HK1188789B - Lactone compounds and materials made therefrom - Google Patents

Description

Lactone compounds and materials prepared therefrom

cross Reference to Related Applications

This application claims priority to U.S. provisional patent application No. 61/459,675, filed on 12/16/2010.

Technical Field

The present invention relates to methods for the preparation of lactone compounds, e.g., fused ring lactone compounds, and methods for the preparation of other materials, e.g., fused ring indenophenol compounds and fused ring indenopyran compounds, from lactone compounds.

Background

Fused ring indenol compounds, such as indeno-fused naphthols, have many uses, for example, as intermediates in the synthesis of photochromic compounds and materials (e.g., fused ring indenopyrans, including indeno-fused naphthopyrans). Photochromic materials (e.g., indeno-fused naphthopyrans) are responsive to certain wavelengths of electromagnetic radiation (or "actinic radiation"), typically through a transition from one form or state to another, each having a distinguishable or characteristic absorption spectrum associated therewith. Typically, many photochromic materials transform from a closed form (corresponding to an unactivated (or discolored, e.g., substantially colorless) state of the photochromic material) to an open form (corresponding to an activated (or colored) state of the photochromic material) upon exposure to actinic radiation. Such photochromic materials reversibly transform from an activated (or colored) state back to an unactivated (or faded) state in the absence of exposure to actinic radiation. Compositions or articles (e.g., ophthalmic lenses) comprising photochromic materials or having photochromic materials applied thereto (e.g., in the form of photochromic coating compositions) typically exhibit colorless (e.g., clear) and colored states corresponding to the colorless and colored states of the photochromic materials contained therein or applied thereto.

Indeno-fused naphthol materials are typically prepared by a synthetic mechanism involving the reaction of a benzophenone with a dialkyl succinate, commonly referred to as the Stobbe reaction pathway. When asymmetric benzophenones are used, a mixture of indeno-fused naphthol materials is typically obtained from the Stobbe reaction pathway. The mixture of indeno-fused naphthols typically must be separated to isolate the desired indeno-fused naphthol. The isolated indeno-fused naphthol can then be used in a subsequent reaction (e.g., in the synthesis of a photochromic indeno-fused naphthopyran). This separation step typically results in a significant reduction in yield associated with the desired indeno-fused naphthol material. Furthermore, the Stobbe reaction pathway can include two separate closed-loop steps, which are typically performed at different times and in different reaction vessels.

Some photochromic materials (e.g., photochromic indeno-fused naphthopyrans) can be expensive, and thus it is often desirable to reduce the costs associated with the synthesis of such materials in view of economic considerations.

It would be desirable to develop new materials (e.g., intermediates) and new methods of using the newly developed materials to make, for example, indeno-fused naphthols and related materials. Furthermore, it would also be desirable for such newly developed materials and methods to provide improvements over previous synthetic methods, such as increased yields, reduced number of synthetic steps, and reduced costs.

Summary of The Invention

In accordance with the present invention, there is provided a lactone compound selected from the group consisting of lactone compounds represented by the following formulas I and II:

and

formula I

Formula II

Referring to formulas I and II, each of the a and B rings is independently selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted fused ring aryl, substituted fused ring aryl, unsubstituted heteroaryl, and substituted heteroaryl.

With further reference to formulas I and II, m and n are each independently selected from 0 to the linkage capable of R on the rings corresponding to A and B, respectively¹Group or R²Values for many positions of the group. Typically, m and n are each independently 0-4. R is not attached to the A ring¹The position of the group is capable of linking to a hydrogen group. Similarly, R is not attached to the B ring²The position of the group is capable of linking to a hydrogen group. Furthermore, R of each m¹And R of each n²Independently selected from: a hydrocarbyl group optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-、-N(R₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl and combinations of two or more thereof; substituted hydrocarbyl optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-、-N(R₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl and combinations of two or more thereof; halogen; a cyano group; and-N (R)₁₁’)R₁₂', wherein R₁₁' and R₁₂' are each independently selected from hydrogen, hydrocarbyl or substituted hydrocarbyl, or R₁₁' and R₁₂Together form a ring structure optionally including at least one heteroatom.

R of the formulae I and II³And R⁴Each independently selected from: hydrogen; a hydrocarbyl group optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-, and-N (R)₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl; and substituted hydrocarbyl optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-and-N (R)₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl; or R³And R⁴Together form a ring structure optionally including at least one heteroatom. R¹、R²、R³And R⁴Can independently represent in each case one or more precursors of the groups as described above and further herein with reference to those of formulae I and II.

In accordance with the present invention, there is also provided a method of making a fused ring indenol compound represented by at least one of formula III and formula III-2 below:

and

formula III

Formula III-2

Referring to formulas III and III-2, ring A, ring B, m, n, R¹、R²、R³And R⁴Each as described herein before with respect to the lactone compounds shown in formulas I and II. Alternatively, R¹、R²、R³And R⁴Can independently represent one or more precursors of groups as described above and as described herein with reference to, for example, formulae I and II. R of the formulae III and III-2¹²The group is selected from hydrogen, -C (O) -R¹³and-S (O) R¹³Wherein R is¹³Selected from the group consisting of hydrocarbyl and halogenated hydrocarbyl.

The preparation method of the fused ring indenol compound shown by the formula III or the formula III-2 comprises the following steps: converting a lactone compound selected from the group consisting of lactone compounds represented by at least one of formulas I and II below to an acid intermediate comprising an acid intermediate represented by at least one of formulas IV and IV-2.

And

formula I

Formula II

Formula IV

Formula IV-2

The method for preparing the fused ring indenol compound represented by formula III or formula III-2 further comprises: converting the acid intermediate of formula IV or IV-2 to the corresponding indeno-fused compound of formula III or III-2.

The invention also provides a preparation method of the lactone compound shown by at least one of the formulas I and II. The method includes reacting an acid ester of at least one of formula VI and formula VII with (i) a metal hydride reducing agent and/or (ii) a nucleophile of at least one of formula VIII and formula IX, thereby producing the lactone compound. Representative of formulas VI, VII, VIII and IX are provided below:

formula VI

Formula VII

R^3’M¹R^4’M²

Formula VIII and formula IX

Reference is made to formulae VI, VII, VIII and IX: r¹⁶Selected from hydrocarbyl and substituted hydrocarbyl; r^3’Is R as described with reference to formulae I and II³(ii) a nucleophile of (a); r^4’Is R as described with reference to formulae I and II⁴(ii) a nucleophile of (a); m¹And M²Each independently selected from Si (R)¹⁸)₃Wherein each R¹⁸Independently selected from C₁-C₈Alkyl, or M¹And M²Each independently represents a counterion comprising a metal selected from the group consisting of Mg, Li, Mn, Cu, Zn, Al, Ti, Ln, and combinations thereof.

In accordance with the present invention, there is further provided a process for the preparation of fused ring indenopyran compounds represented by the following formulas X and X-2.

Formula X

Formula X-2

With reference to formulas X and X-2: ring A, ring B, m, n, R¹、R²、R³And R⁴Each as described herein before, e.g., with respect to the lactone compounds shown in formulas I and II. Alternatively, R¹、R²、R³And R⁴One or more of which are capable of independently representing in each case one or more precursors of groups as described above and as described herein with reference to, for example, formulae I, II, III and III-2.

The B and B' groups of formulae X and X-2 can each be independently selected from: unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, polyalkoxy, and polyalkoxy having a polymerizable group. Alternatively, B and B' of formulae X and X-2 can together form a ring structure selected from: fluoren-9-ylidene, substituted fluoren-9-ylidene, saturated spiro-monocyclic hydrocarbon rings, saturated spiro-bicyclic hydrocarbon rings, and spiro-tricyclic hydrocarbon rings.

A method of preparing fused ring indenopyran compounds of formulae X and X-2 comprising: converting the lactone compound of at least one of formula I and formula II to an acid intermediate comprising the acid intermediate represented by at least one of formulae IV and IV-2, each as previously described herein. The process further comprises converting the acid intermediate represented by formula IV and/or IV-2 to the corresponding fused ring indenol compound represented by formula III and/or III-2, as previously described herein.

The method of preparing the compound of formula X or X-2 further comprises reacting the fused ring indenol compound of at least one of formulas III and III-2 with propargyl alcohol of formula XI below.

Formula XI

Thereby producing a compound represented by the formula X and/or X-2. The B and B' groups of the propargyl alcohol of formula XI are each as described herein before for compounds of formula X or X-2. Alternatively, one or more of the B and B' groups of formula XI can independently represent in each case one or more precursors of those groups as described above and further as described herein for, for example, formula X or X-2.

Detailed Description

The term "actinic radiation" as used herein and in the claims means electromagnetic radiation capable of transforming a photochromic material from one form or state to another.

The term "photochromic" as used herein and in the claims means having at least a visible radiation absorption spectrum that changes at least in response to absorption of actinic radiation. Further, the term "photochromic material" as used herein denotes any substance adapted to exhibit photochromic properties, i.e. adapted to have at least a visible radiation absorption spectrum that changes at least in response to the absorption of actinic radiation and comprising at least one photochromic compound.

As used herein and in the claims, the description of a "linear or branched" group (e.g., a linear or branched alkyl group) is understood to include: methylene or methyl; linear radicals (e.g. linear C)₂-C₂₀Alkyl) and suitably branched groups (e.g. branched C)₃-C₂₀Alkyl groups).

The term "halo" and similar terms (e.g., halo, halogen, and halogen radicals) as used herein and in the claims denotes F, Cl, Br, and/or I, e.g., fluoro, chloro, bromo, and/or iodo.

Unless indicated to the contrary, all ranges or ratios disclosed herein are to be understood to encompass any and all subranges and sub-ratios subsumed therein. For example, a range or ratio stated to be "1-10" should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; i.e., all subranges or sub-ratios beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, such as, but not limited to: 1-6.1, 3.5-7.8 and 5.5-10.

The articles "a," "an," and "the" as used herein and in the claims include plural referents unless expressly and unequivocally limited to one referent otherwise.

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about".

Combinations of the foregoing and further described hereinVarious groups of the compounds and intermediates (including R of the lactone compounds of formulas I and II)¹、R²、R³And R⁴Groups) can be independently selected from hydrocarbyl and substituted hydrocarbyl in each instance.

The term "hydrocarbyl" and similar terms (e.g., "hydrocarbyl substituent" and "hydrocarbyl group") as used herein and in the claims means: linear or branched C₁-C₂₀Alkyl (e.g. linear or branched C)₁-C₁₀Alkyl), linear or branched C₂-C₂₀Alkenyl (e.g. linear or branched C)₂-C₁₀Alkenyl), linear or branched C₂-C₂₀Alkynyl (e.g. linear or branched C)₂-C₁₀Alkynyl), C₃-C₁₂Cycloalkyl (e.g. C)₃-C₁₀Cycloalkyl), C₃-C₁₂Heterocycloalkyl (having at least one heteroatom in the ring), C₅-C₁₈Aryl (including polycyclic aryl) (e.g. C)₅-C₁₀Aryl group), C₅-C₁₈Heteroaryl (having at least one heteroatom in the aromatic ring) and C₆-C₂₄Aralkyl (e.g. C)₆-C₁₀Aralkyl).

Representative alkyl groups include, but are not limited to: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl. Representative alkenyl groups include, but are not limited to: vinyl, allyl, and propenyl. Representative alkynyl groups include, but are not limited to: ethynyl, 1-propynyl, 2-propynyl, 1-butynyl and 2-butynyl. Representative cycloalkyl groups include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl substituents. Representative heterocycloalkyl groups include, but are not limited to: tetrahydrofuranyl, tetrahydropyranyl and piperidinyl. Representative aryl groups include, but are not limited to, phenyl and naphthyl. Representative heteroaryl groups include, but are not limited to, furyl, pyranyl, and pyridyl. Representative aralkyl groups include, but are not limited to, benzyl and phenethyl.

The term "substituted hydrocarbyl" as used herein and in the claims means a hydrocarbyl group whose at least one hydrogen is replaced with a non-hydrogen radical group (such as, but not limited to, a halogen radical, a hydroxyl radical, an ether radical, a thiol radical, a thioether radical, a carboxylic acid radical, a carboxylate radical, a phosphoric acid radical, a phosphate radical, a sulfonic acid radical, a sulfonate radical, a nitro radical, a cyano radical, a hydrocarbyl radical (such as an alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and aralkyl radical) and an amino radical (such as-N (R)₁₁’)(R₁₂') wherein R is₁₁' and R₁₂' are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, or R₁₁' and R₁₂Together form a ring optionally including at least one heteroatom (e.g., -O-and/or-S-)).

The term "substituted hydrocarbyl" includes halocarbyl (or halo-substituted hydrocarbyl) substituents. The term "halohydrocarbyl" and similar terms (e.g., halo-substituted hydrocarbyl) as used herein and in the claims means that at least one hydrogen atom of a hydrocarbyl group (e.g., alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and aralkyl) is substituted with a halogen atom selected from chlorine, bromine, fluorine, and iodine. The degree of halogenation can range from at least one hydrogen atom being substituted by a halogen atom (e.g., fluoromethyl) to fully halo (perhalo) (e.g., trifluoromethyl or perfluoromethyl) wherein all of the substitutable hydrogen atoms on the hydrocarbyl group are substituted by halogen atoms. Thus, the term "perhalogenated hydrocarbon group" as used herein and in the claims means a hydrocarbon group in which all the substitutable hydrogen atoms are substituted by halogen. Examples of perhalogenated hydrocarbon groups include, but are not limited to: perhalophenyl and perhaloalkyl.

Various radicals or substituents (e.g. R)¹、R²、R³And R⁴) The hydrocarbyl and substituted hydrocarbyl radicals which can each be selected from can in each case independently and optionally be substituted by-O-, -S-, -C (O) -, -C (O) O-, -S (O) -, -SO₂-、-N(R₁₁') -. As used herein and in the claims, substituted with-O-, -S-, -C (O) -, -C (O) O-, -S (O) -, -SO₂-、-N(R₁₁') -at least one interruption represents a hydrocarbon group or a substituentAt least one but not all of the carbons of the hydrocarbyl-substituted group are independently substituted in each instance by one of the divalent linking groups. The hydrocarbyl and substituted hydrocarbyl groups can be interrupted by two or more of the above linking groups, which can be adjacent to each other or separated by one or more carbons.

The expression "linear or branched" or "linear, branched or cyclic" group (e.g. linear or branched alkyl, or linear, branched or cyclic alkyl) as used herein and in the claims is understood herein to include: methylene or methyl; linear radicals (e.g. linear C)₂-C₂₅Alkyl), suitably branched groups (e.g. branched C)₃-C₂₅Alkyl) and a suitably cyclic group, e.g. C₃-C₂₅Cycloalkyl (or cyclic alkyl).

Each group (e.g., R) for the compounds and intermediates described herein (e.g., fused ring compounds of formulas I and II, fused ring indenol compounds of formulas III and III-2) herein and in the claims¹、R²、R³、R⁴The term "precursor" and related terms (e.g., "precursors") as used in connection with B and B') denote groups that can be converted in one or more steps to the final or desired group. As non-limiting examples: precursors of hydroxyl (-OH) groups include, but are not limited to: a carboxylate group (-OC (O) R, wherein R is hydrogen or an optionally substituted hydrocarbyl group); precursors of carboxylate groups (-OC (O) R) include, but are not limited to: a hydroxyl group (-OH), which can react, for example, with a carboxylic acid halide, such as acetic acid chloride (or acetyl chloride).

Unless indicated to the contrary, the left-to-right representation of a linking group (e.g., a divalent linking group) as used herein and in the claims encompasses other possible orientations, such as right-to-left orientations. As non-limiting examples: the left to right representation of a divalent linking group-C (O) O-includes the right to left representation thereof-O (O) C-.

The groups and substituents of the lactone compounds (e.g., as shown in formulas I and II), fused ring indenol compounds (e.g., as shown in formula III), fused ring indenopyran compounds (e.g., as shown in formula X), and compounds and intermediates used in their preparation are described in more detail below.

The a and B ring groups of the lactone compounds of formulas I and II can each independently be selected from unsubstituted aryl, substituted aryl, unsubstituted fused ring aryl, substituted fused ring aryl, unsubstituted heteroaryl, and substituted heteroaryl. The substituents of the substituted aryl, fused ring aryl and heteroaryl groups can each be independently selected from hydrocarbyl and substituted hydrocarbyl groups, each of which can be optionally substituted with-O-, -S-, -C (O) O-, -S (O) -, -SO₂-、-N(R₁₁') -, as previously described herein. Examples of aryl groups from which the a and B rings can each be independently selected include, but are not limited to, phenyl and biphenyl. Fused ring aryl groups from which the A and B rings can each be independently selected include, but are not limited to, polycyclic aromatic hydrocarbons such as naphthyl and anthracenyl. Examples of heteroaryl groups from which rings a and B can be independently selected include, but are not limited to, furyl, pyranyl, indolyl, thienyl, benzothienyl, and pyridyl.

For some embodiments of the invention, R for each m¹And R of each n²Independently selected from: reactive substituents, compatible substituents, halogen selected from iodine, bromine, fluorine and chlorine, C₁-C₂₀Alkyl radical, C₃-C₁₀Cycloalkyl, substituted or unsubstituted phenyl or-O-R₁₀' or-C (O) -R₁₀' OR-C (O) -OR₁₀', wherein R₁₀' is hydrogen, C₁-C₂₀Alkyl, phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkyl-substituted phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl (C)₁-C₂₀) Alkyl, (C)₁-C₂₀) Alkoxy (C)₂-C₂₀) Alkyl radical, C₃-C₁₀Cycloalkyl or mono (C)₁-C₂₀) Alkyl substituted C₃-C₁₀A cycloalkyl group. The phenyl substituent (i.e., substituent substituted for phenyl) can be selected from hydroxy, halogen, carbonyl, C₁-C₂₀Alkoxy radicalCarbonyl, cyano, halo (C)₁-C₂₀) Alkyl radical, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group.

For some further embodiments, R for each m¹And R of each n²Independently and more particularly in each case from: c₁-C₆Alkyl radical, C₃-C₇Cycloalkyl, substituted or unsubstituted phenyl, -O-R₁₀' or-OC (= O) R₁₀', wherein R₁₀' is hydrogen, C₁-C₆Alkyl, phenyl C₁-C₃Alkyl, mono C₁-C₆Alkyl-substituted phenyl C₁-C₃Alkyl, mono C₁-C₆Alkoxy-substituted phenyl C₁-C₃Alkyl radical, C₁-C₆Alkoxy radical C₂-C₄Alkyl radical, C₃-C₇Cycloalkyl or mono C₁-C₄Alkyl substituted C₃-C₇A cycloalkyl group. The phenyl substituent (i.e. substituent substituted for phenyl) can be more particularly selected from hydroxy, halogen, carbonyl, C₁-C₆Alkoxycarbonyl, cyano, halo (C)₁-C₆) Alkyl radical, C₁-C₆Alkyl or C₁-C₆An alkoxy group.

Alternatively or in addition to the foregoing classes and examples, R for each m¹And R of each n²Can be independently selected from: -N (R)₁₁’)R₁₂', wherein R₁₁' and R₁₂' independently of one another are hydrogen, C₁-C₂₀Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, C₁-C₂₀Alkylaryl group, C₃-C₁₀Cycloalkyl radical, C₄-C₂₀Bicycloalkyl radical, C₅-C₂₀Tricycloalkyl or C₁-C₂₀Alkoxyalkyl, wherein the aryl is phenyl or naphthyl; or R₁₁' and R₁₂' together with the nitrogen atom form C₃-C₂₀Hetero-bicycloalkyl ring or C₄-C₂₀A heterotricycloalkyl ring.

Further alternatively or in addition to the foregoing classes and examples, R for each m¹And R of each n²Can be independently selected from: nitrogen containing rings of the following scheme XIIA:

formula XIIA

For nitrogen ring substituents of formula XIIA, each-Y-is independently at each occurrence selected from: -CH₂-、-CH(R₁₃’)-、-C(R₁₃’)₂-, -CH (aryl) -, -C (aryl)₂-and-C (R)₁₃') (aryl) -; z is-Y-, -O-, -S (O) -, -SO₂-、-NH-、-N(R₁₃') -or-N (aryl) -, wherein each R is₁₃' independently is C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl groups); each aryl group is independently phenyl or naphthyl; m is an integer 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-.

Additionally or alternatively, R for each m¹And R of each n²And in each case independently from the nitrogen-containing ring substituents of the formula XIIB and/or of the formula XIIC:

formula XIIB formula XIIC

For nitrogen containing ring substituents of formulas XIIB and XIIC, R₁₅、R₁₆And R₁₇Each independently is hydrogen, C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl), phenyl or naphthyl, or the radical R₁₅And R₁₆Together form a ring of 5 to 8 carbon atoms; each R^dIndependently at each occurrence is selected from C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl group), C₁-C₂₀Alkoxy (e.g. C)₁-C₆Alkoxy), fluorine or chlorine; q is an integer of 0,1, 2 or 3.

Further alternatively or additionally, R for each m¹And R of each n²Can also be selected independently in each case from: unsubstituted, mono-or disubstituted C₄-C₁₈A spirobicyclic amine; or unsubstituted, mono-and disubstituted C₄-C₁₈Spirotricyclic amine wherein the substituents are independently aryl, C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl group), C₁-C₂₀Alkoxy (e.g. C)₁-C₆Alkoxy) or phenyl (C)₁-C₂₀) Alkyl (e.g. phenyl (C)₁-C₆) Alkyl groups).

For some embodiments of the invention, two adjacent R' s¹Group and/or two adjacent R²The groups can together form a group of formula xid or formula XIIE:

formula XIID formula XIIE

For the groups of the formulae XIID and XIIE, T and T' are each independently oxygen or a group-NR₁₁-, wherein R₁₁、R₁₅And R₁₆Each as described previously herein.

For some embodiments of the invention, R³And R⁴The groups can each be independently selected from: reactive substituent, compatible substituent, hydrogen, hydroxyl and C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl group), C₁-C₂₀Haloalkyl (e.g. C)₁-C₆Haloalkyl), C₃-C₁₀Cycloalkyl (e.g. C)₃-C₇Cycloalkyl), allyl, benzyl or monosubstituted benzyl. The benzyl substituent can be selected from halogen, C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl) or C₁-C₂₀Alkoxy (e.g. C)₁-C₆Alkoxy groups).

For some further embodiments of the invention, R³And R⁴The groups can each be independently selected from: unsubstituted, mono-, di-or tri-substituted radicals selected from phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl or indolyl. The substituent groups can in each case be independently selected from halogen, C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl) or C₁-C₂₀Alkoxy (e.g. C)₁-C₆Alkoxy groups).

For some embodiments of the invention, R³And R⁴The radicals can also each independently be chosen from monosubstituted phenyl radicals, where the phenyl radical has a substituent in its para position, which is a linking group- (CH)₂)_t-or-O- (CH)₂)_tLinked to an aryl group as part of one (or another) photochromic material (e.g., naphthopyran, indeno-fused naphthopyran, or benzopyran); t is selected from the integers 1,2, 3,4, 5 or 6.

Alternatively, R³And R⁴The radicals can each be independently selected from the group-CH (R)¹⁰) G, wherein R¹⁰Is hydrogen, C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl) or unsubstituted, mono-or disubstituted aryl, phenyl or naphthyl; g is-CH₂OR¹¹Wherein R is¹¹Is hydrogen, -C (O) R¹⁰、C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl group), C₁-C₂₀Alkoxy (C)₁-C₂₀) Alkyl (e.g. C)₁-C₃Alkoxy (C)₁-C₆) Alkyl), phenyl (C)₁-C₂₀) Alkyl (e.g. phenyl (C)₁-C₃) Alkyl), mono (C)₁-C₂₀) Alkoxy-substituted phenyl (C)₁-C₂₀) Alkyl (e.g. mono (C)₁-C₆) Alkoxy-substituted phenyl (C)₁-C₃) Alkyl) or an unsubstituted, mono-or di-substituted aryl group, such as phenyl or naphthyl. The substituents of phenyl and naphthyl can each be independently selected from C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl) or C₁-C₂₀Alkoxy (e.g. C)₁-C₆Alkoxy groups).

For some embodiments of the invention, R³And R⁴Can together form a spiro substituent selected from a substituted or unsubstituted spiro carbocyclic ring comprising 3 to 6 carbon atoms, a substituted or unsubstituted spiroheterocyclic ring comprising 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spiro carbon atom. The spiro carbocyclic ring and the spiro heterocyclic ring are each fused with 0,1 or 2 benzene rings. The substituents of the spiro ring can be selected from hydrogen or C₁-C₂₀Alkyl (e.g. C)₁-C₆Alkyl groups).

For some embodiments of the invention, R for each m¹And R of each n²Independently selected from unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl radical, C₃-C₇Cycloalkyl radical, C₁-C₈Haloalkyl, iodine, bromine, fluorine, chlorine and-O-R₁₀'. For a further embodiment of the invention, R³And R⁴Each independently selected from hydrogen and C₁-C₈Alkyl radical, C₁-C₈Haloalkyl and C₃-C₇Cycloalkyl, or R³And R⁴Together form a spiro substituent selected from substituted or unsubstituted spiro carbocycles containing 3 to 6 carbon atoms.

According to some further embodiments of the invention, R for each m¹And R of each n²Can be independently selected from the group represented by formula XIII below in each instance:

-(S₁)_c-(Q₁-(S₂)_d)_d’-(Q₂-(S₃)_e)_e’-(Q₃-(S₄)_f)_f’-S₅-P

formula XIII

For formula XIII, Q₁、Q₂And Q₃Each independently selected from the following divalent groups: unsubstituted or substituted aromatic groups, unsubstituted or substituted alicyclic groups, unsubstituted or substituted heterocyclic groups, and mixtures thereof.

Q₁、Q₂And Q₃Substituents each of which can be selected from substituted aromatic groups, substituted alicyclic groups, and substituted heterocyclic groups are independently selected from: a group represented by P (described in more detail herein), a liquid crystal mesogen, a halogen, a poly (C)₁-C₁₈Alkoxy group), C₁-C₁₈Alkoxycarbonyl group, C₁-C₁₈Alkylcarbonyl group, C₁-C₁₈Alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoro (C)₁-C₁₈) Alkoxy, perfluoro (C)₁-C₁₈) Alkoxycarbonyl, perfluoro (C)₁-C₁₈) Alkylcarbonyl, perfluoro (C)₁-C₁₈) Alkylamino, di (perfluoro (C)₁-C₁₈) Alkyl) amino, perfluoro (C)₁-C₁₈) Alkylthio radical, C₁-C₁₈Alkylthio radical, C₁-C₁₈Acetyl, C₃-C₁₀Cycloalkyl radical, C₃-C₁₀Cycloalkoxy, or mono-substituted with cyano, halogen or C₁-C₁₈Alkoxy or halogen-polysubstituted straight-chain or branched C₁-C₁₈An alkyl group.

Additionally or alternatively, Q₁、Q₂And Q₃Substituted aromatic group, substituted alicyclic group each of which can be selected fromThe substituents of the group and the substituted heterocyclic group can be selected from and can be further independently selected from the group represented by one of the following formulae XIIIA and XIIIB:

-M(T)_(t-1)M(OT)_(t-1)

formula XIIIA formula XIIIB

Referring to formulas XIIIA and XIIIB, M is selected from the group consisting of aluminum, antimony, tantalum, titanium, zirconium, and silicon; t is selected from the group consisting of organofunctional groups, organofunctional hydrocarbon groups, aliphatic hydrocarbon groups, and aromatic hydrocarbon groups; t is the valence of M.

Q₁、Q₂And Q₃Liquid crystal mesogens each of which can be independently selected include, but are not limited to, liquid crystal mesogens known in the art. For some embodiments, the liquid crystal mesogen can be selected from those described in U.S. patent application publication No. US2009/0323011a1, see [0052 ]]-[0095]Paragraph and table 1, the disclosure of which is incorporated herein by reference in its entirety.

With further reference to formula XIII, subscripts c, d, e, and f are each independently selected from integers ranging from 1 to 20, inclusive (e.g., from 2 to 15 or from 3 to 10).

S of formula XIII₁、S₂、S₃、S₄And S₅Each group is independently selected from spacer units. The spacing units can be independently selected in each case from: - (CH)₂)_g-、-(CF₂)_h-、-Si(CH₂)_g-、-(Si(CH₃)₂O)_h-, where g is independently selected at each occurrence from 1 to 20 and h is an integer from 1 to 16, inclusive. Alternatively or additionally, the spacer unit can be independently selected from-N (Z) -, -C (Z) = C (Z) -, -C (Z) = N-, -C (Z') -or a single bond, wherein Z is independently selected at each occurrence from hydrogen, C, or a single bond₁-C₁₈Alkyl radical, C₃-C₁₀Cycloalkyl and aryl, Z' being independently at each occurrence selected from C₁-C₁₈Alkyl radical, C₃-C₁₀Cycloalkyl groups and aryl groups. Further alternatively or additionally, the spacer units can be independently selected from-O-, -C (O)) -, -C.ident.C-, -N = N-, -S-, -S (O) -, -S (O) -, - (O) S (O) O-, -O (O) S (O) O-or linear or branched C₁-C₂₄An alkylene residue of₁-C₂₄The alkylene residue is unsubstituted, mono-substituted by cyano or halogen or poly-substituted by halogen.

Further reference is made to formula XIII: when two heteroatom-containing spacer units are linked together, the spacer units are linked such that the heteroatoms are not directly linked to each other; s₁And between ring A and ring S₁And each bond between the B rings being free of two heteroatoms bonded to each other, S₅And the linkage between P does not contain two heteroatoms attached to each other.

The P group of formula XIII is selected from: hydroxy, amino, C₂-C₁₈Alkenyl radical, C₂-C₁₈Alkynyl, azido, silyl, siloxy, silylhydride, (tetrahydro-2H-pyran-2-yl) oxy, thio, isocyanate, thioisocyanate, acryloxy, methacryloxy, 2- (acryloxy) ethylcarbamoyl, 2- (methacryloxy) ethylcarbamoyl, aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylic ester, acryloylamino, methacryloylamino, aminocarbonyl, C₁-C₁₈Alkylaminocarbonyl, aminocarbonyl (C)₁-C₁₈) Alkyl radical, C₁-C₁₈Alkoxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy (C)₁-C₁₈) Alkyl radical, C₁-C₁₈Alkyl radical, C₁-C₁₈Alkoxy, amino (C)₁-C₁₈) Alkyl radical, C₁-C₁₈Alkylamino radical, di (C)₁-C₁₈) Alkylamino radical, C₁-C₁₈Alkyl radical (C)₁-C₁₈) Alkoxy radical, C₁-C₁₈Alkoxy (C)₁-C₁₈) Alkoxy, nitro, poly (C)₁-C₁₈) Alkyl ether, (C)₁-C₁₈) Alkyl radical (C)₁-C₁₈) Alkoxy (C)₁-C₁₈) Alkyl, polyethyleneoxy, polypropyleneoxy, ethyleneGroup (C), acryloyl group, acryloyloxy group₁-C₁₈) Alkyl, methacryloyl, methacryloyloxy (C)₁-C₁₈) Alkyl, 2-chloropropenoyl, 2-phenylpropenoyl, acryloxyphenyl, 2-chloropropenoylamino, 2-phenylpropenoylaminocarbonyl, oxetanyl, glycidyl, cyano, isocyanato (C)₁-C₁₈) Alkyl, itaconate, vinyl ether, vinyl ester, styrene derivatives, main and side chain liquid crystalline polymers, siloxane derivatives, ethyleneimine derivatives, maleic acid derivatives, fumaric acid derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives substituted with at least one of methyl, methoxy, cyano, and halogen, or substituted or unsubstituted chiral or achiral monovalent and divalent groups selected from steroid groups, terpene groups, alkaloid groups, and mixtures thereof. The substituents of the groups from which P can be selected are independently selected from C₁-C₁₈Alkyl radical, C₁-C₁₈Alkoxy, amino, C₃-C₁₀Cycloalkyl radical, C₁-C₁₈Alkyl radical (C)₁-C₁₈) Alkoxy, fluoro (C)₁-C₁₈) Alkyl, cyano (C)₁-C₁₈) Alkyl, cyano (C)₁-C₁₈) Alkoxy groups or mixtures thereof. For some embodiments, P can be a structure having 2-4 reactive groups. For further embodiments, P can be an unsubstituted or substituted ring opening metathesis polymerization precursor.

With further reference to formula XIII, subscripts d ', e', and f 'are each independently selected from 0,1, 2, 3, and 4, provided that the sum of d' + e '+ f' is at least 1.

In some embodiments, the a and B rings of the lactone compounds represented by formulas I and II are each independently selected from substituted and unsubstituted aryl groups, such as substituted and unsubstituted phenyl groups. According to some embodiments of the invention, the lactone compound is selected from lactone compounds represented by at least one of formula Ia and formula IIa below:

formula Ia

Formula IIa

For formulae Ia and IIa, m, n, R¹、R²、R³And R⁴Each as described previously herein.

In some embodiments, the lactone compound of at least one of formula I and formula II can be prepared or formed by a process comprising: reacting an acid ester of at least one of formula VI and formula VII with a nucleophile of at least one of formula VIII and/or formula IX, as defined herein to include an organometallic hydride reducing agent, as previously described herein. The reaction for producing the lactone compound can be shown by the following scheme-1.

Scheme-1

For the process of the present invention capable of preparing lactone compounds, for example, as shown with reference to scheme-1, when R³And R⁴When each is hydrogen, a metal hydride reducing agent is generally used. In some embodiments, the metal hydride reducing agent can be selected from sodium borohydride and lithium aluminum hydride or organometallic hydride reducing agents. The organometallic hydride reducing agent can be one or more di (C)₁-C₂₀Alkyl) aluminium hydride reducing agents, e.g. one or more di (C)₁-C₆Alkyl) aluminum hydride reducing agents, such as diethylaluminum hydride and diisobutylaluminum hydride.

According to some embodiments of the invention, of formulae VIII and IXM¹And M²Also includes halogen, and can be represented by (M)¹X)⁺And (M)²X)⁺Wherein X is halogen. M of the formulae VIII and IX¹And M²Each can be selected from (MgX)⁺Wherein X is selected from halogens, e.g. Cl, Br and I, e.g. (MgCl)⁺、(MgBr)⁺And (MgI)⁺。

For some embodiments of the invention, the nucleophiles represented by formulas VIII and IX are each Grignard reagents and the reaction represented by scheme-1 is a Grignard reaction, which is carried out under Grignard reaction conditions. The reaction shown in scheme-1 is typically carried out in the presence of a suitable solvent, such as Tetrahydrofuran (THF), under atmospheric conditions (e.g., about 1atm) under an inert atmosphere (e.g., under a nitrogen purge) at, for example, -30 ℃ to 60 ℃ or-20 ℃ to 45 ℃ or-10 ℃ to 30 ℃, optionally under reflux.

The reaction of the acid ester of formula VI and/or VII with the nucleophile of formula VIII and/or IX can in some embodiments be carried out in the presence of a metal salt. Examples of metal salts that can be present include, but are not limited to, aluminum chloride (AlCl)₃) Tin chloride, zinc chloride, bismuth triflate, alkali metal halides, anhydrous alkali metal halides, rare earth metal salts (e.g., lanthanide halides, such as lanthanum III chloride and lanthanide triflate, and combinations thereof). Examples of alkali metal halides that can be present include, but are not limited to: sodium and/or potassium halides, for example sodium chloride (NaCl) and/or potassium chloride (KCl). Examples of alkali metal halides that can be present include, but are not limited to, anhydrous calcium halides, anhydrous lithium halides, and/or anhydrous magnesium halides, such as calcium chloride, lithium chloride, and magnesium chloride. The metal salt is typically present in an amount of from 0.1 mole% to 600 mole%, or from 1.0 to 100 mole%, or from 10 to 50 mole%, based on 100 mole% of the starting material. The mole percent is defined as the moles of metal salt per liter of solute based on the total moles of acid ester of formula VI and/or VII and nucleophile of formula VIII and IX per liter of solute in scheme-1.

When the method of the present invention comprises producing the lactone compound represented by formula Ia and/or IIa, the acid ester is represented by the following formulae VIa and VIIa.

And

formula VIa

VIIa。

The acid esters of formulae VI and VII can be prepared by suitable methods. For some embodiments of the invention, the acid esters of formulas VI and VII are prepared from the reaction between an A-ring B-ring ketone and a succinic diester, as shown in scheme-2 below.

Scheme-2

Referring to scheme-2, A Ring B Ring ketone (a) is reacted with succinic diester (B) in a strong base (e.g., alkali metal alkoxide, e.g., NaOR)¹⁶(e.g., sodium ethoxide)) in the presence of a base, wherein R is¹⁶As described previously herein (e.g., each R¹⁶Can be ethyl). The reaction of scheme-2 is carried out under suitable conditions, for example at the boiling temperature of the solvent under reflux, in an inert atmosphere in the presence of a suitable solvent, for example tetrahydrofuran or toluene. Details of the reaction are described in more detail in the examples.

The present invention also provides a method for preparing a fused ring indanol compound represented by at least one of formula III and formula III-2, as previously described herein. As previously described herein, the process comprises converting a lactone compound represented by at least one of formulas I and II to an acid intermediate comprising an acid intermediate represented by at least one of formula IV and formula IV-2, each as previously described herein. The conversion of the lactone compound is typically carried out in the presence of one or more metal salts (which include organometallic salts). For some embodiments, the metal salt is selected from:

(i)Bi⁽³⁺⁾(^-O-SO₂-R¹⁵)₃wherein R is¹⁵Selected from the group consisting of hydrocarbyl and halogenated hydrocarbyl (e.g., perhalogenated hydrocarbyl); and/or (ii) BiX₃Wherein each X is independently selected from halogen (e.g., F, Cl and Br). R of the metal organic salt¹⁵The groups are selected for some embodiments from perhalogenated hydrocarbyl groups, e.g., perhalogenated (C)₁-C₂₀) Alkyl radicals, e.g. including perfluoro (C)₁-C₆) Alkyl radicals, e.g. CF₃、-C₂F₅and-C₃F₇. The metal salt is typically present in an amount of, for example, 0.001 mole% to 50 mole%, or 0.01 to 30 mole%, or 0.1 to 20 mole%, based on 100 mole% of the starting material. In the conversion of a lactone of formula I and/or II to an acid intermediate of formula IV and/or IV-2, mole percent is defined herein as the mole percent of metal salt per liter of solute based on the total moles of lactone of formula I and/or II per liter of solute.

The conversion of the lactone compound of formula I or II to an acid intermediate (e.g., in the presence of a metal salt) results in the formation of an acid intermediate of formula IV and/or formula IV-2. Depending on factors including, but not limited to, the lactone compound present, the steric effect and/or the difference in electron abundance between the a and B rings of the lactone compound discussed herein below, the conversion can result in the production of an acid intermediate consisting of (e.g., consisting essentially of) an acid intermediate represented by, inter alia, formula IV or formula IV-2, or a combination or mixture of acid intermediates represented by formula IV or formula IV-2.

It should be noted that the conversion of the lactone compounds represented by the mixtures of formulas I and II can result in the formation of an acid intermediate consisting essentially or specifically of an acid intermediate represented by formula IV or formula IV-2 or a mixture of two acid intermediates.

Moreover, the conversion of the lactone compounds of formulas I and II can result in the formation of a combination or mixture of acid intermediates, as shown in scheme-3 below.

Scheme-3

Referring to scheme-3, the formation of a combination or mixture of acid intermediates IV and IV-2 is described. For some embodiments, acid intermediates IV and IV-2 can each be separated, and one or both of the separated acid intermediates can be further converted to the relevant indeno-fused compound. For example, further conversion of the acid intermediate of formula IV results in the formation of a compound of formula III; similarly, the conversion of the acid intermediate represented by formula IV-2 results in the formation of the compound represented by formula III-2.

Formula III

Formula III-2

For some embodiments of the invention, acid intermediates IV and IV-2 are not separated or isolated, and subsequent conversion thereof results in the formation of a combination or mixture of compounds represented by formulas III and III-2. Mixtures of the compounds of formulas III and III-2 can optionally be separated or isolated from each other, for example, prior to further reaction therewith (e.g., to form an indeno-fused pyran compound).

In accordance with the present invention, the conversion of a mixture of lactone compounds of formula I and II can result in the formation of a greater amount (i.e., a greater amount) of one acid intermediate than the other, i.e., a greater amount of the acid intermediate of formula IV than the acid intermediate of formula IV-2. For example, the conversion can result in at least 50 mole% (or at least 60 mole%, or at least 70 mole%, or at least 75 mole%, or at least 80 mole%) of the acid intermediate of formula IV based on the total moles of the acid intermediate of formula IV and the acid intermediate of formula IV-2. The acid intermediate of formula IV can be produced in an amount less than or equal to 100 mole% (or less than or equal to 95 mole%, or less than or equal to 90 mole%) based on the total moles of the acid intermediate of formula IV and the acid intermediate of acid IV-2. The amount of acid intermediate of formula IV produced can range between any combination of these upper and lower values (inclusive), e.g., 50 to 100 mole%, or 60 to 95 mole%, or 70 to 90 mole%, of the acid intermediate of formula IV, based on the total moles of the acid intermediate of formula IV and the acid intermediate of formula IV-2. In the same manner, the amount of the acid intermediate represented by the formula IV-2 can be more generated than the acid intermediate represented by the formula IV.

The conversion of a lactone compound comprising a mixture of lactone compounds of formula I and II to result in the production of a greater amount of one of the two acid intermediates of formula IV and formula IV-2 can be achieved, for example, based on steric effects and/or electron abundance between the a and B rings of the lactone compound. The selective transformation can also be performed in a process selected from Bi⁽³⁺⁾(^-O-SO₂-R¹⁵)₃And/or BiX₃In the presence of a metal salt of (a), each as herein before described.

The term "steric effect" as used herein and in the claims means and relates to the steric configuration of one ring compared to another ring (e.g., the a ring of a lactone compound compared to the B ring of a lactone compound) having a greater effect on the rate, nature, and extent of the reaction. For example, the size and shape of atoms and molecules, the geometry of bond angles, and the presence of substituents influence the progress of the reaction, as is known to those skilled in the art. Lactone compounds having a fluorine substituent at the 2-position of the B ring (e.g., examples 3 and 6) appear to contribute to steric hindrance of the B ring, making it less susceptible to participating in the reaction, resulting in the formation of more of the product of formula IV.

The term "electron abundance" as used herein and in the claims means and relates to the donor electron attached to the A and B rings when the A and B rings are the sameGroups and/or electron withdrawing groups (one or more R)¹And R²Group), type, number and position. Electron abundance is measured by Hammett Sigma values, which relates to the relative intensities of electron donating and electron withdrawing groups. The Hammett (sigma) value is a comparison of para (sigma) of benzene rings_p) Or meta (σ)_m) The relative measure of the electronic effect of a substituent in a position to the electronic effect of a hydrogen substituted at a para or meta position. Typically, for aromatic substituents, a generally negative sigma indicates that the group or substituent has an electron donating effect on the pi-electron system (i.e., an electron donating group), and a positive sigma indicates that the group or substituent has an electron withdrawing effect on the pi-electron system (i.e., an electron withdrawing group).

Without wishing to be bound by any theory, we believe that the effect of electron abundance on reaction selectivity is as follows: hammett (sigma.) of electron withdrawing or electron donating groups on the A and B rings of lactones_p) Or (sigma)_m) When the difference between the values is small, the selectivity is low. When the difference between these values is large, the selectivity is low. The reaction proceeds towards the A or B ring substituted with less electron withdrawing or more electron donating groups to give the corresponding acid intermediate of formula IV or IV-2.

In example 1, both rings a and B are benzene rings. The A ring has 3, 5-dibromo substitution. Hammett (sigma) of 5-bromo_p) The value was 0.23. Ring B has a 4-trifluoromethyl substituent. Hammett (sigma) of the 4-trifluoromethyl group_m) The value was 0.43. Whether the isomer of formula I or formula II is used as a starting material, the product of formula IV is preferentially produced because the B ring has less electron abundance than the a ring. In example 5, both ring a and ring B are benzene rings. Ring A has a 4-methoxy substituent. Hammett (sigma) of 4-methoxy_m) The value was 0.12. Ring B has a 3, 5-dichloro substituent. Hammett (sigma) of 5-chloro_p) The value was 0.23. Because the a ring has a greater electron abundance than the B ring, there is limited formation of the product shown in formula IV.

When the a and B rings are different, "electron abundance" is related not only to the substituents attached to the rings, but also to the electronic properties of the rings. In example 7, ring A is a thiophene ring and ring B is a benzene ring having a 4-fluoro substituent. Unshared pairs of electrons on the sulfur atom of the thiophene ring affect the reaction occurring on the a ring, thus limiting the formation of the product shown in formula IV.

Sigma of various substituents_pAnd σ_mA comparative list can be found in expanding QSAR, Hydrophobic, Electronic, and Steric Constants, C.Handch, A.Leo, and D.Hoekman, eds., public hedby The American Chemical Society, Washington, D.C.,1995, The disclosure of which is incorporated herein by reference. Examples of electron donors include, but are not limited to, amino, monoalkylamino, dialkylamino, morpholino, ethoxy, methoxy, p-aminophenyl, methyl, phenyl, and tolyl. Examples of electron withdrawing groups include, but are not limited to, halogen, perfluoroalkyl, and perfluoroalkoxy.

Furthermore, the conversion of the acid intermediate (e.g., of formula IV or IV-2) to formula III or III-2 can be carried out in two steps, wherein R is¹²Is hydrogen. An ester intermediate of formula V or formula V-2 is first formed, which is then reacted with a protic acid to form the corresponding compound of formula III or formula III-2, wherein R is¹²Is hydrogen as shown in scheme-4 and scheme-4-2 below.

Scheme-4

Referring to scheme-4, R of the indeno-fused ester intermediate product of formula V¹⁴The group is selected from-C (O) -R¹³and-S (O) R¹³Wherein R is¹³Independently selected from hydrocarbyl (e.g. C) in each occurrence₁-C₁₀Alkyl) and halogenated hydrocarbon groups (e.g. C)₁-C₁₀Perhaloalkyl).

Scheme-4-2

Referring to scheme-4-2, R of intermediate product represented by formula V-2¹⁴The group is selected from-C (O) -R¹³and-S (O) R¹³Wherein R is¹³Independently selected from hydrocarbyl (e.g. C) in each occurrence₁-C₁₀Alkyl) and halogenated hydrocarbon groups (e.g. C)₁-C₁₀Perhaloalkyl).

The first conversion or reaction of step- (a) of scheme-4 and scheme-4-2 is typically carried out in the presence of a material selected from the group consisting of carboxylic acid halides, carboxylic acid anhydrides, sulfonyl halides, sulfonyl anhydrides, and combinations thereof. The carboxylic acid halide, carboxylic acid anhydride, sulfonyl halide, and/or sulfonyl anhydride is generally present in an amount that is at least equimolar with respect to the amount of substituted acid intermediate (e.g., the acid intermediate of formula IV). The carboxylic acid halides which can be used in step (a) can be represented by the structure R^c-C (O) -X, wherein R^cSelected from hydrocarbyl or substituted hydrocarbyl; x is selected from halogen (e.g., Cl). The sulfonyl halide that can be used in step- (a) can be of the formula R^d(O) X, wherein R^dSelected from hydrocarbyl or substituted hydrocarbyl; x is selected from halogen (e.g., Cl). The carboxylic anhydride which can be used in step (a) can be of the formula R^e-C(O)-O-C(O)-R^fIn which R is^eAnd R^fEach independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl (e.g. halohydrocarbyl, e.g. C)₁-C₁₀Perhaloalkyl radicals, e.g. CF₃). The sulfonyl anhydride which can be used in step (a) can be of the formula R^g-S(O₂)-O-S(O₂)-R^hIn which R is^gAnd R^hEach independently selected from hydrocarbyl or substituted hydrocarbyl.

In step (b) of scheme-4 and scheme-4-2, the intermediates represented by formula V and formula V-2 are converted to formula III and formula III-2, respectively, (wherein R is¹²Is hydrogen) to the corresponding compound. The protic acid can be selected from the group consisting of hydrohalic acids (HX, where X is a halogen, e.g., HCl), sulfonic acids, phosphoric acids, and/or carboxylic acids. Examples of sulfonic acids include, but are not limited to, p-toluenesulfonic acid and dodecylbenzenesulfonic acid. Examples of phosphoric acid include, but are not limited to, phosphoric acid. Examples of carboxylic acids include, but are not limited to, oxalic acid and acetic acid. The base can be selected fromFrom sodium hydroxide and potassium hydroxide.

The protic acid or base can be present in excess relative to the amount of intermediate product, for example as shown in formula V. For example, the conversion of step- (b) can be carried out in the presence of concentrated hydrohalic acid (e.g., concentrated HCl), base (e.g., sodium hydroxide). The conversion of step- (b) is typically carried out in the presence of a solvent (e.g., methanol or a methanol/water mixture) under reflux conditions (e.g., at a temperature from 20 ℃ to the reflux temperature of the solvent, or from 25 ℃ to 90 ℃ or from 30 ℃ to 55 ℃) under atmospheric conditions (e.g., about 1atm) and under an inert atmosphere (e.g., a nitrogen purge).

Acid intermediates (e.g., of formula IV) to compounds of formula III (wherein R is¹²Is hydrogen) can be carried out essentially in one step in the presence of a protic acid. The protic acid can be selected from the group consisting of carboxylic acids, sulfonic acids, phosphoric acids, each of which can be selected from those species and examples previously described herein.

For the preparation of the compounds of formula III and formula III-2, the compounds and intermediates used and prepared therewith (e.g., the lactone compounds of formula I and II, the acid intermediates of formula IV and IV-2), the various groups and indices associated therewith (e.g., n, m, R¹、R²、R³And R⁴) Each as described previously herein. For some embodiments, for example, R for each m¹And R of each n²Independently selected from C in each occurrence₁-C₆Alkyl radical, C₃-C₇Cycloalkyl radical, C₁-C₈Haloalkyl, fluorine, iodine, bromine, chlorine and-O-R₁₀'. For other embodiments, R³And R⁴Each independently selected from hydrogen and C₁-C₈Alkyl radical, C₁-C₈Haloalkyl and C₃-C₇Cycloalkyl, or R³And R⁴Together form a spiro substituent selected from substituted or unsubstituted carbocyclic spiro rings containing 3 to 6 carbon atoms.

In accordance with some embodiments of the present invention, for the preparation of the compounds of formula III and formula III-2, each of ring a and ring B can be a benzene ring. For example, the compound represented by formula III can be represented by formula IIIa below, and the compound represented by formula III-2 can be represented by formula III-2a below.

Formula IIIa formula III-2a

For embodiments according to the invention wherein the compound is represented by formula IIIa and/or formula III-2a and the lactone compound is represented by formula Ia and IIa, as previously described herein, the acid intermediate can be represented by formula IVa and formula IV-2a below.

Formula IVa formula IV-2a

The invention further provides a process for the preparation of fused ring indenopyran compounds of formula X and formula X-2, as described herein before. The method includes converting a lactone compound selected from the group consisting of lactone compounds represented by formulas I and/or II to an acid intermediate comprising acid intermediates represented by formulas IV and IV-2 according to one or more embodiments previously described herein. In accordance with one or more embodiments described previously herein, the acid intermediates of formulas IV and IV-2 are converted to fused ring indenol compounds of formulas III and III-2. The fused ring indenol compound of formula III is then reacted with a propargyl alcohol of formula XI as previously described herein. The reaction is shown in scheme-5 below.

Scheme-5

Referring to scheme-5, a compound of formula III is reacted or coupled with a propargyl alcohol of formula XI in the presence of a catalytic amount of a protic acid, such as dodecylbenzenesulfonic acid (DBSA) or p-toluenesulfonic acid (pTSA), in the presence of a suitable solvent, such as a haloalkyl group (e.g., trichloromethane), in an inert atmosphere (e.g., nitrogen sweep) and at a temperature range from 0 ℃ to the boiling point of the solvent (e.g., 0 ℃ to 55 ℃ or 10 ℃ to 45 ℃ or 20 ℃ to 25 ℃).

A similar reaction of the compound of formula III-2 with propargyl alcohol (XI) results in the formation of a fused ring indenopyran compound represented by formula X-2 below.

Formula X-2

Respective subscripts and groups (e.g., m, n, R) associated with formulas III, XI, X and X-2¹、R²、R³、R⁴B and B') are as described herein before. The B and B' groups of, for example, formulas X, X-2 and XI are described in more detail below. More particularly, B and B' can each be independently selected from: aryl monosubstituted with a reactive substituent or a compatibilizing substituent; a substituted phenyl group; a substituted aryl group; substituted 9-julolidinyl; a substituted heteroaryl group selected from pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl. Phenyl, aryl, 9-julolidinyl or heteroaryl substituents are selected from: a reactive substituent R; unsubstituted, mono-, di-or tri-substituted phenyl or aryl; 9-julolidine or an unsubstituted, mono-substituted or di-substituted heteroaryl group selected from pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl.

The phenyl, aryl and heteroaryl substituents of the B and B' groups (i.e., the substituents of the substituted phenyl, aryl and heteroaryl groups) can each be independently selected from: a hydroxyl group; base ofgroup-C (= O) R₂₁Wherein R is₂₁is-OR₂₂、-N(R₂₃)R₂₄Piperidinyl or morpholinyl, wherein R₂₂Is allyl, C₁-C₂₀Alkyl, phenyl, mono (C)₁-C₂₀) Alkyl substituted phenyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl, phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkyl-substituted phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl (C)₁-C₂₀) Alkyl, (C)₁-C₂₀) Alkoxy (C)₂-C₂₀) Alkyl or C₁-C₂₀Haloalkyl, R₂₃And R₂₄Each independently is C₁-C₂₀Alkyl radical, C₅-C₁₀Cycloalkyl, phenyl or substituted phenyl, the phenyl substituent being C₁-C₂₀Alkyl or C₁-C₂₀Alkoxy, halo substituents are chloro, iodo, bromo or fluoro; an aryl group; mono (C)₁-C₂₀) An alkoxyaryl group; two (C)₁-C₂₀) An alkoxyaryl group; mono (C)₁-C₂₀) An alkylaryl group; two (C)₁-C₂₀) An alkylaryl group; a halogenated aryl group; c₃-C₁₀A cycloalkyl aryl group; c₃-C₁₀A cycloalkyl group; c₃-C₁₀A cycloalkoxy group; c₃-C₁₀Cycloalkoxy (C)₁-C₂₀) An alkyl group; c₃-C₁₀Cycloalkoxy (C)₁-C₂₀) An alkoxy group; aryl radical (C)₁-C₂₀) An alkyl group; aryl radical (C)₁-C₂₀) An alkoxy group; an aryloxy group; aryloxy radical (C)₁-C₂₀) An alkyl group; aryloxy radical (C)₁-C₂₀) An alkoxy group; mono or di (C)₁-C₂₀) Alkylaryl (C)₁-C₂₀) An alkyl group; mono or di (C)₁-C₂₀) Alkoxyaryl (C)₁-C₂₀) An alkyl group; mono or di (C)₁-C₂₀) Alkylaryl (C)₁-C₂₀) An alkoxy group; mono or di (C)₁-C₂₀) Alkoxyaryl (C)₁-C₂₀) Alkoxy radicalA group; an amino group; mono or di (C)₁-C₂₀) An alkylamino group; a diarylamino group; a piperazinyl group; n- (C)₁-C₂₀) An alkyl piperazinyl group; n-arylpiperazinyl; an aziridinyl group; an indolinyl group; a piperidinyl group; morpholinyl; a thiomorpholinyl group; a tetrahydroquinolyl group; tetrahydroisoquinolinyl; a pyrrolidinyl group; c₁-C₂₀An alkyl group; c₁-C₂₀A haloalkyl group; c₁-C₂₀An alkoxy group; mono (C)₁-C₂₀) Alkoxy (C)₁-C₂₀) An alkyl group; an acryloxy group; methacryloxy or halogen.

In some embodiments, the phenyl, aryl, and heteroaryl substituents of the B and B' groups (i.e., substituents that substitute for phenyl, aryl, and heteroaryl) can each be independently and more specifically selected from: a hydroxyl group; group-C (= O) R₂₁Wherein R is₂₁is-OR₂₂、-N(R₂₃)R₂₄Piperidinyl or morpholinyl, wherein R₂₂Is allyl, C₁-C₆Alkyl, phenyl, mono (C)₁-C₆) Alkyl substituted phenyl, mono (C)₁-C₆) Alkoxy-substituted phenyl, 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, (C)₁-C₆) Alkoxy (C)₂-C₄) Alkyl or C₁-C₆Haloalkyl, R₂₃And R₂₄Each independently is C₁-C₆Alkyl radical, C₅-C₇Cycloalkyl, phenyl or substituted phenyl, the phenyl substituent being C₁-C₆Alkyl or C₁-C₆Alkoxy, halo substituents are chloro, iodo, bromo or fluoro; an aryl group; mono (C)₁-C₁₂) An alkoxyaryl group; two (C)₁-C₁₂) An alkoxyaryl group; mono (C)₁-C₁₂) An alkylaryl group; two (C)₁-C₁₂) An alkylaryl group; a halogenated aryl group; c₃-C₇A cycloalkyl aryl group; c₃-C₇Cycloalkyl radicals；C₃-C₇A cycloalkoxy group; c₃-C₇Cycloalkoxy (C)₁-C₁₂) An alkyl group; c₃-C₇Cycloalkoxy (C)₁-C₁₂) An alkoxy group; aryl radical (C)₁-C₁₂) An alkyl group; aryl radical (C)₁-C₁₂) An alkoxy group; an aryloxy group; aryloxy radical (C)₁-C₁₂) An alkyl group; aryloxy radical (C)₁-C₁₂) An alkoxy group; mono or di (C)₁-C₁₂) Alkylaryl (C)₁-C₁₂) An alkyl group; mono or di (C)₁-C₁₂) Alkoxyaryl (C)₁-C₁₂) An alkyl group; mono or di (C)₁-C₁₂) Alkylaryl (C)₁-C₁₂) An alkoxy group; mono or di (C)₁-C₁₂) Alkoxyaryl (C)₁-C₁₂) An alkoxy group; an amino group; mono or di (C)₁-C₁₂) An alkylamino group; a diarylamino group; a piperazinyl group; n- (C)₁-C₁₂) An alkyl piperazinyl group; n-arylpiperazinyl; an aziridinyl group; an indolinyl group; a piperidinyl group; morpholinyl; a thiomorpholinyl group; a tetrahydroquinolyl group; tetrahydroisoquinolinyl; a pyrrolidinyl group; c₁-C₁₂An alkyl group; c₁-C₁₂A haloalkyl group; c₁-C₁₂An alkoxy group; mono (C)₁-C₁₂) Alkoxy (C)₁-C₁₂) An alkyl group; an acryloxy group; methacryloxy or halogen.

The B and B' radicals can also each independently be an unsubstituted or monosubstituted radical from the group consisting of pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, the substituents each being C₁-C₂₀Alkyl (e.g. C)₁-C₁₂Alkyl group), C₁-C₂₀Alkoxy (e.g. C)₁-C₁₂Alkoxy), phenyl or halogen.

Furthermore, the B and B' groups can each be independently selected from the group represented by the following general formulae XIVA and XIVB:

formula XIVA formula XIVB

Independently of each of the formulae XIVA and XIVB, K is-CH₂-or-O-; m is-O-or substituted nitrogen, with the proviso that when M is substituted nitrogen, K is-CH₂-is ready to use; the substituent of the substituted nitrogen being hydrogen, C₁-C₂₀Alkyl or C₁-C₂₀An aryl group; each R₂₅Independently at each occurrence is selected from C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, hydroxy and halogen; r₂₆And R₂₇Each independently is hydrogen or C₁-C₂₀An alkyl group; u is an integer in the range of 0-2.

Each B and B' group can independently be a group of the formula XV:

formula XV

For the group of formula XV, R₂₈Is hydrogen or C₁-C₁₂An alkyl group; r₂₉Is an unsubstituted, mono-or di-substituted radical selected from the group consisting of naphthyl, phenyl, furyl and thienyl. The substituents of the mono-or disubstituted naphthyl, phenyl, furyl and thienyl are in each case independently selected from C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy or halogen.

The B and B' groups can together form a ring selected from: fluoren-9-ylidene, mono-substituted fluoren-9-ylidene or di-substituted fluoren-9-ylidene. The substituents of the substituted fluoren-9-ylidene and disubstituted fluoren-9-ylidene can in each case be selected independently from C₁-C₂₀Alkyl (e.g. C)₁-C₁₂Alkyl group), C₁-C₂₀Alkoxy (e.g. C)₁-C₁₂Alkoxy) or halogen.

For some embodiments of the invention, further reference is made to the indeno-fused pyrans represented by formula X, R for each m¹And R of each n²Independently selected from C in each occurrence₁-C₆Alkyl radical, C₃-C₇Cycloalkyl radical, C₁-C₈Haloalkyl, fluorine, chlorine, iodine, bromine and-O-R₁₀’；R³And R⁴Each independently selected from hydrogen and C₁-C₈Alkyl radical, C₁-C₈Haloalkyl and C₃-C₇A cycloalkyl group; or together form a spiro substituent selected from a substituted or unsubstituted spiro carbocyclic ring comprising 3 to 6 carbon atoms; b and B' are each independently selected from C₁-C₆Aryl of alkoxy and aryl substituted with morpholinyl.

For some embodiments of the invention, ring A and ring B can each be a benzene ring, in which case the fused ring indenopyran of formula X can be represented by formula Xa and the fused ring indenopyran of formula X-2 can be represented by the following formula X-2 a.

Formula Xa formula X-2a

For some embodiments of the present invention, B and B' can each be independently selected from polyalkoxy groups and polyalkoxy groups having polymerizable groups. The polyalkoxy group from which B and B' can each be independently selected and the polyalkoxy group having a polymerizable group can be represented by the following formulae XXV and XXVI:

-Z[(OC₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]Z’

formula XXV

-[(OC₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]Z’

Formula XXVI

For formulas XXV and XXVI, -Z is selected from-C (O) -or-CH₂-; z' is selected from C₁-C₃Alkoxy or polymerizable groups. The term "polymerizable group" as used herein and in the claims means any functional group capable of participating in a polymerization reaction.

For some embodiments, polymerization of the polymerizable indeno-fused naphthopyrans can be carried out by a mechanism described in connection with the definition of "polymerization" in Hawley's condensed Chemical Dictionary, third Edition,1997, John Wiley & Sons, pages 901-902. These mechanisms include: "addition", in which a free radical is an initiator which reacts with the ethylenically unsaturated double bond of the monomer by being added thereto on the one hand while generating new free electrons on the other hand; "condensation" includes by separating a component (e.g., a water molecule) into two reactive monomers; and so-called "oxidative coupling".

Examples of polymerizable groups include, but are not limited to: hydroxyl, thiol, isocyanate, oxirane (e.g., oxiranylmethyl), free-radically polymerizable ethylenically unsaturated groups, allyl, (meth) acryloyl, and 2- (methacryloyl) ethylcarbamoyl. When two or more polymerizable groups are present on the naphthopyran, they can be the same or different.

For some embodiments, and with further reference to formulae XXV and XXVI: group- (OC)₂H₄)_x-can represent polyoxyethylene; group- (OC)₃H₆)_y-can represent polyoxypropylene; group- (OC)₄H₈)_z-can represent polyoxybutylene. When used in combination, the polyoxyethylene, polyoxypropylene and polyoxybutylene groups of formulas XXV and XXVI can be in random or block order within the polyalkoxy moiety. The subscript letters x, y and z of formulas XXV and XXVI are each independently a number between 0 and 50, and the sum of x, y and z is from 2 to 50. The sum of x, y and z can be any number falling within the range of 2-50 (e.g., 2, 3,4, … …, 50). The sum can also be in the range of 2-50Ranging from any smaller value to any larger value (e.g., 6-50, 31-50). The values of x, y and z are all averages and can be fractional (e.g., 9.5).

As previously mentioned, some groups (e.g., R) of the various compounds and intermediates described herein¹、R²、R³、R⁴B and B' groups) can each be independently selected from or include at least one reactive substituent and/or compatible substituent. If each of the compounds and/or intermediates described previously herein (e.g., the indeno-fused compound of formula III and/or the indeno-fused pyran compound of formula X) includes multiple reactive substituents and/or multiple compatible substituents, each reactive substituent and each compatible substituent can be independently selected.

The reactive substituent and the compatibilizing group can each independently be represented in each instance by one of the following:

A’-D-E-G-J(XVI)；-G-E-G-J(XIX)；-D-E-G-J(XXII)；

-A’-D-J(XVII)；-D-G-J(XX)；-D-J(XXIII)；

-a' -G-j (xviii); -G-j (xxi); and-A' -J (XXIV).

For formulas (XVI) - (XXIV), non-limiting examples of groups that, -A' -can represent, in accordance with the various non-limiting embodiments disclosed herein, include-O-, -C (= O) -, -CH₂-, -OC (= O) -, and-NHC (= O) -, provided that if-a '-represents-O-, then-a' -forms at least one bond with-J.

According to various non-limiting embodiments, non-limiting examples of groups that-D-can represent include: a diamine residue or derivative thereof, wherein a first amino nitrogen of the diamine residue is capable of bonding to-A' -or a substituent or vacant position on the compound (e.g., indeno-fused naphthol or indeno-fused naphthopyran) and a second amino nitrogen of the diamine residue is capable of bonding to-E-, -G-, or-J; and an aminoalcohol residue or derivative thereof, wherein the amino nitrogen of the aminoalcohol residue is capable of bonding to a substituent or a vacant position on-A' -or the compound (e.g., indeno-fused naphthol or indeno-fused naphthopyran) and the alcohol oxygen of the aminoalcohol residue is capable of bonding to-E-, -G-or-J. Alternatively, in accordance with various non-limiting embodiments disclosed herein, the amino nitrogen of the amino alcohol residue can be bonded to-E-, -G-, or-J, and the alcohol oxygen of the amino alcohol residue can be bonded to a substituent or a vacant position on-A' -or the compound (e.g., an indeno-fused compound or an indeno-fused pyran compound).

Non-limiting examples of suitable diamine residues that can be represented by-D-include aliphatic diamine residues, cycloaliphatic diamine residues, diazacycloalkane residues, azacyclaliphatic amine residues, diazacrown ether residues and aromatic diamine residues. Specific non-limiting examples of diamine residues that can be used in conjunction with the non-limiting embodiments disclosed herein include the following:

non-limiting examples of suitable amino alcohol residues that can be represented by-D-include aliphatic amino alcohol residues, cycloaliphatic amino alcohol residues, azacyclo aliphatic alcohol residues, diazacycloaliphatic alcohol residues and aromatic amino alcohol residues. Specific non-limiting examples of amino alcohol residues that can be used in conjunction with the non-limiting embodiments disclosed herein include the following:

with continued reference to formulas (XVI) - (XXIV) above, in accordance with various non-limiting embodiments disclosed herein, -E-can represent a dicarboxylic acid residue or derivative thereof, wherein a first carboxyl group of the dicarboxylic acid residue can be bonded to-G-or-D-and a second carboxyl group of the dicarboxylic acid residue can be bonded to-G-. Non-limiting examples of suitable dicarboxylic acid residues that can be represented by-E-include aliphatic dicarboxylic acid residues, cycloaliphatic dicarboxylic acid residues, and aromatic dicarboxylic acid residues. Specific non-limiting examples of dicarboxylic acid residues that can be used in conjunction with the non-limiting embodiments disclosed herein include the following:

in accordance with various non-limiting embodiments disclosed herein, -G-can represent: group- [ (OC)₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]-O-, wherein x, y and z are each independently selected from the range of 0 to 50, the sum of x, y and z being in the range of 1 to 50; a polyol residue or derivative thereof, wherein a first polyol oxygen of the polyol residue is capable of bonding to-A' -, -D-, -E-, or a substituent or free position on the indeno-fused naphthopyran; the second polyol oxygen of the polyol can be bonded to-E-or-J-or a combination thereof, wherein the first polyol oxygen of the polyol residue is bonded to the group- [ (OC)₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]Bonding (i.e. formation of the group- [ (OC)₂H₄)_x(OC₃H₆)_y(OC₄H₈)_z]-O-), the second polyol oxygen is bonded to-E-or-J-. Non-limiting examples of suitable polyol residues that can be represented by-G-include aliphatic polyol residues, cycloaliphatic polyol residues, and aromatic polyol residues.

More particularly, in accordance with various non-limiting embodiments disclosed herein, illustrative, non-limiting examples of polyols capable of forming-G-capable polyol residues include: (a) low molecular weight polyols having an average molecular weight of less than 500, such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028 at column 4, lines 48-50 and column 4, line 55 to column 6, line 5, the disclosure of which is hereby expressly incorporated herein by reference; (b) polyester polyols such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028, column 5, lines 7-33, the disclosure of which is hereby expressly incorporated herein by reference; (c) polyether polyols, such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028, column 5, lines 34-50, the disclosure of which is hereby incorporated by reference herein; (d) amide-containing polyols such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028, column 5, lines 51-62, the disclosure of which is hereby expressly incorporated herein by reference; (e) epoxy-based polyols such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028, column 5, line 63 through column 6, line 3, the disclosure of which is hereby expressly incorporated herein by reference; (f) polyhydroxy polyvinyl alcohols, such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028, column 6, lines 4-12, the disclosure of which is hereby expressly incorporated herein by reference; (g) urethane polyols such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028, column 6, lines 13-43, the disclosure of which is hereby expressly incorporated herein by reference; (h) polyacrylic polyols, such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028, column 6, line 43 to column 7, line 40, the disclosure of which is hereby expressly incorporated herein by reference; (i) polycarbonate polyols such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028, column 7, lines 41-55, the disclosure of which is hereby expressly incorporated herein by reference; and (j) mixtures of these polyols.

With further reference to formulae (XVI) - (XXIV), -J can represent a group-K in accordance with various non-limiting embodiments disclosed herein, wherein-K represents, for example and without limitation, the following groups: -CH₂COOH、-CH(CH₃)COOH、-C(O)(CH₂)_wCOOH、-C₆H₄SO₃H、-C₅H₁₀SO₃H、-C₄H₈SO₃H、-C₃H₆SO₃H、-C₂H₄SO₃H and-SO₃H, wherein "w" is in the range of 1-18. According to other non-limiting embodiments, -J can represent hydrogen, which bonds to the oxygen or nitrogen of the linking group to form a reactive moiety such as-OH or-NH. For example, according to various non-limiting embodiments disclosed herein, -J can represent hydrogen, provided that if-J represents hydrogen, -J is bonded to the oxygen of-D-or-G-or the nitrogen of-D-)And (4) finishing.

According to a further non-limiting embodiment, -J can represent a group-L or a residue thereof, wherein-L can represent an active moiety. For example, in accordance with various non-limiting embodiments disclosed herein, -L can represent, for example and without limitation, the following groups: acryl, methacryl, crotyl, 2- (methacryl) ethylcarbamoyl, 2- (methacryl) ethoxycarbamoyl, 4-vinylphenyl, vinyl, 1-chloroethenyl or epoxy. The terms acrylyl, methacrylyl, crotyl, 2- (methacrylyl) ethylcarbamoyl, 2- (methacrylyl) ethoxycarbamoyl, 4-vinylphenyl, vinyl, 1-chloroethenyl and epoxy as used herein represent the following structures:

as previously mentioned, -G-can represent the residue of a polyol, which is defined herein as including hydroxyl-containing carbohydrates, such as those set forth in U.S. patent No. 6,555,028 at column 7, line 56 to column 8, line 17, the disclosure of which is hereby expressly incorporated herein by reference. The polyol residue is formed, for example and without limitation, by reacting one or more polyol hydroxyl groups with a precursor of-A' (e.g., a carboxylic acid or a methylene dihalide), a polyalkoxylated group (e.g., a polyalkylene glycol), or a hydroxyl substituent of an indeno-fused naphthopyran. The polyol can be represented by q- (OH)_aThe residue of the polyol can be represented by the formula-O-q- (OH)_a-1Wherein q is the backbone of the polyol; "a" is at least 2.

Further, as previously described, one or more of the polyol oxygens of-G-can form a bond with-J (i.e., form the group-G-J). For example, although not limiting herein, wherein the reactive and/or compatible substituent comprises a group-G-J, if-G-represents a polyol residue, -J represents a group-K comprising a carboxyl end group, then-G-J is capable of reacting through one or more hydroxyl groups of the polyol to form the group-K (e.g., -G-J) is capable of reacting through one or more hydroxyl groups of the polyol to form the group-KAs discussed for reactions B and C at column 13, line 22 to column 16, line 15 of U.S. patent No. 6,555,028, the disclosure of which is hereby expressly incorporated herein by reference) to produce carboxylated polyol residues. Alternatively, if-J represents a-K group containing a sulfo or sulfonyl end group, although not limited thereto, -G-J can be prepared by reacting with HOC, respectively₆H₄SO₃H、HOC₅H₁₀SO₃H、HOC₄H₈SO₃H、HOC₃H₆SO₃H、HOC₂H₄SO₃H or H₂SO₄Acid condensation of one or more polyol hydroxyl groups. Further, although not limited thereto, if-G-represents a polyol residue and-J represents a group-L selected from the group consisting of an acryl group, a methacryl group, a 2- (methacryloyl) ethylcarbamoyl group and an epoxy group, then-L can be added by condensing the polyol residue with acryloyl chloride, methacryloyl chloride, 2-isocyanatoethylmethacrylate or epichlorohydrin, respectively.

The indeno-fused pyran compounds (e.g., indeno-fused naphthopyrans) prepared by the methods of the present invention can be used to impart photochromic properties to compositions and/or articles. Examples of articles that the indeno-fused pyran compounds of the present invention are capable of making photochromic include, but are not limited to: an optical element, a display, a window (or a patterned window), a mirror, and a liquid crystal cell. The term "optical" as used herein means relating to or relating to light and/or vision. Examples of optical elements that can become photochromic include, but are not limited to: ophthalmic elements, display elements, windows, mirrors, and liquid crystal cell elements. The term "ophthalmic" as used herein means relating to or relating to the eye and vision. Non-limiting examples of ophthalmic elements include corrective and non-corrective lenses, including mono-vision 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) and other elements for correcting, protecting, or enhancing (cosmetic or other) vision, including, but not limited to, magnifying lenses, protective lenses, goggles, and lenses for optical instruments (such as cameras and telescopes). The term "display" as used herein means a visual or machine-readable representation of information in the form of words, values, symbols, designs or patterns. Non-limiting examples of display elements include screens, monitors, and security elements (e.g., security markers). The term "window" as used herein means an opening adapted to transmit radiation therethrough. Non-limiting examples of windows include transparencies for automobiles and aircraft, windshields, filters, shutters, and optical switches. The term "mirror" as used herein means a surface that specularly reflects a substantial portion of incident light. The term "liquid crystal cell" as used herein denotes a structure comprising a liquid crystal material capable of ordering. One non-limiting example of a liquid crystal cell is a liquid crystal display.

The indeno-fused pyran compounds of the present invention are capable of imparting photochromic properties to articles by processes including, but not limited to, imbibition processes, cast-in-place processes, coating processes, in-mold coating processes, top molding processes, and lamination processes. For imbibition methods, the indeno-fused pyran compound is typically diffused into the polymeric material of a previously formed or prepared article (e.g., a substrate or a pre-applied coating or film). Imbibing can be performed with or without heating by immersing a preformed or prepared article in a solution containing the indeno-fused pyran compound. The indeno-fused pyran compound can then, although not necessarily, be combined with a polymeric material, such as a polymeric material of a substrate or coating.

For the cast-in-place process, the indeno-fused pyran compound can be mixed with the polymer and/or oligomer composition in solution or melt form or the monomer composition in liquid form to form a castable photochromic composition. The castable photochromic composition is then typically introduced into the cavity of a mold (e.g., a lens mold). The castable photochromic composition is then solid stated (e.g., cured) within the mold to form the photochromic article.

For articles comprising a substrate, the fused ring indenopyran compounds of the present invention can be combined with at least a portion of the substrate as part of a coating that is bonded to at least a portion of the substrate. The matrix can be a polymer matrix or an inorganic matrix (such as, but not limited to, a glass matrix). The fused ring indenopyran compounds of the present invention can be incorporated into at least a portion of a coating composition prior to applying the coating composition to a substrate. Alternatively, the coating composition can be applied to a substrate, at least partially solid stated, and then the fused ring indenopyran compound of the present invention can be impregnated into at least a portion of the coating. The term "solid stating" as used herein includes, but is not limited to: curing, polymerization, crosslinking, cooling and drying.

Photochromic articles can be prepared using the fused ring indenopyran compounds of the present invention by in-mold coating (or in-mold casting) methods known in the art. For the in-mold coating process, a photochromic coating composition comprising the fused ring indenopyran compound of the present invention, which can be a liquid coating composition or a powdered coating composition, is applied to at least a portion of the interior surface of the mold and then at least partially solid stated. A polymer solution or melt or oligomer or monomer solution or mixture is then poured or molded into the mold cavity and contacted with the previously applied photochromic coating composition and at least partially solid stated. The resulting photochromic article is then removed from the mold. Non-limiting examples of coating powders that can use fused ring indenopyran compounds according to various non-limiting embodiments disclosed herein are provided in U.S. Pat. No. 6,068,797 at column 7, line 50 to column 19, line 42, the disclosure of which is hereby expressly incorporated herein by reference.

Photochromic articles prepared using the fused ring indenopyran compounds of the present invention can also be prepared by top molding methods known in the art. The top molding process generally involves forming a substrate within a mold, then forming an interior space between the substrate and the interior surface of the mold, then introducing (e.g., injecting) the photochromic coating composition therein and then curing (e.g., curing). Alternatively, the top-molding process can include introducing a pre-prepared substrate into a mold such that an interior space is defined between the substrate and the mold interior surface, and then introducing (e.g., injecting) a photochromic coating composition into the interior space.

Photochromic articles prepared using the fused ring indenopyran compounds prepared by the process of the present invention can also be made by lamination processes known in the art. For lamination processes, a film comprising the fused ring indenopyran compounds of the present invention can be adhered or otherwise bonded to a portion of the substrate with or without the use of an adhesive and/or the application of heat and pressure. However, if desired, a second substrate can be applied over the first substrate, and the two substrates can be laminated together (e.g., by application of heat and pressure) to form an element in which the fused ring indenopyran compound is interposed between the two substrates. Methods of forming thin films comprising photochromic materials can include, for example and without limitation: combining a photochromic material with a polymeric or oligomeric solution or mixture; casting or extruding a film therefrom; and, if desired, at least partially solid stating the film. Additionally or alternatively, a thin film (with or without a photochromic material) can be formed and impregnated with the photochromic material.

The fused ring indenopyran compounds prepared by the process of the present invention can be used alone or in combination with other photochromic materials. Classes of photochromic materials that can be used in combination (e.g., in a mixture) with the fused ring indenopyran compounds of the present invention include, but are not limited to: spiro (indoline) phenoxazines and spiro (indoline) benzoxazines, for example as described in U.S. patent nos. 3,562,172, 3,578,602, 4,215,010, 4,342,668, 5,405,958, 4,637,698, 4,931,219, 4,816,584, 4,880,667 and 4,818,096; benzopyrans, such as described in U.S. Pat. nos. 3,567,605, 4,826,977, 5,066,818, 4,826,977, 5,066,818, 5,466,398, 5,384,077, 5,238,931, and 5,274,132; photochromic organometallic dithiozonates, such as (arylnitrogen) -thioformic arylhydrazidates, e.g., mercurius dithiozonate, such as described in U.S. Pat. No. 3,361,706; and fulgides and fulgimides, such as the 3-furyl and 3-thienyl fulgides and fulgimides described in U.S. Pat. No. 4,931,220 at column 20, line 5 to column 21, line 38.

Examples

In the first part of the examples, the synthetic procedures used to prepare the lactones of examples 1-8, the naphthol of example 7B and the photochromic materials of examples 1A-6A. Section 2 describes the photochromic performance tests and results of the photochromic compounds of examples 1A-6A.

Part 1: synthesis of the lactones of examples 1-8, the naphthol of example 7B and the photochromic materials of examples 1A-6A

Example 1

Step 1

A2L flask with tribromobenzene (100g) and a magnetic stir bar was dried in a vacuum oven at 80 ℃ for 4 hours. Dry THF (500ml) was added. The resulting mixture was placed in a NaCl saturated ice bath. 3M isopropyl magnesium chloride (160mL) was added dropwise to the solution at a rate that controlled the internal temperature to-20 ℃ to 0 ℃. The addition is completed in about 30 minutes to 1 hour. The mixture was stirred at the same temperature for half an hour, and bis [2- (N, N-dimethylamino) ethyl ] ether (61g) was slowly added over a period of 5 minutes to form a large amount of precipitate. The resulting mixture was stirred for 20 minutes and a mixture of 4-trifluoromethylbenzoyl chloride (73g) and THF (100mL) was added over a period of 5 minutes. The resulting mixture was stirred overnight. Water (100mL) was added slowly and the pH adjusted to 2 with 3N HCl. The resulting organic layer was collected with a separatory funnel, washed with 5% NaOH/water and NaCl/water, dried and concentrated. Methanol (300mL) was added to the recovered oil and the product crystallized. The product was collected by vacuum filtration. NMR showed that the resulting white crystals (87g) had a structure consistent with that of 3, 5-dibromo-4' -trifluoromethylbenzophenone.

Step 2

The product of step 1 (75g), dimethyl succinate (32.2g) and toluene (800ml) were placed in a three-necked 5L flask equipped with a mechanical stirrer. Potassium tert-butoxide (22.6g) was added portionwise over a period of 30 minutes. An exothermic reaction was observed with the formation of a large amount of precipitate. After 2 hours, water (500mL) was added. The pH of the mixture was adjusted to about 2 with 3N HCl. After stirring at room temperature for 10 minutes, the resulting organic layer was collected, washed with NaCl/water and dried over MgSO 4. After concentration, hexane was added to yield white crystals. The crystals were collected by vacuum filtration. NMR showed the resulting product (62 g) to have a structure consistent with (E) -4- (3, 5-dibromophenyl) -3- (methoxycarbonyl) -4- (4- (trifluoromethyl) phenyl) but-3-enoic acid. This procedure was repeated to prepare more product for the next step.

Step 3

The anhydrous lanthanum (III) chloride solid (100g) was ground to a very fine powder and then mixed with lithium chloride (52g) and dry THF (1 liter) in a 5 liter three-neck flask equipped with a mechanical stirrer and a dropping funnel. The mixture was refluxed for several hours until it dissolved. The product of step 2 was dissolved in the mixture. The mixture was then cooled to-15 ℃. A solution of 3M methyl magnesium chloride (238mL) was added to the dropping funnel. The first 30% portion of Grignard was slowly added to the mixture. The formation of bubbles and an increase in the temperature of the mixture were observed. The remainder of the Grignard was added to the mixture over 2 minutes while the temperature returned to-15 ℃. After 30 minutes, water (1L) was slowly added to the mixture and the pH was adjusted to acidic using acetic acid. The mixture became clear and two layers were formed. The aqueous layer was drained off. The recovered organic layer was washed 4 times with NaCl/water and then concentrated to dryness. A slightly yellowish solid was recovered and dissolved in toluene. The solution was filtered using a gel plug column and the recovered clear solution was concentrated to dryness. The product was obtained as a white solid and used in the next step without further purification. A portion of the product was recrystallized from methanol and NMR showed the purified crystals to have a structure consistent with (E) - (β - ((3, 5-dibromophenyl) (4- (trifluoromethyl) phenyl) methylene)) - γ, γ -dimethyl- γ -butyrolactone. NMR also showed that the unpurified white solid product had a mixture of E/Z isomers of β - ((3, 5-dibromophenyl) (4- (trifluoromethyl) phenyl) methylene)) - γ, γ -dimethyl- γ -butyrolactone.

Example 1A

Step 1

A mixture of the product of example 1, toluene (500mL), bismuth triflate (20g) and acetic acid (0.24g) was stirred at reflux for 1 hour. After cooling to room temperature, acetic anhydride (100mL) was added. The mixture was heated to reflux again. After 1 hour, the mixture was cooled to room temperature and filtered through a silica plug column and eluted with toluene. The resulting clear solution was concentrated. Acetone (50mL) was added to give a slurry. To the slurry mixture, methanol (250mL) was added, and the mixture was cooled in an ice bath. The white crystals were collected and dried to give 58g of a solid. NMR showed the product to have a structure consistent with 8, 10-dibromo-7, 7-dimethyl-3- (trifluoromethyl) -7H-benzo [ c ] fluoren-5-yl acetate.

Step 2

Methanol (20mL) and tetrahydrofuran (10mL) were added to a flask containing the product of step 1 (2.42 g). Concentrated hydrochloric acid (1mL) was added and the solution heated to reflux for 4 h. The solution was removed under vacuum and the residue was purified by column plug on silica gel using a 4:1 hexane/ethyl acetate mixture as eluent. The fractions containing the desired material were grouped and concentrated to provide a cream colored solid (1.63 g). NMR of the cream colored solid showed structure consistent with 8, 10-dibromo-7, 7-dimethyl-3- (trifluoromethyl) -7H-benzo [ c ] fluoren-5-ol.

Step 3

1- (4-methoxyphenyl) -1-phenylpropan-2-yn-1-ol (4g) and p-toluenesulfonic acid (32mg) were added to a solution of the product of step 2 in dichloroethane (100 mL). The solution was heated to reflux for 2 h. The reaction mixture was concentrated under reduced pressure. The purified product was isolated on a silica gel plug and then recrystallized from acetone/methanol. The grey crystals (7.6g) were collected by vacuum filtration. NMR analysis of the product showed a structure consistent with 3- (4-methoxyphenyl) -3-phenyl-10, 12-dibromo-6-trifluoromethyl-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran.

Example 2

The procedure of step 1 to step 3 of example 1 was followed except that 3, 5-difluorobenzoyl chloride was used instead of 4-trifluoromethylbenzoyl chloride. A white solid was obtained as product. NMR showed the product to have a structure consistent with a mixture of E/Z isomers of (β - ((3, 5-dibromophenyl) (3, 5-difluorophenyl) methylene)) - γ, γ -dimethyl- γ -butyrolactone.

Example 2A

The procedure of step 1-step 3 of example 1A was followed except that: the product of example 2 was used in place of the product of example 1 in step 1; in step 2, the appropriate product, 8, 10-dibromo-2, 4-difluoro-7, 7-dimethyl-7H-ben [ c ] fluoren-5-ol, was recrystallized from ethyl acetate as solvent; in step 3, 1- (4-fluorophenyl) -1- (4- (N-morpholino) phenyl) prop-2-yn-1-ol is used instead of 1- (4-methoxyphenyl) -1-phenylprop-2-yn-1-ol. NMR confirmed that the final product had a structure consistent with 3- (4-fluorophenyl) -3- (4-morpholinophenyl) -10, 12-dibromo-5, 7-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran.

Example 3

The procedure of step 1 to step 3 of example 1 was followed except that 2, 4-difluorobenzoyl chloride was used instead of 4-trifluoromethylbenzoyl chloride in step 1. A white solid was obtained as product. NMR showed the product to have a structure consistent with a mixture of E/Z isomers of (β - ((3, 5-dibromophenyl) (2, 4-difluorophenyl) methylene)) - γ, γ -dimethyl- γ -butyrolactone.

Example 3A

The procedure of step 1-step 3 of example 1A was followed except that: the product of example 3 was used in place of the product of example 1 in step 1; in step 3, 1-bis (4-methoxyphenyl) prop-2-yn-1-ol is used instead of 1- (4-methoxyphenyl) -1-phenylprop-2-yn-1-ol. NMR analysis of the resulting off-white crystals showed the structure to be consistent with 3, 3-bis (4-methoxyphenyl) -10, 12-dibromo-6, 8-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran.

Example 4

The procedure of step 1-step 3 of example 1 was followed except that 3, 5-difluorobromobenzene and 2-methoxybenzoyl chloride were used instead of tribromobenzene and 4-trifluoromethylbenzoyl chloride in step 1 and the product of step 2 was purified by column separation. A clear oil was obtained as product. NMR showed the product to have a structure consistent with a mixture of E/Z isomers of β - ((3, 5-dibromophenyl) (2-methoxyphenyl) methylene)) - γ, γ -dimethyl- γ -butyrolactone.

Example 4A

The procedure of step 1-step 3 of example 1A was followed except that: the product of example 4 was used in place of the product of example 1 in step 1; in step 1, the toluene solution is washed with water, dried over magnesium and passed through before acetic anhydride is added againFiltering with filter aid to remove bismuth trifluoromethanesulfonate; in step 3, 1-bis (4-methoxyphenyl) prop-2-yn-1-ol is used instead of 1- (4-methoxyphenyl) -1-phenylprop-2-yn-1-ol. NMR confirmed the off-white crystalline product to have identity with 3, 3-bis (4-methoxyphenyl) -9-methoxy-5, 7-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1,2-b ]]Pyrans have a consistent structure.

Example 5

The procedure of step 1-step 3 of example 1 was followed, except that 3, 5-difluorobromobenzene and 4-methoxybenzoyl chloride were used in place of tribromobenzene and 4-trifluoromethylbenzoyl chloride in step 1. A white solid was obtained as product. NMR showed the product to have a structure consistent with a mixture of E/Z isomers of β - ((3, 5-dibromophenyl) (4-methoxyphenyl) methylene)) - γ, γ -dimethyl- γ -butyrolactone.

Example 5A

Step 1

The procedure of step 1 of example 1A was followed except that the product of example 5 was used instead of the product of example 1. An off-white solid was obtained as product. NMR showed the product to have a structure consistent with 2, 4-dichloro-9-methoxy-7, 7-dimethyl-7H-benzo [ c ] fluoren-5-yl acetate.

Step 2

A mixture of the product of step 1 (5g), N-bromosuccinimide (2.7g), and DMF (100mL) was stirred in a reaction flask and heated at 90 ℃ for 2 hours. The reaction mixture was poured into water (400mL) and extracted with 1/1 ethyl acetate/THF (200 mL). The organic layer was collected, washed 2 times with aqueous sodium bisulfite solution, dried and concentrated. To the resulting crude product, methanol (100mL) was added. After filtration, an off-white solid (4.4g) was obtained as the product. NMR showed the product to have a structure consistent with 10-bromo-2, 4-dichloro-9-methoxy-7, 7-dimethyl-7H-benzo [ c ] fluoren-5-yl acetate.

Step 3

A mixture of the product of step 2 (4.3g), 4'- (4-trans-pentylcyclohexyl) -N- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) - [1,1' -diphenyl ] -4-carboxamide (4.94g), sodium carbonate (4g), THF (200mL), water (20mL), and tetrakis (triphenylphosphine) palladium (0) (1g) was placed in a reaction flask and degassed by bubbling gas through the mixture for 10 minutes. The mixture was then heated to reflux for 17 hours. Potassium carbonate (5g) and ethanol (50mL) were then added to the reaction mixture. After refluxing for another 8 hours, THF (200mL) and saturated water with sodium chloride (200mL) were added. The resulting organic layer was collected and washed three times with 100mL1N HCl, 1 time with 100mL1N aqueous sodium sulfite solution, once with saturated sodium chloride water, dried over magnesium sulfate and concentrated. The resulting residue was dissolved in 10/1 toluene/THF (200mL), then passed through a silica gel plug column and eluted with 10/1 toluene/THF. The resulting clear solution was concentrated and stirred in methanol for half an hour. The resulting solid was collected and dried. An off-white solid (7.5g) was obtained as the product. NMR showed the product to have a structure consistent with N- (4- (2, 4-dichloro-5-hydroxy-9-methoxy-7, 7-dimethyl-7H-benzo [ c ] fluoren-10-yl) phenyl) -4'- (4-trans-pentylcyclohexyl) - [1,1' -diphenyl ] -4-carboxamide.

Step 4

The product of step 3 (3g), 1- (4-butoxyphenyl) -1- (4-methoxyphenyl) prop-2-yn-1-ol (1.8g), p-toluenesulfonic acid (73mg), and dichloroethane (50mL) were placed in a reaction flask. The mixture was stirred at reflux for 4 hours. All solvents were removed. Using the catalyst obtained from Teledyne ISCORf purify the product. A black solid (2g) was obtained as the product. NMR showed the structure to be in agreement with 3- (4-butoxyphenyl) -3- (4-methoxyphenyl) -10- [4- (4- (4- (4-trans-pentylcyclohexyl) phenyl) benzoylamino) phenyl]-5, 7-dichloro-11-methoxy-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4]Naphtho [1,2-b ]]The pyrans are consistent.

Example 6

The procedure of step 1 to step 3 of example 1 was followed except that 2, 5-difluorobenzoyl chloride was used instead of 4-trifluoromethylbenzoyl chloride in step 1. A white solid was obtained as product. NMR showed the product to have a structure consistent with a mixture of E/Z isomers of β - ((3, 5-dibromophenyl) (2, 5-dichlorophenyl) methylene)) - γ, γ -dimethyl- γ -butyrolactone.

Example 6A

Step 1

The procedure of step 1 of example 1A was followed using the product of example 6. White crystals were obtained as product. NMR showed the product to have a structure consistent with 8, 10-dibromo-1, 4-difluoro-7, 7-dimethyl-7H-benzo [ c ] fluoren-5-yl acetate.

Step 2

Triphenylphosphine (0.32g) and palladium acetate (0.1g) were added to a degassed solution of toluene (40mL) and ethanol (40 mL). The product of step 1 (2.00g) and 4'- (4-trans-pentylcyclohexyl) -N- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) - [1,1' -diphenyl ] were added]4-carboxamide (2.22g), the solution was degassed for 10 min. Potassium carbonate (1.67g) was added to the solution, and the resulting mixture was heated under reflux for 6 h. The reaction mixture was cooled to room temperature and eluted with ethyl acetate (200 mL). Passing the mixture throughFilter aid bed, filtrate collected and concentrated to provide residue. The residue was purified on a silica gel column using 19/1 toluene/ethyl acetate as eluent. To the resulting pasty, colored residue, toluene was added to precipitate the product. The resulting precipitate was collected by vacuum filtration and dried to provide a cream coloured solid (0.6 g).

Step 3

The procedure of step 3 of example 1A was followed except that 1- (4-butoxyphenyl) -1- (4-fluorophenyl) prop-2-yn-1-ol and the product of step 2 were used instead of 1- (4-methoxyphenyl) -1-phenylprop-2-yn-1-ol and the product of step 2 of example 1A. NMR analysis of the resulting solid showed a structure consistent with 3- (4-butoxyphenyl) -3- (4-fluorophenyl) -10- [4- (4- (4- (4-trans-pentylcyclohexyl) phenyl) benzamido) phenyl ] -5, 8-difluoro-13, 13-dimethyl-3H, 13H-indeno [2 ', 3': 3,4] naphtho [1,2-b ] pyran.

Example 7

The procedure of step 2 to step 3 of example 1 was followed except that (4-fluorophenyl) (thiophen-2-yl) ketone was used instead of 3, 5-dibromo-4' -trifluoromethylbenzophenone in step 2. An oil was obtained as the product. NMR showed the product to have a structure consistent with a mixture of E/Z isomers of β - ((4-fluorophenyl) (thiophen-2-yl) methylene)) - γ, γ -dimethyl- γ -butyrolactone.

Example 7B

Using the structure of example 7, the procedure of steps 1 and 3 of example 1A was followed. NMR showed the resulting black solid product to have a structure consistent with that of 1- (3-fluoro-5-hydroxy-7, 7-dimethyl-7H-benzo [6,7] indeno [1,2-b ] thiophen-9-yl) ethanone.

Example 8

The procedure of step 2 to step 3 of example 1 was followed except that furan-2-yl (phenyl) acetophenone (prepared using the literature procedure of the Friedel-Crafts reaction (Sarvari, M.H.; Sharghi, H.J.Org.Chem.2004,69, 6953-one 6956)) was used in place of 3, 5-dibromo-4' -trifluoromethylbenzophenone in step 2. An oil was obtained as the product. NMR showed the product to have a structure consistent with a mixture of E/Z isomers of β - (phenyl (furan-2-yl) methylene)) - γ, γ -dimethyl- γ -butyrolactone.

Section 2: photochromic Performance test and results

The photochromic properties of the photochromic materials of examples 1A-6A were determined as follows. Will calculate to generate 1.5 x 10^-3A test amount of photochromic material of M solution was added to a flask containing 50 grams of a monomer blend of 4 parts ethoxylated bisphenol a dimethacrylate (BPA2EO DMA), 1 part poly (ethylene glycol) 600 dimethacrylate, and 0.033 weight percent 2, 2' -azobis (2-methylpropanenitrile) (AIBN). The photochromic material is dissolved in the monomer blend by stirring and, if necessary, slight heating. After a clear solution was obtained, it was vacuum degassed and then injected into a flat plate mold having internal dimensions of 2.2mm x6 inches (15.24cm) x6 inches (15.24 cm). The mold was sealed and placed in a horizontal air flow programmed oven, programmed from 40 ℃ to 95 ℃ over a 5 hour interval, held at 95 ℃ for 3 hours, and then cooled to 60 ℃ over a2 hour interval. After opening the mold, the polymer sheet was cut using a utility knife, scored on the surface and folded into 2 inch (5.1cm) test squares.

The photochromic test squares prepared as described above were tested for photochromic response on an optical bench. Prior to testing on the optical bench, the photochromic test squares were exposed to 365nm ultraviolet light for about 15 minutes to convert the photochromic material from the ground state form to the excited state form, and then placed in a 75 ℃ oven for about 15 minutes to convert the photochromic material back to the ground state form. The test squares were then cooled to room temperature, exposed to fluorescent room lights for at least 2 hours, then left covered (i.e., in a dark environment) for at least 2 hours, and then tested on an optical bench maintained at 73 ° F (23 ℃).

The intensity of the radiation used to activate the sample was controlled using an optical bench equipped with a Schott3mm KG-2 bandpass filter, a neutral density filter, and a Newport Model # 67005300-watt xenon arc lamp with a Model #69911 power supply in combination with a Newport Model689456Digital Exposure/Timer. Uniblitz model # CS25S3ZM0 with model # VMM-D3 controller, high speed computer controlled shutter, fused silica condenser lens for beam collimation of the activated lamp beam through the quartz glass water bath sample chamber.

A custom broadband light source for monitoring response measurements was directed through the sample such that the angle between the activating light source and the monitoring beam was 30 ℃, and the sample was positioned perpendicular to the monitoring beam. The broadband light source was obtained by separately collecting and combining filtered light from a 100 watt tungsten halogen lamp (controlled by a Lambda UP60-14 constant voltage power supply) with split-ended bifurcated fiber optic cables to increase the intensity of the short wavelength light. After passing through the sample, the monitoring light was again focused into a2 inch integrating sphere and fed into an Ocean Optics S2000 spectrophotometer via a fiber optic cable. The optical bench operation was determined and controlled using Ocean Optics spectra suite and PPG proprietary software.

λ_max-visIs the wavelength of the visible spectrum at which the photochromic compound in the test block reaches maximum absorption. Lambda [ alpha ]_max-visThe wavelength was determined by measuring the photochromic test block in a Varian Cary4000 UV-Vis spectrophotometer.

The change in saturated optical density of each test sample was determined by opening the shutter from the xenon lamp and measuring the light transmittance after exposing the test piece to 3W/m2UVA radiation for 30 minutes. The change in saturated optical density was calculated using the following formula: Δ OD = log (% Tb/% Ta), where% Tb is the percent transmittance of the faded state and% Ta is at λ_max-visThe percentage of light transmittance in the excited state is 10 on the base of the logarithm. First fade half life ("T_1/2") or fade rate is the delta of the saturation value at room temperature (23 deg.C) for the absorbance of the excited state form of the photochromic material in the test block after removal of the excitation light sourceHalf the OD time in seconds. Sensitivity (Δ OD/Min) is a measure of the rate of darkening of the sample, given by the equation Δ OD_sen=ΔOD_5minx 12.

TABLE 1 photochromic Performance test results

The invention has been described with reference to specific details of particular embodiments thereof. These details are not intended to be considered as limitations on the scope of the invention, which is included in the accompanying claims.

Claims (29)

1. A lactone compound selected from lactone compounds represented by at least one of formulas I and II:

wherein ring a and ring B are each independently selected from aryl and heteroaryl;

m and n are each independently selected from 0-4;

r of each m¹And R of each n²Independently selected from:

halogen selected from fluorine, iodine, bromine and chlorine;

C₇-C₂₀an alkyl group;

C₃-C₁₀a cycloalkyl group;

substituted or unsubstituted phenyl, the substituents of which are selected from the group consisting of hydroxy, halogen, carbonyl, C₁-C₂₀Alkoxycarbonyl, cyano, halo (C)₁-C₂₀) Alkyl radical, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group;

-O-R₁₀' or-C (O) -R₁₀' OR-C (O) -OR₁₀', wherein R₁₀' is hydrogen, C₁-C₂₀Alkyl, phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkyl-substituted phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl (C)₁-C₂₀) Alkyl, (C)₁-C₂₀) Alkoxy (C)₂-C₂₀) Alkyl radical, C₃-C₁₀Cycloalkyl or mono (C)₁-C₂₀) Alkyl substituted C₃-C₁₀A cycloalkyl group;

-N(R₁₁’)R₁₂', wherein R₁₁' and R₁₂' independently of one another are hydrogen, C₁-C₂₀Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, C₁-C₂₀Alkylaryl group, C₃-C₁₀Cycloalkyl radical, C₄-C₂₀Bicycloalkyl radical, C₅-C₂₀Tricycloalkyl or C₁-C₂₀Alkoxyalkyl wherein the aryl is phenyl or naphthyl, or R₁₁' and R₁₂' together with the nitrogen atom form C₃-C₂₀Hetero-bicycloalkyl ring or C₄-C₂₀A heterotricycloalkyl ring;

nitrogen containing rings of the following scheme XIIA:

wherein each-Y-is independently at each occurrence selected from: -CH₂-、-CH(R₁₃’)-、-C(R₁₃’)₂-, -CH (aryl) -, -C (aryl)₂-and-C (R)₁₃') (aryl) -; z is-Y-, -O-, -S (O) -, -SO₂-、-NH-、-N(R₁₃') -or-N (aryl) -, wherein each R is₁₃' independently is C₁-C₂₀An alkyl group; each aryl group is independently phenyl or naphthyl; m is an integer 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-; a group represented by one of the following formulae XIIB or XIIC:

wherein R is₁₅、R₁₆And R₁₇Each independently is hydrogen, C₁-C₂₀Alkyl, phenyl or naphthyl, or the radical R₁₅And R₁₆Together form a ring of 5 to 8 carbon atoms; each R^dIndependently at each occurrence is selected from C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, fluoro or chloro; q is an integer of 0,1, 2 or 3; and unsubstituted, mono-or disubstituted C₄-C₁₈A spirobicyclic amine; or unsubstituted, mono-and disubstituted C₄-C₁₈Spirotricyclic amine wherein the substituents are independently aryl, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy or phenyl (C)₁-C₂₀) An alkyl group; or

Two adjacent R¹Radicals or two adjacent R²The groups independently together form a group represented by one of XIID and XIIE:

wherein T and T' are each independently oxygen or a group-NR₁₁' -, wherein R₁₁’、R₁₅And R₁₆As described above; and

R³and R⁴Each independently selected from: a hydrocarbyl group optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-、-N(R₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl; and substituted hydrocarbyl optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-, and-N (R)₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl; or R³And R⁴Together form a ring structure optionally including at least one heteroatom.

2. The lactone compound of claim 1, wherein:

ring a and ring B are each independently selected from unsubstituted aryl and substituted aryl; and

R³and R⁴Each independently selected from:

(i)C₁-C₂₀alkyl radical, C₁-C₂₀Haloalkyl, C₃-C₁₀Cycloalkyl, allyl, benzyl or mono-substituted benzyl, the substituents of the benzyl being selected from halogen, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group;

(ii) unsubstituted, mono-, di-or tri-substituted radicals from the group consisting of phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl or indolyl, the substituents of said radicals being in each case independently selected from the group consisting of halogen, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group; or

(iii) A monosubstituted phenyl radical, which is in the para position, is- (CH)₂)_t-or-O- (CH)₂)_t-, where t is an integer 1,2, 3,4, 5 or 6, said substituents being attached to an aryl group as part of the photochromic material;

(iv) group-CH(R¹⁰) G, wherein R¹⁰Is hydrogen, C₁-C₂₀An alkyl group or an unsubstituted, mono-or di-substituted aryl group; g is-CH₂OR¹¹Wherein R is¹¹Is hydrogen, -C (O) R¹⁰、C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy (C)₁-C₂₀) Alkyl, phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl (C)₁-C₂₀) An alkyl group or an unsubstituted, mono-or di-substituted aryl group; or

(v)R³And R⁴Together form a spiro substituent selected from a substituted or unsubstituted spiro carbocyclic ring comprising 3 to 6 carbon atoms, a substituted or unsubstituted spiro heterocyclic ring comprising 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spiro carbon atom, the spiro carbocyclic ring and the spiro heterocyclic ring being fused to 0,1 or 2 phenyl rings, said substituent being hydrogen or C₁-C₂₀An alkyl group.

3. The lactone compound of claim 1, wherein R for each m¹And R of each n²Independently selected from C in each occurrence₃-C₇Cycloalkyl radical, C₁-C₈Haloalkyl, fluorine, iodine, bromine, chlorine and-O-R₁₀’。

4. The lactone compound of claim 3, wherein R³And R⁴Each independently selected from C₁-C₈Alkyl radical, C₁-C₈Haloalkyl and C₃-C₇Cycloalkyl, or R³And R⁴Together form a spiro substituent selected from substituted or unsubstituted spiro carbocycles containing 3 to 6 carbon atoms.

5. The lactone compound of claim 1, wherein the lactone compound is selected from the group consisting of lactone compounds represented by at least one of formulas Ia and IIa:

6. the lactone compound of claim 1, wherein each of the a and B rings is independently selected from fused ring aryl groups.

7. The lactone compound of claim 2, wherein the aryl group in (iv) is selected from the group consisting of phenyl and naphthyl, each of which has a substituent C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group.

8. A method of preparing a fused ring indenol compound represented by at least one of formula III and formula III-2:

wherein ring a and ring B are each independently selected from aryl and heteroaryl;

m and n are each independently selected from 0-4;

r of each m¹And R of each n²Independently selected from:

halogen selected from fluorine, iodine, bromine and chlorine;

C₇-C₂₀an alkyl group;

C₃-C₁₀a cycloalkyl group;

substituted or unsubstituted phenyl, the substituents of which are selected from the group consisting of hydroxy, halogen, carbonyl, C₁-C₂₀Alkoxycarbonyl, cyano, halo (C)₁-C₂₀) Alkyl radical, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group;

-O-R₁₀' or-C (O) -R₁₀' OR-C (O) -OR₁₀', wherein R₁₀' is hydrogen, C₁-C₂₀Alkyl, phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkyl-substituted phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkoxy radicalSubstituted phenyl (C)₁-C₂₀) Alkyl, (C)₁-C₂₀) Alkoxy (C)₂-C₂₀) Alkyl radical, C₃-C₁₀Cycloalkyl or mono (C)₁-C₂₀) Alkyl substituted C₃-C₁₀A cycloalkyl group;

-N(R₁₁’)R₁₂', wherein R₁₁' and R₁₂' independently of one another are hydrogen, C₁-C₂₀Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, C₁-C₂₀Alkylaryl group, C₃-C₁₀Cycloalkyl radical, C₄-C₂₀Bicycloalkyl radical, C₅-C₂₀Tricycloalkyl or C₁-C₂₀Alkoxyalkyl wherein the aryl is phenyl or naphthyl, or R₁₁' and R₁₂' together with the nitrogen atom form C₃-C₂₀Hetero-bicycloalkyl ring or C₄-C₂₀A heterotricycloalkyl ring;

nitrogen containing rings of the following scheme XIIA:

wherein each-Y-is independently at each occurrence selected from: -CH₂-、-CH(R₁₃’)-、-C(R₁₃’)₂-, -CH (aryl) -, -C (aryl)₂-and-C (R)₁₃') (aryl) -; z is-Y-, -O-, -S (O) -, -SO₂-、-NH-、-N(R₁₃') -or-N (aryl) -, wherein each R is₁₃' independently is C₁-C₂₀An alkyl group; each aryl group is independently phenyl or naphthyl; m is an integer 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-; a group represented by one of the following formulae XIIB or XIIC:

wherein R is₁₅、R₁₆And R₁₇Each independently is hydrogen, C₁-C₂₀Alkyl, phenyl or naphthyl, or the radical R₁₅And R₁₆Together form a ring of 5 to 8 carbon atoms; each R^dIndependently at each occurrence is selected from C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, fluoro or chloro; q is an integer of 0,1, 2 or 3; and unsubstituted, mono-or disubstituted C₄-C₁₈A spirobicyclic amine; or unsubstituted, mono-and disubstituted C₄-C₁₈Spirotricyclic amine wherein the substituents are independently aryl, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy or phenyl (C)₁-C₂₀) An alkyl group; or

Two adjacent R¹Radicals or two adjacent R²The groups independently together form a group represented by one of XIID and XIIE:

wherein T and T' are each independently oxygen or a group-NR₁₁' -, wherein R₁₁’、R₁₅And R₁₆As described above; and

R³and R⁴Each independently selected from: a hydrocarbyl group optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-、-N(R₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl and combinations of two or more thereof; and substituted hydrocarbyl optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-、-N(R₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl and combinations of two or more thereof; or R³And R⁴Together form a ring structure optionally including at least one heteroatom;

R¹²selected from hydrogen, -C (O) -R¹³and-S (O) R¹³Wherein R is¹³Selected from the group consisting of hydrocarbyl and halogenated hydrocarbyl;

the method comprises the following steps:

(a) converting a lactone compound selected from the group consisting of lactone compounds represented by at least one of formulas I and II below to an acid intermediate comprising a lactone represented by at least one of formulas IV and IV-2;

and

(b) converting the acid intermediate represented by at least one of formulas IV and IV-2 to the fused ring indenol compound represented by at least one of formulas III and III-2.

9. The method of claim 8 wherein the a and B rings are each independently selected from fused ring aryl groups.

10. The process of claim 8, wherein the conversion of the lactone compound is carried out in the presence of a catalyst selected from one or more lewis acids; and

the conversion of the acid intermediate of at least one of formulas IV and IV-2 to the compound of at least one of formulas III and III-2 is carried out in the presence of a material selected from the group consisting of carboxylic acid halides, carboxylic acid anhydrides, sulfonyl halides, sulfonyl anhydrides, and combinations thereof, thereby forming an intermediate of at least one of formulas V and V-2:

wherein R is¹⁴Selected from the group consisting of-C (O) -R¹³and-S (O) R¹³Wherein R is¹³Selected from the group consisting of hydrocarbyl and halogenated hydrocarbyl;

optionally then hydrolyzing the intermediate product represented by at least one of formulas V and V-2 in the presence of a protic acid or base, thereby forming the fused ring indenol compound represented by at least one of formulas III and III-2, wherein R is¹²Is hydrogen.

11. The method of claim 10, wherein the electron abundance of the a ring of the lactone compound is greater than the electron abundance of the B ring of the lactone compound, and the lewis acid is selected from at least one of: bi⁽³⁺⁾(^-O-SO₂-R¹⁵)₃Wherein R is¹⁵Selected from the group consisting of hydrocarbyl and halogenated hydrocarbyl; and BiX₃Wherein each X is independently selected from halogen.

12. The method of claim 11, wherein R¹⁵Is CF₃。

13. The process of claim 8, wherein the conversion of the lactone compound is carried out in the presence of a catalyst selected from one or more lewis acids; and

the conversion of the acid intermediate of formula IV to the fused ring indenol compound of formula III is carried out in the presence of a protic acid, wherein R¹²Is hydrogen.

14. The method of claim 13, wherein the protic acid is selected from the group consisting of carboxylic acids, sulfonic acids, phosphoric acids, and combinations thereof.

15. The method of claim 8, wherein:

ring a and ring B are each independently selected from unsubstituted aryl and substituted aryl; and

R³and R⁴Each independently selected from:

(i)C₁-C₂₀alkyl radical, C₁-C₂₀Haloalkyl, C₃-C₁₀Cycloalkyl, allyl, benzyl or mono-substituted benzyl, the benzyl substituent being selected from halogen, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group;

(ii) unsubstituted, monosubstituted, disubstituted or trisubstituted radicals from the group consisting of phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl or indolyl, the substituents of which are in each case independently selected from halogen, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group; or

(iii) Mono-substituted phenyl, said substituent being in para position, is- (CH)₂)_t-or-O- (CH)₂)_t-, where t is an integer 1,2, 3,4, 5 or 6, which substituent is attached to an aryl group as part of the photochromic material;

(iv) the radical-CH (R)¹⁰) G, wherein R¹⁰Is hydrogen, C₁-C₆An alkyl group or an unsubstituted, mono-or di-substituted aryl group; g is-CH₂OR¹¹Wherein R is¹¹Is hydrogen, -C (O) R¹⁰、C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy (C)₁-C₂₀) Alkyl, phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl (C)₁-C₂₀) An alkyl group or an unsubstituted, mono-or di-substituted aryl group; or

(v)R³And R⁴Together form a spiro substituent selected from a substituted or unsubstituted spiro carbocyclic ring comprising 3 to 6 carbon atoms, a substituted or unsubstituted spiro heterocyclic ring comprising 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spiro carbon atom, the spiro carbocyclic ring and the spiro heterocyclic ring being fused to 0,1 or 2 phenyl rings, said substituent being hydrogen or C₁-C₂₀An alkyl group.

16. The method of claim 15, wherein said aryl group in (iv) is selected from the group consisting of phenyl and naphthyl, each of said phenyl and naphthyl having substituent C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group.

17. The method of claim 15, wherein R for each m¹And R of each n²Independently selected from C in each occurrence₃-C₇Cycloalkyl radical, C₁-C₈Haloalkyl, fluorine, iodine, bromine, chlorine and-O-R₁₀’。

18. The method of claim 17, wherein R³And R⁴Each independently selected from C₁-C₈Alkyl radical, C₁-C₈Haloalkyl and C₃-C₇A cycloalkyl group; or R³And R⁴Together form a spiro substituent selected from substituted or unsubstituted spiro carbocycles containing 3 to 6 carbon atoms.

19. The method of claim 8, wherein the fused ring indenol compound represented by formula III is represented by the following formula IIIa:

the lactone compound is represented by at least one of the following formulas Ia and IIa:

and the acid intermediate of formula IV is represented by the following formula IVa:

20. a method for producing a lactone compound selected from lactone compounds represented by at least one of formulas I and II:

wherein ring a and ring B are each independently selected from aryl and heteroaryl;

m and n are each independently selected from 0-4;

r of each m¹And R of each n²Independently selected from:

halogen selected from fluorine, iodine, bromine and chlorine;

C₁-C₂₀an alkyl group;

C₃-C₁₀a cycloalkyl group;

substituted or unsubstituted phenyl, the substituents of which are selected from the group consisting of hydroxy, halogen, carbonyl, C₁-C₂₀Alkoxycarbonyl, cyano, halo (C)₁-C₂₀) Alkyl radical, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group;

-O-R₁₀' or-C (O) -R₁₀' OR-C (O) -OR₁₀', wherein R₁₀' is hydrogen, C₁-C₂₀Alkyl, phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkyl-substituted phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl (C)₁-C₂₀) Alkyl, (C)₁-C₂₀) Alkoxy (C)₂-C₂₀) Alkyl radical, C₃-C₁₀Cycloalkyl or mono (C)₁-C₂₀) Alkyl substituted C₃-C₁₀A cycloalkyl group;

-N(R₁₁’)R₁₂', wherein R₁₁' and R₁₂' independently of one another are hydrogen, C₁-C₂₀Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, and the like,C₁-C₂₀Alkylaryl group, C₃-C₁₀Cycloalkyl radical, C₄-C₂₀Bicycloalkyl radical, C₅-C₂₀Tricycloalkyl or C₁-C₂₀Alkoxyalkyl wherein the aryl is phenyl or naphthyl, or R₁₁' and R₁₂' together with the nitrogen atom form C₃-C₂₀Hetero-bicycloalkyl ring or C₄-C₂₀A heterotricycloalkyl ring;

nitrogen containing rings of the following scheme XIIA:

wherein each-Y-is independently at each occurrence selected from: -CH₂-、-CH(R₁₃’)-、-C(R₁₃’)₂-, -CH (aryl) -, -C (aryl)₂-and-C (R)₁₃') (aryl) -; z is-Y-, -O-, -S (O) -, -SO₂-、-NH-、-N(R₁₃') -or-N (aryl) -, wherein each R is₁₃' independently is C₁-C₂₀An alkyl group; each aryl group is independently phenyl or naphthyl; m is an integer 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-; a group represented by one of the following formulae XIIB or XIIC:

wherein R is₁₅、R₁₆And R₁₇Each independently is hydrogen, C₁-C₂₀Alkyl, phenyl or naphthyl, or the radical R₁₅And R₁₆Together form a ring of 5 to 8 carbon atoms; each R^dIndependently at each occurrence is selected from C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, fluoro or chloro; q is an integer of 0,1, 2 or 3; and unsubstituted, mono-or disubstituted C₄-C₁₈A spirobicyclic amine; or unsubstituted, mono-and disubstituted C₄-C₁₈Spirotricyclic amine wherein the substituents are independently aryl, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy or phenyl (C)₁-C₂₀) An alkyl group; or

Two adjacent R¹Radicals or two adjacent R²The groups independently together form a group represented by one of XIID and XIIE:

wherein T and T' are each independently oxygen or a group-NR₁₁' -, wherein R₁₁’、R₁₅And R₁₆As described above; and

R³and R⁴Each independently selected from: a hydrocarbyl group optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-, and-N (R)₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl; and substituted hydrocarbyl optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-, and-N (R)₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl; or R³And R⁴Together form a ring structure optionally including at least one heteroatom;

the method comprises the following steps: reacting an acid ester of at least one of formulas VI and VII with at least one of a metal hydride reducing agent and a nucleophile of at least one of formulas VIII and IX, thereby forming the lactone compound,

wherein R is¹⁶Selected from hydrocarbyl and substituted hydrocarbyl; m, n, R of formula VI and VII¹、R²Ring A and ring B are each independently as described for formula I and formula II, R³Is R as described with reference to formulae I and II³(ii) a nucleophile of (a); r⁴Is R as described with reference to formulae I and II⁴(ii) a nucleophile of (a); m¹And M²Each independently selected fromSi(R¹⁸)₃Wherein each R¹⁸Independently selected from C₁-C₈Alkyl, or M¹And M²Each independently represents a counterion comprising a metal selected from the group consisting of Mg, Li, Mn, Cu, Zn, Al, Ti, Ln, and combinations thereof.

21. The method of claim 20 wherein the a and B rings are each independently selected from fused ring aryl groups.

22. The method of claim 20, wherein the lactone compound is represented by one of the following formulas Ia and IIa:

the acid ester is represented by at least one of formulas VIa and VIIa:

23. a process for preparing a fused ring indenopyran compound represented by at least one of the following formulae X and X-2:

wherein ring a and ring B are each independently selected from aryl and heteroaryl;

m and n are each independently selected from 0-4;

r of each m¹And R of each n²Independently selected from:

halogen selected from fluorine, iodine, bromine and chlorine;

C₁-C₂₀an alkyl group;

C₃-C₁₀a cycloalkyl group;

substituted or unsubstituted phenyl, the substituents of which are selected from the group consisting of hydroxy, halogen, carbonyl, C₁-C₂₀Alkoxycarbonyl, cyano, halo (C)₁-C₂₀) Alkyl radical, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group;

-O-R₁₀' or-C (O) -R₁₀' OR-C (O) -OR₁₀', wherein R₁₀' is hydrogen, C₁-C₂₀Alkyl, phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkyl-substituted phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl (C)₁-C₂₀) Alkyl, (C)₁-C₂₀) Alkoxy (C)₂-C₂₀) Alkyl radical, C₃-C₁₀Cycloalkyl or mono (C)₁-C₂₀) Alkyl substituted C₃-C₁₀A cycloalkyl group;

-N(R₁₁’)R₁₂', wherein R₁₁' and R₁₂' independently of one another are hydrogen, C₁-C₂₀Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, C₁-C₂₀Alkylaryl group, C₃-C₁₀Cycloalkyl radical, C₄-C₂₀Bicycloalkyl radical, C₅-C₂₀Tricycloalkyl or C₁-C₂₀Alkoxyalkyl wherein the aryl is phenyl or naphthyl, or R₁₁' and R₁₂' together with the nitrogen atom form C₃-C₂₀Hetero-bicycloalkyl ring or C₄-C₂₀A heterotricycloalkyl ring;

nitrogen containing rings of the following scheme XIIA:

wherein each-Y-is independently at each occurrence selected from: -CH₂-、-CH(R₁₃’)-、-C(R₁₃’)₂-, -CH (aryl) -, -C (aryl)₂-and-C (R)₁₃') (aryl radical) -; z is-Y-, -O-, -S (O) -, -SO₂-、-NH-、-N(R₁₃') -or-N (aryl) -, wherein each R is₁₃' independently is C₁-C₂₀An alkyl group; each aryl group is independently phenyl or naphthyl; m is an integer 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-; a group represented by one of the following formulae XIIB or XIIC:

wherein R is₁₅、R₁₆And R₁₇Each independently is hydrogen, C₁-C₂₀Alkyl, phenyl or naphthyl, or the radical R₁₅And R₁₆Together form a ring of 5 to 8 carbon atoms; each R^dIndependently at each occurrence is selected from C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, fluoro or chloro; q is an integer of 0,1, 2 or 3; and unsubstituted, mono-or disubstituted C₄-C₁₈A spirobicyclic amine; or unsubstituted, mono-and disubstituted C₄-C₁₈Spirotricyclic amine wherein the substituents are independently aryl, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy or phenyl (C)₁-C₂₀) An alkyl group; or

Two adjacent R¹Radicals or two adjacent R²The groups independently together form a group represented by one of XIID and XIIE:

wherein T and T' are each independently oxygen or a group-NR₁₁' -, wherein R₁₁’、R₁₅And R₁₆As described above; and

R³and R⁴Each independently selected from: a hydrocarbyl group optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-, and-N (R)₁₁') -, wherein R is₁₁' selected from hydrogen, hydrocarbonsA radical or substituted hydrocarbyl radical; and substituted hydrocarbyl optionally interrupted by at least one of: -O-, -S-, -C (O) O-, -S (O) -, -SO₂-, and-N (R)₁₁') -, wherein R is₁₁' is selected from hydrogen, hydrocarbyl or substituted hydrocarbyl; or R³And R⁴Together form a ring structure optionally including at least one heteroatom, an

B and B 'are each independently selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, polyalkoxy and polyalkoxy having a polymerizable group, or B and B' together form a ring structure selected from: unsubstituted fluoren-9-enyl, substituted fluoren-9-enyl, saturated spiro monocyclic hydrocarbon ring, saturated spiro bicyclic hydrocarbon ring, and spiro tricyclic hydrocarbon ring;

the method comprises the following steps:

(a) converting a lactone compound selected from the group consisting of lactone compounds represented by at least one of formulas I and II below to an acid intermediate comprising at least one of formulas IV and IV-2;

(b) converting the acid intermediate represented by at least one of formulas IV and IV-2 to a fused ring indenol compound represented by at least one of formulas III and III-2;

wherein R is¹²Selected from hydrogen, -C (O) -R¹³and-S (O) R¹³Wherein R is¹³Selected from the group consisting of hydrocarbyl and halogenated hydrocarbyl; m, n, R of the formulae III and III-2¹、R²、R³、R⁴Ring A and ring B are each independently as described for formula X and formula X-2, and

(c) reacting a fused ring indenol compound represented by at least one of formulas III and III-2 with a propargyl alcohol represented by formula XI;

thereby forming the fused ring indenopyran compound represented by at least one of formulas X and X-2.

24. The method of claim 23 wherein the a and B rings are each independently selected from fused ring aryl groups.

25. The method of claim 23, wherein:

ring a and ring B are each independently selected from aryl;

R³and R⁴Each independently selected from:

(i)C₁-C₂₀alkyl radical, C₁-C₂₀Haloalkyl, C₃-C₁₀Cycloalkyl, allyl, benzyl or mono-substituted benzyl, the benzyl substituent being selected from halogen, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group;

(ii) unsubstituted, mono-, di-or tri-substituted radicals selected from the group consisting of phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl and indolyl, the substituents of which are selected from the group consisting of halogen, C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group; or

(iii) A monosubstituted phenyl radical, which is in the para position, is- (CH)₂)_t-or-O- (CH)₂)_t-, where t is an integer 1,2, 3,4, 5 or 6, which substituent is attached to an aryl group as part of the photochromic material;

(iv) the radical-CH (R)¹⁰) G, wherein R¹⁰Is hydrogen、C₁-C₆An alkyl group or an unsubstituted, mono-or di-substituted aryl group; g is-CH₂OR¹¹Wherein R is¹¹Is hydrogen, -C (O) R¹⁰、C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy (C)₁-C₂₀) Alkyl, phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl (C)₁-C₂₀) An alkyl group or an unsubstituted, mono-or di-substituted aryl group; or

(v)R³And R⁴Together form a spiro substituent selected from a substituted or unsubstituted spiro carbon ring containing 3 to 6 carbon atoms, a substituted or unsubstituted spiro heterocyclic ring containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms inclusive of the spiro carbon atoms, said spiro carbon ring and spiro heterocyclic ring being fused to 0,1 or 2 benzene rings, said substituent being hydrogen or C₁-C₂₀An alkyl group; and

b and B' are each independently:

a substituted phenyl group; a substituted aryl group; substituted 9-julolidinyl; or a substituted heteroaryl group selected from pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl, wherein the substituent of said phenyl, aryl, 9-julolidinyl or heteroaryl group is selected from unsubstituted, mono-, di-or tri-substituted aryl; 9-julolidinyl; or an unsubstituted, mono-or di-substituted heteroaryl group selected from pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl, wherein each substituent of the aryl and heteroaryl groups is independently selected from:

a hydroxyl group; the radical-C (═ O) R₂₁Wherein R is₂₁is-OR₂₂、-N(R₂₃)R₂₄Piperidinyl or morpholinyl, wherein R₂₂Is allyl, C₁-C₂₀Alkyl, phenyl, mono (C)₁-C₂₀) Alkyl substituted phenyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl, phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkyl-substituted phenyl (C)₁-C₂₀) Alkyl, mono (C)₁-C₂₀) Alkoxy-substituted phenyl (C)₁-C₂₀) Alkyl, (C)₁-C₂₀) Alkoxy (C)₂-C₂₀) Alkyl or C₁-C₂₀Haloalkyl, R₂₃And R₂₄Each independently is C₁-C₂₀Alkyl radical, C₅-C₁₀Cycloalkyl, phenyl or substituted phenyl, the phenyl substituent being C₁-C₂₀Alkyl or C₁-C₂₀Alkoxy, halo substituents are chloro, iodo, bromo or fluoro; an aryl group; mono (C)₁-C₂₀) An alkoxyaryl group; two (C)₁-C₂₀) An alkoxyaryl group; mono (C)₁-C₂₀) An alkylaryl group; two (C)₁-C₂₀) An alkylaryl group; a halogenated aryl group; c₃-C₁₀A cycloalkyl aryl group; c₃-C₁₀A cycloalkyl group; c₃-C₁₀A cycloalkoxy group; c₃-C₁₀Cycloalkoxy (C)₁-C₂₀) An alkyl group; c₃-C₁₀Cycloalkoxy (C)₁-C₂₀) An alkoxy group; aryl radical (C)₁-C₂₀) An alkyl group; aryl radical (C)₁-C₂₀) An alkoxy group; an aryloxy group; aryloxy radical (C)₁-C₂₀) An alkyl group; aryloxy radical (C)₁-C₂₀) An alkoxy group; mono or di (C)₁-C₂₀) Alkylaryl (C)₁-C₂₀) An alkyl group; mono or di (C)₁-C₂₀) Alkoxyaryl (C)₁-C₂₀) An alkyl group; mono or di (C)₁-C₂₀) Alkylaryl (C)₁-C₂₀) An alkoxy group; mono or di (C)₁-C₂₀) Alkoxyaryl (C)₁-C₂₀) An alkoxy group; an amino group; mono or di (C)₁-C₂₀) An alkylamino group; a diarylamino group; a piperazinyl group; n- (C)₁-C₂₀) An alkyl piperazinyl group; n-arylpiperazinyl; an aziridinyl group; an indolinyl group; a piperidinyl group; morpholinyl;a thiomorpholinyl group; a tetrahydroquinolyl group; tetrahydroisoquinolinyl; a pyrrolidinyl group; c₁-C₂₀An alkyl group; c₁-C₂₀A haloalkyl group; c₁-C₂₀An alkoxy group; mono (C)₁-C₂₀) Alkoxy (C)₁-C₂₀) An alkyl group; an acryloxy group; methacryloxy or halogen;

an unsubstituted or mono-substituted radical selected from the group consisting of pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, each of said substituents being C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, phenyl or halogen;

a group represented by:

wherein K is-CH₂-or-O-; m is-O-or substituted nitrogen, with the proviso that when M is substituted nitrogen, K is-CH₂-; the substituent of the substituted nitrogen being hydrogen, C₁-C₂₀Alkyl or C₁-C₂₀An alkenyl group; each R₂₅Independently at each occurrence is selected from C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy, hydroxy and halogen; r₂₆And R₂₇Each independently is hydrogen or C₁-C₂₀An alkyl group; u is an integer in the range of 0-2; or a group represented by:

wherein R is₂₈Is hydrogen or C₁-C₂₀An alkyl group; r₂₉Is an unsubstituted, mono-or di-substituted radical selected from the group consisting of naphthyl, phenyl, furyl and thienyl, wherein the substituent is C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy or halogen; or

B and B' together form one of the following: fluoren-9-ylidene, monosubstituted fluoren-9-ylidene or bisSubstituted fluoren-9-ylidene, each substituent of fluoren-9-ylidene being independently selected from C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy and halogen.

26. The method of claim 25, wherein said aryl in (vi) is selected from the group consisting of phenyl and naphthyl, each of said phenyl and naphthyl having substituent C₁-C₂₀Alkyl or C₁-C₂₀An alkoxy group.

27. The method of claim 25, wherein:

r of each m¹And R of each n²Independently selected from C in each occurrence₃-C₇Cycloalkyl radical, C₁-C₈Haloalkyl, fluorine, chlorine and-O-R₁₀’；

R³And R⁴Each independently selected from C₁-C₈Alkyl radical, C₁-C₈Haloalkyl and C₃-C₇A cycloalkyl group; or together form a spiro substituent selected from a substituted or unsubstituted spiro carbocyclic ring comprising 3 to 6 carbon atoms; and

b and B' are each independently selected from C₁-C₆Aryl of alkoxy and aryl substituted with morpholinyl.

28. The method of claim 25, wherein said aryl group in an unsubstituted, mono-, di-, or tri-substituted aryl group is phenyl.

29. The method of claim 23, wherein the fused ring indenopyran compound is represented by the following formula Xa: