CN1278248A - [Indole] naphthopyrans, prepn., compositions and (co) polymer matrics contg. them, synthesis intermediates - Google Patents
[Indole] naphthopyrans, prepn., compositions and (co) polymer matrics contg. them, synthesis intermediates Download PDFInfo
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- CN1278248A CN1278248A CN 98810841 CN98810841A CN1278248A CN 1278248 A CN1278248 A CN 1278248A CN 98810841 CN98810841 CN 98810841 CN 98810841 A CN98810841 A CN 98810841A CN 1278248 A CN1278248 A CN 1278248A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
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Abstract
The object of the present invention is novel [indole]naphthopyrans compounds as well as the compositions and (co)polymer matrices containing them. Said compounds have interesting photochromic properties. Another object of the present invention is a method of preparing said novel compounds, as well as intermediates useful in said preparation.
Description
The present invention relates to novel [indoles] naphthopyran compounds, it especially has photochromic properties.The invention still further relates to:
-be used to prepare compound, the synthetic intermediate of described [indoles] aphthopyrans;
The preparation method of-described synthetic intermediate and described [indoles] aphthopyrans;
-contain the photochromic composition and the photochromic ophthalmic goods (as eyeglass) of described [indoles] aphthopyrans.
Under the influence of polychromatic light or monochromatic ray (as UV-light), photochromic compound can change color, and, when stopping photoirradiation, or in temperature and/or be different under first kind the polychromatic light or monochromatic influence, photochromic compound can recover its original color.
These photochromic compounds can be applicable to various fields, for example, be used to produce ophthalmic lens, contact lens, solar protection glasses, optical filtering, camera optical system, photographic instrument optical system or other opticinstrument and observation instrument, glass port, ornament, ticket element, perhaps even be used to use up the information storage of learning into (coding) method.
In the opticianry field, particularly in spectacles industry, comprise that the photochromic lens of one or more photochromic compounds must possess:
-high transmission rate when not having ultraviolet ray,
-low-transmittance (high-color rendering) when terrestrial solar radiation,
-suitable the colour developing and the kinetics of fading,
-the color (grey or brown are advisable) that can be accepted by the human consumer, and, be preferably in the eyeglass colour developing and the process of fading and can keep selected color,
-can in 0-40 ℃ temperature range, keep performance,
-because required object lens are expensive senior corrective lens, require significantly long weather resistance.
In fact the characteristic of these eyeglasses is to be determined by contained active photochromic compound; In addition, these photochromic compounds must be compatible well with the organic or inorganic carrier that constitutes eyeglass.
And, it should be noted that the color that obtains grey or brown need use have different colours at least two kinds of photochromic things of (promptly having different maximum absorption wavelengths in visible-range).Therefore, such mixing has also proposed other requirement to photochromic compound.Particularly the colour developing of the active photochromic compound of two or more blended and the kinetics of fading must be basic identical.To their stability in time and with the consistency of plastics or inorganic carrier identical requirement is arranged also.
In the described many photochromic compounds of prior art, but referenced patents or patent application US-A-3,567,605, US-A-3,627,690, US-A-4,826,977, US-A-5,200,116, US-A-5,238,981, US-A-5,411,679, US-A-5,429,744, US-A-5,451,344, US-A-5,458,814, WO-A-9505382, FR-A-2,718,447, chromene or the aphthopyrans described in WO-A-96 14596, WO-A-97 21698 and the open No.36144 of research.These compounds have following structural formula:
These compounds it is said and can satisfy above-mentioned requirements.In fact, even these compounds have one or more desired essential propertys really, for example high light transmittance when not having UV-light and the high-color rendering energy when terrestrial solar radiation are not made the desired whole over-all propertieies of gratifying goods but described so far all compounds do not have industrially scalable ground.Especially do not have a kind of gray own or brown in these compounds, still need use other photochromic thing to obtain one of these two kinds of colors.
WO-A-96 14596 has disclosed several compounds, and they have two strongly and more or less complementary visible region absorption bands.These two absorption bands are usually located at yellow/orange and purple/blueness.Yet first absorption band (yellow) is nowhere near strongly, and these compounds are far unsatisfactory for the stability of photochromic timeliness.
Although the general formula I A of patent application WO-A-97 21698 comprises [indoles] aphthopyrans, yet with regard to the method that described document is not pointed out any synthetic described [indoles] aphthopyrans, this prior art document undeclared described [indoles] aphthopyrans.Described document has disclosed [indeno] aphthopyrans effectively, but does not point out to obtain the method for [indoles] aphthopyrans.The applicant's contribution is the method (effectively synthetic method) that has proposed to obtain this compounds and has found that this compounds has particularly advantageous photochromic properties.More specifically, this compounds has first absorption band of special intensive in Huang/orange district, even still have the second absorption band of high λ maximum and high-color rendering energy in the time of 40 ℃, also has the kinetics of fading fast.
Therefore, of the present invention to liking [indoles] naphthopyran compounds of chemical formula (I):
In the formula: ● R
1And R
2Identical or different, expression separately :-hydrogen,-contain the straight or branched alkyl of 1-12 carbon atom,-contain the cycloalkyl of 3-12 carbon atom,-aryl or heteroaryl have 6-24 carbon atom or 4-24 carbon atom respectively and are selected from least one heteroatoms in sulphur, oxygen and the nitrogen in its basic structure; Described basic structure can randomly selected next group freely at least one substituting group replace :+halogen, particularly fluorine, chlorine and bromine, + contain the straight or branched alkyl of 1-12 carbon atom ,+contain the straight or branched alkoxyl group of 1-12 carbon atom ,+correspond respectively to above-mentioned (C
1-C
12) alkyl and (C
1-C
12) alkoxyl group is by the fluoro-alkyl of straight or branched haloalkyl or halogenated alkoxy that at least one halogen atom replaced, particularly this type ,+contain straight or branched thiazolinyl, particularly vinyl or the allyl group of 2-12 carbon atom ,+-NH
2Group; +-NHR group, R represent to contain the straight or branched alkyl of 1-6 carbon atom; +
Group; R ' and R "; identical or different; that expression contains the straight or branched alkyl of 1-6 carbon atom separately, form with the nitrogen-atoms that is connected perhaps that 5-7 is first to be encircled, described ring can have at least one other heteroatoms that is selected from oxygen, sulphur and nitrogen; described nitrogen-atoms can randomly be replaced by R group; described R group is the straight or branched alkyl that contains 1-6 carbon atom ,+methacryloyl or acryl ,+have an epoxy group(ing) of following chemical formula:
N=1 wherein, 2 or 3-aralkyl or heteroaralkyl, its alkyl is a straight or branched, contains 1-4 carbon atom, the definition of its aryl or heteroaryl is as above; Perhaps described two substituent R
1And R
2Constitute adamantyl, norcamphyl (norbornyl), fluorenylidene, two (C together
1-C
6) alkyl anthrylene or spiral shell (C
5-C
6) the cycloalkyl anthrylene; Described group can be randomly by above-mentioned R
1, R
2By at least one listed in aryl or heteroaryl substituting group is replaced; ● R
3And R
4Identical or different, expression separately :-hydrogen,-halogen, particularly fluorine, chlorine and bromine,-contain the straight or branched alkyl (better being to contain 1-6 carbon atom) of 1-12 carbon atom,-contain the cycloalkyl of 3-12 carbon atom,-contain the straight or branched alkoxyl group (better being to contain 1-6 carbon atom) of 1-12 carbon atom,-correspond respectively to abovementioned alkyl, cycloalkyl, alkoxyl group by haloalkyl, halogenated cycloalkyl or the halogenated alkoxy of at least one halogen atom (particularly being selected from fluorine, chlorine and bromine) replacement,-aryl or heteroaryl, its definition is with above to R
1, R
2The definition that provides is identical ,-aralkyl or heteroaralkyl, and its alkyl is a straight or branched, contains 1-4 carbon atom, the definition of its aryl or heteroaryl and above to R
1, R
2The definition that provides is identical ,-amino or amido (amine or amide group) :-NH
2,-NHR ,-CONH
2,-CONHR,
R, R ', R " are respectively above-mentioned R
1, R
2By in aryl or the heteroaryl amine substituting group being given a definition;--OCOR
6Or-COOR
6Group, R
6The expression contain the straight or branched alkyl of 1-6 carbon atom or contain 3-6 carbon atom cycloalkyl or can be randomly by above-mentioned R
1, R
2Be the phenyl that at least one substituting group replaced listed in aryl or the heteroaryl; ● each integer of 0-4 naturally of m and n; ● R
5Expression :-hydrogen ,-contain the straight or branched alkyl (better being to contain 1-6 carbon atom) of 1-12 carbon atom ,-cycloalkyl of 3-12 carbon atom contained,-contain the straight or branched thiazolinyl of 2-12 carbon atom, particularly vinyl or allyl group ,-phenyl or benzyl can be randomly by above-mentioned R
1, R
2By at least one listed in aryl or heteroaryl substituting group is replaced,--COR
7,-COOR
7Or CONHR
7Group, R
7The expression contain 1-6 carbon atom the straight or branched alkyl, contain 3-6 carbon atom cycloalkyl, contain 2-12 carbon atom straight or branched thiazolinyl (particularly allyl group) or can be randomly by above-mentioned R
1, R
2Be phenyl that at least one substituting group replaced or benzyl listed in aryl or the heteroaryl;-methacryloyl or acryl ,-have an epoxy group(ing) of following chemical formula:
N=1 wherein, 2 or 3.In the described compound of following formula (I), be preferably the have following formula compound of (I1):
In the formula: ● R
1And/or R
2, identical or different, expression can be chosen the aryl or the heteroaryl of replacement wantonly separately, and the basic structure of described aryl or heteroaryl is selected from phenyl, naphthyl, xenyl, pyridyl, furyl, benzofuryl, dibenzofuran base, N-(C
1-C
6) alkyl carbazole, thienyl, benzothienyl, dibenzothiophene base and julolidine groups; R
1And/or R
2It better is the phenyl that is illustrated in para-orientation; ● R
3And R
4Identical or different, represent hydrogen separately, contain straight or branched alkoxyl group, the halogen of 1-6 carbon atom, the straight or branched alkyl that contains 1-6 carbon atom, morpholino base or dialkyl amido-NR ' R ", wherein R ' and R " represent to contain the straight or branched alkyl of 1-6 carbon atom separately; ● R
5Expression hydrogen, the straight or branched alkyl that contains 1-6 carbon atom, the phenyl that can choose replacement wantonly or benzyl ,-COR
7,-COOR
7Or CONHR
7Group, R
7Expression contains the straight or branched alkyl of 1-6 carbon atom, perhaps can choose the phenyl or the benzyl of replacement wantonly.
Substituting group (R at The compounds of this invention
1, R
2, R
5) in, there are some substituting groups to contain and/or form at least one polymerizable and/or crosslinkable reactive group.Exist these reactive groups can be proved to be favourable.Therefore; first object of the present invention comprises as defined above [indoles] naphthopyran compounds; its structure comprises at least one polymerization and/or crosslinked reactive group, and described group comprises thiazolinyl (better being vinyl or allyl group) or methacryloyl, acryl or epoxy group(ing).
Therefore, the The compounds of this invention that belongs to the above-mentioned type can be regarded as has identical or different character, can react the monomer that forms homopolymer and/or multipolymer mutually or with other comonomer, described homopolymer and/or multipolymer have photochromic functional group (as long as the monomer of the invention described above has above-mentioned photochromic functional group), and have macromolecular mechanical property.
Then, of the present invention another to as if form by these straight or branched homopolymer that constitute by The compounds of this invention to small part or multipolymer.
Equally, the invention described above compound also can be regarded linking agent as, and it has can have photochromism or not have to form between the polymer chain of photochromism the response function of bridged bond.The reticulation that can make (reticulates) (cross-linking products) also constitutes another object of the present invention like this.
[indoles] aphthopyrans of compound-chemical formula of the present invention (I)-can with universal method by condensation following formula (II) the compound and the propargyl alcohol derivative of following formula (III) or obtain by the compound of condensation following formula (II) in the presence of four titan-alkoxides (especially purity titanium tetraethoxide) and the aldehyde of following formula (III '):
In the formula, R
3, R
4, the definition in m and n such as the following formula (I);
In the formula, R
1And R
2(condensation reaction can be carried out in solvent (as toluene or tetrahydrofuran (THF)) in the presence of catalyzer (as tosic acid or bromoacetic acid) as the definition in the following formula (I).)
In the formula, R
1And R
2As the definition in the following formula (I) (for example referring to EP-A-0 562 915).
For preparing wherein R
5Compound (following formula (the I of the chemical formula of ≠ H (I)
b)), have a following formula (I with what above-mentioned condensation reaction obtained
a) (R in the formula (I)
5=H) The compounds of this invention carries out deprotonation in the presence of sodium hydride after, can be R randomly with chemical formula
5The suitable electrophilic compound reaction of X, wherein X is a leavings group; This available following reaction formula is represented:
Therefore, synthetic [indoles] of the present invention aphthopyrans uses the compounds of formula (II) on the one hand, uses the compound or the corresponding aldehyde derivatives of formula (III) on the other hand.
● described formula (III) compound is well known by persons skilled in the art, is obtained by corresponding ketone according to the special method of describing among the patent application WO-A-9614596.This ketone can be itself to buy, or make according to currently known methods (coming the Ford reaction as Fei Ruide-Ke) (referring to WO-A-96 14596 and the bibliography of being quoted).The aldehyde derivatives of formula (III) is reset acquisition (referring to J.Org.Chem.1977,42,3403) in acid medium.
● the described compounds of following formula (II) has been opened up [indoles] aphthopyrans that a novelty and good approach prepare formula of the present invention (I).
Therefore, other purpose of the present invention comprises:
-by the method (method as noted above) of described formula (II) compound described [indoles] aphthopyrans;
The described compound of-Shi (II) itself; With
The method of the described compound of-preparation formula (II); Method as described below.
The described compound of formula (II) obtains according to the synthetic schemes of novelty, and each step of this scheme is well known by persons skilled in the art, has perhaps adopted the method in the document.Described synthetic schemes comprises:
-make the compound of formula V
In the formula, R
3, R
4, m and n define with reference to following formula (I);
Z represents hydrogen or unsettled protecting group, as ethanoyl;
Carry out the Ku Ertisi rearrangement reaction, to obtain the compound of formula (VII):
-at HNO
2Existence down by the described compound of diazotization (diazotation) activation formula (VII), make described compound that is activated and reaction of sodium azide, with the corresponding trinitride (azide) of acquisition formula (VIII):
-photochemistry is decomposed described trinitride, to obtain corresponding carbazole, (supposes when Z ≠ H) if necessary then hydroxyl to be gone protection.
(is formula (V when the Z=H according to application WO-A-96 14596 described route of synthesis by the acid that corresponding benzophenone can easily obtain formula V
a); When Z ≠ H is formula (V
b)), this sour hydroxy functional group with or unsettled Z group of no use protect.
Described acid has been experienced the Ku Ertisi rearrangement reaction by known method own, with the amine of production (VII).Preferably under the condition of gentleness, carry out described Ku Ertisi rearrangement reaction according to following reaction scheme:
(Z ≠ H, particularly Z=ethanoyl).
(V
aThe transformation of) → (VI) can be passed through J.Am.Chem.Soc., and 1972,94, the method reasoning described in the 6203-6205 obtains.Ku Ertisi rearrangement reaction (V
b) → (VI) usually the diphenylphosphine trinitride (diphenylphosphorazide, DPPA), triethylamine (NEt
3) and the existence of the trimethyl carbinol (tBuOH) under in the toluene that refluxes, carry out.
The trifluoroacetic acid that the protected amine functional group of compound (VI) is used in the methylene dichloride usually goes protection, to obtain compound (VII).
The aromatics nucleophilic substitution (transformation of (VII) → (VIII)) of being undertaken by the diazotization of arylamine is well known to those skilled in the art, record and narrate especially in Vogel ' s Textbook of Practical Organic Chemistry (the 5th edition, the 922nd page reaches hereinafter).
At last, trinitride (VIII) obtains the carbazole of formula (II) by photochromic rearrangement reaction.The rearrangement of the adjacent nitrine biphenyl of this class (ortho-azidobiphenyl) is described in The Chemistry of Heterocycles (GeorgThieme Verlag Stuttgart, New York, 1995) especially, as the method that obtains carbazole.
Suppose Z ≠ H, the hydroxy functional group of gained carbazole still must go protection.Carry out this with known method own and go to protect step.Therefore, for to this functional group's deacylated tRNA, better be to carry out under the following mild conditions: in 0 ℃ the tetrahydrofuran (THF) that contains 0.5N sodium hydroxide.
The applicant's contribution is the compounds that has prepared and tested above-mentioned formula (I); Described compound has good especially photochromic properties.More specifically, these compounds have the color developing of height, and its λ maximum value is higher than the known aphthopyrans of similar structures.
In addition, the carrier matrix of these compounds and organic polymer or inorganic materials is compatible, and these compounds can be included in the described matrix and as the coating of described matrix.
In solution or polymeric matrix, the initial conditions of The compounds of this invention is colourless or little color that has, and shows dark color under the irradiation of UV-light (365 nanometer) or sunlight class light source rapidly.At last, compound just recovers initial color when irradiation stops.
Another object of the present invention relates to the application of described formula of the present invention (I) compound as photochromic agent.In other words, the applicant proposes at this:
-by mix separately, mutually and/or with the tinting material blended of at least a other another kind of photochromic compound and/or at least a non-photochromic novel photochromic compound formed of aphthopyrans derivative ([indoles] aphthopyrans) as defined above;
-novel photochromic composition, it contains at least a (being total to) polymkeric substance and/or the reticulation that comprises at least a described aphthopyrans derivative of the present invention at least a derivative of aphthopyrans as defined above ([indoles] aphthopyrans) and/or the structure.These photochromic compositions can contain the tinting material and/or at least a stablizer of at least a other another kind of photochromic compound and/or at least a non-photochromic.
Above-mentioned another kind of photochromic compound, non-photochromic tinting material, stablizer are the known prior art products of those skilled in the art.
Optimum is the tone that the mixture of the mixture of photochromic compound of the present invention and/or photochromic compound of the present invention and another kind of prior art photochromic compound is used for producing grey or brown.
Compound of the present invention (particularly as photochromic compound) can be used in the solution.Therefore, at least a described compound dissolution can be obtained photochromic solution in as toluene, methylene dichloride, tetrahydrofuran (THF) or alcoholic acid organic solvent.Gained solution is normally water white.In case be exposed under the sunlight, these solution just show very dark color, in case place them in the place that solar radiation must lack (be them no longer by ultraviolet irradiation time), just recover its colourless state.In general, using very, the product of lower concentration (order of magnitude of 0.01-5% (weight)) just is enough to obtain dark color.
Compound of the present invention ([indoles] aphthopyrans of formula (I)) also can be used as and is dispersed in the polymeric matrix or its lip-deep photochromic material.In fact, the maximum purposes of The compounds of this invention is that photochromic thing is evenly dispersed in polymkeric substance, multipolymer or the polymeric blends, perhaps is evenly dispersed on their surface.(being total to) polymeric matrix that contains the photochromic thing of the invention described above (photochromic thing at least a unbound state as defined above and/or (being total to) polymkeric substance and/or reticulation form and/or the photochromic composition form) constitutes another object of the present invention.
The implementation method that can be used to obtain this matrix is diversified.In method known to those skilled in the art, can exemplify for example have from photochromic thing silicone oil, aliphatic series or aromatic hydrocarbon, dibasic alcohol suspension or solution or from another kind of polymeric matrix photochromic thing is diffused to (being total to) polymkeric substance.According to the character of polymeric matrix, this diffusion is generally carried out under 50-200 ℃, continues 15 minutes to several hours.Another kind of technical application is included in the prescription of polymerizable material and sneaks into photochromic thing, with this mixture deposition from the teeth outwards or place mould, carries out copolyreaction then.Crano etc. are being published in Applied PhotochromicPolymer Systems, the article “ spirooxazine of Ed.Blackie and Son Ltd-1992 and the application in photochromic lens thereof (Spiroxazines and their use in photochromic lenses) " in these and other technology has been described.
A kind of variation of this object according to the present invention can also be grafted to photochromic thing on (being total to) polymkeric substance.Therefore, the invention still further relates to at least a described photochromic thing grafted (being total to) polymkeric substance.Therefore, " (being total to) polymeric matrix that contains at least a photochromic thing of the present invention " this statement is meant that portion within it contains the matrix of described photochromic thing, contains the matrix of described photochromic thing on its surface and with described photochromic thing grafted matrix.
The example of the preferred polymeric materials that photochromic compound of the present invention is used aspect optics comprises following products:
-can choose alkyl ester, cycloalkyl ester, aryl ester or the aralkyl ester of halogenated many (single, double, three or four) vinylformic acid or many (single, double, three or four) methacrylic acid wantonly, perhaps have at least one ether and/or ester and/or carbonic ether and/or carbamate and/or thiocarbamate and/or urea and/or amide group
-polystyrene, polyethers, polyester, polycarbonate (as the polycarbonate of dihydroxyphenyl propane, the polycarbonate of diallyl glycol ether), polyurethane(s), polyepoxides, polyureas, urethane, polythiourethane, polysiloxane, polyacrylonitrile, polymeric amide, aliphatic series or aromatic polyester, vinyl polymer, rhodia, cellulose triacetate, cellulose acetate propionate or polyvinyl butyral acetal
The multipolymer of-at least two types of copolymerizable monomer, described copolymerizable monomer be selected from polymkeric substance listed above precursor monomer (particularly being selected from (methyl) acrylic acid or the like, vinyl-based, allylic and composition thereof) and
-resin, has the nano level double structure, carrying out copolymerization by the mixture to the difunctional monomer of the difunctional monomer of at least a or broad variety (a) and one or more types (b) obtains: one or more difunctional monomers of * type (a) have one of following chemical formula (A) and (A '):
+ chemical formula (A):
In the formula :-R
1, R '
1, R and R ', identical or different, each is hydrogen or methyl naturally; Each integer of 0-4 (comprising 0 and 4) naturally of-m and n better equals 1 or 2 separately;-X and X ', identical or different, be halogen, better represent chlorine and/or bromine;-p and q, each is the integer of 0-4 (comprising 0 and 4) naturally;
+ chemical formula (A '):
In the formula:
-R
1And R '
1, identical or different, each is hydrogen or methyl naturally;
-R is the straight or branched alkyl, the cycloalkyl that contains 3-6 carbon atom that contain 2-8 carbon atom, have chemical formula (R '-ether of O-R "), wherein R ' and R ", identical or different, each contains the straight or branched alkyl of 2-4 carbon atom naturally;
* the difunctional monomer of one or more types (b)-long-chain olefinic Difunctional oligomers-have following chemical formula (B), (B ') and (one of B "):
+ chemical formula (B):
In the formula:
-R
1, R
1', R
2And R '
2, identical or different, each is hydrogen or straight or branched alkyl naturally, better is the straight chained alkyl with 1-4 carbon atom; Good especially is methyl;
-R
3And R
4Difference is one respectively and is hydrogen that another is the thiazolinyl that contains 2-6 carbon atom, better is the thiazolinyl that contains 2-4 carbon atom, and good especially is pseudoallyl;
-R '
3And R '
4Difference is one respectively and is hydrogen that another is the thiazolinyl that contains 2-6 carbon atom, better is the thiazolinyl that contains 2-4 carbon atom, and good especially is pseudoallyl;
-Z represent carbamate-functional (NH-CO-O-), thiocarbamate functional group (NH-CO-S-) or urea functional group (NH-CO-NH-);
-Z ' is independent of Z, better is respectively to Z, Z ' expression carbamate-functional (O-CO-NH-), thiocarbamate functional group (S-CO-NH-) or urea functional group (NH-CO-NH-);
-R ', expression contains the straight or branched alkyl of 2-4 carbon atom;
-R, identical or different, when n 〉=2, for containing the straight or branched alkyl of 2-4 carbon atom;
-Y, identical or different, when n 〉=2, be oxygen or sulphur;
-n is an integer, and its definite method is that the contained the total number of carbon atoms of long-chain that is arranged between two main group (motifs) Z and the Z ' equals 18 at least, better is 18-112 (comprising 18 and 112);
+ chemical formula (B '):
In the formula:
-R
1, R
2, R
3, R
4, R '
1, R '
2, R '
3, R '
4, R and Y such as above definition to formula (B);
-n is an integer, its definite method be major portion (motifs) (R-Y)
nLong-chain in contained the total number of carbon atoms equal 22 at least, better be 22-104 (comprising 22 and 104); + chemical formula (B "):
In the formula:
-R
1, R
2, R
3, R
4, R '
1, R '
2, R '
3, R '
4, R, R ' and Y such as above definition to formula (B);
-Z ' be carbamate-functional (O-CO-NH-) or Z ' be thiocarbamate functional group (S-CO-NH-);
-n is an integer, and its definite method is major portion (R-Y)
nLong-chain in contained the total number of carbon atoms equal 22 at least, better be 22-104 (comprising 22 and 104).
Described resin is explanation among the french patent application FR 9705458 on May 2nd, 1997 by the applicant in the applying date.These resins are mixed at least a short chain difunctionality (methyl) acrylic monomer (the above-mentioned type (a)) and at least a long-chain difunctionality olefinic type monomers (the above-mentioned type (b)) wherein.This mixing energy accesses the net effect of very gratifying photochromic properties/mechanical property.
[indoles] aphthopyrans of formula of the present invention (I) has in described resin introduces the photochromic properties of noting very much.
About described resin, need point out to add tetrem oxidation bisphenol a dimethacrylate (formula (A) compound, wherein R=R '=H, R
1=R '
1=CH
3, m=n=2 and p=q=0) be best as the difunctional monomer of type (a); Adding is by at least a thiazolinyl isocyanic ester (3-pseudoallyl-α especially, α-Er Jiajibianji isocyanic ester or m-TMI
) and at least aly have a chemical formula H
2N-(R-O)
n-R '-NH
2(wherein R and R ' are as above definition to formula (B)) (C
2-C
4Alkyl) the long-chain polyoxyalkylene difunctionality olefinic oligomer that diamines (diamine) reaction obtains is best as the difunctionality " monomer " of type (b).
At last, need point out that usually in described resin, for 100 weight part types (a) and monomeric mixture (b), one or more monomeric content of type (a) are the 40-99 weight part.
The consumption of photochromic thing depends on the deepening degree of requirement in (being total to) polymeric matrix.General its consumption is 0.001-20% (weight).
Photochromic compound of the present invention can use separately, or mixes use to form liquid or solid-state composition, the composition of routine solution as noted above or suspensoid form with other products.Therefore, these compositions that constitute an object of the invention described above comprise that compound of the present invention and other can provide the additional photochromic compound of dark (as grey or brown), and described color is desired for the public in as the application of glasses or sunglasses industry.These additional photochromic compounds are known to one skilled in the art, and existing in the literature the description, as chromene class (chromenes) (US-A-3,567,605, US-A-5,238,981, WO-A-94 22850, EP-A 562 915), spiro-pyrans class or naphtho-spiro-pyrans class (US-A-5,238,981) are (Crano's etc. " Applied Photochromic Polymer Systems, " Ed.Blackie﹠amp with spirooxazine; SonLtd., 1992, the 2 chapters).
The described present composition can also comprise:
-can regulate the non-photochromic colouring matter of tone;
-and/or one or more stablizers, as oxidation inhibitor;
-and/or one or more uvioresistant photo etchings;
-and/or one or more antifree radical agents;
-and/or one or more photochemical excitation attitude deactivators.
These additives can obviously improve the weather resistance of described composition.
According to relevant with the application of The compounds of this invention on the other hand, of the present invention another to as if the ophthalmology goods, the goods of glasses or sunglasses industry for example, these goods comprise at least a compound of the present invention, and/or at least aly form (being total to) polymkeric substance and/or reticulation by one or more The compounds of this invention to small part, and/or at least a composition that contains at least a The compounds of this invention, and/or at least a aforesaid matrix, described matrix be by the organic polymer material that is mixed with at least a The compounds of this invention or inorganic materials or or even inorganic-organic mixed material make.
In practice, the modal goods that the present invention relates to are photochromic glasses eyeglass or sun glasses eyeglass, glass port (buildings, locomotive, automotive glazing), opticinstrument, decorated articles, solar protection goods, data storing goods etc.
Embodiment synthetic and photochromic confirmation by following The compounds of this invention ([indoles] aphthopyrans) illustrates the present invention.The Compound C 1 of described compound of the present invention and prior art compares.
Embodiment 1: synthetic compound (1) (R
1=R
2=p-C
6H
4OCH
3, R
3=R
4=H, R
5=CH
3)
Step 1: restrain acid (the chemical formula V that obtains by corresponding benzophenone according to WO-A-96 14596 with 10.58
a) (R
3=R
4=H) under envrionment temperature, add 4 gram NaH (60%, in mineral oil) in the suspension of 200 milliliters of THF.Under refluxing, stirred 30 minutes, mixture is cooled to 0 ℃, and adds 3.12 milliliters of Acetyl Chloride 98Min.s.After envrionment temperature stirs 1h30, refluxed 30 minutes, with 100 ml waters reaction mixture is hydrolyzed, extract with 200 milliliters of ethyl acetate then.1N sodium hydroxide solution with 2 * 100 milliliters extracts organic phase, and the water that is combined carries out acidifying, uses 2 * 100 milliliters ethyl acetate to extract then.After also evaporation is desolvated through dried over mgso, recrystallization in the mixture of diisopropyl ether/heptane, 6.36 grammeter look crystal (formula V can emanate out
bCompound).
Step 2: will place 100 milliliters of toluene by the product that step 1 obtains, and form suspension, and add 3.1 milliliters of triethylamines then.Under envrionment temperature, stirred 10 minutes, and added 5.39 milliliters of diphenylphosphine trinitride, continue under the envrionment temperature and stirred 30 minutes.Add 2.36 milliliters of trimethyl carbinols, under refluxing, continue to stir and spend the night.After boiling off solvent, mixture is added in the ethyl acetate, wash with sodium hydrogen carbonate solution.Through dried over mgso, boil off solvent then, with the brown oil crystallization in methyl alcohol that obtains, obtain the white solid (protected formula VII compound) of 5.28 grams.
Step 3: the product of step 2 is placed the solution (0 ℃) of 90 milliliters of trifluoroacetic acids at 1/1 mixture of methylene dichloride.After 0 ℃ was stirred 30 minutes, diluted reaction mixture in 150 milliliters of toluene boiled off solvent under vacuum.The oil that obtains is added in 100 milliliters of ethyl acetate, wash with sodium hydrogen carbonate solution then.Through after the dried over mgso, boil off solvent, segregation obtains 4.03 gram true yellow (just yellow) oil (de-protected formula VII compound).
Step 4: the product of step 3 is dissolved in 60 milliliters of acetone, in 0 ℃ of stirring.Add 10 milliliters of 12N HCl, add 1.105 gram Sodium Nitrites (in containing the solution of minimal amount of water) then.Continue to stir 10 minutes in 0 ℃, add 1.3 gram solid sodiumazide then carefully and (carefully may discharge hydrazoic acid! ) stirred 15 minutes in 0 ℃, be diluted in 200 milliliters the ethyl acetate, pour in the solution of potassium carbonate carefully.With 2 * 50 milliliters ethyl acetate extraction water, the organic phase that makes merging is through dried over mgso, and evaporation is until drying.After recrystallization from methyl alcohol, the 3.74 gram grey powder (compound of chemical formula VIII) of emanating out.
Step 5: the product of 1.35 gram steps 4 is dissolved among 30 milliliters of THF, and gained solution places quartzy susceptor.With 2 ultraviolet lamps (Prolabo is used for the pipe of darkroom CN15 for 15W, 254 and 365 nanometers) irradiation reaction mixture 4 days.Boil off solvent then.After recrystallizing methanol, 770 milligrams the yellow powder (protected formula II compound) of emanating out.
Step 6: the solution of 275 milligrams of step 5 products in 20 milliliters of THF is cooled to 0 ℃, adds 10 milliliters through refrigerative 0.5N NaOH solution.In 0 ℃ of stirred reaction mixture 20 minutes, make this reaction quencher with 10 milliliters 1N HCI solution then.Extract with 100 milliliters of ethyl acetate, make organic phase process dried over mgso and boil off solvent.Obtain 225 milligrams true yellow solid (compound of Formulae II) thus.
Step 7: the bromoacetic acid of catalytic amount (spatula point) is added the product of 150 milliliters of steps 6 and 174 milligram of two (p-methoxyphenyl) propargyl alcohol in the solution of 20 milliliters of toluene.Under refluxing, stir spend the night after, (elutriant: this reaction mixture of purifying of diisopropyl ether/EtoAc), the photochromic thing of recrystallization from the mixture of diisopropyl ether/heptane obtains 130 milligrams of green solid (compound of formula I, wherein R through neutral alumina
5=H).
Step 8: the solution of product in 5 milliliters of anhydrous THF of 120 milligrams of steps 7 is cooled to 0 ℃, adds 50 milligrams of NaH (60%, in mineral oil) and 0.2 milliliter of methyl-iodide then in succession.In 0 ℃ of stirred reaction mixture 15 minutes, make the reaction quencher with 10 milliliters saturated ammonium chloride solution then.With 100 milliliters of EtOAc extractive reaction mixtures, through MgSO
4Drying boils off solvent.From the mixture of diisopropyl ether/heptane behind the recrystallize, 65 milligrams green solid product (1) (compound of Formula I, wherein R emanates out
5=CH
3).
Embodiment 2 Compound C 1
Consider the Compound C 1 of prior art, be described among the RD 31 144 to have chemical formula:
This compound can be buied.
Embodiment 3
Evaluate the photochromic properties of described compound (1) and C1.
For this purpose, described compound is sneaked in the matrix with the consumption of about 0.05% (weight).
In fact carry out the mixing of raw material, raw material properties and add-on are following to be pointed out; Pouring mixture into thickness is in 2 millimeters the lens mold, in 75 ℃ of sclerosis cycles of carrying out 2 hours, carries out 1 hour in 120 ℃ then then.
The precursor raw material of matrix is:
0.05 weight part photo-chromic colorant: compound (1) or C1;
Be used for
11.5 weight part Vinylstyrene;
2.9 weight part methacrylic acid 2-ethylhexyl;
14.4 weight part benzyl methacrylate;
0.5 weight part n-dodecane mercaptan;
0.2 weight part AMBN (2,2 '-azo two (2-methylbutyronitrile), by AKZO (Perkadox
) provide);
42.3 weight part DIACRYL 121 derives from AKZO Chimie (tetrem oxidation bisphenol a dimethacrylate);
28.8 weight part [m-TMI
+ poly-(oxygen ethene) diamines (M=600)+poly-(oxygen ethene) diamines (M=2000)] the pseudoallyl oligopolymer of type.
Described pseudoallyl oligopolymer is that the reaction by following material obtains:
● 36.13% (weight) 3-pseudoallyl-α, α-Er Jiajibianji isocyanic ester (CYTEC);
● 44.71% (weight) JEFFAMINE
ED 600 (by the polypropyleneoxide diamine of TEXACO sale);
● 19.16% (weight) JEFFAMINE
ED 2 000 is (by the polyoxypropylene two of TEXACO sale
Amine);
Contain described photochromic compound in the described matrix, be exposed to ultraviolet light irradiation (light source: xenon lamp).The λ maximum value of visible light and the kinetics of fading have been provided in the following table.
Show that by these observed values the λ maximum value of The compounds of this invention is higher than does not have the similar compound of indole ring articulating on 5,6 of aphthopyrans.In addition, The compounds of this invention exists two absorption bands, and this makes it possible to cover the visible range of broad.And, observe first absorption band at visible region, it will firmly get manyly for The compounds of this invention, also has the kinetics of fading faster simultaneously.The ultraviolet light belt that is also noted that The compounds of this invention (1) further moves towards visible region, and this can improve the susceptibility of The compounds of this invention to sunlight.
Claims (13)
1. the compound of chemical formula (I):
In the formula: ● R
1And R
2Identical or different, expression separately :-hydrogen,-contain the straight or branched alkyl of 1-12 carbon atom,-contain the cycloalkyl of 3-12 carbon atom,-aryl or heteroaryl have 6-24 carbon atom or 4-24 carbon atom respectively and are selected from least one heteroatoms in sulphur, oxygen and the nitrogen in its basic structure; Described basic structure can randomly selected next group freely at least one substituting group replace :+halogen, particularly fluorine, chlorine and bromine, + contain the straight or branched alkyl of 1-12 carbon atom ,+contain the straight or branched alkoxyl group of 1-12 carbon atom ,+correspond respectively to above-mentioned (C
1-C
12) alkyl and (C
1-C
12) alkoxyl group is by the fluoro-alkyl of straight or branched haloalkyl or halogenated alkoxy that at least one halogen atom replaced, particularly this type ,+contain straight or branched thiazolinyl, particularly vinyl or the allyl group of 2-12 carbon atom ,+-NH
2Group; +-NHR group, R represent to contain the straight or branched alkyl of 1-6 carbon atom; +
Group; R ' and R "; identical or different; that expression contains the straight or branched alkyl of 1-6 carbon atom separately, form with the nitrogen-atoms that is connected perhaps that 5-7 is first to be encircled, described ring can have at least one other heteroatoms that is selected from oxygen, sulphur and nitrogen; described nitrogen-atoms can randomly be replaced by R group; described R group is the straight or branched alkyl that contains 1-6 carbon atom ,+methacryloyl or acryl ,+have an epoxy group(ing) of following chemical formula:
R, R ', R " are respectively above-mentioned R
1, R
2By in aryl or the heteroaryl amine substituting group being given a definition;--OCOR
6Or-COOR
6Group, R
6The expression contain the straight or branched alkyl of 1-6 carbon atom or contain 3-6 carbon atom cycloalkyl or can be randomly by above-mentioned R
1, R
2Be the phenyl that at least one substituting group replaced listed in aryl or the heteroaryl; ● each integer of 0-4 naturally of m and n; ● R
5Expression :-hydrogen ,-contain the straight or branched alkyl (better being to contain 1-6 carbon atom) of 1-12 carbon atom ,-cycloalkyl of 3-12 carbon atom contained,-contain the straight or branched thiazolinyl of 2-12 carbon atom, particularly vinyl or allyl group ,-phenyl or benzyl can be randomly by above-mentioned R
1, R
2By at least one listed in aryl or heteroaryl substituting group is replaced,--COR
7,-COOR
7Or CONHR
7Group, R
7The expression contain 1-6 carbon atom the straight or branched alkyl, contain 3-6 carbon atom cycloalkyl, contain 2-12 carbon atom straight or branched thiazolinyl (particularly allyl group) or can be randomly by above-mentioned R
1, R
2Be phenyl that at least one substituting group replaced or benzyl listed in aryl or the heteroaryl;-methacryloyl or acryl ,-have an epoxy group(ing) of following chemical formula:
2. compound as claimed in claim 1, it has chemical formula (II):
In the formula: ● R
1And/or R
2, identical or different, expression can be chosen the aryl or the heteroaryl of replacement wantonly separately, and the basic structure of described aryl or heteroaryl is selected from phenyl, naphthyl, xenyl, pyridyl, furyl, benzofuryl, dibenzofuran base, N-(C
1-C
6) alkyl carbazole, thienyl, benzothienyl, dibenzothiophene base and julolidine groups; R
1And/or R
2It better is the phenyl that is illustrated in para-orientation; ● R
3And R
4Identical or different, represent hydrogen separately, contain straight or branched alkoxyl group, the halogen of 1-6 carbon atom, the straight or branched alkyl that contains 1-6 carbon atom, morpholino base or dialkyl amido-NR ' R ", wherein R ' and R " represent to contain the straight or branched alkyl of 1-6 carbon atom separately; ● R
5Expression hydrogen, the straight or branched alkyl that contains 1-6 carbon atom, the phenyl that can choose replacement wantonly or benzyl ,-COR
7,-COOR
7Or CONHR
7Group, R
7Expression contains the straight or branched alkyl of 1-6 carbon atom, perhaps can choose the phenyl or the benzyl of replacement wantonly.
3. the compound of chemical formula (II):
In the formula, ● R
3And R
4, m and n, as in the claim 1 to the definition of formula (I).
4. prepare the method for formula (II) compound of claim 3, it is characterized in that described method comprises:
-make the compound of formula V
In the formula, R
3, R
4, in m and n such as the claim 1 to the definition of formula (I),
Z represents hydrogen or unsettled protecting group, as ethanoyl;
Carry out the Ku Ertisi rearrangement reaction, to obtain the compound of formula (VII):
-at HNO
2Existence under described compound by diazotization activation formula (VII), make described compound that is activated and reaction of sodium azide, with the corresponding trinitride of acquisition formula (VIII):
-photochemistry is decomposed described trinitride, to obtain corresponding carbazole, (supposes when Z ≠ H) if necessary then hydroxyl to be gone protection.
5. prepare the method for formula (I) compound of claim 1, it is characterized in that this method comprises:
-with formula (II) compound:
In the formula, R
3, R
4, in m and n such as the claim 1 to the definition of formula (I),
Perhaps
+ carry out condensation reaction with the propargyl alcohol derivative of following formula (III):
In the formula, R
1And R
2As in the claim 1 to the definition of formula (I);
Perhaps
+ aldehyde with following formula (III ') in the presence of four titan-alkoxides carries out condensation reaction:
In the formula, R
1And R
2As in the claim 1 to the definition of formula (I); To obtain wherein R
5Formula (I) compound of expression hydrogen;
-in the presence of sodium hydride to described wherein R
5Formula (I) compound of expression hydrogen carries out deprotonation, and to make they and chemical formula be R
5The electrophilic compound reaction of X, wherein R
5As in the claim 1 definition but be not hydrogen, X is a leavings group, to obtain wherein R
5It or not formula (I) compound of hydrogen.
6. (be total to) polymkeric substance and/or reticulation, by polymerization and/or the crosslinked at least a monomer of forming by the compound of at least a claim 1 or 2 and obtain.
7. photochromic compound, it is characterized in that it is made up of the compound of claim 1 or 2, perhaps form, perhaps form by the mixture of the tinting material of the compound of at least a claim 1 or 2 and at least a other another kind of photochromic compound and/or at least a non-photochromic by the mixture of the compound of at least two kinds of claims 1 or 2.
8. photochromic composition is characterized in that it comprises:
-at least a claim 1 or 2 compound and/or (being total to) polymkeric substance and/or the reticulation of at least a claim 6,
-and, optional, the tinting material of at least a other another kind of photochromic compound and/or at least a non-photochromic and/or at least a stablizer.
9. (be total to) polymeric matrix, it is characterized in that it comprises:
-at least a claim 1 or 2 compound,
-and/or altogether (polymkeric substance) and/or the reticulation of at least a claim 6,
-and/or the composition of at least a claim 8.
10. matrix as claimed in claim 9 is characterized in that (being total to) polymkeric substance is selected from following material:
-can choose alkyl ester, cycloalkyl ester, aryl ester or the aralkyl ester of halogenated many (single, double, three or four) vinylformic acid or many (single, double, three or four) methacrylic acid wantonly, perhaps have at least one ether and/or ester and/or carbonic ether and/or carbamate and/or thiocarbamate and/or urea and/or amide group
-polystyrene, polyethers, polyester, polycarbonate, polyurethane(s), polyepoxides, polyureas, urethane, polythiourethane, polysiloxane, polyacrylonitrile, polymeric amide, aliphatic series or aromatic polyester, vinyl polymer, rhodia, cellulose triacetate, cellulose acetate propionate or polyvinyl butyral acetal
The multipolymer of-two or more type monomers, or above-mentioned mixture of polymers and
-resin, carry out copolymerization by the mixture to the difunctional monomer of the difunctional monomer of at least a or broad variety (a) and one or more types (b) and obtain:
* one or more difunctional monomers of type (a) have one of following chemical formula (A) and (A '):
+ chemical formula (A):
In the formula:
-R
1, R '
1, R and R ', identical or different, each is hydrogen or methyl naturally;
Each integer of 0-4 naturally of-m and n comprises 0 and 4, better equals 1 or 2 separately;
-X and X ', identical or different, be halogen, better represent chlorine and/or bromine;
-p and q, each is the integer of 0-4 naturally, comprises 0 and 4;
+ chemical formula (A '):
In the formula:
-R
1And R '
1, identical or different, each is hydrogen or methyl naturally;
-R is the straight or branched alkyl, the cycloalkyl that contains 3-6 carbon atom that contain 2-8 carbon atom, have chemical formula (R '-ether of O-R "), wherein R ' and R ", identical or different, each contains the straight or branched alkyl of 2-4 carbon atom naturally;
* the difunctional monomer of one or more types (b)-long-chain olefinic Difunctional oligomers-have following chemical formula (B), (B ') and (one of B "):
+ chemical formula (B):
In the formula:
-R
1, R
1', R
2And R '
2, identical or different, each is hydrogen or straight or branched alkyl naturally, better is the straight chained alkyl with 1-4 carbon atom; Good especially is methyl;
-R
3And R
4Difference is one respectively and is hydrogen that another is the thiazolinyl that contains 2-6 carbon atom, better is the thiazolinyl that contains 2-4 carbon atom, and good especially is pseudoallyl;
-R '
3And R '
4Difference is one respectively and is hydrogen that another is the thiazolinyl that contains 2-6 carbon atom, better is the thiazolinyl that contains 2-4 carbon atom, and good especially is pseudoallyl;
-Z represent carbamate-functional (NH-CO-O-), thiocarbamate functional group (NH-CO-S-) or urea functional group (NH-CO-NH-);
-Z ' is independent of Z, better is respectively to Z, Z ' expression carbamate-functional (O-CO-NH-), thiocarbamate functional group (S-CO-NH-) or urea functional group (NH-CO-NH-);
-R ', expression contains the straight or branched alkyl of 2-4 carbon atom;
-R, identical or different, when n 〉=2, for containing the straight or branched alkyl of 2-4 carbon atom;
-Y, identical or different, when n 〉=2, be oxygen or sulphur;
-n is an integer, and its definite method is that contained the total number of carbon atoms equals 18 at least in the long-chain between two main group Z and Z ', better is 18-112, comprises 18 and 112;
+ chemical formula (B '):
In the formula:
-R
1, R
2, R
3, R
4, R '
1, R '
2, R '
3, R '
4, R and Y such as above definition to formula (B);
-n is an integer, and its definite method is major portion (R-Y)
nLong-chain in contained the total number of carbon atoms equal 22 at least, better be 22-104, comprise 22 and 104; + chemical formula (B "):
In the formula:
-R
1, R
2, R
3, R
4, R '
1, R '
2, R '
3, R '
4, R, R ' and Y such as above definition to formula (B);
-Z ' be carbamate-functional (O-CO-NH-) or Z ' be thiocarbamate functional group (S-CO-NH-);
-n is an integer, and its definite method is major portion (R-Y)
nLong-chain in contained the total number of carbon atoms equal 22 at least, better be 22-104, comprise 22 and 104.
11. ophthalmology goods or sunglasses goods comprise:
-at least a claim 1 or 2 compound,
-and/or (being total to) polymkeric substance and/or the reticulation of at least a claim 6,
-and/or the composition of at least a claim 8,
-and/or the matrix of at least a claim 9 or 10.
12. goods as claimed in claim 11 is characterized in that it is made of eyeglass.
13. glass port and/or opticinstrument comprise:
-at least a claim 1 or 2 compound,
-and/or (being total to) polymkeric substance and/or the reticulation of at least a claim 6,
-and/or the composition of at least a claim 8,
-and/or the matrix of at least a claim 9 or 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9713769A FR2770524B1 (en) | 1997-11-03 | 1997-11-03 | [INDOLE] NAPHTOPYRANS, PREPARATION, COMPOSITIONS AND MATRICES (CO) POLYMERS CONTAINING THEM, INTERMEDIATES OF SYNTHESIS |
| FR97/13769 | 1997-11-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1278248A true CN1278248A (en) | 2000-12-27 |
Family
ID=9512951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98810841 Pending CN1278248A (en) | 1997-11-03 | 1998-10-20 | [Indole] naphthopyrans, prepn., compositions and (co) polymer matrics contg. them, synthesis intermediates |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1042289A4 (en) |
| JP (1) | JP2001521922A (en) |
| CN (1) | CN1278248A (en) |
| AR (1) | AR017542A1 (en) |
| AU (1) | AU743353B2 (en) |
| BR (1) | BR9813140A (en) |
| CA (1) | CA2305753A1 (en) |
| FR (1) | FR2770524B1 (en) |
| WO (1) | WO1999023071A1 (en) |
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| CN113024553A (en) * | 2021-03-16 | 2021-06-25 | 皖南医学院 | Triazolo tetrahydro-beta-carboline derivative and preparation method and application thereof |
| CN113227098A (en) * | 2018-12-21 | 2021-08-06 | 光学转变有限公司 | Indol naphthopyrans |
| CN113227259A (en) * | 2018-12-21 | 2021-08-06 | 光学转变有限公司 | Indol naphthopyrans and photochromic compositions comprising same |
| CN113227099A (en) * | 2018-12-21 | 2021-08-06 | 光学转变有限公司 | Articles comprising indole naphthopyrans |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2783250B1 (en) * | 1998-09-11 | 2001-02-23 | Flamel Tech Sa | C6-C7 ANNELED NAPHTHOPYRANS, THEIR PREPARATION, AND THE POLYMERIC COMPOSITIONS AND MATRICES (CO) CONTAINING THEM |
| FR2786186B1 (en) * | 1998-11-20 | 2001-03-02 | Flamel Tech Sa | [PYRROLE] NAPHTOPYRANS, THEIR PREPARATION, THE POLYMERIC COMPOSITIONS AND MATRICES (CO) CONTAINING THEM |
| FR2794748B1 (en) * | 1999-06-10 | 2001-09-21 | Corning Sa | C5-C6 ANNELED NAPHTHOPYRANS WITH A LACTAM-TYPE C6 CYCLE AND THE POLYMERIC COMPOSITIONS AND MATRICES (CO) CONTAINING THEM |
| US6660727B1 (en) | 1999-11-10 | 2003-12-09 | Rodenstock Gmbh | Photochromic heterocyclically anellated indenochromene compounds |
| WO2002022594A1 (en) * | 2000-09-14 | 2002-03-21 | Optische Werke G. Rodenstock | H-annellated benzo[f]chromenes |
| US9052438B2 (en) | 2005-04-08 | 2015-06-09 | Johnson & Johnson Vision Care, Inc. | Ophthalmic devices comprising photochromic materials with reactive substituents |
| US9028728B2 (en) | 2005-04-08 | 2015-05-12 | Transitions Optical, Inc. | Photochromic materials that include indeno-fused naphthopyrans |
| US8147725B2 (en) | 2005-04-08 | 2012-04-03 | Transitions Optical, Inc | Photochromic materials having extended pi-conjugated systems and compositions and articles including the same |
| US8158037B2 (en) | 2005-04-08 | 2012-04-17 | Johnson & Johnson Vision Care, Inc. | Photochromic materials having extended pi-conjugated systems and compositions and articles including the same |
| US8647538B2 (en) | 2005-04-08 | 2014-02-11 | Transitions Optical, Inc. | Photochromic compounds having at least two photochromic moieties |
| US9139552B2 (en) | 2005-04-08 | 2015-09-22 | Transitions Optical, Inc. | Indeno-fused naphthopyrans having ethylenically unsaturated groups |
| US8277699B2 (en) | 2010-04-30 | 2012-10-02 | Transistions Optical, Inc. | Photochromic materials that include 6-amino substituted indeno-fused naphthopyrans |
| US8535577B2 (en) | 2010-04-30 | 2013-09-17 | Transitions Optical, Inc. | Photochromic materials that include 6-amino substituted indeno-fused naphthopyrans |
| CN113227053A (en) * | 2018-12-21 | 2021-08-06 | 光学转变有限公司 | Process for preparing indole naphthopyrans |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2161697A (en) * | 1932-02-18 | 1939-06-06 | Gen Aniline Works Inc | Hydroxybenzocarbazole compounds |
| FR2688782A1 (en) * | 1992-03-19 | 1993-09-24 | Essilor Int | NOVEL HETEROCYCLIC CHROMES AND THEIR USE IN THE FIELD OF OPHTHALMIC OPTICS. |
| US5651923A (en) * | 1993-12-09 | 1997-07-29 | Transitions Optical, Inc. | Substituted naphthopyrans |
-
1997
- 1997-11-03 FR FR9713769A patent/FR2770524B1/en not_active Expired - Fee Related
-
1998
- 1998-10-20 WO PCT/US1998/021930 patent/WO1999023071A1/en not_active Application Discontinuation
- 1998-10-20 BR BR9813140-0A patent/BR9813140A/en not_active IP Right Cessation
- 1998-10-20 AU AU10963/99A patent/AU743353B2/en not_active Ceased
- 1998-10-20 CN CN 98810841 patent/CN1278248A/en active Pending
- 1998-10-20 JP JP2000518947A patent/JP2001521922A/en not_active Withdrawn
- 1998-10-20 CA CA002305753A patent/CA2305753A1/en not_active Abandoned
- 1998-10-20 EP EP98953636A patent/EP1042289A4/en not_active Withdrawn
- 1998-11-02 AR ARP980105489 patent/AR017542A1/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113227098A (en) * | 2018-12-21 | 2021-08-06 | 光学转变有限公司 | Indol naphthopyrans |
| CN113227259A (en) * | 2018-12-21 | 2021-08-06 | 光学转变有限公司 | Indol naphthopyrans and photochromic compositions comprising same |
| CN113227099A (en) * | 2018-12-21 | 2021-08-06 | 光学转变有限公司 | Articles comprising indole naphthopyrans |
| CN113024553A (en) * | 2021-03-16 | 2021-06-25 | 皖南医学院 | Triazolo tetrahydro-beta-carboline derivative and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1042289A4 (en) | 2003-06-11 |
| WO1999023071A1 (en) | 1999-05-14 |
| BR9813140A (en) | 2000-10-31 |
| AR017542A1 (en) | 2001-09-12 |
| FR2770524B1 (en) | 2000-03-17 |
| AU1096399A (en) | 1999-05-24 |
| EP1042289A1 (en) | 2000-10-11 |
| AU743353B2 (en) | 2002-01-24 |
| CA2305753A1 (en) | 1999-05-14 |
| FR2770524A1 (en) | 1999-05-07 |
| JP2001521922A (en) | 2001-11-13 |
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