CN103339123B

CN103339123B - There is the indeno fused ring compound of photochromic property

Info

Publication number: CN103339123B
Application number: CN201180066436.5A
Authority: CN
Inventors: 何猛; A·库玛; D·R·达布迪恩
Original assignee: Transitions Optical Inc
Current assignee: Transitions Optical Inc
Priority date: 2010-12-16
Filing date: 2011-12-01
Publication date: 2016-11-30
Anticipated expiration: 2031-12-01

Abstract

The present invention relates to lower formula (I) and the compound shown in (II), (I) (II)

Description

There is the indeno fused ring compound of photochromic property

The related application of cross reference

The application is that the part of U.S. Patent Application Serial No.12/329092 of December in 2008 submission on the 5th continues Shen Please, it is the part continuation application of U.S. Patent Application Serial No.10/846629 that on May 17th, 2004 submits to, this U.S. Patent application Ser. No No.10/846629 is present United States Patent (USP) No.7342112 and enjoys submission on July 1st, 2003 The rights and interests of U.S. Provisional Application Serial No. No.60/484100, whole documents is hereby incorporated by reference with all of which.

Invention field

The present invention relates to indeno fused ring compound, including indeno condensed ring pyrylium compound, it can be photochromic chemical combination Thing, and include compositions and the goods of the photochromic compound of the present invention.

Background of invention

Photochromic compound typically has at least two state, and the first state has the first absorption spectrum and the second shape State has the second absorption spectrum being different from this first absorption spectrum, and it is next at two kinds of shapes to respond at least photochemical radiation Switch between state.Additionally, the photochromic compound of routine can be thermal reversion.That is, photochromic compound can respond At least photochemical radiation and switch between the first state and a second state, and respond heat energy time be restored back to the first state. As used herein, " photochemical radiation " represents such electromagnetic radiation, radiates such as but not limited to Uv and visible light, its Response can be caused.More specifically, conventional photochromic compound can experience when response light chemical radiation different from one Structure body is converted into another kind, and each isomer has distinctive absorption spectrum, and can be the most extensive when responding heat energy Return the first isomer (that is, being thermal reversion) again.The photochromic compound of such as conventional thermal reversion is usually in response It is switched to the second state such as " coloured state " from the first state such as " clear state " during photochemical radiation and is restored back to when responding heat energy " transparent " state.

Dichroic compound is such compound, and it can be to one of the two of transmission light orthogonal planar polarization component Another component of absorptance is higher.Therefore, dichroic compound can linear polarization transmission light.As used herein, " the most inclined Shake " represent the vibration of the electric vector of light wave is restricted to a direction or plane.But, although dichroic material can preferentially be inhaled Receive one of two orthogonal planar polarization components of transmission light, but if the molecule of dichroic compound is unsuitable for location or row Row, the most also will can not realize the clean linear polarization of transmission light.That is, owing to the random orienting of dichroic compound molecule, single The selective absorbing of molecule will cancel each other out, and so can not realize clean or overall linear polarization effect.Therefore, typically required Suitably location or the arrangement in another material of dichroic compound molecule is formed the linear polarizing element of routine, such as, is used for The linear polarization filter of sunglasses or lens.

Contrary with dichroic compound, the photochromic compound molecule being typically without location or arrangement routine is formed Conventional photochromic element.The most conventional photochromic element such as can be with example for the lens of photochromic glasses As by being spun on lens surface containing the solution of conventional photochromic compound and " leading " material, and suitably solidify institute The coating formed or layer, and without being formed so that any concrete orientation arranges this photochromic compound.Even if additionally, The molecule of conventional photochromic compound is suitable to dichroic compound as discussed above and orients like that or arrange, but Because the photochromic compound of routine can not show strong dichroism, therefore it is frequently not strong by its made element Linear polarization.

It is desirable that the new photochromic compound of exploitation, it can show useful photochromic and/or be in The dichroic performance of at least one state, and its may be used for multiple should be for giving photochromic and/or dichroic performance.

Summary of the invention

According to the present invention, it is provided that the compound such as indeno fused ring compound shown in following formula I,

Ring A in Formulas I and other relevant formulas further disclosed herein is selected from (R¹)_m-group, unsubstituted aryl, take The aryl in generation, unsubstituted fused rings aryl, substituted fused rings aryl, unsubstituted heteroaryl and substituted heteroaryl.? In some embodiments, ring A is selected from aryl, fused rings aryl and heteroaryl.

Q ' group in Formulas I and other relevant formulas further disclosed herein is selected from halogen ,-OH ,-N₃,-NR^aR^a,-N (R^a) C (O) Q ' ', Q ' ' ,-CN ,-C (O) OR^a,-C ≡ C-R^a,-C (R^a)=C(R^a)(R^a) ,-OC (O) R^a,-OC (O) OR^a,-SR^a,- OS(O₂)R^b,-C (O) NR^aR^aWith lengthening agent L (as further described herein).Each R^aIndependently selected from hydrogen, alkyl and substituted Alkyl, each alkyl and substituted alkyl optionally and independently by following at least one are interrupted :-O-,-S-,-C (O)-,-C (O) O-,-S (O)-,-S (O₂)-,-N=N-,-N (R₁₁')-, wherein R₁₁' selected from hydrogen, alkyl or substituted alkyl ,-Si (OR₁₄)_u (R₁₄)_v-, wherein u and v is each independently selected from 0-2, condition be u and v sum be 2, and each R₁₄Independently selected from hydrogen, alkyl With substituted alkyl and its two or more combination.Selectable, two R^aGroup can be with-N and appointing selected from N and O The other hetero atom of choosing forms Heterocyclylalkyl together.R^bGroup is selected from perhalogeno alkyl, and Q ' ' is selected from halogen ,-OH ,- NR^aR^a,-C (O) OR^a,-SR^aWith optionally substituted aryl, wherein this substituent group is selected from-OH ,-NR^aR^a,-C (O) OR^a,-SR^a。

Subscript i of Formulas I is selected from 0-3.Subscript t of Formulas I is selected from 0 to R²The sum of the position can being bonded on ring A, such as 0-10 or 0-7 or 0-5 or 0-4 or 0-3.R¹Group is not bonded to ring position thereon can be instead by hydrogen group It is bonded on it.It is similar to, R²Group is not bonded to the position of ring A thereon and can be instead bonded on it by hydrogen group. With further reference to Formulas I, for each i, R¹With for each t, R², it is each independently selected from alkyl and substituted alkyl, each hydrocarbon Base and substituted alkyl optionally and independently by following at least one are interrupted :-O-,-S-,-C (O)-,-C (O) O-,-S (O)-,-S (O₂)-,-N=N-,-N (R₁₁')-, wherein R₁₁' selected from hydrogen, alkyl or substituted alkyl ,-Si (OR₁₄)_u(R₁₄)_v-, its Middle u and v is each independently selected from 0-2 (such as 0,1 or 2), condition be u and v sum be 2, and each R₁₄Independently selected from hydrogen, hydrocarbon Base and substituted alkyl and its two or more combination；Halogen；Cyano group；With-N (R₁₁’)R₁₂', wherein R₁₁' and R₁₂' each From independently selected from hydrogen, alkyl or substituted alkyl or R₁₁' and R₁₂' formed together and optional comprise at least one hetero atom Ring structure.

The R of Formulas I³And R⁴Group is each independently selected from hydrogen；Alkyl and substituted alkyl, each alkyl and substituted alkyl Optionally and independently by following at least one it is interrupted :-O-,-S-,-C (O)-,-C (O) O-,-S (O)-,-S (O₂)-,-N= N-,-N (R₁₁')-, wherein R₁₁' selected from hydrogen, alkyl or substituted alkyl ,-Si (OR₁₄)_u(R₁₄)_v-, wherein u and v is each independent Ground selected from 0-2 (such as 0,1 or 2), condition be u and v sum be 2, and each R₁₄Independently selected from hydrogen, alkyl and substituted hydrocarbon Base and its two or more combination.Selectable R³And R⁴Can form that optional to comprise at least one heteroatomic together Ring structure.

The R of Formulas I⁵Group is selected from hydrogen ,-C (O)-R¹³Or-S (O₂)R¹³, wherein R¹³It it is optionally substituted alkyl or optionally substituted Halohydrocarbyl.

According to the present invention, it is further provided a kind of compound such as indeno condensed ring pyrylium compound shown in Formula Il,

The different groups of Formula II and subscript such as R¹, R², R³And R⁴, subscript i and t, and ring A, each as previously mentioned and so Place is described further about the compound shown in Formulas I.The Q '″ group of Formula II is selected from halogen ,-OH ,-N₃,-NR^aR^a,-N (R^a)C (O) Q ' ', Q ' ' ,-CN ,-C (O) OR^a,-C ≡ C-R^a,-C (R^a)=C(R^a)(R^a) ,-OC (O) R^a,-OC (O) OR^a,-SR^a,-OS (O₂)R^bWith-C (O) NR^aR^a.Each R^aGroup is independently selected from hydrogen, alkyl and substituted alkyl, each alkyl and substituted alkyl Optionally and independently by following at least one it is interrupted :-O-,-S-,-C (O)-,-C (O) O-,-S (O)-,-S (O₂)-,-N= N-,-N (R₁₁')-, wherein R₁₁' selected from hydrogen, alkyl or substituted alkyl ,-Si (OR₁₄)_u(R₁₄)_v-, wherein u and v is each independent Ground selected from 0-2, condition be u and v sum be 2, and each R₁₄Independently selected from hydrogen, alkyl and substituted alkyl and its two kinds or More kinds of combinations, or two R^aGroup and-N and form heterocycle alkane together with the optional other hetero atom of N and O Base.R^bGroup is selected from perhalogeno alkyl, and Q ' ' is selected from halogen ,-OH ,-NR^aR^a,-C (O) OR^a,-SR^aWith substituted aryl.

B and the B ' group of Formula II is each independently selected from hydrogen, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl Base, substituted heteroaryl, poly-alkoxyl, and there is the poly-alkoxyl of polymerisable group, or formed selected from not together with B with B ' Substituted fluorenes-9-subunit, substituted fluorenes-9-subunit, saturated spiral shell monocycle hydrocarbon ring, saturated spiral shell dicyclo hydrocarbon ring and spiral shell tricyctic hydrocarbon ring Ring structure.

According to the present invention, it is further provided photochromic composition and goods, these goods include the present invention one or Multiple compounds, the such as compound shown in Formula II.

Accompanying drawing explanation

Fig. 1 is to be property embodiment according to different unconditional disclosed herein, uses cassette method (CELL METHOD) institute The diagram of two mean difference absorption spectrums of the photochromic compound obtained.

Detailed description of the invention

As herein with claim in use, term " photochemical radiation " represents such electromagnetic radiation, and it can Photochromic material is become another kind from a kind of form or State Transferring.

As herein with claim in use, term " photochromic " represent have at least visible radiation Absorption spectrum, it changes when responding at least photochemical radiation absorption.Additionally, as used herein, term " light-induced variable Color material " represent any material for showing photochromic properties, i.e. for there is absorbing light at least visible radiation Spectrum, it changes when responding at least photochemical radiation absorption, and it includes at least one photochromic compound.

As herein with claim in use, the molecular weight values of polymer such as weight average molecular weight (Mw) sum is divided equally Son amount (Mn) is by gel permeation chromatography, uses suitable reference material such as polystyrene standards to measure.

As herein with claim in use, polydispersity index (PDI) value represents the weight average molecular weight of polymer (Mw) with the ratio (that is, Mw/Mn) of number-average molecular weight (Mn).

As herein with claim in use, term " halogen " and similar terms such as halo group, halogen and halogen Group represents F, Cl, Br and/or I, such as fluorine, chlorine, bromine and/or iodine.

Unless otherwise directed, four corner the most disclosed herein or ratio are understood to include be included in any With whole subranges or sub-ratio.Such as " 1-10 " described scope or ratio should be believed to comprise minima 1 and maximum 10 Between any and whole subrange (with including 1 and 10)；That is, from minima 1 or bigger from the beginning of, to maximum 10 or less end Whole subranges or sub-ratio, such as but not limited to 1-6.1,3.5-7.8 and 5.5-10.

As using with in claim herein, article " ", " a kind of " and " being somebody's turn to do " include plural, unless bright True and unambiguous be restricted to one and refer to thing.

Except operating in embodiment or one-tenth the most indicated otherwise, otherwise used in expression description and claims Point, whole numerals of the amount of reaction condition etc. are understood to be in the case of all and use term " about " correction.

As herein with claim in use, term " precursor " and relational language, as with compound described herein and Intermediate, such as the indeno fused ring compound shown in Formulas I, the different group of indeno condensed ring pyrylium compound shown in Formula II is such as R¹, R², R³, R⁴, R⁵, Q ', Q '″, B, B ' and " precursor " relevant with L, represent such group, it can one or more steps In change into final or desired group.In unconditional is property explanation: the precursor of hydroxyl (-OH) includes but not limited to carboxylate Group (-OC (O) R, wherein R is hydrogen or optionally substituted alkyl)；Include with the precursor of carboxylate group (-OC (O) R) but do not limit In hydroxyl (-OH), it can such as react with carboxylic acid halide's such as monoxone (or chloroacetic chloride).

Above different with intermediate with compound the most described further groups, such as but not limited to Formulas I and II and phase The R of compound shown in the formula of pass¹, R², R³, R⁴, R⁵, Q ', Q '″, B, B ' and lengthen agent L group, can be independently in each situation Selected from alkyl and substituted alkyl.

As herein with claim in use, term " alkyl " and similar terms such as " hydrocarbyl substituent " and " alkyl " Represent: straight chain or branched C₁-C₂₀Alkyl (such as straight chain or branched C₁-C₁₀Alkyl)；Straight chain or branched C₂-C₂₀ Alkenyl (such as straight chain or branched C₂-C₁₀Alkenyl)；Straight chain or branched C₂-C₂₀Alkynyl (such as straight chain or The C changed₂-C₁₀Alkynyl)；C₃-C₁₂Cycloalkyl (such as C₃-C₁₀Cycloalkyl)；C₃-C₁₂Heterocyclylalkyl (has at least one miscellaneous in ring Atom)；C₅-C₁₈Aryl (including polyaromatic) (such as C₅-C₁₀Aryl)；C₅-C₁₈Heteroaryl (has at least one in aromatic ring Individual hetero atom)；And C₆-C₂₄Aralkyl (such as C₆-C₁₀Aralkyl).

Representative alkyl includes but not limited to methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, tertiary fourth Base, amyl group, neopentyl, hexyl, heptyl, octyl group, nonyl and decyl.Representative alkenyl includes but not limited to vinyl, allyl Base and acrylic.Representative alkynyl includes but not limited to acetenyl, 1-propinyl, 2-propynyl, ethyl acetylene base and 2-butyne base. Representative cycloalkyl includes but not limited to cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl and ring octyl substituents.Representative heterocycle Alkyl includes but not limited to tetrahydrofuran base, THP trtrahydropyranyl and piperidyl.Representative aryl includes but not limited to phenyl and naphthalene Base.Representative heteroaryl includes but not limited to furyl, pyranose and pyridine radicals.Representative aralkyl includes but not limited to benzyl And phenethyl.

As herein with claim in use, term " substituted alkyl " represent alkyl, wherein its at least one Hydrogen has been substituted with a group that be other than hydrogen, such as but not limited to halogen group, hydroxyl, ether group, thiol group, sulfide group, carboxylic Acid groups, carboxylate group, phosphate group, bound phosphate groups, sulfonic acid group, sulfonate ester group, nitro, cyano group, alkyl is (such as Alkyl, alkenyl, alkynyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and aralkyl) and amine groups, such as-N (R₁₁’) (R₁₂'), wherein R₁₁' and R₁₂' it is each independently selected from hydrogen, alkyl and substituted alkyl or R₁₁' and R₁₂' form ring together, What it was optional comprises at least one hetero atom (such as-O-,-Si-and/or-S-).

Term " substituted alkyl " includes halohydrocarbyl (or alkyl of halo) substituent group.As herein and claim Middle use, term " halohydrocarbyl " and the alkyl of similar terms, such as halo, represent alkyl (such as alkyl, alkenyl, alkynes Base, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl and aralkyl) at least one hydrogen atom be selected from the halogen of chlorine, bromine, fluorine and iodine Element atom is replaced.Halogenation degree can be replaced (such as methyl fluoride) to whole halogenations from least one hydrogen atom by halogen atom (perhalogenation), wherein whole on this alkyl alternative hydrogen atoms is replaced (such as trifluoromethyl or perfluor first by halogen atom Base).Accordingly, as herein with claim in use, term " perhalogeno alkyl " represents such alkyl, the most all Replaceable hydrogen is replaced by halogen.The example of perhalogeno alkyl includes but not limited to fully halogenated phenyl and fully halogenated alkane Base.

Alkyl and substituted alkyl (different groups and substituent group such as R¹, R², R³, R⁴, R⁵, Q ', Q '″ and L is each can With selected from this group) can be interrupted by following at least one with optional independently in each situation :-O-,-S-,-C (O)-,-C (O) O-,-S (O)-,-S (O₂)-,-N=N-,-N (R₁₁')-, and-Si (OR₁₄)_u(R₁₄)_v-.As wanting with right herein Ask middle use, be interrupted by following at least one :-O-,-S-,-C (O)-,-C (O) O-,-S (O)-,-S (O₂)-,-N=N-,- N(R₁₁')-, and-Si (OR₁₄)_u(R₁₄)_v-, it means that at least one carbon of this alkyl or substituted alkyl, but be less than all Carbon, substituted with one of described divalent linker the most independently.This alkyl and substituted alkyl can be used Two or more above-mentioned linking groups are interrupted, and it can be adjacent one another are or adjacent by one or more carbon respectively.

As herein with claim in use, unless otherwise directed, linking group such as divalent linker from a left side to Right expression includes other suitable directions, direction the most from right to left.In unconditional is property explanation, divalent linker Group's-C (O) O-expression from left to right includes its expression-O (O) C-from right to left.

As using with in claim herein, statement " straight chain or branched " or " straight chain, branched or ring " base Group such as straight chain or branched alkyl, or straight chain, branched or cycloalkyl, be interpreted as at this including: methylene or methyl；Directly Chain group such as straight chain C₂-C₂₅Alkyl；The most branched group, the most branched C₃-C₂₅Alkyl；With the group of suitably cyclisation, example Such as C₃-C₂₅Cycloalkyl (or ring C₃-C₂₅Alkyl) group.

In some embodiments of the present invention, it is provided that the photochromic compound of a kind of thermal reversion, it has and is in Above and the Q ' of position the most described further or Q '″ group, and the most optional one or more lengthen group L. Other unconditional are that property embodiment provides a kind of photochromic compound, and it is suitable to have at least the first state and the second shape State, the wherein photochromic compound of this thermal reversion cassette method (CELL that basis is described below in detail at least one state METHOD) average absorption ratio measured by is more than 2.3.Additionally, be property embodiment according to different unconditional, this thermal reversion Photochromic compound is more than 2.3 when the state of activation according to the average absorption ratio measured by cassette method (CELL METHOD).Make For used herein, term " photochromic compound " (PC) refers to one or more photochromic compounds, including but not It is limited to the photochromic compound of the present invention, the such as compound shown in Formula II.As herein in regard to photochromic compound institute Using, term " state of activation " refers to this photochromic compound to be caused at least when being exposed to enough photochemical radiations This photochromic compound of a part is in switching state.Additionally, as used herein, term " compound " represents two kinds Or more kinds of element, component, composition or partly combine the material formed, and include, without being limited to by two or more Element, component, composition or partly combine the molecule formed and macromole (such as polymer or oligomer).

As a rule, the cassette method (CELL METHOD) of the average absorption ratio measuring photochromic compound includes obtaining The absorption spectrum of this photochromic compound, it is in activation or its non-activated state, is in the every of two orthogonal polarization orientation On individual, this photochromic compound is at least part of simultaneously arranges in being contained in the liquid crystal media of arrangement of case assembly. More specifically, this case assembly comprises two relative substrate of glass, its 20 microns of interval +/-1 micron.By this substrate along two Opposite side seals and forms box.Being coated with polyimide coating on the inner surface of each substrate of glass, its surface has been passed through to wipe Wipe and at least partly orient.The orientation of this photochromic compound is by photochromic compound and liquid crystal media being incorporated into In case assembly, and the arrangement on the polyimide surface of friction of this liquid crystal media is realized.Because this is photochromic Compound is included in liquid crystal media, and therefore the orientation of liquid crystal media causes the arrangement of this photochromic compound.This area Skilled artisan will appreciate that the selection of liquid crystal media used in testing and temperature can affect measured absorbance.Therefore, as Being described in detail in embodiment, in cassette method (CELL METHOD), Optical thin film is in room temperature (73 °F of +/-0.5 °F Or more preferably) carry out, and liquid crystal media is(it it is reported it is cyanobiphenyl and cyano group triphenyl to E7 The mixture of liquid-crystal compounds).

Once liquid crystal media and photochromic compound arrangement, then this case assembly is placed on optical bench (its in an embodiment More detailed description).In order to obtain the average absorption ratio of the state of activation, the activation of this photochromic compound is such as reality of getting off Existing: this photochromic compound to be exposed to UV and radiates time enough, reach saturated or close to saturated state (i.e., Such state, wherein the absorbability of this photochromic compound is not changed in measuring the time interval carried out substantially).Right In be perpendicular to optical bench plane (referred to as 0 ° plane of polarization or direction) internal linear polarize light and be parallel to optical bench Plane (referred to as 90 ° planes of polarization or direction) internal linear polarization light for, absorptiometry is with following order, with 3 Second is spaced in what the regular hour interior (typical 10-300s) was carried out: 0 °, 90 °, 90 °, 0 ° etc..For whole test wavelengths, By the absorbance of the linearly polarized photon of box in each time interval measurement, and deduct on the wavelength of same range Non-activated absorbance (that is, having the absorbance of the box of liquid crystal material and non-activated photochromic compound) obtains this Photochromic compound absorption spectrum in each 0 ° and 90 ° of planes of polarization, obtain be in saturated or close to saturated shape This photochromic compound of state mean difference absorption spectrum in each plane of polarization.

It is to illustrate and see in Fig. 1 in unconditional, which show the mean difference absorbing light in a plane of polarization Spectrum (being typically expressed as 10), it is available from the photochromic chemical combination according to a kind of unconditional disclosed herein being property embodiment Thing.Average absorption spectrum (being typically expressed as 11) is mean difference absorption spectrum, available from light identical in cross-polarization plane Cause electrochromic compound.

Based on the mean difference absorption spectrum available from this photochromic compound, the average absorption of this photochromic compound Rate such as acquisition of getting off.This photochromic compound corresponds at the absorbance of each wavelength of the wavelength of preset range λ_max-vis+/-5nm (is typically expressed as 14) in FIG, wherein λ_max-visIt is that this photochromic compound has in any plane Wavelength residing during the highest average absorption ratio, it calculates according to equation below:

AR_λi=Ab¹ _λi/Ab² _λiEquation 1

Wherein AR_λiIt is the absorbance in wavelength X i, Ab¹ _λiIt is that (that is, 0 ° or 90 °) have higher absorption in polarization direction The average absorption ratio of wavelength X i of rate, and Ab² _λiIt it is the average absorption ratio of wavelength X i on remaining polarization direction.As it was previously stated, " absorptance " refer to first plane internal linear polarization radiation absorbance with in the plane interior lines being orthogonal to the first plane Property polarization the ratio of absorbance of radiation of phase co-wavelength, wherein take this first plane as the plane with maximum absorption rate.

Then according to equation below, by (that is, the λ of the wavelength at preset range averagely obtained_max-vis+/-5nm) In the single absorbance of wavelength, calculate the average absorption ratio (" AR ") of this photochromic compound:

AR=(λAR_λi)/n_iEquation 2

Wherein AR is the average absorption ratio of this photochromic compound, AR_λiIt is wavelength (that is, the λ at preset range_max-vis +/-5nm) in the single absorbance (as determined by equation 1 above) of each wavelength, and n_iIt it is average single absorption The number of rate.

Cut as it was previously stated, the photochromic compound of the thermal reversion of routine is adapted to respond to photochemical radiation from the first state Change to the second state, and response heat energy is restored back to the first state.More specifically, the photochromic compound energy of conventional thermal reversion Enough response light chemical radiations and be converted into another isomeric forms from a kind of isomeric forms (such as and be not limited to closing form) (such as and be not limited to opening mode), and it is restored back to closing form when be exposed to heat energy.But, as it was previously stated, the most conventional What the photochromic compound of thermal reversion was the strongest shows dichroism.

As it has been described above, unconditional disclosed herein is the photochromic chemical combination that property embodiment provides a kind of thermal reversion Thing, it is more than 1.5, and/or one according to the average absorption ratio measured by cassette method (CELL METHOD) at least one state Planting the photochromic compound of thermal reversion, it can serve as the intermediate of the photochromic compound preparing absorbance more than 1.5. Therefore according to this unconditional be the photochromic compound of the thermal reversion of property embodiment can show photochromic Performance and/or useful photochromic and dichroic performance.That is, the photochromic compound of this thermal reversion can be thermal reversion Photochromic and/or photochromic-dichroic compound.Used as herein in regard to this photochromic compound described herein , term " photochromic-dichroic " expression demonstrates photochromic and both dichroic performances, this performance under certain conditions Can measure at least through instrument.

Being property embodiment according to other unconditional, the photochromic compound of this thermal reversion can be the photic of thermal reversion Variable color-dichroic compound, its at least one state according to the average absorption ratio measured by cassette method (CELL METHOD) It is 4-20,3-30 or 2.0-50.It will be appreciated by those skilled in the art that the average absorption ratio of this photochromic compound is the highest, should The linear polarization of photochromic compound is the biggest.So, it is property embodiment according to different unconditional, this thermal reversion photic Electrochromic compound can have required any average absorption ratio, realizes desired level of linear polarization.

Another unconditional is the photochromic compound that property embodiment provides a kind of thermal reversion, and it does not has Piperazine, and be suitable to that there is at least the first state and the second state, wherein this photochromic compound root at least one state It is at least 1.5 according to the average absorption ratio measured by cassette method (CELL METHOD).Additionally, be that property is implemented according to this unconditional Scheme, at least one state, can be 1.5-50 according to this average absorption ratio that cassette method (CELL METHOD) is measured.

Those compounds as shown in Formulas I and II of the compounds of this invention and the group of related compound and substituent group will be at these In describe in more detail, and compound and the intermediate in their preparation describes in greater detail below.

The ring A of the compounds of this invention compound as shown in Formulas I and II can be independently selected from not taking in each situation The aryl in generation, substituted aryl, unsubstituted fused rings aryl, substituted fused rings aryl, unsubstituted heteroaryl and replacement Heteroaryl.Typically, ring A is except (R¹)_iOutside-group, selected from unsubstituted aryl, unsubstituted fused rings aryl and not Substituted heteroaryl (or aryl, fused rings aryl and heteroaryl).Ring A can include selected from the example of its aryl but not limit In phenyl and biphenyl.Ring A can selected from its example of fused rings aryl include but not limited to polycyclic aromatic hydrocarbon, such as naphthyl and Anthryl.Ring A can include but not limited to furyl, pyranose and pyridine radicals selected from the example of its heteroaryl.

The Q ' of the compounds of this invention and Q '″ group is the most each can be independently selected from-N₃,-CN ,- C(O)OR^a,-C ≡ C-R^a,-C (R^a)=C(R^a)(R^a) ,-OC (O) R^a,-OC (O) OR^a,-SR^a,-OS (O₂)R^bWith-C (O) NR^aR^a, The most each R^aIndependently selected from hydrogen, alkyl and substituted alkyl, each alkyl and substituted alkyl optionally and independently by Previously described divalent group is interrupted.In some embodiments, for Q ' and Q '″, each R^aGroup independently selected from Hydrogen, the unsubstituted or substituted alkyl with 1-18 carbon atom, unsubstituted or substituted aryl, unsubstituted or replacement The alkene with 2-18 carbon atom or alkyne groups, wherein said substituent group is selected from halogen and hydroxyl, and R^bSelected from tool There is the perfluorinated alkyl of 1-18 carbon atom.The example of perfluorinated alkyl includes but not limited to perfluoro-methyl (-CF₃), perfluor second Base (-CF₂CF₃), perfluoro propyl, including perfluor n-pro-pyl, perfluoroisopropyl, perfluoro butyl, including its isomer, such as perfluor Normal-butyl and perfluoro-t-butyl, and perfluoro capryl, including its isomer.

In some other embodiments of the present invention, for Q ' and Q '″, each R^aGroup independently selected from Hydrogen and the alkyl with 1-6 carbon atom, and R^bSelected from the perfluorinated alkyl with 1-6 carbon atom.

Q ' and Q '″ group can be each independently selected from bromine, fluorine, chlorine ,-N in some embodiments₃,-NR^aR^a,-N (R^a) C (O) Q ' ', Q ' ' ,-C (O) OR^a,-C ≡ C-R^a,-C (R^a)=C(R^a)(R^a) ,-OC (O) R^a,-OC (O) OR^a,-SR^a,-OS (O₂)R^b,-C (O) NR^aR^a.Q ' can also be to lengthen agent L (as described further herein).Each R^aGroup can be independently selected from Hydrogen, the unsubstituted or substituted alkyl with 1-18 carbon atom, unsubstituted or substituted aryl, unsubstituted or replacement The alkene with 2-18 carbon atom or alkyne groups, wherein said substituent group be selected from halogen and hydroxyl.Selectable, two Individual R^aGroup can with-N and selected from the other hetero atom of N and O together with form Heterocyclylalkyl.R^bGroup can be selected from having 1- The fluoridized alkyl of 18 carbon atoms.Q ' ' group can be selected from-OH ,-NR^aR^a,-C (O) OR^a,-SR^a, and optionally substituted Aryl, wherein this substituent group is selected from-OH ,-NR^aR^a,-C (O) OR^a,-SR^a。

In further embodiment, Q ' and Q '″ are each independently selected from bromine, chlorine ,-NR^aR^aWith-C (O) OR^a.Q ' also may be used To be lengthening agent L.Each R^aIndependently selected from hydrogen and the alkyl with 1-6 carbon atom.Selectable, two R^aGroup and-N Heterocyclylalkyl is formed together with other atom N.R^bGroup is selected from the fluoridized alkyl with 1-6 carbon atom.

In some embodiments of the present invention, Q '″ is selected from lengthening agent L.

The R of the indeno fused ring compound of the present invention⁵Group, such as formula I above and Formulas I a (as being described further herein) The R of shown those⁵Group, can be selected from hydrogen ,-C (O)-R¹³Or-S (O₂)R¹³, wherein R¹³It is alkyl or halohydrocarbyl.One In a little embodiments, R⁵Selected from hydrogen and-C (O)-R¹³.Typically, R¹³C can be selected from₁-C₁₂Or C₁-C₆Alkyl or perhaloalkyl radical, Such as perfluoroalkyl.

Indeno fused ring compound as shown in formula I and the indeno condensed ring pyrylium compound as shown in Formula II are come Say, for each i, R¹With for each t, R²It is each independently selected from: (a)-C (O) X₂₄；(b)-OX₇With-N (X₇)₂；(c)- SX₁₁；Shown in (d) formula i containing azo-cycle, as will be further described herein；E the group shown in () formula ii and iii, as herein Will be further described；(f) or the R of next-door neighbour¹Group and the R of next-door neighbour²Group, shape independently together in each situation Accepted way of doing sth vii, the group shown in viii or ix, as will be further described herein；Lengthening agent L shown in (g) formula III, as Will be further described herein；(h) group B, as will be further described herein.

In some embodiments, for each i, R¹With for each t, R²It is each independently selected from, (a)-C (O) X₂₄, Wherein X₂₄Selected from lengthening agent L (as being described further herein), hydroxyl, C₁-C₁₈Alkyl, C₁-C₁₈Alkoxyl, unsubstituted or Use C₁-C₁₈Alkyl or C₁-C₁₈The mono-substituted phenyl of alkoxyl, unsubstituted, with the C of at least one₁-C₁₈Alkyl, phenyl, benzyl With naphthyl list or dibasic amino.

In some other embodiments, for each i, R¹With for each t, R²It is each independently selected from (a)-C (O)X₂₄, wherein X₂₄Selected from lengthening agent L (as being described further herein), hydroxyl, C₁-C₁₂Alkyl, C₁-C₁₂Alkoxyl, not Substituted or use C₁-C₆Alkyl or C₁-C₆The mono-substituted phenyl of alkoxyl, unsubstituted, with the C of at least one₁-C₆Alkyl, benzene Base, benzyl and naphthyl list or dibasic amino.

According in other embodiments, for each i, R¹With for each t, R²It is each independently selected from (a)-C (O) X₂₄, wherein X₂₄Selected from hydroxyl, C₁-C₆Alkyl, C₁-C₆Alkoxyl, unsubstituted or use C₁-C₆Alkyl or C₁-C₆Alkoxyl list Substituted phenyl, unsubstituted, with the C of at least one₁-C₆Alkyl, phenyl, benzyl and naphthyl list or dibasic amino.

In some embodiments, for each i, R¹With for each t, R²It is each independently selected from (b)-OX₇With-N (X₇)₂, the most each X₇Independently selected from four classes group (i), (ii), (iii) and (iv).In some embodiments, X₇It is selected from I () hydrogen, lengthens agent L (as being described further herein), C₁-C₁₈Alkyl, C₁-C₁₈Acyl group, phenyl (C₁-C₁₈) alkyl, single (C₁-C₁₈) alkyl substituted phenyl (C₁-C₁₈) alkyl, single (C₁-C₁₈) alkoxyl substituted phenyl (C₁-C₁₈) alkyl；C₁-C₁₈Alkane Epoxide (C₁-C₁₈) alkyl；C₃-C₁₀Cycloalkyl；Single (C₁-C₁₈) the substituted C of alkyl₃-C₁₀Cycloalkyl, C₁-C₁₈Haloalkyl, allyl Base, benzoyl, mono-substituted benzoyl, naphthoyl or mono-substituted naphthoyl, the most each described benzoyl and The substituent group of naphthoyl is independently selected from C₁-C₁₈Alkyl, and C₁-C₁₈Alkoxyl.Each X₇Can be independently selected from (ii)-CH (X₈)X₉, wherein X₈Selected from hydrogen, lengthen agent L, or C₁-C₁₈Alkyl, and X₉Selected from lengthening agent L ,-CN ,-CF₃Or-COOX₁₀, its Middle X₁₀Selected from hydrogen, lengthen agent L (as being described further herein) or C₁-C₁₈Alkyl.Each X₇Can (iii)-C independently (O)X₆, wherein X₆Selected from least one following: hydrogen, lengthen agent L (as being described further herein), C₁-C₁₈Alkoxyl, not Substituted, use C₁-C₁₈Alkyl or C₁-C₁₈Alkoxyl list or dibasic phenoxy group, unsubstituted, use C₁-C₁₈Alkyl or C₁- C₁₈Alkoxyl list or dibasic aryl, unsubstituted, use C₁-C₁₈Alkyl list or dibasic amino, and unsubstituted, Use C₁-C₁₈Alkyl or C₁-C₁₈Alkoxyl list or dibasic phenyl amino.The most each X₇Can be independently selected from (iv) three (C₁-C₁₈) aIkylsilyl groups, three (C₁-C₁₈) alkyl siloxy, three (C₁-C₁₈) alkoxysilyl, three (C₁-C₁₈) Alkoxy silicane epoxide, two (C₁-C₁₈) alkyl (C₁-C₁₈Alkoxyl) silicyl, two (C₁-C₁₈) alkyl (C₁-C₁₈Alcoxyl Base) siloxy, two (C₁-C₁₈) alkoxyl (C₁-C₁₈Alkyl) silicyl or two (C₁-C₁₈) alkoxyl (C₁-C₁₈Alkane Base) siloxy.

In other embodiments of the present invention, for each i, R¹With for each t, R²Be each independently selected from (b)- OX₇With-N (X₇)₂, the most each X₇Independently selected from (i) hydrogen, lengthen agent L, C₁-C₁₂Alkyl, C₁-C₁₂Acyl group, phenyl (C₁-C₁₂) Alkyl, single (C₁-C₁₂) alkyl substituted phenyl (C₁-C₁₂) alkyl, single (C₁-C₁₂) alkoxyl substituted phenyl (C₁-C₁₂) alkyl； C₁-C₁₂Alkoxyl (C₁-C₁₂) alkyl；C₃-C₇Cycloalkyl；Single (C₁-C₁₂) the substituted C of alkyl₃-C₇Cycloalkyl, C₁-C₁₂Alkyl halide Base, pi-allyl, benzoyl, mono-substituted benzoyl, naphthoyl or mono-substituted naphthoyl, the most each described benzene first The substituent group of acyl group and naphthoyl is independently selected from C₁-C₆Alkyl, and C₁-C₆Alkoxyl.Each X₇Can also be independently selected from (ii)-CH(X₈)X₉, wherein X₈Selected from hydrogen, lengthen agent L or C₁-C₁₂Alkyl；And X₉Selected from lengthening agent L ,-CN ,-CF₃Or- COOX₁₀, wherein X₁₀Selected from hydrogen, lengthen agent L or C₁-C₁₂Alkyl.Each X₇Can additionally be selected from (iii)-C (O) X₆, wherein X₆Choosing From at least one following: hydrogen, lengthen agent L, C₁-C₁₂Alkoxyl, unsubstituted, use C₁-C₁₂Alkyl or C₁-C₁₂Alkoxyl list or The dibasic phenoxy group of person, unsubstituted, use C₁-C₆Alkyl or C₁-C₆Alkoxyl list or dibasic aryl, unsubstituted , use C₁-C₆Alkyl list or dibasic amino, and unsubstituted, use C₁-C₆Alkyl or C₁-C₆Alkoxyl list or two Substituted phenyl amino.

In other embodiments of the present invention, for each i, R¹With for each t, R²Be each independently selected from (b)- OX₇With-N (X₇)₂, the most each X₇Independently selected from (i) hydrogen, C₁-C₆Alkyl, C₁-C₆Acyl group, phenyl (C₁-C₆) alkyl, single (C₁- C₆) alkyl substituted phenyl (C₁-C₆) alkyl, single (C₁-C₆) alkoxyl substituted phenyl (C₁-C₆) alkyl；C₁-C₆Alkoxyl (C₁-C₆) alkyl；C₃-C₅Cycloalkyl；Single (C₁-C₆) the substituted C of alkyl₃-C₅Cycloalkyl, C₁-C₆Haloalkyl, pi-allyl, benzene first Acyl group, mono-substituted benzoyl, naphthoyl or mono-substituted naphthoyl, the most each described benzoyl and naphthoyl Substituent group is independently selected from C₁-C₃Alkyl and C₁-C₃Alkoxyl.Each X₇(ii)-CH (X can also be selected from₈)X₉, wherein X₈It is selected from Hydrogen or C₁-C₆Alkyl；And X₉Selected from-CN ,-CF₃Or-COOX₁₀, wherein X₁₀Selected from hydrogen or C₁-C₆Alkyl.Each X₇Can also enter One step is selected from (iii)-C (O) X₆, wherein X₆Selected from hydrogen, C₁-C₁₂Alkoxyl, unsubstituted, use C₁-C₆Alkyl or C₁-C₆Alkoxyl Single or dibasic phenoxy group, unsubstituted, use C₁-C₃Alkyl or C₁-C₃Alkoxyl list or dibasic aryl, do not take Generation, use C₁-C₃Alkyl list or dibasic amino, and unsubstituted, use C₁-C₃Alkyl or C₁-C₃Alkoxyl list or two Substituted phenyl amino.

In some embodiments, for each i, R¹With for each t, R²It is each independently selected from (c)-SX₁₁, wherein X₁₁Selected from hydrogen, lengthen agent L, C₁-C₁₈Alkyl, C₁-C₁₈Haloalkyl, unsubstituted or use C₁-C₁₈Alkyl, C₁-C₁₈Alkoxyl Or halogen list or dibasic aryl.-SX₁₁X₁₁Group can also be selected from C₁-C₆Alkyl, C₁-C₆Haloalkyl, unsubstituted Or use C₁-C₆Alkyl, C₁-C₆Alkoxy or halogen such as chlorine, bromine or fluorine list or dibasic aryl (such as phenyl).

In some embodiments, for each i, R¹With for each t, R²It is each independently selected from shown in (d) following formula i Containing azo-cycle:

About formula i, there is place independently selected from-CH each in each-Y-₂-,-CH (R₁₃')-,-C (R₁₃’)₂-,-CH (virtue Base)-,-C (aryl)₂-, and-C (R₁₃') (aryl)-, and Z be-Y-,-O-,-S-,-S (O)-,-SO₂-,-NH-,-N (R₁₃')-, Or-N (aryl)-, the most each R₁₃' it is to lengthen group L, or C independently₁-C₂₀Alkyl (such as C₁-C₁₂Alkyl or C₁-C₆ Alkyl), each aryl is phenyl or naphthyl independently, and m is integer 1,2 or 3, and p is integer 0,1,2 or 3, and condition is to work as p Be 0, then Z is-Y-.

In further embodiment, for each i, R¹With for each t, R²Be each independently selected from (e) following formula ii or Group shown in formula iii,

About formula ii and iii, X₁₄, X₁₅And X₁₆Place occurs independently selected from hydrogen each, lengthen agent L, C₁-C₁₈Alkyl, phenyl Or naphthyl, or X₁₄And X₁₅Forming the ring of 5-8 carbon atom together, p is selected from 0,1 or 2 integers, and X₁₇At each appearance only On the spot selected from lengthening agent L, C₁-C₁₈Alkyl, C₁-C₁₈Alkoxy or halogen.

According to other embodiments, for each i, R¹With for each t, R²It is each independently selected from formula ii or formula iii Shown group, as it appears from the above, wherein X₁₄, X₁₅And X₁₆Place occurs independently selected from hydrogen each, lengthen agent L, C₁-C₁₂Alkyl, benzene Base or naphthyl, or X₁₄And X₁₅Form the ring of 5-7 carbon atom together；P is the integer selected from 0,1 or 2, and X₁₇At each appearance Independently selected from lengthening agent L, C₁-C₁₂Alkyl, C₁-C₁₂Alkoxy or halogen.

According to other embodiments, for each i, R¹With for each t, R²It is each independently selected from formula ii or formula iii Shown group, as it appears from the above, wherein X₁₄, X₁₅And X₁₆Place occurs independently selected from hydrogen, C each₁-C₆Alkyl or phenyl, or X₁₄And X₁₅Form the ring of 5-7 carbon atom together；P is the integer selected from 0,1 or 2, and X₁₇Each occur place independently selected from C₁-C₆Alkyl, C₁-C₆Alkoxy or halogen.

According to some embodiments, the R of next-door neighbour¹Group and the R of next-door neighbour²Group independently together forms in each situation Group shown in following formula vii, viii or ix,

About formula vii and viii, W and W ' there is place independently selected from-O-,-N (X each in W and W '₇)-,-C (X₁₄)-and-C (X₁₇)-.With further reference to formula vii, viii and ix, X₁₄And X₁₅Place occurs independently selected from hydrogen each, lengthen agent L, C₁-C₁₈Alkane Base, phenyl or naphthyl, or X₁₄And X₁₅Form the ring of 5-8 carbon atom together；And X₁₇Place occurs independently selected from lengthening each Agent L, C₁-C₁₈Alkyl, C₁-C₁₈Alkoxy or halogen.Seeing formula ix, q is the integer selected from 0,1,2,3 and 4.

In some embodiments of the present invention, can be shown in following formula-(XI) and-(XII) containing azo-cycle shown in formula i Option.

Formula-(XI)

Formula-(XII)

In the case of formula-(XI) and-(XII), R₁₇' in each case independently selected from hydrogen or alkyl, such as C₁- C₆Alkyl, or optionally substituted aryl, the most optionally substituted phenyl, and accordingly, this contain azo-cycle selected from substituted or Unsubstituted piperidyl (such as formula-XI), and/or substituted or unsubstituted morpholinyl (such as formula-XII).

According to other embodiments of the present invention, the R of next-door neighbour¹Group and the R of next-door neighbour²Group in each situation independently Forming formula vii together, the group shown in viii or ix, as it has been described above, wherein there is place independently selected from-O-,-N each in W and W ' (X₇)-,-C (X₁₄)-and-C (X₁₇)-。X₁₄And X₁₅Group is selected from hydrogen independently of one another at each appearance, lengthens agent L, C₁-C₁₂Alkane Base, phenyl or naphthyl, or X₁₄And X₁₅Form the ring of 5-7 carbon atom together；And X₁₇Place occurs independently selected from lengthening each Agent L, C₁-C₁₂Alkyl, C₁-C₁₂Alkoxy or halogen.Additionally q is the integer selected from 0-3.

According to other embodiments of the present invention, the R of next-door neighbour¹Group and the R of next-door neighbour²Group in each situation independently Forming formula vii together, the group shown in viii or ix, as it has been described above, wherein there is place independently selected from-O-,-N each in W and W ' (X₇)-,-C (X₁₄)-and-C (X₁₇)-。X₁₄And X₁₅There is place independently selected from hydrogen, C each in group₁-C₆Alkyl, phenyl or naphthyl, Or X₁₄And X₁₅Form the ring of 5-7 carbon atom together；And X₁₇Place occurs independently selected from C each₁-C₆Alkyl, C₁-C₆Alcoxyl Base or halogen.Additionally q is the integer selected from 0-3.

The indeno fused ring compound of the present invention and the different groups of indeno condensed ring pyrylium compound, include but not limited to, right In each i, R¹With for each t, R², Q ' and Q '″ can include or independently of one another selected from the lengthening agent L shown in Formula Il I,

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

III

As use with claim herein, term " lengthens agent L " and similar terms is as lengthened agent and lengthening group, table Show in each situation, independently selected from the group of group shown in formula III described above and as detailed further below 's.

As used herein, term " connects " expression by another group Direct Bonding or indirect linkage.Therefore example As, it is property embodiment according to different unconditional disclosed herein, L can be straight as the substituent group on the compounds of this invention Connect and be bonded on this compound, or L can be another group (the such as R being bonded directly on this compound¹Shown group) On substituent group (that is, on L indirect linkage to this compound).Although the most not limiting, but according to different unconditional it is Property embodiment, L may be coupled on this compound, extends or lengthen this compound being in the state of activation so that should The absorbance of the compound (such as this photochromic compound) extended is improved compared with there is not the compound lengthening agent. Although the most not limiting, but being property embodiment according to different unconditional, L link position on compound can select Select so that L by this compound in the direction parallel with the theoretical transitional dipole square of the compound of activated form or vertical At least one side in direction upwardly extends.About the position of L, it can be connected to this subsequently on the position of Q ' or Q '″ group On compound.The compounds of this invention can have at least one Q ' or Q '″ group, and optional one on shown position Or multiple L group.As used herein, term " theoretical transitional dipole square " refers to by electromagnetic radiation and molecule phase interaction Polarize with produced transient dipole.See for example IUPAC Compendium of Chemical Technology, second edition, International Union of Pure and AppliedChemistry(1997)。

In some embodiments, each Q of formula III₁, Q₂And Q₃Place occurs independently selected from divalent group each, its choosing From unsubstituted or substituted aromatic group, unsubstituted or substituted alicyclic group, unsubstituted or substituted heterocyclic radical Group and mixture thereof.This substituent group Q₁, Q₂And Q₃The group shown in P, liquid crystal mesomorphic, halogen, poly-(C can be selected from₁-C₁₈Alcoxyl Base), C₁-C₁₈Alkoxy carbonyl, C₁-C₁₈Alkyl-carbonyl, C₁-C₁₈Alkoxyl carbonyloxy group, aryloxy group carbonyloxy group, perfluor (C₁-C₁₈) Alkoxyl, perfluor (C₁-C₁₈) alkoxy carbonyl, perfluor (C₁-C₁₈) alkyl-carbonyl, perfluor (C₁-C₁₈) alkyl amino, two (perfluors (C₁-C₁₈) alkyl) amino, perfluor (C₁-C₁₈) alkyl sulfide, C₁-C₁₈Alkyl sulfide, C₁-C₁₈Acetyl group, C₃-C₁₀Cycloalkyl, C₃-C₁₀ Cycloalkyloxy, with cyano group, halogen or C₁-C₁₈Alkoxyl is mono-substituted or with the polysubstituted straight chain of halogen or branched C₁- C₁₈Alkyl, and comprise the group of one of following formula :-M (T)_(t-1)With-M (OT)_(t-1), wherein M is selected from aluminum, antimony, tantalum, titanium, zirconium and silicon, T is selected from functional organic group, functional organic alkyl, aliphatic alkyl and aromatic hydrocarbyl, and t is the quantivalence of M.

Subscript c of formula-III, each integer being independently selected from 0-20 of d, e and f, including described value.The S of formula-III₁、 S₂、S₃、S₄And S₅Each, group occurs that place is selected from following kind (1), (2) and the spacer units of (3) independently of one another.Kind The spacer units of class (1) includes-(CH₂)_g-,-(CF₂)_h-,-Si (Z ')₂(CH₂)_g-,-(Si (CH₃)₂O)_h-, the most each Z ' is only On the spot selected from hydrogen, C₁-C₁₈Alkyl, C₃-C₁₀Cycloalkyl and aryl；There is place independently selected from 1-20 each in g；H is the whole of 1-16 Number, including endpoint value.The spacer units of kind (2) include-N (Z)-,-C (Z)=C (Z)-,-C (Z)=N-,-C (Z ')-C (Z ')- Or singly-bound, wherein there is place independently selected from hydrogen, C each in Z₁-C₁₈Alkyl, C₃-C₁₀Cycloalkyl and aryl, and Z ' is in each appearance Place is independently selected from C₁-C₁₈Alkyl, C₃-C₁₀Cycloalkyl and aryl.The spacer units of kind (3) include-O-,-C (O)-,-C ≡ C-,-N=N-,-S-,-S (O)-,-S (O) (O)-,-(O) S (O)-,-(O) S (O) O-,-O (O) S (O) O-or straight chain or branched C₁-C₂₄Alkylidene residue, described C₁-C₂₄Alkylidene residue is unsubstituted, mono-substituted with cyano group or halogen or uses halogen Element is polysubstituted.About S₁、S₂、S₃、S₄And S₅Can be selected from its spacer units, what condition was is when comprising heteroatomic two When spacer units links together, this spacer units is connected to hetero atom and is the most directly connected with each other.About S₁、S₂、S₃、S₄ And S₅Can be selected from its spacer units, further condition is to work as S₁When being connected to the compound of the present invention such as Formulas I, S₅Even When receiving P, S₁And S₅It is connected to two hetero atoms in each case the most directly connected to each other.

Further relating to formula-III, P is selected from: hydroxyl, amino, C₂-C₁₈Alkenyl, C₂-C₁₈Alkynyl, azido, monosilane Base, siloxy, silyl hydride, (tetrahydrochysene-2H-pyrans-2-base) epoxide, in sulfur generation, NCO, sulfur is for isocyanide Perester radical, acryloxy, methacryloxy, 2-(acryloxy) ethylaminocarbonyl, 2-(methacryloxypropyl Base) ethylaminocarbonyl, aziridinyl, allyloxy carbonyloxy group, epoxy radicals, carboxylic acid, carboxylate, acrylamido, methyl Acrylamido, amino carbonyl, C₁-C₁₈Alkyl amino-carbonyl, amino carbonyl (C₁-C₁₈) alkyl, C₁-C₁₈Alkoxyl carbonyloxy group, Halogen carbonyl, hydrogen, aryl, hydroxyl (C₁-C₁₈) alkyl, C₁-C₁₈Alkyl, C₁-C₁₈Alkoxyl, amino (C₁-C₁₈) alkyl, C₁-C₁₈Alkane Base amino, two (C₁-C₁₈) alkyl amino, C₁-C₁₈Alkyl (C₁-C₁₈) alkoxyl, C₁-C₁₈Alkoxyl (C₁-C₁₈) alkoxyl, nitre Base, poly-(C₁-C₁₈) alkyl ether, (C₁-C₁₈) alkyl (C₁-C₁₈) alkoxyl (C₁-C₁₈) alkyl, poly-ethyleneoxy group, polytrimethylene Epoxide, vinyl, acryloyl group, acryloxy (C₁-C₁₈) alkyl, methylacryloyl, methacryloxy (C₁-C₁₈) Alkyl, 2-chloropropene acyl group, 2-phenyl acryloyl, acryloxy phenyl, 2-chloropropene acylamino-, 2-phenylacryloyl ammonia Base carbonyl, oxetanyl, glycidyl, cyano group, NCO (C₁-C₁₈) alkyl, itaconate, vinyl ethers, Vinyl esters, styrene derivative, main chain and side chain liquid crystalline polymer, silicone derivative, ethylenimine derivatives, maleic acid Derivant, fumaric acid derivatives, unsubstituted cinnamic acid derivative, take with the methyl of at least one, methoxyl group, cyano group and halogen The cinnamic acid derivative in generation, or substituted or unsubstituted chirality or achirality unit price or divalent group, selected from class Sterin group, terpenoid group, alkaloid group and mixture thereof, wherein this substituent group is independently selected from C₁-C₁₈Alkyl, C₁-C₁₈ Alkoxyl, amino, C₃-C₁₀Cycloalkyl, C₁-C₁₈Alkyl (C₁-C₁₈) alkoxyl, fluorine (C₁-C₁₈) alkyl, cyano group, cyano group (C₁-C₁₈) Alkyl, cyano group (C₁-C₁₈) alkoxyl or its mixture, P is the structure with 2-4 reactive group, or P is not Substituted or substituted ring-opening metathesis polymerization precursor, or P is substituted or unsubstituted photochromic compound.

Subscript d of formula-III ', e ' and f ' can be each independently selected from 0,1,2,3 and 4, and condition is d '+e '+f ' sum It is at least 1 in some embodiments, or is at least 2 in some other embodiments, or in some other enforcement Scheme is at least 3.

Being property embodiment according to different unconditional disclosed herein, when P is polymerisable group, this is polymerisable Group can be any functional group being adapted to participate in polyreaction.Polyreaction unconditional is that the example of property includes being described inHawley’s Condensed Chemical Dictionary Thirteenth Edition, 1997, John Wiley& Sons, those in " polymerization " definition of the 901-902 page, the disclosure of which is hereby incorporated by reference.Although the most herein Not limiting, but polyreaction includes: " addition polymerization ", wherein free radical is initiator, and it is by adding it side, simultaneously Produce new free electron at opposite side, and react with the double bond of monomer；" polycondensation ", two of which reaction molecular combines Form bigger molecule, and eliminate little molecule such as hydrone；" oxidative coupling polymerization ".Additionally, the non-bar of polymerizable groups Part is that the example of property includes hydroxyl, acryloxy, methacryloxy, 2-(acryloxy) ethylaminocarbonyl, 2-(methacryloxy) ethylaminocarbonyl, isocyanates, aziridine, allyl carbonate, and epoxy such as epoxy second Alkane methyl.

Being property embodiment according to other unconditional, P can be selected from main chain or side chain liquid crystalline polymer and liquid crystal is situated between Brilliant.As used herein, term liquid crystal " mesomorphic (mesogen) " represents strong shape or discotic liquid-crystalline molecules.Additionally, as this Place uses, and term " backbone crystal copolymer " refers to such polymer, at main chain (that is, the main chain) knot of this polymer Structure has liquid crystal mesomorphic.As used herein, term " side chain liquid crystalline polymer " refers to such polymer, and it has The liquid crystal mesomorphic being connected on this polymer lateral chain.Although the most not limiting, but generally mesomorphic is by two or more virtues Race's ring is constituted, and which limit the movement of liquid crystal polymer.The suitably example of rod shaped liquid crystal mesomorphic includes, without being limited to: replace Or unsubstituted aromatic ester, substituted or unsubstituted straight chain aromatic compounds, and substituted or unsubstituted three Phenyl.

Being property embodiment according to another unconditional, P can be selected from steroid group, and such as and to be not limited to gallbladder solid Alcoholic compound.

In some embodiments of the present invention, for each i, R¹With for each t, R²It is each independently selected from group B.In some embodiments, group B can be selected from (i) hydrogen, C₁-C₁₈Alkyl, C₂-C₁₈Thiazolinyl (alkylidene), C₂-C₁₈Alkynes Base (alkylidyne), vinyl, C₃-C₁₀Cycloalkyl, C₁-C₁₈Haloalkyl, pi-allyl, halogen, and unsubstituted or with extremely Few a kind of C₁-C₁₈Alkyl and C₁-C₁₈The mono-substituted benzyl of alkoxyl.In further embodiment, group B can be selected from (i)C₁-C₁₂Alkyl, C₃-C₇Cycloalkyl, C₁-C₁₂Haloalkyl and unsubstituted or with the C of at least one₁-C₆Alkyl and C₁- C₆The mono-substituted benzyl of alkoxyl.In other embodiments still, group B can be selected from (i) C₁-C₆Alkyl, C₃-C₅Ring Alkyl, C₁-C₆Haloalkyl and unsubstituted or with the C of at least one₁-C₃Alkyl and C₁-C₃The mono-substituted benzyl of alkoxyl.

According to embodiment of the present invention, group B can take with selected from following at least one in para-position selected from (ii) For the mono-substituted phenyl of base: C₁-C₁₈Alkoxyl, straight chain or side chain C₁-C₂₀Alkylidene, straight chain or side chain C₁-C₄Poly (oxyalkylene) Base, ring C₃-C₂₀Alkylidene, phenylene, naphthylene, C₁-C₁₈The substituted phenylene of alkyl, list or polyurethanes (C₁- C₂₀) alkylidene, list or polyester (C₁-C₂₀) alkylidene, list or Merlon (C₁-C₂₀) alkylidene, poly-silicylene, poly-Asia Siloxy group and mixture thereof, wherein this at least one substituent group is connected on the aryl of photochromic material.

In some other embodiments, group B can be selected from (iii)-CH (CN)₂With-CH (COOX₁)₂, wherein X₁ Selected from least one following: hydrogen, lengthen agent L, unsubstituted or with the mono-substituted C of phenyl₁-C₁₈Alkyl, uses C₁-C₁₈Alkyl, C₁-C₁₈Haloalkyl or C₁-C₁₈Alkoxyl mono-substituted phenyl (C₁-C₁₈) alkyl, and virtue unsubstituted, single or dibasic Base, the substituent group of the most each aryl is independently selected from C₁-C₁₈Alkyl and C₁-C₁₈Alkoxyl, and lengthen agent L.At some additionally Embodiment in, group B can be selected from-CH (CN)₂With-CH (COOX₁)₂, wherein X₁Selected from least one following: hydrogen, add Long agent L, unsubstituted or with the mono-substituted C of phenyl₁-C₁₂Alkyl, uses C₁-C₆Alkyl or C₁-C₆The mono-substituted phenyl of alkoxyl (C₁-C₆) alkyl, and aryl unsubstituted, single or dibasic, the substituent group of the most each aryl is independently selected from C₁-C₆ Alkyl and C₁-C₆Alkoxyl；With lengthening agent L.In further other embodiments, group B can be selected from-CH (CN)₂With- CH(COOX₁)₂, wherein X₁Selected from hydrogen, unsubstituted or with the mono-substituted C of phenyl₁-C₆Alkyl, uses C₁-C₃Alkyl or C₁-C₃Alkane Epoxide mono-substituted phenyl (C₁-C₃) alkyl, and aryl unsubstituted, single or dibasic, the substituent group of the most each aryl Independently selected from C₁-C₃Alkyl and C₁-C₃Alkoxyl；With lengthening agent L.

In some embodiments, group B can be selected from (iv)-CH (X₂)(X₃)。X₂Group can selected from following at least One of: hydrogen, lengthen agent L, C₁-C₁₈Alkyl, and aryl unsubstituted, single or dibasic, the substituent group of the most each aryl Independently selected from C₁-C₁₈Alkyl and C₁-C₁₈Alkoxyl.X₃Group can be selected from least one following :-COOX₁、-COX₁、- COX₄With-CH₂OX₅, wherein X₄Selected from least one following: morpholinyl, piperidyl, unsubstituted, use C₁-C₁₈Alkyl list or The dibasic amino of person, and unsubstituted, single or dibasic selected from phenyl amino with the group of diphenyl amino, the most often Individual substituent group is independently selected from C₁-C₁₈Alkyl or C₁-C₁₈Alkoxyl；And X₅Selected from hydrogen, lengthen agent L ,-C (O) X₂, unsubstituted Or with (C₁-C₁₈) alkoxyl or the mono-substituted C of phenyl₁-C₁₈Alkyl, with (C₁-C₁₈) alkoxyl mono-substituted phenyl (C₁- C₁₈) alkyl, and aryl unsubstituted, single or dibasic, the substituent group of the most each aryl is independently selected from C₁-C₁₈Alkyl And C₁-C₁₈Alkoxyl.

In some other embodiments, group B can be selected from-CH (X₂)(X₃)。X₂Group can selected from following extremely One of few: lengthen agent L, C₁-C₁₂Alkyl, and aryl unsubstituted, single or dibasic, the substituent group of the most each aryl is only On the spot selected from C₁-C₆Alkyl and C₁-C₆Alkoxyl.X₃Group can be selected from least one following :-COOX₁,-COX₁,-COX₄ With-CH₂OX₅, wherein: X₄Selected from least one following: morpholinyl, piperidyl, unsubstituted, use C₁-C₆Alkyl list or two Substituted amino, and unsubstituted, single or dibasic selected from phenyl amino with the group of diphenyl amino, the most each takes Dai Ji is independently selected from C₁-C₆Alkyl or C₁-C₆Alkoxyl；And X₅Selected from hydrogen, lengthen agent L ,-C (O) X₂, unsubstituted or With (C₁-C₁₂) alkoxyl or the mono-substituted C of phenyl₁-C₁₂Alkyl, with (C₁-C₁₂) alkoxyl mono-substituted phenyl (C₁-C₁₂) alkane Base, and aryl unsubstituted, single or dibasic, the substituent group of the most each aryl is independently selected from C₁-C₆Alkyl and C₁- C₆Alkoxyl.

In some further other embodiments, group B can be selected from-CH (X₂)(X₃)。X₂Group can selected from At least one under: lengthen agent L, C₁-C₆Alkyl and aryl unsubstituted, single or dibasic, the replacement of the most each aryl Base is independently selected from C₁-C₃Alkyl and C₁-C₃Alkoxyl.X₃Selected from least one following :-COOX₁、-COX₁、-COX₄With- CH₂OX₅, wherein: X₄Group can be selected from least one following: morpholinyl, piperidyl, unsubstituted, use C₁-C₃Alkyl list or The dibasic amino of person, and unsubstituted, single or dibasic selected from phenyl amino with the group of diphenyl amino, the most often Individual substituent group is independently selected from C₁-C₃Alkyl or C₁-C₃Alkoxyl；And X₅Selected from hydrogen, lengthen agent L ,-C (O) X₂, unsubstituted Or with (C₁-C₆) alkoxyl or the mono-substituted C of phenyl₁-C₆Alkyl, with (C₁-C₆) alkoxyl mono-substituted phenyl (C₁-C₁₂) Alkyl, and aryl unsubstituted, single or dibasic, the substituent group of the most each aryl is independently selected from C₁-C₃Alkyl and C₁-C₃Alkoxyl.

Group B in some embodiments can, mono-, di-unsubstituted selected from (v) or trisubstituted aryl；The long Lip river of 9- Ni Dingji；Or heteroaromatic group unsubstituted, single or dibasic, it is selected from pyridine radicals, furyl, benzofuran-2- Base, benzofuran-3-base, thienyl, benzothiophene-2-base, benzothiophene-3-base, dibenzofuran group, dibenzothiophenes Base, carbazyl, benzo pyridine radicals, indolinyl, or fluorenyl.Each aryl and heteroaromatic group substituent group can respectively go out Now place independently selected from: (1) lengthen agent L；(2)-COOX₁Or-C (O) X₆；(3) aryl, halogen, halogenated aryl, C₃-C₁₀Cycloalkyl Aryl, and use C₁-C₁₈Alkyl or C₁-C₁₈Alkoxyl list or dibasic aryl；(4)C₁-C₁₈Alkyl, C₃-C₁₀Cycloalkyl, C₃-C₁₀Cycloalkyloxy (C₁-C₁₈) alkyl, aryl (C₁-C₁₈) alkyl, aryloxy group (C₁-C₁₈) alkyl, single or two (C₁-C₁₈) alkane Base aryl (C₁-C₁₈) alkyl, single or two (C₁-C₁₈) alkoxy aryl (C₁-C₁₈) alkyl, C₁-C₁₈Haloalkyl, and single (C₁- C₁₈) alkoxyl (C₁-C₁₈) alkyl；(5)C₁-C₁₈Alkoxyl, C₃-C₁₀Cycloalkyloxy, cycloalkyloxy (C₁-C₁₈) alkoxyl, aryl (C₁-C₁₈) alkoxyl, aryloxy group (C₁-C₁₈) alkoxyl, single or two (C₁-C₁₈) alkylaryl (C₁-C₁₈) alkoxyl, and single or Person two (C₁-C₁₈) alkoxy aryl (C₁-C₁₈) alkoxyl；(6) amino carbonyl, amino carbonyl (C₁-C₁₈) alkylidene, amino, single Or dialkyl amido, ammonia diaryl base, piperazinyl, N-(C₁-C₁₈) alkylpiperazinyl, N-arylpiperazinyl, '-aziridino, two Hydrogen indyl, piperidyl, morpholinyl, thio-morpholinyl, tetrahydric quinoline group, tetrahydro isoquinolyl, pyrrolidinyl, hydroxyl, propylene Acyloxy, methacryloxy and halogen；(7)-OX₇Or-N (X₇)₂；(8)-SX₁₁；(9) shown in formula i containing azo-cycle；(10) Group shown in formula ii or iii；(11) unsubstituted or mono-substituted group, selected from pyrazolyl, imidazole radicals, pyrazoline Base, imidazolinyl, pyrrolidinyl, phenothiazinyl, phenazinyl, phenazinyl or acridinyl, the most each substituent group is selected independently From lengthening agent L, C₁-C₁₈Alkyl, C₁-C₁₈Alkoxyl, phenyl, hydroxyl, amino or halogen.

Each aryl and heteroaromatic group substituent group can be selected from (12) formula iv or formula v in addition and independently at each appearance Shown group,

About formula iv and v:(I) V ' in each formula independently selected from-O-,-CH-, C₁-C₆Alkylidene and C₃-C₁₀Ring alkylene Base；(II) V in each formula independently selected from-O-or-N (X₂₁)-, wherein X₂₁It is hydrogen, lengthens agent L, C₁-C₁₈Alkyl and C₂- C₁₈Acyl group, condition is if V is-N (X₂₁The V ' of)-, then is-CH₂-；(III)X₁₈And X₁₉It is each independently selected from hydrogen, lengthens agent L, And C₁-C₁₈Alkyl；(IV) k is selected from 0,1 and 2, and each X₂₀Place occurs independently selected from lengthening agent L, C each₁-C₁₈Alkyl, C₁-C₁₈Alkoxyl, hydroxyl and halogen.

Each aryl and heteroaromatic group substituent group can be selected from shown in (13) formula vi in addition and independently at each appearance Group,

About formula vi:(I) X₂₂Selected from hydrogen, lengthen agent L and C₁-C₁₈Alkyl；(II) X₂₃Selected from lengthening agent L and unsubstituted , single or dibasic group, it is selected from naphthyl, and phenyl, furyl and thienyl, the most each substituent group is at each appearance Independently selected from C₁-C₁₈Alkyl, C₁-C₁₈Alkoxyl and halogen.

According to some other embodiments, group B can be selected from unsubstituted, mono-, di-or trisubstituted aryl；9- Julolidine groups；Or heteroaromatic group unsubstituted, single or dibasic, it is selected from pyridine radicals, furyl, benzo furan Mutter-2-base, benzofuran-3-base, thienyl, benzothiophene-2-base, benzothiophene-3-base, dibenzofuran group, dibenzo Thienyl, carbazyl, benzo pyridine radicals, indolinyl or fluorenyl.Each aryl and heteroaromatic group substituent group are in each appearance Place independently selected from: (1) lengthen agent L；(2)-COOX₁Or-C (O) X₆；(3) aryl, halogenated aryl, C₃-C₇Cycloalkylaryl, and Use C₁-C₁₂Alkyl or C₁-C₁₂Alkoxyl list or dibasic aryl；(4)C₁-C₁₂Alkyl, C₃-C₇Cycloalkyl, C₃-C₇Cycloalkanes Epoxide (C₁-C₁₂) alkyl, aryl (C₁-C₁₂) alkyl, aryloxy group (C₁-C₁₂) alkyl, single or two (C₁-C₁₂) alkylaryl (C₁- C₁₂) alkyl, single or two (C₁-C₁₂) alkoxy aryl (C₁-C₁₂) alkyl, haloalkyl, and single (C₁-C₁₂) alkoxyl (C₁- C₁₂) alkyl；(5)C₁-C₁₂Alkoxyl, C₃-C₇Cycloalkyloxy, cycloalkyloxy (C₁-C₁₂) alkoxyl, aryl (C₁-C₁₂) alkoxyl, Aryloxy group (C₁-C₁₂) alkoxyl, single or two (C₁-C₁₂) alkylaryl (C₁-C₁₂) alkoxyl, and single or two (C₁-C₁₂) alkane Epoxide aryl (C₁-C₁₂) alkoxyl；(6) amide groups, amino, list or dialkyl amido, ammonia diaryl base, piperazinyl, N- (C₁-C₁₈) alkylpiperazinyl, N-arylpiperazinyl, '-aziridino, indolinyl, piperidyl, morpholinyl, thio-morpholinyl, Tetrahydric quinoline group, tetrahydro isoquinolyl, pyrrolidinyl, hydroxyl, acryloxy, methacryloxy and halogen；(7)-OX₇ Or-N (X₇)₂；(8) unsubstituted or mono-substituted group, it is selected from pyrazolyl, imidazole radicals, pyrazolinyl, imidazolinyl, pyrrole Coughing up alkyl, phenothiazinyl, phenazinyl, phenazinyl or acridinyl, the most each substituent group is independently selected from lengthening agent L, C₁-C₆ Alkyl, C₁-C₆Alkoxyl, phenyl, hydroxyl, amino or halogen.

According to some other embodiments, group B can be selected from unsubstituted, mono-, di-or trisubstituted aryl；9- Julolidine groups；Or heteroaromatic group unsubstituted, single or dibasic, it is selected from pyridine radicals, furyl, benzo furan Mutter-2-base, benzofuran-3-base, thienyl, benzothiophene-2-base, benzothiophene-3-base, dibenzofuran group, dibenzo Thienyl, carbazyl, benzo pyridine radicals, indolinyl or fluorenyl.

Each substituent group can each occur place independently selected from: (1) lengthen agent L；(2)-C(O)X₆；(3) aryl, halo Aryl, C₃-C₇Cycloalkylaryl, and use C₁-C₁₂Alkyl or C₁-C₁₂Alkoxyl list or dibasic aryl；(4)C₁-C₆Alkane Base, C₃-C₅Cycloalkyl, C₃-C₅Cycloalkyloxy (C₁-C₆) alkyl, aryl (C₁-C₆) alkyl, aryloxy group (C₁-C₆) alkyl, single or Two (C₁-C₆) alkylaryl (C₁-C₆) alkyl, single or two (C₁-C₆) alkoxy aryl (C₁-C₆) alkyl, haloalkyl, and single (C₁-C₆) alkoxyl (C₁-C₆) alkyl；(5)C₁-C₆Alkoxyl, C₃-C₅Cycloalkyloxy, cycloalkyloxy (C₁-C₆) alkoxyl, aryl (C₁-C₆) alkoxyl, aryloxy group (C₁-C₆) alkoxyl, single or two (C₁-C₆) alkylaryl (C₁-C₆) alkoxyl, and single or Two (C₁-C₆) alkoxy aryl (C₁-C₆) alkoxyl；(6) amino carbonyl, amino carbonyl (C₁-C₁₈) alkylidene, amino, single or Dialkyl amido, ammonia diaryl base, piperazinyl, N-(C₁-C₁₈) alkylpiperazinyl, N-arylpiperazinyl, '-aziridino, dihydro Yin Diindyl base, piperidyl, morpholinyl, thio-morpholinyl, tetrahydric quinoline group, tetrahydro isoquinolyl, pyrrolidinyl, hydroxyl, acryloyl-oxy Base, methacryloxy and halogen；(7)-OX₇Or-N (X₇)₂；(8) unsubstituted or mono-substituted group, its choosing From pyrazolyl, imidazole radicals, pyrazolinyl, imidazolinyl, pyrrolidinyl, phenothiazinyl, phenazinyl, phenazinyl or acridinyl, The most each substituent group is independently selected from lengthening agent L, C₁-C₃Alkyl, C₁-C₃Alkoxyl, phenyl, hydroxyl, amino or halogen.

The such as indeno fused ring compound shown in Formulas I of the present invention and the such as indeno condensed ring pyrylium compound shown in Formula II R³And R⁴Group can be each independently selected from: (i) hydrogen, C₁-C₂₀Alkyl, C₁-C₂₀Haloalkyl, C₃-C₁₀Cycloalkyl, allyl Base, benzyl or mono-substituted benzyl, described benzyl substituent is selected from halogen, C₁-C₂₀Alkyl or C₁-C₂₀Alkoxyl；(ii) do not take In generation, mono-, di-or trisubstituted group, it is selected from phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuran Base, thienyl, benzothienyl, dibenzofuran group, dibenzothiophenes base, carbazyl or indyl, described group substitution Independently selected from halogen in each situation, C₁-C₂₀Alkyl or C₁-C₂₀Alkoxyl；(iii) mono-substituted phenyl, is positioned at para-position On described substituent group be-(CH₂)_t-or-O-(CH₂)_t-, wherein t is integer 1,2,3,4,5 or 6, and described substituent group is connected to On aryl in photochromic material composition；(iv) group-CH (R¹⁰) G, wherein R¹⁰It is hydrogen, C₁-C₂₀Alkyl or unsubstituted, Single or dibasic aryl phenyl or naphthyl, and G is-CH₂OR¹¹, wherein R¹¹It is hydrogen ,-C (O) R¹⁰, C₁-C₂₀Alkyl, C₁- C₂₀Alkoxyl (C₁-C₂₀) alkyl, phenyl (C₁-C₂₀) alkyl, single (C₁-C₂₀) alkoxyl substituted phenyl (C₁-C₂₀) alkyl, or Aryl phenyl unsubstituted, single or dibasic or naphthyl, each described phenyl and naphthyl substituted base are C₁-C₂₀Alkyl or Person C₁-C₂₀Alkoxyl.

According to some selectable embodiments, (v) R³And R⁴Spiral shell substituent group can be formed together, its selected from substituted or The unsubstituted spiral shell carbocyclic ring containing 3-6 carbon atom of person, substituted or unsubstituted containing 1 or 2 oxygen atom and 3-6 carbon The spiroheterocyclic of atom (including spiral shell carbon atom).This spiral shell carbocyclic ring and spiroheterocyclic is each condenses with 0,1 or 2 phenyl ring.Taking of this volution Hydrogen or C can be selected from for base₁-C₂₀Alkyl (such as C₁-C₆Alkyl).

According to other embodiments of the present invention, R³And R⁴It is each independently selected from hydrogen, C₁-C₈Alkyl, C₁-C₈Haloalkyl And C₃-C₇Cycloalkyl.Selectable, R³And R⁴Spiral shell substituent group can be formed together, its selected from substituted or unsubstituted containing The spiral shell carbocyclic ring of 3-6 carbon atom.

B and the B ' group of the such as indeno condensed ring pyrylium compound shown in Formula II of the present invention can be each independently selected from Before relative to those kinds, group and example described in group B.

Selectable, B with B ' in some embodiments can together with form fluorenes-9-subunit, single or dibasic fluorenes- 9-subunit, or saturated C₃-C₁₂Spiral shell monocycle hydrocarbon ring, saturated C₇-C₁₂Spiral shell dicyclo hydrocarbon ring, saturated C₇-C₁₂Spiral shell tricyctic hydrocarbon ring；With The substituent group of described fluorenes-9-subunit is selected from C₁-C₄Alkyl, C₁-C₄Alkoxyl, bromine, fluorine and chlorine.

The most selectable, B with B ' in some embodiments can together with form fluorenes-9-subunit, single or two replacements Fluorenes-9-subunit or saturated C₃-C₈Spiral shell monocycle hydrocarbon ring, saturated C₇-C₁₀Spiral shell dicyclo hydrocarbon ring, saturated C₇-C₁₀Spiral shell tricyctic hydrocarbon Ring, the substituent group of described fluorenes-9-subunit is selected from C₁-C₃Alkyl, C₁-C₃Alkoxyl, fluorine and chlorine.

In some embodiments, together with B with B ', form fluorenes-9-subunit, sub-adamantyl, bornenyl, sub-norborneol Base or dicyclo (3.3.1) nonyl-9-subunit.

This indeno fused ring compound can represent by following formula I a in some embodiments of the present invention,

About Formulas I a, subscript (t) is selected from 0-4, and group R¹, R², R³, R⁴, R⁵And Q ' and subscript (i) each so on institute State.

About other embodiments, the Q ' of the indeno fused ring compound shown in Formulas I a is selected from-CN ,-C (O) OR^a,-C ≡ C-R^a,-C (R^a)=C(R^a)(R^a) ,-OC (O) R^a,-OC (O) OR^a,-SR^a,-OS (O₂)R^bWith-C (O) NR^aR^a, wherein R^aAnd R^bRespectively From upper described independently.

According to some embodiments of the invention, this indeno condensed ring pyrylium compound Formula Il a represents,

About Formula II a, subscript (t) is selected from 0-4, and group R¹, R², R³, R⁴, Q '″, B and B ' and subscript (i) are each so Upper described.Numeral in Formula II a ring structure illustrates the position that different groups can be bonded to.The each bonding of such as B and B ' To position-3, R³And R⁴Each position-13 that are bonded to, and Q '″ is bonded to position-10.R¹Group can be bonded to position-9, and 11 With 12, and R²Group can be bonded to position-5, and 6,7 and 8.

In further embodiment, 12 of the indeno condensed ring pyrylium compound shown in Formula II a have and are bonded on it Hydrogen, and Q '″ is-CN.

In further embodiment, and the indeno condensed ring pyrylium compound with further reference to Formula II a, i is at least 1,12 Position has and is bonded to R thereon¹, and Q '″ is selected from-N₃,-C (O) OR^a,-C ≡ C-R^a,-C (R^a)=C(R^a)(R^a) ,-OC (O) R^a,- OC(O)OR^a,-SR^aWith-OS (O₂)R^b。

According to other embodiments of the present invention, the indeno fused ring compound of the present invention and indeno condensed ring pyrylium compound Each lengthening agent L can be independently selected from following compound.

The indeno condensed ring pyrylium compound (those shown in such as Formula II and IIa) of the present invention may be used for giving compositions And/or goods are with photochromism.The goods of photochromism can be given by the indeno condensed ring pyrylium compound of the present invention Example include but not limited to optical element, display, window (or clear glass), mirror and the parts of liquid crystal cell or unit Part.As used herein, term " optics " represents and belongs to or relevant with light and/or vision.Photochromism can be given The example of optical element can include, without being limited to ophthalmic devices, display element, window, mirror and liquid crystal cell element.As Used herein, term " ophthalmology " represents and belongs to or relevant with eyes and vision.Ophthalmic devices unconditional is the example bag of property Including rectification and non-correcting lens, including single vision or many visions lens, it can be many visions lens of segmentation or non-segmentation (such as but not limited to bifocal lens, three focus lens and progressive lens), and other are used for correcting, protect or strengthen and (make up Or other) vision element, include but not limited to amplifying lens, protect lens, protective eye lens, goggles and for optical instrument The lens of (such as photographing unit and telescope).As used herein, term " shows " and represents visible or machine-readable Word, numeral, symbol, the information representation that designs or draw.Display element unconditional is that the example of property includes screen, supervision Device and safety element such as safety label.As used herein, term " window " expression is used for allowing light transmitted through hole therein.Window Unconditional is that the example of property includes automobile and aircraft clear glass, windshield, wave filter, baffle plate and optical converter.As Used herein, term " mirror " represents the surface of the most incident illumination of direct reflection.As used herein, term " liquid Jingjing unit " refer to the structure containing the liquid crystal material that can orient.A kind of unconditional of liquid crystal cell element is that property example is Liquid crystal display.

Goods can give photochromism by the indeno condensed ring pyrylium compound of such method present invention, its Include but not limited to inhalation method, appropriate location casting method, painting method, in-mould coating method, post forming method and layer Conjunction method.With inhalation method, this indeno condensed ring pyrylium compound is typically diffused into the goods example being previously formed or making In the coating such as substrate or applied in advance or the polymeric material of film.Suction can be by the system that will be previously formed or make The polymeric material of product is immersed in the solution containing this indeno condensed ring pyrylium compound, heats or does not heats.Thereafter, although Need not, but this indeno condensed ring pyrylium compound can be with this polymeric material (polymeric material of such as substrate or coating Material) bonding.

With the casting method of appropriate location, this indeno condensed ring pyrylium compound can be with following mixing: be in solution or The polymer of person's melt form and/or oligomeric composition；Or it is in the monomer composition of liquid form, is formed and can be cast Photochromic composition.This castable photochromic composition is the most typically incorporated into mould (such as lens die) In chamber.Then this castable photochromic composition consolidates (such as solidification) in mould and forms photochromic article.

In the goods including substrate, the indeno condensed ring pyrylium compound of the present invention can be at least some of as being connected to The part of this suprabasil coating, be connected in this substrate at least one of.This substrate can be polymeric substrates Or inorganic substrates (such as but not limited to substrate of glass).Before by this coating composition paint substrate, the indenes of the present invention And condensed ring pyrylium compound can be incorporated at least one of coating composition.Selectable, can be by coating composition In paint substrate, at least part of consolidation, the indeno condensed ring pyrylium compound of the present invention can absorb at least one thereafter In the coating divided.As used herein, term " consolidates " and " consolidation " includes, without being limited to solidification, polymerization, crosslinking, cooling With dry.

Photochromic article can use the indeno condensed ring pyrylium compound of the present invention, by coating in generally acknowledged mould Prepared by (or curtain coating in mould) method.Use in-mould coating method, the light of the indeno condensed ring pyrylium compound of the present invention will be included At least one of mutagens color coating composition (it can be liquid coating composition or powder paint compositions) paint mould Divide on inner surface, and the most at least part of consolidation.Thereafter, by polymer solution or melt, or oligomer or monomer molten Liquid or mixture are cast in mold cavity or mould and contact with the photochromic coating compositions applied in advance, and at least partly Consolidation.Then the photochromic article formed is removed from mould.Powdery paints unconditional is that the example of property (wherein may be used It is the indeno condensed ring pyrylium compound of property embodiment with use different unconditional disclosed herein) in United States Patent (USP) No.6068797 the 7th hurdle the 50th row is set forth to the 19th hurdle the 42nd row, and the disclosure of which is expressly incorporated by reference at this.

The photochromic article prepared by indeno condensed ring pyrylium compound using the present invention can also be public by this area The post forming method known is formed.Post forming method be typically include in mould formation substrate, then this substrate with Form inner space between mould inner surface, be subsequently introduced (such as injecting) photochromic coating compositions the most wherein, so Rear consolidation (such as solidification).Selectable, post forming method can include introducing in mould by the substrate being previously formed, so Between this substrate and mold surface, condition is inner space, and photochromic coating compositions is introduced (such as thereafter It is injected into) in this inner space.

The photochromic article prepared by indeno condensed ring pyrylium compound using the present invention can also be public by this area The laminating method known is formed.Use laminating method, the film of the indeno condensed ring pyrylium compound comprising the present invention can adhere to or Person is connected in this substrate of a part, uses or does not use bonding agent and/or apply heat and pressure.Thereafter, if it is desired to, the Two substrates can be applied in the first substrate, and two substrates can be laminated to together (such as by applying heat and pressure) and come Form element, wherein comprise the film of this indeno condensed ring pyrylium compound between two substrates.Formation comprises photochromic material The method of the film of material can include such as and be not limited to photochromic material and polymer solution or oligomer solution or mixed Compound combines, and is cast or extrudes film therein, and if it is required, this film of at least part of consolidation.Additionally or alternatively select, film (with or without photochromic material) can be formed and absorb with this photochromic material.

The indeno condensed ring pyrylium compound of the present invention can be used alone or is applied in combination with other photochromic materials.Energy The kind of the photochromic material that enough indeno condensed ring pyrylium compounds combination (such as mixing) with the present invention use include but not It is limited to: spiral shell (indoline) naphtho-piperazine and spiral shell (indoline) benzimidazole dihydrochloride, such as United States Patent (USP) No.3562172,3578602, Described in 4215010,4342668,5405958,4637698,4931219,4816584,4880667 and 4818096；Benzo pyrrole Mutter, such as United States Patent (USP) No.3567605,4826977,5066818,4826977,5066818,5466398,5384077, Described in 5238931 and 5274132；Photochromic organic-metallic dithizone, such as diphenylthiocarbazone, such as hydrargyrum dithizone, It is described in such as United States Patent (USP) No.3361706；With fulgide and fulgenimide, such as 3-furyl and 3-thiophene Base fulgide and fulgenimide, it is described in row the-the 21 hurdle the 38th, United States Patent (USP) No.4931220 the 20th hurdle the 5th row.

The invention still further relates to a kind of photochromic composition, comprising: the indeno condensed ring pyrylium compound of (a) present invention； (b) organic material, it is selected from polymer, oligomer, monomer and its two or more combination.This photochromic composition Polymer can be selected from Merlon, polyamide, polyimides, poly-(methyl) acrylate, polycyclic olefin, polyurethane, poly- (urea) carbamate, polysulfide carbamate, polysulfide (urea) carbamate, polyhydric alcohol (allyl carbonate), acetate fiber Element, cellulose diacetate, Triafol T, cellulose acetate propionate, acetylbutyrylcellulose, polyolefin, polyalkylene-second Vinyl acetate, poly-(vinyl acetate), poly-(vinyl alcohol), poly-(vinyl chloride), poly-(vinyl dimethoxym ethane), poly-(vinyl second contracts Aldehyde), poly-(vinylidene chloride), poly-(ethylene glycol terephthalate), polyester, polysulfones, polyolefin, its copolymer and combinations thereof.

The photochromic composition of the present invention is optional farther includes at least one additive, and it is selected from dyestuff, Sequence accelerator, light trigger, thermal initiator, polymerization inhibitor, solvent, light stabilizer, heat stabilizer, releasing agent, rheology control agent, Levelling agent, free radical quencher and adhesion promotor.

The invention still further relates to a kind of photochromic coating compositions, comprising: the indeno condensed ring pyrans chemical combination of (a) present invention Thing；B () is selected from curable resin composition, the film-forming composition of thermoplastic resin composition and combinations thereof；(c) optional molten Agent compositions.

The invention still further relates to photochromic article, it includes the indeno condensed ring pyrylium compound of the present invention.The light of the present invention The example of mutagens colour product includes but not limited to selected from least one optical element following: ophthalmic devices, display element, window, Mirror, packaging material, active liquid crystal wafer element and passive liquid crystal wafer element.

As used herein, term " liquid crystal cell " refers to the structure containing the liquid crystal material that can orient.Active Liquid crystal cell is such box, and wherein by applying external force such as electric field or magnetic field, liquid crystal material can be in orderly and disordered state Between switching or between two order states switch.Passive liquid crystal wafer is such box, and wherein liquid crystal material maintains Sequence state.Active liquid crystal wafer element or one unconditional of device be the example of property be liquid crystal display.

The example of the photochromic ophthalmic element of the present invention includes but not limited to correcting lens, non-correcting lens, and contact is thoroughly Mirror, intraocular lens, amplifying lens, protection lens and protective eye lens.The example of display element includes but not limited to screen, monitor and Safety element.

Additionally, can when the state of activation according to the photochromic compound that the unconditional that the present invention is different is property embodiment To have according to the average absorption ratio measured by cassette method (CELL METHOD) at least 1.5.It is that property is real according to other unconditional Executing scheme, this photochromic compound can according to the average absorption ratio measured by cassette method (CELL METHOD) in the state of activation To be 4-20,3-30 or 2.5-50.Being property embodiment according to other unconditional still, this photochromic compound is being lived Change state can be 1.5-50 according to the average absorption ratio measured by cassette method (CELL METHOD).

The different unconditional of the formation present invention is the reaction of the photochromic compound (having L group) of property embodiment Order is disclosed in response hierarchy A to the J of United States Patent (USP) 7342112, and in K, M, N, P, Q, T, the disclosure of which is incorporated herein by Reference.

Under Ru Ci discussed in described scheme, compound 105 represents one of indeno fused ring compound described herein.It is also The basis preparing other indeno fused ring compounds described herein can be served as.Such as it can come as shown in scheme 1,2,3,4 and 5 Preparation.Once prepare, then the hydroxy functionality of compound 105 may be used for pyrans and formed and 105 or its one of precursor 408 Halogen may be used for changing into Q '.Entire infrastructure from scheme 6 is indeno fused ring compound described herein.

The detailed chemical reaction that can be used in changing into 105 604 can be observed in scheme 7,8 and 9.For inciting somebody to action Pyrylium dye 606 changes into the detailed chemical reaction of 605 and can find in scheme 10.

In whole schemes, X can be selected from halogen such as F, Br, Cl and I.Each t and i is selected from 0 to available position The integer of sum.From scheme 1-scheme 6, R¹Each occur place can independently selected from hydrogen, halogen and optionally substituted chirality or Person's achirality group, selected from alkyl, perfluoroalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxyl, perfluoroalkoxy Base, miscellaneous alkyl, Heterocyclylalkyl, alkyl hydrosulfide, aryl mercaptan, amino carbonyl, aryloxycarbonyl, alkoxy carbonyl, amino Carbonyloxy group, alkoxycarbonyl amino, aryloxycarbonylamino, cyclo alkoxy carbonyl amino, heterocyclealkoxycarbonyl amino and miscellaneous Aryloxycarbonylamino.R²Selected from R¹。

Scheme 1

Scheme 1 illustrates a kind of mode preparing compound 105.R₃And R₄Can be selected from optionally substituted chirality or non- The most miscellaneous alkyl of chiral radicals, alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and Heterocyclylalkyl.

Aryl ketones 101 can be to buy or by Friedel-Crafts method known in the art or Grignard Or prepared by Cuperate method.For example, see open source literatureFriedel-Crafts and Related Reactions, George A.Olah, Interscience Publishers, volume 1964,3, XXXI chapter (aromatic ketone synthesis)； " Regioselective Friedel-Crafts Acylation of1,2,3,4-Tetrahydroquinoline and Related Nitrogen Heterocycles:Effect on NH Protective Groups and Ring Size ", Ishihara, Yugi et al., J.Chem.Soc., Perkin Trans.1, the 3401-3406 page, 1992；“Addition of Grignard Reagents to Aryl Acid Chlorides:An efficient synthesis of aryl Ketones ", Wang, Xiao-jun et al., Organic Letters, the 25th phase of volume 7,5593-5595,2005 and wherein List of references, these open source literatures relating to aforementioned synthetic methods are incorporated herein by reference with all of which at this.Aryl ketones 101 React the condensation product providing compound 102 with dimethyl succinate Stobbe in the presence of potassium tert-butoxide, its experience exists Ring-closure reaction in acetic anhydride, is followed by Methanol Decomposition to form the product of compound 103.

The nucleophilic aromatic substitution reaction that compound 103 can also be regulated by ester, is begun through this area skill by compound 106 Prepared by method known to art personnel, such as, further describe at Synthesis, January nineteen ninety-five, the 41-43 page；The Journal of Chemistry Society Perkin Transaction1,1995,235-241 page and United States Patent (USP) Method in No.7557208B2, these relate to the open source literature of such synthetic method and introduce as ginseng using all of which at this Examine.

Compound 103 can be further converted into having on bridging carbon of compound 105 via different multistep reactions Different substituted indeno-fused products, it can be in United States Patent (USP) No.5645767；5869658；5698141；5723072； 5961892；6113814；5955520；6555028；6296785；6555028；6683709；6660727；6736998； 7008568；7166357；7262295；Finding in 7320826 and 7557208, this relates to the public affairs of the substituent group on bridging carbon Open document to be incorporated herein by reference with all of which at this.Scheme 1 illustrates compound 103 and Grignard reagent reacting, subsequently Compound 105 is provided by ring-closure reaction.

Scheme 2

Scheme 2 illustrates the second way that compound 103 changes into compound 105.Hydrolyze at compound 103, with After rear ring-closure reaction, it is thus achieved that compound 202.The carbonyl of compound 202 can be organic with nucleopilic reagent such as Grignard reagent Lithium reagent or the reaction of perfluoroalkyl trimethyl silane form compound 203.R³Can selected from optionally substituted chirality or The most miscellaneous alkyl of achirality group, alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl and Heterocyclylalkyl. The hydroxyl of compound 203 can readily change into R⁴, it can be selected from halogen and optionally substituted chirality or achirality base Group's such as alkoxyl, siloxy group, heteroaryloxy and aryloxy group.

Scheme 3

Scheme 3 illustrates the third mode that compound 103 changes into compound 105.Compound from scheme 2 202 can use Wolff-Kishner reduction or its improved form to be reduced into 301.Example can be at " Practical procedures for the preparation of N-tert-butyldimethylsilylhydrozones and their use inmodified Wolff-Kishner reductions and in the synthesis of vinyl Halides and gem-dihalides ", Furrow, M.E. et al., J Am Chem Soc:126 (17): 5436-45,2004 Finding on May 5, in and list of references therein, these these documents relating to Wolff-Kishner reduction are incorporated herein by Reference.After hydroxyl protection, compound 302 once with after alkali such as LDA or methyl Grignard deprotonation, has the closeest The carbon of nuclearity.It will be understood by those skilled in the art that the compound 302 of this deprotonation can be by by it with electrophilic reagent such as Alkyl halide, carbon dioxide, acid chloride, hydrazine and chlorocarbonate derivatives reaction and change into R³And R⁴.As a result, compound 105 can be with selected from following R³And R⁴Preparing: hydrogen, optionally substituted chirality or achirality group, this group is selected from miscellaneous alkane Base, alkyl, cycloalkyl, carboxyl, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl, alkoxy carbonyl, amino carbonyl, aryl carbonyl Base, aryloxycarbonyl, or R³And R⁴Can be formed selected from oxa-together with any interruption atom, optionally substituted cycloalkyl and The group of optionally substituted Heterocyclylalkyl.

Scheme 4 and 5 summarizes the two kinds of new methods preparing compound 105, and it did not describe before it is believed that.

Scheme 4

Scheme 4 is from the beginning of aryl ketones 401.R₃Hydrogen, optionally substituted chirality or achirality group example can be selected from Such as miscellaneous alkyl, alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl and Heterocyclylalkyl.

After the Stobbe with dimethyl succinate reacts, compound 402 is changed into anhydride 403.This anhydride is permissible By using aluminum chloride to change into indone acid 404.Isosorbide-5-Nitrae-additive reaction can use nucleopilic reagent such as organometallic reagent, Amine, alcohol and mercaptan are carried out.This reaction creates dihydroindene keto acid 405.R₄Can be selected from hydrogen, optionally substituted chirality or The most miscellaneous alkyl of achirality group, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, Heterocyclylalkyl, amino, alkoxyl and Mercaptan.After acidity arranges, compound 405 can form compound 407 with Grignard reagent 406 reaction.Compound 407 experienced by the ring-closure reaction in acetic anhydride, form product 408, its side of being used directly for by Methanol Decomposition subsequently Case 6 or become compound 105 by hydrolysis.

Scheme 5

Scheme 5 is from the beginning of Stobbe product 102, and it provides compound 501 with Grignard reagent reacting.R₃And R₄Can With selected from optionally substituted chirality or the most miscellaneous alkyl of achirality group, alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, Heteroaryl, cycloalkyl and Heterocyclylalkyl.With trifluoromethayl sulfonic acid bismuth toluene and subsequently in acetic anhydride process after, same There occurs two ring-closure reactions successively in still.This reaction creates compound 408, and it can change into compound 105.

Scheme 6

Scheme 6 illustrates and compound 105 (having-OH) or 408 (having acetas) is changed into other indeno annelations The method of compound.The hydroxyl of 105 may be used in the chemistry of formation pyrylium dye 606, and its halogen can change into Q '″, as Observed by scheme 10.The halogen X of 105 can change into Q ', and forms compound 604.Details is discussed in scheme 7-9. Compound 604 can react with propargyl alcohol and form pyrylium dye 605.The Q ' of 604 can also change into shown in lengthening group L Different Q '.When using Suzuki reaction, the Q '″ of boronic acid derivatives 601 ' with A " together with form the Q ' on 602.Synthesis boron The method of acid derivative can be at " Palladium (0)-Catalyzed Cross-Coupling Reaction of Alkoxydiboron with Haloarenes:A Direct Procedure for Arylboronic Esters, J.Org.Chem.60, the 7508-7519 page, 1995 ", Miyaura, Norio et al. and list of references therein find, should The open source literature relating to such synthetic method is hereby incorporated by reference.As described here, G can be-OH or-O-alkyl； A ' ' can be selected from aryl, alkenyl, alkynyl and heteroaryl；Q '″ ' halogen ,-OH ,-N can be selected from₃,-NR^aR^a,-N (R^a)C (O) Q ' ', Q ' ' ,-CN ,-C (O) OR^a,-C ≡ C-R^a,-C (R^a)=C(R^a)(R^a) ,-OC (O) R^a,-OC (O) OR^a,-SR^a,-OS (O₂)R^b, C (O) NR^aR^aWith lengthening agent L.Group Q '″ ' with A " together with form Q ' group.B and B ' can be to select independently of one another From L, hydrogen, halogen, and optionally substituted chirality or achirality group such as metallocenyl, alkyl or perfluoroalkyl, alkene Base, alkynyl, miscellaneous alkyl, alkoxyl, perfluoro alkoxy, aryl, heteroaryl, Heterocyclylalkyl, and cycloalkyl, or wherein B and B ' The most optionally substituted cycloalkyl of group and optionally substituted Heterocyclylalkyl is formed together with any interruption atom.

Group Q ' can be selected from halogen ,-OH ,-N₃,-NR^aR^a,-N (R^a) C (O) Q ' ', Q ' ' ,-CN ,-C (O) OR^a,-C ≡ C- R^a,-C (R^a)=C(R^a)(R^a) ,-OC (O) R^a,-OC (O) OR^a,-SR^a,-OS (O₂)R^b, C (O) NR^aR^aWith lengthening agent L.Group Q '″ Halogen ,-OH ,-N can be selected from₃,-NR^aR^a,-N (R^a) C (O) Q ' ', Q ' ' ,-CN ,-C (O) OR^a,-C ≡ C-R^a,-C (R^a)=C(R^a) (R^a) ,-OC (O) R^a,-OC (O) OR^a,-SR^a,-OS (O₂)R^bWith C (O) NR^aR^a

Scheme 7,8 and 9 illustrates the details that halogen changes into Q '.This chemistry is to open from compound 105 in the hydroxyl stage Beginning, it is expressed as representing the compound 701 of naphthols in scheme 7 and 8.Product (representing with the compound 801) conduct of scheme 8 Parent material forms shown compound in scheme 9.Compound 702,706,708,709,710,802,803,807, Each hydroxy product of 809,810,811,812,901,903,904 and 906 can turn with the propargyl alcohol chemistry shown in operational version 6 Chemical conversion pyrans photochromic compound.

Scheme 7

Scheme 8

Scheme 9

Scheme 10 illustrates the chemical reaction that can carry out on this photochromic dichroic dyestuff.A ' ' ' is from scheme The reduced form of the 606 of 6.Scheme 10 confirms how to be changed into by-X-Q '″ group such as cyano group, aldehyde, carboxylic acid, and optionally substituted Chirality or achirality group, it is selected from imines, alkoxy carbonyl, amino carbonyl and aryloxycarbonyl, and is in described Position.This cyaniding and method for oxidation have been described in the open No.2009/0309076A1 of United States Patent (USP), wherein these cyanidings and Method for oxidation is hereby incorporated by reference.

Scheme 10

In the embodiment that the present invention is more specifically described below, its purpose is merely illustrative, because the most numerous Change and change will be apparent to those skilled in the art.Unless otherwise directed, whole numbers It is unit of weight with all percentages.

Embodiment

Part 1 describes embodiment 1-18 corresponding to naphthols and embodiment 1A-5A corresponding to indenonaphthopyrans, The preparation of 9A, 10A and 13A-18A.Part 2 describes the survey of the photochromic properties of embodiment 2A-5A, 10A, 13A and 18A Examination.

In the following embodiments, abbreviation below has following implication.If abbreviation not definition, then its tool There is the implication that it is generally approved.

BINAP=2, double (diphenylphosphine)-1 of 2'-, 1'-dinaphthalene

Double (OTf)₃=trifluoromethayl sulfonic acid bismuth

CuI=Copper diiodide

DHP=3,4-dihydro-2H-pyrans

DCC=dicyclohexylcarbodiimide

DCM=dichloromethane

DBSA=DBSA

DIBAL=diisobutyl aluminium hydride

DMAP=4-dimethylaminopyridine

DME=dimethyl ether

DMF=DMF

DMSO=dimethyl sulfoxide

Double (diphenylphosphine) ferrocene of Dppf=1,1'-

EtMgBr=ethylmagnesium bromide

Et₂O=Anaesthetie Ether

G=gram

H=hour

HPLC=high speed liquid chromatography method

(iPr)₂NH=diisopropylamine

HOAc=acetic acid

LDA=lithium diisopropylamide

KMnO₄=potassium permanganate

M=millimole (molar concentration)

MCPBA=m-chloro-benzoic acid peroxide

MeLi=lithium methide

Mg=milligram

Min=minute

ML=milliliter

Mmol=mM

MM=millimole

NatOBu=sodium tert-butoxide

N=equivalent (equivalent concentration)

Ng=nanogram

Nm=nanometer

NM=nM amount

NMP=N-Methyl pyrrolidone

NMR=nuclear magnetic resonance, NMR

Pd(OAc)₂=acid chloride

Pd₂(dba)₃=tri-(dibenzalacetone) two palladium (0)

PPh₃=triphenylphosphine

PPTS=pyridine p-toluenesulfonic acid ester

PTSA=p-methyl benzenesulfonic acid

PdCl₂(PPh₃)₂=bis-(triphenylphosphine) Palladous chloride. (II)

PBS=phosphate buffered saline (PBS)

TBAF=tetra-n-butyl ammonium fluoride

THF=oxolane

TLC=thin layer chromatography

T-BuOH=tert-butyl alcohol

(Tf)₂O=Trifluoromethanesulfonic anhydride

μ L=microlitre

μM=micromolar

Zn(OAc)₂=zinc acetate

Zn(CN)₂=zinc cyanide

Part 1-prepares embodiment

Embodiment 1

Step 1

By 4-bromoacetophenone (148g), the mixture of dimethyl succinate (130g) and toluene (2.5L) is in suitably reaction Mechanical agitation in flask.Disposably add potassium tert-butoxide (100g) and form precipitate.Water (1L) is added after mixing 1 hour. The water-bearing layer toluene (200ml) reclaimed is cleaned twice and is acidified to pH2 with the HCl of 12N.This product ethyl acetate is extracted Take, then recrystallization from ethylether/hexane (1/1) mixture.Obtain white crystal (170g).NMR shows this product Structure is identical with (E)-4-(4-bromophenyl)-3-(methoxycarbonyl) amyl-3-olefin(e) acid.

Step 2

By from product (160g) and the 50wt% sodium hydrate aqueous solution (200g) of step 1 and water (4 liters) at four liters of beakers Middle mixing.This mixture is heated to boiling, after 1 hour, the HCl that the pH of this solution uses 12N is adjusted to about 2.By institute The precipitate formed is collected by filtration.Obtain shallow white crystal (152g).NMR shows structure and (E)-2-of this product (1-(4-bromophenyl) ethylidene) succinic acid is identical.

Step 3

By the product (152g) from step 2, the mixture of DBSA (5g) and toluene (1L) joins reaction flask and adds Heat is to backflow, and uses Dean-Stark trap except water, carries out 2 hours.The mixture formed is passed through silica gel plug column, and And clean plug column by 2/8 (v/v) ethyl acetate/hexane, and concentrate.This silica gel type used with in other embodiments It is Grade60,230-400 mesh.Hexane (1L) is added in the oil formed.Product crystallizes out, and is collected by filtration And vacuum drying.Obtain shallow white crystal (130g).NMR shows structure and (E)-3-(1-(4-bromophenyl) Asia of this product Ethyl) dihydrofuran-2,5-diketone is identical.

Step 4

In the aluminum chloride (130g) and dichloromethane (1L) mixture of stirring, in 5 minutes intervals, point three parts add to come From the product (125g) of step 3.After being stirred at room temperature 2 hours, HPLC display reaction completes, and forms two kinds of products.Should Reactant mixture slowly pours in water (2L).Observe generation smog.Define substantial amounts of yellow solid.THF (1L) is added Enter and this mixture dissolves this yellow solid.Solid NaCl is saturated for water layer, is then removed by separatory funnel.To back The organic layer received is dried over magnesium sulfate and concentrates.Add ethyl acetate (200ml) and the yellow crystals formed is carried out Collect and be dried (50g).NMR shows structure and 2-(6-bromo-3-methyl isophthalic acid-oxa--1H-indenes-2-base) the acetic acid phase of this product With.

Step 5

By the reaction flask containing manganese chloride (7.46g) and the mixture of lithium chloride (5g) in the vacuum drying oven of 200 ° of C It is dried 1 hour.Add THF (200ml) under nitrogen protection.After 30 minutes, add copper chloride (I) (0.59g) and from step 4 Product (19.4g).This mixture is stirred into transparent, is then cooled to 0 ° of C.To the mixture formed in 2 hours In be added dropwise over the THF solution (99ml) of 2M of butyl magnesium bromide.After addition, this mixture is stirred 2 hours at 0 ° of C, and Add water (200ml).The HCl that the pH of this mixture uses 12N adjusts and is about 2.Add ethyl acetate (200ml).To reclaim Organic moiety be dried and concentrate.By this product by from Teledyne ISCO'sRf purifies.Obtain Oil (4g) as product.NMR shows structure and 2-(5-bromo-1-butyl-1-methyl-3-oxa--2, the 3-bis-of this product Hydrogen-1H-indenes-2-base) acetic acid is identical.

Step 6

Solid magnesium (1.5g) is placed in be equipped with Dropping funnel reaction flask neutralize be dried in an oven.Add THF (60ml) with 1-bromo-4-trifluoromethylbenzene (15.3g).Start with the glycol dibromide of, start to form Grignard Reagent.Use ice bath to control temperature and be in room temperature.After 2 hours, by the product (4.2g) from step 5 at anhydrous THF (20mL) solution in is placed in Dropping funnel, and joins in this reactant mixture in interval at 10 minutes.After addition, will This mixture is stirred at room temperature 2 hours, and adds water (100ml).PH is adjusted to about 2 by the HCl using 12N.Add acetic acid Ethyl ester (100ml).The organic facies formed is collected by separatory funnel, cleans with NaCl/ water, be dried over magnesium sulfate and dense Contracting.The oil obtained is re-dissolved in the toluene (100ml) in reaction flask.Add acetic anhydride (10g) and fluoroform Sulfonic acid bismuth (0.5g).This mixture is refluxed 1 hour and is cooled to room temperature.Add methanol (100ml) and the HCl (1ml) of 12N. This mixture is refluxed 12 hours.Remove whole solvent.Silica gel plug column is separated and is used for this crude product.Obtain as product Oil (3g).NMR show the structure of this product and 10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes- 5-alcohol is identical.

Embodiment 1A

Product (3g) from embodiment 1 step 6 is placed in reaction flask.1-(4-fluorobenzene is added in this flask Base)-1-(4-(N-morpholine is also) phenyl) acrylate-2-alkynes-1-alcohol (2.1g), 1,2-dichloroethanes (30ml) and p-methyl benzenesulfonic acid (70mg).This mixture is refluxed 4 hours.Remove whole solvent.Silica gel plug column is used to purify this product.Obtain conduct The brown oil (2g) of product.NMR shows structure and 3-(4-fluorophenyl)-3-(4-(N-morpholine is also) the phenyl)-10-of this product Bromo-6-Trifluoromethyl-1 3-methyl isophthalic acid 3-butyl-3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Embodiment 2

According to the program of embodiment 1, except: use the THF solution of the 1.4M of methyl-magnesium-bromide to replace butyl in steps of 5 Magnesium bromide；1-bromo-4-(Trifluoromethoxy)benzene is used to replace 1-bromo-4-trifluoromethylbenzene in step 6.NMR shows this product Structure 7,7-bromo-with 10-dimethyl-3-(trifluoromethoxy)-7H-benzo [c] fluorenes-5-alcohol identical.

Embodiment 2A

According to the program of embodiment 1A, except: use the 10-bromo-7,7-dimethyl-3-(trifluoromethoxy) of embodiment 2- 7H-benzo [c] fluorenes-5-alcohol replaces 10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-alcohol；Use 1,1-double (4-methoxyphenyl) acrylate-2-alkynes-1-alcohol replacement 1-(4-fluorophenyl)-1-(4-(N-morpholine is also) phenyl) acrylate-2-alkynes- 1-alcohol.NMR shows structure (4-the methoxyphenyl)-10-bromo-6-trifluoromethoxy-13,13-diformazan double with 3,3-of this product Base-3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Embodiment 3

According to the program of embodiment 1, except using 1-bromo-4-fluorobenzene to replace 1-bromo-4-trifluoromethylbenzene in step 6. NMR shows that structure 7-bromo-with 10-butyl-3-fluoro-7-methyl-7H-benzo [c] fluorenes-5-alcohol of this product is identical.

Embodiment 3A

According to the program of embodiment 1A, except: use the 10-bromo-7-butyl-3-fluoro-7-methyl-7H-benzo of embodiment 3 [c] fluorenes-5-alcohol replaces 10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-alcohol；Use 1,1-double (4-methoxyphenyl) acrylate-2-alkynes-1-alcohol replaces 1-(4-fluorophenyl)-1-(4-(N-morpholine is also) phenyl) acrylate-2-alkynes-1-alcohol. NMR shows structure (4-the methoxyphenyl)-10-bromo-6-fluoro-13-methyl isophthalic acid 3-butyl-3,13-two double with 3,3-of this product Hydrogen-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Embodiment 4

According to the program of embodiment 1, except using 1-bromo-3 in step 6,5-difluorobenzene replaces 1-bromo-4-trifluoromethyl Benzene.NMR shows that structure 7-bromo-with 10-butyl-2,4-two fluoro-7-methyl-7H-benzo [c] fluorenes-5-alcohol of this product is identical.

Embodiment 4A

According to the program of embodiment 1A, except: use 10-bromo-7-butyl-2 of embodiment 4,4-bis-fluoro-7-methyl-7H- Benzo [c] fluorenes-5-alcohol replaces 10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-alcohol；Use 1,1- Double (4-methoxyphenyl) acrylate-2-alkynes-1-alcohol replaces 1-(4-fluorophenyl)-1-(4-(N-morpholine is also) phenyl) acrylate-2-alkynes-1- Alcohol.NMR show double (4-methoxyphenyl) the bromo-5,7-of-10-bis-fluoro-13-methyl isophthalic acid 3-butyl of the structure of this product and 3,3-- 3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Embodiment 5

Step 1

The 2L flask with tribromo-benzene (100g) and magnetic stirring bar is dried 4 hours at vacuum drying oven at 80 ° of C.Add nothing Water THF (500ml).The mixture formed is placed in the saturated ice bath of NaCl.By 3M isopropylmagnesium chloride (160ml) with one Fixed speed is added dropwise in this solution, by internal temperature control to-20 to 0 ° C.This is added on about 30 minutes-1 hour Inside complete.This mixture is stirred half an hour in same temperature, and was slowly added to double [2-(N, N-bis-in interval at 5 minutes Methylamino) ethyl] ether (61g), define substantial amounts of precipitate.The mixture formed is stirred more than 20 minute, and 5 4-trifluoromethyl benzoyl chloride (73g) and the mixture of THF (100ml) is added in minute interval.The mixture formed is stirred Mix a whole night.Slowly add water (100ml), and with the HCl of 3N, pH is adjusted to 2.Organic layer is collected by separatory funnel, uses 5%NaOH/ water and NaCl/ water clean, and are dried and concentrate.In the oil reclaimed, add methanol (300ml), and this product is tied Brilliant.This product is collected by filtration.NMR shows structure and the bromo-4 '-trifluoro of 3,5-bis-of obtained white crystal (87g) Methyl benzophenone is identical.

Step 2

By from the 3 of step 1,5-bis-bromo-4 '-trifluoromethyl benzophenone (75g), dimethyl succinate (32.2g) and The mixture of toluene (800ml) is placed in and is equipped with in churned mechanically three neck 5L flasks.It is dividedly in some parts uncle in interval at 30 minutes Butanol potassium solid (22.6g).Observe an exothermic reaction, concurrently form substantial amounts of precipitate.Water is added after 2 hours , and obtain milk shape mixture (500ml).The pH of this mixture is adjusted to about 2 by the HCl using 3N.It is stirred at room temperature After 10 minutes, collected organic layer, cleans with NaCl/HCl, is dried over mgs 04.After concentration, add hexane and form white crystalline substance Body.This crystal is collected by filtration.NMR show the structure of obtained product (62g) and (E)-4-(3,5-dibromo phenyl)- 3-(methoxycarbonyl)-4-(4-(trifluoromethyl) phenyl) butyl-3-olefin(e) acid is identical.

Step 3

Solid water-free lanthanum chloride (III) (100g) is ground to form the thinnest powder, then with lithium chloride (52g) and anhydrous THF (1 liter) mixes in the 5 liters of three-neck flasks be equipped with mechanical agitation and Dropping funnel.This mixture is refluxed several hours directly Dissolve to it.By solid (E)-4-(3,5-dibromo phenyl)-3-(methoxycarbonyl)-4-(4-(trifluoromethyl) from step 2 Phenyl) butyl-3-olefin(e) acid (106g) dissolving is in the mixture.Then this mixture is cooled to-15 ° of C.By 3M methyl-magnesium-chloride Solution (238ml) is placed in Dropping funnel.The Grignard of the one 30% is slowly added in this mixture.Observe bubble Produce.After temperature returns-15 ° of C, remaining Grignard was added in this mixture in 2 minutes.After 30 minutes, by water (1L) it is slowly added in this mixture, and uses acetic acid that pH is adjusted to acidity.This mixture becomes transparent, defines two Individual layer.Water layer is drained.Organic layer NaCl/ water is cleaned four times, then concentrates and be dried.One bright yellow solid is reclaimed Be dissolved in toluene.Use silica gel plug column to filter this solution, and the clear solution concentration of recovery is dried.Obtain White solid product, and without purify further and in next step.This product of a part is heavily tied from methanol Crystalline substance, and NMR analyzes structure and (the E)-4-((3,5-dibromo phenyl) (4-(trifluoromethyl) phenyl) of the crystal showing this purification Methylene)-5,5-dimethyl dihydrofuran-2 (3H)-one is identical.

Step 4

The product from step 3, toluene (500ml), trifluoromethayl sulfonic acid bismuth (20g) and acetic acid is added in reaction flask (0.24g).The mixture formed is stirred 1 hour under reflux.After it is cooled to room temperature, acetic anhydride (100ml) is added. This mixture is reheated to backflow and after 1 hour, this mixture is cooled to room temperature and is filtered by silica gel plug column.Will The clear solution reclaimed concentrates and is dried.Add acetone (50ml) and form slurry in obtained solid, be subsequently added methanol (250ml).The mixture formed cooling is formed crystal.White crystal (58g) NMR reclaimed is analyzed, its display The structure of this product 7,7-bromo-with 8,10-bis-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-yl acetate is identical.

Step 5

To containing 8,10-bis-bromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-base from step 4 The flask of acetas (2.42g) adds methanol (20mL) and oxolane (10mL).Add concentrated hydrochloric acid (1mL), and should Solution is heated to the 4h that refluxes.Solvent is removed under vacuum, purifications that residue is such as got off: by silica gel connector, use 4:1 hexane/ Ethyl acetate mixture filters as eluent.There is provided cream-colored solid by the part combination containing expectation material and concentration Body (1.63g).NMR analyze this cream colored solid show its structure and 8,10-bis-bromo-7,7-dimethyl-3-(trifluoromethyl)- 7H-benzo [c] fluorenes-5-alcohol is identical.

Embodiment 5A

1-(4-butoxy is added in the chloroformic solution (100mL) of the product (36.24g) of the step 5 from embodiment 5 Phenyl)-1-(4-methoxyphenyl) acrylate-2-alkynes-1-alcohol (28.00g) and 4-DBSA (2.40g).By this solution It is heated to the 8h that refluxes.Oily residue is provided by this reactant mixture concentrating under reduced pressure.This residue is passed through purified by chromatography 9:1 hexane ethyl acetate mixture is used to purify as eluent.To combine containing the part of expectation material and be condensed into oil Shape residue.By this residue recrystallization from dichloromethane and methanol.Crystal is collected by vacuum filtration and is dried and carry For gray solid (20.00g).NMR analyzes this gray solid and shows its structure and 3-(4-butoxy phenyl)-3-(4-methoxyl group Phenyl)-10,12-two bromo-6-Trifluoromethyl-1 3,13-dimethyl-3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] Pyrans is identical.

Embodiment 6

By from the 8 of embodiment 5 step 4,10-bis-bromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5- Yl acetate (53.88g) and 4 '-(4-trans-pentylcyclohexyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxy ring penta Borine-2-base) phenyl)-[1,1 '-biphenyl]-4-Methanamide (56.27g) is dissolved in containing toluene (1000mL) and ethanol (1000mL) in the reaction flask of 1:1 mixture.Potassium carbonate (42.26g) and triphenyl phasphine (8.02g) are added, and should Solution is deaerated by nitrogen bubble 20min.Add acid chloride (2.29g), and this mixture is heated to the 3h that refluxes.Should Reactant mixture is cooled to room temperature, and adds double (triphenylphosphine) Palladous chloride. (II) (7.15g) at toluene (100mL) and ethanol (100mL) in the suspension of the degassing in.This reactant mixture is heated to the 16h that refluxes.This reactant mixture is cooled to room Gentle ethyl acetate (500mL) dilutes.This mixture is passed through celiteFilter aid bed filters, by filtrate collection with true Empty concentration provides residue.By this residue by purified by chromatography, use 19:1 toluene and ethyl acetate mixture conduct Eluent purifies.The part comprising expectation product is combined and is concentrated in vacuo cream-colored residue is provided.Toluene is added This residue precipitates this product.The precipitate formed is collected by vacuum filtration and is dried cream colored solid is provided (32g).NMR analyzes this cream colored solid and shows its structure and 7,7-dimethyl-3-Trifluoromethyl-1 0-[(((4-is anti-for 4-for 4-for 4- Formula-pentylcyclohexyl) phenyl) benzamide) phenyl]-7H-benzo [c] fluorenes-5-alcohol is identical.

Embodiment 7

Step 1-step 4

According to the program of step 1-4 of embodiment 5, except using 3 in step 1,5-dichloro-bromobenzene and 4-methoxybenzene Formyl chloride replaces tribromo-benzene and 4-trifluoromethyl benzoyl chloride.Obtain the shallow white solid as product.NMR shows this product Structure 9-chloro-with 2,4-bis-methoxyl group-7,7-dimethyl-7H-benzo [c] fluorenes-5-yl acetate identical.

Step 5

By the product (5g) from step 4, the mixture of NBS (2.7g) and DMF (100ml) stirs in reaction flask, And it is heated to 90 ° of C.After 2 hours, reactant mixture is poured into water (400ml) and neutralizes with 1/1 ethyl acetate/THF (200ml) extraction.Collected organic layer, cleans three times with aqueous solution of sodium bisulfite, is dried and concentrates.In the product of this recovery Add methanol (100ml).After filtration, it is thus achieved that as the shallow white solid (4.4g) of product.NMR show the structure of this product with The bromo-2,4-of 10-bis-chloro-9-methoxyl group-7,7-dimethyl-7H-benzo [c] fluorenes-5-yl acetate is identical.

Embodiment 8

By the bromo-2,4-of product 10-bis-chloro-9-methoxyl group-7,7-dimethyl-7H-benzo [c] fluorenes-5-from embodiment 7 Yl acetate (4.3g), 4 '-(4-trans-pentylcyclohexyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxy ring penta boron Alkane-2-base) phenyl)-[1,1 '-biphenyl]-4-Methanamide (4.94g), sodium carbonate (4g), THF (200ml), water (20ml) and four The mixture of (triphenylphosphine) palladium (0) (1g) is placed in reaction flask, and within 10 minutes, is taken off by this mixture of nitrogen bubble Gas.It is heated to reflux 17 hours by this mixture, and adds potassium carbonate (5g) and ethanol (50ml), the mixture that will be formed Reflux 8 hours, use THF and saturated aqueous sodium chloride to extract.Collect the organic layer formed, with the 1N's of 100ml HCl cleans three times, cleans once with the sodium sulfite aqueous solution of the 1N of 100ml, cleans once by saturated aqueous sodium chloride, It is dried on magnesium sulfate and concentrates.The residue of recovery is dissolved in 10/1 (v/v) toluene/THF (200ml), then passes through silicon Glue plug column, will use 10/1 toluene/THF to clean and reclaim this product.The clear solution formed is concentrated and joins first In alcohol, and stir half an hour.Collect the solid formed and be dried, the shallow white solid as product is provided (7.5g).NMR shows structure and N-(4-(the 2,4-bis-chloro-5-hydroxyl-9-methoxyl group-7,7-dimethyl-7H-benzo of this product [c] fluorenes-10-base) phenyl)-4'-(4-trans-pentylcyclohexyl)-[1,1'-biphenyl]-4-Methanamide is identical.

Embodiment 9

According to the program of embodiment 5, except using 3 in step 1,5-difluoro benzoyl chloride replaces 4-trifluoromethylbenzene first Acyl chlorides produces the desired product of step 5, is used ethyl acetate to carry out recrystallization as solvent.NMR shows this product Structure 2,4-bromo-with 8,10-bis-bis-fluoro-7,7-dimethyl-7H-benzo [c] fluorenes-5-alcohol is identical.

Embodiment 9A

According to the program of embodiment 1A, except: use the 8 of embodiment 9,10-bis-bromo-2,4-bis-fluoro-7,7-dimethyl- 7H-benzo [c] fluorenes-5-alcohol replaces 10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-alcohol and use 1-(4-fluorophenyl)-1-(4-(N-piperidyl) phenyl) acrylate-2-alkynes-1-alcohol replaces 1-(4-fluorophenyl)-1-(4-(N-morpholine is also) Phenyl) acrylate-2-alkynes-1-alcohol.NMR shows structure and 3-(4-the fluorophenyl)-3-(4-(N-piperidyl) phenyl)-10 of this product, The bromo-5,7-of 12-bis-bis-fluoro-13,13-dimethyl-butyl-3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans phase With.

Embodiment 10

According to the program of embodiment 5, except using 2,4 difluorobenzene formyl chloride to replace 4-trifluoromethylbenzene first in step 1 Acyl chlorides.NMR analyzes the structure showing this product and the bromo-1,3-of 8,10-bis-bis-fluoro-7,7-dimethyl-7H-benzo [c] fluorenes-5-alcohol Identical.

Embodiment 10A

According to the program of embodiment 1A, except using 8,10-bis-bromo-1,3-bis-fluoro-7,7-dimethyl-7H-benzo [c] Fluorenes-5-alcohol replaces 10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-alcohol and uses the double (4-of 1,1- Methoxyphenyl) acrylate-2-alkynes-1-alcohol replacement 1-(4-fluorophenyl)-1-(4-(N-morpholine is also) phenyl) acrylate-2-alkynes-1-alcohol.NMR Show the structure and 3 of this product, double (the 4-methoxyphenyl)-10 of 3-, 12-bis-bromo-6,8-bis-fluoro-13,13-dimethyl-3,13- Dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Embodiment 11

According to the program of the step 1-step 4 of embodiment 5, except using 2 in step 1,5-difluoro benzoyl chloride replaces 4-trifluoromethyl benzoyl chloride.NMR analyzes the structure and 8 showing this product, the bromo-Isosorbide-5-Nitrae of 10-bis--two fluoro-7,7-dimethyl-7H- Benzo [c] fluorenes-5-yl acetate is identical.

Embodiment 12

According to the program of embodiment 6, except using 8, the bromo-Isosorbide-5-Nitrae of 10-bis--two fluoro-7,7-dimethyl-7H-benzo [c] fluorenes- 5-yl acetate replaces 8,10-bis-bromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-yl acetate.NMR divides Analyse this solid and show its structure and 7,7-dimethyl-fluoro-10-of Isosorbide-5-Nitrae-two [4-(4-(4-(4-trans-pentylcyclohexyl) phenyl) Benzamide) phenyl]-7H-benzo [c] fluorenes-5-alcohol is identical.

Embodiment 13

Step 1

Magnesium (3.9g) and THF (50ml) being placed in the dry flask being equipped with Dropping funnel, it comprises 2,4,6-tribromos THF (800mL) solution of toluene (53g).In in Dropping funnel, the THF solution of 1/10th adds this flask, and this is anti- Flask is answered to come to life.This reaction flask is placed in ice bath used, and this reactant mixture is maintained at 0 ° of C and will drip In liquid funnel, remaining solution was added dropwise within half an hour.After stirring 1.5h, add double [2-(N, N-dimethylamino) second Base] ether (28.4g).After stirring 1 hour, disposably add 3,4-dimethoxy-benzoyl chloride (35.5g).The mixing that will be formed Thing stirs a whole night, is added by water (500mL) in this mixture and uses the HCl of 12N that pH adjusts about 2.Being added by DCM should In mixture (500ml), and collecting formed organic layer, washing once, is cleaned once with sodium bicarbonate, over magnesium sulfate It is dried and concentrates.Obtain a kind of yellow oil (65g).This oil is directly used in next step.

Step 2

The product (65g) of step 1, dimethyl succinate (30g) and toluene (500mL) are joined and is equipped with mechanical agitation In the reaction flask of device, Dropping funnel and blanket of nitrogen.This mixture is stirred at room temperature until solid dissolves.Added by Dropping funnel Enter the toluene solution (25wt%, 87.4g) of tert-pentyl alcohol potassium, and this mixture is stirred at room temperature 2 hours.The reaction that will be formed Mixture pours in the water of 1L, and collects water-bearing layer, and it comprises product.This toluene layer 200mL water is extracted.Will combination Water extract toluene clean.HCl (12N) is joined in water extract, until pH is adjusted to 5.Precipitate a kind of yellow Oil.The mixture ethyl acetate extraction that will be formed, is dried over magnesium sulfate, is concentrated in vacuo and is dried.Obtain as product A kind of yellow glassy oil (35g) of thing.It is directly used in next step.

Step 3

By the Stobbe acid product (35g) from step 2, trifluoromethayl sulfonic acid bismuth (2.1g), dichloromethane (200mL) and The mixture of acetic anhydride (27g) mixes in reaction flask in room temperature and stirs 1 hour.The mixture formed is passed through vacuum Evaporation concentrates, and adds methanol (500mL) and HCl (12N, 2mL).The mixture formed is refluxed 4 hours and concentrates Oil is provided.This oil passes through silica gel plug column separate, recrystallization from 2/8 (v/v) ethyl acetate/hexane subsequently.Obtain White crystal (5g) as product.NMR shows structure and 1-(3,5-bis-bromo-4-aminomethyl phenyl)-4-hydroxyl-6 of this product, 7-dimethoxy-2-2-methyl naphthoate is identical.

Step 4

Product (1.5g) from step 3 is dissolved in the oven drying flask being equipped with Dropping funnel and magnetic stirring bar 30mL anhydrous THF in.This mixture is stirred at room temperature, and the THF being added dropwise over the 3M of the methyl-magnesium-bromide of 7mL is molten Liquid.After addition, this mixture is stirred at room temperature a whole night.Then this reactant mixture pours in 100mL water.Use HCl (12N) pH value of this mixture is adjusted to about 5.Add ethyl acetate (100mL).The organic layer formed is separated, at sulfur It is dried on acid magnesium, is concentrated in vacuo and is dried.The white solid (1.5g) reclaimed is directly used in next step.

Step 5

Product (1.5g) from step 4, toluene (100mL) and trifluoromethayl sulfonic acid bismuth (0.04g) are joined equipment Have in the reaction flask of magnetic stirring bar.The mixture formed is refluxed 4 hours.This reactant mixture is passed through silica gel connector Post.Obtain white solid (0.8g) after concentration.NMR shows the structure and 8 of this white solid, 10-bis-bromo-2,3-dimethoxy Base-7,7,9-trimethyl-7H-benzo [c] fluorenes-5-alcohol are identical.

Embodiment 13A

Double (the 4-first of 1,1-is added in the reaction flask of the toluene solution (20ml) of the product (0.8g) containing embodiment 13 Phenyl) acrylate-2-alkynes-1-alcohol (0.8g) and a small amount of p-methyl benzenesulfonic acid crystal.After being stirred at room temperature 1 hour, evaporation is all Solvent.The product of recovery is passed throughPurify, recrystallization from ether ether subsequently.Obtain as product The white crystal (0.95g) of thing.NMR shows the structure and 3 of this product, double (the 4-methoxyphenyl)-10 of 3-, 12-bis-bromo-6,7- Dimethoxy-11,13,13-trimethyl-3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Embodiment 14A

Step 1

In reaction flask, the dioxane (100mL) of degassing and the mixture of toluene (100mL) add 2,2 '-bis-(two Phenylphosphine)-1,1 '-dinaphthalene (1.20g) and acid chloride (II) (0.30g).Add the step 4 from embodiment 5 under nitrogen flowing Product 8,10-bis-bromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-yl acetate (5.10g), add subsequently Enter 1-formyl piperazine (2.80g).Add sodium tert-butoxide (2.80g), and this solution is heated to the 22h that refluxes.By this reaction Mixture is cooled to room Gentle oxolane dilution.This solution is passed through celiteFilter aid bed filters, and will leach Liquid is concentrated under vacuum.By this residue by purified by chromatography, use 1:4 (v:v) dichloromethane and ethyl acetate mixture Purify as eluent.To be combined containing the part of expectation material and concentrate.This residue (1.25g) is directly used In next step.NMR analyze this residue show its structure and 4-(8-bromo-5-hydroxyl-7,7-dimethyl-3-(trifluoromethyl)- 7H-benzo [c] fluorenes-10-base) piperazine-1-formaldehyde is identical.

Step 2

By product (0.69g) and 1-(4-butoxy phenyl)-1-(4-fluorophenyl) the acrylate-2-alkynes-1-alcohol of step 1 (0.60g) it is dissolved in the 1,2-dichloroethanes (20mL) of reaction flask.Add p-methyl benzenesulfonic acid (0.1g), and by this solution It is heated to the 18h that refluxes.This reactant mixture is cooled to room temperature and solvent removed in vacuo.Residue is made by purified by chromatography Purify as eluent with 1:1 hexane and dichloromethane mixture.By the part combination containing expectation material and concentration.Will This residue (0.75g) is directly used in next step.

Step 3

The product (2.00g) of step 2 is dissolved in the dioxane (30mL) of reaction flask.Add 10%HCl aqueous solution (5mL) 2h that refluxes, and by this solution it is heated to.This reactant mixture is cooled to room temperature and pours into saturated sodium bicarbonate In aqueous solution (300mL).Water-bearing layer ethyl acetate (300mL) extraction that will be reclaimed.By this ethyl acetate solution with anhydrous Sodium sulfate is dried, and filtering and concentrating provides residue.This residue is used 1:1 (v:v) acetic acid second by purified by chromatography Ester and carbinol mixture purify as eluent.By the part combination containing expectation material and concentration.Collect this residue to make For product.NMR shows its structure and 3-(4-fluorophenyl)-3-(4-butoxy phenyl)-10-(piperazine-1-base)-6-fluoroform Base-13,13-dimethyl-3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Embodiment 15A

Step 1

According to the program of embodiment 5A, except using 1-(4-fluorophenyl)-1-(4-butoxy phenyl) acrylate-2-alkynes-1-alcohol Replace 1-(4-butoxy phenyl)-1-(4-methoxyphenyl) acrylate-2-alkynes-1-alcohol.NMR analyzes this purple colored product and shows it Structure and 3-(4-butoxy phenyl)-3-(4-fluorophenyl)-10,12-two bromo-6-Trifluoromethyl-1 3,13-dimethyl-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Step 2

The product (2.00g) of the step 1 in reaction flask and 4-(4,4,5,5-tetramethyl-1,3,2-dioxy ring penta boron Alkane-2-base) mixture of phenol (0.57g) solution in the THF (25mL) of 1:1 and the mixture of water (25mL) adds fluorination Potassium (1.5g).This solution is deaerated by nitrogen bubble 10min.Double (triphenylphosphine) chlorination is added in the solution of this degassing Palladium (II) (0.25g).This solution is heated to the 8h that refluxes.This reactant mixture is cooled to room Gentle ethyl acetate dilution. Then this mixture is passed through celiteFilter aid bed filters, and filter liquor ethyl acetate and moisture is joined.Collect vinegar Acetoacetic ester extract, being dried with anhydrous sodium sulfate and concentrating provides oily residue.By this residue by purified by chromatography, 9:1 (v:v) hexane and ethyl acetate mixture is used to purify as eluent.By comprise expectation product part combination and It is concentrated in vacuo and oily residue is provided.The dichloromethane that this oil is dissolved in minimum neutralizes the first being added dropwise over strong stirring In alcoholic solution.The precipitate formed is collected by vacuum filtration and is dried solid (1.00g) is provided.It is solid that NMR analyzes this Body shows that its structure is bromo-with 3-(fluorophenyl)-3-(4-butoxy phenyl)-10-(4-hydroxy phenyl)-6-Trifluoromethyl-1 2- 13,13-dimethyl-3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Embodiment 16

Double (dibenzalacetone) palladium (0) (0.55g) of addition in three neck round bottom (100mL), 2-di-t-butyl phosphine- 3,4,5,6-tetramethyls-2 ', 4 ', 6 '-triisopropyl-1,1 '-biphenyl (1.14g), the potassium phosphate (8.72g) of crushing, from reality Execute 8,10-bis-bromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-yl acetate of the step 4 of example 5 (5.00g) with 4-hydroxybenzamide (2.15g).By flask emptying and fill with nitrogen.Add the tert-butyl alcohol (30mL) of degassing With this mixture is heated to reflux 6h.This reactant mixture is cooled to room Gentle EtOAc dilution.This solution is passed through the third of the twelve Earthly Branches Formula saltFilter aid bed filters and collects filter liquor.This filter liquor is concentrated and residue is used 4:1 by purified by chromatography (v:v) ethyl acetate and hexanes mixtures purify as eluent.Part combination containing expectation material and concentration are carried Fuel feeding.This oil joins in the ethyl acetate of minimum and adds hexane, and provides crystal by flask scraping.Should Crystal is collected by vacuum filtration and is dried provides color white solid (4.27g).NMR analyzes this color white solid and shows Its structure and N-(8-bromo-5-hydroxyl-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-10-base)-4-hydroxy benzenes first Amide is identical.

Embodiment 16A

According to the program of embodiment 5A, except using 1-(4-fluorophenyl)-1-(4-butoxy phenyl) acrylate-2-alkynes-1-alcohol Replace 1-(4-butoxy phenyl)-1-(4-methoxyphenyl) acrylate-2-alkynes-1-alcohol and use the product of embodiment 16A to replace 8, 10-bis-bromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-alcohol.NMR analyzes this cream colored solid and shows that it is tied Structure and 3-(fluorophenyl)-3-(4-butoxy phenyl)-10-(4-hydroxybenzamide) the bromo-13,13-of-6-Trifluoromethyl-1 2-bis- Methyl-3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Embodiment 17

By from embodiment 16A N-(8-bromo-5-hydroxyl-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes- 10-yl)-4-hydroxybenzamide (5.00g), potassium carbonate (5.10g), 2-butanol (50mL) and methanol (50mL) add round bottom and burn Bottle neutralizes degassing 10min.Add tetra-triphenylphosphine palladium (0) (0.55g) and be heated to the 2h that refluxes under a nitrogen.This reaction is mixed Thing is cooled to room temperature, and passes through celiteFilter aid bed filters.Filter liquor is concentrated, and residue is passed through post Shape chromatography uses 4:1 (v:v) ethyl acetate and hexanes mixtures to purify as eluent.By the portion containing expectation material Subassembly and concentration provide foams (4.00g).NMR analyze show structure and the 4-hydroxy-n of these foams-(5-hydroxyl- 7,7-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-10-base) Benzoylamide is identical.

Embodiment 17A

According to the program of embodiment 5A, except using 1-(4-fluorophenyl)-1-(4-butoxy phenyl) acrylate-2-alkynes-1-alcohol Replace 1-(4-butoxy phenyl)-1-(4-methoxyphenyl) acrylate-2-alkynes-1-alcohol and use the product of embodiment 17A to replace 8, 10-bis-bromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo [c] fluorenes-5-alcohol.NMR analyzes this cream colored solid and shows that it is tied Structure and 3-(fluorophenyl)-3-(4-butoxy phenyl)-10-(4-hydroxybenzamide)-6-Trifluoromethyl-1 3,13-dimethyl- 3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Embodiment 18

Step 1

Magnesium (5.38g) and THF (50mL) being placed in the dry flask being equipped with Dropping funnel, it is bromo-that this flask comprises 1- 3,5-dichloro-benzenes (50g) and the mixture of THF (300mL).This solution of 30ml is added in flask by Dropping funnel.Also add Having entered several Bromofumes in this flask, after a few minutes, the solvent in this reaction flask comes to life.By in Dropping funnel Remaining solution is added dropwise over.Frozen water is used to help this reactant mixture is maintained at room temperature once in a while.After addition, this is mixed Compound is stirred at room temperature 2 hours.Benzonitrile (22.82g) is added in this reactant mixture, and mixture is refluxed 2 days.Add The HCl (300ml) of 3N, stirs this mixture 4 hours, then uses ethyl acetate extraction.Collected organic layer and then concentrating. The oil (49g) of this recovery is used for next step without purifying further.

Step 2

The product (47g) of step 1, dimethyl succinate (36g) and toluene (500mL) are joined and is equipped with mechanical agitation Device, in the reaction flask of solid charging hopper and blanket of nitrogen.This mixture is stirred at room temperature until solid dissolves.Added by solid Funnel adds solid potassium tert-butoxide (23.1g), and this mixture is stirred at room temperature 4 hours.The reaction mixing that will be formed Thing pours in the water of 1L, and collects water-bearing layer, and it comprises product.Toluene layer 200mL water is extracted.Water-soluble by merge Liquid toluene cleans.Add HCl (3N), in this aqueous solution, pH is adjusted to 5.The mixture ethyl acetate that will be formed Extraction, is dried over magnesium sulfate, is concentrated in vacuo and is dried.Obtain the oil (65g) as product.It is directly used in next Step.

Step 3

Carry out mixing and being equipped with the anti-of condenser by the product (65g) of step 2 and the mixture of acetic anhydride (200mL) Answer in flask and reflux.After 1 hour, acetic anhydride is removed by vacuum evaporation, the oil (67g) obtained is directly used in next Step.

Step 4

Methanol (500mL) and HCl (12N, 1mL) is added in the reaction flask containing the product (67g) of in steps 3.Should Mixture refluxes 2 hours.Methanol is removed by vacuum evaporation.The oil of recovery is dissolved in dichloromethane, satisfies with sodium bicarbonate And aqueous cleaning, it is dried over magnesium sulfate, is concentrated in vacuo and is dried.Obtain clean oil (48g).Use ethyl acetate/oneself ((v/v) crystallizes this product to alkane (1/9).Obtaining white crystal (12g), it is less desirable regional isomer.Mother solution is dense Contracting.Obtain oil (31g).Structure and 1-(3,5-the Dichlorobenzene base)-4-hydroxyl of most product (80%) in NMR display oil- 2-2-methyl naphthoate is identical.

Step 5

The product (31g) of step 4 is dissolved in the nothing in the oven drying flask being equipped with Dropping funnel and magnetic stirring bar In water THF (500ml).This mixture is stirred at room temperature mixing, and is added dropwise over the toluene/THF of the 1.6M of methyl-magnesium-bromide (1:1) solution (160ml).After addition, this mixture is stirred at room temperature about 16 hours.Then this reactant mixture is poured into In the frozen water of 2L.HCl (12N) is used to be adjusted to about 2 the pH value of this mixture.Add ethyl acetate (500mL).To be formed Organic layer separate, be dried over magnesium sulfate, be concentrated in vacuo and be dried.The product (oil of 30g) reclaimed is directly used in next Step.

Step 6

Product (30g) and the dimethylbenzene (300mL) of step 5 are joined in the reaction flask being equipped with magnetic stirring bar.Add Enter p-methyl benzenesulfonic acid (1g), the mixture formed is refluxed 8 hours.Dimethylbenzene is removed by vacuum evaporation, and by institute The oil product formed is dissolved in ethyl acetate, cleans with water, is dried over magnesium sulfate and concentrates.The crude product obtained is oil (20g).The CombiFlash Rf from Teledyne ISCO is used to purify this product (1.8g) of fraction.Separate After obtain two kinds of components.NMR analyzes structure and the 8,10-bis-chloro-7,7-dimethyl-7H-benzo [c] of display key component Fluorenes-5-alcohol is identical.

Embodiment 18A

The crude product (18g) of embodiment 18 step 6 is placed in reaction flask.Double (the 4-methoxy of 1,1-is added to this flask Base phenyl) acrylate-2-alkynes-1-alcohol (20g), a small amount of p-methyl benzenesulfonic acid crystal and dichloromethane (300ml).This mixture room temperature is stirred Mix 1 hour.Product is used from Teledyne ISCO'sRf purifies, subsequently from ethylether Recrystallization.Obtain the gray solid (10g) as product.NMR analyzes the structure showing this product (4-methoxyl group double with 3,3- Phenyl)-10,12-two chloro-13,13-trimethyl-3,13-dihydro-indeno [2 ', 3 ': 3,4] naphtho-[1,2-b] pyrans is identical.

Part 2-photochromic properties is tested

Prepared by part 2A-test square

Test is to use embodiment 2A-5A, and compound described in 10A, 13A and 18A is carried out in the following manner.To calculate Produce 1.5 × 10^-3A certain amount of compound of gram-molecular weight solution joins in flask, and the monomer that this flask contains 50g mixes Compound: the bisphenol a dimethacrylate (BPA2EO DMA) of the ethoxylation of 4 parts, PEG 600 dimethyl of 1 part Acrylate, and the 2 of 0.033 weight %, 2 '-azo two (2-methyl propionitrile) (AIBN).Each compound by stirring and is needed During when wanting, mild heat is dissolved into this monomer mixture.Obtaining after clear solution, by this sample in vacuum drying oven 25 Torr degassing 5-10 minute.Using syringe, it is 2.2mm+/-0.3mm × 6 inch (15.24cm) that sample pours into inside dimension In the flat plate mold of × 6 inches (15.24cm).By this die sealing and being placed in horizontal air baking oven able to programme, at 5 hours Time interval in be warmed up to 95 ° of C from 40 ° of C, 95 ° of C temperature keep 3 hours, cool in the time interval of 2 hours 60 ° of C, then keep 16 hours at 60 ° of C.After hardening, die sinking, the use diamond chip sawing of this polymer sheet is slit into 2 inches (5.1cm) test square.

Part 2B-response test

Before response test on optical bench, regulation that the test square from part 2A is such as got off: with big away from light source They are exposed to 365nm ultraviolet light 10 minutes by the distance of about 14cm, carry out the photochromic compound in pre-activate sample.Sample UVA irradiance on product surface Licor Model Li-1800 spectroradiometric measurements, and it was found that be 22.2W/ m².Then this sample is placed under Halogen light (500W, 120V) about 10 minutes with the distance away from lamp about 36cm, bleach or Person inactivates the photochromic compound in sample.Illuminance at sample Licor spectroradiometric measurements, and send out It is now 21.9Klux.Keep at least 1 hour cooling down and persistently fading in dark surrounds by this sample the most before test Return to background state.

This optical bench is provided with Newport model #67005300 watt xenon arc lamp and 69911 model power supplys, Vincent The baffle plate that Associates (VS25S2ZM0R3 model has VMM-D4 controller) high-speed computer controls, Schott3mm KG-2 band filter, which removes shortwave radiation, and Midst density filter attenuation gathers from the light of xenon arc lamp, aerosil Optical lens is used for light beam acquiring, and aerosil water box/sample retainer, is used for keeping sample temperature, by be tested Sample is inserted.Temperature in water box is to control by the water circulation system of pumping, is wherein passed through by water and is placed in cooling list Copper coiling in metamemory.For keeping the water box of test sample to comprise aerosil sheet on front-back to eliminate work Change or the spectrum change of monitoring light beam.Water for the filtration passing through water box of photochromic response test be maintained at 72 °F ± 2°.Newport689456 type figure exposure timer is used to control the brightness of xenon arc lamp in sample activation process.

Arrange being used for the wideband light source monitoring response measurement in the way of being perpendicular to case assembly surface.Shorter visible light wave The long signal such as acquisition of getting off improved: collect with point two parts fiber optic cables of end and combination is from 100 watts of tungsten halogen lamps The light filtered respectively of (being controlled by Lambda UP60-14 constant voltage source).By the light Schott from tungsten halogen lamp side KG1 filters filter absorbs heat and Hoya B-440 filters filter makes shorter wavelength pass through.Opposite side is just With Schott KG1 filters filter or unfiltered.Described just such as collection of getting off: will from as described in lamp each The light of side focuses on point an end for the difference of two parts fiber optic cables of end, and is subsequently merged into from the single-end of cable out One light source.By 4, " light pipe is connected to the single end of cable and guarantees correctly to mix.After passing through sample, light reassembles into 2 inches of integrating spheres and being supplied on Ocean Optics S2000 spectrophotometer by fiber optic cables.Use Ocean Software privately owned for Optics SpectraSuite and PPG is measured response and controls the operation of optical bench.

Irradiation for sample response test on optical bench is use International on sample surfaces Light Research radiometer, IL-1700 model sets up, and it has and comprises SED033 type detector, B wave filter and expansion Dissipate the detecting system of device.The Output Display Unit of this radiometer is relative to Licor1800-02Optical Calibration (the factor values setting) that Calibrator corrects, makes display value represent watt/square metre UVA.Initial communication is tested The irradiance of sample spot be set as 3.0 watt/square metre UVA and about 8.6Klux illuminance.At sample response test process In, if dimmed sample has exceeded acceptable power of test limit, irradiance is reduced to 1.0 watt/square metre UVA or Person reproduces when sample is in a half strength in the copolymer.

The adjustment of the output of the xenon arc lamp filtered completes as got off: improve or reduce the electric current by controller to lamp And/or increase or remove the Midst density wave filter in light path.Test sample is exposed to the surface normal 31 ° with it, simultaneously It is perpendicular to monitor the activation light of light.

Sample is activated 30 minutes in the water box that 73 °F (22.8 ° of C) is controlled, then makes it take off under room optical condition Color, until the change of optical density (OD) of activated sample fade to it the highest blackness (saturated) state 1/4 or fade Big 30 minutes.

Optical density (OD) (Δ OD) is by setting up initial transmission from bleached state to the change of dimmed state, open from The baffle plate of xenon arc lamp provides ultraviolet radiation (that is, dimmed) state that test lens becomes activation from bleached state to be come really Fixed.Data are to collect in selected time interval, measure the absorbance in the state of activation, and according to formula: Δ OD=log (%Tb/%Ta) change of calculating optical density, wherein %Tb is the percentage transmission of bleached state, and %Ta is the transmission of the state of activation Percentage rate, and the truth of a matter of this logarithm is 10.

λ in visible-range_max-visIt is such wavelength in visible spectrum, when this wavelength, there occurs activation shape The absorption maximum of the photochromic compound of formula.λ_max-visIt is by Varian Cary4000UV-visible spectrophotometer Or in suitable device, test what photochromic test square was measured.

Δ OD/Min, which represent the sensitivity of photochromic compound response UV light, is the UV first five (5) second Measure in exposure, be then based on per minute expression.Saturation optics density (Δ OD time saturated) is to take under the same conditions , except UV classification duration altogether in addition to 30 minutes.Fade half is photochromic compound in test square After the Δ OD of activated form reaches 30 minutes, or realize saturated or the most saturated after, room temperature remove activation light source (example As by closing baffle plate) time interval (second) of the half of Δ OD measured afterwards.The results are shown in Table 1.

Table 1-photochromic properties test result

Embodiment #	λ_max-vis(nm)	Sensitivity (Δ OD/Min)	Δ OD time saturated	T1/2(s)
					2A	572	0.44	0.27	35
3A	564	0.46	0.34	44
					4A	551	0.65	0.44	35
5A	565	0.23	0.09	14
					9A	603	0.33	0.18	28
10A	562	0.28	0.10	14
					13A	572	0.26	0.26	93
18A	550	0.49	0.36	39

The present invention is described by reference to the detail of its specific embodiments.Such details be not intended to by It is considered limitation of the scope of the invention, except they include the most such degree.

Claims

1. the indeno condensed ring pyrylium compound shown in Formula Il a,

Wherein,

Q " ' selected from chlorine and bromine；

I is selected from 0 to 4, and the R for each i selected from 0-3, t¹With the R for each t²It is each independently selected from: Hydrogen；Br；Cl；OX₇, wherein X₇Selected from C₁-C₁₂Alkyl and C₁-C₁₂Haloalkyl；

R³And R⁴It is each independently selected from C₁-C₈Alkyl；With

B and B ' is each independently selected from mono-substituted phenyl, and wherein the substituent group of phenyl is each independently selected from fluorine, piperidyl With-OX₇, wherein X₇Selected from C₁-C₆Alkyl.

2. the indeno condensed ring pyrylium compound of claim 1,12 of wherein said indeno condensed ring pyrylium compound have bonding To hydrogen thereon, and Q " ' selected from chlorine and bromine.

3. the indeno condensed ring pyrylium compound of claim 1, wherein i is at least 1, and 12 have and are bonded to R thereon¹。

4. the indeno condensed ring pyrylium compound of claim 1, wherein

Q " ' selected from chlorine and bromine,

R for each i¹With the R for each t²It is each independently selected from hydrogen；Br；Cl；OX₇, wherein X₇It is selected from C₁-C₁₂Alkyl and C₁-C₁₂Haloalkyl,

R³And R⁴It is each independently selected from methyl and butyl；With

B and B ' is each independently selected from the mono-substituted phenyl being replaced in its para-position, and wherein the substituent group of phenyl is each independent Ground is selected from fluorine, piperidyl and-OX₇, wherein X₇Selected from C₁-C₆Alkyl.

5. a photochromic composition, it comprises:

The indeno condensed ring pyrylium compound of (a) claim 1；With

B () is selected from polymer, oligomer, monomer and the organic material of its two or more combination.

6. the photochromic composition of claim 5, wherein said polymer is selected from Merlon, polyamide, polyimides, gathers (methyl) acrylate, polycyclic olefin, polyurethane, poly-(urea) carbamate, polysulfide carbamate, polysulfide (urea) amino first Acid esters, polyhydric alcohol (allyl carbonate), cellulose acetate, cellulose diacetate, Triafol T, cellulose acetate propionate, Acetylbutyrylcellulose, polyolefin, polyalkylene-vinyl acetate, poly-(vinyl acetate), poly-(vinyl alcohol), poly-(chloroethene Alkene), poly-(vinyl dimethoxym ethane), poly-(vinyl acetal), poly-(vinylidene chloride), poly-(ethylene glycol terephthalate), poly- Ester, polysulfones, polyolefin, its copolymer, and combinations thereof.

7. the photochromic composition of claim 6, it comprises selected from least one following additive further: dyestuff, row Sequence accelerator, light trigger, thermal initiator, polymerization inhibitor, solvent, light stabilizer, heat stabilizer, releasing agent, rheology control agent, stream Flat agent, free radical quencher and adhesion promotor.

8. photochromic coating compositions, it comprises:

The indeno condensed ring pyrylium compound of (a) claim 1；

B () is selected from the film-forming composition of curable resin composition, thermoplastic resin composition and combinations thereof；With

C solvent compositions that () is optional.

9. photochromic article, it comprises the indeno condensed ring pyrylium compound of claim 1.

10. the photochromic article of claim 9, wherein said photochromic article be selected from following at least one optics unit Part: ophthalmic devices, display element, window, mirror, packaging material, active liquid crystal wafer element and passive liquid crystal wafer element.

The photochromic article of 11. claim 10, wherein said ophthalmic devices is selected from correcting lens, non-correcting lens, contact Lens, intraocular lens, amplifying lens, protection lens and protective eye lens.

The photochromic article of 12. claim 10, wherein said display element is selected from screen, monitor and safety element.