6,025,026, column 3 line to column 11 line 40, and U.S. patent 6,150,430, column 2 line 39 to column 7 line 58, the disclosures of which are expressly incorporated herein by reference.

[0068] The term "transitional coating" as used herein refers to a coating that helps create a gradient of properties between two coatings. For example, without limiting the disclosure herein, a transitional coating may help create a hardness gradient between a relatively hard coating (e.g., an abrasion-resistant coating) and a relatively soft coating (e.g., a photochromic coating). Non-limiting examples of transitional coatings include radiation-hardened, acrylate-based films, as described in paragraphs [0079] - [0173] of U.S. patent application publication 2003/0165686, the contents of which are specifically incorporated herein by reference.

[0069]The term "wear-resistant coating" as used herein is meant to indicate a greater wear resistance than the standard reference material, for example, as specified by CR-39The protective polymeric material of the monomer-made polymer (available from PPG Industries, Inc) was tested using a method comparable to ASTM F-735 (standard test method for determining abrasion resistance of clear plastics and coatings using the swing sandbag method). Non-limiting examples of wear-resistant coatings include: abrasion-resistant coatings comprising organosilanes, organosiloxanes, abrasion-resistant coatings based on inorganic materials such as silica gel, titanium dioxide and/or zirconium oxide, and organic abrasion-resistant coatings of the uv-curable type.

[0070] Non-limiting examples of anti-reflective coatings include single layer, multilayer coatings of metal oxides, metal fluorides, or other such materials, which can be deposited onto the articles disclosed herein (or onto a self-supporting coating film (applied to the article)), for example, by vacuum deposition, sputtering, and the like.

[0071] Non-limiting examples of conventional photochromic coatings include, but are not limited to, coatings comprising conventional photochromic materials.

[0072] Non-limiting examples of polarizing coatings and polarizing stretch-films include, but are not limited to: coatings (such as those described in U.S. patent application publication No. 2005/0151926) and stretch-films comprising dichroic compounds known in the art.

[0073] As discussed herein, according to various non-limiting embodiments, an additional at least partial coating or film can be formed on the substrate, followed by forming a coating comprising the photochromic materials according to the various non-limiting embodiments disclosed herein on the substrate. For example, according to certain non-limiting embodiments, an underlayer or compatible coating may be formed on the substrate prior to application of the coating composition comprising the photochromic material. Additionally or alternatively, after forming a coating comprising a photochromic material according to various non-limiting embodiments disclosed herein on a substrate, an additional at least partial coating may be formed on the substrate, for example as an overcoat on the photochromic coating. For example, according to certain non-limiting embodiments, a transitional coating may be formed over the coating comprising the photochromic material, and an abrasion-resistant coating may be formed over the transitional coating.

[0074] For example, according to one non-limiting embodiment, a photochromic article is provided comprising: a substrate (such as, but not limited to, a plano-concave or plano-convex ophthalmic lens substrate) comprising an abrasion-resistant coating on at least a portion of a surface thereof; a primer or compatibility coating on at least a portion of the wear-resistant coating; a photochromic coating comprising a photochromic material according to the various non-limiting embodiments disclosed herein over at least a portion of the primer or compatible coating; a transitional coating over at least a portion of the photochromic coating; and a wear-resistant coating on at least a portion of the transitional coating. Further, in accordance with this non-limiting embodiment, the photochromic article can also include, for example, an antireflective coating associated with the surface of the substrate and/or a polarizing coating or film associated with the surface of the substrate.

[0075] Non-limiting methods of making photochromic compositions and photochromic articles, such as optical elements, according to various non-limiting embodiments disclosed herein are now discussed. One non-limiting embodiment provides a method of preparing a photochromic composition comprising: a photochromic material is incorporated into at least a portion of the organic material. Non-limiting methods of incorporating photochromic materials into organic materials include, for example: mixing the photochromic material into a solution or melt of the polymer, oligomer or monomer species, followed by at least partially fixing the polymer, oligomer or monomer species (with or without bonding the photochromic material to the organic material); and infiltrating the photochromic material into the organic material (with or without bonding the photochromic material to the organic material).

[0076] Another non-limiting embodiment provides a method of making a photochromic article comprising attaching the photochromic materials discussed above according to the various non-limiting embodiments to at least a portion of a substrate. For example, if the substrate comprises a polymeric material, the photochromic material can be attached to at least a portion of the substrate using at least one of an in-situ casting process and infiltration. For example, in a cast-in-place process, the photochromic material can be mixed with a polymer solution or melt, or with other oligomer and/or monomer solutions or mixtures, which are then cast into a mold having the desired shape and at least partially set to form the substrate. Optionally, according to this non-limiting embodiment, the photochromic material may be bonded to a portion of the polymeric material of the substrate, for example, by way of copolymerization with a monomeric precursor thereof. In the infiltration method, after the substrate is formed, the photochromic material may be diffused into the polymeric material of the substrate, for example, by immersing the substrate in a solution containing the photochromic material, with or without heating. Thereafter, the photochromic material can be bonded to the polymeric material, even if not required.

[0077] Other non-limiting embodiments disclosed herein provide methods of making an optical element, comprising: the photochromic material is attached to at least a portion of the substrate using at least one of in-mold casting, coating, and lamination. For example, according to one non-limiting embodiment, wherein the substrate comprises a polymeric material, the photochromic material can be attached to at least a portion of the substrate by in-mold casting. According to this non-limiting embodiment, a coating composition comprising a photochromic material (which may be a liquid coating composition or a powder coating composition) is applied to the mold surface and at least partially set. Thereafter, a polymer solution or melt or oligomer or monomer solution or mixture is cast onto the coating and at least partially fixed. After fixing, the coated substrate is removed from the mold. Non-limiting examples of powder coatings that may be used with photochromic materials according to various non-limiting embodiments disclosed herein are set forth in U.S. patent No.6,068,797 at column 7, line 50 to column 19, line 42, the disclosure of which is expressly incorporated herein by reference.

[0078] According to another non-limiting embodiment, wherein the substrate comprises a polymeric material or an inorganic material, such as glass, the photochromic material can be attached to at least a portion of the substrate using a coating. Non-limiting examples of suitable coating methods include spin coating, spray coating (e.g., using liquid or powder coatings), curtain coating, roll coating, spin and spray coating, over-mold, and combinations thereof. For example, according to one non-limiting embodiment, the photochromic material can be attached to the substrate by an over-mold process. According to this non-limiting embodiment, a coating composition comprising a photochromic material (which may be a liquid coating composition or a powder coating composition as previously discussed) may be applied to the mold, and the substrate may then be placed in the mold such that the substrate contacts the coating such that it coats at least a portion of the surface of the substrate. Thereafter, the coating composition can be at least partially set and the coated substrate can be removed from the mold. Alternatively, the over-filling may be performed as follows: the substrate is placed in the mold to define an open area between the substrate and the mold, after which a coating composition comprising a photochromic material is injected into the open area. Thereafter, the coating composition can be at least partially set and the coated substrate can be removed from the mold.

[0079] Additionally or alternatively, the coating composition (with or without the photochromic material) can be applied to the substrate (e.g., by any of the previous methods), the coating composition is at least partially fixed, and thereafter, the photochromic material can be infiltrated (as previously discussed) into the coating composition.

[0080] According to yet another non-limiting embodiment, wherein the substrate comprises a polymeric material or an inorganic material, such as glass, lamination can be utilized to attach the photochromic material to at least a portion of the substrate. According to this non-limiting embodiment, a film comprising a photochromic material can be adhered or attached to a portion of a substrate, with or without an adhesive and/or heat and pressure. Thereafter, if desired, a second substrate can be applied to the first substrate, and the two substrates can be laminated together (i.e., by using heat and pressure) to form an element with the film comprising the photochromic material embedded between the two substrates. Methods of forming a coating film comprising a photochromic material may include, for example, but are not limited to: the photochromic material is mixed with the polymer solution or oligomer solution or mixture from which the film is cast or extruded and, if desired, at least partially set. Additionally or alternatively, the film may be formed (with or without a photochromic material) and infiltrated with a photochromic material (as discussed above).

[0081] Further, various non-limiting embodiments disclosed herein include using different combinations of the foregoing methods to form photochromic articles according to various non-limiting embodiments disclosed herein. For example, and without limitation, herein, according to one non-limiting embodiment, a photochromic material can be attached to a substrate by incorporation into the organic material forming the substrate (e.g., using an in-situ casting process and/or an infiltration process), and then the photochromic material (which can be the same as or different from the photochromic material previously described) can be attached to a portion of the substrate using the in-mold casting, coating and/or lamination process discussed above.

[0082] Further, it will be appreciated by those skilled in the art that the photochromic compositions and articles according to the various non-limiting embodiments disclosed herein may further comprise other additives capable of facilitating the processing 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 Hindered Amine Light Stabilizers (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 hexanediol diacrylate and coupling agents), and combinations and mixtures thereof.

[0083] According to various non-limiting embodiments, the photochromic materials described herein can be used in an amount (or ratio) such that the organic material or substrate into which the photochromic material is incorporated or incorporated exhibits the desired optical properties. For example, the amount and type of photochromic material can be selected such that when the photochromic material is in a closed-form (i.e., a bleached or unactivated state), the organic material or substrate can be clear or colorless, and when the photochromic material is in an open-form (i.e., when activated by actinic radiation), the desired resulting color can be exhibited. The precise amount of photochromic material used in the various photochromic compositions and articles described herein is not critical, provided that a sufficient amount is used to produce the desired effect. It should be understood that the specific amount of photochromic material used may depend on a number of factors, such as, but not limited to: the absorption characteristics of the photochromic material, the color and intensity of the desired tint when activated, and the method used to incorporate or incorporate the photochromic material into the substrate. Although not limiting herein, according to various non-limiting embodiments disclosed herein, the amount of photochromic material incorporated into the organic material can range from 0.01 to 40 weight percent, based on the weight of the organic material.

[0084] In the following non-limiting examples, various non-limiting embodiments disclosed herein are illustrated.

Examples

[0085]In part I of the examples, synthetic methods for preparing photochromic materials according to certain non-limiting embodiments disclosed herein are set forth inExamples 1 to 4. In part II, the formation of methacrylate test chips, and determination of fade rate (T) incorporating certain photochromic materials described herein, as well as comparative photochromic materials, are described_1/2) Maximum absorbance wavelength and saturated optical density.

Part I: synthesis method

Example 1

Step 1

[0086] Piperidine (23.4 grams ("g")), 4' -difluorobenzophenone (60 grams), triethylamine (30.6 grams) were added to a reaction flask containing 100 milliliters ("mL") of dimethylsulfoxide. The resulting mixture was heated to 105 ℃ and stirred overnight under nitrogen. After 24 hours at 105 ℃, the reaction was quenched in 1400 ml of water with vigorous stirring and a light brown solid was observed to precipitate. The solid was filtered, washed with water and air-dried to obtain 79.5 g of the desired product, 4-fluoro-4' -piperidinobenzophenone. This material was used in the next step without further purification.

Step 2

[0087] The product of step 1, 4-fluoro-4' -piperidinobenzophenone (78 g), was added to a reaction flask containing 500 ml of N, N-dimethylformamide (saturated with acetylene). The resulting mixture was stirred at room temperature under a nitrogen atmosphere using a mechanical stirrer. Sodium acetylene in xylene/mineral oil (73.5 grams of an 18% by weight solution) was added to the reaction mixture over thirty minutes while stirring. After stirring for one hour at room temperature, the reaction was quenched in 4L of water with vigorous stirring and a tan solid was observed to precipitate. The solid was filtered, washed with water and air dried to yield 85 g of the desired product, 1- (4-fluorophenyl) -1- (4-piperidinophenyl) -2-propyn-1-ol. This material was used in step 7 without further purification.

Step 3

[0088] Potassium tert-butoxide (68.8 g) was weighed into a reaction flask equipped with a mechanical stirrer, placed under nitrogen, 700 ml of toluene was added followed by 4, 4' -difluorobenzophenone (100 g). The reaction mixture was mechanically stirred and heated to 70 ℃. 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 ℃ for 4 hours. After cooling to room temperature, the reaction mixture was poured into 500 ml of water and the toluene layer was removed. The aqueous layer was extracted with ether (1 × 400 ml), the neutral product was removed, and then the aqueous layer was acidified with concentrated HCl. A tan oily solid was obtained from the aqueous layer and extracted with 3 × 300 ml of ethyl acetate. The organic layers were combined, washed with saturated NaCl solution (1 × 500 ml) and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation to give 122 g of 4, 4-bis (4-fluorophenyl)) -3-methoxycarbonyl-3-butenoic acid as a pale brown oily solid. This material was used directly in the next step without further purification.

Step 4

[0089] The product of step 3 (4, 4-bis (4-fluorophenyl)) -3-methoxycarbonyl-3-butenoic acid, 122 g) and acetic anhydride (250 ml) were added to a reaction flask. The reaction mixture was heated at reflux under nitrogen for 5 hours. The reaction mixture was cooled to room temperature and then poured into 1200 ml of water. The resulting precipitate was collected by vacuum filtration and washed with cold water to give 110 g of 1- (4-fluorophenyl) -2-methoxycarbonyl-4-acetoxy-6-fluoronaphthalene. This product was used in the subsequent reaction without further purification.

Step 5

[0090] The 1- (4-fluorophenyl) -2-methoxycarbonyl-4-acetoxy-6-fluoronaphthalene from step 4 (110 g) and 400 ml methanol were combined in a reaction flask. 5 ml of concentrated hydrochloric acid was added to the reaction flask and heated under reflux for 4 hours under nitrogen atmosphere. The reaction mixture was cooled to room temperature and then to 0 ℃. White crystals of the desired product (1- (4-fluorophenyl) -2-methoxycarbonyl-4-hydroxy-6-fluoronaphthalene, 65 g) were obtained, which were subsequently filtered off and dried in vacuo. This material was used directly in the next step without further purification.

Step 6

[0091] The product of step 5 (1- (4-fluorophenyl) -2-methoxycarbonyl-4-hydroxy-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 nitrogen atmosphere. 167 ml of methylmagnesium bromide solution (3M in ether) were added dropwise over thirty minutes. The resulting yellow reaction mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was poured into 400 ml of water and neutralized with concentrated HCl until acidic. The mixture was extracted with three 300 ml portions of ether and the organic portions were combined and washed with 1L of saturated NaCl solution. The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting brown oil (37.8 g) was transferred to a reaction vessel (equipped with a dean-Stark trap) containing 300 ml of xylene, to which five drops of dodecylbenzene sulfonic acid were added. The reaction mixture was heated at reflux for 3 hours and cooled. Xylene was removed by rotary evaporation to yield 35 g of 3, 9-difluoro-7, 7-dimethyl-5-hydroxy-7H-benzo [ C ] fluorene as a light brown oil. This material was used directly in the next step without further purification.

Step 7

[0092] The product of step 6 (3, 9-difluoro-7, 7-dimethyl-5-hydroxy-7H-benzo [ C ] fluorene, 5.55 g), the product of step 2 (1- (4-fluorophenyl) -1- (4-piperidinophenyl) -2-propyn-1-ol, 5.8 g), 8 drops of methanesulfonic acid and 250 ml of chloroform were mixed in a reaction flask and stirred under nitrogen atmosphere at reflux temperature. After two hours, an additional 3.0 g of 1- (4-fluorophenyl) -1- (4-piperidinophenyl) -2-propyn-1-ol and 8 drops of dodecylbenzenesulfonic acid were added to the reaction mixture. The reaction mixture was heated at 50 ℃ overnight and then cooled to room temperature. The reaction mixture was carefully washed with a mixture of 250 ml of saturated sodium bicarbonate solution and 250 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 and ethyl acetate (95/5) as the eluent. The photochromic fractions were collected and concentrated by rotary evaporation to give a blue-white solid (8.0 g). The blue-white foam was further purified by precipitation with methanol to yield 3.5 g of a green colored white solid. NMR spectrum showed the product to have a molecular weight similar to that of 3- (4-fluorophenyl) -3- (4-piperidinophenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

Example 2

Step 1

[0093] The product of example 1, step 2 (1-phenyl-2-methoxycarbonyl-4-acetoxynaphthalene, 50 g) in U.S. patent 5,645,767 was added to a reaction flask containing 500 ml tetrahydrofuran. The resulting mixture was cooled in an ice-water bath and stirred under nitrogen atmosphere. 703 ml of a methylmagnesium chloride solution (1M in tetrahydrofuran) were added dropwise over forty-five minutes. The resulting yellow reaction mixture was stirred at 0 ℃ for 2 hours and slowly warmed to room temperature. The reaction mixture was poured into 2L of ice/water mixture. Ether (1L) was added and the layers were separated. The aqueous layer was extracted with two 500 ml portions of ether and the organic portions were combined and washed with 1L of water. The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The obtained solution was transferred to a reaction vessel (equipped with a dean-Stark trap) containing 500 ml of toluene, and ten drops of dodecylbenzenesulfonic acid were added thereto. The reaction mixture was heated at reflux for 2 hours and cooled. Toluene was removed by rotary evaporation to yield 40.2 g of a pale yellow solid. The NMR spectrum showed that the product had a structure consistent with 7, 7-dimethyl-5-hydroxy-7H-benzo [ C ] fluorene. This material was used directly in the next step without further purification.

Step 2

[0094] The product of step 1, 7-dimethyl-5-hydroxy-7H-benzo [ C ] fluorene (6.0 g), the product of step 2, example 1, 1- (4-fluorophenyl) -1- (4-piperidinophenyl) -2-propyn-1-ol (7.1 g), 7 drops of methanesulfonic acid and 250 ml of chloroform were mixed in a reaction flask and stirred at reflux temperature. After two hours, an additional 2.0 g of 1- (4-fluorophenyl) -1- (4-piperidinophenyl) -2-propyn-1-ol and four drops of methanesulfonic acid were added to the reaction mixture. After this time, an additional 1.0 g of 1- (4-fluorophenyl) -1- (4-piperidinylphenyl) -2-propyn-1-ol was added, and after a further two hours, four drops of methanesulfonic acid were added. The reaction mixture was refluxed and then heated for 6 hours, and then cooled to room temperature. The reaction mixture was carefully washed with a mixture of 200 ml of saturated sodium bicarbonate solution and 200 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 and ethyl acetate (93/7) as the eluent. The photochromic fractions were collected and concentrated by rotary evaporation to give a slightly blue solid (11 g). The blue solid was further purified by crystallization from a 1: 1 mixture of diethyl ether and hexane to yield 9.2 g of a white solid. The NMR spectrum showed that the product had a molecular weight similar to that of 3- (4-fluorophenyl) -3- (4-piperidinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

Example 3

[0095] The product of step 6 of example 1 (3, 9-difluoro-7, 7-dimethyl-5-hydroxy-7H-benzo [ C ] fluorene, 5.0 g), 1- (4-fluorophenyl) -1- (4-morpholinophenyl) -2-propyn-1-ol (5.3 g), 7 drops of methanesulfonic acid and 200 ml of chloroform were mixed in a reaction flask and stirred under nitrogen atmosphere at reflux temperature. After one hour, an additional 5.0 g of 1- (4-fluorophenyl) -1- (4-morpholinophenyl) -2-propyn-1-ol are added to the reaction mixture and heating is continued. After two hours, an additional 2.0 g of 1- (4-fluorophenyl) -1- (4-morpholinophenyl) -2-propyn-1-ol and 4 drops of methanesulfonic acid were added to the reaction mixture. The reaction mixture was heated for an additional four hours and then cooled to room temperature. The reaction mixture was carefully washed with a mixture of 125 ml of saturated sodium bicarbonate solution 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, dichloromethane and ethyl acetate (60/35/5) as the eluent. The photochromic fractions were collected and concentrated by rotary evaporation to give a blue solid (4.0 g). The blue solid was further purified by crystallization from a 1: 1 mixture of diethyl ether and hexane to yield 3.4 g of a white solid. The NMR spectrum showed that the product had a molecular weight similar to that of 3- (4-fluorophenyl) -3- (4-morpholinophenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

Example 4

[0096] The product of step 1, example 2, 7-dimethyl-5-hydroxy-7H-benzo [ C ] fluorene (4.0 g), 1- (4-fluorophenyl) -1- (4-morpholinophenyl) -2-propyn-1-ol (6.3 g), 8 drops of methanesulfonic acid and 200 ml of chloroform were mixed in a reaction flask and stirred at reflux temperature under nitrogen atmosphere. After one hour, an additional 4.6 g of 1- (4-fluorophenyl) -1- (4-morpholinophenyl) -2-propyn-1-ol are added to the reaction mixture and heating is continued. After two hours, an additional 5.0 g of 1- (4-fluorophenyl) -1- (4-morpholinophenyl) -2-propyn-1-ol and 4 drops of methanesulfonic acid were added to the reaction mixture. The reaction mixture was heated overnight and then cooled to room temperature. The reaction mixture was carefully washed with a mixture of 100 ml of saturated sodium bicarbonate solution and 100 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, dichloromethane and ethyl acetate (60/37/3) as the eluent. The photochromic fractions were collected and concentrated by rotary evaporation to give a blue solid (8.2 g). The blue solid was further purified by crystallization from diethyl ether to yield 4.4 g of a white solid. The NMR spectrum showed that the product had a molecular weight similar to that of 3- (4-fluorophenyl) -3- (4-morpholinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

Part II: testing

[0097] The photochromic materials of examples 1-4 and comparative examples CE1-CE6 were tested for photochromic performance using the following optical bench set-up. In addition, a fifth compound, example 5, in accordance with certain non-limiting embodiments of the present disclosure was tested. It will be understood by those skilled in the art that the photochromic materials of example 5 and comparative examples CE1-CE6 can be prepared in accordance with the teachings and disclosure herein of the examples with appropriate modifications as will be apparent to those skilled in the art upon reading this disclosure. Furthermore, those skilled in the art will recognize that various modifications of the disclosed methods, as well as other methods, can be used in preparing the photochromic materials of examples 1-4 without departing from the scope of the present disclosure as set forth in the specification and claims herein.

Methacrylate crumb process

[0098]The calculation can obtain 1.5x10^-3The amount of photochromic material tested for the M solution was added to a flask containing 4 parts of ethoxylated bisphenol A dimethacrylate (BPA 2EO DMA), 1 part of poly (ethylene glycol) 600 dimethacrylate and 0.033 weight percent of a 50 gram monomer mixture of 2, 2' -azabicyclo (2-methylpropanenitrile) ("AIBN"). The photochromic material is dissolved into the monomer mixture by stirring and gentle heating. After obtaining a clear solution, it was vacuum degassed and then poured into a flat plate mold having internal dimensions of 2.2 mm x6 inches (15.24 cm) x6 inches (15.24 cm). The mold was sealed and placed in a horizontal air flow, a programmable oven was programmed to raise the temperature from 40 ℃ to 95 ℃ over a period of 5 hours, hold the temperature at 95 ℃ for 3 hours, and then lower the temperature to 60 ℃ for at least 2 hours. After opening the mold, the polymer sheet was cut into 2 inch (5.1 cm) test square specimens using a diamond blade saw.

[0099]On an optical bench, the photochromic response of the test square specimens (incorporating the photochromic materials prepared as described above) was examined. Photochromic test square specimens were exposed to 365nm ultraviolet light for about 15 minutes prior to testing on an optical bench to convert the photochromic material therein from an unactivated ground state (or whitened) to an activated state (or colored) and then placed in a 75 ℃ oven for about 15 minutes to return the photochromic material to the unactivated state. The test square specimens were then cooled to room temperature, exposed to fluorescent room lighting for at least 2 hours, then left covered (i.e., in the dark) for at least 2 hours, and then left in the darkThe test was carried out on an optical bench maintained at 23 ℃. The test rig was equipped with a 300 watt xenon arc lamp, remote control mask, Melles Griot KG2 filter that changed UV and IR wavelengths and served as a heat sink, neutral color filter and sample holder, within a 23 ℃ water bath in which the square test specimens tested were embedded. The parallel light beam from the tungsten lamp was passed through the square specimen at a small angle (approximately 30 °) to perpendicular to the square specimen direction. After passing through the square sample, the tungsten filament lamp was aimed at the collection sphere where the light was fused and aimed onto an Ocean Optics S2000 spectrometer where the spectrum of the measuring beam was collected and analyzed. Lambda [ alpha ]_max-visIs the wavelength in the visible spectrum at which the maximum absorption of the activated (colored) form of the photochromic material in the test square specimen occurs. Lambda was determined by testing photochromic test square coupons on a Varian Cary 4000 UV-visible spectrophotometer_mas-visWavelength. The output signal of the detector is processed with a radiometer.

[0100]The saturated optical density ("Sat'd OD") of each test square was determined by opening the mask of the xenon lamp and the light transmittance was determined after exposing the test debris to UV radiation for 30 minutes. The lambda at Sat'd OD was calculated using the activation data measured by the S2000 spectrometer on the optical bench_max-vis. By fade half life (i.e. T)_1/2) The fade rate was measured as the time interval (seconds) at which the absorbance of the activated form of the photochromic material in the test square sample reached half the Sat'd OD absorbance value after removal of the excitation light source at room temperature (23 ℃). Performance rating ("PR") is determined by Sat'd OD and T using the following formula_1/2Calculated:

PR＝((Sat′d OD)/T_1/2)x10,000.

photochromic data for certain photochromic materials according to the present disclosure are provided in table 1. Photochromic data for comparative photochromic materials (i.e., photochromic indeno-fused naphthopyrans in which neither group B nor B' is a 4-fluorophenyl or 4-aminophenyl group listed herein) are provided in Table 2.

Table 1: photochromic materials and test results

Ex	Photochromic material	λmax-vis(nm)	Sat’dOD	T1/2(second)	PR
						1	3- (4-fluorophenyl) -3- (4-piperidinophenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	613	0.48	64	75
2	3- (4-fluorophenyl) -3- (4-piperidinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	595	0.97	118	82
						3	3- (4-fluorophenyl) -3- (4-morpholinophenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	595	0.58	74	78
4	3- (4-fluorophenyl) -3- (4-morpholinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	579	1.06	151	70
						5	3- (4-fluorophenyl) -3- (4- (2-methylpiperidino) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	603	1.01	124	82

Table 2: comparative photochromic materials and test results

Ex	Photochromic material	λmax-vis(nm)	Sat’dOD	T1/2(second)	PR
						CE1	3, 3-diphenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	532	1.50	723	21
CE2	3-phenyl-3- (4-piperidinophenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	616	0.73	94	78
						CE3	3-phenyl-3- (4-piperidinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	599	1.04	180	50
CE4	3- (4-morpholinophenyl) -3-phenyl-6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	599	0.84	122	69
						CE5	3- (4-morpholinophenyl) -3-phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	583	1.45	241	60
CE6	3- (4-fluorophenyl) -3-phenyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1, 2-b ]]Pyrans	533	1.53	542	28

[0101] It is to be understood that this specification illustrates aspects of the invention relevant to a clear understanding of the invention. Certain aspects of the present invention that would be apparent to those of ordinary skill in the art, and that, therefore, would not facilitate a better understanding of the invention, have not been provided for the purpose of simplifying the present description. While the invention has been described in connection with certain embodiments, it is not intended to be limited to the specific embodiments disclosed, but is intended to cover modifications within the spirit and scope of the invention as defined by the appended claims.

Claims (20)

1. A photochromic material comprising:

an indeno-fused naphthopyran comprising a group B attached to its 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, wherein the substituent at the 4-position of the 4-substituted phenyl group is-NR¹R²Wherein R is¹And R²Each independently is hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl, or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆Alkoxy, or R¹And R²Linked together with the nitrogen atom to form a nitrogen-containing ring represented by the following structural formula II:

wherein each-Y-is independently at each occurrence selected from: -CH₂-，-CH(R³)-，-C(R³)₂-, -CH (aryl) -, -C (aryl)₂-, and-C (R)³) (aryl) -, Z is-Y-, -S-, -S (O) -, -SO₂-，-NH-，-N(R³) -, or-N (aryl) -, in which each R is³Independently is C₁-C₆Alkyl or hydroxy (C)₁-C₆) Alkyl, each aryl group is independently phenyl or naphthyl, m is the integer 1, 2 or 3, p is the integer 0, 1, 2 or 3, and when p is 0, Z is-Y-.

2. The photochromic material of claim 1 wherein the photochromic material has a faster fade rate than a similar photochromic material comprising an indeno-fused naphthopyran wherein the indeno-fused naphthopyran does not contain a 4-fluorophenyl group and a 4-substituted phenyl group at the 3-position thereof, wherein the substituent at the 4-position is-NR¹R²。

3. The photochromic material of claim 1 wherein the group B' is one of 4- (N, N-dialkylamino) phenyl, 4-piperidinophenyl, 4- (substituted piperidino) phenyl, 4-pyrrolidinophenyl, 4- (substituted pyrrolidino) phenyl, 4-piperazinophenyl, or 4- (substituted piperazino) phenyl, wherein the substituents on the piperidino, pyrrolidino, or piperazino groups comprise (C)₁-C₆) Alkyl or hydroxy (C)₁-C₆) Alkyl, the alkyl groups of dialkylamino being identical or different (C)₁-C₆) An alkyl group.

4. The photochromic material of claim 1 further comprising a first electron-withdrawing group bonded to a carbon in the C-ring of the indeno-fused naphthopyran.

5. The photochromic material of claim 4 wherein a first electron-withdrawing group is bonded to the 6-position of the indeno-fused naphthopyran.

6. The photochromic material of claim 4 wherein the first electron-withdrawing group is fluorine, chlorine, bromine, perfluoroalkyl, perfluoroalkoxy, cyano, -OC (═ O) R⁴，-SO₂X, or-C (═ O) -X, X is hydrogen, C₁-C₆Alkyl, -OR⁵or-NR⁶R⁷Wherein R is⁴、R⁵、R⁶And R⁷Each independently of the other being hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, monosubstituted phenyl, di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group.

7. The photochromic material of claim 4 further comprising a second electron-withdrawing group bonded to the 11-position of the indeno-fused naphthopyran.

8. The photochromic material of claim 7 wherein the second electron-withdrawing group is fluorine, chlorine, bromine, perfluoroalkyl, perfluoroalkoxy, cyano, -OC (═ O) R⁸，-SO₂X, or-C (═ O) -X, X is hydrogen, C_1-C₆Alkyl, -OR⁹or-NR¹⁰R¹¹Wherein R is⁸、R⁹、R¹⁰And R¹¹Each independently of the other being hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl, or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group.

9. The photochromic material of claim 1 further comprising a first fluorine substituent bonded to the 6-position of the indeno-fused naphthopyran and a second fluorine substituent at the 11-position of the indeno-fused naphthopyran.

10. A photochromic material having the structure:

wherein

s is an integer from 0 to 3, q is an integer from 0 to 3, each R¹⁶And each R¹⁷At each occurrence: hydrogen; fluorine; chlorine; bromine; a perfluoroalkyl group; a perfluoroalkoxy group; a cyano group; -OC (═ O) R²¹；-SO₂X; -C (═ O) -X, where X is hydrogen, C₁-C₆Alkyl, -OR²²or-NR²³R²⁴Wherein R is²¹、R²²、R²³And R²⁴Each is independently hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl, or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆An alkoxy group; c₁-C₆An alkyl group; c₃-C₇A cycloalkyl group; substituted or unsubstituted phenyl; -OR²⁵Wherein R is²⁵Is hydrogen, C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical (C)₁-C₆) Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl radicals, or mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl, the phenyl substituent being C₁-C₆Alkyl or C₁-C₆An alkoxy group; a monosubstituted phenyl, said phenyl having a substituent at the para position, wherein the substituent is: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residues or derivatives thereof, polyol residues or derivatives thereof, -CH₂-，-(CH₂)_t-, or- [ O- (CH)₂)_t]_k-, where t is an integer 2, 3, 4, 5 or 6, k is an integer from 1 to 50, and the substituent is attached to an aryl group on another photochromic material; -N (R)²⁶)R²⁷Wherein R is²⁶And R²⁷Each is independently hydrogen, C₁-C₈Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, C₁-C₈Alkylaryl group, C₃-C₂₀Cycloalkyl radical, C₄-C₂₀Bicycloalkyl radical, C₅-C₂₀Tricycloalkyl or C₁-C₂₀Alkoxyalkyl wherein the aryl is phenyl or naphthyl, or, R²⁶And R²⁷Together with nitrogen atoms to form C_3-C₂₀A heterobicycloalkyl ring or C_4-C₂₀A heterotricycloalkyl ring; a nitrogen-containing ring represented by the following structural formula IVA:

wherein each-Y-is independently at each occurrence selected from: -CH₂-，-CH(R²⁸)-，-C(R²⁸)₂-, -CH (aryl) -, -C (aryl)₂-, and-C (R)²⁸) (aryl) -, Z is-Y-, -O-, -S-, -S (O) -, -SO₂-，-NH-，-N(R²⁸) -, or-N (aryl) -, in which each R is²⁸Independently is C₁-C₆Alkyl or hydroxy (C)₁-C₆) Alkyl, each aryl group is independently phenyl or naphthyl, m is the integer 1, 2 or 3, p is the integer 0, 1, 2 or 3, and when p is 0, Z is-Y-; byA group represented by one of the following structural formulae IVB or IVC:

wherein R is³⁰、R³¹And R³²Each independently of the other being hydrogen, C₁-C₆Alkyl, phenyl, or naphthyl, or the radical R³⁰And R³¹Together form a ring of 5 to 8 carbon atoms, each R²⁹Independently at each occurrence is C₁-C₆Alkyl radical, C₁-C₆Alkoxy, fluorine or chlorine, g is the integer 0, 1, 2 or 3; and unsubstituted, mono-or di-substituted C₄-C₁₈Spirobicyclic amines, or unsubstituted, mono-and di-substituted C₄-C₁₈Spirotricyclic amine wherein the substituents are independently aryl, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, or phenyl (C)₁-C₆) An alkyl group; or

R in the 6-position¹⁶Radicals and R in the 7-position¹⁶The groups together form a group represented by one of IVD and IVE:

wherein T and T' are each independently oxygen or a group-NR²⁶-, wherein R²⁶、R³⁰And R³¹As listed above;

R¹⁸and R¹⁹Each is independently: hydrogen; a hydroxyl group; c₁-C₆An alkyl group; c₃-C₇A cycloalkyl group; an allyl group; substituted or unsubstituted phenyl; substituted or unsubstituted benzyl; chlorine; fluorine; a radical-C (═ O) W, where W is hydrogen, hydroxy, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, unsubstituted, mono-or di-substituted aryl radicals phenyl or naphthyl, phenoxy, mono-or di- (C)_1-C₆) Alkoxy-substituted phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, amino, mono (C)₁-C₆) Alkylamino, di (C)₁-C₆) Alkylamino, phenylamino, mono-or di- (C)₁-C₆) Alkyl-substituted phenylamino, or mono-or di- (C)₁-C₆) Alkoxy-substituted phenylamino; -OR³³Wherein R is³³Is C₁-C₆Alkyl, phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkyl-substituted phenyl (C)₁-C₃) Alkyl, mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl radical, C₁-C₆Alkoxy (C)₂-C₄) Alkyl radical, C₃-C₇Cycloalkyl radicals, mono (C)₁-C₄) Alkyl substituted C₃-C₇Cycloalkyl radical, C₁-C₆Chloroalkyl, C₁-C₆Fluoroalkyl, allyl, or a radical-CH (R)³⁴) W', wherein R³⁴Is hydrogen or C₁-C₃Alkyl, W' is CN, CF₃Or COOR³⁵Wherein R is³⁵Is hydrogen or C₁-C₃Alkyl, or R³³Is a group-C (═ O) W 'wherein W' is hydrogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy, unsubstituted, mono-or di-substituted aryl radicals phenyl or naphthyl, phenoxy, mono-or di- (C)₁-C₆) Alkyl-substituted phenoxy, mono-or di- (C)₁-C₆) Alkoxy-substituted phenoxy, amino, mono (C)_1-C₆) Alkylamino, di (C)₁-C₆) Alkylamino, phenylamino, mono-or di- (C)₁-C₆) Alkyl-substituted phenylamino, or mono-or di- (C)₁-C₆) Alkoxy-substituted phenylamino wherein each of the phenyl, benzyl or aryl substituents is independently C₁-C₆Alkyl or C₁-C₆An alkoxy group; or a mono-substituted phenyl, said phenyl having a substituent located at the para position, wherein the substituent is: dicarboxylic acid residues or derivatives thereof, diamine residues or derivatives thereof, amino alcohol residuesOr derivatives thereof, polyol residues or derivatives thereof, -CH₂-，-(CH₂)_t-, or- [ O- (CH)₂)_t]_k-, where t is an integer 2, 3, 4, 5 or 6, k is an integer from 1 to 50, and the substituent is attached to an aryl group on another photochromic material; or, R¹⁸And R¹⁹Together form an oxo group, a spiro-carbocyclic group containing from 3 to 6 carbon atoms, or a spiro-heterocyclic group containing from 1 to 2 oxygen atoms and from 3 to 6 carbon atoms containing spiro carbon atoms, which spiro-carbocyclic and spiro-heterocyclic groups are annelated with 0, 1 or 2 phenyl rings; and

R²⁰is-NR³⁶R³⁷Wherein R is³⁶And R³⁷Each independently of the other being hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl, or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆Alkoxy, or, R³⁶And R³⁷And is linked together with the nitrogen atom to form a nitrogen-containing ring represented by the following structural formula V:

wherein each-Y' -is independently at each occurrence selected from: -CH₂-，-CH(R³⁸)-，-C(R³⁸)₂-, -CH (aryl) -, -C (aryl)₂-, and-C (R)³⁸) (aryl) -, Z 'is-Y' -, -O-, -S-, -S (O) -, -SO₂-，-NH-，-N(R³⁸) -, or-N (aryl) -, in which each R is³⁸Independently is C₁-C₆Alkyl or hydroxy (C)_1-C₆) Alkyl, each aryl group is independently phenyl or naphthyl, m ' is the integer 1, 2 or 3, p ' is the integer 0, 1, 2 or 3, and when p ' is 0, Z ' is-Y ' -;

provided that if R is²⁰Is morpholino, R¹⁶Is not a 4-substituted piperidino group at the 7-position of structure III.

11. The photochromic material of claim 10 wherein R²⁰Including dialkylamino, morpholino, piperidino, substituted piperidino, pyrrolidinyl, substituted pyrrolidinyl, piperazinyl, or substituted piperazinyl, wherein the substituents on the piperidino, pyrrolidinyl, or piperazinyl include (C)₁-C₆) Alkyl or hydroxy (C)₁-C₆) The alkyl groups of the alkyl, dialkylamino groups can be the same or different (C)₁-C₆) An alkyl group.

12. The photochromic material of claim 10 wherein R¹⁶In the 6-position is a fluoro group, R¹⁷In the 11-position is a fluoro group.

13. The photochromic material of claim 10 selected from the group consisting of:

(a)3- (4-fluorophenyl) -3- (4-morpholinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(b)3- (4-fluorophenyl) -3- (4-morpholinophenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(c)3- (4-fluorophenyl) -3- (4-piperidinophenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(d)3- (4-fluorophenyl) -3- (4-piperidinophenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(e)3- (4-fluorophenyl) -3- (4- (2-methylpiperidino) phenyl) -13, 13-dimethyl-3H, 13H-indeno [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-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(g)3- (4-fluorophenyl) -3- (4-piperazinylphenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(h)3- (4-fluorophenyl) -3- (4-piperazinylphenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(i)3- (4-fluorophenyl) -3- (4-pyrrolidinylphenyl) -13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(j)3- (4-fluorophenyl) -3- (4-pyrrolidinylphenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyran;

(k)3- (4-fluorophenyl) -3- (4- (N, N-diethylamino) phenyl) -13, 13-dimethyl-3H, 13H-indeno [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-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

14. A compound represented by the following structure:

wherein R is¹²is-NR¹³R¹⁴Wherein R is¹³And R¹⁴Each is independently hydrogen, C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl, mono-substituted phenyl or di-substituted phenyl, wherein the phenyl substituent is C₁-C₆Alkyl or C₁-C₆Alkoxy, or R¹³And R¹⁴Together with the nitrogen atom to form a nitrogen-containing ring represented by the following structural formula II:

wherein each-Y-is independently at each occurrence selected from: -CH₂-，-CH(R¹⁵)-，-C(R¹⁵)₂-, -CH (aryl) -, -C (aryl)₂-, and-C (R)¹⁵) (aryl) -, Z is-Y-, -O-,-S-，-S(O)-，-SO₂-，-NH-，-N(R³) -, or-N (aryl) -, in which each R is¹⁵Independently is C₁-C₆Alkyl or hydroxy (C)₁-C₆) Alkyl, each aryl group is independently phenyl or naphthyl, m is the integer 1, 2 or 3, p is the integer 0, 1, 2 or 3, and when p is 0, Z is-Y.

15. The compound of claim 14, wherein R¹²Including dialkylamino, morpholino, piperidino, substituted piperidino, pyrrolidinyl, substituted pyrrolidinyl, piperazinyl, or substituted piperazinyl, wherein the substituents on the piperidino, pyrrolidinyl, or piperazinyl include (C)₁-C₆) Alkyl or hydroxy (C)₁-C₆) Alkyl, the alkyl groups of dialkylamino being identical or different (C)₁-C₆) An alkyl group.

16. A method of preparing a photochromic material comprising:

reacting the compound of claim 14 with 7H-benzo [ C ] fluoren-5-ol to form a 3H, 13H-indeno [2 ', 3': 3, 4] naphtho [1, 2-b ] pyrans.

17. A photochromic article comprising: a substrate; and a photochromic material according to claim 1 bonded to at least a portion of the substrate.

The photochromic article of claim 17 wherein the photochromic article is an optical element, said optical element being at least one of: an ophthalmic element, a display element, a window, a mirror, an active liquid crystal cell element or 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 the polymeric material using at least one of the following: mixed with at least a portion of the polymeric material, bonded with at least a portion of the polymeric material, and impregnated into at least a portion of the polymeric material.

20. The photochromic article of claim 17 wherein the photochromic article comprises an at least partial coating associated with at least a portion of the substrate, said at least partial coating comprising said photochromic material.